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EP1071672A1 - 6-substituted 2,4-diamino-1,3,5-triazine derivatives having at least two asymmetrically substituted carbon atoms, the production thereof, and their use as herbicides - Google Patents

6-substituted 2,4-diamino-1,3,5-triazine derivatives having at least two asymmetrically substituted carbon atoms, the production thereof, and their use as herbicides

Info

Publication number
EP1071672A1
EP1071672A1 EP99913191A EP99913191A EP1071672A1 EP 1071672 A1 EP1071672 A1 EP 1071672A1 EP 99913191 A EP99913191 A EP 99913191A EP 99913191 A EP99913191 A EP 99913191A EP 1071672 A1 EP1071672 A1 EP 1071672A1
Authority
EP
European Patent Office
Prior art keywords
cyano
configuration
carbon atom
optionally substituted
chlorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99913191A
Other languages
German (de)
French (fr)
Inventor
Hans-Jochem Riebel
Stefan Lehr
Katharina Voigt
Markus Dollinger
Mark Wilhelm Drewes
Ingo Wetcholowsky
Randy Allen Myers
Yukiyoshi Watanabe
Toshio Goto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Bayer CropScience KK
Original Assignee
Bayer AG
Nihon Bayer Agrochem KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG, Nihon Bayer Agrochem KK filed Critical Bayer AG
Publication of EP1071672A1 publication Critical patent/EP1071672A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • 6-SUBSTITU IERTE 2 4-DIAMIN0-1, 3, 5-TRIAZINE DERIVATIVES WITH AT LEAST TWO ASYMMETRICALLY SUBSTITUTED CARBON ATOMS, THEIR PRODUCTION AND THEIR USE AS HERBICIDES
  • the invention relates to new substituted, optically active amino triazines with at least two asymmetrically substituted carbon atoms, a process for their preparation and their use as herbicides.
  • Substituted aminotriazines are already known from the (patent) literature (cf. US-3 816 419, US-3 932 167, EP-191 496, EP-273 328, EP-411 153 / WO 90/09 378, WO 97 / 00 254, WO 97/08 156). However, these compounds - in some cases also with asymmetrically substituted carbon atoms - have not attained any particular importance.
  • A represents a single bond or straight-chain or branched alkanediyl or oxaalkanediyl each having up to 6 carbon atoms
  • Dialkylaminoalkylidene amino each having up to 6 carbon atoms in the alkyl groups or alkylidene groups
  • R2 represents hydrogen, halogen or optionally alkyl substituted with cyano, halogen or C ] -C4-alkoxy having up to 6 carbon atoms,
  • R3 represents hydrogen, halogen or optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy-substituted alkyl having up to 6 carbon atoms, or together with R ⁇ represents optionally substituted by cyano, halogen or C 1 -C 4 -alkyl with 2 is up to 5 carbon atoms,
  • R4 represents alkyl having up to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms
  • Y for hydrogen, hydroxy, mercapto, amino, cyano, halogen, or for alkyl, alkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylthio, alkylamino or dialkylamino, each optionally substituted by cyano, halogen or C 1 -C 4 alkoxy up to 6 carbon atoms in the alkyl groups, and
  • Phthalazinyl stands, the possible substituents are each preferably selected from the following group:
  • R ⁇ , R3 and Y have the meaning given above and
  • X represents halogen or alkoxy
  • the compounds of the general formula (I) can be converted into other compounds of the general formula (I) according to the above definition of substituents by conventional methods, for example by acylation of compounds of the formula (I) in which R 1 is amino and / or Y is hydroxyl , e.g. with acetyl chloride or propionic acid chloride, or for example by fluorinating compounds of formula (I) in which Y is hydroxy, e.g. with diethylamino sulfur trifluoride ("DAST") - see the preparation examples.
  • DAST diethylamino sulfur trifluoride
  • the new substituted aminotriazines with at least two asymmetrically substituted carbon atoms of the general formula (I) are notable for their strong and selective herbicidal activity. To a certain extent, they also show fungicidal and insecticidal activity. - 6 -
  • hydrocarbon chains as in alkyl - also in connection with heteroatoms, such as in alkoxy or alkylthio - are each straight-chain or branched.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
  • the invention preferably relates to compounds of the formula (I) in which
  • a for a single bond for methylene (-CH2-), dimethylene (ethane-l, 2-diyl,
  • R represents amino, formylamino or methylamino, ethylamino, dimethylamino, acetylamino, propionylamino, n- or i-butyroylamino, N- or n-substituted by cyano, fluorine, chlorine, methoxy or ethoxy
  • R2 represents hydrogen, fluorine, chlorine, bromine, or in each case methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or e
  • R ⁇ represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or together with R ⁇ for in each case optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl dimethylene (ethane-1,2-diyl), trimethylene (propane-1,3-diyl) or
  • R 4 represents methyl, ethyl, n- or i-propyl, or cyclopropyl
  • Y for hydrogen, hydroxy, mercapto, amino, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, n-, i- or, respectively, which are optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy s-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, acetyloxy, propionyloxy, n- or i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or i-propoxycarbonyloxy, methylaminocarbonyloxy , Ethylamino-carbonyloxy, n- or i-propylaminocarbonyloxy, dimethylaminocarbonyl-oxy, methylthio, ethylthio, n- or i-
  • Z for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl. Isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl. Dihydroisobenzothienyl,
  • the invention relates in particular to compounds of the formula (I) in which
  • A represents a single bond, represents dimethylene (ethane-1,2-diyl, -CH 2 CH2-), oxa-ethanediyl (-CH2O-) or 2-oxa-propane-1,3-diyl (-CH2OCH2-), - 10 -
  • Rl represents amino, formylamino or acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino or dimethylamino-methylenamino, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
  • R2 represents hydrogen, fluorine, chlorine, or in each case methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
  • R ⁇ for hydrogen, fluorine, chlorine, bromine, or in each case optionally by
  • Cyano, fluorine, chlorine, methoxy or ethoxy is substituted methyl, ethyl, n- or i-propyl, or together with R ⁇ stands for dimethylene (ethane-1,2-diyl) which is optionally substituted by cyano, fluorine, chlorine or methyl ,
  • R 4 represents methyl or ethyl
  • Y stands for hydrogen, hydroxy, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , Acetyloxy, propionyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, methylaminocarbonyloxy, ethylaminocarbonyloxy or dimethylaminocarbonyloxy, and
  • Z for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, dihydrobenzurobenzyl Isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzdioxolyl. Oxazolyl. Benzoxazolyl,
  • radicals listed above or those specified in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.
  • R is an example of amino, formylamino, acetylamino, propionylamino or dimethylaminomethyleneamino.
  • the triazine substituent with R ⁇ , R3 and Y is an example of the following groups:
  • Rl, R 2 , R and Y have, for example, the meanings given above in Group 1. 16
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 17
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • Rl, R 2 , R and Y have, for example, the meanings given above in Group 1. 18th
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1. 19
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1. 20th
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 21
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1
  • R, R 2 , R J and Y have, for example, the meanings given above in Group 1. 22
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1. 23
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1. 24
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • Rl, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 25th
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1. 26
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1.
  • HR, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R ⁇ and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R- 3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1. 29
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1. 31
  • R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • R, R 2 , R and Y have, for example, the meanings given above in Group 1.
  • Formula (II) provides a general definition of the substituted biguanides to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I).
  • A, R, R 4 and Z preferably or in particular have those meanings which are preferred or particularly preferred for A, R already in connection with the description of the compounds of the formula (I) according to the invention , R 4 and Z were specified.
  • the starting materials of the general formula (II) are known and / or can be prepared by processes known per se (cf. EP-509 544, US-3 816 419, US-3 860 648, WO 97/00 254, WO 97 / 08 156, DE-19 641 691 (Le A 31 995), DE-19 641 692 (Le A 32 037), DE-19 641 693 (Le A 31 975), production examples).
  • Carboxylic acid derivatives are generally defined by the formula (III).
  • R 2 , R3 and Y preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 2 , R3 and Y. were;
  • X preferably represents fluorine, chlorine, bromine or C ⁇ -
  • the starting materials of the general formula (III) are known and / or can be prepared by processes known per se (cf. J. Chem. Soc. Perkin Trans. I, 1979, 2248-2252; preparation examples).
  • the usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium,
  • the process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent.
  • Inert organic solvents are particularly suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone.
  • Butanone or methyl isobutyl ketone Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide. N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Alcohols, - 34 -
  • ethylene glycol monomethyl ether such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
  • reaction temperatures can be carried out when carrying out the process according to the invention.
  • Process can be varied over a wide range. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 100 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
  • the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess.
  • the reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).
  • the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers.
  • the active compounds according to the invention can be used, for example, in the following plants: - 35 -
  • Brassica, lactuca, cucumis, cucurbita Brassica, lactuca, cucumis, cucurbita.
  • Scirpus Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
  • the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops for example forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop- 36
  • plants on ornamental and sports turf and pastures and for selective weed control in annual crops.
  • the compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence process.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, and soluble powders.
  • formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents
  • Agents ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as
  • Possible solid carriers are: for example ammonium salts and natural rock powder. such as kaolins, clays, talc, chalk, quartz, attapulgite. Montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse - 37 -
  • Silicic acid, aluminum oxide and silicates, as solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • Alkylaryl polyglycol ethers alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite leaching and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Further,
  • Additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt,
  • Molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
  • herbicides are suitable for the mixtures. for example acetochlor,
  • Flazasul requirementson Fluazifop (-P-butyl), Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, (Flodium-pyrmethylsulfur) , Flurenol (-butyl), Fluridone, Fluroxypyr (-meptyl), Flurprimidol, Flurtamone, Fluothiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (- isopropylammonium), Halosafen, Haloxyfop (-ethoxy) , Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox
  • sulfocarb prosul
  • prosul Proliferative, prosultivization, pyraflufen (-ethyl), pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridate, pyriminobac (-methyl), pyrithiobac (- sodium), quinchlorac, quinmerac, quinoclamine (Quizallamine, Quizal -ethyl), quizalopop (-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulognion, tebutam, tebuthiuron,
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • Solutions, suspensions, emulsions, powders, pastes and granules are used. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

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Abstract

The invention relates to substituted, optically active aminotriazines having at least two asymmetrically substituted carbon atoms of formula (I), in which A represents a single bond or each straight chained or branched alkandiyl or oxaalkandiyl; R<1> represents amino, formylamino, or each alkylamino, dialkylamino, alkyl carbonyl amino, N-alkyl-N-alkyl carbonyl-amino, alkoxycarbonyl amino, N-alkyl-N-alkoxycarbonyl-amino, alkyl-aminoalkylide amino or dialkylamino alkylide amino which are optionally substituted by cyano, halogen or C1-C4-alkoxy; R<2>, R<3> represent hydrogen, halogen or alkyl which is optionally substituted by cyano, halogen or C1-C4-alkoxy, or R<3> together with R<2> represent alkandiyl which is optionally substituted by cyano, halogen, or C1-C4-alkyl; R<4> represents alkyl or cycloalkyl; Y represents hydrogen, hydroxy, mercapto, amino, cyano, halogen or each alkyl, alkoxy, alkyl carbonyloxy, alkoxycarbonyloxy, alkylamino carbonyloxy, dialkylamino carbonyloxy, alkylthio, alkylamino or dialkylamino which are optionally substituted by cyano, halogen or C1-C4-alkoxy, and; Z represents a monocyclic or bicyclic carbocyclic or heterocyclic radicals which are optionally substituted. The substituents are provided with the provision that R<2>, R<3> and Y are different from one another in each individual case, and that the substituents are bound on both carbon atoms, on which R<2> and R<3> or R<4>. R,R or R,S or S,R or S,S or R,rac or S,rac are configured [the first statement refers to the triazine-substituents -CR<2>R<3>Y, and the second statement refers to the amino-substituents -CHR<4>(A-Z)]. The invention also relates to a method for producing the compounds of formula (I) and to the utilization thereof as herbicides.

Description

6-SUBSTITU IERTE 2 , 4-DIAMIN0-1 , 3 , 5-TRIAZIN DERIVATE MIT MINDESTENS ZWEI ASYMMETRISCH SUBSTITUIERTEN KOHLENSTOFFATOMEN , DEREN HERSTELLUNG UND DEREN VERWENDUNG ALS HERBIZIDE6-SUBSTITU IERTE 2, 4-DIAMIN0-1, 3, 5-TRIAZINE DERIVATIVES WITH AT LEAST TWO ASYMMETRICALLY SUBSTITUTED CARBON ATOMS, THEIR PRODUCTION AND THEIR USE AS HERBICIDES
Die Erfindung betrifft neue substituierte, optisch .aktive Amino triazine mit mindestens zwei asymmetrisch substituierten Kohlenstoffatomen, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide.The invention relates to new substituted, optically active amino triazines with at least two asymmetrically substituted carbon atoms, a process for their preparation and their use as herbicides.
Substituierte Aminotriazine sind bereits aus der (Patent-)Literatur bekannt (vgl. US- 3 816 419, US-3 932 167, EP-191 496, EP-273 328, EP-411 153/WO 90/09 378, WO 97/00 254, WO 97/08 156). Diese Verbindungen - zum Teil auch mit asymmetrisch substituierten Kohlenstoffatomen - haben jedoch bisher keine besondere Bedeutung erlangt.Substituted aminotriazines are already known from the (patent) literature (cf. US-3 816 419, US-3 932 167, EP-191 496, EP-273 328, EP-411 153 / WO 90/09 378, WO 97 / 00 254, WO 97/08 156). However, these compounds - in some cases also with asymmetrically substituted carbon atoms - have not attained any particular importance.
Es wurden nun die neuen substituierten, optisch aktiven Aminotriazine, mit min- destens zwei asymmetrisch substituierten Kohlenstoffatomen, der allgemeinen Formel (I) gefunden,The new substituted, optically active aminotriazines with at least two asymmetrically substituted carbon atoms of the general formula (I) have now been found
R^R ^
Y- -R°Y- -R °
N -^ N R4 (i)N - ^ NR 4 (i)
Rη " N ^' Λ /'R η " N ^ ' Λ /'
in welcherin which
A für eine Einfachbindung oder für jeweils geradkettiges oder verzweigtes Alkandiyl oder Oxaalkandiyl mit jeweils bis zu 6 Kohlenstoffatomen steht,A represents a single bond or straight-chain or branched alkanediyl or oxaalkanediyl each having up to 6 carbon atoms,
R.1 für Amino, für Formylamino oder für jeweils gegebenenfalls durch Cyano,R.1 for amino, for formylamino or for each optionally by cyano,
Halogen oder Cj-C4-Alkoxy substituiertes Alkylamino, Dialkylamino, Alkylcarbonylamino, N-Alkyl-N-alkylcarbonyl-amino, Alkoxycarbonyl- amino, N-Alkyl-N-alkoxycarbonyl-amino, Alkylaminoalkylidenamino oder - 2 -Halogen or Cj-C4-alkoxy substituted alkylamino, dialkylamino, alkylcarbonylamino, N-alkyl-N-alkylcarbonylamino, alkoxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, alkylaminoalkylideneamino or - 2 -
Dialkylaminoalkylidenamino mit jeweils bis zu 6 Kohlenstoffatomen in den Alkylgruppen bzw. Alkylidengruppen steht,Dialkylaminoalkylidene amino each having up to 6 carbon atoms in the alkyl groups or alkylidene groups,
R2 für Wasserstoff, Halogen oder gegebenenfalls durch Cyano, Halogen oder C]-C4-Alkoxy substituiertes Alkyl mit bis zu 6 Kohlenstoffatomen steht,R2 represents hydrogen, halogen or optionally alkyl substituted with cyano, halogen or C ] -C4-alkoxy having up to 6 carbon atoms,
R3 für Wasserstoff, Halogen oder gegebenenfalls durch Cyano, Halogen oder Cι-C-4-Alkoxy substituiertes Alkyl mit bis zu 6 Kohlenstoffatomen steht, oder zusammen mit R^ für gegebenenfalls durch Cyano, Halogen oder C\- C4- Alkyl substituiertes Alkandiyl mit 2 bis 5 Kohlenstoffatomen steht,R3 represents hydrogen, halogen or optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy-substituted alkyl having up to 6 carbon atoms, or together with R ^ represents optionally substituted by cyano, halogen or C 1 -C 4 -alkyl with 2 is up to 5 carbon atoms,
R4 für Alkyl mit bis zu 6 Kohlenstoffatomen oder für Cycloalkyl mit 3 bis 6 Kohlenstoffatomen steht,R4 represents alkyl having up to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms,
Y für Wasserstoff, Hydroxy, Mercapto, Amino, Cyano, Halogen, oder für jeweils gegebenenfalls durch Cyano, Halogen oder Cι-C4-Alkoxy substituiertes Alkyl, Alkoxy, Alkylcarbonyloxy, Alkoxycarbonyloxy, Alkyl- aminocarbonyloxy, Dialkylaminocarbonyloxy, Alkylthio, Alkylamino oder Dialkylamino mit jeweils bis zu 6 Kohlenstoffatomen in den Alkylgruppen steht, undY for hydrogen, hydroxy, mercapto, amino, cyano, halogen, or for alkyl, alkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylthio, alkylamino or dialkylamino, each optionally substituted by cyano, halogen or C 1 -C 4 alkoxy up to 6 carbon atoms in the alkyl groups, and
Z für eine gegebenenfalls substituierte monocyclische oder bicyclische, carbo- cyclische oder heterocyclische Gruppierung aus der Reihe Cyclopentyl, Cyclohexyl, Phenyl, Naphthyl, Tetralinyl, Decalinyl, Indanyl, Indenyl, Furyl, Benzofuryl, Dihydrobenzofuryl, Thienyl, Be zothienyl, Dihydrobenzo- thienyl, Isobenzofuryl, Dihydroisobenzofuryl, Isobenzothienyl, Dihydroiso- benzothienyl, Pyrrolyl, Indolyl, Isoindolyl, Indolinyl, Isoindolinyl, Benz- dioxolyl, Oxazolyl, Benzoxazolyl, Thiazolyl, Benzthiazolyl, Benzimidazolyl, Indazolyl, Oxadiazolyl, Thiadiazolyl, Pyrazolyl, Pyridinyl. Pyrimidinyl, Pyrazinyl, Pyridazinyl, Chinolyl, Isochinolyl, Chinoxalinyl, Cinnolinyl undZ for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzo, dihydrobenzo , Dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, pyadiazolyl, oxadiazolyl, oxadiazolyl, oxadiazolyl, oxadiazolyl, oxadiazolyl. Pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and
Phthalazinyl steht, wobei die möglichen Substituenten jeweils vorzugsweise aus der folgenden Gruppe ausgewählt sind:Phthalazinyl stands, the possible substituents are each preferably selected from the following group:
Hydroxy, Amino, Cyano, Nitro, Carbamoyl, Sulfamoyl, Halogen, jeweils ge- gebenenfalls durch Hydroxy, Cyano oder Halogen substituiertes Alkyl, Alk- oxy, Alkylamino oder Dialkylamino mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, jeweils gegebenenfalls durch Halogen substituiertes Alkylcarbonyl, Alkoxycarbonyl, Alkylcarbonylamino, Alkylaminocarbonyl, Dialkylaminocarbonyl, Alkylthio, Alkylsulfmyl, Alkylsulfonyl, Alkyl- sulfonylamino, Alkylaminosulfonyl oder Dialkylaminosulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, jeweils gegebenenfalls durch Hydroxy, Cyano, Nitro, Halogen, Cj-C^Alkyl, Cj-C^-Halogenalkyl, Cj- C4-Alkoxy oder Cι-C4-Halogenalkoxy substiuiertes Phenyl oder Phenoxy, sowie jeweils gegebenenfalls durch Halogen substituiertes Methylendioxy oder Ethylendioxy,Hydroxy, amino, cyano, nitro, carbamoyl, sulfamoyl, halogen, each optionally substituted by hydroxy, cyano or halogen-substituted alkyl, alkoxy, alkylamino or dialkylamino each having 1 to 6 carbon atoms in the alkyl groups, each optionally substituted by halogen alkylcarbonyl , Alkoxycarbonyl, alkylcarbonylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, alkylsulfmyl, alkylsulfonyl, alkylsulfonylamino, alkylaminosulfonyl or dialkylaminosulfonyl each having 1 to 6 carbon atoms in the alkyl groups, each optionally by hydroxy, cyano, nitro, halogen, Cj-C ^ -C ^ haloalkyl, C j - C4-alkoxy or -CC-C4-haloalkoxy substituted phenyl or phenoxy, and in each case optionally substituted by halogen methylenedioxy or ethylenedioxy,
mit der Maßgabe, daß in jedem Einzelfall R^, R3 und Y verschieden voneinander sind und daß die Substituenten an den beiden Kohlenstoffatomen, an die R^ und R^ bzw. R^ gebunden sind, wie folgt konfiguriert sind:with the proviso that in each individual case R ^, R3 and Y are different from one another and that the substituents on the two carbon atoms to which R ^ and R ^ and R ^ are bound are configured as follows:
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R,R- Diastereomere"),(a) R configuration on the carbon atom to which R ^ and R ^ are attached and R configuration on the carbon atom to which R4 is attached ("R, R diastereomers"),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R,S- Diastereomere"),(b) R configuration on the carbon atom to which R ^ and R ^ are bonded and S configuration on the carbon atom to which R4 is bonded (“R, S diastereomers”),
(c) S-Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („S.R-(c) S configuration on the carbon atom to which R2 and R ^ are bonded and R configuration on the carbon atom to which R4 is bonded (“S.R-
Diastereomere';), (d) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („S,S- Diastereomere"),Diastereomers'; ) (d) S configuration on the carbon atom to which R ^ and R ^ are attached and S configuration on the carbon atom to which R is attached ("S, S diastereomers"),
(e) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R,rac-Diastereomere"),(e) R configuration on the carbon atom to which R ^ and R ^ are attached and racemic configuration on the carbon atom to which R4 is attached ("R, rac diastereomers"),
(f) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („S,rac-Diastereomere").(f) S configuration on the carbon atom to which R ^ and R ^ are attached and racemic configuration on the carbon atom to which R is attached ("S, rac diastereomers").
Da das C-Atom, an welches R2, R3 und Y gebunden sind, nicht in racemischer Form vorliegt, sind somit alle erfindungsgemäßen Verbindungen optisch aktiv.Since the C atom to which R 2 , R 3 and Y are bound is not in racemic form, all of the compounds according to the invention are thus optically active.
Man erhält die neuen substituierten Aminotriazine mit mindestens zwei asymmetrisch substituierten Kohlenstoffatomen der allgemeinen Formel (I), wenn man substituierte Biguanide der allgemeinen Formel (II)The new substituted aminotriazines having at least two asymmetrically substituted carbon atoms of the general formula (I) are obtained if substituted biguanides of the general formula (II)
N ^N R4 N ^ NR 4
(II)(II)
R1' *N' ι\rR 1 ' * N ' ι \ r
H H in welcherH H in which
A, R , R4 und Z die oben angegebene Bedeutung haben,A, R, R4 and Z have the meaning given above,
- und/oder Säureaddukte von Verbindungen der allgemeinen Formel (II) -and / or acid adducts of compounds of the general formula (II)
mit (optisch aktiven) Carbonsäurederivaten der allgemeinen Formel (III) R^with (optically active) carboxylic acid derivatives of the general formula (III) R ^
Y- -RJ Y- -R J
(III)(III)
O <^vO <^ v
in welcherin which
R^, R3 und Y die oben angegebene Bedeutung haben undR ^, R3 and Y have the meaning given above and
X für Halogen oder Alkoxy steht,X represents halogen or alkoxy,
gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt,if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
und gegebenenfalls an den so erhaltenen Verbindungen der allgemeinen Formel (I) im Rahmen der obigen Substituentendefinition weitere Umwandlungen nach üblichen Methoden durchführt.and optionally on the compounds of the general formula (I) thus obtained in the context of the above definition of substituents, further conversions are carried out by customary methods.
Die Verbindungen der allgemeinen Formel (I) können nach üblichen Methoden in andere Verbindungen der allgemeinen Formel (I) gemäß obiger Substituentendefinition umgewandelt werden, beispielsweise durch Acylierung von Verbindungen der Formel (I), in welcher Rl für Amino und/oder Y für Hydroxy steht, z.B. mit Acetylchlorid oder Propionsäurechlorid, oder beispielsweise durch Fluorierung von Verbindungen der Formel (I), in welcher Y für Hydroxy steht, z.B. mit Diethyl- aminoschwefeltrifluorid („DAST") - vgl. die Herstellungsbeispiele.The compounds of the general formula (I) can be converted into other compounds of the general formula (I) according to the above definition of substituents by conventional methods, for example by acylation of compounds of the formula (I) in which R 1 is amino and / or Y is hydroxyl , e.g. with acetyl chloride or propionic acid chloride, or for example by fluorinating compounds of formula (I) in which Y is hydroxy, e.g. with diethylamino sulfur trifluoride ("DAST") - see the preparation examples.
Die neuen substituierten Aminotriazine mit mindestens zwei asymmetrisch substituierten Kohlenstoffatomen der allgemeinen Formel (I) zeichnen sich durch starke und selektive herbizide Wirksamkeit aus. In gewissem Umfang zeigen sie auch fungizide und insektizide Wirksamkeit. - 6 -The new substituted aminotriazines with at least two asymmetrically substituted carbon atoms of the general formula (I) are notable for their strong and selective herbicidal activity. To a certain extent, they also show fungicidal and insecticidal activity. - 6 -
In den Definitionen sind die Kohlenwasserstoffketten, wie in Alkyl - auch in Verbindung mit Heteroatomen, wie in Alkoxy oder Alkylthio - jeweils geradkettig oder verzweigt.In the definitions, the hydrocarbon chains, as in alkyl - also in connection with heteroatoms, such as in alkoxy or alkylthio - are each straight-chain or branched.
Halogen steht im allgemeinen für Fluor, Chlor, Brom oder lod, vorzugsweise fürHalogen generally represents fluorine, chlorine, bromine or iodine, preferably
Fluor, Chlor oder Brom, insbesondere für Fluor oder Chlor.Fluorine, chlorine or bromine, especially for fluorine or chlorine.
Gegenstand der Erfindung sind vorzugsweise Verbindungen der Formel (I), in welcherThe invention preferably relates to compounds of the formula (I) in which
A für eine Einfachbindung, für Methylen (-CH2-), Dimethylen (Ethan-l,2-diyl,A for a single bond, for methylene (-CH2-), dimethylene (ethane-l, 2-diyl,
-CH CH2-), Ethyliden (Ethan-l,l-diyl, -CH(CH3)-), Oxaethandiyl (-CH20-), Trimethylen (Propan-l,3-diyl, -CH2CH2CH2-), Propyliden (Propan-l,l-diyl, -CH(C2H5)-), Propan-2,3-diyl (-CH(CH3)CH2-), 2-Methyl-propan-l,3-diyl (-CH2CH(CH3)CH2-), 3-Oxa-propan-l,3-diyl (-CH2CH20-), 2-Oxa-propan--CH CH 2 -), ethylidene (ethane-l, l-diyl, -CH (CH 3 ) -), oxaethanediyl (-CH 2 0-), trimethylene (propane-l, 3-diyl, -CH2CH2CH2-), Propylidene (propane-l, l-diyl, -CH (C 2 H 5 ) -), propane-2,3-diyl (-CH (CH 3 ) CH 2 -), 2-methyl-propane-l, 3- diyl (-CH 2 CH (CH 3 ) CH 2 -), 3-oxa-propane-l, 3-diyl (-CH 2 CH 2 0-), 2-oxa-propane
1,3-diyl (-CH2OCH2-), Tetramethylen (Butan- 1,4-diyl, -CH2CH2CH2CH2-), Butan-2,4-diyl (-CH(CH3)CH CH2-), Butan-2,3-diyl (-CH(CH3)CH(CH3)-), 3-Methyl-butan-2,4-diyl (-CH(CH3)CH(CH3)CH2-), 4-Oxa-butan-2,4-diyl (-CH(CH3)CH2θ-), Pentan-3,5-diyl (-CH(C2H5)CH2CH2-), 5-Oxa-pentan- 3,5-diyl (-CH(C2H5)CH20-), 4-Oxa-pentan-2,5-diyl (-CH(CH3)CH OCH2-) oder 5-Oxa-hexan-3,6-diyl (-CH(C2H5)CH2OCH2-) steht,1,3-diyl (-CH 2 OCH 2 -), tetramethylene (butane-1,4-diyl, -CH2CH2CH2CH2-), butane-2,4-diyl (-CH (CH3) CH CH 2 -), butane 2,3-diyl (-CH (CH 3 ) CH (CH 3 ) -), 3-methylbutane-2,4-diyl (-CH (CH 3 ) CH (CH 3 ) CH 2 -), 4- Oxa-butane-2,4-diyl (-CH (CH 3 ) CH2θ-), pentane-3,5-diyl (-CH (C 2 H 5 ) CH 2 CH2-), 5-oxapentane-3, 5-diyl (-CH (C 2 H5) CH 2 0-), 4-oxapentane-2,5-diyl (-CH (CH 3 ) CH OCH2-) or 5-oxa-hexane-3,6- diyl (-CH (C 2 H5) CH 2 OCH2-),
R für Amino, für Formylamino oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methylamino, Ethylamino, Dimethylamino, Acetylamino, Propionylamino, n- oder i-Butyroylamino, N-R represents amino, formylamino or methylamino, ethylamino, dimethylamino, acetylamino, propionylamino, n- or i-butyroylamino, N- or n-substituted by cyano, fluorine, chlorine, methoxy or ethoxy
Methyl-N-acetyl-amino, N-Ethyl-N-acetyl-amino, N-Methyl-N-propionyl- amino, Methoxycarbonylamino, Ethoxycarbonylamino, n- oder i-Propoxy- carbonylamino, N-Methyl-N-methoxycarbonyl-amino, N-Ethyl-N-methoxy- carbonyl-amino, N-Methyl-N-ethoxycarbonyl-amino, Methylaminomethylen- amino, Ethylaminomethylenamino, Methylaminoethylidenamino oder Di- methylaminomethylenamino steht, R2 für Wasserstoff, Fluor, Chlor, Brom, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl steht,Methyl-N-acetylamino, N-ethyl-N-acetylamino, N-methyl-N-propionylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, N-methyl-N-methoxycarbonylamino , N-ethyl-N-methoxy-carbonyl-amino, N-methyl-N-ethoxycarbonyl-amino, methylaminomethylene-amino, ethylaminomethyleneamino, methylaminoethylidenamino or dimethylaminomethyleneamino, R2 represents hydrogen, fluorine, chlorine, bromine, or in each case methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R^ für Wasserstoff, Fluor, Chlor, Brom, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl steht, oder zusammen mit R^ für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl oder Ethyl sub- stituiertes Dimethylen (Ethan-l,2-diyl), Trimethylen (Propan-l,3-diyl) oderR ^ represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or together with R ^ for in each case optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl dimethylene (ethane-1,2-diyl), trimethylene (propane-1,3-diyl) or
Tetramethylen (Butan- 1,4-diyl) steht,Tetramethylene (butane-1,4-diyl),
R4 für Methyl, Ethyl, n- oder i-Propyl, oder für Cyclopropyl steht,R 4 represents methyl, ethyl, n- or i-propyl, or cyclopropyl,
Y für Wasserstoff, Hydroxy, Mercapto, Amino, Cyano, Fluor, Chlor, Brom, oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i- oder s-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i- oder s-Butoxy, Acetyloxy, Propionyloxy, n- oder i-Butyroyloxy, Methoxycarbonyloxy, Ethoxycarbonyl- oxy, n- oder i-Propoxycarbonyloxy, Methylaminocarbonyloxy, Ethylamino- carbonyloxy, n- oder i-Propylaminocarbonyloxy, Dimethylaminocarbonyl- oxy, Methylthio, Ethylthio, n- oder i-Propylthio, n-, i- oder s-Butylthio, Methylamino, Ethylamino, n- oder i-Propylamino, n-, i- oder s-Butylamino oder Dimethylamino steht, undY for hydrogen, hydroxy, mercapto, amino, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, n-, i- or, respectively, which are optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy s-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, acetyloxy, propionyloxy, n- or i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or i-propoxycarbonyloxy, methylaminocarbonyloxy , Ethylamino-carbonyloxy, n- or i-propylaminocarbonyloxy, dimethylaminocarbonyl-oxy, methylthio, ethylthio, n- or i-propylthio, n-, i- or s-butylthio, methylamino, ethylamino, n- or i-propylamino, n- , i- or s-butylamino or dimethylamino, and
Z für eine gegebenenfalls substituierte monocyclische oder bicyclische, carbo- cyclische oder heterocyclische Gruppierung aus der Reihe Cyclohexyl, Phenyl, Naphthyl, Tetralinyl, Decalinyl, Indanyl, Indenyl, Furyl, Benzofuryl, Dihydrobenzofuryl, Thienyl, Benzothienyl, Dihydrobenzothienyl. Isobenzo- furyl, Dihydroisobenzofuryl, Isobenzothienyl. Dihydroisobenzothienyl,Z for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl. Isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl. Dihydroisobenzothienyl,
Pyrrolyl, Indolyl, Isoindolyl, Indolinyl, Isoindolinyl, Benzdioxolyl. Oxazolyl, - 8 -Pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzdioxolyl. Oxazolyl, - 8th -
Benzoxazolyl, Thiazolyl, Benzthiazolyl, Benzimidazolyl, Indazolyl, Oxadi- azolyl, Thiadiazolyl, Pyrazolyl, Pyridinyl, Pyrimidinyl, Pyrazinyl, Pyridazin- yl, Chinolyl, Isochinolyl, Chinoxalinyl, Cinnolinyl und Phthalazinyl steht,Benzoxazolyl, thiazolyl, benzthiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazin-yl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl,
wobei die möglichen Substituenten jeweils vorzugsweise aus der folgendenwhere the possible substituents are each preferably from the following
Gruppe ausgewählt sind:Group are selected:
Hydroxy, Amino, Cyano, Nitro, Carbamoyl, Sulfamoyl, Fluor, Chlor, Brom, jeweils gegebenenfalls durch Hydroxy, Cyano, Fluor oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Methylamino, Ethylamino, n- oder i-Hydroxy, amino, cyano, nitro, carbamoyl, sulfamoyl, fluorine, chlorine, bromine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-
Propylamino, n-, i-, s- oder t-Butylamino oder Dimethylamino, jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxy carbonyl, n- oder i-Propoxy- carbonyl, Acetylamino, Propionylamino, n- oder i-Butyroylamino, Methyl- aminocarbonyl, Ethylaminocarbonyl, n- oder i-Propylaminocarbonyl, Di- methylaminocarbonyl, Methylthio, Ethylthio, n- oder i-Propylthio, n-, i-, s- oder t-Butylthio, Methylsulfinyl, Ethylsulfmyl, n- oder i-Propylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulfonyl, Methylsulfonyl- amino, Ethylsulfonylamino, n- oder i-Propylsulfonylamino, Methylamino- sulfonyl, Ethylaminosulfonyl, n- oder i-Propylaminosulfonyl, oder Dimethyl- aminosulfonyl, jeweils gegebenenfalls durch Hydroxy, Cyano, Nitro, Fluor, Chlor, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Difluormethoxy oder Trifluormethoxy substiuiertes Phenyl oder Phenoxy, sowie jeweils ge- gebenenfalls durch Fluor und/oder Chlor substituiertes Methylendioxy oderPropylamino, n-, i-, s- or t-butylamino or dimethylamino, in each case optionally substituted by fluorine and / or chlorine, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxy carbonyl, n- or i-propoxycarbonyl , Acetylamino, propionylamino, n- or i-butyroylamino, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t -Butylthio, methylsulfinyl, ethylsulfmyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino, methylaminosulfonyl, propylsulfonyl, ethylaminosulfonyl, ethylaminosulfonyl , or dimethylaminosulfonyl, each optionally by hydroxy, cyano, nitro, fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n - or i-Propoxy, n-, i-, s- or t-butoxy, difluoromethoxy or trifluoromethoxy substituted P henyl or phenoxy, as well as methylenedioxy or substituted by fluorine and / or chlorine
Ethylendioxy,Ethylenedioxy,
mit der Maßgabe, daß in jedem Einzelfall R^, R3 und Y verschieden voneinander sind und daß die Substituenten an den Kohlenstoffatomen, an die R^ und R^ bzw. R4 gebunden sind, wie folgt konfiguriert sind: - 9 -with the proviso that in each individual case R ^, R3 and Y are different from one another and that the substituents on the carbon atoms to which R ^ and R ^ or R4 are bound are configured as follows: - 9 -
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („R,R- Diastereomere"),(a) R configuration on the carbon atom to which R ^ and R ^ are attached and R configuration on the carbon atom to which R is attached ("R, R diastereomers"),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R,S- Diastereomere"),(b) R configuration on the carbon atom to which R ^ and R ^ are attached and S configuration on the carbon atom to which R 4 is attached ("R, S diastereomers"),
(c) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („S,R-(c) S configuration on the carbon atom to which R ^ and R ^ are attached and R configuration on the carbon atom to which R4 is attached ("S, R-
Diastereomere"),Diastereomers "),
(d) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („S,S- Diastereomere"),(d) S configuration on the carbon atom to which R ^ and R ^ are attached and S configuration on the carbon atom to which R is attached ("S, S diastereomers"),
(e) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („R,rac-Diastereomere"),(e) R configuration on the carbon atom to which R ^ and R ^ are attached and racemic configuration on the carbon atom to which R is attached ("R, rac diastereomers"),
(f) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („ S ,rac-Diastereomere") .(f) S configuration on the carbon atom to which R ^ and R ^ are attached and racemic configuration on the carbon atom to which R is attached ("S, rac diastereomers").
Die Erfindung betrifft insbesondere Verbindungen der Formel (I), in welcherThe invention relates in particular to compounds of the formula (I) in which
A für eine Einfachbindung, für Dimethylen (Ethan-l,2-diyl, -CH2CH2-), Oxa- ethandiyl (-CH2O-) oder 2-Oxa-propan-l ,3-diyl (-CH2OCH2-) steht, - 10 -A represents a single bond, represents dimethylene (ethane-1,2-diyl, -CH 2 CH2-), oxa-ethanediyl (-CH2O-) or 2-oxa-propane-1,3-diyl (-CH2OCH2-), - 10 -
Rl für Amino, für Formylamino oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Acetylamino, Propionyl- amino, Methoxycarbonylamino, Ethoxycarbonylamino, oder Dimethylamino- methylenamino steht,Rl represents amino, formylamino or acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino or dimethylamino-methylenamino, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R2 für Wasserstoff, Fluor, Chlor, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i- Propyl steht,R2 represents hydrogen, fluorine, chlorine, or in each case methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R^ für Wasserstoff, Fluor, Chlor, Brom, oder jeweils gegebenenfalls durchR ^ for hydrogen, fluorine, chlorine, bromine, or in each case optionally by
Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl steht, oder zusammen mit R^ für jeweils gegebenenfalls durch Cyano, Fluor, Chlor oder Methyl substituiertes Dimethylen (Ethan-l,2-diyl) steht,Cyano, fluorine, chlorine, methoxy or ethoxy is substituted methyl, ethyl, n- or i-propyl, or together with R ^ stands for dimethylene (ethane-1,2-diyl) which is optionally substituted by cyano, fluorine, chlorine or methyl ,
R4 für Methyl oder Ethyl steht,R 4 represents methyl or ethyl,
Y für Wasserstoff, Hydroxy, Cyano, Fluor, Chlor, Brom, oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i-Propoxy, Acetyl- oxy, Propionyloxy, Methoxycarbonyloxy, Ethoxycarbonyloxy, Methylamino- carbonyloxy, Ethylaminocarbonyloxy oder Dimethylaminocarbonyloxy steht, undY stands for hydrogen, hydroxy, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , Acetyloxy, propionyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, methylaminocarbonyloxy, ethylaminocarbonyloxy or dimethylaminocarbonyloxy, and
Z für eine gegebenenfalls substituierte monocyclische oder bicyclische, carbo- cyclische oder heterocyclische Gruppierung aus der Reihe Phenyl, Naphthyl, Tetralinyl, Decalinyl, Indanyl, Indenyl, Furyl, Benzofuryl, Dihydrobenzo- furyl, Thienyl, Benzothienyl, Dihydrobenzothienyl, Isobenzofuryl, Dihydro- isobenzofuryl, Isobenzothienyl, Dihydroisobenzothienyl, Pyrrolyl, Indolyl, Isoindolyl, Indolinyl, Isoindolinyl, Benzdioxolyl. Oxazolyl. Benzoxazolyl,Z for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, dihydrobenzurobenzyl Isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzdioxolyl. Oxazolyl. Benzoxazolyl,
Thiazolyl, Benzthiazolyl, Benzimidazolyl, Indazolyl, Pyrazolyl, Pyridinyl, - 11 -Thiazolyl, benzthiazolyl, benzimidazolyl, indazolyl, pyrazolyl, pyridinyl, - 11 -
Pyrimidinyl, Pyrazinyl, Pyridazinyl, Chinolyl, Isochinolyl, Chinoxalinyl, Cinnolinyl und Phthalazinyl steht,Pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl,
wobei die möglichen Substituenten jeweils vorzugsweise aus der folgenden 5 Gruppe ausgewählt sind:the possible substituents are each preferably selected from the following 5 groups:
Hydroxy, Amino, Cyano, Nitro, Carbamoyl, Sulfamoyl, Fluor, Chlor, Brom, jeweils gegebenenfalls durch Hydroxy, Cyano, Fluor oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, Dimethylamino, jeweils gegebenenfalls durch Fluor und/oder 0 Chlor substituiertes Acetyl, Methoxy carbonyl, Ethoxy carbonyl, Dimethyl- aminocarbonyl, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl, Ethylsulfonyl oder Dimethylaminosulfonyl, jeweils gegebenenfalls durch Hydroxy, Cyano, Nitro, Fluor, Chlor, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Trifluormethyl, Methoxy, 5 Ethoxy, n- oder i-Propoxy, Difluormethoxy oder Trifluormethoxy sub- stiuiertes Phenyl oder Phenoxy, sowie jeweils gegebenenfalls durch Fluor und oder Chlor substituiertes Methylendioxy oder Ethylendioxy,Hydroxy, amino, cyano, nitro, carbamoyl, sulfamoyl, fluorine, chlorine, bromine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, methoxy, ethoxy, n- or i-propoxy, dimethylamino, each optionally substituted by fluorine and / or 0 chlorine, acetyl, methoxy carbonyl, ethoxy carbonyl, dimethylaminocarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl , Ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, in each case optionally by hydroxy, cyano, nitro, fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, 5 ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and also methylene dioxy or ethylenedioxy optionally substituted by fluorine and or chlorine,
mit der Maßgabe, daß in jedem Einzelfall R R3 und Y verschieden voneinander 0 sind und daß die Substituenten an den Kohlenstoffatomen, an die R^ und R bzw. R4 gebunden sind, wie folgt konfiguriert sind:with the proviso that in each individual case R R3 and Y are different from one another and that the substituents on the carbon atoms to which R 1 and R or R4 are bonded are configured as follows:
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R3 gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R,R- 5 Diastereomere"),(a) R configuration on the carbon atom to which R ^ and R3 are bonded and R configuration on the carbon atom to which R4 is bonded (“R, R- 5 diastereomers”),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R.S- Diastereomere"),(b) R configuration on the carbon atom to which R ^ and R are attached and S configuration on the carbon atom to which R4 is attached ("R.S diastereomers"),
J 0 - 12 -J 0 - 12 -
(c) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („S,R- Diastereomere"),(c) S configuration on the carbon atom to which R 1 and R are attached and R configuration on the carbon atom to which R is attached ("S, R diastereomers"),
(d) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („S,S- Diastereomere").(d) S configuration on the carbon atom to which R 1 and R are attached and S configuration on the carbon atom to which R is attached (“S, S diastereomers”).
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Reste- definitionen gelten sowohl für die Endprodukte der Formel (I) als auch entsprechend für die jeweils zur Herstellung benötigten Ausgangs- oder Zwischenprodukte. Diese Restedefinitionen können untereinander, also auch zwischen den angegebenen bevorzugten Bereichen beliebig kombiniert werden.The general definitions of radicals listed above or those specified in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.
Beispiele für die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) sind in den nachstehenden Gruppen aufgeführt.Examples of the compounds of the general formula (I) according to the invention are listed in the groups below.
Gruppe 1Group 1
R steht hierbei beispielhaft für Amino, Formylamino, Acetylamino, Propionylamino oder Dimethylaminomethylenamino.R is an example of amino, formylamino, acetylamino, propionylamino or dimethylaminomethyleneamino.
Der Triazin-Substituent mit R^, R3 und Y steht hierbei beispielhaft für folgende Gruppierungen:The triazine substituent with R ^, R3 and Y is an example of the following groups:
-CH(CH3)C2H5, -CH(CH3)C3H7-n, -CH(CH3)C3H7-i, -CH(C2H5)C3H7-n. -CH(C2H5)C3H7-i, -C(CH3)(C2H5)C3H7-n, -C(CH3)(C2H5)C3H7-i, -CH(OH)CH3, - 13 --CH (CH 3 ) C 2 H 5 , -CH (CH 3 ) C 3 H 7 -n, -CH (CH 3 ) C 3 H 7 -i, -CH (C 2 H 5 ) C 3 H 7 - n. -CH (C 2 H 5 ) C 3 H 7 -i, -C (CH 3 ) (C 2 H 5 ) C 3 H 7 -n, -C (CH 3 ) (C 2 H 5 ) C 3 H 7 -i, -CH (OH) CH 3 , - 13 -
-CH(OH)C2H5j -CH(OH)C3H7-n, -CH(OH)C3H7-i, -CH(OCHO)CH3, -CH(OCHO)C2H5; -CH(OCHO)C3H7-n, -CH(OCHO)C3H7-i, -CH(OCOCH3)CH3, -CH(OCOCH3)C2H5? -CH(OCOCH3)C3H7-n, -CH(OCOCH3)C3H7-i, -CH(OCOC2H5)CH3, -CH(OCOC3H7-n)CH3, -CH(OCOC3H7-i)CH3, -C(OH)(CH3)C2H5, -C(OH)(CH3)C3H7-n, -C(OH)(CH3)C3H7-i, -CH(SH)CH3,-CH (OH) C 2 H 5j -CH (OH) C 3 H 7 -n, -CH (OH) C 3 H 7 -i, -CH (OCHO) CH 3 , -CH (OCHO) C 2 H 5 ; -CH (OCHO) C 3 H 7 -n, -CH (OCHO) C 3 H 7 -i, -CH (OCOCH 3 ) CH 3 , -CH (OCOCH 3 ) C 2 H 5? -CH (OCOCH 3 ) C 3 H 7 -n, -CH (OCOCH 3 ) C 3 H 7 -i, -CH (OCOC 2 H 5 ) CH 3 , -CH (OCOC 3 H 7 -n) CH 3 , -CH (OCOC 3 H 7 -i) CH 3 , -C (OH) (CH 3 ) C 2 H 5 , -C (OH) (CH 3 ) C 3 H 7 -n, -C (OH) (CH 3 ) C 3 H 7 -i, -CH (SH) CH 3 ,
-CHBrCH3, -CHBrC2H5, -CHBrC3H7-n, -CHBrC3H7-i, -CBr(CH3)C2H5, -CBr(CH3)C3H7-n, -CBr(CH3)C3H7-i, -CHC1CH3, -CHC1C2H5, -CHClC3H7-n, -CHClC3H7-i, -CC1(CH3)C2H5, -CCl(CH3)C3H7-n, -CCl(CH3)C3H7-i, -CHFCH3, -CHFC2H5, -CHFC3H7-n, -CHFC3H7-i, -CF(CH3)C2H5, -CF(CH3)C3H7-n, -CF(CH3)C3H7-i, -CH(CF3)CH3, -CH(CF3)C2H5j -CH(CF3)C3H7-n,-CHBrCH 3 , -CHBrC 2 H 5 , -CHBrC 3 H 7 -n, -CHBrC 3 H 7 -i, -CBr (CH 3 ) C2H5, -CBr (CH 3 ) C 3 H 7 -n, -CBr ( CH 3 ) C 3 H 7 -i, -CHC1CH 3 , -CHC1C 2 H 5 , -CHClC 3 H 7 -n, -CHClC 3 H 7 -i, -CC1 (CH 3 ) C 2 H 5 , -CCl ( CH 3 ) C 3 H 7 -n, -CCl (CH 3 ) C 3 H 7 -i, -CHFCH 3 , -CHFC 2 H 5 , -CHFC 3 H 7 -n, -CHFC 3 H 7 -i, - CF (CH 3 ) C 2 H 5 , -CF (CH 3 ) C 3 H 7 -n, -CF (CH 3 ) C 3 H 7 -i, -CH (CF 3 ) CH 3 , -CH (CF 3 ) C 2 H 5j -CH (CF 3 ) C 3 H 7 -n,
-CH(CF3)C3H7-i, -C(CF3)(CH3)C2H5, -C(CF3)(CH3)C3H7-n, -C(CF3)(CH3)C3H7-i, -CH(OH)CF3, -C(OH)(CF3)CH3, -CF(OH)CF3, -CH(CH3)OCH3, -CH(C2H5)OCH3, -CH(C3H7-n)OCH3, -CH(C3H7-i)OCH3, -C(CH3)(C2H5)OCH3, -C(CH3)(C3H7-n)OCH3, -C(CH3)(C3H7-i)OCH3, -CH(CH3)OC2H5, -CH(C2H5)OC2H5, -CH(C3H7-n)OC2H5, -CH(C3H7-i)OC2H5, -CH(CH3)OC3H7-n, -CH(CH3)OC3H7-i,-CH (CF 3 ) C 3 H 7 -i, -C (CF 3 ) (CH 3 ) C 2 H 5 , -C (CF 3 ) (CH 3 ) C 3 H 7 -n, -C (CF 3 ) (CH 3 ) C 3 H 7 -i, -CH (OH) CF 3 , -C (OH) (CF 3 ) CH 3 , -CF (OH) CF 3 , -CH (CH 3 ) OCH 3 , - CH (C 2 H 5 ) OCH 3 , -CH (C 3 H 7 -n) OCH 3 , -CH (C 3 H 7 -i) OCH 3 , -C (CH 3 ) (C 2 H 5 ) OCH 3 , -C (CH 3 ) (C 3 H 7 -n) OCH 3 , -C (CH 3 ) (C 3 H 7 -i) OCH 3 , -CH (CH 3 ) OC 2 H 5 , -CH (C 2 H5) OC 2 H5, -CH (C 3 H 7 -n) OC 2 H 5 , -CH (C 3 H 7 -i) OC 2 H5, -CH (CH 3 ) OC 3 H 7 -n, - CH (CH 3 ) OC 3 H 7 -i,
-CH(C2H5)OC3H7-n, -CH(C2H5)OC3H7-i, -CH(CF3)OCH3, -CH(CF3)OC2H5, -CHFCF3, -CHC1CF3, -CF(CH3)CF3, -CF(C2H5)CF3, -CF(C3H7-n)CF3, -CF(C3H7-i)CF3, -CH(CN)CH3, -CH(CN)C2H5, -CH(CN)C3H7-n, -CH(CN)C3H7-i, -C(CN)(CH3)C2H5, -C(CN)(CH3)C3H7-n, -C(CN)(CH3)C3H7-n, -CH(CH3)SCH3, -CH(C2H5)SCH3, -CH(C3H7-n)SCH3, -CH(C3H7-i)SCH3, -C(CH3)(C2H5)SCH3,-CH (C 2 H 5 ) OC 3 H 7 -n, -CH (C 2 H 5 ) OC 3 H 7 -i, -CH (CF 3 ) OCH 3 , -CH (CF 3 ) OC 2 H 5 , -CHFCF 3 , -CHC1CF 3 , -CF (CH 3 ) CF 3 , -CF (C 2 H 5 ) CF 3 , -CF (C 3 H 7 -n) CF 3 , -CF (C 3 H 7 -i ) CF 3 , -CH (CN) CH 3 , -CH (CN) C 2 H 5 , -CH (CN) C 3 H 7 -n, -CH (CN) C 3 H 7 -i, -C (CN ) (CH 3 ) C 2 H 5 , -C (CN) (CH 3 ) C 3 H 7 -n, -C (CN) (CH 3 ) C 3 H 7 -n, -CH (CH 3 ) SCH 3 , -CH (C 2 H 5 ) SCH 3 , -CH (C 3 H 7 -n) SCH 3 , -CH (C 3 H 7 -i) SCH 3 , -C (CH 3 ) (C 2 H 5 ) SCH 3 ,
-C(CH3)(C3H7-n)SCH3, -C(CH3)(C3H7-i)SCH3, -CH(CH3)SC2H5, -CH(C2H5)SC2H5, -CH(C3H7-n)SC2H5, -CH(C3H7-i)SC2H5, -CHFBr, -CHFC1, -CFBrCH3, -CFC1CH3, -CFBiCl, -CH(CH2C1)C1, -CH(CH3)CH2OCH3, -CH(CH3)CH2OC2H5, -CH(C2H5)CH2OCH3, -CH(CH3)CH2CH2OCH3,-C (CH 3 ) (C 3 H 7 -n) SCH 3 , -C (CH 3 ) (C 3 H 7 -i) SCH 3 , -CH (CH 3 ) SC 2 H 5 , -CH (C 2 H5) SC 2 H5, -CH (C 3 H 7 -n) SC 2 H 5 , -CH (C 3 H 7 -i) SC 2 H 5 , -CHFBr, -CHFC1, -CFBrCH 3 , -CFC1CH 3 , -CFBiCl, -CH (CH 2 C1) C1, -CH (CH 3 ) CH 2 OCH 3 , -CH (CH 3 ) CH 2 OC 2 H 5 , -CH (C 2 H 5 ) CH 2 OCH 3 , - CH (CH 3 ) CH 2 CH 2 OCH 3 ,
H, C2H5 C3H7-n C3H7-iH, C 2 H 5 C 3 H 7 -n C 3 H 7 -i
SCH3 SC2H5 14SCH 3 SC 2 H 5 14
-Cl -CH, CH,-Cl -CH, CH,
Cl CH,Cl CH,
F -Cl -CH, V F Cl CH, CH, 'CH,F -Cl -CH, VF Cl CH, CH, ' CH,
■3 " 3 CH, ■ 3 "3 CH,
-Cl -CH, -Cl -CH,
C '2„'H "5πF '2,'H "5. Cl C '2,'H '5C C ~"H '3, C,H_. CH,C '2 "'H" 5 π F '2,' H "5. Cl C '2,' H '5 C C ~ "H' 3, C, H_. CH,
'2' '5'2' '5
.^F -Cl -Cl, ^ F -Cl -Cl
Cl Br Br CH,Cl Br Br CH,
-Cl -Cl Cl CH3 Br Br CH3 -Cl -Cl Cl CH 3 Br Br CH 3
-Cl -Cl Cl C2H5 Br Br -Cl -Cl Cl C 2 H 5 Br Br
C2H5 CH3 C 2 H 5 CH 3
-Cl -CH, F CH, CH,-Cl -CH, F CH, CH,
F -Cl -CH, F F -Cl -CH, F
CH3 ClCH 3 Cl
-Cl -CH, -Cl -CH,
C2H5F C 2 H 5 F
C2H5 Cl C2H5 CH3 C2H5 CH3 Für jedes der hier und in den folgenden Gruppen anhand von Formel und Restedefinitionen aufgeführten Beispiele seien die im Folgenden beschriebenen diastereo- meren Formen besonders hervorgehoben:C 2 H 5 Cl C 2 H 5 CH 3 C 2 H 5 CH 3 For each of the examples listed here and in the following groups on the basis of formula and radical definitions, the diastereomeric forms described below are particularly emphasized:
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R2 und R3 gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („R,R- Diastereomere"),(a) R configuration on the carbon atom to which R 2 and R3 are bonded and R configuration on the carbon atom to which R4 is bonded (“R, R diastereomers”),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R2 und R gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R gebunden ist („R,S-(b) R configuration on the carbon atom to which R 2 and R are bonded and S configuration on the carbon atom to which R is bonded (“R, S-
Diastereomere"),Diastereomers "),
(c) S-Konfiguration an dem Kohlenstoffatom, an welches R2 und R3 gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („S,R- Diastereomere"),(c) S configuration on the carbon atom to which R 2 and R3 are bonded and R configuration on the carbon atom to which R4 is bonded (“S, R diastereomers”),
(d) S-Konfiguration an dem Kohlenstoffatom, an welches R2 und R3 gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R4 gebunden ist („S,S- Diastereomere").(d) S configuration on the carbon atom to which R 2 and R3 are attached and S configuration on the carbon atom to which R 4 is attached ("S, S diastereomers").
Gruppe 2Group 2
Rl , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 16Rl, R 2 , R and Y have, for example, the meanings given above in Group 1. 16
Gruppe 3Group 3
Rz R z
Y- -RJ Y- -R J
N ^ NN ^ N
R1 N J R 1 NJ
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 4Group 4
R^R ^
Y- -RJ Y- -R J
N ^ N CH3 R1 N ^ N CH 3 R 1
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 5Group 5
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 17R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 17
Gruppe 6Group 6
RR
-RJ -R J
N ^ N I 2 5N ^ N I 2 5
R1 N Λ NR 1 N Λ N
HH
^CH, ^ CH,
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 7Group 7
Rz R z
Y- -RJ Y- -R J
N -N -
92H592 H 5
R1/ "N Jk N HR 1 / "N Jk NH
OCH,OCH,
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 8Group 8
R^R ^
Y- -RY- -R
N^N CH3 R^N N HN ^ N CH 3 R ^ NNH
OCH,OCH,
Rl, R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 18Rl, R 2 , R and Y have, for example, the meanings given above in Group 1. 18th
Gruppe 9Group 9
FTFT
-RJ -R J
N ^ N CH,N ^ N CH,
N X' N iNX ' N i
H H
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1.
Gruppe 10Group 10
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 11Group 11
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 19R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1. 19
Gruppe 12Group 12
Rη R η
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 13Group 13
R^R ^
Y- -RΛ Y- -R Λ
C ι H, 3C ι H, 3
R N RN
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 13 aGroup 13 a
FTFT
Y- -Rύ Y- -R ύ
N ^ N C2H5 N ^ NC 2 H 5
R ,1A/ N N H R, 1 A / NNH
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 20R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1. 20th
Gruppe 14Group 14
R^R ^
Y-Y-
N * 2H5N * 2 H 5
R1 N yR 1 N y
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 15Group 15
R^R ^
Y- -RJ Y- -R J
^ N CH3 ^ N CH 3
HH
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 16Group 16
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 21R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 21
Gruppe 17Group 17
FTFT
Y- -RΛ Y- -R Λ
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1.
Gruppe 18Group 18
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen BedeutungenR, R 2 , R ^ and Y have, for example, the meanings given above in Group 1
Gruppe 19Group 19
R'R '
Y- -R*Y- -R *
R , R2, RJ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 22R, R 2 , R J and Y have, for example, the meanings given above in Group 1. 22
Gruppe 20Group 20
R^R ^
Y- -RJ Y- -R J
N s 2 5N s 2 5
R1 IM Jk - CH,R 1 IM Jk - CH,
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1.
Gruppe 21Group 21
RR
Y- -Rä Y- -R ä
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1.
Gruppe 22Group 22
R^R ^
Y« -R°Y «-R °
N^ N CH3 R^N^N" s -cιN ^ N CH 3 R ^ N ^ N " s -cι
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 23R, R 2 , R and Y have, for example, the meanings given above in Group 1. 23
Gruppe 23Group 23
R'R '
Y- -Rύ Y- -R ύ
N • - N CH,N • - N CH,
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 24Group 24
R'R '
Y- -RY- -R
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 25Group 25
FTFT
Y- -RJ Y- -R J
N ^ ΪN CH3 R^N^NN ^ ΪN CH 3 R ^ N ^ N
H H
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 24R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1. 24
Gruppe 26Group 26
Y- -RJ Y- -R J
N NN N
R1 N Λ' N i H R 1 N Λ ' N i H
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 27Group 27
R' R '
Rl, R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.Rl, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 28Group 28
R^R ^
Y- -RJ Y- -R J
HH
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 25R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 25th
Gruppe 29Group 29
R'R '
Y- -RJ Y- -R J
N^N C2H5 N ^ NC 2 H 5
R ι1/' ^ * κN.^' R ι 1 / '^ * κ N. ^ '
I HI H
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 30Group 30
R^R ^
Y- -R* Y- -R *
R 1 / i ^ N x' R 1 / i ^ N x '
I HI H
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 31Group 31
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 26R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1. 26
Gruppe 32Group 32
RR
Y- -RΛ Y- -R Λ
R X > -NX-RX > - N X-
I HI H
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1.
Gruppe 33Group 33
R'R '
Y- -RJ Y- -R J
N^N C2H5 r^^N ^ NC 2 H 5 r ^^
R ι1//^κr.^N N^ ^( R ι 1 / / ^ κr. ^ NN ^ ^ (
H R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.HR, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 34Group 34
R'R '
-RJ -R J
N^NN ^ N
Rι N R ι N
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 27R, R 2 , R and Y have, for example, the meanings given above in Group 1. 27
Gruppe 35Group 35
R , R2, R^ und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R ^ and Y have, for example, the meanings given above in Group 1.
Gruppe 36Group 36
R'R '
Y- -RJ Y- -R J
Rl ι \\Λ ?2Hs Rl ι \\ Λ? 2Hs
H °H °
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 37Group 37
-R3 -R 3
H3CH 3 C
N I ^^N C2H r^NI ^^ NC 2 H r ^
'N N I' H'N N I' H
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 38Group 38
R'R '
Y- -RJ y^\s Y- -R J y ^ \ s
H 28H 28
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 39Group 39
R^R ^
-RJ -R J
f II . //f II. //
HH
R , R2, R-3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R- 3 and Y have, for example, the meanings given above in Group 1.
Gruppe 40Group 40
R^R ^
-RJ -R J
N^N CN ^ N C
H H
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 41Group 41
RR
Y- -RΛ Y- -R Λ
N^N CHN ^ N CH
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 29R, R 2 , R and Y have, for example, the meanings given above in Group 1. 29
Gruppe 42Group 42
R^R ^
-RΛ -R Λ
CH,CH,
Rι/ -N- -N H R ι / -N- -NH
R , R2, R- und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 43Group 43
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 44Group 44
Y- -RJ Y- -R J
C2H5 C 2 H 5
.OCH,.OCH,
R i^ -N' ^X^R i ^ -N ' ^ X ^
I HI H
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 30R, R 2 , R3 and Y have, for example, the meanings given above in Group 1. 30th
Gruppe 45Group 45
R'R '
Y- -RY- -R
N^N C2H5 OCH,N ^ NC 2 H 5 OCH,
H ^H ^
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 46Group 46
R^R ^
Y- -RJ Y- -R J
^ ^r^ ^ r
R1 / TI ^N R 1 / TI ^ N
HH
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 47Group 47
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen. 31R, R 2 , R and Y have, for example, the meanings given above in Group 1. 31
Gruppe 48Group 48
R'R '
Y- -RJ Y- -R J
N^Sj C2 2H CH, " '5N ^ Sj C 2 2H CH, "'5
O.O.
R1/ ^TR 1 / ^ T
I HI H
R , R2, R3 und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R3 and Y have, for example, the meanings given above in Group 1.
Gruppe 49Group 49
R^R ^
Y- -RY- -R
Cl i lϊ ?Λ ICl i lϊ? Λ I
R *N'R * N '
HH
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Gruppe 50Group 50
R , R2, R und Y haben hierbei beispielhaft die oben in Gruppe 1 angegebenen Bedeutungen.R, R 2 , R and Y have, for example, the meanings given above in Group 1.
Verwendet man beispielsweise (S)-l-(l-Phenyl-propyl)-biguanid und (S)-l-Chlor- propionsäure-ethylester als Ausgangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren durch das folgende Formelschema skizziert werden: - 32 -If, for example, (S) -l- (l-phenyl-propyl) -biguanide and (S) -l-chloropropionic acid ethyl ester are used as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula: - 32 -
CU , V^--CcH,CU, V ^ - CcH,
H2N X.X C ^OC^H 2 N XX C ^ OC ^
I H IH
Die beim erfindungsgemäßen Verfahren zur Herstellung von Verbindungen der Formel (I) als Ausgangsstoffe zu verwendenden substituierten Biguanide sind durch die Formel (II) allgemein definiert. In der Formel (II) haben A, R , R4 und Z vor- zugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für A, R , R4 und Z angegeben wurden.Formula (II) provides a general definition of the substituted biguanides to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I). In formula (II), A, R, R 4 and Z preferably or in particular have those meanings which are preferred or particularly preferred for A, R already in connection with the description of the compounds of the formula (I) according to the invention , R 4 and Z were specified.
Die Ausgangsstoffe der allgemeinen Formel (II) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. EP-509 544, US-3 816 419, US- 3 860 648, WO 97/00 254, WO 97/08 156, DE- 19 641 691 (Le A 31 995), DE- 19 641 692 (Le A 32 037), DE- 19 641 693 (Le A 31 975), Herstellungsbeispiele).The starting materials of the general formula (II) are known and / or can be prepared by processes known per se (cf. EP-509 544, US-3 816 419, US-3 860 648, WO 97/00 254, WO 97 / 08 156, DE-19 641 691 (Le A 31 995), DE-19 641 692 (Le A 32 037), DE-19 641 693 (Le A 31 975), production examples).
Die beim erfindungsgemäßen Verfahren weiter als Ausgangsstoffe zu verwendendenThose to be used further as starting materials in the process according to the invention
Carbonsäurederivate sind durch die Formel (III) allgemein definiert. In der Formel (III) haben R2, R3 und Y vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für R2, R3 und Y angegeben wurden; X steht vorzugsweise für Fluor, Chlor, Brom oder C\-Carboxylic acid derivatives are generally defined by the formula (III). In the formula (III), R 2 , R3 and Y preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 2 , R3 and Y. were; X preferably represents fluorine, chlorine, bromine or C \ -
C4- Alkoxy, insbesondere für Methoxy oder Ethoxy.C4 alkoxy, especially for methoxy or ethoxy.
Die Ausgangsstoffe der allgemeinen Formel (III) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. J. Chem. Soc. Perkin Trans. I, 1979, 2248-2252; Herstellungsbeispiele).The starting materials of the general formula (III) are known and / or can be prepared by processes known per se (cf. J. Chem. Soc. Perkin Trans. I, 1979, 2248-2252; preparation examples).
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I) wird vorzugsweise unter Verwendung eines Reaktionshilfsmittels durch- - 33 -The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a reaction auxiliary. - 33 -
geführt. Als Reaktionshilfsmittel für das erfindungsgemäße Verfahren kommen im allgemeinen die üblichen anorganischen oder organischen Basen oder Säureakzeptoren in Betracht. Hierzu gehören vorzugsweise Alkalimetall- oder Erdalkalimetall- -acetate, -amide, -carbonate, -hydrogencarbonate, -hydride, -hydroxide oder - alkanolate, wie beispielsweise Natrium-, Kalium- oder Calcium-acetat, Lithium-,guided. The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium,
Natrium-, Kalium- oder Calcium-amid, Natrium-, Kalium- oder Calcium-carbonat, Natrium-, Kalium- oder Calcium-hydrogencarbonat, Lithium-, Natrium-, Kaliumoder Calcium-hydrid, Lithium-, Natrium-, Kalium- oder Calcium-hydroxid, Natriumoder Kalium- -methanolat, -ethanolat, -n- oder -i-propanolat, -n-, -i-, -s- oder -t- butanolat; weiterhin auch basische organische Stickstoffverbindungen, wie beispielsweise Trimethylamin, Triethylamin, Tripropylamin, Tributylamin, Ethyl-diisopropyl- amin, N,N-Dimethyl-cyclohexylamin, Dicyclohexylamin, Ethyl-dicyclohexylamin, N,N-Dimethyl-anilin, N,N-Dimethyl-benzylamin, Pyridin, 2-Methyl-, 3 -Methyl-, 4- Methyl-, 2,4-Dimethyl-, 2,6-Dimethyl-, 3,4-Dimethyl- und 3,5-Dimethyl-pyridin, 5- Ethyl-2-methyl-pyridin, 4-Dimethylamino-pyridin, N-Methyl-piperidin, 1,4-Diaza- bicyclo[2,2,2]-octan (DABCO), l,5-Diazabicyclo[4,3,0]-non-5-en (DBN), oder 1,8- Diazabicyclo [5 ,4,0] -undec-7-en (DBU).Sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or Calcium hydroxide, sodium or potassium methoxide, ethanolate, n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5- Ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3, 0] -non-5-ene (DBN), or 1,8-diazabicyclo [5, 4.0] -undec-7-ene (DBU).
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I) wird vorzugsweise unter Verwendung eines Verdünnungsmittels durchgeführt. Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kommen vor allem inerte organische Lösungsmittel in Betracht. Hierzu gehören insbesondere aliphatische, alicyclische oder aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie beispielsweise Benzin, Benzol, Toluol, Xylol, Chlorbenzol, Dichlorbenzol, Petrolether, Hexan, Cyclohexan, Dichlormethan, Chloroform, Tetrachlorkohlenstoff; Ether, wie Diethylether, Diisopropylether, Dioxan, Tetrahydrofuran oder Ethylenglykoldimethyl- oder -diethylether; Ketone, wie Aceton. Butanon oder Methyl-isobutyl-keton; Nitrile, wie Acetonitril, Propionitril oder Butyronitril; Amide, wie N,N-Dimethylformamid, N,N-Dimethylacetamid, N-Methyl-formanilid. N-Methyl-pyrrolidon oder Hexamethylphosphorsäuretriamid; Ester wie Essigsäuremethylester oder Essigsäureethylester; Sulfoxide, wie Dimethylsulfoxid; Alkohole, - 34 -The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. Inert organic solvents are particularly suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone. Butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide. N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Alcohols, - 34 -
wie Methanol, Ethanol, n- oder i-Propanol, Ethylenglykolmonomethylether, Ethylen- glykolmonoethylether, Diethylenglykolmonomethylether, Diethylenglykolmono- ethylether, deren Gemische mit W.asser oder reines Wasser.such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßenThe reaction temperatures can be carried out when carrying out the process according to the invention
Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 150°C, vorzugsweise zwischen 10°C und 100°C.Process can be varied over a wide range. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 100 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch möglich, das erfindungsgemäße Verfahren unter erhöhtem oder vermindertem Druck - im allgemeinen zwischen 0,1 bar und 10 bar - durchzuführen.The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
Zur Durchführung des erfindungsgemäßen Verfahrens werden die Ausgangsstoffe im allgemeinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der Komponenten in einem größeren Überschuß zu verwenden. Die Umsetzung wird im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Reaktionshilfsmittels durchgeführt und das Reaktionsgemisch wird im all- gemeinen mehrere Stunden bei der erforderlichen Temperatur gerührt. Die Aufarbeitung wird nach üblichen Methoden durchgeführt (vgl. die Herstellungsbeispiele).To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).
Die erfindungsgemäßen Wirkstoffe können als Defoliants, Desiccants, Krautab- tötungsmittel und insbesondere als Unkrautvernichtungsmittel verwendet werden.The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers.
Unter Unkraut im weitesten Sinne sind alle Pflanzen zu verstehen, die an Orten aufwachsen, wo sie unerwünscht sind. Ob die erfindungsgemäßen Stoffe als totale oder selektive Herbizide wirken, hängt im wesentlichen von der angewendeten Menge ab.Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden: - 35 -The active compounds according to the invention can be used, for example, in the following plants: - 35 -
Dikotyle Unkräuter der Gattungen: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abuti- lon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutlon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Brassica, Lactuca, Cucumis, Cucurbita.Brassica, lactuca, cucumis, cucurbita.
Monokotyle Unkräuter der Gattungen: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monokotyle Kulturen der Gattungen: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen.However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.
Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur Totalunkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen, z.B. Forst, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfen- 36Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, for example forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop- 36
anlagen, auf Zier- und Sportrasen und Weideflächen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden.plants, on ornamental and sports turf and pastures and for selective weed control in annual crops.
Die erfindungsgemäßen Verbindungen der Formel (I) eignen sich insbesondere zur selektiven Bekämpfung von monokotylen und dikotylen Unkräutern in monokotylen und dikotylen Kulturen sowohl im Vorauflauf- als auch im Nachauflauf- Verfahren.The compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence process.
Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lös- liehe Pulver. Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierteThe active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, and soluble powders. Granules, suspension emulsion concentrates, impregnated with active ingredients
Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen.Natural and synthetic substances as well as very fine encapsulation in polymeric substances.
Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktivenThese formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents
Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln.Agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkyl- naphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wieIf water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as
Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dime hylsulfoxid, sowie Wasser.Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
Als feste Trägerstoffe kommen in Frage: z.B. Ammoniumsalze und natürliche Ge- steinsmehle. wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit. Mont- morillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse - 37 -Possible solid carriers are: for example ammonium salts and natural rock powder. such as kaolins, clays, talc, chalk, quartz, attapulgite. Montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse - 37 -
Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol- Ether, z.B. Alkylarylpolyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfit- ablaugen und Methylcellulose.Silicic acid, aluminum oxide and silicates, as solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite leaching and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospho- lipide, wie Kephaline und Lecithine und synthetische Phospholipide. WeitereAdhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Further
Additive können mineralische und vegetabile Öle sein.Additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferro- cyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyanin- farbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt,Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt,
Molybdän und Zink verwendet werden.Molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Herbiziden zur Unkrautbekämpfung Verwendung finden, wobei Fertigformulierungen oder Tankmischungen möglich sind.The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
Für die Mischungen kommen bekannte Herbizide infrage. beispielsweise Acetochlor,Known herbicides are suitable for the mixtures. for example acetochlor,
Acifluorfen(-sodium), Aclonifen, Alachlor, Alloxydim(-sodium), Ametryne, Amido- 38Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amido- 38
chlor, Amidosulfuron, Anilofos, Asul-am, Atrazine, Azafenidin, Azimsulfuron, Ben- azolin(-ethyl), Benfuresate, Bensulfuron(-methyl), Bentazon, Benzofenap, Benzoyl- prop(-ethyl), Bialaphos, Bifenox, Bispyribac(-sodium), Bromobutide, Bromofen- oxim, Bromoxynil, Butachlor, Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone(-ethyl), Chlomethoxyfen, Chloramben, Chloridazon,chlorine, amidosulfuron, anilofos, asul-am, atrazine, azafenidin, azimsulfuron, benzazoline (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzofenap, benzoyl-prop (-ethyl), bialaphos, bifenox, bispyribac ( -sodium), bromobutide, bromofen-oxime, bromoxynil, butachlor, butroxydim, butylates, cafenstrole, caloxydim, carbetamides, carfentrazone (-ethyl), chloromethoxyfen, chloramben, chloridazone,
Chlorimuron- (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop(-propargyl), Clomazone, Clomeprop, Clo- pyralid, Clopyrasulfuron(-methyl), Cloransulam(-methyl), Cumyluron, Cyanazine, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop(-methyl), Diclosulam, Diethatyl(-ethyl),Chlorimuron- (-ethyl), chloronitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulazine (cyclo), cylsulfuron (-methyl), cylsulfuron (-methyl) , Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl),
Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Di- thiopyr, Diuron, Dymron, Epoprodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulf- uron(-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxa- prop(-P-ethyl), Flamprop(-isopropyl), Flamprop(-isopropyl-L), Flamprop(-methyl),Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Diethiopyr, Diuron, Dymron, Epoprodan, EPTC, Esprocarb, Ethametsulfate- Ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop (-P-ethyl), flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (-methyl),
Flazasulfüron, Fluazifop(-P-butyl), Flufenacet, Flumetsulam, Flumiclorac(-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoro- glycofen(-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron(-methyl, -sodium), Flurenol(-butyl), Fluridone, Fluroxypyr(-meptyl), Flurprimidol, Flurtamone, Flu- thiacet(-methyl), Fluthiamide, Fomesafen, Glufosinate(-ammonium), Glyphosate(- isopropylammonium), Halosafen, Haloxyfop(-ethoxyethyl), Haloxyfop(-P-methyl), Hexazinone, Imazamethabenz(-methyl), Imazamethapyr, Imazamox, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Ioxynil, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Meto- bromuron, (alpha-)Metolachlor, Metosulam, Metoxuron, Metribuzin, Met- sulfuron(-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon. Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon. Oxasulf- uron, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonsäure, Pendimethalin, Pent- oxazone, Phenmedipham, Piperophos, Pretilachlor, Primisulfuron(-methyl).Flazasulfüron, Fluazifop (-P-butyl), Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, (Flodium-pyrmethylsulfur) , Flurenol (-butyl), Fluridone, Fluroxypyr (-meptyl), Flurprimidol, Flurtamone, Fluothiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (- isopropylammonium), Halosafen, Haloxyfop (-ethoxy) , Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Ioxynil, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxaflutole, MCP, Linoxilurifon, Loxapyronop , MCPP, Mefenacet, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Nebropamide, Nebropamide Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon. Oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron (-methyl).
Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propyzamide, Pro- - 39 -Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propyzamide, Pro - 39 -
sulfocarb, Prosulfüron, Pyraflufen(-ethyl), Pyrazolate, Pyrazosulfuron(-ethyl), Pyraz- oxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Pyriminobac(-methyl), Pyrithiobac(- sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop(-P-ethyl), Quizalo- fop(-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfen- trazone, Sulfometuron(-methyl), Sulfosate, Sulfosulfüron, Tebutam, Tebuthiuron,sulfocarb, prosulfüron, pyraflufen (-ethyl), pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridate, pyriminobac (-methyl), pyrithiobac (- sodium), quinchlorac, quinmerac, quinoclamine (Quizallamine, Quizal -ethyl), quizalopop (-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfüron, tebutam, tebuthiuron,
Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thi- fensulfuron(-methyl), Thiobencarb, Tiocarbazil, Tralkoxydim, Triallate, Triasulf- uron, Tribenuron(-methyl), Triclopyr, Tridiphane, Trifluralin und Triflusulfuron.Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Thiobencarb, Tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphonuron and Triflusuron, Triflus- furon.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzennährstoffen und Bodenstruktur-verbesserungsmitteln ist möglich.A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertigeThe active ingredients as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use
Lösungen, Suspensionen, Emulsionen, Pulver, Pasten und Granulate angewandt werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen, Streuen.Solutions, suspensions, emulsions, powders, pastes and granules are used. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
Die erfindungsgemäßen Wirkstoffe können sowohl vor als auch nach dem Auflaufen der Pflanzen appliziert werden. Sie können auch vor der Saat in den Boden eingearbeitet werden.The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
Die angewandte Wirkstoffmenge kann in einem größeren Bereich schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im allgemeinen liegen die Aufwandmengen zwischen 1 g und 10 kg Wirkstoff pro Hektar Bodenfläche, vorzugsweise zwischen 5 g und 5 kg pro ha.The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. - 40 -The preparation and use of the active compounds according to the invention can be seen from the examples below. - 40 -
Herstellungsbeispiele: Beispiel 1Production examples: Example 1
HH
Eine Lösung von 2,4 g (44 mMol) Natriummethylat in 10 ml Methanol wird tropfen- weise unter Rühren bei 20°C zu einer Mischung aus 9,7 g (40 mMol) (S)-l-(l-A solution of 2.4 g (44 mmol) of sodium methylate in 10 ml of methanol is added dropwise with stirring at 20 ° C. to a mixture of 9.7 g (40 mmol) (S) -l- (l-
Phenyl-ethyl)-biguanid, 4,5 g (40 mMol) (R)-Milchsäure-ethylester und 80 ml Methanol gegeben und die Reaktionsmischung wird dann noch 15 Stunden bei Raumtemperatur (ca. 20°C) gerührt. Dann wird mit etwa gleichen Volumenmengen Methylenchlorid und Wasser auf etwa das dreifache Volumen verdünnt, nach Durch- schütteln die organische Phase abgetrennt, mit Wasser gewaschen, mit Natriumsulfat getrocknet und filtriert. Vom Filtrat wird das Lösungsmittel im Wasserstrahlvakuum sorgfältig abdestilliert.Phenyl-ethyl) -biguanid, 4.5 g (40 mmol) of (R) -lactic acid ethyl ester and 80 ml of methanol are added and the reaction mixture is then stirred for a further 15 hours at room temperature (approx. 20 ° C.). The mixture is then diluted to about three times the volume with approximately equal volumes of methylene chloride and water, the organic phase is separated after shaking, washed with water, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum.
Man erhält 4,4 g (42% der Theorie) 2-Amino-4-(R)-(l-hydroxy-ethyl)-6-(S)-(l-phe- nyl-ethyl-amino)-l ,3,5-triazin als amorphen Rückstand.4.4 g (42% of theory) of 2-amino-4- (R) - (1-hydroxyethyl) -6- (S) - (1-phenyl-ethyl-amino) -l are obtained, 3,5-triazine as an amorphous residue.
[α]p° = -93,5°.[α] p ° = -93.5 °.
Analog zu Herstellungsbeispiel 1 sowie entsprechend der allgemeinen Beschreibung des erfindungsgemäßen Herstellungsverfahrens können beispielsweise auch die in der nachstehenden Tabelle 1 aufgeführten Verbindungen der Formel (I) hergestellt werden. Die stereochemischen Angaben (zur Charakterisierung der Diastereo- merentypen) sind darin wie oben bei der Definition der Verbindungen der Formel (I) angegeben mit R,R bzw. R,S bzw. S,R bzw. S,S bzw. R,rac bzw. S.rac abgekürzt; d.h. die erste Angabe bezieht sich jeweils auf den Triazin-Substituenten -CR2R3Y und die zweite Angabe auf den Amino-Substituenten -CHR (A-Z). 41Analogously to Preparation Example 1 and in accordance with the general description of the preparation process according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 1 below. The stereochemical information (for characterizing the types of diastereomers) is given as R, R or R, S or S, R or S, S or R, rac, as stated above in the definition of the compounds of the formula (I) or S.rac abbreviated; ie the first statement relates to the triazine substituent -CR 2 R 3 Y and the second statement to the amino substituent -CHR (AZ). 41
R'R '
-RJ -R J
N^N R4 (I)N ^ NR 4 (I)
Rl N N^z Rl NN ^ z
Tabelle 1: Beispiele für die Verbindungen der Formel (I)Table 1: Examples of the compounds of the formula (I)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
2 NH2 H CH3 2 NH 2 H CH 3
H2 C H5 OH A, (amorph) (R,rac)H 2 CH 5 OH A, (amorphous) (R, rac)
3 3 3 3
H - NH2 H CH 2 C H5 OH CH3 (amoφh) (S,rac)H - NH 2 H CH 2 CH 5 OH CH 3 (amoφh) (S, rac)
4 NH2 H CH3 4 NH 2 H CH 3
H2 C2H5 Cl CH3 (amoφh) (S,rac)H 2 C 2 H 5 Cl CH 3 (amoφh) (S, rac)
5 - NH2 H CH3 5 - NH 2 H CH 3
H2 C2H5 Cl CH3 (amoφh) (R,rac)H 2 C 2 H 5 Cl CH 3 (amoφh) (R, rac)
66
H - NH2 H CH3 2 C H5 Cl A (amoφh) (R,rac)H - NH 2 H CH 3 2 CH 5 Cl A (amoφh) (R, rac)
77
HA2 - NH2 H CH3 C H5 Cl A (amoφh) (S,rac)HA 2 - NH 2 H CH 3 CH 5 Cl A (amoφh) (S, rac)
8 A- C2H5 H CH3 C2H5 Cl8 A- C 2 H 5 H CH 3 C 2 H 5 Cl
H 2 H A (amoφh) (R,rac) 42 H 2 HA (amoφh) (R, rac) 42
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
9 A- C2H5 H CH3 Cl9 A- C 2 H 5 H CH 3 Cl
H2 C2H5 H A (amoφh) (S,rac)H 2 C 2 H 5 HA (amoφh) (S, rac)
10 NH2 H CH3 C2H5 OH r ?10 NH 2 H CH 3 C 2 H 5 OH r?
HA2 - -Q [α]D° =HA 2 - -Q [α] D ° =
-8,6° (S,rac)-8.6 ° (S, rac)
11 H2 A- NH2 H CH3 C H5 OH r [α i]2 D 0 =11 H 2 A- NH 2 H CH 3 CH 5 OH r [α i] 2 D 0 =
H2 H 2
-12,1° (R,rac)-12.1 ° (R, rac)
12 c2 NH2 H CH3 C2H5 OH12 c 2 NH 2 H CH 3 C 2 H 5 OH
\ r [α !]2 D 0 =\ r [α!] 2 D 0 =
H2 l> +8,5°H 2 l> + 8.5 °
(R,rac)(R, rac)
13 A c2- NH2 H CH3 C2H5 Cl r i20 13 A c 2 - NH 2 H CH 3 C 2 H 5 Cl ri 20
H2 +8,3°H 2 + 8.3 °
(R,rac)(R, rac)
14 H2 A- NH2 H CH3 C2H5 Cl r [α i]2 D 0 =14 H 2 A- NH 2 H CH 3 C 2 H 5 Cl r [α i] 2 D 0 =
H2 H 2
-8,2° (S,rac)-8.2 ° (S, rac)
15 NH2 H CH3 Cl A- C2H515 NH 2 H CH 3 Cl A- C2H5
H2 y r [α i]2 D 0 =H 2 y r [α i] 2 D 0 =
-6,0° (S,rac) 43 --6.0 ° (S, rac) 43 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y z data and stereo chem. Information
16 A c2- NH2 H CH3 C2H5 Cl16 A c 2 - NH 2 H CH 3 C 2 H 5 Cl
H2 y r -i20 +6,3°H 2 y r -i 20 + 6.3 °
(R,rac)(R, rac)
17 NH2 H CH3 CH3 OH A r [α i]2 D 0 =17 NH 2 H CH 3 CH 3 OH A r [α i] 2 D 0 =
-120° (S,S)-120 ° (S, S)
18 NH2 H CH3 CH3 Cl A r [α i]2 D 0 =18 NH 2 H CH 3 CH 3 Cl A r [α i] 2 D 0 =
-107° (R,S)-107 ° (R, S)
19 NH2 H CH3 CH3 Cl A r i20 -126°19 NH 2 H CH 3 CH 3 Cl A ri 20 -126 °
(S,S)(S, S)
20 NH2 H CH3 C2H5 OH A r i20 -107°20 NH 2 H CH 3 C 2 H 5 OH A ri 20 -107 °
(S,S)(S, S)
21 NH2 H CH3 C2H5 OH A r [α i]2 D 0 =21 NH 2 H CH 3 C 2 H 5 OH A r [α i] 2 D 0 =
-102° (R,S)-102 ° (R, S)
22 NH2 H CH3 C2H5 Cl A (amoφh)22 NH 2 H CH 3 C 2 H 5 Cl A (amoφh)
(S,S) - 44(S, S) - 44
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
23 NH2 H CH3 C2H5 Cl A r A -105°23 NH 2 H CH 3 C 2 H 5 Cl A r A -105 °
(R,S)(R, S)
24 NH2 H CH3 C2H5 F A Öl24 NH 2 H CH 3 C 2 H 5 FA oil
(S,S)(S, S)
25 NH2 H CH3 C2H5 F A Öl25 NH 2 H CH 3 C 2 H 5 FA oil
(R,S)(R, S)
26 H2 A- NH2 H CH3 CH3 F26 H 2 A- NH 2 H CH 3 CH 3 F
H2 A r i20 H 2 A ri 20
+13°+ 13 °
(S,R)(S, R)
27 H2 A- NH2 H CH3 CH3 F [α]D 0 =27 H 2 A- NH 2 H CH 3 CH 3 F [α] D 0 =
H2 A r π2 H 2 A r π 2
-23° (R,R)-23 ° (R, R)
28 CH3 H CH3 CH3 Cl A (R,S)28 CH 3 H CH 3 CH 3 Cl A (R, S)
29 - H CH3 CH3 Cl A (R,S)29 - H CH 3 CH 3 Cl A (R, S)
- 45 - 45
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y z Daten und stereo- chem. AngabenNo. A Rl R2 R3 R 4 Y z data and stereo chem. Information
30 N(CH3)2 H CH3 CH3 Cl A (R,S)30 N (CH 3 ) 2 H CH 3 CH 3 Cl A (R, S)
31 CH3 H CH3 CH3 Cl A (S,S)31 CH 3 H CH 3 CH 3 Cl A (S, S)
32 C2H5 H CH3 CH3 Cl A (S,S)32 C 2 H 5 H CH 3 CH 3 Cl A (S, S)
33 N(CH3)2 H CH3 CH3 Cl A (S,S)33 N (CH 3 ) 2 H CH 3 CH 3 Cl A (S, S)
34 H H CH3 C H5 Cl A (S,S)34 HH CH 3 CH 5 Cl A (S, S)
35 CH3 H CH3 C H5 Cl A (S,S)35 CH 3 H CH 3 CH 5 Cl A (S, S)
36 C2H5 H CH3 C2H5 Cl A (S,S)36 C 2 H 5 H CH 3 C 2 H 5 Cl A (S, S)
37 (CH3)2 H CH3 C2H5 Cl H^% A (S,S)37 (CH 3 ) 2 H CH 3 C 2 H 5 Cl H ^% A (S, S)
38 H H CH3 C H5 Cl H A (R,S)38 HH CH 3 CH 5 Cl HA (R, S)
39 CH3 H CH3 C2H5 Cl39 CH 3 H CH 3 C 2 H 5 Cl
H A (R,S)H A (R, S)
46 46
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
40 C2H5 H CH3 C2H5 Cl40 C 2 H 5 H CH 3 C 2 H 5 Cl
0 N/ 0 N /
H A (R,S)H A (R, S)
41 N(CH3)2 H CH3 C2H5 Cl41 N (CH 3 ) 2 H CH 3 C 2 H 5 Cl
H IA A (R,S)H IA A (R, S)
42 NH2 H CH3 CH3 F A (S,S)42 NH 2 H CH 3 CH 3 FA (S, S)
43 NH2 H CH3 CH3 F A (R,S)43 NH 2 H CH 3 CH 3 FA (R, S)
44 NH2 H CH3 CH3 Cl xr (S,S)44 NH 2 H CH 3 CH 3 Cl xr (S, S)
45 NH2 H CH3 CH3 Cl Xf' (R,S)45 NH 2 H CH 3 CH 3 Cl Xf ' (R, S)
46 NH2 H CH3 CH3 OH XX' (R,S)46 NH 2 H CH 3 CH 3 OH XX ' (R, S)
47 NH2 H CH3 CH3 OH f (S,S)47 NH 2 H CH 3 CH 3 OH f (S, S)
48 NH2 H CH3 CH3 F Xf' (R,S)48 NH 2 H CH 3 CH 3 F Xf ' (R, S)
49 NH2 H CH3 CH3 F Xf (S,S)49 NH 2 H CH 3 CH 3 F Xf (S, S)
- 47 - 47
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
50 NH2 H CH3 CH3 F Xf' Log p: l,80a)50 NH 2 H CH 3 CH 3 F Xf ' Log p: l, 80 a )
(R,R)(R, R)
51 NH2 H CH3 CH3 F xr (S,R)51 NH 2 H CH 3 CH 3 F xr (S, R)
52 NH2 H CH3 CH3 OH xxc"' (S,S)52 NH 2 H CH 3 CH 3 OH xx c "' (S, S)
53 NH2 H CH3 CH3 OH xr (R,S)53 NH 2 H CH 3 CH 3 OH xr (R, S)
54 NH2 H CH3 CH3 Cl f* (S,S)54 NH 2 H CH 3 CH 3 Cl f * (S, S)
55 NH2 H CH3 CH3 Cl ^ CH355 NH 2 H CH 3 CH 3 Cl ^ CH 3
(R,S)(R, S)
56 NH2 H CH3 CH3 F Xf (S,S)56 NH 2 H CH 3 CH 3 F Xf (S, S)
57 NH2 H CH3 CH3 F Xf (R,S)57 NH 2 H CH 3 CH 3 F Xf (R, S)
58 NH2 H CH3 CH3 OH Ar""' (S,S)58 NH 2 H CH 3 CH 3 OH Ar ""' (S, S)
59 NH2 H CH3 CH3 OH Ar""' (R,S)59 NH 2 H CH 3 CH 3 OH Ar ""' (R, S)
- 48 - 48
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
60 NH2 H CH3 CH3 Cl60 NH 2 H CH 3 CH 3 Cl
-^- ^
(S,S)(S, S)
61 NH2 H CH3 CH3 Cl OCH,61 NH 2 H CH 3 CH 3 Cl OCH,
(R,S)(R, S)
62 NH2 H CH3 CH3 62 NH 2 H CH 3 CH 3
(S,S)(S, S)
63 NH2 H CH3 CH3 .OCH,63 NH 2 H CH 3 CH 3 .OCH,
(R,S)(R, S)
64 NH2 H CH3 CH3 OH64 NH 2 H CH 3 CH 3 OH
(R,R)(R, R)
65 NH2 H CH3 CH3 OH65 NH 2 H CH 3 CH 3 OH
(S,R)(S, R)
66 NH2 H CH3 CH3 Cl66 NH 2 H CH 3 CH 3 Cl
(R,R)(R, R)
67 NH2 H CH3 CH3 Cl -^67 NH 2 H CH 3 CH 3 Cl - ^
^^
(S,R)(S, R)
68 NH2 H CH3 CH3 68 NH 2 H CH 3 CH 3
(R,R)(R, R)
69 NH2 H CH3 CH- (S,R) - 49 -69 NH 2 H CH 3 CH- (S, R) - 49 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
70 NH2 H CH3 CH3 Cl ff: (R,S)70 NH 2 H CH 3 CH 3 Cl ff: (R, S)
71 NH2 H CH3 CH3 Cl xx: (S,S)71 NH 2 H CH 3 CH 3 Cl xx: (S, S)
72 NH2 H CH3 CH3 F ff, (R,S)72 NH 2 H CH 3 CH 3 F ff, (R, S)
73 NH2 H CH3 CH3 F /" CH.4 ^CH,73 NH 2 H CH 3 CH 3 F / " CH .4 ^ CH,
(R,R)(R, R)
74 NH2 H CH3 CH3 F74 NH 2 H CH 3 CH 3 F
/—f ^ -CH3 / —F ^ -CH 3
(S,S)(S, S)
75 NH2 H CH3 CH F ff, (S,R)75 NH 2 H CH 3 CH F ff, (S, R)
76 NH2 H CH3 CH3 Cl f (R,S)76 NH 2 H CH 3 CH 3 Cl f (R, S)
77 NH2 H CH3 CH3 Cl f (S,S)77 NH 2 H CH 3 CH 3 Cl f (S, S)
78 NH2 H CH3 CH3 F ff (R,S)78 NH 2 H CH 3 CH 3 F ff (R, S)
79 NH2 H CH3 CH3 F ff (S,S)79 NH 2 H CH 3 CH 3 F ff (S, S)
50 - 50 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
80 NH2 H CH3 CH3 F Xf (R,R)80 NH 2 H CH 3 CH 3 F Xf (R, R)
81 NH2 H CH3 CH3 F f (S,R)81 NH 2 H CH 3 CH 3 F f (S, R)
82 NH2 H CH3 CH3 Cl AC;82 NH 2 H CH 3 CH 3 Cl AC;
(R,S)(R, S)
83 NH2 H CH3 CH3 Cl XX. (S,S)83 NH 2 H CH 3 CH 3 Cl XX. (S, S)
84 NH2 H CH3 CH3 F XX (R,S)84 NH 2 H CH 3 CH 3 F XX (R, S)
85 NH2 H CH3 CH3 F ^\/F 85 NH 2 H CH 3 CH 3 F ^ \ / F
(S,S)(S, S)
86 NH2 H CH3 C2H5 F ,/^-/F 86 NH 2 H CH 3 C 2 H 5 F, / ^ - / F
(R,S)(R, S)
87 NH2 H CH3 C2H5 F XX. (S,S)87 NH 2 H CH 3 C 2 H 5 F XX. (S, S)
88 NH2 H CH CH3 F 0 (R,S)88 NH 2 H CH CH 3 F 0 (R, S)
- 51 - 51
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
89 NH2 H CH3 CH3 F O (S,S)89 NH 2 H CH 3 CH 3 FO (S, S)
90 NH2 H CH3 CH3 F o (R,S)90 NH 2 H CH 3 CH 3 F o (R, S)
91 NH2 H CH3 CH3 F pO (S,S)91 NH 2 H CH 3 CH 3 F pO (S, S)
92 NH2 H CH3 C2H5 Cl92 NH 2 H CH 3 C 2 H 5 Cl
(R,R)(R, R)
93 NH2 H CH3 C2H5 Cl93 NH 2 H CH 3 C 2 H 5 Cl
(S,R)(S, R)
94 NH2 H CH3 C2H5 F94 NH 2 H CH 3 C 2 H 5 F
(S,R)(S, R)
95 NH2 H CH3 C2H5 F95 NH 2 H CH 3 C 2 H 5 F
(R,R)(R, R)
96 H 2 NH2 H CH3 C2H5 F96 H 2 NH 2 H CH 3 C 2 H 5 F
H2 ^ A (R,R) - 52H 2 ^ A (R, R) - 52
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
97 c2\ NH2 H CH3 C2H5 F97 c 2 \ NH 2 H CH 3 C 2 H 5 F
H2 A (R,S)H 2 A (R, S)
98 c2^ NH2 H CH3 C2H5 F98 c 2 ^ NH 2 H CH 3 C 2 H 5 F
H2 A (S,R)H 2 A (S, R)
99 NH2 H CH3 C2H5 F99 NH 2 H CH 3 C 2 H 5 F
H2 A (S,S)H 2 A (S, S)
100 H2 CH3 H CH3 C H5 F H2 H A (R,R)100 H 2 CH 3 H CH 3 CH 5 FH 2 HA (R, R)
101 CH3 H CH3 C2H5 F101 CH 3 H CH 3 C 2 H 5 F
^c"C\ ^ c " C \
H2 A (S,R)H 2 A (S, R)
102 - NH2 H CH3 CH3 F102 - NH 2 H CH 3 CH 3 F
H2 A (R,R)H 2 A (R, R)
103 NH2 H CH3 CH3 F103 NH 2 H CH 3 CH 3 F
H2 A (S,R)H 2 A (S, R)
104 NH2 H CH3 CH3 F104 NH 2 H CH 3 CH 3 F
H2 A (R,S)H 2 A (R, S)
105 NH2 H CH3 CH3 F105 NH 2 H CH 3 CH 3 F
H2 A (S,S)H 2 A (S, S)
106106
H2 - NH2 H CH3 C H5 F A (R,R)H 2 - NH 2 H CH 3 CH 5 FA (R, R)
53 - 53 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
107 NH2 H CH3 107 NH 2 H CH 3
H2 C2H5 F A (S,R)H 2 C 2 H 5 FA (S, R)
108 NH2 H CH3 108 NH 2 H CH 3
H2 C2H5 F A (R,S)H 2 C 2 H 5 FA (R, S)
109 NH2 H CH3 109 NH 2 H CH 3
H2 C2H5 F A (S,S)H 2 C 2 H 5 FA (S, S)
110 - NH2 H CH3 CH3 F <?H3 110 - NH 2 H CH 3 CH 3 F <? H 3
H2 H 2
(R,S)(R, S)
111 ^ NH2 H CH3 CH3 F CH3 111 ^ NH 2 H CH 3 CH 3 F CH 3
H2 H 2
Xf (R,R)Xf (R, R)
112 - NH2 H CH3 CH3 F CH3 112 - NH 2 H CH 3 CH 3 F CH 3
H2 H 2
Xf (S,S)Xf (S, S)
113 NH2 H CH3 CH3 F CH3 113 NH 2 H CH 3 CH 3 F CH 3
H2 H 2
(S,R)(S, R)
114 ^ CH3 H CH3 CH3 F CH3 114 ^ CH 3 H CH 3 CH 3 F CH 3
H2 HH 2 H
(S,R)(S, R)
115 ^c- CH3 A _,115 ^ c - CH 3 A _,
H CH3 CH3 F CH3 H CH 3 CH 3 F CH 3
H2 H f (R,R) 54H 2 H f (R, R) 54
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
116 V- C2H5 H CH3 CH3 F CH3 116 V- C 2 H 5 H CH 3 CH 3 F CH 3
H2 0 N/H 2 0 N /
H Xf (S,R)H Xf (S, R)
117 C2H5 H CH3 CH3 F CH3 117 C 2 H 5 H CH 3 CH 3 F CH 3
H2 oA H-" A„, (R,R)H 2 oA H- "A", (R, R)
118 --c- (CH3)2 H CH3 CH3 F CH3 118 - c - (CH 3 ) 2 H CH 3 CH 3 F CH 3
H2 H «, (S,R)H 2 H «, (S, R)
119 ^ N(CH3)2 H CH3 CH3 F CH3 119 ^ N (CH 3 ) 2 H CH 3 CH 3 F CH 3
H2 H 2
H-"SA jt (R,R)H- "SA j t (R, R)
120 NH2 H CH3 120 NH 2 H CH 3
H2 C2H5 F CH3 H 2 C 2 H 5 F CH 3
Xf (S,R)Xf (S, R)
121 •-c- NH2 H CH3 121 • - c - NH 2 H CH 3
H2 C2H5 F <?H3 H 2 C 2 H 5 F <? H 3
^^ ^cH, (R,R)^^ ^ cH, (R, R)
122 ^ NH2 H CH3 122 ^ NH 2 H CH 3
H2 C2H5 FH 2 C 2 H 5 F
A„, (S,S)A ", (S, S)
123 NH2 H CH3 123 NH 2 H CH 3
H2 C2H5 F CH3 H 2 C 2 H 5 F CH 3
A„, (R,S)A ", (R, S)
124 NH2 H CH3 CH3 F124 NH 2 H CH 3 CH 3 F
H2 Xf (S,R)H 2 Xf (S, R)
125 - NH2 H CH3 CH3 F125 - NH 2 H CH 3 CH 3 F
H2 Xf (R,R)H 2 Xf (R, R)
55 55
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
126 NH2 H CH3 CH3 F126 NH 2 H CH 3 CH 3 F
H2 Xf (S,S)H 2 Xf (S, S)
127 ^ NH2 H CH3 CH3 F127 ^ NH 2 H CH 3 CH 3 F
H2 f (R,S)H 2 f (R, S)
128 ^c" NH2 H CH3 128 ^ c " NH 2 H CH 3
H2 C2H5 F Xf (S,R)H 2 C 2 H 5 F Xf (S, R)
129129
H2 "- NH2 H CH3 C2H5 F f (R,R)H 2 "- NH 2 H CH 3 C 2 H 5 F f (R, R)
130 NH2 H CH3 CH3 F130 NH 2 H CH 3 CH 3 F
H2 A^AH 2 A ^ A
(S,R)(S, R)
131 --c-A NH2 H CH3 CH3 F131 - c -A NH 2 H CH 3 CH 3 F
H2 A CHj H 2 A CHj
(R,R)(R, R)
132 - NH2 H CH3 CH3 F132 - NH 2 H CH 3 CH 3 F
H2 Xf (S,S)H 2 Xf (S, S)
133 NH2 H CH3 CH3 F133 NH 2 H CH 3 CH 3 F
H2 Xf (R,S)H 2 Xf (R, S)
134 ^c- NH2 H CH3 134 ^ c - NH 2 H CH 3
H2 C2H5 F Xf (S,R)H 2 C 2 H 5 F Xf (S, R)
135 - NH2 H CH C2H5 F (R,R)135 - NH 2 H CH C 2 H 5 F (R, R)
H2 AACHj 56H 2 AA CHj 56
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
136 NH2 H CH3 136 NH 2 H CH 3
H2 C2H5 FH 2 C 2 H 5 F
Xf (S,S)Xf (S, S)
137 ^c- NH2 H CH3 137 ^ c- NH 2 H CH 3
H2 C2H5 FH 2 C 2 H 5 F
Xf (R,S)Xf (R, S)
138 ^c" NH2 H CH3 138 ^ c "NH 2 H CH 3
H2 C H5 F ^y^cπ,H 2 CH 5 F ^ y ^ cπ,
(S,S)(S, S)
139 ^c- NH2 H CH3 C2H5 F139 ^ c- NH 2 H CH 3 C 2 H 5 F
H2 Xf (R,S)H 2 Xf (R, S)
140 •-c- NH2 H CH3 CH3 F140 • -c- NH 2 H CH 3 CH 3 F
H2 XXr (R,R)H 2 XX r (R, R)
141 ^c- NH2 H CH3 CH3 F141 ^ c- NH 2 H CH 3 CH 3 F
H2 XX. (R,S)H 2 XX. (R, S)
142 ^ NH2 H CH3 CH3 F142 ^ NH 2 H CH 3 CH 3 F
H2 XX (S,R)H 2 XX (S, R)
143 - NH2 H CH3 CH3 F143 - NH 2 H CH 3 CH 3 F
H2 XX (S,S)H 2 XX (S, S)
144 ^c- NH2 H CH3 144 ^ c- NH 2 H CH 3
H2 C2H5 F XX (S,R) 57 -H 2 C 2 H 5 F XX (S, R) 57 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
145 NH2 H CH3 145 NH 2 H CH 3
H2 C2H5 F f amorph (R,R)H 2 C 2 H 5 F f amorphous (R, R)
146 ^CΑ NH2 H CH3 146 ^ C Α NH 2 H CH 3
H2 C H5 F XX (S,S)H 2 CH 5 F XX (S, S)
147 NH2 H CH3 147 NH 2 H CH 3
H2 C H5 F XX, (R,S)H 2 CH 5 F XX, (R, S)
148 \/0\/ NH2 H CH3 CH3 F xO (S,R)148 \ / 0 \ / NH 2 H CH 3 CH 3 F xO (S, R)
149 \/0\/ NH2 H CH3 CH3 F A (R,R)149 \ / 0 \ / NH 2 H CH 3 CH 3 FA (R, R)
150 \Z°\/ NH2 H CH3 CH3 F A (S,S) 150 \ Z ° \ / NH 2 H CH 3 CH 3 FA (S, S)
58 -58 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
151 \/0 / NH2 H CH3 CH3 F A (R,S)151 \ / 0 / NH 2 H CH 3 CH 3 FA (R, S)
152 ^0-^ NH2 H CH3 C2H5 F χO (S,R)152 ^ 0 - ^ NH 2 H CH 3 C 2 H 5 F χO (S, R)
153 ^0^/ NH2 H CH3 C2H5 F153 ^ 0 ^ / NH 2 H CH 3 C 2 H 5 F
XO (R,R)XO (R, R)
154 \/0v/ NH2 H CH3 C2H5 F A (S,S)154 \ / 0 v / NH 2 H CH 3 C 2 H 5 FA (S, S)
155 \/0^/ NH2 H CH3 C2H5 F O (R,S)155 \ / 0 ^ / NH 2 H CH 3 C 2 H 5 FO (R, S)
156 \z°^/ NH2 H CH3 CH3 F ff (S,R)156 \ z ° ^ / NH 2 H CH 3 CH 3 F ff (S, R)
157 ^°^/ NH2 H CH3 CH3 F ^^ .Cl157 ^ ° ^ / NH 2 H CH 3 CH 3 F ^^ .Cl
(R,R)(R, R)
158 X/0^/ NH2 H CH3 CH3 F Xf (S,S)158 X / 0 ^ / NH 2 H CH 3 CH 3 F Xf (S, S)
159 ^° / NH2 H CH3 CH3 F xf (R,S)159 ^ ° / NH 2 H CH 3 CH 3 F xf (R, S)
160 X/°^/ NH2 H CH3 C2H5 F Xf (S,R) 59 -160 X / ° ^ / NH 2 H CH 3 C 2 H 5 F Xf (S, R) 59 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
161 \/0^ NH2 H CH3 C2H5 F Xf (R,R)161 \ / 0 ^ NH 2 H CH 3 C 2 H 5 F Xf (R, R)
162 N^0^ NH2 H CH3 C2H5 F Xf (S,S)162 N ^ 0 ^ NH 2 H CH 3 C 2 H 5 F Xf (S, S)
163 \^o^ NH2 H CH3 C H5 F xxa (R,S)163 \ ^ o ^ NH 2 H CH 3 CH 5 F xx a (R, S)
164 vV NH2 H CH3 CH3 F XX (S,R)164 vV NH 2 H CH 3 CH 3 F XX (S, R)
165 v NH2 H CH3 CH3 F xf (S,S)165 v NH 2 H CH 3 CH 3 F xf (S, S)
166 ^0^/ NH2 H CH3 CH3 F xf (R,R)166 ^ 0 ^ / NH 2 H CH 3 CH 3 F xf (R, R)
167 ^°^/ NH2 H CH3 CH3 F xf (R,S)167 ^ ° ^ / NH 2 H CH 3 CH 3 F xf (R, S)
168 \^0^ NH2 H CH3 C2H5 F xf (S,R)168 \ ^ 0 ^ NH 2 H CH 3 C 2 H 5 F xf (S, R)
169 \^°\/ NH2 H CH3 C2H5 F XX (R,R)169 \ ^ ° \ / NH 2 H CH 3 C 2 H 5 F XX (R, R)
170 \/0^/ NH2 H CH3 C2H5 F XX (S,S) 60170 \ / 0 ^ / NH 2 H CH 3 C 2 H 5 F XX (S, S) 60
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
171 \/0\/ NH2 H CH3 C2H5 F A" (R,S)171 \ / 0 \ / NH 2 H CH 3 C 2 H 5 FA " (R, S)
172 \/0\/ NH2 H CH3 CH3 F T (S,R)172 \ / 0 \ / NH 2 H CH 3 CH 3 FT (S, R)
173 \^0^ NH2 H CH3 CH3 F Xf (R,R)173 \ ^ 0 ^ NH 2 H CH 3 CH 3 F Xf (R, R)
174 \/0^ NH2 H CH3 CH3 F /- CH3174 \ / 0 ^ NH 2 H CH 3 CH 3 F / - CH 3
(S,S)(S, S)
175 ^O^/ NH2 H CH3 CH3 F ^Y'™3 175 ^ O ^ / NH 2 H CH 3 CH 3 F ^ Y '™ 3
(R,S)(R, S)
176 ^0-^ NH2 H CH3 C2H5 F ^ CH3176 ^ 0 - ^ NH 2 H CH 3 C 2 H 5 F ^ CH 3
(S,R)(S, R)
177 vV NH2 H CH3 C2H5 F xr (R,R)177 vV NH 2 H CH 3 C 2 H 5 F xr (R, R)
178 ^°^ NH2 H CH3 C2H5 F xr (S,S)178 ^ ° ^ NH 2 H CH 3 C 2 H 5 F xr (S, S)
179 -^0^^/ NH2 H CH3 C2H5 F xr (R,S)179 - ^ 0 ^^ / NH 2 H CH 3 C 2 H 5 F xr (R, S)
180 ^O^ NH2 H CH3 CH3 F180 ^ O ^ NH 2 H CH 3 CH 3 F
Xf (S,R) 61 -Xf (S, R) 61 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
181 \z-0 \/ NH2 H CH3 CH3 F181 \ z - 0 \ / NH 2 H CH 3 CH 3 F
Xf (R,R)Xf (R, R)
182 \/0^/ NH2 H CH3 CH3 F182 \ / 0 ^ / NH 2 H CH 3 CH 3 F
Xf (S,S)Xf (S, S)
183 X/0^-^ NH2 H CH3 CH3 F183 X / 0 ^ - ^ NH 2 H CH 3 CH 3 F
Xf (R,S)Xf (R, S)
184 vV NH2 H CH3 C2H5 F A , (S,R)184 vV NH 2 H CH 3 C 2 H 5 FA, (S, R)
185 \/0v/ NH2 H CH3 C2H5 F185 \ / 0 v / NH 2 H CH 3 C 2 H 5 F
Xf (R,R)Xf (R, R)
186 X/0^-"" NH2 H CH3 C2H5 F186 X / 0 ^ - "" NH 2 H CH 3 C 2 H 5 F
Xf (S,S)Xf (S, S)
187 \/0\/ NH2 H CH3 C2H5 F XX, (R,S)187 \ / 0 \ / NH 2 H CH 3 C 2 H 5 F XX, (R, S)
188 vV NH2 H CH3 CH3 F f (S,R)188 vV NH 2 H CH 3 CH 3 F f (S, R)
189 \/0\/ NH2 H CH3 CH3 F xχr (R,R)189 \ / 0 \ / NH 2 H CH 3 CH 3 F xχ r (R, R)
190 \/0^/ NH2 H CH3 CH3 F XX (S,S) 62 -190 \ / 0 ^ / NH 2 H CH 3 CH 3 F XX (S, S) 62 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
191 V°s/ NH2 H CH3 CH3 F XX (R,S)191 V ° s / NH 2 H CH 3 CH 3 F XX (R, S)
192 V/0^ NH2 H CH3 C2H5 F XX (S,R)192 V / 0 ^ NH 2 H CH 3 C 2 H 5 F XX (S, R)
193 ^O^/ NH2 H CH3 C2H5 F XX (R,R)193 ^ O ^ / NH 2 H CH 3 C 2 H 5 F XX (R, R)
194 ^°- / NH2 H CH3 C2H5 F XX (S,S)194 ^ ° - / NH 2 H CH 3 C 2 H 5 F XX (S, S)
195 \/0\/ NH2 H CH3 C H5 F XX (R,S)195 \ / 0 \ / NH 2 H CH 3 CH 5 F XX (R, S)
196 ^°^ NH2 H CH3 CH3 F196 ^ ° ^ NH 2 H CH 3 CH 3 F
Xf (S,R)Xf (S, R)
197 o^ NH2 H CH3 CH3 F197 o ^ NH 2 H CH 3 CH 3 F
Xf (R,R)Xf (R, R)
198 ^0^ NH2 H CH3 CH3 F198 ^ 0 ^ NH 2 H CH 3 CH 3 F
Xf (S,S)Xf (S, S)
199 \^ ^^ NH2 H CH3 CH3 F199 \ ^ ^ ^ NH 2 H CH 3 CH 3 F
X^yy C ,X ^ y y C ,
(R,S)(R, S)
200 \/0\/ NH2 H CH3 C2H5 F200 \ / 0 \ / NH 2 H CH 3 C 2 H 5 F
Xf-CH3 Xf-CH 3
(S.R) 63 -(SR) 63 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal. Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenEx. Physical. No. A Rl R 2 R3 R 4 Y data and stereo chem. Information
201 NHπ H CH3 C2H5 201 NHπ H CH 3 C 2 H 5
CH,CH,
(R,R)(R, R)
202 \/L NHo H CH3 C2H5 202 \ / L NHo H CH 3 C 2 H 5
CH,CH,
(S,S)(S, S)
203 ^L NHn H CH3 C2H5 203 ^ L NHn H CH 3 C 2 H 5
(R,S)(R, S)
204 ^L NH, H CH3 CH3 (S,R)204 ^ L NH, H CH 3 CH 3 (S, R)
205 ^L NHπ H CH3 CH3 205 ^ L NHπ H CH 3 CH 3
(R,R) (R, R)
206 N^ NH-j H CH3 CH3 (S,S)206 N ^ NH-j H CH 3 CH 3 (S, S)
207 \^L NH H CH3 CH3 F (R,S)207 \ ^ L NH H CH 3 CH 3 F (R, S)
208 ^L NHπ H CH3 C H5 (S,R)208 ^ L NHπ H CH 3 CH 5 (S, R)
209 NHπ H CH3 C2H5 (R,R)209 NHπ H CH 3 C 2 H 5 (R, R)
210 NH- H CH3 C2H5 (S,S)210 NH-H CH 3 C 2 H 5 (S, S)
J L - 64 -JL - 64 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
211 •^L NHπ H CH3 C2H5 (R,S)211 • ^ L NHπ H CH 3 C 2 H 5 (R, S)
212 ^L NH, H CH3 CH3 212 ^ L NH, H CH 3 CH 3
(S,R) (S, R)
213 NH7 H CH3 CH3 (R,R)213 NH 7 H CH 3 CH 3 (R, R)
214 NH~ H CH3 CH3 (S,S)214 NH ~ H CH 3 CH 3 (S, S)
215 \^ NH7 H CH3 CH3 (R,S)215 \ ^ NH 7 H CH 3 CH 3 (R, S)
216 ^L NH H CH3 C H5 (S,R)216 ^ L NH H CH 3 CH 5 (S, R)
217 ^L NHπ H CH3 C2H5 217 ^ L NHπ H CH 3 C 2 H 5
(R,R) 18 \^ NH, H CH3 C2H5 (S,S) (R, R) 18 \ ^ NH, H CH 3 C 2 H 5 (S, S)
219 NHπ H CH3 C H5 (R,S)219 NHπ H CH 3 CH 5 (R, S)
220 NHn H CH3 CH3 (S.R) 65220 NHn H CH 3 CH 3 (SR) 65
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 data and stereo chem. Information
221 NH7 H CH3 CH3 221 NH 7 H CH 3 CH 3
(R,R) (R, R)
222 NH, H CH3 CH3 (S,S)222 NH, H CH 3 CH 3 (S, S)
223 ^ NHo H CH3 CH3 (R,S)223 ^ NHo H CH 3 CH 3 (R, S)
224 N/1- NHn H CH3 C H5 (S,R)224 N / 1 - NHn H CH 3 CH 5 (S, R)
225 NH7 H CH3 C2H5 (R,R)225 NH 7 H CH 3 C 2 H 5 (R, R)
226 NH, H CH3 C H5 (S,S)226 NH, H CH 3 CH 5 (S, S)
227 NHn H CH3 C H5 (R,S)227 NHn H CH 3 CH 5 (R, S)
228 ^L NH7 H CH3 CH3 228 ^ L NH 7 H CH 3 CH 3
(S,R)(S, R)
229 J-^y NH~ H CH3 CH3 o (R,R) 66 -229 J - ^ y NH ~ H CH 3 CH 3 o (R, R) 66 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
230 •^°^ NH2 H CH3 CH3 F230 • ^ ° ^ NH 2 H CH 3 CH 3 F
Λ (S,S)Λ (S, S)
231 \/°^ NH2 H CH3 CH3 F231 \ / ° ^ NH 2 H CH 3 CH 3 F
(R,S)(R, S)
232 X^O^/ NH2 H CH3 C H5 F Λ) (S,R)232 X ^ O ^ / NH 2 H CH 3 CH 5 F Λ) (S, R)
233 \/0\/ NH2 H CH3 C2H5 F ) (R,R)233 \ / 0 \ / NH 2 H CH 3 C 2 H 5 F) (R, R)
234 \ °\/ NH2 H CH3 C2H5 F234 \ ° \ / NH 2 H CH 3 C 2 H 5 F
(S,S)(S, S)
235 ^O^ NH2 H CH3 C2H5 F235 ^ O ^ NH 2 H CH 3 C 2 H 5 F
Λ} (R,S)Λ} (R, S)
236 s^.0^ NH2 H CH3 CH3 F236 s ^ .0 ^ NH 2 H CH 3 CH 3 F
(S,R)(S, R)
237 \/0\/ NH2 H CH3 CH3 F237 \ / 0 \ / NH 2 H CH 3 CH 3 F
(R,R)(R, R)
67 - 67 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
238 NH2 H CH3 CH3 F y (S,S)238 NH 2 H CH 3 CH 3 F y (S, S)
239 ^°^ NH2 H CH3 CH3 F o (R,S)239 ^ ° ^ NH 2 H CH 3 CH 3 F o (R, S)
240 \/0\/ NH2 H CH3 C2H5 F240 \ / 0 \ / NH 2 H CH 3 C 2 H 5 F
(S,R)(S, R)
241 ^°^ NH2 H CH3 C2H5 F o (R,R)241 ^ ° ^ NH 2 H CH 3 C 2 H 5 F o (R, R)
242 \/0\/ NH2 H CH3 C2H5 F242 \ / 0 \ / NH 2 H CH 3 C 2 H 5 F
^°^ NH2 o (S,S)^ ° ^ NH 2 o (S, S)
243 H CH3 C2H5 F243 H CH 3 C 2 H 5 F
H3 CH3 F o (R,S)H 3 CH 3 F o (R, S)
244 H2 NH2 H C H2 Λ (S,R)244 H 2 NH 2 HCH 2 Λ (S, R)
245 H 2 NH2 H CH3 CH3 F y> (R,R)245 H 2 NH 2 H CH 3 CH 3 F y> (R, R)
68 - 68 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
246 c2 NH2 H CH3 CH3 F246 c 2 NH 2 H CH 3 CH 3 F
H2 H 2
(S,S)(S, S)
247 H2 ^ NH2 H CH3 CH3 F247 H 2 ^ NH 2 H CH 3 CH 3 F
H2 H 2
(R,S)(R, S)
248 ^c- NH2 H CH3 C2H5 F248 ^ c - NH 2 H CH 3 C 2 H 5 F
H2 y > (S,R)H 2 y> (S, R)
249 NH2 H CH3 C2H5 F249 NH 2 H CH 3 C 2 H 5 F
H2 H 2
(R,R)(R, R)
250 ^c-A NH2 H CH3 C H5 F250 ^ c -A NH 2 H CH 3 CH 5 F
H2 H 2
(S,S)(S, S)
251 c2 NH2 H CH3 C2H5 F251 c 2 NH 2 H CH 3 C 2 H 5 F
H2 Λ (R,S)H 2 Λ (R, S)
252 H2 252 H 2
^c-A NH2 H CH3 CH3 F^ c -A NH 2 H CH 3 CH 3 F
H2 H 2
(S,R)(S, R)
253 H 2 253 H 2
^c- NH2 H CH3 CH3 F^ c - NH 2 H CH 3 CH 3 F
H2 y (R,R)H 2 y (R, R)
69 69
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- 1 Physikal.Ex. 1 physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
254 c2 NH2 H CH3 CH3 F 2 54 c 2 NH 2 H CH 3 CH 3 F
H2 H 2
NH2 H CH3 CH3 F o (S,S)NH 2 H CH 3 CH 3 F o (S, S)
5555
H2 0 (R,S)H 2 0 (R, S)
256 NH2 H CH3 C H5 F 2 56 NH 2 H CH 3 CH 5 F
H2 H 2
(S,R)(S, R)
251 H2 NH2 H CH3 C2H5 F251 H 2 NH 2 H CH 3 C 2 H 5 F
H2 \H 2 \
H2 H CH3 C H5 F o (R,R)H 2 H CH 3 CH 5 F o (R, R)
258 H2 N H2 2 58 H 2 NH 2
(S,S)(S, S)
259 c2\ NH2 H CH3 C2H5 F 2 59 c 2 \ NH 2 H CH 3 C 2 H 5 F
H2 H 2
(R,S)(R, S)
260 H2 NH2 H CH3 CH3 2 60 H 2 NH 2 H CH 3 CH 3
^c- Cl^ c - Cl
H2 o (S,R)H 2 o (S, R)
961 H2 NH2 H CH3 CH3 Cl H,961 H 2 NH 2 H CH 3 CH 3 Cl H,
(R,R)(R, R)
- 70 - - 70 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
262 c2\ NH2 H CH3 CH3 Cl262 c 2 \ NH 2 H CH 3 CH 3 Cl
H2 H 2
(S,S)(S, S)
263 H2 NH2 H CH3 CH3 Cl H2 263 H 2 NH 2 H CH 3 CH 3 Cl H 2
CH3 C2H5 Cl o (R,S)CH 3 C 2 H 5 Cl o (R, S)
264 H2 ^ NH2 H264 H 2 ^ NH 2 H
H2 H 2
NH2 H CH3 C2H5 Cl o (S,R)NH 2 H CH 3 C 2 H 5 Cl o (S, R)
265 c2 265 c 2
H2 o (R,R)H 2 o (R, R)
266 H 2 NH2 H CH3 C2H5 Cl H2 266 H 2 NH 2 H CH 3 C 2 H 5 Cl H 2
(S,S)(S, S)
267 NH2 H CH3 C2H5 Cl267 NH 2 H CH 3 C 2 H 5 Cl
H2 H 2
(R,S)(R, S)
268 H2 NH2 H CH3 CH3 OH r [ A]D = H2 268 H 2 NH 2 H CH 3 CH 3 OH r [A] D = H 2
-5,8° (S,rac)-5.8 ° (S, rac)
269 NH2 H CH3 CH3 269 NH 2 H CH 3 CH 3
^ OH 20 WD =^ OH 20 W D =
H2 y> +6,5° (R,rac) 71 -H 2 y> + 6.5 ° (R, rac) 71 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
270 H2 270 H 2
^c- NH2 H CH3 CH3 Cl (amorph)^ c - NH 2 H CH 3 CH 3 Cl (amorphous)
H2 JQ (S,rac)H 2 JQ (S, rac)
271 H 2 NH2 H CH3 CH3 Cl r [α 1]2 D 0 = H2 271 H 2 NH 2 H CH 3 CH 3 Cl r [α 1 ] 2 D 0 = H 2
+6,5°+ 6.5 °
(R,rac)(R, rac)
272 NH2 H CH3 CH3 OH (amorph)272 NH 2 H CH 3 CH 3 OH (amorphous)
H2 H 2
CH3 CH3 OH 0 (S,rac)CH 3 CH 3 OH 0 (S, rac)
273 H2 NH2 H rα π]2 D 0 = H2 273 H 2 NH 2 H rα π] 2 D 0 = H 2
+22°+ 22 °
l o [l o [
(R,rac)(R, rac)
274 H 2 NH2 H CH3 CH3 C r [α π]2 D 0 = H2 274 H 2 NH 2 H CH 3 CH 3 C r [α π] 2 D 0 = H 2
-3,8° (S,rac)-3.8 ° (S, rac)
275 H2 NH2 H CH3 CH3 Cl r [α π]2 D 0 = H2 275 H 2 NH 2 H CH 3 CH 3 Cl r [α π] 2 D 0 = H 2
+5,4° (R,rac)+ 5.4 ° (R, rac)
276 NH2 H CH3 C2H5 F276 NH 2 H CH 3 C 2 H 5 F
H2 A (amorph) (S,R) 72H 2 A (amorphous) (S, R) 72
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal. Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenEx. Physical. No. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
277 NH2 H CH3 C2H5 F (amorph)277 NH 2 H CH 3 C 2 H 5 F (amorphous)
H2 A log p: 2J2b-) (R,R)H 2 A log p: 2J2 b -) (R, R)
278 NH2 H CH3 C2H5 OH A r π20 + 108° (S,R)278 NH 2 H CH 3 C 2 H 5 OH A r π 20 + 108 ° (S, R)
279 NH2 H CH3 C2H5 OH xO r i20 279 NH 2 H CH 3 C 2 H 5 OH xO ri 20
+133°+ 133 °
(R,R)(R, R)
280 NH2 H CH3 C2H5 F xO r [« A]D =280 NH 2 H CH 3 C 2 H 5 F xO r [«A] D =
+106° log p: l,65a ) (S,R)+ 106 ° log p: l, 65 a ) (S, R)
281 NH2 H CH3 C2H5 F r [α π]2 D 0 =281 NH 2 H CH 3 C 2 H 5 F r [α π] 2 D 0 =
+152° log p: l ,64a-)+ 152 ° log p: l, 64 a -)
(R,R)(R, R)
282 NH2 H CH3 C2H5 F (amorph)282 NH 2 H CH 3 C 2 H 5 F (amorphous)
H2 -9 (R.R) - 73 -H 2 -9 (RR) - 73 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
283 NH2 H CH3 C2H5 F283 NH 2 H CH 3 C 2 H 5 F
H2 y (amorph) (S,R)H 2 y (amorphous) (S, R)
284 CH3 H CH3 C2H5 F CH3 284 CH 3 H CH 3 C 2 H 5 F CH 3
H2 -^^^^CHj (R,R) HH 2 - ^^^^ CH j (R, R) H
285 ^ H CH3 C2H5 F <?H3 285 ^ H CH 3 C 2 H 5 F <? H 3
H2 ^ C2H5 cAi ^y^c 3 (R,R)H 2 ^ C 2 H 5 cAi ^ y ^ c 3 (R, R)
HAHA
286 N(CH3)2 286 N (CH 3 ) 2
H ^ H CH3 C2H5 F <?H3 2 H ^ H CH 3 C 2 H 5 F <? H 3 2
(R,R)(R, R)
287 NH2 H CH3 C2H5 F CH,287 NH 2 H CH 3 C 2 H 5 F CH,
H2 Ö (R,R)H 2 Ö (R, R)
288 CH3 H CH3 C2H5 F CH3 288 CH 3 H CH 3 C 2 H 5 F CH 3
H2 H X (R,R)H 2 HX (R, R)
289 CH3 H CH3 C2H5 F289 CH 3 H CH 3 C 2 H 5 F
H2 H A (R,R)H 2 HA (R, R)
290 ^ ^ C2H5 H CH3 C2H5 F290 ^ ^ C 2 H 5 H CH 3 C 2 H 5 F
H2 H 2
H AF (R,R) 74HA F (R, R) 74
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
291 ^ N(CH3)2 H CH3 C2H5 F291 ^ N (CH 3 ) 2 H CH 3 C 2 H 5 F
H2 H-A^ A (R,R)H 2 HA ^ A (R, R)
292 \ ^f NH2 H CH3 C2H5 F OCH,292 \ ^ f NH 2 H CH 3 C 2 H 5 F OCH,
H2 O (R,R)H 2 O (R, R)
293 ^ F293 ^ F
H2 ^ CH3 H CH3 C2H5 H 2 ^ CH 3 H CH 3 C 2 H 5
H y (R,R)H y (R, R)
294 ^ CH3 C2H5 F OCH,294 ^ CH 3 C 2 H 5 F OCH,
H2 ^ C2H5 HH 2 ^ C 2 H 5 H
H f (R,R)H f (R, R)
295 x H2 ^ NH2 H CH3 C2H5 F A (R,R)295 x H 2 ^ NH 2 H CH 3 C 2 H 5 FA (R, R)
296 NH2 H CH3 C2H5 F296 NH 2 H CH 3 C 2 H 5 F
H2 ACI (S,R)H 2 A CI (S, R)
297 CH3 H CH3 C2H5 F297 CH 3 H CH 3 C 2 H 5 F
H2 H A (R,R)H 2 HA (R, R)
298 C2H5 H CH3 C2H5 F Cl ^298 C 2 H 5 H CH 3 C 2 H 5 F Cl ^
H2 H y^^^a (R.R) - 75H 2 H y ^^^ a (RR) - 75
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 data and stereo chem. Information
299 N(CH3)2 H CH, C2H5 (R,R)299 N (CH 3 ) 2 H CH, C 2 H 5 (R, R)
300 .0. CH, H CH, C2H5 F300 .0. CH, H CH, C 2 H 5 F
X'X '
O f (R,R)O f (R, R)
301 X NH, H CH, C2H5 301 X NH, H CH, C 2 H 5
H, (R,R)H, (R, R)
302 NH, H CH, C,H302 NH, H CH, C, H
H. (R,R)H. (R, R)
303 .0. NH, H CH, C2H5 303 .0. NH, H CH, C 2 H 5
X' (R,R)X ' (R, R)
304 X. NH, H CH, C2H5 304 X. NH, H CH, C 2 H 5
X' (R,R)X ' (R, R)
305 . NH, H CH, C2H5 305. NH, H CH, C 2 H 5
H„ (S,R)H" (S, R)
306 . NH2 H CH, CΛ306. NH 2 H CH, CΛ
X' (R,R) - 76X ' (R, R) - 76
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
307 NH2 H CH3 C2H5 F CH3 307 NH 2 H CH 3 C 2 H 5 F CH 3
X -X -
H2 H 2
(S,R)(S, R)
308 H3 C2H5 F ?H3 308 H 3 C 2 H 5 F? H 3
H2 ^ CH3 H CH 2 ^ CH 3 HC
H (R,R)H (R, R)
309 ^ H ^ C2H5 H CH3 C2H5 F 9H3 2 H (R,R)309 ^ H ^ C 2 H 5 H CH 3 C 2 H 5 F 9H 3 2 H (R, R)
310 NH2 H CH3 CH3 F log p: l,39a xO (R,R)310 NH 2 H CH 3 CH 3 F log p: l, 39 a xO (R, R)
311 H H CH3 CH3 F xO H (R,R)311 HH CH 3 CH 3 F xO H (R, R)
312 CH3 H CH3 CH3 F x f^yy H (R,R)312 CH 3 H CH 3 CH 3 F xf ^ yy H (R, R)
313 C2H5 H CH3 CH3 F313 C 2 H 5 H CH 3 CH 3 F
XXXX
H (R,R)H (R, R)
314 H H CH3 CH3 F f H (R,S)314 HH CH 3 CH 3 F f H (R, S)
315 CH3 H CH3 CH, F315 CH 3 H CH 3 CH, F
C N XfC N Xf
H^ (R,S) - 77H ^ (R, S) - 77
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
316 C2H5 H CH3 CH3 F xO H (R,S)316 C 2 H 5 H CH 3 CH 3 F xO H (R, S)
317 NH2 H CH3 CH3 F317 NH 2 H CH 3 CH 3 F
XX (R,rac)XX (R, rac)
318 H H CH3 CH3 F xO H (R,rac)318 HH CH 3 CH 3 F xO H (R, rac)
319 H H CH3 C2H5 F log p: 2,52a-> xO (R,R) H319 HH CH 3 C 2 H 5 F log p: 2.52 a -> xO (R, R) H
320 CH3 H CH3 C2H5 F xO H (R,R)320 CH 3 H CH 3 C 2 H 5 F xO H (R, R)
321 C2H5 H CH3 C2H5 F log p: 2,70a4> xO (R,R)321 C 2 H 5 H CH 3 C 2 H 5 F log p: 2.70 a 4> xO (R, R)
HH
322 NH2 H CH3 C2H5 F322 NH 2 H CH 3 C 2 H 5 F
XX (R,R)XX (R, R)
323 H H CH3 C2H5 F323 HH CH 3 C 2 H 5 F
XX H (R,S)XX H (R, S)
324 CH3 H CH3 C2H5 F324 CH 3 H CH 3 C 2 H 5 F
XX H (R,S) 78XX H (R, S) 78
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
325 C2H5 H CH3 C2H5 F xO325 C 2 H 5 H CH 3 C 2 H 5 F xO
H (R,S)H (R, S)
326 C3H7-n H CH3 C2H5 F326 C 3 H 7 -n H CH 3 C 2 H 5 F
XX H (R,S)XX H (R, S)
327 NH2 H CH3 C2H5 F327 NH 2 H CH 3 C 2 H 5 F
XX R,rac)XX R, rac)
328 H H CH3 CH3 F χya log p: 2,61^328 HH CH 3 CH 3 F χy a log p: 2.61 ^
H (R,R)H (R, R)
329 CH3 H CH3 CH3 F329 CH 3 H CH 3 CH 3 F
Ar xxa (R,R)Ar xx a (R, R)
330 C2H5 H CH3 CH3 F Xf log p: 2J9a.» Fp.: 1 19°C330 C 2 H 5 H CH 3 CH 3 F Xf log p: 2J9 a . » Mp: 1 19 ° C
H (R,R)H (R, R)
331 C3H7-i H CH3 CH3 F Xf H (R,R)331 C 3 H 7 -i H CH 3 CH 3 F Xf H (R, R)
332 H H CH3 CH3 F f H (R,S) 79332 HH CH 3 CH 3 F f H (R, S) 79
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
333 CH3 H CH3 CH3 F XX H (R,S)333 CH 3 H CH 3 CH 3 F XX H (R, S)
334 C2H5 H CH3 CH3 F Xf334 C 2 H 5 H CH 3 CH 3 F Xf
H (R,S)H (R, S)
335 C3H7-i H CH3 CH3 F iTA H (R,S)335 C 3 H 7 -i H CH 3 CH 3 F iTA H (R, S)
336 NH2 H CH3 CH3 F Xf (R,rac)336 NH 2 H CH 3 CH 3 F Xf (R, rac)
337 NH2 H CH3 C2H5 F xxa (R,R)337 NH 2 H CH 3 C 2 H 5 F xx a (R, R)
338 H H CH3 C2H5 F xf H (R,R)338 HH CH 3 C 2 H 5 F xf H (R, R)
339 CH3 H CH3 C2H5 F f H (R,R)339 CH 3 H CH 3 C 2 H 5 F f H (R, R)
340 C2H5 H CH3 C2H5 F xx° H (R,R)340 C 2 H 5 H CH 3 C 2 H 5 F xx ° H (R, R)
341 NH2 H CH, C2H5 F XX (R,S) 80341 NH 2 H CH, C 2 H 5 F XX (R, S) 80
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
342 H H CH3 C2H5 F XX H (R,S)342 HH CH 3 C 2 H 5 F XX H (R, S)
343 CH3 H CH3 C2H5 F343 CH 3 H CH 3 C 2 H 5 F
H xf (R,S)H xf (R, S)
344 C2H5 H CH3 C2H5 F344 C 2 H 5 H CH 3 C 2 H 5 F
CAN χya H"" (R,S)CAN χy a H "" (R, S)
345 NH2 H CH3 C2H5 F Xf (R,rac)345 NH 2 H CH 3 C 2 H 5 F Xf (R, rac)
346 NH2 H CH3 C2H5 F / CH3346 NH 2 H CH 3 C 2 H 5 F / CH 3
(R,R)(R, R)
347 H H CH3 CH3 F / CH3347 HH CH 3 CH 3 F / CH 3
H (R,R)H (R, R)
348 CH3 H CH3 CH3 F f^f0"*348 CH 3 H CH 3 CH 3 F f ^ f 0 "*
H (R,R)H (R, R)
349 C2H5 H CH3 CH3 F ^ CH3349 C 2 H 5 H CH 3 CH 3 F ^ CH 3
H (R,R)H (R, R)
350 H H CH3 CH3 F350 HH CH 3 CH 3 F
H (R,S) 81H (R, S) 81
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
351 CH3 H CH3 CH3 F ^ CH3351 CH 3 H CH 3 CH 3 F ^ CH 3
H (R,S)H (R, S)
352 C2H5 H CH3 CH3 F352 C 2 H 5 H CH 3 CH 3 F
H (R,S)H (R, S)
353 NH2 H CH3 CH3 F /^/CH3 353 NH 2 H CH 3 CH 3 F / ^ / CH 3
(R,rac)(R, rac)
354 NH2 H CH3 C2H5 F ^ CH3354 NH 2 H CH 3 C 2 H 5 F ^ CH 3
(R,R)(R, R)
355 H H CH3 C2H5 F -^γ-CH=355 HH CH 3 C 2 H 5 F - ^ γ- CH =
H (R,R)H (R, R)
356 CH3 H CH3 C2H5 F / CH3 XX H (R,R)356 CH 3 H CH 3 C 2 H 5 F / CH 3 XX H (R, R)
357 C2H5 H CH3 C2H5 F / CH3357 C 2 H 5 H CH 3 C 2 H 5 F / CH 3
H (R,R)H (R, R)
368 NH2 H CH3 C2H5 F S^X"*368 NH 2 H CH 3 C 2 H 5 FS ^ X "*
(R,S)(R, S)
359 H H CH3 C,H5 F XX" H (R,S) 82 -359 HH CH 3 C, H 5 F XX "H (R, S) 82 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
360 CH3 H CH3 C2H5 F /yCH,360 CH 3 H CH 3 C 2 H 5 F / yCH,
H (R,S)H (R, S)
361 C2H5 H CH3 C2H5 F /yCH,361 C 2 H 5 H CH 3 C 2 H 5 F / yCH,
H (R,S)H (R, S)
362 NH2 H CH, C2H5 F362 NH 2 H CH, C 2 H 5 F
(R,rac)(R, rac)
363 NH2 H CH3 CH3 F XX (R,R)363 NH 2 H CH 3 CH 3 F XX (R, R)
364 H H CH3 CH3 F ff H (R,R)364 HH CH 3 CH 3 F ff H (R, R)
365 CH3 H CH3 CH3 F XX H (R,R)365 CH 3 H CH 3 CH 3 F XX H (R, R)
366 C2H5 H CH3 CH3 F f H (R,R)366 C 2 H 5 H CH 3 CH 3 F f H (R, R)
367 H H CH3 CH3 F XX H (R,S)367 HH CH 3 CH 3 F XX H (R, S)
368 CH3 H CH, CH3 F XX H (R,S) 83368 CH 3 H CH, CH 3 F XX H (R, S) 83
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
369 C2H5 H CH3 CH3 F369 C 2 H 5 H CH 3 CH 3 F
C N XXC N XX
H"' (R,S)H "' (R, S)
370 NH2 H CH3 CH3 F XX370 NH 2 H CH 3 CH 3 F XX
(R,rac)(R, rac)
371 NH2 H CH3 C2H5 F XX log p: l ,77aJ (R,R)371 NH 2 H CH 3 C 2 H 5 F XX log p: l, 77 a J (R, R)
372 H H CH3 C2H5 F XX H (R,R)372 HH CH 3 C 2 H 5 F XX H (R, R)
373 CH3 H CH3 C2H5 F ff" H (R,R)373 CH 3 H CH 3 C 2 H 5 F ff "H (R, R)
374 C2H5 H CH3 C2H5 F XX374 C 2 H 5 H CH 3 C 2 H 5 F XX
H (R,R)H (R, R)
375 NH2 H CH3 C2H5 F XX (R,S)375 NH 2 H CH 3 C 2 H 5 F XX (R, S)
376 H H CH3 C2H5 F XX H (R,S)376 HH CH 3 C 2 H 5 F XX H (R, S)
377 CH3 H CH3 C2H5 F XX H (R,S) - 84377 CH 3 H CH 3 C 2 H 5 F XX H (R, S) - 84
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
378 C2H5 H CH3 C2H5 F XX H (R,S)378 C 2 H 5 H CH 3 C 2 H 5 F XX H (R, S)
379 NH2 H CH3 C2H5 F iTYF 379 NH 2 H CH 3 C 2 H 5 F iTY F
(R,rac)(R, rac)
380 NH2 H CH3 CH3 F / 0CH3380 NH 2 H CH 3 CH 3 F / 0CH 3
(R,R)(R, R)
381 H H CH3 CH3 F /γOCH,381 HH CH 3 CH 3 F / γOCH,
H (R,R)H (R, R)
382 CH3 H CH3 CH3 F382 CH 3 H CH 3 CH 3 F
C N"" Xf H (R,R)C N "" Xf H (R, R)
383 C2H5 H CH3 CH3 F f ' 383 C 2 H 5 H CH 3 CH 3 F f '
H (R,R)H (R, R)
384 H H CH3 CH3 F Xf' H (R,S)384 HH CH 3 CH 3 F Xf ' H (R, S)
385 CH3 H CH3 CH3 F /γ°CH,385 CH 3 H CH 3 CH 3 F / γ ° CH,
H (R,S)H (R, S)
386 C2H5 H CH3 CH3 F / 0CH3386 C 2 H 5 H CH 3 CH 3 F / 0CH 3
H (R,S) 85-H (R, S) 85-
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
387 NH2 H CH3 CH3 F /^/OCH3 387 NH 2 H CH 3 CH 3 F / ^ / OCH 3
(R,rac)(R, rac)
388 NH2 H CH3 C2H5 F / 0CH3388 NH 2 H CH 3 C 2 H 5 F / 0CH 3
(R,R)(R, R)
389 H H CH3 C2H5 F ^-/OCH,389 HH CH 3 C 2 H 5 F ^ - / OCH,
C N H"' (R,R)CNH "' (R, R)
390 CH3 H CH3 C2H5 F / 0CH3 390 CH 3 H CH 3 C 2 H 5 F / 0CH 3
H (R,R)H (R, R)
391 C2H5 H CH3 C2H5 F / -°CH3 391 C 2 H 5 H CH 3 C 2 H 5 F / - ° CH 3
H (R,R)H (R, R)
392 NH2 H CH3 C2H5 F /^ 0CHι392 NH 2 H CH 3 C 2 H 5 F / ^ 0CH ι
(R,S)(R, S)
393 H H CH3 C2H5 F / 0CH3393 HH CH 3 C 2 H 5 F / 0CH 3
H (R,S)H (R, S)
394 CH3 H CH3 C2H5 F ^γ-0CH>394 CH 3 H CH 3 C 2 H 5 F ^ γ- 0CH >
XXX H (R,S)XXX H (R, S)
395 C2H5 H CH3 C2H5 F / 0CH3395 C 2 H 5 H CH 3 C 2 H 5 F / 0CH 3
H (R,S) 86 -H (R, S) 86 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
396 NH2 H CH3 C2H5 F ^γ-°CH3 396 NH 2 H CH 3 C 2 H 5 F ^ γ- ° CH 3
(R,rac)(R, rac)
397 NH2 H CH3 CH3 F o; 397 NH 2 H CH 3 CH 3 F o ;
(R,R)(R, R)
398 H H CH3 CH3 F /y^398 HH CH 3 CH 3 F / y ^
H (R,R)H (R, R)
399 CH3 H CH3 CH3 F ^ N02399 CH 3 H CH 3 CH 3 F ^ N0 2
H (R,R)H (R, R)
400 C2H5 H CH3 CH3 F Xf' H (R,R)400 C 2 H 5 H CH 3 CH 3 F Xf ' H (R, R)
401 NH2 H CH3 CH3 F ^ N°2401 NH 2 H CH 3 CH 3 F ^ N ° 2
(R,S)(R, S)
402 H H CH3 CH3 F / o! 402 HH CH 3 CH 3 F / o !
H (R,S)H (R, S)
403 CH3 H CH3 CH3 F [TYN°2 H (R,S)403 CH 3 H CH 3 CH 3 F [TY N ° 2 H (R, S)
404 C2H5 H CH3 CH3 F ^o,404 C 2 H 5 H CH 3 CH 3 F ^ o,
H (R,S) - 87 -H (R, S) - 87 -
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
405 NH2 H CH3 CH3 F f^/N0^405 NH 2 H CH 3 CH 3 F f ^ / N0 ^
(R,rac)(R, rac)
406 NH2 H CH3 C2H5 F406 NH 2 H CH 3 C 2 H 5 F
(R,R)(R, R)
407 H H CH3 C2H5 F /V»,407 HH CH 3 C 2 H 5 F / V »,
H (R,R)H (R, R)
408 CH3 H CH3 C2H5 F /y^408 CH 3 H CH 3 C 2 H 5 F / y ^
H (R,R)H (R, R)
409 C2H5 H CH3 C2H5 F409 C 2 H 5 H CH 3 C 2 H 5 F
H xr (R,R)H xr (R, R)
410 NH2 H CH3 C2H5 F f^= N02410 NH 2 H CH 3 C 2 H 5 F f ^ = N0 2
(R,S)(R, S)
411 H H CH3 C2H5 F Xf' H (R,S)411 HH CH 3 C 2 H 5 F Xf ' H (R, S)
412 CH3 H CH3 C2H5 F / N°2412 CH 3 H CH 3 C 2 H 5 F / N ° 2
H (R,S)H (R, S)
413 C2H5 H CH, C2H5 F ιTYN°2 H (R.S) 88413 C 2 H 5 H CH, C 2 H 5 F ιTY N ° 2 H (RS) 88
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
414 NH2 H CH3 C2H5 F f^γNOι414 NH 2 H CH 3 C 2 H 5 F f ^ γ NO ι
(R,rac)(R, rac)
415 NH2 H CH3 CH3 F xr (R,R)415 NH 2 H CH 3 CH 3 F xr (R, R)
416 H H CH3 CH3 F416 HH CH 3 CH 3 F
H xr (R,R)H xr (R, R)
417 CH3 H CH3 CH3 F XX" H (R,R)417 CH 3 H CH 3 CH 3 F XX "H (R, R)
418 C2H5 H CH3 CH3 F418 C 2 H 5 H CH 3 CH 3 F
H xr (R,R)H xr (R, R)
419 NH2 H CH3 CH3 F A3 419 NH 2 H CH 3 CH 3 FA 3
(R,S)(R, S)
420 H H CH3 CH3 F xf H (R,S)420 HH CH 3 CH 3 F xf H (R, S)
421 CH3 H CH3 CH3 F Xf H (R,S)421 CH 3 H CH 3 CH 3 F Xf H (R, S)
422 C2H5 H CH3 CH, F XX" H (R,S) 89 -422 C 2 H 5 H CH 3 CH, F XX "H (R, S) 89 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
423 NH2 H CH3 CH3 F f (R,rac)423 NH 2 H CH 3 CH 3 F f (R, rac)
424 NH2 H CH3 C2H5 F f (R,R)424 NH 2 H CH 3 C 2 H 5 F f (R, R)
425 H H CH3 C2H5 F425 HH CH 3 C 2 H 5 F
H f (R,R)H f (R, R)
426 CH3 H CH3 C2H5 F426 CH 3 H CH 3 C 2 H 5 F
H f (R,R)H f (R, R)
427 C2H5 H CH3 C2H5 F427 C 2 H 5 H CH 3 C 2 H 5 F
H xr (R,R)H xr (R, R)
428 NH2 H CH3 C2H5 F Xf (R,S)428 NH 2 H CH 3 C 2 H 5 F Xf (R, S)
429 H H CH3 C2H5 F429 HH CH 3 C 2 H 5 F
H f (R,S)H f (R, S)
430 CH3 H CH3 C2H5 F XX" H (R,S)430 CH 3 H CH 3 C 2 H 5 F XX "H (R, S)
431 C2H5 H CH3 C2H5 F XX" H (R,S) - 90431 C 2 H 5 H CH 3 C 2 H 5 F XX "H (R, S) - 90
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
432 NH2 H CH3 C2H5 F XX"432 NH 2 H CH 3 C 2 H 5 F XX "
(R,rac)(R, rac)
433 NH2 H CH3 CH3 F433 NH 2 H CH 3 CH 3 F
JÖ (R,R)JÖ (R, R)
434 H H CH3 CH3 F434 HH CH 3 CH 3 F
H f (R,R)H f (R, R)
435 CH3 H CH3 CH3 F435 CH 3 H CH 3 CH 3 F
H xf (R,R)H xf (R, R)
436 C2H5 H CH3 CH3 F436 C 2 H 5 H CH 3 CH 3 F
H f (R,R)H f (R, R)
437 NH2 H CH3 CH3 F f (R,S)437 NH 2 H CH 3 CH 3 F f (R, S)
438 H H CH3 CH3 F438 HH CH 3 CH 3 F
H Ö (R,S)H Ö (R, S)
439 CH3 H CH3 CH3 F439 CH 3 H CH 3 CH 3 F
H f (R,S)H f (R, S)
440 C2H5 H CH3 CH3 F440 C 2 H 5 H CH 3 CH 3 F
H f (R,S) - 91H f (R, S) - 91
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
441 NH2 H CH3 CH3 F441 NH 2 H CH 3 CH 3 F
JÖ (R,rac)JÖ (R, rac)
442 NH2 H CH3 C2H5 F442 NH 2 H CH 3 C 2 H 5 F
JÖ (R,R)JÖ (R, R)
443 H H CH3 C2H5 F443 HH CH 3 C 2 H 5 F
H JÖ (R,R)H JÖ (R, R)
444 CH3 H CH3 C2H5 F444 CH 3 H CH 3 C 2 H 5 F
H JÖ (R,R)H JÖ (R, R)
445 C2H5 H CH3 C2H5 F445 C 2 H 5 H CH 3 C 2 H 5 F
H Ö (R,R)H Ö (R, R)
446 NH2 H CH3 C2H5 F446 NH 2 H CH 3 C 2 H 5 F
JÖ (R,S)JÖ (R, S)
447 H H CH3 C2H5 F447 HH CH 3 C 2 H 5 F
H (R,S)H (R, S)
448 CH3 H CH3 C2H5 F448 CH 3 H CH 3 C 2 H 5 F
H JÖ (R,S)H JÖ (R, S)
449 C2H5 H CH3 C2H5 F449 C 2 H 5 H CH 3 C 2 H 5 F
H JÖ (R,S) 92H JÖ (R, S) 92
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
450 NH2 H CH3 C2H5 F450 NH 2 H CH 3 C 2 H 5 F
JÖ (R,rac)JÖ (R, rac)
451 NH2 H CH3 CH3 F f (R,R)451 NH 2 H CH 3 CH 3 F f (R, R)
452 H H CH3 CH3 F X F} H (R,R)452 HH CH 3 CH 3 FXF} H (R, R)
453 CH3 H CH3 CH3 F453 CH 3 H CH 3 CH 3 F
F H ? (R,R)F H? (R, R)
454 C2H5 H CH3 CH3 F454 C 2 H 5 H CH 3 CH 3 F
H -9 (R,R)H -9 (R, R)
455 NH2 H CH3 CH3 F -9 (R,S)455 NH 2 H CH 3 CH 3 F -9 (R, S)
456 H H CH3 CH3 F456 HH CH 3 CH 3 F
H Xf (R,S)H Xf (R, S)
457 CH3 H CH3 CH3 F X F? H (R,S)457 CH 3 H CH 3 CH 3 FXF? H (R, S)
458 C2H5 H CH3 CH, F458 C 2 H 5 H CH 3 CH, F
0 N/ 0 N /
H f F (R,S) 93H f F (R, S) 93
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 data and stereo chem. Information
459 NH, H CH, CH, (R,rac)459 NH, H CH, CH, (R, rac)
460 NH, H CH, C2H5 (R,R)460 NH, H CH, C 2 H 5 (R, R)
461 H H CH, C2H5 461 HH CH, C 2 H 5
H (R,R)H (R, R)
462 CH3 H CH, C2H5 H (R,R)462 CH 3 H CH, C 2 H 5 H (R, R)
463 C2H5 H CH, C, 2HJ"l5463 C 2 H 5 H CH, C, 2 H J " l 5
O • Hr (R,R)O • Hr (R, R)
464 NH, H CH, C2H5 (R,S)464 NH, H CH, C 2 H 5 (R, S)
465 H H CH, C2H5 θA 465 HH CH, C 2 H 5 θA
H' (R,S)H '(R, S)
466 CH, H CH, C2H5 466 CH, H CH, C 2 H 5
O X' . N H (R,S)OX '. N H (R, S)
467 C2H5 H CH3 C2H5 f 467 C 2 H 5 H CH 3 C 2 H 5 f
(R,S) 94(R, S) 94
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
468 NH2 H CH3 C2H5 F -9 (R,rac)468 NH 2 H CH 3 C 2 H 5 F -9 (R, rac)
469 NH2 H CH3 CH3 F Cl469 NH 2 H CH 3 CH 3 F Cl
JÖ (R,R)JÖ (R, R)
470 H H CH3 CH3 F Cl470 HH CH 3 CH 3 F Cl
H (R,R)H (R, R)
471 CH3 H CH3 CH3 F Cl471 CH 3 H CH 3 CH 3 F Cl
H JÖ (R,R)H JÖ (R, R)
472 C2H5 H CH3 CH3 F Cl472 C 2 H 5 H CH 3 CH 3 F Cl
H f (R,R)H f (R, R)
473 NH2 H CH3 CH3 F Cl x (R,S)473 NH 2 H CH 3 CH 3 F Cl x (R, S)
474 H H CH3 CH3 F Cl474 HH CH 3 CH 3 F Cl
H Ö (R,S)H Ö (R, S)
475 CH3 H CH3 CH3 F Cl475 CH 3 H CH 3 CH 3 F Cl
H JÖ (R,S)H JÖ (R, S)
476 C2H5 H CH3 CH, F Cl476 C 2 H 5 H CH 3 CH, F Cl
H f (R,S) 95H f (R, S) 95
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
477 NH2 H CH3 CH3 F Cl477 NH 2 H CH 3 CH 3 F Cl
JÖ (R,rac)JÖ (R, rac)
478 NH2 H CH3 C2H5 F Cl478 NH 2 H CH 3 C 2 H 5 F Cl
JÖ (R,R)JÖ (R, R)
479 H H CH3 C2H5 F Cl479 HH CH 3 C 2 H 5 F Cl
H JÖ (R,R)H JÖ (R, R)
480 CH3 H CH3 C2H5 F Cl480 CH 3 H CH 3 C 2 H 5 F Cl
H JÖ (R,R)H JÖ (R, R)
481 C2H5 H CH3 C2H5 F Cl θ Hτ" JÖ (R,R)481 C 2 H 5 H CH 3 C 2 H 5 F Cl θ Hτ "JÖ (R, R)
482 NH2 H CH3 C2H5 F Cl482 NH 2 H CH 3 C 2 H 5 F Cl
JÖ (R,S)JÖ (R, S)
483 H H CH3 C2H5 F cι483 HH CH 3 C 2 H 5 F cι
H JÖ (R,S)H JÖ (R, S)
484 CH3 H CH3 C2H5 F Cl484 CH 3 H CH 3 C 2 H 5 F Cl
H JÖ (R,S)H JÖ (R, S)
485 C2H5 H CH3 C2H5 F Cl485 C 2 H 5 H CH 3 C 2 H 5 F Cl
H JÖ (R-S) 96 -H JÖ (RS) 96 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
486 NH2 H CH3 C2H5 F Cl486 NH 2 H CH 3 C 2 H 5 F Cl
JÖ (R,rac)JÖ (R, rac)
487 NH2 H CH3 CH3 F OCH,487 NH 2 H CH 3 CH 3 F OCH,
JÖ (R,R)JÖ (R, R)
488 H H CH3 CH3 F OCH,488 HH CH 3 CH 3 F OCH,
H JÖ (R,R)H JÖ (R, R)
489 CH3 H CH3 CH3 F OCH, oA H"" JÖ (R,R)489 CH 3 H CH 3 CH 3 F OCH, oA H "" JÖ (R, R)
490 C2H5 H CH3 CH3 F OCH,490 C 2 H 5 H CH 3 CH 3 F OCH,
H (R,R)H (R, R)
491 NH2 H CH3 CH3 F ό* (R,S)491 NH 2 H CH 3 CH 3 F ό * (R, S)
492 H H CH3 CH3 F OCH,492 HH CH 3 CH 3 F OCH,
H (R,S)H (R, S)
493 CH3 H CH3 CH3 F493 CH 3 H CH 3 CH 3 F
HH
C2H5 s (R,S)C 2 H 5 s (R, S)
494 H CH, CH3 F OCH,494 H CH, CH 3 F OCH,
H JÖ (R,S) - 97H JÖ (R, S) - 97
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
495 NH2 H CH3 CH3 F OCH,495 NH 2 H CH 3 CH 3 F OCH,
JÖ (R,rac)JÖ (R, rac)
496 NH2 H CH3 C2H5 F OCH,496 NH 2 H CH 3 C 2 H 5 F OCH,
JÖ (R,R)JÖ (R, R)
497 H H CH3 C2H5 F OCH3 497 HH CH 3 C 2 H 5 F OCH 3
H JÖ (R,R)H JÖ (R, R)
498 CH3 H CH3 C2H5 F OCH,498 CH 3 H CH 3 C 2 H 5 F OCH,
H JÖ (R,R)H JÖ (R, R)
499 C2H5 H CH3 C2H5 F OCH,499 C 2 H 5 H CH 3 C 2 H 5 F OCH,
H JÖ (R,R)H JÖ (R, R)
500 NH2 H CH3 C2H5 F OCH.500 NH 2 H CH 3 C 2 H 5 F OCH.
JÖ (R,S)JÖ (R, S)
501 H H CH3 C2H5 F OCH, oA H"" JÖ (R,S)501 HH CH 3 C 2 H 5 F OCH, oA H "" JÖ (R, S)
502 CH3 H CH3 C2H5 F OCH3 502 CH 3 H CH 3 C 2 H 5 F OCH 3
H JÖ (R,S)H JÖ (R, S)
503 OCH,503 OCH,
C2H5 H CH, C2H5 F C 2 H 5 H CH, C 2 H 5 F
H JÖ (R,S) - 98 -H JÖ (R, S) - 98 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
504 NH2 H CH3 CH3 F OCH,504 NH 2 H CH 3 CH 3 F OCH,
JÖ (R,rac)JÖ (R, rac)
505 NH2 H CH3 CH3 F CH,505 NH 2 H CH 3 CH 3 F CH,
JÖ (R,R)JÖ (R, R)
506 H H CH3 CH3 F CH3 506 HH CH 3 CH 3 F CH 3
H JÖ (R,R)H JÖ (R, R)
507 CH3 H CH3 CH3 F <?H3 507 CH 3 H CH 3 CH 3 F <? H 3
H (R,R)H (R, R)
508 C2H5 H CH3 CH3 F508 C 2 H 5 H CH 3 CH 3 F
H y (R,R)H y (R, R)
509 NH2 H CH3 CH3 F i3 (R,S)509 NH 2 H CH 3 CH 3 F i3 (R, S)
510 H H CH3 CH3 F510 HH CH 3 CH 3 F
H y (R,S)H y (R, S)
511 CH3 H CH3 CH3 F CH3 511 CH 3 H CH 3 CH 3 F CH 3
H JÖ (R,S)H JÖ (R, S)
512 C2H5 H CH, CH3 F CH,512 C 2 H 5 H CH, CH 3 F CH,
H f (R,S) 99 -H f (R, S) 99 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
513 NH2 H CH3 CH3 F CH3 J (R,rac)513 NH 2 H CH 3 CH 3 F CH 3 J (R, rac)
514 NH2 H CH3 C2H5 F y (R,R)514 NH 2 H CH 3 C 2 H 5 F y (R, R)
515 H H CH3 C2H5 F CH3 515 HH CH 3 C 2 H 5 F CH 3
JÖ (R,R)JÖ (R, R)
516 CH3 H CH3 C2H5 F CH3 oA H-" JÖ (R,R)516 CH 3 H CH 3 C 2 H 5 F CH 3 oA H- "JÖ (R, R)
517 C2H5 H CH3 C2H5 F CH3 517 C 2 H 5 H CH 3 C 2 H 5 F CH 3
H JÖ (R,R)H JÖ (R, R)
518 NH2 H CH3 C2H5 F CH,518 NH 2 H CH 3 C 2 H 5 F CH,
JÖ (R,S)JÖ (R, S)
519 H H CH3 C2H5 F CH, θ Hτ" JÖ (R,S)519 HH CH 3 C 2 H 5 F CH, θ Hτ "JÖ (R, S)
520 CH3 H CH3 C2H5 F520 CH 3 H CH 3 C 2 H 5 F
H J5 (R,S)H J5 (R, S)
521 C2H5 H CH3 C2H5 F CH3 521 C 2 H 5 H CH 3 C 2 H 5 F CH 3
H JÖ (R,S) 100H JÖ (R, S) 100
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 data and stereo chem. Information
522 NH, H CH, C2H5 (R,rac)522 NH, H CH, C 2 H 5 (R, rac)
523 NH, H CH, CH, (R,R)523 NH, H CH, CH, (R, R)
524 H H CH, CH, oA 524 HH CH, CH, oA
H' (R,R)H '(R, R)
525 CH3 H CH, CH, o 525 CH 3 H CH, CH, o
Hr (R,R)Hr (R, R)
526 C2H5 H CH, CH, 526 C 2 H 5 H CH, CH,
H (R,R)H (R, R)
527 NH, H CH, CH, (R,S)527 NH, H CH, CH, (R, S)
528 H H CH, CH, θ Hl' (R,S)528 HH CH, CH, θ Hl '(R, S)
529 CH3 H CH, CH, θA H' (R,S)529 CH 3 H CH, CH, θA H '(R, S)
530 C2H5 H CH, CH, H (R,S) - 101 -530 C 2 H 5 H CH, CH, H (R, S) - 101 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
531 NH, H CH, CH3 (R,rac)531 NH, H CH, CH 3 (R, rac)
532 NH, H CH, C2H5 (R,R)532 NH, H CH, C 2 H 5 (R, R)
533 H H CH3 C2H5 533 HH CH 3 C 2 H 5
O' O'
H (R,R)H (R, R)
534 CH3 H CH, C2H5 534 CH 3 H CH, C 2 H 5
Ar (R,R)Ar (R, R)
535 C2H5 H CH, C2H5 535 C 2 H 5 H CH, C 2 H 5
H (R,R)H (R, R)
536 NH, H CH, C2H5 (R,S)536 NH, H CH, C 2 H 5 (R, S)
537 H H CH, C2H5 oA- (R,S)537 HH CH, C 2 H 5 oA- (R, S)
538 CH3 H CH, C2H5 θA H' (R,S)538 CH 3 H CH, C 2 H 5 θA H '(R, S)
539 C2H5 H CH, C, 2HU5 539 C 2 H 5 H CH, C, 2H U 5
H (R,S) 102H (R, S) 102
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
540 NH2 H CH3 C2H5 F y. (R,rac)540 NH 2 H CH 3 C 2 H 5 F y. (R, rac)
541 NH, H CH3 CH3 F /^ C2HS541 NH, H CH 3 CH 3 F / ^ C 2 H S
(R.R)(R.R)
542 H H CH3 CH3 F χχCΛ H (R.R)542 HH CH 3 CH 3 F χχ CΛ H (RR)
543 CH3 H CH3 CH3 F / C2H5 543 CH 3 H CH 3 CH 3 F / C 2 H 5
H (R,R)H (R, R)
544 C2H5 H CH3 CH3 F /%% ^C2H5544 C 2 H 5 H CH 3 CH 3 F / %% ^ C 2 H 5
H (R,R)H (R, R)
545 NH2 H CH3 CH3 F / -/C2H5 f545 NH 2 H CH 3 CH 3 F / - / C 2 H 5 f
(R,S)(R, S)
546 H H CH3 CH3 F /^/C2H5 546 HH CH 3 CH 3 F / ^ / C 2 H 5
H (R,S)H (R, S)
547 CH3 H CH3 CH3 F ^^/C2H5547 CH 3 H CH 3 CH 3 F ^^ / C 2 H 5
H (R,S)H (R, S)
548 C2H5 H CH3 CH3 F XX"' 548 C 2 H 5 H CH 3 CH 3 F XX "'
H (R.S) 103H (RS) 103
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
549 NH2 H CH3 CH3 F yCΛ 549 NH 2 H CH 3 CH 3 F y CΛ
(R,rac)(R, rac)
550 NH2 H CH3 CH3 F550 NH 2 H CH 3 CH 3 F
(R,R)(R, R)
551 H H CH3 CH3 F551 HH CH 3 CH 3 F
H f> (R,R)H f> (R, R)
552 CH3 H CH3 CH3 F Γ\ H (R,R)552 CH 3 H CH 3 CH 3 F Γ \ H (R, R)
553 C2H5 H CH3 CH3 F553 C 2 H 5 H CH 3 CH 3 F
H (R,R)H (R, R)
554 NH2 H CH3 CH3 F554 NH 2 H CH 3 CH 3 F
(R,S)(R, S)
555 H H CH3 CH3 F Γ\ H (R,S)555 HH CH 3 CH 3 F Γ \ H (R, S)
556 CH3 H CH3 CH3 F556 CH 3 H CH 3 CH 3 F
H (R,S)H (R, S)
557 C2H5 H CH3 CH3 F557 C 2 H 5 H CH 3 CH 3 F
XL} H (R,S) - 104XL} H (R, S) - 104
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
558 NH2 H CH3 CH3 F Γ\558 NH 2 H CH 3 CH 3 F Γ \
(R,rac)(R, rac)
559 H H CH3 C2H5 F559 HH CH 3 C 2 H 5 F
H (R,R)H (R, R)
560 CH3 H CH3 C2H5 F560 CH 3 H CH 3 C 2 H 5 F
H (R,R)H (R, R)
561 C2H5 H CH3 C2H5 F561 C 2 H 5 H CH 3 C 2 H 5 F
H (R,R)H (R, R)
562 NH2 H CH3 C2H5 F Γ\562 NH 2 H CH 3 C 2 H 5 F Γ \
(R,S)(R, S)
563 H H CH3 C2H5 F563 HH CH 3 C 2 H 5 F
H (R,S)H (R, S)
564 CH3 H CH3 C2H5 F564 CH 3 H CH 3 C 2 H 5 F
H (R,S)H (R, S)
565 C2H5 H CH3 C2H5 F Γ\ H (R,S)565 C 2 H 5 H CH 3 C 2 H 5 F Γ \ H (R, S)
566 NH, H CH3 C,H5 F XL) (R,rac) - 105 -566 NH, H CH 3 C, H 5 F XL) (R, rac) - 105 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
567 NH2 H CH3 CH3 F567 NH 2 H CH 3 CH 3 F
CH3 F P (R,R)CH 3 F P (R, R)
568 H H CH3 568 HH CH 3
HH
H CH3 CH, F P (R,R)H CH 3 CH, F P (R, R)
569 CH3 569 CH 3
H 0 (R,R)H 0 (R, R)
570 C2H5 H CH3 CH3 F570 C 2 H 5 H CH 3 CH 3 F
H P (R,R)H P (R, R)
571 NH2 H CH3 CH3 F571 NH 2 H CH 3 CH 3 F
X (R,S)X (R, S)
572 H H CH3 CH3 F572 HH CH 3 CH 3 F
H / P (R,S)H / P (R, S)
573 CH3 H CH3 CH3 F573 CH 3 H CH 3 CH 3 F
H 0 (R,S)H 0 (R, S)
574 C2H5 H CH3 CH, F574 C 2 H 5 H CH 3 CH, F
H 0 (R.S) - 106 -H 0 (RS) - 106 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
575 NH2 H CH3 CH3 F575 NH 2 H CH 3 CH 3 F
P (R,rac) P (R, rac)
576 NH2 H CH3 C2H5 F 0 (R,R)576 NH 2 H CH 3 C 2 H 5 F 0 (R, R)
577 H H CH3 C2H5 F577 HH CH 3 C 2 H 5 F
H 0 (R,R)H 0 (R, R)
578 CH3 H CH3 C2H5 F578 CH 3 H CH 3 C 2 H 5 F
HH
F P (R,R)F P (R, R)
579 C2H5 H CH3 C2H5 579 C 2 H 5 H CH 3 C 2 H 5
H 0 (R,R)H 0 (R, R)
580 NH2 H CH3 C2H5 F580 NH 2 H CH 3 C 2 H 5 F
H3 C2H5 F P (R,S)H 3 C 2 H 5 F P (R, S)
581 H H C581 H H C
H 0 (R,S)H 0 (R, S)
582 CH3 H CH3 C2H5 F582 CH 3 H CH 3 C 2 H 5 F
H P (R,S) - 107H P (R, S) - 107
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 data and stereo chem. Information
583 2H5 H CH, C2H5 583 2 H 5 H CH, C 2 H 5
O^N (R,S) O ^ N (R, S)
584 NH, H CH, C2H5 584 NH, H CH, C 2 H 5
(R,rac) (R, rac)
585 NH, H CH, CH, cι585 NH, H CH, CH, cι
(R,R) (R, R)
586 H H CH, CH, cι586 H H CH, CH, cι
H (R,R) H (R, R)
587 CH3 H CH, CH, ci587 CH 3 H CH, CH, ci
H (R,R) H (R, R)
588 C2H5 H CH, CH, cι588 C 2 H 5 H CH, CH, cι
O^NO ^ N
H (R,R) H (R, R)
589 NH, H CH, CH, Cl589 NH, H CH, CH, Cl
(R,S) (R, S)
590 H CH3 CH, cι f ι\T590 H CH 3 CH, cι f ι \ T
H (R,S) - 108 -H (R, S) - 108 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
591 CH3 H CH, CH, Cl591 CH 3 H CH, CH, Cl
H (R,S) H (R, S)
592 C2H5 H CH, CH, Cl592 C 2 H 5 H CH, CH, Cl
H (R,S) H (R, S)
593 NH, H CH, CH3 ci593 NH, H CH, CH 3 ci
(R,rac) (R, rac)
594 NH, H CH, C2H5 cι594 NH, H CH, C 2 H 5 cι
(R,R) (R, R)
595 H H CH, C2H5 cι595 HH CH, C 2 H 5 cι
O^N' O ^ N '
H (R,R) H (R, R)
596 CH3 H CH, C2H5 cι596 CH 3 H CH, C 2 H 5 cι
H (R,R) H (R, R)
597 C,H5 H CH, C2H5 ci597 C, H 5 H CH, C 2 H 5 ci
O f H (R,R) O f H (R, R)
598 NH, H CH, C,H5 ci598 NH, H CH, C, H 5 ci
(R-S) - 109 -(RS) - 109 -
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
599 H H CH, C2H5 ci599 HH CH, C 2 H 5 ci
H (R,S) H (R, S)
600 CH3 H CH, C2H5 ci600 CH 3 H CH, C 2 H 5 ci
H (R,S) H (R, S)
601 C2H5 H CH, C2H5 Cl601 C 2 H 5 H CH, C 2 H 5 Cl
H (R,S) H (R, S)
602 NH, H CH, C2H5 cι602 NH, H CH, C 2 H 5 cι
(R,rac) (R, rac)
603 NH, H CH, CH,603 NH, H CH, CH,
(R,R) (R, R)
CH,CH,
604 H H CH, CH,604 H H CH, CH,
,/, /
%%
H (R,R)H (R, R)
CH,CH,
605 CH3 H CH, CH3 605 CH 3 H CH, CH 3
,/ H (R,R), / H (R, R)
CH, 110 -CH, 110 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
606 C2H5 H CH, CH,606 C 2 H 5 H CH, CH,
,/, /
^^
H (R,R)H (R, R)
CH,CH,
607 NH, H CH, CH,607 NH, H CH, CH,
,/, /
(R,S)(R, S)
CH,CH,
608 H H CH, CH,608 H H CH, CH,
,/, /
%%
H (R,S)H (R, S)
CH,CH,
609 CH3 H CH, CH,609 CH 3 H CH, CH,
A- ,/A-, /
%%
(R,S)(R, S)
CH,CH,
610 C2H5 H CH, CH,610 C 2 H 5 H CH, CH,
„/"/
%%
H (R,S)H (R, S)
CH,CH,
611 NH, H CH, CH,611 NH, H CH, CH,
,/, /
^>^>
(R,rac)(R, rac)
CH,CH,
612 NH, H CH, C2H5 612 NH, H CH, C 2 H 5
S^S ^
(R,R)(R, R)
CH, - 111CH, - 111
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. Rl R 2 R3 R 4 Y data and stereo chem. Information
613 H H CH, C2H5 613 HH CH, C 2 H 5
,/, /
%%
H (R,R)H (R, R)
CH,CH,
614 CH3 H CH, C2H5 614 CH 3 H CH, C 2 H 5
,/, /
% H (R,R)% H (R, R)
CH,CH,
615 C2H5 H CH, C2H5 y ,/615 C 2 H 5 H CH, C 2 H 5 y, /
%%
H (R,R)H (R, R)
CH,CH,
616 NH, H CH, C2H5 616 NH, H CH, C 2 H 5
,/-, / -
%%
(R,S)(R, S)
CH,CH,
617 H H CH, C2H5 617 HH CH, C 2 H 5
././
C N' %C N '%
H (R,S)H (R, S)
CH,CH,
618 CH3 H CH, C, 2HU5618 CH 3 H CH, C, 2H U 5
,/, /
% H (R,S)% H (R, S)
CH,CH,
619 C2H5 H CH, C2H5 f 5^619 C 2 H 5 H CH, C 2 H 5 f 5 ^
(R,S)(R, S)
CH, 112CH, 112
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
620 NH2 H CH3 C2H5 F620 NH 2 H CH 3 C 2 H 5 F
H 4 (R,rac)H 4 (R, rac)
CH3 CH 3
621 H 2 H CH3 CH3 F621 H 2 H CH 3 CH 3 F
^c C\ ^ c C \
H2 H f> (R,R)H 2 H f> (R, R)
622 H 2 CH3 H CH3 CH, F622 H 2 CH 3 H CH 3 CH, F
^c^C\ JΓ\^ c ^ C \ JΓ \
H2 H (R,R)H 2 H (R, R)
623 H2 C2H5 H CH3 CH3 F623 H 2 C 2 H 5 H CH 3 CH 3 F
^c-C^ s^ c- C ^ s
H2 H (R,R)H 2 H (R, R)
624 H 2 H H CH3 CH3 F624 H 2 HH CH 3 CH 3 F
^c c^^ c c ^
H2 H y> (R,S)H 2 H y> (R, S)
625 H2 CH3 H CH3 CH3 F625 H 2 CH 3 H CH 3 CH 3 F
^c"c^^ c " c ^
H2 H (R,S)H 2 H (R, S)
626 H 2 C2H5 H CH3 CH3 F626 H 2 C 2 H 5 H CH 3 CH 3 F
^c/C\ ^ c / C \
H2 XL}H 2 XL}
H (R.S)H (R.S)
113 113
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
627 H 2 NH2 H CH3 CH3 F627 H 2 NH 2 H CH 3 CH 3 F
^c C\ ^ c C \
H2 (R,rac)H 2 (R, rac)
628 H2 H H CH3 C2H5 F628 H 2 HH CH 3 C 2 H 5 F
^c"C\ ^ c " C \
H2 H Λ} (R,R)H 2 H Λ} (R, R)
629 H2 CH3 H CH3 C2H5 F629 H 2 CH 3 H CH 3 C 2 H 5 F
^c^C\ JΓ\^ c ^ C \ JΓ \
H2 H (R,R)H 2 H (R, R)
630 H2 C2H5 H CH3 C2H5 F630 H 2 C 2 H 5 H CH 3 C 2 H 5 F
^c"C\ ^ c " C \
H2 H (R,R)H 2 H (R, R)
631 H 2 H H CH3 C2H5 F631 H 2 HH CH 3 C 2 H 5 F
^c C\ ^ c C \
H2 H (R,S)H 2 H (R, S)
632 H 2 CH3 H CH3 C2H5 F632 H 2 CH 3 H CH 3 C 2 H 5 F
H2 H (R,S)H 2 H (R, S)
633 H 2 C2H5 H CH3 C2H5 F633 H 2 C 2 H 5 H CH 3 C 2 H 5 F
^c/C\ ^ c / C \
H2 H f (R.S)H 2 H f (RS)
114 114
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 data and stereo chem. Information
634 H„ NH, H CH, C2H5 634 H "NH, H CH, C 2 H 5
VV
(R,rac)(R, rac)
635 H„ H H CH, CH,635 H "H H CH, CH,
H H (R,R)HH (R, R)
636 H. CH3 H CH, CH,636 H. CH 3 H CH, CH,
H„ H (R,R)H "H (R, R)
637 H„ C2H5 H CH, CH,637 H "C 2 H 5 H CH, CH,
OO
H„ (R,R)H" (R, R)
638 H„ H H CH, CH,638 H "H H CH, CH,
H. H (R,S)H. H (R, S)
639 H„ CH3 H CH, CH,639 H "CH 3 H CH, CH,
H. H (R,S)H. H (R, S)
640 H„ C2H5 H CH, CH,640 H "C 2 H 5 H CH, CH,
O'O'
H. H (R,S) -115-H. H (R, S) -115-
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
641 H„ NH, H CH, CH, T641 H "NH, H CH, CH, T
H„ (R,rac)H" (R, rac)
642 H. H H CH, C2H5 642 H. HH CH, C 2 H 5
H„ H (R,R)H "H (R, R)
643 H., CH3 H CH, C,H643 H., CH 3 H CH, C, H
H„ H (R,R)H "H (R, R)
644 i-L C2H5 H CH, C2H5 644 iL C 2 H 5 H CH, C 2 H 5
O^NO ^ N
H. H (R,R)H. H (R, R)
645 H„ H H CH, C2H5 645 H H H CH, C 2 H 5
O^N' O ^ N '
H. H (R,S)H. H (R, S)
646 H„ CH3 H CH, C2H5 646 H "CH 3 H CH, C 2 H 5
H„ H (R,S)H "H (R, S)
647 H C2H5 H CH, C2H5 T (R.S) - 116647 HC 2 H 5 H CH, C 2 H 5 T (RS) - 116
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
648 H 2 NH2 H CH3 C2H5 F648 H 2 NH 2 H CH 3 C 2 H 5 F
^c/C^^ c / C ^
H2 P (R,rac)H 2 P (R, rac)
649 H 2 NH2 H CH3 CH3 F649 H 2 NH 2 H CH 3 CH 3 F
H2 X (R,R)H 2 X (R, R)
650 2 H H CH3 CH3 F H,C650 2 HH CH 3 CH 3 FH, C
^c-C^^ c- C ^
H2 H - (R,R)H 2 H - (R, R)
651 H 2 CH3 H CH3 CH3 F H.C651 H 2 CH 3 H CH 3 CH 3 F HC
^c c^^ c c ^
H2 H X (R,R)H 2 HX (R, R)
652 H 2 C2H5 H CH3 CH3 F H,C652 H 2 C 2 H 5 H CH 3 CH 3 FH, C
^c"c\ ^ c " c \
H2 H X (R,R)H 2 HX (R, R)
653 H 2 NH2 H CH3 CH3 F H,C653 H 2 NH 2 H CH 3 CH 3 FH, C
^C ^^ C ^
H2 X (R,S)H 2 X (R, S)
654 2 H H CH, CH, F H,C654 2 HH CH, CH, FH, C
^c/C\ ^ c / C \
H2 H X (R,S)H 2 HX (R, S)
- 117 - - 117 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
655 2 CH3 H CH3 CH3 F H,C655 2 CH 3 H CH 3 CH 3 FH, C
H2 H X (R,S)H 2 HX (R, S)
656 H 2 C2H5 H CH3 CH3 F H.C656 H 2 C 2 H 5 H CH 3 CH 3 F HC
H2 H X (R,S)H 2 HX (R, S)
657 H 2 NH2 H CH3 CH3 F H,C657 H 2 NH 2 H CH 3 CH 3 FH, C
H2 X (R,rac)H 2 X (R, rac)
658 H 2 NH2 H CH3 C2H5 F H,C658 H 2 NH 2 H CH 3 C 2 H 5 FH, C
^c/C^^ c / C ^
H2 X (R,R)H 2 X (R, R)
659 H 2 H H CH3 C2H5 F H,C659 H 2 HH CH 3 C 2 H 5 FH, C
^c-C^^ c- C ^
H2 H X (R,R)H 2 HX (R, R)
660 H2 CH3 H CH3 C2H5 F H,C660 H 2 CH 3 H CH 3 C 2 H 5 FH, C
^c/C\ ^ c / C \
H2 H X (R,R)H 2 HX (R, R)
661 2 C2H5 H CH, C,H5 F H,C661 2 C 2 H 5 H CH, C, H 5 FH, C
^c/C\ ^ c / C \
H2 H X (R,R)H 2 HX (R, R)
118 118
Tabelle 1; (Fortsetzung)Table 1; (Continuation)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
662 H2 NH2 H CH3 C2H5 F H,C662 H 2 NH 2 H CH 3 C 2 H 5 FH, C
^c-C^^ c- C ^
H2 X (R,S)H 2 X (R, S)
663 H 2 H H CH3 C2H5 F H,C663 H 2 HH CH 3 C 2 H 5 FH, C
^c C^^ c C ^
H2 H X (R,S)H 2 HX (R, S)
664 2 CH3 H CH3 C2H5 F H,C664 2 CH 3 H CH 3 C 2 H 5 FH, C
^c C^^ c C ^
H2 H (R,S)H 2 H (R, S)
665 C2H5 H CH3 C2H5 F H.C665 C 2 H 5 H CH 3 C 2 H 5 F HC
H2 H X (R,S)H 2 HX (R, S)
666 2 NH2 H CH3 C2H5 F H,C666 2 NH 2 H CH 3 C 2 H 5 FH, C
^c/C\ ^ c / C \
H2 X (R,rac)H 2 X (R, rac)
667 H 2 H H CH3 CH3 F667 H 2 HH CH 3 CH 3 F
^c-C\ ^ c- C \
H2 H j (R,R)H 2 H j (R, R)
668 H2 CH3 H CH, CH3 F668 H 2 CH 3 H CH, CH 3 F
H2 H J (R.R)H 2 HJ (RR)
119 119
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
669 H 2 C2H5 H CH3 CH3 F669 H 2 C 2 H 5 H CH 3 CH 3 F
^c^^ c ^
H2 H y (R,R)H 2 H y (R, R)
670 H 2 H H CH3 CH3 F670 H 2 HH CH 3 CH 3 F
^c C^^ c C ^
H2 H yj (S,R)H 2 H yj (S, R)
671 2 CH3 H CH3 CH3 F671 2 CH 3 H CH 3 CH 3 F
^c C^^ c C ^
H2 H JO (S,R)H 2 H JO (S, R)
672 H 2 C2H5 H CH3 CH3 F672 H 2 C 2 H 5 H CH 3 CH 3 F
H2 H JÖ (S,R)H 2 H JÖ (S, R)
673 H2 NH2 H CH3 CH3 F673 H 2 NH 2 H CH 3 CH 3 F
^c c^^ c c ^
H2 JÖ (R,rac)H 2 JÖ (R, rac)
674 2 H H CH3 C2H5 F674 2 HH CH 3 C 2 H 5 F
H2 H O (R,R)H 2 HO (R, R)
675 2 CH3 H CH, C2H5 F675 2 CH 3 H CH, C 2 H 5 F
H2 H O (R,R)H 2 HO (R, R)
- 120 - - 120 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
676 2 C2H5 H CH3 C2H5 F676 2 C 2 H 5 H CH 3 C 2 H 5 F
H2 H XJ (R,R)H 2 H XJ (R, R)
677 H 2 H H CH3 C2H5 F677 H 2 HH CH 3 C 2 H 5 F
^c^C\ ^ c ^ C \
H2 H XJ (S,R)H 2 H XJ (S, R)
678 H 2 CH3 H CH3 C2H5 F678 H 2 CH 3 H CH 3 C 2 H 5 F
H2 H XJ (S,R)H 2 H XJ (S, R)
679 H 2 C2H5 H CH3 C2H5 F679 H 2 C 2 H 5 H CH 3 C 2 H 5 F
H2 H y (S,R)H 2 H y (S, R)
680 H 2 NH2 H CH3 C2H5 F680 H 2 NH 2 H CH 3 C 2 H 5 F
H2 XJ (R,rac)H 2 XJ (R, rac)
681 H 2 NH2 H CH3 CH3 F CH,681 H 2 NH 2 H CH 3 CH 3 F CH,
H2 X (R,R)H 2 X (R, R)
682 H2 H H CH3 CH, F682 H 2 HH CH 3 CH, F
H2 H S (R.R)H 2 H S (RR)
121 121
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
683 H„ CH3 H CH, CH,683 H "CH 3 H CH, CH,
XT H„ H (R,R) XT H "H (R, R)
684 H, C2H5 H CH, CH,684 H, C 2 H 5 H CH, CH,
H, H (R,R) H, H (R, R)
685 H NH, H CH, CH, T H, (S,R) 685 H NH, H CH, CH, TH, (S, R)
686 H„ H H CH, CH, T H„ H (S,R) 686 H "HH CH, CH, TH" H (S, R)
687 H, CH3 H CH3 CH,687 H, CH 3 H CH 3 CH,
H„ H (S,R) H "H (S, R)
688 H„ C2H5 H CH, CH, T O^N688 H "C 2 H 5 H CH, CH, TO ^ N
H (S,R) H (S, R)
689 2 NH, H CH, CH,689 2 NH, H CH, CH,
H, (R,rac) 122H, (R, rac) 122
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 Y data and stereo chem. Information
690 H„ NH, H CH, CH, T H„ (R,R) 690 H "NH, H CH, CH, TH" (R, R)
691 H, H H CH, CH,691 H, H H CH, CH,
H„ H (R,R) H "H (R, R)
692 H„ CH3 H CH, CH, T H, H (R,R) 692 H "CH 3 H CH, CH, TH, H (R, R)
693 H C2H5 H CH, CH,693 HC 2 H 5 H CH, CH,
Ho H (R,R) Ho H (R, R)
694 H NH, H CH, CH,694 H NH, H CH, CH,
Ho (S,R) Ho (S, R)
695 Ho H H CH, CH, xr695 Ho H H CH, CH, xr
Ho H (S,R) Ho H (S, R)
696 Ho CH, H CH, CH,696 Ho CH, H CH, CH,
XT O Ho (S,R) 123 -XT O Ho (S, R) 123 -
Tabelle 1: (Fortsetzung)Table 1: (continued)
Bsp.- Physikal.Ex. Physical.
Nr. A Rl R2 R3 R4 Y Z Daten und stereo- chem. AngabenNo. A Rl R 2 R3 R 4 YZ data and stereo chem. Information
697 H2 C2H5 H CH3 CH3 F697 H 2 C 2 H 5 H CH 3 CH 3 F
H2 H O (S,R)H 2 HO (S, R)
698 H 2 NH, H CH3 CH3 F698 H 2 NH, H CH 3 CH 3 F
^c/C\ ^ c / C \
H2 H 2
X ( ,rac) X (, rac)
Die Bestimmung der in Tabelle 1 angegebenen log p- Werte erfolgte gemäß EEC- Directive 79/831 Annex V.A8 durch HPLC (High Performance Liquid Chromato- graphy) an einer Phasenumkehrsäule (C 18). Temperatur: 43°C.The log p values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.
a) Eluenten für die Bestimmung im sauren Bereich: 0,1 % wäßrige Phosphorsäure, Acetonitril; linearer Gradient von 10 % Acetonitril bis 90 % Acetonitril - entsprechende Meßergebnisse sind in Tabelle 1 mit a) markiert, b) Eluenten für die Bestimmung im neutralen Bereich: 0,01 -molare wäßrige Phosphatpuffer-Lösung, Acetonitril; linearer Gradient von 10 % Acetonitril bis 90 %a) eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with a ), b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90%
Acetonitril - entsprechende Meßergebnisse sind in Tabelle 1 mit b) markiert. Die Eichung erfolgte mit unverzweigten Alkan-2-onen (mit 3 bis 16 Kohlenstoffatomen), deren log p- Werte bekannt sind (Bestimmung der log p- Werte anhand der Rententionszeiten durch lineare Interpolation zwischen zwei aufeinanderfolgenden Alkanonen).Acetonitrile - corresponding measurement results are marked in Table 1 with b ). The calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), the log p values of which are known (determination of the log p values on the basis of the retention times by linear interpolation between two successive alkanones).
Die lambda-max- Werte wurden an Hand der UV-Spektren von 200 nm bis 400 nm in den Maxima der chromatographischen Signale ermittelt. - 124 -The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. - 124 -
Ausgangsstoffe der Formel (II):Starting materials of formula (II):
Beispiel (IM)Example (IM)
H„ N ^NH "N ^ N
H2N HCI H 2 N HCl
72 g Salzsäure (33%ig) werden bei Raumtemperatur unter Rühren zu einer Lösung von 81 g (0,60 Mol) (S)-l-Phenyl-ethylamin in 150 ml Methanol gegeben. Die Mischung wird mit Toluol auf etwa das dreifache Volumen verdünnt und die flüchtigen Komponenten werden im Wasserstrahlvakuum sorgfältig abdestilliert. Der Rückstand wird nach Zugabe von 50,4 g (0,60 Mol) Cyanoguanidin drei Stunden lang bei 150°C bis 170°C (Innentemperatur; Badtemperatur ca. 200°C) verschmolzen.72 g of hydrochloric acid (33%) are added at room temperature with stirring to a solution of 81 g (0.60 mol) of (S) -l-phenylethylamine in 150 ml of methanol. The mixture is diluted to about three times the volume with toluene and the volatile components are carefully distilled off in a water jet vacuum. After adding 50.4 g (0.60 mol) of cyanoguanidine, the residue is melted for three hours at 150 ° C. to 170 ° C. (internal temperature; bath temperature approx. 200 ° C.).
Man erhält 142 g (98 % der Theorie) (S)-l-(l-Phenyl-ethyl)-biguanid-Hydrochlorid als glasartige Masse, welche ohne weitere Reinigung für die Umsetzung gemäß dem erfindungsgemäßen Verfahren (vgl. Beispiel 1) eingesetzt werden kann.142 g (98% of theory) of (S) -l- (l-phenyl-ethyl) -biguanide hydrochloride are obtained as a glass-like mass, which can be used without further purification for the reaction according to the process of the invention (cf. Example 1) can.
Die Verbindung (S)-l-(l-Phenyl-propyl)-biguanid-Hydrochlorid kann analog Beispiel (II- 1) ausgehend von (S)-l-Phenyl-propylamin hergestellt werden. The compound (S) -l- (l-phenyl-propyl) -biguanide hydrochloride can be prepared analogously to Example (II-1) starting from (S) -l-phenyl-propylamine.
- 125 -- 125 -
Ausgangsstoffe der Formel (III):Starting materials of formula (III):
Beispiel (III-l)Example (III-l)
HΛ^CH3 HΛ ^ CH 3
CT ^OCH 3 CT ^ OCH 3
Stufe 1step 1
/S02CH3 / S0 2 CH 3
O hk ..CH 3O hk ..CH 3
CT OCH3 CT OCH 3
34,3 g (0,30 Mol) Methansulfonsäurechlorid werden innerhalb von 15 Minuten portionsweise unter Rühren zu einer mit Eis gekühlten Lösung von 27,9 g (0,29 Mol) (R)-Milchsäure-methylester in 100 ml Pyridin gegeben. Die Reaktionsmischung wird zwei Stunden bei 5°C gerührt, anschließend auf 100 ml Wasser gegeben und dreimal mit je 100 ml Methyl-t-butyl-ether (MTBE) extrahiert. Die vereinigten MTBE-34.3 g (0.30 mol) of methanesulfonic acid chloride are added in portions over a period of 15 minutes with stirring to an ice-cooled solution of 27.9 g (0.29 mol) of methyl (R) -lactic acid in 100 ml of pyridine. The reaction mixture is stirred at 5 ° C. for two hours, then added to 100 ml of water and extracted three times with 100 ml each of methyl t-butyl ether (MTBE). The united MTBE
Phasen werden mit eiskalter 6N-Salzsäure (2x 100 ml), mit Wasser (2x 100 ml) und mit eiskalter Natriumhydrogencarbonat-Lösung (3x 100 ml) gewaschen, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird 30 Minuten mit Aktivkohle (Norit A) gerührt und erneut filtriert. Vom Filtrat wird im Wasserstrahlvakuum das Lösungsmittel sorgfältig abdestilliert.Phases are washed with ice-cold 6N hydrochloric acid (2x 100 ml), with water (2x 100 ml) and with ice-cold sodium hydrogen carbonate solution (3x 100 ml), dried with sodium sulfate and filtered. The filtrate is stirred for 30 minutes with activated carbon (Norit A) and filtered again. The solvent is carefully distilled off from the filtrate in a water jet vacuum.
Man erhält (R)-α-Methylsulfonyloxy-propionsäure-methylester als amorphen Rückstand, welcher ohne weitere Reinigung gemäß Beschreibung von Stufe 2 (nachstehend) umgesetzt werden kann. - 126 -This gives (R) -α-methylsulfonyloxy-propionic acid methyl ester as an amorphous residue, which can be reacted without further purification as described in step 2 (below). - 126 -
Stufe 2Level 2
H . /CH3H . / CH 3
o x- y X,3CH,o x- y X, 3CH,
18,8 g (0,32 Mol) Kaliumfluorid werden unter Rühren zu einer auf 125°C erwärmten18.8 g (0.32 mol) of potassium fluoride are heated to 125 ° C. with stirring
Mischung aus 47,9 g (0,26 Mol) (R)-α-Methylsulfonyloxy-propionsäure-methylester und 250 g Acetamid gegeben. Dann werden 8 ml einer 1 -molaren Tetrabutylammo- niumfluorid-Lösung in Tetrahydrofuran tropfenweise zur Mischung gegeben. Die Reaktionsmischung wird dann 5 Stunden bei 125°C und 15 Stunden bei Raum- temperatur (ca. 20°C) gerührt, anschließend auf 90°C erwärmt und unter starkemMixture of 47.9 g (0.26 mol) of (R) -α-methylsulfonyloxy-propionic acid methyl ester and 250 g of acetamide. Then 8 ml of a 1 molar solution of tetrabutylammonium fluoride in tetrahydrofuran are added dropwise to the mixture. The reaction mixture is then stirred at 125 ° C. for 5 hours and at room temperature (approx. 20 ° C.) for 15 hours, then heated to 90 ° C. and vigorously
Rühren mit 250 ml Wasser versetzt. Nach Abkühlen auf Raumtemperatur wird dreimal mit je 250 ml Dichlormethan extrahiert. Die vereinigten organischen Phasen werden mit gesättigter wässriger Kochsalz-Lösung (2x 100 ml) und dann mit Wasser (lx 100 ml) gewaschen, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird 30 Minuten mit Aktivkohle gerührt und erneut filtriert. Vom Filtrat wird dann imStirred with 250 ml of water. After cooling to room temperature, the mixture is extracted three times with 250 ml of dichloromethane each time. The combined organic phases are washed with saturated aqueous sodium chloride solution (2 × 100 ml) and then with water (1 × 100 ml), dried with sodium sulfate and filtered. The filtrate is stirred with activated carbon for 30 minutes and filtered again. The filtrate is then in the
Wasserstrahlvakuum das Lösungsmittel sorgfältig abdestilliert.Water jet vacuum carefully distilled off the solvent.
Man erhält (S)-α-Fluor-propionsäure-methylester als amorphen Rückstand, welcher ohne weitere Reinigung für die Umsetzung gemäß dem erfindungsgemäßen Verfahren (vgl. Beispiel 1) eingesetzt werden kann.This gives (S) -α-fluoropropionic acid methyl ester as an amorphous residue, which can be used without further purification for the reaction according to the process of the invention (cf. Example 1).
Die Verbindung (R)-α-Fluor-propionsäure-methylester kann analog Beispiel (III- 1) ausgehend von (S)-Milchsäure-methylester hergestellt werden. - 127 -The compound (R) -α-fluoropropionic acid methyl ester can be prepared analogously to Example (III-1) starting from (S) -lactic acid methyl ester. - 127 -
Anwendungsbeispiele:Examples of use:
Beispiel AExample A
Post-emergence-TestPost emergence test
Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 -The active ingredient preparation is used to inject test plants which are 5 -
15 cm haben so, daß die jeweils gewünschten Wirkstoffmengen pro Flächeneinheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 1000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden.15 cm so that the desired amounts of active ingredient are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 1000 l of water / ha.
Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle.After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
Es bedeuten:It means:
0 % = keine Wirkung (wie unbehandelte Kontrolle)0% = no effect (like untreated control)
100 % = totale Vernichtung100% = total annihilation
In diesem Test zeigen beispielsweise die Verbindungen gemäß Herstellungsbeispiel 1 , 18, 19, 22 und 23 starke Wirkung gegen Unkräuter. 99/46249In this test, for example, the compounds according to Preparation Examples 1, 18, 19, 22 and 23 show a strong action against weeds. 99/46249
-128-128
Tabelle A-l: Post-emergence-Test/Ge ächshausTable A-1: Post emergence test / Ge ächshaus
Wirkstoff gemäß AufwandSetaria Abutilon AmaXanthiumActive ingredient according to expenditureSetaria Abutilon AmaXanthium
Herstellungsbeispiel-Nr. menge ranthusProduction example no. lot of ranthus
(g ai./ha)(g ai./ha)
-1 .....CH3 N^N CH3 H. ^ ^ -^ ^-1 ..... CH 3 N ^ N CH 3 H. ^ ^ - ^ ^
HH
(1) 1000 90 80 100 95 (1) 1000 90 80 100 95
129 -129 -
Tabelle A-2: Post-emergence-Test / GewächshausTable A-2: Post emergence test / greenhouse
Wirkstoff gemäß AufAvena Se- Abu- AmaGaSinaXanHerstellungsbeispiel-Nr. wandfatua taria tilon ranthus lium pis thium mengeActive ingredient according to AufAvena Se- Abu- AmaGaSinaXanManufacturing example no. Wandfatua taria tilon ranthus lium pis thium quantity
(g ai./ha)(g ai./ha)
CH3 CH 3
er -,'CH3 he -, 'CH 3
(19) 1000 95 100 100 100 100 100 100 (19) 1000 95 100 100 100 100 100 100
130130
Tabelle A-3: Post-emergence-Test / GewächshausTable A-3: Post emergence test / greenhouse
Wirkstoff gemäß AufwandSetaria Abu- AmaSinapis XanHerstellungsbeispiel-Nr. menge tilon ranthus thiumActive ingredient according to expenditureSetaria Abu- AmaSinapis XanManufacturing example no. lot of tilon ranthus thium
(g ai./ha)(g ai./ha)
QH3 QH 3
.H.H
'CH,'CH,
(18) 1000 100 100 100 100 100(18) 1000 100 100 100 100 100
,CH,CH
H N f NH, ,NHN f NH, , N
Cl' CH,Cl'CH,
(22) 1000 95 95 100 100 100(22) 1000 95 95 100 100 100
.CH,.CH,
41 x NH,41 x NH,
N, N,
Cl' 'CH,Cl '' CH,
(23) 1000 80 95 100 100 100 - 131 -(23) 1000 80 95 100 100 100 - 131 -
Beispiel BExample B
Pre-emergence-TestPre-emergence test
Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschteTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired level
Konzentration.Concentration.
Samen der Testpflanzen werden in normalen Boden ausgesät. Nach ca. 24 Stunden wird der Boden mit der Wirkstoffzubereitung gespritzt, so daß die jeweils ge- wünschten Wirkstoffmengen pro Flächeneinheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 1000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden.Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active ingredient preparation, so that the desired amounts of active ingredient are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 1000 l of water / ha.
Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle.After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
Es bedeuten:It means:
0 % = keine Wirkung (wie unbehandelte Kontrolle) 100 % = totale Vernichtung0% = no effect (like untreated control) 100% = total destruction
In diesem Test zeigt beispielsweise die Verbindung gemäß Herstellungsbeispiel 1 bei guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Sonnenblumen, starke Wirkung gegen Unkräuter. - 132In this test, for example, the compound according to Preparation Example 1, with good tolerance to crop plants, such as sunflowers, shows a strong action against weeds. - 132
Tabelle B-l; Pre emergence / GewächshausTable B-1; Pre emergence / greenhouse
Wirkstoff gemäß AufwandMais Alo- Setaria Abuti- GaBeispiel-Nr. menge pecurus lon liumActive ingredient according to effort Corn Alosetaria Abuti-GaExample no. amount of pecurus lon lium
(g ai./ha)(g ai./ha)
H3C Cl Chiral X^H 3 C Cl Chiral X ^
H>C> T^^ T°\ HA x A "»2 H> C > T ^^ T ° \ HA x A " » 2
CH3 CH 3
(5) 1000 20 - 100 100 100(5) 1000 20 - 100 100 100
Chiral fö HChiral fö H
H3C |H 3 C |
NH2 NH 2
(6) 1000 10 100 - 100 100 (6) 1000 10 100 - 100 100
133133
Tabelle B-2: Pre emergence / GewächshausTable B-2: Pre emergence / greenhouse
Wirkstoff gemäß AufwandMais Alo- Setaria Abuti- AmaSinaBeispiel-Nr. menge pecurus lon ranpis thusActive ingredient according to effort Corn Alo- Setaria Abuti- AmaSina Example no. amount of pecurus lon ranpis thus
(g ai./ha)(g ai./ha)
CH3 ChiralCH 3 Chiral
^ffo^ N γ-o, f γ^ ffo ^ N γ-o, f γ
(2) 1000 20 100 100 100 80 -(2) 1000 20 100 100 100 80 -
H CyC' Chira, HC y C 'Chira,
H3C- X. 3 N^ N 0H 3 C-X. 3 N ^ N 0
U H U H
(9) 1000 20 95 95 100 100 (9) 1000 20 95 95 100 100
- 134- 134
Tabelle B-3: Pre emergence / GewächshausTable B-3: Pre emergence / greenhouse
Wirkstoff gemäß AufwandAlo- Setaria Abuti- AmaGaSinaBeispiel-Nr. menge pecu- lon ranthus lium pis rusActive ingredient according to expenditure Alo-Setaria Abuti-AmaGaSina, example no. amount of peculon ranthus lium pis rus
(g ai./ha)(g ai./ha)
?H3 Chiral? H 3 Chiral
f Y NHj f Y NH j
(3) 2000 - 100 100 100 100 100(3) 2000 - 100 100 100 100 100
H,C^ ,.CI ChiralH, C ^, .CI Chiral
/ CH. N Ύγ 1/ CH. N Ύγ 1
(4) 2000 100 100 100 95 100 100(4) 2000 100 100 100 95 100 100
Chiral f\ H ?Hs γ H3C Y YγN O NH2 Chiral for \ H ? Hs γ H 3 CY Yγ NO NH 2
(7) 1000 95 95 100 100 100 100(7) 1000 95 95 100 100 100 100
Cl H3C.,,,,/ Chira| -Cl H 3 C. ,,,, / Chira | -
H3C- )= V-N / HH 3 C-) = VN / H
SS
(15) 1000 100 100 100 100 100 100 135 -(15) 1000 100 100 100 100 100 100 135 -
Tabelle B-4: Pre-emergence/GewächshausTable B-4: Pre-emergence / greenhouse
Wirkstoff gemäß AufwandSetaria Abutilon Galium SinapisActive ingredient according to expenditureSetaria Abutilon Galium Sinapis
Beispiel-Nr. mengeExample No. quantity
(g ai./ha)(g ai./ha)
Cl 3C' Chiral -N l ^NH2 Cl 3 C 'Chiral -N l ^ NH 2
H3C- )=N V-N / HH 3 C-) = N VN / H
(14) 1000 100 100 95 100 (14) 1000 100 100 95 100
- 136 -- 136 -
Tabelle B-5: Pre-emergence / GewächshausTable B-5: Pre-emergence / greenhouse
Wirkstoff gemäß AufwandAlo- Setaria Abuti- Galium SinaXan¬Active ingredient according to expenditure Alo-Setaria Abuti- Galium SinaXan¬
Beispiel-Nr. menge pecu- lon pis thium rus (g ai./ha)Example No. amount pecu- lon pis thium rus (g ai./ha)
Cl H3C.„,,,/ Chjra| N Cl H 3 C. ",,, / Chjra | N
N7/ ^NH2 H3C^ )=NN 7 / ^ NH 2 H 3 C ^) = N
V-N / HV-N / H
(13) 1000 95 100 100 100 95 90 (13) 1000 95 100 100 100 95 90

Claims

- 137 -Patentansprüche - 137 patent claims
1. Substituierte Aminotriazine mit mindestens zwei asymmetrisch substituierten Kohlenstoffatomen der allgemeinen Formel (I),1. Substituted aminotriazines with at least two asymmetrically substituted carbon atoms of the general formula (I),
R'R '
Y- -RJ Y- -R J
-.4-.4
N^ N R4 (I)N ^ NR 4 (I)
R1 N "N i H in welcherR 1 N " N i H in which
A für eine Einfachbindung oder für jeweils geradkettiges oder verzweig- tes Alkandiyl oder Oxaalkandiyl mit jeweils bis zu 6 Kohlenstoffatomen steht,A represents a single bond or a straight-chain or branched alkanediyl or oxaalkanediyl each having up to 6 carbon atoms,
Rl für Amino, für Formylamino oder für jeweils gegebenenfalls durch Cyano, Halogen oder C1 -C4- Alkoxy substituiertes Alkylamino, Di- alkylamino, Alkylcarbonylamino, N-Alkyl-N-alkylcarbonyl-amino,Rl for amino, for formylamino or for alkylamino, dialkylamino, alkylcarbonylamino, N-alkyl-N-alkylcarbonylamino, optionally substituted by cyano, halogen or C1-C4alkoxy,
Alkoxycarbonylamino, N-Alkyl-N-alkoxycarbonyl-amino, Alkyl- aminoalkylidenamino oder Dialkylaminoalkylidenamino mit jeweils bis zu 6 Kohlenstoffatomen in den Alkylgruppen bzw. Alkyliden- gruppen steht,Alkoxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, alkylaminoalkylideneamino or dialkylaminoalkylideneamino each having up to 6 carbon atoms in the alkyl groups or alkylidene groups,
R2 für Wasserstoff, Halogen oder gegebenenfalls durch Cyano, Halogen oder C1-C4- Alkoxy substituiertes Alkyl mit bis zu 6 Kohlenstoffatomen steht.R2 represents hydrogen, halogen or alkyl which is optionally substituted by cyano, halogen or C1-C4-alkoxy and has up to 6 carbon atoms.
RJ für Wasserstoff, Halogen oder gegebenenfalls durch Cyano. Halogen oder C]-C4-Alkoxy substituiertes Alkyl mit bis zu 6 Kohlenstoff- - 138 -R J for hydrogen, halogen or optionally by cyano. Halogen or C] -C4-alkoxy substituted alkyl with up to 6 carbon - 138 -
atomen steht, oder zusammen mit R2 für gegebenenfalls durch Cyano, Halogen oder C1-C4- Alkyl substituiertes Alkandiyl mit 2 bis 5 Kohlenstoffatomen steht,stands for atoms, or together with R2 stands for alkanediyl with 2 to 5 carbon atoms optionally substituted by cyano, halogen or C1-C4-alkyl,
R^ für Alkyl mit bis zu 6 Kohlenstoffatomen oder für Cycloalkyl mit 3 bis 6 Kohlenstoffatomen steht,R ^ represents alkyl having up to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms,
Y für Wasserstoff, Hydroxy, Mercapto, Amino, Cyano, Halogen, oder für jeweils gegebenenfalls durch Cyano, Halogen oder Cj-C4-Alkoxy substituiertes Alkyl, Alkoxy, Alkylcarbonyloxy, Alkoxycarbonyloxy,Y stands for hydrogen, hydroxy, mercapto, amino, cyano, halogen, or for alkyl, alkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, which are each optionally substituted by cyano, halogen or C j -C4-alkoxy,
Alkylaminocarbonyloxy, Dialkylaminocarbonyloxy, Alkylthio, Alkylamino oder Dialkylamino mit jeweils bis zu 6 Kohlenstoffatomen in den Alkylgruppen steht, undAlkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylthio, alkylamino or dialkylamino each having up to 6 carbon atoms in the alkyl groups, and
Z für eine gegebenenfalls substituierte monocyclische oder bicyclische, carbocyclische oder heterocyclische Gruppierung aus der Reihe Cyclopentyl, Cyclohexyl, Phenyl, Naphthyl, Tetralinyl, Decalinyl, Indanyl, Indenyl, Furyl, Benzofuryl, Dihydrobenzofuryl, Thienyl, Benzothienyl, Dihydrobenzothienyl, Isobenzofuryl, Dihydroisobenzo- furyl, Isobenzothienyl, Dihydroisobenzothienyl, Pyrrolyl, Indolyl, Iso- indolyl, Indolinyl, Isoindolinyl, Benzdioxolyl, Oxazolyl, Benz- oxazolyl, Thiazolyl, Benzthiazolyl, Benzimidazolyl, Indazolyl, Oxadi- azolyl, Thiadiazolyl, Pyrazolyl, Pyridinyl, Pyrimidinyl, Pyrazinyl, Pyridazinyl, Chinolyl, Isochinolyl, Chinoxalinyl, Cinnolinyl und Phthalazinyl steht,Z for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydroobenzothurylbenzoburyl Isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzdioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, benzimidazolyl, indazolyl, pyadiazolyl, thiadiazolylyl, pyrazole Isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl,
wobei die möglichen Substituenten jeweils vorzugsweise aus der folgenden Gruppe ausgewählt sind:the possible substituents are each preferably selected from the following group:
Hydroxy, Amino, Cyano, Nitro, Carbamoyl, Sulfamoyl, Halogen, je- weils gegebenenfalls durch Hydroxy, Cyano oder Halogen substituiertes Alkyl, Alkoxy, Alkylamino oder Dialkylamino mit jeweils 1 bis - 139 -Hydroxy, amino, cyano, nitro, carbamoyl, sulfamoyl, halogen, each optionally substituted by hydroxy, cyano or halogen-substituted alkyl, alkoxy, alkylamino or dialkylamino, each with 1 to - 139 -
6 Kohlenstoffatomen in den Alkylgruppen, jeweils gegebenenfalls durch Halogen substituiertes Alkylcarbonyl, Alkoxycarbonyl, Alkyl- carbonylamino, Alkylaminocarbonyl, Dialkylaminocarbonyl, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylsulfonylamino, Alkylamino- sulfonyl oder Dialkylaminosulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, jeweils gegebenenfalls durch Hydroxy, Cyano, Nitro, Halogen, Cι-C4-Alkyl, Cι-C4-Halogeι dkyl, C1-C4- Alkoxy oder C]-C4-Halogenalkoxy substiuiertes Phenyl oder Phenoxy, sowie jeweils gegebenenfalls durch Halogen substituiertes Methylendioxy oder Ethylendioxy,6 carbon atoms in the alkyl groups, each optionally substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonylamino, alkylaminosulfonyl or dialkylaminosulfonyl each having 1 to 6 carbon atoms in the alkyl groups, each optionally , Cyano, nitro, halogen, C 1 -C 4 -alkyl, C 1 -C 4 halo dkyl, C1-C4-alkoxy or C] -C4-haloalkoxy-substituted phenyl or phenoxy, and in each case optionally substituted by halogen methylenedioxy or ethylenedioxy,
mit der Maßgabe, daß in jedem Einzelfall R^, R3 und Y verschieden voneinander sind und daß die Substituenten an den beiden Kohlenstoffatomen, an die R^ und R^ bzw. R^ gebunden sind, wie folgt konfiguriert sind:with the proviso that in each individual case R ^, R3 and Y are different from one another and that the substituents on the two carbon atoms to which R ^ and R ^ and R ^ are bound are configured as follows:
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,R-Diastereomere"),(a) R configuration on the carbon atom to which R ^ and R ^ are attached and R configuration on the carbon atom to which R ^ is attached ("R, R diastereomers"),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,S-Diastereomere"),(b) R configuration on the carbon atom to which R ^ and R ^ are bonded and S configuration on the carbon atom to which R ^ is bonded ("R, S diastereomers"),
(c) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ ge- bunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,R-Diastereomere"),(c) S configuration on the carbon atom to which R ^ and R ^ are attached and R configuration on the carbon atom to which R ^ is attached ("S, R diastereomers"),
(d) S-Konfiguration an dem Kohlenstoffatom, an welches R~ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,S-Diastereomere"), - 140 -(d) S configuration on the carbon atom to which R ~ and R ^ are attached and S configuration on the carbon atom to which R ^ is attached ("S, S diastereomers"), - 140 -
(e) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R- gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,rac-Diastereomere"),(e) R configuration on the carbon atom to which R ^ and R- are bonded and racemic configuration on the carbon atom to which R ^ is bonded ("R, rac diastereomers"),
(f) S -Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,rac-Diastereomere").(f) S configuration on the carbon atom to which R2 and R ^ are attached and racemic configuration on the carbon atom to which R ^ is attached ("S, rac diastereomers").
2. Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß darin2. Compounds of formula (I) according to claim 1, characterized in that therein
A für eine Einfachbindung, für Methylen (-CH2-), Dimethylen (Ethan-1,2- diyl, -CH2CH2-), Ethyliden (Ethan-l,l-diyl, -CH(CH3)-), Oxaethandiyl (-CH20-), Trimethylen (Propan-l,3-diyl, -CH2CH2CH2-), Propyliden (Propan-l,l-diyl, -CH(C H5)-), Propan-2,3-diyl (-CH(CH3)CH2-), 2-A for a single bond, for methylene (-CH2-), dimethylene (ethane-1,2-diyl, -CH 2 CH 2 -), ethylidene (ethane-l, l-diyl, -CH (CH 3 ) -), Oxaethanediyl (-CH 2 0-), trimethylene (propane-l, 3-diyl, -CH 2 CH 2 CH2-), propylidene (propane-l, l-diyl, -CH (C H5) -), propane-2 , 3-diyl (-CH (CH 3 ) CH 2 -), 2-
Methyl-propan-l,3-diyl (-CH2CH(CH3)CH2-), 3-Oxa-propan-l,3-diyl (-CH2CH20-), 2-Oxa-propan-l,3-diyl (-CH2OCH2-), Tetramethylen (Butan- 1,4-diyl, -CH2CH2CH2CH2-), Butan-2,4-diylMethyl propane-l, 3-diyl (-CH 2 CH (CH 3 ) CH 2 -), 3-oxa-propane-l, 3-diyl (-CH 2 CH 2 0-), 2-oxa-propane 1,3-diyl (-CH 2 OCH 2 -), tetramethylene (butane-1,4-diyl, -CH 2 CH 2 CH 2 CH 2 -), butane-2,4-diyl
(-CH(CH3)CH2CH2-), Butan-2,3-diyl (-CH(CH3)CH(CH3)-), 3-Methyl- butan-2,4-diyl (-CH(CH3)CH(CH3)CH2-), 4-Oxa-butan-2,4-diyl(-CH (CH 3 ) CH 2 CH 2 -), butane-2,3-diyl (-CH (CH 3 ) CH (CH 3 ) -), 3-methylbutane-2,4-diyl (-CH (CH 3 ) CH (CH 3 ) CH 2 -), 4-oxa-butane-2,4-diyl
(-CH(CH3)CH20-), Pentan-3,5-diyl (-CH(C2H5)CH2CH2-), 5-Oxa- pentan-3,5-diyl (-CH(C2H5)CH 0-), 4-Oxa-pentan-2,5-diyl(-CH (CH 3 ) CH 2 0-), pentane-3,5-diyl (-CH (C 2 H 5 ) CH 2 CH 2 -), 5-oxapentane-3,5-diyl (-CH (C 2 H 5 ) CH 0-), 4-oxapentane-2,5-diyl
(-CH(CH3)CH2OCH2-) oder 5-Oxa-hexan-3,6-diyl(-CH (CH 3 ) CH 2 OCH 2 -) or 5-oxa-hexane-3,6-diyl
(-CH(C2H5)CH OCH2-) steht,(-CH (C 2 H 5 ) CH OCH 2 -) stands,
Rl für Amino, für Formylamino oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl- amino, Ethylamino, Dimethylamino, Acetylamino, Propionylamino, n- oder i-Butyroylamino, N-Methyl-N-acetyl-amino, N-Ethyl-N- acetyl-amino. N-Methyl-N-propionyl-amino, Methoxycarbonylamino. Ethoxycarbonylamino, n- oder i-Propoxycarbonylamino, N-Methyl-N- - 141 -Rl for amino, for formylamino or for methylamino, ethylamino, dimethylamino, acetylamino, propionylamino, n- or i-butyroylamino, N-methyl-N-acetylamino, optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, N-ethyl-N-acetyl-amino. N-methyl-N-propionyl-amino, methoxycarbonylamino. Ethoxycarbonylamino, n- or i-propoxycarbonylamino, N-methyl-N- - 141 -
methoxycarbonyl-amino, N-Ethyl-N-methoxycarbonyl-amino, N-Me- thyl-N-ethoxycarbonyl-amino, Methylaminomethylenamino, Ethyl- aminomethylenamino, Methylaminoethylidenamino oder Dimethyl- aminomethylenamino steht,methoxycarbonyl-amino, N-ethyl-N-methoxycarbonyl-amino, N-methyl-N-ethoxycarbonyl-amino, methylaminomethyleneamino, ethylaminomethylenamino, methylaminoethylidenamino or dimethylaminoomethylamino,
R2 für Wasserstoff, Fluor, Chlor, Brom, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl steht,R2 represents hydrogen, fluorine, chlorine, bromine, or in each case methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R^ für Wasserstoff, Fluor, Chlor, Brom, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl steht, oder zusammen mit R^ für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl oder Ethyl substituiertes Dimethylen (Ethan-1,2- diyl), Trimethylen (Propan-l,3-diyl) oder Tetramethylen (Butan- 1,4- diyl) steht,R ^ represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or together with R ^ for in each case optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl dimethylene (ethane-1,2-diyl), trimethylene (propane-l, 3-diyl) or tetramethylene (butane-1,4 - diyl) stands,
R4 für Methyl, Ethyl, n- oder i-Propyl, oder für Cyclopropyl steht,R4 represents methyl, ethyl, n- or i-propyl, or cyclopropyl,
Y für Wasserstoff, Hydroxy, Mercapto, Amino, Cyano, Fluor, Chlor,Y for hydrogen, hydroxy, mercapto, amino, cyano, fluorine, chlorine,
Brom, oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n- , i- oder s-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i- oder s- Butoxy, Acetyloxy, Propionyloxy, n- oder i-Butyroyloxy, Methoxy- carbonyloxy, Ethoxycarbonyloxy, n- oder i-Propoxycarbonyloxy, Me- thylaminocarbonyloxy, Ethylaminocarbonyloxy, n- oder i-Propyl- aminocarbonyloxy, Dimethylaminocarbonyloxy, Methylthio, Ethyl- thio, n- oder i-Propylthio, n-, i- oder s-Butylthio, Methylamino. Ethyl- amino, n- oder i-Propylamino, n-, i- oder s-Butylamino oder Di- methylamino steht, und - 142 -Bromine, or for methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, n each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy -, i- or s-butoxy, acetyloxy, propionyloxy, n- or i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or i-propoxycarbonyloxy, methylaminocarbonyloxy, ethylaminocarbonyloxy, n- or i-propylaminocarbonyloxy, dimethylaminocarbonyloxy, Methylthio, ethylthio, n- or i-propylthio, n-, i- or s-butylthio, methylamino. Ethylamino, n- or i-propylamino, n-, i- or s-butylamino or dimethylamino, and - 142 -
für eine gegebenenfalls substituierte monocyclische oder bicyclische, carbocychsche oder heterocyclische Gruppierung aus der Reihefor an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series
Cyclohexyl, Phenyl, Naphthyl, Tetralinyl, Decalinyl, Indanyl, Indenyl,Cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl,
Furyl, Benzofuryl, Dihydrobenzofuryl, Thienyl, Benzothienyl, Di- hydrobenzothienyl, Isobenzofuryl, Dihydroisobenzofuryl, Isobenzo- thienyl, Dihydroisobenzothienyl, Pyrrolyl, Indolyl, Isoindolyl, Indolinyl, Isoindolinyl, Benzdioxolyl, Oxazolyl, Benzoxazolyl, Thiazolyl, Benzthiazolyl, Benzimidazolyl, Indazolyl, Oxadiazolyl, Thiadiazolyl, Pyrazolyl, Pyridinyl, Pyrimidinyl, Pyrazinyl, Pyridazinyl, Chinolyl, Isochinolyl, Chinoxalinyl, Cinnolinyl undFuryl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, oxazolylyloxolylylololyl, benzolylazolyl, benzolylazolyl, benzazolyl Thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and
Phthalazinyl steht,Phthalazinyl stands,
wobei die möglichen Substituenten jeweils vorzugsweise aus der folgenden Gruppe ausgewählt sind: Hydroxy, Amino, Cyano, Nitro, Carbamoyl, Sulfamoyl, Fluor, Chlor,the possible substituents are each preferably selected from the following group: hydroxy, amino, cyano, nitro, carbamoyl, sulfamoyl, fluorine, chlorine,
Brom, jeweils gegebenenfalls durch Hydroxy, Cyano, Fluor oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t- Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxj, , Methylamino, Ethylamino, n- oder i-Propylamino, n-, i-, s- oder t- Butylamino oder Dimethylamino, jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, Acetylamino, Propionylamino, n- oder i-Butyroylamino, Methyl- aminocarbonyl, Ethylaminocarbonyl, n- oder i-Propylaminocarbonyl, Dimethylaminocarbonyl, Methylthio, Ethylthio, n- oder i-Propylthio, n-, i-, s- oder t-Butylthio, Methylsulfinyl, Ethylsulfinyl, n- oder i- Propylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propyl- sulfonyl, Methylsulfonylamino, Ethylsulfonylamino, n- oder i-Propyl- sulfonylamino, Methylaminosulfonyl. Ethylaminosulfonyl, n- oder i- Propylaminosulfonyl, oder Dimethylaminosulfonyl, jeweils gegebenenfalls durch Hydroxy, Cyano. Nitro, Fluor, Chlor, Methyl, - 143 -Bromine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n- , i-, s- or t-butoxj,, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino or dimethylamino, each optionally substituted by fluorine and / or chlorine, acetyl, propionyl , n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl, methylthio, ethylthio - or i-Propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino, methylaminosulfonyl. Ethylaminosulfonyl, n- or i-propylaminosulfonyl, or dimethylaminosulfonyl, each optionally by hydroxy, cyano. Nitro, fluorine, chlorine, methyl, - 143 -
Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Difluor- methoxy oder Trifluormethoxy substiuiertes Phenyl oder Phenoxy, sowie jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methylendioxy oder Ethylendioxy,Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoro- methoxy or trifluoromethoxy-substituted phenyl or phenoxy, and also methylene dioxy or ethylenedioxy optionally substituted by fluorine and / or chlorine,
mit der Maßgabe, daß in jedem Einzelfall R2, R3 und Y verschieden voneinander sind und daß die Substituenten an den Kohlenstoffatomen, an die R^ und R^ bzw. R^ gebunden sind, wie folgt konfiguriert sind:with the proviso that in each individual case R2, R3 and Y are different from one another and that the substituents on the carbon atoms to which R ^ and R ^ or R ^ are bound are configured as follows:
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,R-Diastereomere"),(a) R configuration on the carbon atom to which R2 and R ^ are bonded and R configuration on the carbon atom to which R ^ is bonded (“R, R diastereomers”),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,S-Diastereomere"),(b) R configuration on the carbon atom to which R ^ and R ^ are bonded and S configuration on the carbon atom to which R ^ is bonded ("R, S diastereomers"),
(c) S -Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ ge- bunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,R-Diastereomere"),(c) S configuration on the carbon atom to which R ^ and R ^ are bound and R configuration on the carbon atom to which R ^ is bound ("S, R diastereomers"),
(d) S-Konfiguration an dem Kohlenstoffatom, an welches R2 und R-> gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,S-Diastereomere"),(d) S configuration on the carbon atom to which R2 and R-> are bonded and S configuration on the carbon atom to which R ^ is bonded (“S, S diastereomers”),
(e) R-Konfiguration an dem Kohlenstoffatom, an welches R^ und RJ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,rac-Diastereomere"), - 144 -(e) R configuration on the carbon atom to which R ^ and R J are attached and racemic configuration on the carbon atom to which R ^ is attached ("R, rac diastereomers"), - 144 -
(f) S-Konfiguration an dem Kohlenstoffatom, an welches R^ und R^ gebunden sind und racemische Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,rac-Diastereomere").(f) S configuration on the carbon atom to which R ^ and R ^ are attached and racemic configuration on the carbon atom to which R ^ is attached ("S, rac diastereomers").
Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß darinCompounds of formula (I) according to claim 1, characterized in that therein
A für eine Einfachbindung, für Dimethylen (Ethan-l,2-diyl, -CH2CH2-), Oxaethandiyl (-CH20-) oder 2-Oxa-propan-l,A for a single bond, for dimethylene (ethane-l, 2-diyl, -CH 2 CH 2 -), oxaethanediyl (-CH 2 0-) or 2-oxa-propane-l,
3-diyl (-CH2OCH2-) steht,3-diyl (-CH 2 OCH 2 -)
Rl für Amino, für Formylamino oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Acetyl- amino, Propionylamino, Methoxycarbonylamino, Ethoxycarbonyl- amino, oder Dimethylaminomethylenamino steht,Rl represents amino, formylamino or acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino or dimethylaminomethyleneamino which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R2 für Wasserstoff, Fluor, Chlor, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl steht,R2 represents hydrogen, fluorine, chlorine, or in each case methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R3 für Wasserstoff, Fluor, Chlor, Brom, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertesR3 represents hydrogen, fluorine, chlorine, bromine, or in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy
Methyl, Ethyl, n- oder i-Propyl steht, oder zusammen mit RX für jeweils gegebenenfalls durch Cyano, Fluor, Chlor oder Methyl sub- stituiertes Dimethylen (Ethan-l,2-diyl) steht,Is methyl, ethyl, n- or i-propyl, or together with RX is in each case optionally substituted by cyano, fluorine, chlorine or methyl-dimethylene (ethane-1,2-diyl),
R4 für Methyl oder Ethyl steht,R4 represents methyl or ethyl,
Y für Wasserstoff, Hydroxy, Cyano, Fluor, Chlor, Brom, oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy. n- oder i- - 145 -Y for hydrogen, hydroxy, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, which are each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy. n- or i- - 145 -
Propoxy, Acetyloxy, Propionyloxy, Methoxycarbonyloxy, Ethoxy- carbonyloxy, Methylaminocarbonyloxy, Ethylaminocarbonyloxy oder Dimethylaminocarbonyloxy steht, undPropoxy, acetyloxy, propionyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, methylaminocarbonyloxy, ethylaminocarbonyloxy or dimethylaminocarbonyloxy, and
für eine gegebenenfalls substituierte monocyclische oder bicyclische, carbocychsche oder heterocyclische Gruppierung aus der Reihe Phenyl, Naphthyl, Tetralinyl, Decalinyl, Indanyl, Indenyl, Furyl, Benzofuryl, Dihydrobenzofuryl, Thienyl, Benzothienyl, Dihydro- benzothienyl, Isobenzofuryl, Dihydroisobenzofuryl, Isobenzothienyl, Dihydroisobenzothienyl, Pyrrolyl, Indolyl, Isoindolyl, Indolinyl, Iso- indolinyl, Benzdioxolyl, Oxazolyl, Benzoxazolyl, Thiazolyl, Benz- thiazolyl, Benzimidazolyl, Indazolyl, Pyrazolyl, Pyridinyl, Pyrimidinyl, Pyrazinyl, Pyridazinyl, Chinolyl, Isochinolyl, Chinoxalinyl, Cinnolinyl und Phthalazinyl steht,for an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzothobyloburyl, dihydrobenzyloburyl, dihydrobenzyloburyl, dihydrobenzylobienyl, dihydrobenzylobienyl, dihydrobenzylbenzylbenzylbenzylbenzyl, , Indolyl, isoindolyl, indolinyl, isoindolinyl, benzdioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolinylzinolinylzinoxalinozolinylzinoxaline,
wobei die möglichen Substituenten jeweils vorzugsweise aus der folgende Gruppe ausgewählt sind:the possible substituents are each preferably selected from the following group:
Hydroxy, Amino, Cyano, Nitro, Carbamoyl, Sulfamoyl, Fluor, Chlor, Brom, jeweils gegebenenfalls durch Hydroxy, Cyano, Fluor oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Hydroxy, amino, cyano, nitro, carbamoyl, sulfamoyl, fluorine, chlorine, bromine, each optionally substituted by hydroxy, cyano, fluorine or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -
Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, Dimethylamino, jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Acetyl, Methoxycarbonyl, Ethoxycarbonyl, Dimethylaminocarbonyl, Methyl- thio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Ethylsulfmyl, Methylsulfonyl, Ethylsulfonyl oder Dimethylaminosulfonyl, jeweils gegebenenfalls durch Hydroxy, Cyano, Nitro, Fluor, Chlor. Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluormethoxy oder Trifluor- methoxy substiuiertes Phenyl oder Phenoxy, sowie jeweils gegebenen- falls durch Fluor und/oder Chlor substituiertes Methylendioxy oderButyl, methoxy, ethoxy, n- or i-propoxy, dimethylamino, each optionally substituted by fluorine and / or chlorine, acetyl, methoxycarbonyl, ethoxycarbonyl, dimethylaminocarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfmyl, methylsulfonyl , Ethylsulfonyl or Dimethylaminosulfonyl, each optionally by hydroxy, cyano, nitro, fluorine, chlorine. Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or phenoxy, as well as given in each case - if methylenedioxy substituted by fluorine and / or chlorine or
Ethylendioxy, - 146 -Ethylenedioxy, - 146 -
mit der Maßgabe, daß in jedem Einzelfall R2, R3 und Y verschieden voneinander sind und daß die Substituenten an den Kohlenstoffatomen, an die R^ und R^ bzw. R^ gebunden sind, wie folgt konfiguriert sind:with the proviso that in each individual case R2, R3 and Y are different from one another and that the substituents on the carbon atoms to which R ^ and R ^ or R ^ are bound are configured as follows:
(a) R-Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebunden sind und R-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,R-Diastereomere"),(a) R configuration on the carbon atom to which R 2 and R ^ are bonded and R configuration on the carbon atom to which R ^ is bonded (“R, R diastereomers”),
(b) R-Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („R,S-Diastereomere"),(b) R configuration on the carbon atom to which R 2 and R ^ are bonded and S configuration on the carbon atom to which R ^ is bonded (“R, S diastereomers”),
(c) S-Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebun- den sind und R-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,R-Diastereomere"),(c) S configuration on the carbon atom to which R 2 and R ^ are bonded and R configuration on the carbon atom to which R ^ is bonded (“S, R diastereomers”),
(d) S-Konfiguration an dem Kohlenstoffatom, an welches R2 und R^ gebunden sind und S-Konfiguration an dem Kohlenstoffatom, an welches R^ gebunden ist („S,S-Diastereomere").(d) S configuration on the carbon atom to which R 2 and R ^ are attached and S configuration on the carbon atom to which R ^ is attached ("S, S diastereomers").
4. Verfahren zur Herstellung von Verbindungen der Formel (I) gemäß Anspruch4. A process for the preparation of compounds of formula (I) according to claim
1 , dadurch gekennzeichnet, daß man substituierte Biguanide der Formel (II),1, characterized in that substituted biguanides of the formula (II),
i-L Hi-L H
R4 R 4
Rι (II) R ι (II)
' NIM' N A/Z ' N IM ' NA / Z
I II I
H H in welcherH H in which
A, Rl , R4 und Z die in Anspruch 1 angegebene Bedeutung haben. - 147 -A, Rl, R4 and Z have the meaning given in claim 1. - 147 -
und/oder Säureaddukte von Verbindungen der allgemeinen Formel (II)and / or acid adducts of compounds of the general formula (II)
mit (optisch aktiven) Carbonsäurederivaten der allgemeinen Formel (III)with (optically active) carboxylic acid derivatives of the general formula (III)
R2 R 2
-R3 -R 3
^ (III) ^ (III)
in welcherin which
R2, R3 und Y die in Anspruch 1 angegebene Bedeutung haben undR2, R3 and Y have the meaning given in claim 1 and
X für Halogen oder Alkoxy steht,X represents halogen or alkoxy,
gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt,if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
und gegebenenfalls an den so erhaltenen Verbindungen der allgemeinen Formel (I) im Rahmen der obigen Substituentendefinition weitere Umwandlungen nach üblichen Methoden durchführt.and optionally on the compounds of the general formula (I) thus obtained in the context of the above definition of substituents, further conversions are carried out by customary methods.
5. Herbizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung der Formel (I) gemäß Anspruch 1.5. Herbicidal agents, characterized in that they contain at least one compound of the formula (I) according to Claim 1.
6. Verwendung von Verbindungen der Formel (I) gemäß Anspruch 1 zur Bekämpfung von unerwünschtem Pflanzenwachstum.6. Use of compounds of formula (I) according to claim 1 for combating undesirable plant growth.
7. Verfahren zur Bekämpfung von Unkräutern, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) gemäß Anspruch 1 auf die Unkräuter oder ihren Lebensraum einwirken läßt. - 148 -7. A method of combating weeds, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on the weeds or their habitat. - 148 -
8. Verfahren zur Herstellung von herbiziden Mitteln, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt. 8. A process for the preparation of herbicidal compositions, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents.
EP99913191A 1998-03-11 1999-02-26 6-substituted 2,4-diamino-1,3,5-triazine derivatives having at least two asymmetrically substituted carbon atoms, the production thereof, and their use as herbicides Withdrawn EP1071672A1 (en)

Applications Claiming Priority (3)

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DE19810394 1998-03-11
DE19810394A DE19810394A1 (en) 1998-03-11 1998-03-11 New aminotriazine derivatives useful as herbicides, especially for selective weed control
PCT/EP1999/001234 WO1999046249A1 (en) 1998-03-11 1999-02-26 6-substituted 2,4-diamino-1,3,5-triazine derivatives having at least two asymmetrically substituted carbon atoms, the production thereof, and their use as herbicides

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BR9908589A (en) 2000-11-14
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CA2322417A1 (en) 1999-09-16
JP2002506062A (en) 2002-02-26
KR20010041351A (en) 2001-05-15
AU3141899A (en) 1999-09-27
CN1299352A (en) 2001-06-13
AU752788B2 (en) 2002-10-03
US6358886B1 (en) 2002-03-19

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