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CN1073675A - Herbicidal cyclohexanes - Google Patents

Herbicidal cyclohexanes Download PDF

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Publication number
CN1073675A
CN1073675A CN92114386A CN92114386A CN1073675A CN 1073675 A CN1073675 A CN 1073675A CN 92114386 A CN92114386 A CN 92114386A CN 92114386 A CN92114386 A CN 92114386A CN 1073675 A CN1073675 A CN 1073675A
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alkyl
group
compound
phenyl
formula
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A·J·利帕
A·霍夫曼
R·H·尼尔恩
C·T·裴
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Dunlena Pty Ltd
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Dunlena Pty Ltd
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    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/42—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/52—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The new compound of formula (1) and its isomer and/or change form, wherein A, X and R 1To R 9It is different substituting groups.The agricultural composition of these compounds, and these compounds are as the application method preceding and/or emerge back weedicide and plant-growth regulator of emerging.

Description

Herbicidal cyclohexanes
The present invention relates to have the organic compound of weeding activity and plant growth regulating activity; The method of herbicidal composition and these compounds of application; And plant growth regualting composition and these method for compositions of application.
Known in the prior art and used some hexanaphthene-1.3-derovatives as dogstail section weedicide.So, for example, " agricultural chemicals handbook; the 8th edition " (C.R.Worthing Editor, The British Crop Protection Council, Thornton Heath, hexanaphthene-1 as the selectivity herbicide after seedling has been described UK), the 3-derovatives, known commercial as alloxydim (E)-(RS)-3-(1-(allyl oxygen imines) butyl)-4-hydroxyl-6, the sodium salt of 6-dimethyl-2-oxygen hexamethylene-3-olefinic carboxylic acid methyl ester, cycloxydim (RS)-2-(1-(ethoxy imino) butyl)-3-hydroxyl-5-thiophene alkane-3-basic ring oneself-2-ketenes and sethoxydim (RS)-(ZE)-2-(1-ethoxy imino butyl)-5-(2-(ethylenebis dithiocarbamate) propyl group)-3-hydroxyl hexamethylene-2-ketenes.Alloxydim and sethoxydim once were disclosed in U.S. Patent No. 4,011 respectively, 256 and Australian patent application No.35314/78 in.
Chevron Research Company United States Patent (USP) 4 under one's name, 440,566 disclose the molten and similar weeding haloalkyl of sethoxydim with dogstail, 2-(the 1-(oxo amino) alkylidene group that halogenated alkenyl and halogenated aryl replace)-hexanaphthene-1.3-diketone.Wherein disclosing especially has the chloro allyl group on the oxo amino group, halogeno-benzyl, or the substituent compound of trifluoromethyl benzyl.
United States Patent (USP) 5,022,914 claimed a series of hexanaphthene ketoxime ether compounds that are similar to following formula I compound of BASF AG the difference is that the substituting group on the oxo amino group is made up of the phenyl of any replacement, and it is to pass through C 4Alkylidene group or alkylene group bridge chain are connected with ether oxygen atom, and only at 4 bit strips a substituting group are arranged on hexanaphthene ketone ring.Claimed these of this patent have the herbicidal compounds of highly selective to gramineous weeds.
At nearest disclosed European patent application EP O 456 069A1(1991.11.13) in, BASF AG is claimed, and those are different with US 5,022,914, and its jackshaft chain is C 3, C 5And C 6The weedicide of alkylidene group or alkylene group.Claimed single substituting group is selected from C on 4 on hexanaphthene ketone ring 1-C 4Alkoxy-C 1-C 4Alkyl, C 1-C 4Alkylthio-C 1-C 6-alkyl, the C that replaces arbitrarily 3-C 7Cycloalkyl, contain one or two five yuan of saturated heterocyclic that are selected from O or the heteroatomic any replacement of S, contain one or two the first heterocycle of saturated or unsaturated 6-7 that is selected from O or the heteroatomic any replacement of S, the hetero-aromatic ring that contains any replacement of one or two nitrogen-atoms and Sauerstoffatom or sulphur atom, or for can be selected from halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl and C 1-C 4Phenyl or pyridyl that the substituting group of halogenated alkoxy replaces; Although do not comprise among the present invention that these compounds have very wide claim, the substituting group that EP 0 456 069 discloses especially on 4 of hexanaphthene ketone has only ethylenebis dithiocarbamate propyl group, cyclohexyl, one of cyclohexenyl or a series of heterocyclic radicals, for example, tetrahydrofuran base, tetrahydrochysene thio-phenyl, dioxo penta cyclic group, dithio penta cyclic group, dihydro pyranyl, THP trtrahydropyranyl, 1.2-thiazolyl, tetrahydro thiapyran base.
We find, with US 4,440,566, US 5,022,914 is similar with disclosed person among the EP 0 456 069, rather than in this document disclosed generation compound, (wherein oxime band cap group comprises phenyl or substituted phenyl) is highly actively to emerge preceding and/or emerge back weedicide or plant-growth regulator, and is specially adapted to control Gramineae ruderal in dry land or rice field.
Therefore, the invention provides the new compound of general formula (1), the agricultural composition of these compounds and use these compounds method preceding and/or emerge back weedicide and plant-growth regulator of doing to emerge:
Figure 921143869_IMG3
Wherein
A is selected from C 1-C 3Alkylidene group and C 3Alkylene group, wherein each group can be selected from C alone by 1-4 1-C 3The substituting group of alkyl at random replaces;
X is selected from group O, and singly-bound;
R 1Be selected from H, C 1-C 4Alkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl group, C 5-C 6Cycloalkyl, C 5-C 6Cycloalkenyl, chain triacontanol base, fragrant and mellow base, C 1-C 4Alkyl sulphonyl, aryl sulfonyl, benzenesulfonyl, C 1-C 4Alkyl-carbonyl, C 2-C 8Alkoxyalkyl, C 2-C 8Alkyl-thio-alkyl, C 7-C 10Phenylalkyl, M and can be selected from down the phenyl that substituting group that group comprises replaces arbitrarily by 1-3, this organizes substituting group is halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl, amino, and C 1-C 4Halogenated alkoxy;
R 2Be selected from C 1-C 6Alkyl, C 2-C 6Alkenyl, C 2-C 6Alkynyl group, C 1-C 4Haloalkyl, C 1-C 4Alkylthio, C 3-C 6Cycloalkyl, C 5-C 6Cycloalkenyl, C 2-C 8Alkoxyalkyl, C 2-C 8Alkyl-thio-alkyl is selected from the C that following one group substituting group replaces 1-C 4Alkyl, these substituting groups are phenyl, phenoxy group and sulphur phenoxy group, and wherein said substituent aromatic ring can be selected from halogen, C by 1-3 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, amino, C 1-C 4Haloalkyl and C 1-C 4The substituting group of halogenated alkoxy replaces arbitrarily, and can be by 1-3 phenyl that is selected from any replacement of following one group substituting group, and this group substituted radical is a halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl, amino, and C 1-C 4Halogenated alkoxy;
R 3And R 4Be selected from H respectively, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, and cyano group, or R 3Or R 4One of separately with R 5And R 6In one link together by ring carbon atom, form 5-or 6-unit ring;
R 5And R 6Be selected from H respectively, C 1-C 6Alkyl, C 2-C 4Alkenyl, C 2-C 8Alkyl-thio-alkyl, C 1-C 4Haloalkyl, C 2-C 4Halogenated alkenyl, C 3-C 6Cycloalkyl, alkyl wherein, alkenyl and cycloalkyl can at random be replaced by 1-3 substituting group that is selected from down group respectively, and these substituted radicals comprise OR 12, NR 13R 14, R 15CO-(C 1-C 4Alkyl), NR 18SO 2(C 1-C 4Alkyl), C(OR 16) (OR 17) R 22, C(SR 19) (SR 20) R 23, C 1-C 4Carbalkoxy and can be selected from halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl and C 1-C 4The phenyl that the substituting group of haloalkoxy alkyl replaces arbitrarily; Or
R 5And R 6Be connected to form saturated or unsaturated 3-to 7-unit carbocyclic ring with ring carbon atom, saturated or undersaturated 5-is to 7-unit heterocycle, and this heterocycle contains 1-3 and is selected from the heteroatoms that comprises 0-3 nitrogen, a 0-2 oxygen and 0-2 sulphur atom; Carbocyclic ring or heterocycle can be selected from halogen, C respectively by 1-4 1-C 4Alkyl, C 1-C 4Haloalkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl group, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, C 1-C 4Carbalkoxy ,-COOH, C 2-C 8Alkoxyalkyl, C 2-C 8Alkyl-thio-alkyl and can be selected from halogen, C by one 1-C 4Alkoxyl group, C 1-C 4Alkylthio, C 1-C 4Haloalkyl, nitro, cyano group and C 1-C 4The substituting group of the phenyl that the substituting group of halogenated alkoxy at random replaces replaces; Carbon atom of carbocyclic ring and heterocyclic can be at random with carbonyl or its corresponding dimethyl, and the form of diethyl or ethene or propylene ketal exists;
R 7, R 8And R 9Be selected from H respectively; Halogen; C 1-C 4Alkyl; C 1-C 4Alkoxyl group; C 1-C 4Alkylthio; C 1-C 4Alkyl sulphinyl; C 1-C 4Alkyl sulphonyl, C 1-C 4Haloalkyl; C 1-C 4Halogenated alkoxy; Nitro; Cyano group; C 1-C 4Carbalkoxy; C 1-C 4Alkyl amino-carbonyl; C 2-C 6Dialkyl amino carbonyl; Aminocarboxyl; Amino; C 1-C 4Alkylamino; And C 2-C 6Dialkyl amido; Or be selected from benzenesulfonyl, benzoyl benzene, benzyl, benzyloxy, pyridyl, phenoxy group, phenyl sulfo-, phenyl amino and phenyl groups, but individual halogen, the C of being selected from respectively of described group 1-3 1-C 4Alkyl, C 1-C 4Alkoxyl group and CF 3Substituting group replace arbitrarily;
M is selected from Li +, Na +, K +, NH + 4And N(R 11) + 4, R wherein 11Be C 1-C 4Alkyl;
R 12Be selected from H, C 1-C 4Alkyl, benzyl, CO(C 1-C 4And CO alkyl), 2(C 1-C 4Alkyl) group;
R 13, R 15, R 18, R 22And R 23Be selected from H and C respectively 1-C 3Alkyl;
R 14, R 16, R 17, R 19And R 20Be selected from C respectively 1-C 3Alkyl;
R 16And R 17Can be connected into together-(CH 2) 2-or-(CH 2) 3-; And
R 19And R 20Can be connected into together-(CH 2) 2-or-(CH 2) 3-; Condition is:
A) when A be CH 2And X is singly-bound, and R 1Be H, C 1-C 4Alkyl-carbonyl, aryl carbonyl or M, R 2Be C 1-C 6Alkyl or phenyl, R 3And R 4Be H, R 5And R 6Be H, C 1-C 3Alkyl or C 2-C 8During alkyl-thio-alkyl, R at least then 7, R 8And R 9In one be not H, CF 3, nitro or halogen;
B) when A be C 2-C 3Alkylidene group, X are O, R 1Be H, R 2Be C 3Alkyl, R 3And R 4Be H, R 5And R 6Be CH 3The time, R at least then 7, R 8And R 9In one be not H;
C) when A be CH 2, or by 1-3 C 1-C 3The C that alkyl group replaces arbitrarily 3Alkylene group or C 3Alkenyl, and X is singly-bound, R 1Be H, R 3And R 4All be H, R 5Or R 6In one be that hydrogen and another are C 2-C 8Alkyl-thio-alkyl is by O(C 1-C 4Alkyl) C of Qu Daiing 1-C 4Alkyl, or by OR 12Any C that replaces 3-C 6Cycloalkyl, wherein R 12Be C 1-C 4When alkyl or H, R at least then 7, R 8Or R 9In one be not H, halogen, nitro, cyano group, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Haloalkyl, C 1-C 4Halogenated alkoxy, C 1-C 4Carbalkoxy or the phenyl that replaces arbitrarily.
In above-mentioned definition, " alkyl " speech no matter separately or the compound word as " alkylthio " or " haloalkyl " in, the alkyl of all representing straight or branched, for example methyl, ethyl, propyl group, n-propyl, sec.-propyl or different butyl, amyl group or hexyl isomer.
The alkoxyl group of " alkoxyl group " expression straight or branched, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy and different butoxy isomer.
The group that " alkenyl " expression is formed by the straight or branched alkene, for example vinyl, 1-propenyl, 2-propenyl, 3-propenyl etc.
The group that " alkynyl group " expression is formed by the straight or branched alkyne, for example ethynyl, 1-proyl, 2-propynyl and different butine isomer.
" alkyl sulphonyl " expression methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base and different butyl alkylsulfonyl isomer.
" alkylthio ", " alkyl sulphinyl ", " alkylamino " etc. define in above-mentioned similar mode.
" cycloalkyl " representative ring propyl group, cyclobutyl, cyclopentyl, cyclohexyl and suberyl.
" halogen " speech no matter separately or in the compound word as " haloalkyl ", is all represented fluorine, chlorine, bromine or iodine.Ought be used for the compound word in addition, alkyl can be partially halogenated or be replaced fully by halogen atom described in " haloalkyl ", and these haloalkyls can be identical or different.For example, haloalkyl comprises CH 2CH 2F, CF 2CF 3And CH 2CHFCl.
" alkyl-carbonyl " expression ethanoyl, propionyl and different butyryl radicals isomer.
" carbalkoxy " expression methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, different third oxygen carbonyl and different butoxy carbonyl isomer.
The sum of carbon atom is represented with Ci-Cj in substituting group, and specifying wherein i and j in advance is 1 to 10 integer.C for example 2-C 3Alkyl-thio-alkyl will be appointed as-CH 2SCH 3,-CH 2SC 2H 5,-CH 2CH 2SCH 3Or-CH(CH 3) SCH 3, and C 2-C 5Alkoxyalkyl will be represented-CH 2OCH 3To-(CH 2) 4OCH 3Or-CH 2O(CH 2) 3CH 3, and be included in the constitutional isomer of wherein each kind.
" alkylidene group " expression methylene radical (CH 2-), ethylidene (CH 2CH 2-), propylidene and butylidene; " alkylene group " expression-CH=CHCH 2-,-CH=CHCH 2CH 2-and-CH 2CH=CHCH 2-.
Several groups of compounds of preferred following general formula (1) are that they comprise because it synthesizes easily and bigger herbicide action is arranged:
(1) general formula 1 compound, wherein
R 1Be H, alkyl sulphonyl, aryl sulfonyl or M, and R 2Be C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 2-C 4Alkenyl or C 2-C 4Alkynyl group.
(2) in above-mentioned formula (1) compound,
A is C 1-C 2Alkylidene group or by CH 3Or C 2H 5Any C that replaces 3-C 4Alkenylene;
R 7, R 8And R 9Be respectively H, Cl, Br, F, C 1-C 3Alkyl, C 1-C 3Alkoxyl group, C 1-C 3Alkylthio, C 1-C 3Haloalkyl, C 1-C 3Halogenated alkoxy, nitro, cyano group or C 1-C 3Carbalkoxy; Or by the individual halogen, C of being selected from of 1-3 1-C 4Alkyl, C 1-C 4Alkoxyl group or CF 3The phenyl sulfonyl that replaces arbitrarily of substituting group, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl sulfo-or phenylamino.
(3) wherein X is the above-claimed cpd (2) of O.
(4) wherein X is single bonded above-claimed cpd (2).
(5) above-claimed cpd (4) is wherein:
A is-CH 2-,-CH 2CH 2-,-CH 2CH=CH-or-CH 2CMe=CH-;
R 1Be H, Li +, Na +Or K +;
R 2Be CH 3, C 2H 5, n-C 3H 7Or n-C 4H 9;
R 3And R 4Be respectively H, CH 3Or C 2H 5; And
R 7, R 8And R 9Each is H naturally, Cl, Br, F, CH 3, C 2H 5, OCH 3, OC 2H 5, SCH 3, SC 2H 5, CF 3, CHF 2, CF 2CF 3, OCHF 2, OCF 3, OCH 2CF 3, NO 2, CN, CO 2CH 3, Ph, SO 2Ph, COPh, CH 2Ph, OCH 2Ph, OPh, SPh, NHPh or N(Me) Ph.
(6) above-claimed cpd (4), wherein R 5And R 6Each is C naturally 1-C 4Alkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl group, C 1-C 4Alkylthio or C 2-C 6Alkyl-thio-alkyl.
(7) above-claimed cpd (4), wherein R 5And R 6Connect the saturated or unsaturated 5-of formation with carbon atom, 6-or 7-unit carbocyclic ring, this ring can be by 1-4 CH 3Group at random replaces.
(8) above-claimed cpd (7), wherein:
A is-CH 2-,-CH 2CH 2-or CH 2CH=CH-;
R 1Be H, Li +, Na +Or K +; R 2Be CH 3, C 2H 5, n-C 3H 7Or n-C 4H 9;
R 3And R 4Each is H or CH naturally 3; And
R 7, R 8And R 9Each is H naturally, Cl, Br, F, CH 3, C 2H 5, OCH 3, OC 2H 5, SCH 3, SC 2H 5, CF 3, CHF 2, CF 2CF 3, OCHF 2, OCF 3, OCH 2CF 3, NO 2, CN, CO 2CH 3, Ph, SO 2Ph, COPh, CH 2Ph, OCH 2Ph, OPh, SPh, NHPh or N(Me) Ph.
(9) above-claimed cpd (4), wherein:
R 5And R 6Connect formation with carbon atom and contain 1-2 heteroatomic saturated or undersaturated 5-, 6-or 7-unit heterocycle, heterocycle is selected from and comprises 0-2 nitrogen, the group of 0-1 oxygen and 0-2 sulphur atom; Described ring can be by 1-4 CH 3Group replaces arbitrarily.
(10) above-mentioned compound (9), wherein:
A is-CH 2,-CH 2CH 2-or CH 2CH=CH-;
R 1Be H, Li +, Na +Or K +;
R 2Be CH 3, C 2H 5, n-C 3H 7Or n-C 4H 9;
R 3And R 4Each is H naturally, CH 3Or C 2H 5; And
R 7, R 8And R 9Each is H naturally, Cl, Br, F, CH 3, C 2H 5, OCH 3, OC 2H 5, SCH 3, SC 2H 5, CF 3, CHF 2, CF 2CF 3, OCHF 2, OCF 3OCH 2CF 3, NO 2, CN, CO 2CH 3, Ph, SO 2Ph, COPh, CH 2Ph, OCH 2Ph, OPh, SPh, NHPh or N(Me) Ph.
Examples for compounds in the scope of the invention is shown in down in the tabulation 1.
Table 1
Formula 1, R 1=R 9=H, the X=singly-bound
Formula 1, R 1=R 9=H, the X=singly-bound
A R 2R 3R 4R 5R 6R 7R 8
1.1 CH 2Pr H H H H 4-Ph H
1.2 CH 2Pr H H H H 4-(4-F)Ph H
1.3 CH 2Pr CO 2Me H H H 4-(4-F)Ph H
1.4 CH 2Pr CO 2Et H H H 4-(4-F)Ph H
1.5 CH 2Pr Me H H H 4-Ph H
1.6 CH 2Pr Me H H H 4-(4-F)Ph H
1.7 CH 2-CH=CH Pr Me H H H 4-F H
1.8 CH 2-CH=CH Pr Me H H H 2-F 4-Cl
1.9 CH 2-CH=CH Pr Me H H H 2-Cl 4-F
1.10 CH 2-CH=CH Pr Me H H H 2-Cl 4-Cl
1.11 CH 2-CH=CH Pr Me H H H 2-F 4-F
1.12 CH 2Pr Me CO 2Me H H 4-Ph H
1.13 CH 2Pr Me CO 2Me H H 4-(4-F)Ph H
1.14 CH 2Pr Me CO 2Et H H 4-(4-F)Ph H
1.15 CH 2Pr H H Me H 4-Ph H
1.16 CH 2Pr H H Me H 4-(4-F)Ph H
1.17 CH 2-CH=CH Pr H H H H 4-F H
1.18 CH 2-CH=CH Pr H H H H 2-F 4-Cl
1.19 CH 2-CH=CH Pr H H H H 2-Cl 4-F
1.20 CH 2-CH=CH Pr H H H H 2-Cl 4-Cl
1.21 CH 2-CH=CH Pr H H H H 2-F 4-F
1.22 CH 2Pr CO 2Me H Me H 4-Ph H
1.23 CH 2Pr CO 2Me H Me H 4-(4-F)Ph H
1.24 CH 2Pr CO 2Et H Me H 4-(4-F)Ph H
1.25 CH 2Pr Me H Me H 4-Ph H
1.26 CH 2Pr Me H Me H 4-(4-F)Ph H
1.27 CH 2-CH=CH Pr Me H Me H 4-F H
1.28 CH 2-CH=CH Pr Me H Me H 2-F 4-Cl
1.29 CH 2-CH=CH Pr Me H Me H 2-Cl 4-F
1.30 CH 2-CH=CH Pr Me H Me H 2-Cl 4-Cl
1.31 CH 2-CH=CH Pr Me H Me H 2-F 4-F
1.32 CH 2Pr Me CO 2Me Me H 4-(4-F)Ph H
1.33 CH 2-CH=CH Pr H H Me Me 4-Ph H
1.34 CH 2Me H H Me Me 4-Ph H
1.35 CH 2Et H H Me Me 4-Ph H
1.36 CH 2Me H H Me Me 4-(4-F)Ph H
1.37 CH 2Et H H Me Me 4-(4-F)Ph H
1.38 CH 2Pr H H Me Me 3-Ph H
1.39 CH 2Pr H H Me Me 4-Ph H
1.40 CH 2Pr H H Me Me 2-F 4-Ph
1.41 CH 2Pr H H Me Me 3-F 4-Ph
A R 2R 3R 4R 5R 6R 7R 8
1.42 CH 2Pr H H Me Me 4-F 3-Ph
1.43 CH 2Pr H H Me Me 4-(4-F)Ph H
1.44 CH 2-CH=CH Pr H H Me Me 4-F H
1.45 CH 2-CH=CH Pr H H Me Me 2-F 4-Cl
1.46 CH 2-CH=CH Pr H H Me Me 2-Cl 4-F
1.47 CH 2-CH=CH Pr H H Me Me 2-Cl 4-Cl
1.48 CH 2-CH=CH Pr H H Me Me 2-F 4-F
1.49 CH 2Pr H H Me Me 4-(4-Ph)Ph H
1.50 CH 2Pr CO 2Me H Me Me 4-Ph H
1.51 CH 2Pr CO 2Et H Me Me 4-Ph H
1.52 CH 2Pr CO 2Me H Me Me 4-(4-F)Ph H
1.53 CH 2Pr CO 2Et H Me Me 4-(4-F)Ph H
1.54 CH 2Pr H H Me Et 4-Ph H
1.55 CH 2Pr H H Me Et 4-(4-F)Ph H
1.56 CH 2-CH=CH Pr H H Me Et 4-F H
1.57 CH 2-CH=CH Pr H H Me Et 2-F 4-Cl
1.58 CH 2-CH=CH Pr H H Me Et 2-Cl 4-F
1.59 CH 2-CH=CH Pr H H Me Et 2-Cl 4-Cl
1.60 CH 2-CH=CH Pr H H Me Et 2-F 4-F
1.61 CH 2Pr H H Me iso-Pr 4-Ph H
1.62 CH 2Pr H H Me iso-Pr 4-(4-F)Ph H
1.63 CH 2Pr Me H Me Me 4-Ph H
1.64 CH 2Pr Me H Me Me 4-(4-F)Ph H
1.65 CH 2Pr Me CO 2Me Me Me 4-Ph H
1.66 CH 2Pr Me CO 2Et Me Me 4-(4-F)Ph H
1.67 CH 2Pr Me CO 2Me Me Me 4-Ph H
1.68 CH 2Pr Me CO 2Et Me Me 4-(4-F)Ph H
1.69 CH 2Pr Me H Me Et 4-(4-F)Ph H
1.70 CH 2Pr Me H Me iso-Pr 4-Ph H
1.71 CH 2Pr Me Me Me Me 3-Ph H
1.72 CH 2Pr Me Me Me Me 4-Ph H
1.73 CH 2Me Me Me Me Me 4-(4-F)Ph H
1.74 CH 2Pr Me Me Me Et 4-Ph H
1.75 CH 2Pr Me Me Me iso-Pr 4-Ph H
1.76 CH 2Pr H H Et H 4-Ph H
1.77 CH 2-CH=CH Pr H H Et H 4-Ph H
1.78 CH 2Pr H H Et H 4-(4-F)Ph H
1.79 CH 2-CH=CH Pr H H Et H 4-F H
1.80 CH 2-CH=CH Pr H H Et H 2-F 4-Cl
1.81 CH 2-CH=CH Pr H H Et H 2-Cl 4-F
1.82 CH 2-CH=CH Pr H H Et H 2-Cl 4-Cl
1.83 CH 2-CH=CH Pr H H Et H 2-F 4-F
1.84 CH 2Pr CO 2Me H Et H 4-(4-F)Ph H
1.85 CH 2Pr H H Pr H 4-Ph H
1.86 CH 2-CH=CH Pr H H Pr H 4-Ph H
A R 2R 3R 4R 5R 6R 7R 8
1.87 CH2 Pr H H Pr H 4-(4-F)Ph H
1.88 CH 2-CH=CH Pr H H Pr H 4-F
1.89 CH 2-CH=CH Pr H H Pr H 2-F 4-Cl
1.90 CH 2-CH=CH Pr H H Pr H 2-Cl 4-F
1.91 CH 2-CH=CH Pr H H Pr H 2-Cl 4-Cl
1.92 CH 2-CH=CH Pr H H Pr H 2-F 4-F
1.93 CH2 Pr CO 2Me H Pr H 4-(4-F)Ph H
1.94 CH 2Pr H H isoPr H 4-Ph H
1.95 CH 2-CH=CH Pr H H isoPr H 4-Ph H
1.96 CH 2Pr H H isoPr H 4-(4-F)Ph H
1.97 CH 2-CH=CH Pr H H isoPr H 4-F H
1.98 CH 2-CH=CH Pr H H isoPr H 2-F 4-Cl
1.99 CH 2-CH=CH Pr H H isoPr H 2-Cl 4-F
1.100 CH 2-CH=CH Pr H H isoPr H 2-Cl 4-Cl
1.101 CH 2-CH=CH Pr H H isoPr H 2-F 4-F
1.102 CH 2Pr CO 2Me H isoPr H 4-(4-F)Ph H
1.103 CH 2Pr H H Bu H 4-Ph H
1.104 CH 2-CH=CH Pr H H Bu H 4-Ph H
1.105 CH 2Pr H H Bu H 4-(4-F)Ph H
1.106 CH 2Pr CO 2Me H Bu H 4-(4-F)Ph H
1.107 CH 2Pr H H i-Bu H 4-Ph H
1.108 CH 2Pr H H i-Bu H 4-(4-F)Ph H
1.109 CH 2Pr CO 2Me H i-Bu H 4-(4-F)Ph H
1.110 CH 2Pr H H s-Bu H 4-Ph H
1.111 CH 2Pr H H s-Bu H 4-(4-F)Ph H
1.112 CH 2Pr CO 2Me H s-Bu H 4-(4-F)Ph H
1.113 CH 2Pr H H t-Bu H 4-Ph H
1.114 CH 2Pr H H t-Bu H 4-(4-F)Ph H
1.115 CH 2Pr CO 2Me H t-Bu H 4-(4-F)Ph H
1.116 CH 2-CH=CH Pr H H Me Me 4-Cl H
1.117 CH 2-CH=CH Me H H Me Me 2-Cl 4-Cl
1.118 CH 2-CH=CH Et H H Me Me 2-Cl 4-Cl
1.119 CH 2-CH=CH Bu H H Me Me 2-Cl 4-Cl
1.120 CH 2-CH=CH Me H H Me Me 2-F 4-F
1.121 CH 2Pr H H CH=CMe 2H 4-Ph H
1.122 CH 2-CH=CH Pr H H Me Me 2-NO 2H
1.123 CH 2Pr H H C 2H 4OMe H 4-Ph H
1.124 CH 2-CMe=CH Pr H H Me Me 4-Cl H
1.125 CH 2-CMe=CH Pr H H Me Me 4-F H
1.126 CH 2-CH=CMe Pr H H Me Me 4-Cl H
Because have maximum herbicide action and/or have maximum selectivity and/or easy the most synthetic and particularly preferred compound to be to paddy rice:
2-(1-(4-phenyl benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone (compound 1.3g)
2-(1-(4-(4-fluorophenyl) benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone (compound 1.43)
2-(1-(3-(2,4-dichlorophenyl) allyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone (compound 1.47)
2-(1-(3-(2,4-difluorophenyl) allyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone (compound 1.48)
2-(1-(4-(4-fluorophenyl) benzyloxy amino) butylidene)-and 5-normenthane-1,3-diketone (compound 1.96)
2-(1-(3-(2,4-dichlorophenyl) allyloxy amino) propylidene)-5,5-dimethyl cyclohexane-1,3-diketone (compound 1.118)
R wherein 1The similar preferred compound that is not hydrogen is:
2-(1-(3(2,4-dichlorophenyl) allyloxy amino) butylidene)-5,5-dimethyl-1-phenyl sulfonyloxy hexamethylene-1-alkene-3-ketone (compound 2.1)
2-(1-(4-phenyl) benzyloxy amino) butylidene)-5,5-dimethyl-1-phenyl-sulfonyloxy hexamethylene-1-alkene-3-ketone (compound 2.2)
Should be realized that R1 is that the compound (1) of hydrogen can change among the present invention.All tautomers include within the scope of the invention.
Compound of the present invention can be by conventional synthetic method preparation, comprising US 4,440, and the method for general introduction in 566.Specific cyclohexanedione can obtain the product that C-replaces by the acetylize and the enol ester isomerization (fries' rearrangement) of oxygen.The derivative of C-acidylate can react with the oxyamine that the O-that produces from suitable precursor in position replaces, and obtains wherein R 1It is the row biology of the general formula (1) of hydrogen.
Also can prepare wherein R by the synthetic method of routine 1It or not the compound of the general formula of the present invention (1) of hydrogen.For example, R wherein 1Be the cationic general formula of the present invention of organic or inorganic (1) compound, can be from R wherein 1General formula of the present invention (1) compound that is hydrogen makes it to make with the reaction of suitable inorganic or organic bases.
R wherein 1Be sulfonylation, etherificate or the esterification of the divinyl acid in formula of the present invention (1) compound of H, some other weeding and plant growth regulating derivative is provided.
The activity of The compounds of this invention
Test-results shows that The compounds of this invention has and high emerge preceding and/or emerge back weeding activity or plant growth regulating activity.These compounds are used in granule cereal as some gramineous weeds of control in wheat (Triticum aestivum) and barley (Hordenum vulgare), and the example of these cereal also comprises but is not only limited to Centurk wheat, Era wheat, Igri barley and Klages barley.Chemical compound lot among the present invention to optionally control example such as wild avena sativa (Avena fatua), mouse tail amur foxtail (Alopecurus myosoides), to rise lady's-grass (Digitaria sanguinalis), Herba Setariae Viridis (Setaria spp) and Itanlian rye gramineous weedss such as (Lolium multiflorum) particularly useful.These compounds are also particularly useful for some gramineous weeds of control in dry land and paddy rice (Orysa sativa), and the example of these crops includes but are not limited to the various crop of India and Japan.Chemical compound lot among the present invention is for optionally control is particularly useful as barnyard grass gramineous weedss such as (Echinochloacrusgalli) in rice terrace.
Under suitable usage quantity, these compounds can also be controlled the place of various plants at needs, are used to control the preceding and/or back weeds that emerge of emerging of wide spectrum.In addition, these compounds can be used for coordinate plant growth.
The suitable ratio of The compounds of this invention can be by multiple factor decision.These factors comprise the quantity, growth conditions etc. of plant of preparation, application process, the existence of selection.Usually, the amount of application of motif compound is 0.005 to the 5kg/ hectare, preferred consumption 0.01 in the scope of 1kg/ hectare.Control needed level according to weeds, those skilled in the art can determine applicating ratio at an easy rate.
The compounds of this invention can be used separately or mix use with other commodity weedicide, sterilant or sterilant.Therefore, in further embodiment, the invention provides formula (1) herbicidal compound that contains at least a aforementioned definitions and the herbicidal composition of at least a other Herbicidal mixtures.
In embodiment further, the invention provides a kind of method of coordinate plant growth, it comprises the seed of plant, plant or the value of plant-growth is used formula (1) compound of the aforementioned definitions of significant quantity.
The amount of application of these compounds can be subjected to many Effect of Environmental, and should determine it according to the condition of practical application.To the gramineous weeds in the gramineous crop,, all can be killed usually when to be no less than 0.1 during to the processing of the ratio of about 1kg activeconstituents/hectare.
Compound of the present invention can mix with mycocide, bactericide, miticide, nematocides, sterilant or other bioactive compounds, and to spend the minimum time, labour and material are obtained expected result.The quantity that joins these biologically active substances in the present composition can change between 0.05 to 25 weight part in parts by weight.Such appropriate formulations is well known to those skilled in the art.
Preparation
The useful preparation that can prepare the compound in the scope of the invention by ordinary method.They comprise that the many kinds in pulvis, granule, tablet, solution, emulsion, wettable powder, these preparations can directly use: sprayable preparation can be with suitable Jie's base expansion, and is raised in per hectare one under the sprayed volume of several hectolitres and uses.The high strength composition is initial preparation, be used as in the midbody preparation of further preparation, say from wide region and contain about by weight activeconstituents of 1% to 99% and at least a about tensio-active agent of 0.1% to 20% and about 5% to 99% solid or liquid inert diluent.More particularly, provided the approximate ratio of these compositions that they contain in the following table.
Weight percent
Preparation type activeconstituents thinner tensio-active agent
Wettable powder 20-90 0-74 1-10
Oil suspension, emulsion 5-50 40-95 0-15
But solution comprises emulsion concentrate
Aqeous suspension 10-50 40-84 1-20
Pulvis 1-25 70-99 0-5
Granule and tablet 1-95 5-99 0-15
High strength composition 90-99 0-10 0-2
Certainly, the activeconstituents of the lower or higher level of existence depends on the purposes of expection and the physical properties of compound.Sometimes need be with respect to a high proportion of tensio-active agent of activeconstituents.And obtain by being blended in the preparation or by the jar mixing.
Composition can be the form of pulvis or granule, wherein contains activeconstituents and its solid diluent or carrier, kaolin for example, wilkinite, diatomite, rhombspar, lime carbonate, talcum, powder magnesium oxide, bleaching clay, gypsum, diatomite, and Chinese clay.This composition can also be the form of dispersion powder or granule, wherein contains to make pulvis or small-particle be easy to be distributed to wetting agent in the liquid, can contain solid diluent, filler and suspension agent in the composition.
People such as Watkins are at " Handbook of Insecticide Dust Diluents and Carriers ", 2nd Ed., and Dorland Books, Caldwell has described the typical solid thinner among the N.J..The thinner that adsorptivity is stronger relatively is suitable for wettable powder, and the thinner that density is bigger is suitable for pulvis.Can contain minor amounts of additives in all preparations to reduce foam, caking, corrosion, microorganism growth etc.
Kind of clothing agent composition for example, can contain helpful composition and be adhered to preparation (for example mineral oil) on the seed.
Liquid dispersant or emulsion can be by being dissolved in activeconstituents in the organic solvent that contains wetting, dispersion or emulsifying agent arbitrarily, then said mixture joined in the water that also can contain wetting, dispersion or emulsifying agent and make.The solvent that is fit to is acetone, ethylene dichloride, Virahol, propylene glycol, Pyranton, toluene, kerosene, methylnaphthalene, dimethylbenzene and the trichloroethane auxiliary agent together with other.Solubleness less than 0.1% be suitable for suspension concentrate, 0 ℃ of following strong solution more stably competing phase separate." McCutcheon ' s Detergents and Emulsifiers Annual ", MC Publishing Corp., Ridgewood, N.J., and Sisely and Wood, " Encyclopedia of Surface Active Agents ", Chemical Publishing Co., Inc., New York has listed the purposes of tensio-active agent and recommendation in 1964.
The method for preparing above-mentioned composition is known.Can prepare solution by mixing each composition simply.By mixing, in sledge mill or fluid energy mill, grind usually and prepare thin solids composition.By wet-milling (as referring to Littler, U.S. Patent number 3,060,084) prepare suspension.By preparing granule and tablet to active substance spray cloth at the ready-formed particulate vector or by the technology of condensing.
Now illustrate the synthetic method and the biologic activity of general formula 1 compound by following non-restrictive example.
Embodiment 1
2-(1-(4-phenyl benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1, the preparation of 3-diketone (compound 1.39)
(a) 4-phenylbenzyl chlorine
Thionyl chloride (11.8ml) is added drop-wise to ice bath refrigerative 4-phenylbenzyl alcohol (10.9g) 1, in the suspension of the stirring in the 2-ethylene dichloride (25ml).At room temperature stirred solution is 2 hours, refluxes then 1 hour, removes under reduced pressure and desolvates and excessive reagent, does not need further purification residue can be used for next procedure.
(b) phthalimide N-(4-phenyl benzyloxy)
At N, the thick chloride soln of dinethylformamide (DMF) in (20ml) joins the adjacent dicarboximide (9.7g) of N-oxybenzene and the N of stirring, the DMF(30ml of N-diisopropyl ethyl amine (15.4g)) in the solution.20 ℃ placed 48 hours and 45 ℃ place 48 hours after water (100ml) diluted mixture thing and filter it.Water thorough washing residue obtains white solid product (13.8g), and m.p.196-7 ℃, δ (CDCl 3And CH 3COOH), 5.3, s, CH 2; 7.2-7.6, m, 9ArH and 7.76, s, 4 ArH.
(c) 2-butyryl-5,5-dimethyl cyclohexane-1,3-diketone
Three-N-propyl group amine (31.5g) is added drop-wise to 5,5-dimethyl cyclohexane-1,3-diketone (14g), butanoic anhydride (17.4g) and N, N-(4-dimethylamino) in the mixture of pyridine (1g), at room temperature stirred the mixture 16 hours.This solution of cooling in ice also uses ether (x3) to extract with the hcl acidifying of 2N to pH3.Wash the ether extract of merging with water, drying, decompression removes down and desolvates.1mm pressure and 50 ℃ of following heating to remove butyric acid residual in the product and butanoic anhydride fully, residue does not need further purification promptly to can be used for next procedure.
(d) 2-(1-(4-phenyl benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone
N, N-diethyl ethylene diamine (1g) joins N-(4-phenyl benzyloxy) in the suspension of the stirring of phthalimide (2.2g) in ethanol (24ml).After forming settled solution, add butyric acid compound (1.3g), solution is buffered to pH4 by adding Glacial acetic acid.Under 20 ℃ reaction was reduced pressure after 16 hours down, remove and desolvate, with dilute hydrochloric acid residue is acidified to pH2-3, use ether (3x) to extract then, wash the ether extract of merging with water, ether is removed in evaporation, with silica gel chromatography purifying residue, obtains colorless solid product (1.3g), m.p.49-51 ℃, δ (CDCl 3) 0.98, t, J 7 Hz, CH 3CH 2; 1.05, s, 2xCH 3; 1.3-1.7, m, 2H, CH 2CH 3; 1.2,1.35, s, s, ring CH 2; 2.85-3.05, m, CH 2CH 2CH 3; 5.05, s, ArCH 2And 7.3-7.65, m, 9ArH.
Embodiment 2
2-(1-4-(4-fluorophenyl) benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1, the preparation of 3-diketone (compound 1.43)
(a) 4-methyl isophthalic acid-(4-fluorophenyl) hexalin
1-bromo-4-fluorobenzene (25g) and magnesium (3.5g) is added in is cooled to 0 ℃ of preparation Grignard reagent in the ether (200ml), dropwise add 4-methylcyclohexanone (16g) and handle it, stirred these mixtures 15 minutes down, refluxed then 30 minutes at 20 ℃.Solution is poured in saturated ammonium chloride (200ml) solution, extracted mixture and use Anhydrous potassium carbonate thorough drying extract with ether (3x50ml).Decompression is removed the crude product (25.5g) that ether stays light yellow oily down, does not need further purification directly to use it for next procedure.
(b) toluene 4-(4-fluorophenyl)
The alcohol (25.5g) that obtains as stated above is dissolved in the formic acid (98%), and solution stirring is spent the night.Mixture is poured in the water, and the tetrahydrobenzene that (3x50ml) dehydration of alcohols is generated extracts in the ether (3x50ml).Earlier use sodium bicarbonate aqueous solution, wash ether extract with salt then, use at last the anhydrous magnesium sulfate thorough drying it.After ether is removed in evaporation, sulphur (7.7g) is joined in the residue and with mixture to descend to heat at 180-200 ℃, up to further not emitting hydrogen sulfide (about 4 hours).The dark-brown reaction mixture was stirred 1 hour in methyl alcohol (200ml), remove by filter sulphur excessive in the mixture then.Evaporation is used the recrystallizing methanol residue after removing and desolvating, and obtains product (6g), and m.p.75-79 ℃, δ (CDCl 3) 2.42, s, CH2 and 7.0-7.7, m, 8 ArH.
(c) N-(4-fluorophenyl)-the benzyloxy phthalimide
The 4-(4-fluorophenyl) toluene (5.9g) and N-bromosuccinimide (6.2g) refluxed 8 hours in containing the tetracol phenixin of dibenzoyl peroxide (100ml).Make the mixture cool to room temperature, filter and under reduced pressure remove and desolvate.Rough bromotoluene is dissolved in DMF(20ml), and this solution joined N-hydroxyl phthalimide (4.6g) and N, N-diisopropylethylamine (7.4g) is at DMF(20ml) in mixture in.Stirred solution is 48 hours under the room temperature, adds entry (50ml) and makes the product precipitation, filters it then.Wash throw out with ethanol, and from chloroform recrystallization, obtain the phthalimide (8.2g) of colourless crystallization, m.p.161-163 ℃, δ (CDCl 3) 5.2, CH 2And 7.0-7.9, m, 12 ArH.
(d) butylidene 2-(1-(4-(4-fluorophenyl) benzyloxy amino))-5,5-dimethyl cyclohexane 1,3-diketone (compound 1.43)
N, N-diethyl ethylene diamine (0.5g) joins the N-(4-fluorophenyl of stirring) in the suspension of benzyloxy phthalimide (1g) in ethanol (12ml).After forming settled solution, (1c 0.6g), is buffered to pH4 through adding Glacial acetic acid with reaction mixture to add rough triketone.After 24 hours, volatile matter is removed in decompression, and residue is stirred to (50ml) and usefulness ether extraction gained mixture in the water.Wash ether extract with salt, ether is removed in dry and evaporation.With the abundant purifying residue of silica gel chromatography,, obtain light yellow oily product (0.6g), δ (CDCl with ethyl acetate-petroleum naphtha (1: 20) wash-out 3) 0.8-1.2, m, 2XCH 3And CH 2CH 3; 1.4-1.7, M, CH 2CH 3; 2.2,2.4, s, s, 2X encircles CH 2; 2.8-3.1, m, CH 3CH 2CH 2; 5.06, s ArCH 2And 7.0-7.7, M, 8 ArH.
Embodiment 3
Adopt above-mentioned general method, preparation is the compound shown in the tabulation 1 down; Their fusing point and characteristic nuclear magnetic resonance spectrum after the compound sequence number, have been provided.
Compound 1.1 m.p.70 ℃, CDCl 3, δ 0.98, t, J7Hz, CH 3; 1.4-2.1, m,
CH 3CH 2And CH 2CH 2CH 2; 2.2-2.7, m, CH 2CH 2CH 2; 2.9, t, J7Hz; CH 2CH 2CH 3;
5.1.s.CH 2Ar and 7.3-7.7, m, 9ArH
Compound 1.2 m.p.122 ℃, CDCl 3, δ 0.96, t, J7Hz, CH 3; 1.2-2.0, m,
CH 3CH 2And CH 2CH 2CH 2; 2.3-2.7, m, CH 2CH 2CH 2; 2.9, t, J7Hz, CH 2CH 2CH 3;
5.1.s.CH 2Ar and 7.3-7.7, m, 8ArH
Compound 1.15 oil, CDCl 3, δ 0.85-1.1, m, CH 3CH 2And CH 3CH; 1.4-1.8,
M, CH 3CH 2; 1.9-2.7, m, CH 3CH and 2xCH 2CO; 2.95, t, J7Hz, CH 3CH 2CH 2; 5.1,
S, CH 2Ar and 7.3-7.7, m, 9ArH
Compound 1.16 oil, CDCl 3,δ 0.88, t, J7Hz, CH 3CH 2; 1.04, d, J3Hz, CH 3CH
; 1.3-2.6, m, CH 3CH 2, 2xCH 2CO and CH 3CH; 2.92, t, J7Hz, CH 3CH 2CH 2; 5.1, s,
CH 2Ar and 7.0-7.6, m, 8ArH
Compound 1.25 oil, CDCl 3, δ 0.85-2.4, m, the H of 15 aliphatic series; 2.9, t, J7Hz,
CH 3CH 2CH 2; 5.05, s, CH 2Ar and 7.3-7.8, m, 9 ArH
Compound 1.35 colorless oil, CDCl 3, δ 0.96, s, 2xCH 3; 1.06, t, J7Hz,
CH 3CH 2; 2.1-2.4, m, 2xCH 2CO; 2.9, t, J7Hz, CH 3CH 2; 5.0, s, CH 2Ar and 7.2-7.7, m, 9 ArH
Compound 1.38 oily CDCl 3, δ 0.94, s, 2xCH 3; 0.92, t, J7Hz, CH 3CH 2; 1.3-
1.7, m, CH 3CH 2; 2.2 with 2.4 single wide s, 2xCH 2CO; 2.9, t, J7Hz, CH 3CH 2CH 2;
5.04, s, CH 2Ar and 7.0-7.6, m, 9ArH
Compound 1.44 oil; CDCl 3, δ 0.92, t, J7Hz, CH 3CH 2; 1.04, s, 2xCH 3; 1.35-
1.7, m, CH 3CH 2; 2.31, wide s, 2xCH 2CO; 2.91, t, J7Hz, CH 3CH 2CH 2; 4.65, d
J5Hz, CH 2Ar, 6.1-7.5, m, CH=CH and 4ArH
Compound 1.48 oil; CDCl 3, δ 0.96, t, J7Hz, CH 3CH 2; 1.08, s, 2xCH 3; 1.4-
1.8, m, CH 3CH 2; 2.32 with 2.42, single wide s, 2xCH 2CO; 2.95, t, J7Hz,
CH 3CH 2CH 2; 4.88, d, J5Hz, CH 2Ar and 6.15-7.6, m, 3 ArH and CH=CH
Compound 1.55 oil; CDCl 3, δ 0.72-1.08,2t, 2xCH 3CH 2; 1.07, s, 2xCH 3;
1.2-1.8, m, 2xCH 3CH 2; 2.34, wide s, 2xCH 2CO; 3.01, t, J7Hz, CH 3CH 2CH 2; 5.12, s, CH 2Ar and 7.01-7.7, m, 8 ArH
Compound 1.56 oil; CDCl 3, δ 0.72-1.04,2t, 2xCH 3CH 2; 0.98, s, 2xCH 3;
1.2-1.7, m, 2XCH 3CH 2; 2.32, wide s, 2xCH 2CO; 2.92, t, J7Hz, CH 3CH 2CH 2; 4.67, d, J5Hz, CH 2Ar and 6.1-7.5, m, 3ArH and CH=CH
Compound 1.96 oil; CDCl 3, δ 0.85-1.05, m, CH 3CH 2And CH (CH 3) 2; 1.3-
1.7, m, CH 3CH 2, 2xCH 2CO and CH-CH; 2.94, t, J7Hz, CH 3CH 2CH 2; 5.1, s,
CH 2Ar and 7.0-7.6, m, 8ArH
Compound 1.107 oil; CDCl 3, δ 0.8-1.2, m, 3xCH 3And CH 3CH 2; 1.4-2.7, m,
CH 3CH 2, 2xCH 2CO and CH; 3.0, t, J7Hz, CH 3CH 2CH 2; 5.15, s, CH 2Ar and 7.1-
7.7,m,8ArH
Compound 1.116 oil; CDCl 3, δ 0.94, t, J7Hz, CH 3CH 2; 1.04, s, 2xCH 3; 1.4-1.8, m, CH 3CH 2; 2.33, wide s, 2xCH 2CO; 2.93, t, J7Hz, CH 3CH 2CH 2; 4.65, d, J5Hz, CH 2Ar, 6.1-6.8, m, CH=CH and 7.3, s, 4ArH
Compound 1.117 oil; CDCl 3, δ 1.14, s, 2xCH 3, 2.32 and 2.42, single wide s, 2x
CH 2CO; 2.44, s, CH 3; 4.78, d, J5Hz, CH 2Ar and 6.15-7.6, m, 3ArH and CH=CH
Compound 1.118 oil; CDCl 3, δ 1.07, t, J7Hz, CH 3CH 2; 1.04, s, 2xCH 3; 2.3 with 236, single wide s, 2xCH 2CO; 2.92, t, J7Hz, CH 3CH 2; 4.68, d, J5Hz, CH 2Ar and
6.15-7.5, m, 3ArH and CH=CH
Compound 1.119 oil; CDCl 3, δ 0.92, t, J7Hz, CH 3CH 2; 1.08, s, 2xCH 3; 1.3-1.7, m, CH 3CH 2CH 2CH 2; 2.26 with 2.38, single wide s, 2xCH 2CO; 2.95, t, J7Hz,
CH 3CH 2CH 2CH 2; 4.69, d, J5Hz, CH 2Ar and 6.15-7.6, m, 3ArH and CH=CH
Compound 1.120 oil; CDCl 3, δ 1.08, s, 2xCH 3; 2.47, s, 2xCH 2CO; 2.49, s, CH 3;4.67, d, J5Hz, CH 2Ar, and 6.15-7.6, m, 3ArH and CH=CH
Compound 1.121 oil; CDCl 3, δ 0.96, t, J7Hz, CH 3CH 2; 1.58,1.64, s, s, 2xCH 3; 2.1-2.6, m,, 2xCH 2CO and CH; 2.94, t, J7Hz, CH 3CH 2; 5.06, s, CH 2Ar and 7.2-7.6, m, 9ArH
Compound 1.122 oil; CDCl 3, δ 0.93, t, J7Hz, CH 3CH 2; 1.06, s, 2xCH 3; 1.4-
1.8, m, CH 3CH 2; 2.36, s, 2xCH 2CO; 2.93, t, J7Hz, CH 3CH 2CH 2; 4.75, d, J5Hz, CH 2Ar, 6.1-7.9, m, CH=CH and 4ArH
Compound 1.123 oil; CDCl 3, δ 0.96, t, J7Hz, CH 3CH 2; 1.2-2.5, m, 2xCH 2CO; CH 3CH 2And CHCH 2; 2.93, t, J7Hz, CH 3CH 2CH 2; 3.32, s, OCH 3; 3.39, t, J5Hz,
CH 2COCH 3; 5.06, s, CH 2Ar and 7.2-7.6, m, 9 ArH
Compound 1.124 oil; CDCl 3, δ 0.97, t, J7Hz, CH 3CH 2; 1.08, s, 2xCH 3; 1.4-
1.8,m,CH 3CH 2;1.88,s,CH 3;2.36,s 2xCH 2CO;2.93,t,J7Hz,CH 3CH 2CH 2;
4.61, s, CH 2Ar, 6.47, s, C=CH and 7.3, s, 4ArH
Compound 1.125 oil; CDCl 3, δ 0.95, t, J7Hz, CH 3CH 2; 1.13, s, 2xCH 3; 1.4-
1.7,m,CH 3CH 2;1.83, s,CH 3;2.37,s,2xCH 2CO;2.93,t,J7Hz,CH 3CH 2CH 2;
4.54, s, CH 2Ar; 6.51, s, C=CH and 6.9-7.4, m, 4ArH
Compound 1.126 oil; CDCl 3, δ 0.95, t, J7Hz, CH 3CH 2; 1.03, s, 2xCH 3; 1.4-
1.7, m, CH 3CH 2; 2.07, s, CH 3; 2.35, s, 2xCH 2CO; 2.92, t, J7Hz, CH 3CH 2CH 2; 4.69, d, J5Hz, CH 2Ar, 5.87, t, J5Hz, C=CH and 7.29, s, 4ArH
R among the following example explanation preparation the present invention 1It or not the general method of the compound of hydrogen.
Embodiment 4
(a) butylidene 2-(1-(3-(2,4-dichlorophenyl) allyloxy amino))-5,5-dimethyl cyclohexane-1, the preparation of 3-diketone (compound 1.47)
At room temperature stir N-(3-(2,4-dichlorophenyl) allyl group) oxo phthalimide (0.7g) and N, the mixture of N-diethyl ethylene diamine (0.35g) in ethanol (8ml) is up to forming clear soln.Add 2-butyryl radicals-5,5-dimethyl cyclohexane-1,3-diketone (0.42g) is adjusted to pH4 to mixture through adding acetate.After at room temperature reacting 16 hours, ethanol is removed in decompression, and residue is dissolved in ether and uses 5% sodium hydroxide extraction.With dilute hydrochloric acid alkaline extract is acidified to pH4, with the collected organism of ether extraction and through silicon gel layer analyse abundant purifying it, obtain colorless oil product (22mg), CDCl after removing ether 3, δ 0.98, t, J7Hz, CH 3CH 2; 1.04, s, 2X CH 3; 1.4-1.7, m, CH 3CH 2; 2.32 wide s, 2X CH 2CO; 2.94, t, J7Hz, CH 3CH 2CH 2; 4.69, d, J5Hz, CH 2Ar and 6.1-7.5, m, 3 ArH and CH=CH.
(b) butylidene 2-(1-(3-(2,4-dichlorophenyl) allyloxy amino))-5, the preparation of 5-dimethyl-1-phenyl sulfonyloxy hexamethylene-1-alkene-3-ketone (compound 2.1)
Stir down to the interior benzene sulfonyl chloride that adds of pyridine (1.5ml) solution that is cooled to 0 ℃ oxime (7.8g is by above-mentioned (a) described method preparation).Reaction was used aqueous citric acid solution (20ml, 20%) diluted reaction mixture after 24 hours under the room temperature, and extracted with ether (3x).After ether was removed in evaporation, residue obtained colorless oil product (0.62g), CDCl through the abundant purifying of silica gel column chromatography 3, δ 0.82, t, J7Hz, CH 3CH 2; 1.02,1.04, s, s, 2X CH 3; 1.2-1.5, m, CH 3CH 2; 2.15, t, J7Hz, CH 3CH 2CH 2; 2.32 with 2.79, single s, 2X CH 2CO; 4.58, d .J5Hz, CH 2Ar and 6.1-7.9, m, 8 ArH and CH=CH.
Embodiment 5
(a) butylidene 2-(1-(4-phenyl) benzyloxy amino))-5, the preparation of 5-dimethyl-1-phenyl sulfonyloxy hexamethylene-1-alkene-3-ketone (compound 2.2)
Employing the foregoing description 4(b) method, make 2-(1-(4-phenyl) benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone (compound 1.39) and benzene sulfonyl chloride reaction, generate the title compound of colorless oil, nuclear magnetic resonance spectroscopy result: CDCl 3, δ 0.81, t, J7Hz, CH 2CH 2CH 3; 1.12, s, 2X CH 3; 1.2-1.6, m, CH 2CH 2CH 3; 2.3, t, J7Hz, CH 2CH 2CH 3; 2.31,2.78, single s, 2X CH 2; 5.01, s, CH 2Ar and 7.2-7.9, m, 14ArH.
Embodiment 6
In order to confirm formula of the present invention (1) compound as the validity of weedicide, table 2 show with 0.1 and the ratio of 0.4kg/ hectare use the test-results of formula (1) compound before to barnyard grass and rice seedling.The data of weeding are shown in Table 2.0 expression does not have effect in the table, 10 expression plant death.Although a few compounds, particularly 1.48 and 1.118 have enough activity of killing paddy rice under experimental concentration, it can also be seen that formula (1) compound can optionally control the barnyard grass grass in the rice field.Second shaker test adopted lower usage ratio (30 and 60g/ hectare), the selectivity that these compounds all demonstrate.
Table 2
Compound (0.1Kg/ hectare) (0.4Kg/ hectare)
(table 1) barnyard grass paddy rice barnyard grass paddy rice
1.15 10 1 10 8
1.16 10 1 10 4
1.25 9 2 10 1
1.35 9 2 9 1
1.38 9 0 10 0
1.39 9 2 9 2
1.43 10 3 10 8
1.44 9 10 2 8
1.48 10 9 10 8
1.55 9 1 9 3
1.56 9 2 10 6
1.96 10 0 10 2
1.116 10 6 10 9
1.117 9 2 10 5
1.118 10 8 10 9
1.119 3 0 5 0
1.120 9 1 10 7
1.121 9 1 10 0
1.122 9 5 9 6
1.123 10 2 10 4
1.124 10 2 10 7
1.125 10 2 10 8
1.126 10 1 10 4
Table 3
Compound (public of 0.03Kg/) (0.06Kg/ hectare)
(table 1) barnyard grass paddy rice barnyard grass paddy rice
1.48 9 0 10 2
1.118 10 0 10 0

Claims (26)

1, formula (I) compound and their isomer and/or change form:
Wherein
A is selected from C 1-C 3Alkylidene group and C 3Alkylene group, wherein each group can be selected from C alone by 1-4 1-C 3Alkyl substituent at random replaces;
X is selected from group 0, and singly-bound;
R 1Be selected from H, C 1-C 4Alkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl group; C 5-C 6Cycloalkyl, C 5-C 6Cycloalkenyl, chain triacontanol base, fragrant and mellow base, C 1-C 4Alkyl sulphonyl, aryl sulfonyl, benzenesulfonyl, C 1-C 4Alkyl-carbonyl, C 2-C 8Alkoxyalkyl, C 2-C 8Alkyl-thio-alkyl, C 7-C 10Phenylalkyl, M and can be selected from down the phenyl that substituting group that group comprises replaces arbitrarily by 1-3, this organizes substituting group is halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl, amino, and C 1-C 4Halogenated alkoxy;
R 2Be selected from C 1-C 6Alkyl, C 2-C 6Alkenyl, C 2-C 6Alkynyl group, C 1-C 4Haloalkyl, C 1-C 4Alkylthio, C 3-C 6Cycloalkyl, C 5-C 6Cycloalkenyl, C 2-C 8Alkoxyalkyl, C 2-C 8Alkyl-thio-alkyl is selected from following one group of substituting group that comprises, the C of replacement 1-C 4Alkyl, these substituting groups are phenyl, phenoxy group and sulfo-phenoxy group, and wherein said substituent aromatic ring can be selected from halogen, C by 1-3 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, amino, C 1-C 4Haloalkyl and C 1-C 4The substituting group of halogenated alkoxy replaces arbitrarily and can be by 1-3 phenyl that is selected from any replacement of following one group of substituting group that comprises, this group substituted radical is a halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl, amino, and C 1-C 4Halogenated alkoxy;
R 3And R 4Be selected from H respectively, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, and cyano group, or R 3Or R 4One of separately with R 5And R 6In one link together by ring carbon atom, form 5-or 6-unit ring;
R 5And R 6Be selected from H respectively, C 1-C 6Alkyl, C 2-C 4Alkenyl, C 2-C 8Alkyl-thio-alkyl, C 1-C 4Haloalkyl, C 2-C 4Halogenated alkenyl, C 3-C 6Cycloalkyl, alkyl wherein, alkenyl and cycloalkyl can at random be replaced by 1-3 substituting group that is selected from down group respectively, and these substituted radicals comprise OR 12, NR 13R 14, NR 15CO-(C 1-C 4Alkyl), NR 18SO 2(C 1-C 4Alkyl), C (OR 16) (OR 17) R 22, C (SR 19) (SR 20) R 23, C 1-C 4Carbalkoxy and can be selected from halogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, nitro, cyano group, C 1-C 4Haloalkyl and C 1-C 4The phenyl that the substituting group of haloalkoxy alkyl replaces arbitrarily; Or
R 5And R 6Be connected to form saturated or unsaturated 3-to 7-unit carbocyclic ring with ring carbon atom, saturated or undersaturated 5-is to 7-unit heterocycle, and this heterocycle contains individual being selected from of 1-3 and comprises 0-3 nitrogen, the heteroatoms of 0-2 oxygen and 0-2 sulphur atom; Carbocyclic ring or heterocycle can be selected from halogen, C respectively by 1-4 1-C 4Alkyl, C 1-C 4Haloalkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl group, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, C 1-C 4Carbalkoxy ,-COOH, C 2-C 8Alkoxyalkyl, C 2-C 8Alkyl-thio-alkyl and can be selected from halogen, C by one 1-C 4Alkoxyl group, C 1-C 4Alkylthio, C 1-C 4Haloalkyl, nitro, cyano group and C 1-C 4The substituting group of the phenyl that the substituting group of halogenated alkoxy at random replaces replaces, and carbon atom of carbocyclic ring and heterocyclic can be at random with carbonyl or its corresponding dimethyl, and the form of diethyl or ethene or propylene ketal exists;
R 7, R 8And R 9Be selected from H respectively, halogen; C 1-C 4Alkyl; C 1-C 4Alkoxyl group, C 1-C 4Alkylthio; C 1-C 4Alkyl sulphinyl; C 1-C 4Alkyl sulphonyl, C 1-C 4Haloalkyl; C 1-C 4Halogenated alkoxy; Nitro; Cyano group; C 1-C 4Carbalkoxy; C 1-C 4Alkyl amino-carbonyl; C 2-C 6Dialkyl amino carbonyl; Aminocarboxyl; Amino; C 2-C 4Alkylamino; And C 2-C 6Dialkyl amido; Or be selected from benzenesulfonyl, and benzoyl, benzyl, benzyloxy, pyridyl, phenoxy group, the phenyl sulfo-, phenyl amino and phenyl groups, described group can be selected from halogen, C respectively by 1-3 1-C 4Alkyl, C 1-C 4Alkoxyl group and CF 3Substituting group replace arbitrarily;
M is selected from Li +, Na +, K +, NH 4 +, and N (R 11) 4 +Group,
R wherein 11Be C 1-C 4Alkyl;
R 12Be selected from H, C 1-C 4Alkyl, benzyl, CO (C 1-C 4Alkyl) and
CO 2(C 1-C 4Alkyl) group;
R 13, R 15, R 18, R 22And R 23Be selected from H and C respectively 1-C 3Alkyl;
R 14, R 16, R 17, R 19And R 20Be selected from C respectively 1-C 3Alkyl;
R 16And R 17Can be connected into together-(CH 2) 2-or-(CH 2) 3-, and
R 19And R 20Can be connected into together-(CH 2) 2-or-(CH 2) 3-;
Condition is:
A) when A be CH 2And X is singly-bound, and R 1Be H, C 1-C 4Alkyl-carbonyl, aryl carbonyl or M, R 2Be C 1-C 6Alkyl or phenyl, R 3And R 4Be H, R 5And R 6Be H, C 1-C 3Alkyl or C 2-C 8During alkyl-thio-alkyl, R at least then 7, R 8And R 9In one be not H, CF 3, nitro or halogen.
B) when A be C 2-C 3Alkylidene group, X are O, R 1Be H, R 2Be C 3Alkyl, R 3And R 4Be H, R 5And R 6Be CH 3The time, R at least then 7, R 8And R 9In one be not H;
C) when A be CH 2, or by 1-3 C 1-C 3The C that alkyl group replaces arbitrarily 3Alkylidene group or C 3Alkylene group, and X is singly-bound, R 1Be H, R 3And R 4Be H, R 5And R 6In one be that hydrogen and another are C 2-C 8Alkyl-thio-alkyl is by O (C 1-C 4Alkyl) C of Qu Daiing 1-C 4Alkyl, or by OR 12Any C that replaces 3-C 6Cycloalkyl, wherein R 12Be C 1-C 4When alkyl or H, R at least then 7, R 8Or R 9In one be not H, halogen, nitro, cyano group, C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Haloalkyl, C 1-C 4Halogenated alkoxy, C 1-C 4Carbalkoxy or the phenyl that replaces arbitrarily.
2, according to formula 1 compound of claim 1, R wherein 1Be H, alkyl sulphonyl, aryl sulfonyl or M; And R 2Be C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 2-C 4Alkenyl or C 2-C 4Alkynyl group.
3, according to formula 1 compound of claim 2, wherein A is C 1-C 2Alkylidene group or by CH 3Or C 2H 5Any C that replaces 3-C 4Alkylidene group;
R 7, R 8And R 9Be respectively H, Cl, Br, F, C 1-C 3Alkyl, C 1-C 3Alkoxyl group, C 1-C 3Alkylthio, C 1-C 3Haloalkyl, C 1-C 3Halogenated alkoxy, nitro, cyano group or C 1-C 3Carbalkoxy; Or can be selected from halogen, C by 1-3 1-C 4Alkyl, C 1-C 4Alkoxyl group or CF 3The benzenesulfonyl that replaces arbitrarily of substituting group, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl sulfo-or phenylamino.
4, according to formula 1 compound of claim 3, wherein X is 0.
5, according to formula 1 compound of claim 3, wherein X is a singly-bound.
6, according to formula 1 compound of claim 5, wherein
A is-CH 2-,-CH 2CH 2-,-CH 2CH=CH-or-CH 2CMe=CH-;
R 1Be H, Li +, Na +Or K +;
R 2Be CH 3, C 2H 5, n-C 3H 7Or n-C 4H 9;
R 3And R 4Be respectively H, CH 3Or C 2H 5; And
R 7, R 8And R 9Each is H naturally, Cl, Br, F, CH 3, C 2H 5, OCH 3, OC 2H 5, SCH 3, SC 2H 5, CF 3, CHF 2, CF 2CF 3, OCHF 2, OCF 3, OCH 2CF 3, NO 2, CN, CO 2CH 3, Ph, SO 2PH, COPh, CH 2Ph, OCH 2Ph, OPh, SPh, NHPh or N(Me) Ph.
7, according to formula 1 compound of claim 5, R wherein 5And R 6Each is C naturally 1-C 4Alkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl group, C 1-C 4Alkylthio or C 2-C 6Alkyl-thio-alkyl.
8, according to formula 1 compound of claim 5, R wherein 5And R 6Be connected to form saturated or unsaturated 5-with carbon atom, 6-or 7-unit carbocyclic ring, this ring can be replaced arbitrarily by 1-4 methyl group.
9, formula 1 compound according to Claim 8, wherein
A is-CH 2-,-CH 2CH 2-,-CH 2CH=CH-or-CH 2CMe=CH-; R 1Be H, Li +, Na +Or K +; R 2Be CH 3, C 2H 5, n-C 3H 7Or n-C 4H 9; R 3And R 4Each is H or CH naturally 3; And
R 7, R 8And R 9Each is H naturally, Cl, Br, F, CH 3, C 2H 5, OCH 3, OCH 2H 5, SCH 3, SC 2H 5, CF 3, CHF 2, CF 2CF 3, OCHF 2, OCF 3, OCH 2CF 3, NO 2, CNCO 2CH 3, Ph, SO 2Ph, COPh, CH 2Ph, OCH 2Ph, OPh, SPh, NHPh or N(Me) Ph.
10, according to formula 1 compound of claim 5, R wherein 5And R 6Be connected to form with carbon atom and contain 1-2 heteroatomic saturated or undersaturated 5-, 6-or 7-unit heterocycle, heteroatoms is selected from and comprises 0-2 nitrogen, the group of 0-1 oxygen and 0-2 sulphur atom, described ring can be by 1-4 CH 3Group at random replaces.
11, according to formula 1 compound of claim 10, wherein:
A is-CH 2-,-CH 2CH 2-,-CH 2CH=CH-or-CH 2CMe=CH-;
R 1Be H, Li +, Na +Or K +;
R 2Be CH 3, C 2H 5, n-C 3H 7Or n-C 4H 9;
R 3And R 4Each is H naturally, CH 3Or C 2H 5; And
R 7, R 8And R 9Each is H naturally, Cl, Br, F, CH 3, C 2H 5, OCH 3, OC 2H 5, SCH 3, SC 2H 5, CF 3, CHF 2, CF 2CF 3, OCHF 2, OCF 3, OCH 2CF 3, NO 2, CN, CO 2CH 3, Ph, SO 2Ph, COPh, CH 2Ph, OCH 2Ph, OPh, SPh, NHPh or N(Me) Ph.
12,2-(1-(4 phenyl benzyloxy amino) butylidene)-5,5-dimethyl cyclohexane-1,3-diketone.
13, butylidene 2-(1-(4-(4 oxygen phenyl) benzyloxy amino))-5,5-dimethyl-hexanaphthene-1,3-diketone.
14, butylidene 2-(1-(3-(2,4-dichlorophenyl) allyloxy amino))-5,5-dimethyl cyclohexane-1,3-diketone.
15, butylidene 2-(1-(3-(2,4-difluorophenyl) allyloxy amino))-5,5-dimethyl cyclohexane-1,3-diketone.
16, butylidene 2-(1-(4-(4-fluorophenyl) benzyloxy amino))-and 5-normenthane-1, the 3-diketone.
17, propylidene 2-(1-(3-(2,4-dichlorophenyl) allyloxy amino))-5,5-dimethyl cyclohexane-1,3-diketone.
18, butylidene 2-(1-(3-(2,4-dichlorophenyl) allyloxy amino))-5,5-dimethyl-1-phenyl sulfonyloxy hexamethylene-1-alkene-3-diketone.
19, butylidene 2-(1-(4-phenyl) benzyloxy amino))-5,5-dimethyl-1-phenyl sulfonyloxy hexamethylene-1-alkene-3-diketone.
20, listed any compound in the table 1.
21, plant growth regulating, plant damage or plant are killed and wounded composition, it is characterized in that containing in the composition formula (1) compound and its inert carrier of with good grounds claim 1 definition.
22, the method for coordinate plant growth is characterized in that plant, the seed of plant, or the growth medium of plant is used formula (1) compound according to claim 1 definition of significant quantity.
23, in crop, optionally suppress, damage or kill and wound the method for gramineous weeds, it is characterized in that doing or formula (1) compound according to claim 1 definition of significant quantity is used in its growth place.
24, herbicidal composition is characterized in that containing in the composition formula (1) compound and at least a other weedicide that root claim 1 defines.
25, plant growth regualting composition is characterized in that containing in the composition formula (1) compound and its inert carrier that with good grounds claim 1 defines.
26, formula (1) compound is as the purposes of weedicide or plant-growth regulator.
CN92114386A 1991-11-15 1992-11-14 Herbicidal cyclohexanes Pending CN1073675A (en)

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DE19510183A1 (en) * 1994-03-31 1995-10-05 Basf Ag New imino:alkyl-aminomethyl-cyclohexenone derivs.
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