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WO1997037981A1 - Procede de production d'oxazolidine-2,4-diones - Google Patents

Procede de production d'oxazolidine-2,4-diones Download PDF

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Publication number
WO1997037981A1
WO1997037981A1 PCT/EP1997/001425 EP9701425W WO9737981A1 WO 1997037981 A1 WO1997037981 A1 WO 1997037981A1 EP 9701425 W EP9701425 W EP 9701425W WO 9737981 A1 WO9737981 A1 WO 9737981A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
aryl
formula
process according
iii
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.)
Ceased
Application number
PCT/EP1997/001425
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German (de)
English (en)
Inventor
Lutz Heuer
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 AG
Original Assignee
Bayer AG
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 filed Critical Bayer AG
Priority to AU21588/97A priority Critical patent/AU2158897A/en
Publication of WO1997037981A1 publication Critical patent/WO1997037981A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D263/44—Two oxygen atoms

Definitions

  • the present invention relates to a particularly advantageous and simple to carry out process for the preparation of oxazolidine-2,4-diones from amides and
  • R, R 2 and R are the same or different and each for one of the following
  • OCF 3 OCF 2 H, OCFH 2 , OCF 2 CF 3 , OCH 2 CF 3 , OCO (C r C 12 alkyl or C 6 -C 10 aryl), OP (C, -C 12 alkyl or C 6 -C, 0 -aryl) 3 , OP (OC, -C 10 - alkyl or O- (C 6 -C 10 - or C 6 -C 10 aryl) can be substituted
  • R 2 and K ⁇ can independently represent hydrogen
  • X represents halogen may, for example, a sulfonate group or one or more sulfonate group-containing radical preferably stands for chlorine, bromine, C, -C 4 alkyl phenyl sulfonate, tosylate, perfluoro-C r C 4 -alkylsulfonate, T ⁇ fluormethanesulfonat or mesylate
  • R 1 has the meaning given for formula (1), or of the formula (III B)
  • n an integer from 2 to 30,
  • R 2 and R have the meaning given for formula (I) and X for formula (II) and
  • Y represents hydroxy, halogen, C, -C 6 alkoxy or C 6 -C 10 aryloxy or OCO-R,
  • Halogen can mean e.g. fluorine, chlorine, bromine or iodine
  • alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl,
  • alkoxy groups are methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy and
  • Dodecyloxy each of which can be straight-chain or branched and / or optionally substituted with fluorine.
  • hetaryl groups are pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl,
  • Amines of the formula (III B) are, for example: ethylene, butylene, hexylene, pentylene, octylene, decylene and dodecylene diamine, 1,4-diaminobenzene, 1,4'-benzidine,
  • hydrazine derivatives of the formula (V) can also be used, optionally in proportion
  • R and R ⁇ have the meaning given for formula (I).
  • Amides of the formula (II) in which R 1 , R 2 and R 1 independently of one another each represent one of the following radicals are preferred.
  • 0-C ⁇ -Q-alkyl or OC 6 -C 10 aryl N (C, -C 6 alkyl or C 6 -C 10 aryl) 2 , COO-C, -C 6 -Alkyl, COO-C 6 -C 10 -aryl, CONH- C, -C 6 -alkyl, CON (C, -C 6 -alkyl) 2 , OS (C r C 6 -alkyl or phenyl), O 2 S (C r C 6 - alkyl or phenyl), CHO, CN, OC (C r C 6 alkyl or phenyl), NO 2 , CF 3 , OCF 3 , OCF 2 H, OCFH 2 , OCO (C r C 6 - Alkyl or phenyl) or HNCO (C, -C 6 -alkyl or phenyl) may be substituted,
  • R 2 and / or R 3 can also represent hydrogen
  • Amides of the formula (II) in which R 1 represents one of the following radicals are particularly preferred: methyl, ethyl, n-propyl, l-propyl, butyl, cyclohexyl, phenyl, pyrazolyl, imidazolyl, pyrrolyl, furanyl, thienyl, py ⁇ dinyl, Quinolinyl, isoquinolinyl, quinazolyl, indolyl, benzyl, tolyl and xylyl, which are optionally once or twice by methoxy, ethoxy, phenyl, CHO, CN, Cl, F, Br, OCF 3 , OCF 2 H, C arb oxymethyl, carboxyethyl or NO 2 can be substituted and
  • the usual commercial product can be used as carbon dioxide in the process according to the invention.
  • isotope-enriched e.g. B 13 C and / or 14 C containing carbon dioxide can be used
  • R 2 and R 3 can also together stand for one of the following radicals in divalent form C, -C 30 alkyl, C 4 -C 12 cycloalkyl, C 5 -C 30 alkenyl, C 8 - C 30 alkynyl, C 7 -C 20 aralkyl, C 8 -C 20 aralkenyl, C 8 -C 20 alkenaryl and up to 3
  • Oxygen, sulfur and / or nitrogen atoms in the ring system contained C 5 - C ⁇ -Alkenhetaryl and C 5 -C, 3 -Alk ⁇ nhetaryl,
  • Oxygen, sulfur, N (C, -C 12 alkyl or C 6 -C 10 aryl) -, CO-, COO-, SO-, SO 2 - or SO (O) O- or OP (C ] -C 12 alkyl or C 6 -C 10 aryl) groups can be interrupted
  • amide equivalent used for example 0.01 to 10,000 equivalents of carbon dioxide can be used in the process according to the invention.
  • This ratio is preferably 1 0.5 to 1 1000, in particular 1 1 to 10
  • the basic compounds include, for example, basic salts, oxides, Hydrides and hydroxides in question. Examples include: lithium hydride, sodium hydride, potassium hydride, calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium oxide, sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, barium oxide, magnesium oxide, • strontium oxide,
  • Sodium sulfide, sodium hydrogen sulfide and / or their naturally occurring or synthetically obtainable mixtures such as, for example, dolimite or magnesium oxide carbonate and / or compounds which contain sodium or potassium metal in dispersed form on the corresponding carbonates.
  • Al potassium carbonates and / or hydrogen carbonates are preferred, very particularly preferably potassium carbonate.
  • the basic compounds can be used in anhydrous form or, in the case of salts which crystallize with water of hydration, also in hydrated form.
  • Anhydrous compounds are preferably used
  • the basic compounds can be used, for example, in amounts of 0.5 to 10 mol per mol of the amide of the formula (II) used. This amount is preferably in the range from 0.8 to 5 mol, particularly preferably in the range from 1 to 2.5 mol, in each case per mol of amide of the formula (II) used.
  • auxiliary bases i.e. in the presence of further bases, for example in an amount of less than 1.0 mol, preferably less than 0.5 mol, in each case based on 1 mol of the basic compound.
  • auxiliary bases are: halides of alkali metals, zeolites, potassium acetate, potassium formate, sodium acetate, titanium alkonates, titanium acid amides, amidine bases or guanidine bases such as 1,5-diazabicyclo-
  • the process according to the invention is carried out in the presence of solvents.
  • the solvent is advantageously used in such an amount that the reaction mixture remains readily stirrable throughout the process.
  • suitable solvents are hydrocarbons such as petroleum ether, benzene, toluene, chlorobenzene and dichlorobenzene , Hexane, cyclohexane, methane, cyclohexane, pentane, heptane, octane and technical hydrocarbon mixtures, for example so-called white spins with components with boiling points in the range from, for example, 40 to 250 ° C., ethers such as dimethyl, diethyl, dipropyl, diisopropyl , Dibutyl, methyl t-butyl ether, tetrahydrofuran, 1,4-dioxane and polyethers of ethylene oxide and / or propylene oxide, amines such as t ⁇ methyl, triethyl, t
  • Tetramethylethylenediamine esters such as methyl, ethyl and butyl acetate, as well as dimethyl, dibutyl and ethylene carbonate, nitro compounds such as nitromethane, nitroethane, nitropropane and nitrobenzene, nit ⁇ le such as acetonitrile, propionite and benzonite, as well as compounds such as tetrahydroth- thylene sulfoxide and dimethyl sulfoxide, diphenoxide and sulfonium oxide, dimethyl sulfoxide and dimethyl sulfoxide, diphenoxide and sulfonium oxide, dimethyl sulfoxide and diphenyl sulfoxide, diphenoxide and sulfonium oxide, dimethyl sulfoxide and diphenoxide, diphenoxide and sulfonium oxide, , Benzylmethyl sulfoxide, dnsobutyl sulfoxide, di
  • Preferred solvents are dimethylformamide and dimethyl sulfoxide and mixtures of these with other of the solvents mentioned
  • the process according to the invention is generally carried out by bringing the amide and the carbon dioxide together in the presence of a basic compound and a solvent and allowing them to react with one another
  • the process according to the invention can be carried out, for example, at temperatures of
  • the pressure is not critical in the process according to the invention. In principle, it is possible to work with normal pressure, but also with increased or reduced pressure.
  • the process is preferably carried out under normal pressure or with pressures of up to
  • the process according to the invention can be carried out under a carbon dioxide atmosphere, but also in an atmosphere which contains carbon dioxide and still other, preferably inert, gases.
  • a carbon dioxide atmosphere but also in an atmosphere which contains carbon dioxide and still other, preferably inert, gases.
  • this is preferably done in a closed vessel at the autogenous pressure which arises.
  • You can also work in supercritical carbon dioxide, but then you have to apply pressure of e.g. 80 to 200 bar
  • the process according to the invention has a number of surprising advantages. It allows the preparation of compounds of formula (I) in a technically simple, economically advantageous manner while avoiding the use of phosgene, chlorine, formic acid esters, isocyanates, carbamoyl chlorides and carbonates, which in many cases are entirely require considerable effort for plant safety. It can be carried out under mild reaction conditions and the reaction mixtures can often be used directly, for example for hydrogenations, Chlorination, bromination, oxidation, condensation, polymerization and / or for nucleophilic substitutions as described in WO 94/18 181
  • the compound of formula (I) can be used to easily introduce radioactive or labeled C atoms into organic molecules. If the compound of formula (I) is to be isolated in pure form, this can also be done in a simple manner, for example by separating the salt mixture present in the reaction mixture, removing the volatile constituents of the reaction mixture and then removing the product, for example by Distillation or crystallization, isolated. Since the process according to the invention is heterogeneous, it is also suitable for continuous implementation, in which case solvents and
  • Base optionally after regeneration, can be returned to the reaction mixture. This is particularly favorable for the solvent, since it allows direct reuse without the use of an aqueous phase during processing.
  • Products of the formula (I) are important substances in the chemical industry which can be used, for example, as intermediates for active ingredients or as active ingredients in crop protection (in particular insecticides, pesticides, fungicides and herbicides) and in the pharmaceutical sector. They can also be used as intermediates for plastics, Lacquers and polymers serve
  • Some particularly important compounds of the formula (I) which can be prepared according to the invention are e.g. Trimethadione, paramethadione, malidone, vinclozolin, ethadione, propazone, chlozolinate, RN 24 261 -46-9, 129 143-39-1,
  • reaction was carried out in a manner similar to that described in DE-OS 4 318 889, but with the difference that all the reactants were introduced together and carbon dioxide was introduced at the same time under pressure or over a longer period of time without significant pressure.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne la production d'oxazolidine-2,4-diones par réaction d'amides avec du dioxyde de carbone dans un solvant et en présence d'un ou de plusieurs composés basiques.
PCT/EP1997/001425 1996-04-03 1997-03-21 Procede de production d'oxazolidine-2,4-diones Ceased WO1997037981A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU21588/97A AU2158897A (en) 1996-04-03 1997-03-21 Process for the production of oxazolidine-2,4-diones

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19613333.5 1996-04-03
DE1996113333 DE19613333A1 (de) 1996-04-03 1996-04-03 Verfahren zur Herstellung von Oxazolidin-2,4-dionen

Publications (1)

Publication Number Publication Date
WO1997037981A1 true WO1997037981A1 (fr) 1997-10-16

Family

ID=7790369

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/001425 Ceased WO1997037981A1 (fr) 1996-04-03 1997-03-21 Procede de production d'oxazolidine-2,4-diones

Country Status (3)

Country Link
AU (1) AU2158897A (fr)
DE (1) DE19613333A1 (fr)
WO (1) WO1997037981A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056966A1 (fr) * 1981-01-24 1982-08-04 BASF Aktiengesellschaft Procédé pour la préparation de 2,4-oxazolidinediones
DE3115650A1 (de) * 1981-04-18 1982-11-04 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von n-substituierten oxazolidin-2,4-dionen
WO1994018181A1 (fr) * 1993-02-01 1994-08-18 Monsanto Company Procede de preparation de n-substitue-oxazolidine-2,4-diones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056966A1 (fr) * 1981-01-24 1982-08-04 BASF Aktiengesellschaft Procédé pour la préparation de 2,4-oxazolidinediones
DE3115650A1 (de) * 1981-04-18 1982-11-04 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von n-substituierten oxazolidin-2,4-dionen
WO1994018181A1 (fr) * 1993-02-01 1994-08-18 Monsanto Company Procede de preparation de n-substitue-oxazolidine-2,4-diones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARIA ANTONIETTA CASADEI: "Electrochemical studies on haloamides.Part XII.Electrosynthesis of oxazolidine-2,4-diones", TETRAHEDRON, vol. 51, no. 20, 15 May 1995 (1995-05-15), OXFORD GB, pages 5891 - 5900, XP002032723 *

Also Published As

Publication number Publication date
DE19613333A1 (de) 1997-10-09
AU2158897A (en) 1997-10-29

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