GB1599623A - 2-(2,2-dihalovinyl)-thiophenes - Google Patents

2-(2,2-dihalovinyl)-thiophenes Download PDF

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GB1599623A
GB1599623A GB14644/80A GB1464480A GB1599623A GB 1599623 A GB1599623 A GB 1599623A GB 14644/80 A GB14644/80 A GB 14644/80A GB 1464480 A GB1464480 A GB 1464480A GB 1599623 A GB1599623 A GB 1599623A
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group
thiophene
dihalovinyl
general formula
thiophenes
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GB14644/80A
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Sagami Chemical Research Institute
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Sagami Chemical Research Institute
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Priority claimed from JP2605077A external-priority patent/JPS53112868A/en
Priority claimed from JP2604977A external-priority patent/JPS53112867A/en
Priority claimed from JP2917677A external-priority patent/JPS53116367A/en
Priority claimed from JP2917577A external-priority patent/JPS53116366A/en
Priority claimed from JP5642777A external-priority patent/JPS53144567A/en
Priority claimed from JP5642677A external-priority patent/JPS53149967A/en
Priority claimed from JP6105977A external-priority patent/JPS53147063A/en
Priority claimed from JP14610577A external-priority patent/JPS603309B2/en
Priority claimed from JP14610677A external-priority patent/JPS5479266A/en
Application filed by Sagami Chemical Research Institute filed Critical Sagami Chemical Research Institute
Publication of GB1599623A publication Critical patent/GB1599623A/en
Expired legal-status Critical Current

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    • 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
    • C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
    • 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
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen 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
    • C07D333/06—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
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • 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
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Liquid Crystal Substances (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

( 21) Application No 14644/80 ( 22) Filed 10 M
( 62) Divided out of No 1599621 ( 31) Convention Application No 52/146105 ( 32) Filed 7 Dec 1977 in ( 33) Japan (JP) ( 44) Complete Specification published 7 Oct 1981 ( 51) INT CL 3 C 07 D 333/04 ( 52) Index at acceptance arch 1978 C 2 C 1510 200 215 246 247 254 25 Y 30 Y 313 31 Y 339 366 368 37 X 47 X 491 628 658 65 X 776 AA AB BL ZN ( 54) 2-( 2,2-DIHALOVINYL)THIOPHENES ( 71) We, SAGAMI CHEMICAL RESEARCH CENTER, a Japanese body corporate of No 4-5, Marunouchi, 1Chome, Chiyoda-ku, Tokyo, Japan do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the
following statement:
The present invention relates to 2-( 2,2dihalovinyl)-thiophenes.
According to the present invention novel 2-( 2,2-dihalovinyl) thiophenes are provided having the general formula R' (I) R 15 R CH=CX 2 wherein R' and R 2, which may be the same or different, each represent hydrogen, a halogen, an alkyl group, an aroyl group or an alkanoyl group; and X represents chlorine, bromine or iodine.
Typical examples of compounds of general formula (I) are the 2-( 2,2dihalovinyl) thiophenes represented by the general formula U 3 CH=CX 2 S wherein X is as defined above.
The compounds of general formula (I) can be converted to 2-thiopheneacetic acids and esters thereof and such 2thiopheneacetic acids are very useful as chemical modifiers of penicillin and cephalosporin (Cf J Amer Chem Soc, 84, 3401 ( 1962)).
The 2-( 2,2-dihalovinyl)thiophenes can be prepared for example by the reduction of atrihalomethyl-2-thiophenemethanols having the general formula R 7 R,2 D-VLCHCX 3 OH (III) and the a trihalomethyl 2 thiophenemethanols themselves aree easily obtainable by reacting thiophenes having the general formula (IV) with a trihaloacetaldehyde represented by the general formula CX 3 CHO under acidic conditions wherein R', R 2 and X have the meaning given above This preparation of the a trihalomethyl 2 thiophenemethanols is described and claimed in our copending Patent Application 7932164 (Serial No 1599621).
Examples of thiophenes of general formula (IV) are thiophene, 2chlorothiophene, 2-bromothiophene, 2,3dichlorothiophene, 2-methylthiophene, 2ethylthiophene, 2-methyl 3 chlorothiophene and 2 chloro 3 methylthiophene.
The compounds of general formula (III) can be prepared for example by reacting compounds of general formula (IV) with trihaloacetaldehyde under acidic conditions, and the acidic condition is, preferably, established by using a Lewis acid, e g titanium tetrachloride, in the presence of a titanium alkoxide in order to minimise the formation of byproducts, and it is preferable to use a solvent customarily employed in Friedel-Crafts reactions, for example an aliphatic hydrocarbon such as hexane or heptane, a halogenated hydrocarbon such as methylene chloride or trichloroethane, or carbon di-sulfide.
Usually, the reaction proceeds at room PATENT SPECIFICATION ( 11) 1 599 623 R' R 2 AS i 1,599,623 temperature, but if desired, the reaction may be accelerated by heating.
In place of the compounds of general formula III it is possible to use a trihalomethyl 2 thiophenemethanol derivatives of the general formula R' R 1 HOR (v) (wherein R', R 2 and X have the meanings given above and R is an alkyl group, an acyl group, an arylsulphonyl group, or an alkanesulphonyl group).
Reduction of compounds having the general formula (III) or the general formula (V) may be effected with a reducing agent and the preferred reducing agent is zincacetic acid which acts readily and smoothly.
The use of a solvent is not always required during reduction but, if desired, an ether e g diethyl ether or tetrahydrofuran, a hydrocarbon e g benzene, toluene or hexane, or an alcohol e g methanol or ethanol, or acetic acid which may form part of the reducing agent, may be used The reaction proceeds smoothly at a temperature from room temperature of to the refluxing temperature of the solvent used.
The 2-( 2,2-dihalovinyl)thiophenes of this invention can readily be converted to 2thiopheneacetic acids or esters thereof by hydrolysis or alcoholysis under a basic condition The establishment of the basic condition may be effected by using an alkali metal salt e g sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide, or an alkali metal alkoxide e g.
sodium methoxide, sodium ethoxide or potassium methoxide, in the presence of water or alcohol The reaction proceeds smoothly at a temperature range of from room temperature up to the boiling point of water or the alcohol At this stage, a compound having the general formula:
R 1 S CH=CI / (VI) OR' and/or R 1 R'XL,OR/ R 2 ii 17 CHH= C (VII) \OR/ wherein R' is hydrogen or an alcohol residue, and R', R 2 and X have the meanings given above is formed, in which at least one of the halogen atoms of the 50 dihalovinyl group has undergone hydrolysis or alcoholysis It is preferred to subject this reaction mixture to an acidic condition.
This step can be accelerated by the direct addition of an acidic substance to the 55 reaction system Examples of such acidic substances are an inorganic acid e g.
hydrochloric acid or sulphuric acid, ammonium chloride, and an organic acid e.g acetic acid, benzoic acid or p-toluene 60 sulphonic acid This step also proceeds smoothly from a temperature from room temperature or by heating.
The following Examples are purely illustrative 65 Examples 5, 6 and 7 are given for reference purposes only As the internal standard used in NMR measurement, tetramethylsilane was used in every case and the values were shown by X, in ppm 70 Example I
2,2,2-Trichloro 1 ( 2-thiophene) ethyl acetate ( 18 g) was dissolved in acetic acid ( 108 ml), and then zinc dust ( 3 g) was added to this solution, and the mixture was heated under reflux with vigorous stirring Two other portions of zinc dust each of 3 g were added with an interval of one hour, and after 5 hours the mixture was cooled to room temperature Acetic acid was distilled off under reduced pressure and the residue was extracted with diethylether The ether extract was washed with a saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate.
After treating with activated carbon, the crude crystals ( 10 8 g, yield 91 5 %) which remained after distilling off the solvent, were distilled under a reduced pressure to give 2-( 2,2 dichlorovinyl)thiophene ( 9 23 g), boiling at 103-108 C/20 mm Hg This crystallized on standing.
Yield 78 2/ mp: 38-39 C IR (Nujol): 1605, 1510, 1420, 1350, 1310, 1282, 1245, 1215, 1120, 1075, 1050 and 910 (cm-,).
NMR (CDCI 3): 6 88-7 30 (m, 3 H, ring H) and 6 93 (s, 1 H, CH=CCI 2).
Calculated for C 6 H 4 C 12 S: C, 40 25; H, 2 25 % Found: C 40 38: H, 2 410 "Nujol"' is a registered Trade Mark.
Example 2 a Trichloromethyl 2 thiophene methanol ( 300 mg, 1 3 mmol) was dissolved 105 in acetic acid ( 3 ml), then zinc dust ( 170 mng, 2 6 mmol) was added and the 3 1,599,623 mixture was heated under reflux for 3 hours with vigorous stirring After cooling, water and ethyl acetate were added and the organic layer was separated The organic layer was washed successively with water, an aqueous solution of sodium bicarbonate, and then water, and dried with anhydrous magnesium sulphate The solution was filtered and concentrated to give 200 mg of an oily material Analysis by gas chromatography ( 20 o EGA, lm, 120 C) showed the formation of 2 ( 2,2 dichlorovinyl)thiophene in 77 O yield.
Example 3
Zinc dust ( 170 mg, 2 6 mmol) and sodium acetate ( 11 mg, 0 13 mmol) were added to a solution of a trichloromethyl 2 thiophenemethanol ( 300 mg, 1 3 mmol) in acetic acid ( 3 ml) The mixture was heated under reflux with vigorous stirring After 4 hours, zinc dust ( 100 mg, 1 5 mmol) was added and the mixture was further heated under reflux for another 3 hours After cooling, the mixture was treated in the same manner as in Example 2, and analyzed by gas chromatography, which showed that 2 ( 2,2-dichlorovinylthiophene was formed in 68 % yield.
Example 4
Acetic anhydride ( 400 mg) was added with stirring and cooling with ice-water to a solution of a-trichloromethyl 2 thiophenemethanol ( 300 mg, 1 3 mmol) in pyridine ( 500 mg) The temperature of the mixture was allowed to rise gradually to room temperature, and after 2 hours, acetic acid ( 3 ml) and zinc dust ( 170 mg, 2 6 mmol) were added, and the reaction mixture was heated under reflux with vigorous stirring.
After 2 hours, zinc dust ( 80 mg) was added, and after 30 minutes a further portion of zinc dust ( 80 mg, 1 2 mmol) was added.
After heating under reflux for a total of 3 hours, the mixture was cooled The mixture was then treated in the same manner as in Example 2, and analyzed by gas chromatography, showing the formation of 2 ( 2,2 dichlorovinyl)thiophene in 74 % overall yield.
Example 5
Titanium tetraisopropoxide ( 4 26 g, 15 mmol) was added under an argon atmosphere with stirring and under water cooling to a solution of titanium tetrachloride in methylene chloride ( 1 I molar concentration; 30 ml, 30 mmol).
After 10 minutes, thiophene ( 2 52 g, 30 mmol) was added and then chloral ( 8 82 g, mmol) was added dropwise during 10 minutes with stirring and under ice-water cooling After the addition was completed, stirring was continued for a further 10 minutes, and then water and methylene chloride were added successively, and the organic layer was separated The organic layer was washed with water and dried over anhydrous magnesium sulphate The solution was filtered and, after removal of the solvent by distillation under a reduced pressure with an aspirator, the residue was distilled to yield chloral isopropyl alcoholate initially and then 5 0 g of cr trichloromethyl 2 thiophenemethanol.
Yield: 72 % (based on thiophene) B.Pt 95-97 C/0 7 mm Hg (literature value: 140-142 C/10 mm Hg) IR(cm-1): 3425, 1065, 1044, 822 and 710.
NMR (CDCI 3): 3 48 (d, J= 5 Hz, 1 H), 5 40 (d, J= 5 Hz, IH) and 6 88-7 50 (m, 3 H).
Example 6
A mixture of a-trichloromethyl 2thiophenemethanol ( 15 5 g, 67 1 mmol) and acetyl chloride ( 15 5 ml) was heated under reflux with stirring for 15 hours in accordance with the literature procedure (V W Floutz, J Amer Chem Soc, 71, 2859 ( 1949)) Acetyl chloride was distilled off under reduced pressure and the residue was extracted with diethylether The organic layer was washed with an aqueous solution of sodium bicarbonate and then with water, and dried with anhydrous magnesium sulphate After filtration, the solvent was distilled off to give 2,2,2 trichloro I ( 2 thiophene)ethyl acetate ( 18 0 g, Yield:
97.8 %) as white crystals.
Example 7
A solution of sodium methoxide was prepared by the addition of sodium ( 1 53 g) to methanol ( 85 ml) 2 ( 2,2 dichlorovinyl)thiophene ( 3 O g, 16 8 mmol) was added to this solution and the resulting mixture was heated overnight under reflux.
After confirming the disappearance of the starting material by thin-layer chromatography, the reaction solution was acidified by bubbling hydrogen chloride gas through it under cooling with ice-water, and the mixture was heated overnight under reflux Methanol was distilled off under reduced pressure and the residue was extracted with diethyl-ether The ether layer was washed with water, and dried with anhydrous magnesium sulphate After filtration, the solution was concentrated and the residue was distilled under reduced pressure to give methyl 2 thiopheneacetate ( 2 10 g) boiling at 109-111 C/23 mm Hg.
Yield: 80 2 % NMR (C C 14): 3 65 (s, 3 H), 3 70 (s, 2 H) and 6.75-7 20 (min, 3 H).
1,599,623 1,599,623

Claims (6)

WHAT WE CLAIM IS:-
1 2 ( 2,2 Dihalovinyl)thiophenes having the general formula:
RI R Ri LCH=CX 2 wherein R 1 and R 2, which may be the same or different, each represent hydrogen, a halogen, an alkyl group, an aroyl group or an alkanoyl group; and X represents chlorine, bromine or iodine.
2 Thiophenes as claimed in claim 1, in which RI and R 2 each represent hydrogen.
3 A thiophene as claimed in claim 2 in which X represents chlorine.
4 Process for the preparation of a 2 ( 2,2 dihalovinyl) thiophene which comprises reducing an a-trihalomethyl-2thiophenemethanol of the general formula:
R' p 1 Ri D 47 LCHCX 3 OH wherein R', R 2 and X have the meanings given in claim I and R represents hydrogen, an alkyl group, an alkanoyl group, an arylsulphonyl group or an alkanesulphonyl group.
Process as claimed in claim 4, in which reduction is effected with zinc and acetic acid.
6 Process for the preparation of a 2 ( 2,2 dihalovinyl) thiophene of the formula given in claim I, substantially as hereinbefore described with reference to and as illustrated in any of Examples 1 to 4 W P THOMPSON & CO, Coopers Building, Church Street, Liverpool Ll 3 AB.
Chartered Patent Agents.
Printed for Her Majesty's Stationery Office, by the Courier Press, Leamington Spa 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A IAY, from ' which copies may be obtained.
GB14644/80A 1977-03-11 1978-03-10 2-(2,2-dihalovinyl)-thiophenes Expired GB1599623A (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2605077A JPS53112868A (en) 1977-03-11 1977-03-11 Production of thienylacetic acid derivative
JP2604977A JPS53112867A (en) 1977-03-11 1977-03-11 Production of alpha-trihalomethyl-2-thiophenemethanol
JP2917677A JPS53116367A (en) 1977-03-18 1977-03-18 Preparation of thienylglycollic acids
JP2917577A JPS53116366A (en) 1977-03-18 1977-03-18 2-(dichloroacetyl)thiophene and process for its preparation
JP5642777A JPS53144567A (en) 1977-05-18 1977-05-18 Preparation of thienylacetic acids
JP5642677A JPS53149967A (en) 1977-05-18 1977-05-18 Preparation of thienylacetic acids
JP6105977A JPS53147063A (en) 1977-05-27 1977-05-27 Preparation of alpha-acyloxythienyl acetic acids
JP14610577A JPS603309B2 (en) 1977-12-07 1977-12-07 2-(2,2-dihalobinyl)thiophene and its manufacturing method
JP14610677A JPS5479266A (en) 1977-12-07 1977-12-07 Producion of 2-thienylacetic acid or its ester

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GB1599623A true GB1599623A (en) 1981-10-07

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Application Number Title Priority Date Filing Date
GB9497/78A Expired GB1599621A (en) 1977-03-11 1978-03-10 Process for preparing thiophene derivatives
GB14644/80A Expired GB1599623A (en) 1977-03-11 1978-03-10 2-(2,2-dihalovinyl)-thiophenes
GB32164/79A Expired GB1599622A (en) 1977-03-11 1978-03-10 Processes for preparing thiophene derivatives

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Application Number Title Priority Date Filing Date
GB9497/78A Expired GB1599621A (en) 1977-03-11 1978-03-10 Process for preparing thiophene derivatives

Family Applications After (1)

Application Number Title Priority Date Filing Date
GB32164/79A Expired GB1599622A (en) 1977-03-11 1978-03-10 Processes for preparing thiophene derivatives

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DE (1) DE2810262A1 (en)
FR (1) FR2415109A1 (en)
GB (3) GB1599621A (en)
NL (1) NL7802623A (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1584120A (en) * 1977-07-21 1981-02-04 Sagami Chem Res Process for the preparation of thiophene derivatives and thiophene derivatives obtained therethrough
EP0011279B1 (en) * 1978-11-14 1982-05-05 Sagami Chemical Research Center Process for the preparation of aromatically substituted acetic acids
EP0020172A3 (en) * 1979-06-05 1981-04-01 FMC Corporation Nematicidal haloethenylthiophenes and their use
FR2470127A1 (en) * 1979-11-19 1981-05-29 Hoechst France Crystalline racemic sodium 2:thienyl glycolate - prepd. from 2-di:chloroacetyl thiophene, is a stable intermediate for 2:thienyl-acetic acid
FR2545086B1 (en) * 1983-04-29 1985-12-27 Hoechst France PROCESS FOR THE PREPARATION OF ALKANOIC ACIDS
FR2588870B1 (en) * 1985-10-21 1989-01-20 Hoechst France PROCESS FOR OBTAINING ALKANOIC ACIDS
FR2588869B1 (en) * 1985-10-21 1988-08-12 Hoechst France PROCESS FOR THE MANUFACTURE OF ALKANOIC ACIDS
US4782079A (en) * 1986-06-02 1988-11-01 Fmc Corporation 2-(2,2-dihaloethenyl)-5-arylthiophene pesticides
DE3700732A1 (en) * 1987-01-13 1988-07-21 Boehringer Mannheim Gmbh NEW CARBONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS

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Publication number Publication date
GB1599621A (en) 1981-10-07
FR2415109A1 (en) 1979-08-17
DE2810262A1 (en) 1978-09-28
FR2415109B3 (en) 1981-09-11
NL7802623A (en) 1978-09-13
GB1599622A (en) 1981-10-07

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