DE2727612A1 - CYAN-SUBSTITUTED CYCLOPROPAN DERIVATIVES AND METHOD FOR MANUFACTURING THEREOF - Google Patents

Description

DR. ING. F. WUK8TIIOFF DR. Β.τ.PEOHM ANN DK. ING. D. BEIIHKNS DIPU. ING. R. GOBTZ PATKMTAN WlI.TI

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1A-49 423

Applicant: SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. Carel van Bylandtlaan 30, The Hague, Netherlands

Title: Cyano-substituted Cyolopropaneivate und Process for their manufacture

709881/0805

DH. TNG. F. WUKSTHOFF DH. K. τ. PKOJIM ANN DH. ING. IJ. IJKiIHKNS DiTl .. ING. H. (iOKTZ PATENT LAWYERS

8OOO MUNCIIKN OO SC1IWEHIE11STHASSE 2 TKI.RFON (080) β TII.KI S 24 070 TKI- Ka RAMM K t

7727612

1A-49 423

description

The invention relates to the production of cyano-substituted cyclopropane derivatives, which are used as intermediates for Production of insecticides are suitable, such as o (-Cyan-3-phenoxybenzyl ester of 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid.

The invention now relates to a process for the preparation of GyclopropanecarbcL ^ nitriles of the general formula

H CH = C (Hal) ₂

(D

1 2
wherein R and R are an alkyl group with 1-6 carbon atoms and Hal is a fluorine, chlorine or bromine atom, in which a cyclopropanecarboxylate of the general formula

H CH = C (Hal) ₂

(II)

COOX

is heated in (rainwater of a polar, aprotic solvent, where X is a quaternary ammonium group. A quaternary

709881/0805

-2-

AmtDoniumgruppe is a group that is obtained by adding a proton to the nitrogen atom of ammonia: or a primary, secondary or tertiary amine.

The process according to the invention generally leads to a yield of about 80-90 # _f therefore has a high selectivity for the compounds of the formula I. "Selectivity" is understood here to mean the yield of the desired compound, calculated on the amount of material used.

The polar, aprotic solvent that the Cyclopropanecarboxylate of the formula II is able to dissolve, for example Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Dimethyl sulfoxide, N-methylpyrrolldone or acetonitrile. the Conversion of the compound according to formula II is generally highest for a given time with Ν, Ν-dimethylformamide.

They used cyclopropanecarboxylates as starting materials of formula II, in which X is a quaternary ammonium group, can be prepared by adding a carboxylic acid of the formula

H CH = C (Hal) ₉

R ¹ CN

2 \

R CO.OH

is reacted with ammonia or an amine, v / whether ammonia or amine is to be used in a superstoichiometric amount. The excess serves as a solvent for the salt formed. This excess can be absent or present

-3-

709881/0805

another polar, aprotic solvent is used reach. Optionally, you can carboxylic acid and ammonia or Amine in equimolar amounts in the presence of a polar aprotic Use solvent. Examples of useful amines are pyridine, quinoline, isoquinoline, n-hexylamine, aniline, N-methylaniline and Ν, Ν-dimethylaniline. Ammonium cyclopropanecarboxylate of formula II are preferred.

The heating temperature and time for a particular starting material can easily be determined. The temperature is generally between 100 and 200 ^° C., the heating time between 10 and 70 h and of course depends on the temperature.

1 2

R and R in formula II can be the same or different be and are e.g. methyl, ethyl, n-propyl, i-propyl, η-butyl, sec-butyl, tert-butyl, n-P-entyl or u-hexyl. Preferred

1 ρ are methyl groups for the substituents R and R. Shark is preferably a chlorine atom. An example of a substance according to formula II is ammonium 1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate.

The compounds of the formula II are new and their preparation is the subject of a simultaneous application.

The invention is further illustrated by the following examples.

Example 1-5

Example 1 was carried out as follows! Ammonia at 22 ⁰ C by a solution of 6.4 mmol of 1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate in 10 cnr ΪΓ, Ν-dimethylformamide to passed through to stop the ammonia uptake, then held at 130 ^° C. for 18 h, cooled ^{to 22 ° C.}

709881/0805 -4-

I-

and poured into 150 cm ^ of water. Bas mixture was three times extracted with 15 cm η-Peηtan, the combined extracts over dried anhydrous magnesium sulphate, magnesium sulphate filtered off and n-pentane driven off. The residue was weighed out and the purity determined by NMR spectrum.

The raffinate contained after extraction with η-pentane unreacted amoonium-1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate and Ν, Ν-dimethylformamide. It was acidified with concentrated hydrochloric acid and extracted the acidic solution with methylene chloride. The extract phase was dried with anhydrous magnesium sulphate, flow-dry solution evaporated and the residue weighed. The proportion of 1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid was determined by NMR spectral analysis. This showed an implementation of the starting material of 97 ^ as can be seen in column 6 of the results in the following table. The selectivity for 2- (2,2-dichlorovinyl) -3 »3-dimethylcyclopropanecarbo-quitrile was 84 # (column 7 of the Tabel).

Examples 2-5 were carried out analogously to Example 1. The differences, however, are given in the table in columns 2-5 and 8. In Examples 4 and 5, 10 cm ⁵ (79 mmol) of Ν, Ν-dimethylaniline were used. In Example 4, the above ammonium salt was heated. In - ^ example 5 there was no introduction of ammonia, so 6.4 mmol of N, N-dimethylaniline-1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate, which was dissolved in 72, was heated , 6 mmol Ν, Ν-dimethylaniline. The conversion of the starting products and the selectivity are given in the table. The products from Example 5 were determined by the NMR spectrum and gas-plus chromatography of the solution at the end of the reaction time.

709881/0805

Tabel

Example starting solution reaction temp. Conversion selek material medium time h ⁰ C <f> activity D *

1 1 N, N-Di-
methyl-
formamide 18th 130 97 84 8.5 mmol
Starting
material 2 1 Dimethyl
sulfoxide 23 125 93 83 3 1 N-methyl-
pyrrole
idon 171/2 130 2) 7O ⁵ > 4th 1 N, N-Di-
methyl-
aniline 64 125 70 86 5 2 N, N-Di-
methyl-
aniline 64 125 75 8o

1) 1: ammonium 2-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate

2: 1-Cyano-2- (2,2-dichlorovinyl) 3,3-dimethylcyclopropanecarboxylic acid

2) not determined

3) Yield based on starting compound 1.

709881/0805

Claims (5)

Claim 1 2
wherein R ¹ and R are an alkyl group with 1 to 6 carbon atoms and Hai is a fluorine, chlorine or bromine atom. 2. Process for the preparation of the cyclopropanecarbonitriles of claim 1, characterized in that one is a cyclopropanecarboxylate of the formula H CH = C (Hal) j> R ¹ CO.OX CN (II) wherein X is a quaternary ammonium group, heated in the presence of a polar, aprotic solvent. 3. The method according to claim 2, characterized in that the solvent Ν, Ν-dimethylformamide, Ν, Η-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone or Acetonitrile used. 709881/0808 ORIGINAL INSPECTED 4. The method according to claim 2 or 3, characterized in that one uses an output product whose quaternary ammonium group is derived from ammonia, pyridine, Quinoline, isoquinoline, n-hexylamine, aniline, N-methylaniline or Ν, Ν-dimethylaniline. 5. The method of claim 2 to 4, characterized in that the mixture is heated to 100 to 200 ⁰ C. 709881/0805