DE3445504A1 - Novel esters of vinylcyclopropanecarboxylic acid derivatives, a process for their preparation, and insecticide containing them - Google Patents

Abstract

The invention relates to a process for the preparation of esters, some of which are novel, of vinylcyclopropanecarboxylic acid derivatives of the formula …<IMAGE>… in which X represents a halogen, preferably chlorine or bromine, and R1 represents a geraniol- and citronellol-derived radical, and to insecticides and acaricides containing these compounds as active substances.

Description

New esters of derivatives of vinylcyclopropanecarboxylic acid and processes for their preparation and insecticidal agents containing them

The invention relates to a process for the preparation of new derivatives of the vinyl cyclopropane carboxylic acid in all possible isomeric forms having insecticidal and milbenab- Q-killing effect of the following formula

wherein X is independently chlorine or bromine and R _{1 is} an alkyl radical derived from geraniol (3,7-dimethyl-6-octadiene-1-oil) or citronellol (3,7-dimethyl-6-octene-1-oil) is.

The pelitre or pyrethrum is obtained from the painting of flowers of the species pyrethrum or chrysanthemum

QQ cinerari aefolium, P. roseum and P. carenuum. From these yellow powders an extract with the appearance of an oily liquid is obtained, which contains the pyrethrins I and II together with four other components, namely the zinerins I and II and the jasmolines I and II, corresponding to the various esters of pyrethrins and Chrysanthemic acid with the pyrethronol, zinerol and

Types of jasmine alcohol. Own these natural types of alcohol a central ring with an unsaturated carbon atom, that is linked to a methyl group, while the other adjacent carbon atom that leads to Belongs to the same unsaturated group, with an unsaturated side chain with 4 or 4 carbon atoms connected is. These structural units are, with regard to the electron density and their spatial distribution, identified with the alcohols geraniol and citronellol, which is why a similar behavior between the natural esters and those according to the invention are given as effective active ingredients of insecticides.

15th

Processes for Production of esters of cyclopropanecarboxylic acid with benzyl alcohols (DE-PS 26 58 074 and GB-PS 44.151 / 79), Furylmethyl alcohol (JP-PS 140.657 / 74), phenoxybenzyl alcohol (CH-PS 11.077 / 78-6, 8.204 / 79-1, 13.287 / 77, 9.991 / 78, 3.047 / 79-8 and 981 / 80-1, GB-PS 2.763 / 77, 12. 210/77, 36.714 / 77 and 36.715 / 77) described, according to the invention However, alcohols used are in

nowhere mentioned in these publications. 25th

According to the method according to the invention, the production new derivatives of vinylcyclopropanecarboxylic acid in all its possible isomer forms of the following formula

30th

(D

35

allows where X is independently chlorine or bromine and R. is a geraniol (3,7-dimethyl-2,6-octadiene-1-oil) declining alkyl radical (a)

Χ-, a,

10 CH ₃ CH *

or on citronellol (3, V-dimethyl-ö-octan-i-ol) leaving remainder (b)

(b)

A distinction is made between two levels.

1. Obtaining the chloride of trans-2,2-dimethyl-3- (2,2-dichloro- (or dibromo) vinyl cyclopropanecarboxylic acid.

(R, S) -trans-2,2-Dimethyl 1-3- (2,2-dihalovinyl) -cyclopropane-1-carboxylic acid is made to react with thionyl chloride using benzene as the solvent.

(Br) CIv

\ C = HC

(Br) Cl

Acid + SOClg - * - 35

The reaction mixture is heated for a few hours, whereupon the solvent and the excess thionyl chloride is removed under reduced pressure.

2. Conversion of the acid chloride to the corresponding ester

The chloride of trans-2,2-dimethyl-3- (2,2-dihalovinyl) -cyclopropanecarboxylic acid obtained in the previous stage is reacted in benzene as a solvent with the alcohols geraniol (a) and citronellol (b).

After the reaction mixture has warmed to a temperature of 36 to 4O ⁰ C, a Trxethylamxnlosung in benzene is added dropwise while maintaining the temperature, and stirred for 15 to 21 hours. First hydrochloric acid and then sodium hydrogen carbonate are then added to the reaction medium in order to neutralize the acidity, whereby two phases are formed. The organic phase is dried over sodium sulfate and filtered, the solvent is removed under reduced pressure and the concentrated crude end product is obtained in the form of an oil.

To analyze this end product, a sample is chromatographed on a silica gel column using Benzene eluted as the eluent. The compounds obtained in this way correspond to the following formulas:

1R-CXS- or iR-trans-2,2-dimethyl-3 (2,2-dichlorovinyl) -cyclopropane-i-carboxylate of 3,7-dimethyl-2,6-octadiene (I-a).

3U5504

(Br) OL

CH,

iR-cis- or 1R-trans-2,2-dimethyl-3- (2,2-dichlorovinylcyclopropane-1-carboxylate of 3, V-dimethyl-e-octane (I-b)

(Br) Cl

CH.

CH.

(I-b)

nine insecticidal activity towards these new products the fruit fly (fruit and vinegar fly) was

grasslands.

The activity tests are described in Example 3.

3U55CH

example 1

Synthesis of (R, S) -trans-2,2-Diinethyl-3- (2, 2-dichloroviny1) -cyclopropanecarboxyl chloride.

In a 250 cc flask with a magnetic stirrer, The reflux condenser and oil bath are 8.36 g (0.040 mol) of (R, S) -trans-2,2-dimethyl-S- (2,2-dichlorovinyl) -cyclpropane-1-

carboxylic acid, 60 ecm benzene and 11.42 g (0.096 mol) Thionyl chloride given. The reaction mixture is refluxed for 3 hours and then the Benzene and the excess thionyl chloride removed under reduced pressure on a rotary evaporator.

Synthesis of (R, S) -trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate of 3,6-dimethyl-2,6-oetadiene.

The Reaktxonsprodukt obtained in the preceding step, 80 cc of benzene and 6.17 g (0.040 mole) of 3,7-dimethyl-2,6-octadiene-1-oil, dissolved in 10 cc of benzene, admixed to, and the mixture to 40 ⁰ C is heated. After the reaction mixture has reached this temperature, a solution of 4.4 g (0.044 mol) of triethylamine, dissolved in 20 cm ^{3 of} benzene, is added for 1 hour, whereupon the reaction mixture is ^{stirred at 36 to 40 °} C. for 15 hours. Then 5 0 ecm of cold 1M hydrochloric acid are added twice to the reaction mixture, whereupon it is neutralized with twice 50 ecm of a 10% strength sodium carbonate solution and 5 0 ecm of water. This creates two phases. After drying over sodium sulfate, the organic phase is filtered and the solvent is removed under reduced pressure on a rotary evaporator.

-Μ A sample of the crude product is eluted chromatographically in a silica gel column using benzene as the eluent. The analyzes carried out on the purified product by IR and RMN give the following results

IR imax 2980 (CH), 1740 (CO, 1175 (-CO) cm " ¹ 10

RMN (90 Mh ₂ , _ccl \ _en g. ^ ₂₂ / _{1S 3H>} _ _CH y

Q
-CH ₃ ), 1.5 (1H, m, CH-C-), 1.55-1.6 (9H, 3S, -CH ₃ ), 2.1-2.3 (1H, m, ^ CH -), 2.1 (4H, 2CH ₂ , 1S), 4.55 (2H, 1d, 0-CH ₂ - 78 H ₂ ) 5.3 (1H, 1t, = CH-CH ₂ -5.6 ( 1H, iS, ^ c = CH, J, 8H ₂ ).

Example 2

Synthesis of (R, S) -trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate of 3,7-dimethyl-6-octene-I-OI.

The synthesis of (R, S) -trans-2,2-dimethyl 1-3-2,2-dimethyl-3- (2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic chloride is carried out as in Example 1.

The reaction product obtained in this synthesis

80 cc of benzene and 6.87 g (0.044 mol) of 3,7-dimethyl-6-octan-Ι-0Ι dissolved in 10 cc of benzene was added, followed by heating to 40 ⁰ C. After this temperature has been reached, in

1 h 4.4 g (0.044 mol) was added dropwise in 20 cc of benzene Dissolved triethylamine, whereupon 16h stirred while maintaining a temperature of 36 to 4O ⁰ C. The solution obtained in this way is added twice with 50 ecm of cold 1M hydrochloric acid and then twice with 50 ecm of 10% sodium bicarbonate and 50 ecm of water , two phases being formed. The organic phase is dried over sodium sulfate and filtered. The solvent is removed under reduced pressure on a rotary evaporator. The weight of the crude product in the form of oil is 15 g.

A sample of the crude product is eluted by chromatography on a column using benzene as the eluent. The analyzes of the pure product by IR andRNM give the following results:

IR J max 2910-2980 (CH), 1745 (CO) cm " ¹

RMN

(90 MH ₂ ), J ", 1.3 (1S, 3H, -CH ₃ CyCIo), 1.4 (1S, 3H,

_{2 3}

-CH ₃ CyClO), 1-2 (3S, 9H, -3XCH ₃ ), 2.1 (1C, 1H, _Ζ

3.7 (1t, 2H, <T7HJ (2.3, 2 /, 1H, CH ¹ D "9H), 5.7 (1d,

^1H '= ° - ^Η

Example 3

Biological activity tests using the new esters.

Draft flies are released in a chamber made of methyl methacrylate with a capacity of 34 liters. Inside the chamber, the product whose biological activity is to be tested is atomized, dissolved in 2.5 ecm of pure hexane (p.a.). The dis-

-14-1

Dusting takes place with the help of a glass sprayer for the development of fine-layer chromatography plates. 5 Hexane is chosen because of its negligible effect on fruit flies.

The results are shown in the table below.

Tabel

Summary of the biological activities of various Connections to fruit flies.

Connection number of

Concentration of flies I-a 2%

1-1 4%

1-1 6%

30 I-b 2%

I-b 4%

Time exhausted dead ι flies begin to 10 0 begin to Min. To fly the exhausted die 19th die 10 11th Recover flies 27 60 31 not and ver the exhaustion represents 41 120 36 end slowly slowly settle in 0 5 3 15th 0 15th 5 20th 0 21 10 25th begin to perish 11th 14th 59 28 45 31 38 60 21 3 4th 7th 13th 9 20th 13th 36 15th 26th 20th 17th 23 9 60 10 20th 40 120

Claims (8)

European Patent Attorneys German Patent Attorneys Dr. Paul Deufel Dipl.-Chem., Dipl.-Wirtsch.-Ing. Dr. Alired Sdiön Dr. MüUer-ΒοΓέ and Partner · POB 26 02 tt ■ D-8000 Mündjen 26 Dipl.-Chem. Werner Hertel Dipl.-Phys. Dietrich Lewald Dipl.-Ing. Dr.-Ing. Dieter Otto Dipl.-Ing. Brit. Chartered Patent Agent B. David P. Wetters M. A. (Oxon) Ch. Chem. M. R. S. C. U 1062 S / MsI Union Explosivos Rio Tinto S.A. Paseo de la Castellana 20 28001 Madrid / Spain New esters of derivatives of vinylcyclopropanecarboxylic acid and process for their preparation as well as insecticidal agent containing them. Patent claims 1.J New esters of derivatives of vinylcyclopropanecarboxylic acid in their racemic or optically active form with insecticidal properties, namely i-R-cis-trans-3- (2,2-dichlorovinyl) 2,2-dimethylcyclopropanecarboxylate of 3,7-dimethyl-2,6-octadien-1-yl the formula D-8000 Munich 2 POB 26 02 47 Cable: Telephone Telecopier Infotec 6400 B Telex ■ - - * - · η, ™ »» «. ·; —J nc · x * .. "i " t ηοηιηοΐΛαο τ Π TT j. TTT in 801 22?) Fi 43 5-24285 CH. CH. 2. 1-R-cis, trans -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate of 3,7-dimethyl-6-octan-1-yl of the formula Cl II COH ₂ O 3. Process for the preparation of new esters of derivatives of vinylcyclopropanecarboxylic acid in its racemic or optically active form with insecticidal properties the formula - 0 - H- (D where X is a halogen, preferably chlorine or bromine, and R _{1 is} a radical (a) or (b) going back to geraniol and citronellol, η! (a) H ₃ C. CH, CH. (b) characterized in that a vinylcyclopropanecarboxylic acid or an esterifiable derivative thereof the formula -H ₂ (ID - A - in which X has the meaning given above and R _{2 is} —OH or halogen, preferably Cl, with an alcohol of the formula RQ, where R is a radical (a) or (b) as defined above and Q is —OH or halogen , is implemented. 4. The method according to claim 3, characterized in that the esterification reaction in the presence of a suitable inert solvent, preferably benzene. 5. The method according to claims 3 and 4, characterized in that that the esterification reaction is carried out in the presence of triethylamine or pyridine. 6. The method according to claim 3, characterized in that the esterification reaction between a vinylcyclopropanecarboxylic acid or an esterifiable derivative thereof of the formula (II) O »HC \ ö = il «V CH- CH- (II) where X and R _{2 have} the meanings given, and a citral of the formula is carried out in the presence of a water-soluble alkali metal cyanide, ¹ ^ an aprotic solvent and a catalyst for phase transfer. 7. The method according to claims 3 and 6, characterized in that that the alkali metal cyanide used, sodium cyanide, the solvent n-heptane and the catalyst for phase transfer is a quaternary ammonium salt, preferably tetrabutylamine chloride, a basic ion exchange resin, preferably Amberlitte TRA-400 or a nonionic surface-active one Agent is made from a mixture of oxyethylated alkanes having a 9 to 11 carbon fatty chains containing atoms 8. Insecticidal and miticidal agent, thereby characterized in that it contains one or more compounds according to one of the preceding claims as an active ingredient contains.