DE2639777A1 - VINYLCYCLOPROPANE CARBOXYLATETER AND METHOD OF MANUFACTURING IT - Google Patents

Description

DIPL.-IjiG. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS

'8 MÜNCHEN 86, POSTFACH 86 02 45

Dr. Berg "Dipl.-lng. Stapf and Partner, 8 Munich 86, P.O. Box 860245 Your sign Our sign 07 ^ iI 7 8 MÜNCHEN 80 ·, Qp ^ i-p ^ pj, iq7fi Yniirrrf Our ref ^ ' J ⁿ ' Mauerkircherstraße45 -> · «« ^ UClUUCX JJ / U Your Fef. Our ref. Lawyer file no .: 2?

THE WELLCOME FOUNDATION LIMITED London, N.W. 1 / Great Britain

Vinylcyelopropane carboxylate esters and processes for their preparation

The present invention relates to a novel process for the preparation of known Vinylcyclopropancarboxylatester, the esters so prepared and to certain novel useful for _s, the method and synthesis intermediates.

^{X / R} 7098 10/1 189 " ² "

ichen banks: Bayerische Vereinsbank Munich A

Hypo-Bank Munich 3892623 Postscheck Munich 65343-808

^ t WSPECTED-

(089) 98 82 72 Telegrams: BERGSTAPFPATENT Munich Banks: Bayerische Vereinsbank Munich 453100

987043. TELEX: 0524560 BERG d Hypo-Bank Munich 3892623

98 3310 '* Post check Munich 65343-808

- O ~

British patent specification 1413'491 describes compounds of the general formula A- '"■■■' ■■ ^: *

H, C QH,

3 ι Λ

R - * - C = CH-CH-CH-COOR

p. in which, inter alia, each of R and R is halogen and the radical R is alkyl, hydrogen (or a salt or an acid halide derivative of the acid), as intermediates for the synthesis of insecticidal esters of the general formula I, in which B is a cyclic radical, as defined in more detail and explained below, means -and each of the radicals R and R ^ is halogen. In this description means Halogen, chlorine or bromine. These insecticidal esters showed promising activity against a wide variety of arthropod pests (arthropod pests).

H, C CH,

2 V ³

R ² A

₃ f A-

R-> -C = CH-CH-CH-COOB

One synthetic method involves the reaction of 1,1-dihalo-4-methy1-1,3-pentadiene with an alkyl diazoacetate. However, this synthesis is in terms of toxicity and the explosive character of the diazoacetate dangerous.

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Another synthetic method involves a Wittig synthesis according to the following reaction scheme:.

/ Ph R§ R ^ -

2 P ~ Ph + ^ p-halogen ₀ * - O2 = P. - Ph

+. OCH-CH-CH-COpR

\ / Connection of the

■ ^ general formula I.

2 3
wherein the radicals R ₅ R and R have the same meaning as in

of the general formula A, but unfortunately in this synthesis the formation of an undesired impurity as well as a ring opening takes place. (J. Chem. Soc. 247O _a and Supplement Publication No. SUP 2113, page 9)

It has now been found that the esters of the general formula I can be obtained very conveniently by the synthetic route, which is shown in Scheme A below.

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X ι

ίϋ

ο — ο

OJ

'ΚΛ

M M

6 ω Xi ο

χ ι

CM'

H! O

ΝΛ

Ix! O Il O

OJ

/ γΛ

ro

Π3

ΟΙ

CM

709810/1189

This route includes the formation of compounds of the general formulas II to VII, in which each of the radicals R and R is chlorine or bromine and X is nitrile, carboxyl, carbonamide, optionally substituted by one or two lower alkyl groups, carbony halide or one Is ester group. Suitable ester groups have the general formula COOM ₃ where M is a lower alkyl radical, such as, for example, ethyl, aralkyl, such as, for example, benzyl and aryl groups, such as, for example, those of the general formula B defined below.

In the process of the present invention it has surprisingly been found that the dihalogen compounds III can be prepared very easily by halogenation of the acetyl compounds II without contamination with the monohalogen compounds or formation of the corresponding trihalogen compounds. In addition, it has been found that it is possible to convert the secondary alcohols IV into the desired vinyl compounds VI by first preparing an ester V in which R 0 is a group to be eliminated and, in step (d), eliminating ^{the acid R 1 OH} which can then be reused for the formation of further ester V without opening the cyclopropane ring.

The chlorination of the acetyl compounds II is preferred

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under use; carried out by SuIfurylchl © rid. The reaction can be carried out at low temperatures, for example at temperatures from 0 ° to 50 ° C. , although reflux temperatures can also be used in an amount two to four times, or even ten times the molar equivalent of an acetyl compound = 11. Preferably, the reaction is carried out in the absence of a solvent, although one such as carbon tetrachloride can be used if desired.

The chlorination can likewise also be effected by using molecular chlorine in the presence of a catalyst, such as, for example, a peroxide (eg benzoyl peroxide) or light, in particular ultraviolet light. Optional ^: is ^: a catalyst is not required if the chlorination ^: using. molecular chlorine in carbon tetra chloride is effected, which reaction is suitably carried out at room temperature. - ■■ '■' ■ - ■ -. ■ -.- ■ ·

The bromination of the Äcetylverbindungen II may be Verwen- 'dung vo.n, ^c inert be achieved such as by liquid ether-bromo Current Map in a LÖsungsmittelSj; the reaction; runs off easily at room temperature; - '■

- 7 -7 0 9 8 1 0/1 1 8 9 ^r ; ^: ·

The reduction (b) of the dihalogen compounds III to the Hydroxy compounds IV can be prepared by any method known for the reduction of ketones to secondary alcohols be effected. Such methods include the use of sodium with ethanol, sodium or aluminum amalgam and water, catalytic hydrogenation with, for example, a nickel catalyst such as Raney nickel, and the Ponndorf process using an alcohol and an aluminum alkoxide such as aluminum isopropoxide and isopropanol. Preferably the reduction is carried out using a hydride, for example Sodium borohydride, preferably in the presence of a solvent such as an alkanol, an ether such as dioxane, or an aqueous solution thereof.

In step (c), an alcohol IV can be converted into its ester V by reaction with the acid R · 0Η, o: that of a reactive derivative thereof, such as, for example, the acid chloride or the acid bromide or the acid anhydride. The acid R 0Η is a strong acid, preferably a strong organic acid, and is preferably an alkyl, aralkyl or aryl sulfonic acid, for example p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid > p-bromobenzenesulfonic acid, or a haloalkanoic acid, such as trichloroacetic acid or trifluoroacetic acid .

- 8 70981Ό / 1.1 89 ■ .. ■.

Suitably a solvent such as eyridine is used and the reaction can be carried out easily perform at room temperature. The olefin VI can then from the ester V by elimination of the acid R OH in Presence of a base. In order to reduce the competing substitution reaction to a minimum, the conditions should be chosen which favor the elimination using a strong base. Examples of such reactants include an alkali metal alkoxide such as sodium methoxide or ethoxide, or potassium tert-butoxide, in the corresponding Alkanolj an alkali metal hydroxide such as Sodium hydroxide in an alkanol; and potassium tert-butoxide in a non-polar solvent such as benzene or toluene, or in a halogenated aliphatic Hydrocarbon solvents such as carbon tetrachloride, dichloromethane or dichloroethane; the reaction can be carried out at room temperature or with heating to the reflux temperature of the reaction mixture be performed.

Using the synthetic route as given in Reaction Scheme A, it goes without saying, if desired, possible to change the value of the radical X from one group to another within the definition given above

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- 9 -: ■: .- ■■

vary; ζ. BV can then suitably carry out "" step (a) using an alkyl ester, but then convert the compound of the general formula III into the desired ester of an alcohol "B OH" before the further course of the "synthesis." Similarly, it is essential that for any particular stage / residue X should be compatible with the 'reaction participants used.'"'' ■ '". """'''

If in the compound of the general formula VI the variable Radical X 'is an ester of the desired en' alcohol B * 0H, in which B has the same meaning as' below, then is the resulting olefin is the desired irisecticidal ester of the general formula Γ. Optionally, the olefin VI in the appropriate ester by conventional techniques such as - "" ' for example transesterification or by hydrolysis (where "it is necessary) to be converted into the acid VII / followed by an esterification.

For example, compounds of the general formula VI, in which X has a different meaning than carboxyl, into the corresponding carboxylic acid of the general formula VII using standard techniques, "such as acidic or alkaline Hydrolysis. Suitably, using suitable conditions for the elimination

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nation reaction (see above) and an excess of one suitable base converts a compound of the general formula V directly into the carboxylic acid VII without isolating the intermediate product VI to be converted.

The insecticidal esters of the general formula I can be obtained by esterifying the alcohol BQ or a reactive derivative of the same, with the acid VII or a reactive derivative thereof of the general formula VIII

. ■ -: .-: ■ - ■■ = -. Η, σ OH _x -: - .. ·. ■ - ■ ^: - ■ ■■ - ■■■■ - ■ ■: -> ■

2 V

'3 I / \ ₁

R -> - C = GH-CH-CH-COQ;, ... ■ (VIII)

in which the radicals R and R ^ each Are halogen, and Q and Q are functional groups or atoms that react with each other to form an ester bond yaw, and "B" has the value defined below.

Suitably the acid VII, its acid anhydride with chloroformic acid, or the acid chloride (formula VIII: Q is chlorine) reacted with an alcohol BOH; or a halide BHaI is combined with an acid VII salt, for example the sodium, silver or triethylammonium salt reacted; or an acid VII or a reactive derivative thereof,

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709810/1189

-I-

such as an alkali metal salt, is mixed with a quaternary Ammonium salt BA Hai reacted, in which A is, for example, an alkylamine and Hai "is a halide. Optional an ester of the general formula VI (in which X is a group COOM) can be transesterified with an alcohol BOH in the presence be subjected to a basic catalyst.

The output acety! Connections II can after any known methods such as that described in US Pat. No. 3,397,223 Process, for example, by those in Scheme B below, wherein R and X have the same meaning as in FIG Formula II have shown reaction.

Scheme B

. CH, SCH, + Hal-CH ₀ X - ^ H, C-S ⁺ -CH ₀ X Hai

3 3 2 3 £

(IX) (X) (XI)

I I

· - H ₃ C — S = CH-X + H ₃ C — C = CH-CO-CH ₃ · - (II)

(XII) (XIII)

In this scheme, the compounds of formula II are through

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709810/1189

Reaction of mesityl oxide XIII with a dimethylsulfuranylidene compound XII produced. The last-mentioned reactant XII can itself be prepared from an appropriately substituted dimethylsulfonium salt XI, which in turn is obtained from the compound X ₃ in which "Hai" is a halogen, such as bromine, and dimethyl sulfide.

The sulfonium compound XI is preferably prepared by reacting dimethyl sulfide with the compound X in a polar or non-polar solvent prepared at room temperature. The sulfonium product XI obtained can then by a base such as alkali metal hydroxide, alkoxide or hydride can be dehydrohalogenated in an alkanol. Preferably, an aqueous alkali metal carbonate solution and chloroform are used to decompose the ylide XII to reduce to a minimum.

Those acetyl compounds II which are esters of an alcohol BOH are suitably prepared using known techniques made from other corresponding acetyl compounds. For example, by transesterification of the alkyl ester or by Hydrolysis and esterification analogous to the conversion of an olefin of the general formula VI to a compound of the general Formula I.

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In the desired insectic esters of the general formula I, the cyclic radical B is selected from the class of the formula BOH, in which B is one of the following formulas up to XIX: \ '^;

7 09810/1189

-CH

Z-Y

R ^c

(XIV)

10

-R '

«11 Il CH ₇ .R

^R 0 ■■

12 (XV)

N-CH-.

Z ¹ *

Z ² n (XVII)

CH ₂ -CaCCH ₂ -CXVIII)

rs-

OCH ₂ , C = C. CH ₂ -

7 0 981 0/1189

Z can have the meaning -0-, -S-, -CHp- or -CO-, Y is hydrogen or an alkyl, alkenyl or alkynyl group or an aryl or furyl group, either unsubstituted or in the ring by one or more alkyl, alkenyl, alkoxy or halogen groups is substituted, means;

8th

R and R, which can be the same or different, each Represent hydrogen or an alkyl or alkenyl group,

R ^ is hydrogen or a methyl group, 11
R and R- '., Which can be the same or different, each denotes hydrogen or an alkyl group,

12th

R is an organic radical with carbon-carbon unsaturation is in the α-position to the -CHp group,

12th

with which R is connected,

(A / Sj indicates an aromatic ring or a dihydro or tetrahydro analog thereof,

2 "5 4

X, X, X and X, which are the same or different, are each hydrogen, chlorine or a methyl group, and

Z- ^{5 has} the meaning -CH ₂ - or -0- or -S- or -CO-,

D has the meaning H, CN or -CECH,

12 '
Z and Z, which can be the same or different,

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each represent chlorine or a methyl group, and η is 0, 1 or 2.

Highly active examples of such insecticidal esters of general formula I include those derived from 5-benzyl-3-furylmethyl alcohol (in formula XIV: Z-Y is 5-benzyl,

7 8
D = R '= R is hydrogen and m-phenoxybenzyl alcohol

(in formula XVII: 7? is oxygen, D is hydrogen, η is 0). Other specific esters within the scope of the above classes are described in detail in British Patent 1,413,491.

The synthesis of the acetyl compounds II by the in the Reaction Scheme B given gives the desired reactions pure trans isomers and the subsequent reaction sequence to the vinyl esters VI retains the trans configuration. Regardless of this, any trans compound of formulas II to VII can be included in it, if so desired cis isomer or a mixture of cis / trans isomers for Purpose of making the cis or cis / trans insecticides Compounds of general formula I are converted.

Suitably a cis / trans mixture can be converted by converting a compound of the formulas II, III, V or VI in its acid chloride, and heating the acid chloride to over 100 C,

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for example 'at 110 ° C to 150 ° C. The heating of the acid VII acid chloride results in an equilibrium mixture of the cis / trans ratio of 20 to 25 ^: 80 to 75 * Mixtures can be separated by any known method including distillation of an ester (R is alkyl) or fractional crystallization of the corresponding acids (R is hydrogen).

The intermediates of the formulas II to VII ₅ and the insecticidal esters of the formula I can have both optical and geometric isomerism.

The formation of the cyclopropane ring in an early stage of the Synthetic route, to compounds VI and VII allowed ^ if desired j the separation of the optical isomers from the racematic Starting acetyl compounds II to the more active insecticides (+) - Isomers of the compounds I via the (+) - isomers of 'Connections II to V. ·'

The raeemates of any of these compounds can be in the ("+ '■)"' and (-j-isomers for the production of the corresponding C +) · ^ 'or (-) - insecficidal esters are separated, or it can use the racemates themselves to produce the 'racemic

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1639777

insecticides. Ester.der formula I can be used.

The racemates of the compounds II to VI can be prepared according to known Process are separated, preferably by optical separation of the corresponding. (+.) - Acid with an optical active base, for example an alkaloid such as quinine, or a-phenylethylamine, or threo-1-p-nitropheny1-2- (N, N-dimethylamino) propane-1,3-diol.

Accordingly, the present invention has the following Features that are also considered in the claims, but the invention is not limited thereto and is intended to include all new features described in the present description and claims:

(a) A compound of the formulas III-, IV and V.

(b) A compound of formulas III, IV and V with a trans configuration.

(c) A Verbindung.der formulas III _s IV and V in the form of their racemates.

(d). The synthesis of a compound of formula III which • the halogenation of a compound of the. Formula II includes.

(e) The synthesis of a compound of Formula IV which comprises reducing a compound of Formula III.

(f) The esterification of a compound of formula IV with a

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ι ■

Acid R OH to create an ester of formula V.

(g) The elimination of the acid R OH from a compound of Formula V (optionally with simultaneous hydrolysis) to create a compound of Formula VI (or or their acid of the formula VII) and where the ester VI has been formed, hydrolysis of the ester to acid VII.

(h) The synthesis of a compound of formula I wherein B is a cyclic radical as described above, soft the esterification of an acid of formula VII or a reactive derivative thereof with an alcohol BOH or a reactive derivative thereof, wherein the acid or reactive derivative thereof is derived from a compound of formula V.

(i) The synthesis according to section (h), in which the compound of the formula V is derived from a compound of the formula IV,

(j) The synthesis of section (i), wherein the compound of the formula IV is derived from a compound of the formula III.

(k) The synthesis of section (j), wherein the compound • of the formula III is derived from a compound of the formula II.

The following examples serve to illustrate the invention .

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Example 1 A: Carboethoxymethyldimethylsulfonium bromide

A solution of ethyl bromoacetate (530 g, 3 ₃ 17 mol) and dimethyl sulfide (228 g, 3.67 mol) in acetone (1.0 liter) was stirred at room temperature for three days. Filtration of the mixture provided the sulfonium bromide as a white crystalline solid; Melting point 78 to 79 ° C.

B: A'thy! - (dimethy! Sulfuranylidene) acetate

A solution of sulfonium (85 _a 7 g ₃ O ₃ 37 mole) in chloroform (280 ml) was vigorously stirred at 5 to 10 ° C and with a mixture of saturated potassium carbonate solution (212 ml) and sodium hydroxide-I2,5n Solution (29.5 ml) treated in one serving. The reaction mixture was heated to 15-20 ° C. and held at this temperature for 15 minutes. After removing the salt by filtration, the filtrate was separated and the upper chloroform layer was dried over anhydrous potassium carbonate for 2 hours. Removal of the solvent in vacuo at 25 ° C. and 1 mm mercury pressure gave the ylid in the form of a light yellow oil.

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C: (±) -trans-ethyl-3 ~ acetyl-2j2-dimethylcyclopropane-1-carboxylate

A solution of the ylide (49.3 g, 0.33 mol) and mesityl oxide (146 g, 1.49 mol) in dry benzene (750 ml) was refluxed for 18 hours. After removing the solvent and the excess reagent by distillation, a residue was obtained. This liquid return ■ supernatant was fractionally distilled and the mm at 45 ° C and O ₃ I mercury pressure boiling fraction collected separately. The desired cyclopropane was obtained in the form of a colorless liquid,

. B e i s ρ i e 1 2

(±) -trans-ethyl-3 ~ dichloroacetyl-2 ₃ 2-dimethylcyclopropane-1- . carboxylate

Sulfuryl chloride (59.4 g, Q, 44 mol) was added dropwise Ethyl 3-acetyl-2,2-dimethylcyclopropane-1-carboxylate (20.4 g, 0.11 mol) below. Ice cooling added. The solution was stirred at room temperature for 16 hours. The excess Reagent was removed in vacuo and the residue in Ether (50 ml) dissolved. The ether was washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo. A light yellow liquid was obtained with a Boiling point of 85 ° C / 0.05 mm Hg.

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Example 3

(±) -trans-Α'thy 1-3- (3, ß-dichloro-α-hydroxyethyl) -2,2-dimethylcyclopropane-1-carboxylate

Solid sodium borohydride (2.4 g, 0.063 mol) was added portionwise to a cooled solution of (±) -trans-ethyl-3-dichloroacetyl-2,2-dimethylcyclopropane-1-carboxylate (16.0 g, 0.063 mol) in methanol (160 ml) was added. The reaction mixture was stirred at room temperature for 3 hours. Most of the methanol was removed in vacuo and the residue poured into ice water (150 ml). The water was extracted with ether (3 x 100 ml), the essential Combined extracts, dried over anhydrous sodium sulfate and concentrated in vacuo. The hydroxy compound was obtained as a light yellow liquid with a boiling point of 110 ° C / 0.07 mm Hg.

Example 4

(±) -trans-ethyl-3- (β, ß-dichloro-α-hydroxyethyl) -2,2-dimethylcyclopropane-1-carboxylate

Aluminum isopropoxide (0.97 g, 0.005 mole) and (±) -trans -ethyl 1-3-dichloroacetyl-2,2-dimethylcyclopropane-1-carboxylate (1.0 g, 0.004 mol) were in isopropanol (6.0 ml) for 16 hours heated to reflux. After cooling, the mixture became in

- 23 - 709810/1189

Poured 2N hydrochloric acid (50 ml) and then extracted with ether (3 x 30 ml). The united organic Layers were extracted with water (2 × 50 ml), dried and concentrated in vacuo. A colorless oil was obtained. This product was identical [NMR and IR spectra and gas-liquid chromatography (GLC)] with that by sodium borohydride reduction obtained title compound of Example 3.

Example 5

(±) -trans-ethyl-3- (ßass-dichloro-q-tosyloxyethyl) -2 _a 2-dimethylcyclopropane-1-carboxylate

A solution of (±) -trans-ethyl-3- (ß, ß-dichloro-α-hydroxyethyl) -2,2-dimethylcyclopropane-1-carboxylate (28.0 g, O ₃ Il mol) in pyridine (168 ml ) was added dropwise to a solution of tosyl chloride (44.2 g, 0.23 mol) in pyridine (224 ml) kept at 40 ° C. After the addition was complete, the mixture was stored at 4 ° C for 3 days. Most of the pyridine was removed in vacuo at 40 ° C. and the remainder was poured into ice water (200 ml). After acidification with concentrated hydrochloric acid, this mixture was extracted with ether (3 × 100 ml), the ethereal layers combined, dried and evaporated to a light yellow oil which crystallized on standing. That

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Tosylate was recrystallized from cyclohexane and had a melting point of 71 ° C.

Example 6

(±) -trans-ethyl-3- (β, β-dichlorovinyl) -2 ^ -dimethylcyclopropane-1-carboxylate

(±) -trans-Ethy1-3- (ß, ß-dichloro-a-tosyloxyäthy1) -2,2-dimethy1-cyclopropane-1-carboxylate (0.5 g, 0.0012 mol) and n-sodium hydroxide solution (2.5 ml) in ethanol (2.5 ml) were refluxed for 1 hour. After cooling, the Mixture poured into water (20 ml), acidified with concentrated hydrochloric acid and washed with ether (3 χ 10 ml) extracted. The combined organic phases were washed with water (2 × 15 ml) over anhydrous sodium sulfate dried and concentrated in vacuo. A colorless oil was obtained. This oil was identical (NMR and IR spectra and GLC) with an authentic sample of the title ester.

Example 7

(±) -trans-3- (ß _i ß-Diehlorvinyl) -2,2-dimethylcyclopropane-1-carboxylic acid

(±) -trans-ethyl-3- (β3β-dichlorovinyl) -2,2-dimethylcyclopropane-1-carboxylate (4.2 g, 0.018 mol) and n-sodium hydroxide

- 25 -70 9 810/118 9 ,,

Solution (36.0 ml) in ethanol (36.0 ml) was added for 1 hour heated to reflux. After cooling, the mixture was poured into water (200 ml) and treated with concentrated hydrogen chloride acidified. It was extracted with ether (3 × 100 ml), the ethereal layers were combined with water (2 × 100 ml), dried over anhydrous sodium sulfate and evaporated in vacuo. The title compound was obtained as an almost white pest that was recrystallized from cyclohexane; Melting point 94 to 95 ° C

Example 8

(±) -trans-3 "(ß ₃ 3-dichlorovinyl) -2,2-dimethyleyclopropane-1-carboxylic acid

A mixture of (±) -trans-ethyl-3- (3, ß-dichloro-a-tosyloxyäthylJ - ^^ - dimethylcyclopropane-l-carboxylate (10.0 g, 0.024 mol) in ethanol (100 ml) and n- Sodium hydroxide solution (100 ml) was heated to reflux for 1 hour. The excess alcohol was removed in vacuo and the residue was acidified with concentrated hydrochloric acid and extracted with ether (3 × βθ ml). The combined ether extracts were washed with saturated sodium chloride solution (2 × 100 ml), extracted, dried over anhydrous sodium sulfate and concentrated in vacuo. The acid was obtained as a creamy solid which was recrystallized from cyclohexane; melting point 93 to 95 ° C (lit .: 95 to 96 ° C). "''-

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7098 1 0/11 8 9 _-: ■ -.- ■■

Example 9

(±) -trans-m-Phenoxybenzy1-3- (β, ß-dichloroviny1) -2,2-dimethylcyclopropane-1-carboxylate

(±) -trans -3- (β, β-dichlorovinyl) -2,2-dimethylcyclopropane-lcarboxylic acid (1.0 g, 0.0048 mol), m-phenoxybenzyl alcohol (1.0 g, 0.0050 mol) and p-Toluenesulfonic acid (0.01 g) in toluene (100 ml) was refluxed with a Dean-Stark trap for 36 hours. After cooling, the solution was extracted with 5% aqueous sodium bicarbonate (2 × 50 ml) ₃ then with water (2 × 50 ml), dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was applied to an acid-washed alumina column using petroleum ether (boiling point 80 ° to 100 ° C.) as the eluent. Evaporation of the solvent gave a colorless oil which crystallized on standing. The product was identical (NMR, IR and UV spectra, TLC and GLC) to an authentic sample of the title compound.

Example 10

A: (±) -trans-ethyl-3- (ß, ß-dichloro-a-bros.yloxyethyl) -2-dimethylcyclopropane-1-carboxylate

A solution of (±) -trans-ethyl-3- (ß, ß "-ciichlor-a-hydroxy-

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7 0 9 8 1 night / 1 1 a 9

ethyl) -2 _a 2-dimethylcycLopropane-1-earboxylate (5.0 g, 0.020 mol) in pyridine (30 ml) was added dropwise to a solution of brosyl chloride (10.18 g, 0.040 mol) in pyridine (3.0 ml), the was kept at 40 ° C, was added. After completion of the addition, the mixture at room temperature for 3 days ^has been stirred und.dann in water (200 ml), acidified with concentrated hydrochloric acid, with ether (3 x 80 ml), dried over anhydrous magnesium sulfate and concentrated in vacuo. A white plague was obtained which was recrystallized from cyclohexane; Melting point 83 ° C.

B: In a similar reaction in which mesyl chloride was used instead of brosyl chloride, (±) -trans-ethyl-'3- (3a ß-dichloro-α-mesyloxyethyl) -2,2-dimethylcyclopropane-1-carboxylate was obtained in Form of a light yellow liquid. 0 (CDCl ₃ ) 1.12 to 1.39 (9H ₃ m), 1.62 to 2.15 (2H, m),

3.18 (3H, s), / i |, 18 (2H, q, J 7 Hz.), 4.70 (IH, d of d, J 3 & 9 Hz), 6.03 (IH, d, J 3 Hz).

B e i s.p i e 1 11

(±) -trans-ethyl-3- (3, ß-dichlorovinyl) -2,2-dime; thylcyclopropane-1-carboxylate '"" ..... ".

A: A mixture of the brosylate product from Example 10A

'- 28 -

7098 10/1 89 ^; : -. = . ■; ;?, ■

(1.3 g, 0.0027 mol) in ethanol (5.4 ml) and n-sodium hydroxide solution (5.4 ml) was refluxed for 1 hour. After cooling, the reaction mixture was in Poured water (100 ml) and acidified with concentrated hydrochloric acid. It was extracted with ether (3 × 50 ml), dried over anhydrous magnesium sulfate and concentrated in vacuo. The product was obtained in the form of a colorless oil.

B: The mesylate product of Example 10B was similarly converted to the title compound.

Example 12

(±) -trans-Ethy1-3- (ß > β-dichloro-α-trifluoroacetoxyethyl) -2,2-dimethylcyclopropane-1-carboxylate

(±) -trans-Ethy1-3- (ß, ß-dichloro-α-hydroxyäthy1) -2,2-dimethy1-cyclopropane-1-carboxylate (1.0 g, 0.004 mol) was treated with trifluoroacetic anhydride (5.0 g, 0.024 mol) and the mixture at room temperature for 16 hours in a stirred in a moisture-free atmosphere. The excess reagent was removed in vacuo and the trifluoroacetate remained in the form of a light yellow liquid. This was stored in the absence of moisture and without further Cleaning used.

- 29 7 0 9 8 1 U / 1 1 8 9

) 1.08 to 1.41 (9 Hz, m), 1.57 to 2.07 C2H, m), -4.18 (2Hj q, J 7Hz), 5.06 (IH, d of d, J_ 5 & 9 Hz), 5.92 (IH, d, J 5 Hz). =;

' Example 13 "■

(±) -trans-Sthy1-5- (3 ₉ ß-dichlorovinyl) -2,2-dimethylcyelopropan-1-carboxylate

The trifluoroacetate product of Example 12 (2.0 g, 0 ^ 0057 Mol) was in dry benzene (-15 ml) - with potassium tert-butoxide (0.96 g, 0.0086 mol) and the mixture stirred at room temperature for 20 hours. Then im Concentrated in vacuo and the residue extracted with 40/60 petroleum ether. After filtration, the petroleum ether was evaporated and the residue separated by GiLC.

■ B is ρ ie 1 14 ' trans-3-acetyl-2,2- ^ dimethylcyclopropane-1-carboxylic acid

Ethyl-1-acetyl-Zj ^ -di'methyleyclopropane-1-erboxylate (3'6> O g, 0.2 mol) and n-potassium hydroxide (391 ml) in ethanol (391 ml) were for 2 hours on Heated to reflux. The excess alcohol was removed in vacuo and the solution obtained was' ^{acidified with concentrated hydrochloric acid (■ '' v-:} 40ml) ^! acidifies. As a result, a solid was precipitated ^ which with -

- 30 7 0 9 8 10/1 1 8 θ

Ether (3 x 200 ml) was extracted. The ether extract was dried over anhydrous magnesium sulfate and in vacuo constricted. A cream-like pest with a melting point of 111 ° C. was obtained.

Example 15 (tj-transO-acetyl ^^ - dimethylcyclopropane-1-carboxamide

Thionyl chloride (45.7 g »0.40 mol) was added dropwise a solution of 5-acetyl-2,2-dimethylcyclopropäri-1-carboxylic acid (30.0 g, 0.20 mol) in benzene (300 ml) and the mixture heated under reflux for 2 hours. Excess The solvent and reagent were removed in vacuo and the The residue was dissolved in dimethoxyethane (320 ml). This solution became dimethoxyethane (1600 ml) with ammonia gas saturated 'was added and the mixture allowed to stand at room temperature for 16 hours. After removal of any inorganic salts by filtration, the filtrate was concentrated in vacuo to obtain one white solid identified as the desired amide.

- 31 7098 10/1180

639777

B e i s, ρ i e 1 16 (±) -trans-5 ~ acetyl-1-cyano-2,2-diinethylcyclopropane

Phosphorus oxychloride (202.4 g, 1.3-2 moles) was added dropwise to a solution of 3-acetyl-2,2-dimethylcyclopropane-lcarboxamide (3.6 g, 0.22 mol) in benzene (140 ml) and the resulting mixture is refluxed for 3 hours. The excess reagents were removed in vacuo and the residue dissolved in ether (100 ml). The ether was washed with water (3 × 60 ml) over anhydrous Magnesium sulfate dried and concentrated in vacuo. A dark oil with a boiling point of 72 to 75 C / 1.0 mm Hg.-

Example 17

(±) -trans-benzyl-3-acety1-2,2-dimethylcyclopropane carboxylate

Thionyl chloride (25.5 g _s 0.21 mol) was added dropwise to a solution of ^ -acetyl ^^ - dimethylcyclopropane-l-carboxylic acid (16.7 g, 0.11 mol) in dry benzene (250 ml) and then the mixture was refluxed for 2 hours. This mixture was concentrated in vacuo, the residue was taken up in benzene (100 ml) and concentrated again. This residue was dissolved in benzene (150 ml) and benzyl

- 32 7098 1 U / 1 1 8 9.

alcohol (13.1 g, 0.12 mol) added. After the Mixture in ice, pyridine (11.3 g, 0.12 mol) was added dropwise added and the mixture stirred at room temperature for 16 hours. This organic phase was washed with 2N sodium hydroxide solution (2 χ 80 ml) ,. Water (2 80 ml), n-hydrochloric acid (2 80 ml), water (2 χ 80 ml) and saline solution (1 χ 80 ml) extracted, then dried over anhydrous magnesium sulfate and concentrated in vacuo. A pale yellow oil was obtained. Purification was carried out by applying to a clay column (75 g) using 40/60 petroleum ether as the eluent. One received so a clear viscous oil.

Example 18

(±) -trans-benzyl-3 ~ dichloroacetyl-2 _? 2-dimethylcyclopropane-1-carboxylate

Sulfuryl chloride (39 »5 g> 0.29 mol) was added dropwise to benzyl ^ -aetyl ^^ - dimethylcyclopropane-1-carboxylate (18.0 g, 0.07 mol) was added with ice cooling. This solution was stirred at room temperature for 16 hours. The excess Reagent was removed in vacuo and the residue dissolved in ether (100 ml). The a'ther was mixed with water (2 χ 50 ml) washed, dried over anhydrous magnesium sulfate and concentrated in vacuo. A viscous oil was obtained.

- 33 7 0 9 8 10/1189

1.38 (3H, β), 1.58 (3Η, s) ₅ 2.74 (IH, d, J 6 Hz), 3.17 (IH ₃ d, j -6 Hz), 5.41 (2H , s), 6.11 (IH, s), 7.69 (5H, sj '.-''.'■; - · ■■■■ -.- "

Be is ρ i e-1 19. "■■■■" ·

(±) -trans-benzyl-3 ~ (ß, ß-diehlor-g-hydroxyäthy1) -2,2-dimethyΙο ycIoprορan-1-carboxylate . ■

Solid sodium borohydride (2.56 g, 0.068 mol) was added portionwise to a cooled solution of the product from Example 18 (21.3 g, 0.068 mol) in methanol (200 ml). The reaction mixture was stirred at room temperature for 3 hours and then most of the methanol was removed under vacuum. The residue was poured into ice water (200 ml) and extracted with ether (3 × 10 ml). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated in vacuo to a yellow oil. Purification was (g 100, Grade III) by task in a Tonerdesäüle using 4o / 60 ^ ^P.! Etrolätherals "Eluiermittei to remove a fast running-product causes the subsequent further elution with Toluol'lie- ferte the desired dichloro .... alcoholic ^'J ·: ·: ..: · ■■ · 0 (CDCl ₃₎ 1.32 (6H, s) V to ^1V52; l, 91 (2Hi m) ,: 2y62 (IH; - ^ ^; Broad s, interchangeable with. 'DpO-) ■,' 3 ^ 51 to 3 '-, 79 ·' (IH, m) ;, 5.79 (IH, ^ J ^ H ^ l V ₃ W ( 5H, s), ^{: ?} -

709810/1189

(Film) 3 ^ 57, 1730, 1165, 1117, 791, 733, 698 cm " ¹

Example 20

(±) -trans-Benzy 1-3- (β, 3-dichloro-ot-tosyioxyäth.y 1) -2,2-dimethylcyclopropane -! - carboxylate

A solution of the product from Example 19 (5.0 g, 0.016 mol) in pyridine (30 ml) was added dropwise to a solution of tosyl chloride (6.0 g, 0.032 mol) in pyridine (30 ml) and the mixture was allowed to stand at room temperature for 3 days. Most of the pyridine was removed in vacuo and the residue poured into ice water (200 ml). It was then acidified with concentrated hydrochloric acid and extracted with ether (3 × 100 ml). The combined layers of ether were poured over anhydrous magnesium sulfate dried and concentrated in vacuo to a thick oil. This was triturated with 40/60 petroleum ether and obtained the tosylate as an almost white pest. The recrystallization from 60/80 petroleum ether gave a product with a melting point of 98 ° C.

6 (CDCl ₃ ) 1.21 (3H, s), 1.24 (3H, s), 1.76-2.22 (2H, m), 2.52 (3H, s), 4.72 (IH , d of d, J 3 & 9Hz), 5.22 (2H, s), 5.99 (IH, d, J 3 Hz), 7.26 to 7.95 (9H, m). ^;

^v max ^(mull >! 726, 1217, 1177, 920, 840, cm " ¹

- 35 709810/11 8, a

639777

Example 21

(±) -trans-Benzy1-3- (3,3-dichlorovinyl) -2,2-dimethylcyclopropane-1-carboxylate

Potassium tertiary butoxide (0.74 g, 0.0066 moles) became the product from Example 18 (2.0 g, 0.0044 mol) in dry benzene (100 ml) was added and the mixture was refluxed for 16 hours. After cooling, the reaction mixture became poured into ice water (200 ml) and acidified with concentrated hydrochloric acid. The organic layer was separated and the aqueous layer extracted with ether (2 × 100 ml). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated in vacuo to a brown oil. This was done by giving up on a clay column (6 g, grade III) using 60/80 petroleum ether as the eluent. One received in this way the desired compound in the form of a colorless oil. The product was identical (NMR and IR spectra, TLC and GLC) with an authentic sample.

6 (CDCl _x ) 1.18 (3H, s), 1.3 ¹ J (3H, s), 1.67 (IH, d, J 6 Hz) ₅ " j

2.29 (IH, d of d, J 6 & 9Hz), 5.18 (2H, s), 5.67 (IH, d, J 9 Hz), 7.42 (5H, s). v _m (film) 1731, 1225, II66 / III7, 882, 698 cm " ¹

ITIcLX

7 0 9 8 1 night / 1 1 8 9

Example 22 . m-Phenoxybenzyl (dimethyIsulfuranylidene) acetate

A solution of carbo- (m-phenoxybenzoxy) -methyl-dimethylsulfonium bromide (50.0 g, 0.13 mol) in chloroform (103 ml) was stirred vigorously at 5 to 10 ° C and in a portion with a mixture of saturated potassium carbonate Solution (78 ml) and I2.5N sodium hydroxide solution (1O ₅ 3 ml). The reaction mixture was warmed to 15-20 ° C. and held at that temperature for 15 minutes. After removing the salt by filtration, the piltrate was separated and the upper chloroform layer was dried over anhydrous potassium carbonate for 2 hours. Removal of the solvent in vacuo at 25 ° C. and 1 mm Hg gave the ylid in the form of a light yellow oil.

Example 23

(±) -trans-m-phenoxybenzyl-3-acetyl-2j2-dimethylcyclopropane-1-carboxylate

(a) A solution of the product from Example 22 (34.6 g, 0.11 mole) and mesityl oxide (44.7 g, 0.46 mole) in ethanol (330 ml) was refluxed for 16 hours. The distance of the solvent and excess reagent in vacuo yielded a 37.5 g residue

- 37 7 0 9 8 10/1189

by placing on a Torierdesäule. (120 g, grade III) under Use of..60: 7.Sö-rPefcroläther with a content of less than 10% Purified toluene as the eluent and so the · compound · ^ in '^ orm' of a light yellow oil was obtained. ' . ·

(b) A ¹ solution of (+ j-trans ^ -Acet'yl ^^ - dimethylcyclo ^ - propane-1-carboxylic acid ^: (33 _s 3 g:>'- Ö., 21 mol) in dry benzene ¹ ( 500 'ml> - was treated with thionyl chloride (50.8 g, 0-, 42MoI)' and refluxed for 2 hours '. Then it was concentrated in vacuo to remove the excess' and the residue . (300 ml) in'trockenem benzene to the cooled solution was added m-Phenoxybehzy alcohol (38.3 g, 0 _a ^{21-; i} mol)! and ans'chließend dropwise 'pyridine (16.8 g, 0,21MoI The reaction mixture was stirred at room temperature for 16 hours. After filtration, the "solution was mixed with 2N sodium hydroxide solution (2 × 100 ml), water (2 × 100 ml), n-hydrochloric acid (2 × 100 ml) ml), water (2 χ lÖ ^ Wk ^ -undiige "saturated KbGhSaI ^ solution ■ Cl x ^ -10O- ml> * - ··· - · extracted, then dried over anhydrous magnesium sulfate and finally concentrated in vacuo So the Ester, who with ^! the 'ob'en about' the Suifuryiid'hergesteliten '""'"i dentiWäii liar - (TFt and "NMR spectra, TLÖ and'GLC) V ■ * '*'

- 38 9.8 107Ϊ 18 £ ' ^! . ^{! ;} · ^Ν: ^ · ^: '

B el ^: -s ρ '

(±) -trans * · m-Pherio'xybehzyl-3 ^> ~ dichloroacetyl-2,2-dimethyi ^a · " ^; - ' ^r cy cloprop'an-1-c-arbo'xylat ■ -''''>^; - ^: ~ ->'"- ^: ■■'<- ■ '· - ^; · ^ ··

(a) Chlorine gas (2.1 g; 0.03 mol) would be dissolved in ice-cold carbon tetrachloride (5Ö räl) and added to this solution of m-phenoxybenzyl-S-acetyl- ^ jS-diniethyl'cyciöpropän-l- ArBoicylät " (1.3 g ₃ 0.004 mol) was added. The KoIbeff" was sealed and allowed to stand at room temperature for '16 hours'. “After removing the solvent” in vacuo, a light yellow oil remained. This material was purified by "Chromätograpilie an" alumina building (8 g, grade III) under "Vergewehdürig" of 40 liters petroleum ether as the eluent, collecting the slowest running compound. Spectroscopic identification of this compound showed that it the

desired 'connection ^; would be. '■ - - ■ ··, -' ■ - - ^: --- ^: ■■■■ '- ■■' - '- ■ - ■ - ■ ■ = ----- ■ --- ■ " -

6 (CDCI) 1.29 (3H, s),% M ^; (3H, ^ W ^ ^: M "(^^^ 5 ^: ^ z) _s 3.02 (IH, d, J 5 Hz), 4.73 (2H, s), 5.22 (IH, s), '''■■'$; Ϊ2 '( ¹ IH ", - s7, ' S, 96 to Y; 6l (9R ^,! M). '"' * '"'" ^

(b) Eide solution of '■ ^; 3-Tue ^! chrorac ^T etyr-2,2-dimethyicyc ^: loprOpan-1-carbonic acid ^; ( ^J 1, O g, ' % ₃ 004' MoI) in "tröckenek benzene" (25 "mlj" was treated with 'TtiiohVichlörid (1.2 g, 0,' Öök mbff and '' refluxed for 2 hours'Heitz'tV"Darin" was """in a vacuum" for the Eritfer- """nung'" of the surplus Reägeritien and

7 0 9 8 1 0/1 1 3 9 ^ ' ^{: j} : => ^v ■ ■

the residue was dissolved in dry benzene (25 ml). m-phenoxybenzyl alcohol (0.8 g, 0.00.4 mol) was added, the Mixture chilled in ice and pyridine (0.4 g, 0.005 mol) added dropwise. The reaction mixture was at Stirred at room temperature for 16 hours. After filtration, the solution was treated with 2N sodium hydroxide solution (2 × 20 ml), water , (2 χ 20 ml), n-hydrochloric acid (2 χ 20 ml), Water (2 χ 20 ml) and saturated saline solution (1 χ 20 ml) extracted j, then dried over anhydrous magnesium sulfate and finally concentrated in vacuo. In this way, the ester is obtained as a pale yellow oil, that with the above produced material was identical (IR and NMR spectra, TLC and GLC). ·

Example 25

(±) -trans-m-phenoxybenzy1-3- (8> 8-dichloro-q-hydroxyethy1) -2,2-dimethylcyclopropane-1-carboxylate

Sodium borohydride (3.17 g _s 0.084 mol) was added portionwise to a cooled solution of the product from Example 24 (34.0 g · 0.084 mol) in methanol (300 ml). The reaction mixture was stirred at room temperature for 3 hours and then most of the methanol was removed in vacuo before the residue was poured into ice water (300 ml). Then it was extracted with ether (3 x 150 ml), the combined

- 40 7 0981 0/1 18a ---, -. ■ ·. · - ..

th ether extracts dried over anhydrous magnesium sulfate and the ether finally evaporated, whereby a viscous oil was obtained as a residue. Purification was carried out by chromatography on a clay column (150 g, grade III) using 60/80 petroleum ether as the eluent to remove a fast running by-product. The subsequent further elution with 60/80 petroleum ether containing 10 % toluene yielded the desired dichloro alcohol.

6 (CDCl ₃ ) 1.39 (6H, s), 1.69 to 1.94 (2H, m), 2.63 (IH, s, interchangeable with D ₂ O), 3.54 to 3.83 ( IH, m), 5.20 (2H, s), 5.81 (IH, d, J 5 Hz), 6.99 to 7.56 (9H, m).

ν (film) 3462, 1732, 1589, 1490, 1258, 1216, 1165, 692 cm " ¹

Example 26

(±) -trans ~ m-Phenoxybenzyl-3- (ß, ß-dichloro-a-tosyloxyethyl) -2,2-dimethylcyclopropane-1-carboxylate

A solution of the product from Example 25 (12.5 g, 0.03 mol) in pyridine (50 ml) was added dropwise to a solution of Tosyl chloride (12.1 g, 0.063 mol) in pyridine (50 ml) was added and the mixture was allowed to stand at room temperature for 3 days. Most of the pyridine was removed in vacuo

- 41 7 0 9 8 10/1189

639777

and the residue poured into ice water (300 ml). It was then acidified with concentrated hydrochloric acid and with Ether (3 x 150 ml) extracted »The combined ether extracts were dried over anhydrous magnesium sulfate and after Concentration in vacuo gave a viscous oil. This oil was eluted through a clay column (50 g, grade III) purified using 40/60 petroleum ether as the eluant.

0 (CDCl ₃ ) 0.94 (3H, s), 1.08 (3H _S s), 1.38 to 1.90 (2H, m), ■ 2.25. (3H-, s), 4.49 (IH, d of d, J 3 & 9 Hz), 4.96 (2H, s), 5.92 (IH, d, J 3 Hz), 6.75 to 7.81 (13H, m).
v _m o _V (film) 1732, 1590, 1491, 1258, 1216, 1178, 692 cm " ¹ .

Example 27

(±) -trans-m-phenoxybenzyl-3- (β, β-dichloroviny1) -2,2-dimethylcyclopropane-1-carboxylate

Potassium tertiary butoxide (0.45 g, 0.004 mole) became the product from Example 26 (1.0 g, 0.002 mol) in dry benzene (20 ml) was added and the mixture was refluxed for 16 hours. After cooling, the reaction mixture became Poured into ice water (100 ml) and acidified with concentrated hydrochloric acid. The organic layer was separated and the aqueous layer with ether (2 χ 50 ml)

- 42 7 0 9.8 10/1 1 8 a "'· ■■

extracted. The combined organic layers were dried over anhydrous magnesium sulfate and in vacuo concentrated to a yellow oil. The purification was carried out by chromatography on a clay column (3 g, grade III) below Elute with 40/60 petroleum ether to give a white plague with a melting point of 45 ° C. The product was identical (IR and NMR spectra and TLC and GLC) with an authentic material.

Example 28

(±) -trans-ethyl-3-dibromoacetyl-2 ₃ 2-dimethylcyclopropane carboxylate

To ethyl 3-acetyl-2,2-dimethylcyclopropane-1-carboxylate (12.0 g, 0.065 mol) in ether (600 ml) was added dropwise bromine (26.0 g, 0.160 mol). The solution was with 10 ^ iger sodium bicarbonate solution (3 × 200 ml) and water (2 × 200 ml) extracted, dried over anhydrous magnesium sulfate and concentrated in vacuo. A light yellow one was obtained Liquid from which no further attempts have been made to purify it.

Example 29

(±) -trans-ethyl-3- (ß, ß-dibromo-α-hydroxyethyl) -2,2-dimethylcyclopropane-1-carboxylate

- 43 709810/1189

Solid sodium borohydride (2.38 g, 0.063 mol) was added portionwise to a cooled solution of the dibromoketone product of Example 28 (21.6 g, 0.06.3 mol) in methanol (300 ml) admitted. The reaction mixture was stirred at room temperature for 3 hours. The bulk of the methanol was removed in vacuo and the residue poured into ice water (200 ml). Then it was extracted with ether (3 × 100 ml), the essential extracts combined, dried over anhydrous magnesium sulfate and evaporated in vacuo. One received the hydroxy compound as a light yellow oil; Boiling point 130 ° C / 0.1 mm Hg.

Example 30

(±) -trans-ethyl-3- (3, ß-dibromo-a-tosyloxyethyl) -2,2-dimethylcyclopropane-1-carboxylate

A solution of the product from Example 29 (11.0 g, 0.032 mol) in pyridine (63 ml) was added dropwise to a solution of tosyl chloride (12.7 g _s 0.067 mol) in pyridine (92 ml) and the mixture 3 days left to stand for a long time at room temperature. Most of the pyridine was removed in vacuo and the residue poured into ice water (100 ml). After acidification with concentrated hydrochloric acid, the mixture was extracted with ether (3 × 50 ml), the ether extracts were combined, washed with water (3 × 50 ml), then saline

7 09810/1189

solution (1 × 100 ml) washed over anhydrous magnesium sulfate dried and concentrated in vacuo. A pale yellow oil (15.1 g) was obtained. This oil was in petroleum ether (600 ml) and the tosylate crystallized in the form of white prisms on standing. The product was in 40/60 petroleum ether recrystallized; melting point 84 ° C.

Example 31

(±) -trans -3 (β, β-dibromoviny1) -2,2-dimethylcyclopropane-1-carboxylic acid

A mixture of the product from Example 30 (3 ₅ 7 gj 0.0074 mol) in ethanol (30 ml) and n-sodium hydroxide solution (29.6 ml) was refluxed for 3 hours. The excess alcohol was removed in vacuo and the residue acidified with concentrated hydrochloric acid. A light yellow precipitate separated out on standing and was filtered off, washed with water and dried. The product was recrystallized from 40/60 petroleum ether; Melting point 125 to 126 ° C.

B. e f S. P. 1 e 1 U 32 A. U t r e η η η g

trans-3 ~ acetyl-2a2-dimethylcyclopropane-1-carboxylic acid

- 45 709810/1189

(±) -trans-3-acetyl-2,2-dimethylcyclopropane-1-carboxylic acid (1.0 g, 0.026 mol) was dissolved in a mixture of diisopropyl ether (170 ml) and methanol (30 ml) heated to 60 ° C and (+) - a-methylbenzylamine (3 »1 g ₃ O _s O26 mol) The mixture was heated for 30 minutes at reflux and then cooled The resulting crystals were removed by filtration and recrystallized twice from a mixture.. recrystallized from diisopropyl ether and methanol (80:10), giving a solid (2.3 g) with a constant specific rotation of + 10.12 ° Hydrolysis of this salt with 2N hydrochloric acid (30 ml), extraction with ether (2 × 20 ml), drying the ether extracts over anhydrous magnesium sulfate and subsequent concentration in vacuo gave the (+) - acid (1.1 g, 54 % yield). Recrystallization took place from ethanol Using Eu (hfc), showed that the optical purity was 62 % ' (+) and 38 % (-) .

Example 33

(±) -trans -3-dichloroacetyl-2,2-dimethylcyclopropane carboxylic acid

To (±) -trans-3-AcetyT-2,2-dimethylcyclopropane ⁱ -l-carboxylic acid (10.0 g, 0.064 mol) in ether (100 ml) was added dropwise sulfuryl chloride (69.1 g ₃ 0.51 Mol) added.

- 46 7098 10/1189

The solution was stirred at room temperature for 16 hours. The excess reagent and solvent were in vacuo removed and the residue dissolved in ether (100 ml). The ether was washed with water over anhydrous magnesium sulfate dried and concentrated in vacuo to give a light yellow liquid; Boiling point 130 ° C / 0.7 mm Hg.

Example 34

Isomerization of the (±) -trans-3 ~ acetyl-2,2-dimethylcyclop r op an-1- carb ο ns acid e

(±) -trans-3-acetyl-2,2-dimethylcyclopropane-1-carboxylic acid (2.0 g, 0.013 mol) and thionyl chloride (3.28 g, 0.026 mol) in toluene (10 ml) were added on for 1 hour Heated to reflux. The excess of reagent and solvent was removed in vacuo and the remaining acid chloride was heated to 144 ° C. for 7 hours. After cooling, the mixture was neutralized with 2N sodium hydroxide solution and then acidified with concentrated hydrochloric acid. The mixture was extracted with ether (3 × 30 ml), the ether was dried over anhydrous magnesium sulfate and evaporated in vacuo. A white plague was obtained (1.9 g, yield 95 %) . HPLC on an ods column showed the presence of the cis isomer (approximate ratio of

- 47 7098 10/1189

70/30 trans / cis) and NMR of the product was identical to the trans isomer.

- 48 7 0 9 8 10/1189

Claims (32)

Claims 1. Process for producing a vinyl compound of the general formula VI R- H, C CH, ³ \ / ³ = CH-CH-CH-X (VI) 2 3
in which each of the radicals R and R is chlorine or bromine, and X is nitrile, carboxyl, carbonamide optionally substituted by one or two lower alkyl groups, carbonyl halide, or a group -COOM, in which M is lower alkyl, aralkyl, aryl or a group B. which means one of the following radicals XIV to XIX: D γ- 4 "-f (XIV); 10- CH ₂ -R 12th (XV) 709810/1 189 N-CH, (XVI); • Lin ^ Y (XVII); Zn CH ₂ -C = CCH ₂ (XVIII); OCH ₂ .ChC.CH ₂ (XIX); 7 098 10/11 8 9 Z can have the meaning -0-, -S-, -CHp- or -CO-, Y is hydrogen or an alkyl, alkenyl or alkynyl group or an aryl or puryl group, either unsubstituted or in the ring by one or more alkyl, alkenyl, alkoxy or halogen groups is substituted, means 8th R and R, which can be the same or different, each Represent hydrogen or an alkyl or alkeny group, R ^ is hydrogen or a methyl group, R and R, which can be the same or different, each represent hydrogen or an alkyl group, 12th R is an organic radical with carbon-carbon unsaturation is in the α-position to the -CHp group, 1 ?
with which R is connected, A / SJ is an aromatic ring or a dihydro- or Indicates tetrahydro analogue thereof X j X, X ^ and X, which are the same or different, are each hydrogen, chlorine or a methyl group ₅ and Z- ^{5 has} the meaning -CHp- or -0- or -S- or -CO-, D has the meaning H, CN or -CECH, 2 Z and Z j which can be the same or different, - 51 709810/1189 each represent chlorine or a methyl group, and η has the value 0, 1 or 2, characterized in that one Acid R OH from a compound of the general formula V , C CH, 2 \ R ² µ (ν) 3 I / \ R 1 -CH-CH-CH-CH-X I ₁ OR ¹ 2 3
where R, R and X have the same meaning as in the general own my formula VI and R is a residue that see from a strong acid of the general formula R OH is eliminated. 2. The method according to claim 1, characterized that the acid R OH is a strong organic acid. 3. The method according to any one of claims 1 and 2, characterized in that the acid R OH is an alkyl sulfonic acid, aryl sulfonic acid, aralkyl sulfonic acid or haloalkanoic acid. 4. The method according to any one of claims 1 to 3 _a da - characterized in that the acid R OH - 52 - 709 810/1189 p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, p-bromobenzenesulfonic acid, trichloroacetic acid or Is trifluoroacetic acid. 5 · The method according to any one of claims 1 to 4, characterized in that the acid R OH is p-toluenesulfonic acid. 6. The method according to any one of claims 1 to 5, characterized in that the elimination is effected using a strong base. 7. Method according to claim 6, characterized that the base is an alkali metal alkoxide in an alkanol, or an alkali metal hydroxide in is an alkanol. 8. The method according to claim 6, characterized in that the base is potassium tert-butoxide is in a non-polar solvent, an alkanol, or a halogenated aliphatic hydrocarbon. 9 · Method according to claim 8, characterized that the solvent is benzene, toluene, carbon tetrachloride, Di chlorine than and / or dichloroethane is. - 53 709810/1189 10. The method according to any one of claims 1 to 9, d a through marked that the reaction is carried out at a temperature in the range up to the reflux temperature of the reaction mixture. 11. The method according to any one of claims 1 to 10, characterized in that the connection of the general formula V by reacting the acid of the allege me men formula R OH as defined in claim 1, or a reactive derivative thereof, with an alcohol of general formula IV H, C CH, \ / R ² V (IV) 3 I ⁷ ^ R- * - CH-CH-CH-CH-X -. "■■." "■■" I OH 2 pts in which R and R ^{J have} the same meaning as in the general formula VI and X has the same meaning as in claim 1, is prepared. 12. The method according to claim 11, characterized in that the reactive derivative the acid R OH is selected from acid chloride and acid bromide and acid anhydride. - 54 709810/1189 13. Method according to one of Claims 11 and 12, characterized characterized in that the alcohol of the general formula IV by reducing a ketone of the general Formula III H, C CH,
3/3 R ² \ (III) R ^ -CH-CO-CH-CH-X 2 3 where R and R have the same meaning in general Have formula VI and X is a group as defined in claim 1 with a suitable selective reducing agent will be produced. 14. The method according to claim 13, characterized in that the reduction using of sodium in ethanol or water, aluminum amalgam in water, one. Alcohol and an aluminum alkoxide, a hydride or catalytic hydrogenation is carried out. 15. The method according to any one of claims 13 and 14, characterized in that the ketone of the general formula III by halogenation of a compound of the general formula II H, C CH, ³ V / ³ C (II) / V CH ₃ CO-CH-CH-X - 55 - 709810/118 9 wherein X has the same meaning as in claim 1 is prepared. 16. - The method according to claim 15 * characterized in that the connection of the general Formula II is chlorinated using sulfuryl chloride or molecular chlorine. 17. Process according to Claim 15 _}, characterized in that the compound of the general formula II is brominated with liquid bromine. 18. Process for the preparation of a compound of the general formula VI according to one of claims 1 to 17 »d. a through characterized in that if X is a group other than the -COOB group, the compound of the general formula VI, if desired, into an esterifiable one Derivative of the general formula VIII H, C CH, R ² C (VIII) IT — C = CH-CH-CH-COQ- ¹ - converts, in which R and R ^ have the same meaning as in the general formula VI, and you have the connec tion of the general formula VIII with a compound BQ - 56 7098 10/1189 converts, in which B has the same meaning as in claim and Q and Q are functional groups or atoms that react with each other to form an ester bond, so as to obtain the desired insecticidal ester of the general Formula VI in which X is a group -COOB as defined in claim 1. 19. The method according to any one of claims 1 to 18, characterized in that, if in of the compound of the general formula V, the radical X is a radical other than carboxyl or a group -COOB, the compound with a base to create an acid of the general formula VII H, C CH, 3/3 R ² V (VII) 3 I ' \ t · ⁵ —C = CH-CH-CH- COOH 2 3
in which R and R ^ have the same meaning as in the general formula V, and optionally via a compound of the general formula VIII, the compound of the general formula VII to create the desired insecticidal ester of the general formula VI according to claim 18 is esterified. 20. Process for producing a connection of the general - 57 7 0 3 8 10/1189 mean formula III, since g e k e η η ζ e i c h η e t j that a compound of the general formula II is halogenated. 21. The method according to any one of claims 1 to 18 and 20, dadu r ch g e k enn ζ e i chnet that X is carboxyl, AlkyIoxycarbonyl or Aralkyloxycarbonyl. 22. The method according to any one of claims 1 to 18, 20 and 21, characterized in that X Is ethoxycarbonyl or benzyloxycarbonyl. 23 · method according to one of claims 1 to 17 and 20, characterized in that X is a Group -COOB as defined in claim 1. 24. The method according to any one of claims 1 to 17, 20 and 23, characterized in that B m-phenoxybenzyl is. 25 · Method according to one of Claims 1 to 24, characterized in that a connection of the general formulas II, III, IV, V, VI, VII or VIII possesses the trans configuration. - 58 7098 10/1189 26. Process for the preparation of a compound of the general formulas III, IV, V, VI ₃ VII or VIII, essentially as described above with particular reference to the examples. 27. The method according to any one of claims 1 to 19 and 23 to 26, characterized in that the compound of the general formula VI trans- (±) -m-phenoxybenzyl-3- (2,2-dichloroviny1) -2,2-dimethylcyclopropane carboxylate is. 28. Compound of the general formulas III, IV, V, VI, VII or VIII according to claims 13, 11, I ₃ 1, 19 or 18, characterized in that it is prepared by the process according to claim 26. 29. A compound of the general formula VI, in which X is a group -COOB as defined in claim 1, d a through characterized in that it is produced by the method according to claim 26. 30. Compound of the general formulas II, III, IV and V according to claims 15, 13, H and 1, respectively, in which X is a group -COOB as defined in claim 1. - 59 ■ 7 0 3 8 10/1189 31. Compound of the general formulas III, IV and V according to claims 13 j H or 1, wherein X Nitrile, carboxyl, carbonyl halide, optionally substituted Is carbonamide or a group -COOM in which M is alkyl, aryl or aralkyl. 32. Connection selected from (±) -trans-Ethy1-3-dichloroacety1-2,2-dimethylcyclopropane-1-carboxylate ,. (±) -trans-Ethy1-3 ~ (ß, ß-dichloro-a-hydroxyäthy1) -2,2-dimethy1-cyclopropane-1-carboxylate, (±) -trans-ethyl-3- (ß, ß-dichloro -a-tosyloxyethyl) -2,2-dimethylcyclopropane-1-carboxylate, (±) -trans-Ethy1-3- (βjß ~ dichloro-a-brosyloxyethyl) -2,2-dimethyl-cyclopropane-1-carboxylate, (± ) -trans-ethyl-3 ~ (ß 3 ß-dichloro-a-trifluoroacetoxyethyl) -2,2-dimethylcyclopropane-1-carboxylate, (±) -trans-benzyl-3 ~ acety1-2,2-dimethylcyclopropane-1- carboxylate, (±) -trans-benzyl-3-dichloroacetyl-2,2-dimethylcyclopropane-1-carboxylate, (±) -trans-benzyl-3- (ß, ß-dichloro-a-hydroxyethyl) -2,2-dimethylcyclopropane-1-carboxylate, (±) -trans-Benzy1-3- (β, ß-dichloro-a-tosyloxyäthy1) -2,2-dimethylcyclopropane-1-carboxylate, '- 60 - 7 over 9 8 1 07 1189 (±) -trans-Benzy1-3- (β ₃ ß-di chlorviny1) -2 ₅ 2-dimethyIcyclopr op an-1 - carb ο xy lat, m-phenoxybenzyl-dimethylsulfuronylidene J-acetate, (±) -trans-m-phenoxybenzyl-3-acetyl-2,2-dimethylcyclopropane-1-carboxylate, (±) -trans-m-phenoxybenzyl-3-dichloroacetyl-2j2-dimethylcyclopropane-1-carboxylatej (±) -trans-m-phenoxybenzyl-3- (3jß ~ dichloro-α-hydroxyethyl) -2 ₃ 2-dimethylcyclopropane-1-carboxylate ₃ (±) -trans-m-phenoxybenzyl-3- (β, β-dichloro -a-tosyloxyäthy1) -2,2-dimethylcyclopropane-1-carboxylate (±) -trans-ethyl-3 "dibromacety1-2,2-dimethylcyclopropane-1-carboxylate, (±) -trans-ethyl-3- (β , ß-dibromo-α-hydroxyethyl) -2,2-dimethy1-cyclopropane-1-carboxylate , and (±) -trans-ethyl-3- (ß, ß-dibromo-a-tosyloxyethyI) -2 ₃ 2-dimethyl-cyclopropane-1-carboxylate. 0 9 8 10/1189