DD140248A5 - PROCESS FOR THE PREPARATION OF HALOGENATED BUTTERIC ACID CHLORIDES - Google Patents

Abstract

Halogenated butyric acid chlorides of the formula

Description

-Λ-

Berlin, March 1, 1979, AP G Ό7 C / 209 276

.-,; .. GZ'54 522 12 ..

Process for the preparation of halogenated butyric acid chlorides

Field of application of the invention

The invention relates to the preparation of novel halogenated butyric acid chlorides which are intermediates for the preparation of pesticides *

Well-known technical solutions

The starting materials for the preparation of the compounds of this invention are also known as one of the intermediates occurring

Cl Cl

It

01-0-CJH ₂ -O-COO C ₂ H ^ H Cl

is known (CA £ 3, 24333g

Object of the invention

It is an object of the invention to provide new readily available and cheap intermediates which have a chemical

Berlin, March 1, 1979. AP O 07 C / 209 276

peculiar synthesis can be converted into pyrethoid pesticides

Essence of the invention. ··

The invention has for its object to develop a process for the preparation of new halogenated Buttersäurechloriden to "-) ©

The halogenated butyric acid chlorides correspond to the formula

Cl Cl

Il

XC-CH ₀ -C-COCl (I),

T Cl

v / orin

X is fluorine and Y is hydrogen or fluorine or X is chlorine and Y is hydrogen or chlorine.

The compounds of formula I may be prepared), 'that a compound of the formula

CCl ₃ -CO-Z (II)

in the presence of a catalyst and in the presence of an organic solvent, to a compound of the formula

(HI)

Berlin, the Ί · 3 · 1979 AP C 07 C / 209 276

attached, wherein X and Y have the meaning given under formula I and

Z is -01, -OH or -Oalkyl with 1-4 C-atoms, and the intermediates of the formula Ia

Cl Cl t t

ZC-CH ₀ -C-CO-Z (Ia)

Y Cl

in which. '^; ... ·.

Z represents -OH or -Oalkyl with 1-4 carbon atoms, then converted into a compound of formula I.

Preference is given to compounds of the formula I in which Σ and Y are each fluorine and especially those in which X and Y are each chlorine O

The starting compounds of formulas II and III are used in at least stoichiometric amount, but preferably an excess of compound of formula III, for example about 0.5 to 2-fold molar excess, wherein the compound of formula II optionally also as a solvent can serve.

• -if ..

Catalysts which can be used per se in the process of the invention are compounds known per se, such as metals of main group VIII and subgroups VIA, VIIA and Ib of the Periodic Table (according to the textbook of anorgan.Chemie, Holleman-Wiberg, U.de Gruyter & Co., Berlin ), Eg Iron, cobalt, nickel, ruthenium, rhodium, palladium, chromium, molybdenum, manganese and copper. These metals can be used in elemental form or in the form of compounds. Suitable such compounds are, for example, oxides, halides, sulfates, SuI-. fite, sulfides, nitrates, acetates, citrates, carbonates, cyanides and rhodanides, as well as complexes with ligands such as phosphines, Benzoinι benzoyl-r and acetylacetonates, phosphites, nitriles, isonitriles and carbon monoxide. ·

Examples which may be mentioned are: copper (II) oxide, iron (II) oxide Cu (I), Cu (II), Fe (II) and Fe (III) bromides and especially chlorides and the chlorides of ruthenium, Rhodium, palladium of ₅ cobalt and nickel; Cu (II) sulphate, Fe (II) and Fe (III) sulfate; Cu (II) nitrate and iron (III) nitrate; Manganese (III) ace did, copper (II) acetate, copper (II) stearate; Iron (III) citrate, · Cu (I) cyanide, · ruthenium (II) dichloro-tris-triphenylphosphine, rhodium-tris - (triphenylphosphine) chloride, chromium and nickel acetylacetonate, copper (II) acetylacetonate, iron (III) acetylacetonate, cobalt (H) and cobalt (IH) acetylacetonate, manganese (H) acetylacetonate, copper (II) benzoylacetonate, ironcarbonyl-cyclopentadienyl complex, molybdenumcarbonylcyclopentadienyl complex, chromium 'tricarbonylaryl complexes, ruthenium (II) acetate complex, chromium and molybdenum hexacarbonyl, nicitenetracarbonyl, Iron pentacarbonyl, cobalt and manganese carbonyl.

It is also possible to use mixtures of said metals with metal compounds and / or other additives, such as copper powder in combination with one of the abovementioned copper compounds; Mixtures of copper powder with lithium halides, such as lithium chloride, or with isocyanides,

-S 209 276

such as tert-butyl isocyanide; Mixtures of iron powder with iron (III) chloride, optionally with the addition of carbon monoxide ; Mixtures of iron (III) chloride and benzoin, mixtures of iron (II) or iron (III) chloride and trialkyl phosphites; Mixtures of iron pentacarbonyl and iodine.

Preference is given to iron (II) salts and iron (III) salts and complexes and iron powders, but above all to copper powders, copper (I) salts and copper (II) salts and complexes, such as Cu (I) chloride, Cu (II) chloride, Cu (I) bromide, Cu (II) bromide, Cu (II) acetylacetonate, Cu (II) benzoylacetonate, Cu (II) sulfate, Cu (II) nitrate and Cu (I) cyanide.

Very particular preference is given to copper powder, copper (I) chloride and copper (II) chloride or bromide, and mixtures thereof.

The catalysts are generally used in amounts of about 0.01 to 10 l.%, Preferably 0.1 to 5 mol.%, Based on the compound of formula III.

The reaction according to the invention is carried out in an organic solvent. Suitable organic solvents are those in which the catalysts are sufficiently soluble or which can form complexes with the catalysts, but which are inert to the starting compounds of the formula II and III. Examples of such solvents are alkylnitriles, especially those with 2-5 ~

C-ethers, such as acetonitrile, propionitrile and butyronitrile, · 3-alkoxypropionitriles having 1 or 2 C atoms in the alkoxy moiety, such as 3-methoxypropionitrile and 3-ethoxypropionitrile; aromatic nitriles, especially benzonitrile; aliphatic ketones preferably having a total of 3-8 C atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tert-butyl ketone; Alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of 2-6 C atoms, such as ants

-6- 209 27 6

Acid methyl and ethyl ester, methyl, ethyl, n-butyl and isobutyl acetate and 1-acetoxy-2-methoxyethane; cyclic ethers, such as. Tetrahydrofuran, tetrahydropyran and dioxane; Dialkyl ethers each having 1-4 C atoms in the alkyl moieties, such as diethyl ether, di-n-propyl ether and di-isopropyl ether; Ν, Ν-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, such as N, N-DimethyIformamid, N ₅ N-dimethylacetamide, Ν, Ν-diethylacetamide and N, N-dimethylmethoxy-acetamide, · ethylene glycol- and Diäthylenglykoldialkyläther each having 1-4 C atoms in the alkyl moieties, such as Aethylenglykoldimethyl-, diethyl- and di-n-butyl ether, Diäthylenglykoldiäthyl- and di-n-butylätherj Hexamethylphosphorsäuretriamidj

Preferred solvents are alkylnitriles with .2-5 C atoms. and 3-alkoxypropionitriles having 1 or 2 C atoms in the alkoxy moiety, in particular acetonitrile and 3-methoxypropionitrile

The reaction temperature is generally not critical and may vary within wide limits. Preferably, the reaction temperatures are between about 60 and 200 ⁰ C, in particular between about 80 and 170 ⁰ C. The reaction can be carried out under pressure or without pressure.

The compound of the formula III is preferably used trichloroacetic acid chloride or a Trichloressigsäurealkylester having 1 or 2 C-atoms in the alkyl moiety.

Intermediates of the formula Ia in which Z = -OH can be converted into compounds of the formula I in a manner known per se by treatment with suitable gelling agents, such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, oxalyl chloride, phosgene, thionyl chloride, benzoyl chloride or phthaloyl chloride.

If, as the compound of the formula III, a trichloroacetic acid alkyl ester as defined is used, the resulting intermediate of the formula Ia with Z = -Oalkyl having 1-4 C atoms can be hydrolyzed in a manner known per se in the presence of strong acids, such as concentrated hydrochloric acid, to the corresponding butyric acid to which, as mentioned above, by treatment with suitable chlorinating agents in compounds of formula I.

After completion of the reaction, the compounds of formula I can be isolated in a conventional manner and if necessary purified, for example by distillation.

The compounds of formula I are valuable intermediates for the preparation of pesticides. They may also be converted to pyretebroid pesticides or precursors thereof after a novel, peculiar synthesis. Such compounds, for example those of the formula

^{! j} 'C = CH - CH> CH - COOR (IV),

in which X and Y have the meaning given under formula I, one of R- and R _{2 is} methyl and the other is hydrogen or methyl or R- and R ₂ together denote alkyls having 2-4 C atoms,

R is hydrogen, alkyl having 1-4 C atoms or a

Grouping ~. ,

Ij -jjci_p represents, where

Ro is -0-, -S- or -CH = CH-,

L · I

R, hydrogen, alkyl having 1-4 C atoms, benzyl, phenoxy or phenyltnercapto,

R _{5 is} hydrogen or alkyl having 1-4 C atoms and R _{6 is} hydrogen or ethynyl or, if one of R ^ and R "is methyl and the other is hydrogen or methyl, R 1 is -CH = CH-, R, phenoxy and R ₅ mean hydrogen, also represent alkyl having 1-5 C atoms,

can be obtained by reacting a compound of formula 1 in the presence of a dehalogenating agent with a compound of formula

CH ₂ = C

(V)

to a compound of the formula

R,

Cl

Cl

CH ₀ -C -XY

(VI)

reacting the compounds of formula VI in the presence of a catalyst in a compound of formula

Cl

R,

..ο

Cl

-CH ₀ -C -X

ν Δ ι

(VII)

rearranged and converted the compound of formula VII in the presence of a base in a compound of formula IV.

Z 1 ö

In the reaction of the compounds of formula I with the 'dehalogenation agent is a ketene of the formula

Cl Cl

XC-CH ₂ -C = C = O (VIII)

formed, which cycioaddiert with the compounds of formula V to compounds of formula VI. Dehalogenating agents which can be used are halogen-splitting agents known per se. In particular, optionally by HCl, copper or silver activated zinc, tin, Raney nickel, Raney cobalt, mercury, silver and magnesium come into consideration. Preferred dehalogenating agent is zinc which may be in any desired form, e.g. can be used as a powder, in the form of zinc wool or ZinkspMnen.

Said reaction is conveniently carried out in an inert organic solvent, such as ethers of the aforementioned type, especially dialkyl ethers having 1-4 carbon atoms in the alkyl moieties, aliphatic ketones, especially those which are branched in the α-position, such as diisopropyl ketone and methyl tert-butyl ketone, or alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of 2-6 C atoms, of methyl and ethyl formate, methyl, ethyl, η-butyl and isobutyl acetate, and acetoxy-2-methoxyäthan.

In general, it is also expedient to carry out the reaction in the presence of weak Lewis acids, such as ammonium chloride, sodium, potassium and mercury iodide, zinc chloride, MePOCl ₂ , POClq or even elemental iodine. It is also possible to use mixtures of such Lewis acids.

The reaction temperatures are advantageously between about 15 and 80 ⁰ C, in particular between about 25 and 65 ⁰ C.

 -ίo- 209 27 6

The olefins of the formula V are used in at least an equimolar amount, based on the acid chloride of the formula I or the ketene of the formula VIII formed in situ. In general, however, an excess of olefin of the formula V is advantageously used.

The ketene of the formula VIII and the compounds of the formula

VI and VII are new. ,

As catalysts for the rearrangement of the compounds of formula VI in compounds of formula VII, for example, acids, bases or quaternary ammonium halides can be used. The rearrangement may be carried out in the melt or in a suitable inert organic solvent.

As bases for the conversion of the compounds of the formula

VII in compounds of formula IV can e.g. Alkali metal and alkaline earth metal hydroxides or alcoholates are used.

According to this novel inventive synthesis, compounds of the formula IV can be prepared via the novel intermediates of the formulas VI and VII in comparison with previously known processes [cf. Farkas et al., Coll. Czech Chem. Com. 24,2230 (1959) and Chem. Styly, 52, 688 (1958); British Patent 1,285,350; Belgian Patent 850,402; German Offenlegungssbriften 2,439,177, 2,539,895, 2,544,150, 2,547,510, 2,552,615, 2,554,380, 2,605,398, 2,615,159, 2,615,160, 2,616,528, 2,621,830, 2,621,832, 2,621,833, 2,621,835, 2,623,777, 2,630,981 and 2,639,777; US Pat. No. 3,961,070 and Japanese Laid-Open Patents 69872/76 and 47966/76] are produced in a particularly simple and economical manner, in good to very good yields and with high proportions of the desired ice form, which is particularly effective in certain applications. In contrast to previously known processes, the starting materials are light

-.11-

accessible, the reagents used are relatively cheap and ecologically cheap, all reaction steps can be carried out under relatively mild conditions and without great expenditure on equipment and safety measures. The intermediates of formulas VI and VII 'oxidize the oxidation state required for their further use, so that neither oxidations nor reductions are necessary. The individual process steps can be carried out without isolation of the respective intermediate product immediately after each other, so that this synthesis (') is very well suited for the large-scale' production of compounds of formula IV.

Compounds of the formula IV in which R is hydrogen or alkyl having 1-4 C atoms can be converted in a manner known per se into active compounds of the formula IV with R 1 H or alkyl having 1-4 C atoms, or else in compounds of formula IV, wherein R ^ additionally -CN, for example by reaction with corresponding halides or alcohols, if appropriate with prior conversion into the acid chloride, or by transesterification [cf. e.g. German Offenlegungsschriften 2,553,991 and 2,614,648].

O '

Compounds of formula IV with R f H or alkyl having 1-4 C atoms are suitable for controlling a wide variety of animal and plant pests, especially as insecticides. The properties, uses and uses of these agents are described in the literature (see, for example, Nature, 2_46, 169-70 (1973); Nature, 248_, 710-11 (1974); Proceedings 7th British Insecticide and Fungicide Conference, 721-728 (1973); Proceedings 8th British Insecticide and Fungicide Conference, 373-78 (1975); J.Agr.Food Chem. ', £ 3,115 (1975); U.S. Patent 3,961,070; German Offenlegungsschriften 2,553,991, 2,439,177; 2,326,077 and 2,614,648].

H 209 276

example 1

a) 242.5 g (2.5 mol) of 1, l-Diehloräthylen ', 356 g (2MoI) trichloroacetic acid methyl ester, 12.8 g of copper (I) chloride and 800 ml of acetonitrile are kept for 24 hours at 115 ° C. The reaction mixture is clear filtered and evaporated. The residue is distilled. This gives 293.7 g of 2,2,4,4,4-Pentachlorbuttersäuremethylester; Bp 118-122 ° C / 15 mm Hg.

IR spectrum (film) in cm ^-1 : 1755 and 1772 (CO) NMR spectrum (100 MHz, CDCl ₃ ) in ppm: 4.08 (s,

¹ J (CH) ^{= 139 Hz); 3 '93 (S' 3H 'CH} 3' ¹ ^ (C, H). ^

Elemental analysis for C ₅ H ₅ Cl ₅ O ₂ (molecular weight 274.36): calculated C 21.89% H 1.84% Cl 64.61% Found C 22.0% H 1.8% Cl 64.3%.

156.7 g of methyl bis (2 ', 2', 2'-trichloroethyl) chloroacetate are distilled off as by-product at 15 ° C./15 mm Hg; M.p. 65-67 ° C (recrystallized from η-hexane); NMR (100 MHz ₃ CDCl ₃ ) in ppm: 3.86 (s, 3H, CH ₃ ); 3.77 (AB system, 4 ¹ H, CH ₂ ).

b) 145.4 g (1.5 mol) of I ₅ 1-dichloroethylene, 712 g (4 mol) of methyl trichloroacetate, 12.8 g of copper (I) chloride and 800 ml of acetonitrile are reacted as described under a). After the same work-up, 289 g of 2,2,4,4,4-pentachlorobutyrate are obtained. In this case, virtually no by-product of the type described under a) is formed.

Example 2

382.9 g (2 mol) Trichloressigsäureäthylester, 242.8 g (2.5 mol) of 1,1-dichloroethylene ₃ 400 ml of acetonitrile and 6.0 g of copper (I) chloride are heated to 140 ⁰ C for 4 hours. The reaction mixture is clear filtered and distilled. This gives 209.9 g of 2,2,4,4,4-Pentachlorbuttersäureäthylester; Bp 14O-145 ° C / 2O mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1770 (CO).

NMR spectrum (60 MHzm _CDCl3) in ppm: 4.1 (s, 2H, 4.30 (q, 2H, CH ₂₎ :, 1.40 (t, 3H, CH _3).

-13 909 'LI

Elemental analysis for CgH ₇ Cl ₅ O ₂ (molecular weight 288, AO): Calculated C 24.99% H 2.45% Cl 61.47% Found C 24.9% H 2.4% Cl 61.2%.

Example 3

a) 145.4 g (1.5 mol) l _s l-dichloroethylene, 182 g (1 mol) of trichloroacetic acid chloride, 3.0 g of copper (I) chloride and 200 ml of acetonitrile are kept at 140 ⁰ C for 4 hours

 The reaction solution is clear filtered and evaporated

The residue is distilled. The fraction of 88-102 ⁰ C / 10 mm Hg is redistilled. 115.7 g of 2,2,4,4,4-pentachlorobutyric acid chloride are obtained; Bp. 95-96 ⁰ C / 10 mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1785 (CO).

NMR spectrum (60 MHz, CDCl ₃ ) in ppm: 4.10 (s, CH ₂ ).

Elemental analysis for 0, H ₂ CIgO (molecular weight 278.80):

calculated C 17 23% H 0 , 72% Cl 76 , 307c found C 17 8th% H 1 , 0% Cl 75 , 5%.

b) 137 g (0.5 mol) of 2,2,4,4,4-Pentachlorbuttersäuremethylesters obtained according to Example 1 are boiled with 700 ml of concentrated hydrochloric acid for 40 hours. After cooling, it is extracted with toluene. The extracts are extracted with dilute sodium hydroxide solution. The alkaline, aqueous phase is washed with diethyl ether, acidified with hydrochloric acid and extracted with diethyl ether. This extract is washed with water, dried over magnesium sulfate and evaporated. The residue is kept at 70 ^° C. for 2 hours with 200 ml of thionyl chloride. The dark reaction mixture is evaporated to dryness. The residue is distilled. 102.9 g of 2,2,4,4,4-pentachlorobutyric acid chloride are obtained; Bp 100-102 ° C / 14 mm Hg. The spectroscopic data of the resulting acid chloride are identical to those of the product prepared according to a).

209 27 6

c) In a manner analogous to that described under b), the 2,2,4,4,4-pentachlorobutyric acid ethyl ester obtained according to Example 2 can be converted into the corresponding acid chloride.

In the following, the conversion of the 2,2,4,4,4-Pentachlorbuttersäurechlorids in two compounds of the formulas VI, VII and IV or .. is described: - ¹ '' -.

A (I) 2-chloro-2- (2 ', 2', 2 '-trichloräthyl) -3,3-diisopropyl dimethylcyclobutanole 150 ml at room temperature (20-25 ⁰ C) saturated with isobutylene. To this are added 26.1 g of zinc shavings, 0.54 g of ammonium chloride and 0.17 g of potassium iodide. For 1 hour, a solution of 27.9 g (O ₅ I mol) of 2,2,4,4,4-pentachlorobutyric acid chloride in 50 ml of diisopropyl ketone is added dropwise at 30 ⁰ C and with introduction of a weak stream of isobutylene. Subsequently, stirring is continued for 4.5 hours at 30 ° C. The reaction mixture is clear filtered, washed with dilute hydrochloric acid and water, dried over magnesium sulfate and evaporated. The residue is crystallized from η-hexane. This gives 13.7 g (52% of theory) of 2-chloro-2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethylcyclobutanone; Mp. 73-75 ° C.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1805 (CO).

H-KMR spectrums (100 MHz, CDCl ₃ ) in ppm: '1.42 and 1.45 (each Is, 6H, each ICH ₃ ); 2.91-3.28 (m, 2H, CH ₂ ) J 3.37-3.76 (m, 2H, CH ₂ ).

" ⁵ C-NMR spectrum (CDCl ₃ ) in ppm: 196 (s, CO); 95.3

(s, CH _3); 80.8 (s, C-2); 57.0 (t, CK ₂ ); 56.4 (t, CH ₂ ); 37.9 (s, C-3); 25, l '(q, CH ₃ ); 23.8 (q, _CH3).

Elemental analysis for CgH ₁₀ Cl ₄ O (molecular weight 263.98):

Calculated C 36.40% H 3.82% 0 6.02% Cl 53.72% Found C 36.4% H 3.9% 0 6.2% Cl 53.5% ·

A (2) 2- (2 ', 2''-trichloroethyl) -S-S-dimethyl-chlorocyclobutane

132 g (0.5 mol) of 2-chloro-2- (2'-2 ^!, 2'-trichloroethyl) -3 _s 3-dimethylcyclobutan-1-one are dissolved in 700 ml of toluene, treated with 1 ml of triethylamine and under Reflux cooked. After 13 hours of reaction time, another 1 ml of triethylamine is added and boiling is continued for 7 hours. After cooling, the reaction mixture is first washed with dilute hydrochloric acid and then with water, dried and evaporated. The solidified, thin-layer chromatographically uniform residue (124 g, 94% of theory) is crystallized from η-hexane. This gives 105.8 g of 2- (2 ^!, 2 ^f , 2'-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one; Mp. 56-57 ⁰ C.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1800 (CO).

• ^ H-NMR spectrum (100 MHz, CDCl ₃₎ in ppm: 4.77 (d, J = 2 Hz, IH, H on C-4); 3.47 (m, IH, H to Q-2); 2.73-3.26 (m, 2H, CH ₂ ); 2.63 (s, 3H, CH _3); 1.14 (s, 3H, CH _3).

¹³ C-NMR spectrum (CDCl ₃ ) in ppm: 197.0 (s, CO); 97.8 (s, CCl ₃ ); 69.4 (d, C-4); 60.6 (d, C-2); 49.5 (t, CH ₂ -CCl ₃ ); 36.8 (s, C-3); 27.4 (q, CH ₃ ); 18.6 (q, _CH3).

Elemental analysis for CgH ₁ Cl, O (molecular weight 263.98):

calculated C 36 40% H 3 , 82% 0 6 , O27o Cl 53 , 72% found C 36 6% H 3 ,8th% 0 6 , 2% Cl 53 , 6%.

A (3) 2- (2 ', 2' -Dichlorvinyl) -S ^ -dimethylcyclopropancarbonsäure 13.2 g (0.05 mol) of 2- (2 ', 2 ^I, 2 ^l -Trichloräthyl) -3,3-dimethyl 4-chlorocyclobutanone are mixed with 150 ml of 107 _o sodium hydroxide solution and stirred vigorously. After 5 minutes, a clear solution has formed, which is heated to 100 ⁰ C (bath temperature) for 1 hour. The reaction solution is washed with diethyl ether, acidified under cooling with concentrated hydrochloric acid and extracted with diethyl ether The ether phase is washed with water, dried over magnesium sulphate and evaporated The solid residue (10.35) precipitates according to the NMR spectrum 80 % By weight of ice and 20% by weight of trans-2- (2 ¹ , 2'-dichlorovinyl) -S-dimethyl-cyclopropane-1-carboxylic acid crystallization from η-hexane affords pure iced acid; 85-87 ° C.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1710 (CO), 1625 (C = C).

NMR spectrum (100 MHz, - CDCl ₃ ZD ₂ O) in ppm: 1.30 (s, 6H, 2 times CH ₃ ); 1.85 (d, J = 8.5 Hz, IH, HC-I); 2.02-2.19 (m, IH, HC-2); 6.17 (d, J = 8 Hz, IH, CH = CCl ₂ ).

A (4) Ice-2- (2 ', 2 * -dichlorovinyl ·) -S ^ -dimethylcyclopropanecarboxylic acid-g-cyano-m-phenoxybenzyl ester

10 g (0.047 mol) of cis-2- (2 ', 2 ¹ -dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid are stirred in 100 ml of benzene with 12.1 ml (0.141 mol) of oxalyl chloride for 24 hours at room temperature. After evaporating the reaction solution, the brown residue is distilled under reduced pressure. This gives 9.1 g of a clear liquid; Bp. 5O ° C / O, O4 mm Hg. 3.0 g of this clear liquid are dissolved in 30 ml of toluene and treated with 2 ml of pyridine. At room temperature, 2.9 g of α-cyano-mphenoxybenzylalkohol are added dropwise in 20 ml of toluene, and the reaction mixture is then further stirred for 16 hours at room temperature. The reaction mixture is washed first with water, then with saturated sodium bicarbonate solution and then with brine, dried over magnesium sulfate and evaporated. The residue is chromatographed on silica gel (elution with diethyl ether / n-hexane 1: 2). Man. is obtained pure cis-2- (2 ', 2'-dichlorovinyl) -3,3-dimethylcyclopropancarbonsäure oc-cyan-m-phenoxybenzylester as a mixture of diastereoisomers.

NMR spectrum (60 MHz ₅ CDCl ₃ ) in ppm: 1.20-1.43 (m, 6H, CH ₃ ); 1.67-2.35 (m, 2H, 2x CH); 6.25 (d, J = 9Hz, IH, CH-CCl ₂ ); 6.40 and 6.45 (each Is, each 0.5H, CH-CN); 6.98-7.65 (m, 9H).

- η- 209 27 6

Example 4

a) 181.8 g (1 mol) of trichloroacetic acid chloride, 3 g of copper (I) chloride and 200 ml of acetonitrile are introduced into a tantalum autoclave After pressing 93.7 g (1.5 mol) of vinyl chloride, the autoclave becomes 4 hours . heated to 140 ⁰ C. The reaction mixture is then distilled to give 2,2, 4,4-tetrachloroethane butyryl chloride as a colorless liquid;.. b.p. 100-105 ⁰ C / 20 mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1790 (CO).

NMR spectrum (60 MHz, CDCl ₃ ) in ppm: 3.60 (d, 2H, CH ₂ ); 6.06 (t, IH, CH).

Elemental analysis for C 1 H ₃ Cl ₅ O (molecular weight 244.40): Calculated C 19.67% H 1.24% Cl 72.56% Found C 20.0% H 1.3% Cl 71.5%

b) 191.4 g (1 mol) Trichloressigsäureätbylester, 3 g of copper (I) chloride and 200 ml of acetonitrile are presented in a tantalum autoclave. After pressing 93.7 g (1.5 mol) of vinyl chloride, the autoclave is heated to 140 ⁰ C for 4 hours. The reaction mixture is then distilled. This gives 208.5 g (82% of theory) of 2,2,4,4-Tetrachlorbuttersäureäthylester; Bp 127-13O ° C / 20 mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 , 1770 (CO).

• NMR spectrum (60 MHz, CDCl ₃₎ in ppm: 1.41 (t, 3H, CH 3);

3.48 (d, 2H, CH ₂ ); 4.36 (q, 2H, CH ₂ ); 6.01 (t, IH, CH).

Elemental analysis for C ₆ HgCl, O ₂ (molecular weight 237.95):

Calculated C 28.38%, H 3.18% Cl 55.85% Found C 28.7% H 3.5% Cl 54.8%

c) 50.8 g (0.2 mol) of 2,2,4,4-Tetrachlorbuttersäureäthylester and 200 ml of concentrated hydrochloric acid are heated for 72 hours at reflux. After cooling, the reaction mixture is extracted with toluene. The extract is washed with water, dried over magnesium sulfate and evaporated.

209 27 6

The residue is distilled. This gives 40.2 g (86% of theory) of 2,2,4,4-tetrachlorobutyric acid; Bp 155-160 ° C / 18 mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1750 (CO).

NMR spectrum (60 MHz, CDCl ₃ ) in ppm: 3.50 (d, 2H, CH ₂ ); 6.01 (t, IH, CH); 9.9 (s, IH, OH).

Elemental analysis for C ₄ H ₄ Cl, O ₂ (molecular weight 225.89):

calculated C 21.27% H 1.78% Cl 62.78% found C 21.9% H 1.9% Cl 61.9%.

d) 45.18 g (0.2 mol) of 2,2,4,4-tetrachlorobutyric acid and 100 ml of thionyl chloride are heated to 70 ⁰ C for 2 hours. After cooling, the reaction mixture is evaporated. Distillation under reduced pressure gives 2,2,4,4-tetrachlorobutyric acid chloride as a colorless liquid; Bp 101-104 ° C / 20 mm Hg.

The spectroscopic data of the acid chloride obtained are identical to those of the 2,2,4,4-tetrachlorobutyric acid chloride prepared according to a).

The working up to compounds of the formula VI, VII and IV is described below:

500 ml of diisopropyl ketone are saturated at room temperature with isobutylene. Add 100 g of zinc shavings, 2.2 g of ammonium chloride and 0.7 g of potassium iodide. During 2.5 hours, 101.8 g (0.4 mol) of 2,2,4,4-tetrachlorobutyric acid chloride are added dropwise at room temperature and with a slight flow of isobutylene. Subsequently. is stirred for 3 hours. After working up analogously to Example 3, 69.7 g of a non-crystallizing oil are obtained. Distillation at 0.2 mm Hg provides between 86 and 91 ° C a clear, "mobile" liquid identified as 2-chloro-2- (2 ¹ , 2 ^! -Dichloroethyl) -3,3-dimethylcyclobutanone.

-20- 209- 276

IR spectrum (CHCl ₃ ) in cm ^-1 : 1795 (CO).

• NMR spectrum (100 MHz, CDCl ₃₎ in ppm: 1,39- (s, 3H, CH _3); 1.42 (s, 3H, CH ₃ ); 2.80-3.20 (m, 411, 2xCH ₂ ); 6.03 (t, J = 6Hz, IH, CHCl ₂ ).

5 g (21.7 mmol) of 2-chloro-2- (2 ', 2'-dichloräthyl) -3,3-dimethylcyclobutanon and 1.7 g of tetrabutylammonium chloride are switched together · 1.5 hours at 125 ⁰ C stirred. The cooled melt is taken up in diethyl ether and filtered through silica gel. The evaporated filtrate (4.5 g) is chromatographed on silica gel (elution with cyclohexane / toluene in a 1: 1 volume mixture). The major fraction (colorless oil) is identified as 2- (2 ', 2'-dichloroethyl) -3,3-dimethyl-4-chlorocyclobutanone.

IR spectrum (CHCl ₃ ) in cm ^-1 * 1795 (CO).

• hl-NMR spectrum (100 MHz, CDCl ₃₎ in ppm: 1.07 (s, 3H, CH ₃₎ J 1.57 (s, 3H, CH _3); 2.15-3.40 (m, 3H); 4.68 (d, J-2Hz, IH, HC ₄ ); 5.80-5.95 (m, IH, CHCl ₂ ).

¹³ C-NMR spectrum (CDCl ₃ ) in ppm: 198.7 (s, CO); 71.1 (d, CHCl ₂ ); 69.3 (d, C-4); 59.7 (d, C-2); 38.3 (t, CH ₂ ); 36.3 (s, C-3); 27.6 and 18.7 (each q, each CH ₃ ).

4.2 g (18.3 mmol) of 2- (2 ', 2'-dichloroethyl) -3,3-dimethyl-4-chlorocyclobutanone are mixed with a solution of 2.16 g (54.9 mmol) of NaOH in the 50th ml of water and stirred for 3 hours at room temperature. The resulting clear solution is heated to 100 ⁰ C for 2 hours. The reaction mixture is worked up to acid in the usual way. The known 2- (2'-chlorovinyl) -3, S-dimethylcyclopropanecarboxylic acid is obtained as a mixture of isomers. ,

IR spectrum (CDCl ₃ ) in cm ^-1 : 1710 (CO).

209 27 6

Example 5

a) 192 g (1 mol) Trichloressigsäureäthylester, 200 ml of acetonitrile and 3 g of copper (I) chloride are placed in an autoclave. After pressing 130 g (2 mol) of 1,1-difluoroethylene is heated to 160 ⁰ C for 8 hours. The reaction mixture is then fractionally distilled. 4,4-Difluoro-2,2,4-trichlorobutyric acid ethyl ether is obtained; Bp 89-91 ° C / 2O mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1770 (CO).

NMR spectrum (60 MHz, CDCl ₃ ) in ppm: 1.40 (t, 3H, CH ₃ ); 3.47-3.90 (t, 2H, CH ₂ ); 4.20-4.57 (q, 2H, CH ₂ -CH ₃ ).

Elemental analysis for C ^ H ₇ Cl ₃ F ₂ O ₂ :

calculated Cl 41.63% F 14.87% found Cl 42.5% F 13.3%.

b) 76.6 g (0.3 mol) of 4,4-difluoro-2,2,4-trichlorobuttersäureäthylester and 150 ml of concentrated hydrochloric acid are heated in a bomb tube at 130 ⁰ C for 10 hours. The non-aqueous layer of the reaction mixture is separated, washed with water, taken up in toluene, dried over magnesium sulfate and evaporated. The residue is distilled. 4,4-Difluoro-2,2,4-trichlorobutyric acid is obtained as a pale yellow-colored OeI; Bp 12O-122 ° C / 2O mm Hg.

IR spectrum (CHCl ₃ ) in cm ^-1 : 1750 (CO).

c) 24.5 g (0.1 mol) of 4,4-difluoro-2,2,4-trichlorobutyric acid and 60 g (0.5 mol) of thionyl chloride are mixed with .3 drops of N, N-dimethylformamide and 3 hours at 40-45 ⁰ C held. The mixture is then refluxed for 6 hours. The excess thionyl chloride is evaporated and the residue is subjected to distillation. This gives colorless 4 ₃ 4-difluoro-2,2 _J 4-trichlorobuttersäurechlorid; Bp 1O5-1O9 ° C / 18 mm Hg.

Claims (4)

Berlin, the 1 "3 · 1979 C 07 C / 209 276 - 209 27έ invention claim 1. A process for the preparation of compounds of the formula Cl Cl
t X - C - CH ₀ - C - COCl
Y Cl wherein X is fluorine and Y is hydrogen or fluorine or X is chlorine and Y is hydrogen or chlorine, characterized in that a compound of the formula CClyCO-Z in the presence of a catalyst and in the presence of an inert organic solvent, to a compound of the formula = C attaches j wherein X and Y have the meaning given above and Z represents -Cl, -OH or -Oalkyl with 1-4 C-atoms, and the intermediates of the formula Cl Cl
XC CH ₀ - C --CO - Cl ZY. in which Z is -OH or -Oalkyl having 1-4 C atoms, converted into the end compounds using suitable chlorinating agents Berlin, March 1, 1979 O 07 C / 209 276 2. The method according to item 1, characterized in that the solvent used is an alkylnitrile having 2-5 C-atoms, especially acetonitrile. 3 «method according to item 1, characterized in that the solvent used is a 3-alkoxypropionitrile having 1 or 2 O atoms in the alkoxy moiety, especially 3-methoxypropionitrile,« 4 * Process according to item 1, characterized in that the catalyst used is copper (I) chloride, copper (I) bromide, copper (II) chloride, copper (II) bromide, copper powder or mixtures thereof.