CA1111445A - Process for the preparation of 2-(2',2',2'- trihalogenoethyl)-4-halogenocyclobutan-1-ones - Google Patents
Process for the preparation of 2-(2',2',2'- trihalogenoethyl)-4-halogenocyclobutan-1-onesInfo
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- CA1111445A CA1111445A CA299,990A CA299990A CA1111445A CA 1111445 A CA1111445 A CA 1111445A CA 299990 A CA299990 A CA 299990A CA 1111445 A CA1111445 A CA 1111445A
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- formula
- trihalogenoethyl
- halogenocyclobutan
- bromine
- carbon atoms
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/38—Acyl halides
- C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
- C07C53/50—Acyl halides containing halogen outside the carbonyl halide group of acids containing three or more carbon atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Abstract of the Disclosure A novel process for the preparation of 2-(2',2',2'-trihalogeno-ethyl)-4-halogenocyclobutan-l-ones of the formula
Description
, The present invention relates -to a process for'the pre-paration of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-l-ones of the formula I
. ~ , ' ` .
', CX3 CH2-- C~l-- C = O
Rl - f ---CHY
':
,, in which one of the radicals Rl and R2 is methyl and the other ' is hydrogen or methyl, or Rl and R2 together are an alkylene ~ group having 2 to 4 carbon atoms, and X and Y are each chlorine : or bromine, but if X is bromine Y must always also be bromine.
The present inven-tion also relates to the novel 2-'~ (2',2',2'-trihalogenoe-thyl)-4-halogenocyclobutan-1-ones of the ,', formula I which can be prepared by the process according to the invention and also to novel intermediates which can be used .: ., .
fo,r their preparation, ' It is kno~m that a-halogenocycloalkanones are converted on heating in the presence of bases, such as alkali metal hydroxides and alkali metal alcoholates, to cycloalkanecarboxy-lic acids having the same number of carbon atoms, or esters ,~
thereof, with contraction of the ring (Favorski reaction).
This reaction is the basis for an industrially important pro-. cess for the preparation of cyclopropanecarboxylic acid deriva-tives and their esters having an insecticidal action, i,e. the pyrethroids, from a-halogenocyclobutanones. However, it
. ~ , ' ` .
', CX3 CH2-- C~l-- C = O
Rl - f ---CHY
':
,, in which one of the radicals Rl and R2 is methyl and the other ' is hydrogen or methyl, or Rl and R2 together are an alkylene ~ group having 2 to 4 carbon atoms, and X and Y are each chlorine : or bromine, but if X is bromine Y must always also be bromine.
The present inven-tion also relates to the novel 2-'~ (2',2',2'-trihalogenoe-thyl)-4-halogenocyclobutan-1-ones of the ,', formula I which can be prepared by the process according to the invention and also to novel intermediates which can be used .: ., .
fo,r their preparation, ' It is kno~m that a-halogenocycloalkanones are converted on heating in the presence of bases, such as alkali metal hydroxides and alkali metal alcoholates, to cycloalkanecarboxy-lic acids having the same number of carbon atoms, or esters ,~
thereof, with contraction of the ring (Favorski reaction).
This reaction is the basis for an industrially important pro-. cess for the preparation of cyclopropanecarboxylic acid deriva-tives and their esters having an insecticidal action, i,e. the pyrethroids, from a-halogenocyclobutanones. However, it
2 -.'.' ~
... . .. , . . .. .. , . .. . . , ~ . . . . . . ~. -4~5 was not possible to use this process, which is technically simple to carry out, for the preparation of pyrethroids which are derived from 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxy-lic acid, since corresponding a-halogenocyclobutanones suitable for the prepara-tion of such cyclopropanecarboxylic acid deriva-tives were not available.
It has already been proposed to prepare a-halogenocyclo-butanones by reacting a halogenoketene with an olefine Pro-cesses of this type are describedS for example, in German Offenlegungsschrift 2,539,048 and British Patent Specification 1,194,604 and also in J. Amer. Chem. Soc. 87, 5257-5259 (1965) and in Tetrahedron Letters No. 1, 135-139 (1966). This synthesis principle has not been used hitherto for the prepara-tion of ~-halogenobutanones, which are suitable as intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropane , .
carboxylic acids and their esters having an insecticidal action.
This is in particular due to the fact that the synthesis poss-ibilities which are conceivable on the basis of the above-mentioned method, i.e.
a) reaction of a halogenated olefine with a halogenoketene ln accordance with the equation:
3C-C~2-CH=C ~ ~ Y-CH=C=O / ~ 3C CH2-f-CI=o R2 - Rl - ~- H-Y
or : . .
. .
~ - 3 -.':
.
R] \ X3C-CH2-C-C=O
/C=C~I Y ~~3C-C~2-CH=C=O / -- ~ C~ Y
or - b) reaction of an unhalogenated olefine with a halogenoketene - in accordance with the equation:
.
X3C - CH2 - l=C=O ~ ~ C=C1~2 ~ X3C CH2~ ==o ~, 12 the symbols Rl, R2, X and Y in the above equations being as defined under formula I, do not lead to the 2-(2',2',2'-tri-halogenoethyl)-4~halogenocyclobutan-1-ones of the formula I, which are required as intermediates, since the reaction accord-ing to a) does not take place because of the deactivation of the olefine which is associated with the substitution by halo-gen and the reaction according to b) results in a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one which cannot be converted into a 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxy-lic acid, or an ester thereof, using an alkali metal hydroxide or alkali metal alcoholate.
The object on which the present invention is based is, therefore, to provide a process for -the preparation of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula I which uses readily accessible starting materials ar.d ~ ~ _ :
. is simple to carry out.
A further object on which -the present invention is : based is to make available the 2-(2',2',2i-trihalogenoethyl)-4-:: halogenocyclobutan-l-ones of the formula I, which have not been known hitherto and which on heating with strong bases, such as alkali metal hydroxides or alkali me-tal alcohola-tes, give the : corresponding 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives, with contraction of the ring and, at the same :. time, the elimination of 2 mols of hydrogen halide, and also readily accessible in-termediates which can be used for the pre-paration of ~-halogenocyclobutanones of the formula I
: It has now been found that 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula I can be prepared in a simple manner by reacting a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II
X3C- CH2 _ fH COCl . (II) :~ . Y
in which X and Y are as defined under formula I, in the presence of an organic base with an olefine of the formula III
.. ~Rl ' CH2 -C (III) : \
: R2 in whic'n Rl and R2 are as defined under formula I, to give a ... , .. ,. , . . . , ., ., .. . ~.. . . . ... , .. ...... , ,.. ~.. .... ..... .
4~5 : 2-(2~,2',2~-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV
~ X3C - CH2 - C - C = O (IV) .. . .
',' ~1 1 C H2 .... -' ' `-' 'R2 `
.:.`' , in which Rl, R2, X and Y are as defined under formula I, and .. , then rearranging the latter, in the presence of a catalyst, in-to a 2-(2',2',2~-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I, ~: The 2,4,4,4-tetrahalogenobu-tyric acid chlorides of the formula II are novel compounds, They can be prepared in a :~ manner known per se by adding a carbon tetrahalide of the ` formula V
.
~. X
~'" X--C.--Y
X ~ (V) ~ . ' ' .
.: in which X and Y are as defined under formula I, onto a com-. pound of the formula VI
- CH2 CH - Z (VI) .: .
in which Z is chlorocarbonyl, carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl group, or cyano, and convert-ing resulting co~pounds of the forLula VII
,'~' ~ .
:
114~
~...`
'~:
` X3C C~12 - CH - Z (VII) .' . Y
.,'" .
- . . .
~ in which X and Y are as defined under formula I and Z is -:~. carboxyl, alkoxycarbonyl or cyano, into compounds of the ... .
formula VII in which Z is chlorocarbonyl, A further possibility for the preparation of 2,4,4,4-tetrahalogenobutyric acid chlorides of the formula II comprises adding a compound of the formula VIa CH - z (VIa) ., ` , in which Z is as defined under formula VI, onto l,l-dichloro-ethylene and converting resulting compounds of the formula VIIa .~:
- . C1 (VIIa) . C13C CH2 - C~ Z
.
-, in which Z is carboxyl, alkoxycarbonyl or cyano, into compounds : of the formula VIIa in which Z is chlorocarbonyl, ~ nen adding a carbon tetrahalide of the formula V onto an acrylic acid derivative of the formula VI and also when adding a dichloroacetic acid derivative of the formula VIa onto ;' ~ 7 --l4~5 ,.......................................................................... .
dichloroethylene, the carbon tetrahalide of the formula V
and, respectively, the dichloroacetic acid derivative of the formula VIa can be employed in the s-toichiome-tric amount Preferably, however, an excess of the carbon tetrahalide of the formula V or the dichloroacetic acid derivative of the formula VIa, for example an approximately 0.5-fold to 2-fold molar excess, is used and -the carbon tetrahalide of the formula V can also serve as a solvent The adding of a carbon tetrahalide of the formula V
onto a compound of the formula VI, and also the adding of a compound of the formula VIa onto l,l-dichloroethylene, is !`
carried out in the presence of catalysts. Suitable cata-lysts are metals of principal group VIII and sub-groups VIa, VIIa and Ib of the periodic system, for example iron, cobalt, nickel, ruthenium, rhodium, palladium, chromium, molybdenum, manganese and copper. These metals can be employed in the elementary form or in the form of compounds. Suitable compounds of these metals are, for example, oxides, halides, .
sulphates, sulphites, sulphides, nitrates, acetates, citrates, carbonates, cyanides and -thiocyanates, and also complexes with ; ligands, such as phosphines, phosphites, benzoin, benzoyl- and ~ acetyl-acetonates, nitriles, isonitriles and carbon monoxide.
:~ Examples of compounds of the abovementioned metals which are suitable as catalysts are: copper-II oxide, iron-III
oxide, the bromides, and in particular the chlorides, of Cu-I, - Cu-II, Fe-II and Fe-III, and also the chlorides of ruthenium, , .
rhodium, palladium, cobalt and nickel; Cu-II sulphate, Fe-II
,: , '' . , ~
,'' .
l4~5 . .
sulphate and Fe-III sulphate; Cu-II nitrate and iron-III nit-rate; manganese-III ace-ta-te and copper-II acetate; copper-II
stearate; iron-III citrate; Cu-I cyanide; ruthenium-II di-chloro-tris-triphenylphosphlne and rhodium tris-(triphenyl-phosphine) chloride; chromium acetylace-tonate and nickel acetylacetonate, copper-II acetylacetonate, iron-III acetyl-acetonate, cobal-t-II acetylacetona-te and cobal-t-III acetyl-acetonate, manganese-II acetylacetonate and copper-II benzoyl-acetona-te; iron carbonyl-cyclopentadienyl complex; molybdenum carbonyl-cyclopentadienyl complex, chromium tricarbonyl-aryl complexes, ruthenium-II acetocomplex, chromium hexacarbonyl and molybdenum hexacarbonyl, nickel tetracarbonyl, iron penta-carbonyl, cobalt carbonyl and manganese carbonyl, Mixtures of the said metals with metal compounds and/or other additives can also be used, 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, such as tert,-butyl isocyanide;
mixtures of iron powder with iron-III chloride, if desired with the addition of carbon monoxide; mixtures of iron-III chloride and benzoin; mixtures of iron-II chloride or iron-III chloride and trialkyl phosphites; and mixtures of iron pentacarbonyl and iodine, Preferred catalysts are iron-II salts and complexes and iron-III salts and complexes and also iron powder, but in particular copper powder, copper-I salts and complexes and copper-II salts and complexes, such as Cu-I chloride, Cu-II
''''' :' -' ' ' ~ , , ~ .
-"` 1~114~5 chloride, Cu-I bromide, Cu-II brornide, Cu-II acetylacetona-te, Cu-II benzoylacetonate, Cu-II sulphate, Cu-II nitrate and Cu-I
cyanide.
Very particularly preferred catalys-ts are copper powder, copper-I chloride and bromide and copper-II chloride and brom-ide, as well as mixtures thereof.
The said catalysts are generally used in amounts of about 0.01 to 10 mol %, preferably 0.1 to 5 mol %, based on the compound of the formula III or the l,l-dichloroethylene.
The addition reactions are carried out in an organic solvent. Suitable organic solvents are those in which the catalysts are adequately soluble or which can form complexes with the catalysts, but which are inert towards the starting compounds Examples of such solvents are alkylnitriles, especially those having 2-5 C atoms, such as acetonitrile, propionitrile and butyronitrile; 3-alkoxypropionitriles having 1 or 2 C atoms in the alkoxy moiety, such as 3-methoxypropio-nitrile and 3-ethoxypropionitrile; aromatic nitriles, in particular benzonitrile; aliphatic ketones having, preferably, a total of 3-8 C atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone and methyl tert.-butyl ketone; alkyl esters and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of 2-6 C atoms, such as .
methyl formate and ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate and isobutyl acetate, and also l-acetoxy-2-methoxyethane; cyclic ethers, such as tetrahydrofurane, tetra-hydropyrane and dioxane; dialkyl ethers having 1-4 C atoms in ,, .
. . .
., .' ,. , ' each alkyl moiety, such as die-thyl ether, di~n-propyl ether and di isopropyl ether; N,N-dialkylamides of aliphatic mono-carboxylic acids having 1-3 C atoms in the acid moiety, such as N,N-dime-thylformamide, N,N-dimethylace-tamide, N,N-diethylacet-amide and N,N-dimethylmethoxy-acetamide; e-thylene glycol dialkyl ethers and diethylenc glycol dialkyl ethers having 1-4 C atoms in each alk-yl moie-ty, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glcyol di-n-butyl ether, and diethylene glycol diethyl ether and diethylene glycol di-n-butyl ether; and hexamethylphosphoric acid tri-amide (Hexametapol).
Preferred solvents are alkylnitriles having 2-5 C
atoms and 3-alkoxypropionitriles having 1 or 2 C atoms in the alkoxy moiety, especially ace-tonitrile and 3-me-thoxypropio-nitrile.
The reaction temperature is in general not critical and can vary within wide limi-ts. Preferably, the reaction temperatures are between about 60 and 200C and especially between about 80 and 170C.
The compound of the formula VI or VIa which is used is preferably acrylic acid chloride or, respectively, dichloro-acetyl chloride. By using these compounds the desired 2,4,4,4-tetrahalogenobutyric acid chlorides are obtained by a direct route in the pure form and in high yields. Further preferred compounds of the formulae VI and VIa are acrylic acid and dichloroacetic acid respectively. The free 2,4,4,4-tetrahalogenobutyric acids obtained using these com-.... ... . . . . ....... .. .. .... ... . .. . . . . .. . . .
' ' ' ' : ~ .
4~
pounds can subsequently easily be eonverted, in a manner knownper se, to the corresponding acid ch].orides by reaction with inorganic acid chlorides, such as phosphorus -trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene and thionyl chloride The esters or nitriles of a 2 ,4 ,4,4-tetrahalogenobutyric acid of -the formula VII (Z = alkoxycarbonyl or cyano) which are obtained when compounds of the formula VI or VIa in which Z is alkoxycarbonyl or cyano are used are first hydrolysed, in the presence of s-trong acids, such as concentrated hydrochlorie aeid, to the eorresponding free 2,4,4,4-tetrahalogenobutyrie aeid and this is then eonver-ted to the eorresponding aeid ehloride in -the abovemen-tioned manner.
The reaetion of the 2,4,4,4-tetrahalogenobutyrie aeid ehlorides of the formula II with olefines of the fgrmula III is advantageously earried out in the presenee of an iner-t organie solvent. Suitable solvents are, for example, aromatie or .
; aliphatie hydroearbons, whieh ean be halogenated, sueh as .~ .
~ benzene, toluene, xylenes, ehlorobenzene, diehloro- and tri-. . .
1 -- ehloro-benzenes, n-pentane, n-hexane, n-oetane, methylene : ehloride, ehloroform, earbon tetraehloride, 1,1,2,2-tetra-ehloroethane and -triehloroethylene. Further suitable sol-vents are eyeloaliphatie hydroearbons sueh as eyelopentane or .~ eyelohexane, eyeloaliphatic ketones such as cyelopen-tanone and eyelohexanone, and also aliphatie ketones, aliphatie and eyelie ethers, alkylnitriles and 3-alkoxypropionitriles having 1 or 2 earbon atoms in the alkoxy group, espeeially acetonitrile and .
,~
.'.
... . .. , . . .. .. , . .. . . , ~ . . . . . . ~. -4~5 was not possible to use this process, which is technically simple to carry out, for the preparation of pyrethroids which are derived from 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxy-lic acid, since corresponding a-halogenocyclobutanones suitable for the prepara-tion of such cyclopropanecarboxylic acid deriva-tives were not available.
It has already been proposed to prepare a-halogenocyclo-butanones by reacting a halogenoketene with an olefine Pro-cesses of this type are describedS for example, in German Offenlegungsschrift 2,539,048 and British Patent Specification 1,194,604 and also in J. Amer. Chem. Soc. 87, 5257-5259 (1965) and in Tetrahedron Letters No. 1, 135-139 (1966). This synthesis principle has not been used hitherto for the prepara-tion of ~-halogenobutanones, which are suitable as intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropane , .
carboxylic acids and their esters having an insecticidal action.
This is in particular due to the fact that the synthesis poss-ibilities which are conceivable on the basis of the above-mentioned method, i.e.
a) reaction of a halogenated olefine with a halogenoketene ln accordance with the equation:
3C-C~2-CH=C ~ ~ Y-CH=C=O / ~ 3C CH2-f-CI=o R2 - Rl - ~- H-Y
or : . .
. .
~ - 3 -.':
.
R] \ X3C-CH2-C-C=O
/C=C~I Y ~~3C-C~2-CH=C=O / -- ~ C~ Y
or - b) reaction of an unhalogenated olefine with a halogenoketene - in accordance with the equation:
.
X3C - CH2 - l=C=O ~ ~ C=C1~2 ~ X3C CH2~ ==o ~, 12 the symbols Rl, R2, X and Y in the above equations being as defined under formula I, do not lead to the 2-(2',2',2'-tri-halogenoethyl)-4~halogenocyclobutan-1-ones of the formula I, which are required as intermediates, since the reaction accord-ing to a) does not take place because of the deactivation of the olefine which is associated with the substitution by halo-gen and the reaction according to b) results in a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one which cannot be converted into a 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxy-lic acid, or an ester thereof, using an alkali metal hydroxide or alkali metal alcoholate.
The object on which the present invention is based is, therefore, to provide a process for -the preparation of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula I which uses readily accessible starting materials ar.d ~ ~ _ :
. is simple to carry out.
A further object on which -the present invention is : based is to make available the 2-(2',2',2i-trihalogenoethyl)-4-:: halogenocyclobutan-l-ones of the formula I, which have not been known hitherto and which on heating with strong bases, such as alkali metal hydroxides or alkali me-tal alcohola-tes, give the : corresponding 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives, with contraction of the ring and, at the same :. time, the elimination of 2 mols of hydrogen halide, and also readily accessible in-termediates which can be used for the pre-paration of ~-halogenocyclobutanones of the formula I
: It has now been found that 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula I can be prepared in a simple manner by reacting a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II
X3C- CH2 _ fH COCl . (II) :~ . Y
in which X and Y are as defined under formula I, in the presence of an organic base with an olefine of the formula III
.. ~Rl ' CH2 -C (III) : \
: R2 in whic'n Rl and R2 are as defined under formula I, to give a ... , .. ,. , . . . , ., ., .. . ~.. . . . ... , .. ...... , ,.. ~.. .... ..... .
4~5 : 2-(2~,2',2~-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV
~ X3C - CH2 - C - C = O (IV) .. . .
',' ~1 1 C H2 .... -' ' `-' 'R2 `
.:.`' , in which Rl, R2, X and Y are as defined under formula I, and .. , then rearranging the latter, in the presence of a catalyst, in-to a 2-(2',2',2~-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I, ~: The 2,4,4,4-tetrahalogenobu-tyric acid chlorides of the formula II are novel compounds, They can be prepared in a :~ manner known per se by adding a carbon tetrahalide of the ` formula V
.
~. X
~'" X--C.--Y
X ~ (V) ~ . ' ' .
.: in which X and Y are as defined under formula I, onto a com-. pound of the formula VI
- CH2 CH - Z (VI) .: .
in which Z is chlorocarbonyl, carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl group, or cyano, and convert-ing resulting co~pounds of the forLula VII
,'~' ~ .
:
114~
~...`
'~:
` X3C C~12 - CH - Z (VII) .' . Y
.,'" .
- . . .
~ in which X and Y are as defined under formula I and Z is -:~. carboxyl, alkoxycarbonyl or cyano, into compounds of the ... .
formula VII in which Z is chlorocarbonyl, A further possibility for the preparation of 2,4,4,4-tetrahalogenobutyric acid chlorides of the formula II comprises adding a compound of the formula VIa CH - z (VIa) ., ` , in which Z is as defined under formula VI, onto l,l-dichloro-ethylene and converting resulting compounds of the formula VIIa .~:
- . C1 (VIIa) . C13C CH2 - C~ Z
.
-, in which Z is carboxyl, alkoxycarbonyl or cyano, into compounds : of the formula VIIa in which Z is chlorocarbonyl, ~ nen adding a carbon tetrahalide of the formula V onto an acrylic acid derivative of the formula VI and also when adding a dichloroacetic acid derivative of the formula VIa onto ;' ~ 7 --l4~5 ,.......................................................................... .
dichloroethylene, the carbon tetrahalide of the formula V
and, respectively, the dichloroacetic acid derivative of the formula VIa can be employed in the s-toichiome-tric amount Preferably, however, an excess of the carbon tetrahalide of the formula V or the dichloroacetic acid derivative of the formula VIa, for example an approximately 0.5-fold to 2-fold molar excess, is used and -the carbon tetrahalide of the formula V can also serve as a solvent The adding of a carbon tetrahalide of the formula V
onto a compound of the formula VI, and also the adding of a compound of the formula VIa onto l,l-dichloroethylene, is !`
carried out in the presence of catalysts. Suitable cata-lysts are metals of principal group VIII and sub-groups VIa, VIIa and Ib of the periodic system, for example iron, cobalt, nickel, ruthenium, rhodium, palladium, chromium, molybdenum, manganese and copper. These metals can be employed in the elementary form or in the form of compounds. Suitable compounds of these metals are, for example, oxides, halides, .
sulphates, sulphites, sulphides, nitrates, acetates, citrates, carbonates, cyanides and -thiocyanates, and also complexes with ; ligands, such as phosphines, phosphites, benzoin, benzoyl- and ~ acetyl-acetonates, nitriles, isonitriles and carbon monoxide.
:~ Examples of compounds of the abovementioned metals which are suitable as catalysts are: copper-II oxide, iron-III
oxide, the bromides, and in particular the chlorides, of Cu-I, - Cu-II, Fe-II and Fe-III, and also the chlorides of ruthenium, , .
rhodium, palladium, cobalt and nickel; Cu-II sulphate, Fe-II
,: , '' . , ~
,'' .
l4~5 . .
sulphate and Fe-III sulphate; Cu-II nitrate and iron-III nit-rate; manganese-III ace-ta-te and copper-II acetate; copper-II
stearate; iron-III citrate; Cu-I cyanide; ruthenium-II di-chloro-tris-triphenylphosphlne and rhodium tris-(triphenyl-phosphine) chloride; chromium acetylace-tonate and nickel acetylacetonate, copper-II acetylacetonate, iron-III acetyl-acetonate, cobal-t-II acetylacetona-te and cobal-t-III acetyl-acetonate, manganese-II acetylacetonate and copper-II benzoyl-acetona-te; iron carbonyl-cyclopentadienyl complex; molybdenum carbonyl-cyclopentadienyl complex, chromium tricarbonyl-aryl complexes, ruthenium-II acetocomplex, chromium hexacarbonyl and molybdenum hexacarbonyl, nickel tetracarbonyl, iron penta-carbonyl, cobalt carbonyl and manganese carbonyl, Mixtures of the said metals with metal compounds and/or other additives can also be used, 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, such as tert,-butyl isocyanide;
mixtures of iron powder with iron-III chloride, if desired with the addition of carbon monoxide; mixtures of iron-III chloride and benzoin; mixtures of iron-II chloride or iron-III chloride and trialkyl phosphites; and mixtures of iron pentacarbonyl and iodine, Preferred catalysts are iron-II salts and complexes and iron-III salts and complexes and also iron powder, but in particular copper powder, copper-I salts and complexes and copper-II salts and complexes, such as Cu-I chloride, Cu-II
''''' :' -' ' ' ~ , , ~ .
-"` 1~114~5 chloride, Cu-I bromide, Cu-II brornide, Cu-II acetylacetona-te, Cu-II benzoylacetonate, Cu-II sulphate, Cu-II nitrate and Cu-I
cyanide.
Very particularly preferred catalys-ts are copper powder, copper-I chloride and bromide and copper-II chloride and brom-ide, as well as mixtures thereof.
The said catalysts are generally used in amounts of about 0.01 to 10 mol %, preferably 0.1 to 5 mol %, based on the compound of the formula III or the l,l-dichloroethylene.
The addition reactions are carried out in an organic solvent. Suitable organic solvents are those in which the catalysts are adequately soluble or which can form complexes with the catalysts, but which are inert towards the starting compounds Examples of such solvents are alkylnitriles, especially those having 2-5 C atoms, such as acetonitrile, propionitrile and butyronitrile; 3-alkoxypropionitriles having 1 or 2 C atoms in the alkoxy moiety, such as 3-methoxypropio-nitrile and 3-ethoxypropionitrile; aromatic nitriles, in particular benzonitrile; aliphatic ketones having, preferably, a total of 3-8 C atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone and methyl tert.-butyl ketone; alkyl esters and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of 2-6 C atoms, such as .
methyl formate and ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate and isobutyl acetate, and also l-acetoxy-2-methoxyethane; cyclic ethers, such as tetrahydrofurane, tetra-hydropyrane and dioxane; dialkyl ethers having 1-4 C atoms in ,, .
. . .
., .' ,. , ' each alkyl moiety, such as die-thyl ether, di~n-propyl ether and di isopropyl ether; N,N-dialkylamides of aliphatic mono-carboxylic acids having 1-3 C atoms in the acid moiety, such as N,N-dime-thylformamide, N,N-dimethylace-tamide, N,N-diethylacet-amide and N,N-dimethylmethoxy-acetamide; e-thylene glycol dialkyl ethers and diethylenc glycol dialkyl ethers having 1-4 C atoms in each alk-yl moie-ty, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glcyol di-n-butyl ether, and diethylene glycol diethyl ether and diethylene glycol di-n-butyl ether; and hexamethylphosphoric acid tri-amide (Hexametapol).
Preferred solvents are alkylnitriles having 2-5 C
atoms and 3-alkoxypropionitriles having 1 or 2 C atoms in the alkoxy moiety, especially ace-tonitrile and 3-me-thoxypropio-nitrile.
The reaction temperature is in general not critical and can vary within wide limi-ts. Preferably, the reaction temperatures are between about 60 and 200C and especially between about 80 and 170C.
The compound of the formula VI or VIa which is used is preferably acrylic acid chloride or, respectively, dichloro-acetyl chloride. By using these compounds the desired 2,4,4,4-tetrahalogenobutyric acid chlorides are obtained by a direct route in the pure form and in high yields. Further preferred compounds of the formulae VI and VIa are acrylic acid and dichloroacetic acid respectively. The free 2,4,4,4-tetrahalogenobutyric acids obtained using these com-.... ... . . . . ....... .. .. .... ... . .. . . . . .. . . .
' ' ' ' : ~ .
4~
pounds can subsequently easily be eonverted, in a manner knownper se, to the corresponding acid ch].orides by reaction with inorganic acid chlorides, such as phosphorus -trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene and thionyl chloride The esters or nitriles of a 2 ,4 ,4,4-tetrahalogenobutyric acid of -the formula VII (Z = alkoxycarbonyl or cyano) which are obtained when compounds of the formula VI or VIa in which Z is alkoxycarbonyl or cyano are used are first hydrolysed, in the presence of s-trong acids, such as concentrated hydrochlorie aeid, to the eorresponding free 2,4,4,4-tetrahalogenobutyrie aeid and this is then eonver-ted to the eorresponding aeid ehloride in -the abovemen-tioned manner.
The reaetion of the 2,4,4,4-tetrahalogenobutyrie aeid ehlorides of the formula II with olefines of the fgrmula III is advantageously earried out in the presenee of an iner-t organie solvent. Suitable solvents are, for example, aromatie or .
; aliphatie hydroearbons, whieh ean be halogenated, sueh as .~ .
~ benzene, toluene, xylenes, ehlorobenzene, diehloro- and tri-. . .
1 -- ehloro-benzenes, n-pentane, n-hexane, n-oetane, methylene : ehloride, ehloroform, earbon tetraehloride, 1,1,2,2-tetra-ehloroethane and -triehloroethylene. Further suitable sol-vents are eyeloaliphatie hydroearbons sueh as eyelopentane or .~ eyelohexane, eyeloaliphatic ketones such as cyelopen-tanone and eyelohexanone, and also aliphatie ketones, aliphatie and eyelie ethers, alkylnitriles and 3-alkoxypropionitriles having 1 or 2 earbon atoms in the alkoxy group, espeeially acetonitrile and .
,~
.'.
3~methoxypropionitrile.
Particularly suitable solvents are aliphatic, cyclo-aliphatic and aromatic hydrocarbons, in particular alkanes having 5 to 8 carbon atoms, benzene and toluene, and especially n-hexane and cyclohexane However, excess olefine of the formula III can also serve as the solvent.
Suitable organic bases, in -the presence of which the reactlon of a 2,4,4,4-te-trahalogenobutyric acid chloride of the formula II with an olefine of the formula III is carried out, are, for example, tertiary amines, in par-ticular trialkylamines having 1 to 4 carbon atoms, and especially 2 to 4 carbon atoms, in each alkyl group, cyclic amines, such as pyridine, quinoline, and N-alkyl pyrrolidines, N-alkyl-piperidines, N,N-dialkyl-piperazines and N-alkyl-morpholines or dialkylanilines having 1 or 2 carbon atoms in each alkyl group, such as N-methyl-pyrrolidine, N-ethyl-piperidine, N,N'-dimethyl-piperazine, N-ethyl-morpholine and N,N-dimethylaniline, and also bicyclic amidines, such as 1,5-diazabicyclo[5.4 0]undec-5-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, and bicyclic diamines, such as 1,4-diazabicyclo[2.2.2]octane.
The reaction of 2,4,4,4-tetrahalogenobutyric acid chlorides of the formula II with olefines of the formula III is preferably carried out in -the presence of trialkyamines having 1 to 4 carbon atoms in each alkyl group. Particularly suitable bases are triethylamine and pyridine.
The organic base is employed in at least the equimolar . , .
' .
- 1~1.14~5 amount, or in a sligh-t excess, based on the 2,L~,4,4-tetra-halogenobu-tyric acid chloride of the formula Il.
The olefines of the formula III are likewise used in . at least the equimolar amount, based on -the 2,4,4,4-tetra--j halogenobutyric acid chloride of the formula II It is, however, generally advantageous to use an excess of the olefine, in which case the olefine can, as already mentioned, also serve .: as the solvent When readily vola-tile olefines are used, the reaction can be carried out under pressure : The olefines of the formula III are in par-ticular those in which one of the radicals Rl and R2 is methyl and the other is hydrogen or methyl, or Rl and R2 together are an all~ylene group having 2 to 3 carbon a-toms, i.e isobu-tylene, propene, methylenecyclopropane and methylenecyclobutane Isobutyl-. .
:. ene and me-thylenecyclopropane are particularly preferred The reaction temperatures can vary within wide limits They are in general between 0 and 200C and preferably between 20 and 160C.
The 2-(2',2',2'--trihalogenoethyl)-2-halogenocyclobutan-ones of the formu~a IV are also novel compounds Cata-lysts which can be used for the rearrangement of the 2-(2',2',2'-. trihalogenoethyl)-2-halogenocyclobutan-l-ones of the formula IV, which are first obtained, into 2-(2',2',2'-trihalogeno-. ethyl)-4-cyclobutan-l-ones of the formula I are acids, bases or quaternary ammonium halides The rearrangement, according to -the invention, of 2-(2',2',2'-trihalogenoethyl)-2 halogenocyclobutan-l-ones of the .'.'~ . - 14 _ .
~114~5 formula I~ in-to 2-(2',2',2'-trihalogenoe-thyl)~L~-halogenocyclo-butan l-ones of the formula I is unexpected and is not known in the case of cyclobutanones monohalogenated in the a-position.
It is particularly surprising -tha-t no elimination of HX takes place at the trihalogenoethyl group when -the rearrangement is carried-out in the presence of a basic catalyst. The re-arrangement proceeds with excellent, and frequently quantitative, yield.
The rearrangement, according to the invention, of 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-ones of the formula IV into 2-(2',2',2'-trihalogenoethyl)-~halogenocyclo-butan-l-ones of the formula I is preferably carried out in the presence of basic catalysts. The basic catalysts are organic bases, such as primary, secondary and especially tert-iary amines of the formula /
in which Ql is alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, benzyl or phenyl and Q2 and Q3 independently of one another are hydrogen or alkyl having 1 to 8 carbon atoms. -Suitable basic catalysts are, for example, triethylamine, tri-n-butylamine, tri-isopentylamine, tri-n-octylamine, N,N-dimethylcyclohexylamine, M,N-dimethylbenzyl-amine, N,N-dimethyl-2-ethylhexylamine, N,N-diethylaniline and . . .. . . ... ... ~ . . .. . ... .. ..
' :
~` also cyclic amines, such as pyrldine, quinoline, lutidine, . .
N-alkylmorpholines, such as N-methylmorpholines, N-alkyl-piperidines, such as N-methyl- and ~-ethyl-piperidine, N-alkyl-pyrrolidines, such as N-methyl- and N-ethyl-pyrrolidine, diamines, such as N,N,N',N'-te-tramethyle-thylenediamine and N,N,N',N'-tetramethyl-1,3-diaminobutane, N,N'-dialkylpipera-zines, such as N,N'~dirne-thylpiperazine, bicyclie arnines, such as 1,4-diazabicyclo[2.2.2~octane, and bieyclic amidines, such as 1,5-diazabicyclo[5.4.0]undec-5-ene and 1,5-diazabicyclo-[4.3.0]non-5-ene, and finally polymerie basie compounds, sueh as p-dimethylaminomethylpolystyrene.
Fur-ther suitable basie eatalysts for the rearrangement, aecording to the invention, of a 2-(2',2',2'-trihalogenoethyl)-2-halogenoeyclobu-tan-1-one of -the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyelobutan-1-one of the formula I
are phosphines, especially trialkylphosphines, for example tri-butylphosphine.
Aeid eatalysts whieh ean be used for the rearrangement ,i~. . .
of 2-(2',2',2'-trihalogenoethyl)-2-halogenoeyclobutan-1-ones of the formula IV into 2-(2',2',2'-trihalogenoethyl)-4-halogeno-eyelobutan-l-ones of the formula I are inorganic or organle proton aeids. Suitable inorganic proton acids are, for example, hydrogen halide aeids, such as hydrogen chloride, hydrogen bromide, hydrogen fluoride and hydrogen iodide, nitric acid, phosphorie acid and sulphuric acid. Preferred inor-ganic proton acids are hydrogen halide acids.
If aeids or bases are employed in exeess, they e~n ~ 16 ~
1~ 45 also serve as solvents.
Furthermore, salts of pro-ton acids, especially hydrogen halide acids, with ~rnrnonia or a nitrogen-containing organic base, and also quaternary arnmonium halides, quaternary phos-phonium halides and sulphoniurn halides can be employed.
Suitable nitrogen-con-taining organic bases are aliphatic, cycloaliphatic, araliphatic and aroma-tic primary, secondary and tertiary amines, as well as heterocyclic nitrogen bases Examples are: primary aliphatic amines having up -to 12 C atoms, such as methylarnine, ethylamine, n-butylarnine, n-octylamine, n-dodecylamine, hexamethylenediarnine, cyclohexylamine and benzylamine; secondary aliphatic amines having up to 12 C
a-toms, such as dimethylamine, diethylamine, di-n-propylarnine, dicyclohexylarnine, pyrrolidine, piperidine, piperazine and morpholine; -tertiary aliphatic amines, especially -trialkyl-amines having 1-4 C atoms in each alkyl moiety, such as tri-..~
ethylarnine, tri-n-butylamine, N-methylpyrrolidine, N-methyl-~; -morpholine, 1,4-diazabicyclo[2.2.2]octane and quinuclidine;
; substituted or unsubs-ti-tuted primary, secondary and ter-tiary aromatic amines, such as aniline, toluidine, naphthylamine, N-methylaniline, diphenylamine and N,N-diethylaniline; and also - pyridine, picoline, indoline and quinoline.
Quaternary phosphonium halides which can be used are, for example: hexadecyltributylphosphonium bromide and methyl-; and ethyl-triphenylphosphonium bromide; and a sulphonium halide which can be used is, for exarnple-, trimethylsulphonium iodide.
. .
Preferred salts are those of the ~ormula ~5 M- 'Q ~ Q
' ' Q7 '~. in which M is fluorine, bromine or iodine and especially chlor-" ine, Q4 is hydrogen5 alkyl having 1-18 C atoms, cyclohexyl, .. benzyl, phenyl or naphthyl and Q5, Q6 and ~ independently o~
,. one another are hydrogen or alkyl having 1~18 C atoms, and also "'. N-alkyl-pyridinium halides having 1-18 C a-toms in -the alkyl, ~,,' especially the corresponding chlorides, ,~. Examples of such salts are: ammonium chloride, .~. , ., ammonium bromide, methylamine hydrochloride, cyclohexylamine ` hydrochloride, aniline hydrochloride, dime-thylamine hydro-,' chloride, di~isobutylamine hydrochloride, triethylamine hydro-., chloride, triethylamine hydrobromide, tri-n-octylamine hydro-,' chloride, benzyl-dimethylamine hydrochloride, tetramethylammon ' iu,m chloride, bromide and iodide, tetraethylammonium chloride, -,' bromide and iodide, tetra-n-propylammonium chloride, bromide '' and iodide, tetra-n-bu-tylammonium chloride, bromide and iodide, trimethyl-hexadecylammonium chloride, benzyldimethylhexadecyl-' ammonium chloride, benzyldimethyltetradecylammonium chloride, benzyl-trimethyl-, -triethyl- and -tri-n-butyl-ammonium chlor-: ide, n-butyl-tri-n-propylammonium bromide, octadecyl-trimethyl-ammonium bromide, phenyltrimethylammonium bromide or chloride and hexadecylpyridinium bromide -and chloride.
Additional co-catalysts which can be used are alkali '-metal halides, such as potassium iodide, sodium iodide, li-thium iodide, potassium bromide, sodium bromide, li-thium bromide, potassium chloride, sodium chloride, lithium chloride, potass-ium fluoride, sodium fluoride and lithium fluoride.
These co-catalysts ca-talyse the reaction even in the absence of the above ammonium salts, but additions of open-chain or macrocyclic polye-thers (crown ethers) are -then advan-tageous for a rapid course of reaction. Examples of such crown ethers are: 15-crown~5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and 5,6,14,15-dibenzo-7,13-diaza-1,4-dioxa-cyclopentadeca-5,14-diene, The amount of catalyst employed can vary wi-thin wide limits. In some cases it suffices if the catalyst is pres-ent in traces. In general, however, the catalyst is prefe~ly employed in an amolmt of about 0.1 -to 15 per cent by weight, based on the compound of the formula VI.
The rearrangement can be carried out either in the melt or in an inert organic solvent. The reaction temperatures for the rearrangement in the melt are in general between about 60 and 150C and especially about 80 and 130C.
Suitable catalysts for the rearrangement in the melt are, in particular, the abovementioned organic bases, especially trialkylamines having 1-8 C atoms in each alkyl moiety; and also salts of hydrogen halide acids with ammonia or organic nitrogen-containing bases, such as trialkylamine hydrochlorides and hydrobromides having 1- 8 C atoms in each alkyl moiety, and very particularly tetraalkylammonium halides, in particular .
. "'. .: :
49~5 : `
tetraalkylammonium chlorides, b:romides and iodides, having . 1-18 C atoms in each alkyl moie-ty.
~. Examples of sui~table inert organic solvents are ali-phatic, cycloaliphatic or aromatic hydrocarbons, which can be ~ nitrated or halogenated, such as n-hexane, n-pentane, cyclo-:. hexane, benzene, toluene, xylenes, nitrobenzene, chloroform, ; carbon te-trachloride, -trichloroethylene, 1,1,2,2-tetrachloro-. ethane, nitromethane, chlorobenzene, dichlorobenzenes and tri-chlorobenzenes; lower aliphatic alcohols, for example those l having up to 6 C atoms, such as methanol, ethanol, propanol, :. isopropanol, butanols and pentanols; aliphatic diols, such as : ethylene glycol and diethylene glycol; ethylene glycol monoalkyl ethers and diethylene glycol monoalkyl ethers having, in each case, 1-4 C atoms in the alkyl moieties, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, diethylene .. . .
glycol monomethyl ether and diethylene glycol monoethyl ether;
cycllc amides, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-~-caprolactam; amides of carbonic acid, such as tetramethylurea and dimorpholinocarbonyl; amides of phosphorous acid, of phosphoric acid, of phenylphosphonic acid or of aliphatic phosphonic acids having 1-3 C atoms in the acid moiety, such as phosphoric acid triamide, phosphoric acid tris-(dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolinide, phosphoric acid bis-(dimethylamide)-morpholide, phosphoric acid dimethylamide-diethylamide-morpholide, phos-phorous acid tri.s-(dimethylamide) and the tetramethyldiamide of methanephosphonic acid; amides of sulphuric acid and of : .
' ,:
.~ aliphatic or aromatic sulphonic acids, such as -tetrame-thyl-2m~e, -the dimethylamide of methanesulphonic acid or p-toluenesulphonic acid amide; sulphur-contai.ning solvents, such as organic sulphones and sulphoxides, for example dimethyl-sulphoxide and su]pholane; and aliphatic and aromatic nitriles, 3-alkoxypropionitriles, alipha-tic ketones, alkyl and alkoxyalkyl :~: esters of a].ipha-tic monocarboxylic acids, cyclic ethers, dialkyl . ethers, N,N-disubsti-tuted amides of aliphatic monocarboxylic ., , acids and ethylene glycol dialkyl ethers and diethylene glycol dialkyl ethers of the type mentioned under process stage 1) For the rearrangement in the presence of an acid cata-lyst, polar solven-ts are advantageously used, especially lower alcohols, such as methanol, ethanol and butanols, N,N-dialkyl-amides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, especially N,N-dimethylformamide, or dialkyl-sulphoxides, such as dimethylsulphoxide.
In aprotic, strongly polar solvents, such as the above-mentioned N,N-disubstituted amides of alipha-tic monocarboxylic acids, cyclic amides, amides of carbonic acid, amides of phos-phorous acid, of phosphoric acid, of phenylphosphonic acid or of aliphatic phosphonic acids, amides of sulphuric acid or of aliphatic or aromatic sulphonic acids, and also dialkylsulphox-ides, such as dimethylsulphoxide, the reaction also proceeds without the addition of base or acid. In these cases, the solvent acts as the catalyst.
In general, however, when the rearrangement is carried out in the presence of an inert organic solvent a catalyst is . .
_ 21 -:
, .. .....
.
., , ~ i~L1~45 , . .
added, preferably an organic base having a PKa value of more than 9, especially trialkylam:lnes having 1 g C atoms in each :
alkyl moiety, such as triethylamine, tri-n~bu-tylamine and tri-n-octylamine; and also hydrogen halide acids, especially HCl ; and HBr, and tetraalkylammonium halides, èspecially tetraalkyl-~,, .
ammonium chlorides, bromides and iodides having 1-18 C atoms in each alkyl moiety.
Particularly preferred solven-ts are aliphatic alcohols having 1-4 C atoms, toluene, xylenes, chlorobenzene, dioxane, acetoni-trile, 3-methoxypropioni-trile, ethylene glycol diethyl ether and di-isopropyl ketone The reaction temperatures for the rearrangement in the presence of an incrt organic solvent are in general between about 0 and 150C and preferably between about 80 and 130C
By means of the process according -to the invention, novel 2-(2',2',2'--trihalogenoethyl)-4--halogeno-cyclobutan-1-ones of the formula I, which are substituted in the 3-position and are suitable as intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives sub-stituted in the 3-positionj are available in a simple manner and in good yield, using readily accessible starting materials The process according to the invention is especially suitable for the preparation of 2-(2',2',2'-trichloroethyl)-4-halogeno-..
cyclobutan-l-ones of the formula I which are substituted in the 3-position The course of the process according to the invention is extremely surprising and completely unforeseeable, since, when a 2,4,4,4-tetrahalogenobu-tyric acid chloride of -the . . .
_ 22 -::' :..
` ~.114~
formula II, or a halogenGke-tene formed -therefrom in situ by the : elimination of hydrogen chloricle, is reacted with an olefine of the formula III, a 2-(2',2',2'-trihalogenoethyl)-2-halogeno-; cyclobutan~1-one of the formula IV, which is unsui-table for further conversion into a 2-(2',2'-dihalogenovinyl)-cyclopro-. panecarboxylic acid derivative subs-titu-ted in the 3-position, is first formed and this is then conver-ted, by a novel re-arrangement, not hi-therto observed in the case of cyclobu-tanones, monohalogenated in the ~-position, into a 2-(2',2',2'-tri-halogenoethyl)-4-halogenocyclobutan-1-one of the formula I, which is suitable for further conversion into a 2-(2',2'-di--halogenovinyl)-cyclopropanecarboxylic acid derivative substitu-: -ted in the 3-positi.on.
The 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acids substituted in the 3-position, and their esters having an :: insecticidal action, which can be prepared using novel 2-(2',2',2'-trihalogenoe-thyl)-4-chlorocyclobutan-1 ones of the .formula I as the starting materials, can be described by the following formula VIII:
Rl ~ 2 : C (VIII) , .X2C = CH - CH Cll - COOR
in which X, Rl and R2 are as defined under formula I and R is hydrogen, alkyl having 1 to 4 carbon atoms or a group of the formula IX
. - 23 -.' ' ~ - ~ .
.;" -., , -`
~-~ R~
--C11----C ~
I ~ 1~R5 (IX) R6 C C~l R
, ,' in which R3 is oxygen, sulphur or a vinylene group, R4 is hydrogen, alky] having 1 to 4 carbon atoms, benzyl, phenoxy - or phenylmercapto, R5 is hydrogen or an alkyl group having 1 to ~ 4 carbon atoms and R6 is hydrogen, cyano or ethynyl, or, if one , ~ of the radicals Rl and R2 is me-thyl and the o-ther is hydrogen or ... ~
methyl, R3 is the vinylene group, R4 is phenoxy and R5 is hydro-1 . ~ .
gen, also alkyl having 1 to 5 carbon atoms.
The 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives of -the formula VIII in which R is a group of the formula IX are suitable for combating diverse animal on plan-t pests, especially insects The properties, fields of application and use forms of these active compounds are described in the literature (c.f., for example, Nature, 246, 169-170 (1973); Nature, 248, 710~711 (1974); Proceedings .
7th British Insecticide and Fungicide Conference, 721-728 (1973); Proceedings 8th British Insecticide and Fungicide Con-ference, 373-78 (1975); J. Agr. Food Chem. 23, 115 (1973);
U.S. Patent Specification 3,961,070; and German Offenlegungs-schriften 2,553,991, 2,439,177, 2,326,077 and 2,614,648).
The conversion of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-l-ones of the formula I into 2-(2',2'-di-halogenovinyl)-cyclopropanecarboxylic acid derivatives of the , .
` - 24 _ ' .. .. .. ..
-` lil~445 formula VIII is carried out in a manner known per se, by heating in the presence of suital,le bases. Exarnples of sui-table bases are alkali metal hydroxides and alkaline earth rnetal hydroxides, such as sodium hydroxide, potassium hydroxide, calcium hydroxide and bariurn hydroxide. Alkali me-tal carbonates and bicarbonates and alkaline earth metal carbonates and bicarbonates, such as calciurn carbona-te, barium carbonate, potassium carbonate, sodium carbona-te, sodium bicarbona-te and potassium bicarbonate, can also be used as bases Further suitable bases are alcoholates derived from the radical R
according to -the above definition, especially the corresponding sodiurn alcoholates and po-tassium alcoholates. The use of such alcoholates has the advantage -that -the corresponding éster is obtained direct, whilst when alkali metal hydroxides and alkaline ear-th metal hydroxides are used, -the salts of these bases with the 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid formed are firstobtained. These salts can, however, also be conver-ted into es-ters in a simple manner which is known per se, for example by converting them into the corresponding acid chloride and reacting the latter with an alcohol derived from the radical R.
Depending on the nature of the base used, -the conversion of a 2-(2',2',2'--trihalogenoethyl)-4-halogenocyclobutan-l-one of the formula I into a 2-(2',2'-dihalogenovinyl)-cyclopropane-carboxylic acid derivative of the formula VIII is advantageously carried out in an aqueous, aqueous-organic or organic medium.
When the base used is an alkali me-tal carbonate or alkaline earth , .- - 25 -, . ' ' , `':
' me-tal carbonate, the reac-tio~ is carried out in an aqueous or aqueous-organic medium. The reaction in the presence of alkali metal hydroxides or alka]ine earth metal hydroxides and alkali metal bicarbonates is also advantageously carried out in an aqueous or aqueous-organic medium. In this case, the free 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acids of the formula VIII (R = H) are obtained af-ter acidifying -the reaction mixture, for example by adding concentrated hydro-chloric acid~
Suitable solvents for the conversion of 2-(2~,2'S2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of -the formula I
into 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives of -the formula VIII in an aqueous-organic or organic medium are lower alcohols, for example those having 1 to 6 -:.
carbon atoms, benzyl alcohol, aliphatic or cyclic ethers, such as diethyl ether, di-n-propyl ether, diisopropyl ether, -tetra-hydrofurane and dioxane, and also alipha-tic, cycloaliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclo~
hexane, benzene, toluene and xylenes.
The conversion of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula I to 2-(2',2'-dihalo-genovinyl)-cyclopropanecarboxylic acid derivatives of the formula VIII is generally carried out at the boiling point of the reaction medium chosen. Reaction -temperatures of ~ between 40 and 120C are particularly suitable.
-~ When 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan~
l-ones of the formula I are converted into 2-(2',2'-dihalogenc-vinyl)-cyclopropanecarbcxylic acid deriva-tlves of the formula VIII, the corresponding 2-(2',2',2'--trihalogenoethyl)-cyclo~
propanecarboxylic acid derivatives of the formula X
~ ' . \C~.`/ ' ' (X) X3~ - CH~ - CH --- ~ CH - COOR
in which R, Rl, R2 and X are as defined, are formed as inter-mediates, These produc-ts can be isola^ted if the reaction tempera-ture is kept below 4oc and/or a less than equivalent - amount of base is used. Above 1~0C, these in-termediates are converted to -the corresponding 2-(2',2'~dihalogenovinyl)-cyclopropanecarboxylic acid der~ivatives of the formula VIII on the addition of further base, with the elimina-tion of HX.
. ~:
The 2-(2',2',2'-trlhalogenoethyl)-cyclopropanecarboxylic acid derivatives of the formula X can also be prepared photo-chemically from 2-(2',2~,2~-trihalogenoethyl)-L~-halogenocyclo-:.
butan-l-ones of the formula I, by irradiation with W light, ; - if necessary with the addition of conventional sensitisers (for example ketones, such as acetone, cyclohexanone, benzo-~,' phenone, acetophenone and higher alkylaryl ketones, thioxan-- thone and the like), in the presence of reagents containing `, hydroxyl groups, which at the same -time can serve as solvents, , Examples of reagents containing hydroxyl groups are alkanols, such as methanol, ethanol and the Iike, and in particular water.
The process according to the invention is illustrated ' ~3~1~4~5 in more detail by the fol.lowin~ eYamples ple ]
a) ~r~ f~ ~ 4l_ ~ tet-ra ~ ;r ~o:d ehloride 452 5 g (5 mols) of acrylic acid chloride (-technical grade purity), 1 5 litres of carbon tetrachloride, 1 5 litres of acetonitrile and 30 g of copper-I chloride are kept at 115C
for 24 hours The reaction r~lix-ture is fil-tered to give a clear filtrate and the latter is evaporated under a waterpump vacuum The residue is distilled This gives 922 g (76% of theory) of 2,4,4,4-te-trachlorobutyric acid chloride;
boiling point 78-80C/ll mm Hg.
IR spectrum (CIIC13) in cm 1 1780 (C=0) NMR spectrum (100 MHz, CDC13) in ppm: 3 16-3 94 (m, 2H, CH2);
Particularly suitable solvents are aliphatic, cyclo-aliphatic and aromatic hydrocarbons, in particular alkanes having 5 to 8 carbon atoms, benzene and toluene, and especially n-hexane and cyclohexane However, excess olefine of the formula III can also serve as the solvent.
Suitable organic bases, in -the presence of which the reactlon of a 2,4,4,4-te-trahalogenobutyric acid chloride of the formula II with an olefine of the formula III is carried out, are, for example, tertiary amines, in par-ticular trialkylamines having 1 to 4 carbon atoms, and especially 2 to 4 carbon atoms, in each alkyl group, cyclic amines, such as pyridine, quinoline, and N-alkyl pyrrolidines, N-alkyl-piperidines, N,N-dialkyl-piperazines and N-alkyl-morpholines or dialkylanilines having 1 or 2 carbon atoms in each alkyl group, such as N-methyl-pyrrolidine, N-ethyl-piperidine, N,N'-dimethyl-piperazine, N-ethyl-morpholine and N,N-dimethylaniline, and also bicyclic amidines, such as 1,5-diazabicyclo[5.4 0]undec-5-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, and bicyclic diamines, such as 1,4-diazabicyclo[2.2.2]octane.
The reaction of 2,4,4,4-tetrahalogenobutyric acid chlorides of the formula II with olefines of the formula III is preferably carried out in -the presence of trialkyamines having 1 to 4 carbon atoms in each alkyl group. Particularly suitable bases are triethylamine and pyridine.
The organic base is employed in at least the equimolar . , .
' .
- 1~1.14~5 amount, or in a sligh-t excess, based on the 2,L~,4,4-tetra-halogenobu-tyric acid chloride of the formula Il.
The olefines of the formula III are likewise used in . at least the equimolar amount, based on -the 2,4,4,4-tetra--j halogenobutyric acid chloride of the formula II It is, however, generally advantageous to use an excess of the olefine, in which case the olefine can, as already mentioned, also serve .: as the solvent When readily vola-tile olefines are used, the reaction can be carried out under pressure : The olefines of the formula III are in par-ticular those in which one of the radicals Rl and R2 is methyl and the other is hydrogen or methyl, or Rl and R2 together are an all~ylene group having 2 to 3 carbon a-toms, i.e isobu-tylene, propene, methylenecyclopropane and methylenecyclobutane Isobutyl-. .
:. ene and me-thylenecyclopropane are particularly preferred The reaction temperatures can vary within wide limits They are in general between 0 and 200C and preferably between 20 and 160C.
The 2-(2',2',2'--trihalogenoethyl)-2-halogenocyclobutan-ones of the formu~a IV are also novel compounds Cata-lysts which can be used for the rearrangement of the 2-(2',2',2'-. trihalogenoethyl)-2-halogenocyclobutan-l-ones of the formula IV, which are first obtained, into 2-(2',2',2'-trihalogeno-. ethyl)-4-cyclobutan-l-ones of the formula I are acids, bases or quaternary ammonium halides The rearrangement, according to -the invention, of 2-(2',2',2'-trihalogenoethyl)-2 halogenocyclobutan-l-ones of the .'.'~ . - 14 _ .
~114~5 formula I~ in-to 2-(2',2',2'-trihalogenoe-thyl)~L~-halogenocyclo-butan l-ones of the formula I is unexpected and is not known in the case of cyclobutanones monohalogenated in the a-position.
It is particularly surprising -tha-t no elimination of HX takes place at the trihalogenoethyl group when -the rearrangement is carried-out in the presence of a basic catalyst. The re-arrangement proceeds with excellent, and frequently quantitative, yield.
The rearrangement, according to the invention, of 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-ones of the formula IV into 2-(2',2',2'-trihalogenoethyl)-~halogenocyclo-butan-l-ones of the formula I is preferably carried out in the presence of basic catalysts. The basic catalysts are organic bases, such as primary, secondary and especially tert-iary amines of the formula /
in which Ql is alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, benzyl or phenyl and Q2 and Q3 independently of one another are hydrogen or alkyl having 1 to 8 carbon atoms. -Suitable basic catalysts are, for example, triethylamine, tri-n-butylamine, tri-isopentylamine, tri-n-octylamine, N,N-dimethylcyclohexylamine, M,N-dimethylbenzyl-amine, N,N-dimethyl-2-ethylhexylamine, N,N-diethylaniline and . . .. . . ... ... ~ . . .. . ... .. ..
' :
~` also cyclic amines, such as pyrldine, quinoline, lutidine, . .
N-alkylmorpholines, such as N-methylmorpholines, N-alkyl-piperidines, such as N-methyl- and ~-ethyl-piperidine, N-alkyl-pyrrolidines, such as N-methyl- and N-ethyl-pyrrolidine, diamines, such as N,N,N',N'-te-tramethyle-thylenediamine and N,N,N',N'-tetramethyl-1,3-diaminobutane, N,N'-dialkylpipera-zines, such as N,N'~dirne-thylpiperazine, bicyclie arnines, such as 1,4-diazabicyclo[2.2.2~octane, and bieyclic amidines, such as 1,5-diazabicyclo[5.4.0]undec-5-ene and 1,5-diazabicyclo-[4.3.0]non-5-ene, and finally polymerie basie compounds, sueh as p-dimethylaminomethylpolystyrene.
Fur-ther suitable basie eatalysts for the rearrangement, aecording to the invention, of a 2-(2',2',2'-trihalogenoethyl)-2-halogenoeyclobu-tan-1-one of -the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyelobutan-1-one of the formula I
are phosphines, especially trialkylphosphines, for example tri-butylphosphine.
Aeid eatalysts whieh ean be used for the rearrangement ,i~. . .
of 2-(2',2',2'-trihalogenoethyl)-2-halogenoeyclobutan-1-ones of the formula IV into 2-(2',2',2'-trihalogenoethyl)-4-halogeno-eyelobutan-l-ones of the formula I are inorganic or organle proton aeids. Suitable inorganic proton acids are, for example, hydrogen halide aeids, such as hydrogen chloride, hydrogen bromide, hydrogen fluoride and hydrogen iodide, nitric acid, phosphorie acid and sulphuric acid. Preferred inor-ganic proton acids are hydrogen halide acids.
If aeids or bases are employed in exeess, they e~n ~ 16 ~
1~ 45 also serve as solvents.
Furthermore, salts of pro-ton acids, especially hydrogen halide acids, with ~rnrnonia or a nitrogen-containing organic base, and also quaternary arnmonium halides, quaternary phos-phonium halides and sulphoniurn halides can be employed.
Suitable nitrogen-con-taining organic bases are aliphatic, cycloaliphatic, araliphatic and aroma-tic primary, secondary and tertiary amines, as well as heterocyclic nitrogen bases Examples are: primary aliphatic amines having up -to 12 C atoms, such as methylarnine, ethylamine, n-butylarnine, n-octylamine, n-dodecylamine, hexamethylenediarnine, cyclohexylamine and benzylamine; secondary aliphatic amines having up to 12 C
a-toms, such as dimethylamine, diethylamine, di-n-propylarnine, dicyclohexylarnine, pyrrolidine, piperidine, piperazine and morpholine; -tertiary aliphatic amines, especially -trialkyl-amines having 1-4 C atoms in each alkyl moiety, such as tri-..~
ethylarnine, tri-n-butylamine, N-methylpyrrolidine, N-methyl-~; -morpholine, 1,4-diazabicyclo[2.2.2]octane and quinuclidine;
; substituted or unsubs-ti-tuted primary, secondary and ter-tiary aromatic amines, such as aniline, toluidine, naphthylamine, N-methylaniline, diphenylamine and N,N-diethylaniline; and also - pyridine, picoline, indoline and quinoline.
Quaternary phosphonium halides which can be used are, for example: hexadecyltributylphosphonium bromide and methyl-; and ethyl-triphenylphosphonium bromide; and a sulphonium halide which can be used is, for exarnple-, trimethylsulphonium iodide.
. .
Preferred salts are those of the ~ormula ~5 M- 'Q ~ Q
' ' Q7 '~. in which M is fluorine, bromine or iodine and especially chlor-" ine, Q4 is hydrogen5 alkyl having 1-18 C atoms, cyclohexyl, .. benzyl, phenyl or naphthyl and Q5, Q6 and ~ independently o~
,. one another are hydrogen or alkyl having 1~18 C atoms, and also "'. N-alkyl-pyridinium halides having 1-18 C a-toms in -the alkyl, ~,,' especially the corresponding chlorides, ,~. Examples of such salts are: ammonium chloride, .~. , ., ammonium bromide, methylamine hydrochloride, cyclohexylamine ` hydrochloride, aniline hydrochloride, dime-thylamine hydro-,' chloride, di~isobutylamine hydrochloride, triethylamine hydro-., chloride, triethylamine hydrobromide, tri-n-octylamine hydro-,' chloride, benzyl-dimethylamine hydrochloride, tetramethylammon ' iu,m chloride, bromide and iodide, tetraethylammonium chloride, -,' bromide and iodide, tetra-n-propylammonium chloride, bromide '' and iodide, tetra-n-bu-tylammonium chloride, bromide and iodide, trimethyl-hexadecylammonium chloride, benzyldimethylhexadecyl-' ammonium chloride, benzyldimethyltetradecylammonium chloride, benzyl-trimethyl-, -triethyl- and -tri-n-butyl-ammonium chlor-: ide, n-butyl-tri-n-propylammonium bromide, octadecyl-trimethyl-ammonium bromide, phenyltrimethylammonium bromide or chloride and hexadecylpyridinium bromide -and chloride.
Additional co-catalysts which can be used are alkali '-metal halides, such as potassium iodide, sodium iodide, li-thium iodide, potassium bromide, sodium bromide, li-thium bromide, potassium chloride, sodium chloride, lithium chloride, potass-ium fluoride, sodium fluoride and lithium fluoride.
These co-catalysts ca-talyse the reaction even in the absence of the above ammonium salts, but additions of open-chain or macrocyclic polye-thers (crown ethers) are -then advan-tageous for a rapid course of reaction. Examples of such crown ethers are: 15-crown~5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and 5,6,14,15-dibenzo-7,13-diaza-1,4-dioxa-cyclopentadeca-5,14-diene, The amount of catalyst employed can vary wi-thin wide limits. In some cases it suffices if the catalyst is pres-ent in traces. In general, however, the catalyst is prefe~ly employed in an amolmt of about 0.1 -to 15 per cent by weight, based on the compound of the formula VI.
The rearrangement can be carried out either in the melt or in an inert organic solvent. The reaction temperatures for the rearrangement in the melt are in general between about 60 and 150C and especially about 80 and 130C.
Suitable catalysts for the rearrangement in the melt are, in particular, the abovementioned organic bases, especially trialkylamines having 1-8 C atoms in each alkyl moiety; and also salts of hydrogen halide acids with ammonia or organic nitrogen-containing bases, such as trialkylamine hydrochlorides and hydrobromides having 1- 8 C atoms in each alkyl moiety, and very particularly tetraalkylammonium halides, in particular .
. "'. .: :
49~5 : `
tetraalkylammonium chlorides, b:romides and iodides, having . 1-18 C atoms in each alkyl moie-ty.
~. Examples of sui~table inert organic solvents are ali-phatic, cycloaliphatic or aromatic hydrocarbons, which can be ~ nitrated or halogenated, such as n-hexane, n-pentane, cyclo-:. hexane, benzene, toluene, xylenes, nitrobenzene, chloroform, ; carbon te-trachloride, -trichloroethylene, 1,1,2,2-tetrachloro-. ethane, nitromethane, chlorobenzene, dichlorobenzenes and tri-chlorobenzenes; lower aliphatic alcohols, for example those l having up to 6 C atoms, such as methanol, ethanol, propanol, :. isopropanol, butanols and pentanols; aliphatic diols, such as : ethylene glycol and diethylene glycol; ethylene glycol monoalkyl ethers and diethylene glycol monoalkyl ethers having, in each case, 1-4 C atoms in the alkyl moieties, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, diethylene .. . .
glycol monomethyl ether and diethylene glycol monoethyl ether;
cycllc amides, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-~-caprolactam; amides of carbonic acid, such as tetramethylurea and dimorpholinocarbonyl; amides of phosphorous acid, of phosphoric acid, of phenylphosphonic acid or of aliphatic phosphonic acids having 1-3 C atoms in the acid moiety, such as phosphoric acid triamide, phosphoric acid tris-(dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolinide, phosphoric acid bis-(dimethylamide)-morpholide, phosphoric acid dimethylamide-diethylamide-morpholide, phos-phorous acid tri.s-(dimethylamide) and the tetramethyldiamide of methanephosphonic acid; amides of sulphuric acid and of : .
' ,:
.~ aliphatic or aromatic sulphonic acids, such as -tetrame-thyl-2m~e, -the dimethylamide of methanesulphonic acid or p-toluenesulphonic acid amide; sulphur-contai.ning solvents, such as organic sulphones and sulphoxides, for example dimethyl-sulphoxide and su]pholane; and aliphatic and aromatic nitriles, 3-alkoxypropionitriles, alipha-tic ketones, alkyl and alkoxyalkyl :~: esters of a].ipha-tic monocarboxylic acids, cyclic ethers, dialkyl . ethers, N,N-disubsti-tuted amides of aliphatic monocarboxylic ., , acids and ethylene glycol dialkyl ethers and diethylene glycol dialkyl ethers of the type mentioned under process stage 1) For the rearrangement in the presence of an acid cata-lyst, polar solven-ts are advantageously used, especially lower alcohols, such as methanol, ethanol and butanols, N,N-dialkyl-amides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, especially N,N-dimethylformamide, or dialkyl-sulphoxides, such as dimethylsulphoxide.
In aprotic, strongly polar solvents, such as the above-mentioned N,N-disubstituted amides of alipha-tic monocarboxylic acids, cyclic amides, amides of carbonic acid, amides of phos-phorous acid, of phosphoric acid, of phenylphosphonic acid or of aliphatic phosphonic acids, amides of sulphuric acid or of aliphatic or aromatic sulphonic acids, and also dialkylsulphox-ides, such as dimethylsulphoxide, the reaction also proceeds without the addition of base or acid. In these cases, the solvent acts as the catalyst.
In general, however, when the rearrangement is carried out in the presence of an inert organic solvent a catalyst is . .
_ 21 -:
, .. .....
.
., , ~ i~L1~45 , . .
added, preferably an organic base having a PKa value of more than 9, especially trialkylam:lnes having 1 g C atoms in each :
alkyl moiety, such as triethylamine, tri-n~bu-tylamine and tri-n-octylamine; and also hydrogen halide acids, especially HCl ; and HBr, and tetraalkylammonium halides, èspecially tetraalkyl-~,, .
ammonium chlorides, bromides and iodides having 1-18 C atoms in each alkyl moiety.
Particularly preferred solven-ts are aliphatic alcohols having 1-4 C atoms, toluene, xylenes, chlorobenzene, dioxane, acetoni-trile, 3-methoxypropioni-trile, ethylene glycol diethyl ether and di-isopropyl ketone The reaction temperatures for the rearrangement in the presence of an incrt organic solvent are in general between about 0 and 150C and preferably between about 80 and 130C
By means of the process according -to the invention, novel 2-(2',2',2'--trihalogenoethyl)-4--halogeno-cyclobutan-1-ones of the formula I, which are substituted in the 3-position and are suitable as intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives sub-stituted in the 3-positionj are available in a simple manner and in good yield, using readily accessible starting materials The process according to the invention is especially suitable for the preparation of 2-(2',2',2'-trichloroethyl)-4-halogeno-..
cyclobutan-l-ones of the formula I which are substituted in the 3-position The course of the process according to the invention is extremely surprising and completely unforeseeable, since, when a 2,4,4,4-tetrahalogenobu-tyric acid chloride of -the . . .
_ 22 -::' :..
` ~.114~
formula II, or a halogenGke-tene formed -therefrom in situ by the : elimination of hydrogen chloricle, is reacted with an olefine of the formula III, a 2-(2',2',2'-trihalogenoethyl)-2-halogeno-; cyclobutan~1-one of the formula IV, which is unsui-table for further conversion into a 2-(2',2'-dihalogenovinyl)-cyclopro-. panecarboxylic acid derivative subs-titu-ted in the 3-position, is first formed and this is then conver-ted, by a novel re-arrangement, not hi-therto observed in the case of cyclobu-tanones, monohalogenated in the ~-position, into a 2-(2',2',2'-tri-halogenoethyl)-4-halogenocyclobutan-1-one of the formula I, which is suitable for further conversion into a 2-(2',2'-di--halogenovinyl)-cyclopropanecarboxylic acid derivative substitu-: -ted in the 3-positi.on.
The 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acids substituted in the 3-position, and their esters having an :: insecticidal action, which can be prepared using novel 2-(2',2',2'-trihalogenoe-thyl)-4-chlorocyclobutan-1 ones of the .formula I as the starting materials, can be described by the following formula VIII:
Rl ~ 2 : C (VIII) , .X2C = CH - CH Cll - COOR
in which X, Rl and R2 are as defined under formula I and R is hydrogen, alkyl having 1 to 4 carbon atoms or a group of the formula IX
. - 23 -.' ' ~ - ~ .
.;" -., , -`
~-~ R~
--C11----C ~
I ~ 1~R5 (IX) R6 C C~l R
, ,' in which R3 is oxygen, sulphur or a vinylene group, R4 is hydrogen, alky] having 1 to 4 carbon atoms, benzyl, phenoxy - or phenylmercapto, R5 is hydrogen or an alkyl group having 1 to ~ 4 carbon atoms and R6 is hydrogen, cyano or ethynyl, or, if one , ~ of the radicals Rl and R2 is me-thyl and the o-ther is hydrogen or ... ~
methyl, R3 is the vinylene group, R4 is phenoxy and R5 is hydro-1 . ~ .
gen, also alkyl having 1 to 5 carbon atoms.
The 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives of -the formula VIII in which R is a group of the formula IX are suitable for combating diverse animal on plan-t pests, especially insects The properties, fields of application and use forms of these active compounds are described in the literature (c.f., for example, Nature, 246, 169-170 (1973); Nature, 248, 710~711 (1974); Proceedings .
7th British Insecticide and Fungicide Conference, 721-728 (1973); Proceedings 8th British Insecticide and Fungicide Con-ference, 373-78 (1975); J. Agr. Food Chem. 23, 115 (1973);
U.S. Patent Specification 3,961,070; and German Offenlegungs-schriften 2,553,991, 2,439,177, 2,326,077 and 2,614,648).
The conversion of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-l-ones of the formula I into 2-(2',2'-di-halogenovinyl)-cyclopropanecarboxylic acid derivatives of the , .
` - 24 _ ' .. .. .. ..
-` lil~445 formula VIII is carried out in a manner known per se, by heating in the presence of suital,le bases. Exarnples of sui-table bases are alkali metal hydroxides and alkaline earth rnetal hydroxides, such as sodium hydroxide, potassium hydroxide, calcium hydroxide and bariurn hydroxide. Alkali me-tal carbonates and bicarbonates and alkaline earth metal carbonates and bicarbonates, such as calciurn carbona-te, barium carbonate, potassium carbonate, sodium carbona-te, sodium bicarbona-te and potassium bicarbonate, can also be used as bases Further suitable bases are alcoholates derived from the radical R
according to -the above definition, especially the corresponding sodiurn alcoholates and po-tassium alcoholates. The use of such alcoholates has the advantage -that -the corresponding éster is obtained direct, whilst when alkali metal hydroxides and alkaline ear-th metal hydroxides are used, -the salts of these bases with the 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid formed are firstobtained. These salts can, however, also be conver-ted into es-ters in a simple manner which is known per se, for example by converting them into the corresponding acid chloride and reacting the latter with an alcohol derived from the radical R.
Depending on the nature of the base used, -the conversion of a 2-(2',2',2'--trihalogenoethyl)-4-halogenocyclobutan-l-one of the formula I into a 2-(2',2'-dihalogenovinyl)-cyclopropane-carboxylic acid derivative of the formula VIII is advantageously carried out in an aqueous, aqueous-organic or organic medium.
When the base used is an alkali me-tal carbonate or alkaline earth , .- - 25 -, . ' ' , `':
' me-tal carbonate, the reac-tio~ is carried out in an aqueous or aqueous-organic medium. The reaction in the presence of alkali metal hydroxides or alka]ine earth metal hydroxides and alkali metal bicarbonates is also advantageously carried out in an aqueous or aqueous-organic medium. In this case, the free 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acids of the formula VIII (R = H) are obtained af-ter acidifying -the reaction mixture, for example by adding concentrated hydro-chloric acid~
Suitable solvents for the conversion of 2-(2~,2'S2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of -the formula I
into 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid derivatives of -the formula VIII in an aqueous-organic or organic medium are lower alcohols, for example those having 1 to 6 -:.
carbon atoms, benzyl alcohol, aliphatic or cyclic ethers, such as diethyl ether, di-n-propyl ether, diisopropyl ether, -tetra-hydrofurane and dioxane, and also alipha-tic, cycloaliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclo~
hexane, benzene, toluene and xylenes.
The conversion of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula I to 2-(2',2'-dihalo-genovinyl)-cyclopropanecarboxylic acid derivatives of the formula VIII is generally carried out at the boiling point of the reaction medium chosen. Reaction -temperatures of ~ between 40 and 120C are particularly suitable.
-~ When 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan~
l-ones of the formula I are converted into 2-(2',2'-dihalogenc-vinyl)-cyclopropanecarbcxylic acid deriva-tlves of the formula VIII, the corresponding 2-(2',2',2'--trihalogenoethyl)-cyclo~
propanecarboxylic acid derivatives of the formula X
~ ' . \C~.`/ ' ' (X) X3~ - CH~ - CH --- ~ CH - COOR
in which R, Rl, R2 and X are as defined, are formed as inter-mediates, These produc-ts can be isola^ted if the reaction tempera-ture is kept below 4oc and/or a less than equivalent - amount of base is used. Above 1~0C, these in-termediates are converted to -the corresponding 2-(2',2'~dihalogenovinyl)-cyclopropanecarboxylic acid der~ivatives of the formula VIII on the addition of further base, with the elimina-tion of HX.
. ~:
The 2-(2',2',2'-trlhalogenoethyl)-cyclopropanecarboxylic acid derivatives of the formula X can also be prepared photo-chemically from 2-(2',2~,2~-trihalogenoethyl)-L~-halogenocyclo-:.
butan-l-ones of the formula I, by irradiation with W light, ; - if necessary with the addition of conventional sensitisers (for example ketones, such as acetone, cyclohexanone, benzo-~,' phenone, acetophenone and higher alkylaryl ketones, thioxan-- thone and the like), in the presence of reagents containing `, hydroxyl groups, which at the same -time can serve as solvents, , Examples of reagents containing hydroxyl groups are alkanols, such as methanol, ethanol and the Iike, and in particular water.
The process according to the invention is illustrated ' ~3~1~4~5 in more detail by the fol.lowin~ eYamples ple ]
a) ~r~ f~ ~ 4l_ ~ tet-ra ~ ;r ~o:d ehloride 452 5 g (5 mols) of acrylic acid chloride (-technical grade purity), 1 5 litres of carbon tetrachloride, 1 5 litres of acetonitrile and 30 g of copper-I chloride are kept at 115C
for 24 hours The reaction r~lix-ture is fil-tered to give a clear filtrate and the latter is evaporated under a waterpump vacuum The residue is distilled This gives 922 g (76% of theory) of 2,4,4,4-te-trachlorobutyric acid chloride;
boiling point 78-80C/ll mm Hg.
IR spectrum (CIIC13) in cm 1 1780 (C=0) NMR spectrum (100 MHz, CDC13) in ppm: 3 16-3 94 (m, 2H, CH2);
4 84-4.96 (m, lH, CH) 2,4,4,4-Tetrachlorobutyric acid chloride can also be prepared as follows:
90 5 g (1 mol) of acrylic acid chloride, 0.5 litre of carbon tetrachloride, 0 2 litre of butyronitrile and 3 g of copper powder are heated at 115C for 20 hours The re-action mixture is filtered, the filtrate is evaporated and -the residue is distilled This gives 167 8 g (69% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride; melting point:
80-81C/12 mm Hg The spectroscopic data are identical -to those of the 2,4,4,4-tetrachlorobutyric acid chloride prepared according to paragraph 1.
If the copper powder is replaced by copper-I chloride and the butyronitrile is replaced by 3-methoxypropionitrile and .
.
-the procedure is o-ther~ise identical, 2,4,4,4-tetrachlorobu-tyric acid chloride is obtained in a yield of 71% of theory 226 g (1 mol~ of 2,4,4,4-tetrachlorobutyric acid [pre-pared in accordance with Israeli Patent Specification 18,771 =
CA, 63, 13089e (1965)], 600 g of -thionyl chloride and 1 ml of N,N-dimethylformamide are warmed at 50C for 2 hours and at 75C
for 2 hours. Af-ter evaporating off the excess -thionyl chloride, the residue is dis-tilled. This gives 227 6 g (930/0 of theory) of 2,4,4,4-te-trachlorobutyric acid chloride;
boiling point 90-91~/15 mm Hg 145.9 g (1.5 mols) of l,l-dichloroethylene, 147 .4 g (1 mol) of dichloroace-tyl chloride, 200 ml of ace-tonitrile and 3 g of copper I chloride are heated at 130C for 8 hours. The reac-tion mixture is evaporated and the residue is subjected to fractional distillation. This gives 2,4,4,4-tetrachloro-butyric acid chloride in the form of a colourless liquid;
boiling point 78~80C/ll mm Hg. The spectroscopic data of the substance obtained are identical to those of the 2,4,4,4-tetrachlorobutyric acid chloride prepared according to paragraph 1.
b) Preparation of 2-chloro-2-(2',2' 2'-trichloroethyl)-3 3-dimeth~lcyclobutan-l-one 280 g of isobutylene are inJec-ted into 122 g (0.5 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 600 ml of cyclo-hexane, in an autoclave. A solution of 51 g (0 5 mol) of triethylamine in 500 ml of cyclohexane is pumped in at 65C in the course of 4 hours. The reaction mixture is then kept ~ 29 .
.44S
a-t 65C for a further 3 hours. The hydrochloride of tri~
ethylarnine, which has precipi-ta-ted, is filtered off and ~he filtrate is evaporated The crystals thus obtained are filtered off This gives 79.4 g (60% of -theory) OL 2-chloro-2~(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutan-1-one with a melting point of 75-76C.
IR spectrum (CHC13) in cm : 1805 (C=0).
spectrum (100 MUIz, CDC13) in ppm: 1.42 and 1.45 (in each case ls, 6H and in each case 1 CH3); 2.91-3.28 (m, 2H, CH2); 3.37-3.76 (m, 2H, CH2).
13C NMR spectrum (CDC13) in ppm: 196 (s, C0); 95.3 (s, CH3);
80~8 (s, C-2); 57.0 (t, CH2); 56.4 (t, CH2); 37.9 (s, C-3);
25 1 (q, CH3); 28.8 (q, CH3).
Elementary analysis for C8HloCl~0 (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%.
c) Prepara-tion of 2-~t2t 2'-trichloroeth~ 3~3-dirneth~1-4=
chlorocycl butan-l-one 132 g (0 5 mol) of the resulting 2-chloro-2-(2',2',2'-trichloroethyl)-3,3-.dimethylcyclobutan~l-one are dissolved in 700 ml of toluene, 1 ml of triethylarnine is added and the mix-ture is boiled under reflux After a reaction -time of 13 hours, a further 1 ml of triethylamine is added and the mix-ture is boiled for a further 7 hours After cooling, the reaction mixture is washed, first with dilute hydrochloric acid and then with water, dried and evaporated The solidified residue (124 g; 94% of theory), which according to thin layer .
chroma-tography is a single compound, is crys-tallised from n-hexane. This gives 105 8 g of 2-(2l,2',2'-trichloro-ethyl)~3,3-dimethyl-4-chlorocycloblltan-1-one; mel-ting point 56-57C.
IR spec-trum (CHC13) in crn 1 1800 (C=0) lH NMR spectrum (100 MHz, CDC13) in ppm: 4.77 (d, J=2 Hz, lH, H on C-4-); 3.47 (m, lH, H on C-2); 2.73-3.26 (rn, 2H, CH2);
2.63 (s, 3H, CH3); 1.14 (s, 3H, CH3) 3C-N~ spectr~n (CDCl~) in ppm: 197 0 (s, C0); 97 8 (s, CC13);
69 4 (d, C-4); 60.6 (d, C-2); 49.5 (t, CH2-CC13); 36.8 (s, C-3); 27.4 (q, CH3); 18 6 (q, C~I3).
Elemen-tary analysis for C8IIloC140 (molecular weight 263.g8):
calcula-ted C 36.40% ~ 3.82% 0 6.02% Cl 53 72%
found C 36 6% H 3 8% 0 6 2% Cl 53 60~o .... ' .
The above compound can also be prepared as follows:
2.64 g (0 01 mol) of 2-chloro~2~(2',2',2'-trichloroe-thyl)-3,3-methylcyclobutanone and 220 mg (0.0008 mol) of te-tra-n-butyl-ammonium chloride are stirred for 6.5 hours at 124C. The cooled melt is boiled vp with hot n-hexane and fil-tered -to give a clear filtrate. As the filtra-te cools, 2.19 g (83% of theory) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutanone with a melting poin-t of 53-56C precipitate.
d) Prepara-tion of 2-(2',2' dichlorovinyl)-3 3-dime-thylcyclo propa~ c~ ylic acid - 13.2 g (0.05 mol) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutan-1-one are added to 150 ml of 10%
strength sodium hydroxide solution and the mixture is stirred intensively. After 5 minutes a clear solution has formed and this is warmed at 100C (bath temperature) for 1 hour.
The reaction solution is wàshed with diethyl e-ther, acidified with concentrated hydrochloric acid, with cooling, and ex-tracted with die-thyl e-ther. The ether phase is washed with water, dried over magnesium sulphate and evaporated.
According to the NMPL spectrum, the solid residue (10.35 g) consists of 80% by weight of cis-2-(2',2'-dichlorovinyl)-3,3-dime-thylcyclopropane-l-carboxylic acid and 20% by weight of trans-2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid. Crystallisation from n-hexane gives the pure cis-acid; mel-ting point 85-87C.
IR spectrum (CHC13) in cm 1 1710 (C0), 1625 (C=C).
NMR spectrum (100 MHz, CDC13/D20) in ppm: 1.30 (s, 6H, 2 x CH3);
1.85 (d, J=8.5 Hz, lH, HC-l); 2.02-2.19 (m, lH, HC-2); 6.17 (d, J=8 Hz, lH, CH=CC12).
Example 2 421 g of propylene, 244 g (1 mol) of 2,4,4,4-tetra-chlorobutyric acid chloride and 1.25 litres of cyclohexane are initially introduced into a 6.3 litre autoclave. A solu-tion of 101 g (1 mol) of triethylamine in 1 litre of cyclo-hexane is pumped in at 50C in the course of 4 hours and the reaction mixture is then kept at 50C for 3 hours. The re-action mixture is filtered and the resulting filtrate is washed with dilute hydrochloric acid and then with water, dried over magnesium sulphate and evaporated. The residue is crystal-lised from n-hexane. This gives 77.2 g of 2-chloro-2-~1.114~S
(2',2',2'-trichloroe-thyl)-3-methylcyclobutan-1-one; melting point 80-81C
IR spectrum (CHC13) in cm 1 1785 (C0).
lH NMR spectrum (100 MHz, C~C13) in ppm: 3.28-3.73 (m, 3H);
2 65-2.95 (m, 2H); 1.43 (d, J=6.5 Hz, 3H, CH~).
13C NMR spectrum (CDC13) in ppm: 196.5 (s, C0); 95.1 (s, CC13);
77.8 (s, C-2); 55.3 (t, CH2-CC13); 50.9 (t, C-4); 38.1 (d, ,, .
C-3); 15.8 (q, CH3).
1 ml of -triethylamine is added to 50 g (0.2 mol) of the resulting 2-chloro-2-(2',2',2'-trichloroethyl)-3-methylcyclo-butan-l-one in 500 ml of toluene and -the mixture is stirred for 18 hours at a bath -tempera-ture of 120C. After cooling, the reaction mixture is fil-tered to give a clear filtrate and the filtrate is washed, first with dilute hydrochloric acid and then with water, boiled up briefly with ac-tive charcoal, fil tered again and evaporated. Distillation of the residue gives 38.7 g (77% of theory) of 2-(2',2',2'-trichloroethyl)-3-methyl-4-chlorocyclobutan-1-one; boiling poin-t 130-131C/
12 mm Hg.
IR spectrum (CHC13) in cm 1 1805 (C0).
MMR spectrum (100 ~z, CDC13) in ppm: 1.20 (d, J=7 Hz, o.6H, CH~); 1.46 (d, J=7 Hz, 0 45H, CH3); 1.66 (d, J=6.5 Hz, 1.95 H, CH3); 2.1-3.5 (m, 4H); 4.55 (dd, J=8 and 2 Hz, 0.65 H, CH);
90 5 g (1 mol) of acrylic acid chloride, 0.5 litre of carbon tetrachloride, 0 2 litre of butyronitrile and 3 g of copper powder are heated at 115C for 20 hours The re-action mixture is filtered, the filtrate is evaporated and -the residue is distilled This gives 167 8 g (69% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride; melting point:
80-81C/12 mm Hg The spectroscopic data are identical -to those of the 2,4,4,4-tetrachlorobutyric acid chloride prepared according to paragraph 1.
If the copper powder is replaced by copper-I chloride and the butyronitrile is replaced by 3-methoxypropionitrile and .
.
-the procedure is o-ther~ise identical, 2,4,4,4-tetrachlorobu-tyric acid chloride is obtained in a yield of 71% of theory 226 g (1 mol~ of 2,4,4,4-tetrachlorobutyric acid [pre-pared in accordance with Israeli Patent Specification 18,771 =
CA, 63, 13089e (1965)], 600 g of -thionyl chloride and 1 ml of N,N-dimethylformamide are warmed at 50C for 2 hours and at 75C
for 2 hours. Af-ter evaporating off the excess -thionyl chloride, the residue is dis-tilled. This gives 227 6 g (930/0 of theory) of 2,4,4,4-te-trachlorobutyric acid chloride;
boiling point 90-91~/15 mm Hg 145.9 g (1.5 mols) of l,l-dichloroethylene, 147 .4 g (1 mol) of dichloroace-tyl chloride, 200 ml of ace-tonitrile and 3 g of copper I chloride are heated at 130C for 8 hours. The reac-tion mixture is evaporated and the residue is subjected to fractional distillation. This gives 2,4,4,4-tetrachloro-butyric acid chloride in the form of a colourless liquid;
boiling point 78~80C/ll mm Hg. The spectroscopic data of the substance obtained are identical to those of the 2,4,4,4-tetrachlorobutyric acid chloride prepared according to paragraph 1.
b) Preparation of 2-chloro-2-(2',2' 2'-trichloroethyl)-3 3-dimeth~lcyclobutan-l-one 280 g of isobutylene are inJec-ted into 122 g (0.5 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 600 ml of cyclo-hexane, in an autoclave. A solution of 51 g (0 5 mol) of triethylamine in 500 ml of cyclohexane is pumped in at 65C in the course of 4 hours. The reaction mixture is then kept ~ 29 .
.44S
a-t 65C for a further 3 hours. The hydrochloride of tri~
ethylarnine, which has precipi-ta-ted, is filtered off and ~he filtrate is evaporated The crystals thus obtained are filtered off This gives 79.4 g (60% of -theory) OL 2-chloro-2~(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutan-1-one with a melting point of 75-76C.
IR spectrum (CHC13) in cm : 1805 (C=0).
spectrum (100 MUIz, CDC13) in ppm: 1.42 and 1.45 (in each case ls, 6H and in each case 1 CH3); 2.91-3.28 (m, 2H, CH2); 3.37-3.76 (m, 2H, CH2).
13C NMR spectrum (CDC13) in ppm: 196 (s, C0); 95.3 (s, CH3);
80~8 (s, C-2); 57.0 (t, CH2); 56.4 (t, CH2); 37.9 (s, C-3);
25 1 (q, CH3); 28.8 (q, CH3).
Elementary analysis for C8HloCl~0 (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%.
c) Prepara-tion of 2-~t2t 2'-trichloroeth~ 3~3-dirneth~1-4=
chlorocycl butan-l-one 132 g (0 5 mol) of the resulting 2-chloro-2-(2',2',2'-trichloroethyl)-3,3-.dimethylcyclobutan~l-one are dissolved in 700 ml of toluene, 1 ml of triethylarnine is added and the mix-ture is boiled under reflux After a reaction -time of 13 hours, a further 1 ml of triethylamine is added and the mix-ture is boiled for a further 7 hours After cooling, the reaction mixture is washed, first with dilute hydrochloric acid and then with water, dried and evaporated The solidified residue (124 g; 94% of theory), which according to thin layer .
chroma-tography is a single compound, is crys-tallised from n-hexane. This gives 105 8 g of 2-(2l,2',2'-trichloro-ethyl)~3,3-dimethyl-4-chlorocycloblltan-1-one; mel-ting point 56-57C.
IR spec-trum (CHC13) in crn 1 1800 (C=0) lH NMR spectrum (100 MHz, CDC13) in ppm: 4.77 (d, J=2 Hz, lH, H on C-4-); 3.47 (m, lH, H on C-2); 2.73-3.26 (rn, 2H, CH2);
2.63 (s, 3H, CH3); 1.14 (s, 3H, CH3) 3C-N~ spectr~n (CDCl~) in ppm: 197 0 (s, C0); 97 8 (s, CC13);
69 4 (d, C-4); 60.6 (d, C-2); 49.5 (t, CH2-CC13); 36.8 (s, C-3); 27.4 (q, CH3); 18 6 (q, C~I3).
Elemen-tary analysis for C8IIloC140 (molecular weight 263.g8):
calcula-ted C 36.40% ~ 3.82% 0 6.02% Cl 53 72%
found C 36 6% H 3 8% 0 6 2% Cl 53 60~o .... ' .
The above compound can also be prepared as follows:
2.64 g (0 01 mol) of 2-chloro~2~(2',2',2'-trichloroe-thyl)-3,3-methylcyclobutanone and 220 mg (0.0008 mol) of te-tra-n-butyl-ammonium chloride are stirred for 6.5 hours at 124C. The cooled melt is boiled vp with hot n-hexane and fil-tered -to give a clear filtrate. As the filtra-te cools, 2.19 g (83% of theory) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutanone with a melting poin-t of 53-56C precipitate.
d) Prepara-tion of 2-(2',2' dichlorovinyl)-3 3-dime-thylcyclo propa~ c~ ylic acid - 13.2 g (0.05 mol) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutan-1-one are added to 150 ml of 10%
strength sodium hydroxide solution and the mixture is stirred intensively. After 5 minutes a clear solution has formed and this is warmed at 100C (bath temperature) for 1 hour.
The reaction solution is wàshed with diethyl e-ther, acidified with concentrated hydrochloric acid, with cooling, and ex-tracted with die-thyl e-ther. The ether phase is washed with water, dried over magnesium sulphate and evaporated.
According to the NMPL spectrum, the solid residue (10.35 g) consists of 80% by weight of cis-2-(2',2'-dichlorovinyl)-3,3-dime-thylcyclopropane-l-carboxylic acid and 20% by weight of trans-2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid. Crystallisation from n-hexane gives the pure cis-acid; mel-ting point 85-87C.
IR spectrum (CHC13) in cm 1 1710 (C0), 1625 (C=C).
NMR spectrum (100 MHz, CDC13/D20) in ppm: 1.30 (s, 6H, 2 x CH3);
1.85 (d, J=8.5 Hz, lH, HC-l); 2.02-2.19 (m, lH, HC-2); 6.17 (d, J=8 Hz, lH, CH=CC12).
Example 2 421 g of propylene, 244 g (1 mol) of 2,4,4,4-tetra-chlorobutyric acid chloride and 1.25 litres of cyclohexane are initially introduced into a 6.3 litre autoclave. A solu-tion of 101 g (1 mol) of triethylamine in 1 litre of cyclo-hexane is pumped in at 50C in the course of 4 hours and the reaction mixture is then kept at 50C for 3 hours. The re-action mixture is filtered and the resulting filtrate is washed with dilute hydrochloric acid and then with water, dried over magnesium sulphate and evaporated. The residue is crystal-lised from n-hexane. This gives 77.2 g of 2-chloro-2-~1.114~S
(2',2',2'-trichloroe-thyl)-3-methylcyclobutan-1-one; melting point 80-81C
IR spectrum (CHC13) in cm 1 1785 (C0).
lH NMR spectrum (100 MHz, C~C13) in ppm: 3.28-3.73 (m, 3H);
2 65-2.95 (m, 2H); 1.43 (d, J=6.5 Hz, 3H, CH~).
13C NMR spectrum (CDC13) in ppm: 196.5 (s, C0); 95.1 (s, CC13);
77.8 (s, C-2); 55.3 (t, CH2-CC13); 50.9 (t, C-4); 38.1 (d, ,, .
C-3); 15.8 (q, CH3).
1 ml of -triethylamine is added to 50 g (0.2 mol) of the resulting 2-chloro-2-(2',2',2'-trichloroethyl)-3-methylcyclo-butan-l-one in 500 ml of toluene and -the mixture is stirred for 18 hours at a bath -tempera-ture of 120C. After cooling, the reaction mixture is fil-tered to give a clear filtrate and the filtrate is washed, first with dilute hydrochloric acid and then with water, boiled up briefly with ac-tive charcoal, fil tered again and evaporated. Distillation of the residue gives 38.7 g (77% of theory) of 2-(2',2',2'-trichloroethyl)-3-methyl-4-chlorocyclobutan-1-one; boiling poin-t 130-131C/
12 mm Hg.
IR spectrum (CHC13) in cm 1 1805 (C0).
MMR spectrum (100 ~z, CDC13) in ppm: 1.20 (d, J=7 Hz, o.6H, CH~); 1.46 (d, J=7 Hz, 0 45H, CH3); 1.66 (d, J=6.5 Hz, 1.95 H, CH3); 2.1-3.5 (m, 4H); 4.55 (dd, J=8 and 2 Hz, 0.65 H, CH);
5,00 (dd, J=9 and 2.5 Hz, 0.15 H, CH); 5.15 (dd, J=9 and 1.5 Hz, 0.2 H, CH).
According to the NMR spectrum and the gas chromatogram, the compound consists of 3 stereoisomers in a weight ratio of , ' .
, ':
13:4:3.
10 5 g of the resul-ting 2-(2',2',2'-trichloroethyl)-3-methyl-4-chlorocyclobutan-1-one are stlrred with 100 ml of 10% strength sodium hydroxide solution for 50 minutes. The solution which has formed is then heated at 100C for 1 hour The reaction mixture is then washed with diethyl ether and carefully acidified wi-tl~ concen~rated hydrochloric acid. I-t is then extracted with diethyl e-ther The ether extract is , .
washed with water, dried over magnesium su]phate and evapora-ted This gives 2-(2',2'-dichlorovinyl)-3-methylcyclopropane-1-carboxylic acid; mel-ting point 75-78C (recrystallised from n-hexane).
IR spectrum (KBr) in cm 1 16~5 (C=O), 1625 (C=C).
NMR spectrum (100 MHz, CDC13/D20) in ppm: 1.25 (d, J=5 5 Hz, 3H, CH3); 1 54-2 18 (m, 3H); 3.96 (d, J--8 Hz, lH, CH-CC12) _~e~
A solution of 25.3 g (0.25 mol) of triethylamine in 50 ml of n-hexane is added dropwise, in the course of 7 hours, with stirring, to a solu-tion, which is kept under reflux, of 25 g (0 37 mol) of methylenecyclobutane and 61.1 g (0 25 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 200 ml of n-hexane, After the reaction mixture has been stirred under reflux for a fur-ther 2 hours, it is freed, whilst still hot, from the ammonium salt formed, by filtration. The filtra-te is concentrated to about 1/3rd its ~olu~.e. On cooling, l-chloro-1-(2',2',2'-trichloroethyl)-spiro[3.3]hep-tan-2-one of the formula - 3~ -., ~ , o ,;. i' L ~ c7l2cc~3 ~;~ c~
pre-ipi-ta-tes in a crys-talline form; mel-ting point 93-94C, IR spectrum (CC1L~) in crn 1 1790 (C-0), NMR spectrum (100 MHz, CDC13) in ppm: 1,70-2,~0 (m, 6H);
3,15-3,60 (m, 4H), A solution of 27,6 g (0,1 mol) of the resulting 1-chloro-1-(2',2',2'-trichloroethyl)spiroC3,3]heptan-2-one in 100 ml of toluene, toge-ther wi-th 0,93 g (5 mmols) of tributyl-amine, is refluxed for 9 hours, The reaction mixture is then evaporated and the residue is distilled in vacuo, This gives l-chloro-3-(2',2',2'~-trichloroe-thyl)spiro[3,3]heptan-2-one of the formula . '~/ . .
Cl C1~2CCl~
,,, ' .
; in the form of a slightly yellowish oil; boiling point 85-90C/
0,005 mm Hg; n20 = 1,5242, IR spectrum (film) in cm 1 1795 (C=0), NMR spectrum (100 I~Iz, CDC13) in ppm: 1,80-3,85 (m, ~H); 4,68, ` 4,93 (each one d, -together 1 H), 11,0 g (40 mmols) of the resul-ting 1-chloro-3-(2',2',2'-- trichloroethyl)spiro[3,3]heptan-2-one are stirred together with _ ~5 _ ::
. ' ''.
:
95 ml (about 240 rnrnols) of 10% strength sodiurn hydroxide solu-tion lor 6 hours at 95C, ~fter cooling, -the rrlixture is washed ~rith several porti.o~s of diethyl e-ther, acidified with sulphuric acid and extracted wi-th diethyl e-ther, . The ether extracts are evapora-ted after drying over sodium sulphate, A small amount of strongly polar impurities is eliminated by filtering the residue from ten times the arnount by ~eight ol sili.ca gel (eluan-t n-hexane/diethyl e-ther in a volurne ra-tio of 1:1), After concen-trating the fil.tra-te, 2-(2',2'-dichloro-vinyl)spiro[2.3]hexane-1-carboxylic acid o:E -the formula ~' ' Y
C1~
is obtained in -the form of a 2:1 cis/trans mixture; melting point 121-28C, IR spectrum (CC14) in cm 1 1705 (C=0).
NMR spectrurn (100 MHz, CDC13) in ppm: 1.60-2.60 (rn, 8H); 5.34, 5.g7 (each one d, together lH); 11.80-11.50 (broad s, lH).
Example 4 280 g of isobutylene are injec-ted into 122 g (0.5 mol) of 2,4,4,4-tetrachlorobu-tyric acid chloride in 600.ml of cyclo-hexane, in an autoclave. 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane are pumped in a-t 65C in the course of 4 hours. The reaction mixture is then kep-t at 65C for 3 hours and ~hen heated a-t 125C for 18 hours. During this time, 2.0 g of triethylamine in 50 ml of cycl.ohexane are -. 3~ _ . . ~.
, pumped in every 3 hours. I'he reaction mix-tu-re is poured on-to ice, acidified with hydrochloric ac1d and ex-tr~cted with cyclohexane. The evaporated ex-trac-t is fil-tered in tolucne/
cyclohexane (1:1 mixture by voll~e) through 1 kg of silica gel ..: .., in order to remove s-trongly polar impurities. The filtrate is evaporated and the residue is crystallised from n-hexane.
This gives 31.8 g of 2-(2',2',2'~-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutan~l-one; melting point 56-57C.
Example 5 a) 26.1 g (9g mmols) of 2 (2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutanone are added to 260 ml of a 10%
streng-th sodium hydroxide solution, at 11C, with stirring.
The temperature rises to 28C in the course of 2.L~ hours ano then falls to 20C in the course of a further 2 hours. The reaction mixture is diluted with 200 ml of water, washed wi-th die-thyl ether, rendered strongly acid wi-th concen-trated hydro-chloric acid and extracted with die-thyl ether. The extract is washed with water, dried over magnesium sulphate and evapora-ted. This gives 24.3 g (100~ of theory) of a pale yellow residue (melting point 80-81C), which consists exclusively of cis- and trans-2-(2',2l,2'-trichloroethyl)-3,3-dimethylcyclo-propanecarboxylic acid. The mixture can be separated into the pure cis and trans compounds by fractional crystallisa-tion or by column chromatography.
NMR spectrum (100 MHz, CDC13/D20) in ppm: 2.75-3.33 (m, 2E-I);
1.50 1.97 (m, 2H); 1.32 (s, 2 x CH3 cis); 1 27 and 1.38 (2 x s, 2 x CH3 trans).
,, .
~ 37 ~
; ' ' . :
L4~5 b) 8 0 g (30 3 mmols) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclohu-tarlone in L~oo ml of acetone and 100 ml -` of water are irradia-ted., through pyrex glass, with a Philipps HPK 125 watt lamp unti.l no further s-tarting material can be detec-ted by chromatography. The reac-tion mixture is evaporated and the residue is worked up to -the acid as indicated under a) This gives 6.95 g (93% of -theory) of a cis/
trans mixture of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-~: cyclopropanecarboxylic acid, the spectroscopic data of which are iden-tical to -those of -the mixture ob-tained according -to a) c) 24.55 g (0 1 mol) of 2-(2',2',2'-trichloroethyl)-3,3-dime-thylcyclopropanecarboxylic acid are suspended in 350 ml of 10% streng-th sodilml hydroxide solu-tion and the suspension is stirred for 4 5 hours at a bath temperature of 100C. The reaction solution is washed with die-thyl ether, acidified with hydrochloric acid and extrac-ted with chloroform The .. extrac-t is washed with water, dried over magnesium sulph~te and : evaporated After crystallisation from n-hexane, 17 55 g . . (84% of theory) of colourless 2-(2',2'-dichlorovinyl)-3,3-dime-thylcyclopropanecarboxylic acid are obtai.ned Exarnple 6 v 145 g (0 5 mol) of 2-bromo-4,4,4-trichlorobutyric acid ~`~ chloride, 280 g (5 mols) of isobutylene and 600 ml of cyclo-~: hexane are initially introduced into an autoclave 51 g (0 5 rnol) of triethylamine in 500 ml of cyclohexane are pumped in at 65C in the course of 4 hours The mixture is then stirred for a fur-ther 3 hours at this temperature The - ~8 -~ ' ' ' ' : ~
' 4~5 , '. ' '?
reaction rnj~ture is fil-tered The filtra-te is evaporated and -the residue is crys-tallised :~rorn n--hexane This gives 74 5 g (48nj~ Of -theory) o:~ 2-bromo 2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobu-tanone in -the form of a light beige powder;
melting poin-t 46-49C.
IR spectru~ (CHC13) in cm 1 1885 (C0).
H ~ ~ spectr~rn (100 ~z, pyridine-d5) in ppm: 3.79 (AB, 2H, CH2); 3 10 (l)B, 2H, CH2); 1 37 and 1 42 (ls in each case, total 6H, CII3 in each case).
13C NMR spec-trum (CDC13) in ppm: 196.8 (C0); 95 6 (CC13);
74 8 (C-2); 56.5 and 56.3 (CH2 in each case); 38.0 (C-3);
27.4 and 24.7 (CH3 in each case).
20 g (0.065 mol) of 2-bromo~2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutanone and 5 g of tetrabu-tyla~monium bromide are stirred for 30 minutes at 80C and for 10 minu~tes a-t 100C.
The solidified mel-t is chromatographed on silica gel (elution with toluene/cyclohexane, 1:1). 2 (2',2',2'-Trichloroethyl)-3,3-dimethyl-4-bromocyclobutanone, which crystallises on stand-ing, is obtained in this way: melting point 56C.
lH NMR spectrum (100 MHz, CDC13) in ppm: 4.99 (d, J=2Hz, lH, H on C-4); 3.58 (X moiety of ABX, addi-tionally resolved with .:
; J=2Hz, lH, H on C-2); 3.05 (AB moiety of ABX, 2H, CH2); 1.22 ;~ and 2.67 (ls in each case, 3H in each case, CH3 in each case).
, 13C NMR spectrum (CDC13) in ppm: 196.7 (s, C0); 97.7 (s, CC13);
60.7 (d, C-2); 59.8 (d, C-4); 50.0 (-t, CH2-CC13); 36.4 (s, C-3); 27.6 (q, CH3); 21.0 (q, CH3).
A solution of 3.2 g of NaO~ in 70 ml of water is added ,...
. - 3~ -"' , ' ~ ' " . ' ' :;' . , s to 3.1 g (10 6 mmols) of 2-(2',2',2'~trichloroethyl)-3,3-dimethyl-4-brGmocyclobutanone and -the mixture is s-tirred for 2 hours. I-t is then stirred for a further 3 hours a-t 100C.
The reaction rnixture is washed with die-thyl ether and acidified with dilute hydrochloric acid. This aqueous phase is ex--tracted wi-th diethyl ether. The extrac-t i~ washed with water, dried over magnesium sulphate and evaporated. The residue is crystallised from n-hexane. This gives 2.55 g of cis-2-(2',2'-dichlorovinyl)-3,3-dimethylcyc~opropanecarboxylic acid; melting poin-t 86C.
IR spectrum (CH~l~) in cm 1 1710 (C0), 1625 (C=C).
NMR spectrum (100 ~-Iz, CDC13/D20) in ppm: 1.30 (s, 6H, 2 x CH3); 1.85 (d, J=8.5 Hz, lH, HC-1); 2.02-2.19 (m, lH, HC-2);
According to the NMR spectrum and the gas chromatogram, the compound consists of 3 stereoisomers in a weight ratio of , ' .
, ':
13:4:3.
10 5 g of the resul-ting 2-(2',2',2'-trichloroethyl)-3-methyl-4-chlorocyclobutan-1-one are stlrred with 100 ml of 10% strength sodium hydroxide solution for 50 minutes. The solution which has formed is then heated at 100C for 1 hour The reaction mixture is then washed with diethyl ether and carefully acidified wi-tl~ concen~rated hydrochloric acid. I-t is then extracted with diethyl e-ther The ether extract is , .
washed with water, dried over magnesium su]phate and evapora-ted This gives 2-(2',2'-dichlorovinyl)-3-methylcyclopropane-1-carboxylic acid; mel-ting point 75-78C (recrystallised from n-hexane).
IR spectrum (KBr) in cm 1 16~5 (C=O), 1625 (C=C).
NMR spectrum (100 MHz, CDC13/D20) in ppm: 1.25 (d, J=5 5 Hz, 3H, CH3); 1 54-2 18 (m, 3H); 3.96 (d, J--8 Hz, lH, CH-CC12) _~e~
A solution of 25.3 g (0.25 mol) of triethylamine in 50 ml of n-hexane is added dropwise, in the course of 7 hours, with stirring, to a solu-tion, which is kept under reflux, of 25 g (0 37 mol) of methylenecyclobutane and 61.1 g (0 25 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 200 ml of n-hexane, After the reaction mixture has been stirred under reflux for a fur-ther 2 hours, it is freed, whilst still hot, from the ammonium salt formed, by filtration. The filtra-te is concentrated to about 1/3rd its ~olu~.e. On cooling, l-chloro-1-(2',2',2'-trichloroethyl)-spiro[3.3]hep-tan-2-one of the formula - 3~ -., ~ , o ,;. i' L ~ c7l2cc~3 ~;~ c~
pre-ipi-ta-tes in a crys-talline form; mel-ting point 93-94C, IR spectrum (CC1L~) in crn 1 1790 (C-0), NMR spectrum (100 MHz, CDC13) in ppm: 1,70-2,~0 (m, 6H);
3,15-3,60 (m, 4H), A solution of 27,6 g (0,1 mol) of the resulting 1-chloro-1-(2',2',2'-trichloroethyl)spiroC3,3]heptan-2-one in 100 ml of toluene, toge-ther wi-th 0,93 g (5 mmols) of tributyl-amine, is refluxed for 9 hours, The reaction mixture is then evaporated and the residue is distilled in vacuo, This gives l-chloro-3-(2',2',2'~-trichloroe-thyl)spiro[3,3]heptan-2-one of the formula . '~/ . .
Cl C1~2CCl~
,,, ' .
; in the form of a slightly yellowish oil; boiling point 85-90C/
0,005 mm Hg; n20 = 1,5242, IR spectrum (film) in cm 1 1795 (C=0), NMR spectrum (100 I~Iz, CDC13) in ppm: 1,80-3,85 (m, ~H); 4,68, ` 4,93 (each one d, -together 1 H), 11,0 g (40 mmols) of the resul-ting 1-chloro-3-(2',2',2'-- trichloroethyl)spiro[3,3]heptan-2-one are stirred together with _ ~5 _ ::
. ' ''.
:
95 ml (about 240 rnrnols) of 10% strength sodiurn hydroxide solu-tion lor 6 hours at 95C, ~fter cooling, -the rrlixture is washed ~rith several porti.o~s of diethyl e-ther, acidified with sulphuric acid and extracted wi-th diethyl e-ther, . The ether extracts are evapora-ted after drying over sodium sulphate, A small amount of strongly polar impurities is eliminated by filtering the residue from ten times the arnount by ~eight ol sili.ca gel (eluan-t n-hexane/diethyl e-ther in a volurne ra-tio of 1:1), After concen-trating the fil.tra-te, 2-(2',2'-dichloro-vinyl)spiro[2.3]hexane-1-carboxylic acid o:E -the formula ~' ' Y
C1~
is obtained in -the form of a 2:1 cis/trans mixture; melting point 121-28C, IR spectrum (CC14) in cm 1 1705 (C=0).
NMR spectrurn (100 MHz, CDC13) in ppm: 1.60-2.60 (rn, 8H); 5.34, 5.g7 (each one d, together lH); 11.80-11.50 (broad s, lH).
Example 4 280 g of isobutylene are injec-ted into 122 g (0.5 mol) of 2,4,4,4-tetrachlorobu-tyric acid chloride in 600.ml of cyclo-hexane, in an autoclave. 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane are pumped in a-t 65C in the course of 4 hours. The reaction mixture is then kep-t at 65C for 3 hours and ~hen heated a-t 125C for 18 hours. During this time, 2.0 g of triethylamine in 50 ml of cycl.ohexane are -. 3~ _ . . ~.
, pumped in every 3 hours. I'he reaction mix-tu-re is poured on-to ice, acidified with hydrochloric ac1d and ex-tr~cted with cyclohexane. The evaporated ex-trac-t is fil-tered in tolucne/
cyclohexane (1:1 mixture by voll~e) through 1 kg of silica gel ..: .., in order to remove s-trongly polar impurities. The filtrate is evaporated and the residue is crystallised from n-hexane.
This gives 31.8 g of 2-(2',2',2'~-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutan~l-one; melting point 56-57C.
Example 5 a) 26.1 g (9g mmols) of 2 (2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutanone are added to 260 ml of a 10%
streng-th sodium hydroxide solution, at 11C, with stirring.
The temperature rises to 28C in the course of 2.L~ hours ano then falls to 20C in the course of a further 2 hours. The reaction mixture is diluted with 200 ml of water, washed wi-th die-thyl ether, rendered strongly acid wi-th concen-trated hydro-chloric acid and extracted with die-thyl ether. The extract is washed with water, dried over magnesium sulphate and evapora-ted. This gives 24.3 g (100~ of theory) of a pale yellow residue (melting point 80-81C), which consists exclusively of cis- and trans-2-(2',2l,2'-trichloroethyl)-3,3-dimethylcyclo-propanecarboxylic acid. The mixture can be separated into the pure cis and trans compounds by fractional crystallisa-tion or by column chromatography.
NMR spectrum (100 MHz, CDC13/D20) in ppm: 2.75-3.33 (m, 2E-I);
1.50 1.97 (m, 2H); 1.32 (s, 2 x CH3 cis); 1 27 and 1.38 (2 x s, 2 x CH3 trans).
,, .
~ 37 ~
; ' ' . :
L4~5 b) 8 0 g (30 3 mmols) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclohu-tarlone in L~oo ml of acetone and 100 ml -` of water are irradia-ted., through pyrex glass, with a Philipps HPK 125 watt lamp unti.l no further s-tarting material can be detec-ted by chromatography. The reac-tion mixture is evaporated and the residue is worked up to -the acid as indicated under a) This gives 6.95 g (93% of -theory) of a cis/
trans mixture of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-~: cyclopropanecarboxylic acid, the spectroscopic data of which are iden-tical to -those of -the mixture ob-tained according -to a) c) 24.55 g (0 1 mol) of 2-(2',2',2'-trichloroethyl)-3,3-dime-thylcyclopropanecarboxylic acid are suspended in 350 ml of 10% streng-th sodilml hydroxide solu-tion and the suspension is stirred for 4 5 hours at a bath temperature of 100C. The reaction solution is washed with die-thyl ether, acidified with hydrochloric acid and extrac-ted with chloroform The .. extrac-t is washed with water, dried over magnesium sulph~te and : evaporated After crystallisation from n-hexane, 17 55 g . . (84% of theory) of colourless 2-(2',2'-dichlorovinyl)-3,3-dime-thylcyclopropanecarboxylic acid are obtai.ned Exarnple 6 v 145 g (0 5 mol) of 2-bromo-4,4,4-trichlorobutyric acid ~`~ chloride, 280 g (5 mols) of isobutylene and 600 ml of cyclo-~: hexane are initially introduced into an autoclave 51 g (0 5 rnol) of triethylamine in 500 ml of cyclohexane are pumped in at 65C in the course of 4 hours The mixture is then stirred for a fur-ther 3 hours at this temperature The - ~8 -~ ' ' ' ' : ~
' 4~5 , '. ' '?
reaction rnj~ture is fil-tered The filtra-te is evaporated and -the residue is crys-tallised :~rorn n--hexane This gives 74 5 g (48nj~ Of -theory) o:~ 2-bromo 2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobu-tanone in -the form of a light beige powder;
melting poin-t 46-49C.
IR spectru~ (CHC13) in cm 1 1885 (C0).
H ~ ~ spectr~rn (100 ~z, pyridine-d5) in ppm: 3.79 (AB, 2H, CH2); 3 10 (l)B, 2H, CH2); 1 37 and 1 42 (ls in each case, total 6H, CII3 in each case).
13C NMR spec-trum (CDC13) in ppm: 196.8 (C0); 95 6 (CC13);
74 8 (C-2); 56.5 and 56.3 (CH2 in each case); 38.0 (C-3);
27.4 and 24.7 (CH3 in each case).
20 g (0.065 mol) of 2-bromo~2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutanone and 5 g of tetrabu-tyla~monium bromide are stirred for 30 minutes at 80C and for 10 minu~tes a-t 100C.
The solidified mel-t is chromatographed on silica gel (elution with toluene/cyclohexane, 1:1). 2 (2',2',2'-Trichloroethyl)-3,3-dimethyl-4-bromocyclobutanone, which crystallises on stand-ing, is obtained in this way: melting point 56C.
lH NMR spectrum (100 MHz, CDC13) in ppm: 4.99 (d, J=2Hz, lH, H on C-4); 3.58 (X moiety of ABX, addi-tionally resolved with .:
; J=2Hz, lH, H on C-2); 3.05 (AB moiety of ABX, 2H, CH2); 1.22 ;~ and 2.67 (ls in each case, 3H in each case, CH3 in each case).
, 13C NMR spectrum (CDC13) in ppm: 196.7 (s, C0); 97.7 (s, CC13);
60.7 (d, C-2); 59.8 (d, C-4); 50.0 (-t, CH2-CC13); 36.4 (s, C-3); 27.6 (q, CH3); 21.0 (q, CH3).
A solution of 3.2 g of NaO~ in 70 ml of water is added ,...
. - 3~ -"' , ' ~ ' " . ' ' :;' . , s to 3.1 g (10 6 mmols) of 2-(2',2',2'~trichloroethyl)-3,3-dimethyl-4-brGmocyclobutanone and -the mixture is s-tirred for 2 hours. I-t is then stirred for a further 3 hours a-t 100C.
The reaction rnixture is washed with die-thyl ether and acidified with dilute hydrochloric acid. This aqueous phase is ex--tracted wi-th diethyl ether. The extrac-t i~ washed with water, dried over magnesium sulphate and evaporated. The residue is crystallised from n-hexane. This gives 2.55 g of cis-2-(2',2'-dichlorovinyl)-3,3-dimethylcyc~opropanecarboxylic acid; melting poin-t 86C.
IR spectrum (CH~l~) in cm 1 1710 (C0), 1625 (C=C).
NMR spectrum (100 ~-Iz, CDC13/D20) in ppm: 1.30 (s, 6H, 2 x CH3); 1.85 (d, J=8.5 Hz, lH, HC-1); 2.02-2.19 (m, lH, HC-2);
6.17 (d, J=8 Hz, lH, CH=CC12).
~xam~le 7 ._ 90 5 g (1 mol) of acrylic acid chloride, 364.8 g (1.1 ` mol) of carbon tetrabromide, 200 ml of acetonitrile and 5.0 g of copper-I chloride are hea-ted at 115C for 6 hours After cooling, the reaction mixture is distilled direct. This - gives 136.6 g (33% of theory) of 2,4,4,4-tetrabromobutyric acid chloride; boiling point 135-140C, 12 mm Hg.
350 ml of cyclohexane are saturated with isobutylene . . .
at room tempera-ture (20-25C). 42.2 g (0.1 mol) of 2,4,4,4-tetrabromobutyric acid chloride are dissolved therein.
10.1 g (0.1 mol) of triethylamine-in 50 ml of cyclohexane are then added dropwise at room temperature in -the course of 2 hours, with stirring and under a gentle stream of isobu~tylene. The '' - 1~o --, ~
' ' .445 resul-ting reac-tion rni~.ture is stirred for 3 hol~rs and ~ater is then added. I'he o~ganic layer is separa-ted off, washed with water, dried ovèr ma,,rnesiurn su]pha-te and evapora-ted.
The residue is fil-tered through silica gel (eluant: cyclohex-ane/toluene, 1:1 mixture by volume). The filtrate is evaporated. The residue is crystallised from n-hexane.
2-Brorno-2-(2',2',2l-tribromoethyl)-3,3-dimethy].cyclo-butanone is obtained; melting point 61-63C.
IR Spec-trum (CHC13) in cm 1 1780 (C0).
H NMR spectrurn (100 ~-Iz, CDC13) in ppm: 3.97 (AB, 2H, CH2);
3.13 (AB, 2H, CH2); 1.51 and 1.61 (ls in each case, 3H in each case, CII3 in each case).
3C NMR spectrum (CDC13) in ppm: 196.7 (C0); 76.8 (C~2);
60.0 and 56.6 (CI-I2 in each case); 38.1 (C~3); 31.7 (CBr3);
27.7 and 25.0 (CH3 in each case).
9.6 g (21.8 mmols) of 2~bromo-2-(2',2l,2l-tribromo-ethyl)-3,3-dimethylcyclobutanone and 2 0 g of tetrabutylammoniurn bromide are stirred at 90C for 30 minutes. The cooled melt .
is chromatographed on silica gel (elution wi-th toluene/cyclo~
.- hexane, 1:1). This gives 2-(2l,2l,2l--tribromoethyl)-3,3-s dimethyl-4-bromocyclobutanone in the form of an oil which ;~ crys-tallises slowly and which is recrystallised from diethyl ether/n-hexane; melting point 91-93C.
IR spectrum (CHC13) in cm 1 1795 (C0).
~`~ lH NMR spectrum (100 MHz, CDC13) in ppm: 4.96 (d, J=2Hz, lH, ;.,-H on C-4); 3.12-3.67 (ABX, the X moiety addi~tionally being resolved wi-th J=2Hz, 3H, CH2-CH); 1.18 and 1.67 (ls in each .44S
case, ~,T in each case, ~i3 ln each case).
3C ~TI~ spectrum (CDC13) 195.4 (s, CO); 63.2 (d, C-2);
59.9 (d, C-4); 54.6 (t, CH2); 38.4 (s, CBr3); 36.4 (s, C-3);
27 8 and 21.3 (q in each case, CH3 in each case).
700 mg (1.56 mmols) of 2--(2',2',2'-tribrornoethyl)-3,3-dirnethyl-4-bromocyclobutanone are stirred wi-th a solu-tion of 190 mg of l~iaOH in 5 ml of wa-ter, -to which 0.5 ml of dioxane has been added, for 2 hours at room temperature The mixture is then stirred for 1 hour at 80C The clear solution is worked up to the acid in the customary way. 4-10 mg (88~' of theory) of cls-2-(2',2'-dibromovinyl)-3,3-dimethylcyclo-propanecarboxylic acid are ob-tained IR spectrum (CHC13) in cm 1 1695 (CO) NMP. spectrum (100 ~-Iz, CDC13/D20)in ppm: 6.70 (6d, J--8Hz, lH, CH--CBr2); 1.82-2.14 (m, 2H); 1 30 and 1 33 (ls in each case, .:
to-tal 6H, CH3 in each case) Example 8 10 1 g (0 1 mo]) of triethylamine in 100 ml of cyclo-hexane are added dropwise in -the course of 2 hours, a-t 65C, to a solution of 14 g (0 17 mol) of methylenecyclopen-tane and 26 4 g (0 1 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 220 ml of cyclohexane, with stirring The mixture is then stirred at this temperature for a further 3 hours The reaction mixture is washed with dilute hydrochloric acid and then with water, dried over magneslum sulphate and evaporated The residue is crystallised from n-hexane~ This gives 16.6 g of 1-chloro-1--(2',2',2'-trichloroethyl)spiro[3 4]octan-_ 42 -'' ' ' : ~
,:
: ~
2-one of the formula ~` ~ CII~CC13 ; mel-ting poin-t 70~73C.
.
IR spectrum (CHC13) in cm 1 17~5 (C0) NMR spectrum (100 MHz, CDC13) in ppm: 1 60 2 30 (m, 8H); 3 08 (AB, 2H, CH2)j 3.60 (AB, 2H, CH2).
12 0 g (0 041 mo]) of 1-chloro-1~(2',2',2'~trichloro-ethyl)spiro[3.4]octan~2~one are s-tirred with 3 6 g of tetra~
bu-tylammonium chloride at a ba-th temperature of 125C Af-ter 1 5 hours, the reaction mixture is chromatographed on silica gel (elution wi-th toluene/cyclohexane, 1:1) 9.7 g (81% of theory) of l-chloro-3-(2',2',2'-trichloroethyl)spiro[3 4]oc-tan~
2-one of -the formula ."",.,, - r\ -Cl~2CCl3 ,.-'' \~ ' -, . ~ .
..... . .
are ob-tained in this way in the form of a colourless oil IR spec-trum (CHC13) in cm 1 1800 (C0) NMR spectrum (100 MHz, CDC13) in ppm: 4.87 (d, J=2Hz, lH, CHCl); 3.70 (X moiety of ABX, additionally resolved with J=2Hz, lH, CH): 2.73-3.29 (AB moiety of ABX, 2H, CH2); 1.45-2.23 (m, 8H).
4.83 g (16.6 mmols) of 1-chloro-3-(2',2',2'-trichloro-. 43 ethyl)spiro[3.4~octan-2-one are added to a solution of 2,0 g of NaOH in 40 rnl of ~la-ter and 3 ml of dioxane and the mixture is stirred for 2 hours at room -tempera-ture and then for 3 hours at 100C. The reaction solution is washed with diethyl ether and acidified with dilute hydrochlorlc acid. The acid solu-tion is extracted with die-thyl e-t~;er. The extracts are washed with wa-ter, dried over magnesium sulphate and evapora-ted, The residue is crys~tallised from n-hexane.
This gives 3.3 g of 2~(2',2'-dichlorovinyl)spiro[2.4]heptane-arboxylic acid of the formula ~
Cl~ ~
C-CI~ COOII
in the form of a whi-te po~der; mel-ting poin-t 90-105C.
IR spectrum (CHC13) in cm 1 1705 (CO), 1620 (C=C).
NMR spectrum (100 MHz, CDC13/D20) in ppm: 6.15 (d, J=9Hz, 0.8H, CH=CC13cis); 5.51 (d, J=9Hz, 0.2H, CH=CC12 -trans); 2.00-2.40 (m, 2H); 1.60-1.95 tm, 8H).
Example 9 33,6 g (0.62 mol) of methylenecyclopropane and 152 g (0.62 mol) of 2,4,4,4-tetrachlorobu-tyric acid chloride in 620 ml of n-pentane are initially introdvced into a 2,5 litre autoclave, 62.8 g (0.62 mol) of triethylamine in 120 m]
of n-pentane are pumped in in the course of 6 hours, at 60C, and the reaction mixture is then kep-t at 60C for 6 hours.
The reaction mixture is filtered, -the f'iltrate is evaporated ,:
:
i and -the residue is distilled in vacuo The fraction ha.virAg a boiling range of 45-80C/0 09 mm ~Ig is then chromatographed on - 250 g of silica gel using hexane/0-50/0 by weight -toluene.
The pure fracticns are evaporated and the residue is distilled.
This gives l-chloro-1-(2',2',2'--trichloroe-thyl)spiro[3.2]hexan-2-one of -the formula . . .
. ~frC~l~,CC13 .. C~i.
having a boiling point of 70-71C/0.08 mm Hg.
~; `
IR spec-trurn (CHC13) in cm 1 1776 (C0).
H NMR spec-trum (lOOM~Iz CDC13) in pprn: 0.8-1.8 (m, 4H);
2.6-3.8 (m, 4H).
A solution of 11 0 g (42 mmols) of 1 chloro-1-(2',2',2'--trichloroethyl)spiro[3 2]hexan-2-one and 1.17 g (6.3 mrnols) of tributylamine in 15 ml of toluene is refluxed for 5 hours.
A~ter cooling, the reaction mixture is dilu-ted wi-th n-pentane.
The mixture is washed with 2 N sulphuric acid and then with saturated sodium chloride solution, dried over sodium sulphate and evaporated. The residue is distilled in vacuo.
This gives l-chloro-3-(2',2',2'-trichloroe-thyl~spiro[3.2]hexan-2-one of the formula ., .
C~c~l2ccl3 - having a boiling point of 60C/0.01 mm Hg.
.'; . .
, .
`~ 4~5 IR spec-trum (CC14) in c~ 1 1780 (CO).
N~ spectrurn (100 ~!r~lz ~ CDCl~) :in ppm: 0 8-1.7 (m, 4H); 2.6-4.2 (m, 3H); 4,75, 5.15 (one d in each case; together lH)
~xam~le 7 ._ 90 5 g (1 mol) of acrylic acid chloride, 364.8 g (1.1 ` mol) of carbon tetrabromide, 200 ml of acetonitrile and 5.0 g of copper-I chloride are hea-ted at 115C for 6 hours After cooling, the reaction mixture is distilled direct. This - gives 136.6 g (33% of theory) of 2,4,4,4-tetrabromobutyric acid chloride; boiling point 135-140C, 12 mm Hg.
350 ml of cyclohexane are saturated with isobutylene . . .
at room tempera-ture (20-25C). 42.2 g (0.1 mol) of 2,4,4,4-tetrabromobutyric acid chloride are dissolved therein.
10.1 g (0.1 mol) of triethylamine-in 50 ml of cyclohexane are then added dropwise at room temperature in -the course of 2 hours, with stirring and under a gentle stream of isobu~tylene. The '' - 1~o --, ~
' ' .445 resul-ting reac-tion rni~.ture is stirred for 3 hol~rs and ~ater is then added. I'he o~ganic layer is separa-ted off, washed with water, dried ovèr ma,,rnesiurn su]pha-te and evapora-ted.
The residue is fil-tered through silica gel (eluant: cyclohex-ane/toluene, 1:1 mixture by volume). The filtrate is evaporated. The residue is crystallised from n-hexane.
2-Brorno-2-(2',2',2l-tribromoethyl)-3,3-dimethy].cyclo-butanone is obtained; melting point 61-63C.
IR Spec-trum (CHC13) in cm 1 1780 (C0).
H NMR spectrurn (100 ~-Iz, CDC13) in ppm: 3.97 (AB, 2H, CH2);
3.13 (AB, 2H, CH2); 1.51 and 1.61 (ls in each case, 3H in each case, CII3 in each case).
3C NMR spectrum (CDC13) in ppm: 196.7 (C0); 76.8 (C~2);
60.0 and 56.6 (CI-I2 in each case); 38.1 (C~3); 31.7 (CBr3);
27.7 and 25.0 (CH3 in each case).
9.6 g (21.8 mmols) of 2~bromo-2-(2',2l,2l-tribromo-ethyl)-3,3-dimethylcyclobutanone and 2 0 g of tetrabutylammoniurn bromide are stirred at 90C for 30 minutes. The cooled melt .
is chromatographed on silica gel (elution wi-th toluene/cyclo~
.- hexane, 1:1). This gives 2-(2l,2l,2l--tribromoethyl)-3,3-s dimethyl-4-bromocyclobutanone in the form of an oil which ;~ crys-tallises slowly and which is recrystallised from diethyl ether/n-hexane; melting point 91-93C.
IR spectrum (CHC13) in cm 1 1795 (C0).
~`~ lH NMR spectrum (100 MHz, CDC13) in ppm: 4.96 (d, J=2Hz, lH, ;.,-H on C-4); 3.12-3.67 (ABX, the X moiety addi~tionally being resolved wi-th J=2Hz, 3H, CH2-CH); 1.18 and 1.67 (ls in each .44S
case, ~,T in each case, ~i3 ln each case).
3C ~TI~ spectrum (CDC13) 195.4 (s, CO); 63.2 (d, C-2);
59.9 (d, C-4); 54.6 (t, CH2); 38.4 (s, CBr3); 36.4 (s, C-3);
27 8 and 21.3 (q in each case, CH3 in each case).
700 mg (1.56 mmols) of 2--(2',2',2'-tribrornoethyl)-3,3-dirnethyl-4-bromocyclobutanone are stirred wi-th a solu-tion of 190 mg of l~iaOH in 5 ml of wa-ter, -to which 0.5 ml of dioxane has been added, for 2 hours at room temperature The mixture is then stirred for 1 hour at 80C The clear solution is worked up to the acid in the customary way. 4-10 mg (88~' of theory) of cls-2-(2',2'-dibromovinyl)-3,3-dimethylcyclo-propanecarboxylic acid are ob-tained IR spectrum (CHC13) in cm 1 1695 (CO) NMP. spectrum (100 ~-Iz, CDC13/D20)in ppm: 6.70 (6d, J--8Hz, lH, CH--CBr2); 1.82-2.14 (m, 2H); 1 30 and 1 33 (ls in each case, .:
to-tal 6H, CH3 in each case) Example 8 10 1 g (0 1 mo]) of triethylamine in 100 ml of cyclo-hexane are added dropwise in -the course of 2 hours, a-t 65C, to a solution of 14 g (0 17 mol) of methylenecyclopen-tane and 26 4 g (0 1 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 220 ml of cyclohexane, with stirring The mixture is then stirred at this temperature for a further 3 hours The reaction mixture is washed with dilute hydrochloric acid and then with water, dried over magneslum sulphate and evaporated The residue is crystallised from n-hexane~ This gives 16.6 g of 1-chloro-1--(2',2',2'-trichloroethyl)spiro[3 4]octan-_ 42 -'' ' ' : ~
,:
: ~
2-one of the formula ~` ~ CII~CC13 ; mel-ting poin-t 70~73C.
.
IR spectrum (CHC13) in cm 1 17~5 (C0) NMR spectrum (100 MHz, CDC13) in ppm: 1 60 2 30 (m, 8H); 3 08 (AB, 2H, CH2)j 3.60 (AB, 2H, CH2).
12 0 g (0 041 mo]) of 1-chloro-1~(2',2',2'~trichloro-ethyl)spiro[3.4]octan~2~one are s-tirred with 3 6 g of tetra~
bu-tylammonium chloride at a ba-th temperature of 125C Af-ter 1 5 hours, the reaction mixture is chromatographed on silica gel (elution wi-th toluene/cyclohexane, 1:1) 9.7 g (81% of theory) of l-chloro-3-(2',2',2'-trichloroethyl)spiro[3 4]oc-tan~
2-one of -the formula ."",.,, - r\ -Cl~2CCl3 ,.-'' \~ ' -, . ~ .
..... . .
are ob-tained in this way in the form of a colourless oil IR spec-trum (CHC13) in cm 1 1800 (C0) NMR spectrum (100 MHz, CDC13) in ppm: 4.87 (d, J=2Hz, lH, CHCl); 3.70 (X moiety of ABX, additionally resolved with J=2Hz, lH, CH): 2.73-3.29 (AB moiety of ABX, 2H, CH2); 1.45-2.23 (m, 8H).
4.83 g (16.6 mmols) of 1-chloro-3-(2',2',2'-trichloro-. 43 ethyl)spiro[3.4~octan-2-one are added to a solution of 2,0 g of NaOH in 40 rnl of ~la-ter and 3 ml of dioxane and the mixture is stirred for 2 hours at room -tempera-ture and then for 3 hours at 100C. The reaction solution is washed with diethyl ether and acidified with dilute hydrochlorlc acid. The acid solu-tion is extracted with die-thyl e-t~;er. The extracts are washed with wa-ter, dried over magnesium sulphate and evapora-ted, The residue is crys~tallised from n-hexane.
This gives 3.3 g of 2~(2',2'-dichlorovinyl)spiro[2.4]heptane-arboxylic acid of the formula ~
Cl~ ~
C-CI~ COOII
in the form of a whi-te po~der; mel-ting poin-t 90-105C.
IR spectrum (CHC13) in cm 1 1705 (CO), 1620 (C=C).
NMR spectrum (100 MHz, CDC13/D20) in ppm: 6.15 (d, J=9Hz, 0.8H, CH=CC13cis); 5.51 (d, J=9Hz, 0.2H, CH=CC12 -trans); 2.00-2.40 (m, 2H); 1.60-1.95 tm, 8H).
Example 9 33,6 g (0.62 mol) of methylenecyclopropane and 152 g (0.62 mol) of 2,4,4,4-tetrachlorobu-tyric acid chloride in 620 ml of n-pentane are initially introdvced into a 2,5 litre autoclave, 62.8 g (0.62 mol) of triethylamine in 120 m]
of n-pentane are pumped in in the course of 6 hours, at 60C, and the reaction mixture is then kep-t at 60C for 6 hours.
The reaction mixture is filtered, -the f'iltrate is evaporated ,:
:
i and -the residue is distilled in vacuo The fraction ha.virAg a boiling range of 45-80C/0 09 mm ~Ig is then chromatographed on - 250 g of silica gel using hexane/0-50/0 by weight -toluene.
The pure fracticns are evaporated and the residue is distilled.
This gives l-chloro-1-(2',2',2'--trichloroe-thyl)spiro[3.2]hexan-2-one of -the formula . . .
. ~frC~l~,CC13 .. C~i.
having a boiling point of 70-71C/0.08 mm Hg.
~; `
IR spec-trurn (CHC13) in cm 1 1776 (C0).
H NMR spec-trum (lOOM~Iz CDC13) in pprn: 0.8-1.8 (m, 4H);
2.6-3.8 (m, 4H).
A solution of 11 0 g (42 mmols) of 1 chloro-1-(2',2',2'--trichloroethyl)spiro[3 2]hexan-2-one and 1.17 g (6.3 mrnols) of tributylamine in 15 ml of toluene is refluxed for 5 hours.
A~ter cooling, the reaction mixture is dilu-ted wi-th n-pentane.
The mixture is washed with 2 N sulphuric acid and then with saturated sodium chloride solution, dried over sodium sulphate and evaporated. The residue is distilled in vacuo.
This gives l-chloro-3-(2',2',2'-trichloroe-thyl~spiro[3.2]hexan-2-one of the formula ., .
C~c~l2ccl3 - having a boiling point of 60C/0.01 mm Hg.
.'; . .
, .
`~ 4~5 IR spec-trum (CC14) in c~ 1 1780 (CO).
N~ spectrurn (100 ~!r~lz ~ CDCl~) :in ppm: 0 8-1.7 (m, 4H); 2.6-4.2 (m, 3H); 4,75, 5.15 (one d in each case; together lH)
7.1 g (27 mmols) of 1-chloro-3 (2',2',2'-trichloroethyl)-spiro[3.2]hexan-2-one, together wlth 54 ml (about 135 mmols) of 10% strength NaO~, are refluxed for 2 hours. After cooling, the mixture is washed wi-th several po~-tions o:C diethyl ether, acidified with sulphuric acid and extracted with diethyl ether.
The ether extracts are evapora-ted after drying over sodium sulphate. A small amount of strongly polar irnpurities is removed by filtering on si]ica gel (eluant: diethyl ether).
Af-ter concentrating the filtrate, 2-(2',2'-dichlorovinyl)spiro-[2,2]pen-tane-1-carboxylic acid of the formula i, .
` C12C-CII~ rOO~I
"'`' ~
.
is obtained as an approximately 3:1 cis/trans mixture; melting point 77-78C.
IR spectrum (CC14) in cm 1 1675 (CO) NMR spectrum (100 MHz, CDC13) in ppm: 0,8-2 85 (m, 6H); 5 56 and 6.11 (one d in each case, together lH); 10,~ (broad s, lH).
The examples which follow describe the preparation of some insecticidal ac-tive compounds _xample 10 Preparation of the ~ r of 2~ 2'-dichloro-vinyl)-3.3-dime~ La~ rbo ~
.
~ _ 46 -'' ' a) /+.1~ g (0,02 rliol) of 2 (2',2'-dichloro~inyl)-3,3~
dimethylcyclopropane-l-carboxylic acid and 20 rnl of thionyl chlor~de are ~armed at 70C for 3 hour,s. The excess thionyl chloride is then evaporated of, the residue is taken up in 100 ml of benzene and the mixture is evaporated again. A
solution of 4.o g (~.02 mol) of m-phenoxybenzyl alcohol in 40 M1 of a'bsolute benzen~ is aclded -to this residue [2-(2',2'-dichloro vinyl)-3,3-dimethy1cyclopropanecarboxylic acid chloride] and the mix-ture is warmed -to 40C, 2.2 g (0,022 mol) OI trie-thyl-amine in 10 ml o~ absolute benzene are added dropwise to -this mixture in the course ofone hour and the reaction mix-ture is stirred for a further 1 hour at this temperature, The re-action mix-ture is washed with dilu-te hydrochloric acid, dried over magnesium sulpha-te and evaporated, The residue is chromatographed on silica gel using diethyl ether/n-hexane as the eluant (1:4 mixture by volume), This gives the m-phenoxybenzyl ester of 2-(2',2l-dichlorovinyl)-3,3~dimethyl-cyclopropane-l-carboxylic acid having a refraction of n20 =
1,5628, b) 5,28 g (0,02 mol) of 2~(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobu-tan-1-one, dissolved in 25 ml of absolute dime-thoxyethane, are added dropwise to a solution of 4,0 g (0,02 mol) of m-phenoxybenzyl alcohol, 0,5 g (0,021 mol) of NaII and 40 ml of absolute dimethoxyethane, The reaction mix-ture is then stirred for 1 hour at 45C, 2,25 g (0.02 mol) of potassium tert,-butylate are -then added and the mixture is refluxed for 3 hours, Af-ter it has been discharged in-to wa-ter, it is acidified with dilute hydrochloric acid and extract-ed with ben7.er~e ~`he evapora-ted ex-trac-t is chrorrla-tographc?d on silica gel uslng dlethyl e-ther/n-hexane as the eluant (1:4 mix-ture by volume) This gives the m~phenoxybenzyl es-ter of 2-(2',2' dichlorovinyl)-3,3~dime-thylcycJopropalle-l-carboxylic acid in the form of a viscous oil, whlch has the same properties as the substance obtained according to a) a~ e ] cis~2-(2'~2'-dic7n~orovinyl ~3 3-d~
., ~
1) 10 g (0 047 mol) of cis-2~(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid in 100 ml of benzene are stirred with 12.1 ml (0.141 mol) of oxalyl chloride for 24 hours at room tempera-ture. After evapora-ting the reaction solution, the brown residue is distilled under reduced pressure.
This gives 9.1 g of a clear liquid; boiling point 50~C/0.04 mm Hg. 3.0 g of this clear liquid are dissolved in 30 ml of toluene and 2 rnl of pyridine are added. 2.9 g of ~-cyano-m-phenoxybenzyl alcohol in 20 ml of toluene are added dropwise to this mixture at room tempera-ture and the reaction mixture is then stirred for a further 16 hours at room temperature. The reaction mixture is washed, first with water, then with satur-ated sodium bicarbonate solution and subsequently with salt water, dried over magnesium sulphate and evaporated. The - residue is chromatographed on silica gel (elution with die-thyl ether/n-hexane, 1:2). This gives pure ~-cyano-m-phenoxy-benzyl cis-2-(2 ,2'-dichlorovinyl) 3,3~dimethylcyclopropane-..'~
. " . :
49~5 ~: carboxyla-te e~ a mix-ture Gf di. astereomers.
R spec-trulll (G()I~z, CD~l3) .i.n ppm: I 2()~1 43 (rn, 6H, CH3);
1 67-2.35 (m, 2H, 2 x CII); 6.25 (d, J=9Hz, l.H, C~-I~CC]2), 6 40 , .
.` and 6r45 (ls in each case, 0~5H in each case, C--CN);
~ 6.98-7 65 (m, 9H) ::. Exa~p]e 12 : 7 8 g (0 1 mol) of absolu-te pyri.dlne are added dropwise, .~ at room temperature, -to a solu-tion of 22.75 g (0.1 mol) of crude 2-(2',2'-dichlorovinyl)-3,3-dirnetllylcyclopropanecarboxylic acid ~- chl.oride [prepared according to Example la)] and 21 5 g (0 1 mol) of 3-phenoxy-a-hydroxyethylbenzene in 250 ml of abso].ute ; -toluene The reactlon mixture is stirred for 15 hours a-t ;-: room tempera-ture (20-25C), washed with dilute hydrochloric .~ acid and then with ~a-ter, drie~d (over sodium sulphate) and :
evaporated.. The residue is chromatographed on silica gel ~: using n-hexane/diethyl ether as the e]uant (l:1 rnixture by , .
............... volume) This gives ~-methyl-m~phenoxybenY.yl 2-(2',2'-dichlorovinyl)-3,3~dimethylcyclopropanecarboxylate in -the forrn of a colourless oil of n20 = l.563.
'.~
:~ _ 49 _ .
.
The ether extracts are evapora-ted after drying over sodium sulphate. A small amount of strongly polar irnpurities is removed by filtering on si]ica gel (eluant: diethyl ether).
Af-ter concentrating the filtrate, 2-(2',2'-dichlorovinyl)spiro-[2,2]pen-tane-1-carboxylic acid of the formula i, .
` C12C-CII~ rOO~I
"'`' ~
.
is obtained as an approximately 3:1 cis/trans mixture; melting point 77-78C.
IR spectrum (CC14) in cm 1 1675 (CO) NMR spectrum (100 MHz, CDC13) in ppm: 0,8-2 85 (m, 6H); 5 56 and 6.11 (one d in each case, together lH); 10,~ (broad s, lH).
The examples which follow describe the preparation of some insecticidal ac-tive compounds _xample 10 Preparation of the ~ r of 2~ 2'-dichloro-vinyl)-3.3-dime~ La~ rbo ~
.
~ _ 46 -'' ' a) /+.1~ g (0,02 rliol) of 2 (2',2'-dichloro~inyl)-3,3~
dimethylcyclopropane-l-carboxylic acid and 20 rnl of thionyl chlor~de are ~armed at 70C for 3 hour,s. The excess thionyl chloride is then evaporated of, the residue is taken up in 100 ml of benzene and the mixture is evaporated again. A
solution of 4.o g (~.02 mol) of m-phenoxybenzyl alcohol in 40 M1 of a'bsolute benzen~ is aclded -to this residue [2-(2',2'-dichloro vinyl)-3,3-dimethy1cyclopropanecarboxylic acid chloride] and the mix-ture is warmed -to 40C, 2.2 g (0,022 mol) OI trie-thyl-amine in 10 ml o~ absolute benzene are added dropwise to -this mixture in the course ofone hour and the reaction mix-ture is stirred for a further 1 hour at this temperature, The re-action mix-ture is washed with dilu-te hydrochloric acid, dried over magnesium sulpha-te and evaporated, The residue is chromatographed on silica gel using diethyl ether/n-hexane as the eluant (1:4 mixture by volume), This gives the m-phenoxybenzyl ester of 2-(2',2l-dichlorovinyl)-3,3~dimethyl-cyclopropane-l-carboxylic acid having a refraction of n20 =
1,5628, b) 5,28 g (0,02 mol) of 2~(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobu-tan-1-one, dissolved in 25 ml of absolute dime-thoxyethane, are added dropwise to a solution of 4,0 g (0,02 mol) of m-phenoxybenzyl alcohol, 0,5 g (0,021 mol) of NaII and 40 ml of absolute dimethoxyethane, The reaction mix-ture is then stirred for 1 hour at 45C, 2,25 g (0.02 mol) of potassium tert,-butylate are -then added and the mixture is refluxed for 3 hours, Af-ter it has been discharged in-to wa-ter, it is acidified with dilute hydrochloric acid and extract-ed with ben7.er~e ~`he evapora-ted ex-trac-t is chrorrla-tographc?d on silica gel uslng dlethyl e-ther/n-hexane as the eluant (1:4 mix-ture by volume) This gives the m~phenoxybenzyl es-ter of 2-(2',2' dichlorovinyl)-3,3~dime-thylcycJopropalle-l-carboxylic acid in the form of a viscous oil, whlch has the same properties as the substance obtained according to a) a~ e ] cis~2-(2'~2'-dic7n~orovinyl ~3 3-d~
., ~
1) 10 g (0 047 mol) of cis-2~(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid in 100 ml of benzene are stirred with 12.1 ml (0.141 mol) of oxalyl chloride for 24 hours at room tempera-ture. After evapora-ting the reaction solution, the brown residue is distilled under reduced pressure.
This gives 9.1 g of a clear liquid; boiling point 50~C/0.04 mm Hg. 3.0 g of this clear liquid are dissolved in 30 ml of toluene and 2 rnl of pyridine are added. 2.9 g of ~-cyano-m-phenoxybenzyl alcohol in 20 ml of toluene are added dropwise to this mixture at room tempera-ture and the reaction mixture is then stirred for a further 16 hours at room temperature. The reaction mixture is washed, first with water, then with satur-ated sodium bicarbonate solution and subsequently with salt water, dried over magnesium sulphate and evaporated. The - residue is chromatographed on silica gel (elution with die-thyl ether/n-hexane, 1:2). This gives pure ~-cyano-m-phenoxy-benzyl cis-2-(2 ,2'-dichlorovinyl) 3,3~dimethylcyclopropane-..'~
. " . :
49~5 ~: carboxyla-te e~ a mix-ture Gf di. astereomers.
R spec-trulll (G()I~z, CD~l3) .i.n ppm: I 2()~1 43 (rn, 6H, CH3);
1 67-2.35 (m, 2H, 2 x CII); 6.25 (d, J=9Hz, l.H, C~-I~CC]2), 6 40 , .
.` and 6r45 (ls in each case, 0~5H in each case, C--CN);
~ 6.98-7 65 (m, 9H) ::. Exa~p]e 12 : 7 8 g (0 1 mol) of absolu-te pyri.dlne are added dropwise, .~ at room temperature, -to a solu-tion of 22.75 g (0.1 mol) of crude 2-(2',2'-dichlorovinyl)-3,3-dirnetllylcyclopropanecarboxylic acid ~- chl.oride [prepared according to Example la)] and 21 5 g (0 1 mol) of 3-phenoxy-a-hydroxyethylbenzene in 250 ml of abso].ute ; -toluene The reactlon mixture is stirred for 15 hours a-t ;-: room tempera-ture (20-25C), washed with dilute hydrochloric .~ acid and then with ~a-ter, drie~d (over sodium sulphate) and :
evaporated.. The residue is chromatographed on silica gel ~: using n-hexane/diethyl ether as the e]uant (l:1 rnixture by , .
............... volume) This gives ~-methyl-m~phenoxybenY.yl 2-(2',2'-dichlorovinyl)-3,3~dimethylcyclopropanecarboxylate in -the forrn of a colourless oil of n20 = l.563.
'.~
:~ _ 49 _ .
.
Claims (21)
1, A process for the preparation of a 2-(2',2',2'-tri-halogenoethyl)-4-halogenocyclobutan-1-one of the formula I
(I) in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are an alkylene group having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine Y must always also be bromine, which comprises reacting a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II
(II) in which X and Y are as defined under formula I, in the pres-ence of an organic base with an olefine of the formula III
(III) in which R1 and R2 are as defined under formula I, to give a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV
(IV) in which R1, R2, X and Y are as defined under formula I, and then rearranging the latter, in the presence of a catalyst, into a2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutann-l-one of the formula I.
2, A process according to claim 1, which comprises using
(I) in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are an alkylene group having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine Y must always also be bromine, which comprises reacting a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II
(II) in which X and Y are as defined under formula I, in the pres-ence of an organic base with an olefine of the formula III
(III) in which R1 and R2 are as defined under formula I, to give a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV
(IV) in which R1, R2, X and Y are as defined under formula I, and then rearranging the latter, in the presence of a catalyst, into a2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutann-l-one of the formula I.
2, A process according to claim 1, which comprises using
2,4,4,4-tetrachlorobutyric acid chloride as the 2,4,4,4-tetra-halogenobutyric acid chloride of the formula II.
3. A process according to claim 1, which comprises using an olefine of the formula III in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are an alkylene group having 2 to 3 carbon atoms.
4. A process accoridng to claim 1, which comprises using isobutylene as the olefine of the formula III.
5. A process according to claim 1, which comprises using methylenecyclopropane as the olefine of the formula III.
6. A process according to claim 1, which comprises carrying out the reaction of a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II with an olefine of the formula III in the presence of pyridine or of a trialkylamine having 1 to 4 carbon atoms in each alkyl group and in the presence of an inert organic solvent.
7. A process according to claim 1, which comprises carrying out the reaction of a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II with an olefine of the formula III in the presence of triethylamine.
8. A process according to claim 1, which comprises using an inorganic or organic proton acid as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogeno-cyclobutan-1-one of the formula IV into a 2-(2',2',2'-tri-halogenoethyl)-4-halogenocyclobutan-1-one of the formula I.
9. A process according to claim 1, which comprises using a hydrogen halide acid as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV in to a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I
10. A process according to claim 1, which comprises using an organic base as the catalyst for the rearrangement of a 2-(2'2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-onee of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogeno-cyclobutan-1-one of the formula I.
11. A process according to claim 1, which comprises using an amine of the formula in which Q1 is alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 5 carbon atoms, benzyl or phenyl and Q2 and Q3 independently of one another are hydrogen or alkyl having 1 to 8 carbon atoms, as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutann-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogeno-cyclobutan-1-one of the formula I.
12. A process according to claim 1, which comprises using a salt of a proton acid with ammonia, a nitrogen-containing organic base or a quaternary ammonium salt as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogeno-cyclobutan-1-one of the formula IV into a 2-(2',2',2'-tri-halogenoethyl)-4-halogenocyclobutan-1-one of the formula I.
13. A process according to claim 1, which comprises using a salt of a hydrogen halide acid with an aliphatic, cyclo-aliphatic, araliphatic or aromatic primary, secondary or tert-iary amine or a heterocyclic nitrogen base as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclo-butan-1-one of the formula IV into a 2-(2',2',2'-trihalogeno-ethyl)-4-halogenocyclobutan-1-one of the formula I.
14. A process according to claim 1, which comprises using a salt of the formula , in which M is fluorine, bromine, iodine or chlorine, Q4 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or naphthyl and Q5, Q6 and Q7 in-dependently of one another are hydrogen or alkyl having 1. to 18 carbon atoms, or a N-alkylpyridinium halide having 1 to 18 carbon atoms in the alkyl group, as the catalyst for the rearrangement a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogeno-cyclobutan-1-one of the formula 1.
15. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-cyclobutan-1-one of the formula I at temperatures of between 80 and 130°C.
16. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV in-to a 2-(2',2',2'-trihalogenoethyl)-4-cyclobutan-1-one of the formula I in the melt at a temperature of between 80 and 130°C in the presence of a trialkylamine having 1 to 8 carbon atoms in each alkyl group or of a tetraalkylammonium halide having 1 to 18 carbon atoms in the alkyl groups.
17, A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I
in the presence of an inert solvent,
in the presence of an inert solvent,
18. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I in an aliphatic alcohol having 1 to 4 carbon atoms, toluene, xylene, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol, diethyl ether or diisopropyl ketone, as the solvent.
19. 2-(2',2',2'-Trihalogenoethyl)-halogenocyclobutan-11-ones of the formula in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are alkylene having 2 to 4 carbon atoms, X is chlorine or bromine, and Y' and Y" are each hydrogen, chlorine or bromine, with the proviso that if one of Y' and Y" is chlorine or bromine the other must be hydrogen and that if X is bromine, Y' or Y" must always be bromine.
20. A2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutann-1-one of the formula IV
(IV) in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are alkylene having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine, Y must always also be bromine.
(IV) in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are alkylene having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine, Y must always also be bromine.
21. A2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutann-1-one of the formula I
(I) in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are alkylene having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine Y must always also be bromine.
(I) in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are alkylene having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine Y must always also be bromine.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4071/77 | 1977-03-31 | ||
| CH407177 | 1977-03-31 | ||
| CH1440477 | 1977-11-24 | ||
| CH14404/77 | 1977-11-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111445A true CA1111445A (en) | 1981-10-27 |
Family
ID=25694571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA299,990A Expired CA1111445A (en) | 1977-03-31 | 1978-03-29 | Process for the preparation of 2-(2',2',2'- trihalogenoethyl)-4-halogenocyclobutan-1-ones |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS53121740A (en) |
| AR (1) | AR219939A1 (en) |
| AT (1) | AT353770B (en) |
| AU (1) | AU523027B2 (en) |
| BR (1) | BR7801977A (en) |
| CA (1) | CA1111445A (en) |
| CS (1) | CS199523B2 (en) |
| DD (1) | DD137097A5 (en) |
| DE (1) | DE2813337A1 (en) |
| DK (1) | DK140578A (en) |
| ES (1) | ES468360A1 (en) |
| FI (1) | FI780930A (en) |
| FR (1) | FR2385672A1 (en) |
| GB (2) | GB1601552A (en) |
| GR (1) | GR71707B (en) |
| HU (1) | HU178911B (en) |
| IL (1) | IL54395A0 (en) |
| IT (1) | IT1094010B (en) |
| MX (1) | MX5101E (en) |
| NL (1) | NL189706C (en) |
| NO (2) | NO781112L (en) |
| PL (1) | PL116458B2 (en) |
| SE (1) | SE437658B (en) |
| TR (1) | TR20405A (en) |
| YU (1) | YU40698B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2638356A1 (en) * | 1976-08-26 | 1978-03-02 | Bayer Ag | METHOD FOR PRODUCING VINYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS |
| EP0012722B1 (en) * | 1978-12-15 | 1981-12-09 | Ciba-Geigy Ag | Process for the preparation of optically active 3-substituted 2-(2',2'-dihalovinyl)-cyclopropane-1-carboxylic acids and their derivatives; 4-(2',2',2'-trihaloethyl)-cyclobutane-1-sulphonic acid salts and their preparation |
| JPS5692830A (en) * | 1979-12-07 | 1981-07-27 | Ciba Geigy Ag | 22*2**2**dichloroo3**3**3**trifluoropropyl** and 22*2**2**3**trichloroo3**3** difluoropropyl**44chlorocyclobutanee11one and their manufacture |
| IT1135265B (en) * | 1981-02-02 | 1986-08-20 | Montedison Spa | PROCESS FOR THE PREPARATION OF INTERMEDIATES FOR PYRETROIDS |
| JP4712405B2 (en) * | 2005-02-07 | 2011-06-29 | 文化シヤッター株式会社 | Locking device for shutter device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE835888C (en) * | 1950-06-22 | 1952-04-07 | Basf Ag | Process for the preparation of derivatives of butyric acid |
| GB1437832A (en) * | 1973-04-16 | 1976-06-03 | Shell Int Research | Halocyclobutanones |
| HU176610B (en) * | 1974-09-04 | 1981-03-28 | Shell Int Research | Process for producing cyclobutanones |
| JPS51136649A (en) * | 1975-05-16 | 1976-11-26 | Kuraray Co Ltd | Process for preparation of substituted cyclopropanecarboxylic acid est ers |
| DE2638356A1 (en) * | 1976-08-26 | 1978-03-02 | Bayer Ag | METHOD FOR PRODUCING VINYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS |
-
1978
- 1978-03-28 FI FI780930A patent/FI780930A/en not_active Application Discontinuation
- 1978-03-28 DE DE19782813337 patent/DE2813337A1/en active Granted
- 1978-03-29 CA CA299,990A patent/CA1111445A/en not_active Expired
- 1978-03-29 DD DD78204455A patent/DD137097A5/en unknown
- 1978-03-29 GR GR55289A patent/GR71707B/el unknown
- 1978-03-30 NO NO781112A patent/NO781112L/en unknown
- 1978-03-30 DK DK140578A patent/DK140578A/en not_active IP Right Cessation
- 1978-03-30 IT IT21802/78A patent/IT1094010B/en active
- 1978-03-30 GB GB12557/78A patent/GB1601552A/en not_active Expired
- 1978-03-30 YU YU757/78A patent/YU40698B/en unknown
- 1978-03-30 SE SE7803600A patent/SE437658B/en unknown
- 1978-03-30 BR BR7801977A patent/BR7801977A/en unknown
- 1978-03-30 AR AR271608A patent/AR219939A1/en active
- 1978-03-30 CS CS782048A patent/CS199523B2/en unknown
- 1978-03-30 ES ES468360A patent/ES468360A1/en not_active Expired
- 1978-03-30 FR FR7809241A patent/FR2385672A1/en active Granted
- 1978-03-30 AT AT225078A patent/AT353770B/en not_active IP Right Cessation
- 1978-03-30 IL IL54395A patent/IL54395A0/en not_active IP Right Cessation
- 1978-03-30 HU HU78CI1821A patent/HU178911B/en unknown
- 1978-03-30 GB GB31151/80A patent/GB1601553A/en not_active Expired
- 1978-03-31 NL NLAANVRAGE7803465,A patent/NL189706C/en active Search and Examination
- 1978-03-31 PL PL1978205739A patent/PL116458B2/en unknown
- 1978-03-31 MX MX786986U patent/MX5101E/en unknown
- 1978-03-31 JP JP3801978A patent/JPS53121740A/en active Granted
- 1978-03-31 TR TR20405A patent/TR20405A/en unknown
- 1978-03-31 AU AU34643/78A patent/AU523027B2/en not_active Expired
-
1985
- 1985-10-09 NO NO853995A patent/NO853995L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO781112L (en) | 1978-10-03 |
| PL205739A1 (en) | 1979-06-04 |
| CS199523B2 (en) | 1980-07-31 |
| DK140578A (en) | 1978-10-01 |
| SE7803600L (en) | 1978-10-01 |
| IT1094010B (en) | 1985-07-26 |
| BR7801977A (en) | 1979-01-02 |
| FR2385672A1 (en) | 1978-10-27 |
| FR2385672B1 (en) | 1980-09-19 |
| JPS53121740A (en) | 1978-10-24 |
| HU178911B (en) | 1982-07-28 |
| YU75778A (en) | 1983-01-21 |
| AT353770B (en) | 1979-12-10 |
| AU523027B2 (en) | 1982-07-08 |
| JPS6228772B2 (en) | 1987-06-23 |
| ES468360A1 (en) | 1979-07-16 |
| IT7821802A0 (en) | 1978-03-30 |
| TR20405A (en) | 1981-06-10 |
| YU40698B (en) | 1986-04-30 |
| SE437658B (en) | 1985-03-11 |
| DE2813337A1 (en) | 1978-10-05 |
| FI780930A (en) | 1978-10-01 |
| ATA225078A (en) | 1979-05-15 |
| MX5101E (en) | 1983-03-16 |
| GR71707B (en) | 1983-06-21 |
| DE2813337C2 (en) | 1989-03-02 |
| DD137097A5 (en) | 1979-08-15 |
| NO853995L (en) | 1978-10-03 |
| GB1601552A (en) | 1981-10-28 |
| GB1601553A (en) | 1981-10-28 |
| AU3464378A (en) | 1979-10-04 |
| PL116458B2 (en) | 1981-06-30 |
| NL7803465A (en) | 1978-10-03 |
| AR219939A1 (en) | 1980-09-30 |
| IL54395A0 (en) | 1978-06-15 |
| NL189706C (en) | 1993-07-01 |
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