CA1123006A - Preparation of cyclopropane derivatives - Google Patents
Preparation of cyclopropane derivativesInfo
- Publication number
- CA1123006A CA1123006A CA277,560A CA277560A CA1123006A CA 1123006 A CA1123006 A CA 1123006A CA 277560 A CA277560 A CA 277560A CA 1123006 A CA1123006 A CA 1123006A
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- Canada
- Prior art keywords
- process according
- carried out
- general formula
- chlorine
- alkyl group
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A B S T R A C T
A process for the preparation of cyano-substitute cyclopropane derivatives of general formula:- (II) (wherein Hal represents a fluorine, chlorine or bromine atom;
and R1 and R2 each individually represents an alkyl group of 1 to 4 carbon atoms) which comprises:-(a) cyclizing and dehydrohalogenating a compound of general formula:-
A process for the preparation of cyano-substitute cyclopropane derivatives of general formula:- (II) (wherein Hal represents a fluorine, chlorine or bromine atom;
and R1 and R2 each individually represents an alkyl group of 1 to 4 carbon atoms) which comprises:-(a) cyclizing and dehydrohalogenating a compound of general formula:-
Description
This invention relates to a process for the preparation of cyano-~ubstituted cyclopropane derivfltives which Are useful intermediates in the prepar~tion of insecticidally Acti~e compound~, for example the 3-phenoxybenzyl e~ter of 2-(2,2-dichlorovinyl)-3,3-di~ethylcyclopropane-carboxylic acid.
Con~iderable effort hàs been expended in attempting the synthesis of the above-men~ioned c~clopropane carboxylic acid - 80~ for example Netherlands patent applications 7510479 and 7509631 - and, ~o far, all published route~ to this acid are cumberaome and involve many procesa step~. The Applicant has found a simple rout~ to the following key in~ermediate in the manufacture of the above-mentioned acid:-H CH~CCl CH3 ~ CN (I) It will be appreciated that the intermediate I can be readily converted by known m~thods into the corr~ponding cyclopropane carboxylic acid.
The pre~ent invention therofore p~vides a process for the preparation of cyano-sub~tituted cyclopropane derivatives of general for~ula:-H CH-C(H~1)2 CN (II) R~ H
(wherein Xal repre~ents a fluorine, chlorine or bromine atom and Rl and R each repre~ent~ an alkyl group of l to 4 cnrbon atom~, preferably methyl); which comprise~:-~a) cyclizing and dehydrohalo~enatin~ a compound of ~eneral for~ula:-X Y
/ C~-CH2-C( ~A~
C \ (III) R~ CHCC0~3 CN
Con~iderable effort hàs been expended in attempting the synthesis of the above-men~ioned c~clopropane carboxylic acid - 80~ for example Netherlands patent applications 7510479 and 7509631 - and, ~o far, all published route~ to this acid are cumberaome and involve many procesa step~. The Applicant has found a simple rout~ to the following key in~ermediate in the manufacture of the above-mentioned acid:-H CH~CCl CH3 ~ CN (I) It will be appreciated that the intermediate I can be readily converted by known m~thods into the corr~ponding cyclopropane carboxylic acid.
The pre~ent invention therofore p~vides a process for the preparation of cyano-sub~tituted cyclopropane derivatives of general for~ula:-H CH-C(H~1)2 CN (II) R~ H
(wherein Xal repre~ents a fluorine, chlorine or bromine atom and Rl and R each repre~ent~ an alkyl group of l to 4 cnrbon atom~, preferably methyl); which comprise~:-~a) cyclizing and dehydrohalo~enatin~ a compound of ~eneral for~ula:-X Y
/ C~-CH2-C( ~A~
C \ (III) R~ CHCC0~3 CN
2--(wherein X and Y each repre~ent~ a chlorine or brsmine atom; and R~ repre~ents a hydrogen atom or an alkyl group Or 1 to 4 carbon atoms) in the pres~nce of a base; and (b) thermally decarboxylating the resultin6 cycliz~d dehydroh~loge~ated 2roduc~ to ~orm the compound of general formula II.
In Btep (A) 0~ the proce~s accordin~ to the invention only mild tempera~ure6, e.g. ambient temperature6l a ffl nece6sary but the reaction will take place at temperatures in the range 30 to 150 C. Higher than ambient temperatures are gener~lly preferred in order to achieve short~r reaction times, e~g. temperatures in the range 60 -100 C. Generally ~0 speaking, cyclization and dehydrohalogenation take6 place ~imultaneouslybut if very mild conditions are employed, ~or example a lXw solution of hydroxide in methanol at 20-~0C, an intermediate cyclopropane derivative of the ~ollowing general formula i6 pffl dominantly produced:-y H CH2-C(Hal)2 X
~ ~ C~ (IV) R2 COOR~
(wherein ~ , R2 and Y have the meaningB hereinbefore ~pecified and R4 i6 a hydrogen or alkali metal or alkaline earth metal atom, an ammonium or alkyl-subetituted ammoniuml or an alkyl group of 1-4 carbon atom~
Co~pounds of the general formula IV are novel compounds and accordingly represent a novel intermediate in the proce~s according to $he i~vention.
The cyclizati~n and de~ydrohalogenation 6tep has to be carried out in the presence of a base and in general mild bases are su~ficient, for example alkali metal, alkaline earth metal and ammonium hydr~xide~ acetates, carbonates, bicarbonates; and ammonia and alkyl-~ubstituted ammonias e.g.
primary, secondary and tertiary amine~. Good results have been obtained with nitrogenous basefi and alkali metal acetates, carbonate~ and bicarbonates;
particularly preferred bases are ammonia and sodium acetate.
Step (a) is preferably carri0d out in the abaence o~ water and in the pre6ence of u non-aqueou~ e~olvent - e.6~ an alkanol such as methanol or ethanol, or dimothyl formamide. The latter ~olvent ha6 been found to be particularly u6eful.
Step (b), the decarboxylation ~tep in the proce6s according to the invention, i8 preferably effccted at a temperature in the range 100 to 150 C and it has been found that decarboxylation proceed~ smoothly when the free acid, the ammonium 6alt or the alkali metal 6alt is employed.
AdYantageously, a polar aprotic solvent, e.g, dimethyl for~amide i~ used in the decarboxylation step.
Surprisingly it h~s been found that ~tep (a) and step (b) can be carried out in the same reaction zone or pot and that the two steps appear to take place simultaneously, that is to say cyclization, dehydrohalogellation and decarboxylation all appear to be taki4g place at the same time. Such a combination of che~ical reaction3 renders thi6 aspect of the proces~ according to the invention particularly valuable as an improvement in the route to the important pyrethroid in6ecticide intermediate~ 2-dichlorovinyl~-3,3-dimethylcyclopropanecarboxyli acid.
~0 hs might be expected, the conditions required to achieve this combinationof reactions have to be carefully selected in order to obtain maximum yields of the end-product.
According to a prefarred a~pect of the invention, the ffl fore, the proce~6 is carried out in one reaction &one or pot in the preeence of a nitrogenous base and an inert non-aqueou6 solvent at a temperature in the raage 70 to 160 C prefera~ly in the range 80 to 150 C0 Better ~e6ults have been obtained with a~monia or sodium acetate as the nitrogenous ba6e and dimethyl ~ormamide or N-methyl_pyrollidone a~ the non-aqueou~ solvent.
Also anhydrou6 conditions 6hould pre~erably be employed.
Those compounds of ~eneral formula IV are novel compound~ and as such -$~
are included within th~ ~cope of the invention. A particular preferr~d novel compound i~ l-cyano-2-(~,2-dichlorovinyl)-3,3-di~ethylcyclopropane-carboxylic acid together with the alkali metal alkaline earth metal and ammonium and ~ubtituted ammonium salt6 thersof. The6e derivatives are useful intermediates in the preparation of 2-(2,2-dichlorovinyl)-3,~-dimethylcyclopropanecarboxylic acid~ certain e6ters of which po~6es~
in~cticidal activity.
The invention iB further illu~trated in the following Exampl2~.
EXAMPLE I Prep~ration of ~ ,2-dichloroYinx1)-3,3-dimet~ylc~cl~propano nitrile (A) ____ Step (a) Prepar~tion of l-d~no-2-(2,2-dichlorovi~yl)-3,3-dimethyl-cyclo~ropanecarboxylic acid (B) Methyl 4-bromo-2 cyano-~3-climethyl-6,6,6-trichlorohexanoate (64.06, 0.166m) was add~d over a p~riod of 25 minutos to a ~u6pension of potas~iu~ hydroxide (120.06, 1.8m) in methanol (2100~1) at 20C~
~he mixture waG then stirred ~or 1 hour at 35 C and then heated under reflux for 2.5 hours. The solvent was then removed undor reduced pressure and the re6idue was di~solved in water (1500ml). The aqueous phase wa~
washed once with dichloro~ethane and then acidi~ied with concentrated hytrochloric acid to about pH 1. The mixture wa~ then extracted thr~e time with dichloro~ethane and the extract~ were driedO The ~olvent waE then re~oved under reduced pressure to yield the require~l acid 1-cyano-2-(2,2-dichlorovinyl) 3,3-dimethylcyclopropanecarboxylic acid, as a white crystalline 601id (m.p. 128-132 C, yield 37.5g, 97%)0 The NMR spe~trum of the compound measured at 60MHz in deuterochloroform solution 6howed the followin~ absorptions relative to a tetra~ethyl-~ilane ~t~ndard~ On the ba~is of the sp~ctrum it was est~bli~hed that the product consi6ted of two geometric isomer~, Z and E, in the ratio Z:E = 56:44.
S = 6.10 ppm (doublet, -CH = Z-i~omer) ~- 5.78 ppm (doublet~ -CH = E-isomer) ~= 2~83 ppm (doublet, ring ~ E-isomer) ~= 2.65 ppm (doublet, ring H 8-i~omer) 0, 1.38 ppm (singlets, two CH3 Z-isomer) ~ - 1.47, 143 ppm (6inglets, two CH3 E i~omer) 1-Cyano-2-(2,2 dichloroYinyl)-3~3-dimethylcyclopropanecarboxylic acid (1.5g) was di~solv*d in dimethylformamide (lOml) and the Rolution was s~turated with gaseous ammonia ~t 20 C. The ~olution waR then stirr~d at 130 C for 18 hours, then diluted with water (150ml) and extracted with pentane. The extra~tR were dri~d (M~S04) and the solvent was removed under reduced pres~ure to give the required 2-(2,2-dichlorovinyl)-~3,3~dimethylcyclopropane nitrile yield 82%.
AMPLE II
Tha procedure of Example I was repeated using methyl 4-chloro-2-cyano-3,3-dimethyl-6,6,6-trichlorohexanoate afi 6tarting material. The yield o~ 1-cyano-2-(2~-dichlorovinyl)-3,3-dimeth~lcyclopropanecarboxylic acid was ~5-96%.
EXAMPLE III Preparation of (A) in one reaction ve~8el using N~3 a~ ba~e 4-Chloro-2-cyano-3t3-dimethyl 6,6,6-trichlorohexanoic acid (40g) was dis~olved in dimethyl formamid~ (55ml) and the so~ution was ~aturated with gaseou~ ammonla at room tamperature with no external cooling. The solution wa8 ~tirred at 140C for 5 hours, then diluted with water and &xtracted with ether (3 x lOOml). The ~ther ~olution wa~
wafihed Wit~l s~turated ~aCl, dri~d ovar MgS04 and evaporated to afford Compound A a~ a yellow oil (purity 85~) which partly crystallized on 6tanding. Yield 79~.
EXAMPL~ IV
a8 base ___ 4-Chloro-2-cyano-3,3-dimethyl~6,6,6-trichlorohexanoic acid (3~07g) a~d sodium acetate (2.05g; water-free) were dissolved in di~ethyl formamide (o.Oml). The ~olution was then 6tirred at 145C for 12 hour The working-up procedure wa8 the sa~e as indicated in Example III a~d yielded 1~856 of Gompound A with purity 90X~ Yield 86~.
In Btep (A) 0~ the proce~s accordin~ to the invention only mild tempera~ure6, e.g. ambient temperature6l a ffl nece6sary but the reaction will take place at temperatures in the range 30 to 150 C. Higher than ambient temperatures are gener~lly preferred in order to achieve short~r reaction times, e~g. temperatures in the range 60 -100 C. Generally ~0 speaking, cyclization and dehydrohalogenation take6 place ~imultaneouslybut if very mild conditions are employed, ~or example a lXw solution of hydroxide in methanol at 20-~0C, an intermediate cyclopropane derivative of the ~ollowing general formula i6 pffl dominantly produced:-y H CH2-C(Hal)2 X
~ ~ C~ (IV) R2 COOR~
(wherein ~ , R2 and Y have the meaningB hereinbefore ~pecified and R4 i6 a hydrogen or alkali metal or alkaline earth metal atom, an ammonium or alkyl-subetituted ammoniuml or an alkyl group of 1-4 carbon atom~
Co~pounds of the general formula IV are novel compounds and accordingly represent a novel intermediate in the proce~s according to $he i~vention.
The cyclizati~n and de~ydrohalogenation 6tep has to be carried out in the presence of a base and in general mild bases are su~ficient, for example alkali metal, alkaline earth metal and ammonium hydr~xide~ acetates, carbonates, bicarbonates; and ammonia and alkyl-~ubstituted ammonias e.g.
primary, secondary and tertiary amine~. Good results have been obtained with nitrogenous basefi and alkali metal acetates, carbonate~ and bicarbonates;
particularly preferred bases are ammonia and sodium acetate.
Step (a) is preferably carri0d out in the abaence o~ water and in the pre6ence of u non-aqueou~ e~olvent - e.6~ an alkanol such as methanol or ethanol, or dimothyl formamide. The latter ~olvent ha6 been found to be particularly u6eful.
Step (b), the decarboxylation ~tep in the proce6s according to the invention, i8 preferably effccted at a temperature in the range 100 to 150 C and it has been found that decarboxylation proceed~ smoothly when the free acid, the ammonium 6alt or the alkali metal 6alt is employed.
AdYantageously, a polar aprotic solvent, e.g, dimethyl for~amide i~ used in the decarboxylation step.
Surprisingly it h~s been found that ~tep (a) and step (b) can be carried out in the same reaction zone or pot and that the two steps appear to take place simultaneously, that is to say cyclization, dehydrohalogellation and decarboxylation all appear to be taki4g place at the same time. Such a combination of che~ical reaction3 renders thi6 aspect of the proces~ according to the invention particularly valuable as an improvement in the route to the important pyrethroid in6ecticide intermediate~ 2-dichlorovinyl~-3,3-dimethylcyclopropanecarboxyli acid.
~0 hs might be expected, the conditions required to achieve this combinationof reactions have to be carefully selected in order to obtain maximum yields of the end-product.
According to a prefarred a~pect of the invention, the ffl fore, the proce~6 is carried out in one reaction &one or pot in the preeence of a nitrogenous base and an inert non-aqueou6 solvent at a temperature in the raage 70 to 160 C prefera~ly in the range 80 to 150 C0 Better ~e6ults have been obtained with a~monia or sodium acetate as the nitrogenous ba6e and dimethyl ~ormamide or N-methyl_pyrollidone a~ the non-aqueou~ solvent.
Also anhydrou6 conditions 6hould pre~erably be employed.
Those compounds of ~eneral formula IV are novel compound~ and as such -$~
are included within th~ ~cope of the invention. A particular preferr~d novel compound i~ l-cyano-2-(~,2-dichlorovinyl)-3,3-di~ethylcyclopropane-carboxylic acid together with the alkali metal alkaline earth metal and ammonium and ~ubtituted ammonium salt6 thersof. The6e derivatives are useful intermediates in the preparation of 2-(2,2-dichlorovinyl)-3,~-dimethylcyclopropanecarboxylic acid~ certain e6ters of which po~6es~
in~cticidal activity.
The invention iB further illu~trated in the following Exampl2~.
EXAMPLE I Prep~ration of ~ ,2-dichloroYinx1)-3,3-dimet~ylc~cl~propano nitrile (A) ____ Step (a) Prepar~tion of l-d~no-2-(2,2-dichlorovi~yl)-3,3-dimethyl-cyclo~ropanecarboxylic acid (B) Methyl 4-bromo-2 cyano-~3-climethyl-6,6,6-trichlorohexanoate (64.06, 0.166m) was add~d over a p~riod of 25 minutos to a ~u6pension of potas~iu~ hydroxide (120.06, 1.8m) in methanol (2100~1) at 20C~
~he mixture waG then stirred ~or 1 hour at 35 C and then heated under reflux for 2.5 hours. The solvent was then removed undor reduced pressure and the re6idue was di~solved in water (1500ml). The aqueous phase wa~
washed once with dichloro~ethane and then acidi~ied with concentrated hytrochloric acid to about pH 1. The mixture wa~ then extracted thr~e time with dichloro~ethane and the extract~ were driedO The ~olvent waE then re~oved under reduced pressure to yield the require~l acid 1-cyano-2-(2,2-dichlorovinyl) 3,3-dimethylcyclopropanecarboxylic acid, as a white crystalline 601id (m.p. 128-132 C, yield 37.5g, 97%)0 The NMR spe~trum of the compound measured at 60MHz in deuterochloroform solution 6howed the followin~ absorptions relative to a tetra~ethyl-~ilane ~t~ndard~ On the ba~is of the sp~ctrum it was est~bli~hed that the product consi6ted of two geometric isomer~, Z and E, in the ratio Z:E = 56:44.
S = 6.10 ppm (doublet, -CH = Z-i~omer) ~- 5.78 ppm (doublet~ -CH = E-isomer) ~= 2~83 ppm (doublet, ring ~ E-isomer) ~= 2.65 ppm (doublet, ring H 8-i~omer) 0, 1.38 ppm (singlets, two CH3 Z-isomer) ~ - 1.47, 143 ppm (6inglets, two CH3 E i~omer) 1-Cyano-2-(2,2 dichloroYinyl)-3~3-dimethylcyclopropanecarboxylic acid (1.5g) was di~solv*d in dimethylformamide (lOml) and the Rolution was s~turated with gaseous ammonia ~t 20 C. The ~olution waR then stirr~d at 130 C for 18 hours, then diluted with water (150ml) and extracted with pentane. The extra~tR were dri~d (M~S04) and the solvent was removed under reduced pres~ure to give the required 2-(2,2-dichlorovinyl)-~3,3~dimethylcyclopropane nitrile yield 82%.
AMPLE II
Tha procedure of Example I was repeated using methyl 4-chloro-2-cyano-3,3-dimethyl-6,6,6-trichlorohexanoate afi 6tarting material. The yield o~ 1-cyano-2-(2~-dichlorovinyl)-3,3-dimeth~lcyclopropanecarboxylic acid was ~5-96%.
EXAMPLE III Preparation of (A) in one reaction ve~8el using N~3 a~ ba~e 4-Chloro-2-cyano-3t3-dimethyl 6,6,6-trichlorohexanoic acid (40g) was dis~olved in dimethyl formamid~ (55ml) and the so~ution was ~aturated with gaseou~ ammonla at room tamperature with no external cooling. The solution wa8 ~tirred at 140C for 5 hours, then diluted with water and &xtracted with ether (3 x lOOml). The ~ther ~olution wa~
wafihed Wit~l s~turated ~aCl, dri~d ovar MgS04 and evaporated to afford Compound A a~ a yellow oil (purity 85~) which partly crystallized on 6tanding. Yield 79~.
EXAMPL~ IV
a8 base ___ 4-Chloro-2-cyano-3,3-dimethyl~6,6,6-trichlorohexanoic acid (3~07g) a~d sodium acetate (2.05g; water-free) were dissolved in di~ethyl formamide (o.Oml). The ~olution was then 6tirred at 145C for 12 hour The working-up procedure wa8 the sa~e as indicated in Example III a~d yielded 1~856 of Gompound A with purity 90X~ Yield 86~.
3~
EXAMPLE Y Pr~parntion of (A) in one r~Action vcs~el u~in6 ammoniA
_._ undsr pressure ae ba~e A solution of 4-chloro-2-cynno-3,3-dimethyl-6,6,6-trichlorohexanoic acid (6.14g) in dimethyl formamide (l~ml) wa6 stirred at 145 C for
EXAMPLE Y Pr~parntion of (A) in one r~Action vcs~el u~in6 ammoniA
_._ undsr pressure ae ba~e A solution of 4-chloro-2-cynno-3,3-dimethyl-6,6,6-trichlorohexanoic acid (6.14g) in dimethyl formamide (l~ml) wa6 stirred at 145 C for
4 hour~ under an ammonia atmo~phere with initially 5 bar pressure.
After release of the pre6~ure the mixture was ~tirred for another 6 hour~ at 145 C. After cooling down over 90% of the ~olYent wa~
fla~hed off (bath tempera~ure max. 60C, pres6ure 12~ ). The residue wa6 mixed ~ith toluene, wa~hod ~ubsequently with aqueous hydrochloric acid and aqueou~ sodium bicarbonate~ After dryin~
of the organic pha~e the solvent wa~ Yamov~d under reduced pres5ure to yield 3.3g of the required 2-~2,2-dichlorovinyl)-~,3-dimethylcyclo-propane nitrile (97X pure, 89% yield).
EXAMPLE VI Pre~ration of (A) in one reaction ves~el u8in~ N?N-diisopro ~l-N-eth~lamine a6 base -A solution of 4-chloro-2-cy~no-3,3~dimethyl-6,6,6-trichlorohexauoic acid (2.5g) and N,N-diisopropyl-N-ethylamine (206~) in dimethyl form~mide (25ml) wa~ he~ted At 14S C for 5 hours. After cooling to room temperature the reaction mixture wa~ worked up a8 indicated in Example III~
This yielded 1.4~ of the required 2-(212-dichlorovinyl~-3,~-dimethyl-cyclopropane nitrile with purity 79%. Yi~ld 73%.
After release of the pre6~ure the mixture was ~tirred for another 6 hour~ at 145 C. After cooling down over 90% of the ~olYent wa~
fla~hed off (bath tempera~ure max. 60C, pres6ure 12~ ). The residue wa6 mixed ~ith toluene, wa~hod ~ubsequently with aqueous hydrochloric acid and aqueou~ sodium bicarbonate~ After dryin~
of the organic pha~e the solvent wa~ Yamov~d under reduced pres5ure to yield 3.3g of the required 2-~2,2-dichlorovinyl)-~,3-dimethylcyclo-propane nitrile (97X pure, 89% yield).
EXAMPLE VI Pre~ration of (A) in one reaction ves~el u8in~ N?N-diisopro ~l-N-eth~lamine a6 base -A solution of 4-chloro-2-cy~no-3,3~dimethyl-6,6,6-trichlorohexauoic acid (2.5g) and N,N-diisopropyl-N-ethylamine (206~) in dimethyl form~mide (25ml) wa~ he~ted At 14S C for 5 hours. After cooling to room temperature the reaction mixture wa~ worked up a8 indicated in Example III~
This yielded 1.4~ of the required 2-(212-dichlorovinyl~-3,~-dimethyl-cyclopropane nitrile with purity 79%. Yi~ld 73%.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of cyano-substituted cyclopropane derivatives of general formula:- (II) (wherein Hal represents a fluorine, chlorine or bromine atom; and R1 and R2 each individually represents an alkyl group of 1 to 4 carbon atoms) which comprises:-(a) cyclizing and dehydrohalogenating a compound of general formula:- (III) (wherein X and Y each individually represents a chlorine or bromine atom;
and R4 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms) in the presence of a base; and (b) thermally decarboxylating the resulting cyclized and dehydrohalogenated product to form the compound of general formula II.
and R4 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms) in the presence of a base; and (b) thermally decarboxylating the resulting cyclized and dehydrohalogenated product to form the compound of general formula II.
2. A process according to claim 1 wherein step (a) is carried out at a temperature in the range 30° to 160°C.
3. A process according to claims 1 or 2 wherein step (a) is carried out in the presence of an inert non-aqueous solvent.
4. A process according to claim 1 wherein step (a) is carried out in the presence of a nitrogenous base, an alkali metal acetate, carbonate or bicarbonate.
5. A process according to claim 1 wherein step (a) is carried out in the presence of ammonia or sodium acetate.
6. A process according to claim 1 wherein step (b) is carried out at a temperature in the range 100°-150°C.
7. A process according to claim 1 wherein step (b) is carried out in the presence of an inert non-aqueous solvent.
8. A process according to claim 1 wherein step (a) and step (b) are carried out in one reaction zone or pot in the presence of a nitrogenous base and an inert non-aqueous solvent at a temperature in the range 70°-100°C.
9. A process according to claim 8 wherein the temperature range is 80° to 150°C.
10. A process according to claim 8 or 9 wherein the nitrogenous base is ammonia and the inert non-aqueous solvent is dimethyl formamide.
11. A process according to claim 1 or 8 which is carried out under substantially anhydrous conditions.
12. A process according to claim 1 or 8 wherein in the compounds of formulae II and III R1 and R2 are both methyl groups.
13. Compounds of the general formula:- wherein R1 and R2 each individually represents an alkyl group of 1 to 4 carbon atoms, Hal represents a fluorine, chlorine or bromine atom, Y is a chlorine or bromine atom, and R4 is a hydrogen or alkali metal or alkaline earth metal atom, an ammonium or quaternary ammonium group, or an alkyl group of 1 to 4 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB25896/76 | 1976-06-22 | ||
| GB2589676A GB1580203A (en) | 1976-06-22 | 1976-06-22 | Preparation of cyclopropane derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1123006A true CA1123006A (en) | 1982-05-04 |
Family
ID=10235120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,560A Expired CA1123006A (en) | 1976-06-22 | 1977-05-03 | Preparation of cyclopropane derivatives |
Country Status (11)
| Country | Link |
|---|---|
| JP (2) | JPS52156839A (en) |
| BE (1) | BE855691A (en) |
| BR (1) | BR7703975A (en) |
| CA (1) | CA1123006A (en) |
| CH (1) | CH629758A5 (en) |
| DE (1) | DE2727613A1 (en) |
| DK (1) | DK156955C (en) |
| FR (1) | FR2355811A1 (en) |
| GB (1) | GB1580203A (en) |
| IT (1) | IT1080226B (en) |
| NL (1) | NL7706755A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4853579A (en) * | 1978-07-18 | 1980-01-24 | Imperial Chemical Industries Limited | Preparation of unsaturated cyclic nitrile |
| FR2485004A1 (en) * | 1980-06-20 | 1981-12-24 | Roussel Uclaf | CYCLOPROPANE-1-CARBOXYLIC DERIVATIVES AND THEIR SALTS, THEIR PREPARATION AND THEIR APPLICATION TO THE SYNTHESIS OF INTERMEDIATES OF PYRETHRINOID COMPOUNDS OF CIS CONFIGURATION |
| DE3260178D1 (en) * | 1981-04-30 | 1984-06-28 | Shell Int Research | Process for the preparation of cyclopropane compounds |
| NL8203002A (en) * | 1981-08-06 | 1983-03-01 | Shell Int Research | STEREO-SPECIFIC DECARBOXYLATION OF DIHALOGENE VINYL CYCLOPROPANIC CARBONIC ACIDS. |
| GB2127012A (en) * | 1982-09-22 | 1984-04-04 | Shell Int Research | Process for the preparation of cyclopropane compounds |
-
1976
- 1976-06-22 GB GB2589676A patent/GB1580203A/en not_active Expired
-
1977
- 1977-05-03 CA CA277,560A patent/CA1123006A/en not_active Expired
- 1977-06-15 BE BE1008190A patent/BE855691A/en not_active IP Right Cessation
- 1977-06-20 IT IT2486677A patent/IT1080226B/en active
- 1977-06-20 FR FR7718843A patent/FR2355811A1/en active Granted
- 1977-06-20 CH CH752677A patent/CH629758A5/en not_active IP Right Cessation
- 1977-06-20 DK DK271877A patent/DK156955C/en not_active IP Right Cessation
- 1977-06-20 DE DE19772727613 patent/DE2727613A1/en active Granted
- 1977-06-20 NL NL7706755A patent/NL7706755A/en not_active Application Discontinuation
- 1977-06-20 BR BR7703975A patent/BR7703975A/en unknown
- 1977-06-20 JP JP7226277A patent/JPS52156839A/en active Granted
-
1986
- 1986-03-24 JP JP61064300A patent/JPS61233658A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61233658A (en) | 1986-10-17 |
| BE855691A (en) | 1977-12-15 |
| GB1580203A (en) | 1980-11-26 |
| JPS638100B2 (en) | 1988-02-19 |
| DK271877A (en) | 1977-12-23 |
| DE2727613A1 (en) | 1977-12-29 |
| DK156955C (en) | 1990-02-26 |
| IT1080226B (en) | 1985-05-16 |
| FR2355811A1 (en) | 1978-01-20 |
| BR7703975A (en) | 1978-04-25 |
| CH629758A5 (en) | 1982-05-14 |
| DK156955B (en) | 1989-10-23 |
| FR2355811B1 (en) | 1980-12-05 |
| NL7706755A (en) | 1977-12-27 |
| DE2727613C2 (en) | 1988-03-03 |
| JPS52156839A (en) | 1977-12-27 |
| JPS6140660B2 (en) | 1986-09-10 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |