CA1087204A - Preparation of 0-(1-alkoxycarbonyl-1-propen-2-yl)-phosphorohalidates - Google Patents
Preparation of 0-(1-alkoxycarbonyl-1-propen-2-yl)-phosphorohalidatesInfo
- Publication number
- CA1087204A CA1087204A CA286,137A CA286137A CA1087204A CA 1087204 A CA1087204 A CA 1087204A CA 286137 A CA286137 A CA 286137A CA 1087204 A CA1087204 A CA 1087204A
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- formula
- compound
- alkyl
- cis
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
Abstract
O-(1-ALKOXY CARBONYL-1-PROPEN-2-YL)-PHOSPHOROHALIDATES
Abstract of the Disclosure The present invention relates to a novel process for the production of thiophosphoric acid derivatives of the formula wherein R1 is C1-C5 alkyl X is H, C1 or Br Y1 is C1-C5 alkoxy, C1 or Br and Y2 is C1 or Br and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety.
The compounds of formula I are useful intermediates in the production of known insecticides.
Abstract of the Disclosure The present invention relates to a novel process for the production of thiophosphoric acid derivatives of the formula wherein R1 is C1-C5 alkyl X is H, C1 or Br Y1 is C1-C5 alkoxy, C1 or Br and Y2 is C1 or Br and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety.
The compounds of formula I are useful intermediates in the production of known insecticides.
Description
o ~ ~01~7204 O-(l-ALKOXY CARBONYL-l-PROPEN-2-YL)-PHOSPHOROHALIDATES
The present invention rélates to a process for the production of thiophosphoric acld derivatives.
. Accordlngly the pxesent invention provides a process for the production of acompound of formula I
.
p_o x ~ .
Y2 ~ ~ C - C ~
~ ~ '~
CH3 COORl ;
wherein Rl ls Cl-C5 alkyl, X is H, Cl or Br, Yl is Cl-C5 alkoxy, Cl or Br, and Y2 is Cl or Br~
and the -CH3 and -COORl radicals ~.
are Cis one to another in the crotonic acid moiety, which comprises condensing a compound of formula II
n CH3-c-cHx-cooRl II
wherein X and Rl are as defined above ~ .
'; ' r.
72~4 wlth a compound of formula III
: ~ P-Y3 III
wherein Yl and Y2 are as defined above~
and Y3 ls Cl or Br~
ln an aqueous organic two phase system, in the presence of an alkali and a catalytic amount of a phase transfer catalyst.
Appropriate phase transfer catalysts are quaternary ammonium and quaternary phosphonium compounds as well as crown ethers. Preferred are quaternary am~onlum and quaterna~y phosphonium compounds.
Preferred quaternary ammonium salts are tetra(Cl-C20)allkyl and benzyl tri(Cl-C20)alkyl ammonlum salts such as the sulphate, phosphate, benzene sulphonate, toluene sulphonate and part$cularly the hydrohalide salts such as the chloride~
bromide and iodide.
Specific examples of quaternary ammonium ~alts are benzyltrimethyl ammonium bromlde and , ~ ' `
.
10~7Z~4 hydroxide, benzyltriethyl ammonium bromide and chlorlde, benzyltributylammonium bromide, cetyltrlmethyl ammonium bromide, methyltributyl ammonium iodide, tetraethyl ammonium chloride, bromide, iodide and hydroxide, tricaprylylmethyl ammonium chloride, Centrimide- (trade mark) and tetrabutyl ammonium chloride, bromide, iodide, hydrogen sulphate and hydroxide.
Preferred quaternary phosphonium salts are tetraphenyl, triphenyl(Cl-C20)alkyl and tetra(Cl-C20) alkyl phosphonium salts such as the halide salts.
Specific examples of quaternary phosphonium salts are benzyltriphenyl phosphonium chloride and tetra-phenylphosphonium bromide and chloride.
Examples of crown ethers are 18-crown-6, 15-crown-5 and 12-crown-4.
Preferred alkalls are sodlum or potasslum hydroxlde especially when present in the aqueous phase ln amounts of 10-30% by weight~especially 15 to 25%
by weight.
The organic phase may comprise any appropriate inert water immisclble solvent such as halogenated hydrocarbons, e.g. O-dichloro benzene, methylene 1~ .
. ~ .
_ _ . _ .. _ . . . . . .. . _ ... . .
dlchlorlde, 1,2-dichloroethylene, trlchloroethylene, tetrachloroethylene and chloroform.
The reaction is preferably effected at a ~~
temperature in the range -10 to +25C., and particularly in the range -S to +5C.
The process enables the stereospecific synthesis of ~ompounds of formula I in high yield and in a high state of purity.
The compounds of formula I are useful known intermediates in the production of compounds of formula IV
S
R20 ~ n p-O X
3NH C=C IV
wherein Rl is Cl-C5 alkyl, X is H, Cl or Br, R is C -C alkyl and R3 is Cl-C5 alkyl~
and the -CH3 and -COORl radicals are Cis one to another in the crotonic acid moiety, . , . , .. . . . , . . _ . ..
The compounds of formula IV may be produced a) by condensing a compound o formula Ia
The present invention rélates to a process for the production of thiophosphoric acld derivatives.
. Accordlngly the pxesent invention provides a process for the production of acompound of formula I
.
p_o x ~ .
Y2 ~ ~ C - C ~
~ ~ '~
CH3 COORl ;
wherein Rl ls Cl-C5 alkyl, X is H, Cl or Br, Yl is Cl-C5 alkoxy, Cl or Br, and Y2 is Cl or Br~
and the -CH3 and -COORl radicals ~.
are Cis one to another in the crotonic acid moiety, which comprises condensing a compound of formula II
n CH3-c-cHx-cooRl II
wherein X and Rl are as defined above ~ .
'; ' r.
72~4 wlth a compound of formula III
: ~ P-Y3 III
wherein Yl and Y2 are as defined above~
and Y3 ls Cl or Br~
ln an aqueous organic two phase system, in the presence of an alkali and a catalytic amount of a phase transfer catalyst.
Appropriate phase transfer catalysts are quaternary ammonium and quaternary phosphonium compounds as well as crown ethers. Preferred are quaternary am~onlum and quaterna~y phosphonium compounds.
Preferred quaternary ammonium salts are tetra(Cl-C20)allkyl and benzyl tri(Cl-C20)alkyl ammonlum salts such as the sulphate, phosphate, benzene sulphonate, toluene sulphonate and part$cularly the hydrohalide salts such as the chloride~
bromide and iodide.
Specific examples of quaternary ammonium ~alts are benzyltrimethyl ammonium bromlde and , ~ ' `
.
10~7Z~4 hydroxide, benzyltriethyl ammonium bromide and chlorlde, benzyltributylammonium bromide, cetyltrlmethyl ammonium bromide, methyltributyl ammonium iodide, tetraethyl ammonium chloride, bromide, iodide and hydroxide, tricaprylylmethyl ammonium chloride, Centrimide- (trade mark) and tetrabutyl ammonium chloride, bromide, iodide, hydrogen sulphate and hydroxide.
Preferred quaternary phosphonium salts are tetraphenyl, triphenyl(Cl-C20)alkyl and tetra(Cl-C20) alkyl phosphonium salts such as the halide salts.
Specific examples of quaternary phosphonium salts are benzyltriphenyl phosphonium chloride and tetra-phenylphosphonium bromide and chloride.
Examples of crown ethers are 18-crown-6, 15-crown-5 and 12-crown-4.
Preferred alkalls are sodlum or potasslum hydroxlde especially when present in the aqueous phase ln amounts of 10-30% by weight~especially 15 to 25%
by weight.
The organic phase may comprise any appropriate inert water immisclble solvent such as halogenated hydrocarbons, e.g. O-dichloro benzene, methylene 1~ .
. ~ .
_ _ . _ .. _ . . . . . .. . _ ... . .
dlchlorlde, 1,2-dichloroethylene, trlchloroethylene, tetrachloroethylene and chloroform.
The reaction is preferably effected at a ~~
temperature in the range -10 to +25C., and particularly in the range -S to +5C.
The process enables the stereospecific synthesis of ~ompounds of formula I in high yield and in a high state of purity.
The compounds of formula I are useful known intermediates in the production of compounds of formula IV
S
R20 ~ n p-O X
3NH C=C IV
wherein Rl is Cl-C5 alkyl, X is H, Cl or Br, R is C -C alkyl and R3 is Cl-C5 alkyl~
and the -CH3 and -COORl radicals are Cis one to another in the crotonic acid moiety, . , . , .. . . . , . . _ . ..
The compounds of formula IV may be produced a) by condensing a compound o formula Ia
2 ~
p_o ~ X Ia y ~ C=C~
CH3 COOR~
wherein Rl, X, R2 and Y2 are as defined above, and the -CH3 and -COORl radicals are Cis one to another in the crotonic acid moiety, with a compound of formula V
p_o ~ X Ia y ~ C=C~
CH3 COOR~
wherein Rl, X, R2 and Y2 are as defined above, and the -CH3 and -COORl radicals are Cis one to another in the crotonic acid moiety, with a compound of formula V
3 H2 V
wherein R3 is as defined above, or b) by condensing a compound of formula Ib y~ S
1 ~ "
~ ~C=C ~ Ib 2 CH3 COORl wherein Y2, X and Rl are as defined above and Yi is Cl or Br ~72~4 130-3795 and the -CH3 and COORl radicals are Cis one to another in the crotonic acid moiety, with a compound of formula VI
wherein R2 ls as defined above and M ls H or an alkali metal or ammonium cation to produce a compound of formula I_ and then following the procedure of process a) above.
The compounds of formula IV are known useful insecticides.
The invention is illustrated by the following Examples wherein temperatures are expressed in C and parts are by weight.
10~72~4 . 130-3795 Example 1: cls_~l-carboiso~ro~oxy-1-~ro~en_2-ylL__ thiono~hos~horic acid dichloride 144.2 g (1 moll of acetoacetic acid i50-propylester are added at 0~ to a solution of 169.4 g (1 mol) of thiophosphoryl chloride in 1.2 1 of chloroform, and 22.8 g ~0.1 mol) of benzyltrlethyl-ammonium chloride are subfiequently added. A solution of 40 g of sodium hydroxide in 0.2 1 of water is added wlth vigorous stirring to the mlxture which is kept b at 0 and stirring is continued for 15 minutes at 0.
The chloroform phase is allowed to settle, then partiticned off in a separating funnel, washed with 0.2 1 of lce-cold water and dried over anhydrous sodium sulphate. After evaporating off the solvent in a vacuum on 21 rotary evaporator, the residue is subjected to high vacuum at 10 torr ~bath temperature soo ) .
The trans isomer could not be detected in the residue. The purity is tested by thin-layer ~4 chromatography on ~ilica gel plates, with n-hexaneJ
acetone (4:1) as the eluant, and the samples rendered visible by spraying with alkallne permanganate ,: - . .
10~720~ 130-37~5 solution. The Rf values of the title product and starting materials are as follows:
C~5~ - (1-carboisopropoxy-1-propen-2-yl)-thionophosphoric acid dichloride, Rf= 0.66 o ~ -bis-(l-carboisopropoxy l-propen-2yl)-thionophosphoric acid chlorlde Rf = 0.52 acetoacetic acid isopropylester Rf = 0.32 If an oily residue is obtalned after the solvent is evaporated off, it may be filtered through a filtering aid such as "Hyflo"*. The title compound which adheres to the "Hyflo"* may be washed out by txeat-ment with pet~oleu~ ether in whlch it is soluble.
ExamPle 2: cis~Q~ carboi_o~ro~ox~ roEen-2yl)-_ thiono~hos~horic acid dichloride ______ ___ _____________________ 19!; q (1.15 mols) of thionophosphoryl chloride are dissolved in 1.2 1 of chloroform. 22.8 g ~0.1 mols) of benzyltriethylammonium chloride are added with good stirriny to the solution which is kept constantly at -5, and 240 ml of 20% aqueous caustic soda (1.2 mols) are added over the course of 10 minutes in a sl~ghtly exothermic reaction. Immediately afterwards, 144.17 g (1 mol) of acetoacetic acid isopropylester are added *Trademark . - 9 -"~`'~1 .,~ , .
1~8720~ 130 3795 dropwise at -5 over the course of 30 minutes. Stirring take~ place for another l/4 hour at 0 and the procesa ls completed as descrlbed ln Example l. No trans compound can be detected.
The cis-o-(l-carboisopropoxy-l-propen-2-yl)-thionophosphoric acid dichloride produced in Examples l and 2 may be dlstilled if desired in a high vacuum at 43/5xlO mm; nD = 1.5078.
The cls and trans title compounds are distinguished by the NMR signals, primarily from the substituents on the vinylic double compound.
NMR ~, ppm in CDCl3) cis~ carboisopropoxy-l-propen-2-yl)-thionophosphoric , acid dichloride =CH 5.9 multiplet ; CH3C= 2.52 ppm t,, trans-0~ carboisopropoxy-l-propen-2-yl)-thionophosphoric w1d dichlorlde =CH 5.62 multlplet ; CH3C = 2.20 ppm.
.
~ - .
:, , 1~87ZC~4 130-3795 Example 3: cis-0~ carboiso~ro~oxy-1-~ro~en-2-yl)--methyl-thiono~hos~horic acid chloride _ _ _ _ _ _ _ _ _ _ _ _ 165 g (1 mol) of 0-methyl-thionophosphor$c ac$d dichloride are dissolved in 500 ml of chloroform.
57 g (0.25 mols) of benzyltriethylammonium chloride are added with stirring at 0 and 144 g (1 mol) of acetoacetic acid isopropylester are subsequently added with vigorous stirring at 0. 1 mol of 20% aqueous caustlc soda is subsequently added dropwise at the same ~;
temperature over the course of 1/2 hour, and the mixture is stirred for another 1/4 hour at 0. The chloroform phase is now separated off and washed for a short time in a separating funnel with 0.2 1 of ice-cold water.
After drying over sodium sulphate and evaporating off the solvent in a rotary evaporator under vacuum, the title compound is obtained. The purity of the product may be tested by gas chromatography.
The test with gas chromatography showed practically pure cis-0-(1-carboisopropoxy-1-propen-2yl)--methyl-thionophosphoric acid chloride.
The test for purity may also be effected by I thin-layer chromatography on silica gel plates, with .
.
n-hexane/acetone (4:1) as the eluant, the samples bein~ vislble by spraylng with alkaline permanganate ~olution.
The title compound may be distilled ln a high vacuum.
Bp. 67/0.05 mm, nD = 1.4926.
Example 4: cis~ -carboiso~ro~oxy~ ro~en-2-yl)-O-methyl-N-ethyl-thiono~hos~horic acid e~;teramide 0 405 ml (10 mols) of anhydrous methanol are cooled to about -5. 194.8 g (1.15 mols) of thiono-phosphoric acid chloride are then added and the mixture stlrred for about 10 minutes at 10. 1.2 1 of ice-cold water are added, the mixture is decanted from the o-methyl-thionophosphoric acid chloride which settles on the bottom, and washed twice, each tlmR with 120 ml of lce-cold water. ~he o-me~hyl-thionophosphoric acld dichloride thus obtained [165 g (1 mol)] is dissolved in 500 ml of chloroform. 57 g (0.25 mols) of benzyl-~o triethylammonium chloride are then added with stirring at 0, and 144 g (1 mol) of acetoacetic acid ., .
~ - 12 -.
b ~
} ~ . ' 10872~ 130-3795 isopropylester are subsequently added with vigorous stirring at 0. 1 mol of 20% a~ueous caustic soda is subsequently added dropwise at the same temperature over the course of 1/2 hour, and this is further stirred at 0 for 1/4 hour. Immediately afterwards, 129 g (2 mols) of ethylamine are added in the form of a 70% aqueous solution at -5 over the course of 1/4 hour. The mixture is stirred for another 1/2 hour at 0, thechloroform phase is then partitioned off in a separating funnel and washed once with 0.2 1 of water. After drying over sodium sulphate, the solvent is evaporated off on a rotary evaporator under a water jet vacuum. The residue is subjected to a temperature of 70 under a high vacuum (10 4 torr) for 1/2 hour. It is then treated with petroleum ether ~boiling range 100~125). The ether phase which contains the title compound is evaporated on a rotary evaporator under a water jet vacuum, and subsequently subjected to high vacuum for 1/2 hour.
The title con,pound is obtained in at least 90% purity. It can be distilled at 87-89/5 10 3 torr.
nD = 1.495 ... .
wherein R3 is as defined above, or b) by condensing a compound of formula Ib y~ S
1 ~ "
~ ~C=C ~ Ib 2 CH3 COORl wherein Y2, X and Rl are as defined above and Yi is Cl or Br ~72~4 130-3795 and the -CH3 and COORl radicals are Cis one to another in the crotonic acid moiety, with a compound of formula VI
wherein R2 ls as defined above and M ls H or an alkali metal or ammonium cation to produce a compound of formula I_ and then following the procedure of process a) above.
The compounds of formula IV are known useful insecticides.
The invention is illustrated by the following Examples wherein temperatures are expressed in C and parts are by weight.
10~72~4 . 130-3795 Example 1: cls_~l-carboiso~ro~oxy-1-~ro~en_2-ylL__ thiono~hos~horic acid dichloride 144.2 g (1 moll of acetoacetic acid i50-propylester are added at 0~ to a solution of 169.4 g (1 mol) of thiophosphoryl chloride in 1.2 1 of chloroform, and 22.8 g ~0.1 mol) of benzyltrlethyl-ammonium chloride are subfiequently added. A solution of 40 g of sodium hydroxide in 0.2 1 of water is added wlth vigorous stirring to the mlxture which is kept b at 0 and stirring is continued for 15 minutes at 0.
The chloroform phase is allowed to settle, then partiticned off in a separating funnel, washed with 0.2 1 of lce-cold water and dried over anhydrous sodium sulphate. After evaporating off the solvent in a vacuum on 21 rotary evaporator, the residue is subjected to high vacuum at 10 torr ~bath temperature soo ) .
The trans isomer could not be detected in the residue. The purity is tested by thin-layer ~4 chromatography on ~ilica gel plates, with n-hexaneJ
acetone (4:1) as the eluant, and the samples rendered visible by spraying with alkallne permanganate ,: - . .
10~720~ 130-37~5 solution. The Rf values of the title product and starting materials are as follows:
C~5~ - (1-carboisopropoxy-1-propen-2-yl)-thionophosphoric acid dichloride, Rf= 0.66 o ~ -bis-(l-carboisopropoxy l-propen-2yl)-thionophosphoric acid chlorlde Rf = 0.52 acetoacetic acid isopropylester Rf = 0.32 If an oily residue is obtalned after the solvent is evaporated off, it may be filtered through a filtering aid such as "Hyflo"*. The title compound which adheres to the "Hyflo"* may be washed out by txeat-ment with pet~oleu~ ether in whlch it is soluble.
ExamPle 2: cis~Q~ carboi_o~ro~ox~ roEen-2yl)-_ thiono~hos~horic acid dichloride ______ ___ _____________________ 19!; q (1.15 mols) of thionophosphoryl chloride are dissolved in 1.2 1 of chloroform. 22.8 g ~0.1 mols) of benzyltriethylammonium chloride are added with good stirriny to the solution which is kept constantly at -5, and 240 ml of 20% aqueous caustic soda (1.2 mols) are added over the course of 10 minutes in a sl~ghtly exothermic reaction. Immediately afterwards, 144.17 g (1 mol) of acetoacetic acid isopropylester are added *Trademark . - 9 -"~`'~1 .,~ , .
1~8720~ 130 3795 dropwise at -5 over the course of 30 minutes. Stirring take~ place for another l/4 hour at 0 and the procesa ls completed as descrlbed ln Example l. No trans compound can be detected.
The cis-o-(l-carboisopropoxy-l-propen-2-yl)-thionophosphoric acid dichloride produced in Examples l and 2 may be dlstilled if desired in a high vacuum at 43/5xlO mm; nD = 1.5078.
The cls and trans title compounds are distinguished by the NMR signals, primarily from the substituents on the vinylic double compound.
NMR ~, ppm in CDCl3) cis~ carboisopropoxy-l-propen-2-yl)-thionophosphoric , acid dichloride =CH 5.9 multiplet ; CH3C= 2.52 ppm t,, trans-0~ carboisopropoxy-l-propen-2-yl)-thionophosphoric w1d dichlorlde =CH 5.62 multlplet ; CH3C = 2.20 ppm.
.
~ - .
:, , 1~87ZC~4 130-3795 Example 3: cis-0~ carboiso~ro~oxy-1-~ro~en-2-yl)--methyl-thiono~hos~horic acid chloride _ _ _ _ _ _ _ _ _ _ _ _ 165 g (1 mol) of 0-methyl-thionophosphor$c ac$d dichloride are dissolved in 500 ml of chloroform.
57 g (0.25 mols) of benzyltriethylammonium chloride are added with stirring at 0 and 144 g (1 mol) of acetoacetic acid isopropylester are subsequently added with vigorous stirring at 0. 1 mol of 20% aqueous caustlc soda is subsequently added dropwise at the same ~;
temperature over the course of 1/2 hour, and the mixture is stirred for another 1/4 hour at 0. The chloroform phase is now separated off and washed for a short time in a separating funnel with 0.2 1 of ice-cold water.
After drying over sodium sulphate and evaporating off the solvent in a rotary evaporator under vacuum, the title compound is obtained. The purity of the product may be tested by gas chromatography.
The test with gas chromatography showed practically pure cis-0-(1-carboisopropoxy-1-propen-2yl)--methyl-thionophosphoric acid chloride.
The test for purity may also be effected by I thin-layer chromatography on silica gel plates, with .
.
n-hexane/acetone (4:1) as the eluant, the samples bein~ vislble by spraylng with alkaline permanganate ~olution.
The title compound may be distilled ln a high vacuum.
Bp. 67/0.05 mm, nD = 1.4926.
Example 4: cis~ -carboiso~ro~oxy~ ro~en-2-yl)-O-methyl-N-ethyl-thiono~hos~horic acid e~;teramide 0 405 ml (10 mols) of anhydrous methanol are cooled to about -5. 194.8 g (1.15 mols) of thiono-phosphoric acid chloride are then added and the mixture stlrred for about 10 minutes at 10. 1.2 1 of ice-cold water are added, the mixture is decanted from the o-methyl-thionophosphoric acid chloride which settles on the bottom, and washed twice, each tlmR with 120 ml of lce-cold water. ~he o-me~hyl-thionophosphoric acld dichloride thus obtained [165 g (1 mol)] is dissolved in 500 ml of chloroform. 57 g (0.25 mols) of benzyl-~o triethylammonium chloride are then added with stirring at 0, and 144 g (1 mol) of acetoacetic acid ., .
~ - 12 -.
b ~
} ~ . ' 10872~ 130-3795 isopropylester are subsequently added with vigorous stirring at 0. 1 mol of 20% a~ueous caustic soda is subsequently added dropwise at the same temperature over the course of 1/2 hour, and this is further stirred at 0 for 1/4 hour. Immediately afterwards, 129 g (2 mols) of ethylamine are added in the form of a 70% aqueous solution at -5 over the course of 1/4 hour. The mixture is stirred for another 1/2 hour at 0, thechloroform phase is then partitioned off in a separating funnel and washed once with 0.2 1 of water. After drying over sodium sulphate, the solvent is evaporated off on a rotary evaporator under a water jet vacuum. The residue is subjected to a temperature of 70 under a high vacuum (10 4 torr) for 1/2 hour. It is then treated with petroleum ether ~boiling range 100~125). The ether phase which contains the title compound is evaporated on a rotary evaporator under a water jet vacuum, and subsequently subjected to high vacuum for 1/2 hour.
The title con,pound is obtained in at least 90% purity. It can be distilled at 87-89/5 10 3 torr.
nD = 1.495 ... .
Claims (5)
1. A process for the production of a compound of formula I
I
wherein R1 is C1-C5 alkyl, X is H, C1 or Br, Y1 is C1-C5 alkoxy, C1 or Br, and Y2 is C1 or Br, and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety, which comprises condensing a compound of formula II
II
wherein X and R1 are as defined above, with a compound of formula III
III
wherein Y1 and Y2 are as defined above and Y3 is C1 or Br, in an aqueous organic two phase system, in the presence of an alkali and a catalytic amount of a phase transfer catalyst.
I
wherein R1 is C1-C5 alkyl, X is H, C1 or Br, Y1 is C1-C5 alkoxy, C1 or Br, and Y2 is C1 or Br, and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety, which comprises condensing a compound of formula II
II
wherein X and R1 are as defined above, with a compound of formula III
III
wherein Y1 and Y2 are as defined above and Y3 is C1 or Br, in an aqueous organic two phase system, in the presence of an alkali and a catalytic amount of a phase transfer catalyst.
2. A process according to claim 1 wherein the phase transfer catalyst is a quaternary ammonium or quaternary phosphonium catalyst.
3. A process according to claim 2 wherein the phase transfer catalyst is a tetra(C1-C20)alkyl or benzyltri(C1-C20)alkyl quaternary ammonium salt.
4. A process according to claim 1, 2 or 3 when effected at a temperature in the range -10 to +25°C.
5. A process for the production of a compound of formula IV
IV
wherein R1 and X are as defined in Claim 1, R2 is C1-C5 alkyl and R3 is C1-C5 alkyl.
and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety comprising the step of producing, as an intermediate, a compound of formula I as defined in claim 1 in accordance with the process of claim 1, and converting it consequently to a compound of formula IV
a) by condensing a compound of formula Ia Ia wherein R1, X, R2 and Y2 are as defined above, and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety, with a compound of formula V
wherein R3 is as defined above, or b) by condensing a compound of formula Ib Ib wherein Y2, X and R1 are as defined above, and Y? is C1 or Br, and the -CH3 and COOR1 radicals are Cis one to another in the crotonic acid moiety, with a compound of formula VI
wherein R2 is as defined above, and M is H or an alkali metal or ammonium cation, to produce a compound of formula Ia ;
and then following the procedure of process a) above.
IV
wherein R1 and X are as defined in Claim 1, R2 is C1-C5 alkyl and R3 is C1-C5 alkyl.
and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety comprising the step of producing, as an intermediate, a compound of formula I as defined in claim 1 in accordance with the process of claim 1, and converting it consequently to a compound of formula IV
a) by condensing a compound of formula Ia Ia wherein R1, X, R2 and Y2 are as defined above, and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety, with a compound of formula V
wherein R3 is as defined above, or b) by condensing a compound of formula Ib Ib wherein Y2, X and R1 are as defined above, and Y? is C1 or Br, and the -CH3 and COOR1 radicals are Cis one to another in the crotonic acid moiety, with a compound of formula VI
wherein R2 is as defined above, and M is H or an alkali metal or ammonium cation, to produce a compound of formula Ia ;
and then following the procedure of process a) above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH11387/76 | 1976-09-08 | ||
| CH1138776A CH623593A5 (en) | 1976-09-08 | 1976-09-08 | Process for the preparation of vinylthionophosphoryl halides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087204A true CA1087204A (en) | 1980-10-07 |
Family
ID=4373027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA286,137A Expired CA1087204A (en) | 1976-09-08 | 1977-09-06 | Preparation of 0-(1-alkoxycarbonyl-1-propen-2-yl)-phosphorohalidates |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE858435A (en) |
| CA (1) | CA1087204A (en) |
| CH (1) | CH623593A5 (en) |
-
1976
- 1976-09-08 CH CH1138776A patent/CH623593A5/en not_active IP Right Cessation
-
1977
- 1977-09-06 BE BE180697A patent/BE858435A/en not_active IP Right Cessation
- 1977-09-06 CA CA286,137A patent/CA1087204A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH623593A5 (en) | 1981-06-15 |
| BE858435A (en) | 1978-03-06 |
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| MKEX | Expiry |