GB1587913A - Process for the production of unsaturated thiophosphate esters and ester amides - Google Patents

Process for the production of unsaturated thiophosphate esters and ester amides Download PDF

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GB1587913A
GB1587913A GB3633777A GB3633777A GB1587913A GB 1587913 A GB1587913 A GB 1587913A GB 3633777 A GB3633777 A GB 3633777A GB 3633777 A GB3633777 A GB 3633777A GB 1587913 A GB1587913 A GB 1587913A
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compound
formula
cis
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mol
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Sandoz AG
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Sandoz AG
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Priority claimed from CH1138776A external-priority patent/CH623593A5/en
Priority claimed from CH1138976A external-priority patent/CH636360A5/en
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    • 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

Description

(54) PROCESS FOR THE PRODUCTION OF UNSATURATED THIOPHOSPHATE ESTERS AND ESTER AMIDES (71) We, SANDOZ LTD., of 35 Lichtstrasse, 4002 Basle, Switzerland, a Swiss Body Corporate, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a process for the production of thiophosphoric acid derivatives.
Accordingly the present invention provides a process for the production of a compound of formula I
wherein R1 is C1-C5 alkyl Xis H. Cl or Br Y is C ,-Ch alkoxy. Cl or Br and Y2 is Cl or Br and the -CHa and -COOR1 radicals are Cis one to another in the crotonic acid moiety which comprises condensing a compound of formula II
wherein X and R1 are as defined above with a compound of formula III
wherein Y and Y, are as defined above and Y3 is Cl or Br in 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 ammonium and quaternary phosphonium compounds.
Preferred quaternary ammonium salts are tetra (C1-C20) alkyl and benzyl tri(C1-C20)alkyl ammonium salts such as the sulphate, phosphate, benzene sulphonate, toluene sulphonate and particularly the hydrohalide salts such as the chloride bromide and iodide.
Specific examples of quaternary ammonium salts are benzyltrimethyl ammonium bromide.
and hydroxide, benzyltriethyl ammonium bromide and chloride, benzyltributylammonium bromide, cetyltrimethyl ammonium bromide, methyltributyl ammonium iodide, tetraethyl ammonium chloride, bromide, iodide and hydroxide, tricaprylylmethyl ammonium chloride, cetrimide (registered trade mark; a cetyl trimethylammonium bromide) and tetrabutyl ammonium chloride, bromide, iodide, hydrogen sulphate and hydroxide.
Preferred quaternary phosphonium salts are tetraphenyl, triphenyl (Cl-C20) alkyl and tetra (C1-C20) alkyl phosphonium salts such as the halide salts.
Specific examples of quaternary phosphonium salts are benzyltriphenyl phosphonium chloride and tetraphenylphosphonium bromide and chloride.
Examples of crown ethers are 18-crown-6, 15-crown-5 and 12-crown-4.
Preferred alkalis are sodium or potassium hydroxide especially when present in the aqueous phase in amounts of 10-30% by weight especially 15 to 25 % by weight.
The organic phase may comprise any appropriate inert water-immiscible solvent such as halogenated hydrocarbons, e.g. 0-dichloro benzene, methylene dichloride, 1,2dichloroethylene, trichloroethylene, tctrachloroethylene and chloroform.
The reaction is preferably effected at a temperature in therange-10 to +25 Cparticularly in the range -5 to + 5"C.
The process enables the stereospecific synthesis of compounds 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
wherein R1 and X are as defined above R2 is Cl-C54 alkyl and R3 is Ct-C5 alkyl.
and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety.
The compounds of formula IV may be produced (a) by condensing a compound of formula Ia
wherein R,. 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 RlNH2 V wherein Rl is as defined above.
or (b) by condensing a compound of formula Ib
wherein Y2, X and R1 are as defined above and it is Cl orBr and the -CH3 and COOR1 radicals are Cis one to another in the crotonic acid moiety, with a compound of formula VI R2OM 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.
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.
Example 1: cis- O-(1 carboisopropoxy- 1 -propen-2-yl) -thionophosphoric acid chloride 144.2 g (1 mol) of acetoacetic acid isopropylester 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 benzyltriethylammonium chloride are subsequently added. A solution of 40 g of sodium hydroxide in 0.2 1 of water is added with vigorous stirring to the mixture which is kept at 0 and stirring is continued for 15 minutes at 0 . The chloroform phase is allowed to settle, then partitioned off in a separating funnel, washed with 0.2 1 of ice-cold water and dried over anhydrous sodium sulphate. After evaporating off the solvent in a vacuum on a rotary evaporator, the residue is subjected to high vacuum at 10-4 torr (bath temperature 50 ).
The trans isomer could not be detected in the residue. The purity is tested by thin-layer chromatography on silica gel plates, with n-hexane/acetone (4:1) as the eluant, and the samples rendered visible by spraying with alkaline permanganate solution. The Rf values of the title product and starting materials are as follows: cis-0-(1-carboisopropoxy-1-propen-2-yl)-thionophosphoric acid dichloride, Rf = 0.66 acetoacetic acid isopropylester Rf = 0.32 If an oily residue is obtained after the solvent is evaporated off, it may be filtered through a filtering aid such as Hyflo (registered trade mark; a silicagel). The title compound which adheres to the Hyflo may be washed out by treatment with petroleum ether in which it is soluble.
Example 2: cis-O-(I - carb oisoprop oxy- 1-propen-2yl) -thionophosphoric acid chloride 195 g (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 stirring 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 slightly exothermic reaction. Immediately afterwards, 144.17 g (1 mol) of acetoacetic acid isopropylester are added dropwise at -5 over the course of 30 minutes. Stirring takes place for another 1/4 hour at 0 and the process is completed as described in Example 1. No trans compound can be detected.
The cis-0-( 1 -carboisopropoxy- 1 -propen-2-yl)-thionophosphoric acid dichloride produced in Examples land 2 may be distilled if desired in a high vacuum at 43 /5 x 10 mum; nD = 1.5078.
The cis and trans title compounds are distinguished by the NMR signals, primarily from the substituents on the vinylic double compounds.
NMR (8, ppm in CDC13) cis-0-( I -carboisopropoxy- t -propen-2-yl)-thionophosphoric acid dichloride = CH 5.9 multiplett; CH3C = 2.52 ppm trans-0-) 1 -carboisopropoxy- 1 -propen-2-yl)-thionophosphoric acid dichloride = CH 5.62 multiplett; CH3C = 2.20ppm.
Example 3: cis- O-( 1 -carboisoprnpoxy-' 1-propen-2-yl) - O-methyl-thionophosphoric acid chloride 165 g (1 mol) of 0-methyl-thionophosphoric acid 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 00. 1 mol of 20% aqueous caustic 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 00. 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)-0-methyl-thionophosphoric acid chloride.
The test for purity may also be effected by thin-layer chromatography on silica gel plates, with n-hexane/ acetone (4: 1) as the eluant, the samples being visible by spraying with alkaline permanganate solution.
The title compound may be distilled in a high vacuum.
Bp.670/0.05mm, = 1.4926.
Example 4: cis-O-(1 -carboisopropoxy- 1-propen-2-yl) - O-methyl-N-ethyl-thionophosphoric acid esteramide 405 ml (10 mols) of anhydrous methanol are cooled to about -5 . 194.8 g (1.15 mols) of thionophosphoric acid trichloride are then added and the mixture stirred for about 10 minutes at 10 . 1.2 1 of ice-cold water are added, the mixture is decanted from the desired 0-methyl-thionophosphoric acid dichloride which settles on the bottom, and the desired dichloride product washed twice, each time with 120 ml of ice-cold water. The 0-methyl thionophosphoric acid dichloride thus obtained [165 g (1 mol)] is dissolved in 500 ml of chloroform. 57 g (0.25 mols) of benzyl-triethylammonium chloride are then added with stirring at 0 , and 144 g (1 mol) of acetoacetic acid isopropylester are subsequently added with vigorous stirring at 00. 1 mol of 20% aqueous 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 , the chloroform phase is then partitioned off in a separating funnel and washed once with 0.21 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 compound is obtained in at least 90% purity. It can be distilled at 87-890/5 10-3 torr. %20 = 1.495 WHAT WE CLAIM IS: I. A process for the production of a compound of formula I
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (8)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    substituents on the vinylic double compounds.
    NMR (8, ppm in CDC13) cis-0-( I -carboisopropoxy- t -propen-2-yl)-thionophosphoric acid dichloride = CH 5.9 multiplett; CH3C = 2.52 ppm trans-0-) 1 -carboisopropoxy- 1 -propen-2-yl)-thionophosphoric acid dichloride = CH 5.62 multiplett; CH3C = 2.20ppm.
    Example 3: cis- O-( 1 -carboisoprnpoxy-' 1-propen-2-yl) - O-methyl-thionophosphoric acid chloride
    165 g (1 mol) of 0-methyl-thionophosphoric acid 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 00. 1 mol of 20% aqueous caustic 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 00. 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)-0-methyl-thionophosphoric acid chloride.
    The test for purity may also be effected by thin-layer chromatography on silica gel plates, with n-hexane/ acetone (4: 1) as the eluant, the samples being visible by spraying with alkaline permanganate solution.
    The title compound may be distilled in a high vacuum.
    Bp.670/0.05mm, = 1.4926.
    Example 4: cis-O-(1 -carboisopropoxy- 1-propen-2-yl) - O-methyl-N-ethyl-thionophosphoric acid esteramide
    405 ml (10 mols) of anhydrous methanol are cooled to about -5 . 194.8 g (1.15 mols) of thionophosphoric acid trichloride are then added and the mixture stirred for about 10 minutes at 10 . 1.2 1 of ice-cold water are added, the mixture is decanted from the desired 0-methyl-thionophosphoric acid dichloride which settles on the bottom, and the desired dichloride product washed twice, each time with 120 ml of ice-cold water. The 0-methyl thionophosphoric acid dichloride thus obtained [165 g (1 mol)] is dissolved in 500 ml of chloroform. 57 g (0.25 mols) of benzyl-triethylammonium chloride are then added with stirring at 0 , and 144 g (1 mol) of acetoacetic acid isopropylester are subsequently added with vigorous stirring at 00. 1 mol of 20% aqueous 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 , the chloroform phase is then partitioned off in a separating funnel and washed once with 0.21 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 compound is obtained in at least 90% purity. It can be distilled at 87-890/5 10-3 torr. %20 = 1.495 WHAT WE CLAIM IS: I. A process for the production of a compound of formula I
    wherein R1 is C1-C5 alkyl Xis H, Cl or Br Y1 is C-C5 alkoxy, Cl or Br and Y2 is Cl 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
    wherein X and R1 are as defined above with a compound of formula III
    wherein Y andY2 are as defined above andY3 is Cl orBr in an aqueous organic two phase system, in the presence of an alkali and a catalytic amount of a phase transfer catalyst.
  2. 2. A process according to claim 1 wherein the phase transfer catalyst is a quaternary ammonium or quaternary phosphonium compound.
  3. 3. A process according to claim 2 wherein the phase transfer catalyst is a tetra (C,-C20) alkyl or benzyltri(C1-C20)alkyl quaternary ammonium salt.
  4. 4. A process according to any one of the preceding claims when effected at a temperature intherange-lOto +25 C.
  5. 5. A process according to claim 1 substantially as described herein with reference to the Examples.
  6. 6. A compound of formula I whenever produced by the process of any one of the preceding claims.
  7. 7. A process for the production of a compound of formula 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 using as an intermediate, a compound of formula I when prepared in accordance with any one of Claims 1 to 5 and converting it consequently to a compound of formula IV a) by condensing a compound of formula Ia
    wherein R1, X, R2 areas defined above and Y2 is as defined in claim 1, and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety, with a compound of formula V R3NH2 V wherein R3 is as defined above, orb) by condensing a compound of formula Ib
    wherein Y2. X and Rt as defined above andY1 is Cl or Br and the -CH3 and -COOR1 radicals are Cis one to another in the crotonic acid moiety, wqith a compound of formula VI R2OM 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.
  8. 8. A compound of formula IV whenever produced by the process of Claim 7.
    Reference has been directed in pursuance of section 9, subsection (1) of the Patents Act 1949, to patent No. 1,262,760.
GB3633777A 1976-09-08 1977-08-31 Process for the production of unsaturated thiophosphate esters and ester amides Expired GB1587913A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1138776A CH623593A5 (en) 1976-09-08 1976-09-08 Process for the preparation of vinylthionophosphoryl halides
CH1138976A CH636360A5 (en) 1976-09-08 1976-09-08 Process for the preparation of vinylthionophosphoric acid esters

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GB1587913A true GB1587913A (en) 1981-04-15

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BR (1) BR7705950A (en)
DE (1) DE2739310A1 (en)
DK (1) DK144190C (en)
ES (1) ES462188A1 (en)
FR (1) FR2364222A1 (en)
GB (1) GB1587913A (en)
IE (1) IE45582B1 (en)
IT (1) IT1091117B (en)
NL (1) NL7709690A (en)
PL (1) PL109053B1 (en)
SU (1) SU676167A3 (en)

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CN112645977A (en) * 2020-12-23 2021-04-13 天津阿尔塔科技有限公司 Synthesis method of de-isopropylaminophos

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DE737270C (en) * 1941-02-18 1943-07-09 Hauhinco Maschf Impact tool
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DK390577A (en) 1978-03-09
DE2739310C2 (en) 1988-08-25
DK144190B (en) 1982-01-11
JPS6143359B2 (en) 1986-09-26
IT1091117B (en) 1985-06-26
SU676167A3 (en) 1979-07-25
ES462188A1 (en) 1980-12-16
DK144190C (en) 1982-06-14
JPS5334728A (en) 1978-03-31
FR2364222A1 (en) 1978-04-07
PL109053B1 (en) 1980-05-31
PL200711A1 (en) 1978-10-23
IE45582L (en) 1978-03-08
BR7705950A (en) 1978-06-27
FR2364222B1 (en) 1984-05-11
DE2739310A1 (en) 1978-03-09
NL7709690A (en) 1978-03-10
IE45582B1 (en) 1982-10-06

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Effective date: 19970830