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US2938919A - Thiophosphoric acid esters and a process for their manufacture - Google Patents

Thiophosphoric acid esters and a process for their manufacture Download PDF

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US2938919A
US2938919A US789259A US78925959A US2938919A US 2938919 A US2938919 A US 2938919A US 789259 A US789259 A US 789259A US 78925959 A US78925959 A US 78925959A US 2938919 A US2938919 A US 2938919A
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ester
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acid
following formula
thiophosphoric acid
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Lorenz Walter
Schrader Gerhard
Dorken August
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Bayer AG
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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 Table
    • 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
    • C07F9/1653—Esters of thiophosphoric acids with arylalkanols

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  • alkyl mercapto compounds furthermore may be oxidizedby known methods to the corresponding sulfoxides or sulfones.
  • The. first may be obtained by oxidizing the sulfides in glacial acetic acid with molar amounts of hydrogen peroxide at lower temperatures, whereas the sulfones are obtained by using an excessof hydrogen peroxide (at least 2 mols) at higher temperatures.
  • the oxidation may also be carried out after the condensation with the 1-alkyl-mercapto-phenyl-thiophosphoric acid esters has taken place.
  • Suitable inert solvents in the sense of this invention are e.g. lower aliphatic alcohols, such as methanol or ethanol, lower aliphatic ketones, such as acetone or methylethyl ketone, or aromatic hy'-- drocarbons, such as benzene, toluene, and the like.
  • salts of the 0.0-dialkylthiolor -thionothiolphosphoric acids which are especially suitable for the inventive re-- action, there may be named the alkali metal salts or antmoniurn salts.
  • alkali metal salts or antmoniurn salts As halomethyl-(alkyl)-phenylthio ethers- (or their corresponding sulfoxides or sulfones), especial-- ly the chloromethyl compounds may be used.
  • the compounds of the present invention are generally valuable insecticides and plant-protecting agents. They kill pests such as aphids, flies and mites and exhibit a: very remarkable systemic action. They are especially valuable contact insecticides with a remarkably low toxicity against mammals.
  • the special advantage of the inventive compounds consists also in their acaricidal activity and in that they are especially active against the eggs of red mites.
  • the application of these compounds should be carried out according to the use of other known phosphorous insecticides, i.e. in dilution or solution with solid or liquid carriers,.such as chalk, talc, bentonite, water, alcohols, liquid hydrocarbons, etc.
  • the inventive compounds may further be used in combination with other known insecticides or pesticides, etc. Effective concentrations of the compounds may vary also; generally concentrations of 0. 0001% to 1.0% kill pests effectively.
  • the combinations of the compounds may be sprayed or dusted or otherwise brought in contact with pests or plants to be protected. They may
  • the above ester is mixed with the same amount of dimethyl formamide; to this solution 50% by weight of a commercial emulsifier consisting of a benzyl hydroxy diphenyl polyglycol ether is added.
  • Example 4 40 grams of the ammonium salt of 0.0-diethylthiolphosphoric acid are di Sfllved in 150 ccm. of methylethyl ketone. There is added at a temperature of about 30 C. asolutio'n 'of 44 grams of the sulfone of the following formula dissolved in 100 ccm. methylethyl ketone:
  • the above shown sulfone may be prepared as follows: 95 grams of 2-chloromethyll-methylthio-anisol are dissolved in 240 m1. of glacial acetic acid. At a temperature of 50 C. there are added 250 ml. of hydrogen peroxide (concentration 35%) within minutes. The reaction is completed by standing for another hour and half a 5 6 Wh le cool n the u furic ys z and may be recrystallized (if necessary) from benzene; M.P. 84 C.
  • Example 5 SO-OH
  • the reaction mixture is kept for 5 hours at a temperature of 60 C. and then it is worked up in the usual manner. There 'are obtained 73 grams of the new ester of the following formula SCL-CH: G H O l CH;
  • the new ester- shows a medium toxicity of 1000 mg./kg.
  • the above shown sulfoxide may be prepared as follows: grams of 2-chloro-methyl-4-methyl-thioanisol are dissolved in 240 ml. of glacial acetic acid. At 0 C. there are added within 1 hour ml. of hydrogen peroxide (concentration 35%). The reaction is completed within 2 /2 hours and the acetic acid and water is distilled ofif in vacuum. The sulfoxide remains as an oil and is pure enough for being further reacted according to the above example.
  • Example 6 0 coin.
  • Example 7 30.5 grams (0.2 mol) of 4- methylmercaptorbenzylchloride are added dropwise to a solution of 44 (0.22 mol) of diethyl-thionothiol-phosphoric acid ammonium salt in 100 ccmhof acetone starting at a temperature of 20 C. After the slightly exothermic reaction subsides, the solution is heated to 5060 C. for one hour, the reaction product is then poured into water, the oil is taken up in benzene, washed and dried. By distillation 56 grams of thionot hiolphosphoric acid-Q0- die thyI-S-A-methyImercapto-benzyl ester of B.P. 125 C./ 0.01 mm..Hg are obtained in the form of a pale yellow, almost colorless oil. Yield: 87% of the theoretical.
  • Example 8 omso-Q-orn-s- 30.6 grams of the ester obtained according to Example 6 are dissolved in 75. ccm. of methanol and treated with 0.5 ccm. of 50% sulfuric acid. The calculated amount of a high-percent hydrogen peroxide is added dropwise with cooling at 40-50 C., the solution is stirred for one hour during which it cools.
  • the toxicity (LD of the ester lies between to mg./kg. on rats per es. With concentrations of 1:100.000 spider mites and their eggs are completely killed. 7
  • Example 11 S 0Ct 1l OClHrl 56 grams of ammonium diisopropyl-thinothiol-phosphate are dissolvedin 15 0 ccm. of acetone, and grams of p-methylmercapto-benzyl chloride of B.P. 59 C./ 0.01 mm. Hg are added dropwise at C. Working up is carried out as indicated in Example 10. 66 grams of the new ester are obtained in the form of a pale yellow oil which is clear soluble in cyclohexane. Yield: 99% of the theoretical.
  • a thiophosphoric acid ester of the following formula INC/O R1 3.
  • a thiophosphoric acid ester of the following formula 5 0 0,11, ems-Q0 H,--si
  • cmso-Q-cmw-K 9 10.
  • a thiophosphoric acid ester of the following formula S O 01H; OH SOQGHQ-S 1 12.
  • Patent should read a s corrected belo or appears in the printed specification ng correction and that the said Letters Column 3, lines 25 to 31 the formula should appear as shown below instead of as in the patent:

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Description

United States Patent THIOPHOSPHQR C ACID ESTERS AND A PROCESS FOR THEIR MANUFACTURE Walter Lorenz, Wuppertal-Vohwinkel, Gerhard Schrader,
Wuppertal-Cronenberg, and August Dorken, Wuppertal-Sonnborn, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverknsen, Germany, a coriteration of Germany No Drawing. Filed Jan. 27, 1959, Ser. No. 789,259 Claims priority, application Germany July 10, 1956 14 Claims. (Cl. 260-461) This invention relates to and has as its objects new and useful thiophosphonic acid esters and their production. Generally the new inventive esters may be repre sented by the following formula wherein R, R and R stand for alkyl radicals, R stands for hydrogen or an alkyl radical, the alkyl radicals being especially lower alkyl radicals containing 1 to 4 carbon atoms, z stands for zero or a whole number up to two, and the group CEh-HaH-MeS- -------9 S (O) (Oh-S-R CHr-S-P +MeHai a The starting materials, if they are 1-alkyl-mercapto-2- halomethyl-4-alkylbenzenes are easily obtainable from the corresponding 1-alkyl-mercapto-4alkylbenzenes with formaldehyde and hydrochloric acid as it is described e.g-. in, the German patent specification No. 569,569. Thesealkyl mercapto compounds furthermore may be oxidizedby known methods to the corresponding sulfoxides or sulfones. The. first may be obtained by oxidizing the sulfides in glacial acetic acid with molar amounts of hydrogen peroxide at lower temperatures, whereas the sulfones are obtained by using an excessof hydrogen peroxide (at least 2 mols) at higher temperatures. The oxidation may also be carried out after the condensation with the 1-alkyl-mercapto-phenyl-thiophosphoric acid esters has taken place.
2,938,919 Patented May 31, 1960 thiolphosphates and the alkyl-mercapto-( or alkyl-sulfoxylor alkyl-sulfonyl-)-halomethyl-(alkyl)=benzenes preferably may be carried out at slightly elevated temperatures, say between about 20 and C. and in the presence of an inert solvent. Suitable inert solvents in the sense of this invention are e.g. lower aliphatic alcohols, such as methanol or ethanol, lower aliphatic ketones, such as acetone or methylethyl ketone, or aromatic hy'-- drocarbons, such as benzene, toluene, and the like. As salts of the 0.0-dialkylthiolor -thionothiolphosphoric acids which are especially suitable for the inventive re-- action, there may be named the alkali metal salts or antmoniurn salts. As halomethyl-(alkyl)-phenylthio ethers- (or their corresponding sulfoxides or sulfones), especial-- ly the chloromethyl compounds may be used.
The compounds of the present invention are generally valuable insecticides and plant-protecting agents. They kill pests such as aphids, flies and mites and exhibit a: very remarkable systemic action. They are especially valuable contact insecticides with a remarkably low toxicity against mammals. The special advantage of the inventive compounds consists also in their acaricidal activity and in that they are especially active against the eggs of red mites. The application of these compounds should be carried out according to the use of other known phosphorous insecticides, i.e. in dilution or solution with solid or liquid carriers,.such as chalk, talc, bentonite, water, alcohols, liquid hydrocarbons, etc. The inventive compounds may further be used in combination with other known insecticides or pesticides, etc. Effective concentrations of the compounds may vary also; generally concentrations of 0. 0001% to 1.0% kill pests effectively. The combinations of the compounds may be sprayed or dusted or otherwise brought in contact with pests or plants to be protected. They may also be used as aerosols.
As a special example for the utility of the inventive compounds the QO-diisopropyl-S [2- (meth'yl-mereapto) 4-tmethylpheny1-( 1)l-methyl-dithiophosphate of the following formula (CHs):-CHO fi P-S-CH (OHM-GEO has been tested against black bean aphids, and the toxicity has been determined on rats orally. The above ester is mixed with the same amount of dimethyl formamide; to this solution 50% by weight of a commercial emulsifier consisting of a benzyl hydroxy diphenyl polyglycol ether is added. This mixture is diluted with water to an emul-- sion containing 0.01% of active ingredient, and that com-- position kills black bean aphids completely when in-- fected plants are sprayed with this solution. Poisoned. baits when fed to rats are well tolerated up to an amount: of 1 g. active ingredient per kg. animal.
The activity of the-following compound was tested on dwarf zbeans (Phaseolus vulgaris). Plants,-
;- heavily infested withspider mites of the type Tetranychus' aithae Hanst. were sprayed to the run ofl with aqueous emulsions prepared as described above. After 48 hours' Example 1 58 grams of the ammonium salt of 0.0-diethylthiolphosphoric acid are dissolved in 200 com. of methylethyl ketone. At a temperature of about 40 C., 58 grams of 4-methyl-2-chloromethyl-thioanisol in 50 com. methylethyl ketone are added while stirring. The reaction product is kept at a temperature of about 75 C. for 75 minutes while stirring. Then it is cooled and the ammonium chloride is filtered off with suction. The solvent is removed by distillation in vacuo. The residue is taken up in ether, washed with water and the etherical solution is dried over sodium sulfate. There are obtained 87 grams of the new ester of the formula S--CH| CaHsO S P-B-CH1 CHIO At a pressure of 0.01 mm. the new ester distills at a temperature of about 144 C.
The new ester shows a medium toxicity of about 100 mg./kg. on rats orally. Spider mites are killed completely at concentrations of 0.01%
By exactly the same procedure but using instead of the ammonium salt of 0.0-diethylthiol-phosphoric acid, the corresponding amount of the ammonium salts of 0.0-dimethylor 0.0-diisopropyl-thiolphosphoric acid, and instead of the '4-methyl-2-chloro-methylthioanisol, also exactly the corresponding molecular amount of 4-ethyl- 2-chloro-methylthionanisol or 4-methyl-2-chloro-methylthiophenetole there are obtained the following com- Example 2 42 grams of'dried and filtered potassium carbonate are suspended in 180 com. of methylethyl ketone. There are added at a temperature of about 50 C. 47 grams of diethyl-dithiophosphoric acid. Furthermore there are added while stirring at a temperature of 60 48 grams of 4- methy1-2-chloromethyl-thioanisol (dissolved in 70 com. methylethyl ketone). After a reaction time of 4 hours at a temperature of 65-70 C. the mixture is cooled to room temperature and the potassium chloride is filtered off with suction. The solvent is then removed by distillation. The residue is taken up in ccm. of ether andwashed with water. After drying the etherical solution the ether 'is evaporated in vacuum. There are obtained 85 grams of the new ester of theformula At a pressure of 0.01 mm. the new ester boils at 127- 130' C. Spider mites are killed completely with concentrations of about 0.01%.
By exactly the same way but using instead of 0.0-diethyl-dithiophosphoric acid potassium salt, the corresponding molecular amount of the corresponding diinethyl ester and instead of the 4-methyl-2-chloromethylthioanisol, exactly the corresponding molecular amount of, 4 ethyl 2 chloromethyl-thioanisol or 4 methyl-2- chloromethylthiophenetole there are obtained the following compounds:
isopropyl-dithiophosphoric acid. Thereafter there is added a solution of 48 grams 4-methyl-2-chloromethylthioanisol in 70 com. of methylethyl ketone during 20- minutes. The reaction product is kept for 3 hours at a temperature of about 65 Cjand then is worked up as described in Example 2. There are obtained'87.5 grams of the new ester of the formula S-CH (cam-0H0 s Yield: 96% of the theoretical. Even in high vacuum the new ester is not distillable without decomposition. The new ester shows a toxicity LD of 500-1000 mg./kg. on rats orally. 0.01% solutions kill black bean aphids completely.
Example 4 40 grams of the ammonium salt of 0.0-diethylthiolphosphoric acid are di Sfllved in 150 ccm. of methylethyl ketone. There is added at a temperature of about 30 C. asolutio'n 'of 44 grams of the sulfone of the following formula dissolved in 100 ccm. methylethyl ketone:
SOr-CHl (hHsQ Yield: 81% of the theoretical. After a short period the raw product is crystallized; M.P. 63 C. The new ester shows a toxicity of 100 mg./kg. (LD on rats orally. Spider mites are killed completely with concentrations of about 0.1%
The above shown sulfone may be prepared as follows: 95 grams of 2-chloromethyll-methylthio-anisol are dissolved in 240 m1. of glacial acetic acid. At a temperature of 50 C. there are added 250 ml. of hydrogen peroxide (concentration 35%) within minutes. The reaction is completed by standing for another hour and half a 5 6 Wh le cool n the u furic ys z and may be recrystallized (if necessary) from benzene; M.P. 84 C.
Example 5 SO-OH| OHr-Cl The reaction mixture is kept for 5 hours at a temperature of 60 C. and then it is worked up in the usual manner. There 'are obtained 73 grams of the new ester of the following formula SCL-CH: G H O l CH;
The new ester-shows a medium toxicity of 1000 mg./kg.
. .6 on rats orally. Mosquito larvae are killed completely with concentrations of about 0.0001%.
The above shown sulfoxide may be prepared as follows: grams of 2-chloro-methyl-4-methyl-thioanisol are dissolved in 240 ml. of glacial acetic acid. At 0 C. there are added within 1 hour ml. of hydrogen peroxide (concentration 35%). The reaction is completed within 2 /2 hours and the acetic acid and water is distilled ofif in vacuum. The sulfoxide remains as an oil and is pure enough for being further reacted according to the above example.
Example 6 0 coin.
52 grams (0.3 mol) of 4-methylmercapto-benzylchloride of B.P. 96.-98 C./2 mm. Hg are added dropwise at 40- 50 C. to a suspension of 67 grams (0.33 mol) of diethyl-thiolphosphoric acid ammonium salt in 150 oem. of acetone. The mixture is heated for a further hour to 50-60 C. to complete the reaction. The precipitated ammonium chloride is filtered off with suction. and the filtrate poured into water. The oil is taken up in benzene, washed with water and a sodium bicarbonate solution, dried and distilled. 77 grams of thiolphosphoric acid-0.0-diethyl-S-4-methylmercapto-benzyl ester are obtained in the form of a yello w, thinly liquid oil of B.P. 124 C./0.0l mm. Hg. Yield: 81.3% of the theoretical.
The ester shows atoxicity (LD of 10 mg/kg. on rats per os. Spider mites are killed to 60% even with dilutions of l:100.000.
Example 7 30.5 grams (0.2 mol) of 4- methylmercaptorbenzylchloride are added dropwise to a solution of 44 (0.22 mol) of diethyl-thionothiol-phosphoric acid ammonium salt in 100 ccmhof acetone starting at a temperature of 20 C. After the slightly exothermic reaction subsides, the solution is heated to 5060 C. for one hour, the reaction product is then poured into water, the oil is taken up in benzene, washed and dried. By distillation 56 grams of thionot hiolphosphoric acid-Q0- die thyI-S-A-methyImercapto-benzyl ester of B.P. 125 C./ 0.01 mm..Hg are obtained in the form of a pale yellow, almost colorless oil. Yield: 87% of the theoretical.
The ester shows a toxicity (LD of 50 mg./kg. on rats per os. 0.001% solutions kill spider mites to 100%.
0 CiHa Example 8 omso-Q-orn-s- 30.6 grams of the ester obtained according to Example 6 are dissolved in 75. ccm. of methanol and treated with 0.5 ccm. of 50% sulfuric acid. The calculated amount of a high-percent hydrogen peroxide is added dropwise with cooling at 40-50 C., the solution is stirred for one hour during which it cools. After the addition of water, the oil is taken up in benzene, washed with water and dried; the solvent is distilled oil; 29.5 grams of thiolphosphorio acid-0.0-diethyl-S-4-methyl-sulfinyl-benzyl ester are obtained in theform of a pale yellow, water-insoluble oil which is not distillable.
The toxicity (LD of the ester lies at 20 mg./kg. on rats per os. At a concentration of 0.01% the ester still shows a 100% actionagainst the eggs of the red spider.
'If the ester obtained according to Example 6 is oxidized, with the calculated amount of potassium permanganate in 2,9ss,91a
diluted sulfuric acid there is obtained the ester of the following formula oom- J CH. O UB P Example 9 8 OCgH;
O CiHt As described in Example 8, 25 grams of the ester obtained according to Example 7 are oxidized in 50 ccm. of methanol in the presence of a small amount of dilute sulfuric acid with the calculated quantity of hydrogen peroxide. After working up in conventional manner 25 grams of thionothiol-phosphoric acid-0.0-diethyl-S-4- methyl-sulfinyl-benzyl ester are obtained. The colorless to pale yellow ester is water-insoluble and not distillable.
The toxicity (LD of the ester lies between to mg./kg. on rats per es. With concentrations of 1:100.000 spider mites and their eggs are completely killed. 7
Example 10 O OOH:
45 grams of ammonium dimethylthiolphosphate are dissolved in 150 ccm. ofacetone, and p-methyl-mercaptobenzyl-chloride of B.P. 59 C./0.01 mm. Hg is added dropwise at 40-35 C. The solution is subsequently heated to 60 C. for a half hour. After cooling, the salt is filtered oif and the solution is diluted with benzene and shaken out twice with water. The benzene solution is dried over sodium sulfate and the solvent removed in vacuum. 41 grams (corresponding to 74% of the theoretical) of the new ester are obtained in the form of an almost colorless oil.
Analysis.Calculated: P 11.13%; Found: P=9.76%; S=22.85%.
Example 11 S 0Ct 1l OClHrl 56 grams of ammonium diisopropyl-thinothiol-phosphate are dissolvedin 15 0 ccm. of acetone, and grams of p-methylmercapto-benzyl chloride of B.P. 59 C./ 0.01 mm. Hg are added dropwise at C. Working up is carried out as indicated in Example 10. 66 grams of the new ester are obtained in the form of a pale yellow oil which is clear soluble in cyclohexane. Yield: 99% of the theoretical.
Analysis.Calculated: P=9.26%; S=28.77%. Found: P -8.73%; S=26.73%.
Example 12 magma? 0 CHI! 53 grams of ammonium diisopropyl-thiolphosphate are dissolved in 150 ccm. of acetone, and 35 grams of pmethyl-mercapto-benzyl chloride of B.P. 59 C./ 0.01 mm. Hg are added dropwise at C. The reaction mixture is heated to the boil under reflux on a water bath for lhour. Working up is carried out as described in Example 10. The new ester is obtained in the form of a pale yellow oil. Yield: 63 grams corresponding to 99% of the theoretical.
Analysis.--Calculated: P=9.73% S=20.15%, Found: P=8.94%; S=17.3 2%.
Weclaim: I l. A thiophosphoric acid ester of the following formula INC/O R1 3. A thiophosphoric acid ester of the following formula S-CH: CgHsO S P-S-CH 4. A thiophosphoric acid ester of the following formula CH O l 5. A thiophosphoric acid ester of the following formula S-CH (CHah-CHO S 6. A thiophosphoric acid ester of the following formula 7. A thiophosphoric acid ester of the following formula 8. A thiophosphoric acid ester of the following formula 5 0 0,11, ems-Q0 H,--si
o O1H| 9. A thiophosphoric acid ester of the following formula O O C2H| cmso-Q-cmw-K 9 10. A thiophosphoric acid ester of the following formula 0 0 01H. CH:S0|CHr-S- \O C211; 5 11. A thiophosphoric acid ester of the following formula S O 01H; OH=SOQGHQ-S 1 12. A thiophosphoric acid ester of the following formula OCH:
13. A thiophosphoric acid ester of the following formula S O oaH' i ll CHaS-CHzSP\ O CaH7l 14. A thiophosphoric acid ester of the following formula O C :H'li
References Cited in the file of this patent UNITED STATES PATENTS 2,803,580 Metivier Aug. 20, 1957 Patent No,, 2,938,919
May 31, 1960 Walter llorenz et al.3
Patent should read a s corrected belo or appears in the printed specification ng correction and that the said Letters Column 3, lines 25 to 31 the formula should appear as shown below instead of as in the patent:
1 SCH C H O column 5, lines 25 to 31, the formula should appear as shown below instead of as in the patent:
2 5 O SOg-CHg P-S-CH C H O column 7, line 49, for "thinothiol-" read thionothiol same column 7,
lines 60 to 64, shown below in stead of as in the patent the formula should appear as CH3 H2S-P (SEAL) attest:
KARL a Lttesting Officer W and sealed this 10th day of January 1961.,
ROBERT C. WATSON Commissioner of Patents

Claims (1)

1. A THIOPHOSPHORIC ACID ESTER OF THE FOLLOWING FORMULA
US789259A 1958-02-06 1959-01-27 Thiophosphoric acid esters and a process for their manufacture Expired - Lifetime US2938919A (en)

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DEF20758A DE1035153B (en) 1958-02-06 1958-02-06 Process for the preparation of insecticidally active thiophosphoric acid esters
DEF0024992 1958-02-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294874A (en) * 1962-01-24 1966-12-27 Bayer Ag Omicron-alkyl-omicron-cycloalkyl-s-alkylthiolphosphoric acid esters
US3933947A (en) * 1970-03-25 1976-01-20 Bayer Aktiengesellschaft O-ethyl-S-propyl-S-benzyl-phosphorodithiolates
US4448733A (en) * 1981-04-06 1984-05-15 Nihon Tokushu Noyaku Seizo K.K. Production of alkylsulfinyl substituted organophosphoric acid esters

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL302624A (en) * 1963-01-04

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803580A (en) * 1955-03-05 1957-08-20 Rhone Poulenc Sa Phosphorus derivatives, process for their preparation and compositions containing same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE830509C (en) * 1950-05-24 1952-02-04 Bayer Ag Process for the preparation of neutral esters of thiophosphoric acid
DE885176C (en) * 1951-10-02 1953-08-03 Bayer Ag Pest repellants
DE949231C (en) * 1955-05-03 1956-09-13 Bayer Ag Process for the preparation of chlorinated benzyl esters of thiol or thionothiol phosphoric acids
DE1018053B (en) * 1955-10-29 1957-10-24 Bayer Ag Process for the preparation of S-chlorobenzyl esters of O, O-dialkyl-thiolphosphoric acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803580A (en) * 1955-03-05 1957-08-20 Rhone Poulenc Sa Phosphorus derivatives, process for their preparation and compositions containing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294874A (en) * 1962-01-24 1966-12-27 Bayer Ag Omicron-alkyl-omicron-cycloalkyl-s-alkylthiolphosphoric acid esters
US3933947A (en) * 1970-03-25 1976-01-20 Bayer Aktiengesellschaft O-ethyl-S-propyl-S-benzyl-phosphorodithiolates
US4448733A (en) * 1981-04-06 1984-05-15 Nihon Tokushu Noyaku Seizo K.K. Production of alkylsulfinyl substituted organophosphoric acid esters

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FR1178349A (en) 1959-05-06
GB864433A (en) 1961-04-06

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