US2938919A - Thiophosphoric acid esters and a process for their manufacture - Google Patents
Thiophosphoric acid esters and a process for their manufacture Download PDFInfo
- Publication number
- 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
- Authority
- US
- United States
- Prior art keywords
- ester
- grams
- acid
- following formula
- thiophosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title claims description 15
- 238000000034 method Methods 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000002148 esters Chemical class 0.000 description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 241000700159 Rattus Species 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- -1 mercapto compounds Chemical class 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 231100000419 toxicity Toxicity 0.000 description 8
- 230000001988 toxicity Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 241001454295 Tetranychidae Species 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 150000003457 sulfones Chemical class 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- XPKDQBYOXNXKGG-UHFFFAOYSA-N 2-(chloromethyl)-4-methyl-1-methylsulfanylbenzene Chemical compound CSC1=CC=C(C)C=C1CCl XPKDQBYOXNXKGG-UHFFFAOYSA-N 0.000 description 3
- 241000238876 Acari Species 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241001425390 Aphis fabae Species 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 235000013601 eggs Nutrition 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VWVZFHRDLPHBEG-UHFFFAOYSA-N 1-(chloromethyl)-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(CCl)C=C1 VWVZFHRDLPHBEG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- SBLXUAYEKKRANO-UHFFFAOYSA-N chloro-(4-methylphenyl)methanethiol Chemical compound CC1=CC=C(C(S)Cl)C=C1 SBLXUAYEKKRANO-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- MQHRCVXVEKBXFA-UHFFFAOYSA-N dihydroxy-propan-2-ylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)SP(O)(O)=S MQHRCVXVEKBXFA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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 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
Definitions
- 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:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20758A DE1035153B (de) | 1958-02-06 | 1958-02-06 | Verfahren zur Herstellung von insektizidwirksamen Thiophosphorsaeureestern |
| DEF0024992 | 1958-02-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2938919A true US2938919A (en) | 1960-05-31 |
Family
ID=25973980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US789259A Expired - Lifetime US2938919A (en) | 1958-02-06 | 1959-01-27 | Thiophosphoric acid esters and a process for their manufacture |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2938919A (de) |
| CH (2) | CH359146A (de) |
| DE (2) | DE1035153B (de) |
| FR (1) | FR1178349A (de) |
| GB (2) | GB808879A (de) |
Cited By (3)
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL302624A (de) * | 1963-01-04 |
Citations (1)
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE830509C (de) * | 1950-05-24 | 1952-02-04 | Bayer Ag | Verfahren zur Herstellung von neutralen Estern der Thiophosphorsaeure |
| DE885176C (de) * | 1951-10-02 | 1953-08-03 | Bayer Ag | Schaedlingsbekaempfungsmittel |
| DE949231C (de) * | 1955-05-03 | 1956-09-13 | Bayer Ag | Verfahren zur Herstellung von chlkorierten Benzylestern der Thiol- bzw. Thionothiolphosphorsaeuren |
| DE1018053B (de) * | 1955-10-29 | 1957-10-24 | Bayer Ag | Verfahren zur Herstellung von S-Chlorbenzylestern der O, O-Dialkyl-thiolphosphorsaeure |
-
0
- DE DENDAT1074034D patent/DE1074034B/de active Pending
-
1957
- 1957-06-21 CH CH359146D patent/CH359146A/de unknown
- 1957-07-04 GB GB21241/57A patent/GB808879A/en not_active Expired
- 1957-07-10 FR FR1178349D patent/FR1178349A/fr not_active Expired
-
1958
- 1958-02-06 DE DEF20758A patent/DE1035153B/de active Pending
-
1959
- 1959-01-23 CH CH6868459A patent/CH367832A/de unknown
- 1959-01-27 US US789259A patent/US2938919A/en not_active Expired - Lifetime
- 1959-02-04 GB GB4006/59A patent/GB864433A/en not_active Expired
Patent Citations (1)
| 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)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CH359146A (de) | 1961-12-31 |
| CH367832A (de) | 1963-03-15 |
| FR1178349A (fr) | 1959-05-06 |
| DE1035153B (de) | 1958-07-31 |
| GB864433A (en) | 1961-04-06 |
| GB808879A (en) | 1959-02-11 |
| DE1074034B (de) | 1960-01-28 |
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