US2910500A - Phenyl sulfoxy and lower alkyl sulfoxy o, o-di (lower alkyl) thiophosphate esters and process for preparation - Google Patents
Phenyl sulfoxy and lower alkyl sulfoxy o, o-di (lower alkyl) thiophosphate esters and process for preparation Download PDFInfo
- Publication number
- US2910500A US2910500A US696029A US69602957A US2910500A US 2910500 A US2910500 A US 2910500A US 696029 A US696029 A US 696029A US 69602957 A US69602957 A US 69602957A US 2910500 A US2910500 A US 2910500A
- Authority
- US
- United States
- Prior art keywords
- grams
- lower alkyl
- sulfoxy
- benzene
- millilitres
- 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
- -1 Phenyl sulfoxy Chemical group 0.000 title description 16
- 238000000034 method Methods 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 4
- 125000000217 alkyl group Chemical group 0.000 title description 3
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title description 3
- 125000005332 alkyl sulfoxy group Chemical group 0.000 title 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 52
- 239000000243 solution Substances 0.000 description 28
- 150000002148 esters Chemical class 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 241001425390 Aphis fabae Species 0.000 description 9
- 241001454295 Tetranychidae Species 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000009885 systemic effect Effects 0.000 description 6
- 239000002917 insecticide Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- JCWBGXXPAPSAFE-UHFFFAOYSA-N 4-chlorobenzenesulfinyl chloride Chemical compound ClC1=CC=C(S(Cl)=O)C=C1 JCWBGXXPAPSAFE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CXAVWUXAKZJEBR-UHFFFAOYSA-N ethanesulfinyl chloride Chemical compound CCS(Cl)=O CXAVWUXAKZJEBR-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000006501 nitrophenyl group Chemical group 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- AOQYAMDZQAEDLO-UHFFFAOYSA-N 4-chlorobenzenesulfinic acid Chemical compound OS(=O)C1=CC=C(Cl)C=C1 AOQYAMDZQAEDLO-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000238876 Acari Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- JGSYKOGZFMBYAQ-UHFFFAOYSA-N CC[P]CC Chemical compound CC[P]CC JGSYKOGZFMBYAQ-UHFFFAOYSA-N 0.000 description 1
- 241001107116 Castanospermum australe Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001325166 Phacelia congesta Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000238515 Thymus pulegioides Species 0.000 description 1
- 235000017715 Thymus pulegioides Nutrition 0.000 description 1
- 240000001260 Tropaeolum majus Species 0.000 description 1
- 241000607479 Yersinia pestis Species 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
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 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
- DKENIBCTMGZSNM-UHFFFAOYSA-N benzenesulfinyl chloride Chemical compound ClS(=O)C1=CC=CC=C1 DKENIBCTMGZSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000021279 black bean Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- MBWRLGQNVZIZBI-UHFFFAOYSA-N chloro-diethyl-dihydroxy-$l^{5}-phosphane Chemical compound CCP(O)(O)(Cl)CC MBWRLGQNVZIZBI-UHFFFAOYSA-N 0.000 description 1
- JEYZNPCFNNYIEQ-UHFFFAOYSA-N chloro-dihydroxy-dimethyl-$l^{5}-phosphane Chemical compound CP(C)(O)(O)Cl JEYZNPCFNNYIEQ-UHFFFAOYSA-N 0.000 description 1
- TWFHAEGZFQHISA-UHFFFAOYSA-N chlorobenzene;sodium Chemical compound [Na].ClC1=CC=CC=C1 TWFHAEGZFQHISA-UHFFFAOYSA-N 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011555 saturated liquid Substances 0.000 description 1
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003454 sulfinic acid halides Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000000772 tip-enhanced Raman spectroscopy Methods 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
-
- 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
- C07F9/1654—Compounds containing the structure P(=X)n-X-acyl, P(=X)n-X-heteroatom, P(=X)n-X-CN (X = O, S, Se; n = 0, 1)
-
- 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
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
Definitions
- the present invention relates to and has as its objects new and useful phosphoric acid esters, which may be represented by the following formula in which R stands for alkyl and aryl radicals, R and R stand for alkyl radicals especially lower alkyl radicals up to 4 carbon atoms, and X is oxygen or sulfur.
- R stands for alkyl radicals, such as methyl, ethyl, propyl (n-propyl or isopropyl), nbutyl, isobutyl, tert. butyl, or aryl radicals, such as phenyl, 0-, mor p-tolyl, 0-, mor p-chloro phenyl, nitrophenyl, methoxyphenyl, p-chloro-m-nitrophenyl, p-nitro m-chloro phenyl, and the like.
- esters of the above shown formula may be obtained by various methods.
- tag. the phosphoric acid esters of the above shown formula these are those esters in which X of the above shown formula stands for oxygen, may be obtained by reacting the corresponding aliphatic or aromatic sulfinic acids or their salts with 0.0-dia1kyl phosphorous acid halides. This reaction may be seen from the following scheme, using sodium benzene sulfinate and 0.0-diethyl phosphorous acid chloride as reaction components:
- the free acids may be used in combination with suitable organic acid binding agents, suchas tert. amines, e.g. pyridine.
- suitable organic acid binding agents such as tert. amines, e.g. pyridine.
- This reaction generally should be carried out in the presence of inert solvents, such as methanol,
- reaction furthermore may be carried out at temperatures from about 0 to' 0., especially suitable are slightly elevated temperatures between 40 to 60 C.
- reaction action also should be carried out usually in the presence of inert organic solvents, such as especially benzene, toluene, lower saturated liquid hydrocarbons (benzine or ligroine) or chlorinated aliphatic hydrocarbons, such as methylene chloride, ethylene chloride, chloroform, and the like.
- inert organic solvents such as especially benzene, toluene, lower saturated liquid hydrocarbons (benzine or ligroine) or chlorinated aliphatic hydrocarbons, such as methylene chloride, ethylene chloride, chloroform, and the like.
- inert organic solvents such as especially benzene, toluene, lower saturated liquid hydrocarbons (benzine or ligroine) or chlorinated aliphatic hydrocarbons, such as methylene chloride, ethylene chloride, chloroform, and the like.
- This reaction may be carried out also between about 0 to 100 C., but especially suitable in this case are temperatures somewhat lower than room
- the aforementioned method also may successfully be used for the preparation of corresponding thiophosphoric acid esters.
- These are compounds of the above shown formula in whic X is sulfur.
- corresponding trialk'yl monothiophosphites or dialkyl monothiophosphites may be used instead of trialkyl phosphites.
- This reaction may be shown by the following scheme, using ethyl sulfinic acid chloride and diethyl thiolphosphite as starting materials:
- the compounds of the present invention are generally valuable insecticides especially systematically active insecticides and kill effectively insects such as flies, aphids, mites and the like.
- a special advantage of the inventive compounds is their activity against sucking insects, such as caterpillars. Usuallythey are to be applied in the same manner as other well known phosphorus containing insecticides, i.e. in concentrations from about 0.0001 to about 1% in dilution with liquid or solid carriers.
- liquid carriers examples include water, alcohols,
- the benzenic solution is washed twice with 50 millilitres of water, whereupon the benzenic layer is dried over unhydrous sodium sulfate.
- the benzene is distilled off in vacuo. A small amount of impurities crystallizes and can be removed by freezing and filtration. The remaining oil is distilled in vacuo at 85 to 86 C. There are obtained 100 grams ofthe above shown ester as slightly yellowish colored Water-unsoluble oil.
- LD rat per os 10 rug/kg.
- Example 2 45 grams of p-chloro-benzene sulfinic acid are dissolved in 100 millilitres of methyl ethyl ketone. There are added while stirring 21 grams of pyridine and 40 grams of diethyl phosphorous acid monochloride are dropped into this solution at a temperature of 35 C. The temperature is kept at 40 C. for half an hour and the reaction mixture then is cooled to room temperature. The reaction mixture is poured into 200 millilitres of ice-water and the oil is taken up in 200 millilitres of benzene. The benzene layer is separated, washed twice with 50 millilitres of water and dried over sodium sulfate. After distilling ofi? the solvent there are obtained 35 grams of the above ester boiling at 0.01 mm. at 108 to 110 C. 0.1% solutions exhibit complete systemic action on black bean aphids and spider mites and also kill caterpillars effectively.
- Example 4 O OCzH O O CgH 36 grams of benzene sulfinic acid are dissolved in 100 millilitres of methyl ethyl ketone; 21 grams of pyridine are added. While stirring there are dropped into this solution at 50 C. 43 grams of diethyl phosphorus acid monochloride dissolved in 44 millilitres of toluene. The reaction mixture is kept at 65 C. for 1 further hour, and worked up as described in the foregoing examples. There are obtained 30 grams of the new ester of the above shown formula.
- Example 6 36 grams (0.85 mole) of p-chloro-benzene sulfinic acid chloride are dissolved in 50 millilitres of benzene, and treated dropwise while cooling at 15 to 25 C. into a solution of 46 grams (0.37 mole) of trimethyl phosphite in 150 millilitres of benzene. After the addition has been completed the mixture is stirred for a short period of time and the solvent then is removed by distillation. The remaining oily residue is stirred half an hour with water, and the aqueous layer is neutralized with diluted potassium carbonate solution.
- Example 7 A solution of 48.5 grams (0.25 mole) of p-chloro-benzene sulfinic acid chloride in 50 millilitres of benzene is added dropwise while cooling to to C. to a solution of 49.8 grams (0.3 mole) of triethyl phosphite in 75 millilitres of benzene. After the addition has been completed the reaction mixture is stirred for further half an hour. The solvent then is distilled Off and the remainder is washed with water and neutralized with a diluted potassium carbonate solution. The remaining oil is taken up in benzene, washed twice with water, dried over sodium sulfate and at last the benzene is distilled 01f.
- ester may be obtained by using 42 grams of diethyl phosphite instead of 49.8 grams of triethyl phosphite.
- the working up procedure is the same as shown above.
- the yield is slightly higher, it amounts up to about 56% of the theoretical.
- Example 8 39 grams of p-chloro-benzene sulfinic acid chloride are dissolved in 200 millilitres of petrol ether (boiling point about 60 C.). At a temperature of 20 to C. this solution is added dropwise while cooling to 47 grams (0.3 mole) of diethyl thiolphosphite. After the addition has been completed the reaction mixture is stirred for further 10 minutes. 100 millilitres of water are added. The layers are separated again and this procedure is continued, until the organic layer reacts neutrally.
- Example 9 49.5 grams (0.25 mole) of p-chloro-benzene sulfinic acid chloride are dissolved in 50 millilitres of benzene, and this solution is dropped while cooling at 10 to 20 C. Into a solution of 63 grams (0.3 mole) of triisopropyl phosphite in 200 millilitres of benzene. After the reaction has been completed the mixture is stirred for further half an hour and the solvent then is distilled off. The remaining oil is washed with water and neutralized with sodium hydrocarbonate. Then the oil is taken up in benzene, and the benzenic solution is washed with water, dried over unhydrous sodium sulfate and distilled.
- the phosphoric acid ester of the following formula S OC2H5 01-s-i i ⁇ O C2115 References Cited in the file of this patent UNITED STATES PATENTS 2,648,696 Whetstone June 19, 1951 2,690,451 Gilbert et a1. Sept. 28, 1954 2,828,241 Birum Mar. 25, 1958 OTHER REFERENCES Ser. No. F10,047, Wegriken Bayer, Germany, published July 26, 1956.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF24038A DE1058050B (de) | 1957-09-26 | 1957-09-26 | Verfahren zur Herstellung von Thiophosphorsaeure- bzw. Phosphor-saeureestern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2910500A true US2910500A (en) | 1959-10-27 |
Family
ID=7091077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US696029A Expired - Lifetime US2910500A (en) | 1957-09-26 | 1957-11-13 | Phenyl sulfoxy and lower alkyl sulfoxy o, o-di (lower alkyl) thiophosphate esters and process for preparation |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US2910500A (en(2012)) |
| BE (1) | BE562136A (en(2012)) |
| CH (1) | CH368156A (en(2012)) |
| DE (1) | DE1058050B (en(2012)) |
| FR (1) | FR1216922A (en(2012)) |
| GB (2) | GB811268A (en(2012)) |
| NL (2) | NL99399C (en(2012)) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328360A (en) * | 1962-07-06 | 1967-06-27 | Exxon Research Engineering Co | Polymers containing phosphorus |
| US4155958A (en) * | 1977-09-26 | 1979-05-22 | Standard Oil Company (Indiana) | Beta-phosphosulfoxy alcohols |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3179688A (en) * | 1962-06-20 | 1965-04-20 | Monsanto Co | Phosphonyl- and thiophosphonyl-thio-nylamines and process of preparing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2648696A (en) * | 1951-06-19 | 1953-08-11 | Shell Dev | Mixed acid anhydrides and process for production of same |
| US2690451A (en) * | 1951-09-28 | 1954-09-28 | Allied Chem & Dye Corp | Method for preparation of sulfur-containing esters of phosphoric acid |
| US2828241A (en) * | 1954-05-25 | 1958-03-25 | Monsanto Chemicals | O,o-dialkyl s-arylmercapto phosphoro-dithioate compositions and method of destroyinginsects |
-
0
- NL NL222488D patent/NL222488A/xx unknown
- BE BE562136D patent/BE562136A/xx unknown
- NL NL99399D patent/NL99399C/xx active
-
1957
- 1957-09-26 DE DEF24038A patent/DE1058050B/de active Pending
- 1957-10-21 FR FR749821A patent/FR1216922A/fr not_active Expired
- 1957-10-30 CH CH5211457A patent/CH368156A/de unknown
- 1957-11-13 US US696029A patent/US2910500A/en not_active Expired - Lifetime
- 1957-12-04 GB GB37825/57A patent/GB811268A/en not_active Expired
- 1957-12-13 GB GB38898/57A patent/GB812045A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2648696A (en) * | 1951-06-19 | 1953-08-11 | Shell Dev | Mixed acid anhydrides and process for production of same |
| US2690451A (en) * | 1951-09-28 | 1954-09-28 | Allied Chem & Dye Corp | Method for preparation of sulfur-containing esters of phosphoric acid |
| US2828241A (en) * | 1954-05-25 | 1958-03-25 | Monsanto Chemicals | O,o-dialkyl s-arylmercapto phosphoro-dithioate compositions and method of destroyinginsects |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328360A (en) * | 1962-07-06 | 1967-06-27 | Exxon Research Engineering Co | Polymers containing phosphorus |
| US4155958A (en) * | 1977-09-26 | 1979-05-22 | Standard Oil Company (Indiana) | Beta-phosphosulfoxy alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1058050B (de) | 1959-05-27 |
| FR1216922A (fr) | 1960-04-29 |
| NL99399C (en(2012)) | |
| CH368156A (de) | 1963-03-31 |
| GB811268A (en) | 1959-04-02 |
| BE562136A (en(2012)) | |
| GB812045A (en) | 1959-04-15 |
| NL222488A (en(2012)) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3309371A (en) | Organophosphorothioate compounds and method of preparing same | |
| US2992265A (en) | Phenyl phosphonic acid esters | |
| US3153663A (en) | Phosphoric (phosphonic, phosphinic) or thiophosphoric (-phosphonic, -phosphinic) acidesters and processes for their production | |
| US2862019A (en) | Thiophosphoric acid esters and their production | |
| US3056825A (en) | Thiophosphoric acid esters and a process for their production | |
| US3248412A (en) | Thiophosphonic acid esters | |
| US2923730A (en) | Dithiophosphoric acid esters and their preparation | |
| US2910500A (en) | Phenyl sulfoxy and lower alkyl sulfoxy o, o-di (lower alkyl) thiophosphate esters and process for preparation | |
| US2910501A (en) | Thiophosphoric acid esters and process for their manufacture | |
| US2931755A (en) | Omicron, omicron-dialkyl or omicron, omicron-bis (haloalkyl) s-dichloromethyl phosphorothioates | |
| US3180873A (en) | O-ortho(t-aminomethyl phenyl) neutral esters of pentavalent phosphorus acids | |
| US3030404A (en) | Thiophosphoric acid esters and process for producing them | |
| US2928863A (en) | Thiophosphoric acid esters and their production | |
| US2956074A (en) | Thiophosphoric acid esters | |
| US3076012A (en) | Phosphoric acid esters and processes for their production | |
| US3234305A (en) | Thiophosphorus acid esters | |
| US3156718A (en) | Process for preparing thiophosphoric, thiophosphonic, and thiophosphinic acid esters | |
| US3166581A (en) | S-acyloxyalkyl and s-acyloxyalkenyl esters of o, o-diorgano-phosphorothiolic acids | |
| US2931824A (en) | Thiophosphoric acid esters and their production | |
| US3060217A (en) | Thiophosphoric acid esters | |
| US2983748A (en) | Thionophosphonic acid esters | |
| US2961458A (en) | Phosphorus containing insecticidal compounds and a process for their production | |
| US2962518A (en) | Phosphonic acid esters | |
| US2829111A (en) | Azidoethyl-thiophosphoric acid esters | |
| US3164623A (en) | O-cyanophenyl esters of alkylphosphonic, alkylthiophosphonic, dialkylphosphinic, anddialkylthiophosphinic acids |