US2952700A - Thiophosphoric acid esters and their production - Google Patents
Thiophosphoric acid esters and their production Download PDFInfo
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- US2952700A US2952700A US645403A US64540357A US2952700A US 2952700 A US2952700 A US 2952700A US 645403 A US645403 A US 645403A US 64540357 A US64540357 A US 64540357A US 2952700 A US2952700 A US 2952700A
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- 150000003580 thiophosphoric acid esters Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000003921 oil Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229960003010 sodium sulfate Drugs 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- -1 sulfonyl- Chemical group 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 150000003462 sulfoxides Chemical class 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 229960002163 hydrogen peroxide Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000009885 systemic effect Effects 0.000 description 4
- 241001425390 Aphis fabae Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 241000700159 Rattus Species 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 2
- 241000256113 Culicidae Species 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 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
- 241000238876 Acari Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001107116 Castanospermum australe Species 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 102400000675 Chondrosurfactant protein Human genes 0.000 description 1
- 101800000362 Chondrosurfactant protein Proteins 0.000 description 1
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000021279 black bean Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- URWAJWIAIPFPJE-YFMIWBNJSA-N sisomycin Chemical compound O1C[C@@](O)(C)[C@H](NC)[C@@H](O)[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@@H](CC=C(CN)O2)N)[C@@H](N)C[C@H]1N URWAJWIAIPFPJE-YFMIWBNJSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 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
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Definitions
- this invention relates to 5 ethyl)l-0,0-dialkyl-thiol-(and thiono-thiol-) phosphoric States 2,952,700
- Cl. 260-461) relates to and has as its objects new and useful thiophosphorlc acid esters and their production. More specifically this invention is concerned with 232 5 g" and dithiophosphofic acid-esters 9 the ing these compounds consists in reacting a salt of an 8 rm v V appropriate 0,0-dialkyl-thiol(or thlOIlO-IhlOD PhOSPhOI-f fif I ic acid with the desired alkyl-mercapto- (or sulfoxylor RYA,-SP sulfonyl-) alkyl halide as shown by the following equa- ER!
- Hal stands for halogen
- dialkylphosphites may be reacted with the appropriate.
- the pres.ent pq there i alkyl thiocyanides or dialkylphosphoric or thionophosfound a new class of phoric acid-halides may be reacted with alkyl-mercaptoacid esters of the above general formula, particularly alkyl 7 mercaptans
- S (fi haloalkyl o,o dialkyl such tlllO- and dtthiophosphonc ac1d esters of the 40 h H hi ihi L) phosphoric acid esters may be formula reacted with suitable mercaptans, thus yielding the de- X sired alkylmercapto-branche d alkylesters.
- sulfonyl- Q/ alkylesters are desired it is also possible to add ap'pro v v V priate vinylalkylsulfones to 0,0;dialkyl-thiol-(or thionof a 7 thiol-)-phosphoric acids or to react alkylsulfonylalkyl- 4 sulfohahdes wlth O,O-d1alkyl-phosphor1c aclds.
- m'whlch X and Y have the s-ame slgmficvanqesulfoxyl and sulfonylalkylesters may be prepared by oxidizing the corresponding alkylmercaptoalkylesters. This last method is described 'e.g'. in US. application Ser. No. 544,832 (sulfoxides) and Ser. No. 526,557 (sulfones). All the above mentioned'metho'ds of preparations refer to unbranched alkyl compounds.
- the inventive new esters may be prepared aecording to all these methods and by using exactly the amount of branched alkyl-reactant instead of the corresponding molecularamount of unbranched alkyl-compound.
- f concentrations from 0.00001% to about 1% are usually 1 fcinr-s-cnron--sr sufiicient" enough tof guarantee efiectivenessx
- the new I. I C v esters mayfurthermore be usedincombination witlr solid 0 0 CH and liquid carriers such as talc, chalk, bentonite, clayor t v a 3 water (if necessary with suitablecommercial emulsifiers) T- H-T ?P I alcohols, lower aliphatic hydrocarbons, aromatic hydro- (lint ooh, carbons etc. Most of the new vcompounds exhibit also my; strong systemic activity.
- the compounds thus, maybe Il/f j brought incontactinany way with insects to bekilled or FT H. i plantstoibeprotectedgJ14; oi:
- Spray solutions were prepared by dissolving the active ingredient in'the same amount of dimethylformamide. After having added about 10% this weight of a commercial emulsifier e.g. a benzyl hydroxydiphenyl polyglycol ether having about 15 glycol residues in its chain or a sultonated glycol ester of a long chain fatty acid, the organic solution is diluted with water to the concentrations indicated below. Forlthe'determination of toxicity rats were fed with baits containing the active ingredient. indicated below. The figures under toxicity, show from right to left the quantity of animals; tested/with symptoms/killed.
- a commercial emulsifier e.g. a benzyl hydroxydiphenyl polyglycol ether having about 15 glycol residues in its chain or a sultonated glycol ester of a long chain fatty acid.
- ammonium salt of 0,0-dipropyl-thiolphosphoric acid are dissolved in 300 ml. methanol. While stirring there are added slowly at 60"C. 148 'g'. '(Z-chlord-T- methyl-ethyl( l)-.) (ethyl-)sulfide. .The temperature is kept at 60 C. for one further hour and'then after cooling the reaction mixture is filtered with sulfur. The methanol isremoved by distillation and. the residue is taken up in. 500 ml. benzene and washed thrice with 50 ml. water. The benzene'layer then is dried over anhydrous sodium v p sulfate. After distilling oil the benzene the residue may be purified by vacuum' distillation. There are obtained 224 g. of the new ester of the above formula.
- Example 3 CrHsS-CHrCH- S g t on. e. f 190 g. of an ammonium salt of diethylthiol phosphoric;
- the temperature isltept 'at '0. for one :hour, .the salts.
- Example 4 V S OCH: Il/ mms-om-cm-s-r on. '0 CH1 17 g. of potassium hydroxide are dissolved in 50 ml.
- Example 5 T methylethylthioethyl ether are added dropwise to the solution. The temperature is kept at 4'5" C., ior one hour. The solution is then cooled to room temperature, 300ml. of ether are added, the ethereal layer is separated,
- the precipitated ester is taken up in methylene chloride, the aqueous phase is shaken once more with methylene chloride, both methylene chloride solutions arecombined, dried with sodium sulfate and the solvent is removed in vacuum; 32 g. of the crude sulfoxide are obtained as colorless water-insoluble oil. The yield is 82.2% of the theoretical.
- i CH3 OCaHs are dissolved in 75 ml. of methanol and mixed with 0.5 ml. of 50% sulfuric acid. Beginning at 20 C.; the calculated quantity of hydrogen peroxide (about 30%) is rapidly added in drops, the temperature rising to 4050 C. This temperature is maintained by cooling from outside. After the dropwise addition of the hydrogen peroxide cooling is stopped and the solution is allowed to cool. After about 30 minutes the reaction is complete. . The solution is diluted with 100 ml. of water, neutralized with potassium carbonate solution and'filteredf- The filtrate is mixed with cold, saturated potassium carbonate solution until the sulfoxide separates. The-sulfoxide is isolated by exhaustively extracting with methylene chloride. The methylene layer is dried with sodium sulfate and the methylene chloride removed by distillationjini-vacuum 3.8 g. of the new sulfoxide are obtained as colorless Watersoluble oil. The yield is 88% of the theoretical.
- Example "11 Y O H .T- H- i- 5 omcl '.J'I.'.”; 4? g. (0.15 mol) of the ester of the following com position HzCl i are suspended in dilute methanol "cQntaining OIS of sulfuric acid. Oxidizing is carried out with the calculated quantity of hydrogen peroxide at 40.-50 C. in the manner. The previously suspended ester 'dissolyesfpom pletely.
- Example. 12 added until the solution is colorless. The solution is then saturated with sulfate and the resulting sulfone ester taken up in methylene chloride by shaking.” After distillingand drying, 36 g. of the sulfone are obtained as olor'less oil which is miscible with water. The purity of the crude product is satisfactory so that distillation is not ifeguired, prior to use. Yield: 88% of the theoretical.
- Example 13 1 O OCQH C:HsSOr-CHrCHSP CH1 OCQHs 16.2 g. (0.0595 .mol) of the sulfide group-contamin g qster ofthetollowing composition 7 7 mms-cm-o-s-r (His 0 C1 8 Example .15
- 17.5 giofthe sulfoxide groupcontainingester of the following composition Y a .OQOIHE n/ I Q!H 9' r- B are added dropwise at- 5 -10 C. to a suspension orsolw tion of l 4;2 gfipotassium permanganate and 12.7 g;' magnesium suliate'200 ml. of water andl30 ml. of acetone.
- R and R stands for lower alkyl radicals
- R stands for a member selected from the group consisting of lower alkyl and lower chloroalkyl
- A stands for a lower alkylene chain of at least two carbon atoms
- X stands for a member selected fi'om the group consisting of oxygen and sulfur
- Y stands for a member selected from the group consisting of S, SO and S0,.
- R, R and R stand for lower alkyl radicals
- X stands for a member selected from the group consisting of oxygen and sulfur.
- R, R and R stand for lower alkyl radicals.
- R, R and R stand for lower alkyl radicals
- X stands for a member selected from the group consisting of oxygen and sulfur.
- a thiophosphoric acid ester of the formula 12 A thiophosphoric acid ester of the formula CH; OCHI References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Bacon et al.: J. Am. Chem. Soc. 76, 670-676 (1954).
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- Molecular Biology (AREA)
Description
. as described above. Thus, this invention relates to 5 ethyl)l-0,0-dialkyl-thiol-(and thiono-thiol-) phosphoric States 2,952,700
I Patented Sept. 13,1950
295m 7' Y i i/ z V CHq-S-CHg-CH-S-P THIOPHOSPHORIC ACID ESTERS AND THEIR H3 PRODUCTION O OCH Walter Lorenz Wnppertal-Elberfeld and Gerhard '7 H J Schrader, wuppertal-Cronenberg, Germany, asc t S T S signors to Farbenfabriken Bayer Aktiengesell- 7 I Hi OCiHI schaft, Leverkusen, Germany, a corporation of V I I v fi/OCaH i G 10 4 om-s-cm-Cn-s-r "No Drawing. Filed Mal-.12, 1957, Ser. No. 645,403 5 Claims priority, application Germany Nov. 22,195 Y 1 The corresponding sulfoxyl and sulfonyl branched alkylene compounds as well as the corresponding thiolthiono analogs of the above mentioned thiol-phosphoric acid esters are, of course, also within the scopeof the present invention.
The preparation of these compounds may be effected by various methods. Thus, a general method for obtain- 12 Claims. Cl. 260-461) invention relates to and has as its objects new and useful thiophosphorlc acid esters and their production. More specifically this invention is concerned with 232 5 g" and dithiophosphofic acid-esters 9 the ing these compounds consists in reacting a salt of an 8 rm v V appropriate 0,0-dialkyl-thiol(or thlOIlO-IhlOD PhOSPhOI-f fif I ic acid with the desired alkyl-mercapto- (or sulfoxylor RYA,-SP sulfonyl-) alkyl halide as shown by the following equa- ER! OR: 11011: I. in which R, R and R stand for alkyl, especially lower 2 2 a ii alkyl radicals, A stands for a lower branched alkylenc :jf. f f chain, X standsforeither oxygen or sulfur and Y stands R: on: 1 OR for SISO 01.802" V V t p Q in these formulae R, R R X and Y have the same LThioand dithiophosphoric acid esters arefknown as effective insecticides and especially such compounds 'ofthe above indicated type in which the alkylene chain is not branched have become of special importancerecently. Considerable work has been done in' this field to find more effective and less toxic thiophosphoric acid esters of the above type.
3o significance as shown iabove, Hal stands for halogen and.
v Me for a salt forming radical. This method is known e.g. from German Patent 830,509 (alkylmercapto-alkylhalides as reaction compounds).
Other known methods, however, may also success fully be used to prepare the inventive compounds. Thus, dialkylphosphites may be reacted with the appropriate. In accordance Wlth the pres.ent pq there i alkyl thiocyanides or dialkylphosphoric or thionophosfound a new class of phoric acid-halides may be reacted with alkyl-mercaptoacid esters of the above general formula, particularly alkyl 7 mercaptans Also S (fi haloalkyl o,o dialkyl such tlllO- and dtthiophosphonc ac1d esters of the 40 h H hi ihi L) phosphoric acid esters may be formula reacted with suitable mercaptans, thus yielding the de- X sired alkylmercapto-branche d alkylesters. If sulfonyl- Q/ alkylesters are desired it is also possible to add ap'pro v v V priate vinylalkylsulfones to 0,0;dialkyl-thiol-(or thionof a 7 thiol-)-phosphoric acids or to react alkylsulfonylalkyl- 4 sulfohahdes wlth O,O-d1alkyl-phosphor1c aclds. -F1nally-,; m'whlch X and Y have the s-ame slgmficvanqesulfoxyl and sulfonylalkylesters may be prepared by oxidizing the corresponding alkylmercaptoalkylesters. This last method is described 'e.g'. in US. application Ser. No. 544,832 (sulfoxides) and Ser. No. 526,557 (sulfones). All the above mentioned'metho'ds of preparations refer to unbranched alkyl compounds. The inventive new esters may be prepared aecording to all these methods and by using exactly the amount of branched alkyl-reactant instead of the corresponding molecularamount of unbranched alkyl-compound.
S [alkylmerca1:ito-(sulffoxyl and sulfonyl-)-(branclied-- aeid esters. Without restricting this invention in any way, there may be mentioned as example the compounds T11 of the following formulae: A V Y 1. CH: 00H, a The new esters are generally valuable insecticides of o OCH; high activity and low toxicity." They may be used to L flies, mosquitos, aphids, mites and the-lik e." The ap r phcations may be etlected m the usual way 1.e. as other 0 9 phosphorous insecticides may be used. Thus, for example,
f concentrations from 0.00001% to about 1% are usually 1 fcinr-s-cnron--sr sufiicient" enough tof guarantee efiectivenessx The new I. I C v esters mayfurthermore be usedincombination witlr solid 0 0 CH and liquid carriers such as talc, chalk, bentonite, clayor t v a 3 water (if necessary with suitablecommercial emulsifiers) T- H-T ?P I alcohols, lower aliphatic hydrocarbons, aromatic hydro- (lint ooh, carbons etc. Most of the new vcompounds exhibit also my; strong systemic activity. The compounds, thus, maybe Il/f j brought incontactinany way with insects to bekilled or FT H. i plantstoibeprotectedgJ14; oi:
r Q QEZ Q'; :;-,;As-a.sp cial exampleiorthe ot someio ftheiins ventive compounds there are given below the activities of some compounds. The tests are carried out as follows:
' Spray solutions were prepared by dissolving the active ingredient in'the same amount of dimethylformamide. After having added about 10% this weight of a commercial emulsifier e.g. a benzyl hydroxydiphenyl polyglycol ether having about 15 glycol residues in its chain or a sultonated glycol ester of a long chain fatty acid, the organic solution is diluted with water to the concentrations indicated below. Forlthe'determination of toxicity rats were fed with baits containing the active ingredient. indicated below. The figures under toxicity, show from right to left the quantity of animals; tested/with symptoms/killed.
Toxicity 10 m kg. s/s/s (Rats orally) 25 lug/kg; 5/5/5-(LD 95) iwticidalvames mosquitolarvaenwli :001 70 systemic action on 0.1 100 black bean aphids.
s oo'iE'n V n/ CsBlrS0CH:--CHSP CH: 001m "Ioxicity -10 mg.-Ikg.3//5 g U I (Rats orally) -25 mg./kg.5/5/5 (LD 05) v i" r I Percent Percent fiies 0.1 100 grliidirb eshid 0 01- 132 ac .eanep s values mosquito-larvae, 0.001 100 systemic action on H 7 0]. 100
7 black bean aphids. q
/ fi/OCHr; CzHr-SQr-C:CH-SP V 1 cm :OCHI -T0xictty;..-'.' -100-mg:/lrg. 515 5 (L'Des (Bats orally) 7 I I Percent? Percent d flies---;- 0.1 100 I I V V blackbean aphids-.." 80 Goloradobeetles 40 a i d re es r i t si 0 m q to ae a 10o systemic act-ion on 1 I 100 black beanaphids.
The following -eramples are given by way of flflgen'only and without restrictingthe present invention Example]. V -0 o'c V m-s-cHT-{CH sTiV ...2: J ocr n 80 g. ammonium salt of 0,0-dim ethyI-thiol phospliorie airtime-dissolved in IQ water. -At 6t 3hereare to 96 g.
added slowly 74 g. (2 chloro-2'-methyl-et hyl(1)-) (ethyl-) sulfide. The temperature of 60 is kept for one further hour. 250 ml. benzeneare added and the benzene layer is separated, Washed twice with water and then dried over sodium sulfate (anhydrous). The benzene is distilled ed and the residue fractioiied in vacuo. Themain portion distills axe-011- ;mm. Hg at 83?, the yield -,Example2 V V o jozcsflr e msTcnfien sgr CH; ooarn 190-g. ammonium salt of 0,0-dipropyl-thiolphosphoric acidare dissolved in 300 ml. methanol. While stirring there are added slowly at 60"C. 148 'g'. '(Z-chlord-T- methyl-ethyl( l)-.) (ethyl-)sulfide. .The temperature is kept at 60 C. for one further hour and'then after cooling the reaction mixture is filtered with sulfur. The methanol isremoved by distillation and. the residue is taken up in. 500 ml. benzene and washed thrice with 50 ml. water. The benzene'layer then is dried over anhydrous sodium v p sulfate. After distilling oil the benzene the residue may be purified by vacuum' distillation. There are obtained 224 g. of the new ester of the above formula.
Example 3 CrHsS-CHrCH- S g t on. e. f 190 g. of an ammonium salt of diethylthiol phosphoric;
. acid :are dissolved in 400 of 98% alcohol, 140 g. of
2-chloro-2' -methylethylthioethyl ether are added at C;
The temperature isltept 'at '0. for one :hour, .the salts.
are filtered off with suction "and the methyl alcohol isseparated by distillation in vacuum. The residue is taken. up in .500 ml. of ether, the ethereal solution is washed twice with 50 ml. of water, dried and distilled- :175 g.
of the new ether ofB.P. 0.01 -mm./.92. 1C. are obtained as colorless water-insoluble oil. V
Example 4 V S OCH: Il/ mms-om-cm-s-r on. '0 CH1 17 g. of potassium hydroxide are dissolved in 50 ml.
- of water. 53 g. of dimethyl dithiophosphoric acid are action product is thoroughly shaken with 300 ml. of
benzene. The benzene solution is washed twice with-l00 ml. of water, separated and dried. After removing the benzene the new ester distills over under a pressure of 0.01 mm./ C. '35 :g. of'the ester are obtained as colorless water-insoluble oil."
Example 5 T methylethylthioethyl ether are added dropwise to the solution. The temperature is kept at 4'5" C., ior one hour. The solution is then cooled to room temperature, 300ml. of ether are added, the ethereal layer is separated,
- washed twice with l00 ml. each of water, dried and distilled- 49 g. of the new ester of the RP; 0.01 mm./ 104 C, are obtained'as water-insoluble colorless oil.
wise in form of a 30% aqueous solution so that a tem-' perature of 40-50 C. is maintained. The'solu'tion is stirred for another 30 minutes without heating. Excess hydrogen peroxide which may be presentin slight quantities, can be removed with bisulfite. The solution is diluted with 100 ml. of water and the acid is neutralized with dilute potassium carbonate solution. Some kiesel-' guhr is added and the crude product filtered off from a slight amount of a precipitate. The filtrate is mixed while stirring with solid potassium carbonate in a quantity so that the sulfoxide begins to precipitate. The precipitated ester is taken up in methylene chloride, the aqueous phase is shaken once more with methylene chloride, both methylene chloride solutions arecombined, dried with sodium sulfate and the solvent is removed in vacuum; 32 g. of the crude sulfoxide are obtained as colorless water-insoluble oil. The yield is 82.2% of the theoretical.
Example 7 CzH SO-CHf-OH-S-P (7H3 ocaHs 40 g. of. the sulfide group-containing ester of the following composition: I 00,11,
i CH3 OCaHs are dissolved in 75 ml. of methanol and mixed with 0.5 ml. of 50% sulfuric acid. Beginning at 20 C.; the calculated quantity of hydrogen peroxide (about 30%) is rapidly added in drops, the temperature rising to 4050 C. This temperature is maintained by cooling from outside. After the dropwise addition of the hydrogen peroxide cooling is stopped and the solution is allowed to cool. After about 30 minutes the reaction is complete. .The solution is diluted with 100 ml. of water, neutralized with potassium carbonate solution and'filteredf- The filtrate is mixed with cold, saturated potassium carbonate solution until the sulfoxide separates. The-sulfoxide is isolated by exhaustively extracting with methylene chloride. The methylene layer is dried with sodium sulfate and the methylene chloride removed by distillationjini-vacuum 3.8 g. of the new sulfoxide are obtained as colorless Watersoluble oil. The yield is 88% of the theoretical.
"' p 1 v soon; I
ll/ C2HsSO-GH:CHSP I v v H3 00H; To a solution of 31.2 g. (0.1 mol) of the'sulfide gro containing ester of the following composition: I
S OCH: 1 I j 7 I omss ourt ln s CH3 OCH:
the sulfide groups-containing peraturefor one hour. a .slight excess ofhydrogenfperox ide is removed withsodium bisulfitesolution'. The'solu- 1 413g. (0.15 mol) of the ester of the following position i v I vs ocgn,
' ll/ GzH5SCH:-(|JH-SP\ v CH3 OCgHs T I '3 are oxidized to the sulfoxide by addition of 75 ml. of methanol and 0.5 mol of 50% sulfuric acid with 15 m1. oil a hydrogen peroxide solution (about 30%) at40-50 C. After stirring for another 30 minutes; the solution is; diluted with water, the. excess acid' removed with dilute sodium'carbonate solution'and the precipitated oil "taken" upfinfbenzene. After working up as usual, 40.5 g. of the sulfoxide are obtained as "colorless water-insoluble oil; Yield: 89.7% of the theoretical. 51"..
Example 10 onnso- H,-oH-si ooH=),
41.8 g. (0.15 m l) ofthe ester of the following com position I HzCl are dissolved in ml. of water and 70 ml., of methanol. and mixed with 0.5 of*50% sulfuric acid. While cooling the calculated'quantity of hydrogenperoxide is added dropwise at 40-50". C. The solution is stirred for another 30'minutes without. heating. Slight amounts of hydrogen peroxide :are removed with bisulfit'e solutions After diluting the solution with'50' ml. of water, thesolu tion isadjusted to pH 6 with potassium .carbon'ate solution and the sulfoxide ester is extracted from the aqueous solution by repeatedly shaking with methylene chloride. After drying the solution over sodium sulfate, and dis. tilling off the solvent 38.3 g. of the crude sulfoxide ester are obtained as yellowish water-soluble oil. The yield is 86.8% of the theoretical.
Example "11 Y O H .T- H- i-= 5 omcl '.J'I.'."; 4? g. (0.15 mol) of the ester of the following com position HzCl i are suspended in dilute methanol "cQntaining OIS of sulfuric acid. Oxidizing is carried out with the calculated quantity of hydrogen peroxide at 40.-50 C. in the manner. The previously suspended ester 'dissolyesfpom pletely. 1The'solution is ,diluted water, adjustedto 'ffii -h qt m s tb na e sd h s l i d j is extracted fromthe solution byrep'eatedly shaking with methylene' chloi'ide. "After woi'king ='up as 42" the sulfoxide ester are obtained 'as yellowish, watensohr bie oil.-ield: 86.7% of the theoretical.
" 7 Example. 12 r added until the solution is colorless. The solution is then saturated with sulfate and the resulting sulfone ester taken up in methylene chloride by shaking." After distillingand drying, 36 g. of the sulfone are obtained as olor'less oil which is miscible with water. The purity of the crude product is satisfactory so that distillation is not ifeguired, prior to use. Yield: 88% of the theoretical. Example 13 1 O OCQH C:HsSOr-CHrCHSP CH1 OCQHs 16.2 g. (0.0595 .mol) of the sulfide group-contamin g qster ofthetollowing composition 7 7 mms-cm-o-s-r (His 0 C1 8 Example .15
CHaCl 31; g. (0.1 mol) ,of the ester ,of the following comr7 r o C;H -SCH:CHSL E =(O C255):
are added dropwise at 5-10 C. to a suspension or solu- V tion'of 142 g'. (0.0869 mol) of potassium permanganate and 12.7 g; (0.052mol) ofmagnesium sulfate in 200 m1. of water and :30 ml. of acetone. After stirring for another 30"minutes, sulfurous acid is introduced until the solution becomes 'colorlesa' The ester form is'separated by addition ofsodium sulfate and taken up in methylene chloride. J The methylene chloride layer is. dried'with sodium sulfate and the solvent removed by distillation in vacuum. i. J 15.8 g. of the new suifone are obtained as water-soluble, oil. The yield is 92.1% of'the theoretical.
38 g. (0.137 mol) of the ester'of the following composition .12:. ;:Il1i-7 .1"; fr? if 'J:
are added dropwise at 5- -10" "Cato a suspension of 35 g. of potassium permanganate and 33 g. of magnesium ini400 of water- The suspension is stirred at -C .;for. another v30 minutes and-sulfurous acid is then added untiltthe suspension becomes colorless.- .'I he'.pre c ip te sti in' 9 hs 4 e a ummer ape-obtained aspale yellow, viscous oil of limited y/ater filg i i yaillie nurse-w nt h mental.
V miscible water.
areaddeddropwise at .5.10 C. to a suspensionof 27 g. oil potassium permanganate and 22 got magnesium sulfate in 300 of water. After stirring at 5-10 Cgfor' 30 minutes; sulfurousjacid is introduceduntil the ganese' dioxide is discolored and the sulfone ester form is V separated by addition of sodium sulfate; By repeatedly shaking with methylene chloride, the ester is extracted from thesolution'. After drying and distilling; of the solvent, 2l g'. of the new sulfonc, ester are obtained as a' The yield is 62.8% of the theoreticali T .Efxample ld 7 on, OCH:
39 g. of the sulfoxide group-containing ester of the following composition r O OCH:
L (in, OCH:
are added dropwise at 5- 10 C. to a suspension of 33 g. (0.21 mol) of potassium permanganate and 32 g. (0.13 mol) of magnesium sulfate in 250 ml. of water and tat-acetone. The-suspension is stirred at 10 C. for another /2 hour. The manganese dioxide'which precipitates contains still a small .excms of potassium permanganate. Sulfurous acid is added to remove this until the solution is colorless. The solution is saturated with sodium sulfate and the resulting sulfone ester is extracted with methylene chloride. After distilling and drying, 3 3 g; of the sulfone are obtained as colorless oil whichis Example 17 V V lot/005E;
oimsor onr orks-r' .I I v CH; .OCaH; v v
17.5 giofthe sulfoxide groupcontainingester of the following composition Y a .OQOIHE n/ I Q!H 9' r- B are added dropwise at- 5 -10 C. to a suspension orsolw tion of l 4;2 gfipotassium permanganate and 12.7 g;' magnesium suliate'200 ml. of water andl30 ml. of acetone.
, Stirring is continued for-another 30'minutes and then 7 sulfurous acid is introduced until the solution becomes 'colorless. 'Ihe'ester is separated by the addition of ei v e ti a an f r e fid a PIQCdlII.'&',Of thepreceding examples is followed. 7
sodium sulfate and then takenup in "methylene chloride. The methylene chloride layer is dried with sodium sul fate and the solvent removed by distillation in ,vacuum.
-f f newjsulione are obtained as w tsnsbluble, viscous on. We claim: E
1. A thiophosphoric acid ester of the formula Elli/ 011. s ism 1 s aw:
yellowish oil whichdissolves in water only sparingly.
9 in which R and R stands for lower alkyl radicals, R stands for a member selected from the group consisting of lower alkyl and lower chloroalkyl, A stands for a lower alkylene chain of at least two carbon atoms, X stands for a member selected fi'om the group consisting of oxygen and sulfur, and Y stands for a member selected from the group consisting of S, SO and S0,.
2. A thiophosphoric acid ester of the formula I 0R R-Y-CHz-(FH-S-I R1 OR in which R, R and R stand for lower alkyl radicals, X stands for a member selected from the group consisting of oxygen and sulfur, and Y stands for a member selected from the group consisting of 8, SO and S0 3. A thiophosphoric acid ester of the formula in which R, R and R stand for lower alkyl radicals.
4. A thiophosphoric acid ester of the formula x OR II/ R-SO--GHCHSP R1 OR:
in which R, R and R stand for lower alkyl radicals, and X stands for a member selected from the group consisting of oxygen and sulfur.
5. A thiophosphoric acid ester of the formula 0 011* II/ RSO-GH:-CHSP in which R, R and R stand for lower alkyl radicals.
6. A thiophosphoric acid ester of the formula 5 on: H/ RSOCH(|)HSP R on:
in which R, R and R stand for lower alkyl radicals.
7. A thiophosphoric acid ester of the formula II/ R-SO:CH:CHSP
in which R, R and R stand for lower alkyl radicals, and X stands for a member selected from the group consisting of oxygen and sulfur.
8. A thiophosphoric acid ester of the formula 0 OCH:
9. A thiophosphoric acid ester of the formula ll cnns-cHr-cH-s-P H: OCH:
10. A thiophosphoric acid ester of the formula 11/ onns-om-cn-s-p 11. A thiophosphoric acid ester of the formula 12. A thiophosphoric acid ester of the formula CH; OCHI References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Bacon et al.: J. Am. Chem. Soc. 76, 670-676 (1954).
STATES EPATENT 'oFxfma v CERTIFICATION F CORRECTION 2.952 100 September 15 1960 atent No.
Walter Lorenz, et a1.
It is hereby cei'tified b a are in the above numbered patent requiring d Letters Patent should read as corrected below.
line 36 to 40 the formula should appear as the patent:
Column 7,
toad of as in shown below ins o oc n Signed and sealed Lhi (SEAL) Attest:
ERNEST we SWIDER DAVID L. LADD Commissioner of Patents Attesting Officer
Claims (1)
1. A THIOPHOSPHORIC ACID ESTER OF THE FORMULA
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE350963X | 1955-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2952700A true US2952700A (en) | 1960-09-13 |
Family
ID=6265505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US645403A Expired - Lifetime US2952700A (en) | 1955-11-22 | 1957-03-12 | Thiophosphoric acid esters and their production |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2952700A (en) |
| BE (1) | BE552774A (en) |
| CH (1) | CH350963A (en) |
| FR (1) | FR1168934A (en) |
| GB (1) | GB823732A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3151147A (en) * | 1961-10-12 | 1964-09-29 | Shell Oil Co | Omicron, omicron-dialkyl omicron-1-sulfonylvinyl and omicron, omicron-dialkyl omicron-1-sulfinylvinyl phosphates |
| US3153664A (en) * | 1961-09-06 | 1964-10-20 | Bayer Ag | S-(3-alkylmercapto 2-halo propyl) and s-(3-alkylmercapto 2-halo propenyl) esters of pentavalent phosphorus acids |
| US3205131A (en) * | 1961-06-03 | 1965-09-07 | Bayer Ag | Stable concentrates of organic phosphorus insecticides |
| US3742097A (en) * | 1969-12-10 | 1973-06-26 | Exxon Research Engineering Co | Process for preparing diadducts of hydrocarbylthiophosphoric acids |
| US3878267A (en) * | 1973-05-09 | 1975-04-15 | American Cyanamid Co | Oxygenated derivatives of s-(tert-butylthio)methyl o,o-diethyl phosphorodithioate and phosphorothioate |
| US3939263A (en) * | 1973-05-09 | 1976-02-17 | American Cyanamid Company | Methods of combatting insects and acarina using oxygenated derivatives of S-(tert-bulythio)methyl O,O-diethyl phosphorodithioate and phosphorothioate |
| US4299783A (en) * | 1980-04-28 | 1981-11-10 | Chevron Research Company | 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660543A (en) * | 1969-03-04 | 1972-05-02 | Exxon Research Engineering Co | S-2-hydrocarbylthio-alkyl esters of thiophosphorus acids |
| CN115232164B (en) * | 2022-07-04 | 2024-08-06 | 新乡医学院 | Preparation method of sulfonyl substituted thiophosphate compound |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2565920A (en) * | 1948-03-26 | 1951-08-28 | American Cyanamid Co | Triesters of dithiophosphoric acid |
| US2565921A (en) * | 1948-03-26 | 1951-08-28 | American Cyanamid Co | Condensation of o, o-diesters of dithiophosphoric acid and aliphatic alcohols or mercaptans with higher aliphatic aldehydes |
| DE836349C (en) * | 1950-05-10 | 1952-04-10 | Bayer Ag | Process for the preparation of neutral esters of thiophosphoric acid |
| US2596076A (en) * | 1948-03-26 | 1952-05-06 | American Cyanamid Co | Dithiophosphate esters as insecticides |
| US2597534A (en) * | 1949-05-07 | 1952-05-20 | Bayer Ag | Neutral esters of thiolphosphoric acid |
| DE876691C (en) * | 1951-07-06 | 1953-05-18 | Bayer Ag | Process for the preparation of dithiophosphoric acid esters |
| DE876692C (en) * | 1951-07-07 | 1953-05-18 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| US2791599A (en) * | 1952-12-31 | 1957-05-07 | Pest Control Ltd | O, o'-dialkyl s (alkyl sulfoxyethyl) phosphorothiolates as pesticides |
-
0
- BE BE552774D patent/BE552774A/xx unknown
-
1956
- 1956-11-12 CH CH350963D patent/CH350963A/en unknown
- 1956-11-22 FR FR1168934D patent/FR1168934A/en not_active Expired
- 1956-11-22 GB GB35752/56A patent/GB823732A/en not_active Expired
-
1957
- 1957-03-12 US US645403A patent/US2952700A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2565920A (en) * | 1948-03-26 | 1951-08-28 | American Cyanamid Co | Triesters of dithiophosphoric acid |
| US2565921A (en) * | 1948-03-26 | 1951-08-28 | American Cyanamid Co | Condensation of o, o-diesters of dithiophosphoric acid and aliphatic alcohols or mercaptans with higher aliphatic aldehydes |
| US2596076A (en) * | 1948-03-26 | 1952-05-06 | American Cyanamid Co | Dithiophosphate esters as insecticides |
| US2597534A (en) * | 1949-05-07 | 1952-05-20 | Bayer Ag | Neutral esters of thiolphosphoric acid |
| DE836349C (en) * | 1950-05-10 | 1952-04-10 | Bayer Ag | Process for the preparation of neutral esters of thiophosphoric acid |
| DE876691C (en) * | 1951-07-06 | 1953-05-18 | Bayer Ag | Process for the preparation of dithiophosphoric acid esters |
| DE876692C (en) * | 1951-07-07 | 1953-05-18 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| US2791599A (en) * | 1952-12-31 | 1957-05-07 | Pest Control Ltd | O, o'-dialkyl s (alkyl sulfoxyethyl) phosphorothiolates as pesticides |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3205131A (en) * | 1961-06-03 | 1965-09-07 | Bayer Ag | Stable concentrates of organic phosphorus insecticides |
| US3153664A (en) * | 1961-09-06 | 1964-10-20 | Bayer Ag | S-(3-alkylmercapto 2-halo propyl) and s-(3-alkylmercapto 2-halo propenyl) esters of pentavalent phosphorus acids |
| US3151147A (en) * | 1961-10-12 | 1964-09-29 | Shell Oil Co | Omicron, omicron-dialkyl omicron-1-sulfonylvinyl and omicron, omicron-dialkyl omicron-1-sulfinylvinyl phosphates |
| US3742097A (en) * | 1969-12-10 | 1973-06-26 | Exxon Research Engineering Co | Process for preparing diadducts of hydrocarbylthiophosphoric acids |
| US3878267A (en) * | 1973-05-09 | 1975-04-15 | American Cyanamid Co | Oxygenated derivatives of s-(tert-butylthio)methyl o,o-diethyl phosphorodithioate and phosphorothioate |
| US3939263A (en) * | 1973-05-09 | 1976-02-17 | American Cyanamid Company | Methods of combatting insects and acarina using oxygenated derivatives of S-(tert-bulythio)methyl O,O-diethyl phosphorodithioate and phosphorothioate |
| US4299783A (en) * | 1980-04-28 | 1981-11-10 | Chevron Research Company | 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB823732A (en) | 1959-11-18 |
| FR1168934A (en) | 1958-12-18 |
| CH350963A (en) | 1960-12-31 |
| BE552774A (en) |
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