US2952700A - Thiophosphoric acid esters and their production - Google Patents

Thiophosphoric acid esters and their production Download PDF

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Publication number
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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ester
water
solution
thiophosphoric acid
formula
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Lorenz Walter
Schrader Gerhard
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—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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US645403A 1955-11-22 1957-03-12 Thiophosphoric acid esters and their production Expired - Lifetime US2952700A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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 (zh) * 2022-07-04 2024-08-06 新乡医学院 一种砜基取代的硫代磷酸酯类化合物的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US2565920A (en) * 1948-03-26 1951-08-28 American Cyanamid Co Triesters of dithiophosphoric acid
DE836349C (de) * 1950-05-10 1952-04-10 Bayer Ag Verfahren zur Herstellung von neutralen Estern der Thiophosphorsaeure
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
DE876692C (de) * 1951-07-07 1953-05-18 Bayer Ag Verfahren zur Herstellung von Thiophosphorsaeureestern
DE876691C (de) * 1951-07-06 1953-05-18 Bayer Ag Verfahren zur Herstellung von Dithiophosphorsaeureestern
US2791599A (en) * 1952-12-31 1957-05-07 Pest Control Ltd O, o'-dialkyl s (alkyl sulfoxyethyl) phosphorothiolates as pesticides

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US2565920A (en) * 1948-03-26 1951-08-28 American Cyanamid Co Triesters of dithiophosphoric 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
DE836349C (de) * 1950-05-10 1952-04-10 Bayer Ag Verfahren zur Herstellung von neutralen Estern der Thiophosphorsaeure
DE876691C (de) * 1951-07-06 1953-05-18 Bayer Ag Verfahren zur Herstellung von Dithiophosphorsaeureestern
DE876692C (de) * 1951-07-07 1953-05-18 Bayer Ag Verfahren zur Herstellung von Thiophosphorsaeureestern
US2791599A (en) * 1952-12-31 1957-05-07 Pest Control Ltd O, o'-dialkyl s (alkyl sulfoxyethyl) phosphorothiolates as pesticides

Cited By (7)

* Cited by examiner, † Cited by third party
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

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CH350963A (de) 1960-12-31
BE552774A (en(2012))
GB823732A (en) 1959-11-18

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