BE603255A - - Google Patents

Description

       

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 EMI1.1
 



  . ", 'louV8aux esters tb1oph'8 and their process.-..., .J" fl \ -.;: "t of preparation.'.



  <The present invention relates to O, S- esters
 EMI1.2
 dialkylphosphoric or -thiophosphoriceaJ6 corresponding to the following general formula:
 EMI1.3
 

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 in which R and R1 represent any alkyl groups, while R2 signifies an aliphatic radical. any cycloaliphatic or aromatic, optionally substituted.



  The Applicant has just found that it is possible to react O, S-dialkylphosphorous acid monohlorides with any alcohols or phenols or with any aliphatic or aromatic mercaptans in the presence of a suitable aid acceptor, in such a way that the esters or thiol esters of 0, S-dialkylphosphorous acid are formed. By adding sulfur, the very stable esters or thiol esters of O, S-dialkyl-thionophosphoric acids are obtained.



  This process will be explained in more detail by the following equation
 EMI2.1
 The symbols have the meanings already indicated.



  It has proved useful in this case not to isolate the unstable intermediate products, but to add the sulfur directly. The new process offers the advan-

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 stage of being able to be applied to practically all
 EMI3.1
 alcohols # meroaptan8 or phenols. In this way, a large number of thionophosphates are obtained which are distinguished by good insecticidal properties.



  Further work on the subject of the invention has shown that the products resulting from the
 EMI3.2
 reaction of O, S-dialkylphosphorous acid mcnochlorides with any alcohols, phenols or mercaptans can also be converted with oxy-water.
 EMI3.3
 hampered by the corresponding O (a) -alkyl, -oyoioaryl or 11c esters of O, S-dialkylphosphoric acid. This reaction will be illustrated by the following equation!
 EMI3.4
 in which the symbols R, R1 and R2 correspond to the definitions given above.



  Surprisingly, in the reaction of reaction products obtained from acid monochlorides
 EMI3.5
 O, S-dialk3rlphosphoreuz and mercaptans, namely thiol esters of O, S-dialkylphosphorous acid with hydrogen peroxide, no oxy-

 <Desc / Clms Page number 4>

 dation of thiol sulfur. Such behavior of the thiol esters of O, S-dialkylphosphorous acid is surprising and was not to be expected.



  In the implementation of this method, it is also not
 EMI4.1
 it is no longer necessary to isolate the O (S) -a7.kyl, -cycloalkyl or -aryl esters of O, S-d.ialkyl-phosphorous acid obtained as intermediate products; on the contrary, it is preferable to immediately oxidize, using hydrogen peroxide, the products resulting from the reaction of O, S-dialkylphosphorus monohlorides with alcohols or phenols or mercaptans.



  These compounds also have insecticidal properties and must consequently find their application as agricultural parasiticides, in particular in the field of plant protection.



  Always following the inventive idea which is the basis of the invention, it has been found that it is possible to react the chlorides of O, S-dialkylphosphorous acid also with alkylene oxides, thus obtaining good ren -
 EMI4.2
 demente'leti O, S-dialkyl-0-chloralkyl esters of phosphorous acid.

   By addition of sulfur or by oxidation of these esters of phosphorous acid, one obtains
 EMI4.3
 holds Ols-dialkyl-O-ohloralkyl esters of (thio-) phosphoric acid.

 <Desc / Clms Page number 5>

 We @a explain this process by taking for example
 EMI5.1
 The reaction of 0,8-alphoepho-, # 6fiiSl - aide chloride reaction: ij '/ y]' "fè ';' 1: e ethylene oxide and the sublot treatment Of 'ïJ" , .J ", * sequent with sulfur or hydrogen peroxide of
 EMI5.2
 > ....; "!: if {O, 8-diethyl-O-B-ohlcr6tbyl ester of phosphorous aid
 EMI5.3
 Reaction I is advantageously carried out in the presence of a suitable inert solvent or diluent, while in the subsequent treatment with sulfur, or in the subsequent oxidation, it is not necessary to operate in the presence of a solvent. or thinner.



  Since these esters have a reactive chlorine atom, they are, among other things, valuable intermediate products for the manufacture.
 EMI5.4
 other phoaphor3quea esters with insecticidal activity. They also possess insecticidal properties by themselves.

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 EMI6.1
 The 098-alkylphosphorous acid monochlorides used as intermediates and having the general formula
 EMI6.2
 in which R and R 1 represent an optionally substituted alkyl radical are not yet described in the chemical literature.

   It has surprisingly been found that readily available O-alkylphosphorous acid dichlorides can be readily converted into them.
 EMI6.3
 OpS-alkylphosphorous acid monochlorarea when reacted in the presence of an inert solvent with a suitable tertiary base and equivalent amounts of any mercaptan.



  As solvents have been found to be particularly suitable low boiling point hydrocarbons, such as petroleum ether and ligoline; but it is also possible to use in this reaction low-boiling anhydrous ethers, such as, for example, diethyl ether.



  As tertiary bases, pyridine, triethylamine, dimethylaniline and the like can be considered in particular.

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  This reaction is advantageously carried out at relatively low temperatures, which should not exceed approximately 0 C. O, S-dialkylphosphorous acid chlorides are then obtained with particularly good yields.



  It is also possible to obtain the O, S-dialkylphosphorous acid monochlorides by reacting aliphatic meroaptans with an excess of phosphorus trichloride and by reacting the resulting 8-alkyl-phosphorous acid dichlorides with alcohols in the presence of a tertiary base.



  This latter process will be illustrated by the reaction diagram below:
 EMI7.1
 / 1 Risa + POl3> R1-S-P, Cl + Hel / 1 OR base wrong. - RO -01 + baae wrong Ho W R1S> In this equation the symbols R and R1 have the meaning indicated above.



  This reaction is advantageously also carried out in the presence of an organic solvent, for example of an anhydrous ether at low boiling point, such as diethyl ether; but one can also consider oomme solvents very volatile hydrocarbons, such as petroleum ether, benzene or ligrolne.

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 EMI8.1
 



  To fix l t 8014..uorc1r1Q. \\. strength an oom * de la j <; * 1 <'j <j r6.01; 10n,:, 011 can en1J ut, i, a.r 4 ...... tar-,? 'u.a: 1r., ¯lle.h¯ ",' - que la pr, d3.as; ',,';. 's tri-" µéthyiaààe .. ... \' làlùanaine. ethylamine or, i 'a', Ï yjy - a.7 * .ae. ", 6th; yllUline 1. 1..t 5 '; .. (sànm%' e, aonTo edit xcatta r 'oeoonda1res: we con- # i +, i #% rnqy ;; ..' <dued this reaction: tlce .4 des tewpératM'ea s.latxt 0 + 70oG: "yG ranging +10 C <.ypootdMt, from .la O, OZ'1Je, we ob-. -1: <; '",. +. /. i <f? 7 * '. t, kf? pe: holds the products of the process with doo redptuts par- ....... ".: ... o., r tioulieresent good and 4 the state of graÍ140 <pun "6.



  % iou1iéXnen% bona i'éiat) 1 ",". ' "'" K lCU "
 EMI8.2
 In the examples which follow the parts indicated are understood to be by weight.



  Example
 EMI8.3
 
 EMI8.4
 27 g (0.25 mol) of! 3-ethya.mercapto-ethanol are dissolved
 EMI8.5
 in 150 oc of toluene. To this solution is added with stirring 25 parts of anhydrous pyridine and the mixture is introduced.
 EMI8.6
 44 g of 0, S: diéthy.phosphorous acid chloride (P.E. 1 '46oC) then drop by drop at 30-400C, passing through a nitrogen cutter. Stirring is continued for one hour at 400C and then introduced

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 EMI9.1
 8 "of 8ouln. 9 LI M.4tuon of lO1be ube loia ter-" O "." 1 .. ", ...... eo .... turn * 90'6. '.:,",' . -J la ", P and anaiµl 1 * M & <4 <j% cn a? Â <beM <M. 'II.) L. <11 pillaeiewN" priJ8et ;,.' ,:, '.cmiJb1' "wt, luis on 1. î ;; 1" we have 4 "4th b1carbonate 00 -du suuate ao and fi: f.rf.O'U0IU16e.



  We get & tu1 ".4Ú, .. ft., 'Bo'8w ... t.



  8700 knots 0.01 M, Theory $ 1 clear.
 EMI9.2
 Example
 EMI9.3
 
 EMI9.4
 31 g (0.25 mol) of α-6thylmeoapto-6thylmeroaptan is dissolved in 100 cc of toluene. To this solution we
 EMI9.5
 add 25 g of pyridine and add dropwise
 EMI9.6
 to 3000 44 g of 0,8-dieth-lhoaphorous acid chloride, passing through a stream of anote. Stirred for one hour at 50 Q and then added z of sulfur.



  The reaction mixture is heated for an additional hour at 9000 and then processed as deozlt in

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 EMI10.1
 1 'oxow>, we ob% i * xt * in1 35 dn such enter bo4tu ", IIO'ori under 0.01 M. lemàmm-ta 5 1'% d at / A / f. Example 3
 EMI10.2
 
 EMI10.3
 Z 6 (0 # 25 mol) of p-chlorophenol is dissolved in iso this 3rd total and 25 g of anhydrous pyridine are added thereto. 2Ute 44 g of ti8-d3thylphoephoreuz aid chloride are introduced dropwise by passing a stream of nitrogen. We maintain the temperature
 EMI10.4
 ture for andMore one hour at 40 C and then added 8 g of sulfur. The reaction mixture is heated for one hour at 90 ° C. and then treated as described in Example 1. 47 g of the new ester are thus obtained, boiling at 96 ° C. under 0.01 mm.

   Yields 63% of theory.



  Example 4
 EMI10.5
 

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 EMI11.1
 41 g (Ou25 sole) of 294-dîcbloropbizol are dissolved in 100 cc of toluana. 25 l of pyridine were added and 30 - 4000 44 l of acid chloride was added to drop, -d.8tblpbosoreu are passed through a stream for 4 '. Stirred for one hour at 40 and this then add an additional 8 a. The reaction mixture is then added for another hour at 19 a C and treated as described in axazpla 1. This gives ...,., new ester boiling at 99 C under 0.01 mm.



  Yield: 54% of theory.



   Example 5
 EMI11.2
 
 EMI11.3
 50 g (0.25 mol) of 2p495-trichloroph6nol are dissolved in 150% of toluene. 25 g of pyridine are added thereto and 44 g of
 EMI11.4
 0 # 8-di6ethylphosphorous acid chloride. After heating for one hour at 40 ° C., 8 g of sulfur are added and the reaction mixture is maintained for another hour at 90 ° C.

   The treatment is continued as described in Example 1 and 50 g of the new ester are obtained in the form of a weakly yellow oil, insoluble in water. Yield: 55% of theory.

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The calculation gives for a molecular weight of 366:
 EMI12.1
 , /. ¯ ,, <'Cl 29.2% S 17.5% 2 8.5% Ô / µ We found: Cl 28.6% S 17p3% P 8.4 leaked
Example 6
 EMI12.2
 36 g (0.25 mole) of 6-naphthol are dissolved in 100 cc of toluene. 25 g of pyridine are added thereto and 44 g of O, S-diethylphosphorous acid chloride are introduced dropwise by passing through a stream of nitrogen. The reaction mixture is heated for one hour at 40 ° C. 8 g of sulfur are then added and the mixture is heated for a further hour at 9000.

   The treatment is continued as described in Example 1 and 40 g of the new ester are obtained in the form of a weakly yellow oil, insoluble in water. Yields 51% of theory.



  The calculation gives for a molecular weight of 312:
S 20.5 P 10.0% We found S 19.2% P 10.2%
Example 7
 EMI12.3
 

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 28 g (0.25 mol) of thiophenol are dissolved in 150% of toluene. 25 g of pyridine are added thereto and 44 g of O, S-diethylphosphorous acid chloride are introduced dropwise while passing through a nitrogen flow. It is heated for half an hour at 40 ° C. and 8 g of sulfur are then added. The reaction mixture is maintained for one hour at 90 ° C. and then treated as described in Example 1. 40 g of the new ester are thus obtained, boiling at 10 6 0 under 0.01 mm. Yield: 58% of theory.



    Example
 EMI13.1
 36 g (0.25 mol) of p-chlorophenylmercaptan are dissolved in 150 cc of toluene. 25 g of pyridine are added thereto and 44 g of O, S-diethylphosphorous acid chloride are introduced dropwise by passing through a stream of nitrogen.



  The reaction mixture is maintained for one hour at 40 ° C.



  8 g of sulfur are then introduced with stirring and the mixture is heated for a further hour at 80 ° C. After usual preparation, 37 g of the new ester are obtained, boiling at 119 ° C. under 0.01 mm. Yield: 48% of theory.

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  Example
 EMI14.1
 39 g (0.25 mol) of p-methylmercaptothiophenol are dissolved in 150 cc of toluene. 25 g of pyridine are added and 44 g of O, S-diethylphosphorous aoid chloride are then introduced dropwise by passing through a nitrogen flow. The reaction mixture is maintained for one hour at 4000. 8 g of sulfur are then added and the mixture is heated for a further hour at 90 C. After the usual preparation, 58 g of the new ester are obtained in the form of a yellow oil, insoluble in the water. Yield: 72% of theory.



   Example 10
 EMI14.2
 35 g (0.25 mol) of p-methylmeroaptophenol are dissolved in 150% of toluene. 25 g of pyridine are added thereto and 44 g of O, S-diethylphosphorous acid chloride are introduced dropwise at 30-40 ° C. The reaction mixture is maintained for half an hour at 40 C. Then 8 g of sulfur are added and the mixture is heated for a further hour at 90 C. The operation is continued as described in Example 1 and thus 40 is obtained. g of the new ester boiling at 105 ° C. under 0.01 mm. Yield: 52% of theory.

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  Example 11
 EMI15.1
 30 g (0.25 mol) of p-cyanophenol are dissolved in 150% of toluene. To this solution is added 25 g of pyridine.



  44 g of O, S-diethylphosphorous acid chloride are then introduced dropwise at 30 C by passing through a stream of nitrogen. The mixture is stirred for one hour at 30 ° C. and 8 g of sulfur are then added. The reaction mixture is heated for one hour at 90 ° C. and then treated as described in Example 1. 34 g of the new ester are obtained, boiling at 98 ° C. under 0.01 mm. Yield: 47% of theory.



   Example 12
 EMI15.2
 34 g (0.25 mol) of p-nitrophenol are dissolved in 150 cc of toluene. 25 g of pyridine are added thereto and 44 g of O, S-diethylphosphorous acid chloride are brought in dropwise at 30 ° C. by passing through a stream of nitrogen.



  The mixture is stirred for one hour at 4000 and then 8 g of sulfur is added. We maintain the reaction mixture

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 EMI16.1
 ...., ¯.U "1 \ 90 0 * <we haveQ¯ '", on 1 .... 1 \ ... ", aoaame'? T.,;.! T.4 1, .. ..Jl. 1. on Ob1iR 3 du nçuvel tatar ,,: JO. ' 1 \ "". 'Mdr \ t .W \., Iululir 4ana 1'u. \ U ..



  '191 "." T'. ' te 4th la, ¯60, he.



  ) 'lUII1I.Jl
 EMI16.2
 
 EMI16.3
 We make a 1.aoudre 44 (0125 mole) 49 $ -ohlom-4-Mtrùphenel daa 150 00 4Ç% Oluènot A 30 0 we ADD 44 e 4a Chloride decides a, 9-detylponhorut by tatlanting p, saer through a ran d ' aote, On MAIntiont 1A 'e'n1 \ R'. p dani one: hour at 3000 and added alocé 8 G to dhows The reaction mb7.ae tm4an 'is heated for another hour at 9000 and it is then treated vpmtr iiqu6 dana Ilexe # aple 1, We obtain aine% 52 g of new outer aoua tome of yellow oil, insoluble in water, yields 61% of the
 EMI16.4
 theory.



  Example 14
 EMI16.5
 
 EMI16.6
 39 g (0.25 mol) of 4-thyeopto-ethylphenol was dissolved in 150% of toluene, 25 6 of pyridine was added and drip fed to 44 g of d. chloride

 <Desc / Clms Page number 17>

 
 EMI17.1
 .... "" "'r ¯1118 & .. CI84 .. ptu <Hr au traers ± ± - -: -t.-J..1! e ....." "1.1tt .ta t lra- mother JMQIdant De ----- t M ² .. v p ..: r-? " pM ,, ± fl, ¯ L¯ fi "., ..........." "118 -) .. - rio! ') ,,:" "... l'! ':' * '' '1, "" J'j, 1DI8 .1Itw: r8 1. 90 o.



  Î * @. <MMMt <Nkét.tJwM1 obtained 1 Frr, ", 4 ''., R, x i" '. o1lU8I11i 74. "., td ..-- ,." '; t ;, .. p +, in- "' * ^ 2 w *, (Jo ..



  ', rr 1t
 EMI17.2
 
 EMI17.3
 Ca II J J J11. 2T g (o * 25 ..- J.) .. net% 1-thioethyl ether b- 150 ce is re. GIll. 7 qn 25 g of pyridine and we: have arrested you ......- die .. JlAIie .. 3dC, 44 of 4'S-c..orrahert acid chloride nt1wm <t "" 81 "at traTe1 ' 8 a current 3 "aaoe. h 1III8: t .... 3a 1'-Pza "'" for another half d .. 7 ajoa; te a1.era 8 C of aoufre. We heat: the mixture .- -r.t 1ID8 âdare at 90 C and cragge it e <anme -fimiH ...... 1 * ex +> 1. We thus obtain 40 g of: a'.OUYe]. es: er A 84 C 8OU8 0.01 mm. Yield: 58 "Theory.
 EMI17.4
 

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 EMI18.1
 



  30 S (0.25 mole) of n-he3t, yl'Mrcaptan dama 150 ce 'too toloene are dieed. We 'add 2µ of and we let drop .. qoarte y 3d' 14 a of 4'ac14e chloride O, 5-d1ethylw, "'- (f' / 1 ,, - '.. o-' I- .6 o? 1! 'C, â.e, Se' ü is a stream of nitrogen.



  :.,. ,, - 4. * b F 'sP:?:,. ^' r 'r,, x On 881J1Umt la / ¯ ¯ "* ,,, JIt is a half hour at 40C and we add' t! dI8Íd.te, '. 8 84th µµµro. The reaction mixture is heated for '1 r 9ûaC and then treated ....., ,,>. ", \:;: - ²" "' * count 1nd1qu6, fay ypQ ± le f, On thus obtains 41 g of the toning DOUY1 eater A 82 C 8OU8 0, 01 tm. Yield: 67% of theory.



   Example 17
 EMI18.2
 30 g (0.25 mol) of ethyl thioglycolate are dissolved in 150 cc of toluene. 25 g of pyridine are added and
 EMI18.3
 drop by drop to 3o c 44 g of acid chloride 01,3-d: iethyl: Lphosphorus = by passing through a stream of nitrogen. The temperature is maintained for a further half an hour at 30 and then 8 g of sulfur are added. The reaction mixture is heated for one hour at 90 C and then treated as described in Example 1. 44 g of the new enter boiling at 84 C we 0.01 mm are obtained.



  Yield: 61% of theory.

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  Example 18
 EMI19.1
 56 g (11.4 mol) of p-methylmercapto-phenol and 40 g of pyridine are dissolved in 300 cc of toluene. While stirring and passing a stream of nitrogen is introduced dropwise into this solution at 30 - 40 C, 81 g of acid monochloride
 EMI19.2
 0-ethyl-S-isobutylphfephorous (M.p. 1: 570C) then the mixture is kept for a further hour at 40 ° C. and 13 g of sulfur are added to it all at once. The reaction mixture is then heated for one hour at 90 ° C. and treated as indicated in Example 1. 115 g (95% of theory) of the above-mentioned ester are thus obtained. (P.E.0.01: 136 C).



   Example 19
 EMI19.3
 To a solution of 56 g (0.4 mol) of p-methylmercaptophenol and 40 g of pyridine in 300 of toluene is added while stirring at 30 - 4000 75 g of 0-ethyl-Sisopropylphosphorous acid monochloride (PE1: 52 C) while passing a stream of nitrogen. The temperature is maintained for one hour at 40 ° C. and 13 g of sulfur are then added. The reaction mixture is stirred for an additional hour at 9000 and then treated as described in Example 1. This gives

 <Desc / Clms Page number 20>

 thus 105 g (91% of theory), of the above-mentioned ester, the boiling point of which is 128 C at 0.01 mm.



  Example 20
 EMI20.1
 32 g (0.3 mol) of ss-ethylmercaptoethanol and 36 g of pyridine are dissolved in 300 cc of toluene. While stirring, a stream of nitrogen is passed through and 54 g of O-methyl-S-methylphosphorous acid monochloride (m.p. 2.34 C) are added to the solution at 30-40 C; the reaction is allowed to continue for one hour at 40 ° C. and 10 g of sulfur are then added. While stirring, the reaction mixture is heated for a further hour at 90 ° C. and treated as described in Example 1. In this way 56 g (89% of theory) of the ester indicated above are obtained, boiling at 82 C under 0.01 mm.



   Example 21
 EMI20.2
 53 g (0.5 mol) of ss-ethylmrcaptoethanol and 50 g of pyridine are dissolved in 300 cc of toluene; While stirring and passing a stream of nitrogen, 80 g of O-ethyl-S-methylphosphorous acid monochloride are added to the solution at 30-40 C. The temperature is maintained for one hour at

 <Desc / Clms Page number 21>

 
 EMI21.1
 4ofl6 * fl <Mt 1 <tTnit eors 1D41.fú dane 1 eµ-ple 1. We obtain aúd 122 g (9C 4 <the theory) of eater oi-des8U8,, toId11.n. O 80118 0.01 - ,.
 EMI21.2
 
 EMI21.3
 



  DIu UN solutioss of 53 s (0.5 8018) of 9-tbrlmeroaptos': '' * 1101 and 50 9 of plrsldins 4au 3oe cc of toluene on 1DtZ04u1't .. 30 - 4d'c, tottt a shaking and silent pass tn courmt dasrots, 95 a of JIOJ3Dchloride 4'ac1de 0-ethyl-StHI1 "On1If: 1Hênns (yE1s52oC); then, we add had 1 riu-t: 1otJul 16 a further and we heat it for gm o 1 bou 4 geo, The operation is carried out as described in Example 1, and one thus obtisnt 99 i (92 of theory) of the new ester Cl "" O, 01 s92oC).



  Bxexwle 23
 EMI21.4
 
 EMI21.5
 53% (0.05%) of S-6ih11mercapt06thanol and 50 g of "..ri4: 1M dom 300 cc of toluene are dissolved and to this 801 μl are added.
 EMI21.6
 
 EMI21.7
 tion everything; then pass a stream of nitrogen, 4 40'OCP 101 17nochlorur. of 0-6thyl-8-isobutylphosphoyeax C: r''1'1 "O ', BD.81d.t., is heated for a further

 <Desc / Clms Page number 22>

 hour 40 C and add 16 g of sulfur, the mixture is heated
 EMI22.1
 reaction for = or # one hour at 900 and then treated as indicated in Example 1. 130 g (96% of theory) are thus obtained 4e 'l' ..ter suonentioml (P.2, qf 96 c ).

   Example 24
 EMI22.2
 
 EMI22.3
 To a solution of 61 g (0.5 mol) of 8-ethylmercaptoethyl-mercaptan in 400 cc of benzene is added 50 g of anhydrous pyridine; drop by drop while stirring and passing through a stream of nitrogen at 30 C,
 EMI22.4
 37 g (0.5 mol) of 0-8-dizbthylphosphorous acid saoaoahlorura (PE2: 34 C) and the reaction mixture is heated for a further hour at 40 C. This done, 16 g of sulfur, the mixture is heated for one more hour at 80 ° C. and treated as indicated in Example 1. In this way 103 g (79 of theory) of OS-dimethyl-S- are obtained.
 EMI22.5
 (B-bthy1mercapto-bt% y1) -thionophosphate as a yellow oil, insoluble in water.



  Analysis: Calculated for a molecular weight of 262:
S 48.8% P 11.8% we found! S 49.0% P 11.5%.

 <Desc / Clms Page number 23>

 
 EMI23.1
 Example 25 1. X .. ¯ It '1,,,' ù> ',' 1 "
 EMI23.2
 
 EMI23.3
 dissolves 33- 0.25 -mole) s "r7;, Nr [, a., l'r ,, .. dissolves 33 g (0.25 mole) of p-chlorophénoenaemble.aveo 25 g of anhydrous pyridine in 150 cc de = tolune:

   Tou, t. "In,, .i,, ¯,;,, '..." i. /: ¯.i '"' r '*' '', # 5 stirring we add to this solutionâ 30 - 40 C 44 gas0, 25.,> I oz li.i.,;>, R> ..,;> > mole) of 0.8-dibthylphosphoeuid monohydride 4 boiling at 46 ° C. Under 1, the mixture is stirred for a further hour at 40 ° C., and then added, under external cooling, 30 g of hydrogen peroxide at 35 ° C. %, the addition being adjusted so that the internal temperature does not appreciably exceed 30 - 30 C. As soon as the dropwise addition of the hydrogen peroxide is completed, the reaction product is mixed with 200 cc of water. When frozen, the toluene layer is separated, washed with water and dried over sodium sulfate.

   After removing the solvent by distillation and subjecting the residue to fractional distillation, one obtains
 EMI23.4
 46 g (66 56 of theory) of O, S-diethyl-0- (p-chlorophnsrl) - phosphate boiling at 96 C under 0.01 mm.
Example 26
 EMI23.5
 

 <Desc / Clms Page number 24>

 
 EMI24.1
 HM ooa from 93 to.5 dw d.,. Adry .'- 6wlithOP, d = a * 400 oc do d K, * $% rW 4V pi due there m * xoa <y ,. 'a S 3 tot agitât ..1 "" @ = U! iMM Mxw> yes in aaR t haoe # µ,' ét-M, 88, de moaaahl.asure dada '7 es at eoatinna shake for more lÀlÀ-W at 3 we add 50 to 36 oxygenated water in such a way that the to2affl 40 reactioa which, À4iãe gae 35 C.% n fMa <ïo 1le nt nr the hydrogen peroxide-l completed, agttw Voûdmt 0 * "00 , autea and one & 3oa then to the product t 'igm uomsti tac agiamwe of 200 ce dt U, éue6o and of 50 because dflmddo d & << MM <! <20 6.

   We $ pae''1a bensimâqmo on 1 * Um mm MW solution of uo * 9oemate at 4% and this a'e <ommltw <Mar zur sodium sulfate. during the 3ra.atia cm 6 * tlmt 7% (60% of theoyj.e) of 0,8-diethylÔ-B-% Ey> eoew phosphate boiling at 840 knots 0.0 m ..
 EMI24.2
 Example 27
 EMI24.3
 
 EMI24.4
 82 g (0.5 mol) of 2 '". F-d.j1'l phenol are dissolved with stirring in 400 cc of benzene, added to the mixture, # è'Ó'w.)' I.



  50 g of pyridine and then, at 30 ° C., its g key zdgoctl6r w of 0.8-dié% hylphoephorous acid; we heat 'the & 16 of
 EMI24.5
 
 EMI24.6
 reaction for one hour at 30-35 C and -a, a e u1 "1-

 <Desc / Clms Page number 25>

 stirring is equivalent to 50 g of 36% hydrogen peroxide dropwise at 35 C. Heating is continued for a further hour at 35 ° C. and the reaction product is then poured into water acidified with a little dilute hydrochloric acid. The benzene solution is separated, washed with water and dried with sodium sulfate. In the subsequent fractional distillation 104 g (66% of theory) of #, S-diethyl-O- (2,4-dichlorophenyl) -phosphate are obtained, boiling at 1080 under 0.01 mm.



   Example 28
 EMI25.1
 55 g (0.5 mol) of thiophenol are dissolved in 400 cc of benzene. To the solution obtained is added with stirring 50 g of pyridine, then introduced dropwise at 30 - 35 C, while continuing to stir, 88 g of O, S-diethylphosphorous acid monochloride, the mixture is maintained for a further period. one hour at 30 - 350C and finally 50 g of hydrogen peroxide at 36%. The reaction mixture was heated for a further hour at 35 ° C. and then worked up as described in the previous examples.

   85 g (65% of theory) of O, S-diethyl-S-phenylphosphate are thus obtained, boiling at 90 ° C. under 0.01 mm.

 <Desc / Clms Page number 26>

 Example 29
 EMI26.1
 To a solution of 61 g (0.5 mol) of ss-ethylmercaptoethylmercaptan in 400 cc of benzene is added 50 g of pyridine and then 88 g of O, S-diethylphosphorous acid monochloride are added dropwise at 35 C. The reaction mixture is heated for a further hour at 35 ° C. and then 50 g of 36% hydrogen peroxide are added at this temperature.



  Once the addition is complete, the reaction mixture is heated for an additional hour at 35 ° C. and then treated as indicated in Examples 25 - 27. This gives 79 g (58% of theory) of 0 -S-diethyl-S- (B-ethylmercaptoethyl) -phosate boiling at 8800 under 0.01 mm.



   Example 30
 EMI26.2
 To a solution of 77 g (0.5 mol) of 4-methylmercapto-3methylphenol in 400 cc of benzene is added with stirring 50 g of pyridine and then introduced dropwise at 40 C 88 g of acid monochloride O, S-diethylphosphorous.



  The reaction mixture is heated for a further hour at 35 - 4000 and mixed at this temperature with 50 g.

 <Desc / Clms Page number 27>

 36% hydrogen peroxide. After an additional hour of stirring at 35 C, the operation is carried out as described in the examples.
 EMI27.1
 25-27 and 67 g of 0.8-diethyl-0- (4-methylmercapto-3-aethylphnyl) -phosphate are obtained, which corresponds to a yield of 44% of theory. the ester boils at 11000 under 0.01 mm.



   Example 31
 EMI27.2
 To a solution of 70 g (0.5 mol) of p-methylmercaptophenol in 400 cc of benzene is added with stirring 50 g of anhydrous pyridine and then brought dropwise to 30 -
 EMI27.3
 35 C 88 g of 09S-diethylphosphorous acid chloride. Stirring is continued for a further hour. Then 50 g of 35% hydrogen peroxide are added dropwise at 30 ° C., the mixture is heated for an additional hour at 35 ° C. and the procedure is then carried out as described in the preceding examples. 88 g (60% of theory) of O, S-diethyl-O- (p-methylmercaptophenyl) - phosphate are thus obtained, boiling at 104 ° C. under 0.01 mm.



   Example 32
 EMI27.4
 

 <Desc / Clms Page number 28>

   , '.x'.: '. ß; 'rT .t! e. Y "ç: n: .., 3 a Joz, -'r0:, .. 'QL.-tt4".



  .t.'J, ßßß, d K, r # b. ', i :. 'bzz W Y -9 - "vl7 .t ya r 0" Í 0'. G 'lf., ..' 1, ^ 3u. "Y l4.Fi.'sf 1 o 1f.: \;" O "t ....", z, I. q., n ..t S '') .. ce ",. 4 'ï" to. . ':} ":' '' ': Ibzz; c, 1'1' ...; '>.



  "" t ", 'fl",. f,:> -'! r 10 '"..... J ..,;'! ...- I-"> to, / ..- (. . 'lt \ *:: c. l'.,.: - 1 5 * i7J7rr; "'ü.'rr', o ... t:", 'II \ "$".



  "" 1 rice 1. ::. J ,.



  , a '0, + ìÀ 0 1 5.;. ', ï: .. iS. , tt 0 <90; ';;;. t4 fotl .: ...



  '0> 1 A' 'Js fi' 7 (1, .. t ':' 1) .¯ $ l "U.fJ ÎJ.



  : \ "20- -:] 1: ;;;, -. Bzz '-. \;.; - :: \ l 4.: / J'. R.> Ar. 'É
 EMI28.1
 : "" '. - 50 g of anhydrous pyridine are added to a 9 ′ (0.5 mole) tfÓlt1ti6 of 2,4,5-trichlorophenol in 400 cc of tmo4m.,: J'.f1l. Then you introduce dropwise ± SJ "OE, 1r6 # tant, 88 g of acid chloride o * g ... & ftlî11p1ï ', M; z; 1: heat the reaction mixture pendâd tJ1Jtf d <M! F <4 fi': 3500 and all with stirring then 3% <? 96 g 4f, # 35% oxygenated, the reaction mixture is heated for a further hour at 35 ° C. and then treated as described.
 EMI28.2
 in example 25. 110 g 8d fdftr64 .i: trichlorophenyl) -phosphate are obtained, which OO: r "1't1t1f1 (J1! d j tm:! 'sMH8A-t of 63% of theory.

   The compound boils at 4,112 C at 0.01 mm,
Example 33
 EMI28.3
 
 EMI28.4
 72 g (0.5 mol) of p-ehlo'b5héi'3SS of 400 cc of benzene are dissolved. To this solution is first added 50 g of anhydrous pyridine and then introduced dropwise
 EMI28.5
 at about 400C 88 g of O, g.dlhthyl1h6ph & rous acid chloride. After half an hour, add bt! Se'iaa do drip reaction at 30 - 5aC! 5ôg of 35% 6XYGEFIED WATER, then heated for another half hour at 35 ° C and finally treated as described in the example.
 EMI28.6
 ple 25.

   There is thus obtained 86 g (58% of lâ t11hl11'ie) of (j, {J-ethyl-S- (p-cel9ophenyl) -phosphate, boiling 4 1050 ÕUµ 0.01 mm.

 <Desc / Clms Page number 29>

 Example 34
 EMI29.1
 To a solution of 66 g (0.5 mol) of B-diethylaminoethyl-mercaptan (M.p. 10:54 C) in 400 cc of benzene is added
 EMI29.2
 at 35 0 and with stirring ¯88g; O, S-diethylphosphorous acid dechloride. The reaction mixture is heated for a period of
 EMI29.3
 hour at 40009 was then added to 3500 50 g of 35% hydrogen peroxide; stirring is continued for one more hour at 35 ° C. and a solution of 20 g of caustic soda in 300 cc of water is introduced dropwise at room temperature.



  After the dropwise addition is complete, the benzene layer is separated, washed with water, dried with sodium sulfate and subjected to fractional distillation. After evaporation of the solvent, by rectifying the residue, 86 g (60% of theory) are obtained
 EMI29.4
 of 09S-diethyl-S- (B-dibthylaminoethyl) -phosphate, boiling at 86 C under 0.01 mm.



   Example 35
 EMI29.5
 68 g (0.5 mol) of p-nitrophenol are dissolved in 400 cc of benzene, 50 g of anhydrous pyridine are added to this solution and then introduced dropwise at 40 C while stirring,
 EMI29.6
 88 g of O, S-di6thylphosphorous acid chloride. After the

 <Desc / Clms Page number 30>

 end of the addition, heated for one more hour at 35 C, then added while stirring at 30 C 50 g of hydrogen peroxide at 35%; the reaction mixture is heated for an additional half hour at 35 ° C. and the procedure is then carried out as described in Example 25.
 EMI30.1
 78 g of O, S-dîethyl-O- (p-nitrophenyl) -phosphatey are obtained, which corresponds to a yield of 54% of theory. The ester boils at 118 C under 0.01 mm.



    Example 36
 EMI30.2
 87 g of 0-ethyl-S-ethylphosphorous acid monochloride (M.p. 1:46 C) are dissolved in 300 cc of carbon tetrachloride.



  While passing a stream of nitrogen is added to this solution at a temperature of +5 C and stirring a solution of 35 g of ethylene oxide in 100 cc of carbon tetrachloride, stirred for a further 12 hours and the reaction product is then fractionated in vacuo. We thus obtain
 EMI30.3
 55 g of 0, S-diethyl-O- (C-chlorethyl) -phosphorous acid ester, which corresponds to a yield of 51% of theory, (M.p. 1: 73-75 C).



  Analysis: The calculation gives for a molecular weight of 217.5:
Cl 16.3% P 14.2% S 14.7 we found: C1 16.0% P 14.7% S 15.3%.

 <Desc / Clms Page number 31>

 



  Example 37
 EMI31.1
 54.5 g (0.25 mole) of acid ester are mixed with stirring
 EMI31.2
 0, S-diethyl-O- (B-ehlorethyl) -phosphorous at room temperature with 8 g of sulfur by passing through a stream of nitrogen. The temperature of the reaction mixture thereby rises from 25 ° C. to 110 ° C. After the reaction has subsided, it is stirred for a further half an hour at 90 ° C. and the product obtained is then fractionated. We obtain 59 g
 EMI31.3
 of OIS-diethyl-O- (B-chlor6thyl) -thionophosphate boiling at 102 C under 1 mm.



  Analysis: The calculation gives for a molecular weight of 249.5:
S 25.6% P 12.4% Cl 14.2% we found: S24.4% P 13.3% C1 14.7 Example 38
 EMI31.4
 50 g of epichlorohydrin is added to 88 g (0.5 mole) of O, S-diethylphosphorous acid monochloride, while stirring and passing a stream of nitrogen over it, the addition being adjusted so that temperature

 <Desc / Clms Page number 32>

 
 EMI32.1
 dtt arilen, r ee dipasss pse 4do0.

   Cnefoia that the addition this terminates in ebtmfft 1 <* 61affl reaction for a further a8! Mmr <t A tofl6. t0a that the addition is off, we cbantte the sil its r6sat.ox paàs.ut enaore zie 40 C ot on * jou> 4 ton per set = t 16 9 of Dhow reduced in potsd'e titië; ôili3 ra e enta um bon de aa ,. 1. ,,. "* fl" "" more at 8o c. The reaction mixture was then prepared with 200 cc of benzene and 'or' 2, washed with water. After having
 EMI32.2
 dried the beazéaiq] ae snr solution, eoà.ua sulphate, it is sooeù with fractional distillation, lprés evaporation of the sol9ant, we obtain 101 g (67 14 of the theory) of 0, S- aiethyl-0- (1 , 3-âichloro-isogrQp.j-thionophoaphate boiling at 820th us 0,, Ol M.

   The mean toxicity (ID) of the compound administered to rats orally is 250 mg / kg.
Example 39
 EMI32.3
 58 g (0.5 mol) of propylene oxide are mixed at 30 C with
 EMI32.4
 88 g (0.5 mole) of O, S-diethylphosphorous acid monochloride while passing through a stream of nitrogen; the mixture is stirred for a further hour at said temperature and 16 g of fine powdered sulfur are then added in portions. Then the reaction mixture is heated for an additional hour at 65 ° C. and finally taken up in 200 cc of benzene. The benzene solution is washed with water until

 <Desc / Clms Page number 33>

 neutral reaction, dried over sodium sulfate and subjected to fractional distillation.

   After having
 EMI33.1
 The solvent was removed by distillation, we obtain 70 653 7 of theory) of 0, S-ditthyl- (2-cM.ero-n-proByl) thionophoaphate, boiling 4 'lix4E eons 1 r.



  Applied to rats by the b = oal route, the average toxicity of 250 mg / kg is obtained.



    Example 40
 EMI33.2
 73.5 g (0.5 mol) of ethylphosphorous acid dichloride is dissolved in 300 cc of petroleum ether. While stirring well, a mixture in the form of 41 g of anhydrous pyridine, 31 g of ethyl mercaptan and 100 cc of petroleum ether is added at 0 ° C.



  To avoid any oxidation, nitrogen is passed which loses condensation through the reaction mixture. After about an hour, the reaction is complete. The pyridine hydrochloride formed is removed with suction and washed thoroughly with petroleum ether. When the filtrate is fractionated, 56 g of monochloride are obtained
 EMI33.3
 of 0, S-diethylphosphorous acid boiling at 460C under 1 mm. Yield: 69% of theory. O, Sdiethylphosphorous acid monochloride is a stable and colorless compound which hardly emits smoke in the open air and which water hydrolyzes only slowly.

 <Desc / Clms Page number 34>

 



  Example 41
 EMI34.1
      147 g (1 mole) of ethylphosphorous acid dichloride are dissolved in 1500 cc of petroleum ether. While stirring well is added dropwise at 0 C a mixture formed of
 EMI34.2
 62, g d 5th ,, ylatercaptgu ,. 10'i g of triethylgmine and 100 cc of petroleum ether. Stirring is continued for one hour at 0 - + 5 ° C. and the triethylamine hydrochloride formed is separated off with suction. The filtrate is subjected to distillation.
 EMI34.3
 lation:! 'r: .c1onnlte, and 48 g of acid monohioride O, S-df.6thylphoephoreuz boiling at 62 C under 12 mm are obtained.

   Yield: 51% of theory.
Example 42
 EMI34.4
 133 g (1 mole) of methylphosphorous acid dichloride (m.p. 760: 93-95 C) are dissolved in 700 cc of petroleum ether. While stirring and passing a stream of nitrogen, a mixture formed of 50 g of methyl mercaptan and 81 g of pyridine is added dropwise to this solution at 0 C.

 <Desc / Clms Page number 35>

 and 200 cc of petroleum ether; the mixture is kept for a further hour at 0 ° C. and the pyridinium hydrochloride formed is filtered off with low suction. The filtrate was added to fractional distillation to give 60 g (41% of theory) of O-S-dimethylphosphorous acid monochloride, boiling at 34 ° C at 2 mm.



   Example 43
 EMI35.1
 147 g (1 mole) of ethylphosphorous acid dichloride are dissolved in 700 cc of petroleum ether. Nitrogen is passed through the solution obtained, then a mixture formed of 50 g of methyl mercaptan, 81 g of pyridine and 200 cc of petroleum ether is added dropwise with stirring at 0 ° C.; the mixture is maintained for a further hour at 0-10 C and the pyridinium hydrochloride formed is separated off with suction. The filtrate is subjected to fractional distillation, and in this way O-ethyl-S-methylphosphorous acid monochloride is obtained, boiling at 47 ° C. under 5 mm. Yield: 100 g = 63% of theory.



   Example 44
 EMI35.2
 

 <Desc / Clms Page number 36>

 
Into a solution of 147 g (1 mol) of ethylphosphorous acid dichloride in 700 cc of petroleum ether is introduced dropwise, at 0 ° C. while stirring and passing a stream of nitrogen, a mixture formed from 77 g of isopropylmercaptan, 81 g of pyridine and 200 cc of petroleum ether.



   Stirring is continued for a further hour at 10 ° C., then the pyridinium hydrochloride formed is separated off by suction. The filtrate is subjected to fractional distillation, and there is thus obtained 100 g (54% of theory) of O-ethyl-S-isopropylphosphorous acid monochloride, boiling at 52 C /,
1 mm.



   Example 45
 EMI36.1
 147 g (1 mole) of ethylphosphorous acid dichloride are dissolved in 700 cc of petroleum ether. While stirring and passing a stream of nitrogen is added dropwise to this solution, a mixture formed of 90 g of isobutylmercaptan, 81 g of pyridine and 200 cc of petroleum ether. The mixture is maintained for a further hour at 1000, the pyridinium hydrochloride formed is removed by suction, and the filtrate is fractionated. O-ethyl-S-isobutylphosphorous acid monochloride is thus obtained, boiling at 570 under 1 mm, with a yield of 105 g, ie 52% of theory.

 <Desc / Clms Page number 37>

 



  Example 46
 EMI37.1
 147 g (1 mole) of ethylphosphorous acid dichloride are dissolved in 700 cc of petroleum ether. Into this solution is introduced dropwise at 0 C, while stirring and passing a stream of nitrogen, a mixture formed of 122 g
 EMI37.2
 of 2-ethylmercapto-ethylmercaptanl 81 g of pyridine and 200 cc of petroleum ether; stirring is continued for a further hour at 1000 and the pyridinium hydrochloride formed is removed by suction. During fractionation of the filtrate, 140 g (60% of theory) of monochloride are obtained.
 EMI37.3
 of 0-ethyl-S- (B-ethylmercaptoethyl) -phosphorous acid, boiling at 111 C under 1 mm.



   Example 47
 EMI37.4
 To a solution of 149 g (1 mol) of S-methylphosphorous acid dichloride (PE2: 37 C) in 1000 cc of anhydrous ether is added at 0 - 5 C while stirring and passing a stream of nitrogen, a mixture formed from 32 g of methanol, 80 g of pyridine and 200 cc of anhydrous ether. One hour after the end of the addition, the hydrochloride is separated by suction

 <Desc / Clms Page number 38>

 of pyridinium formed, and the filtrate is subjected to fractional distillation. This gives 85 g (59% of theory)
 EMI38.1
 of 0, S-dimethylphosphorous acid mono chloride boiling at 34 C under 2 mm.



   Example 48
 EMI38.2
 163 g (1 mole) of S-ethylphosphorous acid dichloride (M.P. 1:45 C) are dissolved in 1000 cc of benzene. To this solution is added dropwise with stirring and passing a stream of nitrogen, a mixture formed of 48 g (1 mole) of anhydrous ethyl alcohol, 200 cc of benzene and 80 g of pyridine. The reaction mixture is stirred for an additional hour to complete the reaction and the pyridinium hydrochloride is removed with suction. By fractional distillation of the filtrate and after evaporation of the solvent, 101 g (58% of theory) of O, S-diethylphosphorous acid monochloride boiling at 46 ° C. under 1 mm are obtained.


    

Claims (1)

CLAIMS 1 Process for preparing thiophosphoric esters, characterized in that chlorides are reacted EMI39.1 of 0, S-dialkylphosphorous acids with any alcohols, phenols or mercaptans, and the products of this reaction are washed off with about the equivalent amount of sulfur, or are subjected to oxidation with about the calculated amount hydrogen peroxide. 2 A method according to claim 1, characterized in that one reacts chlorides of O, S-dialkylphosphorous acids with alkylene oxides and that the acid esters of O, S-dialkyl- are then treated. O-choroalkylphosphorus which result with the equivalent amount of sulfur, or are subjected to oxidation with about the calculated amount of hydrogen peroxide. 3 As new industrial products, O (S) -alkyl or-aryl esters of O, S-dialkyl- (thiono-) phosphoric acids. 4 Pest control method, characterized in that use is made of compounds of formula according to claim 3. Agricultural parasiticides which are or contain compounds according to claim 3.