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US2597534A - Neutral esters of thiolphosphoric acid - Google Patents

Neutral esters of thiolphosphoric acid Download PDF

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US2597534A
US2597534A US184335A US18433550A US2597534A US 2597534 A US2597534 A US 2597534A US 184335 A US184335 A US 184335A US 18433550 A US18433550 A US 18433550A US 2597534 A US2597534 A US 2597534A
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Schrader Gerhard
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/08—Systemic pesticides

Definitions

  • alkyl 0 S alkyl in particular the esters in which alkyl of the above formula is methyl, ethyl, propyl and isobutyl, were prepared by reacting salts of thiolphosphoric acid of the formula:
  • the reaction is most conveniently carried out in an inert solvent, e. g. in benzene or its homologues, chlorobenzene and also in ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, and others. Slight heating, as a rule to about 40 to 60 0., is required.
  • the alkyl radicals of the alkyl thiocyanates employed may belong to the lower or higher alkyls such as methyl, ethyl, propyl, butyl, hexyl, dodecyl.
  • alkyl thiocyanates containing the SON- group twice may be used in which case the reaction shown in the above equation will take place with two molecules of the alkali salts of dialkyl phosphites.
  • alkyl thiocyanates also aralkyl thiocyanates may be used.
  • R in this formula means alkyl, preferably methyl or ethyl, or aryl, in particular phenyl or substituted phenyl.
  • the radical designated alk in this formula stands for a straight or branched alkylene chain.
  • R1 and R2 are alkyl radicals which may be the same or different, and are preferably lower radicals such as methyl, ethyl, or propyl.
  • alkali dialkyl thiophosphates with mercapto alkyl halides of the formula R. S. alk. hal.
  • the alkali dialkyl thiophosphates react, as is known, e. g. from Journal of American Chemical Society 6'7 [1945], pp. 1662-1664 (T. W. Mastin, G. R. Norman and E. A. Weilmuenster) in their tautomeric form 2:
  • R 0 S.alk.S.R alkali halide It is carried out in the presence of inert solvents of the kind mentioned above at elevated temperatures, usually at about 40 to about 0.
  • reaction is carried through in the presence of an inert solvent ofxthe mentioned kind at elevated temperatures, usually at about 40 to about 100 C.
  • Neutral aliphatic esters of. thiophosphoricaeid substituted in one ester group by the. radical of an aliphatic or aromatic mercaptan obtainable by one of the forementioned processes are e. g.:
  • Example 1 70 grams of diethyl phosphite are mixedwith 2 cc; of absolute alcoholand diluted with 100 cc. of toluene: 12 grams of sodium are caused to act uporr the solution thus "obtained: When the sodium has dissolved, 37 grams of methyl thiocyanate are added dropby drop with stirring at 40 Cb Stirring is-continued at40 C. for 2 hours.
  • Example 2 "Sodium salt prepared from 12' grams of sodium and 70 grams of diethyl phosphite in benzene as described in Example 1 is heated to 45-50" C. with stirring. At'this temperature'l grams of ethyl thiocyanate are added drop, by drop Within 10 minutes” controlling the temperature by cooling. The reaction mixture is then heated to 55 C. ior-::one;hour.c.After-workingup as usual grams of 0,0-diethyl S-ethyl thiolpho'sphate, boiling at 98 C. at 2 mm. pressure, are obtained. The new product is soluble in water to a limited degree.
  • Example 3 52 grams of n-propyl thiocyanate are reacted at 40 C. with the sodium salt prepared from 12 grams of sodium-and '70 grams of diethyl phosphiteinzbenzene as described in Example 1. The reactionmixturesobtained is heated to 55 C. for one hour andthen worked up' as usual. 40 grams of OD-diethyl S1-propyl thiolphosphate, boiling at.103-1053.C. at .1- mm. pressure, are obtained. Theproduct isinsoluble in. water.
  • Example 4 57.5 grams of isobutyl thiocyanate are reacted at 40 C. with the sodium salt prepared from 12 grams of sodium and 70 grams of diethyl phosphite as described in Example 1. The reaction mixture. thus obtained is heated to 55 C. for one hour and subsequently worked up as usual. 74 grams of 0,0'-diethy1 S-isobutyl thiolphosphate, boiling at 105 C. at .5 mm. pressure, are obtainedJi'iThe product is insoluble in water.
  • Ezcample 5 65 gramsof n-hexy'l thiocyanate are reacted at 40? C..with thesodium salt prepared from 12 grams of sodium and 70 grams of diethyl phos- The reaction mixture is heated to' 55-60 C. for one hour and Worked up as usual. 48 grams of 0,0-diethyl S-hexyl thiolphosphate of the boiling point C. at .1 mm. pressure are obtained.
  • Emample 7 The sodium salt prepared from 12 grams of 'sodium and '70 grams of diethyl phosphite as described in Example 1 is heated to 45 C. At this temperature 76 grams ofbenzyl thiocyanate are added drop by drop with stirring. The reaction mixture' is-further heated to 40 C. for halfan hour and is then-workedup asusual. 70'grams of 0,0-diethyl S-benzyl thiolphosphate with a boiling point of 165-17 0 C. at 2 'mm.'pres sure are obtained.
  • Example 8 [grams of sodium are suspendedin' ,cc. of toluene. I 42. grams of diethyl phosphite are added and the mixture isstirred at'40 50 C., until'allsodium is. dissolved. With stirring 44 grams of ,9 ethylmercapto ethyl thiocyanate (boiling at 90 C. at 1mm. pressure) are added drop bydrop at a temperature of 40 C. The.
  • the product is alight-yellow oil which is insoluble in water.
  • Example 1 0 '40 grams of B-methylmercapto-ethyl thiocyanate are added drop by drop with stirring art-40 C. to the sodium salt solution obtained according to Example 9. The temperature is kept for one hour at 50 C. and is then worked up in the usual manner. Thus 34 grams of boiling at l34138 C. at 2 mm. pressure ar obtained. 1
  • Example 11 63 grams of fl-mercapto-ethyl ethyl sulfide CzH5.S.C2H4.SI-I (described in Annalen der Chemie 240, p. 311) are added to 12 grams of finely dispersed sodium in 1'70 cc. of toluene drop'by drop, while stirring. The temperature is raised to 60 C. and then kept for half an hour. The sodium will then be dissolved. Thereafter the finely dispersed sodium salt of the mercaptan is cooled to C. Thereto under constant outside cooling 8? grams of diethyl phosphoric monochloride, dissolved in 100 cc. of toluene, are added drop by drop within 20 minutes, while stirring.
  • Example 12 '7 grams of finely pulverized sodium are suspended in 100 cc. of toluene. 43 grams of diethyl phosphite are added thereto at a temperature of 40 C. The temperature of 40 C. is kept for half an hour. Then the sodium will be dissolved. Thereafter, 10 grams of sulfur are added to the reaction product at a temperature of 60 and it is then heated for another hour to 105 C. The sodium diethyl thiophosphate being now finely dispersed is reacted with 34 grams of chloromethyl ethyl sulfide C2H5.S.CH2.C1 (cf.
  • Example 13 Sodium diethyl thiophosphate finely dispersed is prepared from the same quantities as in Example 1. 52 grams of chloromethyl 4-methylphenyl sulfide CH3.C6H4.S.CH2.C1 (cf. Berichte der Deutschen Chemischen Deutschen 69 [1936], p. 16 12) are added to this suspension. The reaction mixture is heated for 4 hours to 105 C.; the formed salts are then brought into a filterable form by adding 10 cc. of water, the toluene layer is separated and fractionated. 60 grams of 0,0 diethyl S-4-methylphenylmercapto-methyl thiolphosphate with a boiling point of 178 C. under .5 mm. pressure are obtained, corresponding to a yield of 65 per cent. The new substance is a colorless oil insoluble in water.
  • Sodium diethyl thiophosphate is prepared from the same quantities as in Example 1. To this salt 37 grams of B- chloroethyl ethyl sulfide C2H5.S.C2H4.Cl (cf. Annalen der Chemie 240 [1887], p. 310) are added at'a temperature of 70 C., while stirring; The reaction mixture is then heated for another two hours to C., and the salts are removed by means of water as in the preceding examples.
  • Example 16 Young peach trees infested with peach-aphides are sprayed with an aqueous solution containing 0.005 per cent of the following compound:
  • This aqueous solution may also be used in the presence of alkaline reacting agents for simultaneously combating fungi.
  • Example 17 is ground with the following substance:

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)

Description

Patented May 20, 1952 UNITED STATES PATENT OFFICE NEUTRAL ESTERS- g! THIOLPHOSPHORIC A D Gerhard Schrader, Opladen-Bruchhausen, Germany, assignor to Farbenfabriken Bayer, Leverkusen, Germany No Drawing. Application September 11, 1950, Serial No. 184,335. In Germany May 7, 1949 1 The present invention relates to the manufacture of neutral esters of thiolphosphoric acid,
and to new esters of this series.
Hitherto the neutral esters of thiolphosphoric acid of the formula:
alkyl. 0 0
alkyl. 0 S alkyl in particular the esters in which alkyl of the above formula is methyl, ethyl, propyl and isobutyl, were prepared by reacting salts of thiolphosphoric acid of the formula:
alkyl. 0 O
alk.0\ %O alkali NCS.alkyl alk.0\ O
The reaction is most conveniently carried out in an inert solvent, e. g. in benzene or its homologues, chlorobenzene and also in ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, and others. Slight heating, as a rule to about 40 to 60 0., is required. The alkyl radicals of the alkyl thiocyanates employed may belong to the lower or higher alkyls such as methyl, ethyl, propyl, butyl, hexyl, dodecyl. Also alkyl thiocyanates containing the SON- group twice may be used in which case the reaction shown in the above equation will take place with two molecules of the alkali salts of dialkyl phosphites. Besides alkyl thiocyanates, also aralkyl thiocyanates may be used.
These neutral aliphatic esters of thiolphosphoric acid are, as a rule, oily liquids of a high i 4 Claims. (Cl. 260-461) 2 boiling point, and are distinguished by insecticidal properties.
It has further been found that neutral esters of thiolphosphoric acid of particular value and interest are obtained when in the above described new process instead of simple alkyl thiocyanates thiocyanates of the formula R. S. alk. SCN are used. R in this formula means alkyl, preferably methyl or ethyl, or aryl, in particular phenyl or substituted phenyl. The radical designated alk in this formula stands for a straight or branched alkylene chain. Compounds obtained by means of these thiocyanates correspond to the general formula:
in which R1 and R2 are alkyl radicals which may be the same or different, and are preferably lower radicals such as methyl, ethyl, or propyl. These new esters of thiolphosphoric acid are distinguished by very good insecticidal properties, in particular by their systemic insecticidal properties.
It has further been found that these valuable compounds can also be prepared by reacting alkali dialkyl thiophosphates with mercapto alkyl halides of the formula R. S. alk. hal. The alkali dialkyl thiophosphates react, as is known, e. g. from Journal of American Chemical Society 6'7 [1945], pp. 1662-1664 (T. W. Mastin, G. R. Norman and E. A. Weilmuenster) in their tautomeric form 2:
O.alkali Rlo 1 2 The reaction takes place according to the following equation:
R 0 Salkali R O\ O R 0 B.a1kali hel.alk.S.R
R 0 S.alk.S.R alkali halide It is carried out in the presence of inert solvents of the kind mentioned above at elevated temperatures, usually at about 40 to about 0.
Another new process of preparing these com pounds consists in reacting dialkyl phosphoric chlorides with alkali salts of mercapto alkyl mer- 3 captans of the formula R. S. alk. SH. The reaction takes place according to the following equation:
Also here the reaction is carried through in the presence of an inert solvent ofxthe mentioned kind at elevated temperatures, usually at about 40 to about 100 C.
Neutral aliphatic esters of. thiophosphoricaeid substituted in one ester group by the. radical of an aliphatic or aromatic mercaptan obtainable by one of the forementioned processes are e. g.:
0,0-diethyl s-fi-ethylmercapto' ethyl thiolphosphate 0,0-diethyl S-B-methylmercapto=ethyl thiollzphosphate 0,Q-.diethy1 S- 3A-methylphenylmercaptoeethyl thiolphosphate O,O -die.thyl S-ethylmercapto-methylthiolphos- *phate 0,0-ediethylz SHiemethylphenyImercaptoemethyl :thiolphosphate 0,0-di-1isopropyl s-p ethylmercapto-ethyli;tliio1- lxphosphate The present invention is illustrated btfithefollowing examples; it is, however, not restricted thereto:
Example 1 70 grams of diethyl phosphite are mixedwith 2 cc; of absolute alcoholand diluted with 100 cc. of toluene: 12 grams of sodium are caused to act uporr the solution thus "obtained: When the sodium has dissolved, 37 grams of methyl thiocyanate are added dropby drop with stirring at 40 Cb Stirring is-continued at40 C. for 2 hours.
15 cc. of water are then added to the reaction mixture and r the precipitated salts are removed by filtering." 48 grams of 0,0-dimethyl S-nethyl thiolphosphatehaving -a-boiling pointof 112-113" C: at 14==mm.' pressure are obtained. The *prod not is soluble in-Water.
Example 2 "Sodium salt prepared from 12' grams of sodium and 70 grams of diethyl phosphite in benzene as described in Example 1 is heated to 45-50" C. with stirring. At'this temperature'l grams of ethyl thiocyanate are added drop, by drop Within 10 minutes" controlling the temperature by cooling. The reaction mixture is then heated to 55 C. ior-::one;hour.c.After-workingup as usual grams of 0,0-diethyl S-ethyl thiolpho'sphate, boiling at 98 C. at 2 mm. pressure, are obtained. The new product is soluble in water to a limited degree.
Example 3 52 grams of n-propyl thiocyanate are reacted at 40 C. with the sodium salt prepared from 12 grams of sodium-and '70 grams of diethyl phosphiteinzbenzene as described in Example 1. The reactionmixturesobtained is heated to 55 C. for one hour andthen worked up' as usual. 40 grams of OD-diethyl S1-propyl thiolphosphate, boiling at.103-1053.C. at .1- mm. pressure, are obtained. Theproduct isinsoluble in. water.
phite as described in Example 1.
4 Example 4 57.5 grams of isobutyl thiocyanate are reacted at 40 C. with the sodium salt prepared from 12 grams of sodium and 70 grams of diethyl phosphite as described in Example 1. The reaction mixture. thus obtained is heated to 55 C. for one hour and subsequently worked up as usual. 74 grams of 0,0'-diethy1 S-isobutyl thiolphosphate, boiling at 105 C. at .5 mm. pressure, are obtainedJi'iThe product is insoluble in water.
Ezcample 5 65 gramsof n-hexy'l thiocyanate are reacted at 40? C..with thesodium salt prepared from 12 grams of sodium and 70 grams of diethyl phos- The reaction mixture is heated to' 55-60 C. for one hour and Worked up as usual. 48 grams of 0,0-diethyl S-hexyl thiolphosphate of the boiling point C. at .1 mm. pressure are obtained.
- Example 6 115 grams of dodeoyl thiocyanate are reacted at-50 C; with the-sodium salt preparedfrom 12 grams of sodium and '70 grams of diethyl phosphite as described in'Example 1. The reaction mixture is heated to 5560 C. for one hour and is then worked up as usual. 60 grams of 0,0-diethyl S-dodecyl thiolphosphate, having a boiling point of 185-190" C. at. .5: mm. pressure; are obtained.
Emample 7 The sodium salt prepared from 12 grams of 'sodium and '70 grams of diethyl phosphite as described in Example 1 is heated to 45 C. At this temperature 76 grams ofbenzyl thiocyanate are added drop by drop with stirring. The reaction mixture' is-further heated to 40 C. for halfan hour and is then-workedup asusual. 70'grams of 0,0-diethyl S-benzyl thiolphosphate with a boiling point of 165-17 0 C. at 2 'mm.'pres sure are obtained.
Example 8 Example 9 [grams of sodium are suspendedin' ,cc. of toluene. I 42. grams of diethyl phosphite are added and the mixture isstirred at'40 50 C., until'allsodium is. dissolved. With stirring 44 grams of ,9 ethylmercapto ethyl thiocyanate (boiling at 90 C. at 1mm. pressure) are added drop bydrop at a temperature of 40 C. The.
mixture is kept for one .hour at' 50 C. and is then worked up. in the usual manner. .Thus 28 gramsof '(C2H5O)2PO.S.C2H4.S.CzI-I5 boiling at 137-141 C.'at 1.mm. pressure are obtained.
The product is alight-yellow oil which is insoluble in water.
Example 1 0 '40 grams of B-methylmercapto-ethyl thiocyanate are added drop by drop with stirring art-40 C. to the sodium salt solution obtained according to Example 9. The temperature is kept for one hour at 50 C. and is then worked up in the usual manner. Thus 34 grams of boiling at l34138 C. at 2 mm. pressure ar obtained. 1
Example 11 63 grams of fl-mercapto-ethyl ethyl sulfide CzH5.S.C2H4.SI-I (described in Annalen der Chemie 240, p. 311) are added to 12 grams of finely dispersed sodium in 1'70 cc. of toluene drop'by drop, while stirring. The temperature is raised to 60 C. and then kept for half an hour. The sodium will then be dissolved. Thereafter the finely dispersed sodium salt of the mercaptan is cooled to C. Thereto under constant outside cooling 8? grams of diethyl phosphoric monochloride, dissolved in 100 cc. of toluene, are added drop by drop within 20 minutes, while stirring. After adding the chloride the reaction product is kept at room temperature for a further hour. By adding 20 cc. of water the salts are then turned into a filterable form. After distilling oil the toluene the remaining oil distils at a boiling point of 136 C. under 1 mm. pressure. 93 grams of 0,0-diethyl S-p-ethylmercapto-ethyl thiolphosphate, a slightly yellow oil, insoluble in water are obtained. Yield: 72 per cent of theory.
In a similar way can be obtained:
CgHsO O PS.CH,.OH.S.CH:
boiling at 135 C. under 2 mm. pressure not distillable Example 12 '7 grams of finely pulverized sodium are suspended in 100 cc. of toluene. 43 grams of diethyl phosphite are added thereto at a temperature of 40 C. The temperature of 40 C. is kept for half an hour. Then the sodium will be dissolved. Thereafter, 10 grams of sulfur are added to the reaction product at a temperature of 60 and it is then heated for another hour to 105 C. The sodium diethyl thiophosphate being now finely dispersed is reacted with 34 grams of chloromethyl ethyl sulfide C2H5.S.CH2.C1 (cf. Berichte der Deutschen Chemischen Gesellschaft 69 [1936], p. 1612) at a temperature of 55 C. The temperature of the reaction mixture is kept for another hour at 55 C., then 8 cc. of water are added, the toluene layer is removed and fractionated. 40 grams of 0,0-diethyl S-ethyllrnercapto-methyl thiolphosphate of a boiling point of 129-130" C. at 1.5 mm. pressure are obtained. The yield corresponds to 60 per cent of theory. The new thiolester is insoluble in water.
Example 13 Sodium diethyl thiophosphate finely dispersed is prepared from the same quantities as in Example 1. 52 grams of chloromethyl 4-methylphenyl sulfide CH3.C6H4.S.CH2.C1 (cf. Berichte der Deutschen Chemischen Gesellschaft 69 [1936], p. 16 12) are added to this suspension. The reaction mixture is heated for 4 hours to 105 C.; the formed salts are then brought into a filterable form by adding 10 cc. of water, the toluene layer is separated and fractionated. 60 grams of 0,0 diethyl S-4-methylphenylmercapto-methyl thiolphosphate with a boiling point of 178 C. under .5 mm. pressure are obtained, corresponding to a yield of 65 per cent. The new substance is a colorless oil insoluble in water.
Example, 1 4
Sodium diethyl thiophosphate is prepared from the same quantities as in Example 1. To this salt 37 grams of B- chloroethyl ethyl sulfide C2H5.S.C2H4.Cl (cf. Annalen der Chemie 240 [1887], p. 310) are added at'a temperature of 70 C., while stirring; The reaction mixture is then heated for another two hours to C., and the salts are removed by means of water as in the preceding examples. By fractionating the toluene layer 54 grams of 0,0-diethy1 S-flethylmercapto-ethyl thiolphosphate are obtained, corresponding to a yield of 70 per cent; colorless oil insoluble in water having a boiling point of 136 C. under 1 mm. pressure.
In a similar way e. g. the following compound can be produced:
C H O boiling at 134 0. under 2 mm. pressure Example 15 7 grams of sodium :powder are suspended in 100 cc. of toluene and heated with 42 grams of diisopropyl phosphite to 50 C., until the sodium is dissolved. Thereafter 9 grams of sulfur are added and the mixture is heated for another hour to 90-95 C. It is then cooled to 50 C., and at this temperature 37 grams of p-chloroethyl ethyl sulfide are added drop by drop. The reaction mixture is kept for further 4 hours at 90-95 C., while stirring. By adding 5 cc. of water the salts formed are thereupon brought into a filterable form. After sucking oil the salts the solvent is removed from the toluene solution. The remaining crude product is now kept for 10 minutes at an inside temperature of C. under a vacuum of 2 mm. to remove the last traces of the volatile solvent. 0,0-di-isopropyl S-B-ethylmercaptoethyl thiolphosphate thus obtained is a brownyellow oil insoluble in water (60 grams). At a pressure of 2 mm. the ester can only be distilled with strong decomposition.
Example 16 Young peach trees infested with peach-aphides are sprayed with an aqueous solution containing 0.005 per cent of the following compound:
P-S. CH CH,.S.CH;
After some hours all aphides are killed.
This aqueous solution may also be used in the presence of alkaline reacting agents for simultaneously combating fungi.
Example 17 Tale is ground with the following substance:
PS.CH2.0H1.S.C2H5
so-that a 5wpen=centidust iszobtained: :Thiss'dust is applied to. "branches with -caterpi1lars(Malacosomw-neustria) r'l'he fcaterpillarsware killed after a short-time.
This ,:applicationis a-seontinuationein-part or" myoopending :,.ear1ier;application:Serial' N0'.--94,- 721-; filed May 21,11949.
I claim:
1. As new compounds neutral esters of thiolphosphoric acid of thegeneral'formula:
whereinaeRi and R2 stand: for lower Lalkyl radi cals, e alk' stands for a lower: alky'leneichain', and R stands for one of the group consistingof lower alkyl radicals, phenyl radicals and lower alkyl substituted" phenyl radicals.
2.- As-new compounds neutral: esters of 'thiol phosphoric acid of the-general formula:
Rio
6- wherein R, ..-Rr:- and Rzstandior. lower alkyl radicals, and X is one of the integers 1 and 2. 3% As new-compound the-neutral ester of thiolphosphoric acid of the formula:
C|H|O O 0,330 SR'JHiLCHjISDaHt 4;. Aszneweompoundthe neutral ester oilthiolphosphorioacid' of. the formula:
SQC Hi CIhS. CHI
GERHARD SCHRADER.
- No references cited.

Claims (1)

1. AS NEW COMPOUNDS NEUTRAL ESTERS OF THIOLPHOSPHORIC ACID OF THE GENERAL FORMULA:
US184335A 1949-05-07 1950-09-11 Neutral esters of thiolphosphoric acid Expired - Lifetime US2597534A (en)

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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758091A (en) * 1947-10-28 1956-08-07 Shell Dev Lubricating compositions
US2759010A (en) * 1952-08-01 1956-08-14 Bayer Ag Alkylmercaptoalkyl-o, o-dialkyldithiophosphate
DE961083C (en) * 1954-08-02 1957-04-04 Bayer Ag Process for the preparation of S-ª ‰ -Merkapto-aethyl-O, O-dialkyl-thiol-phosphoric acid esters
DE1032247B (en) * 1954-12-04 1958-06-19 Bayer Ag Process for the production of organic phosphorus compounds
US2862016A (en) * 1954-03-04 1958-11-25 Ciba Ltd Process for preparation of alkali salts of o,o-thiolphosphoric acid asymmetrical diesters
US2875228A (en) * 1955-12-30 1959-02-24 Monsanto Chemicals Esters of thiolcarboxylic acids
US2894973A (en) * 1955-09-07 1959-07-14 Bayer Ag Thiophosphoric acid esters and their production
US2915546A (en) * 1955-05-13 1959-12-01 Bayer Ag Process for the manufacture of thiophosphoric acid esters
US2943015A (en) * 1956-10-19 1960-06-28 Ici Ltd Omicron:omicron'-diethyl s-(beta-dimethyl amino-beta-methyl)-propyl phosphorothiolates and pesticidal compositions containing same
DE1087591B (en) * 1958-11-07 1960-08-25 Bayer Ag Process for the preparation of dithiophosphoric acid esters
US2952700A (en) * 1955-11-22 1960-09-13 Bayer Ag Thiophosphoric acid esters and their production
US2976309A (en) * 1955-10-29 1961-03-21 Bayer Ag Process for the production of thiolphosphoric acid esters
US2976311A (en) * 1956-12-10 1961-03-21 Bayer Ag Dithiophosphoric acid esters
US2976312A (en) * 1956-12-13 1961-03-21 Bayer Ag Process for making thionophosphoric acid esters of alpha-hydroxy-methyl-thioethers
US3004980A (en) * 1954-08-02 1961-10-17 Bayer Ag Thiophosphoric acid esters
US3025316A (en) * 1958-10-18 1962-03-13 Bayer Ag Thiophosphoric acid esters and a process for their production
US3060217A (en) * 1957-10-25 1962-10-23 Bayer Ag Thiophosphoric acid esters
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US2758091A (en) * 1947-10-28 1956-08-07 Shell Dev Lubricating compositions
US2759010A (en) * 1952-08-01 1956-08-14 Bayer Ag Alkylmercaptoalkyl-o, o-dialkyldithiophosphate
US2862016A (en) * 1954-03-04 1958-11-25 Ciba Ltd Process for preparation of alkali salts of o,o-thiolphosphoric acid asymmetrical diesters
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US3004980A (en) * 1954-08-02 1961-10-17 Bayer Ag Thiophosphoric acid esters
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US2881201A (en) * 1954-12-04 1959-04-07 Bayer Ag Substituted mercaptoalkyl esters of phosphoric acids and their derivatives
US2915546A (en) * 1955-05-13 1959-12-01 Bayer Ag Process for the manufacture of thiophosphoric acid esters
US2894973A (en) * 1955-09-07 1959-07-14 Bayer Ag Thiophosphoric acid esters and their production
US2976309A (en) * 1955-10-29 1961-03-21 Bayer Ag Process for the production of thiolphosphoric acid esters
US2952700A (en) * 1955-11-22 1960-09-13 Bayer Ag Thiophosphoric acid esters and their production
US2875228A (en) * 1955-12-30 1959-02-24 Monsanto Chemicals Esters of thiolcarboxylic acids
US2943015A (en) * 1956-10-19 1960-06-28 Ici Ltd Omicron:omicron'-diethyl s-(beta-dimethyl amino-beta-methyl)-propyl phosphorothiolates and pesticidal compositions containing same
US2976311A (en) * 1956-12-10 1961-03-21 Bayer Ag Dithiophosphoric acid esters
US2976312A (en) * 1956-12-13 1961-03-21 Bayer Ag Process for making thionophosphoric acid esters of alpha-hydroxy-methyl-thioethers
US3060217A (en) * 1957-10-25 1962-10-23 Bayer Ag Thiophosphoric acid esters
US3065256A (en) * 1958-07-26 1962-11-20 Bayer Ag Phosphorus ester derivatives of vinyl sulfide and a process for their production
US3025316A (en) * 1958-10-18 1962-03-13 Bayer Ag Thiophosphoric acid esters and a process for their production
DE1087591B (en) * 1958-11-07 1960-08-25 Bayer Ag Process for the preparation of dithiophosphoric acid esters
US3073857A (en) * 1959-12-28 1963-01-15 Pure Oil Co Method of preparing phosphorotetrathioate esters
US3248459A (en) * 1961-11-24 1966-04-26 Bayer Ag Thiol-phosphoric, -phosphonic, -phosphinic or thionothiol-phosphoric, -phosphonic, -phosphinic acid esters and processes for the production thereof
US3294874A (en) * 1962-01-24 1966-12-27 Bayer Ag Omicron-alkyl-omicron-cycloalkyl-s-alkylthiolphosphoric acid esters
US3462530A (en) * 1964-06-12 1969-08-19 Stauffer Chemical Co S-chlorophenoxy-methyl,thio,dithio phosphonates or phosphates as insecticides and acaricides
JPS5010377B1 (en) * 1966-04-28 1975-04-21
JPS5581894A (en) * 1978-12-15 1980-06-20 Nippon Tokushu Noyaku Seizo Kk Plant systemic dipropyl thiolphosphate, its preparation, and resistant insect expellent comprising it as active constituent
US4755311A (en) * 1986-08-14 1988-07-05 The Lubrizol Corporation Phosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same

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