Патент USA US3070503код для вставки
3,070,493 "ice United States Patented Dec. 25. 1962 2. 1 lyzed as 10.0% P‘ and 21.6% S compared to 10.7% P 3,070,493 and 22.1% S theoretical for ' ‘ PHOSPHORO CARBIMIDATES NCaHs Glenn R. Price, South Chicago Heights, and Edward N. Walsh, Chicago Heights, 111., and James T. Hallett, (02H5o.)a1>.(0)—s-s~0 Saratoga, Cali?, assignors to Stau?er Chemical Com 002E‘ pauy, New York, N.Y., a corporation of Delaware EXAMPLE 2 No Drawing. Filed Apr. 10, 1961, Ser. No. 101,673 23 Claims. (Cl. 167-30) Following the procedure of Example 1, but using N-p This invention relates to .a new class of phosphor-us 10 chlorophenyl-O-ethyl thiocarbam-ate, 36 grams (96%) of containing pesticides ‘and a process for utilizing the same. (oiHtmrr(0)-1s_s_o=NotHio1 In particular this invention relates to new compounds (I) CzHs having a novel disul?de con?guration which provides new was prepared which analyzed 7.4% P and 16.0% S com and valuable characteristics. These new compounds have pared to 8.1% P and 16.7% S theoretical. I been found to be useful in the elimination and control of EXAMPLE 3 numerous insect pests as will be shown hereafter. These new compounds are phosphoro carbimidates Following the procedure of Example 1 but using ‘N which may be represented by the formula: R10 0 phenyl-O-methyl thiocarbamate, 60.0 grams (92%) of NR3 (G2H5O)2—'P(O)~S~—S—C=NC0H5 20 CH3 was prepared which had an index of refraction ND25=\1.5540 wherein R1 and R2 are the same or ‘di?erent alkyl redicals, R3 may be alkyl or iaryl, R4 may be alkyl or aryl and X is oxygen or sulfur. They may be prepared according to the and analyzed 8.6% P and 18.7% S compared to 9.25% P and 19.1% S theoretical. following general reaction: v (R10) EXiAM-PLE'4 In [a similar manner but using N-phenyle‘O-isopropyl thiocarbamate, a 90% yield of‘ product was obtained. P(O)SY + RgNHC (S)XR4 + REN __’ This material analyzed as 8.55% P and 17.4% S com (R20) (R10) P (O)—S——S—C % (R20) pared with 8.5% P and 17.6% S theoretical for NR3 C2H50)2P_(O)—S—S—C=NCBH5 OC3H1 EXAMPLE 5 -|- RsN-HY X34 wherein R1, R2, R3, R4 and X are as de?ned above, Y is a halogen, and R5N is a tertiary amine hydrogen halide ac _Following the procedure of Example 1 but using ‘0,0 ceptor. dimethylphosphorosulfenyl chloride, 57 grams (93% Among the alkyl radicals which we have found suitable for the phosphorus ester portion of the molecule are the 40 yield) of methyl, ethyl, propyl, butyl, ‘octyl, and decyl radicals as well as combinations resulting in mixed esters such as methyl ethyl, ethyl octyl, methyl, butyl, ethyl propyl and the like. Suitable alkyl or aryl radicals for R3 and R4 include methyl, ethyl, propyl, butyl, octyl, phenyl, chloro 45 - <OH.o)iP(0)-s‘-s—o=NCiH. OCzHa was prepared which analyzed as 8.9% P 18.8% S compared with 9.65% P and 19.9% S theoretical. EXAMPLE 6 phenyl, nitrophenyl and the like. The hydrogen halide acceptor may be any of the well known alkaline compounds suitable for this use. In par ticular we prefer to use tertiary amines such as pyridine, triethyl‘amine, trimethylamine and the like. In a similar manner (CBHUOMP (O)—s—-S—C:NC6H5 60 The process is preferably carried out in ‘an inert solvent in the presence of the hydrogen halide acceptor by adding approximately stoichiometric amounts of 0,0-dialkyl O CH: was made in 84.5% yield, ND35=1.5-1:24, ‘analysis 6.05% P and 12.5% S (theoretical 6.16% P, 12.7%. S). phosphorosulfenyl halide to the appropriate thiocarba 55 mate. The reaction is nearly instantaneous at tempera EXAMPLE 7 The following examples illustrate the compounds of EXAMPLE 8 In a similar manner tures from about 0° C. to ordinary room temperature, al (CsHnO) (021350) P (O).-——S -—S —C=NCOH5 though it is best to stir the ?nal thickened reaction mixture for a short while to ensure complete reaction. The prod~ 0 011(0113): not is then recovered by ?ltering ‘off the halide salt or by 60 was made in 99% yield, ND25=1.5176. other well-known means such as washing out the salt. our invention: To a solution of 29.7 grams of N-phenyl-S-ethyl‘ dithio EXAMPLE 1 c-arbamate in 150 ml. of ether was added 15.2 grams of To a solution of 7.9 grams voi:'-pyridine and 18.1 grams 65 .triethylarnine. The solution was cooled to 10° C. and 30.6 grams of 0,0-diethylphosphorosulfenyl chloride was of N-phenyl-O-ethyl-thiocarbamate in 200 cc. 'of ether added over a 30 minute period. The reaction mixture was was added 20.4 grams of 0,0-diethylphosphorosulfenyl chloride over a 30 minute period at 10° C. The crude product was stirred for two hours at room temperature and then ?ltered to, remove the pyridine hydrochloride. The crude product was stabilized to 50° C. at 1.0 mm. of Hg to yield 30.5 grams (87% yield). The product ana stirred for an additional hour at room temperature and then at re?ux for 30 minutes. After ?ltering and remov ing the solvent, the product was stabilized to 50° C. at 1.0 mm. Hg pressure. A yield of 51.5 grams (95.5%) was obtained with an index of refraction ND25‘==1.5802 and 3,070,493 11 water.” The latter contains 2.5 grams of Vatsol and 1.0 gram of Methocel per 20 liters of water. Each solution is then sprayed onto the insects using a DeVilbiss hand sprayer in a fume hood. Mortality is reported after 72 hours as percent kill/percent concentration. Q which analyzed 7.32% P and 26.4% S compared to 8.5% P and 26.3% S for (CzH5O)zP(O)-—S-—S—C=NC5H5 SCzHt EXAMPLE v9 In addition to the above insects, tests were also run on the two-spotted mite, Tetranychus telarius (designated Following the procedure of Example 8, but using N phenyl-S-butyl dithiocarbamate, 51.0 grams of (C2HsO)IP(O)-—S—-S~—C=NCeHa 28M) and the effects were additionally noted on the eggs (designated 2SME). The tests were conducted by in 10 festing young Pinto bean plants in the primary leaf stage with several hundred mites. The infested plants were then sprayed to run-off using the sprayer and solutions previously described. The results are again reported as ND25= l .5704 percent kill/percent concentration. The miticidal activ and analyzed as 7.5% P and 25.2% S compared to 8.5% 15 ity is determined after seven days but the ovicidal results require fourteen days. P and 26.3% S theoretical. The following results were obtained using the com Using the process as outlined above the following addi pounds of this invention. tional compounds were made. s 048:9 was prepared which had an index of refraction “A Theoretical Example R; R: R: .9 E X B4 N 1:25 Per cent S Per om The class of compounds characterized by the foregoing examples has been found to have valuable pesticidal prop erties. In particular, these compounds are valuable in the control of common insect pests. By the term “insect” Ur we do not intend to be limited to the narrow technical 28M usage of this term to include only six-legged pests but 28MB intend the broader more common usage which includes spiders, mites, ticks, caterpillars, nematodes and the like. In the following described tests demonstrating the util ity of our new compounds, four insect species represent ing four insect orders were used. These species are: ( 1) American cockroach—-Periplanela arnericana—-Or thoptera (designated AR) (2) Confused ?our beetle—Trib0lium confusum-Cole optera (designated CFB) (3) House ?y—-Musca domestica-Diptera (designated HF) (4) Spotted milkweed bug—0ncopelms fasciatus—I-Ieter optera (designated MWB) In conducting the tests, the compounds are made up 10 10 From these data it can be seen that these new com pounds are valuable insecticides. Although the speci?c examples show the use of aqueous solutions of these compounds as insecticides, they may also be used in the into solutions, normally 0.1% concentration, using “wet 75 form of emulsions, non-aqueous solutions, wettable pow 3,070,498 5 110. The compound represented by the formula ders, vapors, and dusts as may be best ?tted to the con ditions of use. NCaE»; The concentration normally used for initial testing is a 0.1% solution. As noted above, however, many of these (CzHsO)zP(O)—-S—S-O 0 03117 new compounds are effective pesticides at much lower levels, as low as 0.000l% in some instances. 11. The compound represented by the formula Since the e?ective concentration may vary with each compound and each pest to which it is applied, a general numerical (CHSOMP (O)—S-——S—C range of concentrations cannot be stated. It is well with ¢NC3H7 O C3H1 in the skill of the art, however, to determine the effective 10 concentration necessary to kill a signi?cant proportion 12. A process for controlling pests comprising apply of a speci?c pest or combination of pests under certain ing thereto an elfective concentration of a compound conditions of application. represented by the formula The foregoing description is given for clearness of un derstanding only and no unnecessary limitations should be 15 understood therefrom as modi?cation will be obvious to those skilled in the art. We claim: wherein R1 and R2 are alkyl radicals, R3 and R4 are mem bers of the class consisting of lower alkyl, phenyl and 1. Compounds having the formula 20 substituted phenyl radicals and X is a member of the class consisting of oxygen and sulfur. 13. A process for controlling pests comprising apply R20 ing thereto an effective concentration of the compound XR4 claim 2. wherein R1 and R2 are alkyl radicals, R3 and R4 are 25 of 14. A process for controlling pests members of the class consisting of lower alkyl, phenyl ing thereto an e?ective concentration and substituted phenyl radicals and X is a member of the of claim 3. class consisting of oxygen and sulfur. 15. A process for controlling pests 2. The compound represented by formula ing thereto an effective concentration 30 of claim 4. 16. A process for controlling pests ing thereto ‘an effective concentration comprising apply of the compound comprising apply of the compound comprising apply of the compound of claim 5. 3. The compound represented by the formula (ClH50):P(O)-S—S—C NCuH4C1 % OCZH; . The compound represented by the formula NCoHi (C:HsO):P(0)—S-S—C 0 CH: 5. The compound represented by the formula NGoHs . 35 % (C?HltO)2P(O)-S—S—0 O C3H7 6. The compound represented by the formula of claim 6. 18. A process for controlling pests comprising apply ing thereto an effective concentration 40 of claim 7. 19. A process for controlling pests ing thereto an effective concentration of claim 8. 20. A process for controlling pests 45 ing thereto an elfective concentration of claim 9. p 21. A process for controlling pests ing thereto an effective concentration of claim 10. 22. A process for controlling pests 60 ing thereto an effective concentration of claim 11. formula (C2H50)IP (O)—-S—S—C OCzHI 55 . The compound represented by the formula NCgH: (CQH50)2P(O)-S—S—G NClH? (C2HsO)2P (O)—S—-S—C OCH: comprising apply of the compound comprising apply of the compound comprising apply of the compound R‘O\(u’P~S—S-—-C=N.Ra XR4 and substituted phenyl radicals and X is a member of the class consisting of oxygen and sulfur, which comprises reacting substantially stoichiometric quantities of a com pound having the formula 65 Rio P(O)SY O CzHs % of the compound ' R20 8. The compound represented by the formula . The compound represented by the formula comprising apply wherein R1 and R2 are alkyl radicals, R3 and R4 are 60 members of the class consisting of lower alkyl, phenyl 0 C211; Noni, % of the compound 23. A process for preparing compounds having the N C4Hu (CzHsOhP (O)——S—S—-C 17. A process for controlling pests comprising apply ing thereto an etfective concentration of the compound R20 wherein Y is a halogen atom with a compound having 70 the formula R3NHC(S)XR4 in the presence of a hydro gen halide acceptor. No references cited.