US3758645A - Cis thiophosphoric acid amide esters - Google Patents
Cis thiophosphoric acid amide esters Download PDFInfo
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- US3758645A US3758645A US00054837A US3758645DA US3758645A US 3758645 A US3758645 A US 3758645A US 00054837 A US00054837 A US 00054837A US 3758645D A US3758645D A US 3758645DA US 3758645 A US3758645 A US 3758645A
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- -1 thiophosphoric acid amide esters Chemical class 0.000 title abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 115
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 30
- 239000000460 chlorine Chemical group 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 37
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 20
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052794 bromium Chemical group 0.000 abstract description 4
- 239000000575 pesticide Substances 0.000 abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 33
- 239000002253 acid Substances 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000011541 reaction mixture Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007858 starting material Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 7
- 241001425390 Aphis fabae Species 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 241000244206 Nematoda Species 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 4
- 241001143309 Acanthoscelides obtectus Species 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 240000006677 Vicia faba Species 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000244199 Panagrellus redivivus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 241000233835 Tradescantia Species 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000001069 nematicidal effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000238876 Acari Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000907225 Bruchidius Species 0.000 description 1
- 241000254001 Carausius Species 0.000 description 1
- 241000254000 Carausius morosus Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000630736 Ephestia Species 0.000 description 1
- 241000122098 Ephestia kuehniella Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000238814 Orthoptera Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940096118 ella Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KLBOFRLEHJAXIU-UHFFFAOYSA-N tributylazanium;chloride Chemical compound Cl.CCCCN(CCCC)CCCC KLBOFRLEHJAXIU-UHFFFAOYSA-N 0.000 description 1
- OOLLAFOLCSJHRE-ZHAKMVSLSA-N ulipristal acetate Chemical compound C1=CC(N(C)C)=CC=C1[C@@H]1C2=C3CCC(=O)C=C3CC[C@H]2[C@H](CC[C@]2(OC(C)=O)C(C)=O)[C@]2(C)C1 OOLLAFOLCSJHRE-ZHAKMVSLSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2412—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic alcohols
-
- 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 System
- 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
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/26—Amides of acids of phosphorus containing P-halide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
WHEREIN R1 is alkyl of one to four carbon atoms, R2 is alkyl of one to four carbon atoms, R3 is alkyl of one to five carbon atoms, and X is hydrogen, chlorine or bromine. The compounds are useful pesticides.
The present invention concerns new thiophosphoric acid amide esters of the formula :
The present invention concerns new thiophosphoric acid amide esters of the formula :
Description
Leber et al.
[ Sept. 11, 1973 ClS-Tl-llOPHOSPHORlC ACID AMIDE ESTERS [75] Inventors: Jean-Pierre Leber; Karl Lutz, both of Basle, Switzerland [73] Assignee: Sandoz Ltd., (a/K/A) Sandoz AG,
Basle, Switzerland [22] Filed: July 14, 1970 [21] Appl. No.: 54,837
[30] Foreign Application Priority Data July 18, I969 Switzerland llO28/69 Jan. 21, l970 Switzerland 797/70 [52] US. Cl 260/941, 260/973, 260/984,
[51] Int. Cl A0ln 9/36, C07f 9/l6, C07f 9/72 [58] Field of Search 260/94l [56] References Cited UNITED STATES PATENTS 3,216,894 11/1965 Lorenz et al 260/941 X 3,014,955 12/1961 Beriger 260/941 3,053,729 9/1962 Sun 260/941 X Primary Examiner-Lewis Gotts Assistant ExaminerRichard L. Raymond Attorney-Gerald D. Sharkin, Robert 8'. Honor, Frederick H. Weinfeldt, Richard E. Vila and Walter F.
Jewell [57] ABSTRACT The present invention concerns new thiophosphoric acid amide esters of the formula wherein R is alkyl of one to four carbon atoms, R is alkyl of one to four carbon atoms,
R is alkyl of one to five carbon atoms, and
X is hydrogen, chlorine or bromine.
The compounds are useful pesticides.
16 Claims, No Drawings The present invention relates to new thiophosphoric acid amide esters of formula I,
( 3H: COOR:
possessed by those compounds wherein the -CH, and
-COOR radicals are cis to one another in the crotonic acid radical. Thus, it is to be understood that definitions forthe compounds I essentially contemplate compounds having said cis configuration, although compounds comprising a mixture of the cis form and a certain amount of the trans form are also contemplated. The configuration of compounds I is dependent on the configuration of the starting materials employed in the processes described below, and the process for the production of the starting materials described below result in a predominant proportion of compounds having the cis configuration.
According to the present invention a process for the production of a compound of formula I comprises a. reacting a compound of formula V,
wherein R R and X are as defined aboveg and Y is halogen,
with an amine of formula IV,
RQNH,
Z is hydrogen or an alkali metal, in the presence of an acid acceptor when Z is hydrogen, and optionally in the presence of an acid acceptor when Z is an alkali metal.
Preferably Y is chlorine or bromine, and Z is hydrogen or sodium.
In one method of effecting process a) of the invention, a compound of formula [V and an acid acceptor such as triethylamine, trimethylamine, dimethyl aniline, diethyl aniline or sodium carbonate, are added at a temperature of between 20 and +50C, preferably between l0 and 0C, to a compound of formula V in an inert solvent, e.g., an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorobenzene or chloroform, or an ether such as dioxane, over a period of between one-half hour and 2 hours.
Preferably an equivalent amount of the compound of formula IV with respect to the compound of formula V is employed, and the amount of the acid acceptor is preferably such as to be equivalent with respect to the compound of formula V, for taking up the hydrohalic acid produced in the reaction. However, it will be appreciated that when a compound of formula IV itself is employed as acid acceptor, then the amount of the compound of formula IV is preferably two equivalents with respect to the compound of formula V.
The reaction mixture is stirred at room temperature over a'period of between [0 and 20 hours. The solvent is subsequentlyremoved in a vacuum at a bath temperature of between 20 and 50C. The residue is distilled in a high vacuum. The pure compound of formula I is obtained as a colourless oil which can be distilled without decomposition. I
In one method of effecting process b) of the invention, a compound of formula III and an acid acceptor such as triethylamine, trimethylamine, dimethyl aniline or diethyl aniline, are added at a temperature of between -20 and +50C, preferably between 0 and 20C, to a compound of formula VI in an inert solvent,
e.g., an aromatic,hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorobenm wherein R is as defined above, and
-zene or-chloroform, or an ether such asdioxane, over a period of between one-half hour and 2 hours.
Preferably an equivalent amou'ntof the compound of formula II] with respect to the'compou'nd' of formula VI is'employed, and the amount of acid acceptor is preferably such as to be equivalent with respect to the compound of formula-Vl,"forthe acceptance of displaced Yradicals. t t The reaction mixture is subsequently stirred at 20C over a period of between 20 and hours,and the reaction mixture is then worked up in the usualmanner, to yield the compound-of formula I. r The compound of formula V employed as starting material in process a) above may be produced by reacting a compound of formula ll,
wherein R,, X and Y are as defined above,
with a compound of formula III, optionally in the pres ence of an acid acceptor.
The resulting reaction mixture may be employed directly for reaction with the compound of formula IV in accordance with process a) above without isolation of the compound of formula V. One method of effecting process a) of the invention starting with the production of a compound of formula V and continuing through to the production of a compound of formula I, without isolation of the compound of formula V, comprises adding preferably at least one equivalent of a compound of formula III, at a temperature of between -20 and +50C, preferably between -lC and room temperature, to a compound of formula II in an inert solvent, e.g., an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorobenzene or chloroform, or an ether such as dioxane, over a period of between one-half hour and 2 hours, in the presence of an acid acceptor such as triethylamine, trimethylamine, dimethyl aniline or diethyl aniline.
Preferably the acid acceptor is present in an amount such as to be equivalent with respect to the compound of formula II, for the acceptance of displayed Y radicals.
Without isolation of the compound of formula V,
- produced by the preceding process, from the reaction mixture, a mixture of an amine of formula IV, preferably in an equivalent amount, with an acid acceptor, such as triethylamine, trimethylamine, dimethyl aniline or diethyl aniline, preferably tri-n-butyl amine, preferably also in an equivalent amount, is added at a temperature of between and +50C, preferably between l0C and room temperature, over a period of between one-half hour and 2 hours to the reaction mixture. The reaction mixture is stirred at room temperature for about 20 hours. The reaction mixture is then worked up in the usual manner to yield the compound of formula I.
In an alternative method of effecting process a) of the invention commencing first with the production of a compound of formula V and then continuing through to the production of a compound of formula 1, without isolation of .the compound of formula V from the reaction mixture, a compound of formula II is reacted with a compound of formula III in a manner such as hereinbefore described, but in the absence of an acid acceptor. Subsequent reaction of the resulting compound still contained in the reaction mixture with a compound of formula IV may be effected by employing at least three equivalents of the compound of formula IV, which compound in addition to reacting with the compound of formula V, also serves as acid acceptor, by reacting with the hydrohalic acid produced during the overall reaction, including the reaction between the compounds of formulae II and Ill.
The production of a compound of formula VI, employed as starting material in process b) above for the production of a compound of formula I, may be effected by reacting a compound of formula II with a compound of formual IV, preferably in equivalent amounts, in the presence of an acid acceptor.
As already indicated, the compounds I of the invention essentially contemplate compounds wherein the -CH and -COOR radicals are cis to one another in the crotonic acid radical. This configuration, or a predominant proportion of compounds of formula I having this configuration (more than 80 by weight) can be achieved by preparing the above compounds of formula II in a specific manner. In general, the compounds of formula Il may be produced by reacting a phosphoric oxxyor thiochloride or bromide with a compound of formula VI],
CI-I COCHXCOOR Vll wherein R and X are as defined above, or with a salt thereof, in the presence of an acid acceptor. The compounds of formula II predominantly have a cis configuration in the crotonic acid radical (i.e. the -CH group is cis to the -COOR group) when an organic base, e.g., tri-n-butylamine or triethylamine, is used as acid acceptor. When, for example, sodium bicarbonate is used as acid acceptor, the portion of cis configuration in the crotonic acid radical of the compound of formula II is smaller than when triethylamine is used. When, for example, a sodium acetoacetic acid ester is used in place of the acetoacetic ester of formula VII and'an acid acceptor, then compounds of formula Il=predominantly having the trans form in the crotonic acid radical are obtained. Thus, in order to obtain compounds of the desired high proportion of cis configuration,- the acid acceptor employed in the production of compounds II needs to be, for example, tri-n-butylamine or triethylamine, and the sodium acetoacetic acid ester is normally not a suitable starting material in the production of compounds II.
In the case wherein a compound of formula II is required as a starting material in a process for the eventual production of a compound I according to process a) above, and involving the intermediate production of a compound of formula V, the process may be effected by reacting a compound of formula VII with a phosphorus thiohalide, e.g., phosphorus thiochloride, in the presence of an acid acceptor, e.g., tri-n-butyl amine, and without isolating the resulting compoundof formula II from the reaction mixture adding thereto a compound of formula III together with an acid acceptor. After the reaction, without isolating the resulting compound of formula V, a compound of formula IV together with an acid acceptor are added to the reaction mixture under the conditions as hereinbefore described, and the reaction allowed to proceed. The resulting reaction mixture is worked up in conventional manner to yield the compound of formula I.
Thethiophosphoric acid amine esters of fonnula I obtained in accordance with the invention areoils which can be distilled in a high vacuum without decomposition. When they are produced in accordance with the processes a) and b) described above, the same ratio of the cis with respect to the trans isomer thereof in the crotonic acid radical is obtained as is present in the starting materials of formulae V and VI and'hence II respectively. The compound I are soluble in organic solvents and may be readily emulsified with water.
The compounds of formula I are .useful pesticides. More particularly, the compounds possess insecticidal, acaricidal and nematocidal properties. They are effective against chewing and sucking insects, particularly against spider mites.
The compounds have a low level of toxicity in warm- 1 tection of plants and animals againstnoxious organisms, e.g., insects, mites and nematodes.
The combatting of noxious organisms may be carried out by conventional methods, e.g. by treating the subjects or locus to be protected with a composition containing a compound of formula I as active agent. For use as pesticides, e.g. in plant protection, the compounds of formula I may be added to carrier materials to form dusting or spraying agents, e.g., solutions or dispersions, employing water or suitable organic solvents, e.g., alcohol, petroleum or tar distillates, optionally in combination with emulsifying agents, e.g., liquid polyglycol ethers derived from high molecular weight alcohols, mercaptans or alkyl phenols with an alkylene oxide. Suitable organic solvents such as ketones, aromatic, optionally halogenated hydrocarbons, or mineral oils, may also be added as solution aids.
Spraying and dusting agents may contain the usual inert carrier materials, e.g., talc, diatomaceous earth, bentonite, pumice, or other additives such as cellulose derivatives and the like, as well as conventional wetting agents and adhesives.
The compounds of formula I may be present in compositions as mixtures with other known active materials. The compositions may contain between 2 and 90 preferably between 5 and 50 by weight of active agent. For application, the compositions, which may be in diluted form, may contain between 0.02 and 90 preferably between 0.1 and 20 by weight of the compound of formula I.
It should be understood that it is not essential that the com-pounds of formula I be free from the trans isomer thereof for use in pesticidal compositionsThis is pertinent in the case wherein in theprocess of production of the compounds of formula I, a certain amount of trans isomer thereof is also produced." 7
The following examples are illustrative of concentrates containing a compound of formula I as active pesticidal agent.
a. 25 parts by weight of a compound of formula I are mixed with 25 parts by weight of isooetylphenyldecaglycol ether and 50 parts by weight of xylene, whereby a clear solution is obtained, which can easily be emulsified in water. The concentrate is diluted with water to the desired concentration before use. i
b. 25 parts by weight of a compound of formula I are mixed with 30 parts by weightof isooctyl phenylocataglycol ether and 45 parts by weight of a-petroleum fraetionhavinga B.P. of 2l0280 (0 0.92). The concentrate is diluted withwater to the desired concentration before use.
mixed with parts by weightof isooctylphenyloctaglycol ether. A clear concentrate is obtained, which may be readily emulsified in water and which is diluted with water-to the desired concentration before use. The following application examples illustrate'the effectiveness of the compounds of formula I. Insecticidal effect against Bruchidius obtectus (bean weevil) contact effect 0.1 to 0.2 cc of en emulsion containing 0.0125 of the active agent of formula l are sprayed with a spraying nozzle into a number of 7 cm diameter Petri dishes. The emulsion in the dishes is then dried for about 4 hours, and then Bruchidius images are placed in each 50 parts by weight of a compound of formula I are I dish which is covered with a lid of fine mesh brass wire grating. The animals are kept without food at room temperature.
After 48 hours the rate of mortality is determined. The mortality rate is indicated as a precentage. means that all the bean weevils were killed, 0 means that no bean weevil was killed. The evaluation is given in the following Table l.
insecticidal effect against Ephestia Kiiehniel la (flour moth) contact effect Petri dishes having a diameter of 7 cm, each containing 10 caterpillars of 10 to 12 mm length, are sprayed by means of a spraying nozzle with 0.1 to 0.2 cc of an emulsion containing 0.05 of the active agent of for- TABLE :2 (unlmuml "lAliLl'I 'l llulu of mm'lnllty Rule of umlln lly In pi-rm'nlv nllm' In [it'llllll Actlvo agent days Acllvo ugmll :iflvr ll-l hours (1,1150 s 100 (11130 s im.
7' {I l. 1) 11-031mm 0- 1=o1tcooc1n ll-CglizNII 0-( 3=cn-c00c1n cm cm GU30 S 100 01130 s 100 y P P i-C3H1NII 0C=CH-c00CIn CzH NII O-C=CHCOOi-C:II.-
i CH3 CH3 C2H5O S 100 g I u-CgHyNH OC=CHCOOCH: Insecticidal effect against Carausius morosus E (Indian rod locust) feed effect C H O s 100 2 Tradescantia branches are immersed for 3 seconds in- 2 0 5 an emulsion containing 0.0125 of a compound of formula 1. After drying, each of the Tradescantia CtHsNH I Oi-CaH1 branches is inserted into a small glass tube filled with water, and this is placed in a glass dish. 10 Carausius larvae in the second stage of development are counted into each dish which is then closed with a wire mesh lid.
After 5 days the rate of mortality is determined by counting out the live and dead animals. The mortality rate is indicated as a percentage. 100 means that all the rod locusts were killed, 0 means that no rod locust was killed. The evaluation is indicated in the following Table 3.
i raisin a Rate of mortality in percent- Active agent after 5 days CHaO S 100 n-CsHrNH O?=CH-COOCH3 CHaO S 100 P i-CaIl'7NII O(]}=GH-COOCH:
(JzlIaU s .1uo
Il-C3ll7Nll O(IJ =:CIIUOOGH:|
(Ella OIIJO S 100 P CzHsNH O(]7=CHCO0l-CJH:
ins cticidal ctlect against Aphis fabae (black bean aphid) contact efiect Broad bean plants (Vicia faba) are sprayed to run off with a spraying liquor containing 0.0125 of active agent. The broad bean plants are strongly infected with all the forms of development of the black bean aphid (Aphis fabae).
After 2 days the rate of mortality is determined. The mortality rate is indicated as a percentage. 100 means that all the bean aphids were killed, 0 means that no bean aphid was killed. The evaluation is indicated in the following Table 4.
Nematocidal effect against Panagrellus redivivus (paste nematode) 1 cc of an aqueous suspension of Panagrellus redivivus, containing about 120 nematodes, is placed in a small cup having a diameter of 5.5 cm and a height of 3.2 cm, and containing 7 g of Terralite. 1 cc of an emulsion containing a compound of formula I is then spread over the Terralite. After 48 hours the contents of the cup are examined in accordance with Baermann's extraction method (G.Baermann, Meded.Geneesk.Lab.'- Weltefreden 1917, 41-47), and the live nematodes are counted out under a binocular magnifying glass. The rate of mortality is indicated as a range of 0 to 9 (9 maximum effect, no live nematodes, 0 no effeccover live nematodes). The evaluation is indicated in the following Table 5.
The following Examples illustrate the prmimnkm of the compounds, but in no way limit the wipe of 0m in vention. The temperatures'are indicated in degiees Centigrade.
EXAMPLE 1: 0-( l Carboisopropoxy-l -propen-2-yl O-methyl-N-ethyl-phosphorothioamidate (process a OC=CHCOOCH(Cllz)g CHaO pyl ester and 178 g (1.05 mols) of'thiophosphoryl chloride while stirring and cooling to about 3 during the course of 1 hour. The solution which turns viscous is stirred at to 3 for a further half hour, whereby the solution is mixed as thoroughly as possible. As soon as a viscous oil starts to separate, 20 cc of toluene are added. 1.2 liters of petroleum ether are added, the mix-' ture is stirred for a short period and the tributyl ammonium chloride is filtered off. The filtrate is concentrated in a vacuum at a bath temperature of 30. 128 g (4.0 mols) of methanol are added to the residue as rapidly as possible at 0 and the mixture is stirred at 0 for 4 hours. 226 g of a 70 aqueous solution of ethylamine (3.5 mols) are then added at within one-half hour, and the mixture is stirred at 0 for a further onehalf hour. The reaction mixture is extracted twice in a separatory funnel with 120 cc amounts of approximately hydrochloric acid (25 cc of concentrated hydrochloric acid with 100 g of crushed ice). The separation of the phases during the first washing with aqueous hydrochloric acid is effected without the addition of petroleum ether; petroleum ether is preferably added during the second washing with aqueous hydrochloric acid in order to complete the separation. The petroleum ether phase isagain washed with water and with hydrogen carbonate solution, is dried with sodium sulphate, and the solventis removed. The resulting 0- 1 carboisopropoxyl propen-2-yl)-0-methyl-N-ethylphosphorothioamidate hasa B.'P. of 8789/5.10" mm of Hg. n 1.495.
Analysis: C H NO PS Molecular weight: 281.3 Calculated: C 42.7 H 7.2 N 5.0 P 11.0 S 11.4
Found: 42.1 6.8 5.3 11.0 10.9 1 1 EXAMPLE 2: 0-(1Carboisopropoxy-l-propen-2-yl)- O-ethyl-N-npropyl-phosphorothioamidate (process a) 286.7 g (1 mol) of cis-0*ethy1-0-(l-carboisopropoxy- 1-propen 2-yl)-thionophosphorochloridate [Cl(C,1-l,,. O)P(S)OC(CH )=CHCOOCH(CH dissolved in 1 liter of toluene, are'added to a mixture of.59.1 g .(1 mol) of propylamine and 101.2 g (1 mol) of triethylamine at a reaction temperature of 20 with '2 hours. The reaction mixture is stirred at 20 for'a further 36 hours, and the precipitated triethylamine hydrochloride is subsequently filtered off. The filtrate is washed with water, dried, the solvent is removed by evaporation, and the resulting product is distilled in a vacuum. 0-( l-Carboisopropoxy- 1 propen-2-yl)-0-ethyl-N-npropylphosphorothioamidate has a 8.1. of 87-89 at a pressure of 5.10' mm of Hg. It is obtained almost exclusively with the cis form in the crotonic acid radical. "D20 Analysis: C,,H NO,PS Molecular weight: 309.4 Calculated: C 46.6 H 7.8 N 4.5 P 10.0 S 10.4
% Found: 46.7 7.8 4.8 9.9 10.6
The 0-ethyl-0-(1carboisopropoxy-1-propen-2-yl)- thioph sphorochloridate, required as starting material, may be produced as follows:
277.1 g (1 mol) of cis-0-( l-carboisopropoxy-lpropen-Z-yl)rthiophosphorodichloridate are added at a reaction temperature of 5 to 276 g (6, mols) of ethanol. The temperature is then allowed to rise to 1012, and the mixture is kept at this temperature for one-half hour. The reaction mixture is subsequently diluted with 500 cc of toluene and is made neutral with 200 cc of a 20 caustic soda solution at 10 to 5 while stirring vigorously. The reaction mixture is added to 200 cc of ice water, the organic phase is separated, is washed well with a sodium hydrogen carbonate solution and subsequently with water, is dried with magnesium sulphate, filtered and concentrated by evaporation in a vacuum at 40. The resulting product may be purified by distillation in a high vacuum. It is also possible to use the crude product in the reaction for the production of the corresponding compound of formula I.
0-( 1 -Carboisopropoxy-1-propen-2-y1)-thiophosphoro-dichloridate is obtained in the following manner:
105 g (1.03 mols) of triethylamine are added at 10 while stirring within one-half hour to a mixture of 169.4 g (1 mol) of thiophosphoryl chloride, and 144.2 g (l mol)-of acetoacetic acid isopropyl ester, whereby triethylamine hydrochloride precipitates. The reaction mixture is subsequently stirred at a temperature'between 10 and +10 for one-half hour, and at for 320 g lmol). of 0-( 1 chlorof 1 carbethoxy-l -pr open- 2-yl)-N-n propyl-phosphoramidochloridothionate [Cltrans 9:1) are dissolved inamixture of 500 cc of tolufe'ne and 500cc of chloroform. A mixture of 32.1 g (1 ,mol) of methanol and1'101.2 g (1 mol) of triethylamine is added at 0 to this solution within Z-hours. Thereaction mixture is then stirred at 0 for 5 hours','and subsequently at 20 for 100 hours. The precipitated triethylamine hydrochloride is filtered off. and the filtrate is washed, driedand distilled. The resulting 0-( l-chlorolcarbethoxy-l propen-Z-yl )-0-methyl-Nn-propyl-phosphorothioamidate has a 8.1. of 107 at 0.01 mm of Hg. The ratio of the cisztrans isomers in the crotonic acid radical amounts to 9:1.
Analysis: C H,,ClNO,PS Molecularweight: 315.8
Calculated: C 38.0 H 6.1 C1 11.2 N 4.4 P 9.8 185 10.2 v Found: 38.4 6.3 11.5 4.4 9.7 10.8
The 0-( l-chloro-lcarbethoxy-1-propen-2-yl)-N-npropyl-phosphoroamidochloridothionate, required as starting material, may be produced in the following manner: a
A solution of 297.5 g (1 mol) of '0-(l-chloro-1- carbethoxyl propen-2-yl )-thiophosphorodichloridate in 1 liter of toluene is reacted at with a mixture of 59.1 g (1 mol) n-propylamine ri-orpoylamine and 102 g (1 mol) of triethylamine during the course of 1 hour. The reaction mixture is subsequently stirred at 0 for one-half hour, and at 20 for 1 hour. The precipitated triethylamine hydrochloride is subsequently filtered off, the filtrate 1s washed with water, dried with sod1um l h t d d nll wherein X signifies a hydrogen atom, which are ob- 0-( l -Chlorol -carbethoxy-l-propen-2-yl)-th1ophostamed as a mixture with the trans isomer in some cases, phorodichloridate may be obtained in a manner analothe ratio of the cisztrans isomers 1n the crotomc acid gous to the d chlor date descr bed n Example 2, radical being substantially the same as thatof the start- The following compounds (see Table WhlCh follows) mg materials, may be obtained ina manner analogous of formula I, to that described 1n Examples 1, 2 and 3.
Ratio Analysis, percent cisztrans Molec in the cm- Calculated Found Empirical ular 13.13.. tonic acid R5 formula weight C. 1in'- radical C II N l S C II N l S CH5 C7HHNO4PS 230.2 11-80 1.501 Cis 35.1 5.0 5.0 12.0 13.4 85.0 0.2 0.0 13.0 13.4 CH: 0111051011 8 201.3 80-01 1.501 018 40.4 0.8 5.2 11.0 12.0 40.3 0.1 5.1 11.0 12.0 CH: CDHIBNO4PS 201.3 10-80 1.408 018 40.4 0.8 5.2 11.0 12.0 41.0 0.3 5.5 12.1 13.0 105H: C11H22NO4PS 205.3 84-85 1.401 0:1 44.1 1.5 4.1 10.5 10.0 44.4 1.5 5.1 10.8 11.1 CH: 01011100104188 281.3 88-80 1.401 85:15 42.1 1.2 5.0 11.0 11.4 42.1 1.3 5.1 10.0 11.1 CH: 01110510188 253.3 84 1.504 05:5 31.0 0.4 5.5 12.2 12.1 31.1 0.5 5.0 12312.0 H3 C1H11NO4PS 253.3 88 1.503 03:1 31.0 0.4 5.5 12.2 12.1 38.3 0.4 5.5 12.0 12.0 CH: ommNoms 201.3 -00 1.400 05:5 40.4 0.8 5.2 11.0 12.0 40.3 0.8 5.2 11.0 12.3 CH: omm Noms 281.3 18 1.400 Cis 42.1 1.2 5.0 11.0 11.4 42.4 1.2 5.2 11.3 11.4 0111 (31110010118 201.3 01-02 1.500 00:10 40.4 0.8 5.2 11.0 12.0 40.3 0.0 5.0 11.4 12.4 CH: 010112001011 8 281.3 02-04 1.400 :15 42.1 1.2 5.0 11.0 11.4 43.0 1.0 5.1 11.5 12.0 CH; C11H23NO4PS 205.3 04-00 1.405 00:10 44.1 1.5 4.1 10.5 10.0 45.5 0.0 4.5 11.1 11.0 011: 011110100 23 205.3 81 -80 1.403 05:5 44.1 1.5 4.1 10.5 10.0 44.5 1.4 4.8 10.1 11 CH: CHHHNOJPS 300.4 00-08 1.403 00:10 40.0 1.8 4.5 10.0 10.4 40.1 1.0 4.1 10.8 10 CH0 00111431011 8 201.3 81 1.400 018 40.4 0.8 5.2 11.0 12.0 30.1 0.1 5.5 11.1 12.3 CH5 ommuNmPs 281.3 85-80 1.405 00:10 42.1 1.2 5.0 11.0 11.4 41.1 1.1 5.4 11.1 11.0 CH3 Ci1Hz2NO4PS 205.3 80 1.403 01:3 44.1 1.5 4.1 10.5 10.0 44.4 1.1 4.1 10.0 10.0 CH; CuHgzNOdS 205.3 81-84 1.480 Cis 44.1 1.5 4.1 10.5 10.0 44.1 1.5 4.4 11.2 11.1 CH: C0H0No1Ps 205.3 03-04 1.403 05:5 44.1 1.5 4.1 10.5 10.0 45.0 1.0 5.0 10.0 11.0 CH1 C13Hz5N01PS 323.4 01-03 1.400 85:15 48.3 8.1 4.3 0.0 0.0 41.1 8.1 4.2 10.1 10.8 01H: C:H::N0iPs 253.3 81-88 1.504 05:5 31.0 0.4 5.5 12.2 12.1 38.5 0.4 5.8 11.8 13.1 02H: 0:11: 510418 201.3 81 1.400 015 40.4 0.8 5.2 11.0 12.0 40.0 1.0 0.1 11.0 11.3 02115 C4H11NO4PS 201.3 84-80 1.408 (315 40.4 0.8 5.2 11.0 12.0 40.4 0.1 4.0 12.5 12.3 0213, C H NO PS 281.31 8581 1.400 05:5 42.1 1.2 5.0 11.0 11.4 42.0 1.3 5.1 11.0 11.5 01115 01 111531011 8 205.3 05-00 1.403 05:5 44.1 1.5 4.1 10.5 10.0 45.2 1.5 4.0 10.1 11.3 04H: 00112251011 8 205.3 80-00 1.402 05:5 44.1 1.5 4.1 10510. 44.5 1.5 4.0 10.8 11.3 (32H, C H NOdS 281.3 0008 1.400 05:5 42.1 1.2 5.0 11.0 11.4 42.1 1.1 5.3 10.1 12.0 0211: 001122010198 205.3 05-00 1.401 01:3 44.1 1.5 4.1 10.5 10.0 45.0 1.0 4.0 11.2 11.3 01H: O12H:1NO:PS 300.4 02-04 1.402 Ois 40.0 1.8 4.5 10.0 10.4 40.1 8.0 4. 10.5 10.2 04H: C12Hz4NO4PS 300.4 88-80 1.480 05:5 40.0 1.8 4.5 10.0 10.4 40.8 1.0 4.3 10.3 10.4 C4H5 C10Hz NO4PS 281.3 03-04 1.402 Cis 42.1 1.2 5.0 11.0 11.4 42.3 1.3 5.2 11.0 11.4 01H: C11H22N04PS 205.3 80-02 1.480 05:5 44.1 1.5 4.1 10.5 10.0 44.0 1.3 4.0 10.0 11.1 o 0:13 C1:H:1N0iPs 300.4 04 1.480 Cis 40.0 1.8 4.5 10.0 10.4 40.4 8.0 4.0 10.8 10.8 .10511: 10:11: 01H: C12H24NO|PS 300.4 01-02 1.485 Cis 40.0 1.8 4.5 10.0 10.4 40.1 1.0 4.1 10.2 10.4 -11C4H9 101B: 0,121 CHIIIBNOlPS 331.4 03-04 1.480 Cis 40.8 8.4 4.2 0.2 0.5 40.1 8.5 4.2 0.4 0.2 1C4H0 11C1H0 C2H5 C11H28NO4PS 337.4 104-06 1.484 018 49.8 8.4 4.2 9.2 9.5 49.4 8.7 4.4 9.9 9.6 OH: CH; 00:11: 0111011011 8 201.3 02 1.502 80:11 40.4 0.8 5.2 11.0 12.0 40.5 0.8 5.1 12.1 13.4 CH3 CzHu 1161111 C10H111NO4PS 281.3 96 1.498 9525 42.7 7.2 5.0 11.0 11.4 42.8 7.3 5.6 11.6 12.2 CH3 iC1H1 11031-11 CuHzzNOflS 295.3 92 1.494 :10 44.7 7.5 4.7 10.5 10.9 45.1 7.8 5.0 10.7 11.4 0:113 CH; 1103H1 010114011011 8 281.3 02-04 1.405 05:5 42.1 1.2 5.0 11.0 11.4 43.0 1.2 5.0 11.4 11.0 04H: nCaH-l 00:11: 00111101011 8 300.4 101-05 1.401 81:13 40.0 1.8 4.5 10.0 10.4 40.3 1.8 4.8 0.0 10.2 01H: 1C:H1 1101111 01111001011 81 300.4 08 1.488 00:10 40.0 1.8 4.5 10.0 10.4 41.0 1.1 5.0 10.2 11.0 110111: 0411: 110111: 01411115101881 300.4 104-05 1.400 05:5 40.0 1.8 4.5 10.0 10.4 41.0 1.0 4.2 10.5 10.8 .00111: nCaH1 nCaH: CHHNNOAPS 323.4 111 1.480 05:0 48.3 8.1 4.3 0.0 0.0 48.4 8.0 4.0 0.1 10.0 .ncm: 1C:H1 1103111 ou'mgNoms 323.4 102-03 1.481 00:10 48.3 8.1 4.3 0.0 0.0 48.0 8.3 3.1 0.1 10.4 004111 CHHMNmPS 205.3 011-01 1.400 Cis 44.1 1.5 4.1 10.5 10.0 45.0 1.0 5.1 10.8 11.2 004111 011110110403 300.4 115-011 1.488 ()is 40.0 1.8 4.5 10.0 10.4 40.3 1.8 4.1 10.3 10.3 1104111 011111101011 0 323.4 104-05 1.480 015 48.3 8.1 4.3 0.0 0.0 41.0 8.0 4.0 0.8 10.2 1101111 01111411101811 323.4 04-00 1.483 Cls 48.3 8.1 4.3 0.0 0.0 48.0 8.1 3.0 0.0 0.0 10:11: C0H0N0u s 201.3 01 1.400 03:1 40.4 0.8 5.2 11.0 12.0 40.4 0.1 4.8 11.0 12.0 10:11: 0011011041 8 205.3 05-01 1.405 05:5 44.1 1.5 4.1 10.5 10.0 44.4 1.4 4.8 10.8 12.0 10:11: C11Hz-1NO1PS 205.3 80 1.402 85:15 44.1 1.5 4.1 10.5 10.0 45.4 8.0 4.0 10.3 10.8 103111 C10 :5N01Ps 281.3 01-03 1.402 01:3 42.1 1.2 5.0 11.0 11.4 43.3 1.3 5.0 10.1 11.0 10 111 G12H2|NO4PS 300.4 00-02 1.480 05:5 40.0 1.8 4.5 10.0 10.4 40.5 1.1 4.0 10.0 10.3 1C:H1 C11H25NO1PS 323.4 1.488 00:10 48.3 8.1 4.3 0.0 0.0 48.1 1.0 4.3 0.0 0.8 10311: 011115111011 8 205.3 05-01 1.400 01:3 44.1 1.5 4.1 10.5 10.0 45.2 1.0 4.1 10.8 11.0 103111 (31: :moms 3004 08-00 1.488 03:1 40.0 1.8 4.5 10.0 10.4 41.3 1.8 4.1 10.2 10.8 103111 CHHZBNOlPS 323.4 101-03 1.481 01:3 48.3 8.1 4.3 0.0 0.0 48.3 8.1 4.5 0.0 0.2 103111 013114010011 8 323.4 01-08 1.485 01:3 48.3 8.1 4.3 0.0 0.0 48.4 8.1 4.3 0.0 10.1 103E: CHHQQNOJS 331.4 100-03 1.483 015 40.8 8.4 4.2 0.2 0.5 50.2. 8.5 4.1 0.4 0.1 10:11: Ci1H22NO1PS 205.3 00-02 1.488 015 44.1 1.5 4.1 10.5 10.0 44.1 1.3 4.0 10.8 11.0 10:11: Oi2H24NO1PS 300.4 011-112 1.485 Cis 40.0 1.8 4.5 10.0 10.4 40.4 1.1 4.5 10.3 10.4 10311: Ci1H2aNO1PS 323.4 011-101 1.485 Cis 48.3 8.1 4.3 0.0 0.0 41.0 1.0 4.8 10.0 10.0 10311: C1:H::N0i1 s 323.4 80 1.482 015 48.3 8.1 4.3 0.0 0.0 41.0 8.0 3.0 10.2 0.0 0:115 C10HQQNO4PS 281.3 01-00 1.400 88:12 42.1 1.2 5.0 11.0 11.4 42.1 1.1 4.0 11.1 11.0 02111 cmu NoiPs 281.3 81-00 1.401 88:12 42.1 1.2 5.0 11.0 11.4 42.1 1.4 4.0 10.0 12.1 10. 011: 11C3H1 11C:H: 011114401011 8 205.3 102 1.400 00:10 44.1 1.5 4.1 10.5 10.0 45.4 1.4 4.0 11.1 12.3 @2115 0,11 11C3H: 01111121001188 205.3 00 1.403 00:10 44.1 1.5 4.1 10.5 10.0 44.3 1.2 4.8 10.3 10.0 g c 0H 03H: 0111121110188 205.3 104-00 1.403 05:5 44.1 1.5 4.1 10.5 10. 44.0 1.3 4.5 10.2 10.8
What is claimed is: 1. A compound of the formula:
wherein R, is alkyl of one to four carbon atoms, R, is alkyl of one to four carbon atoms, R is alkyl of one to five carbon atoms, and X is hydrogen, chlorine or bromine, in which -CH is cis to the -COOR in the crotonic acid moiety.
2. The compound of claim 1, wherein R, is methyl, R is methyl, R is isopropyl and X is hydrogen.
3. The compound of claim 1, wherein R, is methyl, R is ethyl, R is methyl and X is hydrogen.
4. The compound of claim 1, wherein R, is methyl, R and R are ethyl and X is hydrogen.
5. The compound of claim 1, wherein R, is methyl, R is ethyl, R, is isopropyl and X is hydrogen.
6. The compound of claim 1, wherein R, is methyl, R is n-propyl, R is methyl and X is hydrogen.
7. The compound of claim 1, wherein R, is methyl, R is n-propyl, R is ethyl and X is hydrogen.
8. The compound of claim 1, wherein R, is methyl, R, is isopropyl, R is methyl and X is hydrogen.
9. The compound of claim 1, wherein R, is methyl, R and R are isopropyl and X is hydrogen.
10. The compound of claim 1, wherein R, is ethyl, R, is methyl, R is ethyl and X is hydrogen.
11. The compound of claim 1, wherein R, is ethyl, R is isopropyl, R is methyl and X is hydrogen.
12. The compound of claim 1, wherein R, is ethyl, R and R are isopropyl and X is hydrogen.
13. The compound of claim 1, wherein R, is n-propyl, R is methyl, R is isopropyl and X is hydrogen.
14. The compound of claim 1, wherein R, is isopropyl, R, is methyl, R is ethyl and X is hydrogen.
15. The compound of claim 1, wherein R, is methyl,
R, is n-propyl, R is ethyl and X is chlorine.
16. A compound of claim 1 in which R; is isopropyl and X is hydrogen.
Claims (15)
- 2. The compound of claim 1, wherein R1 is methyl, R2 is methyl, R3 is isopropyl and X is hydrogen.
- 3. The compound of claim 1, wherein R1 is methyl, R2 is ethyl, R3 is methyl and X is hydrogen.
- 4. The compound of claim 1, wherein R1 is methyl, R2 and R3 are ethyl and X is hydrogen.
- 5. The compound of claim 1, wherein R1 is methyl, R2 is ethyl, R3 is isopropyl and X is hydrogen.
- 6. The compound of claim 1, wherein R1 is methyl, R2 is n-propyl, R3 is methyl and X is hydrogen.
- 7. The compound of claim 1, wherein R1 is methyl, R2 is n-propyl, R3 is ethyl and X is hydrogen.
- 8. The compound of claim 1, wherein R1 is methyl, R2 is isopropyl, R3 is methyl and X is hydrogen.
- 9. The compound of claim 1, wherein R1 is methyl, R2 and R3 are isopropyl and X is hydrogen.
- 10. The compound of claim 1, wherein R1 is ethyl, R2 is methyl, R3 is ethyl and X is hydrogen.
- 11. The compound of claim 1, wherein R1 is ethyl, R2 is isopropyl, R3 is methyl and X is hydrogen.
- 12. The compound of claim 1, wherein R1 is ethyl, R2 and R3 are isopropyl and X is hydrogen.
- 13. The compound of claim 1, wherein R1 is n-propyl, R2 is methyl, R3 is isopropyl and X is hydrogen.
- 14. The compound of claim 1, wherein R1 is isopropyl, R2 is methyl, R3 is ethyl and X is hydrogen.
- 15. The compound of claim 1, wherein R1 is methyl, R2 is n-propyl, R3 is ethyl and X is chlorine.
- 16. A compound of claim 1 in which R3 is isopropyl and X is hydrogen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1102869A CH526585A (en) | 1969-07-18 | 1969-07-18 | Anti parasitic thio phosphoric acid imide esters |
CH79770 | 1970-01-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3758645A true US3758645A (en) | 1973-09-11 |
Family
ID=25685710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00054837A Expired - Lifetime US3758645A (en) | 1969-07-18 | 1970-07-14 | Cis thiophosphoric acid amide esters |
Country Status (14)
Country | Link |
---|---|
US (1) | US3758645A (en) |
JP (2) | JPS5016778B1 (en) |
BE (1) | BE753579A (en) |
DK (1) | DK133695B (en) |
EG (1) | EG10369A (en) |
ES (2) | ES381927A1 (en) |
FR (1) | FR2102407A5 (en) |
GB (1) | GB1315708A (en) |
IE (1) | IE34387B1 (en) |
IL (1) | IL34939A (en) |
NL (1) | NL171161C (en) |
PL (1) | PL81642B1 (en) |
RO (2) | RO64797A (en) |
YU (3) | YU36036B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4263288A (en) * | 1978-01-03 | 1981-04-21 | Rohm And Haas Company | Acaricidal, insecticidal, and nematocidal phosphoramidothioates |
EP0253762A2 (en) * | 1986-06-16 | 1988-01-20 | Sandoz Ag | Oil in water emulsion |
US4999346A (en) * | 1984-12-20 | 1991-03-12 | Sandoz Ltd. | Novel composition and process for control of cockroach population |
CN105131033A (en) * | 2015-08-10 | 2015-12-09 | 河北工业大学 | N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt and application thereof |
-
1970
- 1970-07-05 YU YU1800/70A patent/YU36036B/en unknown
- 1970-07-06 GB GB3265170A patent/GB1315708A/en not_active Expired
- 1970-07-08 NL NLAANVRAGE7010066,A patent/NL171161C/en not_active IP Right Cessation
- 1970-07-11 EG EG322/70*UA patent/EG10369A/en active
- 1970-07-14 US US00054837A patent/US3758645A/en not_active Expired - Lifetime
- 1970-07-16 FR FR7026163A patent/FR2102407A5/fr not_active Expired
- 1970-07-16 IL IL34939A patent/IL34939A/en unknown
- 1970-07-16 ES ES381927A patent/ES381927A1/en not_active Expired
- 1970-07-16 BE BE753579D patent/BE753579A/en not_active IP Right Cessation
- 1970-07-16 RO RO7076698A patent/RO64797A/en unknown
- 1970-07-16 IE IE922/70A patent/IE34387B1/en unknown
- 1970-07-16 RO RO63938A patent/RO61454A/ro unknown
- 1970-07-17 JP JP45062740A patent/JPS5016778B1/ja active Pending
- 1970-07-17 DK DK371770AA patent/DK133695B/en not_active IP Right Cessation
-
1971
- 1971-01-26 PL PL14583271A patent/PL81642B1/xx unknown
-
1973
- 1973-01-16 ES ES410649A patent/ES410649A1/en not_active Expired
- 1973-01-24 JP JP1019873A patent/JPS5637207B1/ja active Pending
-
1978
- 1978-01-17 YU YU00098/78A patent/YU9878A/en unknown
- 1978-01-17 YU YU00099/78A patent/YU9978A/en unknown
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4263288A (en) * | 1978-01-03 | 1981-04-21 | Rohm And Haas Company | Acaricidal, insecticidal, and nematocidal phosphoramidothioates |
US4999346A (en) * | 1984-12-20 | 1991-03-12 | Sandoz Ltd. | Novel composition and process for control of cockroach population |
EP0253762A2 (en) * | 1986-06-16 | 1988-01-20 | Sandoz Ag | Oil in water emulsion |
EP0253762A3 (en) * | 1986-06-16 | 1990-06-13 | Sandoz Ag | Oil in water emulsion |
CN105131033A (en) * | 2015-08-10 | 2015-12-09 | 河北工业大学 | N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt and application thereof |
CN105131033B (en) * | 2015-08-10 | 2017-05-31 | 河北工业大学 | N (amino of 1,2 diphenyl 2) thiophosphoryl amine salt and its application |
Also Published As
Publication number | Publication date |
---|---|
RO64797A (en) | 1981-06-26 |
JPS5637207B1 (en) | 1981-08-29 |
IL34939A0 (en) | 1970-09-17 |
PL81642B1 (en) | 1975-08-30 |
YU36036B (en) | 1981-11-13 |
IE34387L (en) | 1971-01-18 |
NL7010066A (en) | 1971-01-20 |
FR2102407A5 (en) | 1972-04-07 |
IE34387B1 (en) | 1975-04-30 |
DE2035103A1 (en) | 1971-01-28 |
YU9978A (en) | 1985-12-31 |
NL171161C (en) | 1983-02-16 |
DE2035103B2 (en) | 1975-06-12 |
ES410649A1 (en) | 1976-06-01 |
YU9878A (en) | 1985-12-31 |
ES381927A1 (en) | 1973-04-16 |
DK133695C (en) | 1976-11-22 |
GB1315708A (en) | 1973-05-02 |
EG10369A (en) | 1976-02-29 |
BE753579A (en) | 1971-01-18 |
JPS5016778B1 (en) | 1975-06-16 |
DK133695B (en) | 1976-07-05 |
IL34939A (en) | 1973-03-30 |
RO61454A (en) | 1977-01-15 |
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