US3481731A - Alkoxy vinyl phosphono dithioates as herbicides - Google Patents
Alkoxy vinyl phosphono dithioates as herbicides Download PDFInfo
- Publication number
- US3481731A US3481731A US612101A US3481731DA US3481731A US 3481731 A US3481731 A US 3481731A US 612101 A US612101 A US 612101A US 3481731D A US3481731D A US 3481731DA US 3481731 A US3481731 A US 3481731A
- Authority
- US
- United States
- Prior art keywords
- grams
- mole
- reaction mixture
- added
- ethoxyvinylphosphonodithioate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 Alkoxy vinyl phosphono dithioates Chemical class 0.000 title description 36
- 239000004009 herbicide Substances 0.000 title description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 78
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 34
- 239000011541 reaction mixture Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 230000002363 herbicidal effect Effects 0.000 description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 8
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000000068 chlorophenyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 2
- 244000055702 Amaranthus viridis Species 0.000 description 2
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- 244000056139 Brassica cretica Species 0.000 description 2
- 235000003351 Brassica cretica Nutrition 0.000 description 2
- 235000003343 Brassica rupestris Nutrition 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000009344 Chenopodium album Nutrition 0.000 description 2
- 235000005484 Chenopodium berlandieri Nutrition 0.000 description 2
- 235000009332 Chenopodium rubrum Nutrition 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 235000010460 mustard Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical class OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- QIUCYKBVFAPWRR-UHFFFAOYSA-N 1-ethenoxy-3-methylbutane Chemical compound CC(C)CCOC=C QIUCYKBVFAPWRR-UHFFFAOYSA-N 0.000 description 1
- SHHYVKSJGBTTLX-UHFFFAOYSA-N 1-ethenoxy-6-methylheptane Chemical compound CC(C)CCCCCOC=C SHHYVKSJGBTTLX-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- FGBVJFREPSJSNG-UHFFFAOYSA-N 2,4-dichlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1Cl FGBVJFREPSJSNG-UHFFFAOYSA-N 0.000 description 1
- UCJMHYXRQZYNNL-UHFFFAOYSA-N 2-Ethyl-1-hexanethiol Chemical compound CCCCC(CC)CS UCJMHYXRQZYNNL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PWOBDMNCYMQTCE-UHFFFAOYSA-N 2-chlorobenzenethiol Chemical compound SC1=CC=CC=C1Cl PWOBDMNCYMQTCE-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- FWMKPJYJDJSEHR-UHFFFAOYSA-N 2-propylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCC)=CC=C21 FWMKPJYJDJSEHR-UHFFFAOYSA-N 0.000 description 1
- HVXRCAWUNAOCTA-UHFFFAOYSA-N 4-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=C(O)C=C1 HVXRCAWUNAOCTA-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 235000003499 redwood Nutrition 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- RTVVXRKGQRRXFJ-UHFFFAOYSA-N sodium;2-sulfobutanedioic acid Chemical compound [Na].OC(=O)CC(C(O)=O)S(O)(=O)=O RTVVXRKGQRRXFJ-UHFFFAOYSA-N 0.000 description 1
- AIMUHNZKNFEZSN-UHFFFAOYSA-M sodium;decane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCS([O-])(=O)=O AIMUHNZKNFEZSN-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002680 soil gas Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229940104261 taurate Drugs 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical class OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4015—Esters of acyclic unsaturated acids
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/42—Halides thereof
Definitions
- the present invention is related to the invention in Regel et a1.
- application 596,412 filed Nov. 23, 1966, now Patent No. 3,416,912 wherein 2-alkylthiovinylphosphono dithioates were prepared and found to have herbicidal activity.
- the present invention relates to substituted vinylphosphonodithioates.
- Another object is to develop novel herbicides.
- An additional object is to prepare herbicides having selective pre-emergent herbicidal activity.
- a further object is to prepare herbicides having selective post-mergent herbicidal activity.
- R is lower alkyl, eg of 1 to 8 carbon atoms, most preferably of 1 to 4 carbons, R and R are alkyl of 1 to 8 carbons, phenyl, lower alkyl phenyl or chlorophenyl, R and R can be the same or diiferent.
- the compounds of Formula I are readily prepared by reacting an alkyl vinyl ether with phosphorus pentachloride preferably dissolved in a solvent such as carbon tetrachloride to form the 2-alkoxy-2-chloroethylphosphonyldichloride.
- the complex is treated with two moles of sulfur dioxide. Dehydrohalogenation of the intermediate formed in this reaction occurs simultaneously or upon removal of the phosphorus oxychloridethionylchloride-solvent mixture to yield alkoxyinylphosphonyldichloride.
- alkoxyvinylphosphonodithioates are formed by esterification of the alkoxyvinylphosphonyldichloride with a mercaptan in the presence of a tertiary amine, e.g. triethylamine, tripropylamine, N,N-
- alkyl vinyl ethers as starting materials there can be employed methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec. butyl vinyl ether, amyl vinyl ether, isoamyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, isooctyl vinyl ether.
- mercaptans there can be used methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, butyl mercaptan, isobutyl mercaptan, hexyl mercaptan, cyclohexyl mercaptan, amyl mercaptan, heptyl mercaptan, octyl mercaptan, isooctyl mercaptan, 2-ethylhexyl mercaptan, thiophenol, p-methylthiophenol, 2- chlorothiophenol, 2,4-dichlorothiophenol, 4-butylthiophen01.
- EXAMPLE 1 29 grams (0.5 mole) of methyl vinyl ether was added to a stirring suspension of 208 grams (1 mole) of phosphorus pe'ntachloride in 8-10 volumes of carbon tetrachloride. The reaction mixture was cooled to 10-20 C. throughout the addition. After the addition was completed, the reaction mixture was allowed to warm to room temperature (25 C.) and was then stirred for 12- 14 hours.
- EXAMPLE 2 144 grams (2 moles) of ethyl vinyl ether was added dropwise to a stirring suspension of 833 grams (4 moles) of phosphorus pentachloride in 8-10 volumes of carbon tetrachloride. The reaction mixture was cooled to 10-20 C. throughout the addition. After the addition was completed, the reaction mixture was allowed to warm to room temperature and then stirred for 12-14 hours.
- the 2-isobutoxyvinylphosphonyldichloride was obtained by direct distillation of the reaction mixture, B.P. 92 C.; r15 1.48 68; yield 72%.
- EXAMPLE 4 17.5 grams (0.1 mole) of 2-(methoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 12.5 grams (0.2 mole) of ethyl mercaptan was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
- EXAMPLE 5 13.5 grames (0.08 mole) of 2-(methoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 12.5 grams (0.16 mole) of isopropyl mercaptan was then added. 15.2 grams (0.15 mole) of triethylamines was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30- 35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
- EXAMPLE 12 21.7 grams (0.1 mole) of 2-(isobutoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 13.7 grams (0.22 mole) of ethyl mercaptan was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
- EXAMPLE 13 21.7 grams (0.1 mole) of 2-(isobutoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 16 grams (0.22 mole) of 2-propanethiol was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-25 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate.
- EXAMPLE 14 10.9 grams (0.05 mole) of 2-(isobutoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 10 grams (0.11 mole) of l-butanethiol was then added. 10.1 grams (0.1 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
- the herbicides of the present invention can be used alone or they can be applied together with inert solids to form dusts, or can be dispersed in a suitable liquid dilute, e.g. organic solvents or water.
- the active ingredients can be from 0.01 to 95% by weight of the entire composition.
- organic solvents there can be employed hydrocarbons, e.g. benzene, toluene, xylene, kerosene, diesel fuel, fuel oil and petroleum naphtha, ketones such as acetone,
- chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and perchloroethylene
- esters such as ethyl acetate, amyl acetate and butyl acetate
- ethers e.g. ethylene glycol monomethyl ether and diethylene glycol taurate.
- Turkey red oil sodium dibutyl naphthalene sulfonate, sodium lignin sulfonate, polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether (Nonionic 218), long chain ethylene oxide-propylene oxide condensation products, e.g.
- the surface of the soil gas such as dichlorodifluorornethane or trichlorofluoro- Was sprayed with an acetone solution of the test commethane and other Freons and Genetrons, for example. pound the same day as the seeds were planted.
- the flats The pesticides of the present invention can also be apwhich were planted were 14 inches long, 10 inches wide plied with adjuvants or carriers such as talc, pyrophyllite, n 3.5 inches deep.
- test material was synthetic fine silica, attapulgus clay, kieselguhr, chalk, diluted to ml. with acetone.
- diatomaceous earth, lime, calcium carbonate, bentonite when applied to the flat was equivalent to 1 1b./ acre of Fullers earth, cottonseed hulls, wheat flour, soybean flour, test al (active ingredient)- Th6 requisite number pumice, tripoli, wood flour, walnut shell flour, redwood 20 of ml. of the acetone solution was diluted to ml. and flou and lignin, this diluted mixture was sprayed on the flats, e.g.
- Typical classes of surface active agents include alkyl and emerge The results ill thfi pfs-emel'gent herbicide sulfonate salts, alkylaryl sulfonate salts, alkylaryl polyare set forth in Table 1.
- ether alcohols fatty acid esters of polyhydric alcohols and the alkylene oxide addition products of such esters, and addition products of long chain mercaptans and alkylene oxides.
- surface active agents include the sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, alkylphenol ethylene oxide condensation products, e.g. p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g.
- sodium stearate and potassium oleate sodium salt of propyl-naphthalene sulfonic acid, di (Z-ethylhexyl) ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium decane sulfonate, sodium salt of the sulfonated monoglyceride of cocoanut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether, polyethylene glycol esters of fatty acids and rosin acids, e.g.
- S,S-diisopropylpound is selected from the group consisting of Z-methoxyvinylphosphonodithioate (Compound 7375 S S diiso propyl-2-methoxyv1nylphosphonodithioate, S,S dnsopropyl 2 1sobutoxyvmylphosphonodithloate SS diethy1 z ethoxyvinylphosphonodithioate; (compcfurfd 7676) and f P?
- a process according to claim 6 wherein the comthe i zza g f tg 23213 13 efiectlve amount of a pound is selected from the group consisting of c u avm omp g e S,S-di1sopropyl-2-methoxyvinylphosphonodlthioate;
- R 00H 0HP i 8.
- R 1s lower alkyl and R and R are selected References Cited from the group consisting of alkyl of 1 to 8 carbon UNITED STATES PATENTS atoms, phenyl, lower alkyl phenyl and chlorophenyl.
- a process of killing plants comprising applying LEWIS GOTTS Prima EX to the plant habitat a herbicidally effective amount of ry animer a compound according to claim 1 having the formula CATHERINE MILLS Asslstant Exammer 0 SE, US. Cl. X.R. fll/ 260950, 956
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Description
United States Patent 3,481,731 ALKOXY VINYL PHOSPHONO DITHIOATES AS HERBICIDES Erik K. Regel, Mission, Kans., and Marion F. Botts,
Independence, Mo., assignors to Chemagro Corporation, Kansas City, Mo., a corporation of New York No Drawing. Filed Jan. 27, 1967, Ser. No. 612,101
The portion of the term of the patent subsequent to Dec. 17, 1985, has been disclaimed Int. Cl. A01n 9/36 US. Cl. 7187 8 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula RiOCH=CHP where R is lower alkyl and R and R are lower alkyl, phenyl, alkyl phenyl or chlorophenyl are prepared by (1) reacting alkyl vinyl ethers with phosphorus pentachloride, (2) converting the complex to alkoxy 2-chloroethyl phosphonyldichloride by treatment with sulfur dioxide with simultaneous dehydrohalogenation to alkoxyvinylphosphonyldichloride and (3) reacting with two moles of a mercaptan in the presence of a tertiary amine. The new compounds are useful as preand post-emergent herbicides. S,S diisopropyl 2 isobutoxyvinylphosphonodithioate Was the overall best herbicide tested.
The present invention is related to the invention in Regel et a1. application 596,412, filed Nov. 23, 1966, now Patent No. 3,416,912 wherein 2-alkylthiovinylphosphono dithioates were prepared and found to have herbicidal activity.
The present invention relates to substituted vinylphosphonodithioates.
It is an object of the invention to prepare novel substituted vinyl phosphonodithioates.
Another object is to develop novel herbicides.
An additional object is to prepare herbicides having selective pre-emergent herbicidal activity.
A further object is to prepare herbicides having selective post-mergent herbicidal activity.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications Within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
It has now been found that these objects are obtained by preparing compounds having the formula:
and applying them as preand post-emergent herbicides.
In the formulae R is lower alkyl, eg of 1 to 8 carbon atoms, most preferably of 1 to 4 carbons, R and R are alkyl of 1 to 8 carbons, phenyl, lower alkyl phenyl or chlorophenyl, R and R can be the same or diiferent.
3,481,731 Patented Dec. 2, 1959 ice S,S-diethyl-2-methoxyvinylphosphonodithioate, S,S-diisipropyl-2-methoxyvinylphosphonodithioate, S,S-dimethyl-Z-ethoxyvinylphosphonodithioate, S,S-diethyl-2-ethoxyvinylphosphonodithioate, S,S-dipropyl-2-ethoxyvinylphosphonodithioate, S,S-diisopropyl-Z-ethoxyvinylphosphonodithioate, S,S-dibutyl-2-ethoxyvinylphosphonodithioate, S,S-diphenyl-2-ethoxyvinylphosphonodithioate, S,S-diethyl-2-isobutoxyvinylphosphonodithioate, S,S dibutyl-2-isobutoxyvinylphosphonodithioate, S,S-dimethyl-2-rnethoxyvinylphosphonodithioate, S,S-dimethyl-Z-propoxyvinylphosphonodithioate, S,S-dimethyl-Z-isopropoxyvinylphosphonodithioate, S,S-dimethyl-2-butoxyvinylphosphonodithioate, S,S-dimethyl-2-sec. butoxyvinylphosphonodithioate, S-methyl-S-propyl-2-isobutoxyvinylphosphonodithioates, S,S-diethyl-Z-isoamyloxyvinylphosphonodithioate, S,S-diethyl-Z-octoxyvinylphosphonodithioate, S,S-dipropyl-2-methoxyvinylphosphonodithioate, S,S-dibutyl-Z-methoxyvinylphosphonodithio-ate, S,S-di sec. butyl-2-methoxyvinylphosphonodithioate, S,S-diamyl-2-methoxyvinylphosphonodithioate, S,S-dioctyl-2-methoxyvinylphosphonodithioate, S,S-diphenyl-Z-methoxyvinylphosphonodithioate, S,S-di-p-totyl-2-methoxyvinylphosphonodithioate, S,S-di-o-tolyl-2-methoxyvinylphosphonodithioate, S,S-di-p-butylphenyl-2-methoxyvinylphosphonodithioate, S,S-di-p-chlorophenyl-2-methoxyvinylphosphonodithioate, S-ethyl-S-p-chlorophenyl-2-methoxyvinylphosphonodithioate, S-ethyl-S-propyl-2-ethoxyvinylphosphonodithioate, S-propyl-S-butyl-2-ethoxyvinylphosphonodithioate, S,S-diamyl-Z-ethoxyvinylphosphonodithioate, S,S-dihexyl-Z-ethoxyvinylphosphonodithioate, S,S-dicyclohexyl-2-ethoxyvinylphosphonodithioate, S,S-diheptyl-2-ethoxyvinylphosphonodithioate, S,S-diphenyl-2-ethoxyvinylphosphonodithioate, S,S-di-o-chlorophenyl-2-ethoxyvinylphosphonodithioate, S,S-diethyl-2-propoxyvinylphosphonodithioate, S,S-dipropyl-2-propoxyvinylphosphonodithioate, S,S-dibutyl-Z-propoxyviuylphosphonodithioate, S,S-dihexyl-2-propoxyvinylphosphonodithioate, S,S-diisooctyl-Z-propoxyvinylphosphonodithioate, S,S-dim-tolyl-2-propoxyvinylphosphonodithioate, S,S-dipropyl-2-isopropoxyvinylphosphonodithioate, S,S-disiopropyl-2-isopropoxyvinylphosphonodithioate, S,S-dibutyl-2-isopropoxyvinylphosphonodithioate, S,S-diethyl-2-butoxyvinylphosphonodithioate, S,S-dihexyl-Z-butoxyvinylphosphonodithioate, S,S-diamyl-2-isobutoxyvinylphosphonodithioate, S,S-di 2',4'-dichlor0phenyl) -2-isobutoxyvinylphosphonm dithioate.
The compounds of Formula I are readily prepared by reacting an alkyl vinyl ether with phosphorus pentachloride preferably dissolved in a solvent such as carbon tetrachloride to form the 2-alkoxy-2-chloroethylphosphonyldichloride. The complex is treated with two moles of sulfur dioxide. Dehydrohalogenation of the intermediate formed in this reaction occurs simultaneously or upon removal of the phosphorus oxychloridethionylchloride-solvent mixture to yield alkoxyinylphosphonyldichloride. The alkoxyvinylphosphonodithioates are formed by esterification of the alkoxyvinylphosphonyldichloride with a mercaptan in the presence of a tertiary amine, e.g. triethylamine, tripropylamine, N,N-
ll 4) 23/811 ZNEta ROCH=CHP ZEt NHC As alkyl vinyl ethers as starting materials there can be employed methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec. butyl vinyl ether, amyl vinyl ether, isoamyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, isooctyl vinyl ether.
As mercaptans there can be used methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, butyl mercaptan, isobutyl mercaptan, hexyl mercaptan, cyclohexyl mercaptan, amyl mercaptan, heptyl mercaptan, octyl mercaptan, isooctyl mercaptan, 2-ethylhexyl mercaptan, thiophenol, p-methylthiophenol, 2- chlorothiophenol, 2,4-dichlorothiophenol, 4-butylthiophen01.
Unless otherwise indicated all parts and percentages are by weight.
EXAMPLE 1 29 grams (0.5 mole) of methyl vinyl ether was added to a stirring suspension of 208 grams (1 mole) of phosphorus pe'ntachloride in 8-10 volumes of carbon tetrachloride. The reaction mixture was cooled to 10-20 C. throughout the addition. After the addition was completed, the reaction mixture was allowed to warm to room temperature (25 C.) and was then stirred for 12- 14 hours.
Gaseous sulfur dioxide was then bubbled into the stirring suspension at a rapid rate. Cooling was maintained at 10-20 C. throughout the addition. Completion of the reaction was evidenced by disappearance of the solid phase and the formation of a clear solution. The 2-methoxyvinyl phosphonyl dichloride was obtained by direct distillation of the reaction mixture, B.P. 85 C.; n 1.4997; yield 85%.
EXAMPLE 2 144 grams (2 moles) of ethyl vinyl ether was added dropwise to a stirring suspension of 833 grams (4 moles) of phosphorus pentachloride in 8-10 volumes of carbon tetrachloride. The reaction mixture was cooled to 10-20 C. throughout the addition. After the addition was completed, the reaction mixture was allowed to warm to room temperature and then stirred for 12-14 hours.
Gaseous sulfur dioxide was then bubbled into the stirring suspension at a rapid rate. Cooling was maintained at l0-20 C. throughout the addition. Completion of the reaction was evidenced by the disappearance of the solid phase and the formation of a clear solution. The 2-ethoxyvinylphosphonyldichloride was obtained by direct distillation of the reaction mixture, B.P.27 142 C.; n;, 1.4950; yield 75%.
EXAMPLE 3 100 grams (1 mole) of isobutyl vinyl ether was added dropwise to a stirring suspension of 417 grams (2 moles) of phosphorus pentachloride in 8-10 volumes of carbon tetrachloride. The reaction mixture was cooled to 10-20 4 C. throughout the addition. After the addition was completed, the reaction mixture was allowed to warm to room temperature (25 C.) and then stirred for 12-14 hours.
Gaseous sulfur dioxide was then bubbled into the stirring suspension at a rapid rate. Cooling was maintained at 10-20 C. throughout the addition. Completion of the reaction was evidenced by the disappearance of the solid phase and the formation of a clear solution.
The 2-isobutoxyvinylphosphonyldichloride was obtained by direct distillation of the reaction mixture, B.P. 92 C.; r15 1.48 68; yield 72%.
EXAMPLE 4 17.5 grams (0.1 mole) of 2-(methoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 12.5 grams (0.2 mole) of ethyl mercaptan was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. (If the water wash was acid, as occurred in some experiments, the benzene layer was extracted with 5% sodium bicarbonate solution. The benzene layer was then further washed until all washes were neutral.) The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S-diethyl-2- methoxyvinylphosphonodithioate (Compound 7374) as the product. B.P. C.; n 1.5529; yie1d=67%.
EXAMPLE 5 13.5 grames (0.08 mole) of 2-(methoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 12.5 grams (0.16 mole) of isopropyl mercaptan was then added. 15.2 grams (0.15 mole) of triethylamines was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30- 35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. (If the water wash was acid, as occurred in some experiments, the benzene layer was extracted with 5% sodium bicarbonate solution. The benezene layer was then further washed until all washes were neutral.) The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S-diisopropyl- 2-methoxyvinylphosphonodithioate (Compound 7375) as the product.
B.P. 117 C.; n;, 1.5340; yield=75% EXAMPLE 6 19 grams (0.1 mole) of 2-(ethoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 11.5 grams (0.24 mole) of methyl mercaptan was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S dimethyl 2 ethoxyvinylphosphonodithioate (Compound 7579) as the product.
B.P. C.; 11 1.5456; yield=94% EXAMPLE 7 19 grams (0.1 mole) of 2-(ethoxy) vinyl phosphonyl dichloride was diluted with volumes of dry benzene. 12.5 grams (0.2 mole) of ethyl mercaptan was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35" C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S diethyl 2 ethoxyvinylphosphonodithioate (Compound 7576) as the product.
B.P. 126 C.; n 1.5456; yield=94% EXAMPLE 8 19 grams (0.1 mole) of Z-(ethoxy) vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 16 grams (0.22 mole) of l-propanethiol was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S dipropyl 2 ethoxyvinylphosphonodithioate (Compound 7577) as the product.
19 grams (0.1 mole) of 2-(ethoxy)vii. phosphonyl dichloride was diluted with 10 volumes or dry benzene. 16.7 grams (0.22 mole) of 2-propanethiol was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S,-diisopropyl-Z-ethoxyvinylphosphonodithioate (Compound 7578) as the product.
B.P. 115 C.; 11 1.5269; yield=75% EXAMPLE 10 19 grams (0.1 mole) of 2-(ethoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 18.5 grams (0.2 mole) of l-butanethiol was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 3035 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S dibutyl 2 ethoxyvinyl phosphonodithioate (Compound 7580) as the product. B.P. 147 C.; n 1.5251; yield=92%.
EXAMPLE 11 19 grams (0.1 mole) of 2-(ethoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene.
24 grams (0.22 mole) of thiophenol was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 3035 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached 25 C.).
The reaction mixture was then Washed with cold water, The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S diphenyl 2 ethoxyvinylphosphonodithioate (Compound 7604) as the product. M.P. 82 C.; yield=98%.
EXAMPLE 12 21.7 grams (0.1 mole) of 2-(isobutoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 13.7 grams (0.22 mole) of ethyl mercaptan was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain- S,S-diethyl 2 isobutoxyvinylphosphonodithoate (Compound 7675) as the product. 11 1.5291; yield-=%.
EXAMPLE 13 21.7 grams (0.1 mole) of 2-(isobutoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 16 grams (0.22 mole) of 2-propanethiol was then added. 20.2 grams (0.2 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-25 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S diisopro-pyl 2 isobutoxyvinylphosphonodithioate (Compound 7676) as the product. B.P. 145 C.; 11 1.5226; yield=91%.
EXAMPLE 14 10.9 grams (0.05 mole) of 2-(isobutoxy)vinyl phosphonyl dichloride was diluted with 10 volumes of dry benzene. 10 grams (0.11 mole) of l-butanethiol was then added. 10.1 grams (0.1 mole) of triethylamine was added to this stirring solution at such a dropwise rate to keep the exothermic reaction temperature at 30-35 C. After the addition was completed, the reaction mixture was allowed to stir until room temperature was reached (25 C.).
The reaction mixture was then washed with cold water. The benzene layer was then dried over anhydrous sodium sulfate. The solvent was stripped in vacuo on a steam bath; and the resulting crude oil was distilled to obtain S,S-dibutyl 2 isobutoxyvinylphosphonodithioate (Com- 7677) as the product. 11 1.5142; yield=93%.
The herbicides of the present invention can be used alone or they can be applied together with inert solids to form dusts, or can be dispersed in a suitable liquid dilute, e.g. organic solvents or water.
There can also be added surface active agents or wetting agents and/or inert solids in the liquid formulations. In such case, the active ingredients can be from 0.01 to 95% by weight of the entire composition.
As organic solvents there can be employed hydrocarbons, e.g. benzene, toluene, xylene, kerosene, diesel fuel, fuel oil and petroleum naphtha, ketones such as acetone,
methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and perchloroethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, ethers, e.g. ethylene glycol monomethyl ether and diethylene glycol taurate. Turkey red oil, sodium dibutyl naphthalene sulfonate, sodium lignin sulfonate, polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether (Nonionic 218), long chain ethylene oxide-propylene oxide condensation products, e.g.
monomethyl ether, alcohols, e.g. methanol, ethanol, iso- Pluronic 61 (molecular weight 1000), polyethylene glycol propanol, amyl alcohol, ethylene glycol, propylene glycol, ester of tall oil acids, sodium octyl phenoxyethoxyethyl butyl carbitol acetate and glycerine. Mixtures of water sulfate, tris (polyoxyethylene) sorbitan monostearate and organic solvents, either as solutions or emulsions, can (Tween 60), and sodium dihexyl sulfosuccinate. b employed, The compounds of the present invention were tested as The novel herbicides can also be applied as aerosols. pre-emergent herbicides at the indicated dosages against e.g. by dispersing them in air by means of a compressed the indicated plants. In this test the surface of the soil gas such as dichlorodifluorornethane or trichlorofluoro- Was sprayed with an acetone solution of the test commethane and other Freons and Genetrons, for example. pound the same day as the seeds were planted. The flats The pesticides of the present invention can also be apwhich were planted were 14 inches long, 10 inches wide plied with adjuvants or carriers such as talc, pyrophyllite, n 3.5 inches deep. 3 grams of the test material was synthetic fine silica, attapulgus clay, kieselguhr, chalk, diluted to ml. with acetone. Each ml. of this solution diatomaceous earth, lime, calcium carbonate, bentonite, when applied to the flat was equivalent to 1 1b./ acre of Fullers earth, cottonseed hulls, wheat flour, soybean flour, test al (active ingredient)- Th6 requisite number pumice, tripoli, wood flour, walnut shell flour, redwood 20 of ml. of the acetone solution was diluted to ml. and flou and lignin, this diluted mixture was sprayed on the flats, e.g. for 15 As stated, it is frequently desirable to incorporate a lbs/acre 15 ml. of the original acetone solution was disurface active agent in the herbicidal compositions of the luted to 40 m With acetone d or 5 lbs./ acre 5 ml. of present invention. Such surface active or wetting agents the original acetone solution was diluted to 40 ml. with are advantageously employed in both the olid and liquid 25 acetone. In the pre-emergent herbicide test the results are compositions, The surface active agent can be anionic, expressed on a 0-10 scale With 0 indicating no effect and cationic or nonionic in character. 10 indicating complete inhibition of seeds to germinate Typical classes of surface active agents include alkyl and emerge The results ill thfi pfs-emel'gent herbicide sulfonate salts, alkylaryl sulfonate salts, alkylaryl polyare set forth in Table 1.
TABLE 1 Lbs. AI per Sugar Morning Wild Water Johnson acre Oats beets glory Radish Flax Millet Pigweed mustard grass grass Compound:
ether alcohols, fatty acid esters of polyhydric alcohols and the alkylene oxide addition products of such esters, and addition products of long chain mercaptans and alkylene oxides. Typical examples of such surface active agents include the sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, alkylphenol ethylene oxide condensation products, e.g. p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g. sodium stearate and potassium oleate, sodium salt of propyl-naphthalene sulfonic acid, di (Z-ethylhexyl) ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium decane sulfonate, sodium salt of the sulfonated monoglyceride of cocoanut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether, polyethylene glycol esters of fatty acids and rosin acids, e.g. Ethofat 7 and 13, sodium N-methyl-N-oleyl 9 were dissolved in acetone in the same manner as in the pre-emergent herbicide tests. The flats, however, were sprayed 10 to 14 days after planting and the herbicidal activity was observed one week after the application of 10 where R R and R are all alkyl groups of l to 4 carbon atoms.
4. A process according to claim 3 wherein the compound is applied to the soil prior to the emergence of the test compound. The results are set forth in Table 2. 5 the plant.
TABLE 2 per Wild Sugar Morning Water- Johnson Compound acre Pigweed mustard beets glory grass Millet grass 7675 s 10 10 10 9 s 2 4 3 7 e t 7677 s 10 1o 9 9 7 2 1o 9 s s. 7
All of the compounds tested showed high post-emergent 5. A process according to claim 4 wherein the cornherbicidal activity at the 8 lb./acre rate. S,S-diisopropylpound is selected from the group consisting of Z-methoxyvinylphosphonodithioate (Compound 7375 S S diiso propyl-2-methoxyv1nylphosphonodithioate, S,S dnsopropyl 2 1sobutoxyvmylphosphonodithloate SS diethy1 z ethoxyvinylphosphonodithioate; (compcfurfd 7676) and f P? S,S-di-n-propyl-2-ethoxyvinylphosphonodithioate; phonodithloate (Compound 7677) possessed hlgh activity S,s diisopropyl z ethoxyvinylphosphonodithioate; and even at the 2 Ill/acre level- S,S-diisopropyl-Z-isobutoxyvinylphosphonodithioate.
The most fi coinPound for overall preand Post- 6. A process according to claim 3 wherein the comemergeni herincldail acuvlty was Compound 7676' pound is applied to the plants after the emergence of What is claimed 1s: the plants A Proms? of klllmg l?lants compr ismg applying to 7. A process according to claim 6 wherein the comthe i zza g f tg 23213 13 efiectlve amount of a pound is selected from the group consisting of c u avm omp g e S,S-di1sopropyl-2-methoxyvinylphosphonodlthioate;
0 SR S,S-diisopropyl-2-isobutoxyvinylphosphonodithiote; and H i 40 S,S-dibutyl-Z-isobutoxyvinylphosphonodithioate. R 00H=0HP i 8. A process accordlng to claim 3 wherein the compound is S,S diisopropyl 2 isobutoxyvinylphosphonodithioate. where R 1s lower alkyl and R and R are selected References Cited from the group consisting of alkyl of 1 to 8 carbon UNITED STATES PATENTS atoms, phenyl, lower alkyl phenyl and chlorophenyl.
2. A process according to claim 1 wherein the com- Sggggg: pound is S,S diisopropyl 2 methoxyvinylphosphonodithioate. 3,294,876 12/1966 Regel 260-972 3. A process of killing plants comprising applying LEWIS GOTTS Prima EX to the plant habitat a herbicidally effective amount of ry animer a compound according to claim 1 having the formula CATHERINE MILLS Asslstant Exammer 0 SE, US. Cl. X.R. fll/ 260950, 956
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US3029270A (en) * | 1959-02-04 | 1962-04-10 | Bayer Ag | Phosphonic acid esters and process for their production |
US3047605A (en) * | 1957-06-05 | 1962-07-31 | Bayer Ag | Phosphonic acid esters and their production |
US3294876A (en) * | 1962-01-26 | 1966-12-27 | Chemagro Corp | Preparation of dithiophosphorus compounds |
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US3047605A (en) * | 1957-06-05 | 1962-07-31 | Bayer Ag | Phosphonic acid esters and their production |
US3029270A (en) * | 1959-02-04 | 1962-04-10 | Bayer Ag | Phosphonic acid esters and process for their production |
US3294876A (en) * | 1962-01-26 | 1966-12-27 | Chemagro Corp | Preparation of dithiophosphorus compounds |
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