IL35203A - O-methyl o-(2,2,2-trihaloethyl)o-(2',2'-dihalovinyl)-phosphates,their production and use as pesticides - Google Patents
O-methyl o-(2,2,2-trihaloethyl)o-(2',2'-dihalovinyl)-phosphates,their production and use as pesticidesInfo
- Publication number
- IL35203A IL35203A IL35203A IL3520370A IL35203A IL 35203 A IL35203 A IL 35203A IL 35203 A IL35203 A IL 35203A IL 3520370 A IL3520370 A IL 3520370A IL 35203 A IL35203 A IL 35203A
- Authority
- IL
- Israel
- Prior art keywords
- methyl
- phosphate
- formula
- trihaloethyl
- phosphite
- Prior art date
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000575 pesticide Substances 0.000 title 1
- 235000021317 phosphate Nutrition 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 38
- 239000010452 phosphate Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 16
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 claims description 15
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 13
- YTGSYRVSBPFKMQ-UHFFFAOYSA-N 2,2,2-tribromoacetaldehyde Chemical compound BrC(Br)(Br)C=O YTGSYRVSBPFKMQ-UHFFFAOYSA-N 0.000 claims description 11
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 241000607479 Yersinia pestis Species 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 230000000361 pesticidal effect Effects 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000013543 active substance Substances 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- -1 trialkylamin.es Chemical class 0.000 description 15
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 241001465754 Metazoa Species 0.000 description 13
- 150000003014 phosphoric acid esters Chemical class 0.000 description 12
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 230000000749 insecticidal effect Effects 0.000 description 9
- 241000257226 Muscidae Species 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 241000255925 Diptera Species 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 241000254179 Sitophilus granarius Species 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 241000691880 Planococcus citri Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 241000256118 Aedes aegypti Species 0.000 description 3
- 241001674044 Blattodea Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241001425390 Aphis fabae Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 241001232715 Granaria Species 0.000 description 2
- 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 2
- 241000254022 Locusta migratoria Species 0.000 description 2
- 241000238675 Periplaneta americana Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 241000254181 Sitophilus 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000001418 larval effect Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 125000006000 trichloroethyl group Chemical group 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 241000239223 Arachnida Species 0.000 description 1
- 241000238888 Argasidae Species 0.000 description 1
- 241000238662 Blatta orientalis Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- 241000238660 Blattidae Species 0.000 description 1
- 241001388466 Bruchus rufimanus Species 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001124134 Chrysomelidae Species 0.000 description 1
- 241000256057 Culex quinquefasciatus Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 241001641896 Dermestes lardarius Species 0.000 description 1
- 241000131287 Dermestidae Species 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- 241000630736 Ephestia Species 0.000 description 1
- 241000122098 Ephestia kuehniella Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 241000238889 Ixodidae Species 0.000 description 1
- 241000258915 Leptinotarsa Species 0.000 description 1
- 241000258916 Leptinotarsa decemlineata Species 0.000 description 1
- 241000254023 Locusta Species 0.000 description 1
- 241000257229 Musca <genus> Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 241001415279 Pseudococcidae Species 0.000 description 1
- 244000046095 Psophocarpus tetragonolobus Species 0.000 description 1
- 241000255893 Pyralidae Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241001494139 Stomoxys Species 0.000 description 1
- 241001494115 Stomoxys calcitrans Species 0.000 description 1
- 241000254107 Tenebrionidae Species 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 229940087675 benzilic acid Drugs 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019993 champagne Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004491 dispersible concentrate Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 210000002683 foot Anatomy 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical group 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940059835 pyrethrines Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 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
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 210000003371 toe Anatomy 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
AGRIPAT. S.A.
The present invention concerns new O-methyl 0-(2,2,2,-trihaloethyl) -(2' ,2' -dihalovinyl) phosphoric acid esters, process for the production thereof as well as pesticidal compositions containing these phosphoric acid esters as active ingredients and method for the con rol of pests using the new active substances or compositions containing them.
The new O-methyl 0- (2 , 2 , 2- rihaloethyl) 0- (2 ', 2 ' -dihalovinyl) phosphoric acid esters correspond to the Formula I: 11 OCH^ .
CX.QUO — P ^1) . ^ 0CH= CY2 In this formula: X represents, fluorine or chlorine ,. and Y represents chlorine or bromine.
The new phosphoric acid esters of Formula I are produced according to the invention by converting trimethyl phosphite or 0 ,0-dimethyl phosphorous acid chloride in the presence of a base with a trihaloethano'l of the Formula II CX3CH2OH (II) into an 0 , 0-dimethyl 0- ( 2 , 2 , 2- trihaloethyl) phosphite and reacting this with chloral or bromal.
According to a modification of the process according to the invention, the phosphoric acid esters of Formula I are produced by reacting rime hy1 phosphite and phosphorus trichloride in the presence of an acid-binding agent with a trihaloethanol of the Formula II and chloral or bromal.
For the process according to the ivrvention, the following bases, for example, can be employed: tertiary amines such as trialkylamin.es, pyridine and pyridine bases, inorganic bases such as hydroxides, carbonates and cyanides of alkali metals. Moreover, alkali metal alkanolates can also be employed; such an alkanolate is also formed during the reaction after the addition of metallic alkali metal to the reaction mixture. Tertiary amines, in particular, as well as the inorganic bases listed may be employed to take up the hydrogen halide formed during the reaction of trimethyl phosphite and phosphorus trichloride with trihaloethanol.
The reactions according to the invention' may be performed in the presence or absence of a solvent or diluent. It is advisable to perform the reaction of trimethyl phosphite and phosphorus trichloride with trihaloethanol in the presence of a solvent which is inert towards the reaction componei^ts ; for this purpose aromatic hydrocarbons such as benzene, toluene, xylenes, and halogenated hydrocarbons such as chloroform, carbontetrachloride and" chlorobenzene have proved suitable. For the process according to the invention, it has been found expedient to employ the trimethyl phosphite in excess, the other reaction components, however, in molar equivalents. If 0,0-dimethyl phosphorous acid chloride is used in place of trimethyl phosphite, the reaction components are employed in equimolar amounts. Whereas by the interchange of ester radicals-- rimethyl; phosphite/ trihaloethanol-- the base can be employed in catalytic amounts; when the chloride is employed, equimolar amounts of the base are necessary. The reaction temperatures for interchange of ester radicals are in the range of 60-150°C, for the reaction of acid chloride/ trihaloethanol in the range of 0 - 50°, preferably 0 - 30°C. The methaitol which forms in the reaction is continuously removed by distillation from the reaction mixture, the hydrochloride base is removed by filtration. The intermediate product, 0,0- dimethyl 0- (2 , 2 , 2- trihaloethy1) phosphite, is then separated by distillation and purified. The reaction of this phosphite with chloral or bromal is performed at temperatures between 20 and 100°C, preferably at 50 to 80°C.
Depending on the reactivity of the individual reaction components, heating or cooling of the reaction mixture is required.
The modification of the process according to the invention is a "one-container" process. The 0,0-dimethyl 0- (trihaloethy1) phosphite resulting as intermediate can be reacted directly without further purification with chloral or bromal. The phosphoric acid esters of Formula I are then separated from the reaction mixture by distillation; they are obtained in high purity and very good yields. Trimethyl phosphite and phosphorus trichloride are employed in the reaction in a ratio of chloride to phosphite of 1:2 to 1:3, preferably 1:2; trihaloethanol, chloral or bromal and acid-binding agent (base) are employed in equimolar amounts relative to the phosphorus compounds; this corresponds to 3 - 4 mol of the individual reactants , preferably 3 mol. The reaction temperatures for. the reaction of phosphite and trihaloethanol are in the range of 0-50°, preferably 0-30°C; for the reaction of the inter- mediate with chloral or bromal they are from 20-100°, preferably 50-80°C.
From the literature a number of asymmetric 0,0-dialkyl 0- (2 , 2-dichlorovin.yl) phosphoric acid esters are known (cf. for example U . S . patents N os . 2,956,073 and 3,116,201; German patent No. 1,251,745). In general, they are produced by reaction of asymmetric trialkyl phosphorous acid esters (trialkyl phosphites) with chloral according to W. Perkow [cf. Naturwissenschaften 3.9, 353 ff (1952)]. 0-Alkyl 0- (2-chloroethyl) 0- (21 , 2 ' -dichlorovinyl) phosphoric acid esters are obtained according to British patent No. 806,638 from cyclic phosphorous acid esters with chloral. In German patent No. 1,178,420, the production of 0- (2 , 2-dichlorovinyl) phosphoric acid esters with one or two identical or differing halogenated tertiary alkyl radicals from corresponding 0- ( ter -haloalkyl) 0-alkyl phosphorous acid esters and chloral is described. The phosphorous acid esters are obtained in turn from PCl^ a d appropriate alcohols. Since on the one hand the chlorine atoms of the PCl^ cannot be exchanged in exact steps, and on the other hand a separation and isolation of asymmetric ti-ialkyl phosphites having lower alkyl radicals is very difficult, this method of producing the 0,0-di— methyl 0- ( 2 , 2 , 2- trihaloethy1) phosphite could not be used.
The replacement of a trichloroethyI group by the dichlorovinyl radical in tris- (2 , 2-dichloroethyl) phosphorous acid ester v/ith chloral led to 0 ,0-bis- (2 , 2 , 2- trichloroethyl)-l-hydroxy-2,2,2 trichloroethyl phosphonic acid [cf. B.A.Arbuzov, Dokl.Akad.
Nauk USSR 160, 99 ff (1965)].
. By the. process according to the invention, the not-previously-described 0,0-dimethyl 0- (2 , 2 , 2- trihaloethyj.) phosphorous acid esters necessary for the production of the new phosphoric acid ester of Formula I are obtained without difficulty. . They are isolated by distillation from the reaction mixture. In the modification of the process according to the invention, isolation is not necessary; chloral or bro al can be added directly to the reaction mixture after the separation of the precipitated salt.
The new 0-methyl 0- (2 , 2 , 2- trihaloethy1) 0- ( 2 2 ' -dichlorovinyl) phosphoric acid esters of Formula I have excellent insecticidal and acaricidal properties. Compared with known 0-alkyl 0- (21 , 2 ' -dichlorovinyl) phosphoric acid esters, for example the widely used 0 ,0-dimethyl-0-(2 ' ^'-dichlorovinyl pho phate (DDVP) , 0-methyl 0- ( 1-methyl- 1~ trichloro-methyl- ethyl) 0- (2 ', 2 ' -dichlorovinyl) phosphate and 0-methyl 0-(2-chloroethyl) 0- (2 2 ' -dichlorovinyl) phosphate (loc. cit) , the new active substances have a substantially more favorable toxicity for warm-blooded animals and a long-lasting insecticidal effect. They are thus suited, in particular for the protection of stored goods and for the control of insects in buildings, stables, etc.
In the following comparison table the toxicity for warmblooded animals is given.
Active substance: rat UL^Q PER OS O-methyl 0- (2 , 2 , 2- trichloroethyl) 0- (2 ', 2 * -di-bromovinyl) phosphate 1100-1700 mg/kg 0-methyl 0- ( 2 , 2 , 2- trifluoroethyl) 0- (2 ',2' -di-bromovinyl) phosphate 1400 mg/kg tri 0-methyl 0- ( 2 , 2 , 2-, :hloroethyl) 0-(2\2'--di-chlorovinyl) phosphate '' ~ 1000 mg/kg 0-methyl 0- (2 , 2 , 2-trifluoroethyl) 0-(2',2 dichlorovinyl) phosphate . 1100 mg/kg 0,0-dimethyl 0- (2 ' -21 -dichlorovinyl) phosphate (DDVP) , known insecticide - 80 mg/kg (see G. Schrader, "Die Entwicklung neuer , insektizider Phosphorsaureester , page 40-50, Tests with compounds of the Formula I on insects and arachnids showed that these active substances are good to very good stomach and coiitact poisons and also have a systemic insecticidal dffect..
It has thus been found that the active substances of the Formula I have, in. particular , an excellent, long-lasting effect against insects of the families Muscidae, Stomoxidae and Culicidae, e.g. against the polyvalent-resistant and normally sensitive house lies ( usca domestica) , stable flies (Stomoxys calcitrans) and mosquitoes (e.g. Aedes Aegypti, Culex fatigans , Anophenles Stephens!); against insects of the families Curculinidae , Bruchididae, Dermes- tidae, Tenebrionidae and Chrysomelidae , e.-g. granary weevil's' (Sitophilus granarius) , bean beetles (Bruchidus obtectus) , ' larder beetles (Der estes vulpinus) , mealworms (Teiebrio olitor) , Colorado potato beetles (Leptinotarsa . decemlineata) and their larval stages; against insects of the family Pyralididae, e.g. Mediterranean flour moths (Ephestia klihniella) ; of the family Blattidae, e.g. cock-roaches (Phyllodromia germanica , . Periplaneta americana, Blatta orientalis) ; of the family Aphididae, e.g. bean aphicls (Aphis fabae) ; of the family Pseudococcidae , e.g. citrus mealybugs (Planococcus citri) and of the family Locustidae, e.g. migratory locusts (Locusta inigratoria).
Tests on the said bean aphids and migratory locusts showed an excellent systemic effect.
In addition, the active substances of the Formula I according to the invention have a good action on the larval Ixodidae, Arachnidae and Argasidae. Ψ . In admixture with synergists and auxiliaries having a similar action such as dibutyl succinate, piperonyl butoxide, olive oil, and peanut oil, etc., the range of action of the said active substances can be broadened and in particular the insecticidal -and acaricidal action can be improved.
Likewise, the insecticidal action can be substantially broadened and adjusted to the prevailing conditions by the addition of other insecticides such as, for example, phosphoric, phosphonic , thio- and dithiophosphoric acid esters and amides , halogeiiated hydrocarbons and analogs of DDT-active substance as well as pyrethrines and synergists thereof, acaricidally active substances such as halogeno-benzilic acid. esters such as 4 ' , 41 -dichlorobenzilic acid esters and 41 ,41 -dibromobenzilic acid esters ,, insecticidal and acaricidal carbamates, for example oxime carbamates, aryl carbamates and carbamates of heterocyclic compounds which are enolizable.
Comparison Tests: The insecticidal activity of the new asymmetric phosphoric esters is illustrated by the following tests, using as comparison compound the 0 -methyl 0-- [ 1' , 1' -dimethyl-2 ' , 2 ' , 2 ' trichloroethyl] .-0-[2 , 2 -dichlorovinyl ] phosphate, disclosed in the German patent specification No. 1 178 420. 1. Effect _as .insecticidal. contact, p_ois_oji_ Petri dishes are coated with acetone solutions of the active substances so that they are covered with 0.15 g of active substance per square meter. After one hour the following test animals are placed in the dishes: 1) polyvalent-resistant house flies (Musca. domestica), 2) mosquitoes (Aedes aegypti) 3) granary weevils (Sitophilus granaria) 4) stable flies (Stomoxys calcitzrans).
The time is determined after which all (100%) of the animals are in dorsal position (see Table 1) : Table 1 Active Substance 1007o of the animals in dorsal po 1 mosqui- grana house flies • toes weevi O-me hyl 0- (2 , 2 , 2-trichloroethyl) · 0-(2' , 2 ' -dibromovinyl) phosphate 66 10 78 O-methyl 0- (2 , 2 , 2-trichloroethyl) 0-(2' , 2 ' -dichlorovinyl) phosphate 55 1 . 28 O-methyl 0- (2 , 2 , 2-trifluoroethyl) 0- (2 2 ' -dibromovinyl) phosphate 10 10 60 O-methyl 0- ( 2 , 2 , 2-trifluoroethyl) 0- (2 ' , 2 ' -dichlorovinyl) phosphate 20 23 30 O-methyl 0- [ 1* , 1' -dimethyl-2 ! ,2 \ 2 * -trichloroethyl] 0-[ 2, 2 -dichlorovinyl] phosphate (comparison) no activity 120 no act Longr lasting insecticidal effect Petri dishes which have been coated with 1.5 mg and 0.15 mg of active substance per square meter · . ■ -are allowed to stand for 6 days at 24° C. · .- _ ■ Then polyvalent-resistant house flies (Musca domestica) and mosquitoes (Aedes aegypti) are placed on the coatings. The time is determined after which all (1007o) of the animals are in dorsal position.
Table 2 Active Substance 100% of the animals in dor X minutes house flies 1.5 mg/m^ 0 of active substance o 0-methyl 0- (2 , 2 , 2-trichloroethyl) 0- (2 ' , 2 ' -dibromovinyl) phosphate 32 0-methyl 0- (2 , 2 , 2-trichloroethyl) 0-(2' , 2 ' -dichlorovinyi) phosphate 26 0-methyl 0- (2 , 2 , 2-trifluoroethyl) 0-(2' , 2 ' -dibromovinyl) phosphate 26 0-methyl 0- (2 , 2 , 2-trifluoroethyl) 0-(2' , 2 ' -dichlorovinyi) phosphate 0-methyl 0-[l' ,1' -dimethyl-2' ,2' ,2' -trichloroethyl ] 0-[ 2 , 2-dichlorovin i] phosphate (comparison) 300 Effect as insectic_id JL^_sj^ma_ch_-poison^ Filter paper is soaked with 207> honey-water and an acetone solution of 20 rag of active substance. After hours the moist filter paper, freed of acetone, is placed in with hungry polyvalent-resistant house flies for two hours. . After this the animals are fed water and sugar and kept at 22°C. In the following table the time is given in minutes after which all (1007.) of the animals are in dorsal position (see table 3) Table 3 Active Substance 1007, of the animals in dorsal position after X minutes 0-methyl 0- (2 , 2 , 2- trichloroethyl) 0-(2' , 2 ' -drbromovinyl) phosphate 5 0-m thyl 0- ( 2 , 2 , 2- trifuloroethy1) 0-(2' , 2.' -dibromovinyl) phosphate 15 0-methyl 0- ( 2 , 2 , 2- trifluoroethyl) 0-(2' , 2 ' -dichlorovinyl) phosphate 0-methyl 0-[l" ,1' -dimethyl-2' ,2' ,2* -trichloroethyl ] 0-[ 2, 2 -dichlorovinyl] phosphate (comparison) no activity 4 . Effect as insecticidal_contact_2oisgn_ a) 50 g of wheat are mixed' ith 100 nig of a 1% dust; granary weevils (Sitophilus granaria) are then added. The animals are then kept at 2 2 - 24 ° C under normal conditions. The test was evaluated after 1 , 2 and 5 days. b) 2 0 g of a 1% dust are evenly distributed in Petri, dishes. Cockroaches (Phyllodromia germanica and Periplaneta americana) are then placed in the dishes and kept under normal conditions at 2 2 - 24°C. ■c) Tomato plants infested with citrus mealybugs (Planococcus citri) are sprayed with a O . 0 257o emulsion (produced from a 10% emulsifiable concentrate) and kept in a greenhouse at 24°C and 7 07o relative humidity.
In the following table the time is given after which the animals of the tests (a) , (b) , and (c) were in dorsal position, (see table 4) Table 4 Active Substance 1007c of the animals in dorsal pos a) granary weevils b) cockroaches after days after minute : O-methyl 0- ( 2 , 2 , 2- richloroethyl) 0-(2' , 2 ' -dibromovinyl) phosphate 1 85 : 0-methyl 0- ( 2 , 2 , 2-trifluoroethyl) 0- (2 2 ' -dibromovinyl) phosphate 1 . 0-methyl 0- (2 ; 2 , 2-trichloroethyl) 0-(2' .2 ' -dichlorovinyl) phosphate 1 30 0-methyl 0- (2 , 2 , 2-trifluoroethyl) 0-(2! , 2 ' -dichlorovinyl ) phosphate 1 25 0-methyl 0-[l' ,1' -dimethyl-2' ,2' ,2 t _ . trichloroethyl] 0-[2 ,2-dichlorovinyl] phosphate (comparison) no activity no activity The following examples illustrate the production" of the active substances according to the invention. The temperatures are given in degrees centigrade. The table which follows contains other examples of 0-(2,2,2-trihalo) 0-(2' , 2 * -dihalo-vinyl) phosphates which have been produced by the methods described. ample 1 . 129 g of trimethyl phosphite, 155 g of 2 , 2 , 2- trichloroethanol and 0.5 g of sodium are heated together to 110°. The methanol which forms is continuously distilled off. During a period of 3 hours the inner temperature is raised from 98° to 150°. After this the reaction mixture is distilled at 12 Torr. 130.6 g of 0,0-dimethyl 0-(2,2,2- trichloroethyl) phosphite having a boiling point of 40-47° at 0.1 to 0.2 Torr, are obtained.
Analysis : calculated: C 19.90% H 3.34% Cl 44.04% P 12.85% found: 20.6 % 3.6 % 43.7 % . 12,8 % 38.8 g (24.5 ml) of phosphorus trichloride are added dropwise with cooling at 0° to 5° to 70 g of trimethyl phosphite. The mixture is' first stirred at 0° to 5° and then at room temperature for 16 hours. The reaction mixture is diluted with 800 ml of benzene and then added dropwise at 20° to 25°, to a solution of 126 g of 2 , 2 , 2- trichloroethanol and 85.4 g of triethyl- arnine in 200 ml of benzene, whereby a white precipitate of triethylamine hydrochloride separates. After completion of the addition, the mixture is stirred for another hour at room temperature. The precipitated salt is removed by filtration and the filtrate is concentrated in vacuum. By distilling the residue, 47.5 g of 0,0-dimethyl 0- (2 , 2 , 2- trichloroethyl) phosphite, b.p. 43-45° at 0.25 Torr, are. obtained.
Analysis : calculated: C 19..90% H .3.43% CI 44.04% found: 20.2 % 3.4 44 ,,3 % . 50 g of 0 ,0- dimethyl 0- (2 , 2 , 2- richloroethyl) phosphite are added dropwise at 25° to 58.2 g (21.8 ml) of technical bromal. The exothermic reaction is kept at 50° with a cooling bath. The mixture is then heated to 80° for 15 minutes and subsequently distilled in high vacuum. The 0-methyl 0- (2 , 2 , 2- trichloroeth l) 0- (21 , 2 ' -dibromovinyl) phosphate has a boiling point of 125-129°/ 0.01 Torr (yield: 32.4 g) .
Analysis : calculated: C 14.05% H 1.42%. CI 24.907.. P found: 14.4.% 1.5 % 25.5 % Example 2 97 g of phosphorus trichloride are added dropwise at 0° during 2 hours to 175 g of trimethyl phosphite. The solution is diluted with 2 liters of benzene and during 2 hours a solution of 315 g of 2 , 2 , 2- t ichloroethanol and 213 g of triethylamine in 500 ml of benzene are added dropwise at 15-20°. The triethylamine hydrochloride which precipitates is separated and the filtrate is slowly added dropwise at reftiix .temperature to a solution of 565 g of bromal in 200 ml of benzene. The methyl bromide which' forms during this reaction is continuously removed by distillation.., the completion of the distillation also being the completion of the reaction. Then the reaction mixture is washed with 10% aqueous sodium carbonate solution and concentrated sodium chloride solution (brine) , and dried; the benzene is removed by distillation in vacuum. The residue is distilled in vacuum. 535 g (89% of theory) of 0-methyl 0- (2 , 2 , 2- trichloroethyl) 0- (21 , 21 -dibromovinyl) phosphate (see Example lc) are obtained .
Analysis : calculated: c 19.90% 11 3.34%.. CI 44.04% P 12.85% found: 20.6 % 3.6 % 43.7 12.8% Exam le 3 a) 38.8 g (24.5 ml) of phosphorus trichloride are added dropwise while cooling with an icebath to 0° to 5°, to 70 g (66.3 ml) of trimethyl phosphite. The mixture is first stirred at 0° to 5° and then at room temperature for 16 hours. Then a solution of 84.5 g (60.7 ml) of 2,2 ,2-trifluoroethanol and 85.4 g (116 ml) of triethyl- amine in 200 ml of ether is added dropwise while cooling at 15° to 20°. After completion of the addition, stirring is continued at room temperature for another hour. The salt which precipitates is removed by filtration and the filtrate is concentrated in vacuum. By distilling the residue, 100 g of 0,0-dimethyl 0- (2 , 2 , 2- trifluoroethyl) phosphite having a boiling point of 39-45° at 40 to 50 Torr, are obtained. b) 19.2 g of 0,0-dimethyl 0- (2 , 2 , 2- trifluoroethyl) phosphite are added dropwise at 50° to 14.8 g of technical chloral. After completion of the addition, the mixture is stirred for 3 hours at 50° and for 30 minutes at 70°. The reaction mixture is distilled directly in high vacuum.
After a preliminary run of 5.7 g having a boiling point of 54-55° at 0.003 Torr, consisting of about 907. of the desired product; 13.5 g of 0-methyl 0- (2 , 2 , 2- rifluoroethyl) 0- (21 , 21 -dichloroviny1) phosphate, b.p. 55° at 0.003 Torr, distill over.
Analysis calculat 20.78%: .H .2.08% .CI 24.54% F 19.72%. found : 20.9 % 2.1 % 24.4 % 19.9 % calculat 10.74% found : 10.8..% The following phosphoric acid esters of the Formula were likewise produced according to the previous example Compound physical data 0-methyl 0- (2 , 2 , 2- trifluoroethyl) 0-(2' , 2 ' -dibromovinyl) phosphate b.p. 83°/0.002 Torr 0-methyl 0- ( 2 , 2 , 2- trichloroethyl) 0-(2' , 2 ' -dichlorovinyl) phosphate b.p. 98-100°/ 0.001 Torr The production of pes icidal compositions according to the invention is performed in known manner by intimately mixing and grinding the active substances of the Formula I with suitable carriers, optionally with the' addition of dispersing agents or solvents, which are inert towards the active substances. The novel active substances can be prepared in the following forms: solid preparations: dusts, scattering agents, granulates, (coated granulates, impregnated granulates and homogeneous granulates); water-dispersible concentrates of the active substance: wettable powders, pastes, emulsions; liquid preparations: solutions, aerosols.
The concentration of active substance in these preparations is from 0.01 to 807o. Other biocidally active substances or agents can be admixed with the compositions of the invention. Thus, in addition to the said active substances of the Formula I and salts thereof, the new compositions may contain, for example, other insecticides, fungicides, bactericides, fungistatic and bacteriostatic substances or other nematocides in order to broaden the range of action.
The- compositions according to the invention may also contain plant fertilizers, trace elements, etc. pesticidal compositions according to the invention are presented to illustrate the invention; where not expres stated otherwise, "parts" mean parts by weight.
Dust The following ingredients are used to produce a) a 5% and b) a 2% dust: a) . 5 parts of O-methyl 0- (2 , 2 , 2- trichloroethyl) 0- (21 , 21 -dichlorovinyl) phosphate, 95 parts of talcum; b) 2 parts of 0-methyl 0- (2 , 2 , 2- trichloroethyl) 0-(2' , 21 -dibromovinyl) phosphate, 1 part of highly dispersed silicic acid, 97 . parts of talcum.
The active substances are mixed and ground with the carriers. The dusts obtained are used, for example, for the coiitrol of cockroaches and ants, etc. in buildings, but also in the protection of plants.
Granulate The following ingredients are used to produce a 5% granulate: parts of O-methyl 0- (2 , 2 , 2-trichloroethyl) 0- (21 , 2 ■ -dichlorovinyl) phosphate, 0.25 part of epichlorohydri , 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol ("Carbowax") , 91 parts of kaolin (granular size 0.3 - 0.8 mm).
The active ingredient is mixed with epichlorohydrin and dissolved with 6 parts of acetone; then the polyethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed onto kaolin and then the acetone is evaporated in vacuum. The granulate obtained is suitable for the protection of plants and stored goods.
Wettable powder To produce a a) 40%, b) 50%, c) 25%, and d) 10% wettable powder, the following components are used: a) -40 parts of.O-methyl 0- (2 , 2 , 2- trichloroethyl) 0- (2 ' , 2 ' -dichlorovinyl) phosphate, parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate 54 parts of silicic acid; b) 50 parts of 0-methyl 0- (2 , 2 , 2- trichloroethyl) 0-(2' ,2' -dichlorovinyl) phosphate, parts of alkyl aryl sulphonate ("Tinovetine B") , parts of calcium lignin sulphonate, 1 part of Champagne chalk/hydroxyethyl cellulose · mixture (1:1), parts of silicic acid, 14 parts of kaolin; c) 25 parts of 0-methyl 0- (2 , 2 , 2- trifluoroethyl) 0- (2 ' , 2 ' -dibromovinyl) phosphate, parts of the sodium salt of bleylmethyl tauride, 2.5 parts of naphthalene sulphonic acid/ formaldehyde condensation product, 0.5 part of carboxymethyl cellulose, parts of neutral potassium aluminum silicate, 62 parts of kaolin; d) parts of O-methyl 0- (2 , 2 , 2~ trifluoroethyl) -dichlorovinyl) phosphate, 3 parts of mixture of sodium salts of saturated fatty alcohol sulphates, parts of naphthalene sulphonic acid/ formaldehyde condensation product, 82 parts of kaolin.
The active substances are intimately mixed in suitabl mixers with the additives and ground on appropriate mills and rollers. Wettable powders are obtained which may be diluted with water to suspensions of any desired concentration. Such suspensions are chiefly used in plant protection for the'control of biting and sucking insects.
Spray .
To produce a) a 5% and b) a 2% spray, the following components are used: a) 5 . parts of O-methyl 0- (2 , 2 , 2- trichloroethyl) 0- (21 , 21 -dibromovinyl) phosphate are treated with 1 part of epichlorohydrin and then dissolved in 94 parts of benzine (boiling range 160-190°); b) 2 parts of 0-methyl 0- (2 , 2 , 2-dichloroethyl) 0- (21 , 2 ' -dichlorovinyl) phosphate and 3 parts of 4,4,-dichlorodiphenyl-trichloroethane- active substance . are dissolved in 95 parts of kerosene.
These solutions are sprayed with pressure sprayers. The solution (a) is advantageously used for the control of aphids on fruit trees and other plants. The solution (b) is used in particular for the control of flies and mosquitoes in living quarters, warehouses and slaughterhouses.
Claims (7)
1. New 0-methyl 0- (2 , 2 ,2- trihaloethyl) 0-(2\2'- dihalovinyl) phosphates of the Formula I wherein represents fluorine or chlorine, and Y represents chlorine or bromine,
2. 0-methyl 0-(2 ,2 , 2 -trichloroethyl) 0-(2' ,2' .dibromo- vinyl) phosphate.
3. Process for the production of 0-methyl 0- (2,2,2- trihaloethyl) 0- (2 ' , 2 ' -dihalovinyl) phosphates of the Formula I defined in Claim 1, which comprises converting trimethyl phosphite or 0,0-dimethyl phosphorous acid chloride in the presence of a base with a trihaloethanol of the Formula II CX3CH2OH (II) wherein X represents fluorine or chlorine, into an 0,0-dimethyl 0- (2 , 2 , 2- trihaloethyl) phosphite and reacting this with chloral or bromal. .4, Process according to Claim 3, which comprises ■ reacting trimethyl phosphite and phosphorus trichloride in the presence of an acid-binding agent with one equivalent of 2 , 2 , 2- trihaloethanol of Formula II and then with chloral or bromal.
4
5. Process according to Claim -5-, which comprises reacting trimethyl phosphite and phosphorous trichloride with 2,2,2- \t trihaloethanol and chloral or bromal without isolating the intermediate product 0,0-dimethyl 0-(2 , 2 , 2 -trihaloethyl) phosphite.
6. Pesticidal composition, which comprises as active ingredient at least one 0 -methyl 0- (2, 2 ,2-trihaloethyl) 0 - (2 ', 21 -dihalovinyl) phosphate of the Formula I defined in Claim 1 together with carriers and/or dispersing agents suitable for the protection of plants and optionally with other herbicid-ally and biocidally active ingredients.
7. Method for the control of pests, which comprises applying to said pests a pesticidally effective amount of an 0 -methyl" 0-(2,2,2-trihaloethyl) 0- (2 2 '-dihalovinyl) phosphate of the Formula I as defined in Claim 1 or of compositions containing such phosphates as active ingredients.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1330969A CH520473A (en) | 1969-09-02 | 1969-09-02 | O-methyl-O- (trihaloethyl) -O- (dihalovinyl) -phosphoric acid ester as an active component in a pest control agent and the use of this agent for controlling pests |
Publications (2)
Publication Number | Publication Date |
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IL35203A0 IL35203A0 (en) | 1970-11-30 |
IL35203A true IL35203A (en) | 1973-02-28 |
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Application Number | Title | Priority Date | Filing Date |
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IL35203A IL35203A (en) | 1969-09-02 | 1970-09-01 | O-methyl o-(2,2,2-trihaloethyl)o-(2',2'-dihalovinyl)-phosphates,their production and use as pesticides |
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JP (1) | JPS4832659B1 (en) |
AU (1) | AU1940170A (en) |
BE (1) | BE755577A (en) |
BG (1) | BG17934A3 (en) |
CH (1) | CH520473A (en) |
DE (1) | DE2043382C3 (en) |
ES (2) | ES383290A1 (en) |
FR (1) | FR2060763A5 (en) |
GB (1) | GB1322555A (en) |
IL (1) | IL35203A (en) |
NL (1) | NL7012937A (en) |
SU (1) | SU363234A3 (en) |
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JPS5948571U (en) * | 1982-09-21 | 1984-03-31 | 落合 敬一 | pricing label |
CN117465088B (en) * | 2023-12-27 | 2024-02-23 | 四川海纳尔服饰有限公司 | Fireproof flame-retardant multilayer composite fabric for fire-fighting clothing and preparation method thereof |
-
0
- BE BE755577D patent/BE755577A/en unknown
-
1969
- 1969-09-02 CH CH1330969A patent/CH520473A/en not_active IP Right Cessation
-
1970
- 1970-09-01 BG BG015578A patent/BG17934A3/en unknown
- 1970-09-01 SU SU1478601A patent/SU363234A3/ru active
- 1970-09-01 NL NL7012937A patent/NL7012937A/xx unknown
- 1970-09-01 DE DE2043382A patent/DE2043382C3/en not_active Expired
- 1970-09-01 GB GB4175670A patent/GB1322555A/en not_active Expired
- 1970-09-01 FR FR7031782A patent/FR2060763A5/fr not_active Expired
- 1970-09-01 ES ES383290A patent/ES383290A1/en not_active Expired
- 1970-09-01 JP JP45076609A patent/JPS4832659B1/ja active Pending
- 1970-09-01 ES ES383289A patent/ES383289A1/en not_active Expired
- 1970-09-01 IL IL35203A patent/IL35203A/en unknown
- 1970-09-01 AU AU19401/70A patent/AU1940170A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
AU1940170A (en) | 1972-03-09 |
SU363234A3 (en) | 1972-12-30 |
DE2043382C3 (en) | 1973-11-08 |
NL7012937A (en) | 1971-03-04 |
ES383290A1 (en) | 1973-02-16 |
FR2060763A5 (en) | 1971-06-18 |
ES383289A1 (en) | 1973-01-01 |
BG17934A3 (en) | 1974-03-05 |
CH520473A (en) | 1972-03-31 |
DE2043382B2 (en) | 1973-04-05 |
IL35203A0 (en) | 1970-11-30 |
GB1322555A (en) | 1973-07-04 |
DE2043382A1 (en) | 1971-08-05 |
JPS4832659B1 (en) | 1973-10-08 |
BE755577A (en) | 1971-03-01 |
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