US3671547A - Dialkyl dihydrothienyl phosphates - Google Patents
Dialkyl dihydrothienyl phosphates Download PDFInfo
- Publication number
- US3671547A US3671547A US885291A US3671547DA US3671547A US 3671547 A US3671547 A US 3671547A US 885291 A US885291 A US 885291A US 3671547D A US3671547D A US 3671547DA US 3671547 A US3671547 A US 3671547A
- Authority
- US
- United States
- Prior art keywords
- phosphate
- reaction
- phosphates
- hydrogen
- tetrahydrothiophen
- 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
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- 229910019142 PO4 Inorganic materials 0.000 title abstract description 44
- 235000021317 phosphate Nutrition 0.000 title abstract description 43
- -1 dihydrothienyl phosphates Chemical class 0.000 title description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical group 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 17
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 12
- 230000000749 insecticidal effect Effects 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- 239000010452 phosphate Substances 0.000 description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000007363 ring formation reaction Methods 0.000 description 9
- DSXFPRKPFJRPIB-UHFFFAOYSA-N thiolan-3-one Chemical compound O=C1CCSC1 DSXFPRKPFJRPIB-UHFFFAOYSA-N 0.000 description 9
- 241000238876 Acari Species 0.000 description 8
- 241001124076 Aphididae Species 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 230000009885 systemic effect Effects 0.000 description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- 240000008067 Cucumis sativus Species 0.000 description 2
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 241000257226 Muscidae Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical class O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 230000000699 topical effect Effects 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000045232 Canavalia ensiformis Species 0.000 description 1
- 241000258920 Chilopoda Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 101100286286 Dictyostelium discoideum ipi gene Proteins 0.000 description 1
- 238000006228 Dieckmann condensation reaction Methods 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000258913 Oncopeltus fasciatus Species 0.000 description 1
- 235000010617 Phaseolus lunatus Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- 241000255993 Trichoplusia ni Species 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005057 dihydrothienyl group Chemical group S1C(CC=C1)* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 1
- TUSSXVYKOOVOID-UHFFFAOYSA-N methyl 3-oxothiolane-2-carboxylate Chemical compound COC(=O)C1SCCC1=O TUSSXVYKOOVOID-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AJAZMOFONMJGNP-WMZOPIPTSA-N n-[(2s)-4-methyl-1-oxo-1-[[(2s)-3-oxo-4-(pyridin-2-ylsulfonylamino)butan-2-yl]amino]pentan-2-yl]-1-benzofuran-2-carboxamide Chemical class O=C([C@H](C)NC(=O)[C@@H](NC(=O)C=1OC2=CC=CC=C2C=1)CC(C)C)CNS(=O)(=O)C1=CC=CC=N1 AJAZMOFONMJGNP-WMZOPIPTSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 1
- 229940046307 sodium thioglycolate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
-
- 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
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
Definitions
- R and R and alkyl of 1 to 4 carbon atoms wherein R and R and alkyl of 1 to 4 carbon atoms, R-' is hydrogen, halogen of atomic number 17 to 35 or alkyl of one to three carbon atoms and R, R and R are hydrogen or alkyl or one to three carbon atoms and n is 0, l or 2.
- These phosphates are insecticidal.
- This invention is directed to novel dihydrothienyl phosphates and their use as pesticides. More specifically, it concerns 2,3-dihydrothien-4-yl phosphates and their use as insecticides.
- the compounds of this invention are dialkyl 2,3- dihydrothien-4-yl phosphates in which the alkyls are individually of one to four carbon atoms and the dihydrothienyl group is optionally substituted in positions 2 and 3 by alkyl of one to three carbon atoms and in position 5 by alkyl of one to three carbon atoms or halogen of atomic number 17 to 35, i.e., chlorine or bromine.
- phosphates may be represented by the formula wherein R and R are alkyl of one to four carbon atoms each, R is hydrogen, alkyl of one to three carbon atoms or halogen of atomic number 17 to 35, R, R and R are hydrogen or alkyl of one to three carbon atoms and n is O, 1 or 2.
- the alkyl groups represented by R, R, R R, R and R which contain more than two carbon atoms may be straight chained or branched.
- Preferred compounds are those wherein n is 0, R R, R" and R are hydrogen and R and R are the same and are methyl or ethyl.
- the dihydrothienyl phosphates of formula (1) above may be prepared by reacting a 2-halo-tetrahydrothiophen-3-one with a trialkyl phosphite.
- the l-oxo and 1,1-dioxo compounds (where n represents 1 or 2) may be prepared by oxidizing the product of the tetrahydrothiophen-3-one/phosphite reaction.
- the phosphite/tetrahydrothiophen-3-one reaction may be represented by the following equation:
- X is halogen of atomic number 17 to 35
- R is alkyl of l to 4 carbon atoms
- R, R, R, R and R are as defined previously.
- This reaction is preferably carried out in an organic liquid diluent which does not react with the starting materials under the reaction conditions.
- Preferred among such diluents are aromatic hydrocarbons such as benzene, toluene and xylene.
- the reaction temperature will normally be in the range of about l0 to +130 C. For convenience reflux temperature may be used.
- the reaction pressure is not critical and subor superatmospheric pressures may be used if desired. Atmospheric or autogenous pressure will usually be employed.
- the 2-halo-tetrahydrothiophen-3-one reactant may be prepared by halogenating the corresponding tetrahydrothiophen-Ii-one with a mild halogenating agent such as sulfuryl chloride in the presence of a substantially non-polar organic solvent.
- a mild halogenating agent such as sulfuryl chloride
- the chlorination may also be effected with molecular chlorine.
- I-Ialogenation temperatures will usually be in the range of 40 to +20 C.
- either one or two halogens will be added to the 2-position. The extent of halogenation is determined by the relative concentration of the two reactants as well as the time and temperature of reaction.
- Tetrahydrothiophen-3-one and the alkyl substituted tetrahydrothiophen-Zi-ones required in the above described halogenation reaction may be prepared by the well known Dieckmann condensation of an a, fi-dicarbalkoxydialkyl sulfide, Organic Reactions, Vol. XV, Ed. by R. Adams et al., published by J. Wiley and Sons, Inc., New York, 1967, pages 14, 17-18, 123-129, and Journal of the American Chemical Society, Vol. 68, pages 2,229-2,235 (1946).
- a suitably substituted 0:, B'-diester dialkyl sulfide is cyclized to form a 2- and/or 4-carbalkoxy tetrahydrothiophen-3-one which is converted to the corresponding tetrahydrothiophen- 3-one by hydrolysis and decarboxylation.
- Cyclization of the a, B'-dicarbalkoxydialkyl sulfides is accomplished by heating the diester under anhydrous conditions in the presence of a base catalyst.
- Satisfactory catalysts for this reaction include the alkali metal alkoxides, hydridcs, and amides.
- the preferred catalyst is sodium alkoxide in which the alkoxide corresponds to the alcohol portions of the diester.
- the cyclization of a, [3'-carbomethoxydialkyl sulfide in the presence of sodium methoxide is especially preferred.
- This cyclization reaction may be carried out in the absence of any solvent or preferably in an inert aprotic solvent such as toluene, benzene, xylene, tetrahydrofuran, diethyl ether and dimethyl sulfoxide.
- the temperature of the reaction is frequently at the boiling point of the solvent; and may be within the range of 15 to 150 C. Pressure is not critical, but the reaction is commonly run under atmospheric pressure at the reflux temperature of the solvent with constant removal of the by-product alcohol formed during reaction, thereby increasing the yield of cyclic ketone.
- the cyclization reaction should be carried out in an inert, dry atmosphere. Dry, oxygen-free nitrogen is preferred. All traces of moisture and air should be removed from the reaction vessels before addition of the catalyst.
- the hydrolysis and decarboxylation of the carbalkoxy group of a 2- and/or 4-carbalkoxy tetrahydrothiophen-B-one may be accomplished by heating this compound with water or aqueous alcohol and an acid at temperatures in the range of 65 to 150 C.
- Inorganic acids such as sulfuric, phosphoric or hydrochloric acid will normally be employed. Reaction times for hydrolysis and decarboxylation will usually be within the range of 2 to 20 hours.
- the a, B-dicarbalkoxydialkyl sulfide used in the cyclization reaction may be obtained by the addition of an ester of thioglycolic or substituted thioglycolic acid to an ester of a, B- unsaturated acid such as acrylic acid, methacrylic acid or crotonic acid.
- This addition reaction is also base catalyzed.
- Satisfactory catalysts include the organic amines such as piperidine, morpholine, etc., as well as the stronger alkali metal catalysts listed above for the cyclization reaction.
- the reaction may be carried out with or without a solvent.
- the organic bases are preferred in a solvent free process. Typical solvents for this reaction include those previously listed for the cyclization reaction.
- the addition reaction takes place at temperatures in the range of 0 to 50 C., and reaction times are generally in the range of 10 to minutes.
- the unsaturated ester is preferably added to the thioglycolate-catalyst mixture.
- One convenient and preferred method of carrying out the preparation of the cyclic ester intermediates of this invention involves a sodium thioglycolate catalyzed addition of a thioglycolate to a linear, unsaturated ester in a solvent such as dimethylsulfoxide followed by cyclization without separation and purification of the a, B'-dicarbalkoxydialkyl sulfide.
- the temperature is maintained on the low side, i.e., about 0 to 10 C. during sulfide preparation, and is then raised to higher temperatures to cause cyclization.
- Oxidation of the heterocyclic sulfur atom in the tetrahydrothiophen-3-one ring to form the l-oxo (sulfoxide) and the 1,1-dioxo (sulfone) derivatives may be accomplished by reacting the phosphate product of the above formula (1) 65.4 g. of tetrahydrothiophen-3-one was collected at 6365 C. This material appeared as a water-white liquid.
- tetrahydrothiophen-3-one prepared above, 20.4 g. was mixed with 100 cc. of toluene in a vessel. To this was with suitable oxidizing agents such as hydrogen peroxide or added dropwise 27.0 g. of sulfuryl chloride over a period of 20 organic peracids such as perbenzoic, perphthalic, mminutes at 20 to 30 C. with dry nitrogen being introduced chloroperbenzoic and peracetic. The amount of oxidizing vigorously into the mixture.
- suitable oxidizing agents such as hydrogen peroxide or added dropwise 27.0 g. of sulfuryl chloride over a period of 20 organic peracids such as perbenzoic, perphthalic, mminutes at 20 to 30 C.
- Suitable solvents include the chlorinated raphy to detennine the progress of the reaction. After the hydrocarbons such as dichloromethane, chlorobenzene, and above-mentioned 1 hour period the mixture was stripped the like. under vacuum at 80 C. In this way, 47.6 g. of diethyl-2,3-
- Triethyl phosphitc Dretliyl 2,3-d1methyl-2et11yl2,3-d1hydrotlnen-l-yl phosphate. 2-t-111om- -propyltvti-ul1ydrothiomien-3on0 Trinwtliyl phosphitv 1methy15-propyld.3-dihydrotluen-i-yl phosphate. .Z-brmno-B-mvthyI-LS-diethyltetrahydrothiophon one 'Iriethyl phosplnte...
- Example 1 Preparation of diethyl 2,3-dihydrothien-4-yl phosphate Sodium. 46.0 g. was dissolved in 800 cc. of methanol in a vessel. 212.2 g. of methyl a-mercaptoacetate were added to that solution. The combined mixture was stirred at 50 C. for minutes. The reaction mixture was then stripped under vacuum leaving a yellow solid which was dissolved in 1 liter of dimethyl sulfoxide. This sulfoxide solution was cooled to 10 C. and 198.0 g. of methyl acrylate were added dropwise to it at 10 to 12 C. over a 30 minute period. After this addition, the mixture was stirred at 12 to 20 C. for l hour.
- the crude 2-carbomethoxy tetrahydrothiophen-Ii-one prepared above,160 g. was mixed with 500 g. of a 10 percent aqueous solution of H 50, in a vessel. This mixture was heated to reflux for 5 hours, followed by cooling to 10 C. The reaction mixture was extracted twice with 500 cc. portions of ether. The combined ether extracts were dried over MgSO and then filtered. The ether was stripped at 30 C. under vacuum. The crude reaction mixture was then distilled and Analysis of this crude product was as follows: Calculated for C H OPS: P, 12.98; S, 13.48;Found: P, 13.38; S, 13.87.
- Example 2 Preparation of dimethyl 5'chloro-2,3- dihydrothien-4-yl phosphate
- a reaction vessel was charged with 50 ml. of sulfuryl chloride which was cooled to 0 C. Then while vigorously passing nitrogen through the sulfuryl chloride, 10.2 g. of tetrahydrothiophen-B-one was added dropwise over a period of about 10 minutes. The reaction mixture was stirred for 5 more minutes and then ml. of toluene was added. Stirring was continued for 1 hour during which time the temperature rose to 23 C. At the end of this time the excess sulfuryl chloride was removed by evaporation at 30 C. under a vacuum to give a red toluene solution of 2,2- diehlorotetrahydrothiophen-3-one.
- Example 3 Preparation of dimethyl dihydrothien-4-yl phosphate 3-methyl tetrahydrothiophen-4-one was prepared from methyl thioglycolate and methyl methacrylate by essentially the same process as described in Example 1. This ketone, 1 1.6 g. was dissolved in 100 m1. of toluene and cooled to 20 C.
- Example 4 Preparation of dimethyl l,l-dioxo--chloro-2,3- dihydrothien-4-yl phosphate
- the product of Example 2 8.1 g., was dissolved in 150 ml. of dichloromethane. Then 14.5 g. of 85 percent m-chloroperbenzoic acid was added in small increments over a period of 1 hour. When addition was complete, the reaction mixture was stirred for 16 hours at 23 C. At the end of this time, the mixture was filtered, washed with aqueous sodium bicarbonate (20 g. in 400 ml. water), and with water. It was then dried over anhydrous magnesium sulfate.
- Example 5 Preparation of diethyl l-oxo-5-chloro-2,3- dihydrothien-4-yl phosphate Diethyl 5-chloro-2,3-dihydrothien-4-yl phosphate was prepared by essentially the same process as in Example 2 using triethyl phosphite in place of trimethyl phosphite. A flask was charged with 22.0 g. of diethyl 5-chloro-2,3dihydrothien-4-yl phosphate and 150 ml. of dichloromethane. To this solution there was added 16.2 g. of 85 percent m-chloroperbenzoic acid in increments over a period of minutes.
- German Cockroach (Blaltella germanica L): A 100 ppm. acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the above described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
- Houseflies (Musca domestica): A 250 ppm. acetone solution of the candidate toxicant was placed in a syringe. A random mixture of anesthetized male and female DDT-resistant houseflies was placed on cardboard squares. A 0.5 microgram dose of the acetone solution was applied directly to each fly. The flies were then placed in a recovery cage. Mortality readings were taken after 24 hours.
- Aphids (Aphids gossypii Glover): An acetone solution of the test compound was prepared and diluted with water containing a small amount of nonionic surfactant to 30 ppm. 3 replicate cucumber leaf sections each infested with at least 20 aphids were dipped into this acetone-water solution. Excess solution was drained from the section and they were held under controlled conditions for 24 hours. Mortality readings were then made on 20 randomly selected aphids per replicate and the percent mortality based on the average of these readings was calculated.
- Mites (Telranychus telarius L): An acetone solution of the test compound was prepared and diluted with water containing a small amount of nonionic surfactant to 100 ppm. 3 replicate lima bean leaf sections each infested with at least 20 mites were dipped into this acetone-water solution. Excess solution was drained from the section and they were held under controlled conditions for 24 hours. Mortality readings were then made on 20 randomly selected mites per replicate and the percent mortality based on the average of these readings was calculated.
- SYSTEMIC TESTS Aphids (Aphids gossypii Glover) and Mites (Tetranychus telarium L): An acetone solution of the test compound (with a small amount of nonionic surfactant added) was prepared and diluted with water to 500 ppm. 40 ml. of this solution was applied to the soil in a 4 inch pot containing two plants (pinto bean for mites; cucumber for aphids). Forty-eight hours after this application these plants were infested with the test insects. Mortality readings were taken 48 hours after infestation and a percent mortality was calculated from these readings.
- Phosphates of this invention also have exhibited excellent Percent Element analyses Compound Dimathyl .2,3-dihydrothian-4-yl phosphate Diethyl 5-ch101'0-2,3-dihydrothien4-yl phosphate Diethyl 2-n1ethy1-2,3-dihyd1'0thien-4-yl phosphate Dimethyl 2-1nethy1-2,3-dihydrothienA-yl phosphatev Dimethyl 2-111ethyl-5-chl0ro-2,3-dihydrothien-4-yl phosphate Diethyl 1,l-dioito-ZB-dihhydrothielH-yl phosphate Dlethyl 1,l-dloxo-fi-chlol'o-12,3-di-hydrothien4-yl phosphate UTILITY
- the dihydrothienyl phosphates of this invention exhibit a wide spectrum of insecticid
- Mites Aphids Mites this invention may be applied in other liquid or solid formulations to the pests described above, their environment or hosts susceptible to attack from such pests. For example, when applied as insecticides they may be sprayed or otherwise applied directly to plants or soil so as to eflect control of insects coming into contact therewith. When used as nematocides, they will normally be applied directly to nematode-infested soil at dosage levels between 3 and 40 pounds per acre. (Solid formulations may be plowed into the soil; liquid formulations ma be sgrayed or ingected.)
- t e compounds of tlus invention will comprise a toxic amount of one or more phosphates and a biologically inert carrier. Usually they will also contain a wetting agent to facilitate their penetration and dispersion into the soil and/or hosts to which they are applied. Solid carriers such as clay, talc, sawdust and the like may be used insuch formulations. Liquid diluents which may be used with these compounds include xylene, toluene, acetone and benzene.
- insecticide and insect refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects.
- insect is used not only to include small invertebrate animals belonging to the class Inseam but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.
- R and R are alkyl of one to four carbon atoms
- R is hydrogen, alkyl of one to three carbon atoms or halogen of atomic number 17 to 35
- R, R and R are hydrogen or alkyl of one to three carbon atoms and n is 0, l or 2.
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Abstract
WHEREIN R and R1 and alkyl of 1 to 4 carbon atoms, R2 is hydrogen, halogen of atomic number 17 to 35 or alkyl of one to three carbon atoms and R3, R4 and R5 are hydrogen or alkyl or one to three carbon atoms and n is 0, 1 or 2. These phosphates are insecticidal.
Compound of the formula:
Compound of the formula:
Description
United States Patent 1 June 20, 1972 Stevick [54] DIALKYL DIHYDROTHIENYL PHOSPHATES [72] Inventor: Lawrence E. Stevick, San Francisco, Calif.
[73] Assignee: Chevron Research Company, San Francisco, Calif.
[22] Filed: Dec. 15, 1969 [21] Appl. No.: 885,291
[52] US. Cl. ..260/329 P, 260/3321, 260/3322 C, 260/3323 R, 260/332.5, 424/275 [51] lnt.Cl. ..C07d 63/08 [58] Field ofSearch ..260/329 P, 332.1, 332.5
[56] References Cited UNITED STATES PATENTS 3,106,565 10/1963 Newallis ..260/332.1 3,475,452 10/1969 3,205,238 9/l965 3,341,553 9/1967 3,234,238 2/1966 Weil et a1 ..260/329 2/1966 Greenbaum ..260/329 3,228,965 1/1966 Greenbaum et al. ..260/332.l
Primary Examiner-Henry R. Jiles Assistant Examiner-Cecilia M. Shurko Attorney-J. A. Buchanan, J r., G. F. Magdeburger, .lohn Stoner, J r., and Raymond Awyang [57] ABSTRACT Compound of the formula:
wherein R and R and alkyl of 1 to 4 carbon atoms, R-' is hydrogen, halogen of atomic number 17 to 35 or alkyl of one to three carbon atoms and R, R and R are hydrogen or alkyl or one to three carbon atoms and n is 0, l or 2. These phosphates are insecticidal.
7 Claims, No Drawings DIALKYL DIHYDROTI'IIENYL Pl-IOSPI-IATES FIELD OF INVENTION This invention is directed to novel dihydrothienyl phosphates and their use as pesticides. More specifically, it concerns 2,3-dihydrothien-4-yl phosphates and their use as insecticides.
DESCRIPTION OF INVENTION The compounds of this invention are dialkyl 2,3- dihydrothien-4-yl phosphates in which the alkyls are individually of one to four carbon atoms and the dihydrothienyl group is optionally substituted in positions 2 and 3 by alkyl of one to three carbon atoms and in position 5 by alkyl of one to three carbon atoms or halogen of atomic number 17 to 35, i.e., chlorine or bromine. These phosphates may be represented by the formula wherein R and R are alkyl of one to four carbon atoms each, R is hydrogen, alkyl of one to three carbon atoms or halogen of atomic number 17 to 35, R, R and R are hydrogen or alkyl of one to three carbon atoms and n is O, 1 or 2. The alkyl groups represented by R, R, R R, R and R which contain more than two carbon atoms may be straight chained or branched. Preferred compounds are those wherein n is 0, R R, R" and R are hydrogen and R and R are the same and are methyl or ethyl.
The dihydrothienyl phosphates of formula (1) above may be prepared by reacting a 2-halo-tetrahydrothiophen-3-one with a trialkyl phosphite. The l-oxo and 1,1-dioxo compounds (where n represents 1 or 2) may be prepared by oxidizing the product of the tetrahydrothiophen-3-one/phosphite reaction. The phosphite/tetrahydrothiophen-3-one reaction may be represented by the following equation:
wherein X is halogen of atomic number 17 to 35, R is alkyl of l to 4 carbon atoms and R, R, R, R, R and R are as defined previously. This reaction is preferably carried out in an organic liquid diluent which does not react with the starting materials under the reaction conditions. Preferred among such diluents are aromatic hydrocarbons such as benzene, toluene and xylene.
The reaction temperature will normally be in the range of about l0 to +130 C. For convenience reflux temperature may be used. The reaction pressure is not critical and subor superatmospheric pressures may be used if desired. Atmospheric or autogenous pressure will usually be employed.
The 2-halo-tetrahydrothiophen-3-one reactant may be prepared by halogenating the corresponding tetrahydrothiophen-Ii-one with a mild halogenating agent such as sulfuryl chloride in the presence of a substantially non-polar organic solvent. The chlorination may also be effected with molecular chlorine. I-Ialogenation temperatures will usually be in the range of 40 to +20 C. Depending on the extent of halogenation, either one or two halogens will be added to the 2-position. The extent of halogenation is determined by the relative concentration of the two reactants as well as the time and temperature of reaction.
Tetrahydrothiophen-3-one and the alkyl substituted tetrahydrothiophen-Zi-ones required in the above described halogenation reaction may be prepared by the well known Dieckmann condensation of an a, fi-dicarbalkoxydialkyl sulfide, Organic Reactions, Vol. XV, Ed. by R. Adams et al., published by J. Wiley and Sons, Inc., New York, 1967, pages 14, 17-18, 123-129, and Journal of the American Chemical Society, Vol. 68, pages 2,229-2,235 (1946). In this reaction, a suitably substituted 0:, B'-diester dialkyl sulfide is cyclized to form a 2- and/or 4-carbalkoxy tetrahydrothiophen-3-one which is converted to the corresponding tetrahydrothiophen- 3-one by hydrolysis and decarboxylation.
Cyclization of the a, B'-dicarbalkoxydialkyl sulfides is accomplished by heating the diester under anhydrous conditions in the presence of a base catalyst. Satisfactory catalysts for this reaction include the alkali metal alkoxides, hydridcs, and amides. The preferred catalyst is sodium alkoxide in which the alkoxide corresponds to the alcohol portions of the diester. In particular the cyclization of a, [3'-carbomethoxydialkyl sulfide in the presence of sodium methoxide is especially preferred.
This cyclization reaction may be carried out in the absence of any solvent or preferably in an inert aprotic solvent such as toluene, benzene, xylene, tetrahydrofuran, diethyl ether and dimethyl sulfoxide. The temperature of the reaction is frequently at the boiling point of the solvent; and may be within the range of 15 to 150 C. Pressure is not critical, but the reaction is commonly run under atmospheric pressure at the reflux temperature of the solvent with constant removal of the by-product alcohol formed during reaction, thereby increasing the yield of cyclic ketone.
The cyclization reaction should be carried out in an inert, dry atmosphere. Dry, oxygen-free nitrogen is preferred. All traces of moisture and air should be removed from the reaction vessels before addition of the catalyst.
The hydrolysis and decarboxylation of the carbalkoxy group of a 2- and/or 4-carbalkoxy tetrahydrothiophen-B-one may be accomplished by heating this compound with water or aqueous alcohol and an acid at temperatures in the range of 65 to 150 C. Inorganic acids such as sulfuric, phosphoric or hydrochloric acid will normally be employed. Reaction times for hydrolysis and decarboxylation will usually be within the range of 2 to 20 hours.
The a, B-dicarbalkoxydialkyl sulfide used in the cyclization reaction may be obtained by the addition of an ester of thioglycolic or substituted thioglycolic acid to an ester of a, B- unsaturated acid such as acrylic acid, methacrylic acid or crotonic acid. This addition reaction is also base catalyzed. Satisfactory catalysts include the organic amines such as piperidine, morpholine, etc., as well as the stronger alkali metal catalysts listed above for the cyclization reaction. The reaction may be carried out with or without a solvent. The organic bases are preferred in a solvent free process. Typical solvents for this reaction include those previously listed for the cyclization reaction. The addition reaction takes place at temperatures in the range of 0 to 50 C., and reaction times are generally in the range of 10 to minutes. In order to minimize competing side reactions the unsaturated ester is preferably added to the thioglycolate-catalyst mixture. One convenient and preferred method of carrying out the preparation of the cyclic ester intermediates of this invention involves a sodium thioglycolate catalyzed addition of a thioglycolate to a linear, unsaturated ester in a solvent such as dimethylsulfoxide followed by cyclization without separation and purification of the a, B'-dicarbalkoxydialkyl sulfide. In this in situ method of cyclic ester preparation, the temperature is maintained on the low side, i.e., about 0 to 10 C. during sulfide preparation, and is then raised to higher temperatures to cause cyclization.
Oxidation of the heterocyclic sulfur atom in the tetrahydrothiophen-3-one ring to form the l-oxo (sulfoxide) and the 1,1-dioxo (sulfone) derivatives may be accomplished by reacting the phosphate product of the above formula (1) 65.4 g. of tetrahydrothiophen-3-one was collected at 6365 C. This material appeared as a water-white liquid.
Of the tetrahydrothiophen-3-one prepared above, 20.4 g. was mixed with 100 cc. of toluene in a vessel. To this was with suitable oxidizing agents such as hydrogen peroxide or added dropwise 27.0 g. of sulfuryl chloride over a period of 20 organic peracids such as perbenzoic, perphthalic, mminutes at 20 to 30 C. with dry nitrogen being introduced chloroperbenzoic and peracetic. The amount of oxidizing vigorously into the mixture. When addition was comple agent employed is generally in the range of 90 to l percent nitrogen flow was continued for 45 minutes as the temperaof theoretical, i.e., for each mole of sulfide, from 0.9 to 1.1 ture was allowed to rise to 10 C. A vacuum was drawn on moles of oxidizing agent is used for conversion to the sulfoxide the mixture for 10 minutes at approximately .5 C. (The color derivative and more than 1.8 moles, preferably over 2.0 moles of the mixture turned very pale clear blue at this higher temof oxidizing agent, is used for conversion to the sulfone derivaperature.) This cool mixture was added rapidly to 49.8 g. of tive. This reaction is exothermic and the oxidizing agent is 'triethylphosphite in 150 cc. of benzene at reflux temperature. preferably added slowly or in small increments while main- The color of the combined mixture immediately became pale taining the temperature in the range of 0 to 50 C., preferably yellow. It was stirred for 1 hour at reflux temperature (approx- 15 to C. Oxidatively stable solvents may be employed in imately 90 C.) with repeated checks by gas liquid chromatogthis reaction.v Suitable solvents include the chlorinated raphy to detennine the progress of the reaction. After the hydrocarbons such as dichloromethane, chlorobenzene, and above-mentioned 1 hour period the mixture was stripped the like. under vacuum at 80 C. In this way, 47.6 g. of diethyl-2,3-
The following table lists representative phosphates of for- 20 dihydrothien-4-yl phosphate was thus recovered as a clear mula (l) and the reactants which may be used to prepare bright red oil. The infrared spectrum and gas liquid chromatothese phosphates. graphic analyses of this product indicated that the phosphate TABLE I I V r Reactants Tetrahydrothiophehone Phosphite Dihydrothicnyl phosphate product 2- 11 r -tetrah drothio hen-3one 'li'ibutyl phosphite Dibutyl 2.3 dihydrothien-4-y1 phosphate. 221i]grg4j-dici hyltetnfiiydrothiophen-Elone Trimethylph0sphit0. Dimethyl2,3-d1ethyl-2,3-d1hydroth1cn-4-yl phosphate. lie]1loro-l-pmpyltctl'uhyd1'othi0phtu3-0l10 'Iripropylpl10spl1it0. D propyl 3-D1'0pyl-5-chlor0-2,3{l1l1ydr0th1en-4-yl phosphate.
libromotutmhydrothiophei1-3one 'lrietllyl phosplnte iethyl 5-b101no-2 3-dihydrotluen-4-yl phosphate. g-broi1io-5-vtliyltvtmllydrothiophvn-Zi-ox1e 'lrimtthyl pliosphitt n. Duuethyl Q-ethyl:2,3-d1hydrothlenA-yl phosphate. 2-vhloro-l,fi-dimuthyltutmliydrotlnophvn-Ii-ouv 'lriisopropyl phosplutcn l) us0p 0Dy 2,3-dnnethy1-2,3-d111ydroth1en-4-yl phosphate. LZ-diuhlom-l-xnothyl-5-ctliyltvtmhydrothiophcu-3-ou0. Trimethyl phosplute. bulnetthyl2-ethy1-3-1net11y1-5-chloi'o-2,3-dihydrotluen-i-ylphos p 10. G. l,B-dichloro-l-vl.hyl-fi-isopi'opytotmhydrothiophcn-B-ouc Triethyl phosphito DieIthLyI 2-isopropy1-3-ethy1-5-c11101'0-2,3-di11yd1'ot11ieiH-y1 phosl.) 13. 0. t 2,2- 1 --l.5- 1i nttli 'ltct.ruhydroiliio 110118-0111 Tripropyl pl1osphitc. Dipi'opyl 2,3-dimetliyl-5-b1o1no-2 B-dihydrothieuA-yl phosphate. w 1SL382 fi-triiniwhylivtmliydi'othioplibn-lroiu Trimcthyl phosphitenu Dimethyl 2,2 ,3-t111118t11371-2341111ll'0tlllQl1:1-yl phosphate. 24mm, 0 intothvl-5-vthyltotrnhydrothioplwn-is-onu. Triethyl phosphitc Dretliyl 2,3-d1methyl-2et11yl2,3-d1hydrotlnen-l-yl phosphate. 2-t-111om- -propyltvti-ul1ydrothiomien-3on0 Trinwtliyl phosphitv 1methy15-propyld.3-dihydrotluen-i-yl phosphate. .Z-brmno-B-mvthyI-LS-diethyltetrahydrothiophon one 'Iriethyl phosplnte... D ethyl 2, 3-diethyl-5-metl1yl-2,3- 11hydrotl11en4-y1 phosphate. .Z-ch1oro-2-ct11yl-i-isopropyltctrahydrothiophmr-S-one Tributyl phosphite Diethyl 21sopropy1-5-ethyl-LZ,3-dihydrothien-1-yl phosphate.
EXAMPLES was contaminated with minor amounts of starting materials.
The following examples illustrate the methods which may be used to prepare the tetrahydrothiophen-3-one, the halotetrahydrothiophen-B-one reactants described above and the phosphates of this invention. These examples are intended as illustrativeonly and are not meant to limit the invention described herein in any manner. Unless otherwise indicated, percentages are by weight.
Example 1 Preparation of diethyl 2,3-dihydrothien-4-yl phosphate Sodium. 46.0 g. was dissolved in 800 cc. of methanol in a vessel. 212.2 g. of methyl a-mercaptoacetate were added to that solution. The combined mixture was stirred at 50 C. for minutes. The reaction mixture was then stripped under vacuum leaving a yellow solid which was dissolved in 1 liter of dimethyl sulfoxide. This sulfoxide solution was cooled to 10 C. and 198.0 g. of methyl acrylate were added dropwise to it at 10 to 12 C. over a 30 minute period. After this addition, the mixture was stirred at 12 to 20 C. for l hour. The mixture was'then poured into 1,500 cc. of ice water and 200 cc. concentrated HCl. It was extracted twice with 1 liter portions of ether. The combined ether extracts were washed with 600 cc. of ice water and dried overnight with MgSO The combined extracts were filtered and the ether was stripped off under vacuum leaving 307 g. of crude 2-carbomethoxy tetrahydrothiophen-3-one as a clear yellow oil.
The crude 2-carbomethoxy tetrahydrothiophen-Ii-one prepared above,160 g.,was mixed with 500 g. of a 10 percent aqueous solution of H 50, in a vessel. This mixture was heated to reflux for 5 hours, followed by cooling to 10 C. The reaction mixture was extracted twice with 500 cc. portions of ether. The combined ether extracts were dried over MgSO and then filtered. The ether was stripped at 30 C. under vacuum. The crude reaction mixture was then distilled and Analysis of this crude product was as follows: Calculated for C H OPS: P, 12.98; S, 13.48;Found: P, 13.38; S, 13.87. Example 2 Preparation of dimethyl 5'chloro-2,3- dihydrothien-4-yl phosphate A reaction vessel was charged with 50 ml. of sulfuryl chloride which was cooled to 0 C. Then while vigorously passing nitrogen through the sulfuryl chloride, 10.2 g. of tetrahydrothiophen-B-one was added dropwise over a period of about 10 minutes. The reaction mixture was stirred for 5 more minutes and then ml. of toluene was added. Stirring was continued for 1 hour during which time the temperature rose to 23 C. At the end of this time the excess sulfuryl chloride was removed by evaporation at 30 C. under a vacuum to give a red toluene solution of 2,2- diehlorotetrahydrothiophen-3-one.
The above described toluene solution was added rapidly to a refluxing solution of 18.6 g. of trimethyl phosphite in 50 ml. of toluene. Afier addition was complete the reaction mixture was stirred for 1% hours at the reflux temperature,. cooled somewhat and treated with charcoal. After filtration, the toluene solvent was removed by heating at 60 C. under vacuum. In this way there was obtained 23 g. of crude product. A 16 g. portion was distilled to give dimethyl 5- chloro-2,3-dihydrothien-4-yl phosphate, b.p.- 122 C. at 0.1 mm Hg. Analysis gave the following results: Calculated for C H ClOJS: Cl, 14.50; P, 12.63; S, 13.10; Found: C], 14.20; P, 12.50; S, 13.03. Example 3 Preparation of dimethyl dihydrothien-4-yl phosphate 3-methyl tetrahydrothiophen-4-one was prepared from methyl thioglycolate and methyl methacrylate by essentially the same process as described in Example 1. This ketone, 1 1.6 g. was dissolved in 100 m1. of toluene and cooled to 20 C.
3-methy1-2,3-
Then, while passing nitrogen through the solution and keeping the temperature in the range of 20 to 30 C., 13.5 g. of sulfuryl chloride was added rapidly. Five minutes after the addition was complete, the solution was placed under vacuum and the temperature was slowly raised to C. At this temperature, the vacuum was released and 18.6 g. of trimethyl phosphite was added and the temperature was rapidly raised to the reflux. Heating was continued at the reflux for 3 hours. Then the toluene solvent was removed by heating at 70 C. under a vacuum. In this way there was obtained 19.5 g. of crude phosphate product.
The crude product was then charged to a silica gel chromatographic column and washed with a 2:1 hexanezether solution to remove impurities. When this solvent system failed to remove any more material from the column, the desired product was eluted from the column using a 1:1 hexanezether mixture. in this way there was obtained 8.1 g. of dimethyl 3- methyl-2,3-dihydrothien-4-yl phosphate, which analyzed as follows. Calculated for C7H13O4PS: P, 13.78; S, 14.30; Found: P, 13.81;S, 14.24.
Example 4 Preparation of dimethyl l,l-dioxo--chloro-2,3- dihydrothien-4-yl phosphate The product of Example 2, 8.1 g., was dissolved in 150 ml. of dichloromethane. Then 14.5 g. of 85 percent m-chloroperbenzoic acid was added in small increments over a period of 1 hour. When addition was complete, the reaction mixture was stirred for 16 hours at 23 C. At the end of this time, the mixture was filtered, washed with aqueous sodium bicarbonate (20 g. in 400 ml. water), and with water. It was then dried over anhydrous magnesium sulfate. After filtering and evaporation of the solvent, there was obtained 6.0 g. of product. Analysis was as follows: Calculated for C H CIO PS: Cl, 12.81; P, 11.18; S, 11.60; Found: C1, 12.98;P, 10.90; S, 11.49.
Example 5 Preparation of diethyl l-oxo-5-chloro-2,3- dihydrothien-4-yl phosphate Diethyl 5-chloro-2,3-dihydrothien-4-yl phosphate was prepared by essentially the same process as in Example 2 using triethyl phosphite in place of trimethyl phosphite. A flask was charged with 22.0 g. of diethyl 5-chloro-2,3dihydrothien-4-yl phosphate and 150 ml. of dichloromethane. To this solution there was added 16.2 g. of 85 percent m-chloroperbenzoic acid in increments over a period of minutes. After all the acid was added, the solution was stirred for 30 minutes at 0 C., and at 23 C. for 4 hours. At the end of this time the reaction mixture was filtered and diluted with an equal volume of diethyl ether. The resulting solution was washed with 10 percent sodium carbonate and with ice water. It was dried over magnesium sulfate. After filtration and solvent removal there was obtained g. of product. Analysis was as follows: Calculated for C H ClO PS: Cl, 12.30; P, 10.70; S, 11.1 1; Found: Cl, 1 1.62; P, 10.58; S, 10.62
Using the above described procedures. other dihydrothienyl phosphates and oxidized dihydrothienyl phosphates were prepared. These phosphates, along with their analyses, are reported in Table 11.
TABLE 11 Representative phosphates of this invention were tested by the following procedures to illustrate the insecticidal properties of the group. The test results are reported in Table III.
CONTACT TESTS German Cockroach (Blaltella germanica L): A 100 ppm. acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the above described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
Houseflies (Musca domestica): A 250 ppm. acetone solution of the candidate toxicant was placed in a syringe. A random mixture of anesthetized male and female DDT-resistant houseflies was placed on cardboard squares. A 0.5 microgram dose of the acetone solution was applied directly to each fly. The flies were then placed in a recovery cage. Mortality readings were taken after 24 hours.
Aphids (Aphids gossypii Glover): An acetone solution of the test compound was prepared and diluted with water containing a small amount of nonionic surfactant to 30 ppm. 3 replicate cucumber leaf sections each infested with at least 20 aphids were dipped into this acetone-water solution. Excess solution was drained from the section and they were held under controlled conditions for 24 hours. Mortality readings were then made on 20 randomly selected aphids per replicate and the percent mortality based on the average of these readings was calculated.
Mites (Telranychus telarius L): An acetone solution of the test compound was prepared and diluted with water containing a small amount of nonionic surfactant to 100 ppm. 3 replicate lima bean leaf sections each infested with at least 20 mites were dipped into this acetone-water solution. Excess solution was drained from the section and they were held under controlled conditions for 24 hours. Mortality readings were then made on 20 randomly selected mites per replicate and the percent mortality based on the average of these readings was calculated.
SYSTEMIC TESTS Aphids (Aphids gossypii Glover) and Mites (Tetranychus telarium L): An acetone solution of the test compound (with a small amount of nonionic surfactant added) was prepared and diluted with water to 500 ppm. 40 ml. of this solution was applied to the soil in a 4 inch pot containing two plants (pinto bean for mites; cucumber for aphids). Forty-eight hours after this application these plants were infested with the test insects. Mortality readings were taken 48 hours after infestation and a percent mortality was calculated from these readings.
ln topical tests similar to those described above phosphates included within this invention exhibited control of milkweed bug, cabbage looper, mosquito larvae, dock beetle larvae and mite eggs.
Phosphates of this invention also have exhibited excellent Percent Element analyses Compound Dimathyl .2,3-dihydrothian-4-yl phosphate Diethyl 5-ch101'0-2,3-dihydrothien4-yl phosphate Diethyl 2-n1ethy1-2,3-dihyd1'0thien-4-yl phosphate Dimethyl 2-1nethy1-2,3-dihydrothienA-yl phosphatev Dimethyl 2-111ethyl-5-chl0ro-2,3-dihydrothien-4-yl phosphate Diethyl 1,l-dioito-ZB-dihhydrothielH-yl phosphate Dlethyl 1,l-dloxo-fi-chlol'o-12,3-di-hydrothien4-yl phosphate UTILITY The dihydrothienyl phosphates of this invention exhibit a wide spectrum of insecticidal activity in both topical as well as systemic applications. In such applications insecticidal quantities of one or more of these phosphates are applied directly to the insects or their environment.
Cale.
Cale.
Found Found TABLE III Percent mortullty Contact tests Systemic tests mp n Flies Aphids r0232: Mites Aphids Mites this invention may be applied in other liquid or solid formulations to the pests described above, their environment or hosts susceptible to attack from such pests. For example, when applied as insecticides they may be sprayed or otherwise applied directly to plants or soil so as to eflect control of insects coming into contact therewith. When used as nematocides, they will normally be applied directly to nematode-infested soil at dosage levels between 3 and 40 pounds per acre. (Solid formulations may be plowed into the soil; liquid formulations ma be sgrayed or ingected.)
orm atlons of t e compounds of tlus invention will comprise a toxic amount of one or more phosphates and a biologically inert carrier. Usually they will also contain a wetting agent to facilitate their penetration and dispersion into the soil and/or hosts to which they are applied. Solid carriers such as clay, talc, sawdust and the like may be used insuch formulations. Liquid diluents which may be used with these compounds include xylene, toluene, acetone and benzene.
The terms insecticide and insect" as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect" is used not only to include small invertebrate animals belonging to the class Inseam but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.
As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.
I claim:
1. A compound of the formula:
wherein R and R are alkyl of one to four carbon atoms, R is hydrogen, alkyl of one to three carbon atoms or halogen of atomic number 17 to 35, R, R and R are hydrogen or alkyl of one to three carbon atoms and n is 0, l or 2.
2. The compound of claim 1 wherein said halogen is chlorine.
3. The compound of claim 1 wherein n is 0, R and R are the same and are methyl or ethyl, and R R, R and R are hydrogen.
4. The compound of claim 1 wherein n is 0, R and R are the same and are methyl or ethyl, R is chlorine, R is hydrogen or methyl, and R and R are hydrogen.
5. The compound of claim I wherein n is 2, R and R are the same and are methyl or ethyl, R is hydrogen or chlorine, and R, R and R are hydrogen.
6. The compound of claim 1 wherein Rand R are ethyl, n is l, R is chlorine and R", R and R are hydrogen.
7. The compound of claim 1 wherein R and R are the same and are methyl or ethyl, R R and R are hydrogen, R is methyl, and n is 0.
Claims (6)
- 2. The compound of claim 1 wherein said halogen is chlorine.
- 3. The compound of claim 1 wherein n is 0, R and R1 are the same and are methyl or ethyl, and R2, R3, R4 and R5 are hydrogen.
- 4. The compound of claim 1 wherein n is 0, R and R1 are the same and are methyl or ethyl, R2 is chlorine, R3 is hydrogen or methyl, and R4 and R5 are hydrogen.
- 5. The compound of claim 1 wherein n is 2, R and R1 are the same and are methyl or ethyl, R2 is hydrogen or chlorine, and R3, R4 and R5 are hydrogen.
- 6. The compound of claim 1 wherein R and R1 are ethyl, n is 1, R2 is chlorine and R3, R4 and R5 are hydrogen.
- 7. The compound of claim 1 wherein R and R1 are the same and are methyl or ethyl, R2, R3 and R4 are hydrogen, R5 is methyl, and n is 0.
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US88529169A | 1969-12-15 | 1969-12-15 |
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US3755214A (en) * | 1971-11-12 | 1973-08-28 | M & T Chemicals Inc | Thiophene condensates as flame retardants for polyurethane foam |
US4128562A (en) * | 1975-02-14 | 1978-12-05 | Roussel Uclaf | Novel 3-(phosphoryloxy) and (phosphonyloxy)-thiophenes |
US4461764A (en) * | 1982-09-22 | 1984-07-24 | Chevron Research Company | Pesticidal phosphoryl- and phosphinyl-thioalkyl cyclic sufones |
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US3106565A (en) * | 1960-05-02 | 1963-10-08 | Monsanto Chemicals | Organophosphorus esters |
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US3234238A (en) * | 1961-11-02 | 1966-02-08 | Hooker Chemical Corp | Substituted tetrahydrothiophenes and their preparation |
US3341553A (en) * | 1964-07-15 | 1967-09-12 | Stauffer Chemical Co | S-(2, 5-dichloro-3-thienyl-thiomethyl)-o, o-diethylphosphorodithioate |
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US3106565A (en) * | 1960-05-02 | 1963-10-08 | Monsanto Chemicals | Organophosphorus esters |
US3234237A (en) * | 1961-11-02 | 1966-02-08 | Hooker Chemical Corp | Novel substituted tetrahydrothiophenes and the preparation thereof |
US3234238A (en) * | 1961-11-02 | 1966-02-08 | Hooker Chemical Corp | Substituted tetrahydrothiophenes and their preparation |
US3228965A (en) * | 1962-01-08 | 1966-01-11 | Hooker Chemical Corp | Organothiophosphate derivatives of halogenated cyclic sulfones |
US3341553A (en) * | 1964-07-15 | 1967-09-12 | Stauffer Chemical Co | S-(2, 5-dichloro-3-thienyl-thiomethyl)-o, o-diethylphosphorodithioate |
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US3755214A (en) * | 1971-11-12 | 1973-08-28 | M & T Chemicals Inc | Thiophene condensates as flame retardants for polyurethane foam |
US4128562A (en) * | 1975-02-14 | 1978-12-05 | Roussel Uclaf | Novel 3-(phosphoryloxy) and (phosphonyloxy)-thiophenes |
US4155996A (en) * | 1975-02-14 | 1979-05-22 | Roussel Uclaf | 3-(Phosphoryloxy) and (phosphonyloxy)-thiophenes |
US4461764A (en) * | 1982-09-22 | 1984-07-24 | Chevron Research Company | Pesticidal phosphoryl- and phosphinyl-thioalkyl cyclic sufones |
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