CN1220679C - Preparation of thiol carbamate and thiocyanic ester compound - Google Patents
Preparation of thiol carbamate and thiocyanic ester compound Download PDFInfo
- Publication number
- CN1220679C CN1220679C CNB031082378A CN03108237A CN1220679C CN 1220679 C CN1220679 C CN 1220679C CN B031082378 A CNB031082378 A CN B031082378A CN 03108237 A CN03108237 A CN 03108237A CN 1220679 C CN1220679 C CN 1220679C
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- Prior art keywords
- salt
- compound
- acid
- reaction
- preparation
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- 238000002360 preparation method Methods 0.000 title claims description 31
- -1 thiol carbamate Chemical class 0.000 title description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 148
- 150000001875 compounds Chemical class 0.000 claims abstract description 137
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 37
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 8
- 239000012433 hydrogen halide Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000000749 insecticidal effect Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 83
- 238000006243 chemical reaction Methods 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 37
- 239000000203 mixture Substances 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000010410 layer Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 235000011167 hydrochloric acid Nutrition 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- UMSVPCYSAUKCAZ-UHFFFAOYSA-N propane;hydrochloride Chemical compound Cl.CCC UMSVPCYSAUKCAZ-UHFFFAOYSA-N 0.000 description 8
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 8
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- FYWVSYHXSQVHMW-UHFFFAOYSA-N n,n-dimethyl-1-oxodithiolan-4-amine;hydrochloride Chemical compound Cl.CN(C)C1CSS(=O)C1 FYWVSYHXSQVHMW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 150000003613 toluenes Chemical class 0.000 description 4
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 3
- 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 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- IMLSAISZLJGWPP-UHFFFAOYSA-N 1,3-dithiolane Chemical compound C1CSCS1 IMLSAISZLJGWPP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- UEAOWHWVNVSMSM-UHFFFAOYSA-N n,n-dimethyldithiolan-4-amine;hydrochloride Chemical compound Cl.CN(C)C1CSSC1 UEAOWHWVNVSMSM-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical compound CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/02—Thiosulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a method for producing a compound represented by the formula; wherein R1 and R2 independently represent a alky group, or a salt thereof, which comprises reacting a compound represented by the formula; where each symbol has the same meaning as defined above, or a salt thereof, with a salt of sulfurous acid under pH 4 to 11 at a temperature below 60 DEG C to provide a compound represented by the formula; where M is an alkaline or alkaline earth metal as ammonium and the other symbols have the same meaning s as defined above, or a salt thereof, and the reacting the resulting compound with prussic acid or a salt thereof. The compound (I) or a salt thereof is useful as an intermediate for synthesis of thiolcarbamate derivatives which have excellent insecticidal activities. According to the method of the present invention, compound (I) or a salt thereof can be obtained in high yield.
Description
The application is to be the dividing an application of Chinese patent application 99123998.9 on September 15th, 1999 applying date.
The compound or its salt of having described a kind of formula (I) expression in JP-B-42177/1976 has strong insecticidal activity,
R wherein
1And R
2Represent alkyl independently, or R
1And R
3Form a nitrogenous 5-or 6-unit heterocyclic radical (abbreviating hereinafter, " compound (I) " sometimes as) with adjacent nitrogen-atoms.A kind of synthetic insecticide activity thiolcarbonic acid ester derivative stronger, that formula (III) is represented or important intermediate of its salt of being used for also described in JP-B-10969/1967,
Wherein each symbol has meaning same as described above (hereinafter abbreviating " compound (III) " sometimes as).
About the preparation method of formula (I) compound or its salt, the method for corresponding dihalide and thiocyanic ester reaction, corresponding thiosulphate (hereinafter being called for short bunte salts sometimes) and the method for the method of prussiate reaction, corresponding dimercapto compound and halogen prussiate (halogen cyan) reaction and the method for corresponding stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate compound and prussiate (hydrocyanide) reaction in JP-B-18012/1964, JP-B-19524/1969, JP-A-34316/1972 and JP-B-28905/1988, have been reported respectively.
A kind of formula (IV) compound or its salt has been described in JP-B-17404/1970,
R wherein
1And R
2Have meaning same as described above, M is metal or ammonium (hereinafter abbreviating " compound (IV) " sometimes as), and it has strong insecticidal activity, and is to be used for that the synthetic insecticide activity is stronger, the important intermediate of thiol-carbamate (III).
About the preparation method of formula (IV) compound or its salt, in JP-B-17404/1970, reported the method for corresponding dihalide and thiosulphate (sodium byposulfite salt) reaction.
But, according to prior art, intractable waste water, and also have the low problem of productive rate.In addition, it is useless that the filtrate (depleted) that produces in the step to thiol-carbamate (III) that fabulous insecticidal activity is arranged in preparation is carried out crystallization, so prior art is with its burning.Because above-mentioned refuse contains sulfur hydroxyamino acid ester derivative, from economize on resources angle this be a serious environmental problem.
In addition, according to the method for describing, have the problem that productive rate is lower in JP-B-18012/1964 or JP-B-17404/1970, reason is to have produced the by product that formula V is represented:
Wherein X represents group SCN or SSO
3M (wherein M represents metal or ammonium), the meaning of other symbol defines as above,
Such as S, S '-(dimethylaminomethyl) ethylene two (Sulfothiorine) and dimethylaminomethyl ethyl two (thiocyanic ester), they are respectively the isomer of above-mentioned product.
The inventor has concentrated and has studied the productive rate height, wastewater treatment is simple and the thiol-carbamate production stage that can circulate during the compound (I), (III) or (IV) or the preparation method of its salt of the refuse that produces.As a result, the inventor is surprised to find, formula (II) compound or its salt:
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms,
When itself and prussic acid or its reactant salt, the dithiolane (dithiolanering) of compound (II) splits, and high productivity generates compound (I) or its salt.
In addition, the inventor is surprised to find, formula (II) compound or its salt:
Wherein each symbol has the meaning identical with above-mentioned definition,
When itself and sulfurous acid or its reactant salt, the dithiolane of compound (II) splits, and high yield high purity ground generates compound (IV) or its salt.This compound (IV) or its salt also can with prussic acid or its reactant salt, generate compound (I) or its salt.
In addition, the inventor has also carried out concentrated research based on these knowledge, thereby has finished the present invention.
In other words, the present invention relates to:
[1] preparation method of the compound or its salt of a kind of formula (I) expression,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms,
It comprises the compound or its salt of formula (II) expression
Wherein each symbol has meaning same as described above,
With prussic acid or its reactant salt,
[2] as [1] described method, wherein R
1And R
2Represent alkyl independently,
[3] as [1] described method, wherein R
1And R
2All represent methyl,
[4] preparation method of the compound or its salt of a kind of formula (III) expression,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms,
It comprises the compound or its salt of formula (II) expression
Wherein each symbol has meaning same as described above,
With prussic acid or its reactant salt, generate the compound or its salt of a kind of formula (I) expression,
Wherein each symbol has meaning same as described above,
Then the compound that generates is hydrolyzed and reacts or in the presence of hydrogen halide, react with a kind of lower alcohol,
[5] preparation method of the compound or its salt of a kind of formula (IV) expression,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms, M is metal or ammonium,
It comprises the compound or its salt of formula (II) expression
Wherein each symbol has meaning same as described above,
With sulfurous acid or its reactant salt,
[6] as [5] described method, wherein R
1And R
2Represent alkyl independently,
[7] as [5] described method, wherein R
1And R
2All represent methyl,
[8] preparation method of the compound or its salt of a kind of formula (I) expression,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms,
It comprises the compound or its salt of formula (II) expression
The above-mentioned identical meaning of each symbol wherein,
With sulfurous acid or its reactant salt, generate the compound or its salt of a kind of formula (IV) expression,
Wherein M is metal or ammonium, and other symbol has meaning same as described above,
Then with the compound and prussic acid or its reactant salt that generate; With
[9] preparation method of the compound or its salt of a kind of formula (III) expression,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms,
It comprises:
(i) Biao Shi compound or its salt formula) II)
Wherein each symbol has meaning same as described above,
With sulfurous acid or its reactant salt, generate the compound or its salt of a kind of formula (IV) expression,
Wherein M is metal or ammonium, and other symbol has meaning same as described above,
(ii) with the compound and prussic acid or its reactant salt that generate, the compound or its salt that production (I) is represented
Wherein each symbol has meaning same as described above,
With
(iii) the compound that generates is hydrolyzed and reacts or in the presence of hydrogen halide, react with a kind of lower alcohol.
R
1And R
2The alkyl of expression comprises can contain two keys or the triple-linked straight chain, side chain or cyclic aliphatic hydrocarbyl, aryl or aralkyl.Can use alkyl, thiazolinyl, alkynyl, aryl or aralkyl especially.Wherein preferred C
1-19Alkyl.
Alkyl comprises C straight chain or side chain
1-6Alkyl or C
3-14Cycloalkyl for example comprises C
1-6Alkyl or C
3-14Cycloalkyl is such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, isopentyl, neo-pentyl, cyclopropyl, cyclopentyl, n-hexyl, isohexyl or cyclohexyl.
Thiazolinyl comprises the C of straight or branched
2-6Alkenyl or C
3-14Cycloalkenyl group for example comprises C
2-6Thiazolinyl or C
3-14Cycloalkenyl group is such as allyl group, pseudoallyl, isobutenyl, pentenyl, 2-hexenyl or 2-cyclohexenyl.
Alkynyl comprises C
2-6Alkynyl is such as proyl, 2-butyne base, 3-butynyl, 3-pentynyl or 3-hexin base.
Aryl comprises C
6-14Aryl is such as phenyl, naphthyl or anthryl.
Aralkyl comprises C
7-19Aralkyl is such as phenyl-C
1-4Alkyl (for example benzyl, styroyl, hydrocinnamyl etc.), diphenyl-methyl or trityl.
In formula
In the group of expression, R
1And R
2The nitrogenous 5-or the 6-unit heterocyclic radical that form with adjacent nitrogen-atoms comprise that pyrrolidino, piperidino-(1-position only), Piperazino, morpholino base, thiomorpholine are for base or thiazolidyl.
R
1And R
2The low alkyl group that 1-4 carbon atom arranged of preferred straight or branched.Wherein, special preferable methyl.
The salt of compound (I) comprises the salt that forms with the mineral acid of all example hydrochloric acids, sulfuric acid and phosphoric acid or the salt that forms with organic acid such as Phenylsulfonic acid, tosic acid and oxalic acid.
Compound (I) or its salt can pass through compound (II) or its salt and prussic acid or its salt and give birth to weakly alkaline, particularly prepared in reaction under the condition of pH5-9, preferred pH7-9 at weak acid.
The prussic acid that can use in the present invention or its salt comprise the solid alkali metal salt of prussic acid, such as the sodium cyanide and the potassium cyanide that can obtain from market, or use hydrocyanic acid gas, if possible, can use ammonium salt or alkaline earth salt (for example calcium salt, magnesium salts etc.), heavy metallic salt (for example iron, copper, zinc etc.).Sodium cyanide (sodium cyanide) and potassium cyanide (potassium cyanide) use as preferred prussic acid or its salt.
The salt of compound (II) comprises the identical salt of salt with above-claimed cpd (I).
Because this reaction is carried out quantitatively at short notice, for 1 mole compound (II), 2 moles of hydrogen cyanic acid or its salt are competent on stoichiometry.If desired, can use excessive prussic acid or its salt, but from economize on resources and processing reaction after the angle of the refuse that generates consider that this is undesirable.
As the solvent that in reaction, uses, preferably use soluble compound (II) or its salt and one of prussic acid or its salt or both solvents, even but solvent can not dissolve both well, and this reaction also can fully be carried out.But, consider that it is undesirable that the character of reaction reagent, compound (I) and compound (II) or its salt, pH are tended to solvent extremely acid or extremely alkalescence.Therefore, if a kind solvent is a neutral almost, then to reaction not any solvent of influence can use.This kind solvent comprises rudimentary aliphatic alcohol, such as methyl alcohol, ethanol, Virahol etc.; Lower aliphatic ketone is such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; Rudimentary chain or cyclic aliphatic ethers are such as ether, tetrahydrofuran (THF), dioxane etc.; The lower alphatic carboxylic acid derivative is such as ethyl acetate, acetonitrile, dimethyl formamide etc.; Rudimentary chain or cyclic aliphatic sulphur compound are such as dithiocarbonic anhydride, dimethyl sulfoxide (DMSO), tetramethylene sulfone etc.If desired, can make water or lower aliphatic halohydrocarbon, such as methylene dichloride, chloroform or tetracol phenixin; Or aromatic hydrocarbons, such as benzene,toluene,xylene or chlorobenzene.These solvents can use separately or two or more (preferably being no more than wherein three kinds) in them be mixed use in the proper ratio.In addition, when reaction mixture is not equal phase time, for example under the situation of water and aromatic hydrocarbons or aliphatic halogenated hydrocarbons, reaction system becomes two-phase, but in this case, preferably adds a small amount of phase-transfer catalyst, such as quaternary ammonium salt, sulfonium salt or phosphonium salt.Two kinds of solvents of preferred use are such as water and a kind of not miscible with water solvent (for example toluene or benzene), because carry out lock out operation easily.
In the method for the invention, compound (II) or its salt are contacted with prussic acid or its salt in the solvent that is fit to, begin reaction immediately.But reaction heat release ground carries out.To thermally labile, therefore, it is ideal that temperature of reaction remains below 40 ℃ to the compound (I) that generates, and is generally room temperature or is not higher than room temperature under the form of free alkali.If desired, cooling reactor from the outside.The preferred 0-20 of temperature of reaction ℃.
Also have, the reaction in the inventive method is gently carried out under these conditions, finishes to a few hours in common 1 hour, but according to circumstances can finish at several minutes or tens of minutes.
Because compound (I) or its salt lack the stability to alkali, the reaction times unnecessarily prolong and the situation of the compound (I) that generates and excessive cryanide ion Long contact time under, may cause variable color or reduction productive rate.Therefore, cooling immediately after finishing reaction is ideal through extraction with the reallocation of suitable solvents (for example toluene, benzene etc.) is separated the material of needs from reaction system.
By can easily determine finishing of reaction such as thin-layer chromatography (TLC), high performance liquid chromatography analyses such as (HPLC).
Compound (I) or its salt can be converted into the compound or its salt (hereinafter abbreviating compound (III) sometimes as) of formula (III) expression of fabulous insecticidal activity according to JP-B-19520/1970 or the described method of JP-B-10969/1967
Wherein each symbol has meaning same as described above.
In other words, compound (I) or its salt are hydrolyzed reaction or compound (I) or its salt reacted with lower alcohol in the presence of following hydrogen halide can prepare compound (III) or its salt.
The starting material compound of this reaction (I) or its salt just can use without isolated or purified after the preparation that aforesaid method according to the present invention carries out.Can certainly use isolated or purified compound (I) or its salt.
[hydrolysis reaction]
Compound (I) or the hydrolysis under acidic conditions of its salt.The acid of using comprises mineral acid, all example hydrochloric acids, sulfuric acid, phosphoric acid, Hydrogen bromide etc.Preferred especially hydrochloric acid and sulfuric acid.The preferred 5-98% of concentration of acid.Preferred 5% saturated hydrochloric acid or 10-60% sulfuric acid.The preferred 0-100 of temperature of reaction ℃, preferred 20-80 ℃ especially.
This reaction can be carried out in acidic aqueous solution, if desired, can be added in about describe and organic solvent that do not influence reaction the reaction for preparing compound (I) or its salt from compound (II) or its salt.When using not, can add above-mentioned phase-transfer catalyst with the miscible organic solvent of water.
[with the reaction of hydrogen halide]
At hydrogen halide (HX)-such as hydrogen chloride gas and bromize hydrogen gas---in the presence of, compound (I) or its salt and lower alcohol (R ' OH; R ' represents rudimentary C
1-4Alkyl is such as methyl, ethyl etc.) reaction, generate intermediate (IX) or its salt, do not separate then, heated mixt under decompression or normal pressure, or mixture placed room temperature, the cancellation alkyl halide (R ' X), preparation mixture (III) or its salt.
The reaction of preparation intermediate (IX) can be carried out preferred 0-40 ℃ under the temperature between the boiling point of the lower alcohol that uses at 0 ℃.This reaction can relatively promptly be carried out, and to continue to finish in 2-12 hour be ideal but will react.For compound (I), the amount of hydrogen halide is preferably greater than 10 equivalents greater than 3 equivalents.
Lower alcohol comprises methyl alcohol, ethanol etc.As hydrogen halide, preferred especially hydrogen chloride gas.
The salt of compound (III) comprises the identical salt of salt with above-claimed cpd (I).
Compound (III) or its salt can separate and purifying with known method itself, such as extraction, pH regulator, reallocation, concentrate, concentrating under reduced pressure, crystallization and recrystallization etc.
For example, after finishing reaction, when reaction mixture is the aqueous solution, extract and need not other operation, when reaction mixture contains can be with the mixed uniformly organic solvent of water the time, behind the concentrating under reduced pressure, add almost water-fastly, extract then such as lower aliphatic halohydrocarbon such as methylene dichloride or chloroforms or such as aromatic hydrocarbons such as benzene,toluene,xylene or chlorobenzenes.Concentrate the organic layer that obtains like this, obtain the crude product crystal of compound (III).By crystallization in ether, toluene etc. after adding mineral acid such as all example hydrochloric acids, sulfuric acid, phosphoric acid, Hydrogen bromide or adding organic acids such as Phenylsulfonic acid, tosic acid, oxalic acid, can obtain isolated compound (III) with the form of salt.
Can prepare compound (II) or its salt that uses in the method for the present invention according to known method itself, for example use Chemistry at Agricultural and Biological, 34,935-940, the method described in 1974.
Above-claimed cpd (I) or its salt can use compound (II) or its salt to obtain according to following another kind of method.
In other words, by compound (II) or its salt and sulfurous acid or its reactant salt, the compound or its salt of production (IV) expression,
Wherein M is metal or ammonium, and other symbol has meaning same as described above,
Make compound and prussic acid or its reactant salt of generation then, can prepare compound (I) or its salt.
M is that metal is (for example such as basic metal such as sodium, potassium; Such as alkaline-earth metal such as calcium, magnesium) or ammonium group.Wherein, preferred sodium or potassium.
When pH is about 4 the time, compound (IV) can form the inner salt of formula (VI) expression:
Wherein each symbol has meaning same as described above.This class inner salt is also included within the scope of compound (IV).This inner salt shows low water solubility, therefore can be used as crystal separation.In this case, it often has crystal water.
Compound (IV) or its salt can pass through compound (II) or its salt and sulfurous acid or its salt in slightly acidic to weakly alkaline, prepared in reaction under the condition of pH4-11, preferred especially pH4-8 preferably.
The salt of compound (IV) comprises the identical salt of salt with above-claimed cpd (I).
As sulfurous acid or its salt, comprise an alkali metal salt of sulfurous acid, such as S-WAT, potassium sulfite etc.; Ammonium sulphite; Hydrosulphite (with alkali-metal salt) is such as sodium bisulfite, Potassium hydrogen sulfite etc.; The sulphite of alkaline-earth metal is such as calcium sulfite, magnesium sulfite etc.; Sulphurous acid gas etc.
Wherein the solid alkali metal salt of preferred sulfurous acid can obtain from market, such as S-WAT or potassium sulfite.
Because this reaction is carried out quantitatively at short notice, for 1 mole compound (II), 2 moles of sulfurous acid or its salt are competent on stoichiometry.If desired, can allow excessive about 2-4 mole.
Solvent as using in the reaction preferably uses soluble compound (II) or its salt and one of sulfurous acid or its salt or both solvents, even but solvent can not dissolve both well, and this reaction also can fully be carried out.But, consider that it is undesirable that the character of reaction reagent, compound (IV) and compound (II), pH are tended to solvent extremely acid or extremely alkalescence.Therefore, if a kind solvent is a neutral almost, then to reaction not any solvent of influence can use.This kind solvent comprises the water and the another kind of solvent of dissolving sulfurous acid or its salt needs, comprises for example rudimentary aliphatic alcohol, such as methyl alcohol, ethanol, Virahol etc.; Lower aliphatic ketone is such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; Rudimentary chain or cyclic aliphatic ethers are such as ether, tetrahydrofuran (THF), dioxane etc.; The lower alphatic carboxylic acid derivative is such as ethyl acetate, acetonitrile, dimethyl formamide etc.; Rudimentary chain or cyclic aliphatic sulphur compound are such as dithiocarbonic anhydride, dimethyl sulfoxide (DMSO), tetramethylene sulfone etc.; The lower aliphatic halohydrocarbon is such as methylene dichloride, chloroform or tetracol phenixin etc.; Or aromatic hydrocarbons, such as benzene,toluene,xylene or chlorobenzene etc.These solvents can use separately or in the proper ratio two or more (preferably being no more than wherein three kinds) in them be mixed use with water.
In the method for the invention, compound (II) or its salt are contacted with sulfurous acid or its salt in the solvent that is fit to, begin reaction immediately.It is ideal that temperature of reaction remains below 60 ℃, is generally 50 ℃ or be not higher than 50 ℃.The preferred 20-50 of temperature of reaction ℃.
Also have, the reaction in the inventive method is gently carried out under these conditions, finishes during a few hours at 30 minutes usually.
By can easily determine finishing of reaction as thin-layer chromatography (TLC), high performance liquid chromatography analyses such as (HPLC).
Compound (IV) or its salt can be converted into compound (I) or its salt of fabulous insecticidal activity according to the described method of JP-B-19524/1969.
In addition, compound (IV) or its salt can separate and purifying with known method itself, such as pH regulator, ion-exchange chromatography, concentrate, concentrating under reduced pressure, crystallization and recrystallization etc.
For example, when reaction mixture is the aqueous solution,, need not other operation with the mineral acid of equivalent or excessive a little all example hydrochloric acids, sulfuric acid, phosphoric acid or such as the organic acid neutralization of Phenylsulfonic acid, tosic acid, oxalic acid; When reaction mixture contains can be with the mixed uniformly organic solvent of water the time, after concentrating under reduced pressure was removed organic solvent, the water layer of gained neutralized with aforesaid method, and isolated compound (VI) inner salt is highly purified crystal.
Compound (I) or its salt can be used compound (IV) or its salt and prussic acid or the preparation of its reactant salt.This reaction is available and above-mentioned to prepare compound (I) or its salt from compound (II) or its salt reacting phase with condition carry out.The starting material compound of this reaction (IV) or its salt just can use without isolated or purified after method for preparing according to the present invention.Can certainly use isolated or purified compound (IV) or its salt.
The compound that obtains like this (I) or its salt can change into compound (III) with method same as described above.
Embodiment
The following example is used to describe in detail the present invention, should not think limiting the scope of the invention.
Embodiment 1
Preparation 2-(dimethylamino) trimethylene two (thiocyanic ester)
2.49g (98.3%, 0.05 mole of purity) sodium cyanide (sodium cyanide) is dissolved in 22.06g water, mixture is cooled to 5 ℃ then.In mixture, add 25ml toluene, Dropwise 5 .04g (0.025 mole) 4-dimethylamino-1 in about 1 hour time then, 2-dithiolane-1-oxide hydrochloride is dissolved in the solution that 20.16g water forms.After adding, under identical temperature, stirred the mixture 1 hour, be divided into toluene layer and water layer.Analyze this toluene layer with HPLC, obtain 2.35g 2-(dimethylamino) trimethylene two (thiocyanic ester) (productive rate: 46.7%) and 0.82g 4-dimethylamino-1,2-dithiolane (productive rate: 21.996).
Embodiment 2
Preparation 2-(dimethylamino) trimethylene two (thiocyanic ester)
(5.04g 0.025 mole) 4-dimethylamino-1,2-dithiolane-1-oxide hydrochloride is dissolved in 35g water.In mixture, add 25ml toluene, mixture is cooled to 5 ℃ then.This moment, pH was 2.6.
2.49g (purity: 98.3%, 0.05 mole) sodium cyanide is dissolved in 6.86g water in addition.This solution was added drop-wise in the mixture of above-mentioned acquisition in about 1 hour time.During this period, the hydrochloric acid with 5N is controlled at 8 with pH.After adding, under identical temperature, stirred the mixture about 1 hour.With the NaOH of 4N with pH regulator to 10 after, mixture is divided into toluene layer and water layer.Analyze this toluene layer with HPLC, obtain 4.91g 2-(dimethylamino) trimethylene two (thiocyanic ester) (productive rate: 97.6%).Under reduced pressure toluene layer is concentrated, the residue that obtains recrystallization from methyl alcohol obtains crystal 2-(dimethylamino) trimethylene two (thiocyanic ester) (fusing point: 53-54 ℃).
Embodiment 3
Preparation 2-(dimethylamino) trimethylene two (thiocyanic ester)
(13.19g 0.071 mole) 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt is dissolved in 250ml water.In mixture, add 100ml toluene, then because reaction is heat release, so at the sodium hydroxide that is cooled to be lower than dropping 28% under 45 ℃ of conditions up to pH=9.After pH regulator to 9, at the hydrogen peroxide that in 1 hour, drips 7.59g (0.078 mole) 35% under the identical temperature.During this period, with 28% sodium hydroxide pH is controlled at 9.After adding, stirred reaction mixture is about 1 hour under identical temperature, and mixture is divided into toluene layer and water layer then.Add the hydrochloric acid of 15ml water and 17.1g (0.1645 mole) 35% in toluene layer, mixture is divided into toluene layer and water layer then.The result who analyzes water layer with HPLC has obtained 12.5g (0.0675 mole) 4-(dimethylamino)-1,2-dithiolane hydrochloride.In remaining on this aqueous solution of 10 ℃, drip the superoxol of 6.56g (0.0675 mole) 35% under agitation during about 1 hour.After adding, at room temperature stirred the mixture about 1 hour.Result with the HPLC analyze reaction mixture has obtained 12.93g (0.0641 mole) 4-(dimethylamino)-1,2-dithiolane-1-oxide hydrochloride.Add 65ml toluene in this mixture, mixture is cooled to 5 ℃, then during about 1 hour in the solution that in 17.6g water, prepares of dropping 6.38g (98.3%, 0.13 mole of purity) sodium cyanide (sodium cyanide).During this period, with the hydrochloric acid of 5N pH is controlled at and is not more than 7.After adding, stirred the mixture under identical temperature about 1 hour, the sodium hydroxide of using 4N is with pH regulator to 10, and mixture is divided into toluene layer and water layer.Analyze this toluene layer with HPLC, obtain 12.00g 2-(dimethylamino) trimethylene two (thiocyanic ester) (productive rate: 84.096,, 3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt) based on 1.
Embodiment 4
Preparation S, S '-(2-dimethylamino) trimethylene two (Sulfothiorine)
7.96g (95%, 0.06 mole of purity) S-WAT is dissolved in 24.90g water.In this mixture, add 80ml toluene, then with concentrated hydrochloric acid with pH regulator to 7.0.After solution was heated to 30 ℃, Dropwise 5 .04g in about 1.5 hours (0.025 mole) 4-dimethylamino-1,2-dithiolane-1-oxide hydrochloride were dissolved in the solution that 20.16g water forms.Between charge period, pH is remained on 7 with concentrated hydrochloric acid.After stirring the mixture under the identical temperature about 1 hour, the sodium hydroxide with 28% is with pH regulator to 9.0, and separating mixture obtains the aqueous solution of title compound then.Analyze water layer with HPLC, obtain 7.82gS, S '-(2-dimethylamino) trimethylene two (Sulfothiorine) (productive rate: 88.096).
Embodiment 5
Preparation S, S '-(2-dimethylamino) trimethylene two (Sulfothiorine)
13.27g (95%, 0.10 mole of purity) S-WAT is dissolved in 44.41g water.In this mixture, add 80ml toluene, then with concentrated hydrochloric acid with pH regulator to 7.0.After solution was heated to 30 ℃, Dropwise 5 .04g in about 1.5 hours (0.025 mole) 4-dimethylamino-1,2-dithiolane-1-oxide hydrochloride were dissolved in the solution that 20.16g water forms.Between charge period, pH is remained on 7 with concentrated hydrochloric acid.After identical temperature stirred the mixture about 1 hour, the sodium hydroxide with 28% was with pH regulator to 9.0, and separating mixture obtains the aqueous solution of title compound.Analyze water layer with HPLC, obtain 8.71g S, S '-(2-dimethylamino) trimethylene two (Sulfothiorine) (productive rate: 98.096).
Embodiment 6
Preparation S, S '-(2-dimethylamino) trimethylene two (Sulfothiorine)
(13.19g 0.071 mole) 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt is dissolved in 250ml water.In mixture, add 100ml toluene, then because reaction is heat release, so at the sodium hydroxide that is cooled to be lower than dropping 28% under 45 ℃ of conditions up to pH=9.After pH regulator to 9, at the hydrogen peroxide that in 1 hour, drips 7.59g (0.078 mole) 35% under the identical temperature.During this period, with 28% sodium hydroxide pH is controlled at 9.After adding, stirred the mixture under identical temperature about 1 hour, mixture is divided into toluene layer and water layer then.Add the hydrochloric acid of 15ml water and 17.1g (0.1645 mole) 35% in toluene layer, mixture is divided into toluene layer and water layer then.The result who analyzes water layer with HPLC has obtained 12.5g (0.0675 mole) 4-(dimethylamino)-1,2-dithiolane hydrochloride.In remaining on this aqueous solution of 10 ℃, drip the superoxol of 6.56g (0.0675 mole) 35% under agitation during about 1 hour.After adding, at the stirring at room mixture about 1 hour.Result with the HPLC analyze reaction mixture has obtained 12.93g (0.0641 mole) 4-(dimethylamino)-1,2-dithiolane-1-oxide hydrochloride.
In addition, 34.02g (95%, 0.256 mole of purity) S-WAT is dissolved in 113.1g water.In this mixture, add 205ml toluene, then with concentrated hydrochloric acid with pH regulator to 7.0.After drips of solution is added to 30 ℃, in about 1.5 hours, drip the 4-dimethylamino-1 of the above-mentioned preparation of all amounts (12.93g, 0.0641 mole), the 2-dithiolane-1-oxide hydrochloride aqueous solution.Between charge period, pH is remained on 7 with concentrated hydrochloric acid.After stirring the mixture under the identical temperature about 1 hour, the sodium hydroxide with 28% is with pH regulator to 9.0, and separating mixture obtains the aqueous solution of title compound.Analyze this water layer with HPLC, obtain 21.64gS, S '-(2-dimethylamino) trimethylene two (Sulfothiorine) (productive rate: 85.7%, based on 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt).
Embodiment 7
Preparation 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt
According to at the identical reaction conditions described in the embodiment 2, by 10.09g (0.05 mole) 4-dimethylamino-1, the preparation of 2-dithiolane-1-oxide hydrochloride contains the toluene solution of 2-(dimethylamino) trimethylene two (thiocyanic ester).In concentrated resistates that obtains of this toluene solution and 30ml methanol mixture, fed hydrogen chloride gas 2 hours.Reaction mixture under reduced pressure concentrates, and removes methylene dichloride and methyl alcohol.The resistates recrystallization obtains 12.18g (89%) 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt.
Embodiment 8
Preparation 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane
To according to the mixture of 20.1g (0.1 mole) 2-(dimethylamino) trimethylene two (thiocyanic ester) that obtain at the identical reaction conditions described in the embodiment 2 and 4ml water in feeding hydrogen chloride gas 8 hours.Reaction mixture is dissolved in 35ml water.This solution neutralizes with sodium bicarbonate.After ice-cooled, filter the crystal that collecting precipitation goes out.Dried crystals, recrystallization in ethanol obtains 12.1g (51%) 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane.
Embodiment 9
Preparation 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt
According to embodiment 5 same procedure, by 10.09g (0.05 mole) 4-dimethylamino-1, the preparation of 2-dithiolane-1-oxide hydrochloride contains S, S '-(2-dimethylamino) trimethylene two (Sulfothiorine) aqueous solution.
4.90g (0.10 mole) sodium cyanide portions joins in this aqueous solution, mixture stirred 30 minutes down ice-cooled then.Filter the crystal that collecting precipitation goes out, obtain 8.56g 2-(dimethylamino) trimethylene two (thiocyanic ester) (productive rate: 85%,, 2-dithiolane-1-oxide hydrochloride) based on 4-dimethylamino-1.
In compound that obtains like this and 30ml methanol mixture, fed hydrogen chloride gas 2 hours.Reaction mixture under reduced pressure concentrates, and removes methylene dichloride and methyl alcohol.Resistates is recrystallization in methyl alcohol, obtains 11.46gl, 3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane hydrochloride salt (productive rate: 83%, based on 4-dimethylamino-1,2-dithiolane-1-oxide hydrochloride).
The method according to this invention has generated the water-soluble inorganic salt as by product from compound (II) preparation compound (I), thus the product of wishing, and oil loving compound (I) can easily separate after reaction is finished.For example, when making water and can be from water as reaction solvent under the situation of isolating a kind of organic solvent,, can collect sulfocyanic ester compound quantitatively as high-purity product by being divided into the water layer that contains inorganic salt and containing the organic layer of wishing product.Therefore, can easily handle the refuse that the inventive method produces, be special useful in addition from antipollution angle.
This compounds (I) or its salt also can be by compound (IV) or the preparations of its salt.The method of compound produced according to the present invention (I) and compound (IV) does not generate the isomer such as compound (V) as by product, so compound (I) and compound (IV) can high yield obtain.
In addition; the sulfur hydroxyamino acid ester derivative that strong insecticidal activity is arranged that the compound (I) that obtains according to the inventive method or its salt are synthetic compound (III) expression (for example; 1,3-two (formamyl sulfenyl)-2-(N, N-dimethylamino) propane) useful as intermediates.
In addition, compound (IV) but or the expression of its salt drawing-in system (VIII) as the thiosulfonic acid ester derivative of strong insecticidal activity is arranged as described in the JP-B-13755/1971:
R wherein
1And R
2Have meaning same as described above, or R
3It is lower alkoxy; Can have and contain the low alkyl group of Sauerstoffatom as heteroatomic saturated heterocyclyl; The 10-camphyl; Can have alkyl, lower alkoxy, lower alkylthio, halogen or amido as substituent phenyl; Or naphthyl.
Therefore, compound (IV) or its salt can be used as the compound that intermediate is used to prepare fabulous insecticidal activity.Above-claimed cpd (VIII) can be according to the described method preparation of JP-B-32350/1988.
In addition, use the following step, the thiocarbamate acid ester derivant crystalline filtrate of containing that generates in its preparation process can be introduced in compound (II) or its salt.Filtrate hydrolysis under alkaline condition, oxidation then obtains compound (VII) or its salt (at this, salt comprises the identical salt of salt with above-claimed cpd (I)) that formula (VII) is represented:
Wherein each symbol has meaning same as described above,
The compound that oxidation generates under acidic conditions obtains compound (II) or its salt then.In addition, the method according to this invention can obtain compound (I) or its salt from compound (II) or its salt, and therefore, it can be used for the synthetic of compound (II) or its salt as the intermediate circulation.From the angle that economizes on resources, it is extremely useful that these methods are considered to, because can intermediate be used further to agrochemicals by collecting from refuse.
Claims (5)
1. the preparation method of the compound or its salt represented of a following formula,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms, M is metal or ammonium, and it comprises the compound or its salt that following formula is represented
Wherein each symbol has meaning same as described above, with sulfurous acid or its reactant salt.
2. the method for claim 1, wherein R
1And R
2Represent alkyl independently.
3. the method for claim 1, wherein R
1And R
2All represent methyl.
4. the preparation method of the compound or its salt represented of a following formula,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms, it comprises the compound or its salt that following formula is represented
Wherein each symbol has meaning same as described above, with sulfurous acid or its reactant salt, generates the compound or its salt that a kind of following formula is represented,
Wherein M is metal or ammonium, and other symbol has meaning same as described above, then with the compound and prussic acid or its reactant salt that generate.
5. the preparation method of the compound or its salt represented of a following formula,
R wherein
1And R
2Represent alkyl independently, or R
1And R
2Form a nitrogenous 5-or 6-unit heterocyclic radical with adjacent nitrogen-atoms, it comprises:
(i) compound or its salt that following formula is represented
Wherein each symbol has meaning same as described above, with sulfurous acid or its reactant salt, generates the compound or its salt that a kind of following formula is represented,
Wherein M is metal or ammonium, and other symbol has meaning same as described above,
(ii), generate the compound or its salt that following formula is represented with the compound and prussic acid or its reactant salt that generate
Wherein each symbol have meaning same as described above and
(iii) the compound that generates is hydrolyzed and reacts or in the presence of hydrogen halide, react with lower alcohol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP265283/1998 | 1998-09-18 | ||
| JP26528398A JP4078439B2 (en) | 1998-09-18 | 1998-09-18 | Method for producing thiocyanate compound |
| JP26528998A JP4078440B2 (en) | 1998-09-18 | 1998-09-18 | Production method of organic thiosulfate |
| JP265289/1998 | 1998-09-18 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991239989A Division CN1142138C (en) | 1998-09-18 | 1999-09-15 | Preparation of thiol-carbamate and sulfocyanic ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1495162A CN1495162A (en) | 2004-05-12 |
| CN1220679C true CN1220679C (en) | 2005-09-28 |
Family
ID=26546920
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031082378A Expired - Lifetime CN1220679C (en) | 1998-09-18 | 1999-09-15 | Preparation of thiol carbamate and thiocyanic ester compound |
| CNB991239989A Expired - Lifetime CN1142138C (en) | 1998-09-18 | 1999-09-15 | Preparation of thiol-carbamate and sulfocyanic ester compound |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991239989A Expired - Lifetime CN1142138C (en) | 1998-09-18 | 1999-09-15 | Preparation of thiol-carbamate and sulfocyanic ester compound |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR100634076B1 (en) |
| CN (2) | CN1220679C (en) |
| HK (2) | HK1029103A1 (en) |
| IN (1) | IN186610B (en) |
| TW (2) | TWI241288B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519371B (en) * | 2008-05-18 | 2012-06-20 | 杭州宇龙化工有限公司 | Preparation method of cartap hydrochloride intermediate, i.e., 2-N, N-dimethyl-1, 3-dithio-cyano propane |
| CN103864795B (en) * | 2012-12-14 | 2018-01-23 | 济南大学 | Cis anabasine compound containing dithiolane and its preparation method and application |
-
1999
- 1999-09-15 TW TW093120568A patent/TWI241288B/en not_active IP Right Cessation
- 1999-09-15 CN CNB031082378A patent/CN1220679C/en not_active Expired - Lifetime
- 1999-09-15 KR KR1019990039565A patent/KR100634076B1/en not_active IP Right Cessation
- 1999-09-15 IN IN789CA1999 patent/IN186610B/en unknown
- 1999-09-15 CN CNB991239989A patent/CN1142138C/en not_active Expired - Lifetime
- 1999-09-15 TW TW088115886A patent/TWI230704B/en active
-
2000
- 2000-12-28 HK HK00108447A patent/HK1029103A1/en not_active IP Right Cessation
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- 2004-07-27 HK HK04105521A patent/HK1062674A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TWI230704B (en) | 2005-04-11 |
| KR20000023182A (en) | 2000-04-25 |
| HK1029103A1 (en) | 2001-03-23 |
| HK1062674A1 (en) | 2004-11-19 |
| CN1263089A (en) | 2000-08-16 |
| TWI241288B (en) | 2005-10-11 |
| CN1142138C (en) | 2004-03-17 |
| IN186610B (en) | 2001-10-13 |
| CN1495162A (en) | 2004-05-12 |
| KR100634076B1 (en) | 2006-10-13 |
| TW200422286A (en) | 2004-11-01 |
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