CN1206709A - 制备异硫氰酸吡啶基甲酯的方法 - Google Patents
制备异硫氰酸吡啶基甲酯的方法 Download PDFInfo
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- 125000005344 pyridylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 10
- -1 pyridylmethyl isothiocyanates Chemical class 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 12
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 239000011591 potassium Substances 0.000 abstract description 5
- 239000003085 diluting agent Substances 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 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 abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 150000004659 dithiocarbamates Chemical class 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 150000002540 isothiocyanates Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- XPARFBOWIYMLMY-UHFFFAOYSA-N (6-chloropyridin-3-yl)methanamine Chemical compound NCC1=CC=C(Cl)N=C1 XPARFBOWIYMLMY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MSGVGTJUFIDURD-UHFFFAOYSA-N [K].ClC1=NC=C(C=C1)CNC(S)=S Chemical compound [K].ClC1=NC=C(C=C1)CNC(S)=S MSGVGTJUFIDURD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- PQLFROTZSIMBKR-UHFFFAOYSA-N ethenyl carbonochloridate Chemical compound ClC(=O)OC=C PQLFROTZSIMBKR-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/40—Acylated substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/12—Dithiocarbonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
- C07D213/61—Halogen atoms or nitro radicals
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Abstract
本发明涉及一种新的制备通式(Ⅰ)所示异硫氰酸吡啶基甲酯的方法,其特征在于,第一步反应中,通式(Ⅱ)所示的胺与通式(Ⅲ)所示黄原酸盐,如果适宜的话在稀释剂存在下,反应,及第二步反应中,所得通式(Ⅳ)所示的新的二硫代氨基甲酸盐,如果适宜的话在稀释剂存在下,氧化,制得通式(Ⅰ)的异硫氰酸盐化合物,其中,R1代表卤素或C1－C4－烷基,其中,R1如上所述,其中,R2代表C1－C4－烷基,优选甲基或乙基及M代表碱金属优选钠和钾或代表铵,其中,R1和M分别如上所述。
Description
本发明涉及一种新的制备异硫氰酸吡啶基甲酯的方法及其新中间体。
现有制备异硫氰酸吡啶基甲酯的方法是将通式(A)所示吡啶基甲基胺与二硫化碳和例如氯甲酸乙酯在碱如氢氧化钠存在的条件下按下列反应式进行反应：
Py=选择性取代的吡啶基，例如2-氯-5-吡啶基(参见EP-A0 302 389)
然而，上述方法的不利之处在于选用二硫化碳作为反应参与物。此外还会生成氧硫化碳副产物。
现已发现制备具有良好产率和高纯度通式(Ⅰ)所示异硫氰酸吡啶基甲酯的方法，
其中，R1代表卤素或C1-C4-烷基，
第一步反应中，通式(Ⅱ)所示的胺与通式(Ⅲ)所示黄原酸盐，如果适宜的话在稀释剂存在下，反应，其中，R1如上所述，
其中，
R2代表C1-C4-烷基，优选甲基或乙基，及
M代表碱金属，优选钠和钾，或代表铵，及
第二步反应中，所得通式(Ⅳ)所示的二硫代氨基甲酸盐，如果适宜的话在稀释剂存在下，氧化，制得通式(Ⅰ)的异硫氰酸化合物，
其中，
R1和M分别如上所述。
式(Ⅰ)为本发明制得的异硫氰酸吡啶基甲酯化合物的通式。此通式中，R1优选为氯或甲基。
令人惊奇地是，式(Ⅰ)所示异硫氰酸吡啶基甲酯在本发明制备方法中收率良好并且纯度较高，尽管式(Ⅲ)黄原酸盐中的含硫基团MSH是比醇基团R2OH更好的离去基团，而该反应机制因此本应推断为：
本发明所述制备反应的优越性在于不采用二硫化碳作为反应参与物。此外，反应情况简单(无放热反应)并且反应过程中无副反应。
反应中采用例如5-氨基甲基-2-氯吡啶和乙基黄原酸钾作为起始反应物并以NaOCl水溶液作为氧化剂，本发明所述方法的反应过程如下列反应式所示：
作为本发明所述方法第一步反应中的起始反应物的式(Ⅱ)所示胺化合物是已知的(参见，例如EP-A 0 391 205或US-P 4 499 097)和／或可通过常规方法制得。
作为本发明方法第一步反应的另一起始反应物的式(Ⅲ)所示黄原酸盐也是公知化合物。
式(Ⅳ)代表本发明所述制备方法第一步反应的产物二硫代氨基甲酸盐的结构通式。此通式中，R1优选为氯或甲基并且M优选为钠，钾或铵。
式(Ⅳ)的二硫代氨基甲酸盐是新化合物并且也是本申请的发明主题之一。
本发明所述方法的第二步反应的优选氧化剂是：次氯酸钠或次氯酸钾溶液和铜(Ⅱ)化合物例如硫酸铜。
本发明所述方法中第一步反应的适宜稀释剂是常规有机溶剂。其中优选烃类，例如甲苯或二甲苯；醚，例如甲基叔丁基醚、甲基叔戊基醚、1，2-二甲氧基乙烷、1，2-二乙氧基乙烷、四氢呋喃或二噁烷；醇，例如甲醇、乙醇、正丙醇、异丙醇、正-、异-、仲-或叔-丁醇；腈，例如乙腈、丙腈或丁腈；以及酰胺，例如二甲基甲酰胺。
进行本发明方法第一步时的反应温度可在相对较宽的范围内变化。通常，反应温度介于30-150℃之间，优选介于50-120℃之间。
在本发明所述方法第一步反应中优选采用等摩尔量反应。然而，反应亦允许价廉的式(Ⅲ)所示黄原酸盐有相对较大的过量，优选过量100％。
反应结束后生成新的式(Ⅳ)所示二硫代氨基甲酸盐并且可用常规方法分离出该化合物(参见：制备实施例)。
本发明所述方法的第二步氧化反应的优选稀释剂是水和另一惰性微水溶的溶剂，例如烃类、氯代烃、醚、腈、酮或酰胺。
本发明所述方法第二步中的反应温度可在相对较宽范围内变化。通常，反应温度介于-30℃-50℃之间，优选介于-10℃-10℃之间。
以每摩尔二硫代氨基甲酸盐计，本发明所述方法第二步反应中所用氧化剂通常是4-5摩尔，优选4-4．5摩尔。
反应结束后得到式(Ⅰ)的异硫氰酸吡啶基甲酯并且可用常规方法将其分离(参见：制备实施例)。
通过本发明所述制备方法制得的式(Ⅰ)异硫氰酸吡啶基甲酯可作为作为制备生物活性化合物例如杀虫剂的中间体(参见：例如EP-A 0302 389)。
制备实施例实施例1
(第二步反应)
将51．3g(0．2mol)的2-氯-5-吡啶基甲基二硫代氨基甲酸钾(参见：第一步反应)溶解在200ml水中并再混入200ml的二氯甲烷。
在0℃下，将460ml浓度为13％的NaOCl水溶液维持反应温度不超过5℃滴加到上述溶液中。反应混合物在0-5℃下搅拌30分钟，然后分离出有机相，水相用二氯甲烷萃取三次，合并有机相并用硫酸钠干燥。
蒸除溶剂，在冰箱内结晶出31．3g(为理论产率的82％)的2-氯-5-吡啶基甲基异硫氰酸酯(熔点：22℃)。
(第一步反应)
将2．85g(20mmol)2-氯-5-氨基甲基-吡啶和3．2g(20mmol)乙基黄原酸钾在30ml乙醇中搅拌下回流过夜。
冷却并过滤反应混合物：得到4．4g(为理论产率的86％)熔点为252℃(分解)的2-氯-5-吡啶基甲基二硫代氨基甲酸钾。
Claims (4)
1．一种通式(Ⅰ)所示异硫氰酸吡啶基甲酯的制备方法
其中，R1代表卤素或C1-C4-烷基，
其特征在于：
第一步反应中，通式(Ⅱ)所示的胺与通式(Ⅲ)所示黄原酸盐，如果适宜的话在稀释剂存在下，反应，
其中，R1如上所述，
其中，
R2代表C1-C4-烷基，及
M代表碱金属或铵，
第二步反应中，所得通式(Ⅳ)所示的二硫代氨基甲酸盐，如果适宜的话在稀释剂存在下，氧化，制得通式(Ⅰ)的异硫氰酸盐化合物，
其中，R1和M分别如上所述。
2．通式(Ⅳ)所示的二硫代氨基甲酸盐其中，R1代表卤素或C1-C4-烷基，及M代表碱金属或铵。
3．通式(Ⅳ)所示二硫代氨基甲酸盐的制备方法，
其中，
R1和M分别如权利要求1所述，
其特征在于，式(Ⅱ)所示的胺与式(Ⅲ)所示黄原酸盐，如果适宜的话在稀释剂存在下，反应，式(Ⅱ)为其中，R1如权利要求1所述，
其中，
R2代表C1-C4-烷基，及
M代表碱金属或铵。
4．通式(Ⅳ)所示二硫代氨基甲酸盐在制备通式(Ⅰ)所示异硫氰酸吡啶基甲酯中的应用，通式(Ⅳ)为其中，R1和M分别如权利要求2所述，通式(Ⅰ)为
其中，R1代表卤素或C1-C4-烷基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19731782.0 | 1997-07-24 | ||
| DE19731782A DE19731782A1 (de) | 1997-07-24 | 1997-07-24 | Verfahren zur Herstellung von Pyridylmethylisocyanaten |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1206709A true CN1206709A (zh) | 1999-02-03 |
| CN1114595C CN1114595C (zh) | 2003-07-16 |
Family
ID=7836723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98116170A Expired - Fee Related CN1114595C (zh) | 1997-07-24 | 1998-07-24 | 制备异硫氰酸吡啶基甲酯的方法 |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5936093A (zh) |
| EP (1) | EP0893441B1 (zh) |
| JP (1) | JP4338237B2 (zh) |
| KR (1) | KR100499901B1 (zh) |
| CN (1) | CN1114595C (zh) |
| DE (2) | DE19731782A1 (zh) |
| DK (1) | DK0893441T3 (zh) |
| ES (1) | ES2186057T3 (zh) |
| HK (1) | HK1018262A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229551A (zh) * | 2011-04-29 | 2011-11-02 | 浙江工业大学 | 一种异硫氰酸酯的制备方法 |
| CN102993073A (zh) * | 2012-03-27 | 2013-03-27 | 中国农业科学院兰州畜牧与兽药研究所 | 异硫氰酸2，6-二甲基苯酯的制备方法 |
| CN103012226A (zh) * | 2012-12-27 | 2013-04-03 | 济南圣泉唐和唐生物科技有限公司 | 一种异硫氰酸乙酯的制备方法 |
| CN112979632A (zh) * | 2021-03-15 | 2021-06-18 | 台州学院 | 一种4-羟基-1,3-噻嗪-2-硫酮类化合物的合成方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735128B (zh) * | 2009-12-31 | 2013-11-20 | 北京农鹰现代农业技术研究院 | 制取异硫氰酸烯丙酯的方法 |
| CN103086933B (zh) * | 2013-01-23 | 2014-07-02 | 安徽工程大学 | 一种苯基异硫氰酸酯的制备方法 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE7700500L (sv) * | 1976-01-20 | 1977-07-21 | Hoechst Ag | Tiazolidinderivat och forfarande for deras framstellning |
| DE10399003I2 (de) * | 1987-08-01 | 2004-07-01 | Sumitomo Chem Takeda Agro Co | Alpha-ungesättigte Amine, ihre Herstellung und Verwendung. |
-
1997
- 1997-07-24 DE DE19731782A patent/DE19731782A1/de not_active Withdrawn
-
1998
- 1998-07-13 ES ES98112969T patent/ES2186057T3/es not_active Expired - Lifetime
- 1998-07-13 EP EP98112969A patent/EP0893441B1/de not_active Expired - Lifetime
- 1998-07-13 DK DK98112969T patent/DK0893441T3/da active
- 1998-07-13 DE DE59806793T patent/DE59806793D1/de not_active Expired - Lifetime
- 1998-07-14 KR KR1019980028339A patent/KR100499901B1/ko not_active IP Right Cessation
- 1998-07-15 JP JP21475898A patent/JP4338237B2/ja not_active Expired - Fee Related
- 1998-07-16 US US09/116,267 patent/US5936093A/en not_active Expired - Lifetime
- 1998-07-24 CN CN98116170A patent/CN1114595C/zh not_active Expired - Fee Related
-
1999
- 1999-04-23 US US09/298,593 patent/US6166214A/en not_active Expired - Lifetime
- 1999-07-22 HK HK99103169A patent/HK1018262A1/xx not_active IP Right Cessation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229551A (zh) * | 2011-04-29 | 2011-11-02 | 浙江工业大学 | 一种异硫氰酸酯的制备方法 |
| CN102229551B (zh) * | 2011-04-29 | 2014-07-02 | 浙江工业大学 | 一种异硫氰酸酯的制备方法 |
| CN102993073A (zh) * | 2012-03-27 | 2013-03-27 | 中国农业科学院兰州畜牧与兽药研究所 | 异硫氰酸2，6-二甲基苯酯的制备方法 |
| CN103012226A (zh) * | 2012-12-27 | 2013-04-03 | 济南圣泉唐和唐生物科技有限公司 | 一种异硫氰酸乙酯的制备方法 |
| CN103012226B (zh) * | 2012-12-27 | 2014-11-19 | 济南圣泉唐和唐生物科技有限公司 | 一种异硫氰酸乙酯的制备方法 |
| CN112979632A (zh) * | 2021-03-15 | 2021-06-18 | 台州学院 | 一种4-羟基-1,3-噻嗪-2-硫酮类化合物的合成方法 |
| CN112979632B (zh) * | 2021-03-15 | 2022-08-30 | 台州学院 | 一种4-羟基-1,3-噻嗪-2-硫酮类化合物的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US6166214A (en) | 2000-12-26 |
| KR100499901B1 (ko) | 2006-04-12 |
| JPH1192453A (ja) | 1999-04-06 |
| DK0893441T3 (da) | 2003-03-24 |
| JP4338237B2 (ja) | 2009-10-07 |
| DE59806793D1 (de) | 2003-02-06 |
| EP0893441A1 (de) | 1999-01-27 |
| KR19990013838A (ko) | 1999-02-25 |
| CN1114595C (zh) | 2003-07-16 |
| US5936093A (en) | 1999-08-10 |
| HK1018262A1 (en) | 1999-12-17 |
| DE19731782A1 (de) | 1999-01-28 |
| EP0893441B1 (de) | 2003-01-02 |
| ES2186057T3 (es) | 2003-05-01 |
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