CN1214012C - 制备羰基二咪唑的方法 - Google Patents
制备羰基二咪唑的方法 Download PDFInfo
- Publication number
- CN1214012C CN1214012C CNB998083860A CN99808386A CN1214012C CN 1214012 C CN1214012 C CN 1214012C CN B998083860 A CNB998083860 A CN B998083860A CN 99808386 A CN99808386 A CN 99808386A CN 1214012 C CN1214012 C CN 1214012C
- Authority
- CN
- China
- Prior art keywords
- imidazoles
- mixture
- dimethylbenzene
- carbonyl dimidazoles
- nitrogenous base
- 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 - Fee Related
Links
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 4
- 229930013930 alkaloid Natural products 0.000 claims description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 abstract description 3
- -1 C1-C4 alkyl radical Chemical class 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 2
- 239000001257 hydrogen Substances 0.000 abstract 2
- GRSTVVGJSKHCCS-UHFFFAOYSA-N bis(1h-imidazol-2-yl)methanone Chemical class N=1C=CNC=1C(=O)C1=NC=CN1 GRSTVVGJSKHCCS-UHFFFAOYSA-N 0.000 abstract 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KLBOFRLEHJAXIU-UHFFFAOYSA-N tributylazanium;chloride Chemical compound Cl.CCCCN(CCCC)CCCC KLBOFRLEHJAXIU-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
Abstract
本发明涉及一种制备具有通式(Ia)、(Ib)、(Ic)的羰基二咪唑或其混合物的方法,其中R1为氢原子或C1-4-烷基且R2为氢原子或甲基。按照本发明,将至少一种具有通式(IIa)和(IIb)的咪唑,其中R1和R2具有上述含义,与光气在惰性溶剂中进行反应,向该反应混合物中加入基于咪唑的化学计算量的、pKb低于咪唑的有机含氮碱。
Description
本发明涉及一种由咪唑和光气制备羰基二咪唑以避免偶联产物咪唑盐酸盐的改进方法。
羰基二咪唑(CDI)是一种常用于引入羰基,例如用于制备碳酸酯、脲或氨基甲酸乙酯,或在酯或酰胺合成中用于活化非活性反应物(应用化学(Angew.Chem.)74(1962),407)。
制备羰基二咪唑的两种方式原则上是已知的。化学通讯(Chem.Ber.)93(1960),2804和美国专利4965366描述了一种两步法,如以下方案所示,其中首先将咪唑与三甲基甲硅烷基氯反应得到1-三甲基甲硅烷基咪唑。然后将后者与光气反应得到CDI。
尽管三甲基甲硅烷基氯可循环使用,但该合成路径的时间过长,并导致所需产物的时空产率不好。此外,水解敏感性三甲基甲硅烷基氯的处理对反应装置有附加要求。
制备CDI的更好方式是来源于Staab等人的咪唑直接光气化,且描述于各种出版物(Liebigs Ann.Chem.609(1957),75;Chem.Ber.96(1963),3374;有机合成文集(Org.Synth.Coll.)Vol.V(1973),201)。尽管这样得到2摩尔作为偶联产物的咪唑盐酸盐/每摩尔CDI,但前者可通过碱性处理而转化成咪唑并返回光气化体系:
EP-A-0692476仅通过一种将溶剂脱水的方法来扩展以前参考文献中描述的合成路径。但原始方法的一个主要困难仍然存在。作为偶联产物同时形成的咪唑盐酸盐必须在高温(80-100℃)在排除水分的情况下从含CDI的反应溶液中过滤去除。由于CDI对水解特别敏感,因此要保持足够高质量的产物需要非常复杂的技术。
迄今所有的咪唑直接光气化方法的缺点在于形成偶联产物咪唑盐酸盐,它必须在附加工艺步骤中循环并导致时空产率减半。
具有较早优先权但未公开的出版物的WO98/31672涉及一种通过将例如,咪唑与光气在有机碱,如三(正丁基)胺的存在下进行反应来制备,例如CDI的方法。
本发明的一个目的是提供一种由咪唑和光气来制备羰基二咪唑以避免所述缺点的方法。
已经发现,该目的通过一种制备具有通式Ia、Ib、Ic的羰基二咪唑或其混合物的方法而得以实现:
其中R1为氢原子或C1-4-烷基且R2为氢原子或甲基,该方法包括将至少一种具有通式IIa和IIb的咪唑:
其中R1和R2具有上述含义,与光气在惰性溶剂中进行反应,其中向该反应混合物中加入基于咪唑的化学计算量或过量最高30%摩尔的pKb值低于咪唑的有机含氮碱。
在该方法中,通过加入有机碱而避免了咪唑盐酸盐的形成,这样所用咪唑可完全转化成羰基二咪唑。通过这种合成设计,作为副产物不可避免产生的盐酸被比咪唑更强的碱结合,这样使用的所有咪唑可反应生成羰基二咪唑。因此,仅需要从产物中分离出辅助碱的盐酸盐,并在转化成游离碱后循环到合成体系中。
咪唑本身是一种弱碱(pKb值约7)并在光气化反应中同时用作试剂和酸捕获剂。通过在合成过程中加入一种更强的含氮碱,例如叔脂族胺,尤其是三丁胺,在合成中要么直接将该更强的碱优先质子化,要么由所形成的盐酸盐重新形成咪唑:
如此再次成为游离碱形式的咪唑可进一步光气化。为了保证所使用的所有咪唑完全转化,按照以下的总反应式,需要当量的叔含氮碱。
该方法的优点尤其在于其时空产率是前述方法的两倍,因为所用咪唑完全转化,且无需将作为盐酸盐的未用的一半咪唑进行循环。
该反应在惰性溶剂中,优选在60-100℃,特别优选60-80℃的温度下,在取代芳烃中进行。二甲苯或氯苯优选用于此,且二甲苯可以是邻-、间-和对-二甲苯的混合物或异构体之一。特别优选使用二甲苯及其异构体的混合物。
合适的叔含氮碱原则上是pKb低于咪唑pKb的任何碱。
优选使用具有通式NR3的叔胺作为含氮碱,其中R基团相互独立地分别为支化或未支化C1-10-烷基,或两个该基团与一个氮原子形成一个可另外被一个或两个氧或氮原子间断的5-或6-元杂环脂族或杂芳族环。
含氮碱优选为叔脂族胺,其中R基团相同且为C1-4-烷基,如三甲基-、三乙基-、三丙基-、三异丙基-、三正丁基-、三异丁基-、三仲丁基-胺。特别优选三正丁胺。其中两个基团形成一个环的胺的例子为N-烷基吡咯烷和N-烷基哌啶。被杂原子间断的环的例子为N-烷基吗啉和N,N’-二烷基哌嗪。
以下描述的工艺步骤是羰基二咪唑(CDI)的例子。但该方法也可用于上述取代化合物。
所形成的胺盐酸盐预期会从反应混合物中作为固相沉淀出。在所述方法中,反应溶液在高温(50-60℃)下保持均匀。羰基二咪唑只有在冷却时才作为无色针从反应混合物中沉淀,而三丁胺盐酸盐则完全留在溶剂中。在不受一种理论局限的情况下,显然,CDI通过盐析作用被胺盐酸盐从溶液中排挤出,而三丁胺盐酸盐则由于其较长的极性烷基基团而仍溶解在溶剂中。
所形成的CDI可通过冷却反应混合物而结晶出来并作为固体取出,而由含氮碱形成的盐酸盐则留在有机溶剂中。沉淀的CDI可通过在惰性气体下简单吸滤或使用离心去除法从溶剂/胺盐酸盐混合物中去除。即使没有洗涤,它也足够纯,可进一步使用。这是该方法的一个明显优点,因为这种对水分非常敏感的产物仅接触空气一次。溶解在溶剂中的叔胺盐酸盐可用更强的含水无机碱,优选NaOH或KOH的水溶液进行中和之后,变回到游离碱,留在有机溶剂中。在有机溶剂中释放的含氮碱可随后与水相分离并循环到合成中。
本发明通过以下实施例进一步说明。
实施例1:
所有反应在一个容积为2升、夹套加热、并具有二氧化碳冷凝器(-78℃)和搅拌器的HWS容器中进行。
将185.4克三丁胺(1摩尔)溶解在1010克二甲苯中。将该溶液加热回流,并且将二甲苯蒸馏到脱水器中,直到水不再分离出(总共约10毫升)。将68克(1摩尔)咪唑加入该反应混合物,然后在30分钟内,将总共51克(0.5摩尔)光气在68-80℃下通入。加入结束之后,反应在65℃下继续60分钟。将该反应的均匀出料转移到用干燥氩气冲洗的Erlenmeyer烧瓶中。室温冷却之后,无色晶体在短时间内析出并在氩气下吸滤,然后每次用50毫升无水二甲苯洗涤两次。真空干燥之后,得到59克的熔点112℃的CDI。
元素分析:计算值:C:51.84 H:3.74 N:34.56
实测值:C:51.90 H:3.80 N:34.60
实施例2:
伴随再次反应的三丁胺盐酸盐循环
在搅拌下将40%浓度的氢氧化钠溶液加入来自实施例1的母液中,直到pH值保持恒定在12(总共:克)。分离出水(下方)相,将三丁胺的二甲苯溶液转移到反应容器中,然后将二甲苯蒸馏到脱水器中,直到水不再分离出。冷却该反应混合物之后,加入68克(1摩尔)二甲苯和21克(0.1摩尔)三丁胺。
在72-83℃,将总共51克(0.5摩尔)光气在30分钟内通入。在光气计量加料完成之后,在65℃下继续搅拌60分钟。按照实施例1进行处理。干燥之后,得到57克的熔点112℃的CDI。
实施例3:
将来自实施例2的母液按照类似于实施例2所述的工艺步骤进行处理,然后在70-79℃下光气化。
处理之后,得到53克的熔点109℃的CDI。
实施例4(实施例1的重复):
将185.4克三丁胺(1摩尔)溶解在1010克二甲苯中。将该溶液加热回流,并将二甲苯蒸馏到脱水器中,直到水不再分离出(总共约10毫升)。将68克(1摩尔)咪唑加入该反应混合物,然后在30分钟内,将总共56克(0.57摩尔)光气在68-78℃下通入。加入结束之后,反应在65℃下继续60分钟。将该反应的均匀出料转移到用干燥氩气冲洗的Erlenmeyer烧瓶中。室温冷却之后,无色晶体在短时间内析出并在氩气下吸滤,然后每次用50毫升无水二甲苯洗涤两次。真空干燥之后,得到62克的熔点114℃的CDI。
实施例5:
使用氯苯作为溶剂,按照实施例1和4进行合成。在相同工艺步骤和处理下,得到50克的熔点114℃的CDI。
Claims (1)
1.一种制备具有通式Ia、Ib、Ic的羰基二咪唑或其混合物的方法:
其中R1为氢原子或C1-4-烷基且R2为氢原子或甲基,该方法将至少一种具有通式IIa和IIb的咪唑:
其中R1和R2具有上述含义,与光气在二甲苯或其异构体的混合物或氯苯中于60-100℃温度下进行反应,其特征在于,向该反应混合物中加入基于咪唑的化学计算量的有机含氮碱三正丁胺,其中所形成的羰基二咪唑通过冷却反应混合物而结晶出来并作为固体分离出,而形成的含氮碱的盐酸盐则留在有机溶液中,所述含氮碱的盐酸盐被NaOH或KOH中和,以变回到游离碱而留在二甲苯或其异构体的混合物或氯苯中,并且其中将在二甲苯或其异构体的混合物或氯苯中释放的含氮碱与水相分离并循环到合成体系中。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19830556.7 | 1998-07-08 | ||
DE19830556A DE19830556A1 (de) | 1998-07-08 | 1998-07-08 | Verfahren zur Herstellung von Carbonyldiimidazolen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1308613A CN1308613A (zh) | 2001-08-15 |
CN1214012C true CN1214012C (zh) | 2005-08-10 |
Family
ID=7873373
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998083860A Expired - Fee Related CN1214012C (zh) | 1998-07-08 | 1999-07-06 | 制备羰基二咪唑的方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6353115B1 (zh) |
EP (1) | EP1095024B1 (zh) |
JP (1) | JP2002520318A (zh) |
KR (1) | KR20010071762A (zh) |
CN (1) | CN1214012C (zh) |
AU (1) | AU5409899A (zh) |
CA (1) | CA2336657C (zh) |
DE (2) | DE19830556A1 (zh) |
HU (1) | HUP0102739A3 (zh) |
WO (1) | WO2000002863A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10359797A1 (de) * | 2003-12-19 | 2005-07-21 | Bayer Chemicals Ag | Verfahren zur Herstellung von N,N'-Carbonyldiazolen |
KR101126954B1 (ko) * | 2004-03-30 | 2012-03-23 | 호도가야 가가쿠 고교 가부시키가이샤 | N,n'-카르보닐디이미다졸의 제조 방법 |
CN102321026A (zh) * | 2011-08-02 | 2012-01-18 | 海门瑞一医药科技有限公司 | 羰基二咪唑的生产工艺 |
KR102473775B1 (ko) * | 2022-04-15 | 2022-12-05 | ㈜파인켐 | 카르밤산염 유도체 화합물 제조방법 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4118585B1 (zh) * | 1963-11-04 | 1966-10-26 | ||
GB1408877A (en) * | 1971-12-07 | 1975-10-08 | Boots Co Ltd | Substituted imidazoles and their use as pesticides |
GB1469772A (en) * | 1973-06-21 | 1977-04-06 | Boots Co Ltd | Fungicidal imidazole derivatives |
JPS5816639A (ja) * | 1981-04-23 | 1983-01-31 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | 塩、レシチン及び親水性シリカを含有する脂肪組成物 |
DE3134933A1 (de) * | 1981-09-03 | 1983-03-31 | Hoechst Ag, 6230 Frankfurt | "harnstoffderivate, verfahren zu ihrer herstellung und diese enthaltende medikamente sowie deren verwendung" |
JPS58152863A (ja) * | 1982-03-04 | 1983-09-10 | Sumitomo Chem Co Ltd | カルボニルジイミノビスベンゼンスルホニルクロリド類の製造方法 |
US4957933A (en) * | 1989-04-21 | 1990-09-18 | E. I. Du Pont De Nemours And Company | Fungicidal oxazolidinones |
US5270317A (en) * | 1990-03-20 | 1993-12-14 | Elf Sanofi | N-substituted heterocyclic derivatives, their preparation and the pharmaceutical compositions in which they are present |
JP3021705B2 (ja) * | 1991-03-01 | 2000-03-15 | 住友化学工業株式会社 | 対称型1,3−ジ置換尿素の製造法 |
HU215699B (hu) * | 1992-11-13 | 1999-02-01 | E. I. Du Pont De Nemours And Co. | Eljárás 2,4-oxazolidin-dionok és intermedierjeik előállítására |
DE4424400A1 (de) | 1994-07-11 | 1996-01-18 | Bayer Ag | Verbessertes Verfahren zur Herstellung von N,N'-Carbonyldiazolen, insbesondere N,N'-Carbonyldiimidazol |
JPH08253456A (ja) * | 1995-03-17 | 1996-10-01 | Mitsubishi Chem Corp | 2−ペルヒドロピリミジノン誘導体及びそれを有効成分とする除草剤、並びにその製造中間体 |
EP1019381A1 (en) * | 1997-01-17 | 2000-07-19 | Ppg Industries, Inc. | Method of producing n,n'-diazole compounds |
DE19833913A1 (de) * | 1998-07-28 | 2000-02-03 | Bayer Ag | Verfahren zur Herstellung von N,N'-Carbonyldiazolen |
-
1998
- 1998-07-08 DE DE19830556A patent/DE19830556A1/de not_active Withdrawn
-
1999
- 1999-07-06 DE DE59907811T patent/DE59907811D1/de not_active Expired - Fee Related
- 1999-07-06 HU HU0102739A patent/HUP0102739A3/hu unknown
- 1999-07-06 US US09/720,913 patent/US6353115B1/en not_active Expired - Fee Related
- 1999-07-06 WO PCT/EP1999/004729 patent/WO2000002863A1/de active Search and Examination
- 1999-07-06 KR KR1020017000204A patent/KR20010071762A/ko not_active Application Discontinuation
- 1999-07-06 CA CA002336657A patent/CA2336657C/en not_active Expired - Fee Related
- 1999-07-06 JP JP2000559094A patent/JP2002520318A/ja active Pending
- 1999-07-06 AU AU54098/99A patent/AU5409899A/en not_active Abandoned
- 1999-07-06 CN CNB998083860A patent/CN1214012C/zh not_active Expired - Fee Related
- 1999-07-06 EP EP99939989A patent/EP1095024B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
WO2000002863A1 (de) | 2000-01-20 |
DE19830556A1 (de) | 2000-01-13 |
HUP0102739A3 (en) | 2003-03-28 |
DE59907811D1 (de) | 2003-12-24 |
KR20010071762A (ko) | 2001-07-31 |
EP1095024A1 (de) | 2001-05-02 |
HUP0102739A2 (hu) | 2001-11-28 |
US6353115B1 (en) | 2002-03-05 |
JP2002520318A (ja) | 2002-07-09 |
CN1308613A (zh) | 2001-08-15 |
CA2336657A1 (en) | 2000-01-20 |
EP1095024B1 (de) | 2003-11-19 |
CA2336657C (en) | 2009-02-24 |
AU5409899A (en) | 2000-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0225823B1 (fr) | Procédé de préparation de dérivés de la ptéridine | |
CN1214012C (zh) | 制备羰基二咪唑的方法 | |
SK8997A3 (en) | Process for the preparation of 5-amino-2,4,6-triiodine-1,3- -benzenedicarboxylic acid | |
RU97120751A (ru) | Способ получения моногидрата ропивакаина гидрохлорида и моногидрат ропивакаина гидрохлорида, полученный этим способом | |
CN1029402C (zh) | 5-氨基-3-氯磺酰基-1,2,4-三唑的制备方法 | |
KR100687167B1 (ko) | α-(2-4-디술포페닐)-N-tert-부틸니트론 및 제약상허용되는 그의 염의 신규 제조 방법 | |
KR20010014340A (ko) | 유사 무수 매질내 클로로포름중 시클로도데칸의광화학니트로소화 반응 | |
JP3821977B2 (ja) | 四級アルキルアンモニウム塩の製造方法 | |
US5847205A (en) | Method for producing homocystine | |
CN1013674B (zh) | 制备n-氨磺酰-3-(2-胍基-噻唑-4-基-甲硫基)-丙脒的方法 | |
US5208351A (en) | Process for the preparation of n-cyanoimidocarbonates | |
JP2002155058A (ja) | 1位置換ヒダントイン類の製造方法 | |
TWI809089B (zh) | 用於製備具有酸不穩定的酮保護基團官能之n-醯化胺基酸酯的方法 | |
US6034280A (en) | Process for the production of 2,5-dimethyl-2,5-di-t-butylperoxy-hexane | |
KR0163344B1 (ko) | 아세토니트릴을 용매로 사용하는 3-니트로-9-에틸카바졸의 제조방법 | |
KR101130793B1 (ko) | 신규한 이온성 액체 및 이를 이용한 이온성 액체의 제조방법 | |
Petrus et al. | Preparation of O-(3-azido-2-hydroxypropyl) cellulose and its photolysis to O-(2-formyl-2-hydroxyethyl) cellulose | |
JP2917497B2 (ja) | 光学活性1,2―プロパンジアミンの製造方法 | |
CN117658963A (zh) | 一种维生素c衍生物的非对映异构体及其制备和应用 | |
US5399678A (en) | Process for sultamicillin intermediate | |
JP3316917B2 (ja) | 新規フェニルアラニン塩結晶とその製造法 | |
KR800001550B1 (ko) | 5-(4-히드록시페닐) 히단토인의 제조법 | |
KR0173545B1 (ko) | 고체산을 이용한 이소프로필티오크산톤의 제조방법 | |
US6437181B1 (en) | Method for producing (S,S)-N,N′-ethylenediaminedisuccinic acid, analogous compounds or salts thereof | |
US6953859B2 (en) | Production process for 5-alkyl-oxazolidin-2,4-dione |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050810 Termination date: 20100706 |