CN104496906B - 一种咪唑的制备方法 - Google Patents
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- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 3
- LEZWWPYKPKIXLL-UHFFFAOYSA-N 1-{2-(4-chlorobenzyloxy)-2-(2,4-dichlorophenyl)ethyl}imidazole Chemical compound C1=CC(Cl)=CC=C1COC(C=1C(=CC(Cl)=CC=1)Cl)CN1C=NC=C1 LEZWWPYKPKIXLL-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- BYBLEWFAAKGYCD-UHFFFAOYSA-N Miconazole Chemical group ClC1=CC(Cl)=CC=C1COC(C=1C(=CC(Cl)=CC=1)Cl)CN1C=NC=C1 BYBLEWFAAKGYCD-UHFFFAOYSA-N 0.000 description 2
- 229960004022 clotrimazole Drugs 0.000 description 2
- VNFPBHJOKIVQEB-UHFFFAOYSA-N clotrimazole Chemical compound ClC1=CC=CC=C1C(N1C=NC=C1)(C=1C=CC=CC=1)C1=CC=CC=C1 VNFPBHJOKIVQEB-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229960003913 econazole Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960002509 miconazole Drugs 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OWEGWHBOCFMBLP-UHFFFAOYSA-N 1-(4-chlorophenoxy)-1-(1H-imidazol-1-yl)-3,3-dimethylbutan-2-one Chemical compound C1=CN=CN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 OWEGWHBOCFMBLP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229960003344 climbazole Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- C07D233/58—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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
本发明公开了一种咪唑的制备方法，它通过氨基乙醛缩二乙醇和丙二酰胺制备得到双咪唑，再由双咪唑制备得到咪唑。与现有技术相比，本发明经过对反应条件和其它试剂用量的不断优化，总转化率可以达到91％，远高于现有工艺。且本发明反应条件温和，反应过程中所用溶剂和催化剂均可回收循环利用，成本较低，适于实用。
Description
技术领域
本发明属于化工领域，具体涉及一种咪唑的制备方法。
背景技术
咪唑是一种重要的精细化工原料，主要用于医药和农药的合成以及环氧树脂的固化剂.在医药中用于咪唑类抗真菌药物，是双氯苯咪唑，益康唑，酮康唑，克霉唑等药物的主要原料之一，还广泛地用于水果的防腐剂.用作环氧树脂固化剂，作为铜的防锈剂，医药、农药原料，也用作脲醛树脂固化剂、摄影药物、粘合剂、涂料、橡胶硫化剂、防静电剂等的原料及有机合成中间体。作为医药工业的中间体，咪唑用于制备克霉唑、咪康唑、益康唑、酮康唑等抗真菌药物；用作环氧树脂的固化剂；用作咪唑衍生物甘宝素、羰基二咪唑等原料；在pH6.2-7.8范围内有效的缓冲液；用于天冬氨酸、谷氨酸滴定。
自然界只存在咪唑衍生物，而无游离的咪唑。目前市场上几种制备咪唑的工艺路线均不如人意，现有技术中转化效率最高的制备方法，收率为76％，不足80％。因此，开发设计出一条高效，实用的制备咪唑的工艺路线，具有十分广阔的市场前景。
发明内容
本发明要解决的技术问题是提供一种高收率的咪唑的制备方法，以解决现有技术在该产品的制备上转化效率较低的问题。
为解决上述技术问题，本发明采用的技术方案如下：
一种咪唑的制备方法，它包括如下步骤：
(1)在反应釜中，将氨基乙醛缩二乙醇溶于水中，以60转/分钟的转速进行搅拌，同时滴加硝酸水溶液；
(2)向步骤(1)中所得的混合体系中加入丙二酰胺，混合充分后130～170℃下反应10～15h；
(3)向步骤(2)中所得的混合体系中加入氯仿进行萃取，取有机相；
(4)向步骤(3)中所得的有机相中加入冰醋酸，混合充分后缓慢加入四氢铝锂粉末，以40转/分钟的转速搅拌3～5h；
(5)将步骤(4)中所得的混合体系过滤，弃去滤渣，过滤后所得的液相常压蒸馏后，即得咪唑。
其中，步骤(1)中，硝酸水溶液的浓度为1.3～2.2mol/L。
其中，步骤(1)中，氨基乙醛缩二乙醇与水的固液比为1g：10～15mL。
其中，步骤(2)中，氨基乙醛缩二乙醇与硝酸水溶液固液比为1g：0.2～0.3mL。
其中，步骤(4)中，氨基乙醛缩二乙醇和丙二酰胺用量的质量比为2.7～3.5：1。
其中，步骤(4)中，四氢铝锂粉末与氨基乙醛缩二乙醇的质量比为1：20～50。
其中，步骤(3)中，所述的氯仿的用量与步骤(1)中水的用量相同。
其中，步骤(3)中，所述的冰醋酸与氯仿的用量的体积比为1：45～60。
本发明反应式如下：
有益效果：与现有技术相比，本发明具有如下优势：本发明采用先用氨基乙醛缩二乙醇和丙二酰胺生成双咪唑，再分解成咪唑的工艺路线，经过对反应条件和其它试剂用量的不断优化，总转化率可以达到91％，远高于现有工艺。且本发明反应条件温和，反应过程中所用溶剂和催化剂均可回收循环利用，成本较低，适于实用。
具体实施方式
实施例1
双咪唑的制备：
(1)在反应釜中，将300g氨基乙醛缩二乙醇溶于4L水中，并滴加1.5mol/L硝酸水溶液80mL，同时以60转/分钟的转速进行搅拌；
(2)向步骤(1)中所得的混合体系中加入100g丙二酰胺，混合充分后150℃下反应10h；
(3)向步骤(2)中所得的混合体系中加入4L氯仿进行萃取，取有机相；
实施例2
由双咪唑制备咪唑：
(1)向实施例1中所得的有机相中加入80ml冰醋酸，混合充分后缓慢加入四氢铝锂粉末10g，以40转/分钟的转速搅拌3h；
(5)将步骤(4)中所得的混合体系过滤，弃去滤渣，过滤后所得的液相常压蒸馏后，即得咪唑。
实施例3
一种咪唑的制备方法，它包括如下步骤：
(1)在反应釜中，将330g氨基乙醛缩二乙醇溶于4L水中，以60转/分钟的转速进行搅拌，同时滴加1.7mol/L硝酸水溶液70mL；
(2)向步骤(1)中所得的混合体系中加入100g丙二酰胺，混合充分后160℃下反应13h；
(3)向步骤(2)中所得的混合体系中加入4L氯仿进行萃取，取有机相；
(4)向步骤(3)中所得的有机相中加入80mL冰醋酸，混合充分后缓慢加入四氢铝锂粉末，以40转/分钟的转速搅拌4.5h；
(5)将步骤(4)中所得的混合体系过滤，弃去滤渣，过滤后所得的液相常压蒸馏后，即得咪唑。
本实施例所述的制备条件下，制备得到咪唑106.8g，产率达到91％。
Claims (6)
1.一种咪唑的制备方法，其特征在于，包括如下步骤：
(1)在反应釜中，将氨基乙醛缩二乙醇溶于水中，以60转/分钟的转速进行搅拌，同时滴加硝酸水溶液；
(2)向步骤(1)中所得的混合体系中加入丙二酰胺，混合充分后130～170℃下反应10～15h；
(3)向步骤(2)中所得的混合体系中加入氯仿进行萃取，取有机相；
(4)向步骤(3)中所得的有机相中加入冰醋酸，混合充分后缓慢加入四氢铝锂粉末，以40转/分钟的转速搅拌3～5h；
(5)将步骤(4)中所得的混合体系过滤，弃去滤渣，过滤后所得的液相常压蒸馏后，即得咪唑；
其中，
步骤(3)中，氯仿的用量与步骤(1)中水的用量相同；
步骤(3)中，冰醋酸与氯仿的体积比为1：45～60。
2.根据权利要求1所述的咪唑的制备方法，其特征在于，步骤(1)中，所述的硝酸水溶液中，溶质硝酸的浓度为1.3～2.2mol/L。
3.根据权利要求1所述的咪唑的制备方法，其特征在于，步骤(1)中，氨基乙醛缩二乙醇与水的固液比为1g：10～15mL。
4.根据权利要求1所述的咪唑的制备方法，其特征在于，步骤(1)中，氨基乙醛缩二乙醇与硝酸水溶液固液比为1g：0.2～0.3mL。
5.根据权利要求1所述的咪唑的制备方法，其特征在于，步骤(2)中，氨基乙醛缩二乙醇和丙二酰胺的质量比为2.7～3.5：1。
6.根据权利要求1所述的咪唑的制备方法，其特征在于，步骤(4)中，四氢铝锂粉末与氨基乙醛缩二乙醇的质量比为1：20～50。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177299A (zh) * | 1995-01-09 | 1998-03-25 | 史密丝克莱恩比彻姆公司 | 用作细胞因子的某些1,4,5－三取代咪唑化合物 |
| CA2783258A1 (en) * | 2009-12-23 | 2011-06-30 | Elan Pharmaceuticals, Inc. | Pteridinones as inhibitors of polo-like kinase |
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2014
- 2014-11-05 CN CN201410619061.6A patent/CN104496906B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177299A (zh) * | 1995-01-09 | 1998-03-25 | 史密丝克莱恩比彻姆公司 | 用作细胞因子的某些1,4,5－三取代咪唑化合物 |
| CA2783258A1 (en) * | 2009-12-23 | 2011-06-30 | Elan Pharmaceuticals, Inc. | Pteridinones as inhibitors of polo-like kinase |
Non-Patent Citations (3)
| Title |
|---|
| Condensation of LActams with 2-AminoacetylaldehydeDiethyl Acetal. A One-Pot Synthesis of Bicyclic Imidazoles;Duy H. Hua, et.al.;《J. Org. Chem.》;19941231;第59卷(第17期);第5084～5087页 * |
| Synthesis of di(imdazolium) and di(pyrazolium) salts;Tatiana V, et.al.;《Procedia Chemistry》;20141031(第10期);第485～489页 * |
| Synthesis of Substituted Imidazoles via Organocatalysis;Doug E. Frantz, et.al.;《ORGANIC LETTERS》;20040211;第6卷(第5期);第843～846页 * |
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Address after: 200042 Yueda International Building A 16C, 1118 Changshou Road, Putuo District, Shanghai Co-patentee after: JIANGSU CALE NEW MATERIAL CO.,LTD. Patentee after: SHANGHAI HAODENG MATERIAL TECHNOLOGY CO.,LTD. Address before: 200042 Yueda International Building A 16C, 1118 Changshou Road, Putuo District, Shanghai Co-patentee before: JIANGSU CALE NEW MATERIALS Co.,Ltd. Patentee before: SHANGHAI HAODENG MATERIAL TECHNOLOGY CO.,LTD. |
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Effective date of registration: 20210114 Address after: 201800 room 1-203, No. 337 Shahe Road, Jiangqiao Town, Jiading District, Shanghai -193 Patentee after: SHANGHAI HOLDEN MATERIAL Co.,Ltd. Address before: 200042 Yueda International Building A 16C, 1118 Changshou Road, Putuo District, Shanghai Patentee before: SHANGHAI HAODENG MATERIAL TECHNOLOGY Co.,Ltd. Patentee before: JIANGSU CALE NEW MATERIAL Co.,Ltd. |
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Denomination of invention: A preparation method of imidazole Effective date of registration: 20230307 Granted publication date: 20160323 Pledgee: Industrial Bank Co.,Ltd. Shanghai Branch Pledgor: SHANGHAI HOLDEN MATERIAL CO.,LTD.|NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd.|JIANGSU CALE NEW MATERIAL CO.,LTD. Registration number: Y2023310000048 |
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Granted publication date: 20160323 Pledgee: Industrial Bank Co.,Ltd. Shanghai Branch Pledgor: SHANGHAI HOLDEN MATERIAL CO.,LTD.|NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd.|JIANGSU CALE NEW MATERIAL CO.,LTD. Registration number: Y2023310000048 |
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Denomination of invention: A preparation method of imidazole Granted publication date: 20160323 Pledgee: Industrial Bank Co.,Ltd. Shanghai Changning sub branch Pledgor: SHANGHAI HOLDEN MATERIAL CO.,LTD.|NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2024310000177 |