CN116655526B - 一种合成3-溴-2-（溴甲基）吡啶的方法 - Google Patents
一种合成3-溴-2-（溴甲基）吡啶的方法 Download PDFInfo
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- FVIZOBDAEIFYGH-UHFFFAOYSA-N 3-bromo-2-(bromomethyl)pyridine Chemical compound BrCC1=NC=CC=C1Br FVIZOBDAEIFYGH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims abstract description 16
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000013067 intermediate product Substances 0.000 claims abstract description 12
- KBDIRPOTVAODSA-UHFFFAOYSA-N 3-bromopyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=C1Br KBDIRPOTVAODSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000010025 steaming Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003039 volatile agent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001262 acyl bromides Chemical class 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- -1 lithium aluminum hydride Chemical compound 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AIPWPTPHMIYYOX-UHFFFAOYSA-N 3-bromo-2-methylpyridine Chemical compound CC1=NC=CC=C1Br AIPWPTPHMIYYOX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
本发明涉及医药中间体技术领域，尤其涉及一种合成3‑溴‑2‑（溴甲基）吡啶的方法，包括以下步骤：S1、向反应瓶中加入二氯甲烷，搅拌后加入3‑溴‑2‑吡啶羧酸，搅拌并降温后滴加三溴化磷，然后升温至室温并搅拌4‑6h，减压浓缩，90‑100℃蒸至无馏分，得到中间产物；S2、将上述中间产物加入含有二氯乙烷的反应瓶中，搅拌溶解后加入二苄醚和铁粉，在45‑54℃的温度下搅拌8h，过滤，得到滤液，去除滤液中的挥发物，析晶，过滤，烘干，得到目标产物。采用3‑溴‑2‑羧酸吡啶为原料，通过三溴化磷转化成酰溴，再用铁粉还原成目标产物，整个操作步骤简单，原料价格便宜。
Description
技术领域
本发明涉及医药中间体技术领域，尤其涉及一种合成3-溴-2-(溴甲基)吡啶的方法。
背景技术
3-溴-2-(溴甲基)吡啶是许多抗病毒药物以及嘧啶类抗癌药物合成的中间体，其在药物合成上具有很重要的作用。目前，3-溴-2-（溴甲基）吡啶常用的合成方法有以下几种：
第一种：以3-溴-2-羧酸吡啶为原料用氢化铝锂还原得到醇，再用三溴化磷进行溴代反应。此过程用到氢化铝锂，在生产存在较大的安全隐患，且不易于大生产操作，其反应原理为：。
第二种：采用2-甲基-3-溴吡啶为原料，通过NBS上溴，该工艺原料贵，且收率较低，其反应原理为：。
发明内容
为了解决上述技术问题，本发明提供一种合成3-溴-2-（溴甲基）吡啶的方法。
本发明提供的一种合成3-溴-2-（溴甲基）吡啶的方法采用如下技术方案：
一种合成3-溴-2-（溴甲基）吡啶的方法，包括以下步骤：
S1、向反应瓶中加入二氯甲烷，搅拌后加入3-溴-2-吡啶羧酸，搅拌并降温后滴加三溴化磷，然后升温至室温并搅拌4-6h，减压浓缩，90-100℃蒸至无馏分，得到中间产物，其反应原理为：；
S2、将上述中间产物加入含有二氯乙烷的反应瓶中，搅拌溶解后加入二苄醚和铁粉，在45-54℃的温度下搅拌8h，过滤，得到滤液，去除滤液中的挥发物，析晶，过滤，烘干，得到目标产物，其反应原理为：。
优选的，S1中二氯甲烷、3-溴-2-羧酸吡啶与三溴化磷的质量之比为：4:0.9:1.1。
优选的，S1中搅拌并降温至温度为0-5℃。
优选的，S2中二苄醚和铁粉的质量比为9:1。
优选的，将S2中的粗产物添加到乙腈中进行析晶。
优选的，滤液在旋转蒸发器中减压去除滤液中的挥发物。
综上所述，本发明具有如下的有益技术效果：
1.该合成3-溴-2-（溴甲基）吡啶的方法的创新点在于：采用3-溴-2-羧酸吡啶为原料，通过三溴化磷转化成酰溴，再用铁粉还原成目标产物，整个操作步骤简单，原料价格便宜。
2.添加3-溴-2-羧酸吡啶和三溴化磷作为反应物，三溴化磷取代3-溴-2-羧酸吡啶中的羧酸形成酰溴，选择性地进行溴代反应，只在目标化合物的特定位置引入溴原子，副产少。
3.该方法合成的3-溴-2-（溴甲基）吡啶反应条件温和，便于控制，安全性较高，收率高，适合放大生产。
附图说明
图1是本发明产品的核磁共振图；
图2是本发明产品的气相色谱图。
具体实施方式
实施例1
向反应瓶中加入二氯甲烷4kg，搅拌，加入3-溴-2-羧酸吡啶900g，搅拌并降温，控制温度0-5℃，滴加1.1kg三溴化磷，升至室温并搅拌4-6h，减压浓缩，90-100℃蒸至无馏分，得到中间产物。
将上述中间产物添加到含有10L二氯乙烷的反应瓶中，搅拌溶解，之后加入900g二苄醚和100g铁粉，在45℃下搅拌8h，过滤去除不溶物，滤液在旋转蒸发器中减压除去挥发物，加入乙腈后析晶，过滤，烘干，得到目标产物3-溴-2-（溴甲基）吡啶905g，收率为80.92%。
第二步的反应原理为：
实施例2
向反应瓶中加入二氯甲烷2kg，搅拌，加入3-溴-2-羧酸吡啶450g，搅拌并降温，控制温度0-5℃，滴加0.55kg三溴化磷，升至室温并搅拌4-6h，减压浓缩，90-100℃蒸至无馏分，得到中间产物。
将上述中间产物添加到含有5L二氯乙烷的反应瓶中，搅拌溶解，之后加入450g二苄醚和50g铁粉，在45℃下搅拌8h，过滤去除不溶物，滤液在旋转蒸发器中减压除去挥发物，加入乙腈后析晶，过滤，烘干，得到目标产物3-溴-2-（溴甲基）吡啶454g，收率为81.19%。
第二步的反应原理为：
实施例3
向反应瓶中加入二氯甲烷8kg，搅拌，加入3-溴-2-羧酸吡啶1.8kg，搅拌并降温，控制温度0-5℃，滴加2.2kg三溴化磷，升至室温并搅拌4-6h，减压浓缩，90-100℃蒸至无馏分，得到中间产物。
将上述中间产物添加到含有20L二氯乙烷的反应瓶中，搅拌溶解，之后加入1.8kg二苄醚和200g铁粉，在45℃下搅拌8h，过滤去除不溶物，滤液在旋转蒸发器中减压除去挥发物，加入乙腈后析晶，过滤，烘干，得到目标产物3-溴-2-（溴甲基）吡啶1807g，收率为80.79%。
第二步的反应原理为：
以上均为本发明的较佳实施例，并非依此限制本发明的保护范围，故：凡依本发明的结构、形状、原理所做的等效变化，均应涵盖于本发明的保护范围之内。
Claims (6)
1.一种合成3-溴-2-（溴甲基）吡啶的方法，其特征在于：包括以下步骤：
S1、向反应瓶中加入二氯甲烷，搅拌后加入3-溴-2-吡啶羧酸，搅拌并降温后滴加三溴化磷，然后升温至室温并搅拌4-6h，减压浓缩，90-100℃蒸至无馏分，得到中间产物，其反应原理为：；
S2、将上述中间产物加入含有二氯乙烷的反应瓶中，搅拌溶解后加入二苄醚和铁粉，在45-54℃的温度下搅拌8h，过滤，得到滤液，去除滤液中的挥发物，析晶，过滤，烘干，得到目标产物，其反应原理为：。
2.根据权利要求1所述的一种合成3-溴-2-（溴甲基）吡啶的方法，其特征在于：S1中二氯甲烷、3-溴-2-羧酸吡啶与三溴化磷的质量之比为：4:0.9:1.1。
3.根据权利要求1所述的一种合成3-溴-2-（溴甲基）吡啶的方法，其特征在于：S1中搅拌并降温至温度为0-5℃。
4.根据权利要求1所述的一种合成3-溴-2-（溴甲基）吡啶的方法，其特征在于：S2中二苄醚和铁粉的质量比为9:1。
5.根据权利要求1所述的一种合成3-溴-2-（溴甲基）吡啶的方法，其特征在于：将S2中的粗产物添加到乙腈中进行析晶。
6.根据权利要求1所述的一种合成3-溴-2-（溴甲基）吡啶的方法，其特征在于：在S2中，滤液在旋转蒸发器中减压去除滤液中的挥发物。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU872525A1 (ru) * | 1980-01-30 | 1981-10-15 | Одесский Ордена Трудового Красного Знамени Государственный Университет Им.И.И.Мечникова | Способ получени хлористого бензила |
| DE19703906A1 (de) * | 1997-02-03 | 1998-08-06 | Bayer Ag | Verfahren zur Umwandlung von Dibenzylether in Benzylchlorid und Herstellung reiner Salzsäure aus salzsauren Abwässern der Benzylalkoholsynthese |
| CN103380130A (zh) * | 2011-02-18 | 2013-10-30 | 埃科特莱茵药品有限公司 | 用作为食欲素拮抗剂的新颖的吡唑和咪唑衍生物 |
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| US8889839B2 (en) * | 2008-05-07 | 2014-11-18 | Syracuse University | Pyridine-bis (oxazoline)(“pybox”) moiety as a chelator and sensitizer for lanthanide ion (Ln (III)) Luminescence |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU872525A1 (ru) * | 1980-01-30 | 1981-10-15 | Одесский Ордена Трудового Красного Знамени Государственный Университет Им.И.И.Мечникова | Способ получени хлористого бензила |
| DE19703906A1 (de) * | 1997-02-03 | 1998-08-06 | Bayer Ag | Verfahren zur Umwandlung von Dibenzylether in Benzylchlorid und Herstellung reiner Salzsäure aus salzsauren Abwässern der Benzylalkoholsynthese |
| CN103380130A (zh) * | 2011-02-18 | 2013-10-30 | 埃科特莱茵药品有限公司 | 用作为食欲素拮抗剂的新颖的吡唑和咪唑衍生物 |
Non-Patent Citations (1)
| Title |
|---|
| 朱彬.有机合成.西南交通大学出版社,2014,(第第一版版),第196页. * |
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