CN106279230B - 一种合成二乙基烷氧基硼烷的工艺 - Google Patents
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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Abstract
本发明公开了一种合成二乙基烷氧基硼烷的工艺，属于硼化学合成领域。将2‑2.2当量乙基格氏试剂或乙基锂与硼化试剂反应，反应结束后淬灭，得到的中间体加入醇和脱水溶剂，精馏后得到二乙基烷氧基硼烷。该方法原料易得，操作方便，比较适合工业化放大合成。
Description
技术领域
本发明涉及一种合成二乙基烷氧基硼烷的工艺，属于硼化学合成领域。
背景技术
阿比特龙是一种CYP17抑制剂，与泼尼松联用治疗既往接受含多烯紫杉醇化疗转移后，作为治疗晚期前列腺癌的靶向药物。其合成中，涉及关键的中间体二乙基(3-吡啶基)硼烷，检索文献和专利发现，该化合物的合成方法不多，但都需要用到二乙基甲氧基硼烷作为硼化试剂。
二乙基甲氧基硼烷的合成目前已有的文献方法主要包括：采用三乙基硼烷与甲醇反应，参考J. Organomet. Chem., 1986 , 314,19;或者采用二乙基硼烷二聚体与甲醇钠反应，参考Gmelin Handbook: B: B-Verb.14,4.4,185；以上方法所用硼试剂原料活性非常高，极易燃烧，工艺放大量制备时，存在极大的安全隐患。
发明内容
为了克服上述缺陷，本发明公开了一种合成二乙基烷氧基硼烷的工艺。将2-2.2当量乙基格氏试剂或乙基锂与硼化试剂反应，反应结束后淬灭，得到的中间体加入醇和脱水溶剂，精馏后得到二乙基烷氧基硼烷。该方法原料易得，操作方便，比较适合工业化放大合成。
一种合成二乙基烷氧基硼烷的工艺，其特征在于包括以下步骤：
控温-20℃以下，将2-2.2当量乙基格氏试剂或乙基锂加入硼化试剂与溶剂的混合溶液中，反应结束后淬灭，调节PH=2-5，有机层干燥后蒸干，加入醇和正庚烷或甲苯，分水结束，精馏后得到二乙基烷氧基硼烷。
进一步地，在上述技术方案中，硼化试剂选自硼酸三甲酯、硼酸三乙酯、硼酸三异丙酯或硼酸三丁酯。
进一步地，在上述技术方案中，醇选自甲醇、乙醇、异丙醇或丁醇。
进一步地，在上述技术方案中，溶剂选自四氢呋喃、2-甲基四氢呋喃、二乙氧基甲烷或环戊基甲基醚。
进一步地，在上述技术方案中，淬灭反应时，可以选用碱淬灭或酸淬灭；选用碱淬灭时，需要再加入酸调节成酸性后，加入溶剂萃取。
进一步地，在上述技术方案中，得到的二乙基烷氧基硼烷可以加入四氢呋喃配制成50%溶液存放。
发明的有益效果
本发明消除了已有合成方法中的工艺安全问题，所采用的工艺方法，反应条件温和，原料廉价易得，操作简便，同时也可以采用此方法得到系列产品，经过保存实验验证，得到的产物稳定性，随着烷氧基中的烷基位阻增加而增加，方便了存放和运输。
具体实施方案
实施例1
在反应瓶内加入硼酸三甲酯（20.8克，0.2摩尔）和2-甲基四氢呋喃80毫升，搅拌均匀后，降温至-50℃，将1M乙基溴化镁2-甲基四氢呋喃（400毫升，0.4摩尔）溶液缓慢滴加入上述溶液，滴加过程中维持反应温度在-50℃至-40℃，滴加完毕，保温反应1-2小时，饱和氯化铵淬灭，有机层饱和食盐水洗涤，无水硫酸镁干燥，蒸干有机层后加入无水甲醇20毫升和正庚烷110毫升回流分水，反应结束，精馏收集得到14.1克无色透明状液体二乙基甲氧基硼烷，收率70%，GC：98.4%，加入四氢呋喃后配制成50%溶液可长时间存放。
实施例2
在反应瓶内加入硼酸三甲酯（20.8克，0.2摩尔）和2-甲基四氢呋喃80毫升，搅拌均匀后，降温至-60℃，将2M乙基氯化镁2-甲基四氢呋喃（200毫升，0.4摩尔）溶液缓慢滴加入上述溶液，滴加过程中维持反应温度在-60℃至-50℃，滴加完毕，保温反应1-2小时，饱和氯化铵淬灭，分层后，饱和食盐水洗涤，无水硫酸镁干燥，蒸干有机层后加入无水乙醇22毫升和正庚烷110毫升回流分水，反应结束，精馏收集得到16.6克二乙基乙氧基硼烷，收率73%，GC：98.1%。
实施例3
在反应瓶内加入硼酸三异丙酯（37.6克，0.2摩尔）和四氢呋喃80毫升，搅拌均匀后，降温至-70℃，将1.3M乙基锂乙醚溶液（338毫升，0.44摩尔）溶液缓慢滴加入上述溶液，滴加过程中维持反应温度在-70℃至-60℃，滴加完毕，保温反应1-2小时，加入氢氧化钠淬灭，有机层弃去，水层加入盐酸和乙酸乙酯后调节PH=3-4，饱和食盐水洗涤，无水硫酸镁干燥，蒸干有机层后加入无水异丙醇25毫升和甲苯120毫升回流分水，反应结束，精馏收集得到17.4克二乙基异丙氧基硼烷，收率68%，GC：98.7%。
Claims (6)
1.一种合成二乙基烷氧基硼烷的工艺，其特征在于包括以下步骤：控温-20℃以下，将2-2.2当量乙基格氏试剂或乙基锂加入硼化试剂与溶剂的混合溶液中，反应结束后淬灭，调节pH=2-5，有机层干燥后蒸干，加入醇和正庚烷或甲苯，分水结束，精馏后得到二乙基烷氧基硼烷。
2.根据权利要求1所述一种合成二乙基烷氧基硼烷的工艺，其特征在于：硼化试剂选自硼酸三甲酯、硼酸三乙酯、硼酸三异丙酯或硼酸三丁酯。
3.根据权利要求1所述一种合成二乙基烷氧基硼烷的工艺，其特征在于：醇选自甲醇、乙醇、异丙醇或丁醇。
4.根据权利要求1所述一种合成二乙基烷氧基硼烷的工艺，其特征在于：溶剂选自四氢呋喃、2-甲基四氢呋喃、二乙氧基甲烷或环戊基甲基醚。
5.根据权利要求1所述一种合成二乙基烷氧基硼烷的工艺，其特征在于：淬灭反应时，选用碱淬灭或酸淬灭；选用碱淬灭时，需要再加入酸调节成酸性后，加入溶剂萃取。
6.根据权利要求1所述一种合成二乙基烷氧基硼烷的工艺，其特征在于：得到的二乙基烷氧基硼烷可以加入四氢呋喃配制成50%溶液存放。
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| 二乙基甲氧基硼烷的工业合成;谢贤清等;《现代化工》;20150720;第35卷(第7期);第115-117页 * |
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