CN104788481B - 一种制备环戊(己)烯-1-硼酸频那醇酯的方法 - Google Patents
一种制备环戊(己)烯-1-硼酸频那醇酯的方法 Download PDFInfo
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Abstract
本发明公开了一种从环戊(己)烯‑1‑羧酸甲酯出发,经过三步连续操作制备环戊(己)烯‑1‑硼酸频那醇酯的方法。首先原料经过碱解形成相应的烯基‑1‑羧酸;随后与溴素加成,接着在DBU或DMAP存在下,同时发生消除和脱羧生成环戊(己)烯‑1‑溴;最后环戊(己)烯‑1‑溴、甲氧基硼酸频那醇酯在金属镁存在下一锅法成酯得到环戊(己)烯‑1‑硼酸频那醇酯。本发明所提供的工艺方法连续性强,操作简便,无需低温反应,同时也可以高纯度得到环戊(己)烯‑1‑澳中间体,满足市场上需求。一锅法格氏/酯化,操作上更便捷,副产物少,产品更容易精馏提纯。
Description
技术领域
本发明涉及一种制备环戊(己)烯-1-硼酸频那醇酯的方法,属于药物中间体合成领域。
背景技术
环戊(己)烯基硼酸酯的合成一直以来都是硼化学中研究中的难点,已有的合成方法主要包括:1)从环酮出发,经过1-2步先变成环烯-1-氯/溴/碘/OTf,然后在乙醚中与金属锂和硼试剂(参考:WO2012/148511A1)或金属钯催化下与联硼酸频那醇酯偶联得到(参考:J.Am.Chem.Soc.,2002,124,8001);2)从环酮出发,在铜催化下与联硼酸频那醇酯发生加成,随后在TsOH存在下发生消除后得到(参考:J.Org.Chem.,2014,79,7199);3)从环酮出发,先与TsNHNH2发生脱水反应,随后再与金属锂和硼试剂超低温下反应得到(参考:Tetrahedron,2014,70,678)。
以上合成方法存在成本高,所用溶剂不适合放大,需要超低温等缺点。
发明内容
为了克服上述缺点,本发明采用了从市场上易得的原料出发,经过水解,加成/脱羧消除和一锅法格氏/酯化三个步骤后得到产品。本发明提供了一种制备环戊(己)烯-1-硼酸频那醇酯的方法,包括以下步骤:本文中提到的“环戊(己)烯”字样指的是“环戊烯或环己烯”。
第一步,环戊(己)烯-1-羧酸甲酯在碱性条件下发生水解反应生成环戊(己)烯-1-羧酸;
第二步,在有机溶剂中,环戊(己)烯-1-羧酸与Br2发生加成反应,然后加入DBU或DMAP,同时发生消除反应和脱羧反应生成环戊(己)烯-1-溴;
第三步,缓慢滴加环戊(己)烯-1-溴、甲氧基硼酸频那醇酯和四氢呋喃混合溶液到金属镁和几小粒引发剂单质碘中,反应后得到环戊(己)烯-1-硼酸频那醇酯。
进一步地,所述第二步中有机溶剂为CH2Cl2。
进一步地,所述第二步中环戊(己)烯-1-羧酸与Br2的摩尔比为1∶0.98-1。
进一步地,所述第二步中环戊(己)烯-1-羧酸与DBU或DMAP的摩尔比为1∶1-5。
进一步地,所述第三步中环戊(己)烯-1-溴与金属镁、甲氧基硼酸频那醇酯的摩尔比为1∶1.1-1.2∶1.2-1.5。
进一步地,所述第三步中四氢呋喃用量为原料环戊(己)烯-1-溴重量的5-15倍。
反应式如下图:
发明有益效果
本发明所提供的工艺方法连续性强,操作简便,无需低温反应,同时也可以高纯度得到环戊(己)烯-1-溴,满足了市场上需求。一锅法格氏/酯化,操作上更便捷,副产物少,产品容易精馏提纯。
具体实施方式
实施例1:一种制备环戊烯-1-硼酸频那醇酯的方法,包括以下步骤:
在反应瓶内加入环戊烯-1-羧酸甲酯126g(1mol)和二氯甲烷280mL,室温下慢慢加入3M KOH水溶液500mL(1.5mol),加入完毕后,搅拌反应1-2小时,TLC检测原料消失后,再加入2M盐酸调PH为4-5,分出有机层,水层再加入150mL二氯甲烷,再次分层后,合并有机层后,饱和食盐水洗涤,得到环戊烯-1-羧酸的二氯甲烷溶液,GC检测纯度大于98%(扣除溶剂后),直接用于下步反应中。
在装有滴加漏斗、回流冷凝器和蒸馏装置的反应瓶内加入上述环戊烯-1-羧酸的二氯甲烷溶液,室温下分3-4批滴加入溴素148g(0.93mol),每次待上次滴入的溴素颜色消失后,再接着加入。加入完毕后,先室温搅拌反应30分钟,TLC(茚三酮显色)检测不到原料后,再补加1-3%的环戊烯-1-羧酸,减压蒸馏溶剂至不流液后,加入100mL环丁砜溶解,升温至40-50度,开始滴加495g DBU(3.23mol),滴加过程中有气泡冒出,根据气泡的逸出快慢控制滴加DBU的速度,滴加完毕后,待气泡不再逸出时,升温至80-90度反应2-3小时,减压蒸馏得到浅黄色液体环戊烯-1-溴89.6g,两步收率61%。如需得到无色产品,需要再次精馏纯化,回收率96%,颜色不影响下步反应进行。1H-NMR(400MHz,CDCl3):5.82(m,1H),2.57-2.62(m,2H),2.30-2.36(m,2H),1.96-2.03(m,2H)。
氮气保护下,在反应瓶内加入金属镁8.0g(0.33mol)和几粒碘,在滴液漏斗里事先加入混合均匀的甲氧基硼酸频那醇酯56.9g(0.36mol)、环戊烯-1-溴44g(0.3mol)和无水四氢呋喃320mL,外浴升温至40-45度,先滴加入25mL混合溶液,待碘颜色消失格氏引发后,维持内温在40-55度之间将剩余的混合溶液滴加完毕,随后逐渐升温至回流继续反应2-3小时,GC检测原料消失后,将反应液降至0-10度,缓慢加入饱和NH4Cl淬灭,调PH为5-6,分出有机层,水层再用MTBE180mL萃取一次,合并有机层,饱和食盐水洗涤,有机层减压浓缩将溶剂蒸干,随后更换高真空油泵,收集64-66℃馏分,得到无色透明液体45.4g,收率78%。1H-NMR(400MHz,CDCl3):6.55(m,1H),2.38-2.47(m,4H),1.80-1.88(m,2H),1.29(s,12H)。
实施例2:一种制备环己烯-1-硼酸频那醇酯的方法,包括以下步骤:
在反应瓶内加入环己烯-1-羧酸甲酯70g(0.5mol)和二氯甲烷200mL,室温下慢慢加入3M KOH水溶液250mL(0.75mol),加入完毕后,搅拌反应1-2小时,TLC检测原料消失后,再加入6M盐酸调PH为4-5,分出有机层,水层再加入100mL二氯甲烷,再次分层后,合并有机层后,饱和食盐水洗涤,得到环己烯-1-羧酸的二氯甲烷溶液,GC检测纯度大于97%(扣除溶剂后),直接用于下步反应中。
在装有滴加漏斗、回流冷凝器和蒸馏装置的反应瓶内加入上述环己烯-1-羧酸的二氯甲烷溶液,室温下分3-4批滴加入溴素76.8g(0.48mol),每次待上次滴入的溴素颜色消失后,再接着加入。加入完毕后,先室温搅拌反应30分钟,TLC(茚三酮显色)检测不到原料后,再补加1-3%的环己烯-1-羧酸,减压蒸馏溶剂至不流液后,加入50mL环丁砜溶解,升温至45-50度,开始滴加61g DMAP(1mol)的环丁砜溶液,滴加过程中有气泡冒出,根据气泡的逸出快慢控制滴加DBU的速度,滴加完毕后,待气泡不再逸出时,升温至80-90度反应2-4小时,减压蒸馏得到浅黄色液体环己烯-1-溴53g,两步收率66%。如需得到无色产品,需要再次精馏纯化,回收率95%,颜色不影响下步反应进行。1H-NMR(400MHz,CDCl3):6.05(m,1H),2.38-2.46(m,2H),2.02-2.11(m,2H),1.70-1.76(m,2H),1.56-1.62(m,2H)。
氮气保护下,在反应瓶内加入金属镁8.0g(0.33mol)和几粒碘,在滴液漏斗里事先加入混合均匀的甲氧基硼酸频那醇酯56.9g(0.36mol)、环己烯-1-溴48.3g(0.3mol)和无水四氢呋喃300mL,外浴升温至40-45度,先滴加入25mL混合溶液,待碘颜色消失格氏引发后,维持内温在40-55度之间将剩余的混合溶液滴加完毕,随后逐渐升温至回流继续反应2-3小时,GC检测原料消失后,将反应液降至0-10度,缓慢加入饱和NH4Cl淬灭,调PH为5-6,分出有机层,水层再用MTBE 150mL萃取一次,合并有机层,饱和食盐水洗涤,有机层减压浓缩将溶剂蒸干,随后更换高真空油泵,收集80-83℃馏分,得到无色透明液体50.5g,收率81%。1H-NMR(400MHz,CDCl3):6.57(m,1H),2.10(m,4H),1.60(m,4H),1.26(s,12H)。
Claims (6)
1.一种制备环戊/己烯-1-硼酸频那醇酯的方法,其特征在于包括以下步骤:
第一步,环戊/己烯-1-羧酸甲酯在碱性条件下发生水解反应生成环戊/己烯-1-羧酸;
第二步,在有机溶剂中,环戊/己烯-1-羧酸与Br2发生加成反应,然后加入DBU或DMAP,同时发生消除反应和脱羧反应生成环戊/己烯-1-溴;
第三步,缓慢滴加环戊/己烯-1-溴、甲氧基硼酸频那醇酯和四氢呋喃混合溶液到金属镁和几小粒引发剂单质碘中,反应后得到环戊/己烯-1-硼酸频那醇酯。
2.根据权利要求1所述一种制备环戊/己烯-1-硼酸频那醇酯的方法,其特征在于:所述第二步中有机溶剂为CH2Cl2。
3.根据权利要求1所述一种制备环戊/己烯-1-硼酸频那醇酯的方法,其特征在于:所述第二步中环戊/己烯-1-羧酸与Br2的摩尔比为 1:0.98-1。
4.根据权利要求1所述一种制备环戊/己烯-1-硼酸频那醇酯的方法,其特征在于:所述第二步中环戊/己烯-1-羧酸与DBU或DMAP的摩尔比为1:1-5。
5.根据权利要求1所述一种制备环戊/己烯-1-硼酸频那醇酯的方法,其特征在于:所述第三步中环戊/己烯-1-溴与金属镁、甲氧基硼酸频那醇酯的摩尔比为1 :1.1-1.2:1.2-1.5。
6.根据权利要求1所述一种制备环戊/己烯-1-硼酸频那醇酯的方法,其特征在于:所述第三步中四氢呋喃用量为原料环戊/己烯-1-溴重量的5-12倍。
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