CN107867987A - 一种alpha,alpha‑二溴代酮的制备方法 - Google Patents

一种alpha,alpha‑二溴代酮的制备方法 Download PDF

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CN107867987A
CN107867987A CN201610861101.7A CN201610861101A CN107867987A CN 107867987 A CN107867987 A CN 107867987A CN 201610861101 A CN201610861101 A CN 201610861101A CN 107867987 A CN107867987 A CN 107867987A
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CN107867987B (zh
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张伟
吴平
胥森瀚
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Fudan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/562—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with nitrogen as the only hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals

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Abstract

本发明属于精细化工产品制备、药物中间体合成领域，涉及一种新的alpha,alpha‑二溴代酮的制备方法，尤其是利用二溴海因或N‑溴代琥珀酰亚胺将烯烃转化为alpha,alpha‑二溴代酮的方法。相比已有报道，本方法原料易得、成本低廉，所用试剂毒性较小，具有较大的成本和环保优势。具有广泛的应用前景。

Description

一种alpha，alpha-二溴代酮的制备方法
技术领域
本发明属于精细化工产品制备、药物中间体合成领域，具体涉及一种新的利用二溴海因或N-溴代琥珀酰亚胺将烯烃转化为alpha,alpha-二溴代酮的方法。
背景技术
alpha,alpha-二溴代酮类化合物在有机化学、药物化学、生物化学以及材料科学中都有广泛的用途。现有技术公开了该类化合物传统的制备方法是以酮为原料，使用溴素或其它溴源进行溴代((1)J.Am.Chem.Soc.1913,35,1770-1774；(2)TetrahedronLett.1984,25,3369-3372；(3)Synth.Commum.2002,32,3711-3717)；此方法需使用毒性较大的试剂，收率较低且操作不便。近年来，研究者转向使用炔烃为原料进行alpha,alpha-二溴代酮的制备(J.Org.Chem.1994,59,5550-5555；(2)J.Org.Chem.2004,69,8561-8563；(3)Adv.Synth.Catal.2005,347,1341-1344)；但该方法大多需要贵金属催化，且原料来源受限，与酮及炔烃相比，烯烃是更容易获得的原料，如，苯乙烯为可轻易获取的大宗化工原料；其它非商品化的烯烃可以由醛做最初原料，经由维蒂希反应制得。
因此，基于现有技术的现状，本申请的发明人拟提供一种新的利用二溴海因或N-溴代琥珀酰亚胺将烯烃转化为alpha,alpha-二溴代酮的方法。本方法使用烯烃为原料制备alpha,alpha-二溴代酮具有较大的优势。
发明内容
本发明的目的是基于现有技术的现状，提供一种新的alpha,alpha-二溴代酮的制备方法，尤其是利用二溴海因或N-溴代琥珀酰亚胺将烯烃转化为alpha,alpha-二溴代酮的方法。相比已有报道，本方法原料易得、成本低廉，所用试剂毒性较小，具有较大的成本和环保优势。
本发明的目的通过下述技术方案实现：
以烯烃为反应物，使用二溴海因或N-溴代琥珀酰亚胺，通过控制烯烃和二 溴海因或N-溴代琥珀酰亚胺的当量比及反应时间，制备得alpha,alpha-二溴代酮。
更具体的，本发明提供了一种alpha,alpha-二溴代酮的制备方法，其特征在于，该方法以烯烃为原料、使用二溴海因或N-溴代琥珀酰亚胺将烯烃转化为alpha,alpha-二溴代酮。
本发明中，所述的烯烃具有如下结构特征：
式中，R1、R2选自以下基团：C1～C30的直链或支链烷基，C1～C30的直链或支链烷氧基，酯基，氢，芳香环或芳杂环；
所述的R1和R2还可以通过环合的形式组成环状烯烃。
本发明方法中，按下述合成路线制备alpha,alpha-二溴代酮：
式中，R1、R2选自：C1～C30的直链或支链烷基，C1～C30的直链或支链烷氧基，酯基，氢，芳香环或芳杂环；其中，R1和R2还可以通过环合的形式组成环状烯烃。
本发明方法中，选用的溶剂可以是水、醇类、醚类、烃类、酮类或由它们组成的混合物；
本发明方法转化条件中，二溴海因(或N-溴代琥珀酰亚胺)与烯烃的摩尔比为1：1～20：1；
本发明方法转化条件中，反应温度为0～150摄氏度；
本发明方法转化条件中，反应时间为0.5～24小时。
本发明提供了一种alpha,alpha-二溴代酮的制备方法，其具有的优点有，本发明的方法条件温和、易于操作，所采用原料易得、成本低廉，所用试剂毒性较小，具有较大的成本和环保优势，具有广泛的应用前景。
为了便于理解，以下将通过具体的实施例对本发明进行详细地描述。需要特别指出的是，具体实例仅是为了说明，显然本领域的普通技术人员可以根据本文说明，在本发明的范围内对本发明做出各种各样的修正和改变，这些修正和改变也纳入本发明的范围内。另外，本发明引用了公开文献，这些文献是为了更清楚地描述本发明，它们的全文内容均纳入本文进行参考，就好像它们的全文已经在本文中重复叙述过一样。
具体实施方式
制备通法：将二溴海因(或N-溴代琥珀酰亚胺)3mmol，烯烃1mmol，加入5ml的乙二醇二甲醚中，再加入0.5ml水，然后加热至80摄氏度并搅拌4h。向体系中加入足量Na2SO3固体后以乙酸乙酯萃取三次，分出有机层，减压浓缩除去有机溶剂，通过柱层析或重结晶分离，得到产物。
实施例1 制备2,2-二溴苯乙酮
以苯乙烯为原料，按通法制备，收率87％，产物的核磁共振波谱数据如下： 1HNMR(400MHz,CDCl3)δ8.10–8.05(m,2H),7.64(t,J＝7.4Hz,1H),7.51(t,J＝7.7Hz,2H),6.72(s,1H)。
实施例2 制备2,2-二溴-2’-甲基苯乙酮
以邻甲基苯乙烯为原料，按通法制备，收率70％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ7.68(d,J＝7.6Hz,1H),7.46(t,J＝7.3Hz,1H),7.34–7.28(m,2H),6.68(s,1H),2.52(s,3H)。
实施例3 制备2,2-二溴-4’-甲基苯乙酮
以对甲基苯乙烯为原料，按通法制备，收率80％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ7.98(d,J＝8.3Hz,2H),7.31(d,J＝8.0Hz,2H),6.70(s,1H),2.44(s,3H)。
实施例4 2,2,3’-三溴苯乙酮
以间溴苯乙烯为原料，按通法制备，收率81％。产物的核磁共振波谱数据如 下：1HNMR(400MHz,CDCl3)δ8.21(s,1H),8.03(d,J＝7.0Hz,1H),7.76(d,J＝7.6Hz,1H),7.44–7.36(m,1H),6.61(s,1H)。
实施例5 制备2,2,4’-三溴苯乙酮
以对溴苯乙烯为原料，按通法制备，收率75％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ7.98(d,J＝7.0Hz,2H),7.66(d,J＝7.4Hz,2H),6.60(s,1H)。
实施例6 制备2,2-二溴-3’-硝基苯乙酮
以间硝基苯乙烯为原料，按通法制备，收率33％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ8.96(s,1H),8.52–8.45(m,2H),7.75(t,J＝8.0Hz,1H),6.62(s,1H)。
实施例7 制备2,2-二溴-4’-硝基苯乙酮
以对硝基苯乙烯为原料，按通法制备，收率49％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ8.35(d,J＝8.9Hz,2H),8.30(d,J＝8.8Hz,2H),6.60(s,1H)。
实施例8 制备2,2-二溴-1-(2-吡啶基)-1-乙酮
以2-乙烯基吡啶为原料，按通法制备，收率63％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ8.70(d,J＝3.9Hz,1H),8.19(d,J＝7.8Hz,1H),7.92(t,J＝7.7Hz,1H),7.64(s,1H),7.61–7.53(m,1H)。
实施例9 2,2-二溴-1-四氢萘酮
以1,2-二氢萘为原料，按通法制备，收率74％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ8.18(d,J＝7.9Hz,1H),7.56(t,J＝7.4Hz,1H),7.40(t,J＝7.3Hz,1H),7.27(d,J＝7.1Hz,1H),3.10(d,J＝7.1Hz,4H)。
实施例10 制备1,1-二溴-4’-叔丁基苯乙酮
以4-叔丁基苯乙烯为原料，按通法制备，收率91％。产物的核磁共振波谱数据如下：1HNMR(400MHz,CDCl3)δ8.03(d,J＝8.5Hz,2H),7.52(d,J＝8.5Hz,2H),6.71(s,1H),1.35(s,9H)。

Claims (7)

1.一种alpha,alpha-二溴代酮的制备方法，其特征在于该方法以烯烃为原料、使用二溴海因或N-溴代琥珀酰亚胺将烯烃转化为alpha,alpha-二溴代酮。
2.如权利要求1所述的制备方法，其特征在于，所述的烯烃具有如下结构特征：
式中，R1、R2选自以下基团：C1～C30的直链或支链烷基，C1～C30的直链或支链烷氧基，酯基，氢，芳香环或芳杂环；
R1和R2还通过环合的形式组成环状烯烃。
3.如权利要求1所述的制备方法，其特征在于，该制备方法中，按下述合成路线图制备alpha,alpha-二溴代酮：
式中，R1、R2选自：C1～C30的直链或支链烷基，C1～C30的直链或支链烷氧基，酯基，氢，芳香环或芳杂环；其中，R1和R2还通过环合的形式组成环状烯烃。
4.如权利要求1所述的制备方法，其特征在于，该方法中采用的转化条件，其中二溴海因或N-溴代琥珀酰亚胺与烯烃的摩尔比为1：1～20：1。
5.如权利要求1所述的制备方法，其特征在于，该方法中采用的转化条件，其中反应温度为0～150摄氏度。
6.如权利要求1所述的制备方法，其特征在于，该方法中采用的转化条件，其中反应时间为0.5～24小时。
7.如权利要求1所述的制备方法，其特征在于，该方法中采用的溶剂是水、醇类、醚类、烃类、酮类或由它们组成的混合物。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409159A (zh) * 2020-11-19 2021-02-26 北京科技大学 一种氧化-氯化法合成扁桃酸的方法
CN114805044A (zh) * 2021-01-19 2022-07-29 兰州大学 一种新型合成二溴化合物的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108069839A (zh) * 2016-11-10 2018-05-25 复旦大学 利用二溴海因将烯烃转化为alpha-溴代酮的方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108069839A (zh) * 2016-11-10 2018-05-25 复旦大学 利用二溴海因将烯烃转化为alpha-溴代酮的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAMAL KRISHNA RAJBONGSHI，等: "Metal-free protocol for the synthesis of a-bromo ketones from olefins using TsNBr2", 《TETRAHEDRON LETTERS》 *
VALERIA CONTE，等: "Oxybromination of Ethynylbenzene Catalysed by Molybdenum Complexes in Organic Solvent and in Ionic Liquids", 《ADV. SYNTH. CATAL.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409159A (zh) * 2020-11-19 2021-02-26 北京科技大学 一种氧化-氯化法合成扁桃酸的方法
CN112409159B (zh) * 2020-11-19 2022-04-15 北京科技大学 一种氧化-氯化法合成扁桃酸的方法
CN114805044A (zh) * 2021-01-19 2022-07-29 兰州大学 一种新型合成二溴化合物的方法

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