CN106699527A - 一种间氯苯丙酮的合成方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
本发明公开了一种间氯苯丙酮的合成方法。镁与溴乙烷在四氢呋喃(THF)溶液生成Grignard试剂,而后与间氯苯甲腈反应生成间氯苯丙酮。该合成方法,操作简单,工艺先进,溶剂可回收利用,易于工业化生产。用该合成方法制得的间氯苯丙酮,收率达到92.6%,液相纯度高达99.93%以上。
Description
技术领域
本发明属于药物中间体化合物合成领域,具体涉及一种间氯苯丙酮的合成方法。
技术背景
安非他酮是一类新型抗抑郁药,而且还能通过阻断神经对多巴胺、5-羟色胺和去甲肾上腺素的摄取而发挥戒烟作用在临床上广泛应用,间氯苯丙酮是合成安非他酮的关键中间体。目前,国内外间氯苯丙酮工业化生产的传统工艺是1,2-二氯乙烷作溶剂,三氯化铝作催化剂,苯丙酮与氯气反应得到间氯苯丙酮,但1,2-二氯乙烷易燃、高毒、且有高致癌性;三氯化铝其蒸气对呼吸道有刺激性而引起支气管炎,并且对皮肤、粘膜具有强烈的刺激作用,且生产时还产生大量的酸性废水,工业化生产十分困难。因此寻求工艺先进,生产成本低,开发间氯苯丙酮的绿色生产工艺势在必行。
以下是近几年改进的2种合成间氯苯丙酮的方法:
1.专利(申请号:200410065482.5)中报道,在1,2-二氯乙烷作溶剂,无水三氯化铝催化下,苯丙酮和氯气发生氯代反应合成间氯苯丙酮,收率为89%。因该方法在合成时使用了大量1,2-二氯乙烷作反应溶剂,长期接触和使用会对人体造成很大的伤害,药厂已经禁止使用含有二氯乙烷残留的间氯苯丙酮作原料生产抗抑郁药安非他酮。
2.在文献(AdvancedSynthesis&Catalysis)中报道,在钯炭催化剂作用下,间氯苯甲酸硫代乙酯与乙基锌反应合成间氯苯丙酮,收率83%。因该方法所用的原材料和催化剂都非常昂贵,成本难以控制,因此不适合工业化生产。
3.在文献(精细石油化工,2005)中报道,以间氯苯甲酸、丙酸为原料,在铁粉和二氧化锰催化下合成间氯苯基丙酮,收率为70%。该方法生产的间氯苯基丙酮含有间氯苯甲酸残留,且第一步缩合反应温度为140℃,第二步脱羧反应温度需要280℃,反应条件苛刻,不适合工业生产。
发明内容
本发明的目的在于克服目前工业上合成间氯苯基丙酮存在成本高、收率低的缺点,提供一种间氯苯基丙酮的绿色合成方法。为解决上述技术问题,本发明采用以下技术方案:
在装有回流冷凝管、滴液漏斗的反应器中加入镁粉、四氢呋喃(THF),从滴液漏斗中滴加溴乙烷,控制反应液温度40-100℃,使溶液一直保持微沸状态,以利于金属镁在四氢呋喃(THF)的作用下完全反应生成Grignard试剂。在搅拌下,将间氯苯甲腈缓慢滴加到Grignard试剂中,乙基溴化镁与间氯苯甲腈发生亲核加成反应生成中间体I,反应3.0-4.0h,反应完毕,冷水浴下滴加3mol/L的盐酸,中间体I发生水解反应,反应完成后,分出无机相,有机相经常压蒸馏除去THF,减压蒸馏,得到间氯苯丙酮,
本发明的有益效果如下:
1、提供的间氯苯丙酮方法,成本低,操作简单,工艺先进,溶剂可回收利用,易于工业化生产。
2、用该合成方法制得的间氯苯丙酮,收率达到92.6%,液相纯度高达99.93%以上。
附图说明
图1为本实施例得到的间氯苯丙酮的1HNMR。
图2为本实施例得到的间氯苯丙酮的GC-MS。
图3为本实施例得到的间氯苯丙酮的液相图谱。
具体实施方式
以下结合实施例对本发明作进一步说明,但本发明要求保护的范围并不局限于实施例表述的范围。
间氯苯丙酮的合成方法如下:
实施例1:
装有回流冷凝管、滴液漏斗的反应器中加入镁粉48.0g(2.0mol),四氢呋喃(THF)溶液400mL,从滴液漏斗中缓慢加入溴乙烷218.0g(2.0mol),控制反应液温度50-60℃,使溶液一直保持微沸状态,滴加完毕后加热回流1.0-1.5h,保证镁反应完全,得到Grignard试剂。搅拌下,将间氯苯甲腈275.2g(2.0mol)缓慢滴加到上述制得的格氏试剂中,滴加完后,反应3.0-4.0h,生成中间体I,反应完毕,不需分离,缓慢滴加3mol/L的盐酸水解中间体I,分出无机相,有机相经常压蒸馏除去THF,减压蒸馏,得到间氯苯丙酮。收率81.2%。1H NMR(DMSO-d6,400MHz)δ:8.021-7.91(m,2H,Ar-H),7.70(d,1H,Ar-H),7.56(d,1H,Ar-H),3.06(q,2H,CH2),1.07(t,3H,CH3).GC-MS m/z(%):168(M+,17.56),139(100.00),111(45.32).
实施例2:
溴乙烷的量增加到239.7g(2.2mol),间氯苯甲腈302.6g(2.2mol),其它同实例1,间氯苯丙酮的收率为85.8%。
实施例3:
溴乙烷的量增加到261.5g(2.4mol),间氯苯甲腈330.2g(2.4mol),其它同实例1,间氯苯丙酮的收率为89.1%。
实施例4:
溴乙烷的量增加到283.3g(2.6mol),间氯苯甲腈357.7g(2.6mol),其它同实例1,间氯苯丙酮的收率为92.6%。
实施例5:
溴乙烷的量增加到305.1g(2.8mol),间氯苯甲腈385.2g(2.8mol),其它同实例1,间氯苯丙酮的收率为90.5%。
实施例6:
溴乙烷的量增加到326.9g(3.0mol),间氯苯甲腈412.7g(3.0mol),其它同实例1,间氯苯丙酮的收率为87.3%。
实施例7:
溴乙烷的量增加到348.6g(3.2mol),间氯苯甲腈440.2g(3.2mol),其它同实例1,间氯苯丙酮的收率为83.2%。
Claims (3)
1.一种间氯苯丙酮的合成方法,其特征在于该方法包括以下步骤:在装有回流冷凝管、滴液漏斗的反应器中加入镁粉、四氢呋喃THF,从滴液漏斗中滴加溴乙烷,控制反应液温度40-100℃,使溶液一直保持微沸状态,滴加完毕后加热回流1.0-1.5h,保证镁反应完全,得到格氏试剂,搅拌下,将间氯苯甲腈缓慢滴加到格氏试剂中,滴加完后,反应3.0-4.0h,反应完毕,冷水浴下滴加3mol/L的盐酸,分解加成产物,分出无机相,有机相经常压蒸馏除去THF,减压蒸馏,得到间氯苯丙酮,
2.根据权利要求1所述的间氯苯丙酮的合成方法,其特征在于:镁粉、溴乙烷、间氯苯甲腈的物质的量之比为1.0:1.0-1.5:1.0-1.5,溶剂四氢呋喃THF的重量为镁粉重量8-10倍。
3.根据权利要求1所述的间氯苯丙酮的合成方法,其特征在于:合成间氯苯丙酮的反应温度为50-60℃;减压蒸馏所述的压力为-0.095MPa--0.10MPa、蒸馏温度为180-190℃。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3819706A (en) * | 1969-12-04 | 1974-06-25 | Burroughs Wellcome Co | Meta chloro substituted-alpha-butylamino-propiophenones |
CA977778A (en) * | 1969-12-04 | 1975-11-11 | Nariman B. Mehta | Intermediates for biologically active ketones |
CN102503794A (zh) * | 2011-10-25 | 2012-06-20 | 凯莱英医药集团(天津)股份有限公司 | 一种制备含氟取代苯基酮的方法 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3819706A (en) * | 1969-12-04 | 1974-06-25 | Burroughs Wellcome Co | Meta chloro substituted-alpha-butylamino-propiophenones |
CA977778A (en) * | 1969-12-04 | 1975-11-11 | Nariman B. Mehta | Intermediates for biologically active ketones |
CN102503794A (zh) * | 2011-10-25 | 2012-06-20 | 凯莱英医药集团(天津)股份有限公司 | 一种制备含氟取代苯基酮的方法 |
Non-Patent Citations (1)
Title |
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李韶辉,王占奇: "4-(N,N-二乙基胺)苯甲酮的制备", 《精细化工》 * |
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Application publication date: 20170524 |