CN106518707A - 一种制备酰胺的方法 - Google Patents
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
- C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
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Abstract
本发明公开了一种制备酰胺的方法,属于有机化学领域。该方法以1,1‑二氯环庚三烯作为高效有机催化剂,在有机溶剂中,酮肟在催化剂的作用下催化重排反应生成酰胺。本发明相比现有的催化体系具有用量低、温和、高效、来源广、合成简单、种类多、范围广、不含金属等明显的优势。该方法具有步骤简单、副产少、目标产物收率高等特点。
Description
技术领域
本发明属于有机化学领域,具体涉及一种制备酰胺的方法。
背景技术
有机小分子催化剂由于其在催化不对称合成反应中所表现出的优异催化效果,已经成为了人们近年来研究的热点。与过渡金属催化剂和酶催化剂相比,有机小分子催化剂具有结构简单、易于制备、不含金属离子、反应条件温和、原料廉价易得、稳定性强和对环境友好等优点,但是它们也存在着一些缺陷,其中最为显著的就是催化剂的用量较大。这对于那些价格稍微昂贵或者需要经过多步反应才能合成的有机小分子催化剂而言,无疑阻碍了它们在有机合成领域和工业化生产方面更加广泛的应用。所以,开发能够在较低催化剂负载量下仍然具有很强催化活性的新型有机小分子催化剂越来越受到化学工作者的重视。
贝克曼反应由于其重要性所以一直被人们关注。己内酰胺是制造尼龙6纤维和薄膜的重要原料。己内酰胺(CPL)是一种重要的有机化工原料,主要用于生产尼龙-6工程塑料和尼龙-6纤维。尼龙-6工程塑料主要用作汽车、船舶、电子电器、工业机械和日用消费品的构件和组件等;尼龙-6纤维可制成纺织品、工业丝和地毯用丝等。目前工业上采用的生产己内酰胺的主要工艺都经过环己酮与羟胺反应生成环己酮肟这一过程。由于此工艺存在副产硫酸铵多、采用有毒羟胺和腐蚀性强的浓硫酸等缺点(化工进展2005,24,565),近年来国外大公司纷纷加大科技投入,积极研究开发己内酰胺的绿色生产新技术。环己酮肟的贝克曼重排反应是生产己内酰胺最重要的反应步骤,目前传统重排反应过程以发烟硫酸作为催化剂,将环己酮肟经液相贝克曼重排为己内酰胺硫酸盐,然后再以氨水中和而得到己内酰胺。虽然整个反应环己酮肟的转化率几乎为100%,己内酰胺的选择率为99%,但整个反应不仅产生大量低价值的硫酸铵,而且催化的浓硫酸对整个设备所引起的腐蚀、环境污染等问题。
发明内容
有鉴于上述问题,本发明的主要目的在于提供一种有机催化重排反应制备酰胺的方法,即提供一种新型高效有机催化剂催化酮肟的重排反应。该方法具有用量低、温和、高效、来源广、合成简单、种类多、范围广、不含金属等明显的优势。
一种制备酰胺的方法,该方法以1,1-二氯环庚三烯作为高效有机催化剂,在有机溶剂中,酮肟在催化剂的作用下催化重排反应生成酰胺。
其催化剂的结构如下:
催化剂,可以是纯品,或者由环庚三烯酮和草酰氯原位生成的。
催化剂纯品由环庚三烯酮和草酰氯摩尔比1比1室温反应30分钟,然后旋干,然后重结晶得到淡黄色固体,即为1,1-二氯环庚三烯。
其中,该酮肟选自丙酮肟、丁酮肟、二苯甲酮肟、4,4-二甲氧基二苯甲酮肟、苯乙酮肟、3-甲氧基苯乙酮肟、4-溴苯乙酮肟、4-甲基苯乙酮肟、2-甲基苯乙酮肟、3-甲基苯乙酮肟、苯基环丙基甲酮肟、二苄基甲酮肟、环己基苯基甲酮、孕烯醇酮醋酸酯酮肟、L-薄荷酮肟、4-羟基苯乙酮肟、苯基-2-吡啶基酮肟、环戊酮肟、环己酮肟、环庚酮肟、环辛酮肟或环十二酮肟。
酮肟与1,1-二氯环庚三烯的摩尔比为200∶1-1∶1。
本发明的反应时间为1分钟至24小时。
所选用的反应溶剂为乙腈、四氢呋喃、二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、三甲苯、乙酸乙酯、乙酸丁酯、乙酸戊酯、1,2-二氯乙烷或氯丁烷。
所述在有机溶剂的反应在0℃-150℃条件下进行。
有益效果:
(1)采用1,1-二氯环庚三烯作为新型高效的有机催化剂,不会腐蚀仪器设备,不会造成环境污染,而且节约资源;
(2)催化剂用量低;
(3)反应体系简单,不需要另外加入其它助催化剂;
(4)反应条件温和,在常压和室温到100℃下进行;
(5)酮肟重排反应转化率高,选择性好;
(6)酮肟重排反应后处理简单,具有较好的工业可操作性;
本发明相比现有的催化体系具有用量低、温和、高效、来源广、合成简单、种类多、范围广、不含金属等明显的优势。该方法具有步骤简单、副产少、目标产物收率高等特点。
附图说明
以下,结合附图来详细说明本发明的实施例,其中:
图1:用1,1-二氯环庚三烯作催化剂制备得到的乙酰苯胺的1H NMR谱图;
图2:用1,1-二氯环庚三烯作催化剂制备得到的4-甲基乙酰苯胺的1H NMR谱图;
图3:用1,1-二氯环庚三烯作催化剂制备得到的w-月桂精内酰胺的1H NMR谱图;
图4:以1,1-二氯环庚三烯为催化剂制备得到的4-甲氧基苯甲酰4-甲氧基苯胺的1H NMR谱图。
具体实施方式
通过下列实施例可以进一步说明本发明,实施例是为了说明而非限制本发明的。本领域的任何普通技术人员都能够理解这些实施例不以任何方式限制本发明,可以对其做适当的修改和数据变换而不违背本发明的实质和偏离本发明的范围。
实施例1
在50ml三口圆底烧瓶中,加入0.135g苯乙酮肟,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持Ar氛围下,然后加入10ml乙腈,搅拌加热至80℃。然后加入10ul的环庚三烯酮和8.6ul草酰氯,回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):10min时原料转化70%,20min内原料完全转化,目标产物乙酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13C NMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58.
实施例2
在50ml三口圆底烧瓶中,加入0.197g二苯甲酮肟,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持Ar氛围下,然后加入10ml乙腈,搅拌加热至80℃。然后加入10ul的环庚三烯酮和8.6ul草酰氯,回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):30min时原料转化70%,1h内原料完全转化,目标产物苯甲酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的苯甲酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.93(s,1H),7.85(t,2H),7.64(t,2H),7.54(t,1H),7.47(t,2H),7.36(t,2H),7.15(t,1H).13C NMR(101MHz,CDCl3)δ165.93,138.07,135.14,131.94,129.21,128.90,127.16,124.70,120.39.
实施例3
在50ml三口圆底烧瓶中,加入0.135g苯乙酮肟和8mg 1,1-二氯环庚三烯的,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持N2氛围下,然后加入10ml乙腈,搅拌加热至80℃回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):10min时原料转化72%,20min内原料完全转化,目标产物乙酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13CNMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58.
实施例4
在50ml三口圆底烧瓶中,加入0.149g对甲基苯乙酮肟和8mg 1,1-二氯环庚三烯的,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持N2氛围下,然后加入10ml乙腈,搅拌加热至80℃回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):3min时原料转化62%,10min内原料完全转化,目标产物乙酰对甲基苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰对甲基苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13C NMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58.
实施例5
在50ml三口圆底烧瓶中,加入0.197g环十二酮肟和8mg 1,1-二氯环庚三烯的,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持N2氛围下,然后加入10ml甲苯,搅拌加热至80℃回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):2min时原料转化62%,10min内原料完全转化,目标产物w-月桂精内酰胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的w-月桂精内酰胺,白色固体。1H NMR(400MHz,CDCl3)δ5.91(brs,1H),3.27(t,2H),2.19(t,2H),1.65(m 2H),1.48(m,2H),1.29(m,12H).13C NMR(101MHz,CDCl3)δ204.51,173.61,39.15,37.00,28.42,26.87,26.46,26.32,25.84,25.33,25.05,24.78,24.04.
实施例6
在50ml三口圆底烧瓶中,加入0.203g苯基环己基酮肟和8mg 1,1-二氯环庚三烯的,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持N2氛围下,然后加入10ml甲苯,搅拌加热至80℃回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):2min时原料转化62%,10min内原料完全转化,目标产物苯甲酰环己基胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的苯甲酰环己基胺,白色固体。1H NMR(400MHz,CDCl3)δ7.73(d,2H),7.40(m,3H),6.04 (brs,1H),3.98(m,1H),2.03(m,2H),1.77-1.62(m,3H),1.43(m,2H),1.25(m,3H).13C NMR(101MHz,CDCl3)δ166.77,135.23,131.33,128.61,126.94,48.81,33.34,25.70,25.04.
实施例7
在50ml三口圆底烧瓶中,加入0.214g对溴苯乙酮肟和8mg 1,1-二氯环庚三烯的,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持N2氛围下,然后加入10ml乙腈,搅拌加热至80℃回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):3h时原料转化22%,24h原料完全转化,目标产物乙酰对甲基苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰对甲基苯胺,白色固体。1H NMR(400MHz,DMSO-δ6)δ10.05(s,1H),7.54(d,2H),7.46(d,2H),2.04(s,3H).13CNMR(101MHz,DMSO-δ6)δ168.47,138.66,131.45,120.88,114.50,24.01.
实施例8
在50ml三口圆底烧瓶中,加入0.214g环己酮肟和8mg 1,1-二氯环庚三烯的,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持N2氛围下,然后加入10ml二氯甲烷室温搅拌反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):1h时原料转化22%,24h原料完全转化,目标产物己内酰胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的己内酰胺,白色固体。1H NMR(400MHz,CDCl3)δ6.75(brs,1H),3.17(m,2H),2.43(m,2H),1.72-1.62(m,6H).13C NMR(101MHz,CDCl3)δ179.40,42.91,36.81,30.69,29.83,23.32.
实施例9
在50ml三口圆底烧瓶中,加入0.135g苯乙酮肟,连有球型冷凝管,在schlenk上,进行抽气换气3次,体系维持Ar氛围下,然后加入10ml甲苯,搅拌加热至150℃。然后加入10ul的环庚三烯酮和8.6ul草酰氯,回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):1min时原料转化80%,5min内原料完全转化,目标产物乙酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13C NMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58.
实施例10
在50ml三口圆底烧瓶中,加入0.135g苯乙酮肟,在Schlenk上,进行抽气换气3次,体系维持Ar氛围下,然后加入10ml二氯甲烷,室温搅拌。然后加入10ul的环庚三烯酮和8.6ul草酰氯,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):30min时原料转化40%,6h内原料完全转化,目标产物乙酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13CNMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58.
实施例11
在50ml三口圆底烧瓶中,加入0.135g苯乙酮肟,在Schlenk上,进行抽气换气3次,体系维持Ar氛围下,然后加入10ml乙腈,室温搅拌。然后加入1ul的环庚三烯酮和0.86ul草酰氯,回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释):30min时原料转化20%,12h 内原料完全转化,目标产物乙酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13CNMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58.
实施例12
在50ml三口圆底烧瓶中,加入0.135g苯乙酮肟,在Schlenk上,进行抽气换气3次,体系维持Ar氛围下,然后加入10ml二氯甲烷,室温搅拌。然后加入0.1ml的环庚三烯酮和0.086ml草酰氯,回流反应,通过液相色谱分析跟踪反应(取样后往样品中加入少许乙酸乙酯稀释)12min时原料转化60%,2h内原料完全转化,目标产物乙酰苯胺的选择性>98%。反应结束后将溶剂减压蒸馏除去,通过快速制备色谱,得到纯的乙酰苯胺,白色固体。1H NMR(400MHz,CDCl3)δ7.90(brs,1H),7.49(d,2H),7.29(t,2H),7.09(t,1H),2.14(s,3H).13CNMR(101MHz,CDCl3)δ168.90,138.10,129.03,124.39,120.18,24.58。
Claims (7)
1.一种制备酰胺的方法,其特征在于:在有机溶剂介质中,酮肟在有机催化剂的作用下催化重排反应生成酰胺,所述的有机催化剂为1,1-二氯环庚三烯。
2.根据权利要求1所述的制备酰胺的方法,其特征在于:所述的催化剂由环庚三烯酮和草酰氯原位生成。
3.根据权利要求1所述的制备酰胺的方法,其特征在于:所述的酮肟选自丙酮肟、丁酮肟、二苯甲酮肟、4,4-二甲氧基二苯甲酮肟、苯乙酮肟、3-甲氧基苯乙酮肟、4-溴苯乙酮肟、4-甲基苯乙酮肟、2-甲基苯乙酮肟、3-甲基苯乙酮肟、苯基环丙基甲酮肟、二苄基甲酮肟、环己基苯基甲酮、孕烯醇酮醋酸酯酮肟、L-薄荷酮肟、4-羟基苯乙酮肟、苯基-2-吡啶基酮肟、环戊酮肟、环己酮肟、环庚酮肟、环辛酮肟或环十二酮肟。
4.根据权利要求1所述的制备酰胺的方法,其特征在于:所述的酮肟与1,1-二氯环庚三烯的摩尔比为200∶1-1∶1。
5.根据权利要求1所述的制备酰胺的方法,其特征在于:反应时间为1分钟至24小时。
6.根据权利要求1所述的制备酰胺的方法,其特征在于:所述的有机溶剂为乙腈、四氢呋喃、二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、三甲苯、乙酸乙酯、乙酸丁酯、乙酸戊酯、1,2-二氯乙烷或氯丁烷。
7.根据权利要求1所述的制备酰胺的方法,其特征在于:在有机溶剂的反应在0℃-150℃条件下进行。
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