CN1058488C - 1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法 - Google Patents
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Abstract
本发明涉及式(1)代表的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法,其制备方法包括使式(2)代表的N,N′,N″-三烷基二亚乙基三胺与脲、光气或二氧化碳反应;式(1)和式(2)如下式中R是C1-C8烷基。
Description
1,3-二甲基-2-咪唑啉酮和N-甲基-2-吡咯烷酮是公知的常规疏质子极性化合物。
这些化合物是有用的溶剂,尤其是聚酰胺、聚氯乙烯、聚乙烯醇、聚苯乙烯、聚氨酯、酚醛树脂和其它高聚物的极好的溶剂。而且,这些化合物也可用作许多有机反应的溶剂。然而,公知的疏质子极性化合物存在许多问题。例如1,3-二甲基-2-咪唑啉酮在高温下抗氧化性差,N-甲基-2-吡咯烷酮会引起染色体畸变。
本发明的目的是提供溶剂效应极佳的新的疏质子极性化合物。
为了开发出新的疏质子极性溶剂,本发明人进行了深入的研究,结果成功地制备了具有与1,3-二甲基-2-咪唑啉酮类似的环状脲结构的并预期是强极性的1,3,6-三烷六氢-1,3,6-三氮杂辛因-2-酮,并且发现,该新化合物作为疏质子极性物质能够产生极佳的溶剂效应。从而完成了本发明。
也就是说,本发明的一个方面是式(1)代表的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮:式中R是C1-C8烷基。
本发明的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮表现出比常规疏质子极性溶剂优异的溶剂效应。
因此,本发明能够提供溶剂效应极佳的新的疏质子物质,从而具有重要的意义。
图1是1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮的IR光谱图;
图2是1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的IR光谱图;
图3是1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的IR光谱图。
在式(1)中,R是具有1-8个碳原子的烷基。所述烷基的例子包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、2-戊基、3-戊基、新戊基、正己基、异己基、正庚基、异庚基、正辛基和异辛基。
必要时,也可通过在相应的烷基胺的共存下使N,N′-二烷基亚乙基二胺与1,2-二卤代乙烷反应来制备所述三元胺。将这样得到的N,N′,N″-三烷基二亚乙基三胺与脲、光气或二氧化碳反应,经环化作用得1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮。
在优选的制备中间体N,N′,N″-三烷基二亚乙基三胺的方法中,烷基胺与1,2-二卤代乙烷的摩尔比优选4-6。当烷基胺的摩尔比率太高时,中间体副产物N,N′-二烷基亚乙基二胺的量容易增加。
对于1,2-二卤代乙烷胺化的反应温度没有特别限制,只要温度在能给出适当反应速率的范围内就行。优选的温度范围是80-150℃。
胺化反应可根据反应温度而在加压下进行。在实践中,当使用沸点高于正丁胺沸点(沸点:78℃)的胺时,反应可在大气压力下进行。然而,当使用沸点低于正丁胺沸点的胺时,反应必须在加压下进行。
已知的常规溶剂均可用于胺化反应,不存在任何问题。然而,胺化反应通常在无溶剂情况下进行,即仅在烷基胺和1,2-二囟代己烷的存在下进行。
这样生成的N,N′,N″-三烷基二亚乙基三胺可通过用氢氧化钠或其它适当的碱中和胺化反应混合物并蒸除未反应的烷基胺的方法来分离。进一步蒸馏残余物可获得纯产物。
在本发明方法的第一步中,先使N,N′,N″-三烷基二亚乙基三胺与脲反应生成脲中间体。反应温度优选在100-155℃、更优选在120-145℃的范围内。反应温度高于155℃将导致脲的分解。另一方面,当反应温度低于100℃时,则反应速率太低。在该起始反应中,脲中间体的生成定量地进行,反应的终点可通过测定随反应进行而释放出的氨气来检测。
脲中间体的分解反应是通过随后将反应温度升至180℃或高、优选200-260℃、更优选210-240℃进行的。这样便可高收率地得到1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮。当温度低于180℃时,分解反应太慢。另一方面,300℃左右的温度会使加热设备产生问题。
在本发明方法中,对于1mol脲,N,N′,N″-三甲基二亚乙基三胺的用量为0.8-2.5mol,优选1.0-2.0mol,更优选1.2-1.7mol。当N,N′,N″-三甲基二亚乙基三胺的用量少于0.8mol时,副产物的生成加剧。另一方面,用量超过2.5mol将导致工业中的不利因素,例如,体积效率降低。
本发明方法中可用的溶剂包括例如乙醇、甲基·异丁基酮、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、二甘醇二甲醚和三甘醇二甲醚。然而,本发明方法也可在无溶剂条件下实施。也就是说,即使在仅有N,N′,N″-三烷基二亚乙基三胺和脲存在下进行反应得到1,3,6-三烷基六氢-1,3,6-三氢杂辛因-2-酮的收率也等于或高于有溶剂存在下所得的收率。因此,从免除复杂程序如蒸除溶剂的观点来看,最好使反应在无溶剂条件下进行。而且,当使用高沸点溶剂时,反应可在大气压力下进行。然而,当使用低沸点溶剂时,则需要在加压下进行反应,从生产设施的角度来看,这在工业上是不利的。然而,在N,N′,N″-三烷基二亚乙基三胺中,N,N′,N″-三甲基二亚乙基三胺的沸点最低,但仍可达201℃。因而,不需要加压,从而优选在无溶剂条件下进行反应。
这样生成的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮可通过蒸馏提纯。未反应的N,N′,N″-三烷基二亚乙基三胺作为1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮的初馏物被回收并可再次使用。
下面通过实施例和对比例来详细说明本发明。
实施例1
向5.0升装有温度计和搅拌器的高压釜中投入1286.5g(13mol)1,2-二氯乙烷和2018.9g(65mol)甲胺。搅拌加热至100℃,保持该温度,继续胺化反应2小时。
随后,将反应混合物冷却至室温,通过将反应器减压来回收过量的甲胺。用气相色谱分析此阶段的反应物料。1,2-二氯乙烷全部转化。随后,投入1072.2g 97%的片状氢氧化钠以中和反应物料,然后蒸馏回收未反应的甲胺。蒸馏后,滤除反应物料中沉淀的氯化钠,将滤液蒸馏,分离出229.4g N,N′,N″-三甲基二亚乙基三胺。
向0.5升装有回流冷凝器、温度计和搅拌器的烧瓶中投入217.9g(1.5mol)N,N′,N″-三甲基二亚乙基三胺和60.1g(1.0mol)脲,于125-140℃搅拌反应4小时。
随后,将温度升至215-225℃,在该温度下进行脲中间体的分解反应2小时。反应完毕后,用气相色谱测定1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮。基于脲计,收率为80.3%。蒸馏反应混合物,回收63.2g在第一步中未反应的N,N′,N″-三甲基二亚乙基三胺,然后得127.1g 1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮。产物的沸点为258℃,纯度为99.0%。
用′H NMR、13C NMR、IR和MS m/z:171(M+)鉴定1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮的结构。○ 1H NMR,δ(CDCl3,400MHz)
2.42(s,3H,④),2.66(m,4H,③),
2.78(s,6H,①),3.33(m,4H,②),○ 13C NMR,δ(CDCl3,100MHz)
36.8(q,①),46.6(q,④),
53.8(t,②),54.7(t,③),
图1是1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮的IR图。
实施例2
用与实施例1相同的方法进行反应和分析,只是要用正丙胺来代替甲胺。结果,1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的收率为66.5%(基于脲计算)。1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的结构用′HNMR、13C NMR、IR和MS m/z:297(M+)鉴定:
○ 1H NMR,δ(CDCl3,400MHz)
0.89(t,9H,①和⑧),
1.50(m,2H,⑦),1.56(m,4H,②),
2.47(t,2H,⑥),2.70(m,4H,④),
3.09(t,4H,③),3.35(t,4H,⑤),
○ 13C NMR,δ(CDCl3,100MHz)
11.5(q,①),11.7(q,⑧),
20.4(t,⑦),21.0(t,②),
51.5(t,③),51.8(t,⑤),
53.3(t,④),60.3(t,⑥),
163.5(s,C=0,⑨),
其中(①-⑧)代表下式中的位置;
图2是1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的IR图。
实施例3
用与实施例1相同的方法进行反应和分析,只是要用正丁胺来代替甲胺,并且N,N′,N″-三正丁基二亚乙基三胺的合成在大气压力下进行。结果,1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的收率为51.5%(基于脲计算)。1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的结构用′HNMR、13C NMR、IR和MS m/z:256(M+)鉴定。○1H NMR,δ(CDCl3,400MHz)
0.90(t,3H,⑩),0.91(t,6H,①),
1.30(m,6H,②and⑨)
1.42(m,2H,⑧),1.52(m,4H,③),
2.48(t,2H,⑦),2.67(m,4H,⑤),
3.11(t,4H,④),3.34(m,4H,⑥),○ 13C NMR,δ(CDCl3,100MHz)
13.8(q,①),13.9(q,⑩),
20.1(t,②),20.3(t,⑨),
29.4(t,⑧),29.6(t,③),
49.5(t,④),51.8(t,⑥),
53.2(t,⑤),58.0(t,⑦),
163.4(s,C=0,)其中(①-⑩)代表下式中的位置;
图3是1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的IR图。
对比例1
向0.3升装有搅拌器和温度计的反应器中投入25.1g(0.1mol)4,4′-二氯二苯酮、24.0g(0.22mol)间氨基苯酚、12.9g(0.22mol)96%的氢氧化钾和150g用作溶剂的得自实施例1的1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮,于150-160℃反应8小时。
反应完成后,将反应物料冷却至室温,滤除生成的无机盐。从滤液中减压蒸除溶剂。将残余物与20.8g 35%的盐酸和100g水混合,加热溶解。随后向所得溶液中加入11.7g氯化钠,在搅拌下冷却至20-25℃以沉淀盐酸盐。滤出盐酸盐,用10%氯化钠水溶液重结晶,然后在50%异丙醇水溶液中,用氨水溶液中和。过滤沉淀的晶体,水洗、干燥,得25.6g(收率:88.3%)4,4′-二(3-氨基苯氧基)二苯酮白色晶体。用高效液相色谱测得纯度为99.5%。
对比例2
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为1,3,6-三正丙基六氢-1,3,6-三氮杂辛-2-酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为88.0%。
对比例3
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为1,3,6-三正丁基六氢-1,3,6-三氮杂辛-2-酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为87.5%。
对比例4
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为1,3-二甲基-2-咪唑啉酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为87.0%。
对比例5
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为N-甲基-2-吡咯烷酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为76.5%。
Claims (5)
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