CN114773285A - 一种高效的α-胺基噁唑啉化合物的制备方法 - Google Patents

一种高效的α-胺基噁唑啉化合物的制备方法 Download PDF

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CN114773285A
CN114773285A CN202210297680.2A CN202210297680A CN114773285A CN 114773285 A CN114773285 A CN 114773285A CN 202210297680 A CN202210297680 A CN 202210297680A CN 114773285 A CN114773285 A CN 114773285A
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oxazoline
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胡梦杰
包明
张胜
冯秀娟
于晓强
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Abstract

本发明提供一种高效的α‑胺基噁唑啉化合物的制备方法，以2‑烷基噁唑啉及其衍生物为原料，在芳基亚砜、活化剂、无水有机溶剂条件下，在‑20℃下反应3小时，在碱存在的情况下，在‑40℃下反应1小时，在芳基胺存在的情况下，在‑40℃下反应12小时，即可得到相应的α‑胺基噁唑啉化合物。本方法反应选择性好，收率高，产物易分离、操作简单；本方法所用原料廉价易得，反应条件温和，避免了传统方法中反应条件要求严格，反应底物受到限制的缺点；本反应设计新颖，为噁唑啉化合物α‑位胺基化开辟了新的合成途径；利用该方法合成的α‑胺基噁唑啉化合物可进一步官能化得到各类化合物，应用于天然产物、功能材料及精细化学品的开发与研究。

Description

一种高效的α-胺基噁唑啉化合物的制备方法
技术领域
本发明属于精细化学品及相关化学技术领域，提供了一种高效的α-胺基噁唑啉化合物的制备方法。
背景技术
羰基化合物在有机化学中占据了重要的地位，醛、酮、羧酸以及羧酸衍生物(酸酐，酰卤，酰胺，酯)等都含有羰基官能团。这一反应模式涉及到多个人名反应，如Aldol反应、Claisen酯缩合反应、Dieckmann酯缩合反应。与此不同，近年来，借助三价碘与羰基的配位/氧化作用，可以实现羰基化合物α位的极性反转，从而使原本具有亲核性的α–碳具有了亲电性，使其能与亲核试剂偶联。但高价碘与羰基化合物形成的中间体以及高价碘自身的不稳定性，导致这类反应的官能团兼容性较差、底物适用范围窄，限制了该类反应的应用。
噁唑啉作为羰基化合物的一种前体，可以通过简单的水解转化为羰基衍生物，因此研究噁唑啉的α–官能团化同样具有重要的意义。此外，由α-胺基噁唑啉化合物水解得到的α-胺基酯类化合物是制备一类受突触活性诱导表达的蛋白激酶分子的重要前体，而该蛋白激酶是帕金森病的潜在治疗靶点(Bioorg.Med.Chem.Lett.2013,23,2743-2749)，因此，研究开发不同取代的α-胺基噁唑啉化合物，为药物分子合成提供更为丰富的中间体具有重要的现实意义。
发明内容
为了克服现有技术中存在的缺陷，本发明提供了一种制备α-胺基噁唑啉化合物的新方法。该反应方法创新性高，条件温和，选择性好，收率高，官能团兼容性强。
本发明的技术方案：
一种高效的α-胺基噁唑啉化合物的制备方法，其特征在于，以2-烷基噁唑啉及其衍生物为原料，在芳基亚砜和活化剂存在的情况下，在无水有机溶剂条件下，在-20℃下反应3小时，在碱存在的情况下，在-40℃下反应1小时，在芳基胺存在的情况下，在-40℃下反应12小时，即可得到相应的α-胺基噁唑啉化合物，合成路线如下：
Figure BDA0003564040200000021
R1选自C2～C8直链烷基、烷基硅醚取代的C3烷基、烯烃取代的C5烷基、卤代芳烃取代的C2烷基、吲哚取代的C2烷基、
Figure BDA0003564040200000022
Figure BDA0003564040200000023
R2选自甲氧基、烷基，R2位于芳烃胺基的间位或对位；
2-烷基噁唑啉及其衍生物与芳基亚砜的摩尔比为1:1～1:2；
2-烷基噁唑啉及其衍生物与活化剂的摩尔比为1:1～1:1.5；
2-烷基噁唑啉及其衍生物与碱的摩尔比为1:2～1:3；
2-烷基噁唑啉及其衍生物与芳基胺的摩尔比为1:1～1:2；
2-烷基噁唑啉及其衍生物在体系中的摩尔浓度为0.1mmol/mL。
所述的无水有机溶剂为乙醚、甲基叔丁基醚、1,4-二氧六环、甲基环戊基醚、二氯甲烷、四氢呋喃、1,2-二氯乙烷中的一种或两种以上混合。
所述的活化剂为三氟甲磺酸酐、对甲苯磺酸酐、三氯乙酸酐、三氟乙酸酐、甲磺酸酐中的一种或两种以上混合。
所述的碱为1,8-二偶氮杂双螺环[5.4.0]十一-7-烯、三乙烯二胺、N,N'-二异丙基乙胺、三乙胺中的一种或两种以上混合。
分离方法包括重结晶、柱层析等。
重结晶方法使用的溶剂包括石油醚、乙酸乙酯、乙醚、丙酮、氯仿、正己烷、二氯甲烷。
用柱层析方法进行产物分离时，可以使用硅胶或者中性氧化铝作为固定相，展开剂一般为极性与非极性的混合溶剂，如乙酸乙酯-石油醚、乙酸乙酯-正己烷、二氯甲烷-石油醚、甲醇-石油醚。
与现有方法相比，本方法通过2-烷基噁唑啉与芳基胺在温和条件下合成α-胺基噁唑啉化合物，其优势在于：
1)本方法反应选择性好，收率高，产物易分离、操作简单；
2)本方法所用原料廉价易得，反应条件温和，避免了传统方法中反应条件要求严格，反应底物受到限制的缺点；
3)本反应设计新颖，为噁唑啉化合物α-位胺基化开辟了新的合成途径。
4)利用该方法所合成的α-胺基噁唑啉化合物可以进一步官能化得到各类化合物，应用于天然产物、功能材料及精细化学品的开发与研究。
附图说明
图1是实施例1中α-胺基噁唑啉化合物2a的1H核磁谱图。
图2是实施例1中α-胺基噁唑啉化合物2a的13C核磁谱图。
图3是实施例2中α-胺基噁唑啉化合物2b的1H核磁谱图。
图4是实施例2中α-胺基噁唑啉化合物2b的13C核磁谱图。
图5是实施例3中α-胺基噁唑啉化合物2c的1H核磁谱图。
图6是实施例3中α-胺基噁唑啉化合物2c的13C核磁谱图。
图7是实施例4中α-胺基噁唑啉化合物2d的1H核磁谱图。
图8是实施例4中α-胺基噁唑啉化合物2d的13C核磁谱图。
图9是实施例5中α-胺基噁唑啉化合物2e的1H核磁谱图。
图10是实施例5中α-胺基噁唑啉化合物2e的13C核磁谱图。
图11是实施例6中α-胺基噁唑啉化合物2f的1H核磁谱图。
图12是实施例6中α-胺基噁唑啉化合物2f的13C核磁谱图。
图13是实施例7中α-胺基噁唑啉化合物2g的1H核磁谱图。
图14是实施例7中α-胺基噁唑啉化合物2g的13C核磁谱图。
图15是实施例8中α-胺基噁唑啉化合物2h的1H核磁谱图。
图16是实施例8中α-胺基噁唑啉化合物2h的13C核磁谱图。
图17是实施例9中α-胺基噁唑啉化合物2i的1H核磁谱图。
图18是实施例9中α-胺基噁唑啉化合物2i的13C核磁谱图。
图19是实施例10中α-胺基噁唑啉化合物2j的1H核磁谱图。
图20是实施例10中α-胺基噁唑啉化合物2j的13C核磁谱图。
具体实施方式
本发明所述的α-胺基噁唑啉化合物的制备方法，具有原料价格低廉、反应无过渡金属参与、反应条件温和、便于操作和反应收率高等优点。
下面结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1：α-胺基噁唑啉化合物2a的合成
Figure BDA0003564040200000041
在干燥的25mL反应器中，加入上式所示的2-烷基噁唑啉化合物(1a，0.057g,0.5mmol)、芳基亚砜(0.108g,0.5mmol)，加入无水二氯甲烷5.0mL，-20℃下加入三氟乙酸酐(0.104mL，0.75mmol)，搅拌3h。-40℃下向混合物中加入三乙胺(1.5mmol，3.0equiv)。搅拌1h后，加入4-甲氧基苯胺(1.0mmol，2.0equiv)，反应12h。柱层析分离(硅胶，200-300目；展开剂，乙酸乙酯-石油醚)得到淡黄色固体状产物2a，0.085g，产率72％。
1H NMR(600MHz,CDCl3):δ6.75(d,J＝8.9Hz,2H),6.63(d,J＝8.9Hz,2H),4.29–4.15(m,2H),4.03(t,J＝6.4Hz,1H),3.82(t,J＝9.4Hz,2H),3.72(s,3H),1.88–1.75(m,2H),0.99(t,J＝7.4Hz,3H)；13C NMR(151MHz,CDCl3):δ168.9,152.5,141.2,115.1,114.9,67.8,55.8,54.22,54.20,26.6,10.2；IR(neat,cm-1):3269,2960,2831,1656,1508,1458,1230,1141,953,816.HRMS(ESI-TOF):calculated for[C13H19N2O2(M+H+)]:235.1441,found:235.1452.
实施例2：α-胺基噁唑啉化合物2b的合成
Figure BDA0003564040200000051
操作同实施例1，由上式所示的2-烷基噁唑啉化合物(1b，0.071g,0.5mmol)得到相应的α-胺基噁唑啉化合物2b,0.111g，淡黄色固体，产率84％。
1H NMR(600MHz,CDCl3):δ6.76(d,J＝8.9Hz,2H),6.63(d,J＝8.9Hz,2H),4.30–4.14(m,2H),4.07(d,J＝4.3Hz,1H),3.82(t,J＝9.4Hz,2H),3.77(s,1H),3.73(s,3H),1.81–1.71(m,2H),1.46–1.31(m,4H),0.90(t,J＝7.1Hz,3H)；13C NMR(151MHz,CDCl3):δ169.1,152.6,141.2,115.1,114.9,67.7,55.8,54.2,53.0,33.4,27.9,22.6,14.0；IR(neat):3275,2955,2830,1654,1508,1440,1235,1178,982,812,772；HRMS(ESI-TOF):calculated for[C15H23N2O2(M+H+)]:263.1754,found:263.1759.
实施例3：α-胺基噁唑啉化合物2c的合成
Figure BDA0003564040200000061
操作同实施例1，由上式所示的2-烷基噁唑啉化合物(1c，0.099g,0.5mmol)得到相应的α-胺基噁唑啉化合物2c，0.112g，淡黄色固体，产率70％。
1H NMR(600MHz,CDCl3):δ6.75(d,J＝8.8Hz,2H),6.63(d,J＝8.8Hz,2H),4.30–4.13(m,2H),4.07(t,J＝6.5Hz,1H),3.89–3.74(m,3H),3.72(s,3H),1.83–1.69(m,2H),1.48–1.34(m,2H),1.31–1.16(m,10H),0.87(t,J＝7.0Hz,3H)；13C NMR(151MHz,CDCl3):δ169.1,152.5,141.2,115.1,114.8,67.7,55.7,54.2,53.0,33.6,31.9,29.5,29.4,29.3,25.7,22.7,14.2；IR(neat):3257,2918,2849,1658,1467,1230,1036,951,828,717；HRMS(ESI-TOF):calculated for[C19H31N2O2(M+H+)]:319.2380,found:319.2383.
实施例4：α-胺基噁唑啉化合物2d的合成
Figure BDA0003564040200000062
在干燥的25mL反应器中，加入上式所示的2-烷基噁唑啉化合物(1d，0.129g,0.5mmol)、芳基亚砜(0.108g,0.5mmol)，加入无水四氢呋喃5.0mL，-20℃下加入三氟甲磺酸酐(0.127mL，0.75mmol)，搅拌3h。-40℃下向混合物中加入三乙胺(1.5mmol，3.0equiv)。搅拌1h后，加入4-甲氧基苯胺(1.0mmol，2.0equiv)，反应12h。柱层析分离(硅胶，200-300目；展开剂，乙酸乙酯-石油醚)得到淡黄色固体状产物2d，0.143g，产率75％。
1H NMR(600MHz,CDCl3):δ6.77(d,J＝8.9Hz,2H),6.65(d,J＝8.9Hz,2H),4.32–4.16(m,2H),4.11(t,J＝6.5Hz,1H),3.89–3.78(m,3H),3.74(s,3H),3.65(t,J＝6.2Hz,2H),1.93–1.82(m,2H),1.70–1.59(m,2H),0.90(s,9H),0.05(s,6H)；13C NMR(151MHz,CDCl3):δ169.0,152.6,141.2,115.1,114.9,67.8,62.7,55.8,54.2,52.9,30.0,29.0,26.1,18.4,–5.2；IR(neat,cm-1):3313,2952,2855,1651,1521,1463,1234,1103,986,835；HRMS(ESI-TOF):calculated for[C20H35N2O3Si(M+H+)]:379.2411,found:379.2419.
实施例5：α-胺基噁唑啉化合物2e的合成
Figure BDA0003564040200000071
操作同实施例4，由上式所示的2-烷基噁唑啉化合物(1e，0.090g,0.5mmol)得到相应的α-胺基噁唑啉化合物2e，0.107g，淡黄色固体，产率71％。
1H NMR(600MHz,CDCl3):δ6.75(d,J＝8.9Hz,2H),6.62(d,J＝8.9Hz,2H),5.82–5.73(m,1H),4.99–4.96(m,1H),4.93–4.91(m,1H),4.29–4.14(m,2H),4.07(t,J＝6.7Hz,1H),3.86–3.74(m,3H),3.72(s,3H),2.06–2.00(m,2H),1.82–1.70(m,2H),1.46–1.32(m,6H)；13C NMR(151MHz,CDCl3):δ169.0,152.5,141.1,139.0,115.0,114.8,114.4,67.7,55.7,54.2,53.0,33.7,33.6,28.9,28.7,25.6；IR(neat,cm-1):3271,2922,2851,1655,1508,1462,1230,1141,953,816；HRMS(ESI-TOF):calculated for[C18H27N2O2(M+H+)]:303.2067,found:303.2066.
实施例6：α-胺基噁唑啉化合物2f的合成
Figure BDA0003564040200000072
在干燥的25mL反应器中，加入上式所示的2-烷基噁唑啉化合物(1f，0.112g,0.5mmol)、芳基亚砜(0.108g,0.5mmol)，加入无水二氯甲烷5.0mL，-20℃下加入三氟乙酸酐(0.127mL，0.75mmol)，搅拌3h。-40℃下向混合物中加入1,8-二偶氮杂双螺环[5.4.0]十一-7-烯(1.5mmol，3.0equiv)。搅拌1h后，加入4-甲氧基苯胺(1.0mmol，2.0equiv)，反应12h。柱层析分离(硅胶，200-300目；展开剂，乙酸乙酯-石油醚)得到淡黄色固体状产物2f，0.135g，产率78％。
1H NMR(600MHz,CDCl3):δ7.24(d,J＝8.3Hz,2H),7.12(d,J＝8.3Hz,2H),6.76(d,J＝8.9Hz,2H),6.60(d,J＝8.9Hz,2H),4.29–4.14(m,2H),4.08(t,J＝6.0Hz,1H),3.85(s,1H),3.80(t,J＝9.5Hz,2H),3.73(s,3H),2.74(t,J＝7.0Hz,2H),2.14–2.01(m,2H)；13C NMR(151MHz,CDCl3):δ168.7,152.7,140.9,139.7,131.8,130.0,128.6,115.2,114.9,67.9,55.8,54.2,52.2,34.9,31.3；IR(neat,cm-1):3268,2929,2833,1654,1507,1235,1089,1011,949,813；HRMS(ESI-TOF):calculated for[C19H22ClN2O2(M+H+)]:345.1364,found:345.1368.
实施例7：α-胺基噁唑啉化合物2g的合成
Figure BDA0003564040200000081
操作同实施例6，由上式所示的2-烷基噁唑啉化合物(1g，0.191g,0.5mmol)得到相应的α-胺基噁唑啉化合物2g，0.188g，淡黄色固体，产率75％。
1H NMR(600MHz,CDCl3):δ7.98(d,J＝8.3Hz,1H),7.74(d,J＝8.3Hz,2H),7.43(d,J＝7.8Hz,1H),7.36(s,1H),7.32–7.28(m,1H),7.23–7.15(m,3H),6.74(d,J＝8.8Hz,2H),6.59(d,J＝8.8Hz,2H),4.28–4.19(m,2H),4.17–4.11(m,1H),3.94(s,1H),3.83(t,J＝9.5Hz,2H),3.73(s,3H),2.86–2.77(m,2H),2.29(s,3H),2.25–2.10(m,2H)；13C NMR(101MHz,CDCl3):δ168.6,152.7,144.8,140.9,135.4,135.3,130.9,129.9,126.8,124.8,123.1,123.0,122.2,119.5,115.2,114.9,113.8,67.9,55.8,54.2,52.4,32.5,21.6,21.1；IR(neat,cm-1):3272,3108,2917,1664,1506,1447,1363,1232,1039,815；HRMS(ESI-TOF):calculated for[C28H30N3O4S(M+H+)]:504.1952,found:504.1950.
实施例8：α-胺基噁唑啉化合物2h的合成
Figure BDA0003564040200000091
操作同实施例6，由上式所示的2-烷基噁唑啉化合物(1h，0.178g,0.5mmol)得到相应的α-胺基噁唑啉化合物2h，0.168g，淡黄色固体，产率70％。
1H NMR(600MHz,CDCl3):δ7.67(d,J＝16.0Hz,1H),7.51(d,J＝3.7Hz,2H),7.40–7.32(m,3H),6.75(d,J＝8.7Hz,2H),6.63(d,J＝8.7Hz,2H),6.44(d,J＝16.0Hz,1H),4.27–4.14(m,4H),4.07(t,J＝6.4Hz,1H),3.80(t,J＝9.4Hz,2H),3.71(s,3H),1.84–1.63(m,4H),1.46–1.24(m,12H)；13C NMR(151MHz,CDCl3):δ169.0,167.1,152.5,144.6,141.2,134.5,130.2,128.9,128.1,118.3,115.0,114.8,67.7,64.7,55.7,54.2,52.9,33.6,29.4,29.38,29.36,29.2,28.7,26.0,25.7；IR(neat,cm-1):3265,2920,2849,1701,1632,1526,1462,1238,1163,980,827；HRMS(ESI-TOF):calculated for[C29H39N2O4(M+H+)]:479.2904,found:479.2908.
实施例9：α-胺基噁唑啉化合物2i的合成
Figure BDA0003564040200000092
操作同实施例6，由上式所示的2-烷基噁唑啉化合物(1i，0.170g,0.5mmol)得到相应的α-胺基噁唑啉化合物2i，0.202g，淡黄色固体，产率78％。
1H NMR(600MHz,CDCl3):δ7.57(d,J＝4.0Hz,1H),6.92(d,J＝4.0Hz,1H),6.76(d,J＝8.9Hz,2H),6.63(d,J＝8.9Hz,2H),4.30–4.18(m,4H),4.07(t,J＝6.7Hz,1H),3.82(t,J＝9.3Hz,2H),3.73(s,3H),1.82–1.68(m,4H),1.48–1.35(m,4H),1.33–1.23(m,12H)；13CNMR(151MHz,CDCl3):δ169.2,161.5,152.6,141.2,137.2,132.9,132.3,127.3,115.1,114.9,67.8,65.9,55.8,54.2,53.1,33.7,29.6,29.59,29.56,29.49,29.3,28.7,26.0,25.8；IR(neat,cm-1):3259,2916,2849,1708,1655,1510,1424,1235,1089,826,743；HRMS(ESI-TOF):calculated for[C27H38ClN2O4S(M+H+)]:521.2235,found:521.2244.
实施例10：α-胺基噁唑啉化合物2j的合成
Figure BDA0003564040200000101
在干燥的25mL反应器中，加入上式所示的2-烷基噁唑啉化合物(1b，0.071g,0.5mmol)、芳基亚砜(0.108g,0.5mmol)，加入无水二氯甲烷5.0mL，-20℃下加入三氟乙酸酐(0.104mL，0.75mmol)，搅拌3h。-40℃下向混合物中加入三乙胺(1.5mmol，3.0equiv)。搅拌1h后，加入3,5-二甲基苯胺(1.0mmol，2.0equiv)，反应12h。柱层析分离(硅胶，200-300目；展开剂，乙酸乙酯-石油醚)得到淡黄色固体状产物2j，0.093g，产率71％。
1H NMR(600MHz,CDCl3):δ6.39(s,1H),6.31(s,2H),4.32–4.20(m,2H),4.20–4.14(m,1H),3.98(s,1H),3.84(t,J＝9.4Hz,2H),2.23(s,6H),1.87–1.70(m,2H),1.44–1.31(m,4H),0.91(t,J＝7.1Hz,3H)；13C NMR(151MHz,CDCl3):δ169.0,147.1,138.9,120.0,111.3,67.8,54.2,51.8,33.4,27.8,22.5,21.6,14.1；IR(neat,cm-1):3266,2955,2858,1659,1599,1462,1332,1186,947,855.HRMS(ESI-TOF):calculated for[C16H25N2O(M+H+)]:261.1961,found:261.1956.
应用例1：
Figure BDA0003564040200000111
在25mL反应器中，依次加入上式所示的化合物2a(0.5mmol，0.117g)，MeOH(2mL)，H2SO4(3M,1mL)。加热回流12h，用饱和NaHCO3水溶液淬灭反应，用DCM萃取并真空浓缩。柱层析分离(硅胶，200-300目；展开剂，乙酸乙酯-石油醚)，得到棕色油状液体化合物3a，0.088g，产率79％。
1H NMR(400MHz,CDCl3):δ6.76(d,J＝8.8Hz,2H),6.59(d,J＝8.8Hz,2H),3.97(t,J＝6.5Hz,1H),3.73(s,3H),3.70(s,3H),1.88-1.70(m,2H),1.00(t,J＝7.0Hz,3H)。13C NMR(101MHz,CDCl3):δ174.9,152.7,141.1,115.1,115.0,59.0,55.7,52.0,26.3,10.1。
由应用例1得到的化合物3a为一种已知的重要中间体(Org.Lett.2021,23,3207-3210)，可用于多种中间体或者药物的合成。

Claims (5)

1.一种一种高效的α-胺基噁唑啉化合物的制备方法，其特征在于，以2-烷基噁唑啉及其衍生物为原料，在芳基亚砜和活化剂存在的情况下，在无水有机溶剂条件下，在-20℃下反应3小时；在碱存在的情况下，在-40℃下反应1小时；在芳基胺存在的情况下，在-40℃下反应12小时，即得到α-胺基噁唑啉化合物，合成路线如下：
Figure FDA0003564040190000011
R1选自C2～C8直链烷基、烷基硅醚取代的C3烷基、烯烃取代的C5烷基、卤代芳烃取代的C2烷基、吲哚取代的C2烷基、
Figure FDA0003564040190000012
Figure FDA0003564040190000013
R2选自甲氧基、烷基，R2位于芳烃胺基的间位或对位；
2-烷基噁唑啉及其衍生物与芳基亚砜的摩尔比为1:1～1:2；
2-烷基噁唑啉及其衍生物与活化剂的摩尔比为1:1～1:1.5；
2-烷基噁唑啉及其衍生物与碱的摩尔比为1:2～1:3；
2-烷基噁唑啉及其衍生物与芳基胺的摩尔比为1:1～1:2；
2-烷基噁唑啉及其衍生物在体系中的摩尔浓度为0.1mmol/mL。
2.根据权利要求1所述的制备方法，其特征在于，所述的无水有机溶剂为乙醚、甲基叔丁基醚、1,4-二氧六环、甲基环戊基醚、二氯甲烷、四氢呋喃、1,2-二氯乙烷中的一种或两种以上混合。
3.根据权利要求1或2所述的制备方法，其特征在于，所述的活化剂为三氟甲磺酸酐、对甲苯磺酸酐、三氯乙酸酐、三氟乙酸酐、甲磺酸酐中的一种或两种以上混合。
4.根据权利要求1或2所述的制备方法，其特征在于，所述的碱为1,8-二偶氮杂双螺环[5.4.0]十一-7-烯、三乙烯二胺、N,N'-二异丙基乙胺、三乙胺中的一种或两种以上混合。
5.根据权利要求3所述的制备方法，其特征在于，所述的碱为1,8-二偶氮杂双螺环[5.4.0]十一-7-烯、三乙烯二胺、N,N'-二异丙基乙胺、三乙胺中的一种或两种以上混合。
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