CN112961019A - 一种简便高效合成芳香族烯烃衍生物的方法 - Google Patents
一种简便高效合成芳香族烯烃衍生物的方法 Download PDFInfo
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Abstract
本发明提供一种简便高效合成芳香族烯烃衍生物的方法,以含α氢芳香族酮类为原料,将酮羰基在三氟磺酸和硅氢烷的共同作用下经还原脱氧生成相应烯烃。本发明的方法具有出色的选择性和简易的操作流程,使用廉价的催化反应体系,收率良好,具有巨大应用潜力。
Description
技术领域
本发明属于烯烃制备技术领域,涉及一种简便高效合成芳香族烯烃衍生物的 方法。
背景技术
芳香族烯烃类衍生物在有机精细化工领域,诸如药物合成、香精香料及有机 功能材料开发方面上都有着巨大的应用价值。从廉价易得的芳香酮类化合物到芳 香族烯烃的直接催化转化有着实际应用价值。当前,现有合成技术报道存在诸多 问题,反应条件苛刻危险(需要高温高压条件),且大多数催化体系使用昂贵的 金属配合物做催化剂。例如,2016年Ana C.Fernandes等利用铼配合物在170℃ 下催化异丙醇氢转移反应还原芳香酮化合物成相应烯烃化合物。2015年,Stephan 课题组报道了缺电子的B(C6F5)3作为催化剂在H2(60atm)惰性气体氛围及无水 条件下,甲苯溶液中加氢催化还原芳香酮类化合物生成相应烯烃化合物。综上, 尽管当前有廉价芳香酮向芳香族烯烃合成转化领域取得了一些进步,但是目前的 合成手段依然存在的操作条件苛刻,催化反应体系成本过高等问题,其适用的芳 香酮类小分子也存在很大局限性。因此,进一步发展简易高效的方法进行芳香酮 化合物转化合成芳香族烯烃仍需进一步发展探索。此外,一些重要芳香族烯烃化 合物有着实际需求而缺乏有效的市面供应渠道,这也使得开发该类合成转化方法 愈发重要。
发明内容
本发明的目的解决现有技术存在的催化体系成本高,反应条件苛刻,底物适 用范围窄的问题,发明了一种简便高效的芳香族烯烃化合物合成方法。采用三氟 磺酸/硅氢烷共催化转化芳香族酮类化合物,简便高效选择性地合成芳香族烯烃 化合物。
本发明的技术方案为:
以含α氢芳香族酮类为原料,将酮羰基在三氟磺酸和硅氢烷的共同作用下经 还原脱氧生成相应烯烃。
其中代表性的一种示例性反应式如:
反应式I:三氟磺酸/硅氢烷共催化芳香酮向芳香烯烃的转化
其中,所述含α氢芳香族酮类为芳香酮、含杂原子硫、氧、氮的杂环芳香族 酮类化合物中的一种;所述α氢芳香族酮类的酮基的一侧具有取代或未被取代的 吸电子基苯环;
优选的,所述含α氢芳香族酮类为上述化合物I;
其中,
n为1-5的整数,优选为1、2或3;
R1各自独立地为(即苯环或芳香杂环上连接的n个R1可以互不 相同)H、卤素、醚基、烷基、卤代烷基、硝基、取代硝基、硝基氧基、取代的 硝基氧基、磺酰基、取代磺酰基、氰基;优选为H、卤素C1-4的醚基、C1-4取代 的烷基、C1-4取代的卤代烷基、硝基、C1-4取代的硝基烷基、C1-4取代的硝基氧 基、磺酰基、C1-4取代的磺酰基、氰基;
R2为烷基、环烷基、取代烷基、取代环烷基、烷基苯基、取代 烷基苯基;优选为C1-7的烷基、C1-7的环烷基、C1-7的取代烷基、C1-7的取代环 烷基、C1-7的烷基苯基、C1-7的取代烷基苯基;
最优选的化合物I具有以下结构:
其中,所述硅氢烷为含有Si-H键且Si上具有至少一个C1-6取代基取代的化 合物;优选为1,1,3,3-四甲基二硅氧烷、二苯基硅烷、苯基硅烷、三异丙基硅基 硅烷;最优选为1,1,3,3-四甲基二硅氧烷;
其中,所述溶剂为有机溶剂,优选为四氢呋喃、1,4-二噁烷、乙醚中的一种, 最优选为四氢呋喃。
其中,所述方法中,反应过程需要在惰性气体保护下,搅拌并加热20-70℃ 温度下进行,优选为35-70℃。
优选的,所述溶剂的浓度为0.2-0.5M,最优选为0.33-0.5M;反应时间为1-24h。
优选的,所述含α氢芳香族酮类化合物、三氟磺酸、硅氢烷的投料当量比为 1:1.3:3。
其中,所述方法还包括后处理步骤,包括:用饱和碳酸氢钠溶液中和反应液, 再用乙酸乙酯稀释并萃取,合并有机相,有无水硫酸钠干燥,减压浓缩去除溶剂 得到残余物,再将残余物经硅胶柱层析分离,得到化合物II的目标烯烃产物。
相对于现有技术,本发明的有益效果如下:
本发明的方法具有出色的选择性和简易的操作流程,并且通过廉价的稳定含 α氢芳香酮类化合物,可大量合成市面上昂贵的烯烃产物,使用廉价的催化反应 体系,原料来源广泛、反应条件温和、操作简便、产物选择性高,收率良好,具 有巨大应用潜力。
以其中一种反应示例为例,本发明的反应机理如下:
本发明中,选取的含α氢芳香族酮类化合物具有吸电子基团,在还原过程中 更容易受到超强酸和小位阻硅氢烷的共同催化作用,同时一步脱水,使反应更加 偏向烯烃选择性,目标反应物产率高。
具体实施方式
以下结合具体实施例,对本发明做进一步详述。在下文中,如无特殊说明, 所述方法均为本领域常规方法,所使用得试剂均可通过商业途径购买获得。
实施例1-8反应条件典型实验
以下式1所示酮类化合物,探讨了不同反应条件下,对溴苯乙酮1a转化为 相应对溴苯乙烯目标产物式2a的产率变化。见以下代表性的实施例1-8
反应式1如下:
实施例1
由表1所示选用不同的溶剂在30℃下,于25mL Schlenk反应管中加入对溴 苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol) 和三氟磺酸(1.2equiv.,0.6mmol),该混合物在0.5M有机溶液中于氮气保护下 反应5h。具体反应结果如表1:
表1
实施例2
由表2所示,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5 mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol)和三氟磺酸(1.2equiv.,0.6 mmol)。在30℃条件下下,该混合物在不同浓度的四氢呋喃溶液(基于1a)中 于氮气保护下反应5h。具体反应结果如表2:
表2
实施例3
在30℃下,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5 mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol)和酸(1.3equiv.,0.6mmol), 该混合物在四氢呋喃(1.5mL)溶液中于氮气保护下反应5h。具体反应结果如 表3:
表3
实施例4
选用不同剂量的三氟磺酸来测试反应效果,于25mL Schlenk反应管中加入 对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol) 和三氟磺酸,该混合物在0.33M四氢呋喃溶液中于30℃氮气保护下反应5h。 反应结果如表4所示:
表4
实施例5
选用不同的硅氢烷与三氟磺酸催化转化1a成烯烃2a。25mL Schlenk反应管 中加入对溴苯乙酮1a(0.5mmol,99.5mg),硅氢烷(3.0equiv.,1.5mmol)和 三氟磺酸(1.3equiv.,0.65mmol),该混合物在0.33M四氢呋喃溶液中于30℃ 氮气保护下反应5h。结果如表5所示:
表5
实施例6
选用不同浓度1,1,3,3-四甲基二硅氧烷来实验反应效果,25mL Schlenk反应 管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷和三氟磺 酸(1.3equiv.,0.65mmol),该混合物在0.3M四氢呋喃溶液中于30℃氮气保 护下反应5h。结果如表6所示:
表6
实施例7
不同的温度下,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5 mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol),三氟磺酸(1.2equiv.,0.6 mmol),该混合物在0.3M四氢呋喃溶液中于氮气保护下反应5h。结果如表7 所示:
表7
实施例8
检测反应的最佳时间条件,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol),三氟磺酸(1.2equiv.,0.6mmol),该混合物在0.3M四氢呋喃溶液中于氮气保护下反应。 结果如表8所示:
表8
由实施例1-8可以看出最佳溶剂式四氢呋喃(0.3M),最佳的催化剂式三氟 磺酸(1.2equiv.,0.6mmol),最佳硅氢烷是1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5 mmol),最佳温度是35℃,最佳芳香酮原料1a,三氟磺酸及1,1,3,3-四甲基二硅 氧烷的配比是1:1.3:3。
通过以上实施例,最佳溶剂式四氢呋喃,最佳的催化剂是三氟磺酸,最佳硅 氢烷是1,1,3,3-四甲基二硅氧烷,最佳温度是35℃,最佳原料与磺酸硅氢烷的配 比是1:1.3:3为例,本发明的典型操作如下:
向25mL Schlenk反应管中加入式1所示的对溴苯乙酮1a(0.5mmol,99.5 mg),1,1,3,3-四甲基二硅氧烷(3equiv.,1.5mmol)四氢呋喃(1.5mL,0.33M) 三氟磺酸(1.3equiv.,0.65mmol),随后使用双排管将反应器内气氛用氮气置换 并将反应溶液在35℃下搅拌,经TLC,GC检测原料完全消耗的时间为(5小时), 即反应完全。该反应混合液冷却后用乙酸乙酯(10ml)稀释,加入饱和碳酸氢 钠溶液至混合液不再有气泡产生(PH≈7-8)。使用分液漏斗萃取得到有机相溶 液(乙酸乙酯溶液,合并有机相并用无水硫酸钠干燥,减压浓缩得到残余物经硅 胶柱层析分离(洗脱剂为石油醚)即得到式1所示的目标产物2a:
4-溴苯乙烯(2a)
1H NMR(400MHz,CDCl3):δ7.41(d,J=8.0Hz,2H),7.23(d,J=8.0Hz,2H), 6.62(dd,J=10.3,6.2Hz,1H),5.71(d,J=16.4,1H),5.24(d,J=10.3Hz,1H)ppm.
反应底物扩展实验:
在获得最佳反应条件的基础上,发明人进一步对该催化反应条件下,对不同 结构第五的适应性进行了研究。
实施例1b-q芳香酮类化合物的适应性研究,对应的芳香烯烃产物如下:
化合物2b-2n的数据表征如下:
(2-methylprop-1-en-1-yl)benzene(2b)
2b:1H NMR(400MHz,CDCl3):δ7.30(d,J=7.5Hz,2H),7.24-7.16(m,3H), 6.27(s,1H),1.90(s,3H),1.86(s,3H)ppm.
(E)-1,2-diphenylethene(2c)
2c:1H NMR(400 MHz,CDCl3):δ7.53-7.29(m,10H),7.13(s,2H)ppm.
1,2-dihydronaphthalene(2d)
2d:1H NMR(400MHz,CDCl3):δ7.10-7.01(m,3H),6.95-6.91(m,1H),6.38 (d,J=9.6Hz,1H),5.98-5.91(m,1H),2.72(t,J=8.2Hz,2H),2.24(tdd,J=8.0,4.4, 1.8Hz,2H)ppm.
(cyclopentylidenemethyl)benzene(2e)
2i:1H NMR(400MHz,CDCl3):δ7.35-7.34(m,4H),7.22-7.17(m,1H),6.41 -6.39(m,1H),2.61-2.57(m,2H),2.55-2.51(m,2H),1.86-1.79(m,2H),1.74- 1.67(m,2H)ppm.
1-allyl-4-bromobenzene(2f)
2f:1H NMR(400MHz,CDCl3):δ7.40(t,J=8.4Hz,2H),7.05(d,J=8.4Hz,2H),5.87-5.97(m,1H),5.03-5.09(m,2H),3.33(d,J=6.8Hz,2H)ppm.
1-methoxy-3-vinylbenzene(2g)
2g:1H NMR(400MHz,CDCl3):δ7.29-7.25(m,1H),7.04(d,J=7.6Hz,1H), 6.98(s,1H),6.86-6.83(m,1H),6.76-6.69(m,1H),5.77(d,J=17.6Hz,1H),5.28 (d,J=10.8Hz,1H),3.84(s,3H)ppm.
1-fluoro-3-vinylbenzene(2h)
2h:1H NMR(400MHz,CDCl3):δ7.56(s,1H),7.40-7.31(m,2H),7.22-7.18 (m,1H),6.69-6.61(m,1H),5.76(d,J=17.6Hz,1H),5.31(d,J=10.8Hz,1H)ppm.
1-chloro-4-vinylbenzene(2i)
2i:1H NMR(400MHz,CDCl3):δ7.35-7.28(m,4H),6.71-6.64(m,1H),5.73 (d,J=17.6Hz,1H),5.28(d,J=10.8Hz,1H)ppm.
1-iodo-4-vinylbenzene(2j)
2j:1H NMR(400MHz,CDCl3)δ7.65(d,J=8.2Hz,1H),7.15(d,J=8.2Hz, 1H),6.63(dd,J=17.6,10.9Hz,1H),5.75(d,J=17.6Hz,1H),5.27(d,J=10.9Hz, 1H)ppm.
2-iodo-4-vinylbenzene(2k)
2k:1HNMR(400MHz,CDCl3)d 7.84(dd,J=7.6,1.6Hz,1H),7.52(dd,J= 7.6,1.6Hz,1H),7.32(dd,J=7.6,7.6Hz,1H),6.95(ddd,J=7.6,7.6,1.6Hz,1H), 6.88(dd,J=17.4,10.8Hz,1H),5.63(d,J=17.4Hz,1H),5.32(d,J=10.8Hz,1H) ppm.
1-(trifluoromethyl)-4-vinylbenzene(2l)
2l:1H NMR(400MHz,CDCl3):δ7.60-7.49(m,4H),6.79-6.72(m,1H),5.86 (d,J=17.6Hz,1H),5.39(d,J=10.8Hz,1H)ppm.
1-(methylsulfonyl)-4-vinylbenzene(2m)
2m:1H NMR(400MHz,CDCl3):δ7.90(d,J=8.2Hz,2H),7.58(d,J=8.1Hz, 2H),6.77(dd,J=17.5,11.0Hz,1H),5.92(d,J=17.6Hz,1H),5.47(d,J=10.9Hz,1H), 3.05(s,3H)ppm.
1,3-difluoro-2-vinylbenzene(2n)
2n:1H NMR(400MHz,CDCl3):δ7.16(dq,J=6.3,2.0Hz,1H),6.89-6.85(m, 2H),6.73(dd,J=18.0,11.9Hz,1H),6.04(d,J=18.0Hz,1H),5.58(dd,J=11.9, 1.0Hz,1H)ppm.
3,5-dichloro-2-vinylbenzene(2o)
2o:1H NMR(400MHz,CDCl3):δ7.27(d,J=1.8Hz,2H),7.24(t,J=1.8Hz, 1H),6.59(dd,J=17.5,10.8Hz,1H),5.78(d,J=17.5Hz,1H),5.36(d,J=10.8Hz,1H) ppm.
1-nitro-4-vinylbenzene(2p)
2p:1H NMR(400MHz,CDCl3):δ8.28–8.11(m,2H),7.64–7.47(m,2H),6.78 (dd,J=17.6,10.9Hz,1H),5.93(d,J=17.6Hz,1H),5.50(d,J=10.9Hz,1H)ppm.
4-vinylbenzonitrile(2q)
2q:1H NMR(400MHz,CDCl3):δ7.62-7.60(m,2H),7.49-7.47(m,2H),6.76 -6.69(m,1H),5.87(d,J=17.6Hz,1H),5.45(d,J=10.8Hz,1H)ppm.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明 的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的 保护范围之内。
Claims (9)
1.一种烯烃衍生物合成方法,以含α氢芳香族酮类为原料,将酮羰基在三氟磺酸和硅氢烷的共同作用下经还原脱氧生成相应烯烃。
2.根据权利要求1所述的方法,其特征在于,所述含α氢芳香族酮类为芳香酮、含杂原子硫、氧、氮的杂环芳香族酮类化合物中的一种;所述α氢芳香族酮类的酮基的一侧具有取代或未被取代的吸电子基苯环。
3.根据权利要求1所述的方法,其特征在于,所述α氢芳香族酮类为下述化合物I:
其中,
n为1-5的整数,优选为1、2或3;
R1各自独立地为H、卤素、醚基、烷基、卤代烷基、硝基、取代硝基、硝基氧基、取代的硝基氧基、磺酰基、取代磺酰基、氰基;优选为H、卤素C1-4的醚基、C1-4取代的烷基、C1-4取代的卤代烷基、硝基、C1-4取代的硝基烷基、C1-4取代的硝基氧基、磺酰基、C1-4取代的磺酰基、氰基;
R2为烷基、环烷基、取代烷基、取代环烷基、烷基苯基、取代烷基苯基;优选为C1-7的烷基、C1-7的环烷基、C1-7的取代烷基、C1-7的取代环烷基、C1-7的烷基苯基、C1-7的取代烷基苯基;
最优选的化合物I具有以下结构:
4.根据权利要求1所述的方法,其特征在于,所述硅氢烷为含有Si-H键且Si上具有至少一个C1-6取代基取代的化合物;优选为1,1,3,3-四甲基二硅氧烷、二苯基硅烷、苯基硅烷、三异丙基硅基硅烷;最优选为1,1,3,3-四甲基二硅氧烷。
5.根据权利要求1所述的方法,其特征在于,所述溶剂为有机溶剂,优选为四氢呋喃、1,4-二噁烷、乙醚中的一种,最优选为四氢呋喃。
6.根据权利要求1所述的方法,其特征在于,所述方法中,反应过程需要在惰性气体保护下,搅拌并加热20-70℃温度下进行,优选为35-70℃。
7.根据权利要求1所述的方法,其特征在于,所述溶剂的浓度为0.2-0.5M,最优选为0.33-0.5M;反应时间为1-24h。
8.根据权利要求1所述的方法,其特征在于,所述含α氢芳香族酮类化合物、三氟磺酸、硅氢烷的投料当量比为1:1.3:3。
9.根据权利要求1所述的方法,其特征在于,还包括后处理步骤,包括:用饱和碳酸氢钠溶液中和反应液,再用乙酸乙酯稀释并萃取,合并有机相,有无水硫酸钠干燥,减压浓缩去除溶剂得到残余物,再将残余物经硅胶柱层析分离,得到化合物II的目标烯烃产物。
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