CN111704558B - 一种钯催化制备苯基-2-（2’-氰基苯基）乙炔类化合物的方法 - Google Patents

一种钯催化制备苯基-2-（2’-氰基苯基）乙炔类化合物的方法 Download PDF

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CN111704558B
CN111704558B CN202010571136.3A CN202010571136A CN111704558B CN 111704558 B CN111704558 B CN 111704558B CN 202010571136 A CN202010571136 A CN 202010571136A CN 111704558 B CN111704558 B CN 111704558B
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蔡荣荣
韩伊潇
李静宁
谢倩倩
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Jiyang College of Zhejiang A&F University
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Abstract

本发明公开了一种钯催化制备式(Ⅳ)所示的苯基‑2‑(2’‑氰基苯基)乙炔类化合物的方法，制备方法为：式(Ⅰ)所示的苯甲腈类化合物、式(Ⅱ)所示的乙炔和式(Ⅲ)所示的碘代苯类化合物，以氯化钯为催化剂，以碳酸钠为碱，以二甲基亚砜为溶剂，在氧气下充分反应反，所述的反应产物通过后处理制得苯基‑2‑(2’‑氰基苯基)乙炔类化合物。本发明方法化剂高效，符合绿色环保要求；催化体系适应性广，适用于大规模医药化工中间体生产。
Figure DDA0002549582100000011

Description

一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法
技术领域
本发明属于医药化工中间体制备技术领域，具体涉及钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法。
背景技术
苯基-2-(2’-氰基苯基)乙炔类化合物是一类非常重要的化工原料和合成中间体，广泛用于制造药物、合成纤维和塑料。同时苯基-2-(2’-氰基苯基)乙炔类化合物常用于电镀业、采矿业(提取金、银等)，制造各种树脂和合成腈类化合物。有时也用于仓库和船舱烟熏灭鼠。苯基-2-(2’-氰基苯基)乙炔类化合物最重要的性质是它在弱碱性介质中较稳定。因此，在肥皂、洗涤剂等产品中能够代替醛类以增加香精的稳定性。已报道的苯基-2-(2’-氰基苯基)乙炔类化合物制备方法主要是通过金属催化，经过多步的-CN基取代才能得到，存在反应步骤多、反应效率低和反应过程易生成剧毒氢氰酸等缺点。本方法通过采用催化效率高的氯化钯作为催化剂，多组分一锅法实现苯基-2-(2’-氰基苯基)乙炔类化合物的绿色制备。具有成本低廉、操作简单、安全可靠、产率优良等优点。在苯基-2-(2’-氰基苯基)乙炔类化合物相关的药物中间体合成工业领域具有重要的应用前景。
发明内容
针对现有技术中存在的问题，本发明目的在于在提供一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法。
本发明通过以下技术方案加以实现：
所述的一种钯催化制备式(Ⅳ)所示的苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于制备方法为：式(Ⅰ)所示的苯甲腈类化合物、式(Ⅱ)所示的乙炔和式(Ⅲ)所示的碘代苯类化合物，以金属盐为催化剂，以碳酸盐为碱，以有机溶剂为介质，在氧气下充分反应，制得目标反应产物，所述反应产物通过后处理制得苯基-2-(2’-氰基苯基)乙炔类化合物；所述金属盐催化剂为氯化钯，所述的碳酸盐为碳酸钠，所述的有机溶剂为二甲基亚砜；
Figure GDA0004150103230000021
反应式中，R1选自下列之一：氢、甲基、二亚甲氧基；R2选自下列之一：氢、甲基、甲氧基、三氟甲基、二甲氨基、苯基。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与碘代苯类化合物的比例为5mmol：6mmol：5mmol。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与氯化钯的比例为5mmol：6mmol：0.5mmol。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与碳酸钠的比例为5mmol：6mmol：10mmol。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与溶剂二甲基亚砜的比例为5mmol：6mmol：15mL。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与碘代苯类化合物的当量比为1:(1-1.2)：1。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的反应在氧气气氛下进行，反应温度为100℃，反应时间为10小时。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述后处理的具体方法由以下步骤组成：
1)萃取：反应产物常温冷却至室温后，往反应产物中添加20mL饱和氯化钠水溶液，然后用乙酸乙酯萃取3次，每次20mL，萃取液合并；
2)浓缩：将萃取液用无水硫酸钠干燥，用旋转蒸发仪旋干，得浓缩物；
3)将所得浓缩物用柱层析硅胶吸附，加入到200-300目的层析硅胶柱中，以正己烷：乙酸乙酯按一定的比例快速柱层析，洗脱液合并，旋转蒸发仪旋干，油泵抽得产物苯基-2-(2’-氰基苯基)乙炔类化合物。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于步骤2)中干燥时间为10小时。
所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于步骤3)中正己烷和乙酸乙酯的体积比例为4:1-1:1。
附图说明
图1为本发明中产物4a的1H NMR谱；
图2为本发明中产物4a的13C NMR谱；
图3为本发明中产物4b的1H NMR谱；
图4为本发明中产物4b的13C-NMR谱；
图5为本发明中产物4c的1H NMR谱；
图6为本发明中产物4c的13C-NMR谱；
图7为本发明中产物4d的1H NMR谱；
图8为本发明中产物4d的13C NMR谱；
图9为本发明中产物4e的1H NMR谱；
图10为本发明中产物4e的13C-NMR谱；
图11为本发明中产物4f的1H NMR谱；
图12为本发明中产物4f的13C NMR谱；
图13为本发明中产物4g的1H NMR谱；
图14为本发明中产物4g的13C-NMR谱；
图15为本发明中产物4h的1H NMR谱；
图16为本发明中产物4h的13C NMR谱；
具体实施方式
以下结合具体实施例对本发明予以进一步详述。
本发明合成步骤，在一个25mL的圆底烧瓶中依此加入5mmol苯甲腈类化合物1、6mmol乙炔2和5mmol的碘代苯类化合物3，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4的纯品，产率75-93％。具体实施例和表征数据如下。
Figure GDA0004150103230000051
实施例1：4a产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol苯甲腈、6mmol乙炔和5mmol的4-三氟甲基碘苯，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4a(1220mg，产率90％，黄色粉末)。4a1H NMR图谱见图1，13C NMR图谱见图2。
2-((4-(Trifluoromethyl)phenyl)ethynyl)benzonitrile(4a).Mp 105-106℃；
1H NMR(400MHz,CDCl3)δ7.58-7.72(m,6H),7.40-7.48(m,2H)；
13C NMR(100MHz,CDCl3)δ134.4,134.0,133.3,132.8,132.6,132.4,132.3,129.0,127.7,126.5,125.9,125.5(q,J＝3.89Hz,1C),122.5,117.5,117.2,115.9,115.6,94.2,87.8；
HRMS(ESI-TOF)[M+H]+Calcd for C16H9F3N 272.0687,found 272.0702.
实施例2：4b产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol苯甲腈、6mmol乙炔和5mmol的6-甲氧基-2-碘萘，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4b(1302mg，产率92％，黄色粉末)。4b1H NMR图谱见图3，13C NMR图谱见图4。
2-((6-Methoxynaphthalen-2-yl)ethynyl)benzonitrile(4b).Mp113-114℃；
1H NMR(400MHz,CDCl3)δ8.06(s,1H),7.54-7.74(m,6H),7.39(td,J＝7.7,1.3Hz,1H),7.17(dd,J＝8.9,2.5Hz,1H),7.12(d,J＝2.5Hz,1H),3.92(s,3H)；
13C NMR(100MHz,CDCl3)δ158.8,134.8,132.8,132.5,132.2,132.1,129.7,129.0,128.5,128.1,127.6,127.1,119.7,117.8,116.9,115.3,105.9,96.9,85.5,55.5；
HRMS(ESI-TOF)[M+H]+Calcd for C20H14NO 284.1075,found284.1071.
实施例3：4c产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol苯甲腈、6mmol乙炔和5mmol的2-碘吡啶，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4c(908mg，产率89％，黄色粉末)。4c1H NMR图谱见图5，13C NMR图谱见图6。
2-(Pyridin-2-ylethynyl)benzonitrile(4c).Mp 116-117℃；
1H NMR(400MHz,CDCl3)δ8.63(d,J＝4.5Hz,1H),7.64-7.72(m,4H),7.57(td,J＝7.7,1.3Hz,1H),7.42-7.46(m,1H),7.25-7.29(m,1H)；
13C NMR(100MHz,CDCl3)δ150.3,142.5,136.4,132.8,132.2,129.1,128.6,128.2,126.3,123.7,117.4,115.7,94.6,85.0；
HRMS(ESI-TOF)[M+H]+Calcd for C14H9N2 205.0766,found 205.0775.
实施例4：4d产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol苯甲腈、6mmol乙炔和5mmol的2-碘噻吩，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4d(1045mg，产率81％，黄色粉末)。4d1H NMR图谱见图7，13C NMR图谱见图8。
2-(Thiophen-3-ylethynyl)benzonitrile(4d).Mp 82-83℃；
1H NMR(400MHz CDCl3)δ7.52-7.65(m,4H),7.36-7.41(m,1H),7.30-7.32(m,1H),7.24(d,J＝4.9Hz,1H)；
13C NMR(100MHz,CDCl3)δ132.8,132.5,132.1,130.5,130.0,128.3,127.3,125.8,121.2,117.7,115.1,91.3,85.4；
HRMS(ESI-TOF)[M+H]+Calcd for C13H8NS 210.0377,found 210.0388.
实施例5：4e产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol3,4-二氧亚甲基苯甲腈、6mmol乙炔和5mmol的对甲氧基碘苯，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4e(1080mg，产率78％，黄色粉末)。4e1H NMR图谱见图9，13C NMR图谱见图10。
6-((4-Methoxyphenyl)ethynyl)benzo[d][1,3]dioxole-5-carbonitrile(4e).Mp 102-103℃；
1H NMR(400MHz,CDCl3)δ7.51(d,J＝7.0Hz,2H),6.99(d,J＝13.7Hz,2H),6.87(d,J＝8.8Hz,2H),6.07(s,2H),3.82(s,3H)；
13C NMR(100MHz,CDCl3)δ160.3,151.3,147.6,133.5,132.4,123.6,117.9,114.2,113.8,111.6,108.4,102.7,95.0,84.6,55.4；
HRMS(ESI-TOF)[M+H]+Calcd for C17H12NO3 278.0817,found 278.0824.实施例6：4f产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol3-吲哚甲腈、6mmol乙炔和5mmol的碘苯，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4f(911mg，产率75％，黄色粉末)。4f1H NMR图谱见图11，13C NMR图谱见图12。
2-(Phenylethynyl)benzofuran-3-carbonitrile(4f).Mp 95-96℃；
1H NMR(400MHz,CDCl3)δ7.81(d,J＝7.8Hz,1H),7.62-7.64(m,2H),7.55(d,J＝3.6Hz,2H),7.38-7.46(m,4H)；
13C NMR(100MHz,CDCl3)δ155.3,132.1,129.7,129.2,129.0,128.7,126.3,125.0,121.9,121.7,116.4,112.4,111.3,100.9,76.0；
HRMS(ESI-TOF)[M+H]+Calcd for C17H10NO 244.0762,found 244.0760.
实施例7：4g产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol3-吡啶甲腈、6mmol乙炔和5mmol的碘苯，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4g(949mg，产率93％，黄色粉末)。4g1H NMR图谱见图13，13C NMR图谱见图14。
2-(Phenylethynyl)nicotinonitrile(4g).Mp 108-109℃；
1H NMR(400MHz,CDCl3)δ8.76(d,J＝4.1Hz,1H),7.97(d,J＝7.7Hz,1H),7.68(d,J＝7.0Hz,2H),7.32-7.44(m,4H)；
13C NMR(100MHz,CDCl3)δ153.0,146.0,140.0,132.6,130.0,128.7,122.2,121.0,116.1,112.9,96.2,85.8；
HRMS(ESI-TOF)[M+H]+Calcd for C14H9N2 205.0766,found 205.0758.实施例8：4h产物的制备
室温下，在一个25mL的圆底烧瓶中依此加入5mmol3-喹啉甲腈、6mmol乙炔和5mmol的4-二甲氨基碘苯，然后依次加入15mL的二甲基亚砜、0.5mmol氯化钯和10mmol的碳酸钠，反应在氧气下，100℃下搅拌10小时。冷却后向体系中加入20mL饱和氯化钠水溶液，用乙酸乙酯萃取3次，每次20mL，合并有机相，用无水硫酸钠干燥后，蒸除溶剂，200-300目的硅胶柱层析得苯基-2-(2’-氰基苯基)乙炔类化合物4h(1233mg，产率83％，黄色粉末)。4h1H NMR图谱见图15，13C NMR图谱见图16。
2-((4-(Dimethylamino)phenyl)ethynyl)quinoline-3-carbonitrile(4h).Mp113-114℃；
1H NMR(400MHz,CDCl3)δ8.44(s,1H),8.08(d,J＝8.5Hz,1H),7.78-7.83(m,2H),7.56-7.61(m,3H),6.64(d,J＝8.8Hz,2H),3.00(s,6H)；
13C NMR(100MHz,CDCl3)δ151.2,148.8,143.7,142.0,134.2,133.1,129.3,128.1,124.6,116.8,111.6,109.4,107.2,99.0,85.9,40.1；
HRMS(ESI-TOF)[M+H]+Calcd for C20H16N3 298.1344,found 298.1357.

Claims (10)

1.一种钯催化制备式(Ⅳ)所示的苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于制备方法为：式(Ⅰ)所示的苯甲腈类化合物、式(Ⅱ)所示的乙炔和式(Ⅲ)所示的碘代苯类化合物，以金属盐为催化剂，以碳酸盐为碱，以有机溶剂为介质，在氧气下充分反应，制得反应产物，所述的反应产物通过后处理制得苯基-2-(2’-氰基苯基)乙炔类化合物；金属盐催化剂为氯化钯，所述的碳酸盐为碳酸钠，所述的有机溶剂为二甲基亚砜；
Figure FDA0002549582070000011
反应式中，R1选自下列之一：氢、甲基、二亚甲氧基；R2选自下列之一：氢、甲基、甲氧基、三氟甲基、二甲氨基、苯基。
2.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与碘代苯类化合物的比例为5mmol：6mmol：5mmol。
3.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与氯化钯的比例为5mmol：6mmol：0.5mmol。
4.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与碳酸钠的比例为5mmol：6mmol：10mmol。
5.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与溶剂二甲基亚砜的比例为5mmol：6mmol：15mL。
6.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的苯甲腈类化合物、乙炔与碘代苯类化合物的当量比为1:(1-1.2)：1。
7.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述的反应在氧气气氛下进行，反应温度为100℃，反应时间为10小时。
8.根据权利要求1所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于所述后处理的具体方法由以下步骤组成：
1)萃取：反应产物常温冷却至室温后，往反应产物中添加20mL饱和氯化钠水溶液，然后用乙酸乙酯萃取3次，每次20mL，萃取液合并；
2)浓缩：将萃取液用无水硫酸钠干燥，用旋转蒸发仪旋干，得浓缩物；
3)将所得浓缩物用柱层析硅胶吸附，加入到200-300目的层析硅胶柱中，以正己烷：乙酸乙酯按一定的比例快速柱层析，洗脱液合并，旋转蒸发仪旋干，油泵抽得产物苯基-2-(2’-氰基苯基)乙炔类化合物。
9.根据权利要求8所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于步骤2)中干燥时间为10小时。
10.根据权利要求8所述的一种钯催化制备苯基-2-(2’-氰基苯基)乙炔类化合物的方法，其特征在于步骤3)中正己烷和乙酸乙酯的体积比例为4:1-1:1。
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