CN114149298B - 一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法 - Google Patents

一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法 Download PDF

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CN114149298B
CN114149298B CN202111385681.4A CN202111385681A CN114149298B CN 114149298 B CN114149298 B CN 114149298B CN 202111385681 A CN202111385681 A CN 202111385681A CN 114149298 B CN114149298 B CN 114149298B
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arylboronic acid
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朱纯银
夏鸿宇
张文凯
赵东波
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Jiangxi Maihao Chemical Technology Co ltd
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Abstract

本发明属于有机化学合成技术领域，公开了一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，在该方法中，腙可以同时作为金属配体和光催化剂，即双功能催化剂，在空气作为氧化剂的温和条件下合成联芳烃。在该方法中，使用空气作为氧化剂、可见光作为能量源，实现了温和条件下联芳烃的合成。该方法绿色环保，并且使用廉价金属，价格十分低廉，适合工业化应用。

Description

一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法
技术领域
本发明属于有机化学合成技术领域，具体涉及一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法。
背景技术
腙官能团由三原子结构C＝N-N组成，由于其模块化、合成简单、水解稳定性好(跟亚胺相比)，广泛应用于有机合成、药物化学和超分子化学中。在有机合成中，人名反应Enders SAMP/RAMP腙烷基化反应，就是使用腙作为手性辅基。此外，不同类型的腙类化合物，特别是N-芳基磺酰腙，在各种交叉偶联中作为卡宾前体得到了广泛的应用。尽管存在这些有机反应，与广泛应用的亚胺衍生催化剂(例如，用于烯烃聚合的双齿苯氧亚胺/酮亚胺配体)相比，腙作为配体/催化剂在有机合成中的应用较少。虽然有一些关于腙金属配合物的报道，但大多集中在生物化学、材料科学、分子制动器、化学传感器、分子逻辑电路、光电化学开关等领域的应用。鉴于目前报道的腙金属配合物，腙可以作为过渡金属催化反应的良好配体。此外，还有一些大π系的多齿腙配体，如吡啶醛-2-吡啶酰腙，这类腙通常在可见光下具有吸收，是可见光诱导反应的潜在光催化剂。因此，我们推测，在可见光诱导的过渡金属催化反应中，腙既可作为配体又可作为光催化剂，即双功能催化剂。
联芳烃是药物、聚合物和配体的基本组成部分，已引起了合成化学家的广泛关注。芳基卤化物和有机金属之间的各种交联偶联已被应用于合成联芳烃化合物，如Suzuki,Negishi,stile,Kumada和Hiyama反应。此外，通过芳基卤化物的还原偶联和有机硼化合物的氧化偶联也可以制备对称和不对称的联芳烃。其中，芳基硼酸的氧化偶联具有重要的应用，因为硼酸来源广泛，很容易商业获得，与其他常用的有机金属偶联反应相比，其合成方便，稳定性高，毒性低。有很多研究使用钯、铜、金、铑等多种催化剂及其纳米材料来催化芳基硼酸的氧化偶联，然而，这些方法通常需要较长的反应时间和较高的温度，这在一定程度上限制了它们在有机合成中的实际应用。因此，寻找更温和的反应方法仍然具有重要的研究意义。
发明内容
本发明的目的在于提供一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，在该方法中，腙可以同时作为金属配体和光催化剂，即双功能催化剂，在空气作为氧化剂的温和条件下合成联芳烃。
该发明的具体技术方案如下：在反应瓶中加入腙、金属盐和溶剂，室温搅拌1小时，然后加入芳基硼酸和碱，将反应体系置于蓝光或者白光之下，继续敞口反应8小时，得到偶联产物。反应式如下：
其中，Ar1、Ar2选自芳香环；优选地，Ar1、Ar2选自苯基或含取代基的苯基、萘基或含取代基的萘基、吡啶基或含取代基的吡啶基、呋喃基或含取代基的呋喃基、吡咯基或含取代基的吡咯基、噻吩基或含取代基的噻吩基。
所述腙选自如下结构(A,B,C)的化合物中的任一种：
其中，R1、R2、R3均为吡啶环的取代基，可在吡啶环上任意合理的位置，选自氢、烷基、卤素、烷氧基、胺基或三氟甲基；R4为苯环的取代基，可在苯环上任意合理的位置，选自氢、烷基、卤素、烷氧基、胺基或三氟甲基；R5、R6、R7和R8选自烷基、苯基或含取代基的苯基。
所述金属盐选自铜盐、钴盐、镍盐或钯盐；优选地，金属盐选自碘化铜、碘化亚铜、溴化铜、溴化亚铜、氯化铜、氯化亚铜、氯化钴、醋酸钴、溴化镍、氯化镍、氯化钯或醋酸钯。
所述的碱选自TEA(三乙胺)、DBU(1，8-二氮杂二环十一碳-7-烯)、DIPEA(二异丙基乙胺)、KOH、K2CO3,NaOH、Na2CO3、Cs2CO3、CsOH、NaH、K3PO4、K2HPO4、Na3PO4或者Na2HPO4中的任一种或多种的混合物。
所述腙与芳基硼酸的物质的量的比例为0.01～0.1:1；金属盐与芳基硼酸的物质的量的比例为0.01～0.1:1；碱与芳基硼酸的物质的量的比例为1～2:1。
所述溶剂为二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、甲醇、乙腈或水中的一种或几种。
本发明的有益效果为：
本发明提供了一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，在该方法中，腙可以同时作为金属配体和光催化剂，即双功能催化剂，同时使用空气作为氧化剂、可见光作为能量源，实现了温和条件下联芳烃的合成。该方法绿色环保，并且使用廉价金属，价格十分低廉，适合工业化应用。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
实施例中先列举了三种腙的制备方法：
(1)腙的制备方法(通用方法一)：
在反应瓶中加入吡啶肼(10mmol)、吡啶甲醛(10mmol)和溶剂乙醇(20mL)，搅拌下回流反应8小时，反应结束后，用水和二氯甲烷萃取三次.除去水层，有机层用无水硫酸钠干燥，过滤，浓缩，用20mL乙醇重结晶得腙A。
具体地，腙A1的制备步骤为：
吡啶肼选用2-肼吡啶，吡啶甲醛选用吡啶-2-甲醛，按照通用步骤一的方法制备腙A1.1H NMR:δ8.59(d,J＝7.5Hz,1H),8.01(d,J＝7.5Hz,1H),7.85(dd,J＝7.5,7.5Hz,1H),7.42(dd,J＝7.5,7.5Hz,1H),2.63(s,3H).13C NMR:δ164.7,164.5,157.4,149.2,137.2,124.2,123.6,20.5。
(2)腙的制备方法(通用方法二)：
在反应瓶中加入酰肼(10mmol)、吡啶甲醛(10mmol)和溶剂乙醇(20mL)，搅拌下回流反应10小时，反应结束后，用水和二氯甲烷萃取三次.除去水层，有机层用无水硫酸钠干燥，过滤，浓缩，用20mL乙醇重结晶得腙B。
具体地，腙B1的制备步骤为：
酰肼选用月桂酰肼，吡啶甲醛选用吡啶-2-甲醛，按照通用步骤二的方法制备腙B1.1H NMR:δ8.59(d,J＝7.5Hz,1H),8.01(d,J＝7.5Hz,1H),7.85(dd,J＝7.5,7.5Hz,1H),7.42(dd,J＝7.5,7.5Hz,1H),2.63(s,3H).13C NMR:δ164.7,164.5,157.4,149.2,137.2,124.2,123.6,20.5。
(3)腙的制备方法(通用方法三)：
在反应瓶中加入靛红(10mmol)、酰肼(10mmol)和溶剂乙醇(20mL)，搅拌下回流反应10小时，反应结束后，用水和二氯甲烷萃取三次.除去水层，有机层用无水硫酸钠干燥，过滤，浓缩，用20mL乙醇重结晶得腙C。
具体地，腙C1的制备步骤为：
酰肼选用月桂酰肼，靛红选用无取代的靛红，按照通用步骤三的方法制备腙C1.1HNMR:δ8.59(d,J＝7.5Hz,1H),8.01(d,J＝7.5Hz,1H),7.85(dd,J＝7.5,7.5Hz,1H),7.42(dd,J＝7.5,7.5Hz,1H),2.63(s,3H).13C NMR:δ164.7,164.5,157.4,149.2,137.2,124.2,123.6,20.5。
由芳基硼酸制备联芳烃类化合物的通用步骤：
在反应瓶中加入上述配体(0.6mmol)、金属盐(0.5mmol)，和溶剂(10mL)，室温搅拌1小时，然后加入芳基硼酸(10mmol)和碱(12mmol)接通氧气或空气，并照射蓝光或白光，反应结束后，用水和乙酸乙酯萃取三次，收集有机相，用无水硫酸钠干燥，用旋转蒸发仪除去溶剂，然后将其通过硅胶色谱纯化，得到纯的联芳烃化合物。
实施例1
联苯的制备：芳基硼酸选用苯硼酸，配体选用A1，金属盐选用溴化铜，碱选用DBU，溶剂选用N,N-二甲基甲酰胺，按照通用步骤的方法，使用15w蓝光LED照射，制得联苯，产率86％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.67-7.65(m,4H),7.44-7.40(m,4H),7.35-7.31(m,2H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)141.3,128.8,127.3,127.2。
实施例2
4，4'-二甲基联苯的制备：芳基硼酸选用对甲基苯硼酸，配体选用A2，金属盐选用氯化亚铜，碱选用K3PO4，溶剂选用乙腈，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-二甲基联苯，产率88％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.48-7.46(d,J＝8.0Hz,4H),7.23-7.21(d,J＝8.0Hz,4H),2.38(s,6H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)138.3,136.7,129.5,126.9,21.2。
实施例3
3，3′-二甲基联苯的制备:芳基硼酸选用间甲基苯硼酸，配体选用A3，金属盐选用氯化钴，碱选用Cs2CO3，溶剂选用N,N-二甲基乙酰胺，按照通用步骤的方法，使用15w白光LED照射，制得3，3′-二甲基联苯，产率85％，1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.54-7.51(m,4H),7.45(t,J＝8.0Hz,2H),7.28(d,J＝7.1Hz,2H),2.55(s,6H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)141.7,138.4,128.7,128.1,128.0,124.4,21.7。
实施例4
4，4'-二氟联苯的制备：芳基硼酸选用对氟苯硼酸，配体选用A1，金属盐选用溴化镍，碱选用DIPEA，溶剂选用二甲基亚砜，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-二氟联苯，产率86％。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.51-7.48(m,4H),7.13(t,J＝8.6Hz,4H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)162.4(d,J＝237.2Hz),136.4(d,J＝3.2Hz),128.6(d,J＝7.8Hz),115.7(d,J＝21.3Hz)。
实施例5
4，4'-二氯联苯的制备：芳基硼酸选用对氯苯硼酸，配体选用A1，金属盐选用氯化钯，碱选用K2HPO4，溶剂选用N,N-二甲基甲酰胺，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-二氯联苯，产率87％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.46-7.49(m,4H),7.40-7.42(m,4H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)138.4,133.8,129.1,128.2。
实施例6
4，4'-二溴联苯的制备：芳基硼酸选用对溴苯硼酸，配体选用A3，金属盐选用溴化亚铜，碱选用K3PO4，溶剂选用N,N-二甲基乙酰胺，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-二溴联苯，产率81％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.56(m,4H),7.42(m,4H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)138.9,132.0,128.5,121.8。
实施例7
4，4'-二甲氧基联苯的制备：芳基硼酸选用对甲氧基苯硼酸，配体选用A1，金属盐选用碘化亚铜，碱选用Na 3PO4，溶剂选用N,N-二甲基甲酰胺，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-二甲氧基联苯，产率85％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.49(d,J＝8.6Hz,4H),6.97(d,J＝8.6Hz,4H),3.86(s,6H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)158.7,133.5,127.8,114.2,55.4。
实施例8
4，4'-联苯二甲腈的制备：芳基硼酸选用对腈基苯硼酸，配体选用A2，金属盐选用醋酸钯，碱选用TEA，溶剂选用N,N-二甲基甲酰胺，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-联苯二甲腈，产率81％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.74(q,J1＝8.2Hz,J2＝33.2Hz,8H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)143.5,132.9,127.9,118.4,112.4。
实施例9
2，2'-联吡啶的制备：芳基硼酸选用吡啶-2-硼酸，配体选用A3，金属盐选用醋酸钴，碱选用DBU，溶剂选用N,N-二甲基甲酰胺，按照通用步骤的方法，使用15w白光LED照射，制得，2，2'-联吡啶，产率76％，淡黄色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)8.67-8.68(m,2H),8.38-8.40(m,2H),7.79-7.83(m,2H),7.28-7.32(m,2H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)156.2,149.2,137.0,123.7,121.1。
实施例10
4，4'-双(三氟甲基)联苯的制备：芳基硼酸选用对三氟甲基苯硼酸，配体选用A1，金属盐选用氯化镍，碱选用CsOH，溶剂选用N,N-二甲基甲酰胺，按照通用步骤的方法，使用15w白光LED照射，制得4，4'-双(三氟甲基)联苯，产率88％，白色固体。1H NMR(400MHz,CDCl3,TMS)δ(ppm)7.76-7.70(m,8H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm)143.2,130.5(d,J＝33.5Hz),127.6,125.9(q,J＝4.1Hz),124.1(d,J＝272.9Hz)。

Claims (7)

1.一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，该方法以芳基硼酸为原料，腙和金属盐为催化剂，空气作为氧化剂，在碱和光照条件下合成联芳烃，其反应式如下：
其中，Ar1、Ar2均选自苯基或含取代基的苯基；
其中，腙选自如下化合物：
R1、R2均为吡啶环的取代基，可在吡啶环上任意合理的位置，选自氢、烷基、卤素、烷氧基、胺基或三氟甲基；R5选自烷基、苯基或含取代基的苯基；
其中，金属盐选自铜盐、钴盐、镍盐或钯盐。
2.如权利要求1所述的一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，所述腙选自如下化合物：
3.如权利要求1所述的一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，金属盐选自碘化铜、碘化亚铜、溴化铜、溴化亚铜、氯化铜、氯化亚铜、氯化钴、醋酸钴、溴化镍、氯化镍、氯化钯或醋酸钯。
4.如权利要求1所述的一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，所述的碱选自三乙胺TEA、1，8-二氮杂二环十一碳-7-烯DBU、二异丙基乙胺DIPEA、KOH、K2CO3,NaOH、Na2CO3、Cs2CO3、CsOH、NaH、K3PO4、K2HPO4、Na3PO4或者Na2HPO4中的任一种或多种的混合物。
5.如权利要求1所述的一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，所述腙与芳基硼酸的物质的量的比例为0.01～0.1:1；金属盐与芳基硼酸的物质的量的比例为0.01～0.1:1；碱与芳基硼酸的物质的量的比例为1～2:1。
6.如权利要求1所述的一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，具体反应步骤为：在反应瓶中加入腙、金属盐和溶剂，室温搅拌一定时间，然后加入芳基硼酸和碱，将反应体系置于蓝光或者白光之下，继续敞口反应数小时，得到偶联产物。
7.如权利要求6所述的一种腙催化剂实现的由芳基硼酸制备联芳烃类化合物的方法，其特征在于，所述溶剂为二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、甲醇、乙腈或水中的一种或几种，室温搅拌时间为1小时，敞口反应时间为8小时。
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