CN108623439A - 一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法 - Google Patents

一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法 Download PDF

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CN108623439A
CN108623439A CN201810298659.8A CN201810298659A CN108623439A CN 108623439 A CN108623439 A CN 108623439A CN 201810298659 A CN201810298659 A CN 201810298659A CN 108623439 A CN108623439 A CN 108623439A
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diazonium salts
aryl diazonium
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arylsulfonyl hydrazine
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赵保丽
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Abstract

本发明公开了一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，包括：在钯催化剂、配体和添加剂的作用下，芳基重氮盐和芳基磺酰肼在有机溶剂中发生脱氮偶联反应，反应结束后经过后处理得到所述的联芳烃。本发明的方法的底物价格低廉，性质稳定，便于操作，同时，反应收率高，底物的普适性较好。

Description

一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法
技术领域
本发明属于有机合成领域，具体涉及一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法。
背景技术
近年来,经由C-N键活化而不是C-X键或C-O键断裂启动金属催化循环来构筑化合物的方法已经成为有机金属化学研究的新途径和新思路。在这类研究中,芳基重氮盐因其独特的性质成为偶联反应中极具研究价值的亲电试剂，成为新的研究热点。其主要原因在于芳基重氮盐具有以下特点：
(1)芳基重氮盐可以很容易地由廉价的芳香胺合成，而且收率很高,几乎可以定量得到,易于大量制备且便于操作。
(2)在钯催化的偶联反应中,芳基重氮盐作为亲电试剂的反应活性高于其对应的卤代烃和芳香酯.在反应中随着氮气分子的离去形成芳香钯中间体来启动催化循环,该步骤通过热力学计算可知其所需要能量很低,室温下就能进行,一般不会成为反应的决速步。
(3)以重氮盐为亲电试剂的偶联反应条件都较温和,一般在室温下就能进行,且通常不需要加入碱或配体等作为添加剂,易于后处理和分离。
(4)重氮基团在反应中以氮气分子的形式离残留,符合绿色化学的要求.反应一般不需要惰性气体的保护,在空气中就能很好的进行。
(5)重氮基团相对于卤素在偶联反应的化学选择性上也是具有优势的. 利用其与卤素取代基的活性差异可以制备氯、溴或碘取代的产物,具有良好的官能团耐受性,还可以分步制备非对称的并具备多取代结构的药物和农药中间体。([1]Bonin,H.；Fouquet,E.；Felpin,F.X.Adv.Synth.Catal. 2011,353,3063；[2]Roglans,A.；Pla-Quintana,A.；M.Chem. Rev.2006,106,4622；[3]Taylor,J.G.；Moro,A.V.；Correia,C.R.D.Eur.J. Org.Chem.2011,1403；[4]Xiao,Q.；Zhang,Y.；Wang,J.Acc.Chem.Res.2013,46,236；[5]Mo,F.；Dong,G.；Zhang,Y.；Wang,J.Org.Biomol.Chem. 2013,11,1582)
芳基磺酰肼是一类稳定性好,易制备,低毒性的固体化合物,在有机合成中一般用作还原剂来还原双键；接着研究发现磺酰肼也可以作为砜基来源,通过加热等条件可以直脱掉肼基生成相应的亚磺酸根负离子,与亲电试剂反应得到砜基产物；还可以与不饱和的共轭醛和酮生成腙和合成五元杂环化合物等。最近的研究发现,芳基磺酰肼还可以在Pd等过渡金属催化下脱掉肼基和砜基,作为一种新型芳基来源；芳基磺酰肼还可以作为一种新型硫源合成二芳基硫醚化合物.[1]Aziz,J.；Messaoudi,S.；Alami,M.； Hamze,A.Org.Biomol.Chem.2014,12,9743.
发明内容
本发明提供了一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，该方法采用的原料稳定性好，同时反应收率高。
一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，包括：在钯催化剂、配体和添加剂的作用下，芳基重氮盐和芳基磺酰肼在有机溶剂中发生脱氮偶联反应，反应结束后经过后处理得到所述的联芳烃；
所述的联芳烃的结构如式(I)所示：
所述的芳基重氮盐的结构如式(II)所示：
所述的芳基磺酰肼的结构如式(III)所示：
式(I)～(III)中，R1和R2独立地选自H、甲基、甲氧基、F、-CN、乙酰基、羟基、氨基、甲酰基、Cl、-CF3、-NO2中的一个或者多个。
作为优选，所述的R1和R2独立地选自H、C1～C5烷基、C1～C5烷氧基、卤素、-CN、C1～C5烷酰基、羟基、氨基、-CF3、-NO2中的一个或者多个。
钯催化剂的种类会对反应的结果产生较大的影响，作为优选，所述的钯催化剂为PdCl2。
同时，配体的种类也会对反应效率产生较大的影响，作为优选，所述的配体为Dcypm，此时，反应收率较高。
作为优选，所述的碱为KOAc。
作为优选，所述的添加剂为TBAI。
作为优选，所述的溶剂为DMSO。
作为优选，反应温度为90～110℃，反应时间为12～24小时。
作为优选，所述的联芳烃为以下化合物中的一种：
同现有技术相比，本发明的有益效果体现在：
本发明的偶联反应采用价格便宜，性质稳定的原料作为反应试剂，操作条件简单，底物适应性广；同时，反应收率较高，具有较好的应用价值。
具体实施方式
实施例1
在反应瓶中，加入苯磺酰肼(1mmol)、苯基重氮盐(1.1mmol)、TBAI(四丁基碘化铵)(1.5mmol)、KOAc(2.0mmol)、钯催化剂(0.05mmol)、配体(0.1mmol)和2mL DMSO，然后加热至100℃进行反应，反应12小时后，TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应条件和反应结果见表1，反应式如下：
表1
表格中所提到的收率为分离收率。
实施例2
在反应瓶中，加入苯基磺酰肼(1mmol)、苯基重氮盐(1.1mmol)、添加剂(1.5mmol)、碱(2.0mmol)、PdCl2(0.05mmol)、配体Dcypm(双(二环己基膦)甲烷)(0.1mmol)和2mL溶剂，然后加热至100℃进行反应，反应 12小时后，TLC监测反应完全，降至室温，滤除固体，加入1mL水后用 2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应条件和反应结果见表2，反应式如下：
表2
实施例3
在反应瓶中，加入苯基磺酰肼(1mmol)、芳基重氮盐(1.1mmol)， TBAI(1.5mmol),KOAc(2.0mmol),PdCl2(0.05mmol)、配体Dcypm (0.1mmol)和2mL DMSO，然后加热至100℃进行反应，反应12小时后， TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应式和反应结果见下式：
实施例4
在反应瓶中，加入芳基磺酰肼(1mmol)、苯基重氮盐(1.1mmol)， TBAI(1.5mmol),KOAc(2.0mmol),PdCl2(0.05mmol)、配体Dcypm (0.1mmol)和2mL DMSO，然后加热至100℃进行反应，反应12小时后，TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应式和反应结果见下式：
部分产物的表征数据如下：
3-Phenyl-pyridine(CAS#1008-88-4,3p)
m.p.115–116℃；1H NMR(400MHz,DMSO):δ8.92(d,J＝2.0Hz,1H),8.58(m,1H),8.16-8.00(m,1H),7.84-7.64(m,2H),7.57-7.48(m,3H),7.45(d,J＝7.2Hz,1H).MS(EI):m/e(％)155(100),154(22),76(11).
2-Phenylpyrazine(CAS#29460-97-7,3q)
m.p.75–76℃；1H NMR(400MHz,CDCl3)δ9.03(s,1H),8.73-8.59(m,1H),8.51(d,J＝2.4Hz,1H),8.03(m,2H),7.64-7.37(m,3H)；MS(EI)m/e 156(100),129(23),103(92), 76(25),51(17),39(6).
1,1′-Biphenyl-4-amine(CAS#92-67-1,4f).
m.p.46-47℃；1H NMR(400MHz,DMSO)δ7.60-7.47(m,2H),7.35(t,J＝8.0Hz,4H),7.21(t,J＝7.2Hz,1H),6.63(d,J＝8.4Hz,2H),5.23(s,2H)；MS(EI)m/e 169(100),139(10),115(8),83(11).
1,1′-Biphenyl-4-ol(CAS#92-69-3,4g)
m.p.164-166℃；1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.0Hz,2H),7.49(d,J＝8.4Hz, 2H),7.43(t,J＝7.6Hz,2H),7.32(t,J＝7.2Hz,1H),6.91(d,J＝8.4Hz,2H),4.73(s,1H)； MS(EI)m/e 170(100),169(91),141(34),115(23),83(10).
5-Phenylpyrimidine(CAS#34771-45-4,4p)
m.p.41+42℃；1H NMR(400MHz,CDCl3)δ9.21(s,1H),8.94(s,2H),7.62-7.56(m,2H), 7.54-7.49(m,2H),7.48-7.41(m,1H).MS(EI):m/e(％)156(100),102(72),76(16),51(21).
3-Phenyl-quinoline(CAS#1666-96-2,4q)
m.p.49-51℃；1H NMR(400MHz,CDCl3)δ9.22(d,J＝3.2Hz,1H),8.31(d,J＝2.0Hz,1H),8.15(d,J＝8.4Hz,1H),7.88(d,J＝7.6Hz,1H),7.73(m,3H),7.65-7.49(m,3H), 7.47-7.38(m,1H).MS(EI):m/e(％)205(100),176(13),151(8),102(16),88(12),76(29), 51(5).
4-Phenylisoquinoline(CAS#19571-30-3,4r)
m.p.78-79℃；1H NMR(400MHz,CDCl3)δ9.25(s,1H),8.48(s,1H),8.03(d,J＝7.6Hz, 1H),7.91(d,J＝8.2Hz,1H),7.72-7.59(m,2H),7.57-7.40(m,5H).MS(EI):m/e(％)205 (100),176(21),151(9),102(23),88(20),76(14).
3-Phenyl-thiophene(CAS#2404-87-7,4s)
m.p.90-91℃；1H NMR(400MHz,CDCl3)δ7.62(m,2H),7.48-7.44(m,1H),7.43-7.36(m,4H),7.31(m,1H).MS(EI):m/e(％)160(100),115(34).

Claims (9)

1.一种由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，包括：在钯催化剂、配体和添加剂的作用下，芳基重氮盐和芳基磺酰肼在有机溶剂中发生脱氮偶联反应，反应结束后经过后处理得到所述的联芳烃；
所述的联芳烃的结构如式(I)所示：
所述的芳基重氮盐的结构如式(II)所示：
所述的芳基磺酰肼的结构如式(III)所示：
式(I)～(III)中，R1和R2独立地选自H、C1～C5烷基、C1～C5烷氧基、卤素、-CN、C1～C5烷酰基、羟基、氨基、-CF3、-NO2中的一个或者多个。
2.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，R1和R2独立地选自H、甲基、甲氧基、F、-CN、乙酰基、羟基、氨基、甲酰基、Cl、-CF3、-NO2中的一个或者多个。
3.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，所述的钯催化剂为PdCl2、Pd(OAc)2、Pd(TFA)2、Pd(OTf)2、Pd(CH3CN)2Cl2、Pd(PhCN)2Cl2、Pd(dppf)Cl2、Pd(dppe)Cl2或Pd(dppp)Cl2。
4.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，所述的配体为Dcypm、Dppp、Xantphos、DPEphos、Dcype或Dcypp。
5.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，所述的碱为KOAc。
6.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，所述的添加剂为TBAI。
7.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，所述的溶剂为DMSO、DMF或DMA。
8.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，反应温度为90～110℃，反应时间为12～24小时。
9.根据权利要求1所述的由芳基重氮盐和芳基磺酰肼制备联芳烃的方法，其特征在于，所述的联芳烃为以下化合物中的一种：
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US11827610B2 (en) 2021-09-15 2023-11-28 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

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