CN108383698B - 一种芳香酮的制备方法 - Google Patents

一种芳香酮的制备方法 Download PDF

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CN108383698B
CN108383698B CN201810156179.8A CN201810156179A CN108383698B CN 108383698 B CN108383698 B CN 108383698B CN 201810156179 A CN201810156179 A CN 201810156179A CN 108383698 B CN108383698 B CN 108383698B
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程凯
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Abstract

本发明公开了一种芳香酮的制备方法，在钯催化剂和含氮配体的作用下，腈类化合物与芳基磺酰肼在有机溶剂中发生脱硫加成反应，反应结束后经过后处理得到所述的芳香酮。该反应不仅适用于芳香族腈类化合物，还适用于脂肪族腈类化合物，反应具有广泛的底物适用性和官能团耐受性，在芳基‑羰基的构筑方面具有潜在的应用价值。

Description

一种芳香酮的制备方法
技术领域
本发明属于有机合成领域，具体涉及一种芳香酮的制备方法。
背景技术
酮类化合物是许多有机分子的核心结构，比如功能材料、香料和药物分子等。而芳香酮是有机合成中的十分重要的合成砌块，其广泛存在于天然产物的核心结构中并广泛应用于生物活性化合物。(a)de Meijere,A.； Diederich,F.Metal-Catalyzed Cross-Coupling reactions,John Wiley&Sons, Weinheim,Germany,2nd edn,2004.(b)Surburg,H.；Panten,J.Common Fragrance and Flavor Materials,Wiley-VCH,Weinheim,5th edn,2006.
芳基酮的合成有大量的成熟方法，而最经典的芳香酮合成策略不外乎相应的仲醇的氧化，芳烃化合物同酰氯在腐蚀性的三氯化铝存在下的 Friedel–Crafts酰基化反应。而过渡金属催化的反应提供了芳香酮合成的很多机会，其中一类反应是通过芳基金属络合物对极性多重键，比如腈类化合物的插入反应提供了有用的芳香酮的合成策略。(a)Sartori,G.；Maggi,R. Advances in Friedel–Crafts Acylation Reactions:Catalytic andGreen Process, CRC Press,Florida,2010.(b)Olah,G.A.Friedel–Crafts Chemistry,Wiley, New York,1973.
芳基磺酰肼是有机合成化学中常见的试剂，易通过相应芳基磺酰氯的肼解制备，多作为前驱体用于腙类化合物的合成。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。(a)Barluenga,J.；Valdés,C.Angew.Chem.,Int.Ed.2011,50,7486.(b)Shao,Z.； Zhang,H.Chem.Soc.Rev.2012,41,560.
近年来，经由C-S键活化而不是C-X、C-O或C-N键断裂启动过渡金属催化循环来构筑化合物的方法已成为有机金属化学研究的新途径和新思路。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。我们利用芳基磺酰肼作为芳基源，实现了腈类化合物的脱氮和脱硫性芳基化加成反应。Yuan,K.；Soulé,J.-F.； Doucet,H.ACS Catal.2015,5,978.Ortgies,D.H.；Hassanpour,A.；Chen,F.； Woo,S.；Forgione,P.Eur.J.Org.Chem.2016,408.
腈类化合物传统上是有机合成中非常稳定的和来源广泛的底物，可以简便应用于官能团转换中，比如醛、酰胺、胺、羧酸衍生物和杂环化合物等等。一般来说腈类化合物是在有机金属反应中是惰性的，所以乙腈和苯甲腈常作为很多金属催化的反应中的溶剂或者配体使用。近几年来，过渡金属催化的加成反应提供了从腈类化合物合成芳香酮的新的选择。大量研究表明过渡金属络合物，尤其是钯、钌和镍催化下可以实现腈类化合物的插入反应。(a)Rach,S.F.；Kühn,F.E.Chem.Rev.2009,109,2061.(b) Fleming,F.F.；Wang,Q.Z.Chem.Rev.2003,103,2035.(c)Kukushkin,V.Y.； Pombeiro,A.J.L.Chem.Rev.2002,102,1771.
传统上来说，该类反应都是通过有机硼试剂来完成的，比如ArB(OH)2, ArBF3K和Ar4Bna。(a)Zhou,C.X.；Larock,R.C.J.Am.Chem.Soc.2004, 126,2302；(b)Wang,X.；Liu,M.；Xu,L.；Wang,Q.；Chen,J.；Ding,J.；Wu,H. J.Org.Chem.2013,78,5273.(c)Ueura,K.；Satoh,T.；Miura,M.Org.Lett. 2005,7,2229.
Hsieh et al.报道了新颖的NiCl2(DME)/dppp/Zn体系实现了碘代芳烃通过C-I键的断裂对腈类化合物的插入反应。Hsieh,J.-C.；Chen,Y.-C.；Cheng, A.；Tseng,H.-C.Org.Lett.2012,14,1282.Larhed et al.描述了一种二价钯催化的芳基羧酸通过C-C键的断裂的脱羧性加成对腈类化合物的插入反应。不过反应主要适用于邻位取代的负电子芳基羧酸和脂肪族的腈类化合物。 Lindh,J.；
Figure BDA0001581401230000021
P.；Larhed,M.Angew.Chem.Int.Ed.2010,49,7733.最近通过C-S键的断裂来启动有机金属化合物的形成的已经成为了一种具有吸引力的选择。事实上，在过去的几年中已经观察到了几类相近的ArSO2X (X＝Na and H)化合物作为芳基源实现脱硫性的对腈类化合物的加成反应的应用。(a)Miao,T.；Wang,G.-W.Chem.Commun.2011,47,9501；(b)Liu,J.； Zhou,X.；Rao,H.；Xiao,F.；Li,C.-J.；Deng,G.-J.Chem.Eur.J.2011,17,7996；(c)Behrends,M.；
Figure BDA0001581401230000031
J.；
Figure BDA0001581401230000032
P.J.R.；Larhed,M.ACS Catal.2011, 1,1455；(d)Chen,J.；Li,J.；Su,W.Molecules 2014,19,6439.而芳基磺酰肼的此类反应则未见报道。
发明内容
本发明提供了一种芳香酮的制备方法，该制备方法所用的原料价廉易得，并且稳定性好，同时反应条件温和。
一种芳香酮的制备方法，在钯催化剂和含氮配体的作用下，腈类化合物与芳基磺酰肼在有机溶剂中发生反应，反应结束后经过后处理得到所述的芳香酮；
所述的腈类化合物的结构如式(II)所示：
N≡C-R1 (II)
所述的芳基磺酰肼的结构如式(III)所示：
Figure BDA0001581401230000033
所述的芳香酮的结构如式(I)所示：
Figure BDA0001581401230000034
R1选自取代或者为取代的C1～C6烷基、取代或者未取代的芳基，所述的烷基上的取代基选自苯基或者乙酰基，所述芳基上的取代基选自卤素、硝基、C1～C4烷基、苄氧基或二甲氨基；
R2选自卤素、硝基、C1～C4烷基、C1～C4烷氧基、三氟甲基或二甲氨基。
作为优选，R1中，所述的芳基为苯基；
所述的芳基上的取代基选自F、Cl、Br、硝基、甲基、苄氧基或二甲氨基。
作为优选，R2选自F、Cl、Br、硝基、甲基、甲氧基、三氟甲基或二甲氨基。
作为优选，所述的钯催化剂为Pd(PhCN)2Cl2、Pd(CH3CN)2Cl2或 Pd(OAc)2。
作为优选，所述的含氮配体为双齿含氮配体；作为进一步优选，所述的含氮配体选自以下化合物中的一种：
Figure BDA0001581401230000041
作为优选，所述的有机溶剂为DMF或DMSO。
作为优选，反应温度为70～90℃，反应时间为5～7小时。
作为优选，反应过程中添加微量的水，所加入的水与腈类化合物的摩尔比为1.5～2.5：1。
同现有技术相比，本发明的有益效果体现在：
(1)该方法所用的原料价廉易得，并且稳定性好，并且反应条件温和。
(2)该方法不仅适用于芳香族腈类化合物，还适用于脂肪族腈类化合物，反应具有广泛的底物适用性和官能团耐受性，在芳基-羰基的构筑方面具有潜在的应用价值。
具体实施方式
下面结合具体实施例对本发明做进一步的描述。
实施例1～24
在惰性气体保护下，将苯基磺酰肼(1.1mmol)、苯腈(1.0mmol)、钯催化剂(2mol％)和联喹啉(bq,3mol％)分散于有机溶剂(2mL)中，然后加入H2O(2mmol)，升温至80℃反应6小时。然后将反应液用Et2O(5mL) 萃取三次，合并有机相，减压旋干溶剂，得到的粗产物用硅胶柱(300-400目) 进行柱层析，洗脱剂为石油醚和乙酸乙酯的混合物，得到目标产品，反应条件和反应结果见表1，反应式如下：
Figure BDA0001581401230000042
表1实施例1～24的反应条件和反应结果
Figure DEST_PATH_IMAGE001
实施例25～38
在惰性气体保护下，将苯基磺酰肼(1.1mmol)、苯腈(1.0mmol)、醋酸钯(2mol％)和含氮配体(3mol％)分散于DMSO(2mL)中，然后加入 H2O(2mmol)，升温至80℃反应6小时。然后将反应液用Et2O(5mL)萃取三次，合并有机相，减压旋干溶剂，得到的粗产物用硅胶柱(300-400目) 进行柱层析，洗脱剂为石油醚和乙酸乙酯的混合物，得到目标产品，反应条件和反应结果见表2。
表2实施例25～38的反应条件和反应结果
Figure BDA0001581401230000061
实施例39～53
在惰性气体保护下，将芳基磺酰肼(1.1mmol)、苯腈(1.0mmol)、醋酸钯(2mol％)和含氮配体bq(3mol％)分散于DMSO(2mL)中，然后加入H2O(2mmol)，升温至80℃反应6小时。然后将反应液用Et2O(5mL) 萃取三次，合并有机相，减压旋干溶剂，得到的粗产物用硅胶柱(300-400目) 进行柱层析，洗脱机为石油醚和乙酸乙酯的混合物，得到目标产品，反应条件和反应结果见表3，反应式如下：
Figure BDA0001581401230000062
表3实施例39～53的反应条件和反应结果
Figure BDA0001581401230000063
实施例54～68
在惰性气体保护下，将苯基磺酰肼(1.1mmol)、腈类化合物(1.0 mmol)、醋酸钯(2mol％)和含氮配体bq(3mol％)分散于DMSO(2mL) 中，然后加入H2O(2mmol)，升温至80℃反应6小时。然后将反应液用 Et2O(5mL)萃取三次，合并有机相，减压旋干溶剂，得到的粗产物用硅胶柱(300-400目)进行柱层析，洗脱机为石油醚和乙酸乙酯的混合物，得到目标产品，反应条件和反应结果见表4，反应式如下：
Figure BDA0001581401230000071
表4实施例54～68的反应条件和反应结果
Figure BDA0001581401230000072
实施例69～74
在惰性气体保护下，将苯基磺酰肼(1.1mmol)、腈类化合物(1.0 mmol)、醋酸钯(2mol％)和含氮配体邻菲啰啉(phen,3mol％)分散于 DMF(2mL)中，然后加入H2O(2mmol)，升温至80℃反应6小时。然后将反应液用Et2O(5mL)萃取三次，合并有机相，减压旋干溶剂，得到的粗产物用硅胶柱(300-400目)进行柱层析，洗脱机为石油醚和乙酸乙酯的混合物，得到目标产品，反应条件和反应结果见表5，反应式如下：
Figure BDA0001581401230000073
表5实施例69～74的反应条件和反应结果
Figure DEST_PATH_IMAGE002
实施例75～94
在惰性气体保护下，将芳基磺酰肼(1.1mmol)、醋酸钯(2mol％)和含氮配体phen(3mol％)分散于乙腈(2mL)中，然后加入H2O(2mmol)，升温至100℃反应6小时。然后将反应液用Et2O(5mL)萃取三次，合并有机相，减压旋干溶剂，得到的粗产物用硅胶柱(300-400目)进行柱层析，洗脱机为石油醚和乙酸乙酯的混合物，得到目标产品，反应条件和反应结果见表6，反应式如下：
Figure BDA0001581401230000082
表6实施例75～94的反应条件和反应结果
Figure BDA0001581401230000091
部分产物的表征数据如下：
4-Methoxy-benzophenone(3a)White solid,m.p.59–60℃.1H NMR (400MHz,CDCl3,TMS)δ7.83(d,J＝8.4Hz,2H),7.75(t,J＝7.6Hz,2 H),7.56(t,J＝7.6Hz,1H),7.45(t,J＝7.6Hz,2H),6.95(d,J＝8.4Hz,2 H),3.88(s,3H).13C NMR(100MHz,CDCl3)δ195.61,163.22,138.26, 132.61,131.95,130.11,129.76,128.22,113.56,55.53.HRMS(EI)Calcdfor C14H12O2(M+)212.0837,Found 212.0843.
Benzophenone(3b)White solid,m.p.46–48℃.1H NMR(400MHz, CDCl3,TMS)δ7.80(d,J＝8.4Hz,4H),7.58(t,J＝7.6Hz,2H),7.47(t, J＝8.0Hz,4H).13C NMR(100MHz,CDCl3)δ196.94,137.60,132.44, 130.08,128.30.HRMS(EI)Calcd for C13H10O(M+)182.0732,Found 182.0738.
4-Fluorobenzophenone(3c)White solid,m.p.45–46℃.1H NMR(400 MHz,CDCl3,TMS)δ7.86(dd,J1＝8.4Hz,J2＝5.0Hz,2H),7.78(d,J＝ 7.2Hz,2H),7.57(t,J＝7.2Hz,1H),7.48(t,J＝7.6Hz,2H),7.16(t,J＝ 8.4Hz,2H).13C NMR(100MHz,CDCl3)δ195.30,165.81(d,J＝252Hz), 137.48,133.8(d,J＝3.1Hz),132.70(d,J＝9.0Hz),132.51,129.90,128.38, 115.47(d,J＝21.5Hz).HRMS(EI)Calcd for C13H9FO(M+)200.0637,Found200.0638.
4-Nitrobenzophenone(3d)Light yellow solid,m.p.141–143℃.1H NMR(400MHz,CDCl3,TMS)δ8.34(d,J＝8.4Hz,2H),7.94(d,J＝8.4 Hz,2H),7.81(d,J＝7.2Hz,2H),7.67(t,J＝7.6Hz,1H),7.53(t,J＝7.2 Hz,2H).13C NMR(100MHz,CDCl3)δ194.79,149.81,142.88,136.28, 133.48,130.70,130.11,128.69,123.54.HRMS(EI)Calcd forC13H9NO3(M+) 227.0582,Found 227.0586.
4-Trifluoromethyl-benzophenone(3e)White solid,m.p.117–118℃.1H NMR(400MHz,CDCl3,TMS)δ7.89(d,J＝8.0Hz,2H),7.81(d,J＝7.2 Hz,2H),7.75(d,J＝8.4Hz,2H),7.63(t,J＝7.6Hz,1H),7.52(t,J＝7.6 Hz,2H).13C NMR(100MHz,CDCl3)δ195.56,140.71,136.70,133.66(dd, J1＝64.6Hz,J2＝32.6Hz),133.12,130.16(d,J＝3.8Hz),128.54,125.35 (dd,J1＝7.2Hz,J2＝3.6Hz),123.71(d,J＝271.2Hz).HRMS(EI)Calcd forC14H9F3O(M+)250.0605,Found 250.0602.
4-Methylbenzophenone(3f,4c)White solid,m.p.55–56℃.1H NMR (400MHz,CDCl3,TMS)δ7.80(d,J＝6.8Hz,2H),7.74(d,J＝8.0Hz,2 H),7.57(t,J＝8.0Hz,1H),7.48(t,J＝7.2Hz,2H),7.29(d,J＝8.0Hz,2 H),2.45(s,3H).13C NMR(100MHz,CDCl3)δ196.52,143.26,137.96, 134.89,132.18,130.33,129.95,128.99,128.22,21.68.HRMS(EI)Calcdfor C14H12O(M+)196.0888,Found 196.0893.
3-Methyl-benzophenone(3g)Colorless oil.1H NMR(400 MHz,CDCl3, TMS)δ7.80(d,J＝7.2Hz,2H),7.63(s,1H),7.58(d,J＝7.2Hz,2H), 7.49(t,J＝7.6Hz,2H),7.33-7.41(m,2H),2.42(s,3H).13C NMR(100 MHz,CDCl3)δ197.05,138.18,137.73,137.61,133.25,132.40,130.50, 130.08,128.28,128.12,127.42,21.42.HRMS(EI)Calcd for C14H12O(M+)196.0888,Found 196.0883.
2-Methylbenzophenone(3h)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.81(d,J＝8.4Hz,2H),7.60(t,J＝7.6Hz,1H),7.48(t,J＝7.6 Hz,2H),7.41(t,J＝7.2Hz,1H),7.24-7.34(m,3H),2.35(s,3H).13C NMR(100MHz,CDCl3)δ198.66,138.62,137.74,136.76,133.14,131.00, 130.24,130.14,128.52,128.47,125.19,20.00.HRMS(EI)Calcd forC14H12O (M+)196.0888,Found 196.0882.
4-Chloro-benzophenone(3i,4d)White solid,m.p.75–76℃.1H NMR (400MHz,CDCl3,TMS)δ7.77(t,J＝7.2Hz,4H),7.60(t,J＝7.2Hz,1 H),7.50(t,J＝8.0Hz,2H),7.46(d,J＝8.8Hz,2H).13C NMR(100MHz, CDCl3)δ197.58,138.91,137.21,135.84,132.70,131.50,129.96,128.66, 128.43.HRMS(EI)Calcd for C13H9ClO(M+)216.0342,Found216.0347.
3-Chloro-benzophenone(3j)White solid,m.p.83–85℃.1H NMR(400 MHz,CDCl3,TMS)δ7.79(d,J＝6.8Hz,2H),7.78(s,1H),7.67(d,J＝ 6.8Hz,1H),7.62(t,J＝7.2Hz,1H),7.56(d,J＝8.0Hz,1H),7.50(t,J＝ 7.6Hz,2H),7.42(t,J＝8.0Hz,1H).13C NMR(100MHz,CDCl3)δ 195.30,139.24,136.92,134.57,132.89,132.40,130.06,129.92,129.66,128.49,128.15.HRMS(EI)Calcd for C13H9ClO(M+)216.0342,Found 216.0335.
2-Chlorobenzophenone(3k)White solid,m.p.43–45℃.1H NMR(400 MHz,CDCl3,TMS)δ7.81(d,J＝8.4Hz,2H),7.60(t,J＝7.6Hz,1H), 7.41-7.49(m,4H),7.36-7.39(m,2H).13C NMR(100MHz,CDCl3)δ 195.29,138.61,136.48,133.71,131.32,131.15,130.09,129.13,128.63, 126.70.HRMS(EI)Calcd for C13H9ClO(M+)216.0342,Found 216.0340.
2,3,4,5,6-Pentamethyl-benzophenone(3l)White solid,m.p.136–137℃. 1HNMR(400MHz,CDCl3,TMS)δ7.83(d,J＝7.2Hz,2H),7.55(t,J＝ 7.6Hz,1H),7.44(t,J＝7.6Hz,2H),2.28(s,3H),2.21(s,6H),2.02(s, 6H).13C NMR(100MHz,CDCl3)δ201.99,137.68,135.57,133.44,132.90, 129.55,129.04,128.73,17.56,16.79,15.99.HRMS(EI)Calcd for C18H20O (M+)252.1514,Found 252.1516.
4-Bromobenzophenone(3m)White solid,m.p.80–82℃.1H NMR(400 MHz,CDCl3,TMS)δ7.77(d,J＝8.4Hz,2H),7.58-7.69(m,5H),7.49(t, J＝7.6Hz,2H).13C NMR(100MHz,CDCl3)δ195.68,137.14,136.28, 132.73,131.63,131.61,129.97,128.45,127.55.HRMS(EI)Calcd for C13H9BrO(M+)259.9837,Found 259.9832.
2-Benzoylthiophene(3n)White solid,m.p.53–54℃.1H NMR(400 MHz,CDCl3,TMS)δ7.86(d,J＝7.2Hz,2H),7.72(d,J＝4.8Hz,1H), 7.64(d,J＝3.6Hz,1H),7.59(t,J＝7.2Hz,1H),7.48(t,J＝7.2Hz,2H), 7.16(t,J＝4.4Hz,1H).13C NMR(100MHz,CDCl3)δ188.24,143.64, 138.15,134.88,134.24,132.29,129.18,128.44,127.99.HRMS(EI)Calcdfor C11H8OS(M+)188.0296,Found 188.0299.
3-Benzoylpyridine(3o)White solid,m.p.40–42℃.1H NMR(400MHz, CDCl3,TMS)δ8.99(s,1H),8.81(d,J＝7.6Hz,1H),8.12(d,J＝8.0Hz, 1H),7.82(d,J＝8.4Hz,2H),7.64(t,J＝7.6Hz,1H),7.44-7.54(m,3 H).13C NMR(100MHz,CDCl3)δ195.00,152.83,150.91,137.18,136.64, 133.18,133.10,130.01,128.61,123.36.HRMS m/z(ESI)calcd forC12H10NO [M+H]+184.0757,found 184.0750.
4-Benzyloxy-benzophenone(4a)White solid,m.p.83–85℃.1H NMR (400MHz,CDCl3,TMS)δ7.82(d,J＝8.4Hz,2H),7.75(t,J＝7.2Hz,2 H),7.55(t,J＝7.6Hz,1H),7.32-7.48(m,7H),7.03(d,J＝8.8Hz,2H), 5.14(s,2H).13C NMR(100MHz,CDCl3)δ195.54,162.38,138.26,136.24, 132.59,131.92,130.38,129.76,128.72,128.27,128.21,127.52,114.43,70.19. HRMS(EI)Calcd for C20H16O2(M+)288.1150,Found 288.1143.
4-(Dimethylamino)benzophenone(4b)White solid,m.p.92-94℃.1H NMR(400MHz,CDCl3,TMS)δ7.80(d,J＝9.2Hz,2H),7.71(d,J＝8.4 Hz,2H),7.52(t,J＝7.2Hz,1H),7.44(t,J＝7.6Hz,2H),6.66(d,J＝7.6 Hz,2H),3.06(s,6H).13C NMR(100MHz,CDCl3)δ195.18,153.27, 139.30,132.77,131.16,129.47,128.04,124.67,110.54,40.09.HRMS m/z (ESI)calcd for C15H16NO[M+H]+226.1226,found 226.1223.
3-Nitrobenzophenone(4e)Light yellow solid,m.p.96–97℃.1H NMR (400MHz,CDCl3,TMS)δ8.62(s,1H),8.45(d,J＝8.0Hz,1H),8.14(d, J＝8.0Hz,1H),7.81(d,J＝7.2Hz,2H),7.72(t,J＝7.6Hz,1H),7.66(t, J＝7.6Hz,1H),7.54(t,J＝7.6Hz,2H).13C NMR(100MHz,CDCl3)δ 194.18,148.08,139.04,136.25,135.48,133.39,130.02,129.68,128.75, 126.74,124.70.HRMS(EI)Calcd for C13H9NO3(M+)227.0582,Found 227.0586.
3,4-Dimethylbenzophenone(4f)White solid,m.p.47–48℃.1H NMR (400MHz,CDCl3,TMS)δ7.80(d,J＝8.0Hz,2H),7.64(s,1H), 7.53-7.61(m,2H),7.49(t,J＝7.6Hz,2H),7.24(t,J＝8.0Hz,1H),2.36 (s,3H),2.34(s,3H).13C NMR(100MHz,CDCl3)δ196.73,141.99, 138.08,136.76,135.30,132.10,131.20,129.95,129.45,128.18,128.06,20.04,19.79.HRMS(EI)Calcd for C15H14O(M+)210.1045,Found 210.1040.
3,4-Dichlorobenzophenone(4g)White solid,m.p.103–104℃.1H NMR (400MHz,CDCl3,TMS)δ7.90(s,1H),7.77(d,J＝6.8Hz,2H),7.64(t, J＝8.0Hz,2H),7.58(d,J＝8.0Hz,1H),7.50(t,J＝8.0Hz,2H).13C NMR(100MHz,CDCl3)δ194.21,137.20,137.02,136.67,133.00,131.84, 130.46,129.92,129.08,128.57.HRMS(EI)Calcd for C13H8Cl2O(M+) 249.9952,Found 249.9956.
3,5-Bis(trifluoromethyl)benzophenone(4h)White solid,m.p.108–110 ℃.1HNMR(400MHz,CDCl3,TMS)δ8.24(s,2H),8.10(s,1H),7.79 (d,J＝7.6Hz,2H),7.69(t,J＝7.6Hz,1H),7.56(d,J＝7.6Hz,2H).13C NMR(100MHz,CDCl3)δ193.57,139.39,135.90,133.62,132.01(dd,J1＝ 67.2Hz,J2＝33.6Hz),130.00,129.81(d,J＝2.1Hz),128.87,125.63(t,J＝ 3.9Hz),124.25,121.54(q,J＝271Hz).HRMS(EI)Calcd for C15H8F6O (M+)318.0479,Found 318.0481.
4-Iodobenzophenone(4i)White solid,m.p.101–103℃.1H NMR(400 MHz,CDCl3,TMS)δ7.84(d,J＝8.4Hz,2H),7.77(d,J1＝7.6Hz,2H), 7.60(t,J＝7.2Hz,1H),7.46-7.53(m,3H).13C NMR(100MHz,CDCl3) δ195.89,137.61,137.11,136.87,132.72,131.49,129.98,128.44,100.18. HRMS(EI)Calcd for C13H9IO(M+)307.9698,Found 307.9692.
1-Naphthyl-benzophenone(4j)White solid,m.p.76–78℃.1H NMR (400MHz,CDCl3,TMS)δ8.10(d,J＝7.6Hz,1H),8.00(d,J＝8.4Hz,1 H),7.91(d,J＝7.2Hz,1H),7.86(d,J＝8.4Hz,2H),7.42-7.61(m,7H). 13C NMR(100MHz,CDCl3)δ198.08,138.30,136.33,133.73,133.29, 131.32,130.96,130.46,128.48,128.45,127.84,127.31,126.51,125.71, 124.38.HRMS m/z(ESI)calcd for C17H13O[M+H]+233.0961,found 233.0961.
2-Benzoylpyridine(4k)White solid,m.p.42–43℃.1H NMR(400MHz, CDCl3,TMS)δ8.72(d,J＝4.8Hz,1H),8.02-8.08(m,3H),7.89(t,J＝ 7.6Hz,1H),7.59(d,J＝7.2Hz,1H),7.48(t,J＝7.6Hz,3H).13C NMR (100MHz,CDCl3)δ194.05,155.07,148.57,137.08,136.25,132.95,130.99, 128.18,126.20,124.64.HRMS(EI)Calcd for C12H9NO(M+)183.0684,Found 183.0683.
2,6-Difluorobenzophenone(4l)White solid,m.p.134–136℃.1H NMR (400MHz,CDCl3,TMS)δ7.80(d,J＝8.4Hz,2H),7.64(t,J＝7.6Hz,1 H),7.52(t,J＝7.6Hz,2H),7.31(dt,J1＝7.2Hz,J2＝2.4Hz,2H),7.05(tt, J1＝8.4Hz,J2＝2.4Hz,1H).13C NMR(100MHz,CDCl3)δ193.91,162.62 (dd,J1＝250Hz,J2＝11.6Hz),140.55(t,J＝7.2Hz),136.37,133.15, 129.97,128.57,112.92(dd,J1＝18.3Hz,J2＝7.4Hz),107.70(t,J＝25.1 Hz).HRMS(EI)Calcd for C13H8F2O(M+)218.0543,Found 218.0549.
2,5-Difluorobenzophenone(4m)White solid,m.p.99–100℃.1H NMR (400MHz,CDCl3,TMS)δ7.84(d,J＝8.4Hz,2H),7.62(t,J＝7.6Hz,1 H),7.48(d,J＝7.6Hz,2H),7.19-7.28(m,2H),7.11-7.17(m,1H).13C NMR(100MHz,CDCl3)δ192.11,159.73,157.20(d,J＝252Hz),136.76, 133.78,129.81,128.61,128.10(dd,J1＝17.2Hz,J2＝6.4Hz),119.65(dd,J1＝23.6Hz,J2＝8.6Hz),117.77(dd,J1＝24.8Hz,J2＝8.0Hz),117.01(dd,J1＝18.4Hz,J2＝7.2Hz).HRMS(EI)Calcd for C13H8F2O(M+)218.0543, Found 218.0548.
3,4,5-Trifluorobenzophenone(4n)White solid,m.p.121–123℃.1H NMR(400MHz,CDCl3,TMS)δ7.78(d,J＝7.2Hz,2H),7.66(t,J＝7.6 Hz,1H),7.54(t,J＝8.0Hz,2H),7.50(t,J＝7.2Hz,1H).13C NMR(100 MHz,CDCl3)δ192.87,152.22(dd,J1＝41.2Hz,J2＝12Hz),149.69(dd,J1＝40.8Hz,J2＝14Hz),144.01(t,J＝62.4Hz),141.43(t,J＝61.6Hz),136.16,133.14,129.81,128.64,114.57(dd,J1＝64Hz,J2＝24.8Hz).HRMS (EI)Calcd forC13H7F3O(M+)236.0449,Found 236.0438.
2,3,4,5,6-Perfluoro-benzophenone(4o)White solid,m.p.36–37℃.1H NMR(400MHz,CDCl3,TMS)δ7.86(d,J＝7.6Hz,2H),7.69(t,J＝7.6 Hz,1H),7.54(t,J＝7.6Hz,2H).13C NMR(100MHz,CDCl3)δ185.23, 135.94,135.05,129.70,129.10.HRMS(EI)Calcdfor C13H5F5O(M+) 272.0261,Found 272.0265.
1,2-Diphenylethanone(T5-1)White solid,m.p.55–57℃.1H NMR (400MHz,CDCl3,TMS)δ8.01(d,J＝7.8Hz,2H),7.54(t,J＝7.2Hz,1 H),7.44(t,J＝7.2Hz,2H),7.22-7.34(m,5H),4.28(s,3H).13C NMR (100MHz,CDCl3)δ197.64,136.62,134.57,133.19,129.50,128.70,128.67, 128.64,126.91,45.52.HRMS m/z(ESI)calcd for C14H13O[M+H]+197.0961, found 197.0962.
Benzoylacetone(T5-2)Colorless oil.1H NMR(400MHz,CDCl3,TMS) δ7.87(d,J＝7.2Hz,2H),7.51(t,J＝7.2Hz,1 colorless oil.H),7.44(t,J ＝7.2Hz,2H),6.17(s,2H),2.19(s,3H).13C NMR(100MHz,CDCl3)δ 193.78,183.34,134.88,132.2-9,128.83,128.61,127.00,96.70,25.84.HRMS m/z(ESI)calcd for C10H11O2[M+H]+163.0754,found163.0749.
Propiophenone(T5-3)Colorless oil.1H NMR(400MHz,CDCl3,TMS) δ7.90(d,J＝7.6Hz,2H),7.48(t,J＝7.6Hz,1H),7.38(t,J＝7.6Hz,2 H),2.93(q,J＝7.2Hz,2H),1.15(t,J＝7.2Hz,3H).13C NMR(100MHz, CDCl3)δ200.62,136.86,132.81,128.48,127.90,31.69,8.16.HRMS m/z (ESI)calcd for C9H11O[M+H]+135.0804,found 135.0802.
Pentanophenone(T5-4)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.94(d,J＝7.2Hz,2H),7.53(t,J＝7.2Hz,1H),7.42(t,J＝7.6 Hz,2H),2.95(t,J＝7.6Hz,2H),1.67-1.75(m,2H),1.37-1.43(m,2H), 0.94(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3)δ200.47,137.05, 132.84,128.52,128.01,38.29,26.45,22.48,13.94.HRMS m/z(ESI)calcd forC11H15O[M+H]+163.1117,found 163.1109.
Isobutyrophenone(T5-5)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.95(d,J＝7.6Hz,2H),7.53(t,J＝7.2Hz,1H),7.44(t,J＝7.2 Hz,2H),3.55(m,1H),1.21(d,J＝6.8Hz,6H).13C NMR(100MHz, CDCl3)δ204.38,136.16,132.77,128.58,128.28,35.29,19.12.HRMS m/z (ESI)calcd for C10H13O[M+H]+149.0961,found 149.0957.
Cyclopentyl(phenyl)methanone(T5-6)Colorless oil.1H NMR(400 MHz,CDCl3,TMS)δ7.97(d,J＝7.2Hz,2H),7.53(t,J＝7.2Hz,1H), 7.44(t,J＝7.2Hz,2H),3.66-3.75(m,1H),1.86-1.94(m,4H),1.60-1.77 (m,4H).13C NMR(100MHz,CDCl3)δ202.75,136.90,132.69,128.49, 128.44,46.33,29.96,26.32.HRMS m/z(ESI)calcd for C12H15O[M+H]+175.1117,found 175.1109.
4'-Ethoxyacetophenone(6a)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.79(d,J＝8.8Hz,2H),6.77(d,J＝8.8Hz,2H),3.94(q,J＝7.2 Hz,2H),2.41(s,3H),1.30(t,J＝7.2Hz,3H).13C NMR(100MHz, CDCl3)δ196.46,162.80,130.44,129.96,113.97,63.61,26.14,14.55.HRMS (EI)Calcd for C10H12O2(M+)164.0837,Found 164.0833.
4'-Methoxyacetophenone(6b)Colorless oil.1H NMR(400MHz, CDCl3,TMS)δ7.86(d,J＝8.8Hz,2H),6.86(d,J＝8.8Hz,2H),3.78(s, 3H),2.48(s,3H).13C NMR(100MHz,CDCl3)δ196.65,163.42,130.51, 130.22,113.62,55.38,26.25.HRMS(EI)Calcd forC9H10O2(M+)150.0681, Found 150.0689.
3'-Methoxyacetophenone(6c)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.38(d,J＝7.6Hz,1H),7.33(s,1H),7.21(t,J＝8.0Hz,1H), 6.96(d,J＝7.2Hz,1H),3.68(s,3H),2.43(s,3H).13C NMR(100MHz, CDCl3)δ197.60,159.66,138.32,129.45,120.92,119.28,112.31,55.15, 26.48.HRMS(EI)Calcd for C9H10O2(M+)150.0681,Found150.0677.
4'-Dimethylaminoacetophenone(6d)Colorless oil.1H NMR(400MHz, CDCl3,TMS)δ7.86(d,J＝8.4Hz,2H),6.63(d,J＝8.0Hz,2H),3.03(s, 6H),2.50(s,3H).13C NMR(100MHz,CDCl3)δ196.37,153.38,130.50, 125.25,110.58,40.00,26.00.HRMS(EI)Calcdfor C10H13NO(M+)163.0997, Found 163.0991.
4'-Methylthioacetophenone(6e)Colorless oil.1H NMR(400MHz, CDCl3,TMS)δ7.82(d,J＝8.0Hz,2H),7.21(d,J＝8.0Hz,2H),2.52(s, 3H),2.47(s,3H).13C NMR(100MHz,CDCl3)δ197.09,145.89,133.40, 128.69,124.88,26.40,14.70.HRMS(EI)Calcd forC9H10OS(M+)166.0452, Found 166.0460.
4'-Methylacetophenone(6f)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.76(d,J＝6.8Hz,2H),7.14(d,J＝7.2Hz,2H),2.45(s,3H), 2.30(s,3H).13C NMR(100 MHz,CDCl3)δ197.55,143.72,134.60,129.15, 128.35,26.36,21.49.HRMS(EI)Calcd forC9H10O(M+)134.0732,Found 134.0728.
3'-Methylacetophenone(6g)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.76(s,1H),7.74(d,J＝7.2Hz,2H),7.36(d,J＝7.6Hz,1H), 7.33(t,J＝7.2Hz,1H),2.57(s,3H),2.40(s,3H).13C NMR(100MHz, CDCl3)δ198.34,138.32,137.13,133.85,128.77,128.44,125.58,26.65, 21.31.HRMS(EI)Calcd for C9H10O(M+)134.0732,Found134.0739.
3',5'-Dimethylacetophenone(6h)Colorless oil.1H NMR(400MHz, CDCl3,TMS)δ7.55(s,2H),7.17(s,1H),2.55(s,3H),2.34(s,6H). 13C NMR(100MHz,CDCl3)δ198.52,138.13,137.19,134.70,126.09,26.66, 21.17.HRMS(EI)Calcd for C10H12O(M+)148.0888,Found 148.0895.
2',4',6'-Trimethylacetophenone(6i)Colorless oil.1H NMR(400MHz, CDCl3,TMS)δ6.82(s,2H),2.43(s,3H),2.27(s,3H),2.21(s,6H). 13C NMR(100MHz,CDCl3)δ208.10,139.97,138.13,132.21,128.49,32.06, 20.95,19.03.HRMS(EI)Calcd forC11H14O(M+)162.1045,Found 162.1052.
3'-Cyanoacetophenone(6j)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ8.21(s,1H),8.16(d,J＝7.6Hz,2H),7.82(d,J＝6.8Hz,1H), 7.61(t,J＝8.0Hz,1H),2.62(s,3H).13C NMR(100MHz,CDCl3)δ 195.90,137.70,136.00,132.25,131.99,129.72,117.94,113.08,26.59.HRMS (EI)Calcd for C9H7NO(M+)145.0528,Found 145.0522.
4'-Fluoroacetophenone(6k)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.81(d,J＝8.4Hz,2H),6.96(d,J＝8.4Hz,2H),2.41(s,3H). 13C NMR(100MHz,CDCl3)δ196.15,165.52(d,J＝251.8Hz),133.45(d,J ＝2.8Hz),130.79(d,J＝9.1Hz),115.38(d,J＝22.4Hz),26.19.HRMS(EI) Calcd for C8H7FO(M+)138.0481,Found 138.0486.
3'-Fluoroacetophenone(6l)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.69(d,J＝8.0Hz,1H),7.58(d,J＝9.6Hz,1H),7.37-7.43(m,1 H),7.18-7.24(m,1H),2.55(s,3H).13C NMR(100MHz,CDCl3)δ 196.68(d,J＝2.5Hz),162.77(d,J＝246.0Hz),139.11(d,J＝5.2Hz),130.24 (d,J＝7.4Hz),124.11(d,J＝5.2Hz),120.03(d,J＝21.4Hz),114.81(d,J＝ 22.2Hz),26.58.HRMS(EI)Calcd for C8H7FO(M+)138.0481,Found 138.0489.
2'-Fluoroacetophenone(6m)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.79(t,J＝8.0Hz,1H),7.44(q,J＝6.4Hz,1H),7.79(t,J＝7.6 Hz,1H),7.05(t,J＝9.6Hz,1H),2.55(s,3H).13C NMR(100MHz, CDCl3)δ195.58(d,J＝3.0Hz),162.12(d,J＝252.6Hz),134.60(d,J＝8.6 Hz),130.47(d,J＝2.6Hz),125.58(d,J＝2.7Hz),124.27(d,J＝3.9Hz),116.55(d,J＝23.7Hz),31.24(d,J＝6.7Hz).HRMS(EI)Calcd for C8H7FO (M+)138.0481,Found 138.0474.
4'-Nitroacetophenone(6n)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ8.24(d,J＝8.8Hz,2H),8.08(d,J＝8.4Hz,2H),2.65(s,3H). 13C NMR(100MHz,CDCl3)δ196.39,150.26,141.37,129.30,123.78,26.94. HRMS(EI)Calcd for C8H7NO3(M+)165.0426,Found165.0421.
3'-Nitroacetophenone(6o)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ8.69(s,1H),8.35(d,J＝7.2Hz,1H),8.26(d,J＝8.4Hz,1H), 7.67(t,J＝8.0Hz,1H),2.66(s,3H).13C NMR(100MHz,CDCl3)δ 195.73,148.33,138.18,133.86,129.96,127.33,123.08,26.71.HRMS(EI) Calcd for C8H7NO3(M+)165.0426,Found 165.0429.
2'-Nitroacetophenone(6p)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.95(d,J＝8.0Hz,1H),7.65(t,J＝7.2Hz,1H),7.53(t,J＝8.0 Hz,1H),7.40(d,J＝7.6Hz,1H),2.66(s,3H).13C NMR(100MHz, CDCl3)δ199.85,145.83,137.50,134.27,130.82,127.39,124.22,29.94. HRMS(EI)Calcd for C8H7NO3(M+)165.0426,Found 165.0420.
4'-Bromoacetophenone(6q)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.69(d,J＝8.8Hz,2H),7.46(d,J＝8.4Hz,2H),2.47(s,3H). 13C NMR(100MHz,CDCl3)δ196.76,135.70,131.76,129.77,128.13,26.46. HRMS(EI)Calcd for C8H7BrO(M+)197.9680,Found197.9687.
3'-Bromoacetophenone(6r)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.83(s,1H),7.64(d,J＝7.6Hz,1H),7.43(d,J＝9.2Hz,1H), 7.12(t,J＝8.0Hz,1H),2.37(s,3H).13C NMR(100MHz,CDCl3)δ 196.13,138.56,135.67,130.99,130.10,126.78,122.73,26.43.HRMS(EI) Calcd for C8H7BrO(M+)197.9680,Found 197.9681.
2'-Bromoacetophenone(6s)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ7.55(d,J＝8.0Hz,1H),7.42(d,J＝7.2Hz,1H),7.32(t,J＝7.6 Hz,1H),7.24(d,J＝7.6Hz,1H),2.57(s,3H).13C NMR(100MHz, CDCl3)δ201.22,141.33,133.80,131.83,128.92,127.46,118.82,30.29. HRMS(EI)Calcd for C8H7BrO(M+)197.9680,Found 197.9675.
2-Acetylnaphthalene(6t)Colorless oil.1H NMR(400MHz,CDCl3, TMS)δ8.33(s,1H),7.95(d,J＝8.8Hz,1H),7.84(d,J＝8.0Hz,1H), 7.75(d,J＝7.6Hz,2H),7.51(d,J＝6.8Hz,1H),7.46(d,J＝6.8Hz,1 H),2.61(s,3H).13C NMR(100MHz,CDCl3)δ197.92,135.49,134.36, 132.44,130.16,129.54,128.44,128.33,127.73,126.73,123.80,26.60.HRMS(EI)Calcd for C12H10O(M+)170.0732,Found 170.0741.

Claims (4)

1.一种芳香酮的制备方法，其特征在于，在钯催化剂和含氮配体的作用下，腈类化合物与芳基磺酰肼在有机溶剂中发生脱硫加成反应，反应结束后经过后处理得到所述的芳香酮；
所述的腈类化合物的结构如式(II)所示：
N≡C-R1 (II)
所述的芳基磺酰肼的结构如式(III)所示：
Figure FDA0002871903000000011
所述的芳香酮的结构如式(I)所示：
Figure FDA0002871903000000012
R1选自取代或者未取代的C1～C6烷基、取代或者未取代的芳基，所述的烷基上的取代基选自苯基或者乙酰基，所述芳基上的取代基选自卤素、硝基、C1～C4烷基、苄氧基或二甲氨基；
R2选自卤素、硝基、C1～C4烷基、C1～C4烷氧基、三氟甲基或二甲氨基；
所述的钯催化剂为Pd(PhCN)2Cl2、Pd(CH3CN)2Cl2或Pd(OAc)2；
反应过程中添加微量的水，所加入的水与腈类化合物的摩尔比为1.5～2.5：1；
所述的有机溶剂为DMF或DMSO；
所述的含氮配体选自以下化合物中的一种：
Figure FDA0002871903000000013
2.根据权利要求1所述的芳香酮的制备方法，其特征在于，R1中，所述的芳基为苯基；
所述的芳基上的取代基选自F、Cl、Br、硝基、甲基、苄氧基或二甲氨基。
3.根据权利要求1所述的芳香酮的制备方法，其特征在于，R2选自F、Cl、Br、硝基、甲基、甲氧基、三氟甲基或二甲氨基。
4.根据权利要求1所述的芳香酮的制备方法，其特征在于，反应温度为70～90℃，反应时间为5～7小时。
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