2,3,4-三甲氧基苯基-苯基-烯酮与乙氧基乙炔的加成重排反应

doi:10.7503/cjcu20140053

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (8): 1681.doi: 10.7503/cjcu20140053

2,3,4-三甲氧基苯基-苯基-烯酮与乙氧基乙炔的加成重排反应

王泽东, 岳晓东, 陈莉()

南开大学元素有机化学国家重点实验室, 天津 300071

收稿日期:2014-01-16 出版日期:2014-08-10 发布日期:2019-08-01
作者简介:联系人简介: 陈莉, 女, 博士, 副教授, 主要从事有机合成方法学及天然产物全合成研究.E-mail: chenliyss@nankai.edu.cn
基金资助:
国家自然科学基金(批准号: 21072103)和天津市自然科学基金(批准号: 10JCYBJC04200)资助

Reaction of 2-Phenyl-2-(2,3,4-trimethoxyphenyl)ketene with Ethoxyethyne^†

WANG Zedong, YUE Xiaodong, CHEN Li^*()

State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China

Received:2014-01-16 Online:2014-08-10 Published:2019-08-01
Contact: CHEN Li E-mail:chenliyss@nankai.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.21072103) and the Natural Science Foundation of Tianjin, China(No.10JCYBJC04200)

摘要/Abstract

摘要：

研究了2,3,4-三甲氧基苯基-苯基-烯酮(9)与乙氧基乙炔的加成-重排反应, 得到2种薁酮异构体产物(11和12), 其结构经核磁共振波谱和X射线单晶衍射分析进行了确证. 该研究结果为Woodward所提出的分步反应机理提供了实验依据.

关键词: 薁酮, 二芳基烯酮, 重排, 降蒈二烯

Abstract:

Nieuwenhuis and Arens discovered the reaction of diarylketenes with alkynyl ethers leads to substituted azulenones in 1958. This reaction involved the construction of four C—C bonds in a single operation and provided facile access to a functionalized bicyclo[5.3.0]decane skeleton. Although the mechanism of this transformation was rationalized later by Woodward and Barton, respectively, the synthetic value of this reaction has not been demonstrated so far. In this work, 2-phenyl-2-(2,3,4-trimethoxyphenyl)ketene(9) as a new ketene was first synthesized from 1,2,3-trimethoxybenzene and ethyl 2-chloro-2-oxoacetate through 5 steps. The reaction of compound 9 with ethoxyethyne(2) produced two novel angular aryl-substituted azulenone products 11 and 12, whose isomeric structures were characterized by NMR and X-ray crystallographic analysis. Treatment of azulenone 11 with Lewis acid afforded azulenone 12. These results provided an additional experimental supported for a stepwise pathway rationalized by Woodward earlier on.

Key words: Azulenone, Diarylketene, Rearrangement, Norcaradiene(Ed.: P, H, N, K)

中图分类号:

O621.3

TrendMD:

王泽东, 岳晓东, 陈莉. 2,3,4-三甲氧基苯基-苯基-烯酮与乙氧基乙炔的加成重排反应. 高等学校化学学报, 2014, 35(8): 1681.

WANG Zedong, YUE Xiaodong, CHEN Li. Reaction of 2-Phenyl-2-(2,3,4-trimethoxyphenyl)ketene with Ethoxyethyne^†. Chem. J. Chinese Universities, 2014, 35(8): 1681.

图/表 6

Scheme 1 Formation of azulenone: Woodward and Barton mechanism

Scheme 2 Synthesis routes of 2-chloro-2-phenyl-2-(2,3,4-trimethoxyphenyl)acetyl chloride(8)

Scheme 3 Synthesis routes of methyl 2-phenyl-2-(2,3,4-trimethoxyphenyl)acetate(10)

Scheme 4 Synthesis routes of azulenones(11 and 12)

Scheme 5 Proposed formation mechanism of azulenone

Table 1 X-Ray crystallographic data of compounds 11 and 12

Compound	11	12
Empirical formula	C₂₁H₂₂O₅	C₂₁H₂₂O₅
Formula mass	354.39	354.39
Crystal system	Triclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$
a/nm	0.9420(3)	0.87035(11)
b/nm	1.1725(4)	1.02348(14)
c/nm	1.6971(5)	1.11669(18)
α/(°)	96.668(5)	66.61(3)
β/(°)	95.867(5)	80.03(4)
γ/(°)	101.572(5)	85.95(4)
V/nm³	1.8088(10)	0.8992(2)
Z	4	2
T/K	113(2)	113(2)
Wavelength/nm	0.071073	0.071073
Calculated density/(g·cm^-3)	1.301	1.309
Absorption coefficient/mm^-1	0.092	0.093
Absorption correction	Semi-empirical from equivalents	Semi-empirical from equivalents
F(000)	752	376
Theta range for data collection(°)	1.22—27.86	2.01—32.58
Max. and min. transmission	0.9890 and 0.98181	0.9889 and 0.9817
Refinement method	Full-matrix least-squares on F²	Full-matrix least-squares on F²
Data/restraints/parameters	8511/0/477	6465/0/239
θ ranges(h, k, l)	-12≤h≤12, -14≤k≤15, -22≤l≤22	-13≤h≤13, -15≤k≤15, -16≤l≤15
Reflections collected/unique	19142/8511 [R_int=0.0448]	14635/6465 [R_int=0.0442]
Completeness to θ=25.02°	98.5%	98.6%
Goodness-of-fit on F²	1.017	0.93
Final R indices[I>2σ(I)]	R₁=0.0457, wR₂=0.0915	R₁=0.0426, wR₂=0.1016
R indices(all data)	R₁=0.0734, wR₂=0.0998	R₁=0.0595, wR₂=0.1070

Table 1 X-Ray crystallographic data of compounds 11 and 12

Compound	11	12
Empirical formula	C₂₁H₂₂O₅	C₂₁H₂₂O₅
Formula mass	354.39	354.39
Crystal system	Triclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$
a/nm	0.9420(3)	0.87035(11)
b/nm	1.1725(4)	1.02348(14)
c/nm	1.6971(5)	1.11669(18)
α/(°)	96.668(5)	66.61(3)
β/(°)	95.867(5)	80.03(4)
γ/(°)	101.572(5)	85.95(4)
V/nm³	1.8088(10)	0.8992(2)
Z	4	2
T/K	113(2)	113(2)
Wavelength/nm	0.071073	0.071073
Calculated density/(g·cm^-3)	1.301	1.309
Absorption coefficient/mm^-1	0.092	0.093
Absorption correction	Semi-empirical from equivalents	Semi-empirical from equivalents
F(000)	752	376
Theta range for data collection(°)	1.22—27.86	2.01—32.58
Max. and min. transmission	0.9890 and 0.98181	0.9889 and 0.9817
Refinement method	Full-matrix least-squares on F²	Full-matrix least-squares on F²
Data/restraints/parameters	8511/0/477	6465/0/239
θ ranges(h, k, l)	-12≤h≤12, -14≤k≤15, -22≤l≤22	-13≤h≤13, -15≤k≤15, -16≤l≤15
Reflections collected/unique	19142/8511 [R_int=0.0448]	14635/6465 [R_int=0.0442]
Completeness to θ=25.02°	98.5%	98.6%
Goodness-of-fit on F²	1.017	0.93
Final R indices[I>2σ(I)]	R₁=0.0457, wR₂=0.0915	R₁=0.0426, wR₂=0.1016
R indices(all data)	R₁=0.0734, wR₂=0.0998	R₁=0.0595, wR₂=0.1070

参考文献 19

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2,3,4-三甲氧基苯基-苯基-烯酮与乙氧基乙炔的加成重排反应

Reaction of 2-Phenyl-2-(2,3,4-trimethoxyphenyl)ketene with Ethoxyethyne^†

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2,3,4-三甲氧基苯基-苯基-烯酮与乙氧基乙炔的加成重排反应

Reaction of 2-Phenyl-2-(2,3,4-trimethoxyphenyl)ketene with Ethoxyethyne†

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Reaction of 2-Phenyl-2-(2,3,4-trimethoxyphenyl)ketene with Ethoxyethyne^†