岡伯格-巴赫曼反應

Gomberg–Bachmann反應（又稱岡伯格-巴克曼反應、岡伯格-巴赫曼反應、Gomberg芳基偶聯反應等）以烏克蘭裔美國化學家摩西·岡伯格（Moses Gomberg）和美國化學家沃納·以馬利·巴赫曼（Werner Emmanuel Bachmann）的名字命名^[1]^[2]^[3]，是指重氮鹽的酸性溶液用氫氧化鈉或乙酸鈉的水溶液處理時，發生芳基的偶聯反應，生成聯芳烴的衍生物的反應。例如，對溴苯胺與苯偶聯，得到對溴聯苯^[4]。

BrC₆H₄NH₂ + C₆H₆ → BrC₆H₄−C₆H₅

這個反應能應用於各種類型的芳香環，包括二茂鐵^[5] 和醌類。由於重氮鹽能發生許多副反應，因此反應產率一般不高，通常低於 40％。

Gomberg–Bachmann 反應的分子內版本為 Pschorr反應（下圖）。^[6]^[7] 其中 Z 基一般是 CH₂；CH₂CH₂；NH；CO，產物為芴、芴酮和咔唑類化合物。^[8]

一般認為是自由基歷程：

{\rm {\ C_{6}H_{5}N_{2}Cl\rightarrow C_{6}H_{5}\cdot +N_{2}+Cl\cdot }}

（均裂）

{\rm {\ C_{6}H_{5}\cdot +C_{6}H_{5}NO_{2}\rightarrow {\mathit {p}}\!-\!C_{6}H_{5}\!-\!C_{6}H_{4}NO_{2}+H\cdot }}

{\rm {\ H\cdot +Cl\cdot \rightarrow HCl}}

[1]
M. Gomberg, W. E. Bachmann. The Synthesis of Biaryl Compounds by Means of the Diazo Reaction. J. Am. Chem. Soc. 1924, 42: 2339–2343. doi:10.1021/ja01675a026.
[2]
W. Pötsch. Lexikon bedeutender Chemiker (VEB Bibliographisches Institut Leipzig, 1989) (ISBN 3817110553)
[3]
M. B. Smith, J. March. March's Advanced Organic Chemistry (Wiley, 2001) (ISBN 0-471-58589-0)
[4]
M. Gomberg and W. E. Bachmann (1941). "p-Bromobiphenyl". Org. Synth.; Coll. Vol. 1: 113.
[5]
D. F. DeTar, Org. Reactions, 9, 411 (1957).
[6]
R. Pschorr. Neue Synthese des Phenanthrens und seiner Derivate. Chem. Ber. 1896, 29 (1): 496–501. doi:10.1002/cber.18960290198.
[7]
March, Jerry (1985). Advanced Organic Chemistry, Reactions, Mechanisms and Structure, third Edition, John Wiley & Sons. ISBN 0-471-85472-7.
[8]
Stephen A. Chandler,a Peter Hanson, Alec B. Taylor, Paul H. Walton and Allan W. Timmsb. Sandmeyer reactions. Part 5.1 Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics. J. Chem. Soc., Perkin Trans. 2. 2001: 214–228. doi:10.1039/b006184k.

[1] [1]
M. Gomberg, W. E. Bachmann. The Synthesis of Biaryl Compounds by Means of the Diazo Reaction. J. Am. Chem. Soc. 1924, 42: 2339–2343. doi:10.1021/ja01675a026.

[2] [2]
W. Pötsch. Lexikon bedeutender Chemiker (VEB Bibliographisches Institut Leipzig, 1989) (ISBN 3817110553)

[3] [3]
M. B. Smith, J. March. March's Advanced Organic Chemistry (Wiley, 2001) (ISBN 0-471-58589-0)

[4] [4]
M. Gomberg and W. E. Bachmann (1941). "p-Bromobiphenyl". Org. Synth.; Coll. Vol. 1: 113.

[5] [5]
D. F. DeTar, Org. Reactions, 9, 411 (1957).

[6] [6]
R. Pschorr. Neue Synthese des Phenanthrens und seiner Derivate. Chem. Ber. 1896, 29 (1): 496–501. doi:10.1002/cber.18960290198.

[7] [7]
March, Jerry (1985). Advanced Organic Chemistry, Reactions, Mechanisms and Structure, third Edition, John Wiley & Sons. ISBN 0-471-85472-7.

[8] [8]
Stephen A. Chandler,a Peter Hanson, Alec B. Taylor, Paul H. Walton and Allan W. Timmsb. Sandmeyer reactions. Part 5.1 Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics. J. Chem. Soc., Perkin Trans. 2. 2001: 214–228. doi:10.1039/b006184k.

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岡伯格-巴赫曼反應

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岡伯格-巴赫曼反應

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反應機理

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