3-溴甲苯

3-溴甲苯
别名	间溴甲苯; 3-甲基溴苯
识别
CAS号	591-17-3
PubChem	11560
SMILES	CC1=CC(=CC=C1)Br;
性质
化学式	C7H7Br
摩尔质量	171.03 g·mol−1
外观	无色液体
密度	1.4022 g·cm−3（25 °C）
熔点	−39.8 °C（233.3 K）
沸点	183.7 °C（456.8 K）
溶解性（水）	难溶
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

3-溴甲苯是一种有机化合物，化学式为C₇H₇Br，是溴甲苯的同分异构体之一。

合成

3-溴甲苯可由3-溴苯甲醛在钯碳催化剂存在下被氢气还原得到，^[3]或通过3-甲基苯胺的重氮化-溴化反应制得。^[4]3-甲基苯肼盐酸盐和三溴化硼在二甲基亚砜中反应，也可以得到3-溴甲苯。^[5]

反应

3-溴甲苯和苯硼酸可以发生铃木偶联反应（C–C偶联），生成3-甲基联苯：^[6]

类似地，在三(二亚苄基丙酮)二钯催化下，它和格氏试剂可以发生熊田偶联反应，如和4-甲氧基苯基溴化镁反应，得到3-甲基-4'-甲氧基联苯。^[7]该催化剂也可催化3-溴甲苯与胺的反应，如3-溴甲苯和哌啶在碱的存在下反应，可以得到C–C偶联产物1-(3-甲基苯基)哌啶。^[8]

乙酸钯和三苯基膦可以催化其脱溴反应：^[9]

它和氯磺酸在三氯甲烷中反应，可以得到4-溴-2-甲苯磺酰氯。^[10]它可以被氧气、过氧化叔丁醇等氧化剂催化氧化为3-溴苯甲酸。^[11]^[12]^[13]

参考文献

^ Hussey, Allen S.; Dyer, John R. The Monomagnesium Derivatives of Dibromotoluenes. Journal of the American Chemical Society. 2002, 73 (2): 603–604. ISSN 0002-7863. doi:10.1021/ja01146a031.
^ ^2.0 ^2.1 "PhysProp" data were obtained from Syracuse Research Corporation of Syracuse, New York (US). Retrieved from SciFinder. [2021-07-11].
^ Wang, Shuguo; Zhou, Peng; Jiang, Liang; Zhang, Zehui; Deng, Kejian; Zhang, Yuhua; Zhao, Yanxi; Li, Jinlin; Bottle, Steven; Zhu, Huaiyong. Selective deoxygenation of carbonyl groups at room temperature and atmospheric hydrogen pressure over nitrogen-doped carbon supported Pd catalyst. Journal of Catalysis. 2018, 368: 207–216. ISSN 0021-9517. doi:10.1016/j.jcat.2018.10.017.
^ Beletskaya, Irina; Sigeev, Alexander; Peregudov, Alexander; Petrovskii, Pavel. Catalytic Sandmeyer Bromination. Synthesis. 2007, 2007 (16): 2534–2538. ISSN 0039-7881. doi:10.1055/s-2007-983784.
^ Phuc Tran, Dat; Nomoto, Akihiro; Mita, Soichiro; Dong, Chun-ping; Kodama, Shintaro; Mizuno, Takumi; Ogawa, Akiya. Metal- and base-free synthesis of aryl bromides from arylhydrazines. Tetrahedron Letters. 2020, 61 (23): 151959. ISSN 0040-4039. doi:10.1016/j.tetlet.2020.151959.
^ Wang, Ai-E; Zhong, Jun; Xie, Jian-Hua; Li, Kai; Zhou, Qi-Lin. Highly Efficient Suzuki Cross-Coupling Catalyzed by Palladium/Phosphine-Imidazolium Carbene System. Advanced Synthesis & Catalysis. 2004, 346 (6): 595–598. ISSN 1615-4150. doi:10.1002/adsc.200404015.
^ Pal, Anwesha; Ghosh, Raju; Adarsh, N.N.; Sarkar, Amitabha. Pyrazole-tethered phosphine ligands for Pd(0): useful catalysts for Stille, Kumada and Hiyama cross-coupling reactions. Tetrahedron. 2010, 66 (29): 5451–5458. ISSN 0040-4020. doi:10.1016/j.tet.2010.05.026.
^ Mudithanapelli, Chandrashekar; Dhorma, Lama Prema; Kim, Mi-hyun. PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)–H or C(sp3)–H: Nitration via C–N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water. Organic Letters. 2019, 21 (9): 3098–3102. ISSN 1523-7060. doi:10.1021/acs.orglett.9b00751.
^ Chen, Jingbo; Zhang, Yushun; Yang, Liquan; Zhang, Xiang; Liu, Jianping; Li, Liang; Zhang, Hongbin. A practical palladium catalyzed dehalogenation of aryl halides and α-haloketones. Tetrahedron. 2007, 63 (20): 4266–4270. ISSN 0040-4020. doi:10.1016/j.tet.2007.03.061.
^ Chen, Qiao-Hong; Rao, P.N. Praveen; Knaus, Edward E. Design, synthesis, and biological evaluation of N-acetyl-2-carboxybenzenesulfonamides: a novel class of cyclooxygenase-2 (COX-2) inhibitors. Bioorganic & Medicinal Chemistry. 2005, 13 (7): 2459–2468. ISSN 0968-0896. doi:10.1016/j.bmc.2005.01.039.
^ Zheng, Kun; Yan, Xiaoyu; Zhang, Guofu; Yan, Xinhuan; Li, Xiaoqing; Xu, Xiangsheng. Photoinduced Carbon Tetrabromide Initiated Aerobic Oxidation of Substituted Toluenes to Carboxylic Acids. Synlett. 2019, 31 (03): 272–274. ISSN 0936-5214. doi:10.1055/s-0039-1691534.
^ Ozen, Recep. Pyridinium Chlorochromate Catalyzed Oxidation of Toluenes to Aromatic Carboxylic Acids with Molecular Oxygen in Sub-critical Water. Asian Journal of Chemistry. 2014, 26 (3): 941–942. ISSN 0970-7077. doi:10.14233/ajchem.2014.16651.
^ Mohammadpour, Pegah; Safaei, Elham. Catalytic C–H aerobic and oxidant-induced oxidation of alkylbenzenes (including toluene derivatives) over VO2+ immobilized on core–shell Fe3O4@SiO2 at room temperature in water. RSC Advances. 2020, 10 (40): 23543–23553. ISSN 2046-2069. doi:10.1039/D0RA03483E.

[1] Hussey, Allen S.; Dyer, John R. The Monomagnesium Derivatives of Dibromotoluenes. Journal of the American Chemical Society. 2002, 73 (2): 603–604. ISSN 0002-7863. doi:10.1021/ja01146a031.

[phys-2] 2.0 ^2.1 "PhysProp" data were obtained from Syracuse Research Corporation of Syracuse, New York (US). Retrieved from SciFinder. [2021-07-11].

[3] Wang, Shuguo; Zhou, Peng; Jiang, Liang; Zhang, Zehui; Deng, Kejian; Zhang, Yuhua; Zhao, Yanxi; Li, Jinlin; Bottle, Steven; Zhu, Huaiyong. Selective deoxygenation of carbonyl groups at room temperature and atmospheric hydrogen pressure over nitrogen-doped carbon supported Pd catalyst. Journal of Catalysis. 2018, 368: 207–216. ISSN 0021-9517. doi:10.1016/j.jcat.2018.10.017.

[4] Beletskaya, Irina; Sigeev, Alexander; Peregudov, Alexander; Petrovskii, Pavel. Catalytic Sandmeyer Bromination. Synthesis. 2007, 2007 (16): 2534–2538. ISSN 0039-7881. doi:10.1055/s-2007-983784.

[5] Phuc Tran, Dat; Nomoto, Akihiro; Mita, Soichiro; Dong, Chun-ping; Kodama, Shintaro; Mizuno, Takumi; Ogawa, Akiya. Metal- and base-free synthesis of aryl bromides from arylhydrazines. Tetrahedron Letters. 2020, 61 (23): 151959. ISSN 0040-4039. doi:10.1016/j.tetlet.2020.151959.

[6] Wang, Ai-E; Zhong, Jun; Xie, Jian-Hua; Li, Kai; Zhou, Qi-Lin. Highly Efficient Suzuki Cross-Coupling Catalyzed by Palladium/Phosphine-Imidazolium Carbene System. Advanced Synthesis & Catalysis. 2004, 346 (6): 595–598. ISSN 1615-4150. doi:10.1002/adsc.200404015.

[7] Pal, Anwesha; Ghosh, Raju; Adarsh, N.N.; Sarkar, Amitabha. Pyrazole-tethered phosphine ligands for Pd(0): useful catalysts for Stille, Kumada and Hiyama cross-coupling reactions. Tetrahedron. 2010, 66 (29): 5451–5458. ISSN 0040-4020. doi:10.1016/j.tet.2010.05.026.

[8] Mudithanapelli, Chandrashekar; Dhorma, Lama Prema; Kim, Mi-hyun. PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)–H or C(sp3)–H: Nitration via C–N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water. Organic Letters. 2019, 21 (9): 3098–3102. ISSN 1523-7060. doi:10.1021/acs.orglett.9b00751.

[9] Chen, Jingbo; Zhang, Yushun; Yang, Liquan; Zhang, Xiang; Liu, Jianping; Li, Liang; Zhang, Hongbin. A practical palladium catalyzed dehalogenation of aryl halides and α-haloketones. Tetrahedron. 2007, 63 (20): 4266–4270. ISSN 0040-4020. doi:10.1016/j.tet.2007.03.061.

[10] Chen, Qiao-Hong; Rao, P.N. Praveen; Knaus, Edward E. Design, synthesis, and biological evaluation of N-acetyl-2-carboxybenzenesulfonamides: a novel class of cyclooxygenase-2 (COX-2) inhibitors. Bioorganic & Medicinal Chemistry. 2005, 13 (7): 2459–2468. ISSN 0968-0896. doi:10.1016/j.bmc.2005.01.039.

[11] Zheng, Kun; Yan, Xiaoyu; Zhang, Guofu; Yan, Xinhuan; Li, Xiaoqing; Xu, Xiangsheng. Photoinduced Carbon Tetrabromide Initiated Aerobic Oxidation of Substituted Toluenes to Carboxylic Acids. Synlett. 2019, 31 (03): 272–274. ISSN 0936-5214. doi:10.1055/s-0039-1691534.

[12] Ozen, Recep. Pyridinium Chlorochromate Catalyzed Oxidation of Toluenes to Aromatic Carboxylic Acids with Molecular Oxygen in Sub-critical Water. Asian Journal of Chemistry. 2014, 26 (3): 941–942. ISSN 0970-7077. doi:10.14233/ajchem.2014.16651.

[13] Mohammadpour, Pegah; Safaei, Elham. Catalytic C–H aerobic and oxidant-induced oxidation of alkylbenzenes (including toluene derivatives) over VO2+ immobilized on core–shell Fe3O4@SiO2 at room temperature in water. RSC Advances. 2020, 10 (40): 23543–23553. ISSN 2046-2069. doi:10.1039/D0RA03483E.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]