对苯二甲醛

对苯二甲醛
别名	1,4-苯二甲醛; 苯-1,4-二甲醛
识别
CAS号	623-27-8
性质
化学式	C8H6O2
摩尔质量	134.13 g·mol−1
熔点	114—115 °C（387—388 K）
溶解性（水）	0.11 g（25 °C）
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

对苯二甲醛是一种有机化合物，化学式为C₈H₆O₂。

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合成

对苯二甲醛可由对苯二甲醇的催化氧化反应制得。^[2]^[3]

对苯二甲酸在叔戊酸酐存在下、钯配合物催化下氢化，可以得到对苯二甲醛；^[4]它也可由对苯二甲腈经三(二烷基氨基)氢化钠还原得到。^[5]

2,5-二羟基-1,4-苯二甲醛在二氯甲烷中和三溴化硼反应，也能得到对苯二甲醛。^[6]

反应

对苯二甲醛具有醛的通性，如可以和胺缩合，形成C=N-C键，并可进一步被硼氢化钠还原为仲胺（C-NH-C）。^[7]它可以发生亨利反应，如和硝基甲烷反应，生成α,α'-二(硝基甲基)对苯二甲醇。^[8]它和氰乙酸乙酯发生Knoevenagel缩合反应，生成3,3'-(1,4-苯二基)二(2-氰基-2-丙烯酸乙酯)。^[9]

除了氰乙酸乙酯外，它和丙二腈、丙二酸二乙酯、巴比妥酸等活泼亚甲基化合物^[10]的反应也是已知的。在溴化氰和乙醇钠存在下，它和丙二腈反应，生成1,4-二(2,2,3,3-四氰基环丙基)苯。^[11]

在三乙胺催化下，它可以和亚磷酸二甲酯反应，得到(1,4-苯二基)二(羟甲基膦酸二甲酯)。^[12]

参考文献

[1]
Doleschall, Gábor. Novel aldehyde syntheses based on selective reduction of s-triazole derivatives. Tetrahedron. January 1976, 32 (21): 2549–2558. ISSN 0040-4020. doi:10.1016/0040-4020(76)88025-8.
[2]
Lai, Ya-Liang; Wang, Xue-Zhi; Dai, Rui-Rong; Huang, Yong-Liang; Zhou, Xian-Chao; Zhou, Xiao-Ping; Li, Dan. Self-assembly of mixed-valence and heterometallic metallocycles: efficient catalysts for the oxidation of alcohols to aldehydes in ambient air. Dalton Transactions. 2020, 49 (22): 7304–7308 [2022-07-29]. ISSN 1477-9226. PMID 32427249. doi:10.1039/d0dt01340d. eISSN 1477-9234. （原始内容存档于2022-08-06）.
[3]
Namboodiri, Vasudevan V.; Polshettiwar, Vivek; Varma, Rajender S. Expeditious oxidation of alcohols to carbonyl compounds using iron(III) nitrate. Tetrahedron Letters. December 2007, 48 (50): 8839–8842. ISSN 0040-4039. doi:10.1016/j.tetlet.2007.10.068.
[4]
Nagayama, Kazuhiro; Shimizu, Isao; Yamamoto, Akio. Direct Hydrogenation of Carboxylic Acids to Corresponding Aldehydes Catalyzed by Palladium Complexes in the Presence of Pivalic Anhydride. Chemistry Letters. November 1998, 27 (11): 1143–1144 [2022-07-29]. ISSN 0366-7022. doi:10.1246/cl.1998.1143. eISSN 1348-0715. （原始内容存档于2022-07-29）.
[5]
Cha, Jin Soon; Jeoung, Min Kyoo; Kim, Jong Mi; Kwon, Oh Oun; Lee, Jae Cheol. Conversion of Aromatic Nitriles to Aldehydes by Sodium Tris(dialkylamino)aluminum Hydrides. Organic Preparations and Procedures International. October 1994, 26 (5): 583–588 [2022-07-29]. ISSN 0030-4948. doi:10.1080/00304949409458063. eISSN 1945-5453. （原始内容存档于2022-07-29）.
[6]
Greenaway, R. L.; Santolini, V.; Bennison, M. J.; Alston, B. M.; Pugh, C. J.; Little, M. A.; Miklitz, M.; Eden-Rump, E. G. B.; Clowes, R.; Shakil, A.; Cuthbertson, H. J.; Armstrong, H.; Briggs, M. E.; Jelfs, K. E.; Cooper, A. I. High-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis. Nature Communications. 20 July 2018, 9 (1) [2022-07-29]. PMC 6054661 . PMID 30030426. doi:10.1038/s41467-018-05271-9. eISSN 2041-1723. （原始内容存档于2022-07-29）.
[7]
Pettersson, Sofia; Pérez-Nueno, Violeta I.; Ros-Blanco, Laia; Puig de La Bellacasa, Raimon; Rabal, María Obdulia; Batllori, Xavier; Clotet, Bonaventura; Clotet-Codina, Imma; Armand-Ugón, Mercedes; Esté, José; Borrell, José I.; Teixidó, Jordi. Discovery of Novel Non-Cyclam Polynitrogenated CXCR4 Coreceptor Inhibitors. ChemMedChem. 20 October 2008, 3 (10): 1549–1557 [2022-07-29]. ISSN 1860-7179. PMID 18671217. doi:10.1002/cmdc.200800145. eISSN 1860-7187. （原始内容存档于2022-07-29）.
[8]
Alizadeh, Abdolhamid; Khodaei, Mohammad M.; Abdi, Gisya; Kordestani, Davood. The First Report on Chemoselective Biguanide-Catalyzed Henry Reaction under Neat Conditions. Bulletin of the Korean Chemical Society. 20 November 2012, 33 (11): 3640–3644 [2022-07-29]. ISSN 0253-2964. doi:10.5012/bkcs.2012.33.11.3640. （原始内容存档于2022-07-29）.
[9]
Kühbeck, Dennis; Saidulu, G.; Reddy, K. Rajender; Díaz, David Díaz. Critical assessment of the efficiency of chitosan biohydrogel beads as recyclable and heterogeneous organocatalyst for C–C bond formation. Green Chem. 2012, 14 (2): 378–392 [2022-07-29]. ISSN 1463-9262. doi:10.1039/C1GC15925A. eISSN 1463-9270. （原始内容存档于2022-07-29）.
[10]
Siddiqui, Zeba N.; Khan, Tabassum. Sulfuric acid-modified PEG-6000 (PEG–OSO3H): a biodegradable, reusable solid acid catalyst for highly efficient and eco-friendly synthesis of novel bis-Knoevenagel products under solvent-free conditions. Tetrahedron Letters. July 2013, 54 (29): 3759–3764. ISSN 0040-4039. doi:10.1016/j.tetlet.2013.05.012.
[11]
Noroozi Pesyan, Nader; Rezaee, Mohammad. Solvent-free, one-pot synthesis of pentasubstituted cyclopropanes in the presence of BrCN and EtONa by milling. Monatshefte für Chemie - Chemical Monthly. 8 April 2014, 145 (7): 1165–1171 [2022-07-29]. ISSN 0026-9247. doi:10.1007/s00706-014-1180-2. eISSN 1434-4475. （原始内容存档于2022-07-29）.
[12]
Mou, Zehuai; Wang, Yinjun; Man, Xi. An efficient and green method to prepare bis-α-hydroxy phosphonates using triethylamine as catalyst. Phosphorus, Sulfur, and Silicon and the Related Elements. 28 September 2020, 196 (2): 195–199 [2022-07-29]. ISSN 1042-6507. doi:10.1080/10426507.2020.1825435. eISSN 1563-5325. （原始内容存档于2022-07-29）.

[1] [1]
Doleschall, Gábor. Novel aldehyde syntheses based on selective reduction of s-triazole derivatives. Tetrahedron. January 1976, 32 (21): 2549–2558. ISSN 0040-4020. doi:10.1016/0040-4020(76)88025-8.

[2] [2]
Lai, Ya-Liang; Wang, Xue-Zhi; Dai, Rui-Rong; Huang, Yong-Liang; Zhou, Xian-Chao; Zhou, Xiao-Ping; Li, Dan. Self-assembly of mixed-valence and heterometallic metallocycles: efficient catalysts for the oxidation of alcohols to aldehydes in ambient air. Dalton Transactions. 2020, 49 (22): 7304–7308 [2022-07-29]. ISSN 1477-9226. PMID 32427249. doi:10.1039/d0dt01340d. eISSN 1477-9234. （原始内容存档于2022-08-06）.

[3] [3]
Namboodiri, Vasudevan V.; Polshettiwar, Vivek; Varma, Rajender S. Expeditious oxidation of alcohols to carbonyl compounds using iron(III) nitrate. Tetrahedron Letters. December 2007, 48 (50): 8839–8842. ISSN 0040-4039. doi:10.1016/j.tetlet.2007.10.068.

[4] [4]
Nagayama, Kazuhiro; Shimizu, Isao; Yamamoto, Akio. Direct Hydrogenation of Carboxylic Acids to Corresponding Aldehydes Catalyzed by Palladium Complexes in the Presence of Pivalic Anhydride. Chemistry Letters. November 1998, 27 (11): 1143–1144 [2022-07-29]. ISSN 0366-7022. doi:10.1246/cl.1998.1143. eISSN 1348-0715. （原始内容存档于2022-07-29）.

[5] [5]
Cha, Jin Soon; Jeoung, Min Kyoo; Kim, Jong Mi; Kwon, Oh Oun; Lee, Jae Cheol. Conversion of Aromatic Nitriles to Aldehydes by Sodium Tris(dialkylamino)aluminum Hydrides. Organic Preparations and Procedures International. October 1994, 26 (5): 583–588 [2022-07-29]. ISSN 0030-4948. doi:10.1080/00304949409458063. eISSN 1945-5453. （原始内容存档于2022-07-29）.

[6] [6]
Greenaway, R. L.; Santolini, V.; Bennison, M. J.; Alston, B. M.; Pugh, C. J.; Little, M. A.; Miklitz, M.; Eden-Rump, E. G. B.; Clowes, R.; Shakil, A.; Cuthbertson, H. J.; Armstrong, H.; Briggs, M. E.; Jelfs, K. E.; Cooper, A. I. High-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis. Nature Communications. 20 July 2018, 9 (1) [2022-07-29]. PMC 6054661 . PMID 30030426. doi:10.1038/s41467-018-05271-9. eISSN 2041-1723. （原始内容存档于2022-07-29）.

[7] [7]
Pettersson, Sofia; Pérez-Nueno, Violeta I.; Ros-Blanco, Laia; Puig de La Bellacasa, Raimon; Rabal, María Obdulia; Batllori, Xavier; Clotet, Bonaventura; Clotet-Codina, Imma; Armand-Ugón, Mercedes; Esté, José; Borrell, José I.; Teixidó, Jordi. Discovery of Novel Non-Cyclam Polynitrogenated CXCR4 Coreceptor Inhibitors. ChemMedChem. 20 October 2008, 3 (10): 1549–1557 [2022-07-29]. ISSN 1860-7179. PMID 18671217. doi:10.1002/cmdc.200800145. eISSN 1860-7187. （原始内容存档于2022-07-29）.

[8] [8]
Alizadeh, Abdolhamid; Khodaei, Mohammad M.; Abdi, Gisya; Kordestani, Davood. The First Report on Chemoselective Biguanide-Catalyzed Henry Reaction under Neat Conditions. Bulletin of the Korean Chemical Society. 20 November 2012, 33 (11): 3640–3644 [2022-07-29]. ISSN 0253-2964. doi:10.5012/bkcs.2012.33.11.3640. （原始内容存档于2022-07-29）.

[9] [9]
Kühbeck, Dennis; Saidulu, G.; Reddy, K. Rajender; Díaz, David Díaz. Critical assessment of the efficiency of chitosan biohydrogel beads as recyclable and heterogeneous organocatalyst for C–C bond formation. Green Chem. 2012, 14 (2): 378–392 [2022-07-29]. ISSN 1463-9262. doi:10.1039/C1GC15925A. eISSN 1463-9270. （原始内容存档于2022-07-29）.

[10] [10]
Siddiqui, Zeba N.; Khan, Tabassum. Sulfuric acid-modified PEG-6000 (PEG–OSO3H): a biodegradable, reusable solid acid catalyst for highly efficient and eco-friendly synthesis of novel bis-Knoevenagel products under solvent-free conditions. Tetrahedron Letters. July 2013, 54 (29): 3759–3764. ISSN 0040-4039. doi:10.1016/j.tetlet.2013.05.012.

[11] [11]
Noroozi Pesyan, Nader; Rezaee, Mohammad. Solvent-free, one-pot synthesis of pentasubstituted cyclopropanes in the presence of BrCN and EtONa by milling. Monatshefte für Chemie - Chemical Monthly. 8 April 2014, 145 (7): 1165–1171 [2022-07-29]. ISSN 0026-9247. doi:10.1007/s00706-014-1180-2. eISSN 1434-4475. （原始内容存档于2022-07-29）.

[12] [12]
Mou, Zehuai; Wang, Yinjun; Man, Xi. An efficient and green method to prepare bis-α-hydroxy phosphonates using triethylamine as catalyst. Phosphorus, Sulfur, and Silicon and the Related Elements. 28 September 2020, 196 (2): 195–199 [2022-07-29]. ISSN 1042-6507. doi:10.1080/10426507.2020.1825435. eISSN 1563-5325. （原始内容存档于2022-07-29）.

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