2-メチル-6-ニトロ安息香酸無水物

2-メチル-6-ニトロ安息香酸無水物
	IUPAC名 2-methyl-6-nitrobenzoic anhydride
識別情報
CAS登録番号	434935-69-0
PubChem	10472648
	SMILES O=C(OC(C1=C(C)C=CC=C1[N+]([O-])=O)=O)C2=C([N+]([O-])=O)C=CC=C2C;
特性
化学式	C16H12N2O7
モル質量	344.276 g/mol
外観	微黄色の結晶性粉末
	特記なき場合、データは常温 (25 °C)・常圧 (100 kPa) におけるものである。

2-メチル-6-ニトロ安息香酸無水物（2-メチル-6-ニトロあんそくこうさんむすいぶつ、2-methyl-6-nitrobenzoic anhydride 略称：MNBA）とは、2-メチル-6-ニトロ安息香酸が分子間で脱水縮合した構造をもった化合物であり、椎名試薬^[1]^[2]^[3]^[4]^[5]^[6]^[7]^[8]^[9]^[10]^[11]^[12]^[13]とも呼ばれる縮合剤である。

2002年、椎名勇らが開発した^[14]^[15]^[16]。穏やかな条件下で脱水縮合反応を進行させることができるため、13,000件以上の使用例が報告されている。

概要

ヒドロキシカルボン酸から分子内閉環にて中・大員環ラクトンを形成する合成反応（椎名ラクトン化反応）に用いられる。反応は室温で塩基性および中性条件下で進行する。マクロラクトン化だけでなく、エステル化やアミド化にも利用可能。

脚注

[脚注の使い方]

^ https://www.elsevier.com/books/organic-synthesis/smith/978-0-12-800720-4
^ Eiseman, J. L.; Bai, L.; Jung W.-H.; Moura-Letts, G.; Day, B. W.; Curran, D. P. (2008). “Improved Synthesis of 6-epi-Dictyostatin and Antitumor Efficacy in Mice Bearing MDA-MB231 Human Breast Cancer Xenografts”. J. Med. Chem. 51 (21): 6650. doi:10.1021/jm800979v.
^ Nicolaou, K. C.; Baker, T. M.; Nakamura, T. (2011). “Synthesis of the WXYZA′ Domain of Maitotoxin”. J. Am. Chem. Soc. 133 (2): 220. doi:10.1021/ja109533y.
^ Müller, S.; Mayer, T.; Sasse, F.; Maier, M. E. (2011). “Synthesis of a Pladienolide B Analogue with the Fully Functionalized Core Structure”. Org. Lett. 13 (15): 3940. doi:10.1021/ol201464m.
^ Yamamoto, A.; Ueda, A.; Brémond, P.; Tiseni, P. S.; Kishi, Y. (2012). “Total Synthesis of Halichondrin C”. J. Am. Chem. Soc. 134 (2): 893. doi:10.1021/ja2108307.
^ Ueda, A.; Yamamoto, A.; Kato, D.; Kishi, Y. (2014). “Total Synthesis of Halichondrin A, the Missing Member in the Halichondrin Class of Natural Products”. J. Am. Chem. Soc. 136 (13): 5171. doi:10.1021/ja5013307.
^ Beveridge, R. E.; Batey, R. A. (2014). “An Organotrifluoroborate-Based Convergent Total Synthesis of the Potent Cancer Cell Growth Inhibitory Depsipeptides Kitastatin and Respirantin”. Org. Lett. 16 (9): 2322. doi:10.1021/ol500484f.
^ Janetzko, J.; Batey, R. A. (2014). “Organoboron-Based Allylation Approach to the Total Synthesis of the Medium-Ring Dilactone (+)-Antimycin A_1b”. J. Org. Chem. 79 (16): 7415. doi:10.1021/jo501134d.
^ Wünsch, S.; Breit, B. (2015). “Probing o-Diphenylphosphanyl Benzoate (o-DPPB)-Directed C－C Bond Formation: Total Synthesis of Dictyostatin”. Chem. Eur. J. 21 (6): 2358. doi:10.1002/chem.201406252.
^ Goodreid, J. D.; Da Silveira Dos Santos, E.; Batey, R. A. (2015). “A Lanthanide(III) Triflate Mediated Macrolactonization/Solid-Phase Synthesis Approach for Depsipeptide Synthesis”. Org. Lett. 17 (9): 2182. doi:10.1021/acs.orglett.5b00781.
^ Sato, E.; Tanabe, Y.; Nakajima, N.; Ohkubo, A.; Suenaga, K. (2016). “Total Synthesis of Biselyngbyolide B”. Org. Lett. 18 (9): 2047. doi:10.1021/acs.orglett.6b00660.
^ Ogawa, H.; Iwasaki, A.; Sumimoto, S.; Iwatsuki, M.; Ishiyama, A.; Hokari, R.; Otoguro, K.; Omura, S. et al. (2017). “Isolation and Total Synthesis of Hoshinolactam, an Antitrypanosomal Lactam from a Marine Cyanobacterium”. Org. Lett. 19 (4): 890. doi:10.1021/acs.orglett.7b00047.
^ Yahata, K.; Ye, N.; Iso, K.; Naini, S. R.; Yamashita, S.; Ai, Y.; Kishi, Y. (2017). “Unified Synthesis of Right Halves of Halichondrins A–C”. J. Org. Chem. 82 (17): 8792. doi:10.1021/acs.joc.7b01283.
^ Shiina, I.; Ibuka, R.; Kubota, M. (2002). “A New Condensation Reaction for the Synthesis of Carboxylic Esters from Nearly Equimolar Amounts of Carboxylic Acids and Alcohols Using 2-Methyl-6-nitrobenzoic Anhydride”. Chem. Lett. 31 (3): 286. doi:10.1246/cl.2002.286.
^ Shiina, I.; Hashizume, M.; Yamai, Y.; Oshiumi, H.; Shimazaki, T.; Takasuna, Y.; Ibuka, R. (2005). “Enantioselective Total Synthesis of Octalactin A Using Asymmetric Aldol Reactions and a Rapid Lactonization To Form a Medium-Sized Ring”. Chem. Eur. J. 11: 6601–6608. doi:10.1002/chem.200500417. PMID 16118824.
^ Shiina, I. (2014). “An Adventurous Synthetic Journey with MNBA from Its Reaction Chemistry to the Total Synthesis of Natural Products”. Bull. Chem. Soc. Jpn. 87 (2): 196. doi:10.1246/bcsj.20130216.

外部リンク

[1] ttps://www.elsevier.com/books/organic-synthesis/smith/978-0-12-800720-4

[2] Eiseman, J. L.; Bai, L.; Jung W.-H.; Moura-Letts, G.; Day, B. W.; Curran, D. P. (2008). “Improved Synthesis of 6-epi-Dictyostatin and Antitumor Efficacy in Mice Bearing MDA-MB231 Human Breast Cancer Xenografts”. J. Med. Chem. 51 (21): 6650. doi:10.1021/jm800979v.

[3] Nicolaou, K. C.; Baker, T. M.; Nakamura, T. (2011). “Synthesis of the WXYZA′ Domain of Maitotoxin”. J. Am. Chem. Soc. 133 (2): 220. doi:10.1021/ja109533y.

[4] Müller, S.; Mayer, T.; Sasse, F.; Maier, M. E. (2011). “Synthesis of a Pladienolide B Analogue with the Fully Functionalized Core Structure”. Org. Lett. 13 (15): 3940. doi:10.1021/ol201464m.

[5] Yamamoto, A.; Ueda, A.; Brémond, P.; Tiseni, P. S.; Kishi, Y. (2012). “Total Synthesis of Halichondrin C”. J. Am. Chem. Soc. 134 (2): 893. doi:10.1021/ja2108307.

[6] Ueda, A.; Yamamoto, A.; Kato, D.; Kishi, Y. (2014). “Total Synthesis of Halichondrin A, the Missing Member in the Halichondrin Class of Natural Products”. J. Am. Chem. Soc. 136 (13): 5171. doi:10.1021/ja5013307.

[7] Beveridge, R. E.; Batey, R. A. (2014). “An Organotrifluoroborate-Based Convergent Total Synthesis of the Potent Cancer Cell Growth Inhibitory Depsipeptides Kitastatin and Respirantin”. Org. Lett. 16 (9): 2322. doi:10.1021/ol500484f.

[8] Janetzko, J.; Batey, R. A. (2014). “Organoboron-Based Allylation Approach to the Total Synthesis of the Medium-Ring Dilactone (+)-Antimycin A_1b”. J. Org. Chem. 79 (16): 7415. doi:10.1021/jo501134d.

[9] Wünsch, S.; Breit, B. (2015). “Probing o-Diphenylphosphanyl Benzoate (o-DPPB)-Directed C－C Bond Formation: Total Synthesis of Dictyostatin”. Chem. Eur. J. 21 (6): 2358. doi:10.1002/chem.201406252.

[10] Goodreid, J. D.; Da Silveira Dos Santos, E.; Batey, R. A. (2015). “A Lanthanide(III) Triflate Mediated Macrolactonization/Solid-Phase Synthesis Approach for Depsipeptide Synthesis”. Org. Lett. 17 (9): 2182. doi:10.1021/acs.orglett.5b00781.

[11] Sato, E.; Tanabe, Y.; Nakajima, N.; Ohkubo, A.; Suenaga, K. (2016). “Total Synthesis of Biselyngbyolide B”. Org. Lett. 18 (9): 2047. doi:10.1021/acs.orglett.6b00660.

[12] Ogawa, H.; Iwasaki, A.; Sumimoto, S.; Iwatsuki, M.; Ishiyama, A.; Hokari, R.; Otoguro, K.; Omura, S. et al. (2017). “Isolation and Total Synthesis of Hoshinolactam, an Antitrypanosomal Lactam from a Marine Cyanobacterium”. Org. Lett. 19 (4): 890. doi:10.1021/acs.orglett.7b00047.

[13] Yahata, K.; Ye, N.; Iso, K.; Naini, S. R.; Yamashita, S.; Ai, Y.; Kishi, Y. (2017). “Unified Synthesis of Right Halves of Halichondrins A–C”. J. Org. Chem. 82 (17): 8792. doi:10.1021/acs.joc.7b01283.

[14] Shiina, I.; Ibuka, R.; Kubota, M. (2002). “A New Condensation Reaction for the Synthesis of Carboxylic Esters from Nearly Equimolar Amounts of Carboxylic Acids and Alcohols Using 2-Methyl-6-nitrobenzoic Anhydride”. Chem. Lett. 31 (3): 286. doi:10.1246/cl.2002.286.

[15] Shiina, I.; Hashizume, M.; Yamai, Y.; Oshiumi, H.; Shimazaki, T.; Takasuna, Y.; Ibuka, R. (2005). “Enantioselective Total Synthesis of Octalactin A Using Asymmetric Aldol Reactions and a Rapid Lactonization To Form a Medium-Sized Ring”. Chem. Eur. J. 11: 6601–6608. doi:10.1002/chem.200500417. PMID 16118824.

[16] Shiina, I. (2014). “An Adventurous Synthetic Journey with MNBA from Its Reaction Chemistry to the Total Synthesis of Natural Products”. Bull. Chem. Soc. Jpn. 87 (2): 196. doi:10.1246/bcsj.20130216.

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概要

脚注

関連項目

外部リンク