Selective synthesis of naphthalenedicarboxylic acid

萘二甲酸的选择性合成

• 批准号: 05555248
• 负责人: HIRAI Hidefumi
• 金额: $ 6.4万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05555248/
• 关键词: 2-Naphthalenecarboxylic acid; Naphthalenedicarboxylic acid; Carboxylation; Carbon tetrachloride; Cyclodextrin; 2, 6-naphthalenedicarboxylic acid; Inclusion complex; Nuclear magnetic resonance spectroscopy

1.2, 6-Naphthalenedicarboxylic acid (2, 6-NDA) is a useful intermediate for the syntheses of high performance polymers and liquid crystalline compounds. Poly (ethylene 2, 6-naphthalene-dicarboxylate) is superior to poly (ethylene terephthalate) in mechanical properties, thermostability and gas-barrier ability of films. The synthesis of 2, 6-NDA was attempted by oxudation of 2, 6-dialkylnaphthalene, and by oxidation of 2-alky-6-acylnaphthalene. We reported preliminarily the selective carboxylation of 2-naphthalenecarboxylic acid using beta-cyclodextrin (beta-CyD) as catalyst. The present research has been carried out to search the optimum conditions for the selective synthesis of 2, 6-NDA from 2-naphthalenecarboxylic acid, carbon tetrachloride and copper powder in aqueous alkali by the use of beta-CyD.2. The yield of 2, 6-NDA increased with increasing amounts of beta-CyD, and took a maximum (39 mol% with 78% selectivity) at the initial mole ratio of beta-CyD to 2-naphtalenecarboxylic ac … More id of 1.0, where the 2, 7-DNA and 1, 6-NDA were 9.1 mol% and 1.7mol%, respectivelv. When alpha-CyD or gamma-CyD was used instead of beta-CyD, the reaction hardly proceeded.3. The yield of 2, 6-NDA increased with increasing amounts of carbon tetrachloride, and had a maximal value (58 mol% with 83% selectivity) at the initial mole ratio of carbon tetrachloride to 2-naphthalenecarboxylic acid of 5.0. The efficient addition of carbon tetrachloride was affempted. The reaction was started with the addition of 0.6 mmol of carbon tetrachloride to the aqueous sodium hydroxide solution containing 2-naphthalenecarboxylic acid, beta-CyD and copper powder, and was continued for 8 h by adding 0.6 mmol or carbon tetrachloride to the reaction mixture at 15 min intervals. The resulting yields of 2, 6-NDA was 67 mol% with 84% selectivity.4. The conformation of beta-CyD-2-naphthalenecarboxylate inclusion complex in aqueous alkali was determined by the nuclear magnetic resonance spectroscopy using ^1H homonuclear Overhauser enhancement on the rotating frame. The very high selectivity was ascribed to the conformation of the beta-CyD-2-naphthalenecarboxylate inclusion complex. Less

1.2，6-萘二甲酸(2，6-NDA)是合成高性能聚合物和液晶化合物的重要中间体。聚2，6-萘二甲酸乙二酯在力学性能、热稳定性和阻气性能方面优于聚对苯二甲酸乙二酯。尝试了2，6-二烷基-6-萘氧化和2-烷基-6-酰基-2-萘氧化合成2，6-NDA的方法。本文初步报道了β-环糊精(β-CyD)催化2-萘甲酸的选择性羧化反应。研究了在碱性条件下，以β-CyD2为催化剂，以2-萘甲酸、四氯化碳和铜粉为原料，选择性合成2，6-NDA的最佳条件。随着β-CyD用量的增加，2，6-NDA的产率增加，在β-Cyd与2-萘甲酸乙酯…的初始摩尔比时，2，6-NDA的产率达到最大值(39mol%，选择性78%)More id=1.0，其中2，7-DNA和1，6-NDA分别为9.1mol%和1.7mol%。当用α-Cyd或γ-Cyd代替β-Cyd时，反应几乎不进行。随着四氯化碳用量的增加，2，6-NDA的产率增加，当四氯化碳与2-萘甲酸的初始摩尔比为5.0时，2，6-NDA的产率达到最大值(58mol%，选择性83%)。四氯化碳的有效添加受到了限制。在含有2-萘甲酸、β-环糊精和铜粉的氢氧化钠水溶液中加入0.6 mmo1的四氯化碳开始反应，每隔15 m in加入0.6 mmo1或四氯化碳继续反应8 h。2，6-NDA的产率为67%，选择性为84%。用~1H同核Overhaser增强的核磁共振波谱测定了β-CyD-2-萘甲酸酯包合物在碱性水溶液中的构象。很高的选择性归因于β-CyD-2-萘羧酸盐包合物的构象。较少

项目成果

Hidefumi Hirai, Hisashi Mihori and Rikinori Terakado: "Selective synthesis of 2, 6-naphthalenedicarboxylic acid using cyclodextrin as catalyst" Makromol. Chem., Rapid Commun.Vol. 14, No. 7. 439-443 (1993)

Hidefumi Hirai、Hisashi Mihori 和 Rikinori Terakado：“使用环糊精作为催化剂选择性合成 2, 6-萘二甲酸”Makromol。

Hidefumi Hirai, Yukihide Shiraishi, Hisashi Mihori and Tokiji Kawamura: "Conformation of beta-cyclodextrin-2-naphthalenecarboxylate inclusion complex in aqueous solution" Polym. J.Vol. 27, No. 10. 1064-1067 (1995)

Hidefumi Hirai、Yukihide Shiraishi、Hisashi Mihori 和 Tokiji Kawamura：“水溶液中 β-环糊精-2-萘甲酸包合物的构象”Polym。

Hidefumi HIRAI: "Syntheses of key monomers for advanced polymer materials using cyclodextrin as catalyst" J.Macromol.Sci.-Pure Appl.Chem.A31. 1491-1500 (1994)

Hidefumi HIRAI：“使用环糊精作为催化剂合成先进聚合物材料的关键单体”J.Macromol.Sci.-Pure Appl.Chem.A31。

Hidefumi HIRAI: "Conformation of β-cyclodextrin-2-naphthalenecarboxylate inclusion complex in aqueous solution" Polym.J.27. 1064-1067 (1995)

Hidefumi HIRAI：“水溶液中 β-环糊精-2-萘甲酸酯包合物的构象”Polym.J.27 (1995)。

Hidefumi Hirai: "Syntheses of key monomers for advanced polymer materials using cyclodextrin as catalyst" J.Macromol. Sci-Pure Appl. Chem.Vol. A31, No. 11. 1491-1500 (1994)

Hidefumi Hirai：“使用环糊精作为催化剂合成先进聚合物材料的关键单体”J.Macromol。