二苯基吡啶-2,6-二羧酸酯 | 10448-12-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 中文名称: 二苯基吡啶-2,6-二羧酸酯
• 英文名称: 2,6-pyridinedicarboxylic acid diphenyl ester
• 英文别名: pyridine-2,6-dicarboxylic acid diphenyl ester；Pyridin-2,6-dicarbonsaeure-diphenylester；Dipicolinsaeure-diphenylester；Diphenyl pyridine-2,6-dicarboxylate
• CAS: 10448-12-1
• 化学式: C₁₉H₁₃NO₄
• 分子量: 319.317
• InChiKey: HGRACXZSQPEEPI-UHFFFAOYSA-N

物化性质

• 熔点：
  179 °C
• 沸点：
  520.8±35.0 °C(Predicted)
• 密度：
  1.279±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  65.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  二苯基吡啶-2,6-二羧酸酯 、 环己酮 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以41%的产率得到2,6-Bis<(2-oxocyclohexanyl)carbonyl>pyridine
  参考文献：
  名称：

  Chelation-Controlled Regioselectivity in the Synthesis of Substituted Pyrazolylpyridine Ligands. 2. Tridentates

  摘要：

  A new, more reliable synthesis of tetraketone 4 was found. With (t)BuNHNH(2), PhNHNH(2), and 4-hydrazinobenzoic acid, it condensed to give mostly in,in-disubstituted derivatives (7ii-9ii) of the parent, C-linked 2,6-bis(pyrazol-3-yl)pyridine 5, along with some in,out materials. MeNHNH(2) also provided some out,out isomer (6oo). This same derivative was also produced by NaH-mediated methylation of 5 with CH3I, presumably via a Na+ chelate that disallowed access to the inner pyrazole nitrogens, and was able, as a tridentate, to solubilize solid sodium picrate (NaPic) into CDCl3, with H-1-NMR detection of the complex. In contrast, the bidentate in,out isomer did not solubilize NaPic. Similarly, ethyl bromoacetate produced 10oo and it also solubilized NaPic. Previously reported alkylations of 5 had also given out,out products that bound alkali metal ions. 10oo was hydrolyzed to the disalt 13oo. In the presence of ZnCl2, 1 reacted with PhNHNH(2) to give the out,out derivative 8oo, presumably through a metal-mediated activation of the inner carbonyls of 1. Though 8oo also solubilized NaPic, a better NMR spectrum was obtained by treatment with CF3COOD, which indicated multidentate binding of D+. The same phenomenon was also observed with the out,out diester 1 loo, which was obtained by the nucleophilic aromatic substitution by 5 of ethyl 4-fluorobenzoate, presumably via a Kf chelate that also disallowed in substitution. A mono-out-substituted product 12 was also isolated from this reaction. Apart from mechanistic arguments and the ability or inability to dissolve NaPic, the aromatic H-1-NMR regions were diagnostic of the regiochemistries: In all cases, the pyridine H-3/5 doublet lay upfield of the H-4 triplet for in,in. isomers and downfield for out,out isomers, while in,out isomers showed one doublet on either side of the triplet. The binding of Na+ or D+ by the out,out isomers resulted in shifts of the H-3/5 doublets to upfield positions. The deuteration of in,in isomers did not. This situation was analogous to that of the bidentates reported in the accompanying paper and was similarly interpreted in conformational terms, with support from MM2 calculations: Like terpyridine, the imino nitrogens of the out,out materials prefer anti orientations due to electronic and steric repulsions (calculated Delta G(syn-anti) > 2.7 kcal/mol between rotamers about each pyridine-pyrazole bond in 6oo and 7oo and about the out-substituted pyrazole-pyridine bonds of 6io and 7io), but they are forced into syn orientations upon binding Na+ or D+. This induces a shielding interaction between the pyridine H-3/5 and neighboring CH2 groups. This same shielding is present in any conformation of the in,in products and of the in-substituted side of in,out isomers, which are much closer in energy (/Delta G(syn-anti)/ less than or equal to 0.4 kcal/mol for any ring-ring bond in 6ii and 7ii and for the in-substituted pyrazole-pyridine bonds of 6io and 7io).

  DOI：

  10.1021/jo00086a029
• 作为产物：
  描述：

  苯酚 在 palladium diacetate 、 乙酸酐 、 三乙胺 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 乙腈 为溶剂， 反应 3.5h， 生成 二苯基吡啶-2,6-二羧酸酯
  参考文献：
  名称：

  钯催化的芳基，烯基和烯丙基卤与羰基甲酸酯的羰基化反应

  摘要：

  据报道，用甲酸苯基酯可以高效地钯催化芳基，烯基和烯丙基卤的羰基化反应。该方法不使用一氧化碳，并且以优异的产率提供了一个碳长的羧酸苯基酯。该反应在温和条件下平稳进行，并能耐受各种官能团，包括醛，醚，酮，酯和氰基。此外，可以将多种杂芳族溴化物高产率地转化为相应的苯基酯。

  DOI：

  10.1021/ol301192s

文献信息

• MODIFIER FOR AROMATIC POLYESTER AND AROMATIC POLYESTER RESIN COMPOSITION COMPRISING THE SAME
  申请人：TABATA Masayoshi

  公开号：US20110224343A1

  公开（公告）日：2011-09-15

  The present invention provides a modifier for aromatic polyesters which enhances the melt fluidity of aromatic polyesters without a significant decrease in the heat resistance of the aromatic polyesters, and an aromatic polyester resin composition including the modifier for aromatic polyesters. The present invention relates to a modifier for aromatic polyesters comprising polyhydric phenol residues and residues of aromatic polycarboxylic acid, acid halide or acid anhydride thereof, and the modifier comprises a material having a structure composed of a first residue selected from the group consisting of divalent residues represented by Formula (I): —Ar—W 1 x —Ar— and by Formula (II): —Ar—, the first residues being bonded to two identical or different second residues selected from the group consisting of monovalent residues represented by Formula (III): and monovalent residues represented by Formula (IV): —O—C(O)—R 7 —.

  本发明提供了一种用于芳香族聚酯的改性剂，可以增强芳香族聚酯的熔融流动性，而不明显降低芳香族聚酯的耐热性，以及包括该改性剂的芳香族聚酯树脂组合物。本发明涉及一种用于芳香族聚酯的改性剂，包括多羟基酚残基和芳香族多羧酸、酸卤或其酸酐残基，该改性剂包括具有以下结构的材料：第一残基，选择自由式(I)所代表的二价残基：—Ar—W1x—Ar—和自由式(II)所代表的：—Ar—，第一残基与选择自由式(III)所代表的单价残基：和自由式(IV)所代表的单价残基：—O—C(O)—R7—的两个相同或不同的第二残基结合。
• AROMATIC POLYESTER
  申请人：Muroran Institute of Technology

  公开号：EP2479203A1

  公开（公告）日：2012-07-25

  The present invention provides an aromatic polyester which is substantially free from the occurrence of coloration and retains significantly high transparency even after being thermally processed at high temperature and which has high flowability. The aromatic polyester contains a polyhydric phenol residue and a residue of any one of aromatic polycarboxylic acid, halide thereof, and anhydride thereof, and terminals of the aromatic polyester have a structure represented by the formula -C(O)-R. The aromatic polyester has an end-capping rate of 90% or higher and a weight average molecular weight (Mw) ranging from 3,000 to 1,000,000.

  本发明提供了一种芳香族聚酯，该聚酯基本上不会发生着色，即使在高温热加工后仍能保持明显的高透明度，并且具有高流动性。芳香族聚酯含有多羟基苯酚残留物和芳香族多羧酸、其卤化物和其酸酐中任意一种的残留物，芳香族聚酯的端基具有式 -C(O)-R 所代表的结构。芳香族聚酯的端盖率为 90% 或更高，重量平均分子量（Mw）为 3,000 至 1,000,000 之间。
• Meyer, Recueil des Travaux Chimiques des Pays-Bas, 1925, vol. 44, p. 328
  作者：Meyer

  DOI：——

  日期：——
• RASSHOFER W.; MUELLER W. M.; VOEGTLE F., CHEM. BER. 1979, 112, NO 6, 2095-2119
  作者：RASSHOFER W.、 MUELLER W. M.、 VOEGTLE F.

  DOI：——

  日期：——
• US8129493B2
  申请人：——

  公开号：US8129493B2

  公开（公告）日：2012-03-06