dimethyl 2-(bromomethyl)-1,3-benzenedicarboxylate | 16281-93-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl 2-(bromomethyl)-1,3-benzenedicarboxylate
• 英文别名: dimethyl 2-bromomethylbenzene-1,3-dicarboxylate；2,6-Dicarbomethoxy-benzylbromid；Dimethyl 2-(bromomethyl)isophthalate；dimethyl 2-(bromomethyl)benzene-1,3-dicarboxylate
• CAS: 16281-93-9
• 化学式: C₁₁H₁₁BrO₄
• 分子量: 287.11
• InChiKey: KRJSSQZVMROWLC-UHFFFAOYSA-N

物化性质

• 熔点：
  96-98 °C
• 沸点：
  381.4±37.0 °C(Predicted)
• 密度：
  1.474±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险类别：
  8
• 危险性防范说明：
  P264,P270,P271,P280,P303+P361+P353,P304+P340,P305+P351+P338,P310,P330,P331,P363,P403+P233,P501
• 危险品运输编号：
  3261
• 危险性描述：
  H302,H314
• 包装等级：
  III

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(bromomethyl)-1,3-benzenedicarboxylate 在 盐酸 、 氢氧化钾 、 氯化亚砜 作用下， 反应 2.75h， 生成 1-oxo-3H-2-benzofuran-4-carbonyl chloride
  参考文献：
  名称：

  Convenient Syntheses of 1,3-Dihydro-1-oxo-4-isobenzofurancarboxylic Acid, 1,3-Dihydro-3-oxo-4-isobenzofurancarboxylic Acid, and the Homologous Acetic Acids

  摘要：

  通过扩展戴维斯和珀金的邻苯二甲酸合成法，制备了 1-二氢-1-氧代和 1,3-二氢-3-氧代-4-异苯并呋喃羧酸，并通过 Arndt-Eistert 反应将其同源化为相应的乙酸衍生物。

  DOI：

  10.1055/s-1990-26963
• 作为产物：
  描述：

  间苯二甲腈 在 氢氧化钾 、 硫酸 、 溴 、 lithium diisopropyl amide 作用下， 以 四氯化碳 为溶剂， 生成 dimethyl 2-(bromomethyl)-1,3-benzenedicarboxylate
  参考文献：
  名称：

  Design and Synthesis of a Trifunctional Chiral Porphyrin with C2 Symmetry as a Chiral Recognition Host for Amino Acid Esters

  摘要：

  An intrinsic chiral recognition host, (R,R)- or (S,S)-[trans-5,15-bis(2-hydroxyphenyl)-10-{2,6-bis((methoxycarbonyl)methyl)phenyl}-2,3,17,18-tetraethylporphyrinato]zinc(II) (1), was synthesized by the coupling between (3,3',4,4'-tetraethyl-5,5'-bis(alpha-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane (8) and dimethyl 2-(bis(2-pyrryl)-methyl)-1, 3-benzenediacetate (16). This pyrrylmethanol method made it possible to perform the regiospecific coupling between differently functionalized dipyrromethane units. Host 1 was designed to have three recognition elements: metal coordination, hydrogen bond donor, and hydrogen bond acceptor (and/or steric repulsion) groups. These groups are arranged in a convergent fashion, forming a chiral recognition pocket. Host 1 was resolved into two enantiomers, (+)-1 and (-)-1. The binding constants in CHCl3 were determined by UV-vis titration. Host (+)-1 was found to show an enantioselectivity of 2.0-2.8 in respect to L- and D-enantiomers of Ile-OMe, Leu-OMe, Leu-OBzl, Val-OMe, Pro-OMe, and Phe-OMe. Host (+)-1 showed an enantioselectivity of 0.47 in respect to L- and D-enantiomers of serine benzyl ester, indicating that the enantioselectivity was reversed. Reference porphyrins 2-4, which lack some of recognition groups, were also synthesized by the pyrrylmethanol method to clarify the roles of the recognition groups of (+)-1 in thermodynamics of the binding processes. Total free energy change upon binding of L- and D-Ile-OMe to host (+)-1 (Delta G degrees(total) for L, -5.05, and D, -4.46 kcal/mol) was separated into three terms: metal coordination energy (Delta G degrees(Zn)), -4.15 kcal/mol; hydrogen bond energy (Delta Delta G degrees(OH)), -1.30 kcal/mol; and steric repulsion energy (Delta Delta G degrees(COOMe)(L) or Delta Delta G degrees(COOMe)(D)), +0.40 kcal/mol for L- and +0.99 kcal/mol for D-Ile-OMe. The third recognition group (CH(2)CO(2)Me) of (+)-1 was found to destabilize the complexes due to steric repulsions. In contrast, the CH(2)CO(2)Me group was found to stabilize the complex between D-Ser-OBzl and (+)-1, suggesting that hydrogen bonding between the OH group of serine and the C=O group of (+)-1 takes place. On the basis of these thermodynamic studies, chiral recognition was found to be achieved by cooperative functions of these three recognition groups.

  DOI：

  10.1021/ja00089a013

文献信息

• Synthesis of 9-Methoxymethyl-18-methyl-2,11-dithia[3.3]metacyclophane: a Dithia[3.3]metacyclophane With a Protected Internal Benzylic Functional Group
  作者：YH Lai、QM Tan

  DOI：10.1071/ch9901783

  日期：——

  A synthetic route to a dithia [3.3] metacyclophane with a benzylic functional ( methoxymethyl ) group at C9 is described. The benzylic function however had to be introduced at a later stage in the synthetic scheme to optimize the overall yield. Only the anti isomer of the desired dithiacyclophane (7) was isolated. The entire methoxymethyl group lies within the shielding zone of the opposite benzene ring as indicated in the 1H n.m.r. spectrum. Attempts to convert anti-(7) into the novel aromatic system (5b) by a rearrangement-elimination sequence however failed.

  本文介绍了一种在 C9 位带有苄基官能团（甲氧基甲基）的二硫[3.3]偏环烷的合成路线。不过，苄基官能团必须在合成方案的后期引入，以优化总产率。只分离出了所需的二硫代环烷（7）的反异构体。如 1H n.m.r. 光谱所示，整个甲氧基甲基位于对侧苯环的屏蔽区内。然而，通过重排-消除顺序将反（7）转化为新型芳香系统（5b）的尝试失败了。
• Synthesis and conformational study of 9,18-(ethylenedioxy)-2,11-dithia[3.3]metacyclophane: the propelling behavior of the three bridges in a [3.4.3](1,2,3)cyclophane
  作者：Yee Hing Lai、Chin Wee Tan

  DOI：10.1021/jo00001a050

  日期：1991.1

  A general approach which involved first the introduction of the central oxy or dioxy bridge and subsequent intramolecular coupling reactions to form the two thia bridges was employed in the syntheses of the 1,2,3-triply bridged cyclophanes 2, 3, and 4. The attempted routes to potential precursors of 2 were unsuccessful while the tetrabromide 16 could be synthesized. Intramolecular cyclizations of the latter, however, failed to yield 4, possibly due to unfavorable stereochemistry of the intermediate leading to the second intramolecular coupling reaction. The tetrabromide 18, with a central bridge of an appropriate length, successfully led to the formation of 3. The conformational behavior of 3 was analyzed by dynamic H-1 NMR spectroscopy. The ethylenedioxy bridge is believed to adopt the symmetrical ''boat'' conformation. All three bridges, however, undergo unrestricted pseudorotation, represented by free conformational interconversion 3b reversible 3c, at room temperature. A relatively frozen conformation 3b (3c) was observed at the low-temperature limit. Flipping processes of the ethylenedioxy bridge and the two thia bridges are found to be interdependent, resulting in an overall propelling process with a common conformational barrier estimated at ca. 45 kJ mol-1.
• Intramolecular nucleophilic participation. VI. Forced carbomethoxy group participation in the solvolysis of 1-(2,6-dicarbomethoxyphenyl)ethyl bromide
  作者：M. J. Strauss、L. J. Andrews、R. M. Keefer

  DOI：10.1021/ja01015a033

  日期：1968.6
• SKEEAN, RICHARD W.;GOEL, O. P., SYNTHESIS,(1990) N, C. 628-630
  作者：SKEEAN, RICHARD W.、GOEL, O. P.

  DOI：——

  日期：——
• LAI, YEE-HING;TAN, QUEE-MAY, AUSTRAL. J. CHEM., 43,(1990) N0, C. 1783-1788
  作者：LAI, YEE-HING、TAN, QUEE-MAY

  DOI：——

  日期：——