2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylic acid | 168031-70-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylic acid
• 英文别名: 1,3-Benzodioxole-4-carboxylic acid, 2-(1,1-dimethylethyl)-2-methyl-
• CAS: 168031-70-7
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: OBKLBZDYLDXACZ-UHFFFAOYSA-N

物化性质

• 沸点：
  335.2±31.0 °C(Predicted)
• 密度：
  1.194±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylic acid 在 nitronium tetrafluoborate 、 六氟丙烯 、 二乙胺 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 6.0h， 生成 methyl 2-tert-butyl-2-methyl-5-nitro-1,3-benzodioxole-4-carboxylate
  参考文献：
  名称：

  Synthesis and characterization of asymmetric o- and m-nitrobenzoic acids with a 1,3-benzodioxole skeleton

  摘要：

  A symmetric o- and m-nitrobenzoic acids with a 1,3-benzodioxole skeleton have been synthesized and characterized. The synthesis involved nitration at either the C-5 or C-6 position of 2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylate derived from catechol. These were then resolved with chiral solid-phased HPLC columns into each of enantiomers (>99% ee), which were characterized by circular dichroism. The (S)-enantiomers were also obtained by fractional crystallization of the precursor prior to the nitration. When applied as chiral derivation agents for alcohols and amines, m-nitrobenzoic acid showed notable ability to separate the enantiomers in both HPLC and NMR analyses. On the other hand, H-1 NMR and X-ray data of their ester and amide derivatives strongly suggested that the o-nitrobenzoic acid would serve as a fluorescent building block useful for the assembly of beta-peptide linkages with a defined conformation. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.10.030
• 作为产物：
  描述：

  methyl 2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylate 在 Candida antarctica lipase B 作用下， 以 癸烷 为溶剂， 反应 73.0h， 以12%的产率得到2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylic acid
  参考文献：
  名称：

  化学酶法合成2-叔丁基-2-甲基-1,3-苯并二恶唑-4-羧酸（TBMB）酸的两种对映体

  摘要：

  由外消旋酮制备2-叔丁基-2-甲基-1,3-苯并二恶唑-4-羧酸（TBMB）酸的对映异构体，它们在乙缩醛碳上具有一个独特的季手性中心。基团被三氟乙酰基取代。首先，用真菌还原，白色念珠菌提供了（2 S，1 'S）-和（2 R，1 'S）-1'-（2-叔丁基-2-甲基-1,3-苯并二恶唑-4- yl）-2'，2'，2'-三氟乙醇的对映体选择性很高。乙酰化后，将所得非对映异构体混合物提交南极假丝酵母脂肪酶B催化的酯交换反应。该反应在缩醛碳的手性中心的影响下以立体选择性的方式进行，即使已从酯羰基碳上除去了六个原子。尽管两种底物在仲醇处具有相同的绝对构型，但一种立体异构体的反应速率比另一种异构体的反应速率高72倍。该差异反应性的原因主要归因于立体异构体之间的V max（app）的较大差异。产物乙酸盐和醇易于通过色谱分离，然后分别衍生为（R）-和（S）-TBMB酸，分别具有> 99.2％ee的酸。

  DOI：

  10.1002/adsc.201000446

文献信息

• Synthesis of an artificial glycoconjugate polymer carrying P k -antigenic trisaccharide and its potent neutralization activity against Shiga-like toxin
  作者：Hirofumi Dohi、Yoshihiro Nishida、Mitsuharu Mizuno、Masashige Shinkai、Takeshi Kobayashi、Tae Takeda、Hirotaka Uzawa、Kazukiyo Kobayashi

  DOI：10.1016/s0968-0896(99)00129-7

  日期：1999.9

  Fluorescence-labeled glycoconjugate polymers carrying carbohydrate segments of a globotriaosyl ceramide (Gb3) were synthesized and subjected to biological assays using Escherichia coli O-157 strains and Shiga-like toxins (Stx-I and Stx-II). For the fluorescence labeling, a new polymerizable fluorescent monomer with a TBMB carbonyl chromophore (Ex. 325 nm, Em. 410 nm) was designed. A glycosyl monomer of the trisaccharide segment of Gb3 was prepared from p-nitrophenyl beta-lactoside and copolymerized with acrylamide and the fluorescent monomer to prepare a fluorescence-labeled glycoconjugate copolymer carrying [alpha-D-galactopyranosyl-(1-->4)-beta-D-galactopyranosyl]-(1-->4)-beta- D-glucopyranoside. The polymer showed potent neutralization activity against Stx-I and also binding activity onto E. coli O-157 strains.
• Total Synthesis of Photoactivatable or Fluorescent Anandamide Probes: Novel Bioactive Compounds with Angiogenic Activity
  作者：Laurence Balas、Thierry Durand、Sattyabrata Saha、Inneke Johnson、Somnath Mukhopadhyay

  DOI：10.1021/jm8011382

  日期：2009.2.26

  Endocannabinoids are endogenous polyunsaturated fatty acids involved in a multitude of health and disease processes. Recently, several lines of evidence suggest the presence of a novel non-CB1/CB2 anandamide receptor in endothelial cells. Thus, we synthesized two types of photoaffinity probes that contain either an arylazide group or a diazirin moiety, together with a fluorescent analogue. The key steps rely on selective hydrogenation of skipped tetrayne backbones and on copper-mediated cross-coupling reactions between diynic precursors. Three synthetic routes were investigated. In biological functional assays, we found that both the arylazide and the fluorescent probes induced robust increases in matrix metalloprotease activity and produced positive angiogenic responses in in vitro endothelial cell tube formation assays. Irradiation of the arylazide probe nicely enhanced this effect in both HUVEC and CBI-KO HUVEC. These results suggest that the arylazide and the fluorescent probes can be used to identify "non-C131/CB2 anandamide receptor" from endothelial cells.
• 1,3-Benzodioxole-based β- and γ-Peptide Linkages Exhibiting Unique Fluorescence, Conformation, and Self-association Properties
  作者：Masaya Suzuki、Yuya Ohguro、Kazukiyo Kobayashi、Yoshihiro Nishida

  DOI：10.3987/com-05-10490

  日期：——

  Four types of beta- and gamma-peptide models were prepared from our previous asymmetric 1,3-benzodioxole and characterized by means of fluorescence and H-1 NMR spectroscopy. A beta-peptide model carrying secondary amide linkages at both of the C- and N-termini took a rigid coplanar conformation, emitting the strongest fluorescence [Ex.(max) 340 nm and Em.(max) 424 nm] among the four models. Dual intra-molecular hydrogen bonds were associated with the stable coplanar conformation. A tertiary beta-peptide model carrying a tertiary amide linkage at the C-terminus took a twisted conformation around the C-terminal to afford a pair of rotational isomers (atropisomers) detectable with H-1 NMR spectroscopy. Both secondary and tertiary gamma-peptide models showed a notable self-association property to afford dimers made of complementary intra- and intermolecular hydrogen bonds.
• US6313247B1
  申请人：——

  公开号：US6313247B1

  公开（公告）日：2001-11-06
• Synthesis and characterization of asymmetric o- and m-nitrobenzoic acids with a 1,3-benzodioxole skeleton
  作者：Masaya Suzuki、Yoshihiro Nishida、Yuya Ohguro、Yoshiko Miura、Akiko Tsuchida、Kazukiyo Kobayashi

  DOI：10.1016/j.tetasy.2003.10.030

  日期：2004.1

  A symmetric o- and m-nitrobenzoic acids with a 1,3-benzodioxole skeleton have been synthesized and characterized. The synthesis involved nitration at either the C-5 or C-6 position of 2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylate derived from catechol. These were then resolved with chiral solid-phased HPLC columns into each of enantiomers (>99% ee), which were characterized by circular dichroism. The (S)-enantiomers were also obtained by fractional crystallization of the precursor prior to the nitration. When applied as chiral derivation agents for alcohols and amines, m-nitrobenzoic acid showed notable ability to separate the enantiomers in both HPLC and NMR analyses. On the other hand, H-1 NMR and X-ray data of their ester and amide derivatives strongly suggested that the o-nitrobenzoic acid would serve as a fluorescent building block useful for the assembly of beta-peptide linkages with a defined conformation. (C) 2003 Elsevier Ltd. All rights reserved.