2-bromo-6-methyl-α-methylbenzyl alcohol | 148517-72-0

• 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: 2-bromo-6-methyl-α-methylbenzyl alcohol
• 英文别名: 1-(2-Bromo-6-methylphenyl)ethan-1-ol；1-(2-bromo-6-methylphenyl)ethanol
• CAS: 148517-72-0
• 化学式: C₉H₁₁BrO
• 分子量: 215.09
• InChiKey: USHJQKVZEFOWSV-UHFFFAOYSA-N

物化性质

• 沸点：
  285.3±25.0 °C(Predicted)
• 密度：
  1.406±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-6-methyl-α-methylbenzyl alcohol 在 4-二甲氨基吡啶 、 氢氧化钾 、 正丁基锂 、 4 A molecular sieve 、 lithium perchlorate 、 铜 、 sodium hydride 、 对甲苯磺酸 、 溶剂黄146 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 、 苯 为溶剂， 反应 17.5h， 生成 4-(2-biphenylyl)-6,6-dimethoxy-2,4-cyclohexadien-1-one
  参考文献：
  名称：

  Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate

  摘要：

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.

  DOI：

  10.1021/jo00064a017
• 作为产物：
  描述：

  2-溴-6-甲基苯甲酰氯 在 sodium tetrahydroborate 作用下， 以 乙醇 、 正己烷 、 水 、 甲苯 为溶剂， 反应 36.0h， 生成 2-bromo-6-methyl-α-methylbenzyl alcohol
  参考文献：
  名称：

  Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate

  摘要：

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.

  DOI：

  10.1021/jo00064a017

文献信息

• Design of spontaneously blinking fluorophores for live-cell super-resolution imaging based on quantum-chemical calculations
  作者：Ryo Tachibana、Mako Kamiya、Akihiko Morozumi、Yoshiyuki Miyazaki、Hiroyoshi Fujioka、Aika Nanjo、Ryosuke Kojima、Toru Komatsu、Tasuku Ueno、Kenjiro Hanaoka、Toshitada Yoshihara、Seiji Tobita、Yasuteru Urano

  DOI：10.1039/d0cc05126h

  日期：——

  Spontaneously blinking fluorophores are powerful tools for live-cell super-resolution imaging under physiological conditions. Here we show that quantum-chemical calculations can predict key parameters for fluorophore design. We applied this methodology to develop a spontaneously blinking fluorophore with yellow fluorescence for super-resolution imaging of microtubules in living cells.

  自发闪烁的荧光团是在生理条件下进行活细胞超分辨率成像的强大工具。在这里，我们证明了量子化学计算可以预测荧光团设计的关键参数。我们应用此方法开发了具有黄色荧光的自发闪烁荧光团，用于活细胞中微管的超分辨率成像。
• INDANYL COMPOUNDS
  申请人：Daiichi Sankyo Company, Limited

  公开号：EP2374788B1

  公开（公告）日：2013-04-03
• CYCLIC AMINE COMPOUNDS
  申请人：Daiichi Sankyo Company, Limited

  公开号：EP2374794B1

  公开（公告）日：2015-11-04
• SPIROCYCLIC COMPOUNDS AS TRYPTOPHAN HYDROXYLASE INHIBITORS
  申请人：Karos Pharmaceuticals, Inc.

  公开号：EP3041842B1

  公开（公告）日：2019-10-23
• US8173631B2
  申请人：——

  公开号：US8173631B2

  公开（公告）日：2012-05-08