methyl 2-benzyl-2-methylbutanoate | 57144-64-6

• 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: methyl 2-benzyl-2-methylbutanoate
• 英文别名: alpha-Ethyl-alpha-methyl-dihydrocinnamic acid methyl ester
• CAS: 57144-64-6
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: UCVIEQWQPCBFKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 2-benzyl-2-methylbutanoate 在 草酰氯 、 三乙胺 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.0h， 生成 2-benzyl-2-methyl-N-(quinolin-8-yl)butanamide
  参考文献：
  名称：

  镍催化未活化 C(sp3)-H 键的位点选择性烷基化

  摘要：

  脂肪族酰胺的未活化 sp(3) CH 键的直接烷基化是通过镍催化在双齿导向基团的帮助下实现的。该反应有利于甲基的 CH 键而不是亚甲基的 CH 键，并且可以耐受各种官能团。此外，该反应表明，在环金属化步骤中，甲基的 sp(3) CH 键通过五元环中间体优先于芳烃的 sp(2) CH 键。

  DOI：

  10.1021/ja413131m
• 作为产物：
  描述：

  2,2-二甲基丁酸 在 palladium diacetate dipotassium hydrogenphosphate 、 草酰氯 、 silver carbonate 、 对苯醌 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， 反应 13.0h， 生成 methyl 2-benzyl-2-methylbutanoate
  参考文献：
  名称：

  Palladium-Catalyzed Methylation and Arylation of sp² and sp³ C−H Bonds in Simple Carboxylic Acids

  摘要：

  The use of preformed sodium carboxylates as substrates led to the first observation of facile Pd-insertions into sp(3) beta-C-H bonds in simple aliphatic acids. Consequently, Pd-catalyzed methylation and arylation of o-C-H bonds in benzoic acids and beta-C-H bonds in aliphatic acids using either a phenylboronate, methylboronic acid, or ArI have been achieved via a C-H activation/C-C coupling sequence.

  DOI：

  10.1021/ja0701614

文献信息

• Copper-Catalyzed Site-Selective Intramolecular Amidation of Unactivated C(sp³)H Bonds
  作者：Xuesong Wu、Yan Zhao、Guangwu Zhang、Haibo Ge

  DOI：10.1002/anie.201311263

  日期：2014.4.1

  of aliphatic amides, directed by a bidentate ligand, was developed using a copper‐catalyzed sp3 CH bond functionalization process. The reaction favors predominantly the CH bonds of β‐methyl groups over the unactivated methylene CH bonds. Moreover, a preference for activating sp3 CH bonds of β‐methyl groups, via a five‐membered ring intermediate, over the aromatic sp2 CH bonds was also observed in

  脂肪族酰胺的分子内酰胺化脱氢，由双齿配体定向，使用铜-催化的SP被开发3 Ç  H键官能化方法。该反应有利于主要的C  β甲基团与未活化的亚甲基] C H键 H键。此外，用于激活SP的偏好3 Ç  β甲基基团的H键，经由五元环中间，在所述芳族SP 2个ç  H键在环金属化步骤中也观察到。此外，SP 3个Ç 未活化二次属的H键3 Ç 通过使环碳原子优先于线性碳原子，可以使H键官能化。
• Indaneacetic acid derivatives
  申请人：Hexachimie Societe Anonyme

  公开号：US04166131A1

  公开（公告）日：1979-08-28

  This invention provides new compounds of formula I, ##STR1## wherein R.sub.1 is lower alkyl, R.sub.2 is hydrogen or lower alkyl, R.sub.3 is hydrogen or lower alkyl, R.sub.4 is hydrogen or lower alkyl, R.sub.5 is hydrogen, chlorine or lower alkyl, and each of R.sub.6 and R.sub.7 is hydrogen, or, when R.sub.5 is hydrogen, R.sub.6 may also be chlorine or lower alkyl, and R.sub.7 chlorine or lower alkyl, Useful as anti-phlogistic and anti-arthritic agents.

  这项发明提供了新的化合物，其化学式为I，其中R.sub.1是较低的烷基，R.sub.2是氢或较低的烷基，R.sub.3是氢或较低的烷基，R.sub.4是氢或较低的烷基，R.sub.5是氢、氯或较低的烷基，R.sub.6和R.sub.7中的每一个是氢，或者当R.sub.5是氢时，R.sub.6也可以是氯或较低的烷基，而R.sub.7是氯或较低的烷基。可用作抗炎和抗关节炎药物。
• METHOD FOR PRODUCING a-SUBSTITUTED CYSTEINE OR SALT THEREOF OR SYNTHETIC INTERMEDIATE OF a-SUBSTITUTED CYSTEINE
  申请人：API Corporation

  公开号：US20160083341A1

  公开（公告）日：2016-03-24

  According to the present invention, it becomes possible to perform a process for converting into an α-substituted cysteine represented by general formula (1) or a salt thereof at low cost and on an industrial scale by employing a process that is routed through a compound represented by general formula (3) to a compound represented by general formula (6). Particularly, by employing a process that is routed through a compound represented by general formula (7-2), it becomes possible to detach a tert-butyl protection group in a simple manner and to produce the compound represented by general formula (1) with high purity. Furthermore, by employing a process that is routed through tert-butylthiomethanol or a process that is routed through a compound represented by general formula (9), it becomes possible to produce a compound represented by general formula (2) without generating bischloromethylether that is an oncogenic substance. In the production of an α-substituted-D-cysteine or a salt thereof, it becomes possible to perform a process for converting the compound represented by general formula (2) into a compound represented by general formula (3S) in one step by allowing an enzyme or the like to act on the compound represented by general formula (2).

  根据本发明，通过采用经由一种化合物（通式（3）表示）到一种通式（6）表示的化合物的过程，可以以低成本和工业化规模进行将其转化为通式（1）表示的α-取代半胱氨酸或其盐的过程。特别是，通过采用经由一种通式（7-2）表示的化合物的过程，可以简单地去除叔丁基保护基，并以高纯度生产通式（1）表示的化合物。此外，通过采用经由叔丁基硫代甲醇或经由一种通式（9）表示的化合物的过程，可以生产通式（2）表示的化合物，而不产生致癌物质双氯甲醚。在生产α-取代-D-半胱氨酸或其盐时，可以通过允许酶或类似物作用于通式（2）表示的化合物，一步将其转化为通式（3S）表示的化合物。
• Nickel-Catalyzed Direct Arylation of C(sp³)–H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance
  作者：Yoshinori Aihara、Naoto Chatani

  DOI：10.1021/ja411715v

  日期：2014.1.22

  The Ni-catalyzed, direct arylation of C(sp(3))-H (methyl and methylene) bonds in aliphatic amides containing an 8-aminoquinoline moiety as a bidentate directing group with aryl halides is described. Deuterium-labeling experiments indicate that the C-H bond cleavage step is fast and reversible. Various nickel complexes including both Ni(II) and Ni(0) show a high catalytic activity. The results of a

  描述了 Ni 催化的 C(sp(3))-H（甲基和亚甲基）键在脂肪族酰胺中的直接芳基化，其中包含一个 8-氨基喹啉部分作为与芳基卤化物的双齿导向基团。氘标记实验表明 CH 键裂解步骤快速且可逆。包括 Ni(II) 和 Ni(0) 在内的各种镍配合物显示出高催化活性。一系列机理实验的结果表明，催化反应不是通过 Ni(0)/Ni(II) 催化循环进行，而是通过 Ni(II)/Ni(IV) 催化循环进行。
• Copper-Catalyzed Intramolecular C(sp³)H and C(sp²)H Amidation by Oxidative Cyclization
  作者：Zhen Wang、Jizhi Ni、Yoichiro Kuninobu、Motomu Kanai

  DOI：10.1002/anie.201311105

  日期：2014.3.24

  The first copper‐catalyzed intramolecular C(sp3)H and C(sp2)H oxidative amidation has been developed. Using a Cu(OAc)2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various β‐lactams were obtained in excellent yield, even

  第一铜催化的分子内C（SP 3） H和（SPç 2） ħ氧化酰胺化得到了发展。在二氯乙烷溶剂中使用Cu（OAc）2催化剂和Ag 2 CO 3氧化剂，在末端甲基以及烷基链的内部苄基位置处进行C（SP 3）H酰胺化反应。该反应具有广泛的底物范围，即使以克为单位，也能以优异的收率获得各种β-内酰胺。在O 2下使用CuCl 2和Ag 2 CO 3但是，在二甲基亚砜中的空气会通过C（SP 2）H酰胺化选择性地生成2-吲哚酮。动力学同位素效应（KIE）的研究表明，Ç  H键活化是速率决定步骤。可以通过氧化除去5-甲氧基喹啉基。