2,4'-dimethyl-deoxybenzoin | 4779-60-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,4'-dimethyl-deoxybenzoin
• 英文别名: 2,4'-Dimethyl-desoxybenzoin；2'-methyl-2-(p-tolyl)acetophenone；1-(2-Methylphenyl)-2-(4-methylphenyl)ethanone
• CAS: 4779-60-6
• 化学式: C₁₆H₁₆O
• mdl: MFCD12605223
• 分子量: 224.302
• InChiKey: BLTXZPGOMJVNSA-UHFFFAOYSA-N

物化性质

• 沸点：
  140-147 °C(Press: 3 Torr)
• 密度：
  1.047±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.187
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 Fuller's Earth 、 二氧化碳 作用下， 生成 2,4'-dimethyl-deoxybenzoin 、 甲苯
  参考文献：
  名称：

  On the Catalytic Action of Japanese Acid Earth. XI. The Isomerisation of Aldehydes to Ketones and the Explanation of the Migration of the Radicals from the Standpoint of the Electronic Theory

  摘要：

  DOI：

  10.1246/bcsj.16.196

文献信息

• On the Catalytic Action of Japanese Acid Earth. XI. The Isomerisation of Aldehydes to Ketones and the Explanation of the Migration of the Radicals from the Standpoint of the Electronic Theory (<i>Continued and concluded</i>)
  作者：Koshiro Ishimura

  DOI：10.1246/bcsj.16.293

  日期：1941.9

  (1) All the phenomena hitherto ascribed to the characteristic catalytic action of Japanese acid earth can be explained by taking its strong electron-seeking property into consideration. Thus its ability to promote the hydrolysis of cane sugar or starch and the oxidation of pyrogallol and its property to give various oxidase-like colour reactions are all due to its selective adsorptive power for hydroxyl ion. The facts can similarly be explained that the dehydration or deamination of various organic compounds takes place through its catalytic action followed by the intramolecular rearrangement, as observed in the reaction of producing cyclopentane derivatives from cyclohexanol, cyclohexylamine or their methyl derivatives.The initial step of the formation of β,β′-dinaphthyl from naphthalene in the presence of the earth is the polarisation of the naphthalene molecule promoted by its electron-seeking property.(2) Several diarylacetaldehydes have been newly synthesised and found to rearrange themselves to give the corresponding ketones, when heated at 300°C. in the presence of the earth. Thus phenyl p-tolyl and m-tolyl p-tolyl acetaldehydes gave phenyl p-methylbenzyl and m-tolyl p-methylbenzyl ketones respectively, while o-tolyl p-tolyl and p-tolyl p-chlorophenyl acetaldehydes gave the respective mixtures of o-toly p-methylbenzyl and p-tolyl o-methylbenzyl ketones and of p-chlorophenyl p-methylbenzyl and p-tolyl p-chlorobenzyl ketones.(3) By comparing the yields in the isomeric ketones thus produced the order of the facility of separation of the different aryl groups was determined as follows:—Phenyl, m-tolyl>p-chlorophenyl>o-tolyl>p-tolyl.The phenyl group may most probably have the greater migratory tendency than the m-tolyl.(4) The mechanism of the conversion of the aldehydes to the ketones has been discussed. It has been postulated that an electromeric displacement of electrons in the carbonyl group (Remark: Graphics omitted.) is promoted by the action of the earth, and one of the aryl groups migrates with its valency electrons from the adjacent a-carbon atom to the depleted carbonyl carbon. A proton is then splitted from the carbonyl carbon and unites with the carbonyl oxygen to give the enolic form of the ketone, isomeric to the aldehyde. The conclusion has been reached that the more electron-attracting of the two aryl groups must be first separated as anion.(5) It was confirmed that the capacity of the p-tolyl group for electron-release is much larger than those of o-tolyl, m-tolyl, phenyl and p-chlorophenyl groups. By these results a new chemical evidence has been given for the tautomeric effect of the methyl group.(6) Following compounds have been newly synthesised and their constitutions were confirmed:— a-phenyl a-p-tolyl, a-m-tolyl a-p-tolyl, a-o-tolyl a-p-tolyl and a-p-chlorophenyl a-p-tolyl ethylene glycols and their benzoyl derivatives; p-tolyl m-methylbenzyl, m-tolyl p-methylbenzyl, o-tolyl p-methylbenzyl, p-tolyl o-methylbenzyl, p-chlorophenyl p-methyl-benzyl and p-tolyl p-chlorobenzyl ketones and their oximes and semi-carbazones; m-tolyl p-tolyl, o-tolyl p-tolyl and p-tolyl p-chlorophenyl acetic acids; p-methylbenzoyl carbinol, p-chlorobenzoyl methyl acetate and p-chlorobenzoyl carbinol.(7) o-Tolyl p-methylbenzyl and m-tolyl p-methylbenzyl ketones have been found to be oxidised slowly by the action of atmospheric oxygen on long standing, giving the mixtures of o-toluic and p

  (1) 考虑到日本酸土的强电子寻找特性，迄今为止所有归因于其催化作用特征的现象都可以得到解释。因此，日本酸土能够促进蔗糖或淀粉的水解、焦酚的氧化以及产生各种类似氧化酶的颜色反应，都是由于它对羟基离子具有选择性吸附力。同样，在环己醇、环己胺或其甲基衍生物生成环戊烷衍生物的反应中也可以看到，各种有机化合物的脱水或脱氨基反应是在其催化作用下进行的，随后发生分子内重排。(2)新合成了几种二芳基乙醛，并发现它们在有土的情况下于 300°C 加热时会重新排列，生成相应的酮。因此，苯基对甲苯基和间甲苯基对甲苯基乙醛分别生成苯基对甲基苄基和间甲苯基对甲基苄基酮，而邻甲苯基对甲苯基和对甲苯基对氯苯基乙醛分别生成邻甲苯基对甲基苄基和对甲苯基邻甲基苄基酮的混合物，以及对氯苯基对甲基苄基和对甲苯基对氯苄基酮的混合物。(3) 通过比较由此生成的异构酮的产率，确定了不同芳基的分离便利性顺序如下：苯基、间甲苯基>对氯苯基>邻甲苯基>对甲苯基。据推测，在地球的作用下，羰基（注：图形省略）中的电子发生了电迁移，其中一个芳基带着其价电子从相邻的 a 碳原子迁移到耗尽的羰基碳上。然后，一个质子从羰基碳上分离出来，与羰基氧结合，得到酮的烯醇形式，与醛同分异构。(5)经证实，对甲苯基释放电子的能力远远大于邻甲苯基、间甲苯基、苯基和对氯苯基。这些结果为甲基的同分异构效应提供了新的化学证据。(6) 新合成了下列化合物，并确认了它们的组成：- a-苯基 a-对甲苯基、a-间甲苯基 a-对甲苯基、a-邻甲苯基 a-对甲苯基和 a-对氯苯基 a-对甲苯基乙二醇及其苯甲酰衍生物；对甲苯基间甲基苄基、间甲苯基对甲基苄基、邻甲苯基对甲基苄基、对甲苯基邻甲基苄基、对氯苯基对甲基苄基和对甲苯基对氯苄基酮及其肟和半咔唑酮；间甲苯基对甲苯、邻甲苯基对甲苯和对甲苯基对氯苯乙酸；对甲基苯甲酰基甲 醛、对氯苯甲酰甲基乙酸酯和对氯苯甲酰甲醇。(7) 研究发现，邻甲苯基对甲基苄基和间甲苯基对甲基苄基酮在大气中的氧气作用下，长期存 在会被缓慢氧化，生成邻甲苯基和间甲苯基对甲基苄基酮的混合物。
• Alkali Ion Exchanged Nafion as a Confining Medium for Photochemical Reactions†
  作者：Selvanathan Arumugam、Lakshmi S. Kaanumalle、V. Ramamurthy

  DOI：10.1562/2005-05-05-ra-515

  日期：——

  beads were used as microreactors to control the photochemical reaction pathways. Product selectivity in three unimolecular reactions, namely, the photo-Fries rearrangement of naphthyl esters, Norrish Type I reaction of 1-phenyl-3-p-tolyl-propan-2-one and Norrish Type I and Type II reactions of benzoin alkyl ethers were examined. The influence of cations over the photodimerization of acenaphthylene and

  甲醇溶胀的Nafion珠用作微反应器，以控制光化学反应路径。在三个单分子反应中的产物选择性，即萘酯的光-弗里斯重排，1-苯基-3-对甲苯基丙烷-2-酮的Norrish I型反应和安息香烷基醚的Norrish I型和II型反应被检查了。还研究了阳离子对Na烯的光二聚化以及Na烯与Nafion中包括的N-苄基马来酰亚胺之间的交叉光二聚化的影响。与它们的溶液光化学法相比，Nafion中上述底物的光化学行为发生了显着变化。特别令人感兴趣的是，发现产物分布取决于Nafion的抗衡阳离子。
• US4263311A
  申请人：——

  公开号：US4263311A

  公开（公告）日：1981-04-21
• 10.1002/cctc.202400735
  作者：Wang, Shiyang、Xia, Zongxiang、Sheng, Jie、Cui, Jiaxue、Yao, Tong、Liu, Yu、Liu, Chunhui、Liu, Zuyong、Tao, Jie、Wu, Yuanqi

  DOI：10.1002/cctc.202400735

  日期：——

  In the absence of directing auxiliaries, catalytic addition of nucleophiles to unactivated alkynes with accurate control of regioselectivity remains an ongoing challenge in organic chemistry. Herein, we realized a Ag‐catalysed regiospecific hydration process of unactivated alkynes. Computational investigations offered insights into the origin of the regiochemical outcome. The practicability and efficacy of the protocol was exemplified by its simple reaction conditions without incorporation of acidic additives, as well as the toler‐ance of a wide range of alkynes equipped with various functional groups, leading to the ketone products in up to 98% yield. Direct modification of bioactive organic molecules and gram‐scale experiments further showcased the application potential of the strategy. The catalyst control principles are expected to advance efforts towards the development of general site‐selective addition of nucleophile to unsaturated substrates, removing the requirement for neighboring activating groups.
• On the Catalytic Action of Japanese Acid Earth. XI. The Isomerisation of Aldehydes to Ketones and the Explanation of the Migration of the Radicals from the Standpoint of the Electronic Theory
  作者：Koshiro Ishimura

  DOI：10.1246/bcsj.16.196

  日期：1941.7