(Z)-3-hydroxy-1,3-bis(4-methylphenyl)-2-propen-1-one | 62375-98-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (Z)-3-hydroxy-1,3-bis(4-methylphenyl)-2-propen-1-one
• 英文别名: 3-hydroxy-1,3-bis(4-tolyl)prop-2-en-1-one；di-p-toluoylmethane；Hdtm；2-Propen-1-one, 3-hydroxy-1,3-bis(4-methylphenyl)-, (2Z)-；(Z)-3-hydroxy-1,3-bis(4-methylphenyl)prop-2-en-1-one
• CAS: 62375-98-8
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: BEAQJCSIBXPJBM-WJDWOHSUSA-N

物化性质

• 沸点：
  421.8±45.0 °C(Predicted)
• 密度：
  1.130±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Ti(OtBu)[{(O-2,4-tBu2C6H2)-6-CH2}3N] 、 (Z)-3-hydroxy-1,3-bis(4-methylphenyl)-2-propen-1-one 以 苯 为溶剂， 以67%的产率得到[nitrilotris(3,5-di-tert-butyl-2-cresolato)](di-p-toluoylmethanato)titanium(IV)
  参考文献：
  名称：

  Six-Coordinate Titanium Complexes of a Tripodal Aminetris(phenoxide) Ligand:  Synthesis, Structure, and Dynamics

  摘要：

  The five-coordinate titanium(IV) alkoxide LTi(O'Bu) (LH3 = tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine) is protonolyzed readily by the conjugate acids of monoanionic bidentate ligands, both symmetrical (tropolone, acetylacetone, di-p-toluoylmethane) and unsymmetrical (8-hydroxyquinoline, salicylaldehyde, 2,6-diformyl-p-cresol, anthrarufin). The geometry of these complexes, which is pseudo-octahedral with the tripodal ligand adopting a chiral, propeller-like conformation, has been confirmed in four cases by X-ray crystallography. Variable-temperature NMR spectroscopy indicates that the six-coordinate complexes undergo two dynamic processes. First, the ligands undergo a twisting motion that results in racemization, a process which is over 10(4) times faster than in five-coordinate complexes. The rate acceleration upon binding of an equatorial ligand is ascribed to steric repulsions with one of the cis phenoxides; the dynamics of a binuclear dibenzyl phosphate-bridged compound, which has a unique conformation of the tripodal ligand, indicates that flexing the cis pheroxide is the rate-limiting step in racemization. Second, the complexes undergo a process that interchanges the inequivalent arms of the tripodal ligand, This process involves a trigonal twist that shifts the bidentate ligand between clefts in the tripod. The intermediate geometry in the reaction appears to be a transition state and not a long-lived intermediate, as judged from the relative rates of interconversion of tripod arms and chelate ends in the ditoluoylmethane complex, Tripod arm interchange takes place without partial dissociation of the bidentate chelate, a reaction that has been observed on a slower time scale in one case.

  DOI：

  10.1021/ic048403d
• 作为产物：
  描述：

  4-amino-2,4-bis(4-tolyl)-1-azabuta-1,3-diene 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以95%的产率得到(Z)-3-hydroxy-1,3-bis(4-methylphenyl)-2-propen-1-one
  参考文献：
  名称：

  Reactions of N-Unsubstituted 4-Amino-1-azadienes Towards Electrophiles

  摘要：

  本文描述了与N-未取代氮杂二烯1的弱亲核性相关的几种反应。因此，1与烷基化剂和碘代双吡啶四氟硼酸盐（IPy2BF4）的反应分别产生了C-取代氮杂二烯3和5。氮杂二烯1和3通过温和的水解转化为羰基衍生物2和4。另一方面，氮杂二烯1、3和5通过氮原子与几种以羰基为中心的亲电体反应，生成氮杂环，如嘧啶6和9以及二氢嘧啶11。所有这些过程都是完全选择性的，氮杂二烯1和3在氮原子上表现出比N-取代氮杂二烯更低的亲核性。

  DOI：

  10.1055/s-1996-4160

文献信息

• Preparation of <i>β</i>-Keto Esters and <i>β</i>-Diketones by C-Acylation/Deacetylation of Acetoacetic Esters and Acetonyl Ketones with 1-Acylbenzotriazoles
  作者：Alan R. Katritzky、Zuoquan Wang、Mingyi Wang、Chavon R. Wilkerson、C. Dennis Hall、Novruz G. Akhmedov

  DOI：10.1021/jo049274l

  日期：2004.10.1

  Acyl-, aroyl-, and heteroaroyl-acetic esters 6a−f and 8a−l are prepared by reactions of 1-acylbenzotriazoles 1a−k with acetoacetic esters 5 or 7a,b in the presence of sodium hydride followed by regioselective deacetylation. Similar C-acylation/deacetylation of acetylacetone and benzoylacetone affords β-diketones 10a−d and 13a−c, respectively.

  酰基，芳酰基和杂芳基乙酸酯6a - f和8a - 1通过在氢化钠存在下1-酰基苯并三唑1a - k与乙酰乙酸酯5或7a，b反应，然后进行区域选择性脱乙酰反应制得。乙酰丙酮和苯甲酰丙酮的类似的C-酰化/脱乙酰基分别提供β-二酮10a - d和13a - c。
• Catalytic cascade synthesis of cyanohydrin esters <i>via</i> water/O₂-induced cyanide transfer from K₃Fe(CN)₆
  作者：Anupam Kumar Singh、Shivani Singh Chauhan、Sukalyan Bhadra

  DOI：10.1039/d3cc02743k

  日期：——

  water/O2-induced release of cyanide ions from K3Fe(CN)6 and a benzil-cyanide reaction. This strategy gives expedient access to cyanohydrin esters starting directly from broadly accessible aryl benzyl ketones. The cyanide release strategy was further integrated with a copper catalyzed oxygenation-decarbonylation sequence to produce cyanohydrin esters from 1,3-diketones.

  铜催化的芳基苄基酮的α-氧化与独特的水/O 2诱导的K 3 Fe(CN) 6中氰化物离子的释放以及苯偶酰氰反应相结合。该策略可以方便地直接从广泛使用的芳基苄基酮开始制备氰醇酯。氰化物释放策略进一步与铜催化氧化-脱羰序列相结合，从 1,3-二酮生产氰醇酯。
• Co‐Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters†
  作者：Shuo Gao、Wentao Hao、Yuqi Ji、Xiulin Li、Chunyan Zhang、Guoying Zhang

  DOI：10.1002/cjoc.202400481

  日期：2024.11.15

  practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters, facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones. We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols, and propose a plausible reaction mechanism supported by control experiments

  催化脱氢具有卓越的原子经济性和化学选择性，为将多种环保醇转化为关键分子提供了一种非常理想但具有挑战性的方法。此外，利用基于地球上发现的丰富元素的催化剂进行醇脱氢以生产丙烯酸酮，作为合成众多制药应用关键构件的通用策略，具有重要的前景。本研究描述了仲醇与酯的实用共催化级联脱氢 Claisen 缩合反应，促进了广泛的 3-羟基-丙-2-烯-1-酮的合成。我们引入了一种基于新型且可扩展的吲唑 NNP 配体的催化系统，该配体与钴配位，用于仲醇的高效脱氢，并提出了一种由对照实验和标记研究支持的合理反应机制。值得注意的是，它允许在一个罐中简化多种药物的合成。