(Z)-2-phenyl-4-(chloromethylene)-5(4H)-oxazolone | 89363-86-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (Z)-2-phenyl-4-(chloromethylene)-5(4H)-oxazolone
• 英文别名: 4-(chloromethylene)-2-phenyl-5(4H)-oxazolone；4-chloromethylene-2-phenyl-5(4H)-oxazolone；4-chloromethylene-2-phenyloxazol-5(4H)-one；(Z)-4-chloromethylene-5(4H)-oxazolone；4-(E)-chloromethylene-2-phenyl-4H-oxazol-5-one；2-Phenyl-4-chlormethylen-5(4H)-oxazolon；4,5-Dihydrooxazole-5-one, 4-chloromethylene-2-phenyl-；(4Z)-4-(chloromethylidene)-2-phenyl-1,3-oxazol-5-one
• CAS: 89363-86-0
• 化学式: C₁₀H₆ClNO₂
• 分子量: 207.616
• InChiKey: FSFZBUCNVBXRQH-VURMDHGXSA-N

物化性质

• 沸点：
  263.7±50.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-2-phenyl-4-(chloromethylene)-5(4H)-oxazolone 在 三氯化铝 、 三氟化硼乙醚 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 3-benzoylamino8-methyl-2-oxo-2H-1-benzopyran-7-yl β-D-glucopyranoside
  参考文献：
  名称：

  Novobiocin-related compounds: synthesis of 3-benzoylamino-2-oxo-2H-1-benzopyran-7-yl d-glycopyranosides by the trichloroacetimidate methodology

  摘要：

  A general stereoselective method for the synthesis of 4-deoxynovobiocin-related glycosides is described. 3-Benzoylamino-2H-1-benzopyran-7-yl 2,3,4,6-tetra-O-acetyl-D-glycopyranosides of glucose, galactose and mannose were synthesised from appropriate O-glycosyltrichloroacetimidates and N-(7-hydroxy-2-oxo-2H-1-benzopyran-3-yl)benzamides in boiling methylene chloride in the presence of boron trifluoride etherate. Heating of these products in a mixture of triethylamine and methanol gave the corresponding deprotected 3-benzoylamino-2-oxo-2H-1-benzopyran-7-yl beta-D-glycopyranosides. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(00)00142-7
• 作为产物：
  描述：

  4-乙氧基亚甲基-2-苯基恶唑啉-5-酮 在 盐酸 、 草酰氯 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 76.0h， 生成 (Z)-2-phenyl-4-(chloromethylene)-5(4H)-oxazolone
  参考文献：
  名称：

  Synthesis of (E)- and (Z)-cyclopropyl-3-chloroalanine

  摘要：

  DOI：

  10.1021/jo00183a027

文献信息

• A Novel Class of Conformationally Constrained, Masked Cysteines:  Synthesis of 2-Alkyl- and 2-Arylsulfanyl-1-aminocyclopropanecarboxylic Acids
  作者：F. Clerici、M. L. Gelmi、D. Pocar

  DOI：10.1021/jo9810011

  日期：1999.2.1

  4-(chloromethylene)oxazolone 1 and mercaptans 2. Oxazolones 3 were used as starting materials for the preparation of unknown 2-sulfanyl-1-aminocyclopropanecarboxylic acid derivatives 5 and7. Oxazolones 3 were cyclopropanated at the exocyclic double bond with diazomethane, giving a mixture of the two (Z)- and (E)-spirocyclopropane oxazolones 4 with good diastereoselectivity. These were then treated with

  从4-（氯亚甲基）恶唑酮1和硫醇2开始实现了4-硫烷基亚甲基-5（4H）-恶唑酮3的方便合成。恶唑酮3被用作制备未知的2-硫烷基-1-氨基环丙烷羧酸的起始原料导数5和7。恶唑酮3在环外双键处与重氮甲烷环丙烷化，得到具有良好非对映选择性的两种（Z）-和（E）-螺环丙烷恶唑酮4的混合物。然后将它们用乙醇和DMAP处理以产生相应的羧酸盐5。使用碘在乙醇溶液中的溶液，将三苯甲基衍生物5d转化为非对映异构体二硫化物6的混合物。二硫化物6是用于制备3-硫烷基取代的2,3-甲基氨基酸7的便利合成子。
• 5(4H)-oxazolones. Part XIII. A new synthesis of 4-ylidene-5(4H)-oxazolones by the Stille reaction
  作者：Egle Maria Beccalli、Francesca Clerici、Maria Luisa Gelmi

  DOI：10.1016/s0040-4020(98)01070-9

  日期：1999.1

  4-Chloromethylene-2-phenyl-5(4H)-oxazolone 1 was used as the starting material for the preparation of a series of 4-ylideneoxazolones 3 by the Stille reaction. When compound 1 was reacted with organostannanes 2 in the presence of the palladium catalyst, oxazolones 3 were obtained in good yields in mild reaction conditions.

  使用4-氯亚甲基-2-苯基-5（4 H）-恶唑酮1作为通过Stille反应制备一系列4-亚甲基恶唑酮3的起始原料。当化合物1在钯催化剂的存在下与有机锡烷2反应时，在温和的反应条件下以高收率获得了恶唑酮3。
• Density Functional Theory Guided Design of Exo-Selective Dehydroalanine Dienophiles for Application Toward the Synthesis of Palau'amine
  作者：Timothy A. Cernak、James L. Gleason

  DOI：10.1021/jo701866g

  日期：2008.1.1

  Diels−Alder cycloadditions of dehydroalanine derivatives with cyclopentadiene, applicable to the synthesis of palau'amine, were investigated experimentally and using DFT computations at the B3LYP/6-31G* level of theory. Oxazolone and thiohydantoin dienophiles were found to be significantly more reactive than hydantoins or dehydroalanine methyl esters. The increased reactivity of the thiohydantoins

  对脱氢丙氨酸衍生物与环戊二烯的Diels-Alder环加成反应（适用于合成帕劳胺）进行了实验研究，并在理论水平B3LYP / 6-31G *下使用DFT计算。发现恶唑酮和巯基乙内酰脲二烯亲和剂比乙内酰脲或脱氢丙氨酸甲酯具有明显更高的反应活性。硫代乙内酰脲相对于乙内酰脲的反应性增加归因于氮孤对与硫代羰基的缀合增加。由于过渡态中的空间相互作用，β-取代作用大大减缓了环加成反应，而氯的任何电子活化作用都超过了该作用。乙内酰脲和巯基乙内酰脲被发现是选择性的，而相应的恶唑酮和脱氢丙氨酸则是非选择性的。
• Stable 5-Substituted Cyclopentadienes for the Diels-Alder Cycloaddition and their Application to the Synthesis of Palau'amine
  作者：Jonathan Hudon、Timothy A. Cernak、James A. Ashenhurst、James L. Gleason

  DOI：10.1002/anie.200803344

  日期：2008.11.3
• A Highly Diastereoselective Approach to Conformationally Constrained Serine Analogues:  Synthesis of an α-Amino-β-hydroxycyclohexenecarboxylic Acid and Derivatives
  作者：Francesca Clerici、Maria Luisa Gelmi、Andrea Gambini

  DOI：10.1021/jo9821877

  日期：1999.8.1

  A diastereospecific synthesis of alpha-amino-beta-hydroxycyclohexenecarboxylic acid (7) was found starting from 4-chloromethylene-5(4H)-oxazolone (1) which reacted with 2,3-dimethylbutadiene in the presence of EtAlCl2. The Diels-Alder reaction gave two diastereoisomeric cycloadducts 2 and 3, depending on the configuration of the starting dienophile 1. Compounds 2a and 3 were transformed into the ester 4 and the oxazoline 6, respectively, by reaction with MeOH and p-TSA. The reaction of 2a and 3 with dimethylamine in ethanol solution gave the corresponding amides 8 and 9, respectively, which were transformed into the bicyclic oxazoline 10 on reaction with Na2CO3 in acetonitrile. On acidic hydrolysis both oxazolines 6 and 10 were transformed into alpha-amino-beta-hydroxycyclohexenecarboxylic acid (7) that includes the serine skeleton.