(3Z)-3-(bromomethyl)-4-phenylbut-3-en-2-one | 42967-97-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (3Z)-3-(bromomethyl)-4-phenylbut-3-en-2-one
• 英文别名: (Z)-3-(bromomethyl)-4-phenylbut-3-en-2-one
• CAS: 42967-97-5
• 化学式: C₁₁H₁₁BrO
• 分子量: 239.112
• InChiKey: VPQYCWSOERORKT-YRNVUSSQSA-N

物化性质

• 熔点：
  52.5-53 °C
• 沸点：
  310.0±30.0 °C(Predicted)
• 密度：
  1.377±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (3Z)-3-(bromomethyl)-4-phenylbut-3-en-2-one 在 yeast type II from Saccharomyces cerevisiae 作用下， 以 水 为溶剂， 反应 8.0h， 以53%的产率得到(R)-3-methyl-4-phenylbutan-2-one
  参考文献：
  名称：

  Enantiodivergence in the reduction of α-methyl and α-halomethyl enones by microorganisms

  摘要：

  Enones (Z)-3-methyl-(Z)-3-chloromethyl- and (Z)-3-bromomethyl-4-R-3-buten-2-one (R = n-pentyl, phenyl, 2'- and 4'-chlorophenyl, 3'- and 4'-nitrophenyl, 4'-methoxyphenyl) were synthesized and subjected to reduction by the microorganisms Saccharomyces cerevisiae and Geotrichum candidum. Whereas the bioreduction of 3-methy-4-R-3-buten-2-ones afforded the corresponding (S)-4-R-3-methybutan-2-ones, the bioreduction of 3-chloromethyl- and 3-bromomethyl-4-R-3-buten-2-ones afforded the corresponding (R)-4-R-3-methybutan-2-ones. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.07.007
• 作为产物：
  描述：

  3-(hydroxyphenylmethyl)but-3-en-2-one 在 氢溴酸 作用下， 反应 0.02h， 以81%的产率得到(3Z)-3-(bromomethyl)-4-phenylbut-3-en-2-one
  参考文献：
  名称：

  Baylis-Hillman反应：（Z）-酮基烯丙基溴和氯化物的简便合成方法

  摘要：

  描述了从Baylis-Hillman加合物简单且方便地合成（Z）-酮烯丙基溴和氯化物。

  DOI：

  10.1016/s0040-4020(99)00326-9

文献信息

• New CC Bond Formation via Nonstoichiometric Titanium(IV) Halide Mediated Vicinal Difunctionalization of α,β-Unsaturated Acyclic Ketones
  作者：Guigen Li、Joe Gao、Han-Xun Wei、Mason Enright

  DOI：10.1021/ol9904040

  日期：2000.3.1

  [reaction: see text] Highly stereoselective vicinal difuctionalization of alpha,beta-unsaturated ketones for the synthesis of multifunctionalized trisubstituted alkenes is described. The new reaction employs titanium(IV) halides (0.5 equiv) as promoters and inexpensive commercial chemicals as starting materials. The reaction can be performed at room temperature in a convenient vial without the protection

  [反应：见正文]描述了用于多官能化三取代烯烃的高度立体选择性邻位二官能化的α，β-不饱和酮。该新反应使用卤化钛（IV）（0.5当量）作为促进剂，并使用廉价的商业化学品作为起始原料。该反应可以在室温下在方便的小瓶中进行，而无需保护惰性气体。在大多数情况下（16个例子），都实现了良好到优异的产率和高Z / E立体选择性。
• Efficient nucleophilic substitution reactions of highly functionalized allyl halides in ionic liquid media
  作者：S.R.S.Saibabu Kotti、Xin Xu、Guigen Li、Allan D. Headley

  DOI：10.1016/j.tetlet.2003.12.051

  日期：2004.2

  Nucleophilic substitution reactions of highly functionalized allyl halides with three anions, N3−, AcO−, and PhSO2−, in ionic liquid media were conducted. The ionic liquid, [Bmim][BF4], was found to be superior to classical organic solvents to give higher yields and faster reaction rates. The resulting products belong to multifunctionalized trisubstituted α,β-unsaturated ketones, which are useful building

  的亲核取代反应高度官能化的烯丙基卤化物与3根阴离子，N 3 -，ACO - ，和PhSO 2 - ，在离子液体介质进行的。发现离子液体[Bmim] [BF 4 ]优于经典有机溶剂，可提供更高的产率和更快的反应速率。所得产物属于多官能化的三取代的α，β-不饱和酮，是有机合成的有用组成部分。
• γ-Selective Allylation of (<i>E</i>)-Alkenylzinc Iodides Prepared by Reductive Coupling of Arylacetylenes with Alkyl Iodides
  作者：Fedor E. Zhurkin、Xile Hu

  DOI：10.1021/acs.joc.6b01306

  日期：2016.7.1

  allylic alkenylation using organozinc reagents are reported. (E)-Alkenylzinc iodides were prepared by Fe-catalyzed reductive coupling of terminal arylalkynes with alkyl iodides. In the presence of a copper catalyst, these reagents reacted with allylic bromides derived from Morita–Baylis–Hillman alcohols to give 1,4-dienes in high yields. The reactions are highly γ-selective (generally γ/α > 49:1) and tolerate

  报道了使用有机锌试剂的Cu催化的γ-选择性烯丙基烯基化的第一个实例。（E）-烯基碘化锌是通过铁催化的末端芳基炔烃与烷基碘的还原偶联而制得的。在铜催化剂的存在下，这些试剂与衍生自森田-贝利斯-希尔曼醇的烯丙基溴反应生成高产率的1,4-二烯。这些反应具有很高的γ选择性（通常γ/α> 49：1），并且可以耐受各种官能团，例如酯，氰基，酮基和硝基。
• Palladium-Catalyzed Domino Cyclization (5-<i>exo</i>/3-<i>exo</i>), Ring- Expansion by Palladium Rearrangement, and Aromatization: An Expedient Synthesis of 4-Arylnicotinates from Morita-Baylis-Hillman Adducts
  作者：Ko Hoon Kim、Se Hee Kim、Hyun Ju Lee、Jae Nyoung Kim

  DOI：10.1002/adsc.201300211

  日期：2013.7.8

  Various 4‐arylnicotinate derivatives were synthesized via a palladium‐catalyzed cascade reaction of N‐(2‐bromoallyl)‐N‐cinnamyltosylamides in a one‐pot procedure in good yields. The reaction involves a domino 5‐exo/3‐exo carbopalladation, ring‐expansion by palladium rearrangement, and an aromatization process.

  通过N-（2-溴代烯丙基）-N-肉桂基甲苯磺酰胺的钯催化级联反应以高收率合成了各种4-芳基烟酸酯衍生物。该反应涉及多米诺骨牌5 exo / 3 exo碳钯，通过钯重排进行的扩环，以及芳构化过程。
• 2,3-Dichloro-5,6-dicyano-<i>para</i>-benzoquinone (DDQ)/Methanesulfonic Acid (MsOH)-Mediated Intramolecular Arene-Alkene Oxidative Coupling
  作者：Ko Hoon Kim、Cheol Hee Lim、Jin Woo Lim、Jae Nyoung Kim

  DOI：10.1002/adsc.201301169

  日期：2014.3.10

  An efficient intramolecular arene‐alkene oxidative coupling of 1,4‐diaryl‐1,3‐butadienes has been developed involving the use of a 2,3‐dichloro‐5,6‐dicyano‐para‐benzoquinone (DDQ)/acid catalyst. The reaction involves the generation of a radical cation by abstraction of an electron from the substrate with DDQ, an intramolecular Friedel–Crafts‐type reaction, and the loss of hydrogen radical.

  已经开发出一种有效的1,4-二芳基-1,3-丁二烯分子内芳烃-烯烃氧化偶联方法，其中涉及使用2,3-二氯-5,6-二氰基对对苯二酚（DDQ）/酸催化剂。该反应涉及通过用DDQ从底物中提取电子来产生自由基阳离子，分子内Friedel-Crafts型反应以及氢自由基的损失。