2,3-Dibromo-1-(phenylsulfonyl)-1-propene | 128496-94-6

• 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: 2,3-Dibromo-1-(phenylsulfonyl)-1-propene
• 英文别名: (E)-2,3-Dibromo-1-(phenylsulfonyl)-1-propene；[(E)-2,3-dibromoprop-1-enyl]sulfonylbenzene
• CAS: 128496-94-6
• 化学式: C₉H₈Br₂O₂S
• 分子量: 340.035
• InChiKey: NMJCDFKJASKHFY-BQYQJAHWSA-N

物化性质

• 沸点：
  410.6±45.0 °C(Predicted)
• 密度：
  1.847±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-Dibromo-1-(phenylsulfonyl)-1-propene 在 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 Methyl 5-oxa-7-(bromomethyl)-6-methyl-8-(phenylsulfonyl)-7-octenoate
  参考文献：
  名称：

  以2,3-二溴-1-（苯基磺酰基）-1-丙烯为关键试剂的二取代环戊烯酮的新途径

  摘要：

  2，3-二溴-1-（苯基磺酰基）-1-丙烯对1，3-二酮和β-酮​​酸酯起双亲电子作用，从而可进入包括顺式-茉莉酮在内的各种2，3-二取代的环戊烯酮。

  DOI：

  10.1016/s0040-4039(00)97009-6
• 作为产物：
  描述：

  苯硫酚 在 盐酸 、 aluminum oxide 、 sodium hydroxide 、 titanium(III) chloride 、 双氧水 、 溴 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 为溶剂， 反应 6.0h， 生成 2,3-Dibromo-1-(phenylsulfonyl)-1-propene
  参考文献：
  名称：

  2,3-Dibromo-1-(苯磺酰基)-1-丙烯 (DBP) 的改进合成

  摘要：

  2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP, 1) 的简便制备方法是通过一锅法炔丙基化和苯硫酚氧化得到炔丙基砜 11，后者在另一个中异构化和溴化一锅反应。与现有技术相比，新的制备方法明显更具可扩展性，以及更方便和更稳健。

  DOI：

  10.1055/s-2004-831230

文献信息

• Mechanism of the Palladium-Catalyzed Intramolecular Hydroalkylation of 7-Octene-2,4-dione
  作者：Hua Qian、Ross A. Widenhoefer

  DOI：10.1021/ja0293002

  日期：2003.2.1

  cis-2-acyl-3,4-dideuteriocyclohexanone (cis-3-3,4-d(2)) in 64% yield as the exclusive isotopomer. This experiment, in conjunction with additional deuterium labeling experiments, was in accord with a mechanism for the conversion of 1 to 3 catalyzed by 2 involving attack of the enol carbon atom on a palladium-complexed olefin followed by palladium migration and protonolysis from a palladium enolate complex

  PdCl(2)(CH(3)CN) 催化 (E)-7,8-dideuterio-7-octene-2,4-dione [(E)-1-7,8-d(2)] 的环化(2) (2) 以 64% 的产率形成了 cis-2-acyl-3,4-dideuteriocyclohexanone (cis-3-3,4-d(2)) 作为唯一的同位素。该实验与额外的氘标记实验相结合，符合由 2 催化的 1 到 3 转化的机制，包括烯醇碳原子对钯络合烯烃的攻击，随后钯迁移和来自钯烯醇化物的质子分解复杂的。
• A Sulfone-Based Strategy for the Preparation of 2,4-Disubstituted Furan Derivatives
  作者：Nathan R. Haines、Aaron N. VanZanten、Anthony A. Cuneo、John R. Miller、William J. Andrews、David A. Carlson、Ryan M. Harrington、Adam M. Kiefer、Jeremy D. Mason、Julie A. Pigza、S. Shaun Murphree

  DOI：10.1021/jo201529s

  日期：2011.10.7

  3-dibromo-1-phenylsulfonyl-1-propene (DBP, 2) with 1,3-diketones under basic conditions. The furan-forming step involves a deacetylation, and the selectivity of this process depends upon the steric demand of the R group. The substituent in position 4 is elaborated by reaction of sulfonyl carbanions with alkyl halides, acyl halides, and aldehydes. Oxidative or reductive desulfonylation produces the 2,4-disubstituted

  通过在碱性条件下用1,3-二酮处理2,3-二溴-1-苯基磺酰基-1-丙烯（DBP，2）来制备2,4-二取代的呋喃。呋喃形成步骤涉及脱乙酰基，并且该过程的选择性取决于R基团的空间需求。通过磺酰基碳负离子与烷基卤化物，酰基卤化物和醛的反应来精制4位上的取代基。氧化或还原性磺酰化可产生2,4-二取代的呋喃，产率为60-92％。此策略已用于制备rabdoketone A（12）和天然存在的线毒糠酸13。
• Tunable regioselectivity associated with the reaction of 2,3-dihalo-1-(phenylsulfonyl)-1-propenes with ambident nucleophilic reagents
  作者：Albert Padwa、David J. Austin、Masaru Ishida、Cheryl L. Muller、S. Shaun Murphree、Philip E. Yeske

  DOI：10.1021/jo00030a024

  日期：1992.2

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes, obtained by the addition of bromine or iodine onto (phenylsulfonyl)propadiene, were found to exhibit interesting reactivity as both mono- and dielectrophiles, with the mode of reactivity depending upon the nature of the nucleophile as well as the reaction conditions. Thus, amines or thiophenols smoothly effected substitution at the allylic site, while sodium methoxide reacted at the vinylic position through an addition-elimination process. In the realm of ambident nucleophiles, beta-dicarbonyl compounds in a medium of NaH/tert-butoxide/THF gave 2-alkyl-3-acyl-4-[(phenylsulfonyl)methyl]furans, produced by initial allylic S(N)2 displacement followed by 5-exo-trig cyclization. Conversely, such beta-dicarbonyls in a methoxide/methanol system yielded 2-alkyl-4-[(phenylsulfonyl)methyl]furans, where reaction proceeds by initial addition-elimination on the vinyl sulfone moiety. In contrast, silyl enol ethers in the presence of silver tetrafluoroborate resulted in products derived from S(N)2 displacement at the allylic site. Thioamides could be used to form 2-substituted thiazoles by initial allylic displacement by the sulfur atom followed by an addition-elimination reaction. Thus, a variety of compounds were prepared from 2,3-dihalo-1-(phenylsulfonyl)-1-propenes by the proper choice of reagents and reaction conditions.
• 2,3-Dihalo-1-(phenylsulfonyl)-1-propenes as versatile reagents for the synthesis of annulated furans and cyclopentenones
  作者：Albert Padwa、Masaru Ishida、Cheryl L. Muller、S. Shaun Murphree

  DOI：10.1021/jo00030a025

  日期：1992.2

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes (DBP and DIP) are conveniently prepared by treating 1-(phenylsulfonyl)-1,2-propadiene with the appropriate halogen. These novel reagents undergo reaction with a variety of simple beta-dicarbonyl anions to give substituted and annulated furans. When the reaction is carried out in polar solvents, 2,3,4-trisubstituted furans are formed. The reaction proceeds by an initial addition-elimination of the carbanion onto the vinyl carbon of the unsaturated sulfone which is followed by intramolecular ring closure on the enolate oxygen atom. When sodium methoxide is used as the base, the initially produced adduct undergoes deacylation and subsequent cyclization to give a 2,4-disubstituted furan. The synthetic utility of the method is demonstrated by a synthesis of (R)-menthofuran. Treatment of DIP with various trimethylsilyl enol ethers in the presence of silver tetrafluoroborate give alkylation products derived from S(N)2 displacement of the terminal halide. These compounds readily cyclize with base to produce an isomeric set of furans. Anions derived from 1,3-dicarbonyls substituted in the C-2 position are found to induce a complete reversal in the mode of ring closure. The major products obtained are 3-[(phenylsulfonyl)methyl]-substituted cyclopentenones. The internal displacement reaction leading to the furan ring apparently encounters an unfavorable A1,3-interaction in the transition state when a substituent group is present at the 2-position of the dicarbonyl compound. This steric interaction is not present in the transition state leading to the cyclopentenone ring. An efficient synthesis of cis-jasmone was carried out using this methodology.
• Use of 2,3-dibromo-1-(phenylsulfonyl)-1-propene as a reagent for the synthesis of annulated furans
  作者：Albert Padwa、S. Shaun Murphree、Philip E. Yeske

  DOI：10.1021/jo00301a006

  日期：1990.7