1-Chlorobutyl p-tolyl sulfoxide | 134857-79-7

• 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: 1-Chlorobutyl p-tolyl sulfoxide
• 英文别名: p-tolyl 1-chlorobutyl sulfoxide；1-chlorobutyl p-tolyl sulfone；Benzene, 1-[(1-chlorobutyl)sulfinyl]-4-methyl-；1-(1-chlorobutylsulfinyl)-4-methylbenzene
• CAS: 134857-79-7
• 化学式: C₁₁H₁₅ClOS
• 分子量: 230.758
• InChiKey: FIAJSUFBCZXQJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Chlorobutyl p-tolyl sulfoxide 在 草酰氯 、 二甲基亚砜 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 4-chloro-1-phenyl-4-(p-tolylsulfinyl)-3-heptanone
  参考文献：
  名称：

  1-卤代烷基芳基亚砜作为合成α-卤代酮的有用试剂：α-卤代酮、α-卤代α,β-不饱和酮和醛类α-卤代交叉二烯酮的新合成

  摘要：

  α-卤代α-亚磺酰基酮由1-卤代烷基芳基亚砜和醛以高产率分两步合成。用乙基溴化镁在乙醚中在低温下对α-卤代α-亚磺酰基酮进行脱硫酰化，通过烯醇镁以高产率得到α-卤代酮。烯醇镁中间体被各种亲电子试剂捕获，例如氧化氘、氯甲酸乙酯和氯三甲基硅烷。用羰基化合物捕获烯醇镁中间体提供了一种新型的定向醛醇反应。α-卤代α-亚磺酰基酮的亚磺酰基在热条件下脱亚磺酰化得到α-卤代α,β-不饱和酮或α-卤代交叉二烯酮。

  DOI：

  10.1246/bcsj.65.2800

文献信息

• New method for generation of β-oxido carbenoid via ligand exchange reaction of sulfoxides: A versatile procedure for one-carbon homologation of carbonyl compounds
  作者：Tsuyoshi Satoh、Norifumi Itoh、Kaoru Gengyo、Sae Takada、Naoyuki Asakawa、Yumi Yamani、Koji Yamakawa

  DOI：10.1016/s0040-4020(01)89299-1

  日期：1994.1

  one-carbon homologation of carbonyl compounds is described. The method is based on the rearrangement of β-oxido carbenoid which is generated via the ligand exchange reaction of the sulfinyl group of α-chloro β-hydroxy sulfoxide with tert-butyllithium. Addition of the carbanion of aryl 1-chloroalkyl sulfoxides to carbonyl compounds gave the adducts in good yields. The β-oxido carbenoid rearrangement of the

  描述了一种新的羰基化合物一碳同系化方法。该方法基于通过α-氯β-羟基亚砜的亚磺酰基与叔丁基锂的配体交换反应而产生的β-氧化类胡萝卜素的重排。将芳基1-氯烷基亚砜的碳负离子加到羰基化合物上，以高收率得到加合物。加合物的β-氧化类胡萝卜素重排得到具有α-烷基取代基的一碳同系羰基化合物。衍生自羰基化合物的加合物与氯甲基对甲苯基亚砜的类似反应产生了亚甲基插入的程序。还讨论了β-氧化类胡萝卜素重排的立体化学。
• A novel method for generation of carbenoid from α-chloro sulfoxides: A new and versatile procedure for one-carbon homologation of carbonyl compounds to carbonyl compounds having an α-alkyl substituent
  作者：Tsuyoshi Satoh、Norifumi Itoh、Kaoru Gengyo、Koji Yamakawa

  DOI：10.1016/s0040-4039(00)60819-5

  日期：——

  Addition of the carbanion of 1-chloroalkyl p-tolyl sulfoxides to carbonyl compound gave the adducts, which were treated with a base followed by t-butyllithium to afford one-carbon homologated carbonyl compounds having an alkyl group at the α-position, via the β-oxido carbenoids, in moderate to good yields.

  将1-氯烷基对甲苯基亚砜的碳负离子加到羰基化合物上，得到加合物，将其用碱处理，然后用叔丁基锂处理，以得到通过α-位在烷基上具有烷基的一碳均聚羰基化合物。 β-氧化类胡萝卜素，产量中等至良好。
• A new synthesis of α,α-disubstituted carbonyl compounds from carbonyl compounds with one-carbon homologation
  作者：Tsuyoshi Satoh、Kohsuke Miyashita

  DOI：10.1016/j.tetlet.2004.04.154

  日期：2004.6

  with carbonyl compounds to afford adducts in high to quantitative yields. The adducts were treated with t-BuMgCl or LDA to give magnesium or lithium alkoxides, which were treated with i-PrMgCl or t-BuLi to afford the enolate with one-carbon elongation through β-oxido carbenoids. The enolate intermediates were found to be able to be trapped with electrophiles to give α,α-disubstituted carbonyl compounds

  使1-氯烷基对甲苯基亚砜的α-亚磺酰基锂与羰基化合物反应，以高收率或定量收率得到加合物。用t- BuMgCl或LDA处理加合物得到镁或锂的醇盐，将其用i- PrMgCl或t - BuLi处理以得到通过β-氧化类胡萝卜素具有一碳延伸的烯醇化物。发现烯醇酸酯中间体能够被亲电子试剂捕获，以中等至良好的产率得到α，α-二取代的羰基化合物。总的来说，该方法提供了一种新的良好方法，该方法仅需两个合成步骤即可从羰基化合物中合成具有碳原子同构关系的α，α-二取代羰基化合物。
• 1-Chloroalkyl<i>p</i>-Tolyl Sulfoxides as Acetylide Anion Equivalent: A Novel Synthesis Including Asymmetric Synthesis of Propargylic Alcohols from Carbonyl Compounds
  作者：Tsuyoshi Satoh、Yasumasa Hayashi、Koji Yamakawa

  DOI：10.1246/bcsj.64.2153

  日期：1991.7

  Addition of the carbanion of 1-chloroalkyl p-tolyl sulfoxide to carbonyl compounds gave the adducts, which were heated in refluxing toluene or xylene to give vinyl chlorides in high overall yield. Dehydrochlorination of the vinyl chlorides with excess n-BuLi afforded propargylic alcohols in high yields. Asymmetric synthesis of both enantiomers of the propargylic alcohols was realized using optically

  将 1-氯烷基对甲苯基亚砜的碳负离子加成到羰基化合物中得到加合物，将其在回流的甲苯或二甲苯中加热以得到高总收率的氯乙烯。用过量的正丁基锂对氯乙烯进行脱氯化氢，以高产率得到炔丙醇。炔丙醇的两种对映异构体的不对称合成是使用光学活性的 1-氯烷基对甲苯基亚砜和醛实现的。
• Nucleophilic Ring-Opening of Chlorooxiranes: A New Synthesis of α-Hydroxy α′-Substituted Ketones from Carbonyl Compounds and 1-Chloroalkyl<i>p</i>-Tolyl Sulfoxides
  作者：Tsuyoshi Satoh、Asako Ogura、Youko Ikeda、Koji Yamakawa

  DOI：10.1246/bcsj.64.1582

  日期：1991.5

  The addition of 1-chloroalkyl p-tolyl sulfoxides to carbonyl compounds gave adducts which were then converted to chlorooxiranes in two steps with good overall yields. The treatment of the chlorooxiranes with various nucleophiles gave α-hygroxy α′-substituted ketones or α-hydroxy ketones in good yields.

  1-chloroalkyl p-tolyl sulfoxides 与羰基化合物的加成反应产生了加合物，然后通过两个步骤将其转化为氯环氧乙烷，总产率很高。用各种亲核剂处理氯环氧乙烷，可以得到α-羟基α′-取代酮或α-羟基酮，收率很高。