2-苯硫基丙二酸二乙基酯 | 14064-08-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: 2-苯硫基丙二酸二乙基酯
• 英文名称: diethyl 2-(phenylthio)malonate
• 英文别名: diethyl (phenylthio)malonate；phenylsulfanyl-malonic acid diethyl ester；Phenylmercapto-malonsaeure-diaethylester；Diethyl(phenylsulfanyl)propanedioate；diethyl 2-phenylsulfanylpropanedioate
• CAS: 14064-08-5
• 化学式: C₁₃H₁₆O₄S
• 分子量: 268.334
• InChiKey: CTRLRNRJBJRETO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  77.9
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2930909090

反应信息

• 作为反应物：
  描述：

  2-苯硫基丙二酸二乙基酯 在 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 27.0h， 生成 2-cyclopentylidenemalonic acid diethyl ester
  参考文献：
  名称：

  Stepwise Introduction of π-Electron Cross-Conjugation:  A Possible Access to [5]Radialenes?

  摘要：

  As starting points to the stepwise access to the corresponding [5]radialene, the unsaturated esters 14a and 18a have been prepared. These compounds have been isolated along with their isomers 14b and 18b, resulting from an intracyclic double-bond migration. Moreover a subsequent base-catalyzed process mediated the total isomerization of these mixtures to the latter more stable compounds 14b and 18b. The energy contents of the various compounds, and the corresponding tri- and tetrasubstituted higher homologues 19 and 20, have been calculated at the ab initio level, using several minimal as well as extended basis sets, and the observed experimental results rationalized.

  DOI：

  10.1021/jo970107d
• 作为产物：
  描述：

  Ethyl-bis(phenylthio)malonat 在 sodium ethanolate 、 乙硫醇钠 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以89%的产率得到2-苯硫基丙二酸二乙基酯
  参考文献：
  名称：

  关于控制碳上的亚磺酰基

  摘要：

  通过控制还原易得的双-磺基化产物，可以实现与吸电子基团相邻的碳上的受控单磺基化。

  DOI：

  10.1039/c39820001183

文献信息

• KI-catalyzed C–S bond formation <i>via</i> an oxidation relay strategy: efficient access to various α-thio-β-dicarbonyl compounds
  作者：Yi Jiang、Jiao-Xia Zou、Long-Tao Huang、Xue Peng、Jie-Dan Deng、Long-Qing Zhu、Yu-Hang Yang、Yi-Yue Feng、Xiao-Yun Zhang、Zhen Wang

  DOI：10.1039/c8ob00080h

  日期：——

  An efficient and practical methodology to obtain α-thio-β-dicarbonyl compounds was presented under alkaline conditions via potassium iodide (KI) catalysis.

  在碱性条件下，通过碘化钾（KI）催化，提出了一种获得α-硫代-β-二羰基化合物的高效实用方法。
• Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides: control of disfavored equilibrium reaction
  作者：Mieko Arisawa、Yuri Nihei、Masahiko Yamaguchi

  DOI：10.1016/j.tetlet.2012.07.132

  日期：2012.10

  diaryl disulfides were employed depending on the substrate: di(p-chlorophenyl) disulfide was used for the thiolation reaction of 1-nitroalkanes, 1-nitrocyclopentane and 1-nitrocycloheptane with acidic α-protons (pKa 16 and 17); di(p-methoxyphenyl) disulfide for 1-nitrocyclobutane and 1-nitrocyclohexane with less acidic α-protons (pKa ca. 18). Related reactivities were observed in the thiolation reactions

  在催化量的RhH（PPh 3）4和1,2-双（二苯基膦基）乙烷（dppe）存在下，1-硝基烷烃与二芳基二硫化物反应，在空气中生成1-芳硫基-1-硝基烷烃。铑催化的巯基氧化为二硫化物和水的反应使形成热力学不利产物的平衡发生了变化。环状硝基烷烃的硫醇化反应可以高收率进行，只要根据基材使用合适的二芳基二硫化物即可：二（对氯苯基）二硫化物用于1-硝基烷烃，1-硝基环戊烷和1-硝基环庚烷与酸性α的硫醇化反应。 -质子（p K a 16和17）; 二（p甲氧基苯基）二硫化物1-nitrocyclobutane和1-硝基环己烷较少酸性α质子（对ķ一个约18）。在丙二酸酯和1,2-二苯乙酮的硫醇化反应中观察到相关的反应性。
• Sulfenylation of Active Methylene Compounds with Sulfenamides
  作者：Takanobu Kumamoto、Susumu Kobayashi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.45.866

  日期：1972.3

  secondary alkylamines with active methylene compounds afforded mono-sulfenylated compounds in good yields. The reactions of 2 mol of sulfenamides derived from imides with 1 mol of active methylene compounds in the presence of a base gave di-sulfenylated compounds. It was found that α-mono-sulfenylated ketones were prepared by the reactions of enamines with sulfenamides derived from imides. α-gem-Di-sulfenylated

  衍生自仲烷基胺的次磺酰胺与活性亚甲基化合物的等摩尔反应以良好的产率提供单次磺酰化的化合物。2 mol 衍生自酰亚胺的次磺酰胺与 1 mol 活性亚甲基化合物在碱存在下反应，得到二亚磺酰化化合物。发现α-单-亚磺酰化酮是通过烯胺与衍生自酰亚胺的次磺酰胺反应制备的。α-gem-Di-sulfenylated 酮是通过 α-mono-sulfenylated 酮与衍生自酰亚胺的亚磺酰胺在碱存在下反应制备的。还研究了N-苯基硫代苯甲脒盐酸盐的制备和反应。
• Regioselective Mono- and Bis-Sulfenylation of Active Methylene Compounds
  作者：Namita Devi、Rajjakfur Rahaman、Kuladip Sarma、Pranjit Barman

  DOI：10.1002/ejoc.201501148

  日期：2016.1

  Selective mono- and bis-sulfenylation of active methylene groups with a variety of disulfides at an ambient temperature is reported. Sulfenylation is promoted by iodine as a catalyst and sulfenyl iodides as intermediates, under metal-free conditions. The method is greener in terms of solvent selection and the use of less hazardous DMSO as an oxidant. The procedure is highly efficient with readily available

  据报道，在环境温度下，活性亚甲基与多种二硫化物的选择性单-和双-亚磺酰化反应。在无金属条件下，以碘为催化剂，以亚硫基碘为中间体，可促进亚磺酰化。该方法在溶剂选择和使用危害较小的 DMSO 作为氧化剂方面更环保。该程序非常有效，使用容易获得的起始材料，并提供良好的收率。
• A CONVENIENT SYNTHESIS OF SULFENYLATED ACTIVE METHYLENE COMPOUNDS USING DIARYL DISULFIDES
  作者：Tamotsu Fujisawa、Kazumi Hata、Takakazu Kojima

  DOI：10.1246/cl.1973.287

  日期：1973.3.5

  sulfenylated active methylene compounds has been investigated by the reaction of diaryl disulfides with active methylene compounds in a basic media. Malonates, acetoacetate, acetylacetone, and malononitrile gave selectively the corresponding monosulfenylated compounds at room temperature. At elevated temperatures, only malononitrile afforded a disulfenylated compound, while reactions with other active methylene

  通过二芳基二硫化物与活性亚甲基化合物在碱性介质中的反应，研究了一种新的磺酰化活性亚甲基化合物的制备方法。丙二酸酯、乙酰乙酸酯、乙酰丙酮和丙二腈在室温下选择性地产生相应的单磺酰化化合物。在升高的温度下，只有丙二腈提供二磺酰化的化合物，而与其他活性亚甲基化合物的反应导致单磺酰化的产物分解。