S-(1-methylallyl) S-methyl dithiocarbonate | 40486-60-0

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: S-(1-methylallyl) S-methyl dithiocarbonate
• 英文别名: 3-buten-2-yl methyl dithiocarbonate；dithiocarbonic acid S-methyl ester S-(1-methyl-allyl) ester；1-Methylallyl-methyl-dithiocarbonat；But-3-en-2-ylsulfanyl(methylsulfanyl)methanone
• CAS: 40486-60-0；142109-03-3
• 化学式: C₆H₁₀OS₂
• 分子量: 162.277
• InChiKey: RQUOIXYRMMSYII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-(1-methylallyl) S-methyl dithiocarbonate 在 C.I.酸性橙108 作用下， 生成 丁-3-烯-2-硫醇
  参考文献：
  名称：

  Harano,K.; Taguchi,T., Chemical and pharmaceutical bulletin, 1972, vol. 20, p. 2348 - 2356

  摘要：

  DOI：
• 作为产物：
  描述：

  O-[(E)-but-2-enyl] methylsulfanylmethanethioate 生成 S-(1-methylallyl) S-methyl dithiocarbonate
  参考文献：
  名称：

  方便且立体选择性地合成烯丙基硫化物

  摘要：

  0-（2-烯基或2-环烯基）S-烷基二硫代碳酸酯（黄原酸酯）的分馏得到2-烯基或2-环烯基烷基硫化物。该反应涉及黄原酸酯的[3，3]-σ重排，以产生S-（2-烯基或2-环烯基）S-烷基二硫代碳酸酯，随后挤出氧硫化碳，得到2-烯基或2-环烯基烷基硫化物。

  DOI：

  10.1016/s0040-4039(00)98992-5

文献信息

• Stereoselective formation of allylic sulfides via two sequential (3,3)-sigmatropic rearrangements of allylic xanthates and its mechanistic aspects.
  作者：Kazunobu HARANO、Norihide OHIZUMI、Keisuke MISAKA、Shigeru YAMASHIRO、Takuzo HISANO

  DOI：10.1248/cpb.38.619

  日期：——

  O-(2-Alkynyl) S-alkyl dithiocarbonates (allylic xanthates) were pyrolyzed to give 2-alkenyl alkyl sulfides (allylic sulfides) via the corresponding allylically isomeric S-(2-alkenyl) S-alkyl dithiocarbonates. The reaction follows the first-order rate law with relatively low sensitivity to the ionizing power of the medium and sizeably negative entropies of activation. When a mixture of two dithiol esters having different S-(2-alkenyl) groups and different S-alkyl groups was pyrolyzed, a "cross product" was not observed. The reaction was found to be facilitated by the presence of phenolic compounds or Lewis acids.Based on these findings together with modified neglect of diatomic overlap (MNDO) calculation data, the mechanism for the formation reaction of 2-alkenyl alkyl sulfides is discussed.

  O-(2-炔基) S-烷基二硫代碳酸酯（烯丙基黄原酸酯）通过相应的烯丙异构S-(2-烯基) S-烷基二硫代碳酸酯，热解生成2-烯基烷基硫醚（烯丙基硫醚）。该反应遵循一级速率定律，对介质的电离能力相对不敏感，并且活化熵显著为负。当含有不同S-(2-烯基)基团和不同S-烷基基团的两种二硫酯混合物进行热解时，未观察到“交叉产物”。发现反应在酚类化合物或路易斯酸的存在下得到促进。基于这些发现以及改进的原子间重叠忽略（MNDO）计算数据，讨论了2-烯基烷基硫醚生成反应的机理。
• Deoxygenation of allylic alcohols to terminal olefins via stannylation/destannylation
  作者：Yoshio Ueno、Hiroshi Sano、Makoto Okawara

  DOI：10.1016/s0040-4039(00)77832-4

  日期：1980.1

  Deoxygenation of allylic alcohols to terminal olefins was performed via three steps; 1) [3,3]-sigmatropic rearrangement of O-allylxanthates, 2) the successive stannolysis with tributyltin hydride yielding allylic stannanes, and 3) final protolysis of allylic stannanes to terminal olefins.

  烯丙基醇的脱氧反应通过三个步骤进行；1）O-烯丙基黄原酸酯的[3,3]-σ重排，2）用氢化三丁基锡进行连续锡锡酸酯化，生成烯丙基锡烷，和3）最终将烯丙基锡烷酮分解为末端烯烃。
• Catalytic behavior of phenols in pyrolytic conversion of allylic dithiolcarbonates to allylic sulfides.
  作者：Kazunobu HARANO、Shigeru YAMASHIRO、Keisuke MISAKA、Takuzo HISANO

  DOI：10.1248/cpb.38.2956

  日期：——

  Pyrolytic conversion of S-(2-alkenyl) S-alkyl dithiocarbonates (allylic dithiolcarbonates) to 2-alkenyl alkyl sulfides (allylic sulfides) was catalyzed by phenols bearing electron-attracting substituents. The reaction is pseudo-first-order and the apparent first-order rate constants are proportional not only to the concentration of phenols but also to the hydrogen-bonding capability of phenols. The entropy of activation for the phenol-catalyzed reaction is ca. 8 e.u. smaller than that for the uncatalyzed reaction. The reactivity of S-(1-phenylallyl) S-alkyl dithiocarbonates did not obey Hammett's or Taft's equation. Based on these findings together with the MNDO (modified neglect of diatomic overlap) calculation data, a possible role of phenols in the pyrolytic conversion of allylic dithiolcarbonates to allylic sulfides is discussed.

  在具有电子吸引取代基的酚类催化下，S-(2-烯基)S-烷基二硫代碳酸盐（烯丙基二硫代碳酸盐）发生热解转化，生成2-烯基烷基硫化物（烯丙基硫化物）。反应呈现伪一级动力学特征，表观一级速率常数不仅与酚类浓度成正比，还与酚类的氢键形成能力成正比。与非催化反应相比，酚类催化反应的活化熵减少了约8熵单位。S-(1-苯基烯丙基)S-烷基二硫代碳酸盐的反应活性不遵循Hammett或Taft方程。结合MNDO（修正的双原子重叠忽略）计算数据，基于这些发现，讨论了酚类在烯丙基二硫代碳酸盐热解转化为烯丙基硫化物过程中的可能作用。
• Effect of >CO···H–Ar interaction on endo/exo selectivity in the Diels–Alder reaction of phenyl-substituted cyclopentadienones
  作者：Yasuyuki Yoshitake、Hidetoshi Nakagawa、Masashi Eto、Kazunobu Harano

  DOI：10.1016/s0040-4039(00)00602-x

  日期：2000.6

  e with S-allyl S-methyl dithiocarbonate gave the endo cycloadduct whereas phencyclone gave a mixture of the endo and exo cycloadducts. The X-ray analysis of the cycloadduct of phencyclone and S-allyl S-methyl dithiocarbonate indicated the presence of a short contact of Ar–H···OC< type. A possible role of the interaction in determining the endo/exo selectivity was discussed based on the X-ray crystallographic

  的2,5-双（甲氧基羰基）-3,4- diphenylcyclopentadienone与环加成小号-烯丙基小号-甲基二硫代碳酸酯，得到内型环加成而phencyclone得到的混合物内切和外切cycloadducts。X射线分析苯环酮和S-烯丙基S-甲基二硫代碳酸酯的环加合物表明存在Ar–H···OC<类型的短接触。基于X射线晶体学数据和MO计算数据的过渡结构，讨论了相互作用在确定内/外选择性方面的可能作用。
• Rearrangement and -elimination against the chugaev reaction rule
  作者：T. Taguchi、Y. Kawazoe、K. Yoshihira、H. Kanayama、M. Mori、K. Tabata、K. Harano

  DOI：10.1016/s0040-4039(01)99531-0

  日期：1965.1