2-(methylpropylidene)-1,3-dithiane | 36998-38-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: 2-(methylpropylidene)-1,3-dithiane
• 英文别名: 2-(propan-2-ylidene)-1,3-dithiane；2-(2-propylidene)-1,3-dithiane；2-isopropylidene-1,3-dithiane；2-isobutylidene-1,3-dithiane；2-Isopropyliden-1,3-dithian；2-isopropylidene-[1,3]dithiane；2-propan-2-ylidene-1,3-dithiane
• CAS: 36998-38-6
• 化学式: C₇H₁₂S₂
• 分子量: 160.304
• InChiKey: JVJZONAXPGALSZ-UHFFFAOYSA-N

物化性质

• 沸点：
  105-108 °C(Press: 12 Torr)
• 密度：
  1.088±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(methylpropylidene)-1,3-dithiane 在 四甲基乙二胺 、 仲丁基锂 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 4-methyl-2-phenyl-4-phenylselanyl-1-oxa-6,10-dithiaspiro[4.5]decane
  参考文献：
  名称：

  Ketene thioacetal route to .gamma.-lactones. Effect of carbonyl hardness on reaction-site selectivity and a unique preparation of 3-methyl-5-phenyl-2(5H)-furanone

  摘要：

  DOI：

  10.1021/jo01299a039
• 作为产物：
  描述：

  2-(1-Chloro-1-methyl-ethyl)-[1,3]dithiane 在 氢氧化钾 作用下， 以 苯 为溶剂， 反应 1.0h， 以92%的产率得到2-(methylpropylidene)-1,3-dithiane
  参考文献：
  名称：

  Ketene Thioacetals from α-Chloromercaptals

  摘要：

  Excellent yields of ketene thioacetals are obtained from 2-(1-chloroalkyl)-1,3-dithiolanes or 2-(1-chloroalkyl)-1,3-dithianes.

  DOI：

  10.1080/00397919308011176

文献信息

• Total Synthesis of (−)-Salvinorin A
  作者：Nathan J. Line、Aaron C. Burns、Sean C. Butler、Jerry Casbohm、Craig J. Forsyth

  DOI：10.1002/chem.201604853

  日期：2016.12.12

  κ‐opioid receptor. A total synthesis has been developed that parlays the stereochemistry of l‐(+)‐tartaric acid into that of (−)‐1 via an unprecedented allylic dithiane intramolecular Diels–Alder reaction to obtain the trans‐decalin scaffold. Tsuji allylation set the C9 quaternary center and a late‐stage stereoselective chiral ligand‐assisted addition of a 3‐titanium furan upon a C12 aldehyde/C17 methyl

  Salvinorin A（1）是与人κ阿片受体结合的天然致幻剂。已开发出一种总合成方法，可通过空前的烯丙基二噻烷分子内Diels-Alder反应将l -（+）-酒石酸的立体化学与（-）- 1的立体化学相结合，以获得反-decalin支架。Tsuji烯丙基化作用可确定C9季铵盐中心，并在C12醛/ C17甲基酯上的后期立体选择性手性配体辅助添加3-钛呋喃，从而建立了呋喃基内酯部分。酒石酸二醇最终转化为C1，C2酮乙酸酯。
• Stereoselectivity in intramolecular diels-alder reactions; a short total synthesis of (±)-estrone
  作者：Michael E Jung、Kim M Halweg

  DOI：10.1016/s0040-4039(01)81177-1

  日期：1984.1

  A new synthesis of estrone via an internal Diels-Alder reaction is reported.

  据报道，通过内部Diels-Alder反应可以合成雌酮。
• Synthesis and reactions of .alpha.-methylene-.beta.-keto sulfones
  作者：Andreas Weichert、H. Martin R. Hoffmann

  DOI：10.1021/jo00013a007

  日期：1991.6

  Modified Jones oxidation of 2-(benzenesulfonyl)-2-alken-1-ols and rapid nonnucleophilic workup below 0-degrees-C yields a variety of alpha-methylene-beta-keto sulfones 4, including crystalline parent 4a and also e-h, which can be stored at -20-degrees-C without change. In the absence of nucleophiles, the new compounds are stable (heating in benzene) toward dimerization and polymerization. Thus, selective cross-reactions are feasible. With alcohols, including sterically hindered tertiary alcohols and also with 2-(ethoxycarbonyl)cyclopentanone, the compounds function as efficient Micheal acceptors, even in the absence of base catalysis. In moist ether, 2-(benzenesulfonyl)-1-penten-3-one (4b) suffers rearrangement to 2-(benzenesulfonyl)ethyl propanoate (9). Sulfonylated alcohol 7 and strained alpha-hydroxyoxetane 8 are assumed as intermediates. Toward electron-rich aromatics and heteroaromatics, alpha-methylene-beta-keto sulfones 4 behave as electrophiles in Friedel-Crafts-type functionalizations. The new compounds are also dienophilic: of the two groups (acetyl and benzenesulfonyl) attached to the ethylenic terminus in 4a, benzenesulfonyl has been found to preferentially adopt the endo position in cycloadditions of cyclopentadiene and also cyclohexadiene. Prototype 3-(benzenesulfonyl)-3-buten-2-one (4a) is a crystalline methyl vinyl ketone (MVK) equivalent which, unlike MVK, undergoes controlled free-radical additions with nucleophilic radicals. In hetero-Diels-Alder reactions, 4a serves as a 1-oxa-1,3-butadiene unit, combining with a wide range of alkenes of graded nucleophilicity. Electron deficient 4a also reacts as an enophile toward 1,1-dialkylated ethylenes. In the presence of ZnCl2.OEt2, the ene reaction with beta-piene can be suppressed completely in favor of cycloaddition, giving a robustadial building block in 85% yield. In further applications to natural products chemistry, the synthesis of frontalin and novel oxatricyclics are described.
• Conjugate addition of dithianylidene anions to α,β-unsaturated ketones. An application to the total synthesis of (±)-aromatin and (±)-confertin
  作者：Frederick E. Ziegler、Jim Min Fang、Coretta Chan Tam

  DOI：10.1021/ja00389a047

  日期：1982.12
• Groebel,B.-T. et al., Synthesis, 1976, p. 121 - 123
  作者：Groebel,B.-T. et al.

  DOI：——

  日期：——