2-methoxycarbonyl-3,6-dihydro-4,5-dimethyl-2H-thiopyran | 89141-10-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫吡喃类
• 英文名称: 2-methoxycarbonyl-3,6-dihydro-4,5-dimethyl-2H-thiopyran
• 英文别名: methyl 5,6-dihydro-3,4-dimethyl-2H-thiin-6-carboxylate；Methyl 4,5-dimethyl-3,6-dihydro-2H-thiine-2-carboxylate；3,6-Dihydro-2-methoxycarbonyl-4,5-dimethyl-2H-thiopyran；Methyl 4,5-dimethyl-3,6-dihydro-2H-thiopyran-2-carboxylate
• CAS: 89141-10-6
• 化学式: C₉H₁₄O₂S
• 分子量: 186.275
• InChiKey: LZLVVYNJOCBWKV-UHFFFAOYSA-N

物化性质

• 沸点：
  253.5±40.0 °C(Predicted)
• 密度：
  1.077±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methoxycarbonyl-3,6-dihydro-4,5-dimethyl-2H-thiopyran 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 生成 4,5-Dimethyl-3,6-dihydro-2H-thiine-2-carboxylic acid
  参考文献：
  名称：

  通过碱催化烷基邻苯二甲酰亚胺基硫烷基乙酸酯的裂解形成的亲二烯丙基硫代醛和二硫代酸酯

  摘要：

  在室温下用三乙胺处理乙基和亚甲基邻苯二甲硫基乙酸乙酸乙酯1a和1b产生[eqn。（1）]瞬态硫醛，乙基和甲基硫代乙酸甲酯2，已用2,3-二甲基-1,3-二烯就地捕获，从而以高收率生产了Diels-Alder环加合物8a和8b。类似地，分别获得了硫代氧乙酸乙酯2a和蒽，环己-1，3-二烯和环戊二烯的环加合物9、10和11a和12a。以endo ：exo = 7：3的比例形成的环戊二烯的endo -11a和exo -12a环加合物，在甲苯中加热回流时可逆分解，得到相同的平衡混合物，endo：exo＝ 3∶7，因此可以切断作为硫代乙酸乙酯2a的“清洁”辅助前体。因此，当环加合物11a和12a的混合物依次与二甲基丁二烯和（E，E）-1，4-二苯基丁-1，3-二烯，得到相应的二烯环加合物8a和13。出乎意料的是，在二甲基丁二烯存在下，用三乙胺（1摩尔当量）和4-二甲基氨基吡啶（DMAP）（0.1摩尔

  DOI：

  10.1039/p19960000977
• 作为产物：
  描述：

  2-异丙烯基-2-甲基-1-(甲硫基)环丙烷-1-羧酸甲酯 以14%的产率得到
  参考文献：
  名称：

  ISHIBASHI NIROYUKI; OKADA MOTOFUMI; NAKATANI HIROSHI; IKEDA MASAZUMI; TAM+, J. CHEM. SOC. PERKIN TRANS.,(1986) N 10, 1763-1767

  摘要：

  DOI：

文献信息

• Reactions of Wittig Reagents with Episulfides or Elemental Sulfur
  作者：Kentaro Okuma、Yuji Tachibana、Jun-ichi Sakata、Takashi Komiya、Isao Kaneko、Yasuo Komiya、Yusuke Yamasaki、Shin-ichi Yamamoto、Hiroshi Ohta

  DOI：10.1246/bcsj.61.4323

  日期：1988.12

  The reactions of Wittig reagents with episulfides gave symmetrical olefins and triphenylphosphine sulfide in moderate yields. The same olefins were obtained by reactions of Wittig reagents with elemental sulfur. These reactions might proceed through thiocarbonyl intermediates, the existence of which was confirmed by Diels–Alder reactions with dienes.

  Wittig 试剂与环硫化物的反应以中等产率得到对称的烯烃和硫化三苯基膦。通过 Wittig 试剂与元素硫反应获得相同的烯烃。这些反应可能通过硫代羰基中间体进行，硫代羰基中间体的存在已通过与二烯的 Diels-Alder 反应证实。
• Synthesis and thermal transformation of stable monocyclic λ4-thiabenzenes
  作者：Hiroshi Shimizu、Noriaki Kudo、Tadashi Kataoka、Mikio Hori

  DOI：10.1039/b102806p

  日期：——

  The stable monocyclic λ4-thiabenzenes 6a–e, which are stabilized with electron-withdrawing substituents such as benzoyl, cyano and alkoxycarbonyl groups, are synthesized in high yields by proton abstraction from the corresponding thiopyranium salts 5a–e with triethylamine in ethanol. The ylidic properties of the λ4-thiabenzenes are established based on spectral and chemical evidence. Thermal decomposition of the λ4-thiabenzenes affords alkyl-rearranged products 7, 8, and 9, thienofuran derivatives 10 (from benzoyl-substituted λ4-thiabenzenes), and thiophene derivatives 11. A plausible mechanism for the formation of those products is also discussed.

  稳定的单环λ4-噻苯（6a–e），通过苯甲酰、氰基和醇基羧基等电子吸引取代基得到高产率合成。这是通过用三乙胺在乙醇中从相应的噻吡啶盐（5a–e）中抽取质子实现的。λ4-噻苯的卤化属性则是根据光谱和化学证据确立的。λ4-噻苯的热分解得到烷基重排产物7、8和9、噻吩呋喃衍生物10（来自苯甲酰取代的λ4-噻苯）和噻吩衍生物11。文中还讨论了这些产物形成的合理机制。
• Preparation of cycloaddition chemistry of thio- and selenocarbonyls derived from reaction of elemental sulfur and selenium with stabilized α-halo anions
  作者：Matthew M. Abelman

  DOI：10.1016/0040-4039(91)80114-l

  日期：1991.12

  Reaction of diethyl chloromalonate with Cs2CO3 in the presence of elemental S8 or Sen generates the corresponding diethyl thioxo- or selenoxomalonates which are subsequently trapped in situ with various 1,3-dienes. Similarly, the chalcogen carbonyls can be prepared from other halogenated using DBU as the base and effectively trapped in Diels-Alder fashion with 2,3-dimethyl-1,3-butadiene (Table 2).

  氯丙二酸二乙酯与Cs 2 CO 3在元素S 8或Se n的存在下反应，生成相应的二乙基硫代肟酸或亚硒酸丙二酸酯，随后将其与各种1,3-二烯原位捕获。同样，硫族化合物羰基化合物可以用DBU作为碱从其他卤代物中制备，并以Diels-Alder方式有效地被2,3-二甲基-1,3-丁二烯捕获（表2）。
• A Novel Formation of Thiocarbonyl Compounds from Phosphorus Ylides with Cyclic Polysulfide as the Sulfuration Reagent
  作者：Ryu Sato、Shin-ichi Satoh

  DOI：10.1055/s-1991-26574

  日期：——

  The reaction of cyclic polysulfides, such as 5H-1,2,3,4-benzotetrathiepin and 6H-1,2,3,4,5-benzopentathiocin as the sulfuration reagent with relatively stable phosphorus ylides affords efficiently thiocarbonyl compounds such as thioaldehydes and thioketones, which further react with 2,3-dimethyl-1,3-butadiene or cyclopentadiene in situ to give various 5,6-dihydro-2H-thiopyrans and 2-thiabicyclo[2.2.1]hept-5-enes in satisfactory yields.

  将环状多硫化物（如 5H-1,2,3,4-苯并四硫杂卓和 6H-1,2,3,4,5-苯并五硫杂卓作为硫化试剂）与相对稳定的酰化磷反应，可高效生成硫代羰基化合物（如硫代醛和硫酮）、 这些化合物与 2,3-二甲基-1,3-丁二烯或环戊二烯发生原位反应，生成各种 5,6-二氢-2H-硫代吡喃和 2-硫杂双环[2.2.1]庚-5-烯，产量令人满意。
• Generation of thioaldehydes by base-catalysed cleavage of N-(alkoxycarbonylmethylthio)phthalimides
  作者：Gordon W. Kirby、Alistair W. Lochead

  DOI：10.1039/c39830001325

  日期：——

  temperature with triethylamine to generate the corresponding alkyl thioxoacetates, which have been trapped, in situ, by cycloaddition to conjugated dienes; the endo- and exo-adducts of cyclopentadiene and ethyl thioxoacetate dissociate at 111 °C thereby allowing transfer of the thioaldehyde to other conjugated dienes.

  N-（甲氧羰基甲硫基）-和N-（乙氧羰基甲硫基）-邻苯二甲酰亚胺在室温下与三乙胺反应生成相应的烷基硫代氧代乙酸烷基酯，它们已通过环加成反应被原位捕获在共轭二烯中；的内切-和外切在111环戊二烯和乙基硫代乙酸乙酯解离的-adducts℃，从而使硫醛转移到其它共轭二烯。