N-allyl-α-chloro-N-methyl-α-(phenylthio)acetamide | 80716-60-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: N-allyl-α-chloro-N-methyl-α-(phenylthio)acetamide
• 英文别名: N-Allyl-N-methyl-α-chloro-α-(phenylthio)acetamide；2-chloro-N-methyl-2-phenylsulfanyl-N-prop-2-enylacetamide
• CAS: 80716-60-5
• 化学式: C₁₂H₁₄ClNOS
• 分子量: 255.768
• InChiKey: AJTWHGFWJCIPCK-UHFFFAOYSA-N

物化性质

• 沸点：
  334.9±42.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  45.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-allyl-α-chloro-N-methyl-α-(phenylthio)acetamide 在 偶氮二异丁腈 、 三正丁基氢锡 、 sodium ethanolate 作用下， 以 乙醇 、 苯 为溶剂， 反应 3.0h， 生成 trans-1,4-dimethyl-3-phenylthiopyrrolidin-2-one
  参考文献：
  名称：

  Sato, Tatsunori; Wada, Yasuko; Nishimoto, Mami, Journal of the Chemical Society. Perkin transactions I, 1989, p. 879 - 886

  摘要：

  DOI：
• 作为产物：
  描述：

  N-allyl-N-methyl-α-(phenylthio)acetamide 在 N-氯代丁二酰亚胺 作用下， 以 四氯化碳 为溶剂， 反应 4.0h， 生成 N-allyl-α-chloro-N-methyl-α-(phenylthio)acetamide
  参考文献：
  名称：

  Sato, Tatsunori; Wada, Yasuko; Nishimoto, Mami, Journal of the Chemical Society. Perkin transactions I, 1989, p. 879 - 886

  摘要：

  DOI：

文献信息

• Cationic polar cycloaddition with chloromethyl phenyl sulfides
  作者：Y. Tamura、K. Ishiyama、Y. Mizuki、H. Maeda、H. Ishibashi

  DOI：10.1016/s0040-4039(01)82017-7

  日期：1981.1

  Chloromethyl phenyl sulfides 3 underwent [4+ +2] type polar cyclo-additions with styrene, trans-stilbene, and phenylacetylene in the presence of stannic chloride to afford the thiochroman 4, 5 and thiochromen derivatives 6. Under the same reaction conditions, N-allyl-α-chloro-α-(phenylthio)acetamide (7) gave the intramolecular cycloaddition product 8.

  在氯化锡的存在下，与苯乙烯，反式苯乙烯和苯乙炔进行氯甲基苯基硫化物3的[4 + +2]型极性环加成反应，得到硫代铬烷4、5和硫代色素衍生物6。在相同的反应条件下，N -烯丙基-α-氯-α-（苯硫基）乙酰胺（7）得到分子内环加成产物8。
• Ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic .alpha.-chloro-.alpha.-thioacetamides. Synthesis of (-)-trachelanthamidine and formal total synthesis of (.+-.)-haemanthidine and (.+-.)-pretazettine
  作者：Hiroyuki Ishibashi、Nahoko Uemura、Hiroshi Nakatani、Mika Okazaki、Tatsunori Sato、Nobuyuki Nakamura、Masazumi Ikeda

  DOI：10.1021/jo00061a005

  日期：1993.4

  A new method for the synthesis of five-membered lactams by ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic alpha-chloro-alpha-thioacetamides and the application of the method to the synthesis of the title alkaloids are described. A benzene solution of N-allyl-N-methyl-alpha-chloro-alpha-(phenylthio)acetamide (6) was heated at 140-degrees-C in the presence of RuCl2(PPh3)3 to give alpha-thio-beta-(chloromethyl)-substituted gamma-lactam 8 as a mixture of cis and trans isomers in a ratio of ca. 3:7. NH congener 11, however, gave no cyclization product. Heating chloro sulfides 18 and 19, prepared from L-prolinol, with RuCl2(PPh3)3 afforded bicyclic lactams 20 and 21, respectively. Treatment of 20 with cesium propanoate gave predominantly cyclopropane derivative 25, whereas S-methyl congener 21 provided esters 24 in good yield. Desulfurization of 24 with Raney nickel followed by reduction with LiAlH4 furnished (-)-trachelanthamidine (28). On the other hand, N-(cyclohex-2-en-1-yl) derivative 30, when heated with RuCl2(PPh3)3, afforded octahydroindol-2-ones 31a,b. The formation of 31a,b indicated that the intramolecular addition of the chloro sulfide of 30 to the olefinic bond proceeded in an anti-mode. By contrast, 2-phenyl-substituted derivative 38 gave syn-addition product 39. The difference between the modes of cyclization of 30 and 38 can be explained by assuming the intermediacy of radical 34. When R = H, the chlorine atom attacks the convex face of the fused bicyclic system of 34 to lead to 31a,b, whereas the steric bulk of the angular phenyl group (R = Ph) is apparently sufficient to direct the chlorine atom to the concave face. Heating chloro sulfide 48, prepared in a highly stereocontrolled manner from cyclohexene 42, with RuCl2(PPh3)3 afforded bicyclic lactam 49. Oxidation of 49 with m-CPBA followed by Pummerer rearrangement/hydrolysis gave keto lactam 51, which was dehydrochlorinated with DBU to give olefin 52. LiAlH4 reduction of 52 and acylation with pivaloyl chloride provided ester 54, a key intermediate in Martin's total synthesis of (+/-)-haemanthidine (41) and (+/-)-pretazettine (40).
• Ishibashi, Hiroyuki; Okada, Motofumi; Sato, Kazumi, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 1, p. 90 - 95
  作者：Ishibashi, Hiroyuki、Okada, Motofumi、Sato, Kazumi、Ikeda, Masazumi、Ishiyama, Ko-ichi、Tamura, Yasumitsu

  DOI：——

  日期：——
• SATO, TATSUNORI;WADA, YASUKO;NISHIMOTO, MAMI;ISHIBASHI, HIROYUKI;IKEDA, M+, J. CHEM. SOC. PERKIN TRANS. PT 1,(1989) N, C. 879-886
  作者：SATO, TATSUNORI、WADA, YASUKO、NISHIMOTO, MAMI、ISHIBASHI, HIROYUKI、IKEDA, M+

  DOI：——

  日期：——
• TAMURA, Y.;ISHIYAMA, K.;MIZUKI, Y.;MAEDA, H.;ISHIBASHI, H., TETRAHEDRON LETT., 1981, 22, N 38, 3773-3774
  作者：TAMURA, Y.、ISHIYAMA, K.、MIZUKI, Y.、MAEDA, H.、ISHIBASHI, H.

  DOI：——

  日期：——