N-cyclohex-2-en-1-yl-N-methyltrichloroacetamide | 133165-64-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-cyclohex-2-en-1-yl-N-methyltrichloroacetamide
• 英文别名: 2,2,2-trichloro-N-cyclohex-2-en-1-yl-N-methylacetamide
• CAS: 133165-64-7
• 化学式: C₉H₁₂Cl₃NO
• 分子量: 256.559
• InChiKey: RYQBMHTYJIITDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N-cyclohex-2-en-1-yl-N-methyltrichloroacetamide 在 sodium hydroxide 、 三乙胺 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 4.0h， 生成 2-chloro-N-cyclohex-2-en-1-yl-N-methylacetamide
  参考文献：
  名称：

  Effects of temperature on atom transfer cyclization reactions of allylic .alpha.-iodo esters and amides

  摘要：

  Atom-transfer cyclizations of allyl iodoacetates and N-allyl-N-methyliodoacetamides are much more efficient at 80-degrees-C than at 25-degrees-C. At 80-degrees-C, beta-(iodomethyl) lactones and lactams are formed rapidly and in good yield under standard atom-transfer conditions (sunlamp irradiation of iodide and 10% hexabutylditin in benzene for 10-60 min). It is proposed that this temperature effect is responsible for some unusual observations by Jolly and Livinghouse in the cyclization of N-cyclohexenyl-N-methyliodoacetamide. The results suggest that the beneficial effect of temperature arises because an increase in the rate of rotation of the OC-O or OC-N bond in the intermediate radicals begins to convert syn radicals (which cannot cyclize) to anti radicals (which can cyclize). Consistent with this hypothesis, the radical derived from N,N-diallyliodoacetamide (which always has a favorable arrangement for cyclization) closes with excellent efficiency at 25-degrees-C.

  DOI：

  10.1021/jo00008a032
• 作为产物：
  描述：

  cyclohex-2-en-1-yl 2,2,2-trichloroacetimidate 在 18-冠醚-6 sodium hydride 作用下， 以 xylene 为溶剂， 反应 42.5h， 生成 N-cyclohex-2-en-1-yl-N-methyltrichloroacetamide
  参考文献：
  名称：

  Effects of temperature on atom transfer cyclization reactions of allylic .alpha.-iodo esters and amides

  摘要：

  Atom-transfer cyclizations of allyl iodoacetates and N-allyl-N-methyliodoacetamides are much more efficient at 80-degrees-C than at 25-degrees-C. At 80-degrees-C, beta-(iodomethyl) lactones and lactams are formed rapidly and in good yield under standard atom-transfer conditions (sunlamp irradiation of iodide and 10% hexabutylditin in benzene for 10-60 min). It is proposed that this temperature effect is responsible for some unusual observations by Jolly and Livinghouse in the cyclization of N-cyclohexenyl-N-methyliodoacetamide. The results suggest that the beneficial effect of temperature arises because an increase in the rate of rotation of the OC-O or OC-N bond in the intermediate radicals begins to convert syn radicals (which cannot cyclize) to anti radicals (which can cyclize). Consistent with this hypothesis, the radical derived from N,N-diallyliodoacetamide (which always has a favorable arrangement for cyclization) closes with excellent efficiency at 25-degrees-C.

  DOI：

  10.1021/jo00008a032

文献信息

• Synthesis of α-Chlorolactams by Cyanoborohydride-Mediated Radical Cyclization of Trichloroacetamides
  作者：Guilhem Coussanes、Harald Jakobi、Stephen Lindell、Josep Bonjoch

  DOI：10.1002/chem.201800210

  日期：2018.6.7

  A cyanoborohydride‐promoted radical cyclization methodology has been developed to access α‐chlorolactams in a simple and efficient way using NaBH3CN and trichloroacetamides easily available from allylic and homoallylic secondary amines. This methodology allowed the synthesis of a library of α‐chlorolactams (mono‐ and bicyclic), which were tested for herbicidal activity, trans‐3‐chloro‐4‐methyl‐1‐(

  已开发出一种氰基硼氢化物促进的自由基环化方法，可使用NaBH 3 CN和三氯乙酰胺（可从烯丙基和均烯丙基仲胺中轻松获得）以简单有效的方式获得α-氯内酰胺。这种方法学允许合成α-氯内酰胺（单环和双环）文库，并对其除草活性进行了测试，反式-3-氯-4-甲基-1-（3-三氟甲基）苯基-2-吡咯烷酮是最活跃。
• Directed Dihydroxylation of Cyclic Allylic Alcohols and Trichloroacetamides Using OsO₄/TMEDA
  作者：Timothy J. Donohoe、Kevin Blades、Peter R. Moore、Michael J. Waring、Jon J. G. Winter、Madeleine Helliwell、Nicholas J. Newcombe、Geoffrey Stemp

  DOI：10.1021/jo026161y

  日期：2002.11.1

  The oxidation of a range of cyclic allylic alcohols and amides with OsO4/TMEDA is presented. Under these conditions, hydrogen bonding control leads to the (contrasteric) formation of the syn isomer in almost every example that was examined. Evidence for the bidentate binding of TMEDA to OsO4 is presented and a plausible mechanism described.

  介绍了用OsO4 / TMEDA氧化一系列环状烯丙醇和酰胺的方法。在这些条件下，几乎在每个所研究的实施例中，氢键控制导致顺式异构体的（对映体）形成。提供了TMEDA与OsO4的双齿结合的证据，并描述了一个可能的机制。
• CURRAN, DENNIS P.;TAMINE, JOHN, J. ORG. CHEM., 56,(1991) N, C. 2746-2750
  作者：CURRAN, DENNIS P.、TAMINE, JOHN

  DOI：——

  日期：——