2,12-dimethylcyclododecan-1-one | 32399-58-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,12-dimethylcyclododecan-1-one
• 英文别名: 2.12-dimethylcyclododecanone
• CAS: 32399-58-9
• 化学式: C₁₄H₂₆O
• 分子量: 210.36
• InChiKey: ZVQNMDFGLFPHQJ-UHFFFAOYSA-N

物化性质

• 沸点：
  291.1±8.0 °C(Predicted)
• 密度：
  0.843±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,12-dimethylcyclododecan-1-one 在 盐酸 、 水 、 碳酸氢钠 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 反应 1.5h， 生成
  参考文献：
  名称：

  Study of Consecutive Biradicals from 2-Hydroxy-2,12-dimethylcyclododecanone by TR-CIDNP, TREPR, and Laser Flash Photolysis

  摘要：

  Several time-resolved spectroscopic techniques (H-1 CIDNP, time-resolved EPR, and nanosecond laser flash photolysis) have been used to investigate geminate reactions of consecutive biradicals generated from photolysis of 2-hydroxy-2,12-dimethylcyclododecanone (1). It is shown that the primary photochemical process is Norrish type I cleavage, yielding an acyl-ketyl biradical, which is transformed to an alkyl-ketyl biradical via decarbonylation. The rate constant for decarbonylation, estimated by theoretical modeling of the TR-CIDNP kinetics, is (4.2 +/- 1.0) x 10(5) s(-1) The calculations are based on the numerical solution of the stochastic Liouville equation for the Fourier transform of the biradical spin density matrix. The lifetime of the acylketyl biradical (tau = 67 +/- 8 ns) has been measured using laser flash photolysis. The distribution of reaction products in the photolysis of 1, including recombination to the starting ketone, was determined from the CIDNP amplitude and kinetics, The reaction products include unstable compounds containing enol functional groups, which are transformed to the keto form during the dark reaction of tautomerization.

  DOI：

  10.1021/jp9711196
• 作为产物：
  描述：

  环十二酮 以 甲醇 为溶剂， 生成 2-甲基环十二碳壬 、 2,12-dimethylcyclododecan-1-one
  参考文献：
  名称：

  Methylation of cyclohexanone with simultaneous dehydrogenation

  摘要：

  在铜和/或银催化剂的存在下，通过将至少带有一个甲基或亚甲基基团的酮与一次醇反应，进行烷基化反应的催化过程。

  公开号：

  US03932518A1

文献信息

• A Convenient Ruthenium-Catalysed α-Methylation of Carbonyl Compounds using Methanol
  作者：Tuan Thanh Dang、Abdul Majeed Seayad

  DOI：10.1002/adsc.201600562

  日期：2016.11.3

  effective for the one‐pot sequential α‐alkylation–α‐methylation of methyl ketones and conjugate reduction–α‐methylation of α,β‐unsaturated ketones to synthesise α‐branched ketones. An application of the α‐methylation of esters using the ruthenium catalyst was demonstrated for an alternative catalytic synthesis of Ketoprofen.

  首次报道了一种有效的钌催化剂，它使用甲醇作为绿色甲基化剂来催化酮和酯的α-甲基化。在原位从复合物中产生的催化剂〔RuCp *氯2 ] 2或[RuCp *氯2 ] Ñ与dpePhos中的仅20摩尔％的锂的存在下提供高达定量产率叔丁醇（LiO-叔卜）为基础。区域选择性的单或多甲基化可以通过温度有效控制。该催化剂体系对于一锅顺序的甲基酮的α-烷基化-α-甲基化和α，β-不饱和酮的共轭还原-α-甲基化也有效，以合成α-支链的酮。已证明使用钌催化剂对酯进行α-甲基化可用于酮洛芬的另一种催化合成。
• Casanova,J.; Waegell,B., Bulletin de la Societe Chimique de France, 1971, # 4, p. 1289 - 1295
  作者：Casanova,J.、Waegell,B.

  DOI：——

  日期：——
• US3932518A
  申请人：——

  公开号：US3932518A

  公开（公告）日：1976-01-13
• Study of Consecutive Biradicals from 2-Hydroxy-2,12-dimethylcyclododecanone by TR-CIDNP, TREPR, and Laser Flash Photolysis
  作者：Olga B. Morozova、Alexandra V. Yurkovskaya、Yuri P. Tsentalovich、Renad Z. Sagdeev、Tina Wu、Malcolm D. E. Forbes

  DOI：10.1021/jp9711196

  日期：1997.11.1

  Several time-resolved spectroscopic techniques (H-1 CIDNP, time-resolved EPR, and nanosecond laser flash photolysis) have been used to investigate geminate reactions of consecutive biradicals generated from photolysis of 2-hydroxy-2,12-dimethylcyclododecanone (1). It is shown that the primary photochemical process is Norrish type I cleavage, yielding an acyl-ketyl biradical, which is transformed to an alkyl-ketyl biradical via decarbonylation. The rate constant for decarbonylation, estimated by theoretical modeling of the TR-CIDNP kinetics, is (4.2 +/- 1.0) x 10(5) s(-1) The calculations are based on the numerical solution of the stochastic Liouville equation for the Fourier transform of the biradical spin density matrix. The lifetime of the acylketyl biradical (tau = 67 +/- 8 ns) has been measured using laser flash photolysis. The distribution of reaction products in the photolysis of 1, including recombination to the starting ketone, was determined from the CIDNP amplitude and kinetics, The reaction products include unstable compounds containing enol functional groups, which are transformed to the keto form during the dark reaction of tautomerization.
• Methylation of cyclohexanone with simultaneous dehydrogenation
  申请人：Hoechst Aktiengesellschaft

  公开号：US03932518A1

  公开（公告）日：1976-01-13

  Catalytic process for alkylating ketones carrying at least one methyl or methylene group in .alpha.-position to the carbonyl group by reacting them with primary alcohols in the presence of copper and/or silver catalysts.

  在铜和/或银催化剂的存在下，通过将至少带有一个甲基或亚甲基基团的酮与一次醇反应，进行烷基化反应的催化过程。