2-cyano-2-propyl tosylate | 73341-21-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-cyano-2-propyl tosylate
• 英文别名: p-Toluolsulfonsaeure-(α-cyan-isopropylester)；2-Methyl-2-[(4-methylbenzenesulfonyl)oxy]propanenitrile；2-cyanopropan-2-yl 4-methylbenzenesulfonate
• CAS: 73341-21-6
• 化学式: C₁₁H₁₃NO₃S
• 分子量: 239.295
• InChiKey: ZTYVSOMYSKJEKI-UHFFFAOYSA-N

物化性质

• 熔点：
  97-98 °C
• 沸点：
  396.6±17.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  75.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-cyano-2-propyl tosylate 在 2,6-二甲基吡啶 作用下， 以 various solvent(s) 为溶剂， 生成 甲基丙烯腈
  参考文献：
  名称：

  在不受限制的系统中，磺酸酯的溶剂分解中的H /α-CN与H /β-CN比率。氰基部分可对结合的碳阳离子进行共轭稳定化的其他证据

  摘要：

  已经测量了H /α-CN和H /β-CN的比率，以对相对简单的非环状脂族醇的磺酸酯进行溶剂分解。发现β-CN功能比α-CN功能具有更大的延迟速率。

  DOI：

  10.1016/s0040-4039(01)90304-1
• 作为产物：
  描述：

  4-甲苯磺酸酐 、 氰化钾 、 丙酮 在 吡啶 、 sodium hydrogensulfite 作用下， 生成 2-cyano-2-propyl tosylate
  参考文献：
  名称：

  Bimolecular nucleophilic displacement at tertiary carbon centers: Aminolyses of 2-cyano-2-propyl and 1-cyanocyclooctyl arenesulfonates

  摘要：

  Kinetic studies were carried out on the reactions of anilines with 2-cyano-2-propyl and 1-cyanocyclooctyl arenesulfonates in acetonitrile at 50.0 degrees C. The second-order rate constants for the former are in general greater than those for the latter but the rates of the two become comparable for a strong nucleofuge, The cross-interaction constants, rho(XZ) (and beta(XZ)), are considerably smaller (ca -0.04) than those for the primary (ca 0.33) and secondary (ca 0.12) compounds, The negative sign and small magnitude are consistent with a dissociative S(N)2 mechanism with a loose transition state structure. The ab initio MO theoretical results for Cl- + RCl reversible arrow ClR + Cl- at the MP2 level (MP2/6-31 + G*//MP2/6-31 + G*) confirm the,looseness of the transition state for the tertiary (R) alkyl compounds. The average r((Cl ... Cl))* value is 4.88 +/- 0.03 Angstrom, which is larger than those for the reactions at primary (4.68 +/- 0.02 Angstrom) and secondary (4.80 +/- 0.02 Angstrom) carbon centers. Thus a looser transition state with a smaller magnitude of rho(XZ) for the tertiary carbon centers has a larger theoretical r((Cl ... Cl))* value.

  DOI：

  10.1002/(sici)1099-1395(199610)9:10<683::aid-poc840>3.0.co;2-k

文献信息

• The .alpha.-cyano group as a substituent in solvolysis reactions. An evaluation of inductive destabilization vs. mesomeric stabilization of cations by the cyano moiety
  作者：Paul G. Gassman、John J. Talley

  DOI：10.1021/ja00523a076

  日期：1980.1
• H/α-CN versus H/β-CN rate ratios in the solvolysis of sulfonate esters in unconstrained systems. Additional evidence for conjugative stabilization of attached carbocations by the cyano moiety
  作者：Paul G. Gassman、Katsuhiro Saito

  DOI：10.1016/s0040-4039(01)90304-1

  日期：1981.1

  H/α-CN and H/β-CN rate ratios have been measured for the solvolysis of sulfonate esters of relatively simple, noncyclic aliphatic alcohols. The β-CN function was found to be far more rate retarding than the α-CN function.

  已经测量了H /α-CN和H /β-CN的比率，以对相对简单的非环状脂族醇的磺酸酯进行溶剂分解。发现β-CN功能比α-CN功能具有更大的延迟速率。
• Bimolecular nucleophilic displacement at tertiary carbon centers: Aminolyses of 2-cyano-2-propyl and 1-cyanocyclooctyl arenesulfonates
  作者：Hyuck Keun Oh、Young Bong Kwon、Dong Soo Chung、Ikchoon Lee

  DOI：10.1002/(sici)1099-1395(199610)9:10<683::aid-poc840>3.0.co;2-k

  日期：1996.10

  Kinetic studies were carried out on the reactions of anilines with 2-cyano-2-propyl and 1-cyanocyclooctyl arenesulfonates in acetonitrile at 50.0 degrees C. The second-order rate constants for the former are in general greater than those for the latter but the rates of the two become comparable for a strong nucleofuge, The cross-interaction constants, rho(XZ) (and beta(XZ)), are considerably smaller (ca -0.04) than those for the primary (ca 0.33) and secondary (ca 0.12) compounds, The negative sign and small magnitude are consistent with a dissociative S(N)2 mechanism with a loose transition state structure. The ab initio MO theoretical results for Cl- + RCl reversible arrow ClR + Cl- at the MP2 level (MP2/6-31 + G*//MP2/6-31 + G*) confirm the,looseness of the transition state for the tertiary (R) alkyl compounds. The average r((Cl ... Cl))* value is 4.88 +/- 0.03 Angstrom, which is larger than those for the reactions at primary (4.68 +/- 0.02 Angstrom) and secondary (4.80 +/- 0.02 Angstrom) carbon centers. Thus a looser transition state with a smaller magnitude of rho(XZ) for the tertiary carbon centers has a larger theoretical r((Cl ... Cl))* value.