2-deuterio-3-methyl-2-butanol | 89830-40-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-deuterio-3-methyl-2-butanol
• 英文别名: 3-methyl-2-butanol-2-d；2-deuterio-3-methyl-butan-2-ol；3-Methyl-2-deutero-butanol-(2)
• CAS: 89830-40-0
• 化学式: C₅H₁₂O
• 分子量: 89.1417
• InChiKey: MXLMTQWGSQIYOW-UICOGKGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.02
• 重原子数：
  6.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-deuterio-3-methyl-2-butanol 、 对甲苯磺酰氯 在 吡啶 作用下， 生成 (3-Methyl-2-deutero-sek.-butyl)-tosylat
  参考文献：
  名称：

  Secondary and tertiary 2-methylbutyl cations. 1. Trifluoroacetolysis of 3-methyl-2-butyl tosylate

  摘要：

  Trifluoroacetolysis rates for 3-methyl-2-butyl tosylate (4) and kinetic isotope effects st C(1) (k(H)/k(D) = 1.083 per H atom), C(2) (k(H)/k(D) = 1.10), and C(3) (k(H)/k(D) = 1.32) were determined. The products are 2-methyl-2-butyl trifluoroacetate (5, 98.5%) and 3-methyl-2-butyl trifluoroacetate (6, 1.5%). GC-MS analysis of products from labeled tosylates 4-1-d(3) and 4-2-d showed that 42% of the apparently unrearranged 6 had a methyl group shifted from the original C(3) to the original C(2), whereas 3.6% methyl shift occurred in 5. The results do not substantiate a k(s)-k(Delta) competition mechanism. Instead, two carbocations, the tertiary 2-methyl-2-butyl (1) and the nominally secondary 3-methyl-2-butyl (2) intervene. The intimate structure of 2 is not established, but a symmetrical, methyl-bridged ion (3) does not agree with the results. A high beta isotope effect does not require hydrogen assistance to ionization; ionization concerted with (assisted by) hydrogen migration is unimportant in formation of 1 (and 5) from 4. Instead, the reaction involves reversible formation of an intimate ion pair with subsequent rate-determining H shift (which for 2.OTs- is in competition with Me shift and ca. 25% elimination) followed by solvent capture. Methyl migration in 2 may occur in the solvent-separated ion pair; alternatively, methyl or hydrogen migration is conformationally determined. At least 9% of 1 is formed from 2 which has undergone methyl shift. Nucleophilic attack an 4 appears important only in strongly nucleophilic media like aqueous ethanol. The claim that nucleophilic solvent assistance is significant in solvolysis of other secondary alkyl substrates in TFA or 97% hexafluoro-2-propanol is evaluated. Such a conclusion cannot be accepted on the basis of rate correlations alone, (i.e without product studies to support it). The implications of our results for the trifluoroacetolysis of 2-butyl tosylate are briefly discussed.

  DOI：

  10.1021/jo00080a025
• 作为产物：
  描述：

  3-甲基-2-丁酮 在 甲酸 、 C₂₀H₂₅IrN₂O₃⁽¹⁺⁾*O₄S^(2-) 、 重水 作用下， 反应 48.0h， 以99%的产率得到2-deuterio-3-methyl-2-butanol
  参考文献：
  名称：

  在铱催化剂上通过H + / D +交换将D2O中的甲酸脱氢而高效生成D2：在转移氘代合成氘代化合物中的应用

  摘要：

  氘代化合物在学术界和工业领域都受到越来越多的关注。但是，由于经济和实际原因，这些化合物的制备受到限制。在此，通过使用具有4,4'-二羟基-2,2'-联吡啶的半三明治铱络合物，证明了方便的氘气（D 2）生成和氘代化合物在实验室规模上的制备。在温和的条件下，通过连续的反应，即阳离子H + / D +交换反应和阴离子氢化物或氘代转移，实现了水的氢原子的“反极性​​”（即极性反转）。通过使用HCO 2实现了选择性的D 2析出（纯度高达89％）H为电子源，D 2 O为氘源；在类似条件下，铑类似物可提供HD气体（98％）。此外，通过在玻璃高压釜中在D 2 O中使用DCO 2 D，产生了没有CO气体的加压D 2（98％）。通过在D 2 O中使用HCO 2 H ，酮的转移氘代化制得的α氘代​​醇几乎定量，并且氘含量高。机理研究表明，氢化铱络合物中的H + / D +交换反应比β-快得多。消除和氢化物（氘代）转移。

  DOI：

  10.1002/chem.201200576

文献信息

• Fragmentation processes of methylbutyl trifluoroacetates studied by tandem quadrupole mass spectrometry and isotope labeling
  作者：Chang S. Hsu、Dan F??rcaşiu

  DOI：10.1002/oms.1210240906

  日期：1989.9

  AbstractThe fragmentation patterns of 3‐methyl‐2‐butyl trifluoroacetate and 2‐methyl‐2‐butyl trifluoroacetate were investigated by GC/MS/MS, with electron impact and collision‐induced dissociation, on regular and isotope‐labeled (deuterium and 18O) esters. The atoms found in various fragments could be traced back to specific positions in the parent molecules. In this way, molecular rearrangements potentially occurring during the formation of esters by trifluoroacetolysis of 3‐methyl‐2‐butyl p‐toluenesulfonate or trifluoroacetic acid addition to various 2‐methylbutenes could be shown. Rearrangements also occurred during the fragmentation, particularly during the expulsion of the small fragments CO, C2H4 and F2CO. For the decompositions of oxygen‐containing ions these rearrangements were highly specific. By contrast, alkyl cations lead to fragments that are fully scrambled (statistical label distribution). Alkene radical cations ([CnH2n]+ ˙) fragment to daughter ions that are extensively, but less than statistically scrambled. Hydrogen scrambling may also occur in fluoroalkyl cation fragments.