3-methylbutan-2-ol-3-d1 | 56688-19-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methylbutan-2-ol-3-d1
• 英文别名: 3-Methyl-2-butanol-3-d；(3D)-3-Methyl-2-butanol；3-deuterio-3-methyl-butan-2-ol；3-Deuterio-3-methylbutan-2-ol
• CAS: 56688-19-8
• 化学式: C₅H₁₂O
• 分子量: 89.1417
• InChiKey: MXLMTQWGSQIYOW-QYKNYGDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-methylbutan-2-ol-3-d1 在 sodium dichromate 、 硫酸 作用下， 生成 <3-D>-3-Methyl-2-butanon
  参考文献：
  名称：

  异丙基-2-d1-(p-取代苯基)乙基酮的红外 C-D 拉伸和 2 H NMR 光谱。C-D 基团与芳香族 π 电子之间氢键式相互作用的证据

  摘要：

  异丙基-2-d 1-(pX-苯基)乙基酮（其中，X=H、NO2、Br、Cl、C2H5、CH3 和 NH2）在 C-D 拉伸区域有两个吸收带。较高频率（约 2177 cm-1）的吸收带被分配给 C–D…π 接近的构象异构体，高频位移归因于空间压缩的影响。通过测量取代基对形成常数和C-D...π接近构象异构体的相对焓的影响，表明存在弱C-D...π氢键。

  DOI：

  10.1246/bcsj.59.3529
• 作为产物：
  描述：

  2-甲基-2-丁烯 在 borane-d3-tetrahydrofuran 、 双氧水 、 sodium hydroxide 作用下， 生成 3-methylbutan-2-ol-3-d1
  参考文献：
  名称：

  一般的，辅助启用的光诱导 Pd 催化的脂肪醇远程去饱和

  摘要：

  已经开发了一种通用的、有效的和位点选择性的可见光诱导的 Pd 催化的脂肪醇远程去饱和成有价值的烯丙基、高烯丙基和双高烯丙基醇。这种转变通过混合 Pd 自由基机制进行，该机制协同结合了自由基方法的有利特征，例如简便的远程 CH HAT 步骤，与过渡金属催化化学（选择性β-氢消除步骤）的特征。与通过最先进的去饱和方法获得的那些相比，这允许在醇的去饱和中实现更高程度的区域选择性和收率。未激活的 C(sp3)-H 站点的 HAT 由易于安装/可拆卸的 Si 助剂启用。烷基碘化物和 Pd(0) 配合物的可见光可有效诱导关键杂化烷基 Pd-自由基中间体的形成。值得注意的是，该方法不需要外源性光敏剂或外部氧化剂。

  DOI：

  10.1021/jacs.7b08459

文献信息

• New amine-stabilized deuterated borane–tetrahydrofuran complex (BD3–THF): convenient reagent for deuterium incorporations
  作者：Robert C. Todd、M. Mahmun Hossain、Kanth V. Josyula、Peng Gao、John Kuo、C.T. Tan

  DOI：10.1016/j.tetlet.2007.01.134

  日期：2007.3

  Convenient methods for the preparation of BD3–THF complex were developed. Certain amines stabilize the BD3–THF for long-term storage. Regioselectivity studies were carried out with the new amine-stabilized BD3–THF with representative olefins. Hydroboration of olefins provides a convenient tool for making corresponding deuterated alcohols after oxidation.

  开发了方便的BD 3 -THF配合物的制备方法。某些胺可稳定BD 3 -THF以长期保存。使用具有代表性烯烃的新型胺稳定BD 3 -THF进行了区域选择性研究。烯烃的氢硼化为氧化后制备相应的氘代醇提供了方便的工具。
• Secondary and tertiary 2-methylbutyl cations. 1. Trifluoroacetolysis of 3-methyl-2-butyl tosylate
  作者：Dan Farcasiu、Gaye Marino、J. Milton Harris、Bruce A. Hovanes、Chang S. Hsu

  DOI：10.1021/jo00080a025

  日期：1994.1

  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.
• Intermediate ion structures in the fragmentation of metastable 3-methylbutan-2-ol radical cations
  作者：M. George、John L. Holmes

  DOI：10.1002/oms.1210251108

  日期：1990.11

  AbstractIonized 3‐methylbutan‐2‐ol displays four low‐energy fragmentations, loss of CH3· and C3H7· and loss of CH4 and C3H8, the latter pair being produced by metastable ion decompositions. The electron‐impact, metastable‐ion and collision‐induced dissociation mass spectra of 13C and 2H‐labelled isotopomers have been recorded, together with appearance energy measurements. It was found that the fast (ion source) losses of CH3· and C3H7· involved only simple bond cleavages between C(1) and C(2) and between C(2) and C(3), respectively, and without any positional interchange of isotopes. The loss of C3H8 produces ionized vinyl alcohol containing only C(l) and C(2). The H atoms involved are only those attached to C(1) and C(3). In deuterium‐labelled analogues, the deuterium is preferentially located in the propane, e.g. metastable CD3CH(OH)CH(CH3)2 yields predominantly C3H6D2. On the basis of all the observations, it is proposed that low‐energy molecular ions can form a stable proton‐bridged molecule‐radical complex, , and that this key intermediate is responsible for the isotope distribution in propane loss and also for the relatively low importance of the lowest energy dissociation, the simple C(1)C(2) bond cleavage.