正丁醇-D2 | 32586-14-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 正丁醇-D2
• 中文别名: 氘代正丁醇
• 英文名称: [1,1-d2]-1-butanol
• 英文别名: n-butanol-1,1-d2；<1,1-D2>-1-Butanol；1-Butanol-1,1-d(2)；1,1-Dideuteriobutan-1-ol
• CAS: 32586-14-4
• 化学式: C₄H₁₀O
• 分子量: 76.1069
• InChiKey: LRHPLDYGYMQRHN-APZFVMQVSA-N

物化性质

• 沸点：
  116-117 °C
• 密度：
  0.8169 g/cm3(Temp: 25 °C)
• 溶解度：
  可微溶于水

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  5
• 可旋转键数：
  2
• 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：

  正丁醇-D2 在 potassium iodide 作用下， 以 磷酸 为溶剂， 反应 5.0h， 以50%的产率得到1-(1,1-2H2)-iodobutane
  参考文献：
  名称：

  Site-selective deuterium labeling of the tetrabutylammonium cation

  摘要：

  Four separate selectively deuterated samples of tetrabutylammonium iodide have been prepared in which each one of the four nonequivalent alkyl carbons is separately and fully deuterated. These samples were prepared for nuclear magnetic resonance (NMR) studies of the aggregation of ion pairs in low polarity solvents.

  DOI：

  10.1002/(sici)1099-1344(200004)43:5<473::aid-jlcr333>3.0.co;2-s
• 作为产物：
  描述：

  丁酸酐 在 lithium aluminium deuteride 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以90%的产率得到正丁醇-D2
  参考文献：
  名称：

  Site-selective deuterium labeling of the tetrabutylammonium cation

  摘要：

  Four separate selectively deuterated samples of tetrabutylammonium iodide have been prepared in which each one of the four nonequivalent alkyl carbons is separately and fully deuterated. These samples were prepared for nuclear magnetic resonance (NMR) studies of the aggregation of ion pairs in low polarity solvents.

  DOI：

  10.1002/(sici)1099-1344(200004)43:5<473::aid-jlcr333>3.0.co;2-s

文献信息

• Regioselective deuteration of alcohols in D₂O catalysed by homogeneous manganese and iron pincer complexes
  作者：Sayan Kar、Alain Goeppert、Raktim Sen、Jotheeswari Kothandaraman、G. K. Surya Prakash

  DOI：10.1039/c8gc01052h

  日期：——

  We report a convenient and cost-effective protocol for the regioselective deuteration of primary and secondary alcohols using Earth abundant homogeneous first row transition metal pincer catalysts. D2O is utilized as both a deuterium source and a solvent, allowing for a benign inexpensive process. Depending on the metal selected (Mn or Fe), a high degree of deuterium incorporation was observed selectively

  我们报告了一种方便和具有成本效益的协议，用于使用地球丰富的均质的第一行过渡金属钳催化剂催化伯醇和仲醇的区域选择性氘化。D 2 O既用作氘源又用作溶剂，从而实现了良性廉价的工艺。取决于所选择的金属（Mn或Fe），对于伯醇，选择性地在α和β位置（Mn）或仅在α位置（Fe）观察到高度的氘掺入。这种简单，有效且具有成本效益的醇C–H键氘代的方案是大规模合成氘代分子的有力工具。
• Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base Resistance
  作者：Sean A. Lutz、Anne K. Hickey、Yafei Gao、Chun-Hsing Chen、Jeremy M. Smith

  DOI：10.1021/jacs.0c07300

  日期：2020.9.9

  3/2) organometallic iron(I) complex is a catalyst for the isomerization of alkenes. A combination of experimental and computational mechanistic studies supports a mechanism in which alkene isomerization occurs by the allyl mechanism. Importantly, while substrate binding occurs on the S = 3/2 surface, oxidative addition to an η1-allyl intermediate only occurs on the S = 1/2 surface. Since this spin state

  低配位、高自旋 (S = 3/2) 有机金属铁 (I) 配合物是烯烃异构化的催化剂。实验和计算机制研究的结合支持了一种通过烯丙基机制发生烯烃异构化的机制。重要的是，虽然底物结合发生在 S = 3/2 表面，但对 η1-烯丙基中间体的氧化加成仅发生在 S = 1/2 表面。由于这种自旋态变化只有在烯烃底物结合时才有可能，由于高自旋态的反键相互作用，催化剂对典型的 σ 碱毒物表现出高度的免疫力。
• Cryptoregiochemistry of a Brassica napus fatty acid desaturase (FAD3): a kinetic isotope effect study
  作者：Christopher K. Savile、Darwin W. Reed、Dauenpen Meesapyodsuk、Patrick S. Covello、Peter H. Buist

  DOI：10.1039/b008111f

  日期：——

  α-Linolenic acid ((Z,Z,Z)-octadeca-9,12,15-trienoic acid) is biosynthesized by a series of regio- and stereoselective dehydrogenation reactions which are catalyzed by a set of enzymes known as fatty acid desaturases. As part of ongoing research into the mechanism of these remarkable catalysts, we have examined the cryptoregiochemistry (site of initial oxidation) of extraplastidial ω − 3 desaturation as it occurs in the commercially important plant Brassica napus (oilseed rape or canola). The individual deuterium kinetic isotope effects associated with the C–H bond cleavages at C-15 and C-16 of a thiaoleoyl analogue were measured using a convenient in vivo yeast expression system. Competition experiments using appropriately deuterium-labelled 7-thia substrates revealed a large kinetic isotope effect (KIE) (kH/kD = 7.5 ± 0.4) for the C–H bond-breaking step at C-15 while the C–H bond cleavage at C-16 was found to be insensitive to deuterium substitution (kH/kD = 1.0 ± 0.14). These results point to C-15 as the site of initial oxidation in ω − 3 desaturation since the first chemical step in this type of reaction is rupture of a strong, unactivated C–H bond—an energetically difficult process which typically exhibits a large KIE.

  α-亚麻酸（(Z,Z,Z)-十八碳-9,12,15-三烯酸）是由一系列区域选择性和立体选择性脱氢反应生物合成的，这些反应由一组被称为脂肪酸去饱和酶的酶催化。作为对这些卓越催化剂机理的持续研究的一部分，我们研究了重要经济作物油菜（油籽或菜籽）中质体外ω-3去饱和作用的隐秘化学选择性（初始氧化位点）。通过一个方便的活体内酵母表达系统，测量了噻酯类似物C-15和C-16处的C-H键断裂所伴随的单独氘动力学同位素效应。使用适当氘标记的7-噻基底物的竞争实验揭示了C-15处的C-H键断裂步骤具有较大的动力学同位素效应（KIE）（kH/kD = 7.5 ± 0.4），而C-16处的C-H键断裂则对氘置换不敏感（kH/kD = 1.0 ± 0.14）。这些结果表明，C-15是ω-3去饱和作用中初始氧化的位点，因为在这种类型的反应中，第一个化学步骤是断裂一个强力的、未活化的C-H键——这是一个能量上困难的过程，通常表现出较大的KIE。
• Experimental and Theoretical Study of Tunable 1,3-Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd-Catalyzed Cross-Coupling Reactions
  作者：Jinbo Zhao、Yu Liu、Qiwen He、Yuxue Li、Shengming Ma

  DOI：10.1002/chem.200900325

  日期：2009.10.26

  transmetallation and Pd‐catalyzed Negishi coupling reactions afforded 1,1‐diaryl or 1,3‐diaryl allenes with high selectivity. Deuterium‐labeling cross experiments indicated that an intermolecular lithiation process occurred in both 1,3‐lithium shift conditions (conditions B and D). 1‐Arylalka‐1,2‐diene was confirmed experimentally to be the intermediate. A computational study at the B3LYP level for the isomerization

  在1-芳基烷基-1-炔的去质子化反应中，实现了从1-芳基烷基1,2-二烯-1-基锂到1-芳基烷基1,2-dien-3-基锂的异构化的高度选择性调节（条件A和B）和1-芳基丁3烯-1-炔与烷基锂的碳环化反应（条件C和D）。随后的金属转移和Pd催化的Negishi偶联反应提供了具有高选择性的1,1-二芳基或1,3-二芳基异戊烯。氘标记的交叉实验表明，分子间锂化过程发生在两种1,3-锂转移条件下（条件B和D）。实验证明1-芳基1,2-二烯是中间体。在B3LYP级别进行异构化的计算研究表明，在3位H的酸度比在1苯基1，2-丁二烯1位的H的酸度高。在条件B下，我镨2 NH作为质子载体完成1,3-锂移。在溶剂化模型中确定速率的步骤的总活化势垒为≈21.0kcal mol -1，这表明异构化在室温下是合理的。对于在条件D下的异构化，DFT计算表明添加TMEDA（四甲基乙二胺）和HMPA（六甲基磷酰胺）会
• Synthesis of sequentially deuterated 1-n-Butyl-3-methylimidazolium ionic liquids
  作者：Alexander Khrizman、Hiu Yan Cheng、Guillermo Moyna

  DOI：10.1002/jlcr.1884

  日期：2011.6.30

  Deuterium isotopologues of the ionic liquid (IL) 1–n-butyl-3-methylimidazolium chloride ([C4mim]Cl) sequentially labeled on the C-1″, C-1′, C-2′, C-3′, and C-4′ positions of the N-alkyl groups were prepared following a strategy that minimizes the number of distinct reactions through the use of analogous synthetic routes. In several cases, good yields after the initial deuterium incorporation reaction were achieved by combining well-established chemical transformations into efficient single-step processes. Copyright © 2011 John Wiley & Sons, Ltd.

  氘同位素的离子液体（IL）1–n-丁基-3-甲基咪唑氯化物（[C4mim]Cl）在N-烷基侧基的C-1″、C-1′、C-2′、C-3′和C-4′位点上逐步标记，采用了一种通过类似合成路径最小化不同反应数量的策略。在多个案例中，通过将成熟的化学转化结合为高效的单一步骤过程，初步氘掺入反应后获得了良好的产率。版权 © 2011 John Wiley & Sons, Ltd.