3-甲基丁烷-1,2-二醇 | 50468-22-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3-甲基丁烷-1,2-二醇
• 英文名称: 3-methylbutane-1,2-diol
• 英文别名: 3-methyl-1,2-butanediol
• CAS: 50468-22-9
• 化学式: C₅H₁₂O₂
• 分子量: 104.149
• InChiKey: HJJZIMFAIMUSBW-UHFFFAOYSA-N

物化性质

• 熔点：
  50.86°C (estimate)
• 沸点：
  209.24°C (rough estimate)
• 密度：
  0.9987
• LogP：
  -0.462 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  7
• 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：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 海关编码：
  2905399090

反应信息

• 作为反应物：
  描述：

  3-甲基丁烷-1,2-二醇 在 R(+)-alpha-甲基苄胺 、 (R)-ω-transaminase from Mycobacterium vanbaalenii 、 2,3 butanediol dehydrogenase from Bacillus subtilis 、 polyol dehydrogenase from from Gluconobacter oxydans 、 β-烟酰胺腺嘌呤二核苷酸 作用下， 生成 L-缬氨醇
  参考文献：
  名称：

  外消旋环氧化合物的不对称开环，可通过辅因子自足的级联生物催化系统进行对映选择性合成（S）-β-氨基醇†

  摘要：

  报道了一种新的一锅式环氧水解酶/醇脱氢酶/转氨酶级联方法，用于外消旋环氧化物不对称开环成对映体纯的β-氨基醇。（S）-β-氨基醇的产物是从易获得的外消旋环氧化物中以97-99％ee和79-99％的转化率获得的。

  DOI：

  10.1039/c8cy02377h
• 作为产物：
  描述：

  2-羟基-3-甲基丁酸 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以75%的产率得到3-甲基丁烷-1,2-二醇
  参考文献：
  名称：

  Reactivity of the lithium anion of the (S,S)-bis-p-tolylsulfinyl methane. A versatile synthesis of enantiopure alkylidene 1,1-bis-p-tolylsulfoxides

  摘要：

  We describe herein a new synthesis of enantiopure alkylidene 1,1-bis-p-tolyl-sulfoxides (5), based on a two-steps sequence. The first one involves the alkylation of the lithium anion of the (S,S)-bis-p-tolylsulfinylmethane (1) with aldehydes. The second one consists in a mild dehydration of the sulfinyl alcohols 3 and 4 with the morpho CDI reagent. Some features (reactivity, diastereoselectivity) of the alkylation reaction are discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01210-4

文献信息

• Synthesis of 1,1-Dibromo-3-hydroxyalkanes via Opening of Cyclic Sulfates
  作者：Hans Christian Stiasny

  DOI：10.1055/s-1996-4193

  日期：1996.2

  3-Alkoxy-1,1-dibromoalkanes are interesting substrates for diastereoselective bromine/lithium exchange reactions. A general route to the precursor 1,1-dibromo-3-hydroxyalkanes is described here via reaction of dibromomethyllithium with cyclic sulfates of 1,2-diols.

  3-烷氧基-1,1-二溴烷是用于二氨基酸选择性溴锂交换反应的有趣底物。本文通过二溴甲基锂与1,2-二醇的环硫酸酯反应，描述了一种制备前体1,1-二溴-3-羟基烷的通用路线。
• Determination of enantiomeric purity of glycols RCHOHCH2OH
  作者：Ernest L. Eliel、Kwang-Youn Ko

  DOI：10.1016/s0040-4039(00)88164-2

  日期：1983.1

  The enantiomeric purity of primary-secondary glycols, RCHOHCH2OH, is conveniently determined by conversion to a pair of epimeric 1,3-dioxolanes through condensation with benzaldehyde, followed by NMR spectroscopy in presence of a chiral shift reagent with observation of the benzylic protons.

  伯-仲二醇RCHOHCH 2 OH的对映体纯度可通过与苯甲醛缩合转化为一对对映体1,3-二氧戊环方便地确定，然后在手性移位试剂存在下进行NMR光谱分析并观察苄基质子。
• Reduction of aromatic and aliphatic keto esters using sodium borohydride/MeOH at room temperature: a thorough investigation
  作者：Juryoung Kim、Kathlia A. De Castro、Minkyung Lim、Hakjune Rhee

  DOI：10.1016/j.tet.2010.04.062

  日期：2010.6

  Reduction of keto esters is a valuable alternative to produce diols. Sodium borohydride/MeOH system at room temperature and short reaction time efficiently reduced α, β, γ, and δ-keto esters having α-keto esters as the most reactive. The ester functionality was reduced effectively due to the presence of oxo group that somehow facilitates the formation of ring intermediate. As expected, the chemoselective

  还原酮酯是生产二醇的有价值的替代方法。在室温和短的反应时间下，硼氢化钠/ MeOH系统有效地还原了以α-酮酸酯为最具反应性的α，β，γ和δ-酮酸酯。由于存在以某种方式促进环中间体形成的氧代基团，有效地降低了酯的官能度。如预期的那样，化学选择性实验表明，使用该系统不会降低酯的官能度。这项研究提出了各种酮酯向其相应的二醇的简单，简便且良性的还原过程。
• Synthesis of Some 2'-C-Alkyl Derivatives of 9-(2-Phosphonomethoxyethyl)adenine and Related Compounds
  作者：Hana Dvořáková、Antonín Holý、Ivan Rosenberg

  DOI：10.1135/cccc19942069

  日期：——

  To study the effect of β-substitution in 2'-alkyl derivatives of 9-(2-phosphonomethoxyethyl)adenine (Ia) on the antiviral activity or group specificity, these derivatives were synthesized. 9-(2-Hydroxyalkyl)adenines VIII were prepared by alkylation of adenine with suitably substituted oxiranes XIII or 2-hydroxyalkyl p-toluenesulfonates IV and VI. After protection of the adenine amino group by benzoylation (compounds IX) or amidine formation (compounds X), the intermediates were alkylated with diisopropyl p-toluenesulfonyloxymethanephosphonate (XI) in the presence of sodium hydride. After deprotection, the obtained phosphonate diesters XII were converted into phosphonic acids I by transsilylation and hydrolysis. This synthetic scheme was used for the preparation of ethyl (Ie), propyl (If), 2-propyl (Ig), 2-methylpropyl (Ih), cyclopropyl (Ii), cyclohexyl (Ij), benzyl (Ik) and phenyl (Il) derivatives. The 2'-trifluoromethyl derivative XXIIa was prepared analogously from 9-(2-hydroxy-3,3,3-trifluoropropyl)adenine (XXa), obtained by alkylation of adenine sodium salt with 2-hydroxy-3,3,3-trifluoropropyl bromide. 2'-Trimethylsilyl derivative XIXa was obtained by alkylation of adenine with 2-diisopropylphosphonomethoxy-3-(4-toluenesulfonyloxy)propyltrimethylsilane (XVII) followed by transsilylation and hydrolysis of diester XVIIIa. 2,6-Diaminopurine derivatives XVIIId and XXIIb were obtained analogously. 9-(3-Phosphonomethoxybutyl)adenine (XXVIII) and 9-(2-methyl-2-phosphonomethoxypropyl)adenine (XXXV) were prepared from the corresponding hydroxy derivatives XXVIb and XXXII, respectively, by the same reaction pathway as derivatives I.

  为了研究9-(2-磷酸甲氧基乙基)腺嘌呤（Ia）的2'-烷基衍生物中β-取代对抗病毒活性或基团特异性的影响，合成了这些衍生物。通过将腺嘌呤与适当取代的环氧烷（XIII）或2-羟基烷基对甲苯磺酸酯（IV和VI）烷基化制备了9-(2-羟基烷基)腺嘌呤（VIII）。在通过苯甲酰化（化合物IX）或酰胺化（化合物X）保护腺嘌呤氨基后，中间体在氢化钠存在下与二异丙基对甲苯磺酸氧甲基膦酸酯（XI）烷基化。去保护后，得到的膦酸二酯（XII）通过转硅烷化和水解转化为膦酸（I）。这种合成方案用于制备乙基（Ie）、丙基（If）、2-丙基（Ig）、2-甲基丙基（Ih）、环丙基（Ii）、环己基（Ij）、苄基（Ik）和苯基（Il）衍生物。2'-三氟甲基衍生物（XXIIa）类似地从9-(2-羟基-3,3,3-三氟丙基)腺嘌呤（XXa）制备，后者通过腺嘌呤钠盐与2-羟基-3,3,3-三氟丙基溴化物烷基化获得。2'-三甲基硅基衍生物（XIXa）通过腺嘌呤与2-二异丙基膦酸甲氧基-3-(4-对甲苯磺酰氧基)丙基三甲基硅烷（XVII）烷基化后，转硅烷化和水解膦酸二酯（XVIIIa）获得。2,6-二氨基嘌呤衍生物（XVIIId和XXIIb）类似地获得。9-(3-磷酸甲氧基丁基)腺嘌呤（XXVIII）和9-(2-甲基-2-磷酸甲氧基丙基)腺嘌呤（XXXV）分别从相应的羟基衍生物（XXVIb和XXXII）通过与衍生物I相同的反应途径制备。
• Product distributions from the OH radical-induced oxidation of but-1-ene, methyl-substituted but-1-enes and isoprene in NOx-free air
  作者：Heinz-Jürgen Benkelberg、Olaf Böge、Ralph Seuwen、Peter Warneck

  DOI：10.1039/b002053m

  日期：——

  Product distributions resulting from the OH-induced oxidation of but-1-ene, 2-methylbut-1-ene, 3-methylbut-1-ene and isoprene in air were measured in the absence of nitrogen oxides and compared with predictions based on currently accepted oxidation mechanisms. In the case of butenes, the observed distributions of carbonyl compounds, hydroxyketones, hydroxyalkanals and diols were evaluated to obtain

  在没有氮氧化物的情况下测量了空气中 OH 诱导的 1-1-烯、2-甲基丁-1-烯、3-甲基丁-1-烯和异戊二烯的氧化产物分布，并与基于目前的预测进行了比较公认的氧化机制。在丁烯的情况下，对观察到的羰基化合物、羟基酮、羟基链烷醛和二醇的分布进行了评估，以获得 OH 自由基初始攻击双键外部位置的概率（对于 2-Me-​​but，γ = 0.90 ± 0.03 -1-ene 和 γ = 0.76 ± 0.05（对于 but-1-ene 和 3-Me-but-1-ene），用于在二级 β-羟基过氧自由基的自反应中形成稳定产物的概率（kssb /kss = 0.29 ± 0.07 对于丁-1-烯和 kssb/kss = 0.19 ± 0.06 对于 3-Me-but-1-ene)，以及与氧气反应的比率 s。β-羟基烷氧基自由基的分解，k3[O2]/(k4 + k3[O2]) = 0.25 ± 0.04