rac-3-hydroxy-3-methyl-4-pentenenitrile | 665-81-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: rac-3-hydroxy-3-methyl-4-pentenenitrile
• 英文别名: 3-hydroxy-3-methylpent-4-enenitrile；4-Cyano-3-methyl-1-buten-3-ol；1-Cyan-2-hydroxy-2-methylbuten-3
• CAS: 665-81-6
• 化学式: C₆H₉NO
• 分子量: 111.144
• InChiKey: BDIMTIXTEJCWDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  rac-3-hydroxy-3-methyl-4-pentenenitrile 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以83%的产率得到5-Amino-3-methyl-1-penten-3-ol
  参考文献：
  名称：

  Sila-Riechstoffe und Riechstoff-Isostere, 13. Mitt.Grimmsche Hydridisostere im Bereich der Duftstoffklasse des Linalools

  摘要：

  Substitution of the (CH3)(3)CH=CH group by (CH3)(2)C=N in linalool as well as by the (CPT3)(2)CH-CH2 group in linalool and in sila-linalool does not lead to noticeable changes of their scent qualities. On the contrary, substitution of the OH group at the tertiary C atom by NH2 or CH3 - hydride isosteric to OH according to Grimm - affords fishy or etheric instead of the original flowery smells thus indicating a transition to different basic classes of odor. Similar results were obtained with the linalool-like scents of benzyldimethylcarbinol and phenylethyldimethylcarbinol. Therefore the theory of Amoore, after which only shape and size of molecules are ruling their odor qualities, must be called in question.

  DOI：

  10.1007/bf00813801
• 作为产物：
  描述：

  1-氯-2-甲基丁-3-烯-2-醇 、 氰化钾 在 18-冠醚-6 作用下， 以 乙腈 为溶剂， 以36%的产率得到rac-3-hydroxy-3-methyl-4-pentenenitrile
  参考文献：
  名称：

  Sila-Riechstoffe und Riechstoff-Isostere, 13. Mitt.Grimmsche Hydridisostere im Bereich der Duftstoffklasse des Linalools

  摘要：

  Substitution of the (CH3)(3)CH=CH group by (CH3)(2)C=N in linalool as well as by the (CPT3)(2)CH-CH2 group in linalool and in sila-linalool does not lead to noticeable changes of their scent qualities. On the contrary, substitution of the OH group at the tertiary C atom by NH2 or CH3 - hydride isosteric to OH according to Grimm - affords fishy or etheric instead of the original flowery smells thus indicating a transition to different basic classes of odor. Similar results were obtained with the linalool-like scents of benzyldimethylcarbinol and phenylethyldimethylcarbinol. Therefore the theory of Amoore, after which only shape and size of molecules are ruling their odor qualities, must be called in question.

  DOI：

  10.1007/bf00813801

文献信息

• Ruthenium-catalyzed formation of pyrazoles or 3-hydroxynitriles from propargyl alcohols and hydrazines
  作者：Julia Kaufmann、Elisabeth Jäckel、Edgar Haak

  DOI：10.24820/ark.5550190.p010.893

  日期：——

  Functionalized pyrazoles are generated from secondary propragyl alcohols and hydrazines in a rutheniumcatalyzed cascade process, consisting of redox isomerization, Michael addition, cyclocondensation and dehydrogenation steps. The same bifunctional catalyst mediates the conversion of tertiary propargyl alcohols with hydrazine to 3-hydroxynitriles via anti-Markovnikov hydroamination followed by elimination

  官能化吡唑是在钌催化的级联过程中由仲丙醇和肼生成的，包括氧化还原异构化、迈克尔加成、环缩合和脱氢步骤。相同的双功能催化剂通过反马尔可夫尼科夫加氢胺化随后消除氨来介导炔丙醇叔醇与肼的转化为 3-羟基腈。
• Regiospecific opening of 1,2-expoxides with acetone cyanohydrin under mildly basic conditions
  作者：David Mitchell、Thomas M Koenig

  DOI：10.1016/s0040-4039(00)92067-7

  日期：1992.6

  Acetone cyanohydrin with stoichiometic triethylamine opens epoxides regiospecifically to give β-hydroxy nitriles. As expected, addition of cyanide occurs at the least substituted carbon.

  丙酮氰醇与化学计量的三乙胺在区域上特异性地打开环氧化物以生成β-羟基腈。如所期望的，在至少取代的碳上发生氰化物的添加。
• Enantioselective Ring Opening of Epoxides with Cyanide Catalysed by Halohydrin Dehalogenases: A New Approach to Non-Racemic β-Hydroxy Nitriles
  作者：Maja Majerić Elenkov、Bernhard Hauer、Dick B. Janssen

  DOI：10.1002/adsc.200505333

  日期：2006.3

  Halohydrin dehalogenases (HheA, HheB and HheC) were found to efficiently catalyse a carbon-carbon bond forming reaction between terminal aliphatic epoxides and cyanide, yielding β-hydroxy nitriles. With all three enzymes nucleophilic ring opening of epoxides proceeds with high regioselectivity to the β-carbon atom. Activity, enantioselectivity and enantiopreference depend on the type of enzyme and

  发现卤代醇脱卤素酶（HheA，HheB和HheC）可有效催化末端脂肪族环氧化物与氰化物之间的碳-碳键形成反应，生成β-羟基腈。通过所有这三种酶，环氧化物的亲核开环以对β-碳原子的高区域选择性进行。活性，对映选择性和对映选择性取决于酶的类型和底物结构。发现HheC在测试的酶中具有最高的选择性。对单取代环氧化物的对映选择性从中等到高（E = 5–106）变化，而2,2-二取代环氧化物的拆分以非常高的对映选择性（E= 141和200）。结果表明，卤代醇脱卤酶可能成为从外消旋环氧化物容易地制备对映纯β-羟基腈的有吸引力的催化剂。
• Sauleau,A. et al., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1979, vol. 289, p. 105 - 108
  作者：Sauleau,A. et al.

  DOI：——

  日期：——
• SAULEAU A.; SAULEAU J.; HUET J., C. R. ACAD. SCI., 1979 C 289, NO 3, 105-108
  作者：SAULEAU A.、 SAULEAU J.、 HUET J.

  DOI：——

  日期：——