β-Acetoxyglutaronitrile | 58048-90-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: β-Acetoxyglutaronitrile
• 英文别名: InChI=1/C7H8N2O2/c1-6(10)11-7(2-4-8)3-5-9/h7H,2-3H2,1H；1,3-dicyanopropan-2-yl acetate
• CAS: 58048-90-1
• 化学式: C₇H₈N₂O₂
• 分子量: 152.153
• InChiKey: FKKMPYMFRFERPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  β-Acetoxyglutaronitrile 反应 65.0h， 以45%的产率得到(+/-)-3-O-(acetyl)-4-cyanobutanoic acid
  参考文献：
  名称：

  Stereoselective hydrolysis of nitriles and amides under mild conditions using a whole cell catalyst

  摘要：

  An immobilised whole cell Rhodococcus sp. (SP 361) has been shown to be an effective catalyst for the stereoselective hydrolysis of both racemic and prochiral nitrile containing compounds. 2-Alkyl-arylacetonitriles 6a-8a were hydrolysed to (S)-acids and (R)-amides whereas the closely related substrate 9a gave the (R)-acid. A series of prochiral dinitriles 10a-13a were hydrolysed to the corresponding (S)-acids with e.e.'s 22-84%. Models to account for the stereoselectivity of the enzymic hydrolyses have been proposed.

  DOI：

  10.1016/s0957-4166(00)80215-3
• 作为产物：
  描述：

  3-羟基戊二腈 、 乙酸酐 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 以92%的产率得到β-Acetoxyglutaronitrile
  参考文献：
  名称：

  Selective Hydrolysis of Aliphatic Dinitriles to Monocarboxylic Acids by a Nitrilase from Arabidopsis thaliana

  摘要：

  描述了使用来自阿拉伯芥（Arabidopsis thaliana）的重组植物腈水解酶在大肠杆菌中表达，对多种二腈（dinitriles）进行水解的过程，这些二腈包括α,ω-二氰烷烃1、β-取代的戊二腈5和γ-氰基庚腈7。二腈1a-f转化为ω-氰基羧酸2a-f的水解转化率和选择性依赖于链长。从丙二腈（1a）到辛烯二腈（1f），酶活性显著增加。然而，选择性与转化速率并不相关。对于6个碳原子以下的链长，氰基羧酸是唯一的产品，即使起始材料完全转化。庚腈（1e）在转化率达到73%时，仅被水解为氰基羧酸2e，而未形成二酸（<1%）。戊二腈5a-c也被水解为相应的氰基丁酸6a-c，具有完美的选择性。腈水解酶专门水解7的原料氰基，生成3,5-二氰基庚酸（8a），相比于未取代的庚腈（1e），选择性略有降低。如果在转化率≤90%时终止水解，可以以72%的产率（转化率92%）单独分离出纯8a。在将8a酯化为甲酯8b后，只有5-氰基基团而不是酯功能被酶催化水解，生成氰基庚二酸单酯（10）。

  DOI：

  10.1055/s-2001-17523

文献信息

• Polyfunctional Aliphatic Compounds. II.¹ The Cyclization of Dinitriles by Anhydrous Halogen Acids. Pyridines
  作者：Francis Johnson、J. P. Panella、A. A. Carlson、D. H. Hunneman

  DOI：10.1021/jo01054a044

  日期：1962.7
• Crosby John A., Parratt Julian S., Turner Nicholas J., Tetrahedron, 3 (1992) N 12, S 1547-1550
  作者：Crosby John A., Parratt Julian S., Turner Nicholas J.

  DOI：——

  日期：——
• Stereoselective hydrolysis of nitriles and amides under mild conditions using a whole cell catalyst
  作者：Timothy Beard、Mark A. Cohen、Julian S. Parratt、Nicholas J. Turner、John Crosby、Jock Moilliet

  DOI：10.1016/s0957-4166(00)80215-3

  日期：1993.6

  An immobilised whole cell Rhodococcus sp. (SP 361) has been shown to be an effective catalyst for the stereoselective hydrolysis of both racemic and prochiral nitrile containing compounds. 2-Alkyl-arylacetonitriles 6a-8a were hydrolysed to (S)-acids and (R)-amides whereas the closely related substrate 9a gave the (R)-acid. A series of prochiral dinitriles 10a-13a were hydrolysed to the corresponding (S)-acids with e.e.'s 22-84%. Models to account for the stereoselectivity of the enzymic hydrolyses have been proposed.
• Selective Hydrolysis of Aliphatic Dinitriles to Monocarboxylic Acids by a Nitrilase from Arabidopsis thaliana
  作者：Franz Effenberger、Steffen Oßwald

  DOI：10.1055/s-2001-17523

  日期：——

  The hydrolysis of a variety of dinitriles including α,ω-dicyanoalkanes 1, β-substituted glutaronitriles 5, and γ-cyanopimelonitrile 7 with a recombinant plant nitrilase from Arabidopsis thaliana, expressed in E. coli, is described. Conversion rate and selectivity of the hydrolysis of dinitriles 1a-f to ω-cyanocarboxylic acids 2a-f depend on the chain length. The enzyme activity markedly increases from malononitrile (1a) to octanedinitrile (1f). The selectivity, however, does not correlate with the rates. Up to a chain length of 6 C-atoms, the cyanocarboxylic acid is the only product, even at complete conversion of the starting material. Pimelonitrile (1e) is hydrolyzed to the cyanocarboxylic acid 2e without formation of diacid (<1%) up to 73% conversion. Glutaronitriles 5a-c were also hydrolyzed to the corresponding cyanobutanoic acids 6a-c with perfect selectivity. The nitrilase hydrolyzes exclusively the primary cyano group of 7 to give 3,5-dicyanoheptanoic acid (8a), whereby the selectivity is slightly reduced compared to the unsubstituted pimelonitrile (1e). If the hydrolysis is terminated at conversions ≤90%, pure 8a can be isolated in 72% yield (92% referred to conversion). After esterification of 8a to the methyl ester 8b, only the 5-cyano group but not the ester function was hydrolyzed enzymatically to give cyanoheptanedioic acid monoester (10).

  描述了使用来自阿拉伯芥（Arabidopsis thaliana）的重组植物腈水解酶在大肠杆菌中表达，对多种二腈（dinitriles）进行水解的过程，这些二腈包括α,ω-二氰烷烃1、β-取代的戊二腈5和γ-氰基庚腈7。二腈1a-f转化为ω-氰基羧酸2a-f的水解转化率和选择性依赖于链长。从丙二腈（1a）到辛烯二腈（1f），酶活性显著增加。然而，选择性与转化速率并不相关。对于6个碳原子以下的链长，氰基羧酸是唯一的产品，即使起始材料完全转化。庚腈（1e）在转化率达到73%时，仅被水解为氰基羧酸2e，而未形成二酸（<1%）。戊二腈5a-c也被水解为相应的氰基丁酸6a-c，具有完美的选择性。腈水解酶专门水解7的原料氰基，生成3,5-二氰基庚酸（8a），相比于未取代的庚腈（1e），选择性略有降低。如果在转化率≤90%时终止水解，可以以72%的产率（转化率92%）单独分离出纯8a。在将8a酯化为甲酯8b后，只有5-氰基基团而不是酯功能被酶催化水解，生成氰基庚二酸单酯（10）。

表征谱图