羟基(苯基)乙腈 | 28549-12-4

• 物质功能分类: 有机原料 - 醇、酚、酚醇类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 羟基(苯基)乙腈
• 中文别名: 禾大壮；环草丹；杀草丹；禾草敌；S-(-)-苯乙醇腈
• 英文名称: (S)-mandelonitrile
• 英文别名: (S)-2-hydroxy-2-phenylacetonitrile；2-hydroxy-2-phenylacetonitrile；(2S)-2-hydroxy-2-phenylacetonitrile
• CAS: 28549-12-4
• 化学式: C₈H₇NO
• 分子量: 133.15
• InChiKey: NNICRUQPODTGRU-MRVPVSSYSA-N

物化性质

• 沸点：
  282.7±20.0 °C(Predicted)
• 密度：
  1.169±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  羟基(苯基)乙腈 在 盐酸 、 sodium tetrahydroborate 作用下， 反应 2.0h， 生成 去甲伪麻黄碱
  参考文献：
  名称：

  Applications of Optically Active Aryl Cyanohydrins in the Synthesis of α-Hydroxy Aldehydes, α-Hydroxy Ketones and β-Hydroxy Amines

  摘要：

  从芳基醛中制备的高光学纯度氰基卤素可转化为 α-羟基醛、β-羟基酮和β-羟基胺，且无任何外消旋化现象，在新引入的立体中心处，赤式二对映异构体通常具有良好的立体选择性（90%）。

  DOI：

  10.1071/ch9902045
• 作为产物：
  描述：

  (R)-(+)-苯乙醇腈 在 甲烷磺酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲醇 为溶剂， 生成 羟基(苯基)乙腈
  参考文献：
  名称：

  Warmerdam, E. G. J. C.; Brussee, J.; Kruse, C. G., Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 3 - 6

  摘要：

  DOI：
• 作为试剂：
  描述：

  糠醛 、 氢氰酸 在 cyclo-<(R)-phenylalanyl-(R)-histidyl> 、 羟基(苯基)乙腈 作用下， 以 甲苯 为溶剂， 反应 7.0h， 生成 (2S)-2-呋喃基(羟基)乙腈 、 (2R)-2-(2-呋喃基)-2-羟基-乙腈
  参考文献：
  名称：

  Examination and Enhancement of Enantioselective Autoinduction in Cyanohydrin Formation by Cyclo[(R)-His-(R)-Phe]

  摘要：

  The cyclic dipeptide cyclo[(R)-His-(R)-Phe] (1) has been known since 1981 to catalyze the enantioselective formation of cyanohydrins from aldehydes and HCN. Although 1 has proved to be very effective in the production of optically active cyanohydrins, the precise structure of its catalytically active form remains unresolved. The reaction of 3-phenoxybenzaldehyde and HCN in the presence of 1 has also been shown to exhibit enantioselective autocatalysis: the product (S)-3-phenoxymandelonitrile reacts with 1 to form a new, more enantioselective catalytic species. It is now demonstrated that this autocatalytic phenomenon is general and that, furthermore, it can be used to improve the enantioselectivity of cyanohydrin formation for several problematic substrates. Upon addition of a small (8 mol %) quantity of (S)-mandelonitrile or (S)-3-phenoxymandelonitrile to these reactions, the enantioselectivity of cyanohydrin formation was improved by as much as 20% ee. This effect has been ascribed to the formation of a complex between the added (S)-cyanohydrin and 1 that exhibits superior enantioselectivity to 1, either alone or complexed to the cyanohydrins of problematic substrates. A mathematical model has been developed, on the basis of a two-state equilibrium between 1 and a complex of 1 and cyanohydrin and used to explain the enantioselective autoinduction phenomenon in terms of five parameters: rate constants for the production of (R)- and (S)-cyanohydrin by both 1 and its cyanohydrin complex and an association constant for the formation of a cyanohydrin complex by 1. Two versions of this model, based on monomeric and dimeric 1, have been evaluated in light of the available data. Examination of the results reveals that the complexes of 1 and many of the cyanohydrins studied are highly enantioselective catalysts but that the complexes of 1 and cyanohydrins are only weakly associated; moreover, the complexation of 1 with most cyanohydrins leaves the rate of cyanohydrin formation unchanged, though both autocatalysis and enantioselective poisoning have been observed as well.

  DOI：

  10.1021/jo972238k

文献信息

• Substrate Evaluation of<i>Rhodococcus erythropolis</i>SET1, a Nitrile Hydrolysing Bacterium, Demonstrating Dual Activity Strongly Dependent on Nitrile Sub-Structure
  作者：Tracey M. Coady、Lee V. Coffey、Catherine O'Reilly、Claire M. Lennon

  DOI：10.1002/ejoc.201403201

  日期：2015.2

  Rhodococcus erythropolis SET1, a novel nitrile hydrolysing bacterial isolate, has been undertaken with 34 nitriles, 33 chiral and 1 prochiral. These substrates consist primarily of β-hydroxy nitriles with varying alkyl and aryl groups at the β position and containing in several compounds different substituents α to the nitrile. In the case of β-hydroxy nitriles without substitution at the α position

  红球菌 SET1 是一种新型腈水解细菌分离株，已使用 34 种腈、33 种手性和 1 种前手性进行了评估。这些底物主要由 β-羟基腈组成，在 β 位具有不同的烷基和芳基，并且在几种化合物中含有与腈不同的 α 取代基。在 α 位没有取代的 β-羟基腈的情况下，由于分离物的腈水解酶活性，酸是获得的主要产物，以及生物转化后回收的腈。出乎意料的是，当 β-羟基腈在该位置具有乙烯基时，发现酰胺是主要的水解产物。为了进一步探索这种行为，评估了在 α 位置包含吸电子基团的其他相关底物，在 SET1 存在下的生物转化过程中也观察到了酰胺。因此，这种新的分离物也证明了对似乎是底物依赖性的腈类的 NHase 活性。
• Probing the enantioselectivity of a diverse group of purified cobalt-centred nitrile hydratases
  作者：S. van Pelt、M. Zhang、L. G. Otten、J. Holt、D. Y. Sorokin、F. van Rantwijk、G. W. Black、J. J. Perry、R. A. Sheldon

  DOI：10.1039/c0ob01067g

  日期：——

  In this study a diverse range of purified cobalt containing nitrile hydratases (NHases, EC 4.2.1.84) from Rhodopseudomonas palustris HaA2 (HaA2), Rhodopseudomonas palustris CGA009 (009), Sinorhizobium meliloti 1021 (1021), and Nitriliruptor alkaliphilus (iso2), were screened for the first time for their enantioselectivity towards a broad range of chiral nitriles. Enantiomeric ratios of >100 were found for the NHases from HaA2 and CGA009 on 2-phenylpropionitrile. In contrast, the Fe-containing NHase from the well-characterized Rhodococcus erythropolis AJ270 (AJ270) was practically aselective with a range of different α-phenylacetonitriles. In general, at least one bulky group in close proximity to the α-position of the chiral nitriles seemed to be necessary for enantioselectivity with all NHases tested. Nitrile groups attached to a quaternary carbon atom were only reluctantly accepted and showed no selectivity. Enantiomeric ratios of 80 and >100 for AJ270 and iso2, respectively, were found for the pharmaceutical intermediate naproxennitrile, and 3-(1-cyanoethyl)benzoic acid was hydrated to the corresponding amide by iso2 with an enantiomeric ratio of >100.

  在本研究中，首次对来自红假单胞菌HaA2（HaA2）、红假单胞菌CGA009（009）、豌豆根瘤菌1021（1021）和嗜碱氮裂解菌（iso2）的多种纯化钴含氮裂解酶（NHases，EC 4.2.1.84）对一系列手性腈的立体选择性进行了筛选。对于2-苯基丙腈，来自HaA2和CGA009的NHases的立体异构比大于100。相比之下，来自已知红球菌AJ270（AJ270）的含铁NHase对一系列不同α-苯基乙腈实际上没有选择性。总的来说，对于所有测试的NHases来说，似乎至少需要一个在α-位附近的大体积基团才能实现立体选择性。连接在四级碳原子上的腈基团仅勉强被接受，并且没有显示出选择性。对于药物中间体萘普生腈，AJ270和iso2的立体异构比分别为80和大于100；iso2还将3-（1-氰乙基）苯甲酸水合为相应的酰胺，立体异构比大于100。
• Unsymmetric salen ligands bearing a Lewis base: intramolecularly cooperative catalysis for cyanosilylation of aldehydes
  作者：Ye-Qian Wen、Wei-Min Ren、Xiao-Bing Lu

  DOI：10.1039/c1ob05695f

  日期：——

  A series of unsymmetric salen ligands derived from 1,2-diaminocyclohexane bearing an appended Lewis base on the three-position of one aromatic ring were synthesized by the reaction of various functional salicyaldehydes with the condensation product of 1,2-diaminocyclohexane mono(hydrogen chloride) and 3,5-di-tert-butylsalicylaldehyde. These ligands in conjunction with Ti(OiPr)4 exhibited excellent activity in catalyzing the cyanosilylation of aldehydes with trimethylsilyl cyanide (TMSCN) at mild conditions. The highest activity was observed in the catalyst system with regard to the salen ligand bearing a diethylamino group, which proved to be active even at a high [aldehyde]/[catalyst] ratio up to 50000. In a low catalyst loading of 0.05 mol%, the quantitative conversion of benzaldehyde to the corresponding cyanosilylation product was found within 10 min. at ambient temperature. An intramolecularly cooperative catalysis was proposed wherein the central metal Ti(IV) is suggested to play a role of Lewis acid to activate aldehydes while the appended Lewis base to activate TMSCN.

  一系列基于1,2-二氨基环己烷并带有附加路易斯碱于一个芳环3号位的不对称salen配体，通过不同功能的水杨醛与1,2-二氨基环己烷单(盐酸)和3,5-二叔丁基水杨醛的缩合产物反应合成。这些配体与Ti(OiPr)4联合展现出了在温和条件下催化醛与三甲基氰硅烷(TMSCN)的氰硅化反应的优秀活性。在含有二乙氨基的salen配体的催化体系中观察到了最高的活性，即使在高达50000的[醛]/[催化剂]比例下也显示出活性。在低催化剂负载量0.05 mol%下，室温下10分钟内可以发现苯甲醛到相应氰硅化产物的定量转化。提出了一种分子内协同催化，其中中心金属Ti(IV)被认为扮演了激活醛的路易斯酸的角色，而附加的路易斯碱则激活了TMSCN。
• Asymmetric trimethylsilylcyanation of aldehydes utilizing chiral bismuth compounds. A frontier in bismuth mediated synthetic reactions
  作者：Makoto Wada、Toshikazu Takahashi、Terutomo Domae、Tomohiro Fukuma、Norikazu Miyoshi、Keith Smith

  DOI：10.1016/s0957-4166(97)00570-3

  日期：1997.12

  found to work efficiently as a versatile catalyst for cyanation of aldehydes with trimethylsilyl cyanide to afford the corresponding cyanohydrins in high yields. Triphenylbismuthan (Ph3Bi) is also effective. The reaction has been applied to the asymmetric cyanation of a variety of aldehydes in high yields with moderate to good enantioselectivities by use of a chiral bismuth catalyst prepared in situ

  发现氯化铋（III）（BiCl 3）可以有效地用作通用的催化剂，用三甲基甲硅烷基氰化物氰化醛，从而以高收率提供相应的氰醇。三苯基双muthan（Ph 3 Bi）也有效。通过使用由BiCl 3和（2 R，3 R）-（+）-酒石酸二乙酯原位制备的手性铋催化剂，该反应已用于高产率，中等至良好对映选择性的各种醛的不对称氰化反应。。
• Enantioselective cyanosilylation of aldehydes catalyzed by novel camphor derived Schiff bases-titanium(IV) complexes
  作者：Ewelina Błocka、Mariusz J. Bosiak、Mirosław Wełniak、Agnieszka Ludwiczak、Andrzej Wojtczak

  DOI：10.1016/j.tetasy.2014.03.001

  日期：2014.4

  Five tridentate Schiff bases have been prepared from (1R,2S,3R,4S)-3-amino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol and salicylaldehydes. X-ray structure investigation revealed differences in their molecular conformation, and their titanium(IV) complexes have been studied with NMR techniques. Among them the complex with the Schiff base obtained from 2-hydroxy-3-isopropylbenzaldehyde, is the most selective

  五三齿席夫碱已经从（1制备- [R，2小号，3 - [R，4小号）-3-氨基- 1,7,7-三甲基二环[2.2.1]庚-2-醇和水杨醛。X射线结构的调查显示在它们的分子构象的差异，和它们的钛（IV）络合物进行了研究NMR技术。它们之间的复合物与由2-羟基-3-异丙基苯甲醛得到的席夫碱，为脂肪族，脂环族，芳族，杂芳族和醛的硅氰化反应最有选择性的催化剂。最高的对映选择性，> 99％时，在加入三甲基氰硅烷的给肉桂醛实现。