phenyl 2-cyanobenzoate | 216585-42-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 缩酚酸和缩酚酸环醚类
• 英文名称: phenyl 2-cyanobenzoate
• 英文别名: phenyl o-cyanobenzoate；2-cyano-benzoic acid phenyl ester；2-Cyan-benzoesaeure-phenylester
• CAS: 216585-42-1
• 化学式: C₁₄H₉NO₂
• 分子量: 223.231
• InChiKey: XZZCSVUEAANCNW-UHFFFAOYSA-N

物化性质

• 熔点：
  73 °C
• 沸点：
  406.0±28.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  phenyl 2-cyanobenzoate 在 platinum(IV) oxide 氢气 作用下， 以 四氢呋喃 、 氯仿 、 苯酚 为溶剂， 反应 4.0h， 生成 phenyl 2-aminomethylbenzoate hydrochloride
  参考文献：
  名称：

  通用碱和通用酸催化酯的分子内氨解。2-氨基甲基苯甲酸的酯环化为邻苯二甲酰亚胺。

  摘要：

  在30摄氏度下于H（2）O中将三氟乙基和2-氨基甲基苯甲酸苯酯环化为邻苯二甲酰亚胺的对数k（0）与pH的关系图呈线性，斜率在pH> 3时为1.0。环化反应中表观OH（-​​）催化的二级速率常数k（OH）的值为1.7 x 10（5）和5.7 x 10（7）M（-）（1）s（-）（ 1）。这些速率常数比三氟乙基和苯甲酸苯酯的碱水解大10（5）-和10（7）-倍。用于甲酯环化的k（OH）为7.2 x 10（3）M（-）（1）s（-）（1）。双分子一般的碱催化发生在中性物种的分子内亲核反应中。三氟乙基酯的布朗斯台德系数β的值为0.7。一般碱催化反应中的限速步骤涉及质子转移以及离去基团的离开。然后可以将涉及速率决定质子转移的机理以该系列的甲酯为例（β= 1.0），可以认为是该机理的限制性例子。当离去基团良好时，也会发生中性物质反应的一般酸催化或动力学等价反应（pK（a）

  DOI：

  10.1021/jo9906835
• 作为产物：
  描述：

  4-methyl-1-phenyl-1H-1,4-epoxido-benzo[d][1,2]dioxepin-5-one oxime 在 五氯化磷 作用下， 生成 phenyl 2-cyanobenzoate
  参考文献：
  名称：

  Criegee et al., Justus Liebigs Annalen der Chemie, 1953, vol. 583, p. 1,28

  摘要：

  DOI：

文献信息

• Kinetic Study of Hydrolysis of Benzoates. Part XXV. Ortho Substituent Effect in Alkaline Hydrolysis of Phenyl Esters of Substituted Benzoic Acids in Water
  作者：Vilve Nummert、Mare Piirsalu、Vahur Mäemets、Ilmar Koppel

  DOI：10.1135/cccc20060107

  日期：——

  The second-order rate constants k₂ for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C₆H₄CO₂C₆H₅ (X = H, 3-Cl, 3-NO₂, 3-CH₃, 4-NO₂, 4-Cl, 4-F, 4-CH₃, 4-OCH₃, 4-NH₂, 2-NO₂, 2-CN, 2-F, 2-Cl, 2-Br, 2-I, 2-CH₃, 2-OCH₃, 2-CF₃, 2-NH₂), and of substituted phenyl esters of benzoic acid, C₆H₅CO₂C₆H₄-X (X = 2-I, 2-CF₃, 2-C(CH₃)₃, 4-Cl, 4-CH₃, 4-OCH₃, 4-NH₂), have been measured spectrophotometrically in water at 25 °C. The substituent effect in alkaline hydrolysis of phenyl esters of para-substituted benzoic acids, similar to that for ethyl esters of para-substituted benzoic acids, was found to be precisely described by the Hammett relationship (ρ = 1.7 in water). The log k value for alkaline hydrolysis of phenyl and ethyl esters of meta-, para- and ortho-substituted benzoic acids, X-C₆H₄CO₂R, was nicely correlated with log k_m,p,ortho = log k_o + (ρ)_m,pσ + (ρ_I)_orthoσ_I + (ρ°_R)_orthoσ°_R + δ_orthoE_s^B where σ, σ_I, σ°_R are the Hammett polar, Taft inductive and Taft resonance (σ°_R = σ° - σ_I) substituent constants, respectively. E_s^B is the steric scale for ortho substituents calculated on the basis of the log k values for the acid hydrolysis of ortho- substituted phenyl benzoates in water owing to the ortho substituent in the phenyl of phenyl benzoates. In water, the main factors responsible for changes in the ortho substituent effect in alkaline hydrolysis of phenyl and ethyl esters of ortho-substituted benzoic acids, X-C₆H₄CO₂R, were found to be the inductive and steric factors while the role of the resonance term was negligible ((ρ°_R)_ortho ca. 0.3). In alkaline hydrolysis of substituted benzoates in neat water, the ortho inductive effect appeared to be 1.5 times and steric influence 2.7 times higher than the corresponding influences from the ortho position in the phenyl of phenyl benzoates. The contributions of the steric effects in alkaline hydrolysis of esters of ortho-substituted benzoic acids was found to be approximately the same as in acid hydrolysis of esters of ortho-substituted benzoic and acid esterification of ortho-substituted benzoic acids.

  对苯酸酯碱水解的二阶速率常数 k2，对邻、对、间取代苯甲酸的苯酯 X-C6H4CO2C6H5（X = H、3-Cl、3-NO2、3-CH3、4-NO2、4-Cl、4-F、4-CH3、4-OCH3、4-NH2、2-NO2、2-CN、2-F、2-Cl、2-Br、2-I、2-CH3、2-OCH3、2-CF3、2-NH2）以及苯甲酸苯酯的取代苯酯 C6H5CO2C6H4-X（X = 2-I、2-CF3、2-C(CH3)3、4-Cl、4-CH3、4-OCH3、4-NH2）在25°C的水中进行了分光光度测定。对邻取代苯甲酸的苯酯碱水解的取代基效应，类似于对邻取代苯甲酸的乙酯，被发现可以精确地由 Hammett 关系描述（ρ = 1.7 在水中）。对邻、对、间取代苯甲酸的苯酯和乙酯 X-C6H4CO2R 的碱水解的 log k 值与 log km,p,ortho = log ko + (ρ)m,pσ + (ρI)orthoσI + (ρ°R)orthoσ°R + δorthoE sB 相关联，其中σ、σI、σ°R 是 Hammett 极性、Taft 归纳和Taft 共振（σ°R = σ° - σI）取代基常数，E sB 是基于对苯甲酸苯酯的苯基中取代基的酸水解 log k 值计算的对位取代基的立体规模。在水中，对苯酸酯碱水解的对取代基效应的主要因素被发现为归纳和立体因素，而共振项的作用微乎其微（（ρ°R）ortho 约为0.3）。在水中，对苯酸酯碱水解的对位取代基的立体影响似乎比对苯甲酸苯酯的苯基中的对位影响高出1.5倍，而归纳影响则高出2.7倍。对苯酸酯碱水解的对位取代基的立体效应的贡献与对苯酸酯碱水解的酸和对位取代基酯化的酸酯化大致相同。
• Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr
  作者：Vilve Nummert、Mare Piirsalu、Signe Vahur、Oksana Travnikova、Ilmar A. Koppel

  DOI：10.1135/cccc2008019

  日期：——

  The second-order rate constants k (in dm³ mol^–1 s^–1) for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H₄CO₂C₆H_5, have been measured spectrophotometrically in aqueous 0.5 and 2.25 M Bu₄NBr at 25 °C. The substituent effects for para and meta derivatives were described using the Hammett relationship. For the ortho derivatives the Charton equation was used. For ortho-substituted esters two steric scales were involved: the E_sB and the Charton steric (υ) constants. When going from pure water to aqueous 0.5 and 2.25 M Bu₄NBr, the meta and para polar effects, the ortho inductive and resonance effects in alkaline hydrolysis of phenyl esters of substituted benzoic acids, became stronger nearly to the same extent as found for alkaline hydrolysis of C₆H₅CO₂C₆H₄-X. The steric term of ortho-substituted esters was almost independent of the media considered. The rate constants of alkaline hydrolysis of ortho-, meta- and para-substituted phenyl benzoates (X-C₆H₄CO₂C₆H₅, C₆H₅CO₂C₆H₄-X) and alkyl benzoates, C₆H₅CO₂R, in water, 0.5 and 2.25 M Bu₄NBr were correlated with the corresponding IR stretching frequencies of carbonyl group, (Δν_CO)_X.

  对苯甲酸酯的碱水解的二阶速率常数 k（以 dm³ mol⁻¹ s⁻¹ 计量），在25°C下，在水溶液中0.5和2.25 M Bu₄NBr下，用分光光度法测定了对位、间位和邻位取代苯甲酸的苯基酯的速率常数。对于对位和间位衍生物，取代基效应使用 Hammett 关系描述。对于邻位衍生物，使用了 Charton 方程。对于邻位取代酯，涉及两种立体参数：EsB 和 Charton 立体（υ）常数。从纯水到水溶液0.5和2.25 M Bu₄NBr，对苯基酯的碱水解中，对位和间位极性效应，对苯甲酸酯的碱水解中的邻位感应和共振效应，几乎与对 C₆H₅CO₂C₆H₄-X 的碱水解发现的情况一样强。邻位取代酯的立体项几乎独立于考虑的介质。对苯基苯甲酸酯（X-C₆H₄CO₂C₆H₅，C₆H₅CO₂C₆H₄-X）和烷基苯甲酸酯 C₆H₅CO₂R 在水、0.5和2.25 M Bu₄NBr中的碱水解速率常数与羰基的对应 IR 伸缩频率（ΔνCO）X 相关联。
• Influence of solvent on the <i>ortho</i> substituent effect in the alkaline hydrolysis of phenyl esters of substituted benzoic acids
  作者：Vilve Nummert、Mare Piirsalu、Ilmar A. Koppel

  DOI：10.1002/poc.1628

  日期：2010.6

  (dm3 mol−1 s−1) for the alkaline hydrolysis of phenyl esters of meta‐, para‐ and ortho‐substituted benzoic acids in aqueous 5.3 M NaClO4 and 1.0 M Bu4NBr were measured by UV/Vis spectrophotometry at 25 °C. The variations in the ortho inductive, ortho resonance, as well as meta and para polar effects with solvent parameters were studied using data for the alkaline hydrolysis of phenyl esters of substituted benzoic

  二阶速率常数ķ（DM 3 摩尔-1 小号-1为苯基酯的碱性水解）间位- ，对位和-邻-取代的苯甲酸在含水为5.3μm的NaClO 4和1.0M卜4测定NBR通过在25℃下的UV / Vis分光光度法。使用在各种介质中对苯甲酸的苯基酯进行碱水解的数据，研究了邻位感应，邻位共振以及间位和对极效应随溶剂参数的变化。的依赖邻上溶剂取代效果可通过下面的等式来精确描述的：Δlog ķ邻 =登录ķ邻 -日志ķ ħ  = 0.059 + 2.19 σ我 + 0.304 σ ° - [R  + 2.79 ë  - 0.016Δ Eσ我 - 0.085Δ Eσ ° ř，其中ΔE是溶剂的亲电性，ΔE  =  E S  -  E H2O，表征了溶剂的氢键给体能力。在增加元和随着溶剂氢键供体容量（亲电子性）的降低，对极性取代基的影响与邻位取代基的共振项大致相同（-0.068ΔEσ ° m，p）。邻取代基的空间术语与
• Thiazole derivatives
  申请人：Nakajima Takao

  公开号：US20070105919A1

  公开（公告）日：2007-05-10

  (Wherein n is an integer of from 0 to 3; R 1 is substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, a substituted or unsubstituted alicyclic heterocyclic group, or a substituted or unsubstituted aromatic heterocyclic group; R 2 is halogen, substituted or unsubstituted lower alkyl, substituted or unsubstituted aryl, a substituted or unsubstituted alicyclic heterocyclic group, a substituted or unsubstituted aromatic heterocyclic group, —COR 8 , or the like; R 3 and R 4 may be the same or different, and each represents a hydrogen atom, substituted or unsubstituted lower alkyl, substituted or unsubstituted aralkyl, —COR 12 , or the like) For example, provided are adenosine A 2A receptor antagonists comprising, as the active ingredient, a thiazole derivative represented by a general formula (I), or a pharmaceutically acceptable salt thereof, and the like.

  其中n为0至3的整数；R1代表取代或未取代的环烷基、取代或未取代的芳基、取代或未取代的脂环杂环基或取代或未取代的芳香杂环基；R2代表卤素、取代或未取代的低碳基、取代或未取代的芳基、取代或未取代的脂环杂环基、取代或未取代的芳香杂环基、-COR8或类似物；R3和R4可以相同也可以不同，每个代表氢原子、取代或未取代的低碳基、取代或未取代的芳基烷基、-COR12或类似物。例如，提供了包含噻唑衍生物的腺苷A2A受体拮抗剂作为活性成分，其表示为通式（I）或其药学上可接受的盐等。
• THIAZOLE DERIVATIVES
  申请人：Nakajima Takao

  公开号：US20110105486A1

  公开（公告）日：2011-05-05

  Wherein n is an integer of from 0 to 3; R 1A is a 5-membered aromatic heterocyclic group containing at least one oxygen atom; R 2A is —COR 8 (wherein R 8 is aryl); R 3A is hydrogen or lower alkyl; and R 12 represents cycloalkyl, aryl, aralkyl, alicyclic heterocyclic group, aromatic heterocyclic group, alicyclic hetocyclic-alkyl, or aromatic heterocyclic-alkyl, and R 1A , R 2A , R 3A and R 12 are individually optionally substituted.

  其中n是0到3的整数；R1A是一个含有至少一个氧原子的5-成员芳香杂环基团；R2A是-COR8（其中R8是芳香基）；R3A是氢或较低的烷基；而R12代表环烷基，芳香基，芳基烷基，脂环杂环基团，芳香杂环基团，脂环杂环烷基或芳香杂环烷基，R1A，R2A，R3A和R12都可以个别地选择性地被取代。