(1-Phenyl-2-nitro-ethylmercapto)-essigsaeure-methylester | 91134-32-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1-Phenyl-2-nitro-ethylmercapto)-essigsaeure-methylester
• 英文别名: methyl {[alpha-(nitromethyl)benzyl]thio}acetate；Acetic acid, [(2-nitro-1-phenylethyl)thio]-, methyl ester；methyl 2-(2-nitro-1-phenylethyl)sulfanylacetate
• CAS: 91134-32-6
• 化学式: C₁₁H₁₃NO₄S
• 分子量: 255.295
• InChiKey: JTPZSQGUPSQDOC-UHFFFAOYSA-N

物化性质

• 沸点：
  372.9±42.0 °C(Predicted)
• 密度：
  1.259±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1-Phenyl-2-nitro-ethylmercapto)-essigsaeure-methylester 在 溶剂黄146 、 锌 作用下， 反应 72.0h， 以59%的产率得到2-phenylthiomorpholin-5-one
  参考文献：
  名称：

  2-Arylthiomorpholine derivatives as potent and selective monoamine oxidase B inhibitors

  摘要：

  2-Arylthiomorpholine and 2-arylthiomorpholin-5-one derivatives, designed as rigid and/or non-basic phenylethylamine analogues, were evaluated as rat and human monoamine oxidase inhibitors. Molecular docking provided insight into the binding mode of these inhibitors and rationalized their different potencies. Making the phenylethylamine scaffold rigid by. xing the amine chain in an extended six-membered ring conformation increased MAO-B (but not MAO-A) inhibitory activity relative to the more flexible alpha-methylated derivative. The presence of a basic nitrogen atom is not a prerequisite in either MAO-A or MAO-B. The best K-i values were in the 10(8) M range, with selectivities towards human MAO-B exceeding 2000-fold. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2010.01.029
• 作为产物：
  描述：

  β-硝基苯乙烯 、 巯基乙酸甲酯 在 C₃₇H₅₆N₄O₄ 、 lanthanum(lll) triflate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.0h， 以99%的产率得到(1-Phenyl-2-nitro-ethylmercapto)-essigsaeure-methylester
  参考文献：
  名称：

  镧催化的巯基乙酸盐向查尔酮类化合物的高对映选择性共轭加成：低催化剂负载和显着的手性扩增

  摘要：

  加强：使用手性N，N'-二氧化物-La III络合物作为催化剂，开发了标题反应。反应以高产率和对映选择性进行。显着地观察到高的不对称扩增，因为使用1mol％的L / La（OTf）3达到98％  ee，其中L的ee 值为2％  ee。Tf ＝三氟甲磺酰基。

  DOI：

  10.1002/anie.201000105

文献信息

• Kinetics of reversible thiolate ion addition to substituted .beta.-nitrostyrenes in water. Radicaloid transition state or principle of nonperfect synchronization?
  作者：Claude F. Bernasconi、David F. Schuck

  DOI：10.1021/jo00034a032

  日期：1992.4

  The kinetics of reversible nucleophilic thiolate ion (RS- with R = n-Bu, HOCH2CH2, MeO2CCH2CH2 and MeO2CCH2) addition to Z-substituted beta-nitrostyrenes (Z = 4-Me2N, 4-MeO, 4-MeS, 4-Me, H, 3-Cl, 4-Cl, 3-CN, 4-CN, and 3-NO2), to form ArCH(RS)CH = NO2-, have been measured in water at 20-degrees-C. Rate constants in the forward (k1) and reverse direction (k-1) and equilibrium constants (K1) correlate reasonably well with Hammett sigma-constants for the non-pi-donor substituents but show deviations for the pi-donors 4-Me2N, 4-MeO, and 4-MeS. These deviations are negative for K1 but positive for k1 and k-1; the positive deviations for the pi-donor substituents are also observed when plotting log k1 vs log K1 (Bronsted plots). The negative deviations of K1 are a consequence of resonance stabilization of the olefin. The positive deviations are attributed to a transition-state stabilization stemming from a preorganization created by the pi-donor which leads to a better delocalization of the negative charge into the nitro group. An alternative interpretation of the rate acceleration in terms of a radicaloid transition state (Gross, Z.; Hoz, S.J. Am. Chem. Soc. 1988, 110, 7489) cannot be ruled out but is shown to be less attractive and unnecessary. Bronsted parameters such as beta(nuc), beta(eq), beta(nuc)n, and beta(lg)n, and intrinsic rate constants (k(o) = k1 k-1 when K1 = 1) were determined from the dependence on RS- basicity for beta-nitrostyrene and 3-cyano-beta-nitrostyrene. Beta(eq) is low (0.5), indicating that the carbon basicity of RS- is less sensitive to electronic effects in R than its proton basicity. Beta(nuc) (beta(nuc)n) is very low, suggesting a transition state with very little C-S bond formation. The low beta(nuc)n (0.22) contrasts with a large alpha(nuc)n = d log k1/d log K1 = 0.74 (variation of Z), indicating a large transition-state imbalance (alpha(nuc)n - beta(nuc)n), as previously observed in the reaction of RS- with alpha-nitrostilbenes. The intrinsic rate constant (log k(o) = 3.5) is also similar to that for the reaction of RS- with alpha-nitrostilbenes and significantly higher than for the reaction of amines with beta-nitrostyrenes. Most of these features can, at least in part, be attributed to the soft acid-soft base interactions of RS- with the nitroolefins. Rate constants for carbon protonation of several of the ArCH(RS)CH = NO2- adducts by acetic acid (k(p)HA) were also determined. They display the unusual, but for nitronate ions typical, acceleration when Ar and/or R is made more electron withdrawing.
• MONTANINI; MARTANI; BERSI, Bollettino Chimico Farmaceutico, 1964, vol. 103, p. 187 - 191
  作者：MONTANINI、MARTANI、BERSI

  DOI：——

  日期：——
• Highly Enantioselective Conjugate Addition of Thioglycolate to Chalcones Catalyzed by Lanthanum: Low Catalyst Loading and Remarkable Chiral Amplification
  作者：Yonghai Hui、Jun Jiang、Wentao Wang、Weiliang Chen、Yunfei Cai、Lili Lin、Xiaohua Liu、Xiaoming Feng

  DOI：10.1002/anie.201000105

  日期：——

  Ramping it up: The titled reaction has been developed using a chiral N,N′‐dioxide–LaIII complex as the catalyst. The reaction proceeded with high yield and enantioselectivity. Remarkably, a high asymmetric amplification was observed, as 98 % ee was achieved using 1 mol % L/La(OTf)3 in which the ee value of L was 2 % ee. Tf=trifluoromethanesulfonyl.

  加强：使用手性N，N'-二氧化物-La III络合物作为催化剂，开发了标题反应。反应以高产率和对映选择性进行。显着地观察到高的不对称扩增，因为使用1mol％的L / La（OTf）3达到98％  ee，其中L的ee 值为2％  ee。Tf ＝三氟甲磺酰基。
• 2-Arylthiomorpholine derivatives as potent and selective monoamine oxidase B inhibitors
  作者：Susan Lühr、Marcelo Vilches-Herrera、Angélica Fierro、Rona R. Ramsay、Dale E. Edmondson、Miguel Reyes-Parada、Bruce K. Cassels、Patricio Iturriaga-Vásquez

  DOI：10.1016/j.bmc.2010.01.029

  日期：2010.2

  2-Arylthiomorpholine and 2-arylthiomorpholin-5-one derivatives, designed as rigid and/or non-basic phenylethylamine analogues, were evaluated as rat and human monoamine oxidase inhibitors. Molecular docking provided insight into the binding mode of these inhibitors and rationalized their different potencies. Making the phenylethylamine scaffold rigid by. xing the amine chain in an extended six-membered ring conformation increased MAO-B (but not MAO-A) inhibitory activity relative to the more flexible alpha-methylated derivative. The presence of a basic nitrogen atom is not a prerequisite in either MAO-A or MAO-B. The best K-i values were in the 10(8) M range, with selectivities towards human MAO-B exceeding 2000-fold. (C) 2010 Elsevier Ltd. All rights reserved.