methyl 3-mercaptopropionate ion | 59177-13-8

• 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: methyl 3-mercaptopropionate ion
• 英文别名: methyl 3-mercaptopropionate；3-Methoxy-3-oxopropane-1-thiolate
• CAS: 59177-13-8
• 化学式: C₄H₇O₂S
• 分子量: 119.164
• InChiKey: LDTLDBDUBGAEDT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  7
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  27.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-(1-nitroethene-1,2-diyl)dibenzene 、 methyl 3-mercaptopropionate ion 在 N-甲基吗啉 、 potassium chloride 作用下， 以 水 、 二甲基亚砜 为溶剂， 生成
  参考文献：
  名称：

  烯烃的亲核加成。第 23 部分。 高固有速率常数和硫醇盐离子添加到取代的 α-硝基芪中的大不平衡

  摘要：

  加成 d' 离子硫醇盐 RS − (R=Et, HOCH 2 CH 2 , CH 3 OCOCH 2 CH 2 , et CH 3 OCOCH 2 ) a l'α-nitrostilbene et de HOCH 2 CH 2 S − a des α-nitrostilbenes sur l'α-苯基 (Me-4, H, Br-4, NO 2 -3, et NO 2 -4)

  DOI：

  10.1021/ja00230a038
• 作为产物：
  描述：

  methyl 3-S-nitrosomercaptopropionate 生成 methyl 3-mercaptopropionate ion
  参考文献：
  名称：

  Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

  摘要：

  The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (alpha(1g) approximate to -1.30), but virtually independent of the basicity of the thiol (beta(nuc) approximate to 0-10)This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (beta(d)) that is followed by the attack of the thiolate ion on the nitroso group (beta'(nuc)) via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonarni de were used to obtain the equilibrium constants for the different reactions involved. By using rate-equilibrium correlations, the parameters alpha(norm)(1g) ,beta(d), and beta('norm)(nuc) were obtained. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.060

文献信息

• Reactions of [Aryloxy(phenyl)carbene]pentacarbonylchromium(0) Complexes with Thiolate Ions. Decreasing Reactivity with Increasing Basicity of the Nucleophile
  作者：Claude F. Bernasconi、Moisés Pérez-Lorenzo、Sara J. Codding

  DOI：10.1021/jo701422z

  日期：2007.12.1

  A kinetic study of the reactions of thiolate ions with three Fischer-type [aryloxy(phenyl)carbene]pentacarbonyl chromium(0) complexes in 50% MeCN−50% water (v/v) is reported. Brønsted plots of the second-order rate constants are biphasic with an initial steep rise for weakly basic thiolate ions (βnuc ≈ 1.0) followed by a slightly descending leg with a negative slope (βnuc ≈ −0.2) for strongly basic

  动力学研究了硫醇离子与三种Fischer型[芳氧基（苯基）卡宾]五羰基铬（0）络合物在50％MeCN-50％水（v / v）中反应的动力学研究。二阶速率常数的布朗斯台德图是两相的，弱碱性硫醇盐离子（βnuc≈1.0）的初始陡峭上升，随后是强碱性硫醇盐离子的负斜率（βnuc≈- 0.2）的略微下降的曲线。这表明从低p的限速离去基团离开到高p的限速亲核附着发生了变化。负βnuc这些值是由于过渡态中C-S键形成的最小进展与亲核体进入过渡态之前部分脱溶剂的要求共同导致的。讨论了可能会影响Fischer卡宾配合物反应以及其他不饱和亲电试剂与硫醇盐离子反应的键形成程度的可能因素。
• Physical Organic Chemistry of Transition Metal Carbene Complexes. 16.¹ Reactions of (CO)₅MC(OR)Ph (M = Cr or W; R = Me or Et) with Thiolate Ions in Aqueous Acetonitrile. Complete Kinetic Dissection of the Two-Step Mechanism
  作者：Claude F. Bernasconi、Kevin W. Kittredge、Francis X. Flores

  DOI：10.1021/ja9908265

  日期：1999.7.1

  high pH formation of a tetrahedral intermediate, (CO)5MC(OR‘)(SR)Ph, is observed. Upon addition of acid the intermediate is converted into the substitution product. For the reactions of most thiolate ions a detailed kinetic analysis allowed the determination of the rate constants for nucleophilic attack on the carbene complexes (k1) and its reverse (k-1), the equilibrium constant for nucleophilic addition

  (CO)5MC(OR')Ph 反应的动力学研究 (1a, M = Cr, R' = Me; 1b, M = W, R' = Me; 1c, M = Cr, R' = Et; 1d, M = W, R' = Et) 与 n-PrS-、HOCH2CH2S-、MeO2CCH2CH2S- 和 MeO2CCH2S- 在 50% MeCN-50% 水 (v/v) 中在 25 °C 报告。在低 [RS-] 和相对低的 pH 值下，反应会产生亲核取代产物 (CO)5MC(SR)Ph，而没有任何中间体的积累。在高 [RS-] 和高 pH 值下，观察到四面体中间体 (CO)5MC(OR')(SR)Ph 的形成。加入酸后，中间体转化为取代产物。对于大多数硫醇盐离子的反应，详细的动力学分析允许确定卡宾配合物上亲核攻击的速率常数 (k1) 及其反向 (k-1)，亲核加成的平衡常数 (K1 = k1/k- 1), 以及醇盐离子离开由
• 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.
• Physical Organic Chemistry of Transition Metal Carbene Complexes. 17.¹ Kinetics of the Reactions of (Arylthioalkoxycarbene)pentacarbonyl Complexes of Chromium(0) and Tungsten(0) with Thiolate Ions in Aqueous Acetonitrile:  p<i>K</i>_a Values of the Metal-Protonated Tetrahedral Adducts Formed between Carbene Complexes and Thiolate Ion
  作者：Claude F. Bernasconi、Mahammad Ali

  DOI：10.1021/ja992741+

  日期：1999.12.1

  Rate and equilibrium constants for the nucleophilic attachment of various thiolate ions to (CO)(5)M= C(SMe)Ph (M = Cr and W) and for the attachment of HOCH2CH2S- to (CO)(5)W=C(SCH2CH2OH)C(6)H(4)Z (Z = CF3, Cl, F, H, Me, MeO, and Me2N) have been determined in 50% MeCN-50% water (v/v) at 25 degrees C. For some of the adducts, those of the general structure (CO)(5)MC(SR,SR')C(6)H(4)Z, a kinetic determination of the pK(a) of their metal-protonated conjugate acid, (CO)(5)M(H)C(SR,SR')C(6)H(4)Z, is also reported. On the basis of Br phi nsted coefficients, Hammett rho values and comparisons with the reactions of the same thiolate ions with methoxy carbene complexes such as (CO)(5)M=C(OMe)Ph, insights into the role played by desolvation of the nucleophile prior to C-S bond formation, by the smaller pi-donor and inductive but larger steric effects of the MeS compared to the MeO group, by transition state imbalances, etc. are discussed. The pK(a) values obtained for (CO)(5)M(H)C(SR,SR')C(6)H(4)Z were used to resolve a mechanistic ambiguity in the hydrolysis of Fischer carbenes that have acidic protons on the alpha-carbon, e.g., (CO)(5)Cr=C(OMe)Me.
• Bernasconi, Claude F.; Fassberg, Julianne; Killion Jr., Robert B., Journal of the American Chemical Society, 1990, vol. 112, # 8, p. 3169 - 3177
  作者：Bernasconi, Claude F.、Fassberg, Julianne、Killion Jr., Robert B.、Rappoport, Zvi

  DOI：——

  日期：——