n-propanethiolate | 20733-14-6

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: n-propanethiolate
• 英文别名: n-propyl mercaptyl anion；propanethiolate；Propylthiolate ion；1-propanethiolate；Propanethiolate anion；Thiopropoxide；propane-1-thiolate
• CAS: 20733-14-6
• 化学式: C₃H₇S
• 分子量: 75.1546
• InChiKey: SUVIGLJNEAMWEG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  4
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  n-propanethiolate 、 alkaline earth salt of/the/ methylsulfuric acid 在 potassium chloride 作用下， 以 水 、 乙腈 为溶剂， 生成 4-硝基苯酚阴离子
  参考文献：
  名称：

  [芳氧基（苯基）卡宾]五羰基铬（0）配合物与硫醇离子的反应。随着亲核碱度的增加，反应性降低†

  摘要：

  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。

  DOI：

  10.1021/jo701422z
• 作为产物：
  描述：

  在 potassium chloride 作用下， 以 水 、 二甲基亚砜 为溶剂， 生成 n-propanethiolate 、 2-[(E)-2-nitro-1,2-diphenylethenyl]sulfanylethanol
  参考文献：
  名称：

  Bernasconi, Claude F.; Fassberg, Julianne; Killion Jr., Robert B., Journal of the American Chemical Society, 1990, vol. 112, # 8, p. 3169 - 3177

  摘要：

  DOI：
• 作为试剂：
  描述：

  5-benzyloxy-3-carbomethoxy-1,4-dimethoxy-7-methoxymethoxy-2,6-dimethylnaphthalene 在 N,N-二甲基丙烯基脲 、 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 n-propanethiolate 、 sodium acetate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 为溶剂， 反应 39.0h， 生成 8-Benzyloxy-1,4-dimethoxy-6-methoxymethoxy-3,7-dimethyl-5-propionyl-naphthalene-2-carboxylic acid
  参考文献：
  名称：

  Synthesis of highly functionalized naphthoate precursors to damavaricin D — Observation of kinetically stable benzocyclohexadienones in the bromination reactions of highly functionalized β-naphthol derivatives

  摘要：

  Selective syntheses of the highly substituted bromonaphthoates 4a, 4b, 19, and 22 are reported. These compounds were targeted as precursors to the naphthoquinone nucleus of damavaricin D; compound 22 ultimately was used in the successful total synthesis. The synthesis of 22 features the Diels-Alder reaction of the oxygenated diene 5 and 2,6-dibromo-3-methylbenzoquinone 6 to establish the core naphthalenic unit. The quinone was protected throughout this synthesis as a 1,4-bis-methoxymethyl-1,4-dihydroquinone (see 36). The C-2-carboalkoxy group of 22 was added by carboxylation of the aryllithium intermediate generated from 36, and protected as a beta -trimethylsilylethyl ester. Finally, the C-8-Br substituent was introduced by NBS bromination of 38. This reaction proceeds by way of bromobenzocyclohexadienone 39. Related bromobenzo-cyclohexadienones 13 and 29 were observed in the NBS brominations of the highly functionalized beta -naphthyl MOM ethers 11 and 28. The bromobenzocyclohexadienones 29 and 39 undergo facile substitution reactions with chloride ion and reduction with bromide ion at rates competitive with base-promoted aromatization. The surprising kinetic stability of these intermediates is attributed to a combination of steric and stereoelectronic factors.

  DOI：

  10.1139/cjc-79-11-1711

文献信息

• Structure−Reactivity Relationships and Intrinsic Reaction Barriers for Nucleophile Additions to a Quinone Methide:  A Strongly Resonance-Stabilized Carbocation
  作者：John P. Richard、Maria M. Toteva、Juan Crugeiras

  DOI：10.1021/ja9937526

  日期：2000.3.1

  constants for the addition of Cl- and AcO-. The values of log kNu show a linear correlation with the Ritchie nucleophilicity parameter N+ with a slope s = 0.92 ± 0.10 that is essentially the same as the electrophile-independent value of 1.0 for highly resonance-stabilized carbocations. Marcus intrinsic barriers Λ of 12.4, 13.9, 15.4, and 19.8 kcal/mol are reported for the addition of I-, Br-, Cl-, and

  二级速率常数 kNu (M-1 s-1) 被确定用于将各种亲核试剂添加到简单的醌甲基化物 4-[双（三氟甲基）亚甲基]环六-2,5-二烯酮 (1) 中，得到亲核试剂加合物 1-Nu 在水中。确定了将 HBr 和 HI 全部添加到 1 以得到 H-1-Nu 的平衡常数，并且使用数据来计算将 Br- 和 I- 添加到 1 的平衡常数，并估计平衡常数添加 Cl- 和 AcO-。log kNu 的值显示与 Ritchie 亲核性参数 N+ 的线性相关性，斜率 s = 0.92 ± 0.10，这与高度共振稳定的碳正离子的亲电独立值 1.0 基本相同。据报道，添加 I-、Br-、Cl-、12.4、13.9、15.4 和 19.8 kcal/mol 的 Marcus 固有势垒 Λ 为 和 AcO- 分别为 1。将 Br-、Cl- 和 AcO- 添加到 1 的热力学势垒 ΔG° 和本征势垒 Λ 为 8.4
• The Ever-Surprising Chemistry of Boron: Enhanced Acidity of Phosphine⋅Boranes
  作者：Marcela Hurtado、Manuel Yánez、Rebeca Herrero、Andrés Guerrero、Juan Z. Dávalos、José-Luis M. Abboud、Brahim Khater、Jean-Claude Guillemin

  DOI：10.1002/chem.200802307

  日期：2009.4.27

  The acidity‐enhancing effect of BH3 in gas‐phase phosphine⋅boranes compared to the corresponding free phosphines is enormous, between 13 and 18 orders of magnitude in terms of ionization constants. Thus, the enhancement of the acidity of protic acids by Lewis acids usually observed in solution is also observed in the gas phase. For example, the gas‐phase acidities (GA) of MePH2 and MePH2⋅BH3 differ

  酸度提高效果BH的3在气相膦⋅硼烷相比于相应的游离的膦是巨大的，大小为13级18之间的订单在电离常数的条款。因此，在气相中也观察到通常在溶液中观察到的路易斯酸对质子酸酸度的增强。例如，麦菲的气相酸度（GA）2和麦菲2 ⋅ BH 3由约118千焦摩尔不同-1（见图）。
• Structure−Reactivity Relationships for Addition of Sulfur Nucleophiles to Electrophilic Carbon:  Resonance, Polarization, and Steric/Electrostatic Effects
  作者：Maria M. Toteva、John P. Richard

  DOI：10.1021/ja0021868

  日期：2000.11.1

  to those for addition of substituted alkyl alcohol ROH to the much more electrophilic 1-(4-methoxyphenyl)ethyl carbocation (5+). The larger value of βnuc = 0.32 for addition of ROH to 5+ than βnuc = 0.11 for addition of RS- to 1 shows that there are important differences in the reaction coordinate profiles for these nucleophile addition reac...

  用于直接添加取代链烷硫醇阴离子的二级速率常数 kRS 和 kRSH (M-1 s-1) RS- 和中性硫醇 RSH 和三级速率常数 (kRSH)H (M-2 s-1) 用于酸报道了在水中将 RSH 催化加成到简单的醌甲基化物 4-[双（三氟甲基）亚甲基]环六-2,5-二烯酮 (1) 中。还测定了加入 Me2S 和 H+ 以产生 H-1-SMe2+ 的速率和平衡常数。将 RS- 添加到 1 的数据与 Bronsted 系数 βnuc = 0.11 相关，这类似于将 RS- 添加到其他高度共振稳定的碳正离子的数据。RS- 加成到 1 的速率常数类似于将取代的烷基醇 ROH 加成到更亲电的 1-(4-甲氧基苯基) 乙基碳正离子 (5+) 的速率常数。βnuc = 0 的较大值。
• 1H-pyrazole-1-(branched)alkanamides as antiarrhythmic agents,
  申请人：Sterling Drug Inc.

  公开号：US04988725A1

  公开（公告）日：1991-01-29

  N-[(alkylamino)alkyl]-3,4(or 4,5)-diaryl-1H-pyrazole-1-(branched)alkanamides and pyrazole-1-alkanamines useful for treating cardiac arrhythmias in mammals, are prepared by reacting a lower-alkyl ester of pyrazole-1-acetic acid with an appropriate diamine followed by reduction or by reacting the anion of a lower-alkyl ester of a pyrazole-1-acetic acid with an alkylating agent followed by displacement of the ester by an appropriate amine.

  用于治疗哺乳动物心律失常的N-[(烷基)氨基烷基]-3,4或4,5-二芳基-1H-吡唑-1-(支链)烷酰胺和吡唑-1-烷胺，通过将吡唑-1-乙酸较低烷基酯与适当的二胺反应后还原或通过将较低烷基吡唑-1-乙酸酯的阴离子与烷基化试剂反应后，再用适当的胺取代酯来制备。
• 1H-pyrazole-1-alkanamides, antiarrhythmic compositions and use
  申请人：Sterling Drug, Inc.

  公开号：US04870095A1

  公开（公告）日：1989-09-26

  N-[(disubstituted amino)alkyl]-3,4 (or 4,5)-diaryl-1H-pyrazole-1-acetamides and pyrazole-1-propanamides, useful for treating cardiac arrhythmias in mammals, are prepared by reacting a lower-alkyl ester of pyrazole-1-acetic or propanoic acid with an appropriate diamine or by reacting a lower-alkyl ester of a pyrazole-1-acetic or propanoic acid with an .omega.-aminoalkanol, followed by activation of the alcohol and displacement by an appropriate amine.

  用于治疗哺乳动物心律失常的N-[(二取代氨基)烷基]-3,4(或4,5)-二芳基-1H-吡唑-1-乙酰胺和吡唑-1-丙酰胺是通过将吡唑-1-乙酸或丙酸的较低烷基酯与适当的二胺反应或将吡唑-1-乙酸或丙酸的较低烷基酯与.omega.-氨基烷醇反应，随后激活醇并被适当的胺替换而制备的。