Ethoxy-(4-nitrophenoxy)methanethione | 177170-39-7

• 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: Ethoxy-(4-nitrophenoxy)methanethione
• CAS: 177170-39-7
• 化学式: C₉H₉NO₄S
• 分子量: 227.241
• InChiKey: BYDJGZKLDZPEAU-UHFFFAOYSA-N

物化性质

• 沸点：
  318.3±44.0 °C(Predicted)
• 密度：
  1.339±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  96.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  piperidinium cation 、 Ethoxy-(4-nitrophenoxy)methanethione 在 potassium chloride 作用下， 以 水 为溶剂， 生成
  参考文献：
  名称：

  Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Ethyl Thionocarbonates

  摘要：

  The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0 degrees C, ionic strength 0.2 M (KCI). Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T-+/-) and an anionic (T-) one, whereby amine catalysis (deprotonation of T-+/- to give T-) is kinetically important. Both the pK(a) of T-+/- and the rate coefficient for proton transfer (k(3) ca. 10(10) s(-1) M(-1)) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Bronsted type plots for amine basicity have slopes beta(N) ca, 0.2 for rate-determining amine attack (k(1)) and beta(N) ca. 0.8 for amine expulsion from T-+/- (k(-1)), in accord with the beta(N) values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k(2)) from T-+/- (which competes with amine deprotonation of T-+/-) relative to the same expulsion from the analogous oxy intermediate.

  DOI：

  10.1021/jo951726u
• 作为产物：
  描述：

  在 potassium chloride 作用下， 以 水 为溶剂， 生成 piperidinium cation 、 Ethoxy-(4-nitrophenoxy)methanethione
  参考文献：
  名称：

  Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Ethyl Thionocarbonates

  摘要：

  The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0 degrees C, ionic strength 0.2 M (KCI). Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T-+/-) and an anionic (T-) one, whereby amine catalysis (deprotonation of T-+/- to give T-) is kinetically important. Both the pK(a) of T-+/- and the rate coefficient for proton transfer (k(3) ca. 10(10) s(-1) M(-1)) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Bronsted type plots for amine basicity have slopes beta(N) ca, 0.2 for rate-determining amine attack (k(1)) and beta(N) ca. 0.8 for amine expulsion from T-+/- (k(-1)), in accord with the beta(N) values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k(2)) from T-+/- (which competes with amine deprotonation of T-+/-) relative to the same expulsion from the analogous oxy intermediate.

  DOI：

  10.1021/jo951726u

文献信息

• Kinetics and Mechanism of the Pyridinolysis of Alkyl Aryl Thionocarbonates
  作者：Enrique A. Castro、María Cubillos、José G. Santos、Jimena Téllez

  DOI：10.1021/jo961921o

  日期：1997.4.1

  among them and with similar ones permits the following conclusions: (i) There is no variation of k(N) by substitution of methoxy by ethoxy as the nonleaving group of the substrate. (ii) The pK(a)(o) value is smaller for the less basic aryloxide nucleofuge due to a larger k(2) value. (iii) The change of C=S by C=O as the electrophilic center of the substrate results in larger values for both k(-)(1)

  在水中进行动力学研究甲基4-硝基苯基，乙基4-硝基苯基和2,4-二硝基苯基硫代碳酸乙酯（分别为MNPTOC，ENPTOC和EDNPTOC）与一系列3-和4-取代的吡啶的反应，温度为25.0摄氏度，离子强度为0.2 M（用KCl保持）。在胺过量的情况下，获得伪一级速率系数（k（obsd）），其与游离吡啶浓度成线性比例。获得二阶速率系数（k（N））作为这些图的斜率。发现的两个一硝基衍生物的布朗斯台德图在一条直线上（斜率和截距相同）等于斜率β= 1.0。EDNPTOC热解显示弯曲的布朗斯台德图，斜率beta（1）= 0.1（高pK（a）），beta（2）= 1.0（低pK（a））和pK（a）（o）= 6 。8（曲率中心处的pK（a）值）。这些图与反应路径上两性离子四面体中间体（T（+/-））的存在是一致的，由此在低pK（k）下从T（+/-）排出芳氧基阴离子是速率确定的（k（2）步骤）。 a）对于
• Novel prodrugs for antimicrobial amidines
  申请人：——

  公开号：US20020019437A1

  公开（公告）日：2002-02-14

  A methods of treating an infection comprises administering a therapeutically effective amount of a compound described by the Formula (I): 1 wherein: X may be O, S, or NR′ wherein R′ is H or loweralkyl; R 1 and R 2 may be independently selected from the group consisting of H, loweralkyl, oxyalkyl, alkoxyalkyl, cycloalkyl, aryl, hydroxyalkyl, aminoalkyl, and alkylaminoalkyl; R 3 and R 4 are each independently selected from the group consisting of H, loweralkyl, halogen, oxyalkyl, oxyaryl, and oxyarylalkyl; R 5 is represented by a formula selected from the group consisting of: 2 wherein: X 1 , X 2 , and X 3 are independently selected from O and S; and R 6 and R 7 are independently selected from the group consisting of loweralkyl, aryl, alkylaryl, oxyaryl, an ester-containing substituent, and oxyalkyl; or a pharmaceutically acceptable salt thereof.

  一种治疗感染的方法包括给予公式（I）描述的化合物的治疗有效量：其中：X可以是O、S或NR′，其中R′为H或较低烷基；R1和R2可以独立地选择自H、较低烷基、氧烷基、烷氧基烷基、环烷基、芳基、羟基烷基、氨基烷基和烷基氨基烷基的群；R3和R4各自独立地选择自H、较低烷基、卤素、氧烷基、氧芳基和氧芳基烷基的群；R5由以下公式中选择：其中：X1、X2和X3独立选择自O和S；R6和R7独立选择自较低烷基、芳基、烷基芳基、氧芳基、含酯基取代基和氧烷基的群；或其药学上可接受的盐。
• NOVEL PRODRUGS FOR ANTIMICROBIAL AMIDINES
  申请人：UNIVERSITY OF NORTH CAROLINA AT CHAPEL HILL

  公开号：EP1242059A2

  公开（公告）日：2002-09-25
• US6486200B1
  申请人：——

  公开号：US6486200B1

  公开（公告）日：2002-11-26
• US6503940B2
  申请人：——

  公开号：US6503940B2

  公开（公告）日：2003-01-07