bis(4-nitrophenyl) thionocarbonate | 5070-14-4

• 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: bis(4-nitrophenyl) thionocarbonate
• 英文别名: bis-(4-nitrophenyl) thiocarbonate；thiocarbonic acid O,O'-bis-(4-nitro-phenyl ester)；Thiokohlensaeure-O,O'-bis-(4-nitro-phenylester)；o,o-Bis(4-nitrophenyl) carbonothioate；bis(4-nitrophenoxy)methanethione
• CAS: 5070-14-4
• 化学式: C₁₃H₈N₂O₆S
• 分子量: 320.282
• InChiKey: FICYQLPUFKQUKP-UHFFFAOYSA-N

物化性质

• 熔点：
  196-197 °C
• 沸点：
  479.9±55.0 °C(Predicted)
• 密度：
  1.521±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  142
• 氢给体数：
  0
• 氢受体数：
  7

安全信息

• 海关编码：
  2930909090

反应信息

• 作为反应物：
  描述：

  bis(4-nitrophenyl) thionocarbonate 生成 thiocarbonic acid O,S-bis-(4-nitro-phenyl ester)
  参考文献：
  名称：

  A Study of the Schönberg Rearrangement of Diaryl Thioncarbonates to Diaryl Thiolcarbonates¹

  摘要：

  DOI：

  10.1021/ja01614a035
• 作为产物：
  描述：

  硫光气 、 lithium 4-nitrophenolate 以 四氢呋喃 为溶剂， 生成 bis(4-nitrophenyl) thionocarbonate
  参考文献：
  名称：

  Structure−Reactivity Correlations in the Aminolysis and Pyridinolysis of Bis(phenyl) and Bis(4-nitrophenyl) Thionocarbonates

  摘要：

  The reactions of a series of secondary alicyclic amines with bis(phenyl) and bis(4-nitrophenyl) thionocarbonates (BPTOC and BNPTOC, respectively), and a series of pyridines with the latter substrate, are subjected to a kinetic investigation in water, 25.0 degrees C, ionic strength 0.2 M (KCl). All the reactions obey pseudo-first-order kinetics under amine excess over the substrate. The reactions of piperidine with BPTOC are first order in amine, but those of the same substrate with the other secondary alicyclic amines exhibit a complex order, consistent with the existence of both a zwitterionic (T+/-) and an anionic (T-) tetrahedral intermediates on the reaction pathway. Deprotonation of T+/- by a secondary amine to give T- (rate coefficient k(3)) competes with expulsion of the amine moiety from T+/- (k(-1)), except in the reactions of 1-formylpiperazine whereby k(-1) much greater than k(3) [1-formylpiperazine], and a kinetics second order in amine is observed. The reactions of secondary alicyclic amines with BNPTOC are all first order in amine and show a nonlinear Bronsted-type plot with limiting slopes beta = 0.1 (high amine pK(a)) and beta = 0.5 (low amine pK(a)). This slight curvature is consistent with a concerted mechanism (one step). The intermediate T+/- is not formed because of its high kinetic instability due to a large k(-1) value. The pyridinolysis of BNPTOC exhibits a first order in amine kinetics and a linear Bronsted-type plot of slope beta = 1.0, which is consistent with the existence of T+/- whereby the expulsion of the leaving group from T+/- is the rate-determining step. This intermediate is less unstable than that with a secondary amine due to the fact that k(-1) is smaller for a pyridine compared to an isobasic secondary alicyclic amine.

  DOI：

  10.1021/jo970624w

文献信息

• Kinetic Study of the Phenolysis of Bis(4-nitrophenyl) Carbonate, Bis(4-nitrophenyl) Thionocarbonate, and Methyl 4-Nitrophenyl Thionocarbonate
  作者：Enrique A. Castro、Mauricio Angel、David Arellano、José G. Santos

  DOI：10.1021/jo0101252

  日期：2001.10.1

  The reactions of a homogeneous series of phenols with bis(4-nitrophenyl) carbonate (BNPC), bis(4-nitrophenyl) thionocarbonate (BNPTOC), and methyl 4-nitrophenyl thionocarbonate (MNPTOC) are subjected to a kinetic investigation in water, at 25.0 degrees C and ionic strength of 0.2 M (KCl). Under excess of phenol over the substrate, all the reactions obey pseudo-first-order kinetics and are first order

  均相系列苯酚与碳酸双（4-硝基苯酯），双（4-硝基苯基）硫代碳酸酯（BNPTOC）和4-硝基苯基硫代碳酸甲酯（MNPTOC）的反应在水中进行25.0摄氏度，离子强度为0.2 M（KCl）。在底物上过量的苯酚下，所有反应均遵循拟一级反应动力学，并且在酚盐阴离子中为一级反应。BNPC的反应显示出线性的Bönsted型图，斜率β= 0.66，与一致的机理一致（一个步骤）。相比之下，BNPTOC和MNPTOC的双相布朗斯台德图在高pK（a）时斜率分别为β= 0.30和0.44，在低pK（a）时斜率分别为β= 1.25和1.60，与逐步一致机制。对于两种硫代碳酸酯的反应，布朗斯台德图中心（pK（a）（0））的pK（a）值为7.1，它对应于4-硝基苯酚的pK（a）。这证实了硫代碳酸酯的酚类是逐步过程，形成了阴离子四面体中间体。通过比较标题反应和相似反应的动力学和机理，可以得出以下结论：（i）在阴离子四
• 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
• Kinetics and mechanism of the anilinolysis of aryl 4-nitrophenyl thionocarbonates in aqueous ethanol
  作者：Enrique A. Castro、Rayen Acevedo、José G. Santos

  DOI：10.1002/poc.1814

  日期：2011.7

  aniline concentration are linear, with the slopes (kN) pH independent, kN being the rate coefficient for the anilinolysis of the thionocarbonates. The Brønsted plot (log kN vs. pKa of anilinium ions) for thionocarbonate 1 is linear, with slope (β) 0.62, which is consistent with a concerted mechanism. The Brønsted plots for thionocarbonates 2 and 3 are curved, with slopes 0.1 at high pKa for both reaction

  双（4-硝基苯基），3-氯苯基4-硝基苯基，和3-甲氧基苯基4-硝基苯基thionocarbonates（的反应1，2，和3，分别地）与一系列苯胺经受在44重量动力学调查。 ％乙醇-水，在25.0°C，离子强度为0.2M。在苯胺过量的情况下，发现拟一级反应速率系数（k obs）。k obs对苯胺浓度的曲线是线性的，其斜率（k N）与pH无关，k N是硫代碳酸盐的苯胺分解的速率系数。布朗斯台德图（log  k N vs. p K一苯胺离子）为硫羰碳酸酯1是直链的，具有斜率（β）0.62，这与协同机制是一致的。所述布朗斯台德地块为thionocarbonates 2和3是弯曲的，与高磷斜坡0.1 ķ一个用于两个反应系列和斜坡0.84和0.79，在低p- ķ一个用于反应2和3分别。后者图是根据到一个步进机制，通过两性离子的四面体中间体（T ±）及其阴离子类似物（T - ），后者是用T的去质子化形成±通过缓冲区的基本形式（HPO
• Nesynov,E.P.; Pel'kis,P.S., Journal of Organic Chemistry USSR (English Translation), 1967, vol. 3, p. 831 - 835
  作者：Nesynov,E.P.、Pel'kis,P.S.

  DOI：——

  日期：——
• A Study of the Schönberg Rearrangement of Diaryl Thioncarbonates to Diaryl Thiolcarbonates¹
  作者：H. R. Al-Kazimi、D. S. Tarbell、Derek Plant

  DOI：10.1021/ja01614a035

  日期：1955.5