4-nitrophenyl N-benzylsulfamate

• 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: 4-nitrophenyl N-benzylsulfamate
• 英文别名: 4-nitrophenyl benzylsulfamate；(4-nitrophenyl) N-benzylsulfamate
• 化学式: C₁₃H₁₂N₂O₅S
• 分子量: 308.315
• InChiKey: PKURSRYWBNMHDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-nitrophenyl N-benzylsulfamate 在 potassium chloride 、 四丁基溴化铵 、 水 、 potassium carbonate 作用下， 以 苯 为溶剂， 反应 72.5h， 生成 4-nitrophenyl 4'-fluorobenzylsulfamate
  参考文献：
  名称：

  苯基和苄基4-硝基苯基氨基磺酸酯的水解机理†

  摘要：

  研究了一系列苯氨基磺酸酯1在中等酸强度（pH区间2-5）下的水解动力学，发现它们通过缔合S N 2（S）机理与水 充当亲核试剂攻击硫，裂解S–O键，同时与a的氧形成新的S–O键 水 分子导致 氨基磺酸 和 苯酚作为产品。在中性至中度碱性溶液（pH≥〜6–9）中，遵循解离（E1cB）途径，其中包括：i）氨基电离，然后ii）从电离酯中单分子驱离离去基团，得到N-磺胺[HN SO 2 ]作为中间体。在更碱性溶液中的酯的共轭碱的进一步电离发生以得到排出的芳基氧化物的离去基团，得到新颖的双阴离子物种Ñ -sulfonylamine阴离子[ - Ñ SO 2 ]; 在最后一步中，氢氧根离子或氢氧根离子的快速侵蚀水 分子再次导致 氨基磺酸。在6.4–14的pH范围内水解了一系列取代的4-硝基苯基氨基磺酸苄酯4，形成了Hammett关系，该关系的反应常数与E1cB机理一致。

  DOI：

  10.1039/c0ob00362j
• 作为产物：
  描述：

  4-nitrophenyl 1H-imidazole-1-sulfonate 以 二氯甲烷 、 乙腈 为溶剂， 生成 4-nitrophenyl N-benzylsulfamate
  参考文献：
  名称：

  O-(Aminosulfonylation) of phenols and an example of slow hydrolytic release

  摘要：

  Sequential replacement of imidazole from sulfonyldiimidazole by phenols and then amines leads to O-arylsulfamate esters. Application of this coupling method to 19 phenols and 6 amines generates a library of 114 sulfamate esters, Ar-OSO2-NR2. A sulfamate based conjugate of ethinyl estradiol was prepared by using the steroid 3-hydroxyl as the phenol component, and an amino amide derived from linoleic acid as the amine. Hydrolysis of this conjugate was studied in aqueous buffer at pH values 2, 5, and 7.4, and (essentially identical) respective half-lives of 6.8, 6.6, and 6.7 days were observed. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.10.065

文献信息

• Aminolysis and hydrolysis of sulphamate esters: Substantial N?S bonding in the transition state leading to N?sulfonylamines
  作者：William J. Spillane、Geraldine Hogan、Paul McGrath

  DOI：10.1002/poc.610080907

  日期：1995.9

  −ONp and sometimes also by the disapperance of ester. The reaction was found to be independent of amine type and concentration and at the high pHs that obtain the substrate esters are fully ionized. A Hammett ρacyl of −;1·8 was obtained for the decomposition of the sulphamate anions and this is consistent with substantial NS bonding in the transition state leading to N-sulphonylamine, RNSO2. This intermediate

  的几个氨基磺酸酯的氨解和水解，RNHSO 2 ONP（R =的PhCH 2中，Ph，4-MEC 6 ħ 4 4，3-MEC 6 ħ 4，4-FC 6 H ^ 4，4-CLC 6 ħ 4，3在各种温度下于50％（v / v）的乙腈水溶液中研究了-ClC 6 H 4，H; Np = 4-NO 2 C 6 H 4）。与胺（R酯的反应1 NH 2）给出- ONP和两个硫酰胺，（RNHSO 2 NHR 1）和氨基磺酸盐（RNHSO 2 O - R 1 NH 3 +）产物。一阶速率通过的外观来确定- ONP有时也通过酯的disapperance。发现该反应不依赖于胺的类型和浓度，并且在高pH下获得的底物酯被完全离子化。获得了-; 1·8的哈米特ρ酰基用于氨基磺酸根阴离子的分解，这与在过渡态下产生N-磺酰胺RN SO 2的大量N S键合是一致的。然后该中间体非常迅速地分配，并与R 1 NH 2和H反应2
• Change in Rate-Determining Step in an E1cB Mechanism during Aminolysis of Sulfamate Esters in Acetonitrile
  作者：William J. Spillane、Paul McGrath、Chris Brack、Andrew B. O'Byrne

  DOI：10.1021/jo015691b

  日期：2001.9.1

  The kinetics of the reactions of the nitrogen-sulfur(VI) esters 4-nitrophenyl N-methylsulfamate (NPMS) with a series of pyridines and a series of alicyclic amines and of 4-nitrophenyl N-benzylsulfamate (NPBS) with pyridines, alicyclic amines, and a series of quinuclidines have been investigated in acetonitrile (ACN) in the presence of excess amine at various temperatures. Pseudo-first-order rate constants

  氮-硫（VI）酯4-硝基苯基N-甲基氨基磺酸酯（NPMS）与一系列吡啶和一系列脂环族胺的反应动力学和4-硝基苯基N-苄基氨基磺酸盐（NPBS）与吡啶，脂环族胺反应的动力学，并且已经在各种温度下在过量胺存在下在乙腈（ACN）中研究了一系列喹核苷。伪一阶速率常数（k（obsd））已通过监视4-硝基苯酚/ 4-硝基苯酚的释放获得。从k（obsd）对[胺]的图的斜率，获得了NPMS的吡啶分解的二阶速率常数（k'（2）），以及log k'（2）对pK的布朗斯台德图。 （a）吡啶给出一条直线，β= 0.45。但是，使用NPMS的脂环族胺进行氨解产生了两相布朗斯台德图（beta（1）= 0.6，beta（2）大约等于0）。用NPBS的脂环族胺和喹核苷进行吡啶解和氨解也得到了类似的两相布朗斯台德图。这种两相行为是根据E1cB机理从（E1cB）（irrev）（少碱性胺）到（E1cB）（rev）（更多碱性胺）
• Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile
  作者：William J. Spillane

  DOI：10.1039/a801505h

  日期：——

  The observation of biphasic Brønsted plots (β1ca. 0.7 and β2ca. 0) in the aminolysis (alicyclic amines, pyridines) of 4-nitrophenyl N-benzylsulfamate 1a in MeCN is interpreted as being due to a mechanistic change from (ElcB)irrev to (ElcB)rev; the change in rate-determining step occurs at approximately the pKa of 1a and other more basic substrates give straight line plots; an entropy study supports the change from a bimolecular to a unimolecular mechanism.

  在 MeCN 中的氨解（脂环胺、吡啶）过程中观察到双相布氏图（β1ca.在 MeCN 中对 4-硝基苯基 N-苄基氨基磺酸 1a 进行氨基分解（脂环胺、吡啶）时观察到的双相布氏图谱（β1ca 0.7 和 β2ca 0）被解释为是由于机理从 (ElcB)irrev 转变为 (ElcB)rev；速率决定步骤的变化发生在 1a 的 pKa 附近，而其他碱性更强的底物则给出了直线图谱；熵研究支持从双分子机理转变为单分子机理。
• Spillane, William J.; Hogan, Geraldine; McGrath, Paul, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1996, vol. 10, p. 2099 - 2104
  作者：Spillane, William J.、Hogan, Geraldine、McGrath, Paul、King, Joseph、Brack, Chris

  DOI：——

  日期：——
• O-(Aminosulfonylation) of phenols and an example of slow hydrolytic release
  作者：Baocheng Yang、Zhexun Sun、Changzhi Liu、Yan Cui、Zhilei Guo、Yuwei Ren、Zhijian Lu、Spencer Knapp

  DOI：10.1016/j.tetlet.2014.10.065

  日期：2014.12

  Sequential replacement of imidazole from sulfonyldiimidazole by phenols and then amines leads to O-arylsulfamate esters. Application of this coupling method to 19 phenols and 6 amines generates a library of 114 sulfamate esters, Ar-OSO2-NR2. A sulfamate based conjugate of ethinyl estradiol was prepared by using the steroid 3-hydroxyl as the phenol component, and an amino amide derived from linoleic acid as the amine. Hydrolysis of this conjugate was studied in aqueous buffer at pH values 2, 5, and 7.4, and (essentially identical) respective half-lives of 6.8, 6.6, and 6.7 days were observed. (C) 2014 Elsevier Ltd. All rights reserved.