N-isopropyl hydroxylamine hydrogen oxalate | 858220-30-1

• 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: N-isopropyl hydroxylamine hydrogen oxalate
• 英文别名: N-isopropylhydroxylamine hydrogen oxalate；N-isopropylhydroxylamine oxalate；N-Isopropylhydroxylamin-oxalat；isopropylhydroxylamine oxalate；N-Isopropylhydroxylamineoxalate；oxalic acid;N-propan-2-ylhydroxylamine
• CAS: 858220-30-1
• 化学式: C₂H₂O₄*C₃H₉NO
• 分子量: 165.146
• InChiKey: SRMYKGRGIIURAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.47
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  107
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N-isopropyl hydroxylamine hydrogen oxalate 、 苯甲酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以76%的产率得到N-hydroxy-N-isopropylbenzamide
  参考文献：
  名称：

  Lawesson试剂与N-烷基异羟肟酸的反应机理

  摘要：

  通过研究 2,4-双（4-甲氧基苯基）-1,3,2,4-二硫代二膦烷 2,4-二硫化物（劳森试剂，LR）和N-烷基异羟肟酸 HA 1. 主要中间体是一种加合物，O-二硫代膦酰化异羟肟酸 19，它分解产生偏硫代膦酸酯 (AnsPOS)、一个硫原子和一个酰胺。同时，由于 19 和间二硫代膦酸酯 (AnsPSS) 在平衡状态下共存，羰基被硫代化。还已经确定，在还原和硫化过程中形成的单体 AnsPOS 不会低聚成环状三聚体 5 和线性低聚物，这是酰胺与 LR 反应的典型特征。由于反应混合物中有未反应的HA 1，AnsPOS 参与受控转化以形成二聚体，即相应的焦硫代膦酸酯 3，以及中间体 O-硫代膦酰化异羟肟酸 2。AnsPOS 的水解产物，即 (4-甲氧基苯基) 硫代膦酸 4，参与最后的反应。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  DOI：

  10.1002/ejoc.200400727
• 作为产物：
  描述：

  2-硝基丙烷 、 草酸 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 生成 N-isopropyl hydroxylamine hydrogen oxalate
  参考文献：
  名称：

  Ozaki, Shigeko; Nishiguchi, Susumu; Masui, Masaichiro, Chemical and pharmaceutical bulletin, 1984, vol. 32, # 7, p. 2609 - 2616

  摘要：

  DOI：

文献信息

• S-Thioacyldithiophosphates in the Synthesis of Thiohydroxamic Acids and O-Thioacylhydroxylamines
  作者：Leszek Doszczak、Janusz Rachon

  DOI：10.1055/s-2002-31957

  日期：——

  S-Thioacyldithiophosphates proved to be excellent thioacylating agents. They are easily available from carboxylic acids. Due to their low reactivity towards oxygen nucleophiles and high reactivity towards nitrogen ones they found application in the synthesis of thiohydroxamic acids directly from hydroxylamines without protection on the hydroxy group. However, in cases of steric hindrance O-thioacyl hydroxylamines are formed and can be isolated with high yield.

  S-硫代酰基二硫代磷酸盐被证明是非常优秀的硫代酰化试剂，它们可从羧酸中容易地获得。由于它们对氧亲核试剂的反应性低，但对氮亲核试剂的反应性高，因此它们在直接从羟胺合成硫代羟肟酸时无需对羟基进行保护。然而，在存在立体阻碍的情况下会形成O-硫代酰基羟胺，并且可以高产率地分离出来。
• Synthesis of S-thioacyl dithiophosphates, efficient and chemoselective thioacylating agentsProofs for the reversibility of isomerisation of anhydrides 1 to 2, melting points of amides and thioamides obtained from anhydrides 5–7 and 1H, 13C NMR and IR data of isolated anhydrides 5–7, 17 are available as supplementary data. For direct access, see http://www.rsc.org/suppdata/p1/b2/b201233b/
  作者：Leszek Doszczak、Janusz Rachon

  DOI：10.1039/b201233b

  日期：2002.5.10

  Easily available acyl dithiophosphates are not stable and isomerise reversibly to O-thioacyl monothiophosphates, especially when subjected to heating. Much slower but probably irreversible isomerisation to S-thioacyl monothiophosphates occurs. Since equilibrium states are established and S-thioacyl (mono)thiophosphates form slowly, reaction mixtures contain generally both thioacylating and acylating agents, and consequently cannot be used for efficient thioacylation. On the other hand, treatment of a mixture of isomeric anhydrides with an excess of a dithiophosphoric acid leads to exclusive formation of S-thioacyl dithiophosphates. They appear to be excellent thioacylating agents: relatively stable, inert towards water and oxygen and therefore easy to handle. Reactions with nitrogen or sulfur nucleophiles proceed very rapidly under ambient conditions, yielding respective thioacyl derivatives. Isolation of the products is very simple. Due to the low reactivity of S-thioacyl dithiophosphates towards oxygen nucleophiles they can be used for direct thioacylation of multifunctional nucleophiles with unprotected hydroxy groups. Respective thioacyl derivatives cannot readily be obtained using other methods.

  容易获得的酰基二硫代磷酸酯不稳定，特别是在加热条件下，可以可逆地异构化为O-硫代酰基单硫代磷酸酯。转变为S-硫代酰基单硫代磷酸酯的过程要慢得多，但可能是不可逆的。由于建立了平衡状态，S-硫代酰基（单）硫代磷酸酯的形成较慢，反应混合物通常既含有硫代酰化剂也含有酰化剂，因此无法用于高效的硫代酰化反应。另一方面，将异构酸酐混合物与过量的二硫代磷酸反应，会导致仅形成S-硫代酰基二硫代磷酸酯。它们似乎是非常优秀的硫代酰化剂：相对稳定，对水和氧气不敏感，因此易于处理。它们在常温下与氮或硫亲核试剂的反应非常迅速，产生相应的硫代酰基衍生物。产品的分离非常简单。由于S-硫代酰基二硫代磷酸酯对氧亲核试剂的反应性较低，因此它们可以用于直接硫代酰化多功能亲核试剂，而不需要保护羟基。使用其他方法不易获得相应的硫代酰基衍生物。
• Oxaza heterocycles and pharmaceutical compositions containing same
  申请人：Biofor, Ltd.

  公开号：US04892870A1

  公开（公告）日：1990-01-09

  A novel class of 5, 6 or 7 member heterocycles which belong to the 3-isoxazolidinone, 2H-1,2-oxazin-3 (4H)-one and 3-isoxazepinone series of compounds and which are substituted at the 4-carbon by a benzylidene radical. The compounds have utility as analgesic agents, immunomodulating agents, anti-inflammatory agents and anti-pyretic agents and they may be combined with excipients to provide formuations which are useful in treating arthritis and conditions generally associated with that disease.

  一类新型的5、6或7成员杂环化合物，属于3-异噁唑烷酮、2H-1,2-噁唑-3(4H)-酮和3-异噁唑烷酮系列化合物，其在4-碳上被苯甲亚基取代。这些化合物可用作镇痛剂、免疫调节剂、抗炎剂和退热剂，并可与赋形剂结合以提供用于治疗关节炎和通常与该疾病相关的疾病的制剂。
• Lawesson's reagent for direct thionation of hydroxamic acids: Substituent effects on LR reactivity
  作者：Witold Przychodzeń

  DOI：10.1002/hc.20259

  日期：——

  To explore the generality and scope of direct thionation of hydroxamic acids (HAs), the reaction of various structurally diverse HAs with Lawesson's reagent was investigated. The yield of thiohydroxamic acid (THAs) is poor when HAs possess bulky acyl and/or N-substituents, acidic α-hydrogen atoms, or an N-phenyl ring. THAs yields were correlated with Brown sigma parameter. The relative rates of two

  为了探索异羟肟酸 (HA) 直接硫化的一般性和范围，研究了各种结构不同的 HA 与劳森试剂的反应。当 HA 具有庞大的酰基和/或 N-取代基、酸性 α-氢原子或 N-苯环时，硫代异羟肟酸 (THA) 的产率很低。THA 产量与 Brown sigma 参数相关。还测量了两个后续过程 k 和 k 的相对速率。还发现了 N-异丙基苯并硫代异羟肟酸的次甲基质子化学位移的相关性。© 2006 Wiley Periodicals, Inc. 杂原子化学 17:676–684, 2006; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20259
• N-Hydroxyisothioharnstoffe, 2. Mitt. Addition von N-substituierten Hydroxylaminen an Methylthiocyanat
  作者：Bernd Clement、Stefan Wissel

  DOI：10.1002/ardp.19883211018

  日期：——

  N‐Hydroxyisothioureas, Part 2: Addition of N‐Substituted Hydroxylamines to Methylthiocyanate

  N-羟基异硫脲，第 2 部分：将 N-取代的羟胺添加到甲基硫氰酸酯中