1-nitro-2-(2-nitrovinyl)benzene

• 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: 1-nitro-2-(2-nitrovinyl)benzene
• 英文别名: β,2-dinitrostyrene；beta,2-Dinitrostyrene；1-nitro-2-(2-nitroethenyl)benzene
• 化学式: C₈H₆N₂O₄
• 分子量: 194.147
• InChiKey: INIQBBVYBCGEIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  91.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-nitro-2-(2-nitrovinyl)benzene 在 Amberlyst A-26 (OH^-) 、 双氧水 作用下， 以 1,4-二氧六环 为溶剂， 反应 8.0h， 以82%的产率得到邻硝基苯甲酸
  参考文献：
  名称：

  Transformation of Β-Nitrostyrenes to Carboxylic Acids Using Amberlyst A-26 Supported Hydroperoxide

  摘要：

  Nitrostyrenes are conveniently converted to the corresponding carboxylic acids in high C yields at room temperature with Amberlyst A-26 supported hydroperoxide which is prepared in situ from 35% hydrogen peroxide and amberlyst A-26 (OH-).

  DOI：

  10.1007/s007060200089
• 作为产物：
  描述：

  2-nitrocinnamic acid 在 硝酸 作用下， 生成 1-nitro-2-(2-nitrovinyl)benzene
  参考文献：
  名称：

  Functional hyperandrogenism detected by corticotropin and GnRH-analogue stimulation tests in women affected by apparently idiopathic hirsutism

  摘要：

  The etiologic diagnosis of hirsutism is often difficult. Previous studies have reported normal basal androgen and SHBG concentrations in 33-50% of hirsute women, suggesting the presence of an "idiopathic" form of hirsutism as the most frequent cause of this problem. The recent use of GnRH-analogues together with the corticotropin stimulation test allows better understanding of whether the cause of hirsutism is androgen excess and, if so, whether the origin of the latter is ovarian, adrenal or both. The present study evaluated adrenal and ovarian function in 48 young hirsute women as well as in 78 normal women matched for body mass index and age, who acted as control group. To determine ovarian function, a single 100-mug dose of GnRH analogue triptorelin was injected sc; thereafter, gonadotropins, 17-hydroxyprogesterone (17-OHP), Delta4-androstenedione (Delta4), total testosterone (T) and estradiol were determined. To better understand the adrenal function, 250 mug of 1,24 ACTH were administrated as iv infusion for 5 h, and plasma cortisol (F), 17-OHP, Delta4, DHEAS, T, 11-desossicortisol were measured. The combined use of these two stimulation tests was able to detect mild to moderate abnormalities in the steroidogenesis of ovaries alone (23%), adrenals alone (16.6%), or both (35.4%) in most hirsute women (75%) with otherwise normal baseline androgen concentrations. In particular, patients showed significantly increased responses of 17-OHP, Delta4, total T, 11-desossicortisol, and F to 1,24-ACTH administration. Moreover, they also had significantly higher 17-OHP and T responses to triptorelin. In conclusion, milder forms of functional ovarian and/or adrenal hyperandrogenism, similar to those found in clearly hyperandrogenic women, were observed and could be an underlying mechanism of idiopathic hirsutism. (J. Endocrinol. Invest. 24: 491-498, 2001) (C) 2001, Editrice Kurtis.

  DOI：

  10.1007/bf03343881

文献信息

• Cyanomethyl anion transfer reagents for diastereoselective Corey–Chaykovsky cyclopropanation reactions
  作者：Renè Hommelsheim、Katharina J. Hock、Christian Schumacher、Mohanad A. Hussein、Thanh V. Nguyen、Rene M. Koenigs

  DOI：10.1039/c8cc05602a

  日期：——

  A readily available and bench-stable cyanomethyl sulfonium salt was used in highly diastereoselective Corey–Chaykovsky cyclopropanation reactions of electron-poor olefins. This efficient method provides a rapid route to access densely functionalized cyclopropyl nitriles.

  一种易于获得且稳定的氰基甲基methyl盐被用于高度非对映选择性的电子贫烯烃的Corey-Chaykovsky环丙烷化反应中。这种有效的方法提供了一种快速途径来获取致密的官能化环丙基腈。
• Novel thiourea-amine bifunctional catalysts for asymmetric conjugate addition of ketones/aldehydes to nitroalkenes: rational structural combination for high catalytic efficiency
  作者：Jia-Rong Chen、Yi-Ju Cao、You-Quan Zou、Fen Tan、Liang Fu、Xiao-Yu Zhu、Wen-Jing Xiao

  DOI：10.1039/b925962g

  日期：——

  A series of thiourea-amine bifunctional catalysts have been developed by a rational combination of prolines with cinchona alkaloids, which are connected by a thiourea motif. The catalyst 3a, prepared from L-proline and cinchonidine, was found to be a highly efficient catalyst for the conjugate addition of ketones/aldehydes to a wide range of nitroalkenes (up to 98/2 dr and 96% ee). The privileged cinchonidine

  一系列 硫脲-胺双功能催化剂是通过脯氨酸与金鸡纳生物碱的合理组合而开发的，金鸡纳生物碱通过硫脲基序连接。催化剂3a由大号脯氨酸 和 辛可尼定被发现是一种高效的催化剂，用于将酮/醛共轭加成到各种各样的硝基烯烃中（高达98/2 dr和96％ee）。特权的辛可尼定骨架和硫脲基序对于反应活性和对映选择性是必不可少的。
• Primary Amine-Thioureas with Improved Catalytic Properties for “Difficult” Michael Reactions: Efficient Organocatalytic Syntheses of (S)-Baclofen, (R)-Baclofen and (S)-Phenibut
  作者：Michail Tsakos、Christoforos G. Kokotos、George Kokotos

  DOI：10.1002/adsc.201100636

  日期：2012.3

  Among the class of primary amine‐thioureas based on tert‐butyl esters of α‐amino acids, the most efficient organocatalyst for “difficult” Michael reactions was identified. The derivative based on (S)‐di‐tert‐butyl aspartate and (1R,2R)‐diphenylethylenediamine provided the products of the reaction between aryl methyl ketones and nitroolefins in excellent yields and enantioselectivities. In addition

  在基于α-氨基酸叔丁基酯的伯胺硫脲类中，发现了“难”迈克尔反应最有效的有机催化剂。基于（S）-二叔丁基天冬氨酸盐和（1 R，2 R）-二苯基乙二胺的衍生物提供了芳基甲基酮与硝基烯烃之间反应的产物，收率和对映选择性极好。另外，这种新催化剂可以以低催化剂负载量（5mol％）使用。有效合成（S）-baclofen，（R）-baclofen和（S）-phenibut的方法突显了这种方法的实用性。
• A Recyclable Organocatalyst for Asymmetric Michael Addition
  作者：Mei Yang、Yuecheng Zhang、Jiquan Zhao、Qiusheng Yang、Yi Ma、Xiaohui Cao

  DOI：10.1007/s10562-016-1693-x

  日期：2016.3

  In this study, a new organocatalyst derived from proline was developed and shown to be an efficient catalyst for asymmetric Michael addition reactions of ketones and aldehydes to nitroolefins with high diastereo- and enantioselectivities. (syn;anti up to 99:1, ee. up to 98 %.). Furthermore, the catalyst is easily recovered and could be reused six times without significant loss of its ability to affect

  在这项研究中，开发了一种衍生自脯氨酸的新型有机催化剂，它是酮和醛与硝基烯烃的不对称迈克尔加成反应的有效催化剂，具有高非对映选择性和对映选择性。（syn;anti 高达 99:1，ee。高达 98%。）。此外，催化剂很容易回收，可以重复使用六次，而不会显着丧失其影响不对称反应结果的能力。此外，对模型反应进行了 B3LYP/6-311G(d,p)//6-311 + G(2dp,f) 水平的计算研究，并证实了以下假设：首先，羧基之间的氢键基团和硝基在催化中起重要作用，其次是酮反应形成2S的重新攻击的能垒，3R 产物低于导致 2S、3R 产物的 si-face 攻击。Graphical Abstract 使用先前报道的有机催化剂（图中的铅化合物）的结构改性设计了一种高效且可回收的有机催化剂，用于不对称迈克尔加成。引入的羧基不仅提高了对映选择性，而且为催化剂的回收带来了便利。
• Samarium(0) and 1,1‘-Dioctyl-4,4‘-Bipyridinium Dibromide:  A Novel Electron-Transfer System for the Chemoselective Reduction of Aromatic Nitro Groups
  作者：Chengzhi Yu、Bin Liu、Longqin Hu

  DOI：10.1021/jo005666q

  日期：2001.2.1

  A mild and efficient electron-transfer method was developed for the chemoselective reduction of aromatic nitro groups using samarium(0) metal in the presence of a catalytic amount of 1,1'-dioctyl-4,4'-bipyridinium dibromide. This method was found to give the product aromatic amine in 79-99% yield with selectivity over a number of other functional and protecting groups such as alkene, azide, benzyl

  在催化量的1,1'-二辛基-4,4'-联吡啶二溴化物存在下，开发了一种温和有效的电子转移方法，用于使用sa（0）金属化学选择性还原芳香族硝基。发现该方法以79-99％的收率提供了产物芳香胺，对许多其他官能团和保护基团（例如烯烃，叠氮化物，苄基醚，腈，酰胺，卤化物，对甲苯磺酰胺，t-Boc，叔丁基二苯基甲硅烷基醚和脂肪族硝基。我们的结果还表明sa（0）在还原过程中起着重要作用，而1,1'-二辛基-4,4'-联溴化二溴化物充当电子转移催化剂，并且在激活（（0 ）金属。