1-N-乙酰基-3-硝基对亚苯二胺 | 6086-29-9

• 物质功能分类: 有机原料 - 氨基化合物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-N-乙酰基-3-硝基对亚苯二胺
• 中文别名: N-(4-氨基-3-硝基苯基)乙酰胺；乙酰胺,N-(4-氨基-3-硝基苯基)-；4-氨基-3-硝基乙酰苯胺
• 英文名称: 4-Amino-3-nitro-acetanilid
• 英文别名: 4-acetylamino-1-amino-2-nitrobenzene；N-(4-Amino-3-nitrophenyl)acetamide
• CAS: 6086-29-9
• 化学式: C₈H₉N₃O₃
• mdl: MFCD00035890
• 分子量: 195.178
• InChiKey: MGVDUDAXURKVCE-UHFFFAOYSA-N

物化性质

• 熔点：
  211.5-212.0 °C
• 沸点：
  332.7±27.0 °C(Predicted)
• 密度：
  1.428±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.125
• 拓扑面积：
  101
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 海关编码：
  2921590090

反应信息

• 作为反应物：
  描述：

  1-N-乙酰基-3-硝基对亚苯二胺 在 盐酸 、 水 、 铁粉 、 溶剂黄146 作用下， 生成 1,2,4-triaminobenzene N¹,N⁴-diacetate
  参考文献：
  名称：

  Buelow; Mann, Chemische Berichte, 1897, vol. 30, p. 986

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N'-二乙酰-1,4-苯二胺 在 硫酸 、 硝酸 作用下， 反应 0.92h， 生成 1-N-乙酰基-3-硝基对亚苯二胺
  参考文献：
  名称：

  Hypoxia-Selective Agents Derived from Quinoxaline 1,4-Di-N-oxides

  摘要：

  Hypoxic cells, which are a common feature of solid tumors, but not normal tissues, are resistant to both anticancer drugs and radiation therapy. Thus the identification of drugs with selective toxicity toward hypoxic cells is an important objective in anticancer chemotherapy. The benzotriazine di-N-oxide (SR 4233, Tirapazamine) has been shown to be an efficient and selective cytotoxin for hypoxic cells. Since the bioreductive activation of Tirapazamine is thought to be due to the presence of the 1,4-di-N-oxide moiety, a series of 3-aminoquinoxaline-2-carbonitrile 1,4-di-N-oxides with a range of electron-donating and -withdrawing substituents in the 6- and/or 7- positions has been synthesized and evaluated for toxicity to hypoxic cells. Electrochemical studies of the quinoxaline di-N-oxides and Tirapazamine showed that as the electron-withdrawing nature of the 6(7)-substituent increases, the reduction potential becomes more positive and the compound is more readily reduced. Apart from the unsubstituted 6a and the 6,7-dimethyl derivative 6c, the quinoxaline di-N-oxides have reduction potentials significantly more positive than Tirapazamine (E(pc)-0.90 V). The most potent cytotoxins to cells in culture were the 6,7,-dichloro and 6,7-difluoro derivatives 6i and 6l, which were 30-fold more potent than Tirapazamine. The 6(7)-fluoro and 6(7)-chloro compounds, 6e and 6h, showed the greatest hypoxia selectivity. Four of the compounds, 6e, 6f, 6h and 6i, killed the inner cells of multicellular tumor spheroids in vitro. In vivo Balb/c mice tolerated a dose of these four compounds twice the size of that of Tirapazamine. This study demonstrates that quinoxaline 1,4-di-N-oxides could provide useful hypoxia-selective therapeutic agents.

  DOI：

  10.1021/jm00010a023

文献信息

• [EN] FAR SUPERIOR OXIDATION CATALYSTS BASED ON MACROCYCLIC COMPOUNDS<br/>[FR] CATALYSEURS D'OXYDATION NETTEMENT SUPÉRIEURS À BASE DE COMPOSÉS MACROCYCLIQUES
  申请人：UNIV CARNEGIE MELLON

  公开号：WO2017053564A1

  公开（公告）日：2017-03-30

  An especially robust compound and its derivative metal complexes that are approximately one hundred-fold superior in catalytic performance to the previously invented TAML analogs is provided having the formula (I) wherein Y1, Y2, Y3 and Y4 are oxidation resistant groups which are the same or different and which form 5- or 6-membered rings with a metal, M, when bound to D; at least one Y incorporates a group that is significantly more stable towards nucleophilic attack than the organic amides of TAML activators; D is a metal complexing donor atom, preferably N; each X is a position for addition of a labile Lewis acidic substituent such as (i) H, deuterium, (ii) Li, Na, K, alkali metals, (iii) alkaline earth metals, transition metals, rare earth metals, which may be bound to one or more than one D, (iv) or is unoccupied with the resulting negative charge being balanced by a nonbonded counteraction; at least one Y may contain a site that is labile to acid dissociation, providing a mechanism for shortening complex lifetime. The new complexes deliver catalytic performances that promise to revolutionize multiple oxidation technology spaces including water purification.

  提供了一种特别强大的化合物及其衍生金属配合物，其催化性能大约比先前发明的TAML类似物优越一百倍，其化学式为（I），其中Y1、Y2、Y3和Y4是抗氧化的基团，可以相同也可以不同，并且与金属M结合时形成5-或6-成员环；至少一个Y包含一个对亲核攻击更稳定的基团，比TAML活化剂的有机酰胺更稳定；D是金属络合给体原子，优选为N；每个X是用于添加易失去的Lewis酸性取代基的位置，例如（i）H、氘，（ii）Li、Na、K、碱金属，（iii）碱土金属、过渡金属、稀土金属，可以与一个或多个D结合，（iv）或者未被占据，由非键合的对应作用平衡产生的负电荷；至少一个Y可能包含一个易于酸解离的位点，提供缩短配合物寿命的机制。这些新配合物提供了催化性能，有望彻底改变多种氧化技术领域，包括水净化。
• o-Nitroaniline derivatives. Part 10. 5- and 6-Amino-1H-benzimidazole 3-oxides
  作者：Michael D. McFarlane、David J. Moody、David M. Smith

  DOI：10.1039/p19880000691

  日期：——

  Cyclisation of N-(4- or 5-acylamino-2-nitrophenyl)glycine esters in basic media gives alkyl 5- or 6-acylaminobenzimidazole-2-carboxylate N-oxides, e.g. (11a) or (11b). Acid hydrolysis of the latter, followed by reaction with ammonia, gives the title compounds (1b) and (1c), in acceptable yield. The corresponding reaction sequence with 4-acylamino-N-cyanomethyl-o-nitroanilines also gives (1b); where

  环化ñ - （4-或5-酰氨基-2-硝基苯基）在碱性介质中的甘氨酸酯给出烷基的5-或6- acylaminobenzimidazole -2-甲酸甲酯Ñ -oxides，例如。（11a）或（11b）。后者的酸水解，然后与氨反应，以可接受的收率得到标题化合物（1b）和（1c）。与4-酰基氨基-N-氰基甲基-邻-硝基苯胺的相应反应序列也给出了（1b）；和。其中酰基为甲基磺酰基，但最终产物为5-甲磺酰胺基苯并咪唑N-氧化物（9）。化合物 （还可以通过还原然后水解从5-硝基苯并咪唑-2-羧酸N-氧化物乙酯获得1b）。
• Regioselective N-acetylation as a route of nitro-p-phenylenediamine metabolism by rat liver cytosol.
  作者：Mitsuo NAKAO、Yukiko GOTO、Yasuhiko MATSUKI、Akira HIRATSUKA、Tadashi WATABE

  DOI：10.1248/cpb.38.2561

  日期：——

  Regioselectivity in N-acetylation of nitro-p-phenylenediamine, a widely used hair dye component, by rat liver cytosolic N-acetyltransferases was studied in relation to its substituent effects on enzymatic N-acetylation of mono-substituted anilines. Nitro-p-phenylenediamine was acetylated specifically at the N4-position to afford the N4-monoacetate, a major urinary metabolite in the rat, when incubated with rat liver cytosol fortified with acetyl-coenzyme A. N1-Acetylation of nitro-p-phenylenediamine did not take place even when the N4-monoacetate was used as a substrate, suggesting a strong steric hindrance effect of the ortho nitro group on the enzymatic N1-acetylation. The steric hindrance effect of the nitro group on the cytosolic N-acetylation of the ortho amino group was revealed by a comparative study carried out by using aniline, three respective regioisomers of nitroanilines and phenylenediamines as model substrates. The comparative study also indicated the enzymatic N-acetylation of the mono-substituted anilines to be strongly influenced by the electronic effect of the substituents.Regioselective N-acetylation in the hepatic cytosol was also investigated with N1- and N4-monoacetates of 1, 2, 4-triaminobenzene. The monoacetates yielded the N1, N4-diacetate, another major urinary metabolite of the hair dye component, in the rat, without concomitant formation of the N2, N4-diacetate or the N1, N2, N4-triacetate. The triacetate was formed only from the N1, N2-diacetate in the enzymatic reactions. A comparative study, carried out by using N-mono-acetates of three regioisomeric phenylenediamines, indicated that the N-acetyl group had a potent steric hindrance effect on the primary amino group at the ortho position.Thus, the present in vitro study strongly suggested that the two major urinary metabolites, nitro-p-phenylenediamine N4-acetate and 1, 2, 4-triaminobenzene N1, N4-diacetate, of the hair dye component could be formed, at least in the rat liver, by the enzymatic N-acetylation of the corresponding amines.

  研究了大鼠肝细胞质N-乙酰转移酶对一种广泛使用的染发剂成分——硝基对苯二胺的N-乙酰化中的区域选择性，并与其取代基对单取代苯胺酶促N-乙酰化的影响进行了关联。硝基对苯二胺在与富含乙酰辅酶A的大鼠肝细胞质孵育时，特异性地在N4位进行乙酰化，生成N4-单乙酸盐，这是大鼠的主要尿代谢产物。即使在使用N4-单乙酸盐作为底物的情况下，硝基对苯二胺的N1-乙酰化仍未发生，这表明邻位硝基对酶促N1-乙酰化有很强的立体阻碍效应。通过使用苯胺、三个相应的硝基苯胺和苯二胺的区域异构体作为模型底物进行的比较研究揭示了硝基对邻位氨基的细胞质N-乙酰化的立体阻碍效应。该比较研究还表明，单取代苯胺的酶促N-乙酰化受取代基电子效应的强烈影响。 在肝细胞质中，对1, 2, 4-三氨基苯的N1-和N4-单乙酸盐进行了区域选择性N-乙酰化的研究。这些单乙酸盐在反应中生成N1, N4-二乙酸盐，这是染发剂成分在大鼠的另一个主要尿代谢产物，而没有同时形成N2, N4-二乙酸盐或N1, N2, N4-三乙酸盐。三乙酸盐仅在酶促反应中由N1, N2-二乙酸盐形成。通过使用三种区域异构体苯二胺的N-单乙酸盐进行的比较研究表明，N-乙酰基对邻位的一级氨基具有强大的立体阻碍效应。因此，本体外研究强烈表明，染发剂成分的两个主要尿代谢产物——硝基对苯二胺N4-乙酸盐和1, 2, 4-三氨基苯N1, N4-二乙酸盐，至少可以通过对应胺的酶促N-乙酰化在大鼠肝脏中形成。
• N-oxides and related compounds. Part XXVIII. 5-Amino- and 5-hydroxy-benzofuroxans
  作者：A. J. Boulton、P. B. Ghosh、A. R. Katritzky

  DOI：10.1039/j39660000971

  日期：——

  benzofuroxans and their precursors. Careful hydrolysis of 5-acetoxy- and 5-acylamino-benzofuroxan led to the isolation of 5-hydroxy- and 5-amino-benzofuroxan hydrochloride. The structures of these compounds are discussed.

  描述了多种5-取代的苯并呋喃喃及其前体的合成。5-乙酰氧基-和5-酰基氨基-苯并呋喃的仔细水解导致分离出5-羟基-和5-氨基-苯并呋喃盐酸盐。讨论了这些化合物的结构。
• Environmental protection series of reactive dyestuffs and their use
  申请人：Chen Hsiao-San

  公开号：US20050203286A1

  公开（公告）日：2005-09-15

  An environmental protection reactive dyestuff of the following formula (I) is disclosed, wherein R 1 , R 2 , D, M are defined as in the specification. The dyestuff of the invention is distinguished by a high fixation and a very good build-up. It is distinguished also by a green environmental protection and a low salt, a low base, a high exhaustion, non-contain heavy metal and halogen atoms, and it has fiber-reactive properties and is very highly suitable for dyeing and printing of materials containing either cellulose fibers, such as cotton, synthetic cotton, hemp, and synthetic hemp, or amide containing fibers such as wool and nylon.

  揭示了以下化学式(I)的一种环保反应性染料，其中R1、R2、D、M的定义如规范中所述。该发明的染料具有高固定性和非常良好的建立性。它还具有绿色环保、低盐、低碱、高耗尽、不含重金属和卤原子的特点，具有纤维反应性能，非常适合于含有纤维素纤维（如棉花、合成棉、大麻和合成大麻）或含酰胺纤维（如羊毛和尼龙）的材料的染色和印花。