对硝基苯胂酸 | 98-72-6

• 物质功能分类: 分析化学 - 分析试剂 - 离子色谱试剂
• 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: 对硝基苯胂酸
• 中文别名: 硝苯胂酸；4-硝基苯胂酸
• 英文名称: nitarsone
• 英文别名: (4-Nitro-phenyl)-arsonsaeure；p-nitrophenylarsonic acid；4-nitrophenylarsonic acid；p-Nitrophenylarsonsaeure；(4-nitrophenyl)arsonic acid
• CAS: 98-72-6
• 化学式: C₆H₆AsNO₅
• 分子量: 247.039
• InChiKey: FUUFQLXAIUOWML-UHFFFAOYSA-N

物化性质

• 熔点：
  300°C(lit.)
• 沸点：
  540.9±52.0 °C(Predicted)
• 溶解度：
  可溶于DMSO（少许）、甲醇（少许）
• 物理描述：
  Solid

计算性质

• 辛醇/水分配系数(LogP)：
  -0.84
• 重原子数：
  13
• 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：
  103
• 氢给体数：
  2
• 氢受体数：
  5

ADMET

代谢

砒霜主要通过吸入或摄入被吸收，较少程度上通过皮肤接触。然后它被分布到全身，如果需要，它会被还原成亚砷酸盐，然后通过亚砷酸盐甲基转移酶甲基化成单甲基砷（MMA）和二甲基硅酸（DMA）。砒霜及其代谢物主要通过尿液排出。已知砒霜能诱导金属结合蛋白金属硫蛋白，通过绑定砒霜和其他金属并使其生物活性失效，以及作为抗氧化剂的作用，从而减少砒霜和其他金属的有毒效果。

Arsenic is absorbed mainly by inhalation or ingestion, as to a lesser extent, dermal exposure. It is then distributed throughout the body, where it is reduced into arsenite if necessary, then methylated into monomethylarsenic (MMA) and dimethylarsenic acid (DMA) by arsenite methyltransferase. Arsenic and its metabolites are primarily excreted in the urine. Arsenic is known to induce the metal-binding protein metallothionein, which decreases the toxic effects of arsenic and other metals by binding them and making them biologically inactive, as well as acting as an antioxidant. (L20)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

砒霜及其代谢物通过多种机制干扰ATP的产生。在柠檬酸循环层面，砒霜抑制了丙酮酸脱氢酶，并通过与磷酸竞争解耦了氧化磷酸化，从而抑制了与能量相关的NAD+还原、线粒体呼吸和ATP合成。过氧化氢的产生也增加了，这可能会形成活性氧物种和氧化应激。砒霜的致癌性受到砒霜与微管蛋白结合的影响，导致非整倍体、多倍体和有丝分裂停滞。其他砒霜蛋白靶点的结合也可能导致DNA修复酶活性改变、DNA甲基化模式改变和细胞增殖。

Arsenic and its metabolites disrupt ATP production through several mechanisms. At the level of the citric acid cycle, arsenic inhibits pyruvate dehydrogenase and by competing with phosphate it uncouples oxidative phosphorylation, thus inhibiting energy-linked reduction of NAD+, mitochondrial respiration, and ATP synthesis. Hydrogen peroxide production is also increased, which might form reactive oxygen species and oxidative stress. Arsenic's carcinogenicity is influenced by the arsenical binding of tubulin, which results in aneuploidy, polyploidy and mitotic arrests. The binding of other arsenic protein targets may also cause altered DNA repair enzyme activity, altered DNA methylation patterns and cell proliferation. (T1, A17)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

3, 无法归类其对人类致癌性的级别。

3, not classifiable as to its carcinogenicity to humans. (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

低血容量，由于毛细血管泄漏（第三间隙液体潴留）是一种常见、严重、早期的效应。肌肉痉挛、面部水肿、支气管炎、呼吸困难、胸痛、脱水、强烈的口渴和液体电解质紊乱在显著暴露后也很常见。呼吸和粪便中可能也会有类似大蒜的气味。吸收后，砷可能通过抑制含巯基的酶而导致多器官衰竭。脑病，伴有头痛、乏力、精神混乱、幻觉、情绪不稳、记忆丧失和谵妄可能出现；严重急性暴露后24小时内可能出现癫痫、昏迷、惊厥、昏迷和死亡。心律失常（尤其是QTc间期延长和尖端扭转型室速）、心肌病、ARDS、肝炎、横纹肌溶解症、溶血和肾功能衰竭可能在几天内发展。慢性中毒的序列包括色素沉着过度、湿疹样和过敏性皮炎。肌肉纤维颤动；明显震颤；共济失调；不协调；精神混乱。随后可能出现肌肉无力、肢体疼痛和行走困难。最后阶段包括手和脚的周围感觉神经病变。这可能与运动神经病变有关（T36）。

Hypovolemia from capillary leakage (third-spacing of fluids) is a common, serious, early effect. Muscle cramps, facial edema, bronchitis, dyspnea, chest pain, dehydration, intense thirst, and fluid-electrolyte disturbances are also common following significant exposures. A garlic-like odor of the breath and feces may also occur. After absorption, arsenic may cause multi-organ failure by inhibiting sulfhydryl-containing enzymes. Encephalopathy, with headache, lethargy, mental confusion, hallucinations, emotional lability, memory loss and delirium may occur; seizures, stupor, convulsions, coma, and death may follow within 24 hours of a severe acute exposure. Dysrhythmias (particularly QTc prolongation and torsade de pointes), cardiomyopathy, ARDS, hepatitis, rhabdomyolysis, hemolysis, and renal failure may develop over several days. The sequence of chronic poisoning involves hyperpigmentation, and eczematoid and allergic dermatitis. muscle fasciculations; gross tremors; ataxia; incoordination; and mental confusion. Muscular weakness, limb tenderness and difficulty walking may follow. The final phase consists of peripheral sensory neuropathy of the hands and feet. That may be associated with a motor neuropathy as well (T36).

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L2）；吸入（L2）；皮肤给药（L2）

Oral (L2) ; inhalation (L2); dermal (L2)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

砒霜摄入的初期症状包括嘴唇灼热、喉咙紧缩和吞咽困难，随后会出现剧烈的腹部疼痛、出血性胃炎、胃肠炎、严重恶心、喷射性呕吐、大量“米汤样”腹泻，以及可能导致低血压和不规则脉搏的低血容量。慢性中毒的过程包括虚弱、厌食、肝肿大、黄疸和胃肠道不适，随后可能出现结膜炎、喉咙和呼吸道的刺激。慢性暴露的其他影响包括伴有刺激和流泪的结膜炎；头发、皮肤和指甲的变化；手和脚的过度角化；以及角膜和结膜上皮的色素斑。周围神经系统症状可能包括手和脚的麻木、灼热和刺痛；疼痛；感觉异常；以及压痛（T36）。

Initial signs and symptoms of arsenic ingestion include burning lips, throat constriction and dysphagia, followed by excruciating abdominal pain, hemorrhagic gastritis, gastroenteritis, severe nausea, projectile voting, profuse "rice water-like" diarrhea, with hypovolemia that may result in hypotension and an irregular pulse. The sequence of chronic poisoning involves weakness, anorexia, hepatomegaly, jaundice, and gastrointestinal complaints, followed by conjunctivitis, irritation of the throat and respiratory tract. ther effects of chronic exposure include conjunctivitis with irritation and lacrimation; hair, skin and nail changes; hyperkeratosis of feet and hands; and melanosis, with pigment spots in corneal and conjunctival epithelium. Peripheral nervous system symptoms may include numbness, burning, and tingling of the hands and feet; pain; paresthesias; tenderness (T36).

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• 危险等级：
  6.1
• 海关编码：
  2931900090
• 危险品运输编号：
  UN3465 6.1/PG 3
• 储存条件：
  库房应保持通风、低温和干燥，并与食品原料分开储运。

SDS

第一部分：化学品名称

制备方法与用途

化学性质

淡黄色叶状结晶。熔点在298-300℃（分解）。可溶于热水和热醇，极微溶于冷水和冷醇。

用途

用作医药中间体，并且也是一种分析试剂。

生产方法

由对硝基苯胺重氮化、胂化而得。首先将对硝基苯胺加入盐酸中搅拌2小时，然后投入冰块降温至-5℃，在15分钟内逐步加入亚硝酸钠溶液，搅拌约1小时得到重氮盐溶液。接着将三氧化二砷和碳酸钠溶解于水中冷却至25℃以下，再滴加硫酸铜溶液，并缓慢加入上述重氮盐溶液，控制反应温度不超过25℃，即获得对硝基苯胂酸。

分类

有毒物品

毒性分级

高毒

急性毒性

口服-大鼠LDL0: 100毫克/公斤

可燃性危险特性

受热分解产生有毒的氧化氮和砷化物气体

储运特性

应存放在库房通风、低温干燥处；与食品原料分开储存运输

灭火剂

二氧化碳、砂土、水

职业标准

时间加权平均容许浓度（TWA）0.5毫克/立方米，短时间接触容许浓度（STEL）0.6毫克/立方米 (砷)

反应信息

• 作为反应物：
  描述：

  对硝基苯胂酸 在 盐酸 、 铁粉 作用下， 生成 对氨基苯砷酸
  参考文献：
  名称：

  DE468757

  摘要：

  公开号：
• 作为产物：
  描述：

  二氯(4-硝基苯基)胂 在 水 、 氯 作用下， 生成 对硝基苯胂酸
  参考文献：
  名称：

  Kokorev, G. I.; Yambushev, F. D.; Kut'in, S. V., Journal of general chemistry of the USSR, 1986, vol. 56, # 2, p. 424

  摘要：

  DOI：

文献信息

• Ascorbic Acid/Iodine and Triphenylphosphine/Iodine as Reducing Agents for the As(V)[dbnd]O Group
  作者：Theodore D. Sideris、Panayiotis V. Ioannou

  DOI：10.1080/10426500500272335

  日期：2006.6

  The scope of ascorbic acid/iodine and triphenylphosphine/iodine in methanol for the direct reduction of arsenic(V) compounds having the As˭O group has been investigated. Ascorbic acid/iodine reduces arsonic acids, diphenylarsinic acid (but not dimethylarsinic acid), and triphenylarsine oxide. The rates of reduction depend on the electronic effects of the ligands bound to arsenic and on the hydrogen-bonding

  已经研究了抗坏血酸/碘和三苯基膦/碘在甲醇中用于直接还原具有 As˭O 基团的砷 (V) 化合物的范围。抗坏血酸/碘可减少胂酸、二苯基胂酸（但不包括二甲基胂酸）和氧化三苯基胂酸。还原速率取决于与砷结合的配体的电子效应以及存在时该物种的氢键强度。当 As(V) 化合物具有 -NH 2 或 -NH 3 + 基团时，还原产物与酮形式的脱氢抗坏血酸反应，得到缩合产物。三苯基膦/碘缓慢地还原两性离子邻氨基苯胂酸，但更快地还原相同酸的盐酸盐。
• Substituted phenylarsonic acids; structures and spectroscopy
  作者：Nicholas C. Lloyd、Hugh W. Morgan、Brian K. Nicholson、Ron S. Ronimus

  DOI：10.1016/j.jorganchem.2008.04.033

  日期：2008.7

  Full NMR and ESI-MS spectra, and differential scanning calorimeter data are presented for 15 substituted phenylarsonic acids, including two new fluoro-substituted examples. X-ray crystal structure determinations of five examples (phenylarsonic acid and the 4-fluoro-, 4-fluoro-3-nitro-, 3-amino-4-hydroxy- and 3-amino-4-methoxy-substituted derivatives) were determined and the H-bonding crystal-packing

  给出了15个取代的苯基ar磺酸的完整NMR和ESI-MS光谱以及差示扫描量热仪数据，其中包括两个新的氟取代的实例。测定了五个实施例（苯ar酸和4-氟-，4-氟-3-硝基-，3-氨基-4-羟基和3-氨基-4-甲氧基取代的衍生物）的X射线晶体结构测定。并分析了H键的晶体堆积图案。
• Barriers to pseudorotation in spiroarsoranes
  作者：Jeremiah P. Casey、Kurt Mislow

  DOI：10.1039/c29700001410

  日期：——

  Barriers to pseudorotation in AsV species, in which a five-membered ring is constrained to span the equatorial positions in the trigonal bipyramidal intermediates, are in the range of 20–23 kcal mol–1, and thus are comparable with the corresponding barriers in PV systems with similar structures.

  As V物种伪旋转的障碍（其中一个五元环被约束跨越三角双锥体中间体中的赤道位置）的范围在20-23 kcal mol –1范围内，因此可与P V系统的相似的结构。
• Dithiol Aryl Arsenic Compounds as Potential Diagnostic and Therapeutic Radiopharmaceuticals
  作者：Anthony J. DeGraffenreid、Yutian Feng、Donald E. Wycoff、Ryan Morrow、Michael D. Phipps、Cathy S. Cutler、Alan R. Ketring、Charles L. Barnes、Silvia S. Jurisson

  DOI：10.1021/acs.inorgchem.6b01175

  日期：2016.8.15

  nuclear properties useful for positron emission tomography (PET) and radiotherapy, respectively. The thiophilic nature of arsenic led to the evaluation of dithioarylarsines for potential use in radiopharmaceuticals. Several dithioarylarsines were synthesized from their arylarsonic acids and dithiols and were fully characterized by NMR, ESI-MS, and X-ray crystallography. This chemistry was translated to

  Arsenic-72（72 As）和77 As具有其核性质，分别可用于正电子发射断层扫描（PET）和放射疗法。砷的亲硫性质导致人们对二硫代芳氨酸在放射性药物中的潜在用途进行了评估。由它们的芳基松香酸和二硫醇合成了几种二硫代芳氨酸，并通过NMR，ESI-MS和X射线晶体学对其进行了全面表征。该化学反应转化为无载体添加（nca）77 As的水平。由于砷仅以[ 77 As]砷酸盐的形式在nca纳摩尔浓度下可用，因此需要将芳基直接加到As上以形成[ 77 As]芳基磺酸。[ 77 As]砷酸盐从77 As（V）至77 As（III），并使用修饰的Bart反应将芳基环引入77 As，然后加入二硫醇。各种修改和优化导致nca [ 77 As]对乙氧基苯基-1，2-乙二硫基花生四氢呋喃的放射化学产率为95％。
• Penta‐, Hexa‐, and Heptanuclear Organotin–Oxygen Arsonate Clusters Constructed from an Acetate Drum Cluster Precursor and Different Arsonate Anions
  作者：Yun‐Peng Xie、Jian‐Fang Ma、Jin Yang、Ying‐Ying Liu、Ji‐Cheng Ma、Min‐Zhong Su

  DOI：10.1002/ejic.200900135

  日期：2009.5

  [nBuSn(O)O 2 CMe] 6 with different arsonic acids gave seven organotin arsonate clusters: [(nBuSn) 5 (μ 3 -O)(OH)(R'0)3(RAsO 3 )4(RAsO 3 H)] [R = 2-NO 2 C 6 H 4 , R' = Me (la and 1b)], [(nBuSn)3(RAsO 3 )(μ 3 -Ο)-(CH 3 CΟ 2 ) 3 (R'O) 2 ] 2 [R = 2,4-(NO 2 ) 2 C 6 H 3 , R' = Me (2)], [(nBuSn)3(RAsO 3 ) 2 (RAsO 3 H)(μ 3 -O)(R'O)2]2 [R =4-NO 2 C 6 H 4 , R' = Me (3)], and [(nBuSn)3(RAsO 3 ) 3 (μ 3 -O)(OH)(R'O)2]2Sn

  用不同的砷酸处理醋酸盐鼓 [nBuSn(O)O 2 CMe] 6 得到七个有机锡砷酸盐簇：[(nBuSn) 5 (μ 3 -O)(OH)(R'0)3(RAsO 3 )4 (RAsO 3 H)] [R = 2-NO 2 C 6 H 4 , R' = Me (la 和 1b)], [(nBuSn)3(RAsO 3 )(μ 3 -Ο)-(CH 3 CΟ 2 ) ) 3 (R'O) 2 ] 2 [R = 2,4-(NO 2 ) 2 C 6 H 3 , R' = Me (2)], [(nBuSn)3(RAsO 3 ) 2 (RAsO 3 H )(μ 3 -O)(R'O)2]2 [R =4-NO 2 C 6 H 4 , R' = Me (3)] 和 [(nBuSn)3(RAsO 3 ) 3 (μ 3 -O)(OH)(R'O)2]2Sn [R =C 6 H 5 CH 2 , R' = Me (4); R