3,3,4,4-四氯偶氮苯 | 14047-09-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 中文名称: 3,3,4,4-四氯偶氮苯
• 中文别名: 3,3?5,5四氯-4,4-二羟基联苯；3,3",4,4"-四氯偶氮苯
• 英文名称: 3,3',4,4'-tetrachloroazobenzene
• 英文别名: 1,2-bis(3,4-dichlorophenyl)diazene；3,3',4,4'-tetrachloroazobenzole；3,4,3',4'-tetrachloroazobenzene；TCAB；bis-(3,4-dichloro-phenyl)-diazene；Bis-(3,4-dichlor-phenyl)-diazen；bis(3,4-dichlorophenyl)diazene
• CAS: 14047-09-7
• 化学式: C₁₂H₆Cl₄N₂
• 分子量: 320.005
• InChiKey: SOBGIMQKWDUEPY-UHFFFAOYSA-N

物化性质

• 熔点：
  195.5 °C
• 沸点：
  475.54°C (rough estimate)
• 密度：
  1.5718 (rough estimate)
• 颜色/状态：
  Bright orange, crystalline solid
• 蒸汽压力：
  1.56X10-7 mm Hg at 25 °C (est)
• 分解：
  When heated to decomposition it emits very toxic fumes of /chlorine and oxides of nitrogen/.

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

3,3',4,4'-四氯偶氮苯（TCAB）是一种重要的环境和职业性毒物，在大鼠肝脏微粒体的NADPH生成系统中对其代谢进行了研究。通过结合使用高压液相色谱（HPLC）和气相色谱-质谱（GC-MS）来描绘代谢途径。使用诱导的微粒体时，(14C)TCAB的代谢速率为381 +/- 59 pmol/min/mg微粒体蛋白。大约13%的(14C)TCAB底物的放射性在2小时培养期结束时共价结合到宏分子沉淀中。此外，从有机提取物中分离出三种不同的TCAB代谢物，并随后进行了鉴定。一氧化碳、2-二乙氨基乙基2,2-二苯基戊酸盐酸盐（SKF 525-A）和控制（未诱导）微粒体的实验表明，细胞色素P-450依赖性单加氧酶参与了这一过程。

The metabolism of 3,3',4,4'-tetrachloroazobenzene (TCAB), an important environmental and occupational toxicant, by rat liver microsomes has been examined in a NADPH-generating system. The metabolic pathways were delineated by the combined use of high pressure liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). The rate of (14C)TCAB metabolism using induced microsomes was found to be 381 +/- 59 pmol/min/mg microsomal protein. Approximately 13% of the radioactivity from the (14C)TCAB substrate was covalently bound to the macromolecular pellet at the end of a 2 hr incubation period. In addition, three distinct TCAB metabolites were isolated from the organic extracts and subsequently identified. Experiments with carbon monoxide, 2-diethylaminoethyl 2,2-diphenylvalerate hydrochloride (SKF 525-A), and control (uninduced) microsomes indicated the participation of the cytochrome P-450-dependent monooxygenases. ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

在静脉注射(14C)3,3',4,4'-四氯偶氮苯(TCAB)（3.2 mg/kg）后，... 通过液相色谱/质谱（LC/MS）鉴定了尿中的TCAB代谢物。主要的代谢物是羟基化的一氯或二氯苯胺衍生物的硫酸酯结合物。其中一些代谢物也被乙酰化了。

Following intravenous administration of (14C)3,3',4,4'-Tetrachloroazobenzene (TCAB) (3.2 mg/kg), ... TCAB metabolites in urine were identified using LC/MS. The major metabolites were sulfate ester conjugates of hydroxylated mono- or dichloroaniline derivatives. Some of these metabolites were also acetylated.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

国际癌症研究机构致癌物：3,3′,4,4′-四氯偶氮苯

IARC Carcinogenic Agent:3,3�,4,4�-Tetrachloroazobenzene

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构（IARC）致癌物分类：2A组：可能对人类致癌

IARC Carcinogenic Classes:Group 2A: Probably carcinogenic to humans

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构专著：第117卷：（2019）五氯苯酚及其相关化合物

IARC Monographs:Volume 117: (2019) Pentachlorophenol and Some Related Compounds

来源:International Agency for Research on Cancer (IARC)

毒理性

• 解毒与急救

/SRP:/ 立即急救：确保已经进行了充分的中和。如果患者停止呼吸，请开始人工呼吸，最好使用需求阀复苏器、球囊阀面罩设备或口袋面罩，按训练操作。如有必要，执行心肺复苏。立即用缓慢流动的水冲洗受污染的眼睛。不要催吐。如果患者呕吐，让患者向前倾或将其置于左侧（如果可能的话，头部向下），以保持呼吸道畅通，防止吸入。保持患者安静，维持正常体温。寻求医疗救助。 /毒物A和B/

/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on the left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 基本治疗：建立专利气道（如有需要，使用口咽或鼻咽气道）。如有必要，进行吸痰。观察呼吸不足的迹象，如有需要，辅助通气。通过非循环呼吸面罩以10至15升/分钟的速度给予氧气。监测肺水肿，如有必要，进行治疗……。监测休克，如有必要，进行治疗……。预防癫痫发作，如有必要，进行治疗……。对于眼睛污染，立即用水冲洗眼睛。在运输过程中，用0.9%的生理盐水（NS）连续冲洗每只眼睛……。不要使用催吐剂。对于摄入，如果患者能吞咽、有强烈的呕吐反射且不流口水，则用水冲洗口腔，并给予5毫升/千克，最多200毫升的水进行稀释……。在去污染后，用干燥的无菌敷料覆盖皮肤烧伤……。/毒药A和B/

/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

3,3',4,4'-四氯偶氮苯（TCAB）是在合成3,4-二氯苯胺和3,4-二氯苯胺衍生物农药过程中产生的一种污染物。TCAB与2,3,7,8-四氯二苯并-p-二恶英是同构体，并且已被证实能够与Ah受体结合。在口服给药(14C)TCAB（3.2和32 mg/kg）后，39-45%的放射性剂量通过尿液排出，53-56%在48小时内通过粪便回收。在96小时内检查的组织中，剩余的放射性剂量不到6%。在静脉给药（3.2 mg/kg）后6小时内，33%的剂量通过胆汁排出。口服生物利用度确定为30%。TCAB的广泛偶氮还原作用在口服给药后减少了其系统吸收，从而限制了可用于与Ah受体互动的母体化合物的量，并减少了Ah受体介导的毒性。

3,3',4,4'-Tetrachloroazobenzene (TCAB) is a contaminant generated during the synthesis of 3,4-dichloroaniline and 3,4-dichloroaniline-derived pesticides. TCAB is isosteric to 2,3,7,8-tetrachlorodibenzo-p-dioxin and has been shown to bind to the Ah receptor. Following oral administration of (14C)TCAB (3.2 and 32 mg/kg), 39-45% of the dosed radioactivity was excreted into the urine and 53-56% was recovered in the feces within 48 hr. Less than 6% of the dosed radioactivity remained in the tissues examined at 96 hr. After intravenous administration (3.2 mg/kg), 33% of the dose was excreted in the bile during 6 hr. ... The absolute oral bioavailability was determined to be 30%. The extensive azo reduction of TCAB decreases its systemic absorption after oral administration and thereby limits the amount of parent compound available to interact with the Ah receptor and decreases the Ah receptor-mediated toxicity.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 海关编码：
  2927000090
• 储存条件：
  室温

反应信息

• 作为反应物：
  描述：

  3,3,4,4-四氯偶氮苯 在 乙醇 、 铁粉 、 calcium chloride 作用下， 反应 0.42h， 以87%的产率得到3,4-二氯苯胺
  参考文献：
  名称：

  一种使用铁粉/氯化钙进行芳基硝基还原和裂解偶氮化合物的有效方法

  摘要：

  揭示了一种新颖、高效的 Fe/CaCl(2) 系统，用于通过催化转移氢化 (CTH) 还原硝基芳烃和还原裂解偶氮化合物。据报道，在敏感官能团（包括卤化物、羰基、羟基、醛、甲基、甲氧基、乙酰基、腈和酯取代基）存在的情况下，硝基化合物的选择性还原具有极好的收率。简单的实验程序和易于纯化使该协议具有优势。

  DOI：

  10.1055/s-0030-1259067
• 作为产物：
  描述：

  3,4-二氯苯胺 在 sodium perborate 、 sodium molybdate dihydrate 作用下， 以 溶剂黄146 为溶剂， 反应 1.0h， 以89%的产率得到3,3,4,4-四氯偶氮苯
  参考文献：
  名称：

  用过硼酸盐和Mo（VI）将苯胺在乙酸中转化为偶氮苯：反应性的相关性

  摘要：

  偶氮苯被广泛用于纺织品和皮革的染色，通过调节环中的取代基，可以获得鲜艳的色彩。在这里，我们报道了在温和条件下，使用过硼酸钠（SPB）和催化量的Na 2 MoO 4由市售苯胺以高收率制备大量的偶氮苯。冰醋酸是首选的溶剂，苯胺到偶氮苯的转化率是零，相对于SPB，Na 2 MoO 4来说，是一阶和一阶和苯胺。根据动力学级数，紫外可见光谱和循环伏安图，提出了转化机理。在20–50°C时约50个苯胺的反应速率及其能量和活化熵分别符合等动力学或Exner关系和补偿效应。然而，由迄今为止采用的方法推导的反应速率不能符合哈米特相关性。通过改进的计算获得的分子苯胺的特定反应速率符合哈米特关系。因此，这项工作提出了一种方便，廉价，无害的制备大量偶氮苯的方法，

  DOI：

  10.1007/s11696-018-0599-z

文献信息

• Mechanism and reactivity in perborate oxidation of anilines in acetic acid
  作者：Chockalingam Karunakaran、Ramasamy Kamalam

  DOI：10.1039/b208199g

  日期：2002.12.6

  Perborate but not percarbonate in acetic acid generates peracetic acid on standing and the peracetic acid oxidation of anilines is fast. The oxidation with a fresh solution of perborate in acetic acid is smooth and second order but the specific oxidation rate increases with increasing [perborate]0 or [boric acid]. Perborate on dissolution affords hydrogen peroxide and a borate; the latter assists the former in the oxidation. The oxidation rates of anilines under identical conditions do not conform to any of the linear free energy relationships but the reaction rates of molecular anilines do. Perborate oxidation proceeds via two reaction paths but the overall oxidation rates of molecular anilines conform to structure–reactivity relationships; the transition states do not differ significantly. Analysis of the oxidation rates of perborate and percarbonate reveals that while perborate oxidation is faster than percarbonate it is at least as selective as the latter.

  在乙酸中，过硼酸盐而非过碳酸盐静置时会产生过乙酸，而过乙酸对苯胺的氧化反应迅速。使用新鲜配制的乙酸过硼酸盐溶液进行氧化反应平稳且具有二级反应特性，但特定的氧化速率随[过硼酸盐]0或[硼酸]浓度的增加而增加。过硼酸盐溶解时产生过氧化氢和硼酸盐；后者在氧化过程中辅助前者。在相同条件下，苯胺的氧化速率不符合任何线性自由能关系，但分子苯胺的反应速率却符合。过硼酸盐氧化通过两条反应路径进行，但分子苯胺的整体氧化速率符合结构-反应活性关系；过渡态的差异不大。对过硼酸盐和过碳酸盐氧化速率的分析显示，尽管过硼酸盐的氧化速率更快，但其选择性至少不亚于过碳酸盐。
• Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes
  作者：Wengang Liu、Leilei Zhang、Wensheng Yan、Xiaoyan Liu、Xiaofeng Yang、Shu Miao、Wentao Wang、Aiqin Wang、Tao Zhang

  DOI：10.1039/c6sc02105k

  日期：——

  Co–N–C is identified to be CoN4C8-1-2O2, where the Co center atom is coordinated with four pyridinic N atoms in the graphitic layer, while two oxygen molecules are weakly adsorbed on Co atoms in perpendicular to the Co–N4 plane. This single-atom dispersed Co–N–C catalyst presents excellent performance for the chemoselective hydrogenation of nitroarenes to produce azo compounds under mild reaction conditions

  Co-N-C催化剂是在电催化和有机转化中替代铂的有希望的候选者。然而，由高温热解引起的 Co 物种的异质性阻碍了活性位点的结构鉴定。在此，我们报道了一种自支撑 Co-N-C 催化剂，其中钴仅作为单个原子分散。通过使用亚埃分辨率 HAADF-STEM 结合 XAFS 和 DFT 计算，Co-N-C 的确切结构被确定为CoN 4 C 8 -1-2O 2，其中 Co 中心原子与石墨层中有四个吡啶N原子，而两个氧分子弱吸附在Co原子上，垂直于Co-N 4飞机。这种单原子分散的 Co-N-C 催化剂在温和的反应条件下对硝基芳烃的化学选择性加氢产生偶氮化合物具有优异的性能。
• Unprecedented Direct Conversion of N-N and N=N bonds to N-(tert-Butyloxy)-carbamates
  作者：S. Chandrasekhar、Ch. Raji Reddy、R. Jagadeeshwar Rao

  DOI：10.1055/s-2001-17439

  日期：——

  For the first time a one step direct conversion of aromatic hydrazines and azo compounds to N-(tert-butoxycarbonyl) amines is achieved via reductive cleavage of N-N and N=N bonds using the inexpensive and safe hydride source polymethylhydrosiloxane (PMHS) and di-tert-butyl dicarbonate [(Boc)2O] in the presence of a catalytic amount of 10% Pd-C.

  首次通过使用廉价且安全的氢化物源聚甲基氢硅氧烷（PMHS）与二叔丁基二碳酸酯[（Boc）2O]，在10% Pd-C催化剂的催化作用下，实现了芳香肼和偶氮化合物通过还原断裂N-N与N=N键，一步直接转化为N-（叔丁氧羰基）胺。
• Chemoselective electrochemical reduction of nitroarenes with gaseous ammonia
  作者：Liu Chang、Jin Li、Na Wu、Xu Cheng

  DOI：10.1039/d1ob00077b

  日期：——

  Valuable aromatic nitrogen compounds can be synthesized by reduction of nitroarenes. Herein, we report electrochemical reduction of nitroarenes by a protocol that uses inert graphite felt as electrodes and ammonia as a reductant. Depending on the cell voltage and the solvent, the protocol can be used to obtain aromatic azoxy, azo, and hydrazo compounds, as well as aniline derivatives with high chemoselectivities

  可以通过还原硝基芳烃来合成有价值的芳族氮化合物。在这里，我们报告了通过使用惰性石墨毡作为电极和氨作为还原剂的协议对硝基芳烃进行电化学还原。根据电池电压和溶剂的不同，该协议可用于获得芳族a氧基，偶氮和化合物以及具有高化学选择性的苯胺衍生物。该方案可以轻松放大至> 10 g，而产量不会降低，证明了其潜在的合成效用。提出了逐步的阴极还原途径以依次解释产物的世代。
• Structure−Reactivity Correlation of Anilines in Acetic Acid
  作者：Chockalingam Karunakaran、Ramasamy Kamalam

  DOI：10.1021/jo0158433

  日期：2002.2.1

  The oxidation of aniline in glacial acetic acid with percarbonate, a dry carrier of hydrogen peroxide, is a second-order reaction conforming to the isokinetic relationship. The hitherto followed method of correlation of the reaction rates in terms of the structure-reactivity relationships is unsatisfactory and erroneous. But the reaction rates of molecular anilines, obtained for the first time, conform

  冰醋酸中苯胺与过碳酸盐（过氧化氢的干燥载体）的氧化是符合等动力学关系的二级反应。迄今为止按照结构-反应性关系进行反应速率相关的跟踪方法是不令人满意的并且是错误的。但是首次获得的分子苯胺的反应速率符合结构-反应性关系。