4,4-亚甲基双(n-甲基苯胺) | 1807-55-2

• 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: 4,4-亚甲基双(n-甲基苯胺)
• 英文名称: 4,4'-methylenebis(N-methylaniline)
• 英文别名: bis(4-(N-methyl)aminophenyl)methane；N,N'-Dimethyl-4,4'-diaminodiphenylmethan；N,N'-dimethyl-4,4'-diaminodiphenylmethane；N,N'-Dimethyl-p,p'-diaminodiphenylmethan；N-methyl-4-[[4-(methylamino)phenyl]methyl]aniline
• CAS: 1807-55-2
• 化学式: C₁₅H₁₈N₂
• mdl: MFCD00035805
• 分子量: 226.321
• InChiKey: ZMVMYBGDGJLCHV-UHFFFAOYSA-N

物化性质

• 熔点：
  55-56 °C
• 沸点：
  357.94°C (rough estimate)
• 密度：
  0.9543 (rough estimate)
• 溶解度：
  In water, 50.7 mg/L at 25 °C (est)
• 蒸汽压力：
  1.76X10-5 mm Hg at 25 °C (et)
• 分解：
  When heated to decomposition it emits toxic fumes of NOx.

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  24.1
• 氢给体数：
  2
• 氢受体数：
  2

ADMET

代谢

... 4,4'-[14C]-亚甲基双(对二甲苯胺)(RMK)的主要尿液代谢物，占总尿液中回收放射性活度的36%，是大鼠尿液中的N，N'-二乙酰-4,4'-(羟基亚甲基)二苯胺。RMK的体外微粒体代谢涉及去甲基化。产物包括N，N-二甲基-4,4'-亚甲基二苯胺，N，N'-二甲基-4,4'-亚甲基二苯胺，N-甲基-4,4'-亚甲基二苯胺和4,4'-亚甲基二苯胺，分别占总回收放射性活度的44.7%，5.3%，11.8%和6.9%。...

... The major urinary metabolite of 4,4'-[14C]-methylenebis(N,N-dimethyl)benzamine (RMK), representing 36% of the total radioactivity recovered in the urine /of rats/, was N,N'-diacetyl-4,4'-(hydroxymethylene)dianiline. In vitro microsomal metabolism of RMK involved demethylation. Products included N,N-dimethyl-4,4'-methylenedianiline, N,N'-dimethyl-4,4'-methylenedianiline, N-methyl-4,4'-methylenedianiline, and 4,4'-methylenedianiline, representing 44.7, 5.3, 11.8, and 6.9%, respectively, of the total radioactivity recovered from the reaction mixture. ...

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 副作用

高铁血红蛋白血症 - 血液中高铁血红蛋白含量增加；该化合物被归类为继发性毒性效应。

Methemoglobinemia - The presence of increased methemoglobin in the blood; the compound is classified as secondary toxic effect

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

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、袋阀面罩装置或口袋面罩，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。如果发生呕吐，让患者前倾或置于左侧（如果可能，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。寻求医疗关注。 /苯胺及其相关化合物/

/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 as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on 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. /Aniline and related compounds/

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。密切观察呼吸不足的迹象，如有必要，进行辅助通气。通过非重复呼吸面罩以10至15升/分钟的速度给予氧气。监测休克迹象，并在必要时进行治疗……。预见并治疗癫痫发作……。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，如果患者能够吞咽、有强烈的干呕反射且不流口水，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。给予活性炭……。/苯胺及其相关化合物/

/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 necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. 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 patent can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Aniline and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 高级治疗：对于无意识、严重肺水肿或严重呼吸困难的病人，考虑进行口咽或鼻咽气管插管以控制气道。监测心率和必要时治疗心律失常...开始静脉输注D5W /SRP: "保持开放"，最低流量/。如果出现低血容量的迹象，使用0.9%盐水（NS）或乳酸钠林格液（LR）。对于伴有低血容量迹象的低血压，谨慎给予液体。如果血容量正常但低血压，考虑使用血管加压药。注意液体过载的迹象...如果病人在严重低氧血症、发绀和心脏受累（对氧疗无反应）有症状，给予1%亚甲基蓝溶液。仅限医生直接指令...用安定或劳拉西泮治疗癫痫...使用丙美卡因氢氯化物协助眼部冲洗.../苯胺及其相关化合物/

/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Administer 1% solution methylene blue if patient is symptomatic with severe hypoxia, cyanosis, and cardiac compromise not responding to oxygen. DIRECT PHYSICIAN ORDER ONLY ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Aniline and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 非人类毒性摘录

尽管在标准沙门氏菌伤寒测试中没有微囊代谢物是直接致突变剂，但当与9000 X g肝脏上清液和还原型烟酸腺嘌呤二核苷酸磷酸一起孵化时，所有代谢物都可以被激活为致突变剂。将4,4'-亚甲基二苯胺激活为致突变剂表明，还原米歇尔酮（RMK）中的甲基团对于将RMK转化为活性亲电子体并非必需。

/GENOTOXICITY/ Although none of the microsomal metabolites was a direct-acting mutagen in the standard Salmonella typhimurium assay, all could be activated to mutagens when incubated with 9000 X g liver supernatants and reduced nicotinamide adenine dinucleotide phosphate. The activation of 4,4'-methylenedianiline to a mutagen suggests that the methyl groups of /reduced Michler's ketone, RMK)/ are not required for the conversion of RMK to a reactive electrophile.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

对4,4'-[14C]-亚甲基双(二甲基)苯胺(还原米歇尔酮, RMK)在体内和体外的处置进行了研究。奥斯本-门德尔大鼠在24小时后保留了口服[14C]RMK剂量的78%。在腹腔注射后24小时，脂肪、肝脏和肠是放射性沉积的主要部位...

Studies on the in vivo and in vitro disposition of 4,4'-[14C]-methylenebis(N,N-dimethyl)benzamine (reduced Michler's ketone, RMK) were performed. Osborne-Mendel rats retained, after 24 hr, 78% of a /oral/ dose of [14C]RMK. At 24 hr after an i.p. dose, fat, liver, and intestine represented major sites for deposition of radioactivity. ...

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 海关编码：
  2921590090

反应信息

• 作为反应物：
  描述：

  4,4-亚甲基双(n-甲基苯胺) 在 aluminum (III) chloride 、 sodium tetrahydroborate 、 乙醇 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 29.5h， 生成 bis[p-(methyl(2,2,2-trifluoroethyl)amino)]benzhydrylium tetrafluoroborate
  参考文献：
  名称：

  氨基取代的苄鎓离子的合成，结构和性质–普通碳正离子与中性亲电试剂之间的联系

  摘要：

  描述了直接获取十一种氨基取代的二芳基甲基四氟硼酸酯的优化合成方法。这些苯甲酸铵离子的亲电性涵盖了七个数量级的范围，并提供了普通碳正离子与中性亲电子之间的联系。这些高稳定度的四氟硼酸苄基铵盐中有五个通过单晶X射线晶体学表征。尽管实验确定的固态键长和键长与DFT方法计算出的气相和水溶液的键长和夹角完全吻合，但与固态填充物相比，晶体堆积说明了固态中芳基的扭曲角存在较大差异。计算结构。

  DOI：

  10.1002/ejoc.201800835
• 作为产物：
  描述：

  1,1',5,5'-bis[methylenedi(p-phenylene)]-di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) 生成 4,4-亚甲基双(n-甲基苯胺)
  参考文献：
  名称：

  摘要：

  The reaction of bis(hydroxymethyl)phenylphosphine with 4,4'-diaminodiphenylmethane in DMF afforded 1,1',5,5'-bis[metylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis. Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2 and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of bis(hydroxymethyl)phenylphosphine with bis(4-N-methylaminophenyl)methane in DMF followed by sulfurization yielded monocyclic bis{methylenedi[p-phenylene(N-methyl)amino-methyl]}di(P-phenyl)phosphine sulfide (4).

  DOI：

  10.1023/a:1015086419302

文献信息

• MELANIN PRODUCTION INHIBITOR
  申请人：Yokoyama Kouji

  公开号：US20110243865A1

  公开（公告）日：2011-10-06

  Disclosed is a melanin production inhibitor which has an excellent inhibitory activity on the production of melanin and is highly safe. The melanin production inhibitor comprises a compound represented by general formula (1) (excluding clotrimazole), and/or a pharmacologically acceptable salt thereof. In the formula, A1, A2 and A3 are independently selected from a hydrogen atom, an aryl group which may have a substituent, and an aromatic heterocyclic group which may have a substituent, wherein at least one of A1, A2 and A3 is selected from the aryl group and the aromatic heterocyclic group, the total number of carbon atoms contained in A1, A2 and A3 is 6 to 50 and, when at least two of A1, A2 and A3 represent the aryl groups or the aromatic heterocyclic groups, the adjacent two aryl or aromatic heterocyclic groups may be bound to each other via an alkyl chain or an alkenyl chain to form a ring; m represents an integer of 0 to 2; X represents a hetero atom, a hydrogen atom, or a carbon atom; R1 and R2 are independently selected from a hydrogen atom and an oxo group, wherein when one of R1 and R2 is an oxo group, the other is not present; and R3 is selected from a hydrogen atom, and a C 1-8 hydrocarbon group in which one or some of hydrogen atoms or carbon atoms may be substituted by a hetero atom or hetero atoms, wherein the number of R3's present in the compound corresponds to the number of X's and, when two or more R3's are present, the R3's are independently present and the adjacent two R3's may be bound to each other to form, together with X, a ring, and the terminal of R3 may be bound to a carbon atom to which A1, A2 and A3 are bound, thereby forming a ring.

  披露了一种黑色素生产抑制剂，它对黑色素的生产具有出色的抑制活性且高度安全。该黑色素生产抑制剂包括由通用公式（1）表示的化合物（不包括克霉唑）和/或其药理上可接受的盐。在公式中，A1、A2和A3独立地选自氢原子、可能带有取代基的芳基团和可能带有取代基的芳香杂环团，其中至少A1、A2和A3之一选自芳基团和芳香杂环团，A1、A2和A3中包含的碳原子总数为6至50，并且当至少两个A1、A2和A3表示芳基团或芳香杂环团时，相邻的两个芳基或芳香杂环团可以通过烷基链或烯基链相互连接形成环；m代表0至2的整数；X代表异原子、氢原子或碳原子；R1和R2独立地选自氢原子和氧代基，其中当R1和R2之一是氧代基时，另一个不出现；R3选自氢原子和C 1-8 碳氢化合物组，其中一些或所有的氢原子或碳原子可能被异原子或异原子取代，其中化合物中存在的R3的数量对应于X的数量，并且当存在两个或更多R3时，R3独立地存在，并且相邻的两个R3可以相互连接以与X一起形成环，并且R3的末端可以与A1、A2和A3连接的碳原子结合，从而形成环。
• Copper(II)‐Catalysed Aerobic Oxidative Coupling of Arylamines with Hexafluoroisopropanol: An Alternative Methodology for Constructing Fluorinated Compounds
  作者：Liangying Wu、Yang Song、Zhanchong Li、Jiabao Guo、Xiaoquan Yao

  DOI：10.1002/adsc.202001048

  日期：2021.1.5

  The selective functionalisation of arylamine derivatives with hexafluoroisopropanol through copper(II)‐catalysed aerobic oxidative coupling was developed to generate various fluoroalkylated arylamines under mild conditions. This method has a wide substrate scope with excellent functional group tolerance and provides the fluorinated products in good to excellent yields. Furthermore, preliminary studies

  开发了在铜（II）催化的需氧氧化偶联作用下，六氟异丙醇对芳胺衍生物的选择性官能化反应，可在温和条件下生成各种氟代烷基化芳基胺。该方法具有广泛的底物范围，具有优异的官能团耐受性，并且以良好至优异的产率提供了氟化产物。此外，初步研究表明该反应是通过自由基机理发生的。该协议使用大气中的O 2作为氧化剂，为构建氟化化合物提供了另一种绿色途径。
• [EN] SILICA-BASED ZINC CATALYSTS. THEIR PREPARATION AND USE IN THE ALKOXYCARBONYLATION OF AMINES<br/>[FR] CATALYSEURS AU ZINC À BASE DE SILICE, LEUR PRÉPARATION ET LEUR UTILISATION DANS L'ALCOXYCARBONYLATION D'AMINES
  申请人：COVESTRO DEUTSCHLAND AG

  公开号：WO2018210711A1

  公开（公告）日：2018-11-22

  The present invention relates to silica-based heterogeneous zinc compounds which are suitable as catalysts in the reaction of amines with dialkyl carbonates to produce carbamates. The catalysts have the formula [SiO2]-CH2-CHR-X-COOZn[Y], wherein [SiO2] represents a silica carrier selected from the group consisting of ordered mesoporous silica and irregular amorphous narrow pore silica, R represents a moiety selected from the group consisting of hydrogen, -CH3, and -CH2CH3, preferably hydrogen, X is an aliphatic chain of 2 to 11 carbon atoms that optionally comprises ether moieties and [Y] represents a mono anion. The invention is also directed towards a method for the preparation of the aforementioned compounds and towards method for the alkoxycarbonylation of amines.

  本发明涉及硅基杂化锌化合物，适用于作为催化剂在胺与二烷基碳酸酯反应中产生氨基甲酸酯。催化剂的化学式为[SiO2]-CH2-CHR-X-COOZn[Y]，其中[SiO2]代表从有序介孔硅和不规则非晶窄孔硅组成的硅载体，R代表从氢、-CH3和-CH2CH3组成的基团，优选为氢，X是由2至11个碳原子组成的脂肪链，可选地包含醚基团，[Y]代表单阴离子。该发明还涉及上述化合物的制备方法以及胺的烷氧羰基化方法。
• [EN] LATENT ACIDS AND THEIR USE<br/>[FR] ACIDES LATENTS ET LEUR UTILISATION
  申请人：BASF SE

  公开号：WO2016124493A1

  公开（公告）日：2016-08-11

  Compounds of the formula (I) and (IA) wherein X is -O(CO)-; R1 is C1-C12haloalkyl or C6-C10haloaryl; R2 is located in position 7 of the coumarinyl ring and is OR8; R2a, R2b and R2C independently of each other are hydrogen; R3 is C1-C8haloalkyl or C1-C8haloalkyl; R4 is hydrogen; and R8 is C1-C6alkyI; are suitable as photosensitive acid donors in the preparation of photoresist compositions such as used for example in the preparation of spacers, insulating layers, interlayer dielectric films, insulation layers, planarization layers, protecting layers, overcoat layers, banks for electroluminescence displays and liquid crystal displays (LCD).

  化合物的化学式（I）和（IA），其中X为-O(CO)-；R1为C1-C12卤代烷基或C6-C10卤代芳基；R2位于香豆素环的第7位，为OR8；R2a、R2b和R2C彼此独立地为氢；R3为C1-C8卤代烷基或C1-C8卤代烷基；R4为氢；R8为C1-C6烷基，适用于作为感光酸给体，用于制备光刻胶组合物，例如用于制备间隔层、绝缘层、层间介质膜、绝缘层、平坦化层、保护层、覆盖层、电致发光显示器和液晶显示器（LCD）的制备。
• Application of a Regioselective Mannich Reaction on Naringenin and its Use in Fluorescent Labeling
  作者：Zhu-Jun Yao、Lei Chen、Tai-Shan Hu、Jing Zhu、Houming Wu

  DOI：10.1055/s-2006-941564

  日期：——

  A novel strategy for site-specific fluorescent labeling on naringenin (1) was established by a new direct Mannich reaction in combination with a Huisgen [3+2]-cycloaddition reaction. High ­regioselectivity was observed for direct Mannich reactions on ­naringenin and several other flavonones using a variety of amines and aldehydes.

  建立了一种针对奈林素（1）的特定位置荧光标记的新策略，该策略结合了新的直接曼尼希反应和霍伊斯根 [3+2] 加成反应。通过多种胺和醛，对奈林素及其他几种黄酮类化合物的直接曼尼希反应观察到了很高的区域选择性。

表征谱图