N,N,N',N'-四甲基-O-亚苯基二胺 | 704-01-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: N,N,N',N'-四甲基-O-亚苯基二胺
• 中文别名: N1,N1,N2,N2-四甲苯-1,2-二胺
• 英文名称: N,N,N',N'-tetramethyl-o-phenylenediamine
• 英文别名: N¹,N¹,N²,N²-tetramethylbenzene-1,2-diamine；N,N,N',N'-tetramethyl-1,2-phenylenediamine；N1,N1,N2,N2-tetramethylbenzene-1,2-diamine；1,2-bis(dimethylamino)benzene；o-phenylenebis(dimethylamine)；tetramethylphenylenediamine；1,2-Benzenediamine, N,N,N',N'-tetramethyl-；1-N,1-N,2-N,2-N-tetramethylbenzene-1,2-diamine
• CAS: 704-01-8
• 化学式: C₁₀H₁₆N₂
• mdl: MFCD00014865
• 分子量: 164.25
• InChiKey: CJVYYDCBKKKIPD-UHFFFAOYSA-N

物化性质

• 熔点：
  8.9°C
• 沸点：
  281.73°C (rough estimate)
• 密度：
  0.9560
• 保留指数：
  1246

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2921590090

反应信息

• 作为反应物：
  描述：

  N,N,N',N'-四甲基-O-亚苯基二胺 在 aluminum tri-bromide 、 溴 作用下， 以 氯仿 、 硝基苯 为溶剂， 反应 4.5h， 生成 4,5-bis(dimethylamino)phthalonitrile
  参考文献：
  名称：

  Mikhalenko, S. A.; Derkacheva, V. M.; Luk'yanets, E. A., Journal of general chemistry of the USSR, 1981, vol. 51, # 7, p. 1405 - 1411

  摘要：

  DOI：
• 作为产物：
  描述：

  二氧化碳 、 N-甲基-1,2-苯二胺 在 dichlorotetrakis(dimethylsulfoxide)ruthenium(II) 、 苯硅烷 、 正丁基二(1-金刚烷基)膦 作用下， 以 甲苯 为溶剂， 100.0 ℃ 、3.0 MPa 条件下， 以63%的产率得到N,N,N',N'-四甲基-O-亚苯基二胺
  参考文献：
  名称：

  二氧化碳对胺的一般催化甲基化作用

  摘要：

  使CO 2发挥作用：在还原条件下，二氧化碳是仲，伯，芳族和脂族胺的通用选择性甲基化试剂。从CO 2和可商购的硅烷以高收率获得各种叔胺，并且对腈，烯烃，醚，酯和羟基具有良好的耐受性。

  DOI：

  10.1002/anie.201301349
• 作为试剂：
  描述：

  2-oxo-2-phenylethyl 2-(tert-butoxycarbonylamino)acetate 在 N,N,N',N'-四甲基-O-亚苯基二胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以100%的产率得到BOC-甘氨酸
  参考文献：
  名称：

  Protecting Groups That Can Be Removed through Photochemical Electron Transfer:  Mechanistic and Product Studies on Photosensitized Release of Carboxylates from Phenacyl Esters

  摘要：

  Photolysis of electron-donating photosensitizers in the presence of various phenacyl esters (PhCOCH2-OCOR) results in C-O bond scission leading to the formation of acetophenone (PhCOCH3) and the corresponding carboxylic acid(RCO2H). Preparative experiments showed that the carboxylic acids are generated in high or quantitative isolated yields. It is argued that this reaction is initiated by a photoinduced electron transfer from the excited state sensitizer to the phenacyl ester. The latter process forms the anion radical of the phenacyl ester which in turn undergoes rapid C-O bond scission leading to the phenacyl radical and the corresponding carboxylate anion. This mechanism is supported by the following observations. (1) The phenacyl esters quench fluorescence from the sensitizers. (2) Analysis of the redox potentials of the sensitizer excited states and the substrates shows that the proposed electron transfer step is exergonic by 15-20 kcal/mol. (3) The byproducts are indicative of the proposed ion radical intermediates. In particular N-methylaniline is detected when N,N-dimethylaniline is used as a sensitizer. (4) Competing processes are observed in phenacyl esters whose acid components are themselves labile to single-electron transfer. For example, phenacyl 4-bromophenylacetate showed bromide elimination in competition with deprotection.

  DOI：

  10.1021/jo970495j

文献信息

• Supercritical methanol as solvent and carbon source in the catalytic conversion of 1,2-diaminobenzenes and 2-nitroanilines to benzimidazoles
  作者：Zhuohua Sun、Giovanni Bottari、Katalin Barta

  DOI：10.1039/c5gc01040c

  日期：——

  Benzimidazoles and N-methylbenzimidazoles were synthesized by simply heating 1,2-diaminobenzenes in supercritical methanol over copper-doped porous metal oxides.

  苯并咪唑和N-甲基苯并咪唑是通过在掺铜多孔金属氧化物中超临界甲醇中加热1,2-二氨基苯合成的。
• BORON OR ALUMINUM COMPLEXES
  申请人：Armand Michel

  公开号：US20110171112A1

  公开（公告）日：2011-07-14

  The present invention relates to boron and aluminum complexes, to the preparation thereof, and to the use thereof for solubilizing ionic compounds. The complexes have one of the following formulae: in which D represents B or Al; R 1 represents R, R F , NO 2 , CN, C(═O)OR, RSO 2 , or R F SO 2 ; —X 1 —, —X 2 —, —X 3 — and X 4 each represent a divalent group >C═O, >C═NC≡N, >C═C(C≡N) 2 , >CR 2 R 3 or >SO 2 ; —Y 1 —, —Y 2 — and —Y 3 — each represent a divalent group —O—, >N(C≡N), >N(COR F ), >N(SO 2 R 4 ), >NR 4 , >N(COR 4 ) or >N(SO 2 R F ); R, R 2 and R 3 each represent H, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an oxaalkyl group or an alkenyl group; R 4 represents an alkyl group, an aryl group, an alkylaryl group, a heteroaryl group, an arylalkyl group, an oxaalkyl group, an alkenyl group or an R F CH 2 — group; R F is a perfluoroalkyl group, a partially fluorinated alkyl group, or a partially or totally fluorinated phenyl group; each of the R′ 2 and R′ 3 groups represents R or F.

  本发明涉及硼和铝配合物，其制备方法以及用于溶解离子化合物的用途。这些配合物具有以下公式之一： 其中D代表B或Al；R1代表R、RF、NO2、CN、C(═O)OR、RSO2或RF SO2；—X1—、—X2—、—X3—和X4每个代表一个二价基团>C═O、>C═NC≡N、>C═C(C≡N)2、>CR2R3或>SO2；—Y1—、—Y2—和—Y3—每个代表一个二价基团—O—、>N(C≡N)、>N(CORF)、>N(SO2R4)、>NR4、>N(COR4)或>N(SO2RF)；R、R2和R3每个代表H、烷基、芳基、烷基芳基、芳基烷基、氧代烷基或烯基；R4代表烷基、芳基、烷基芳基、杂芳基、芳基烷基、氧代烷基、烯基或RFCH2—基团；RF是全氟烷基、部分氟化烷基或部分或完全氟化苯基；R′2和R′3中的每个代表R或F。
• Process for the preparation of urethanes
  申请人：Jacob Andreas

  公开号：US20090275771A1

  公开（公告）日：2009-11-05

  Urethanes are prepared by oxidative carbonylation of at least one amino compound in the presence of carbon monoxide, oxygen and organic, at least one hydroxyl-group-carrying compound. The carbonylation is carried out in the absence of halogen-containing promoters. The carbonylation is also carried out in the presence of a metal complex catalyst which contains neutral bidentate N-chelate ligands of the (N˜N) type, two monoanionic N,O-chelate ligands of the general type (N˜O) − or tetradentate dianionic chelate ligands (O˜N˜N˜O) 2− .

  聚氨酯是通过氧化羰基化至少一种氨基化合物来制备的，在碳一氧化碳、氧气和有机物存在下，至少还有一种带有羟基的化合物。羰基化是在不存在含卤素的促进剂的情况下进行的。羰基化也是在含有中性双齿N-螯合配体（N˜N）类型的金属络合物催化剂存在下进行的，这种配体是两个单负离子N,O-螯合配体的一般类型(N˜O) − 或四个双负离子螯合配体（O˜N˜N˜O） 2− 。
• METHOD FOR PRODUCING URETHANES
  申请人：Gärtner Felix

  公开号：US20130303740A1

  公开（公告）日：2013-11-14

  The invention relates to a method for producing urethanes or ureas or mixtures of urethanes and ureas by oxidative carbonylation of organic amines in the presence of carbon monoxide, oxygen and a catalyst, where the catalyst used is a transition metal complex containing the structural feature: [Mn+(O˜N˜O)2−](n-2)+(L)m(Z−)n-2 and the method is carried out under halogen-free reaction conditions. The invention further relates to transition metal complexes containing said structural feature and also to the use of such transition metal complexes as catalysts in the production of urethanes or ureas or mixtures of urethanes and ureas.

  本发明涉及一种通过氧化羰基化有机胺在碳一氧化碳、氧气和催化剂存在下生产尿素或尿素或尿素和尿素的混合物的方法，其中使用的催化剂是一种含有以下结构特征的过渡金属配合物：[Mn+(O˜N˜O)2−](n-2)+(L)m(Z−)n-2，该方法在无卤素反应条件下进行。本发明进一步涉及含有上述结构特征的过渡金属配合物，以及将这种过渡金属配合物作为催化剂用于生产尿素或尿素或尿素和尿素的混合物。
• General Catalytic Methylation of Amines with Formic Acid under Mild Reaction Conditions
  作者：Iván Sorribes、Kathrin Junge、Matthias Beller

  DOI：10.1002/chem.201402124

  日期：2014.6.23

  A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines including [N‐13C]‐labelled drugs in good to excellent yields under mild conditions.

  已经开发了一种用于胺甲基化的一般催化方案，这是首次使用甲酸作为C 1结构单元，使用硅烷作为还原剂。各种各样的芳香族和脂肪族伯胺和仲胺都已被转化为相应的叔胺，包括[ N - 13 C]标记的药物，在温和的条件下具有良好或优异的收率。

表征谱图