N-硝二甲胺 | 4164-28-7

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 中文名称: N-硝二甲胺
• 英文名称: N-nitrodimethylamine
• 英文别名: N,N-dimethylnitramine；dimethylnitramine；N,N-dimethylnitramide
• CAS: 4164-28-7
• 化学式: C₂H₆N₂O₂
• mdl: MFCD00626512
• 分子量: 90.0818
• InChiKey: XRWKADIRZXTTLH-UHFFFAOYSA-N

物化性质

• 熔点：
  58°C
• 沸点：
  167.26°C (rough estimate)
• 密度：
  1.1090
• 蒸汽压力：
  0.36 mmHg
• 大气OH速率常数：
  3.84e-12 cm3/molecule*sec

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.1
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2928000090

反应信息

• 作为反应物：
  描述：

  N-硝二甲胺 以 苯 为溶剂， 生成 亚硝基二甲胺
  参考文献：
  名称：

  Mechanisms of Nitramine Thermolysis

  摘要：

  The thermal decomposition of a number of nitramines was studied in dilute solution and in the melt, The nitramines included acyclic mononitramines [dimethylnitramine (DMN), diethylnitramine (DEN), dipropylnitramine (DPN), and diisopropylnitramine (DIPN)], cyclic mononitramines [N-nitropiperidine (NPIP) and N-nitropyrrolidine (NPyr)], cyclic dinitramines [N-dinitropiperazine (pDNP), 1,3-dinitro-1,3-diazacyclopentane (DNI), and 1,3-dinitro-1,3-diazacyclohexane (mDNP)], and 1,3,5-trinitro-1,3,5-triazocyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexanitrohexaazaisowurtzitane (HNIW), and 1,3,3-trinitroazetidine (TNAZ). For the acyclic and cyclic mono- and dinitramines, the corresponding nitrosamines were the only or major condensed-phase product. Kinetics and activation parameters were determined for the thermolysis of dilute solutions (0.01-1.0 wt %) over the range 200-300 degrees C. The thermolyses were found to be first-order with the rate constants unaffected by the use of deuterated solvent. As the nitramines became more complex than dimethylnitramine (DMN), the rate of decomposition increased and the product distribution became more complex. As the length of the aliphatic chain increased (DMN < DEN < DPN), the rate of thermolysis increased, yet nitrosamine remained the only observed condensed-phase product. When a secondary carbon was attached to the N-nitramine (DIPN) rather than the primary (DPN), the rate of decomposition increased and a new condensed-phase product was observed. Among the cyclic nitramines, the rate of decomposition increased as the number of NNO2 groups increased (NPIP < pDNP; NPyr < DNI; mDMP < RDX). The position of the nitramine groups affected the decomposition: meta NNO2 groups (mDNP) decomposed faster than para (pDNP). Ring strain decreased stability: mDNP < DNI; HMX < RDX. In complex nitramines, the increase in decomposition rate, the appearance of new products, and the change in the relative importance of nitrosamine and of N-2 and N2O are attributed to new decomposition routes available to them. However, since complex nitramines (e.g. RDX) maintain first-order kinetics and since most have activation energies in the range of 40-50 kcal/mol, it is believed that the triggering mechanism remains N-NO2 homolysis. Intramolecular hydrogen transfer is also considered an important mode of nitramine decomposition.

  DOI：

  10.1021/j100079a019
• 作为产物：
  描述：

  亚硝基二甲胺 在 氧气 作用下， 生成 N-硝二甲胺
  参考文献：
  名称：

  气相中二甲基亚硝胺的光解†

  摘要：

  在室温下辐照到S 1（nπ*）S 0（363.5 nm）和S 2（ππ*）S 0（248.1 nm）跃迁后，已经研究了气相（〜1 Torr）中二甲基亚硝胺的光分解。具有单位的量子产率，激励成S 1状态产生的片段（CH 3）2 N·和NO，然后重新结合不留光化。O 2的添加仅产生一种光产物，即（CH 3）2 NNO 2。辐射到S 2状态，生成的产物CH 2 NCH 3（通过毛细管气相色谱质谱法鉴定了2 NCH 3）3，CH 2 NOH，N 2 O，NO，H 2和N 2。在存在N 2作为缓冲气体的情况下，光产物仅为CH 2 NCH 3，（CH 2 NCH 3）3，N 2 O和H 2。对于这两种激发条件，提出了一种机制，该机制涉及裂解N，N键作为主要的主要光解过程。

  DOI：

  10.1002/hlca.19810640405
• 作为试剂：
  描述：

  endo-Dicyclopentadien 在 盐酸 、 lithium aluminium tetrahydride 、 N-硝二甲胺 、 氧气 作用下， 生成 exo-9-dimethylamino-endo-tricyclo<5.2.1.0>dec-3-en-exo-8-ol 、 trans,cic,trans-2,4-bishydroxymethylbicyclo<3.3.0>oct-6-ene
  参考文献：
  名称：

  Chow, Yuan L.; Richard, Herve, Journal of the Chemical Society. Perkin transactions I, 1982, p. 1405 - 1418

  摘要：

  DOI：

文献信息

• The nitrolysis of N,N-dialkylcarboxamides in liquid carbon dioxide
  作者：I. V. Kuchurov、I. V. Fomenkov、S. G. Zlotin

  DOI：10.1007/s11172-010-0371-1

  日期：2010.11

  A method for the synthesis of N,N-dialkylnitramines by the ninrolysis of N,N-dialkylcarboxamides with a mixture of N2O5 and 100% HNO3 in liquid carbon dioxide was developed.

  开发了一种通过 N,N-二烷基甲酰胺与 N2O5 和 100% HNO3 的混合物在液态二氧化碳中的氨解来合成 N,N-二烷基硝胺的方法。
• Synthesis of N,N-dialkylnitramines from secondary ammonium nitrates in liquid or supercritical carbon dioxide
  作者：I. V. Kuchurov、I. V. Fomenkov、S. G. Zlotin

  DOI：10.1007/s11172-009-0282-1

  日期：2009.10

  An efficient explosion-proof method was developed for the preparation of N,N-dialkylnitramines by treatment of dialkylammonium nitrates with a mixture of nitric acid and acetic anhydride in the presence of ZnCl2 in liduid or supercritical carbon dioxide.

  开发了一种有效的防爆方法，通过在液态或超临界二氧化碳中在 ZnCl2 存在下用硝酸和乙酸酐的混合物处理二烷基硝酸铵来制备 N,N-二烷基硝胺。
• Formation of <i>N</i>-Nitrosamines and <i>N</i>-Nitramines by the Reaction of Secondary Amines with Peroxynitrite and Other Reactive Nitrogen Species:  Comparison with Nitrotyrosine Formation
  作者：Mitsuharu Masuda、Howard F. Mower、Brigitte Pignatelli、Irena Celan、Marlin D. Friesen、Hoyoku Nishino、Hiroshi Ohshima

  DOI：10.1021/tx990120o

  日期：2000.4.1

  mechanism, involving one-electron oxidation by peroxynitrite of secondary amines to form amino radicals (R(2)N(*)), which react with nitric oxide ((*)NO) or nitrogen dioxide ((*)NO(2)) to yield nitroso and nitro secondary amines, respectively. Reaction of morpholine with NO(*) and superoxide anion (O(2)(*)(-)), which were concomitantly produced from spermine NONOate and by the xanthine oxidase systems, respectively

  活性氮物质包括氮氧化物（N（2）O（3）和N（2）O（4）），过氧亚硝酸盐（ONOO（-））和硝酰氯（NO（2）Cl）被暗示为引起炎症和癌症的原因。我们研究了仲胺与过氧亚硝酸盐的反应，发现同时形成了N-亚硝胺和N-硝胺。在碱性pH下，过氧亚硝酸盐比在中性pH下更容易被亚硝酸盐亚硝化，而在pH 8.5下，过氧亚硝酸盐的硝化作用是最佳的。该反应中亚硝基吗啉的收率是碱性pH下亚硝基吗啉的3倍，而在pH <7.5下形成的亚硝基吗啉是亚硝基吗啉的2倍。对于吗啉-过亚硝酸盐反应，低浓度的碳酸氢盐可增强硝化作用，但过量的碳酸氢盐可抑制硝化作用。亚硝酸盐被过量的碳酸氢盐抑制。在此基础上，我们提出了一种自由基机理，涉及一种通过仲胺的过氧亚硝酸盐单电子氧化形成氨基（R（2）N（*））的基团，该基团与一氧化氮（（*）NO）或二氧化氮反应（（*）NO（2））分别产生亚硝基和硝基仲胺。吗啉与NO（*）和超氧阴离子（
• Clean nitrations: Novel syntheses of nitramines and nitrate esters by nitrodesilylation reactions using dinitrogen pentoxide (N 2 O 5 )
  作者：Ross W. Millar、Simon P. Philbin

  DOI：10.1016/s0040-4020(97)00093-8

  日期：1997.3

  with conventional substrates (amines or alcohols). These nitrodesilylation reactions proceed cleanly and in good yield, and the scope of the reaction is illustrated by. 29 examples, some of which produce high energy compounds, notably plasticisers and an energetic polymer precursor. These reactions are therefore potentially clean nitrations for the manufacture of energetic compounds which will minimise

  在这种新型的硝化方法中，使用惰性溶剂中的五氧化二氮（N 2 O 5）作为硝化剂，从而无需使用强酸作为反应介质。N 2 O 5分别在甲硅烷基胺和甲硅烷基醚中裂解杂原子-硅键，得到所需的高能基团（分别为硝胺或硝酸酯），而不会释放常规底物（胺或醇）会发生的酸。这些氮代甲硅烷基化反应清洁且收率良好，反应范围如下所示。29个实例，其中一些可以生产高能化合物，尤其是增塑剂和高能聚合物前体。因此，这些反应是潜在的清洁硝化反应，可用于生产高能化合物，这将在将来最大程度地降低这种活性对环境的影响。
• Electroreduction of primary nitramines on platinum in MeCN
  作者：V. A. Petrosyan、V. A. Frolovsky、D. A. Sad9lenko

  DOI：10.1007/bf02494405

  日期：1999.1

  Reduction of primary nitramines RNHNO2 (R=Me, Et, Pri, α-pyridyl) in anhydrous MeCN at a Pt cathode was studied by voltammetry and electrolysis. The process includes one-electron transfer and nitramine deprotonation to give the corresponding anions. The products ofN-alkylation of these anions can be obtained only when their potassium salts are used (but not tetrabutylammonium salts). This is due to

  通过伏安法和电解研究了在 Pt 阴极处无水 MeCN 中伯硝胺 RNHNO2（R=Me、Et、Pri、α-吡啶基）的还原。该过程包括单电子转移和硝胺去质子化以产生相应的阴离子。这些阴离子的N-烷基化产物只有在使用它们的钾盐（而不是四丁基铵盐）时才能获得。这是由于离子缔合的影响，会影响所研究的阴离子的双重反应性。

表征谱图