glyoxal mono-N,N-dimethylhydrazone | 133643-19-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: glyoxal mono-N,N-dimethylhydrazone
• 英文别名: glyoxal(N,N-dimethyl)monohydrazone；glyoxal-N,N-dimethyl monohydrazone；(dimethyl-hydrazono)-acetaldehyde；Glyoxal mono-dimethylhydrazone；(2E)-2-(dimethylhydrazinylidene)acetaldehyde
• CAS: 133643-19-3
• 化学式: C₄H₈N₂O
• 分子量: 100.12
• InChiKey: WJYMBVJBSFMDLE-HWKANZROSA-N

物化性质

• 沸点：
  135.8±23.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  glyoxal mono-N,N-dimethylhydrazone 以62%的产率得到
  参考文献：
  名称：

  SEVERIN T.; POCHLMANN H., CHEM. BER., 1978, 111, NO 4, 1564-1577

  摘要：

  DOI：
• 作为产物：
  描述：

  草酸醛 、 偏二甲肼 以 水 为溶剂， 以91%的产率得到glyoxal mono-N,N-dimethylhydrazone
  参考文献：
  名称：

  Chiral aminal termplates 61. Diastereoselectivity of hydrazone alkylation. Asymmetric synthesis of α-aminoaldehydes

  摘要：

  Glyoxal is efficiently transformed into the chiral aminals bearing the hydrazone functionality 2a and 2b. These compounds react under complete diastereocontrol with various organolithium reagents, affording chiral hydrazines 3-9. Reduction with Raney nickel leads to aminal protected alpha-aminoaldehydes, which, in turn, are easily hydrolyzed to the free chiral aldehydes (after tBoc protection of the amine).

  DOI：

  10.1016/s0040-4039(00)92036-7

文献信息

• Synthesis of 4,5-Disubstituted Benzo[c][2,7]naphthyridines by Combined Metalation-Palladium-Catalysed Cross-Coupling Strategies. Preparation of 8h-Pyrido[4,3,2-<i>mn</i>]acridone as a Model of Cystodytin Alkaloids
  作者：F. Guillier、F. Nivoliers、C. Cochennec、A. Godard、F. Marsais、G. Quéguiner

  DOI：10.1080/00397919608003845

  日期：1996.12

  Abstract A short and efficient synthesis of 8H-pyrido[4,3,2-mn]acridone is described. The strategy involves the preparation of 4-chloro-5-methylbenzo[c][2,7]naphtyridine, as key intermediate, by metalation and Palladium catalyzed cross-coupling reaction. A second cross-coupling reaction and subsequent oxydation by SeO2 led to the title compound.

  摘要 描述了 8H-吡啶并[4,3,2-mn]吖啶酮的快速高效合成。该策略涉及通过金属化和钯催化的交叉偶联反应制备作为关键中间体的 4-氯-5-甲基苯并[c][2,7]萘啶。第二次交叉偶联反应和随后的 SeO2 氧化得到标题化合物。
• Chiral Aminal Templates: Diastereoselective Addition to Hydrazones; An Asymmetric Synthesis of α-Amino Aldehydes
  作者：Alex Alexakis、Nathalie Lensen、Jean-Philippe Tranchier、Pierre Mangeney、J. Feneau-Dupont、J. P. Declercq

  DOI：10.1055/s-1995-4042

  日期：1995.8

  The monohydrazone of glyoxal may be derivatized into a chiral aminal with diamine 7. The resulting chiral reagent 13 reacts with complete diastereocontrol with organolithium reagents in THF. This sterically controlled reaction may be altered to chelation control by using Grignard reagents in toluene, affording the opposite diastereomer in excellent de. The N-N bond of the hydrazine functionality is then cleaved with Raney nickel, assisted by ultrasound. After protection of the resulting primary amino functionality, the aminal is hydrolyzed to afford the desired α-amino aldehydes without epimerization. The same reaction sequence, without cleavage of the N-N bond, affords an α-hydrazino aldehyde.

  乙二醛的单氢肼可与二胺7衍生化为一个手性氨胺。所得的手性试剂13在四氢呋喃中与有机锂试剂反应，具有完全的非对映体选择性。通过在甲苯中使用格氏试剂，这一立体控制反应可被改变为螯合控制，从而生成相反的非对映体，并获得优异的对映选择性。接着，利用超声波的辅助下，水合肼的N-N键被拉尼镍裂解。在保护产物中的初级氨基功能基后，氨胺被水解，生成所需的α-氨基醛而不发生表异构化。相同的反应序列，如果不裂解N-N键，则会生成α-肼醛。
• Indium-Mediated Allylation of the <i>N</i>,<i>N</i>-Dimethyl Glyoxal Mono-Hydrazone: One-Pot Synthesis of Bis-Homoallyl, and of Homoallyl-Alkyl 1,2-Diols
  作者：Vanda Cerè、Francesca Peri、Salvatore Pollicino、Alfredo Ricci

  DOI：10.1055/s-1999-2881

  日期：——

  Hydrazones behave as highly reactive species in the allylation under Barbier conditions. Nucleophilic addition of an alkyllithium to the carbonyl moiety of the glyoxal mono-hydrazone followed by indium-mediated allylation, leads in high yields to bis-functionalized 1,2-diols in a one-pot two-step reaction.

  在Barbier条件下，肼酮表现为高度反应活性物质。烷基锂对醛酮单肼的羰基部分进行亲核加成，随后通过印媒介催化的烯丙基化反应，能在一步两阶段反应中高产率地得到双功能化的1,2-二醇。
• Synthesis of 2-formyl-1-aza-dibenzo[<i>e</i>,<i>h</i>]azulenes
  作者：Dijana Pešić、Ivana Ozimec Landek、Ana Čikoš、Biserka Metelko、Vesna Gabelica、Barbara Stanić、Mladen Merćep、Milan Mesić

  DOI：10.1002/jhet.5570440524

  日期：2007.9

  Synthesis of a novel heterocyclic class of compounds, 1-aza-dibenzo[e,h]azulenes [1] (6a-c and 7a-c), derived from dibenzo[b,f]oxepin, its 8-chloro analogue and dibenzo[b,f]thiepin, respectively, is described. Aldol condensation of the starting ketones 4a-c with (dimethyl-hydrazono)-acetaldehyde affords hydrazonoethylidene derivatives 5a-c, which on reduction with sodium dithionite and subsequent cyclization

  衍生自二苯并[ b，f ]氧杂环丁烯，其8-氯类似物和二苯并的新型杂环化合物1-氮杂-二苯并[ e，h ] azulenes [1]（6a-c和7a-c）描述了[ b，f ] thiepin。起始酮4a-c与（二甲基-肼基）-乙醛的醛醇缩合得到肼基亚乙基衍生物5a-c，其经连二亚硫酸钠还原并随后环化后提供目标四环1-氮杂-二苯并[ e，h ] azulenes 6a- c。的区域特异性甲酰化用Vilsmeier试剂在图6a-c中得到2-甲酰基衍生物7a-c。测试了一系列衍生物6a-c和7a-c的抗炎活性，作为体外肿瘤坏死因子α（TNF-α）产生的潜在抑制剂。
• SAR of 4-hydroxypiperidine and hydroxyalkyl substituted heterocycles as novel p38 map kinase inhibitors
  作者：Laszlo Revesz、Franco E Di Padova、Thomas Buhl、Roland Feifel、Hermann Gram、Peter Hiestand、Ute Manning、Alfred G Zimmerlin

  DOI：10.1016/s0960-894x(00)00200-6

  日期：2000.6

  The 4-hydroxypiyeridine substituent was found to confer high p38 selectivity devoid of COX-1 affinity, when attached to a series of pyridinyl substituted heterocycles. Pyridinyloxazole 11 showed a promising in vivo profile with bioavailability of 64% and ED50 in rat collagen induced arthritis of 10 mg/kg po bid. In contrast to pyridinylimidazoles such as SE 203580, 11 did not inhibit human cytochrome P450 isoenzymes. (C) 2000 Elsevier Science Ltd. All rights reserved.