(E)-1,1-dimethyl-2-(3-phenylpropylidene)hydrazine | 145803-14-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-1,1-dimethyl-2-(3-phenylpropylidene)hydrazine
• 英文别名: (E)-dihydrocinnamaldehyde N,N-dimethylhydrazone；(E)-3-phenypropanal (N,N-dimethylhydrazone)；(E)-3-phenylpropanal N,N-dimethylhydrazone；3-Phenylpropanal dimethylhydrazone；N-methyl-N-[(E)-3-phenylpropylideneamino]methanamine
• CAS: 145803-14-1
• 化学式: C₁₁H₁₆N₂
• 分子量: 176.261
• InChiKey: GDDUTUNPOYLHEQ-ZRDIBKRKSA-N

物化性质

• 沸点：
  100-110 °C(Press: 0.1 Torr)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1,1-dimethyl-2-(3-phenylpropylidene)hydrazine 在 cerium(III) chloride 作用下， 反应 19.0h， 生成 3--1-phenylheptane
  参考文献：
  名称：

  Organocerium additions to hydrazones: effects of reagent stoichiometry on efficiency and selectivity

  摘要：

  The effects of reagent stoichiometry on the efficiency and selectivity of organocerium additions to chiral and achiral hydrazones have been investigated. rhe reagent formed in-situ from 1 equiv of CH3Li and 0.33 equiv of CeCl3 adds efficiently (>65% yield) to N,N-dimethylhydrazone 1, but this same reagent reacts only sluggishly with chiral SAMEMP hydrazone 2 (<30% yield). The optimal stoichiometry of the organocerium reagent is 1:1 CH3Li/CeCl3, despite the fact that not all of the CeCl3 ig consumed in the transmetalation. At least 2 equiv of methyl nucleophile is required to obtain acceptable yields in additions to 2, suggesting that the auxiliary side chain inhibits the reactivity of the first equivalent of organometallic reagent and that binding of the reagent to one of the hydrazone nitrogen atoms facilitates addition. This hypothesis is supported by the observation that competitive ligands such as amines or alkoxides effectively inhibit the addition of organocerium reagents to 1. The active reagent formed at all mixing stoichiometries is proposed to be a trimethyllanthanide species on the basis of reactivity and the presence of ur reacted MCl3 at less than 3:1 CH3Li/MCl3 mixing ratios.

  DOI：

  10.1021/jo00055a008
• 作为产物：
  描述：

  苯丙醛 、 偏二甲肼 在 sodium sulfate 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到(E)-1,1-dimethyl-2-(3-phenylpropylidene)hydrazine
  参考文献：
  名称：

  N,N-二烷基腙在纯水中的非催化Strecker型反应

  摘要：

  醛和酮 N,N-二烷基腙作为一类稳定的亚胺替代物，在 Strecker 反应中与原位生成的 HCN 表现出独特的反应性，在没有共溶剂、催化剂或促进剂的情况下在纯水中进行。实验证据表明，该反应受到二烷基氨基酮对对 HCN 的分子内活化的辅助。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）

  DOI：

  10.1002/ejoc.200800297

文献信息

• Organocerium additions to proline-derived hydrazones: synthesis of enantiomerically enriched amines
  作者：Scott E. Denmark、James P. Edwards、Theodor Weber、David W. Piotrowski

  DOI：10.1016/j.tetasy.2010.04.042

  日期：2010.5

  The addition of organocerium reagents (from both organolithium and organomagnesium precursors) to chiral aldehyde hydrazones prepared from 1-aminoproline derivatives has been studied. The additions proceed in good yield and high diastereoselectivity and with good nucleophile (Me, n-Bu, i-Pr, t-Bu, Ph, etc.) and substrate scope (alkyl, alkenyl and aryl). The resulting hydrazines can be converted to

  已经研究了将有机铈试剂（来自有机锂和有机镁前体）添加到由1-氨基脯氨酸衍生物制备的手性醛中。添加以高收率和高非对映选择性以及良好的亲核试剂（Me，n- Bu，i- Pr，t- Bu，Ph等）和底物范围（烷基，烯基和芳基）进行。生成的肼可通过氢解（阮内镍）的N–N键裂解或通过Li / NH 3的酰化和裂解而转化为胺。。通过改变取代基以包括更多的配位原子（氧和氮）以及去除配位原子，研究了侧链对非对映选择性的影响。带有2-甲氧基乙氧基甲基的SAMEMP助剂具有最高的非对映选择性。值得注意的是，带有简单甲基和异丁基取代基的助剂也具有很高的选择性。给出了选择性起源的假设。
• Uncatalyzed Strecker-Type Reaction of<i>N</i>,<i>N</i>-Dialkylhydrazones in Pure Water
  作者：Eugenia Marqués-López、Raquel P. Herrera、Rosario Fernández、José M. Lassaletta

  DOI：10.1002/ejoc.200800297

  日期：2008.7

  Aldehyde and ketone N,N-dialkylhydrazones behave as a stable class of imine surrogates exhibiting a unique reactivity in the Strecker reaction with in situ generated HCN, that proceeds in pure water in the absence of co-solvents, catalysts or promoters. Experimental evidence suggests that the reaction is assisted by an intramolecular activation of HCN by the dialkyl amino lone pair.(© Wiley-VCH Verlag

  醛和酮 N,N-二烷基腙作为一类稳定的亚胺替代物，在 Strecker 反应中与原位生成的 HCN 表现出独特的反应性，在没有共溶剂、催化剂或促进剂的情况下在纯水中进行。实验证据表明，该反应受到二烷基氨基酮对对 HCN 的分子内活化的辅助。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• Asymmetric organocatalytic Strecker-type reactions of aliphatic N,N-dialkylhydrazones
  作者：Aurora Martínez-Muñoz、David Monge、Eloísa Martín-Zamora、Eugenia Marqués-López、Eleuterio Álvarez、Rosario Fernández、José M. Lassaletta

  DOI：10.1039/c3ob41437j

  日期：——

  The enantioselective organocatalytic Strecker-type reaction of aliphatic N,N-dialkylhydrazones is presented. Using trimethylsilyl cyanide (TMSCN) as the cyanide source, the reaction can be efficiently catalyzed by a tert-leucine-derived bifunctional thiourea to afford the corresponding hydrazino nitriles in good to excellent yields (50–96%) and moderate to good enantioselectivities, up to 86% ee. Further

  提出了脂族N，N-二烷基hydr的对映选择性有机催化Strecker型反应。使用三甲基甲硅烷基氰化物（TMSCN）作为氰化物源，可以由叔亮氨酸衍生的双官能硫脲有效地催化反应，从而以高至优异的收率（50-96％）和中等至良好的对映选择性获得相应的肼基腈。到86％ee。腈官能团的进一步转化允许获得有用的受保护的肼基酸和咪唑烷酮。有趣的是，某些肼基腈及其衍生物可以高回收率重结晶，从而产生基本纯的对映异构体。
• Synthesis of α-phenylselanyl and α-phenylsulfanyl nitriles from aldehyde N,N-dialkylhydrazones
  作者：Michaël Ternon、Xavier Pannecoucke、Francis Outurquin、Claude Paulmier

  DOI：10.1016/s0040-4020(02)00232-6

  日期：2002.4

  dimethylhydrazones 1 (R2=H) and derived from linear aliphatic aldehydes, has led to α-phenylselanyl hydrazones 2. α-Phenylselanyl nitriles 3 were, however, isolated when an excess of base and of PhSeX (X=Cl, Br) were used. Hydrazones 1 bearing an α-alkyl substituent (R2≠H) gave also nitriles 3. SAMP-hydrazones 4 showed the same reactivity and the corresponding nitriles 3 were obtained in a racemic form. The use of

  azaenolates的Phenylselenenylation，通过LDA处理dimethylhydrazones形成1（R 2 = H），并从直链脂族醛衍生的，已经导致α-phenylselanyl腙2。但是，当使用过量的碱和PhSeX（X = Cl，Br）时，会分离出α-苯基硒基腈3。腙1轴承α-烷基取代基（R 2 ≠H），得到也腈3。SAMP-腙4显示了同样的反应性和相应的腈3外消旋形式得到。用PhSCl代替PhSeBr可以从1生成α-苯硫基腈6衍生自α-支化醛（R 2 ≠H）。
• Reaction of Tantalum-Alkyne Complexes with Hydrazones. Stereoselective Synthesis of (E)-Allylic Hydrazines.
  作者：Kazuhiko Takai、Seiji Miwatashi、Yasutaka Kataoka、Kiitiro Utimoto

  DOI：10.1246/cl.1992.99

  日期：——

  Treatment of tantalum-alkyne complexes with dimethylhydrazones by the assistance of Me 3 Al in a mixed solvent of DME, benzene, and THF at 45°C for 16 h gives (E)-allylic hydrazines stereoselectively

  在二甲醚、苯和四氢呋喃的混合溶剂中，在 Me 3 Al 的帮助下，在 45°C 下用二甲基腙处理钽-炔配合物 16 小时，立体选择性地得到 (E)-烯丙基肼