N-isopropyl-(E)-crotonaldimine | 77499-83-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-isopropyl-(E)-crotonaldimine
• 英文别名: (E,E)/(Z,E)-N-Isopropyl-1-aza-1,3-pentadien；(E)-N-propan-2-ylbut-2-en-1-imine
• CAS: 77499-83-3
• 化学式: C₇H₁₃N
• 分子量: 111.187
• InChiKey: TXVBMRBYDNEBDJ-FKQQABSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-isopropyl-(E)-crotonaldimine 在 potassium tert-butylate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 25.5h， 生成 2-(1-Isopropyl-1,4,5,6-tetrahydro-pyridin-3-yl)-propionitrile
  参考文献：
  名称：

  Synthesis of 3-vinylpiperidines, 3-ethylidenepiperidines and 5-functionalized-1,2,3,4-tetrahydropyridines

  摘要：

  Reaction of 1-azapentadienyl anions, generated by deprotonation of N-(2-buten-1-ylidene)alkylamines, with 1-bromo-3-chloropropane led to the formation of N-[2-(3-chloropropyl)-3-buten-1-ylidene]alkylamines. By reaction with nucleophiles and bases, the latter functionalized imines were converted into unsaturated piperidines, i.e. 3-vinylpiperidines, 3-ethylidenepiperidines, 5-vinyl-1,2,3,4-tetrahydropyridines and 5-(2-cyanoethyl)-1,2,3,4-tetrahydropyridines. 5-Vinyl-1,2,3,4-tetrahydropyridines proved to be suitable dienes in Diels-Alder reactions with N-phenylmaleimide, giving rise to octahydro-1H-pyrrolo[3,4h]quinoline-1,3-diones. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00019-2
• 作为产物：
  描述：

  巴豆醛 、 异丙胺 在 tamis moleculaires 作用下， 以 乙醚 为溶剂， 反应 12.0h， 以60%的产率得到N-isopropyl-(E)-crotonaldimine
  参考文献：
  名称：

  丁二烯和丁二烯催化共镍低聚：Contrôlede lasélectivité

  摘要：

  描述了丁二烯与杂二烯和杂烯烃的镍（0）催化的共低聚。显示了如何通过杂原子在杂配体中的位置以及所用催化体系的性质来控制这些反应的选择性。

  DOI：

  10.1016/s0040-4020(01)96748-1

文献信息

• Reactions of monoazadienes with metal carbonyl complexes III. Thermal conversion of n-alkyl-(e)-crotonaldimine with ru3(co)12 to σ-n,μ2-η3-allyl and μ2-η3-azaallyl bonded six electron fragments coordinated to a hexacarbonyl diruthenium unit. X-ray single crystal structure determinations of ru2(co)6{σ-n,μ2-η3-ch2cc(h)c(h)nc4h9-t} and ru2(co)6{μ2-η3-c2h5cc(h)nc4h9−}
  作者：L.H. Polm、C.J. Elsevier、W.P. Mul、K. Vrieze、M.J.N. Christophersen、F. Muller、C.H. Stam

  DOI：10.1016/s0277-5387(00)83868-1

  日期：1988.1

  complexes Ru2(CO)6L that arise from thermal reactions of monoazadienes (E)-CH3C(H)C(H)C(H)NR (1); (R = t−C4H9, i−C3H7, c−C6H11) with Ru3(CO)12 are reported. The bonding of the six-electron donating organic fragments in the complexes Ru2(CO)6σ-N,μ2-η3-CH2CC(H)C(H)NC4H9−t} (4a) and Ru2(CO)6C2H5CC(H) NC4H9−t} (5a) is described on the basis of their X-ray single crystal structure determinations

  由单氮二烯（E）-CH 3 C（H）C（H）C（H）NR（1）的热反应产生的两个络合物Ru 2（CO）6 L ；报道了具有Ru 3（CO）12的（R ＝t C 4 H 9，i C 3 H 7，c C 6 H 11）。六电子在复合性有机片段的Ru的接合2（CO）6 σ-N，μ 2 -η 3 -CH 2 CC（H）C（H）NC 4 ħ 9-t }（图4a）和Ru 2（CO）6 C 2 H ^ 5 CC（H）NC 4 ħ 9 -t }（图5a）它们的X射线单晶结构测定的基础上进行说明。在化合物4a中的有机配位体是σ-N，μ 2 -η 3配位的且含有一个扭曲η 3 -烯丙基片段桥接两个的Ru（CO）3个部分。化合物5a中设有μ 2 -η 3 -azaallyl二价阴离子桥接在钌的钌中心2（CO）6核。讨论了形成4a和5a的可能途径，分别涉及脱氢和1,2-H转移。
• Wolf, Gerhard; Wuerthwein, Ernst-Ulrich, Chemische Berichte, 1991, vol. 124, # 4, p. 889 - 896
  作者：Wolf, Gerhard、Wuerthwein, Ernst-Ulrich

  DOI：——

  日期：——
• Synthèse régio et st'eréosélective de dehydroindanes trisubstitutés
  作者：P. Brun、A. Tenaglia、J.P. Zahra、B. Waegell

  DOI：10.1016/s0040-4039(01)91179-7

  日期：1984.1
• Cyclometalation of 1-aza-1,3-dienes in reactions with Ru3(CO)12 with formation of four- and five-membered azaruthenacycles
  作者：Wilhelmus P. Mul、Cornelis J. Elsevier、Louis H. Polm、Kees Vrieze、Martin C. Zoutberg、Dick Heijdenrijk、Casper H. Stam

  DOI：10.1021/om00053a030

  日期：1991.7

  The dinuclear compounds Ru2(CO)6[R1CH2CC(H)NR2] (2a-e) and Ru2(CO)6[R1C = C(H)CH2NR2] (3a,b,d) are the first isolable products during thermal reactions of Ru3(CO)12 with 1-aza 1,3-dienes R1C(H) = C(H)C(H) = Nr2 (R1,R2-MAD; R1, R2 = CH3, i-Pr (1a), CH3, c-Hex (1b), CH3, t-Bu (1c), C6H5, i-Pr (1d), C6H5, t-Bu (1e)). Both primary products 2 and 3 contain an isomerized MAD ligand that is part of a four- (2) or five-membered (3) azaruthenacycle. The molecular structure of 3a has been solved by X-ray crystallography: space group P1BAR, with a = 22.511 (4) angstrom, b = 13.740 (3) angstrom, c = 12.443 (2) angstrom, alpha = 103.21 (1)-degrees, beta = 113.00 (1)-degrees, gamma = 77.71 (1)-degrees, V = 851.3 angstrom, Z = 2, and R = 0.027 (R(w) = 0.042), for 2540 observed reflections. Compound 3a contains a formally 6-electron donating enyl-amido ligand and is mu-N,sigma-C-beta,eta-2-C = C-coordinated to a ''sawhorse'' Ru2(CO)6 core. In solution both 2 and 3 stereochemically nonrigid, due to ''windshield wiper'' motions of the asymmetrically bridged amido ligands. This process is more facile for 2 (DELTA-G double-ended-dagger almost-equal-to 35 kJ mol-1) than for 3 (DELTA-G double-ended-dagger almost-equal-to 62 kJ mol-1), and the DELTA-G double-ended-dagger value for 3 was shown to be independent of the R1 and R2 substituents. In refluxing heptane 2 and 3 are converted into the linear 66-electron cluster Ru4(CO)10[R1C = C(H)C(H) = NR2]2 (5a-e), albeit conversion of 2 into 5 proceeded very slowly and incompletely. Conversion of 3 into 5 proceeds via the intermediacy of (mu-H)Ru2(CO)5[R1C = C(H)C(H) = NR2] (4), which air-sensitive compound could be observed and isolated for R1, R2 = C6H5, i-Pr (4d). Reaction of 3a,b with CH3,R2-MAD or crotonaldehyde in heptane at 90-degrees-C results in the formation of Ru2(CO)6[CH2CC(H)C(H) = NR2] (6a,b). During this conversion the coordinated ligand is dehydrogenated whereas the added substrate acts as a hydrogen acceptor. For crotonaldehyde it was shown that the olefin moiety was hydrogenated chemoselectively. The formation of 2 and 3 out of Ru3(CO)12 and R1,R2-MAD and their conversion into 4-6 are discussed.
• Polm, Louis H.; Mul, Wilhelmus P.; Elsevier, Cornelis J., Organometallics, 1988, vol. 7, # 2, p. 423 - 429
  作者：Polm, Louis H.、Mul, Wilhelmus P.、Elsevier, Cornelis J.、Vrieze, Kees、Christophersen, Martin J. N.、Stam, Casper H.

  DOI：——

  日期：——