1,2,3,10a-tetrahydrophenanthrene-1,1,2,2-tetracarbonitrile | 51958-62-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 1,2,3,10a-tetrahydrophenanthrene-1,1,2,2-tetracarbonitrile
• 英文别名: 1,1,2,2-Phenanthrenetetracarbonitrile, 3,10a-dihydro-；3,10a-dihydrophenanthrene-1,1,2,2-tetracarbonitrile
• CAS: 51958-62-4
• 化学式: C₁₈H₁₀N₄
• 分子量: 282.304
• InChiKey: VGCWNNAHNQZECD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  95.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-乙烯萘 、 四氰基乙烯 以 氯仿 、 乙酸乙酯 为溶剂， 以93%的产率得到1,2,3,10a-tetrahydrophenanthrene-1,1,2,2-tetracarbonitrile
  参考文献：
  名称：

  Molecular Complexation and Kinetics for Diels−Alder Condensation of Naphthylalkenes with Tetracyanoethylene

  摘要：

  The charge-transfer spectra of 1:1 molecular complexes of seven 1-alkyl-1-(2-naphthyl)ethenes (where R = alkyl group: H, Me, Et, n-Pr, i-Pr, t-Bu, Neopent) and 1-vinylnaphthalene with TCNE were determined in ClCH2CH2Cl as solvent at 27.1 degrees C. Equilibrium constants, K, for these complexes vary with R, as based on two opposing factors, viz. (a) the polar substituent factor sigma* and (b) the angle-of-twist theta between the planes of the naphthyl and vinyl groups. For R = Neopent (sigma* dominant) K is 50 times as large as for R = t-Bu (theta dominant). Except for R = t-Bu, kinetics of reaction conform with the equation D + TCNE reversible arrow (K) D.TCNE reversible arrow (k(1)/k(-1)) P, where D is the donor alkene, P is the Diels-Alder 1,4-cycloaddition product, and k(1) and k(-1) are first-order reaction rate constants. Values of k(1) vary from 0.71 min(-1) (R = H) to 55.5 min(-1) (R = Neopent) and the corresponding relative second-order rate constants k(2) (or k(1)K) from 1 to 4000. The rate constant k(-1) was measured only for 1b (R = Me, 0.0017 min(-1)) in the solvent mixture p-xylene/ClCH2CH2Cl. Formation of 1b.TCNE complex gives Delta H = 10.0 kcal/mol and Delta S = 38.4 eu, and conversion to P shows an Arrhenius activation energy of E-a = 7.24 kcal/mol. It is proposed that the preferred conformation of a naphthylalkene for complexation has the R and vinyl groups projecting outward from opposite sides of the plane of the naphthalene ring. The TCNE molecule then aligns parallel to the naphthalene ring on the vinyl side where (except for R = t-Bu) it can slide into the geometry of the transition state to form P.

  DOI：

  10.1021/jo9804902

文献信息

• Molecular Complexation and Kinetics for Diels−Alder Condensation of Naphthylalkenes with Tetracyanoethylene
  作者：LeRoy H. Klemm、Wayne C. Solomon、Amir P. Tamiz

  DOI：10.1021/jo9804902

  日期：1998.9.1

  The charge-transfer spectra of 1:1 molecular complexes of seven 1-alkyl-1-(2-naphthyl)ethenes (where R = alkyl group: H, Me, Et, n-Pr, i-Pr, t-Bu, Neopent) and 1-vinylnaphthalene with TCNE were determined in ClCH2CH2Cl as solvent at 27.1 degrees C. Equilibrium constants, K, for these complexes vary with R, as based on two opposing factors, viz. (a) the polar substituent factor sigma* and (b) the angle-of-twist theta between the planes of the naphthyl and vinyl groups. For R = Neopent (sigma* dominant) K is 50 times as large as for R = t-Bu (theta dominant). Except for R = t-Bu, kinetics of reaction conform with the equation D + TCNE reversible arrow (K) D.TCNE reversible arrow (k(1)/k(-1)) P, where D is the donor alkene, P is the Diels-Alder 1,4-cycloaddition product, and k(1) and k(-1) are first-order reaction rate constants. Values of k(1) vary from 0.71 min(-1) (R = H) to 55.5 min(-1) (R = Neopent) and the corresponding relative second-order rate constants k(2) (or k(1)K) from 1 to 4000. The rate constant k(-1) was measured only for 1b (R = Me, 0.0017 min(-1)) in the solvent mixture p-xylene/ClCH2CH2Cl. Formation of 1b.TCNE complex gives Delta H = 10.0 kcal/mol and Delta S = 38.4 eu, and conversion to P shows an Arrhenius activation energy of E-a = 7.24 kcal/mol. It is proposed that the preferred conformation of a naphthylalkene for complexation has the R and vinyl groups projecting outward from opposite sides of the plane of the naphthalene ring. The TCNE molecule then aligns parallel to the naphthalene ring on the vinyl side where (except for R = t-Bu) it can slide into the geometry of the transition state to form P.