2-lithio-N,N,N′,N′-tetramethyl-1,4-phenylenediamine | 68317-83-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-lithio-N,N,N′,N′-tetramethyl-1,4-phenylenediamine
• CAS: 68317-83-9
• 化学式: C₁₀H₁₅LiN₂
• 分子量: 170.183
• InChiKey: RVABWCAUDWXQOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.87
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-lithio-N,N,N′,N′-tetramethyl-1,4-phenylenediamine 在 氢溴酸 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 32.0h， 生成 2,5-(N,N,N',N'-tetramethyldiamino)-1-(2,3,7,8,13,17-hexaethyl-12,18-dimethylporphyrin-5-yl)benzene
  参考文献：
  名称：

  Charge transfer in covalently-linked porphyrin-donor complexes from picosecond transient absorption spectroscopy

  摘要：

  Octaalkyl free base porphyrins have been synthesized with covalently attached electron donors at a single meso position. Singlet-state lifetimes were determined from fluorescence quenching in three solvents and were found to be less-than-or-equal-to 1.5 ps for the N,N,N,N'-tetramethyl-1,4-phenylenediamine (TMPD) appended complex, 1.3 ns for the phenyl-TMPD-appended complex, and greater-than-or-equal-to 5 ns for the phertyl-appended, N,N-dimethylaniline (DMA) appended, and DMA-TMPD-appended porphyrin complexes in o-difluorobenzene. Single photon counting measurements and fluorescence quantum yield quenching studies of the phenyl-appended control and phenyl-TMPD charge-transfer complex gave 14 +/- 3 and 2 +/- 0.3 ns excited-state lifetimes, respectively. Fluorescence quantum yields of the TMPD and phenyl-TMPD porphyrins were higher in solvents with lower dielectric constants. Picosecond absorption spectroscopy was performed on molecules exhibiting fluorescence quenching to characterize the charge-transfer state and to determine the recombination kinetics. Conclusive evidence of charge transfer was obtained by observing the donor cation absorption at 606 nm for the TMPD and phenyl-TMPD porphyrins. Picosecond absorption changes in the 380-500-nm region are complete within 50 ps for the TMPD-appended free base porphyrin and 11.5 ns for the phenyl-TMPD-appended free base porphyrin. First-order kinetic analysis indicates that the charge recombination rates are 26 +/- 3 ps and 3.5 +/- 0.4 ns for the TMPD-appended and phenyl-TMPD-appended complexes, respectively. These data yield beta = 0.8-1.1 angstrom-1 for the exponent in the distance dependence of the electron-transfer rate, exp{-beta(r-r0)}. Inasmuch as similar beta values have been determined for electron transfer through saturated bonds, it can be concluded that the pi system of the meso substituents is ineffective in mediating electron transfer, as expected from the near orthogonality of the porphyrin and substituent rings. This is the first systematic study of electron transfer in porphyrin-donor complexes.

  DOI：

  10.1021/j100137a021
• 作为产物：
  描述：

  N,N,N',N'-四甲基对苯二胺 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 、 环己烷 为溶剂， 反应 19.0h， 生成 2-lithio-N,N,N′,N′-tetramethyl-1,4-phenylenediamine
  参考文献：
  名称：

  ortho-Lithiations Reassessed: the Advantages of Deficiency Catalysis in Hydrocarbon Media

  摘要：

  Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODM.A), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many eases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.

  DOI：

  10.1021/om301120e

文献信息

• Horner, L.; Simons, G., Phosphorus and Sulfur and the Related Elements, 1983, vol. 14, p. 253 - 266
  作者：Horner, L.、Simons, G.

  DOI：——

  日期：——
• HORNER, L.;SIMONS, G., PHOSPH. AND SULFUR, 1983, 14, N 2, 253-260
  作者：HORNER, L.、SIMONS, G.

  DOI：——

  日期：——
• FRIEDMANN G.; LINDER P.; BRINI M.; CHEMINAT A., J. ORG. CHEM., 1979, 44, NO 2, 237-239
  作者：FRIEDMANN G.、 LINDER P.、 BRINI M.、 CHEMINAT A.

  DOI：——

  日期：——