(E)-3,4-Bis{[(tert-butyl)dimethylsilyloxy]methyl}-1-(4-nitrophenyl)-6-(trimethylsilyl)hex-3-ene-1,5-diyne | 326500-35-0

• 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)-3,4-Bis{[(tert-butyl)dimethylsilyloxy]methyl}-1-(4-nitrophenyl)-6-(trimethylsilyl)hex-3-ene-1,5-diyne
• 英文别名: [(E)-3,4-bis[[tert-butyl(dimethyl)silyl]oxymethyl]-6-(4-nitrophenyl)hex-3-en-1,5-diynyl]-trimethylsilane
• CAS: 326500-35-0
• 化学式: C₂₉H₄₇NO₄Si₃
• 分子量: 557.953
• InChiKey: NZMNXQHJKXIVMI-OCEACIFDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.17
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-3,4-Bis{[(tert-butyl)dimethylsilyloxy]methyl}-1-(4-nitrophenyl)-6-(trimethylsilyl)hex-3-ene-1,5-diyne 在 甲醇 、 四甲基乙二胺 、 4 A molecular sieve 、 potassium carbonate 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 (E,E)-3,4,9,10-Tetrakis{[(tert-butyl)dimethylsilyloxy]methyl}-1,12-bis(4-nitrophenyl)dodeca-3,9-diene-1,5,7,11-tetrayne
  参考文献：
  名称：

  Synthesis and Physical Investigation of Donor–Donor and Acceptor–Acceptor End-Functionalized Monodisperse Poly(triacetylene) Oligomers

  摘要：

  Two series of monodisperse, terminally donor-donor [D-D, D=4-(dimethylamino)phenyl] and acceptor-acceptor [A-A, A=4-nitrophenyl] functionalized poly(triacetylene) (PTA) oligomers ranging from monomer to hexamer were synthesized by oxidative Hay oligomerization under end-capping conditions. The corresponding D-D and A-A end-substituted polymers with an average degree of polymerization (DP) of n approximate to 18 and n approximate to 12, respectively, were also prepared and served as reference points for the corresponding infinitely long polymers. These terminally functionalized PTA oligomers and polymers are yellow- to orange-colored compounds, displaying excellent solubility in aprotic solvents with melting points above 200 degreesC for the hexamers. For the 4-(dimethylamino)phenyl substituted compounds, a consistent first oxidation potential around + 0.42 V versus Fc/Fc(+) (ferrocene/ferricinium) was observed, whereas the 4-nitrophenyl functionalized systems underwent a reversible reductive two-electron transfer around -1.40 V versus Fc/Fc(+). The nature of the end-groups has a dramatic influence on the electronic absorption spectra. Saturation of the linear optical properties in the D-D series occurs at significantly shorter chain-length [effective conjugation length (ECL) of n approximate to 4 monomer units] than in the A-A substituted or the previously reported Me3Si- and Et3Si-end-capped PTA oligomer series (ECL: n approximate to 10 monomer units). Similar observations with respect to the ECL were made by measurement of the Raman-active <()over tilde>((C=C)) stretches. Third-harmonic generation (THG) and degenerate four-wave mixing (DFWM) experiments showed that shorter oligomers of terminally D-D or A-A functionalized PTAs display higher second hyperpolarizabilities gamma than the corresponding R3Si-end-capped series (R=alkyl), Moreover, they disclose a distinct peak of the nonlinearity per monomer unit at intermediate backbone lengths. In THG experiments, the second hyperpolarizabilities for long D/A-functionalized PTA oligomers attained the same saturation values as observed for the corresponding R3Si-end-capped rods. The nonlinearities measured by DFWM of the D-D and A-A substituted PTAs were found to be larger than for the silylated ones, which can be explained by the closeness of the two-photon resonance.

  DOI：

  10.1002/1521-3765(20001201)6:23<4400::aid-chem4400>3.0.co;2-a
• 作为产物：
  描述：

  4-硝基碘苯 、 [(E)-3,4-bis[[tert-butyl(dimethyl)silyl]oxymethyl]hex-3-en-1,5-diynyl]-trimethylsilane 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以95%的产率得到(E)-3,4-Bis{[(tert-butyl)dimethylsilyloxy]methyl}-1-(4-nitrophenyl)-6-(trimethylsilyl)hex-3-ene-1,5-diyne
  参考文献：
  名称：

  Synthesis and Physical Investigation of Donor–Donor and Acceptor–Acceptor End-Functionalized Monodisperse Poly(triacetylene) Oligomers

  摘要：

  Two series of monodisperse, terminally donor-donor [D-D, D=4-(dimethylamino)phenyl] and acceptor-acceptor [A-A, A=4-nitrophenyl] functionalized poly(triacetylene) (PTA) oligomers ranging from monomer to hexamer were synthesized by oxidative Hay oligomerization under end-capping conditions. The corresponding D-D and A-A end-substituted polymers with an average degree of polymerization (DP) of n approximate to 18 and n approximate to 12, respectively, were also prepared and served as reference points for the corresponding infinitely long polymers. These terminally functionalized PTA oligomers and polymers are yellow- to orange-colored compounds, displaying excellent solubility in aprotic solvents with melting points above 200 degreesC for the hexamers. For the 4-(dimethylamino)phenyl substituted compounds, a consistent first oxidation potential around + 0.42 V versus Fc/Fc(+) (ferrocene/ferricinium) was observed, whereas the 4-nitrophenyl functionalized systems underwent a reversible reductive two-electron transfer around -1.40 V versus Fc/Fc(+). The nature of the end-groups has a dramatic influence on the electronic absorption spectra. Saturation of the linear optical properties in the D-D series occurs at significantly shorter chain-length [effective conjugation length (ECL) of n approximate to 4 monomer units] than in the A-A substituted or the previously reported Me3Si- and Et3Si-end-capped PTA oligomer series (ECL: n approximate to 10 monomer units). Similar observations with respect to the ECL were made by measurement of the Raman-active <()over tilde>((C=C)) stretches. Third-harmonic generation (THG) and degenerate four-wave mixing (DFWM) experiments showed that shorter oligomers of terminally D-D or A-A functionalized PTAs display higher second hyperpolarizabilities gamma than the corresponding R3Si-end-capped series (R=alkyl), Moreover, they disclose a distinct peak of the nonlinearity per monomer unit at intermediate backbone lengths. In THG experiments, the second hyperpolarizabilities for long D/A-functionalized PTA oligomers attained the same saturation values as observed for the corresponding R3Si-end-capped rods. The nonlinearities measured by DFWM of the D-D and A-A substituted PTAs were found to be larger than for the silylated ones, which can be explained by the closeness of the two-photon resonance.

  DOI：

  10.1002/1521-3765(20001201)6:23<4400::aid-chem4400>3.0.co;2-a

文献信息

• Synthesis and Physical Investigation of Donor–Donor and Acceptor–Acceptor End-Functionalized Monodisperse Poly(triacetylene) Oligomers
  作者：Rainer E. Martin、Ulrich Gubler、Corinne Boudon、Christian Bosshard、Jean-Paul Gisselbrecht、Peter Günter、Maurice Gross、François Diederich

  DOI：10.1002/1521-3765(20001201)6:23<4400::aid-chem4400>3.0.co;2-a

  日期：2000.12.1

  Two series of monodisperse, terminally donor-donor [D-D, D=4-(dimethylamino)phenyl] and acceptor-acceptor [A-A, A=4-nitrophenyl] functionalized poly(triacetylene) (PTA) oligomers ranging from monomer to hexamer were synthesized by oxidative Hay oligomerization under end-capping conditions. The corresponding D-D and A-A end-substituted polymers with an average degree of polymerization (DP) of n approximate to 18 and n approximate to 12, respectively, were also prepared and served as reference points for the corresponding infinitely long polymers. These terminally functionalized PTA oligomers and polymers are yellow- to orange-colored compounds, displaying excellent solubility in aprotic solvents with melting points above 200 degreesC for the hexamers. For the 4-(dimethylamino)phenyl substituted compounds, a consistent first oxidation potential around + 0.42 V versus Fc/Fc(+) (ferrocene/ferricinium) was observed, whereas the 4-nitrophenyl functionalized systems underwent a reversible reductive two-electron transfer around -1.40 V versus Fc/Fc(+). The nature of the end-groups has a dramatic influence on the electronic absorption spectra. Saturation of the linear optical properties in the D-D series occurs at significantly shorter chain-length [effective conjugation length (ECL) of n approximate to 4 monomer units] than in the A-A substituted or the previously reported Me3Si- and Et3Si-end-capped PTA oligomer series (ECL: n approximate to 10 monomer units). Similar observations with respect to the ECL were made by measurement of the Raman-active <()over tilde>((C=C)) stretches. Third-harmonic generation (THG) and degenerate four-wave mixing (DFWM) experiments showed that shorter oligomers of terminally D-D or A-A functionalized PTAs display higher second hyperpolarizabilities gamma than the corresponding R3Si-end-capped series (R=alkyl), Moreover, they disclose a distinct peak of the nonlinearity per monomer unit at intermediate backbone lengths. In THG experiments, the second hyperpolarizabilities for long D/A-functionalized PTA oligomers attained the same saturation values as observed for the corresponding R3Si-end-capped rods. The nonlinearities measured by DFWM of the D-D and A-A substituted PTAs were found to be larger than for the silylated ones, which can be explained by the closeness of the two-photon resonance.