(E)-3,4-Bis{[(tert-butyl)dimethylsilyloxy]methyl}-1-(4-nitrophenyl)hex-3-ene-1,5-diyne | 326500-37-2

• 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)hex-3-ene-1,5-diyne
• 英文别名: tert-butyl-[(E)-3-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-ethynyl-5-(4-nitrophenyl)pent-2-en-4-ynoxy]-dimethylsilane
• CAS: 326500-37-2
• 化学式: C₂₆H₃₉NO₄Si₂
• 分子量: 485.771
• InChiKey: SXAUIHFTIOLYTN-GHVJWSGMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.92
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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)hex-3-ene-1,5-diyne 、 [6-((1S,2R,4S)-1-Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)-hexyl]-(4-iodo-phenyl)-methyl-amine 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 反应 24.0h， 以60%的产率得到[6-((1S,2R,4S)-1-Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)-hexyl]-{4-[(E)-3,4-bis-(tert-butyl-dimethyl-silanyloxymethyl)-6-(4-nitro-phenyl)-hex-3-ene-1,5-diynyl]-phenyl}-methyl-amine
  参考文献：
  名称：

  Synthesis and properties of a ROMP backbone polymer with efficient, laterally appended nonlinear optical chromophores

  摘要：

  The synthesis and properties of a new ROMP backbone polymer bearing lateral donor - acceptor- substituted (E)-diethynylethene (( E)-hex-3-ene-1,5-diyne) chromophores are described. The polymer with an average of 40 monomeric repeat units is readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane and chloroform. Good optical-quality films were obtained by spin coating. The third-order susceptibility chi((3)) at a wavelength of 1907 nm was determined to be 100 times greater than that of fused silica. After electrical poling, the polymer also showed a significant second-order nonlinear optical coefficient (d(33)) value, which decays by a factor of two over a period of one month at room temperature.

  DOI：

  10.1039/b314789d
• 作为产物：
  描述：

  [(E)-3,4-bis[[tert-butyl(dimethyl)silyl]oxymethyl]hex-3-en-1,5-diynyl]-trimethylsilane 在 bis-triphenylphosphine-palladium(II) chloride 甲醇 、 copper(l) iodide 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 (E)-3,4-Bis{[(tert-butyl)dimethylsilyloxy]methyl}-1-(4-nitrophenyl)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 properties of a ROMP backbone polymer with efficient, laterally appended nonlinear optical chromophores
  作者：Jean-Manuel Raimundo、Steve Lecomte、Michael J. Edelmann、Simona Concilio、Ivan Biaggio、Christian Bosshard、Peter Günter、François Diederich

  DOI：10.1039/b314789d

  日期：——

  The synthesis and properties of a new ROMP backbone polymer bearing lateral donor - acceptor- substituted (E)-diethynylethene (( E)-hex-3-ene-1,5-diyne) chromophores are described. The polymer with an average of 40 monomeric repeat units is readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane and chloroform. Good optical-quality films were obtained by spin coating. The third-order susceptibility chi((3)) at a wavelength of 1907 nm was determined to be 100 times greater than that of fused silica. After electrical poling, the polymer also showed a significant second-order nonlinear optical coefficient (d(33)) value, which decays by a factor of two over a period of one month at room temperature.
• 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.