p-Methoxy-phenyl-hexatriin | 38177-92-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: p-Methoxy-phenyl-hexatriin
• 英文别名: 1-Hexa-1,3,5-triynyl-4-methoxybenzene
• CAS: 38177-92-3
• 化学式: C₁₃H₈O
• 分子量: 180.206
• InChiKey: OQWHSXNDTOSFDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  p-Methoxy-phenyl-hexatriin 在 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 various solvents 为溶剂， 反应 1.0h， 以50.2 mg的产率得到1,12-bis(4-methoxy-phenyl)dodeca-1,3,5,7,9,11-hexayne
  参考文献：
  名称：

  Synthesis, Structure, and Nonlinear Optical Properties of Diarylpolyynes

  摘要：

  A series of alpha,omega-diarylpolyynes has been synthesized. In addition to the synthesis of three hexaynes (3a-c), a notably improved synthesis of 1,16-diphenylhexadecaoctayne (5) is described. The third-order nonlinear optical characteristics for these molecules have been studied and show a substantial increase in molecular hyperpolarizability (gamma) as a function of increasing length. The unusual solid-state structures of compounds 3a and 3b are reported.

  DOI：

  10.1021/ol047931q
• 作为产物：
  描述：

  p-Methoxyphenyl-trimethylsilyl-butadiin-keton 在 正丁基锂 、 potassium carbonate 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 p-Methoxy-phenyl-hexatriin
  参考文献：
  名称：

  Synthesis, Structure, and Nonlinear Optical Properties of Diarylpolyynes

  摘要：

  A series of alpha,omega-diarylpolyynes has been synthesized. In addition to the synthesis of three hexaynes (3a-c), a notably improved synthesis of 1,16-diphenylhexadecaoctayne (5) is described. The third-order nonlinear optical characteristics for these molecules have been studied and show a substantial increase in molecular hyperpolarizability (gamma) as a function of increasing length. The unusual solid-state structures of compounds 3a and 3b are reported.

  DOI：

  10.1021/ol047931q

文献信息

• Silylation as a protective method in Cadiot-Chodkiewicz couplings
  作者：R. Eastmond、D.R.M. Walton

  DOI：10.1016/0040-4020(72)80040-1

  日期：1972.1

  Other XC6H4(CC)nGeEt3 compounds (n = 2,3; excluding X = NO2) were also prepared by the Grignard method. Couplings between phenylacetylene and the reagents, BrCCSiMe3(V), and ICCSiR3 (R = Me, Et) give the appropriate silylated phenylbutadiynes in poor yield because of symmetrical oxidative coupling (iodo compounds) or of base-sensitivity of the trimethylsilyl-acetylene bonds.

  Cadiot-Chodkiewicz arylacetylenes的联接器（I），XC 6 H ^ 4 CCH（X = H;米-Br，-Me; p -F，-NO 2，-OMe）与溴乙炔基（三乙基）硅烷（II）， BrCCSiEt 3，得到甲硅烷基化二炔，XC 6 H ^ 4（CC）2 SIET 3，从该终端二炔（III），XC 6 H ^ 4 CC）2 H，通过与水性处理定量地释放甲醇碱。反过来II与III的反应生成甲硅烷基化三炔，XC 4 ħ 4 CC）3 SIET 3，用碱生成游离的芳基六炔，XC 6 H 4（CC）3 H（IV）。II，BrCCGeEt的锗类似物3，同样地夫妇I（X = H，p -NO 2），得到XC 6 H ^ 4（CC）2 GEET 3或III，得到XC 6 H ^ 4（C C）3 GeEt 3。产物（X = H）与从格氏试剂，C 6 H 5（CC）n
• Rates of base cleavage of X·C₆H₄·[CC]_n·MEt₃compounds (n= 2 and 3, M = Si and Ge), and their significance for theories of substituent effects
  作者：C. Eaborn、R. Eastmond、D. R. M. Walton

  DOI：10.1039/j29710000127

  日期：——

  The rates of cleavage of X·C6H4·[CC]n·MEt3 compounds (n= 2 and 3, M = Si and Ge) by aqueous-methanolic alkali at 29·6 °C have been measured spectrophotometrically. The ease of cleavage increases as n is raised; e.g., for the C6H5·[CC]n·SiEt3 compounds with n= 1, 2, and 3 the approximate relative rates are 1 : 240 : 4100. Germanium compounds are less reactive than the corresponding silicon compounds.The rates of cleavage of X·C6H4·[CC]3·SiEt3 compounds with X =p-OMe, H, p-F, m-Br, and p-NO2 correlate well with the simple Hammett substituent constants, σ, which normally refer to reactions involving markedly smaller distances between the substituent X and the reaction site. This casts some doubt on the validity of treatments of substituent effects which involve separation into (a) field effects which depend only on the distance between the substituent site and the reaction site, and (b) resonance effects which depend on the effectiveness of conjugation between the sites. Substituent constants calculated according to one such treatment (that by Dewar and Grisdale) are less satisfactory than σ-constants for the cleavages studied.

  采用分光光度法测量了 29·6 °C 的甲醇碱水溶液对 X·C6H4·[CC]n·MEt3 化合物（n= 2 和 3，M = Si 和 Ge）的裂解速率。随着n的增加，裂解的容易程度增加；例如，对于 n= 1、2 和 3 的 C6H5·[CC]n·SiEt3 化合物，近似相对速率为 1 : 240 : 4100。 锗化合物的反应性低于相应的硅化合物。 X 的裂解速率·C6H4·[CC]3·SiEt3 化合物，其中 X =p-OMe、H、p-F、m-Br 和 p-NO2 与简单的 Hammett 取代基常数 σ 密切相关，该常数通常指涉及之间距离明显更小的反应取代基X和反应位点。这对取代基效应处理的有效性产生了一些疑问，取代基效应涉及分为（a）场效应，仅取决于取代基位点和反应位点之间的距离，以及（b）共振效应，取决于取代基位点和反应位点之间的共轭有效性。网站。根据一种此类处理（由 Dewar 和 Grisdale 进行）计算的取代基常数不如所研究的裂解的 σ 常数令人满意。
• Regioselective Trapping of Terminal Di-, Tri-, and Tetraynes with Benzyl Azide
  作者：Thanh Luu、Robert McDonald、Rik R. Tykwinski

  DOI：10.1021/ol062522a

  日期：2006.12.1

  The reaction of benzyl azide with terminal di-, tri-, and tetraynes appended with a range of functional groups has been explored. Standard reaction conditions for BnN3 catalyzed by CuSO(4)(.)5H(2)O gave alkynyl, butadiynyl, and hexatriynyl triazoles in moderate to good yields. The reaction proceeds regioselectively as determined by the X-ray crystallographic analysis of three derivatives (1c, 1d, and 3c), and no evidence of multiple azide addition to the polyyne framework is observed.
• Synthesis, Structure, and Nonlinear Optical Properties of Diarylpolyynes
  作者：Thanh Luu、Erin Elliott、Aaron D. Slepkov、Sara Eisler、Robert McDonald、Frank A. Hegmann、Rik R. Tykwinski

  DOI：10.1021/ol047931q

  日期：2005.1.1

  A series of alpha,omega-diarylpolyynes has been synthesized. In addition to the synthesis of three hexaynes (3a-c), a notably improved synthesis of 1,16-diphenylhexadecaoctayne (5) is described. The third-order nonlinear optical characteristics for these molecules have been studied and show a substantial increase in molecular hyperpolarizability (gamma) as a function of increasing length. The unusual solid-state structures of compounds 3a and 3b are reported.