cyclohepta-1′,3′,5′-trien-1′-ylmethyl-phosphonate diethyl ester | 267900-02-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: cyclohepta-1′,3′,5′-trien-1′-ylmethyl-phosphonate diethyl ester
• 英文别名: (cyclohepta-1,3,5-trien-1-ylmethyl)diethylphosphonate；(cyclohepta-1,3,5-trienyl-1-methyl)diethylphosphonate；1-(diethoxyphosphorylmethyl)cyclohepta-1,3,5-triene
• CAS: 267900-02-7
• 化学式: C₁₂H₁₉O₃P
• 分子量: 242.255
• InChiKey: DNQHUMMTQSCUOH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  [{(4-CH3C6H4)4CBD}CoCpCHO] 、 cyclohepta-1′,3′,5′-trien-1′-ylmethyl-phosphonate diethyl ester 在 四丁基溴化铵 、 sodium hydroxide 作用下， 以 水 、 苯 为溶剂， 反应 6.0h， 以67.4%的产率得到(E)-1-[(tetra-p-tolyl-η⁴-cyclobutadiene)(η⁵-cyclopentadienediyl)-cobalt(I)]-2-(cyclohepta-1′,3′,5′-trien-1′-yl)ethene
  参考文献：
  名称：

  偶极Sesquifulvalene化合物与（四芳-η 4 -cyclobutadiene）（η 5 - cyclopentadienediyl）钴（I）配合物的单位作为电子供体

  摘要：

  钴及其乙烯基衍生物的单核单氢七氟戊烯络合物[（Ar 4 CBD）Co（Cp-ZC 7 H 7）]（Ar 4 CBD = C 4 Ar 4 ; Ar = p -XC 6 H 4 ; X = H，Z = –（4）; X = H，−C 2 H 2 –（9a）; X = Cl，Z = −C 2 H 2 –（9b）; X = Me，Z = −C 2 H 2 –（9c））; X = OMe，Z = -C 2 H 2 –（9d）; X = NMe2，Z = -C 2 H 2 –（9e）；X = H，Z =-（C 2 H 2）2 –（10）；合成X = H，Z =-（C 2 H 2）3 –（11）），并通过氢化物提取将其转化为[（Ar 4 CBD）Co（Cp-ZC 7 H 6）] +的相应偶极倍半富烯配合物（Ar 4 CBD = C 4 Ar 4； Ar = p -XC 6 H 4； X = H，Z = –（5）;

  DOI：

  10.1021/om300710x

文献信息

• Second Harmonic Generation and Two-Photon Fluorescence as Nonlinear Optical Properties of Dipolar Mononuclear Sesquifulvalene Complexes
  作者：Hans Wong、Timo Meyer-Friedrichsen、Tony Farrell、Christoph Mecker、Jürgen Heck

  DOI：10.1002/(sici)1099-0682(200004)2000:4<631::aid-ejic631>3.0.co;2-e

  日期：2000.4

  reduction is localised on the tropylium entity. In the electronic absorption spectra two intense bands are observed in the region 400 < λ < 900 nm which undergo strong negative solvatochromic shifts. The origin of the high-energy absorption band is assumed to be an interligand charge-transfer (LL–CT) transition, and the low-energy absorption band is assigned to a donor-acceptor charge-transfer (DA–CT) transition

  为了研究非线性光学性质，特别是有机金属配合物的二次谐波产生 (SHG)，已经合成了许多一般形式 [Mc-Z- ]+ 的偶极单阳离子倍半富瓦烯配合物（Mc = 金属茂基），其中金属茂基部分Mc 作为电子供体，Tropylium 阳离子 C7H6+ 作为电子受体。供体和受体基团的相互电子影响由连接间隔物 Z 保证，它是一个单键 [Mc = CpFeC5H4 (4a); Mc = CpRuC5H4 (4b)]，包含烯烃的不饱和桥 [Z = (E-CHCH)n: n = 1, Mc = CpFeC5H4 (25a), Mc = CpRuC5H4 (25b); n = 2，Mc = CpFeC5H4 (26)；n = 3，Mc = CpFeC5H4 (27)]，或噻吩单元 [Z = 2,5-C4H2S，Mc = CpFeC5H4 (28)；Z = 5,5'-(2,2'- )2，Mc =
• Vinylogue Mono‐ and Bimetallic Cationic Sesquifulvalene and Monohydro Sesquifulvalene Complexes for Second Harmonic Generation
  作者：Timo Meyer‐Friedrichsen、Hans Wong、Marc H. Prosenc、Jürgen Heck

  DOI：10.1002/ejic.200390125

  日期：2003.3

  of the mono- and dicationic complexes 3a−6b. The β values obtained for the cationic sesquifulvalene complexes 4−6b are among the largest ever measured for ruthenocenyl containing complexes due to a strong resonance enhancement: the sesquifulvalene complexes 4−6a, 6b show first hyperpolarisabilities which range between 360 and 700 × 10−30 esu, whereas β for the monohydrosesquifulvalene complexes are considerably

  [(η5-C5H5)Ruµ-(η5-C5H4)C2H2(η6-C7H7)}ML](PF6)n [n = 0: ML] = 无 (1), Cr(CO)3 (2); n = 1: ML = Ru(η5- ) (3a), Ru(η5-C5Me5) (3b)] 和 [(η5- )Ruµ-(η5- ) (η7-C7H6)}ML ](PF6)n [n = 1: ML = 无 (4), Cr(CO)3 (5); n = 2：ML = Ru(η5- ) (6a)、Ru(η5-C5Me5) (6b)] 分别已合成，并在光谱和结构上进行了表征。通过 1 H NMR 光谱研究进行了电荷转移相关性研究，发现基态供体-受体相互作用增加，顺序为 5 < 6b < 4 < 6a。3a 和 3b 中相应的供体-受体相互作用变化不大。应用超瑞利散射 (HRS) 来确定单和双阳离子复合物 3a-6b
• Cellulose-Based Polymers with Long-Chain Pendant Ferrocene Derivatives as Organometallic Chromophores
  作者：Fan Zhang、Volkmar Vill、Jürgen Heck

  DOI：10.1021/om0343216

  日期：2004.8.1

  Selective transmetalation reactions via 1,1'-distannylated ferrocene enables the synthesis of the new ferrocenyl chromophore [Fe(eta(5)-C5H4-CH2OH)(eta(5)-C5H4-CH=CH-C7H7)] (6). Coupling reactions of complex 6 with corresponding alkyl halides reveal the sandwich compounds [Fe(eta(5)-C5H4-CH2OCH3)(eta(5)-C5H4-CH=CH-C7H7)] (7), [Feeta(5)-C5H4-CH2O(CH2)(6)Br}(eta(5)-C5H4-CH=CH-C7H7)] (8), [Feeta(5)-C5H4-CH2O(CH2)(6)OTHP}(eta(5)-C5H4-CH=CH-C7H7)] (9) (THP = tetrahydropyranyl), and [Feeta(5)-C5H4-CH2O(CH2)(6)I}(eta(5)-C5H4-CH=CH-C7H7)] (10), which are potential precursors for dipolar donor-acceptor complexes, providing nonlinear optical properties. The synthesis of the THP derivative 9 was intended as a precursor for the hydroxy-terminated compound [Feeta(5)-C5H4-CH2O(CH2)(6)OH}(eta(5)-C5H4-CH=CH-C7H7)] (11), which would be a suitable starting material for a coupling reaction with modified cellulose. However, an acid-catalyzed cleavage of the THP group of 9 in ethanol solution resulted in the formation of [Fe(eta(5)-C5H4-CH2OCH2CH3)(eta(5)-C5H4-CH=CH-C7H7)] (12) instead of 11. The fixation of ferrocenyl chromophores to 2,3-di-O-methyl cellulose was successful by using the ferrocenyl derivative 10, which reveals 2,3-di-O-methyl-6-O-partially[Feeta(5)-C5H4-CH2O(CH2)(6)}(eta(5)-C5H4-CH=CH-C7H7)] cellulose (18) with different DS [0.1 (18a), 0.2 (18b), 0.3 (18c), 0.5 (18d), 0.6(18e)], depending on the reaction conditions. 1.8a-e were characterized by H-1 NMR, H-1-C-13 correlation spectroscopy, UV/vis spectra, and cyclic voltammetry (18c). Polarization microscopy observations of the cellulose derivative 18c demonstrate its thermotropic and lyotropic liquid crystallinities. Reaction of 12 with [Cp*Ru(CH3CN)(3)]PF6 forms the dipolar monohydro sesquifulvalene complex [Fe(eta(5)-C5H4-CH2OC2H5)eta(5) -C5H4-CH= CH-(eta(6)-C7H7)}RuCp*]PF6 (13), indicating that the ferrocenyl derivatives 7-10 can in principle be transformed to dinuclear, dipolar, monocationic, monohydro sesquifulvalene complexes and opens the feasibility of introducing dinuclear and dipolar sesquifulvalene units as pendant units of a cellulose backbone, which have potential nonlinear optical properties.