4,5-bis[(2-cyanoethyl)thio]-3,6-diethylphthalonitrile | 735277-19-7

• 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: 4,5-bis[(2-cyanoethyl)thio]-3,6-diethylphthalonitrile
• 英文别名: 4,5-bis(2-cyanoethylthio)-3,6-diethylphthalonitrile；4,5-Bis(2-cyanoethylsulfanyl)-3,6-diethylbenzene-1,2-dicarbonitrile
• CAS: 735277-19-7
• 化学式: C₁₈H₁₈N₄S₂
• 分子量: 354.5
• InChiKey: AMYKXRAAPPGDQW-UHFFFAOYSA-N

物化性质

• 熔点：
  65-67 °C
• 沸点：
  540.4±50.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  146
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,5-bis[(2-cyanoethyl)thio]-3,6-diethylphthalonitrile 在 cesium hydroxide 、 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 14.0h， 以13%的产率得到5,6-dicyano-4,7-diethylbenzo[1,2,3]trithiole
  参考文献：
  名称：

  Preparation of Phthalocyanines with Eight Benzylchalcogeno Substituents from 5,6-Dibromo-4,7-diethylbenzo[1,2,3]trichalcogenoles

  摘要：

  Benzo[1,2,3]trichalcogenoles with two bromine atoms on the benzene ring, 5,6-dibromo-4,7-diethylbenzo[1,2,3]trichalcogenoles (1a) and (1b) (chalcogen: 1a = S; 1b = Se), were first prepared by treating 2,3,5,6-tetrabromo-1,4-diethylbenzene (TBDEB) with elemental sulfur or amorphous selenium in DBU at 140 degreesC (for 1a) and 100 degreesC (for 1b) for 24 h. The structures of 1a and 1b were verified by NMR spectroscopy, mass spectrometry, and elemental analysis. X-ray crystallographic analysis ultimately showed that the substitution reactions of TBDEB proceeded at the two adjacent bromine atoms. To apply 1a and 1b to construction of phthalocyanine derivatives with sulfur or selenium functional groups, 4,5-bis(benzylchalcogeno)-3,6-diethylphthalonitriles (5a) and (5b) as key intermediates were prepared by way of introduction of alkyl groups (2-cyanoethyl or 4-nitrophenethyl groups) on two chalcogen atoms, substitution of two bromine atoms with nitrile groups, and subsequent exchange of alkyl groups with benzyl groups. Compound 5a was treated with lithium in n-pentanol at 100 degreesC for 1 h to produce 2,3,9,10,16,17,23,24-octakis(benzylthio)1,4,8,11,15,18,22,25-octaethylphthalocyanine (6a). A similar treatment of 5b in n-hexanol at 100 degreesC for 2 h gave phthalocyanine 6b. The structures of 6a and 6b were determined by H-1 NMR spectroscopy and MALDI-TOFMS. X-ray crystallographic analysis of 6a was also performed. The Q-band absorptions (lambda(max)) for 6a and 6b in UV-vis spectra were observed at 755 nm (log epsilon = 5.1) and 757 nm (log epsilon = 5.1), respectively, and their electrochemical properties were verified by cyclic voltammetry in dichloromethane with Ag/AgNO3 as a reference electrode. Compounds 6a and 6b were further treated with lithium in THF/NH3 at -78 degreesC and then with dibutyltin dichloride to produce phthalocyanine derivatives 8a and 8b with four dichalcogenastannole rings by way of octachalcogenate phthalocyanines 7a and 7b.

  DOI：

  10.1021/jo030354j
• 作为产物：
  描述：

  1,2,4,5-tetrabromo-3,6-diethylbenzene 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 sodium tetrahydroborate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 41.5h， 生成 4,5-bis[(2-cyanoethyl)thio]-3,6-diethylphthalonitrile
  参考文献：
  名称：

  Preparation of Phthalocyanines with Eight Benzylchalcogeno Substituents from 5,6-Dibromo-4,7-diethylbenzo[1,2,3]trichalcogenoles

  摘要：

  Benzo[1,2,3]trichalcogenoles with two bromine atoms on the benzene ring, 5,6-dibromo-4,7-diethylbenzo[1,2,3]trichalcogenoles (1a) and (1b) (chalcogen: 1a = S; 1b = Se), were first prepared by treating 2,3,5,6-tetrabromo-1,4-diethylbenzene (TBDEB) with elemental sulfur or amorphous selenium in DBU at 140 degreesC (for 1a) and 100 degreesC (for 1b) for 24 h. The structures of 1a and 1b were verified by NMR spectroscopy, mass spectrometry, and elemental analysis. X-ray crystallographic analysis ultimately showed that the substitution reactions of TBDEB proceeded at the two adjacent bromine atoms. To apply 1a and 1b to construction of phthalocyanine derivatives with sulfur or selenium functional groups, 4,5-bis(benzylchalcogeno)-3,6-diethylphthalonitriles (5a) and (5b) as key intermediates were prepared by way of introduction of alkyl groups (2-cyanoethyl or 4-nitrophenethyl groups) on two chalcogen atoms, substitution of two bromine atoms with nitrile groups, and subsequent exchange of alkyl groups with benzyl groups. Compound 5a was treated with lithium in n-pentanol at 100 degreesC for 1 h to produce 2,3,9,10,16,17,23,24-octakis(benzylthio)1,4,8,11,15,18,22,25-octaethylphthalocyanine (6a). A similar treatment of 5b in n-hexanol at 100 degreesC for 2 h gave phthalocyanine 6b. The structures of 6a and 6b were determined by H-1 NMR spectroscopy and MALDI-TOFMS. X-ray crystallographic analysis of 6a was also performed. The Q-band absorptions (lambda(max)) for 6a and 6b in UV-vis spectra were observed at 755 nm (log epsilon = 5.1) and 757 nm (log epsilon = 5.1), respectively, and their electrochemical properties were verified by cyclic voltammetry in dichloromethane with Ag/AgNO3 as a reference electrode. Compounds 6a and 6b were further treated with lithium in THF/NH3 at -78 degreesC and then with dibutyltin dichloride to produce phthalocyanine derivatives 8a and 8b with four dichalcogenastannole rings by way of octachalcogenate phthalocyanines 7a and 7b.

  DOI：

  10.1021/jo030354j

文献信息

• Preparation, Structure Determination, and Electrochemical Properties of Bis{[1,4,8,11, 15,18,22,25-octaethyl-2,3,9,10,16,17,23,24-octakis(methylthio)phthalocyaninato]titanium(IV)} Benzene-1,2,4,5-tetrathiolate
  作者：Takeshi Kimura、Jun Kumasaka、Toshiharu Namauo

  DOI：10.1002/ejoc.200800502

  日期：2008.10

  introduced into thephthalocyanine 3 by treatment with titanium(IV) tetrabutoxide in DMF at 130 °C to give the corresponding metal complex 3-TiO. Linking of two molecules of the phthalocyanine 3-TiO with benzene-1,2,4,5-tetrathiol (BTT) produced a double-decker-type compound, bis[octaethyl-octakis(methylthio)phthalocyaninato]titanium(IV)} benzenetetrathiolate (6), in which the two phthalocyanines are

  4,5-双（甲硫基）邻苯二甲腈 2 由 2,3,5,6-四溴二乙苯分四步制备。邻苯二甲腈 2 与正五氧化锂在 115 °C 下进行四聚和环化，生成八乙基八（甲硫基）酞菁 (3)。通过在 DMF 中在 130°C 下用四丁醇钛 (IV) 处理将钛原子引入到酞菁 3 中，得到相应的金属配合物 3-TiO。酞菁 3-TiO 的两个分子与苯-1,2,4,5-四硫醇 (BTT) 连接产生双层型化合物双[八乙基-八(甲硫基)酞菁]钛(IV)}苯四硫醇盐 (6)，其中两个酞菁通过四个钛硫配位键轴向连接。双层衍生物 7 也通过用 BTT 对（四叔丁基酞菁）氧化钛（IV）进行类似处理而获得。6和7的结构由NMR、IR、UV/Vis光谱和FAB质谱确定。如1H和13C NMR谱所示，6的两个酞菁骨架均具有对称结构。6 的电化学性质通过循环伏安法检测，以 Ag/AgNO3 作为参比电极。 (© Wiley-VCH
• Preparation of Phthalocyanines with Eight Benzylchalcogeno Substituents from 5,6-Dibromo-4,7-diethylbenzo[1,2,3]trichalcogenoles
  作者：Takeshi Kimura、Akinori Yomogita、Tomoya Matsutani、Takahiro Suzuki、Ichiro Tanaka、Yasushi Kawai、Yutaka Takaguchi、Takatsugu Wakahara、Takeshi Akasaka

  DOI：10.1021/jo030354j

  日期：2004.7.1

  Benzo[1,2,3]trichalcogenoles with two bromine atoms on the benzene ring, 5,6-dibromo-4,7-diethylbenzo[1,2,3]trichalcogenoles (1a) and (1b) (chalcogen: 1a = S; 1b = Se), were first prepared by treating 2,3,5,6-tetrabromo-1,4-diethylbenzene (TBDEB) with elemental sulfur or amorphous selenium in DBU at 140 degreesC (for 1a) and 100 degreesC (for 1b) for 24 h. The structures of 1a and 1b were verified by NMR spectroscopy, mass spectrometry, and elemental analysis. X-ray crystallographic analysis ultimately showed that the substitution reactions of TBDEB proceeded at the two adjacent bromine atoms. To apply 1a and 1b to construction of phthalocyanine derivatives with sulfur or selenium functional groups, 4,5-bis(benzylchalcogeno)-3,6-diethylphthalonitriles (5a) and (5b) as key intermediates were prepared by way of introduction of alkyl groups (2-cyanoethyl or 4-nitrophenethyl groups) on two chalcogen atoms, substitution of two bromine atoms with nitrile groups, and subsequent exchange of alkyl groups with benzyl groups. Compound 5a was treated with lithium in n-pentanol at 100 degreesC for 1 h to produce 2,3,9,10,16,17,23,24-octakis(benzylthio)1,4,8,11,15,18,22,25-octaethylphthalocyanine (6a). A similar treatment of 5b in n-hexanol at 100 degreesC for 2 h gave phthalocyanine 6b. The structures of 6a and 6b were determined by H-1 NMR spectroscopy and MALDI-TOFMS. X-ray crystallographic analysis of 6a was also performed. The Q-band absorptions (lambda(max)) for 6a and 6b in UV-vis spectra were observed at 755 nm (log epsilon = 5.1) and 757 nm (log epsilon = 5.1), respectively, and their electrochemical properties were verified by cyclic voltammetry in dichloromethane with Ag/AgNO3 as a reference electrode. Compounds 6a and 6b were further treated with lithium in THF/NH3 at -78 degreesC and then with dibutyltin dichloride to produce phthalocyanine derivatives 8a and 8b with four dichalcogenastannole rings by way of octachalcogenate phthalocyanines 7a and 7b.