4,5-bis(benzylthio)-3,6-diethylphthalonitrile | 735277-20-0

• 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: 4,5-bis(benzylthio)-3,6-diethylphthalonitrile
• 英文别名: 4,5-di(benzylthio)-3,6-diethylphthalonitrile；4,5-Bis(benzylsulfanyl)-3,6-diethylbenzene-1,2-dicarbonitrile
• CAS: 735277-20-0
• 化学式: C₂₆H₂₄N₂S₂
• 分子量: 428.622
• InChiKey: QUJIRNTUWGCWIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  98.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,5-bis(benzylthio)-3,6-diethylphthalonitrile 在 lithium 作用下， 以 戊醇 为溶剂， 反应 1.0h， 以39%的产率得到1,4,8,11,15,18,22,25-octaethyl-2,3,9,10,16,17,23,24-(benzylthio)phthalocyanine
  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-bis(2-cyanoethylthio)-3,6-diethyl-4,5-dibromobenzene 在 cesium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 29.0h， 生成 4,5-bis(benzylthio)-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
• 作为试剂：
  描述：

  4,5-dibutoxyphthalonitrile 在 lithium 、 4,5-bis(benzylthio)-3,6-diethylphthalonitrile 作用下， 以 戊醇 为溶剂， 反应 0.92h， 以63%的产率得到2,3,9,10,16,17,23,24-octabutoxyphthalocyanine
  参考文献：
  名称：

  Preparation of Unsymmetric Phthalocyanines with Benzylchalcogeno and Butoxy Groups

  摘要：

  A mixture of 4,5-dibenzylchalcogeno-3,6-diethylphthalonitrile and 4,5-dibutoxyphthalonitrile was treated with lithium in n-pentanol at 110 degrees C to give unsymmetric phthalocyanines. Optical and electrochemical properties of them were examined by UV-vis spectroscopy and cyclic voltammetry.

  DOI：

  10.3987/com-08-s(f)63

文献信息

• Preparation and optical and electrochemical properties of octaethylphthalocyanines fused with several tetrathiafulvalene units
  作者：Takeshi Kimura、Dai Watanabe、Toshiharu Namauo

  DOI：10.1002/hc.20694

  日期：2011.9

  3,6-Diethylphthalonitrile (3) with a tetrathiafulvalene (TTF) unit at 4,5-positions was prepared from 4,5-xylylenedithio-3,6-diethylphthalonitrile (1a) via elimination of the xylylene group, connection of a carbonyl group to benzenedithiolate generated, and condensation of 4,5-bis(methylthio)-1,3-dithiole-2-thione with benzo-1,3-dithiole-2-one (2-O) produced. A 1:1 mixture of phthalonitrile (3) and

  在 4,5-位具有四硫富瓦烯 (TTF) 单元的 3,6-二乙基邻苯二甲腈 (3) 是由 4,5-二甲苯二硫基-3,6-二乙基邻苯二甲腈 (1a) 通过消除二甲苯基团、连接羰基而制备的生成苯二硫醇，并生成 4,5-双(甲硫基)-1,3-二硫醇-2-硫酮与苯并-1,3-二硫醇-2-酮 (2-O) 的缩合反应。邻苯二甲腈 (3) 和 4,5-双(苄硫基)-3,6-二乙基邻苯二甲腈 (1b) 的 1:1 混合物在 120°C 下用锂在正己醇中处理，生成六（苄硫基）单（四硫富瓦烯）酞菁 (5)、四(苄硫基)双(四硫富瓦烯)酞菁(6)和双(苄硫基)三(四硫富瓦烯)酞菁(7)。5、6和7的结构通过1H NMR、FAB MS、MALDI-TOF MS（基质辅助激光解吸电离飞行时间质谱）确定，和紫外-可见光谱。化合物6是反式和顺式异构体（6-反式和6-顺式）的混合物。通过添加三氟乙酸 (TFA)，在氯仿中测量的
• 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.
• Preparation of Unsymmetric Phthalocyanines with Benzylchalcogeno and Butoxy Groups
  作者：Takeshi Kimura、Takeru Obonai、Toshiharu Namauo

  DOI：10.3987/com-08-s(f)63

  日期：——

  A mixture of 4,5-dibenzylchalcogeno-3,6-diethylphthalonitrile and 4,5-dibutoxyphthalonitrile was treated with lithium in n-pentanol at 110 degrees C to give unsymmetric phthalocyanines. Optical and electrochemical properties of them were examined by UV-vis spectroscopy and cyclic voltammetry.