1,2-bis(2-cyanoethylthio)-3,6-diethyl-4,5-dibromobenzene | 735277-18-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1,2-bis(2-cyanoethylthio)-3,6-diethyl-4,5-dibromobenzene
• 英文别名: 3-[4,5-Dibromo-2-(2-cyanoethylsulfanyl)-3,6-diethylphenyl]sulfanylpropanenitrile
• CAS: 735277-18-6
• 化学式: C₁₆H₁₈Br₂N₂S₂
• 分子量: 462.272
• InChiKey: CZQOPFDWFJCPIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  1,2-bis(2-cyanoethylthio)-3,6-diethyl-4,5-dibromobenzene 在 cesium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成
  参考文献：
  名称：

  酞菁和卟啉钛 (IV) 苯二硫醇盐的制备

  摘要：

  摘要 八丁氧基酞菁氧化钛 (IV) (4) 和四苯基卟啉氧化钛 (IV) (6) 与二乙基苯二硫醇 (3a) 或二乙基苯二硒醇 (3b) 反应生成相应的钛 (IV) 配合物 (5) 和 (7a,b)具有钛-硫或钛-硒键。产物的光学和电化学性质通过紫外-可见（UV-Vis）光谱和循环伏安法测定。

  DOI：

  10.1080/10426507.2010.520280
• 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 为溶剂， 反应 36.5h， 生成 1,2-bis(2-cyanoethylthio)-3,6-diethyl-4,5-dibromobenzene
  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 of Octakis (methylthio)octaethylphthalocyaninato Titanium (IV) Benzenedichalcogenolates
  作者：Takeshi Kimura、Arata Yamamoto、Toshiharu Namauo

  DOI：10.1080/10426501003772144

  日期：2010.5.27

  Octakis(methylthio)octaethylphthalocyaninato titanium (IV) oxide (PcSMeTiO) was prepared from octakis(methylthio)octaethylphthalocyanine (PcSMe) upon treatment with titanium (IV) tetrabutoxide in DMF at 130 degrees C. The reaction of PcSMeTiO with benzenedithiol or benzenediselenol produced octakis(methylthio)octaethylphthalocyaninato titanium (IV) benzenedichalcogenolates (4a,b) bearing titanium-sulfur or titanium-selenium bonds.
• Preparation and Electrochemical Properties of Phthalocyaninato Titanium (IV) and Porphyrinato Titanium (IV) Benzenedichalcogenolates
  作者：Takeshi Kimura、Kaori Amano、Arata Yamamoto、Toshiharu Namauo

  DOI：10.3987/com-10-s(e)64

  日期：——

  The reaction of phthalocyaninato titanium(IV) oxides with benzenedithiol or benzenediselenol produced the corresponding complexes with titanium-sulfur or titanium-selenium bonds. Tetraphenylporphyrinato titanium (IV) benzenedichalcogenolates were obtained by the similar procedure. Their optical and electrochemical properties were determined by UV-vis spectroscopy and cyclic voltammetry.
• Preparation of Phthalocyaninato and Porphyrinato Titanium (IV) Benzenedichalcogenolates
  作者：Takeshi Kimura、Kaori Amano、Toshiharu Namauo

  DOI：10.1080/10426507.2010.520280

  日期：2011.5.1

  Abstract The reaction of octabutoxyphthalocyaninato titanium (IV) oxide (4) and tetraphenylporphyrinato titanium (IV) oxide (6) with diethylbenzenedithiol (3a) or diethylbenzenediselenol (3b) produced the corresponding titanium (IV) complexes (5) and (7a,b) with titanium–sulfur or titanium–selenium bonds. Optical and electrochemical properties of the products were determined by ultraviolet-visible

  摘要 八丁氧基酞菁氧化钛 (IV) (4) 和四苯基卟啉氧化钛 (IV) (6) 与二乙基苯二硫醇 (3a) 或二乙基苯二硒醇 (3b) 反应生成相应的钛 (IV) 配合物 (5) 和 (7a,b)具有钛-硫或钛-硒键。产物的光学和电化学性质通过紫外-可见（UV-Vis）光谱和循环伏安法测定。
• 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.