5,6-dibromo-4,7-diethylbenzo[1,2,3]triselenole | 735277-24-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 5,6-dibromo-4,7-diethylbenzo[1,2,3]triselenole
• 英文别名: 5,6-dibromo-4,7-diethylbenzotriselenole；5,6-Dibromo-4,7-diethyl-1,2,3-benzotriselenole
• CAS: 735277-24-4
• 化学式: C₁₀H₁₀Br₂Se₃
• 分子量: 526.877
• InChiKey: SESUJHPGTYNWJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.54
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5,6-dibromo-4,7-diethylbenzo[1,2,3]triselenole 在 sodium tetrahydroborate 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 4,5-bis(4-nitrophenethylseleno)-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
• 作为产物：
  描述：

  1,2,4,5-tetrabromo-3,6-diethylbenzene 在 selenium 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 反应 24.0h， 以54%的产率得到5,6-dibromo-4,7-diethylbenzo[1,2,3]triselenole
  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 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。
• 4,5-Dicyano-3,6-diethylbenzo-1,2-diselenete, a Highly Stable 1,2-Diselenete: Its Preparation, Structural Characterization, Calculated Molecular Orbitals, and Complexation with Tetrakis(triphenylphosphine)palladium
  作者：Takeshi Kimura、Tsukasa Nakahodo、Hisashi Fujihara、Eiichi Suzuki

  DOI：10.1021/ic5000765

  日期：2014.5.5

  with aluminum chloride in toluene. X-ray crystallographic analysis demonstrated that 4 contains a trapezoidal diselenide ring rather than a benzo-1,2-diselenone structure. In crystal form, 4 undergoes self-assembly and generates structures based on layered molecular sheets since the unit cell contains only one molecule. While the cyclic voltammogram of 4 exhibited only one irreversible peak (Ep = 1

  通过4,5-（邻苯二甲撑二硒基）-3的反应制备了第一个可分离的苯并1,2-二硒基4,5-二氰基-3,6-二乙基苯并1,2-二硒基（4）， 6-二乙基邻苯二甲腈（3）与氯化铝的甲苯溶液。X射线晶体分析表明，4包含梯形二硒化物环而不是苯并1,2-二硒酮结构。由于晶胞仅包含一个分子，因此4以晶体形式进行自组装并基于层状分子片生成结构。虽然4的循环伏安图仅显示一个不可逆峰（E p在氧化期间为1.59 V），在还原过程中为两个准可逆偶对，在还原偶的微分脉冲伏安图中观察到三个峰（E 1/2 = -1.19，-0.75和-0.69 V）。尽管在钠金属存在下4的THF溶液对EPR无影响，但在其1 H，13 C和77 Se NMR光谱中很容易观察到各种信号。对4的分子轨道计算表明，HOMO轨道主要位于两个硒原子和四个苯碳原子上，而LUMO轨道仅位于二硒环上。看来4的HOMO和LUMO轨道与未取代的苯并1,2
• 10.1002/chem.202401628
  作者：Kimura, Takeshi、Nakahodo, Tsukasa

  DOI：10.1002/chem.202401628

  日期：——

  Unsymmetric boron (III) subphthalocyanines with a triselenole ring or a diselenete ring and eight fluoro groups were prepared by the reaction of 5,6-dicyano-4,7-diethylbenzo[1,2,3]triselenole and tetrafluorophthalonitrile with trichloroborane in xylene. When boron (III) subphthalocyanine with the diselenete ring was treated with pentachloro antimonate in dichloromethane or sodium metal in hexane/tetrahydrofuran

  通过5,6-二氰基-4,7-二乙基苯并[1,2,3]三硒醇和四氟邻苯二甲腈与三氯硼烷在二甲苯中反应制备了具有三硒醇环或二硒环和八个氟基团的不对称硼(III)亚酞菁。当具有二烯环的亚酞菁硼 (III) 用二氯甲烷中的五氯锑酸盐或己烷/四氢呋喃中的金属钠处理时，溶液显示出强烈的 ESR 信号。
• Preparation and Electrochemical Property of Octaethylphthalocyanine Fused with Four Diselenadithiafulvalene Units
  作者：Takeshi Kimura

  DOI：10.3987/com-13-s(s)72

  日期：——

  3,6-Diethylphthalonitrile (3) fused with diselenadithiafulvalene (DSDTF) was prepared from 5,6-dibromo-4,7-diethylbenzotriselenole (1) and treated with lithium alkoxide to produce octaethylphthalocyanine (6) with four DSDTF units. The structure of the product was determined by H-1 NMR and MALDI-TOF-MS. Electrochemical and optical properties of 6 and its nickel complex (6-Ni) were examined by cyclic voltammetry and UV-vis spectroscopy.
• 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.