To a solution of 4-bromoaniline (30 g,174 mmol，4-溴苯胺 CAS#: 106-40-1) in dry DMF (200 mL) was added1-bromotetradecane (89.3 mL, 366 mmol，1-溴十四烷) and N,N-diisopropylethylamine (62.2 mL, 357 mmol，N,N-二异丙基乙胺). The reaction solution Was heated at 90° C. for 16 hr under argon before being cooled to room temperature.
To this reaction solution was again added 1-bromotetradecane (45 mL, 184 mmol，1-溴十四烷) and N,N-diisopropylethylamine (31 mL, 178 mmol，N,N-二异丙基乙胺) and the reaction mixture was heated at 90° C. for another 15 hr. After cooling, the reaction solution was concentrated in vacumn and the residue was diluted With CH2Cl2 (400 mL). The CH2Cl2 solution Was Washed With 1N aqueous NaOH (2><), H20, and brine（饱和食盐水）, was dried over Na2SO4 and Was concentrated in vacuo to yield a dark brown oil (about 110 g). Preparative column chromatogram phy on silica gel by a Waters 500 Prep LC system eluting With hexane afforded a yellow oil that contained mainly the product (4-bromo-N,N-di-(C14H29)-aniline) along With a minor component 1-bromotetradecane. The latter compound was removed from the mixture by vacuum distillation (bp 105—110° C., 0.6 mm，真空蒸馏) to leave 50.2 g (51 %) of the product as a brown oil.
To a mixture of magnesium turnings(9.60 g, 395 mmol) in dry THF (30 mL) under argon was added dropwise a solution of the above substituted aniline product (44.7 g, 79 mmol) in THF (250 mL). A few crystals of iodine （I2）were added to initiate the formation of the Grignard reagent（格氏试剂）. When the reaction mixture became warm and began to reflux, the addition rate was regulated to maintain a gentle reflux. After addition was complete, the mixture was heated at reflux for an additional hour. The cooled supernatant solution was transferred via cannula （插管）to an addition funnel （漏斗） and added dropwise (over 2.5 hr) to a solution of phenyl lyoxal (11.7 g, 87 mmol，苯甲酰甲醛) in THF (300 mL) at 30°
C. under argon. The reaction mixture was gradually warmed to 0° C. over 1 hr and stirred for another 30 min. The resulting mixture was poured into a mixture of ice water (800 mL) and ethyl acetate (250 mL). The organic phase was separated and the aqueous phase was extracted With ethyl acetate (2*). The combined organic phases were washed with H2O (2*), brine and were dried over MgSO4. Evaporation of the solvent gave 48.8 g of the crude product as a dark
green oily liquid. Flash column chromatography of this liquid (gradient elution With hexane, 1.5:98.5, 3:97, 5:95 ethyl acetate:hexane) afforded 24.7 g (50%) of the benZoin product (LSIMS (C42H69NO2): [M-H]+618.6, 1H NMR (250 MHZ, CDCl3)
was consistent with the expected benZoin product.
To a solution of the benZoin product from above (24.7 g, 40 mmol) in dry toluene (500 mL) was added sequentially 2-mercaptoethanol (25 g, 320 mmol, 巯基乙醇) and TMSCl (100 mL, 788 mmol, 三甲基氯硅烷). The reaction solution was heated at reflux for 23 hr under argon before being cooled to room temperature. To this was added additional TMSCl (50 mL, 394 mmol); and the reaction solution Was heated at refux for another 3 hr. The resulting solution was cooled, Was made basic with cold 2.5N aqueous NaOH and Was extracted With CH2Cl2 (3><). The combined organic layerswere washed with saturated aqueous NaHCO3 (2x) and brine, Was dried over Na2SO4 and was concentrated in vacuo to give a brown oily liquid. Preparative
column chromatography on silica gel by using a waters 500 Prep LC system(gradient elution With hexane, 1:99, 2:98 ethyl acetatehexane) provided 15.5 g(60%) of the C-28 thioxene as an orange-yelloW oil (LSIMS (C44H71NOS):[M-H]+661.6, 1H NMR (250 MHZ, CDCl3) was consistent with the expected C-28thioxene product 2-(4-(N,N-di-(C14H29)-anilino)-3-phenyl thioxene. Silicon Tetra-t-butyl Phthalocyanine:
