4,7-dibroMobenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole)

First, the amine compound (10 g, 30.8 mmol) obtained in Step 2 was dissolved in dehydrated pyridine (300 ml) in a 1, 000 ml three-necked flask under Ar gas, and N-thionylaniline(9.5 g, 66 mmol) and trimethylsilyl chloride (39.5 g, 363.5 mmol) were added. Thereafter, the internal temperature was raised to 80 ° C., and the mixture was stirred overnight.Then, the reaction solution was cooled to room temperature and poured into water (200 ml). Precipitated crystals were collected by filtration, and the solid was washed with THF / n-hexane to obtain 6 g of a solid (crystal).Thereafter, purification was carried out by silica gel chromatography (silica gel 300 g, developing solvent chlorobenzene / hexane = 10: 3) (yield 3 g, yield 27.6percent)Under an argon atmosphere, 0.25 g (0.71 mmol) of 4, 8-dibromoB2T, 0.95 g of trimethyl {[4- (trifluoromethyl) phenyl] ethynyl} tin (IV) crude product, tetrakis (triphenylphosphine) palladium (0) 0.099g(0.086 mmol) in 50 mL of tolueneWas added and stirred at 100 C. for 3 hours.The reaction solution was concentrated and the resulting crude product was separated and purified by silica gel column chromatography (hexane / chloroform) to give compound (C104).0.024 g (6.4% yield) was obtained.0.10 g (0.28 mmol) of 4, 8-dibromoB2T obtained according to the synthesis method described in Advanced Materials Research, 2012, 482-484, page 1221;Trimethyl {[4- (1, 1-difluorohexyl) phenyl] ethynyl} tin (IV) obtained as described aboveTo a crude product of 0.33 g and tetrakis (triphenylphosphine) palladium (0) (0.040 g (0.034 mmol)), 20 mL of toluene was added, followed by stirring at 100 C. for 5 hours.The reaction mixture was concentrated and the resulting crude product was separated and purified by silica gel column chromatography (hexane / chloroform) to give compound (101).0.032 g (18% yield) was obtained.Dibromo-BBT 1 (0.1 g, 0.28 mmol) and 2a (0.7 mmol) , Pd (PPh 3) 4 (20 mg, 0.017 mmol) and 20 mL of toluene were added into a two-necked flask. After the mixture was refluxed for 24 h, additional 2a (0.7 mmol) and Pd (PPh 3) 4 (20 mg, 0.017 mmol) were added to the reaction system. The solution was allowed to reflux for another 24 h. After cooling down to room temperature, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column (hexane) to obtain the product (yield: 55%) . 1H NMR (400 MHz, CDCl 3) , delta (ppm) : 8.83 (2H, s) , 7.28 (2H, s) , 2.73 (4H, d, J = 8 Hz) , 1.77 (2H, m) , 1.32 (80H, m) , 0.9 (12H, m) .In a round flask equipped with a condenser, 3g of bisbenzothiadiazole and 3 g of tributyl(4-(2-decyltetradecyl)thiophen-2-yl) stannane), 13.3 g (2.5 eq), 0.5 g (0.05 eq) of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was dissolved in 50 mL of toluene and refluxed for 12 hours. After 12 hours, extraction was carried out through chloroform and brine. After that, impurities were removed through hexane to obtain Compound A-1.Dibromobenzobisthiadiazole (88.0 mg, 0.25 mmol), 4-tert-butyl-N-(4-tert-butylphenyl)-N-(4-(5'-trimethyl) Tin-based)-(2, 2'-bithienyl)-5-phenyl)phenylamine (342.3 mg, 0.50 mmol) and tetrakis(triphenylphosphine)palladium (14.4 mg, 0.0125 mmol) were dissolved in 30 mL of dry toluene In the inert atmosphere, reflux for 24 hours, and finally silica gel column chromatography (eluent is methylene chloride) to obtain a near-infrared two-zone conjugated small molecule with a yield of 65%.Into a glass reaction vessel equipped with a stirrer and a capacity of 50 mL, 3.4 g (5.4 mmol) of the compound (C14-a)475.2 mg (1.35 mmol) of dibromobenzobisthiadiazole, Dichlorobis (triphenylphosphine) palladium (II) was added to 284.3 mg (0.41 mmol) and dehydrated toluene 22 mL were added, And reacted at an internal temperature of about 100 C. for 7 hours. The reaction solution was concentrated, methyl alcohol was added, and the precipitate was collected by filtration to obtain 1.0 g of a crude product. The resulting crude product was subjected to Soxhlet extraction (toluene), and the extract was cooled to -26 C. and recrystallized to obtain 637 mg of Compound (C14) as a dark green powder.Into a glass reaction vessel equipped with a stirrer and having a capacity of 250 mL, 11.6 g (19.2 mmol) of the compound (C12-a), 1.69 g (4.8 mmol) of dibromobenzobisthiadiazole, 1.01 g of dichlorobis (triphenylphosphine) palladium (II)(1.44 mmol), and dehydrated toluene (77 mL) were added, And reacted at an internal temperature of about 100 C. for 7 hours. The reaction solution was concentrated, methyl alcohol was added, and the precipitate was collected by filtration to obtain 4.0 g of a crude product. The resulting crude product was subjected to Soxhlet extraction (toluene), the extract was cooled to -26 C. and recrystallization was repeated to obtain 974 mg of the compound (C 12) as a dark green powder.Into a glass reaction vessel equipped with a stirrer and a capacity of 100 mL, 4.9 g (7.86 mmol) of the compound (C11-a)693.5 mg of the compound (C10) dibromobenzobisthiadiazole(1.97 mmol), Dichlorobis (triphenylphosphine) palladium(II) 414.8 mg (0.59 mmol), And 31 mL of dehydrated toluene were added and the mixture was reacted at an internal temperature of about 100 C. for 7 hours.The reaction solution was concentrated, methyl alcohol was added, and the precipitate was collected by filtration to obtain a crude product1.5 g was obtained. The obtained crude product was subjected to Soxhlet extraction (toluene)By cooling the extract to -26 C. and recrystallizing it repeatedly, As a dark green powder, 443 mg of the compound (C11) was obtained.Into a glass reaction vessel equipped with a stirrer and a capacity of 50 mL, 1.31 g (2.17 mmol) of the compound (C13-a)1.34 g (2.17 mmol) of the compound (C11-a)763.9 mg (2.17 mmol) of dibromobenzobisthiadiazole, 533.7 mg (1.3 mmol) of 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl, 298.5 mg (0.33 mmol) of tris (dibenzylideneacetone) dipalladium and 17 mL of dehydrated toluene were added, The reaction was carried out at an internal temperature of about 90 C. for 7 hours. The reaction solution was concentrated, methyl alcohol was added, and the precipitate was collected by filtration to obtain 1.75 g of a crude product. Purification by silica gel column chromatography (toluene)As a dark green powder, 355.7 mg of the compound (C13) was obtained.

Molecular Weight:352.0
XLogP3:4.2
Hydrogen Bond Acceptor Count:6
Exact Mass:351.79106
Monoisotopic Mass:349.79311
Topological Polar Surface Area:79.7
Heavy Atom Count:14
Complexity:264
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes