4,8-Bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene

2.2 g of benzo [1, 2-b: 4, 5-b '] dithiophene-4, 8-dione was weighed out in a single-Add zinc powder 1.5g, Sodium hydroxide 6 g, Distilled water 35g, Heating reflux, The oil bath temperature is controlled at 120 ° C, Reaction time: 13h;The solution quickly changed from yellow to red, As the reaction progresses, The solution was homogeneous.At this time, 5.8 g of C8H17Br and 0.11 g of catalytic equivalent of tetrabutylammonium bromide TBAB were added, As the reaction progresses, the solution changes from black to red, Eventually turned pale yellow.Terminate the reaction: add water to quench.Refining process: multiple extraction with ether, anhydrous MgSO4 dry, spin the solvent, Vacuum drying to constant weight, To give the product 4, 8-bis (2-ethyl-hexyloxy) benzo [1, 2-b: 4, 5-b 'Dithiophene3.9 g, The yield was 87percent.2.2 g of benzo [1, 2-b: 4, 5-b '] dithiophene-4, 8-dione In a single-necked flask, 1.5 g of zinc powder was added, Sodium hydroxide 6 g, Distilled water 35g, heated to reflux, oil bath temperature control at 120 , reaction time: 13h;The solution quickly changed from yellow to red, As the reaction progresses, the solution is homogeneous.At this time, 5.8 g of C8H17Br and 0.11 g of catalytic equivalent of tetrabutylammonium bromide TBAB were added, As the reaction progresses, the solution changes from black to red and eventually becomes pale yellow. Terminate the reaction: add water to quench.Refining process: extraction with ether several times, anhydrous MgSO4 dry, spin the solvent, vacuum drying to constant weight, The yield of the product 4, 8-bis (2-ethyl-hexyloxy) benzo [1, 2-b: 4, 5-b '] dithiophene was obtained 3.9 g, in a yield of 87percent.Benzo [1, 2-b: 4, 5-b '] dithiophene-4, 8-dione, RBr, zinc dust, tetrabutylammonium bromide (TBAB), sodium hydroxide, waterThe mass ratio is 1: 2.6: 0.68: 0.05: 2.7: 15.91.In a flask, 4, 8-dihydrobenzo[1, 2-b:4, 5-b′]dithiophen-4, 8-dione (6) (6.6 g, 30 mmol) and zinc powder (4.29 g, 66 mmol) were added to 90 ml of water, then 18 g of NaOH was added into the mixture. After the solution was refluxed for 1 h, 1-bromo-2-ethylhexane (17.4 g, 90 mmol) and a catalytic amount of tetrabutylammonium bromide were added and heated to reflux for another 6 h. Then, cold water (300 ml) was added and the mixture was extracted with ethyl acetate, the extract was dried over anhydrous magnesium sulfate, the residue was purified by column chromatography on silica gel to obtain 4, 8-bis(2-ethylhexyloxy)benzo[1, 2-b:3, 4-b]dithiophene (7) in a 65percent yield. Compound 7 (6.1 g, 13.6 mmol) was added into THF (200 ml) under nitrogen, n-butyllithium (36.3 mmol, 2.2 M) was added dropwise to the mixture at −80 °C and stirred for 1 h, the cooling bath was removed, and the reactant was stirred at ambient temperature for another 1 h. Trimethyltin chloride (8 g, 40.4 mmol) was added in one portion at −80 °C and the reactant was stirred at ambient temperature overnight. After 200 ml cold water was added and the mixture was extracted with hexane, the organic layer was dried over anhydrous magnesium sulfate, after the evaporation of solvent, the residue was recrystallized by ethyl alcohol and obtained 2, 6-bis(trimethyltin)-4, 8-bis(2-ethylhexyl)benzo[1, 2-b:3, 4-b′]dithiophene 8 (6.15 g, 7.96 mmol) in a 58.3percent yield.To the solution of 2 (2.20 g, 10 mmol) in water (40 mL), zincpower (1.96 g, 30 mmol) and sodium hydroxide (8.00 g, 200 mmol)were added and the reaction mixture was refluxed for 1 h. To theresultant solution, catalytic amount of tetra-n-butylammoniumbromide (0.032 g, 0.1 mmol) was added followed by the addition of1-bromo-2-ethylhexane (5.79 g, 30 mmol). The reaction mixturewas refluxed overnight and then poured into water (200 mL). Themixture was extracted with diethyl ether (3 50 mL). The combinedorganic extract was dried over anhydrous Na2SO4. Solventwas removed under reduced pressure and residue was purified bysilica gel column chromatography (1:15 dichloromethane/hexaneeluent) to give the titled compound as white solid (yield 65percent).1H NMR (500 MHz, CDCl3, d ppm): 0.93 (t, J 7.0 Hz, 6H), 1.01 (t, J 7.5 Hz, 6H), 1.34e1.44 (m, 8H), 1.45e1.53 (m, 2H), 1.55e1.75 (m, 6H), 1.76e1.84 (m, 2H), 4.17 (d, J 5.5 Hz, 4H), 7.36 (d, J 5.5 Hz, 2H), 7.47 (d, J 5.5 Hz, 2H).DI water to 4, 8dihydrobenzoin (H2O) in 4.60 ml [1, 2b:4, 5b'] dithiophene 4, 8dione(4, 8dehydrobenzo[l, 2b:4, 5b']dithiophene4, 8dione, 8.0 g, 36.2 mmol) and zinc powder (Zn powder) (5.2 g, 79.6 mmol) into a stirred back, sodiumhydroxide (NaOH, stirring to 24 g) and the mixture was refluxed for 1 hour.The color of the reaction solution turned orange from yellow through red. 2ethylhexylbromide (2ethylhexylbromide, 21.0 g, 108.9 mmol) to the solution and to put the tetrabutylammonium bromide (tetrabutylammonium bromide, as catalyst) werestirred / reflux for 2 hours. If the solution of the red color, or a dark red color to give the addition of zinc powder (zinc powder)further stirred / reflux for 6 hours. This solution was back extracted with 2 poured into diethyl ether (Diethyl ether) times incold water, to remove the residue magnesium sulfate (MgSO4) (Magnesium sulfate). Under reduced pressure, the remainingsolution to remove the solvent, and silica column (silica column, eluent Pet ether: MC = 9: 1) through a colorless liquid.Dihydrobenzo[1, 2-b: 4, 5-b']dithiophene-4, 8-dione (8.0 g, 36.2 mmol) and zinc powder (5.2 g) were dissolved in 60 ml of distilled water G, 79.6 mmol) was added to the reaction mixture, and sodium hydroxide (24 g) was added thereto, and the mixture was refluxed for 1 hour while changing the color of the solution from yellow to red to orange. To this solution was added 2-ethylhexylbromide (21.0 g, 108.9 mmol) and tetrabutylammonium bromide (as catalyst) and stirred / refluxed for 2 hours. The color of the solution was red or dark If red was added, zinc powder was added and stirred / refluxed for 6 hours. The solution was poured into cold water, extracted twice with diethyl ether, and then the residue was removed with magnesium sulfate (MgSO4). The remaining solution was decompressed to remove the solvent, and a colorless liquid of the formula 4-b was obtained through a silica column (silica column, eluent: Pet ether: MC = 9: 1) (Yield: 64.9percent)1.1 In a 250 mL three-necked flask under argon atmosphere, add 5.70 g (12.76 mmol) of 4, 8-bis ((2-ethylhexyl) oxy) benzo [1, 2-b: 4, 5- b '] dithiophene (compound 1) and 120 mL of tetrahydrofuran, the reaction system was lowered to -78 C.1.2. Take 6 mL (14.30 mmol) of n-butyllithium and slowly drop it into the reaction bottle. After the dropwise addition is complete, after reacting at -78 C for 30 minutes, naturally return to room temperature for 30 minutes.1.3. The reaction system was reduced to -78 C again. 4.46 mL (16.59 mmol) of tributyltin chloride was added to the reaction flask at one time, and the room temperature was naturally restored. The reaction was performed for 12 hours.1.4, quench the reaction by adding water, extract the organic phase with petroleum ether, dry the organic phase with anhydrous magnesium sulfate, filter, and remove the solvent to obtain the crude product.1.5. The crude product is a yellow liquid and goes directly to the next step without purification.

Molecular Weight:446.7
XLogP3:10.2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:14
Exact Mass:446.23132280
Monoisotopic Mass:446.23132280
Topological Polar Surface Area:74.9
Heavy Atom Count:30
Complexity:432
Undefined Atom Stereocenter Count:2
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes