][1,4]dioxine (EDOTAlkyl-substituted EDOT monomer 2-dodecyl-2H,3H-thieno[3,4-b][1,4]dioxine Alkyl-substituted EDOT
][1,4]dioxine (EDOTAlkyl-substituted EDOT monomer 2-dodecyl-2H,3H-thieno[3,4-b][1,4]dioxine Alkyl-substituted EDOT monomer 2-dodecyl-2H,3H-thieno[3,4-b][1,4]dioxine C12) and alkoxy-substituted monomer 3,4-bis(hexyloxy)thiophene (3,4-BHOT) were synthe(EDOT-C12) and alkoxy-substituted monomer three,4-bis(hexyloxy)thiophene (three,4-BHOT) (EDOT-C12) and alkoxy-substituted monomer three,4-bis(hexyloxy)thiophene (3,4-BHOT) sized using a modified literature procedure through p-toluenesulfonic acid-catalyzed transetherwere synthesized using a modified literature procedure by way of p-toluenesulfonic acid-catawere synthesized employing a modified literature procedure by way of p-toluenesulfonic acid-cataification [47,48] of 3,4-dimethoxythiophene along with the corresponding alcohol (Schemealcolyzed transetherification [47,48] of 3,4-dimethoxythiophene along with the corresponding two). lyzed transetherification synthesized utilizing one SBP-3264 Protocol particular equivalent and also the corresponding and alcoMonomer EDOT-C12 was [47,48] of three,4-dimethoxythiophene ofone equivalent of 1,2-tetrahol (Scheme 2). Monomer EDOT-C12 was synthesized employing 1,2-tetradecanediol, hol (Scheme 2). Monomer EDOT-C12 was synthesized utilizing one equivalent of 1,2-tetramonomer 3,4-BHOT was synthesized making use of two equivalents of n-hexanol. decanediol, and monomer three,4-BHOT was synthesized utilizing two equivalents of n-hexanol. decanediol, and monomer three,4-BHOT was synthesized employing two equivalents of n-hexanol.Scheme two. Synthesis of ether-substituted thiophene monomers. Scheme two.2. Synthesis of ether-substituted thiophene monomers. Scheme Synthesis of ether-substituted thiophene monomers.Supplies 2021, 14,six of2.two.1. Synthesis of EDOT-C12 To a 1 L three-necked round bottom flask (Chemglass Life Sciences) outfitted using a magnetic stir bar (Fisher Scientific, Hampton, NH, USA), Soxhlet extractor (Chemglass Life Sciences) charged with 4 molecular sieves and high-efficiency condenser Chemglass Life Sciences) was added 1,2-tetradecanediol (17.59 g, 76.3 mmol) and p-toluenesulfonic acid (1.33 g, 7.0 mmol) against a optimistic stress of argon. Toluene (400 mL) was added, and also the flask was sealed using a rubber septum. Stirring was initiated, plus the flask was heated at 60 C. After all solids had dissolved, the septum was removed and three,4-dimethoxythiophene (DMT, 10.00 g, 87.six mmol) was added against a optimistic stress of argon. The flask was resealed, along with the mixture was heated at 120 C for 48 h under argon. The colorless mixture slowly darkened to dark brown over quite a few hours after addition of the DMT. The mixture was then cooled to space temperature and poured into a 1 L separatory funnel (Fisher Scientific). The crude reaction mixture was washed four occasions with portions (ca. 200 mL every) of deionized water. The organic fraction was collected, dried more than anhydrous MgSO4 , and filtered. The Scaffold Library Physicochemical Properties filtrate was evaporated under reduced stress to provide the crude item a dark brown oil. The crude solution was purified by filtration via silica gel with hexanes followed by removal in the solvent beneath lowered pressure. The yellow strong was recrystallized from diethyl ether at -78 C to give 6.02 g (25 ) item as a slightly yellow powder. 1 H NMR (Figure S1, 400 MHz, CDCl3 ) : six.30 (s, 2H), 4.14 (dd, J = 11.three, two.1 Hz, 1H), four.10 (m, 1H), 3.86 (dd, J = 11.three, 7.9 Hz, 1H), 1.67.27 (m, 22H), 0.89 (t, 3H); Lit. [23]: 6.30 (s, 2H), four.12 (m, 2H), 3.86 (m, 1H), 1.40 (m, 22H), 0.88 (t, 3H); MS (Figure S3, m/z): [M H] calcd for C18 H31 O2 S 311.204; located 311.167. 2.two.two. Synthesis o.
