][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 (three,4-BHOT) had been synthe(EDOT-C12) and alkoxy-substituted monomer 3,4-bis(hexyloxy)thiophene (3,4-BHOT) (EDOT-C12) and alkoxy-substituted monomer three,4-bis(hexyloxy)thiophene (three,4-BHOT) sized using a modified literature process by means of p-toluenesulfonic acid-catalyzed transetherwere synthesized using a modified literature process via p-toluenesulfonic acid-catawere synthesized employing a modified literature process by means of p-toluenesulfonic acid-cataification [47,48] of 3,4-dimethoxythiophene and the corresponding alcohol (Schemealcolyzed transetherification [47,48] of three,4-dimethoxythiophene and also the corresponding two). lyzed transetherification synthesized using one particular equivalent plus the corresponding and alcoMonomer EDOT-C12 was [47,48] of 3,4-dimethoxythiophene ofone equivalent of 1,2-tetrahol (Scheme 2). Monomer EDOT-C12 was synthesized utilizing 1,2-tetradecanediol, hol (Scheme two). Monomer EDOT-C12 was synthesized working with a single equivalent of 1,2-tetramonomer three,4-BHOT was synthesized working with two equivalents of n-hexanol. decanediol, and monomer three,4-BHOT was synthesized making use of two equivalents of n-hexanol. decanediol, and monomer three,4-BHOT was synthesized using two equivalents of n-hexanol.Scheme two. Synthesis of ether-substituted thiophene monomers. Scheme 2.two. Synthesis of ether-substituted thiophene monomers. Scheme Synthesis of ether-substituted thiophene monomers.Components 2021, 14,six of2.two.1. Synthesis of EDOT-C12 To a 1 L three-necked round bottom flask (Diversity Library Formulation Chemglass Life Sciences) outfitted with a magnetic stir bar (Fisher Scientific, Hampton, NH, USA), Soxhlet extractor (Chemglass Life Sciences) charged with four 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 constructive stress of argon. Toluene (400 mL) was added, along with the flask was sealed with a rubber septum. Stirring was initiated, plus the flask was heated at 60 C. When all solids had dissolved, the septum was removed and three,4-dimethoxythiophene (DMT, 10.00 g, 87.six mmol) was added against a constructive stress of argon. The flask was resealed, and also the mixture was heated at 120 C for 48 h beneath argon. The colorless mixture slowly darkened to dark brown over various hours right after addition with 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 times with portions (ca. 200 mL every single) of deionized water. The organic fraction was collected, dried more than anhydrous MgSO4 , and filtered. The filtrate was evaporated below lowered stress to provide the crude solution a dark brown oil. The crude product was purified by filtration via silica gel with hexanes followed by removal from the solvent below decreased stress. The yellow solid was recrystallized from diethyl ether at -78 C to give six.02 g (25 ) solution as a BMS-8 Cancer slightly yellow powder. 1 H NMR (Figure S1, 400 MHz, CDCl3 ) : six.30 (s, 2H), 4.14 (dd, J = 11.3, two.1 Hz, 1H), 4.ten (m, 1H), 3.86 (dd, J = 11.3, 7.9 Hz, 1H), 1.67.27 (m, 22H), 0.89 (t, 3H); Lit. [23]: six.30 (s, 2H), 4.12 (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; found 311.167. 2.two.two. Synthesis o.
