* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134
2
[ 36711-69-0 ]
[ 63525-48-4 ]
Yield
Reaction Conditions
Operation in experiment
94%
With silver nitrate In ethanol; water for 0.666667 h; Reflux; Inert atmosphere
General procedure: To a solution of 2d (302 mg, 0.516 mmol) in EtOH (10 mL) was added a solution of AgNO3 (369 mg, 2.17 mmol) in water (4 mL). The resulting mixture was heated at reflux under argon for 40 min. The solution was allowed to cool; AgBr was filtered off and washed with EtOH (2 × 5 mL). The solvent was evaporated and the residue was purifiedby recrystallisation (from hexane) to give 3d (146 mg, 94percent yield) as a white solid
Reference：
[1] Angewandte Chemie - International Edition, 2014, vol. 53, # 26, p. 6786 - 6790[2] Angew. Chem., 2014, vol. 126, # 26, p. 6904 - 6908,5
[3] Synthesis (Germany), 2016, vol. 48, # 20, p. 3509 - 3514
[4] Chemical Communications, 2017, vol. 53, # 53, p. 7266 - 7269
[5] Helvetica Chimica Acta, 1944, vol. 27, p. 274,290
[6] Tetrahedron, 2011, vol. 67, # 22, p. 4110 - 4117
3
[ 1074-24-4 ]
[ 63525-48-4 ]
Reference：
[1] Macromolecules, 2002, vol. 35, # 12, p. 4636 - 4645
[2] Journal of the American Chemical Society, 2017, vol. 139, # 6, p. 2428 - 2434
[3] Journal of the American Chemical Society, 2017, vol. 139, # 7, p. 2786 - 2793
[4] Acta Chemica Scandinavica, Series B: Organic Chemistry and Biochemistry, 1977, vol. 31, p. 135 - 140
[5] Tetrahedron Letters, 1990, vol. 31, # 13, p. 1825 - 1828
[6] Journal of the American Chemical Society, 1990, vol. 112, # 14, p. 5655 - 5657
[7] Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134
[8] Macromolecules, 2005, vol. 38, # 15, p. 6402 - 6410
[9] Organic Letters, 2007, vol. 9, # 18, p. 3571 - 3573
[10] Journal of Physical Organic Chemistry, 2005, vol. 18, # 9, p. 962 - 973
[11] Journal of the Chemical Society, 1952, p. 4085
[12] Journal of the Chemical Society, 1952, p. 4085
[13] Helvetica Chimica Acta, 1944, vol. 27, p. 274,290
[14] Angewandte Chemie - International Edition, 2014, vol. 53, # 26, p. 6786 - 6790[15] Angew. Chem., 2014, vol. 126, # 26, p. 6904 - 6908,5
[16] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 18, p. 4497 - 4503
[17] Synthesis (Germany), 2016, vol. 48, # 20, p. 3509 - 3514
[18] Synthesis (Germany), 2016, vol. 48, # 20, p. 3509 - 3514
[19] Journal of Materials Chemistry A, 2016, vol. 4, # 48, p. 18792 - 18803
[20] Chemical Communications, 2017, vol. 53, # 53, p. 7266 - 7269
[21] Journal of the American Chemical Society, 2018, vol. 140, # 3, p. 984 - 992
4
[ 106-42-3 ]
[ 63525-48-4 ]
Reference：
[1] Organic Letters, 2007, vol. 9, # 18, p. 3571 - 3573
[2] Journal of Physical Organic Chemistry, 2005, vol. 18, # 9, p. 962 - 973
[3] Helvetica Chimica Acta, 1944, vol. 27, p. 274,290
[4] Tetrahedron, 2011, vol. 67, # 22, p. 4110 - 4117
[5] Angewandte Chemie - International Edition, 2014, vol. 53, # 26, p. 6786 - 6790[6] Angew. Chem., 2014, vol. 126, # 26, p. 6904 - 6908,5
5
[ 105653-65-4 ]
[ 63525-48-4 ]
Reference：
[1] Journal of Physical Organic Chemistry, 2005, vol. 18, # 9, p. 962 - 973
[2] Journal of the Chemical Society, 1952, p. 4085
[3] Macromolecules, 2010, vol. 43, # 13, p. 5544 - 5553
[4] RSC Advances, 2016, vol. 6, # 70, p. 65426 - 65433
6
[ 623-27-8 ]
[ 63525-48-4 ]
Reference：
[1] Chemistry - An Asian Journal, 2018, vol. 13, # 18, p. 2691 - 2699
7
[ 128244-10-0 ]
[ 63525-48-4 ]
Reference：
[1] Journal of the American Chemical Society, 1990, vol. 112, # 14, p. 5655 - 5657
8
[ 36711-69-0 ]
[ 124-41-4 ]
[ 63525-48-4 ]
Reference：
[1] Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 10054 - 10059
9
[ 4845-68-5 ]
[ 63525-48-4 ]
Reference：
[1] Journal of Materials Chemistry A, 2016, vol. 4, # 48, p. 18792 - 18803
10
[ 7664-93-9 ]
[ 36711-69-0 ]
[ 63525-48-4 ]
Reference：
[1] Helvetica Chimica Acta, 1944, vol. 27, p. 274,290
With chromium(VI) oxide; sulfuric acid; acetic anhydride; acetic acid; at 0℃; for 4h;
Compound 4 was synthesized according to literature procedure.S1 Sulfuric acid (11 mL) wasadded dropwise into a suspension of 1,4-dibromo-2,5-dimethylbenzene (3.0 g, 11.4 mmol),acetic acid (15 mL) and acetic anhydride (30 mL) at 0 C during stirring and then CrO3 (4.5 g)was added in small portions. The resulting mixture was stirred for another 4 h at the same temperature. The greenishslurry was poured into ice-water and then filtered. The collected white solid was washed with cold water and methanol.The crude product was then hydrolyzed by refluxing with a mixture of water (15 mL), ethanol (15 mL) and sulfuric acid(1.5 mL) overnight. After cooling, the mixture was filtered and then recrystallized in DCM/hexane to give compound 4(1.7 g, 51%) as a light yellow solid. The 1H NMR spectrum of 4 matches well with the reported data. 1H NMR (400MHz, CDCl3, 295K) delta 10.39 (s, 2H), 8.19 (s, 2H).
thioacetic acid <i>S</i>-(4-{4-(4-acetylsulfanyl-phenylethynyl)-2,5-bis-[4-(4-acetylsulfanyl-phenylethynyl)-benzyl]-phenylethynyl}-phenyl) ester[ No CAS ]
Unpurified 2,5-dibromo-alpha,alpha,alpha',alpha'-tetraacetoxy-1,4-xylene (60.5 g, 0.122 mole) was dissolved with stirring in three liters of hot ethanol. Then 450 ml of water was added followed by 75 ml of concentrated sulfuric acid which was added very slowly. After being allowed to reflux for an hour, the reaction mixture was diluted with 900 ml of hot water. Cooling overnight at -10 C. resulted in the recrystallization of 30.9 g (87% yield) of 2,5-dibromoterephthalaldehyde, mp 184-189 C. (lit 189-190.5 C.) which was isolated by filtration. Anal. Calc'd for C8 H4 O2 Br2: C, 32.91; H, 1.38; Br, 54.75; MW, 292. Found: C, 32.68; H, 0.90; Br, 54.60; MW, 292 (mass spectrum).
54
sulfuric acid-ice[ No CAS ]
[ 63525-48-4 ]
[ 536-74-3 ]
2,5-bis(phenylethynyl)terephthaloyl chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With pyridine; triethylamine; triphenylphosphine;palladium diacetate;
EXAMPLE IV 2,5-Bis(phenylethynyl)terephthaloyl Chloride (Method 2) 2,5-Dibromoterephthalaldehyde (29.2 g, 0.100 mole) and phenylacetylene (25.5 g, 0.250 mole) were dissolved at 80 C. under nitrogen in a mixture of freshly distilled triethylamine (200 ml) and pyridine (200 ml). Palladium acetate (0.54 g, 0.0024 mole) and triphenylphosphine (1.26 g, 0.0048 mole) were added to the vigorously stirred red solution. The resultant exotherm did not subside for fifteen minutes and a voluminous white precipitate was formed. After an additional hour at reflux, the red slurry was added with vigorous stirring to a sulfuric acid ice mixture. The slightly gummy brown precipitate was washed several times with water in a blender and isolated by filtration. It was dried overnight over phosphorus pentoxide at 80 C./1.0 mm Hg to yield 39.5 g of light brown solid, mp 145-162 C. The crude product was recrystallized from toluene to give 17.5 g of golden crystals, mp 174-179 C.
With palladium diacetate; sodium carbonate; triphenylphosphine; In water; isopropyl alcohol; at 70℃; for 5h;
General procedure: Triphenyl phosphine (0.015 g, 0.06 mmol), palladium acetate (0.002 g, 0.01 mol), phenylboronic acid (0.24 g, 2 mmol), and 7 (0.29 g, 1 mmol) were added into a flask. A degassed mixture of isopropyl alcohol (10 ml), sodium carbonate (aq) (2 N/L, 3 ml), and water (1 ml) was transferred onto the solids, and the resulting solution was stirred under reflux at 70 C for 4 h. The crude product was extracted with dichloromethane and washed with aq NaHCO3. The organic layer was concentrated under vacuum and purified by column chromatography on silica gel eluting with petroleum/ethyl acetate (30:1) to give white crystals (0.27 g, 95%).
4,4″-dimethoxy-[1,1':4′,1″-terphenyl]-2′,5′-dicarbaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With palladium diacetate; sodium carbonate; triphenylphosphine; In water; isopropyl alcohol; at 70℃; for 12h;
General procedure: Triphenyl phosphine (0.015 g, 0.06 mmol), palladium acetate (0.002 g, 0.01 mol), phenylboronic acid (0.24 g, 2 mmol), and 7 (0.29 g, 1 mmol) were added into a flask. A degassed mixture of isopropyl alcohol (10 ml), sodium carbonate (aq) (2 N/L, 3 ml), and water (1 ml) was transferred onto the solids, and the resulting solution was stirred under reflux at 70 C for 4 h. The crude product was extracted with dichloromethane and washed with aq NaHCO3. The organic layer was concentrated under vacuum and purified by column chromatography on silica gel eluting with petroleum/ethyl acetate (30:1) to give white crystals (0.27 g, 95%).
78%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; at 80℃; for 48h;Inert atmosphere;
2,5-Dibromoterephthalaldehyde 1 (4.00 g, 13.70 mmol), 2a (6.09 g,40.10 mmol), Na2CO3 (8.00 g, 75.48 mmol) and Pd(PPh3)4 (150 mg,0.130 mmol) were added into toluene/H2O (300 mL, v/v=3/2). Thenthe mixture was heated to reflux and stirred for 48 h under a nitrogenatmosphere. After cooling to room temperature, the organic layer wasseparated, the aqueous layer extracted with CH2Cl2, the combined organiclayer dried over anhydrous Na2SO4. Upon evaporating off thesolvent, the crude product was subjected to purification by columnchromatography (silica gel; petroleum ether/CH2Cl2, v/v=1/3), affordinga light yellow solid (3.70 g). Yield 78%. 1H NMR (400 MHz,CDCl3) delta 10.10 (s, 2H), 8.08 (s, 2H), 7.38 (d, J=8.4 Hz, 4H), 7.06 (d,J=8.8 Hz, 4H), 3.91 (s, 6H) (Fig. S12); 13C NMR (100 MHz, CDCl3) delta192.11, 160.09, 143.79, 136.52, 131.31, 130.14, 128.75, 114.24, 55.44(Fig. S13). IR (KBr, cm-1): 617, 638, 691, 729, 789, 818, 840, 913, 946, 1006, 1022, 1051, 1113, 1149, 1178, 1249, 1270, 1297, 1385, 1419, 1438, 1451, 1473, 1518, 1571, 1610, 1686. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C22H18O4 346.1205;Found 346.3822 (Fig. S14). Anal. Calcd (%) for C22H18O4: C 76.29, H5.24; Found: C 76.36, H 5.29.
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; at 80℃; for 48h;Inert atmosphere;
2,5-Dibromoterephthalaldehyde 1 (4.00 g, 13.70 mmol), 2a (7.30 g,38.44 mmol), Na2CO3 (8.00 g, 75.48 mmol) and Pd(PPh3)4 (150 mg,0.130 mmol) were added into toluene/H2O (300 mL, v/v=3/2). Thenthe mixture was heated to reflux and stirred for 48 h under a nitrogenatmosphere. After cooling to room temperature, the organic layer wasseparated, the aqueous layer extracted with DCM, the combined organiclayer dried over anhydrous Na2SO4. Upon evaporating off thesolvent, the crude product was subjected to purification by columnchromatography (silica gel; petroleum ether/DCM, v/v=2/1), affordinga light yellow solid (5.15 g). Yield 89%. 1H NMR (400 MHz,CDCl3) delta 10.08 (s, 2H), 8.14 (s, 2H), 7.83 (d, J=8.0 Hz, 4H), 7.60 (d,J=7.6 Hz, 4H) (Fig. S5); 13C NMR (100 MHz, CDCl3) delta 190.49, 143.57,139.91, 136.57, 130.64, 130.58, 130.30, 125.84, 125.81 (Fig. S6);HRMS (MALDI-TOF) m/z: [M]+ Calcd for C22H12F6O2 422.0741; Found422.3416 (Fig. S7). Anal. Calcd (%) for C22H12F6O2: C 62.57, H 2.86;Found: C 62.63, H 2.78.
80%
With palladium diacetate; sodium carbonate; triphenylphosphine; In water; isopropyl alcohol; at 70℃; for 12h;
General procedure: Triphenyl phosphine (0.015 g, 0.06 mmol), palladium acetate (0.002 g, 0.01 mol), phenylboronic acid (0.24 g, 2 mmol), and 7 (0.29 g, 1 mmol) were added into a flask. A degassed mixture of isopropyl alcohol (10 ml), sodium carbonate (aq) (2 N/L, 3 ml), and water (1 ml) was transferred onto the solids, and the resulting solution was stirred under reflux at 70 C for 4 h. The crude product was extracted with dichloromethane and washed with aq NaHCO3. The organic layer was concentrated under vacuum and purified by column chromatography on silica gel eluting with petroleum/ethyl acetate (30:1) to give white crystals (0.27 g, 95%).
With palladium diacetate; sodium carbonate; In water; N,N-dimethyl-formamide; at 20℃; for 10h;Inert atmosphere;
1. A 10 mL flask was charged with 116.8 mg (0.4 mmol) of 2,5-dibromobenzene-1,4-dicarbaldehyde, 1.0 mL of N, N-dimethylformamide, 0.5 mL of a 2 mol / L aqueous solution of Na2CO3 and 190.04 mg (1.0 mmol) of 4-trifluoromethylphenylboronic acid represented by the formula I-1, stirred and mixed uniformly, Then, 4.4 mg (0.02 mmol) of palladium acetate was added and the mixture was stirred at room temperature for 10 hours in a nitrogen atmosphere. The mixture was extracted with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to remove the solvent. Column chromatography (using a mixture of petroleum ether and ethyl acetate in a 20: 1 volume ratio as eluent)2,5-bis (4-trifluoromethylphenyl) benzene-1,4-dicarbaldehyde of Formula II-1 was obtained.
Ethyl thioglycolate (1.55 cm3, 13.7 mmol) is added to a stirred mixture of 2,5-dibromo-benzene-1 ,4-dicarbaldehyde (2.0 g, 6.9 mmol), triethylamine (1.9 cm3, 13.7 mmol) and ethanol (20 cm3). The mixture is then heated at reflux for 17 hours. Further ethyl thioglycolate (0.8 cm3) and triethylamine (0.95 cm3) is added to the mixture and the mixture heated at reflux for 24 hours. The mixture allowed to cool and poured into water (100 cm3). The precipitate is collected by filtration and washed with water (50 cm3) and methanol (30 cm3). The crude is purified by recrystallisation from 1 ,4- dioxane to give benzo[1 ,2-b;4,5-b']dithiophene-2,6-dicarboxylic acid diethyl ester as an off white solid, (0.05 g, 2%). MS (m/e): 334 (Mu+' 100%),306, 289, 278, 261 , 233, 189.
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