Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[CH2:9][CH2:10][CH3:11].C[CH2:13][O:14][CH2:15][CH3:16].[C:17]1(C)[CH:22]=CC=C[CH:18]=1>>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]#[C:10][C:11]1[CH:22]=[CH:17][CH:18]=[CH:16][C:15]=1[O:14][CH3:13]
Reactant: Cc1ccccc1
Reactant: CCCc1ccccc1OC
Reactant: CCOCC
Product: COc1ccccc1C#Cc1ccccc1OC
Temperature: 25 °C
Reaction time: 2 h
Yield: 97 %

Procedure:
In a dry 25 mL Schlenk-tube, which has been flooded with argon, 1-methoxy-2-(prop-1-yl)benzene (146 mg, 1 mmol), complex 23a.(Et2O) (22 mg, 0.02 mmol, 2 mol %) and molecular sieve (1 g, 5 Å, powder) were suspended in 5 mL of toluene. The reaction mixture was stirred for 2 h at room temperature, was filtered over a short silica gel column (2 cm), the filtrate was concentrated and the residue was purified by column chromatography (SiO2, hexane/EtOAc, 20:1). 1,2-bis(2-methoxyphenyl)ethine (115 mg, 0.48 mmol, 97%) was obtained as colorless solid. M.p.=126-127° C.; 1HNMR (400 MHz, CD2Cl2): δ=7.49 (ddd, J=7.3, 1.6, 0.5 Hz, 2H), 7.33 (ddd, J=7.9, 7.7, 1.9 Hz, 2H), 6.95 (td, J=7.9, 1.0 Hz, 4H), 3.92 (s, 6H); 13C NMR (100 MHz, CD2Cl2): δ=160.3 (2×C), 133.7 (2×CH), 130.1 (2×CH), 120.8 (2×CH), 113.0 (2×C), 111.3 (2×CH), 90.1 (2×C), 56.2 (2×CH3); IR (film): v=3105, 3033, 2998, 2963, 2937, 2833, 1945, 1903, 1863, 1598, 1574, 1498, 1464, 1456, 1432, 1274, 1241, 1184, 1162, 1115, 1047, 1020, 937, 750 cm−1; MS (EI) m/z (%): 238 [M+] (100), 237 (32), 223 (23), 221 (15), 207 (10), 195 (5), 178 (8), 165 (14), 152 (9), 131 (19), 111 (6), 97 (3), 89 (3); HRMS (ESI): m/z: calculated for O16H14O2+Na: 261.0886; found: 261.0884.
Reaction SMILES: C(OC(=O)[N:7]([CH2:12][C:13]1[CH:14]=[N:15][C:16]([C:19]2[S:27][C:26]3[C:21](=[N:22][CH:23]=[CH:24][C:25]=3[O:28][C:29]3[CH:34]=[CH:33][C:32]([NH:35][C:36]([NH:38][C:39](=[O:48])[CH2:40][C:41]4[CH:46]=[CH:45][C:44]([F:47])=[CH:43][CH:42]=4)=[S:37])=[CH:31][C:30]=3[F:49])[CH:20]=2)=[CH:17][CH:18]=1)[CH2:8][CH2:9][O:10][CH3:11])(C)(C)C>C(O)(C(F)(F)F)=O>[F:49][C:30]1[CH:31]=[C:32]([NH:35][C:36]([NH:38][C:39](=[O:48])[CH2:40][C:41]2[CH:42]=[CH:43][C:44]([F:47])=[CH:45][CH:46]=2)=[S:37])[CH:33]=[CH:34][C:29]=1[O:28][C:25]1[CH:24]=[CH:23][N:22]=[C:21]2[CH:20]=[C:19]([C:16]3[CH:17]=[CH:18][C:13]([CH2:12][NH:7][CH2:8][CH2:9][O:10][CH3:11])=[CH:14][N:15]=3)[S:27][C:26]=12
Reactant: COCCN(Cc1ccc(-c2cc3nccc(Oc4ccc(NC(=S)NC(=O)Cc5ccc(F)cc5)cc4F)c3s2)nc1)C(=O)OC(C)(C)C
Solvent: O=C(O)C(F)(F)F
Product: COCCNCc1ccc(-c2cc3nccc(Oc4ccc(NC(=S)NC(=O)Cc5ccc(F)cc5)cc4F)c3s2)nc1
Temperature: 25 °C
Reaction time: 2 h
Yield: 62.6 %

Procedure:
To solid 14 (7.00 g, 9.72 mmol) in a 250 mL round-bottom flask was added TFA (20 mL). The addition was a little bit exothermic. The mixture was stirred at r.t. for 2 h then concentrated and co-evaporated with MTBE (2×100 mL) to obtain a solid that was triturated with MTBE (80 mL) for 2 h. The solid was collected by filtration, washed with MTBE (2×10 mL) and dried in vacuum for 1 h. The dry solid was partitioned between the mixture of DCM/MeOH: (9/1, 300 mL) and NaHCO3 (200 mL). The phases were separated. The organic phase was collected and the aqueous phase was extracted with DCM/MeOH: 9/1 (2×150 mL). Organic phases were combined, washed with brine (100 mL), dried over Na2SO4 and concentrated. The solid residue was triturated with EA (40 mL) for 1 h, collected by filtration, washed with EA (2×5 mL), dried in vacuum for 1 h to afford 15 as beige solid (3.77 g, 63% yield). MS (m/z): 620.6 (M+1).
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.[CH2:13]([OH:17])[CH2:14][C:15]#[CH:16]>C(N(CC)CC)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[OH:17][CH2:13][CH2:14][C:15]#[C:16][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1
Reactant: C#CCCO
Reactant: COC(=O)Cc1ccc(Br)cc1
Agent: [Pd]
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: CCN(CC)CC
Product: COC(=O)Cc1ccc(C#CCCO)cc1
Yield: 80.2 %

Procedure:
To a solution of methyl 4-bromophenylacetate (229 mg, 1.0 mmole) and 3-butyn-1-ol (151 μL, 2.0 mmole) in triethylamine (4.0 mL) was added cuprous bromide (18 mg, 0.12 mmole) and tetra(triphenylphosphine)palladium (46 mg, 0.04 mmole), and the mixture refluxed under a nitrogen atmosphere for 1 hr 20 min. The mixture was evaporated in vacuo and the residue partitioned with water and ether. The organic phase was washed with brine, dried over magnesium sulfate and concentrated in vacuo to an oil. Flash chromatography on silica gel in 7:3 hexane:ethyl acetate afforded the title compound (175 mg) as an oil NMR (CDCl3): δ 1.69 (s, 1H); 2.71 (t, 2H); 3.63 (s, 2H); 3.71 (s, 3H); 3.83 (t, 2H); 7.22 (d, 2H); 7.38 (d, 2H).
Reaction SMILES: [C:1]1([CH2:7][CH:8]=[CH:9][CH:10]2[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H][H]>C(O)C.[Pd]>[C:1]1([CH2:7][CH2:8][CH2:9][CH:10]2[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: C(=CC1CCCCCCCCCCC1)Cc1ccccc1
Reactant: [H][H]
Agent: [Pd]
Solvent: CCO
Product: c1ccc(CCCC2CCCCCCCCCCC2)cc1
Reaction time: 8 h

Procedure:
To 6.4 g (22.5 mmoles) of 1-(3-phenyl-1-propenyl)cyclododecane in 50 mL of ethanol is added 0.48 g of 10% palladium on carbon. The reaction mixture is subjected to hydrogen (50 psi) atmosphere using a Paar hydrogenerator and shaken overnight after which time no starting material is evident by TLC. The reaction mixture is filtered through Celite which is washed with additional ethanol. The filtrate is evaporated and the crude residue (5.8 g) is used directly for the next step: NMR (CDCl3) δ 1.2-1.4 (m, 10H), 1.6 (m, 2H), 2.55 (t, 2H, J=8 Hz), 7.2 (m, 5H).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([NH2:9])=[CH:5][CH:4]=1.[C:10](O)(=O)[CH3:11].[C:14]([BH3-])#N.[Na+].Cl>CO.C1COCC1.CC(C)=O>[CH:10]([NH:9][C:6]1[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=1)([CH3:11])[CH3:14]
Reactant: [BH3-]C#N
Reactant: CC(=O)O
Reactant: COc1ccc(N)cc1
Agent: Cl
Agent: [Na+]
Solvent: CO
Solvent: C1CCOC1
Solvent: CC(C)=O
Product: COc1ccc(NC(C)C)cc1
Temperature: 25 °C
Reaction time: 8 h

Procedure:
To a stirred solution of 4-methoxy-phenylamine (1.24 g) in methanol (15 mL) at ambient temperature was added successively, glacial acetic acid (415 mg), acetone (669 mg), and 1M sodium cyanoborohydride in THF (12.7 mL). The reaction mixture was stirred overnight at room temperature. The pH was adjusted to 2 with 6N HCl and stirred for 30 minutes after which time the excess sodium cyanoborohydride was completely quenched. The pH was then adjusted to 8.5 with 1N NaOH and the resultant solution extracted with diethyl ether (2×50 mL) and ethyl acetate (50 mL). The oganic extracts were combined, dried over sodium sulfate, filtered and concentrated under reduced pressure to give the title compound (1.42 g) as a yellow oil.
Reaction SMILES: C(=O)([O-])[O-].[K+].[K+].[I-].[K+].[NH:9]1[CH:13]=[CH:12][N:11]=[CH:10]1.Cl[CH2:15][C:16]1[CH:21]=[CH:20][C:19]([C:22]#[N:23])=[CH:18][CH:17]=1>CCOCC.CC(C)=O>[NH:9]1[CH:13]=[CH:12][N:11]=[C:10]1[CH2:15][C:16]1[CH:21]=[CH:20][C:19]([C:22]#[N:23])=[CH:18][CH:17]=1
Reactant: c1c[nH]cn1
Reactant: N#Cc1ccc(CCl)cc1
Agent: O=C([O-])[O-]
Agent: [I-]
Agent: [K+]
Solvent: CCOCC
Solvent: CC(C)=O
Product: N#Cc1ccc(Cc2ncc[nH]2)cc1
Reaction time: 26 h

Procedure:
To 48.0 L of acetone under nitrogen is added 4.326 Kg of potassium carbonate, 0.26 Kg of potassium iodide, 3.2 Kg of imidazole and 4.745 Kg of alpha-chloro-4-tolunitrile. The mixture is stirred at 45° under nitrogen for 26 hours. The reaction is cooled, filtered and the solvent is evaporated at reduced pressure. The residue is redissolved in 40 L of methylene chloride, washed with 40 L of water and twice with 10 L of water. The organic phase is dried over magnesium sulfate and evaporated to yield the crude product which is stirred with 6.4 L of ether for 2 hours. The solid is filtered, washed with 9 L of ether and dried at 40° and 20 mm Hg for 17 hours to yield 4-(1-imidazolylmethyl)-benzonitrile, the compound of Example 1.
Reaction SMILES: [C:1]1([S:7]([CH2:10][C:11](O)=O)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl:14][C:15]1[CH:22]=[CH:21][C:18](C=O)=[CH:17][CH:16]=1>>[C:1]1([S:7](/[CH:10]=[CH:11]/[C:18]2[CH:21]=[CH:22][C:15]([Cl:14])=[CH:16][CH:17]=2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: O=Cc1ccc(Cl)cc1
Reactant: O=C(O)CS(=O)(=O)c1ccccc1
Product: O=S(=O)(/C=C/c1ccc(Cl)cc1)c1ccccc1
Yield: 78 %

Procedure:
A solution of phenyl sulfonylacetic acid (0.01 mol) and 4-chlorobenzaldehyde (0.01 mol) was subjected to Procedure 1, Part B. The title compound was obtained in 78-80% yield.
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH3:10])[C:5]#[N:6].[Br:11]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:11][CH2:10][C:9]1[CH:8]=[CH:7][C:4]([C:5]#[N:6])=[CH:3][C:2]=1[F:1]
Reactant: O=C1CCC(=O)N1Br
Reactant: Cc1ccc(C#N)cc1F
Agent: CC(C)(C#N)N=NC(C)(C)C#N
Solvent: ClC(Cl)(Cl)Cl
Product: N#Cc1ccc(CBr)c(F)c1
Yield: 11.1 %

Procedure:
To a solution of 3-fluoro-4-methylbenzonitrile (5.0 g, 0.23 mol) in 100 mL of carbon tetrachloride was added N-bromosuccinimide (4.97 g, 0.28 mol) and AIBN (100 mg, 0.61 mmol) and the mixture was refluxed for six hours. The reaction was cooled and filtered. The filtrate was washed with water, dried over magnesium sulfate, filtered and the solvents were removed under vacuum to afford 5.44 g of the title compound as an off-white solid. 1H NMR indicated the presence of 20% starting material. 1H NMR (400 MHz, CDCl3) for the title compound: δ 7.54-7.30 (m, 3H), 4.83 (s, 2H).
Reaction SMILES: [CH3:1][N:2]1[CH:6]=[C:5]([N+:7]([O-:9])=[O:8])[C:4]([OH:10])=[C:3]1[C:11]([O:13][CH2:14][CH3:15])=[O:12].S(OC)(O[CH3:20])(=O)=O.C(=O)([O-])[O-].[K+].[K+]>CC(C)=O.C(Cl)Cl>[CH3:1][N:2]1[CH:6]=[C:5]([N+:7]([O-:9])=[O:8])[C:4]([O:10][CH3:20])=[C:3]1[C:11]([O:13][CH2:14][CH3:15])=[O:12]
Reactant: COS(=O)(=O)OC
Reactant: CCOC(=O)c1c(O)c([N+](=O)[O-])cn1C
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: ClCCl
Solvent: CC(C)=O
Product: CCOC(=O)c1c(OC)c([N+](=O)[O-])cn1C
Yield: 88.6 %

Procedure:
A mixture of ethyl 1-methyl-4-nitro-3-hydroxypyrrole-2-carboxylate (0.071 g, 0.3315 mmol), dimethyl sulfate (0.055 g, 0.436 mmol) and anhydrous potassium carbonate (0.5 g, 3.90 mmol) in dry acetone (20 mL) was refluxed under a nitrogen atmosphere for 22 h. Potassium carbonate was removed by filtration and the filtrate was evaporated under reduced pressure to afford an orange crystalline solid. Excess dimethyl sulfate was destroyed by treating the residue with aqueous ammonia (1 mL). Water (2 mL) was added and the residue was extracted with ether (30 mL). The combined ether extracts were washed with aqueous sodium hydroxide solution and water. Removal of ether under reduced pressure afforded a cream residue. The residue was dissolved in CH2Cl2 (25 mL), dried with anhydrous Na2SO41 filtered and evaporated under reduced pressure to yield a cream microcrystalline solid (0.067 g, 89%). Recrystallization from acetone/hexane afforded colorless needles, mp 145-147° C.; 1H NMR (300 MHZ, CDCl3) d 1.40 (t, J=7.2 Hz, 3H, CH3—CH2—), 3.90 (s, 3H, CH3—N—), 3.95 (s, 3H, CH3O—), 4.36 (q, J=7.0 Hz, 2H, CH3—CH2—), 7.47 (s, 1H, H-5); 13C NMR (100 MHZ, CDCl3) d 14.22, 38.92, 60.67, 63.02, 114.73, 125.76, 127.79, 146.18, 160.09; MS (EI, 70 eV) m/z (relative intensity) 229 (M+1, 3), 228 (M+, 30), 211 (12), 183 (12), 167 (20), 153 (25), 152 (100), 141 (7), 109 (12), 84 (8), 67 (6), 53 (31), 42 (17), Calcd for C9H12N2O5: 228.20. HRMS (M+H): Calcd for C9H13N2O5 [M+H+]: 229.0824, Found 229.0834. Anal. Calcd for C9H12N2O5: C, 47.37; H, 5.29; N, 12.27. Found. C, 47.44; H, 5.36; N, 12.28. TLC (ethyl acetate/Hexane, 1:3) Rf 0.23.
Reaction SMILES: [O:1]=[C:2]([C:6]1[CH:11]=[CH:10][C:9]([O:12][CH2:13][CH3:14])=[CH:8][CH:7]=1)[C:3]([OH:5])=[O:4].O.[C:16]1(C)[CH:21]=CC(S(O)(=O)=O)=C[CH:17]=1.C1(C)C=CC=CC=1.CCCO>O>[CH2:17]([O:4][C:3](=[O:5])[C:2]([C:6]1[CH:11]=[CH:10][C:9]([O:12][CH2:13][CH3:14])=[CH:8][CH:7]=1)=[O:1])[CH2:16][CH3:21]
Reactant: CCOc1ccc(C(=O)C(=O)O)cc1
Reactant: Cc1ccc(S(=O)(=O)O)cc1
Solvent: Cc1ccccc1
Solvent: O
Solvent: CCCO
Product: CCCOC(=O)C(=O)c1ccc(OCC)cc1

Procedure:
10.4 g (50 mmol) of α-oxo-4-ethoxyphenylacetic acid (Bandyopahyay et al., J. Ind. Chem. Soc. 66(4), 239, 1989) and 1.0 g of p-toluenesulfonic acid-monohydrate are refluxed into a mixture of 100 ml of toluene and 50 ml of N-propanol while in a water separator until no more water separates out. Then, it is concentrated by evaporation in a vacuum, the residue is dispersed between ethyl acetate and sodium bicarbonate solution, the organic phase is dried on magnesium sulfate, filtered and concentrated by evaporation.
Reaction SMILES: B(O)(O)[C:2]1[CH:3]=[CH:4][C:5]([CH3:8])=[CH:6][CH:7]=1.Br[C:12]1[S:13][C:14]([C:17]2[CH:22]=[CH:21][C:20]([CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])=[C:19]([F:28])[CH:18]=2)=[CH:15][CH:16]=1.C(=O)([O-])O.[Na+].C1(C)C=CC=CC=1>C(O)C.C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[F:28][C:19]1[CH:18]=[C:17]([C:14]2[S:13][C:12]([C:2]3[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=3)=[CH:16][CH:15]=2)[CH:22]=[CH:21][C:20]=1[CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]
Reactant: CCCCCc1ccc(-c2ccc(Br)s2)cc1F
Reactant: Cc1ccc(B(O)O)cc1
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: Cc1ccccc1
Solvent: O
Solvent: CCO
Product: CCCCCc1ccc(-c2ccc(-c3ccc(C)cc3)s2)cc1F
Temperature: 80 °C

Procedure:
A mixture of 3.54 g (26.0 mmol) of p-tolylboronic acid, 8.50 g (26.0 mmol) of 2-bromo-5-(3-fluoro-4-pentylphenyl)thiophene, 1.50 g (1.30 mmol) of tetrakis(triphenylphosphine)palladium(0) and 33 ml of 2 M sodium hydrogencarbonate solution in 80 ml of ethanol/toluene=3:2 is heated at 80° C. for 20 h. Toluene and water are added to the mixture, and the organic phase is separated off. The aqueous phase is extracted with toluene, and the combined organic phases are washed with sat. sodium chloride solution. The solution is dried using sodium sulfate and evaporated to dryness. The residue is purified by column chromatography (SiO2, toluene). The further purification is carried out by recrystallisation from ethanol and n-heptane. 2-(3-Fluoro-4-pentylphenyl)-5-p-tolylthiophene is obtained as a solid having an m.p. of 115° C.
Reaction SMILES: [C:1]1([C:7]#[C:8][C:9]2[CH:10]=[C:11]([C:23]([C:25]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=O)=O)[CH:12]=[C:13]([C:15]#[C:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[CH:14]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:33]1([CH2:39][C:40]([CH2:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)=[O:41])[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.C(O)CC.[OH-].C([N+](C)(C)C)C1C=CC=CC=1>C1(C)C=CC=CC=1>[C:1]1([C:7]#[C:8][C:9]2[CH:14]=[C:13]([C:15]3[C:16]([C:17]4[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=4)=[C:42]([C:43]4[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=4)[C:40](=[O:41])[C:39]=3[C:33]3[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=3)[CH:12]=[C:11]([C:23]#[C:25][C:27]3[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=3)[CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: O=C(C(=O)c1cc(C#Cc2ccccc2)cc(C#Cc2ccccc2)c1)c1ccccc1
Reactant: O=C(Cc1ccccc1)Cc1ccccc1
Agent: C[N+](C)(C)Cc1ccccc1
Agent: [OH-]
Solvent: Cc1ccccc1
Solvent: CCCO
Product: O=C1C(c2ccccc2)=C(c2ccccc2)C(c2cc(C#Cc3ccccc3)cc(C#Cc3ccccc3)c2)=C1c1ccccc1
Temperature: 24 °C
Yield: 76.4 %

Procedure:
A portion of the 3,5-bis(phenylethynyl)benzil (10.87 grams, 0.0265 mole), 1,3-diphenylacetone (5.90 grams, 0.0281 mole), anhydrous 1-propanol (300 milliliters) and anhydrous toluene (17 milliliters), both of which had been sparged with dry nitrogen, were added under a dry nitrogen atmosphere to a predried 500 milliliter glass three neck round bottom reactor containing a predried magnetic stirring bar. The reactor was additionally outfitted with a fan cooled spiral condenser and a thermometer with thermostatically controlled heating mantle. Stirring and heating commenced, and once a refluxing clear light yellow colored solution formed, benzyltrimethylammonium hydroxide (40 percent in methanol) (0.91 gram) was added, immediately inducing a dark red color. After maintaining the reflux for 20 minutes, HPLC analysis indicated that full conversion of the 3,5-bis[phenylethynyl)benzil reactant had been achieved. After a cumulative 30 minutes of reaction, the heating mantle was removed from the reactor, and the stirred contents were maintained at 24° C. for the next 16 hours. The product was recovered via filtration through a medium flitted glass funnel. The product cake on the funnel was washed with two portions (50 milliliters) of 1-propanol, then dried in a vacuum oven to provide 11.84 grams (76.4 percent isolated yield) of 4-(3,5-bis(phenylethynyl)phenyl)-2,3,5-triphenylcyclopentadienone (unsymmetrically substituted 3,5-AAB monomer) as a dark red purple colored crystalline product. HPLC analysis revealed the presence of the desired product at 100 area percent. The product's identity was confirmed by 1H NMR and EI MS analysis.
Reaction SMILES: [CH3:1][C:2]([C:5]1[CH:6]=[C:7]([S:16][CH:17]([CH2:21][CH2:22][CH3:23])[C:18](O)=[O:19])[CH:8]=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:10]=1[OH:11])([CH3:4])[CH3:3].[CH2:24]([N:31]1[CH2:36][CH2:35][NH:34][CH2:33][CH2:32]1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>>[CH3:3][C:2]([C:5]1[CH:6]=[C:7]([S:16][CH:17]([CH2:21][CH2:22][CH3:23])[C:18]([N:34]2[CH2:35][CH2:36][N:31]([CH2:24][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)[CH2:32][CH2:33]2)=[O:19])[CH:8]=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:10]=1[OH:11])([CH3:1])[CH3:4]
Reactant: c1ccc(CN2CCNCC2)cc1
Reactant: CCCC(Sc1cc(C(C)(C)C)c(O)c(C(C)(C)C)c1)C(=O)O
Product: CCCC(Sc1cc(C(C)(C)C)c(O)c(C(C)(C)C)c1)C(=O)N1CCN(Cc2ccccc2)CC1

Procedure:
The title compound of Example 44 is converted to its acid chloride and is reacted with N-benzylpiperazine by the method of Example 42 to give the title compound.
Reaction SMILES: [C:1]1([C:7]2[C:12]([OH:13])=[CH:11][CH:10]=[CH:9][N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:14]([Br:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>C(#N)C>[Br-:21].[C:15]1([CH2:14][N+:8]2[CH:9]=[CH:10][CH:11]=[C:12]([OH:13])[C:7]=2[C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: BrCc1ccccc1
Reactant: Oc1cccnc1-c1ccccc1
Solvent: CC#N
Product: Oc1ccc[n+](Cc2ccccc2)c1-c1ccccc1
Product: [Br-]
Temperature: 25 °C
Yield: 80.5 %

Procedure:
To a flame dried round bottom flask equipped with a nitrogen inlet and a condenser was introduced 1.3 gm. (7.59 mmol) 2-phenyl-3-hydroxypyridine, 3.25 gm. 2.26 ml (18.96 mmol) benzylbromide. The contents were dissolved in 30 ml of acetonitrile and the reaction mixture was heated under reflux for a period of 18 hours. The mixture was allowed to cool to room temperature and evaporated in vacuo. The residue was taken up in chloroform followed by treatment with ether to afford a solid precipitate. Upon filtration there was obtained 2.09 gm (81%) of 1-phenylmethyl-2-phenyl-3-hydroxypyridinium bromide. 1H NMR (CDCl3, 400 MHz) δ 8.70 (d, 1H), 8.25 (d, 1H), 7.50 (m, 2H), 7.40 (m, 2H), 7.30–7.20 (m, 5H), 6.90 (d, 2H), 5.60 (s, 2H) ppm. Mass spectrum APCI m/z 262.
Reaction SMILES: [NH2:1][C:2]1[CH:30]=[CH:29][C:5]2[NH:6][C:7]([C:12]3[C:13](=[O:28])[N:14]([CH2:23][CH2:24][CH:25]([CH3:27])[CH3:26])[C:15]4[C:20]([C:21]=3[OH:22])=[CH:19][CH:18]=[CH:17][N:16]=4)=[N:8][S:9](=[O:11])(=[O:10])[C:4]=2[CH:3]=1.[S:31]1[CH:35]=[CH:34][CH:33]=[C:32]1[S:36](Cl)(=[O:38])=[O:37]>N1C=CC=CC=1>[OH:22][C:21]1[C:20]2[C:15](=[N:16][CH:17]=[CH:18][CH:19]=2)[N:14]([CH2:23][CH2:24][CH:25]([CH3:27])[CH3:26])[C:13](=[O:28])[C:12]=1[C:7]1[NH:6][C:5]2[CH:29]=[CH:30][C:2]([NH:1][S:36]([C:32]3[S:31][CH:35]=[CH:34][CH:33]=3)(=[O:38])=[O:37])=[CH:3][C:4]=2[S:9](=[O:11])(=[O:10])[N:8]=1
Reactant: CC(C)CCn1c(=O)c(C2=NS(=O)(=O)c3cc(N)ccc3N2)c(O)c2cccnc21
Reactant: O=S(=O)(Cl)c1cccs1
Solvent: c1ccncc1
Product: CC(C)CCn1c(=O)c(C2=NS(=O)(=O)c3cc(NS(=O)(=O)c4cccs4)ccc3N2)c(O)c2cccnc21
Temperature: 120 °C
Yield: 34.9 %

Procedure:
To the product of Example 205 (21.5 mg, 0.05 mmol) in pyridine (1 mL) was added 2-thiophenesulfonyl chloride (44 mg, 0.24 mmol). The reaction mixture was heated in a microwave reactor at 120° C. for 120 minutes. The reaction was cooled to 25° C. and concentrated under reduced pressure. The residue was triturated with water (1 mL), filtered, and washed with hexane:ethyl acetate (1:1). The crude product was chromatographed on silica gel eluting with 199:1 dichloromethane:methanol to give the title compound (10 mg, 35%). 1H NMR (300 MHz, DMSO-d6): δ 0.97 (d, J=6.25 Hz, 6 H) 1.55 (m, 2 H) 1.66 (m, 1 H) 4.46 (t, J=7.84 Hz, 2 H) 7.16 (dd, J=5.13 Hz, 3.66 Hz, 1 H) 7.48 (m, 2 H) 7.53 (d, J=2.21 Hz, 1 H) 7.56 (d, J=2.55 Hz, 1 H) 7.61 (dd, J=3.68, 1.47 Hz, 1 H) 7.68 (d, J=8.82 Hz, 1 H) 7.96 (dd, J=5.13 Hz, 1.47 Hz, 1 H) 8.53 (dd, J=8.09, 1.84 Hz, 1 H) 8.87 (dd, J=4.78, 1.84 Hz, 1 H) 10.98 (s, 1 H) 14.10 (s, 1 H). MS (ESI−) m/z 572 (M−H)−.
Reaction SMILES: [CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:15]3[N:16]=[CH:17][N:18]=[C:19]([NH:20][CH:21]4[CH2:26][CH2:25][NH:24][CH2:23][CH2:22]4)[C:14]=3[S:13][CH:12]=2)=[CH:7][CH:6]=1)(=[O:4])=[O:3].Cl[C:28]1[N:33]=[CH:32][C:31]([CH2:34][CH3:35])=[CH:30][N:29]=1>>[CH2:34]([C:31]1[CH:30]=[N:29][C:28]([N:24]2[CH2:25][CH2:26][CH:21]([NH:20][C:19]3[C:14]4[S:13][CH:12]=[C:11]([C:8]5[CH:9]=[CH:10][C:5]([S:2]([CH3:1])(=[O:3])=[O:4])=[CH:6][CH:7]=5)[C:15]=4[N:16]=[CH:17][N:18]=3)[CH2:22][CH2:23]2)=[N:33][CH:32]=1)[CH3:35]
Reactant: CCc1cnc(Cl)nc1
Reactant: CS(=O)(=O)c1ccc(-c2csc3c(NC4CCNCC4)ncnc23)cc1
Product: CCc1cnc(N2CCC(Nc3ncnc4c(-c5ccc(S(C)(=O)=O)cc5)csc34)CC2)nc1

Procedure:
The procedure of intermediate 10 was repeated using 7-(4-methanesulfonyl-phenyl)-N-(piperidin-4-yl)thieno[3,2-d]pyrimidin-4-amine obtained in Example 110 and 2-chloro-5-ethylpyrimidine to obtain the title compound.
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-])=O.CC1(C)C(C)(C)OB([C:21]2[S:22][C:23](B3OC(C)(C)C(C)(C)O3)=[CH:24][CH:25]=2)O1.Br[C:37]1[CH:38]=[N:39][CH:40]=[C:41]([F:43])[CH:42]=1>>[F:43][C:41]1[CH:42]=[C:37]([C:23]2[S:22][C:21]3[C:2]4[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=4[NH:10][C:25]=3[CH:24]=2)[CH:38]=[N:39][CH:40]=1
Reactant: COc1ccc(Br)c([N+](=O)[O-])c1
Reactant: CC1(C)OB(c2ccc(B3OC(C)(C)C(C)(C)O3)s2)OC1(C)C
Reactant: Fc1cncc(Br)c1
Product: COc1ccc2c(c1)[nH]c1cc(-c3cncc(F)c3)sc12
Yield: 6.7 %

Procedure:
Compound 2-(5-fluoropyridin-3-yl)-6-methoxy-4H-thieno[3,2-b]indole (W309) was synthesized using the same procedure for the preparation of W270 from 1-bromo-4-methoxy-2-nitrobenzene (104 mg, 0.45 mmol), 2,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene (168 mg, 0.5 mmol), and 3-bromo-5-fluoropyridine (105 mg, 0.6 mmol), as a yellow solid (10 mg, total yield 6.7%). 1H NMR (400 MHz, acetone-d6) δ 10.36 (brs, 1 H), 8.76 (s, 1 H), 8.33 (s, 1 H), 7.83 (m, 2 H), 7.77 (m, 1 H), 7.62-7.60 (m, 1 H), 7.02 (s, 1 H), 6.80 (d, J=8.8 Hz, 1 H), 3.86 (s, 3 H); MS (ESI) m/z 299 (M+H+).