Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH:1]1([C:4]2[CH:9]=[CH:8][N:7]=[CH:6][C:5]=2[NH:10]C(=O)OC(C)(C)C)[CH2:3][CH2:2]1.CO.C(Cl)Cl>Cl.O1CCOCC1>[CH:1]1([C:4]2[CH:9]=[CH:8][N:7]=[CH:6][C:5]=2[NH2:10])[CH2:3][CH2:2]1
Reactant: CC(C)(C)OC(=O)Nc1cnccc1C1CC1
Agent: Cl
Solvent: ClCCl
Solvent: C1COCCO1
Solvent: CO
Product: Nc1cnccc1C1CC1
Temperature: 25 °C
Reaction time: 1 h
Yield: 144.4 %

Procedure:
Tert-butyl 4-cyclopropylpyridin-3-ylcarbamate (393 mg, 1.677 mmol) was dissolved in 4 M HCl in dioxane (30 mL), and stirred at room temperature for 1 hour, the reaction rapidly becoming a white heterogeneous mixture. TLC (SiO2, 5% methanol/CH2Cl2) showed reaction complete after 1 hour. The solvent was removed by rotary evaporation, the residue was triturated with diethyl ether and vacuum filtered to collect the solid, and the solid was dried in a vacuum oven at 50° C. for 1 hour to afford the product as a beige solid (325 mg).
Reaction SMILES: P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:2].[NH2:15][C:16]1[C:17](=O)[NH:18][C:19](=[O:26])[N:20]([CH2:23][CH2:24][CH3:25])[C:21]=1[NH2:22]>N1C=CC=CC=1>[NH2:15][C:16]1[C:17]([SH:2])=[N:18][C:19](=[O:26])[N:20]([CH2:23][CH2:24][CH3:25])[C:21]=1[NH2:22]
Reactant: S=P12SP3(=S)SP(=S)(S1)SP(=S)(S2)S3
Reactant: CCCn1c(N)c(N)c(=O)[nH]c1=O
Solvent: c1ccncc1
Product: CCCn1c(N)c(N)c(S)nc1=O
Temperature: 100 °C
Yield: 69.4 %

Procedure:
Phosphorus pentasulfide (27.1 g, 122 mmol, 1.5 equivalents) was suspended in pyridine (150 mL) and the mixture was heated to 100° C. To the suspension was gradually added 5,6-diamino-1-propyluracil (15.0 g, 81.3 mmol), which was obtained by the method described in Journal of Medicinal Chemistry (J. Med. Chem.), 32 (6), p. 1231, 1989, with heating and stirring, and then the mixture was stirred for 7 hours. After the reaction solution was cooled on ice, the deposited solid was separated by filtration using a filtration aid and washed with pyridine. The filtrate was concentrated, to the residue was added water (90 mL), and the mixture was stirred under reflux with heating for about 40 minutes until intense foaming ceased. The reaction mixture was cooled on ice and then further stirred overnight at room temperature. The deposited yellowish green ocher solid was collected by filtration, sufficiently washed with water and dried under reduced pressure to obtain 5,6-diamino-1,2-dihydro-4-mercapto-2-oxo-1-propylpyrimidine (Compound B4, 11.3 g, 69%). Compound B4 (10.0 g, 50.0 mmol) was suspended in 1,4-dioxane (200 mL) and water (100 mL), to the suspension were added cyclohexanecarboxylic acid (8.06 mL, 65.0 mmol, 1.3 equivalents) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (16.3 g, 85.0 mmol, 1.7 equivalents) at room temperature, and then the mixture was stirred overnight. To the reaction mixture was added 2 mol/L aqueous sodium hydroxide (100 mL), and the mixture was stirred with heating for 2.5 hours. The reaction mixture was cooled on an ice bath, adjusted to pH 6 with 4 mol/L hydrochloric acid and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was dissolved in 0.5 mol/L aqueous sodium hydroxide (150 mL), and to the solution was added methyl iodide (4.70 mL, 75.0 mmol, 1.5 equivalents) and the mixture was stirred overnight at room temperature. The reaction mixture was cooled on an ice bath, adjusted to pH 6.5 with 4 mol/L aqueous hydrochloric acid and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated. Then, the residue was purified by silica gel column chromatography (chloroform:methanol=100:0 to 96:4) to obtain the title compound (11.8 g, 78%).
Reaction SMILES: [CH3:1][C:2]1[C:7]([Cl:8])=[C:6]([O:9][C:10]2[CH:15]=[CH:14][C:13]([C:16](=[O:24])[C:17]3[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][CH:18]=3)=[CH:12][CH:11]=2)[C:5]([CH3:25])=[CH:4][C:3]=1[N+:26]([O-])=O.C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[Pt].C(OCC)(=O)C.CCCCCC>[CH3:1][C:2]1[C:7]([Cl:8])=[C:6]([O:9][C:10]2[CH:11]=[CH:12][C:13]([C:16](=[O:24])[C:17]3[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][CH:18]=3)=[CH:14][CH:15]=2)[C:5]([CH3:25])=[CH:4][C:3]=1[NH2:26]
Reactant: Cc1cc([N+](=O)[O-])c(C)c(Cl)c1Oc1ccc(C(=O)c2ccc(Cl)cc2)cc1
Agent: [Pt]
Solvent: ClC(Cl)Cl
Solvent: CCCCCC
Solvent: CCOC(C)=O
Product: Cc1cc(N)c(C)c(Cl)c1Oc1ccc(C(=O)c2ccc(Cl)cc2)cc1

Procedure:
A mixture of 2,5-dimethyl-3-chloro-4-(4-[4-chlorobenzoyl]phenoxy)nitrobenzene (5.95 g, 14 mmol), toluene (160 mL), and 5% platinum on carbon (0.65 g) was subjected to hydrogenation at the pressure ≤24 psi. After 8 h one reaction was found to be partly completed. Additional catalyst (0.2 g of 5% pt/c) was added. The reaction was close to completion by the end of additional 4 h. The mixture was filtered and the filtrate was concentrated to give an amber foam. This foam was dissolved in an ethyl acetate (5 mL) and hexane (10 mL). Solid formed after the addition of seed crystal and vigorous stirring. A tan powder was obtained after filtration (3.93 g); mp 113°-122°. In a similar experiment a buff powder was obtained; IR (CHCl3) 3020, 2405, 1650, 1600 cm-1 ; NMR (CDCl3) δ 6.6-7.8 (M, 8H), 6.5 (S, 1H) 3.5 (br, 2H), 2.2 (S, 3H), 2.1 (S, 3H)
Reaction SMILES: Cl[C:2]1[N:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][CH:3]=1.C([O-])([O-])=O.[Cs+].[Cs+].[F:18][CH:19]1[CH2:22][NH:21][CH2:20]1>CN(C=O)C.CCOC(C)=O>[F:18][CH:19]1[CH2:22][N:21]([C:2]2[N:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][CH:3]=2)[CH2:20]1
Reactant: Cc1nc(Cl)ccc1[N+](=O)[O-]
Reactant: FC1CNC1
Agent: O=C([O-])[O-]
Agent: [Cs+]
Solvent: CN(C)C=O
Solvent: CCOC(C)=O
Product: Cc1nc(N2CC(F)C2)ccc1[N+](=O)[O-]
Temperature: 80 °C
Yield: 98 %

Procedure:
To a solution of 6-chloro-2-methyl-3-nitropyridine (0.5 g, 2.9 mmol) in DMF (5 mL) was added Cs2CO3 (1.9 g, 5.8 mmol) followed 3-fluoroazetidine (0.64 g, 5.8 mmol) and the reaction mixture was heated for 2 h at 80° C. The reaction mixture was then diluted with EtOAc and the organic layer was washed with saturated aqueous sodium bicarbonate solution. The organic layer was then dried over sodium sulphate and concentrated. The crude material obtained was purified by column chromatography (silica: 100-200 mesh, MeOH:DCM 2-3%) to afford the title compound (0.6 g, 92%). LCMS (ES+) 211.95 (M+H)+, RT 2.33 minutes (method 1).
Reaction SMILES: Br[C:2]1[C:7](=[O:8])[C:6]([O:9][CH3:10])=[CH:5][N:4]([C:11]2[C:24]([F:25])=[CH:23][C:14]3[O:15][C:16]([F:22])([F:21])[C:17]([F:20])([F:19])[O:18][C:13]=3[CH:12]=2)[N:3]=1.[C:26]1([N:32]2[C:36](B3OC(C)(C)C(C)(C)O3)=[CH:35][CH:34]=[N:33]2)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C([O-])([O-])=O.[K+].[K+]>C1(C)C=CC=CC=1.O.[Cl-].[Na+].O.C([O-])(O)=O.[Na+]>[CH3:10][O:9][C:6]1[C:7](=[O:8])[C:2]([C:36]2[N:32]([C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[N:33]=[CH:34][CH:35]=2)=[N:3][N:4]([C:11]2[C:24]([F:25])=[CH:23][C:14]3[O:15][C:16]([F:22])([F:21])[C:17]([F:20])([F:19])[O:18][C:13]=3[CH:12]=2)[CH:5]=1
Reactant: CC1(C)OB(c2ccnn2-c2ccccc2)OC1(C)C
Reactant: COc1cn(-c2cc3c(cc2F)OC(F)(F)C(F)(F)O3)nc(Br)c1=O
Agent: O=C([O-])O
Agent: O=C([O-])[O-]
Agent: [Cl-]
Solvent: O
Solvent: Cc1ccccc1
Product: COc1cn(-c2cc3c(cc2F)OC(F)(F)C(F)(F)O3)nc(-c2ccnn2-c2ccccc2)c1=O
Yield: 65.4 %

Procedure:
A mixture of 3-bromo-5-methoxy-1-(2,2,3,3,7-pentafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)pyridazin-4(1H)-one (200 mg, 0.466 mmol), 1-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (189 mg, 0.699 mmol), K2CO3 (129 mg, 0.932 mmol) and PdCl2{P(t-Bu)2(Ph-p-NMe2)}2 (16.5 mg, 0.0233 mmol) in toluene (2.3 mL) and water (0.23 mL) was heated to reflux for 20 h under Ar. The mixture was diluted with water, brine and saturated NaHCO3 aqueous solution, extracted with AcOEt, dried over Na2SO4, filtered, concentrated in vacuo, purified by column chromatography on basic silica gel (hexane/AcOEt=50/50 to 0/100) and recrystallized with AcOEt/hexane to yield the title compound (150 mg, 66% yield) as a white solid: mp 192-194° C. 1H NMR (DMSO-d6, 300 MHz): δ ppm 3.76 (3H, s), 7.00 (1H, d, J=1.9 Hz), 7.28-7.48 (6H, m), 7.79 (1H, d, J=1.9 Hz), 7.93 (1H, d, J=10.5 Hz), 8.51 (1H, d, J=1.9 Hz). Anal. Calcd for C22H13F5N4O4: C, 53.67; H, 2.66; N, 11.38. Found: C, 53.73; H, 2.72; N, 11.33.
Reaction SMILES: [CH3:1][C:2]([C:4]1[CH:9]=[CH:8][C:7]([I:10])=[CH:6][CH:5]=1)=O.Cl.[CH3:12][O:13][NH2:14].C(N(CC)CC)C>CO>[CH3:12][O:13][N:14]=[C:2]([C:4]1[CH:9]=[CH:8][C:7]([I:10])=[CH:6][CH:5]=1)[CH3:1]
Reactant: CC(=O)c1ccc(I)cc1
Reactant: CON
Agent: Cl
Solvent: CCN(CC)CC
Solvent: CO
Product: CON=C(C)c1ccc(I)cc1
Temperature: 25 °C
Reaction time: 4 h
Yield: 97 %

Procedure:
To a stirred solution of 4-iodo acetophenone (2.0 g, 8.13 mmol) in methanol (25 ml), O-methyl hydroxyl amine hydrochloride (0.7 g, 8.94 mmole) was added followed by triethyl amine (0.904 g, 8.94 mmol). The reaction mixture was stirred at ambient temperature for 4 hours. Reaction mixture was concentrated under vacuum, residual mass was diluted with water (50 ml) and aq. layer was extracted with ethyl acetate (3×30 ml). Organic layer was washed with water (2×30 ml) followed by brine solution, dried over anhydrous sodium sulfate and evaporated to obtain 2.17 g (97% of theory) of 1-(4-iodo-phenyl)-ethanone O-methyl-oxime.
Reaction SMILES: C(OC(=O)[NH:7][CH:8]1[CH2:13][CH2:12][N:11]([C:14]2[CH:15]=[CH:16][CH:17]=[C:18]3[C:23]=2[N:22]=[C:21]([N:24]2[C:28]4[CH:29]=[CH:30][C:31]([OH:33])=[CH:32][C:27]=4[N:26]=[CH:25]2)[CH:20]=[CH:19]3)[CH2:10][CH2:9]1)(C)(C)C.C([O-])([O-])=O.[Cs+].[Cs+].[Br-].[CH:42]1([CH3:45])[CH2:44][CH2:43]1>CN(C=O)C.C(O)(C(F)(F)F)=O>[CH:42]1([CH2:45][O:33][C:31]2[CH:30]=[CH:29][C:28]3[N:24]([C:21]4[CH:20]=[CH:19][C:18]5[C:23](=[C:14]([N:11]6[CH2:12][CH2:13][CH:8]([NH2:7])[CH2:9][CH2:10]6)[CH:15]=[CH:16][CH:17]=5)[N:22]=4)[CH:25]=[N:26][C:27]=3[CH:32]=2)[CH2:44][CH2:43]1
Reactant: CC(C)(C)OC(=O)NC1CCN(c2cccc3ccc(-n4cnc5cc(O)ccc54)nc23)CC1
Reactant: CC1CC1
Agent: O=C([O-])[O-]
Agent: [Br-]
Agent: [Cs+]
Solvent: O=C(O)C(F)(F)F
Solvent: CN(C)C=O
Product: NC1CCN(c2cccc3ccc(-n4cnc5cc(OCC6CC6)ccc54)nc23)CC1
Temperature: 65 °C
Reaction time: 4 h

Procedure:
{1-[2-(5-Hydroxy-benzoimidazol-1-yl)-quinolin-8-yl]-piperidin-4-yl}-carbamic acid tert-butyl ester H (200 mg, 0.435 mmol) was dissolved in 1.5 mL of anhydrous DMF under an atmosphere of dry N2. To this solution was added Cs2CO3 (170 mg, 0.520 mmol) followed by cyclopropyl methane bromide (46 mL, 0.48 mMol). The reaction mixture was subsequently heated to 65° C. and stirred at this temperature for 4 hours. The reaction mixture was then cooled to ambient temperature and partitioned between EtOAc and water. The EtOAc layer was washed 4 more times with water and then with brine. The EtOAc was then dried over Na2SO4, filtered and concentrated under vacuum and the resulting green oil was chromatographed on flash silica gel eluting with MeOH/dichloromethane (DCM) (2:98) to give the a green oil. The oil was dissolved in 1.5 mL of TFA under an atmosphere of dry N2. The reaction mixture was stirred at ambient temperature for 10 minutes after which time it was concentrated under vacuum and the resulting residue was partitioned between DCM and aqueous 0.1 N NaOH. The DCM layer was then washed with basic brine (pH =10), dried over Na2SO4, filtered and concentrated under vacuum to give 118 mg 1-[2-(5-Cyclopropylmethoxy-benzoimidazol-1-yl)-quinolin-8-yl]-piperidin-4-ylamine as a yellow solid. C.I. m/z 414 [M+1]; 1H NMR (CDCl3) δ 8.63 (s, 1 H), 8.37 (d, J=8.9 Hz, 1 H), 8.27 (d, J=8.7 Hz, 1 H), 7.65 (d, J=8.7 Hz, 1 H), 7.44 (m, 2 H), 7.30 (d, J=2.5 Hz, 1 H), 7.24 (m, 1 H), 7.09 (dd, J=2.5, 8.9 Hz, 1 H), 3.87 (m, 4 H), 2.87 (m, 3 H), 2.03 (m, 2 H), 1.81 (m, 2 H), 1.56 (brs, 2 H), 1.32 (m, 1 H), 0.66 (m, 2 H), 0.39 (m, 2 H).
Reaction SMILES: [CH3:1][N:2]([CH3:15])[CH2:3][CH2:4][N:5]1[C:13]2[C:8](=[CH:9][CH:10]=[C:11]([NH2:14])[CH:12]=2)[CH:7]=[N:6]1.[CH2:16]([O:23][C:24]1[CH:29]=[CH:28][C:27]([CH2:30][C:31](O)=[O:32])=[CH:26][CH:25]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.Cl.C(N=C=NC(C)(C)CC)C.ON1C2C=CC=CC=2N=N1.CN1CCOCC1>CN(C=O)C>[CH2:16]([O:23][C:24]1[CH:25]=[CH:26][C:27]([CH2:30][C:31]([NH:14][C:11]2[CH:12]=[C:13]3[C:8]([CH:7]=[N:6][N:5]3[CH2:4][CH2:3][N:2]([CH3:15])[CH3:1])=[CH:9][CH:10]=2)=[O:32])=[CH:28][CH:29]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1
Reactant: CN(C)CCn1ncc2ccc(N)cc21
Reactant: O=C(O)Cc1ccc(OCc2ccccc2)cc1
Agent: CCN=C=NC(C)(C)CC
Agent: Cl
Agent: On1nnc2ccccc21
Solvent: CN(C)C=O
Solvent: CN1CCOCC1
Product: CN(C)CCn1ncc2ccc(NC(=O)Cc3ccc(OCc4ccccc4)cc3)cc21
Temperature: 25 °C
Reaction time: 6 h
Yield: 95 %

Procedure:
A mixture of 1-(2-dimethylamino-ethyl)-1H-indazol-6-ylamine (484 mg, 2 mmol), 4-benzyloxy-phenylacetic acid (200 mg, 2 mmol), ethyldimethylpropylcarbodiimide hydrochloride (460 mg, 2.4 mmol), N-hydroxybenzotriazole (324 mg, 2.4 mmol), and N-methyl morpholine (513 mg, 4.8 mmol) in DMF (15 mL) was stirred at room temperature for 6 hours and concentrated under reduced pressure The residue was purified by flash chromatography (Silica gel, ethyl acetate/triethylamine, 30/1) to provide the title compound as a pale yellow solid (95%). 1H NMR (300 MHz, DMSO-d6) ppm 2.15 (s, 6H), 2.66 (t, J=6.44, 2H), 3.60 (s, 2H), 4.35 (t, J=6.44, 2H), 5.09 (s, 2H), 6.98 (d, J=8.82, 2H), 7.14 (m, 1H), 7.25–7.45 (m, 6H), 7.65 (m, 1H), 7.94 (m, 1H), 7.94 (s, 1H), 7.95 (s, 1H), 8.12 (s, 1H); MS (DCI/NH3) m/z 429 [M+H]+.
Reaction SMILES: B(O)O.Br[C:5]1[N:12]=[CH:11][CH:10]=[CH:9][C:6]=1[CH:7]=[O:8].[O:13]1[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[CH:15]=[C:14]1B(O)O>>[O:13]1[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[CH:15]=[C:14]1[C:5]1[N:12]=[CH:11][CH:10]=[CH:9][C:6]=1[CH:7]=[O:8]
Reactant: OB(O)c1cc2ccccc2o1
Reactant: O=Cc1cccnc1Br
Agent: OBO
Product: O=Cc1cccnc1-c1cc2ccccc2o1

Procedure:
2-(benzofuran-2-yl)nicotinaldehyde was prepared using the general boronic acid coupling procedure for 2-bromonicotinaldehyde and benzofuran-2-ylboronic acid (72 mg, 120.1 mg theoretical, 60%). LC-MS m/z 224.2 (M+1).
Reaction SMILES: Cl.[C:2]1([C:8]([CH:10]2[CH2:15][CH2:14][NH:13][CH2:12][CH2:11]2)=[O:9])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:16][C:17](OC(C)=O)=[O:18]>C(Cl)Cl>[C:8]([CH:10]1[CH2:15][CH2:14][N:13]([C:17](=[O:18])[CH3:16])[CH2:12][CH2:11]1)(=[O:9])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: O=C(c1ccccc1)C1CCNCC1
Reactant: CC(=O)OC(C)=O
Agent: Cl
Solvent: ClCCl
Product: CC(=O)N1CCC(C(=O)c2ccccc2)CC1
Temperature: 25 °C
Reaction time: 8 h

Procedure:
A mixture of phenyl(piperidin-4-yl)methanone hydrochloride (743 mg, 3.29 mmol, Apollo Scientific) in DCM (13.2 mL) and TEA (1.10 mL, 7.90 mmol) was treated with Ac2O (0.373 mL, 3.95 mmol) dropwise over 1 min on an ice bath under argon, and the resulting translucent mixture was immediately removed from the ice bath and stirred at room temperature overnight. The reaction was then partitioned with 1 M HCl (1×8 mL) and 1 M NaOH (1×8 mL), and the organic layer was dried (Na2SO4), filtered, and concentrated to provide the title compound as a translucent beige oil that crystallized upon standing.
Reaction SMILES: [F:1][C:2]1[C:3]2[C:16]([C:17]([F:28])=[C:18]3[C:23]=1[C:22](F)=[C:21](F)[C:20](F)=[C:19]3F)=[C:15]([F:29])[C:14]1[C:5](=[C:6]([F:35])[C:7]3[C:12]([C:13]=1[F:30])=[C:11](F)[C:10](F)=[C:9](F)[C:8]=3F)[C:4]=2[F:36].FC1C2C(F)(F)C3C(F)(F)C4C(F)(F)C5C(=C(F)C(F)=C(F)C=5F)C(F)(F)C=4C(F)(F)C=3C(F)(F)C=2C(F)=C(F)C=1F>>[F:1][C:2]1[C:3]2[C:16](=[C:15]([F:29])[C:14]3[C:5]([C:4]=2[F:36])=[C:6]([F:35])[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[C:13]=3[F:30])[C:17]([F:28])=[C:18]2[C:23]=1[CH:22]=[CH:21][CH:20]=[CH:19]2
Reactant: Fc1c(F)c(F)c2c(F)c3c(F)c4c(F)c5c(F)c(F)c(F)c(F)c5c(F)c4c(F)c3c(F)c2c1F
Agent: Fc1c(F)c(F)c2c(c1F)C(F)(F)C1=C(C(F)(F)C3=C(C1(F)F)C(F)(F)c1c(F)c(F)c(F)c(F)c1C3(F)F)C2(F)F
Product: Fc1c2ccccc2c(F)c2c(F)c3c(F)c4ccccc4c(F)c3c(F)c12

Procedure:
For example, tetradecafluoropentacene (9) is obtained by reacting 1,2,3,4,5,5,6,6,7,7,8,9,10,11,12,12,13,13,14,14-eicosafluoro-5,6,7,12,13,14-hexahydropentacene (7) with a reducing agent (scheme 15). In addition, 5,6,7,12,13,14-hexafluoropentacene (10) is obtained by reacting 5,5,6,7,7,12,12,13,14,14-decafluoro-5,7,12,14-tetrahydropentacene (8) with a reducing agent (scheme 16).
Reaction SMILES: [N+:1]([C:4]1[C:5]([C:10]2[CH:15]=[CH:14][C:13]([CH:16]=[CH2:17])=[CH:12][CH:11]=2)=[N:6][CH:7]=[CH:8][CH:9]=1)([O-])=O.[CH3:18][C:19]([Mg]Br)=[CH:20][CH3:21].[Cl-].[NH4+]>O1CCCC1>[CH3:18][C:19]1[NH:1][C:4]2=[C:5]([C:10]3[CH:15]=[CH:14][C:13]([CH:16]=[CH2:17])=[CH:12][CH:11]=3)[N:6]=[CH:7][CH:8]=[C:9]2[C:20]=1[CH3:21]
Reactant: CC=C(C)[Mg]Br
Reactant: C=Cc1ccc(-c2ncccc2[N+](=O)[O-])cc1
Agent: [Cl-]
Agent: [NH4+]
Solvent: C1CCOC1
Product: C=Cc1ccc(-c2nccc3c(C)c(C)[nH]c23)cc1
Temperature: -78 °C
Reaction time: 1 h

Procedure:
A solution of 3-nitro-2-(4-vinylphenyl)pyridine (4.9 g, 21.6 mmol) prepared in Preparation 9 in anhydrous tetrahydrofuran (150 ml) was cooled to −78° C. and 1-methyl-1-propenyl magnesium bromide (0.5M in anhydrous tetrahydrofuran solution; 130 ml) was slowly added thereto. The reaction mixture was stirred for 1 hour at the same temperature, slowly warmed to room temperature, and then stirred overnight. 20% (w/v) ammonium chloride solution was added to the reaction mixture, which was then extracted with ethyl acetate. The reaction mixture was dried on anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting residue was purified with silica gel column chromatography and then crystallized with ethyl ether to give 612 mg of the titled compound as a white solid.
Reaction SMILES: [C:1]1([C:7]([C:9]2[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=2)=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[BH4-].[Na+]>CO>[N:11]1[CH:12]=[CH:13][CH:14]=[C:9]([CH:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[OH:8])[CH:10]=1
Reactant: O=C(c1ccccc1)c1cccnc1
Agent: [BH4-]
Agent: [Na+]
Solvent: CO
Product: OC(c1ccccc1)c1cccnc1
Temperature: 25 °C
Reaction time: 72 h

Procedure:
50.0 gms of phenyl-3-pyridyl ketone was added to 650 ml of methanol and the system was then cooled to 0° to 5° C. After cooling, 15.5 gms of sodium borohydride was added in 3 parts. After addition, the system was allowed to come to room temperature. The system was then refluxed for 1 hour and stirred for an additional 72 hours at room temperature. The methanol was removed by stripping. Afterwards, 575 ml of 5% HCl solution was added to the residue and the system refluxed for 15 minutes. The acid was neutralized with 50% NaOH solution and the product extracted with methylene chloride to give the 3-pyridylphenylcarbinol as a white solid, m.p. 53° to 60° C.
Reaction SMILES: [C:1]1(C2C=NC(=O)C(=O)C=2C2C=CC=CC=2)C=CC=C[CH:2]=1.C1OCCOCCOCCOCCOCCOC1.[NH2:39][C@H:40]([CH2:47][C:48]([OH:50])=[O:49])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1>C(Cl)Cl>[CH2:1]([O:49][C:48](=[O:50])[CH2:47][C@H:40]([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[NH2:39])[CH3:2]
Reactant: N[C@H](CC(=O)O)c1ccccc1
Reactant: O=C1N=CC(c2ccccc2)=C(c2ccccc2)C1=O
Agent: C1COCCOCCOCCOCCOCCO1
Solvent: ClCCl
Product: CCOC(=O)C[C@@H](N)c1ccccc1

Procedure:
In this example, 0.32 ml of the diphenyl-diketo-pyridine-18-crown-6 was coated on polystyrene, and further coated with CH2Cl2, as described in Example 4. The resulting coated ligand-bound solid support was then placed in a column. A 25° C. 3 ml racemic source solution containing 50 mMolar R and S enantiomers of the ethyl ester of β-phenylalanine, 0.01 M HClO4, and 0.5 M LiClO4 was drawn through the column at a 0.012 ml/min flow rate. Next, a 2 ml aqueous solution of 0.5 M LiCO4 and 0.01 M HClO4 was passed through the column to wash out the loading solution remaining in the column. The β-phenylalanine ester loaded on the column was then eluted in 3 ml of deionized water at 25° C. at a flow rate of from 0.01–0.02 ml/min in two 1.5 ml aliquots.
Reaction SMILES: C([C:3]1[CH:15]=[CH:14][C:13]2[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[CH2:6][C:5]=2[CH:4]=1)=C.[CH:16](C1C=CC2C3C(=CC=CC=3)CC=2C=1)=[CH2:17].C(C(C1C=CC=CC=1)=O)=C.C(C1C=CC2C3C(=CC=CC=3)CC=2C=1)=C.C(C(C1C=CC=CC=1)=O)(C)=C.N(C(C)(C)C#N)=NC(C)(C)C#N>C1(C)C=CC=CC=1>[CH:16]([C:12]1[C:7]2[CH2:6][C:5]3[C:13](=[CH:14][CH:15]=[CH:3][CH:4]=3)[C:8]=2[CH:9]=[CH:10][CH:11]=1)=[CH2:17]
Reactant: C=Cc1ccc2c(c1)Cc1ccccc1-2
Agent: C=C(C)C(=O)c1ccccc1
Agent: C=CC(=O)c1ccccc1
Agent: CC(C)(C#N)N=NC(C)(C)C#N
Solvent: Cc1ccccc1
Product: C=Cc1cccc2c1Cc1ccccc1-2

Procedure:
Concentrated solution polymerizations of three runs P1, P2 and P3, respectively, 2-vinyl fluorene (2VF), 2VF + phenyl vinyl ketone (PVK) and 2VF + phenyl isopropenyl ketone (PIPK) were carried out. In each case the procedure was the same: the monomer(s) was placed in a 6 mm diameter tube, approximately 0.25% azobisisobutyronitrile (AIBN) initiator was added in toluene so as to give a final monomer/solvent ratio of approximately 1/1. The tubes were then flushed with nitrogen and vacuum pumped five times before being left capped under nitrogen. After a variable raction time at 75° C., as shown in Table I the tubes were opened and the polymer was dissolved in toluene; dropwise addition of this solution to methyl alcohol gave a precipitate that was filtered and vacuum dried. Details are given in Table I.
Reaction SMILES: [CH2:1]([OH:4])[C:2]#[CH:3].[C:5]([Si:9](Cl)([CH3:11])[CH3:10])([CH3:8])([CH3:7])[CH3:6].C(N(CC)CC)C>CN(C)C1C=CN=CC=1.C(Cl)Cl>[CH3:10][Si:9]([CH3:11])([C:5]([CH3:8])([CH3:7])[CH3:6])[O:4][CH2:1][C:2]#[CH:3]
Reactant: C#CCO
Reactant: CC(C)(C)[Si](C)(C)Cl
Agent: CN(C)c1ccncc1
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: C#CCO[Si](C)(C)C(C)(C)C

Procedure:
A solution of propargyl alcohol (8.7 ml), t-butyldimethyl silyl chloride (25. g) and 4-dimethylaminopyridine (0.73 g) in methylene chloride (45 ml) was cooled to 0°. Triethylamine (25.1 ml) was added dropwise over 5 mins with stirring. After 18 h the mixture was diluted with methylene chloride (50 ml) and extracted with water (2×75 ml). The aqueous solutions were combined and then extracted with methylene chloride (25 ml). The organic phases were combined and washed with water and saturated aqueous ammonium chloride, dried and evaporated to give an oil (24.9 g). Distillation under reduced pressure afforded the title compound as an oil (20.8 g); bp 60°-62° (24 mm Hg).
Reaction SMILES: [NH:1]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[C@H:2]([C:11]([OH:13])=[O:12])[CH2:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1.[CH3:21][C@H:22]([NH2:37])[C:23]([NH:25][C@H:26]([C:34]([OH:36])=[O:35])[CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:24].[NH2:38][CH2:39][C:40](NN)=[O:41].Cl.N(OCCCC)=O.CN1CCOCC1.[NH2:59][C@H:60]([C:69]([NH2:71])=[O:70])[CH2:61][C:62]1[CH:67]=[CH:66][C:65]([OH:68])=[CH:64][CH:63]=1.Cl>CN(C)C=O.O1CCCC1.CO>[NH:1]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[C@H:2]([C:11]([OH:13])=[O:12])[CH2:3][C:4]1[CH:5]=[CH:6][C:7]([OH:10])=[CH:8][CH:9]=1.[CH3:21][C@H:22]([NH2:37])[C:23]([NH:25][C@H:26]([C:34]([OH:36])=[O:35])[CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:24].[CH:67]1[C:62]([CH2:61][C@H:60]([NH:59][C:40]([CH2:39][NH2:38])=[O:41])[C:69]([NH2:71])=[O:70])=[CH:63][CH:64]=[C:65]([OH:68])[CH:66]=1
Reactant: NC(=O)[C@@H](N)Cc1ccc(O)cc1
Reactant: NCC(=O)NN
Agent: CC(C)(C)OC(=O)N[C@@H](Cc1ccc(O)cc1)C(=O)O
Agent: CCCCON=O
Agent: C[C@H](N)C(=O)N[C@@H](Cc1ccccc1)C(=O)O
Solvent: CN(C)C=O
Solvent: CO
Solvent: CN1CCOCC1
Product: NCC(=O)N[C@@H](Cc1ccc(O)cc1)C(N)=O
Temperature: -30 °C
Reaction time: 0.5 h

Procedure:
2.74 g (4.8 mmoles) Boc-Tyr-ala-Phe-Gly-NH-NH2 (10) are dissolved in 50 ml anhydrous dimethylformamide and cooled at -30° C. 2.0 ml (12 mmoles) 6 N hydrogen chloride in anhydrous tetrahydrofuran and 0.63 ml (5.28 mmoles) n-butyl nitrite are successively added and the reaction mixture is stirred for 30 min. at -30° C. 1.34 ml (12 mmoles) N-methyl-morpholine are added at -40° C., followed by a precooled (-40° C.) solution of 0.865 g (4.0 mmoles) H-Tyr-NH2.HCl (K. Blau and S. G. Waley, Biochem. J., 57, 538, 1954) and 0.456 ml (4.0 mmoles) N-methylmorpholine in 50 ml dimethylformamide. The reaction mixture is allowed to react for 7 days at -10° C., then it is concentrated to small volume, filtered from salt, and the product precipitated by dilution with chloroform. By crystallization from methyl alcohol-chloroform, 2.0 g of (14) are obtained, m.p. 127°-129° C.; [α]D25 +19.9° (C=1, MeOH); RfA =0.15, RfB =0.56.