Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [S:1]1[CH:5]=[CH:4][C:3]([CH2:6][C:7]([OH:9])=[O:8])=[CH:2]1.[CH3:10]O>>[S:1]1[CH:5]=[CH:4][C:3]([CH2:6][C:7]([O:9][CH3:10])=[O:8])=[CH:2]1
Reactant: O=C(O)Cc1ccsc1
Reactant: CO
Product: COC(=O)Cc1ccsc1
Reaction time: 3 h

Procedure:
To 2-(thiophen-3-yl)acetic acid in MeOH at 0° C. was added TMS-CH2N2. The solution was stirred for 3 hours then quenched with a few drops of AcOH. The solvents were evaporated. Column chromatography (SiO2, 3-15% EtOAc/Hex) gave pure methyl 2-(thiophen-3-yl)acetate (E41).
Reaction SMILES: [H-].[Na+].[CH:3]1([C:6]2[CH:7]=[C:8]([CH:18]=[C:19]([O:21][C:22]3[CH:27]=[CH:26][C:25]([C:28]([F:31])([F:30])[F:29])=[CH:24][N:23]=3)[CH:20]=2)[CH2:9]P(=O)(OCC)OCC)[CH2:5][CH2:4]1.[C:32]([N:39]1[CH2:44][CH2:43][CH2:42][CH2:41][C:40]1=O)([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33]>C1COCC1>[CH:3]1([C:6]2[CH:7]=[C:8]([CH:18]=[C:19]([O:21][C:22]3[CH:27]=[CH:26][C:25]([C:28]([F:31])([F:29])[F:30])=[CH:24][N:23]=3)[CH:20]=2)[CH:9]=[C:42]2[CH2:43][CH2:44][N:39]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[CH2:40][CH2:41]2)[CH2:4][CH2:5]1
Reactant: CC(C)(C)OC(=O)N1CCCCC1=O
Reactant: CCOP(=O)(Cc1cc(Oc2ccc(C(F)(F)F)cn2)cc(C2CC2)c1)OCC
Agent: [H-]
Agent: [Na+]
Solvent: C1CCOC1
Product: CC(C)(C)OC(=O)N1CCC(=Cc2cc(Oc3ccc(C(F)(F)F)cn3)cc(C3CC3)c2)CC1
Temperature: 0 °C
Reaction time: 0.5 h
Yield: 46.2 %

Procedure:
To a suspension of sodium hydride (0.11 g, 4.65 mmol) in dry THF (1.5 mL) under an inert atmosphere cooled to 0° C. was added diethyl 3-cyclopropyl-5-(5-(trifluoromethyl)pyridin-2-yloxy)benzylphosphonate (0.8 g, 1.86 mmol) as a solution in THF (6 mL). The mixture was stirred for 30 min at 0° C. N-Boc piperidone (0.37 g, 1.86 mmol) was added as a solution in THF (3 mL) and the mixture was stirred at RT for 5 h. The reaction was cooled to 0° C. and quenched with saturated aqueous ammonium chloride. The mixture was extracted with ethyl acetate three times. The organic layer was washed with brine, dried over Na2SO4 and evaporated to dryness. The residue was purified by silica gel column chromatography (10% ethyl acetate in hexane) to give the title compound (0.408 g, 46%). 1H NMR (500 MHz, CDCl3): δ 8.45 (s, 1H), 7.87 (d, J=8 Hz, 1H), 6.97 (d, J=8.5 Hz, 1H), 6.79 (s, 1H), 6.74 (s, 1H), 6.68 (s, 1H), 6.30 (s, 1H), 3.49 (m, 2H), 3.39 (m, 2H), 2.45 (m, 2H), 2.31 (m, 2H), 1.88 (m, 1H), 1.46 (s, 9H), 0.96 (d, J=8.5 Hz, 2H), 0.69 (d, J=4.5 Hz, 2H); m/z (475.1, M+ H+).
Reaction SMILES: [N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=[CH:3][C:2]=1[C:11]1[CH:12]=[C:13]([NH2:17])[CH:14]=[CH:15][CH:16]=1.[S:18]([CH2:22][CH2:23][C:24](O)=[O:25])(=[O:21])(=[O:20])[NH2:19].C(Cl)CCl.C1C=C2N=NN(O)C2=CC=1.O>CN(C=O)C>[NH2:19][S:18]([CH2:22][CH2:23][C:24]([NH:17][C:13]1[CH:14]=[CH:15][CH:16]=[C:11]([C:2]2[CH:3]=[N:4][C:5]3[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=3)[N:1]=2)[CH:12]=1)=[O:25])(=[O:21])=[O:20]
Reactant: NS(=O)(=O)CCC(=O)O
Reactant: Nc1cccc(-c2cnc3ccccc3n2)c1
Agent: On1nnc2ccccc21
Solvent: CN(C)C=O
Solvent: ClCCCl
Solvent: O
Product: NS(=O)(=O)CCC(=O)Nc1cccc(-c2cnc3ccccc3n2)c1
Temperature: 25 °C
Reaction time: 24 h
Yield: 33.5 %

Procedure:
To a solution of (3-quinoxalin-2-ylphenyl)amine (120 mg, 0.545 mol) and 3-sulfamoylpropanoic acid (100 mg, 0.654 mmol) in dry DMF (3 mL), EDC (115 mg, 0.6 mmol) and HOBt hydrate (92 mg, 0.6 mmol) were added and the reaction mixture stirred at room temperature for 24 hrs. The solvent was evaporated in vacuo (45° C., 0.1 mbar) and the residue was triturated with DCM (10 mL) and filtered. The solid was triturated with hot acetonitrile, filtered hot and dried to afford 3-(aminosulfonyl)-N-[3-(2-quinoxalinyl)phenyl]propanamide (78 mg, 40%). LCMS calculated for C17H16N4O3S (M+H): 357.41. found 357.24. 1H-NMR (DMSO-d6, 400 Mhz) δH: 10.41 (1H, br.), 9.50 (1H, s), 8.53 (1H, m), 8.15 (2H, m), 8.02 (1H, m), 7.94-7.80 (3H, m), 7.55 (1H, m), 6.88 (2H, br.), 3.35 (2H, t, J=7.2 Hz), 2.85 (2H, t, J=7.2 Hz).
Reaction SMILES: Cl.[N:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][O:9][C:10]([NH:12][CH2:13][C:14]2[CH:22]=[CH:21][C:17]([C:18](Cl)=[O:19])=[CH:16][CH:15]=2)=[O:11])[CH:3]=1.[NH:23]1[CH:27]=[CH:26][N:25]=[CH:24]1>O1CCCC1>[N:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][O:9][C:10]([NH:12][CH2:13][C:14]2[CH:22]=[CH:21][C:17]([C:18]([N:23]3[CH:27]=[CH:26][N:25]=[CH:24]3)=[O:19])=[CH:16][CH:15]=2)=[O:11])[CH:3]=1
Reactant: O=C(NCc1ccc(C(=O)Cl)cc1)OCc1cccnc1
Reactant: c1c[nH]cn1
Agent: Cl
Solvent: C1CCOC1
Product: O=C(NCc1ccc(C(=O)n2ccnc2)cc1)OCc1cccnc1
Reaction time: 1 h
Yield: 55.4 %

Procedure:
1 g (2.9 mmole) of 4-[N-(pyridin-3-ylmethoxycarbonyl)aminomethyl]benzoyl chloride hydrochloride was added to a tetrahydrofuran (10 ml) solution including 0.6 g (8.8 mmole) of imidazole, followed by stirring for 1 hour. A deposited imidazole hydrochloride was removed by filtration, and the reaction solution was then concentrated. Ethyl acetate and water were added to the solution to carry out partition, and the organic layer was then treated in an ordinary manner to obtain 0.54 g (yield: 55%) of 1-{4-[N-(pyridin-3-ylmethoxycarbonyl)aminomethyl]benzoyl}imidazole.
Reaction SMILES: [OH:1][CH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[N:6]=[CH:5][CH:4]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[N:33]1[C:37](=[O:38])[C:36]2=[CH:39][CH:40]=[CH:41][CH:42]=[C:35]2[C:34]1=[O:43].CCOC(/N=N/C(OCC)=O)=O>C1COCC1.CCOCC>[N:6]1[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[C:3]([CH2:2][O:1][N:33]2[C:34](=[O:43])[C:35]3=[CH:42][CH:41]=[CH:40][CH:39]=[C:36]3[C:37]2=[O:38])=[CH:4][CH:5]=1
Reactant: O=C1c2ccccc2C(=O)N1O
Reactant: OCc1ccnc2ccccc12
Agent: CCOC(=O)/N=N/C(=O)OCC
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: CCOCC
Solvent: C1CCOC1
Product: O=C1c2ccccc2C(=O)N1OCc1ccnc2ccccc12
Reaction time: 8 h
Yield: 88.4 %

Procedure:
4-(hydroxymethyl)quinoline (1.20 g, 7.55 mmol), triphenyl phosphine (2.27 g, 8.66 mmol, 1.15 equiv) and N-hydroxyphthalimide (1.42 g, 8.71 mmol, 1.15 equiv) were dissolved in 40 mL of dry THF. Diethylazodicarboxylate (1.44 mL, 9.15 mmol, 1.21 equiv) was then added dropwise and the reaction was stirred overnight. The reaction mixture was then diluted with 50 mL of Et2O and filtered. The resulting solid was dissolved in dichloromethane and washed with 1N NaOH, H2O and brine. The organic portion was dried over Na2SO4 and concentrated under reduced pressure to give the title compound (2.03 g) as a fluffy white solid. MS(CI) m/e 305 (M+H)+.
Reaction SMILES: [C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]([O:17][CH2:18][CH2:19][O:20][CH3:21])([C:14]([OH:16])=O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].N1C=CC=CC=1.C(Cl)(=O)C(Cl)=O.[CH3:34][N:35]([CH3:46])[C:36](=[O:45])[O:37][C:38]1[CH:43]=[CH:42][CH:41]=[C:40]([NH2:44])[CH:39]=1>ClC(Cl)C.ClCCl.CN(C=O)C>[CH3:34][N:35]([CH3:46])[C:36]([O:37][C:38]1[CH:39]=[C:40]([NH:44][C:14]([C:11]2([O:17][CH2:18][CH2:19][O:20][CH3:21])[CH2:10][CH2:9][N:8]([C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[CH2:13][CH2:12]2)=[O:16])[CH:41]=[CH:42][CH:43]=1)=[O:45]
Reactant: CN(C)C(=O)Oc1cccc(N)c1
Reactant: COCCOC1(C(=O)O)CCN(C(=O)OC(C)(C)C)CC1
Agent: O=C(Cl)C(=O)Cl
Solvent: CC(Cl)Cl
Solvent: c1ccncc1
Solvent: CN(C)C=O
Product: COCCOC1(C(=O)Nc2cccc(OC(=O)N(C)C)c2)CCN(C(=O)OC(C)(C)C)CC1
Reaction time: 0.5 h
Yield: 88 %

Procedure:
To a solution of 1-(tert-butoxycarbonyl)-4-(2-methoxyethoxy)piperidine-4-carboxylic acid from step B (1.6 g, 5.1 mmol) in dichloroethane was added pyridine (1.6 g, 20 mmol) and DMF (0.05 mL), followed by oxalyl chloride (0.65 g, 5.1 mmol). The mixture was stirred for 30 minutes, and then 3-aminophenyl dimethylcarbamate (0.91 g, 5.04 mmol) was added. The mixture was stirred for 18 hours, then diluted with dichloromethane, washed twice with 1 N aq. HCl and once with brine, dried over MgSO4, and concentrated. Silica gel chromatography (0-5% MeOH:CH2Cl2) gave the title compound in 88% yield. MS (ES+) [M+H]+=480.
Reaction SMILES: [CH3:1][C@H:2]([O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2C2C=CC(C([O-])=O)=CC=2)=[CH:12][C:11]=1[N+:31]([O-:33])=[O:32])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].C[C@H]([O:42]C1C=CC(OC(=O)C2C=CC=CC=2)=CC=1[N+]([O-])=O)CCCCCC>>[CH3:1][C@H:2]([O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:21]=[CH:20][C:19]([OH:42])=[CH:18][CH:17]=2)=[CH:12][C:11]=1[N+:31]([O-:33])=[O:32])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]
Reactant: CCCCCC[C@H](C)Oc1ccc(-c2ccccc2-c2ccc(C(=O)[O-])cc2)cc1[N+](=O)[O-]
Reactant: CCCCCC[C@H](C)Oc1ccc(OC(=O)c2ccccc2)cc1[N+](=O)[O-]
Product: CCCCCC[C@H](C)Oc1ccc(-c2ccc(O)cc2)cc1[N+](=O)[O-]

Procedure:
The benzoyl ester of (S)-4'-(1-methylheptyloxy)-3'-nitro-4-biphenylylbenzoate was saponified using the same procedure as that used for saponification of (S)-[4-(1-methylheptyloxy)-3-nitrophenyl]-benzoate except that the reaction was carried out at 60° C. to give (S)-4'-(1-methylheptyloxy)-3'-nitro-4-hydroxybiphenyl (Compound 17, Scheme II, R2 =(S)--OCH(CH3)C6H13) as a very viscous orange liquid after flash chromatography with hexanes/ethyl acetate [88/12]; Rf [hexanes/ethyl acetate 85/15]: 0.17; 1H NMR (300 MHz, CDCl3): δ0.86(t, 3H, J=6.6 Hz), 1.18-1.52(m, 8H), 1.35(d, 3H, J =6.1 Hz), 1.62(m, 1H), 1.78(m, 1H), 4.50 (m, 1H), 5.22(broad s, 1H), 6.89(d, 2H, J=8.5 Hz), 7.07 (d, 1H, J=8.8 Hz), 7.39 (d, 2H, J=8.5 Hz), 7.62(dd, 1H, J =2.4 Hz, J=8.8 Hz), 7.92 (d, 1H, J=2.4 Hz); 13C NMR (300 MHz, CDCl3): δ13.99, 19.49, 22.50, 25.19, 29.10, 31.65, 36.17, 76.57, 115.94, 116.17, 123.30, 127.99, 131.21, 131.64, 133.09, 141.00, 15.42, 155.52; IR (CHCl3); 350, 3300(broad), 3020, 2920, 2840, 1610, 1540, 1510, 1485, 1350, 1260, 1220, 1160, 1110, 1040, 925, 825 cm-1 ; Mass spectrum, m/z(rel.intensity): 343(M+ 5), 231(100), 185(6), 57(6), 43(12).
Reaction SMILES: [CH3:1][N:2]=[C:3]=[O:4].[NH2:5][CH2:6][CH2:7][CH2:8][O:9][C:10]1[CH:11]=[C:12]([CH2:16][N:17]([CH3:19])[CH3:18])[CH:13]=[CH:14][CH:15]=1>C(#N)C>[CH3:1][NH:2][C:3]([NH:5][CH2:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH2:16][N:17]([CH3:18])[CH3:19])[CH:11]=1)=[O:4]
Reactant: CN=C=O
Reactant: CN(C)Cc1cccc(OCCCN)c1
Solvent: CC#N
Product: CNC(=O)NCCCOc1cccc(CN(C)C)c1

Procedure:
Methyl isocyanate (0.27 ml) and 3-(3-aminopropoxy)-N,N-dimethylbenzenemethanamine (0.97 g) were stirred at room temperature in acetonitrile for 2 hours. The title compound was filtered off, washed with acetonitrile and recrystallised from ethyl acetate as colourless prisms (0.49 g) m.p. 79.5°-80°. TLC silica; methanol:0.88 ammonia (80:1) Rf 0.45.
Reaction SMILES: Cl.[Cl:2][C:3]1[CH:8]=[C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([Cl:15])[CH:10]=2)[N:6]=[C:5]2[CH2:16][CH2:17][CH2:18][C:4]=12.[NH2:19][C:20]1[CH:33]=[CH:32][C:23]([CH2:24][CH:25]([C:29]([NH2:31])=[O:30])[C:26]([NH2:28])=[O:27])=[CH:22][CH:21]=1.C(=O)(O)[O-].[Na+]>Cl.CN1C(=O)CCC1.O>[ClH:2].[Cl:15][C:11]1[CH:10]=[C:9]([C:7]2[N:6]=[C:5]3[CH2:16][CH2:17][CH2:18][C:4]3=[C:3]([NH:19][C:20]3[CH:21]=[CH:22][C:23]([CH2:24][CH:25]([C:26]([NH2:28])=[O:27])[C:29]([NH2:31])=[O:30])=[CH:32][CH:33]=3)[CH:8]=2)[CH:14]=[CH:13][CH:12]=1
Reactant: Clc1cccc(-c2cc(Cl)c3c(n2)CCC3)c1
Reactant: NC(=O)C(Cc1ccc(N)cc1)C(N)=O
Agent: Cl
Agent: O=C([O-])O
Agent: [Na+]
Solvent: CN1CCCC1=O
Solvent: O
Product: NC(=O)C(Cc1ccc(Nc2cc(-c3cccc(Cl)c3)nc3c2CCC3)cc1)C(N)=O
Temperature: 140 °C
Yield: 45 %

Procedure:
A 10-mL microwave vial was charged with 4-chloro-2-(3-chlorophenyl)-6,7-dihydro-5H-cyclopenta[b]pyridine hydrochloride (0.100 g, 0.33 mmol), 2-(4-aminobenzyl)malonamide (0.110 g, 0.53 mmol) and conc. HCl (1 drop) in NMP (3 mL). The resulting mixture was heated at 140° C. under microwave irradiation for 3 h. After this time, the reaction mixture was cooled, diluted with water (15 mL) and then treated with saturated sodium bicarbonate until pH˜8. The resulting solid was isolated by filtration and purified by preparative HPLC (water/acetonitrile with 0.05% TFA) to afford the free base of the title compound (0.070 g, 56%) as an off-white solid. MW=434.92. 1H NMR (DMSO-d6, 500 MHz) δ 8.07 (s, 1H), 7.90 (s, 1H), 7.75-7.70 (m, 1H), 7.46-7.38 (m, 2H), 7.24 (s, 2H), 7.21-7.13 (m, 5H), 7.02 (s, 2H), 4.08-4.00 (m, 1H), 2.96 (d, J=7.0 Hz, 2H), 2.93-2.87 (m, 2H), 2.85-2.78 (m, 2H), 2.22-2.13 (m, 2H). MS: ESI+, m/z 435 [M+H]+. Treatment with 1.25M HCl in methanol (0.19 mL, 0.24 mmol, 1.5 eq.) afforded the title compound (0.048 g, 64%) as an off-white solid. MW=471.38. m.p. 219-222° C. 1H NMR (DMSO-d6, 500 MHz) δ 13.95 (br s, 1H), 9.71 (s, 1H), 7.90-7.87 (m, 1H), 7.70-7.74 (m, 2H), 7.60 (t, J=8.0 Hz, 1H), 7.31 (s, 5H), 7.03 (s, 2H), 6.97 (s, 1H), 3.36-3.33 (m, 1H), 3.13 (t, J=7.5 Hz, 2H), 3.01 (d, J=7.5 Hz, 2H), 3.13 (t, J=7.0 Hz, 2H), 2.28-2.19 (m, 2H); ESI MS m/z 435 [M+H]+.
Reaction SMILES: Cl[Si:2]([NH:5][C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])[CH3:3].[CH-:10]1[C:22]2[CH2:21][C:20]3[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:14]=2[CH2:13][CH2:12][CH2:11]1.[Li+]>C1COCC1>[C:6]([NH:5][Si:2]([CH3:4])([CH3:3])[CH:19]1[C:20]2[CH2:21][C:22]3[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:15]=2[CH2:16][CH2:17][CH2:18]1)([CH3:9])([CH3:8])[CH3:7]
Reactant: CC(C)(C)N[Si](C)(C)Cl
Reactant: c1ccc2c(c1)CC1=C2CCC[CH-]1
Agent: [Li+]
Solvent: C1CCOC1
Product: CC(C)(C)N[Si](C)(C)C1CCCC2=C1Cc1ccccc12
Temperature: 25 °C
Yield: 93.7 %

Procedure:
5.78 g (34.9 mmol) of ClSiMe2NHCMe3 (prepared according to the method described in J. Prakt. Chem, 24(3-4), 226-30 (1964)) was added to 100 ml of THF. To this solution 6.15 g (34.9 mmol) of lithium tetrahydrofluorenide was added. The solution was then brought to reflux for 10 min and the solution cooled to room temperature. Gas chromatographic (GC) analysis showed the reaction to be complete. The solvent was then removed under reduced pressure, the residue extracted with pentane, filtered and the solvent again removed under reduced pressure to give 9.80 g of product (94 percent yield).
Reaction SMILES: C[O:2][CH:3](OC)[C:4]1[CH:9]=[CH:8][N:7]=[CH:6][C:5]=1[O:10][CH2:11][C:12]1[N:17]=[CH:16][C:15]([C:18]([NH:20][S:21]([CH3:24])(=[O:23])=[O:22])=[O:19])=[CH:14][CH:13]=1.[F:27][C:28]([F:33])([F:32])[C:29]([OH:31])=[O:30]>ClCCl>[F:27][C:28]([F:33])([F:32])[C:29]([OH:31])=[O:30].[CH:3]([C:4]1[CH:9]=[CH:8][N:7]=[CH:6][C:5]=1[O:10][CH2:11][C:12]1[CH:13]=[CH:14][C:15]([C:18]([NH:20][S:21]([CH3:24])(=[O:22])=[O:23])=[O:19])=[CH:16][N:17]=1)=[O:2]
Reactant: COC(OC)c1ccncc1OCc1ccc(C(=O)NS(C)(=O)=O)cn1
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: CS(=O)(=O)NC(=O)c1ccc(COc2cnccc2C=O)nc1
Temperature: 40 °C
Reaction time: 3 h

Procedure:
Into a 50-mL round-bottom flask, which was purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 6-([[4-(dimethoxymethyl)pyridin-3-yl]oxy]methyl)-N-methanesulfonylpyridine-3-carboxamide (80 mg, 0.21 mmol, 1.00 equiv) in dichloromethane (5 mL), and trifluoroacetic acid (2 mL). The resulting solution was stirred for 3 h at 40° C. in an oil bath, and then it was concentrated under vacuum. The crude product (60 mg) was purified by Flash-Prep-HPLC with the following conditions (CombiFlash-1): Column, C18 silica gel; mobile phase, CH3CN/H2O=1/99 increasing to CH3CN/H2O=40/60 within 20 min; Detector, UV 254 nm. This resulted in 20 mg (17%) of 6-[[(4-formylpyridin-3-yl)oxy]methyl]-N-methanesulfonylpyridine-3-carboxamide; bis(trifluoroacetic acid) as a white solid. The compound exhibited a melting point of 102-104° C. LC-MS: (ES, m/z):336 [M+1]+/354 [M+1+18]+. H-NMR (300 MHz, DMSO, ppm): 10.53 (s, 1H), 9.07 (s, 1H), 8.78 (s, 1H), 8.43 (d, J=4.5 Hz, 1H), 8.36 (dd, J=8.1 Hz, 1H), 7.84 (d, J=8.4 Hz, 1H), 7.62 (d, J=4.5 Hz, 1H), 5.60 (s, 2H), 3.37 (s, 3H).
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][N:3]=1.[CH3:9][Si:10]([C:13]#[CH:14])([CH3:12])[CH3:11].CCN(CC)CC>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:9][Si:10]([C:13]#[C:14][C:5]1[CH:6]=[CH:7][C:2]([NH2:1])=[N:3][CH:4]=1)([CH3:12])[CH3:11]
Reactant: Nc1ccc(Br)cn1
Reactant: C#C[Si](C)(C)C
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: CN(C)C=O
Solvent: CCN(CC)CC
Product: C[Si](C)(C)C#Cc1ccc(N)nc1
Temperature: 90 °C
Reaction time: 4.5 h
Yield: 75.7 %

Procedure:
A mixture of commercially available 2-amino-5-bromopyridine (50.0 g, 289 mmol), trimethylsilylacetylene (112 mL, 809 mmol), Et3N (120 mL, 867 mmol), PdCl2(PPh3)2 (4.06 g, 2 mol %) and PPh3 (1.52 g, 2 mol %) in DMF (290 mL) was purged for 10 min with argon. Then CuI (340 mg, 1 mol %) was added and the reaction mixture was heated up to 90° C., stirring was continued at 90° C. for 4.5 h. Cooled to 23° C., the reaction mixture was concentrated in vacuum to remove all volatiles, poured the residue onto water (300 mL) and extracted with ethyl acetate (3×500 mL). The combined organic layers were washed with water (300 mL) and brine (2×250 mL), dried over MgSO4. Removal of the solvent in vacuum left a dark brown residue which was purified by flash chromatography with n-heptane and acetone to give the title compound as a brown solid (41.65 g, 76%). MS (ISP) 191 [(M+H)+].
Reaction SMILES: [OH:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[C:10](=[O:25])[CH2:11][C:12](=[O:24])/[CH:13]=[CH:14]/[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[N+:21]([O-])=O)=[CH:4][CH:3]=1.[Sn](Cl)Cl>C(OCC)(=O)C.CO.C(Cl)(Cl)Cl.C([O-])(O)=O.[Na+]>[NH2:21][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1/[CH:14]=[CH:13]/[C:12](=[O:24])[CH2:11][C:10](=[O:25])/[CH:9]=[CH:8]/[C:5]1[CH:4]=[CH:3][C:2]([OH:1])=[CH:7][CH:6]=1
Reactant: O=C(/C=C/c1ccc(O)cc1)CC(=O)/C=C/c1ccccc1[N+](=O)[O-]
Agent: Cl[Sn]Cl
Agent: O=C([O-])O
Agent: [Na+]
Solvent: CCOC(C)=O
Solvent: ClC(Cl)Cl
Solvent: CO
Product: Nc1ccccc1/C=C/C(=O)CC(=O)/C=C/c1ccc(O)cc1
Temperature: 60 °C
Reaction time: 1.5 h
Yield: 46.5 %

Procedure:
To a solution of (1E,6E)-1-(4-hydroxyphenyl)-7-(2-nitrophenyl)hepta-1,6-diene-3,5-dione (26 mg, 77 μmol, synthesized in Example 344) in 3.0 mL of ethyl acetate was added anhydrous tin(II) chloride (57 mg, 0.30 mmol) at room temperature. After being stirred at 60° C. for 1.5 h, the reaction mixture was cooled to room temperature, and was diluted with 10% methanol/chloroform and saturated NaHCO3 aqueous solution, successively. The mixture was shaken before filtration to remove inorganic salts. The organic layer after separation was washed with brine, and dried over MgSO4. After filtration, the filtrate was concentrated in vacuo, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate=70/30 to 60/40) to obtain the title compound as a solid (11.0 mg, 46%) having the following characteristics.
Reaction SMILES: [C:1]1([C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)O)[OH:2].[NH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][NH2:22].[O:23]=O>ClCC(Cl)CCl.ClC=C(Cl)Cl>[C:16]1([C:5]2[C:6](=[O:23])[CH:7]=[CH:8][C:1](=[O:2])[CH:3]=2)[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1.[NH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][NH2:22]
Reactant: Oc1ccccc1O
Reactant: O=O
Agent: NCCCCCCCCCCCCN
Solvent: ClCC(Cl)CCl
Solvent: ClC=C(Cl)Cl
Product: O=C1C=CC(=O)C(c2ccccc2)=C1

Procedure:
About 14.54 g (0.0782 mol) 2-phenyl-hydrooquinone, about 0.2 g (0.0018 mol) catechol (chemical name 1,2-dihydroxybenzene) and about 16 g (0.08 mol) 1,12diaminododecane were dissolved in a solvent mixture comprising of about 30 mL of 1,2,3trichloropropane and 60 mL of trichloroethylene. Oxygen was then passed at a flow rate of about 50 cc/min through the solution for about one hour. About 0.2 g of cupric sulfate was then added to the reaction mixture. Oxygen flow was reinstated for about an additional two hours. At the end of the polymerization reaction most of the trichloroethylene was removed under high vacuum, without raising the temperature above 35° C. This solution of poly-(2-phenyl-benzoquinone-1,12-diaminododecane) polymer can be used directly for coating purposes.
Reaction SMILES: [OH:1][C@@H:2]1[C@@:27]2([CH3:28])[C:6](=[CH:7][CH:8]=[C:9]3[C@@H:26]2[CH2:25][CH2:24][C@@:23]2([CH3:29])[C@H:10]3[CH2:11][CH2:12][C@@H:13]2[C@H:14]([CH3:22])[CH2:15][CH2:16][CH:17]([OH:21])[CH:18]([CH3:20])[CH3:19])[CH2:5][C@@H:4]([OH:30])[CH2:3]1.C(O[C:35](=[O:37])[CH3:36])(=O)C>N1C=CC=CC=1>[C:2]([O:1][C@@H:2]1[C@@:27]2([CH3:28])[C:6](=[CH:7][CH:8]=[C:9]3[C@@H:26]2[CH2:25][CH2:24][C@@:23]2([CH3:29])[C@H:10]3[CH2:11][CH2:12][C@@H:13]2[C@H:14]([CH3:22])[CH2:15][CH2:16][CH:17]([O:21][C:17](=[O:21])[CH3:16])[CH:18]([CH3:20])[CH3:19])[CH2:5][C@@H:4]([O:30][C:35](=[O:37])[CH3:36])[CH2:3]1)(=[O:1])[CH3:3]
Reactant: CC(=O)OC(C)=O
Reactant: CC(C)C(O)CC[C@@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)C[C@H](O)[C@]4(C)[C@H]3CC[C@]12C
Solvent: c1ccncc1
Product: CC(=O)OC(CC[C@@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](OC(C)=O)C[C@H](OC(C)=O)[C@]4(C)[C@H]3CC[C@]12C)C(C)C
Temperature: 0 °C

Procedure:
200 mg of 1α,3β,24trihydroxycholesta-5,7-diene prepared and separated in the same way as in Example 14, (D-1) was reacted with 2ml. of acetic anhydride and 5 ml. of pyridine at 95° C. for 3 hours. The reaction mixture was placed in ice water, and extracted with 40 ml. of diethyl ether. The ethereal phase was washed with dilute hydrochloric acid, then with alkali, and further with water, and dried. The ether was evaporated off to afford 1α,3β,24-triacetoxycholesta-5,7-diene as a slightly yellowish oily substance.
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)(O[CH2:12][CH:13]=[CH:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)OC>>[C:15]1([CH:14]([C:2]2([NH2:1])[CH:7]=[CH:6][CH:5]=[CH:4][CH2:3]2)[CH:13]=[CH2:12])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: Nc1ccccc1
Reactant: COC(=O)OCC=Cc1ccccc1
Product: C=CC(c1ccccc1)C1(N)C=CC=CC1
Reaction time: 24 h

Procedure:
By the procedure with [(COD)IrCl]2 (6.7 mg, 0.010 mmol) and L1 (Sa,Sc,Sc) (10.8 mg, 0.020 mmol) the reaction of aniline (130 mg, 1.40 mmol) and methyl cinnamyl carbonate (188 mg, 0.980 mmol) was conducted at room temperature for 24 h. 1H NMR and GC analysis of the crude reaction mixture showed that the conversion of the reaction was less than 1%.
Reaction SMILES: [N+:1]([O-:4])(O)=[O:2].[C:5]1([CH3:11])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>>[N+:1]([C:8]1[CH:9]=[CH:10][C:5]([CH3:11])=[CH:6][CH:7]=1)([O-:4])=[O:2]
Reactant: Cc1ccccc1
Reactant: O=[N+]([O-])O
Product: Cc1ccc([N+](=O)[O-])cc1

Procedure:
reacting toluene with nitric acid in a single liquid phase reaction in a first reaction zone at an elevated temperature to provide a single phase mononitrotoluene-containing product mixture, using a reaction mixture that is free of sulfuric acid and that comprises a molar ratio of said nitric acid to said toluene of from 20:1 to 30:1, said reaction being conducted using a combination of fresh and recycled aqueous nitric acid, said combination having a nitric acid concentration not exceeding 75% based upon the weight of nitric acid plus water in said dilute aqueous nitric acid,
Reaction SMILES: [H-].[Na+].[NH:3]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:5][C:4]1=[O:12].[CH2:13]([O:15][C:16]([C:18]1[C:19]([O:36][CH3:37])=[C:20]2[N:25]([CH:26]=1)[N:24]=[CH:23][N:22]=[C:21]2NC1C=CC(C)=C(O)C=1)=[O:17])[CH3:14]>C1COCC1>[CH2:13]([O:15][C:16]([C:18]1[C:19]([O:36][CH3:37])=[C:20]2[N:25]([CH:26]=1)[N:24]=[CH:23][N:22]=[C:21]2[CH:5]1[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[NH:3][C:4]1=[O:12])=[O:17])[CH3:14]
Reactant: O=C1Cc2ccccc2N1
Reactant: CCOC(=O)c1cn2ncnc(Nc3ccc(C)c(O)c3)c2c1OC
Agent: [H-]
Agent: [Na+]
Solvent: C1CCOC1
Product: CCOC(=O)c1cn2ncnc(C3C(=O)Nc4ccccc43)c2c1OC
Temperature: 25 °C
Reaction time: 0.33 h
Yield: 15.6 %

Procedure:
To a suspension of NaH (60%, 44 mg, 1.1 mmol) in THF (1 mL) was added oxindole (133 mg, 1 mmol). The reaction mixture was stirred for 20 min. at rt. Compound G of example 96 (0.1 mmol) was added. The reaction was stirred for 2 hrs at 25° C. The crude material was purified by preparative HPLC followed by chromatography on silica gel eluting with ethyl acetate to provide 5.5 mg (16%) of a yellow solid. MS: [M+H]+=353; 1H NMR (CDCl3): δ 8.42 (s, 0.4H), 8.10 (s, 0.6H), 7.79 (s, 1H), 7.75-6.88 (m, 4H), 4.33 (m, 2H), 3.57 (s, 3H), 1.37 (m, 3H).