Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH2:1]([NH:3][C:4](=[O:24])[NH:5][C:6]1[N:11]=[CH:10][C:9](B(O)O)=[C:8]([C:15]2[S:16][CH:17]=[C:18]([C:20]([F:23])([F:22])[F:21])[N:19]=2)[CH:7]=1)[CH3:2].[CH2:25]([N:27]1[C:36]2[C:31](=[CH:32][CH:33]=[C:34](I)[CH:35]=2)[C:30](=[O:38])[C:29]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:28]1)[CH3:26].C(=O)([O-])[O-].[K+].[K+].C(OCC)(=O)C>O1CCOCC1.O.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>[CH2:25]([N:27]1[C:36]2[C:31](=[CH:32][CH:33]=[C:34]([C:9]3[CH:10]=[N:11][C:6]([NH:5][C:4]([NH:3][CH2:1][CH3:2])=[O:24])=[CH:7][C:8]=3[C:15]3[S:16][CH:17]=[C:18]([C:20]([F:23])([F:22])[F:21])[N:19]=3)[CH:35]=2)[C:30](=[O:38])[C:29]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:28]1)[CH3:26]
Reactant: CCOC(=O)c1cn(CC)c2cc(I)ccc2c1=O
Reactant: CCNC(=O)Nc1cc(-c2nc(C(F)(F)F)cs2)c(B(O)O)cn1
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: C1COCCO1
Solvent: CCOC(C)=O
Solvent: O
Product: CCNC(=O)Nc1cc(-c2nc(C(F)(F)F)cs2)c(-c2ccc3c(=O)c(C(=O)OCC)cn(CC)c3c2)cn1
Temperature: 70 °C
Reaction time: 1.5 h
Yield: 46.5 %

Procedure:
To a slurry of 6-(3-ethylureido)-4-(4-trifluoromethylthiazol-2-yl)pyridin-3-ylboronic acid (Intermediate 17, 330 mg, 0.91 mmol), ethyl 1-ethyl7-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate (Intermediate 9, 281 mg, 0.75 mmol) and trans-dichlorobis(triphenylphosphine)palladium (II) (53 mg, 0.075 mmol) in 1,4-dioxane (8 ml) was added a solution of potassium carbonate (210 mg, 1.52 mmol) in water (3 ml). The reaction was stirred for 1.5 hours at 70° C. The reaction was cooled to room temperature, and ethyl acetate (8 mL) was added to help separate the layers. The water was removed, and the organic phase was washed with water (3 mL). The reaction was then concentrated and ethanol (5 mL) was added. The suspension was filtered, and the solid washed with methyl tert-butyl ether (2×, 5 ml). The solid was dried in a vacuum oven at 50° C. for 4 hours to give 195 mg (60%) of ethyl 1-ethyl7-(6-(3-ethylureido)-4-(4-trifluoromethylthiazol-2-yl)pyridin-3-yl)-4-oxo-1,4-dihydroquinoline-3-carboxylate as an off white solid.
Reaction SMILES: [C:1]([Cl:4])(Cl)=[O:2].[C:5]1([CH2:11][CH2:12][CH2:13][CH:14]2[CH2:19][CH2:18][NH:17][CH2:16][CH2:15]2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.N1C=CC=CC=1>C1(C)C=CC=CC=1>[C:5]1([CH2:11][CH2:12][CH2:13][CH:14]2[CH2:15][CH2:16][N:17]([C:1]([Cl:4])=[O:2])[CH2:18][CH2:19]2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1
Reactant: O=C(Cl)Cl
Reactant: c1ccc(CCCC2CCNCC2)cc1
Solvent: c1ccncc1
Solvent: Cc1ccccc1
Product: O=C(Cl)N1CCC(CCCc2ccccc2)CC1
Reaction time: 1 h

Procedure:
Phosgene is passed into 150 ml. of dry toluene at 0°C. until 17 g. of gas has been absorbed. The cooling bath is removed, and to the phosgene solution is added, dropwise, with stirring, during 1 hour, a solution prepared from 27.6. g. of 4-(3-phenylpropyl)piperidine, and 12.3 ml. of pyridine and 100 ml. of toluene. After the end of the addition, the reaction mixture is stored at ambient temperature for 16 hours. At this point, the reaction mixture is filtered, and the filtrate is evaporated in vacuo, leaving 39 g. of the title compound in crude state. The product is contaminated with toluene, but it is sufficiently pure for coupling with alkenesulfonamides.
Reaction SMILES: [CH3:1][O:2][C:3]1[C:10]([O:11][CH3:12])=[CH:9][C:6](C=O)=[C:5]([N+:13]([O-:15])=[O:14])[CH:4]=1.ClC1C=C(C=CC=1)C(OO)=[O:21].FC(F)(F)C(O)=O.[OH-].[Na+].Cl>ClCCl.CO>[CH3:1][O:2][C:3]1[C:10]([O:11][CH3:12])=[CH:9][C:6]([OH:21])=[C:5]([N+:13]([O-:15])=[O:14])[CH:4]=1
Reactant: COc1cc(C=O)c([N+](=O)[O-])cc1OC
Reactant: O=C(OO)c1cccc(Cl)c1
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Solvent: CO
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: COc1cc(O)c([N+](=O)[O-])cc1OC
Temperature: 25 °C
Reaction time: 18 h
Yield: 70.7 %

Procedure:
To a solution of 4,5-dimethoxy-2-nitro-benzaldehyde (3.75 g, 14.2 mmol) in dichloromethane (75 mL) at 0° C. under a nitrogen atmosphere was added meta-chloroperoxybenzoic acid (75% purity, 4.90 g, 28.4 mmol), then trifluoroacetic acid (1.05 mL, 14.2 mmol). The reaction was stirred at room temperature for 18 h, then recooled to 0° C. Excess reagent was quenched with 5% sodium bisulfite solution and the precipitate was removed by filtration, washing with dichloromethane. The organic phase of the filtrate was washed with sodium bicarbonate and brine, was dried (sodium sulfate), and was evaporated to provide a yellow solid. This intermediate was suspended in methanol (50 mL), treated with 2N NaOH (16 mL, 32 mmol), and was stirred at room temperature for 1 h. The reaction was acidified with 1N HCl and was filtered, washing with methanol to provide 4,5-dimethoxy-2-nitro-phenol (2.00 g, 71% yield) as a bright yellow solid. 1H-NMR (CDCl3, 500 MHz) 11.0 (s, 1H), 7.39 (s, 1H), 6.48 (s, 1H), 3.90 (s, 3H), 3.83 (s, 3H) ppm; MS (FIA) 197.9 (M−H); HPLC (Method A) 3.357 min.