Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@@H:10]([S:12][C:13]2[C@H:19]([CH3:20])[C@H:18]3[N:15]([C:16](=[O:24])[C@@H:17]3[C@H:21]([OH:23])[CH3:22])[C:14]=2[C:25]([O:27][CH2:28][CH:29]=[CH2:30])=[O:26])[CH2:9][C@H:8]1[CH2:31][CH2:32][N:33]1[C:37]([CH2:38][OH:39])=[CH:36][N:35]=[CH:34]1)=[O:6])[CH:2]=[CH2:3].[CH3:40][I:41]>CC(C)=O>[I-:41].[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@@H:10]([S:12][C:13]2[C@H:19]([CH3:20])[C@H:18]3[N:15]([C:16](=[O:24])[C@@H:17]3[C@H:21]([OH:23])[CH3:22])[C:14]=2[C:25]([O:27][CH2:28][CH:29]=[CH2:30])=[O:26])[CH2:9][C@H:8]1[CH2:31][CH2:32][N+:33]1[C:37]([CH2:38][OH:39])=[CH:36][N:35]([CH3:40])[CH:34]=1)=[O:6])[CH:2]=[CH2:3]
Reactant: C=CCOC(=O)C1=C(S[C@H]2C[C@@H](CCn3cncc3CO)N(C(=O)OCC=C)C2)[C@H](C)[C@@H]2[C@@H]([C@@H](C)O)C(=O)N12
Reactant: CI
Solvent: CC(C)=O
Product: C=CCOC(=O)C1=C(S[C@H]2C[C@@H](CC[n+]3cn(C)cc3CO)N(C(=O)OCC=C)C2)[C@H](C)[C@@H]2[C@@H]([C@@H](C)O)C(=O)N12
Product: [I-]
Reaction time: 12 h

Procedure:
To a solution of allyl (4R,5S,6S)-3-[(2R,4S)-1-allyloxycarbonyl-2-{2-(5-hydroxymethylimidazol-1-yl)ethyl}pyrrolidin-4-yl]thio-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo [3.2.0]hept-2-ene-2-carboxylate (790 mg) in acetone (4.0 ml) was added methyl iodide (0.88 ml) at room temperature and the solution was allowed to stand for 12 hours. The solvent was evaporated to give allyl (4R,5S,6S)-3-[(2R,4S)-1-allyloxycarbonyl-2-{2-(5-hydroxymethyl-3-methyl-1-imidazolio)ethyl}pyrrolidin-4-yl]thio-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate iodide (991 mg) as a yellow solid. This compound was immediately used as the starting compound for the next step.
Reaction SMILES: [O:1]=[C:2]([CH3:14])[CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][CH:6]=1.C([O-])([O-])=O.[K+].[K+].[N+]([C:24]1[CH:29]=[CH:28][C:27](O)=[CH:26][CH:25]=1)([O-])=O.ClCC(=O)C.C[N:37]([CH:39]=[O:40])C>>[CH3:14][C:2]1([CH2:3][O:4][C:5]2[CH:6]=[CH:7][C:8]([N+:11]([O-:13])=[O:12])=[CH:9][CH:10]=2)[NH:37][C:39](=[O:40])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[O:1]1
Reactant: O=[N+]([O-])c1ccc(O)cc1
Reactant: CN(C)C=O
Reactant: CC(=O)COc1ccc([N+](=O)[O-])cc1
Agent: CC(=O)CCl
Agent: O=C([O-])[O-]
Agent: [K+]
Product: CC1(COc2ccc([N+](=O)[O-])cc2)NC(=O)c2ccccc2O1
Yield: 31 %

Procedure:
Preparation of 4-[2-oxo-propoxy]nitrobenzene—To stirred suspension of K2CO3 (50.0 g, 0.36 mol) in dry DMF (500 mL) was added 4-nitrophenol (25.0 g, 0.18 mol) and stirred for 30 min at 25° C. Chloroacetone (21.5 mL, 0.27 mol) was added to the reaction mixture and stirred for 24 h at 25-30° C. The reaction mixture was filtered through a buchner funnel. The filtrate was poured into water (500 mL) and extracted with ethyl acetate (3×300 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated. The crude compound was purified by column chromatography using EtOAc:Pet. ether (1:2) as eluent to yield the title compound (11.0 g, 31%) as a colourless liquid.
Reaction SMILES: C(O[C:5](=[O:7])[CH3:6])(=O)C.[NH2:8][N:9]1[C:17]2[C:12](=[CH:13][CH:14]=[C:15]([N+:18]([O-:20])=[O:19])[CH:16]=2)[C:11]([C:21]2[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=2)=[CH:10]1.C(N(C(C)C)CC)(C)C>CN(C=O)C.O>[C:25]([C:24]1[CH:23]=[CH:22][C:21]([C:11]2[C:12]3[C:17](=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][CH:13]=3)[N:9]([NH:8][C:5](=[O:7])[CH3:6])[CH:10]=2)=[CH:28][CH:27]=1)#[N:26]
Reactant: CC(=O)OC(C)=O
Reactant: N#Cc1ccc(-c2cn(N)c3cc([N+](=O)[O-])ccc23)cc1
Solvent: CN(C)C=O
Solvent: CCN(C(C)C)C(C)C
Solvent: O
Product: CC(=O)Nn1cc(-c2ccc(C#N)cc2)c2ccc([N+](=O)[O-])cc21
Reaction time: 3 h
Yield: 37.9 %

Procedure:
Add acetic anhydride (214 mg, 2.1 mmol) to a mixture of 4-(1-Amino-6-nitro-1H-indol-3-yl)-benzonitrile (400 mg, 1.4 mmol) and di-isopropylethylamine (194 mg, 2.1 mmol) and N,N-dimethylaminopyridine (2 mg) in DMF (20 mL) and stir for 3 h. Add additional acetic anhydride (214 mg, 2.1 mmol) and di-isopropylethylamine (194 mg, 2.1 mmol) and stir overnight. Dilute the mixture with water and extract with EtOAc. Wash the combined extracts with water and brine, and dry over MgSO4. Purify the crude residue using silica gel chromatography to give 170 mg (38% yield) of N-[3-(4-Cyano-phenyl)-6-nitro-indol-1-yl]-acetamide.
Reaction SMILES: C(=O)([O-])[O-].[K+].[K+].[CH:7]1([NH:10][C:11](=[O:30])[C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[C:14]([C:19]3[CH:20]=[C:21]4[C:26](=[CH:27][CH:28]=3)[C:25](=[O:29])[NH:24][CH:23]=[CH:22]4)[CH:13]=2)[CH2:9][CH2:8]1.Cl[CH2:32][C:33]1[CH:38]=[CH:37][C:36]([CH2:39]Cl)=[CH:35][CH:34]=1.[NH:41]1[CH2:45][CH2:44][CH2:43][CH2:42]1>CN(C=O)C>[CH:7]1([NH:10][C:11](=[O:30])[C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[C:14]([C:19]3[CH:20]=[C:21]4[C:26](=[CH:27][CH:28]=3)[C:25](=[O:29])[N:24]([CH2:32][C:33]3[CH:38]=[CH:37][C:36]([CH2:39][N:41]5[CH2:45][CH2:44][CH2:43][CH2:42]5)=[CH:35][CH:34]=3)[CH:23]=[CH:22]4)[CH:13]=2)[CH2:8][CH2:9]1
Reactant: C1CCNC1
Reactant: ClCc1ccc(CCl)cc1
Reactant: Cc1ccc(C(=O)NC2CC2)cc1-c1ccc2c(=O)[nH]ccc2c1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CN(C)C=O
Product: Cc1ccc(C(=O)NC2CC2)cc1-c1ccc2c(=O)n(Cc3ccc(CN4CCCC4)cc3)ccc2c1
Reaction time: 64 h

Procedure:
A mixture of potassium carbonate (0.34 g), the product of Example 11 (0.1 g) and 1,4-bis(chloromethyl)benzene (0.220 g) in DMF (2 mL) was stirred at room temperature for 2.5 hours. To the reaction mixture was added pyrrolidine (0.3 mL) and stirring continued for a further 64 hours. The reaction mixture was filtered and the filtrate washed with methanol. The liquors were purified by HPLC to give the title compound as a solid (0.095 g).
Reaction SMILES: [I:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[C:15]([C:17]1[CH:24]=[CH:23][C:20]([CH2:21]Br)=[CH:19][CH:18]=1)#[N:16]>C(#N)C.O>[I:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:21][C:20]2[CH:23]=[CH:24][C:17]([C:15]#[N:16])=[CH:18][CH:19]=2)=[CH:4][CH:3]=1
Reactant: Oc1ccc(I)cc1
Reactant: N#Cc1ccc(CBr)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CC#N
Product: N#Cc1ccc(COc2ccc(I)cc2)cc1
Temperature: 80 °C
Reaction time: 6 h

Procedure:
To a stirred solution of 4-iodo phenol (620 mg, 3.18 mmol) in acetonitrile (6 ml) was added K2CO3 (1.31 g, 9.54 mmol), followed by 4-cyanobenzyl bromide (700 mg, 3.18 mmol) at 20-35° C. and the reaction mixture was stirred at 80° C. for 6 h. The progress of the reaction was monitored by TLC. After 6 h of stirring, the mixture was cooled to 20-35° C., diluted with water (50 ml) and extracted with ethyl acetate (2×50 ml). The combined organic layers were washed with brine (50 ml), followed by drying over anhydrous Na2SO4 and filtering. The filtrate was rotary evaporated to get residue which was purified by column chromatography using a mixture of 10% ethyl acetate/hexane as an eluent to get the desired compound as a to pale yellow solid (800 mg, 75%). 1H NMR (400 MHz, DMSO-d6) δ 7.86 (d, J=8.3 Hz, 2H), 7.64-7.59 (m, 4H), 6.90-6.85 (m, 2H), 5.21 (s, 2H).