Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [Cl:1][C:2]1[C:3]([C:33](=[O:43])[N:34]([CH2:39][CH2:40][CH2:41][CH3:42])[CH2:35][CH2:36][CH2:37][CH3:38])=[N:4][N:5]([C:8]2[CH:16]=[CH:15][C:14]([C:17](=[O:32])[NH:18][S:19]([C:22]3[CH:31]=[CH:30][C:29]4[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=4)[CH:23]=3)(=[O:21])=[O:20])=[CH:13][C:9]=2[C:10]([OH:12])=O)[C:6]=1[CH3:7].[Br:44][C:45]1[CH:46]=[N:47][C:48]2[CH2:49][CH2:50][NH:51][CH2:52][C:53]=2[CH:54]=1>>[Br:44][C:45]1[CH:46]=[N:47][C:48]2[CH2:49][CH2:50][N:51]([C:10]([C:9]3[CH:13]=[C:14]([C:17](=[O:32])[NH:18][S:19]([C:22]4[CH:31]=[CH:30][C:29]5[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=5)[CH:23]=4)(=[O:21])=[O:20])[CH:15]=[CH:16][C:8]=3[N:5]3[C:6]([CH3:7])=[C:2]([Cl:1])[C:3]([C:33]([N:34]([CH2:35][CH2:36][CH2:37][CH3:38])[CH2:39][CH2:40][CH2:41][CH3:42])=[O:43])=[N:4]3)=[O:12])[CH2:52][C:53]=2[CH:54]=1
Reactant: Brc1cnc2c(c1)CNCC2
Reactant: CCCCN(CCCC)C(=O)c1nn(-c2ccc(C(=O)NS(=O)(=O)c3ccc4ccccc4c3)cc2C(=O)O)c(C)c1Cl
Product: CCCCN(CCCC)C(=O)c1nn(-c2ccc(C(=O)NS(=O)(=O)c3ccc4ccccc4c3)cc2C(=O)N2CCc3ncc(Br)cc3C2)c(C)c1Cl
Yield: 48.8 %

Procedure:
Following a procedure analogous to that for the synthesis of Intermediate 93B, 2-(4-chloro-3-(dibutylcarbamoyl)-5-methyl-1H-pyrazol-1-yl)-5-(naphthalen-2-ylsulfonylcarbamoyl)benzoic acid (Intermediate 91F, 25 mg, 0.040 mmol) and 3-bromo-5,6,7,8-tetrahydro-1,6-naphthyridine (D-L Chiral, 9 mg, 0.044 mmol) were converted to the title compound (16 mg, 45%) following purification by preparative HPLC. 1H NMR (1:1 CD3OD:CDCl3, 1.5:1 mixture of amide rotamers) δ ppm 8.69-8.65 (m, 1H), 8.47-8.41 (m, 1H), 8.21-8.16 (m, 1H), 8.09-8.05 (m, 2H), 8.04-8.00 (m, 1H), 7.99-7.95 (m, 1.5H), 7.94-7.90 (m, 1H), 7.78-7.74 (m, 0.5H), 7.66-7.57 (m, 1.5H), 7.53-7.43 (m, 1.5H), 4.79-4.73 (m, 1H), 4.57-4.51 (m, 1H), 3.71-3.61 (m, 1.5H), 3.58-3.39 (m, 1H), 3.31-2.85 (m, 5.5H), 2.31 (s, 1.5H), 2.28 (s, 1.5H), 1.57-1.02 (m, 8H), 0.93 (dt, J=14.4, 7.4 Hz, 3H), 0.79 (t, J=7.4 Hz, 1.5H), 0.74 (t, J=7.4 Hz, 1.5H); MS(ESI+) m/z 821.0 (M+H)+.
Reaction SMILES: C([O:5][C:6]([C:8]1[CH:30]=[CH:29][C:11]([O:12][C:13]2[CH:22]=[C:21]3[C:16]([CH:17]([C:23]([O:25][CH3:26])=[O:24])[CH2:18][CH2:19][O:20]3)=[CH:15][C:14]=2[C:27]#[N:28])=[CH:10][CH:9]=1)=[O:7])(C)(C)C.C(O)(C(F)(F)F)=O>C(Cl)Cl>[C:27]([C:14]1[CH:15]=[C:16]2[C:21](=[CH:22][C:13]=1[O:12][C:11]1[CH:29]=[CH:30][C:8]([C:6]([OH:7])=[O:5])=[CH:9][CH:10]=1)[O:20][CH2:19][CH2:18][CH:17]2[C:23]([O:25][CH3:26])=[O:24])#[N:28]
Reactant: COC(=O)C1CCOc2cc(Oc3ccc(C(=O)OC(C)(C)C)cc3)c(C#N)cc21
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: COC(=O)C1CCOc2cc(Oc3ccc(C(=O)O)cc3)c(C#N)cc21
Reaction time: 2 h
Yield: 69.5 %

Procedure:
Methyl 7-(4-(tert-butoxycarbonyl)phenoxy)-6-cyanochroman-4-carboxylate (400 mg, 0.977 mmol) was diluted with CH2Cl2 followed by the addition of TFA (1 mL). After stirring for 2 hours, the reaction was concentrated to yield the title compound (240 mg, 69.5% yield).
Reaction SMILES: [C:1]([O:6][CH3:7])(=[O:5])[C:2]([CH3:4])=[CH2:3].[Br:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18]CO.O>CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[C:1]([O:6][CH2:7][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][Br:8])(=[O:5])[C:2]([CH3:4])=[CH2:3]
Reactant: OCCCCCCCCCCCBr
Reactant: C=C(C)C(=O)OC
Agent: [Ti+4]
Agent: CC(C)[O-]
Solvent: O
Product: C=C(C)C(=O)OCCCCCCCCCCCBr
Reaction time: 3 h
Yield: 91 %

Procedure:
Methyl methacrylate (1.15 L, stabilised with 50 ppm of BHT), 11-bromoundecanol (200 g, 0.8 mole) and titanium tetraisopropoxide (11.4 g, 0.04 mole) are mixed together. A constant slow stream of dry air is bubbled through the reaction mixture during the reaction. The reaction mixture is heated under gentle reflux for 1 hour (internal temperature 90°). After this reflux period the methyl methacrylate/methanol azeotrope is removed under atmospheric distillation. During this time the internal temperature rises to 104° and the temperature at the still head rises from 65° to 101° (a total of 550 ml of distillate is collected). The reaction mixture is then cooled to 40° and quenched with water (1.5 ml, 2 equiv. based on titanium tetraisopropoxide). The resulting mixture is stirred for 3 hours then treated with celite (20 g). After stirring for a further 10 minutes the reaction mixture is filtered through a pad of celite. The filter pad is washed with methyl methacrylate (50 ml). The filtrate and wash are combined and distilled under vacuum (4-10 mmHg) at room temperature, then at 50°-60° to remove last traces of methyl methacrylate. During distillation a slow stream of dry air is bubbled through the residue in the distillation vessel. The product, 11-bromoundecyl methacrylate (233 g, 91% yield) is obtained as a pale yellow oil.
Reaction SMILES: [C:1]1([CH3:24])[CH:6]=[CH:5][C:4]([S:7][CH:8]([C:11]2[CH:16]=[CH:15][C:14]([C:17]([C:19]3[S:20][CH:21]=[CH:22][CH:23]=3)=[O:18])=[CH:13][CH:12]=2)[C:9]#[N:10])=[CH:3][CH:2]=1.[CH3:25][O-].[Na+].CI.[Cl-].[NH4+]>CO>[C:1]1([CH3:24])[CH:2]=[CH:3][C:4]([S:7][C:8]([C:11]2[CH:16]=[CH:15][C:14]([C:17]([C:19]3[S:20][CH:21]=[CH:22][CH:23]=3)=[O:18])=[CH:13][CH:12]=2)([CH3:25])[C:9]#[N:10])=[CH:5][CH:6]=1
Reactant: Cc1ccc(SC(C#N)c2ccc(C(=O)c3cccs3)cc2)cc1
Reactant: C[O-]
Agent: [Cl-]
Agent: [NH4+]
Agent: [Na+]
Solvent: CI
Solvent: CO
Product: Cc1ccc(SC(C)(C#N)c2ccc(C(=O)c3cccs3)cc2)cc1
Yield: 86 %

Procedure:
Anhydrous methanol (3 ml) was added to 351 mg of alpha-(p-tolylthio)[p-(2-thienylcabonyl)phenyl]acetonitrile, and the mixture was stirred in an argon atmosphere under ice cooling. Then, 0.45 ml of a 2.5 M methanol solution of sodium methoxide was added, and 0.10 ml of methyl iodide was added dropwise. The temperature was brought to room temperature and the mixture was stirred for 15 minutes. An aqueous solution of ammonium chloride (0.2 g/30 ml) was added, and the mixture was extracted with 20 ml of methylene chloride three times. The extract was washed with 20 ml of water, dried over anhydrous magnesium sulfate; and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel; methylene chloride) to afford 314 mg (yield 86%) of alpha-(p-tolylthio)-alpha-[p-(2-thienylcabonyl)phenyl]-propionitrile as colorless crystals.
Reaction SMILES: [C:1]1(=[O:8])O[C:5](=[O:6])[CH:4]=[C:2]1[CH3:3].[N:9]1([C:15]2[CH:21]=[CH:20][C:18]([NH2:19])=[CH:17][CH:16]=2)[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]1>N1C=CC=CC=1>[CH3:3][C:2]1[C:1](=[O:8])[N:19]([C:18]2[CH:17]=[CH:16][C:15]([N:9]3[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]3)=[CH:21][CH:20]=2)[C:5](=[O:6])[CH:4]=1
Reactant: CC1=CC(=O)OC1=O
Reactant: Nc1ccc(N2CCCCC2)cc1
Solvent: c1ccncc1
Product: CC1=CC(=O)N(c2ccc(N3CCCCC3)cc2)C1=O
Temperature: 90 °C

Procedure:
A solution of citraconic anhydride (0. 1 M) in pyridine (20 ml)was treated with 4-(1-piperidyl)aniline (0. 1 M). The reaction mixture was heated to 90° C. for six hours. The reaction mixture was then concentrated in vacuo and the residue was extracted into ethyl acetate. The ethyl acetate layer was washed with water and with cold aqueous hydrochloric acid, then dried over sodium sulphate and finally concentrated in vacuo. The residue obtained was chromatographed over silica gel to afford the desired product.
Reaction SMILES: [N+:1]([C:4]1[CH:9]=[C:8]([N+:10]([O-])=O)[CH:7]=[CH:6][C:5]=1[CH2:13][CH2:14][C:15]([O:17]CC)=O)([O-])=O.[H][H]>CO.[Pd]>[NH2:10][C:8]1[CH:9]=[C:4]2[C:5]([CH2:13][CH2:14][C:15](=[O:17])[NH:1]2)=[CH:6][CH:7]=1
Reactant: [H][H]
Reactant: CCOC(=O)CCc1ccc([N+](=O)[O-])cc1[N+](=O)[O-]
Agent: [Pd]
Solvent: CO
Product: Nc1ccc2c(c1)NC(=O)CC2
Temperature: 30 °C
Reaction time: 8 h

Procedure:
Into a 100 mL 3-necked round bottom flask was placed a solution of ethyl 3-(2,4-dinitrophenyl)propanoate (1.5 g, 5.60 mmol) in methanol (20 mL). To the mixture was added Pd/C (0.5 g). Hydrogen gas was passed through. The resulting solution was allowed to react, with stirring, overnight while the temperature was maintained at 30° C. A filtration was performed. The filtrate was concentrated by evaporation under vacuum using a rotary evaporator. This resulted in 0.5 g (55%) of 7-amino-3,4-dihydroquinolin-2(1H)-one as a green-yellow solid.