Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][C:2]([CH3:19])=[C:3]([N:8]1[C@H:11]([CH2:12][CH:13]=[CH2:14])[C@@H:10]([CH:15]([OH:17])[CH3:16])[C:9]1=[O:18])[C:4]([O:6][CH3:7])=[O:5].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH:39](O)=[O:40].N(C(OCC)=O)=NC(OCC)=O>O1CCCC1.C(OCC)(=O)C>[CH3:19][C:2]([CH3:1])=[C:3]([N:8]1[C@H:11]([CH2:12][CH:13]=[CH2:14])[C@@H:10]([C@H:15]([O:17][CH:39]=[O:40])[CH3:16])[C:9]1=[O:18])[C:4]([O:6][CH3:7])=[O:5]
Reactant: C=CC[C@@H]1[C@@H](C(C)O)C(=O)N1C(C(=O)OC)=C(C)C
Reactant: O=CO
Agent: CCOC(=O)N=NC(=O)OCC
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: C1CCOC1
Solvent: CCOC(C)=O
Product: C=CC[C@@H]1[C@@H]([C@@H](C)OC=O)C(=O)N1C(C(=O)OC)=C(C)C
Temperature: 0 °C
Reaction time: 8 h

Procedure:
A 1:3 mixture of methyl 3-methyl-2-[(3S,4R)-3-[(1RS)-1-hydroxyethyl]-2-oxo-4-allylazetidin-1-yl]but-2-enoate (55 mg) was dissolved in tetrahydrofuran (2 ml) and triphenylphosphine (135 mg) and formic acid (19.4 μl) were added to the mixture. This mixture was cooled to 0° C. and a solution of diethyl azodicarboxylate (81 μl) in tetrahydrofuran (1 ml) was added. After stirring at the same temperature overnight, the mixture was diluted with ethyl acetate (30 ml), washed with aqueous sodium bicarbonate and brine, dried over magnesium sulfate and evaporated. The residue was chromatographed on silica gel (5 g) eluting with hexane and ethyl acetate (10:1-2:1) to give 25 mg of methyl 3-methyl-2-[(3S,4R)-3-[(1R)-1-formyloxyethyl]-2-oxo-4-allylazetidin-1-yl]-but-2-enoate.
Reaction SMILES: [N+](C1C=C([C:10]([C:12]2[C:20]3[C:15](=[N:16][CH:17]=[C:18]([C:21]4[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=4)[CH:19]=3)[NH:14][CH:13]=2)=[O:11])C=CC=1)([O-])=O.C([N-]C(C)C)(C)C.[Li+].C1CCCCC1.[C:41]1([CH3:51])[CH:46]=[CH:45][C:44]([S:47](Cl)(=[O:49])=[O:48])=[CH:43][CH:42]=1>O1CCCC1.O>[N:23]1[CH:24]=[CH:25][CH:26]=[C:21]([C:18]2[CH:19]=[C:20]3[C:12]([CH:10]=[O:11])=[CH:13][N:14]([S:47]([C:44]4[CH:45]=[CH:46][C:41]([CH3:51])=[CH:42][CH:43]=4)(=[O:49])=[O:48])[C:15]3=[N:16][CH:17]=2)[CH:22]=1
Reactant: O=C(c1cccc([N+](=O)[O-])c1)c1c[nH]c2ncc(-c3cccnc3)cc12
Reactant: Cc1ccc(S(=O)(=O)Cl)cc1
Agent: CC(C)[N-]C(C)C
Agent: [Li+]
Solvent: C1CCCCC1
Solvent: C1CCOC1
Solvent: O
Product: Cc1ccc(S(=O)(=O)n2cc(C=O)c3cc(-c4cccnc4)cnc32)cc1
Reaction time: 0.5 h

Procedure:
To (3-nitro-phenyl)-(5-pyridin-3-yl-1H-pyrrolo[2,3-b]pyridin-3-yl)-methanone (536, 291 mg, 0.85 mmol) in tetrahydrofuran (7 mL) was added 1.5 M of lithium diisopropylamide in cyclohexane (676 μl, 1.59 mmol) at −78° C. under an atmosphere of nitrogen. After 30 minutes, p-toluenesulfonyl chloride (209 mg, 1.10 mmol) was added in tetrahydrofuran and the reaction was stirred for three hours. The reaction was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate and concentrated. All solids were filtered and purified by silica gel column chromatography eluting with 60% ethyl acetate in hexane to give the compound (537, 182 mg, 43%). MS(ESI)[M+H+]+=499.2.
Reaction SMILES: [C:1]([C:5]1[O:9][N:8]=[C:7]([NH:10][C:11](=[O:39])[CH2:12][C:13]2[CH:18]=[CH:17][C:16]([C:19]3[N:23]4[CH:24]=[CH:25][C:26]([C:28]5[CH:29]=[N:30][N:31](S(=O)(=O)N(C)C)[CH:32]=5)=[CH:27][C:22]4=[N:21][CH:20]=3)=[CH:15][CH:14]=2)[CH:6]=1)([CH3:4])([CH3:3])[CH3:2]>C(Cl)Cl.CO.Cl.CCOCC.CC(O)=O>[C:1]([C:5]1[O:9][N:8]=[C:7]([NH:10][C:11](=[O:39])[CH2:12][C:13]2[CH:14]=[CH:15][C:16]([C:19]3[N:23]4[CH:24]=[CH:25][C:26]([C:28]5[CH:29]=[N:30][NH:31][CH:32]=5)=[CH:27][C:22]4=[N:21][CH:20]=3)=[CH:17][CH:18]=2)[CH:6]=1)([CH3:4])([CH3:2])[CH3:3]
Reactant: CN(C)S(=O)(=O)n1cc(-c2ccn3c(-c4ccc(CC(=O)Nc5cc(C(C)(C)C)on5)cc4)cnc3c2)cn1
Agent: Cl
Solvent: CO
Solvent: CC(=O)O
Solvent: CCOCC
Product: CC(C)(C)c1cc(NC(=O)Cc2ccc(-c3cnc4cc(-c5cn[nH]c5)ccn34)cc2)no1
Reaction time: 1 h

Procedure:
Dissolve N-(5-tert-Butyl-isoxazol-3-yl)-2-{4-[7-(1-dimethylsulfamoyl-1H-pyrazol-4-yl)-imidazo[1,2-a]pyridin-3-yl]-phenyl}-acetamide in CH2Cl2, methanol and 1 N HCl in ether in equal volumes and then concentrate to give a solid. Dissolve the solid in HOAc and stir for 1 hour. Concentrate and purify by silica gel chromatography with 0-5% MeOH in CH2Cl2. MS(ES), m/z 441 (M+1).
Reaction SMILES: [H-].[Na+].[Cl:3][C:4]1[CH:10]=[C:9]([C:11]([F:14])([F:13])[F:12])[CH:8]=[C:7]([Cl:15])[C:5]=1[NH2:6].[CH3:16][N:17]1[C:22](=[O:23])[CH:21]=[C:20]([C:24]([F:27])([F:26])[F:25])[N:19]=[C:18]1SC.Cl>C(Cl)(Cl)Cl.C(OCC)(=O)C.CN(C=O)C>[Cl:3][C:4]1[CH:10]=[C:9]([C:11]([F:14])([F:13])[F:12])[CH:8]=[C:7]([Cl:15])[C:5]=1[NH:6][C:18]1[N:17]([CH3:16])[C:22](=[O:23])[CH:21]=[C:20]([C:24]([F:27])([F:25])[F:26])[N:19]=1
Reactant: Nc1c(Cl)cc(C(F)(F)F)cc1Cl
Reactant: CSc1nc(C(F)(F)F)cc(=O)n1C
Agent: Cl
Agent: [H-]
Agent: [Na+]
Solvent: CCOC(C)=O
Solvent: CN(C)C=O
Solvent: ClC(Cl)Cl
Product: Cn1c(Nc2c(Cl)cc(C(F)(F)F)cc2Cl)nc(C(F)(F)F)cc1=O
Reaction time: 0.5 h
Yield: 40 %

Procedure:
Sodium hydride (60% in oil, 0.31 g, 7.65 mmol) was added to DMF (5 ml) solution of 2,6-dichloro-4-trifluoromethylaniline (0.80 g, 3.48 mmol), followed by stirring for 30 minutes. Then, 3-methyl-2-methylthio-6-trifluoromethyl-4(3H)-pyrimidinone (0.70 g, 3.13 mmol) was added, followed by stirring at 50° C. for 8 hours. After completion of the reaction, 1 N hydrochloric acid (30 ml) and ethyl acetate (20 ml) were added to the reaction solution to separate the organic layer, and the resulting aqueous layer was extracted with ethyl acetate (50 ml). The organic layers were combined, washed with water (30 ml×2) and saturated brine (70 ml) and then dried over anhydrous magnesium sulfate. The drying agent was removed by filtration, and the resulting filtrate was concentrated under a reduced pressure. By recrystallizing the thus obtained crude product from toluene and then from chloroform, white solid of 2-(2,6-dichloro-4-trifluoromethylphenyl)amino-3-methyl-6-trifluoromethyl-4(3H)-pyrimidinone [Compound No. 28] was obtained.
Reaction SMILES: [O:1]([C:8]1[CH:9]=[C:10](/[CH:14]=[CH:15]/[C:16](=O)[CH3:17])[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[NH2:20][OH:21].N1C=CC=CC=1>CO.CCOCC>[O:1]([C:8]1[CH:9]=[C:10](/[CH:14]=[CH:15]/[C:16](=[N:20][OH:21])[CH3:17])[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: NO
Reactant: CC(=O)/C=C/c1cccc(Oc2ccccc2)c1
Agent: Cl
Solvent: c1ccncc1
Solvent: CCOCC
Solvent: CO
Product: CC(/C=C/c1cccc(Oc2ccccc2)c1)=NO
Reaction time: 1 h
Yield: 96 %

Procedure:
The product from step (a) (10.0 g) and hydroxylamine hydrochloride (7 g) were taken up in methanol (50 ml), pyridine (15 ml) was added and the mixture stirred for 1 hour. The mixture was then stripped, redissolved in ether, washed with 2N aqu. HCl and satd. aqu. NaCl, dried over MgSO4, and stripped to give the desired product (10.2 g).
Reaction SMILES: [CH:1]1[C:6]([OH:7])=[CH:5][CH:4]=[C:3]([CH3:8])[CH:2]=1.ClCCCl.[N+:13]([O-])([OH:15])=[O:14]>O>[N+:13]([C:5]1[C:6]([OH:7])=[CH:1][CH:2]=[C:3]([CH3:8])[CH:4]=1)([O-:15])=[O:14]
Reactant: Cc1ccc(O)cc1
Reactant: O=[N+]([O-])O
Solvent: ClCCCl
Solvent: O
Product: Cc1ccc(O)c([N+](=O)[O-])c1
Temperature: 110 °C
Reaction time: 8 h
Yield: 99.1 %

Procedure:
A 100 mL reaction flask fitted with reverse dean-stark apparatus was charged with 10.804 g (0.1 mol) p-cresol, 65 mL 1,2 dichloro ethane, and 2.161 g of catalyst as prepared in example 5. The flask was flushed with nitrogen. The reaction mixture was refluxed at 110° C. for 1 h followed by dropwise addition of 8.6 mL (0.133 mol) 70% HNO3. The water formed during the reaction was removed using reverse dean-stark apparatus. The reaction was carried out for 8 h. The reaction was monitored by GC analysis. In this reaction, 98.7% conversion of p-cresol was obtained with 99.1% 2-nitro p-cresol and 0.9% of other products.
Reaction SMILES: [CH3:1][C:2]1([CH3:14])[C:6]2[CH:7]=[CH:8][CH:9]=[C:10]([N+:11]([O-:13])=[O:12])[C:5]=2[Se:4][NH:3]1.C(N(CC)CC)C.[Cl:22][CH2:23][C:24](Cl)=[O:25].[Cl-].C([NH+](CC)CC)C>C1COCC1.C(OCC)(=O)C.O>[Cl:22][CH2:23][C:24]([N:3]1[C:2]([CH3:14])([CH3:1])[C:6]2[CH:7]=[CH:8][CH:9]=[C:10]([N+:11]([O-:13])=[O:12])[C:5]=2[Se:4]1)=[O:25]
Reactant: CC1(C)N[Se]c2c([N+](=O)[O-])cccc21
Reactant: O=C(Cl)CCl
Agent: CC[NH+](CC)CC
Agent: [Cl-]
Solvent: CCOC(C)=O
Solvent: CCN(CC)CC
Solvent: O
Product: CC1(C)c2cccc([N+](=O)[O-])c2[Se]N1C(=O)CCl
Temperature: 5 °C
Reaction time: 1 h

Procedure:
To a solution of 3,3-dimethyl-7-nitrobenzisoselenazoline (1.28 g, 5 mmol), in 20 ml of anhydrous THF, containing triethylamine (0.83 ml, 6 mmol), cooled to 5° C. by an ice bath, is added dropwise chloroacetyl chloride (0.48 ml, 6 mmol). The dark brown reaction medium lightens rapidly, becoming luminous orange; as soon as the addition of the acid chloride is complete, a considerable precipitate, corresponding to triethylammonium chloride, appears. The amide formation reaction is exothermic. The ice bath is taken away and stirring is continued for about 1 hour at room temperature. After the addition of 20 ml of water and 20 ml of ethyl acetate, followed by separation, the organic phase is washed with 10 ml of a saturated aqueous solution of NaCl, then dried over MgSO4 and evaporated.
Reaction SMILES: [CH2:1]([C:8]1[S:9][C:10]([CH3:27])=[C:11]([CH3:26])[C:12]=1[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:24]=[CH:23][C:22]([OH:25])=[CH:21][CH:20]=2)=[CH:15][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[O:29][C:30](=[O:40])[C@H:31]([CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)O>>[CH2:1]([C:8]1[S:9][C:10]([CH3:27])=[C:11]([CH3:26])[C:12]=1[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:20]=[CH:21][C:22]([O:25][C@H:31]([CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:30]([OH:40])=[O:29])=[CH:23][CH:24]=2)=[CH:15][CH:14]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: COC(=O)[C@@H](O)Cc1ccccc1
Reactant: Cc1sc(Cc2ccccc2)c(-c2ccc(-c3ccc(O)cc3)cc2)c1C
Product: Cc1sc(Cc2ccccc2)c(-c2ccc(-c3ccc(O[C@H](Cc4ccccc4)C(=O)O)cc3)cc2)c1C

Procedure:
The title compound was prepared from 4′-(2-benzyl-4,5-dimethyl-thiophen-3-yl)-biphenyl-4-ol, and (S)-(−)-3-phenyllactic acid methyl ester, in substantially the same manner, as described in Example 29, and was obtained as an off-white solid, mp 142-144° C.; MS m/e 517 (M−H)+;