Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [OH:1][C:2]1[C:22]([CH2:23][CH2:24][CH3:25])=[CH:21][C:5]2[CH:6]=[C:7]([C:9]3[CH:14]=[C:13]([O:15][CH3:16])[C:12]([O:17][CH3:18])=[C:11]([O:19][CH3:20])[CH:10]=3)[O:8][C:4]=2[CH:3]=1>C(O)(=O)C.[Pd]>[OH:1][C:2]1[C:22]([CH2:23][CH2:24][CH3:25])=[CH:21][C:5]2[CH2:6][CH:7]([C:9]3[CH:14]=[C:13]([O:15][CH3:16])[C:12]([O:17][CH3:18])=[C:11]([O:19][CH3:20])[CH:10]=3)[O:8][C:4]=2[CH:3]=1
Reactant: CCCc1cc2cc(-c3cc(OC)c(OC)c(OC)c3)oc2cc1O
Agent: [Pd]
Solvent: CC(=O)O
Product: CCCc1cc2c(cc1O)OC(c1cc(OC)c(OC)c(OC)c1)C2
Reaction time: 2.5 h
Yield: 77 %

Procedure:
A solution of 6-Hydroxy-2-(3,4,5-trimethoxyphenyl)-5-propylbenzofuran (200 mg) in glacial acetic acid (1 ml) containing 10% palladium-on-charcoal was hydrogenated for 2.5 hours. The mixture was filtered and the filtrate was evaporated in vacuo to give 6-hydroxy-2-(3,4,5-trimethoxyphenyl)-5-propyl-2,3-dihydrobenzofuran (155 mg).
Reaction SMILES: O.[ClH:2].Cl.C([O:11][C:12]1[CH:29]=[CH:28][C:15]([O:16][CH2:17][CH2:18][NH:19][CH2:20][CH2:21][CH2:22][N:23]2[CH:27]=[CH:26][N:25]=[CH:24]2)=[CH:14][CH:13]=1)C1C=CC=CC=1>[Pd].CO>[ClH:2].[ClH:2].[N:23]1([CH2:22][CH2:21][CH2:20][NH:19][CH2:18][CH2:17][O:16][C:15]2[CH:14]=[CH:13][C:12]([OH:11])=[CH:29][CH:28]=2)[CH:27]=[CH:26][N:25]=[CH:24]1
Reactant: c1ccc(COc2ccc(OCCNCCCn3ccnc3)cc2)cc1
Agent: [Pd]
Agent: Cl
Solvent: O
Solvent: CO
Product: Oc1ccc(OCCNCCCn2ccnc2)cc1

Procedure:
N-[2-(4-Benzyloxyphenoxy)ethyl]-3-(imidazol-1-yl)propylamine dihydrochloride hydrate (4.24 g) was suspended in IMS (200 ml) and methanol (10 ml) and hydrogenated at atmospheric pressure using 10% palladium/charcoal as a catalyst (0.44 g). The mixture was filtered and the filtrate evaporated to give a residue which was triturated with warm ether and filtered to give a solid which was recrystallised from methanol/ether to give 4-{2-[3-(imidazol-1-yl)propylamino]ethoxy}phenol dihydrochloride, m.p. 195-197° C.
Reaction SMILES: [CH2:1]([O:3][C:4]1[CH:28]=[CH:27][C:7]2[CH:8]3[CH2:14][CH2:13][C:12]([C:16]4[CH:21]=[CH:20][C:19]([O:22][CH2:23][CH3:24])=[C:18]([F:25])[C:17]=4[F:26])(O)[CH2:11][CH:9]3[O:10][C:6]=2[C:5]=1[F:29])[CH3:2].O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4]1[CH:28]=[CH:27][C:7]2[CH:8]3[CH2:14][CH:13]=[C:12]([C:16]4[CH:21]=[CH:20][C:19]([O:22][CH2:23][CH3:24])=[C:18]([F:25])[C:17]=4[F:26])[CH2:11][CH:9]3[O:10][C:6]=2[C:5]=1[F:29])[CH3:2]
Reactant: CCOc1ccc(C2(O)CCC3c4ccc(OCC)c(F)c4OC3C2)c(F)c1F
Agent: Cc1ccc(S(=O)(=O)O)cc1
Solvent: O
Solvent: Cc1ccccc1
Product: CCOc1ccc(C2=CCC3c4ccc(OCC)c(F)c4OC3C2)c(F)c1F

Procedure:
8.5 g (20.8 mmol) of (±)-(4aR*, 9bS*)-7-ethoxy-3-(4-ethoxy-2,3-difluorophenyl)-6-fluoro-1,2,3,4,4a,9b-hexahydrodibenzofuran-3-ol in 200 ml of toluene are heated on a water separator for 30 min together with 396 mg (2.08 mmol) of p-toluenesulfonic acid monohydrate. After cooling, the batch is filtered adsorptively (SiO2, ethyl acetate:n-heptane=4:1), and the filtrate is concentrated to dryness. The product mixture obtained in this way can be used directly for the following reaction.
Reaction SMILES: [CH3:1][O:2][CH2:3][CH2:4]OS(C)(=O)=O.[Cl:10][C:11]1[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][C:12]=1[B:18]1[O:22][C:21]([CH3:24])([CH3:23])[C:20]([CH3:26])([CH3:25])[O:19]1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C(=O)C>[Cl:10][C:11]1[CH:16]=[CH:15][C:14]([O:17][CH2:4][CH2:3][O:2][CH3:1])=[CH:13][C:12]=1[B:18]1[O:22][C:21]([CH3:24])([CH3:23])[C:20]([CH3:26])([CH3:25])[O:19]1
Reactant: CC1(C)OB(c2cc(O)ccc2Cl)OC1(C)C
Reactant: COCCOS(C)(=O)=O
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC(=O)N(C)C
Product: COCCOc1ccc(Cl)c(B2OC(C)(C)C(C)(C)O2)c1

Procedure:
Methanesulfonic acid 2-methoxyethyl ester (70.5 mg, 0.50 mmol) and 2-[2-chloro-5-hydroxyphenyl]-4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane (Preparation 66,100 mg, 0.42 mmol) were stirred together in N,N-dimethylacetamide (4 ml). Potassium carbonate (58 mg, 0.42 mmol) was added and the resultant solution was heated to 100° C. for 10 hours. The reaction mixture was cooled then quenched with water (10 ml) and extracted with ethylacetate (10 ml). The organic layer was dried over anhydrous MgSO4 (s), filtered and evaporated in vacuo to give crude title compound. Material taken on without further purification.
Reaction SMILES: Br[C:2]1[S:6][C:5]([C:7]2[N:11]=[CH:10][N:9]([CH3:12])[N:8]=2)=[CH:4][CH:3]=1.[C:13]([O:17][C:18]([N:20]1[CH2:25][CH:24]=[C:23](B2OC(C)(C)C(C)(C)O2)[CH2:22][CH2:21]1)=[O:19])([CH3:16])([CH3:15])[CH3:14].ClCCl.C([O-])([O-])=O.[Na+].[Na+].[O-]S([O-])(=O)=O.[Mg+2]>O1CCOCC1>[C:13]([O:17][C:18]([N:20]1[CH2:21][CH:22]=[C:23]([C:2]2[S:6][C:5]([C:7]3[N:11]=[CH:10][N:9]([CH3:12])[N:8]=3)=[CH:4][CH:3]=2)[CH2:24][CH2:25]1)=[O:19])([CH3:16])([CH3:14])[CH3:15]
Reactant: Cn1cnc(-c2ccc(Br)s2)n1
Reactant: CC(C)(C)OC(=O)N1CC=C(B2OC(C)(C)C(C)(C)O2)CC1
Agent: O=C([O-])[O-]
Agent: O=S(=O)([O-])[O-]
Agent: [Mg+2]
Solvent: ClCCl
Solvent: C1COCCO1
Product: Cn1cnc(-c2ccc(C3=CCN(C(=O)OC(C)(C)C)CC3)s2)n1
Temperature: 80 °C
Reaction time: 8 h
Yield: 86.7 %

Procedure:
To a large pressure flask were charged compound 3-(5-bromo-thiophen-2-yl)-1-methyl-1H-[1,2,4]triazole (3.1 g, 12.8 mmols) (5BW), 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (3.6 g, 11.65 mmols), [1,1′-bis(diphenylphosphino)-ferrocene]dichloro-palladium (II), complex with dichloromethane (1:1) (0.475 g, 0.89 mmols), Na2CO3 (8.5 ml) and dioxane (40 ml). The mixture was briefly degassed with Ar for ˜0.5 minute, capped and stirred at 80° C. overnight. After cooling, the reaction mixture was diluted with EtOAc and brine. Organic layer was isolated, and dried MgSO4. After concentration, the residue was purified on silica gel. Elution with EtOAc (100%) gave the desired product (6BW) (3.5 g).
Reaction SMILES: [F:1][C:2]1[C:7]([F:8])=[CH:6][N:5]=[C:4]([NH:9]C(=O)C(C)(C)C)[CH:3]=1.[OH-].[Na+]>Cl>[F:1][C:2]1[C:7]([F:8])=[CH:6][N:5]=[C:4]([NH2:9])[CH:3]=1
Reactant: CC(C)(C)C(=O)Nc1cc(F)c(F)cn1
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Product: Nc1cc(F)c(F)cn1
Temperature: 25 °C

Procedure:
N-(4,5-difluoropyridin-2-yl)-2,2-dimethylpropanamide (47-2; 0.380 g) in concentrated HCl was heated at 95° C. for 5 h. The reaction mixture was cooled to RT, diluted with ice cold water (20 mL) and basified with 10% aqueous sodium hydroxide solution. The reaction mixture was extracted with ethyl acetate (2×50 mL). The combined organic layers were dried over sodium sulphate and concentrated under vacuum to afford the title compound. 1H NMR (400 MHz, DMSO) δ 7.72-7.67 (m, 1H), 6.59-6.55 (m, 1H), 6.48 (bs, 2H).
Reaction SMILES: [NH2:1][C:2]1[C:11]2[N:12]=[C:13]([CH2:23][O:24][CH2:25][CH3:26])[N:14]([NH:15][CH2:16][CH2:17][CH2:18][NH:19][C:20](=[O:22])[CH3:21])[C:10]=2[C:9]2[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=2[N:3]=1.O.[OH-].[Na+]>C(O)(C(F)(F)F)=O.C(Cl)(Cl)Cl.[Pt](=O)=O>[NH2:1][C:2]1[C:11]2[N:12]=[C:13]([CH2:23][O:24][CH2:25][CH3:26])[N:14]([NH:15][CH2:16][CH2:17][CH2:18][NH:19][C:20](=[O:22])[CH3:21])[C:10]=2[C:9]2[CH2:8][CH2:7][CH2:6][CH2:5][C:4]=2[N:3]=1
Reactant: CCOCc1nc2c(N)nc3ccccc3c2n1NCCCNC(C)=O
Agent: O=[Pt]=O
Agent: [Na+]
Agent: [OH-]
Solvent: O=C(O)C(F)(F)F
Solvent: O
Solvent: ClC(Cl)Cl
Product: CCOCc1nc2c(N)nc3c(c2n1NCCCNC(C)=O)CCCC3
Temperature: 25 °C
Reaction time: 18 h
Yield: 28.5 %

Procedure:
A solution of N-(3-{[4-amino-2-(ethoxymethyl)-1H-imidazo[4,5-c]quinolin-1-yl]amino}propyl)acetamide (0.220 g, 0.617 mmol) in 15 mL of TFA was treated with platinum (IV) oxide (0.140 g, 0.617 mmol). The mixture was placed under an atmosphere of hydrogen (3.8×105 Pa) and shaken at ambient temperature. After 18 h, the reaction mixture was diluted with CHCl3 (15 mL) and filtered through a pad of CELITE filter agent and rinsed with several portions of CHCl3 (1% TFA). The filtrate was concentrated under reduced pressure to yield an off-white oil. The oil was suspended in a minimum amount of H2O and treated with 50% NaOH solution until the pH of the liquid was 12–13. The mixture was extracted with CH2Cl2 (3×15 mL). The combined organic extracts were washed with brine (15 mL), dried over Na2SO4, filtered and concentrated under reduced pressure to yield an off-white solid. The solid was purified by chromatography (SiO2, 15–20% (80:18:2 CHCl3:MeOH:NH4OH) in CHCl3) to yield a white solid. The solid was recrystallized from MeCN to yield N-(3-{[4-amino-2-(ethoxymethyl)-6,7,8,9-tetrahydro-1H-imidazo[4,5-c]quinolin-1-yl]amino}propyl)acetamide (0.0633 g) as white crystals. mp 198–200° C.; 1H NMR (500 MHz, DMSO-d6) δ 7.80 (t, J=5.0 Hz, 1H), 6.30 (t, J=6.0 Hz, 1H), 5.78 (s, 2H), 4.61 s, 2H), 3.55 (q, J=7.0 Hz, 2H), 3.12 (q, J=6.7 Hz, 2H), 3.05–3.01 (m, 4H), 2.66 (t, J=5.9 Hz, 2H), 1.78–1.73 (m, 7H), 1.62 (p, J=7.1 Hz, 2H), 1.14 (t, J=7.0 Hz, 3H); 13C NMR (125 MHz DMSO-d6) δ 169.4, 149.9, 149.3, 147.1, 137.6, 122.7, 105.5, 65.7, 63.4, 51.6, 36.8, 32.5, 27.9, 23.9, 23.0, 23.0, 22.5, 15.3; MS (APCI) m/z 361 (M+H)+; Anal. Calcd for C18H28N6O2: C, 59.98; H, 7.83; N, 23.31;
Reaction SMILES: [I:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH2:8].[C:9](O)(=[O:13])[C:10]#[C:11][CH3:12].C1(N=C=NC2CCCCC2)CCCCC1>ClCCl>[I:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9](=[O:13])[C:10]#[C:11][CH3:12]
Reactant: Nc1ccccc1I
Reactant: CC#CC(=O)O
Agent: C(=NC1CCCCC1)=NC1CCCCC1
Solvent: ClCCl
Product: CC#CC(=O)Nc1ccccc1I
Temperature: 0 °C
Reaction time: 3 h
Yield: 99.8 %

Procedure:
A mixture of 2-iodo-phenylamine (10 g, 45.7 mmol) and but-2-ynoic acid (4.6 g, 54.8 mmol) in dichloromethane (50 ml) was cooled to 0° C. Then 1,3-dicyclohexylcarbodiimide (14 g, 68.6 mmol) was added. After stirring for 3 hours at room temperature, the mixture was washed with water (20 ml). The organic layer was dried over sodium sulfate and concentrated to give the crude product but-2-ynoic acid (2-iodo-phenyl)-amide (13.0 g, 100%) as a yellow solid which was used in next step without purification. MS calcd. for C10H8INO 285.1, obsd. (ESI+) [(M+H)+] 286.0.
Reaction SMILES: [Cl-].[CH3:2][C@:3]12[C@@:20]3([CH3:21])[C@@H:11]([C@:12]4([CH3:25])[C@@H:17]([CH2:18][CH2:19]3)[C:16]([CH3:23])([CH3:22])[C:15](=[O:24])[CH2:14][CH2:13]4)[CH2:10][CH2:9][C@@H:8]1[C@H:7]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:6]1([NH3+:32])[CH2:5][CH2:4]2.[O-]P(OP(OP([O-])([O-])=O)([O-])=O)(=O)[O-].[K+].[K+].[K+].[K+].[K+].Cl[CH2:52][CH2:53]Cl>C(#N)C>[N:32]1([C@:6]23[CH2:28][CH2:27][C@@H:26]([C:29]([CH3:31])=[CH2:30])[C@@H:7]2[C@@H:8]2[C@@:3]([CH3:2])([CH2:4][CH2:5]3)[C@@:20]3([CH3:21])[C@@H:11]([C@:12]4([CH3:25])[C@@H:17]([CH2:18][CH2:19]3)[C:16]([CH3:22])([CH3:23])[C:15](=[O:24])[CH2:14][CH2:13]4)[CH2:10][CH2:9]2)[CH2:53][CH2:52]1
Reactant: C=C(C)[C@@H]1CC[C@]2([NH3+])CC[C@]3(C)[C@H](CC[C@@H]4[C@@]5(C)CCC(=O)C(C)(C)[C@@H]5CC[C@]43C)[C@@H]12
Reactant: ClCCCl
Agent: O=P([O-])([O-])OP(=O)([O-])OP(=O)([O-])[O-]
Agent: [Cl-]
Agent: [K+]
Solvent: CC#N
Product: C=C(C)[C@@H]1CC[C@]2(N3CC3)CC[C@]3(C)[C@H](CC[C@@H]4[C@@]5(C)CCC(=O)C(C)(C)[C@@H]5CC[C@]43C)[C@@H]12
Temperature: 130 °C

Procedure:
A mixture of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-aminium chloride (1.09 g, 2.359 mmol) and potassium triphosphate (2.7 g, 12.72 mmol) in 1,2-dichloroethane (12 mL) and acetonitrile (24 mL) was placed in a thick-walled resealable vessel. The reaction vessel with its contents were flushed with nitrogen, sealed, and warmed to 130° C. for 36 hours. The crude reaction mixture was cooled to RT, filtered through a short bed (−1″ thick) of silica gel type-H, washed with ethyl acetate (150 mL). The filtrate was concentrated into a free flowing solid (1.1 g, quantitative) which was taken to the next step without further purification. MS: m/e 452.35 (M+H)+, 3.12 min (method 21). 1H NMR (400 MHz, CHLOROFORM-d) δ 4.77 (d, J=2.5 Hz, 1H), 4.62 (dd, J=2.5, 1.5 Hz, 1H), 2.74-2.56 (m, 2H), 2.55-2.36 (m, 3H), 2.10-2.00 (m, 1H), 1.96-1.86 (m, 1H), 1.85-1.75 (m, 1H), 1.74-1.67 (m, 2H), 1.68 (s, 3H), 1.55-1.24 (m, 16H), 1.16-1.10 (m, 1H), 1.08 (s, 3H), 1.07 (s, 3H), 1.04 (s, 3H), 0.98 (s, 3H), 0.96 (d, J=2.8 Hz, 2H), 0.94 (s, 3H).
Reaction SMILES: C(O[C:4]([C:6]1[CH:11]=[CH:10][C:9]([O:12][CH2:13][C:14]2[C:15]([C:21]3[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=3)=[N:16][O:17][C:18]=2[CH2:19][OH:20])=[CH:8][N:7]=1)=[O:5])C.[F:28][C:29]([F:33])([F:32])[CH2:30][NH2:31]>>[F:28][C:29]([F:33])([F:32])[CH2:30][NH:31][C:4]([C:6]1[CH:11]=[CH:10][C:9]([O:12][CH2:13][C:14]2[C:15]([C:21]3[CH:22]=[CH:23][C:24]([F:27])=[CH:25][CH:26]=3)=[N:16][O:17][C:18]=2[CH2:19][OH:20])=[CH:8][N:7]=1)=[O:5]
Reactant: NCC(F)(F)F
Reactant: CCOC(=O)c1ccc(OCc2c(-c3ccc(F)cc3)noc2CO)cn1
Product: O=C(NCC(F)(F)F)c1ccc(OCc2c(-c3ccc(F)cc3)noc2CO)cn1
Yield: 81 %

Procedure:
As described for example 31, 5-[3-(4-fluoro-phenyl)-5-hydroxymethyl-isoxazol-4-ylmethoxy]-pyridine-2-carboxylic acid ethyl ester (75 mg, 0.2 mmol) was converted, using 2,2,2-trifluoroethylamine instead of 1,1,1-trifluoro-isopropylamine, to the title compound (70 mg, 81%), which was obtained as a colourless gum. MS: m/e=426.2 [M+H]+.
Reaction SMILES: C([N:4]1[C:12]2[C:7](=[C:8]([CH3:27])[C:9]([CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[C:10]([CH3:20])[C:11]=2[NH:13][C:14](=[O:19])[C:15]([CH3:18])([CH3:17])[CH3:16])[CH2:6][CH2:5]1)(=O)C.[O-]CC.[Na+].S(=O)(=O)(O)O.[OH-].[Na+]>C(OCC)(=O)C.C(O)C.O>[CH2:25]([O:24][C:22]([CH2:21][C:9]1[C:8]([CH3:27])=[C:7]2[C:12](=[C:11]([NH:13][C:14](=[O:19])[C:15]([CH3:17])([CH3:16])[CH3:18])[C:10]=1[CH3:20])[NH:4][CH2:5][CH2:6]2)=[O:23])[CH3:26]
Reactant: CCOC(=O)Cc1c(C)c2c(c(NC(=O)C(C)(C)C)c1C)N(C(C)=O)CC2
Agent: CC[O-]
Agent: O=S(=O)(O)O
Agent: [Na+]
Solvent: CCO
Solvent: CCOC(C)=O
Solvent: O
Product: CCOC(=O)Cc1c(C)c2c(c(NC(=O)C(C)(C)C)c1C)NCC2
Yield: 104.9 %

Procedure:
To a mixture of N-(1-acetyl-5-ethoxycarbonylmethyl-4,6-dimethylindolin-7-yl)-2,2-dimethylpropanamide obtained in Example 9 (3.5 g) and ethanol (35 ml) was added dropwise sodium ethoxide (20 wt % ethanol solution) while keeping the reaction temperature below 30° C., and the resulting mixture was refluxed for 1 hour. After cooling to 0–5° C., concentrated sulfuric acid (6.88 g, 7.5 equivalent) was added dropwise with stirring under cooling condition while keeping the reaction temperature below 30° C., and the resulting mixture was refluxed for 2 hours. Water (17.5 ml) was added to the reaction mixture, and ethanol was evaporated off in vacuo. To the residue obtained was added ethyl acetate (35 ml), and pH of the resulting mixture was adjusted with 25% aqueous sodium hydroxide solution (the aqueous layer was adjusted to pH 12–13), and the resulting mixture was partitioned between ethyl acetate and water. The separated organic layer was furthermore washed with water (35 ml). The washing and the aqueous layer separated above were combined and reextracted with ethyl acetate (35 ml). The extract and the organic layer separated above were combined and concentrated under reduced pressure to afford the title compound (3.26 g) as a crude product.
Reaction SMILES: [CH3:1][CH:2]([O:4][C:5](=[O:22])[NH:6][C@H:7]1[C:16]2[C:11](=[CH:12][CH:13]=[C:14](Br)[CH:15]=2)[N:10]([C:18](=[O:20])[CH3:19])[C@@H:9]([CH3:21])[CH2:8]1)[CH3:3].[CH:23]([C:25]1[CH:30]=[CH:29][C:28](B(O)O)=[CH:27][CH:26]=1)=[O:24].C([O-])([O-])=O.[K+].[K+]>C(O)C.C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][CH:2]([O:4][C:5](=[O:22])[NH:6][C@H:7]1[C:16]2[C:11](=[CH:12][CH:13]=[C:14]([C:28]3[CH:29]=[CH:30][C:25]([CH:23]=[O:24])=[CH:26][CH:27]=3)[CH:15]=2)[N:10]([C:18](=[O:20])[CH3:19])[C@@H:9]([CH3:21])[CH2:8]1)[CH3:3]
Reactant: CC(=O)N1c2ccc(Br)cc2[C@H](NC(=O)OC(C)C)C[C@@H]1C
Reactant: O=Cc1ccc(B(O)O)cc1
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: Cc1ccccc1
Solvent: CCO
Product: CC(=O)N1c2ccc(-c3ccc(C=O)cc3)cc2[C@H](NC(=O)OC(C)C)C[C@@H]1C
Temperature: 90 °C
Reaction time: 16 h
Yield: 96 %

Procedure:
A mixture of 1-methylethyl[(2S,4R)-1-acetyl-6-bromo-2-methyl-1,2,3,4-tetrahydro-4-quinolinyl]carbamate (for a preparation see intermediate 100) (1 g, 2.71 mmol) and 4-formylbenzeneboronic acid (0.487 g, 3.25 mmol) in ethanol (4.7 mL) and toluene (4.70 mL) was treated with K2CO3 (0.449 g, 3.25 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.156 g, 0.135 mmol). The resulting mixture was stirred under nitrogen at 90° C. for 16 h then was cooled to room temperature and concentrated in vacuovacuo. The residue was partitioned between water (8.5 mL) and EtOAc (3 mL) and the resulting biphasic mixture was stirred at room temperature for 30 min then the insoluble residue was filtered off and dried under house vacuo at 40° C. for 1 hr to give 1-methylethyl[(2S,4R)-1-acetyl-6-(4-formylphenyl)-2-methyl-1,2,3,4-tetrahydro-4-quinolinyl]carbamate (1.0759 g, 2.59 mmol, 96% yield) as a light yellow solid.
Reaction SMILES: [O-2].[Cd+2:2].[C:3]([OH:22])(=[O:21])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]>>[C:3]([O-:22])(=[O:21])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].[Cd+2:2].[C:3]([O-:22])(=[O:21])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]
Reactant: CCCCCCCCCCCCCCCCCC(=O)O
Agent: [Cd+2]
Agent: [O-2]
Product: CCCCCCCCCCCCCCCCCC(=O)[O-]
Temperature: 90 °C

Procedure:
Cadmium oxide (0.127 g, 1 mmol) and stearic acid (0.500 g) were reacted at 220° C. for 10 min, cooled to 90° C., then a cadmium stearate (precursor) was formed. Into said system, toluene (10 ml), trioctylphosphine oxide (3.866 g) and trioctylphosphine (3.7 g) were added. Then a 0.05M aqueous solution of sodium sulfide (10 ml) was added. After the system was reacted at 90° C. for 3 h, a clear yellow sol containing CdS nanoparticles was obtained. Said sol has the typical excition absorption peak, can result in a quantum size effect and emit a fairly strong blue light under the irradiation of a UV lamp.
Reaction SMILES: [CH3:1][O:2][CH2:3][CH2:4][N:5]([CH2:7][C:8]1[CH:9]=[C:10]([CH:15]=[C:16]([CH3:18])[CH:17]=1)[C:11]([O:13]C)=[O:12])[CH3:6].O.[OH-].[Li+]>CO.O1CCCC1>[CH3:1][O:2][CH2:3][CH2:4][N:5]([CH2:7][C:8]1[CH:9]=[C:10]([CH:15]=[C:16]([CH3:18])[CH:17]=1)[C:11]([OH:13])=[O:12])[CH3:6]
Reactant: COCCN(C)Cc1cc(C)cc(C(=O)OC)c1
Agent: [Li+]
Agent: [OH-]
Solvent: O
Solvent: C1CCOC1
Solvent: CO
Product: COCCN(C)Cc1cc(C)cc(C(=O)O)c1
Temperature: 25 °C
Reaction time: 2 h

Procedure:
To a stirred solution of methyl 3-{[(2-methoxyethyl)(methyl)amino]methyl}-5-methylbenzoate (180 mg, 0.72 mmol) in methanol (2 mL), tetrahydrofuran (1 mL), and water (1 mL) is added lithium hydroxide (302 mg, 7.2 mmol) and the reaction mixture stirred at room temperature for 2 h. The reaction mixture is concentrated under reduced pressure, dissolved in methylene chloride, filtered, and the filtrate concentrated under reduced pressure to provide the title compound. ESI MS m/z 238 [M+H]+.
Reaction SMILES: Cl[CH2:2][C:3]([CH3:6])([OH:5])[CH3:4].[OH:7][C:8]1[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[CH:10][CH:9]=1.C([O-])([O-])=O.[K+].[K+]>O.C(O)C>[OH:5][C:3]([CH3:6])([CH3:4])[CH2:2][O:7][C:8]1[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[CH:10][CH:9]=1
Reactant: N#Cc1ccc(O)cc1
Reactant: CC(C)(O)CCl
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CCO
Solvent: O
Product: CC(C)(O)COc1ccc(C#N)cc1
Temperature: 80 °C
Yield: 94 %

Procedure:
A mixture of 1-chloro-2-methyl-propan-2-ol (10 mL), 4-hydroxybenzonitrile (2 g, 16.8 mmol), K2CO3 (9.3 g, 67.3 mmol) in water (6 mL) and ethanol (60 mL) was heated at 80° C. for 16 hours. The reaction mixture was cooled and the solvent was concentrated in vacuo. The residue was diluted with ether (200 mL) and filtered and the filtrate was washed sequentially with water (50 mL) and brine solution (50 mL). The organics were separated and dried over MgSO4 and solvent was removed in vacuo to give a residue which was purified by silica gel column chromatography using (0-100%) EtOAc/DCM as eluent to give 4-(2-hydroxy-2-methyl-propoxy)benzonitrile (3.0 g, 94%) as a yellow solid. ESI-MS m/z calc. 191.1, found 192.3 (M+1)+; Retention time: 1.05 minutes (3 min run).
Reaction SMILES: [CH3:1][NH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[Cl:9][CH2:10][CH2:11][C:12](Cl)=[O:13]>O1CCCC1>[Cl:9][CH2:10][CH2:11][C:12]([N:2]([CH3:1])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)=[O:13]
Reactant: O=C(Cl)CCCl
Reactant: CNc1ccccc1
Solvent: C1CCOC1
Product: CN(C(=O)CCCl)c1ccccc1
Yield: 92.6 %

Procedure:
A solution of 107.2 g (1.00 mole) of N-methylaniline in 150 ml of tetrahydrofuran was added dropwise to a solution of 90.4 g (0.71 mole) of 3-chloropropionyl chloride in 250 ml of tetrahydrofuran. The reaction temperature was maintained between 5° and 15° C. throughout the addition. After the final addition, the solution was filtered to remove a solid precipitate, and the filtrate was concentrated under reduced pressure to yield 130.0 g (91%) of a dark oil. An analytical sample was prepared by filtering the oil through a small bed of silica gel and eluting with ethyl acetate-hexane (1:5). The fractions containing the desired product were combined and concentrated under reduced pressure to give a light-yellow liquid. The liquid was partitioned between ethyl acetate and a saturated sodium bicarbonate solution. The ethyl acetate layer was washed with water and brine, dried (MgSO4), and concentrated under reduced pressure to give the title compound as a light-yellow oil.
Reaction SMILES: [2H][C:2]1[C:7]([2H])=[C:6]([NH2:9])[C:5]([NH2:10])=[C:4]([2H])[C:3]=1[2H].C(O)(=O)C(O)=O.[Br:19][C:20]1[CH:21]=[C:22]([CH:25]=[CH:26][CH:27]=1)[CH:23]=O>C(O)C.O>[Br:19][C:20]1[CH:21]=[C:22]([C:23]2[NH:10][C:5]3[CH:4]=[CH:3][CH:2]=[CH:7][C:6]=3[N:9]=2)[CH:25]=[CH:26][CH:27]=1
Reactant: [2H]c1c([2H])c([2H])c(N)c(N)c1[2H]
Reactant: O=Cc1cccc(Br)c1
Agent: O=C(O)C(=O)O
Solvent: O
Solvent: CCO
Product: Brc1cccc(-c2nc3ccccc3[nH]2)c1
Temperature: 80 °C
Reaction time: 8 h
Yield: 26.6 %

Procedure:
O-phenylenediamine (81.8 g, 756.6 mmol) and oxalic acid (3.4 g, 37.8 mmol) were completely dissolved in EtOH—H2O/1:1 (2 L) previously warmed at 80° C. 3-Bromobenzaldehyde (44.10 mL, 378.30 mmol) was then added dropwise to the solution. The reaction mixture was stirred overnight at 70° C. to the open air. The day after solid was filtered off and triturated with MeOH (150 mL) to give the product as a pale yellow solid (27.50 g). 3.8 g were recovered from the mother liquors. Total yield 31.30 g (30%).