Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([OH:17])=[CH:7][C:8]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:9]2)=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[CH2:24](Br)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.O>CN(C=O)C>[CH2:24]([O:17][C:6]1[C:5]2[C:10](=[CH:11][C:2]([Br:1])=[CH:3][CH:4]=2)[CH:9]=[C:8]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:7]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1
Reactant: CCOC(=O)c1cc(O)c2ccc(Br)cc2c1
Reactant: BrCc1ccccc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CN(C)C=O
Product: CCOC(=O)c1cc(OCc2ccccc2)c2ccc(Br)cc2c1
Temperature: 25 °C
Reaction time: 11 h
Yield: 986.4 %

Procedure:
A solution of 6 (8.04 g, 2.2 mmol) in anhydrous DMF (150 mL) under Ar was treated with K2CO3 (5.65 g, 40.9 mmol), benzyl bromide (5.59 g, 32.7 mmol, 1.2 equiv) and BU4NI (402 mg, 1.1 mmol, 0.04 equiv). After stirring for 11 h at 25° C., the reaction mixture was poured into H2O (200 mL) and extracted with EtOAc (3×200 mL). The combined organic layers were washed with saturated aqueous NaCl, dried (MgSO4) and concentrated. The resulting solid was recrystallized from 5% EtOAc-hexane to afford 12 (8.36 g, 10.49 g theoretical, 80%) as white needles. An additional 2.13 g (20%) of 12 was obtained by chromatography (SiO2, 4×20 cm, 10% EtOAc-hexane) of the crystallization mother liquors: mp 105° C. (needles, hexane); 1H NMR (CDCl3, 250 MHz) δ8.19 (d, 1H, J=8.8 Hz), 8.10 (s, 1H), 8.05 (d, 1H, J=1.8 Hz), 7.61 (dd, 1H, J=1.9, 8.9 Hz), 7.50 (m, 6H), 5.28 (s, 2H), 4.45 (q, 2H, J=7.1 Hz), 1.46 (t, 3H, J=7.1 Hz); 13C NMR (CDCl3, 100 MHz) δ166.5, 154.7, 136.4, 134.7, 130.8, 130.7, 129.1, 128.7, 128.3, 127.6, 126.3, 124.2, 122.5, 121.5, 104.6, 70.4, 61.4, 14.4; IR (KBr) vmax 2986, 1716, 1589, 1578, 1406, 1369, 1331, 1279, 1238, 1098, 1025, 962, 892, 816, 767, 725, 691 cm-1 ; FABHRS (NBA) m/z 384.0370 (M+, C20H17BrO3 requires 384.0361).
Reaction SMILES: [CH2:1]1[O:10][C:4]([CH2:6][CH2:7][CH2:8]Cl)([CH3:5])[O:3][CH2:2]1.[F:11][C:12]([F:42])([F:41])[C:13]1[CH:14]=[C:15]([CH:34]=[C:35]([C:37]([F:40])([F:39])[F:38])[CH:36]=1)[C:16]([N:18]1[CH2:23][CH2:22][NH:21][CH2:20][C@H:19]1[CH2:24][C:25]1[C:33]2[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=2)[NH:27][CH:26]=1)=[O:17].C(N(C(C)C)CC)(C)C.CN(C)C=O>O>[F:40][C:37]([F:38])([F:39])[C:35]1[CH:34]=[C:15]([CH:14]=[C:13]([C:12]([F:11])([F:41])[F:42])[CH:36]=1)[C:16]([N:18]1[CH2:23][CH2:22][N:21]([CH2:8][CH2:7][CH2:6][C:4]2([CH3:5])[O:10][CH2:1][CH2:2][O:3]2)[CH2:20][C@H:19]1[CH2:24][C:25]1[C:33]2[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=2)[NH:27][CH:26]=1)=[O:17]
Reactant: O=C(c1cc(C(F)(F)F)cc(C(F)(F)F)c1)N1CCNC[C@H]1Cc1c[nH]c2ccccc12
Reactant: CC1(CCCCl)OCCO1
Solvent: CN(C)C=O
Solvent: O
Solvent: CCN(C(C)C)C(C)C
Product: CC1(CCCN2CCN(C(=O)c3cc(C(F)(F)F)cc(C(F)(F)F)c3)[C@H](Cc3c[nH]c4ccccc34)C2)OCCO1
Temperature: 90 °C
Yield: 39.9 %

Procedure:
A mixture of 5-chloro-2-pentanone ethylene ketal (0.54 g), (2R)-1-[3,5-bis(trifluoro-methyl)benzoyl]-2-(1H-indol-3-ylmethyl)piperazine (1.37 g), diisopropylethylamine (0.6 mL), and dimethylformamide (25 mL) was heated overnight, at 90°C. After cooling to room temperature the mixture was poured in water and extracted with ethyl acetate. The organic layer was dried (Na2SO4), and concentrated in vacuo. The residue was purified by flash chromatography (SiO2, CH2Cl2/MeOH 95/15) to afford (2R)-1-[3,5-bis(trifluoromethyl)benzoyl]-2-(1H-indol-3-ylmethyl)-4-[3-(2-methyl-1,3-dioxolan-2-yl)propyl]piperazine (0.7 g, 40%). MH+ 584.
Reaction SMILES: [C:1]1([CH:7]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:8](OC)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O.[NH2:19][NH2:20]>CCO>[C:1]1([CH:7]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:8]([NH:19][NH2:20])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: COC(=O)C(c1ccccc1)c1ccccc1
Reactant: NN
Solvent: CCO
Solvent: O
Product: NNC(=O)C(c1ccccc1)c1ccccc1
Reaction time: 1 h
Yield: 97 %

Procedure:
To a stirred solution of methyl 2,2-diphenylacetate (0.5 g, 1 equiv) in anhydrous EtOH (150 mL) was added hydrazine hydrate (8 mL) and heated to reflux. Stirring was then continued for 1 hour. The reaction mixture was then cooled and the solvents removed under reduced pressure. The crude oil was diluted with EtOAc and washed with H2O and the organic phase dried over Na2SO4, filtered, and the solvents removed under reduced pressure to yield a yellow oil (0.97 g, 97%) that was used without further purification.
Reaction SMILES: [NH2:1][CH2:2][CH2:3][NH:4][C:5]1[N:10]=[C:9]([C:11]2[CH:16]=[CH:15][C:14]([C:17]#[N:18])=[CH:13][CH:12]=2)[C:8]([C:19]2[NH:20][CH:21]=[CH:22][N:23]=2)=[CH:7][N:6]=1.Cl[C:25]1[CH:30]=[CH:29][C:28]([C:31]([F:34])([F:33])[F:32])=[CH:27][N:26]=1.CCN(C(C)C)C(C)C>CC(N(C)C)=O.C(OCC)(=O)C>[NH:20]1[CH:21]=[CH:22][N:23]=[C:19]1[C:8]1[C:9]([C:11]2[CH:16]=[CH:15][C:14]([C:17]#[N:18])=[CH:13][CH:12]=2)=[N:10][C:5]([NH:4][CH2:3][CH2:2][NH:1][C:25]2[CH:30]=[CH:29][C:28]([C:31]([F:34])([F:33])[F:32])=[CH:27][N:26]=2)=[N:6][CH:7]=1
Reactant: FC(F)(F)c1ccc(Cl)nc1
Reactant: N#Cc1ccc(-c2nc(NCCN)ncc2-c2ncc[nH]2)cc1
Solvent: CCOC(C)=O
Solvent: CCN(C(C)C)C(C)C
Solvent: CC(=O)N(C)C
Product: N#Cc1ccc(-c2nc(NCCNc3ccc(C(F)(F)F)cn3)ncc2-c2ncc[nH]2)cc1
Temperature: 80 °C
Reaction time: 12 h
Yield: 5 %

Procedure:
A mixture of 4-{2-[(2-aminoethyl)amino]-5-imidazolylpyrimidin-4-yl}benzene-carbonitrile (30 mg, 0.098 mmol), 2-chloro-5-(trifluoromethyl)pyridine (18 mg, 0.098 mmol), and Hünig's base (70 uL, 0.4 mmol) in DMA (500 uL) were heated to 80° C. After stirring for 12 hours, the reaction was diluted with ethyl acetate (10 ml) and extracted with sat. aq. NaHCO3 (2×5 ml), water (3×5 ml), brine (5 ml), dried with Na2SO4, filtered, and concentrated. The product was purified by preparative HPLC using a reverse phase column and a water/acetonitrile gradient. The product 4-{5-imidazolyl-2-[(2-{[5-(trifluoromethyl)(2-pyridyl)]amino}ethyl)amino]pyrimidin-4-yl}benzenecarbonitrilewas obtained as a off-white solid in 5% yield.
Reaction SMILES: [C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][CH:15]([CH2:20][C:21]#[N:22])[C:16]([O:18][CH3:19])=[O:17])[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2]>CC(O)=O.[Pd]>[NH2:22][CH2:21][CH2:20][CH:15]([CH2:14][C@H:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[C:10]([O:12][CH3:13])=[O:11])[C:16]([O:18][CH3:19])=[O:17]
Reactant: COC(=O)C(CC#N)C[C@H](NC(=O)OC(C)(C)C)C(=O)OC
Agent: [Pd]
Solvent: CC(=O)O
Product: COC(=O)C(CCN)C[C@H](NC(=O)OC(C)(C)C)C(=O)OC
Reaction time: 3 h

Procedure:
To a solution of (2S)-dimethyl 2-((tert-butoxycarbonyl)amino)-4-(cyanomethyl)pentanedioate (10.0 g, 31.8 mmol) in AcOH (240 mL) was added 10% Pd/C (2.0 g) and the mixture was stirred under H2 atmosphere (70 psi) for 3 h. The mixture was filtered through a pad of Celite and the filtrate was evaporated under reduced pressure. The residue was treated with MTBE and evaporated again to afford (4S)-dimethyl 2-(2-aminoethyl)-4-((tert-butoxycarbonyl)amino)pentanedioate (crude) as a light pink solid.
Reaction SMILES: BrC[CH2:3][C:4]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7].[F:15][C:16]1[CH:17]=[C:18]([OH:23])[CH:19]=[C:20]([F:22])[CH:21]=1>>[Cl:14][C:11]1[CH:12]=[CH:13][C:4]([CH2:3][O:23][C:18]2[CH:17]=[C:16]([F:15])[CH:21]=[C:20]([F:22])[CH:19]=2)=[C:5]([CH:10]=1)[C:6]([O:8][CH3:9])=[O:7]
Reactant: Oc1cc(F)cc(F)c1
Reactant: COC(=O)c1cc(Cl)ccc1CCBr
Product: COC(=O)c1cc(Cl)ccc1COc1cc(F)cc(F)c1

Procedure:
The title compound was prepared according to the procedure described in step 1 of Example 1 from methyl 2-(bromoethyl)-5-chlorobenzoate and 3,5-difluorophenol:
Reaction SMILES: [ClH:1].C(O[C:7](=O)[N:8]([C@H:10]([C:12](=[O:46])[NH:13][C@H:14]1[CH2:20][S:19][C:18]2[C:21]([NH:25][C:26](=[O:33])[CH2:27][O:28][CH2:29][CH2:30][O:31][CH3:32])=[CH:22][CH:23]=[CH:24][C:17]=2[N:16]([CH2:34][C:35]2[C:44]3[C:39](=[CH:40][CH:41]=[CH:42][CH:43]=3)[CH:38]=[CH:37][CH:36]=2)[C:15]1=[O:45])[CH3:11])C)(C)(C)C>O1CCOCC1>[ClH:1].[CH3:32][O:31][CH2:30][CH2:29][O:28][CH2:27][C:26]([NH:25][C:21]1[C:18]2[S:19][CH2:20][C@H:14]([NH:13][C:12](=[O:46])[C@@H:10]([NH:8][CH3:7])[CH3:11])[C:15](=[O:45])[N:16]([CH2:34][C:35]3[C:44]4[C:39](=[CH:40][CH:41]=[CH:42][CH:43]=4)[CH:38]=[CH:37][CH:36]=3)[C:17]=2[CH:24]=[CH:23][CH:22]=1)=[O:33]
Reactant: COCCOCC(=O)Nc1cccc2c1SC[C@H](NC(=O)[C@H](C)N(C)C(=O)OC(C)(C)C)C(=O)N2Cc1cccc2ccccc12
Agent: Cl
Solvent: C1COCCO1
Product: CN[C@@H](C)C(=O)N[C@H]1CSc2c(NC(=O)COCCOC)cccc2N(Cc2cccc3ccccc23)C1=O
Temperature: 25 °C
Reaction time: 1 h
Yield: 40 %

Procedure:
Hydrogen chloride gas was bubbled into a solution of ((S)-1-{(R)-9-[2-(2-methoxy-ethoxy)-acetylamino]-5-naphthalen-1-ylmethyl-4-oxo-2,3,4,5-tetrahydro-benzo[b][1,4]thiazepin-3-ylcarbamoyl}-ethyl)-methyl-carbamic acid tert-butyl ester (70 mg, 108 μmol) in dioxane (5 mL) at 0° C. for 1 min, the mixture was warmed to RT and stirred for 1 h. The mixture was concentrated, the residue was triturated with Et2O and the resulting solid was filtered, washed with Et2O and dried to give the title compound (25 mg, 40%). HR-MS: calcd for C29H34N4O5S (MH+) 551.2326. found 551.2323.
Reaction SMILES: Cl[C:2]12[O:8][CH:7]1[CH2:6][CH2:5][C:4](Cl)([Cl:9])[CH:3]2[CH3:11].Cl>CN(C=O)C>[Cl:9][C:4]1[C:3]([CH3:11])=[C:2]([OH:8])[CH:7]=[CH:6][CH:5]=1
Reactant: CC1C(Cl)(Cl)CCC2OC21Cl
Agent: Cl
Solvent: CN(C)C=O
Product: Cc1c(O)cccc1Cl
Yield: 89.2 %

Procedure:
2 g (9.28 mmol) of epoxide 2h in solution in 5 cm3 of anhydrous DMF were heated to reflux for 3 h. The solution was acidified (pH=1) with 3N HCl, extracted with ether (4×25 cm3), dried over MgSO4, filtered and evaporated down. The crude product obtained was purified by flash chromatography on silica (eluent: ether/petroleum ether=5/95). 1.18 g of phenol 4e were obtained (macrobore GC purity>96%). The yield of compound 4e was 89%.
Reaction SMILES: [C:1]([O:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[NH:13][C:12]([CH3:19])([CH3:18])[CH2:11]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:20]([O:24]O)([CH3:23])(C)C>[Mo](=O)(=O)=O.CCCCCCCC>[C:1]([O:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[N:13]([O:24][CH2:20][CH2:23][CH2:6][CH2:7][CH2:2][CH2:3][CH2:4][CH3:5])[C:12]([CH3:19])([CH3:18])[CH2:11]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: CC(C)(C)OO
Reactant: CC1(C)CC(OC(=O)c2ccccc2)CC(C)(C)N1
Agent: O=[Mo](=O)=O
Solvent: CCCCCCCC
Product: CCCCCCCCON1C(C)(C)CC(OC(=O)c2ccccc2)CC1(C)C
Temperature: 120 °C

Procedure:
A mixture of 55.3 grams (0.2 mol) of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2.8 grams of molybdenum trioxide and 250 ml of n-octane is heated to 120° C. A solution of 90.2 grams (0.7 mol) of 70% aqueous tert-butyl hydroperoxide is added dropwise to the hot reaction mixture. Water is removed by azeotropic distillation and collected in a Dean-Stark trap. The reaction mixture is heated at reflux till the red color of the intermediate N-oxyl compound disappears. Solids are removed by filtration, and the filtrate is concentrated under vacuum to give an oil. Purification of the oil by flash chromatography on silica gel (100:3 heptane:ethyl acetate) affords 4-benzoyloxy-1-octyloxy-2,2,6,6-tetramethylpiperidine as a mixture of octyloxy isomers. Further elution of the chromatographic column with 50:3 heptane:ethyl acetate affords the title compound as a mixture of octanediyl isomers.
Reaction SMILES: [O:1]=[C:2]([NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[CH3:14])[CH:3]=[C:4]([CH3:6])[CH3:5].C(=O)([O-])[O-]>S(=O)(=O)(O)O>[CH3:5][C:4]1([CH3:6])[C:13]2[C:8](=[C:9]([CH3:14])[CH:10]=[CH:11][CH:12]=2)[NH:7][C:2](=[O:1])[CH2:3]1
Reactant: CC(C)=CC(=O)Nc1ccccc1C
Agent: O=C([O-])[O-]
Agent: O=S(=O)(O)O
Product: Cc1cccc2c1NC(=O)CC2(C)C

Procedure:
N-(1-oxo-3-methyl-but-2-en-yl)-2-methylaniline (0.5 g) was added with stirring to 98% w/w sulphuric acid (10 cm3) at 0°. After 2 hours at room temperature (20°) the mixture was poured carefully onto ice (30 g) and the resulting solution was basified to pH 9 with saturated carbonate solution. The mixture was then extracted wilth dichloromethane (2×200 cm3), and the combined and dried (MgSO4) organic extracts were evaporated in vacuo to give a solid which was chromatographed on silica (Merck "MK 60.9385" [Trade mark]). Elution with dichloromethane, followed by combination and evaporation of appropriate fractions gave the title compound, m.p. 120° (0.21 g).
Reaction SMILES: [S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:37](=[O:38])[N:12]2[C:13]([C:21]([O:23]C(C3C=CC=CC=3)C3C=CC=CC=3)=[O:22])=[C:14]([C:17](=[O:20])[CH2:18][CH3:19])[CH2:15][S:16][C@H:11]12)=[O:8].C1(OC)C=CC=CC=1.FC(F)(F)C(O)=O>CCCCCCC>[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:37](=[O:38])[N:12]2[C:13]([C:21]([OH:23])=[O:22])=[C:14]([C:17](=[O:20])[CH2:18][CH3:19])[CH2:15][S:16][C@H:11]12)=[O:8]
Reactant: CCC(=O)C1=C(C(=O)OC(c2ccccc2)c2ccccc2)N2C(=O)C(NC(=O)Cc3cccs3)[C@H]2SC1
Solvent: CCCCCCC
Solvent: COc1ccccc1
Solvent: O=C(O)C(F)(F)F
Product: CCC(=O)C1=C(C(=O)O)N2C(=O)C(NC(=O)Cc3cccs3)[C@H]2SC1
Temperature: 5 °C
Yield: 92 %

Procedure:
To a cooled (5° C.), stirred slurry of 0.168 g. of benzhydryl 7-(2-thienylacetamido)-3-propionyl-3-cephem-4-carboxylate in 2 ml. of anisole was added 1 ml. of cold trifluoroacetic acid. The reaction mixture was allowed to stir with cooling for 20 minutes after which time 30 ml. of n-heptane was added. After the resulting solution was evaporated in vacuo to a low volume to remove excess trifluoroacetic acid, an additional 30 ml. of n-heptane was added. After stirring the reaction mixture in an ice bath for five minutes the mixture was filtered. The solid was dissolved in acetone, and the acetone solution was filtered. The filtrate was evaporated to low volume and subsequently transferred to a separatory funnel with the aid of cold ethyl acetate. The ethyl acetate solution was extracted twice with cold aqueous sodium bicarbonate solution. The aqueous extracts were combined, layered with cold ethyl acetate, and acidified with cold 1N.HCl. The organic layer was separated and washed twice with brine and dried over anhydrous sodium sulfate. Evaporation in vacuo to dryness provided 0.108 g. (92 percent) of the title product as a white solid:
Reaction SMILES: [C:1]([OH:6])(=[O:5])[C:2]([OH:4])=[O:3].Br[C:8]1[CH:9]=[C:10]([CH:26]=[CH:27][CH:28]=1)[CH2:11][CH:12]1[C:21]2[C:16](=[CH:17][C:18]([O:24][CH3:25])=[C:19]([O:22][CH3:23])[CH:20]=2)[CH2:15][CH2:14][NH:13]1.[OH-].[Na+].[C:31]1(B(O)O)[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Na+].[Na+].O.O.C(O)(=O)C(O)=O>CC([O-])=O.CC([O-])=O.[Pd+2].C(Cl)Cl>[C:1]([OH:6])(=[O:5])[C:2]([OH:4])=[O:3].[C:8]1([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:28]=[CH:27][CH:26]=[C:10]([CH2:11][CH:12]2[C:21]3[C:16](=[CH:17][C:18]([O:24][CH3:25])=[C:19]([O:22][CH3:23])[CH:20]=3)[CH2:15][CH2:14][NH:13]2)[CH:9]=1
Reactant: OB(O)c1ccccc1
Reactant: COc1cc2c(cc1OC)C(Cc1cccc(Br)c1)NCC2
Agent: [Pd+2]
Agent: CC(=O)[O-]
Agent: O=C(O)C(=O)O
Solvent: O
Solvent: ClCCl
Product: COc1cc2c(cc1OC)C(Cc1cccc(-c3ccccc3)c1)NCC2
Temperature: 25 °C

Procedure:
1-biphenyl-3-ylmethyl-6,7-dimethoxy-1,2,3,4-tetrahydro-isoquinoline oxalate (43) was prepared as follows: 1-(3-bromo-benzyl)-6,7-dimethoxy-1,2,3,4-tetrahydro-isoquinoline oxalate (0.910 g, 2.01 mmol) was added to a mixture of 50 mL CH2Cl2 and 50 ml of 1N NaOH. The reaction mixture was stirred at room temperature. After dissolving of precipitate organic phase was separated, dried over Na2SO4, filtered and evaporated. A residue was dissolved in 10 mL i-PrOH. Phenyl-boronic acid (0.268 g, 2.2 mmol) was added. The resulting solution was stirred for 30 min at room temperature. Pd(OAc)2 (2 mg, 0.0089 mmol), PPh3 (11 mg, 0.042 mmol) and 2N Na2CO3 (1.3 mL, 2.6 mmol) were added, the reaction mixture was refluxed for 6 h under Ar and evaporated. A residue was dissolved in chloroform and washed with 1N NaOH. Organic phase was dried under Na2SO4, filtered and evaporated. A residue was dissolved in MeOH, a solution of oxalic acid dihydrate (0.510 g, 4.05 mmol) was added under reflux. Oxalic acid salt was crystallized from MeOH-Et2O mixture. Yield is 0.558 g (61.7%)
Reaction SMILES: C([O:4][C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][C:6]=1[N:12]1[N:16]=[C:15]2[CH:17]=[CH:18][C:19]([CH2:21][CH3:22])=[CH:20][C:14]2=[N:13]1)(=O)C.[OH-].[Na+].Cl>C(O)C>[OH:4][C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][C:6]=1[N:12]1[N:16]=[C:15]2[CH:17]=[CH:18][C:19]([CH2:21][CH3:22])=[CH:20][C:14]2=[N:13]1
Reactant: CCc1ccc2nn(-c3cc(C)ccc3OC(C)=O)nc2c1
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Solvent: CCO
Product: CCc1ccc2nn(-c3cc(C)ccc3O)nc2c1
Temperature: 80 °C
Yield: 53.3 %

Procedure:
Pure 2(2-hydroxy-5-methylphenyl)-5-ethyl-2H-benzotriazole was obtained by the hydrolysis of 2(2-acetoxy-5-methylphenyl)5-ethyl-2H-benzotriazole. A solution of 2(2-acetoxy-5-methylphenyl)5-ethyl-2H-benzotriazole (5.9 g, 0.02 mole) and 10 ml of ethanol was poured into a solution of sodium hydroxide (2.0 g, 0.05 mole). The resulting fine dispersion was heated to 80° C. for 3 hours. After cooling to room temperature, the homogeneous solution was acidified with 1 N aqueous hydrochloric acid solution and the solid precipitate was extracted with carbon tetrachloride. The solution was chromatographed and the eluate concentrated under reduced pressure. The residue was recrystallized from n-hexane by cooling the solution to -78° C. White needles were obtained which were collected by filtration, washed with cold n-hexane and dried. 2.7 g (54% yield) of 2(2-hydroxy-5-methylphenyl)5-ethyl-2H-benzotriazole was obtained, which had following properties.
Reaction SMILES: [C:1]([C:3]1[CH:11]=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[CH:5][CH:4]=1)#[N:2].[C:12](O)([CH3:15])([CH3:14])[CH3:13].Cl.CN(C)CCCN=C=NCC>CN(C=O)C.CN(C)C1C=CN=CC=1>[C:1]([C:3]1[CH:11]=[CH:10][C:6]([C:7]([O:9][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:8])=[CH:5][CH:4]=1)#[N:2]
Reactant: CC(C)(C)O
Reactant: N#Cc1ccc(C(=O)O)cc1
Agent: CCN=C=NCCCN(C)C
Agent: CN(C)c1ccncc1
Agent: Cl
Solvent: CN(C)C=O
Product: CC(C)(C)OC(=O)c1ccc(C#N)cc1
Temperature: 25 °C
Reaction time: 8 h

Procedure:
Dissolve 22.1 g 4-cyanobenzoic acid and 28.2 ml t-butanol in 500 ml DMF. Add 9.15 g 4-(dimethylamino) pyridine and 31.5 g 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. Stir the mixture overnight at RT. Remove the DMF in vacuo, and partition the resultant residue between ethyl acetate and water. Wash the organic layer successively with cold 0.5 N aqueous HCl, water, 5% aqueous NaHC03 and brine. Dry the organic layer over MgSO4 and evaporate the solvent to obtain the title compound. m.p. 75°-78° C. Rf (silica gel; 5% EtOAc in hexane)=0.3; IR 2240 cm-1 ; 1730 cm-1.
Reaction SMILES: [OH-].[Sr+2:2].[OH-].[B:4]([OH:7])([OH:6])[OH:5]>>[B:4]([O-:7])([O-:6])[O-:5].[B:4]([O-:7])([O-:6])[O-:5].[B:4]([O-:7])([O-:6])[O-:5].[B:4]([O-:7])([O-:6])[O-:5].[B:4]([O-:7])([O-:6])[O-:5].[B:4]([O-:7])([O-:6])[O-:5].[Sr+2:2].[Sr+2:2].[Sr+2:2].[Sr+2:2].[Sr+2:2].[Sr+2:2].[Sr+2:2].[Sr+2:2].[Sr+2:2]
Reactant: OB(O)O
Agent: [OH-]
Agent: [Sr+2]
Product: [O-]B([O-])[O-]

Procedure:
The starting phosphor is first washed in a solution, preferably saturated solution of strontium hydroxide. This is generally done in a number of wash steps to produce a first washed phosphor. The washing is done primarily to remove residual boric acid which is present on the surface of the phosphor particles as a result of the phosphor manufacturing process. In this washing step, strontium hydroxide reacts with the boric acid to produce strontium hexaborate which is more soluble than the strontium borate phosphor itself.
Reaction SMILES: Cl[C:2]1[C:11]2[C:6](=[CH:7][C:8]([Cl:12])=[CH:9][CH:10]=2)[N:5]=[CH:4][CH:3]=1.[CH3:13][N:14]([CH2:16][CH2:17][CH2:18][NH2:19])[CH3:15]>C(OCC)(=O)C.CCCCCC>[Cl:12][C:8]1[CH:7]=[C:6]2[C:11]([C:2]([CH:16]([N:14]([CH3:15])[CH3:13])[CH2:17][CH2:18][NH2:19])=[CH:3][CH:4]=[N:5]2)=[CH:10][CH:9]=1
Reactant: Clc1ccc2c(Cl)ccnc2c1
Reactant: CN(C)CCCN
Solvent: CCOC(C)=O
Solvent: CCCCCC
Product: CN(C)C(CCN)c1ccnc2cc(Cl)ccc12

Procedure:
From 4,7-dichloroquinoline and 3-(N,N-dimethylamino)-propylamine; colourless crystals from ethyl acetate-hexane, m.p.: 111°-113° C.
Reaction SMILES: F[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=[C:10]([C:14]([C:16]([C:18]3[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[C:20]([Cl:26])[CH:19]=3)=[O:17])=[O:15])[CH:11]=[CH:12][CH:13]=2)=[CH:4][CH:3]=1.[CH3:33][S:34]([O-:36])=[O:35].[Na+]>CN(C)C=O>[CH3:33][S:34]([C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=[C:10]([C:14]([C:16]([C:18]3[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[C:20]([Cl:26])[CH:19]=3)=[O:17])=[O:15])[CH:11]=[CH:12][CH:13]=2)=[CH:4][CH:3]=1)(=[O:36])=[O:35]
Reactant: COc1ccc(C(=O)C(=O)c2cccc(-c3ccc(F)cc3)c2-c2ccccc2)cc1Cl
Reactant: CS(=O)[O-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: COc1ccc(C(=O)C(=O)c2cccc(-c3ccc(S(C)(=O)=O)cc3)c2-c2ccccc2)cc1Cl
Yield: 47.4 %

Procedure:
Following the procedure of Example 53, Step 4 using the benzil from Step 2 (2.8 g, 9.6 mmol) and sodium methylsulfinate (1.25 g, 12 mmol) in dimethylformamide (25 ml), there was obtained 2.3 g (70%) of the desired product: mp 163-166° C. Anal. Calc'd. for C16H13ClO5S (MW 352.79): C, 54.47; H, 3.71; S, 9.09. Found: C, 54.11; H, 3.52; S, 9.30.
Reaction SMILES: [C:1]([CH2:6][C:7]([O:9][CH3:10])=[O:8])(=[O:5])[CH:2]([CH3:4])[CH3:3].[F:11][C:12]1[CH:19]=[CH:18][C:15]([C:16]#[N:17])=[CH:14][CH:13]=1.C1(C)C=CC=CC=1.[Sn](Cl)(Cl)(Cl)Cl>CCCCCC>[NH2:17][C:16](=[C:6]([C:1](=[O:5])[CH:2]([CH3:4])[CH3:3])[C:7]([O:9][CH3:10])=[O:8])[C:15]1[CH:18]=[CH:19][C:12]([F:11])=[CH:13][CH:14]=1
Reactant: COC(=O)CC(=O)C(C)C
Reactant: N#Cc1ccc(F)cc1
Agent: Cl[Sn](Cl)(Cl)Cl
Solvent: Cc1ccccc1
Solvent: CCCCCC
Product: COC(=O)C(C(=O)C(C)C)=C(N)c1ccc(F)cc1
Temperature: 80 °C
Reaction time: 3 h
Yield: 75.2 %

Procedure:
75.09 g of methyl isobutyrylacetate (0.50 mol, concentration 96%) and 61.80 g of 4-fluorobenzonitrile (0.50 mol, concentration 98%) were introduced into [500 ml of toluene and treated with 144.7 g of tin tetrachloride (0.55 mol, concentration 99%) at room temperature over the course of 16 min. After half an hour at room temperature, the thick suspension was heated to 80° C. After 3 h, 175 ml of toluene were distilled off at normal pressure, and the mixture was cooled to room temperature and treated with 450 ml of saturated sodium carbonate and 300 ml of ethyl acetate. The organic phase was separated off and the aqueous phase (after dilution with 300 ml of water) was again extracted with 300 ml of ethyl acetate. After drying the combined organic phases over sodium sulphate, the solvent was removed in vacuo (40° C./25 mbar). 127.2 g of crude product were obtained in the form of a slightly yellowish solid, which was dissolved in 160 ml of n-hexane (slightly turbid solution). After hot filtration and subsequent cooling in an ice bath, 99.8 g of methyl 2-[1-amino-1-(4-fluorophenyl)-methylene]-4-methyl-3-oxopentanoate were obtained after filtration in the form of a pale yellow solid.
Reaction SMILES: Cl[CH:2]1[C:8]2[CH:9]=[C:10]([F:13])[CH:11]=[CH:12][C:7]=2[S:6][C:5]2[CH:14]=[C:15]([O:18][CH3:19])[CH:16]=[CH:17][C:4]=2[CH2:3]1.[CH3:20][N:21]1[CH2:26][CH2:25][NH:24][CH2:23][CH2:22]1.[OH-].[Na+]>>[F:13][C:10]1[CH:11]=[CH:12][C:7]2[S:6][C:5]3[CH:14]=[C:15]([O:18][CH3:19])[CH:16]=[CH:17][C:4]=3[CH2:3][CH:2]([N:24]3[CH2:25][CH2:26][N:21]([CH3:20])[CH2:22][CH2:23]3)[C:8]=2[CH:9]=1
Reactant: CN1CCNCC1
Reactant: COc1ccc2c(c1)Sc1ccc(F)cc1C(Cl)C2
Agent: [Na+]
Agent: [OH-]
Product: COc1ccc2c(c1)Sc1ccc(F)cc1C(N1CCN(C)CC1)C2

Procedure:
12 G. of 10-chloro-8-fluoro-10,11-dihydro-3-methoxy-dibenzo[b,f]thiepin are treated with 16.3 g. of N-methylpiperazine and stirred for 10 minutes at 110°-120° C. (internal temperature). Thereafter, the mixture is cooled and treated with 2N sodium hydroxide. The mixture is then extracted with ether and the organic phase washed with water. The ether solution is extracted with dilute methanesulfonic acid and the acidic solution made alkaline with sodium hydroxide and extracted with methylene chloride. The organic phase is washed with water, dried over magnesium sulfate and concentrated, and there is obtained 1-{8-fluoro-10,11-dihydro-3-methoxy-dibenzo[b,f]thiepin-10-yl}-4-methylpiperazine having a melting point of 141°-144° C. This base is converted by treatment with methanesulfonic acid into the methanesulfonate which has a melting point of 208°-210° C.