Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: BrC1C([C@H:8]2[C@H:13]([O:14][CH2:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[C@@H:12]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C@H:11]([O:30][CH2:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)[C@@H:10]([CH2:38][O:39][CH2:40][C:41]3[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=3)[O:9]2)=CC(CC2C=CC(CC)=CC=2)=C(Cl)C=1O.[CH2:58]([O:61][C:62]1[C:67]([O:68][CH2:69][CH:70]=[CH2:71])=[C:66]([Cl:72])[C:65]([CH2:73][C:74]2[CH:79]=[CH:78][C:77]([O:80][CH2:81][CH3:82])=[CH:76][CH:75]=2)=[CH:64][C:63]=1Br)[CH:59]=[CH2:60]>>[CH2:31]([O:30][C@H:11]1[C@H:12]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@@H:13]([O:14][CH2:15][C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C@H:8]([C:63]2[CH:64]=[C:65]([CH2:73][C:74]3[CH:79]=[CH:78][C:77]([O:80][CH2:81][CH3:82])=[CH:76][CH:75]=3)[C:66]([Cl:72])=[C:67]([O:68][CH2:69][CH:70]=[CH2:71])[C:62]=2[O:61][CH2:58][CH:59]=[CH2:60])[O:9][C@@H:10]1[CH2:38][O:39][CH2:40][C:41]1[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=1)[C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1
Reactant: C=CCOc1c(Br)cc(Cc2ccc(OCC)cc2)c(Cl)c1OCC=C
Reactant: CCc1ccc(Cc2cc([C@@H]3O[C@H](COCc4ccccc4)[C@@H](OCc4ccccc4)[C@H](OCc4ccccc4)[C@H]3OCc3ccccc3)c(Br)c(O)c2Cl)cc1
Product: C=CCOc1c([C@@H]2O[C@H](COCc3ccccc3)[C@@H](OCc3ccccc3)[C@H](OCc3ccccc3)[C@H]2OCc2ccccc2)cc(Cc2ccc(OCC)cc2)c(Cl)c1OCC=C

Procedure:
Similar procedure with preparation of 162 proceeded except for using compound 202 to obtain the compound 203.
Reaction SMILES: [CH2:1]([O:3][C:4](=[O:28])[CH:5]([O:25][CH2:26][CH3:27])[CH2:6][C:7]1[CH:12]=[CH:11][C:10]([O:13][CH2:14][CH2:15][NH:16][C:17](=O)[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])=[CH:9][CH:8]=1)[CH3:2].C(O)CCC>C1COCC1>[CH2:1]([O:3][C:4](=[O:28])[CH:5]([O:25][CH2:26][CH3:27])[CH2:6][C:7]1[CH:12]=[CH:11][C:10]([O:13][CH2:14][CH2:15][NH:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])=[CH:9][CH:8]=1)[CH3:2]
Reactant: CCCCCCC(=O)NCCOc1ccc(CC(OCC)C(=O)OCC)cc1
Solvent: CCCCO
Solvent: C1CCOC1
Product: CCCCCCCNCCOc1ccc(CC(OCC)C(=O)OCC)cc1
Temperature: 25 °C
Reaction time: 24 h
Yield: 71.5 %

Procedure:
A solution of the compound obtained in Step d (46 mg) in THF (2 ml) was added with borane/dimethyl sulfide complex (55 μl, Tokyo Kasei Kogyo). The reaction mixture was stirred at room temperature for 24 hours, added with butanol (2 ml) and stirred for 2 hours. The reaction mixture was concentrated, and the resulting residue was applied on a silica gel column and eluted with chloroform/methanol (100:5, then 100:10) to obtain the title compound (31.7 mg).
Reaction SMILES: [CH3:1][N:2]([C:4]1[O:8][N:7]=[C:6]([CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[N:5]=1)[CH3:3].C([Li])CCC.[C:21](=[O:23])=[O:22]>>[CH3:1][N:2]([CH3:3])[C:4]1[O:8][N:7]=[C:6]([CH:9]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:21]([OH:23])=[O:22])[N:5]=1
Reactant: O=C=O
Reactant: CN(C)c1nc(Cc2ccccc2)no1
Agent: [Li]CCCC
Product: CN(C)c1nc(C(C(=O)O)c2ccccc2)no1

Procedure:
5-(Dimethylamino-3-(phenylmethyl)-1,2,4-oxadiazole from part (a) is treated with a solution of butyl lithium and carbon dioxide according to the procedure of Example 1 (b) to yield 5-(dimethylamino)-α-phenyl-1,2,4-oxadiazole-3-acetic acid.
Reaction SMILES: [CH2:1]1[O:9][C:8]2[CH:7]=[CH:6][C:5]([CH:10]3[C:18]4[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=4)[CH:12]([C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=4)[CH:11]3[C:25]([O:27]CC)=[O:26])=[CH:4][C:3]=2[O:2]1.[OH-].[K+]>CCO.C1COCC1>[CH2:1]1[O:9][C:8]2[CH:7]=[CH:6][C:5]([CH:10]3[C:18]4[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=4)[CH:12]([C:19]4[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=4)[CH:11]3[C:25]([OH:27])=[O:26])=[CH:4][C:3]=2[O:2]1
Reactant: CCOC(=O)C1C(c2ccccc2)c2ccccc2C1c1ccc2c(c1)OCO2
Agent: [K+]
Agent: [OH-]
Solvent: CCO
Solvent: C1CCOC1
Product: O=C(O)C1C(c2ccccc2)c2ccccc2C1c1ccc2c(c1)OCO2
Temperature: 25 °C
Reaction time: 8 h

Procedure:
To a solution of ethyl(1RS,2SR,3SR)-1-(3,4-methylenedioxyphenyl)-3-phenylindane-2-carboxylate (650 mg, 1.68 mmol) in EtOH containing a few drops of THF was added 6M KOH (1.68 ml, 10.1 mmol). The resulting mixture was allowed to stir at room temperature overnight, then was concentrated under reduced pressure. The residue was partitioned between H2O and Et2O. The aqueous phase was acidified with 3M HCl and extracted several times with EtOAc. The combined EtOAc extracts were washed successively with H2O and saturated aqueous NaCl and dried (MgSO4). The solvent was removed in vacuo to afford an oil, which was crystallized from EtOAc/hexanes. The title compound was obtained as a solid (305 mg, 51%); m.p. 186°-187° C.
Reaction SMILES: [C:1]([C:5]1[CH:9]=[C:8]([C:10]([NH2:12])=O)[O:7][N:6]=1)([CH3:4])([CH3:3])[CH3:2]>C1COCC1>[C:1]([C:5]1[CH:9]=[C:8]([CH2:10][NH2:12])[O:7][N:6]=1)([CH3:4])([CH3:2])[CH3:3]
Reactant: CC(C)(C)c1cc(C(N)=O)on1
Solvent: C1CCOC1
Product: CC(C)(C)c1cc(CN)on1
Temperature: 0 °C
Reaction time: 16 h
Yield: 42.9 %

Procedure:
To a solution of 220 mg (1.27 mmol) of 3-tert-butyl-isoxazole-5-carboxylic acid amide in anhydrous THF (10 mL) are added 2.54 mL (5.08 mmol, 2M solution in THF) of borane-methylsulfide complex at room temperature under nitrogen atmosphere. The reaction is heated to reflux for 3 h. A further portion of borane-methylsulfide complex (1.3 mL) is added and the reaction is heated for 4 h. The reaction mixture is quenched by addition of methanol and allowed to stand at room temperature for 16 h. The mixture is concentrated under reduced pressure and 1M aqueous HCl solution (8 mL) is added. The mixture is heated to reflux for 1 h, then cooled to 0° C., neutralized by addition of 6M aqueous NaOH solution and solid K2CO3. The mixture is extracted with diethyl ether (5×10 mL) and the combined organic extracts are dried (MgSO4), filtered and the filtrate is concentrated under reduced pressure. The residue is purified twice by column chromatography 9silica, eluent DCM, 0-10% methanol) to afford 84 mg of (3-tert-butyl-1,2-oxazol-5-yl)methanamine. Yield: 34%; ES-MS: m/z 155 [M+H]; 1H NMR (250 MHz, CHLOROFORM-d) δ ppm 1.33 (9 H, s), 1.84 (2 H+H2O, br. s.), 3.96 (2 H, s), 6.07 (1 H, s)
Reaction SMILES: [OH:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][C:10]2[CH:24]=[CH:23][C:13]3[CH:14]=[C:15]([CH:17]([NH:19][C:20](=[O:22])[CH3:21])[CH3:18])[O:16][C:12]=3[CH:11]=2)=[CH:4][CH:3]=1.Br[CH:26]1[CH2:30][CH2:29][CH2:28][CH2:27]1>>[CH:26]1([O:1][C:2]2[CH:3]=[CH:4][C:5]([CH2:8][CH2:9][C:10]3[CH:24]=[CH:23][C:13]4[CH:14]=[C:15]([CH:17]([NH:19][C:20](=[O:22])[CH3:21])[CH3:18])[O:16][C:12]=4[CH:11]=3)=[CH:6][CH:7]=2)[CH2:30][CH2:29][CH2:28][CH2:27]1
Reactant: CC(=O)NC(C)c1cc2ccc(CCc3ccc(O)cc3)cc2o1
Reactant: BrC1CCCC1
Product: CC(=O)NC(C)c1cc2ccc(CCc3ccc(OC4CCCC4)cc3)cc2o1
Yield: 25 %

Procedure:
Using N-(1-{6-[2-(4-hydroxyphenyl)ethyl]-1-benzofuran-2-yl}ethyl)acetamide (40.0 mg, 0.123 mmol) obtained in Example 165 and bromocyclopentane (0.147 mL, 1.85 mmol) and in the same manner as in Example 158, the title compound was obtained (11.9 mg, yield 25%) as a white solid.
Reaction SMILES: C([O:5][C:6](=[O:26])[CH2:7][N:8]1[CH2:15][CH2:14][C:13](=[O:16])[N:12]([CH2:17][C:18]([O:20]C(C)(C)C)=[O:19])[CH2:11][CH2:10][C:9]1=[O:25])(C)(C)C>ClCCl>[C:18]([CH2:17][N:12]1[C:13](=[O:16])[CH2:14][CH2:15][N:8]([CH2:7][C:6]([OH:26])=[O:5])[C:9](=[O:25])[CH2:10][CH2:11]1)([OH:20])=[O:19]
Reactant: CC(C)(C)OC(=O)CN1CCC(=O)N(CC(=O)OC(C)(C)C)CCC1=O
Solvent: ClCCl
Product: O=C(O)CN1CCC(=O)N(CC(=O)O)CCC1=O
Reaction time: 8 h

Procedure:
1.4 g of tert-butyl-(5-tert-butoxycarbonylmethyl-2,6-dioxoperhydro-1,5-diazocin-1-yl)acetate (starting material A3) are dissolved in 6 ml of dichloromethane and admixed with 6 ml of trifluoroacefic acid. The mixture is stirred overnight and then concentrated using a rotary evaporator, and the residue is triturated with ethyl acetate/petroleum ether (1:1). The residue is filtered off with suction and dried under reduced pressure. This gives 0.89 g of the title compound of m.p. from 250° C. (decomposition). The mass spectrum shows the molecular peaks MH+ and MNH4+ at 259 and 276 Da.
Reaction SMILES: [OH-].[K+].[CH:3]1[C:13]2[CH2:12][CH2:11][C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[C:8](=[CH:18][C:19]3[CH:20]=[C:21]([OH:25])[CH:22]=[CH:23][CH:24]=3)[C:7]=2[CH:6]=[CH:5][CH:4]=1.Cl[CH:27]([F:29])[F:28]>C(O)(C)C>[F:28][CH:27]([F:29])[O:25][C:21]1[CH:20]=[C:19]([CH:24]=[CH:23][CH:22]=1)[CH:18]=[C:8]1[C:9]2[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=2[CH2:11][CH2:12][C:13]2[CH:3]=[CH:4][CH:5]=[CH:6][C:7]1=2
Reactant: FC(F)Cl
Reactant: Oc1cccc(C=C2c3ccccc3CCc3ccccc32)c1
Agent: [K+]
Agent: [OH-]
Solvent: CC(C)O
Product: FC(F)Oc1cccc(C=C2c3ccccc3CCc3ccccc32)c1
Yield: 20 %

Procedure:
Add pellets of KOH (376 mg, 6.7 mmol) to a solution of 3-(10,11-dihydro-dibenzo[a,d]cyclohepten-5-ylidenemethyl)-phenol (200 mg, 0.67 mmol) in isopropanol (10 mL). Bubble chlorodifluoromethane (Freon 22) slowly into the reaction mixture for 2 h. Concentrate the reaction mixture, and take the residue up in 1N HCl. Extract into ethyl acetate, dry organics (MgSO4), filter, and concentrate to a milky tan oil containing the title compound. Purify via silica gel chromatography (1:20 ethyl acetate:hexanes) to afford 108 mg (20%) of a white solid, mp 91.3° C. 1H NMR (CDCl3) δ 2.66-3.56 (br m, 4H), 6.12 (t, 1H, J=80 Hz), 6.55-7.43 (m, 13H); MS (EI) 348. HPLC shows 97% purity.
Reaction SMILES: Cl[C:2]([F:14])([F:13])[C:3]([O:9][CH:10]([F:12])[F:11])([F:8])[C:4](Cl)([F:6])[F:5].[H-].[Al+3].[Li+].[H-].[H-].[H-].C(OCCOCCOCC)C>>[F:6][CH:4]([F:5])[C:3]([O:9][CH:10]([F:12])[F:11])([F:8])[CH:2]([F:14])[F:13]
Reactant: FC(F)OC(F)(C(F)(F)Cl)C(F)(F)Cl
Agent: [Al+3]
Agent: [H-]
Agent: [Li+]
Solvent: CCOCCOCCOCC
Product: FC(F)OC(F)(C(F)F)C(F)F

Procedure:
The ether XXVI (213 g, 0.79 mole) at 25°C was stirred as 0.9 M lithium aluminum hydride in diethylene glycol diethyl ether (484 ml, 0.436 mole of Li Al H4) was added dropwise. Then the product was distilled at atmospheric pressure through a cold water condensor into an ice cooled receiver until 157 g of IV was collected. This distillate was fractionally distilled to give IV, b760 68.1°-68.2°C, of 99.7% purity (by gas-liquid chromatography) in 93% of the theoretical yield; density at 23°C was 1.554. The structure of IV was confirmed by proton NMR spectroscopy.
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[C:4]([Cl:10])[C:3]=1[C:11]1[C:15]([CH3:16])=[N:14][NH:13][C:12]=1[NH2:17].[C:18](OC)(=O)[CH2:19][C:20](C)=[O:21]>C(O)(=O)C.C(OCC)C>[Cl:10][C:4]1[CH:5]=[C:6]([O:8][CH3:9])[CH:7]=[C:2]([Cl:1])[C:3]=1[C:11]1[C:15]([CH3:16])=[N:14][N:13]2[C:20](=[O:21])[CH:19]=[CH:18][NH:17][C:12]=12
Reactant: COC(=O)CC(C)=O
Reactant: COc1cc(Cl)c(-c2c(C)n[nH]c2N)c(Cl)c1
Solvent: CC(=O)O
Solvent: CCOCC
Product: COc1cc(Cl)c(-c2c(C)nn3c(=O)cc[nH]c23)c(Cl)c1
Yield: 77 %

Procedure:
To a solution of 4-(2,6-dichloro-4-methoxy-phenyl)-5-methyl-2H-pyrazol-3-ylamine (10.1 g, 39 mmol) in acetic acid (17 mL) was added methyl acetoacetate. After the mixture was heated at reflux for 3 hours it was cooled and then diluted with diethyl ether (50 mL) to generate a colorless precipitate. The solid was collected by vacuum filtration and washed with additional ether to afford the title compound as a colorless solid (10.3 g, 77%): +APcI MS (M+1)+338; 1H NMR (methanol-d4) δ: 7.14 (s, 2H), 5.68 (s, 1H), 3.86 (s, 3H), 2.30 (s, 3H), 2.16 (s, 3H).
Reaction SMILES: Cl[CH2:2][CH2:3][CH2:4][S:5]([NH:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][C:16]2[CH:21]=[CH:20][C:19]([CH2:22][CH3:23])=[CH:18][C:17]=2[O:24][CH3:25])=[C:11]([F:26])[CH:10]=1)(=[O:7])=[O:6].[NH:27]1[CH2:32][CH2:31][O:30][CH2:29][CH2:28]1.O>C(#N)C>[CH2:22]([C:19]1[CH:20]=[CH:21][C:16]([O:15][C:12]2[CH:13]=[CH:14][C:9]([NH:8][S:5]([CH2:4][CH2:3][CH2:2][N:27]3[CH2:32][CH2:31][O:30][CH2:29][CH2:28]3)(=[O:7])=[O:6])=[CH:10][C:11]=2[F:26])=[C:17]([O:24][CH3:25])[CH:18]=1)[CH3:23]
Reactant: CCc1ccc(Oc2ccc(NS(=O)(=O)CCCCl)cc2F)c(OC)c1
Reactant: C1COCCN1
Solvent: CC#N
Solvent: O
Product: CCc1ccc(Oc2ccc(NS(=O)(=O)CCCN3CCOCC3)cc2F)c(OC)c1
Temperature: 50 °C
Yield: 36.1 %

Procedure:
To a solution of 3-chloro-N-[4-(4-ethyl-2-methoxyphenoxy)-3-fluorophenyl]propane-1-sulfonamide (0.38 mmol; 153 mg) in dry acetonitrile (2 mL), under argon, was added morpholine (1.1 mmol; 100 μL). The reaction was heated at 50° C. overnight. After cooling to room temperature, the mixture was hydrolysed with 5 mL of water and extracted with dichloromethane (3*2 mL). Combined organic phases were dried over Na2SO4, concentrated in vacuo, the title compound (62 mg; 36%) was obtained after purification by preparative TLC on silica gel (ethyl acetate/cyclohexane—40/60).
Reaction SMILES: CC1(C)[O:7][CH2:6][C:5]([NH:26]C(=O)OC(C)(C)C)([CH2:8][N:9]2[C:17]3[C:12](=[C:13]([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])[CH:14]=[CH:15][CH:16]=3)[CH2:11][CH2:10]2)[CH2:4][O:3]1.CC1(C)OCC(NC(=O)OC(C)(C)C)(CN2C3C(=C(C4N=C(C5C=NC(CCC)=CC=5)ON=4)C=CC=3)CC2)CO1>>[NH2:26][C:5]([CH2:8][N:9]1[C:17]2[C:12](=[C:13]([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])[CH:14]=[CH:15][CH:16]=2)[CH2:11][CH2:10]1)([CH2:6][OH:7])[CH2:4][OH:3]
Reactant: CCCCCCCCc1cccc2c1CCN2CC1(NC(=O)OC(C)(C)C)COC(C)(C)OC1
Agent: CCCc1ccc(-c2nc(-c3cccc4c3CCN4CC3(NC(=O)OC(C)(C)C)COC(C)(C)OC3)no2)cn1
Product: CCCCCCCCc1cccc2c1CCN2CC(N)(CO)CO
Yield: 68 %

Procedure:
When the product of Step E was substituted for tert-butyl 2,2-dimethyl-5-((4-(5-(6-propylpyridin-3-yl)-1,2,4-oxadiazol-3-yl)indolin-1-yl)methyl)-1,3-dioxan-5-ylcarbamate in Example 66, Step F, the identical process afforded the title compound in 68% yield, as colourless solid. 1H-NMR (CDCl3) 0.86 (m, 3H); 1.28 (m, 10H); 1.53 (m, 2H); 1.8 (broad s, 4H+H2O); 2.48 (tr, 2H, J=7.6 Hz); 2.93 (tr, 2H, J=8.2 Hz); 3.08 (s, 2H); 3.46 (tr, 2H, J=8.7 Hz); 3.58 (m, 4H); 6.46 (d, 1H, J=7.8 Hz); 6.53 (d, 1H, J=7.6 Hz); 7.01 (m, 1H).
Reaction SMILES: [CH2:1]([O:3][C:4]([C:6]1[C:10]([CH2:11][CH2:12][CH2:13][N:14]([CH3:16])[CH3:15])=[CH:9][NH:8][C:7]=1[CH3:17])=[O:5])[CH3:2].O=P(Cl)(Cl)Cl.CN([CH:26]=[O:27])C>>[CH2:1]([O:3][C:4]([C:6]1[C:10]([CH2:11][CH2:12][CH2:13][N:14]([CH3:16])[CH3:15])=[C:9]([CH:26]=[O:27])[NH:8][C:7]=1[CH3:17])=[O:5])[CH3:2]
Reactant: CN(C)C=O
Reactant: CCOC(=O)c1c(CCCN(C)C)c[nH]c1C
Solvent: O=P(Cl)(Cl)Cl
Product: CCOC(=O)c1c(C)[nH]c(C=O)c1CCCN(C)C
Yield: 96 %

Procedure:
4-(3-Dimethylaminopropyl)-2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester (600 mg, 2.5 mmol) was formylated using POCl3 and DMF to give 645 mg (96%) of 4-(3-dimethylamino-propyl)-5-formyl-2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester.
Reaction SMILES: Cl[C:2]1[N:7]=[C:6]([N:8]([CH:13]2[CH2:18][C:17]([CH3:20])([CH3:19])[N:16]([CH3:21])[C:15]([CH3:23])([CH3:22])[CH2:14]2)[CH2:9][CH2:10][CH2:11][CH3:12])[N:5]=[C:4]([N:24]([CH:29]2[CH2:34][C:33]([CH3:36])([CH3:35])[N:32]([CH3:37])[C:31]([CH3:39])([CH3:38])[CH2:30]2)[CH2:25][CH2:26][CH2:27][CH3:28])[N:3]=1.[NH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][NH2:47].[OH-].[Na+]>C1(C)C(C)=CC=CC=1.O>[NH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][NH:47][C:2]1[N:7]=[C:6]([N:8]([CH:13]2[CH2:18][C:17]([CH3:20])([CH3:19])[N:16]([CH3:21])[C:15]([CH3:22])([CH3:23])[CH2:14]2)[CH2:9][CH2:10][CH2:11][CH3:12])[N:5]=[C:4]([N:24]([CH:29]2[CH2:30][C:31]([CH3:38])([CH3:39])[N:32]([CH3:37])[C:33]([CH3:35])([CH3:36])[CH2:34]2)[CH2:25][CH2:26][CH2:27][CH3:28])[N:3]=1
Reactant: NCCCCCCN
Reactant: CCCCN(c1nc(Cl)nc(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)n1)C1CC(C)(C)N(C)C(C)(C)C1
Agent: [Na+]
Agent: [OH-]
Solvent: Cc1ccccc1C
Solvent: O
Product: CCCCN(c1nc(NCCCCCCN)nc(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)n1)C1CC(C)(C)N(C)C(C)(C)C1
Reaction time: 8 h
Yield: 89.9 %

Procedure:
56.4 g of 2-chloro-4,6-bis-(1,2,2,6,6-pentamethyl-4-piperidyl-butylamino)-1,3,5-triazine are introduced into a melt of 120 g of hexamethylenediamine at 80°. The reaction mixture is then stirred for 8 hours at 100° and after adding 50 ml of xylene is then stirred for 16 hours at 140°. The reaction mixture is diluted with 200 ml of xylene, a solution of 4.4 g of sodium hydroxide in 50 ml of water is added and the resulting mixture is stirred vigorously for 4 hours at room temperature. The xylene solution is separated off from the aqueous phase in a separating funnel, dried over sodium sulphate and evaporated in vacuo. 57.9 g of the 2-(6-aminohexylamino)-4,6-bis-(1,2,2,6,6-pentamethyl-4-piperidyl-butylamino)-1,3,5-triazine thus obtained are dissolved in 200 ml of xylene and the resulting solution is cooled to 5°. 5.5 g of cyanuric chloride are introduced at this temperature and the reaction mixture is stirred at 5°-10° for 1 hour. After adding 1.2 g of finely powdered sodium hydroxide, the temperature is raised to 35°-40° and the mixture is stirred for 2 hours at this temperature. After adding a further portion of 1.2 g of sodium hydroxide, the reaction mixture is slowly heated to the reflux temperature. After 3 hours under reflux, a final portion of 1.4 g of sodium hydroxide is added and the reaction mixture is then stirred under reflux for 16 hours. After cooling, 200 ml of water are added, the mixture is stirred well for 15 minutes, the aqueous solution is separated off and the xylene solution is washed with 3 times 100 ml of water. The xylene solution is evaporated in vacuo and the residue is then dried under a high vacuum (130°/0.001 mm Hg). The resulting, pale yellowish mass can be comminuted to a virtually colourless powder. The light stabiliser having the above structural formula melts at about 125°.
Reaction SMILES: [F:1][C:2]([F:24])([F:23])[S:3]([NH:6][C:7]1[CH:8]=[C:9]([C:13]2[CH:14]=[C:15]([CH:20]=[CH:21][CH:22]=2)[C:16](OC)=[O:17])[CH:10]=[CH:11][CH:12]=1)(=[O:5])=[O:4].Cl.[NH2:26][C:27]([NH2:29])=[NH:28].C[O-].[Na+]>CN(C)C=O>[F:1][C:2]([F:24])([F:23])[S:3]([NH:6][C:7]1[CH:8]=[C:9]([C:13]2[CH:14]=[C:15]([CH:20]=[CH:21][CH:22]=2)[C:16]([N:26]=[C:27]([NH2:29])[NH2:28])=[O:17])[CH:10]=[CH:11][CH:12]=1)(=[O:5])=[O:4]
Reactant: COC(=O)c1cccc(-c2cccc(NS(=O)(=O)C(F)(F)F)c2)c1
Reactant: N=C(N)N
Agent: C[O-]
Agent: Cl
Agent: [Na+]
Solvent: CN(C)C=O
Product: NC(N)=NC(=O)c1cccc(-c2cccc(NS(=O)(=O)C(F)(F)F)c2)c1
Temperature: 25 °C
Reaction time: 6 h
Yield: 15.3 %

Procedure:
Methyl 3-(3-trifluoromethylsulfonylaminophenyl)-benzoate (1.7 g) was added to the mixture of guanidine hydrochloride (2.26 g) and 28% methanolic sodium methoxide (4.1 ml) in N,N-dimethylformamide (17 ml) and the reaction mixture was stirred for 6 hours at ambient temperature. After evaporating the solvent, the residue was poured into the mixture of ethyl acetate (50 ml) and water (50 ml). The mixture was adjusted to pH 6.2 with 10% hydrochloric acid. The crystalline product was collected by filtration, washed successively with water and methanol and dried in vacuo to afford 2-[3-(3-trifluoromethylsulfonylaminophenyl) benzoyl]guanidine (0.28 g).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[CH2:9][NH:8][CH2:7][C:6]2([CH3:16])[CH3:15].II.C([O-])(=O)C.[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(O)C.O>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[CH:9]=[N:8][CH2:7][C:6]2([CH3:16])[CH3:15]
Reactant: COc1cc2c(cc1OC)C(C)(C)CNC2
Agent: CC(=O)[O-]
Agent: II
Agent: O=S([O-])([O-])=S
Solvent: O
Solvent: CCO
Product: COc1cc2c(cc1OC)C(C)(C)CN=C2
Yield: 72.7 %

Procedure:
A solution of 1.0 g of 1,2,3,4-tetrahydro-6,7-dimethoxy-4,4-dimethyl-isoquinoline in 100 ml of ethanol is treated with 2.3 g of iodine and 0.49 g of sodium acetate and heated under reflux for 1 hour. The reaction mixture is cooled down and 30 ml of a 10% sodium thiosulphate-solution is added. The mixture is then diluted with water and extracted with dichloromethane (2×100 ml). The combined organic extracts are washed with brine, dried over sodium sulfate and concentrated in vacuo. The foamy residue is purified by chromatography (SiO2, dichloromethane-1% ammonia in methanol, 0-12%) to give the title compound as a yellowish oil (0.72 g), MS (ISP) 220.4 (M+H)+.
Reaction SMILES: [C:1]([C:5]1[CH:11]=[C:10]([SH:12])[CH:9]=[C:8]([CH3:13])[C:6]=1[NH2:7])([CH3:4])([CH3:3])[CH3:2].[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[C:32]([O:37][CH3:38])(=[O:36])[C:33]([CH3:35])=[CH2:34].O>C1(C)C=CC=CC=1>[NH2:7][C:6]1[C:8]([CH3:13])=[CH:9][C:10]([S:12][CH2:34][CH:33]([CH3:35])[C:32]([O:37][CH3:38])=[O:36])=[CH:11][C:5]=1[C:1]([CH3:4])([CH3:3])[CH3:2]
Reactant: C=C(C)C(=O)OC
Reactant: Cc1cc(S)cc(C(C)(C)C)c1N
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: [F-]
Solvent: O
Solvent: Cc1ccccc1
Product: COC(=O)C(C)CSc1cc(C)c(N)c(C(C)(C)C)c1
Temperature: 25 °C
Reaction time: 24 h
Yield: 18.6 %

Procedure:
To a stirred solution of 1.00 g (5.1 mmol) of 2-tert-butyl-4-mercapto-6-methylaniline and 0.15 g (0.5 mmol) of tetrabutylammonium fluoride in 5 mL of toluene at -5° C. is added dropwise a solution of 0.51 g (5.1 mmol) of methyl methacrylate in 5 mL of toluene. The reaction mixture is stirred for 24 hours at room temperature. The reaction mixture is then poured into 50 mL of water. The phases are separated and the organic phase is dried over anhydrous sodium sulfate. The solvent is removed in vacuo and the residue is purified by flash column chromatography (silica gel, 4:1, heptane:ethyl acetate eluent) to give 0.28 g (18%) of the title compound as a colorless liquid.
Reaction SMILES: [CH2:1]([O:8][C:9]1[C:10]([NH:15][C:16]([NH:18][C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][CH:20]=2)=S)=[N:11][CH:12]=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH3:26]>>[CH2:1]([O:8][C:9]1[C:10]([NH:15][C:16]([NH:18][C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][CH:20]=2)=[NH:26])=[N:11][CH:12]=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: S=C(Nc1ccc(Cl)cc1)Nc1ncccc1OCc1ccccc1
Reactant: N
Product: N=C(Nc1ccc(Cl)cc1)Nc1ncccc1OCc1ccccc1
Reaction time: 20 h

Procedure:
To a stirring suspension of N-(3-benzyloxy-2-pyridyl)-N'-(4-chlorophenyl)thiourea (1.5 g, 0.00406 mol) in ammonia-saturated methanol (30 ml) was added yellow mercuric oxide (2.2 g, 0.01 mol). Stirring was continued for 20 h, then the solvent evaporated and the black residue treated with chloroform and filtered through celite. The filtrate was evaporated to a whim solid, which was recrystallised from ethyl acetam. Yield 0.76 g (53%), m.p. 170°-172 ° C.
Reaction SMILES: [C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH2:16][CH2:17][O:18][CH3:19])[CH3:15])[C:11]([Cl:20])=[CH:10][C:9]=1[NH2:21])([CH3:4])([CH3:3])[CH3:2].C([O:27][C:28](=O)[CH2:29][C:30]([C:32]1[CH:37]=[CH:36][CH:35]=[C:34]([C:38]2[O:42][N:41]=[C:40]([CH3:43])[CH:39]=2)[CH:33]=1)=[O:31])(C)(C)C>>[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH2:16][CH2:17][O:18][CH3:19])[CH3:15])[C:11]([Cl:20])=[CH:10][C:9]=1[NH:21][C:28](=[O:27])[CH2:29][C:30]([C:32]1[CH:37]=[CH:36][CH:35]=[C:34]([C:38]2[O:42][N:41]=[C:40]([CH3:43])[CH:39]=2)[CH:33]=1)=[O:31])([CH3:4])([CH3:2])[CH3:3]
Reactant: COCCN(C)c1cc(NC(=O)OC(C)(C)C)c(N)cc1Cl
Reactant: Cc1cc(-c2cccc(C(=O)CC(=O)OC(C)(C)C)c2)on1
Product: COCCN(C)c1cc(NC(=O)OC(C)(C)C)c(NC(=O)CC(=O)c2cccc(-c3cc(C)no3)c2)cc1Cl

Procedure:
The title compound was prepared from {2-amino-4-chloro-5-[(2-methoxy-ethyl)-methyl-amino]-phenyl}-carbamic acid tert.-butyl ester (Example J4) (165 mg, 0.5 mmol) and 3-[3-(3-methyl-isoxazol-5-yl)-phenyl]-3-oxo-propionic acid tert.-butyl ester (Example K4) (165 mg, 0.55 mmol) according to the general procedure M. Obtained as an amorphous yellow substance (207 mg).
Reaction SMILES: [C:1]1([SH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:8]([Si:11]([CH3:14])([Cl:13])[Cl:12])C=C.CC(N=NC(C#N)(C)C)(C#N)C>>[S:7]1[CH:1]=[CH:6][CH:5]=[C:4]1[CH2:3][CH2:2][CH2:8][Si:11]([CH3:14])([Cl:13])[Cl:12]
Reactant: C=CC[Si](C)(Cl)Cl
Reactant: Sc1ccccc1
Agent: CC(C)(C#N)N=NC(C)(C)C#N
Product: C[Si](Cl)(Cl)CCCc1cccs1
Temperature: 60 °C
Yield: 88 %

Procedure:
26.8 g thiophenol, 18.8 g allyl (methyl) dichlorosilane and 0.60 mg azobisisobutylonitrile were put in a 100-mL three-neck flask that had been subjected to nitrogen substitution and the mixture was heated at 60° C. for 5 hours. After the reaction, the product was distilled under reduced pressure, obtaining 3-(thiophenyl) propyl (methyl) dichlorosilane with a 88% yield.