Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: F[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[CH3:11][N:12]1[CH2:17][CH2:16][NH:15][CH2:14][CH2:13]1.C(=O)([O-])[O-].[K+].[K+].O>C(#N)C>[CH3:11][N:12]1[CH2:17][CH2:16][N:15]([C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=2)[CH2:14][CH2:13]1
Reactant: O=[N+]([O-])c1ccc(F)cc1
Reactant: CN1CCNCC1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC#N
Solvent: O
Product: CN1CCN(c2ccc([N+](=O)[O-])cc2)CC1
Temperature: 60 °C

Procedure:
To a solution of 25.0 g (0.18 mol) of 1-fluoro-4-nitrobenzene and 19.5 g (0.2 mol) of 1-methylpiperazine in 300 mL of acetonitrile, add 48.9 g (0.35 mol) of anhydrous potassium carbonate. Heat the reaction mixture to 60° C. for 20 h under nitrogen. After this time, add 100 mL of water and concentrate mixture to 200 mL volume. Add another 100 mL of water and extract with 3×200 mL of methylene chloride. Extract the combined methylene chloride extracts with 100 mL of 6N hydrochloric acid solution and 3×200 mL of water. Make the combined aqueous extracts basic (pH=14) with 50% sodium hydroxide solution and extract with 3×200 mL of methylene chloride. Dry the extracts over anhydrous sodium sulfate. Remove the drying agent by filtration and evaporate the solvent in vacuo. Dissolve the residue in 150 mL of methanol and bubble hydrogen chloride gas through the solution until pH=1. Precipitate the product by addition of diethyl ether to obtain the title compound.
Reaction SMILES: [CH3:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1.[Br:13]N1C(=O)CCC1=O>C(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:13][CH2:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1
Reactant: Cc1ccc2ccc(=O)oc2c1
Reactant: O=C1CCC(=O)N1Br
Agent: O=C(OOC(=O)c1ccccc1)c1ccccc1
Solvent: ClC(Cl)Cl
Product: O=c1ccc2ccc(CBr)cc2o1
Yield: 50.8 %

Procedure:
7-Methylcoumarin (28 g), 70% benzoylperoxide (1.68 g), and N-bromosuccinimide (30.8 g) was added to 140 mL chloroform in a one liter flask, and the suspension was refluxed overnight. The solution was diluted with 100 mL chloroform. The resulting crude product was recrystallized from 750 mL acetone. A white solid (21 g) with a melting point of 172-176° C. was obtained.
Reaction SMILES: [C:1]([N:8]1[CH2:15][CH2:14][CH2:13][C@H:9]1[C:10]([OH:12])=O)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].Cl.[CH3:17][O:18][C:19](=[O:25])[C@@H:20]1[CH2:24][CH2:23][CH2:22][NH:21]1>>[CH3:17][O:18][C:19](=[O:25])[C@@H:20]1[CH2:24][CH2:23][CH2:22][N:21]1[C:10](=[O:12])[C@@H:9]1[CH2:13][CH2:14][CH2:15][N:8]1[C:1]([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2]
Reactant: COC(=O)[C@@H]1CCCN1
Reactant: CC(C)(C)OC(=O)N1CCC[C@H]1C(=O)O
Agent: Cl
Product: COC(=O)[C@@H]1CCCN1C(=O)[C@@H]1CCCN1C(=O)OC(C)(C)C

Procedure:
2.15 g (10 mmol) BOC-L-proline and 1.66 g (10 mmol) proline methyl ester HCl salt were coupled according to procedure A. Yield of crude product 2.83 g. The product was purified with a silica column using 5% methanol in ethyl acetate as eluent. Yield 2.40 g (7.4 mmol, 74%)
Reaction SMILES: [OH:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH2:5]O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(Br)(Br)(Br)[Br:30]>C(Cl)Cl>[Br:30][CH2:5][C:4]1[CH:3]=[C:2]([OH:1])[CH:9]=[CH:8][CH:7]=1
Reactant: OCc1cccc(O)c1
Reactant: BrC(Br)(Br)Br
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: ClCCl
Product: Oc1cccc(CBr)c1
Temperature: 25 °C
Yield: 82.3 %

Procedure:
To a suspension of 3-hydroxybenzylalcohol (1.0 g, 8.06 mmol) and PPh3 (3.17 g, 12.08 mmol) in DCM (40 mL) at 0° C. was added CBr4 (4.01 g, 12.08 mmol) dropwise. The reaction was warmed to RT over 90 minutes, concentrated under reduced pressure and purified by silica gel chromatography (5% to 50% EtOAc in Hexanes) to give 3-(bromomethyl)phenol as a light brown crystalline solid (1.24 g, 82%).
Reaction SMILES: [NH2:1][C:2]1[CH:11]=[C:10]([O:12][CH3:13])[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[N:3]=1.Br[CH2:15][C:16](=O)[C:17]([O:19][CH2:20][CH3:21])=[O:18]>C(COC)OC>[CH3:13][O:12][C:10]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[N:3]2[CH:15]=[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[N:1]=[C:2]2[CH:11]=1
Reactant: CCOC(=O)C(=O)CBr
Reactant: COc1cc(N)nc2ccccc12
Solvent: COCCOC
Product: CCOC(=O)c1cn2c(cc(OC)c3ccccc32)n1

Procedure:
350 mg of 2-amino-4-methoxyquinoline [Grout et al., J. C. S. Perkin I, (1973), p. 1314] were dissolved in 10 ml dimethoxyethane and 390 mg of ethyl bromopyruvate were added thereto. The crystalline intermediate thus formed was filtered off, washed with ether and then was dissolved in ethanol. The solution obtained was refluxed for 1 hour and then the solvent was removed under vacuum. The residue was purified by column chromatography (silica gel--chloroform as eluant) and was crystallized from chloroform/ether to give colorless needles of ethyl 5-methoxyimidazo-[1,2-a]-quinoline-2-carboxylate melting at 178°-179° C.
Reaction SMILES: Cl[C:2]1[N:7]=[CH:6][CH:5]=[CH:4][N:3]=1.C(O)(=O)C.[Br:12][C:13]1[CH:19]=[CH:18][C:16]([NH2:17])=[CH:15][CH:14]=1.C(=O)([O-])O.[Na+]>O1CCOCC1>[Br:12][C:13]1[CH:19]=[CH:18][C:16]([NH:17][C:2]2[N:7]=[CH:6][CH:5]=[CH:4][N:3]=2)=[CH:15][CH:14]=1
Reactant: Nc1ccc(Br)cc1
Reactant: Clc1ncccn1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: CC(=O)O
Solvent: C1COCCO1
Product: Brc1ccc(Nc2ncccn2)cc1
Reaction time: 3 h
Yield: 51.6 %

Procedure:
Under an argon atmosphere, 2-chloropyrimidine (2.68 g) and acetic acid (1.97 ml) were added to a solution of 4-bromoaniline (4.03 g) in dioxane (200 ml), and the resulting mixture was stirred for 3 hours while heating the mixture to reflux. Saturated aqueous sodium hydrogen carbonate solution was added in small portions to the reaction solution to neutralize it, and the resulting mixture was concentrated. Ethyl acetate (500 ml) was added to the residue and the resulting mixture was stirred at room temperature for 10 minutes, followed by removing insoluble matter by filtration. The filtrate was washed with saturated aqueous sodium hydrogen carbonate solution and with saturated brine, and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from ethyl acetate to obtain N-(4-bromophenyl)pyrimidin-2-amine (3.02 g).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH2:7]Br)=[CH:5][CH:4]=1.[Cl:11][C:12]1[C:13]([OH:21])=[N:14][CH:15]=[C:16]([N+:18]([O-:20])=[O:19])[CH:17]=1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C>[Cl:11][C:12]1[C:13](=[O:21])[N:14]([CH2:7][C:6]2[CH:9]=[CH:10][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)[CH:15]=[C:16]([N+:18]([O-:20])=[O:19])[CH:17]=1
Reactant: O=[N+]([O-])c1cnc(O)c(Cl)c1
Reactant: COc1ccc(CBr)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CN(C)C=O
Product: COc1ccc(Cn2cc([N+](=O)[O-])cc(Cl)c2=O)cc1
Temperature: 25 °C
Reaction time: 2 h

Procedure:
4-Methoxybenzyl bromide (5.0 mL, 34.4 mmol) was added to a cold (0° C.) mixture 3-chloro-2-hydroxy-5-nitropyridine (5 g, 28.6 mmol) and K2CO3 (7.9 g, 57.3 mmol) in DMF (25 mL). The reaction mixture was allowed to warm to rt, stirred for 2 h, quenched by addition of a saturated aqueous NaHCO3 solution, and extracted with EtOAc. The organic layer was washed with brine, dried (Na2SO4), filtered, and concentrated. The residue was purified by trituration in EtOAc. ESI-MS: tR=0.98 min (LC-MS 1).
Reaction SMILES: [F:1][C:2]([F:12])([F:11])[C:3]1[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=1[CH2:5]Cl.[P:13]([O:20]CC)([O:17][CH2:18][CH3:19])[O:14][CH2:15][CH3:16]>>[F:1][C:2]([F:12])([F:11])[C:3]1[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=1[CH2:5][P:13](=[O:20])([O:17][CH2:18][CH3:19])[O:14][CH2:15][CH3:16]
Reactant: FC(F)(F)c1ccccc1CCl
Reactant: CCOP(OCC)OCC
Product: CCOP(=O)(Cc1ccccc1C(F)(F)F)OCC
Temperature: 160 °C

Procedure:
A mixture of 2-trifluoromethylbenzyl chloride (2.0 g, 10.0 mmol) and triethyl phosphite (2.13 g, 13 mmol) was heated at 160° C. under nitrogen for 3 hours. The excess triethyl phosphite was removed by distillation and the crude product obtained was distilled at 87°-90° C. (0.05 mm Hg) and isolated as a colorless oil; yield, 1.68 g, 56.8%; D.C.I.M.S.[MH+, 297].
Reaction SMILES: Cl[C:2]1[CH:7]=[C:6]([I:8])[CH:5]=[C:4]([Cl:9])[N:3]=1.[CH:10]1([NH2:16])[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]1>C(OCC)(=O)C>[Cl:9][C:4]1[N:3]=[C:2]([NH:16][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[CH:7]=[C:6]([I:8])[CH:5]=1
Reactant: NC1CCCCC1
Reactant: Clc1cc(I)cc(Cl)n1
Solvent: CCOC(C)=O
Product: Clc1cc(I)cc(NC2CCCCC2)n1
Temperature: 150 °C

Procedure:
To a solution of 2,6-dichloro-4-iodopyridine (0.1 g, 0.36 mmol) was added excess (1 mL) cyclohexylamine. The reaction mixture was heated at 150° C. in a microwave for 20 minutes. The reaction mixture was cooled to room temperature and diluted with ethyl acetate, at which time a white solid precipitated from the solution. The solid was filtered off and the organics were washed with sodium bicarbonate, water, brine, dried over MgSO4, filtered, and concentrated. The residue was purified on silica gel by flash chromatography (gradient elution: 0% to 50% ethyl acetate/hexane) to afford the title compound as an oil. m/z 337.0 (DCI, M+H)+.
Reaction SMILES: [Na].Cl[C:3]1[C:12]([N+:13]([O-:15])=[O:14])=[C:11]2[C:6]([CH:7]=[CH:8][CH:9]=[N:10]2)=[CH:5][CH:4]=1.[CH3:16][OH:17]>>[CH3:16][O:17][C:3]1[C:12]([N+:13]([O-:15])=[O:14])=[C:11]2[C:6]([CH:7]=[CH:8][CH:9]=[N:10]2)=[CH:5][CH:4]=1
Reactant: O=[N+]([O-])c1c(Cl)ccc2cccnc12
Reactant: CO
Agent: [Na]
Product: COc1ccc2cccnc2c1[N+](=O)[O-]

Procedure:
To a freshly prepared solution of sodium (16.5 g, 0.720 mol) in methanol (750 mL) was added 7-chloro-8-nitroquinoline (18.72 g, 0.090 mol) [E. Fourneau, M. and Mme. Trefouel, and A. Wancolle, Bull. Soc. Chim. Fr., 47, 738(1930); A. K. Sen, N. K. Ray, V. P. Basu, J. Sci. Ind. Res., 11B, 322(1952) (C.A. 47, 4339e)]. This mixture was refluxed for 3 hr, cooled, then filtered to collect the precipitated solid. This solid was slurried in water, collected on a filter and dried; yield, after recrystallization from toluene, 16.12 g (88%); mp 178°-178.5°: Anal. Calcd for C10H8N2O3 : C, 58.82; H, 3.95; N, 13.72. Found: C, 58.66; H, 3.78; N, 13.69.
Reaction SMILES: [NH:1]1[CH2:6][CH2:5][O:4][CH2:3][CH2:2]1.C(O)(=O)C.[Br:11][C:12]1[CH:13]=[C:14]([CH:17]=[CH:18][C:19]=1[F:20])[CH:15]=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClC(Cl)C>[Br:11][C:12]1[CH:13]=[C:14]([CH:17]=[CH:18][C:19]=1[F:20])[CH2:15][N:1]1[CH2:6][CH2:5][O:4][CH2:3][CH2:2]1
Reactant: O=Cc1ccc(F)c(Br)c1
Reactant: C1COCCN1
Agent: CC(=O)O[BH-](OC(C)=O)OC(C)=O
Agent: [Na+]
Solvent: CC(Cl)Cl
Solvent: CC(=O)O
Product: Fc1ccc(CN2CCOCC2)cc1Br
Temperature: 25 °C
Reaction time: 18 h
Yield: 82 %

Procedure:
Morpholine (0.96 mL) and acetic acid (0.57 mL) are added to a solution of 3-bromo-4-fluorobenzaldehyde (2.03 g) in dichloroethane (40 mL). Sodium triacetoxyborohydride (3.18 g) is added in portions over an hour, and the reaction is stirred at room temperature for 18 hours. The reaction is quenched with a 1 N solution of NaOH (10 mL) and diluted with CH2Cl2 (100 mL). The organic layer is washed with 1 N NaOH (3×35 mL). The aqueous layers are back-extracted with CH2Cl2 (20 mL). The combined organic layers are extracted with 0.1 N HCl (6×25 mL). The combined aqueous layers are basified (pH=12) with 2 N NaOH, and the product is extracted with CH2Cl2 (6×25 mL). The combined organic layers are washed with brine (20 mL) and dried (MgSO4). The solution is concentrated in vacuo to afford 2.23 g (82%) of the title compound as a clear, colorless oil.
Reaction SMILES: [NH:1]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[C@H:2]([C:7]([OH:9])=O)[CH2:3][CH:4]([CH3:6])[CH3:5].O.C1C=CC2N(O)N=NC=2C=1.CC1C=CC(S(O)(=O)=O)=CC=1.[CH:39]1[CH:44]=[CH:43][C:42]([CH2:45][O:46][C:47]([CH2:49][NH2:50])=[O:48])=[CH:41][CH:40]=1.CCN=C=NCCCN(C)C>CN(C=O)C>[NH:1]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[C@H:2]([C:7]([NH:50][CH2:49][C:47]([O:46][CH2:45][C:42]1[CH:43]=[CH:44][CH:39]=[CH:40][CH:41]=1)=[O:48])=[O:9])[CH2:3][CH:4]([CH3:5])[CH3:6]
Reactant: NCC(=O)OCc1ccccc1
Reactant: CC(C)C[C@H](NC(=O)OC(C)(C)C)C(=O)O
Agent: CCN=C=NCCCN(C)C
Agent: Cc1ccc(S(=O)(=O)O)cc1
Agent: On1nnc2ccccc21
Solvent: O
Solvent: CN(C)C=O
Product: CC(C)C[C@H](NC(=O)OC(C)(C)C)C(=O)NCC(=O)OCc1ccccc1
Temperature: -5 °C
Reaction time: 1 h

Procedure:
To a solution of 6.00 g of BOC-Leu-OH.H2O, 3.49 g of HOBT and 9.59 of H-Gly-OBzl.TosOH dissolved in 30 ml of DMF, under cooling at -5° C. and stirring, a solution of 4.97 ml of WSC dissolved in 10 ml of DMF was added dropwise, and after one hour, the temperature was regulated to room temperature, at which stirring was continued overnight. The reaction mixture was concentrated under reduced pressure to evaporate DMF, and the residue was dissolved in ethyl acetate. The ethyl acetate layer was washed successively with 1N hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 9.2 g of BOC-Leu-Gly-OBzl as oily product. Rf1 =0.59.
Reaction SMILES: [I:1][C:2]1[CH:10]=[C:6]([C:7]([OH:9])=[O:8])[C:5]([NH:11][CH3:12])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[C:19](Cl)(Cl)=[O:20]>O>[I:1][C:2]1[CH:10]=[C:6]2[C:7]([O:9][C:19](=[O:20])[N:11]([CH3:12])[C:5]2=[CH:4][CH:3]=1)=[O:8]
Reactant: CNc1ccc(I)cc1C(=O)O
Reactant: O=C(Cl)Cl
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Product: Cn1c(=O)oc(=O)c2cc(I)ccc21
Reaction time: 3 h
Yield: 77.9 %

Procedure:
To a mechanically stirred solution of 5-iodo-N-methylanthranilic acid (40 grams 0.144 mol), potassium carbonate (19.95 grams, 0.144 mol), and 500 ml water at 0° C. was added phosgene (1.93M solution in toluene, 0.2 mol, 104 mL) over a period of 1 hr. the resulting slurry was stirred for an additional 3 hrs and the solids isolated by filtration, washing with water, and a small amount (70 mL) of ether. The solids were dried overnight in vacuo to yield 34 grams (78%) of 5-iodo-N-methylisatoic anhydride. 1H NMR (DMSO-d6) 8.18 (1H, bs, C6-H), 8.08 (1H, bd, 3JHH =8 Hz, C4-H), 7.12 (1H, d, 3JHH =8 Hz, C3-H), 3.42 (3H, s, NCH3).
Reaction SMILES: [C:1]1([C:7](=[O:11])[C:8](=[O:10])[CH3:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:12]Br>C(Cl)(Cl)Cl>[Br:12][CH2:9][C:8](=[O:10])[C:7]([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)=[O:11]
Reactant: BrBr
Reactant: CC(=O)C(=O)c1ccccc1
Solvent: ClC(Cl)Cl
Product: O=C(CBr)C(=O)c1ccccc1
Temperature: 50 °C
Yield: 102 %

Procedure:
5.32 kg of 1-phenylpropane-1,2-dione (98.6% by G.C. equivalent to 5.24 kg, 35.4 mole) were dissolved in 36 liters of chloroform and the solution was heated to 50° C. A solution of 5.66 kg (35.4 mole) of bromine in 8 liters of chloroform was added slowly to maintain a gentle reflux and immediate decolorization of the bromine (approximately 6 hours). The solution was cooled to room temperature overnight and was washed with 20 liters of saturated sodium bicarbonate solution and 20 liters of water and dried over sodium sulfate. The solvent was removed under vacuum to obtain 8.2 kg (100% yield) of a green/yellow oil which was used directly for subsequent reactions after estimation of its purity (approximately 75% by G.C. or N.M.R.).
Reaction SMILES: [OH-].[Li+].C[O:4][C:5]([C:7]1[C:8]([CH3:19])=[N:9][O:10][C:11]=1[C:12]1[CH:17]=[CH:16][C:15]([Br:18])=[CH:14][CH:13]=1)=[O:6]>CO.O>[Br:18][C:15]1[CH:14]=[CH:13][C:12]([C:11]2[O:10][N:9]=[C:8]([CH3:19])[C:7]=2[C:5]([OH:6])=[O:4])=[CH:17][CH:16]=1
Reactant: COC(=O)c1c(C)noc1-c1ccc(Br)cc1
Agent: [Li+]
Agent: [OH-]
Solvent: O
Solvent: CO
Product: Cc1noc(-c2ccc(Br)cc2)c1C(=O)O
Temperature: 60 °C
Reaction time: 1 h

Procedure:
Lithium hydroxide (2 g, 47.7 mmol) was added to a solution of 5-(4-bromo-phenyl)-3-methyl-isoxazole-4-carboxylic acid methyl ester (7 g, 23.6 mmol) in MeOH (50 mL) and H2O (10 mL), and the reaction was stirred at 60° C. for 1 hour. Acidic work-up the title compound.
Reaction SMILES: [C:1]([N:4]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH2:6][CH2:5]1)(=[O:3])[CH3:2].[Br:13]Br.S(=O)(O)[O-].[Na+]>C(O)(=O)C>[Br:13][C:9]1[CH:8]=[C:7]2[C:12](=[CH:11][CH:10]=1)[N:4]([C:1](=[O:3])[CH3:2])[CH2:5][CH2:6]2
Reactant: CC(=O)N1CCc2ccccc21
Reactant: BrBr
Agent: O=S([O-])O
Agent: [Na+]
Solvent: CC(=O)O
Product: CC(=O)N1CCc2cc(Br)ccc21
Temperature: 0 °C

Procedure:
To N-acetylindoline, 116.6 g (0.724 mol) in a 1000 ml 3 neck flash fitted with overhead stirrer, thermometer and gas inlet (to a sodium hydroxide trap) in 150 ml acetic acid was added bromine, 32.25 ml (0.68 mol) over a period of 30 minutes. The mixture was kept at 30° C. with ice bath cooling. When addition was complete, the yellow suspension was slowly poured into one liter of ice water and solid sodium bisulfite was added to destroy any residual bromine. The resulting slightly off white solid was filtered and washed several times with water and allowed to dry overnight. The resulting solid was recrystallized from 800 ml of methanol to give 122.86 g (70.7% by weight yield) of 5-bromo-N-acetylindoline.
Reaction SMILES: [CH3:1][O:2][C:3](=[O:24])[CH:4]([C:9]1[NH:10][C:11]2[C:16]([C:17]=1[CH2:18][CH2:19][N:20]=[N+:21]=[N-:22])=[CH:15][CH:14]=[C:13]([F:23])[CH:12]=2)[C:5]([O:7][CH3:8])=[O:6].[CH3:25][O-].[Na+].CI>CO>[CH3:1][O:2][C:3](=[O:24])[C:4]([C:9]1[NH:10][C:11]2[C:16]([C:17]=1[CH2:18][CH2:19][N:20]=[N+:21]=[N-:22])=[CH:15][CH:14]=[C:13]([F:23])[CH:12]=2)([CH3:25])[C:5]([O:7][CH3:8])=[O:6]
Reactant: COC(=O)C(C(=O)OC)c1[nH]c2cc(F)ccc2c1CCN=[N+]=[N-]
Reactant: C[O-]
Agent: [Na+]
Solvent: CI
Solvent: CO
Product: COC(=O)C(C)(C(=O)OC)c1[nH]c2cc(F)ccc2c1CCN=[N+]=[N-]
Temperature: 0 °C
Reaction time: 0.5 h

Procedure:
To a solution of 2-[3-(2-azidoethyl)-6-fluoro-1H-indol-2-yl]-propanedioic acid dimethyl ester (37 mmol) in dry MeOH (0.25 L) at 0° C. under argon was added a solution of 25% NaOMe in MeOH (8.56 mL, 37.4 mmol). The mixture was stirred for 30 min at 0° C. MeI (3.56 mL, 56.6 mmol) was added. The mixture was refluxed for 42 h, cooled, and concentrated. The residue was partitioned between H2O and Et2O. The Et2O extracts were washed with H2O, dried, and concentrated to an oil. This oil was purified by silica chromatography to give the title compound: TLC Rf=0.50 (CH2Cl2); MS (ESI+) m/z 371.1; 1H NMR (CDCl3, 300 MHz) δ 9.63 (1H), 7.44 (1H), 7.05 (1H), 6.97 (1H), 3.82 (6H), 3.44 (2H), 2.94 (2H), 1.93 (3H).
Reaction SMILES: [OH:1][CH2:2][CH:3]=[C:4]([CH2:6][CH2:7][CH:8]=[C:9]([CH2:11][CH2:12][CH:13]=[C:14]([CH3:16])[CH3:15])[CH3:10])[CH3:5]>[Pd]>[CH3:5][CH:4]([CH2:6][CH2:7][CH2:8][CH:9]([CH3:10])[CH2:11][CH2:12][CH2:13][CH:14]([CH3:16])[CH3:15])[CH2:3][CH2:2][OH:1]
Reactant: CC(C)=CCCC(C)=CCCC(C)=CCO
Agent: [Pd]
Product: CC(C)CCCC(C)CCCC(C)CCO
Temperature: 25 °C
Reaction time: 12 h

Procedure:
Farnesol (572 g, 2.58 mole, 650 mL) was added to a 1000 mL Parr high pressure vessel containing 10% Pd/C (23 g, 4% by weight of farnesol). The reaction vessel was sealed and evacuated under house vacuum for 5 minutes after which time the reaction mixture was pressurized with H2 to 1000 psi. The reaction mixture was stirred at 25° C. and judged to be complete by thin layer chromatography (“TLC”, Rf=0.32, 90:10 hexane:ethyl acetate) after approximately 12 hours. The reaction vessel was depressurized under vacuum followed by venting to a N2 atmosphere. The reaction contents were vacuum filtered over a silica gel (60 {acute over (Å)} from Aldrich) pad followed by washing of the silica gel with ethyl acetate (“EtOAc”, 3 L). The filtrate was concentrated on a rotary evaporator. The isolated product was further dried under high vacuum to remove any residual EtOAc to afford 3,7,11-trimethyldodecan-1-ol as a lightly tinted yellow viscous liquid. 1H-NMR (CDCl3, 500 MHz): δ 3.71(m, 2H), 1.65-1.05 (m, 17H), 0.89-0.83 (overlapping t&d, 12H).
Reaction SMILES: [C:1]1([CH:8]=[CH:7][C:5]([OH:6])=[CH:4][CH:3]=1)[OH:2].O=O.[CH3:11]O>>[CH3:11][O:2][C:1]1[CH:8]=[CH:7][C:5]([OH:6])=[CH:4][CH:3]=1
Reactant: CO
Reactant: Oc1ccc(O)cc1
Agent: O=O
Product: COc1ccc(O)cc1
Reaction time: 4 h

Procedure:
5.0 g of hydroquinone, 40 cm3 of methanol and 1.0 g of sulphonated styrene resin (Amberlyst 15) are fed into the autoclave. The autoclave is pressurised to 5 kg/cm2 with O2 and kept at 105° for 4 hours. 1.04 g of hydroquinone monomethyl ether are obtained (18%).
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([OH:11])[C:5]([N+:8]([O-])=O)=[CH:6][CH:7]=1>[Pd]>[OH:11][C:4]1[CH:3]=[C:2]([F:1])[CH:7]=[CH:6][C:5]=1[NH2:8]
Reactant: O=[N+]([O-])c1ccc(F)cc1O
Agent: [Pd]
Product: Nc1ccc(F)cc1O
Reaction time: 12 h
Yield: 100.1 %

Procedure:
3-fluoro 6-nitro phenol (2 g, 11 mmol) was treated with 10% Pd/C (1 g) at 23° C. The reaction mixture was flushed with hydrogen gas and the reaction was allowed to stir 12 h before it was filtered through celite. The filtrate was concentrated in vacuo to afford the title compound (1.4 g, 77%). EI-MS m/z 169 (M+H)+
Reaction SMILES: [Cl:1][SiH2:2][Cl:3].[CH2:4]=[CH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>>[CH2:4]([SiH:2]([Cl:3])[Cl:1])[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1
Reactant: C=Cc1ccccc1
Reactant: Cl[SiH2]Cl
Product: Cl[SiH](Cl)CCc1ccccc1

Procedure:
Cyclohexylphenethydichlorosilane having the general formula ##STR12## which is produced by reacting a dichlorosilane and styrene in the presence of the catalyst of claim 6 at a temperature of 30°-150° C. for 0.1-60 hours to produce a monophenethyldichlorosilane and reacting said monosubstitute with cyclohexene at a temperature of 80°-150° C. for 5-20 hours.
Reaction SMILES: N[C:2]1[CH:3]=[N:4][C:5]([C:8]#[N:9])=[CH:6][CH:7]=1.N([O-])=[O:11].[Na+]>O.S(=O)(=O)(O)O>[C:8]([C:5]1[N:4]=[CH:3][C:2]([OH:11])=[CH:7][CH:6]=1)#[N:9]
Reactant: N#Cc1ccc(N)cn1
Reactant: O=N[O-]
Agent: O=S(=O)(O)O
Agent: [Na+]
Solvent: O
Product: N#Cc1ccc(O)cn1
Temperature: 100 °C
Reaction time: 3 h
Yield: 63.3 %

Procedure:
A solution of 1 g (8.06 mmol) of 3-amino-6-cyanopyridine in 12 ml of water and 1.2 ml of sulfuric acid is cooled to 0° C. and 1 g (14.5 mmol) of sodium nitrite is added slowly. The reaction mixture is left to return to room temperature and then stirred at 100° C. for 3 hours. It is left to stand overnight in a refrigerator. The precipitate formed is filtered off and washed with iced water. The expected product also present in the filtrate is extracted with ethyl acetate and combined with the previous precipitate. This crude product is purified by chromatography on silica gel using a dichloromethane/methanol mixture (98/2; v/v) as the eluent to give 613 mg of the expected compound in the form of a brown powder (yield=63%).
Reaction SMILES: [CH2:1]([C:4]1[N:8]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]3[C:17]([C:22]([O:24]C(C)(C)C)=[O:23])=[CH:18][CH:19]=[CH:20][CH:21]=3)=[CH:12][CH:11]=2)[C:7]2[CH:29]=[C:30]([C:34]3[N:38]([CH3:39])[C:37]4[CH:40]=[CH:41][CH:42]=[CH:43][C:36]=4[N:35]=3)[CH:31]=[C:32]([CH3:33])[C:6]=2[N:5]=1)[CH2:2][CH3:3].[ClH:44].O>C(O)(=O)C>[CH3:3][CH2:2][CH2:1][C:4]1[N:8]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=3[C:22]([OH:24])=[O:23])=[CH:12][CH:11]=2)[C:7]2[CH:29]=[C:30]([C:34]3[N:38]([CH3:39])[C:37]4[CH:40]=[CH:41][CH:42]=[CH:43][C:36]=4[N:35]=3)[CH:31]=[C:32]([CH3:33])[C:6]=2[N:5]=1.[ClH:44]
Reactant: CCCc1nc2c(C)cc(-c3nc4ccccc4n3C)cc2n1Cc1ccc(-c2ccccc2C(=O)OC(C)(C)C)cc1
Agent: Cl
Solvent: CC(=O)O
Solvent: O
Product: CCCc1nc2c(C)cc(-c3nc4ccccc4n3C)cc2n1Cc1ccc(-c2ccccc2C(=O)O)cc1
Reaction time: 0.17 h

Procedure:
411 g of tert-butyl 4′-[[2-n-propyl-4-methyl-6-(1-methylbenzimidazol-2-yl)benzimidazol-1-yl]methyl]biphenyl-2-carboxylate is suspended in 822 mL of glacial acetic acid and combined with 213 g of concentrated aqueous hydrochloric acid (37%). The mixture is refluxed and about 640 mL of solvent is distilled off. The residue remaining is slowly combined with about 620 mL of water at 50° C. to 60° C. To this mixture is added 20 g of activated charcoal (e.g., Norit SX 2 Ultra) and the resulting mixture is stirred for about 10 minutes at constant temperature. After filtering, the residue is washed three times with 25 mL of glacial acetic acid and about 620 mL of water. The filtrate obtained is again heated to about 50° C. to 60° C. and about 2 L of water are added. After stirring for about 12 hours at about 23° C., the crystals formed are suction filtered and washed twice with about 500 mL of water, once with about 900 mL of acetone, and then dried at about 60° C. Yield: 367 g (92.5%) colorless crystals, melting point: 278° C.