Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [C:1]1([C:7]2[CH:8]=[CH:9][C:10]3[N:11]([C:26]4[CH:41]=[CH:40][C:29]([O:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][OH:39])=[CH:28][CH:27]=4)[C:12]4[C:17]([C:18]=3[CH:19]=2)=[CH:16][C:15]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[CH:14][CH:13]=4)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:42]1([CH3:52])[CH:47]=[CH:46][C:45]([S:48](Cl)(=[O:50])=[O:49])=[CH:44][CH:43]=1.O>C(Cl)Cl.N1C=CC=CC=1>[C:1]1([C:7]2[CH:8]=[CH:9][C:10]3[N:11]([C:26]4[CH:27]=[CH:28][C:29]([O:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][O:39][S:48]([C:45]5[CH:46]=[CH:47][C:42]([CH3:52])=[CH:43][CH:44]=5)(=[O:50])=[O:49])=[CH:40][CH:41]=4)[C:12]4[C:17]([C:18]=3[CH:19]=2)=[CH:16][C:15]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[CH:14][CH:13]=4)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1
Reactant: Cc1ccc(S(=O)(=O)Cl)cc1
Reactant: OCCCCCCCCOc1ccc(-n2c3ccc(-c4ccccc4)cc3c3cc(-c4ccccc4)ccc32)cc1
Solvent: ClCCl
Solvent: c1ccncc1
Solvent: O
Product: Cc1ccc(S(=O)(=O)OCCCCCCCCOc2ccc(-n3c4ccc(-c5ccccc5)cc4c4cc(-c5ccccc5)ccc43)cc2)cc1
Temperature: 25 °C
Yield: 54 %

Procedure:
The obtained 8-[4-(3,6-diphenylcarbazol-9-yl)phenoxy]octan-1-ol (2.80 g, 5.2 mmol) was dissolved in a solvent mixture of methylene chloride (10 mL) and pyridine (5 mL). Then, p-toluenesulfonyl chloride (1.20 g, 6.3 mmol) was added to the resultant solution at −10° C., followed by stirring at room temperature. Next, the mixture was poured to water, followed by extraction with ethyl acetate. In addition, the mixture was washed with diluted hydrochloric acid and water, and dried and the solvent was evaporated, to thereby obtain a crude product. The crude product was purified through silica gel column chromatography using as an eluent a solvent mixture of ethyl acetate/toluene (1/19 by volume), to thereby obtain 1.95 g of toluene-4-sulfonic acid 8-[4-(3,6-diphenylcarbazol-9-yl)phenoxy]octyl ester as colorless plate-like crystals.
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([C:27]2[CH:32]=[CH:31][CH:30]=[C:29]([O:33][CH3:34])[CH:28]=2)[CH:5]=[CH:6][C:7]=1[N:8]1[C:12](=[O:13])[NH:11][N:10]=[C:9]1[CH2:14][C@@H:15]1[CH2:19][CH2:18][N:17]([C:20]([O:22]C(C)(C)C)=O)[CH2:16]1.Cl.[C:36](Cl)(=O)[CH2:37]C.[NH4+].[Cl-]>O1CCOCC1.ClCCl>[F:1][C:2]1[CH:3]=[C:4]([C:27]2[CH:32]=[CH:31][CH:30]=[C:29]([O:33][CH3:34])[CH:28]=2)[CH:5]=[CH:6][C:7]=1[N:8]1[C:9]([CH2:14][C@@H:15]2[CH2:19][CH2:18][N:17]([C:20](=[O:22])[CH2:36][CH3:37])[CH2:16]2)=[N:10][NH:11][C:12]1=[O:13]
Reactant: CCC(=O)Cl
Reactant: COc1cccc(-c2ccc(-n3c(C[C@@H]4CCN(C(=O)OC(C)(C)C)C4)n[nH]c3=O)c(F)c2)c1
Agent: Cl
Agent: [Cl-]
Agent: [NH4+]
Solvent: ClCCl
Solvent: C1COCCO1
Product: CCC(=O)N1CC[C@@H](Cc2n[nH]c(=O)n2-c2ccc(-c3cccc(OC)c3)cc2F)C1
Temperature: 25 °C
Reaction time: 2 h

Procedure:
Into a 4 mL screwcap vial was placed 1,1-dimethylethyl (3S)-3-({4-[3-fluoro-3′-(methyloxy)-4-biphenylyl]-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl}methyl)-1-pyrrolidinecarboxylate (0.226 mmol). Added to the vial was 4N HCl in dioxane (2.0 mL). The vial was capped and the solution was stirred at room temperature for 2 h. The solution was concentrated in vacuo. Into the vial were place dichloromethane (1 mL) and N,N-diisopropylethylamine (0.14 mL). The solution was cooled in an ice bath. Into a separate vial, propanoyl chloride (0.217 mmol) was taken up in dichloromethane (1 mL) and then 0.5 mL of this solution was added to the cold reaction. The vial was capped and stirred for 1 h, allowing the ice bath to slowly warm to room temperature. Since it was determined that the reaction was not complete, additional 0.10 mL of propanoyl chloride solution in dichloromethane was added to the reaction. After 1 h, the reaction was complete. Dichloromethane (1 mL) and saturated aq NH4Cl were added to the reaction. The vial was lightly agitated and the liquid phases were allowed to separate. The organic layer was separated, dried over sodium sulfate, filtered, and concentrated in vacuo. Reverse phase HPLC (10-70% acetonitrile/water+0.1% NH4OH) was utilized in purifying the title compound (21 mg, 21%). MS(ES)+ m/e 424.9 [M+H]+.
Reaction SMILES: C(=O)([O-])[O-].[Cs+].[Cs+].[OH:7][C:8]1[CH:9]=[C:10]([CH:20]=[C:21]([O:23][C@H:24]2[CH2:28][CH2:27][O:26][CH2:25]2)[CH:22]=1)[C:11]([NH:13][C:14]1[CH:18]=[CH:17][N:16]([CH3:19])[N:15]=1)=[O:12].[Cl:29][C:30]1[CH:31]=[C:32]([C:37]([N:39]2[CH2:44][CH2:43][O:42][CH2:41][CH2:40]2)=[O:38])[CH:33]=[N:34][C:35]=1Cl>C(#N)C>[Cl:29][C:30]1[C:35]([O:7][C:8]2[CH:9]=[C:10]([CH:20]=[C:21]([O:23][C@H:24]3[CH2:28][CH2:27][O:26][CH2:25]3)[CH:22]=2)[C:11]([NH:13][C:14]2[CH:18]=[CH:17][N:16]([CH3:19])[N:15]=2)=[O:12])=[N:34][CH:33]=[C:32]([C:37]([N:39]2[CH2:40][CH2:41][O:42][CH2:43][CH2:44]2)=[O:38])[CH:31]=1
Reactant: O=C(c1cnc(Cl)c(Cl)c1)N1CCOCC1
Reactant: Cn1ccc(NC(=O)c2cc(O)cc(O[C@H]3CCOC3)c2)n1
Agent: O=C([O-])[O-]
Agent: [Cs+]
Solvent: CC#N
Product: Cn1ccc(NC(=O)c2cc(Oc3ncc(C(=O)N4CCOCC4)cc3Cl)cc(O[C@H]3CCOC3)c2)n1
Temperature: 120 °C
Yield: 76.9 %

Procedure:
Cesium carbonate (489 mg, 1.5 mmol) was added to a solution of 3-hydroxy-N-(1-methyl-1H-pyrazol-3-yl)-5-[(3S)-tetrahydrofuran-3-yloxy]benzamide (152 mg, 0.5 mmol) and 4-[(5,6-dichloropyridin-3-yl)carbonyl]morpholine (143 mg, 0.55 mmol) in acetonitrile (5 mL) and the mixture heated at 120° C. in a microwave reactor for 2 hours. The acetonitrile was evaporated in vacuo and the residue partitioned between water (25 mL) and ethyl acetate (50 mL). The organic layer was washed with brine, dried (MgSO4) and evaporated to a residue which was chromatographed on silica, eluting with ethyl acetate, to give the desired compound (203 mg). 1H NMR δ (CDCl3): 2.05-2.2 (m, 2H), 3.4-3.7 (m, 8H), 3.7 (s, 3H), 3.85 (m, 2H), 3.95 (d, 2H), 4.9 (m, 1H), 6.7 (d, 1H), 6.8 (d, 1H), 7.15 (d, 1H), 7.25 (d, 2H), 7.85 (d, 1H), 8.0 (d, 1H), 8.95 (s, 1H); m/z 512 (M+H)+.
Reaction SMILES: [CH2:1]([O:3][C:4](=[O:19])[C:5]([O:8][C:9]1[CH:14]=[CH:13][C:12](C(=O)C)=[C:11]([F:18])[CH:10]=1)([CH3:7])[CH3:6])[CH3:2].ClC1C=CC=[C:23]([C:27]([O:29]O)=[O:28])C=1>ClCCl>[CH2:1]([O:3][C:4](=[O:19])[C:5]([O:8][C:9]1[CH:14]=[CH:13][C:12]([O:29][C:27](=[O:28])[CH3:23])=[C:11]([F:18])[CH:10]=1)([CH3:6])[CH3:7])[CH3:2]
Reactant: O=C(OO)c1cccc(Cl)c1
Reactant: CCOC(=O)C(C)(C)Oc1ccc(C(C)=O)c(F)c1
Solvent: ClCCl
Product: CCOC(=O)C(C)(C)Oc1ccc(OC(C)=O)c(F)c1
Temperature: 25 °C
Reaction time: 24 h
Yield: 100.5 %

Procedure:
A solution of 3.0 g (11.2 mmol) of 2-(4-acetyl-3-fluoro-phenoxy)-2-methyl-propionic acid ethyl ester in 30 ml dichloromethane was treated with 4.1 g (70%, 16.8 mmol) of 3-chloro perbenzoic acid. The reaction was stirred at RT. After 1 day additional 1.2 g (70%, 4.7 mmol), after 2 days 0.8 g (70%, 3.1 mmol) and after 3 days 0.6 g (70%, 2.3 mmol) of 3-chloro perbenzoic acid were added. The mixture was poured on ice/aqueous 10% disodium pyrosulfite solution and extracted with ether (three times). The organic phases were washed with aqueous 10% NaHCO3, aqueous saturated NH4Cl, aqueous 10% NaCl and dried over sodium sulfate to give 3.2 g of the title compound as light yellow oil.
Reaction SMILES: [CH:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]=1.B(F)(F)F.C([O:15]O)(C)(C)C.[CH2:17]([OH:21])[CH2:18][CH2:19][CH3:20]>>[CH2:17]([O:21][CH:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[OH:15])[CH2:18][CH2:19][CH3:20]
Reactant: CCCCO
Reactant: CC(C)(C)OO
Reactant: C1=CCCCC1
Agent: FB(F)F
Product: CCCCOC1CCCCC1O
Temperature: 60 °C
Reaction time: 16 h
Yield: 53 %

Procedure:
Cyclohexene (0.05 mole; 4.1 g) and MoO2(acac)2 (0.5 mmol; 162 mg) were dissolved in anhydrous 1-butanol (30 ml). There was then added one spatulaful of dry mole sieve (4 Å) followed by heating to 60° C. There was added 0.08 ml of BF3 etherate (≈0.5 mmol) followed by the dropwise addition of anhydrous tert-butyl hydroperoxide (0.06 mole; 3M in decane, 20 ml) in 30 minutes. The mixture was allowed to afterreact for 16 hours. The product then was further treated as described in Example 1. According to GC analysis, the 2-butoxy-cyclohexanol yield was 53% of theoretical, relative to cyclohexene.
Reaction SMILES: Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[CH:6][CH:5]=1.C([Li])CCC.CCCCCC.[C:24](=[O:26])=[O:25].O>O1CCCC1>[CH3:11][O:10][C:7]1[CH:8]=[CH:9][C:4]([CH:3]([CH3:2])[C:24]([OH:26])=[O:25])=[CH:5][CH:6]=1
Reactant: COc1ccc(C=C(Br)Br)cc1
Reactant: O=C=O
Agent: [Li]CCCC
Solvent: CCCCCC
Solvent: O
Solvent: C1CCOC1
Product: COc1ccc(C(C)C(=O)O)cc1
Temperature: -78 °C
Reaction time: 1.5 h

Procedure:
1-(2,2-dibromovinyl)-4-methoxybenzene (17.38 g, 59.5 mmol) prepared in Reference Synthetic Example 1 was dissolved in tetrahydrofuran (230 ml) in nitrogen atmosphere, and a 2.59 mol/l n-butyllithium/hexane solution was dropwise added at −78° C. After the dropwise addition, the solution was returned to 0° C. and stirred for 90 minutes, and then cooled to −78° C. again, and crushed dry ice was added. After stirring for 30 minutes, water was added to the solution and the solution was concentrated under reduced pressure. The residue was diluted with diethyl ether, and extracted with a 1 mol/l sodium hydroxide aqueous solution twice. The obtained aqueous layer was acidified (pH=1) with hydrochloric acid and extracted with ethyl acetate twice. The obtained organic layer was washed with water and a saturated salt solution, dried over anhydrous sodium sulfate, subjected to filtration and concentrated under reduced pressure to give the desired compound (4-methxoyphenyl)propionic acid (9.73 g, 93%) as crude crystals.
Reaction SMILES: O[CH2:2][CH2:3][N:4]([CH3:37])[C:5]([C:7]1[C:12]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[C:11]([OH:21])[N:10]=[C:9]([CH2:22][C:23]2([N:28]3[C:32]4=[N:33][CH:34]=[CH:35][CH:36]=[C:31]4[CH:30]=[CH:29]3)[CH2:27][CH2:26][CH2:25][CH2:24]2)[N:8]=1)=[O:6].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.CO>ClCCl.C(OCC)(=O)C>[CH2:14]([O:13][C:12]1[C:11](=[O:21])[N:10]=[C:9]([CH2:22][C:23]2([N:28]3[C:32]4=[N:33][CH:34]=[CH:35][CH:36]=[C:31]4[CH:30]=[CH:29]3)[CH2:27][CH2:26][CH2:25][CH2:24]2)[N:8]2[CH2:2][CH2:3][N:4]([CH3:37])[C:5](=[O:6])[C:7]=12)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: CN(CCO)C(=O)c1nc(CC2(n3ccc4cccnc43)CCCC2)nc(O)c1OCc1ccccc1
Agent: CC(C)OC(=O)N=NC(=O)OC(C)C
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: ClCCl
Solvent: CO
Solvent: CCOC(C)=O
Product: CN1CCn2c(CC3(n4ccc5cccnc54)CCCC3)nc(=O)c(OCc3ccccc3)c2C1=O
Reaction time: 0.17 h
Yield: 29.5 %

Procedure:
To a stirred solution of 5-benzyloxy-6-hydroxy-2-(1-pyrrolo[2,3-b]pyridin-1-yl-cyclopentylmethyl)-pyrimidine-4-carboxylic acid (2-hydroxyethyl)-methyl-amide (406) (210 mg, 0.42 mmol) in dichloromethane (30 mL) was added triphenyl phosphine (550 mg, 2.09 mmol) followed by diisopropyl azodicarboxylate (0.2 mL, 1.26 mmol) at room temperature and stirring was continued for 10 min (TLC, 5% methanol in ethyl acetate, Rf=0.2). The reaction mixture was concentrated under reduced pressure to get a crude product, which was purified by Prep-TLC plate (mobile phase 5% methanol in ethyl acetate) to get 9-benzyloxy-2-methyl-6-(1-pyrrolo[2,3-b]pyridin-1-yl-cyclopentylmethyl)-3,4-dihydro-2H-pyrazino[1,2-c]pyrimidine-1,8-dione (407) (60 mg, 30%) as a white solid.
Reaction SMILES: [C:1]([C:5]1[N:10]=[CH:9][C:8]([C:11]2[N:12]([C:32]([N:34]3[CH2:39][CH2:38][C:37]4([CH2:44][CH2:43][NH:42][CH2:41][CH2:40]4)[CH2:36][CH2:35]3)=[O:33])[C@@:13]([C:25]3[CH:30]=[CH:29][C:28]([Cl:31])=[CH:27][CH:26]=3)([CH3:24])[C@@:14]([C:17]3[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][CH:18]=3)([CH3:16])[N:15]=2)=[C:7]([O:45][CH2:46][CH3:47])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].Cl[CH2:49][C:50]([NH2:52])=[O:51]>C(N(CC)CC)C.CN(C)C=O.O>[C:1]([C:5]1[N:10]=[CH:9][C:8]([C:11]2[N:12]([C:32]([N:34]3[CH2:35][CH2:36][C:37]4([CH2:44][CH2:43][N:42]([CH2:49][C:50]([NH2:52])=[O:51])[CH2:41][CH2:40]4)[CH2:38][CH2:39]3)=[O:33])[C@@:13]([C:25]3[CH:30]=[CH:29][C:28]([Cl:31])=[CH:27][CH:26]=3)([CH3:24])[C@@:14]([C:17]3[CH:18]=[CH:19][C:20]([Cl:23])=[CH:21][CH:22]=3)([CH3:16])[N:15]=2)=[C:7]([O:45][CH2:46][CH3:47])[CH:6]=1)([CH3:2])([CH3:3])[CH3:4]
Reactant: CCOc1cc(C(C)(C)C)ncc1C1=N[C@@](C)(c2ccc(Cl)cc2)[C@@](C)(c2ccc(Cl)cc2)N1C(=O)N1CCC2(CCNCC2)CC1
Reactant: NC(=O)CCl
Solvent: O
Solvent: CN(C)C=O
Solvent: CCN(CC)CC
Product: CCOc1cc(C(C)(C)C)ncc1C1=N[C@@](C)(c2ccc(Cl)cc2)[C@@](C)(c2ccc(Cl)cc2)N1C(=O)N1CCC2(CCN(CC(N)=O)CC2)CC1
Temperature: 160 °C
Yield: 91.7 %

Procedure:
The mixture of [(4S,5R)-2-(6-tert-butyl-4-ethoxy-pyridin-3-yl)-4,5-bis-(4-chloro-phenyl)-4,5-dimethyl-4,5-dihydro-imidazol-1-yl]-(3,9-diaza-spiro[5.5]undec-3-yl)-methanone (25 mg, 0.037 mmol, example 75), 2-chloroacetamide (6.9 mg, 0.074 mmol, Aldrich) and triethylamine (1 drop) in dimethylformamide (1 mL) was heated at 160° C. for 10 min using the microwave synthesizer. The mixture was diluted with water, extracted with ethyl ether (2×). The extracts were washed with brine, dried over anhydrous magnesium sulfate and concentrated. The crude was filtered through a plug of silica gel, eluting with 5% methanol-ethyl acetate to give the title product as white solids (24.9 mg). HR-MS (ES, m/z) calculated for C40H51Cl2N6O3 [(M+H)+] 733.3394, observed 733.3392.
Reaction SMILES: [O:1]=[C:2]([OH:14])[C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([C:11]([OH:13])=[O:12])[OH:10])[OH:8])[OH:6])[OH:4].[Na:15][Na].O=C[C@@H]([C@H]([C@@H]([C@@H](CO)O)O)O)O>>[O:1]=[C:2]([O-:14])[C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([C:11]([O-:13])=[O:12])[OH:10])[OH:8])[OH:6])[OH:4].[Na+:15].[Na+:15]
Reactant: O=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(=O)O
Reactant: [Na][Na]
Agent: O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
Product: O=C([O-])[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(=O)[O-]
Product: [Na+]
Yield: 97.9 %

Procedure:
Isolation of glucaric acid as its disodium salt.5 D-Glucose (162.5 g, 0.75 mol) was oxidized using the LabMax reactor as described. Following the completion of the reaction, the reaction solution was concentrated to a white foam in vacuo (10-15 mbar) using a rotary evaporator and water bath at 50° C. The concentrate of organic product(s) and residual nitric acid was diluted with deionized water (150 mL), titrated with sodium hydroxide solution (5 M) to an approximate pH of 9.5 , and then diluted with deionized water (3700 mL), giving an approximate 2.5% (w/w) solids solution. This solution was then filtered using a nanofiltration unit. The nanofiltration unit, built in-house, is comprised of the necessary valves, pump, lines, pressure gauge and an appropriate membrane such as a GE DL2540F membrane. When the permeate volume reached 1000 mL, 1000 mL of reverse osmosis (RO) purified water was added to the feedstock. The typical rate of the permeate flow when reducing the volume by 1000 mL was 48 mL/min. When 2000 mL of permeate was removed, another 1000 mL of RO water was added to the feedstock. The typical rate of permeate flow when removing the second 1000 mL was 45 mL/min. This procedure was repeated until a total of 4000 mL had been removed via the permeate and 4000 mL of RO water had been added to the feedstock. The typical permeate flow rate when removing the last 1000 mL was 43 mL/min. The filtration process was continued after the last 1000 mL of RO water was added to the feedstock until the permeate flow slowed to a trickle at which time the filtration was stopped. The final volumes of the retentate and permeate were 2800 mL and 5200 mL, respectively. Analysis of the permeate and retentate by ion chromatography (IC) indicated that sodium nitrate is the major component of the permeate and is present only in minor amounts in the retentate. The retentate was concentrated under reduced pressure using a rotary evaporator and further dried in a vacuum oven to yield crude disodium D-glucarate (186.52 g, 97.9% based on pure disodium D-glucarate). The salt was then dissolved in water, and the pH of the solution adjusted with sodium hydroxide to pH 8 . The product was precipitated with methanol (1000 mL) as an off white solid (146.24 g, 76.7% based on pure disodium D-glucarate).
Reaction SMILES: [CH2:1]([C:6]1[CH:11]=[CH:10][C:9]([OH:12])=[CH:8][CH:7]=1)[CH2:2][CH2:3][CH2:4][CH3:5].C(=O)([O-])[O-].[K+].[K+].[CH2:19]([C:21]([CH3:23])=[O:22])C>>[CH2:1]([C:6]1[CH:7]=[CH:8][C:9]([O:12][CH2:19][CH:21]2[CH2:23][O:22]2)=[CH:10][CH:11]=1)[CH2:2][CH2:3][CH2:4][CH3:5]
Reactant: CCC(C)=O
Reactant: CCCCCc1ccc(O)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Product: CCCCCc1ccc(OCC2CO2)cc1

Procedure:
A mixture of 44 g of 4-pentylphenol (Eastman Kodak), 50 ml of epichlolorohydrin, 120 g of potassium carbonate in 250 ml methyl ethyl ketone was refluxed for 12 hr. Residual after removal of solid and solvent was distilled through a Kugelrohr adaptor to give the title compound, bp 180°-195°/0.3 mmHg.
Reaction SMILES: Cl.[CH3:2][C:3]1([CH3:16])[C:7]([CH3:9])([CH3:8])[O:6][B:5]([C:10]2[CH2:11][CH2:12][NH:13][CH2:14][CH:15]=2)[O:4]1.[C:17]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])(=[O:20])[CH:18]=[CH2:19].C(=O)([O-])[O-].[K+].[K+].C(#N)C>O>[CH3:9][C:7]1([CH3:8])[C:3]([CH3:16])([CH3:2])[O:4][B:5]([C:10]2[CH2:11][CH2:12][N:13]([CH2:19][CH2:18][C:17]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:14][CH:15]=2)[O:6]1
Reactant: CC1(C)OB(C2=CCNCC2)OC1(C)C
Reactant: C=CC(=O)OC(C)(C)C
Agent: Cl
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CC#N
Product: CC(C)(C)OC(=O)CCN1CC=C(B2OC(C)(C)C(C)(C)O2)CC1
Reaction time: 8 h

Procedure:
A mixture of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine hydrochloride (100 mg), tert-butyl acrylate (0.089 mL), potassium carbonate (169 mg), and acetonitrile (2 mL) was stirred overnight at 70 C. In another reaction vessel, a mixture of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine hydrochloride (1.00 g), tert-butyl acrylate (0.895 mL), potassium carbonate (1.688 g), and acetonitrile (10 mL) was stirred overnight at 70 C. These two reaction mixtures were combined, and water was added thereto, followed by extraction with ethyl acetate. The extract was washed with brine and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (NH, ethyl acetate/hexane) to obtain the title compound (1.11 g).
Reaction SMILES: Cl.[F:2][C:3]([F:25])([F:24])[C:4]1[CH:13]=[C:12]2[C:7]([C:8]([NH:14][C:15]3[CH:23]=[CH:22][C:18]([C:19](Cl)=[O:20])=[CH:17][CH:16]=3)=[CH:9][CH:10]=[N:11]2)=[CH:6][CH:5]=1.C(=O)([O-])[O-].[Na+].[Na+].[F:32][C:33]1[CH:38]=[CH:37][C:36]([S:39]([N:42]([CH3:47])[CH2:43][CH2:44][NH:45][CH3:46])(=[O:41])=[O:40])=[CH:35][CH:34]=1>C(Cl)(Cl)Cl.O>[F:32][C:33]1[CH:34]=[CH:35][C:36]([S:39]([N:42]([CH3:47])[CH2:43][CH2:44][N:45]([CH3:46])[C:19](=[O:20])[C:18]2[CH:22]=[CH:23][C:15]([NH:14][C:8]3[C:7]4[C:12](=[CH:13][C:4]([C:3]([F:25])([F:24])[F:2])=[CH:5][CH:6]=4)[N:11]=[CH:10][CH:9]=3)=[CH:16][CH:17]=2)(=[O:40])=[O:41])=[CH:37][CH:38]=1
Reactant: O=C(Cl)c1ccc(Nc2ccnc3cc(C(F)(F)F)ccc23)cc1
Reactant: CNCCN(C)S(=O)(=O)c1ccc(F)cc1
Agent: Cl
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: ClC(Cl)Cl
Solvent: O
Product: CN(CCN(C)S(=O)(=O)c1ccc(F)cc1)C(=O)c1ccc(Nc2ccnc3cc(C(F)(F)F)ccc23)cc1
Temperature: 25 °C
Yield: 48.3 %

Procedure:
4-(7-Trifluoromethyl-4-quinolinylamino)benzoyl chloride hydrochloride (2.0 g) was added portionwise to a well-stirred mixture of sodium carbonate (8.0 g) and 4-fluoro-N-methyl-N-[2-(methylamino)ethyl]benzenesulphonamide (1.48 g) in chloroform (60 ml) and water (70 ml) at about 10° C. The mixture was warmed to room temperature and, after 1 hour, the chloroform layer was separated, dried (MgSO4) and evaporated under reduced pressure to give an oil, which crystallised on standing. Recrystallisation from ethanol/water gave a white solid, which was further purified by recrystallisation from ethanol, giving the pure title compound (1.4 g), m.p. 191°-3° C.
Reaction SMILES: [OH:1][CH2:2][C:3]1[CH:4]=[CH:5][C:6]2[CH:7]3[CH2:16][CH2:15][CH2:14][CH:8]3[C:9](=[O:13])[NH:10][C:11]=2[CH:12]=1.C[N+]1([O-])CCOCC1>C(Cl)(Cl)Cl.ClCCl.C(#N)C.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[CH2:16]1[CH:7]2[CH:8]([C:9](=[O:13])[NH:10][C:11]3[CH:12]=[C:3]([CH:2]=[O:1])[CH:4]=[CH:5][C:6]=32)[CH2:14][CH2:15]1
Reactant: O=C1Nc2cc(CO)ccc2C2CCCC12
Agent: O=[Ru](=O)(=O)[O-]
Agent: CCC[N+](CCC)(CCC)CCC
Agent: C[N+]1([O-])CCOCC1
Solvent: ClCCl
Solvent: ClC(Cl)Cl
Solvent: CC#N
Product: O=Cc1ccc2c(c1)NC(=O)C1CCCC21
Reaction time: 1.5 h
Yield: 84.3 %

Procedure:
A solution of 187 mg (0.86 mmol) of 7-hydroxymethyl-1,2,3,3a,5,9b-hexahydrocyclopenta[c]quinolin-4-one in 20 ml of chloroform-dichloromethane-acetonitrile (2:1:1) is mixed with 151 mg (1.29 mmol) of N-methylmorpholin-N-oxide and 1.5 g of molecular sieve 4 Å. After 15 mg (0.043 mmol) of tetrapropylammonium perruthenate (TPAP) is added, the batch is stirred for 2.5 hours at room temperature, before another 10 mg (0.028 mmol) of TPAP is added. After 1.5 hours, silica gel is added to the reaction mixture, and the solvent is distilled off in a vacuum. Column chromatography with hexane-ethyl acetate yields 156 mg of product.
Reaction SMILES: [CH2:1]=[CH:2][CH2:3][CH2:4][CH2:5][CH3:6].[Cl:7][SiH2:8][Cl:9].[CH2:10]=[CH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>C1C=CC([P]([Pt]([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>[CH2:1]([Si:8]([CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([Cl:9])[Cl:7])[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6]
Reactant: C=CCCCC
Reactant: C=Cc1ccccc1
Reactant: Cl[SiH2]Cl
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pt]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Product: CCCCCC[Si](Cl)(Cl)CCc1ccccc1
Temperature: 100 °C
Yield: 90.6 %

Procedure:
0.89 mol of 1-hexene, 0.08 mol % of a catalyst of tetrakis(triphenylphosphine)platinum (O) (relative to dichlorosilane) were introduced into a 500 ml pressure-proof stainless steel reactor which was then closed and cooled with a dry-ice-methanol bath. After introducing 0.64 mol of dichlorosilane through a leading pipe, the reactor was sealed and reaction was carried out by heating in an oil bath at 100° C. for 2 hours with stirring. Then this reacted liquid was transferred to a flask. 0.64 mol of styrene was added and reaction was carried out with stirring at 80° C. for 4 hours. After the reaction, distillation was carried out under a reduced pressure to obtain 0.58 mol of n-hexylphenethyldichlorosilane having a boiling point of 120°~123° C./1 mmHg.
Reaction SMILES: [Cl:1][C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[CH:4]=O.[CH3:11][C:12]1[N:13]=[C:14]([CH2:17][C:18]([CH3:20])=O)[S:15][CH:16]=1.[NH2:21]/[C:22](/[CH3:26])=[CH:23]\[C:24]#[N:25]>C(O)(C)C>[Cl:1][C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[CH:4]1[C:17]([C:14]2[S:15][CH:16]=[C:12]([CH3:11])[N:13]=2)=[C:18]([CH3:20])[NH:21][C:22]([CH3:26])=[C:23]1[C:24]#[N:25]
Reactant: O=Cc1ccc(F)cc1Cl
Reactant: CC(=O)Cc1nc(C)cs1
Reactant: C/C(N)=C/C#N
Solvent: CC(C)O
Product: CC1=C(C#N)C(c2ccc(F)cc2Cl)C(c2nc(C)cs2)=C(C)N1
Temperature: 25 °C
Reaction time: 8 h

Procedure:
150 mg (0.946 mmol) of 2-chloro-4-fluorobenzaldehyde, 147 mg (0.811 mmol) of the compound from example 4A and 78 mg (0.811 mmol) of 3-aminocrotononitrile are dissolved in 4 ml of isopropanol and stirred at the reflux temperature overnight. After cooling to room temperature, the volatile components are removed in a rotary evaporator, the crude material is taken up in 5 ml of ethyl acetate, and the precipitated product is then filtered off 199 mg (58% of theory) of the title compound are obtained.