Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][N:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4]([CH:11]=O)=[CH:3]1.[S:13]([NH2:17])([NH2:16])(=[O:15])=[O:14].[BH4-].[Na+]>C(O)C.O>[CH3:1][N:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4]([CH2:11][NH:16][S:13]([NH2:17])(=[O:15])=[O:14])=[CH:3]1
Reactant: NS(N)(=O)=O
Reactant: Cn1cc(C=O)c2ccccc21
Agent: [BH4-]
Agent: [Na+]
Solvent: CCO
Solvent: O
Product: Cn1cc(CNS(N)(=O)=O)c2ccccc21
Temperature: 25 °C
Reaction time: 1 h

Procedure:
N-Methylindole-3-carboxaldehyde (1.66 g, 10.4 mmol) was dissolved in anhydrous ethanol (50 mL). Sulfamide (4.5 g, 47 mmol) was added and the mixture was heated to reflux for 16 hours. Additional sulfamide (1.0 g, 10.4 mmol) was added and the mixture was heated to reflux for 24 hours. The mixture was cooled to room temperature. Sodium borohydride (0.722 g, 12.5 mmol) was added and the mixture was stirred at room temperature for one hour. The reaction was diluted with water (50 mL) and extracted with DCM (3×75 mL). The extracts were concentrated and about 1 mL of methanol was added to create a slurry which was filtered to yield the title compound as a white powder.
Reaction SMILES: [O:1]=[C:2]1[CH2:6][CH2:5][CH2:4][N:3]1[CH2:7][C:8]([O:10]CC)=O.[CH2:13]([N:15]([CH2:19][CH3:20])[CH2:16][CH2:17][NH2:18])[CH3:14]>>[CH2:13]([N:15]([CH2:19][CH3:20])[CH2:16][CH2:17][NH:18][C:8](=[O:10])[CH2:7][N:3]1[CH2:4][CH2:5][CH2:6][C:2]1=[O:1])[CH3:14]
Reactant: CCN(CC)CCN
Reactant: CCOC(=O)CN1CCCC1=O
Product: CCN(CC)CCNC(=O)CN1CCCC1=O

Procedure:
From 12.8 g. of ethyl 2-oxo-1-pyrrolidineacetate and 17.4 g. of 2-(diethylamino)ethylamine [J.A.C.S. 68, 2006 (1946)], following the procedure of Example 1, there is obtained N-[2-(diethylamino)ethyl]-2-oxo-1-pyrrolidineacetamide; b.p. 157° C./0.1 mm.
Reaction SMILES: [OH:1][CH2:2][CH:3]1[CH2:8][CH2:7][CH:6]([OH:9])[CH2:5][CH2:4]1.[C:10]1([C:16](Cl)([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>N1C=CC=CC=1>[C:16]([O:1][CH2:2][CH:3]1[CH2:8][CH2:7][CH:6]([OH:9])[CH2:5][CH2:4]1)([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)([C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1
Reactant: ClC(c1ccccc1)(c1ccccc1)c1ccccc1
Reactant: OCC1CCC(O)CC1
Solvent: c1ccncc1
Product: OC1CCC(COC(c2ccccc2)(c2ccccc2)c2ccccc2)CC1
Temperature: 0 °C
Reaction time: 16 h

Procedure:
4-(Hydroxymethyl)cyclohexanol (2.0 g, 0.015 mol) was dissolved in pyridine (15.0 mL) and the mixture was cooled to 0° C. To the reaction was added triphenylmethyl chloride (4.7 g, 0.017 mol) and the resulting mixture was stirred at 0° C. for 2 hours and at 25° C. for 16 hours. The reaction was then concentrated using a rotory evaporator, and the concentrate was extracted with ethyl acetate. The organic extracts were washed with water, saturated NaCl, dried (MgSO4) and then concentrated in vacuo. The reaction was chromatographed on silica gel using 30% EtOAc/hexanes to give the cis isomer (0.74 g) 1H NMR (CDCl3): δ 7.52 (m, 6H), 7.27 (m, 9H), 3.98 (m, 1H), 2.93 (m, 2H), 1.21-1.68 (m, 9H); and the trans isomer (2.72 g) 1H NMR (CDCl3): δ 7.44 (m, 6H), 7.20-7.31 (m, 9H), 3.54 (m, 1H), 2.88 (m, 2H), 1.98 (m, 2H), 1.88 (m, 2H), 1.60 (m, 1H), 0.99-1.37 (m, 4H).
Reaction SMILES: [N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]=1[O:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH:21]=[O:22].[CH3:23][Mg]I.[Mg].IC>C(OCC)C>[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]=1[O:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH:21]([OH:22])[CH3:23]
Reactant: C[Mg]I
Reactant: O=CCCCCCCCCCOc1ccc2ccccc2n1
Agent: [Mg]
Solvent: CI
Solvent: CCOCC
Product: CC(O)CCCCCCCCCOc1ccc2ccccc2n1

Procedure:
10-(2-Quinolinyloxy)decan-1-al (3.5 g) in dry diethyl ether (15 ml was treated with methyl magnesium iodide in dry ether (2 ml) prepared from magnesium (0.29 g) and iodomethane (0.75 ml). After quenching with satd. aqueous ammonium chloride the reaction was worked-up in the usual manner and the crude product purified by column chromatography on silica (8:2, hexane:ether) to give 11-(2-quinolinyloxy)undecan-2-ol (1.24 g).
Reaction SMILES: [NH2:1][C:2]1[C:7]2=[C:8]([C:12]([NH:14][C@H:15]3[CH2:20][CH2:19][C@H:18]([OH:21])[CH2:17][CH2:16]3)=[O:13])[CH:9]=[C:10](Br)[N:6]2[N:5]=[CH:4][N:3]=1.[F:22][C:23]1[CH:28]=[C:27](B(O)O)[CH:26]=[CH:25][N:24]=1.C(=O)([O-])[O-].[K+].[K+].CCOCC>CN(C=O)C.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[C:7]2=[C:8]([C:12]([NH:14][C@H:15]3[CH2:20][CH2:19][C@H:18]([OH:21])[CH2:17][CH2:16]3)=[O:13])[CH:9]=[C:10]([C:27]3[CH:26]=[CH:25][N:24]=[C:23]([F:22])[CH:28]=3)[N:6]2[N:5]=[CH:4][N:3]=1
Reactant: Nc1ncnn2c(Br)cc(C(=O)N[C@H]3CC[C@H](O)CC3)c12
Reactant: OB(O)c1ccnc(F)c1
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CN(C)C=O
Solvent: CCOCC
Product: Nc1ncnn2c(-c3ccnc(F)c3)cc(C(=O)N[C@H]3CC[C@H](O)CC3)c12
Temperature: 100 °C
Reaction time: 2 h

Procedure:
A suspension of 3A (39 mg, 0.11 mmol), 2-fluoropyridin-4-ylboronic acid (31 mg, 0.22 mmol) and aq. potassium carbonate (0.14 mL, 0.21 mmol) in 2 mL of degassed DMF was treated with 6 mg (0.006 mmol) of tetrakis(triphenylphosphine)palladium(0). The mixture was stirred at 100° C. for 2 h, cooled to RT, and diluted with water. The resulting mixture was extracted three times with 9:1 chloroform-ethanol, and the combined organic extracts dried and concentrated. Trituration from ether afforded 3 (8 mg, 18% yield) as a white powder. HPLC: 5.88 min (YMC S5 ODS, 4.5×50 mm. 4 mL/min, 10-90% methanol-water 0.2% H3PO4, gradient over 12 min). MS (ES): m/z=371 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 10.49 (br. s, 1H); 8.36-8.44 (m, 3H); 8.16 (s, 1H); 8.15 (s, 1H); 8.01-8.04 (m, 1H); 7.95 (s, 1H); 4.65 (d, 1H, J=4.3 Hz); 3.75-3.86 (m, 1H); 3.40-3.51 (m, 1H); 1.85-1.96 (m, 4H); 1.23-1.49 (m, 4H).
Reaction SMILES: [OH:1][CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1.C(=O)([O-])[O-].[K+].[K+].Br[CH2:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20]>C(#N)C>[OH:1][CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[CH:6][CH:5]=1
Reactant: CC(C)(C)OC(=O)CBr
Reactant: OCCc1ccc(O)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC#N
Product: CC(C)(C)OC(=O)COc1ccc(CCO)cc1
Yield: 92.8 %

Procedure:
A mixture of 4-(2-hydroxyethyl)phenol (3.8 ml, 25.834 mmol) was dissolved in acetonitrile (25 ml), potassium carbonate (7.085 g, 51.267 mmol) and tert-butyl bromoacetate (5.000 g, 25.834 mmol) was boiled under reflux for 16 hours. The solvent was evaporated under reduced pressure. The residue was dissolved in EtOAc and washed with brine and water, dried with MgSO4 and evaporated under reduced pressure to give the desired product was obtained (6.00 g, yield 92.8%).
Reaction SMILES: [NH2:1][C:2]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[O:12]([C:19]1[CH:24]=[CH:23][C:22]([N:25]=[C:26]=O)=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(Cl)CCl>C1COCC1.CN(C=O)C>[CH3:11][C:8]1[CH:9]=[CH:10][C:2]2[N:1]=[C:26]([NH:25][C:22]3[CH:23]=[CH:24][C:19]([O:12][C:13]4[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=4)=[CH:20][CH:21]=3)[O:5][C:4](=[O:6])[C:3]=2[CH:7]=1
Reactant: Cc1ccc(N)c(C(=O)O)c1
Reactant: O=C=Nc1ccc(Oc2ccccc2)cc1
Solvent: C1CCOC1
Solvent: ClCCCl
Solvent: CN(C)C=O
Product: Cc1ccc2nc(Nc3ccc(Oc4ccccc4)cc3)oc(=O)c2c1
Temperature: 25 °C
Reaction time: 24 h
Yield: 40.4 %

Procedure:
A solution of 2-amino-5-methylbenzoic acid (172 mg, 1.10 mmol) in THF (1 ml) was treated with 4-phenoxyphenyl isocyanate (241 mg, 1.10 mmol). The mixture was kept at room temperature for 24 h, during which time the solvent was allowed to evaporate to leave a pale brown solid. This was dissolved in DMF (5 ml) and added to a suspension of PS-EDC (0.8 mmol g−1, 2.8 g) in DMF (20 ml). The resulting mixture was agitated at room temperature for 18 h, after which the resin was filtered off and washed with DMF (2×5 ml). The filtrate and washings were combined and evaporated under reduced pressure. Flash column chromatography over silica (20% ethyl acetate in hexane as eluent) afforded the required compound as an off-white solid (153 mg, 40%); δH (400 MHz, DMSO-d6) 2.36 (3H, s, CH3), 6.96 (2H, d, J 8, Ph), 7.04 (1H, d, J 8, Ph), 7.09 (1H, t, J 8, Ph), 7.26 (1H, d, J 8, Ph), 7.34-7.38 (2H, m, Ph), 7.55-7.56 (1H, m, Ph), 7.76-7.78 (4H, m, Ph); m/z (ES+) 345 (MH+).
Reaction SMILES: [ClH:1].[Cl:2][C:3]1[CH:4]=[C:5]([CH:14]=[CH:15][C:16]=1[Cl:17])[C:6](=O)[CH2:7][CH:8]([C:11]#[N:12])[C:9]#[N:10].CCOCC>C(Cl)(Cl)Cl>[Cl:1][C:9]1[NH:10][C:6]([C:5]2[CH:14]=[CH:15][C:16]([Cl:17])=[C:3]([Cl:2])[CH:4]=2)=[CH:7][C:8]=1[C:11]#[N:12]
Reactant: Cl
Reactant: N#CC(C#N)CC(=O)c1ccc(Cl)c(Cl)c1
Solvent: CCOCC
Solvent: ClC(Cl)Cl
Product: N#Cc1cc(-c2ccc(Cl)c(Cl)c2)[nH]c1Cl
Temperature: 0 °C
Reaction time: 0.42 h
Yield: 76 %

Procedure:
Hydrogen chloride gas is bubbled through a mixture of (3,4-dichlorophenacyl)malononitrile (8.3 g, 0.333 mol), ether (150 mL) and chloroform (100 mL) at a moderate rate, keeping the reaction mixture temperature below 35°-40° C. After 25 minutes, TLC shows the reaction is complete by UV analysis. The brown reaction mixture is poured into an ice-water mixture and extracted with ether. The combined organic extracts are washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to obtain a brown solid. The brown solid is washed with methylene chloride and filtered to give the title product as an off-white solid (6.7 g, 76%, mp >200° C.). Identified by IR and NMR spectral analyses.
Reaction SMILES: [NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[F:10][C:11]1[CH:28]=[CH:27][C:14]([CH2:15][CH:16]2[CH2:21][CH2:20][N:19]([C:22](=[O:26])[C:23](O)=[O:24])[CH2:18][CH2:17]2)=[CH:13][CH:12]=1>C(OCC)C>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([NH:1][C:23](=[O:24])[C:22]([N:19]2[CH2:18][CH2:17][CH:16]([CH2:15][C:14]3[CH:13]=[CH:12][C:11]([F:10])=[CH:28][CH:27]=3)[CH2:21][CH2:20]2)=[O:26])=[CH:3][CH:4]=1)#[N:7]
Reactant: N#Cc1ccc(N)cc1
Reactant: O=C(O)C(=O)N1CCC(Cc2ccc(F)cc2)CC1
Solvent: CCOCC
Product: N#Cc1ccc(NC(=O)C(=O)N2CCC(Cc3ccc(F)cc3)CC2)cc1

Procedure:
The title compound is prepared from 4-amino-benzonitrile and [4-(4-fluoro-benzyl)-piperidin-1-yl]-oxo-acetic acid (Example 1b) according to the method described in Example 1c. Melting Point: 167-169° C. (diethylether)
Reaction SMILES: [CH2:1]([CH:5]([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH2:6][C:7]1[S:8][CH:9]=[CH:10][CH:11]=1)[CH2:2][CH2:3][CH3:4].[Li]CCCC.[CH3:23][Sn:24](Cl)([CH3:26])[CH3:25]>C1COCC1.CCCCCC>[CH2:1]([CH:5]([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH2:6][C:7]1[S:8][C:9]([Sn:24]([CH3:26])([CH3:25])[CH3:23])=[CH:10][CH:11]=1)[CH2:2][CH2:3][CH3:4]
Reactant: C[Sn](C)(C)Cl
Reactant: CCCCCCC(CCCC)Cc1cccs1
Agent: [Li]CCCC
Solvent: C1CCOC1
Solvent: CCCCCC
Product: CCCCCCC(CCCC)Cc1ccc([Sn](C)(C)C)s1
Temperature: -78 °C
Reaction time: 0.17 h

Procedure:
A solution of 2-(2-butyloctyl)thiophene (1.52 g, 6.02 mmol) in dry THF (30 mL) was cooled to −78° C., and a solution of n-BuLi (2.5 M, 3.6 mL, 9.0 mmol) was then added slowly. This mixture was stirred at −78° C. for additional 10 minutes, and allowed to warm to room temperature and stirred at room temperature for 30 minutes, before it was cooled back to −78° C. again. A solution of trimethylstannyl chloride (1.0 M, 9 mL, 9.0 mmol) was added slowly. This mixture was stirred at −78° C. for 1 hour, and then allowed to warm to room temperature, and stirred at room temperature overnight. The reaction was quenched by water. The resulting reaction mixture was diluted with hexane, washed with water, dried over Na2SO4, and concentrated on a rotary evaporator, leading to a slightly yellow oil (2.48 g, 99.2%), which was directly used in the next step without further purification.
Reaction SMILES: [Si:1]([O:8][C:9]1[CH:10]=[C:11]([CH:14]=[CH:15][CH:16]=1)[CH2:12]O)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C(N(CC)CC)C.CS([Cl:28])(=O)=O.O>ClCCl>[Si:1]([O:8][C:9]1[CH:10]=[C:11]([CH:14]=[CH:15][CH:16]=1)[CH2:12][Cl:28])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]
Reactant: CS(=O)(=O)Cl
Reactant: CC(C)(C)[Si](C)(C)Oc1cccc(CO)c1
Solvent: CCN(CC)CC
Solvent: O
Solvent: ClCCl
Product: CC(C)(C)[Si](C)(C)Oc1cccc(CCl)c1
Temperature: 0 °C
Reaction time: 25 h

Procedure:
3-(tert-Butyldimethylsilyloxy)benzyl alcohol (101) (prepared by the process described in Wu, Y.-C. et al., J. Am. Chem. Soc., 130, 7148-7152 (2008)) (7.94 g, 31.4 mmol) was dissolved in dichloromethane (150 mL), and cooled to 0° C. To this were sequentially added triethylamine (9.10 mL, 66.7 mmol) and methanesulfonyl chloride (3.80 mL, 49.1 mmol) and stirred for 25 hours after warming up to room temperature. To this was added water, and the product was extracted with dichloromethane (×3). The organic layer was sequentially washed with water (×1) and saturated brine (×1), and dried over anhydrous sodium sulfate. After filtration, the mixture was concentrated under reduced pressure and the residue was purified by silica gel flash column chromatography (n-hexane/ethyl acetate═95/1) to give 3-(tert-butyldimethylsilyloxy)benzyl chloride (102) as a colorless oily substance (5.90 g, 23.0 mmol, 73.1%).
Reaction SMILES: [CH:1]1([CH:6]=[O:7])[CH2:5][CH2:4][CH2:3][CH2:2]1.[C:8]([Mg]Br)#[CH:9]>O1CCCC1>[CH:1]1([CH:6]([OH:7])[C:8]#[CH:9])[CH2:5][CH2:4][CH2:3][CH2:2]1
Reactant: O=CC1CCCC1
Reactant: C#C[Mg]Br
Solvent: C1CCOC1
Product: C#CC(O)C1CCCC1
Temperature: 25 °C
Reaction time: 2 h
Yield: 92 %

Procedure:
A solution of 0.87 ml of cyclopentanecarboxaldehyde (8.15 mmol; Aldrich) in 10 ml of tetrahydrofuran is added to 18 ml of a commercially available 0.5 M solution of ethynylmagnesium bromide in tetrahydrofuran (10 mmol, Aldrich) cooled beforehand to 0° C. The mixture is then stirred for 2 hours at ambient temperature and a saturated solution of NH4Claq is added. The mixture is extracted with ethyl acetate and the organic phases are then combined, washed with a saturated solution of NaClaq, dried over sodium sulphate, filtered, and concentrated under vacuum. 0.931 g of (±)-1-cyclopentylprop-2-yn-1-ol is obtained in the form of a light brown oil with a yield of 92%.
Reaction SMILES: [CH3:1][C:2]1([CH3:19])[CH2:7][CH2:6][C:5]([CH:8]([CH3:11])[CH2:9][OH:10])=[C:4]2[C:12]([CH3:18])([CH3:17])[CH:13]3[CH2:16][C:3]12[CH2:15][CH2:14]3.[CH2:20]1COCC1.[H-].[Na+].CI>CN(C=O)C>[CH3:20][O:10][CH2:9][CH:8]([C:5]1[CH2:6][CH2:7][C:2]([CH3:1])([CH3:19])[C:3]23[CH2:16][CH:13]([CH2:14][CH2:15]2)[C:12]([CH3:18])([CH3:17])[C:4]=13)[CH3:11]
Reactant: CC(CO)C1=C2C(C)(C)C3CCC2(C3)C(C)(C)CC1
Reactant: C1CCOC1
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Solvent: CI
Product: COCC(C)C1=C2C(C)(C)C3CCC2(C3)C(C)(C)CC1
Temperature: 0 °C
Reaction time: 3 h
Yield: 69 %

Procedure:
A solution of 3b (1.0 g, 3.8×10−3 mol) in DMF (5 ml) was added to a THF (8 ml) suspension of sodium hydride (0.27 g of 50% dispersion in mineral oil, washed twice with hexane, 5.6×10−3 mol). After 3 h stirring at r. t., methyl iodide (1.6 g, 0.011 mol) was added under cooling and the reaction mixture was stirred at r. t. for additional 4 h, poured into ice-cold 2M HCl (100 ml) and extracted with MTBE (2×100 ml). The organic phase was washed with brine (2×50 ml), dried (MgSO4), concentrated in vacuo and purified by flash chromatography (MTBE/hexane 1:20) to give 5-(1-methoxyprop-2-yl)-2,2,7,7-tetramethyltricyclo[6.2.1.01,6]undec-5-ene (8b, 0.73 g, 69% yield, colourless oil).
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:17]=[C:16](I)[CH:15]=[C:14]2[C:9]=1[CH2:10][N:11]([CH2:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=1)[C:12](=[O:27])[N:13]2[C:19]1[C:24]([Cl:25])=[CH:23][CH:22]=[CH:21][C:20]=1[Cl:26].[CH:37]([N:40]1[CH2:45][CH:44]2[CH2:46][CH:41]1[CH2:42][NH:43]2)([CH3:39])[CH3:38]>>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:17]=[C:16]([N:43]2[CH2:42][CH:41]3[CH2:46][CH:44]2[CH2:45][N:40]3[CH:37]([CH3:39])[CH3:38])[CH:15]=[C:14]2[C:9]=1[CH2:10][N:11]([CH2:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=1)[C:12](=[O:27])[N:13]2[C:19]1[C:24]([Cl:25])=[CH:23][CH:22]=[CH:21][C:20]=1[Cl:26]
Reactant: COc1ccc(CN2Cc3c(-c4ccccc4Cl)cc(I)cc3N(c3c(Cl)cccc3Cl)C2=O)cc1
Reactant: CC(C)N1CC2CC1CN2
Product: COc1ccc(CN2Cc3c(-c4ccccc4Cl)cc(N4CC5CC4CN5C(C)C)cc3N(c3c(Cl)cccc3Cl)C2=O)cc1

Procedure:
The title compound was prepared from 5-(2-chlorophenyl)-1-(2,6-dichlorophenyl)-7-iodo-3-(4-methoxybenzyl)-3,4-dihydroquinazolin-2(1H)-one (EXAMPLE CCC34) and using 2-isopropyl-2,5-diazabicyclo[2.2.1]heptane (INTERMEDIATE ABA2) as described in EXAMPLE 80. Mass spectrum (ESI): 661.3 (M+1).
Reaction SMILES: [CH3:1][C:2]1(O)[CH2:7][CH2:6][C@@H:5]([C:8]([CH3:10])=[CH2:9])[CH:4]=[CH:3]1.[CH3:12][C:13]1[CH:14]=[C:15]([OH:20])[CH:16]=[C:17]([CH:19]=1)[OH:18].O.O.C(O)(=O)C(O)=O>C1(C)C=CC=CC=1.C(OCC)C>[C:8]([CH:5]1[CH:4]([C:14]2[C:13]([CH3:12])=[CH:19][C:17]([OH:18])=[CH:16][C:15]=2[OH:20])[CH:3]=[C:2]([CH3:1])[CH2:7][CH2:6]1)([CH3:10])=[CH2:9]
Reactant: Cc1cc(O)cc(O)c1
Reactant: C=C(C)[C@H]1C=CC(C)(O)CC1
Agent: O=C(O)C(=O)O
Solvent: CCOCC
Solvent: Cc1ccccc1
Solvent: O
Product: C=C(C)C1CCC(C)=CC1c1c(C)cc(O)cc1O
Reaction time: 5 h
Yield: 154.8 %

Procedure:
(4R)-1-Methyl-4-isopropenylcyclohex-2-ene-1-ol (300 mg, 2 mmoles) was dissolved in toluene (20 ml) and 5-methylresorcinol (248 mg, 2 mmoles) was added in diethyl ether (5 ml). Oxalic acid dihydrate (252 mg, 2 mmoles) was added and the reaction mixture heated with stirring at 80° for 5 hours. The reaction mixture was allowed to cool and diluted with diethyl ether (30 ml). The ether solution washed twice with aqueous sodium bicarbonate and dried over anhydrous magnesium sulphate. The solvents were evaporated under reduced pressure to give the crude product as a brown oil (800 mg). The product was purified using a silica column eluted with ethyl acetate:isohexane 1:9 going to ethyl acetate:isohexane 2:8.
Reaction SMILES: [CH2:1]([N:19]([CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[CH3:56][I:57]>C1COCC1>[I-:57].[CH3:56][N+:19]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37])[CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55]
Reactant: CI
Reactant: CCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC
Solvent: C1CCOC1
Product: CCCCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC
Product: [I-]
Reaction time: 3 h

Procedure:
N-(3β-cholestanyl)-N-methyl-N,N-dioctadecylammonium chloride of the formula (VIII): ##STR16## The gelators of Examples VI-IX are synthesized by the following procedures. N-methyl-N,N,N-trioctadecylammonium iodide is prepared according to the following process. 0.10 g (0.13 mmol) trioctadecylamine is dissolved in 1.5 ml THF (certified grade, Fisher), and 0.1 ml (1.6 mmol) CH3I (99%, Aldrich) is placed in the above solution. The solution is stirred in a nitrogen atmosphere at 38°-40° C. for 3 h. 95 mg (80%) white solid, mp 108°-111° C., is obtained after the solvent is evaporated under house vacuum pressure, and the residue is recrystallized in ethanol (anhydrous). IR (KBr) 2917, 2859 (C-H stretching, vvs), 1473 (C-H bending, w) cm-1. 1HNMR (CDCl3) δ 3.52-3.38 (CH2, m, 6H), 3.31 (CH3, s, 3H), 1.76-0.82 (heptadecyl groups, m, 105H).
Reaction SMILES: [Br:1][C:2]1[CH:3]=[C:4]([CH2:8][OH:9])[CH:5]=[N:6][CH:7]=1.[C:10]([Si:14](Cl)([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)([CH3:13])([CH3:12])[CH3:11].N1C=CN=C1>C(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]([CH2:8][O:9][Si:14]([C:10]([CH3:13])([CH3:12])[CH3:11])([C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:5]=[N:6][CH:7]=1
Reactant: OCc1cncc(Br)c1
Reactant: CC(C)(C)[Si](Cl)(c1ccccc1)c1ccccc1
Agent: c1c[nH]cn1
Solvent: ClCCl
Product: CC(C)(C)[Si](OCc1cncc(Br)c1)(c1ccccc1)c1ccccc1
Reaction time: 1 h

Procedure:
To a solution of 5-bromopyridin-3-ylmethanol (Chem. Pharm. Bull. 1990, 38, 2446) (29 g, 154 mmoL) and tert-butylchlorodiphenylsilane (47.5 g, 173 mmoL) in CH2Cl2 (500 mL) at r.t., there was added imidazole (15.8 g, 232 mmoL). The mixture was stirred for 1 hr. and filtered. The filtrate was evaporated and the residue chromatographed on silica gel eluting with a 1:7 mixture of EtOAc and hexane, to afford the product as a colorless oil.
Reaction SMILES: [NH2:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7](C(OC(C)(C)C)=O)[N:6]=[C:5]2[C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[CH:19]=1.Cl.[N:26]1[CH:31]=[CH:30][C:29]([CH2:32][C:33](O)=[O:34])=[CH:28][CH:27]=1.C(N1C=CN=C1)(N1C=CN=C1)=O.Cl>O1CCCC1.C(N(CC)CC)C>[F:24][C:20]1[CH:19]=[C:18]([C:5]2[C:4]3[C:8](=[CH:9][CH:10]=[C:2]([NH:1][C:33](=[O:34])[CH2:32][C:29]4[CH:30]=[CH:31][N:26]=[CH:27][CH:28]=4)[CH:3]=3)[NH:7][N:6]=2)[CH:23]=[CH:22][CH:21]=1
Reactant: CC(C)(C)OC(=O)n1nc(-c2cccc(F)c2)c2cc(N)ccc21
Reactant: O=C(O)Cc1ccncc1
Agent: Cl
Agent: O=C(n1ccnc1)n1ccnc1
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: O=C(Cc1ccncc1)Nc1ccc2[nH]nc(-c3cccc(F)c3)c2c1
Yield: 21.2 %

Procedure:
A solution of 50 mg of tert-butyl 5-amino-3-(3-fluorophenyl)-1H-1-indazolecarboxylate produced in Production Example I-26, 26 mg of 4-pyridylacetic acid hydrochloride and 0.05 ml of triethylamine in 5 ml tetrahydrofuran was added 37 mg of 1,1′-carbonyldiimidazole as a condensing agent at room temperature. After the completion of the reaction, the reaction mixture was treated with 5 N hydrochloric acid by the procedure of Production Example I-25-b, to give 11 mg of the title compound as a colorless powder.
Reaction SMILES: [CH3:1][O:2][C:3]([C:5]1[CH:10]=[C:9](Cl)[N:8]=[C:7]([Cl:12])[N:6]=1)=[O:4].[Cl:13][C:14]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:15]=1[OH:21]>>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[C:9]([O:21][C:15]2[CH:16]=[CH:17][C:18]([Cl:20])=[CH:19][C:14]=2[Cl:13])[N:8]=[C:7]([Cl:12])[N:6]=1)=[O:4]
Reactant: COC(=O)c1cc(Cl)nc(Cl)n1
Reactant: Oc1ccc(Cl)cc1Cl
Product: COC(=O)c1cc(Oc2ccc(Cl)cc2Cl)nc(Cl)n1
Yield: 90 %

Procedure:
The title compound was prepared in analogy to examples described in WO 01/85700 A2 (Janssen Pharmaceutica) from 2,6-dichloro-pyrimidine-4-carboxylic acid methyl ester (commercially available) and 2,4-dichloro-phenol in 90% yield. MS (ISP): 335.0 [M+H]+.
Reaction SMILES: C(OC1C=CC([NH:10][C:11]([CH2:14][C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])[CH3:12])=CC=1)C.ClC1C=C(C=CC=1)C(OO)=[O:24].[BH4-].[Na+].[CH2:32]([O:34][C:35]1[CH:42]=[CH:41][C:38]([CH:39]=O)=[CH:37][CH:36]=1)[CH3:33].C(N)(CC(C)(C)C)(C)C>C(Cl)Cl.CO>[CH2:32]([O:34][C:35]1[CH:42]=[CH:41][C:38]([CH:39]=[N+:10]([C:11]([CH2:14][C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])[CH3:12])[O-:24])=[CH:37][CH:36]=1)[CH3:33]
Reactant: CCOc1ccc(NC(C)(C)CC(C)(C)C)cc1
Reactant: CCOc1ccc(C=O)cc1
Reactant: O=C(OO)c1cccc(Cl)c1
Agent: CC(C)(C)CC(C)(C)N
Agent: [BH4-]
Agent: [Na+]
Solvent: ClCCl
Solvent: CO
Product: CCOc1ccc(C=[N+]([O-])C(C)(C)CC(C)(C)C)cc1

Procedure:
The title compound was prepared by oxidation of N-(4-ethoxyphenyl)-N-tert-octylamine with m-chloroperoxybenzoic acid in methylene chloride. The amine was synthesized via NaBH4 reduction from the corresponding imine which was acquired by condensation of 4-ethoxybenzaldehyde and tert-octylamine in methanol. The title compound was isolated in 65.0% overall yield as white crystals, m.p. 100.8° C. (Rf=0.33 on silica gel plate using hexanes:EtOAc, 7:3, v/v, as an eluant).