Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH2:1]([NH:8][CH2:9][CH:10]([CH2:21][OH:22])[CH:11]([C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([F:20])[CH:14]=1)[OH:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.[C:30]([Si:34](Cl)([CH3:36])[CH3:35])([CH3:33])([CH3:32])[CH3:31]>C1COCC1>[CH2:1]([NH:8][CH2:9][CH:10]([CH2:21][O:22][Si:34]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:36])[CH3:35])[CH:11]([C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([F:20])[CH:14]=1)[OH:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: OCC(CNCc1ccccc1)C(O)c1ccc(Cl)c(F)c1
Reactant: CC(C)(C)[Si](C)(C)Cl
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CC(C)(C)[Si](C)(C)OCC(CNCc1ccccc1)C(O)c1ccc(Cl)c(F)c1
Temperature: 25 °C
Reaction time: 8 h
Yield: 48.7 %

Procedure:
To a solution of (1RS,2SR)-2-[(benzylamino)methyl]-1-(4-chloro-3-fluorophenyl)propane-1,3-diol (44.5 g) and triethylamine (21.1 ml) in THF (416 mL) was added a solution of tert-butylchlorodimethylsilane (22.8 g) in THF (42 mL) under ice-cooling, and the mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure, and the residue was diluted with ethyl acetate. The diluted solution was washed with distilled water and brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (NH, hexane/ethyl acetate) to give the title compound (29.3 g).
Reaction SMILES: [I:1][C:2]1[CH:12]=[CH:11][C:5]([C:6]([N:8]=[C:9]=[O:10])=O)=[CH:4][CH:3]=1.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([CH2:20][NH:21][C:22](=[O:26])[CH:23]([CH3:25])[CH3:24])=[CH:16][C:15]=1[NH:27][NH:28]C(OC(C)(C)C)=O.FC(F)(F)C(O)=O>C(Cl)Cl>[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([CH2:20][NH:21][C:22](=[O:26])[CH:23]([CH3:25])[CH3:24])=[CH:16][C:15]=1[N:27]1[C:9](=[O:10])[NH:8][C:6]([C:5]2[CH:11]=[CH:12][C:2]([I:1])=[CH:3][CH:4]=2)=[N:28]1
Reactant: O=C=NC(=O)c1ccc(I)cc1
Reactant: CC(C)C(=O)NCc1ccc(Cl)c(NNC(=O)OC(C)(C)C)c1
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: CC(C)C(=O)NCc1ccc(Cl)c(-n2nc(-c3ccc(I)cc3)[nH]c2=O)c1
Yield: 34.4 %

Procedure:
The title compound was prepared according to the procedure described in Example-83 by using 4-iodobenzoyl isocyanate (Intermediate-67, 1.500 g), tert-butyl 2-(2-chloro-5-{[(2-methylpropanoyl)amino]methyl}phenyl)hydrazinecarboxylate (Intermediate-97, 1.0 g), DCM (20 mL), and trifluoro acetic acid (5.0 mL) to afford 0.500 g of the desired product. 1H NMR (400 MHz, DMSO d6): δ 1.02 (d, J=6.9 Hz, 6H), 2.44 (m, 1H), 4.28 (d, J=8.7 Hz, 2H), 7.28 (br s, 1H), 7.35 (d, J=7.8 Hz, 1H), 7.44 (s, 1H), 7.61 (d, J=8.7 Hz, 1H), 7.91 (d, J=8.1 Hz, 2H), 8.38 (m, 1H), 12.61 (m, 1H); MS (m/z): 495.7 (M−H)−.
Reaction SMILES: [CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([N:11]2[CH:15]=[CH:14][N:13]=[CH:12]2)=[CH:7][CH:6]=1)=[O:4].[CH3:16][I:17]>C1COCC1.CO>[I-:17].[CH3:1][O:2][C:3]([C:5]1[CH:6]=[CH:7][C:8]([N+:11]2[CH:15]=[CH:14][N:13]([CH3:16])[CH:12]=2)=[CH:9][CH:10]=1)=[O:4]
Reactant: COC(=O)c1ccc(-n2ccnc2)cc1
Reactant: CI
Solvent: C1CCOC1
Solvent: CO
Product: COC(=O)c1ccc(-[n+]2ccn(C)c2)cc1
Product: [I-]
Temperature: 25 °C
Reaction time: 16 h
Yield: 59 %

Procedure:
A solution of 1-(4′-methoxycarbonylphenyl)imidazole (153 g, 0.76 mol) in 1:1 THF/methanol (600 ml) is admixed with methyl iodide (196 ml, 2.27 mol) and stirred at room temperature under argon for 16 h. After concentration of the solution, the precipitated product is filtered off and washed with THF. Yield: 59%.
Reaction SMILES: [CH3:1][C:2]1([C:20]([OH:22])=[O:21])[C:11]2[C:6](=[CH:7][C:8]([CH:13]3[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]3)=[C:9]([Cl:12])[CH:10]=2)[C:5](=O)[CH2:4][CH2:3]1.O.NN.[OH-].[K+]>C(O)COCCOCCO>[CH3:1][C:2]1([C:20]([OH:22])=[O:21])[C:11]2[C:6](=[CH:7][C:8]([CH:13]3[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]3)=[C:9]([Cl:12])[CH:10]=2)[CH2:5][CH2:4][CH2:3]1
Reactant: CC1(C(=O)O)CCC(=O)c2cc(C3CCCCC3)c(Cl)cc21
Agent: NN
Agent: [K+]
Agent: [OH-]
Solvent: OCCOCCOCCO
Solvent: O
Product: CC1(C(=O)O)CCCc2cc(C3CCCCC3)c(Cl)cc21
Temperature: 195 °C
Yield: 92.1 %

Procedure:
A mixture of 6.7 g of 1-methyl-4-oxo-6-cyclohexyl-7-chloro-1,2,3,4-tetrahydronaphthalene-1-carboxylic acid, 4 g of hydrazine hydrate, 6.7 g of potassium hydroxide and 40 ml of triethyleneglycol is heated for 2 hours at 130°-140°C. Then, while distilling off a mixture of hydrazine and water, the temperature is raised to 195°C and the batch is stirred until nitrogen is no longer being given off, then diluted with 50 ml of water, acidified with concentrated hydrochloric acid and the mixture is extracted with ethyl acetate. The ethyl acetate is evaporated and the residual crude product recrystallized from acetone, to yield 5.9 g of 1-methyl-6-cyclohexyl-7-chloro-1,2,3,4-tetrahydronaphthalene-1-carboxylic acid melting at 167°-168°C, of the formula ##SPC7##
Reaction SMILES: [Br:1][C:2]1[CH:3]=[C:4]([N:12]([CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:5]([F:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].[CH2:27](O)[CH3:28]>S(=O)(=O)(O)O>[CH2:27]([O:8][C:7](=[O:9])[C:6]1[CH:10]=[C:2]([Br:1])[CH:3]=[C:4]([N:12]([CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:5]=1[F:11])[CH3:28]
Reactant: CCO
Reactant: O=C(O)c1cc(Br)cc(N(Cc2ccccc2)Cc2ccccc2)c1F
Agent: O=S(=O)(O)O
Product: CCOC(=O)c1cc(Br)cc(N(Cc2ccccc2)Cc2ccccc2)c1F
Temperature: 25 °C
Yield: 92 %

Procedure:
Dissolve 5-bromo-3-dibenzylamino-2-fluorobenzoic acid (1.53 g, 3.69 mmol) in ethanol (40 mL). Add concentrated sulfuric acid (0.2 mL) as a catalyst and heat to at reflux for 1 day. Cool to room temperature and concentrate. Dissolve the residue in diethyl ether (30 mL) and wash with 10% aqueous potassium carbonate solution (10 mL) and water (10 mL). Dry (magnesium sulfate) and concentrate to give the title compound as an oil (1.50 g, 92%).
Reaction SMILES: [Cl:1][CH:2]([F:24])[C:3]([F:23])([F:22])[O:4][C:5]1[CH:6]=[CH:7][C:8]([N:11]=NC2C=CC([N+]([O-])=O)=CC=2)=[N:9][CH:10]=1.C.[H][H]>C(O)(=O)C.[Pd]>[NH2:11][C:8]1[CH:7]=[CH:6][C:5]([O:4][C:3]([F:23])([F:22])[CH:2]([Cl:1])[F:24])=[CH:10][N:9]=1
Reactant: O=[N+]([O-])c1ccc(N=Nc2ccc(OC(F)(F)C(F)Cl)cn2)cc1
Reactant: [H][H]
Agent: [Pd]
Solvent: CC(=O)O
Product: Nc1ccc(OC(F)(F)C(F)Cl)cn1

Procedure:
In a 1 liter VA stainless steel autoclave, 85.1 g (0.24 mol) of 5-(2-chloro-1,1,2-trifluoroethoxy)-2-(4-nitrophenylazo)pyridine were hydrogenated in 600 ml of acetic acid, with addition of 10 g of palladium (10%) on activated charcoal, using 61 bar (take-up) of hydrogen at 20°-25° C. The mixture was filtered and the solvent removed by distillation on a rotary evaporator. The residue was taken up in 500 ml of dichloromethane, washed with 100 ml of 20% strength aqueous sodium carbonate and four times with 100 ml of water in each case, and dried over sodium sulfate. The solvent was subsequently removed by evaporation on a rotary evaporator and the residue was distilled in a high vacuum.
Reaction SMILES: [Na].[C:2]([C:6]1[CH:10]=[C:9]([NH:11][C:12](=[O:15])[O:13][CH3:14])[O:8][N:7]=1)([CH3:5])([CH3:4])[CH3:3].[CH3:16]O>>[CH3:16][N:11]([C:9]1[O:8][N:7]=[C:6]([C:2]([CH3:5])([CH3:3])[CH3:4])[CH:10]=1)[C:12](=[O:15])[O:13][CH3:14]
Reactant: CO
Reactant: COC(=O)Nc1cc(C(C)(C)C)no1
Agent: [Na]
Product: COC(=O)N(C)c1cc(C(C)(C)C)no1
Temperature: 25 °C
Reaction time: 1 h
Yield: 91.8 %

Procedure:
To a solution of metallic sodium (0.42 g) in methanol (12 ml), a solution of methyl 3-t-butyl-5-isoxazolylcarbamate (3.47 g) in methanol (5.5 ml) is added, and the resultant mixture is stirred at room temperature for 10 minutes. The reaction mixture is evaporated under reduced pressure to remove the methanol. The residue is combined with benzene, which is then evaporated. The residue is again combined with benzene (27 ml), and dimethyl sulfate (2.32 g) is added dropwise. The resultant mixture is stirred at room temperature for 1 hour and then refluxed for 1 hour. After cooling, the reaction mixture is filtered to remove the precipitate. The filtrate is washed with aqueous sodium bicarbonate solution and then water, dried over anhydrous sodium sulfate and evaporated to remove the solvent. The residue is recrystallized from cyclohexanone to give methyl N-methyl-3-t-butyl-5-isoxazolylcarbamate (3.41 g) as crystals melting at 70.5° to 71.5° C. The yield is 91.8%.
Reaction SMILES: [Na].[C:2]1([NH:8][NH2:9])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C/[C:11](=[CH:14]\[CH3:15])/[C:12]#[N:13].[CH2:16](O)C>>[NH2:13][C:12]1[CH2:11][CH:14]([CH2:15][CH3:16])[N:8]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[N:9]=1
Reactant: NNc1ccccc1
Reactant: CCO
Reactant: C/C=C(\C)C#N
Agent: [Na]
Product: CCC1CC(N)=NN1c1ccccc1
Reaction time: 0.08 h

Procedure:
A 0.23 g. amount of sodium metal is dissolved in 75.0 ml. of absolute ethanol, then 10.8 g. of phenylhydrazine is added, followed in 5 minutes by 3.6 g. of α-methylcrotononitrile. The reaction mixture is refluxed for 18 hours, then is evaporated to dryness in vacuo. Water is added to give a gum which solidifies on standing for 16 hours. The solid is collected and dissolved in dichloromethane. The procedure of Example 15 is continued to give 1.6 g. of the desired product as light yellow crystals, m.p. 123°-125° C.
Reaction SMILES: [OH:1][CH2:2][C@H:3]1[O:7][C:6](=[O:8])[CH2:5][CH2:4]1.N1C=CN=C1.[Si:14](Cl)([C:27]([CH3:30])([CH3:29])[CH3:28])([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>CN(C=O)C>[Si:14]([CH:2]([OH:1])[C@H:3]1[O:7][C:6](=[O:8])[CH2:5][CH2:4]1)([C:27]([CH3:30])([CH3:29])[CH3:28])([C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: O=C1CC[C@@H](CO)O1
Reactant: CC(C)(C)[Si](Cl)(c1ccccc1)c1ccccc1
Agent: c1c[nH]cn1
Solvent: CN(C)C=O
Product: CC(C)(C)[Si](c1ccccc1)(c1ccccc1)C(O)[C@@H]1CCC(=O)O1
Temperature: 25 °C
Reaction time: 1 h
Yield: 96.8 %

Procedure:
To a solution of 3 (7.0 g, 60 mmol) and imidazole (9.19 g, 135 mmol) in anhydrous DMF (70 mL) was added tert-butyldiphenylsilyl chloride (18.14 g, 66 mmol, 17.2 mL), and the solution was stirred at room temperature under a nitrogen atmosphere for 1 h. After removal of the solvent by evaporation, the residue was dissolved in CHCl3, washed with water and brine, dried (Na2SO4), filtered, and concentrated. After crystallization from hexane, the oily residue gave the title compound 4 as a white crystalline solid (20.6 g, 97%). M.P. 76° C.; 1H NMR (CDCl3) δ 7.68-7.65 (m, 4H, arom.), 7.47-7.39 (m, 6H, arom.), 4.63-4.61 (m, 1H, H-5), 3.90-3.87 (dd, J=3 & 11 Hz, 1H, CH2OH), 3.70-3.67 (dd, J=3 & 11 Hz, 1H, CH2OH), 2.69-2.65 (m, 1H, H-3), 2.56-2.52 (m, 1H, H-3), 2.32-2.23 (m, 2H, H-4), 1.06 (s, 9H, t-Bu).
Reaction SMILES: [OH:1][C:2]([C:17]1[CH:22]=[CH:21][CH:20]=[C:19](C=O)[N:18]=1)([C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=1)[CH2:3][CH2:4][N:5]1[CH2:9][CH2:8][CH2:7][CH2:6]1.[C:25](O)(=O)[CH2:26][C:27]([OH:29])=[O:28].N1CCCC[CH2:33]1>N1C=CC=CC=1>[CH3:33][O:29][C:27](=[O:28])/[CH:26]=[CH:25]/[C:19]1[CH:20]=[CH:21][CH:22]=[C:17]([C:2]([OH:1])([C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)[CH2:3][CH2:4][N:5]2[CH2:9][CH2:8][CH2:7][CH2:6]2)[N:18]=1
Reactant: C1CCNCC1
Reactant: O=C(O)CC(=O)O
Reactant: Cc1ccc(C(O)(CCN2CCCC2)c2cccc(C=O)n2)cc1
Solvent: c1ccncc1
Product: COC(=O)/C=C/c1cccc(C(O)(CCN2CCCC2)c2ccc(C)cc2)n1

Procedure:
A solution of 2-bromo-6-(1,3-dioxolan-2-yl)pyridine (91 g) in toluene (50 mL) was added under nitrogen to a stirred mixture of butyllithium (260 mL, 1.6M) and toluene (1.1 L) between -60° and -70°. After 2 h a solution of 1-pyrrolidino-3-(4-tolyl)propan-3-one (prepared from 85 g of the corresponding hydrochloride and dried) in toluene (200 mL) was added at -70° and the mixture stirred for a further 3 hours at this temperature. The solution was allowed to warm to -20° and treated with hydrochloric acid (510 ml, 2M). The separated aqueous layer was washed with ether, basified with sodium hydroxide solution (10M) at 0° and extracted with toluene. Evaporation of the dried extracts gave an oil (120 g). This was dissolved in hydrochloric acid (200 mL, 2M) and heated on the steam bath for 30 minutes. Cooling, basification and re-isolation gave 2-[1-hydroxy-3-pyrrolidino-1-(4-tolyl)-propyl]pyridine-6-aldehyde as an oil (115 g). The crude aldehyde was dissolved in pyridine (133 mL) and reacted with malonic acid (58 g) in presence of piperidine (2 mL) at reflux for one hour. After evaporation in vacuo, the residue was dissolved in a small volume of glacial acetic acid, diluted with water (2 L) and set aside at 0 to crystallise. The solid product was esterified with methanol and sulphuric acid giving methyl-(E)-3-{6-[1-hydroxy-3-pyrrolidino-1-(4-tolyl)propyl]-2-pyridyl}acrylate as a dark oil (27 g). A small sample crystallized from petroleum ether in colourless prisms, m.p. 75°-77°. A mixture of the crude ester (25 g) and concentrated sulfuric acid (50 mL) was heated in an oil bath at 160° for 20 minutes. Re-isolation and saponification by the method described in example 5 gave (E)-3-{6-3-[pyrrolidino-1-(4-tolyl)prop-1E-enyl]-2-pyridyl}acrylic acid as off-white crystals, m.p. 218°-219° (decomp.). A further recrystallization from isopropanol raised the melting point to 222° -223°.
Reaction SMILES: [CH2:1]([Mg]Br)[CH3:2].[C:5]([C:7]1[CH:12]=[CH:11][N:10]=[CH:9][CH:8]=1)#N.[OH:13]S(O)(=O)=O.O>C(OCC)C>[C:5]([C:7]1[CH:12]=[CH:11][N:10]=[CH:9][CH:8]=1)(=[O:13])[CH2:1][CH3:2]
Reactant: N#Cc1ccncc1
Reactant: O=S(=O)(O)O
Reactant: CC[Mg]Br
Solvent: CCOCC
Solvent: O
Product: CCC(=O)c1ccncc1
Yield: 95 %

Procedure:
To a solution of 2.845M ethylmagnesium bromide (263 mL, 0.75 mol) in ethyl ether (Et2O) (250 mL) was slowly added a solution of 4-cyanopyridine (39 g, 0.375 mol) in Et2O (750 mL). The reaction mixture was warmed at reflux for 12 hours, treated with concentrated H2SO4 (125 mL)/H2O (125 mL), and then washed three times with Et2O (250 mL). The aqueous portion was made basic (pH 9) with 15% NaOH solution and extracted five times with 250 mL portions of Et2O. The combined Et2O extracts were dried (MgSO4), and the solvent was removed under reduced pressure to afford a brown oil (48.4 g, 95%). Purification by vacuum distillation at 93°-97° (2.6 mm) afforded product as a pale yellow oil (25.35 g, 50%), NMR (CDCl3) δ 1.23 (t, 3H, J= 7 Hz), 3.00 (q, 2H, J=7 Hz), 7.70 (d, 2H, J=6 Hz), and 8.78 (d, 2H, J=6 Hz); IR (film) 1695 cm-1.
Reaction SMILES: C([C@@H]1COC(=O)N1C(=O)[C@H]([CH2:19][S:20]([N:23]1[CH2:28][CH2:27][N:26]([C:29]2[N:34]=[CH:33][C:32]([C:35]3[CH:40]=[CH:39][C:38]([F:41])=[CH:37][CH:36]=3)=[CH:31][N:30]=2)[CH2:25][CH2:24]1)(=[O:22])=[O:21])C(C)C)C1C=CC=CC=1.Cl.Cl.FC1C=CC(C2C=NC(N3CCNCC3)=NC=2)=CC=1.[CH3:64][O:65][C:66]([C:68]1(CS(Cl)(=O)=O)[CH2:73][CH2:72][CH2:71][CH2:70][CH2:69]1)=[O:67]>>[CH3:64][O:65][C:66]([C:68]1([CH2:19][S:20]([N:23]2[CH2:24][CH2:25][N:26]([C:29]3[N:34]=[CH:33][C:32]([C:35]4[CH:36]=[CH:37][C:38]([F:41])=[CH:39][CH:40]=4)=[CH:31][N:30]=3)[CH2:27][CH2:28]2)(=[O:22])=[O:21])[CH2:73][CH2:72][CH2:71][CH2:70][CH2:69]1)=[O:67]
Reactant: COC(=O)C1(CS(=O)(=O)Cl)CCCCC1
Reactant: CC(C)[C@@H](CS(=O)(=O)N1CCN(c2ncc(-c3ccc(F)cc3)cn2)CC1)C(=O)N1C(=O)OC[C@H]1Cc1ccccc1
Agent: Cl
Agent: Fc1ccc(-c2cnc(N3CCNCC3)nc2)cc1
Product: COC(=O)C1(CS(=O)(=O)N2CCN(c3ncc(-c4ccc(F)cc4)cn3)CC2)CCCCC1
Yield: 48 %

Procedure:
Prepared according to the method for the preparation of 4-(R)-benzyl-3-(2-(R)-{4-[5-(4-fluorophenyl)pyrimidin-2-yl]piperazine-1-sulfonylmethyl}-3-methyl-butyryl)oxazolidin-2-one, from 5-(4-fluorophenyl)-2-piperazine-1-ylpyrimidine, dihydrochloride (0.599 g) and 1-chlorosulfonylmethylcyclohexanecarboxylic acid methyl ester (0.575 g), to yield the title compound as a white solid (0.417 g, 48%).
Reaction SMILES: [Cl-].[Al+3].[Cl-].[Cl-].[CH3:5][C:6]1[NH:7][C:8](=[O:11])[NH:9][CH:10]=1.[C:12]1([CH2:18][C:19](Cl)=[O:20])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.Cl>ClCCl>[CH3:5][C:6]1[NH:7][C:8](=[O:11])[NH:9][C:10]=1[C:19](=[O:20])[CH2:18][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
Reactant: O=C(Cl)Cc1ccccc1
Reactant: Cc1c[nH]c(=O)[nH]1
Agent: Cl
Agent: [Al+3]
Agent: [Cl-]
Solvent: ClCCl
Product: Cc1[nH]c(=O)[nH]c1C(=O)Cc1ccccc1

Procedure:
To 26.6 g (0.2 mole) of aluminum chloride in 250 ml of dichloromethane is added 9.8 g (0.1 mole) of 1,3-dihydro-4-methyl-2H-imidazol-2-one and, dropwise, 16.9 g (0.11 mole) of phenylacetyl chloride. The mixture is stirred and heated to reflux for 5 hours. The mixture is cooled and 200 ml of 2N-hydrochloric acid is added dropwise. The resulting precipitate is collected, washed with water, and recrystallized for 50% aqueous ethanol to give the title compound, m.p. 239°-240° C.
Reaction SMILES: [C:1]1([C:7]2[NH:8][C:9]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[C:10]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[N:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.BrC[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:32]([O:34][CH2:35][CH3:36])=O.[C:37](=O)([O-])[O-:38].[K+].[K+]>CC(=O)CC>[CH2:35]([O:34][C:32](=[C:37]=[O:38])[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][N:11]1[C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:9]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[N:8]=[C:7]1[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH3:36]
Reactant: c1ccc(-c2nc(-c3ccccc3)c(-c3ccccc3)[nH]2)cc1
Reactant: CCOC(=O)CCCCCCCBr
Reactant: O=C([O-])[O-]
Agent: [K+]
Solvent: CCC(C)=O
Product: CCOC(=C=O)CCCCCCn1c(-c2ccccc2)nc(-c2ccccc2)c1-c1ccccc1
Yield: 48.5 %

Procedure:
A mixture of 2,4,5-triphenylimidazole (11 g), ethyl 8-bromooctanoate (18.64 g), anhydrous potassium carbonate (51.3 g) and dry butanone (350 ml ) was heated at reflux for 26 h. The cooled reaction mixture was filtered to remove inorganics and the flitrate was evaporated to dryness in vacuo. The residue was stirred in hexane and unreacted 2,4,5-triphenylimidazole was collected by filtration (3.1 g). The flitrate was cooled and a white precipitate was collected. Recrystallisation from hexane gave 1-(7-ethoxy-carbonyl-heptyl)-2,4,5-triphenylimidazole (8.37 g, 48.4%) as a white solid, m.p. 65°-7°.
Reaction SMILES: [NH2:1][C:2]1[CH:3]=[C:4]([C:8]2[C:17]3[C:12](=[C:13]([C:18]([F:21])([F:20])[F:19])[CH:14]=[CH:15][CH:16]=3)[N:11]=[CH:10][C:9]=2[C:22]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[O:23])[CH:5]=[CH:6][CH:7]=1.[C:30]1([N:36]=[C:37]=[O:38])[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>C(N(CC)CC)C>[C:22]([C:9]1[CH:10]=[N:11][C:12]2[C:17]([C:8]=1[C:4]1[CH:3]=[C:2]([NH:1][C:37]([NH:36][C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)=[O:38])[CH:7]=[CH:6][CH:5]=1)=[CH:16][CH:15]=[CH:14][C:13]=2[C:18]([F:21])([F:19])[F:20])(=[O:23])[C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1
Reactant: Nc1cccc(-c2c(C(=O)c3ccccc3)cnc3c(C(F)(F)F)cccc23)c1
Reactant: O=C=Nc1ccccc1
Solvent: CCN(CC)CC
Product: O=C(Nc1ccccc1)Nc1cccc(-c2c(C(=O)c3ccccc3)cnc3c(C(F)(F)F)cccc23)c1

Procedure:
The title compound was prepared from [4-(3-aminophenyl)-8-(trifluoromethyl)quinolin-3-yl](phenyl)methanone and phenyl isocyanate in substantially the same manner as described in Example 61 with one change: no triethylamine was used; off-white solid: MS (EI) m/z 512.2 (M+H)+; 1H NMR (DMSO-d6): δ 6.90 (d, J=7.7 Hz, 1H), 6.96 (t, J=7.3 Hz, 1H), 7.20-7.30 (m, 3H), 7.35-7.47 (m, 6H), 7.57 (t, J=7.5 Hz, 1H), 7.66 (d, J=8.5 Hz, 2H), 7.83 (d, J=7.7 Hz, 1H), 8.35 (d, J=6.9 Hz, 1H), 8.66 (s, 1H), 8.74 (s, 1H), 9.14 (s, 1H).
Reaction SMILES: [Cl-].[Cl:2][C:3]1[C:28]([Cl:29])=[C:27]([O:30][CH3:31])[CH:26]=[C:25]([Cl:32])[C:4]=1[CH2:5][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH2:33]([O:35][C:36](=[O:47])[CH:37]=[C:38]([CH3:46])[CH:39]=[CH:40][CH:41]=[C:42]([CH:44]=O)[CH3:43])[CH3:34]>>[CH2:33]([O:35][C:36](=[O:47])[CH:37]=[C:38]([CH3:46])[CH:39]=[CH:40][CH:41]=[C:42]([CH3:44])[CH:43]=[CH:5][C:4]1[C:25]([Cl:32])=[CH:26][C:27]([O:30][CH3:31])=[C:28]([Cl:29])[C:3]=1[Cl:2])[CH3:34]
Reactant: CCOC(=O)C=C(C)C=CC=C(C)C=O
Reactant: COc1cc(Cl)c(C[P+](c2ccccc2)(c2ccccc2)c2ccccc2)c(Cl)c1Cl
Agent: [Cl-]
Product: CCOC(=O)C=C(C)C=CC=C(C)C=Cc1c(Cl)cc(OC)c(Cl)c1Cl

Procedure:
By the procedure of Example 1, 2,3,6-trichloro-4-methoxy-benzyltriphenyl-phosphonium chloride is reacted with 7-formyl-3-methyl-octa-2,4,6-trien-1-oic acid ethyl ester to obtain 9-(2,3,6-trichloro-4-methoxy-phenyl)-3,7-dimethyl-nona-2,4,6,8-tetraen-1-oic acid ethyl ester of melting point 126°-128° C.
Reaction SMILES: [C:1]1([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][NH:15][C:16]([C:18]2[CH:19]=[C:20]([C:26]3[CH:31]=[CH:30][CH:29]=[C:28]([C:32]([F:35])([F:34])[F:33])[CH:27]=3)[C:21]([OH:25])=[C:22]([Br:24])[CH:23]=2)=[O:17])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl[S:37]([C:40]1[CH:48]=[CH:47][C:43]([C:44]([OH:46])=[O:45])=[C:42]([OH:49])[CH:41]=1)(=[O:39])=[O:38].[K+].[Br-]>>[Br:24][C:22]1[C:21]([O:25][S:37]([C:40]2[CH:48]=[CH:47][C:43]([C:44]([OH:46])=[O:45])=[C:42]([OH:49])[CH:41]=2)(=[O:39])=[O:38])=[C:20]([C:26]2[CH:31]=[CH:30][CH:29]=[C:28]([C:32]([F:35])([F:33])[F:34])[CH:27]=2)[CH:19]=[C:18]([C:16](=[O:17])[NH:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:23]=1
Reactant: O=C(O)c1ccc(S(=O)(=O)Cl)cc1O
Reactant: O=C(NCCCCCCCCc1ccccc1)c1cc(Br)c(O)c(-c2cccc(C(F)(F)F)c2)c1
Agent: [Br-]
Agent: [K+]
Product: O=C(NCCCCCCCCc1ccccc1)c1cc(Br)c(OS(=O)(=O)c2ccc(C(=O)O)c(O)c2)c(-c2cccc(C(F)(F)F)c2)c1

Procedure:
The title compound was prepared as an orange foam (0.455 g, 76%) from 5-bromo-6-hydroxy-3′-trifluoromethyl-biphenyl-3-carboxylic acid (8-phenyl-octyl)-amide and 4-chlorosulfonyl-2-hydroxy-benzoic acid using a procedure similar to step 3 of Example 179. 1H NMR (DMSO-d6) 12.60 (bs, 1H); 11.60 (bs, 1H); 8.68 (t, 1H); 8.21 (d, 1H); 7.84 (d, 1H); 7.71–7.62 (m, 2H); 7.56–7.44 (m, 3H); 7.26–7.10 (m, 5H); 6.96 (dd, 1H); 6.82 (d, 1H); 3.21 (dd, 2H); 2.62 (t, 4H); 2.53 (t, 2H); 1.52 (m, 4H); 1.25 (m, 8H); IR (KBr) 3370, 2950, 2825, 1690, 1640, 1605, 1560, 1540, 1390, 1325, 1195, 1170, 1125 cm−1; mass spectrum [(−)ESI], m/z 660/662 (M−H)−; Anal. Calcd. for C35H33BrF3NO7S: C, 56.16; H, 4.44; N, 1.87. Found: C, 55.65; H, 4.27; N, 1.90.
Reaction SMILES: [C:1]([O:6][CH:7]([O:9][CH2:10][CH2:11][CH2:12][CH3:13])[CH3:8])(=[O:5])[C:2]([CH3:4])=[CH2:3].[C:14]([O:19][CH2:20][CH:21]1[O:23][CH2:22]1)(=[O:18])[C:15]([CH3:17])=[CH2:16].[CH2:24](C(C)=O)C(C)C.N(C(C)(CC)C([O-])=O)=NC(C)(CC)C([O-])=O>CCCCCCC>[C:1]([O:6][CH:7]([O:9][CH2:10][CH2:11][CH2:12][CH3:13])[CH3:8])(=[O:5])[C:2]([CH3:4])=[CH2:3].[C:14]([O:19][CH2:20][CH:21]1[O:23][CH2:22]1)(=[O:18])[C:15]([CH3:17])=[CH2:16].[C:14]([O:19][CH:20]([CH3:24])[CH2:21][O:23][CH3:22])(=[O:18])[CH3:15]
Reactant: CC(=O)CC(C)C
Agent: C=C(C)C(=O)OC(C)OCCCC
Agent: C=C(C)C(=O)OCC1CO1
Agent: CCC(C)(N=NC(C)(CC)C(=O)[O-])C(=O)[O-]
Solvent: CCCCCCC
Product: COCC(C)OC(C)=O
Reaction time: 6 h

Procedure:
Into a 500 ml-volume three-neck flask, 67.1 g (0.36 mol) of 1-n-butoxyethyl methacrylate, 34.1 g (0.24 mol) of glycidyl methacrylate and 300 ml of methyl isobutyl ketone were charged. A catalytic amount of 2,2′-azobis(methyl 2-methyipropionate) was added thereto as a radical polymerization initiator, and polymerization was allowed to proceed at 80° C. for 6 hours in a nitrogen stream. The reaction solution was cooled and then poured in a large amount of heptane to precipitate a polymer. The crystal was collected by filtration and dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were removed by distillation under reduced pressure to obtain Polymer A-1 (1-n-butoxyethyl methacrylate/glycidyl methacrylate) as a propylene glycol monomethyl ether acetate solution.