Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [Cl:1][C:2]1[C:3]([OH:14])=[C:4]2[C:9](=[C:10]([Cl:12])[CH:11]=1)[NH:8][C:7](=[O:13])[CH2:6][CH2:5]2.[OH-].[K+].CO.Cl[CH2:20][CH:21]([CH3:35])[CH2:22][N:23]1[CH2:28][CH2:27][CH:26]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[CH2:25][CH2:24]1>CN(C)C=O>[Cl:1][C:2]1[C:3]([O:14][CH2:20][CH:21]([CH3:35])[CH2:22][N:23]2[CH2:24][CH2:25][CH:26]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[CH2:27][CH2:28]2)=[C:4]2[C:9](=[C:10]([Cl:12])[CH:11]=1)[NH:8][C:7](=[O:13])[CH2:6][CH2:5]2
Reactant: O=C1CCc2c(O)c(Cl)cc(Cl)c2N1
Reactant: CC(CCl)CN1CCC(c2ccccc2)CC1
Agent: [K+]
Agent: [OH-]
Solvent: CO
Solvent: CN(C)C=O
Product: CC(COc1c(Cl)cc(Cl)c2c1CCC(=O)N2)CN1CCC(c2ccccc2)CC1
Yield: 35 %

Procedure:
2.4 Grams of 6,8-dichloro-5-hydroxy-3,4-dihydrocarbostyril and 0.8 g of granular potassium hydroxide were mixed with 60 ml of methanol and concentrated under a reduced pressure to dryness. To the residue thus obtained was added 60 ml of dimethylformamide and mixed well, then 5 g of 1-chloro-2-methyl-3-(4-phenylpiperidyl)propane and heated at 70°-80° C. for 8 hours under stirring condition. The reaction mixture was concentrated under a reduced pressure to dryness, then 60 ml of 5% sodium hydrogencarbonate aqueous solution was added thereto and extracted with chloroform. The chloroform layer was washed with water and dried, then the chloroform was removed by distillation and thus obtained residue was purified by silica-gel column chromatography and recrystallized from ligroin to obtain 1.6 g (yield: 35%) of 6,8-dichloro-5-[2-methyl-3-(4-phenyl-1-piperidyl)propoxy]-3,4-dihydrocarbostyril as in the form of colorless needle-like crystals. Melting point 125°-126° C.
Reaction SMILES: C1(C(C2C=CC=CC=2)(C2C=CC=CC=2)[NH:8][CH2:9][CH2:10][S:11][C:12]([O:14]C2C=CC([N+]([O-])=O)=CC=2)=O)C=CC=CC=1.[CH2:36]([NH2:40])[CH:37]([CH3:39])[CH3:38]>>[CH2:36]([NH:40][C:12]([S:11][CH2:10][CH2:9][NH2:8])=[O:14])[CH:37]([CH3:39])[CH3:38]
Reactant: CC(C)CN
Reactant: O=C(Oc1ccc([N+](=O)[O-])cc1)SCCNC(c1ccccc1)(c1ccccc1)c1ccccc1
Product: CC(C)CNC(=O)SCCN

Procedure:
N-triphenylmethyl-2-paranitrophenoxycarbonylthioethylamine (300 mg) and isobutylamine (185 μl) were subjected to similar reactions to those described in References 2 and 4 to give 2-isobutylaminocarbonylthioethylamine (crude formate: 256 mg) which was then dissolved in anhydrous methanol (5 ml). Triethylamine (376 μl) and mitomycin A (151 mg: 0.8 molar equivalent) were added to the solution. The reaction solution was treated in a similar manner to that described in Example 1 to obtain Compound 24 (71 mg) in the form of grayish blue powders with a yield of 33%.
Reaction SMILES: Br[C:2]1[CH:3]=[N:4][C:5]([NH:8][CH:9]([CH2:16][CH:17]([CH3:19])[CH3:18])[C:10]([NH:12][CH2:13][C:14]#[N:15])=[O:11])=[N:6][CH:7]=1.[C:20]([O:24][C:25]([N:27]1[CH2:32][CH2:31][N:30]([C:33]2[CH:38]=[CH:37][C:36](B(O)O)=[CH:35][CH:34]=2)[CH2:29][CH2:28]1)=[O:26])([CH3:23])([CH3:22])[CH3:21].C(=O)([O-])[O-].[Na+].[Na+].O>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[C:14]([CH2:13][NH:12][C:10]([CH:9]([NH:8][C:5]1[N:4]=[CH:3][C:2]([C:36]2[CH:35]=[CH:34][C:33]([N:30]3[CH2:29][CH2:28][N:27]([C:25]([O:24][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:26])[CH2:32][CH2:31]3)=[CH:38][CH:37]=2)=[CH:7][N:6]=1)[CH2:16][CH:17]([CH3:19])[CH3:18])=[O:11])#[N:15]
Reactant: CC(C)(C)OC(=O)N1CCN(c2ccc(B(O)O)cc2)CC1
Reactant: CC(C)CC(Nc1ncc(Br)cn1)C(=O)NCC#N
Agent: Cl[Pd]Cl
Agent: [Fe+2]
Agent: O=C([O-])[O-]
Solvent: O
Solvent: CN(C)C=O
Product: CC(C)CC(Nc1ncc(-c2ccc(N3CCN(C(=O)OC(C)(C)C)CC3)cc2)cn1)C(=O)NCC#N
Temperature: 90 °C

Procedure:
To 2-[(5-bromo-2-pyrimidinyl)amino]-N-(cyanomethyl)-4-methylpentanamide (123 mg, 0.377 mmol) and 4-[4-(tert-butoxycarbonyl)-1-piperazinyl]phenylboronic acid (140 mg, 0.453 mmol) in DMF (10 mL) under dry nitrogen was added aqueous sodium carbonate (2 M, 0.6 mL, 1.2 mmol) followed by the catalyst PdCl2(dppf) (15 mg, 0.0113 mmol). The reaction was heated to 90° C. for 0.5 hours and more PdCl2(dppf) (15 mg, 0.0113 mmol) was added and the reaction mixture was heated for another 5.5 hours. Water was added and the product extracted with ether (2×), dried over Na2SO4, concentrated in vacuo, and purified by flash chromatography over silica gel (EtOAc/Hex, 7/3) to afford tert-butyl 4-(4-{2-[(1-{[(cyanomethyl)amino]carbonyl}-3-methylbutyl)amino]-5-pyrimidinyl}phenyl)-1-piperazinecarboxylate.
Reaction SMILES: [F:1][C:2]1[C:3]([O:13][Si](C)(C)C)=[N:4][C:5]([O:8][Si](C)(C)C)=[N:6][CH:7]=1.Br[CH2:19][CH2:20][CH2:21][Cl:22].II.[OH-].[Na+]>ClCCCl.O>[Cl:22][CH2:21][CH2:20][CH2:19][N:6]1[CH:7]=[C:2]([F:1])[C:3](=[O:13])[NH:4][C:5]1=[O:8]
Reactant: ClCCCBr
Reactant: C[Si](C)(C)Oc1ncc(F)c(O[Si](C)(C)C)n1
Agent: II
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: ClCCCl
Product: O=c1[nH]c(=O)n(CCCCl)cc1F

Procedure:
A mixture of 5-fluoro-2,4-bis[(trimethylsilyl)oxy]pyrimidine (1 g, commercially available from Lancaster), 1-bromo-3-chloropropane (0.44 mL) and I2 (10 mg) in 1,2-dichloroethane (10 mL) was heated to reflux for 30 h. Then the reaction mixture was treated with water and the pH was brought to 7 using aqueous 6N NaOH solution, the mixture was extracted twice with DCM, the organic phase dried over Na2SO4 and the solvent evaporated under reduced pressure. The crude product was purified by flash chromatography on silica gel eluting with DCM/MeOH 95/5 to give 35 mg of the title compound.
Reaction SMILES: [C:1]([O:9][C@@H:10]1[C@@H:17]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C@H:16]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:15]([CH2:34][O:35]CC2C=CC(Cl)=CC=2)[O:14][C@H:11]1[O:12][CH3:13])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1CCOCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].Cl[Sn](Cl)(Cl)Cl>CC([O-])=O.CC([O-])=O.[Pd+2]>[C:1]([O:9][C@@H:10]1[C@@H:17]([O:18][CH2:19][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[C@H:16]([O:26][CH2:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[C@@H:15]([CH2:34][OH:35])[O:14][C@H:11]1[O:12][CH3:13])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: CO[C@@H]1O[C@H](COCc2ccc(Cl)cc2)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@H]1OC(=O)c1ccccc1
Agent: [Pd+2]
Agent: CC(=O)[O-]
Agent: Cl[Sn](Cl)(Cl)Cl
Solvent: C1COCCN1
Product: CO[C@@H]1O[C@H](CO)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@H]1OC(=O)c1ccccc1
Yield: 78.6 %

Procedure:
The general procedure C using 21 (70.3 mg, 0.117 mmol), morpholine (12.2 μL, 0.140 mmol), Pd(OAc)2 (1.0 mg, 0.0046 mmol), 1-(N,N-dimethylamino)-1′-(dicyclohexylphosphino) biphenyl (1.8 mg, 0.0046 mmol) and K3PO4 (34.8 mg, 0.164 mmol) for 12 h at 100° C. afforded a yellow oil. Cleavage of the aminated intermediate with SnCl4 (140 μL 1.0 M in CH2Cl2, 0.140 mmol) using general procedure D gave 44.0 mg (79%) of 27 as a colorless oil after purification by flash column chromatography on silica gel (50% EtOAc/Hexanes). [α]24D: −28.1° (c 3.24, CH2Cl2); IR (thin film) 3454, 2878, 1726, 1269, 1086 cm−1; 1H-NMR (CDCl3) δ 8.04 (d, J=8.2 Hz, 2H), 7.59 (t, J=8.5 Hz, 1H), 7.38-7.32 (m, 4H), 7.15 (s, 4H), 5.26 (dd, J=8.2, 9.4 Hz, 1H), 4.88 (d, J=11.0 Hz, 1H), 4.78 (d, J=11.0 Hz, 1H), 4.70 (d, J=11.0 Hz, 1H), 4.69 (d, J=11.3 Hz, 1H), 4.51 (d, J=7.9 Hz, 1H), 3.96-3.94 (m, 1H), 3.88 (dd, J=9.2, 9.5 Hz, 1H), 3.80-3.75 (m, 2H), 3.51-3.48 (m, 4H), 2.09-2.07 (m, 1H); 13C-NMR (CDCl3) δ 165.4, 138.0, 137.9, 133.3, 130.0, 128.7, 128.6, 128.5, 128.3, 128.2, 127.9, 102.2, 82.7, 77.8, 75.5, 75.3, 73.9, 62.0, 57.2; FAB MS m/z (M+Na)+: calcd 501.1890, obsd 501.1888.
Reaction SMILES: [OH:1][CH2:2][CH2:3][N:4]([CH2:35][CH2:36][OH:37])[C:5]1[CH:10]=[CH:9][C:8]([NH:11][C:12]2[C:17](=[O:18])[C:16]([CH3:19])=[C:15]([OH:20])/[C:14](=[N:21]\[C:22]3[CH:27]=[CH:26][C:25]([N:28]([CH2:32][CH2:33][OH:34])[CH2:29][CH2:30][OH:31])=[CH:24][CH:23]=3)/[CH:13]=2)=[CH:7][CH:6]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+]>CO.[OH-].[Na+]>[OH:1][CH2:2][CH2:3][N:4]([CH2:35][CH2:36][OH:37])[C:5]1[CH:10]=[CH:9][C:8]([NH:11][C:12]2[CH:13]=[C:14]([NH:21][C:22]3[CH:27]=[CH:26][C:25]([N:28]([CH2:29][CH2:30][OH:31])[CH2:32][CH2:33][OH:34])=[CH:24][CH:23]=3)[C:15]([OH:20])=[C:16]([CH3:19])[C:17]=2[OH:18])=[CH:7][CH:6]=1
Reactant: CC1=C(O)/C(=N\c2ccc(N(CCO)CCO)cc2)C=C(Nc2ccc(N(CCO)CCO)cc2)C1=O
Agent: O=S([O-])S(=O)[O-]
Agent: [Na+]
Agent: [OH-]
Solvent: CO
Product: Cc1c(O)c(Nc2ccc(N(CCO)CCO)cc2)cc(Nc2ccc(N(CCO)CCO)cc2)c1O

Procedure:
13 mg (0.04 mol) of (4Z)-6-({4-[bis(2-hydroxyethyl)-amino]phenyl}amino)-4-({4-[bis(2-hydroxyethyl)amino]-phenyl}imino)-3-hydroxy-2-methylcyclohexa-2,5-dien-1-one are added to a solution containing 16 mg of sodium hydrosulfite in 500 μl of methanol and 5 μl of aqueous sodium hydroxide solution. The reaction medium is stirred and the solution is then worked up according to the usual procedure and characterized. 4,6-Bis({4-[bis(2-hydroxyethyl)amino]phenyl}amino)-2-methyl-benzene-1,3-diol is obtained.
Reaction SMILES: [NH2:1][CH:2]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH:3]([NH:10][C:11]([NH:13][C:14]1[CH:19]=[CH:18][C:17]([C:20]([F:23])([F:22])[F:21])=[CH:16][CH:15]=1)=[O:12])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[C:30]1([CH2:36][C:37](Cl)=[O:38])[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.C(N(CC)CC)C>ClCCl>[C:24]1([CH:2]([NH:1][C:37](=[O:38])[CH2:36][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[CH:3]([C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)[NH:10][C:11]([NH:13][C:14]2[CH:19]=[CH:18][C:17]([C:20]([F:21])([F:22])[F:23])=[CH:16][CH:15]=2)=[O:12])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1
Reactant: O=C(Cl)Cc1ccccc1
Reactant: NC(c1ccccc1)C(NC(=O)Nc1ccc(C(F)(F)F)cc1)c1ccccc1
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: O=C(Cc1ccccc1)NC(c1ccccc1)C(NC(=O)Nc1ccc(C(F)(F)F)cc1)c1ccccc1
Temperature: 25 °C
Reaction time: 2 h
Yield: 54.1 %

Procedure:
To a solution of [R-(R*,R*)] and [S-(R*,R*)]-N-(2-amino-1,2-diphenylethyl)-N'-[4-(trifluoromethyl)phenyl]urea (0.1 g, 0.25 mmol) in dichloromethane (5 mL) is added phenylacetyl chloride (0.05 g, 0.3 mmol) followed by triethylamine (0.03 g, 0.3 mmol) in one portion. The resulting mixture is stirred 2 hours at room temperature before concentrating in vacuo. The residue is dissolved in diethyl ether and the organic layer washed with aqueous 1N NaOH, aqueous saturated NaCl, and dried over MgSO4. Filtration and concentration gives an oil which is purified by flash chromatography (SiO2, EtOAc/hexane eluent). The resulting solid is recrystallized from ethyl acetate/hexane to give 0.07 g (52%) of desired white solid, mp 233.5°-234° C. NMR (DMSO-d6): 3.46 (dd, 2H, J=26.4, 14 Hz), 5.10 (m, 2H), 6.97-7.19 (m, 20H), 7.57 (s, 4H), 8.82 (d, 1H, J=8.3 Hz), 8.98 (s, 1H). Analysis calculated for C30H26F3N3O2.0.71H2O: C, 67.94; H, 5.21; N, 7.92. Found: C, 67.94; H, 4.84; N, 7.86.
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:10]=1[N:9]([CH:11]([CH3:13])[CH3:12])[N:8]=[C:7]2[C:14]1[CH:19]=[CH:18][C:17]([O:20]C)=[CH:16][C:15]=1[CH3:22].B(Br)(Br)Br.C1CCCCC=1>>[Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:10]=1[N:9]([CH:11]([CH3:13])[CH3:12])[N:8]=[C:7]2[C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][C:15]=1[CH3:22]
Reactant: COc1ccc(-c2nn(C(C)C)c3c(Cl)cccc23)c(C)c1
Agent: BrB(Br)Br
Solvent: C1=CCCCC1
Product: Cc1cc(O)ccc1-c1nn(C(C)C)c2c(Cl)cccc12
Yield: 53.2 %

Procedure:
Prepared according to Method D step C from 7-chloro-1-isopropyl-3-(4-methoxy-2-methylphenyl)-1H-indazole (0.090 g, 0.3 mmol), boron tribromide (0.104 mL, 1.1 mmol) and 1.0 mL of cyclohexene to give the product (0.048 g) as a white solid.
Reaction SMILES: [CH:1]([NH:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10](=[O:43])[CH2:11][N:12]1[C:21](=[O:22])[C:20]2[N:19]([CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[C:18]([N:28]3[CH2:33][CH2:32][CH2:31][CH:30]([NH:34]C(OC(C)(C)C)=O)[CH2:29]3)=[N:17][C:16]=2[N:15]([CH3:42])[C:13]1=[O:14])=[O:2].FC(F)(F)C(O)=O.[OH-].[Na+]>C(Cl)Cl>[CH:1]([NH:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10](=[O:43])[CH2:11][N:12]1[C:21](=[O:22])[C:20]2[N:19]([CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[C:18]([N:28]3[CH2:33][CH2:32][CH2:31][CH:30]([NH2:34])[CH2:29]3)=[N:17][C:16]=2[N:15]([CH3:42])[C:13]1=[O:14])=[O:2]
Reactant: CC(C)=CCn1c(N2CCCC(NC(=O)OC(C)(C)C)C2)nc2c1c(=O)n(CC(=O)c1ccccc1NC=O)c(=O)n2C
Agent: [Na+]
Agent: [OH-]
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: CC(C)=CCn1c(N2CCCC(N)C2)nc2c1c(=O)n(CC(=O)c1ccccc1NC=O)c(=O)n2C
Temperature: 25 °C

Procedure:
A solution of 180 mg of 1-[2-(2-formylaminophenyl)-2-oxoethyl]-3-methyl-7-(3-methyl-2-buten-1-yl)-8-[3-(tert-butyloxycarbonylamino)piperidin-1-yl]xanthine in 4 mL of methylene chloride is combined with 1 mL of trifluoroacetic acid and stirred for half an hour at ambient temperature. For working up, the reaction mixture is made slightly alkaline with 1 N sodium hydroxide solution and the aqueous phase is extracted with methylene chloride. The combined organic phases are evaporated down and purified through a silica gel column. Yield: 130 mg (87% of theory); Rf value: 0.38 (Ready-made reversed phase TLC plate (E. Merck), acetonitrile/water/trifluoroacetic acid (100:100:0.1)); mass spectrum (ESI+): m/z=494 [M+H]+.
Reaction SMILES: [C:1](=[Fe:3])=[O:2].[Fe]>>[C-:1]#[O+:2].[C-:1]#[O+:2].[C-:1]#[O+:2].[C-:1]#[O+:2].[C-:1]#[O+:2].[Fe:3]
Reactant: O=C=[Fe]
Agent: [Fe]
Product: [C-]#[O+]

Procedure:
This example illustrates the preparation, by manual mixing of the ingredients followed by spray-drying, of a ferromagnetic toner containing a blue disperse dye, magnetic components and an aqueous alkali-soluble resin, and the application thereof to both paper and polyester. A magnetic toner was prepared from 32.7% of carbonyl iron, 32.7% of Fe3O4, 1.8% of C.I. Disperse Blue 56, 5.5% of ligninsulfonate dispersant and 27.3% of a polyvinyl acetate copolymer resin. The carbonyl iron, used as the soft magnetic material and commercially available under the trade name "Carbonyl Iron" GS-6, is substantially pure iron powder produced by the pyrolysis of iron carbonyl. A suitable Fe3O4 is sold under the trade name "Mapico" Black Iron Oxide and the polyvinyl acetate copolymer resin, under the trade name "Gelva" C5-VIOM. "Gelva" C5-VIOM is an aqueous alkali-soluble copolymer of vinyl acetate and a monomer containing the requisite number of carboxy groups and has a softening point of 123° C.
Reaction SMILES: [C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11]([C:14]2[CH:15]=[CH:16][C:17]3[C:29](=[O:30])[C:28]4[C:27]5[C:22](=[CH:23][C:24]([C:31]#[N:32])=[CH:25][CH:26]=5)[NH:21][C:20]=4[C:19]([CH3:34])([CH3:33])[C:18]=3[CH:35]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>C1COCC1.CO.[Pd]>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([C:14]2[CH:15]=[CH:16][C:17]3[C:29](=[O:30])[C:28]4[C:27]5[C:22](=[CH:23][C:24]([C:31]#[N:32])=[CH:25][CH:26]=5)[NH:21][C:20]=4[C:19]([CH3:34])([CH3:33])[C:18]=3[CH:35]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
Reactant: CC(C)(C)OC(=O)N1CC=C(c2ccc3c(c2)C(C)(C)c2[nH]c4cc(C#N)ccc4c2C3=O)CC1
Agent: [Pd]
Solvent: CO
Solvent: C1CCOC1
Product: CC(C)(C)OC(=O)N1CCC(c2ccc3c(c2)C(C)(C)c2[nH]c4cc(C#N)ccc4c2C3=O)CC1
Reaction time: 19 h

Procedure:
4-(3-Cyano-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazol-8-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (Compound B2-22-1, 16.2 g, 34.6 mmol) was dissolved in THF (800 ml) and methanol (230 ml), added with 10 wt % Pd/C (3.2 g), and stirred under hydrogen atmosphere for 19 hr. The solid was filtered through Celite, eluted with a mixture solvent (400 ml; THF/methanol=4/1), and concentrated under reduced pressure. The residues were dissolved in ethyl acetate (400 ml), and then washed with 1% aqueous solution of N-acetylcysteine, saturated aqueous solution of NaHCO3 and saturated brine. The organic layer was dried over sodium sulfate. The drying agent was removed by filtration and the residues were concentrated under reduced pressure to obtain the title compound as a crude product (white powder, 14.0 g, 86%).
Reaction SMILES: [CH3:1][C:2]1[C:6]([C:7]2[CH:8]=[C:9]([NH:13][CH:14]=[C:15]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:16](OCC)=[O:17])[CH:10]=[CH:11][CH:12]=2)=[C:5]([CH3:26])[O:4][N:3]=1.C1(OC2C=CC=CC=2)C=CC=CC=1>>[CH3:1][C:2]1[C:6]([C:7]2[CH:8]=[C:9]3[C:10]([C:16]([OH:17])=[C:15]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:14]=[N:13]3)=[CH:11][CH:12]=2)=[C:5]([CH3:26])[O:4][N:3]=1
Reactant: CCOC(=O)C(=CNc1cccc(-c2c(C)noc2C)c1)C(=O)OCC
Solvent: c1ccc(Oc2ccccc2)cc1
Product: CCOC(=O)c1cnc2cc(-c3c(C)noc3C)ccc2c1O
Yield: 76 %

Procedure:
Diethyl ({[3-(3,5-dimethyl-4-isoxazolyl)phenyl]amino}methylidene)-propanedioate (for a preparation see Intermediate 5, 75 g, 210 mmol) was suspended in boiling diphenylether (1 L) and heated to reflux for 30 minutes. The reaction mixture was cooled and precipitated with iPr2O to give the title compound as a brown powder (50 g, 76%). 1H NMR (300 MHz, DMSO-d6, ppm) δ: 12.45 (brs, 1H), 8.76 (s, 1H), 8.34 (d, J=8.6 Hz, 1H), 7.76 (s, 1H), 7.59 (d, J=8.6 Hz, 1H), 4.36 (q, J=7.1 Hz, 2H), 2.62 (s, 3H), 2.43 (s, 3H), 1.43 (s, J=7.1 Hz, 3H).
Reaction SMILES: [H-].[Na+].[CH3:3][C:4]1[N:9]=[C:8]2[NH:10][C:11]([CH2:13][CH3:14])=[N:12][C:7]2=[C:6]([CH3:15])[CH:5]=1.Br[CH2:17][C:18]1[CH:23]=[CH:22][C:21]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[C:30]#[N:31])=[CH:20][CH:19]=1>CN(C=O)C>[C:30]([C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=1[C:21]1[CH:20]=[CH:19][C:18]([CH2:17][N:10]2[C:8]3=[N:9][C:4]([CH3:3])=[CH:5][C:6]([CH3:15])=[C:7]3[N:12]=[C:11]2[CH2:13][CH3:14])=[CH:23][CH:22]=1)#[N:31]
Reactant: N#Cc1ccccc1-c1ccc(CBr)cc1
Reactant: CCc1nc2c(C)cc(C)nc2[nH]1
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: CCc1nc2c(C)cc(C)nc2n1Cc1ccc(-c2ccccc2C#N)cc1
Temperature: 25 °C
Reaction time: 0.08 h

Procedure:
To a suspension of 60% NaH (400 mg) in DMF (10 mL) was added the solution of 5,7-dimethyl-2-ethyl-3H-imidazo[4,5-b]pyridine (1.75 g, 10 mmol) DMF (10 mL) at 0° C. After 5 min, 4-bromomethyl-2'-cyano-1,1'-biphenyl (2.72 g, 10 mmol; Eur. Pat. Appl. 324,377, 1989) in DMF (10 mL) was added at 0° C. and the mixture was stirred at rt for 15 hrs. Extractive workup (2×EtOAc) from water followed by purification of the concentrated organic phases (Si02,) gave 3-(2'-cyano-1,1'-biphenyl-4-yl)methyl-5,7-dimethyl-2-ethyl-3H-imidazo[4,5-b]pyridine as a solid.
Reaction SMILES: [CH2:1]([N:3]([CH2:18][CH3:19])[CH2:4][CH2:5][CH2:6][NH:7][C:8]1[C:16]2[C:11](=[CH:12][CH:13]=[C:14](I)[CH:15]=2)[NH:10][N:9]=1)[CH3:2].NC1C2C(=C([I:30])C=CC=2)NN=1>>[CH2:1]([N:3]([CH2:18][CH3:19])[CH2:4][CH2:5][CH2:6][NH:7][C:8]1[C:16]2[C:11](=[C:12]([I:30])[CH:13]=[CH:14][CH:15]=2)[NH:10][N:9]=1)[CH3:2]
Reactant: Nc1n[nH]c2c(I)cccc12
Reactant: CCN(CC)CCCNc1n[nH]c2ccc(I)cc12
Product: CCN(CC)CCCNc1n[nH]c2c(I)cccc12
Yield: 54 %

Procedure:
The same procedures for preparing 3-(3-diethylaminopropylamino)-5-iodoindazole as described in Example 71 were repeated except that 3-amino-7-iodoindazole was employed instead of the 3-amino-5-iodoindazole. As a result, 7.57 g of 3-(3-diethylaminopropylamino)-7-iodoindazole having the following analytical values was obtained in a yield of 54%.
Reaction SMILES: C([N:4]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]2[C:5]1=[CH:6][CH:7]=[CH:8][CH:9]=2)C=C>C1(C)C=CC=CC=1.C([Si](C)(C)O[Si](C=C)(C)C)=C.[Pt]>[CH:6]1[C:5]2[NH:4][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]=2[CH:9]=[CH:8][CH:7]=1
Reactant: C=CCn1c2ccccc2c2ccccc21
Agent: [Pt]
Agent: C=C[Si](C)(C)O[Si](C)(C)C=C
Solvent: Cc1ccccc1
Product: c1ccc2c(c1)[nH]c1ccccc12
Temperature: 25 °C
Reaction time: 1 h

Procedure:
To a solution of 868 mg (0.853 mmol) of POSS and 447 mg (0.853 mmol) FPt-6 in 20 mL anhydrous toluene was added 4 drops of a solution of Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Pt(dvs)) (2 wt. % Pt in xylene). The reaction mixture was stirred at room temperature for 1 hour and then 1.765 g (8.53 mmol) of N-allylcarbazole was added and the reaction mixture was stirred for an additional 16 hours. The reaction mixture was then precipitated out of cold methanol and filtered through a silica plug using dichloromethane as the eluent to give a mixture of lumophore/host functionalized nanoparticles. The reaction mixture was purified chromatographically and three products, (POSS)(carbazole host)8, (POSS)(FPt-6)1(carbazole host)7 and (POSS)(FPt-6)2(carbazole)6 were separately isolated. The structures of the three products were confirmed by MALDI-TOF mass spectrometry. FIG. 7 shows the photoluminescent spectra of (POSS)(FPt-6)1(carbazole host)7 (POSS 61) and (POSS)(FPt-6)2(carbazole)6 (POSS 62). The photoluminescent spectrum of POSS 61 covers a broader region of the visible spectrum compared to that of POSS 62, and thus is a better material for a white-light emitting device. The CIE coordinates for POSS 61 and POSS 62 were (x=0.42, y=0.43) and (x=0.51, y=0.45), respectively, as shown in FIG. 8. As can be seen by FIG. 8, POSS 61 has CIE coordinates that is closer to the achromatic point (which represent the coordinates for white light) and a higher color rendering index (CRI) value. The CRI is a measure of the ability of a light source to reproduce the colors of various objects being lit by the source. The best possible rendition of colors is specified by a CRI of 100, while the very poorest rendition is specified by a CRI of 0.
Reaction SMILES: [O:1]=[C:2]1[C:7]2[NH:8][CH:9]=[C:10]([C:11](=[O:21])[C:12]3[C:17]([F:18])=[CH:16][C:15]([F:19])=[CH:14][C:13]=3[F:20])[C:6]=2[CH:5]=[CH:4][N:3]1[CH2:22][C:23]1[N:24]=[C:25]2[CH:30]=[C:29]([C:31](N)=[O:32])[CH:28]=[CH:27][N:26]2[CH:34]=1.Cl.[OH2:36]>CC#N>[O:1]=[C:2]1[C:7]2[NH:8][CH:9]=[C:10]([C:11](=[O:21])[C:12]3[C:17]([F:18])=[CH:16][C:15]([F:19])=[CH:14][C:13]=3[F:20])[C:6]=2[CH:5]=[CH:4][N:3]1[CH2:22][C:23]1[N:24]=[C:25]2[CH:30]=[C:29]([C:31]([OH:36])=[O:32])[CH:28]=[CH:27][N:26]2[CH:34]=1
Reactant: O
Reactant: NC(=O)c1ccn2cc(Cn3ccc4c(C(=O)c5c(F)cc(F)cc5F)c[nH]c4c3=O)nc2c1
Agent: Cl
Solvent: CC#N
Product: O=C(O)c1ccn2cc(Cn3ccc4c(C(=O)c5c(F)cc(F)cc5F)c[nH]c4c3=O)nc2c1
Temperature: 100 °C

Procedure:
To the product obtained in example 22 (40 mg, 0.083 mmol) suspended in H2O (0.5 mL) was added conc. HCl (0.68 mL, 8.31 mmol). The mixture was placed in a microwave reactor and heated to 100° C. for 10 min. Resulting suspension was diluted with 3:1 MeCN:H2O (2 mL) along with DMSO (1 mL) and purified by reverse phase HPLC (C-18 column) to give the title compound (29 mg). LC/MS: m/z 468(M+H). 1H-NMR (600 MHz, d6-DMSO): δ 5.45 (s, 2H), 6.98 (d, 1H), 7.32 (t, 2H), 7.53 (d, 1H), 7.61 (d, 1H), 7.88 (d, 1H), 8.15 (s, 1H), 8.17 (d, 1H), 8.71 (d, 1H).
Reaction SMILES: [OH:1][CH:2]([C:6]1[CH:11]=[CH:10][C:9]([C:12]2[N:16]=[C:15]([C:17]3[O:21][N:20]=[C:19]([C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)[C:18]=3[C:28]([F:31])([F:30])[F:29])[O:14][N:13]=2)=[CH:8][CH:7]=1)[C:3](O)=[O:4].[NH2:32][CH2:33][CH2:34][NH:35][C:36](=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39].CN1CCOCC1.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>CN(C=O)C>[OH:1][CH:2]([C:6]1[CH:7]=[CH:8][C:9]([C:12]2[N:16]=[C:15]([C:17]3[O:21][N:20]=[C:19]([C:22]4[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=4)[C:18]=3[C:28]([F:31])([F:29])[F:30])[O:14][N:13]=2)=[CH:10][CH:11]=1)[C:3]([NH:32][CH2:33][CH2:34][NH:35][C:36](=[O:42])[O:37][C:38]([CH3:40])([CH3:39])[CH3:41])=[O:4]
Reactant: O=C(O)C(O)c1ccc(-c2noc(-c3onc(-c4ccccc4)c3C(F)(F)F)n2)cc1
Reactant: CC(C)(C)OC(=O)NCCN
Agent: CN(C)C(On1nnc2cccnc21)=[N+](C)C
Agent: F[P-](F)(F)(F)(F)F
Solvent: CN(C)C=O
Solvent: CN1CCOCC1
Product: CC(C)(C)OC(=O)NCCNC(=O)C(O)c1ccc(-c2noc(-c3onc(-c4ccccc4)c3C(F)(F)F)n2)cc1
Reaction time: 1 h
Yield: 33.8 %

Procedure:
(R/S)-2-Hydroxy-2-(4-(5-(3-phenyl-4-(trifluoromethyl)isoxazol-5-yl)-1,2,4-oxadiazol-3-yl)phenyl)acetic acid (Int-V, 170 mg, 0.394 mmol), tert-butyl 2-aminoethylcarbamate (95 mg, 0.591 mmol), 4-methylmorpholine (159 mg, 1.577 mmol), and HATU (195 mg, 0.512 mmol) were dissolved in DMF (1 mL). The reaction mixture was stirred for 1 h and then was purified by prep HPLC (PHENOMENEX® Luna 5u 21×250 mm, gradient elution with Method 1—MeOH/water containing 0.1% trifluoroacetic acid as defined above, 0% B to 100% B over 30 min, 25 mL/min, 220 nM, product retention=31.6 min) to provide (R/S)-tert-butyl 2-(2-hydroxy-2-(4-(5-(3-phenyl-4-(trifluoromethyl)isoxazol-5-yl)-1,2,4-oxadiazol-3-yl)phenyl)acetamido)ethylcarbamate (80 mg, 0.133 mmol, 33.6% yield): LCMS=474.1 [M+H−C5H9O2]+; 1H NMR (400 MHz, methanol-d4) δ ppm 8.17 (2 H, d, J=8.35 Hz), 7.51-7.74 (7 H, m), 5.12 (1 H, s), 3.35 (2 H, br. s.), 3.17-3.22 (2 H, m), 1.43 (9 H, s); HPLC peak RT=9.8 min (Method A).