Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [I:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)=O.[F:9][C:10]([F:25])([F:24])[C:11]([F:23])([F:22])[C:12]([F:21])([F:20])[C:13]([F:19])([F:18])[S:14]([OH:17])(=[O:16])=[O:15].[C:26]1([CH3:32])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>ClCCl>[F:25][C:10]([F:9])([F:24])[C:11]([F:22])([F:23])[C:12]([F:20])([F:21])[C:13]([F:18])([F:19])[S:14]([O-:17])(=[O:16])=[O:15].[CH3:32][C:26]1[CH:31]=[CH:30][C:29]([I+:1][C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=2)=[CH:28][CH:27]=1
Reactant: Cc1ccccc1
Reactant: O=Ic1ccccc1
Reactant: O=S(=O)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
Solvent: ClCCl
Product: Cc1ccc([I+]c2ccccc2)cc1
Product: O=S(=O)([O-])C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
Temperature: 25 °C
Reaction time: 2 h

Procedure:
To a stirred suspension of 4.40 g (20 mmol) of iodosylbenzene in 100 ml of dichloromethane was added dropwise 6.0 g (20 mmol) of nonafluorobutane sulfonic acid at 0° C. under exclusion of moisture. The mixture was stirred at room temperature for 2 hours. The temperature was returned to 0° C. again. 1.84 g (20 mmol) of toluene was added dropwise. After the addition, stirring was continued at room temperature for additional 1 hour. The solvent as evaporated. The oily residue was dissolved in diethyl ether. The solution was cooled to obtain crystals of 4-methylphenyl phenyl iodonium nonafluorobutane sulfonate. The crystals were washed with hexane. The yield was 6.7 g.
Reaction SMILES: [NH2:1][C:2]1[S:3][CH:4]=[C:5]([C:7](=[N:33][O:34][CH3:35])[C:8]([NH:10][CH:11]2[C:31](=[O:32])[N:13]3[C:14]([C:18]([O:20]CC4C=CC([N+]([O-])=O)=CC=4)=[O:19])=[CH:15][CH2:16][S:17][C@H:12]23)=[O:9])[N:6]=1.[OH-].[K+].Cl>C(O)C.O>[NH2:1][C:2]1[S:3][CH:4]=[C:5]([C:7](=[N:33][O:34][CH3:35])[C:8]([NH:10][CH:11]2[C:31](=[O:32])[N:13]3[C:14]([C:18]([OH:20])=[O:19])=[CH:15][CH2:16][S:17][C@H:12]23)=[O:9])[N:6]=1
Reactant: CON=C(C(=O)NC1C(=O)N2C(C(=O)OCc3ccc([N+](=O)[O-])cc3)=CCS[C@H]12)c1csc(N)n1
Agent: Cl
Agent: [K+]
Agent: [OH-]
Solvent: O
Solvent: CCO
Product: CON=C(C(=O)NC1C(=O)N2C(C(=O)O)=CCS[C@H]12)c1csc(N)n1
Temperature: 5 °C
Reaction time: 0.25 h
Yield: 39.9 %

Procedure:
p-Nitrobenzyl 7-[2-(2-amino-4-thiazolyl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylate (syn isomer: 7.8 g.) was suspended in a mixture of ethanol (60 ml.) and water (60 ml.) 1 N Aqueous solution of potassium hydroxide (45 ml.) was added dropwise to the stirred suspension under ice-cooling over 10 minutes and stirred at 5° C. for 15 minutes. The resultant solution was adjusted to pH 7.0 with conc. hydrochloric acid, washed with ethyl acetate and the concentrated under reduced pressure to half of its initial volume. The concentrated solution was adjusted to pH 5.0 and subjected to column chromatography on macroporous, non-ionic adsorption resin "Diaion HP-20" (Trade mark; manufactured by Mitsubishi Chemical Industries Ltd.; 80 ml.), and eluted with 5% aqueous solution of isopropyl alcohol. The fractions containing the object compound were collected and adjusted to pH 3.2 with 10% hydrochloric acid. The precipitating crystals were collected by filtration, and dried to give 7-[ 2-(2-amino-4-thiazolyl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylic acid (syn-isomer: 2.3 g.).
Reaction SMILES: C[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]1[O:10][C:11]2[CH:17]=[C:16]([CH2:18][C:19]([OH:21])=O)[CH:15]=[CH:14][C:12]=2[N:13]=1.[CH3:22][NH:23][CH2:24][CH2:25][O:26][C:27]1[CH:36]=[CH:35][C:30]([C:31]([O:33][CH3:34])=[O:32])=[CH:29][CH:28]=1.[CH3:37]CN=C=NCCCN(C)C.Cl.O>CN(C=O)C.CN(C1C=CN=CC=1)C.C1C=CC2N(O)N=NC=2C=1>[CH3:37][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]1[O:10][C:11]2[CH:17]=[C:16]([CH2:18][C:19]([N:23]([CH2:24][CH2:25][O:26][C:27]3[CH:36]=[CH:35][C:30]([C:31]([O:33][CH3:34])=[O:32])=[CH:29][CH:28]=3)[CH3:22])=[O:21])[CH:15]=[CH:14][C:12]=2[N:13]=1
Reactant: CCN=C=NCCCN(C)C
Reactant: Cc1ccccc1Nc1nc2ccc(CC(=O)O)cc2o1
Reactant: CNCCOc1ccc(C(=O)OC)cc1
Agent: CN(C)c1ccncc1
Agent: Cl
Agent: On1nnc2ccccc21
Solvent: CN(C)C=O
Solvent: O
Product: COC(=O)c1ccc(OCCN(C)C(=O)Cc2ccc3nc(Nc4ccccc4C)oc3c2)cc1
Temperature: 25 °C
Reaction time: 18 h
Yield: 79.5 %

Procedure:
In DMF (6 ml) were dissolved 2-(2-methylphenylamino)-6-benzoxazolylacetic acid (154 mg, 0.55 mmol) and methyl 4-(2-(N-methylamino)ethoxy)benzoate (117 mg, 0.55 mmol). To the resulting solution were added EDC HCl (157 mg, 0.81 mmol), HOBt (5 mg, 0.04 mmol), and DMAP (5 mg, 0.04 mmol). The resulting mixture was stirred at room temperature for 18 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the solvent. The residue was purified by chromatography on a silica gel column, whereby from chloroform-methanol (10:1, v/v) eluate fractions, methyl 4-(2-((2-(2-methylphenylamino)-6-benzoxazolyl)-N-methylacetamido)ethoxy)benzoate (207 mg, 80%) was obtained as a yellow oil.
Reaction SMILES: [CH3:1][N:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[C:10]3[C@:11]4([O:30][CH3:31])[C@@H:16]([CH2:17][C:4]([C:5]=23)=[CH:3]1)[N:15]([CH3:18])[CH2:14][C@H:13]([CH2:19][O:20][C:21]([C:23]1[CH:28]=[N:27][CH:26]=[C:25]([Br:29])[CH:24]=1)=[O:22])[CH2:12]4.C[Si](C)(C)[Cl:34].C1C=CC=CC=1>CC(C)=O>[Br:29][C:25]1[CH:26]=[N:27][CH:28]=[C:23]([CH:24]=1)[C:21]([O:20][CH2:19][CH:13]1[CH2:12][C@@:11]2([O:30][CH3:31])[C@@H:16]([CH2:17][C:4]3[C:5]4[C:6](=[CH:7][CH:8]=[CH:9][C:10]2=4)[N:2]([CH3:1])[C:3]=3[Cl:34])[N:15]([CH3:18])[CH2:14]1)=[O:22]
Reactant: C[Si](C)(C)Cl
Reactant: CO[C@]12C[C@@H](COC(=O)c3cncc(Br)c3)CN(C)[C@@H]1Cc1cn(C)c3cccc2c13
Solvent: CC(C)=O
Solvent: c1ccccc1
Product: CO[C@]12CC(COC(=O)c3cncc(Br)c3)CN(C)[C@@H]1Cc1c(Cl)n(C)c3cccc2c13

Procedure:
Following the process of Example 25, 1 g of nicergoline (8-[(5-bromonicotinoyl)oxymethyl]-1,6-dimethyl-10-methoxyergoline) is reacted with 1.6 ml of trimethylchlorosilane and the obtained product is isolated by chromatography on a Kieselgel column, using a 7:3 mixture of benzene and acetone as eluant, to give the title compound in a yield of 0.65 g (0.00125 mole, 60%).
Reaction SMILES: [CH3:1][C:2]1([CH3:20])[C:6]2[N+:7]([O-])=[C:8]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[N:9]=[N:10][C:5]=2[C:4]([CH3:19])([CH3:18])[O:3]1.C(OP(OCC)OCC)C>>[CH3:1][C:2]1([CH3:20])[C:6]2[N:7]=[C:8]([C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=3)[N:9]=[N:10][C:5]=2[C:4]([CH3:19])([CH3:18])[O:3]1
Reactant: CC1(C)OC(C)(C)c2c1nnc(-c1ccccc1)[n+]2[O-]
Agent: CCOP(OCC)OCC
Product: CC1(C)OC(C)(C)c2nc(-c3ccccc3)nnc21

Procedure:
A mixture of 5.42 g. (0.02 mole) 5,7-dihydro-5,5,7,7-tetramethyl-3-phenylfuro[ 3,4-e]-as-triazine-4oxide and 70 ml. triethylphosphite is refluxed under nitrogen for 18 hours at a bath temperature of 180° C. The solvent is removed in vacuo and the residue recrystallized from aqueous ethanol to give 5,7-dihydro-5,5,7,7-tetramethyl-3-phenylfuro[3,4-e]-as-triazine, m.p. 90°-91° C.
Reaction SMILES: [C:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[OH:13])[C:6]([O:8][CH3:9])=[O:7])#[N:2].CCN(CC)CC.[O:21](S(C(F)(F)F)(=O)=O)[S:22]([C:25]([F:28])([F:27])[F:26])(=O)=[O:23]>C(Cl)Cl.O>[C:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[O:13][S:22]([C:25]([F:28])([F:27])[F:26])(=[O:23])=[O:21])[C:6]([O:8][CH3:9])=[O:7])#[N:2]
Reactant: COC(=O)c1ccc(O)c(C#N)c1
Reactant: O=S(=O)(OS(=O)(=O)C(F)(F)F)C(F)(F)F
Solvent: CCN(CC)CC
Solvent: ClCCl
Solvent: O
Product: COC(=O)c1ccc(OS(=O)(=O)C(F)(F)F)c(C#N)c1
Temperature: 30 °C
Reaction time: 2 h
Yield: 27.4 %

Procedure:
To a mixture of crude methyl 3-cyano-4-hydroxybenzoate (2.50 g) from above and Et3N (1.31 g, 13.0 mmol) in anhydrous DCM (20 mL) was added Tf2O (1.82 g, 6.50 mmol) dropwise and then the reaction mixture was stirred at 30° C. for 2 hours. The resulting mixture was suspended in water (50 mL) and extracted with DCM (50 mL×3), dried over anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel (PE/EtOAc=10/1) to give Intermediate 1 (550 mg, 2-step yield: 28%) as a colorless oil. 1H NMR (CDCl3 300 MHz): δ 8.43 (d, J=2.1 Hz, 1H), 8.37 (dd, J=8.7, 2.1 Hz, 1H), 7.59 (d, J=8.7 Hz, 1H), 3.98 (s, 3H).
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4]([NH:8][C:9]2[C:14]3[CH:15]=[CH:16][N:17]([CH3:18])[C:13]=3[C:12]([C:19]([OH:21])=O)=[CH:11][N:10]=2)[CH:5]=[CH:6][CH:7]=1.CN(C)CCCN=C=NCC.ON1C2C=CC=CC=2N=N1.C(N1CCOCC1)C.[NH:51]1[CH2:56][CH2:55][S:54][CH2:53][CH2:52]1>CN(C)C=O.O>[Cl:1][C:2]1[CH:3]=[C:4]([NH:8][C:9]2[C:14]3[CH:15]=[CH:16][N:17]([CH3:18])[C:13]=3[C:12]([C:19]([N:51]3[CH2:56][CH2:55][S:54][CH2:53][CH2:52]3)=[O:21])=[CH:11][N:10]=2)[CH:5]=[CH:6][CH:7]=1
Reactant: C1CSCCN1
Reactant: Cn1ccc2c(Nc3cccc(Cl)c3)ncc(C(=O)O)c21
Agent: CCN1CCOCC1
Agent: CCN=C=NCCCN(C)C
Agent: On1nnc2ccccc21
Solvent: CN(C)C=O
Solvent: O
Product: Cn1ccc2c(Nc3cccc(Cl)c3)ncc(C(=O)N3CCSCC3)c21
Temperature: 25 °C
Reaction time: 8 h

Procedure:
To a solution of 4-[(3-chlorophenyl)amino]-1-methyl-1H-pyrrolo[3,2-c]pyridine-7-carboxylic acid (0.2 g) in dimethylformamide (5 ml) was added 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (0.15 g), 1-hydroxybenzotriazole (0.14 g), N-ethylmorpholine (0.34 ml) and thiomorpholine (0.13 ml). The solution was stirred at room temperature overnight. The reaction was diluted with water and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with saturated sodium bicarbonate solution followed by saturated sodium chloride solution then dried (MgSO4) and evaporated. The residue was purified by MDAP to afford the title compound as a white solid (236 mg).
Reaction SMILES: C(OC(OCC)C(=O)CC1C=CC(CC)=CC=1)C.[CH:19]1[CH:24]=[CH:23][C:22]([CH2:25][C:26]2[NH:35][C:34]([C:36]3[CH:41]=[CH:40][C:39]([OH:42])=[CH:38][CH:37]=3)=[CH:33][N:32]3[C:27]=2[N:28]=[C:29]([CH2:43][C:44]2[CH:49]=[CH:48][C:47]([OH:50])=[CH:46][CH:45]=2)[C:30]3=[O:31])=[CH:21][CH:20]=1.Cl>O1CCOCC1.O>[CH:19]1[CH:24]=[CH:23][C:22]([CH2:25][C:26]2[C:27]3[N:32]([CH:33]=[C:34]([C:36]4[CH:37]=[CH:38][C:39]([OH:42])=[CH:40][CH:41]=4)[N:35]=2)[C:30]([OH:31])=[C:29]([CH2:43][C:44]2[CH:49]=[CH:48][C:47]([OH:50])=[CH:46][CH:45]=2)[N:28]=3)=[CH:21][CH:20]=1
Reactant: O=c1c(Cc2ccc(O)cc2)nc2c(Cc3ccccc3)[nH]c(-c3ccc(O)cc3)cn1-2
Agent: CCOC(OCC)C(=O)Cc1ccc(CC)cc1
Agent: Cl
Solvent: O
Solvent: C1COCCO1
Product: Oc1ccc(Cc2nc3c(Cc4ccccc4)nc(-c4ccc(O)cc4)cn3c2O)cc1
Temperature: 0 °C
Reaction time: 17 h
Yield: 64.2 %

Procedure:
Under an argon atmosphere, 1,1-diethoxy-3-(4-ethylphenyl)propan-2-one (43) (301 mg, 1.20 mmol) was dissolved in 1,4-dioxane (2 mL) and water (0.4 mL). To this was added coelenteramine (238 mg, 858 μmol) and, after cooling to 0° C., conc. hydrochloric acid (0.20 mL) was further added thereto, and then stirred overnight (17 hours) at 100° C. After cooling to room temperature, the mixture was concentrated under reduced pressure and the residue was purified by silica gel flash chromatography in an argon flow (n-hexane/ethyl acetate═1/2→ethyl acetate→ethyl acetate/methanol═50/1→10/1). The solid obtained was further reprecipitated (n-hexane/acetone) to give et-coelenterazine (44, et-CTZ) as a yellow powder (240 mg, 551 μmol, 64.2%).
Reaction SMILES: [C:1]([NH:9][C@H:10]1[CH2:15][CH2:14][CH2:13][CH2:12][C@H:11]1[C:16]([OH:18])=[O:17])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[CH3:20]N(C)CCCN=C=NCC.C[O-].[Na+].Cl>CO.O1CCCC1.C(#N)C>[C:1]([NH:9][C@H:10]1[CH2:15][CH2:14][CH2:13][CH2:12][C@@H:11]1[C:16]([O:18][CH3:20])=[O:17])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: O=C(N[C@H]1CCCC[C@H]1C(=O)O)c1ccccc1
Reactant: CCN=C=NCCCN(C)C
Agent: C[O-]
Agent: Cl
Agent: [Na+]
Solvent: CC#N
Solvent: CO
Solvent: C1CCOC1
Product: COC(=O)[C@H]1CCCC[C@@H]1NC(=O)c1ccccc1
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 50.9 %

Procedure:
A mixture of (1R,2S)-2-(benzoylamino)cyclohexanecarboxylic acid (2.47 g, 10 mmol), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (2.30 g, 12 mmol), acetonitrile (25 ml) and tetrahydrofuran (25 ml) was stirred at room temperature for 30 min. The reaction mixture was concentrated under reduced pressure, methanol (25 ml) was added, and the mixture was stirred at 60° C. for 3 hrs. The reaction mixture was concentrated under reduced pressure, dil. hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The extract was washed with aqueous sodium hydrogen carbonate solution, then with saturated brine and dried (over anhydrous MgSO4). The solvent was evaporated under reduced pressure. 28% Sodium methoxide in methanol solution (1.93 g, 10 mmol) and methanol (30 ml) were added to the residue and the mixture was heated under reflux for 5 hrs. 1N Hydrochloric acid (11 ml) was added under ice-cooling, and methanol was evaporated under reduced pressure. Aqueous sodium hydrogen carbonate solution was added to the obtained residue, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried (over anhydrous MgSO4), and the solvent was evaporated under reduced pressure. The obtained solid was collected by filtration and washed with diisopropyl ether to give methyl(1S,2S)-2-(benzoylamino)cyclohexanecarboxylate (1.33 g, 51%) as a colorless powder.
Reaction SMILES: [NH2:1][C:2]1[N:7]=[N:6][C:5]([C:8]2[C:16]3[C:11](=[N:12][CH:13]=[CH:14][CH:15]=3)[N:10]([CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[F:24])[N:9]=2)=[N:4][C:3]=1O.[NH3:26]>S(Cl)(Cl)=O.C(#N)C>[F:24][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=1[CH2:17][N:10]1[C:11]2=[N:12][CH:13]=[CH:14][CH:15]=[C:16]2[C:8]([C:5]2[N:6]=[N:7][C:2]([NH2:1])=[C:3]([NH2:26])[N:4]=2)=[N:9]1
Reactant: N
Reactant: Nc1nnc(-c2nn(Cc3ccccc3F)c3ncccc23)nc1O
Solvent: O=S(Cl)Cl
Solvent: CC#N
Product: Nc1nnc(-c2nn(Cc3ccccc3F)c3ncccc23)nc1N
Temperature: 25 °C
Reaction time: 8 h

Procedure:
3.602 g (10.677 mmol) of 6-amino-3-[1-(2-fluorobenzyl)-1H-pyrazolo[3,4-b]pyridin-3-yl]-1,2,4-triazin-5-ol in 45 ml of thionyl chloride were added and heated under reflux for 3 h. The reaction mixture was diluted with 200 ml of dry acetonitrile and, with ice-cooling, added dropwise to 500 ml of concentrated aqueous ammonia solution (35% strength). The mixture was stirred at RT overnight. The acetonitrile was removed on a rotary evaporator and the precipitate was filtered off with suction. This gave 3.541 g (purity 67%, 66% of theory) of the target compound. A small amount was purified by preparative HPLC (mobile phase: acetonitrile/water with 0.1% TFA, gradient 30:70→95:5).
Reaction SMILES: [F:1][C:2]1[CH:3]=[CH:4][C:5]([NH:8][NH2:9])=[N:6][CH:7]=1.[C:10]([N:17]1[CH2:22][CH2:21][CH:20]([CH2:23][CH:24]=O)[CH2:19][CH2:18]1)([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].C(OI(C1C=CC=CC=1)OC(=O)C)(=O)C.[OH-].[Na+]>CCO.C(Cl)Cl.CO>[C:13]([O:12][C:10]([N:17]1[CH2:22][CH2:21][CH:20]([CH2:23][C:24]2[N:6]3[CH:7]=[C:2]([F:1])[CH:3]=[CH:4][C:5]3=[N:8][N:9]=2)[CH2:19][CH2:18]1)=[O:11])([CH3:16])([CH3:15])[CH3:14]
Reactant: CC(C)(C)OC(=O)N1CCC(CC=O)CC1
Reactant: NNc1ccc(F)cn1
Agent: CC(=O)OI(OC(C)=O)c1ccccc1
Agent: [Na+]
Agent: [OH-]
Solvent: ClCCl
Solvent: CCO
Solvent: CO
Product: CC(C)(C)OC(=O)N1CCC(Cc2nnc3ccc(F)cn23)CC1
Temperature: 0 °C
Reaction time: 0.5 h
Yield: 105.9 %

Procedure:
A dark brown solution of (5-fluoro-pyridin-2-yl)-hydrazine (549 mg, 4.32 mmol) and N-Boc-4-piperidine acetaldehyde (Aldrich, 982 mg, 4.32 mmol) in EtOH (10 mL) was stirred at reflux for 30 min, then cooled to 0° C., diluted with DCM (25 mL) and then (diacetoxyiodo)benzene (1.67 g, 5.18 mmol) was added portionwise over 1 min. The purple solution was stirred at RT for 30 min, then aqueous NaOH (1M, 20 mL) was added and the mixture shaken. The aqueous layer was extracted with DCM (2×20 mL), then the combined organics passed through a hydrophobic frit and concentrated in vacuo to leave an orange solid. FCC, using 3% MeOH in DCM, gave the title compound as a pale orange solid (1.53 g, 90%). LCMS (Method 3): Rt 3.15, m/z 235 [M-CO2C4H9+H+].
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.C([O-])([O-])O[CH2:13][CH3:14].CN1CCN(C)C1=O.[N+:25]([N:28]=[C:29]1[NH:33]C[CH2:31][NH:30]1)([O-:27])=[O:26]>S(=O)(=O)(O)O.C(OCC)(=O)C>[CH3:9][C:8]([C:5]1[CH:6]=[CH:7][C:2]([N:1]=[CH:31][N:30]2[CH2:14][CH2:13][NH:33][C:29]2=[N:28][N+:25]([O-:27])=[O:26])=[CH:3][CH:4]=1)=[O:10]
Reactant: CCOC([O-])[O-]
Reactant: CC(=O)c1ccc(N)cc1
Reactant: O=[N+]([O-])N=C1NCCN1
Agent: O=S(=O)(O)O
Solvent: CN1CCN(C)C1=O
Solvent: CCOC(C)=O
Product: CC(=O)c1ccc(N=CN2CCNC2=N[N+](=O)[O-])cc1
Temperature: 140 °C
Reaction time: 0.17 h
Yield: 53 %

Procedure:
A mixture of 5.0 g of p-aminoacetophenone. 6.6 g of ethyl orthoformate, 5 ml of 1,3-dimethyl-2-imidazolidinone and 0.03 g of concentrated sulfuric acid was placed in a reactor equipped with Dean's stark tube and agitated at 140° C. for about 10 minutes, followed by further addition of 5.8 g of nitroiminoimidazolidine and agitation at 160° C. for 1 hour. The reaction mixture was poured into 200 ml of a saturated saline solution, to which 150 ml of ethyl acetate was added. The resultant crystals were collected by filtration, and dried to give 5.4 g of 1-(4-methylcarbonyl-phenyliminomethyl)-2-nitroiminoimidazolidine.
Reaction SMILES: [N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[S:11][N:10]=[CH:9][C:8]=2[CH:12]=1)([O-])=O.CC(O)=O>O.CCOC(C)=O.[Fe]>[NH2:1][C:4]1[CH:5]=[CH:6][C:7]2[S:11][N:10]=[CH:9][C:8]=2[CH:12]=1
Reactant: O=[N+]([O-])c1ccc2sncc2c1
Agent: [Fe]
Solvent: O
Solvent: CC(=O)O
Solvent: CCOC(C)=O
Product: Nc1ccc2sncc2c1
Temperature: 25 °C
Reaction time: 1 h
Yield: 86.7 %

Procedure:
5-Nitrobenzo[d]isothiazole (305 mg, 1.69 mmol), 5% AcOH (aq.) (12 mL) and EtOAc (12 mL) at 65° C. was treated with iron powder (325 mesh, 473 mg) and stirred rapidly for 1 h. The mixture was cooled to ambient temperature, diluted with water and EtOAc and filtered through dicalite. The organic layer was separated and the aqueous layer extracted with further EtOAc. The combined organic extracts were washed with brine, dried (MgSO4) and concentrated in vacuo to give the title compound as a yellow solid (220 mg, 85%).
Reaction SMILES: [CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([NH2:10])[CH:5]=1.[Br:12][C:13]1[CH:14]=[C:15]([CH:18]=[CH:19][CH:20]=1)[CH:16]=O.[CH2:21]=[C:22]([CH3:24])[CH3:23].FC(F)(F)S([O-])(=O)=O.[Yb+3].FC(F)(F)S([O-])(=O)=O.FC(F)(F)S([O-])(=O)=O>C(#N)C.C(OCC)(=O)C>[CH3:1][O:2][C:3]([C:4]1[CH:5]=[C:6]2[C:7]([C:22]([CH3:24])([CH3:23])[CH2:21][CH:16]([C:15]3[CH:18]=[CH:19][CH:20]=[C:13]([Br:12])[CH:14]=3)[NH:10]2)=[CH:8][CH:9]=1)=[O:11]
Reactant: C=C(C)C
Reactant: O=Cc1cccc(Br)c1
Reactant: COC(=O)c1cccc(N)c1
Agent: O=S(=O)([O-])C(F)(F)F
Agent: [Yb+3]
Solvent: CCOC(C)=O
Solvent: CC#N
Product: COC(=O)c1ccc2c(c1)NC(c1cccc(Br)c1)CC2(C)C
Temperature: 85 °C
Reaction time: 18 h
Yield: 39.9 %

Procedure:
To a stirred solution of 3-amino-benzoic acid methyl ester (11.3 g, 78.4 mmol) and 3-bromobenzaldehyde (9.2 mL, 78.4 mmol) in acetonitrile (150 mL) were added isobutene (21.0 mL, 313.5 mmol) and ytterbium(III) trifluoromethanesulfonate (Yb(OTf)3) (5.8 g, 9.5 mmol). The resulting mixture was stirred at 85° C. for 18 h in sealed tube. The mixture was diluted with ethyl acetate (300 mL) and washed with water (100 mL×2) and brine (100 mL×2) and then dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by ISCO combi-flash chromatography (gradient elution, 10-50% ethyl acetate in petroleum ether) to afford 2-(3-bromo-phenyl)-4,4-dimethyl-1,2,3,4-tetrahydro-quinoline-7-carboxylic acid methyl ester (11.7 g, 40.0%) as a light yellow solid: MS (ESI) M+1=374.
Reaction SMILES: [F:1][C:2]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:3]=1[O:4][C:5]1[C:14]2[C:9](=[CH:10][C:11]([OH:15])=[CH:12][CH:13]=2)[N:8]=[CH:7][CH:6]=1.[OH-:23].[Na+].C(Cl)(Cl)Cl.Cl>CC(C)=O.O>[F:1][C:2]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:3]=1[O:4][C:5]1[C:14]2[C:9](=[CH:10][C:11]([O:15][C:14]([CH3:9])([CH3:13])[C:5]([OH:4])=[O:23])=[CH:12][CH:13]=2)[N:8]=[CH:7][CH:6]=1
Reactant: [OH-]
Reactant: O=[N+]([O-])c1ccc(Oc2ccnc3cc(O)ccc23)c(F)c1
Agent: Cl
Agent: [Na+]
Solvent: O
Solvent: CC(C)=O
Solvent: ClC(Cl)Cl
Product: CC(C)(Oc1ccc2c(Oc3ccc([N+](=O)[O-])cc3F)ccnc2c1)C(=O)O
Yield: 72.5 %

Procedure:
To a mixture of 4-(2-fluoro-4-nitrophenoxy)quinolin-7-ol (5 g, 16.7 mmol) and NaOH (6.7 g, 166.7 mmol) in acetone (67 mL) was added chloroform (21.9 g, 183.3 mmol) dropwise at room temperature. After the mixture turned brown color, the reaction was heated to reflux for 1 hour. Water (10 mL) was then added to the reaction mixture, and the resulted solution was adjusted to pH 3˜4 with 1 N HCl solution. The resulted mixture was concentrated in vacuo, and then extracted with EtOAc (30 mL). The organic phase was separated, concentrated in vacuo, and treated with 95% EtOH (10 mL). The resulted solid was collected by filtration, dried in vacuo overnight to afford the title compound as a brown solid (2.34 g, 36.4%).
Reaction SMILES: [CH3:1][C:2]1[C:3](=O)[C:4]2[C:25]([C:26](=O)[C:27]=1[CH3:28])=[CH:24][C:23]1[C:6](=[CH:7][C:8]3[C:21]([CH:22]=1)=[CH:20][C:19]1[C:10](=[CH:11][C:12]4[C:13](=O)[C:14]([CH3:32])=[C:15]([CH3:31])[C:16](=O)[C:17]=4[CH:18]=1)[CH:9]=3)[CH:5]=2.[NH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.[N:42]12[CH2:49][CH2:48]N(CC1)CC2>ClC1C=CC=CC=1.Cl[Ti](Cl)(Cl)Cl>[C:36]1([N:35]=[C:16]2[C:17]3[C:12](=[CH:11][C:10]4[C:19]([CH:18]=3)=[CH:20][C:21]3[C:8](=[CH:7][C:6]5[C:23]([CH:22]=3)=[CH:24][C:25]3[C:26](=[N:35][C:36]6[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=6)[C:27]([CH3:28])=[C:2]([CH3:1])[C:3](=[N:35][C:36]6[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=6)[C:4]=3[CH:5]=5)[CH:9]=4)[C:13](=[N:42][C:49]3[CH:48]=[CH:26][CH:27]=[CH:2][CH:1]=3)[C:14]([CH3:32])=[C:15]2[CH3:31])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1
Reactant: Cc1c(C)c(=O)c2cc3cc4cc5cc6c(=O)c(C)c(C)c(=O)c6cc5cc4cc3cc2c1=O
Reactant: C1CN2CCN1CC2
Reactant: Nc1ccccc1
Agent: Cl[Ti](Cl)(Cl)Cl
Solvent: Clc1ccccc1
Product: Cc1c(C)c(=Nc2ccccc2)c2cc3cc4cc5cc6c(=Nc7ccccc7)c(C)c(C)c(=Nc7ccccc7)c6cc5cc4cc3cc2c1=Nc1ccccc1
Temperature: 125 °C
Reaction time: 1.5 h
Yield: 56.5 %

Procedure:
A solution of TiCl4 (0.15 ml, 1.4 mmol) dissolved in chlorobenzene (5 ml) was slowly added at 75° C. to a mixture of the crude hexacenetetrone (10) (0.118 g), aniline (0.15 ml, 1.6 mmol) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (0.900 g, 8.0 mmol) dissolved in chlorobenzene (20 ml). The reaction mixture was then stirred for 1.5 hours at 125° C. This reaction mixture was then concentrated by passing through a silica gel column (CHCl3). The residue was again dissolved in CHCl3 and re-precipitated in a large amount of acetonitrile. The precipitate was then filtered with Celite, washed with acetonitrile and MeOH, and dried in a vacuum to obtain N,N′,N″,N′″-tetraphenyl-2,3,10,11-tetramethyl-1,4,9,12-hexacenetetrone tetraimine (11) (0.0560 g, 0.075 mmol) at a yield of 25% with respect to 1,4:9,12-dicarboxy-5, 16:8,13-diepoxy-4a,5,8,8a,12a,13,16,16a-octahydro-1,2,3,4,9,10,11,12-octaphenylhexacene (9).
Reaction SMILES: [CH:1]1[C:13]2[C:12](=O)[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[NH2:15][NH2:16]>>[CH:1]1[C:13]2[C:12](=[N:15][NH2:16])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1
Reactant: NN
Reactant: O=C1c2ccccc2-c2ccccc21
Product: NN=C1c2ccccc2-c2ccccc21

Procedure:
Symmetrical charge transport materials can be prepared by the following procedure. In the first step a 9-fluorenone or a derivative compound reacts with an excess of hydrazine at 50-70° C. for 1-6 hours to produce a 9-fluorenone hydrazone compound or derivative thereof. Then, the 9-fluorenone hydrazone compound can be isolated and purified. In the next step, the 9-fluorenone hydrazone reacts with a linking compound having 2 aldehyde groups or ketone groups, such as OCH—CHO, a quinone derivative, or a diphenoquinone derivative, in a mole ratio of 2:1 (2 mole of hydrazine derivative with 1 mole of the linking compound). The desired product can be isolated and purified by recrystalization or/and column chromatography.