Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][CH:2]([C:22](=[O:25])[CH2:23][CH3:24])[C:3]([O:5][CH2:6][C:7]1[C:12]([CH:13]([CH3:15])[CH3:14])=[CH:11][C:10]([CH:16]([CH3:18])[CH3:17])=[CH:9][C:8]=1[CH:19]([CH3:21])[CH3:20])=[O:4].[B-](F)(F)(F)[F:27].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1>O>[F:27][C:2]([CH3:1])([C:22](=[O:25])[CH2:23][CH3:24])[C:3]([O:5][CH2:6][C:7]1[C:12]([CH:13]([CH3:14])[CH3:15])=[CH:11][C:10]([CH:16]([CH3:17])[CH3:18])=[CH:9][C:8]=1[CH:19]([CH3:21])[CH3:20])=[O:4]
Reactant: F[B-](F)(F)F
Reactant: CCC(=O)C(C)C(=O)OCc1c(C(C)C)cc(C(C)C)cc1C(C)C
Agent: F[N+]12CC[N+](CCl)(CC1)CC2
Solvent: O
Product: CCC(=O)C(C)(F)C(=O)OCc1c(C(C)C)cc(C(C)C)cc1C(C)C
Temperature: 0 °C
Reaction time: 0.17 h
Yield: 89.2 %

Procedure:
At 0° C., 444 mg of 2,4,6-triisopropylbenzyl 2-methyl-3-oxopentanoate (1.28 mmol) are dissolved in 10 ml of F-TEDA (0.145 M in MeCN, 1.45 mmol). After equilibration for 10 minutes, 1.28 ml of catalyst C7 (0.05 M in MeCN, 0.064 mmol, 5 mol %) are added dropwise and the resulting cloudy, lemon-yellow solution is stirred at 0° C. for 25 h. The reaction mixture is taken up in water and TBME, and the organic phase is separated off, washed twice with saturated aqueous NaCl solution and concentrated in an RE. Purification of the crude product by liquid chromatography (TBME/hexane 1:25) affords 416 mg (89%) of 2,4,6-triisopropylbenzyl 2-fluoro-2-methyl-3-oxopentanoate as colourless oil with an ee of 85.6%.
Reaction SMILES: [C:1]([O:15]CC)(=O)[CH2:2][O:3][CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH3:13].O.[NH2:19][NH2:20]>C(O)C>[C:1]([NH:19][NH2:20])(=[O:15])[CH2:2][O:3][CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH3:13]
Reactant: NN
Reactant: CCOC(=O)COCCOCCOCCOC
Solvent: O
Solvent: CCO
Product: COCCOCCOCCOCC(=O)NN
Reaction time: 25 h

Procedure:
A solution of 61 g (0.244 mol) of crude ethyl 3,6,9,12-tetra-oxa-tridecanoate and 25 ml (0.488 mol) of hydrazine hydrate in 600 ml of ethanol is left to stand for 25 hours at 25°. The reaction mixture is evaporated and the crude, oily 3,6,9,12-tetra-oxa-tridecanoic acid hydrazide, which is thus obtained, is further processed direct.
Reaction SMILES: [NH2:1][C:2]1[C:7]([I:8])=[CH:6][CH:5]=[C:4]([Cl:9])[N:3]=1.Br.[CH:11](O)(C)[CH3:12]>>[Cl:9][C:4]1[N:3]2[CH:11]=[CH:12][N:1]=[C:2]2[C:7]([I:8])=[CH:6][CH:5]=1
Reactant: CC(C)O
Reactant: Nc1nc(Cl)ccc1I
Agent: Br
Product: Clc1ccc(I)c2nccn12
Temperature: 25 °C

Procedure:
2-amino-3-iodo-6-chloropyridine (2 g, 7.874 mmol) is taken up in isopropanol (30 mL) under N2. Diethoxy-2-bromoacetal (2.5 mL, 15.748 mmol, 2 equiv.) is added to the suspension followed by HBr 48% (2 mL). The resulting mixture is then refluxed for 12 h and cooled down to room temperature. The mixture is partly concentrated under vacuum and the resulting slurry is taken up in diethyl ether which causes the precipitation of a solid that is separated by filtration and washed with little amounts of diethyl ether to afford the desired material as a powder.
Reaction SMILES: [O:1]1[CH2:6][CH2:5][CH2:4][O:3][CH:2]1[CH2:7][NH:8][C:9]1[C:14]([CH2:15][CH3:16])=[CH:13][CH:12]=[CH:11][C:10]=1[CH2:17][CH3:18].C(=O)(O)[O-].[Na+].O1CCOCC1.[Cl:30][CH2:31][C:32](Cl)=[O:33]>CCOCC.O>[Cl:30][CH2:31][C:32]([N:8]([CH2:7][CH:2]1[O:3][CH2:4][CH2:5][CH2:6][O:1]1)[C:9]1[C:14]([CH2:15][CH3:16])=[CH:13][CH:12]=[CH:11][C:10]=1[CH2:17][CH3:18])=[O:33]
Reactant: CCc1cccc(CC)c1NCC1OCCCO1
Reactant: O=C(Cl)CCl
Agent: O=C([O-])O
Agent: [Na+]
Solvent: C1COCCO1
Solvent: O
Solvent: CCOCC
Product: CCc1cccc(CC)c1N(CC1OCCCO1)C(=O)CCl
Reaction time: 0.25 h

Procedure:
N-(1,3Dioxan-2-ylmethyl)-2,6-diethylaniline (25 grams), sodium bicarbonate (10 grams), dioxane (30 ml) and water (4 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture is cooled to a temperature of about 0°C and chloroacetyl chloride (15 grams) is added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about 1 hour. After this time ether (100 ml) is added to the mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue is recrystallized to yield the desired product N-α-chloroacetyl-N-(1,3-dioxan- 2-ylmethyl)-2,6-diethylaniline.
Reaction SMILES: [CH2:1]([O:5][C:6](Cl)=[O:7])[CH:2]([CH3:4])[CH3:3].[NH2:9][C:10]1[C:15]([O:16][CH3:17])=[N:14][C:13]([CH3:18])=[CH:12][N:11]=1.N1C=CC=CC=1>ClCCl>[CH3:17][O:16][C:15]1[C:10]([NH:9][C:6](=[O:7])[O:5][CH2:1][CH:2]([CH3:4])[CH3:3])=[N:11][CH:12]=[C:13]([CH3:18])[N:14]=1
Reactant: CC(C)COC(=O)Cl
Reactant: COc1nc(C)cnc1N
Solvent: c1ccncc1
Solvent: ClCCl
Product: COc1nc(C)cnc1NC(=O)OCC(C)C

Procedure:
Isobutylchloroformate (4.79 ml) was added to a stirred solution of 2-amino-3-methoxy-5-methylpyrazine (5 g) and pyridine (2.91 ml) in dichloromethane (10 ml) at ambient temperature. After 90 minutes the reaction mixture was diluted with dichloromethane (10 ml) and washed with 2M hydrochloric acid (3×20 ml), water (20 ml) and saturated sodium chloride solution (20 ml) and then dried (MgSO4). Volatile material was removed by evaporation to give a solid which was recrystallised from hexane to give isobutyl N-(3-methoxy-5-methylpyrazin-2-yl)carbamate (6.5 g); 1H NMR (CDCl3): 1.0 (d, 6 H), 2.0 (m, 1 H), 2.4 (s, 3 H), 4.0 (d, 2 H), 4.02 (s, 3 H), 7.3 (s, 1 H), 7.8 (s, 1 H); mass spectrum (positive chemical ionisation (+ve CI)): 240 (M+H)+.
Reaction SMILES: CN(C)C1CCCCC1.[CH:10]1[C:15]([OH:16])=[CH:14][CH:13]=[C:12]([CH3:17])[CH:11]=1.[C:18](Cl)(=[O:25])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[Cl-].[Cl-].[Cl-].[Al+3].Cl>ClC1C=CC=CC=1.O>[OH:16][C:15]1[CH:14]=[CH:13][C:12]([CH3:17])=[CH:11][C:10]=1[C:18]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:25]
Reactant: Cc1ccc(O)cc1
Reactant: O=C(Cl)c1ccccc1
Agent: Cl
Agent: [Al+3]
Agent: [Cl-]
Solvent: O
Solvent: CN(C)C1CCCCC1
Solvent: Clc1ccccc1
Product: Cc1ccc(O)c(C(=O)c2ccccc2)c1
Temperature: 50 °C
Yield: 81 %

Procedure:
##STR19## 38 g (0.3 mol) of dimethylcyclohexylamine and 27 g (0.25 mol) of p-cresol in 150 ml of chlorobenzene were initially taken. 35.1 g (0.25 mol) of benzoyl chloride were added dropwise over one hour, the temperature increasing to 50° C. After cooling to room temperature, the suspension was added to 100 ml of water in order to separate off the dimethylcyclohexylamine hydrochloride. The organic phase was separated off and was dried by partial distillation. 33 g (0.25 mol) of aluminum trichloride were then added a little at a time at room temperature in the course of 30 minutes. During this procedure, the internal temperature increased to 50° C. The batch was stirred at 130° C. for about 10 hours until the evolution of HCl gas had ceased. After cooling to 60° C., the reaction mixture was poured onto ice water. The phases were separated and the aqueous phase was extracted twice with chlorobenzene. The combined organic phases were dried over magnesium sulfate and then evaporated down. 43 g (corresponding to a yield of 81%) of 2-hydroxy-5-methylbenzophenone were obtained. 25 g (0.12 mol) of the compound were then dissolved in 150 ml of methanol, and 4.1 g of sodium hydroxide in 30 ml of methanol were then added. The refluxing reaction mixture was stirred for 3 hours and then evaporated down in a rotary evaporator. 27 g (corresponding to a yield of 98%) of the title compound were obtained in the form of an orange solid.
Reaction SMILES: Br[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[C:8]([O:12][C:13](=[O:18])[NH:14][CH2:15][CH2:16][NH2:17])([CH3:11])([CH3:10])[CH3:9].C(N(CC)CC)C>C1COCC1>[C:8]([O:12][C:13]([NH:14][CH2:15][CH2:16][NH:17][CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4])=[O:18])([CH3:11])([CH3:10])[CH3:9]
Reactant: CC(C)(C)OC(=O)NCCN
Reactant: CCOC(=O)CBr
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CCOC(=O)CNCCNC(=O)OC(C)(C)C
Temperature: 25 °C
Reaction time: 18 h

Procedure:
Ethyl bromoacetate (10.35 ml, 94.0 mmol) was added drop wise to a mixture of tert-butyl(2-aminoethyl)carbamate (15.0 g, 94.0 mmol), triethylamine (16.87 ml, 122 mmol) and THF (200 ml) at 0° C. After stirring 18 h at room temperature the reaction mixture was filtered, the filtrate diluted with DCM, washed with water, the organic layer dried over Na2SO4 and evaporated to give the title compound as a yellow oil. 1H NMR (400 MHz, DMSO-d6) δ 6.62 (s, br, 1H), 4.00 (q, 2H), 3.28 (s, 2H), 3.04-2.90 (m, 2H), 2.58-2.49 (m, 2H), 1.26 (s, 9H), 1.11 (t, 3H).
Reaction SMILES: [N:1]1[CH:6]=[C:5]([C:7]([OH:9])=O)[CH:4]=[CH:3][C:2]=1[C:10]([OH:12])=O.[CH2:13]([NH:18][CH2:19][CH2:20][CH:21]([CH3:23])[CH3:22])[CH2:14][CH:15]([CH3:17])[CH3:16]>>[CH2:19]([N:18]([CH2:13][CH2:14][CH:15]([CH3:16])[CH3:17])[C:10]([C:2]1[CH:3]=[CH:4][C:5]([C:7]([N:18]([CH2:19][CH2:20][CH:21]([CH3:23])[CH3:22])[CH2:13][CH2:14][CH:15]([CH3:16])[CH3:17])=[O:9])=[CH:6][N:1]=1)=[O:12])[CH2:20][CH:21]([CH3:23])[CH3:22]
Reactant: CC(C)CCNCCC(C)C
Reactant: O=C(O)c1ccc(C(=O)O)nc1
Product: CC(C)CCN(CCC(C)C)C(=O)c1ccc(C(=O)N(CCC(C)C)CCC(C)C)nc1

Procedure:
N,N,N',N'-tetraisoamyl pyridine-2,5-dicarboxamide was prepared using the method of Example 1 from pyridine-2,5-dicarboxylic acid and diisoamylamine. The crude product in toluene solution was washed several times with 0.5M aqueous sodium hydroxide and then with 0.5M aqueous hydrochloric acid and water. The solution was then treated with charcoal and filtered. The solvent was distilled under reduced pressure, but the product, a brown oil, was not itself distilled. It was made up as a 0.2M solution in AROMASOL H and tested for extraction of copper in the presence of chloride ion using the method of Examples 6 and 7 except that AROMASOL H was used as solvent. The results are given in Table 3. The results indicate that this is a very weak extractant suitable for recovering copper from aqueous solution of high chloride ion concentrations.
Reaction SMILES: [F:1][C:2]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([F:14])[CH:9]=2)=[CH:6][C:5]([CH3:15])=[CH:4][C:3]=1[CH2:16][NH:17][C:18]1[C:19]([CH3:33])=[C:20]([CH:29]=[CH:30][C:31]=1[CH3:32])[O:21][CH2:22][C:23]([O:25]C(C)C)=[O:24].[Li+].[OH-]>C1COCC1>[F:1][C:2]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([F:14])[CH:9]=2)=[CH:6][C:5]([CH3:15])=[CH:4][C:3]=1[CH2:16][NH:17][C:18]1[C:19]([CH3:33])=[C:20]([CH:29]=[CH:30][C:31]=1[CH3:32])[O:21][CH2:22][C:23]([OH:25])=[O:24]
Reactant: Cc1cc(CNc2c(C)ccc(OCC(=O)OC(C)C)c2C)c(F)c(-c2cccc(F)c2)c1
Agent: [Li+]
Agent: [OH-]
Solvent: C1CCOC1
Product: Cc1cc(CNc2c(C)ccc(OCC(=O)O)c2C)c(F)c(-c2cccc(F)c2)c1
Temperature: 25 °C
Reaction time: 8 h
Yield: 40.5 %

Procedure:
To a solution of isopropyl 2-[3-[[2-fluoro-3-(3-fluorophenyl)-5-methyl-phenyl]methylamino]-2,4-dimethyl-phenoxy]acetate (80 mg, 0.18 mmol, 1.0 eq) in THF (8 mL) at 0° C. was added LiOH (2M aqueous solution, 4 mL, 8.0 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight. The THF was removed and the remaining aqueous solution was diluted with water. The pH was adjusted to pH 4-6 by addition of diluted HCl. The solid precipitate that formed was collected by filtration, washed with water and dried in vacuo to give target compound as a yellow solid (30 mg, 41%).
Reaction SMILES: [Cl:1][CH2:2][C@@H:3]([OH:6])[CH2:4]O.S(Cl)(Cl)=O.ClC[C@H]1COS(=O)(=O)O1.Cl[O-].[Na+].[NH2:23][C:24]1[CH:29]=[CH:28][C:27]([N:30]2[CH2:35][CH2:34][O:33][CH2:32][C:31]2=[O:36])=[CH:26][CH:25]=1.C(N(CC)CC)C.CS(O)(=O)=O.C(=O)([O-])O.[Na+]>C(Cl)Cl.O>[Cl:1][CH2:2][C@H:3]([OH:6])[CH2:4][NH:23][C:24]1[CH:25]=[CH:26][C:27]([N:30]2[CH2:35][CH2:34][O:33][CH2:32][C:31]2=[O:36])=[CH:28][CH:29]=1
Reactant: OC[C@H](O)CCl
Reactant: Nc1ccc(N2CCOCC2=O)cc1
Agent: CS(=O)(=O)O
Agent: O=C([O-])O
Agent: O=S1(=O)OC[C@H](CCl)O1
Solvent: ClCCl
Solvent: O=S(Cl)Cl
Solvent: O
Product: O=C1COCCN1c1ccc(NC[C@@H](O)CCl)cc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 62.5 %

Procedure:
Under an atmosphere of nitrogen to a solution of 28.12 g of (S)-3-chloro-1,2-propanediol (MW=110.54; 1 eq.) in 600 mL of methylenechloride were added dropwise 30.26 g of thionylchloride (MW=118.97; 1 eq.). After stirring for 1 h at room temperature, the reaction mixture was concentrated in vacuo to a mass of 255 g. To the concentrate of (R)-4-chloromethyl-[1,3,2]dioxathiolane 2,2-dioxide (MW=156.59; 1 eq.) were added 200 mL of water and 45 mg of RuCl3.3 H2O (MW=261.47; 0.0007 eq.) The mixture was cooled to 0° C. At this temperature, 215 mL of a cold solution of sodium hypochlorite (1.7 M; 1.4 eq.) were added in 60 min. After addition of sodium hypochlorite was finished, the reaction mixture was stirred for 15 min at 0° C. Then the layers were separated. The aqueous layer was extracted twice with 160 mL of methylenechloride. To the combined methylenechloride layers were added 4 mL of isopropanol and 120 mL of water. After stirring for 5 min the layers were separated. To the organic layer, 1.6 g charcoal were added. After 5 min of stirring, the suspension was filtered. To the filtrate were added 32.09 g of 4-(4-aminophenyl)-morpholin-3-one (APMO) (MW=192.22; 0.66 eq.) and 23.28 g (MW=101.12; 0.9 eq.) of triethylamine. The reaction mixture was stirred for 24 h at room temperature. Then the resulting suspension was concentrated in vacuo and the concentrate was dissolved in 1000 mL of acetonitrile. 96 g of methane sulfonic acid (MW=96.11; 3.9 eq.) and 20 g of water (MW=18; 4.4 eq.) were added and the solution was stirred at ambient temperature. After stirring for 5 h, the reaction mixture was neutralized by addition of 127 g of sodium hydrogencarbonate (MW=84.01; 5.9 eq.). The resulting suspension was filtered and the cake washed with 500 mL of acetonitrile. The combined acetonitrile layers were concentrated in vacuo. To the concentrate were added 660 mL of 2-propanol and the mixture was stirred for 1 h at ambient temperature. The resulting slurry was cooled to 0° C. After stirring for at least 2 h at this temperature, the product was isolated by filtration and the filter cake was washed with 125 mL of 2-propanol. After drying in vacuo at 30° C., 29.73 g of the crystalline title compound were isolated. Yield=41.0%.
Reaction SMILES: [C:1](Cl)(=[O:5])[C:2]([CH3:4])=[CH2:3].[C:7]([NH:11][C:12](=[O:16])[C:13]([CH3:15])=[CH2:14])([CH3:10])([CH3:9])[CH3:8].C(N(CC)CC)C.C(OCC)C>C(Cl)Cl>[CH3:4][C:2]([C:1](=[O:5])[N:11]([C:7]([CH3:10])([CH3:9])[CH3:8])[C:12](=[O:16])[C:13]([CH3:15])=[CH2:14])=[CH2:3]
Reactant: C=C(C)C(=O)NC(C)(C)C
Reactant: C=C(C)C(=O)Cl
Solvent: CCOCC
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: C=C(C)C(=O)N(C(=O)C(=C)C)C(C)(C)C
Reaction time: 0.5 h

Procedure:
A solution of 52.7 g of methacrylyl chloride in 570 ml of methylene chloride is added dropwise to a stirred solution, cooled to 0°-5° C., of 71 g of N-tert-butyl-methacrylamide, 50.8 g of triethylamine and 570 ml of methylene chloride. After the addition, the mixture is stirred for 2 1/2 hours and the reaction solution is left to stand for 4 days. The concentrated reaction material is taken up in 0.5 1 of diethyl ether, the mixture is filtered and the solution is concentrated. The red oil obtained is filtered with hexane-diethyl ether (4:1) on silica gel to give the title compound as a white crystalline product (m.p. 47°-48° C).
Reaction SMILES: [CH2:1]([N:8]([CH2:10][CH2:11][C:12]1[C:20]2[C:15](=[CH:16][CH:17]=[C:18]([Cl:21])[CH:19]=2)[NH:14][CH:13]=1)[CH3:9])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[F:22][C:23]1[CH:28]=[CH:27][C:26](I)=[CH:25][CH:24]=1.C([O-])([O-])=O.[K+].[K+].CN1CCCC1=O>O>[CH2:1]([N:8]([CH2:10][CH2:11][C:12]1[C:20]2[C:15](=[CH:16][CH:17]=[C:18]([Cl:21])[CH:19]=2)[N:14]([C:26]2[CH:27]=[CH:28][C:23]([F:22])=[CH:24][CH:25]=2)[CH:13]=1)[CH3:9])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: Fc1ccc(I)cc1
Reactant: CN(CCc1c[nH]c2ccc(Cl)cc12)Cc1ccccc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CN1CCCC1=O
Product: CN(CCc1cn(-c2ccc(F)cc2)c2ccc(Cl)cc12)Cc1ccccc1
Temperature: 165 °C

Procedure:
A mixture of N-benzyl-N-methyl-2-(5-chloro-3-1H-indolyl)ethylamine (16 g, 0.054 mol), 4-fluoro-iodobenzene (14.3 g, 0.064 mol), K2CO3 (11.1 g, 0.080 mol) and 1-methyl-2-pyrrolidinone (200 mL) was heated at 165° C. for 8 h. After cooling to room temperature water (250 mL) was added and the thus formed mixture was extracted with diethyl ether (2×300 mL). The combined organic phases were washed with brine (3×500 mL) and dried (Na2SO4). Evaporation of the solvent afforded an oil that was purified by column chromatography (eluted with ethyl acetate/heptane 1:3) affording pure title compound as an oil: 13.7 g (26%) 1H NMR (CDCl3) δ 2.35 (s, 3 H), 2.70-2.80 (m, 2 H), 2.90-3.00 (m, 2 H), 3.60 (s, 2 H), 7.05-7.40 (m, 12 H), 7.55 (broad s, 1 H).
Reaction SMILES: COC1C=C(C(C2C=CC(OC)=C(OC)C=2)=CC(OC)=O)C=CC=1OC.[CH3:27][O:28][C:29]1[CH:30]=[C:31]([CH:43]=[CH:44][C:45]=1[O:46][CH3:47])[C:32]([C:34]1[CH:39]=[CH:38][C:37]([N+:40]([O-:42])=[O:41])=[CH:36][CH:35]=1)=O.C(OP([CH2:56][C:57]#[N:58])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[CH3:27][O:28][C:29]1[CH:30]=[C:31]([C:32]([C:34]2[CH:39]=[CH:38][C:37]([N+:40]([O-:42])=[O:41])=[CH:36][CH:35]=2)=[CH:56][C:57]#[N:58])[CH:43]=[CH:44][C:45]=1[O:46][CH3:47]
Reactant: CCOP(=O)(CC#N)OCC
Reactant: COc1ccc(C(=O)c2ccc([N+](=O)[O-])cc2)cc1OC
Agent: COC(=O)C=C(c1ccc(OC)c(OC)c1)c1ccc(OC)c(OC)c1
Agent: C[Si](C)(C)[N-][Si](C)(C)C
Agent: [Li+]
Product: COc1ccc(C(=CC#N)c2ccc([N+](=O)[O-])cc2)cc1OC

Procedure:
3-(3,4-Dimethoxyphenyl)-3-(4′-nitrophenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3′,4′-dimethoxyphenyl)acrylate using 3,4-dimethoxy-4′nitrobenzophenone (4 g, 14 mmol), diethylcyanomethylphosphonate (2.5 mL, 15.4 mmol) and lithium hexamethyldisilazide (11.8 mL, 15.4 mmol, 1.3M) with a reaction time of 17 hours at room temperature. The crude product was purified by chromatography (silica gel, 3% hexane/methylene chloride) to afford 2.38 g (55%) of a mixture of the E and Z isomers as a yellow solid: mp 117.5-120° C.; 1HNMR (CDCl3) δ8.40-8.20 (m, 4 H), 7.70-7.46 (m, 4 H), 7.06-6.75 (m, 6 H), 5.84 (s, 1 H), 5.70 (s, 1 H), 3.95 (s, 3 H), 3.93 (s, 3 H), 3.88 (s, 3 H), 3.85 (s, 3 H); 13C NMR (CDCl3) δ160.3, 151.7, 151.1, 149.2, 148.9, 148.7, 148.5, 148.5, 143.5, 130.6, 129.9, 129.6, 128.2, 123.7, 123.1, 122.2, 117.4, 117.3, 112.3, 111.0, 110.5, 96.2, 94.9, 56.0, 56.0; Anal. Calcd for C17H14N2O4. Theoretical: C, 65.80; H, 4.55; N, 9.03. Found: C, 65.45; H, 4.66; N, 8.82.
Reaction SMILES: CC(C)([O-])C.[K+].[CH2:7]([S:9][C:10]1[NH:11][C:12]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[C:13]([C:15]([OH:18])([CH3:17])[CH3:16])[N:14]=1)[CH3:8].[C:24]([N:43]1[C:47]([C:48]2[CH:53]=[CH:52][CH:51]=[CH:50][C:49]=2[C:54]2[CH:61]=[CH:60][C:57]([CH2:58]Br)=[CH:56][CH:55]=2)=[N:46][N:45]=[N:44]1)([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>CN(C)C(=O)C>[CH2:7]([S:9][C:10]1[N:11]([CH2:58][C:57]2[CH:56]=[CH:55][C:54]([C:49]3[CH:50]=[CH:51][CH:52]=[CH:53][C:48]=3[C:47]3[N:43]([C:24]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)([C:31]4[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=4)[C:25]4[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=4)[N:44]=[N:45][N:46]=3)=[CH:61][CH:60]=2)[C:12]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[C:13]([C:15]([OH:18])([CH3:16])[CH3:17])[N:14]=1)[CH3:8]
Reactant: BrCc1ccc(-c2ccccc2-c2nnnn2C(c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Reactant: CCOC(=O)c1[nH]c(SCC)nc1C(C)(C)O
Agent: CC(C)(C)[O-]
Agent: [K+]
Solvent: CC(=O)N(C)C
Product: CCOC(=O)c1c(C(C)(C)O)nc(SCC)n1Cc1ccc(-c2ccccc2-c2nnnn2C(c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Reaction time: 0.5 h
Yield: 78 %

Procedure:
478 mg of potassium t-butoxide were added to a solution of 1.00 g of ethyl 2-ethylthio-4-(1-hydroxy-1-methylethyl)imidazole-5-carboxylate [prepared as described in Preparation 50(ii)] in 20 ml of N,N-dimethylacetamide, whilst ice-cooling, and the mixture was stirred for 30 minutes. At the end of this time, 2.59 g of 4-[2-(trityltetrazol-5-yl)phenyl]benzyl bromide were added in portions to the mixture. Following a procedure similar to that described in Example 105(a) and purifying the residue by column chromatography through silica gel using a 1:5 by volume mixture of ethyl acetate and hexane as the eluent, 2.22 g of the title compound were obtained as an amorphous powder.
Reaction SMILES: C(S[N:6]=[N:7][C:8]1[C:9]([CH3:19])=[C:10]([C:15]([F:18])=[CH:16][CH:17]=1)[C:11]([O:13][CH3:14])=[O:12])(C)(C)C.CC(C)([O-])C.[K+]>CS(C)=O.O>[F:18][C:15]1[CH:16]=[CH:17][C:8]2[C:9](=[CH:19][NH:6][N:7]=2)[C:10]=1[C:11]([O:13][CH3:14])=[O:12]
Reactant: COC(=O)c1c(F)ccc(N=NSC(C)(C)C)c1C
Agent: CC(C)(C)[O-]
Agent: [K+]
Solvent: CS(C)=O
Solvent: O
Product: COC(=O)c1c(F)ccc2n[nH]cc12
Reaction time: 12 h
Yield: 25.3 %

Procedure:
To a solution of a crudely purified product (18.5 g, 65.1 mmol) of methyl 3-[(tert-butylthio)diazenyl]-6-fluoro-2-methylbenzoate in dimethyl sulfoxide (200 mL) was added a solution of potassium tert-butoxide (10.6 g, 98.0 mmol) in dimethyl sulfoxide (125 mL) at room temperature, and the mixture was stirred for 12 hr. The reaction solution was diluted with water, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by flash silica gel column chromatography (ethyl acetate/hexane=1/2) to give the title compound (3.20 g, yield 25%).
Reaction SMILES: C(=O)([O-])[O-].[K+].[K+].S(S([O-])=O)([O-])=O.[Na+].[Na+].[C:15]([O:19][C:20](=[O:45])[NH:21][CH2:22][C:23]1[CH:28]=[CH:27][C:26]([CH2:29][NH:30][C:31]2[C:40]3[C:35](=[CH:36][C:37]([Br:41])=[CH:38][CH:39]=3)[N:34]=[CH:33][C:32]=2[N+:42]([O-])=O)=[CH:25][CH:24]=1)([CH3:18])([CH3:17])[CH3:16]>O.ClCCl.CC[N+]1C=CC(C2C=C[N+](CC)=CC=2)=CC=1.[Br-].[Br-]>[C:15]([O:19][C:20](=[O:45])[NH:21][CH2:22][C:23]1[CH:28]=[CH:27][C:26]([CH2:29][NH:30][C:31]2[C:40]3[C:35](=[CH:36][C:37]([Br:41])=[CH:38][CH:39]=3)[N:34]=[CH:33][C:32]=2[NH2:42])=[CH:25][CH:24]=1)([CH3:18])([CH3:16])[CH3:17]
Reactant: CC(C)(C)OC(=O)NCc1ccc(CNc2c([N+](=O)[O-])cnc3cc(Br)ccc23)cc1
Agent: CC[n+]1ccc(-c2cc[n+](CC)cc2)cc1
Agent: O=C([O-])[O-]
Agent: O=S([O-])S(=O)[O-]
Solvent: ClCCl
Solvent: O
Product: CC(C)(C)OC(=O)NCc1ccc(CNc2c(N)cnc3cc(Br)ccc23)cc1
Reaction time: 20 h
Yield: 100.5 %

Procedure:
Ethyl viologen dibromide (0.069 g, 0.18 mmol), potassium carbonate (12.76 g, 92 mmol) in water (55mL), and sodium hydrosulfite (11.25 g, 65 mmol) in water (55mL) were added sequentially to a solution of tert-butyl{4-[(7-bromo-3-nitroquinolin-4-ylamino)methyl]benzyl}carbamate (9.0 g, 18.5 mmol) in dichloromethane (110 mL). The resulting biphasic mixture was stirred for 20 hours. The reaction was diluted with water (600 mL) and dichloromethane (500 mL). The layers were separated and the aqueous fraction was extracted with dichloromethane. The organic fractions were combined and washed sequentially with water and saturated aqueous sodium chloride. The organic fraction was dried over sodium sulfate, filtered, and concentrated under reduced pressure to yield 8.5 g of tert-butyl{4-[(3-amino-7-bromoquinolin-4-ylamino)methyl]benzyl}carbamate as a yellow-brown amorphous solid.