Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1.Cl.C(N(CC)CC)C.[C:16]([Si:18]([CH3:21])([CH3:20])[CH3:19])#[CH:17]>C(OCC)(=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH3:19][Si:18]([C:16]#[C:17][C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1)([CH3:21])[CH3:20]
Reactant: C#C[Si](C)(C)C
Reactant: Brc1ccncc1
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: [Cu]I
Agent: Cl
Solvent: O
Solvent: CCN(CC)CC
Solvent: CCOC(C)=O
Product: C[Si](C)(C)C#Cc1ccncc1
Temperature: 25 °C
Reaction time: 72 h

Procedure:
A flask was charged with 4-bromopyridine.HCl (2.46 g, 12.65 mmol) and triethylamine (40 mL) and sparged with nitrogen for 15 min. To this was added ethynyltrimethylsilane (1.967 mL, 13.92 mmol) and purged 15 min longer. To this was added copper(I) iodide (0.120 g, 0.633 mmol), and Pd(PPh3)2Cl2 (0.444 g, 0.633 mmol). The reaction was stirred at room temperature for 72 h. The reaction was warmed to 50° C. and held at that temperature for 24 h. The reaction was diluted with ethyl acetate (60 mL) and poured into water. The black heterogeneous emulsion was filtered through a plug of celite and the layers separated. The organics were washed with brine, dried over magnesium sulfate, and concentrated. Column chromatography (5%-->25% EtOAc/Hex) gave 667 mg (30%) as a dark oil. 1H-NMR (CDCl3, 500 MHz) δ 8.58 (d, J=6.1, 2H), 7.33 (d, J=6.1, 2H), 0.29 (s, 9H). 13C-NMR (CDCl3, 126 MHz) δ 149.8, 131.3, 125.9, 102.1, 100.1, −0.2. Mass spec.: 176.14 (MH)+.
Reaction SMILES: [N+:1]([C:4]1[CH:5]=[C:6](C=C[CH:30]=1)[CH:7]=[CH:8][C:9]([CH2:11][C:12]([O:14][CH2:15][CH2:16][O:17][C:18]1[CH:23]=[CH:22][C:21]([NH:24][C:25](=[O:27])[CH3:26])=[CH:20][CH:19]=1)=[O:13])=O)([O-:3])=[O:2].[NH2:31]/[C:32](/[CH3:41])=[CH:33]\[C:34]([O:36][CH2:37][CH2:38][S:39][CH3:40])=[O:35].[CH2:42](O)[CH3:43]>>[CH3:42][C:43]1[NH:31][C:32]([CH3:41])=[C:33]([C:34]([O:36][CH2:37][CH2:38][S:39][CH3:40])=[O:35])[CH:9]([C:8]2[CH:7]=[CH:6][CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:30]=2)[C:11]=1[C:12]([O:14][CH2:15][CH2:16][O:17][C:18]1[CH:19]=[CH:20][C:21]([NH:24][C:25](=[O:27])[CH3:26])=[CH:22][CH:23]=1)=[O:13]
Reactant: CCO
Reactant: CC(=O)Nc1ccc(OCCOC(=O)CC(=O)C=Cc2cccc([N+](=O)[O-])c2)cc1
Reactant: CSCCOC(=O)/C=C(/C)N
Product: CSCCOC(=O)C1=C(C)NC(C)=C(C(=O)OCCOc2ccc(NC(C)=O)cc2)C1c1cccc([N+](=O)[O-])c1
Temperature: -5 °C
Yield: 80 %

Procedure:
15 g (0.04 moles) of 2-(4-acetylaminophenoxy)ethyl 2-(3-nitrobenzylidene)acetylacetate and 6.37 g (0.04 moles) of 2-methylthioethyl 3-aminocrotonate are heated under reflux in 30 ml of ethanol during 8 hours. The solution is then cooled to -5° C. to obtain 2-(4-acetylaminophenoxy)ethyl 2,6-dimethyl-5-(2-methylthioethoxycarbonyl)-4-(3-nitrophenyl)-1,4-dihydropyridine-3-carboxylate as yellow crystals melting--after recrystallisation in ethanol--at 76° C.-80° C. The yield is 80% of the theoretical yield.
Reaction SMILES: [F:1][C:2]1[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[C:3]=1[CH2:4][O:5][C:6]1[C:7]2[N:8]([C:13]([C:17](O)=[O:18])=[C:14]([CH3:16])[N:15]=2)[CH:9]=[C:10]([CH3:12])[CH:11]=1.F[B-](F)(F)F.N1(O[C+](N(C)C)N(C)C)C2C=CC=CC=2N=N1.CN1CCOCC1.[CH3:54][C:55]([NH2:59])([CH3:58])[CH2:56][NH2:57]>CN(C=O)C>[NH2:59][C:55]([CH3:58])([CH3:54])[CH2:56][NH:57][C:17]([C:13]1[N:8]2[CH:9]=[C:10]([CH3:12])[CH:11]=[C:6]([O:5][CH2:4][C:3]3[C:2]([F:1])=[CH:23][CH:22]=[CH:21][C:20]=3[F:24])[C:7]2=[N:15][C:14]=1[CH3:16])=[O:18]
Reactant: Cc1cc(OCc2c(F)cccc2F)c2nc(C)c(C(=O)O)n2c1
Reactant: CC(C)(N)CN
Agent: CN(C)[C+](On1nnc2ccccc21)N(C)C
Agent: F[B-](F)(F)F
Solvent: CN(C)C=O
Solvent: CN1CCOCC1
Product: Cc1cc(OCc2c(F)cccc2F)c2nc(C)c(C(=O)NCC(C)(C)N)n2c1
Temperature: 25 °C
Reaction time: 8 h

Procedure:
100 mg of 8-[(2,6-difluorobenzyl)oxy]-2,6-dimethylimidazo[1,2-a]pyridine-3-carboxylic acid (0.30 mmol), 145 mg of (benzotriazol-1-yloxy)bisdimethylaminomethylium fluoroborate (TBTU, 0.45 mmol) and 122 mg of 4-methylmorpholine (1.20 mmol) were initially charged in 1.9 ml of DMF. 53 mg of 2-methylpropane-1,2-diamine (0.60 mmol) were then added, and the mixture was stirred at RT overnight. The reaction solution was purified by preparative HPLC (RP18 column, mobile phase: acetonitrile/water gradient with addition of 0.1% TFA). The product fractions were taken up in dichloromethane and washed with saturated aqueous sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane. The combined organic phases were dried over sodium sulphate, filtered, concentrated and lyophilized. This gave 94 mg of the title compound (78% of theory).
Reaction SMILES: [C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH:16]([C:22](=O)[CH2:23][CH2:24][CH3:25])[C:17](OCC)=[O:18])=[CH:11][C:10]=1[F:27])#[N:2].[O:28]1[C:32]2([CH2:37][CH2:36][CH:35]([NH:38][C:39]3[NH:43][CH:42]=[N:41][N:40]=3)[CH2:34][CH2:33]2)[O:31][CH2:30][CH2:29]1>>[O:28]1[C:32]2([CH2:33][CH2:34][CH:35]([N:38]3[C:17](=[O:18])[C:16]([CH2:15][C:12]4[CH:13]=[CH:14][C:9]([C:4]5[C:3]([C:1]#[N:2])=[CH:8][CH:7]=[CH:6][CH:5]=5)=[C:10]([F:27])[CH:11]=4)=[C:22]([CH2:23][CH2:24][CH3:25])[N:40]4[N:41]=[CH:42][N:43]=[C:39]34)[CH2:36][CH2:37]2)[O:31][CH2:30][CH2:29]1
Reactant: c1nnc(NC2CCC3(CC2)OCCO3)[nH]1
Reactant: CCCC(=O)C(Cc1ccc(-c2ccccc2C#N)c(F)c1)C(=O)OCC
Product: CCCc1c(Cc2ccc(-c3ccccc3C#N)c(F)c2)c(=O)n(C2CCC3(CC2)OCCO3)c2ncnn12
Temperature: 250 °C
Reaction time: 1 h
Yield: 51 %

Procedure:
A mixture of ethyl 2-[(2′-cyano-2-fluorobiphenyl-4-yl)methyl]-3-oxohexanoate (3.3 g) and N-(1,4-dioxaspiro[4.5]dec-8-yl)-4H-1,2,4-triazol-3-amine (1 g) was stirred at 250° C. for 1 hr under microwave irradiation. The reaction mixture was purified by silica gel column chromatography to give the title compound as a colorless solid (1.2 g, 50%).
Reaction SMILES: [OH:1][C:2]1[CH:7]=[C:6]([OH:8])[CH:5]=[CH:4][C:3]=1[C:9](=[O:12])[CH2:10][CH3:11].Br[CH2:14][C:15]#[CH:16].C([O-])([O-])=O.[K+].[K+]>CC(C)=O>[OH:1][C:2]1[CH:7]=[C:6]([O:8][CH2:16][C:15]#[CH:14])[CH:5]=[CH:4][C:3]=1[C:9](=[O:12])[CH2:10][CH3:11]
Reactant: CCC(=O)c1ccc(O)cc1O
Reactant: C#CCBr
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC(C)=O
Product: C#CCOc1ccc(C(=O)CC)c(O)c1
Yield: 85.5 %

Procedure:
A mixture of 2′,4′-dihydroxy-propiophenone (24.9 g, 0.15 mol), 3-bromo-propyne (24.2 g, 0.20 mol) and K2CO3 (20.7 g, 0.15 mol) in acetone (500 mL) was refluxed for 12 h. The reaction mixture was allowed assume room temperature and the precipitate was removed by filtration. The filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 0→2% MeOH in H2O), to give 26.2 g (85%) of 1-(2-hydroxy-4-prop-2-ynyloxy-phenyl)-propan-1-one.
Reaction SMILES: [OH:1][CH:2]1[CH2:7][CH2:6][C:5]([C:9]([C:11]2[C:19]3[C:14](=[N:15][CH:16]=[C:17]([C:20]4[CH:25]=[C:24]([O:26][CH3:27])[C:23]([O:28][CH3:29])=[C:22]([O:30][CH3:31])[CH:21]=4)[N:18]=3)[NH:13][CH:12]=2)=[O:10])([CH3:8])[CH2:4][CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH:51](O)=[O:52].N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH3:8][C:5]1([C:9]([C:11]2[C:19]3[C:14](=[N:15][CH:16]=[C:17]([C:20]4[CH:21]=[C:22]([O:30][CH3:31])[C:23]([O:28][CH3:29])=[C:24]([O:26][CH3:27])[CH:25]=4)[N:18]=3)[NH:13][CH:12]=2)=[O:10])[CH2:4][CH2:3][CH:2]([O:1][CH:51]=[O:52])[CH2:7][CH2:6]1
Reactant: O=CO
Reactant: COc1cc(-c2cnc3[nH]cc(C(=O)C4(C)CCC(O)CC4)c3n2)cc(OC)c1OC
Agent: CCOC(=O)N=NC(=O)OCC
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: C1CCOC1
Product: COc1cc(-c2cnc3[nH]cc(C(=O)C4(C)CCC(OC=O)CC4)c3n2)cc(OC)c1OC
Temperature: 25 °C
Reaction time: 48 h
Yield: 58.8 %

Procedure:
A solution of (4-hydroxy-1-methyl-cyclohexyl)-[2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazin-7-yl]-methanone (19 mg, 0.045 mmol), triphenyl phosphine (23 mg, 0.088 mmol), and formic acid (0.003 ml, 0.087 mmol), in THF (0.4 ml), was treated with diethyl azodicarboxylate (0.01 ml, 0.092 mmol). After stirring at room temperature for 2 days, the reaction mixture was purified by preparative thin layer chromatography using 70% EtOAc in Hexanes as eluant providing 12 mg (59%) of formic acid 4-methyl-4-[2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazine-7-carbonyl]-cyclohexyl ester as a white solid. M+H=454.
Reaction SMILES: F[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[NH:11]1[CH2:15][CH2:14][CH:13]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:12]1.O>CN(C)C=O>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([N:11]2[CH2:15][CH2:14][CH:13]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:21])([CH3:20])[CH3:22])[CH2:12]2)=[CH:3][CH:4]=1)([O-:10])=[O:9]
Reactant: O=[N+]([O-])c1ccc(F)cc1
Reactant: CC(C)(C)OC(=O)NC1CCNC1
Solvent: O
Solvent: CN(C)C=O
Product: CC(C)(C)OC(=O)NC1CCN(c2ccc([N+](=O)[O-])cc2)C1
Temperature: 25 °C
Reaction time: 8 h

Procedure:
A solution of 1-fluoro-4-nitrobenzene (508 mg, 3.6 mmol) and tert-butyl pyrrolidin-3-ylcarbamate (671 mg, 3.6 mmol) in N,N-dimethylformamide (7 mL) was heated at 55° C. for 1.5 hours and then stirred overnight at room temperature. The reaction mixture was poured into water and the suspension was filtered with water washes to provide the title compound after drying.
Reaction SMILES: Cl[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][N:3]=1.[C:12]([O:16][C:17]([N:19]1[CH2:24][CH2:23][NH:22][CH2:21][CH2:20]1)=[O:18])([CH3:15])([CH3:14])[CH3:13].C1CCN2C(=NCCC2)CC1>O>[C:12]([O:16][C:17]([N:19]1[CH2:24][CH2:23][N:22]([C:2]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[CH:5]=[CH:4][N:3]=2)[CH2:21][CH2:20]1)=[O:18])([CH3:15])([CH3:13])[CH3:14]
Reactant: CC(C)(C)OC(=O)N1CCNCC1
Reactant: Clc1nccc2ccccc12
Solvent: O
Solvent: C1CCC2=NCCCN2CC1
Product: CC(C)(C)OC(=O)N1CCN(c2nccc3ccccc23)CC1
Temperature: 107.5 °C
Yield: 66 %

Procedure:
1-Chloro-isoquinoline (176 mg, 1.07 mmol), piperazine-1-carboxylic acid tert-butyl ester (420 mg, 2.26 mmol) and DBU (0.25 mL, 1.61 mmol) were added into DMP (2 mL). The mixture was heated to 105-110° C. for overnight. The residue was diluted with water and extracted with ether. The organic layer was washed with brine, dried over Na2SO4 and concentrated in vacuo to dryness. The resulting residue was purified by column chromatography (5% to 10% ethyl acetate/hexane) to give 222 mg of the desired product 4-isoquinolin-1-yl-piperazine-1-carboxylic acid tert-butyl ester (yield: 66%).
Reaction SMILES: [N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH2:7][NH2:8])([O-:3])=[O:2].[Cl:12][C:13]1[N:14]=[C:15](Cl)[C:16]2[C:21]([Cl:22])=[C:20]([CH3:23])[S:19][C:17]=2[N:18]=1>>[Cl:12][C:13]1[N:14]=[C:15]([NH:8][CH2:7][C:6]2[CH:9]=[CH:10][CH:11]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=2)[C:16]2[C:21]([Cl:22])=[C:20]([CH3:23])[S:19][C:17]=2[N:18]=1
Reactant: Cc1sc2nc(Cl)nc(Cl)c2c1Cl
Reactant: NCc1cccc([N+](=O)[O-])c1
Product: Cc1sc2nc(Cl)nc(NCc3cccc([N+](=O)[O-])c3)c2c1Cl

Procedure:
Following the procedure of Example 1, the reaction of 3-nitrobenzylamine with 2,4,5-trichloro-6-methyl-thieno-[2,3-d]-pyrimidine yields 2,5-dichloro-6-methyl-4-(3-nitrobenzylamino)-thieno-[2,3-d]-pyrimidine
Reaction SMILES: [NH2:1][C:2]1[N:7]=[C:6](Cl)[C:5]([C:9]#[N:10])=[C:4]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=2)[N:3]=1.[CH2:19]([OH:26])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C1CCN2C(=NCCC2)CC1>COCCOC>[NH2:1][C:2]1[N:7]=[C:6]([O:26][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:5]([C:9]#[N:10])=[C:4]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=2)[N:3]=1
Reactant: OCc1ccccc1
Reactant: N#Cc1c(Cl)nc(N)nc1OCc1ccccn1
Solvent: C1CCC2=NCCCN2CC1
Solvent: COCCOC
Product: N#Cc1c(OCc2ccccc2)nc(N)nc1OCc1ccccn1

Procedure:
From 2-amino-4-chloro-6-(pyridin-2-ylmethoxy)-pyrimidine-5-carbonitrile, benzyl alcohol and DBU in DME. ES-MS m/e (%): 356 (MNa+, 50), 334 (M+H+, 100).
Reaction SMILES: [Si:1]([O:18][CH2:19][CH2:20][CH:21]([CH2:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[C:22]([O-:24])=O)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.CN[O:36][CH3:37].C1C=CC2N(O)N=[N:44][C:42]=2C=1.CCN=C=NCCCN(C)C.Cl>O.CN(C=O)C.C(N(CC)CC)C>[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:22](=[O:24])[NH:44][CH2:42][O:36][CH3:37])[CH2:25][C:26]([O:28][C:29]([CH3:31])([CH3:32])[CH3:30])=[O:27])([C:14]([CH3:17])([CH3:15])[CH3:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: CNOC
Reactant: CC(C)(C)OC(=O)CC(CCO[Si](c1ccccc1)(c1ccccc1)C(C)(C)C)C(=O)[O-]
Reactant: On1nnc2ccccc21
Agent: CCN=C=NCCCN(C)C
Agent: Cl
Solvent: CCN(CC)CC
Solvent: O
Solvent: CN(C)C=O
Product: COCNC(=O)C(CCO[Si](c1ccccc1)(c1ccccc1)C(C)(C)C)CC(=O)OC(C)(C)C
Temperature: 25 °C
Reaction time: 8 h

Procedure:
4-tert-Butyl 2-[2-(tert-butyldiphenylsilanyloxy)ethyl]succinate (437.4 g), triethylamine (171 mL) and DMF (2000 mL) were mixed. To the mixture were added N,O-dimethylhydroxylamine hydrochloride (111 g), HOBt.H2O (161 g) and WSC.HCl (201 g) at ice temperature. After stirring at RT overnight, water (800 mL) was poured into the reaction mixture and the mixture was extracted with hexane (2.4 L). The organic layer was washed with water (1.2 L) and 10 w/v % saline solution (1.2 L). The aqueous layer was extracted with hexane (2.4 L) once again and the combined organic layer was dried over sodium sulfate. The sodium sulfate was filtered off and the filtrate was concentrated in vacuo to give the title compound (425.1 g) as a crude product.
Reaction SMILES: [B:1](OC(C)C)([O:6]C(C)C)[O:2]C(C)C.Br[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[S:21][CH2:22][CH3:23].[Li]CCCC.CCCCCC.Cl>C(OCC)(=O)C>[CH2:22]([S:21][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[B:1]([OH:6])[OH:2])[CH3:23]
Reactant: CC(C)OB(OC(C)C)OC(C)C
Reactant: CCSc1ccccc1Br
Agent: Cl
Agent: [Li]CCCC
Solvent: CCOC(C)=O
Solvent: CCCCCC
Product: CCSc1ccccc1B(O)O
Temperature: -70 °C
Reaction time: 0.5 h

Procedure:
9.5 g (50 mmol) of triisopropyl borate are added to a solution of 10.9 g (50.0 mmol) of 1-bromo-2-ethylsulfanylbenzene kept at −70° C. 33.3 ml of a 15% solution of BuLi in hexane (55 mmol) are then added. The mixture is stirred at −70° C. for a further 30 minutes, then 1 N hydrochloric acid and ethyl acetate are added. The organic phase is separated off, dried and evaporated. The residue is taken up in diethyl ether and filtered. A colourless solid is obtained; FAB 182
Reaction SMILES: N([O-])=O.[Na+].N[C:6]1[CH:30]=[CH:29][C:9]([O:10][C:11]2[C:12]([C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[N:13][N:14]([CH3:22])[C:15]=2[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:8][CH:7]=1.[ClH:31]>O>[Cl:31][C:6]1[CH:30]=[CH:29][C:9]([O:10][C:11]2[C:12]([C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[N:13][N:14]([CH3:22])[C:15]=2[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:8][CH:7]=1
Reactant: Cn1nc(-c2ccccc2)c(Oc2ccc(N)cc2)c1-c1ccccc1
Reactant: Cl
Agent: O=N[O-]
Agent: [Na+]
Solvent: O
Product: Cn1nc(-c2ccccc2)c(Oc2ccc(Cl)cc2)c1-c1ccccc1

Procedure:
A solution of sodium nitrite (3.1 g, 0.0422 mole) in water (10 ml) is added slowly at 0° C to 5° C to a well stirred, chilled solution of 4-(p-aminophenoxy)-1-methyl-3,5-diphenylpyrazole (15.1 g, 0.0442 mole) in concentrated hydrochloric acid (50 ml).
Reaction SMILES: S([C:11]1[C:24]2[C:23](=[O:25])[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16](=[O:26])[C:15]=2[C:14]([S:27]([C:30]2[CH:36]=[CH:35][C:33]([CH3:34])=[CH:32][CH:31]=2)(=[O:29])=[O:28])=[CH:13][CH:12]=1)(C1C=CC(C)=CC=1)(=O)=O.[CH2:37]([NH2:40])[CH2:38][CH3:39]>>[CH2:37]([NH:40][C:11]1[C:24]2[C:23](=[O:25])[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16](=[O:26])[C:15]=2[C:14]([S:27]([C:30]2[CH:31]=[CH:32][C:33]([CH3:34])=[CH:35][CH:36]=2)(=[O:29])=[O:28])=[CH:13][CH:12]=1)[CH2:38][CH3:39]
Reactant: CCCN
Reactant: Cc1ccc(S(=O)(=O)c2ccc(S(=O)(=O)c3ccc(C)cc3)c3c2C(=O)c2ccccc2C3=O)cc1
Product: CCCNc1ccc(S(=O)(=O)c2ccc(C)cc2)c2c1C(=O)c1ccccc1C2=O
Yield: 73 %

Procedure:
1-(n-propylamino)-4-tosylanthraquinone was prepared by reaction of 1,4-ditosylanthraquinone with n-propyl amine. The isolated and purified reaction product has the structure illustrated below (where "Ts" is ##STR10## The yield was 73% and the m.p. 163°-164° C. Mass spec m/e 435 (M+), 406 (M-C2H5), 280 (M-C7H7SO2), 252 (280-CO), 155 (C7H7SO2), 91 (C7H7); 1H-NMR (CD2Cl2)δ10.01 (br s, 1H), 8.21-7.87 (m, 2H), 7.81-7.65 (m, 4H), 7.35-6.96 (m, 4H), 3.41-3.20 (m, 2H), 2.31 (s, 3H), 1.91-1.67 (m,2H), 1.16-1.00 (t, 3H); IR (Nujol) 1368 cm-1 (asymmetrical stretch), 1170 cm-1 (symmetric stretch), 932, 898, 865, 830, 785 cm-1 (S--O--C stretch); UV/VIS max (Xylenes) 501 nm (ε6380).
Reaction SMILES: [CH3:1][CH2:2][OH:3].[K].Cl[C:6]1[C:7]([C:16]([F:19])([F:18])[F:17])=[CH:8][C:9]([N+:13]([O-:15])=[O:14])=[C:10]([NH2:12])[CH:11]=1.Cl>O>[CH2:2]([O:3][C:6]1[C:7]([C:16]([F:17])([F:19])[F:18])=[CH:8][C:9]([N+:13]([O-:15])=[O:14])=[C:10]([NH2:12])[CH:11]=1)[CH3:1]
Reactant: CCO
Reactant: Nc1cc(Cl)c(C(F)(F)F)cc1[N+](=O)[O-]
Agent: Cl
Agent: [K]
Solvent: O
Product: CCOc1cc(N)c([N+](=O)[O-])cc1C(F)(F)F
Yield: 96 %

Procedure:
To EtOH (500 mL) was added potassium metal (ca. 21 g, ca. 537 mmol), and the vigorous reaction had to be cooled with an ice bath. Stirring was continued until all potassium metal was dissolved. Solid commercially available 5-chloro-2-nitro-4-trifluoromethyl-phenylamine [CAS-No. 35375–74–7 (57.74 g, 240 mmol) was added in one portion, and the resulting dark red mixture was stirred at 55–60° C. for 4 days. The warm reaction mixture was slowly poured into H2O (ca. 2000 mL), adjusted pH with conc. HCl to pH 2, the yellow precipitate was filtered off, washed with H2O and dried in air at 60° C. to give a yellow solid (57.81 g, 96%), which was used without further purification. MS (ISN) 249 [M−H].
Reaction SMILES: [Si:1]([O:8][C@@H:9]1[C@H:13]([O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[C@@H:12]([CH2:22][O:23][CH3:24])[O:11][C@H:10]1[N:25]1[CH:33]=[N:32][C:31]2[C:26]1=[N:27][C:28]([C:49](OC)=[O:50])=[N:29][C:30]=2[NH:34][CH2:35][CH:36]([C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].B(OC)(OC)OC.[BH4-].[Li+].O>C(OCC)C>[Si:1]([O:8][C@@H:9]1[C@H:13]([O:14][Si:15]([C:18]([CH3:19])([CH3:20])[CH3:21])([CH3:17])[CH3:16])[C@@H:12]([CH2:22][O:23][CH3:24])[O:11][C@H:10]1[N:25]1[CH:33]=[N:32][C:31]2[C:26]1=[N:27][C:28]([CH2:49][OH:50])=[N:29][C:30]=2[NH:34][CH2:35][CH:36]([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:2])[CH3:3]
Reactant: COC[C@H]1O[C@@H](n2cnc3c(NCC(c4ccccc4)c4ccccc4)nc(C(=O)OC)nc32)[C@H](O[Si](C)(C)C(C)(C)C)[C@@H]1O[Si](C)(C)C(C)(C)C
Agent: COB(OC)OC
Agent: [BH4-]
Agent: [Li+]
Solvent: O
Solvent: CCOCC
Product: COC[C@H]1O[C@@H](n2cnc3c(NCC(c4ccccc4)c4ccccc4)nc(CO)nc32)[C@H](O[Si](C)(C)C(C)(C)C)[C@@H]1O[Si](C)(C)C(C)(C)C
Temperature: 25 °C
Reaction time: 0.17 h
Yield: 74.5 %

Procedure:
A stirred solution of methyl 9-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(methoxymethyl)tetrahydro-2-furanyl]-6-[(2,2-diphenylethyl)amino]-9H-purine-2-carboxylate (7.2 g, 9.64 mmol) (preparation 14) in dry diethyl ether (150 ml) was treated with trimethyl borate (0.11 ml, 0.97 mmol) and lithium borohydride (212 mg, 9.64 mmol) and the mixture heated at reflux for 1 hr under a nitrogen atmosphere. The mixture was then cooled to room temperature, water (100 ml) carefully added and stirring continued for 10 minutes. The organic phase was separated, washed with brine and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue purified by column chromatography on silica gel eluting with a gradient system of diethyl ether:pentane (1:1) changing to diethyl ether:pentane (3:1) to afford the title compound as an oil (5.17 g). MS: 721 (MH+).
Reaction SMILES: [CH2:1]([Br:10])[C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[O:3].[N:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>>[Br-:10].[CH2:1]([N+:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[O:3]
Reactant: O=C(CBr)c1ccccc1
Reactant: c1ccncc1
Product: O=C(C[n+]1ccccc1)c1ccccc1
Product: [Br-]

Procedure:
N-phenacylpyridinium bromide was prepared by slowly adding phenacyl bromide to a stirred flask containing an equimolar quantity of pyridine. The slightly exothermic reaction was accompanied by the precipitation of the solid N-phenacylpyridinium bromide. The salt was then filtered and washed thoroughly with anhydrous ether.
Reaction SMILES: [N+](C1C=C([N+]([O-])=O)C=CC=1[S:13][C:14]1[N:18]([CH2:19][CH2:20][NH:21][S:22]([CH3:25])(=[O:24])=[O:23])[N:17]=[N:16][N:15]=1)([O-])=O.C[O-].[Na+].O>CO>[CH3:25][S:22]([NH:21][CH2:20][CH2:19][N:18]1[C:14]([SH:13])=[N:15][N:16]=[N:17]1)(=[O:24])=[O:23]
Reactant: CS(=O)(=O)NCCn1nnnc1Sc1ccc([N+](=O)[O-])cc1[N+](=O)[O-]
Agent: C[O-]
Agent: [Na+]
Solvent: CO
Solvent: O
Product: CS(=O)(=O)NCCn1nnnc1S
Reaction time: 1 h

Procedure:
5-(2,4-Dinitrophenylthio)-1-(2-methanesulfonamidoethyl)tetrazole (4.46 g, 11.5 mmol) was added to 60 ml of 5% sodium methoxide in methanol. After 1 hour, water was added and the solid material was removed by filtration. The filtrate was concentrated in vacuo and 3N hydrochloric acid was added to the residue to bring the pH to 1.4. The acidic solution was filtered and the filtrate was extracted twice with ethyl acetate. The extracts were combined and concentrated to give a residue which crystallized upon addition of ethyl acetate to give 1-(2-methanesulfonamidoethyl)tetrazole-5-thiol, mp 131°-132°.
Reaction SMILES: [C:1]1([C:7]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)([CH2:14][C:15](OCC)=[O:16])[CH2:8][C:9](OCC)=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CC(CCC(C)=O)=O.CC(C[AlH]CC(C)C)C.CO>C1(C)C=CC=CC=1.O>[C:1]1([C:7]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)([CH2:8][CH:9]=[O:10])[CH2:14][CH:15]=[O:16])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1
Reactant: CCOC(=O)CC(CC(=O)OCC)(c1ccccc1)c1ccccc1
Agent: CC(=O)CCC(C)=O
Agent: CC(C)C[AlH]CC(C)C
Solvent: Cc1ccccc1
Solvent: O
Solvent: CO
Product: O=CCC(CC=O)(c1ccccc1)c1ccccc1
Temperature: 25 °C
Reaction time: 0.67 h

Procedure:
To a rapidly stirring solution of 14.24 g(0.04 mole) of diethyl 3,3-diphenylglutarate, prepared by the method of H. Ivanov and I. Anghelova, Comptes Rendus Acan. Bul. Sci., 18 (6), 529-32(1965), in 320ml of dry toluene at -78° C. under argon was added 61.12 ml (0.11 mole) of 1.86M DIBAL in toluene solution (Aldrich) over a period of 4 minutes. After 40 minutes, 40 ml of methanol was added over 4 minutes to the -78° C., stirring reaction mixture. After an additional 5 minutes of stirring, 80 ml of water was added over a 5 minute period while keeping the temperature of the reaction at -78° C. The reaction mixture was allowed to warm to room temperature and was stirred an addititional hour. The reaction mixture was filtered and the precipitated salts washed with 300 ml of warmed toluene (100° C.) and then 300 ml of boiling methylene chloride. The organic phase of the filtrate was separated, dried over anhydrous magnesium sulfate, filtered, and evaporated in vacuo giving a clear oil. The oil was used in the next step without further purification.