Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [F:1][C:2]([F:11])([F:10])[C:3]1[CH:4]=[CH:5][C:6]([OH:9])=[CH:7][CH:8]=1.C(=O)([O-])[O-].[Cs+].[Cs+].I[C:19]1[CH:26]=[CH:25][C:22]([C:23]#[N:24])=[CH:21][CH:20]=1.Cl.CN(C)CC(O)=O>[Cu]I>[F:1][C:2]([F:10])([F:11])[C:3]1[CH:4]=[CH:5][C:6]([O:9][C:19]2[CH:26]=[CH:25][C:22]([C:23]#[N:24])=[CH:21][CH:20]=2)=[CH:7][CH:8]=1
Reactant: Oc1ccc(C(F)(F)F)cc1
Reactant: N#Cc1ccc(I)cc1
Agent: [Cu]I
Agent: CN(C)CC(=O)O
Agent: Cl
Product: N#Cc1ccc(Oc2ccc(C(F)(F)F)cc2)cc1
Temperature: 90 °C
Yield: 49.8 %

Procedure:
To dried trifluoro-p-cresol (531 mg, 3.27 mmol), copper(I) iodide (83 mg, 0.4 mmol), cesium carbonate (1.42 g, 4.36 mmol), 4-iodobenzonitrile (500 mg, 2.18 mmol) and N,N-dimethylglycine hydrochloride (91 mg, 0.65 mmol) under nitrogen was added degassed 1,4-dioxane (10.0 mL). The whole mixture was heated at 90° C. for 140 hours. The cooled mixture was partitioned between ethyl acetate (50 mL) and water (50 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2×50 mL). The organic layers were combined and washed with brine (100 mL) and dried with Na2SO4 and concentrated in vacuo. The crude liquid was placed on a silica gel column and purified CH2Cl2/Hex (1:8→1:4) and then was recrystallized with hot hexane to give the product as white crystals (286 mg, 50%). 1H NMR (500 MHz, CDCL3) δ(ppm): 7.08 (1H, d, J=8.4 Hz), 7.15 (1H, d, J=8.8 Hz), 7.66 (1H, d, J=8.4 Hz), 7.67 (1H, d, J=8.8 Hz). 13C NMR (125 MHz, CDCL3) δ(ppm): 107.4, 118.7, 119.1 (CH), 120.0 (CH), 122.9, 125.1, 127.0 (1C, q, J=32.5 Hz), 127.3, 127.8 (2CH, q, J=3.8 Hz), 134.5 (CH), 158.2, 160.4. 19F (282 MHz, CDCL3) δ(ppm): −62.05 (3F, s). MS (FAB+): 264 (MH+). HRMS for C14H8F3NO (MH+): calculated: 264.0636; found 264.0621.
Reaction SMILES: [Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[N:4][CH:3]=1.C1C=C(Cl)C=C(C(OO)=[O:20])C=1>C(Cl)(Cl)Cl>[Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[N+:4]([O-:20])[CH:3]=1
Reactant: Brc1cncc2ccccc12
Reactant: O=C(OO)c1cccc(Cl)c1
Solvent: ClC(Cl)Cl
Product: [O-][n+]1cc(Br)c2ccccc2c1
Reaction time: 18 h
Yield: 101.5 %

Procedure:
A solution of 4-bromoisoquinoline (4.16 g, 18.6 mmol) in 100 mL of chloroform was added dropwise over 1 h to a solution of 70% mCPBA (12.4 g, 50.3 mmol) in 100 mL of chloroform at room temperature. After stirring 18 h, the reaction mixture was washed with 1N NaOH (2×150 mL), dried over magnesium sulfate and concentrated in vacuo to afford 4.23 g (94%) of compound 470A as an off-white solid. 1H NMR-400 MHz (CDCl3): δ 8.71 (s, 1H), 8.43 (s, 1H), 8.09 (d, 1H, J=8 Hz), 7.70 (m, 3H).
Reaction SMILES: [Br:1][CH:2]([CH3:18])[C:3]([C:5]1[CH:10]=[CH:9][C:8]([NH:11]C(=O)C)=[C:7]([N+:15]([O-:17])=[O:16])[CH:6]=1)=[O:4].O>Br>[NH2:11][C:8]1[CH:9]=[CH:10][C:5]([C:3](=[O:4])[CH:2]([Br:1])[CH3:18])=[CH:6][C:7]=1[N+:15]([O-:17])=[O:16]
Reactant: CC(=O)Nc1ccc(C(=O)C(C)Br)cc1[N+](=O)[O-]
Agent: Br
Solvent: O
Product: CC(Br)C(=O)c1ccc(N)c([N+](=O)[O-])c1
Temperature: 120 °C
Yield: 353.6 %

Procedure:
11.65 g (37 mM) of N-[4-(2-bromopropanoyl)-2-nitrophenyl]acetamide dissolved in aqueous 47% hydrobromic acid solution are maintained at 120° C. for 15 minutes with stirring. The reaction medium is then poured into water and extracted with ethyl acetate. The organic phase is washed with water, with aqueous sodium hydrogen carbonate solution and finally with saturated aqueous sodium chloride solution. The organic phase is separated out by settling, dried over anhydrous sodium sulfate and then evaporated under vacuum to give 35.7 g of 1-(4-amino-3-nitrophenyl)-2-bromopropan-1-one in the form of a yellow solid.
Reaction SMILES: [C:1]([NH:8][C@H:9]([C@H:17]1[O:21][C:20](=[O:22])[CH2:19][CH2:18]1)[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:33]([O:40][C:41]1[CH:48]=[CH:47][C:44]([CH2:45]I)=[CH:43][CH:42]=1)[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1.CCCCCC.C(OCC)(=O)C>C1COCC1.CN1CCCN(C)C1=O>[C:1]([NH:8][C@H:9]([C@H:17]1[O:21][C:20](=[O:22])[C@H:19]([CH2:45][C:44]2[CH:47]=[CH:48][C:41]([O:40][CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)=[CH:42][CH:43]=2)[CH2:18]1)[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)([O:3][C:4]([CH3:6])([CH3:7])[CH3:5])=[O:2]
Reactant: CC(C)(C)OC(=O)N[C@@H](Cc1ccccc1)[C@@H]1CCC(=O)O1
Reactant: ICc1ccc(OCc2ccccc2)cc1
Agent: C[Si](C)(C)[N-][Si](C)(C)C
Agent: [Li+]
Solvent: CCCCCC
Solvent: CN1CCCN(C)C1=O
Solvent: CCOC(C)=O
Product: CC(C)(C)OC(=O)N[C@@H](Cc1ccccc1)[C@@H]1C[C@@H](Cc2ccc(OCc3ccccc3)cc2)C(=O)O1

Procedure:
In analogy with Example 1h), 1.13 g (3.70 mmol) of 5(S)-[1(S)-(Boc-amino)-2-phenylethyl]dihydrofuran-2-(3H)-one [Example 2b)], dissolved in 4.8 ml of THF and 0.75 ml of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, are deprotonated, at -75° C., with 7.25 ml of a 1M solution of lithium bis(trimethylsilyl)amide in THF, and alkylated (15 min) with 1.2 g (3.7 mmol) of p-benzyloxybenzyl iodide (Example 1d)) in 2 ml of THF. Column chromatography (SiO2, hexane/ethyl acetate, 2:1) affords the pure title compound: TLC Rf (D)=0.30; tRet (I)=28.2 min; FAB-MS (M+H)+ =502.
Reaction SMILES: [NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH:3]=[CH:2]1.Cl[C:11]1[CH:16]=[CH:15][C:14]([CH3:17])=[CH:13][CH:12]=1.CC([O-])(C)C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2OC)CCCCC1.C1(C)C=CC=CC=1>[CH3:17][C:14]1[CH:15]=[CH:16][C:11]([N:1]2[C:9]3[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=3)[CH:3]=[CH:2]2)=[CH:12][CH:13]=1
Reactant: Cc1ccc(Cl)cc1
Reactant: c1ccc2[nH]ccc2c1
Agent: [Pd]
Agent: CC(C)(C)[O-]
Agent: COc1ccccc1-c1ccccc1P(C1CCCCC1)C1CCCCC1
Solvent: Cc1ccccc1
Product: Cc1ccc(-n2ccc3ccccc32)cc1
Temperature: 100 °C
Yield: 93.7 %

Procedure:
An oven-dried test tube was purged with argon and then charged with 2-dicyclohexylphosphino-2′-methoxy-1,1′-biphenyl (14.5 mg, 0.038 mmol, 7.5 mol %) and Pd2(dba)3 (11.6 mg, 0.013 mmol, 5.0 mol % Pd). Toluene (1.0 mL), indole (71 mg, 0.61 mmol), 4-chlorotoluene (60 mL, 0.51 mmol), and NaOt-Bu (70 mg, 0.73 mmol) were then added. The tube was fitted with a septum, purged with argon and heated at 100° C. for 28 h. The reaction was then cooled to room temperature, diluted with ether (20 mL), filtered through Celite and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford 99 mg (94%) of a colorless oil.
Reaction SMILES: Br[C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([N+:12]([O-])=O)[CH:11]=1)[NH:8][C:7](=[O:15])[CH:6]([NH:16][C:17](=[O:19])[CH3:18])[CH2:5]2.C([O-])=O.[NH4+].O>C(O)C.[Pd]>[NH2:12][C:10]1[CH:11]=[CH:2][CH:3]=[C:4]2[C:9]=1[NH:8][C:7](=[O:15])[CH:6]([NH:16][C:17](=[O:19])[CH3:18])[CH2:5]2
Reactant: CC(=O)NC1Cc2cc(Br)cc([N+](=O)[O-])c2NC1=O
Agent: [Pd]
Agent: O=C[O-]
Agent: [NH4+]
Solvent: CCO
Solvent: O
Product: CC(=O)NC1Cc2cccc(N)c2NC1=O
Temperature: 80 °C
Reaction time: 0.5 h
Yield: 84.8 %

Procedure:
N-(6-Bromo-8-nitro-2-oxo-1,2,3,4-tetrahydroquinolin-3-yl)acetamide (15 g) was suspended in ethanol (150 mL), and ammonium formate (28.8 g) and 10% Pd—C (water content: 53%) (1.5 g) were added thereto. The mixture was heated at 80° C. while being stirred for 30 minutes, and water (150 mL) and ethanol (150 mL) were added thereto, followed by filtration while being heated. The filtrate was concentrated under reduced pressure, and the formed precipitates were recovered through filtration. The thus-obtained solid was washed with ethanol and diisopropyl ether, followed by drying, whereby the title compound (8.5 g) was yielded.
Reaction SMILES: [C:1]1([NH:7][CH2:8][C:9]([OH:11])=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:12]([N:16]=[C:17]=[O:18])[CH2:13][CH2:14][CH3:15]>>[C:1]1([N:7]2[CH2:8][C:9](=[O:11])[N:16]([CH2:12][CH2:13][CH2:14][CH3:15])[C:17]2=[O:18])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1
Reactant: CCCCN=C=O
Reactant: O=C(O)CNc1ccccc1
Product: CCCCN1C(=O)CN(c2ccccc2)C1=O
Yield: 43.3 %

Procedure:
N-phenyl glycine (0.15 mole) was added with stirring over a 15 minute period to n-butyl isocyanate (0.15 mole). After the addition was complete the reaction mixture was refluxed for about 6 hours and then allowed to stand at room temperature until it solidified. The solidified mass was crystallized from ethanol and produced 0.065 moles of the above-described product having a melting point of 74° l C.
Reaction SMILES: [CH3:1][S:2]([NH:5][CH2:6][C:7]1[CH:16]=[CH:15][C:10]([C:11](OC)=[O:12])=[CH:9][CH:8]=1)(=[O:4])=[O:3].[H-].[H-].[H-].[H-].[Li+].[Al+3].CO.C(Cl)(Cl)Cl>C1COCC1>[CH3:1][S:2]([NH:5][CH2:6][C:7]1[CH:16]=[CH:15][C:10]([CH2:11][OH:12])=[CH:9][CH:8]=1)(=[O:4])=[O:3]
Reactant: COC(=O)c1ccc(CNS(C)(=O)=O)cc1
Agent: [Al+3]
Agent: [H-]
Agent: [Li+]
Solvent: CO
Solvent: C1CCOC1
Solvent: ClC(Cl)Cl
Product: CS(=O)(=O)NCc1ccc(CO)cc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 80.5 %

Procedure:
To a mixture of methyl 4-[(methanesulfonamido)methyl]benzoate (3.6 g, 15 mmol) in THF (150 mL) was added LiAlH4 (1M in THF, 30 mL, 30 mmol). The reaction mixture was stirred at rt for 1 h and poured into 10% MeOH/CHCl3 containing silica gel. The solids were removed by filtration, washed with 10% MeOH/CHCl3 and the combined washings were evaporated to yield the title compound as a white solid (2.6 g, 80%).
Reaction SMILES: [CH3:1][O:2][C:3]1[C:4]([CH3:13])=[C:5]([CH:10]=[CH:11][CH:12]=1)[C:6]([NH:8][NH2:9])=[O:7].CCO[CH2:17][CH3:18]>CO.C(O)(=O)C>[CH2:6]1[C:17]2[C:18](=[CH:12][CH:3]=[CH:4][CH:13]=2)[CH2:11][CH2:10][C:5]1=[N:9][NH:8][C:6](=[O:7])[C:5]1[CH:10]=[CH:11][CH:12]=[C:3]([O:2][CH3:1])[C:4]=1[CH3:13]
Reactant: CCOCC
Reactant: COc1cccc(C(=O)NN)c1C
Solvent: CO
Solvent: CC(=O)O
Product: COc1cccc(C(=O)NN=C2CCc3ccccc3C2)c1C

Procedure:
3-Methoxy-2-methyl-benzoic acid hydrazide (1.0 g) and P-tetralone (0.9 g) were mixed in 4 mL of methanol with 1 drop of acetic acid at room temperature for 10 minutes. Approximately 10 mL of ether were added and the mixture was refrigerated. Crystals of 3-methoxy-2-methyl-benzoic acid (3,4-dihydro-1H-naphthalen-2-ylidene)-hydrazide formed, which were collected by filtration (0.85 g). 1H NMR (300 MHz, CDCl3)δ(ppm): 6.8-7.3 (m, 4H), 3.75+3.8 (2 s, 3H), 3.45+3.7 (2 s, 2H), 2.85 (t, 2H), 2.4 (t, 2H), 2.27+2.25 (2 s, 3H); multiple conformers; Rf=0.56 (3:1 ethyl acetate:hexane); m.p.=138° C.; m.p. of 3-methoxy-2-methyl-benzoic acid hydrazide=113-116° C.
Reaction SMILES: C([N+](CCCC)(CCCC)CCCC)CCC.C1(CC([NH:27][C@H:28]2[C@H:31]([CH3:32])[N:30]([S:33]([O-:36])(=[O:35])=[O:34])[C:29]2=[O:37])=O)C=CC=CC=1.N1C=CC=CC=1.C(Cl)(Cl)=O.FC(F)(F)C(O)=O>C(Cl)Cl.C1C=CC=CC=1.CO>[NH2:27][C@H:28]1[C@H:31]([CH3:32])[N:30]([S:33]([OH:36])(=[O:34])=[O:35])[C:29]1=[O:37]
Reactant: C[C@H]1[C@H](NC(=O)Cc2ccccc2)C(=O)N1S(=O)(=O)[O-]
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: O=C(Cl)Cl
Solvent: CO
Solvent: c1ccncc1
Solvent: c1ccccc1
Product: C[C@H]1[C@H](N)C(=O)N1S(=O)(=O)O
Temperature: -15 °C
Reaction time: 1.5 h
Yield: 34 %

Procedure:
(3S-trans)-3-[(Phenylacetyl)amino]-4-methyl-2-oxo-1-azetidinesulfonic acid, tetra-n-butylammonium salt (3.79 g) is dissolved in 70 ml of methylene chloride, cooled to -15° C. and 2.3 ml of pyridine is added. The cold mixture is treated with 5.8 ml of a 12% mixture of phosgene in benzene and stirred at -10° C. for 90 minutes. Methanol (35 ml) is added and the mixture is stirred for 30 minutes followed by the addition of 1.62 ml of trifluoroacetic acid. The reaction mixture is allowed to warm to room temperature and stirred for 16 hours. The precipitated material is collected by filtration, washed with methylene chloride and dried to yield 0.43 g of the title compound.
Reaction SMILES: [S:1]1[C:7]2[CH:8]=[CH:9][S:10][C:6]=2[C:5](=O)[NH:4][CH2:3][CH2:2]1.N1C=CC=CC=1.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=S>O>[S:1]1[C:7]2[CH:8]=[CH:9][S:10][C:6]=2[CH2:5][NH:4][CH2:3][CH2:2]1
Reactant: O=C1NCCSc2ccsc21
Agent: S=P12SP3(=S)SP(=S)(S1)SP(=S)(S2)S3
Solvent: O
Solvent: c1ccncc1
Product: c1cc2c(s1)CNCCS2

Procedure:
(acb) 1.0 g of 3,4-dihydro-thieno[2,3-f][1,4]thiazepin-5(2H)-one was heated under reflux for 5 hours together with 15 ml of pyridine and 1.35 g of phosphorus pentasulfide. After cooling the mixture was poured into 90 ml of water and the crystals were removed by filtration. After chromatography on silica gel, the product was recrystallized from ethyl acetate. There was obtained 3,4-dihydro-thieno-[2,3-f][1,4]thiazepine-5(2H-thione as yellow crystals of m.p. 138°-139°.
Reaction SMILES: [Cl:1][C:2]1[C:7](=[O:8])[N:6]([CH3:9])[CH:5]=[C:4]([N:10]2[CH:17]([C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=3)[C:16]3[C:12](=[N:13][N:14](CC4C=CC(OC)=CC=4)[C:15]=3[CH3:25])[C:11]2=[O:35])[CH:3]=1>C(Cl)Cl.CO>[Cl:1][C:2]1[C:7](=[O:8])[N:6]([CH3:9])[CH:5]=[C:4]([N:10]2[CH:17]([C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=3)[C:16]3[C:12](=[N:13][NH:14][C:15]=3[CH3:25])[C:11]2=[O:35])[CH:3]=1
Reactant: COc1ccc(Cn2nc3c(c2C)C(c2ccc(Cl)cc2)N(c2cc(Cl)c(=O)n(C)c2)C3=O)cc1
Solvent: ClCCl
Solvent: CO
Product: Cc1[nH]nc2c1C(c1ccc(Cl)cc1)N(c1cc(Cl)c(=O)n(C)c1)C2=O

Procedure:
The title compound was prepared in analogy to the procedure described in Example 2 using 5-(5-chloro-1-methyl-6-oxo-1,6-dihydropyridin-3-yl)-4-(4-chlorophenyl)-2-(4-methoxybenzyl)-3-methyl-4,5-dihydropyrrolo[3,4-c]pyrazol-6(2H)-one (Step 5.5). tR: 3.55 min (HPLC 1); tR: 0.78 min (LC-MS 2); ESI-MS: 389/391 [M+H]+ (LC-MS 2); Rf=0.34 (CH2Cl2/MeOH 9:1); 1H NMR (400 MHz, DMSO-d6) δ ppm 2.03 (s, 3H) 3.43 (s, 3H) 6.13 (s, 1H) 7.25 (d, J=8.2 Hz, 2H) 7.36 (d, J=8.2 Hz, 2H) 7.90 (d, J=2.4 Hz, 1H) 7.94 (d, J=2.7 Hz, 1H) 13.38 (s, 1H).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH:9]=[O:10])[CH:6]=[CH:5][C:4]=1[C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([CH3:17])[CH:12]=1.[C:18]1([Mg]Br)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C1COCC1>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH:9]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[OH:10])[CH:6]=[CH:5][C:4]=1[C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([CH3:17])[CH:12]=1
Reactant: Br[Mg]c1ccccc1
Reactant: COc1cc(C=O)ccc1-c1cccc(C)c1
Solvent: C1CCOC1
Product: COc1cc(C(O)c2ccccc2)ccc1-c1cccc(C)c1
Temperature: -20 °C
Reaction time: 2 h
Yield: 78 %

Procedure:
The aldehyde 5 were dissolved in dry THF and cooled to −20° C. Phenylmagnesium bromide (1.2 eq, 1.651 mM) was then added to the reaction and the reaction was stirred for an additional 2 hrs. After the completion of the reaction as determined by TLC, the reaction mixture was quenched with 0.1 N HCl, followed by washes with saturated sodium bicarbonate solution and brine. The organic layer was then evaporated and the product was purified by flash chromatography using 20% EtOAc/Hexanes as the solvent system to obtain a white solid. Yield=78.0% (Rf=0.48; 20% EtOAc/Hexanes) 1H NMR, 500 MHz Varian, CDCl3, δ 10.01 (s, 1H), 7.53 (d, J=15.00 Hz, 1H), 7.51 (d, J=15.00 Hz, 1H), 7.49 (d, J=10.00 Hz, 1H), 7.34 (s, 3H), 7.21 (d, J=7.0, 1H), 3.89 (s, 3H), 2.41 s, 3H), MS: m/z (ESI, pos.)=327.8 ([M+23])
Reaction SMILES: O([C:8]([O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]2([CH2:22][N:23]3[CH:27]=[N:26][CH:25]=[N:24]3)[O:21][CH2:20][CH2:19][O:18]2)=[CH:13][CH:12]=1)=O)C1C=CC=CC=1.C(=O)=O>C(OCCOCC)C.C(OCC)C>[O:10]([C:11]1[CH:12]=[CH:13][C:14]([C:17]2([CH2:22][N:23]3[CH:27]=[N:26][CH:25]=[N:24]3)[O:18][CH2:19][CH2:20][O:21]2)=[CH:15][CH:16]=1)[C:8]1[CH:15]=[CH:16][CH:11]=[CH:12][CH:13]=1
Reactant: O=C(Oc1ccccc1)Oc1ccc(C2(Cn3cncn3)OCCO2)cc1
Agent: CCOCCOCC
Agent: O=C=O
Solvent: CCOCC
Product: c1ccc(Oc2ccc(C3(Cn4cncn4)OCCO3)cc2)cc1

Procedure:
11 parts of 2-[p-(Phenoxycarbonyloxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-1,3 -dioxolane are heated in 200 ml ethylene glycol diethyl ether (about 10 hours) at a temperature of 130° C. till the end of the carbon dioxid production. Then the solvent is destilled of under reduced pressure. The oily crude product is cooled to room temperature, solved in 500 ml diethyl ether, washed with two portions of 100 ml water, dried over sodium sulfate and filtered. The solvent is removed by evaporation. The crude product is recrystallised from ethyl acetate/cyclohexane in the presence of active carbon to give colourless crystals with a melting point of 100°-102° C.
Reaction SMILES: [N+:1]([C:4]1[CH:12]=[C:11]([C:13]([F:16])([F:15])[F:14])[CH:10]=[CH:9][C:5]=1[C:6](Cl)=[O:7])([O-:3])=[O:2].[CH:17]1([C:20]([N:22]([CH2:25][CH3:26])[CH2:23][CH3:24])=[CH2:21])[CH2:19][CH2:18]1.C(N(CC)CC)C.C>C1(C)C=CC=CC=1>[CH:17]1([C:20]([N:22]([CH2:25][CH3:26])[CH2:23][CH3:24])=[CH:21][C:6]([C:5]2[CH:9]=[CH:10][C:11]([C:13]([F:16])([F:15])[F:14])=[CH:12][C:4]=2[N+:1]([O-:3])=[O:2])=[O:7])[CH2:19][CH2:18]1
Reactant: O=C(Cl)c1ccc(C(F)(F)F)cc1[N+](=O)[O-]
Reactant: C=C(C1CC1)N(CC)CC
Solvent: CCN(CC)CC
Solvent: Cc1ccccc1
Product: CCN(CC)C(=CC(=O)c1ccc(C(F)(F)F)cc1[N+](=O)[O-])C1CC1
Temperature: 25 °C
Reaction time: 1 h
Yield: 31.4 %

Procedure:
2-nitro-4-trifluoromethylbenzoyl chloride (9.4 g) was added dropwise to a cooled mixture of 1-cyclopropyl-1-diethylaminoethene (5.1 g) and triethylamine (3.7 g) in toluene (100 ml) whilst maintaining the temperature below 10° C. The mixture was then stirred at room temperature for 1 hour. The suspension was treated with decolourising charcoal and filtered. The filtrate was evaporated and the residue was purified by chromatography on silica gel eluted with a mixture of ethyl acetate and dichloromethane (1:9) to give 3-cyclopropyl-3-diethylamino-1-(2-nitro-4-trifluoromethylphenyl)-prop-2-en-1-one (4.1 g) as a red oil with its 1H NMR (in CDCl3) giving peaks at d=0.7-1.8(m, 11H), 3.5(q, 4H), 5.0(s, 1H), 7.5(d, 1H), 7.7(d, 1H),and 7.95(s, 1H).
Reaction SMILES: [Br:1][C:2]1[CH:3]=[CH:4][C:5]([OH:10])=[C:6]([CH:9]=1)[CH:7]=[O:8].C([O-])([O-])=O.[K+].[K+].Br[CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22].O>CN(C)C=O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:10][CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])=[C:6]([CH:9]=1)[CH:7]=[O:8]
Reactant: O=Cc1cc(Br)ccc1O
Reactant: CC(C)(C)[Si](C)(C)OCCBr
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CN(C)C=O
Solvent: O
Product: CC(C)(C)[Si](C)(C)OCCOc1ccc(Br)cc1C=O
Temperature: 60 °C
Reaction time: 16 h
Yield: 100 %

Procedure:
To a solution of 5-bromo-2-hydroxy-benzaldehyde (14 g, 69.6 mmol) (Aldrich) in N,N-dimethylformamide (300 mL) was added K2CO3 (29 g, 208.9 mmol) and (2-bromo-ethoxy)-tert-butyl-dimethyl-silane (20 g, 83.5 mmol) (Aldrich). The reaction mixture was stirred at 60° C. for 16 h. The reaction mixture was cooled to room temperature and poured into water, extracted with ethyl acetate. The organic layers were combined, washed with water, brine, dried over MgSO4, filtered and concentrated to give 5-bromo-2-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-benzaldehyde as brown oil (Yield: 25 g, 100%).
Reaction SMILES: [Br:1][C:2]1[C:11]2[C:6](=[C:7]([Br:21])[CH:8]=[C:9]([C:12]([C:14]3[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=3)=[O:13])[CH:10]=2)[N:5]=[C:4]([O:22][CH3:23])[CH:3]=1.[Cl:24][C:25]1[CH:30]=[CH:29][C:28]([Mg]Br)=[CH:27][CH:26]=1>O1CCCC1>[Cl:20][C:17]1[CH:16]=[CH:15][C:14]([C:12]([C:28]2[CH:29]=[CH:30][C:25]([Cl:24])=[CH:26][CH:27]=2)([C:9]2[CH:10]=[C:11]3[C:6](=[C:7]([Br:21])[CH:8]=2)[N:5]=[C:4]([O:22][CH3:23])[CH:3]=[C:2]3[Br:1])[OH:13])=[CH:19][CH:18]=1
Reactant: COc1cc(Br)c2cc(C(=O)c3ccc(Cl)cc3)cc(Br)c2n1
Reactant: Clc1ccc([Mg]Br)cc1
Solvent: C1CCOC1
Product: COc1cc(Br)c2cc(C(O)(c3ccc(Cl)cc3)c3ccc(Cl)cc3)cc(Br)c2n1
Temperature: 25 °C
Reaction time: 3 h

Procedure:
Into a 100-mL round-bottom flask, was placed a solution of 4,8-dibromo-6-[(4-chlorophenyl)carbonyl]-2-methoxyquinoline (1.5 g, 3.29 mmol, 1.00 equip) in tetrahydrofuran (30 mL). To the resulting mixture was then added (4-chlorophenyl)magnesium bromide (9.87 mL, 3.00 equip, 1 M) dropwise with stirring at 0° C. The resulting solution was stirred for 3 h at room temperature. The reaction was then quenched by the addition of saturated sodium bicarbonate (100 mL). The solids were filtered out and washed with ethyl acetate (100 mL), and the ethyl acetate was combined with the filtrate. The resulting solution was extracted with ethyl acetate (100 mL) and the organic layers combined and dried over anhydrous sodium sulfate. The solids were filtered out. The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1:9) to yield bis(4-chlorophenyl)(4,8-dibromo-2-methoxyquinolin-6-yl)methanol as a yellow solid. LCMS (ES, m/z) 568 [M+H]+
Reaction SMILES: [CH2:1]([C:7]1[CH:8]=[C:9]([C:13]2[N:17]([CH3:18])[C:16]([C:19]([N:21]3[CH2:26][CH2:25][CH:24]([N:27]4[CH2:31][CH2:30][CH2:29][CH2:28]4)[CH2:23][CH2:22]3)=[O:20])=[C:15](I)[N:14]=2)[CH:10]=[CH:11][CH:12]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6].[Cl:33][C:34]1[N:39]=[CH:38][C:37](B(O)O)=[CH:36][CH:35]=1>>[Cl:33][C:34]1[N:39]=[CH:38][C:37]([C:15]2[N:14]=[C:13]([C:9]3[CH:10]=[CH:11][CH:12]=[C:7]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH3:6])[CH:8]=3)[N:17]([CH3:18])[C:16]=2[C:19]([N:21]2[CH2:22][CH2:23][CH:24]([N:27]3[CH2:31][CH2:30][CH2:29][CH2:28]3)[CH2:25][CH2:26]2)=[O:20])=[CH:36][CH:35]=1
Reactant: CCCCCCc1cccc(-c2nc(I)c(C(=O)N3CCC(N4CCCC4)CC3)n2C)c1
Reactant: OB(O)c1ccc(Cl)nc1
Product: CCCCCCc1cccc(-c2nc(-c3ccc(Cl)nc3)c(C(=O)N3CCC(N4CCCC4)CC3)n2C)c1

Procedure:
In analogy to the procedure described for example 7, [2-(3-hexyl-phenyl)-5-iodo-3-methyl-3H-imidazol-4-yl]-(4-pyrrolidin-1-yl-piperidin-1-yl)-methanone (example 2) was reacted with 6-chloro-pyridin-3-yl-boronic acid to give the title compound as light yellow gum. MS: 534.3 (MH+, 1Cl).
Reaction SMILES: [CH2:1]=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[CH:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>>[CH2:1]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]
Reactant: C=CCCCCCC
Reactant: c1ccccc1
Product: CCCCCCCCc1ccccc1
Yield: 70 %

Procedure:
The alkylation of benzene with oct-1-ene. The reaction gave a 70% yield (by GC) of three isomers of octylbenzene. The isomer ratio was determined to be 0.75:1.00:2.03, with the 4-phenyloctene as the major product and 2-phenyloctene as the minor product. During the course of the reaction, isomeration of oct-1-ene to a number of isomers of octene was observed, and the rate of this isomerisation process was considerably faster that the alkylation reaction. It was found that the ionic liquid/catalyst combination remained active on a second run. To confirm that the minor product of the reaction was an octene dimer, the same reaction was performed, but without any benzene present (shown below).