3-(BROMOMETHYL)PYRENE

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 9.78 g (45.04 mmol) sample of diethyl acetamidomalonate, and 1.08 g sodium hydride (45.04 mmol) were suspended in 100 mL of anhydrous THF, under nitrogen, and at 0°C. After stirring for 5 min., 2.5 mL of anhydrous ethanol were added slowly, and the solution returned to room temperature. A solution of 1-(bromomethyl)pyrene (12.03 g, 40.9 mmol, dissolved in 100 mL dry THF) was slowly added to the reaction mixture, and the solution brought to reflux for 18 h. The bulk of the THF was removed under reduced pressure, and the remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2:H2O. The organic fraction was washed 3× with 100 mL H2O, and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to produce Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate (14.70 g, 83.1%) as a light yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.57. Mp=135-140° C. 1H NMR (CDCl3), δ1.37 (t, 6H), 1.95 (s, 3H), 3.76 (s, 2H), 4.30 (q, 6H), 6.42 (s, NH), 8.00-825 (m, 9H from pyrene). at 0°C returned to room temperature to reflux for 18 h The bulk of the THF was removed under reduced pressure the remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2 The organic fraction was washed 3× with 100 mL H2O dried over anhydrous Na2SO4 Solvent was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 10.00 g sample (43.1 mmol) of 1-Pyrenemethanol was dissolved in 250 mL of benzene with slight heating. The mixture was returned to room temperature and 1.63 mL (4.24 g, 17.24 mmol) of phosphorus tribromide were slowly added. The mixture was brought to reflux and stirred for 2 h. The mixture was returned to room temperature, and poured into a separatory funnel containing 500 mL 3:2 Et2O:H2O. The organic fraction was washed twice with 100 mL H2O and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to yield 1-(bromomethyl)pyrene (12.030 g, 95.0%) as a dark yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.95. Mp=270° C. (dec) 1H NMR (CDCl3), δ 5.28 (s, 2H), 8.0-8.3 (m, 9H from pyrene). 13C NMR (CDCl3), δ32.643, 123.258-132.374 16 pks from pyrene. was returned to room temperature to reflux was returned to room temperature poured into a separatory funnel The organic fraction was washed twice with 100 mL H2O dried over anhydrous Na2SO4 Solvent was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 10.00 g sample (43.1 mmol) of 1-Pyrenemethanol was dissolved in 250 mL of benzene with slight heating. The mixture was returned to room temperature and 1.63 mL (4.24 g, 17.24 mmol) of phosphorus tribromide were slowly added. The mixture was brought to reflux and stirred for 2 h. The mixture was returned to room temperature, and poured into a separatory funnel containing 500 mL 3:2 Et2O:H2O. The organic fraction was washed twice with 100 mL H2O and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to yield 1-(bromomethyl)pyrene (12.030 g, 95.0%) as a dark yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.95. Mp=270° C. (dec) 1H NMR (CDCl3), δ 5.28 (s, 2H), 8.0-8.3 (m, 9H from pyrene). 13C NMR (CDCl3), δ32.643, 123.258-132.374 16 pks from pyrene. was returned to room temperature to reflux was returned to room temperature poured into a separatory funnel The organic fraction was washed twice with 100 mL H2O dried over anhydrous Na2SO4 Solvent was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Firstly, 500 mg of (1-pyrenyl)methanol as the starting material was dissolved in 20 mL of dehydrated dichloromethane, and then 1 mL of PBr3 was slowly dropped into the solution that was kept in an ice bath of 0° C. in an N2-atmosphere. After 12 hours of stirring with a magnetic stirrer, the mixture was neutralized with 50 ml of 0.3M sodium bicarbonate solution (4 g/150 mL) three times using a separating funnel, and then CH2Cl2 was used to extract the organic phase in the mixture. After the moisture in the organic phase was removed by anhydrous MgSO4, the solvent in the organic phase was removed under a reduced pressure to obtain 547 mg of (1-pyrenyl)bromomethane in a high purity. The completion of the bromination was confirmed by the 1H-NMR spectrum of the product in FIG. 3A and the mass spectrum (molecular weight=295.17) of the same. to extract the organic phase in the mixture After the moisture in the organic phase was removed by anhydrous MgSO4 the solvent in the organic phase was removed under a reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 10.00 g sample (43.1 mmol) of 1-Pyrenemethanol was dissolved in 250 mL of benzene with slight heating. The mixture was returned to room temperature and 1.63 mL (4.24 g, 17.24 mmol) of phosphorus tribromide were slowly added. The mixture was brought to reflux and stirred for 2 h. The mixture was returned to room temperature, and poured into a separatory funnel containing 500 mL 3:2 Et2O:H2O. The organic fraction was washed twice with 100 mL H2O and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to yield 1-(bromomethyl)pyrene (12.030 g, 95.0%) as a dark yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.95. Mp=270° C. (dec) 1H NMR (CDCl3), δ 5.28 (s, 2H), 8.0-8.3 (m, 9H from pyrene). 13C NMR (CDCl3), δ32.643, 123.258-132.374 16 pks from pyrene. was returned to room temperature to reflux was returned to room temperature poured into a separatory funnel The organic fraction was washed twice with 100 mL H2O dried over anhydrous Na2SO4 Solvent was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 9.78 g (45.04 mmol) sample of diethyl acetamidomalonate, and 1.08 g sodium hydride (45.04 mmol) were suspended in 100 mL of anhydrous THF, under nitrogen, and at 0°C. After stirring for 5 min., 2.5 mL of anhydrous ethanol were added slowly, and the solution returned to room temperature. A solution of 1-(bromomethyl)pyrene (12.03 g, 40.9 mmol, dissolved in 100 mL dry THF) was slowly added to the reaction mixture, and the solution brought to reflux for 18 h. The bulk of the THF was removed under reduced pressure, and the remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2:H2O. The organic fraction was washed 3× with 100 mL H2O, and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to produce Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate (14.70 g, 83.1%) as a light yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.57. Mp=135-140° C. 1H NMR (CDCl3), δ1.37 (t, 6H), 1.95 (s, 3H), 3.76 (s, 2H), 4.30 (q, 6H), 6.42 (s, NH), 8.00-825 (m, 9H from pyrene). at 0°C returned to room temperature to reflux for 18 h The bulk of the THF was removed under reduced pressure the remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2 The organic fraction was washed 3× with 100 mL H2O dried over anhydrous Na2SO4 Solvent was removed under reduced pressure