pyren-1-ylmethanol

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:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Pyrenemethanol (Pyr-OH) (109.6 mg, 0.47 mmol) in 1.0 mL DMF (anh) was treated with 180 μL TEA (anh, 1.29 mmol) and 2-bromoacetyl bromide (132.2 μL, 1.50 mmol) in 1 mL dichloromethane. The mixture was stirred at RT (˜23° C.) for 17 hours. After the solvent was evaporated, the crude product was purified by silica gel column (Hex/EtOAc=2/1) to give 167 mg final product as a yellow solid (yield 90%). 1H NMR (CDCl3, 500 MHz): δ 8.28-8.03 (m, 9H, ArH), 5.94 (s, 2H, ArCH2), 3.90 (s, 2H, CH2Br). ESI: 375, [M+Na]+. After the solvent was evaporated the crude product was purified by silica gel column (Hex/EtOAc=2/1)

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: Thionyl chloride (15 mL, 200 mmol) was added dropwise to a suspension of 1-hydroxymethylpyrene (9.3 g, 40 mmol) in dry benzene (150 mL) at 0° C. and the mixture was stirred at room temperature overnight. Evaporation of the solvent under reduced pressure gave a creamy-white solid, m.p. 146°-148° C., yield: 9.6 g, 96%. Evaporation of the solvent under reduced pressure gave a creamy-white solid, m.p. 146°-148° C., yield: 9.6 g, 96%

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

Procedure: To a suspension of pyrene carboxaldehyde (9.6 g, 42 mmol) in ethanol (50 mL) was added NaBH4 (2 g) and the mixture was stirred at room temperature for 6 hours. Water (100 mL) was added and the mixture was extracted with ether (2×50 mL). The organic layer was dried over MgSO4, and the solvent evaporated under reduced pressure to give a light-yellow solid which was recrystallized from ethyl acetate to afford prisms, m.p. 125°-126° C., yield: 8.3 g, 86%. the mixture was extracted with ether (2×50 mL) The organic layer was dried over MgSO4 the solvent evaporated under reduced pressure to give a light-yellow solid which was recrystallized from ethyl acetate to afford prisms, m.p. 125°-126° C., yield: 8.3 g, 86%

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

Procedure: Thionyl chloride (15 mL, 200 mmol) was added dropwise to a suspension of 1-hydroxymethylpyrene (9.3 g, 40 mmol) in dry benzene (150 mL) at 0° C. and the mixture was stirred at room temperature overnight. Evaporation of the solvent under reduced pressure gave a creamy-white solid, m.p. 146°-148° C., yield: 9.6 g, 96%. Evaporation of the solvent under reduced pressure gave a creamy-white solid, m.p. 146°-148° C., yield: 9.6 g, 96%

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

Procedure: To a suspension of pyrene carboxaldehyde (9.6 g, 42 mmol) in ethanol (50 mL) was added NaBH4 (2 g) and the mixture was stirred at room temperature for 6 hours. Water (100 mL) was added and the mixture was extracted with ether (2×50 mL). The organic layer was dried over MgSO4, and the solvent evaporated under reduced pressure to give a light-yellow solid which was recrystallized from ethyl acetate to afford prisms, m.p. 125°-126° C., yield: 8.3 g, 86%. the mixture was extracted with ether (2×50 mL) The organic layer was dried over MgSO4 the solvent evaporated under reduced pressure to give a light-yellow solid which was recrystallized from ethyl acetate to afford prisms, m.p. 125°-126° C., yield: 8.3 g, 86%

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Pyrenemethanol (Pyr-OH) (109.6 mg, 0.47 mmol) in 1.0 mL DMF (anh) was treated with 180 μL TEA (anh, 1.29 mmol) and 2-bromoacetyl bromide (132.2 μL, 1.50 mmol) in 1 mL dichloromethane. The mixture was stirred at RT (˜23° C.) for 17 hours. After the solvent was evaporated, the crude product was purified by silica gel column (Hex/EtOAc=2/1) to give 167 mg final product as a yellow solid (yield 90%). 1H NMR (CDCl3, 500 MHz): δ 8.28-8.03 (m, 9H, ArH), 5.94 (s, 2H, ArCH2), 3.90 (s, 2H, CH2Br). ESI: 375, [M+Na]+. After the solvent was evaporated the crude product was purified by silica gel column (Hex/EtOAc=2/1)