1-Pyrenecarboxaldehyde

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

Procedure: Using the reductive amination procedure described for 20G, pyrene-1-carbaldehyde (Aldrich) and 2-amino-2-isopropyl-1,3-propanediol acetate (24B) gave 2-isopropyl-2-((1-pyrenylmethyl)amino)-1,3-propanediol hydrochloride mp 244°-245° (dec), (CH3OH/Et2O), (C, H, N, Cl).

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

Procedure: Using the reductive amination procedure described for 20G, pyrene-1-carbaldehyde (Aldrich) and 2-amino-2-isopropyl-1,3-propanediol acetate (24B) gave 2-isopropyl-2-((1-pyrenylmethyl)amino)-1,3-propanediol hydrochloride mp 244°-245° (dec), (CH3OH/Et2O), (C, H, N, Cl).

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

Procedure: Using the reductive amination procedure outlined in 20G, pyrene-1-carbaldehyde (Aldrich) and 2-amino-3-methoxy-2-methyl-1-propanol (22C) gave after workup using the procedure outlined in 1B 3-methoxy-2-methyl-2-((1-pyrenylmethyl)amino)-1-propanol methanesulfonate.1/3H2O mp 158°-160°, (EtOH/Et2O), (C, H, N, S). gave after workup

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask, equipped with a magnetic stirrer, an argon inlet and a Claisen adapter bearing an addition funnel and an argon outlet leading to a mineral oil bubbler, was dried in an oven, assembled hot and cooled under a stream of argon. The flask was charged with methyltriphenyl phosphonium bromide (8.4788 g, 23.73 mmole), potassium t-butoxide (23.7 mL of a 1.0M solution in tetrahydrofuran) and 18-crown-6 (0.180 g). Dry tetrahydrofuran (70 mL) was transferred to the flask under nitrogen using a cannula and the resultant reaction mixture was cooled to 0° C. using an ice-salt bath. Pyrene-1-carboxaldehyde (5.0 g, 21.7 mmole) was dissolved in dry THF (25 mL) and this solution was transferred to the addition funnel, under a nitrogen atmosphere, using a cannula, and then added dropwise to the cold reaction mixture over a period of 10 minutes. The reaction mixture was allowed to warm to room temperature and stirred overnight under an argon atmosphere. The solid which precipitated was filtered, washed with THF (15 mL) on the frit and the combined filtrate was concentrated on a rotary evaporator to give a solid residue, which was dissolved in dry diethyl ether (50 mL). The ether solution was passed through a short bed of neutral alumina washed with ether and the combined ether filtrate was concentrated to give a yellow solid (6.0 g). This yellow solid was chromatographed on silica gel with hexanes as eluent and the chromatographed material thus obtained was further purified by crystallization from 5% water/ethanol to give an off-white crystalline material (2.1655 g), melting point 88°-89° C. (89° C. according to Kamat, P. V.; Basheer, R.; and Fox, M. A. Macromolecules 18, 1366 (1985)). A 250 mL round-bottomed flask, equipped with a magnetic stirrer, an argon inlet was dried in an oven cooled under a stream of argon the resultant reaction mixture added dropwise to the cold reaction mixture over a period of 10 minutes to warm to room temperature The solid which precipitated was filtered washed with THF (15 mL) on the frit the combined filtrate was concentrated on a rotary evaporator to give a solid residue, which washed with ether the combined ether filtrate was concentrated

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask, equipped with a magnetic stirrer, an argon inlet and a Claisen adapter bearing an addition funnel and an argon outlet leading to a mineral oil bubbler, was dried in an oven, assembled hot and cooled under a stream of argon. The flask was charged with methyltriphenyl phosphonium bromide (8.4788 g, 23.73 mmole), potassium t-butoxide (23.7 mL of a 1.0M solution in tetrahydrofuran) and 18-crown-6 (0.180 g). Dry tetrahydrofuran (70 mL) was transferred to the flask under nitrogen using a cannula and the resultant reaction mixture was cooled to 0° C. using an ice-salt bath. Pyrene-1-carboxaldehyde (5.0 g, 21.7 mmole) was dissolved in dry THF (25 mL) and this solution was transferred to the addition funnel, under a nitrogen atmosphere, using a cannula, and then added dropwise to the cold reaction mixture over a period of 10 minutes. The reaction mixture was allowed to warm to room temperature and stirred overnight under an argon atmosphere. The solid which precipitated was filtered, washed with THF (15 mL) on the frit and the combined filtrate was concentrated on a rotary evaporator to give a solid residue, which was dissolved in dry diethyl ether (50 mL). The ether solution was passed through a short bed of neutral alumina washed with ether and the combined ether filtrate was concentrated to give a yellow solid (6.0 g). This yellow solid was chromatographed on silica gel with hexanes as eluent and the chromatographed material thus obtained was further purified by crystallization from 5% water/ethanol to give an off-white crystalline material (2.1655 g), melting point 88°-89° C. (89° C. according to Kamat, P. V.; Basheer, R.; and Fox, M. A. Macromolecules 18, 1366 (1985)). A 250 mL round-bottomed flask, equipped with a magnetic stirrer, an argon inlet was dried in an oven cooled under a stream of argon the resultant reaction mixture added dropwise to the cold reaction mixture over a period of 10 minutes to warm to room temperature The solid which precipitated was filtered washed with THF (15 mL) on the frit the combined filtrate was concentrated on a rotary evaporator to give a solid residue, which washed with ether the combined ether filtrate was concentrated

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

Procedure: The procedure used to prepare 1-vinylpyrene was similar to that of K. Tanikawa, T. Ishizuka, K. Suzuki, S. Kusabayashi, and H. Mikawa, Bull. Chem. Soc. Japan, 41, 2719-2722, (1968) Under an argon atmosphere, methyltriphenylphosphonium bromide (0.16 mole) was mixed with butyllithium (0.16 mole of 2.0 M butyllithium in pentane) in dry ether (660 ml.). After the ylid color was obtained (4-8 hr.), pyrene-1-carboxaldehyde (0.14 mole) in dry tetrahydrofuran (500 ml.) was added dropwise. The mixture was stirred overnight under an argon atmosphere. Ether was removed by evaporation under reduced pressure, and the remaining tetrahydrofuran solution was boiled under reflux for 1 hour. After evaporation to dryness under reduced pressure, the residue was dissolved in toluene and the resulting solution was washed with 30% aqueous sodium sulfite solution and water. Toluene was evaporated under reduced pressure to precipitate the crude product, which, after dissolving in hot ethanol and treatment with charcoal, allowed 1-vinylpyrene to crystallize as a yellow powder (53% yield), m. p. 88°-89° C. (lit 88°-89° C.). The structure was confirmed by proton NMR.

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

Procedure: About 100 grams (0.434 moles) pyrene-1-carboxaldehyde, about 28.7 grams (0.434 moles) malononitrile, about 10.4 milliliters acetic acid, about 3.48 grams ammonium acetate and about 400 milliliters benzene are heated to boiling under reflux conditions for 30 minutes. The entire contents of the flask crystallized, forming a deep orange red product which is soluble in -tetrahydrofuran, moderately soluble in ethanol and very soluble in chlorobenzene. This product is recrystallized from a mixture of chlorobenzene and ethanol (30:70). Yield: 104.4 grams m. p 248°-250° C. The entire contents of the flask crystallized forming a deep orange red product which This product is recrystallized from a mixture of chlorobenzene and ethanol (30:70) p 248°-250° C.

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: 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: About 100 grams (0.434 moles) pyrene-1-carboxaldehyde, about 28.7 grams (0.434 moles) malononitrile, about 10.4 milliliters acetic acid, about 3.48 grams ammonium acetate and about 400 milliliters benzene are heated to boiling under reflux conditions for 30 minutes. The entire contents of the flask crystallized, forming a deep orange red product which is soluble in tetrahydrofuran, moderately soluble in ethanol and very soluble in chlorobenzene. This product is recrystallized from a mixture of chlorobenzene and ethanol (30:70). Yield: 104.4 grams m. p 248°-250° C. The entire contents of the flask crystallized forming a deep orange red product which This product is recrystallized from a mixture of chlorobenzene and ethanol (30:70) p 248°-250° C.

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

Procedure: Using the reductive amination procedure described for 20G, pyrene-1-carbaldehyde (Aldrich) and 2-amino-2-isopropyl-1,3-propanediol acetate (24B) gave 2-isopropyl-2-((1-pyrenylmethyl)amino)-1,3-propanediol hydrochloride mp 244°-245° (dec), (CH3OH/Et2O), (C, H, N, Cl).

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

Procedure: Using the reductive amination procedure outlined in 20G, pyrene-1-carbaldehyde (Aldrich) and 2-amino-3-methoxy-2-methyl-1-propanol (22C) gave after workup using the procedure outlined in 1B 3-methoxy-2-methyl-2-((1-pyrenylmethyl)amino)-1-propanol methanesulfonate.1/3H2O mp 158°-160°, (EtOH/Et2O), (C, H, N, S). gave after workup