2-methylnaphthalen-1-ol

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Phosphorus oxychloride (0.176 mL, 1 equiv) and 2-methylnaphthalen-1-ol (Aldrich, 0.3 g, 1 equiv) were stirred in anhydrous diethyl ether (10 mL). Anhydrous triethylamine was added (0.264 mL, 1 equiv) at −78° C. and stirred for 30 min. The dichloridate was very unstable at room temperature. The progress of the reaction was monitored by 31P NMR. This crude mixture was considered to be a 100% conversion to dichloridate and was used directly. was very unstable at room temperature

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

Procedure: A solution of 9.48 g (60 mmole) of 2-methyl-1-naphthol and 8.10 g (80 mmole) of triethylamine in 50 mL of ethyl acetate was cooled to below 5° C. in an ice-bath. 5.50 g (70 mmole) of acetyl chloride was added at a rate such that the temperature did not rise about 5° C. The reaction mixture was stirred for an additional one hour, diluted with 50 mL of ethyl acetate, and washed with water then brine. The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated to give an oily residue. Crystallization in hexane yielded 7.58 g (63% yield) of the title compound with a melting point of 81°-83° C. and an 1HNMR as follows: (300 MHz, DMSO-d6) δ 2.26 ) (s, 3H), 2.48 (s, 3H), 7.42 (d, 1H, J=9 Hz), 7.46-7.55 (m, 2H), 7.47-7.81 (m, 2H), 7.92 (d, 1H, J=9 Hz). The mass spectrum showed a molecular ion at m/z 200. did not rise about 5° C washed with water The organic layer was dried over anhydrous sodium sulfate filtered evaporated to give an oily residue Crystallization in hexane

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

Procedure: A solution of 9.48 g (60 mmole) of 2-methyl-1-naphthol and 8.10 g (80 mmole) of triethylamine in 50 mL of ethyl acetate was cooled to below 5° C. in an ice-bath. 5.50 g (70 mmole) of acetyl chloride was added at a rate such that the temperature did not rise about 5° C. The reaction mixture was stirred for an additional one hour, diluted with 50 mL of ethyl acetate, and washed with water then brine. The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated to give an oily residue. Crystallization in hexane yielded 7.58 g (63% yield) of the title compound with a melting point of 81°-83° C. and an 1HNMR as follows: (300 MHz, DMSO-d6) δ 2.26 ) (s, 3H), 2.48 (s, 3H), 7.42 (d, 1H, J=9 Hz), 7.46-7.55 (m, 2H), 7.47-7.81 (m, 2H), 7.92 (d, 1H, J=9 Hz). The mass spectrum showed a molecular ion at m/z 200. did not rise about 5° C washed with water The organic layer was dried over anhydrous sodium sulfate filtered evaporated to give an oily residue Crystallization in hexane

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

Procedure: To an ice-cooled solution of 2-methyl-l-naphthol (7.9 g, 0.05 mmol) in dichloromethane, anhydrous aluminum chloride (7.2 g) was slowly added with stirring, followed by slow addition of acetyl chloride (4.7 g) to start reaction. The reaction mixture was stirred at 10° C. or below for 1 h, then at room temperature for 3 h. Thereafter, the mixture was poured into ice water. Then, the reaction product was extracted with dichloromethane and the extracted layer was washed with water. Further, the extracted layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was recrystallized with benzene, giving the desired compound, 2-methyl-4-acetyl-l-naphthol, in an amount of 3.9 g. was slowly added reaction The reaction mixture was stirred at 10° C. or below for 1 h Then, the reaction product was extracted with dichloromethane the extracted layer was washed with water Further, the extracted layer was dried over anhydrous sodium sulfate the solvent was distilled off under reduced pressure The residue was recrystallized with benzene

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

Procedure: To demonstrate the storage stability of the compounds of the present invention, test samples of the title compounds of Examples 1, 2, 3, 4, 5 and 6 were placed in clear glass vials and kept on top of a laboratory desk for the time indicated. Samples of 2-methyl-1-naphthol, 1-naphthol and phenyl trifluoroacetate used as controls were similarly kept. One sample of 2-methyl-1-naphthol was stored under nitrogen and in a dry ice chest (temperature of approximately -50° C). A second sample of 2-methyl-1-naphthol and the remaining test'samples were stored at room temperature. were stored at room temperature

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

Procedure: A solution of 9.48 g (60 mmole) of 2-methyl-1-naphthol and 8.10 g (80 mmole) of triethylamine in 50 mL of ethyl acetate was cooled to below 5° C. in an ice-bath. 5.50 g (70 mmole) of acetyl chloride was added at a rate such that the temperature did not rise about 5° C. The reaction mixture was stirred for an additional one hour, diluted with 50 mL of ethyl acetate, and washed with water then brine. The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated to give an oily residue. Crystallization in hexane yielded 7.58 g (63% yield) of the title compound with a melting point of 81-83° C. and an 1HNMR as follows: (300 Hz, DMSO-d6) δ 2.26 (s, 3H), 2.48 (s, 3H), 7.42 (d, 1H, J=9 Hz), 7.46-7.55 (m, 2H), 7.47-7.81 (m, 2H), 7.92 (d, 1H, J=9 Hz). The mass spectrum showed a molecular ion at m/z 200. did not rise about 5° C washed with water The organic layer was dried over anhydrous sodium sulfate filtered evaporated to give an oily residue Crystallization in hexane

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

Procedure: 2.64 g (26 mmole) of triethylamine were added to a stirred solution of 3.16 g (20 mmole) of 2-methyl-1-naphthol in 25 mL of ethyl acetate, while the solution was maintained in an ice bath. Then 2.36 g (25 mmole) methyl chloroformate were added portionwise to the solution. The reaction mixture was stirred for one hour and then 100 mL diethylether was added. The reaction mixture was filtered over a Celite pad and the filtrate concentrated to give 3.65 g (85% yield) of an oil which was crystallized in hexane. The resulting crystals had a melting point of 54-55° C. The following 1HNMR was obtained: (300 MHz, DMSO-d6) δ2.30 (s, 3H), 3.89 (s, 3H), 7.44 (d, 1H, J=8 Hz), 7.48-7.58 (m, 2H), 7.78 (t, 2H, J=9 Hz), 7.95 (d, 1H, J=8 Hz). The mass spectrum showed a molecular ion at m/z 216. was maintained in an ice bath The reaction mixture was filtered over a Celite pad the filtrate concentrated

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

Procedure: 2.64 g (26 mmole) of triethylamine were added to a stirred solution of 3.16 g (20 mmole) of 2-methyl-1-naphthol in 25 mL of ethyl acetate, while the solution was maintained in an ice bath. Then 2.36 g (25 mmole) methyl chloroformate were added portionwise to the solution. The reaction mixture was stirred for one hour and then 100 mL diethylether was added. The reaction mixture was filtered over a Celite pad and the filtrate concentrated to give 3.65 g (85% yield) of an oil which was crystallized in hexane. The resulting crystals had a melting point of 54-55° C. The following 1HNMR was obtained: (300 MHz, DMSO-d6) δ2.30 (s, 3H), 3.89 (s, 3H), 7.44 (d, 1H, J=8 Hz), 7.48-7.58 (m, 2H), 7.78 (t, 2H, J=9 Hz), 7.95 (d, 1H, J=8 Hz). The mass spectrum showed a molecular ion at m/z 216. was maintained in an ice bath The reaction mixture was filtered over a Celite pad the filtrate concentrated

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

Procedure: We found that both the yield and the enantioselectivity of the arylation of 2-methyl-α-tetralone could be brought to good levels by running the arylation using 10-20 mol % Pd(0)/12-24 mol % BINAP in toluene at 100° C.8,9 It was found that an excess of aryl bromide was necessary to ensure complete conversion of the ketone; 2-methyl-1-naphthol, biaryls, and compounds resulting from aldol condensation were formed as side-products. In some reactions, the α-phenylated ketone was also observed as a side product. Subsequent experiments demonstrated that the latter side product was a result of aryl transfer from the phosphine ligand.10 Using the conditions described above, the arylations of 2-methyl-α-tetralone proceeded with enantioselectivities up to 88% (Table 1).11 We have also briefly examined the reactions of 2-methyl-1-indanone, 1. Using 5 mol % Pd(OAc)2/12 mol % BINAP the reaction with yield at 100° C

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

Procedure: We found that both the yield and the enantioselectivity of the arylation of 2-methyl-α-tetralone could be brought to good levels by running the arylation using 10-20 mol % Pd(0)/12-24 mol % BINAP in toluene at 100° C.8,9 It was found that an excess of aryl bromide was necessary to ensure complete conversion of the ketone; 2-methyl-1-naphthol, biaryls, and compounds resulting from aldol condensation were formed as side-products. In some reactions, the α-phenylated ketone was also observed as a side product. Subsequent experiments demonstrated that the latter side product was a result of aryl transfer from the phosphine ligand.10 Using the conditions described above, the arylations of 2-methyl-α-tetralone proceeded with enantioselectivities up to 88% (Table 1).11 We have also briefly examined the reactions of 2-methyl-1-indanone, 1. Using 5 mol % Pd(OAc)2/12 mol % BINAP the reaction with yield at 100° C

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

Procedure: 0.58 mmol of 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one dimethane sulphonate was dissolved in a mixture of water and ethanol (7.5 ml/1.5 ml). This solution was admixed with 0.58 mmol of 2-methyl-1-naphthol, then with 1.8 ml of concentrated aqueous ammonia, then with 9 ml of hydrogen peroxide.