2,6-dimethylbenzene-1,4-diol

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

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

Procedure: A solution of 2,6-dimethyl-1,4-benzoquinone (Xa) (5.66 g, 42 mmol, Aldrich) in Et2O (200 mL) was shaken vigorously in a separatory funnel with two 200 mL portions of aqueous sodium hydrosulfite solution (sodium dithionite, Na2S2O4, 14.5 g, 83.3 mmol) until the Et2O layer turned bright yellow. The ether layer was washed with brine (200 mL×2), dried (MgSO4) and concentrated in vacuo to obtain 4.865 g (35.3 mmol, Y: 83.9%) of the title compound as a white solid; mp, 148-150° C. (acetone-hexane) [mp reported by L. A. Carpino, S. A. Triolo, and R. A. Berglund in J. Org. Chem., 54, p. 3303 (1989): 145-148° C.]; Rf: 0.47 (10% EtOAc in CH2Cl2); IR(KBr) 3312 cm-1 (OH); 1H-NMR (300 MHz, acetone-d6) δ ppm: 2.15 (6H, s, Me), 6.45 (2H, s, Ar-H), 6.58 (1H, s, OH), 7.47 (1H, s, OH); 13C-NMR (75 MHz, acetone-d6) δ ppm: 16.84, 116.00, 126.45, 147.46, 151.54; MS (isobutane-DCI) m/e: 139 (MH+). The ether layer was washed with brine (200 mL×2) dried (MgSO4) concentrated in vacuo

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

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

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

Procedure: Using 4.70 g of 2,6-dimethyl-1,4-dihydroxybenzene, 4.0 ml of benzoyl chloride and 100 ml of pyridine, reaction and workup carried out as in Reference Example gave 6.35 g of 4-benzoyloxy-2,6-dimethylphenol as white crystals, m.p. 139.5-141.0° C. Using 6.35 g of the white crystals, 1.26 g of sodium hydride, 4.2 ml of benzyl bromide and 50 ml of DMF, reaction and workup carried out as in Example 12 gave 4.22 g of yellow oil.

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

Procedure: Using 4.70 g of 2,6-dimethyl-1,4-dihydroxybenzene, 4.0 ml of benzoyl chloride and 100 ml of pyridine, reaction and workup carried out as in Reference Example gave 6.35 g of 4-benzoyloxy-2,6-dimethylphenol as white crystals, m.p. 139.5-141.0° C. Using 6.35 g of the white crystals, 1.26 g of sodium hydride, 4.2 ml of benzyl bromide and 50 ml of DMF, reaction and workup carried out as in Example 12 gave 4.22 g of yellow oil.

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

Procedure: By following in the same manner as in Example 56 except that 11.2 g. (P=67.7) of methyl ethyl ketone peroxide was used instead of 4-methyl-2-pentanone peroxide, 4.68 g. (33.9 m.moles) of 3,5-dimethylcatechol and 2.17 g. (15.7 m.moles) of 2,6-dimethylhydroquinone were obtained. The yield of dihydric alkylphenols was 73.3%.

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

Procedure: By following in the same manner as in Example 56 except that 0.11 g. of strong acidic sulfontype ion exchange resin Amberlyst 15 (manufactured by Rohm and Hass Co.) was used instead of sulfuric acid, 2.55 g. (18.5 m.moles) of 3,5-dimethylcatechol and 1.26 g. (9.1 m.moles) of 2,6-dimethylhydroquinone were obtained. The yield of dihydric alkylphenols was 65.6%.

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

Procedure: By following in the same manner as in Example 56 except that 0.11 g. of strong acidic sulfontype ion exchange resin Amberlyst 15 (manufactured by Rohm and Hass Co.) was used instead of sulfuric acid, 2.55 g. (18.5 m.moles) of 3,5-dimethylcatechol and 1.26 g. (9.1 m.moles) of 2,6-dimethylhydroquinone were obtained. The yield of dihydric alkylphenols was 65.6%.

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

Procedure: By following the same manner as in Example 56 except that 0.013 g. of sodium hydrogen sulfate monohydrate (NaHSO4.H2O) was used, 3.42 g. (24.8 m.moles) of 3,5-dimethylcatechol and 1.66 g. (12.0 m.moles) of 2,6-dimethylhydroquinone were obtained. The yield of dihydric alkylphenols was 87.4%.

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

Procedure: In a vessel used in Example 55, 100 g. (819 m.moles) of 3,5-dimethylphenol, 5.68 g. (P=42.11) of 4-methyl-2-pentanone peroxide and 0.01 g. of 98% sulfuric acid were placed and the reaction was carried out at 100° C. for 20 minutes in the same manner as in Example 55 and analyzed. 3.67 g. (26.6 m.moles) of 3,5-dimethylcatechol and 1.52 g. (11.0 m.moles) of 2,6-dimethylhydroquinone were obtained. The yield of dihydric alkylphenols was 89.3%. In a vessel used in Example 55, 100 g

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

Procedure: In a vessel used in Example 55, 100 g. (819 m.moles) of 3,5-dimethylphenol, 5.68 g. (P=42.11) of 4-methyl-2-pentanone peroxide and 0.01 g. of 98% sulfuric acid were placed and the reaction was carried out at 100° C. for 20 minutes in the same manner as in Example 55 and analyzed. 3.67 g. (26.6 m.moles) of 3,5-dimethylcatechol and 1.52 g. (11.0 m.moles) of 2,6-dimethylhydroquinone were obtained. The yield of dihydric alkylphenols was 89.3%. In a vessel used in Example 55, 100 g