2,5-dichloro-2,5-dimethylhexane

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

Procedure: 83 ml of hexylbenzene were treated with 1.8 g of aluminium chloride while cooling with ice. After brief stirring a solution of 40 g of 2,5-dichloro-2,5-dimethyl-hexane in 300 ml of carbon disulphide was added dropwise and the mixture was stirred at 0° C. for a further 2 hours. The reaction mixture was poured into ice/6N hydrochloric acid, extracted with ethyl acetate, dried over sodium sulphate and evaporated. The crude product was distilled in a high vacuum. There were obtained 25.5 g of 1,1,4,4-tetramethyl-6-hexyl-1,2,3,4-tetrahydro-naphthalene as a colourless oil, boiling point 141-152° C./0.8 mm. while cooling with ice was added dropwise extracted with ethyl acetate dried over sodium sulphate evaporated The crude product was distilled in a high vacuum

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,5-Dimethyl-2,5-dichlorohexane (183 g, 1 mol) was stirred with m-cresol (129.6 g, 1.2 mol) and aluminum chloride (4 g) was added in one direction. The mixture was heated at 95° C., with stirring for 1.5 h, after which ethylene dichloride (100 mL) was added and then the heating was continued. After 1 h the mixture was cooled to 20° C. and poured onto an ice-water/hydrochloric acid mixture (150 mL, 10% HCl solution). The mixture was then extracted with toluene (500 mL). The organic layer was separated, washed with brine (3×50 mL) and dried (Na2SO4). The solvent was removed by distillation and the residue was crystallized from a hexane/benzene solvent mixture to give 1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (171 g), mp 133°-134° C., GLC purity 99%+. 1H-NMR (CDCl3) δ 6.82 (1H, broad s), 6.35 (1 H, d, J=1.4 Hz), 4.72 (1H, s), 2.30 (3H, s), 1.71 (4H, m), 1.49 (6H, s), 1.34 (6H, s). 13C-NMR (CDCl3) δ 154.2 (1C, s), 147.8 (1C, s), 135.7 (1C, s), 128.0 (1C, s), 120.2 (1C, d), 114.6 (1C, d), 37.9 (1C, t), 35.2 (1C, t), 34.6 (1C, s), 33.7 (1C, s), 32.0 (2C, q), 28.5 (2C, q), 20.8 (1C, q). IR (KBr) 3,503 cm-1, MS (m/e) 218 (M+, 24.7), 203 (100.0), 161 (55.1), 147 (23.9), 57 (10.9). was added in one direction After 1 h the mixture was cooled to 20° C. The mixture was then extracted with toluene (500 mL) The organic layer was separated washed with brine (3×50 mL) dried (Na2SO4) The solvent was removed by distillation the residue was crystallized from a hexane/benzene solvent mixture

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

Procedure: 7 g of aluminum chloride was added by portions to 200 ml solution of 50 g 2,5-dichloro-2,5-dimethylhexane in orthoxylene at 0° C. under stirring. After the mixture was stirred at the same temperature for 15 minutes, it was poured into ice-cold water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and then evaporated to give 60 g of 2,3,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene as a brown oil. After the mixture was stirred at the same temperature for 15 minutes it was poured into ice-cold water extracted with ethyl acetate The organic layer was washed with brine dried over anhydrous magnesium sulfate evaporated

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

Procedure: 7 g of aluminum chloride was added by portions to 200 ml solution of 50 g 2,5-dichloro-2,5-dimethylhexane in orthoxylene at 0° C. under stirring. After the mixture was stirred at the same temperature for 15 minutes, it was poured into ice-cold water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and then evaporated to give 60 g of 2,3,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene as a brown oil. After the mixture was stirred at the same temperature for 15 minutes it was poured into ice-cold water extracted with ethyl acetate The organic layer was washed with brine dried over anhydrous magnesium sulfate evaporated

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

Procedure: 2,5-Dichloro-2,5-dimethylhexane (67.5 g, 0.369 mol) was dissolved in dry toluene (200 ml), and then AlCl3 (4.05 g, 30.4 mmol) was crushed up and added portionwise to the solution. After being left for 2 hours, the reaction mixture was poured into ice/5% HCl and the mixture was extracted with hexane. The organic layer was washed each twice with water, aqueous sodium hydrogen carbonate, and then with water, dried over MgSO4, and the solvent was removed by evaporation. The residue was distilled to give 5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylnaphthalene (70.42 g, yield: 90%). bp 100° C. (solidified at room temperature). added portionwise to the solution the mixture was extracted with hexane The organic layer was washed each twice with water, aqueous sodium hydrogen carbonate with water, dried over MgSO4 the solvent was removed by evaporation The residue was distilled

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

Procedure: 2,5-Dichloro-2,5-dimethylhexane (67.5 g, 0.369 mol) was dissolved in dry toluene (200 ml), and then AlCl3 (4.05 g, 30.4 mmol) was crushed up and added portionwise to the solution. After being left for 2 hours, the reaction mixture was poured into ice/5% HCl and the mixture was extracted with hexane. The organic layer was washed each twice with water, aqueous sodium hydrogen carbonate, and then with water, dried over MgSO4, and the solvent was removed by evaporation. The residue was distilled to give 5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylnaphthalene (70.42 g, yield: 90%). bp 100° C. (solidified at room temperature). added portionwise to the solution the mixture was extracted with hexane The organic layer was washed each twice with water, aqueous sodium hydrogen carbonate with water, dried over MgSO4 the solvent was removed by evaporation The residue was distilled

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

Procedure: 27.5 g (0.2 mol) of anhydrous aluminum chloride were added by spatula to 250.0 g (2.65 mol) of phenol plus 414.5 g (2.27 mol) of 2,5-dichloro-2,5-dimethylhexane in 500 ml of petroleum ether at room temperature while stirring. After 48 hours, the reaction mixture was poured into ice-water and extracted with ether, and the organic phase was washed to neutrality with water, dried over sodium sulfate and evaporated under reduced pressure. Two recrystallizations of the residue from methanol yielded 148.7 g of the title compound of melting point 219°-220° C. extracted with ether the organic phase was washed dried over sodium sulfate evaporated under reduced pressure Two recrystallizations of the residue from methanol

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

Procedure: 27.5 g (0.2 mol) of anhydrous aluminum chloride were added by spatula to 250.0 g (2.65 mol) of phenol plus 414.5 g (2.27 mol) of 2,5-dichloro-2,5-dimethylhexane in 500 ml of petroleum ether at room temperature while stirring. After 48 hours, the reaction mixture was poured into ice-water and extracted with ether, and the organic phase was washed to neutrality with water, dried over sodium sulfate and evaporated under reduced pressure. Two recrystallizations of the residue from methanol yielded 148.7 g of the title compound of melting point 219°-220° C. extracted with ether the organic phase was washed dried over sodium sulfate evaporated under reduced pressure Two recrystallizations of the residue from methanol

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

Procedure: To a one necked round bottom flask 2,6-dimethylphenol (13.88 g, 113.6 mmol), 2,5-dichloro-dimethylhexane were added followed by 460 mL of nitromethane. A clear light yellow solution was cooled in a water bath. Aluminum chloride (15.2 g, 113.9 mmol) was added in small portions into the flask. The reaction mixture changed color from pale yellow to green then brown during the addition of aluminum chloride. The reaction was stirred overnight at room temperature and quenched with water. The content was extracted with ethyl acetate and washed with sodium bicarbonate and brine. Crude product was purified by plug of silica gel 5:95 ethyl acetate:hexane to obtain 19.3 g of 1,3,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-ol. 1H NMR (300 MHz, CDCl3) δ 1.40 (s, 6H), 1.67(m, 4H), 2.16 (s, 3H), 2.36 (s, 3H), 2.56 (s, 3H), 3.90 (s, 3H), 5.03(d, 1H, J=3.59 Hz), 6.33 (s, 1H), 6.89(d, 1H, J=3.59 Hz), 7.07 (s, 1H), 7.11(d, 1H, J=3.59 Hz), 8.29 (bs, 1H). A clear light yellow solution was cooled in a water bath quenched with water The content was extracted with ethyl acetate washed with sodium bicarbonate and brine Crude product was purified by plug of silica gel 5:95 ethyl acetate

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

Procedure: A flame dried 3 L three neck round bottom flask fit with a magnetic stirrer, condenser, heating mantle, and nitrogen inlet was charged with indane (49 mL, 0.40 mol, Aldrich), anhydrous methylene chloride (800 mL, Aldrich), and 2,5-dichloro-2,5-dimethylhexane. The mixture was heated to reflux and the aluminum chloride (5.65 g, 0.042 mol). was added portionwise while refluxing the reaction. The reaction mixture was quenched in 1 L 5% HCl/ice, the layers separated, and the combined organics washed with water until neutral to pH paper. The organics were then dried over anhydrous magnesium sulfate, stripped of solvent by rotary evaporation and distilled to yield 5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indane (32.1 g, 105-110° C./0.4-0.45 mm Hg, 76-89% pure by GC). 1HNMR (CDCl3, 500 MHz) δ7.19 (s, 2H); 2.86 (t, J=7.5 Hz, 4H); 2.04 (p, J=7.5 Hz, 2H); 1.67 (s, 4H); 1.28 (s, 12H). A flame dried 3 L three neck round bottom flask fit with a magnetic stirrer, condenser heating mantle The mixture was heated to reflux was added portionwise while refluxing the reaction The reaction mixture was quenched in 1 L 5% HCl/ice the layers separated the combined organics washed with water until neutral The organics were then dried over anhydrous magnesium sulfate stripped of solvent by rotary evaporation distilled

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

Procedure: A flame dried 3 L three neck round bottom flask fit with a magnetic stirrer, condenser, heating mantle, and nitrogen inlet was charged with indane (49 mL, 0.40 mol, Aldrich), anhydrous methylene chloride (800 mL, Aldrich), and 2,5-dichloro-2,5-dimethylhexane. The mixture was heated to reflux and the aluminum chloride (5.65 g, 0.042 mol). was added portionwise while refluxing the reaction. The reaction mixture was quenched in 1 L 5% HCl/ice, the layers separated, and the combined organics washed with water until neutral to pH paper. The organics were then dried over anhydrous magnesium sulfate, stripped of solvent by rotary evaporation and distilled to yield 5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indane (32.1 g, 105-110° C./0.4-0.45 mm Hg, 76-89% pure by GC). 1HNMR (CDCl3, 500 MHz) δ7.19 (s, 2H); 2.86 (t, J=7.5 Hz, 4H); 2.04 (p, J=7.5 Hz, 2H); 1.67 (s, 4H); 1.28 (s, 12H). A flame dried 3 L three neck round bottom flask fit with a magnetic stirrer, condenser heating mantle The mixture was heated to reflux was added portionwise while refluxing the reaction The reaction mixture was quenched in 1 L 5% HCl/ice the layers separated the combined organics washed with water until neutral The organics were then dried over anhydrous magnesium sulfate stripped of solvent by rotary evaporation distilled

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

Procedure: A 2 L three neck round bottom flask fit with an overhead stirrer, thermometer, and nitrogen inlet was charged with 1.2 L concentrated HCl. The HCl was stirred land chilled in an ice/salt bath to 0° C. Gradually, 150 g of 2,5-dimethyl-2,5-hexanediol (Aldrich) was added to the HCl. The reaction mixture was initially a milky white slurry which gradually thickened and the ice bath was removed to allow the reaction to warm to 10 C. The solids were isolated by filtration, dissolved in methylene chloride (500 mL) and washed repeatedly with water until neutral to pH paper. The organics were dried over anhydrous magnesium sulfate and left in the refrigerator overnight. The resulting mixture stripped on the rotary evaporator to yield)of white crystalline 2,5-dichloro-2,5-dimethylhexane (152 g, 94% pure by GC). 1HNMR (CDCl3, 500 MHz) δ1.95 (s, 4H); 1.60 (s, 12H). the ice bath was removed the reaction to warm to 10 C The solids were isolated by filtration washed repeatedly with water until neutral The organics were dried over anhydrous magnesium sulfate The resulting mixture stripped on the rotary evaporator