2-methylhexan-2-ol

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

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

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methylhexan-2-ol (30.0 g, 0.258 mol) was treated with acetic anhydride (36.6 mL, 0.387 mol). Pyridine (30.0 mL, excess) was added dropwise over a 3 min period at 23° C. Then 4-(N,N-dimethylamino)-pyridine (1.27 g, 10.0 mmol) was added. The reaction was heated to 70° C. for 16 h. The reaction was cooled to 23° C. and poured onto 300 mL of crushed ice. After 15 min of stirring, most of the ice had melted. Solid NaHCO3 was added in portions (bubbling) until the pH was 9. The system was extracted with two portions of diethyl ether (100 mL, then 50 mL). The combined extracts were washed with 1.0 M aq. CuSO4 monohydrate (4×50 mL), dried over MgSO4, and filtered. The filtrate was distilled at ambient pressure at a bath temperature of 80-100° C. to remove most of the diethyl ether. The resulting oil left in the pot was fractionally distilled through a Snyder column with 3 chambers under reduced pressure (6-8 mmHg). A small-volume forerun was collected and discarded (bp<45° C.). The main fraction contained 2-methylhexan-2-yl acetate (bp 45-48° C.). 1H NMR (400 MHz, CDCl3) δ 1.94 (s, 3H), 1.74-1.68 (m, 2H), 1.40 (s, 6H), 1.33-1.22 (m, 4H), 0.88 (t, J=6.8 Hz, 3H). The reaction was cooled to 23° C. The system was extracted with two portions of diethyl ether (100 mL The combined extracts were washed with 1.0 M aq. CuSO4 monohydrate (4×50 mL) dried over MgSO4 filtered The filtrate was distilled at ambient pressure at a bath temperature of 80-100° C. to remove most of the diethyl ether The resulting oil left in the pot was fractionally distilled through a Snyder column with 3 chambers under reduced pressure (6-8 mmHg) A small-volume forerun was collected

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methylhexan-2-ol (30.0 g, 0.258 mol) was treated with acetic anhydride (36.6 mL, 0.387 mol). Pyridine (30.0 mL, excess) was added dropwise over a 3 min period at 23° C. Then 4-(N,N-dimethylamino)-pyridine (1.27 g, 10.0 mmol) was added. The reaction was heated to 70° C. for 16 h. The reaction was cooled to 23° C. and poured onto 300 mL of crushed ice. After 15 min of stirring, most of the ice had melted. Solid NaHCO3 was added in portions (bubbling) until the pH was 9. The system was extracted with two portions of diethyl ether (100 mL, then 50 mL). The combined extracts were washed with 1.0 M aq. CuSO4 monohydrate (4×50 mL), dried over MgSO4, and filtered. The filtrate was distilled at ambient pressure at a bath temperature of 80-100° C. to remove most of the diethyl ether. The resulting oil left in the pot was fractionally distilled through a Snyder column with 3 chambers under reduced pressure (6-8 mmHg). A small-volume forerun was collected and discarded (bp<45° C.). The main fraction contained 2-methylhexan-2-yl acetate (bp 45-48° C.). 1H NMR (400 MHz, CDCl3) δ 1.94 (s, 3H), 1.74-1.68 (m, 2H), 1.40 (s, 6H), 1.33-1.22 (m, 4H), 0.88 (t, J=6.8 Hz, 3H). The reaction was cooled to 23° C. The system was extracted with two portions of diethyl ether (100 mL The combined extracts were washed with 1.0 M aq. CuSO4 monohydrate (4×50 mL) dried over MgSO4 filtered The filtrate was distilled at ambient pressure at a bath temperature of 80-100° C. to remove most of the diethyl ether The resulting oil left in the pot was fractionally distilled through a Snyder column with 3 chambers under reduced pressure (6-8 mmHg) A small-volume forerun was collected

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

Procedure: To a flame-dried, nitrogen-purged 500 mL 3-neck roundbottom flask with 250 mL pressure-equalizing addition funnel and magnetic stirbar was charged 81 mL n-butyl lithium (129 mmol, 1 equiv., 1.6 M in hexanes). A degassed solution of 15.0 g 2-methyl-2-hexanol (129 mmol, 1 eq.) in 100 mL anhydrous tetrahydrofuran was charged to the addition funnel and added to the reaction mixture dropwise at 0° C. over 60 minutes. The reaction mixture was warmed for 15 minutes on hot water bath to ensure the reaction was complete. The reaction vessel was cooled to 0° C. and 14.2 g methacryloyl chloride (135 mmol, 1.05 eq.) was added dropwise and allowed to stir for 15 minutes. The addition funnel was replaced with a reflux condenser and the reaction heated to reflux for 20 hours. After the reaction was complete, it was cooled to 0° C. and quenched aqueous sodium bicarbonate. The product was extracted into ethyl ether and the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine and then dried over magnesium sulfate, filtered, concentrated in vacuo, and stored over a small amount of sodium bicarbonate. The crude product mixture was vacuum distilled through a vacuum-jacketed short-path distillation head to afford 14 g (59%) of 2-methylhexan-2-yl methacrylate (XIII) as a colorless liquid. To a flame-dried, nitrogen-purged 500 mL roundbottom flask with 250 mL pressure-equalizing addition funnel added to the reaction mixture dropwise at 0° C. over 60 minutes The reaction mixture was warmed for 15 minutes on hot water bath The addition funnel was replaced with a reflux condenser the reaction heated to reflux for 20 hours it was cooled to 0° C. quenched aqueous sodium bicarbonate The product was extracted into ethyl ether the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine dried over magnesium sulfate filtered concentrated in vacuo distilled through a vacuum-jacketed short-path distillation head

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

Procedure: To a flame-dried, nitrogen-purged 500 mL 3-neck roundbottom flask with 250 mL pressure-equalizing addition funnel and magnetic stirbar was charged 81 mL n-butyl lithium (129 mmol, 1 equiv., 1.6 M in hexanes). A degassed solution of 15.0 g 2-methyl-2-hexanol (129 mmol, 1 eq.) in 100 mL anhydrous tetrahydrofuran was charged to the addition funnel and added to the reaction mixture dropwise at 0° C. over 60 minutes. The reaction mixture was warmed for 15 minutes on hot water bath to ensure the reaction was complete. The reaction vessel was cooled to 0° C. and 14.2 g methacryloyl chloride (135 mmol, 1.05 eq.) was added dropwise and allowed to stir for 15 minutes. The addition funnel was replaced with a reflux condenser and the reaction heated to reflux for 20 hours. After the reaction was complete, it was cooled to 0° C. and quenched aqueous sodium bicarbonate. The product was extracted into ethyl ether and the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine and then dried over magnesium sulfate, filtered, concentrated in vacuo, and stored over a small amount of sodium bicarbonate. The crude product mixture was vacuum distilled through a vacuum-jacketed short-path distillation head to afford 14 g (59%) of 2-methylhexan-2-yl methacrylate (XIII) as a colorless liquid. To a flame-dried, nitrogen-purged 500 mL roundbottom flask with 250 mL pressure-equalizing addition funnel added to the reaction mixture dropwise at 0° C. over 60 minutes The reaction mixture was warmed for 15 minutes on hot water bath The addition funnel was replaced with a reflux condenser the reaction heated to reflux for 20 hours it was cooled to 0° C. quenched aqueous sodium bicarbonate The product was extracted into ethyl ether the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine dried over magnesium sulfate filtered concentrated in vacuo distilled through a vacuum-jacketed short-path distillation head

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

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

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

Procedure: To a flame-dried, nitrogen-purged 500 mL 3-neck roundbottom flask with 250 mL pressure-equalizing addition funnel and magnetic stirbar was charged 81 mL n-butyl lithium (129 mmol, 1 equiv., 1.6 M in hexanes). A degassed solution of 15.0 g 2-methyl-2-hexanol (129 mmol, 1 eq.) in 100 mL anhydrous tetrahydrofuran was charged to the addition funnel and added to the reaction mixture dropwise at 0° C. over 60 minutes. The reaction mixture was warmed for 15 minutes on hot water bath to ensure the reaction was complete. The reaction vessel was cooled to 0° C. and 14.2 g methacryloyl chloride (135 mmol, 1.05 eq.) was added dropwise and allowed to stir for 15 minutes. The addition funnel was replaced with a reflux condenser and the reaction heated to reflux for 20 hours. After the reaction was complete, it was cooled to 0° C. and quenched aqueous sodium bicarbonate. The product was extracted into ethyl ether and the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine and then dried over magnesium sulfate, filtered, concentrated in vacuo, and stored over a small amount of sodium bicarbonate. The crude product mixture was vacuum distilled through a vacuum-jacketed short-path distillation head to afford 14 g (59%) of 2-methylhexan-2-yl methacrylate (XIII) as a colorless liquid. To a flame-dried, nitrogen-purged 500 mL roundbottom flask with 250 mL pressure-equalizing addition funnel added to the reaction mixture dropwise at 0° C. over 60 minutes The reaction mixture was warmed for 15 minutes on hot water bath The addition funnel was replaced with a reflux condenser the reaction heated to reflux for 20 hours it was cooled to 0° C. quenched aqueous sodium bicarbonate The product was extracted into ethyl ether the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine dried over magnesium sulfate filtered concentrated in vacuo distilled through a vacuum-jacketed short-path distillation head

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

Procedure: 2-Phthalimidoacetonitrile (14.4 g.) was reacted with 2-methylhexan-2-ol (7.5 g.) in glacial acetic acid by the addition of concentrated sulphuric acid (15 ml.) according to the process described in Example 1. The resulting N-(1,1-dimethylpentyl)-2-phthalimidoacetamide was recrystallisedfrom benzene, m.p. 189°-190° C. It was then reacted with hydrazine hydrate (2.8 g.) in ethanol (100 ml.) as in Example 2 and the product purified as its hydrogen oxalate; 2-amino-N-(1,1-dimethylpentyl)acetamide hydrogen oxalate. the product purified as its hydrogen oxalate

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methylhexan-2-ol (30.0 g, 0.258 mol) was treated with acetic anhydride (36.6 mL, 0.387 mol). Pyridine (30.0 mL, excess) was added dropwise over a 3 min period at 23° C. Then 4-(N,N-dimethylamino)-pyridine (1.27 g, 10.0 mmol) was added. The reaction was heated to 70° C. for 16 h. The reaction was cooled to 23° C. and poured onto 300 mL of crushed ice. After 15 min of stirring, most of the ice had melted. Solid NaHCO3 was added in portions (bubbling) until the pH was 9. The system was extracted with two portions of diethyl ether (100 mL, then 50 mL). The combined extracts were washed with 1.0 M aq. CuSO4 monohydrate (4×50 mL), dried over MgSO4, and filtered. The filtrate was distilled at ambient pressure at a bath temperature of 80-100° C. to remove most of the diethyl ether. The resulting oil left in the pot was fractionally distilled through a Snyder column with 3 chambers under reduced pressure (6-8 mmHg). A small-volume forerun was collected and discarded (bp<45° C.). The main fraction contained 2-methylhexan-2-yl acetate (bp 45-48° C.). 1H NMR (400 MHz, CDCl3) δ 1.94 (s, 3H), 1.74-1.68 (m, 2H), 1.40 (s, 6H), 1.33-1.22 (m, 4H), 0.88 (t, J=6.8 Hz, 3H). The reaction was cooled to 23° C. The system was extracted with two portions of diethyl ether (100 mL The combined extracts were washed with 1.0 M aq. CuSO4 monohydrate (4×50 mL) dried over MgSO4 filtered The filtrate was distilled at ambient pressure at a bath temperature of 80-100° C. to remove most of the diethyl ether The resulting oil left in the pot was fractionally distilled through a Snyder column with 3 chambers under reduced pressure (6-8 mmHg) A small-volume forerun was collected

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

Procedure: To a flame-dried, nitrogen-purged 500 mL 3-neck roundbottom flask with 250 mL pressure-equalizing addition funnel and magnetic stirbar was charged 81 mL n-butyl lithium (129 mmol, 1 equiv., 1.6 M in hexanes). A degassed solution of 15.0 g 2-methyl-2-hexanol (129 mmol, 1 eq.) in 100 mL anhydrous tetrahydrofuran was charged to the addition funnel and added to the reaction mixture dropwise at 0° C. over 60 minutes. The reaction mixture was warmed for 15 minutes on hot water bath to ensure the reaction was complete. The reaction vessel was cooled to 0° C. and 14.2 g methacryloyl chloride (135 mmol, 1.05 eq.) was added dropwise and allowed to stir for 15 minutes. The addition funnel was replaced with a reflux condenser and the reaction heated to reflux for 20 hours. After the reaction was complete, it was cooled to 0° C. and quenched aqueous sodium bicarbonate. The product was extracted into ethyl ether and the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine and then dried over magnesium sulfate, filtered, concentrated in vacuo, and stored over a small amount of sodium bicarbonate. The crude product mixture was vacuum distilled through a vacuum-jacketed short-path distillation head to afford 14 g (59%) of 2-methylhexan-2-yl methacrylate (XIII) as a colorless liquid. To a flame-dried, nitrogen-purged 500 mL roundbottom flask with 250 mL pressure-equalizing addition funnel added to the reaction mixture dropwise at 0° C. over 60 minutes The reaction mixture was warmed for 15 minutes on hot water bath The addition funnel was replaced with a reflux condenser the reaction heated to reflux for 20 hours it was cooled to 0° C. quenched aqueous sodium bicarbonate The product was extracted into ethyl ether the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine dried over magnesium sulfate filtered concentrated in vacuo distilled through a vacuum-jacketed short-path distillation head