3-azido-3-methylbutanoic acid

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Borane dimethylsulfide complex (2 M, 15 mL, 30 mmol) was added over 20 min to 3-azido-3-methylbutanoic acid (4.25 g, 30 mmol) in THF (15 mL) at room temperature. The reaction was stirred for 16 h. The reaction mixture was cooled in an ice bath and methanol (50 mL) was added dropwise to the solution over 15 min. Then 4 M HCl in dioxanes (7.5 mL, 30 mmol) was added to the reaction mixture and stirred for 30 min. The reaction mixture was concentrated on a rotovap to a colorless liquid (3.33 g, 91%). This material was used without further purification. 1H NMR (CDCl3, 400 MHz): δ 1.35 (s, 6H), 1.74-1.78 (t, J=6.4, 2H), 3.75-3.80 (t, J=6.4, 2H). LRMS (ESI+) for C5H11N3O (129.1); Found: did not ionize. The reaction mixture was cooled in an ice bath stirred for 30 min The reaction mixture was concentrated on a rotovap to a colorless liquid (3.33 g, 91%) This material was used without further purification

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3-azido-3-methylbutanoic acid (10 g, 69.8 mmol) in anh. dichloroethane (50 mL) was added thionyl chloride in one portion (10.0 mL, 2 equiv, 0.14 mol). The flask was fitted with a condenser and the reaction was heated in a 50° C. oil bath for 2 h. The reaction was concentrated to a brown-black suspension. The residue was vacuum distilled through a short path distillation apparatus. The forerun was discarded and the major fraction distilled at 66° C. at 18 mbar as a pale yellow liquid (9.66 g, 85.6%). 1H NMR (CDCl3, 400 MHz): δ 1.41 (s, 6H), 2.51 (s, 2H), 2.98 (s, 2 H). The flask was fitted with a condenser The reaction was concentrated to a brown-black suspension distilled through a short path distillation apparatus the major fraction distilled at 66° C. at 18 mbar as a pale yellow liquid (9.66 g, 85.6%)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: According to the method of S, Nagarajan and B. Ganem, J. Org. Chem., 51, 4856, (1986), sodium azide (52 g, 0.8 mol) in water (100 mL) was added to a stirred solution of 3,3-dimethylacrylic acid (20 g, 0.2 mol) in glacial acetic acid (50 mL) in one portion. The clear yellow solution was stirred for 1 h at RT, then heated in an oil bath at 95° C. for 2 days. Water (50 mL) was added to the cooled orange solution. This solution was poured into a separatory funnel and extracted with ether (5×200 mL). The combined organic extracts were dried over anhydrous MgSO4 and concentrated to an orange oil. This oil was used without further purification. heated in an oil bath at 95° C. for 2 days This solution was poured into a separatory funnel extracted with ether (5×200 mL) The combined organic extracts were dried over anhydrous MgSO4 concentrated to an orange oil This oil was used without further purification

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3-azido-3-methylbutanoic acid (10 g, 69.8 mmol) in anhydrous 1,2-dichloroethane (50 mL) was added thionyl chloride (10.0 mL, 140 mmol). The flask was fitted with a condenser and the reaction was heated in a 50° C. oil bath for 2 hours. The reaction was concentrated to a brownish-black suspension. The residue was vacuum distilled through a short path distillation apparatus. The forerun was discarded and the major fraction distilled at 66° C. at 18 mbar as a pale yellow liquid (9.66 g, 59.7 mmol, 85.6%). 1H NMR (CDCl3, 400 MHz): δ 1.41 (s, 6H), 2.51 (s, 2H), 2.98 (s, 2H). 1H NMR (CDCl3, 400 MHz): δ 1.44 (s, 6H), 3.10 (s, 2H). The flask was fitted with a condenser The reaction was concentrated to a brownish-black suspension distilled through a short path distillation apparatus

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3,3-dimethylacrylic acid (20 g, 0.2 mol) in glacial acetic acid (50 mL) was added a solution of sodium azide (52 g, 0.8 mol) in water (100 mL) in one portion. The clear yellow solution was stirred for 1 hour at room temperature and then heated in an oil bath at 95° C. for 2 days. Water (50 mL) was added to the cooled orange solution. This solution was poured into a separatory funnel and extracted with ether (5×200 mL). The combined organic extracts were dried over anhydrous MgSO4 and concentrated to an orange oil. This oil was used without further purification. 1H NMR (CDCl3, 400 MHz): δ 1.44 (s, 6H), 2.55 (s, 2H), 11.80 (bs, 1H). heated in an oil bath at 95° C. for 2 days This solution was poured into a separatory funnel extracted with ether (5×200 mL) The combined organic extracts were dried over anhydrous MgSO4 concentrated to an orange oil This oil was used without further purification