tert-butyl N-diazocarbamate

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

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

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

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

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: To a stirred solution of 8.0 g. (0.048 mole) of α-(2-aminomethyl-1,4-cyclohexadienyl)acetic acid and 3.8 g (0.096 mole) of NaOH in 150 ml. of water was added a solution of 10.3 g. (0.072 mole) of t-butoxycarbonylazide in 80 ml. of THF and the mixture was stirred for 18 hours at room temperature. The THF was removed under reduced pressure and the residual solution was washed with ether (2× 100 ml.), acidified with 6 N HCl and extracted with ether (3× 100 ml.). The combined extracts were washed with water (2×100 ml.) and a saturated NaCl solution (100 ml.), dried with Na2SO4 and evaporated to dryness. The oily residue was triturated with n-hexane to give 10.5 g. (82%) of colorless powder melting at 113° C. The THF was removed under reduced pressure the residual solution was washed with ether (2× 100 ml.) extracted with ether (3× 100 ml.) The combined extracts were washed with water (2×100 ml.) a saturated NaCl solution (100 ml.), dried with Na2SO4 evaporated to dryness The oily residue was triturated with n-hexane to give 10.5 g

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

Procedure: To a stirred solution of 8.0 g. (0.048 mole) of α-(2-aminomethyl-1,4-cyclohexadienyl)acetic acid and 3.8 g. (0.096 mole) of NaOH in 150 ml. of water was added a solution of 10.3 g. (0.072 mole) of t-butoxycarbonylazide in 80 ml. of THF and the mixture was stirred for 18 hours at room temperature. The THF was removed under reduced pressure and the residual solution was washed with ether (2×100 ml.), acidified with 6 N HC1 and extracted with ether (3×100 ml.). The combined extracts were washed with water (2×100 ml.) and a saturated NaCl solution (100 ml.), dried with Na2SO4 and evaporated to dryness. The THF was removed under reduced pressure the residual solution was washed with ether (2×100 ml.) extracted with ether (3×100 ml.) The combined extracts were washed with water (2×100 ml.) a saturated NaCl solution (100 ml.), dried with Na2SO4 evaporated to dryness

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

Procedure: A mixture of t-butyl azidoformate (15.81 g) and triethylamine (30 ml) was added dropwise to a stirred suspension of 2-bromoethylamine hydrobromide (20.5 g.), in methylene chloride (100 ml.). The mixture was stirred for 3 hr., then filtered. The filtrate was concentrated to a small volume, and the residue was distributed between ether and water. The ether layer was dried, then distilled under reduced pressure, collecting the fraction b.p. 92°-94°/0.9 nm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.) , then filtered The filtrate was concentrated to a small volume The ether layer was dried distilled under reduced pressure collecting the fraction b.p. 92°-94°/0.9 nm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.)

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

Procedure: A mixture of t-butyl azidoformate (15.81 g) and triethylamine (30 ml) was added dropwise to a stirred suspension of 2-bromoethylamine hydrobromide (20.5 g.); in methylene chloride (100 ml.). The mixture was stirred for 3 hr., then filtered. The filtrate was concentrated to a small volume, and the residue was distributed between ether and water. The ether layer was dried, then distilled under reduced pressure, collecting the fraction b.p. 92°-94°/0.9 mm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.) , then filtered The filtrate was concentrated to a small volume The ether layer was dried distilled under reduced pressure collecting the fraction b.p. 92°-94°/0.9 mm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.)

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

Procedure: A mixture of m-nitrophenylglycine (58.0 g, 0.296 mol), MgO (23.92 g, 0.6 mol) and t-butoxylcarbonyl azide (85.2 g, 0.6 mol) in 50% aqueous dioxane (700 ml) was heated at 45° for 17 hours. The reaction was cooled, water (750 ml) was added and the mixture was filtered. The filtrate was washed with ether (1000 ml), acidified to pH 3 with 40% H3PO4, and extracted with ethyl acetate. The dried extracts were evaporated to give α-t-butoxycarbonylamino-m-nitrophenylacetic acid (70.3 g). was heated at 45° for 17 hours The reaction was cooled the mixture was filtered The filtrate was washed with ether (1000 ml) extracted with ethyl acetate The dried extracts were evaporated

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

Procedure: N-methylhydroxylamine hydrochloride (14.6 g.) in 20 ml. of water was cooled in an ice-bath and treated with 20 g. of t-butyl azidoformate. A solution of 22.4 g. of sodium hydroxide in 80 ml. of water was added dropwise with stirring over 45 minutes while controlling the temperature below 10° C. The mixture was allowed to warm to room temperature with stirring over a 60 minute period after the addition during which time a little more sodium hydroxide solution and N-methyl hydroxylamine were added. The solution was extracted with 2 × 50 ml. of ether, and the extracts were discarded. The aqueous phase, with cooling, was adjusted to pH 3.5 with 6 N hydrochloric acid, and extracted with 5 × 60 ml. of ether. The combined ether extracts were dried over magnesium sulfate and evaporated to 16 g. of oily N-t-butoxycarbonyl-N-methyl hydroxylamine. treated with 20 g the temperature below 10° C with stirring over a 60 minute period were added The solution was extracted with 2 × 50 ml The aqueous phase, with cooling extracted with 5 × 60 ml The combined ether extracts were dried over magnesium sulfate evaporated to 16 g