KBS23 - master page

[KlementineJBS]

Link to HIRAC. Original method from J. Batten's PhD thesis, but a similar method is used by Babin et al..

KBS22 Azidation of 1-naphthylamine.docx

Reaction scheme

[KlementineJBS]

Attempts

Identifier	Link	Yield (%)	Reaction time
1	#25	66, impure	1 h
2	#54	22	4.5 h
3	#56	51	2.5 h
4	#59	73	1 h
5	#146	77, not purified	4 h
6	#160	58	1 h
7	#177	left incomplete
8	#181	84, not purified	overnight

[KlementineJBS]

Characterisation

H NMR

KBS23-4.pdf KBS23-4_1.zip

IR

KBS23-2 F7-15.pdf

[KlementineJBS]

Method

1-napthylamine (1.00 g, 6.98 mmol) was dissolved in hydrochloric acid (3.4 M, 7 mL) and sodium nitrite (629 mg, 9.12 mmol, 1.3 equiv.) dissolved in water (2 mL) was added. The mixture was allowed to stir at 0 C for 15 minutes before sodium azide (628 mg, 9.66 mmol, 1.4 equiv.) dissolved in water (2 mL) was added. The reaction was stirred at 0 C for 1 hour, then diluted with water (5 mL) and extracted with diethyl ether (4 x 30 mL). The resulting dark red solution was washed with sodium bicarbonate (2 x 50 mL) and brine (2 x 50 mL), dried over magnesium sulphate and concentrated under reduced pressure to yield a dark red liquid (897 mg, 73%).

[KlementineJBS]

Alternative routes

1. tert-butyl nitrite + TMS azide in MeCN by Sreeman and Cooper
2. Coban et al use only 1 equiv. of sodium nitrite and 1.2 equiv. of azide - perhaps this would simplify workup and purification?