Sodium Nitrite → 1-((3,5-dimethylisoxazol-4-yl)methyl)-1H-pyrazole-4-carbonyl azide

HRID 658671

Reaction equation

[N:1]([O-])=O.[Na+].[CH3:5][C:6]1[C:10]([CH2:11][N:12]2[CH:16]=[C:15]([C:17]([NH:19][NH2:20])=[O:18])[CH:14]=[N:13]2)=[C:9]([CH3:21])[O:8][N:7]=1>C(O)(=O)C>[CH3:5][C:6]1[C:10]([CH2:11][N:12]2[CH:16]=[C:15]([C:17]([N:19]=[N+:20]=[N-:1])=[O:18])[CH:14]=[N:13]2)=[C:9]([CH3:21])[O:8][N:7]=1

Participants

Conditions

Temperature: 0 °C

Procedure

Sodium nitrite (450 mg, 6.5 mmol, in H2O) (10 mL) was added dropwise, over 10 minutes, to a suspension of 1-((3,5-dimethylisoxazol-4-yl)methyl)-1H-pyrazole-4-carbohydrazide (example 10-1b) (1 g, 4.3 mmol) in 10% aqueous acetic acid (50 mL) and cooled to 0° C. via an ice water bath. The reaction was stirred for an additional 15 minutes then extracted with ethyl acetate (3×, 75 mL). The combined organic extracts were washed with aqueous saturated sodium carbonate (100 mL) followed by H2O (100 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated. The solid product was triturated with ethyl acetate/hexanes (1/9) and dried en vacuo to afford 1-((3,5-dimethylisoxazol-4-yl)methyl)-1H-pyrazole-4-carbonyl azide (1 g, 93%) as a white solid. 1H NMR (CDCl3, 400 MHz): δ2.20 (s, 3H), 2.44 (s, 3H), 5.07 (s, 2H), 7.81 (s, 1H), 7.93 (s, 1H).

Workup

extractionthen extracted with ethyl acetate (3×, 75 mL)
washThe combined organic extracts were washed with aqueous saturated sodium carbonate (100 mL)
dry with materialThe combined organic extracts were dried over sodium sulfate
filtrationfiltered
concentrationconcentrated
customThe solid product was triturated with ethyl acetate/hexanes (1/9)
customdried en vacuo

Sources & evidence

ORD record: ord-ab745a2f7d144fb4bef5f841fce8e631
Source dataset: uspto-grants-2011_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08076491B2

Linked notes

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