Sodium Azide → 3-[4-(Azidomethyl)phenyl]-3-(Trifluoromethyl)-3H-Diazirine

HRID 73141Notes

Reaction equation

[N-:1]=[N+:2]=[N-:3].[Na+].I[CH2:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2([C:16]([F:19])([F:18])[F:17])[N:15]=[N:14]2)=[CH:9][CH:8]=1>CO>[N:1]([CH2:6][C:7]1[CH:8]=[CH:9][C:10]([C:13]2([C:16]([F:19])([F:17])[F:18])[N:14]=[N:15]2)=[CH:11][CH:12]=1)=[N+:2]=[N-:3]

Participants

Conditions

Temperature: 45 °C

Procedure

NaN3 (0.42 g, 6.2 mmol) was added to a MeOH (30 mL) solution of 3-[4-(iodomethyl)phenyl]-3-(trifluoromethyl)-3H-diazirine (1.01 g, 3.1 mmol). The solution was stirred at 45° C. (6 h). The methanol was evaporated and CH2Cl2 (30 mL) and water (30 mL) were added. The organic layer was extracted and the aqueous layer was washed with CH2Cl2 (1×30 mL). The organic layers were combined and concentrated in vacuum. Finally, the residue was purified by silica gel flash chromatography (0→30% EtOAc in hexanes) to obtain 570 mg (77%) of a pale yellow liquid: Rf=0.85 (1/9 EtOAc/hexanes); IR (nujol) 3298, 2927, 2859, 2100 (N3), 1694, 1615, 1459, 1374, 1236, 1162, 1055, 939, 805, 728 cm−1; 1H NMR (CDCl3): δ 4.37 (s, CH2), 7.21 (d, J=7.9 Hz, 2 C6H4), 7.35 (d, J=7.9 Hz, 2 C6H4); 13C NMR (CDCl3): δ 28.3 (q, J=40.2 Hz, C diazirine), 54.1 (CH2N3), 122.1 (q, J=273.0 Hz, CF3), 127.0 (C6H2), 128.5 (C6H2), 129.2 (C6H2), 137.2 (C6H2).

Workup

customThe methanol was evaporated
additionCH2Cl2 (30 mL) and water (30 mL) were added
extractionThe organic layer was extracted
washthe aqueous layer was washed with CH2Cl2 (1×30 mL)
concentrationconcentrated in vacuum
customFinally, the residue was purified by silica gel flash chromatography (0→30% EtOAc in hexanes)

Sources & evidence

ORD record: ord-dbf321d9ab1d4d3d87a50267e89485ad
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08829033B2

Reaction notes

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