Hydrazine hydrate (1:1) → 4-Amino-3-chloro-5-fluoro-6-hydrazinopicolinonitrile

HRID 1913902Notes

Reaction equation

O.[NH2:2][NH2:3].[NH2:4][C:5]1[C:10]([F:11])=[C:9](F)[N:8]=[C:7]([C:13]#[N:14])[C:6]=1[Cl:15]>C1COCC1.CS(C)=O.C(#N)C>[NH2:4][C:5]1[C:10]([F:11])=[C:9]([NH:2][NH2:3])[N:8]=[C:7]([C:13]#[N:14])[C:6]=1[Cl:15]

Participants

Conditions

Temperature: 65 °C

Procedure

To a solution of hydrazine hydrate (3.9 g, 78 mmol) in THF (15 mL) and DMSO (10 mL) was added 4-amino-3-chloro-5,6-difluoropicolinonitrile (5 g, 26 mmol) as a solution in DMSO (5 mL). This solution was heated to 65° C. for 45 min, cooled and diluted with acetonitrile (30 mL) to precipitate the product as a light tan solid. This solid was dried under vacuum at 40° C. for 3 h to give 4-amino-3-chloro-5-fluoro-6-hydrazinopicolinonitrile (5.1 g, 98%): mp 215-220° C. dec; 1H NMR (400 MHz, DMSO-d6) 7.9 (br, 1H), 6.5 (br, 2H), 4.0 (br, 2H); 13C {1H} NMR (101 MHz, DMSO-d6) δ 149.34 (d, J=10.5 Hz, C6), 138.28 (d, J=11.6 Hz, C4), 133.81 (d, J=251.6 Hz, C5), 123.74 (d, J=5.3 Hz, C2), 115.87 (s, C3), 112.57 (s, CN); 19F NMR (376 MHz, DMSO-d6) δ −154.6; ESIMS m/z 203 ([M+H]+). Anal. Calcd for C6H5ClFN5: C, 35.75; H, 2.50; N, 34.74. Found: C, 35.97; H, 2.70: N, 35.01.

Workup

temperaturecooled
customto precipitate the product as a light tan solid
customThis solid was dried under vacuum at 40° C. for 3 h

Sources & evidence

ORD record: ord-349e585bc4d941a78dc50cf458f83cfb
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08609853B2

Reaction notes

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