Hydrochloric Acid → 6,7-Difluoro-2-methyl-4H-3-thia-4,9-diaza-benzo[f]azulen-10-ylamine hydrochloride

HRID 131383

Reaction equation

[F:1][C:2]1[C:7]([F:8])=[CH:6][C:5]([NH:9][C:10]2[S:11][C:12]([CH3:17])=[CH:13][C:14]=2[C:15]#[N:16])=[C:4]([N+:18]([O-])=O)[CH:3]=1.O.O.[Sn](Cl)[Cl:24].Cl>C(O)C>[ClH:24].[F:8][C:7]1[C:2]([F:1])=[CH:3][C:4]2[N:18]=[C:15]([NH2:16])[C:14]3[CH:13]=[C:12]([CH3:17])[S:11][C:10]=3[NH:9][C:5]=2[CH:6]=1

Participants

Conditions

Temperature: 86.5 °C

Procedure

Add 2-(4,5-difluoro-2-nitro-phenylamino)-5-methyl-thiophene-3-carbonitrile (94.0 g, 318 mmol) and tin (II) chloride dihydrate (225 g, 997 mmol) to ethanol (1400 mL) and aqueous 6N HCl (1400 mL) with stirring under nitrogen. Heat at gentle reflux (86-87° C.) for 0.3 hours, and then allow cooling to ambient temperature. Filter, rinse with water (3×250 mL) and dry at 50-60° C. to give 95.7 g (100%) of the title compound. 1H NMR (400 MHz, DMSO-d6) δ 11.41 (bs, 1H), 9.84 (bs, 1H), 9.33 (bs, 1H), 8.93 (bs, 1H), 7.00 (m, 2H), 6.85 (s, 1H), 2.28 (s, 3H). HRMS (ES) exact mass M+H calcd for C12H9F2N3S (freebase) 266.0563; found 266.0555.

Workup

temperatureHeat
temperatureallow cooling to ambient temperature
filtrationFilter
washrinse with water (3×250 mL)
customdry at 50-60° C.

Sources & evidence

ORD record: ord-864a9ab7a1f9408f9ff352b9bb18353c
Source dataset: uspto-grants-2008_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07384934B2

Linked notes

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