4-Fluorophenylhydrazine hydrochloride → 7,8-Dihydro-5H-pyrido[3,2-b]azepine-6,9-dione 9-[(4-fluorophenyl)hydrazone]

HRID 2425862Notes

Reaction equation

[N:1]1[C:11]2[C:10](=O)[CH2:9][CH2:8][C:7](=[O:13])[NH:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.Cl.[F:15][C:16]1[CH:21]=[CH:20][C:19]([NH:22][NH2:23])=[CH:18][CH:17]=1.C([O-])(=O)C.[Na+].[K+].[Br-]>C(O)(=O)C>[F:15][C:16]1[CH:21]=[CH:20][C:19]([NH:22][N:23]=[C:10]2[CH2:9][CH2:8][C:7](=[O:13])[NH:6][C:5]3[CH:4]=[CH:3][CH:2]=[N:1][C:11]2=3)=[CH:18][CH:17]=1

Participants

Conditions

Temperature: 70 °C

Procedure

183 mg (1.04 mmol) 5H-Pyrido[3,2-b]azepine-6,9(7H,8H)-dione and 186 mg (1.14 mmol) (4-fluorophenyl)hydrazine hydrochloride, and 90 mg (1.1 mmol) sodium acetate were suspended in glacial acetic acid (11 ml) and stirred for 1 hour at 70° C. After cooling to room temperature, the mixture was poured into a 5% aqueous sodium acetate solution. The mixture was extracted with 4×20 ml ethyl acetate. The combined organic layers were dried over sodium sulfate, and evaporated to dryness. Recrystallization from ethanol afforded a yellow solid. Yield: 170 mg (58%);m.p. 232-233° C.; IR (KBr): 3286 cm−1 (NH), 3119/3061 cm−1 (CH-arom.) 2956/2888 cm−1 (CH-aliph.), 1674 cm−1 (C═O); 1H-NMR (DMSO-d6, 400 MHz): δ (ppm)=2.54-2.58 (m, 2H, part of AA′XX′-system, azepine-CH2), 3.01-3.04 (m, 2H, part of AA′XX′-system, azepine-CH2), 7.03-7.07 (m, 2H, arom. H), 7.16-7.20 (m, 2H, arom. H), 7.33-7.40 (m, 2H, arom. H), 8.40 (dd, 1H, 4.4/1.6 Hz, arom. H), 9.35 (s, 1H, NH), 9.77 (s, 1H, NH); C15H13FN4O (284.30).

Workup

temperatureAfter cooling to room temperature
extractionThe mixture was extracted with 4×20 ml ethyl acetate
dry with materialThe combined organic layers were dried over sodium sulfate
customevaporated to dryness
customRecrystallization from ethanol
customafforded a yellow solid

Sources & evidence

ORD record: ord-12af29637751424dad40c4131d5a5bed
Source dataset: uspto-grants-2011_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07968535B2

Reaction notes

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