Aniline → 1H-1,2-Diazepine

HRID 988803Notes

Reaction equation

HRID 988803 reaction equation
[NH:1]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=[N:2]1.C[O:9]C(OC)OC.NC1C=CC=CC=1.C(OCC)(=O)C>C(O)(=O)C.CCCCCC>[OH-:9].[NH4+:1].[NH:1]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=[N:2]1

Participants

8

Reactant 4

HCID 6115AnilineHCID 8857Ethyl AcetateHCID 9005Trimethyl orthoformateHCID 1667341H-1,2-Diazepine2×

Product 2

HCID 14923Ammonium HydroxideHCID 1667341H-1,2-DiazepineYield 70%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8058HexaneSolvent

Procedure

Aldehyde 160 (1.08 g, 3.0 mmol) was converted at 25° C. by standard procedures to amine 161, using 99:1 trimethylorthoformate:acetic acid as solvent (20 mL), 1.1 equivalents of aniline (3.3 mmol), and after 1 hour adding 1.5 equivalents (8.9 mmol) of commercial 1M sodium cyanoborohydride THF solution. Aqueous workup and silica gel chromatography (eluent: 90:10:1 ethyl acetate:hexane:ammonium hydroxide) gave amine 161 as a colorless foam (0.93 g, 70%).

Sources & evidence

ORD record
ord-b0aa39c035284ec7aa14d7558abcd70c
Source dataset
uspto-grants-2003_10
Patent number
US06635661B2

Reaction notes

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