Methylamine → HCID 23654284, compound

HRID 597929Notes

Reaction equation

HRID 597929 reaction equation
[CH3:1][NH2:2].FC(F)(F)S(O[C:9]1[C:10]([Br:27])=[CH:11][C:12]2[CH:18]([CH3:19])[CH2:17][N:16]([C:20](=[O:25])[C:21]([F:24])([F:23])[F:22])[CH2:15][CH2:14][C:13]=2[N:26]=1)(=O)=O.C1COCC1.C([O-])(O)=O.[Na+]>CCOC(C)=O>[Br:27][C:10]1[C:9]([NH:2][CH3:1])=[N:26][C:13]2[CH2:14][CH2:15][N:16]([C:20](=[O:25])[C:21]([F:24])([F:23])[F:22])[CH2:17][CH:18]([CH3:19])[C:12]=2[CH:11]=1

Participants

6

Reactant 4

HCID 6329MethylamineHCID 8028TetrahydrofuranHCID 516892Sodium BicarbonateHCID 23654283HCID 23654283, compound

Product 1

HCID 23654284HCID 23654284, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3-bromo-5-methyl-7-(trifluoroacetyl)-6,7,8,9-tetrahydro-5H -pyrido[2,3-d]azepin-2-ol (30.0 mg, 85.0 μmol), Tf2O (50 μl), K2CO3 (18 mg) and DCM (1 ml) was stirred for 16 h at room temperature. The mixture was extracted with sat. aq. NaHCO3, dried over Na2SO4, concentrated in vacuo and purified by column chromatography to yield 11.0 mg (26%) of 3-bromo-5-methyl-7-(trifluoroacetyl)-6,7,8,9-tetrahydro-5H-pyrido[2,3-d]azepin-2-yl trifluoromethanesulfonate. A mixture of methylamine (50 μl), 3-bromo-5-methyl-7-(trifluoroacetyl)-6,7,8,9-tetrahydro-5H-pyrido[2,3-d]azepin-2-yl trifluoromethanesulfonate (11.0 mg, 22.7 μmol), and THF (1 ml) was heated to reflux for 15 h. The reaction mixture was parted between sat. aq. NaHCO3 and EtOAc. The organic layer was dried, concentrated in vacuo and purified with column chromatography to give 5.2 mg (62%) of 3-bromo-N,5-dimethyl-7-(trifluoroacetyl)-6,7,8,9-tetrahydro-5H-pyrido[2,3-d]azepin-2-amine. MS (ESI) m/z 486.2 (M+H+). A mixture of 3-bromo-N,5-dimethyl-7-(trifluoroacetyl)-6,7,8,9-tetrahydro-5H-pyrido[2,3-d]azepin-2-amine (5.2 mg, 14.2 μmol), K2CO3 (15 mg), MeOH (1 ml) and H2O (100 μl) was heated to reflux for 10 min. The reaction mixture was concentrated in vacuo and the resulting residue was purified by column chromatography to yield 2.1 mg (55%) of 3-bromo-N,5-dimethyl-6,7,8,9-tetrahydro-5H-pyrido[2,3-d]azepin-2-amine. MS (ESI) m/z 271.2 (M+H+).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 15 h
  3. customThe organic layer was dried
  4. concentrationconcentrated in vacuo
  5. custompurified with column chromatography

Sources & evidence

ORD record
ord-62909a7218cc46e6b39225c076d52719
Source dataset
uspto-grants-2011_03
Patent number
US07897595B2

Reaction notes

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