Sulfuric Acid → 7-Hydroxy-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid ethyl ester

HRID 925231Notes

Reaction equation

[CH2:1]([O:3][C:4]([N:6]1[CH2:12][CH2:11][C:10]2[CH:13]=[C:14](N)[CH:15]=[CH:16][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2].[OH:18]S(O)(=O)=O.N([O-])=O.[Na+].C1COCC1>O>[CH2:1]([O:3][C:4]([N:6]1[CH2:12][CH2:11][C:10]2[CH:13]=[C:14]([OH:18])[CH:15]=[CH:16][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

Conditions

Temperature: 70 °C

Procedure

Into a 250 ml flask, the product from step (b) (3 g, 12.82 mmol) dissolved in water (15 ml) and concentrated H2SO4 (1.02 ml, 19.23 mmol) was added The reaction mixture was heated to 70° C. and stirred for 15 minutes. A solution of NaNO2 (1.01 g, 14.74 mmol) in water (30 ml) was quickly added, followed by addition of THF (45 ml). The reaction mixture was stirred at 70° C. for 30 minutes and then allowed to cool to room temperature. The reaction mixture was extracted with EtOAc (3×). The combined EtOAc extracts were washed with brine, dried over Na2SO4, and solvent evaporated in vacuo to give the sub-title compound as a yellow solid (2.0 g) that was used without further purification. MS: ESI (positive): 236 (M+H).

Workup

stirringThe reaction mixture was stirred at 70° C. for 30 minutes
temperatureto cool to room temperature
extractionThe reaction mixture was extracted with EtOAc (3×)
washThe combined EtOAc extracts were washed with brine
dry with materialdried over Na2SO4, and solvent
customevaporated in vacuo

Sources & evidence

ORD record: ord-c25dd445368a43d193e3442023421bb5
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09284277B2

Reaction notes

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