Tetrahydrofuran → 2-Amino-1-methoxy-5,6,8,9-tetrahydrobenzocyclohepten-7-one

HRID 1041151Notes

Reaction equation

HRID 1041151 reaction equation
[CH3:1][O:2][C:3]1[C:8]2[CH2:9][CH2:10][C:11](=[O:14])[CH2:12][CH2:13][C:7]=2[CH:6]=[CH:5][C:4]=1[N+:15]([O-])=O.O1CCCC1>Cl.O>[NH2:15][C:4]1[CH:5]=[CH:6][C:7]2[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9][C:8]=2[C:3]=1[O:2][CH3:1]

Participants

5

Reactant 2

HCID 8028TetrahydrofuranHCID 672641411-Methoxy-2-nitro-8,9-dihydro-5H-benzo[7]annulen-7(6H)-one

Product 1

HCID 672634842-Amino-1-methoxy-5,6,8,9-tetrahydrobenzocyclohepten-7-oneYield 60%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

To a stirred solution of 1-methoxy-2-nitro-5,6,8,9-tetrahydro-benzocyclohepten-7-one (400 mg, 0.002 mol) in tetrahydrofuran (10 mL, 0.1 mol) was added dichlorodihydrostannane (600 mg, 0.003 mol) in 12 M of hydrogen chloride in water (8 mL) over 15 min. The mixture was stirred at room temperature for 36 h. The reaction mixture was concentrated in vacuo, diluted with water (4 mL) and made basic with 10 N NaOH. A solid precipitated out of solution and was removed by filtration through celite. The solid was washed with chloroform and the organic layer dried over magnesium sulfate, filtered and concentrated in vacuo to a yellow solid. The solid was triturated with diethyl ether and collected by filtration to give 2-amino-1-methoxy-5,6,8,9-tetrahydrobenzocyclohepten-7-one as a tan solid (200 mg, 60%). 1H NMR (400 MHz, CDCl3) δ 6.82 (d, 1H, J=7.8 Hz), 6.61 (d, 1H, J=7.8 Hz), 3.77 (broad s, 2H), 3.72 (s, 3H), 2.96 (m, 2H), 2.81 (m, 2H), 2.58 (m, 4H).

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. additiondiluted with water (4 mL)
  3. customA solid precipitated out of solution
  4. customwas removed by filtration through celite
  5. washThe solid was washed with chloroform
  6. dry with materialthe organic layer dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo to a yellow solid
  9. customThe solid was triturated with diethyl ether
  10. filtrationcollected by filtration

Sources & evidence

ORD record
ord-a6e34a05ff004410897ca451530a306d
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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