Trichloroacetic Acid → 8-Methoxy-2,3,4,5-tetrahydro-benzo[c]azepin-1-one

HRID 1488668Notes

Reaction equation

HRID 1488668 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][CH2:8][CH2:9][C:10]2=[N:13]O)=[CH:5][CH:4]=1.ClC(Cl)(Cl)C(O)=[O:18]>>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[CH2:7][CH2:8][CH2:9][NH:13][C:10](=[O:18])[C:11]=2[CH:12]=1

Participants

3

Reactant 2

HCID 6421Trichloroacetic AcidHCID 573710067-Methoxy-1-tetralone Oxime

Product 1

HCID 112755298-Methoxy-2,3,4,5-tetrahydro-benzo[c]azepin-1-oneYield 22.3%

Procedure

Following a procedure of Tomita, et. al., H. Chem. Soc. C1969, 183, 7-methoxytetralone oxime (45.0 g, 0.235 mol) was mixed with solid trichloroacetic acid (150 g), and the resulting suspension heated to ca. 80 C. at which time a violent exotherm ensued, yielding a black solid mixture. The residue was cooled, partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution, and the combined organic layers were concentrated in vacuo. The residue was purified by chromatography over silica gel to yield 10.0 g (22%) of 8-methoxy-2,3,4,5-tetrahydro-1H-2-benzazepin-1-one. An analytical sample was obtained by recrystallization from CH2Cl2 /hexanes to yield colorless crystals: mp. 99°-101° C. (lit. (see above) 100°-101° C.); 1H NMR(CDCl3) d7.35(brs, 1H), 7.30(d, J=3 Hz, 1H), 7.10(d, J=9 Hz, 1H), 6.95(dd, J=3, 9 Hz, 1H), 3.82(s, 3H), 3.10(q, J=6 Hz, 2H), 2.80(b, J=6 Hz, 2H), 1.98 (m, 2H).

Workup

  1. temperaturethe resulting suspension heated to ca. 80 C
  2. customyielding a black solid mixture
  3. temperatureThe residue was cooled
  4. custompartitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution
  5. concentrationthe combined organic layers were concentrated in vacuo
  6. customThe residue was purified by chromatography over silica gel

Sources & evidence

ORD record
ord-4eb53c4171a34b4789679f3d247bd836
Source dataset
uspto-grants-1997_10
Patent number
US05674865

Reaction notes

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