2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 12928478, compound

HRID 894472Notes

Reaction equation

HRID 894472 reaction equation
[CH2:1]([N:8]1[CH2:14][CH:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)C2C=C(O)C(O)=CC=2C[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl[C:28]1[C:29](=O)[C:30]([C:38]#N)=[C:31](C#N)[C:32](=[O:35])[C:33]=1Cl.[CH:41]([NH2:54])(C1C=CC=CC=1)[C:42]1C=CC=CC=1.[O:55]1CCCC1>CO.C(O)C>[C:41]([NH:54][C:33]1[C:32]([OH:35])=[CH:31][C:30]2[CH2:38][CH2:9][N:8]([CH2:1][C:2]3[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=3)[CH2:14][CH:13]([C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=3)[C:29]=2[CH:28]=1)(=[O:55])[CH3:42]

Participants

6

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 7036BenzhydrylamineHCID 8028TetrahydrofuranHCID 129284732,3,4,5-Tetrahydro-1-phenyl-3-(phenylmethyl)-1H-3-benzazepine-7,8-diol

Product 1

HCID 12928478HCID 12928478, compound

Reagents, catalysts & solvents 1

HCID 18681192Ethanol, mixt. with methanolSolvent2×

Procedure

A mixture of 16.3 g. (0.0385 mole) of 3-benzyl-7,8-dihydroxy-1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepine and 225 ml. of ethanol-methanol was treated with 10.7 g. (0.00462 mole) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in methanol-ethanol with cooling. After stirring for 30 minutes at 0°, the precipitate is filtered, washed with ethyl acetate and then ether. The quinone is stirred with 200 ml. of tetrahydrofuran and 15 g. of 5 A° molecular sieves while a mixture of 10.6 g. (0.0578 mole) of benzhydrylamine in 30 ml. of tetrahydrofuran was added. The reaction mixture was used and worked up as in Example 1 to give 8.5 g. (57%) of 7,8-amino, hydroxy isomers. Separation of the isomers as described above but with recrystallization from ether gave 8-acetamido-3-benzyl-7-hydroxy-1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepine, m.p. 180.5°, and its 7,8-isomer, m.p. 205°-207°.

Workup

  1. additionA mixture of 16.3 g
  2. filtrationthe precipitate is filtered
  3. washwashed with ethyl acetate
  4. stirringThe quinone is stirred with 200 ml
  5. additionof 5 A° molecular sieves while a mixture of 10.6 g
  6. customto give 8.5 g
  7. customSeparation of the isomers
  8. customwith recrystallization from ether

Sources & evidence

ORD record
ord-d4fdfd3ca8dc4a1baa5a479a9c417548
Source dataset
uspto-grants-1981_08
Patent number
US04284556

Reaction notes

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