2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 14156759, compound

HRID 1904932Notes

Reaction equation

HRID 1904932 reaction equation
ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.[Br:15][C:16]1[CH:17]=[C:18]2[CH2:27][CH2:26][N:25]3[C:19]2=[C:20]([CH:32]=1)[CH:21]=[N:22][C:23]1[CH:31]=[CH:30][CH:29]=[CH:28][C:24]=13.C(N(CC)CC)C>C1(C)C=CC=CC=1.ClCCl>[Br:15][C:16]1[CH:17]=[C:18]2[CH:27]=[CH:26][N:25]3[C:19]2=[C:20]([CH:32]=1)[CH:21]=[N:22][C:23]1[CH:31]=[CH:30][CH:29]=[CH:28][C:24]=13

Participants

6

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8471TriethylamineHCID 14459747HCID 14459747, compound

Product 1

HCID 14156759HCID 14156759, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 6344DichloromethaneSolvent

Procedure

A solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 22 g) in toluene (200 ml) was added dropwise to a refluxing solution of 4-bromo-1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine (10 g) in toluene (750 ml) under nitrogen. The mixture was refluxed for 1 hour, cooled, stirred with triethylamine (3 g) for 10 minutes, and fed to a flash chromatography column (slurry packed with silica, 300 g in dichloromethane). The adsorbed material was eluted with dichloromethane (4 L); 1% methanol/dichloromethane (2 L); and 1% methanol/0.5% ammonium hydroxide/dichloromethane (2 L), whereby the desired product was separated from the remaining quinone. The crude product (10 g) was purified further on a second flash chromatography column (silica gel, 180 g; eluted with 20:80 hexane/dichloromethane, 6 L). The desired product was isolated as a solid (5.4 g). Recrystallization from ethanol (70 ml) at 0° C. gave 3.2 g of crystals which turned to powder after vacuum drying at 110° C., m.p. 122°-123° C.

Workup

  1. temperatureThe mixture was refluxed for 1 hour
  2. temperaturecooled
  3. washThe adsorbed material was eluted with dichloromethane (4 L)
  4. customand 1% methanol/0.5% ammonium hydroxide/dichloromethane (2 L), whereby the desired product was separated from the remaining quinone
  5. customThe crude product (10 g) was purified further on a second flash chromatography column (silica gel, 180 g; eluted with 20:80 hexane/dichloromethane, 6 L)

Sources & evidence

ORD record
ord-dccba6f9b7ad44328d60f21aedc8955b
Source dataset
uspto-grants-1989_06
Patent number
US04840947

Reaction notes

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