Dibromomethane → HCID 86737969, compound

HRID 895013Notes

Reaction equation

HRID 895013 reaction equation
[F:1][C:2]([F:7])([F:6])[C:3]([NH2:5])=[O:4].[Cl:8][C:9]1[C:19]2[CH2:18][CH2:17][NH:16][CH2:15][CH:14]([C:20]3[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][CH:21]=3)[C:13]=2[CH:12]=[C:11]([OH:27])[C:10]=1[OH:28].[F-].[K+].Br[CH2:32]Br>CN(C)C=O>[F:1][C:2]([F:7])([F:6])[C:3]([NH2:5])=[O:4].[Cl:8][C:9]1[C:19]2[CH2:18][CH2:17][NH:16][CH2:15][CH:14]([C:20]3[CH:21]=[CH:22][C:23]([OH:26])=[CH:24][CH:25]=3)[C:13]=2[CH:12]=[C:11]2[O:27][CH2:32][O:28][C:10]=12

Participants

5

Reactant 3

HCID 3024DibromomethaneHCID 522689Potassium FluorideHCID 20572558HCID 20572558, compound

Product 1

HCID 86737969HCID 86737969, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 44 g (0.104 mole) of 6-chloro-7,8-dihydroxy-1-(p-hydroxyphenyl)-2,3,4,5-tetrahydro-1H-3-benzazepine trifluoroacetamide in 700 ml of dry dimethylformamide was treated with 45.5 g (0.784 mole) of potassium fluoride. After five minutes, 11.2 ml (27.6 g, 0.109 mole) of dibromomethane was added. The mixture was heated at 115° and held at 115° for 6 hours. The reaction mixture was concentrated. The residue was dissolved in ethyl acetate and washed several times with water. The dried, concentrated product was chromatographed over 800 g of silica gel with a 1 to 3% methanol in chloroform gradient. The homogeneous fractions gave 30.4 g (71%) of 6-chloro-7,8-methylenedioxy-1-(p-hydroxyphenyl)-2,3,4,5-tetrahydro-1H-3-benzazepine trifluoroacetamide. A sample was crystallized from acetonitrile to give white crystals, m.p. 191°-193°.

Workup

  1. temperatureThe mixture was heated at 115°
  2. waitheld at 115° for 6 hours
  3. concentrationThe reaction mixture was concentrated
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwashed several times with water
  6. customThe dried, concentrated product was chromatographed over 800 g of silica gel with a 1 to 3% methanol in chloroform gradient

Sources & evidence

ORD record
ord-070b60591ff949e6934c688eb15da1dd
Source dataset
uspto-grants-1981_08
Patent number
US04285938

Reaction notes

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