1-Bromo-2,3-dichlorobenzene → 1-(2,3-Dichlorophenyl)-[1,4]diazepine

HRID 16119

Reaction equation

HRID 16119 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[Cl:9].C(OC([N:17]1[CH:23]=[CH:22][CH:21]=[N:20][CH:19]=[CH:18]1)=O)(C)(C)C.C1(P(C2C=CC=CC=2)C2(P(C3C=CC=CC=3)C3C=CC=CC=3)CC=C3C(C=CC=C3)=C2C2C3C(=CC=CC=3)C=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Cl:9][C:3]1[C:4]([Cl:8])=[CH:5][CH:6]=[CH:7][C:2]=1[N:20]1[CH:21]=[CH:22][CH:23]=[N:17][CH:18]=[CH:19]1

Participants

6

Reactant 3

HCID 420661-Bromo-2,3-dichlorobenzeneHCID 57499755[1,4]Diazepine-1-carboxylic acid tert-butylesterHCID 86595863(+/-)-2,2-Bis(diphenylphosphino)-1,1-binaphthyl

Product 1

HCID 686314891-(2,3-Dichlorophenyl)-[1,4]diazepine

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

2.25 g (10 mmol) 1-bromo-2,3-dichloro-benzene was dissolved in dry toluene (50 ml), 2.3 (11 mmol) of [1,4]diazepine-1-carboxylic acid tert-butylester was added followed by 0.2 g BINAP (2,2-bis(diphenylphosphino)-1,1′-binaphtyl), 85 mg tris(dibenzylideneacetone)dipalladium(0) and 1.2 g (12 mmol) sodium-tert-butoxyde. The reaction mixture was refluxed for eight hours and filtered. The organic layer was washed with water, dried and evaporated in vacuo. The residue was purified by chromatography and deprotected at 10° C. using 20 ml ethylacetate saturated with gaseous hydrochloric acid, the precipitate was filtered giving 2.1 g (yield: 75%) hydrochloride salt of the title compound, melting at 182-3° C.

Workup

  1. temperatureThe reaction mixture was refluxed for eight hours
  2. filtrationfiltered
  3. washThe organic layer was washed with water
  4. customdried
  5. customevaporated in vacuo
  6. customThe residue was purified by chromatography
  7. customdeprotected at 10° C.
  8. filtrationthe precipitate was filtered

Sources & evidence

ORD record
ord-7a73e7e5afb045feb1e989fcb8ce389d
Source dataset
uspto-grants-2010_06
Patent number
US07737142B2

Linked notes

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