Methyl Anthranilate → methyl 2-(9H-carbazol-1-ylamino)benzoate

HRID 76379

Reaction equation

HRID 76379 reaction equation
[C:1]([O:10][CH3:11])(=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[NH2:4].Br[C:13]1[C:25]2[NH:24][C:23]3[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=3)[C:17]=2[CH:16]=[CH:15][CH:14]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:22]1([NH:4][C:3]2[CH:5]=[CH:6][CH:7]=[CH:8][C:2]=2[C:1]([O:10][CH3:11])=[O:9])[C:23]2[NH:24][C:25]3[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:18]=2[CH:19]=[CH:20][CH:21]=1

Participants

7

Reactant 4

HCID 8635Methyl AnthranilateHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 112303351-Bromo-9H-carbazole

Product 1

HCID 68242730methyl 2-(9H-carbazol-1-ylamino)benzoate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

35.51 g (234.9 mmol) of methyl anthranilate are dissolved in 500 ml of toluene and degassed well. 52 g (213 mmol) of 1-bromocarbazole, 2.1 g (10.7 mmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 1.19 g (5.34 mmol) of Pd(OAc)2 and 76.5 g (234.9 mmol) of Cs2CO3 are added, and the mixture is then degassed and stirred at 100° C. under a protective-gas atmosphere for 24 h. The solids are subsequently filtered off via Celite, and the organic phase is washed with water, dried over MgSO4 and evaporated. The crude product is washed by stirring with hot heptane, giving 57.4 g (108 mmol), 86% of theory, purity according to HPLC 86%.

Workup

  1. customdegassed well
  2. customthe mixture is then degassed
  3. filtrationThe solids are subsequently filtered off via Celite
  4. washthe organic phase is washed with water
  5. dry with materialdried over MgSO4
  6. customevaporated
  7. washThe crude product is washed
  8. stirringby stirring with hot heptane
  9. customgiving 57.4 g (108 mmol), 86% of theory, purity

Sources & evidence

ORD record
ord-a41f1b89e91147079a468a9da15166a9
Source dataset
uspto-grants-2014_09
Patent number
US08835626B2

Linked notes

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