1-Bromonaphthalene → HCID 68814844, compound

HRID 1821150Notes

Reaction equation

HRID 1821150 reaction equation
[C:1](P(C(C)(C)C)C(C)(C)C)(C)(C)[CH3:2].[C:14]1([NH:20][C:21]2[CH:41]=[CH:40][C:24]3[O:25][C:26]4[C:32]([NH:33][C:34]5[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=5)=[CH:31][CH:30]=[CH:29][C:27]=4[O:28][C:23]=3[CH:22]=2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.Br[C:43]1[C:52]2[C:47](=[CH:48][CH:49]=[CH:50][CH:51]=2)[CH:46]=[CH:45][CH:44]=1.CC(C)([O-])C.[Na+].[C:59]1([CH3:66])[C:60]([CH3:65])=[CH:61][CH:62]=[CH:63][CH:64]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O>[C:43]1([N:20]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:21]2[CH:41]=[CH:40][C:24]3[O:25][C:26]4[C:32]([N:33]([C:65]5[C:60]6[C:59](=[CH:64][CH:63]=[CH:62][CH:61]=6)[CH:66]=[CH:2][CH:1]=5)[C:34]5[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=5)=[CH:31][CH:30]=[CH:29][C:27]=4[O:28][C:23]=3[CH:22]=2)[C:52]2[C:47](=[CH:48][CH:49]=[CH:50][CH:51]=2)[CH:46]=[CH:45][CH:44]=1

Participants

9

Reactant 5

HCID 70011-BromonaphthaleneHCID 7237O-Xylene2×HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 68812893HCID 68812893, compound

Product 1

HCID 68814844HCID 68814844, compoundYield 38.5%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 0.161 g (0.715 mmole) of palladium (II) acetate in 20 ml of xylene was added 0.58 g (2.86 mmoles) of tri-tert-butylphosphine and heated at 80° C. for 30 minutes. The resulting solution was forwarded into a solution heated at 80° C. of 5.24 g (0.0143 mole) of N,N′-diphenyl-2,6-diaminodibenzodioxin, 7.41 g (0.0358 mole) of 1-bromonaphthalene, and 5.77 g (0.06 mole) of sodium tert-butoxide in 260 ml of xylene. The mixture was then heated up to 135° C. and further heated at this temperature with stirring for 4 hours. The mixture was cooled to room temperature, 200 ml of water was added, and the aqueous layer was separated from the organic layer. The aqueous layer was washed with 200 ml of toluene, the toluene washing was mixed with the organic layer, the mixture was concentrated and dried under reduced pressure to give 9.5 g of a crude product. The crude product was subjected to reslurrying under heat with ethyl acetate and dried under reduced pressure to give 3.40 g (0.0055 mole) of N,N′-di(1-naphthyl)-N,N′-diphenyl-2,6-diaminodibenzodioxin in a 38.5% yield. The product thus obtained showed a purity of 98.3 area % (HPLC, 254 nm). The product was further purified by sublimation.

Workup

  1. temperatureThe mixture was then heated up to 135° C.
  2. temperaturefurther heated at this temperature
  3. temperatureThe mixture was cooled to room temperature
  4. customthe aqueous layer was separated from the organic layer
  5. washThe aqueous layer was washed with 200 ml of toluene
  6. additionthe toluene washing was mixed with the organic layer
  7. concentrationthe mixture was concentrated
  8. customdried under reduced pressure
  9. customto give 9.5 g of a crude product
  10. customdried under reduced pressure

Sources & evidence

ORD record
ord-2f02e9a78df14219a19a377bf0d11da7
Source dataset
uspto-grants-2009_10
Patent number
US07605277B2

Reaction notes

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