2-Bromo-5-chlorotoluene → Ethyl(3R)-2-(4-chloro-2-methylphenyl)-4,4,4-trifluoro-3-methylbutanoate

HRID 1476109ノート

反応式

HRID 1476109 の反応式
C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[F:11][C:12]([F:22])([F:21])[C@H:13]([CH3:20])[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16].Br[C:24]1[CH:29]=[CH:28][C:27]([Cl:30])=[CH:26][C:25]=1[CH3:31].C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2N(C)C)CCCCC1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:30][C:27]1[CH:28]=[CH:29][C:24]([CH:14]([C@@H:13]([CH3:20])[C:12]([F:21])([F:22])[F:11])[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:25]([CH3:31])[CH:26]=1

参加物

7

反応物 4

HCID 844762-Bromo-5-chlorotolueneHCID 2733832Lithium HexamethyldisilazideHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 6992847Ethyl(3R)-4,4,4-trifluoro-3-methylbutanoate

生成物 1

HCID 58288191Ethyl(3R)-2-(4-chloro-2-methylphenyl)-4,4,4-trifluoro-3-methylbutanoate

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒3 回

実験手順

22.5 ml (22.5 mmol) of a 1 M solution of lithium hexamethyldisilazide in toluene were cooled to −20° C., and a solution of 2.76 g (50.3 mmol) of ethyl (3R)-4,4,4-trifluoro-3-methylbutanoate in 15 ml of abs. toluene was added dropwise. The mixture was stirred for 10 min. At −20° C., a solution, prepared beforehand, of 4.0 g (19.5 mmol) of 2-bromo-5-chlorotoluene, 101 mg (0.45 mmol) of palladium(II) acetate and 371 mg (0.94 mmol) of 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl in 15 ml of abs. toluene was then added dropwise. After the addition had ended, cooling was removed and the resulting reaction mixture was stirred initially at RT for 1 h and then at 100° C. overnight. After cooling, the mixture was filtered through celite, the residue was washed repeatedly with toluene and the filtrate obtained was concentrated under reduced pressure. This gave 3.10 g of the title compound as a crude product which was directly reacted further.

後処理

  1. customAt −20° C., a solution, prepared beforehand
  2. additionAfter the addition
  3. temperaturecooling
  4. customwas removed
  5. customthe resulting reaction mixture
  6. stirringwas stirred initially at RT for 1 h
  7. customat 100° C.
  8. customovernight
  9. temperatureAfter cooling
  10. filtrationthe mixture was filtered through celite
  11. washthe residue was washed repeatedly with toluene
  12. customthe filtrate obtained
  13. concentrationwas concentrated under reduced pressure
  14. customThis gave 3.10 g of the title compound as a crude product which was directly reacted further

出典と根拠

ORDレコード
ord-930ead0b35944f9faa85ec66bba4c650
出典データセット
uspto-grants-2015_04
特許番号
US09018414B2

反応ノート

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