Pivalic acid → 3-Chloro-10,11-dihydro-5H-benzo(d)naphtho(2,3-b)pyran-8(9H)-one

HRID 590647

反応式

HRID 590647 の反応式
C(O)(=O)C(C)(C)C.C(=O)([O-])[O-].[K+].[K+].Br[C:15]1[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][C:16]=1[CH2:17][O:18][C:19]1[CH:28]=[C:27]2[C:22]([CH2:23][CH2:24][CH2:25][C:26]2=[O:29])=[CH:21][CH:20]=1>CC(N(C)C)=O.C([O-])(=O)C(C)(C)C.[Pd+2].C([O-])(=O)C(C)(C)C.FC1C=CC(P(C2C=CC(F)=CC=2)C2C=CC(F)=CC=2)=CC=1>[Cl:34][C:31]1[CH:32]=[CH:33][C:15]2[C:20]3[CH:21]=[C:22]4[CH2:23][CH2:24][CH2:25][C:26](=[O:29])[C:27]4=[CH:28][C:19]=3[O:18][CH2:17][C:16]=2[CH:30]=1

参加物

7

反応物 3

HCID 6417Pivalic acidHCID 11430Potassium CarbonateHCID 696728137-((2-Bromo-5-chlorophenyl)methoxy)-1,2,3,4-tetrahydronaphthalen-1-one

生成物 1

HCID 696733663-Chloro-10,11-dihydro-5H-benzo(d)naphtho(2,3-b)pyran-8(9H)-one収率 67%

試薬・触媒・溶媒 3

HCID 140387Tris(4-fluorophenyl)phosphine触媒HCID 24905427palladium(II) pivalate触媒HCID 31374Dimethylacetamide溶媒

反応条件

温度
60 °C

実験手順

To a 1 L flask containing palladium(II) pivalate (1.18 g, 3.8 mmol), tri(4-fluorophenyl)phosphine (1.20 g, 3.8 mmol), pivalic acid (2.33 g, 22.8 mmol) and potassium carbonate (31.8 g, 228 mmol) was added a solution of 7-(2-bromo-5-chlorobenzyloxy)-3,4-dihydronaphthalen-1(2H)-one (27.8 g, 76.2 mmol) in dimethyacetamide (380 mL). The flask was evacuated and backfilled with argon 5 times and then stirred under argon at 60° C. for 24 hours. The reaction was cooled to room temperature and diluted with MTBE and water. The resulting biphasic mixture was stirred for 3 hours and filtered through Celite, rinsing with MTBE. The organic layer of the filtrate was separated and then washed twice with water and once with brine. The organics were then dried with magnesium sulfate, filtered, concentrated and purified by flash column chromatography (Hexanes/DCM) to yield 3-chloro-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (14.4 g, 67% yield) as an off-white solid.

後処理

  1. customThe flask was evacuated
  2. temperatureThe reaction was cooled to room temperature
  3. additiondiluted with MTBE and water
  4. stirringThe resulting biphasic mixture was stirred for 3 hours
  5. filtrationfiltered through Celite
  6. washrinsing with MTBE
  7. customThe organic layer of the filtrate was separated
  8. washwashed twice with water and once with brine
  9. dry with materialThe organics were then dried with magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. custompurified by flash column chromatography (Hexanes/DCM)

出典と根拠

ORDレコード
ord-378a72ed2f4340af935a90e193ae548a
出典データセット
uspto-grants-2016_01
特許番号
US09233974B2

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