Methanol → Methyl 2-chloro-4-methylbenzoate

HRID 351120

反応式

HRID 351120 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[Cl:9].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[CH3:46][OH:47].CN([CH:51]=[O:52])C>CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:9][C:3]1[CH:4]=[C:5]([CH3:8])[CH:6]=[CH:7][C:2]=1[C:46]([O:52][CH3:51])=[O:47]

参加物

7

反応物 5

HCID 887MethanolHCID 6228DimethylformamideHCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 1387894-Bromo-3-chlorotoluene

生成物 1

HCID 22019481Methyl 2-chloro-4-methylbenzoate収率 28%

試薬・触媒・溶媒 1

HCID 167845palladium(II) acetate触媒

反応条件

温度
80 °C

実験手順

To 4-bromo-3-chlorotoluene (4.97 g, 24.2 mmol) in DMF (25 mL) is added Pd(OAc)2 (0.54 g, 2.42 mmol), 1,3-bis(diphenylphosphino)propane (0.998 g, 2.42 mmol), triethylamine (12.5 mL) and methanol (12.5 mL). The reaction vessel is evacuated and purged three times with carbon monoxide gas. A balloon filled with carbon monoxide gas is used to maintain the carbon monoxide atmosphere. The reaction mixture is heated at 80° C. for 8 hr. After cooling H2O (50 mL) is added. The mixture is extracted with hexanes (2×50 mL). The combined organic layers are dried over Na2SO4, filtered, concentrated and chromatographed with 0–3% EtOAc in hexanes. 1.24 g (28%) of methyl 2-chloro-4-methylbenzoate is isolated as a colorless oil. EIMS m/e 184 (M+; 35Cl) and 186 (M+; 37Cl).

後処理

  1. customThe reaction vessel is evacuated
  2. custompurged three times with carbon monoxide gas
  3. additionA balloon filled with carbon monoxide gas
  4. temperatureto maintain the carbon monoxide atmosphere
  5. temperatureAfter cooling H2O (50 mL)
  6. additionis added
  7. extractionThe mixture is extracted with hexanes (2×50 mL)
  8. dry with materialThe combined organic layers are dried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customchromatographed with 0–3% EtOAc in hexanes

出典と根拠

ORDレコード
ord-722eefee9f754a47a0574d530b790364
出典データセット
uspto-grants-2007_02
特許番号
US07183320B2

関連ノート

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