Phosphoric Acid → 1,3-Benzenediol, 4-methyl-

HRID 4882

反応式

HRID 4882 の反応式
[OH:1][C:2]1[CH:9]=[C:8]([OH:10])[CH:7]=[CH:6][C:3]=1[CH:4]=O.P(=O)(O)(O)O.[H][H]>CC(O)C.[Pd]>[CH3:4][C:3]1[CH:6]=[CH:7][C:8]([OH:10])=[CH:9][C:2]=1[OH:1]

参加物

6

反応物 3

HCID 1004Phosphoric AcidHCID 72132,4-DihydroxybenzaldehydeHCID 178418361HCID 178418361、化合物2 回

生成物 1

HCID 103331,3-Benzenediol, 4-methyl-収率 98.1%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 3776Isopropanol溶媒

実験手順

2,4-Dihyroxybenzaldehyde (33.97 gm, 0.246 mol) (recrystallized from toluene) was dissolved in spectroscopic grade 2-propanol (3 L) in a round bottom flask fitted with a gas inlet and a bubbler outlet. 10% Palladium on carbon (1.35 gm) was added followed by phosphoric acid (3mL) and the mixture was sparaged with nitrogen. The nitrogen flow was switched to hydrogen and the mixture was rapidly stirred with ice cooling. After 3 hours hydrogen uptake was complete and the catalyst was removed by filtration. The filtrate was stripped down to 200 mL and 200 mL of ethyl acetate was added. The solution was washed with 4×200 mL of water and the combined water extracts back-extracted with ethyl acetate. These organic extracts were water washed and the combined organic layers dried over sodium sulfate and stripped down to afford the product as a colorless crystalline solid (29.95 gm, 98%). M.p.: 106° C. (Lit. 106°-107° C. [J. C. Bell, W. Bridge, and A. Robertson, J. Chem. Soc., 1542-45 (1937)]). NMR (DMSO-d6): δ 1.961 (s, Me), 6.076 (dd, H-6, J[5,6]=8 hz, J[2,6]=2 hz), 6.231 (d, H-2), 6.760 (d, H-5) 8.867 (s, OH), an 9.008 (s, OH).

後処理

  1. customfitted with a gas inlet and a bubbler outlet
  2. customthe catalyst was removed by filtration
  3. additionwas added
  4. washThe solution was washed with 4×200 mL of water
  5. extractionthe combined water extracts back-extracted with ethyl acetate
  6. washwashed
  7. dry with materialthe combined organic layers dried over sodium sulfate

出典と根拠

ORDレコード
ord-237c45c77bf1482fa8552c921abf2dea
出典データセット
uspto-grants-1993_09
特許番号
US05242796

関連ノート

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