2,4-Dihydroxybenzaldehyde → 2-(2,4-Dihydroxy-benzylidene)-5-methyl-furan-3-one

HRID 1944617

반응식

HRID 1944617 반응식
[CH3:1][C:2]1[O:6][CH2:5][C:4](=[O:7])[CH:3]=1.[Cl-].[Ca+2].[Cl-].[OH:11][C:12]1[CH:19]=[C:18]([OH:20])[CH:17]=[CH:16][C:13]=1[CH:14]=O.B(OC(CC)C)(OC(CC)C)OC(CC)C>ClCCl.CN(C)C=O.C(N)CCC.C(O)(=O)C>[OH:11][C:12]1[CH:19]=[C:18]([OH:20])[CH:17]=[CH:16][C:13]=1[CH:14]=[C:5]1[C:4](=[O:7])[CH:3]=[C:2]([CH3:1])[O:6]1

참가 물질

9

반응물 4

HCID 72132,4-DihydroxybenzaldehydeHCID 31077Tris(1-methylpropyl) borateHCID 5284359Calcium ChlorideHCID 127115945-Methylfuran-3-one

생성물 1

HCID 670557422-(2,4-Dihydroxy-benzylidene)-5-methyl-furan-3-one수율 56.2%

시약·촉매·용매 4

HCID 8007Butylamine촉매HCID 176Acetic Acid용매HCID 6228Dimethylformamide용매HCID 6344Dichloromethane용매2회

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온도
2.5 °C

실험 절차

5-methyl-furan-3-one (2, 5.9 g g, 0.060 mol) was dissolved in dichloromethane (80 mL) and taken in a 3-necked 500 mL round bottomed flask fitted with a mechanical agitator and calcium chloride guard tube. 2,4-Dihydroxybenzaldehyde (3d, 7.4 g, 0.053 mol) dissolved in dimethylformamide (8 mL) was added. The mixture was cooled to 0-5° C. with stirring. Tri-sec-butyl borate (13.4 g, 0.058 mol) was added and stirred for 2 h. n-Butyl amine (9 drops) was added over a period of 3 h and the reaction mixture allowed to warm to room temp. on its own and stirred at room temp. overnight. The dark red color solution was poured into 5% aq. acetic acid solution (120 mL) preheated to 60° C. with stirring. This was stirred for 30 min., and then allowed to settle down. The dichloromethane layer was isolated and concentrated under reduced pressure to get red color gummy material. This gummy material was washed with water (3×20 mL). Acetonitrile (20 mL) was added to the gummy material and stirred vigorously. The product precipitated out. This was filtered, washed with acetonitrile (20 mL), and the filtered solid dried in vacuo at 110° C., get pure 2-(2,4-Dihydroxy-benzylidene)-5-methyl-furan-3-one (4d) as a red powder (6.5 g, 50% yield), m.p. 239.4-242.5° C. (decomposes).

후처리

  1. customtaken in a 3-necked 500 mL round bottomed flask
  2. additionwas added
  3. additionwas added over a period of 3 h
  4. temperatureto warm to room temp. on its own
  5. stirringstirred at room temp. overnight
  6. custompreheated to 60° C.
  7. stirringwith stirring
  8. stirringThis was stirred for 30 min.
  9. concentrationconcentrated under reduced pressure
  10. customto get red color gummy material
  11. washThis gummy material was washed with water (3×20 mL)
  12. additionAcetonitrile (20 mL) was added to the gummy material
  13. stirringstirred vigorously
  14. customThe product precipitated out
  15. filtrationThis was filtered
  16. washwashed with acetonitrile (20 mL)
  17. customthe filtered solid dried in vacuo at 110° C.

출처 및 근거

ORD 기록
ord-87c7f4cb9862460da274bb884e8d535d
출처 데이터셋
uspto-grants-2013_03
특허 번호
US08394852B2

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