Oxygen → (R,S)-Equol

HRID 1634369Notes

Reaction equation

HRID 1634369 reaction equation
O=O.[OH:3][C:4]1[CH:21]=[CH:20][C:7]([C:8]2[C:17](=O)[C:16]3[C:11](=[CH:12][C:13]([OH:19])=[CH:14][CH:15]=3)[O:10][CH:9]=2)=[CH:6][CH:5]=1>C(O)(=O)C.[Pd]>[OH:19][C:13]1[CH:12]=[C:11]2[C:16]([CH2:17][CH:8]([C:7]3[CH:20]=[CH:21][C:4]([OH:3])=[CH:5][CH:6]=3)[CH2:9][O:10]2)=[CH:15][CH:14]=1

Participants

5

Reactant 2

HCID 977OxygenHCID 5281708Daidzein

Product 1

HCID 382975(R,S)-EquolYield 75.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolvent

Procedure

A suspension of Palladium-on-charcoal (10%, 2.2 g) in glacial acetic acid (15 ml) was treated with oxygen for three days. The suspension catalyst was added to the solution of 4′,7-dihydroxy isoflavone (0.5 g, mmol) in diglume (60 ml). After 30 min. of catalytic hydrogenation at atmospheric pressure, the solution was filtered and washed with diglume and hot acetic acid. The combined filtrate were evaporoted by using water vacuum pump followed by high vacuum pump. The crude was dissolved in ethylacetate and wished with sodium bicarbonate (5%) and with water till neutral, dried (MgSO4) filtred and evaporeted to give pale white crude (0.385 g) which was recrystallized in aquoes ethanol to give 22a as white crystals (0.361 g), m.p. 156-158° C. (lit. 158° C.). Rfs=IR (KBr) 3380-2720 cm−1. δH (acetone-d6) 2.89 (2H, m, C-4-H2), 3.1 (1H, m, C-3-H) 3.94 (1H, t, J=10.38 Hz, C-2-HA), 4.18 (1H, m, C-2-HE), 6.29 (1H, d, JC-8-H & C-6-H=2.44 Hz, C-8-H), 6.37 (1H, dd, JC-6-H & C-7-H=-8.24 Hz, JC-6-H & C-8-H=2.44 Hz, C-6-H), 6.82 (2H, dd, JC-3′-H & C-2′-H=8.55 Hz. JC-3′ & C-5-H=2.74 H-z,C-3′-H and C-5′-H or C-2′-H and c-6′-H), 6.89 (1H, d, JC-5-H & C-6-H=8.24 Hz, C-5-H), 7.16 (2H, dd, JC-2′-H & C-5′-H=8.24 Hz, JC-2′-H & C-6′-H=2.74 Hz, C-2′-H and C-6′-H or C-3′-H and C-5′-H), 8.15 (1H, br s, C-7-OH or C-4′-OH) and 828 (1H br s, C-4′—OH or C-7-OH). 13CNMR (acetone-d6) MS: m/z (+ve ion FAB in m-NBA, rel. intensity) 242.1 [100, (M)+], [, (M−SO2NH2)+]. MS: m/z (−ve ion FAB in m-NBA, rel. intensity) 394.2 [50, (M−H+NBA)−], 241.2 [100, (M−H)−]. Acc. MS (+ve ion FAB in m-NBA): m/z 242.094 C15H15O3 requires 243.1021. Found: C,; H, 4. C15H14O3 requires C, 74.36; H, 5.82%.

Workup

  1. filtrationthe solution was filtered
  2. washwashed with diglume and hot acetic acid
  3. dissolutionThe crude was dissolved in ethylacetate
  4. dry with materialdried (MgSO4)
  5. customto give pale white crude (0.385 g) which
  6. customwas recrystallized in aquoes ethanol

Sources & evidence

ORD record
ord-a45901d9bf054717ba23ae7941510e90
Source dataset
uspto-grants-2003_01
Patent number
US06506792B1

Reaction notes

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