Sodium borohydride → HCID 20326287, compound

HRID 1605494Notes

Reaction equation

HRID 1605494 reaction equation
[CH3:1][CH2:2][C@@H:3]([C:22]([C@H:24]([C@@H:26]([OH:42])[C@@H:27]([CH2:29][CH2:30][C:31]1[CH:36]=[CH:35][C:34]([CH3:37])=[C:33]([OH:38])[C:32]=1[C:39]([OH:41])=[O:40])[CH3:28])[CH3:25])=[O:23])[C@H:4]1[O:8][C@@:7]([C@@H:11]2[O:16][C@@H:15]([CH3:17])[C@@:14]([OH:20])([CH2:18][CH3:19])[CH2:13][CH2:12]2)([CH2:9][CH3:10])[CH2:6][C@@H:5]1[CH3:21].[BH4-].[Na+]>>[CH3:37][C:34]1[CH:35]=[CH:36][C:31]([CH2:30][CH2:29][CH:27]([CH3:28])[CH:26]([OH:42])[CH:24]([CH3:25])[CH:22]([OH:23])[CH:3]([CH2:2][CH3:1])[CH:4]2[CH:5]([CH3:21])[CH2:6][C:7]([CH2:9][CH3:10])([CH:11]3[CH2:12][CH2:13][C:14]([CH2:18][CH3:19])([OH:20])[CH:15]([CH3:17])[O:16]3)[O:8]2)=[C:32]([C:39]([OH:41])=[O:40])[C:33]=1[OH:38]

Participants

3

Reactant 2

HCID 4311764Sodium borohydride2×HCID 5360807Lasalocid

Product 1

HCID 20326287HCID 20326287, compound

Procedure

To a solution of 10 g of crystalline antibiotic X-537A in 500 ml of absolute ethanaol was added 1.36 g of NaBH4. The reaction was followed by assaying with thin layer chromatography (silica gel - CHCl3 /acetone 8:2) and the reaction was continued overnight after adding an additional 1.0 g of NaBH4. The following morning the solvent was removed under reduced pressure and the heavy oil diluted with methylene chloride, washed with dilute HCl, dried (Na2SO4), and concentrated to a solid foam. The slightly pink solid was chromatographed on a 500 g silica gel column eluting with 2 l. hexane-methylene chloride (1:1), 2 l. methylene chloride 2 l. methylene chloride 2 l. methylene chloride ether (1:1). The 250 ml fractions were assayed by TLC and fractions 13-17 pooled, concentrated to a yellow solid and rechromatographed on a 150 g florisil column eluting with a gradient from hexane to acetone. The fractions containing 3-methyl-6-{4,6-dihydroxy-3,5-dimethyl-7-ethyl-7-[5-ethyl-3-methyl-5-(5-ethyl-5-hydroxy-6-methyl-2-tetrahydropyranyl)-2-tetrahydrofuryl]heptyl} salicylic acid were pooled and concentrated to a small volume from which pure 3-methyl-6-{4,6-dihydroxy-3,5-dimethyl-7-ethyl-7-[ 5-ethyl-3-methyl-5-(5-ethyl-5-hydroxy-6-methyl-2-tetrahydropyranyl)-2-tetrahydrofuryl]heptyl} salicylic acid crystals were recovered, m.p. 151°-153°. From the mother liquor, additional material was crystallized, [α]D25 +0.83 (C=.60%, CH3OH).

Workup

  1. customThe following morning the solvent was removed under reduced pressure
  2. additionthe heavy oil diluted with methylene chloride
  3. washwashed with dilute HCl
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated to a solid foam
  6. customThe slightly pink solid was chromatographed on a 500 g silica gel column
  7. washeluting with 2 l
  8. concentrationconcentrated to a yellow solid
  9. customrechromatographed on a 150 g florisil column
  10. washeluting with a gradient from hexane to acetone
  11. additionThe fractions containing 3-methyl-6-{4,6-dihydroxy-3,5-dimethyl-7-ethyl-7-[5-ethyl-3-methyl-5-(5-ethyl-5-hydroxy-6-methyl-2-tetrahydropyranyl)-2-tetrahydrofuryl]heptyl} salicylic acid
  12. concentrationconcentrated to a small volume from which pure 3-methyl-6-{4,6-dihydroxy-3,5-dimethyl-7-ethyl-7-[ 5-ethyl-3-methyl-5-(5-ethyl-5-hydroxy-6-methyl-2-tetrahydropyranyl)-2-tetrahydrofuryl]heptyl} salicylic acid crystals
  13. customwere recovered
  14. customFrom the mother liquor, additional material was crystallized

Sources & evidence

ORD record
ord-12946f5dc9a24c9ca2921e251c0f3a99
Source dataset
uspto-grants-1976_04
Patent number
US03950320

Reaction notes

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