Sodium borohydride → HCID 20326287, compound

HRID 372615Notes

Reaction equation

HRID 372615 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+]>C(O)C>[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

4

Reactant 2

HCID 4311764Sodium borohydride2×HCID 5360807Lasalocid

Product 1

HCID 20326287HCID 20326287, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 10 g of crystalline antibiotic X-537A in 500 ml of absolute ethanol 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 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-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. additionafter adding an additional 1.0 g
  2. customThe following morning the solvent was removed under reduced pressure
  3. additionthe heavy oil diluted with methylene chloride
  4. washwashed with dilute HCl
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated to a solid foam
  7. customThe slightly pink solid was chromatographed on a 500 g silica gel column
  8. washeluting with 2 l
  9. concentrationconcentrated to a yellow solid
  10. customrechromatographed on a 150 g florisil column
  11. washeluting with a gradient from hexane to acetone
  12. 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
  13. 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-6-methyl-2-tetrahydropyranyl) 2-tetrahydrofuryl]heptyl}salicylic acid crystals
  14. customwere recovered
  15. customFrom the mother liquor, additional material was crystallized

Sources & evidence

ORD record
ord-d35f375df12b454db62747b0171a6e2c
Source dataset
uspto-grants-1978_05
Patent number
USRE029651

Reaction notes

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