Water → 8a-Hydroxy-3-(hydroxymethyl)-2,4',4',5'-tetramethyl-1,3',4-trioxooctahydro-8H-spiro[3,9a-epidithiocyclopenta[4,5]pyrrolo[1,2-a]pyrazine-7,2'-oxolan]-8-yl acetate

HRID 1579973Notes

Reaction equation

HRID 1579973 reaction equation
[CH3:1][CH:2]1[O:7][C@:6]2([C@@H:11]([O:12][C:13]([CH3:15])=[O:14])[C@:10]3([OH:32])[CH2:16][C@@:17]45[S:29][S:28]SS[C@@:21]([CH2:30][OH:31])([N:22]([CH3:25])[C:23]4=[O:24])[C:19](=[O:20])[N:18]5[C@@H:9]3[CH2:8]2)[C:4](=[O:5])[C:3]1([CH3:34])[CH3:33].S(Cl)(Cl)=O.O>N1C=CC=CC=1>[CH3:1][CH:2]1[O:7][C:6]2([CH:11]([O:12][C:13]([CH3:15])=[O:14])[C:10]3([OH:32])[CH2:16][C:17]45[S:29][S:28][C:21]([CH2:30][OH:31])([N:22]([CH3:25])[C:23]4=[O:24])[C:19](=[O:20])[N:18]5[CH:9]3[CH2:8]2)[C:4](=[O:5])[C:3]1([CH3:34])[CH3:33]

Participants

5

Reactant 3

HCID 962WaterHCID 24386Thionyl ChlorideHCID 101593099HCID 101593099, compound

Product 1

HCID 3255178a-Hydroxy-3-(hydroxymethyl)-2,4',4',5'-tetramethyl-1,3',4-trioxooctahydro-8H-spiro[3,9a-epidithiocyclopenta[4,5]pyrrolo[1,2-a]pyrazine-7,2'-oxolan]-8-yl acetate

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Sirodesmin B (50 mg.) in dry pyridine (1.0 ml.) was treated with thionyl chloride (0.1 ml.) for 12 minutes at 0°C., then added to iced-water (25 ml.) and left for 15 minutes. The solution was adjusted to pH 2 with 2N.sulphuric acid, then extracted with chloroform (3 × 20 ml.). The extracts were dried over sodium sulphate, then concentrated to an oil (29.4 mg.) which was essentially Sirodesmin A but contained traces of Sirodesmin B and C. The crude product was purified by preparative t.l.c. on silica gel G.F. (solvent, formic acid: methanol: chloroform, 1:4:95) to yield Sirodesmin A as an oil (12.5 mg.).

Workup

  1. extractionsulphuric acid, then extracted with chloroform (3 × 20 ml.)
  2. dry with materialThe extracts were dried over sodium sulphate
  3. concentrationconcentrated to an oil (29.4 mg.) which
  4. customThe crude product was purified by preparative t.l.c

Sources & evidence

ORD record
ord-1784a5d6cbe74a96a7e43b95dd352719
Source dataset
uspto-grants-1976_01
Patent number
US03932394

Reaction notes

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