Methyl iodide → 7-{7-(3-Hydroxy-3-methyl-4-propoxybut-1-enyl)-1,4-dioxaspiro[4,4]non-6-yl}heptanoic acid

HRID 259204Notes

Reaction equation

HRID 259204 reaction equation
C[Mg]I.[CH3:4]I.[Mg].[O:7]=[C:8]([CH2:33][O:34][CH2:35][CH2:36][CH3:37])[CH:9]=[CH:10][CH:11]1[CH2:19][CH2:18][C:13]2([O:17][CH2:16][CH2:15][O:14]2)[CH:12]1[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][Si](C)(C)C)=[O:27].[Cl-].[NH4+]>C(OCC)C>[OH:7][C:8]([CH3:4])([CH2:33][O:34][CH2:35][CH2:36][CH3:37])[CH:9]=[CH:10][CH:11]1[CH2:19][CH2:18][C:13]2([O:17][CH2:16][CH2:15][O:14]2)[CH:12]1[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]([OH:28])=[O:27]

Participants

7

Reactant 5

HCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 86734959Trimethylsilyl 7-{7-(3-oxo-4-propoxybut-1-enyl)-1,4-dioxaspiro[4,4]non-6-yl}heptanoateHCID 178418373HCID 178418373, compound2×

Product 1

HCID 540128087-{7-(3-Hydroxy-3-methyl-4-propoxybut-1-enyl)-1,4-dioxaspiro[4,4]non-6-yl}heptanoic acidYield 66.4%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent4×

Procedure

A solution (1.66 ml.) of methyl magnesium iodide in diethyl ether [prepared in the manner well known in the art from methyl iodide (6 g.), magnesium (1.07 g.) and diethyl ether (20 ml.)] was added dropwise to a stirred solution of trimethylsilyl 7-{7-(3-oxo-4-propoxybut-1-enyl)-1,4-dioxaspiro[4,4]non-6-yl}heptanoate (0.67 g.) in diethyl ether (25 ml.) at room temperature. The mixture was stirred for 30 minutes and a further quantity of the solution of methyl magnesium iodide in diethyl ether (0.4 ml.) was then added dropwise. The mixture was stirred for a further 30 minutes and then added to saturated aqueous ammonium chloride solution (100 ml.) at 0° C. and stirred for 15 minutes. The ether layer was separated and the aqueous layer was extracted with diethyl ether. The combined ether layers were added to 10% w/v aqueous sodium carbonate solution (25 ml.) and stirred for 1 hour. The aqueous layer was separated and washed with diethyl ether, and then acidified to pH 5 by the addition of 20% w/v aqueous sodium dihydrogen phosphate solution. The aqueous layers were again extracted with diethyl ether and the resulting ether extracts dried over sodium sulphate. The solvent was removed in vacuo to give crude 7-{7-(3-hydroxy-3-methyl-4-propoxybut-1-enyl)-1,4-dioxaspiro[4,4]non-6-yl}heptanoic acid (0.39 g.).

Workup

  1. stirringThe mixture was stirred for a further 30 minutes
  2. stirringstirred for 15 minutes
  3. customThe ether layer was separated
  4. extractionthe aqueous layer was extracted with diethyl ether
  5. additionThe combined ether layers were added to 10%
  6. stirringstirred for 1 hour
  7. customThe aqueous layer was separated
  8. washwashed with diethyl ether
  9. additionacidified to pH 5 by the addition of 20%
  10. extractionThe aqueous layers were again extracted with diethyl ether
  11. dry with materialthe resulting ether extracts dried over sodium sulphate
  12. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-2225b3e98b064db8adbe59a30bee5dbe
Source dataset
uspto-grants-1977_07
Patent number
US04036872

Reaction notes

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