Oxygen → 1-(4-Methylbenzene-1-sulfonyl)azetidine-3-carboxylic acid

HRID 280818Notes

Reaction equation

HRID 280818 reaction equation
[S:1]([N:11]1[CH2:14][C:13]([CH2:17][OH:18])(CO)[CH2:12]1)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].[OH-].[Na+].[O:21]1CCOCC1.O=O>O.[Pt]>[S:1]([N:11]1[CH2:12][CH:13]([C:17]([OH:18])=[O:21])[CH2:14]1)([C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[CH:9][CH:10]=1)(=[O:2])=[O:3]

Participants

7

Reactant 4

HCID 977OxygenHCID 14798Sodium Hydroxide2×HCID 312751,4-DioxaneHCID 21287788HCID 21287788, compound

Product 1

HCID 200291341-(4-Methylbenzene-1-sulfonyl)azetidine-3-carboxylic acid

Reagents, catalysts & solvents 2

HCID 23939PlatinumCatalystHCID 962WaterSolvent

Procedure

N-Tosyl-3,3-bishydroxymethyl azetidine (10 g, 0.037 mol) was suspended in distilled water (100 ml) and 30% NaOH (3 ml) added. Dioxane (50 ml) was then added in order to obtain a homogeneous solution, followed by 1 g of a 5% Pt/C catalyst. This mixture was heated under reflux with rapid stirring whilst a stream of oxygen was bubbled through at the rate of 600 ml.min-1. The pH of the solution was maintained at 9-12 with 30% NaOH and the course of the oxidation followed by 'H nmr. After 24 h another 1 g of catalyst was added and after 48 h a further 2 g was added at which point all of the starting diol had been converted. In order to achieve conversion of any intermediates, a further 1 g catalyst was added after 120 h. After a total reaction time of 144 h, 5 g catalyst had been added and 10 ml 30% NaOH (0.074 mol). The solution was filtered whilst hot and the catalyst washed with dil NaOH and water. The filtrate and washings were then acidified with 4N HCl and extracted with ether (×3). The combined ether extracts were dried and evaporated to leave a white solid which, on recrystallisation from ethyl acetate, gave N-Tosyl azetidine 3-carboxylic acid.

Workup

  1. customto obtain a homogeneous solution
  2. temperatureThis mixture was heated
  3. temperatureunder reflux
  4. customwas bubbled through at the rate of 600 ml.min-1
  5. temperatureThe pH of the solution was maintained at 9-12 with 30% NaOH
  6. additionAfter 24 h another 1 g of catalyst was added and after 48 h a further 2 g
  7. additionwas added at which point all of the starting diol
  8. additiona further 1 g catalyst was added after 120 h
  9. additionAfter a total reaction time of 144 h, 5 g catalyst had been added
  10. filtrationThe solution was filtered whilst hot and the catalyst
  11. washwashed with dil NaOH and water
  12. extractionextracted with ether (×3)
  13. dry with materialThe combined ether extracts were dried
  14. customevaporated
  15. customto leave a white solid which
  16. customon recrystallisation from ethyl acetate

Sources & evidence

ORD record
ord-9bc4708aa7f24bf398a3bf7784c9ce91
Source dataset
uspto-grants-1986_05
Patent number
US04591457

Reaction notes

Loading…