Water → HCID 13096683, compound

HRID 462673Notes

Reaction equation

HRID 462673 reaction equation
[CH3:1][C:2](C)([CH2:6][C:7]1[S:8][CH:9]=[CH:10][CH:11]=1)[C:3](O)=O.C1(P([N:27]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.C(N(CC)CC)C.O>C(O)(C)(C)C>[CH3:1][C:2]([CH3:3])([NH2:27])[CH2:6][C:7]1[S:8][CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 104877462,2-Dimethyl-3-(thiophen-2-yl)propanoic acid

Product 1

HCID 13096683HCID 13096683, compound

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A solution of 2,2-dimethyl-3-(2-thienyl)propanoic acid (11.2 g, 0.06 mole), diphenylphosphorylazide (16.7 g, 0.06 mole) (Aldrich Chemical Company), and triethylamine (6.14 g, 0.06 mole) in t-butanol (100 mL) was heated at reflux for 5 hrs. The solution was poured into water (300 mL) and the crude material extracted with ether. The combined extracts were washed with brine, dried (MgSO4) and evaporated to 11.9 g of an oil. This oil was added to a mixture of ethylene glycol (50 mL), H2O (20 drops) and KOH (10 g). The mixture was heated at reflux for 5 hr, cooled to 25°, diluted with H2O (300 mL) and acidified to pH 1 with conc HCl. Acid insoluble material was removed by washing with ether. The aqueous solution was then made basic with 50% NaOH solution and the product was extracted with ether. The ether extracts were combined, washed with brine, dried (MgSO4) and concentrated in vacuo to 6.9 g (74%) of product. The NMR spectrum is consistent with the structure of this intermediate compound.

Workup

  1. temperatureat reflux for 5 hrs
  2. extractionthe crude material extracted with ether
  3. washThe combined extracts were washed with brine
  4. dry with materialdried (MgSO4)
  5. customevaporated to 11.9 g of an oil
  6. additionThis oil was added to a mixture of ethylene glycol (50 mL), H2O (20 drops) and KOH (10 g)
  7. temperatureThe mixture was heated
  8. temperatureat reflux for 5 hr
  9. temperaturecooled to 25°
  10. additiondiluted with H2O (300 mL)
  11. customAcid insoluble material was removed
  12. washby washing with ether
  13. extractionthe product was extracted with ether
  14. washwashed with brine
  15. dry with materialdried (MgSO4)
  16. concentrationconcentrated in vacuo to 6.9 g (74%) of product

Sources & evidence

ORD record
ord-03292fee6bc248038fe92ba85d843d17
Source dataset
uspto-grants-1985_05
Patent number
US04517188

Reaction notes

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