Hydrochloric Acid → 2,2-Dipropylpentanoic acid

HRID 1076875Notes

Reaction equation

HRID 1076875 reaction equation
[O:1]1CCOCC1.[CH2:7]([C:10]([CH2:17][CH2:18][CH3:19])([CH2:14][CH2:15][CH3:16])[C:11](N)=[O:12])[CH2:8][CH3:9].Cl.N(OCCCC)=O>[OH-].[K+]>[CH2:7]([C:10]([CH2:17][CH2:18][CH3:19])([CH2:14][CH2:15][CH3:16])[C:11]([OH:1])=[O:12])[CH2:8][CH3:9]

Participants

6

Reactant 4

HCID 313Hydrochloric Acid2×HCID 10996Butyl nitriteHCID 312751,4-Dioxane2×HCID 68689Valdipromide

Product 1

HCID 1040672,2-Dipropylpentanoic acidYield 76%

Reagents, catalysts & solvents 1

HCID 14797Potassium HydroxideSolvent

Procedure

In a flask equipped with a dropping-funnel were placed 480 g. of distilled dioxan followed by 80 g. (0.432 mol) of tri-n-propylacetamide which was dissolved by stirring. For a period of 20 minutes a current of dry hydrochloric acid gas was passed through the dioxan solution at room-temperature, which represented a total of 100 g of hydrochloric acid gas. At the end of this operation, 88 g (0.86 mol) of freshly distilled butyl nitrite was slowly added over a period of 2 hours through the dropping-funnel. The temperature of the reaction medium rose from 31° to 43°C which necessitated cooling in a water-bath. The solution was then maintained for 2 hours at 85°-90°C. The dioxan was distilled off under a reduced pressure of 20 mm. Hg and a pasty residue obtained at room-temperature. This residue was dissolved in 290 g of a 10% aqueous solution of potassium hydroxide. The aqueous layer was decanted out and extracted twice with 75 g of ethyl ether. The potassium solution was acidified with 118 g of a 36% solution of hydrochloric acid (at 10° /20°C) after which the oily phase was decanted out. The aqueous phase was extracted twice with 75 g of ethyl ether after which the oily phase and the ethereal extracts were placed together. The ethereal solution was washed twice with 100 g of water and dried for 24 hours over 100 g of anhydrous sodium sulphate. The sodium sulphate was then centrifuged out. The ethyl ether was distilled off under atmospheric pressure and the residue recuperated under 7 mm. Hg. The fraction obtained boiled at 126° to 128°C and crystallized rapidly. In this way, 61 g of crude tri-n-propylacetic acid were obtained, which represents a yield of 76%. The crude product was then dissolved by heating in 75 g of ethyl ether. The ethereal solution was filtered while hot and the filtrate left at a temperature of -30°C for 4 hours. The precipitate which formed was centrifuged out and dried in a desiccator under a reduced pressure of 20 mm. Hg for 6 hours. By this means, 46 g of pure tri-n-propylacetic acid were obtained which represents a yield in pure product of 75.4% and a total yield of 57.3% M.P. 67°C

Workup

  1. customIn a flask equipped with a dropping-funnel
  2. customrose from 31° to 43°C
  3. temperaturenecessitated cooling in a water-bath
  4. temperatureThe solution was then maintained for 2 hours at 85°-90°C
  5. distillationThe dioxan was distilled off under a reduced pressure of 20 mm. Hg
  6. customa pasty residue obtained at room-temperature
  7. customThe aqueous layer was decanted out
  8. extractionextracted twice with 75 g of ethyl ether
  9. customwas acidified with 118 g of a 36% solution of hydrochloric acid (at 10° /20°C)
  10. customwas decanted out
  11. extractionThe aqueous phase was extracted twice with 75 g of ethyl ether after which the oily phase
  12. washThe ethereal solution was washed twice with 100 g of water
  13. dry with materialdried for 24 hours over 100 g of anhydrous sodium sulphate
  14. distillationThe ethyl ether was distilled off under atmospheric pressure
  15. customThe fraction obtained boiled at 126° to 128°C
  16. customcrystallized rapidly

Sources & evidence

ORD record
ord-04cf9a59e4ef4d9ebba070d174f2d9db
Source dataset
uspto-grants-1976_05
Patent number
US03958011

Reaction notes

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