Sulfuric Acid → HCID 22905862, compound

HRID 2257247Notes

Reaction equation

HRID 2257247 reaction equation
[OH:1][S:2]([OH:5])(=[O:4])=[O:3].[CH:6]1([CH2:9][CH2:10][CH2:11][CH2:12][OH:13])[CH2:8][CH2:7]1.[CH3:14][C:15]([CH3:17])=[O:16].OS(O)(=O)=O.[O:23]=[Cr:24](=[O:26])=[O:25].[CH3:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32]>O.CC(C)=O.CC(O)=O.CCOC(C)=O>[CH3:14][C:15]([CH3:17])=[O:16].[OH:4][S:2]([OH:5])(=[O:3])=[O:1].[O:23]=[Cr:24](=[O:26])=[O:25].[CH:29]1([CH2:30][CH2:31][CH2:32][C:15]([O:13][CH2:12][CH2:11][CH2:10][CH2:9][CH:6]2[CH2:8][CH2:7]2)=[O:16])[CH2:27][CH2:28]1

Participants

10

Reactant 4

HCID 1118Sulfuric AcidHCID 8058HexaneHCID 230002215687-83-2HCID 131709961Jones' reagent3×

Product 2

HCID 22905862HCID 22905862, compoundHCID 131709961Jones' reagent

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 180AcetoneSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
23 °C

Procedure

Jones reagent is prepared by carefully adding H2SO4 (321 mL) to a cold solution of CrO3 (366 g) in H2O (600 mL) over a period of 0.5 h. In a 5-L 3-neck flask, equipped with mechanical stirrer, internal thermometer, and 1-L addition funnel is placed a solution of 4-cyclopropylbutan-1-ol (127.0 g) in acetone (300 mL). Stirring is commenced, and the solution is cooled below -10° C. with an ice/MeOH bath. The Jones reagent is added at a rate such that the temperature of the reaction mixture never exceeds +10° C. The reaction mixture becomes dark green and heterogenous. 300 mL of Jones reagent is added over 3.5 h and the reaction appears to be complete by TLC (hexane:EtOAc:HOAc, 3:1:0.05). An additional 50 mL Jones reagent is added, and the red color of the reagent persists. The reaction is quenched by the addition of isopropanol (80 mL), and the mixture is allowed to warm to 23° C. A small amount of green precipitate is filtered off, rinsed with acetone (3×200 mL), and discarded. The filtrate is evaporated to a biphasic mixture, poured onto 1.8 kg ice/water, and made alkaline to indicator paper with 50 wt % NaOH (133 g) added in portions. The resulting green solution is filtered to remove a small amount of solids which are discarded. The filtrate is extracted with Et20 (2×40 mL), and the Et20 layers are dried and evaporated to yield 4-cyclopropylbutyl 4-cyclopropylbutanoate. The aqueous layer is cooled in ice while it is acidified with 12N HCl (139 g). The resulting solution is extracted with EtOAc (3×1 L). The aqueous layer is discarded. The organic phases are combined, dried over MgSO4, filtered through paper and evaporated to yield 4-cyclopropylbutanoic acid as a faint green oil. This can be further purified by filtration through Celite and distillation at reduced pressure (0.2-0.4 mbar, 60°-90° C.).

Workup

  1. customIn a 5-L 3-neck flask, equipped with mechanical stirrer
  2. temperaturethe solution is cooled below -10° C. with an ice/MeOH bath
  3. customThe reaction is quenched by the addition of isopropanol (80 mL)
  4. filtrationA small amount of green precipitate is filtered off
  5. washrinsed with acetone (3×200 mL)
  6. customThe filtrate is evaporated to a biphasic mixture
  7. additionpoured onto 1.8 kg ice/water
  8. additionadded in portions
  9. filtrationThe resulting green solution is filtered
  10. customto remove a small amount of solids which
  11. extractionThe filtrate is extracted with Et20 (2×40 mL)
  12. customthe Et20 layers are dried
  13. customevaporated

Sources & evidence

ORD record
ord-08ebd658803143e1a7da88804936842c
Source dataset
uspto-grants-1997_08
Patent number
US05656661

Reaction notes

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