Hydrochloric Acid → HCID 57909128, compound

HRID 871186Notes

Reaction equation

HRID 871186 reaction equation
[C:1](Cl)(=[O:6])/[C:2](=[CH:4]/[CH3:5])/[CH3:3].[CH3:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=1.Cl>C(Cl)Cl>[CH3:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[C:12]2[C:11]=1[CH:4]([CH3:5])[CH:2]([CH3:3])[C:1]2=[O:6]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 90161,4-DimethoxybenzeneHCID 5325503(2E)-2-Methyl-2-butenoyl chloride

Product 1

HCID 57909128HCID 57909128, compoundYield 12.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A1Cl3 (64 g, 0.48 mol) and CH2Cl2 (250 ml) (dried with magnesium sulfate) were placed under an argon atmosphere in a 500 ml three necked round bottomed flask fitted with a magnetic stirring apparatus, an addition funnel, an inner thermometer and a reflux condenser. A mixture of tigloyl chloride (33) (42 g, 0.35 mol) and 1,4-dimethoxybenzene (48.4 g, 0.35 mol, dissolved in CH2Cl2 (75 ml)) was added over a period of 1 h at −10° C. under vigorous stirring. After 2 h stirring at −2° C. to −5° C. the mixture was allowed to come to ambient temperature and was stirred overnight. The dark red mixture was then refluxed for 2 h, after cooling to ambient temperature the reaction mixture was poured carefully onto a mixture of concentrated HCl (300 ml) and ice (500 g). Then the resulting yellow mixture was transferred to a separation funnel, the lower CH2Cl2 layer was isolated and the aqueous layer extracted with diethyl ether (3×100 ml). The combined organic layers were dried over magnesium sulfate, filtered, and the solvents removed under reduced pressure to give a dark brown liquid. This residue was distilled using a 15 cm Vigreux column to obtain an orange-yellow light viscous liquid (110-115° C., 0.8 mbar). The liquid was purified via column chromatography [(SiO2, 25×9 cm) eluent: cyclohexane:ethylacetate (1:1)] to afford 2,3-dimethyl-4,7-dimethoxy-1-indanone (36) (9.53 g, 12%), Rf 0.35 (cyclohexane:ethylacetate (5:1)) as an orange liquid. The liquid was found to be a mixture of the two isomers of 4,7-dimethoxy-2,3-dimethyl-1-indanone (36a to 36b approximately 4:1).

Workup

  1. customfitted with a magnetic stirring apparatus, an addition funnel
  2. additionwas added over a period of 1 h at −10° C. under vigorous stirring
  3. customto come to ambient temperature
  4. stirringwas stirred overnight
  5. temperatureThe dark red mixture was then refluxed for 2 h
  6. customThen the resulting yellow mixture was transferred to a separation funnel
  7. extractionthe aqueous layer extracted with diethyl ether (3×100 ml)
  8. dry with materialThe combined organic layers were dried over magnesium sulfate
  9. filtrationfiltered
  10. customthe solvents removed under reduced pressure
  11. customto give a dark brown liquid
  12. distillationThis residue was distilled
  13. customto obtain an orange-yellow light viscous liquid (110-115° C., 0.8 mbar)
  14. customThe liquid was purified via column chromatography [(SiO2, 25×9 cm) eluent: cyclohexane:ethylacetate (1:1)]

Sources & evidence

ORD record
ord-c6a826d2d87e42e3aa577c731f9f2c64
Source dataset
uspto-grants-2015_03
Patent number
US08969624B2

Reaction notes

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