Benzene → HCID 13280229, compound

HRID 1918417Notes

Reaction equation

HRID 1918417 reaction equation
[CH:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[Cl-].[Cl-].[Al+3].[C:11](Cl)(=[O:16])/[C:12](=[CH:14]/[CH3:15])/[CH3:13]>Cl>[CH3:13][CH:12]1[CH:14]([CH3:15])[C:6]2[C:1](=[CH:2][CH:3]=[CH:4][CH:5]=2)[C:11]1=[O:16]

Participants

5

Reactant 3

HCID 241BenzeneHCID 5325503(2E)-2-Methyl-2-butenoyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 13280229HCID 13280229, compoundYield 92%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Conditions

Temperature
7 °C

Procedure

Under an argon atmosphere benzene (335 ml, 3.74 mol) and aluminum trichloride (90.78 g, 0.68 mol) were introduced into a 1 liter three necked round bottomed flask fitted with a magnetic stirring apparatus, an addition funnel and a reflux condenser. The stirred orange mixture was cooled to 7° C. and tigloyl chloride (33) (40 g, 0.34 mol) was added dropwise via an addition funnel. After completion of the addition, the mixture was allowed to come to room temperature and then refluxed overnight. Then the reaction mixture was allowed to come to room temperature and poured onto mixture of ice (300 g) and conc. HCl (50 ml). The organic layer was separated and washed with a saturated solution of sodium bicarbonate (3×100 ml), then dried over magnesium sulfate and filtered. The excess benzene was removed under reduced pressure to afford (34) (50.02 g, 92%) as a yellow liquid. The 1H NMR spectrum was identical with the literature (T. E. Ready, J. C. W. Chien, M. D. Rausch, J. Org. Chem. 1999 583, 11-27; J. Sarrazin, A. Tallec, Tetrahedron Letters, 1977, 18, 1579-1582; M. Hiscock, G. B. Porter, J. Chem. Soc. (B), 1971, 1631-1634). 1H NMR (200 MHz, CDCl3): δ [ppm] 7.76-7.34 (m, 4H, arom), 2.94 (dq, 3J=4.9 Hz, 3J=7.0 Hz, 1H, H-position 2), 2.24 (dq, 3J=7.3 Hz, 3J=4.7 Hz, 1H, H-position 3), 1.46 (d, 3J=6.9 Hz, 3H, CH3-position 2), 1.32 (d, 3J=7.3 Hz, 3H, CH3-position 3).

Workup

  1. customfitted with a magnetic stirring apparatus, an addition funnel and a reflux condenser
  2. additionAfter completion of the addition
  3. customto come to room temperature
  4. temperaturerefluxed overnight
  5. customto come to room temperature
  6. customThe organic layer was separated
  7. washwashed with a saturated solution of sodium bicarbonate (3×100 ml)
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customThe excess benzene was removed under reduced pressure

Sources & evidence

ORD record
ord-0b14174ad6e1446fbdc0a1b6c269f029
Source dataset
uspto-grants-2013_12
Patent number
US08618328B2

Reaction notes

Loading…