Hydrochloric Acid → Ethyl 3-[4-(6-acetoxy-2,5,7,8-tetramethyl-4-oxochroman-2-ylmethoxy)phenyl]-2-chloropropionate

HRID 1589706Notes

Reaction equation

HRID 1589706 reaction equation
[ClH:1].N([O-])=O.[Na+].[C:6]([O:9][C:10]1[C:11]([CH3:33])=[C:12]2[C:17](=[C:18]([CH3:21])[C:19]=1[CH3:20])[O:16][C:15]([CH2:23][O:24][C:25]1[CH:30]=[CH:29][C:28](N)=[CH:27][CH:26]=1)([CH3:22])[CH2:14][C:13]2=[O:32])(=[O:8])[CH3:7].[C:34]([O:38][CH2:39][CH3:40])(=[O:37])[CH:35]=[CH2:36]>O.C1C=CC=CC=1.CC(C)=O>[C:6]([O:9][C:10]1[C:11]([CH3:33])=[C:12]2[C:17](=[C:18]([CH3:21])[C:19]=1[CH3:20])[O:16][C:15]([CH2:23][O:24][C:25]1[CH:30]=[CH:29][C:28]([CH2:36][CH:35]([Cl:1])[C:34]([O:38][CH2:39][CH3:40])=[O:37])=[CH:27][CH:26]=1)([CH3:22])[CH2:14][C:13]2=[O:32])(=[O:8])[CH3:7]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8821Ethyl AcrylateHCID 136058312-[(4-Aminophenoxy)methyl]-2,5,7,8-tetramethyl-4-oxo-3,4-dihydro-2H-1-benzopyran-6-yl acetateHCID 23668193Sodium Nitrite

Product 1

HCID 13649224Ethyl 3-[4-(6-acetoxy-2,5,7,8-tetramethyl-4-oxochroman-2-ylmethoxy)phenyl]-2-chloropropionate

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 241BenzeneSolventHCID 962WaterSolvent2×

Procedure

3 ml of concentrated hydrochloric acid and then an aqueous solution of 700 mg of sodium nitrite in 1.1 ml of water were added dropwise to a mixture of 2.1 g of 6-acetoxy-2-(4-aminophenoxymethyl)-2,5,7,8-tetramethylchroman-4-one and 26 ml of acetone, whilst cooling with ice. The mixture was stirred for 30 minutes at the same temperature. 7 g of ethyl acrylate were then added, after which cuprous oxide was added gradually, while keeping the reaction temperature at 30°-35° C. The reaction mixture was then stirred for 1 hour at room temperature. Water and benzene were added to the reaction mixture. The benzene layer was separated, washed with water and dried over anhydrous sodium sulfate. Benzene was distilled off and the residue was subjected to silica gel column chromatography, eluted with a 3:1 by volume mixture of hexane and ethyl acetate, to yield ethyl 3-[4-(6-acetoxy-2,5,7,8-tetramethyl-4-oxochroman-2-ylmethoxy)phenyl]-2-chloropropionate.

Workup

  1. temperaturewhilst cooling with ice
  2. customat 30°-35° C
  3. stirringThe reaction mixture was then stirred for 1 hour at room temperature
  4. customThe benzene layer was separated
  5. washwashed with water
  6. dry with materialdried over anhydrous sodium sulfate
  7. distillationBenzene was distilled off
  8. washeluted with a 3:1 by volume mixture of hexane and ethyl acetate

Sources & evidence

ORD record
ord-49fe09c8103043d08abb0a11eecf4993
Source dataset
uspto-grants-1986_02
Patent number
US04572912

Reaction notes

Loading…