Hydrochloric Acid → HCID 20245643, compound

HRID 1589709Notes

Reaction equation

HRID 1589709 reaction equation
[C:1]([O:4][C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][C:14]=1[C:15]([CH3:18])([CH3:17])[CH3:16])[O:11][C:10]([CH2:20][O:21][C:22]1[CH:27]=[CH:26][C:25](N)=[CH:24][CH:23]=1)([CH3:19])[CH2:9][C:8]2=[O:29])(=[O:3])[CH3:2].[ClH:30].N([O-])=O.[Na+].[C:35]([O:39][CH2:40][CH3:41])(=[O:38])[CH:36]=[CH2:37]>O.C1C=CC=CC=1.CC(C)=O>[C:1]([O:4][C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][C:14]=1[C:15]([CH3:18])([CH3:17])[CH3:16])[O:11][C:10]([CH2:20][O:21][C:22]1[CH:27]=[CH:26][C:25]([CH2:37][CH:36]([Cl:30])[C:35]([O:39][CH2:40][CH3:41])=[O:38])=[CH:24][CH:23]=1)([CH3:19])[CH2:9][C:8]2=[O:29])(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8821Ethyl AcrylateHCID 20245713HCID 20245713, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 20245643HCID 20245643, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

In a similar manner to Preparation 45, to a mixture of 0.42 g of 6-acetoxy-2-(4-aminophenoxymethyl)-7-t-butyl-2-methylchroman-4-one and 5 ml of acetone were added dropwise, whilst cooling with ice, 0.2 ml of concentrated hydrochloric acid and then a solution of 0.09 g of sodium nitrite in 0.5 ml of water. 1.1 g of ethyl acrylate were then added dropwise, after which 16 mg of cuprous oxide were added gradually to the mixture, whilst keeping its temperature at 40°-43° C. Evolution of nitrogen ceased after about 30 minutes. Benzene was added to the reaction mixture, and the organic layer was separated. The resulting benzene extract was washed with water and dried over anhydrous sodium sulfate. The residue after evaporation of the benzene was subjected to silica gel column chromatography, eluted with a 20:1 by volume mixture of benzene and ethyl acetate, to give the desired ethyl 3-[4-(6-acetoxy-7-t-butyl-2-methyl-4-oxochroman-2-ylmethoxy)phenyl]-2-chloropropionate.

Workup

  1. customIn a similar manner to Preparation 45
  2. additionwere added dropwise
  3. customat 40°-43° C
  4. customthe organic layer was separated
  5. extractionThe resulting benzene extract
  6. washwas washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. customThe residue after evaporation of the benzene
  9. washeluted with a 20:1 by volume mixture of benzene and ethyl acetate

Sources & evidence

ORD record
ord-4cfa1916fb4b437b864440b3e3364c86
Source dataset
uspto-grants-1986_02
Patent number
US04572912

Reaction notes

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