Hydrochloric Acid → HCID 13605832, compound

HRID 1589699Notes

Reaction equation

HRID 1589699 reaction equation
[C:1]([O:4][C:5]1[C:6]([CH3:27])=[C:7]2[C:12](=[C:13]([CH3:16])[C:14]=1[CH3:15])[O:11][C:10]([CH2:18][O:19][C:20]1[CH:25]=[CH:24][C:23](N)=[CH:22][CH:21]=1)([CH3:17])[CH2:9][CH2:8]2)(=[O:3])[CH3:2].N([O-])=O.[Na+].[C:32]([O:36][CH2:37][CH3:38])(=[O:35])[CH:33]=[CH2:34].[ClH:39]>CC(C)=O.O>[C:1]([O:4][C:5]1[C:6]([CH3:27])=[C:7]2[C:12](=[C:13]([CH3:16])[C:14]=1[CH3:15])[O:11][C:10]([CH2:18][O:19][C:20]1[CH:25]=[CH:24][C:23]([CH2:34][CH:33]([Cl:39])[C:32]([O:36][CH2:37][CH3:38])=[O:35])=[CH:22][CH:21]=1)([CH3:17])[CH2:9][CH2:8]2)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8821Ethyl AcrylateHCID 9951222HCID 9951222, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 13605832HCID 13605832, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent2×

Procedure

17.5 g of 6-acetoxy-2-(4-aminophenoxymethyl)-2,5,7,8-tetramethylchroman were dissolved in a mixture of 130 ml of acetone and 30 ml of water, and 13 ml of concentrated hydrochloric acid, followed by 4.3 g of sodium nitrite dissolved in 8.5 ml of water, were added dropwise, with ice-cooling, to the product. 37.3 ml of ethyl acrylate were added dropwise, and then 680 mg of cuprous oxide were added gradually to the product, whilst keeping its temperature at 40°-43° C. Generation of nitrogen terminated after about 30 minutes. Benzene was then added to the reaction mixture (which consisted of 2 layers) to extract the organic layer. The benzene extract was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The solvent was then distilled off from the extract. The dark brownish oil thus obtained was subjected to silica gel column chromatography, eluted with a 1:1 by volume mixture of benzene and cyclohexane and then the proportion of benzene was progressively increased until it was eluted with benzene alone. Ethyl 3-[4-(6-acetoxy-2,5,7,8-tetramethylchroman-2-ylmethoxy)phenyl]-2-chloropropionate was obtained from the fractions eluted with a 2:1 by volume mixture of benzene and cyclohexane and with benzene alone. Rf value on thin layer chromatography: 0.39 [silica gel; developing solvent:benzene:ethyl acetate=20:1 by volume].

Workup

  1. additionwere added dropwise, with ice-
  2. temperaturecooling, to the product
  3. customat 40°-43° C
  4. customGeneration of nitrogen terminated after about 30 minutes
  5. additionBenzene was then added to the reaction mixture (which consisted of 2 layers)
  6. extractionto extract the organic layer
  7. extractionThe benzene extract
  8. washwas washed with a saturated aqueous solution of sodium chloride
  9. dry with materialdried over anhydrous sodium sulfate
  10. distillationThe solvent was then distilled off from the extract
  11. customThe dark brownish oil thus obtained
  12. washeluted with a 1:1 by volume mixture of benzene and cyclohexane
  13. temperaturethe proportion of benzene was progressively increased until it
  14. washwas eluted with benzene alone

Sources & evidence

ORD record
ord-9281a1c4cfcc432283f91c505912e481
Source dataset
uspto-grants-1986_02
Patent number
US04572912

Reaction notes

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