Ammonium Chloride → ethyl (E)-6-(3-hydroxyphenyl)hept-5-enoate

HRID 2120491Notes

Reaction equation

HRID 2120491 reaction equation
[Br-].[C:2]([CH2:5][CH2:6][CH2:7][CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([OH:4])=[O:3].[CH3:28][C:29]([CH3:32])([O-:31])C.[K+].COC[O:37][C:38]1[CH:39]=[C:40]([C:44](=O)[CH3:45])[CH:41]=[CH:42][CH:43]=1.[Cl-].[NH4+]>C1COCC1>[OH:37][C:38]1[CH:39]=[C:40](/[C:44](/[CH3:45])=[CH:8]\[CH2:7][CH2:6][CH2:5][C:2]([O:4][CH2:28][CH3:29])=[O:3])[CH:41]=[CH:42][CH:43]=1.[OH:37][C:38]1[CH:39]=[C:40](/[C:44](/[CH3:45])=[CH:8]/[CH2:7][CH2:6][CH2:5][C:2]([O:31][CH2:29][CH3:32])=[O:3])[CH:41]=[CH:42][CH:43]=1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 161236(4-Carboxybutyl)triphenylphosphonium bromideHCID 143614871-[3-(Methoxymethoxy)phenyl]ethan-1-oneHCID 23665647Potassium tert-butoxide

Product 2

HCID 23439913ethyl (E)-6-(3-hydroxyphenyl)hept-5-enoateYield 16%HCID 69927020ethyl (Z)-6-(3-hydroxyphenyl)hept-5-enoateYield 12%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
130 °C

Procedure

21.6 g (48.7 mmol) of (4-carboxybutyl)triphenylphosphonium bromide are dried under vacuum for 1 h by heating to 130° C., and then brought to room temperature and dissolved in 300 ml of anhydrous THF. 10.9 g (97 mmol) of potassium tert-butoxide in 100 ml of THF are then slowly added and then the orange-red mixture is stirred for 15 minutes. A solution of 6.3 g (32.5 mmol) of 1-(3-methoxymethoxyphenyl)-1-ethanone in 50 ml of THF is then added dropwise and the reaction medium is stirred for 15 hours. After treating with a saturated ammonium chloride solution and extracting with ethyl acetate and then drying and evaporating the solvants of the organic phase, the residue is then dissolved in 50 ml of ethanol and then 1 ml of sulphuric acid is added. The reaction medium is heated to reflux temperature and stirred for 2 hours. After treating with water, the medium is extracted with ethyl acetate and then the organic phases are combined, dried and concentrated under reduced pressure. The residue is purified by chromatography on a silica column (eluent heptane 80-ethyl acetate 20) in order to obtain 1 g (12%) of ethyl (Z)-6-(3-hydroxyphenyl)hept-5-enoate and 1.3 g (16%) of ethyl (E)-6-(3-hydroxyphenyl)hept-5-enoate.

Workup

  1. custombrought to room temperature
  2. stirringthe reaction medium is stirred for 15 hours
  3. extractionextracting with ethyl acetate
  4. customdrying
  5. customevaporating the solvants of the organic phase
  6. dissolutionthe residue is then dissolved in 50 ml of ethanol
  7. addition1 ml of sulphuric acid is added
  8. temperatureThe reaction medium is heated
  9. temperatureto reflux temperature
  10. stirringstirred for 2 hours
  11. additionAfter treating with water
  12. extractionthe medium is extracted with ethyl acetate
  13. customdried
  14. concentrationconcentrated under reduced pressure
  15. customThe residue is purified by chromatography on a silica column (eluent heptane 80-ethyl acetate 20) in order

Sources & evidence

ORD record
ord-692febe36ef24d5db02552c103cf7d6e
Source dataset
uspto-grants-2004_02
Patent number
US06689922B1

Reaction notes

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