3-(4-Hydroxy-3-Methoxyphenyl)Prop-2-Enoic Acid → 3-[4-(2,4-Dichlorobenzyloxy)-3-methoxyphenyl]-propionic acid

HRID 435887

Reaction equation

HRID 435887 reaction equation
O=CC1C=CC(O)=C(OC)C=1.[H-].[Na+].[OH:14][C:15]1[CH:20]=[CH:19][C:18]([CH:21]=[CH:22][C:23]([OH:25])=[O:24])=[CH:17][C:16]=1[O:26][CH3:27].OC1C=CC(CCC(O)=O)=CC=1OC.[Cl:42][C:43]1[CH:50]=[C:49]([Cl:51])[CH:48]=[CH:47][C:44]=1[CH2:45]Cl.S(=O)(=O)(O)O>CN(C)C=O>[Cl:42][C:43]1[CH:50]=[C:49]([Cl:51])[CH:48]=[CH:47][C:44]=1[CH2:45][O:14][C:15]1[CH:20]=[CH:19][C:18]([CH2:21][CH2:22][C:23]([OH:25])=[O:24])=[CH:17][C:16]=1[O:26][CH3:27]

Participants

8

Reactant 6

HCID 7093-(4-Hydroxy-3-Methoxyphenyl)Prop-2-Enoic AcidHCID 1118Sulfuric AcidHCID 1183VanillinHCID 72122,4-Dichlorobenzyl chlorideHCID 14340Dihydroferulic AcidHCID 24758Sodium hydride2×

Product 1

HCID 214816273-[4-(2,4-Dichlorobenzyloxy)-3-methoxyphenyl]-propionic acid

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

16.6 g. of vanillin, 22.4 g. of triethylphosphonoacetate, and 5.75 g. of sodium hydride - oil suspension (80%) in 100 ml. of dimethylformamide are reacted analogously to Example 75. Reaction time: 6 hours at 100°. 21 g. of the thus-obtained ethyl ester of 3-(4-hydroxy-3-methoxyphenyl)-acrylic acid is hydrogenated as described in Example 75. 10 g. of the thus-formed ethyl ester of 3-(4-hydroxy-3-methoxyphenyl)-propionic acid is combined in 100 ml. of dimethylformamide with 1.34 g. of sodium hydride - oil suspension (80%), and after 15 minutes at room temperature, 8.8 g. of 2,4-dichlorobenzyl chloride is added thereto. After 2 hours at room temperature, the mixture is poured on 1N sulfuric acid and extracted with ethyl acetate. After drying and evaporation, 17 g. of the ethyl ester of 3-[4-(2,4-dichlorobenzyloxy)-3-methoxyphenyl]-propionic acid is obtained and slowly combined in 200 ml. ether with 7.1 g. Br in 10 ml. of carbon tetrachloride. After the bromine coloring has disappeared, the mixture is extracted with water and potassium bicarbonate solution, and the ether phase is dried and evaporated. After recrystallization from ethanol, 13.9 g. of the ethyl ester of 3-[2-bromo-4-(2,4-dichlorobenzyloxy)-5-methoxyphenyl]-propionic acid is obtained, m.p. 102°-106° By lithium aluminum hydride reduction of 10 g. of this compound in tetrahydrofuran, 7.5 g. of 3-[2-bromo-4-(2,4-dichlorobenzyloxy)-5-methoxyphenyl] -1-propanol is obtained, m.p. 102°-103°. This product is reacted analogously to Example 75 with thionyl chloride and then with sodium imidazole to obtain the final product. Yield: 2.72 g.; m.p. 142°-144° (from acetonitrile).

Workup

  1. customReaction time
  2. custom6 hours
  3. customat 100°
  4. extractionextracted with ethyl acetate
  5. customAfter drying
  6. customevaporation, 17 g

Sources & evidence

ORD record
ord-1e291ed2718147b6ba8150581a337ca4
Source dataset
uspto-grants-1977_02
Patent number
US04006243

Linked notes

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