Bromine → HCID 20377723, compound

HRID 1447649Notes

Reaction equation

HRID 1447649 reaction equation
[C:1]([C:5]1[CH:6]=[CH:7][CH:8]=[C:9]([CH:21]=1)[CH2:10][O:11][CH2:12][C:13]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)=[O:14])([O:3][CH3:4])=[O:2].[Br:22]Br>C(Cl)Cl>[C:1]([C:5]1[CH:6]=[CH:7][CH:8]=[C:9]([CH:21]=1)[CH2:10][O:11][CH:12]([Br:22])[C:13]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)=[O:14])([O:3][CH3:4])=[O:2]

Participants

4

Reactant 2

HCID 24408BromineHCID 53963092HCID 53963092, compound

Product 1

HCID 20377723HCID 20377723, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

g 20 of 5-carbomethoxy-2-benzyloxy-acetophenone, m.p.=86°-88° C. dissolved in methylene chloride (ml 200) were reacted with bromine (9.8 g) at 10° C. for 15 minutes. After treatment with 10% sodium sulphite and water, the organic phase was evaporated to dryness. The residue, crystallized from isorpopyl ether, gave 5-carbomethoxy-2-benzyloxy-ω-bromo-acetophenone (17 g), m.p.=84°-86° C., which was dissolved in dimethylformamide (85 ml) and reacted with anhydrous potassium acetate (5.6 g) at 50° C. for 2 hours. After cooling, and dilution with water, the precipiate was filtered and washed with cold methanol so obtaining 5-carbomethoxy-2-benzyloxy-ω-acetoxy-acetophenone (12.9 g), m.p.=86°-87° C., which was dissolved in tetrahydrofuran (40 ml) and ethanol (20 ml); few drops of concentrated HCl were added and then the solution was hydrogenated at atmospheric pressure and room temperature in the presence of 5% Pd/C(2.5 g) to the theoretical hydrogen consumption. The mixture was filtered to remove the catalyst and the organic solution was evaporated to dryness so obtaining crude 5-carbomethoxy-2-hydroxy-ω-acetoxy-acetophenone (9.2 g), which was dissolved in dioxane (20 ml) and pyridine (10 ml) and reacted with trans-cinnamoyl-chloride (9.4 g) at room temperature for 8 hours. The reaction mixture was diluted with water and acidified to pH 4. The precipitate was filtered, dried and dissolved in methyl-ethyl-ketone (100 ml); anhydrous K2CO3 (9.3 g) was added and the mixture was vigorously stirred under reflux for 5 hours.

Workup

  1. customAfter treatment with 10% sodium sulphite and water, the organic phase was evaporated to dryness
  2. customThe residue, crystallized from isorpopyl ether

Sources & evidence

ORD record
ord-e9b57629c07b49688dbe33384ed207a2
Source dataset
uspto-grants-1979_12
Patent number
US04177286

Reaction notes

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