4-Hydroxybenzophenone → 4-[(1Z)-4-Chloro-1,2-diphenylbut-1-en-1-yl]phenol

HRID 2068228Notes

Reaction equation

HRID 2068228 reaction equation
[OH:1][C:2]1[CH:15]=[CH:14][C:5]([C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=O)=[CH:4][CH:3]=1.[Cl:16][CH2:17][CH2:18][C:19]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=O>O1CCCC1.C(=O)([O-])[O-].[K+].[K+].[Zn]>[Cl:16][CH2:17][CH2:18][C:19]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[C:6]([C:5]1[CH:14]=[CH:15][C:2]([OH:1])=[CH:3][CH:4]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 2

HCID 143474-HydroxybenzophenoneHCID 702953-Chloropropiophenone

Product 1

HCID 539047244-[(1Z)-4-Chloro-1,2-diphenylbut-1-en-1-yl]phenol

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent2×HCID 11430Potassium CarbonateSolvent

Conditions

Temperature
-10 °C

Procedure

Zinc (15.0 g, 0.23 mol) and tetrahydrofuran (THF) (180 ml) was added to the reaction vessel and cooled to −10° C. Titan tetrachloride was added dropwise to the mixture (21.6 g, 0.114 mol) at about −10° C. After the addition was completed the mixture was refluxed for two hours. Then the mixture was cooled to 40° C. and 4-hydroxybenzophenone (7.68 g, 0.039 mol) and 3-chloropropiophenone (6.48 g, 0.039 mol) dissolved in THF (75 ml) were added to the mixture. Refluxing was continued for additional 3.5 hours. The cooled reaction mixture was poured in aqueous potassium carbonate solution (21 g K2CO3+210 ml water) and allowed to stand overnight at the ambient temperature. The mixture was filtered and the precipitate was washed with THF. The filtrate was evaporated to dryness. The residue was dissolved in ethyl acetate and washed with water. Ethyl acetate phase was evaporated to dryness and the residue was crystallized first from methanol-water (8:2) and then from methanol-water (9:1). Yield 5.4 g.

Workup

  1. additionAfter the addition
  2. temperaturewas refluxed for two hours
  3. temperatureThen the mixture was cooled to 40° C.
  4. additionwere added to the mixture
  5. temperatureRefluxing
  6. customThe cooled reaction mixture
  7. waitto stand overnight at the ambient temperature
  8. filtrationThe mixture was filtered
  9. washthe precipitate was washed with THF
  10. customThe filtrate was evaporated to dryness
  11. dissolutionThe residue was dissolved in ethyl acetate
  12. washwashed with water
  13. customEthyl acetate phase was evaporated to dryness
  14. customthe residue was crystallized first from methanol-water (8:2)

Sources & evidence

ORD record
ord-7713ecb9d9914d82bcac18eb4abfbf92
Source dataset
uspto-grants-2012_10
Patent number
US08293947B2

Reaction notes

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