Water → 2-(4-Bromophenyl)-1-(2,4-dichlorophenyl)ethanone

HRID 1392365Notes

Reaction equation

HRID 1392365 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[C:9]([C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[Cl:20])C(O)=O)=[CH:4][CH:3]=1.C(N(CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:35])C=CC=CC=1.O>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[Cl:20])=[O:35])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 692887223-(4-Bromophenyl)-2-(2,4-dichlorophenyl)acrylic acid

Product 1

HCID 634923632-(4-Bromophenyl)-1-(2,4-dichlorophenyl)ethanoneYield 60.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

Part B; 3-(4-Bromophenyl)-2-(2,4-dichlorophenyl)acrylic acid (26.55 gram, 71 mmol) is dissolved in anhydrous toluene (130 mL) and the resulting solution is cooled to 0° C. Triethylamine (7.40 gram, 73 mmol) and diphenylphosphoryl azide (19.8 gram, 72 mmol) are successively added and the resulting mixture Is stirred at 0° C. for 20 minutes and 150 minutes at room temperature. The reaction mixture is poured into water and extracted three times with diethyl ether. The collected organic layers are dried over MgSO4 and the diethyl ether Is removed in vacuo. The resulting toluene layer is slowly added to refluxing toluene (150 mL). t-Butanol is added after 90 minutes and heating at reflux temperature is continued for 1 hour, followed by slow addition of concentrated hydrochloric acid (5 mL). After stirring the resulting solution overnight at 90° C. it is allowed to attain room temperature, washed twice with water, dried over MgSO4, filtered and evaporated in vacuo to give a yellow oil. This oil is crystallised from n-hexane to give 2-(4-bromophenyl)-1-(2,4-dichlorophenyl)ethanone (14.72 gram, 60% yield). Melting point: 69-70° C.

Workup

  1. extractionextracted three times with diethyl ether
  2. dry with materialThe collected organic layers are dried over MgSO4
  3. customthe diethyl ether Is removed in vacuo
  4. additionThe resulting toluene layer is slowly added
  5. temperatureto refluxing toluene (150 mL)
  6. additiont-Butanol is added after 90 minutes
  7. temperatureheating
  8. temperatureat reflux temperature
  9. waitis continued for 1 hour
  10. additionfollowed by slow addition of concentrated hydrochloric acid (5 mL)
  11. stirringAfter stirring the resulting solution overnight at 90° C. it
  12. customto attain room temperature
  13. washwashed twice with water
  14. dry with materialdried over MgSO4
  15. filtrationfiltered
  16. customevaporated in vacuo
  17. customto give a yellow oil
  18. customThis oil is crystallised from n-hexane

Sources & evidence

ORD record
ord-128576c391e24f2c859f1fc0c8eeea7e
Source dataset
uspto-grants-2008_03
Patent number
US07342032B2

Reaction notes

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