Dimethylformamide → 5-Bromo-2-hydroxybenzophenone

HRID 25825

Reaktionsgleichung

Reaktionsgleichung von HRID 25825
O=S(Cl)Cl.[Br:5][C:6]1[CH:7]=[CH:8][C:9]([O:15]C)=[C:10]([CH:14]=1)[C:11]([OH:13])=O.CN(C=O)C.[Al+3].[Cl-].[Cl-].[Cl-]>C1(C)C=CC=CC=1.C1C=CC=CC=1.C(Cl)Cl>[Br:5][C:6]1[CH:7]=[CH:8][C:9]([OH:15])=[C:10]([C:11]([C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][CH:14]=2)=[O:13])[CH:14]=1

Komponenten

8

Edukt 4

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 8817395-Bromo-2-methoxybenzoic acidHCID 6451240Aluminum(III) Chloride

Produkt 1

HCID 2290095-Bromo-2-hydroxybenzophenoneAusbeute 181,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 241BenzeneLösungsmittelHCID 1140TolueneLösungsmittelHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

10.07 ml (138.8 mmol, 2.2 eqv) SOCl2 was added to a solution of 14.77 g (63.9 mmol) 5-Bromo-2-methoxy-benzoic acid (17) in 140 ml dry toluene, followed by 0.5 ml (6.5 mmol, 0.1 eqv) DMF. After stirring this solution for 1.5 h at 70° C. the solvent was evaporated and the the crude acyl chloride was dissolved in 75 ml of dry benzene. This solution was then added cautiously under stirring to a suspension of 10.30 g (77.3 mmol, 1.2 eqv) AlCl3 in 80 ml dry benzene at 10° C. After complete addition the resulting mixture was refluxed for 5 h and then quenched by adding H2O and conc. hydrochloric acid. The aq. layer was extracted with EtOAc and the comb. org. fractions were dried over NaSO4 and evaporated. Column chromatography (CH2Cl2) yielded 16.03 g (57.9 mmol, 90%) 18 as a yellow solid: Rf (CH2Cl2) 0.67; 1H NMR (500 MHz, CDCl3) δ 6.99 (d, 1H, J=8.99 Hz), 7.52-7.68 (m, 6H), 7.70 (d, 1H, J=2.36 Hz), 11.91 (s, 1H); LRMS (EI) m/z 278 (80), 277 (100), 276 (86), 275 (92), 201 (31), 200 (22), 199 (30), 198 (20), 105 (63), 77 (57), 63 (19); HRMS (EI) Calcd. for C13H9BrO2: 275.978591. Found: 275.977717.

Aufarbeitung

  1. customwas evaporated
  2. dissolutionthe the crude acyl chloride was dissolved in 75 ml of dry benzene
  3. additionThis solution was then added cautiously
  4. additionAfter complete addition the resulting mixture
  5. temperaturewas refluxed for 5 h
  6. customquenched
  7. additionby adding H2O and conc. hydrochloric acid
  8. extractionThe aq. layer was extracted with EtOAc
  9. dry with materialfractions were dried over NaSO4
  10. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-d30691bddd8d48238d3f9213ccbef0a1
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06858600B2

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