Dimethylformamide → 5-Bromo-2-hydroxybenzophenone

HRID 25825

反応式

HRID 25825 の反応式
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

参加物

8

反応物 4

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

生成物 1

HCID 2290095-Bromo-2-hydroxybenzophenone収率 181.2%

試薬・触媒・溶媒 3

HCID 241Benzene溶媒HCID 1140Toluene溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
70 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-d30691bddd8d48238d3f9213ccbef0a1
出典データセット
uspto-grants-2005_02
特許番号
US06858600B2

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