Methyl 2-bromobenzoate → Methyl 2-[3-(3-hydroxyphenyl)-3-oxopropyl]benzoate

HRID 2259527ノート

反応式

HRID 2259527 の反応式
Br[C:2]1[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Li+].[Cl-].[Li]O[C:16]([CH3:18])=[O:17].[OH2:19]>CN(C=O)C.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[OH:17][C:16]1[CH:18]=[C:11]([C:10](=[O:19])[CH2:9][CH2:8][C:2]2[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=2[C:4]([O:6][CH3:7])=[O:5])[CH:2]=[CH:3][CH:4]=1

参加物

7

反応物 3

HCID 11894Methyl 2-bromobenzoateHCID 433294Lithium ChlorideHCID 178526219lithium;acetate;hydrate

生成物 1

HCID 10564983Methyl 2-[3-(3-hydroxyphenyl)-3-oxopropyl]benzoate

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

実験手順

To a suspension of 3-(7-chloroquinolin-2-yl)methoxy)benzaldehyde (10.08 g, 33.9 mmol; U.S. Pat. No. 4,851,409 example 16 step 1) in toluene at 0° C. was added dropwise 1M vinylmagnesium bromide in THF (37 mL). After 30 min. the solution was quenched with NH4OAc, extracted with H2O, brine and dried over Na2SO4. The solvent was removed to afford 11.07 g of the allylic alcohol. This alcohol (11.00 g, 32.4 mmol), methyl o-bromobenzoate (7.31 g, 34 mmol), Pd(OAc)2 (218 mg), LiCl (1.37 g) and LiOAc.H2O (9.04 g) in 65 mL of DMF were heated to 100° C. for 3 h. The solution was cooled, poured in H2O (300 mL) and extracted with EtOAc (3×200 mL). The organic fractions were combined, washed with H2O, brine and dried over Na2SO4. Purification by chromatography (5% EtOAc in toluene) yield 12.44 g of LVIII. 1H NMR (300 MHz, CD3COCD3) δ3.30 (4H, m), 3.75 (3H, s), 5.45 (2H, s), 7.30-8.00 (12H, m) and 8.40 (1H, d).

後処理

  1. temperatureThe solution was cooled
  2. extractionextracted with EtOAc (3×200 mL)
  3. washwashed with H2O, brine
  4. dry with materialdried over Na2SO4
  5. customPurification by chromatography (5% EtOAc in toluene) yield 12.44 g of LVIII

出典と根拠

ORDレコード
ord-2aba68ae29cd423c91c8d14d686056ab
出典データセット
uspto-grants-1995_12
特許番号
US05472964

反応ノート

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