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

HRID 2259527노트

반응식

HRID 2259527 반응식
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

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 6228Dimethylformamide용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-2aba68ae29cd423c91c8d14d686056ab
출처 데이터셋
uspto-grants-1995_12
특허 번호
US05472964

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