Hydrochloric Acid → 12,13-Bis-(4-methoxyphenyl)tetrahydropyranyl pentadecan-1,12-diol

HRID 1608736

반응식

HRID 1608736 반응식
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=[O:21])[CH:10]([CH2:19][CH3:20])[C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)=[CH:5][CH:4]=1.C1(C(CC2C=CC(OC)=CC=2)=O)C=CC(OC)=CC=1.C(Br)C.[Li+].CC([N-]C(C)C)C.Br[CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH:63]([CH:65]1[CH2:70][CH2:69][CH2:68][CH2:67][O:66]1)[OH:64].[Mg].Cl>C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([C:9]([OH:21])([CH:10]([C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)[CH2:19][CH3:20])[CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH:63]([CH:65]2[CH2:70][CH2:69][CH2:68][CH2:67][O:66]2)[OH:64])=[CH:7][CH:8]=1

참가 물질

9

반응물 7

HCID 313Hydrochloric AcidHCID 6332Ethyl BromideHCID 67120DesoxyanisoinHCID 2332181,2-Bis(4-methoxyphenyl)butan-1-oneHCID 2724682Lithium diisopropylamideHCID 5462224MagnesiumHCID 1893689211-Bromo-tetrahydropyranyl undecanol

생성물 1

HCID 1893690912,13-Bis-(4-methoxyphenyl)tetrahydropyranyl pentadecan-1,12-diol수율 76%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

4'-methoxy-2-ethyl,2-(4-methoxyphenyl) acetophenone (2) (710 mg, 2.5 mmol, prepared from desoxyanisoin, ethyl bromide and LDA by a known method) in THF (10 ml) were added, under argon, to Grignard reagent prepared from 11-bromo-tetrahydropyranyl undecanol (6.6 g, 19.7 mmoles) and magnesium (0.6 g, 24.7 mmoles) and THF (10 ml). The mixture was stirred for 18 hours, then acidified with 1N HCl and extracted three times with ether. The organic phase was washed with water (X3), dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The residue was chromatographed on Silica-gel (Kieselgel, 60F254, Merck, 0.063-0.200 mm, 100 g). Elution with a mixture of hexane-ethyl acetate (9:1 v/v) gave 12,13-Bis-(4-methoxyphenyl)tetrahydropyranyl pentadecan-1,12-diol (991 mg, 76%) as a mixture of diastereoisomers; colorless oil, IRνmax (neat) 3480, 1600 cm-1 ; 'H-NMR (δ, CDCl3); 0.62 (3H, t, J=7.3 Hz, CH2CH3), 2.73 (1H, 2d, J=9.7 Hz, --CHCH2CH3), 3.25-4.00 (4H, m, --CH2OCHOCH2 --), 3.76 and 3.79 (6H, 2s, --OCH3), 4.57 (1H, t, J=1.1 Hz, --O2 --CH--CH2) and 6.71-7.30 (8H, m,H--Ar)ppm. MS m/e=523 (M+ --H2O).

후처리

  1. extractionextracted three times with ether
  2. washThe organic phase was washed with water (X3)
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customevaporated under reduced pressure
  5. customThe residue was chromatographed on Silica-gel (Kieselgel, 60F254, Merck, 0.063-0.200 mm, 100 g)
  6. washElution
  7. additionwith a mixture of hexane-ethyl acetate (9:1 v/v)

출처 및 근거

ORD 기록
ord-36107f988e4e44339f0304c2d6dd2149
출처 데이터셋
uspto-grants-1995_03
특허 번호
US05395842

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