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

HRID 2380168

반응식

HRID 2380168 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 13 (710 mg, 2.5 mmol, prepared from desoxyanisoin, ethyl bromide and LDA by a known method) in THF (10 ml) are 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, IR νmax (neat) 3480, 1600 cm-1 ; 1H-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, --O3 --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-8ec3a9549a474ae0bcf14e30d5ae4f11
출처 데이터셋
uspto-grants-1994_11
특허 번호
US05364847

연결된 노트

불러오는 중…