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

HRID 1081519

Reaktionsgleichung

Reaktionsgleichung von HRID 1081519
[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

Komponenten

9

Edukt 7

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

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 υmax (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, --O2 --CH--CH2) and 6.71-7.30 (8H, m,H--Ar)ppm. MS m/e=523 (M+ --H2O).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-f0b3134395304fa19eb1864fae2f69a4
Quelldatensatz
uspto-grants-1996_12
Patentnummer
US05585405

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