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

HRID 275529

Reaction equation

HRID 275529 reaction equation
[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

Participants

9

Reactant 7

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

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

Workup

  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)

Sources & evidence

ORD record
ord-dab8c0e2d7bf4f939662208646b938b2
Source dataset
uspto-grants-1995_02
Patent number
US05393785

Linked notes

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