3,4-dihydro-2H-pyran → 2-(7-Bromo-2,2-dimethylheptyloxy)-tetrahydropyran

HRID 661182Notes

Reaction equation

HRID 661182 reaction equation
BrCCC[CH2:5][C:6]([CH3:21])([C:15]1C=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1.[Br:22]CCCCCC(C)(C)CO.O1C=CCCC1>C(Cl)Cl.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[Br:22][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][C:6]([CH3:21])([CH3:5])[CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1

Participants

6

Reactant 3

HCID 80803,4-dihydro-2H-pyranHCID 112104532-(6-Bromo-2-methyl-2-phenylhexyloxy)-tetrahydropyranHCID 113106207-Bromo-2,2-dimethylheptan-1-ol

Product 1

HCID 112090012-(7-Bromo-2,2-dimethylheptyloxy)-tetrahydropyranYield 46%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 6344DichloromethaneSolvent

Procedure

According to the method described for the synthesis of 207d, 206g (36.0 g, 161 mmol) was treated with 3,4-dihydro-2H-pyran (18.5 g, 220 mmol) and p-toluenesulfonic acid hydrate (0.28 g, 1.5 mmol) in CH2Cl2 (60 mL). After filtration through neutral aluminum oxide (200 g) and concentration, the crude product was purified by column chromatography (silica gel; hexanes/ethyl acetate=50/1), affording 207g (23.0 g, 46%) as an oil. 1H NMR (CDCl3): δ 4.54 (t, 1H, J=3.0), 3.84 (m, 1H), 3.51-3.39 (m, 4H), 2.98 (d, 1H, J=9.3), 1.89-1.80 (m, 3H), 1.70-1.40 (m, 7H), 1.29-1.22 (m, 4H), 0.89 (s, 6H). 13C NMR (CDCl3): δ 99.3, 76.6, 62.1, 39.3, 34.3, 34.2, 33.0, 30.8, 29.2, 25.7, 24.7, 23.2, 19.6. HRMS (LSIMS, gly): Calcd for C14H28BrO2 (MH+): 307.1272. found: 307.1245.

Workup

  1. filtrationAfter filtration
  2. concentrationthrough neutral aluminum oxide (200 g) and concentration
  3. customthe crude product was purified by column chromatography (silica gel; hexanes/ethyl acetate=50/1)

Sources & evidence

ORD record
ord-d26ff275b8cb4dd99862b106b448bc80
Source dataset
uspto-grants-2011_12
Patent number
US08084498B2

Reaction notes

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