3,4-dihydro-2H-pyran → 2-(6-Bromo-2-methyl-2-p-tolylhexyloxy)-tetrahydropyran

HRID 47984Notes

Reaction equation

HRID 47984 reaction equation
[O:1]1[CH:6]=[CH:5][CH2:4][CH2:3][CH2:2]1.[Br:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([CH3:22])([C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=1)[CH2:13][OH:14]>ClCCl.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[Br:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([CH3:22])([C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=1)[CH2:13][O:14][CH:6]1[CH2:5][CH2:4][CH2:3][CH2:2][O:1]1

Participants

5

Reactant 2

HCID 80803,4-dihydro-2H-pyranHCID 111968926-Bromo-2-methyl-2-p-tolylhexan-1-ol

Product 1

HCID 113606702-(6-Bromo-2-methyl-2-p-tolylhexyloxy)-tetrahydropyranYield 93.4%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 6344DichloromethaneSolvent

Procedure

Under N2 atmosphere, 3,4-dihydro-2H-pyran (6.39 g, 76.09 mmol) was added drop-wise to a stirred solution of 6-bromo-2-methyl-2-p-tolyl-hexan-1-ol (18.20 g, 63.86 mmol) and p-toluenesulfonic acid hydrate (0.43 g, 2.26 mmol) in dichloromethane (300 mL) at −5° C. The reaction mixture was allowed to warm to rt and stirred for 3 h. The solution was filtered through aluminum oxide (160 g), which was washed with CH2Cl2 (500 mL). The filtrate was concentrated in vacuo to furnish 2-(6-bromo-2-methyl-2-p-tolyl-hexyloxy)-tetrahydropyran (22 g, 93.4%) as an oil. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm) 7.25-7.05 (m, 4H), 4.60-4.48 (m, 1H), 3.82 (m, 2H), 3.48-3.37 (m, 2H), 3.35-3.26 (m, 2H), 2.30 (s, 3H), 1.90-1.40 (m, 11H), 1.40-1.33 (s, 3H), 1.40-1.08 (m, 1H), 13C NMR (75 MHz, CDCl3/TMS): δ (ppm) 142.78, 135.22, 128.81, 126.39, 99.09, 61.99, 41.67, 38.12, 37.87, 33.68, 30.99, 25.96, 23.08, 22.89, 21.12, 20.97, 19.41. HRMS (LSIMS, nba): Calcd. for C19H30O2Br (MH+): 369.1429, found: 369.1451.

Workup

  1. filtrationThe solution was filtered through aluminum oxide (160 g), which
  2. washwas washed with CH2Cl2 (500 mL)
  3. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-c7e4bc97a5c24b69990d5ed281164101
Source dataset
uspto-grants-2004_03
Patent number
US06699910B2

Reaction notes

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