3,4-dihydro-2H-pyran → 2-[(2-Bromophenyl)methoxy]oxane

HRID 2423265Notes

Reaction equation

HRID 2423265 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][OH:9].[O:10]1[CH:15]=[CH:14][CH2:13][CH2:12][CH2:11]1.C([O-])(O)=O.[Na+]>Cl.C(OCC)C>[O:10]1[CH2:15][CH2:14][CH2:13][CH2:12][CH:11]1[O:9][CH2:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[Br:1]

Participants

6

Reactant 3

HCID 80803,4-dihydro-2H-pyranHCID 728502-Bromobenzyl alcoholHCID 516892Sodium Bicarbonate

Product 1

HCID 53150262-[(2-Bromophenyl)methoxy]oxane

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidCatalystHCID 3283Diethyl EtherSolvent

Procedure

Ten drops of concentrated hydrochloric acid were added to a mixture of 2-bromophenylmethanol (34 g, 0.18 mol) and 3,4-dihydro-2H-pyran (18 g, 0.22 mol), and the resulting mixture was stirred overnight at room temperature. The mixture was diluted with diethyl ether, and the organic phase was neutralized with a saturated NaHCO3 aqueous solution. Further, the resultant was dried over anhydrous MgSO4 and was concentrated under reduced pressure to obtain 2-(2-tetrahydro-2H-pyranoxymethyl)bromobenzene, to which dissolved in THF (450 mL) was added a 1.6 M n-BuLi solution in hexane (124 mL, 0.20 mol) at −78° C. over 40 minutes. The resulting solution was stirred for 50 minutes at −78° C., and chlorodimethylsilane (20 g, 0.22 mol) was added thereto. The mixture was warmed gradually at room temperature overnight and then was quenched with water. After evaporation of THF, the residue thereof was extracted with diethylether, and the combined organic layers were washed with brine, and then the resultant was dried over anhydrous MgSO4. The dried resultant was distilled under reduced pressure, thereby obtaining dimethyl[2-(2-tetrahydro-2H-pyranoxymethyl)phenyl]silane (5) (38 g, yield of 83%) as a colorless oil, bp: 135° C. (1.0 mmHg). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J=7.2 Hz, 1H), 7.44 (d, J=7.2 Hz, 1H), 7.40-7.36, (m, 1H), 7.31-7.27 (m, 1H), 4.87 (d, J=12.0 Hz, 1H), 4.74 (s, 1H), 4.60 (d, J=12.0 Hz, 1H), 4.58-4.50 (m, 1H), 4.00-3.95 (m, 1H), 3.62-3.54 (m, 1H), 1.94-1.50 (m, 6H), 0.36 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 143.6, 136.5, 134.7, 129.4, 128.3, 127.0, 98.1, 69.1, 62.1, 30.6, 25.5, 19.3, −3.0, −3.1; Anal. Calcd for C14H22O2Si; C, 67.15; H, 8.86. Found: C, 67.44; H, 8.91.

Workup

  1. dry with materialFurther, the resultant was dried over anhydrous MgSO4
  2. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-a9b553bf21dd4242949e1ee214c6f570
Source dataset
uspto-grants-2011_06
Patent number
US07960571B2

Reaction notes

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