Ethyl Acetate → α-(4-Bromophenyl)-1,3-dioxane-2-propanol

HRID 80388Notes

Reaction equation

HRID 80388 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][O:3][CH:2]1[CH2:7][CH2:8][Mg]Br.[Br:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]=[O:17])=[CH:14][CH:13]=1.C(OCC)(=O)C>C1COCC1>[Br:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]([OH:17])[CH2:8][CH2:7][CH:2]2[O:3][CH2:4][CH2:5][CH2:6][O:1]2)=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 707414-BromobenzaldehydeHCID 178419673HCID 178419673, compound

Product 1

HCID 57610901α-(4-Bromophenyl)-1,3-dioxane-2-propanol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

108 mL of (1,3-dioxan-2-ylethyl) magnesium bromide (0.5M) was added to a solution of 4-bromobenzaldehyde (10 g, 54.0 mmol) in THF (350 mL) at −78° C. under nitrogen and stirred for 2 hours before warming to 0° C. The reaction was quenched with sat NH4Cl soln, diluted with diethyl ether and washed with brine. The crude product was charged (CH2Cl2) to a 40M Biotage silica gel cartridge; Gradient elution 15-100% B over 750 mL (A=Hexanes; B=ethyl acetate) to give Example J1, 1-(4-bromophenyl)-3-(1,3-dioxan-2-yl)propan-1-ol (quantitative yield). 1H NMR (500 MHz, CDCl3) δ 7.44 (d, J=8.5 Hz, 2H), 7.22 (d, J=8.5 Hz, 2H), 4.70-4.66 (m, 1H), 4.57 (t, J=4.9 Hz, 1H), 4.12-4.19 (m, 2H), 3.76 (tt, J=11.9, 2.7 Hz, 2H), 2.87 (d, J=3.7 Hz, 1H), 2.12-2.03 (m, 1H), 1.86-1.87 (m, 2H), 1.74-1.68 (m, 2H), 1.36-1.32 (m, 1H). RT=1.8 minutes (condition 1); LRMS: No parent ion evident.

Workup

  1. customThe reaction was quenched with sat NH4Cl soln
  2. additiondiluted with diethyl ether
  3. washwashed with brine
  4. additionThe crude product was charged (CH2Cl2) to a 40M Biotage silica gel cartridge
  5. washGradient elution 15-100% B over 750 mL (A=Hexanes

Sources & evidence

ORD record
ord-7c94ecf8993441d690e2db5a1a6784dd
Source dataset
uspto-grants-2014_09
Patent number
US08846023B2

Reaction notes

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