3-Bromobenzaldehyde → (E)-5-(3-bromophenyl)pent-4-enoic acid

HRID 2407582Notes

Reaction equation

HRID 2407582 reaction equation
CC(C)([O-])C.[K+].[Br-].[C:8]([CH2:11][CH2:12][CH2:13][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([OH:10])=[O:9].[Br:33][C:34]1[CH:35]=[C:36]([CH:39]=[CH:40][CH:41]=1)[CH:37]=O>O1CCCC1.CS(C)=O>[Br:33][C:34]1[CH:35]=[C:36](/[CH:37]=[CH:13]/[CH2:12][CH2:11][C:8]([OH:10])=[O:9])[CH:39]=[CH:40][CH:41]=1

Participants

6

Reactant 3

HCID 765833-BromobenzaldehydeHCID 10717451(3-Carboxypropyl)(triphenyl)phosphanium bromideHCID 23665647Potassium tert-butoxide

Product 1

HCID 11579732(E)-5-(3-bromophenyl)pent-4-enoic acid

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A 1M solution of potassium tert-butoxide in tetrahydrofuran (80 mL) was added dropwise to (3-carboxypropyl)triphenylphosphonium bromide (17 g, 40 mol) in anhydrous DMSO (20 mL) under nitrogen at 24° C., and the solution was stirred 30 min. before addition of 3-bromobenzaldehyde (4.7 mL, 40 mmol). After several minutes a precipitate was observed and an additional 20 mL of DMSO was added to aid solvation, and the reaction was stirred 18 h. The solution was poured onto water (120 mL) and washed with chloroform. The aqueous layer was acidified with conc. HCl and extracted with chloroform (3×250 mL). The organic phase was concentrated and applied to a 65i Biotage silica gel column, gradient elution from 15-65% B (A=Hexanes; B=ethyl acetate) over 2 L to give J.1, (E)-5-(3-bromophenyl)pent-4-enoic acid, 8.2 g (82%). 1H NMR (300 MHz, CDCl3) δ 7.45 (t, J=1.5 Hz, 1H), 7.30 (dt, J=7.7, 1.5 Hz, 1H), 7.2-7.16 (m, 1H), 7.12 (t, J=7.7 Hz, 1H), 6.40-6.32 (m, 1H), 6.23-6.14 (m, 1H), 2.52 (s, 4H). LC (Cond.-J1): RT=2.0 min; LRMS: Anal. Calcd. for [M−H]− C11H11BrO2: 252.97; found: 252.98.

Workup

  1. waitAfter several minutes a precipitate was observed
  2. additionThe solution was poured onto water (120 mL)
  3. washwashed with chloroform
  4. extractionextracted with chloroform (3×250 mL)
  5. concentrationThe organic phase was concentrated
  6. washapplied to a 65i Biotage silica gel column, gradient elution from 15-65% B (A=Hexanes

Sources & evidence

ORD record
ord-627dbe07219f4b428b33708d2b9d083b
Source dataset
uspto-grants-2014_08
Patent number
US08809548B2

Reaction notes

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