Hydrochloric Acid → 3-(Bromomethyl)benzaldehyde

HRID 1587291Notes

Reaction equation

HRID 1587291 reaction equation
[H-].C([Al+]CC(C)C)C(C)C.[Br:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([C:19]#N)[CH:14]=1.Cl.CC[O:24]CC>ClC1C=CC=CC=1>[Br:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([CH:19]=[O:24])[CH:14]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 3283Diethyl EtherHCID 97249Benzonitrile, 3-(bromomethyl)-HCID 21225700Diisobutylaluminumhydride

Product 1

HCID 71278253-(Bromomethyl)benzaldehydeYield 71%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of diisobutylaluminum hydride (92 ml, 1M in hexanes, 92 mmol) was added dropwise via syringe pump injector over a period of 45 min to a solution of α-bromo-m-tolunitrile (15.000 g, 76.5 mmol) in 155 ml of chlorobenzene at 0° C. The resulting mixture was stirred at 0° C. for 1 h, then 100 ml of 10% aqueous HCl was added and stirring continued at 0° C. for 10 min. The layers were separated and the aqueous layer extracted with ether (2x). The organic solutions were combined and washed vigorously with 10% HCl for 10 min, then water (2x) and brine, dried over MgSO4 and evaporated to give a crystalline solid which was then dissolved in a minimal amount of ether (10-15 ml) and layered with petroleum ether (30-40 ml). The resulting spiny white crystals were collected and washed with ice-cold petroleum ether to yield 10.791 g (71%) of aldehyde 1: m.p. 46°-49° C.; 1H NMR δ 4.54 (s, 1, CH2Br), 7.52 (t, 1, J=8 Hz, H-5), 7.67 (br d, 1, J=8 Hz, H-4), 7.82 (dt, 1, J=8, 1 Hz, H-6), 7.90 (br s, 1, H-2), 10.02 (s, 1, CHO); 13C NMR δ 32.0 (CH2Br), 129.6, 129.7 and 129.8 (C-2, C-5 and C-6), 134.8 (C-4), 136.8 (C-1), 138.9 (C-3), 191.6 (CHO); IR ν 1595 and 1610 (m, C=C), 1710 (s, C=O), 2740 and 2820 (m, CHO) cm-1.

Workup

  1. stirringstirring
  2. waitcontinued at 0° C. for 10 min
  3. customThe layers were separated
  4. extractionthe aqueous layer extracted with ether (2x)
  5. washwashed vigorously with 10% HCl for 10 min
  6. dry with materialwater (2x) and brine, dried over MgSO4
  7. customevaporated
  8. customto give a crystalline solid which
  9. customThe resulting spiny white crystals were collected
  10. washwashed with ice-cold petroleum ether

Sources & evidence

ORD record
ord-16d1fdf4b6874d99a17b279205812a56
Source dataset
uspto-grants-1993_06
Patent number
US05217966

Reaction notes

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