Diethyl methylmalonate → Diethyl 2-(4-bromobenzyl)malonate

HRID 1107496Notes

Reaction equation

HRID 1107496 reaction equation
[CH3:1][CH:2]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[Na].[Br:14][C:15]1[CH:22]=[CH:21][C:18](CBr)=[CH:17][CH:16]=1>C(O)C>[Br:14][C:15]1[CH:22]=[CH:21][C:18]([CH2:1][CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:17][CH:16]=1

Participants

5

Reactant 3

HCID 11857Diethyl methylmalonateHCID 685274-Bromobenzyl bromideHCID 5360545Sodium

Product 1

HCID 10860456Diethyl 2-(4-bromobenzyl)malonateYield 91.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A solution of diethyl methylmalonate (87 g) in absolute ethanol (100 ml) was added to a pre-formed solution of sodium (11.5 g) in ethanol (400 ml) under argon. A hot solution of p-bromobenzylbromide (125 g) in absolute alcohol (200 ml) was added rapidly with vigorous stirring, which was continued for 3 days and the solid so formed was removed by filtration. The filtrate was evaporated and the residue dissolved in ethyl acetate (11), washed with brine (250 ml), dried (MgSO4) and evaporated. The residual oil was distilled under vacuum to give diethyl (4-bromophenyl)methylmalonate (150.7 g) b.p. 130-133/0.03 mm Hg; 1H NMR (d6 -DMSO): 1.33 (t, 6H), 1.4 (s, 3H), 3.27 (s, 2H), 4.30 (q, 4H), 7.23 (d, 2H), 7.6 (d, 2H),

Workup

  1. customthe solid so formed
  2. customwas removed by filtration
  3. customThe filtrate was evaporated
  4. dissolutionthe residue dissolved in ethyl acetate (11)
  5. washwashed with brine (250 ml)
  6. dry with materialdried (MgSO4)
  7. customevaporated
  8. distillationThe residual oil was distilled under vacuum

Sources & evidence

ORD record
ord-3d7220da61eb4598b706a04456829a74
Source dataset
uspto-grants-2000_05
Patent number
US06060475

Reaction notes

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