Toluene → Ethyl 2-(2-methylbenzyl)-3-oxobutanoate

HRID 973919Notes

Reaction equation

HRID 973919 reaction equation
[CH3:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4]Cl.[OH-].[Na+].[C:12]([O:18][CH2:19][CH3:20])(=[O:17])[CH2:13][C:14]([CH3:16])=[O:15].C1(C)C=CC=CC=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH3:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4][CH:13]([C:14]([CH3:16])=[O:15])[C:12]([O:18][CH2:19][CH3:20])=[O:17]

Participants

7

Reactant 4

HCID 1140TolueneHCID 8868Ethyl AcetoacetateHCID 11093alpha-Chloro-o-xyleneHCID 14798Sodium Hydroxide

Product 1

HCID 15588514Ethyl 2-(2-methylbenzyl)-3-oxobutanoate

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolvent

Procedure

344 g (2.45 moles) of o-methylbenzyl chloride and 3.5 moles of 25% strength aqueous NaOH solution were added dropwise to a refluxed, thoroughly stirred solution of 455 g (3.5 moles) of ethyl acetoacetate, 35 g (0.11 moles) of tetrabutylammonium bromide and 1.2 liters of toluene in the course of 2 hours, simultaneously from two dropping funnels. Thereafter, stirring was continued for a further 2 hours with refluxing. After the reaction solution had cooled, water was added, the phases were separated and the organic phase was washed once with water, once with dilute phosphoric acid and again with water and was then stirred with solid sodium bicarbonate. The mixture was filtered, the solution was freed from toluene and the residue was subjected to vacuum distillation over a 10 cm Vigreux column. 390 g (68% of the theoretical yield) of ethyl 2-(o-methylbenzyl)-acetoacetate of boiling point 100°-105° C. at 0.01 mm Hg were obtained.

Workup

  1. temperaturewith refluxing
  2. temperatureAfter the reaction solution had cooled
  3. customthe phases were separated
  4. washthe organic phase was washed once with water, once with dilute phosphoric acid and again with water
  5. stirringwas then stirred with solid sodium bicarbonate
  6. filtrationThe mixture was filtered
  7. distillationthe residue was subjected to vacuum distillation over a 10 cm Vigreux column

Sources & evidence

ORD record
ord-26b7361f94124bf7b0fb4e01f45eec04
Source dataset
uspto-grants-1991_11
Patent number
US05066640

Reaction notes

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