Diethyl (ethoxymethylene)malonate → Diethyl (5-butyl-1,3-dioxan-2-yl)-malonate

HRID 1378269Notes

Reaction equation

HRID 1378269 reaction equation
[CH2:1]([CH:5]([CH2:8][OH:9])[CH2:6][OH:7])[CH2:2][CH2:3][CH3:4].C(O[CH:13]=[C:14]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:15]([O:17][CH2:18][CH3:19])=[O:16])C>O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C1(C)C=CC=CC=1>[CH2:1]([CH:5]1[CH2:8][O:9][CH:13]([CH:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:20]([O:22][CH2:23][CH3:24])=[O:21])[O:7][CH2:6]1)[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 2

HCID 6871Diethyl (ethoxymethylene)malonateHCID 27952592-n-Butylpropane-1,3-diol

Product 1

HCID 22378551Diethyl (5-butyl-1,3-dioxan-2-yl)-malonateYield 89.4%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 1140TolueneSolvent2×

Procedure

A mixture of 17.45 g of 2-butyl-1,3-propanediol, 26.4 g of diethyl (ethoxymethylidene)-malonate, 250 ml of toluene and 0.285 g of p-toluenesulfonic acid monohydrate was heated to boiling for 1 hour, with moist toluene being distilled off and replaced by the addition of fresh toluene. The reaction mixture was neutralized with triethylamine and, after cooling, washed with saturated sodium chloride solution, dried over sodium sulphate and concentrated. The crude product (42.35 g) was chromatographed on 520 g of silica gel with hexane/ethyl acetate (4:1). 33.0 g of oily diethyl (5-butyl-1,3-dioxan-2-yl)-malonate were obtained.

Workup

  1. temperaturewas heated
  2. distillationdistilled off
  3. additionreplaced by the addition of fresh toluene
  4. temperatureafter cooling
  5. washwashed with saturated sodium chloride solution
  6. dry with materialdried over sodium sulphate
  7. concentrationconcentrated
  8. customThe crude product (42.35 g) was chromatographed on 520 g of silica gel with hexane/ethyl acetate (4:1)

Sources & evidence

ORD record
ord-b415ca9aca3246a3bfbecd4fa48c5719
Source dataset
uspto-grants-1997_09
Patent number
US05667721

Reaction notes

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