2-Butene-1,4-diol → 1572-84-5

HRID 1369175Notes

Reaction equation

HRID 1369175 reaction equation
C(N([CH2:6][CH3:7])CC)C.[CH2:8]([OH:13])[CH:9]=[CH:10][CH2:11][OH:12].[C:14](Cl)(=[O:18])[CH2:15][CH2:16][CH3:17].[C:20]([O:24]C)(C)(C)[CH3:21]>CN(C1C=CN=CC=1)C>[CH3:17][CH2:16][CH2:15][C:14]([O:12][CH2:11]/[CH:10]=[CH:9]/[CH2:8][O:13][C:20]([CH2:21][CH2:6][CH3:7])=[O:24])=[O:18]

Participants

6

Reactant 4

HCID 80652-Butene-1,4-diolHCID 8471TriethylamineHCID 8855Butyryl chlorideHCID 15413tert-Butyl methyl ether

Product 1

HCID 120711921572-84-5Yield 95%

Reagents, catalysts & solvents 1

HCID 142844-(Dimethylamino)pyridineCatalyst

Conditions

Temperature
4 °C

Procedure

To a 200 gallon reactor equipped with an efficient cooling system was charged methyl tert-butyl ether (MtBE, 278 L), DMAP (391 g, 3.2 moles), triethylamine (102.3 L, 74.4 kg, 736.2 moles) and 2-butene-1,4-diol (26.4 L, 28.2 kg, 320 moles). The stirrer was started and the temperature of the reaction mixture was cooled to approximately 4° C. Butyryl chloride (69.6 L, 71.5 kg, 672 moles) was added to the reaction mixture at such a rate as to maintain the batch temperature below 20° C. The triethylamine hydrochloride precipitates during the addition and the reaction mixture becomes a thick, but movable slurry. Thin layer chromatographic analysis of the reaction mixture (silica gel plate; Analtech No. 02521, eluted with 9:1 hexane/EtOAc, and visualized with PMA stain) indicated the reaction was complete after stirring for an additional hour after the addition was complete. Water (120 L) was added to the reactor, and the resulting mixture was stirred until all of the solids dissolved. The phases were separated. The lower (aqueous) layer was checked by TLC analysis for the absence of product (if product is present, save the layer for future product recovery). The upper, organic layer was washed with water (72 L), saturated aqueous potassium bicarbonate (72 L, checked to make sure the exiting aqueous layer was basic, evaporated, under reduced pressure, to afford 69.4 kg of 2-butene-1,4-dibutyrate (95% yield) as a pale golden oil. The NMR spectrum was consistent with a reference spectrum.

Workup

  1. customTo a 200 gallon reactor equipped with an efficient cooling system
  2. temperatureto maintain the batch temperature below 20° C
  3. customThe triethylamine hydrochloride precipitates during the addition
  4. washThin layer chromatographic analysis of the reaction mixture (silica gel plate; Analtech No. 02521, eluted with 9:1 hexane/EtOAc, and visualized with PMA stain)
  5. additionafter the addition
  6. additionWater (120 L) was added to the reactor
  7. stirringthe resulting mixture was stirred until all of the solids
  8. dissolutiondissolved
  9. customThe phases were separated
  10. washThe upper, organic layer was washed with water (72 L), saturated aqueous potassium bicarbonate (72 L
  11. customevaporated, under reduced pressure

Sources & evidence

ORD record
ord-34e85cc0261748cdb9927a89f8a2ad38
Source dataset
uspto-grants-2003_06
Patent number
US06576776B1

Reaction notes

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