Acrolein → tert-Butyl 2-(1,1,1-trifluorobut-3-en-2-yloxy)acetate

HRID 1429645Notes

Reaction equation

HRID 1429645 reaction equation
[CH:1]([CH:3]=[CH2:4])=[O:2].[F:5][C:6]([Si](C)(C)C)([F:8])[F:7].CCCC[N+](CCCC)(CCCC)CCCC.[F-].Br[CH2:32][C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34].[OH-].[Na+]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C(OC)(C)(C)C.O.C1COCC1.C1(C)C=CC=CC=1>[F:5][C:6]([F:8])([F:7])[CH:1]([O:2][CH2:32][C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])[CH:3]=[CH2:4]

Participants

12

Reactant 5

HCID 7847AcroleinHCID 14798Sodium HydroxideHCID 79177tert-Butyl bromoacetateHCID 552549(Trifluoromethyl)trimethylsilaneHCID 2724141Tetrabutylammonium Fluoride

Product 1

HCID 86668365tert-Butyl 2-(1,1,1-trifluorobut-3-en-2-yloxy)acetateYield 94.5%

Reagents, catalysts & solvents 6

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 2724141Tetrabutylammonium FluorideCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
2.5 °C

Procedure

A reaction vessel was charged with toluene (3.2 L), THF (0.60 L) and acrolein (0.40 L, 5.985 mol) at rt under nitrogen. (Trifluoromethyl)trimethylsilane (1.003 kg, 7.059 mol) was added at 17° C. The reaction mixture was cooled to 2.5° C. and TBAF (0.01 M in THF, 0.400 L, 0.004 mol) was added over 2 h. During addition of TBAF, the temperature of the reaction mixture increased to 65° C. The reaction mixture was cooled to 0° C., and after 2h, tetra-n-butylammonium hydrogen sulfate (0.171 kg, 0.503 mol) was added, followed by tert-butyl bromoacetate (0.987 kg, 5.064 mol). Sodium hydroxide (50% wt in water, 4.2 kg, 52.6 mol) was added over 2h while maintaining the temperature under 10° C. After 2h at 0−5° C., to the reaction mixture was added water (2.9 L) and methyl tert-butyl ether (6.0 L). The aq. phase was extracted one more time with methyl tert-butyl ether (6.0 L). The organic phases were combined and washed with 14% aq. NaCl (3×1.6 L). The organics were concentrated under vacuum to afford the title compound as an oil (1.150 kg, 94.5%) which was used in the subsequent stage without additional purification. 1H NMR (500 MHz, CDCl3) δ ppm 5.86-5.74 (m, 1H), 5.59 (d, J=17.5 Hz, 1H), 5.56 (d, J=10.9 Hz, 1H), 4.37-4.30 (m, 1H), 4.11 (d, J=16.5 Hz, 1H), 4.06 (d, J=16.4 Hz, 1H), 1.40 (s, 9H); 13C NMR (125 MHz, CDCl3) δ ppm 168.51, 128.49 (d, J=1.7 Hz), 123.86, 123.71 (q, J=281.8 Hz), 82.22, 78.67 (q, J=31.5 Hz), 66.60, 28.02.

Workup

  1. temperaturethe temperature of the reaction mixture increased to 65° C
  2. temperatureThe reaction mixture was cooled to 0° C.
  3. temperaturewhile maintaining the temperature under 10° C
  4. extractionThe aq. phase was extracted one more time with methyl tert-butyl ether (6.0 L)
  5. washwashed with 14% aq. NaCl (3×1.6 L)
  6. concentrationThe organics were concentrated under vacuum

Sources & evidence

ORD record
ord-2f0c4c9145ff4b5dae85a0379bcbefbc
Source dataset
uspto-grants-2015_01
Patent number
US08940734B2

Reaction notes

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