HomeMCPWorkbenchSkills
HomeWorkbenchNotificationsMe
llms.txt · MCP GuidePrivacy Policy · Terms of Service · Supportv1.8.0
  1. Home
  2. /Reaction

Dimethyl (2-oxopropyl)phosphonate → methyl(3E)-2,2-dimethyl-5-oxohex-3-enoate

HRID 410485
Notes
Print preview

Reaction equation

HRID 410485 reaction equation
[O:1]=[C:2]([CH3:10])[CH2:3]P(=O)(OC)OC.CC(C)([O-])C.[K+].[CH3:17][C:18]([CH3:25])([CH:23]=O)[C:19]([O:21][CH3:22])=[O:20]>O1CCCC1>[CH3:17][C:18]([CH3:25])(/[CH:23]=[CH:3]/[C:2](=[O:1])[CH3:10])[C:19]([O:21][CH3:22])=[O:20]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 77872Dimethyl (2-oxopropyl)phosphonateHCID 11137194Methyl 2,2-dimethyl-3-oxopropanoateHCID 23665647Potassium tert-butoxide

Product 1

HCID 86658242methyl(3E)-2,2-dimethyl-5-oxohex-3-enoateYield 47%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of dimethyl (2-oxopropyl)phosphonate (4.09 mL, 30 mmol) in tetrahydrofuran (200 mL) at 0° C. was added potassium tert-butoxide (3.22 g, 28.7 mmol). After 15 minutes, the reaction flask was moved to a 20° C. water bath and then a solution of methyl 2,2-dimethyl-3-oxopropanoate (3.39 g, 26 mmol) in tetrahydrofuran (10 mL) was added. After 20 hours, the opaque reaction mixture was partitioned between diethyl ether (100 mL) and water (100 mL). The layers were separated and the aqueous layer was extracted with diethyl ether (1×100 mL, 1×50 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution and brine, dried over sodium sulfate, filtered, and concentrated. The residue was purified by silica gel flash column chromatography (0-4% methanol/dichloromethane gradient) to afford methyl (3E)-2,2-dimethyl-5-oxohex-3-enoate (2.21 g, 12.21 mmol, 47% yield) as a light yellow oil. 1H NMR (500 MHz, CDCl3) δ 6.95 (d, J=16.3, 1H), 6.09 (d, J=16.3, 1H), 3.71 (s, 3H), 2.29 (s, 3H), 1.37 (d, J=2.3, 614).

Workup

  1. customwas moved to a 20° C.
  2. waitAfter 20 hours
  3. customthe opaque reaction mixture
  4. customwas partitioned between diethyl ether (100 mL) and water (100 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with diethyl ether (1×100 mL, 1×50 mL)
  7. washThe combined organic layers were washed with saturated aqueous sodium bicarbonate solution and brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by silica gel flash column chromatography (0-4% methanol/dichloromethane gradient)

Sources & evidence

ORD record
ord-a9bf348152134b789cf405e4a0d90f8b
Source dataset
uspto-grants-2014_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08759366B2

Reaction notes

Loading…

On this pageParticipantsProcedureWorkupSources & evidenceReaction notes