Acetic Acid → HCID 20315748, compound

HRID 2419459Notes

Reaction equation

HRID 2419459 reaction equation
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].[C:8]1([C:14]#[C:15][C:16](OCC)=[O:17])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C(O)(=O)C>CCCCCC.O1CCCC1>[O:17]=[C:16]([C:15]#[C:14][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 12958Dimethyl methylphosphonateHCID 915162-Propynoic acid, 3-phenyl-, ethyl ester

Product 1

HCID 20315748HCID 20315748, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

N-Butyl-lithium (13.5 ml. of a 2.29 M solution in hexane) was added dropwise to a stirred solution of dimethyl methylphosphonate (3.84 g.) in anhydrous tetrahydrofuran (25 ml.) at -78° under argon. After 15 minutes, a solution of ethyl phenylpropiolate (2.5 g.) in anhydrous tetrahydrofuran (20 ml.) was added. The reaction mixture was stirred for 2 hours at -78° C., allowed to warm to ambient temperature and stirred for 18 hours, and adjusted to pH 5 by addition of glacial acetic acid. The tetrahydrofuran was evaporated at room temperature under reduced pressure and the residue was partitioned between water and diethyl ether. The diethyl ether layer was separated, washed with water and dried, and the solvent was evaporated. Chromatography of the crude product on silica gel MFC (75 g.)., eluting with diethyl ether/ethyl acetate (9:1), gave unreacted ethyl phenylpropiolate, and subsequent elution with diethyl ether/ethyl acetate (1:1), gave dimethyl 2-oxo-4-phenylbut-3-ynylphosphonate as an oil, RF = 0.28 (ethyl acetate). The n.m.r. spectrum in deuteriochloroform showed the following absorptions (δ values):

Workup

  1. temperatureto warm to ambient temperature
  2. stirringstirred for 18 hours
  3. customThe tetrahydrofuran was evaporated at room temperature under reduced pressure
  4. customthe residue was partitioned between water and diethyl ether
  5. customThe diethyl ether layer was separated
  6. washwashed with water
  7. customdried
  8. customthe solvent was evaporated
  9. wash, eluting with diethyl ether/ethyl acetate (9:1)
  10. customgave unreacted
  11. washethyl phenylpropiolate, and subsequent elution with diethyl ether/ethyl acetate (1:1)

Sources & evidence

ORD record
ord-010d7010544f49e39b00cac154f0086d
Source dataset
uspto-grants-1978_08
Patent number
US04105854

Reaction notes

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