Tributylamine → Diethyl(1-chloropropylidene)propanedioate

HRID 564428Notes

Reaction equation

HRID 564428 reaction equation
[C:1]([CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=O)[CH2:2][CH3:3].P(Cl)(Cl)([Cl:18])=O.C(N(CCCC)CCCC)CCC>>[Cl:18][C:1](=[C:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH2:2][CH3:3]

Participants

4

Reactant 3

HCID 7622TributylamineHCID 24813Phosphorus oxychlorideHCID 307201,3-Diethyl 2-(1-oxopropyl)propanedioate

Product 1

HCID 57819400Diethyl(1-chloropropylidene)propanedioate

Conditions

Temperature
115 °C

Procedure

To diethyl propanoylpropanedioate (5.93 g, 27.4 mmol) was added phosphorus oxychloride (38 mL) and tributylamine (6.5 mL, 27.4 mmol) and the mixture was heated to 115° C. for 6 h then stirred at ambient temperature for 16 h. The mixture was concentrated to dryness and the residue added cautiously to aqueous hydrochloric acid (1M, 80 mL) and extracted twice with diethyl ether. The combined organic layers were washed with aqueous hydrochloric acid (1M), water, aqueous sodium hydroxide (1M) then brine, dried and concentrated to dryness to afford 6.81 g of a brown oil. The product was purified by flash chromatography on silica (250 mL) eluting with ethyl acetate/cyclohexane @ 1:10 to afford 3.21 g of the title compound. LC-MS m/z 235, 237 (M+H)+, 3.30 min (ret time).

Workup

  1. concentrationThe mixture was concentrated to dryness
  2. additionthe residue added cautiously to aqueous hydrochloric acid (1M, 80 mL)
  3. extractionextracted twice with diethyl ether
  4. washThe combined organic layers were washed with aqueous hydrochloric acid (1M), water, aqueous sodium hydroxide (1M)
  5. dry with materialbrine, dried
  6. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-0a154748d36b4f7fa7b543cd3654312c
Source dataset
uspto-grants-2011_11
Patent number
US08067408B2

Reaction notes

Loading…