Tributylamine → Diethyl(1-chloropropylidene)propanedioate

HRID 662012Notes

Reaction equation

HRID 662012 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>>[CH2:9]([O:8][C:6](=[O:7])[C:5](=[C:1]([Cl:18])[CH2:2][CH3:3])[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH3:10]

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 evaporated 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 evaporated to dryness to afford 6.81 g of a brown oil. The product was purified by flash chomatography 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. customThe mixture was evaporated 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. customevaporated to dryness

Sources & evidence

ORD record
ord-db070a2fbf3747d68986dac6c10f9351
Source dataset
uspto-grants-2011_12
Patent number
US08084449B2

Reaction notes

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