Diethyl Malonate → Diethyl (ethoxymethylene)malonate

HRID 372407Notes

Reaction equation

HRID 372407 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[CH:12]([O-])([O-])[O:13][CH2:14][CH3:15].C(OC(=O)C)(=O)C.CC(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O.C(OC=C(C([O-])=O)C(OCC)=O)C>[Cl-].[Zn+2].[Cl-].CCOCC>[CH2:14]([O:13][CH:12]=[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])[CH3:15]

Participants

8

Reactant 5

HCID 7761Diethyl Malonate3×HCID 7918Acetic Anhydride2×HCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl esterHCID 53630039Ethylorthoformate2×HCID 858292113-Ethoxy-2-ethoxycarbonylprop-2-enoate

Product 1

HCID 6871Diethyl (ethoxymethylene)malonateYield 85%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 3283Diethyl EtherSolvent

Procedure

A mixture of diethyl malonate (160 g., 1.0 mole), ethyl ortho-formate (148 g., 1.0 mole), acetic anhydride solvent (204 g., 2 moles) and anhydrous zinc chloride catalyst (0.5 g) was heated in an oil bath for 6.5 hr (temperature of contents 104°-113° C). The mixture was then distilled through a short column during 3.5 hr, raising the pot temperature to 124°and yielding 120 ml of distillate. The residue was treated with additional ethyl orthoformate (148 g., 1.0 mole) and acetic and acetic anhydride (204 g., 2.0 moles) and distillation was continued for 3 hr to yield 160 ml of distillate (pot temperature 120°-130°). After standing at 25° for 18 hr the residue was diluted with 250 ml of ether and washed thoroughly with water. The combined extracts were dried over magnesium sulfate and distilled to yield a forerun (26 g.) containing principally diethyl malonate and 156 g. (72%) of ethyl ethoxymethylenemalonate, b.p. 109°-111° (0.9mm) (85% yield based on unrecovered diethyl malonate); NMR (CDCl3): δ 7.62 (s,l,=CH), 4.22 (q. J = 7Hz, 2, CH2), 4.19 (q, J = 7 Hz, 4, CH2), 1.37 (t, J = 7 Hz, 3, CH3), 1.30 (t, J = 7 Hz, 6, CH3).

Workup

  1. temperaturewas heated in an oil bath for 6.5 hr (temperature of contents 104°-113° C)
  2. distillationThe mixture was then distilled through a short column during 3.5 hr
  3. temperatureraising the pot temperature to 124°and
  4. customyielding 120 ml of distillate
  5. customto yield 160 ml of distillate (pot temperature 120°-130°)
  6. waitAfter standing at 25° for 18 hr
  7. washwashed thoroughly with water
  8. dry with materialThe combined extracts were dried over magnesium sulfate
  9. distillationdistilled
  10. customto yield a forerun (26 g.)

Sources & evidence

ORD record
ord-41d8e57bfdc645ac987801b040d8ca60
Source dataset
uspto-grants-1978_05
Patent number
US04091040

Reaction notes

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