Diethyl Malonate → HCID 54718684, compound

HRID 864659Notes

Reaction equation

HRID 864659 reaction equation
[H-].[Na+].C(=O)=O.CC(C)=O.[C:10]([O:18][CH2:19][CH3:20])(=[O:17])[CH2:11][C:12]([O:14]CC)=O.[N+:21]([C:24]1C=CC=[C:26]([CH:27](Cl)Cl)[C:25]=1O)([O-:23])=[O:22]>C(COC)OC.C(Cl)Cl>[OH:14][C:12]1[C:20]2[C:19](=[C:24]([N+:21]([O-:23])=[O:22])[CH:25]=[CH:26][CH:27]=2)[O:18][C:10](=[O:17])[CH:11]=1

Participants

7

Reactant 4

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 18522661Acetone cardiceHCID 67649808HCID 67649808, compound

Product 1

HCID 54718684HCID 54718684, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 80711,2-DimethoxyethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of NaH (6.94 g, 0.291 mole) in dimethoxyethane is cooled using dry ice/acetone cooling, treated dropwise with diethyl malonate (46.6 g, 0.29 mole), allowed to warm to 0° C., treated dropwise with a solution of 3-nitrosalicylyl chloride (19.5 g, 0.10 mole) in dimethoxyethane, allowed to warm to room temperature, stirred for 3 hours at room temperature, heated at 60° C. until reaction is complete by HPLC analysis, cooled to room temperature, poured onto a mixture of ice water and methylene chloride and stirred for about 0.5 hour. The phases are separated, the aqueous phase is acidified with 50% HCl to pH 5 and filtered. The filtercake is dispersed in acetic acid, heated and filtered. This filtercake is air-dried and 8.6 g is dispersed in dimethyl sulfoxide, heated at 100° C. for about 2 hours, cooled to room temperature, poured onto ice water and filtered. The solid is taken up in acetonitrile, filtered hot, cooled and filtered to give the title product, mp 242°-245° C., identified by IR, 1HNMR and mass spectral analyses.

Workup

  1. temperatureto warm to room temperature
  2. temperatureheated at 60° C. until reaction
  3. temperaturecooled to room temperature
  4. stirringstirred for about 0.5 hour
  5. customThe phases are separated
  6. filtrationfiltered
  7. additionThe filtercake is dispersed in acetic acid
  8. temperatureheated
  9. filtrationfiltered
  10. customThis filtercake is air-dried
  11. addition8.6 g is dispersed in dimethyl sulfoxide
  12. temperatureheated at 100° C. for about 2 hours
  13. temperaturecooled to room temperature
  14. additionpoured onto ice water
  15. filtrationfiltered
  16. filtrationfiltered hot
  17. temperaturecooled
  18. filtrationfiltered

Sources & evidence

ORD record
ord-bef3d956cbab4c8e88d771c360a551f2
Source dataset
uspto-grants-1996_10
Patent number
US05563280

Reaction notes

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