Triethylamine → Dimethyl 2,2-dinitropropylmalonate

HRID 1578166

Reaction equation

HRID 1578166 reaction equation
C(N(CC)CC)C.[CH2:8]=[C:9]([C:14]([O:16][CH3:17])=[O:15])[C:10]([O:12][CH3:13])=[O:11].[N+:18]([CH:21]([N+:23]([O-:25])=[O:24])[CH3:22])([O-:20])=[O:19]>CCOCC>[N+:18]([C:21]([N+:23]([O-:25])=[O:24])([CH3:22])[CH2:8][CH:9]([C:14]([O:16][CH3:17])=[O:15])[C:10]([O:12][CH3:13])=[O:11])([O-:20])=[O:19]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 611501,1-DinitroethaneHCID 769061,3-Dimethyl 2-methylenepropanedioate

Product 1

HCID 12489466Dimethyl 2,2-dinitropropylmalonateYield 72%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Triethylamine was added dropwise to a solution of 1.4 g (0.010 mol) of dimethyl methylenemalonate and 1.6 g (0.0133 mol) of 1,1-dinitroethane in 15 ml of ether at 0°, until yellow coloration persisted in the solution. The solution was allowed to stand 1 hr at ambient temperature and was then washed with 10% sodium bicarbonate, 1 N hydrochloric acid and water. The solution was dried over sodium sulfate, and the solvent was removed under vacuum. Column chromatography on a 100 g column of silica gel (CCl4 --CH2Cl2) and recrystallization of the product (methylene chloride-hexane, -78°) gave 1.9 g (72%) of dimethyl 2,2-dinitropropylmalonate, a white crystalline solid, mp 44°: NMR (CDCl3) 3.75 (s, 6 H, CH3), 3.1-3.5 (m, 3 H, CHCH2) and 2.13 (s, 3 H, C--CH3); IR (neat) 1730 (C=O) and 1570 cm-1 (NO2).

Workup

  1. washwas then washed with 10% sodium bicarbonate, 1 N hydrochloric acid and water
  2. dry with materialThe solution was dried over sodium sulfate
  3. customthe solvent was removed under vacuum
  4. customColumn chromatography on a 100 g column of silica gel (CCl4 --CH2Cl2) and recrystallization of the product (methylene chloride-hexane, -78°)

Sources & evidence

ORD record
ord-09cd083f25e24043975f7ac7189b6240
Source dataset
uspto-grants-1981_09
Patent number
US04291171

Linked notes

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