Malonate Ion → Diisopropyl 2-(2,4,6-Triiodophenoxy)-1,3-propanedioate

HRID 1728295Notes

Reaction equation

HRID 1728295 reaction equation
[I:1][C:2]1[CH:19]=[C:18]([I:20])[CH:17]=[C:16]([I:21])[C:3]=1[O:4][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])C(OCC)=O.[C:22]([O-])(=O)[CH2:23][C:24]([O-])=O.I[C:30]1C=C(I)C=C(I)C=1O.[C:39](=[O:42])([O-:41])[O-].[K+].[K+]>CCOCC.CN(C)C=O.C(OCC)(=O)C>[I:21][C:16]1[CH:17]=[C:18]([I:20])[CH:19]=[C:2]([I:1])[C:3]=1[O:4][CH:5]([C:11]([O:13][CH:14]([CH3:15])[CH3:30])=[O:12])[C:39]([O:41][CH:23]([CH3:24])[CH3:22])=[O:42]

Participants

8

Reactant 4

HCID 9084Malonate IonHCID 11430Potassium CarbonateHCID 118622,4,6-TriiodophenolHCID 15343336Diethyl 2-(2,4,6-Triiodophenoxy)-1,3-propanedioate

Product 1

HCID 15343337Diisopropyl 2-(2,4,6-Triiodophenoxy)-1,3-propanedioate

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A stirred solution of 18.8 g (0.1 mol) of diisopropyl malonate in 100 ml carbon tetrachloride was cooled in an ice bath and 15.8 g (0.1 mol) bromine was added dropwise over a 90 minute period. The ice bath was removed and the reaction stirred at room temperature for 20 hours. The reaction solution was concentrated in vacuo and the resulting residue distilled to yield 16.1 g (76%) of the bromomalonate I [H. P. Gallus and A. K. Macbeth, J. Chem. Soc., 1937, 1810-12] as a clear colorless liquid; Bp 51°-2° C./0.1 mm Hg. CI/MS: MH+ 267. 1H-NMR (300 MHZ) spectral data was consistent with the desired structure. Using the same procedure as for 2-(2,4,6-triiodophenoxy)-1,3-propanedioic acid, diethyl ester, but substituting methylene chloride for ethyl acetate in the aqueous extraction, 2-(2,4,6-triiodophenoxy)-1,3-propanedioic acid, diisopropyl ester was prepared from 8.6 g (0.03 mol) of malonate I, 107 g (0.03 mol) of 2,4,6-triiodophenol, 4.5 g (0.03 mol) of milled anhydrous potassium carbonate and 30 ml of dimethylformamide in 69% yield as a tan oil; bp>65° C./0.65 mm Hg after chromatography (hexanes to 5% ether in hexanes). Title Compound: 1H (300 MHz) and 13C (75 MHz) NMR spectra were consistent with the desired structure. FAB/MS: MH+ 659. Calculated for C15H17I3O5 : C, 27.38 H, 2.60; I, 57.86. Found: C, 27.45; H, 2.56; I, 57.82.

Workup

  1. extractionin the aqueous extraction, 2-(2,4,6-triiodophenoxy)-1,3-propanedioic acid, diisopropyl ester

Sources & evidence

ORD record
ord-925cd6cae1ab4ec5aaa0f01d6db924c9
Source dataset
uspto-grants-1994_07
Patent number
US05326553

Reaction notes

Loading…