Derivatives of N,N'-bis[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]ethanediamide

John N. Low, Bruce F. Milne, Jennifer-Nicola Ross, James L. Wardell

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3 Citations (Scopus)


Compound, [(HOCH2)3CNHC(O)]2 (1), obtained from (HOCH2)3CNH2 and EtOC(O)C(O)OEt, reacts with aryl aldehydes, ArCHO, to give the symmetric bis-alkylidene derivatives, N,N'-bis(2-Ar-5-ROCH 2-1,3-dioxan-5-yl)ethanediamides 3 (Ar = Ph, p-MeC6H4 or p-MeOC6H4, R = H). A similar reaction with Me2CO produced N'-bis(2,2-dimethyl-5-hydroxymethyl-1,3-dioxan-5-yl)ethanediamide (2). While three stereoisomers, (Z,Z)-, (Z,E)- and (E,E)-3 (Ar = Ph, R = H), were formed from 1 and PhCHO, only (Z,Z)-3 (Ar = p-MeC6H4 or p-MeOC6H4, R = H) was isolated from ArCHO (Ar = p-MeC6H4 or p-MeOC6H4) [the Z conformations in the solid state and in solution have equatorial-aryl, equatorial-HOCH2 and axial-amido groups: E forms have equatorial-aryl, equatorial-amido and axial-HOCH2 groups]. A 1:1 mixture of (Z,Z)-:(E,E)-3 (Ar = Ph, R = H) co-crystallises. Molecular mechanics calculations have been carried out on the conformation energies of (Z,Z)-and (E,E)-3 (Ar = Ph, R = H) and 1 and support the crystallographic and spectral findings. The stereoisomer, (Z,Z)-3 (Ar = Ph, R = H), is more reactive in alkylation reactions than the (E,E)-form: only (Z,Z)-3 (Ar = Ph, R = Ph3SnCH2) was isolated from the reaction of a mixture of (Z,Z)- and (E,E)-3 (Ar = Ph, R = H) with Ph3SnCH2I. From the reaction of excess allyl bromide with a 1:1 mixture of (Z,Z)- and (E,E)-3 (Ar = Ph, R = H), a 4:3 mixture of (Z,Z)- and (E,E)-3 (Ar = Ph, R = H2C=CHCH2) was isolated. Oxymercuriation of (Z,Z)-3 (Ar = Ph, R = H2C=CHCH2) with Hg(OAc)2 in MeOH, followed by anion exchange using NaCl, produced the single stereoisomer, {N-(Z)-[[(R²)-5-(3-chloromercuri-2-methoxypropyl)oxymethyl]-2-phenyl-1,3 -dioxan-5-yl]}{N'-(Z)-[[(S²)-5-(3-chloromercuri-2-methoxypropyl)oxymethyl]-2-phenyl-1,3-dioxan -5-yl]}ethanediamide (4), characterised by X-ray crystallography.
Original languageEnglish
JournalJournal of the Brazilian Chemical Society
Issue number2
Publication statusPublished - 25 Jun 2002

Bibliographical note


The authors thank Professor George Ferguson, University of Guelph, Canada for the X-ray data collection. JLW thanks CPNq for support as a visiting professor at UFRJ.

Data Availability Statement

Supplementary X-ray data for 4 are available from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033) on request, quoting the deposition number CCDC 153008.


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