Triazene derivatives of (1,x-)diazacycloalkanes. Part VI. 3-({5,5-Dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4, 4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines - Synthesis, characterization, and X-ray crystal structure

Keith Vaughan, Shasta Lee Moser, Reid Tingley, M. Brad Peori, Valerio Bertolasi

Research output: Contribution to journalArticleResearchpeer-review

1 Citation (Scopus)

Abstract

Reaction of a series of diazonium salts with a mixture of formaldehyde and 1,2-diamino-2-methylpropane affords the 3-({5,5-dimethyl-3-[2-aryl-1-diazenyl]- 1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines (1a-1f) in excellent yield. The products have been characterized by IR and NMR spectroscopic analysis, elemental analysis, and X-ray crystallography. The X-ray crystal structure of the p-methoxycarbonyl derivative (1c) establishes without question the connectivity of these novel molecules, which can be described as linear bicyclic oligomers with two imidazolidinyl groups linked together by a one-carbon spacer. This is indeed a rare molecular building block. The molecular structure is corroborated by 1H and 13C NMR data, which correlates with the previously published data of compounds of types 5 and 6 derived from 1,3-propanediamine. The triazene moieties in the crystal of 1c display significant π conjugation, which gives the N-N bond a significant degree of double-bond character. This in turn causes restricted rotation around the N-N bond, which leads to considerable broadening of signals in both the 1H and 13C NMR spectra. The molecular ion of the p-cyanophenyl derivative (1b) was observed using electrospray mass spectrometry (ES + Na). The mechanism of formation of molecules of type 1 is proposed to involve diazonium ion trapping of the previously unreported bisimidazolidinyl methane (13).

Original languageEnglish
Pages (from-to)1294-1300
Number of pages7
JournalCanadian Journal of Chemistry
Volume84
Issue number10
DOIs
Publication statusPublished - 1 Oct 2006
Externally publishedYes

Keywords

  • Bistriazene
  • Imidazolidine
  • NMR spectroscopy
  • Synthesis
  • Triazene
  • X-ray crystallography

Cite this

@article{2edac23e85e442e29e043a6ef4332856,
title = "Triazene derivatives of (1,x-)diazacycloalkanes. Part VI. 3-({5,5-Dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4, 4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines - Synthesis, characterization, and X-ray crystal structure",
abstract = "Reaction of a series of diazonium salts with a mixture of formaldehyde and 1,2-diamino-2-methylpropane affords the 3-({5,5-dimethyl-3-[2-aryl-1-diazenyl]- 1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines (1a-1f) in excellent yield. The products have been characterized by IR and NMR spectroscopic analysis, elemental analysis, and X-ray crystallography. The X-ray crystal structure of the p-methoxycarbonyl derivative (1c) establishes without question the connectivity of these novel molecules, which can be described as linear bicyclic oligomers with two imidazolidinyl groups linked together by a one-carbon spacer. This is indeed a rare molecular building block. The molecular structure is corroborated by 1H and 13C NMR data, which correlates with the previously published data of compounds of types 5 and 6 derived from 1,3-propanediamine. The triazene moieties in the crystal of 1c display significant π conjugation, which gives the N-N bond a significant degree of double-bond character. This in turn causes restricted rotation around the N-N bond, which leads to considerable broadening of signals in both the 1H and 13C NMR spectra. The molecular ion of the p-cyanophenyl derivative (1b) was observed using electrospray mass spectrometry (ES + Na). The mechanism of formation of molecules of type 1 is proposed to involve diazonium ion trapping of the previously unreported bisimidazolidinyl methane (13).",
keywords = "Bistriazene, Imidazolidine, NMR spectroscopy, Synthesis, Triazene, X-ray crystallography",
author = "Keith Vaughan and Moser, {Shasta Lee} and Reid Tingley and Peori, {M. Brad} and Valerio Bertolasi",
year = "2006",
month = "10",
day = "1",
doi = "10.1139/V06-091",
language = "English",
volume = "84",
pages = "1294--1300",
journal = "Canadian Journal of Chemistry",
issn = "0008-4042",
publisher = "NRC Research Press",
number = "10",

}

Triazene derivatives of (1,x-)diazacycloalkanes. Part VI. 3-({5,5-Dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4, 4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines - Synthesis, characterization, and X-ray crystal structure. / Vaughan, Keith; Moser, Shasta Lee; Tingley, Reid; Peori, M. Brad; Bertolasi, Valerio.

In: Canadian Journal of Chemistry, Vol. 84, No. 10, 01.10.2006, p. 1294-1300.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Triazene derivatives of (1,x-)diazacycloalkanes. Part VI. 3-({5,5-Dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4, 4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines - Synthesis, characterization, and X-ray crystal structure

AU - Vaughan, Keith

AU - Moser, Shasta Lee

AU - Tingley, Reid

AU - Peori, M. Brad

AU - Bertolasi, Valerio

PY - 2006/10/1

Y1 - 2006/10/1

N2 - Reaction of a series of diazonium salts with a mixture of formaldehyde and 1,2-diamino-2-methylpropane affords the 3-({5,5-dimethyl-3-[2-aryl-1-diazenyl]- 1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines (1a-1f) in excellent yield. The products have been characterized by IR and NMR spectroscopic analysis, elemental analysis, and X-ray crystallography. The X-ray crystal structure of the p-methoxycarbonyl derivative (1c) establishes without question the connectivity of these novel molecules, which can be described as linear bicyclic oligomers with two imidazolidinyl groups linked together by a one-carbon spacer. This is indeed a rare molecular building block. The molecular structure is corroborated by 1H and 13C NMR data, which correlates with the previously published data of compounds of types 5 and 6 derived from 1,3-propanediamine. The triazene moieties in the crystal of 1c display significant π conjugation, which gives the N-N bond a significant degree of double-bond character. This in turn causes restricted rotation around the N-N bond, which leads to considerable broadening of signals in both the 1H and 13C NMR spectra. The molecular ion of the p-cyanophenyl derivative (1b) was observed using electrospray mass spectrometry (ES + Na). The mechanism of formation of molecules of type 1 is proposed to involve diazonium ion trapping of the previously unreported bisimidazolidinyl methane (13).

AB - Reaction of a series of diazonium salts with a mixture of formaldehyde and 1,2-diamino-2-methylpropane affords the 3-({5,5-dimethyl-3-[2-aryl-1-diazenyl]- 1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines (1a-1f) in excellent yield. The products have been characterized by IR and NMR spectroscopic analysis, elemental analysis, and X-ray crystallography. The X-ray crystal structure of the p-methoxycarbonyl derivative (1c) establishes without question the connectivity of these novel molecules, which can be described as linear bicyclic oligomers with two imidazolidinyl groups linked together by a one-carbon spacer. This is indeed a rare molecular building block. The molecular structure is corroborated by 1H and 13C NMR data, which correlates with the previously published data of compounds of types 5 and 6 derived from 1,3-propanediamine. The triazene moieties in the crystal of 1c display significant π conjugation, which gives the N-N bond a significant degree of double-bond character. This in turn causes restricted rotation around the N-N bond, which leads to considerable broadening of signals in both the 1H and 13C NMR spectra. The molecular ion of the p-cyanophenyl derivative (1b) was observed using electrospray mass spectrometry (ES + Na). The mechanism of formation of molecules of type 1 is proposed to involve diazonium ion trapping of the previously unreported bisimidazolidinyl methane (13).

KW - Bistriazene

KW - Imidazolidine

KW - NMR spectroscopy

KW - Synthesis

KW - Triazene

KW - X-ray crystallography

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DO - 10.1139/V06-091

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