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 language | English |
|---|---|
| Pages (from-to) | 1294-1300 |
| Number of pages | 7 |
| Journal | Canadian Journal of Chemistry |
| Volume | 84 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - 1 Oct 2006 |
| Externally published | Yes |
Keywords
- Bistriazene
- Imidazolidine
- NMR spectroscopy
- Synthesis
- Triazene
- X-ray crystallography
Cite this
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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 journal › Article › Research › peer-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
UR - http://www.scopus.com/inward/record.url?scp=33847687691&partnerID=8YFLogxK
U2 - 10.1139/V06-091
DO - 10.1139/V06-091
M3 - Article
AN - SCOPUS:33847687691
VL - 84
SP - 1294
EP - 1300
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
SN - 0008-4042
IS - 10
ER -