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Ring Transformation of Heterocycles
Adel M. Awadallah
Chemistry Department, Faculty of Science, Islamic University of Gaza, P. O. Box108,
Gaza, Palestine; Tel. +970-8-2823311, Fax: +970-8-2823310, e-mail: [email protected]
Ring Contraction
N
NN
N
O
CH3CH3N
O
CH3CH3Nlight
-N2
Quast et al 1975
• a) Transformation of 4-amino-4,5-oxadiazoles into the aromatic 1,3,4-oxadiazoles.
• Acylation of 4-amino-4,5-dihydro-1,2,4-oxadiazoles 1 in refluxing toluene or treatment of the acyl derivatives of these compounds 2 with trifluoroacetic anhydride brings up ring transformation to the aromatic 1,3,4-oxadiazoles 3 [1].
N
ON
Ar R"
R'
NH2
N
ON
Ar R"
R'
NH
X
O
O
NN
Ar XXCOCl (CF3CO)2O
r.t.
1 23
X = H, CH3, Ph, CH2Cl,
• Similarly, 4-amino-4,5-dihydro-1,2,4-oxadiazoles 4 are transformed into the corresponding 2-arylamino-1,3,4-oxadiazoles (6, X = O) or thiadiazoles (6, X = S) via reaction with phenylisocyanate or phenylisothiocyanate, followed by brief treatment of the resulting adducts 5 with trifluoroacetic anhydride at ambient temperature [2].
N
ON
Ar R"
R'
NH2
N
ON
Ar R"
R'
NH
NHPh
X
X
NN
Ar NHPh
C4
(CF3CO)2O
r.t.
PhNCX
X = O, S
4
5
6
• b) Ring contraction of 1,2,3,4-tetrahydro-1,2,4,5-tetrazines into 1H-1,2,4-triazoles.
• The reaction of nitrile oxides 7 with methylhydrazones 8 in chloroform was found to constitute a convenient synthetic route to the novel 4,5-dihydro-6H-1,2,4,5-oxatriazines 9 [3].
Cl
OHN
R
R"
R'NN
H
CH3 N NH
ON
RR'
R"
CH3
Et3N+CHCl3
7 89
• Risitano and coworkers obtained triazoles 10 directly from the appropriate monomethylhydrazones of aryl aldehydes in refluxing ether for 2 hours [4].
Cl
OHN
R
H
R'NN
H
CH3
N N
OH
N
RR'
H
CH3
N N
NR R'
CH3
+ether
reflux
10
• 1,2,3,4-tetrahydro-1,2,4,5-tetrazines 9 derived from methylhydrazones of aryl aldehydes underwent ring contaction, via elimination of H2O, to yield the respective 1H-1,2,4-triazoles 10. This transformation was envisaged to proceed via the ring-opened (E)-hydrazonoximes which then suffered dehydrative cyclization. The process is acid-catalyzed and was thermally induced. Apparently, the driving force for this transformation was linked to the aromaticity of the triazole product [5].
•
N NH
ON
RR'
H
CH3
N N
OH
N
RR'
H
CH3
N N
NR R'
CH3
or ACOH
9 10
• c) Transformation of dihydrotriazoles into 1-Aryl-3-acetyl-5-methyl-1H-1,2,4-triazole
NN
NH
Ac R
R
ArNN
NAc R
R
Ar
CH3O
NN
NAc
Ar
OCH3
R
R
NN
NAc
Ar
CH3
NN
NAc
Ar
CH3 R
RO
(CH3CO)2O ..
..
..
....
+
..
+ +
11 12
13
• d) Ring Expansion 1,2,4-triazoles into 1,2,3,6-oxatriazine
• Oximic 1,2,4-triazole ligands 15 were prepared from the reaction of triazoles 1 with hydroxylamine hydrochloride at room temperature. At higher temperatures, the reaction afforded, however, the novel ring transformation product 4-amino-2-(4-chlorophenyl)-5-methyl-2H-1,2,3,6-oxatriazine 16. The reaction of the ligands 15 with
• nickel(II) and palladium(II) acetates in ethanol at room temperature yielded the respective square planar complexes 18. X-ray structure determination of one of these complexes revealed that metallation led to unexpected ring transformation of the triazole ligand. It is probable that such ring transformation generated the imidazole-N-oxide intermediate 17 which coordinated to Ni(II) ion, and the 4N-donor set comprises both imidazole nitrogen and arylhydrazone nitrogen. [7]
NN
NH
O
CH3
RR
ArN
NNH
N
CH3
RR
Ar
OHN O
N
N
CH3
NH2
Ar
N
NH
R
R
OCH3
N
NH
Ar
M
N
N N
N
N
RR
OCH3
N
N
RR
OCH3
N
Cl
Cl
NH2OH.HCl
NaOAc
reflux
M(OAc)2
ring transformation
14
15 16
17
18
N
NH
N
CH3
Ar
OH
NNN
Ar
N
OH
CH3
NH
NO
NNNH2
Ar
CH3
N
NN
NH2
Ar
CH3
O
- CH3-CH=CH2
M. Wt = (42)
M.Wt = 266
+-
M.Wt = 224
2a
3
7
8
NN
NH
N
CH3
RR
Ar
OHN
NH
R
R
OCH3
N
NH
Ar
M
N
N N
N
N
RR
OCH3
N
N
RR
OCH3
N
Cl
Cl
M(OAc)2
1517
18
• 3-Acetyl-1,2,4-triazole hydrazones (19) gave Square planar nickel(II) complexes (21) upon reaction with Ni(OAc)2 in EtOH at room temperature in a 2:1 mole ratio. [8]
NN
NH
N
CH3
RR
ArNH2
NH
NH
N
N
NH
Ar
R
R
CH3
Ni
N
N
N
N
NH
N
N
Ar
R
R
CH3
NH
N
N
Ar
R
R
CH3
Ni(OAc)2.4H2Oring transformation
(19) (20)
(21)
في • اللقاء إلىالقدسالشريف
فيكم • الله وبارك