Beruflich Dokumente
Kultur Dokumente
Volume 37.Number 2
15 April ((2011))
Synthesis and Identification of Some New Isoxazolidine compounds by 1,3Dipolar Cycloaddition Reaction of Nitrones and Olefin
Faeza A. Almashal
Department of Chemistry. College of Education
University of Basrah. Basrah-Iraq
ISSN 1817 2695
(Received 16 February 2011; Accepted 30 March 2011)
Abstract:
The 1,3-dipolar cycloaddition reaction of different nitrones(a,b and c) with N-(p-acetyl phenyl)
maleimide under reflux condition proceed isoxazolidines (d,e and f) in good yields . The reaction
mixture was followed by TLC.The yields of products following recrystallization from hexane were be
in the order of 42%-65%.mp., IR,mass-spectra were used for identification of these compounds.
Key Words: Isoxazolidine, Nitrones, 1,3-Dipolar, Cycloaddition.
Introduction:
The nitrone-olefin 1,3-dipolar cycloaddition
is a powerful reaction in that it can create as
many as three new contiguous stereogenic
centers in a single step. Based on an evaluation
of the nitrone cycloaddition[1]. Nitrones are
important synthetic intermediates that have been
used extensively in organic chemistry[28].Some nitrones have been used for the
trapping and identifcation of free radicals[8],
particularly in biological studies [5]. Various
synthetic approaches for the synthesis of
nitrones have been reported by several groups
[919].The most general approach for the
.
Experimental
Melting points were determined with an
electronthermal digital point apparatus type
GallenKamp. IR spectra were obtained using
Shimdzu FT-IR84005 spectrophotometer at
science college . All the spectra were recoreded
as KBr discs.The mass spectra were obtained by
using a Helwett Packard University of Cairo,
Faculty of science, Micro Analytical center TLC
is performed on silica gel 60 F254 sheet layer
(Merck).The materials from Merk , Ridel and
Fluka ) companies.
General Procedure
Nitrones[8]
For
Preparation
of
128
Synthesis
of
N-(p-acetyl
phenyl)
maleimide[25]:
Maleamic acid 4g(0.02mole) was heated on
steam bath in 8.5ml(0.0898mole) of acetic
anhydride
in
the
presence
of
0.82gm(0.0099mole) sodium acetate. Acetic
anhydride was hydrolyzed with iced water and
the reaction mixture was left for 1 hr. at room
temperature. The crystalline product was
filtered, washed 3 times with 25ml cooled
distilled water then with petrolium ether,
recrystallized from cyclohexane to get N-(pacetyl phenyl) maleimides 45% with melting
point (151-153)oC.
Synthesis of:
2-phenyl -5-(p-acetyl phenyl)-3-(4-chloro
phenyl) -4,6dioxo-2,3,3a,4,6,6a
hexahydropyrrolo[3,4-d] isoxazoles(d).
M.p C 0
Rf
Solvent
Recry.
156-157
0.4
Ethanol
115-116
0.63
Ethanol
190-191
0.61
Ethanol
225-226
0.54
Hexane
184-185
0.45
Hexane
250-251
0.65
Hexane
Eluents
Methanol:Toluene
3:7
Methanol:Toluene
3:7
Methanol:Toluene
3:7
Methanol:Toluene
3:7
Methanol:Toluene
3:7
Methanol:Toluene
3:7
Yield
55.6%
42%
46%
65%
51%
54%
129
Almashal
X = - Cl ,- OCH3 , -NO2
Scheme 1:1,3-Dipolar cycloaddition reaction of nitones to olefin
Infrared Spectra
The IR Spectra of the studied prepared
compounds as KBr discs and most of their
representative spectra are shown in Table 2 .
The IR-spectra of the nitrones (a,b and c)
showed the strong absorption bands at 1050,
1072 and 1085 cm-1 that are characteristic of the
(NO) stretching, the spectrum showed weak
bands due to the (C=N) stretching vibration at
1600, 1610 and 1605 cm-1, while the IR spectra
of isoxazolidine compounds (d, e and f) showed
Mass spectra
All
the
spectra
of
isoxazolidines
compounds(d,e
and
f)
show
similar
fragmentations pattern. . All the compounds
exhibit parent peaks, and the base peaks of the
Com.
C=CAr.Str
C=NStr.
C-N Str.
C-OStr.
N-O Str.
C=O Str.
1440-1490
1600(w)
1140(w)
1065(s)
1430-1540
1610(w)
1288(s)
1165(s)
1450-1530
1605(w)
1170(w)
1080(m)
1455-1480
1325(m)
1232(w)
1062(s)
1720(s)
1440-1485
1329(m)
1225(w)
1069(m)
1721(s)
1392-1490
1295(m)
1135(m)
1030(m)
1725(s)
symb.
m/z
Parent ion
M+
231
RC
O+
phN+
ph+
phN+CR
139
91
77
215
446
442
227
135
91
77
215
457
242
150
91
77
215
214
210
225
131
Almashal
132
133
Almashal
134
135
Almashal
Conclusion:
1)This study is concerned with synthesis of
isoxazolidine compounds and consists of three
stages:
a.Synthesis of nitrones
b.Synthesis of N-(p-acetyl phenyl) maleimide.
c.Dipolar cycloaddition reactions
2) By comparing the IR- spectra of nitrones (a-c)
with that of isoxazolidine compounds (d-f), we
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136
-31
/
/ -
. 42%-65%
.
137