Oxidation of bisimines to bisoxaziridines using buffered oxone

Article abstract of DOI:10.1080/10426500214125

N,N′-bisarylidenes are oxidized efficiently and rapidly to the stereoisomeric mixture of bisoxaziridines using buffered oxone.

Full text of DOI:10.1080/10426500214125

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Phosphorus, Sulfur, and Silicon and the Related
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Oxidation of Bisimines to Bisoxaziridines Using
Buffered Oxone
Mohammad A. Bigdeli a , Mir. M. Alavi Nikje a & Majid M. Heravi b
a Department of Chemistry , Teacher Training University , Tehran, Iran
b Department of Chemistry, School of Sciences , Azzahra University , Tehran, Iran
Published online: 27 Oct 2010.
To cite this article: Mohammad A. Bigdeli , Mir. M. Alavi Nikje & Majid M. Heravi (2002) Oxidation of Bisimines to
Bisoxaziridines Using Buffered Oxone, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:10, 2309-2314, DOI:
10.1080/10426500214125
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2309–2314
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DOI: 10.1080/10426500290106040
OXIDATION OF BISIMINES TO BISOXAZIRIDINES
USING BUFFERED OXONE
Mohammad A. Bigdeli,a Mir. M. Alavi Nikje,a
and Majid M. Heravib
Department of Chemistry, Teacher Training University, Tehran,
Irana and Department of Chemistry, School of Sciences, Azzahra
University, Tehran, Iranb
(Received November 22, 2001; accepted)
N,N 0-bisarylidenes are oxidized efficiently and rapidly to the stereoiso-
meric mixture of bisoxaziridines using buffered oxone.
Keywords: Bisimines; bisoxaziridines; buffered oxone; oxidation;
three-membered heterocycles
Oxaziridines, heterocyclic compounds containing oxygen, nitrogen and
carbon atoms in a three membered ring were first reported in the
midfifties.1 Oxaziridines have remarkably high configurational stabil-
ity at nitrogen and can exist in isolable cis and trans isomers.2,3 The
imine-peroxyacid(m-CPBA) reaction generally provide a good rout to
oxaziridines.4 6 Recently, a rapid and efficient synthesis of oxaziridines
and diarylnitrones using oxone is also reported.7
Because of intriguing stereochemical possibilities of bis-oxaziridines,
a facile synthesis of this heterocyclic system could interesting from
the synthetic as well as stereochemical point of view. In spite of these
significance, few method have been reported for the synthesis of bis-
oxaziridines in the literature.8,9 In this communication we wish to re-
port an efficient and facile method for the synthesis of bis-oxaziridines
using buffered oxone.
We are interested in the heterocyclic systems containing
13
nitrogen.10
As a part of a synthetic project, we were searching
an efficient method for the synthesis of dinitrones. Since oxaziridines
can be thermally isomerized to nitrones14 we reasoned that bis-
oxaziridines should thermally isomerize to dinitrones.
Address correspondence to M. M. Heravi, Department of Chemistry, School of Sci-
ences, Azzahra University, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
2309

2310
M. A. Bigdeli et al.
m-CPBA has been extensively used for the conversion of azomethines
to oxaziridines.9 Since this compound is not commercially available
any more, we tried to use a more accessible and inexpensive reagent
for oxidation of bisimines. Oxone in buffered aqueous acetone solution
is reported to give dimethyldioxirane(DMD) that can be isolated by
distillation.7,15
It is also reported that when acetonitrile is used as a solvent the
active oxidizing agent is peroxyimidic acid [MeC(OOH) NH]. Such a
species formed from the reaction of acetonitrile and hydrogen peroxide
has been demonstrated to be a useful reagent for the epoxidation of
alkenes.16 We investigated the reaction of bis-arylidenes with oxone and
KHCO3 in aqueous acetone or acetonitrile solution and found that the
products are bisoxaziridines. Ethylenediamine-N,N0-bis(3-arylidenes)
and 1,3-propanediamine-N,N0-bis(3-arylidenes) were oxidized to the
corresponding 2,20-(1,2-ethanediyl)bis(3-arylidene)oxaziridines and
2,20-(1,3-propanediyl)bis(3-arylidene)oxaziridines (Scheme 1).
SCHEME 1
It is noteworthy to mention that all the reactions should be con-
ducted in an ice bath, since increase of the reaction temperature above
20 C, decreases the yields of the reaction drastically, probably due to
hydrolysis of substrates to parent aldehydes and further oxidation.
Utility of excess (three- and fourfold) oxone affected neither the re-
action time nor the yields. The yields were also found to be essen-
tially the same when either acetone or acetonitrile were used as solvent
(Scheme 1). The conduction of those reactions in a solventless system
using dry or wet-alumina/oxone (so called supported reagent) in the

Bisoxaziridines
2311
presence of aprotic solvents such as hexane, dichloromethane, acetone
or acetonitrile showed only recovered starting materials after 5 h re-
flux. It is noteworthy that the stable isomers of imines and bisimines
are trans and trans-trans isomers respectively,20 so the products are
obtained by the oxidation of these isomers. The attacking process of
the oxidant (dimethyldioxirane or peroxyimidic acid) to the trans-trans
stereoisomers of bisimines caused the formation of the racemic and
meso mixtures of bisoxaziridines (Scheme 2). In our experiments the
1H NMR spectra of the obtained products from ethylenediamine-N,N0-
bis(3-arylidenes) showed two signals for all protons and the 13C NMR
indicated that these compounds are a mixture of two isomers and the
ratio of isomeric mixture is affected by substituents at the aromatic
rings and methylene groups in the parent diamines (Scheme 2).
SCHEME 2
For example 2,20-(1,2-ethanediyl)bis(3-phenyl)oxaziridine shows
a 75:25 and 2,20-(1,2-ethanediyl)bis[3-(4-methylphenyl)]oxaziridine

2312
M. A. Bigdeli et al.
shows a 50:50 mixture of two isomers but in the case of 1,3-
propanediamine-N,N0-bis(3-arylidenes) only one isomer is obtained.
Steric interactions of aromatic segments and limitation in free rota-
tion of carbon-nitrogen sigma bonds can be attributed to this phe-
nomenon. For 1,3-propanediamine-N,N0-bis(3-arylidenes) which have
three methylene groups between two nitrogen atoms, only one isomer is
obtained in the oxidation process due to free rotation of carbon-nitrogen
sigma bonds without any steric hinderances in the aromatic segments
(Scheme 2).
In conclusion, we report here a rapid, inexpensive and new
method for the synthesis of 2,20-(1,2-ethanediyl)- and 2,20-(1,3-
propanediyl)bis(3-arylidene)oxaziridines under mild conditions; yields
are high, reaction times are short, and working up is very simple.
EXPERIMENTAL
1H NMR and 13C NMR spectra were obtained using Bruker instru-
ment at 500 and 125 MHz with CDCl3 as solvent. Mass spectra were
recorded using a Shimadzu QP1100EX instrument. Elemental analysis
were performed on a Heraeus CHNO Rapid Analyzer instrument. Melt-
ing points were measured on a Stuart Scientific aparatus and are not
19
corrected. Bisaldimines were prepared by the literature methods.7,17
Ethylenediamine, 1,3-propanediamine, oxone, KHCO3, benzaldehydes
and solvents were obtained from Merck and were used without further
purification.
General Procedure
To a 1-lit flask equipped with a magnetic stirrer was added the appropri-
ate bisaldimines (5 mmol) in acetone or acetonitrile (31 ml) and KHCO3
(3.5 mol equiv. based on oxone) in distilled water (62 ml) at 0 C. Oxone
(10 mmol) was dissolved in distilled water (62 ml) and was poured onto
the vigorously stirred mixture. The reaction mixture was stirred for
8 min (acetone reaction), 20 min (acetonitrile reaction), cooled to 5 C,
and filtered. The filtered solid was washed with distilled water (2
50 ml), cooled petroleum ether (60–80) (2 25 ml), and crystalized from
appropriate solvents and identified.
2,2 0-(1,2-Ethanediyl)bis(3-phenyl)oxaziridine
Colorless crystals, recrystalized from EtOAc, mp 99–102 C, 1H NMR
(CDCl3) (Major, 75%) 3.16–3.20 (m, 2H), 3.43–3.50 (m, 2H), 4.66
(s, 2H, oxaziridine H), 7.36–7.47 (m, 10H); (Minor, 25%) 3.07–3.09

Bisoxaziridines
2313
(m, 2H), 3.45–3.60 (m, 2H), 4.67 (s, 2H, oxaziridine H), 7.36–7.47
(m, 10H); 13C NMR (CDCl3)
59.66, 59.95, 80.54, 81.25, 127.70,
127.68, 128.48, 128.53, 130.13, 130.18, 134.38, 134.46; MS m/z
268.
2,2 0-(1,2-Ethanediyl)bis[3-(4-methylphenyl)]oxaziridine
Colorless crystals, recrystalized from CH3OH, mp 111–114 C, 1H
NMR (CDCl3) (isomer 1, 50%) 2.38 (s, 6H), 3.05–3.07 (m, 2H), 3.41–
3.43 (m, 2H), 4.64 (s, 2H, oxaziridine H), 7.16–7.18 (d, 4H, j = 8.5 Hz),
7.28–7.30 (d, 4H, j = 8.5 Hz) (isomer 2, 50%) 2.37 (s, 6H), 3.15–3.18
(m, 2H), 3.34–3.38 (m, 2H), 4.63 (s, 2H, oxaziridine H), 7.21–7.23 (d,
4H, j = 8.5 Hz), 7.35–7.37 (d, 4H, j = 8.5 Hz) 13C NMR (CDCl3) 21.44,
21.48, 59.68, 59.95, 80.58, 81.29, 127.65, 127.70, 129.16, 129.23, 131.47,
131.56, 140.12, 140.19, MS m/z 296.
2,2 0-(1,2-Ethanediyl)bis[3-(4-methoxyphenyl)]oxaziridine
Colorless crystals, recrystalized from CH3OH, mp 132–134 C, 1H
NMR (CDCl3) (isomer 1, 50%) 3.04–3.05 (m, 2H), 3.34–3.39 (m, 2H),
3.80 (s, 6H), 4.59 (s, 2H, oxaziridine H), 6.85–6.87 (d, 4H, j = 8.5 Hz),
6.90–6.92 (d, 4H, j = 8.5 Hz); (isomer 2, 50%) 3.12–3.16 (m, 2H), 3.31–
3.34 (m, 2H), 3.81 (s, 6H), 4.58 (s, 2H, oxaziridine H), 7.28–7.30 (d,
4H, j = 8.5 Hz), 7.36–7.38 (d, 4H, j = 8.5 Hz); 13C NMR (CDCl3) 55.30,
55.36, 59.60, 59.88, 80.43, 80.16, 113.80, 113.83, 126.42, 126.50, 129.06,
129.08, 161.09, 161.14; MS m/z 328.
2,2 0-(1,3-Propanediyl)bis(3-phenyl)oxaziridine
1
Colorless crystals, recrystalized from ethylacetate, mp 40–43 C, H
NMR (CDCl3): 2.14–2.18 (m, 2H), 2.61–2.70 (m, 2H), 3.20–3.31 (m,
2H), 4.50 (s, 2H, oxaziridine H), 7.30–7.4 (m, 10H); 13C NMR (CDCl3):
26.81, 59.50, 80.54, 127.70, 128.48, 130.13, 134.3; MS m/z 282; CHN:
calcd for C17H18 N2O2: C 73.34, H 6.38, N 9.92; found: C 73.50, H 6.42,
N 9.90.
2,2 0-(1,3-Propanediyl)bis[3-(4-methylphenyl)]oxaziridine
Colorless crystals, recrystalized from methanol, mp 67–70 C, 1H
NMR (CDCl3): 2.15–2.19 (m, 2H), 2.30 (s, 6H), 2.74–2.79 (m, 2H),
3.34–3.39 (m, 2H), 4.53 (s, 2H, oxaziridine H), 7.18–7.20 (d, 4H,
j = 8.5 Hz), 7.29–7.31 (d, 4H, j = 8.5 Hz); 13C NMR (CDCl3) 21.40,
26.80, 59.59, 80.56, 127.54, 129.23, 131.70, 140.15; MS m/z 310; CHN:
calcd for C19H22N2O2: C 73.55, H 7.10, N 9.03; found: C 73.51, H 7.12,
N 9.10.

2314
M. A. Bigdeli et al.
2,2 0-(1,3-Propanediyl)bis[3-(4-methoxyphenyl)]-
oxaziridine
Colorless crystals, recrystalized from methanol, mp 107–110 C,
1H NMR (CDCl3): 2.14–2.18 (m, 2H), 2.72–2.77 (m, 2H), 3.32–3.37
(m, 2H), 3.81 (s, 6H), 4.51 (s, 2H, oxaziridine H), 6.88–6.95 (d, 4H,
j = 8.5 Hz), 7.32–7.48 (d, 4H, j = 8.5 Hz); 13C NMR (CDCl3) 26.85,
55.36, 59.55, 80.41, 113.98, 126.71, 129.00, 161.11; MS m/z 342; CHN:
calcd for C19H22N2O4: C66.67, H 6.43, N 8.19; found: C 66.70, H 6.40,
N 8.21.
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