[3,2]-Sigmatropic rearrangement of acyloxy nitronic acids into geminal acyloxy nitroso compounds

Article abstract of DOI:10.1023/A:1022593300268

Acylation of secondary nitroalkanes is accompanied by [3,2]-sigmatropic rearrangement of acyloxy nitronic acids into geminal acyloxy nitroso compounds which are formed in preparative yields.

Full text of DOI:10.1023/A:1022593300268

Russian Journal of Organic Chemistry, Vol. 38, No. 10, 2002, pp. 1431 1433. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 10, 2002,
pp. 1484 1486.
Original Russian Text Copyright
2002 by Daineko, Proskurnina, Skornyakov, Trofimov, Zefirov.
[
3,2]-Sigmatropic Rearrangement of Acyloxy Nitronic Acids
*
into Geminal Acyloxy Nitroso Compounds
1
1
1
V. I. Daineko , M. V. Proskurnina , Yu. V. Skornyakov ,
2
1
B. A. Trofimov , and N. S. Zefirov
1
Lomonosov Moscow State University, Vorob’evy gory, Moscow, 119899 Russia
2
Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Received January 8, 2002
Abstract Acylation of secondary nitroalkanes is accompanied by [3,2]-sigmatropic rearrangement of acyloxy
nitronic acids into geminal acyloxy nitroso compounds which are formed in preparative yields.
Since 1975, N.S. Zefirov and S.S. Trach perform
[8, 10],*** (1b) [11], and (1c) [12] (Scheme 1). The
goal of the present study was to analyze the process
described by Eqs. (2a) and (2b) (Scheme 2). This
process is accompanied by change in the degree of
oxidation of nitrogen by two units, i.e., by the trans-
systematic studies aimed at developing a formally
logical approach to description of organic reactions.
The goals of these studies are (1) creation of a hier-
archical classification of organic reactions and a strict
mathematical model for their description [1],
2) search for unknown reactions and reaction types
2, 7, 8], (3) description of transformations of hetero-
cycles [4], (4) development of a methodology for non-
empirical computer synthesis [5], and (5) computer-
aided study of mechanisms of organic reactions [9].
+
1
+3
formation N
N
(which is hardly probable) or
+
3
+5
(
[
N
N , which is more probable for a branched
skeleton, especially when methyl groups are present
and when the process is directed from the right to
the left. This is illustrated by Eq. (2b) which describes
Scheme 1.
Let us consider a symbolic representation of a five-
center [3,2]-sigmatropic rearrangement [Eq. (1) in
*
*
Scheme 1] [2, 7]. Design of unknown reactions
on the basis of this symbolic equation implies com-
binatorial replacement of common (dark circles) and
specific reaction centers by symbols of the corre-
sponding elements [1, 3, 6]. At present, a fairly large
number of reactions are known, which conform to
Eq. (1). Examples are processes described by Eq. (1a)
(
1)
(
1a)
_
___________
*
This study was financially supported by the Russian Founda-
(1b)
tion for Basic Research (project nos. 99-03-35055 and
0
1-03-33085).
*
*
Analysis of monocyclic five-center processes with a single
specific center (additional constraints: bond order variation
equal to 1 and the absence of triple bond or allene frag-
ment in the five-membered ring) with the use of SIMBEQ
program [6] gives 21 symbolic equations, but only two of
them refer to sigmatropic rearrangements. Strictly speaking
(
1c)
_
*
___________
**
It should be noted that the sulfenate sulfoxide rearrange-
ment was discovered almost simultaneously by four dif-
ferent research teams [8, 10] on the basis of different
starting points. Our considerations [8] are based com-
pletely on the formally logical approach (see Scheme 1).
[
3], the process should be regarded as [3,2 -3,2 ]-sigma-
tropic rearrangement (here, the Greek letters denote the
position of specific reaction centers in the initial and final
structures).
1
070-4280/02/3810-1431$27.00 2002 MAIK Nauka/Interperiodica

1
432
DAINEKO et al.
the rearrangement from acyloxy nitro compounds to
spectrometer (300 MHz) in CDCl . The mass spectra
3
-
acyloxy nitroso compounds.
(70 eV) were run on an HP-5990 (HP-5972) instru-
ment (emission current 1000 mA, vaporizer tempera-
ture 70 250 C).
Scheme 2.
2
-Acetoxy-2-nitrosopropane (I). 2-Nitropropane,
10 g (0.11 mol), was added over a period of 30 min
(
2a)
to a suspension of 12.32 g (0.11 mol) of potassium
tert-butoxide in 100 ml of dry diethyl ether under
stirring at 0 C. The mixture was stirred for 30 min at
0
C, and 11.22 g (0.11 mol) of acetic anhydride was
added over a period of 25 min (the solution turned
dark blue). The mixture was stirred for 2 h while
cooling and filtered, and the precipitate was washed
with diethyl ether on a filter until it became colorless.
The blue filtrate was evaporated on a rotary evaporator
without heating, and the residue was distilled under
reduced pressure to isolate 9.8 g (70%) of compound I
as an intensely blue oily substance, bp 60 63 C
(
2b)
Thus, in the first step of our study we tried to
effect acylation of secondary nitro compounds in the
aci form. Such transformation was reported in 1958
by White and Considine [13] for aryl-substituted nitro
compounds. In order to elucidate the scope of its
application, we examined the acylation of nitroalkanes
(60 mm). The product is stable at 10 C, and at room
temperature it undergoes complete dimerization in
1
2
(
4 h. IR spectrum, , cm : 1560, 1580 (N O); 1720
1
C O); 1760 (O C O); 2830 1880 (C H).
H
(Scheme 3).
NMR spectrum, , ppm: 1.37 s (6H, CH ); 2.19 s
3
(
(
(
3H, COCH ). UV spectrum (CH CN):
667 nm
Scheme 3.
3
3
max
N O). GC MS data: retention time 2.66 min; m/z
+
I , %): 101 (45) [M NO] ; 59 (100) [M NO
rel
+
CH2 C O] . The fragmentation pattern of compound
I was in a full agreement with published data for
2-acetoxy-2-nitrosopropane [13]. The reaction with
acetyl chloride as acylating agent was performed in
a similar way. Yield 73%.
1-Acetoxy-1-nitrosocyclohexane (II) was obtained
in a similar way from 11.2 g (0.1 mol) of potassium
tert-butoxide, 12.9 g (0.1 mol) of nitrocyclohexane,
and 10.2 g (0.1 mol) of acetic anhydride. Yield 12 g
I, R = Me; II, RR = (CH ) .
2
5
(70%), intensely blue oily substance, bp 50 53 C
(
0.5 mm); published data [14]: bp 62 78 C (0.3 mm).
In fact, the aci forms generated in situ from secon-
1
Compound II is stable at room temperature. H NMR
spectrum, , ppm: 2.20 s (3H, COCH ), 1.4 1.9 m
dary nitroalkanes (2-nitropropane and nitrocyclo-
hexane) are readily acylated with acetic or trifluoro-
acetic anhydride and acetyl chloride under mild
conditions (in diethyl ether). The reaction is accom-
panied by [3,2]-sigmatropic rearrangement of inter-
mediate acyloxy nitronic acids into geminal acyloxy
nitroso compounds. The latter were isolated in 70
3
(10H, cyclohexane). Mass spectrum, m/z (I , %): 141
rel
+
+
(10) [M NO] , 99 (100) [M NO CH C O] ,
2
+
8
1 (80) [M NO CH2 C O H O] .
2
1
-Nitroso-1-trifluoroacetoxycyclohexane (III).
The reaction of nitrocyclohexane with trifluoroacetic
anhydride was performed in a similar way. The mix-
7
5% yield.
ture was evacuated at 10 2 mm, 20 C. The residue
1
EXPERIMENTAL
The electron absorption spectra were measured on
a Specord M-40 spectrophotometer. The IR spectra
were obtained on a Specord 75IR instrument. The
was a dark blue oily substance. Yield 76%.
H
NMR spectrum, , ppm: 1.1 2.8 m (10H, cyclo-
hexane). Found, %: C 42.47; H 4.46; F 25.21; N 6.11.
C H F NO . Calculated, %: C 42.67; H 4.48;
F 25.31; N 6.22. Compound III completely decom-
poses in 24 h at 20 C.
8
10
3
3
1
H NMR spectra were recorded on a Bruker AC-300
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

[3,2]-SIGMATROPIC REARRANGEMENT OF ACYLOXY NITRONIC ACIDS
1433
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