Oxidation of gem-chloronitroso- and vic-chloronitroso-alkanes and -cycloalkanes to respective chloronitro compounds by novel cetyltrimethylammonium hypochlorite reagent

Article abstract of DOI:10.1007/s12039-011-0090-7

Cetyltrimethylammonium hypochlorite (CTAHC) is prepared and used as an oxidizing agent for nitroso group to nitro group. The gem-chloronitroso and vic-chloronitroso compounds are prepared respectively from ketoximes and olefins by reacting with NOCl generated in situ from chlorotrimethylsilane (TMSC1 (l) and iso-amyl nitrite. CTAHC oxidizes gem-chloronitroso and vic-chloronitroso compounds to the corresponding chloronitro derivatives. While gem-chloronitro compounds are obtained in good yields, the vic-chloronitro derivatives are formed in moderate yields, because of the propensity of the vic-chloronitroso group to tautomerize to α-chlorooxime. The present method is simple and practical, particularly for the preparation of vic-chloronitro compounds, considering the fact that the known methods of their preparation are few and quite involved. Indian Academy of Sciences.

Full text of DOI:10.1007/s12039-011-0090-7

c
J. Chem. Sci. Vol. 123, No. 4, July 2011, pp. 433–441. ꢀ Indian Academy of Sciences.
Oxidation of gem-chloronitroso- and vic-chloronitroso-alkanes
and -cycloalkanes to respective chloronitro compounds by novel
cetyltrimethylammonium hypochlorite reagent†
ABDULKARIM H A MOHAMMEDa,b and GOPALPUR NAGENDRAPPAa,∗
aDepartment of Chemistry, Bangalore University, (Central College Campus), Bangalore 560 001, India
bUniversity of Sana’a, Sana’a, Yemen
e-mail: gnagendrappa@gmail.com
MS received 28 November 2010; revised 23 April 2011; accepted 3 May 2011
Abstract. Cetyltrimethylammonium hypochlorite (CTAHC) is prepared and used as an oxidizing agent for
nitroso group to nitro group. The gem-chloronitroso and vic-chloronitroso compounds are prepared respec-
tively from ketoximes and olefins by reacting with NOCl generated in situ from chlorotrimethylsilane (TMSCl)
and iso-amyl nitrite. CTAHC oxidizes gem-chloronitroso and vic-chloronitroso compounds to the correspond-
ing chloronitro derivatives. While gem-chloronitro compounds are obtained in good yields, the vic-chloronitro
derivatives are formed in moderate yields, because of the propensity of the vic-chloronitroso group to tau-
tomerize to α-chlorooxime. The present method is simple and practical, particularly for the preparation of
vic-chloronitro compounds, considering the fact that the known methods of their preparation are few and quite
involved.
Keywords. Cetyltrimethylammonium hypochlorite; oxidation; gem-chloronitroso compounds;
vic-chloronitroso compounds; gem-chloronitro compounds; vic-chloronitro compounds;
nitroso-to-nitro conversion; nitrosyl chloride; oxime.
1. Introduction
and N,N’-dichlorobis(2,4,6-trichlorophenyl)urea.17 Ni-
trosyl chloride18 and nitryl chloride12 are found to
be efficient reagents to convert oximes to gem-
chloronitroso compounds.
gem-Chloronitro-alkanes and -cycloalkanes are valu-
able starting compounds in organic synthesis. They
are used to prepare nitroalkanes and nitrocycloalka-
nes1 by reductive dechlorination,2 and find other use-
ful applications in organic synthetic procedures.3 They
are generally prepared by the oxidation of the corre-
sponding gem-chloronitroso compounds using oxidiz-
ing agents, such as ozone,4 oxone,5 chlorotriazines,2a
chloroperoxidases,6 peroxyacetic acid,2b trifluoroper-
oxyacetic acid,7 nitric acid,8 hydrogen peroxide,9 N-
bromosuccinimide,10 and sodium hypochlorite alone11
or with tetrabutylammonium hydrogen sulphate as
phase transfer catalyst in a biphasic system.2d Recently,
we have shown that nitryl chloride produced in situ
oxidizes the nitroso group to nitro group.12
vic-Chloronitro compounds exhibit a variety of bio-
logical activities.19 They are found to act as insecti-
cides,20 fungicides,21 bactericides,22 miticides,23 and her-
bicides.21b Vinylic nitroolefins, obtained by the elimi-
nation of HCl from vic-chloronitro compounds, have
been used as dienophiles in several synthetically useful
Diels–Alder reactions, and undergo Michael addition
with a variety of nucleophiles.1d, 24d, 25 In spite of their
many applications, to our knowledge, there are only two
methods of synthesis of vic-chloronitro compounds.
One is by a free radical addition of NO2Cl or N2O4-
chlorine mixture with olefins, especially in the gas
phase, which leads to a mixture of several nitration
products including the vic-chloronitro derivatives.24
The second one is the addition of nitrosyl chloride to
alkenes first to form vic-chloronitroso compounds, the
latter are then allowed to stand for several days with
excess nitrosyl chloride which slowly oxidizes them to
vic-chloronitro derivatives.26 Both these methods pose
problems of purification and give poor yields.
The required starting gem-chloronitroso compounds
are prepared by the chlorination of oximes using ele-
mental chlorine,13 t-butylhypochlorite as well as hy-
pochlorous acid,11,14 N-t-butyl-N-chlorocyanamide,15
hydrogen peroxide-hydrochlric acid,2b N-chlorourea,16
∗For correspondence
†Extracted from the Ph D Thesis of AHAM.
433

434
Abdulkarim H A Mohammed and Gopalpur Nagendrappa
OSiMe3
Cl
ON
Cl
Cl
SiMe3
ON
H
H
NOCl
NOCl
N
Cl
SiMe3
H
H
Scheme 1. Reaction of NOCl with vinylsilanes.
While NOCl reacts with oximes to produce Silica gel (Qualigens) used for column chromatography
gem-chloronitroso derivatives, it adds to alkenes (60–120 mesh size) was activated by heating to 110◦C
and cycloalkenes to give vic-chloronitroso com- before use.
pounds.18b, 27 We have shown earlier that NOCl, con-
Cyclopentanone, cyclohexanone, cycloheptanone,
veniently generated in situ by the reaction of amyl or cyclooctanone, cyclododecanone, norcamphor, and
iso-amyl nitrite with TMSCl under anhydrous condi- propiophenone were obtained from Aldrich Chemical
tions, brings about both these reactions in tandem in its Company. Acetophenone was obtained from SD Fine
reaction with vinylsilanes18a,b (scheme 1).
Chemicals. Dibenzyl ketone was prepared by the liter-
Since the methods employed for the oxidation of ature procedure.30a Hydroxylamine hydrochloride was
both gem- and vic-chloronitro compounds, especially of A.R. grade. The oximes were prepared following the
the latter ones, are beset with deficiencies, we thought known procedure.30b
that introducing more efficient alternative routes for
the preparation of chloronitrocycloalkanes and -alkanes heptene were prepared by dehydration of the cor-
would be useful. responding alcohols; (cyclopentanol and cyclohep-
Cyclopentene, cyclohexene, cycloheptene and 1-
We have developed cetyltrimethylammonium tanol were prepared by reducing cyclopentanone and
hypochlorite (CTAHC) as a novel oxidant for conver- cycloheptanone using sodium-wet ether). Cyclooctene,
sion of both gem- and vic-chloronitroso compounds to cyclododecene (cis-trans mixture) and norbornene
their corresponding chloronitro derivatives. This was were purchased from Aldrich. Chlorotrimethylsilane
formulated based on the fact that cetyltrimethylammo- (TMSCl) and cetyltrimethylammonium bromide were
nium group is an efficient and supportive countercation purchased from Spectrochem, and TMSCl was dis-
in such successful reagents as cetyltrimethylammonium tilled over quinoline (1–2%). iso-Amyl nitrite was pre-
permanganate (CTAP)28 and dichromate (CTAD),29 pared by the literature procedure.30c The liquid start-
and that hypochlorite is a good oxidant for conver- ing compounds obtained from commercial sources were
sion of nitroso to nitro group.2d, 11 We have prepared distilled and their purity checked by G.C. before use.
CTAHC and found it to be a handy, practical oxidizing
agent in homogeneous organic solvent media for oxi-
dizing both gem-chloronitroso and vic-chloronitroso
2.2 Preparation of cetyltrimethylammonium
hypochlorite
compounds, prepared respectively by reacting oximes
and olefins with NOCl generated in situ.18a,b,g The
results are reported here.
A solution of cetyltrimethylammonium bromide (CTAB,
21.0 g, 62.5 mmol) in 100 mL of dichloromethane was
placed in a 1 L 2-necked round bottomed flask equipped
with a mechanical stirrer and a dropping funnel.
Sodium hypochlorite solution (120 mL) containing 4%
chlorine (only Merck company NaOCl worked well;
2. Experimental
2.1 General
The NMR spectra were recorded on a JEOL FX90Q or NaOCl solution from other two commercial sources did
Bruker AC-250 instrument using CDCl3 as solvent and not give CTAHC) was added over 5 min. The mixture
tetramethylsilane (TMS) as internal standard. The IR was stirred for 3–4 h; it was then transferred to a sepa-
spectra were taken on Nicolet Impact 400D single beam rating funnel and allowed to stand until the layers sep-
instrument using KBr pellets for solids and thin film arated (there was frothing that took time to settle). The
between NaCl plates for liquids. GC analyses were car- organic layer was collected, the solvent was removed
ried out on a Varian Vista 6000 instrument using 15% of on a rotary evaporator and the white residue was dried
FFAP on chromosorb-W column (2 × 2 mm i.d.). The over P2O5 under vacuum, yield, 15.6 g (81%). It was
solvents were distilled before use. Diethyl ether was recrystallised from hot ethyl acetate. It decomposed on
washed with 10% FeSO4 solution, dried over CaCl2, heating above 200◦C without melting, and was found to
refluxed over sodium wire-benzophenone and distilled. be soluble in chlorohydrocarbons and also water.

Oxidation of gem-chloronitroso- and vic-chloronitroso-alkanes and -cycloalkanes
435
2.3 Synthesis of gem-chloronitroso compounds:
General procedure
a condenser fitted with a CaCl2 guard tube. A solu-
tion of 4.9 g (14 mmol) of CTAHC in 15 mL of
dichloromethane was added over 15 min. The mix-
ture was stirred until the chloronitroso compound dis-
appeared, as confirmed by GC analysis. The reac-
tion needed 3–13 h for completion depending on the
chloronitroso compound (table 2). The solvent was
removed on a rotary evaporator under vacuum; the
residue was dissolved in 50 mL of ether. The ensu-
ing solution was washed with water (30 × 20 mL) and
saturated NaCl solution (3 × 20 mL), and dried over
Na2SO4. After removing the solvent the product was
chromatographed on silica gel (60–120 mesh) using
petroleum ether (50–55◦C) as eluant. The isolated
yields of the gem-chloronitro compounds varied from
50–70% (table 2).
A solution of 10 mmol of oxime in 10 mL of dry diethyl
ether was taken in a two-necked flask equipped with
a short condenser fitted with a CaCl2 guard tube, and
a dropping funnel. It was cooled to −10◦C with stir-
ring, and 1.03 g (12 mmol) of TMSCl was introduced.
iso-Amyl nitrite (1.40 g, 12 mmol) was added over a
period of 15 min. The reaction mixture was kept stirred
for 1.0–2.5 h depending on the oxime (table 1), and as
determined by TLC analysis. Water (10 mL) was added
and the contents of the flask were transferred to a sep-
arating funnel (the flask was rinsed with 5 mL ether).
The organic layer was separated and washed succes-
sively with water (2 × 15 mL), saturated NaCl solu-
tion (2 × 15 mL), and dried over Na2SO4. The solvent
was removed on a rotary evaporator under reduced pres-
sure and the residue was chromatographed on silica gel
(60–120 mesh) using petroleum ether (b.p. 50–55◦C)
as eluant. The pure gem-chloronitroso products 1a–10a
eluted as blue band. The compounds 5a, 6a, and 11a
were solids, and were recrystallised from ethanol. The
yields were 93–97% (table 1). Their identity was estab-
lished by comparing their spectral properties with those
we reported previously in the case of the reaction of
NO2Cl with the same oximes.12 We have reported the
crystal structure the compound 5a.18d
2.5 Oxime to gem-chloronitro compound: One-pot
reaction
In a 100 mL two-necked flask, equipped with a drop-
ping funnel and condenser fitted with a CaCl2 guard
tube, was placed 10 mmol of oxime, 5 mL of dry ether
was added and the solution was cooled to −10◦C with
stirring. TMSCl (1.2 g, 13 mmol) was added drop-
wise, the solution was stirred for further 10–15 min,
and then 1.4 g (12 mmol) of iso-amyl nitrite was added
over 15–20 min. The reaction mixture was stirred for
1–2.5 h (as mentioned in table 1), and allowed to attain
room temperature. To this was added a solution of 6.0 g
(17.8 mmol) of CTAHC in 25 mL of dichloromethane
2.4 Preparation of gem-chloronitro compounds:
General procedure
A solution of 10 mmol of gem-chloronitroso compound and the mixture was stirred until the chloronitroso com-
in 10 mL of dichloromethane was placed in a 100 mL pound disappeared (TLC analysis). The volatile sub-
two-necked flask equipped with dropping funnel and stances were removed on a rotary evaporator under
Table 1. Preparation of gem-chloronitroso compounds form oximes and NOCl.
Entry
Oxime of
gem-Chloronitroso Compdsa
Reaction time (h) Yield (%) m.p. (◦C)b
1
2
3
4
5
6
7
8
9
10
Cyclopentanone
Cyclohexanone
Cycloheptanone
Cyclooctanone
1-Chloro-1-nitrosocyclopentane
1-Chloro-1-nitrosocyclohexane
1-Chloro-1-nitrosocycloheptane
1-Chloro-1-nitrosocyclooctane
(1a)
(2a)
(3a)
(4a)
(5a)
(6a)
(7a)
(8a)
(9a)
1.5
1.0
1.5
1.5
1.5
1.0
2.5
2.0
1.0
1.0
93
95
95
96
98
98
93
94
96
97
Cyclododecanone 1-Chloro-1-nitrosocyclododecane
50–52
42–44
Norcamphor
Acetophenone
Propiophenone
4-Heptanone
2-Chloro-2-nitrosonorbornane
1-Chloro-1-nitroso-1-phenylethane
1-Chloro-1-nitroso-1-phenylpropane
4-Chloro-4-nitrosoheptane
Dibenzoyl ketone 2-Chloro-2nitroso-1,3-diphenylpropane (10a)
93–95
aWe had earlier obtained the compounds 1a–10a by reacting oximes with NO2Cl12
bExcept 5a, 6a, and 10a, the others are liquids, and decompose rapidly on heating

436
Abdulkarim H A Mohammed and Gopalpur Nagendrappa
Table 2. Oxidation of gem-chloronitroso to gem-chloronitro compounds by CTAHC.
Entry
gem-Chloronitro compound
From 1a–10a (Two steps)
From 1a–10a (One-pot)
Reaction time (h) Yield (%) Reaction time (h) Yield (%)
1
2
3
4
5
6
7
8
9
10
1-Chloro-1-nitrocyclopentane
1-Chloro-1-nitrocyclohexane
1-Chloro-1-nitrocycloheptane
1-Chloro-1-nitrocyclooctane
1-Chloro-1-nitrocyclododecane
2-Chloro-2-nitronorbornane
1-Chloro-1nitro-1-phenylethane
1-Chloro-1-nitro-1-phenylpropane
4-Chloro-4-nitroheptane
(1b)
(2b)
(3b)
(4b)
(5b)
(6b)
(7b)
(8b)
(9b)
13
13
12
13
4
10
3
3
14
12
70
74
70
68
70
70
50
50
53
60
16
16
14
15
5
13
5
5
16
14
72
77
71
73
78
75
51
53
60
65
2-Chloro-2-nitro-1,3-diphenylpropane (10b)
vacuum, the residue was dissolved in 50 mL of ether, filtered off, washed with 10 mL of 10% NaHCO3 solu-
and the solution was washed with water (3 × 25 mL), tion, water (10 mL), and carefully with a little alco-
saturated NaCl (3 × 20 mL), and dried over Na2SO4. hol (under vacuum). The vic-chloronitroso compound
After removing the solvent, gem-chloronitro product was separated from the byproduct α-chlorooxime by
was obtained as mentioned in the previous experiment. chromatographing on silica gel. (Eluant: petroleum
The yields were in the range of 51–78% (table 2).
ether, b.p. 50–55◦C, followed by 5% ethyl acetate in
petroleum ether). The dimers were carefully (they are
fairly soluble in ethanol) recrystallized from ethanol.
We have reported the vic-chloronitroso compounds
11a–17a in an earlier paper,18g where the preparation
method was slightly different.
2.6 Preparation of vic-chloronitroso compounds:
General procedure
2.6a Method A—without solvent: In a 100 mL two-
necked flask equipped with a dropping funnel and a
condenser fitted with a guard tube were placed 10 mmol
of cycloalkene and cooled to −10◦C. TMSCl was added
drop-wise with stirring, followed by iso-amyl nitrite
(12 mmol) over a period of 20 min. The reaction was
followed by GC. The time taken for completion of the
reaction varied widely depending on the cycloalkene,
(table 3). When the cycloalkene had disappeared water
(10 mL) was added, the white dimeric solid product was
2.6b Method B—in dichloromethane: The above
reaction was conducted under the same conditions
by taking the solution of cycloalkene in 10 mL of
dry dichloromethane. At the end of the reaction,
10 mL of water was added, the layers were separated;
organic layer was washed with water (2 × 15 mL), 10%
NaHCO3 solution (15 mL), water (15 mL), saturated
Table 3. Preparation of vic-chloronitroso compounds by adding NOCl to olefins.
Entry
vic-Chloronitroso compda
Solvent-free reaction
Reaction time (h)
Yield (%)a
In CH2Cl2
Reaction time (h)
Yield (%)b
1
2
3
4
5
6
7
1-Chloro-2-nitrosocyclopentane
1-Chloro-2-nitrosocyclohexane
1-Chloro-2-nitrosocycloheptane
1-Chloro-2-nitrosocyclooctane
1-Chloro-2-nitrosocyclododecane
2-Chloro-3-nitrosonorbornane
2-Chloro-1-nitrosoheptane
(11a)
(12a)
(13a)
(14a)
(15a)
(16a)
(17a)
1.0
1.5
2.0
2.5
4.0
0.5
3.0
70 (+20)
65 (+15)
65 (+13)
60 (+20)
80 (+10)
75 (+10)
57 (+10)
1.5
1.8
2.5
2.8
4.0
0.5
3.0
60 (+30)
63 (+30)
60 (+25)
55 (+25)
70 (+20)
70 (+15)
55 (+15)
aWe have described the vic-chloronitroso compounds 11a–17a in an earlier paper18g
bYield of the corresponding α-chlorooxime, the product of tautomerisation

Oxidation of gem-chloronitroso- and vic-chloronitroso-alkanes and -cycloalkanes
437
Table 4. Oxidation of vic-chloronitroso to vic-chloronitro compounds.
Entry
Compounda
Reaction time (h)
Yield (%)
1
2
3
4
5
6
1-Chloro-2-nitro-cyclopentane
1-Chloro-2-nitro-cyclohexane
1-Chloro-2-nitro-cycloheptane
1-Chloro-2-nitro-cyclooctane
2-Chloro-3-nitro-norbornane
2-Chloro-1-nitro-heptane
(11b)
(12b)b
(13b)
(14b)
(16b)b
(17b)b
12
15
13
10
11
10
40 (+10)c
35 (+12)c
37 (+10)c
30 (+10)c
40 (+15)c
35 (+15)c
a1-chloro-2-nitrosocyclododecane (15a) did not get oxidized
b12b,31a 1631b and 17b31c are known in the literature; the other three are not
cThe numbers in parentheses are yields of the respective α-chlorooximes
NaCl solution (15 mL), and dried over Na2SO4. In stirred until the starting compound had disappeared,
this case the byproduct α-chlrooxime was formed in
slightly higher proportion than in the previous case, and
was separated by chromatography as in the previous
experiment, (table 3).
which took 10–15 h depending on the starting com-
pound. All the vic-chloronitroso compounds, except 1-
chloro-2-nitrosocyclododecane, underwent oxidation.
The solvent was removed on a rotary evaporator,
the residue was dissolved in 50 mL of diethyl ether,
and the resulting solution was washed with water
(2 × 30 mL), saturated NaCl solution (2 × 20 mL),
and dried over Na2SO4. After removing the solvent,
the residue was chromatographed on a silica gel col-
umn using petroleum ether (b.p. 50–55◦C) as eluant.
The yields of vic-chloronitro derivatives are modest,
as α-chlorooxime was formed as a by-product in each
case (table 4). The spectral data of vic-chloronitro
2.7 Oxidation of vic-chloronitroso to vic-chloronitro
compounds
A solution of 4.2 g (12 mmol) of CTAHC in 10 mL
of CH2Cl2 was added to a solution of 10 mmol of vic-
chloronitroso compound in 10 mL of CH2Cl2 stirred
vigorously in a 100 mL two-necked flask equipped
with a dropping funnel and a condenser fitted with
a CaCl2 guard tube. The reaction mixture was kept compounds are recorded in table 5.
Table 5. IR, 1H NMR and 13C NMR spectral data for vic-chloronitro compounds.
Compd
IR (neat), ν (cm−1) (selected)
1H NMR (CDCl3) δ (ppm)
13C NMR (CDCl3) δ (ppm)
11b
2976, 2903, 1564, 1471,
1440, 1140, 1357, 1140,
1078, 964, 788, 648
2955, 2878, 1569, 1455,
1440, 1372, 1191, 1000,
984, 866, 762, 695, 545
2966, 2929, 2857, 1564,
1481, 1450, 1362, 1134,
1072, 814, 788, 643
2929, 2862, 1636, 1564,
1466, 1460, 1352, 1222,
1186, 1021, 881, 721, 643
2981, 2888, 1693, 1569,
1455, 1347, 1316, 995,
953, 850, 819, 772, 736
4.532 (m, 1H),
3.079 (m,1H),
1.94-2.644 (m, 6H).
4.76 (m, 1H),
2.56-2.66 (m, 1H),
1.52-2.43 (m, 8H)
4.85 (m, 1H),
2.49-2.68 (m, 1H),
1.522-2.37 (m, 10H)
5.15-5.30 (m, 1H),
2.84-2.97 (m, 1H),
2.55-1.51 (m, 12H)
4.95-4.92 (m, 1H),
4.74-4.77 (m, 1H),
2.20-3.14 (m, 3H),
1.57-1.80 (m, 6H)a
19.13, 32.07, 35.25,
65.17, 107.01
12b
13b
14b
16b
17.84, 21.81, 29.77, 30.73,
60.21, 101.73
20.74, 21.00, 25.10,
29.26, 34.90,
64.87, 107.77
21.81, 24.59, 25.31,
25.96, 30.72, 32.80,
57.63, 103.74
23.51, 26.91, 35.71,
48.31, 53.46, 65.63,
105.52, and 23.46, 26.57,
36.07, 47.98, 52.90,
64.22, 105.52a
17b
2976, 2940, 2883, 1647,
1569, 1471, 1393, 1352,
1093, 866, 783, 674
4.2-4.6 (m, 2H),
2.25-2.46 (m, 1H),
1.15-1.80 (m, 11H)
13.61, 12.76, 23.12,
28.63, 23.19,
64.92, 104.05.
aMixture of two isomers

438
Abdulkarim H A Mohammed and Gopalpur Nagendrappa
(scheme 2), which were obtained in pure form by pass-
3. Results and discussion
3.1 gem-Chloronitro compounds
ing through silica gel column in almost quantitative
yield (table 1). They were identified by their spectral
data as described in our previous paper.12 1-
Chloro-1-nitrosocyclododecane (5a), 2-chloro-2-
nitrosonorbonane (6a) and 2-chloro-2-nitroso-1,3-
diphenylpropane (10a) are stable solids. We have ear-
lier reported the crystal structure of the compound
5a.18d The others (1a–4a and 7a–9a) are liquids, which
decompose slowly at room temperature, and rapidly
on heating. Their blue colour indicates that they exist
in monomeric form. The dimerisation, which is a
common feature of nitroso compounds,18a,b is pre-
vented because of electronegative effect and steric
hindrance of the geminal chlorine group. In contrast,
the vic-chloronitroso compounds dimerise18g easily
(scheme 3).
Cetyltrimethylammonium hypochlorite (CTAHC) was
prepared by a procedure similar to the one used for
the preparation of CTAP.28 When cetyltrimethylammo-
nium bromide in dichloromethane and commercially
available sodium hypochlorite solution are mixed and
mechanically stirred at room temperature, they undergo
double displacement, and CTAHC accumulates in the
dichloromethane phase, which is separated and worked
up to get the white solid. However, CTAHC is relatively
more soluble in water than CTAP, hence needs more
careful work-up. It decomposes without melting above
200◦C, but can be stored intact in refrigerator for several
months.
−
CH3-(CH ) + (CH ) Br(CH Cl ) + NaOCl (aq)
−→ CH3-(CH ) + (CH ) − Cl(CH Cl ) + NaBr (aq)
The oxidation of gem-chloronitroso compounds 1a–
10a was carried out in dichloromethane at room tem-
perature by using about a 40% excess of CTAH. The
reaction takes 3–13 h for completion depending on the
structure of the starting compound (table 2). The gem-
chloronitro derivatives 1b–10b (scheme 2), after isola-
tion by usual work-up and purification by chromato-
graphing on silica gel, were identified by comparing
their spectral data with those described previously.12
2 15 N
3 3
2
2
2 15 N
3 3 O
2
2
(eq 3)
Ten ketoximes 1–10 were treated with TMSCl and
iso-amyl nitrate at −10◦C. The NOCl generated in situ
reacted with oximes to produce the corresponding blue
coloured gem-chloronitroso derivatives 1a–10a
Cl
Cl
NOH
NO
NO2
RONO / Me3SiCl
CTAH
n
n
n
o
dry ether, -10
C
CH2Cl2, RT
1a
2a
3a
4a
5a
1, n = 1
2, n = 2
1b
2b
3b
3, n = 3
4, n = 4
5, n = 8
4b
5b
NOH
NO2
Cl
,,
,,
NO
Cl
,,
6b
6a
6
NOH
R2
Cl NO
NO2
R2
Cl
R1
,,
R1
C
R2
C
R1
C
7, R1 = Ph, R2 = CH3
8, R1 = Ph, R2 = C2H5
9, R1 = R2 = n-C3H7
10, R1 = R2 = Ph-CH2
7a
7b
8a
8b
9b
9a
10a
10b
Scheme 2. Preparation of gem-chloronitro compounds.

Oxidation of gem-chloronitroso- and vic-chloronitroso-alkanes and -cycloalkanes
439
Cl
Cl
Cl
ClSiMe3
RONO
CTAHC
n
n
n
n
NO2
NO
N =
O-
2
11, n = 1
11b
12b
11a
12, n = 2
12a
13a
14a
15a
13, n = 3
14, n = 4
15, n = 8
13b
14b
-
Cl
Cl
NO2
,,
Cl
,,
NO
N =
O-
2
16a
16
16b
Cl
Cl
n-C5H11-C-CH2
Cl
,,
,,
n-C5H11-CH=CH2
n-C5H11-CH-CH2
n-C5H11-C-CH2
NO
-
H
NO2
H
N
2
O
17
17a
17b
Scheme 3. Preparation of vic-chloronitro compounds.
3.2 One-pot procedure for oxime to gem-chloronitro
compound
The vic-chloronitroso compounds were treated at
room temperature, with 20% excess of CTAHC. This
produced 1-chloro-2-nitro compounds 11b–14b, 16b
and 17b, which were obtained after usual work-up
and purification by chromatographing on silica gel col-
umn (table 4). They were identified by their spec-
tral data (table 5). 1-Chloro-2-nitroso-cyclododecane
The oximes could also be converted to their respective
gem-chloronitro derivatives by a one-pot process. In
this method, each oxime in ether solution at −10◦C was
first treated with TMSCl and iso-amyl nitrite to form
gem-chloronitroso compound, after the mixture attained
room temperature, it was treated with the required
quantity of CTAHC in ether solution, stirred until the
chloronitroso compound disappeared, and worked-up
to get the gem-chloronitro derivative. The yields were
slightly better (table 2) than in the case of the reactions
carried out in two separate steps, which is attributable
to single work-up step.
1
(15a) did not undergo oxidation. The H and 13C
NMR data (table 5) clearly indicated that each
monocyclic vic-chloronitro derivative (11b–14b) was
a single stereoisomer and most likely trans. How-
ever, 2-chloro-3-nitronorbornane was a mixture of a
major and a minor component, the major one being
the exo, cis derivative.18a,b, 27l The chloronitroheptane
(17b) contained 10–15% of probably a regioisomeric
impurity. Three of these, i.e., 12b, 16b and 17b
are known in the literature, while the other three
are not.
3.3 vic-Chloronitro compounds
The monomeric adducts with α-hydrogen tend to
tautomerise to give chlorooximes fairly rapidly par-
ticularly in the presence of acidic or basic impu-
rities.18g If excess NOCl is generated, the initially
formed monomer produces α-chlorooxime as interme-
diate which further reacts with NOCl to finally give
1,2-dichloro-1-nitroso derivatives.18b Actually, in these
reactions some amount of α-chlorooximino derivatives
were isolated (table 4). Even during CTAH oxidation
of the pure vic-chloronitroso compounds, some further
quantity of chlorooxime was isolated as by-product in
each case. As a result, the yields of vic-chloronitro
derivatives were less than expected.
Six vic-chloronitro compounds, 11b–14b, 16b and 17b
were prepared by a two-step procedure. In the first step,
vic-chloronitroso compounds 11a–17a were prepared
by adding NOCl, generated in situ, to cycloalkenes
and alkenes 11–17 (scheme 3). While 1-chloro-2-
nitrosocycloheptane (13a) remained as blue monomer,
the other adducts, 11a, 12a, and 14a–17a, were
obtained as white dimeric diazine dioxide products,18g
which exhibited widely varying stability. The dimer
of 2-chloro-3-nitrosonorbornene (16a) is quite stable
even in solution, whereas the other dimers dissociate
into monomers in solution resulting in monomer–dimer
equilibrium.18b,d,g

440
Abdulkarim H A Mohammed and Gopalpur Nagendrappa
Mudryk B, Ros F and Jawdosiuk M 1982 Tetrahedron
4. Conclusions
38 1059; (f) Fridman A L, Surkov V D and Novikov S S
1980 Russ. Chem. Rev. 49 1068
4. Barnes M W and Patterson J M 1976 J. Org. Chem. 41
733
The oxidation of 1-chloro-1-nitroso and 1-chloro-
2-nitroso compounds can be efficiently carried out
using the novel cetyltrimethylammonium hypochlo-
rite (CTAHC) reagent to the corresponding chloronitro
derivatives. Considering the fact that CTAHC is easy to
prepare and to handle, the method offers an easy access
to the gem-chloronitro and vic-chloronitro compounds,
which have many useful synthetic as well as other appli-
cations. The present method is promising particularly
for the preparation of vic-chloronitro compounds, as the
literature methods involve the complicated free radical
reactions of NO2Cl or N2O4+Cl2 mixture with olefins,
which require extensive purification and give low yields
of the desired products.
5. Ceccherelli P, Curini M, Epitano F, Marotullio M C and
Rosati O 1998 Tetrahedron Lett. 39 4385
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9. Paquette L A, Waykole L M and Shen C-e 1988 J. Org.
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10. (a) Marchand A P, Arney Jr B E and Dave P R 1988 J.
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Acknowledgements
AHAM thanks Indian Council for Cultural Relations
(ICCR), NewDelhi, for a fellowship under Cultural
Exchange Programme. The work was partly sup-
ported by UGC-DRS and UGC-COSIST programmes,
NewDelhi. Some equipment used for the work is a 13. (a) Kresze G, Mayer N M and Winkler J 1971 Ann.
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donation to GN by the Alexander von Humboldt Foun-
dation, Germany.
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