Kinetic Study of the Nitrolysis of Haloadamantanes

Article abstract of DOI:10.1134/S1070428020090043

Abstract: The kinetics of nitrolysis of haloadamantanes containing halogen atoms in the bridging and bridgehead positions with fuming nitric acid have been studied. The effective nitrolysis constants of eight haloadamantane derivatives have been determine

Full text of DOI:10.1134/S1070428020090043

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 9, pp. 1525–1531. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 9, pp. 1344–1352.
Kinetic Study of the Nitrolysis of Haloadamantanes
Yu. N. Klimochkina, E. A. Ivlevaa,*, and M. Yu. Skomorokhovb
a Samara State Technical University, Samara, 443100 Russia
b Olainfarm Joint Stock Company, Olaine, 2114 Latvia
*e-mail: elena.a.ivleva@yandex.com
Received April 30, 2020; revised May 3, 2020; accepted May 16, 2020
Abstract—The kinetics of nitrolysis of haloadamantanes containing halogen atoms in the bridging and
bridgehead positions with fuming nitric acid have been studied. The effective nitrolysis constants of eight
haloadamantane derivatives have been determined. The reaction is described by pseudo-first-order kinetic
equation, and the reactivity decreases as the number of halogen atoms in the substrate molecule increases.
Haloadamantanes with less electronegative halogens show higher reactivity.
Keywords: kinetics, haloadamantanes, nitrolysis, mechanism, fuming nitric acid, reactivity
DOI: 10.1134/S1070428020090043
Polyfunctional adamantane derivatives are key
starting materials in the synthesis of biologically active
compounds and advanced materials [1–5]. Among
them, polyhalogenated adamantanes are most synthet-
ically accessible. For example, 1,3-dibromoadamantane
is used as a molecular scaffold in the design of metal–
organic frameworks [6] and polymeric materials [7, 8]
and synthesis of biologically active compounds [9–11]
and alkylboronic acid esters for cross-coupling re-
actions and medicinal chemistry [12, 13]. 1,3-Dibromo-
adamantane was reported to undergo transformations
accompanied by change of the molecular skeleton
[14–17]. The synthetic potential of 1,3-dichloro-
and 1,3-difluoroadamantanes has been explored to
a lesser extent [18, 19]. 1,3,5-Tribromoadamantane is
the basic structural unit of tripod systems [20, 21] and
is used to obtain other polyfunctionalized adamantane
derivatives [22].
corresponding carbocation which is then stabilized by
nitrate ion to form alkyl nitrate as a final product.
Treatment of 1-haloadamantanes with fuming nitric
acid was reported to afford adamantan-1-yl nitrate and
adamantane-1,3-diyl dinitrate [39]; in the reaction of
2-haloadamantanes with nitric acid, the nytrolysis of
the C–Hlg bond was accompanied by oxidation to ada-
mantan-2-one [40].
Cleavage of the C–Hlg bond is likely to involve
one-electron transfer with the formation of adamantyl
radical cation which then decomposes to adamantyl
cation and halogen atom. This was confirmed by
photoelectron spectra of a number of 1-haloadaman-
tanes. The adiabatic ionization potentials were
estimated at 9.63 eV for 1-bromoadamantane [41],
9.30 eV for 1-chloroadamantane [42], and 8.79 eV of
1-iodoadamantane [41].
In order to elucidate mechanistic details of the
C–Hlg bond heterolysis in haloadamantanes, in this
work we studied the kinetics of nitrolysis of haloada-
mantanes containing halogen atoms in the bridging
and bridgehead positions in the system nitric acid–
methylene chloride. The substrates were 1-fluoroada-
mantane (1), 1,3-difluoroadamantane (2), 1,3-dichloro-
adamantane (3), 1,3-dibromoadamantane (4), 2,2-di-
chloroadamantane (5), 2,2-difluoroadamantane (6),
1,3,5-tribromoadamantane (7), and methyl 3-chloro-
adamantane-1-carboxylate (8).
Until present, nucleophilic substitution in the halo-
adamantane series [23–29] and anodic oxidation of
these compounds [30–33] have been well documented.
On the other hand, only a few data are available on
reactions of haloadamantanes involving oxidative
cleavage of the C–Hlg bond [34]. In continuation of
our studies on the mechanisms of oxidation of cage
substrates [35–37], herein we report some kinetic data
for the nitrolysis of polyhaloadamantanes.
The nitrolysis of haloalkanes with nitric acid was
studied in [38]. It was presumed that heterolytic
dissociation of the C–Hlg bond in nitric acid gives the
The kinetic measurements were carried out using
100% nitric acid in methylene chloride. The reaction
1525

KLIMOCHKIN et al.
1526
Table 1. Orders of the reaction of 1-fluoroadamantane (1)a
with nitric acid in adamantane substrate
reactive than unsubstituted adamantane in the reaction
with nitric acid [35]. The conversion of 1-fluoro-
adamantane (1, 0.05 M) at –10°C in a mixture of HNO3
(4 M) and CH2Cl2 was complete even in 30 s.
[HNO3], M
0.75
Reaction order
0
1.00
1.50
1.75
2.00
0.11
0.62
0.91
b
The order of the reaction in the substrate was
determined from the initial rates of nitrolysis of
1-fluoroadamantane (1) as a model (Table 1). It was
found that, as the concentration of nitric acid increases,
the reaction order changes from zero to a fractional
value which then approaches unity. Such change of the
reaction order from first to zero is also typical of
nitroxylation [35] and nitration in inert solvents [45]
and is related to change of the limiting step. At low
nitric acid concentrations, the overall rate of nitrolysis
of reactive substrates depends on the rate of formation
of nitronium cation in the reaction system.
a
b
c0 = 0.025–0.05 M, 20°C.
The initial reaction rate exceeded 8×10–3 mol/s, so that the error
in the determination of the reaction order was very large.
mixtures were analyzed by GLC using 1,4-dinitro-
benzene as internal standard. The reactions were run
at 20°C, the initial substrate concentration was c0 =
0.025 M, and the concentration of nitric acid was
varied from 4 to 8 M. Before GLC analysis, the
reaction mixtures were quenched by pouring onto
crushed ice.
Obviously, change to the first order in substrate is
possible when the reactivity of the latter decreases,
which can be achieved by introduction of additional
electron-withdrawing substituents into haloadamantane
molecule. In fact, the nitrolysis of polyhaloadamantanes
3–8 and methyl 3-chloroadamantane-1-carboxylate (2)
is described by pseudo-first-order kinetic equation:
On the basis of generally accepted theoretical views
and published data [38], the following reactivity order
of adamantyl halides toward nitrolysis can be expected:
I > Br > Cl > F. The relative rates of the reactions of
1-haloadamantanes with nitronium salts in acetonitrile
were determined (competitive reaction method) as
F:Cl:Br:I = 1:6.6:67:240 [43]. The reaction is strongly
exothermic; for instance, the heat effect in the nitrolysis
of tert-butyl chloride with nitric acid (1:1, by weight)
was 80 kJ/mol [44].
c
τ
ô
 keff [c], where keff  k[HNO3 ]n .
Figure 1 shows semilog kinetic curves for the
nitrolysis of polyhaloadamantanes. The observed linear
dependences suggest first order of the reaction in the
adamantane substrate. The effective rate constants for
the nitrolysis of haloadamantanes 2–8 are given in
Table 2. Comparison of the rate constants for the
nitrolysis of methyl 3-chloroadamantane-1-carboxylate
(8) and nitroxylation of methyl adamantane-1-carbox-
ylate {keff = (3.9±0.4)×10–6 s–1 [35]} makes it possible
to roughly estimate the rates of dissociation of tertiary
CAd–Cl and CAd–H bonds by the action of nitric acid.
The ratio of these rate constants is 325:1. It should be
noted that this value was obtained assuming equal
effects of the methoxycarbonyl group on the rates of
nitrolysis and nitroxylation, since analogous ratio for
unsubstituted adamantane is considerably higher. The
rate of nitrolysis of 1-chloroadamantane was so high
that even its approximate estimation was impossible.
Unlike the data of [43], 1-fluoroadamantane (1)
turned out to be at least 3 orders of magnitude more
Table 2. Rate constants for the nitrolysis of haloadaman-
tanes 2–8a
[HNO3]0,
Substrate (no.)
keff, s–1
M
4
4
4
4
4
5
6
7
8
4
2,2-Dichloroadamantane (5)
2,2-Difluoroadamantane (6)
1,3-Dibromoadamantane (4)
1,3-Dichloroadamantane (3)
1,3-Difluoroadamantane (2)
1,3-Difluoroadamantane (2)
1,3-Difluoroadamantane (2)
1,3-Difluoroadamantane (2)
1,3-Difluoroadamantane (2)
1,3,5-Tribromoadamantane (7)
5.61±0.13×10–3
0.15±0.05×10–3
5.92±0.73×10–3
0.72±0.11×10–3
0.64±0.11×10–3
1.62±0.20×10–3
3.47±0.48×10–3
3.72±0.47×10–3
4.50±0.71×10–3
1.94±0.21×10–3
The reactivity increases in the series 1,3-difluoro-
adamantane (2) < 1,3-dichloroadamantane (3) < 1,3-di-
bromoadamantane (4), and the difference in the nitro-
lysis rate constants of dihaloadamantanes 2 and 3 does
not exceed the experimental error, whereas dibromide
Methyl 3-chloroadamantane-
1-carboxylate (8)
4
1.26±0.13×10–3
a
c0 = 0.025 M, CH2Cl2, 20°C.
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KINETIC STUDY OF THE NITROLYSIS OF HALOADAMANTANES
1527
Scheme 1.
R
Hlg
+
2HNO3
R
ONO2 + 1/2Hlg2 + NO2 + H2O
Scheme 2.
Hlg
O
Hlg
+
2HNO3
+
2NO2Hlg (Hlg2 + NO2)
+ H2O
4 is more reactive by approximately an order of magni-
tude. The rate of nitrolysis of 1,3,5-tribromoadaman-
tane (7) is only three times lower than that found for
dibromide 4. Such small differences in the reactivity
can be explained assuming that polar substituent
effects insignificantly influence the transition state
which occupies different positions on the reaction
coordinate for fluoro, chloro, and bromo derivatives.
Moreover, it is quite probable that the nitrolysis of dif-
ferent adamantyl halides follows different mechanisms
[46], though it can be described by a common formal
scheme reflecting its stoichiometry (Scheme 1).
that of 1,3-dichloro isomer 3. In this case, two opposite
effects are operative: negative inductive effect of the
geminal halogen atom destabilizes the transition state,
whereas the stability of intermediate halocarbenium
ion increases due to n–2p resonance interaction [49].
Unlike solvolytic reactions, geminal halogens reduce
the rate of nitrolysis [46], i.e., the inhibitory inductive
effect is stronger than conjugation effect, especially in
the case of difluoride 6.
The order of the reaction in nitric acid (n) can be
determined from the slope of the kinetic curves in the
coordinates logkeff—log[HNO3] using the equation
The given equation, according to which oxidation
of Hlg· to Hlg2 is a necessary condition for nitrolysis,
is inapplicable to the substitution reaction of fluoro
derivatives. The redox potential of nitronium cation
(1.6–1.9 V) is insufficient to oxidize fluoride anion to
fluorine [F–/(1/2F2)g 2.87 V] [47]. Furthermore,
fluorine itself oxidizes nitric acid and nitric anhydride
to give nitryl fluoride [48].
logkeff = logk + nlog[HNO3].
Figure 2 shows the dependence of rate of nitrolysis
of difluoride 2 on the concentration of nitric acid. The
slope is equal to 2.81. Taking into account fairly high
dispersion of the experimental data, the nitrolysis order
in nitric acid can be assumed to be equal to 3. It should
be noted that formally fifth order in nitric acid was
found for the nitroxylation reaction [35]. This value
surprisingly accurately coincides with the order in
nitric acid found by studying the kinetics of nitration of
alkylbenzenes in carbon tetrachloride [50]. High
reaction orders in nitric acid for the nitration in inert
solvents are likely to be general. For example, the
A different reactivity order was observed in the ni-
trolysis of 2,2-dihaloadamantanes which is outlined in
Scheme 2. The reaction with 2,2-difluoroadamantane
(6) is 37 times slower than with 2,2-dichloroadaman-
tane (5) and 4 times slower than with 1,3-difluoro-
adamantane (2). On the other hand, the rate constant of
nitrolysis of geminal dichloride 5 is 8 times higher than
2.0
1.0
y = (2.80±0.39)x – (0.79±0.12);
6
R2 = 0.9177
1.8
2
3
0.8
0.6
0.4
0.2
0.0
1.6
1.4
1.2
1.0
0.8
0.6
7
4
5
0
2
4
6
8
0.5
0.6
0.7
log[HNO3]0
0.8
0.9
τ, min
Fig. 2. Log plot of the effective rate constant for the nitrolysis
of 1,3-difluoroadamantane (2) versus nitric acid concentra-
tion; CH2Cl2, 20°C, c0 = 0.025 M.
Fig. 1. Semilog kinetic curves for the nitrolysis of haloadamantanes
2–7; c0 = 0.025 M, [HNO3]0 = 4 M, CH2Cl2, 20°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 9 2020

KLIMOCHKIN et al.
1528
Scheme 3.
+
NO2
+
NO2Hlg
NO2
Hlg
Hlg
Scheme 4.
+
NO2
·
+·
Hlg
Hlg
Hlg
NO2
NO2
·
NO2 + Hlg
+
nitration of oxiranes in methylene chloride is charac-
terized by third order in nitric acid and second order in
nitric anhydride [51]. The rate of nitration of cellulose
in methylene chloride is also proportional to the con-
centration of nitric acid at a power of 3 (calculated
from the data of [52]). It is attractive to suppose that
the high order in nitric acid is not related to solvent
effect but is intrinsic to the reaction itself. This
assumption is indirectly supported by the kinetic study
of nitration of aromatic substrates with a solution of
nitric anhydride in nitric acid [53], which showed that
the reaction rate increases to a greater extent than the
concentration of nitronium cation in the system. These
findings are likely to reflect oligomeric nature of
fuming nitric acid [54] and the existence of solvation
species and ion–molecular equilibria whose nature has
not been clearly understood [54–56].
We believe that somewhat different reaction scheme
is more probable (Scheme 4). Herein, the transition
state is a superposition of halonium ion and radical pair
formed by haloadamantane radical cation and nitrogen
dioxide, and the primary intermediate is adamantyl
cation. As applied to 2,2-dihaloadamantanes, the inter-
mediate is halocarbenium ion which is converted to
unstable geminal halo nitrate, and the latter decom-
poses to adamantan-2-one and nitryl halide.
In the case of nitrolysis of adamantyl fluorides for
which the formation of halonium ions is hardly prob-
able, a concerted mechanism could not be ruled out.
Dissociation of the C–F bond is likely to be accom-
panied by synchronous formation of C–O bond in the
protonated form of final nitric acid ester due to partic-
ipation of solvation shell of nitronium cation (Fig. 3).
Figure 4 shows the reactivity series of haloada-
mantane derivatives in the nitrolysis in the system
HNO3–CH2Cl2, which was inferred from the results of
our study.
Analysis of our kinetic data for the reactions of
haloadamantanes with nitric acid suggests that several
nitrolysis mechanisms are possible and that the reac-
tion under study is a particular case of oxidative
substitution at a saturated carbon atom [46]. One of the
possible reaction paths is shown in Scheme 3, accord-
ing to which one-electron oxidation of adamantyl
halide with nitronium ion gives intermediate halonium
ion, and the latter decomposes to nitryl halide and
adamantyl cation whose stabilization with a nucleo-
philic species yields final products.
EXPERIMENTAL
Quantitative analysis of the reaction mixtures was
performed with a Thermo Scientific Focus gas
chromatograph (USA) equipped with a 0.5-m×3-mm
column packed with 5% SE-30–3% CKTFT-100 on
Inerton AW-HMDS (0.20–0.25 mm); oven temperature
programming from 80 to 120°C at a rate of 5 deg/min;
injector temperature 120°C; carrier gas helium. The
melting points were measured in capillaries on
an MPM-H2 melting point apparatus (Germany) and
are uncorrected. Compounds 1, 3, and 7 with a purity
of ≥95.0% were provided by A.M. Aleksandrov
(Kukharʼ Institute of Bioorganic and Petroleum
Chemistry, National Academy of Sciences of Ukraine).
1,3-Dibromoadamantane (5) [6], 1,3,5-tribromoada-
F
NO2 NO3
NO2
C
O
H
Fig. 3. Postulated transition state for the nitrolysis of 2,2-di-
fluoroadamantane.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 9 2020

KINETIC STUDY OF THE NITROLYSIS OF HALOADAMANTANES
1529
Br
Br
Cl
Cl
Cl
F
>
>
>
>
F
Br
Cl
Br
Br
COOMe
F
F
>
>
>
Cl
F
Fig. 4. Reactivity series of haloadamantane derivatives in the nitrolysis with nitric acid in methylene chloride at 20°C.
mantane (8) [57], and 2,2-dichloroadamantane (4) [58]
CONCLUSIONS
were synthesized according to reported procedures.
Heterolysis of the C–Hlg bond in haloadamantanes
containing halogen atoms in the bridgehead positions
involves one-electron transfer with intermediate forma-
tion of a radical pair of haloadamantane radical cation
and nitrogen dioxide, which decomposes to adamantyl
cation with liberation of halogen and NO2. Adamantyl
cation is stabilized via addition of nucleophilic species
prevailing in the reaction system.
3-Chloroadamantane-1-carboxylic acid.
1-Chloroadamantane (1), 3 g (0.022 mol), was added
with cooling to 15 mL (0.36 mol) of 98% nitric acid,
and the mixture was kept for 1 h at a temperature not
exceeding 20°C. The mixture was treated with 10 mL
of concentrated aqueous HCl, kept for 1 h at 20°C, and
poured onto ice, and the precipitate was filtered off.
Yield 27%, mp 147–148°C [59].
The nitrolysis of 2,2-dihaloadamantanes initially
gives intermediate halocarbenium ion which is con-
verted to unstable geminal halo nitroxy compound, and
the latter decomposes to adamantan-2-one and nitryl
halide.
Methyl 3-chloroadamantane-1-carboxylate (2)
was synthesized from 3-chloroadamantane-1-carbox-
ylate as described in [60].
Kinetic measurements. The reaction of haloada-
mantanes 1–8 with nitric acid in methylene chloride
was carried out in a glass reactor equipped with
a stirrer, thermometer, and sampler, which was
maintained at a constant temperature within ±0.5°C.
Nitric acid (100%, d = 1.522 g/cm3) was distilled under
reduced pressure (20 torr) just before use. Methylene
chloride was purified by standard method [61]. Com-
ponents of the reaction mixtures were quantitated by
the internal standard method [62] using 1,4-dinitroben-
zene as internal standard. The reactor was charged with
a solution of haloadamantane 1–8 in 5 mL of anhydrous
methylene chloride, the solution was adjusted to
a required temperature, and a solution of 100% nitric
acid in methylene chloride was added over a period of
2 s at that temperature (the overall volume of the mix-
ture was 20 mL). Samples (2 mL each) were withdrawn
at definite time intervals, mixed with 10 mL of ice
water, and neutralized with sodium carbonate. The
organic phase was separated using a separatory funnel,
dried over sodium carbonate, and analyzed by GLC.
Each experiment was carried out in triplicate, and the
rate constants were calculated as a mean of n values.
The order of the reaction with respect to the substrate
was determined from the initial rates at different initial
concentrations [63].
ACKNOWLEDGMENTS
This study was performed using the facilities of the
“Physicochemical Properties of Substances and Materials”
joint center.
FUNDING
This study was performed under financial support by the
Russian Foundation for Basic Research (project no. 20-03-
00869). The synthetic part was financially supported by the
Ministry of Science and Higher Education of the Russian
Federation in the framework of the project part of state
assignment no. 0778-2020-0005.
CONFLICT OF INTEREST
The authors declare the absence of conflict of interest.
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