Russian Journal of Organic Chemistry, Vol. 41, No. 4, 2005, pp. 473–504.

Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005,

pp. 487–516.
Original Russian Text Copyright © 2005 by Borodkin, Shubin.

REVIEW
Nitrenium Ions and Problem of Direct Electrophilic
Amination of Aromatic Compounds
G. I. Borodkin and V. G. Shubin
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: gibor@[Link]

Received May 26, 2004

Abstract—Published data on direct electrophilic amination of aromatic compounds are summarized and
analyzed on the basis of nitrenium ion properties.

1. Introduction ............................................................................................................................................... 473

2. Electronic Structure and Properties of Nitrenium Ions .............................................................................. 474
3. Amination of Arenes with Various Reagents ............................................................................................. 479
3.1. N-Halo Amines ................................................................................................................................... 479
3.2. Reagents Like R2N–OX ...................................................................................................................... 483
3.3. Hydrazoic Acid and Azides ................................................................................................................. 488
3.4. Azodicarboxylic Esters and Hydrazines .............................................................................................. 493
3.5. Aminopyridinium and Aminosulfonium Salts ..................................................................................... 497
4. Radiochemical Generation of Nitrenium Ions ........................................................................................... 500
5. Conclusion ................................................................................................................................................. 500

Gennadii Borodkin was born in 1. INTRODUCTION

1946 in Samara (former Kuibyshev). In
1970, he graduated from the Novo- Aromatic amines constitute an important class of
sibirsk State University. Candidate of organic compounds which give rise to a broad spec-
chemical sciences since 1976; Doctor trum of practical applications. An arylamino group is
of chemical sciences since 1993; Full
Member of the International Academy a structural fragment of many medical agents (anti-
of Sciences of Ecology, Human Safety, biotics, analgetics, antiseptics, etc.) [1–3], pesticides
and Nature; Professor at the Organic [4], dyes [5, 6], luminophores [6], and materials for
Chemistry Department, Novosibirsk lasers and electronics [6, 7]. Aromatic amines are key
State University; Leading scientist of the Organic Reaction
Mechanisms Laboratory, Vorozhtsov Novosibirsk Institute of intermediate products in the synthesis of various prac-
Organic Chemistry, Siberian Division, Russian Academy of tically important organic compounds via diazotization,
Sciences. Fields of scientific interest: chemistry of carbocations nucleophilic substitution, and condensations [2, 4, 6].
and onium ions, molecular rearrangements, physical organic Arylamines also constitute an important class of
chemistry, and ecological aspects of electrophilic reactions.
chemical carcinogens whose action is based on their
Vyacheslav Shubin was born in enzymatic oxidation to hydroxylamines, followed by
1936 in Esiplevo village, Ivanovo
region. In 1959, he graduated from the amination of DNA fragments [8–16].
Moscow State University; Candidate of Substitution of hydrogen in an aromatic ring is
ch emical scien ces since 1976; usually a two- or multistep process including intro-
Doctor of chemical sciences, Professor
since 1993. Head of a laboratory at the
duction of an intermediate functional group or an atom
Vorozhtsov Novosibirsk Institute of which is then transformed into amino group [2, 5,
Organic Chemistry, Siberian Division, 17–20]. An example is the Buchwald–Hartwig reaction
Russian Academy of Sciences. Fields of which has widely been used in the last decade to
scientific interest: theoretical and
applied problems of fine organic synthesis, chemistry of carbo-
convert aryl halides into N-substituted arylamines [20].
cations and organic cationic complexes, molecular rearrangements, The present review discusses methods of direct
“green chemistry.” electrophilic substitution of hydrogen in aromatic

1070-4280/05/4104-0473 © 2005 Pleiades Publishing, Inc.

474 BORODKIN, SHUBIN

compounds by amino group. A number of these they are distributed over partially occupied σ and p
methods have been developed in the recent years, and orbitals. To a first approximation, the energy difference
they are based mainly on the concept implying between the singlet and triplet states (∆EST) is deter-
participation of nitrenium ions 1 and cationic σ-com- mined by the diference in the energies of the two
plexes 2 as intermediates [16, 21] (Scheme 1). nonbonding orbitals (p and σ). Insofar as the σ orbital
is characterized by a greater s order, its energy is
Scheme 1. lower. On the other hand, electron repulsion and ex-
NRR'X +
NRR' + X– change interaction (Hund’s rule) favor σ,p-configura-
1 tion. The predominant existence of nitrenium ions in
the S- or T-state is important, for this factor determines
H NRR'
their reactivity toward arenes. Singlet nitrenium ions
+ +
NRR'
possess a vacant p orbital and unshared electron pair;
therefore, they can act as Lewis acids and bases. By
2
contrast, triplet nitrenium ions possess unpaired elec-
NRR'
trons which could give rise to radical processes. The
energy difference ∆EST is usually determined directly
by photoelectron spectroscopy; however, the applica-
+ H+
tion of the same method to large nitrenium ions is
difficult because of a vast number of vibrational bands
The review was aimed at analyzing and sys- which obscure electronic terms [15]. Therefore, most
tematizing the data published over the last decade on ∆EST values were obtained by quantum-chemical cal-
the direct electrophilc amination of aromatic com- culations.
pounds. Some earlier publications were also involved Up to now, quantum-chemical calculations were
if it was necessary to understand the problems under performed for a wide variety of nitrenium ions: NH+2
discussion and reveal new trends in this field. [22–40], MeNH + [22, 24, 25, 30, 36, 41], Me 2N +
[22, 24, 25, 30, 41], MeAcN + [22], (CH 2) 2N + [42],
2. ELECTRONIC STRUCTURE AND PROPERTIES (CH2)4N+, (CH2)5N+ [22, 24, 25], (XCH=CH)MeN+
OF NITRENIUM IONS (X = H, Cl) [25], (CH)2N+, CHN2+ [43], (CH)6N+ [44],
XN3+ (X = O, S, Se, Te) [45], XNH+ (X = NH2, PH2,
Let us consider the electronic structure of nitrenium OR, SH, Cl, F, Br, I, CN, NC2) [23, 27, 28, 32, 34,
ions and related electron-deficient species which are 36, 40, 46], X(CHO)N+ [X = N, NH2, PH2, OR, SH,
usually assumed to be reactive intermediates in elec- Ph(CH2)nO] [23, 47], ArNH+ [22, 23, 25, 41, 48–65],
trophilic amination of aromatic compounds. Nitrenium ArMeN+ [41, 66–69], Ar(t-Bu)N+ [25], Ph(CHO)N+
ions possess six electrons and a vacant p orbital on the [23], ArAcN+ [22, 41, 52, 56, 57], Ar2N+ [51, 52, 59,
nitrogen atom; therefore, they can exist in the singlet 61], X2N+ {X = F [27, 28, 40, 70–77], Cl, Br, I [27, 28,
(S) or triplet (T) state [15, 16, 21]. In the singlet state, 32, 40], X = NH2, PH2 [78], N2 [79–82], N3 [83, 84],
electrons with antiparallel spins occupy a σ orbital N4 [85], (CO)2 [81]}, F(OH)N+ [86, 87], FClN+ [40].
which has a lower energy than p orbital (Fig. 1) [15].
In the triplet state, the electron spins are parallel, and Unsubstituted nitrenium ion H2N+ (3) exists mainly
in the triplet state, and the energy difference between
the singlet and triplet states was estimated at 89–
p p
152 kJ/mol [22–40]. The best agreement with the
σ σ experimental value (∆EST = 125.9 kJ/mol [88]) was ob-
tained by ab initio calculations (∆EST = 125.8 kJ/mol,
p p CASSCF-MRCI + ZPVE; ∆E ST = 125.6 kJ/mol,
N σ N σ TZ2P(f,d)CASSCF(6,6)-SOCI + ZPVE [33]). Ab initio
0.1043 nm 0.1025 nm
S T H H
N 107.1° N 149.4°
Fig. 1. Schematic representation of the shape of orbitals
and their population in nitrenium ions in the singlet and H H
triplet states. 3 (S) 3 (T)

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 475

calculations [MP4(SDTQ)/6-311 + G(3d2f,2p)// MNDO calculations [22, 25] of Me2N+ ion predict
MP2/6-311 + G(3d,2p)] showed that both singlet and greater stability of triplet state (T)-6 relative to (S)-6,
triplet states of H2N+ ion have an angular structure and while the results of AM1-CI calculations [25] prefer
that the HNH angle in the triplet state is considerably the singlet state.
greater [24]. According to ab initio calculations [24, 42], the
Using the results of calculation of the potential triplet state of cyclic nitrenium ions (CH2)2N+ and
energy surface for NH2+ ion in the X3B1 state [26], (CH2)5N+ is more favorable than the singlet state,
Osmann et al. [38] found that the energy of activation while with (CH2)4N+ the situation is the reverse. Semi-
for the transformation of the angular structure into empirical MNDO and AM1-CI calculations of ions
linear is very small, 1.9 kJ/mol. Taking into account 8–11 predict greater stability of their singlet states
that this barrier is lower than the zero-point energy of [22, 24, 25]. Likewise, the opposite pattern is observed
the bending vibration, NH+2 ion may be regarded as for vinylnitrenium ion (12a) [25]. The singlet state was
quasilinear [89]. found by ab initio calculations to be more favorable
According to the calculations [22, 24, 25, 30, 36, for an analog of tropylium ion, azepinyl cation 13, as
41], the ground state of MeNH+ ion is triplet 4a with well as for cation 12b [25, 44].
a CNH angle of 151.1° [ab initio, HF/6-31G(d)], and
structure 4a is converted into linear form 4b through
a low activation barrier (E a = 4.1 kJ/mol) [24]
N
(Scheme 2). None of the configurations found for the N N
N
singlet state of MeNH+ corresponds to a minimum on
8 9 10 11
the potential energy surface; the minimum is occupied
by structure 5 with a C2v symmetry [24].
X NHX XNCHO
NMe
Scheme 2. N
H H
H 151.1° H H 12a, 12b 13 14a–14e 15a–15e
C N C N H
12, X = H (a), Cl (b); 14, 15, X = NH2 (a), PH2 (b), OH (c),
H H OMe (d), SH (e).
4a 4b
H H Study of the effect of the X substituent in nitrenium
C N ions XNH+ (14a–14e) and (OCH)XN+ (15a–15e) on
H H
the relative stability of the S- and T-states showed that
5 donor groups stabilize the singlet state to a greater

Like MeNH+, the singlet state of dimethylnitrenium NR NR

ion (S)-6 does not occupy a minimum on the potential NR
energy surface [MP2(full)/6-31G(d)], and it is readily
converted into iminium ion 7 [E a = 18.8 kJ/mol,
HF/6-31G(d)] [24] (Scheme 3). Ab initio [24] and 16a, 16b 17a, 17b 18a, 18b

Scheme 3.
H NR
H H H NR
H N H H N
C C C C
19a, 19b 20a, 20b
H H H H H
6 (S) 7
H H NR
N
C C

H 21a, 21b
H H H
6 (T) R = H (a), Ac (b).

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476 BORODKIN, SHUBIN

extent [23]. High-level ab initio calculations (QCISD, stability of ArNH+ ions increases with extension of the
B3LYP) predicted greater stability of the triplet state of aromatic π system and that the barrier to interconver-
NCNH+ [34], while HlgNH+ and Hlg2N+ (Hlg = F, Cl, sion of syn and anti isomers is fairly high [48, 55].
Br, I) were found [MP4/6-311G(2df) + ZPE] to be more According to the B3LYP/6-31G* calculations, fluori-
stable in the singlet state [27, 28]. Arylnitrenium ions nated arylnitrenium ion 31 exists in the singlet state,
16–21 are also more stable in the singlet state [22, 25, and the energy difference between the singlet and
49, 51, 53, 57]. Increase in the acceptor power of triplet states is as large as ~84 kJ/mol [58]. By con-
the substituent in the aromatic ring in nitrenium ions trast, HF/6-31G* calculations showed that the ground
22–24 destabilizes the singlet state relative to triplet state of 31 is triplet and that the energy gap ∆EST is
[25, 53, 69]. An analogous relation is observed for small (21 kJ/mol) [58].
ions 25a–25c [57]. In keeping with the results of AM1 study, the
singlet state of arylnitrenium ions R(Ph)N+ becomes
NH NMe NBu-t less stable than the triplet state as the size of the R
X substituent rises (t-Bu > H) [25]. An analogous effect
ArNCOMe is produced by rupture of conjugation between the
phenyl ring and the NR+ fragment, caused by intro-
X X Y duction of bulky groups into the ortho positions in
diarylnitrenium ions 32–34; unlike cations 32 and 33,
22a–24n 23a–24d 24a–24d 25a–25c
the triplet state of ion 34 is more stable than the singlet
22, X = NMe2 (a), NH2 (b), OH (c), MeO (d), Me (e), CHO (f), state (AM1) [51].
COOH (g), CO2Me (h), COMe (i), CF3 (j), CN (k), Cl (l),
F (m), NO2 (n); 23, X = Me (a), Cl (b), Ph (c), MeO (d); Me Me
24, X = Y = H (a); X = H, Y = Br (b); X = Ac, Y = H (c), Br (d);
25, Ar = 4-biphenylyl (a), 3-pyridyl (b), 4-pyrimidinyl (c). N Me N Me

A linear correlation between ∆EST and substituent Me Me

constants σ+ (or σR+) was revealed for ions 16a and 32 33
22a–22n. This fact suggests a strong similarity be- Bu-t t-Bu
tween arylnitrenium ions and benzyl cations in which
resonance interaction between the substituent in the N
aromatic ring and the cationic center is important [53].
Ab initio and AM1 calculations of bi- and polycyclic Bu-t t-Bu
nitrenium ions 17a, 18a, and 26–30 showed that the 34

NH
Replacement of a CH fragment in the aromatic ring
NH of arylnitrenium ion by nitrogen atom also destabilizes
the S-state relative to T, and the effect becomes
stronger in going from ortho to meta and para posi-
26 27
NH NH NH NH

NH NH N N
N
N N
35a, 35b 36a, 36b 37 38a, 38b
28 29
NH NH NH
F F
N N N N
NH N N
PrNHCO NH
N

F F 39 40 41
30 31 35, 36, 38, syn (a), anti (b).

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 477
Me value for 1,3-dimethylbenzotriazolyl cation 43 is
Me
N N –270.7 kJ/mol, which is well consistent with that
NH N found experimentally using the laser flash photolysis
N
N technique (–276 ± 13 kJ/mol) [90]. The large absolute
Me value of ∆EST may be rationalized in terms of the
H
presence of two nitrogen atoms contiguous to the
42a, 42b 43
cationic center; their lone electron pairs are involved in
42, syn (a), anti (b). conjugation, thus making the dihydrotriazolyl cation
system aromatic. The occurrence of conjugation
tions, as well as with increase in the number of nitro- therein follows from the X-ray diffraction data for salts
gen atoms introduced into the ring (cf. ions 35–41) containing cations 44–50 [91, 94–96, 98, 100]. The
[57]. A large difference in the relative free energies of nitrogen–nitrogen bonds in 44–50 have intermediate
the syn and anti isomers of ion 35 in the singlet state lengths (1.271–1.327 Å) between ordinary N–N
(21.8 kJ/mol) was explained [57] by the anomeric ef- (1.425 Å) and double N=N bonds (1.240 Å) [103].
fect and by favorable electrostatic interaction between As might be expected for charged systems, the
the NH hydrogen atom and lone electron pair on the ∆EST values change considerably if solvation of nitre-
nitrogen atom in position 2 of the syn isomer. The nium ions 16b, 25, and 35–41 with water molecules is
same factors may be responsible for the greater taken into account in terms of the SM5.42R/BPW91/
stability of syn isomer 42a relative to anti isomer 42b DZVP model; here, the singlet state is stabilized to
(∆∆Hf = 31.8 kJ/mol) [55]. a greater extent than the triplet state [57].
The singlet ground state was found for cyclic nitre- Another factor which may be responsible for the
nium ions of the dihydrotriazole (43–47) and tetra- reactivity of nitrenium ions with respect to arenes is
hydrotriazole series (48–50) [90–102]. According to the magnitude of the positive charge on the nitrogen
the BPW91/cc-pVDZ ab initio calculations, the ∆EST atom. Calculations performed by different quantum-
Et Et chemical methods (Tables 1, 2; Fig. 2) give ambiguous
electron density distribution patterns even for a single
N N N N cation. This ambiguity results in part from different
R N R' R N R
approaches to estimation of charges. Therefore, the
44a–46c 45 most reliable is to consider the charge distribution pat-

R' R' R' R' Table 1. Calculated (ab initio) charges on atoms (q) in nitre-
nium ions NHX+ and NXY+
Cl N N Cl
N N N N
1 3
N A1 B1
R R R R Ion
qN qH qX,Y qN qH qX,Y
46a, 46b
NH2+ a –0.138 0.569 –4.000 –0.280 0.642
H
N +a
NHF –0.520 0.547 –0.067 –0.449 0.655 –0.104
N
NHCl+ a –0.327 0.512 –0.815 –0.561 0.615 –0.946
N N N
R
R
N
R' NHBr+ a –0.504 0.494 –1.010 –0.608 0.595 –1.013
47a, 47b 48a–48c NHI+ a –0.749 0.471 –1.278 –0.867 0.570 –1.297
H 2N O NF2+ a –1.164 –0.082 –1.096 –0.048
Ph
Ph NCl2+ a –0.204 –0.602 –0.378 –0.689
N
N N
CH2CH2Cl NBr2+ a –0.470 –0.735 –0.572 –0.786
N N N
NH
R
N
R' NI2+ a –0.864 –0.932 –0.950 –0.975
49 50 NMe2+ b –0.120 –0.560
NMeCOMe+ b –0.131 –0.585
44, R = R' = H (a); R = Me, R' = PhCH2 (b); R = R' = PhCH2 (c); –0.546
45, R = 2,4,6-Cl3C6H2; 46, R = R' = Me (a); RR' = (CH2)5 (b);
a
47, R = H (a), OH (b); 48, R = R' = H (a), R = H, R' = MP2/6-31G(d) [28].
b
Ph (b); R = Me, R' = Ph (c); 50, R = 2,4,6-Cl3C6H2. 3-21G basis set [41].

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 4 2005

478 BORODKIN, SHUBIN

Table 2. Charges on atoms (q) in aryl-substituted nitrenium ions PhNR+

q
R Method 1 2 Reference
N C C C3 C4 C5 C6
H MNDO –0.001 –0.065 –0.233 –0.010 0.382 –0.041 –0.346 [22]
a a a
H CNDO/2 –0.123 –0.112 0.169 –0.112 [21]
H HF/3-21G –0.136 –0.220 –0.315 –0.042 0.274 –0.054 –0.230 [48]
b
H HF/6-31G(d) –0.363b a a a a a a
[55]
H DFT ESP –0.430 –0.440 –0.010 –0.120 0.160 –0.070 –0.090 [52]
C(O)Me DFT ESP –0.510 –0.540 –0.050 –0.100 0.140 –0.060 –0.150 [52]
Ph DFT ESP –0.450 –0.410 –0.100 –0.080 0.050 –0.100 –0.100 [52]
a
No data were given.
b
NPA calculations.

terns obtained in terms of a single quantum-chemical gen atom (Table 2, Fig. 2), and in many cases a con-
method. The data in Table 1 show that MP2/6-31G(d) siderable part of the positive charge is localized on
calculations of nitrenium ions XYN+ give a negative the carbon atoms in the ortho and para positions
total charge on the nitrogen atom when X, Y = H, Cl, with respect to the NR fragment. Correspondingly,
Br, I. Nonempirical calculations of arylnitrenium ions aryl-substituted nitrenium ions can act as both N- and
Ar(R)N+ also showed a negative charge on the nitro- C-electrophiles in reactions with arenes. According to
H H
N –0.242 N –0.255 H –0.210
0.066 0.295 0.136 0.323 0.198 0.266 0.208 0.352
N –0.202 N
0.152 0.313 0.160 0.227 0.053 0.052 H
0.255 0.248
0.067 0.023 0.060 0.038 0.194 0.212 0.189 0.139

0.177 0.312 0.179 0.299 0.072 0.104 0.072 0.126

17a 17a' 18a 18a'

0.132 0.046 0.127 0.067

0.051 0.265 0.051 0.188

0.140 0.140 H
N –0.236 N
0.024 0.172 0.130 0.025 0.175 0.206 –0.238
H
19a 19a'
Ac H H
N N N
0.287 0.083 0.156 0.179
N
–0.019 Ac –0.028 –0.063
0.230

0.164 0.135 0.286 0.218

Ph
0.103

Ph
17b 18b 26a 21a

Ph
H –0.415
H –0.553 –0.476
N N N
N N N
0.006 0.114 0.202
N N N –0.499
H H H
44a 47a 48b

Fig. 2. Calculated Mulliken charges (HF/3-21G; ions 17a, 18a, and 19a) [48] and charge densities (RHF/6-31G*; ions 17b, 18b, 21a,
26a, 44a, 47a, and 48b) [56, 100].

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 479

the UHF/6-31G(d) calculations, the nitrenium nitrogen Scheme 4.

atom in dihydro- and tetrahydroimidazolyl cations pos- Catalyst
PhNH2 + NH2Cl o-C 6H4(NH2)2
sesses a positive charge [100] (Fig. 2).
+ p-C6H4(NH2)2 + PhNHNH2
3. AMINATION OF ARENES WITH VARIOUS
REAGENTS An unusual orientation was observed in the amina-
tion of benzene derivatives with NHCl2 or NCl3 in
Among up-to-date methods for building up new the presence of AlCl3: m-toluidine was obtained from
Carom–N bonds, electrophilic amination attracts a keen toluene (yield 25 and 42%, respectively), m-chloro-
interest, for it makes it possible to introduce in one aniline from chlorobenzene, and 3,5-xylidine from
step various amino groups into an aromatic ring [104]. m-xylene [107, 108]. This reaction direction was
As synthetic equivalents of nitrenium ions, amines rationalized in terms of the addition–elimination mech-
having readily departing groups, such as RR'N–Cl, anism involving initial attack by Cl+ ion on the sub-
RR'N–OR, and RR'N–SO 3 X may be used. More strate and subsequent addition of NCl2– anion [109]
complex compounds whose transformations give rise (Scheme 5). The yield of toluidine in the reaction of
to R1R2N+ ions, e.g., RN3, R1OCON=NCOOR2, and NCl3 with toluene was shown to depend on the nature
R1R2N–NR3R4, can also serve as a source of N-cen- of the Lewis acid (AlCl3, 42%; AlBr3, 25%; SbCl5,
tered electrophilic species. These cations can be 3%; SnCl4 and FeCl3, 0%) and solvent (o-C6H4Cl2,
generated by photolysis of N-aminopyridinium and 34%; 1,2,4-C 6 H 3 Cl 3 , 30%; H 2 O, 30%; SnCl 4 , 8;
S-aminosulfonium salts and their analogs. In the MeNO2, Et2O, and Et3N, 0%) [108].
further treatment, the data are classified with respect to
the type of the aminating agent. Scheme 5.
NCl3 + AlCl3 Cl3N · · · AlCl3
3.1. N-Halo Amines δ+
Cl Cl2NAlCl3
δ–

N-Halo amines have long been used as reagents for X X X

amination of aromatic compounds (see [105–109] and –
Cl+ NCl2
references therein). The amination of benzene, toluene,
tert-butylbenzene, N,N-dimethylaniline, and naphtha- H
lene with chloro(dimethyl)amine in nitromethane or NCl2
Cl H Cl H
nitropropane in the presence of AlCl3 gave the corre- X X
sponding dimethylamino-substituted arenes in 90, 54,
47, 21, and 32% yield, respectively [105]. Using 2 H+
toluene as an example, it was shown that the isomer –HCl –2 Cl+
ratio of the resulting toluidines (ortho : meta : para = NCl2 NH2
14 : 27 : 59) [105] corresponds to electrophilic character X = Me, Cl.
of the process. Chloro(dimethyl)amine reacts in a sim-
ilar way with benzene, toluene, tert-butylbenzene, As noted above, the presence of at least one power-
chlorobenzene, and naphthalene in the presence of ful donor substituent on the nitrogen atom increases
96% H2SO4; in the reaction with toluene, the fraction the stability of nitrenium ion, its singlet state being
of meta-toluidine among isomeric toluidines is con- stabilized to a greater extent than the triplet state.
siderably greater (ortho : meta : para = 9 : 53 : 38) [106]. Singlet N-acyl-N-methoxynitrenium ions are the most
The amination of benzene was also effected with other probable intermediates in reactions of N-chloro-N-
dialkyl(chloro)amines R2NCl [R = Me, Et, Pr; RR = methoxycarboxamides with arenes catalyzed by Lewis
(CH2)5] and catalysts (FeCl3, AlCl3/FeSO4, H2SO4– acids [111–113]. Reactions of N-chloro derivatives
AcOH) [105, 106]. 51a–51d with benzene and substituted benzenes PhX
Belen’kaya et al. [110] showed that chloroamine (X = Me, MeO, CO2Me), as well as with p-xylene and
reacts with aniline in nonaqueous solvents (diethyl naphthalene lead to formation of the corresponding
ether, 1,2-dichloroethane, chlorobenzene) in the pres- electrophilic amination products in high yields [111,
ence of acid catalysts (AlCl 3, KU-23 sulfo cation 112] (Scheme 6). Here, the observed orienting effect of
exchanger, AcOH) to afford o- and p-phenylenedi- the substituent conforms to that typical of electrophilic
amines in a low yield (15–20%; Scheme 4). aromatic substitution [112].

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 4 2005

480 BORODKIN, SHUBIN

Scheme 6. by the nitrenium center on the carbon atom attached to

O O chlorine, followed by migration of chlorine in ion C.
Ag2CO3, CF3COOH
ArH + OMe OMe Kikugawa et al. [113, 114] showed that anhydrous
R N R N
Zn(OAc)2 in nitromethane effectively catalyzes (as
Cl Ar
Lewis acid) cyclization of N-chloro-N-methoxycarbox-
51a–51d 52a–52d
amides obtained from the corresponding N-methoxy
R = Me(CH2)6 (a), Ph (b), t-BuO (c), PhCH2O (d). amides 57–61 by the action of t-BuOCl. The yield of
heterocyclic products 62–66 strongly depended on the
Obviously, nitrenium ions are formed as inter- initial amide structure (Schemes 9–13). N-Chloro-N-
mediates in intramolecular cyclization of N-chloro-N- methoxy-p-methoxyphenylacetamide (67) gave rise to
methoxy amides 53a–53i, which is promoted by AgX two regioisomeric compounds 68 and 69, presumably
(X = BF4, OAc, OCOCF3, OSO2CF3), Ag2X (X = CO3, via intermediate formation of nitrenium ion D [113]
SO4), or FeSO4 [111, 112] (Scheme 7). The yield of (Scheme 14).
1-methoxy-1,2,3,4-tetrahydroquinolin-2-one (0–87%) The yield of compounds 71a–71f in the cyclization
from amide 53n strongly depends on the nature of the of N-alkoxy-N-chloro amides 70a–70f (Scheme 15)
salt and solvent and reaction conditions [112]; partic- depended on the Lewis acid and solvent nature; the
ipation of nitrenium ions in this process follows from best results were obtained with the use of AgBF 4
the data obtained for deuterium-labeled compound 53g in Et 2O or THF [115]. The presence of a methoxy
[112] (Scheme (8). The formation of a considerable group in the para position of the benzene ring in
amount of compound 55 was interpreted [112] in terms amides 72a–72c favored formation of spiro com-
of rearrangement of ion A to ion B via 1,2-hydrogen pounds 73a-73c through intermediate nitrenium ions
shift and subsequent elimination of deuteron (D+), [47, 115] (Scheme 16). Glover et al. [116] used deute-
while indenone 56 was presumed to arise from attack rated N-chloro-N-(2-phenylethoxy)acetamide (74d) to
Scheme 7.
1
R R1 R1
R2 (CH2)n O + – R2 (CH2)n O R2
MmXp ( )n
O
N N
R 3
Cl OMe R 3
OMe R3 N

R 4
R 4
R4 OMe

53a–53o

n = 1, R1 = R2 = R3 = R4 = H (a); R1 = R2 = R4 = H, R3 = Me (b); R1 = Cl, R2 = R3 = R4 = H (c); R1 = R2 = R3 = H, R4 = Cl (d); R1 =

Br, R2 = R3 = R4 = H (e); R1 = R2 = R3 = H, R4 = Br (f); R1 = Cl, R2 = R3 = H, R4 = D (g); R1 = R4 = H, R2 = R3 = MeO (h); R1 = R2 =
R4 = H, R3 = Cl (i), R1 = R2 = R4 = H, R3 = Br (j); R1 = R2 = R4 = H, R3 = Me (k); R1 = R2 = R4 = H, R3 = NHCOMe (l); R1 = R2 =
R4 = H, R3 = NO2 (m); n = 2, R1 = R2 = R3 = R4 = H (n); n = 3, R1 = R2 = R3 = R4 = H (o).

Scheme 8.
Cl Cl Cl
O D
Ag2CO3, CF3COOH
O + O + O
N
Cl OMe N N N

D D OMe OMe Cl OMe

53g 54 55 56

Cl Cl
D
O O O
N N N
H D H Cl
D OMe OMe OMe
A B C

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 481

Scheme 9.
H
N (1) t-BuOCl
OMe (2) Zn(OAc)2, MeNO2
O
O 57–83%
R R N
OMe
57a–57d 62a–62d
R = H (a), Me (b), MeO (c), Ph (d).

Scheme 10.
O
X OMe (1) t-BuOCl X
N (2) Zn(OAc)2, MeNO2
H
73–94%
N O
OMe
58a–58c 63a–63c

X = CH2 (a), CH2CH2 (b), O (c).

Scheme 11.
CONHOMe MeO O

Ph (1) t-BuOCl N
(2) Zn(OAc)2, MeNO2
87%

59 64

Scheme 12.
MeO O
CONHOMe N
(1) t-BuOCl
(2) Zn(OAc)2, MeNO2
87%

60 65

Scheme 13.
RO O
N
(1) t-BuOCl ( )n
(CH2)nCONHOR
(2) Zn(OAc)2, MeNO2
61–95%

61a–61c 66a–66c

n = 1, R = Me (a); n = 2, R = Me (b), Et (c).

Scheme 14.
O
O
CH2CONClOMe CH2CONOMe MeO N
N OMe
Zn(OAc)2 OMe
MeNO2
68

MeO

OMe OMe OMe O

N
67 D
OMe
69

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482 BORODKIN, SHUBIN

Scheme 15.
O ( )n
RO Lewis acid X
N R'
N
Cl Y
70a–70f 71a–71f

70, R = Ph(CH2)2, R' = Ph (a), Me (b); R = Ph(CH2)3, R' = Ph (c); R = Me, R' = PhCH2 (d), Ph(CH2)2 (e), Ph(CH2)3 (f); 71, n = 2,
X = O, Y = PhCO (a), MeCO (b); n = 3, X = O, Y = PhCO (c); X = CO, Y = MeO, n = 1 (d), 2 (e), 3 (f).

Scheme 16.
MeO MeO MeO
O O COR

O O N
( )n N R ( )n N R
( )n O
Cl +
Ag
72a–72c

O
COR
N

( )n O
73a–73c

n = 2, R = Me (a), Ph (b); n = 3, R = Ph (c).

Scheme 17.
(CH2)nON(Cl)COMe (CH2)nONCOMe

Ag+, Et2O

X X
74a, 74d–74f

O O
N N
COMe COMe
n=2 H –H+

X X

O O O
COMe COMe
N N
N ~1,2-C
COMe
n=3 –H+
H

X X X

n = 2, X = H (a), D (d); n = 3, X = H (e), D (f).

demonstrate that the cyclization occurs via direct chain involves mainly ipso attack by the nitrenium
attack at the ortho position of the benzene ring to center on the aromatic ring, followed by 1,2-C–C shift
afford 3,4-dihydro-1H-2,1-benzoxazine (Scheme (17). (Scheme (17) [116]. N-Chloro-N-methoxybenzamide
By contrast, the cyclization of N-chloro-N-(3-phenyl- (75) reacts with benzene or toluene (PhX, X = H, Me)
propoxy)acetamide (74e) having a longer hydrocarbon in diethyl ether in the presence of AgBF4 to give

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 483

intermolecular amination product 76 (X = H, yield nitrenium ions which are capable of reacting at both
49%) or a mixture of isomers 77 and 78 (X = p-Me, nitrogen and carbon atoms due to considerable charge
m-Me; yield 24 and 20%, respectively; Scheme 18) delocalization over the aromatic ring. Amination of
[115]. In the reaction with toluene, the ortho/para ratio arenes PhX with N-phenylhydroxylamine in a mixture
conforms to that typical of electrophilic aromatic sub- of trifluoroacetic and polyphosphoric acids (TFA–
stitution, indicating participation of nitrenium ion E. PPA) [118] involves both N- and C-attack by phenyl-
nitrenium ion on the substrate (Scheme 21), and the
Scheme 18. logarithms of the relative substitution rate constants
Cl are linearly related to the substituent constants σ+. The
AgBF4
N Ph N Ph large absolute ρ+ values for the N- and C-attack (–5.2
MeO MeO
and –4.0, respectively) are consistent with participation
O O of nitrenium ion in the rate-determining stage. Ad-
75 E dition of polar solvents to TFA–PPA was found to
C 6H 4X increase the regioselectivity of amination of anisole
PhX
N Ph and toluene with 4-tolylhydroxylamine [119]. The
MeO
direction of amination of benzene with N-phenyl-
O
hydroxylamine depends on the acidity of the medium
76–78 [120]. The reaction catalyzed by trifluoroacetic acid
76, X = H; 77, X = p-Me; 78, X = m-Me. gives mainly diphenylamine, while in the presence of
a stronger acid, CF3SO3H, p- and o-aminobiphenyls
The above intramolecular cyclizations of N-halo are formed. These results were interpreted assuming
amines occurred in the presence of Lewis acids. No that the reaction in CF3CO2H involves intermediate
such transformations are likely to be possible in the formation of phenylnitrenium ion F (Scheme 22)
absence of a catalyst. Lee et al. [117] recently showed whereas trifluoromethanesulfonic acid gives rise to
that reactions of trifluoroacetic acid with N-chloro dication G (protonated nitrenium ion) which reacts
amines 79 and 80 give only the corresponding electro- with benzene according to a different scheme.
philic chlorination products 81 and 82 (Scheme 19). It should be noted that the direction of acid-cata-
lyzed condensation of 2-methoxy-5-tert-butylphenyl-
Scheme 19. hydroxylamine (83) with p-tert-butylphenol (84)
OMe OMe almost does not depend on the acidity of the medium.
CF3COOH The reactions catalyzed by CF3CO2H, p-TsOH, and
Me CDCl3, (Boc)2O Me
CF3SO3H give the same product (85, Scheme 23)
N N
( )n Cl ( )n OCOBu-t [121]. Under catalysis by K-10 clay and its cation-
Cl
exchanged forms (Al3+, Fe3+, Cr3+, Co2+, Mn2+, Ni2+,
79, 80 81, 82 Cu2+, Ti4+, Zr4+), N-phenylhydroxylamine is converted
into p-nitrosodiphenylamine in 79–100% yield [122].
79, 81, n = 4; 80, 82, n = 11. The fact that the process was not accompanied by
the Bamberger rearrangement was explained by the
3.2. Reagents like R2N–OX layered structure of the catalyst which hinders attack
on the ortho position. Decomposition of N-phenoxy-
Like N-halo amines, R 2N–OX reagents exhibit benzamides 86a–86j by the action of AlCl3 yields
ambident reactivity: depending on the conditions and mainly ortho-substituted phenols 87a–87j (Scheme 24)
nature of the R and X substituents, heterolytic dis- [123]. The authors believe that a concerted mechanism
sociation of the N–O bond could give rise to either of the rearrangement is hardly probable and that the
nitrenium (R2N+) or oxenium ions (OX+) (Scheme 20). reaction involves participation of nitrenium ions. By
Moreover, ambident reactivity is also intrinsic to contrast, the reaction of amide 86a with a mixture of
nitrenium ions formed during the process, e.g., to aryl- Brønsted acids CF3CO2H and CF3SO3H in benzene
Scheme 20. afforded 2- and 4-hydroxybiphenyls 88a (6%) and 88b
R2N+ + OX–
(3%) and 43% of 2-hydroxyphenyl benzoate (89),
R2N–OX indicating intermediate formation of oxenium ion H
R2N– + OX+ (Scheme 25) [123].

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484 BORODKIN, SHUBIN

Scheme 21.
+δ'
NHPh
H NHPh
N-attack
+δ
–H+
NHOH NHOH2 NH
X X
H+
HN
NH2 NH2
+δ'
H C 6H 4X
C-attack
+
–H+
+δ

C 6H 4X
X

Scheme 22.
NHOH NHOH 2 NH NHPh
H NHPh
+
H PhH
–H+

NH2

NHOH2 NH2OH 2 NH 2
H H
+ PhH
H NH2
+
–H2O

G
NH2 NH 2
Ph
H+
+

Ph

Scheme 23.
Bu-t Bu-t Bu-t Bu-t

H+
+
NHOH N
H
OMe OH OMe OH
83 84 85

Acyloxy groups OCOR are classed with so-called C-paths to afford secondary and primary amines 91
readily departing groups; therefore, heterolytic dis- and 92, respectively (Scheme 26) [124]. Methanolysis
sociation of the N–OCOR bond in polar solvents of 2-acetylaminofluorene N-sulfate (93) in the pres-
usually gives the corresponding nitrenium ion. For ence of aniline resulted in formation of amines 94–97
example, it is believed that solvolysis of 4-N-(pivaloyl- (Scheme 27) [125]. Novak et al. [126] presumed
oxy)-2-aminocarboline (90) in aqueous acetonitrile formation of ion pairs by nitrenium cation and appro-
occurs through nitrenium ion I which reacts with the priate counterion in the solvolysis of N-pivaloyloxy-2-
amine formed during the process along both N- and acetylaminofluorene (98) and 4-acetylaminobiphenyl

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 485

Scheme 24.
Cl3Al NHCOPh
ONHCOPh O OAlCl2 COPh
N Al
AlCl3 AlCl3
–HCl H

X, Y X, Y X, Y
86a–86j

OAlCl2 OH
COPh
N H 2O NHCOPh
Al
–HCl

X, Y X, Y
87a–87j

86, Y = H, X = H (a), 3-F (b), 2-Cl (c), 3-Cl (d), 4-Cl (e), 2-Me (f), 4-Me (g); X = 2-Cl, Y = 4-Cl (h); X = 2-F, Y = 5-Br (i); X = 2-Br,
Y = 5-Br (j); 87, Y = H, X = H (a), 4-F (b), 3-Cl (c), 4-Cl (d), 5-Cl (e), 3-Me (f), 5-Me (g); X = 3-Cl, Y = 5-Cl (h); X = 3-F, Y =
6-Br (i); X = 3-Br, Y =6-Br (j).

Scheme 25.
H
N Ph
O O
CF3COOH–CF3SO3H O
86a H + PhCONH2

H
OH OH OH
Ph OCOPh
C6H6, H2O
+ +

Ph
88a 88b 89

Scheme 26.
H H
N N NHOCOBu-t N N NH
H2O, MeCN

90 I
H H
N N N
N-attack
H
N N NH2
H 2N N N
H
91
H
H 2N N N

C-attack

N N NH2
H
92

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486 BORODKIN, SHUBIN

Scheme 27.
NHPh
NHAc NHAc
N-path
+
–
OSO3
NHPh
N 94, 17% 95, 5%
Ac MeOH, PhNH2
C6H4NH2-p
N NHAc
93 C-path Ac
+
C6H4NH2-p
96, 20% 97, 9%

Scheme 28.
OCOBu-t C6H4NH2-p
N N NHAc
Ac CD3OD, PhNH2 Ac
+
NHPh
98 100, 17% 101, 13%
NHPh
NHAc
+

102, 5%

Ac OSO3H Ac NHPh Ac C6H4NH2-p Ac H

N N N N
NHPh
CD3OD–PhNH 2
+ +

Ph Ph Ph Ph
99 103, 2.1% 104, 2.3% 105, 9%
Ac H Ac H
N N
C6H4NH2-p
+ +
C6H4NH2-p
Ph Ph
106, 1.8% 107, 2%

N-sulfate (99) in CD3OD–PhNH2, which gave N- and (115, demethylation product) which were likely to be
C-substitution products 100–107 (Scheme 28). N-Al- formed through intermediate σ-complex J [128]
koxycarbonyloxy-4-methoxyanilines 108a–108c react (Scheme 31). An analogous mechanism involving
with N-methylaniline in THF to form 28–30% of formation of spirocyclic intermediates is typical of
2-methyl(phenyl)amino-4-methoxyaniline (109) [127] reactions of N-methoxy amide 116 [129], 3-aryl-N-
(Scheme 29). In the reaction with meta-methoxy methoxypropionamides 117, and N-(3-arylpropionyl)-
derivative 110 in CF3CO2H, two isomeric products 111 phthalimides 118 with bis(trifluoroacetoxy)-λ3-iodanyl-
and 112 were obtained [128] (Scheme 30). A different benzene or hydroxy(tosyloxy)-λ 3-iodanylbenzene
reaction direction was observed for para-metoxy (HTIB) [130–134] (Schemes 32–34). Spirocyclic inter-
derivative 113. In this case, the products were mediate K is likely to be the key structure in the
6-methoxy-2-methyl-1,2,3,4-tetrahydroquinoline (114) thermal rearrangement of isoxazolidines 119a–119i to
and 6-hydroxy-2-methyl-1,2,3,4-tetrahydroquinoline amines 120a–120i (Scheme 35) [135].

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 487

Scheme 29.
H OCOR
N NH2 Me
N
PhNHMe, THF Ph

OMe OMe
108a–108c 109

R = Me (a), t-Bu (b), PhCH2NHCHMe (c).

Scheme 30.
Me
MeO MeO
NHOH CF3COOH
+
N Me N Me
H H
MeO
110 111, 60% 112, 10%

Scheme 31.
MeO
MeO HO
CF3COOH
+

MeO Me NHOH HN N Me N Me
H H

113 J 114, 8% 115, 20–35%

Scheme 32.
MeO MeO MeO
(CF3COO)2IPh
N N N
MeO COBu-t MeO COBu-t MeO · · COBu-t
MeO N
CH2CONHOMe CH2CONOMe
116 O

MeO MeO
COBu-t COBu-t
N N
N –H+ N
MeO MeO
MeO MeO
O H O

Scheme 33.
R R' R R' R R'
X R X X
Y R' (CF3COO)2IPh Y Y Y
or HTIB O O O
N N + N
Z HN O Z OMe O OMe O OMe
X
MeO
117

HTIB is [hydroxy(tosyloxy)-λ3-iodanyl]benzene.

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488 BORODKIN, SHUBIN

Scheme 34.
X X
(CF3COO)2IPh
or HTIB O
N
Y HN O O R

R
118

117, X = H, Me, i-Pr, MeO, F, Cl; Y = H, Me, F, Cl; Z = OH, MeO, F, Cl, Br; R = H, Me, Bu; R' = H, Me, Bu, PhCH2;
118, R = phthalimido, X = H, Y = MeO, Cl, F; X = Y = F.

Scheme 35.
X X
X
O
O
O
N N N CN–
N CN N N
O
O
Y CN – O
Y
Y
119a–119i K
X

N N
–HCN

Y
120a–120i

119, 120, Y = H (a), X = OEt (a), H (b), Cl (c), NMe2 (d), NO2 (e); X = H, Y = CN (f), MeO (g); X = EtO, Y = MeO (h), CN (i).

3.3. Hydrazoic Acid and Azides acidic systems (HSO 3F–SbF 5, HF–SbF 5, HF–BF 3)
gives aminodiazonium ions L and M rather than
Unlike R2N–Hlg and R2N–OX reagents, azides and iminodiazonium ions N (Scheme 36).
hydrazoic acid exhibit no ambident reactivity in the Presumably, elimination of nitrogen molecule from
amination processes. Mertens et al. [136] showed by aminodiazonium ions should lead to the corresponding
1
H, 13C, and 15N NMR spectroscopy that protonation of nitrenium ions. However, the use of hydrazoic acid and
hydrazoic acid or azides RN3 (R = Me, Et) in super- superacidic systems is not convenient, so that azides

Scheme 36.
H H
N1 N2 N3 N1 N2 N3
R R
HSO3F–SbF5–SO2ClF L M
1 2 3 1 2 3
N N N N N N
R R H
1 2 3
N N N
R
N

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 489

Scheme 37.
NaN3 + AlCl3 AlCl2N3 + NaCl

AlCl2N3 + 2 HCl H2NN2 AlCl4 NH2 AlCl4 + N2

O P

H H
O N N NH2 NH2 N N
or

Xn Xn Xn
Q R

H
NH2
P NH2

Xn Xn Xn
S

and Lewis acids are usually employed as aminating tions of such σ-complexes derived from methyl-sub-
agents. The system NaN3–AlCl3–HCl was shown to be stituted benzenes (o-xylene, mesitylene, durene, and
quite convenient for the amination of arenes [136]. The pentamethylbenzene) showed that structures like Q are
best yields of amines were obtained from benzene and less stable than the corresponding structures like R;
arenes having electron-donor substituents (benzene, therefore, participation of the former seems to be un-
63%, anisole, 49%; toluene, 73%; p-xylene, 70%; mesit- likely [139]. σ-Complexes R are characterized by
ylene, 78%; isodurene, 39%), while in the presence of a very long H2N–N bond (~3 Å), i.e., they are similar
electron-acceptor groups in the benzene ring, the yields to σ-complexes S. The latter can be formed via direct
were considerably lower (chlorobenzene, 25%; nitro- reaction with the nitrenium ion arising from aminodi-
benzene, 2%). In the above reactions, the aromatic azonium ion O via elimination of N2 [139]. As noted
substrate was simultaneously the solvent. Replacement above, the ground state of nitrenium ion NH2+ is triplet
of excess arene by hexane led to reduced yield of the (3NH+2 ). Insofar as the formation of σ-complexes like S
amine, whereas 1,2-dichloroethane and nitromethane requires singlet state of nitrenium ion, the conversion
turned out to be inapplicable as solvents because of of arene should depend on the probability for S →T
strong complex formation with the catalytic system. inversion of that ion. This probability increases with
By contrast, we showed in [137–139] that the use of rise in the number of heavy atoms in solvent molecule
hexane and 1,2-dichloroethane as solvents in the and increase in their atom number. In fact, the conver-
amination of mesitylene ensured, respectively, a mod- sion of mesitylene and o-xylene in the amination with
erate (40%) and high (86%) yields of 2,4,6-trimethyl- NaN3–AlCl3–HCl decreases in the series CH2Cl2 >
aniline. CHCl 3 > CCl 4 , ClCH 2 CH 2 Cl > ClCH 2 CCl 3 , and
Scheme 37 illustrates the most probable mechan- CH2Cl2 > CH2Br2, in keeping with the participation of
isms of amination of arenes with the system NaN3– NH2+ as reactive species. Obviously, the rate-determin-
AlCl 3–HCl [136, 138, 139]. According to [136], ing stage in the amination is formation of σ-complex S.
sodium azide initially reacts with AlCl3; therefore, Taking into account polar character of the latter, the
solvents capable of strongly interacting with AlCl3 conversion (η) of methylbenzenes should depend not
should inhibit the process. In fact, using mesitylene as only on the number of heavy atoms (N) in solvent
an example, we showed [138, 139] that solvents with molecule but also on the dielectric constant (ε) of
a large Gutmann donor number (>2), such as THF, sul- the solvent. This is supported by the existence of the
folane, MeNO2, and PhNO2, afford a very poor yield following two-parameter correlations for the reactions
of 2,4,6-trimethylaniline (<4%). In the second stage, with mesitylene (MsH) and o-xylene (o-XyH) [139]:
protonation of AlCl2N3 gives aminodiazonium ion O
which loses nitrogen molecule to produce nitrenium η(MsH) = (0.29 ± 0.08) + (0.067 ± 0.010)ε
ion P. Reaction of the latter with arene could give rise – (0.107 ± 0.023) NCl;
to σ-complex Q or R. AM1 quantum-chemical calcula- r = 0.97, s = 0.08, n = 9;

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 4 2005

490 BORODKIN, SHUBIN

η(o-XyH) = (0.40 ± 0.10) + (0.059 ± 0.012)ε and acidic medium, which hampers formation of
– (0.143 ± 0.027) NCl; a complex between 18-crown-6 and NH2+. According
r = 0.96, s = 0.1, n = 7. to the AM1 calculations, the crown ether cavity readily
accommodates NH2+ ion, thus producing a quite strong
Nitrenium cation NH2+ generated in the amination complex (∆∆Hf = 296.6 kJ/mol) [139].
of arenes is a very reactive intermediate species. This
follows from the calculated logarithm of the partial We recently studied the effect of Lewis acids in the
rate factor (log fp) and selectivity factor [Sf = log(fp/fm), amination of mesitylene and o-xylene with the systems
where fm and fp are, respectively, the partial substitu- NaN3–MHlgn–HCl [140, 141]. The examined Lewis
tion rate factors at the meta and para positions) for the acids can be ranked as follows with respect to their
amination of toluene with the system NaN3–AlCl3– efficiency: GaCl3 ~ ZrCl4 ~ AlCl3 > AlBr3 > FeCl3 >
HCl: log fp = 0.97, Sf = 0.75; these values approach SbCl5 >> SnCl4, TiCl4 > SbCl3, GeCl4.
those found for the alkylation of toluene with MeBr– According to Takeuchi et al. [142], the amination of
GaBr3 and EtBr–GaBr3 [139]. The high reactivity of arenes with hydrazoic acid in a CF3SO3H–CF3CO2H
NH 2+ is responsible for the low selectivity in the mixture (1 : 3, by volume) yields primary arylamines
amination of arenes [139]. An attempt to increase the without formation of appreciable amounts of diamines.
selectivity in the amination of o-xylene by complex The authors presumed that the reaction follows a con-
formation of NH2+ with 18-crown-6 was unsuccessful: certed mechanism involving attack by protonated hy-
the isomer ratio of 2,3- and 3,4-dimethylanilines did drazoic acid H2N3+ on the substrate with simultaneous
not change to an appreciable extent [139]. Presumably, elimination of nitrogen (Scheme 38). The yield of
the reason is strong interaction between 18-crown-6 arylamines depends on the intial arene: it decreases

Scheme 38.
H
H H NH2
H+ C 6H 6 – nX n δ+ δ+ NH2
HN3 N N2 N N2
–H+ –N2
H H
Xn Xn Xn

Scheme 39.
N3 HN HN
N N – N
H+ CF3SO3
–N2
S S S
OSO2CF3
121 T H
H 2N
N

S
OSO2CF3
123

N3 NH NH
N H+ N CF3SO3– N
+
–N2
S S S
H
122 U OSO2CF3
NH2
N

S
CF3SO2O
124

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 491

Scheme 40.
N N
H+
N3 NH
–N2
R X X

125, 126

N
NH
125, 126 R X
H
H
N
N3
X R

N N
NH2 NH2
R X CF3SO3H R X
N N
N3 HN
X R X R

N
NH2
H 2O R X
N
H 2N
X R
Y
127, 128

R = H, Me; X = O, S; Y = H, OSO2CF3.

upon introduction of electron-acceptor substituents between intermediate nitrenium ion PhNH+ and depart-
into the benzene ring. No reaction occurs in the ing water molecule.
absence of CF 3SO 3H, indicating the necessity of Reactions of 2-(2-azidophenyl)- and 2-(3-azido-
a strongly acidic medium to protonate HN3. phenyl)benzothiazoles 121 and 122 with CF3SO3H
Reaction of BuN3 with benzene or mesitylene in give rise to π-nitrenium ions like T and U which are
CF3SO3H–CF3CO2H leads to formation of the corre- trapped by trifluoromethanesulfonate ion to give tri-
sponding N-arylbutylamine in a relatively poor yield fluoromethylsulfonyl-substituted arylamines 123 and
(5 and 21%, respectively) [142]. Contrastingly, amina- 124 [144] (Scheme 39). Analogous reactions of 2-(4-
tion of benzene, methylbenzenes, and halobenzenes azidophenyl)benzothiazoles and 2-(4-azidophenyl)ben-
with trimethylsilyl azide in CF3SO3H affords aryl- zoxazoles 125 and 126 lead to formation of symmetric
amines in a relatively high yield (73–96%) [143]. The or unsymmetric benzazolyl-substituted 2,2'-diaminobi-
amination of monosubstituted benzenes with all the phenyls 127 and 128 [144] (Scheme 40).
examined azides in acidic medium gives mainly the Photochemical amination of benzene and substi-
corresponding ortho and para isomers, in keeping with tuted benzenes with tetrazolo[1,5-a]pyrimidine in the
electrophilic character of the reactive intermediate. presence of CF3CO2H afforded substituted anilinopyri-
Analogous relations are typical of reactions of mono- midines, as well as 2-aminopyridine, biphenyl, and
substituted benzenes with PhN3 in CF3CO2H, the ρ+ diarylmethanes [145] (Scheme 41). While considering
value in the Hammett equation (–4.5 at 25°C) being the heavy-atom effect of the solvent, the authors pre-
somewhat greater than in the amination with PhNHOH sumed that substituted anilinopyrimidines are formed
(ρ+ = –5.2 at 20°C) [118]. In the latter case, the higher through intermediate nitrenium ion V in the singlet
selectivity is likely to result from specific interaction state and that aminopyrimidine, biphenyl, and diaryl-

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492 BORODKIN, SHUBIN

Scheme 41.

N N N N N N
H
N N PhX
NH + NH + NH
Y– Y– –H+
N N N N H X
N N V (S)
N
HY hν X
N N –N2 X
PhH
N N PhH Ph · Ph Ph
H
N N N H· N
– – +
Y Y · –H
N N3 N N H · N NH2 N NH2
ArCH2Z ArCHZ
V (T)
X
CHZAr

Y = CF3COO, X = H; X = Me, Ar = Ph, Z = H; X = Et, Ar = Ph, Z = Me; X = MeO, Cl.

Scheme 42.
H
CF3SO3H N
CF3COOH
(CH2)9 N3
HN (CH2)9
(CH2)9
129 134, 44%

Scheme 43.

H
CF3SO3H N
CF3COOH
S
S(CH2)n N3
HN (CH2)n S
(CH2)n
130 (n = 7, 9) 135, 32% (n = 7), 16% (n = 9)

Scheme 44.
CF3COOH
(CF3CO)2O
N3 HN HN H

O O (CF3CO)2O O
131

H
CF3CONH H CF3CONH

O O
136, 46%

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 493

Scheme 45.
H2N
CF3SO3H
CF3COOH
N3

132 137

Scheme 46.
COOEt COOEt

H2N
CF3SO3H, CHCl3

N3

133 138, 70%

Scheme 47.
N2 Ph Ph
Ph
Ph O Ph
SnCl4 N N N
N3 Ph Ph
N3 Ph –N2
Ph Ph
OSnCln
ClnSnO ClnSnO O
139 141, 48%

N2
N N
O N3
BF3 · Et2O N O
OBF3 OBF3
–N2 –BF3

140 142, 94%

methanes originate from the same ion but in the triplet Lang et al. [150] showed that epoxy azides 139 and
state. According to quantum-chemical calculations, the 140 undergo a series of transformations by the action
ground state of 2-pyrimidinylnitrenium ion in the gas of Lewis acids. These transformations include regio-
phase is triplet, though the energy gap between the selective amination of the aromatic ring, leading to
triplet and singlet states is small [57]. The formation nitrogen-containing heterocycles 141 and 142 as
of nitrenium ion V is supported by the existence of shown in Scheme 47.
a linear correlation between log k for the formation of
substituted anilinopyrimidines and σ+ constants of sub- 3.4. Azodicarboxylic Esters and Hydrazines
stituents X; here, the relatively low absolute value of
ρ+ (–2.9 at 25°C) indicates higher electrophilicity of Azo diesters are effective reagents for electrophilic
the singlet pyrimidylnitrenium ion as compared to amination of electron-rich aromatic compounds [151–
phenylnitrenium [118]. 158]. As a rule, Lewis or Brønsted acids are used as
It is believed that acid-catalyzed intramolecular catalyst, and the reaction gives mainly substitution
cyclization of arylazides 129 [146], 130 [147], 131 products at the para position with respect to the most
[148], 132, and 133 [149] involves intermediate forma- powerful electron-donor substituent in the aromatic
tion of the corresponding nitrenium ions (Schemes 42– ring (Scheme 48). Apart from symmetrical azo diesters
46) and that the reaction follows either N- or C-path, like 144a and 144b, diesters 148 with dissimilar ester
depending on the initial azide structure; as a result, moieties and amido esters 149a–149g were used in
compounds 134–138 are obtained. electrophilic amination of arenes 146a, 146b, and 147.

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494 BORODKIN, SHUBIN

Scheme 48.
O
H
N
R1 XO N C(O)OX
5
R 6
R 2 R R1
Catalyst
+ XOC(O)N NC(O)OX
R 5
R 3 R4 R2
R4 R3
143a–143h 144a, 144b 145a–145h

143, R1 = OH, R2 = R3 = R4 = R5= R6 = H (a); R1 = MeO, R2 = R3 = R4 = R5 = R6 = H (b); R1 = MeO, R3 = Me, R2 = R4 = R5 = R6 =

H (c); R1 = R2 = MeO, R3 = R4 = R5= R6 = H (d); R1 = MeO, R2 = Br, R3 = R4 = R5 = R6 = H (e); R1 = MeO, R2 = R3 = R5 = R6 = H,
R4 = Br (f); R1 = R3 = R5 = MeO, R2 = R4 = R6 = H (g); R1 = R3 = MeO, R2 = R4 = R6 = H, R5 = MeCO (h); 144, X = CCl3CH2 (a),
X = Et (b); 145, R1 = R2 = R4 = R5 = H, R3 = OH, X = CCl3CH2 (a); R1 = R2 = R4 = R5 = H, R3 = MeO, X = CCl3CH2 (b); R1 =
Me, R2 = R4 = R5 = H, R3 = MeO, X = CCl3CH2 (c); R1 = R4 = R5 = H, R2 = R3 = MeO, X = Et (d); R1 = R4 = R5 = H, R2 = Br, R3 =
MeO, X = CCl3CH2 (e); R1 = MeO, R2 = R3 = R5 = H, R4 = Br, X = CCl3CH2 (f); R1 = MeO, R2 = R4 = H, R3 = R5 = MeO, X =
CCl3CH2 (g); R1 = MeO, R2 = R4 = H, R3 = MeO, R5 = COMe, X = CCl3CH2 (h).

Scheme 49.
O OCH2CCl3
O
Me3Si NH
O N
MeO OMe MeO OMe
ZnCl2, CH2Cl2
+ Me3Si(CH2)2OC(O)N NC(O)OCH2CCl3

R R
146a, 146b 148

O
Me3Si NH2
O N
MeO OMe
Zn, AcOH

R
150a, 150b

As a result, unsymmetrically substituted hydrazines a large effective volume of the reagent, which hinders
150a, 150b, and 151a–151g were obtained; the prod- its attack on the ortho position.
ucts are convenient synthons for the preparation of Bicyclic compounds, such as biphenyl derivative
heterocyclic compounds [152, 156] (Schemes 49, 50). 152, substituted naphthalenes 153 and 154, and anthra-
The high regioselectivity of the amination was cene (155) can also be involved in the amination with
interpreted in terms of formation of an oriented π-com- azo diesters [152, 156, 158] (Schemes 51–54). Electro-
plex as shown in Fig. 3 [153]. Arrangement of com- philic amination of halogenated phenols 163a–163g
ponents in that complex is determined by the maximal with diisopropyl diazenedicarboxylate (164) in the
orbital coefficients of atoms in the highest occupied presence of ZrCl4 is accompanied by migration of
molecular orbital of arene, which overlaps the lower halogen atoms (“halogen dance”) to afford amines 165
unoccupied orbital of the azo reagent; the subsequent and 166 [155] (Scheme 55). In the amination of
formation of σ-complex is followed by elimination of 4-fluorophenol, chloro-substituted compound 165f was
proton [153]. An additional factor ensuring high selec- isolated; its formation was explained by migration of
tivity in the amination with azo esters is likely to be the fluorine atom and its subsequent replacement by

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 495
OH OMe OMe
O –0.48 0.47 0.36
–0.37 –0.32 0.38 0.32 0.53 0.00
RO N
N OR 0.18 0.26 –0.16 –0.26 0.00
–0.36
OMe
O 0.53 –0.52 –0.53

OMe OMe
–0.51 –0.45 –0.47
O MeO COMe Br
–0.27 –0.28 –0.40
–0.38 0.07 –0.42
R 0.29
0.00 0.52 0.12 –0.27 0.14
0.35
Me
0.50 0.52
OMe

Fig. 3. Schematic representation of the interaction between the HOMO of arene and LUMO of azo reagent in the π-complex derived
therefrom and orbital coefficients in the HOMO of some arenes.

chlorine. Groups like NXY behave as readily departing the N–N bond in N-p-tolylaminophthalimide (169) in
groups. Carbazoles 168a–168h were obtained from benzene and that p-tolylnitrenium ion thus formed
N-(diarylamino)phthalimides 167a–167h by the action reacts with benzene along the C-path to give amines
of AlCl3 [159] (Scheme (56). It was presumed that 170 and 171 (Scheme 57) [160]. Likewise, AlCl3 reacts
aluminum trichloride induces heterolytic cleavage of with phenylhydrazines 172a and 172b to produce the

Scheme 50.
OMe

OMe

ZrCl4, CH2Cl2
+ ArNHC(O)N NC(O)OR O
H
N N
Ar N OR
H
O
147 149a–149g 151a–151g, 76–93%

146, 150, R = H (a), MeO (b); 149, 151, Ar = Ph, R = Et (a), i-Bu (b); Ar = 4-MeC6H4, R = Et (c); Ar = 4-MeOC6H4, R = Me (d);
Ar = 4-FC6H4, R = Et (e); Ar = 3-ClC6H4, R = Et (f); Ar = 3,4-Cl2C6H3, R = PhCH2 (g).

Scheme 51.
O O CH2CCl3
O O
CCl3CH2 N NH

(CCl3CH2OCON)2, ZnCl2

MeO OMe MeO OMe

152 156, 100%

Scheme 52.
O OR
O
O NH
OMe XC6H4O N
OR
ZrCl4
+ N N OMe
XC6H4O
O
153 144c, 144d 157, X = 4-Me, R = Et, 86%
158, X = 4-MeO, R = Me, 95%

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496 BORODKIN, SHUBIN

Scheme 53.
O OEt
O
O NH
R EtO N
OEt
Sc(OTf)3
+ N N R
EtO
O
154 159, R = H, 78%; 160, R = Me, 85%
160, R = MeO, 90%

Scheme 54.
O OEt
O
O NH
EtO N
OEt
Sc(OTf)3
+ N N
EtO
O
155 162, 82%

Scheme 55.
OH O OH OH NHC(O)OPr-i
Y OPr-i Y X Y N
ZrCl4 C(O)OPr-i
+ N N +
i-PrO
O
X N X
i-PrOC(O) NHC(O)OPr-i

163a–163g 164 165a–165g, 5–83% 166a–166d, 10–86%

163, X = Y = Cl (a), Br (b); Y = H, X = Cl (c), Br (d), F (f), I (g); Y = F, X = H (e); 165, X = Y = Cl (a), Br (b); X = Cl, Y = H (c);
X = Br, Y = H (d); Y = F, X = H (e); X = Cl, Y = H (f); X = H, Y = H (g); 166, X = Y = Cl (a); X = Cl, Y =H (b); X = Br, Y = H (c);
X = I, Y = H (d).

Scheme 56.

O Z
H H
X Y Y
AlCl3
N N X
N Z N
O X

Z Y

167a–167h

Z
Y

N
X
168a–168h

167, 168, X = Y = Z = H (a); X = Z = H, Y = Cl (b); X = Y = H, Z = Cl (c); X = Br, Y = Z = H (d); X = Z = H, Y = Me (e);

X = Y = H, Z = Me (f); X = Z = Me, Y = H (g); X = Br, Y = Me, Z = H (h).

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 497

Scheme 57.
Me
NH NH2 NH2
O Ph
PhH
+
N NH
Ph
Me Me Me
O
169 170, 14% 171, 9%

Scheme 58.
R NH2 H Ar
N N NH2 NHR
AlCl3, ArH Ar
+ +

Ar
172a, 172b 173a–173e 174a–174g 175a–175g

172, R = H (a), Me (b); 173, Ar = Ph (a), 4-FC6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d), 2,5-Me2C6H3 (e); 174, Ar = Ph (a), 2-FC6H4 (b),
2-ClC6H4 (c), 2-BrC6H4 (d), 4-ClC6H4 (e), 4-BrC6H4 (f), 4-FC6H4 (g); 175, R = Me, Ar = Ph (a), 2-FC6H4 (b), 2-BrC6H4 (c),
2-MeC6H4 (d), 4-FC6H4 (e); 4-BrC6H4 (f), 4-MeC6H4 (g).

corresponding nitrenium ions which then react with and H2N+ [162]. The low regioselectivity in the reac-
benzene derivatives at both nitrogen and carbon tions of toluene and naphthalene with salts 176 and
centers, yielding amines 173a–173e, 174a–174g, and 177 in the presence of CF3CO2H under photolysis
175a–175g [161] (Scheme 58). conditions indicates high reactivity of MeHN+ and
H2N+ ions [162, 164]. The same also follows from the
3.5. Aminopyridinium and Aminosulfonium Salts low absolute ρ+ values in the Hammett equation for the
reaction of alkylbenzenes with nitrenium ion generated
Direct amination of arenes can be effected via gen- by photolysis of 1-amino-2-methyl-4,6-diphenylpyridi-
eration of nitrenium ions by thermolysis or photolysis nium tetrafluoroborate (ρ+ = –2.1) [162] and 1-amino-
of N-aminopyridinium and S-aminosulfonium salts and
their analogs [162–175]. A wide series of such salts R2
was examined with a view to elucidate the effect of the
cation structure and the role of counterion. Photolysis
of 1-amino-, 1-methylamino-, and 1,1-dimethylamino- R1 N R3
2-methyl-4,6-diphenylpyridinium tetrafluoroborates X
176r, 176t, and 176v in benzene or toluene in the 176a–176y
presence of CF3CO2H led to formation of aniline and
isomeric toluidines, respectively, implying participa- X = NH2; R1 = R2 = R3 = H, Y = Br (a), I (b), ClO4 (c),
MsSO3 (d); R1 = Me, R2 = R3 = H, Y = I (e); R1 = MeO, R2 =
tion of nitrenium and alkylnitrenium ions in the singlet R3 = H, Y = MsSO3 (f), ClO4 (g); R1 = R3 = H, R2 = MeO,
state [162, 166] (Scheme 59). Apart from electrophilic Y = MsSO3 (h); R1 = R3 = H, R2 = Me, Y = MsSO3 (i); R1 =
substitution products, biphenyl and phenyltolyl- R3 = H, R2 = Ph, Y = MsSO3 (j); R1 = R3 = H, R2 = MeCO,
methanes are obtained; the latter could be formed Y = MsSO3 (k); R1 = R3 = H, R2 = MeOCO, Y = MsSO3 (l);
R1 = R3 = H, R2 = CH, Y = Br (m), ClO4 (n); MsSO3 (o);
according to the radical reaction path with participa- R1 = R3 = H, R2 = NO2, Y = MsSO3 (p); R1 = R2 = Me, R3 =
tion of triplet nitrenium ion. The yields of electrophilic H, Y = MsSO3 (q); R1 = Me, R2 = R3 = Ph, Y = BF4 (r); R1 =
substitution products from toluene in the photolysis of R2 = R3 = Ph, Y = ClO4 (s); X = NHMe, R1 = Me, R2 = R3 =
salt 176v were lower than in the photolysis of 176r Ph, Y = BF4 (t); X = PhNH, R1 = Me, R2 = R3 = Ph, Y =
BF4 (u); X = NMe2, R1 = Me, R2 = R3 = Ph, Y = BF4 (v); X =
and 176t, while the fraction of phenyltolylmethanes (CH2)5N, R1 = Me, R2 = R3 = Ph, Y = BF4 (w); X = Ac(Ph)N,
was greater. This may be due to higher rate of the R1 = R2 = R3 = Ph, Y = BF4 (x); X = NPh2, R1 = R2 = R3 =
S→T conversion of Me2N+ as compared to MeHN+ Me, Y = BF4 (y).

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498 BORODKIN, SHUBIN

Me

Me Me

MeSO3– MeSO3– 2 MeSO3– Me N Me BF4–

N N N N N
Me H 2N NH2 N
NH2 Me

Ph
177 178 179 180

Ph

Y– ClO4– MsSO3– Ph N Ph BF –
4
N N N
N NH2 N
H 2N
NH2

181a–181h 182 183 184

R
Ph
R S
N N – –
BF4– S 2,4,6-Me3C6H2SO3 X NH R CF3COO
Ph
NH2
O
185 186a, 186b 187a–187d

Ph
C6H4Cl-p
N N
N Ph
N BF4– BF4–
N
N
C6H4Br-p
188 189

181, R = H, Y = Br (a), Cl (b), ClO4 (c), MsSO3 (d); R = Me, Y = ClO4 (e), MsSO3 (f); R = Cl, Y = ClO4 (g), MsSO3 (h);
186, R = Me (a), Ph (b); 187, R = X = H (a); R = H, X = Me (b), NO2 (c); R = Pr, X = NO2 (d).

quinolinium perchlorate (ρ+ = –1.9) [166]. The exist- of salt 180: the relative rate constants did not conform
ence of a linear correlation between log k and substit- to the expected stability of σ-complexes but were
uent constants σ+ for alkyl benzenes suggests a σ-com- consistent with the formation of π-complexes between
plex-like transition state. arylnitrenium ion and arene [172].
The formation of σ-complexes in electrophilic The reactivity of N-aminopyridinium salts 176 and
amination of arenes is supported by the data of [174]. 177 toward arenes in the presence of CF 3CO 2H
The electron absorption spectra of the reaction mix- strongly depends on the substituent in the pyridine ring
tures obtained in the photolysis of salt 176t in the and counterion nature [164, 167]. Electron-acceptor
presence of 1-R-3,5-dimethoxybenzenes (R = H, MeO) substituents increase the selectivity factor S f =
contained a band with its maximum at λ 330 nm, log{2[(p-toluidine)%]/[(m-toluidine)%]}. The fractions
which was assigned to 1-diphenylamino-2-R-4,6-di- of 1- and 2-aminonaphthalenes in the photolysis of
methoxybenzenium ions (R = H, MeO). By contrast, salts 176 and 177 in the system naphthalene–CF3CO2H
no evidences in favor of formation of σ-complexes also depend on the structure of the pyridinium frag-
were obtained in the reactions of activated arenes (such ment and counterion [164]. Analogous relations are
as mesitylene, 1,3,5-triethylbenzene, durene, penta- typical of quinolinium salts 181 in the system toluene–
methylbenzene, and hexamethylbenzene) with N-meth- CF3CO2H [167]. The selectivity factor decreases in the
yl-4-biphenylylnitrenium ion generated by photolysis series Cl– > Br– > MsSO3– > ClO4–, which was inter-

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 NITRENIUM IONS AND PROBLEM OF DIRECT ELECTROPHILIC AMINATION 499

Scheme 59.
PhH
Ph Ph

hν
+ NRR' NRR' Me Me
S0 T1 CH2Ph
Me N Ph Me N Ph PhMe
NRR' +
PhX

CH2Ph
NRR' NRR' NRR' NRR'
H NRR'
Me
X=H X = Me
+ +
–H+ –H+
Me
X
Me
R = R' = H; R = H, R' = Me; R = R' = Me.

preted [167] in terms of variation of the degree of and two 18-crown-6 molecules when the concentration
negative charge localization on the anion. The same of the latter exceeds that corresponding to the maximal
series, Br– > MsSO3– > ClO4– > I–, was found for the yield of aniline. This complex is likely to be less reac-
photolysis of aminopyridinium salts 176a–176e [167]. tive because of hindered approach of benzene mole-
Addition of small amounts of 18-crown-6 to a mix- cule to NH2+ ion bound into the complex [167]. The
ture of benzene with CF3CO2H in the photolysis of yield of aniline and toluidines in the photolysis of
1-aminopyridinium and 1-aminoquinolinium mesit- salts 176d and 178 in benzene–CF3CO2H or PhMe–
ylenesulfonates leads to monotonous increase in the CF3CO2H decreases on addition of heavy atom-con-
yield of aniline, presumably due to stabilization of the taining solvents (CH2Cl2, CH2Br2, CH3I), as well as in
singlet state of NH2+ ion via interaction with the crown the presence of atmospheric oxygen. Presumably, this
ether [167]. In the photolysis of the corresponding is the result of increase in the rate of S–T conversion
perchlorates, the yield of aniline initially increases and of nitrenium ion [164].
then sharply falls down. A probable reason is the Interaction of nitrenium ion with lone electron pair
formation of a sandwich-like complex between NH2+ on the sulfur atom in sulfides is weaker than with
Scheme 60.

Ph Ph
N N Ph
N N
N N Ph
N Ph N Ph
BF4– N + N
BF4– –HBF4
N
Ph N
190 192 193

Cl

R R Ar
N N
N BF4
–
N BF4
– N Ar + R
N N –HBF4 N
N N
Ar Ar N N

191 194 195

191, 194, 195, R = 4-ClC6H4, Ar = 4-BrC6H4.

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 4 2005

500 BORODKIN, SHUBIN

nitrogen lone electron pair in pyridine derivatives; Scheme 61.

therefore, the singlet–triplet conversion of nitrenium PhNT2 PhNTHe+ PhNT+ + He
–β–
ions derived from sulfonium salts should proceed at
a higher rate. This is consistent with the poor yield of toluene and nitrobenzene) by phenylnitrenium ion
amination products in the photolysis of salts 186a and PhNT+ showed that, like in the above described reac-
186b in the systems benzene–CF3CO2H and toluene– tions, the process follows both N- and C-paths, yielding
CF3CO2H [164]. diphenylamines and aminobiphenyls, respectively [21,
Photolysis of salts 176y and 185 under neutral con- 178–180]. In the reaction with toluene, the product was
ditions gave rise to unusual intramolecular cyclization exclusively 4-methyldiphenylamine [178], while nitro-
leading to carbazole (yield 24%) [173] (cf. [52]) and benzene gave rise to both nitrodiphenylamines (16% of
N-phenylphenanthridinone (yield 65%) [168]. ortho, 20% of meta, and 8% of para isomer) and o-, m-
Nitrenium ions can be generated from aminopyri- (40%), and p-aminobiphenyls (16%) [179]. Analysis
of the experimental and calculation (AM1) results [54]
dinium salts not only by photolysis but also by
indicated that the composition of products formed in
thermolysis. However, in the latter case, the presence
the reaction of benzene with radiochemically generated
of at least one electron-donor substituent on the nitro-
phenylnitrenium ion is determined by comparable
gen atom is necessary. For example, thermolysis of salt
contributions of the equilibrium constants for forma-
176x under fairly severe conditions (180°C) in the tion of σ-complexes and rate constants for their
presence of mesitylene afforded 5% of N-phenyl-N-
deprotonation.
(2,4,6-trimethylphenyl)acetamide [163]. 9-Mesitylcar-
bazole was obtained in 35–45% yield by thermolysis 5. CONCLUSION
of 1-(9-carbazolyl)-2,4,6-triphenylpyridinium tetra-
fluoroborate in the presence of mesitylene [171]. The The conception of nitrenium ions is important for
yield increases to 70% under microwave irradiation; understanding mechanisms of direct electrophilic
less reactive arenes also give rise to the corresponding amination of arenes with various reagents. In the
9-arylcarbazoles, but with a considerably lower yield present review, we made an attempt to consider these
(anisole, 56%; p-xylene, 20%; toluene, 1%) [176]. mechanisms in terms of a common concept involving
[1,2,3]Triazolo[1,5-a]quinolinium salt 190 and [1,2,3]- participation of nitrenium ions. However, it should be
triazolo[1,5-b]isoquinolinium salts 191 undergo emphasized that the proposed schemes are often
thermal isomerization with rupture of the N–N bond speculative. Undoubtedly, further studies in the field
and formation of new heterocyclic systems 192–195 of nitrenium ions, including their “direct observation,”
[175] (Scheme 60). should provide clearer realization of the mechanisms
It should be noted that 1-amino-1,10-phenanthro- of electrophilic amination of arenes and a basis for
linium mesitylenesulfonate does not react with mesit- development of new effective methods of synthesis of
ylene and anthracene even at a fairly high temperature aromatic amines.
(150°C) [177], presumably due to very low stability of This review was prepared under financial support
the corresponding nitrenium ion. by the Russian Foundation for Basic Research (project
nos. 02-03-32 431 and 02-03-32 881).
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