Arylation of adamantanamines: III.* Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine and 2,2′-(adamantane-1,3-diyl) diethanamine

Article abstract of DOI:10.1134/S1070428011010027

Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine and 2,2′-(adamantane-1,3-diyl) diethanamine with isomeric bromochloro- and dibromobenzenes was studied. The yields of N,N′-diarylation products depend on the initial diamine and dihalobenzene structure. Side reactions were revealed, which reduced the yield of the target products. The arylation of 2,2′-(adamantane-1,3-diyl)diethanamine gives the corresponding N,N′-diaryl derivatives with better yield. The possibility for synthesizing unsymmetrical N,N′-diaryl derivatives of 2,2′- (adamantane-1,3-diyl)diethanamine was demonstrated.

Full text of DOI:10.1134/S1070428011010027

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 1, pp. 30–40. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.D. Averin, M.A. Ulanovskaya, A.K. Buryak, E.N. Savel’ev, B.S. Orlinson, I.A. Novakov, I. P. Beletskaya, 2011, published in
Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 1, pp. 35–44.
Arylation of Adamantanamines: III.* Palladium-Catalyzed
Arylation of Adamantane-1,3-diyldimethanamine
and 2,2′-(Adamantane-1,3-diyl)diethanamine
A. D. Averina, M. A. Ulanovskayaa, A. K. Buryakb, E. N. Savel’evc, B. S. Orlinsonc,
I. A. Novakovc, and I. P. Beletskayaa
a Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: averin@org.chem.msu.ru
b Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia
c Volgograd State Technical University, Volgograd, Russia
Received February 17, 2010
Abstract—Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine and 2,2′-(adamantane-1,3-di-
yl)diethanamine with isomeric bromochloro- and dibromobenzenes was studied. The yields of N,N′-diarylation
products depend on the initial diamine and dihalobenzene structure. Side reactions were revealed, which
reduced the yield of the target products. The arylation of 2,2′-(adamantane-1,3-diyl)diethanamine gives the
corresponding N,N′-diaryl derivatives with better yield. The possibility for synthesizing unsymmetrical N,N′-di-
aryl derivatives of 2,2′-(adamantane-1,3-diyl)diethanamine was demonstrated.
DOI: 10.1134/S1070428011010027
In the preceding communications [1, 2] we reported
on the results of our studies on palladium-catalyzed
arylation of adamantane-containing monoamines. The
synthesis of nitrogen-containing macrocycles from
2,2′-(adamantane-1,3-diyl)diethanamine was described
in [3, 4]. Insofar as catalytic amination with participa-
tion of adamantane-containing amines is largely deter-
mined by the amine structure, we believed it reason-
able to perform systematic study on palladium-cata-
lyzed arylation of diamines of the adamantane series,
which could give rise to wider diversity of N-aryl
derivatives. Adamantane-1,3-diyldimethanamine and
2,2′-(adamantane-1,3-diyl)diethanamine were synthe-
sized from the corresponding dicarboxylic acids
through their chlorides, amides, and nitriles; the latter
were reduced with lithium tetrahydridoaluminate in
tetrahydrofuran with a yield of up to 63% [5, 6]. Anti-
viral properties of adamantane-1,3-diyldimethanamine
and 2,2′-(adamantan-1,3-diyl)diethanamine hydro-
chlorides were examined in [6], and the latter turned
out to be active against bird influenza viruses.
reactions with aromatic aldehydes, and their biological
activity was studied [7]. Stroganov et al. [8] studied
specificity of vitrification of polymers upon hardening
with diaminoadamantanes. Khardin and Pershin [9]
proposed a procedure for the synthesis of diisocyanates
by treatment of adamantane-containing diamine dihy-
drochlorides with phosgene. Diisocyanates are intro-
duced into polymeric chain of polyurethanes to
enhance their chemical resistance and photostability.
Diamines of the adamantane series were used to syn-
thesize polyamides that are characterized by higher
heat resistance and hydrolytic stability than polymers
based on adamantane-1,3-dicarboxylic acid [10];
moreover, polymers obtained from adamantane-1,3-di-
yldimethanamine showed a higher heat resistance than
those derived from 2,2′-(adamantane-1,3-diyl)diethan-
amine. These diamines were also used to modify
aromatic polyimides [11–13]. Polyimides containing
adamantane fragments are more hydrolytically and
thermally stable. Highly efficient rubber stabilizers
were obtained on the basis of 2,2′-(adamantane-1,3-
diyl)diethanamine [14, 15]. For example, doping with
such its derivatives as 1,3-bis[2-(m-fluorobenzylidene-
amino)ethyl]adamantane and 1,3-bis[2-(p-methoxy-
benzylideneamino)ethyl]adamantane considerably im-
The applications of these amines are quite versatile.
New carbocyclic Schiff bases were synthesized via
* For communication II, see [1].
30

ARYLATION OF ADAMANTANAMINES: III.
31
proves mechanical properties of rubber, whereas
1,3-bis[2-(p-nitrobenzylideneamino)ethyl]adamantane
possesses a high reactivity and probably antibacterial
properties [16]. 2,2′-(Adamantane-1,3-diyl)diethan-
amine is also added to epoxy resins to improve their
optical properties and durability [17].
reaction of diamine I with bromobenzene gave a com-
plex mixture of products, from which N,N′-diaryl
derivative II was isolated in a relatively poor yield
(29%); in addition, amino aldehyde IX and imine X
were formed (Table 1, run no. 1). In the reaction with
more sterically hindered o-bromochlorobenzene the
corresponding diaryl derivative III was obtained in
almost quantitative yield (Table 1, run no. 2). On the
other hand, meta- and para-isomeric bromochloroben-
zenes gave rise to compounds IV and V in moderate
yield (31%; Table 1, run nos. 3, 4). The reaction of
diamine I with m-bromochlorobenzene was accom-
panied by formation of various by-products, including
those resulting from reduction of the C–Cl bond and
oxidation of the initial diamine (compounds II and IX–
XIV); in the reaction with p-bromochlorobenzene
a considerable amount of aldehyde XV was isolated
(Scheme 1).
Antiviral activity of various adamantane-containing
amines was studied [18]. 2,2′-(Adamantane-1,3-diyl)-
diethanamine turned out to be less active than adaman-
tane-1,3-diyldimethanamine at a minimal inhibitory
concentration. On the other hand, adamantane-1,3-di-
yldimethanamine dihydrochloride was patented as
antiviral agent for pets [19, 20].
Development of a convenient procedure for the
synthesis of N,N′-bis(haloaryl) derivatives of adaman-
tane-containing diamines is important from the view-
point of their potential physiological activity, as well
as of their possible application as intermediate prod-
ucts for the preparation of complex macrocyclic com-
pounds containing adamantane fragments via palladi-
um-catalyzed amination.
By-product mixtures (Table 1, run no. 3) were
analyzed by NMR spectroscopy and MALDI-TOF
mass spectrometry. However, it was almost impossible
to estimate their composition, for different components
contained similar molecular fragments. For example,
a fraction isolated by elution with petroleum ether–
methylene chloride (1 :1) contained compound IV,
reduction product XI (one C–Cl bond was reduced;
m/z 380 [M]+), aldehyde XII (m/z 303 [M]+), and
Schiff base XIII (m/z 412 [M]+). Another fraction
(eluent methylene chloride) was a mixture of com-
pound XII with aldehyde IX (m/z 269 [M]+) and Schiff
bases X (m/z 344 [M]+) and XIV (m/z 378 [M]+). The
reaction with o-dibromobenzene was much less suc-
cessful than with o-bromochlorobenzene. Diarylation
product VI was isolated in 30% yield, and a mixture of
Arylation of adamantane-1,3-diyldimethan-
amine. Initially, palladium-catalyzed arylation of ada-
mantane-1,3-diyldimethanamine (I) was studied with
the use of isomeric bromochlorobenzenes in the pres-
ence of fairly universal catalytic system Pd(dba)2–
BINAP [21] and sodium tert-butoxide as base. The
reactions were carried out in boiling dioxane at a di-
amine concentration of 0.1 M and a diamine–dihalo-
benzene ratio of 1:2.2. The products were isolated by
column chromatography on silica gel. Unexpectedly,
diamine I showed unpredictable reactivity, as com-
pared to the reactivity of analogous monoamines. The
Table 1. Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine (I); diamine–dihalobenzene ratio 1:2.2
Run no.
Dihalobenzene
Bromobenzene
Pd/L, molar ratio
Product (yield, %)
1
2
a3a
b4b
5
Pd(dba)2/BINAP, 8:9
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 2:2.5
Pd(dba)2/Xantphos, 4:5
Pd(dba)2/BINAP, 2:2.5
Pd(dba)2/Xantphos, 4:5
II (29), IX (19), X (12)
III (95)
o-Bromochlorobenzene
m-Bromochlorobenzene
p-Bromochlorobenzene
o-Dibromobenzene
m-Dibromobenzene
m-Dibromobenzene
p-Dibromobenzene
p-Dibromobenzene
IV (31)
V (31), XV (25)
VI (30), XVI (4), XVII (14)
VII (0)
6
7
c8c
VII (0)
VIII (traces)
VIII (0)
9
a
b
c
Some fractions contained mixtures of compounds II, IV, and XI and of IX, X, and XII–XIV.
p-Chloroaniline (18%) and benzidine (7%) were also isolated.
p-Bromoaniline (5%) and benzidine (5%) were also isolated.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

AVERIN et al.
32
Scheme 1.
H
NH2
N
Br
R
Pd(dba)2/L
t-BuONa, dioxane
+
H
N
NH2
R
R
I
II–VIII
II, R = H; III, R = o-Cl; IV, R = m-Cl; V, R = p-Cl; VI, R = o-Br; VII, R = m-Br; VIII, R = p-Br.
By-products:
H
NHPh
NHPh
NHPh
N
Cl
H
N
NPh
Cl
CHO
CHO
IX
X
XI
XII
Br
H
H
N
H
H
N
N
Cl
R'
N
Cl
N
Cl
N
R''
CHO
CHO
XIII
XIV
XV
XVI
Br
Br
HN
HN
NH
HN
XVII
XIV, R′ = Cl or H, R″ = H or Br.
aldehyde XVI (yield 4%; (m/z 347 [M]+) with linear
oligomer XVII (14%; (m/z 770 [M]+) was obtained;
oligomer XVII was formed as a result of ortho-di-
amination of dibromobenzene (Table 1, run no. 5). The
most complex pattern was observed in the reactions of
diamine I with m- and p-dibromobenzenes. In the first
case (Table 1, run no. 6), the 1H NMR spectrum of the
reaction mixture contained very weak signals from di-
arylation product VII at δ 2.12 (adamantane fragment)
and 2.81 ppm (CH2N). Signals at δ 2.20, 2.28 and 2.86,
2.90 ppm from the corresponding protons in compounds
like A (X = O, NH, NR) were much more intense.
NHAr
Numerous singlets in the region δ 7.54–7.61 ppm
are typical of azomethine protons (CH=N). Signals in
the aromatic region, assignable to m-bromoaniline
derivatives, were very weak, indicating predominant
contribution of processes involving reduction of
H
X
A
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

ARYLATION OF ADAMANTANAMINES: III.
33
bromoarenes and oxidation of the initial amine. Insofar
as the product mixture was very complex, it was
unreasonable to separate it by chromatography. The
selectivity of the reaction was not improved when less
active ligand (Xantphos) was used (Table 1, run no. 7).
Likewise, low selectivity was observed in the reaction
of p-dibromobenzene with diamine I (Table 1, run
no. 8). By column chromatography we isolated very
small amounts of bromoaniline and biphenyl-4,4′-di-
amine (as a single fraction), but we failed to separate
target compound VIII from other (unidentified) prod-
ucts. In the MALDI-TOF mass spectrum of that
mixture we observed a ion peak with m/z 502, which
corresponds to the molecular ion of compound VIII.
Although the reactions of XVIII with m- and
p-bromochlorobenzenes were characterized by lower
yields of N,N′-diaryl derivatives XXI and XXII (61
and 70%, respectively), the yields were much higher
than those in analogous reactions of adamantane-1,3-
diyldimethanamine (I) (cf. Table 1; run nos. 3, 4).
However, diamine XVIII reacted with o-dibromoben-
zene fairly difficultly: in the presence of Pd(dba)2–
BINAP as catalytic system (regardless of its amount,
4–16 mol %) the yield of diarylation product XXIII
was very poor, but a considerable amount of mono-
arylation product XXVI was formed (Table 2; run
nos. 5, 6). An attempt to improve the results using
DavePHOS as donor ligand was unsuccessful (Table 2,
run no. 7). Compound XXIV (arylation product at both
amino groups with m-dibromobenzene) was obtained
in a higher yield in the presence of 2–4 mol % of the
catalyst containing BINAP as ligand (Table 2; run nos.
8, 10); in all cases, an appreciable amount of linear
oligomer XXVII was formed as a result of facile di-
amination of m-dibromobenzene. A mixture of com-
pound XXIV with reduction product XXVIII and
Arylation of 2,2′-(adamantane-1,3-diyl)diethan-
amine. 2,2′-(Adamantane-1,3-diyl)diethanamine
(XVIII) reacted with dihaloarenes more selectively
than did diamine I. The reaction of XVIII with
2.2 equiv of bromobenzene gave 75% of diarylation
product XIX (Scheme 2; Table 2, run no. 1). In the
reaction with o-bromochlorobenzene the yield of diaryl
derivative XX reached 92% (Table 2, run no. 2).
Scheme 2.
R
NH2
Br
N
H
Pd(dba)2/L
t-BuONa, dioxane
+
R
NH2
N
H
R
XVIII
XIX–XXV
XIX, R = H; XX, R = o-Cl; XXI, R = m-Cl; XXII, R = p-Cl; XXIII, R = o-Br; XXIV, R = m-Br; XXV, R = p-Br.
By-products:
H
H
N
N
N
H
Br
Br
NH
HN
Br
NH2
XXVI
XXVII
Br
Br
N
H
Br
N
Br
N
N
H
H
H
Ph
CHO
Ph
CHO
N
N
H
H
XXVIII
XXIX
XXX
XXXI
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AVERIN et al.
34
Table 2. Palladium-catalyzed arylation of 2,2′-(adamantane-1,3-diyl)diethanamine; ratio diamine–dihalobenzene 1:2.2
Run no.
Dihalobenzene
Bromobenzene
Pd/L, molar ratio
Product (yield, %)
XIX (75)
01
02
Pd(dba)2/BINAP, 8:9
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 16:18
Pd(dba)2/DavePHOS, 8:9
Pd(dba)2/BINAP, 4:4.5
Pd(dba)2/BINAP, 2:2.5
Pd(dba)2/BINAP, 2:2.5
Pd(dba)2/Xantphos, 8:9
Pd(dba)2/BINAP, 4:4.5
o-Bromochlorobenzene
m-Bromochlorobenzene
p-Bromochlorobenzene
o-Dibromobenzene
o-Dibromobenzene
o-Dibromobenzene
m-Dibromobenzene
m-Dibromobenzene
m-Dibromobenzene
m-Dibromobenzene
p-Dibromobenzene
XX (92)
03
XXI (61)
XXII (70)
04
a05a
a06a
07
XXIII (6), XXVI (20)
XXVI (15)
08
b09b
XXIV (39), XXVII (19)
XXIV (26), XXVII (11)
XXIV (27), XXVII (18)
XXIV (26), XXVIII (13)
XXV (11)
10
11
c12c
a
b
c
Joint chromatographic separation of the product mixture isolated in two experiments.
A separate fraction contained compounds XXIV, XXVIII, and XXIX.
Benzidine (9%) was also isolated; a separate fraction contained compounds XXV, XXX, and XXXI.
mixture), but chromatographic isolation of this com-
pound was not complete (Table 2, run no. 12. In addi-
tion, benzidine was isolated as by-product (9%), and
a separate fraction contained a mixture of diarylation
product XXV, reduction product of one C–Br bond
(XXX; m/z 452 [M]+), and partial oxidation product
XXXI (m/z 375 [M]+). The N-substituted aniline frag-
ment in diamine XXX was characterized by the
partial oxidation product of diamine XVIII (aldehyde
XXIX) was isolated as a separate fraction (Table 2,
run no. 9). The N-substituted aniline fragment (reduc-
tion product) in diamine XXVIII gave rise to the fol-
1
lowing signals in the H NMR spectrum, δ, ppm:
3
3
6.59 d (2H, J = 8.6 Hz), 6.68 t (1H, J = 7.4 Hz),
7.16 d.d (2H, 3J = 8.5, 7.3 Hz); the CH2CHO fragment
in XXIX was characterized by signals at δ, ppm: 9.86 t
(1H, 3J = 3.3 Hz), 2.17 d (2H, 3J = 3.3 Hz). The use of
Xantphos to minimize diamination process completely
suppressed the formation of compound XXVII; how-
ever, the yield of target product XXIV decreased, and
compound XXVIII was formed (Table 2, run no. 11).
N,N′-Bis(4-bromophenyl)-substituted diamine XXV
was formed in a fairly good yield (47% in the reaction
1
following signals in the H NMR spectrum, δ, ppm:
6.59 d (2H, 3J = 7.6 Hz), 6.68 t (1H, 3J = 7.3 Hz), 7.17 t
3
(2H, J = 7.9 Hz) (cf. the corresponding data for
XXVIII); the corresponding carbon signals appeared
in the 13C NMR spectrum at δC 112.7 (2C), 117.1 (1C),
and 129.2 ppm (2C). Protons in the CH2CHO fragment
of aldehyde XXXI resonated in the 1H NMR spectrum
Scheme 3.
NH2
NH2
P
P
P
P
+
Pd
Pd
Br
Br
NH2
P
P
P
P
Br
Br
Symmetrization
Pd
+
Pd
H2N
NH2
NH2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

ARYLATION OF ADAMANTANAMINES: III.
35
Scheme 4.
NH2
Br
N
Cl
N
Cl
H
H
Pd(dba)2/BINAP
t-BuONa, dioxane
+
+
NH2
Cl
N
Cl
NH2
H
XVIII
XXXI (35%)
XXXII (30%)
N
Cl
Br
Cl
N
Cl
H
Pd(dba)2/BINAP
t-BuONa, dioxane
H
Cl
+
NH2
N
H
XXXII
XXXIII, 29%
3
3
at δ, ppm: 9.86 t (1H, J = 3.2 Hz), 2.16 d (2H, J =
3.2 Hz); δC 203.3 (1C), 56.8 ppm (1C).
residual proton and carbon signals of the solvent as
reference (CHCl3, δ 7.25 ppm; CDCl3, δC 77.00 ppm).
The MALDI-TOF mass spectra (positive ion detection)
were obtained on a Bruker Daltonics Ultraflex instru-
ment using 1,8,9-trihydroxyanthracene as matrix and
polyethylene glycols as internal standards. Silica gel
(Merck, 40–60 μm) was used for preparative column
chromatography. Commercially available isomeric
bromochloro- and dibromobenzenes, sodium tert-but-
oxide, and phosphine ligands were used without addi-
tional purification. Adamantane-1,3-diyldimethan-
amine (I) and 2,2′-(adamantane-1,3-diyl)diethanamine
(XVIII) were synthesized as described in [23], and
Pd(dba)2 was prepared according to the procedure
reported in [24] and used without additional recrys-
tallization. Dioxane was distilled first over alkali and
then over metallic sodium; methylene chloride, petro-
leum ether, and methanol were distilled prior to use.
The formation of benzidine in the reaction of di-
amine XVIII with p-dibromobenzene may be rational-
ized as shown in Scheme 3. Initially, p-bromoaniline is
formed according to the catalytic mechanism proposed
in [1]. p-Bromoaniline is capable of reacting with
palladium complex to give oxidative addition product
which may undergo so-called symmetrization [22], so
that benzidine is formed from two aminophenyl frag-
ments. Analogous ligand exchange at the palladium
atom could give rise to other products which were
neither isolated as individual substances nor identified,
but their formation could reduce the yield of the target
product and make the product mixture more complex.
We also tried to obtain diarylation products of
2,2′-(adamantane-1,3-diyl)diethanamine (XVIII) with
different aryl substituents on the nitrogen atoms
(Scheme 4). For this purpose, diamine XVIII was
brought into reaction with an equimolar amount of
m-bromochlorobenzene. We thus isolated 30% of
monoaryl derivative XXXII and 35% (calculated on
the initial diamine) of diarylation product XXI. By re-
action of compound XXXII with p-bromochloroben-
zene we obtained 29% of unsymmetrically substituted
diaryl derivative XXXIII.
N,N′-Diaryl-substituted diamines II–VIII, XIX–
XXV, and XXXIII (general procedure). A two-necked
flask was charged under argon with the corresponding
dihaloarene (0.2–0.25 mmol), Pd(dba)2 (2–8 mol %),
and phosphine ligand (2.5–9 mol %), 2 ml of anhy-
drous dioxane, 0.44–0.55 mmol of diamine I or XVIII,
and 1.5–2 equiv of sodium tert-butoxide were added,
and the mixture was heated for 7 h under reflux. The
mixture was cooled, the precipitate was filtered off, the
organic phase was evaporated under reduced pressure,
the solid residue was dissolved in methylene chloride,
the solution was washed with water, and the organic
phase was dried over anhydrous sodium sulfate and
evaporated under reduced pressure. The residue was
EXPERIMENTAL
The H and 13C NMR spectra were recorded from
solutions in CDCl3 on a Bruker Avance-400 spectrom-
eter at 400 and 100.6 MHz, respectively, using the
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

AVERIN et al.
36
3
3
separated by chromatography on silica gel using the
following solvent systems as eluents (in succession):
petroleum ether–methylene chloride (4 :1 to 1:4),
methylene chloride, methylene chloride–methanol
(500:1 to 100:1).
7.11 t (2H, J = 7.8 Hz), 7.24 d (2H, J = 8.3 Hz).
13C NMR spectrum, δC, ppm: 28.3 (2C), 34.7 (2C),
36.3 (1C), 40.1 (4C), 43.8 (1C), 55.4 (2C), 111.1 (2C),
116.6 (2C), 118.9 (2C), 127.7 (2C), 129.0 (2C), 144.6
(2C). Mass spectrum: m/z 414.1603 [M]+. C24H28Cl2N2.
Calculated: M 414.1630.
N-[3-(Phenylaminomethyl)adamantan-1-ylmeth-
yl]aniline (II) was synthesized from 0.25 mmol
(48.5 mg) of diamine I and 0.55 mmol (86 mg) of
bromobenzene in the presence of 11.5 mg (8 mol %) of
Pd(dba)2, 14 mg (9 mol %) of BINAP, and 80 mg
(1.5 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
drous dioxane. Yield (after chromatography; petroleum
ether–CH2Cl2, 1:1) 25 mg (29%), colorless crystals,
3-Chloro-N-[3-(3-chlorophenylaminomethyl)-
adamantan-1-ylmethyl]aniline (IV) was synthesized
from 0.2 mmol (39 mg) of diamine I and 0.44 mmol
(84 mg) of m-bromochlorobenzene in the presence of
4.5 mg (4 mol %) of Pd(dba)2, 5.5 mg (4.5 mol %) of
BINAP, and 80 mg (2 equiv) of sodium tert-butoxide
in 2.5 ml of anhydrous dioxane. Yield (after chroma-
tography; petroleum ether–CH2Cl2, 2:1) 26 mg (31%),
1
mp 101–103°C. H NMR spectrum, δ, ppm: 1.41 s
1
(2H), 1.50–1.64 m (8H), 1.66 br.s (2H), 2.12 br.s (2H),
colorless oily substance. H NMR spectrum, δ, ppm:
1.36 s (2H), 1.45–1.58 m (8H), 1.64 s (2H), 2.12 br.s
(2H), 2.82 d (4H, J = 5.5 Hz), 3.73 br.s (2H),
3
2.85 s (4H), 3.64 br.s (2H), 6.61 d (4H, J = 8.6 Hz),
3
3
3
6.66 t (2H, J = 7.3 Hz), 7.15 d.d (4H, J = 7.3,
13
3
4
8.5 Hz). C NMR spectrum, δC, ppm: 28.5 (2C), 34.6
6.46 d.d.d (2H, J = 8.3, J = 2.2, 0.7 Hz), 6.57 t (2H,
4J = 2.1 Hz), 6.61 d.d.d (2H, 3J = 7.8, 4J = 1.9, 0.8 Hz),
(2C), 36.5 (1C), 40.3 (4C), 43.8 (1C), 56.0 (2C), 112.6
(4C), 116.9 (2C), 129.2 (4C), 149.1 (2C). Mass
spectrum: m/z 346.2390 [M]+. C24H30N2. Calculated:
M 346.2409.
7.03 t (2H, 3J = 8.0 Hz). C NMR spectrum, δC, ppm:
13
28.3 (2C), 34.7 (2C), 36.3 (1C), 40.1 (4C), 43.6
(1C), 55.6 (2C), 111.10 (2C), 112.1 (2C), 116.7 (2C),
130.1 (2C), 135.0 (2C), 150.1 (2C). Mass spectrum:
m/z 414.1699 [M]+. C24H28Cl2N2. Calculated:
M 414.1630. Elution with petroleum ether–CH2Cl2
(1:1) gave a mixture of compound IV, partial reduc-
tion product XI, and compounds XII and XIII. Elution
with methylene chloride gave a mixture of compounds
IX, X, XIII, and XIV.
Elution with methylene chloride gave 9 mg (10%)
of compound II, 14 mg (19%) of IX, and 10 mg
(12%) of X.
3-(Phenylaminomethyl)adamantane-1-carbalde-
1
hyde (IX). H NMR spectrum, δ, ppm: 1.48–1.84 m
(12H), 2.19 br.s (2H), 2.89 s (2H), 3.65 br.s (1H),
3
3
6.61 d (2H, J = 7.7 Hz), 6.67 t (1H, J = 7.3 Hz),
3
7.15 t (2H, J = 7.4 Hz), 9.36 s (1H). Mass spectrum:
4-Chloro-N-[3-(4-chlorophenylaminomethyl)-
adamantan-1-ylmethyl]aniline (V) was synthesized
from 0.2 mmol (39 mg) of diamine I and 0.44 mmol
(84 mg) of p-bromochlorobenzene in the presence of
4.5 mg (4 mol %) of Pd(dba)2, 5.5 mg (4.5 mol%) of
BINAP, and 80 mg (2 equiv) of sodium tert-butoxide
in 2.5 ml of anhydrous dioxane. Yield (after chroma-
tography; petroleum ether–CH2Cl2, 2:1, 1:1) 26 mg
m/z 269.21 [M]+.
N-[3-(Phenylaminomethyl)adamantan-1-ylmeth-
ylidene]aniline (X). 1H NMR spectrum, δ, ppm: 1.48–
1.84 m (12H), 2.28 br.s (2H), 2.90 s (2H), 3.65 br.s
3
3
(1H), 6.61 d (2H, J = 7.7 Hz), 6.67 t (1H, J =
3
3
7.3 Hz), 6.98 d (2H, J = 8.2 Hz), 7.15 t (2H, J =
3
7.4 Hz), 7.31 t (2H, J = 7.8 Hz), 7.57 s (1H); signal
1
(31%), colorless oily substance. H NMR spectrum, δ,
from one proton was not assigned unambiguously.
Mass spectrum: m/z 344.25 [M]+.
ppm: 1.37 s (2H), 1.47–1.59 m (8H), 1.64 br.s (2H),
2.12 br.s (2H), 2.80 s (4H), 3.68 br.s (2H), 6.52 d (4H,
3J = 8.8 Hz), 7.08 d (4H, 3J = 8.8 Hz). 13C NMR spec-
trum, δC, ppm: 28.4 (2C), 34.7 (2C), 36.4 (1C), 40.1
(4C), 43.6 (1C), 56.1 (2C), 113.7 (4C), 121.4 (2C),
129.0 (4C), 147.6 (2C). Mass spectrum: m/z 414.1596
[M]+. C24H28Cl2N2. Calculated: M 414.1630. Elution
with methylene chloride gave 15 mg (25%) of com-
pound XV containing p-chloroaniline (18 mol %) and
benzidine (7 mol %) as impurities.
2-Chloro-N-[3-(2-chlorophenylaminomethyl)-
adamantan-1-ylmethyl]aniline (III) was synthesized
from 0.2 mmol (39 mg) of diamine I and 0.44 mmol
(84 mg) of o-bromochlorobenzene in the presence of
4.5 mg (4 mol %) of Pd(dba)2, 5.5 mg (4.5 mol %) of
BINAP, and 80 mg (2 equiv) of sodium tert-butoxide
in 2.5 ml of anhydrous dioxane. Yield 79 mg (95%),
1
light yellow oily substance. H NMR spectrum, δ,
ppm: 1.44 s (2H), 1.50–1.66 m (8H), 1.67 s (2H),
2.14 br.s (2H), 2.91 d (4H, 3J = 5.9 Hz), 4.37 br.s (2H),
3-(4-Chlorophenylaminomethyl)adamantane-1-
3
3
6.59 t (2H, J = 7.6 Hz), 6.67 d (2H, J = 8.1 Hz),
carbaldehyde (XV). 1H NMR spectrum, δ, ppm: 1.50–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

ARYLATION OF ADAMANTANAMINES: III.
37
1.85 m (12H), 2.19 br.s (2H), 2.85 s (2H), 3.69 br.s
1H NMR spectrum, δ, ppm: 1.38 s (2H), 1.48–1.62 m
3
3
3
(12H), 1.66 br.s (2H), 2.10 br.s (2H), 3.18 t (4H, J =
(1H), 6.52 d (2H, J = 8.7 Hz), 7.08 d (2H, J =
8.7 Hz), 9.35 s (1H). 13C NMR spectrum, δC, ppm:
27.5 (2C), 35.2 (1C), 35.5 (2C), 35.9 (1C), 38.8 (1C),
39.8 (2C), 45.5 (1C) 55.7 (1C), 113.76 (2C), 120.5
(1C), 129.0 (2C), 147.5 (1C), 205.3 (1C). Mass spec-
trum: m/z 303.1388 [M]+. C18H22ClNO. Calculated:
M 303.1390.
8.0 Hz), 4.16 t (2H, 3J = 4.7 Hz), 6.63 t.d (2H, 3J = 7.6,
3
4J = 1.4 Hz), 6.67 d (2H, J = 8.1 Hz), 7.16 t.d (2H,
4
3
4
3J = 7.8, J = 1.4 Hz), 7.26 d.d (2H, J = 7.6, J =
13
1.2 Hz). C NMR spectrum, δC, ppm: 28.9 (2C), 32.7
(2C), 36.4 (1C), 38.2 (2C), 41.9 (4C), 43.3 (2C), 47.6
(1C), 111.0 (2C), 116.8 (2C), 118.9 (2C), 127.7 (2C),
129.0 (2C), 144.1 (2C). Mass spectrum: m/z 442.2002
[M]+. C26H32Cl2N2. Calculated: M 442.1943.
2-Bromo-N-[3-(2-bromophenylaminomethyl)-
adamantan-1-ylmethyl]aniline (VI) was synthesized
from 0.2 mmol (39 mg) of diamine I and 0.44 mmol
(104 mg) of o-dibromobenzene in the presence of
4.5 mg (4 mol %) of Pd(dba)2, 5.5 mg (4.5 mol %) of
BINAP, and 80 mg (2 equiv) of sodium tert-butoxide
in 2.5 ml of anhydrous dioxane. Yield (after chroma-
tography; petroleum ether–CH2Cl2, 2:1) 30 mg (30%),
3-Chloro-N-(2-{3-[2-(3-chlorophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XXI) was syn-
thesized from 0.25 mmol (56 mg) of diamine XVIII
and 0.55 mmol (105 mg) of m-bromochlorobenzene in
the presence of 5.5 mg (4 mol %) of Pd(dba)2, 7 mg
(4.5 mol %) of BINAP, and 80 mg (1.5 equiv) of
sodium tert-butoxide in 2.5 ml of anhydrous dioxane.
Yield 57 mg (61%), light yellow oily substance.
1H NMR spectrum, δ, ppm: 1.32 s (2H), 1.41 t (4H,
3J = 8.0 Hz), 1.43–1.58 m (8H), 1.63 br.s (2H),
1
colorless crystals, mp 135–137°C. H NMR spectrum,
δ, ppm: 1.44 s (2H), 1.50–1.65 m (8H), 1.67 s (2H),
3
2.14 br.s (2H), 2.90 d (4H, J = 5.8 Hz), 4.37 t (2H,
3J = 4.6 Hz), 6.52 t.d (2H, 3J = 7.6, 4J = 1.4 Hz), 6.64 d
3
3
3
4
2.07 br.s (2H), 3.04–3.11 m (4H), 3.57 t (2H, J =
(2H, J = 8.2 Hz), 7.14 t.d (2H, J = 7.8, J = 1.2 Hz),
3
4
7.39 d.d (2H, J = 7.9, J = 1.5 Hz). 13C NMR spec-
trum, δC, ppm: 28.4 (2C), 34.7 (2C), 36.3 (1C), 40.2
(4C), 43.8 (1C), 55.6 (2C), 109.8 (2C), 111.2 (2C),
117.2 (2C), 128.4 (2C), 132.3 (2C), 145.6 (2C). Mass
spectrum: m/z 502.11 [M]+. Using the same eluent,
a mixture of compounds XVI and XVII was isolated.
3
4
4.6 Hz), 6.44 d (2H, J = 8.1 Hz), 6.56 t (2H, J =
3
3
1.9 Hz), 6.64 d (2H, J = 7.7 Hz), 7.06 t (2H, J =
13
8.0 Hz). C NMR spectrum, δC, ppm: 28.8 (2C), 32.7
(2C), 36.3 (1C), 38.4 (2C), 41.9 (4C), 43.4 (2C), 47.7
(1C), 111.0 (2C), 112.1 (2C), 116.8 (2C), 130.1 (2C),
134.9 (2C), 149.6 (2C). Mass spectrum: m/z 442.1919
[M]+. C26H32Cl2N2. Calculated: M 442.1943.
N-{2-[3-(2-Phenylaminoethyl)adamantan-1-yl]-
ethyl}aniline (XIX) was synthesized from 0.25 mmol
(56 mg) of diamine XVIII and 0.55 mmol (86 mg) of
bromobenzene in the presence of 11.5 mg (8 mol %)
of Pd(dba)2, 14 mg (9 mol %) of BINAP, and 80 mg
(1.5 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
drous dioxane. Yield 70 mg (75%), light yellow oily
4-Chloro-N-(2-{3-[2-(4-chlorophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XXII) was syn-
thesized from 0.25 mmol (56 mg) of diamine XVIII
and 0.55 mmol (105 mg) of p-bromochlorobenzene in
the presence of 5.5 mg (4 mol %) of Pd(dba)2, 7 mg
(4.5 mol %) of BINAP, and 80 mg (1.5 equiv) of
sodium tert-butoxide in 2.5 ml of anhydrous dioxane.
Yield 65 mg (70%), light yellow oily substance.
1H NMR spectrum, δ, ppm: 1.31 s (2H), 1.40 t (4H,
3J = 8.0 Hz), 1.42–1.58 m (8H), 1.63 br.s (2H),
1
substance. H NMR spectrum, δ, ppm: 1.37 s (2H),
3
1.46 t (4H, J = 8.1 Hz), 1.48–1.61 m (8H), 1.67 s
(2H), 2.10 br.s (2H), 3.15 t (4H, 3J = 7.9 Hz), 3.51 br.s
3
3
(2H), 6.64 d (4H, J = 7.6 Hz), 6.73 t (2H, J =
3
7.3 Hz), 7.21 d.d (4H, J = 8.5, 7.3 Hz). 13C NMR
3
2.06 br.s (2H), 3.02–3.10 m (4H), 3.51 t (2H, J =
3
3
4.8 Hz), 6.50 d (4H, J = 8.8 Hz), 7.11 d (4H, J =
spectrum, δC, ppm: 28.8 (2C), 32.6 (2C), 36.4 (1C),
38.5 (2C), 41.9 (4C), 43.6 (2C), 47.7 (1C), 112.6 (4C),
117.0 (2C), 129.1 (4C), 148.4 (2C). Mass spectrum:
m/z 374.2790 [M]+. C26H34N2. Calculated: M 374.2722.
13
8.8 Hz). C NMR spectrum, δC, ppm: 28.8 (2C), 32.6
(2C), 36.3 (1C), 38.6 (2C), 41.8 (4C), 43.4 (2C), 47.7
(1C), 113.6 (4C), 121.9 (2C), 128.9 (4C), 147.0 (2C).
Mass spectrum: m/z 442.1887 [M]+. C26H32Cl2N2. Cal-
culated: M 442.1943.
2-Chloro-N-(2-{3-[2-(2-chlorophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XX) was syn-
thesized from 0.25 mmol (56 mg) of diamine XVIII
and 0.55 mmol (105 mg) of o-bromochlorobenzene in
the presence of 5.5 mg (4 mol %) of Pd(dba)2, 7 mg
(4.5 mol %) of BINAP, and 80 mg (1.5 equiv) of
sodium tert-butoxide in 2.5 ml of anhydrous dioxane.
Yield 86 mg (92%), light yellow oily substance.
2-Bromo-N-(2-{3-[2-(2-bromophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XXIII).
a. Compound XXIII was synthesized from 0.25 mmol
(56 mg) of diamine XVIII and 0.55 mmol (130 mg) of
o-dibrombenzene in the presence of 5.5 mg (4 mol %)
of Pd(dba)2, 7 mg (4.5 mol %) of BINAP, and 80 mg
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

AVERIN et al.
38
(1.5 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
drous dioxane.
m/z 530.08 [M]+. Elution with methylene chloride gave
a mixture of compound XXIV, reduction product
XXVIII, and aldehyde XXIX.
b. The synthesis was performed in the presence of
23 mg (16 mol %) of Pd(dba)2 and 28 mg (18 mol %)
of BINAP.
b. The synthesis was performed using double
amounts of the reactants and catalyst. Elution with
methylene chloride gave 73 mg (27%) of compound
XXIV; the subsequent elution with the same eluent
afforded 38 mg (18%) of oligomer XXVII.
The products obtained in the two experiments were
combined and subjected to chromatography using
petroleum ether–CH2Cl2 (2:1) as eluent. Yield 15 mg
1
(6%), colorless oily substance. H NMR spectrum, δ,
N,N′-Bis(2-{3-[2-(3-bromophenylamino)ethyl]-
ppm: 1.38 s (2H), 1.47–1.58 m (12H), 1.63 br.s (2H),
adamantan-1-yl}ethyl)benzene-1,3-diamine
2.08 br.s (2H), 3.16 t (4H, 3J = 7.9 Hz), 4.15 br.s (2H),
1
(XXVII). H NMR spectrum, δ, ppm: 1.31 s (4H),
3
4
3
6.55 t.d (2H, J = 7.6, J = 1.0 Hz), 6.62 d.d (2H, J =
1.38–1.57 m (24H), 1.61 br.s (4H), 2.05 br.s (4H),
3.02–3.12 m (8H), 3.48 br.s (2H), 3.65 br.s (2H),
4
3
4
8.2, J = 1.0 Hz), 7.17 t.d (2H, J = 7.8, J = 1.0 Hz),
3
4
13
3
4
7.40 d.d (2H, J = 7.8, J = 1.1 Hz). C NMR spec-
trum, δC, ppm: 28.9 (2C), 32.8 (2C), 36.4 (1C), 38.6
(2C), 42.0 (4C), 43.3 (2C), 47.7 (1C), 109.6 (2C),
111.1 (2C), 117.4 (2C), 128.5 (2C), 132.3 (2C), 145.1
(2C). Mass spectrum: m/z 530.01 [M]+.
5.85 br.s (1H), 5.99 d.d (2H, J = 8.1, J = 2.1 Hz),
3
4
4
6.48 d.d (2H, J = 8.2, J = 2.1 Hz), 6.70 t (2H, J =
3
3
1.8 Hz), 6.77 d (2H, J = 7.9 Hz), 6.97 t (1H, J =
8.2 Hz), 6.99 t (2H, 3J = 8.1 Hz).
4-Bromo-N-(2-{3-[2-(4-bromophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XXV) was syn-
thesized from 0.25 mmol (56 mg) of diamine XVIII
and 0.55 mmol (130 mg) of p-dibromobenzene in the
presence of 5.5 mg (4 mol %) of Pd(dba)2, 7 mg
(4.5 mol %) of BINAP, and 80 mg (1.5 equiv) of
sodium tert-butoxide in 2.5 ml of anhydrous dioxane.
Yield (after chromatographic separation; petroleum
ether–CH2Cl2, 1:1) 14 mg (11%), colorless oily sub-
Elution with CH2Cl2–MeOH (3:1) gave 37 mg
(20%) of monoarylation product XXVI.
2-Bromo-N-{2-[3-(2-aminoethyl)adamantan-1-
1
yl]ethyl}aniline (XXVI). H NMR spectrum, δ, ppm:
1.36–1.63 m (16H), 2.01 br.s (2H), 2.96–3.03 m (2H),
3
3.09 t (2H, J = 7.2 Hz), 4.10 br.s (1H), 6.52 t.d (1H,
4
3
4
3J = 7.6, J = 1.4 Hz), 6.60 d.d (1H, J = 8.2, J =
3
4
1.1 Hz), 7.15 t.d (1H, J = 7.7, J = 1.4 Hz), 7.37 d.d
1
(1H, J = 7.8, J = 1.4 Hz). 13C NMR spectrum, δC,
ppm: 28.7 (2C), 32.5 (1C), 32.6 (1C), 35.5 (1C), 36.1
(1C), 38.4 (1C), 41.1 (1C), 41.4 (2C), 41.7 (2C), 43.1
(1C), 47.2 (1C), 109.5 (1C), 111.2 (1C), 117.4 (1C),
128.5 (1C), 132.2 (1C), 145.0 (1C). Mass spectrum:
m/z 376.20 [M]+.
3
4
stance. H NMR spectrum, δ, ppm: 1.31 s (2H), 1.40 t
3
(4H, J = 8.1 Hz), 1.42–1.56 m (8H) 1.61 br.s (2H),
2.06 br.s (2H), 3.06 t (4H, 3J = 8.0 Hz), 3.56 br.s (2H),
3
3
6.45 d (4H, J = 8.9 Hz), 7.23 d (4H, J = 8.9 Hz).
13C NMR spectrum, δC, ppm: 28.9 (2C), 32.7 (2C),
36.4 (1C), 38.7 (2C), 41.9 (4C), 43.5 (2C), 47.8 (1C),
108.6 (2C), 114.2 (4C), 131.9 (4C), 147.4 (2C). Mass
spectrum: m/z 530.0880 [M]+. C26H32Br2N2. Calculat-
ed: M 530.0932. Elution with petroleum ether–CH2Cl2
(4:1) gave 4 mg (9%) of benzidine, elution with petro-
leum ether–CH2Cl2 (1:1) gave 3 mg (7%) of p-bromo-
aniline, and a mixture of compound XXV, reduction
product XXX, and aldehyde XXXI was isolated by
elution with methylene chloride.
3-Bromo-N-(2-{3-[2-(3-Bromophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XXIV).
a. Compound XXIV was synthesized from 0.25 mmol
(56 mg) of diamine XVIII and 0.55 mmol (130 mg) of
m-dibromobenzene in the presence of 3 mg (2 mol %)
of Pd(dba)2, 4 mg (2.5 mol %) of BINAP, and 80 mg
(1.5 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
drous dioxane. Yield (after chromatography; petroleum
ether–CH2Cl2, 1:1) 34 mg (26%), colorless oily sub-
N-{2-[3-(2-Aminoethyl)adamantan-1-yl]ethyl}-
3-chloroaniline (XXXII) was synthesized from
0.625 mmol (139 mg) of diamine XVIII and
0.625 mmol (120 mg) of m-bromochlorobenzene in the
presence of 7 mg (2 mol %) of Pd(dba)2, 10 mg
(2.5 mol %) of BINAP, and 100 mg (1.5 equiv) of
sodium tert-butoxide in 2.5 ml of anhydrous dioxane.
By chromatography using petroleum ether–CH2Cl2
(1:1) as eluent we isolated 48 mg (35%) of diarylation
product XXI, and elution with CH2Cl2–MeOH (first
1
stance. H NMR spectrum, δ, ppm: 1.32 s (2H), 1.41 t
3
(4H, J = 8.0 Hz), 1.44–1.56 m (8H), 1.62 br.s (2H),
2.06 br.s (2H), 3.07 t (4H, 3J = 8.0 Hz), 6.48 d.d.d (2H,
4
4
3J = 8.2, J = 2.2, 0.9 Hz), 6.71 t (2H, J = 2.0 Hz),
3
4
6.78 d.d.d (2H, J = 7.8, J = 1.8, 0.9 Hz), 6.99 t (2H,
3J = 8.0 Hz). C NMR spectrum, δC, ppm: 28.9 (2C),
13
32.7 (2C), 36.4 (1C), 38.5 (2C), 41.9 (4C), 43.5 (2C),
47.7 (1C), 111.5 (2C), 115.0 (2C), 119.8 (2C), 123.3
(2C), 130.4 (2C), 149.7 (2C). Mass spectrum:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011

ARYLATION OF ADAMANTANAMINES: III.
39
3. Averin, A.D., Ranyuk, E.R., Buryak, A.K., Save-
lyev, E.N., Orlinson, B.S., Novakov, I.A., and Belets-
kaya, I.P., Mendeleev Commun., 2009, vol. 19, p. 136.
5:1 and then 2.5:1) gave 62 mg (30%) of compound
XXXII as a colorless oily substance. H NMR spec-
1
trum, δ, ppm: 1.25 s (2H), 1.32–1.51 m (12H),
1.57 br.s (2H), 2.01 br.s (2H), 2.76 t (2H, 3J = 8.3 Hz),
3.04 t (2H, 3J = 7.8 Hz), 3.58 br.s (1H), 3.72 br.s (2H),
4. Ranyuk, E.R., Averin, A.D., Buryak, A.K., Save-
l’ev, E.N., Orlinson, B.S., Novakov, I.A., and Belets-
kaya, I.P., Russ. J. Org. Chem., 2009, vol. 45, p. 1555.
3
4
6.42 d.d (1H, J = 8.2, J = 1.4 Hz), 6.53 br.s (1H),
3
3
5. Novikov, S.S., Khardin, A.P., Radchenko, S.S., Orlin-
son, B.S., Blinov, V.F., Gorelov, V.I., and Zamakh, V.P.,
USSR Inventor’s Certificate no. 682507, 1979; Chem.
Abstr., 1979, vol. 91, no. 193887e.
6.61 d (1H, J = 7.7 Hz), 7.03 t (1H, J = 8.0 Hz).
13C NMR spectrum, δ, ppm: 28.8 (2C), 32.6 (2C), 36.1
(1C), 36.3 (1C), 38.4 (1C), 41.7 (2C), 41.8 (2C), 43.4
(1C), 46.2 (1C), 47.6 (1C), 111.0 (1C), 112.1 (1C),
116.8 (1C), 130.1 (1C), 134.9 (1C), 149.6 (1C). Mass
spectrum: m/z 332.2040 [M]+. C20H29ClN2. Calculated
M 332.2019.
6. Novakov, I.A., Kulev, I.A., Radchenko, S.S., Birz-
nieks, K.A., Boreko, E.I., Vladyko, G.V., and Korob-
chenko, L.V., Pharm. Chem. J., 1987, vol. 21, p. 454.
7. Popov, Yu.V., Korchagina, T.K., Chicherina, G.V., and
Ermakova, T.A., Russ. J. Org. Chem., 2002, vol. 38,
p. 350.
3-Chloro-N-(2-{3-[2-(4-chlorophenylamino)-
ethyl]adamantan-1-yl}ethyl)aniline (XXXIII) was
synthesized from 0.186 mmol (62 mg) of compound
XXXII and 0.209 mmol (40 mg) of p-bromochloro-
benzene in the presence of 4.5 mg (4 mol %) of
Pd(dba)2, 6 mg (4.5 mol %) of BINAP, and 40 mg
(2 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
drous dioxane. By chromatography using petroleum
ether–CH2Cl2 (1:1) as eluent we isolated 24 mg (29%)
of compound XXXIII as a colorless oily substance.
1H NMR spectrum, δ, ppm: 1.32 s (2H), 1.41 t (4H,
3J = 8.1 Hz), 1.43–1.57 m (8H) 1.62 br.s (2H),
2.06 br.s (2H), 3.07 t (4H, 3J = 8.1 Hz), 3.51 br.s (2H),
8. Stroganov, V.F., Mikhal’chuk, V.M., Zaitsev, Yu.S., and
Sidorenko, E.V., Dokl. Akad. Nauk USSR, B: Geol.,
Khim. Biol. Nauki, 1987, p. 47.
9. Khardin, A.P. and Pershin, V.V., Zh. Vses. Khim.
Ob–va., 1979, vol. 24, p. 95.
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Eds., New York: Nova Science, 2002, p. 19.
3
6.44 d.d.d (1H, J = 8.2, 4J = 2.1, 0.8 Hz), 6.50 d (2H,
3
3J = 8.8 Hz), 6.55 t (1H, J = 2.0 Hz), 6.64 d.d.d (1H,
12. Novikov, S.S., Khardin, A.P., Radchenko, S.S., Nova-
kov, I.A., Orlinson, B.S., Blinov, V.F., Gerashchen-
ko, Z.V., Zimin, Yu.B., Voishchev, V.S., and Krupe-
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4
3
3J = 7.9, J = 1.8, 0.8 Hz), 7.05 t (1H, J = 8.0 Hz),
7.10 d (2H, 3J = 8.8 Hz). 13C NMR spectrum, δC, ppm:
28.9 (2C), 32.7 (2C), 36.4 (1C), 38.5 (1C), 38.8 (1C),
41.9 (4C), 43.5 (2C), 47.8 (1C), 111.1 (1C), 112.1
(1C), 113.7 (2C), 116.9 (1C), 121.6 (1C), 129.0 (2C),
130.1 (1C), 135.0 (1C), 147.0 (1C), 149.6 (1C). Mass
spectrum: m/z 442.1958 [M]+. C26H32Cl2N2. Calculated
M 442.1943.
13. Korshak, V.V., Novikov, S.S., Vinogradova, S.V.,
Khardin, A.P., Vygodskii, Ya.S., Novakov, I.A., Orlin-
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Russian Patent no. 2233295, 2004; Chem. Abstr., 2004,
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This study was performed under financial support
by the Russian Academy of Sciences (program P-8,
“Development of Methodology of Organic Synthesis
and Design of Compounds with Practically Valuable
Properties”) and by the Russian Foundation for Basic
Research (project no. 10-03-01108).
15. Novakov, I.A., Popov, Yu.V., Korchagina, T.K., Erma-
kova, T.A., Novopol’tseva, O.M., and Tankov, D.Yu.,
Russian Patent no. 2232782, 2004; Chem. Abstr., 2004,
vol. 141, no. 278874.
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