Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles

Article abstract of DOI:10.1134/S107036321604006X

Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.

Full text of DOI:10.1134/S107036321604006X

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 4, pp. 798–805. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Yu.V. Popov, V.M. Mokhov, K.V. Shcherbakova, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 4, pp. 609–616.
Colloid and Nanosized Catalysts in Organic Synthesis:
XIV.1 Reductive Amination and Amidation
of Carbonitriles Catalyzed by Nickel Nanoparticles
Yu. V. Popov, V. M. Mokhov, and K. V. Shcherbakova
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
e-mail: tons@vstu.ru
Received July 9, 2015
Abstract—Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines
led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines
hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of
formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
Keywords: catalysis, nanoparticles, nickel, hydrogenation, nitriles, amines, transamidation, reductive amination
DOI: 10.1134/S107036321604006X
Catalytic hydrogenation of carboxylic acids nitriles
has several disadvantages, like stringent conditions of
the process, the requirement of expensive metal
complex catalysts [2], and side reactions of secondary
and tertiary amines [3]. Hydrogenation of nitriles in
the liquid phase with hydrogen at atmospheric pressure
in the presence of nickel nanoparticles [1] is also
accompanied by side reactions leading to the formation
of secondary amines as main products. The formation
of secondary and tertiary amines occurs due to
interaction with primary amines generated in situ with
intermediate imines [4] (Scheme 1).
When using threefold excess of amine hydrogenation
catalyzed with platinum on carbon (6 atm at 105°C)
was also accompanied by the formation of
unsymmetrical dialkylamines in 67–93% yield; in
addition, symmetrical diamines (22%) were formed as
by-products [8]. Ikawa et al. [9] have studied the effect
of the solvent and other reaction conditions on N-
monoalkylation of primary aromatic amines with
acetonitrile during the hydrogenation catalysed with
Pd/C. It was shown that the nature of the solvent
affects primarily the degree of nitrile conversion. Yield
of N,N-diethylaniline was 0–60% depending on the
process conditions and the structure of the starting
aromatic amine.
Obviously, when adding primary amines of another
structure to the reaction mixture, intermediate imines
formed during the hydrogenation of nitriles would
interact with these amines to give unsymmetrical N,N-
dialkylamines (Scheme 2).
In order to study the possibility of using an
available nickel catalyst for the preparation of
unsymmetrical dialkylamines we carried out the
hydrogenation of nitrites 1a–1d in the presence of
primary amines (Scheme 3).
This reaction has been described in the literature as
reductive amination of nitriles [5–8]. In particular, it
has been shown that the use of platinum nanofibre
catalyst allowed to synthesize unsymmetrical
dialkylamines in yield of 75–96% at a hydrogen
pressure of 1 at and a temperature of 80°C for 20 h. In
addition, symmetrical diamines were also formed
despite the use of twofold excess of amine R2NH2 [5].
The reactions were carried out in the presence of 1–
2 equivalents of amines and 5–10 mol % of the catalyst
in the liquid phase at a temperature of 60–70°C in a
solution of isopropanol, 1-butanol, or tert-butanol for
10–16 h. After separation of the catalyst, the com-
position of the reaction products was analyzed by gas
chromatography-mass spectrometry method. Most of
the compounds were identified by comparing their
1
For communication XIII, see [1].
798

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XIV.
799
Scheme 1.
NHCH2R
H2, kt
H2, kt
H2, kt
RCH=NH
RCN
RCH=NH
RCH2NH2
RCH2NHCH2R + NH3
RCHNH2
Scheme 2.
NHR2
R2NH2
H2, kt
H2, kt
R1CH=NR2
R1CN
R1CH=NH
R1CH2NHR2
_NH3
R1CHNH2
Scheme 3.
Ni0, H2 (1 atm)
60_70oC
R1CN + R2NH2
1а_1d 2а_2d
R1CH2NHR2
R1CH2NHCH2R1
+
R1CH2N=CHR1
+
3а_3e
5а, 5b
4а_4d
R1 = Pr (1а, 4а, 5а); i-Pr (1b, 4b, 5b), PhCH2 (1c, 4c), CH3(CH2)6 (1d, 4d), R2 = Bu (2а), Cy (2b), Ph (2c), PhCH2 (2d);
R1 = Pr, R2 = PhCH2 (3а); R1 = Pr, R2 = Сy (3b); R1 = i-Pr, R2 = Ph (3c); R1 = PhCH2, R2 = Bu (3d), R1 = CH3(CH2)6, R2 =
Ph (3e).
mass spectra with spectrometer database; other com-
pounds were identified by molecular ions peaks.
the use of low basic aniline 2b the reductive amination
of n-octanoic acid nitrile 1d in n-butanol resulted in a
low yield of the target n-octylaniline 3d (16%) along
with the formation of di-n-octylamine 4d (10%), N-
butylaniline (22%), and N-butyl-n-octylamine (24%).
The last two compounds formed due to the alkylation
of aniline and n-octylamine (generated by the hydro-
genation of nitrile 1d) with n-butanol.
Among the reaction products asymmetric dialkyl-
amines 3a–3d were present. However, the proportion
of target products was strongly dependent on the
structure of the starting substrates and excess of amine
2a–2d. So, the use of amine 2d led to the formation of
N,N-dibenzylbutylamine and tribenzylamine due to
benzylamine disproportionation with release of
ammonia. Dibenzylamine formation proceeded faster
than the hydrogenation of n-butyronitrile to imine,
therefore the reaction products included N,N-dibenzyl-
n-butylamine and no target N-n-butylbenzylamine. A
similar reaction occurred in the case of the cyclo-
hexylamine 2b, which also was prone to disproportiona-
tion [10].
It should be noted that in most cases imines 5a–5d
were detected as intermediates in the formation of
symmetric dialkylamines. The possibility of formation
of imines by the hydrogenation of nitriles has been
described in [14]. For example, intermediate imines
can be obtained through cross-coupling of hydro-
genated nitrile and the added amine on a ruthenium
complex under 4 at of H2 using equimolar nitrile–
amine ratio [15], wherein the imines yield was 30–
99% depending on the nature of the used substrates.
Use of primary alcohols as a solvent resulted in a
side alkylation of amines. For example, hydrogenation
of phenylacetonitrile in the presence of n-butylamine
in n-butanol afforded di-n-butylamine and tri-n-
butylamine that can be ascribed not to the amine dis-
proportionation, but to the alkylation of n-butylamine
with n-butanol trough the mechanism of hydrogen
transfer that has been observed previously in the
hydrogenation of nitriles [1, 11] as well as in isolated
reaction [12, 13].
Interesting results were obtained in the hydro-
genation of nitriles in the presence of secondary amines
like piperidine 6a and morpholine 6b (Scheme 4).
Hydrogenation of nitriles 1a and 1b was carried out
in a medium of amines 6a and 6b, which were used as
a solvent to produce a colloidal solution of the catalyst
by reduction of nickel(II) chloride with sodium boro-
hydride. It made possible to eliminate the influence of
alkanols on the reaction selectivity. Of interest is the
presence of the corresponding enamines in the reaction
Selectivity of the reductive amination of nitriles
depends on the basicity of the amine. For example, at
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

800
POPOV et al.
Scheme 4.
R1
R2
R1
Ni0, H2 (1 atm)
60_70oC
N
R1R2CH2CN +
+
N
N
X
X
HN
X
+
R1
R1
R2
R2
R2
R2
R1
9
1а_1d
6а, 6b
8а_8c
7а_7d
R1 = Et, R2 = H (1а, 9); R1 = Me, R2 = Me (1b); R1 = Ph, R2 = H (1c); R1 = CH3(CH2)6, R2 = H (1d); X = CH2 (6а), O (6b);
R1 = Et, R2 = H, X = CH2 (7а, 8а); R1 = Me, R2 = Me, X = О (7b, 8b); R1 = Ph, R2 = H, X = CH2 (7c, 8c); R1 = CH3(CH2)7,
R2 = H, X = CH2 (7d).
Scheme 5.
H2N
R1
HN
X
Ni0, H2 (1 atm)
N
X
R1R2CH2CN
R1R2CH2CН=NН
R2
N
X
Ni0, H2 (1 atm)
N
X
R1
R1
_NH3
R2
R2
Scheme 6.
R1 NH
O
Ni0, H2 (1 atm)
60_70oC
R1CN + R2C(O)NH2
+ R1CH2NHCH2R1
R2
1а_1c, 1e, 1f
11а_11e
4b, 4c, 4e, 4f
10а, 10b
2
R1 = Pr (1а), i-Pr (1b, 4b), PhCH2 (1c, 4c), PhCH=CH (1e),
R = H (10а), Me (10b);
(1е, 4е);
R1 = Pr, R2 = H (11а), R1 = i-Pr, R2 = H (11b); R1 = PhCH2, R2 = H (11c), R1 = PhCH=CH,
R2 = H (11d); R1 =
, R2 = Me (11e).
mixture together with the target products. The content
of enamines 8a and 8b (46–70%) exceeded the content
of the target compounds 7a and 7b. Probably, aminal
formed by alkylation of a secondary amine with imine
eliminates the ammonia molecule to produce enamine
8, which further is hydrogenated to the corresponding
tertiary amine (Scheme 5).
but for selecting conditions of the synthesis of
enamines by reductive amination of nitriles.
Hydrogenation in the presence of phenylacetonitrile
with piperidine in tert-butanol also led to the formation
of N-(2-phenyl)ethylpiperidine 7c (14%) and enamine
8c (64%). Indirect confirmation of the formation of the
latter is the presence of phenylacetaldehyde in the
reaction medium, which formed through partial
hydrolysis of enamine in the catalyst separation
process. At the same time hydrogenation of octanoic
acid nitrile in the presence of piperidine in tert-butanol
provided only two products: N-1-octylpiperidine 7d
(54%) and di-1-octylamine 4d (32%). In addition, the
products of amine alkylation with tert-butanol were
not detected.
Apparently, the reaction conditions did not allow to
hydrogenate completely the unsaturated bond in the
intermediate enamine, although previously we
managed to carry out this reaction under the same con-
ditions [16]. Obviously, an increase in the reaction
duration or more rigid conditions will lead to the
formation of tertiary amines in yields up to 90%.
However, the fact of enamines detection is important
not only for confirming the mechanism of the reaction,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XIV.
801
Studies performed showed the impossibility of
selective preparation of monoalkylamines through
carbonitriles hydrogenation using the catalyst of this
type. However, we developed a new way of
registration of monoalkylamines formation on the basis
of transamidation reaction of carboxamides in the
presence of metal nanoparticles [17]. For the first time
we carried out hydrogenation of carbonitriles with
hydrogen catalyzed by nickel nanoparticles in the
presence of amides of lower carboxylic acids. When
hydrogenating nitriles 1a–1c, 1e and 1f, the formed
primary amines reacted with carboxylic acids amides
10a and 10b (Scheme 6).
≈3 : 2, i. e., selective formation of amides 11 at an
increase in the length and branching of the nitrile
molecules required a larger excess of the amide.
N,N-Dialkylamides were found not to react under
the studied conditions. The hydrogenation of nitrile 1b
in the presence of N,N-dimethylacetamide 10c led to
the formation of dialkylamine 5b and imine 6b.
In summary, the hydrogenation of carbonitriles
catalyzed by nickel nanoparticles in the presence of
primary amines afforded unsymmetrical N,N-dialkyl-
amines due to alkylation of imines generated in situ.
All steps took place simultaneously in the same
reaction vessel at catalysis with the same catalyst. Use
of primary and secondary alcohols as solvents was
found to be impractical because of the possibility of
side alkylation of amines produced. The possibility of
producing enamines by hydrogenation of nitriles in the
presence of secondary amines was demonstrated. A
probability of amines disproportionation on a nickel
catalyst was detected. A method for hydrogenation of
nitriles to primary amines by converting the latter in
situ into amides derived from formamide transamida-
tion was developed. Optimization of the conditions of
the above reactions will allow developing new methods
for the preparation of unsymmetrical N,N-di(tri)-
alkylamines, enamines, and acylated monoalkylamides.
According GC-MS data, the main reaction products
were amides 11a–11f, whose formation was due to
hydrogenation of nitriles with hydrogen to primary
amines which further reacted through two competitive
routes: reaction with the intermediately generated
imines and transamidation of carboxylic acids amides
to form products 11a–11f and to release ammonia.
Obviously, the use of an excess of amides with respect
to the primary amine favored the transamidation
reaction. Thus, the found two-stage one-pot reaction
can be considered as reductive amidation of
carbonitriles. The resulting amine acyl derivatives may
readily be converted into the corresponding amines by
hydrolysis. This process can be used for the selective
hydrogenation of nitriles to primary amines.
EXPERIMENTAL
It was found that the most suitable is the use of
formamide as apparently more reactive amide than
acetamide. A similar relationship was observed pre-
viously when using copper nanoparticles [17]. Use of
acetamide often does not lead to the formation of the
desired product. Thus, the hydrogenation of 2-cyano-
norbornane in the presence of an equimolar amount of
acetamide yielded dialkylamine as the main product,
the expected acetyl derivative content was only 0.3%.
On the other hand, hydrogenation of nitrile 1c in the
presence of formamide even in 7 h at a low conversion
of the starting nitrile gave rise to only target amide
11c; the corresponding primary and secondary amines
were not formed.
GC-MS analysis was performed on a Saturn 2100
T/GC3900 instrument (EI, 70 eV).
Hydrogenation of n-butyronitrile 1a in the pre-
sence of benzylamine 2d. To a suspension of 0.4 g
(0.012 mol) of sodium borohydride in 20 mL of
1-butanol at 60°C was added 0.8 g (0.006 mol) of
anhydrous nickel(II) chloride. After 10 min the
formation of black colloid solution of catalyst was
observed. Then through the mixture hydrogen was
bubbled, and 6.9 g (0.1 mol) of butyronitrile and 12 g
(0.11 mol) of benzylamine were added. The reaction
was carried out for 14 h at 70°C. After cooling, 1 mL
of water was added to the mixture to accelerate the
catalyst coagulation. The precipitate was filtered off,
the filtrate was analyzed. 1-Butylamine, content
0.25%. Mass spectrum, m/e (Irel, %): 73.8 (100) [M +
1], 72.8 (10) [M]+, 71.8 (4) 42.1 (1.5). N-Butylidene-
1-butylamine (5a), content 1.9%. Mass spectrum, m/e
(Irel, %): 127.8 (24) [M + 1], 125.7 (3), 111.8 (12), 83.9
(100), 70.0 (21), 57.0 (26), 56 (29.5), 43.0 (7), 42.1
Use of an excess of amides also affects the reaction
selectivity. Thus, in the case of nitrile 1a equimolar
ratio of amine 2a and amide 10a was sufficient to
selective producing N-butylformamide 9a. The hydro-
genation of cinnamic nitrile 1d in the presence of
twofold excess of formamide led to the formation of a
mixture of compounds 11e and 4e in a molar ratio of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

802
POPOV et al.
(40), 41.1 (29). Di-n-butylamine (4a), content 14.4%.
Mass spectrum, m/e (Irel, %): 130.7 (7) [M + 2], 129.8
(100) [M + 1], 128.9 (18.5) [M]. Tri-1-butylamine,
content 1.7%. Mass spectrum, m/e (Irel, %): 186.9 (2)
[M + 2], 186.0 (15.3) [M + 1], 183.9 (4) [M], 141.8
(100), 100.0 (59), 99.0 (11), 58.1 (53), 44.1 (4). N,N-
Dibenzyl-n-butylamine, content 54%. Mass spectrum,
m/e (Irel, %): 252.9 (1.5) [M + 1], 252.0 (8) [M]+, 161.8
(100), 132.9 (53.5), 132.1 (52.5), 117.9 (6.5), 92.0
(19), 91.1 (77.5), 65.0 (19), 51.1 (6), 41.2 (5). Tri-
benzylamine, content 10%. Mass spectrum, m/e (Irel,
%): 287.0 (3) [M]+, 286.0 (12), 197.1 (12), 196.2
(100), 194.5 (13), 91.2 (2).
idenediisobutylamine, content 0.5%. Mass spectrum,
m/e (Irel, %): 183.9 (3) [M + 1], 156.9 (11), 156.0
(100), 128.0 (9), 99.8 (19), 84.0 (7), 71.8 (17), 57.0
(10). 54.9 (13), 41.0 (12). N-Isobutylideneaniline,
content of 23%. Mass spectrum, m/e (Irel, %): 148.9 (5)
[M + 2], 147.8 (48) [M + 1], 146.8 (44) [M], 146.1
(18), 132.0 (75), 119.1 (10), 104.9 (14), 104.0 (100),
78.1 (12), 77.2 (78), 76.2 (13), 51.1 (35), 50.2 (19),
41.2 (6). N-Isobutylaniline (3c), content of 34%.
Mass spectrum, m/e (Irel, %): 150.8 (3) [M + 2], 149.9
(28) [M + 1], 149.0 (29) [M], 107.0 (8), 106.0 (100),
77.0 (8), 51.1 (6), 50.2 (3), 41.2 (2). N,N-Diisobutyl-
aniline, content 0.3%. Mass spectrum, m/e (Irel, %):
205.8 (3) [M + 1], 204.7 (11) [M], 161.8 (73), 121.0
(10), 120.0 (100), 119.1 (15), 118.1 (9), 104.0 (9), 77.0
(15), 50.9 (8), 43.0 (23), 41.1 (5).
Hydrogenation of butyronitrile 1a in the presence
of cyclohexylamine 2b was performed similarly using
0.4 g (0.011 mol) of sodium borohydride, 15 mL of
tert-butanol, 0.8 g (0.006 mol) of anhydrous nickel(II)
chloride, 6.9 g (0.1 mol) n-butyronitrile and 9.10 g
(0.11 mol) of cyclohexylamine; reaction time 16 h. Di-
n-butylamine (4a), content 13.3%. Mass spectrum,
m/e (Irel, %): 130.8 (2) [M + 2], 129.8 (15) [M + 1],
128.6 (2) [M], 99.8 (8), 85.8 (100), 70 (15), 56.9 (33),
44.1 (20), 43.0 (20), 41.1 (34). N-Butylcyclohexyl-
amine (3b), content 64.3%. Mass spectrum, m/e (Irel,
%): 156.8 (4) [M + 2], 155.9 (33) [M + 1], 154.8 (3)
[M], 111.9 (100), 83.0 (2), 70.2 (6), 57 (3), 56.1 (15),
41.1 (10). Dicyclohexylamine, content 4.1%. Mass
spectrum, m/e (Irel, %): 183.0 (1) [M + 2], 182.0 (11)
[M + 1], 180.8 (12) [M], 152.0 (6), 138.0 (100), 82.0
(4), 56.1 (27), 44.1 (3), 41.1 (6). N-Cyclohexylidene-
cyclohexylimine, content 5.4%. Mass spectrum, m/e
(Irel, %): 180.9 (6) [M + 2], 179.7 (43) [M + 1], 179.0
(64) [M], 150.0 (23), 136.0 (100), 124. 0 (13), 122.1
(19.5), 108.1 (10), 98.1 (98), 94.2 (10), 82.0 (19), 81.1
(22), 79.1 (15), 69.0 (12), 67.2 (17), 56.1 (17), 55.0
(54), 53.1 (13), 41.1 (35).
Hydrogenation of phenylacetonitrile 1c in the
presence of n-butylamine 2a was performed similarly
using 0.4 g (0.011 mol) of sodium borohydride, 20 mL
of 1-butanol, 0.7 g (0.006 mol) of anhydrous nickel(II)
chloride, 7.3 g (0.1 mol) of n-butylamine and 5 g
(0.043 mol) of phenylacetonitrile; reaction time 16 h.
Di-n-butylamine, content 14.5%. Mass spectrum, m/e
(Irel, %): 130.8 (6) [M + 2], 129.8 (63) [M + 1], 127.8
(4) [M], 86.0 (10), 56.9 (3.5), 44.0 (100), 43.1 (4), 41
(8). Tri-n-butylamine, content of 0.8%. Mass spec-
trum, m/e (Irel, %): 184.0 (2), 141.8 (100), 99.9 (75),
58.0 (55), 44.0 (11), 41.0 (8). N-1-Butyl-2-phenyl-
ethylamine (3d), content 69.6%. Mass spectrum, m/e
(Irel, %): 178.9 (12) [M + 2], 178.0 (100) [M + 1],
105.0 (7), 44.0 (18), 42.0 (1). 2-Phenylethyldi-n-
butylamine, content 1%. Mass spectrum, m/e (Irel, %):
234.0 (1) [M + 2], 232.1 (1) [M + 1], 189.9 (7), 142.9
(10), 141.9 (100), 105 (15), 100.1 (52.5), 91.0 (9), 58.0
(40), 57.0 (4), 44.0 (8), 41.0 (6). Di(2-phenylethyl)-
amine (4c), content 13.7%. Mass spectrum, m/e (Irel,
%): 227.0 (4) [М + 2], 226.0 (27) [М + 1], 133.9 (100),
106.0 (6), 105.0 (60), 91.1 (11), 77.1 (9), 65.0 (8), 51.0
(5), 42.1 (3).
Hydrogenation of isobutyronitrile 1b in the
presence of aniline 2c was performed similarly using
0.4 g (0.011 mol) of sodium borohydride, 15 mL of
tert-butanol, 0.8 g (0.006 mol) of anhydrous nickel(II)
chloride, 6.9 g (0.1 mol) of isobutyronitrile and 6.18 g
(0.2 mol) of aniline; reaction time 15 h. N-Isobutyl-
ideneisobutylamine (5b), content 10.4%. Mass spec-
trum, m/e (Irel, %): 127.8 (13) [M + 1], 126.7 (4) [M],
111.9 (8), 83.4 (100), 82.1 (8), 70.0 (10), 67.0 (11),
57.0 (45), 56.0 (38), 55.1 (17), 42.1 (25), 41.2 (47),
40.1 (4). Diisobutylamine (4b), the content of 3%.
Mass spectrum, m/e (Irel, %): 129.8 (5) [M + 1], 128.6
(2) [M], 127.8 (3), 86.8 (6), 85.8 (100), 70.0 (3), 57.0
(27), 55 (5). 44.1 (17), 43.0 (8), 41.1 (27). N-Isobutyl-
Hydrogenation of n-octanoic acid nitrile 1d in
the presence of aniline 2c was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 15 mL
of 1-butanol, 0.33 g (0.0025 mol) of anhydrous
nickel(II) chloride, 6.3 g (0.05 mol) of the n-octanoic
acid nitrile and 4.7 g (0.051 mol) of aniline; reaction
time 16 h. N-n-Butylaniline, content 22%. Mass
spectrum, m/e (Irel, %): 150.8 (6) [M + 2], 149.8 (59)
[M + 1], 148.9 (43) [M], 106.0 (100), 77.0 (7). N-n-
Butyl-N-n-octylamine, content 24%. Mass spectrum,
m/e (Irel, %): 187.0 (7) [M + 2], 186.0 (53) [M + 1],
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XIV.
803
184.2 (3) [M], 142.1 (16), 86.0 (19), 44 (100), 41.1
(10). N-n-Octylaniline (3e), content 16%. Mass spec-
trum, m/e (Irel, %): 207.0 (5) [M + 2], 206.0 (38) [M +
1], 205.1 (25) [M], 107.0 (8), 106.0 (100), 77.2 (5). Di-
N-octylamine (4d), content 10%. Mass spectrum, m/e
(Irel, %): 243.1 (6) [M + 2], 242.2 (32) [M + 1], 241.3
(2) [M], 240.3 (3), 142.0 (82), 69.0 (4), 44.0 (100),
41.1 (12). Unreacted nitrile 1d (22%) also presented in
the mixture.
Hydrogenation of phenylacetonitrile 1c in the
presence of piperidine 6a was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 20 mL
of tert-butanol, 0.33 g (0.0025 mol) of anhydrous
nickel(II) chloride, 3.5 g (0.03 mol) of phenylaceto-
nitrile 1c and 5.1 g of (0.06) piperidine 6a; reaction
time 14 h. 2-Phenylacetaldehyde, content 12.3%.
Mass spectrum, m/e (Irel, %): 121.8 (9) [M + 2], 120.0
(7) [M], 92.0 (17), 91.0 (100), 65.0 (57), 63.1 (25),
51.0 (276), 50.0 (28), 42.1 (8). N-(2-Phenylethyl)
piperidine (7c), content 14%. Mass spectrum, m/e (Irel,
%): 104.8 (4), 103.0 (2), 99.0 (6), 97.9 (100), 70.1
(16), 65.0 (5), 55.1 (5), 42.0 (9), 41.0 (6). N-1-(2-
Phenyl)vinylpiperidine (8c), content 64%. Mass
spectrum, m/e (Irel, %): 189.0 (4) [M + 2], 188.0 (35)
[M + 1], 187.0 (100) [M], 130.2 (7), 110.2 (4), 104.1
(12), 103.2 (4), 96.2 (2), 84.1 (2), 83.2 (3), 77.1 (1),
51.0 (2), 41.0 (3).
Hydrogenation of butyronitrile 1a in the pre-
sence of piperidine 6a. To a suspension of 0.4 g
(0.012 mol) of sodium borohydride in 20 mL of
piperidine 6a at 30°C was added 0.8 g (0.006 mol) of
anhydrous nickel(II) chloride. The mixture was heated
to 60°C to produce black colloid solution of a catalyst.
Butyronitrile (6.9 g, 0.1 mol) was added to the result-
ing catalyst, and hydrogen was passed at 70°C for
14 h. After cooling, 1 mL of water was added to the
mixture to accelerate the catalyst coagulation. The
precipitate was filtered off, the filtrate was analyzed.
N-n-Butylidene-n-butylamine (5a), content 8%.
Mass spectrum, m/e (Irel, %): 128.8 (13) [M + 2], 127.8
(100) [M + 1], 125.9 (4), 111.9 (16), 85.1 (8), 84.1
(53), 83.2 (9), 70.2 (16), 57.2 (26), 56.2 (30), 55.2
(10), 42.1 (50), 41.2 (34), 40.2 (3). N-n-Butyl-
piperidin (7a), content 19%. Mass spectrum, m/e (Irel,
%): 141.9 (6) [M + 1], 140.7 (2) [M], 139.9 (5), 98.9
(6), 98.0 (100), 70.0 (10), 42.1 (7). N-1-Butyl-1-
idenpiperidin (8a), content 39%. Mass spectrum, m/e
(Irel, %): 139.9 (4) [M + 1], 138.8 (20) [M], 138.0 (7),
125.0 (9), 124.0 (100), 110.0 (8), 96.0 (4), 94.0 (5),
68.0 (20), 42.2 (6), 41.2 (9). N-1-Butyl-1-idendi-n-
butylamine (9), content 31%. Mass spectrum, m/e (Irel,
%): 183.0 (12) [M], 182.0 (100), 181.1 (9), 152.2 (6),
124.0 (5), 41.2 (3).
Hydrogenation of n-octanoic acid nitrile 1d in
the presence of piperidine 6a was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 15 mL
of tert-butanol, 0.33 g (0.0025 mol) of anhydrous
nickel(II) chloride, 3.5 g (0.028 mol) of the nitrile 1d,
and 4.3 g (0.05 mol) of piperidine 6a; reaction time
16 h. Di-n-octylamine (4e), content 32%. Mass spec-
trum, m/e (Irel, %): 242.2 (1) [M + 1], 241.2 (17) [M],
240.2 (100), 168.2 (6), 140.1 (76), 112.1 (11), 70.1 (6),
56.0 (8), 41.0 (13). N-1-Octylpiperidine (7d), content
54%. Mass spectrum, m/e (Irel, %): 199.1 (1) [M + 2],
198.1 (8) [M + 1], 196.1 (4) [M – 1], 98.0 (100), 70.1
(8), 42.0 (4).
Hydrogenation of butyronitrile 1a in the pre-
sence of formamide 10a was performed similarly
using 0.4 g (0.01 mol) of sodium borohydride, 20 mL
of tert-butanol, 0.7 g (0.005 mol) of anhydrous ni-
ckel(II) chloride, 13.8 g (0.2 mol) of nitrile 1a, and 9 g
(0.2 mol) of formamide 10a; reaction time 16 h. N-n-
Butylamine, content 5.3%. Mass spectrum, m/e (Irel,
%): 72.7 (5) [M], 71.8 (7), 60.9 (7), 59.0 (7), 56.9 (7),
45.0 (100), 44.0 (16), 42.9 (56), 41.0 (20). N-n-
Butylformamide (11a), content 85%. Mass spectrum,
m/e (Irel, %): 101.0 [M] (7), 87.0 (8), 86.0 (3), 57.8
(100), 56.9 (26), 56.0 (19), 56.0 (8), 55.1 (4) 46.0 (25),
41 (22). Unreacted formamide (5%) also presented in
the mixture.
Hydrogenation of isobutyronitrile 1b in the pre-
sence of morpholine 6b was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 20 mL
of morpholine 6b, 0.33 g (0.0025 mol) of anhydrous
nickel(II) chloride and 6.9 g (0.1 mol) of isobutyro-
nitrile; reaction time 16 h. N-Isobutylmorpholine
(7b), content 42%. Mass spectrum, m/e (Irel, %): 143.9
(2) [M + 1], 142.7 (2) [M], 141.9 (1), 100.9 (5), 100.0
(100), 72.0 (7), 69.9 (20), 55.9 (12), 42.0 (12), 41.0
(6). N-Isobutylenemorpholine (8b), content 46%.
Mass spectrum, m/e (Irel, %): 142.9 (2) [M + 1], 141.9
(30) [M], 141.0 (100), 140.0 (18), 126.0 (73), 112.1
(26), 96.0 (14), 83.0 (14), 82.0 (68), 68.0 (56), 41.9
(18), 41.0 (16).
Hydrogenation of isobutyronitrile 1b in the pre-
sence of formamide 10a was performed similarly
using 0.4 g (0.01 mol) of sodium borohydride, 16 mL
of tert-butanol, 0.7 g (0.005 mol) of anhydrous ni-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

804
POPOV et al.
ckel(II) chloride, 6.9 g (0.1 mol) of the nitrile 1b, and
9 g (0.2 mol) of formamide 10a; reaction time 16 h. N-
Isobutylideneisobutylamine (5b), content 17%. Mass
spectrum, m/e (Irel, %): 127.8 (13) [M + 1], 126.7 (4)
[M], 111.9 (8), 83.9 (100), 82.1 (8), 70.0 (10), 67.0
(11), 57.0 (46), 56.0 (38), 55.0 (15), 42.0 (23), 41.1
(43), 40.1 (4). N-Isobutylformamide (11b), content
66%. Mass spectrum, m/e (Irel, %): 102.7 (5) [M + 2],
101.7 (100) [M + 1], 100.0 (12) [M], 86.0 (13), 59.0
(39), 58.0 (51), 57.1 (12), 56.0 (15), 46.1 (67), 41.1
(35). Diisobutylamine (4b), content 2%. Mass spec-
trum, m/e (Irel, %): 129.8 (12) [M + 1], 128.9 (3) [M],
126.8 (1), 100.8 (29), 99. 8 (75), 85.8 (22), 73.9 (100),
73.0 (19), 72.0 (38), 57.9 (10), 56.9 (26), 56.0 (23), 55
(37). 46.0 (39), 43.0 (19), 41.1 (40).
1.8 g (0.03 mol) acetamide; reaction time 14 h. 2-
Aminomethylnorbornane, content 8%. Mass spec-
trum, m/e (Irel, %): 126.7 (5) [М + 2], 125.8 (55) [М +
1], 124.8 (10) [М], 107.8 (16), 95.1 (16), 79.0 (31),
67.1 (63), 66.0 (100), 56 (14), 41.2 (21). N-n-Butyl-
idene-2-aminomethylnorbornane, content 0.3%. Mass
spectrum, m/e (Irel, %): 180.0 (6) [М + 1], 178.0 (2),
136.8 (11), 135.9 (100), 67.1 (14), 42.1 (9), 41.2 (9).
N-n-Butyl-2-aminomethylnorbornane, content 31%.
Mass spectrum, m/e (Irel, %): 183.0 (11) [М + 2], 182.0
(100) [М + 1], 138.0 (3), 109.1 (5), 44.2 (25). N-
Acetyl-2-aminomethylnorbornane 11d, content 0.3%.
Mass spectrum, m/e (Irel, %): 169.0 (3) [М + 2], 167.8
(29) [М + 1], 166.9 (3) [М], 152.0 (47), 123.8 (6),
107.8 (32), 99.7 (19), 98.8 (22), 94.9 (65), 92.9 (51),
91.0 (24), 80.0 (99.7), 78.9 (58), 77.0 (31), 73.0 (55),
67.0 (100), 66.0 (53), 65.0 (29), 60.0 (62), 56.0 (17),
44.0 (30), 43.0 (95), 41.1 (22). N-(2-Norbornyl)methyl-
ene(2-norbornyl)methylamine, content 0.7%. Mass
spectrum, m/e (Irel, %): 233.0 (1.5) [M + 2], 232.1 (9)
[М + 1], 231.1 (1) [М], 202.0 (10), 163.8 (44), 136.1
(100), 79.0 (11), 67.2 (22), 56.0 (8), 41.2 (10). Bis(2-
norbornylmethyl)amine (4f), content 53%. Mass
spectrum, m/e (Irel, %): 235.1 (16) [M + 2], 234.2 (100)
[М + 1], 138.2 (35) [С7H11CH2NH=CH2]+, 109.1 (15),
67.2 (22), 44 (40).
Hydrogenation phenylacetonitrile 1c in the pre-
sence of formamide 10a was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 20 mL
of tert-butanol, 0.33 g (0.0025 mol) of anhydrous
nickel(II) chloride, 3.5 g (0.03 mol) of phenyl-
acetonitrile 1c and 2.7 g (0.06 mole) formamide 10a;
reaction time 7 h. N-2-Phenylethylformamide (11c),
content 14%. Mass spectrum, m/e (Irel, %): 149.8 (3)
[M + 1], 148.8 (3) [M], 105.0 (10), 104.0 (100), 103.0
(8), 91.1 (29), 78.1 (10), 65.0 (16), 51.0 (6), 50.0 (6). Un-
reacted nitrile 1c (85%) also presented in the mixture.
Hydrogenation of isobutyronitrile 1b in the pre-
sence of N,N-dimethylacetamide 10c was performed
similarly, using 0.2 g (0.005 mol) of sodium boro-
hydride, 20 mL of tert-butanol, 0.33 g (0.0025 mol) of
anhydrous nickel(II) chloride, 3.5 g (0.05 mol) of the
nitrile 1b, and 17.5 g (0.2 mol) N,N-dimethylacetamide
10c; reaction time 15 h. N-Isobutylideneisobutyl-
amine (5b), content 11%. Mass spectrum, m/e (Irel, %):
128.0 (35) [M + 1], 126.8 (7) [M], 111.9 (12), 83.9
(100), 82.1 (8), 70.0 (11), 67.0 (14), 57.0 (57), 56.0
(54), 55.0 (21), 42.0 (33), 41.0 (67), 40.0 (6). Diisobutyl-
amine (4b), content 2.5%. Mass spectrum, m/e (Irel,
%): 129.8 (9) [M + 1], 128.6 (2) [M], 128.0 (4), 87.0
(8), 85.9 (100), 70.0 (2), 57.0 (28), 55 (6). 44.0 (25),
43.0 (10), 41.0 (32). Unreacted dimethylacetamide
(83%) also presented in the mixture.
Hydrogenation of cinnamic nitrile 1d in the pre-
sence of formamide 10a was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 15 mL
of tert-butanol, 0.33 g (0.0025 mol) of anhydrous
nickel(II) chloride, 3.9 g (0.03 mol) of the nitrile 1e,
and 2.7 g (0.06 mol) of formamide 10a; reaction time
16 h. n-Propylbenzene, content 0.3%. Mass spectrum,
m/e (Irel, %): 120.8 (2) [M + 1], 119.8 (21) [M], 90.9
(100), 77.0 (4), 65.0 (16), 49.9 (5). 3-Phenylpropio-
nitrile, content 3.2%. Mass spectrum, m/e (Irel, %):
131.8 (2) [M + 1], 130.7 (12) [M], 91.8 (7), 90.9 (100),
65.0 (15), 50.1 (6). 3-Phenylpropylformamide (11c),
content 46%. Mass spectrum, m/e (Irel, %): 163.8 (100)
[M + 1], 162.9 (15) [M], 118.0 (58), 117.0 (58), 105.1
(9), 91.1 (26), 77.2 (10), 65.0 (16), 59.0 (33), 44.0 (8).
Di(3-phenylpropyl)amine, content 39%. Mass spec-
trum, m/e (Irel, %): 255.0 (2) [M + 2], 255.0 (13) [M +
1], 253.0 (26) [M], 148.0 (43), 91.1 (41), 77.2 (9), 65.0
(13), 44.0 (100).
REFERENCES
1. Popov, Yu.V., Mokhov, V.M., and Kalitina, I.I., Russ. J.
Gen. Chem., 2016, vol. 86, no. 2, p. 281. DOI: 10.1134/
S1070363216020122.
2. Werkmeister, S., Junge, K., and Beller, M., Org. Proc.
Res. Dev., 2014, vol. 18, p. 289. DOI: 10.1021/
op4003278.
Hydrogenation of 2-cyanonorbornane 1f in the
presence of acetamide 2b was performed similarly
using 0.2 g (0.005 mol) of sodium borohydride, 20 mL
of n-butanol, 0.33 g (0.0025 mol) of anhydrous ni-
ckel(II) chloride, 3.6 g (0.03 mol) of the nitrile 1b, and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XIV.
3. de Bellefon, C. and Fouilloux, P., Catal. Rev.-Sci. Eng.,
805
vol. 29, no. 11, p. 1247. DOI: 10.1021/ie50335a011.
1994, vol. 36, no. 3, p. 459. DOI: 10.1080/
01614949408009469.
4. Schärringer, P., Müller, Th.E., and Lercher, J.A.,
J. Catal., 2008, vol. 253, p. 167. DOI: 10.1016/
j.jcat.2007.10.008.
5. Lu, S., Wang, J., Cao, X., Li, X., and Gu, H., Chem.
Commun., 2014, vol. 50, p. 3512. DOI: 10.1039/
C3CC48596J.
11. Werkmeister, S., Bornschein, C., Junge, K., and Beller, M.,
Eur. J. Org. Chem., 2013, no. 18, p. 3671. DOI:
10.1002/ejoc. 201300151.
12. Mokhov, V.M., Popov, Yu.V., and Tankabekyan, N.A.,
Russ. J. Gen. Chem., 2014, vol. 84, no. 5, p. 826. DOI:
10.1134/S1070363214050065.
13. Shimizu, K., Shimura, K., Ohshima, K., Tamura, M.,
and Satsuma, A., Green Chem., 2011, vol. 13, p. 3096.
DOI: 10.1039/C1GC15835J.
6. Bagala, D.B. and Bhanage, B.M., Adv. Synth. Catal.,
2015, vol. 357, p. 883. DOI: 10.1002/adsc.201400940.
14. Dell’Anna, M.M., Gallo, V., Mastrorilli, P., and
Romanazzi, G., Molecules, 2010, vol. 15, p. 3311. DOI:
10.3390/molecules15053311.
15. Srimani, D., Feller, M., Ben-David, Y., and Milstein, D.,
Chem. Commun., 2012, vol. 48, p. 11853. DOI:
10.1039/c2cc36639h.
16. Mokhov, V.M., Popov, Yu.V., and Nebykov, D.N.,
Russ. J. Gen. Chem., 2014, vol. 84, no. 11, p. 2073.
DOI: 10.1134/S1070363214110036.
17. Mokhov, V.M., Popov, Yu.V., and Budko, I.I., Russ. J.
Gen. Chem., 2015, vol. 85, no. 4, p. 820. DOI: 10.1134/
S1070363215040088.
7. Van der Waals, D., Pettman, A., and Williams, J.M.J.,
RSC Adv., 2014, vol. 4, no. 94, p. 51845. DOI: 10.1039/
C4RA11193A.
8. Sharma, S.K., Lynch, J., Sobolewska, A.M., Plucinski, P.,
Watson, R.J., and Williams, J.M.J., Catal. Sci. Technol.,
2013, vol. 3, p. 85. DOI: 10.1039/c2cy20431b.
9. Ikawa, T., Fujita, Y., Mizusaki, T., Betsuin, S.,
Takamatsu, H., Maegawa, T., Monguchi, Y., and Sajiki, H.,
Org. Biomol. Chem., 2012, vol. 10, p. 293. DOI:
10.1039/c1ob06303k.
10. Carswell, T.S. and Morrill, H.L., Ind. Eng. Chem., 1937,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016