Colloid and nanosized catalysts in organic synthesis: XII. Hydrogenation of carbonitriles catalyzed by nickel nanoparticles

Article abstract of DOI:10.1134/S1070363216020110

Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in isopropanol proceeds under atmospheric pressure of hydrogen within 6-15 h to yield mainly secondary amines. Hydrogenation of α-aminonitriles results in reductive decyanation. β-Aminonitriles undergo hydrogenolysis at the nitrogen-carbon bond.

Full text of DOI:10.1134/S1070363216020110

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 2, pp. 273–280. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.M. Mokhov, Yu.V. Popov, K.V. Shcherbakova, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 2, pp. 245–252.
Colloid and Nanosized Catalysts in Organic Synthesis:
XII.1 Hydrogenation of Carbonitriles Catalyzed
by Nickel Nanoparticles
V. M. Mokhov, Yu. V. Popov, and K. V. Shcherbakova
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
e-mail: tons@vstu.ru
Received June 29, 2015
Abstract—Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in isopropanol proceeds under
atmospheric pressure of hydrogen within 6–15 h to yield mainly secondary amines. Hydrogenation of α-
aminonitriles results in reductive decyanation. β-Aminonitriles undergo hydrogenolysis at the nitrogen–carbon
bond.
Keywords: catalysis, nanoparticles, nickel, hydrogenation, nitrile, amine, hydrogenolysis, decyanation
DOI: 10.1134/S1070363216020110
Hydrogenation of nitriles is among the most often
used protocols for preparation of primary amines,
valuable intermediates in the synthesis of dyes and
polymers as well as in pharmacology [2, 3]. Catalytic
hydrogenation proceeds under fairly rigid conditions
(100°C, 50–100 atm) and is accompanied with side
reactions of secondary and tertiary amines formation
[4]. In industry, the reaction is performed in excess of
hydrogen [5]; however, this does not prevent the side
products formation.
N-butylidenbutylamine has been observed in the
course of the reaction. Noteworthily, the reaction
catalyzed by the Raney cobalt has been three times
slower to give 1-butylamine with up to 98%
selectivity.
Dialkylamines formation occurs due to alkylation
of the intermediately formed nitrile imine with the
starting primary amine, followed by elimination of
ammonia molecule and hydrogenation of the formed
alkylated imine with hydrogen [9] (Scheme 1).
Liquid-phase hydrogenation of phenylacetonitrile
with hydrogen using Pd/C catalyst has been described
in [6]. The reaction performed under 6 atm of H2 at 40°C
has provided for complete conversion of the starting
nitrile; the selectivity with respect to the primary
amine being of 35–45%. The reaction is accompanied
with side formation of di- and trialkylamines.
Trialkylamines are formed similarly, due to
alkylation of an imine with the side-formed dialkyl-
amine. In addition, formation of di- and trialkylamines
has been observed even in the course of gas-phase
hydrogenation of nitriles. In particular, selective hydro-
genation of propionitrile into 1-propylamine (90%) in
the gas phase using hybrid copper lanthanide oxides
proceeds at 200°C and overall pressure of 1 atm in the
presence of >50-fold molar excess of hydrogen.
The Raney nickel and cobalt are the most easily
available catalysts for nitriles hydrogenation [7].
Hydrogenation of butyronitrile affording 1-amino-
butane has been reported in [8]. The reaction occurs on
the Raney nickel at 100°C under 30 atm of H2 during
30 min. The selectivity with respect to 1-aminobutane
has been of about 66%; di-n-butylamine has been
obtained as a side product; the formation of intermediate
The data on the C≡N bond hydrogenation using
nanosized catalysts have been scarce. For example,
Fe3O4 nanoparticles modified with silicon liquids and
poly(vinyl pyridine) have been applied for reduction of
a number of aliphatic and aromatic nitriles with
sodium borohydride in aqueous medium [10]. Poly-
mer-supported rhodium complexes have been used for
hydrogenation of benzonitrile with hydrogen [11]:
1
For communication XI, see [1].
273

274
MOKHOV et al.
Scheme 1.
H2, cat
H2, cat
RCH=NH
NHCH2R
RCN
RCH2NH2
RCH=NH
H2, cat
RCH2NHCH2R + NH3
RCHNH2
Scheme 2.
RCH2NH2 + (RCH2)2NH + (RCH2)3N
Ni0, H2 (1 atm)
RCN
1а−1c
60−70oC
2а−2c
3а−3c
4а−4c
R= Pr (а), i-Pr (b), PhCH2 (c).
benzonitrile has been selectively (83%) converted to
N-benzylidenebenzylimine under 20 atm of H2 within
1 h.
through a mixture of cabonitrile and the catalyst under
atmospheric pressure at 60–80°C during 10–16 h
(Scheme 2).
Ruthenium nanoparticles (2–3 nm) have been found
to catalyze hydrogenation of alkylnitriles. For example,
acetonitrile and propionitrile have been hydrogenated
in the presence of the catalyst (0.004 mol%) at 140°C
and hydrogen pressure of 45–90 atm with 40–50%
conversion [12]. Depending on the conditions, the
selectivity with respect to trialkylamines has ranged
between 60 and 100%. The fraction of the primary
amines in the products has not exceeded 4%, and that
of the secondary amines has been below 30%.
Hydrogenation of benzonitrile has proceeded at 140–
290°C and pressure of 32–115 atm to give 57% of
benzylamine, 11–56% of dibenzylamine, 20–47% of
benzylidenebenzylamine, and 0–37% of tribenzyl-
amine. The reaction duration in all the cases has been
of 1–3 d. The reported data have evidenced about the
enhanced selectivity of the primary amine formation
with the increasing hydrogen pressure and the reaction
temperature; decrease of the pressure and the tem-
perature have caused the increase of tribenzylamine
yield, and that of benzylamine has been down to 0–7%.
According to the GC–MS data, hydrogenation of
nitriles 1a–1c with hydrogen under atmospheric
pressure led to the formation of a mixture of primary,
secondary, and tertiary amines, the secondary amines
3a–3c being the major products. In particular,
hydrogenation of isobutyronitrile afforded 4 wt % of
isobutylamine 2b, 48 wt % of diisobutylamine 3b, and
18 wt % of triisobutylamine 4b. Hydrogenation of
phenylacetonitrile during 10 h led to the formation of
phenylethylamine 3c (74%) and bis(2-phenylethyl)-
amine 4a (16%). In addition, the product of alkylation
of benzylamine with isopropanol used as the solvent
(2.1%) was identified in the reaction mixture. Alkyla-
tion of primary amines prepared by hydrogenation of
nitriles with isopropanol has been reported earlier [14–16].
Formation of dialkylamines in the course of liquid-
phase hydrogenation of carbonitriles could be ex-
plained by the low content of hydrogen in the liquid
organic phase, and the formed primary amine therefore
almost completely reacted with the intermediate imine.
In view of that, the proposed hydrogenation procedure
could be recommended exclusively for preparation of
the symmetrical dialkylamines, but not monoalkylamines.
It has been earlier shown that the use of metal
nanoparticles catalyzes the hydrogenation of C=N
bond with hydrogen [13]. In this work we investigated
a possibility of liquid-phase hydrogenation of nitriles
catalyzed by nickel nanoparticles.
Nonborn-5-ene-2-carbonitrile, nitrile of cinnamic
acid, and 2-adamantylideneacetonitrile and its deriva-
tives containing both the conjugated and the isolated
double bonds with various degree of substitution were
used as the model unsaturated nitriles. Hydrogenation
of nonborn-5-ene-2-carbonitrile afforded the secondary
amine as a mixture of endo- and exo-isomers as the
main reaction product (88 wt %). The primary and the
tertiary amines content were of about 5 and 2%,
respectively (Scheme 3).
Saturated and unsaturated α- and β-aminonitriles as
well as α-hydroxynitrile were chosen as the starting
substrates. Colloid solution of nickel prepared via
reduction of anhydrous nickel(II) chloride with sodium
borohydride in isopropanol, n-butanol, or tert-butanol
was used as the catalyst. The reaction was performed
upon bubbling of hydrogen with the rate of 20–25 mL/min
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COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XII.
275
Scheme 3.
Ni0, H2 (1 atm)
CN
NH2
60−70oC
1d
2d, 5.5%
N
+
+
NH
3d, 89.2%
4d, 2%
Scheme 4.
CN
Ni0, H2
60−70oC, 6 h
CN
6e
Ni0, H2
N
H
+
1e
NH2
60−70oC, 16 h
2e
3e
Scheme 5.
NH2
CN
CN
Ni0, H2 (1 atm)
+
+
60−70oC
1f
7f, 5.7%
6f, 75.5%
2f, 13.3%
Cinnamic acid nitrile, with the multiple bond α-
positioned relative to the nitrile group, underwent
hydrogenation by 50% within 6 h to form 3-
phenylpropionitrile; when the reaction duration was
increased to 16 h, 3-phenyl-1-aminopropane (38%) and
the corresponding dialkylamine (57%) were detected
in the reaction mixture. The typical feature of the un-
saturated nitriles hydrogenation was priority saturation
of the multiple carbon–carbon bond (Scheme 4).
Analysis of the products composition showed
significantly larger rate of hydrogenation of even
sterically hindered C=C bond compared to
hydrogenation of nitrile group. The low reactivity of
C≡N bond led to cleavage of the carbon–nitrogen bond
of the primary amine (about 30% of the prepared
amount). Introduction of an alkyl substituent at the
Scheme 6.
Hence, the described hydrogenation protocol could
be again suggested for preparation of symmetrical
dialkylamines, but not monoalkylamines.
R
R
Ni0, H2 (1 atm)
CN
CN
60−70oC
According to GC–MS data, hydrogenation of 2-
adamantylideneacetonitrile led to the formation of a
mixture of 2-adamantylacetonitrile (75.5%), 2-(2-
amino)ethyladamantane (13.7%), and 2-ethyladamantane
(5.7%) (Scheme 5).
1g, 1h
6g, 6h, 75.5−99%
R = Me (g), Et (h).
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MOKHOV et al.
Interestingly, hydrogenation of 2-hydroxy-2-cyano-
Scheme 7.
adamantane as a representative of α-hydroxynitriles
under the similar conditions led to the formation of 2-
hydroxyadamantane in 92% yield as the product of
reductive decyanation as well. The yield of 2-amino-
methyl-2-hydroxyadamantane was of approximately
3% (GC–MS data) (Scheme 9).
O
CN
N
N
Ni0, H2
60−70oC
O
8i
1i
Hydrogenolysis accompanied by a rupture of the
carbon–nitrogen bond of primary amine has been
observed for a number of nitriles [18]; therefore we
expected formation of 2-hydroxy-2-methyladamantane
in the studied case. Hence, the reductive decyanation
was typical of nitrile 1n, similarly to aminonitriles 1i–
1k.
structure of nitriles 1g and 1h led to disappearance of
primary amines in the mixture, and the corresponding
saturated nitriles 2g and 2h were the only reaction
products in that case (Scheme 6).
Reduction of nitrile group in α-aminonitriles has
been recognized among the most obvious methods of
synthesis of 1,2-diaminoethane derivatives. We
attempted to perform hydrogenation of aminonitriles
1i–1l catalyzed by nickel nanoparticles. It was found
that hydrogenation of 2-morpholino-2-cyanoadamantane
1i provided amine 8i as the only reaction product,
confirming the reductive decyanation of the starting
carbonitriles. This phenomenon has been observed
earlier [17] (Scheme 7).
The results of hydrogenation of β-aminonitriles 1m
and 1n (the products of cyanoethylation of morpholine
and piperidine, respectively) under the similar
conditions were unexpected. In that case, hydro-
genolysis of the carbon–nitrogen bond led to the
formation of morpholine and piperidine (60–70 mol %),
respectively. According the GC–MS data, a high-
boiling fraction obtained after distilling off piperidine
and morpholine contained the products of their
alkylation, 1,3-bis-N-morpholino(piperidino)propanes
12m and 12n, instead of expected 3-aminopropyl
derivatives (Scheme 10).
Hydrogenation of nitriles 1j and 1k occurred via
decyanation to give compounds 8j and 8k in 65–80%
yield as well as via C–N bond hydrogenolysis to form
9k and 9l in 15–33% yield. The products of nitrile
group hydrogenation were not detected (Scheme 8).
Besides the above-mentioned products, those with
molecular ions corresponding to the alkylated species
Scheme 8.
Ni0, H2 (1 atm)
NH
N
N
CN
+
60−70oC
8j, 80%
9j, 15%
1j
H
N
H
N
Ni0, H2 (1 atm)
NH2
+
60−70oC
CN
8k, 65%
9k, 33%
1k
Scheme 9.
CN
OH
OH
Ni0, H2 (1 atm)
NH2
+
OH
60−70oC, 1-BuOH
10l, 92%
1l
2l, 3%
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COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XII.
277
Scheme 10.
CN
Ni0, H2 (1 atm)
N
NH
X
70oC, i-PrOH, 16 h
X
1н, о
9m, 9n
N
NPr2
N
N
+
+
+
NH2
X
X
X
13m, 13n (21.3−21.6%)
11
12m, 12n (42−50%)
X = CH2 (m), O (n).
CN
Ni0, H2 (1 atm)
70oC, i-PrOH, 8 h
N
NH2
N
NH
+
O
O
O
1n
2n
9n
of the expected primary amines with two molecules of
1-propylamine or isopropanol 13m and 13n were
detected; dialkylamines were not found. It should be
noted that hydrogenation of nitrile 1n in tert-butanol
provided a mixture of the target nitrile 2n (37 wt %)
with conversion of the starting nitrile about 60%;
23 wt % of morpholine formed as a result of
hydrogenolysis of amine 2n was detected as well.
Hydrogenation of butyronitrile 1a. Anhydrous
nickel(II) chloride (0.5 g, 0.004 mol) was added to a
suspension of sodium borohydride (0.3 g, 0.008 mol)
in 15 mL of tert-butanol; formation of black colloidal
solution was observed. n-Butyronitrile 1a (6.9 g,
0.1 mol) was added to the prepared catalyst under
hydrogen bubbling. The reaction was carried out at
60°C during 10 h. After the reaction was complete, the
mixture was cooled, and water (2 mL) was added to
accelerate the catalyst coagulation. The precipitate was
filtered off, and the filtrate was analyzed by the means
of chromato-mass spectrometry. Di(n-butyl)amine 3a,
content 69 wt %. Mass spectrum, m/e (Irel, %): 130.0
(8) [М + 1], 129 (2) [М], 85.9 (43), 70.0 (7.4), 56.0 (6),
44.0 (100). 1-Butylidene-1-aminobutane, content
7 wt %. Mass spectrum, m/e (Irel, %): 128.9 (1.3) [М +
2], 128.0 (17.6) [М + 1], 111.9 (12), 83.9 (100), 70.0
(24), 57.0 (28), 56.0 (30.6), 41.9 (38).
Formation of amine 2n in the reaction performed
for shorter time confirmed the sequential scheme of
hydrogenolysis and formation of other side products;
only the lateral alkyl groups at the nitrogen-containing
ring underwent hydrogenolysis, the ring remained intact.
In summary, an essential special feature of the
course of the liquid-phase hydrogenation of carbo-
nitriles in the presence of colloidal nickel catalyst was
demonstrated. The nitrile structure was found to be the
main factor of hydrogenation (hydrogenolysis)
direction; deeper understanding of that effect required
further investigation. It was established that the side
reaction of alkylation of the amines produced via
hydrogenation was possible in the presence of primary
or secondary alcohols as solvents. The possibility of
hydrogenolysis of C–N bond in tertiary amines was
demonstrated for the first time; additional research in
this field will likely lead to elaboration of the method
of secondary amines synthesis from tertiary ones.
Hydrogenation of isobutyronitrile 1b was per-
formed similarly, using sodium borohydride (0.3 g,
0.008 mol), 15 mL of tert-butanol, anhydrous nickel(II)
chloride (0.5 g, 0.004 mol), and isobutyronitrile 1b
(6.9 g, 0.1 mol). The reaction duration was 12 h, the
temperature was 70°C. 1-Amino-2-methylpropane
2b, content 4 wt %. Mass spectrum, m/e (Irel, %): 73.8
(48) [М + 1], 72.8 (20) [М], 57.0 (100), 43.0 (16), 41.2
(36). Diisobutylamine 3b, content 48 wt %. Mass
spectrum, m/e (Irel, %): 130.8 (8) [M + 2], 129.7 (100)
[М + 1], 128 (7) [М], 85.8 (7), 57.2 (10), 44.1 (12),
41.1 (13). Triisobutylamine 4b, content 18 wt %.
Mass spectrum, m/e (Irel, %): 185 (2) [M], 170 (2), 143.0
(11), 142.0 (100), 100.0 (6), 86 (25), 57.0 (25), 41.1 (13).
EXPERIMENTAL
Chromato-mass spectral analysis was performed
using a Saturn 2100 T/GC3900 (EI, 70 eV) instrument.
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MOKHOV et al.
Hydrogenation of phenylacetonitrile 1c was
cinnamic acid nitrile (6 g, 0.046 mol). The reaction
duration was 6 h, the temperature was 70°C. 3-Phenyl-
propionitrile 6e, content 48.9 wt %. Mass spectrum,
m/e (Irel, %): 132.0 (10) [М + 1], 130.7 (12) [М]+,
129.0 (2), 104.0 (2), 91.1 (100), 65.0 (14). Starting
cinnamic acid nitrile was also detected in the reaction
mixture, its content was of 47.9 wt %.
performed similarly, using sodium borohydride (0.4 g,
0.011 mol), 20 mL of isopropanol, anhydrous nickel(II)
chloride (0.7 g, 0.006 mol), and phenylacetonitrile 1c
(5 g, 0.043 mol). The reaction duration was 16 h, the
temperature was 70°C. 2-Phenylethylamine 2c,
content 74 wt %. Mass spectrum, m/e (Irel, %): 122.8
(8) [M + 2], 121.9 (100) [M + 1], 121.0 (22) [M], 120.0
(11), 90.9 (12), 65.0 (2). Isopropyl-2-phenyl-
ethylamine, content 2.1 wt %. Mass spectrum, m/e
(Irel, %): 154.8 (4) [M + 2], 163.7 (33) [M + 1], 161.8
(6) [M]+, 147.8 (10), 104.8 (65), 102.8 (14), 90.9 (32),
72.0 (100), 65.0 (15), 56.0 (9), 43.0 (5), 41.2 (11). Di
(2-phenylethyl)amine 3c, content 16 wt %. Mass
spectrum, m/e (Irel, %): 227.0 (17) [M + 2], 226.0 (100)
[M + 1], 224.8 (1) [M]+, 134.9 (41), 117.0 (4), 106.0
(6), 105.1 (44), 91.1 (5), 78.0 (1), 77.1 (4), 65.0 (4).
Hydrogenation of 2-adamantylideneacetonitrile
1f was performed similarly, using sodium borohydride
(0.5 g, 0.014 mol), 20 mL of isopropanol, anhydrous
nickel(II) chloride (0.9 g, 0.007 mol), and 2-
adamantylenacetonitrile 1f (8.7 g, 0.05 mol). The reac-
tion duration was 12 h, the temperature was 70°C. 2-
Ethyladamanthane 7f, content 5.7 wt %. Mass
spectrum, m/e (Irel, %): 165 (2) [M + 1], 164 (13) [M]+,
135 (100), 107 (9), 93 (10), 79 (12). 2-Adamantyl-
acetonitrile 6f, content 75.5 wt %. Mass spectrum, m/e
(Irel, %): 176 (21) [M + 1], 175 (99) [M]+, 174 (37),
148 (14), 135 (100) [Ad]+, 107 (32), 93 (35), 80 (32),
51 (10), 41 (27). 2-Aminoethyladamantane 2f,
content 13.3 wt %. Mass spectrum, m/e (Irel, %): 180
(100) [M + 1], 162 (9), 134(1), 133 (3).
Hydrogenation of nonborn-5-ene-2-carbonitrile
1d was performed similarly, using sodium borohydride
(0.3 g, 0.008 mol), 15 mL of isopropanol, anhydrous
nickel(II) chloride (0.5 g, 0.004 mol), and nitrile 1d
(12 g, 0.1 mol). The reaction duration was 12 h, the
temperature was 70°C. 2-Aminomethylnorbornane
2d, content 5.5 wt %. Mass spectrum, m/e (Irel, %): 125
(27) [М], 108 (16), 95 (21), 79 (38), 66 (100), 56 (18).
Bis(2-norbornylmethyl)amine 3d, content 89 wt %.
Mass spectrum, m/e (Irel, %): 235 (13) [M + 2], 234
(81) [М + 1], 138 (100) [С7H11CH2NH=CH2]+, 109
(19), 67 (35), 44 (42). Tris(2-norbornylmethyl)amine
4d, content 2 wt %. Mass spectrum, m/e (Irel, %): 340
(1) [M – 1], 246 (100) [M – С7H11], 152 (14), 109 (4),
79 (3), 67 (17).
Hydrogenation of 2-adamant-2-ylidenepropio-
nitrile 1g was performed similarly, using sodium boro-
hydride (0.5 g, 0.014 mol), 20 mL of isopropanol,
anhydrous nickel(II) chloride (0.9 g, 0.007 mol), and
nitrile 1g (7.5 g, 0.04 mol). The reaction duration was
12 h, the temperature was 70°C. 2-(2-Adamantyl)-
propionitrile 6g, content 79 wt %. Mass spectrum,
m/e (Irel, %): 191.1 (3) [M], 190.0 (25), 189.1 (21.6),
135 (100) [Ad]+, 107.1 (13), 93.2 (12), 67.2 (13).
Hydrogenation of 2-adamant-2-ylidenebutyro-
nitrile 1h was performed similarly, using sodium
borohydride (0.5 g, 0.014 mol), 15 mL of 1-butanol,
anhydrous nickel(II) chloride (0.9 g, 0.007 mol), and
nitrile 1h (6.0 g, 0.03 mol). The reaction duration was
12 h, the temperature was 70°C. 2-(2-Adamantyl)
butyronitrile 6h, content 87 wt %. Mass spectrum,
m/e (Irel, %): 203.1 (16) [M], 202.1 (100), 201.2 (43),
186.3 (19), 172.2 (19), 133.2 (6), 117.2 (9), 91.1 (10),
65.2 (5.4), 41.1 (5.5).
Hydrogenation of cinnamic acid nitrile 1e. a.
Similarly to the above-described, using sodium
borohydride (0.4 g, 0.011 mol), 20 mL of isopropanol,
anhydrous nickel(II) chloride (0.7 g, 0.006 mol), and
cinnamic acid nitrile 1e (6 g, 0.046 mol). The reaction
duration was 16 h, the temperature was 70°C. 3-Phenyl-
1-aminopropane 2e, content 38 wt %. Mass spectrum,
m/e (Irel, %): 136.9 (9) [М + 2], 136.0 (100) [М + 1],
134.8 (12) [М], 118.0 (60), 117.0 (52), 103.0 (8), 91.1
(16.5), 77.0 (4), 65.0 (7), 44.0 (2). Di(3-phenylprop-
1-yl)amine 3e, content 57 wt %. Mass spectrum, m/e
(Irel, %): 255.2 (20) [М + 2], 254.2 (100) [М + 1],
253.2 (34) [М], 148.0 (6), 118.0 (2), 117.0 (6), 103.0
(6), 91.1 (14), 77.1 (2), 65.0 (3), 44.0 (57).
Hydrogenation of 2-morpholino-2-cyanoada-
mantane 1i was performed similarly, using sodium
borohydride (0.6 g, 0.016 mol), 15 mL of isopropanol,
anhydrous nickel(II) chloride (1.0 g, 0.008 mol), and
nitrile 1i (2.5 g, 0.01 mol). The reaction duration was
12 h, the temperature was 70°C. 2-Morpholino-
adamantane, content 12 wt %. Mass spectrum, m/e
(Irel, %): 223.0 (3) [M + 2], 222.0 (22) [M + 1], 221.1
b. Similarly to the above-described, using sodium
borohydride (0.4 g, 0.011 mol), 20 mL of isopropanol,
anhydrous nickel(II) chloride (0.7 g, 0.006 mol), and
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279
(51) [M], 220.2 (64), 176.2 (49), 135.2 (26), 107.1
(11.6), 100.1 (27) 93.1 (14.5), 91.1 (17.6), 86.1 (100),
79.2 (18.5), 77.2 (15), 67.2 (12), 41.1 (15). The
starting nitrile was also detected in the reaction
mixture, its content was of 83 wt %.
16 h, the temperature was 70°C. 1,3-Bis-N-piperi-
dinopropane 12m, content 42 wt %. Mass spectrum,
m/e (Irel, %): 211 (100) [М + 1], 125 (26), 124 (10),
110 (39), 98 (21). Compound 13m, content 21.6 wt
%. Mass spectrum, m/e (Irel, %): 226 (15) [М], 225
(100) [М – 1], 139 (35), 125 (28), 124 (48), 112 (28),
110 (34), 98 (18).
Hydrogenation of 2-piperidino-2-cyanopropane
1j was performed similarly, using sodium borohydride
(0.2 g, 0.005 mol), 15 mL of tert-butanol, anhydrous
nickel(II) chloride (0.32 g, 0.0025 mol), and nitrile 1j
(3 g, 0.02 mol). The reaction time duration 10 h, the
temperature was 70°C. Piperidine 9j, content 15 wt %.
Mass spectrum, m/e (Irel, %): 85.8 (9) [M + 1], 84.8
(22) [M], 83.9 (100), 69.9 (7.4), 56.9 (13.4), 56.0 (48),
44.0 (15.6), 42.0 (20), 40.0 (27.7). 2-Isopropyl-
piperidine 8j, content 80 wt %. Mass spectrum, m/e
(Irel, %): 127.9 (2) [M + 1], 126.7 (3) [M], 125.8 (4),
112.9 (7.5), 111.9 (100), 84.1 (6), 69.0 (4), 56.2 (10.4),
41.0 (9).
Hydrogenation of 3-N-morpholinopropionitrile
1n. a Similarly to the described above, using sodium
borohydride (0.6 g, 0.016 mol), 15 mL of isopropanol,
anhydrous nickel(II) chloride (1.0 g, 0.008 mol), and
nitrile 1n (14 g, 0.1 mol). The reaction duration was
14 h, the temperature was 70°C. 1,3-Bis-N-morpho-
linopropane 12n, content 50 wt %. Mass spectrum, m/
e (Irel, %): 215 (12) [М + 1], 214 (100) [М], 196 (19),
184 (13), 128 (16) [М – С4Н8NO], 127 (31), 126 (16),
114 (16) [М – С5Н10NO], 112 (77), 100 (72)
[С5Н10NO], 98 (17), 70 (17). Compound 13n, content
21.3 wt %. Mass spectrum, m/e (Irel, %): 228 (9) [М],
227 (55) [М – 1], 208 (13), 196 (19), 139 (16), 128
(20) [М – С4Н8NO], 124 (100), 112 (89), 100 (23)
[С5Н10NO], 70 (10), 43 (4) [C3H7].
Hydrogenation of 2-cyclohexylamino-2-cyano-
propane 1k was performed similarly, using sodium
borohydride (0.2 g, 0.005 mol), 15 mL of tert-butanol,
anhydrous nickel(II) chloride (0.32 g, 0.0025 mol), and
nitrile 1k (3.3 g, 0.02 mol). The reaction duration was
10 h, the temperature was 70°C. Cyclohexylamine,
content 33 wt %. Mass spectrum, m/e (Irel, %): 99.9
(14) [M + 1], 99.0 (14) [M], 98.0 (5), 70.0 (17.6), 56.0
(100), 43.0 (21), 42.0 (22). N-Isopropylcyclo-
hexylamine, content 65 wt %. Mass spectrum, m/e
(Irel, %): 143.0 (1) [M + 2], 142.0 (100) [M + 1], 140.9
(10.4) [M], 126.0 (54), 98.0 (61), 70.1 (16), 56.0 (44),
44.0 (37.4), 42.0 (12).
b. Similarly to the described above, using sodium
borohydride (0.6 g, 0.016 mol), 15 mL of tert-butanol,
anhydrous nickel(II) chloride (1.0 g, 0.008 mol), and
nitrile 1n (14 g, 0.1 mol). The reaction duration was 8
h, the temperature was 70°C. Morpholine 9n, content
22 wt %. Mass spectrum, m/e (Irel, %): 88.8 (2) [М +
2], 87.9 (59) [М + 1], 86.8 (67) [М], 86.0 (100), 56.9
(86), 55.9 (98), 41.9 (28). 3-N-Morpholino-1-amino-
propane 2n, content 59 wt %. Mass spectrum, m/e
(Irel, %): 145.0 (5) [М + 1], 128.0 (1.5), 126.8 (7),
113.0 (32), 101.0 (11), 100.0 (100), 86.0 (7), 72.0 (10),
70.0 (30), 57.0 (11), 56.0 (35), 42.0 (30).
Hydrogenation of 2-hydroxy-2-cyanoadmantane
1l was performed similarly, using sodium borohydride
(0.6 g, 0.016 mol), 15 mL of tert-butanol, anhydrous
nickel(II) chloride (1.0 g, 0.008 mol), and nitrile 1l
(3.5 g, 0.02 mol). The reaction duration was 12 h, the
temperature was 70°C. 2-Hydroxyadamantane 10l,
content 92 wt %. Mass spectrum, m/e (Irel, %): 152 [M]
(8), 151 (80), 150 (100), 121 (6), 104 (11), 91.1 (17),
80.2 (14), 79 (5), 65 (4). 2-Hydroxy-2-aminomethyl-
adamantane, content 3 wt %. Mass spectrum, m/e (Irel,
%): 182.9 (7.5) [M + 2], 182.0 (44.5) [M + 1], 181.0
(16.3) [M], 152.1 (2.6), 106.0 (7), 104.9 (100), 77.0
(70), 51.0 (37.7), 50.0 (24.7).
ACKNOWLEDGMENTS
The work was financially supported by the Ministry
of Education and Science of the Russian Federation in
the frame of the basic part of the governmental
contract no. 2014/16 (project no. 2679) and the
Program of Strategic Development of Volgograd State
Technical University for 2010–2015.
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