Alkyl perchlorates in the Ritter-type reaction. Synthesis of N-alkylamides

Article abstract of DOI:10.1007/s11172-020-2858-8

The Ritter-type reaction of alkyl perchlorates with nitriles of various structures was systematically studied. The reaction has a wide scope and proceeds under extremely mild conditions without any catalysts or special activation of reagents. A structural diversity of the obtained by the Ritter-type reaction N-alkyl amides bearing small ring, double bonds, additional functional groups, aromatic and adamantane fragments, was demonstrated.

Full text of DOI:10.1007/s11172-020-2858-8

Russian Chemical Bulletin, International Edition, Vol. 69, No. 5, pp. 980—985, May, 2020
980
Alkyl perchlorates in the Ritter-type reaction. Synthesis of N-alkylamides*
N. V. Yashin,a P. O. Markov,a K. N. Sedenkova,a,b D. A. Vasilenko,a Yu. K. Grishin,a
T. S. Kuznetsova,a and E. B. Averinaa,b
aDepartment of Chemistry, Lomonosov Moscow State University,
Build. 3, 1 Leninskie Gory, 119991 Moscow, Russian Federation.
Fax: +7 (495) 939 3969. E-mail: elaver@org.chem.msu.ru
bInstitute of Physiologically Active Compounds, Russian Academy of Sciences,
1 Severnyi proezd, 142432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (496) 524 9508
The Ritter-type reaction of alkyl perchlorates with nitriles of various structures was system-
atically studied. The reaction has a wide scope and proceeds under extremely mild conditions
without any catalysts or special activation of reagents. A structural diversity of the obtained by
the Ritter-type reaction N-alkyl amides bearing small ring, double bonds, additional func-
tional groups, aromatic and adamantane fragments, was demonstrated.
Key words: alkyl perchlorates, carboxylic acid N-alkylamides, the Ritter reaction, nucleo-
philic substitution, nitriles.
The amide moieties are present in a great number of
natural compounds and medications,1,2 therefore the
development and practical implementation of the methods
for the amide bond formation are in high demand for
medicinal and organic chemistry. The Ritter reaction is
one of the most commonly used methods for the synthe-
sis of amides, in particular, amides with the secondary and
tertiary alkyl substituents at the nitrogen atoms.3—6 The
standard Ritter reaction conditions, viz., the use of the
strong acids in stoichiometric amounts and heating of the
reaction mixture, seriously limited the structural scope of
the reagents. The modern Ritter-type reactions are cata-
lyzed by different Lewis acids.6 This provides the possibil-
ity to use as the source of the carbocationic intermediates
not only the conventional tertiary alcohols7—12 and al-
kenes13—16 but also alkyl halides,17,18 aldehydes,19—21
esters,22—24 and some other classes of organic com-
pounds.25—28 In our previous short communication,29 we
for the first time have reported on the application of co-
valent perchlorates as the electrophilic substrates in the
reaction with acetonitrile to give the corresponding
N-alkylacetamides in quantitative yields under extremely
mild, catalyst-free conditions. In the present work, we
studied in detail a new Ritter-type reaction involv-
ing various organic perchlorates and nitriles and estab-
lished the scope of this method for the synthesis of carb-
oxamides.
Alkyl perchlorates 2a—e were synthesized by the pro-
cedure developed by us earlier29,30 that involved oxidative
nucleophilic substitution of the iodine atom in the cor-
responding alkyl iodides 1a—e with the perchlorate anion
(Scheme 1).
Scheme 1
R = n-C9H19 (a), n-C7H15 (b), 1-Ad (c), 1-AdCH2 (d),
1-AdOCH2 (e)
Reagents: LiClO4 (5 equiv.), NO2BF4 (2.5 equiv.).
The subsequent reactions of perchlorates 2a—e with
nitriles were carried out under the optimal conditions,29
which were slightly modified depending on the structure
of nitrile. The tolerance of the reaction towards the struc-
ture of organic nitriles was demonstrated by the reactions
of various nitriles with decyl perchlorate 2a. Nitriles with
alkyl and aryl substituents of different bulkiness (3a—g,k),
saturated nitriles (3h—j), and nitriles with additional
functional groups (3l—p) were used as the substrates of
the Ritter-type reaction (Scheme 2, Table 1).
In the most cases, the reactions carried out under the
standard conditions using the large excess of nitriles 3a—p
that served as both reagents and solvents gave the high
yields of the target amides 4a—o (see Table 1). However,
* Based on the materials of the XXI Mendeleev Congress
on General and Applied Chemistry (September 9—13, 2019,
St. Petersburg, Russia).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 0980—0985, May, 2020.
1066-5285/20/6905-0980 © 2020 Springer Science+Business Media LLC

Alkyl perchlorates in Ritter-type reaction
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 5, May, 2020
981
Scheme 2
partial polymerization of the nitriles under the reaction
conditions. The presence of the additional functional
groups in alkyl nitriles 3l—o also decreased the yields of
the target amides 4l—o. β-Cyanoethyl phosphonate 3p did
not react with electrophilic substrate 2a. It should be
emphasized that no bis(amides) were obtained when the
excess of dinitriles 3l,m relative to perchlorate 2a was used
and the low yields of monoamides 4l,m were due to the
difficulties of their isolation from the reaction mixtures
containing the high-boiling starting dinitriles.
To synthesize amides from hardly available and high-
boiling nitriles, we performed the Ritter-type reactions
with these nitriles and compound 2a in different solvents
(benzene, THF, nitromethane, nitrobenzene, diethyl
ether, CH2Cl2, CCl4, and AcOH). It was found that the
reactions of perchlorates with nitriles in the solvents failed
to give the corresponding amides even using 20-fold excess
of nitrile. Nevertheless, we demonstrated that under sol-
vent-free conditions the yield of amide 4k did not change
with decreasing the amount of nitrile down to the reagent
ratio 2a : 3k = 1 : 20. When the amount of nitrile was
decreased to 10 eqiuv., the yield of amide 4k lowered to
72%; while at an equimolar ratio the reaction did not
proceed. Under the solvent-free conditions, we succeeded
to prepare N-decylamides 4q and 4r in the moderate yields
by the reactions with perchlorate 2a with a 4-fold molar
excess of 1-adamantanecarbonitrile (3q) and a 15-fold
excess of 3-methylidenecyclobutanecarbonitrile (3r) (see
Table 1).
the presence of the trace water in the starting nitriles can
decrease the yields of compounds 4a—o due to the side
formation of n-decyl alcohol. The reactions of perchlorate
2a with more labile nitriles bearing the cyclopropane (3f)
and unsaturated alkyl moieties (3h—j) provided the target
products in the moderate yields (40—55%) owing to the
Table 1. Synthesis of N-decylamides from nitriles*
Nitrile
R´
N-Decylamide
Yield (%)
3a
3b
3c
3d
Me
Et
4a
4b
4c
4d
95
90
73
78
Pri
But
3e
4e
4f
75
40
3f**
The possibility to vary the structure of organic perchlor-
ate was demonstrated by the reactions of acetonitrile (3a)
with compounds 2a—e carried out under the standard
conditions (Scheme 3).
3g
3h
4g
4h
89
52
3i***
4i
53
Scheme 3
3j
4j
4k
4l
55
81
26
3k
3l
3m
3n
3o
4m
4n
4o
49
57
56
4
a
s
t
R
Yield (%)
n-C9H19
n-C7H15
1-Ad
95
96
98
It was found that perchlorates 2a—c bearing alkyl and
1-adamantylmethyl moieties gave the corresponding am-
ides 4a,s,t in the quantitative yields. The adamantane-
substituted perchlorates 2d,e in MeCN under the diverse
reaction conditions apparently underwent different carbo-
cationic rearrangements to give the complex product
mixtures from which no target products could be isolated.
The plausible general mechanism of the formation of
amides 4a—t that agrees with the known Ritter reaction
mechanism5,31 is shown in Scheme 4.
3p
—
—
3q
3r
4q
4r
27
22
* The reactions were carried out at 75 C for 3 h.
** The reaction was carried out at 45 C for 3 h.
*** The reaction was carried out at 45 C for 7 h.

982
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 5, May, 2020
Yashin et al.
Scheme 4
2-(1-Adamantoxy)perchloroethane (2e) was synthesized from
alkyl iodide 1e (107 mg), colorless oil, yield 49 mg (50%), Rf 0.35
In this case, the perchlorate group of substrate 2 is
apparently directly substituted with the nucleophilic ni-
trogen center of nitrile 3 via SN2-type mechanism owing
to high nucleofugality of the perchlorate anion.32 The
subsequent hydrolysis of intermediate A led to the final
products, carboxamides 4.
1
(petroleum ether—ethyl acetate, 15 : 1). H NMR (CDCl3), :
1.55—1.70 (m, 6 H, 3 CH2, Ad); 1.71—1.77 (m, 6 H, 3 CH2,
Ad); 2.12—2.20 (m, 3 H, 3 CH, Ad); 3.76—3.79 (m, 2 H, OCH2);
4.60—4.63 (m, 2 H, CH2OClO3). 13C NMR (CDCl3), : 30.6
(3 CH, Ad); 36.4 (3 CH2, Ad); 41.4 (3 CH2, Ad); 56.8 (OCH2);
73.3 (C, Ad); 75.6 (CH2OClO3).
The reactions of covalent perchlorates with nitriles (general
procedure). A mixture of alkyl perchlorate 2 (0.17 mmol) and
anhydrous nitrile 3 (5 mL) was stirred at 45—75 C for 3—7 h
under argon. The reaction mixture was poured into cold distilled
water (10 mL) and extracted with dichloromethane (3×5 mL).
The combined organic layers were washed with distilled water
(10 mL) and dried with MgSO4. The volatiles were removed
in vacuo, product 4 was purified by preparative chromatography
if required.
In summary, we developed a new approach to the
synthesis of carboxylic acid N-alkylamides via the Ritter-
type reaction of alkyl perchlorates with organic nitriles.
The reaction proceeds under mild catalyst-free reaction
conditions and gives the target products in high yields.
The method is general and suitable for the synthesis of
a wide variety of amides bearing the small cycles, the
multiple bonds, the aromatic and adamantane substituents
as well as the additional functional groups.
N-Decylacetamide (4a)29, yellowish oil, yield 32 mg (95%).
Removal of excess acetonitrile in vacuo afforded pure product
4a. 1H NMR (CDCl3), : 0.85—0.90 (m, 3 H, CH3); 1.19—1.36
(m, 14 H, 7 CH2); 1.44—1.53 (m, 2 H, CH2); 1.98 (s, 3 H,
CH3C=O); 3.19—3.26 (m, 2 H, CH2N); 5.60 (br.s, 1 H, NH).
13C NMR (CDCl3), : 14.2 (CH3); 22.8 (CH2); 23.5 (CH3C=O);
27.0 (CH2); 29.4 (2 CH2); 29.65 (2 CH2); 29.72 (CH2); 32.0
(CH2); 39.8 (CH2N); 170.1 (C=O).
N-Decylpropionamide (4b), colorless crystals, yield 33 mg
(90%), m.p. 41 C. Removal of excess acetonitrile in vacuo af-
forded pure product 4b. 1H NMR (CDCl3), : 0.84—0.89 (m, 3 H,
CH3); 1.14 (t, 3 H, CH3, Et, J = 7.6 Hz); 1.20—1.32 (m, 14 H,
7 CH2); 1.43—1.51 (m, 2 H, CH2); 2.18 (q, 2 H, CH2C=O,
J = 7.6 Hz); 3.22 (dt, 2 H, CH2N, J1 = 5.9 Hz, J2 = 7.1 Hz);
5.55 (br.s, 1 H, NH). 13C NMR (CDCl3), : 10.1 (CH3, Et);
14.2 (CH3); 22.8 (CH2); 27.0 (CH2); 29.4 (2 CH2); 29.7 (2 CH2);
29.8 (CH2); 29.9 (CH2); 32.0 (CH2); 39.6 (CH2N); 173.8 (C=O).
MS: found m/z 214.2172 [M + H]+; calculated for C13H28NO
M + H 214.2165; found m/z 236.1985 [M + Na]+; calculated for
C13H27NONa M + Na 236.1985.
Experimental
NMR spectra were recorded with Bruker Avance-400 and
Agilent 400-MR spectrometers (working frequencies of 400.0
(1H) and 100.6 MHz (13C)) in CDCl3 at 25 C. The chemical
shifts are given in the  scale relative to the residual solvent
signals (H 7.26, C 77.16). High resolution mass spectrometry
(HRMS) was performed with a JEOL GCMate II spectrometer
operating in the positive ion mode. Melting points were measured
on an Electrothermal 9100 apparatus. The reaction course and
purity of the products were monitored by TLC on the precoated
Silufol-UV254 plates. Preparative column chromatography was
performed with Macherey-Nagel (40/60) silica gel. Anhydrous
LiClO4 was obtained by calcining LiClO4•3H2O in a muffle
furnace at 240 C for 2 h.
Alkyl perchlorates 2a—c were synthesized by known proce-
dures.29,30 Organic perchlorates 2d,e were prepared as earlier
described.29
CAUSION! Alkyl perchlorates are unstable explosives. These
compounds have to be purified and handled with the appropriate
precautions.
N-Decylisopropylcarboxamide (4c), colorless crystals, yield
28 mg (73%), m.p. 44 C. 1H NMR (CDCl3), : 0.83—0.89
(m, 3 H, CH3); 1.13 (d, 6 H, 2 CH3, Pri, J = 6.9 Hz); 1.20—1.31
(m, 14 H, 7 CH2); 1.43—1.51 (m, 2 H, CH2); 2.32 (sept, 1 H,
CH, J = 6.9 Hz); 3.22 (dt, 2 H, CH2N, J1 = 5.9 Hz, J2 = 7.1 Hz);
5.60 (br.s, 1 H, NH). 13C NMR (CDCl3), : 14.2 (CH3); 19.8
(2 CH3, Pri); 22.8 (CH2); 27.0 (CH2); 29.4 (2 CH2); 29.7 (2 CH2);
29.8 (CH2); 32.0 (CH2); 35.8 (CH); 39.5 (CH2N); 177.0 (C=O).
MS: found m/z 228.2325 [M + H]+; calculated for C14H30NO
M +H = 228.2322; found m/z 250.2140 [M +Na]+; calculated
for C14H29NONa M + Na = 250.2141.
2-(1-Adamantyl)perchloroethane (2d) was synthesized from
alkyl iodide 1d (120 mg), colorless oil, yield 47 mg (44%), Rf 0.40
1
(petroleum ether). H NMR (CDCl3), : 1.51—1.56 (m, 6 H,
3 CH2, Ad); 1.58 (t, 2 H, CH2, J = 7.2 Hz); 1.60—1.68 (m, 3 H,
3 CH2, Ad); 1.69—1.77 (m, 3 H, 3 CH2, Ad); 1.96—2.03 (m, 3 H,
3 CH, Ad); 4.61 (t, 2 H, OCH2, J = 7.2 Hz). 13C NMR (CDCl3),
: 28.6 (3 CH, Ad); 32.1 (C, Ad); 36.9 (3 CH2, Ad); 40.9 (CH2);
42.5 (3 CH2, Ad); 73.2 (OCH2).

Alkyl perchlorates in Ritter-type reaction
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 5, May, 2020
983
N-Decyl-tert-butylcarboxamide (4d), yellowish oil, yield
32 mg (78%), Rf 0.27 (petroleum ether—ethyl acetate, 4 : 1).
1H NMR (CDCl3), : 0.83—0.89 (m, 3 H, CH3); 1.17 (s, 9 H,
3 CH3, But); 1.20—1.31 (m, 14 H, 7 CH2); 1.43—1.51 (m, 2 H,
CH2); 3.20 (dt, 2 H, CH2N, J1 = 5.9 Hz, J2 = 7.1 Hz); 5.65 (br.s,
1 H, NH). 13C NMR (CDCl3), : 14.2 (CH3); 22.8 (CH2); 27.0
(CH2); 27.7 (3 CH3, But); 29.4 (2 CH2); 29.6 (2 CH2); 29.7
(CH2); 32.0 (CH2); 38.7 (C, But); 39.7 (CH2N); 178.4 (C=O).
MS: found m/z 242.2478 [M + H]+; calculated for C15H32NO;
M + H 242.2478; found m/z 264.2295 [M + Na]+; calculated for
C15H31NONa M + Na 264.2295.
N-Decylcyclopropylcarboxamide (4e), colorless crystals, yield
29 mg (75%), m.p. 65 C, Rf 0.21 (petroleum ether—ethyl acetate,
4 : 1). 1H NMR (CDCl3), : 0.68—0.74 (m, 2 H, cyclo-Pr);
0.84—0.89 (m, 3 H, CH3); 0.93—0.99 (m, 2 H, cyclo-Pr);
1.22—1.35 (m, 15 H, 7 CH2 + CH); 1.45—1.54 (m, 2 H, CH2);
3.21—3.28 (m, 2 H, CH2N); 5.67 (br.s, 1 H, NH). 13C NMR
(CDCl3), : 7.1 (2 CH2, cyclo-Pr); 14.3 (CH3); 14.9 (CH); 22.8
(CH2); 27.0 (CH2); 29.4 (2 CH2); 29.7 (2 CH2); 29.9 (CH2);
32.0 (CH2); 39.9 (CH2N); 173.5 (C=O). MS: found m/z 226.2167
[M + H]+; calculated for C14H28NO M + H = 226.2165; found
m/z 248.1979 [M + Na]+; calculated for C14H27NONa M + Na
248.1985.
2-Cyclopropyl-N-decylacetamide (4f), yellowish crystals, yield
17 mg (40%), m.p. 55 C, Rf 0.25 (petroleum ether—ethyl acetate,
4 : 1). The reaction time was 4 h, the reaction temperature was
45 C. 1H NMR (CDCl3), : 0.17—0.22 (m, 2 H, cyclo-Pr);
0.58—0.63 (m, 2 H, cyclo-Pr); 0.85—0.91 (m, 3 H, CH3);
0.89—1.00 (m, 1 H, CH); 1.21—1.36 (m, 14 H, 7 CH2); 1.46—
1.56 (m, 2 H, CH2); 2.16 (d, 2 H, CH2C=O, J = 7.0 Hz);
3.24—3.31 (m, 2 H, CH2N); 5.98 (br.s, 1 H, NH). 13C NMR
(CDCl3),: 4.8 (2 CH2, cyclo-Pr); 7.3 (CH); 14.3 (CH3); 22.8
(CH2); 27.0 (CH2); 29.4 (2 CH2); 29.7 (2 CH2); 29.8 (CH2);
32.0 (CH2); 39.7 (CH2N); 41.6 (CH2C=O); 172.6 (C=O).
MS: found m/z 240.2328 [M + H]+; calculated for C15H30NO
M + H = 240.2322; found m/z 262.2145 [M + Na]+; calculated
for C15H29NONa M + Na 262.2141.
N-Decylbut-3-enamide (4i), colorless crystals, yield 20 mg
(53%), m.p. 41 C, Rf 0.16 (petroleum ether—ethyl acetate, 2 : 1).
1
Reaction time was 7 h, reaction temperature 45 C. H NMR
(CDCl3), : 0.84—0.89 (m, 3 H, CH3); 1.20—1.33 (m, 14 H,
7 CH2); 1.43—1.52 (m, 2 H, CH2); 2.99 (d, 2 H, CH2CO,
J = 7.2 Hz); 3.24 (dt, 2 H, CH2N, J1 = 6.0 Hz, J2 = 7.1 Hz);
5.16—5.24 (m, 2 H, CH2=); 5.59 (br.s, 1 H, NH); 5.92 (ddt,
1 H, CH, J1 = 10.2 Hz, J2 = 17.1 Hz, J3 = 7.2 Hz). 13C NMR
(CDCl3), : 14.3 (CH3); 22.8 (CH2); 27.0 (CH2); 29.41 (CH2);
29.44 (CH2); 29.6 (2 CH2); 29.7 (CH2); 32.0 (CH2); 39.8
(CH2N); 41.9 (CH2C=O); 120.0 (CH2=); 131.7 (CH); 170.5
(C=O). MS: found m/z 226.2161 [M + H]+; calculated for
C14H28NO M + H = 226.2165; found m/z 248.1981 [M + Na]+;
calculated for C14H27NONa M + Na 248.1985.
N-Decylpent-4-enamide (4j), yellowish crystals, yield 22 mg
(55%), m.p. 43 C, Rf 0.20 (petroleum ether—ethyl acetate, 3 : 1).
1H NMR (CDCl3), : 0.83—0.88 (m, 3 H, CH3); 1.18—1.33
(m, 14 H, 7 CH2); 1.42—1.51 (m, 2 H, CH2); 2.22—2.27 (m, 2 H,
CH2C=O); 2.34—2.41 (m, 2 H, CH2); 3.22 (dt, 2 H, CH2N,
J1 = 5.9 Hz, J2 = 7.1 Hz); 4.94—5.00 (m, 1 H, CH2=); 5.00—5.07
(m, 1 H, CH2=); 5.58 (br.s, 1 H, NH); 5.75—5.86 (m, 1 H, CH).
13C NMR (CDCl3), : 14.2 (CH3); 22.8 (CH2); 27.0 (CH2); 29.4
(2 CH2); 29.7 (2 CH2); 29.75 (CH2); 29.83 (CH2); 32.0 (CH2);
36.1 (CH2C=O); 39.7 (CH2N); 115.6 (CH2=); 137.3 (CH); 172.3
(C=O). MS: found m/z 240.2320 [M + H]+; calculated for
C15H30NO M + H 240.2322; found m/z 262.2138 [M + Na]+;
calculated for C15H29NONa M + Na 262.2141.
N-Decylbenzamide (4k)34, colorless crystals, yield 36 mg
(81%), m.p. 58 C, Rf 0.27 (petroleum ether—ethyl acetate, 5 : 1).
1H NMR (CDCl3), : 0.84—0.90 (m, 3 H, CH3); 1.19—1.42
(m, 14 H, 7 CH2); 1.56—1.65 (m, 2 H, CH2); 3.40—3.47 (m, 2 H,
CH2N); 6.20 (br.s, 1 H, NH); 7.39—7.44 (m, 2 H, 2 CH);
7.45—7.51 (m, 1 H, CH); 7.73—7.77 (m, 2 H, 2 CH). 13C NMR
(CDCl3), : 14.3 (CH3); 22.8 (CH2); 27.1 (CH2); 29.43 (CH2);
29.47 (CH2); 29.7 (2 CH2); 29.8 (CH2); 32.0 (CH2); 40.3
(CH2N); 127.0 (2 CH); 128.7 (2 CH); 131.4 (CH); 135.0 (C, Ph);
167.6 (C=O).
N-Decylcyclohexylcarboxamide (4g), colorless crystals, yield
40 mg (89%), m.p. 64 C, Rf 0.32 (petroleum ether—ethyl acetate,
4 : 1). 1H NMR (CDCl3), : 0.84—0.89 (m, 3 H, CH3); 1.19—1.31
(m, 17 H, 7 CH2, Dec + 2 CH2, cyclo-Hex); 1.36—1.51 (m, 4 H,
CH2, Dec + CH2, cyclo-Hex); 1.62—1.69 (m, 1 H, CH2,
cyclo-Hex); 1.74—1.88 (m, 4 H, 2 CH2, cyclo-Hex); 2.0—2.09
(m, 1 H, CH); 3.18—3.24 (m, 2 H, CH2N); 5.49 (br.s, 1 H, NH).
13C NMR (CDCl3), : 14.2 (CH3); 22.8 (CH2, Dec); 25.85 (CH2,
cyclo-Hex); 25.9 (2 CH2, cyclo-Hex); 27.0 (CH2, Dec); 29.4
(2 CH2, Dec); 29.7 (2 CH2, Dec); 29.8 (CH2, Dec); 29.9 (2 CH2,
cyclo-Hex); 32.0 (CH2, Dec); 39.5 (CH2N); 45.8 (CH); 176.1
(C=O). MS: found m/z 268.2632 [M + H]+; calculated for
C17H34NO M + H 268.2635; found m/z 290.2449 [M + Na]+;
calculated for C17H33NONa M + Na 290.2454.
N-Decylcyanoacetamide (4l),35 yellowish crystals, yield 10 mg
(26%), m.p. 71 C, Rf 0.22 (petroleum ether—ethyl acetate, 3 : 1).
1H NMR (CDCl3), : 0.85—0.90 (m, 3 H, CH3); 1.20—1.35
(m, 14 H, 7 CH2); 1.50—1.58 (m, 2 H, CH2); 3.30 (dt, 2 H,
CH2N, J1 = 6.0 Hz, J2 = 7.1 Hz); 3.37 (s, 2 H, CH2CN); 6.10
(br.s, 1 H, NH). 13C NMR (CDCl3), : 14.3 (CH3); 22.8 (CH2);
26.0 (CH2CN); 27.0 (CH2); 29.3 (CH2); 29.39 (CH2); 29.43
(CH2); 29.6 (CH2); 29.7 (CH2); 32.0 (CH2); 40.6 (CH2N); 115.0
(CN); 160.8 (C=O).
5-Cyano-N-decylpentanamide (4m), colorless crystals, yield
22 mg (49%), m.p. 56 C, Rf 0.11 (petroleum ether—ethyl acetate,
5 : 1). 1H NMR (CDCl3), : 0.84—0.89 (m, 3 H, CH3); 1.17—1.32
(m, 14 H, 7 CH2); 1.43—1.51 (m, 2 H, CH2); 1.66—1.73 (m, 2 H,
CH2); 1.74—1.83 (m, 2 H, CH2); 2.17—2.23 (m, 2 H, CH2C=O,
J = 7.0); 2.34—2.39 (m, 2 H, CH2CN); 3.18—3.25 (dt, 2 H,
CH2N, J1 = 6.0 Hz, J2 = 7.1 Hz); 5.56 (br.s, 1 H, NH). 13C NMR
(CDCl3), : 14.2 (CH3); 17.1 (CH2CN); 22.8 (CH2); 24.7 (CH2);
25.0 (CH2); 27.0 (CH2); 29.4 (2 CH2); 29.6 (2 CH2); 29.7 (CH2);
32.0 (CH2); 35.6 (CH2C=O); 39.7 (CH2N); 119.7 (CN); 171.8
(C=O). MS: found m/z 267.2434 [M + H]+; calculated for
C16H31N2O M + H 267.2431; found 289.2252 [M + Na]+; cal-
culated for C16H30N2ONa M + Na 289.2250.
N-Decylacrylamide (4h)33, yellowish crystals, yield 19 mg
(52%), m.p. 43 C, Rf 0.13 (petroleum ether—ethyl acetate, 2 : 1).
Reaction time was 4 h, reaction temperature was 70 C. 1H NMR
(CDCl3), : 0.84—0.89 (m, 3 H, CH3); 1.20—1.35 (m, 14 H,
7 CH2); 1.48—1.57 (m, 2 H, CH2); 3.28—3.35 (br.m, 2 H, CH2N);
5.62 (d, 1 H, CH2=, J = 9.9 Hz); 5.69 (br.s, 1 H, NH); 6.09 (dd,
1 H, CH, J = 9.9 Hz, J = 16.8 Hz); 6.27 (d, 1 H, CH2=, J = 16.8).
13C NMR (CDCl3), : 14.2 (CH3); 22.8 (CH2); 27.1 (CH2); 29.4
(2 CH2); 29.65 (2 CH2); 29.7 (CH2); 32.0 (CH2); 39.8 (CH2N);
126.3 (CH2=); 131.1 (CH); 165.6 (C=O).
4-Chloro-N-decylbutanamide (4n), yellowish crystals, yield
25 mg (57%), m.p. 47 C, Rf 0.15 (petroleum ether—ethyl acetate,

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Russ. Chem. Bull., Int. Ed., Vol. 69, No. 5, May, 2020
Yashin et al.
4 : 1). 1H NMR (CDCl3), : 0.84—0.89 (m, 3 H, CH3); 1.19—1.35
(m, 14 H, 7 CH2); 1.44—1.52 (m, 2 H, CH2); 2.06—2.14 (m, 2 H,
CH2); 2.34 (t, 2 H, CH2C=O, J = 7.1 Hz); 3.20—3.26 (m, 2 H,
CH2N); 3.60 (t, 2 H, CH2Cl, J = 6.2 Hz); 5.57 (br.s, 1 H, NH).
13C NMR (CDCl3), : 14.2 (CH3); 22.8 (CH2); 27.0 (CH2); 28.3
(CH2); 29.4 (2 CH2); 29.7 (2 CH2); 29.8 (CH2); 32.0 (CH2);
33.4 (CH2C=O); 39.7 (CH2N); 44.7 (CH2Cl); 171.6 (C=O).
MS: found m/z 262.1932 [M + H]+; calculated for C14H29ClNO
M + H = 262.1932; found m/z 284.1749 [M + Na]+; calculated
for C14H28ClNONa M + Na 284.1752.
afforded pure product 4t. 1H NMR (CDCl3), : 1.44—1.49 (m,
6 H, 3 CH2, Ad); 1.58—1.65 (m, 3 H, 3 CH2, Ad); 1.67—1.74
(m, 3 H, 3 CH2, Ad); 1.94—1.99 (m, 3 H, 3 CH, Ad); 2.00 (s, 3 H,
CH3); 2.94 (d, 2 H, CH2N, J = 6.5 Hz); 5.49 (br.s, 1 H, NH).
13C NMR (CDCl3), : 23.6 (CH3); 28.3 (3 CH, Ad); 33.7 (C, Ad);
37.0 (3 CH2, Ad); 40.3 (3 CH2, Ad); 51.2 (CH2NH); 170.5
(C=O). MS: found m/z 230.1498 [M + Na]+; calculated for
C13H21NNaO M + Na 230.1511.
References
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yield 23 mg (56%), m.p. 37 C, Rf 0.10 (petroleum ether—ethyl
acetate, 4 : 1). 1H NMR (CDCl3), : 0.83—0.88 (m, 3 H, CH3);
1.21—1.31 (m, 14 H, 7 CH2); 1.43—1.51 (m, 2 H, CH2); 2.43
(t, 2 H, CH2C=O, J = 5.8 Hz); 3.22 (dt, 2 H, CH2N, J1 = 6.0 Hz,
J2 = 7.1 Hz); 3.36 (s, 3 H, OCH3); 3.61 (t, 2 H, OCH2,
J = 5.8 Hz); 6.21 (br.s, 1 H, NH). 13C NMR (CDCl3), : 14.2
(CH3); 22.8 (CH2); 27.0 (CH2); 29.4 (2 CH2); 29.7 (3 CH2);
32.0 (CH2); 37.2 (CH2C=O); 39.5 (CH2N); 58.9 (OCH3); 66.9
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[M + Na]+; calculated for C14H29NO2Na M + Na 266.2091.
N-Decyl(1-adamantane)carboxamide (4q), colorless crystals,
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acetate, 5 : 1). The reaction was carried out using 4 equiv. of
nitrile. Nitrile and perchlorate were thoroughly triturated to a
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smooth paste and subjected to heating. H NMR (CDCl3), :
0.85—0.90 (m, 3 H, CH3); 1.21—1.33 (m, 14 H, 7 CH2);
1.43—1.51 (m, 2 H, CH2); 1.66—1.77 (m, 6 H, 3 CH2, Ad);
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28.3 (3 CH); 29.4 (2 CH2); 29.7 (2 CH2); 29.8 (CH2); 32.0 (CH2);
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7 CH2); 1.44—1.52 (m, 2 H, CH2); 2.79—3.03 (m, 5 H, cyclo-Bu);
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10 H, (CH2)5); 1.62—1.73 (m, 2 H, CH2); 2.51 (s, 3 H,
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Alkyl perchlorates in Ritter-type reaction
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 5, May, 2020
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Received September 26, 2019;
in revised form November 29, 2019;
accepted December 7, 2019