Detailed Studies of the Alkylation Sides of Pyridin-2-yl and 4,6-Dimethylpyrimidin-2-yl-cyanamides

Article abstract of DOI:10.1002/jhet.2621

Pyridin-2-yl- and 4,6-dimethylpyrimidin-2-yl-cyanamides entered into an alkylation reaction in the form of sodium salts. Pyridin-2-yl cyanamide 2 was alkylated at endo-nitrogen atom of pyridine ring, while 4,6-dimethylpyrimidin-2-yl cyanamide 1 was effect

Full text of DOI:10.1002/jhet.2621

Month 2016
Detailed Studies of the Alkylation Sides of Pyridin-2-yl
and 4,6-Dimethylpyrimidin-2-yl-cyanamides
a
b
c
c
*
Alexander S. Shestakov, Amr H. Moustafa, Ivan S. Bushmarinov, Alexander S. Goloveshkin,
Alexey V. Shapovalov,c Khidmet S. Shikhaliev,a Mikhail A. Prezent,d and Oleg E. Sidorenkoa
aDepartment of Chemistry, Voronezh State University, Universitetskaya pl. 1, Voronezh 394006, Russia
bDepartment of Chemistry, Faculty of Science, Sohag University, 82524 Sohag, Egypt
cA.N. Nesmeyanov Institute of Organoelemental Compounds, RAS, Vavilov St., Moscow 119991, Russia
dN.D. Zelinsky Institute of Organic Chemistry, RAS, Leninsky prosp. 47, Moscow 119991, Russia
*
E-mail: amr_hassanegypt@ymail.com
Received October 13, 2015
DOI 10.1002/jhet.2621
Published online 00 Month 2016 in Wiley Online Library (wileyonlinelibrary.com).
Pyridin-2-yl- and 4,6-dimethylpyrimidin-2-yl-cyanamides entered into an alkylation reaction in the form
of sodium salts. Pyridin-2-yl cyanamide 2 was alkylated at endo-nitrogen atom of pyridine ring, while 4,6-
dimethylpyrimidin-2-yl cyanamide 1 was effectively alkylated at exo-nitrogen atom of amino cyanamide
group. The alkylation of cyanamides 1 and 2 with phenacylbromide gave the corresponding acetophenone
derivatives. As a result of their intramolecular cyclization reactions 3-(4,6-dimethylpyrimidin-2-yl)-5-
phenyloxazol-2(3H)-imine in the case of cyanamide 1 and 2-amino-3-benzoylimidazo[1,2-a]pyridine in
the case of cyanamide 2 were formed. The alkylated derivatives of pyridin-2-ylcyanamide 2 possess visible
blue fluorescence with the main peak at 421 – 427 nm.
J. Heterocyclic Chem., 00, 00 (2016).
INTRODUCTION
participation of the heterocyclic moiety. For example,
2-cyanoaminobenzimidazole was alkylated at the two ni-
trogen atoms of benzimidazole ring [9]. In the case of
cyanoaminopyrazines, the alkylation proceeded with the
formation of approximately equal amount of N-alkyl-N-
(pyrazin-2-yl)cyanamides and N-1 alkylated pyrazines
[11]. Thus, the products of N-alkyl hetarylcyanamides
depend on the nature of the reaction centers; their reaction
preferences require a further study. Herein, we report a
facile approach to provide N-alkylation of 4,6-
dimethylpyrimidin-2-yl-cyanamide 1 at exo-nitrogen atom
cyanoamino group and pyridin-2-yl-cyanamide 2 at endo-
nitrogen atom pyridine ring.
Cyanamide and its derivatives have been applied as
building blocks for the synthesis of amidines, guanidines,
and nitrogen-containing heterocycles [1]. Compounds of
this class have been studied extensively because of their
biological activity [2]. Moreover, some of these com-
pounds have been used in the preparation of organometal-
lic compounds [3].
Despite the fact that the reactions of cyanamides have
been well previously studied [1], their alkylation was not
studied independently, only as intermediate compounds
in cyclization reactions. For example, alkylation products
of aryl- and hetarylcyanamides with methyl bromoacetate
[4], ethyl iodoacetate [5], propargyl bromide [6], or
(chloromethyl)thiirane [7] acted as intermediates in the
heterocyclization reactions. Triazinylcyanamides were re-
ported to react with a wide range of haloalkanes and
halocarboxylic acid derivatives [8]. Also, a series of
N-alkyl 2-cyanoaminobenzimidazole derivatives were
obtained [9]. Stanovnik and co-workers pioneered the
methylation of cyanoamino-pyridazines and -pyrazines by
using dimethylformamide-dimethylacetal (DMFDMA)
[10] and diazomethane [11], respectively. As we were well
aware, the alkylation of triazinylcyanamides and
cyanoaminopyridazines was carried out at cyanoamino
group, but in other cases the reaction proceeded with
RESULTS AND DISCUSSION
Initially, 4,6-dimethylpyrimidin-2-yl-cyanamide 1 and
pyridin-2-yl-cyanamide 2 were selected in our work for
studying their alkylation (Scheme 1). In a one-pot proce-
dure, the alkylated cyanamide derivatives were obtained
in a two-stage process. In the first step, when cyanamides
reacted with sodium methoxide (MeONa) in the presence
of methanol, their sodium salt was formed. In fact, the
acidity of the amino group in cyanamides (cyanamide
NH2CN has an acid pKa of 7 [12] and cyanamide 1 has
an acid pKa of 6.95 [13]) is significantly higher than pKa
© 2016 Wiley Periodicals, Inc.

A. S. Shestakov, A. H. Moustafa, I. S. Bushmarinov, A. S. Goloveshkin, A. V. Shapovalov,
Kh. S. Shikhaliev, M. A. Prezent, and O. E. Sidorenko
Vol 000
Scheme 1. The structure of cyanamides 1 and 2, and possible products of their alkylation.
of 15.5 for methanol. When methanol was evaporated, the
resulting sodium salt of cyanamides was dissolved in
dimethylacetamide (DMAC) to interact with alkyl halides.
Hetarylcyanamides are known to exist as amino-imine
tautomers [14]. The direction of the alkylation of 2-
aminopyridine is highly dependent on the position of
the tautomeric equilibrium [15]. However, this is true for
neutral conditions. In the anions of 2-amino-pyridine and
-pyrimidine, both exo-cyclic nitrogen atom of amino cyan-
amide group and endo-cyclic nitrogen atom of heterocycle
are considered potential ambident nucleophiles. Indeed, in
our case the cyanamide anion from the sodium salt partic-
ipated in the reaction, so the formation of N-alkyl deriva-
tives of both exo- and endo-cyclic nitrogen atoms could
be expected. Consequently, the formation of regioisomers
Ia–с and IIa–с can be expected for alkylation of cyana-
mides 1 and 2 (Scheme 1). The structures IIa and IIa′, as
well as Ia and Ia′, correspond to different canonical forms
of the same compound; the question of the best representa-
tion of such compounds has not yet been resolved.
We have performed quantum chemical calculations of
the geometry and electron structure of cyanamide anions
(see Experimental). The calculations showed that HOMO
orbitals in all cyanamides were located in all nitrogen
atoms of hetarylcyanamides. In addition, the alkylation of
substrate cyanamides has been investigated by means of
the calculated molecular electrostatic potentials, which
indicate that the negative charges are roughly equally dis-
tributed over all nitrogen atoms. Therefore, from these data
we cannot give preference to any reaction center. Under
thermodynamic control of the reaction, the energy differ-
ence between the alkylated products should determine the
reaction outcome.
Table 1 shows the calculations for N-benzyl of cyana-
mide derivatives I and II. In all cases ΔE = Ei ꢀEmin, when
Emin is an energy for the most stable isomer. For cyana-
mide 1, isomer Ib is more energetically preferable, but
the difference in the energies of isomers Ia and Ib is small.
For cyanamide 2, the isomers IIa and IIc are energetically
favorable, and the formation of alkylated carbodiimide de-
rivatives Ic and IIc has not been reported for the studied re-
action [4–11]. Thus, we can predict that the reaction with 1
in thermodynamic conditions can produce both Ia and Ib,
with Ib being slightly more favorable, while the only prod-
uct of reaction with 2 will be IIa. It should be noted that
the calculations were carried out without considering the
solvent effects, and the substituent effects can affect the
outcome.
As it turned out, the 4,6-dimethylpyrimidin-2-
ylcyanamide 1 was entirely alkylated at nitrogen atom of
amino cyanamide group (Scheme 2), resulting in products
of Ib type.
Structure of compound 4 has been confirmed unambigu-
1
ously by the following data. First, in H NMR spectra
methyl groups at positions 4 and 6 are represented by one
singlet; in 13C NMR carbons at positions 4 and 6 as well
as carbons of methyl groups are represented by one signal
Table 1
The difference in the energies of possible alkylated products I and II,
ΔE, kcal/mol (R = benzyl).
A
B
C
I
II
2.20
0.50
0
4.73
3.48
0
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Pyridin-2-yl and 4,6-Dimethylpyrimidin-2-yl-cyanamides
Scheme 2
and showed magnetic equivalence, unlike those of N-1 or
N-3 alkylated cyanamide Ia.
nitrogen atom. Compounds 5, 7 (in a basic medium), or 9
(in a neutral medium) [17] may be considered as the
results of cyclization for different alkylated cyanamide
derivatives 4m, 6, and 8, respectively (Scheme 3). As it
turned out, the formation of compound 5 is precisely
defined. The presence of magnetically equivalent protons
and carbons in 1H and 13C NMR spectra shows no changes
in the pyrimidine cycle structure during its alkylation
and cyclization. This would be impossible in the case
of compound 7 or 9. Also, in 1H NMR spectrum the
structure of compound 5 is confirmed by the presence of
signals at 8.16 and 8.40ppm, corresponding to protons
of oxazole cycle and imino group, respectively. In IR
spectrum an imino group shows the absorption bands
at 3290 and 1686 cmꢀ1, corresponding to NH and
C¼N stretching vibrations. Earlier, compounds 4m
and 5 were prepared by converting the reaction product
of 5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine with
phenacylbromide [18].
Second, the IR spectra showed that cyano group is rep-
resented by an absorption band at 2225–2240cmꢀ1, which
is in excellent agreement with the structure ―N(R)―C≡N.
The alkylation of endo-cyclic nitrogen atom should lead to
the formation of cyanoimino =N―C≡N group, in which an
absorption band of cyano group is given at 2150–
2190 cmꢀ1 [9,16].
Third, melting points of compound 4 do not exceed 150°
C, whereas the introduction of alkyl substituents to cyana-
mide at positions 1 or 3 leads to the formation of the com-
pounds with much higher melting points. Thus, minor 2
(1H)cyanoimino-1,4,6-trimethylpyrimidine (Ia, R=CH3)
with a melting point 259°C has been isolated along with
2(N-methylcyanoamino)-4,6-dimethylpyrimidine 4a (melt-
ing point 107–108°C), when N-(4,6-dimethylpyrimidin-2-
yl)formamide oxime was treated with DMFDMA [10].
The results of the interaction of cyanamide 1 with
phenacylbromide and subsequent intramolecular cycliza-
tion of the resulting alkylated cyanamides are the fourth ar-
gument which confirms the alkylation of exo-cyclic
A different picture is observed for alkylation of pyridin-
2-ylcyanamide 2. In IR spectra an absorption band
for nitrile group is observed at 2150–2170cmꢀ1, which
Scheme 3
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. S. Shestakov, A. H. Moustafa, I. S. Bushmarinov, A. S. Goloveshkin, A. V. Shapovalov,
Kh. S. Shikhaliev, M. A. Prezent, and O. E. Sidorenko
Vol 000
Scheme 4
Scheme 5
indicates that the triple bond C≡N is conjugated with
the double bond C¼N to form compound 11 (Scheme 4).
The alkylation of cyanamide 2 with phenacylbromide
and treatment of the resulting alkylated derivative with
triethylamine led to the formation of fused 2-
aminoimidazo[1,2-a]pyridine system 12 (Scheme 5) [19].
The 4e unit cell contains four independent molecules of
4e. The geometry of these molecules in the independent
part is very similar, differing only slightly in the rotation
1
The results of H, 13C NMR, and IR spectroscopy speak
in favor of the formation of compounds 11e and 12, but
1
not 13 and 14. Indeed, the H NMR spectrum shows a
characteristic singlet for NH2 group at 5.61 ppm; in the
13C NMR spectrum a characteristic signal is observed at
181.9 ppm because of a carbon atom of carbonyl group.
In IR spectrum the absorption bands occur at 3300 and
3481 cmꢀ1 (symmetric and asymmetric stretching vibra-
tions within ―NH2 group) and 1699cmꢀ1 because of car-
bonyl group.
Figure 2. X-ray crystal structure of 4e. [Color figure can be viewed in
the online issue, which is available at wileyonlinelibrary.com.]
X-ray crystallography. View of 4d–f, 11b, and 11c are
shown at Figures 1–5, respectively. For other details of
structure determination see Experimental. All structures
have been deposited with CCDC, refcodes 927772–
927774 for 4d,e,f and 927770, 927771 for 11b,c. Atoms
are represented by thermal displacement ellipsoids
(ρ = 50%).
Figure 1. X-ray crystal structure of 4d. [Color figure can be viewed in
Figure 3. X-ray crystal structure of 4f. [Color figure can be viewed in the
the online issue, which is available at wileyonlinelibrary.com.]
online issue, which is available at wileyonlinelibrary.com.]
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Pyridin-2-yl and 4,6-Dimethylpyrimidin-2-yl-cyanamides
aromaticity. The comparison of pyridine- and amino-
substituted fragments should reveal which representation
is more relevant: one can expect little bond redistribution
if the pyridinium fragment retains aromaticity (canonical
structure IIa′).
The bond lengths in heterocyclic and NCN fragments of
4d–f and 11b, c are summarized in Table 2. The N1―C2
and C2―N3 bond lengths, corresponding to the
N≡C―N fragments, remain remarkably similar between
N3- and N9-substituted compounds, indicating that the
conjugation with the CN-group is not significantly affected
by N-alkylation. Indeed, the most pronounced changes
upon moving the substituent from amino group to hetero-
cycle are observed for bonds with C4 atom: N3―C4 bond
is shortened, on average, by 0.066Å, and N9―C4 and
C4―N5(C5) are elongated significantly more than one
can expect upon change from pyridinium to pyrimidine
fragment. The bond redistribution pattern thus is consistent
with canonical structure IIa. The bond length within the ar-
omatic ring, with equal C8―N9 and N9―C4 bond
lengths, also supports the representation IIa. This result
is in agreement with UV spectroscopy studies, which indi-
cate that the studied system is different from both pyridine
and 2-aminopyridine.
Figure 4. X-ray crystal structure of 11b. [Color figure can be viewed in
the online issue, which is available at wileyonlinelibrary.com.]
The resulting alkylated cyanamides 4 and 11 have char-
acteristic ultraviolet absorption spectra, which consist of
low-intensity long-wavelength band and high-intensity
short-wavelength band. The positions of the absorption
bands-maxima for compounds 4 and 11 are different: in
the case of compound 11 they are longer waves shifted
(Table 3). We can suppose that the substituted heterocyclic
moiety of these compounds is responsible for observed
long-wavelength absorption band [20], and acetophenone
fragment—for the shoulder maximum in the spectrum of
compounds 4m, 11e, and 11f [21].
Unlike pyrimidine-containing compound 4, the
alkylated derivatives of pyridin-2-ylcyanamide 2 possess
visible blue fluorescence in solution. The fluorescence
spectra of all studied compounds contain a broad band at
380 – 550nm with the main peak at 421–427nm and
shoulder maxima at about 400 and 460nm. The shape of
the solution fluorescence spectra does not depend on the
excitation wavelength (270nm, 330nm, and 370 nm). Fluo-
rescence excitation spectra of these compounds have
almost the same shape as their absorption spectra. Fluores-
cence quantum yield values of compounds 11a, 11c, and
11d in solution are slightly different (ϕfl ~ 0.28 – 0.32),
for compounds 11b and 11f it is somewhat lower (ϕfl ~
0.22 and ϕfl ~ 0.16, respectively), and for compound 11e
it is almost equal to zero (ϕfl ~ 0.03, Table 3). The fluores-
cence lifetimes for compounds 11a, 11c, and 11d are ap-
proximately 5 ns, but for compounds 11b, 11e, and 11f
they are slightly lower—3.7, 0.4, and 2.7 ns, respectively
(Table 3).
Figure 5. X-ray crystal structure of 11c. [Color figure can be viewed in
the online issue, which is available at wileyonlinelibrary.com.]
of the p-tolyl group; an example molecule is shown in
Figure 2.
The crystal of 11b contains one 11b molecule and one
water molecule in independent part (Fig. 4). The water
formed a hydrogen bond with N1 atom of the NCN group
(N…O 2.865(6) Å, N―H…O 176(3)°), which did not sig-
nificantly affect the bond length distribution in comparison
with 11c (Fig. 5).
This is the first manuscript to report the crystal structures
of pyridines with linear N―C―N substituent (according
to Cambridge Structural Database), so we decided to per-
form a deeper analysis of bond length distribution in these
compounds. One can assume two possible canonical struc-
tures IIa and IIa′ for the studied fragment (Scheme 1),
with the charge separation required for retaining the
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. S. Shestakov, A. H. Moustafa, I. S. Bushmarinov, A. S. Goloveshkin, A. V. Shapovalov,
Kh. S. Shikhaliev, M. A. Prezent, and O. E. Sidorenko
Vol 000
Table 2
The bond lengths (Å) of heterocyclic and NCN fragments in 4d–f and 11b–c.
4d
4eb
4f
11b
11c
N1―C2
C2―N3
1.1505(14)
1.3421(13)
1.4094(13)
1.3343(13)
1.3479(14)
1.3917(15)
1.3905(15)
1.3478(14)
1.3305(13)
1.4786(13)
—
1.151(3)
1.346(4)
1.409(4)
1.335(4)
1.347(4)
1.388(4)
1.384(4)
1.358(4)
1.326(4)
1.497(4)
—
1.1558(12)
1.3430(11)
1.4083(11)
1.3370(11)
1.3446(11)
1.3969(12)
1.3914(13)
1.3506(12)
1.3316(11)
1.4799(11)
—
1.166(3)
1.319(3)
1.347(3)
1.417(4)
1.370(4)
1.417(4)
1.356(4)
1.378(3)
1.378(3)
—
1.1628(13)
1.3212(12)
1.3398(12)
1.4187(13)
1.3657(14)
1.4089(14)
1.3633(14)
1.3705(12)
1.3713(12)
—
N3―C4
C4―N5(C5)a
N5(C5)a―C6
C6―C7
C7―C8
C8―N9
N9―C4
N3―C12
N9-C10
1.471(4)
1.4738(11)
aN5 in 4d,e,f and C5 in 11b,c.
bFor 4e, average bond lengths are provided.
Table 3
Absorption and fluorescent properties of compound 11 in methylene chloride.
Compound
λambasx, nm (ε)
λflmax, nm
ϕ
τ, nс
11a
11b
11c
11d
11e
11f
265 (13 610), 340 (5500)
263 (14 030), 342 (6500)
265 (14 570), 343 (5800)
423
391a, 421
427
425
426
0.29
0.22
0.32
0.28
0.03
0.16
5.2
3.7
5.4
4.8
0.4
2.7
264 (17 010), 342 (7320)
252 (20 460), 268a (13 930), 344 (6270)
269 (26 400), 285a (19 000), 343 (6940)
424
aShoulder maximum.
CONCLUSIONS
(254 nm/365 nm) for visualization. Melting points were detected
with a Büchi B-540 melting point apparatus and were uncor-
rected. Infrared spectra were recorded with a FTIR Bruker Vertex
70 and are given as cmꢀ1 using the attenuated total reflection
(ATR) method. NMR spectra were recorded in DMSO-d6
on a Bruker AC-300 or Bruker DRX-500 spectrometers with
In summary, we have studied the sides of the alkylation
reaction for sodium salts of cyanamides, and we found that,
the exo-cyclic nitrogen atom of amino cyanamide group
was alkylated in the case of N-(4,6-dimethylpyrimidin-2-
yl)cyanamide, while the endo-cyclic nitrogen atom was
found to be the reaction center in the case of pyridin-2-yl
cyanamide. The crystal structures of such compounds have
been reported for the first time. Alkylated cyanamides can
be regarded as potential building blocks for the construc-
tion of heterocyclic compounds. The ability of alkylated
derivatives of pyridin-2-yl cyanamide to fluoresce in a vis-
ible region can be employed in creation of fluorescent la-
bels containing such groups. Presently, 4- and 4,5-
substituted pyrimidin-2-yl cyanamides and their alkylated
derivatives are considered the aim of further study.
1
a 300, 500-MHz NMR spectrometer for H NMR and 75 MHz
for 13C NMR. Chemical shifts (δ) were given in parts per
million (ppm) with reference to tetramethylsilane (TMS) as an
internal standard and the coupling constants (J) were given in
hertz (Hz). Elemental analyses were obtained on a Carlo Erba
NA-1500 CHNS Elemental Analyzer.
Density functional theory (DFT) calculations were performed
using Gaussian 03 program [22] with the B3LYP exchange-
correlation functional. The basis (6-311++G**) was used for all
atoms. Geometry optimizations were performed with full relaxa-
tion of all atoms. Calculations were performed in gas phase with-
out solvent effects. Vibrational frequency calculations were
performed to check that the stable structures had no imaginary
frequency.
Single crystals of 4d–f, 11b, and 11c were grown from
2-propanol, 2-propanol-water, and acetonitrile. Suitable crystals
EXPERIMENTAL
were selected and studied on
a Bruker Apex II Duo
All commercially available reagents were purchased from
Merck, Aldrich, and Fluka and were used without further purifica-
tion. The progress of the reactions was monitored by TLC
using aluminum silica gel plates 60 F254 using UV light
diffractometer. The crystals were kept at 100 K during data
collection. Using Olex2 [23], the structures was solved with
the XS structure solution program [24] using Direct Methods
and refined with the XL refinement package using Least Squares
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Month 2016
Pyridin-2-yl and 4,6-Dimethylpyrimidin-2-yl-cyanamides
minimization. The crystal of 4e has systematic twinning. The
twinning matrix is (0.0, 0.0, 1.0, 0.0, ꢀ1.0, 0.0, 1.0, 0.0, 0.0),
and BASF parameter is 0.44338.
ν
max: 3010, 2227, 1597, 1550, 1500, 1446 cmꢀ1; UV: λ max
232 nm (ε 16 170), 273 nm (ε 4030); 1H NMR (500 MHz,
DMSO-d6): δ 2.39 (s, 6H, 2CH3), 5.07 (s, 2H, CH2), 7.00 (s,
1H, ArH), 7.33–7.42 (m, 5H, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 23.4, 50.2, 111.5, 115.3, 128.1, 128.2, 128.7,
135.4, 157.3, 168.7. Anal. Calcd for C14H14N4: C, 70.57; H,
5.92; N, 23.51. Found: C, 70.55; H, 5.87; N, 23.58.
UV absorption spectra were taken on a Varian Cary 100 spec-
trophotometer. Samples were dissolved in methylene chloride and
scanned in a layer L = 0.1 cm. Fluorescence spectra were mea-
sured on a Horiba Jobin Yvon Fluorolog 3–221 spectrofluorome-
ter an angle 7–10° and 1 × 1 cm quartz cells. All measurements
were carried out at room temperature (298 K). The relative fluo-
rescence quantum yield (ϕfl) was measured in a weakly concen-
trated solution of methylene chloride (C~10ꢀ6 mol/L). The
solution of diphenylanthracene in ethanol was used as standard
solution (ϕfl = 0.9) [25].
General procedure for the synthesis of N-alkyl-N-
(4,6-dimethylpyrimidin-2-yl)cyanamide derivatives (4a–m).
Cyanamide 1 (1.48 g, 10 mmol) was dissolved in a solution of
1M sodium methoxide (10 mL). The solvent was removed under
vacuum, and the remaining sodium salt was dissolved in
DMAC (5 mL). To this reaction mixture, alkyl halide (10 mmol)
and/or (15 mmol for methyl iodide and ethyl bromide) was
added and stirred at 20–60°C for 5 min. After cooling, it was
poured onto ice-cold distilled water (50–100 mL); the obtained
solid was filtered, washed by distilled water, and recrystallized
from 2-propanol to afford 4c–m. The reaction mixture of
compound 4a and/or 4b was extracted three times with
methylene chloride (3 × 30 mL) from distilled water. The
combined extract was dried over Na2SO4, concentrated, and
recrystallized from the same solvent.
X-ray crystallographic data for 4d.
Formula C14H14N4,
M = 238.29, monoclinic, space group P21/c (no. 14), a = 9.6261
(19) Å, b = 6.9517(14) Å, c = 19.192(4) Å, β = 92.29(3)°,
V = 1283.3(4) Å3, Z = 4, T = 100 K, μ(MoKα) = 0.077 mmꢀ1
,
Dcalc = 1.233 g/mm3, 16787 reflections measured (4.24 ≤ 2θ ≤ 61),
3905 unique (Rint = 0.0313) which were used in all calculations.
The final R1 was 0.0424 (>2sigma(I)) and wR2 was 0.1245
(all data).
N-(4,6-Dimethylpyrimidin-2-yl)-N-(4-methylbenzyl)-cyanamide(4e).
Colorless needles (1.74 g, 69% yield), mp 79–80°C. IR (ATR),
ν
max: 3018, 2230, 1591, 1545, 1515, 1452 cmꢀ1; UV: λ max
231 nm (ε 17 850), 273 nm (4180); 1H NMR (300 MHz,
DMSO-d6 + CCl4): δ 2.35 (s, 3H, CH3), 2.41 (s, 6H, 2CH3),
4.99 (s, 2H, CH2), 6.87 (s, 1H, ArH), 7.15 (d, J = 7.2 Hz, 2H,
ArH), 7.29 (d, J = 7.2 Hz, 2H, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 20.6, 23.3, 49.9, 111.5, 115.2, 128.1, 129.2,
132.3, 137.5, 157.3, 168.6. Anal. Calcd for C15H16N4: C, 71.40;
H, 6.39; N, 22.20. Found: C, 71.34; H, 6.45; N, 22.21.
X-ray crystallographic data for 4e.
Formula C15H16N4,
M = 252.32, monoclinic, space group P21/n (no. 14),
a = 28.550(3) Å, b = 6.6861(7) Å, c = 28.535(2) Å, β = 99.264
N-(4,6-Dimethylpyrimidin-2-yl)-N-methylcyanamide (4a).
Colorless prisms, (0.66 g, 41% yield), mp 110–112°C (Lit. [10]:
107–108°C). IR (ATR), νmax: 2945, 2925, 2228, 1597, 1550,
(2)°, V= 5376.0(9) Å3, Z=16, T= 100 K, μ(MoKα) = 0.078 mmꢀ1
,
Dcalc = 1.247 g/mm3, 29 691 reflections measured (1.44 ≤ 2θ ≤ 56.56),
13044 unique (Rint = 0.0897) which were used in all calculations.
The final R1 was 0.0506 (>2sigma(I)) and wR2 was 0.1061
(all data).
1
1437 cmꢀ1; UV: λ max 232 nm (ε 16 530), 273 nm (ε 4310); H
NMR (300 MHz, DMSO-d6 + CCl4): δ 2.38 (s, 6H, 2CH3),
3.39 (s, 3H, CH3), 6.98 (s, 1H, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 23.3, 35.2, 112.3, 114.8, 157.7, 186.4. Anal.
Calcd for C8H10N4: C, 59.24; H, 6.21; N, 34.54. Found: C,
59.32; H, 6.28; N, 34.40.
N-(4,6-Dimethylpyrimidin-2-yl)-N-(2-methylbenzyl)-cyanamide
(4f). Colorless prisms, (2.19 g, 87% yield), mp 120–122°C. IR
(ATR), νmax: 2995, 2226, 1595, 1547, 1495, 1449 cmꢀ1; UV: λ
max 232 nm (ε 16 900), 273 nm (ε 4210); 1H NMR (300MHz,
DMSO-d6 + CCl4): δ 2.38 (s, 3H, CH3), 2.42 (s, 6H, 2CH3), 5.02
(s, 2H, CH2), 6.89 (s, 1H, ArH), 7.13–7.25 (m, 3H, ArH), 7.31
(d, J= 7.2 Hz, 1H, ArH); 13C NMR (75 MHz, DMSO-d6): δ 18.7,
23.3, 48.2, 111.3, 115.3, 126.0, 128.2, 128.7, 130.4, 133.0, 136.6,
157.4, 168.6. Anal. Calcd for C15H16N4: C, 71.40; H, 6.39; N,
22.20. Found: C, 71.45; H, 6.40; N, 22.15.
N-(4,6-Dimethylpyrimidin-2-yl)-N-ethylcyanamide (4b).
Colorless prisms, (1.11 g, 63% yield), mp 68–69°C. IR (ATR),
ν
max: 2970, 2224, 1593, 1547, 1460 cmꢀ1; UV: λ max 233 nm
(ε 19 170), 274 nm (ε 4860); 1H NMR (300 MHz, DMSO-d6
+ CCl4): δ 1.29 (t, J = 7.1 Hz, 3H, CH3CH2), 2.37 (s, 6H,
2CH3), 3.86 (q, J = 7.1 Hz, 2H, CH2CH3), 6.98 (s, 1H, ArH);
13C NMR (75 MHz, DMSO-d6): δ 12.6, 23.4, 42.4, 111.3,
115.0, 157.3, 168.5. Anal. Calcd for C9H12N4: C, 61.34; H,
6.86; N, 31.79. Found: C, 61.30; H, 6.86; N, 31.84.
X-ray crystallographic data for 4f.
Formula C15H16N4,
M = 252.32, monoclinic, space group P21/c (no. 14), a = 9.4605
(5) Å, b = 7.2101(3) Å, c = 19.3871(9) Å, β = 94.025(1)°,
Ethyl 2-(N-(4,6-dimethylpyrimidin-2-yl)cyanamide)acetate (4c).
Colorless prisms, (1.26 g, 54% yield), mp 125–127°C (Lit. [5]:
107–108°C). IR (ATR), νmax: 2973, 2239, 1741, 1597, 1546,
V = 1319.15(11) Å3, Z = 4, T = 100 K, μ(MoKα) = 0.079 mmꢀ1
,
Dcalc = 1.2704 g/mm3,
20 953
reflections
measured
(4.22 ≤ 2θ ≤ 67.34), 5233 unique (Rint = 0.0269) which were used
in all calculations. The final R1 was 0.044956 (I ≥ 2u(I)) and
wR2 was 0.131241 (all data).
N-(4-Chlorobenzyl)-N-(4,6-dimethylpyrimidin-2-yl)-cyanamide
(4g). Colorless needles, (1.91g, 70% yield), mp 88–89°C. IR
(ATR), νmax: 2998, 2233, 1593, 1549, 1489, 1445 cmꢀ1; UV: λ
max 231 nm (ε 20 830), 273 nm (ε 4180); 1H NMR (300 MHz,
DMSO-d6 +CCl4): δ 2.41 (s, 6H, 2CH3), 5.03 (s, 2H, CH2), 6.89
(s, 1H, ArH), 7.36 (d, J = 7.1Hz, 2H, ArH), 7.41 (d, J = 7.1 Hz,
2H, ArH); 13C NMR (75 MHz, DMSO-d6): δ 23.3, 49.5, 111.3,
1
1432 cmꢀ1; UV: λ max 228 nm (ε 13 690), 270 nm (ε 4290); H
NMR (500 MHz, DMSO-d6): δ 1.19 (t, J =7.1 Hz, 3H, CH3CH2),
2.39 (s, 6H, 2CH3), 4.19 (q, J =7.1 Hz, 2H, CH2CH3), 4.68 (s,
2H, CH2N), 7.12 (s, 1H, ArH). 13C NMR (75 MHz, DMSO-d6): δ
13.9, 23.3, 48.5, 61.2, 111.2, 115.5, 156.8, 167.6, 168.6. Anal.
Calcd for C11H14N4O2: C, 56.40; H, 6.02; N, 23.92. Found: C,
56.34; H, 5.95; N, 24.02.
N-Benzyl-N-(4,6-dimethylpyrimidin-2-yl)cyanamide (4d).
Colorless prisms, (1.41 g, 59% yield), mp 76–77°C. IR (ATR),
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. S. Shestakov, A. H. Moustafa, I. S. Bushmarinov, A. S. Goloveshkin, A. V. Shapovalov,
Kh. S. Shikhaliev, M. A. Prezent, and O. E. Sidorenko
Vol 000
115.3, 128.6, 130.0, 132.9, 134.4, 157.1, 168.6. Anal. Calcd for
C14H13ClN4: C, 61.65; H, 4.80; N, 20.54. Found: C, 61.72; H,
4.74; N, 20.63.
N-(4,6-Dimethylpyrimidin-2-yl)-N-(2-oxo-2-phenylethyl)-
cyanamide (4m). Colorless prisms, (2.08 g, 78% yield), mp
146–148°C. IR (ATR), νmax: 2998, 2236, 1704, 1689, 1595,
1541, 1408 cmꢀ1; UV: λ max 234 nm (ε 20 560), 271 nm (ε
N-(3-Chlorobenzyl)-N-(4,6-dimethylpyrimidin-2-yl)-cyanamide
1
5680), 323 nm (ε 340 shoulder maximum); H NMR (300 MHz,
(4h).
Colorless prisms, (2.07g, 76% yield), mp 77–78°C. IR
(ATR), νmax: 3006, 2226, 1595, 1543, 1475, 1443cmꢀ1; UV: λ
DMSO-d6): δ 2.33 (s, 6H, 2CH3), 5.50 (s, 2H, CH2), 6.98 (s,
1H, ArH), 7.59 (t, J = 7.2 Hz, 2H, ArH), 7.72 (t, J = 7.2 Hz, 1H,
ArH), 8.04 (d, J = 7.2 Hz, 2H, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 23.3, 53.4, 111.6, 115.3, 128.0, 129.0, 134.1,
134.3, 157.2, 168.6, 192.6. Anal. Calcd for C15H14N4O: C,
67.65; H, 5.30; N, 21.04. Found: C, 67.72; H, 5.22; N, 21.12.
3-(4,6-Dimethylpyrimidin-2-yl)-5-phenyl-oxazol-2(3H)-
imine (5). To a solution of cyanamide 4m (1.6 g, 6 mmol) in
DMAC (15 mL), triethylamine (0.92 mL, 6.6 mmol) was added.
The reaction mixture was heated at 70°C for 10 h, and then
poured onto distilled water. The crude product was filtered,
dried, and purified by recrystallization from dimethyl-
formamide to give compound 5 as pale yellow prisms, (1.07 g,
67% yield), mp 160–161°C. IR (ATR), νmax: 3290, 3165,
1
max 233 nm (ε 14 910), 274 nm (ε 3970); H NMR (300MHz,
DMSO-d6 + CCl4): δ 2.44 (s, 6H, 2CH3), 5.06 (s, 2H, CH2), 6.90
(s, 1H, ArH), 7.29–7.40 (m, 3H, ArH), 7.43 (s, 1H, ArH); 13C
NMR (75 MHz, DMSO-d6): δ 23.3, 49.5, 111.3, 115.4, 126.7,
127.9, 128.1, 130.6, 133.2, 137.8, 157.1, 168.6. Anal. Calcd for
C14H13ClN4: C, 61.65; H, 4.80; N, 20.54. Found: C, 61.64; H,
4.79; N, 20.47.
N-(2-Chlorobenzyl)-N-(4,6-dimethylpyrimidin-2-yl)-cyanamide
(4i). Colorless prisms, (1.72 g, 63% yield), mp 141–143°C. IR
(ATR), νmax: 3007, 2232, 1600, 1543, 1474, 1448cmꢀ1; UV: λ
1
max 230 nm (ε 15 830), 272 nm (ε 4120); H NMR (300MHz,
DMSO-d6 + CCl4): δ 2.43 (s, 6H, 2CH3), 5.12 (s, 2H, CH2), 6.90
(s, 1H, ArH), 7.30–7.37 (m, 2H, ArH), 7.42–7.50 (m, 2H, ArH);
13C NMR (75 MHz, DMSO-d6): δ 23.4, 48.3, 111.0, 115.5, 127.5,
129.6, 130.2, 130.7, 132.3, 133.1, 157.2, 168.7. Anal. Calcd for
C14H13ClN4: C, 61.65; H, 4.80; N, 20.54. Found: C, 61.58; H,
4.82; N, 20.54.
1686, 1650, 1596, 1531, 1423 cmꢀ1 1H NMR (500 MHz,
;
DMSO-d6): δ 2.48 (s, 6H, 2CH3), 7.11 (s, 1H, ArH), 7.35 (t,
J = 7.5 Hz, 1H, ArH), 7.45 (t, J = 7.6 Hz, 2H, ArH), 7.70 (d,
J = 7.7 Hz, 2H, ArH), 8.16 (s, 1H, ArH), 8.40 (s, 1H, NH); 13C
NMR (75 MHz, DMSO-d6): δ 23.5, 107.1, 115.8, 123.2, 126.9,
128.3, 128.8, 138.2, 152.8, 154.4, 168.1. Anal. Calcd for
C15H14N4O: C, 67.65; H, 5.30; N, 21.04. Found: C, 67.60; H,
5.31; N, 20.97.
N-(4-Bromobenzyl)-N-(4,6-dimethylpyrimidin-2-yl)-cyanamide
(4j). Colorless needles, (2.92 g, 92% yield), mp 105–106°C. IR
(ATR), νmax: 2995, 2236, 1593, 1545, 1487, 1422cmꢀ1; UV: λ
1
max 231 nm (ε 22 900), 272 nm (ε 4320); H NMR (300MHz,
General procedure for the synthesis of (E)-N-(1-alkyl-
pyridin-2(1H)-ylidene)cyanamide derivatives (11a–f).
Cyanamide 2 (0.60 g, 5 mmol) was dissolved in a solution of
1M sodium methoxide (5 mL). The solvent was removed
under vacuum, and the remaining sodium salt was dissolved
in DMAC (2 mL). To this reaction mixture, alkyl halide
(5 mmol) and/or (0.47 mL, 7.5 mmol for methyl iodide)
was added and stirred at 20–60°C for 5 min. After cooling, it
was poured onto ice-cold distilled water (20–30 mL); the
solid obtained was filtered, washed by distilled water, and
recrystallized from 2-propanol to afford 11c–m. The reaction
mixture of compound 11a and/or 11b was extracted three
times with CH2Cl2 (3 × 30 mL) from distilled water. The
combined extract was dried over Na2SO4, concentrated, and
recrystallized from the same solvent.
DMSO-d6 + CCl4): δ 2.41 (s, 6H, 2CH3), 5.03 (s, 2H, CH2), 6.89
(s, 1H, ArH), 7.35 (d, J = 7.3 Hz, 2H, ArH), 7.51 (d, J = 7.3Hz,
2H, ArH); 13C NMR (75 MHz, DMSO-d6): δ 23.3, 49.5, 111.4,
115.4, 121.4, 130.3, 131.6, 134.8, 157.1, 168.7. Anal. Calcd for
C14H13BrN4: C, 53.01; H, 4.13; N, 17.66. Found: C, 52.93; H,
4.14; N, 17.71.
N-(4,6-Dimethylpyrimidin-2-yl)-N-(3-nitrobenzyl)-cyanamide
(4k). Pale yellow prisms, (2.32 g, 82% yield), mp 102–103°C.
IR (ATR), νmax: 3042, 2231, 1593, 1553, 1524, 1452 cmꢀ1; UV:
λ max 230 nm (ε 18 500), 266 nm (ε 11 240), 302 nm (ε 1610,
1
shoulder maximum); H NMR (300 MHz, DMSO-d6 + CCl4): δ
2.43 (s, 6H, 2CH3), 5.20 (s, 2H, CH2), 6.91 (s, 1H, ArH), 7.67 (t,
J = 7.2 Hz, 1H, ArH), 7.85 (d, J = 7.2 Hz, 1H, ArH), 8.20 (d,
J = 7.2 Hz, 1H, ArH), 8.35 (s, 1H, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 23.3, 49.5, 111.3, 115.5, 123.0, 123.1, 130.3,
134.8, 137.7, 147.8, 157.0, 168.8. Anal. Calcd for C14H13N5O2:
C, 59.36; H, 4.63; N, 24.72. Found: C, 59.33; H, 4.68; N, 24.66.
N-(4,6-Dimethylpyrimidin-2-yl)-N-(naphthalene-1-ylmethyl)
(E)-N-(1-Methylpyridin-2(1H)-ylidene)cyanamide (11a).
Colorless prisms, (0.35 g, 52% yield), mp 99–101°C. IR (ATR),
ν
max: 3421, 2171, 1638, 1553, 1517, 1465 cmꢀ1; UV: λ max
265 nm (ε 13 610), 340 nm (ε 5500); 1H NMR (300 MHz,
DMSO-d6): δ 3.63 (s, 3H, CH3), 6.58 (ddd, J = 1.3, 6.6, 7.0 Hz,
1H, ArH), 7.15 (d, J = 8.9 Hz, 1H, ArH), 7.66 (ddd, J = 1.5, 6.6,
8.9 Hz, 1H, ArH), 7.96 (dd, J = 1.4, 6.6 Hz, 1H, ArH); 13C
NMR (75 MHz, DMSO-d6): δ 40.3, 110.5, 116.7, 118.0, 141.0,
141.1, 160.9. Anal. Calcd for C7H7N3: C, 63.14; H, 5.30; N,
31.56. Found: C, 63.21; H, 5.22; N, 31.57.
cyanamide (4l).
Colorless prisms, (1.96 g, 68% yield), mp
121–123°C. IR (ATR), νmax: 3015, 2230, 1597, 1543, 1512,
1434 cmꢀ1; UV: λ max 230 nm (ε 26 840), 264 nm (ε 7030,
shoulder maximum), 272 nm (ε 10 130), 282 nm (ε 10 390),
1
293 nm (ε 5570), 313 nm (ε 390, shoulder maximum); H NMR
(300 MHz, DMSO-d6 + CCl4): δ 2.41 (s, 6H, 2CH3), 5.53 (s,
2H, CH2), 7.04 (s, 1H, ArH), 7.50–7.62 (m, 4H, ArH), 7.93–
8.04 (m, 2H, ArH), 8.10 (m, 1H, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 23.4, 47.9, 111.0, 115.3, 123.1, 125.3, 126.0,
126.7, 127.3, 128.7, 129.0, 130.4, 130.9, 133.3, 157.3, 168.7.
Anal. Calcd for C18H16N4: C, 74.98; H, 5.59; N, 19.43. Found:
C, 75.06; H, 5.54; N, 19.40.
(E)-Methyl 2-(2-(cyanoimino)pyridin-1(2H)-yl)acetate (11b).
Colorless prisms, (0.32 g, 33% yield), mp 119–120°C. IR
(ATR), νmax: 3392, 2154, 1735, 1638, 1552, 1516 cmꢀ1; UV: λ
1
max 263 nm (ε 14 030), 342 nm (ε 6500); H NMR (300 MHz,
DMSO-d6): δ 3.76 (s, 3H, CH3), 4.90 (s, 2H, CH2), 6.62 (ddd,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2016
Pyridin-2-yl and 4,6-Dimethylpyrimidin-2-yl-cyanamides
J = 1.4, 6.6, 7.2 Hz, 1H, ArH), 7.18 (d, J = 9.0 Hz, 1H, ArH), 7.71
(ddd, J = 1.8, 6.6, 8.8 Hz, 1H, ArH), 7.92 (dd, J = 1.8, 6.6 Hz, 1H,
ArH); 13C NMR (75 MHz, DMSO-d6): δ 52.5, 52.9, 110.7, 116.9,
117.2, 140.8, 141.9, 160.8, 167.4. Anal. Calcd for C9H9N3O2: C,
56.54; H, 4.74; N, 21.98. Found: C, 56.46; H, 4.77; N, 22.06.
(E)-N-(1-(2-(4-Methoxyphenyl)-oxoethyl)pyridin-2(1H)-ylidene)
cyanamide (11f). Colorless prisms, (0.89 g, 66% yield), mp
187–188°C. IR (ATR), νmax: 3423, 2154, 1686, 1638, 1601,
1552, 1513 cmꢀ1; UV: λ max 269 nm (ε 26 400), 285 nm (ε
19 000 shoulder maximum), 343 nm (ε 6940); 1H NMR
(300 MHz, DMSO-d6): δ 3.89 (s, 3H, CH3), 5.64 (s, 2H, CH2),
6.63 (ddd, J = 1.6, 6.6, 8.1 Hz, 1H, ArH), 7.04 (d, J = 8.8 Hz,
2H, ArH), 7.21 (d, J = 9.0 Hz, 1H, ArH), 7.71 (ddd, J = 1.8, 6.6,
8.8 Hz, 1H, ArH), 7.86 (dd, J = 1.8, 6.6 Hz, 1H, ArH), 8.02 (d,
J = 8.8 Hz, 2H, ArH); 13C NMR (75 MHz, DMSO-d6): δ 55.7,
57.6, 110.7, 114.3, 117.0, 117.5, 127.1, 130.5, 141.3, 141.7,
160.7, 163.9, 189.8. Anal. Calcd for C15H13N3O2: C, 67.41; H,
4.90; N, 15.72. Found: C, 67.49; H, 4.82; N, 15.81.
X-ray crystallographic data for 11b.
Formula
C9H11N3O3, M = 209.21, monoclinic, space group P21/c (no.
14), a = 11.95(3) Å, b = 17.15(3) Å, c = 5.007(10) Å, β = 97.617
(6)°, V = 1017(4) Å3, Z = 4, T = 100 K, μ(MoKα) = 0.105 mmꢀ1
,
Dcalc = 1.366 g/mm3,
8234
reflections
measured
(3.44 ≤ 2θ ≤ 61.02), 3060 unique (Rint = 0.1726) which were used
in all calculations. The final R1 was 0.0555 (>2sigma(I)) and
wR2 was 0.1245 (all data).
2-Amino-3-benzoylimidazo[1,2-a]pyridine (12).
To a
(E)-N-(1-Benzylpyridin-2(1H)-ylidene)cyanamide (11c).
Colorless prisms, (0.71 g, 67% yield), mp 143–144°C. IR
solution of cyanamide 11e (0.48 g, 2 mmol) in DMAC (5 mL),
triethylamine (0.42 mL, 3 mmol) was added. The reaction
mixture was heated at 90°C for 10 h, and then poured onto
distilled water. The crude product was filtered, dried, and
purified by recrystallization from dimethylformamide to give
compound 12 as pale yellow solid, (0.428 g, 89% yield), mp
202–204°C (Lit. [19b]: mp 196–200°C). IR (ATR) νmax 3481,
(ATR), νmax
:
3080, 3041, 2976, 2139, 1634, 1556,
1510 cmꢀ1; UV: λ max 265 nm (ε 14 570), 343 nm (ε 5800);
1H NMR (300 MHz, DMSO-d6): δ 5.33 (s, 2H, CH2), 6.75 (t,
J = 6.5 Hz, 1H, ArH), 7.18 (d, J = 8.8 Hz, 1H, ArH), 7.26–
7.38 (m, 5H, ArH), 7.76 (ddd, J = 1.1, 6.4, 7.6 Hz, 1H, ArH),
8.16 (dd, J = 1.1, 6.4 Hz, ArH); 13C NMR (75 MHz,
DMSO-d6): δ 54.3, 111.0, 117.4, 117.7, 127.6, 127.8, 128.6,
135.6, 140.5, 141.3, 160.6. Anal. Calcd for C13H11N3: C,
74.62; H, 5.30; N, 20.08. Found: C, 74.62; H, 5.35; N, 20.03.
3300, 3110, 1699, 1644, 1619, 1553, 1516, 1491 cmꢀ1 1H
;
NMR (500 MHz, DMSO-d6): δ 5.62 (s, 2H, NH2), 6.98 (t,
J = 6.8 Hz, 1H, ArH), 7.38 (d, J = 8.8 Hz, 1H, ArH), 7.52 (t,
J = 7.9 Hz, 1H, ArH), 7.56–7.60 (m, 5H, ArH), 9.14 (d,
J = 5.6 Hz, 1H, ArH); 13C NMR (75 MHz, DMSO-d6): δ 112.6,
113.8, 117.0, 126.8, 128.2, 129.2, 130.6, 130.7, 140.3, 147.3,
158.4, 181.9. Anal. Calcd for C14H11N3O: C, 70.87; H, 4.67; N,
17.71. Found: C, 71.03; H, 4.76; N, 17.72.
X-ray crystallographic data for 11c.
Formula C13H11N3,
M = 209.25, monoclinic, space group P21/c (no. 14), a = 9.6282
(7) Å, b = 7.3585(5) Å, c = 15.3953(11) Å, β = 95.5830(10)°,
V = 1085.57(13) Å3, Z = 4, T = 100 K, μ(MoKα) = 0.079 mmꢀ1
,
Dcalc = 1.280g/mm3,
11505
reflections
measured
(4.26 ≤ 2θ ≤ 58), 2882 unique (Rint = 0.0178) which were used in
all calculations. The final R1 was 0.0460 (>2sigma(I)) and wR2
was 0.1303 (all data).
Acknowledgments. This study has been supported by the Ministry
of education and science of Russian Federation in a government job
to the higher education institutions in the field of scientific activities
for 2014-2016 years (project № 4.2100.2014/K).
(E)-N-(1-(2-Fluorobenzyl)pyridin-2(1H)-ylidene)-cyanamide
(11d). Colorless prisms, (0.55 g, 48% yield), mp 162–163°C.
IR (ATR), νmax: 2146, 1632, 1553, 1512 cmꢀ1; UV: λ max
264 nm (ε 17 010), 342 nm (ε 7320); 1H NMR (300 MHz,
DMSO-d6): δ 5.34 (s, 2H, CH2), 6.64 (ddd, J = 1.3, 6.6, 7.3 Hz,
1H, ArH), 7.10–7.25 (m, 4H, ArH), 7.35 (dd, J = 6.5, 12.8 Hz,
1H, ArH), 7.69 (ddd, J = 1.7, 6.6, 8.9 Hz, 1H, ArH), 7.98 (dd,
J = 1.4, 6.6 Hz, 1H, ArH); 13C NMR (75 MHz, DMSO-d6): δ
49.3, 110.9, 115.3, 117.4, 117.5, 122.3, 124.6, 129.7, 130.1,
140.7, 141.5, 160.7, 161.7. Anal. Calcd for C13H10FN3: C,
68.71; H, 4.44; N, 18.49. Found: C, 68.59; H, 4.36; N, 18.37.
(E)-N-(1-(2-Oxo-2-phenylethyl)pyridin-2(1H)-ylidene)-
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cyanamide (11e).
Colorless prisms, (0.75 g, 63% yield), mp
210–212°C (Lit. [19b]: mp 180°C (dec.)). IR (ATR), νmax
:
3423, 3234, 2150, 1693, 1638, 1554, 1515 cmꢀ1; UV: λ max
252 nm (ε 20 460), 268 nm (ε 13 930 shoulder maximum),
344 nm (ε 6270); 1H NMR (500 MHz, DMSO-d6): δ 5.77 (s,
2H, CH2), 6.79 (t, J = 6.6 Hz, 1H, ArH), 7.19 (d, J = 8.9 Hz, 1H,
ArH), 7.62 (t, J = 7.5 Hz, 2H, ArH), 7.75 (t, J = 7.3 Hz, 1H,
ArH), 7.83 (ddd, J = 1.7, 6.6, 8.9 Hz, 1H, ArH), 7.97 (dd,
J = 1.4, 6.6 Hz, 1H, ArH), 8.07 (d, J = 7.5 Hz, 2H, ArH); 13C
NMR (75 MHz, DMSO-d6): δ 58.0, 110.7, 117.0, 117.5, 128.1,
129.1, 134.1, 134.3, 141.2, 141.8, 160.7, 191.6. Anal. Calcd for
C14H11N3O: C, 70.87; H, 4.67; N, 17.71. Found: C, 70.76; H,
4.74; N, 17.83.
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