Synthesis and structure of 2,4-dinitrophenylcyanoacetamide derivatives as CH acids and their organic salts

Article abstract of DOI:10.1007/s11172-009-0342-6

C-Arylation of cyanoacetamides with chloro-2,4-dinitrobenzene was performed in aceto-nitrile in presence of potassium carbonate. The CH acids obtained react with triethylamine or N-methylmorpholine to give salts that contain anions possessing highly conju

Full text of DOI:10.1007/s11172-009-0342-6

Russian Chemical Bulletin, International Edition, Vol. 58, No. 12, pp. 2443—2448, December, 2009
2443
Synthesis and structure of 2,4ꢀdinitrophenylcyanoacetamide
derivatives as CH acids and their organic salts
Yu. G. Gololobov,a I. R. Gol´ding,a F. Terrie,b P. V. Petrovskii,a K. A. Lyssenko,a and I. A. Garbuzovaa
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Science,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: (499) 135 5085. Еꢀmail: Yugol@ineos.ac.ru
bInstitut Lavoisier—Franklin, Université de Versailles,
45 Avenue des EtatsꢀUnis, 78035 Versailles Cedex, France.
СꢀArylation of cyanoacetamides with chloroꢀ2,4ꢀdinitrobenzene was performed in acetoꢀ
nitrile in presence of potassium carbonate. The CH acids obtained react with triethylamine
or Nꢀmethylmorpholine to give salts that contain anions possessing highly conjugated system of
unsaturated bonds.
Key words: 2,4ꢀdinitrophenylacetamides, CH acids, triethylammonium and Nꢀmethylꢀ
morpholinium salts of CH acids, chloroꢀ2,4ꢀdinitrobenzene, Xꢀray diffraction analysis.
The specific features of proton transfer in CH acid—
solvent—an organic base systems were discussed in paꢀ
pers,1—4 the main attention being focused on the study of
the resulting benzyl and benzylidene carbanions containꢀ
ing nitro groups in the ring. Usually, carbanions I were
studied in the solution of deuterated dimethyl sulfoxide,
the carbanions being obtained directly in solution by reꢀ
action of CH acids with bases. Using UV—Vis spectroꢀ
scopy, NMR spectroscopy, and thermodinamics data, it
was found that one of the shown resonance structures
dominates depending on substituents X, Y, Z in anion I
(Scheme 1). Attempts to isolate carbanions as crystalline
salts of the corresponding CH acids are described in some
publications, however either these attempts were unsucꢀ
cesful,5 or the obtained compounds have not been studꢀ
ied.6 Only recently, methods for the preparation of stable
crystalline organic salts and zwitterions with anions
possesing highly conjugated system of delocalized bonds
have been developed. However, cyanoacetamides have
not previously been used in the synthesis of organic salts
of the corresponding CH acids.
Scheme 1
The present paper is dedicated to the synthesis and
structural studies of 2,4ꢀdinitrophenylcyanoacetamide
derivatives as СН acids and their organic salts.
Results and Discussion
Two methods are used for the synthesis of organic
salts of type I carbanions. One of them is based on direct
reaction of methyleneꢀactive compounds with halogenoꢀ
nitrobenzenes in presence of 2 equivs of an organic base7
(usually triethylamine) according to Scheme 2. In this
method, the reaction immediately results in the desired
salts.
The second method assumes the preliminary synthesis
of CH acids with subsequent transformation of the latter
into salts under the action of organic bases.
It is the latter method that was used in the present
study. The corresponding of cyanoacetamide 1 was treated
with chloroꢀ2,4ꢀdinitrobenzene in the presence of dry
potassium carbonate in acetonitrile. Then the reaction
X, Y, Z are electronꢀwithdrawing groups.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2365—2370, December, 2009.
1066ꢀ5285/09/5812ꢀ2443 © 2009 Springer Science+Business Media, Inc.

2444
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Gololobov et al.
Scheme 2
Table 1. The yields and physicochemical characteristics of
CH acids 2a—f
Comꢀ Yield
pound (%)
M.p.
/°С
Found
Calculated
Molecular
formula
(%)
N
C
H
2a
2b
2c
2d
2e
2f
62 132—134 48.64 3.74 17.54 C13H12N4O6
48.65 3.77 17.49
55 130—132 52.85 4.38 17.67 C14H14N4O5
52.83 4.43 17.60
58 175—176 56.59 3.52 16.32 C16H12N4O5
56.47 3.55 16.46
32 171—172 43.11 2.31 22.29 C9H6N4O5
43.21 2.42 22.39
39 154—155 45.61 2.98 21.14 C10H8N4O5
45.46 3.05 21.23
57 130—131 49.44 3.44 19.24 C12H10N4O5
49.65 3.47 19.30
mass was acidified with dilute hydrochloric acid, and CH
acid 2 was isolated from the organic layer (Scheme 3).
The thus obtained CH acids 2 by this method were conꢀ
verted to crystalline salts 3 and 4 by the reactions with
triethylamine or Nꢀmethylmorpholine in a mixture acꢀ
etonitrile — ether. Analytical and physicochemical charꢀ
acteristics of the synthesized compounds are shown in
Tables 1—5.
Table 2. The yields and physicochemical characteristics of
ammonium salts 3 and 4
Comꢀ Yield
pound (%)
M.p.
/°С
Found
Calculated
Molecular
formula
(%)
N
Scheme 3
C
H
3a
4a
3b
3с
4c
3d
3e
93
92
95
93
91
95
72
96—97 54.01 6.49 16.41 C19H27N5O6
54.15 6.45 16.62
104—106 51.30 5.59 16.74 C18H23N5O7
51.30 5.50 16.62
95—96 57.25 7.01 16.58 C20H29N5O5
57.27 6.97 16.69
108—109 59.92 6.12 15.89 C22H27N5O5
59.85 6.16 15.86
135—136 57.06 2.98 15.78 C21H23N5O6
57.14 3.05 15.86
120—121 51.14 5.92 20.07 C15H21N5O5
51.27 6.02 19.93
108—109 52.54 6.37 19.24 C16H23N5O5
52.59 6.34 19.16
Table 3. IR spectra of CH acids 2
Comꢀ
pound
IR spectra, ν/cm–1
1—4: R1R2N = morpholino (a), piperidino (b);
R1 = mꢀtolyl, R2 = H (c); R1 = R2 = H (d);
R1 = Me, R2 = H (e); R1 = allyl, R2 = H (f);
C≡N
C=O
Aromatic
ring
NO2
NH
B = Et N (3), Nꢀmethylmorpholine (4)
3
2a
2b
2c
2d
2e
2f
2244
2248
2252
2251
2250
2250
1683
1677
1673
1676
1675
1660
1612
1614
1612
1597
1601
1597
1536, 1351
1551, 1353
1538, 1354
1537, 1349
1534, 1350
1534, 1350
—
—
3396
3393
3289
3274
The compositions and the structures of CH acids 2
and the corresponding salts 3, 4 followed from the data of
elemental analysis, IR spectroscopy, and 1Н and 13С NMR
spectroscopy. The Xꢀray structure analysis was perꢀ
formed for compound 4a. In the IR spectra of CH acids 2
(see Table 3), the vibration frequencies (ν) of CN,
C(O)NR1R2, NO2 groups and the benzene ring have the
standard values. However, these parameters substantially
change for salts 3 and 4 (see Table 4). Deprotonation of
CH acids 2 leads to decrease of vibration frequencies of
the nitrile, carbonyl, and nitro groups by 50—100 cm–1
(cf. Ref. 7). The presence of the negative charge so much

Carbanions of cyanoacetamides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2445
Table 4. IR spectra of ammonium salts 3 and 4
of signals for the С(7) atom by 26—30 ppm suggest that,
first, the resonance form Ia for anionic part of the salts 3
does not have considerable contribution. Second, taking
into account data from IR and UV—Vis spectroscopy and
Comꢀ
pound
IR spectra, ν/cm–1
NO2
NH NH+
C≡N C=O
Aromatic
ring
Xꢀray diffractional analysis (see below), a conclusion can
be made, that the negative charge is substantially delocalꢀ
ized with involvement all of the functional groups includꢀ
ing the substituted benzene ring. Presently, it is quite
difficult to say to what extent the electronic structure of
the anionic part of salts 3 corresponds to the resonance
forms Ib,c. The considerable lowꢀfield shift of 13С NMR
signals of C atoms of the СN and С=О groups almost by
10 ppm was quite unexpected. Additional study is needed
for explanation of these facts.
The discussion of Xꢀray structural data for the salt 4a
is of considerable interest. The spatial configuration
of the formula unit of salt 4a is shown in Fig. 1, the most
typical bond lengths and angle characteristics are preꢀ
sented in Table 7. It is reasonable to discuss the structure
of 4a in comparison with the literature data13 for the neuꢀ
tral compound 5 closely similar in structure to CH acid
2а. The character of distribution of bond lengths in anion
4a (see Fig. 1, Table 6) compared to the neutral comꢀ
pound 5 (Fig. 2) shows that the delocalization of the
negative charge occures actually with involvement of all
functional groups. The ring with the nitro groups (С6ꢀring)
in 4a is characterized by flattened boat conformation with
atoms С(1) and С(4) deviated from the plane by 0.124(2)
and 0.057(2) Å, whereas in 5 it is planar (the deviation of
3aa
4a
3bb
3c
2149 1594 1288, 1269
2160 1586 1277, 1247
2155 1598 1299, 1270
—
—
—
2652
2673
2699
—
—
—
1634 c
1616 c
—
2164 1586 1298, 1254 3390 2682
4c
3d
3e
2170 1575 1287 ш
2154 1587 1288 ш
2148 1595 1287 ш
3378 2681
3340 2682
3304 2674
—
a UV—Vis spectra: λmax = 494 nm, ε = 32000.
b UV—Vis spectra (acetone): λmax = 497 nm, ε = 28000.
c Concerns the mꢀtolyl ring.
changes the electron configuration of the benzene ring,
that the IR spectra of salts 3 and 4 do not contain characꢀ
teristic bands of aromatic compounds.
Interesting changes are observed in the 1Н and
13С NMR spectra (see Tables 5, 6) on passage from CH
acids 2 to their salts 3 and 4. In the 1Н NMR spectra, the
chemical shifts of protons of the С6ꢀring with nitro groups
experience the expected upꢀfield shift by 0.5—0.8 ppm on
passage from CH acids 2 to the corresponding salts 3
and 4. This is a usual effect observed when a neutral
compound passes to the corresponding anion.7,12 More
complicated dependence is observed in the 13С NMR
spectra of CH acids 2 and salts 3, 4. The lowꢀfield shifts
Table 5. 1Н NMR spectra of compounds 2—4 (δ, J/Hz)*
Compound
Н(3) (d, 1 Н)
Н(5) (dd, 1 Н)
Н(6) (d, 1 Н)
Н(7) (s, 1 Н)
2а
3a
4a
2b
3b
2c
3c
4c
2d
3d
2e
3e
2f
9.01 (J = 2.3)
8.56 (J = 2.0)
8.32 (J = 2.5)
9.01 (J = 2.3)
8.55 (J = 2.3)
8.85 (J = 2.4)
8.30 (J = 2.4)
8.30 (J = 2.4)
8.82 (J = 2.3)
8.24 (J = 2.5)
8.82 (br.s, 1 Н)
8.24 (J = 2.4)
8.82 (J = 2.2)
8.60 (J = 2.3, J = 8.6)
7.88 (J = 2.0, J = 9.4)
7.79 (J = 2.5, J = 9.5)
8.57 (J = 2.3, J = 8.6)
7.83 (J = 2.3, J = 9.4)
8.71 (J = 2.4, J = 8.5)
7.91 (J = 2.4, J = 9.3)
7.91 (J = 2.4, J = 9.4)
8.67 (J = 2.3, J = 8.6)
7.83 (J = 2.5, J = 9.2)
8.66 (J = 8.4)
8.13 (J = 8.6)
7.33 (J = 9.4)
7.11 (J = 9.5)
8.11 (J = 8.6)
7.29 (J = 9.4)
8.10 (J = 8.5)
7.39 (br.s, 1 Н)
7.39 (br.s, 1 Н)
8.03 (J = 8.6)
7.42 (J = 9.2)
8.03 (J = 8.4)
7.33 (br.s, 1 Н)
8.04 (J = 8.6)
5.98
—
—
5.99
—
5.99
—
—
5.85
—
5.85
—
5.89
7.79 (J = 2.4, J = 9.5)
8.68 (J = 2.2, J = 8.6)
* Proton signals of the morpholine ring: 2а — 3.66 (m, 2 Н); 3.77 (m, 4 Н); 3.89 (m, 2 Н); 3а — 3.67 (m, 4 Н); 3.72 (m, 4 Н); 4a — 3.60
(m, 4 Н); 3.73 (m, 8 Н); 3.80 (m, 4 Н); 4с — 3.16 (bs, 4 Н); 3.77 (bs, 4 Н). Proton signals of the piperidine ring: 2b — 1.63 (m, 2 Н);
1.75 (m, 2 Н); 1.83 (m, 2 Н); 3.50 (m, 1 Н); 3.62 (m, 1 Н); 3b — 1.63 (bs, 6 Н); 3.53 (bs, 4 Н). Proton signals of the Me group in
Nꢀmethylmorpholine: 4a — 2.58 (s, 3 Н); 4с — 2.78 (s, 3 Н). Proton signals of the mꢀtolyl ring: 2с — 6.96 (d, 1 Н, J = 7.4); 7.25 (m, 1 H);
7.32 (m, 1 H); 7.37 (bs, 1 Н); 2.29 (s, 3 H; Me); 3c, 4с — 6.75 (d, 1 Н, J = 7.4); 7.09 (m, 1 H); 7.34 (m, 2 H); 2.29 (s, 3 H; Me). Proton
signals of the Et group in Et3N+H: 3a, 3b — 1.16 (t, 9 H, Me, J = 7.3); 2.83 (q, 6 H, CH2, J = 7.3); 3c, 3e — 1.17 (t, 9 H, Me, J = 7.2);
3.09 (q, 6 H, CH2, J = 7.2). Proton signals in the amide group: 2с — 10.84 (bs, 1 Н); 3c, 4c — 8.87 (bs, 1 Н); 2d — 7.85 (s, 1 H); 8.13
(s, 1 H); 3d — 6.20 (bs, 2 Н); 2e — 8.59 (q, 1 H, J = 4.24); 2.67 (d, 3 H, J = 4.2); 3e — 6.86 (q, 1 H, J = 4.3); 2.59 (d, 3 H, J = 4.3);
2f — 8.91 (bs, 1 Н). Proton signals in the allyl group 2f: 3.76 (bs, 2 H, CH2); 5.10 (d, 1 H, cisꢀН, J = 10.2); 5.20 (d, 1 H, transꢀН,
J = 17.5); 5.79 (m, 1 Н, =СН).

2446
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Gololobov et al.
Table 6. 13С NMR spectra (δ) of compounds 2—4
Comꢀ
pound
C atoms
in С6ꢀrings
CH atoms
in С6ꢀrings
С(7) С(9)=О С(8)≡N
exoꢀ
C atoms in heterocycles;
the other C atoms
cyclic
2а
3а
4а
2b
3b
2c
132.7 (C(1)); 148.16 (C(2)); 121.0 (C(3)); 133.1 (C(5));
39.0
65.2
69.9
39.1
69.9
42.4
159.7
169.1
167.7
159.0
169.2
160.5
113.8
121.9
122.7
114.1
122.4
116.3
43.6; 46.9; 65.9; 66.4
(morpholine ring)
147.1 (C(4))
128.1 (C(6))
133.7; 136.5; 142.3
122.6; 123.6; 124.2
44.9; 65.7 (morpholine ring);
7.3 (Me)*; 44.1 (CH2)*
45.2; 52.7; 63.5; 66.4 (morpholine
ring); 42.7 (Me)**
23.9; 25.1; 25.6; 44.5; 47.6
(piperidine ring)
24.8; 26.2; 46.3 (piperidine ring);
8.60 (Me)*; 47.6 (CH2)*
21.1 (Me in the aromatic ring)
132.5; 136.8; 143.8
122.7 (br.s, 2 C); 124.6
133.5 (C(1)); 147.8 (C(2)); 120.7 (C(3)); 133.0 (C(5));
147.1 (C(4))
127.9 (C(6))
133.5; 137.4; 144.3
123.9; 124.1; 124.7
132.8 (C(1)); 147.8 (C(2)); 120.8 (C(3)); 133.2 (C(5));
147.8 (C(4)); 137.9; 138.5
128.6 (C(6)); 116.9; 120.2;
125.3; 128.9
3c
4c
2d
134.2; 137.3; 139.5;
140.3; 142.8
134.3; 137.4; 139.5;
140.3; 142.8
116.5; 119.9; 122.6; 122.6;
124.7; 124.8; 128.1
116.6; 119.9; 122.6; 122.7;
124.7; 124.8; 128.1
69.1
69.4
41.3
164.8
164.8
163.5
123.6
123.6
116.5
8.6 (Me)*; 47.6 (CH2)*;
21.2 (Me in С6ꢀring)
52.8; 63.6 (morpholine ring);
21.3 (Me in С6ꢀring); 42.81**
—
133.1 (C(1)); 147.8 (C(2)); 120.7 (C(3)); 133.5 (C(5));
147.9 (C(4))
128.5 (C(6))
3d
2e
134.0; 139.7; 143.4
132.8 (C(1)); 147.8 (C(2)); 120.8 (C(3)); 133.6 (C(5));
123.0; 124.9; 124.8
68.6
41.1
168.3
162.3
124.4
116.4
9.0 (Me)*; 46.2 (CH2)*
26.6 (NMe)
147.9 (C(4))
128.5 (C(6))
3e
133.3; 138.9; 143.1
123.2; 124.3; 124.6
69.9
166.9
124.0
26.5 (NMe); 8.9 (Me)*;
46.2 (CH2)*
* In Et3N+H.
** In Nꢀmethylmorpholine.
O(3)
O(4)
N(2)
C(4)
the other C atoms of the ring are less than 0.02 Å). The
bond lengths in the С6ꢀring of 4a vary in quite a broad
interval 1.367(1)—1.437(1) Å, whereas in 5 the interval of
bond lengths is considerably narrower: 1.374—1.397 Å.
Such a change in bond lengths is quite typical on radical
anion of benzene,14 which suggests high concentration of
the negative charge in the ring. In addition to the changes
in bond length distribution in the С6ꢀring, a decrease
in bond lengths С(1)—С(7) from 1.550 to 1.414(2) Å
and increase in С(13)—N(3) bond lengths from 1.133 Å
in 5 to 1.1564 Å in 4a are observed. The cyano group is
virtually coplanar with the С6ꢀring, the torsion angle
С(6)—С(1)—С(7)—С(13) is 14.5°. It should be noted
that the amide group slightly deviates from the plane
of the cyano group and the С6ꢀring (torsion angles
С(13)—С(7)—С(8)—N(4) and С(1)—С(7)—С(8)—O(5)
are 41.2 and 27.9°, respectively). It seems that the
observed conformation of amide group is caused by both
crossꢀconjugation and steric reasons (see below). The
nitro group at the C(2) atom is turned by 9.8°, whereas
the nitro group at the С(4) atom is coplanar to the ring.
The substituents at С(1) and С(2) atoms are bent in
opposite directions by 10.3 and 10.1°, which in general is
similar to the pattern observed in periꢀsubstituted naphꢀ
C(3)
C(2)
C(5)
C(6)
O(2)
C(1)
C(7)
N(1)
O(1)
O(5)
C(8)
N(3)
C(13)
C(18)
N(4)
C(12)
H(5N)
N(5)
C(9)
C(14)
C(15)
C(11)
C(17)
C(16)
O(7)
C(10)
O(6)
Fig. 1. General view of salt 4a with atoms presented as thermal
ellipsoids of vibrations (p = 50%).

Carbanions of cyanoacetamides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2447
Table 7. The main bond lengths and bond angles in crystal of 4a
Parameter
Value
Parameter
Value
Parameter
Bond angle
Value
Bond length
d/Å
Bond length
d/Å
ϕ/deg
O(1)—N(1)
N(1)—O(2)
N(1)—C(2)
C(1)—C(7)
C(1)—C(2)
C(1)—C(6)
N(2)—O(4)
N(2)—O(3)
N(2)—C(4)
C(2)—C(3)
N(3)—C(13)
C(3)—C(4)
N(4)—C(8)
N(4)—C(9)
1.2318(13)
1.2430(12)
1.4544(14)
1.4143(16)
1.4350(14)
1.4366(15)
1.2377(13)
1.2418(13)
1.4457(15)
1.3941(16)
1.1564(14)
1.3808(15)
1.3583(15)
1.4603(15)
N(4)—C(12)
C(4)—C(5)
N(5)—C(18)
N(5)—C(14)
N(5)—C(17)
C(5)—C(6)
C(7)—C(13)
C(7)—C(8)
1.4621(15)
1.4102(15)
1.4929(15)
1.4990(15)
1.4994(15)
1.3673(16)
1.4136(15)
1.4821(15)
C(3)—C(2)—N(1) 115.19(9)
C(1)—C(2)—N(1) 121.94(9)
C(4)—C(3)—C(2) 119.01(10)
C(3)—C(4)—C(5) 121.04(10)
C(3)—C(4)—N(2) 119.08(10)
C(5)—C(4)—N(2) 119.86(10)
C(6)—C(5)—C(4) 118.85(10)
C(5)—C(6)—C(1) 123.30(10)
C(13)—C(7)—C(1) 117.91(9)
C(13)—C(7)—C(8) 117.30(9)
C(1)—C(7)—C(8) 122.27(9)
O(5)—C(8)—N(4) 121.17(10)
O(5)—C(8)—C(7) 120.09(10)
N(4)—C(8)—C(7) 118.54(9)
Bond angle
ϕ/deg
C(7)—C(1)—C(2) 125.51(10)
C(7)—C(1)—C(6) 120.36(9)
C(2)—C(1)—C(6) 114.09(9)
C(3)—C(2)—C(1) 122.45(10)
1.133
1.483
thalenes, and, probably, is caused by steric repultion.15
Indeed, the length of the shortest intramolecular contact
О(1)...С(8) in the structure 4a is 2.619(2) Å.
1.4821
1.4136
1.548
1.548
1.549
1.401
Anions are joined into centrosymmetric dimers in the
crystal due to stackingꢀinteraction (the shortest contact
С(6)...С(6) 3.335(2) Å) and interaction of the CN with
the NO2 groups (N(2)…—N(3) 3.111(2) Å). The anionic
dimers are surrounded by four cations, which are bond
due to a strong hydrogen bond with the cyano group
(N(3)...N(5) 2.823(3) Å) and shortened contacts
С—Н...О (Н...О 2.28 and 2.32 Å) with carbonyl group
(Fig. 2, 3). It should be noted that the considered cation—
1.4350
1.4457
1.1564
1.480
1.380
1.376
1.4544
1.550
1.397
1.381
1.374
1.4143
1.4366
1.3673
1.4102
1.3941
1.3808
1.471
Anion of salt 4a
Fig. 2. A comparison of the structure of ethyl 2,4ꢀdinitroꢀ
phenyl(phenyl)cyanoacetate12 5 and anion of salt 4a.
C(18)
C(14)
N(5)
H(5N)
C(17)
C(16)
O(4)
C(15)
C(6)
O(7)
C(5)
N(3)
C(13)
N(2)
C(4)
C(1)
O(3)
C(3)
C(7)
C(8)
C(2)
N(1)
O(5)
O(1)
C(9)
C(10)
C(6)
N(4)
C(12)
C(11)
O(2)
Fig. 3. A fragment of crystal packing illustrating cation—anion hydrogen bonds and anion—anion stacking interaction in the structure 4a.

2448
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Gololobov et al.
Fourier synthesis and refined in the isotropic approximation.
The refinement converged to wR2 = 0.1111 and GOF = 1.015 for
all reflections (R1 = 0.0408 was calculated against F for 6037
observed reflections with I > 2σ(I)). All calculations were
performed using SHELXTL PLUS 5.0 program package.
anionic interactions can also lead to redistribution of the
charge in the anion due to withdrawal of the negative
charge from the carbonyl and cyano groups.16
Experimental
The work was carried out with a financial support
of the Russian Foundation for Basic Research (Project
№ 08ꢀ03ꢀ00196а).
NMR spectra were recorded on a Bruker АVꢀ400 instrument
(1Н, 400.26 MHz; 13C, 100.68 MHz) in CDCl3. IR spectra were
registered on a FTIR spectrometer MagnaꢀIRꢀ750 “Nicolet”
(pellets with KBr). The reactions were performed under dry
nitrogen. The solvents were purified and dried prior to use.
2,4ꢀDinitrophenylcyanoacetic acid morpholide (2а), piperidide
(2b), mꢀtoluidide (2с), amide (2d), methylamide (2е), and
allylamide (2f) were synthesized according to a general procedure.
Finely ground freshly calcined potassium carbonate (9.0 g) was
added to a solution of a cyanocetamide (0.02 mmol) and chloroꢀ
2,4ꢀdinitrobenzene in absolute acetonitrile (30 mL). The mixture
was stirred for 48 h at 20 °С, the solvent was removed, water
(50 mL) and CHCl3 (50 mL) were added to the residue. Then
pH of aqueos layer was adjusted to 2—3 with dulute hydrochloric
acid (1 : 5). The organic layer was separated, the aqueous layer
was extracted with CHCl3 (2Ѕ50 mL), the combined extracts
were dried with sodium sulfate and potassium carbonate
and filtered. The filtrate was concentrated, the residue was
crystallized from chloroform—petroleum ether (2 : 1). The yields,
melting points, and elemental analysis data of compounds 2a—f
are shown in Table 1, 1Н and 13С NMR spectra in Tables 5 and
6, IR spectra in Table 3.
References
1. M. Hojatti, K. T. Leffek, Can. J. Chem., 1984, 62, 2653.
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3. F. Terrier, E. Magnier, E. Kizilian, C. Wakselman, E. Buncel,
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∨
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4. J. Kaválek, V. Machácek, A. Lycka, V. Ctèrba, Collect. Czech.
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8. Yu. G. Gololobov, O. A. Linchenko, Z. A. Starikova, I. A.
Garbuzova, P. V. Petrovskii, Izv. Akad. Nauk, Ser. Khim.,
2005, 2393 [Russ. Chem. Bull., Int. Ed., 2005, 54, 2471].
9. Yu. G. Gololobov, O. A. Linchenko, P. V. Petrovskii,
I. A. Garbuzova, V. N. Khrustalev, Izv. Akad. Nauk, Ser.
Khim., 2006, 1261 [Russ. Chem. Bull., Int. Ed., 2006, 55,
1309].
10. Yu. G. Gololobov, O. A. Linchenko, P. V. Petrovskii, V. N.
Khrustalev, I. A. Garbuzova, Heteroatom Chem., 2007,
18, 421.
11. Yu. G. Gololobov, O. A. Linchenko, P. V. Petrovskii, V. N.
Khrustalev, I. A. Garbuzova, Mendeleev Commun., 2007,
17, 232.
Triethylammonium
carbamoyl(cyano)(2ꢀnitroꢀ4ꢀaciꢀ
nitrohexaꢀ2,5ꢀdienyl)methanide (3d) and its Nꢀderivatives —
morpholinocarbonylꢀ (3а), piperidinocarbonylꢀ (3b), mꢀtolylꢀ (3с),
methylꢀ (3е), and allylꢀ (3f), and Nꢀmethylmorpholinium (morꢀ
pholinocarbonylꢀ (4a), Nꢀmꢀtolylꢀ (4с), and Nꢀmethylcarbamoyl)ꢀ
(cyano)(2ꢀnitroꢀ4ꢀacinitrohexaꢀ2,5ꢀdienyl)methanide (4е) were
synthesized according to a general procedure. A solution of
triethylamine (0.2 g, 2 mmol) or Nꢀmethylmorpholine in ether
(4 mL) was added dropwise to a solution of amide 2b (1 mmol)
in a mixture ether—MeCN (1 : 1, 7 mL). The mixture was
stirred for 5 h at 20 °C. The carmineꢀred residue was separated,
washed with ether, and dried in vacuo. Yields, melting points,
and elemental analysis data of compounds 3a—e and 4a,c are
12. Yu. G. Gololobov, O. V. Dovgan, I. R. Golding, P. V.
Petrovskii, I. A. Garbuzova, Heteroatom Chem., 2002,
13, 36.
13. ZhiꢀSheng Jia, ChenꢀZe Qi, DiꢀLun Yang, Acta Chim.
Sinica, 1996, 54, 521.
1
shown in Table 2, Н and 13С NMR spectra in Tables 5 and 6,
14. I. V. Fedyanin, K. A. Lyssenko, Z. A. Starikova, M. Yu.
Antipin, Izv. Akad. Nauk, Ser. Khim., 2004, 1106 [Russ.
Chem. Bull., Int. Ed., 2004, 43, 1153].
15. A. S. Cieplak, in Structure Correlation, Eds H. B. Bürgi,
J. D. Dunitz, Verlag Chemie, Weinheim, 1994, 205.
16. Yu. V. Nelyubina, M. Yu. Antipin, K. A. Lyssenko, J. Phys.
Chem. A, 2007, 111, 1091.
17. G. M. Sheldrick, SADABS, Bruker AXS Inc., Madison,
WIꢀ53719, USA, 1997.
18. G. M. Sheldrick, SHELXTL PLUS, SHELXTLꢀ97,
Version 5.10, Bruker AXS Inc., Madison, WIꢀ53719, USA,
1997.
IR spectra in Table 4.
Xꢀray diffraction experiment for 4a (C18H23N5O7). At 100 K
crystals of 4a are triclinic, space group Pꢀ1, a = 6.869(2) Å,
b = 10.512(2) Å, c = 14.015(5) Å, α = 84.68(1)°, β = 87.301(12)°,
γ = 77.949(8)°, V = 985.0(5) Å3, Z = 2 (Z´ = 1), M = 421.41,
dcalc = 1.421 g cm–3, μ(MoKα) = 1.11 cm–1 F(000) = 444.
Intensities of 17789 reflections were measured with a Smart
APEX II CCD diffractometer at 100 К (λ(MoKα) = 0.71072 Å,
ωꢀscans, graphite monochromator, 2θ
< 60°), and 4685
max
independent reflections (Rint = 0.0287) were used in the further
refinement. The absorption correction and the merging of
reflections were applied using the SADABS program. The
structure was solved by direct method and refined by the fullꢀ
matrix leastꢀsquares technique against F2 in the anisotropicꢀ
isotropic approximation. Hydrogen atoms were located from the
Received December 18, 2008;
in revised form July 27, 2009