Coupling of ethyl malonate, cyanoacetate, and acetoacetate and malonodinitrile with 2-cyanoaryldiazonium bisulfates

Full text of DOI:10.1023/A:1018860207475

Doklady Chemistry, Vol. 377, Nos. 1–3, 2001, pp. 71–73. Translated from Doklady Akademii Nauk, Vol. 377, No. 1, 2001, pp. 64–66.
Original Russian Text Copyright © 2001 by Shvekhgeimer, Ushakova.
CHEMISTRY
Coupling of Ethyl Malonate, Cyanoacetate, and Acetoacetate
and Malonodinitrile with 2-Cyanoaryldiazonium Bisulfates
M-G. A. Shvekhgeimer and O. A. Ushakova
Presented by Academician N. K. Kochetkov, November 23, 2000
Received November 29, 2000
R1
R2
The reactions of aryldiazonium salts with com-
pounds containing an activated CH2 group give cou-
pling products I
II +H2C
(IV)
+
ArN2X–
CH2
–HX
+
ArNHN C
R
CN
(I)
N
R1
H2O, C2H5OH, CH3COONa
20–25°C
The aryldiazonium salts used in these reactions are
normally chlorides (X = Cl). It should be noted that the
preparation of aryldiazonium salts from aromatic
amines containing strong electron-withdrawing groups
in the ortho-position to the amino group is faced with
substantial difficulties, because the syntheses of the ini-
tial amines are multistep procedures, as well as because
of the low basicity of these amines.
C
R2
N
H
,
(V–XVI)
R, R1, R2 = H, COOC2H5, COOC2H5 (V); H, CN,
COOC2H5 (VI); H, CN, CN (VII); H, COCH3,
COOC2H5 (VIII); Br, COOC2H5, COOC2H5 (IX);
Br, CN, COOC2H5 (X); Br, CN, CN (XI); Br, COCH3,
COOC2H5 (XII); NO2, COOC2H5, COOC2H5 (XIII);
NO2, CN, COOC2H5 (XIV); NO2, CN, CN (XV);
NO2, COCH3, COOC2H5 (XVI).
Previously, we developed an original, simple, and
effective method for the synthesis of 2-cyanoaryldiazo-
nium bisulfates (II), which involves the treatment of
2-hydrazones of isatin and its derivatives (III) with
nitrosylsulfuric acid [1]
R
NNH2
This reaction was carried out at 20 to 25°C in aque-
ous ethanol in the presence of sodium acetate. Com-
pounds V–XVI were characterized by elemental analy-
sis data, melting points, and IR, UV, and 1H NMR spec-
tra.
N
H
O
(III)
The 1H NMR spectra of compounds V and VII each
exhibit two signals corresponding to the NH-group pro-
tons. Hence, these products exist as two (evidently,
rotational) isomers, the Va (or VIIa) to Vb (or VIIb)
ratio being 4 : 6.
R
CN
+
NOHSO4–(NaNO2 + H2SO4)
+
,
N2HSO4–
(II)
NC
R = H, Br, NO2.
H
N
H
N
R1
R2
N
R1
R2
N
In this study, we performed coupling of bisulfates II
with compounds IV, which gave rise to previously
unknown (2-cyanoaryl)hydrazones (V–XVI)
C
C
NC
(V , R1 = R2 = COOC2H5) (Vb, R1 = R2 = COOC2H5)
(VII , R1 = R2 = CN) (VIIb, R1 = R2 = CN)
Moscow State Textile University, Malaya Kaluzhskaya ul. 1,
Moscow, 117071 Russia
0012-5008/01/0003-0071$25.00 © 2001 åÄIä “Nauka /Interperiodica”

72
SHVEKHGEIMER, USHAKOVA
1
The H NMR spectrum of compound VI exhibits cm–1): 2224 (C≡N), 1614 (C=N), 3298 (N–H), 1745
1
only one signal for the NH proton. This compound (C=O), 1092 (C–O–C). H NMR (DMSO-d6-CCl4, δ,
exists as a single isomer, having, apparently, E config- ppm): 1.38 (t, 6H, CH2CH3), 4.26–4.41 (m, 4H,
uration
CH2CH3), 6.91–7.68 (m, 4H, CHarom), 10.83, 12.63
(both m, 1H, NH).
H
N
For C14H15N3O4 anal. calcd. (%): C, 58.12; H, 5.23;
N, 14.53.
NC
N
C
Found (%): C, 58.74; H, 5.03; N, 14.19.
NC
H5C2OCO
2-Cyanophenylhydrazone VI. Yield 56%, mp
153–154°ë (from H2O–DMF). IR (KBr, ν, cm–1): 2228
(C≡N), 1636 (C=N), 3296 (N–H), 1692 (C=O), 1096
(C–O–C). 1H NMR (DMSO-d6-CCl4, δ, ppm): 1.42 (3,
CH2CH3), 4.40–4.48 (m, 2H, CH2CH3), 13.30 (s, NH).
For C12H10N4O2 anal. calcd. (%): C, 59.50; H, 4.16;
N, 23.13.
(VI)
The 1H NMR spectrum of compound VIII exhibits
two signals for the COCH3 protons and two signals for
the NH protons. This indicates the existence of two
geometrical isomers VIIIa (Z) and VIIIb (E) (stabi-
lized by an intramolecular hydrogen bond), present in
the ratio Z : E = 3 : 7.
Found (%): C, 58.91; H, 4.18; N, 22.68.
2-Cyanophenylhydrazone VII. Yield 76%, mp
162–163°ë (from aqueous ethanol). IR (KBr, ν, cm–1):
2232 (C≡N), 1621 (C=N), 3270 (N–H). UV (λmax, nm,
logε): 202.3 (2.09), 216.8 (1.94), 257.6 (1.83), 319.2
(1.59), 350.4 (1.65), 398.4 (1.57). 1H NMR (DMSO-d6-
CCl4, δ, ppm): 6.89–8.00 (m, 4 H, CHarom), 10.84,
11.14 (both s, 1H, NH).
COCH3
CN
N C
N
COOCH2CH3
H
(VIII , Z)
COOCH2CH3
For C10H5N5 anal. calcd. (%): C, 61.53; H, 2.58; N,
35.88.
CN
N C
Found (%): C, 62.01; H, 2.37; N, 36.31.
N
COCH3
2-Cyanophenylhydrazone VIII. Yield 68%, mp
104–106°ë (from H2O–DMF). IR (KBr, ν, cm–1): 2224
(C≡N), 1638 (C=N), 3240 (N–H), 1706 (C=O), for
H
1
(VIIIb, E)
COOC2H5, 1738 (C=O), 1084 (C–O–C). H NMR
(DMSO-d6-CCl4, δ, ppm): 1.36 (t, 3H, CH2CH3), 4.28–
4.42 (m, 2H, CH2CH3), 7.21–7.83 (m, 4H, CHarom),
2.48, 2.57 (both s, 1H, NH).
For C13H13N3O3 anal. calcd. (%): C, 60.22; H, 5.05;
N, 16.21.
EXPERIMENTAL
IR spectra were recorded on a Specord M-80 spec-
trophotometer (KBr pellets); UV spectra were mea-
sured on a Uvidek 610 spectrophotometer in methanol.
1H NMR spectra were recorded on a Bruker AM-300
instrument in DMSO-d6–CCl4 solvent mixtures.
Found (%): C, 60.18; H, 5.41; N, 15.79.
4-Bromo-2-cyanophenylhydrazone IX. Yield
39%, mp 176–177°ë (from H2O–DMF). IR (KBr, ν,
cm–1): 2188 (C≡N), 1614 (C=N), 3248 (N–H), 1736
(C=O), 1118 (C–O–C).
For C14H14BrN3O4 anal. calcd. (%): C, 45.70; H,
3.84; N, 11.42.
2-Cyanophenylhydrazone V. Concentrated sulfu-
ric acid (2.5 ml) was placed in a porcelain beaker and
cooled to 0–5°ë in a water bath, and sodium nitrite
(1.4 g, 0.02 mol) was added with stirring over a period
of 30 min. Hydrazone III (R = H) (1 g, 0.0062 mol) was
added to the resulting mixture with stirring over a
period of 15 min. During this period, glacial acetic acid
(8 ml) was added at intervals. Then the mixture was
stirred for 30 min at 5–10°ë and poured into a mixture
of water (50 ml) and ice (50 g). A solution of ethyl mal-
onate (1.0 g, 0.0062 g) in ethanol (10 ml) was added to
the resulting mixture while it was stirred and cooled
with ice, and a solution of sodium acetate (10 g) in water
(50 ml) was added with stirring. The reaction mixture
was stirred for 1 h at room temperature, heated in a
Found (%): C, 46.12; H, 3.71; N, 11.57.
4-Bromo-2-cyanophenylhydrazone X.Yield 65%,
mp 159–160°ë (from H2O–DMF). IR (KBr, ν, cm–1):
2234 (C≡N), 1612 (C=N), 3204 (N–H), 1734 (C=O),
1118 (C–O–C).
For C12H9BrN4O2 anal. calcd. (%): C, 44.88; H,
2.82; N, 17.45.
Found (%): C, 44.48; H, 2.64; N, 17.78.
4-Bromo-2-cyanophenylhydrazone XI. Yield
water bath at 50°ë for 15 min, and cooled to 20°ë. The 83.8%, mp 175–176°ë (from aqueous ethanol). IR
precipitate was filtered off, washed three times in a fil- (KBr, ν, cm–1): 2240 (C≡N), 1615 (C=N), 3240 (N–H).
ter with water, and recrystallized from a water–DMF UV (λmax, nm, logε): 205.6 (1.91), 216.0 (1.83), 268.0
mixture.Yield 0.5 g (23%), mp 168–169°ë. IR (KBr, ν, (1.56), 348.0 (1.45), 403.2 (1.56).
DOKLADY CHEMISTRY Vol. 377
Nos. 1–3 2001

COUPLING OF ETHYL MALONATE, CYANOACETATE, AND ACETOACETATE
73
For C10H4BrN5 anal. calcd. (%): C, 43.82; H, 1.47;
N, 25.68.
Found (%): C, 50.49; H, 2.87; N, 23.97.
4-Nitro-2-cyanophenylhydrazone XV. Yield
66.9%, mp 201–202°ë (from aqueous ethanol). IR
(KBr, ν, cm–1): 2182 (C≡N), 1628 (C=N), 3240 (N–H),
1564, 1368 (NO2). UV (λmax, nm, logε): 203.2 (2.03),
221.6 (1.94), 263.2 (1.61), 320.8 (1.79).
For C10H4N6O2 anal. calcd. (%): C, 50.00; H, 1.68;
N, 34.99.
Found (%): C, 43.29; H, 1.43; N, 26.17.
4-Bromo-2-cyanophenylhydrazone XII. Yield
70%, mp 117–118°ë (from H2O–DMF). IR (KBr, ν,
cm–1): 2228 (C≡N), 1645 (C=N), 3218 (N–H), 1730
(C=O), for COOC2H5, 1117 (C–O–C).
For C13H12BrN3O3 anal. calcd. (%): C, 46.17; H,
3.58; N, 12.43.
Found (%): C, 50.13; H, 1.87; N, 35.27.
4-Nitro-2-cyanophenylhydrazone XVI. Yield
42%, mp 125–126°ë (from H2O–DMF). IR (KBr, ν,
cm–1): 2220 (C≡N), 1648 (C=N), 1706 (C=O), for
COOC2H5 1733 (C=O), 1117 (C–O–C), 1566, 1324
(NO2).
For C13H12N4O5 anal. calcd. (%): C, 50.31; H, 3.97;
N, 18.41.
Found (%): C, 45.71; H, 3.43; N, 12.21.
4-Nitro-2-cyanophenylhydrazone XIII. Yield
35%, mp 195–197°ë (from H2O–DMF). IR (KBr, ν,
cm–1): 2218 (C≡N), 1620 (C=N), 3328 (N–H), 1730
(C=O), 1121 (C–O–C), 1545, 1334 (NO2).
For C14H14N4O6 anal. calcd. (%): C, 50.30; H, 4.22;
N, 16.76.
Found (%): C, 51.71; H, 3.58; N, 18.03.
Found (%): C, 49.73; H, 5.54; N, 16.28.
4-Nitro-2-cyanophenylhydrazone XIV. Yield
53%, mp 165–167°ë (from H2O–DMF). IR (KBr, ν,
cm–1): 2218 (C≡N), 1621 (C=N), 3228 (N–H), 1722
(C=O), 1117 (C–O–C), 1531, 1334 (NO2).
For C12H9N5O4 anal. calcd. (%): C, 50.18; H, 3.16;
N, 24.38.
REFERENCES
1. Shvekhgeimer, M.-G.A., Moreva, O.A.,Yakovenko, T.I.,
Dokl. Akad. Nauk, 1999, vol. 366, no. 2, pp. 206–209
[Dokl. Chem. (Engl. Transl.), vol. 366, nos. 1–3,
pp. 121–124].
DOKLADY CHEMISTRY Vol. 377
Nos. 1–3
2001