Reactions of polyfluorinated 2-arylhydrazono-3-oxocarboxylic acid esters with o-phenylenediamine

Article abstract of DOI:10.1023/B:RUJO.0000044543.44091.a8

Polyfluorinated 2-arylhydrazono-3-oxocarboxylic acid esters react with o-phenylenediamine in neutral medium to give mainly the corresponding o-aminoanilides which can be converted into 1,5-benzodi-azepin-2-ones. In the reactions with ethyl 2-arylhydrazono

Full text of DOI:10.1023/B:RUJO.0000044543.44091.a8

Russian Journal of Organic Chemistry, Vol. 40, No. 6, 2004, pp. 813–817. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 6, 2004,
pp. 854–858.
Original Russian Text Copyright © 2004 by Khudina, Shchegol’kov, Burgart, Saloutin.
Dedicated to Full Member of the Russian Academy of Sciences
O.N. Chupakhin on his 70th Anniversary
Reactions of Polyfluorinated 2-Arylhydrazono-
3-oxocarboxylic Acid Esters with o-Phenylenediamine
O. G. Khudina, E. V. Shchegol’kov, Ya. V. Burgart, and V. I. Saloutin
Postovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
ul. S. Kovalevskoi/Akademicheskaya 22/20, Yekaterinburg, 620219 Russia
fax: (343)3745954; e-mail: saloutin@ios.uran.ru
Received January 10, 2004
Abstract—Polyfluorinated 2-arylhydrazono-3-oxocarboxylic acid esters react with o-phenylenediamine in
neutral medium to give mainly the corresponding o-aminoanilides which can be converted into 1,5-benzodi-
azepin-2-ones. In the reactions with ethyl 2-arylhydrazono-3-oxobutanoate and its 4,4-di- and 4,4,4-trifluoro
derivatives, ethyl 2-(2-benzimidazolyl)-2-[(4-methylphenyl)hydrazono]ethanoate is also formed.
1
IIa–IIe follows from the presence in their H NMR
spectra of signals from protons of a primary amino
group (δ 3.85–5.35 ppm); in the IR spectra we
observed absorption bands due to symmetric and anti-
symmetric stretching vibrations of that group at 3340–
3420 cm–1 (see Experimental).
Depending on the conditions, fluorinated 3-oxo-
carboxylic acid esters, as well as their fluorine-free
analogs, are capable of reacting with o-phenylene-
diamine at the keto group to give 3-arylamino-
crotonates and/or 2-methylbenzimidazole [1, 2], at the
ester group with formation of N-(2-aminophenyl)-3-
oxocarboxylic acid amides [1] and/or 3-(2-benz-
imidazolyl)-1,1,1-trifluoroacetone [3], or at both these
to afford 1,5-benzodiazepin-2-ones [1, 4]. 3-Oxocar-
boxylic acid esters having an alkyl [5], acetyl, or
ethoxycarbonyl group [6, 7] or chlorine atom [8] in
position 2 react with aromatic o-diamines according
to the “acid” decomposition pattern which leads to
formation of 2-(polyfluoroalkyl)benzimidazoles. Reac-
tions of fluorine-free 2-arylhydrazono-3-oxobutanoates
with 3-methylbenzene-1,2-diamine in o-xylene on
heating give rise to substituted 1,5-benzodiazepin-2-
ones which suppress the activity of the central nervous
system [9].
Amides II can be converted into 1,5-benzodi-
azepin-2-ones III by heating in boiling o-xylene for
a long time. In such a way, from o-aminoanilides IIb
and IId we obtained 4-fluoroalkyl-1H-1,5-benzodi-
azepine-2,3-dione 3-arylhydrazones IIIa and IIIb
(Scheme 1). It should be noted that small amounts of
compounds IIIa and IIIb are formed directly in the
reactions of esters Ib and Id with o-phenylenediamine
(according to the TLC data).
The NMR and IR spectral data of compounds IIIa
and IIIb indicate that they exist in solution and in
crystal as a single tautomer, namely hydrazone–amide.
The formation of intramolecular hydrogen bond in IIIa
and IIIb is confirmed by the reduced frequency of
the amide carbonyl absorption (1630–1640 cm–1) in
the IR spectrum and by the presence of a downfield
broadened singlet from the hydrazone proton (δ 12.48–
The goal of the present work was to examine the
reaction of fluorinated 2-arylhydrazono-3-oxocar-
boxylic acid esters I with o-phenylenediamine. We
have found that esters Ia–Ie do not react with
o-phenylenediamine under mild conditions and that the
reaction in boiling o-xylene or toluene involves the
ester fragment to give the corresponding o-amino-
anilides IIa–IIe as the major products (Scheme 1,
path 1). The o-aminoanilide rather than cyclic 1,2,4,5-
tetrahydro-1,5-benzodiazepine structure of compounds
1
14.24 ppm) in the H NMR spectrum (see Experi-
mental).
Apart from amide IIc, the reaction of ester Ic with
o-phenylenediamine gave N,N'-phenylenediamide IV
as a result of subsequent condensation of product IIc at
the ester group of the second molecule of ester Ic.
1070-4280/04/4006-0813 © 2004 MAIK “Nauka/Interperiodica”

KHUDINA et al.
814
Scheme 1.
C6H4Me-4
C6H4Me-4
C6H4Me-4
NH
N
H
N
N
H
O
N
o-Xylene (toluene)
reflux, 20 h
o-Xylene
reflux, 40 h
NH2
NH2
N
R'
O
R'
+
R'
OR
O
Path 1
N
NH
O
HN
O
H2N
Ia–If
IIa–IIe
IIIa, IIIb
C6H4Me-4
C6H4Me-4
C6H4Me-4
o-Xylene
(toluene)
reflux, 20 h
N
H
N
H
N
H
N
N
N
R'
H
H
R'
O
O
O
N
N
–R'H
Path 2
N
OEt
NH
OEt
N
OEt
NH2
A
B
V
Ia, IIa, R = Et, R' = C6F13; Id, IId, IIIb, R = Et, R' = HCF2; Ie, IIe, R = Et, R' = Me; If, R = Et, R' = CF3; Ib, IIb, IIIa, R = Me,
R' = C4H9; Ic, IIc, R = Me, R' =H(CF2)2.
H
N
O
O
H
N
4-MeC6H4
N
N
O
N
O
N
C6H4Me-4
H
H
CHF2CF2
CF2CHF2
IV
Unlike esters Ia–Ic which contain a “long” poly-
fluorinated alkyl group (tridecafluorohexyl, nona-
fluorobutyl, or tetrafluoroethyl), esters Id and Ie
having a “short” difluoromethyl moiety react with
o-phenylenediamine in boiling o-xylene according to
both path 1 (to give o-aminoanilides IId and IIe) and
path 2, i.e., at the difluoroacetyl group. In these
reactions, we also isolated ethyl 2-(2-benzimidazolyl)-
2-(arylhydrazono)acetate (V) (Scheme 1). Compound
V is likely to be formed by cyclization of intermediate
3-(arylimino)butanoate A at the C=N bond adjacent to
the difluoromethyl group. The resulting 2,2-disub-
stituted dihydrobenzimidazole B readily undergoes
aromatization via elimination of difluoromethane
molecule to afford ethyl 2-(2-benzimidazolyl)-2-(aryl-
hydrazono)ethanoate (V).
gave a mixture of products, from which we succeeded
in isolating only a small amount of ester V. This fact
can be regarded as an indirect evidence for reduced
selectivity of reactions with esters having a short-chain
fluoroalkyl group.
Theoretically, 1,5-benzodiazepin-2-ones III could
be formed by cyclization of not only o-aminoanilides
II but also 3-(arylimino)butanoates A. However, we
failed to detect the latter by TLC. The chromatograms
contained spots belonging to initial esters I, o-amino-
anilides II, and benzimidazole V. Probably, the trans-
formation of intermediates like A into benzimidazole
V is very fast. On the other hand, we have shown that
benzodiazepines III can be obtained from o-amino-
anilides II.
Thus the presence of a bulky polyfluoroalkyl group
in esters Ia–Ic favors their selective reaction with
o-phenylenediamine at the ester group, whereas esters
It should be noted that the reaction of trifluoro-
methyl-substituted ester If with o-phenylenediamine
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REACTIONS OF POLYFLUORINATED 2-ARYLHYDRAZONO-...
815
Id–If having di- and trifluoroacetyl moieties react both
at the ester and at the fluoroacetyl group.
(C–F). 1H NMR spectrum (CDCl3), δ, ppm: 1.42 t (3H,
OCH2CH3, J = 7.0 Hz), 2.37 s (3H, Me), 4.40 q (2H,
OCH2CH3, J = 7.0 Hz), 7.22–7.31 m (4H, C6H4),
We also made an attempt to effect reaction of ester
Ib with o-phenylenediamine in acid medium. No
reaction occurred in methanol containing a catalytic
amount of acetic acid. When methanol was replaced by
1-butanol, a mixture of products was obtained, which
we failed to separate. Likewise, the use of a template
procedure was unsuccessful. Ester Ic did not react with
o-phenylenediamine on heating in boiling ethanol in
the presence of nickel acetate.
19
13.55 br.s (1H, NH). F NMR spectrum (CDCl3), δF,
ppm: 35.73 m (2F, CF2), 39.12 m (2F, CF2), 40.57 m
(2F, CF2), 41.89 m (2F, CF2), 50.34 m (2F, CF2),
81.01 m (3F, CF3). Found, %: C 39.40; H 2.31;
F 44.70; N 5.12. C18H13F13N2O3. Calculated, %:
C 39.15; H 2.37; F 44.72; N 5.07.
Methyl 2-[(4-methylphenyl)hydrazono]-3-oxo-
4,4,5,5,6,6,7,7,7-nonafluoroheptanoate (Ib). Yield
72%, yellow powder, mp 94–96°C (from ethanol).
IR spectrum, ν, cm–1: 3070, 1585 (NH); 1680, 1660
(C=O); 1640, 1520, 1500 (C=N, C=C); 1115–1225
We can conclude that esters I react with o-phe-
nylenediamine in neutral medium (boiling toluene or
o-xylene) predominantly at the ester group, yielding
the corresponding o-aminoanilides. However, this re-
action pathway is not the only possible in the case of
ethyl 2-(arylhydrazono)acetoacetate and its di- and
trifluoro analogs. These compounds also give rise to
ethyl 2-(2-benzimidazolyl)-2-(arylhydrazono)acetate
as a result of concurrent addition of o-phenylenedi-
amine at the (fluoro)acetyl group and partial decom-
position. The latter process was unexpected; according
to published data [2, 5–8], reactions of 3-oxo esters
and their 2-alkyl, acetyl, ethoxycarbonyl, and chloro
derivatives with o-phenylenediamine were accom-
panied only by “acid” cleavage with formation of
2-(fluoroalkyl)benzimidazoles.
1
(C–F). H NMR spectrum (CDCl3), δ, ppm: 2.38 s
(3H, Me), 3.94 s (3H, OMe), 7.23–7.32 m (4H, C6H4),
19
13.55 br.s (1H, NH). F NMR spectrum (acetone-d6),
δF, ppm: 38.92 m (2F, CF2), 43.39 m (2F, CF2),
52.77 m (2F, CF2), 82.80 m (3F, CF3). Found, %:
C 41.20; H 2.53; F 38.83; N 6.35. C15H11F9N2O3.
Calculated, %: C 41.11; H 2.53; F 39.02; N 6.39.
Methyl 2-[(4-methylphenyl)hydrazono]-3-oxo-
4,4,5,5-tetrafluoropentanoate (Ic). Yield 66%,
yellow powder, mp 79–80°C (from ethanol). IR spec-
trum, ν, cm–1: 3130, 1580 (NH); 1680, 1660 (C=O);
1640, 1520, 1500 (C=N, C=C); 1070–1230 (C–F).
1H NMR spectrum (CDCl3), δ, ppm: 2.38 s (3H, Me),
2
3.93 s (3H, OMe), 6.34 t.t [1H, H(CF2)2, JHF = 53.2,
3JHF = 5.6 Hz], 7.24–7.30 m (4H, C6H4), 13.48 br.s
(1H, NH). 19F NMR spectrum (CDCl3), δF, ppm:
EXPERIMENTAL
2
3
The IR spectra were recorded on a Perkin–Elmer
Spectrum One Fourier spectrometer in the range from
400 to 4000 cm–1; samples were prepared as mulls in
24.59 d.t (2F, HCF2, JFH = 53.2, JFF = 7.9 Hz),
42.20 m (2F, CF2). Found, %: C 48.82; H 3.78; F 23.58;
N 8.71. C13N12F4N2O3. Calculated, %: C 48.76; H 3.78;
F 23.73; N 8.75.
1
mineral oil. The H and 13C NMR spectra were
obtained on a Bruker DRX-400 spectrometer at 400
and 100.6 MHz, respectively; the chemical shifts were
measured relative to tetramethylsilane. The 19F NMR
spectra were measured on a Tesla BS-587A instrument
(75 MHz) relative to C6F6. The elemental analyses
were obtained on a Carlo Erba CHNS-O EA 1108
analyzer. The mass spectra were run on a Varian MAT-
311A mass spectrometer.
Ethyl 2-[(4-methylphenyl)hydrazono]-3-oxo-4,4-
difluorobutanoate (Id). Yield 54%, yellow powder,
mp 96–98°C (from ethanol). IR spectrum, ν, cm–1:
3180, 1580 (NH); 1690 (C=O); 1640, 1520, 1500
1
(C=N, C=C); 1110–1220 (C–F). H NMR spectrum
(CDCl3), δ, ppm: 1.42 t (3H, OCH2CH3, J = 7.1 Hz),
2.38 s (3H, Me), 4.41 q (2H, OCH2CH3, J = 7.1 Hz),
2
6.70 t (1H, CHF2, JHF = 54.3 Hz), 7.22–7.28 m
(4H, C6H4), 13.45 br.s (1H, NH). 19F NMR spectrum
Esters I were synthesized by the procedure
described in [10]; newly synthesized compounds Ia–Id
and If were characterized by spectral data.
2
(CDCl3), δ, ppm: 34.44 d (2F, CHF2, JFH = 54.3 Hz).
Found, %: C 54.89; H 4.99; F 13.38; N 9.80.
C13H14F2N2O3. Calculated, %: C 54.93; H 4.96; F 13.37;
N 9.85.
Ethyl 2-[(4-methylphenyl)hydrazono]-3-oxo-
4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononanoate (Ia).
Yield 53%, yellow powder, mp 50–52°C (from
ethanol). IR spectrum, ν, cm–1: 3100, 1590 (NH);
1705, 1660 (C=O); 1530 (C=N, C=C); 1120–1240
Ethyl 2-[(4-methylphenyl)hydrazono]-3-oxo-
4,4,4-trifluorobutanoate (If). Yield 41%, yellow
powder, mp 75–76°C (from ethanol). IR spectrum, ν,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

KHUDINA et al.
816
cm–1: 3100, 1590 (NH); 1690 (C=O); 1630, 1520,
1500 (C=N, C=C); 1080–1200 (C–F). H NMR spec-
(NH); 1660 (C=O); 1640 sh, 1580, 1550, 1500
(C=N, C=C); 1070–1230 (C–F). H NMR spectrum
1
1
trum (DMSO-d6) (mixture of isomers Ia and Ia',
~10:3], δ, ppm: Ia: 1.28 t (3H, OCH2CH3, J = 7.1 Hz),
2.28 s (3H, Me), 4.30 q (2H, OCH2CH3, J = 7.1 Hz),
7.18–7.36 m (4H, C6H4), 11.65 br.s (1H, NH); Ia':
1.30 t (3H, OCH2CH3, J = 7.1 Hz), 2.30 s (3H, Me),
4.25 q (2H, OCH2CH3, J = 7.1 Hz), 7.22–7.43 m
(4H, C6H4), 14.36 br.s (1H, NH). Found, %: C 51.89;
H 4.59; F 18.58; N 9.15. C13H13F3N2O3. Calculated, %:
C 51.66; H 4.34; F 18.86; N 9.27.
(DMSO-d6), δ, ppm: 2.33 s (3H, Me), 5.16 br.s (2H,
NH2), 6.61–7.47 m (8H, 2C6H4), 6.91 t.t [1H, H(CF2)2,
3
2JHF = 52.0, JHF 5.5 = Hz], 9.91 br.s and 14.50 br.s
19
(2H, 2NH). F NMR spectrum (DMSO-d6), δF, ppm:
2
3
24.09 d.t (2F, CHF2, JFH = 52.0, JFF = 9.7 Hz),
46.75 m (2F, CF2). Found, %: C 54.48; H 4.07; F 19.08;
N 14.03. C18H16F4N4O2. Calculated, %: C 54.55; H 4.07;
F 19.17; N 14.14.
N-(2-Aminophenyl)-2-[(4-methylphenyl)hydra-
zono]-3-oxo-4,4-difluorobutanamide (IId). The
product was isolated by column chromatography on
silica gel (40–100 µm) using chloroform as eluent.
Yield 177 mg (51%), yellow powder, mp 140–142°C.
IR spectrum, ν, cm–1: 3410, 3340, 3250, 1590 (NH);
1650 (C=O); 1620, 1580, 1500 (C=N, C=C); 1120–
Reaction of esters Ia–If with o-phenylene-
diamine (general procedure). o-Phenylenediamine,
108 mg (1 mmol), was added to a solution of 1 mmol
of ester Ia–If in 10 ml of o-xylene (compounds Ia–Id)
or toluene (Ie, If), and the mixture was heated for 20 h
under reflux and evaporated to dryness.
1
1230 (C–F). H NMR spectrum (DMSO-d6), δ, ppm:
N-(2-Aminophenyl)-2-[(4-methylphenyl)hydra-
zono]-3-oxo-4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-
nonanamide (IIa). The product was isolated by
column chromatography on silica gel (40–100 µm)
using chloroform as eluent. Yield 418 mg (68%),
yellow powder, mp 132–133°C. IR spectrum, ν, cm–1:
3420, 3340, 3250, 1600 (NH); 1670 (C=O); 1630,
2.33 s (3H, Me), 4.90 br.s (2H, NH2), 6.57–7.47 m
2
(8H, 2C6H4), 6.81 t (1H, CHF2, JHF = 51.6 Hz),
9.85 br.s and 14.20 br.s (2H, 2NH). Found, %:
C 58.68; H 4.47; F 11.08; N 9.03. C17H16F2N4O2.
Calculated, %: C 58.96; H 4.66; F 10.97; N 9.24.
N-(2-Aminophenyl)-2-[(4-methylphenyl)hydra-
zono]-3-oxobutanamide (IIe). Yield 186 mg (60%),
yellow crystals, mp 161–162°C (from benzene). IR
spectrum, ν, cm–1: 3420, 3360, 3240, 3160, 1600 (NH);
1
1550, 1520 (C=N, C=C); 1150–1240 (C–F). H NMR
spectrum (DMSO-d6), δ, ppm: 2.32 s (3H, Me),
5.35 br.s (2H, NH2), 6.59–7.47 m (8H, 2 C6H4),
9.82 br.s and 13.00 br.s (2H, 2NH). Found, %:
C 43.18; H 2.27; F 40.08; N 9.03. C22H15F13N4O2.
Calculated, %: C 43.01; H 2.46; F 40.20; N 9.12.
1
1650 (C=O); 1550, 1520 (C=N, C=C). H NMR
spectrum (CDCl3), δ, ppm: 2.36 s and 2.59 s (6H,
2Me), 3.85 br.s (2H, NH2), 6.81–7.43 m (8H, 2C6H4),
11.11 br.s and 14.72 br.s (2H, 2NH). Found, %:
C 65.76; H 5.71; N 18.12. C17H18N4O2. Calculated, %:
C 65.79; H 5.85; N 18.05.
N-(2-Aminophenyl)-2-[(4-methylphenyl)hydra-
zono]-3-oxo-4,4,5,5,6,6,7,7,7-nonafluoroheptan-
amide (IIb). Yield 329 mg (64%), yellow powder,
mp 146–148°C (from benzene). IR spectrum, ν, cm–1:
3410, 3340, 3250, 1580 (NH); 1650 (C=O); 1535,
N,N'-(1,2-Phenylene)-bis[2-(4-methylphenyl)-
hydrazono-3-oxo-4,4,5,5-tetrafluoropentanamide]
(IV) was isolated by column chromatography on silica
gel (100–250 µm) using chloroform as eluent. Yield
171 mg (25%), yellow powder, mp 144–146°C. IR
spectrum, ν, cm–1: 3350, 3265, 1560 (NH); 1680 sh,
1660 (C=O); 1595, 1555, 1500 (C=N, C=C); 1090–
1
1500 (C=N, C=C); 1115–1215 (C–F). H NMR spec-
trum (DMSO-d6–CCl4), δ, ppm: 2.37 s (3H, Me),
4.83 br.s (2H, NH2), 6.58–7.44 m (8H, 2C6H4),
9.88 br.s and 14.95 br.s (2H, 2NH). 19F NMR spec-
trum (DMSO-d6–CCl4), δF, ppm: 37.46 m (2F, CF2),
42.18 m (2F, CF2), 52.34 m (2F, CF2), 81.80 m (3F,
CF3). Found, %: C 46.39; H 2.94; F 33.64; N 10.86.
C20H15F9N4O2. Calculated, %: C 46.70; H 2.94;
F 33.24; N 10.89.
1
1235 (C–F). H NMR spectrum (DMSO-d6) (mixture
of tautomers IV and IV', ~17:3), δ, ppm: IV: 2.33 s
2
3
(6H, 2Me), 6.77 t.t (2H, 2CHF2, JHF = 52.2, JHF
=
5.5 Hz), 7.29–7.81 m (12H, 3C6H4), 10.48 s and
14.48 s (4H, 4NH); IV': 2.36 s (6H, 2Me), 7.01 t.t
N-(2-Aminophenyl)-2-[(4-methylphenyl)hydra-
zono]-3-oxo-4,4,5,5-tetrafluoropentanamide (IIc).
The product was isolated by column chromatography
on silica gel (100–250 µm) using chloroform as eluent.
Yield 150 mg (38%), yellow powder, mp 146–148°C.
IR spectrum, ν, cm–1: 3410, 3350, 3240, 3200, 1600
2
3
(2H, 2CHF2, JHF = 52.6, JHF = 5.5 Hz), 7.33–7.83 m
(12H, 3C6H4), 10.48 s and 14.15 s (4H, 4NH). Mass
spectrum, m/z (Irel, %): 685 (24.1) [M + 1]+, 684
(70) [M]+·, 396 (25.4), 289 (22.1) [H(CF2)2CO-
(C=NNHC6H4Me)CO]+, 277 (11.6), 276 (82.9), 135
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REACTIONS OF POLYFLUORINATED 2-ARYLHYDRAZONO-...
817
(14.2), 134 (33.5), 121 (19.5), 119 (19.5) [N=NC6H4-
Me]+, 108 (66.1), 107 (100), 106 (78.3) [NHC6H4Me]+,
105 (22.1), 91 (66.1) [C6H4Me]+, 79 (18.4), 77 (11)
[C6H5]+. Found, %: C 52.92; H 3.58; F 21.98; N 12.41.
C30H24F8N6O4. Calculated, %: C 52.64; H 3.53;
F 22.20; N 12.28.
F 34.64; N 11.25. C20H13F9N4O. Calculated, %: C 48.40;
H 2.64; F 34.45; N 11.29.
4-Difluoromethyl-3-(4-methylphenyl)hydrazono-
2,3-dihydro-1H-1,5-benzodiazepin-2-one (IIIb).
Yield 273 mg (83%), yellow crystals, mp 216-217°C
(from chloroform). IR spectrum, ν, cm–1: 3290,
3180, 1575 (NH); 1630 (C=O); 1555, 1500, 1490
Ethyl 2-(2-benzimidazolyl)-2-[(4-methylphenyl)-
hydrazono]ethanoate (V). Yield 64 mg (20%; from
Id), 74 mg (23%; from Ie), 81 mg (25%; from If);
yellow powder, mp 218–220°C. The product was
purified by column chromatography using chloroform
as eluent and washed with ethanol. IR spectrum, ν,
cm–1: 3380, 1575 (NH); 1650 (CO2Et); 1605, 1535,
1
(C=N, C=C); 1125–1260 (C–F). H NMR spectrum
(DMSO-d6–CCl4), δ, ppm: 2.30 s (3H, Me), 6.71 t
2
(1H, CHF2, JHF = 54.9 Hz), 7.09–7.32 m (8H, 2C6H4),
10.41 br.s and 12.48 br.s (2H, 2NH). 19F NMR
2
spectrum (CDCl3), δF, ppm: 42.66 d (2F, CHF2, JFH
=
54.9 Hz). Found, %: C 61.88; H 4.23; F 11.43;
N 17.07. C17H14F2N4O. Calculated, %: C 62.19; H 4.30;
F 11.57; N 17.07.
1
1500 (C=N, C=C). H NMR spectrum (DMSO-d6–
CCl4), δ, ppm: 1.44 t (3H, OCH2CH3, J = 7.1 Hz),
2.35 s (3H, Me), 4.41 q (2H, OCH2CH3, J = 7.1 Hz),
7.19–7.72 m (8H, 2C6H4), 12.32 br.s and 15.09 br.s
(2H, 2NH). 13C NMR spectrum (DMSO-d6–CCl4),
δC, ppm: 14.26, 20.49, 60.51, 112.77, 114.95, 116.56,
118.24, 122.14, 123.59, 129.82, 132.00, 132.66,
140.20, 140.63, 145.85, 164.49. Mass spectrum, m/z
(Irel, %): 324 (21.7) [M + 1]+, 323 (100) [M]+·, 250
(17.2) [M – CO2Et]+, 249 (19.9), 159 (10.1), 147
(19.1), 144 (55.6), 119 (9.4) [N=NC6H4Me]+, 118 (9.8)
[M – EtO2CC=NNHC6H4Me]+, 106 (10.6) [NH-
C6H4Me]+, 105 (43.4), 91 (28.1) [C6H4Me]+, 77 (10)
[C6H5]+. Found, %: C 66.63; H 5.51; N 17.23.
C18H18N4O2. Calculated, %: C 67.06; H 5.63; N 17.38.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 03-03-33118 and 03-03-06471) and by the State
Program for Support of Leading Scientific Schools
(project no. 1766.2003.3).
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C=C); 1115–1220 (C–F). 1H NMR spectrum
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19
2NH). F NMR spectrum (DMSO-d6–CCl4), δF, ppm:
37.35 m (2F, CF2), 41.75 m (2F, CF2), 52.13 m (2F,
CF2), 81.76 m (3F, CF3). Found, %: C 48.46; H 2.43;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004