Cyanothioacetamide and its derivatives in heterocyclic synthesis: A new route for the synthesis of several pyridine and thieno[2,3-b]pyridine derivatives and their biological evaluation

Article abstract of DOI:10.1515/znb-1999-0517

Several new pyridine and thieno[2,3-b]pyridine derivatives were synthesized via the reactions of some pyridinethiones, obtained by the action of acetylacetone on some thiocarboxamidocinnamonitriles, with halogenated esters and ketones. Structures were established based on elemental and spectral data. All the synthesized compounds were tested for their biological activity.

Full text of DOI:10.1515/znb-1999-0517

Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis:
A New Route for the Synthesis of Several Pyridine and
Thieno[2,3-b]pyridine Derivatives and their Biological Evaluation
Sanaa M. Eldin*
Department of Pesticidal Chemistry, National Research Center, Dokki, Giza 12311,
A. R. Egypt
Z. Naturforsch. 54b, 674-680 (1999); received November 9, 1998
Pyridines, Thieno[2,3-b]pyridines, Cyanothioacetamide, Thiocarboxamido-cinnamonitriles,
Michael Condensations
Several new pyridine and thieno[2,3-b]pyridine derivatives were synthesized via the reac-
tions of some pyridinethiones, obtained by the action of acetylacetone on some thiocarbox-
amidocinnamonitriles, with halogenated esters and ketones. Structures were established
based on elemental and spectral data. All the synthesized compounds were tested for their
biological activity.
Introduction
the only isolated reaction products. Therefore, we
re-investigated this reaction. As we found a-thio-
carboxamido-p-methoxyphenylacrylonitrile (2a)
reacted, base catalyzed, with acetylacetone (3) to
yield a reaction product of the molecular formula
C 16H 14 N2S 0 2 which corresponds to the addition
of 2a to 3 with the loss of H20 and two hydrogens.
The IR spectrum of this product showed the pres-
ence of NH, CN, CH3CO and C=S groups. The 'H
NMR spectrum revealed the absence of any sig-
nals in the range of 4-6.8 ppm which, if present,
might be due to pyridine protons. Based on the
above data, the reaction product could be formu-
lated as the dihydropyridine-2 -thione derivative
4a. Concentration and cooling of the mother
liquor afforded another product of the molecular
formula Ci6H 18N2 S 0 2, corresponding to the addi-
tion of 2a to 3 followed by loss of H20. The 'H
NMR spectrum of this product revealed signals of
pyridine H-3 and H-4 at 6.4 and 6 . 8 d ppm, respec-
tively. Accordingly this reaction product could be
formulated as the tetrahydropyridine-2 -thione de-
rivative 5a.
Analogously, 2b reacted with 3 to yield the dihy-
dropyridine-2-thione (4b) and the tetrahydropyri-
dine-2-thione (5b). In all cases, the dihydro deriva-
tive constituted the major product. On the other
hand, compounds 5a,b could be converted into the
corresponding 4a,b by boiling their solutions in
pyridine for 5 h. Compounds 4a,b and 5a,b were
taken as starting materials for the present study.
Thus, it has been found that 4a condensed with
Thiazole and its derivatives are long known for
their antibacterial [1 ] activity and their use as hy-
poglycemic agents [2]. Fungicidal [3], herbicidal
[4], insecticidal [5] and plant-growth regulating [6 ]
properties have been reported for this group of
heterocyclics. In addition, pyridines are also re-
ported to exhibit diverse biological activities as
antimycotic [7], antidepressant [8 ], antiarrhythmic
[9], and antilipemic [10] agents. The fusion of the
thiazole and the pyridine ring might combine the
biological activities of both moieties. The reactions
of cyanothioacetamide (1 ) and its derivatives (2 )
with different halogenated esters and ketones and
active methylene-containing reagents constituted
an easy and logic route for the synthesis of these
heterocyclic derivatives. These reactions could be
considered to be of interest in the chemistry of
1
and 2 [11-18],
Results and Discussion
The reaction of a-thiocarboxamidocinnamoni-
triles (2) with acetylacetone (3) has been leading
to contradictory results. Thus, whereas Litvinov
et al. [19], Ghozlan [20] and Elnagdi et al. [21] re-
ported that the reaction products were dihydro-
pyridine-2-thiones (4), Krauze et al. [22, 23] re-
ported that tetrahydropyridine-2-thiones (5) were
* Reprint requests to S. M. Eldin.
0932-0776/99/0500-0674 $06.00 © 1999 Verlag der Zeitschrift für Naturforschung. Tübingen • www.znaturforsch.com
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S. M. Eldin • Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis
675
chloroacetone (6 ) in methanolic sodium meth- pyridine derivatives 1 0 a,b which cyclized in etha-
oxide to give a reaction product of the molecular
nolic KOH to afford 8 a,b. The structure of 10a,b
formula C19H 18N2 S 0 3. The IR spectrum of this was also confirmed by elemental analysis and
product showed the presence of bands of CN spectral data.
(2220 cm-1) and two carbonyl groups at 1720 and
c)
Carrying out the reaction between 4a,b (or
1708 cm-1. 'H NMR revealed the absence of any 5a,b) and 9 in boiling glacial acetic acid led to di-
signals that might be attributed to the presence of rect formation of 8 a,b.
pyridine protons. Consequently, this product could
be formulated as 5-acetyl-3-cyano-6-methyl-4-(4'- 354 (100%) which corresponds exactly to the for-
methoxyphenyl)-2-S-acetonylpyridine 7a. Simi-
Moreover, the mass spectrum of 8 a gave m/e =
mula weight of C19H 18N2 S0 2 of 8 a. In addition,
larly, 4b reacted with 6 to afford the corresponding the activity of enaminoacetyl moiety in 8 a,b was
2-S-acetonylpyridine derivative 7b whose struc- demonstrated by treatment with nitrous acid to
ture was also established based on analytical and yield the thienopyridopyrizazinones 11a,b. The IR
spectral data.
spectra of 1 1 a,b showed the presence of pyridazi-
Compounds 7a,b could be cyclized by the action none-CO (1722 cm-1) and CH3CO (1695 cm-1)
of boiling 10% ethanolic KOH to give the 2-ace- groups while their !H NMR spectra revealed the
tylthieno[2,3-b]pyridine derivatives 8a,b. The struc-
ture of 8a,b was established via elemental analysis
absence of NH2 signals.
Work was further extended to study the behavi-
and spectral data. A solid evidence for the struc- our of 4a,b and 5a,b towards the action of ethyl a-
ture of 8a,b came from their authentication via dif-
ferent routes as follows:
chloroacetoacetate (12). Thus, 4a and 12 reacted
in methanolic sodium methoxide to give a product
a) Carrying out the reaction of 4a,b with 7 in with the molecular formula C22H22N2 S 0 5. The IR
glacial acetic acid instead of methanolic sodium spectrum of this product showed absorption bands
methoxide.
of CN (2222 cm-1), ester-CO (1745 cm-1) and two
b) The reaction of 4a,b (or 5a,b) with a-chloro- CH3CO groups at 1721 and 1700 cm“1. Also, its 'H
acetylacetone (9) yielded the 2-S-diacetylmethyl- NMR spectrum revealed signals of COOCH2 CH3,
Ar
Ac- ^ W CN
HNO,
10%KOH/A
X
x
H3C ^ N'"^S-CH2
h 3c
H3C
c=o
I
7a,b
COCH3
8a,b
CH,
lla ,b
Chart 1
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676
S. M. Eldin • Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis
CH3, two COCH3 and saturated CH groups in ad- drazides of the thieno[2,3-b]pyridines 16a,b. No
ester-CO band was detected in the IR spectra of
dition to aromatic protons in their proper posi-
tions. Accordingly, this product could be formu- 16a,b. Moreover, their ‘H NMR did not reveal the
lated as 5-acetyl-3-cyano-6-methyl-4-(4'-methoxy- doublet and quartet of the ester-CH2CH3 group in
phenyl)-2-S-(acetylethoxycarbonylmethyl)pyridine
(13a) formed via dehydrochlorination. Analo-
gously 4b yielded 13b on its reaction with 12.
each case.
Compounds 16a,b could be cyclized by the ac-
tion of boiling glacial acetic acid via ammonia
13a,b, cyclized by the action of ethanolic KOH elimination to produce the pyrazolino-[3',4':4,5]-
yielded products that showed IR absorption bands thieno[2,3-b]pyridines 17a,b whose 'H NMR
of NH2, ester-CO and one CH3CO group in each spectra revealed the presence of only two D20 -
case. CN function bands were entirely absent in exchangeable NH protons. It is remarkable to re-
port that trials to dehydrogenate the pyrazoline
moiety to yield the corresponding pyrazolone
each case. ’H NMR spectra revealed signals of
only one CH3CO group. Based on the above data,
these compounds could be formulated as enamino- were unsuccessful under a variety of reaction con-
ethoxycarbonylthieno[2,3-b]pyridines 15a,b. The ditions.
formation of 15a,b in this reaction involves first,
addition to the CN function to yield the imino-
thieno[2,3-b]pyridine 14a,b; to which one molecule
of water is added and then one molecule of acetic
acid liberated yielding the isolated 15a,b rather
than 8 a,b (cf. Chart 2).
Biological Activity
The synthesized comounds were tested in vitro
against some gram negative bacteria such as Neis-
seria polysacchareae, Listeria monocytogenes and
Escherichia coli and some gram postive bacteria
such as Bacillus subtilis and Micrococcus roseus.
Nutrient agar medium has been utilized for grow-
ing test organisms. The diameters of clearing zones
have been used as a parameter to express the anti-
microbial activity where all the compounds were
tested at a unique concentration of 75 /ug/m\. All
the synthesized compounds were biologically eval-
uated and results are reported in Table I.
A r
Experimental
All melting points are uncorrected. IR spectra
in KBr discs were recorded on Pye Unicam SP-
1100 and Perkin-Elmer FT-IR type 4 spectropho-
tometers. !H NMR were recorded on Gemini 200
MHz spectrometer using TMS as an internal
standard in DMSO-d6 and chemical shifts are ex-
pressed as d ppm units. Mass spectra were re-
corded on Hewlett-Packard GC-MS type 2988
series A using DIP technique at 15 and 70 eV.
Microanalyses were performed by the Microana-
lytical Center of Cairo University.
a, A r = C 6H 4-O C H 3-p
b, A r = C 6H„-CI-p
Chart 2
Compounds 2a,b were prepared according to a
literature procedure [24],
Compounds 15a,b could also be confirmed via
two other routes:
Preparation of the starting materials 4a,b and 5a,b
a) Carrying out the reaction of 4a,b with 12 in
glacial acetic acid instead of CH3 ONa, and
b) of 5a,b with 12 in boiling glacial acetic acid.
Compounds 15a,b reacted with hydrazine hy-
drate via ethanol elimination to yield the acid hy-
General procedure
A solution of acetylacetone (4, 0.01 mol) and
each of 2a,b (0.01 mol) in absolute ethanol (30 ml)
containing triethylamine (0.5 ml) was heated
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S. M. Eldin • Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis
677
_
...
Table I. Biological activity
teste(j new comounds.
Comp. Neisseria
Listeria
monocytogenes
Escherichia
coli
Bacillus
Micrococcus
No.
polysacchareae
subtilis
roseus
_
+
—
—
—
+
+
-
4a
4b
5a
5b
7a
7b
8a
-
+
+
+
-
+ +
+ +
—
+
-
—
+
-
+
-
-
+
+
+
+
+
+
-
+ +
-
+ +
+
8b
-
+
-
+
-
10a
10b
11a
lib
13a
13b
15a
15b
16a
16b
17a
17b
-
+ +
+
-
+
-
-
+
+ + +
+ +
+ +
—
+ +
+ + +
+ +
-
+
+
-
+
+
_
_
______________ Highly active: + + + ; large
______________ clearing zone. Slightly ac-
+ +
+ +
+
_i_
+
+
+
+
-
-
-
—
+ +
+ + +
+ +
+
_|_______________ tive: +; small clearing. Mod-
_
_
______________ erately active: + + ; medium
______________ clearing. Inactive: —; no
clearing zone
-
+ +
under reflux for 5 h. The solids obtained were fil- solvent to yield 7a,b, 10a,b and 13a,b respectively
tered off and crystallized from ethanol to give yel- (cf. Tables II and III).
low crystals of 4a [19-21] and 4b [19-21], respec-
tively.
Reactions o f 4a,b and 5a,b with chloro-ketones and
esters in glacial acetic acid
Concentration and cooling of the mother liquor
gave pale yellow solid products which were fil-
tered off and crystallized from ethanol to give 5a
and 5b [22, 23], respectively.
General procedure
The repetition of the experiments described
above in glacial acetic acid and boiling for 5 h re-
sulted in the formation of 8 a,b and 15a,b, respec-
tively (cf. Tables II and III).
Conversion o f 5a,b into 4a,b
A solution of each of 5a,b (1 g) in pyridine
(20 ml) was heated under reflux for 5 h and then
poured onto ice-cold water. Addition of conc. HC1
( 1 ml) yielded yellow solid products that were fil-
tered off, washed with water, then crystallized
from ethanol to give 4a,b, respectively with m.p.
showing no depression when admixed with au-
thentic samples obtained as described above.
Cyclization reactions in ethanolic KO H
General procedure
A solution of each of 7a,b, 10a,b and 13a,b (0.01
mol) in ethanol (30 ml) was heated under reflux
with KOH (10%) for 3 -5 h. The reaction mixture
was then cooled and acidified with dil. HC1 and
the solids precipitated were filtered off, washed
with water and then crystallized from the proper
solvent to give 8 a,b and 15a,b, respectively (cf.
Tables II and III).
Reactions o f 4a,b and 5a,b with chloro-ketones and
esters in methanolic sodium methoxide
General procedure
A solution of each of 4a,b (0.01 mol) and 5a,b,
respectively, and chloroacetone (6 ), a-chloroace-
tylacetone (9) or ethyl-a-chloroacetoacetate (12)
(0 . 0 1 mol) was heated under reflux with metha-
nolic sodium methoxide (prepared from 0 . 0 1 atom
Cyclization o f 16a,b
A solution of each of 16a,b (0.01 mol) in glacial
acetic acid (30 ml) was heated under reflux for 5 h.
of sodium metal in 30 ml of methanol) for 2 -5 h The solid obtained after cooling were filtered off
(TLC). The products obtained after cooling were and crystallized from ethanol to give 17a,b, respec-
filtered off and crystallized from the proper tively (cf. Tables II and III).
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678
S. M. Eldin • Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis
Table II. Characterization data of the newly synthesized compounds.
Molecular
formula
Comp.*
Solvent
of Cryst.
M. p.
[°C]
Yield
[%]
Analysis Calcd/Found [%]
c
H
N
S
Cl
_
64.40
64.1
60.25
60.0
64.40
64.1
60.25
60.1
63.63
63.4
59.92
59.7
62.46
62.7
58.45
58.2
61.97
61.8
58.53
58.3
62.50
62.8
58.68
58.4
58.37
58.1
5.08
5.3
4.18
4.0
5.08
5.2
4.18
4.4
5.05
5.3
4.24
4.1
4.10
4.3
3.24
3.1
5.16
5.3
4.41
4.2
5.20
5.0
4.37
4.1
9.03
9.2
8.92
8.6
9.03
9.1
8.92
8.7
8.08
7.8
7.99
7.8
8.76
8.9
8.66
8.9
7.51
7.4
7.43
7.6
8.33
8.6
8.23
8.1
7a
7b
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
86
81
83
75
69
79
81
60
62
63
59
68
70
66
64
62
60
c 19h 18n 2s o 3
c 18h 15n 2s o 2ci
c 19h 18n 2s o 3
c 18h 15n 2s o 2ci
7.90
7.7
7.81
7.6
7.90
7.6
7.81
7.7
7.07
7.2
6.99
7.1
11.50
11.7
11.36
11.1
6.57
6.3
6.50
6.7
7.29
7.5
7.20
7.0
15.13
15.4
14.95
14.7
11.89
11.6
-
164
9.90
9.7
-
8a
162
-
8b
236-8
120
9.90
9.6
-
10a
10b
11a
lib
13a
13b
15a
15b
16a
16b
17a
17b
c 21h 20n 2s o 4
c 20h 17n 2s o 3ci
c i9h 15n 3s o 3
c 18h 12n 3s o 2ci
c 22h 22n 2s o 5
c 21h 19n 2s o 4ci
C2()H2()N2S 0 4
c 19h 17n 2s o 3ci
c 18h 18n 4s o 3
c 17h 15n 4s o 2ci
c 17h 15n 3s o 3
c 17h 12n 3s o 2ci
-
176
8.86
8.6
-
Toluene
Pet. ether
EtOH
102
-
196-8
158-9
120-2
220-1
206-7
188-9
248-9
295-7
320-2
9.60
9.4
-
EtOH
EtOH
AcOH
EtOH
EtOH
EtOH
EtOH
EtOH
-
8.24
8.0
-
-
9.13
9.4
-
4.86
4.6
4.00
4.2
4.24
4.0
8.64
8.4
8.54
8.3
9.06
9.3
-
54.47
54.2
61.18
61.4
57.06
56.8
9.47
9.2
-
-
11.74
11.5
8.92
8.8
9.93
9.7
3.35
3.2
* All compounds are yellow in color except 15a, orange
and 17a,b; colourless.
Reaction o f 8a,b with H N 0 2
and then heated under reflux for 6 h. The solid
A cold solution of each of 8 a,b (0.01 mol) in
conc. HCl (1 ml) was treated with a cold saturated
solution of N aN 02 (0.015 mol) and then stirred in
P a lle ts obtained after cooling were filtered off
crystallized from the proper solvents to give
16a’b- respectively (Tables II and III).
the ice-chest for 1 h. The solid product obtained
was filtered off, washed with water and crystallized
from the proper solvent to give 11a,b, respectively
Acknowle gement
Thanks are due to Prof. Dr. Y. E. Saleh, Depart-
ment of Botany, Faculty of Science, Cairo Univer-
sity for carrying out the biological activity of the
newly synthesized compounds.
(cf Tables II and III).
Reaction o f 15a,b with hydrazine hydrate
A solution of each of 15a,b (0.01 mol) in ethanol
(30 ml) was treated with hydrazine hydrate (10 ml)
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S. M. Eldin • Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis
Table III. IR and ‘H NMR spectral data.
679
Compd. IR [cm *]
No.
*H NMR [ppm]
7a
2220 (CN); 1720 (acetonyl-CO); 1708 (acetyl-CO)
and 1618 (C=N).
1.2 (s, 3H, pyridine-CH3); 2.1 (s, 6H, two COCH3);
3.1 (s, 2H, CH2); 3.8 (s,3H , COCH3) and 6.9-7.5
(m, 4H, ArH’s).
7b
8a
2222 (CN); 1720 (acetonyl-CO); 1708 (acetyl-CO)
and 1620 (C=N).
3500, 3340 (NH2); 1700 (pyridine-COCH3); 1630
(thiophene-COCH3 with H-bonding) and 1620
(C=N).
1.3 (s, 3H, pyridine-CH3); 2.3 (s, 6H, two COCH3);
3.3 (s, 2H, CH2) and 7-7 .5 (m, 4H, ArH’s)
1.3 (s, 3H, pyridine-CH3); 2.6 (s, 6H, two COCH3);
3.5 (s, 3H, OCH3); 4.5* (s, br, 2H, NH2) and
6.8-7.4 (m, 4H, ArH’s).
8b
3480, 3350 (NH2); 1695 (pyridine-COCH3); 1635
(thiophene-COCH3 with H-bonding) and 1625
(C=N).
1.4 (s, 3H, pyridine-CH3); 2.5 (s, 6H, two COCH3);
4.7* (s, br, 2H, NH2) and 7.0-7.6 (m, 4H, ArH’s).
10a
2220 (CN); 1697 (acetyl-CO) and 1611 (C=N)
1.2 (s, 3H, pyridine-CH3); 2.1 (s, 3H, pyridine-
COCH3); 2.4 (s, 6H, -C H (C O C //3)2); 3.1 (s, 1H,
-C H (COCH3)2); 3.6 (s, 3H, -O C H ,); and 6.6-7.0
(m, 4H, ArH’s).
10b
11a
11b
13a
2223 (CN); 1691 (acetyl-CO) and 1620 (C=N)
1.2 (s, 3H, pyridine-CH3); 2.2 (s, 3H, pyridine-
COCH3); 2.3 (s, 6H, two -C H (C O C //,)2; 3.2 (s,
1H, -C H (COCH3)2) and 6.8-7.2 (m, 4H, ArH’s).
1.3 (s, 3H, pyridine-CH3); 2.2 (s, 3H, pyridine-
COCH3); 3.1 (s, 2H, pyridazinone-CH2); 3.5 (s, 3H,
OCH3); and 6.9-7.3 (m, 4H, ArH’s).
1.3 (s, 3H, pyridine-CH3); 2.3 (s, 3H, pyridine-
COCH3); 3.2 (s, 2H, pyridazinone-CH2) and 7.0-7.4
(m, 4H, ArH’s).
1.2 (s, 3H, pyridine-CH3); 1.8 (t, 3H, CH2C //3); 2.1
(s, 3H, pyridine -C O C H 3); 2.4 (s, 1H, S-C H ); 3.4
(s, 3H, OCH,); 3.6 (q, 2H, C //2CH3) and 7.0-7.3
(m, 4H, ArH’s).
1715 (pyridazinone-CO); 1701 (pyridine-
COCH3); 1625 (N=N) and 1620 (C=N).
1722 (pyridazinone-CO); 1695 (pyridine-
COCH3); 1626 (N=N) and 1615 (C=N).
2222 (CN); 1745 (ester-CO); 1721 (COCH3);
1700 (pyridine-COCH3) and 1628 (C=N).
13b
15a
2219 (CN); 1747 (ester-CO); 1737 (COCH,);
1695 (pyridine-COCH3) and 1625 (C=N).
1.3 (s, 3H, pyridine-CH3); 1.5 (t, 3H, CH2C //,); 2.1
(s, 3H, pyridine -C O C H 3); 2.4 (s, 3H, COCH,); 3.2
(s, 1H, S-C H ); 3.5 (q, 2H, C //,C H 3) and 6 .9 -1 2
(m, 4H, ArH’s).
1.2 (s, 3H, pyridine-CH3); 1.4 (t, 3H, CH2C //3); 2.1
(s, 3H, pyridine -C O C H 3); 3.5 (s, 3H, OCH3); 4.2
(q, 2H, C //2CH3); 5.8* (s, br, 2H, N H ,) and 6 .9 -1 3
(m, 4H, ArH’s).
1695 (pyridine-COCH3); 1675 (ester-CO with
H-bonding) and 1620 (C=N).
15b
16a
1700 (pyridine-COCH3); 1673 (ester-CO with
H-bonding) and 1615 (C=N).
1.1 (s, 3H, pyridine-CH3); 1.5 (t, 3H, CH2C //3); 2.1
(s, 3H, pyridine -C O C H 3); 4.3 (q, 2H ,C //2CH,);
5.7* (s, br, 2H, NH2) and 7.0-7.4 (m, 4H, ArH’s).
1.2 (s, 3H, pyridine-CH3); 2.1 (s, 3H, pyridine
-C O C H 3); 3.7 (s, 3H, OCH3); 5.2* (s, br, 2H,
thiophene-NH2); 6.3* (s, 2H, C O N H N //2); 6.7-7.1
(m, 4H, ArH’s) and 9.0*
3465, 3355, 3297, 3221 (two NH2 and NH);
1696 (pyridine-COCH3); 1630 (hydrazide-CO
with H-bonding) and 1620 (C=N).
(s, br, 1H, C O N //N H 2).
16b
17a
3467, 3312, 3235 (two NH2 and NH); 1692
(pyridine-COCH3); 1618 (hydrazide-CO with
H-bonding) and 1620 (C=N).
1.2 (s, 3H, pyridine-CH3); 2.2 (s, 3H, pyridine-
COCH3); 5.2* (s, br, 2H, thiophene-NH2); 6.3*
(s, 2H, C O N H N //2); 6.9-7.1 (m, 4H, ArH’s) and
9.1* (s, br, 1H, C Ö N //N H 2).
1.3 (s, 3H, pyridine-CH3); 2.1 (s, 3H, pyridine-
COCH3); 3.8 (s, 3H, pyridine -C O C H 3); 3.8 (s, 3H,
OCH3); 6.9-7.1 (m, 4H, ArH’s); 7.8* (s, br, 1H,
pyrazolone, NH) and 8.3* (s, br, 1H, pyrazolone-
CONH).
3221 (NH); 1720 (pyrazolone-CO); 1682
(pyridine-COCH3); and 1625 (C=N).
17b
3222 (NH); 1722 (pyrazolone-CO); 1685
(pyridine-COCH3); and 1615 (C=N).
1.1 (s, 3H, pyridine-CH3); 2.2 (s, 3H, pyridine-
COCH3); 7.0-7.3 (m, 4H, ArH’s); 7.9* (s, br, 1H,
pyrazolone, NH) and 8.5* (s, br, 1H, pyrazolone-
CONH).
* Lost after D 20-exchange.
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680
S. M. Eldin • Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis
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