Reaction of (arylhydrazono)cyanothioacetamides with halo ketones

Article abstract of DOI:10.1023/B:COHC.0000010657.14733.8e

The reaction of (arylhydrazono)cyanothioacetamides with chloro ketones and phenacyl bromides was studied. The products are either thiazoles or 4,5-dihydrothiophenes, depending on the starting thioamides and halo ketones.

Full text of DOI:10.1023/B:COHC.0000010657.14733.8e

Chemistry of Heterocyclic Compounds, Vol. 39, No. 10, 2003
REACTION OF (ARYLHYDRAZONO)-
CYANOTHIOACETAMIDES
WITH HALO KETONES
I. V. Paramonov, N. P. Belskaia, and V. A. Bakulev
The reaction of (arylhydrazono)cyanothioacetamides with chloro ketones and phenacyl bromides was
studied. The products are either thiazoles or 4,5-dihydrothiophenes, depending on the starting
thioamides and halo ketones.
Keywords: (arylhydrazono)thioacetamides, halo ketones, thiazoles, thioamide group, thioimidates,
thiophenes, cyclocondensation.
Due to the broad range of the chemical properties of these compounds have found common use in
synthetic organic chemistry, including heterocyclic synthesis [1-3]. Thus, the reaction of chloroacetone (1a) or
α-bromoacetophenone with cyanoacetamide or N-cyanothioacetanilide 2 (R2 = Ph, X = H2) proceeds through
intermediates 3-5 to give thiazole derivatives 6 (X = H2, R1 = Me, Ph) or 7 (Y = H, R1 = Me, Ph) (see reaction
scheme below) [1, 4].
In the present work, we studied the reaction of chloroacetone 1a and phenacyl bromides 1b and 1c with
various (arylhydrazono)cyanothioacetamides 2a-j to elucidate the effect of the arylhydrazono fragment,
substituent in the thioamide group, and halo ketone structure on the course of this reaction and to synthesize
new sulfur heterocyclic compounds (Scheme 1).
The reaction of halo ketones 1 and thioamides 2a and 2b with an unsubstituted amide groups (R2 = H)
leads to 4-R1-2-(arylhydrazono)cyanomethylthiazoles 6a-d, regardless of the ketone used and nature of the
arylhydrazone group. Thin-layer chromatography of the reaction mixture in all cases showed the formation of
three products, namely, substituted thiazole 6 as well as proposed intermediates 3 and 4. Under the reaction
conditions, these intermediates are rapidly converted to thiazoles 6.
The IR spectra of products 6a-d have a C=N stretching band at 2190-2200 cm-1 as well as bands at
3240-3420 cm-1 characteristic for NH group stretching vibrations. The 13C NMR spectrum of thiazole 6a
(Table 1) shows signals for the benzene ring carbon ring at 114.6, 116.5, 135.7, and 156.9 ppm characteristic for
arylhydrazono derivatives [5]. The finding of an arylhydrazone group in the product eliminates thiadiazepine
structures 8 and 9 and supports the formation of a thiazole ring in the reaction studied.
1
The H NMR spectra of 6a-d given in Table 1 show double signals (two singlets) for the thiazole ring
5-H proton, hydrazone NH group proton, and 4-Me (6a and 6b) or 4-C6H4Me-p groups (6c and 6d) in addition
to signals of the benzene ring protons (HAr). The double set of these signals may result from the existence of
thiazoles 6 as E- and Z-isomers (Scheme 2). The Z-isomer may be stabilized by intramolecular hydrogen
bonding.
__________________________________________________________________________________________
Urals State Technical University, Yekaterinburg 620002, Russia; e-mail: belska@htf.ustu.ru. Translated
from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1572-1583, October, 2003. Original article
submitted March 19, 2001, submitted after revision March 13, 2002.
0009-3122/03/3910-1385$25.00©2003 Plenum Publishing Corporation
1385

Scheme 1
CN
CN
O
O
R2NH
S
+
R1
Hal
X
R1
X
NR2
S
2a–j
1a–c
3
R1 = Me
R2 = Ph
R2 = H
OH
R1
S
Ar
R2 = Ph
HO
HO
Ph
N
R1
R1
N
N
CN
N
CN
S
S
R1 = R3 = Me
7a + 10e
R2N
Y
X
CN
8
5
a–d
4a–d
R1
R1
Ph
R1
Ar
H2N
X
N
N
N
R1
N
CN
CN
S
NPh
S
S
7a–d
S
6a–d
R2N
9
O
10a–p
Y
X
CN
1 a Hal = Cl, b,c Hal = Br, a R1 = Me; b R1= C6H4Me-p, c R1= C6H4NO2-p, 2, 4, 6, 10 X = N–NHC6H4R3-p; 2 a, b R2 = H, c-j R2 = Ph, a, c R3 = NO2, b, h R3 = OMe;
d R3 = COOEt, e R3= Cl, f R3 = H, g R3 = Me, i R3 = OEt, j R3 = OH; 4, 6 a, b R1 = Me, c, d R1 = C6H4Me-p, a, d R3 = NO2; b, c R3 = OMe; 5, 7 Y = –N = NC6H4R3-p;
7 a-d R1 = Ph, a R3 = Me, b R3 = OMe, c R3 = OEt, d R3 = OH, 8, 9 Ar = C6H4R3-p; 10 a-e R1 = Me, f-m R1 = C6H4Me-p, n-p R1 = C6H4NO2-p, a, f, n R3 = NO2;
b, g R3 = COOEt, c, h R3 = Cl, d, i R3 = H, e, j, o R3 = Me; k R3 = OMe, l R3 = OEt, m R3 = OH, p R3 = OEt

Scheme 2
NC
NC
N
S
H
S
N
N
N
N
.
Ar
.
R1
N
.
H
R1
Ar
E-6
Z-6
Thus, the reactions of halo ketones 1a and 1b with thioamides 2a and 2b proceed exclusively through
the unsubstituted thioamide group and lead to thiazoles 6.
A study of the reaction of halo ketones 1a-c with N-phenylthiocarbamoyl derivatives 2c-j showed that
the introduction of a phenyl substituent into the thioamide group of the arylhydrazone molecule leads to
significant changes in the direction of cyclization of thioimidate 3 formed in the first reaction step.
R3
O
+
H2N
+
NH2
S
R1
NH
N
O
R3
S
R1
N
A5
A1
O
H2N
+
O
H
R1
R3
N
R1
N
S
A4
N
H2N
10
+
H
NH
N
NH2
N
+
R3
O
N
S
R1
N
S
A2
A3
Thus, 2-acetyl-3-amino-4-(arylhydrazono)-5-phenylimino-4,5-dihydrothiophenes 10a-d were obtained
in 88-97% yield in the reaction of chloroacetone 1a with (arylhydrazono)cyanothioacetamides 2c-f containing
1
an electron-withdrawing group or hydrogen at C(4) of the aromatic ring. The H NMR spectra of these products
given in Table 2 show signals for an AA'BB' system of aromatic ring protons, a three-proton singlet
corresponding to acetyl group protons, one-proton singlet for the NH group, and two-proton singlet for the NH2
group. The IR spectra of 10 characteristically show a strong band at 1610-1640 cm-1 presumably assigned to the
C=O group linked by a strong hydrogen bond to the NH2 group and amino group stretching vibrations at
3280-3480 cm-1 but lack C=N stretching bands at 2210-2220 cm-1, which was found in the spectra of thiazoles 6
and 7.
Mass spectrometry provided additional evidence for the structure of products 10a-d. Thus, the mass
spectra of these compounds contain peaks for molecular and fragment ions corresponding to decomposition with
loss of substituents in the side-chain (see Table 3).
1387

TABLE 1. 1H NMR Spectra of Thiazoles 6a-d
Chemical shifts (DMSO-d6), δ, ppm (SSCC, J, Hz)
R3
Compound
NH
5-H
4-C6H4Me-p
4-Me
HAr
(1H, two br. s
(1H, two s)
(3H, two s)
(3H, two s)
(3H, two s, OMe)
12.22 and 14.03
11.70 and 13.97
11.82 and 14.02
12.02 and 13.95
7.39 and 7.71
7.23 and 7.56
7.99 and 8.29
7.97 and 8.30
—
2.42 and 2.58
7.57 and 8.25 (4H, AA'BB', J = 9.2)
6.96, 6.99, 7.37 and 7.57 (4H, AA′BB′+AA'BB', J = 9.1)
6.96-7.05 (2H, m); 7.25-7.40 (2H, m); 7.84-7.94 (4H, m)
6a
6b*
—
2.50 and 2.54
3.75 and 3.77
3.76 and 3.78
—
2.35 and 2.38
2.34 and 2.37
—
—
6c
6d
7.02, 7.06, 7.51 and 7.54 (4H, AA'BB' + AA'BB', J = 8.6);
7.87, 7.94 and 8.24 (4H, AA'BB' + AA'BB', J = 8.6)
_______
13
δ
*
C NMR spectrum (CDCl3), , ppm: 17.04 (CH3), 55.56 (OCH3), 106.4 (C–CN), 113.9 (CHthiaz), 114.8, 116.5, 156.9
(CAr), 117.0 (CN), 153.5 (CCH3), 160.0 (Cthiaz).

TABLE 2. Spectral Data of Thiazolidines 7 and 3-Aminothiophenes 10
IR spectrum, ν, cm-1
1Н NMR spectrum (DMSO-d6), δ, ppm (SSCC, J, Hz)
Com-
pound
NH
NH2
4-Me or
5-H
NН
C≡N
C=O
R3
HAr
(1H, br. s)
(2H, br. s)
2-СOMe (3H, s)
(1H, s)
—
—
2190
2190
—
—
—
—
—
—
1.93
1.92
7.03
6.81
3.78 (3H, s, ОMe)
6.95 and 7.42 (4H, AA'BB', J = 8.9, HAr);
7b
7c
7.58-7.64 (5H, m, HPh)
1.36 (3H, t, J = 6.71,
6.84-6.87 (2H, m, HAr); 7.30-7.53 (4H, m, HPh+HAr);
ОСН2СН3); 4.02 (2H, q, 7.53-7.70 (3H, m, HPh)
J = 6.71, ОСН2СН3)
—
—
2200
—
—
—
—
—
1.91
6.85
9.39 (1H, br. s, OH)
6.73 and 7.31(4H, AA'BB', J = 8.45, HAr),
7d
7.47-7.49 (2H, m, HPh), 7.58-7.60 (3H, m, HPh)
7a +
13.15
7.6
2.10 and 1.93
—
2.32 and 2.37
7.11-7.14 (3H, m, HPh+HAr); 7.21-7.24 (3H, m, HPh);
7.35-7.49 (8H, m, HPh+HAr); 7.53-7.70 (4H, m,
HPh+HAr)
6.85
(6H, two s, 2СН3)
10e
3480,
3330
—
—
1640
13.93
13.75
7.82
7.87
2.12
2.11
—
—
7.28-7.34 (1H, m, HPh); 7.38-7.41 (2H, m, HPh);
7.49-7.55 (2H, m, HPh); 7.97 and 8.26 (4H, AA'BB',
J = 9.16, HAr)
7.26-7.32 (1H, m, HPh); 7.38-7.42 (2H, m, HPh);
7.48-7.54 (2H, m, HPh); 7.87 and 8.26 (4H, AA'BB',
J = 8.85, HAr)
10a
3430,
3300
1710
1610
—
1.34 (3H, s, J = 7.1,
СH2 CН3);
10b
4.32 (2H, s, J = 7.1,
СH2CН3)
3390,
3280
—
—
1630
1620
12.81
13.42
7.87
7.73
2.12
2.10
—
—
—
—
7.25-7.30 (1H, m, HPh); 7.45-7.61 (6H, m, HPh+HAr);
7.88-7.95 (2H, m, HAr)
10c
10d
3390,
7.28-7.34 (2H, m, HPh); 7.34-7.51 (2H, m, HPh);
3260
7.76-7.79 (2H, m, HPh)
_______
* See HAr.

TABLE 3. Mass Spectra of 3-Aminothiophenes 10a-p
m/z (I, %)
Compound
[M]+•
Φ1
Φ2
Φ3
Φ4
Φ5
10a
381 (100)
408 (100)
352 (18.48)
379 (32.30)
341 (27.37)
307 (10.40)
303 (4.03)
428 (12.51)
455 (19.87)
418 (9.15)
383 (14.70)
397 (95.68)
413 (32.45)
427 (10.02)
399 (32.05)
459 (5.53)
428 (37.74)
458 (5.70)
244 (63.35)
244 (57.56)
244 (37.99)
244 (14.87)
244 (20.09)
320 (11.83)
320 (16.31)
—
320 (15.53)
320 (13.65)
320 (10.46)
320 (3.62)
320 (17.05)
351 (7.68)
351 (17.24)
351 (13.62)
338 (6.36)
365 (7.11)
327 (5.78)
293 (3.64)
289 (1.08)
—
365 (1.48)
—
293 (2.18)
307 (5.40)
323 (2.40)
—
—
—
—
—
—
—
316 (1.50)
278 (1.56)
244 (14.87)
258 (2.07)
365 (0.29)
392 (1.07)
355 (100)
320 (15.53)
334 (1.25)
350 (1.44)
—
10b
10c
10d
10e
10f
370 (100)
336 (41.42)
350 (72.53)
458 (51.94)
484 (100)
447 (33.80)
412 (100)
119 (100)
119 (88.77)
—
10g
10h
10i
119 (74.79)
119 (100)
119(100)
119 (57.22)
119 (100)
150 (46.87)
150 (24.65)
150 (30.05)
426 (100)
10j
442 (89.49)
457 (23.03)
428 (92.48)
488 (12.28)
457 (100)
10k
10l*
10m
10n
10o
309 (3.36)
338 (2.18)
307 (4.94)
337 (3.85)
336 (1.74)
—
365 (2.54)
395 (2.29)
487 (100)
_1_0_p____
* [M]+ + 1 ion recorded for compound 10 l.

TABLE 4. Spectral Data for 3-Aminothiophenes 10f-p
IR spectrum, ν, cm-1
1Н NMR spectrum (DMSO-d6), δ, ppm (SSCC, J, Hz)
Com-
NH
NH2
C6H4Me
R3
—
HAr
pound
NН
CH
C=O
(1H, br. s)
(2H, br. s)
(3H, s) (R1)
3450 2980 1600
3320 2930
13.67
13.49
12.50
8.34
8.31
8.36
2.34
2.34
2.35
7.26 and 7.50 (4H, AA'BB', J = 8.5, HAr); 7.28 (1H, d, J = 8.2, HPh);
7.37 (2H, d, J = 7.3, HPh); 7.49 (2H, d, J = 8.2, HPh); 8.04 and 8.28 (4H,
AA'BB', J = 9.2, HAr)
10f
3400 2970 1710
1.34 (3H, t, J = 7.02,
СН2СН3); 4.32 (2H, q,
J = 7.02, СН2СН3)
7.25 and 7.49 (4H, AA'BB', J = 7.9, HAr); 7.27 (1H, t, J = 7.35, HPh);
7.37 (2H, d, J = 7.35, HPh); 7.47 (2H, t, J = 7.35, HPh);
7.94 and 8.02 (4H, AA'BB', J = 8.8, HAr)
10g
10h
3300
1610
3450 2970 1600
3310 2920
—
7.23 (2H, d, J = 8.2, HAr); 7.21–7.30 (1H, m, HPh);
7.40-7.55 (8H, m, HPh+HAr); 8.00 (2H, d, J = 8.8, HAr)
—
—
—
—
1600
12.11
12.89
8.15
8.17
—*
2.38
2.38
7.04-7.52 (11H, m, HPh+HAr); 7.83 (2H, d, J = 7.7, HAr)
10i
10j
3460
2.38 (3H, s, Me)
7.15-7.26 (5H, m, HPh+HAr); 7.32–7.45 (4H, m, HPh+HAr);
3330
7.49-7.56 (2H, m, HPh); 7.75 (2H, d, J = 8.2, HAr)
3450 2920 1600
3300
11.93
12.45
8.33
8.25
3.84 (3H, s, ОMe)
2.35
2.38
7.06 and 8.00 (4H, AA'BB', J = 9.2, HAr); 7.26 and 7.52 (4H, AA'BB',
10k
10l
J = 7.9, HAr); 7.18-7.33 (1H, m, HPh); 7.40-7.49 (4H, m, HPh)
3470 2980 1600
1.40 (3H, t, J = 7.0,
ОСН2СН3); 4.09 (2H, q,
J = 7.0, ОСН2СН3)
6.98 and 7.88 (4H, AA'BB', J = 8.8, HAr); 7.17 and 7.52 (4H, AA'BB',
J = 7.6, HAr); 7.18-7.25 (1H, m, HPh); 7.30-7.45 (4H, m, HPh)
2930
3480
3340
—
1600
12.12
13.79
12.81
11.92
8.18
8.49
8.35
8.48
9.74 (1H, br. s, ОН)
2.38
—
6.86 and 7.81 (4H, AA'BB', J = 8.8, HAr); 7.16 (1H, m, HPh);
7.23 and 7.53 (4H, AA'BB', J = 7.9, HAr); 7.36-7.41 (4H, m, HPh)
10m
10n
10o
3440 2970 1600
—
7.25-7.47 (4H, m, HAr); 7.57–7.74 (1H, m, HPh);
3300
7.80 and 8.02 (4H, AA'BB', J = 9.2, HAr) 8.24-8.29 (4H, m, HPh)
3450 2970 1600
3320
3450 2950 1600
2.40 (3H, s, Me)
—
7.17-7.44 (7H, m, HPh+HAr); 7.67–7.84 (4H, m, HPh+HAr);
8.27 (2H, d, J = 8.5, HAr)
1.31 (3H, t, ОСН2СН3);
4.10 (2H, q, ОСН2СН3)
—
7.04 (2H, d, J = 8.5, HAr); 7.24 (1H, br. s, HPh); 7.43 (4H, br. s, HPh+HAr);
10p
7.85 and 8.28 (4H, AA'BB', J = 7.9, HAr); 8.00 (2H, d, J = 7.7, HPh)
_______3300
* See HAr.

The formation of substituted thiophenes 10 probably occurs as the result of an intramolecular reaction
of the CH2 and CN groups in intermediate thioimidate 3.
The reaction of (p-tolylhydrazono)cyano-N-phenylthioacetamide 2g with chloroacetone 1a gives a
mixture of 4-methyl-3-phenyl-2-(p-tolylazocyanomethylene)thiazole (7a) and 2-acetyl-3-amino-5-phenylimino-
4-(p-tolylhydrazono)-4,5-dihydrothiophene (10e).
It is interesting to note that the reactions of N-phenylthioacetamides 2h-j, containing alkoxy and
hydroxy groups in the arylhydrazone moiety, with ketone 1a lead to single 2-(arylazocyanomethylene)-4-
methyl-3-phenylthioazoles 7b-d.
Thus, the direction of the reaction of N-phenylthioamides 2c-j with chloroacetone is a function of the
substituent in the aromatic fragment of the hydrazone molecule.
Regardless of the electronic effect of the substituent at C(4) in the aromatic ring of
arylhydrazonothioacetamides 2, the reaction of thioamides 2c-j gives single 3-amino-2-aroyl-4-(arylhydrazono)-
5-phenylimino-4,5-dihydrothiophenes 10f-p in 78-92% yield. The structures of 10f-p were supported by the
spectral data given in Tables 3 and 4 and the elemental analysis results (Table 5).
TABLE 5. Characteristics of Compounds 2, 6, 7, and 10
Found, %
Com-
pound
Reaction
time, h
Empirical
formula
Yield,
%
Calculated, %
mp, °C
N
S
5
1
2
3
4
6
7
2.0
3.0
3.5
3.0
3.0
2.5
3.0
3.5
4.0
4.0
5.0
6.0
5.0
7.0
26.0
27.0
26.0
25.0
22.0
С9H7N5O2S
28.00
28.11
12.90
12.85
>290
93
92
95
96
96
85
82
82
72
58
85
93
75
59
85
82
92
97
90
2a
2b
2c
2d
2e
2f
С10H10N4OS
С15H11N5O2S
С18H16N4O2S
С15H11 ClN4S
С15H12N4S
23.87
13.75
211-213
245-247
195-196
223-225
195-197
240-242
210-212
235-237
225-226
264-265
115-116
>250
23.93
13.67
21.60
21.54
9.90
9.85
16.02
9.12
15.91
9.09
18.00
17.81
10.25
10.17
19.95
11.60
20.00
11.43
С16H14N4S
19.00
19.05
11.02
10.88
2g
2h
2i
С16H14N4OS
С17H16N4OS
С15H12N4OS
С12H9N5O2S
С13H12N4OS
С19H16N4OS
С18H13N5O2S
С19H16N4OS
С20H18N4OS
С18H14N4OS
С18H15N5O3S
С21H20N4O3S
18.03
10.40
18.06
10.32
17.19
17.28
9.95
9.87
19.05
10.70
2j
18.92
10.81
24.60
24.35
11.02
11.15
6а
6b
6c
6d
7b
7c
7d
10a
10b
20.60
11.70
20.59
11.76
16.05
16.09
9.25
9.20
19.15
8.90
138-139
215-217
158-160
233-235
255-257
202-203
19.28
8.82
15.50
16.09
8.53
9.20
16.16
8.80
15.47
8.84
16.33
16.77
9.80
9.58
14.73
8.91
15.26
8.72
13.60
13.21
8.18
7.54
1392

TABLE 5 (continued)
1
2
3
4
5
6
7
23.0
26.0
32.0
34.0
35.0
34.0
33.0
36.0
36.0
35.0
35.0
34.0
36.0
С18H15ClN4OS
С18H16N4OS
С24H19N5O3S
С21H20N4O3S
С24H19ClN4OS
С24H20N4OS
С25H22N4OS
С25H22N4O2S
С26H24N4O2S
С24H20N4O2S
С23H16N6O5S
С24H19N5O3S
С25H21N5O4S
15.02
15.11
8.45
8.64
185-187
160-162
270-272
220-222
194-195
150-152
110-112
183-185
160-161
235-237
>245
89
88
79
92
95
94
84
86
94
79
83
78
89
10c
16.43
9.58
10d
10f
16.67
9.52
15.14
15.32
7.31
7.00
11.07
7.25
10g
10h
10i
11.57
6.61
13.00
12.54
7.48
7.17
13.55
8.49
13.59
7.77
12.87
13.15
7.65
7.51
10j
12.46
7.25
10k
10l
12.67
7.24
12.38
12.28
7.28
7.02
12.36
7.56
10m
10n
10o
10p
13.08
7.48
17.86
17.21
6.70
6.56
15.40
7.14
220-222
231-233
15.32
7.00
13.83
14.37
7.44
6.57
The formation of the thiophene ring in the reaction of N-phenylthioacetamides 2 with halo ketones may
be explained by the diminution of the nucleophilicity of the thioamide nitrogen atom upon introducing a phenyl
substituent and the concurrent appearance of the electronic effects of the substituent in the aromatic ring of the
arylhydrazone group, which is quite distant from the reaction sites, but nevertheless activates the cyano group
and thereby enables its involvement in cyclization to give product 10.
Comparison of the results of the reaction of 2-arylhydrazono-2-cyanothioacetamides with chloroacetone
and phenacyl bromides showed that the structure of the products depends on the structure of the starting
hydrazones and halo ketones used. While the reaction of thioacetamide and thioacetanilide with halocarbonyl
compounds leads to cyclization only to the corresponding thiazoles 6 (X = H2) and 7 (Y = H), the introduction
of a hydrazone fragment into these molecules permits the formation of both thiazoles 6 (X = NNHAr) or 7
(Y = N=NHAr) and thiophenes 10 (X = NNHAr). Thus, the arylhydrazone group, which does not participate
directly in the reaction, may affect the direction of cyclization since it is a "fine" transmitter of electronic effects
from rather distant parts of the molecule to the reaction site.
EXPERIMENTAL
The reaction and purity of the products were monitored by thin-layer chromatography on Silufol
UV-254 plates using 6:1, 10:1, and 15:1 chloroform–ethanol and 2:1 and 1:1 hexane–ethyl acetate as the
1
eluents. The IR spectra were taken on a UR-20 spectrometer for KBr pellets. The H NMR spectra were taken
on a Bruker WM-250 spectrometer at 250 MHz and Bruker spectrometer at 300 MHz with TMS as the internal
standard. The mass spectra were taken on a Varian MAT-311A spectrometer with 70 eV ionizing radiation and
direct sample inlet into the source.
1393

TABLE 6. Spectral Data for 2-Arylhydrazono-2-cyanothioacetamides 2a-j
IR spectrums, ν, cm-1
1Н NMR spectrum (DMSO-d6), δ, ppm (SSCC, J, Hz)
Com-
pound
HPh (J)
N–NH
(1H, s)
NH
R2NH
R3
HAr(4H,AA'BB')
C≡N
1H, t, p-H
2H, t, 2 m-H
2H, d, 2 o-H
3360, 3240
3420, 3260
3320, 3220
3350, 3230
3320, 3220
3320, 3220
3320, 3230
3320, 3220
3450, 3320
3370, 3230
2210
2220
2210
2210
2220
2210
2220
2210
2220
2220
11.78
11.43
11.61
11.50
11.41
11.20
11.14
11.25
11.07
11.01
9.38 (1H, s),
9.70 (1H, s)
—
—
—
—
7.89 and 8.14
2a
2b
2c
2d
2e
2f
(J = 9.1)
9.47 (1H, s),
3.75
—
—
—
6.91 and 7.66
9.18 (1H, s)
(3H, s, OMe)
(J = 9.3)
12.02
—
7.32 (7.3)
7.31 (7.9)
7.30 (7.3)
7.08 (7.3)
7.24 (7.3)
7.28 (7.3)
7.24 (7.3)
7.23 (7.3)
7.47 (7.3)
7.46 (7.9)
7.45 (7.3)
7.67 (7.6)
7.66 (7.6)
7.65 (7.6)
7.94 and 8.24
(1H, br. s)
(J = 9.5)
11.83
1.32 (3H, t, J = 7.0, СН2 СН3);
4.30 (2H, q, J = 7.0, СН2СН3)
7.85 and 7.95
(1H, br. s)
(J = 8.9)
11.68
—
7.42 and 7.78
(1H, br. s)
(J = 8.8)
11.48
—*
7.22-7.43 (5Н, m); 7.67-7.75 (4H, m)
(1H, br. s)
11.42
2.31
7.39 (7.3)
7.62 (8.0)
7.65 (7.6)
7.68 (7.6)
7.69 (7.6)
7.12 and 7.62
2g
2h
2i
(1H, br. s)
(3H, s, Me)
(J = 8.2)
11.58
3.76
7.43 (7.3)
7.39 (7.3)
7.38 (7.3)
6.96 and 7.72
(1H, br. s)
(3H, s, OMe)
(J = 9.0)
11.43
1.36 (3H, t, J = 7.0, СН2СН3);
4.01 (2H, q, J = 7.0, СН2СН3)
—
6.85 and 7.66
(1H, br. s)
(J = 8.9)
11.39
6.72 and 7.55
2j
(1H, br. s)
(J = 8.9)
_______
* See HPh, HAr.

Starting arylhydrazonocyanothioacetamides 2a-j were obtained from the corresponding aryldiazonium
chlorides and cyanothioacetamide or cyanothioacetanilide according to Dubenko [4] and Belskaya [5]. The
indices for these compounds are given in Tables 5 and 6.
General Method for the Reaction of (Arylhydrazono)cyanothioacetamide 2a-j with Chloroacetone
1a and Phenacyl Bromides 1b and 1c. A sample of corresponding halo ketone 1a-c (10 mmol) and
triethylamine (10 mmol) were added to a solution of 2a-j (10 mmol) in DMF. The reaction mixture was
maintained at 80 C until the starting compounds disappeared as indicated by thin-layer chromatography and,
°
then, poured into water. The precipitated product was filtered off and crystallized from ethanol.
This work was carried out with the financial support of the Russian Basic Research Fund (Grant
No. 01-03-33173a).
REFERENCES
1.
2.
V. P. Litvinov, Usp. Khim., 68, 817 (1999).
H. Tokuyama, T. Amashita, M. T. Reding, Y. Koburagi, and T. Fukuyama, J. Am. Chem. Soc., 121,
3791 (1999).
3.
4.
5.
H. Takahata and E. Yamazaki, Heterocycles, 27, 1953 (1988).
R. G. Dubenko, I. M. Bazavova, and E. F. Gorbenko, Zh. Org. Khim., 20, 577 (1984).
N. P. Belskaia, E. E. Zvereva, W. Dehaen, and V. A. Bakulev, J. Chem. Res. (M), 1367 (2000).
1395