Synthesis and oxidative cyclization of 3-amino-2-arylazo-5-tert- cycloalkylaminothiophenes

Article abstract of DOI:10.1007/s10593-011-0799-8

A series of 3-amino-4-arylazo-4,5-dihydrothiophenes has been synthesized by the reaction of arylhydrazonocyanothioacetamides (containing a tert-cycloalkylamino group) with α-halo ketones, 2-chloroacetonitrile, or 4-nitrobenzyl bromide. Their oxidation in

Full text of DOI:10.1007/s10593-011-0799-8

Chemistry of Heterocyclic Compounds, Vol. 47, No. 5, August 2011 (Russian original Vol. 47, No. 5, May, 2011)
SYNTHESIS AND OXIDATIVE CYCLIZATION OF
3-AMINO-2-ARYLAZO-5-tert-CYCLOALKYLAMINOTHIOPHENES
N. P. Belskaya1*, A. V. Koksharov1, A. I. Eliseeva1,
Z. Fan2, and V. A. Bakulev1
A series of 3-amino-4-arylazo-4,5-dihydrothiophenes has been synthesized by the reaction of aryl-
hydrazonocyanothioacetamides (containing a tert-cycloalkylamino group) with -halo ketones,
2-chloroacetonitrile, or 4-nitrobenzyl bromide. Their oxidation in the presence of metal acetates was
investigated. It was shown that heating in pyridine with Cu(OAc)2 leads to the formation of thieno-
[3,4-d]-1,2,3-triazoliumolates.
Keywords: arylhydrazonothioacetamides, halocarbonyl compounds, thieno[3,4-d]-1,2,3-triazolium-
olates, thiophenes, tert-cycloalkylamines, oxidation.
-Halocarbonyl compounds, including such derivatives as -chloroacetic acid and 2-halo ketones or
phenacyl bromides, are widely used in organic synthesis for the preparation of different heterocyclic compounds
[1–9]. We have previously shown that reaction of arylhydrazonothioacetamides with -halo ketones gives
1,3-thiazoles or 4,5-dihydrothiophenes depending on the electronic effects and steric factors of the substituents
on the nitrogen atom of the thioamide fragment and the nature of the substituent in the aromatic ring [6–9]. The
aim of our work is to determine the area of applicability of this reaction in the synthesis of thiophenes and to
study the chemical properties of the heterocyclic compounds obtained.
The reaction of the arylhydrazonothioacetamides 1a–h (which contain a tert-cycloalkylamine substitu-
ent in the thioamide group) with the -halo ketones 2a,c, chloroacetonitrile 2b, and 4-nitrobenzyl bromide 2d
was carried out by heating in the presence of strong bases.
As a result we obtained the series of 3-amino-2-arylazothiophenes 4a–m, the mechanism of formation of
which can be represented as a nucleophilic addition of the methylene group to the carbon atom of the cyano
1
group in the initially formed intermediate 3. The H NMR spectra of the aminothiophenes 4a–m show the
presence of a signal for the NH2 group as two broad, one-proton singlets or a two-proton singlet in the region
9.00–10.10 ppm together with signals for the proton-containing parts of the substituents R, R1, and tert-cyclo-
_______________
Dedicated to Academician V. N. Charushin on his 60th birthday.
* To whom correspondence should be addressed, e-mail: belska@mail.ustu.ru.
1 Ural Federal University named after the first President of Russia B. N. Yeltsin, 19 Mira Str., Yekaterinburg
620002, Russia.
2 State Key Laboratory for Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 684–691, May, 2011. Original
article submitted February 28, 2011.
0009-3122/11/4705-0564©2011 Springer Science+Business Media, Inc.
564

alkylamino groups. The IR spectra of the 3-aminothiophenes 4 show two absorption bands for the NH2 group in
the region 3260–3450 cm–1. The absorption band corresponding to the C=O stretching vibration is shifted in the
IR spectra of compounds 4a–c,e–g,i–l to the region 1575–1600 cm–1 and this points to the formation of
intramolecular hydrogen bonds in their molecules. With exchange of the acyl or benzoyl substituent R1 in
compounds 4a,c,e for a cyano or a 4-nitrophenyl group the signals for the NH2 group protons are shifted to high
field in the 1H NMR spectra of compounds 4d,h by 2.6–2.0 and 0.6–1.2 ppm and this may be a consequence of
weakening of the hydrogen bonding in which the group participates.
R1
H2N
DMF, 80°C
CN
NC
N
S
S
R1
t-BuONa or KOH
N
N
S
H
R1
N
R
N
+
R
Y
N
N
N
R
N
X
X
X
1a–h
2a–d
3
4a–m
57–96%
1 a–c R = 4-MeOC6H4, a X = CH2, b X = (CH2)2, c X = OCH2, d–h R = Ph, d X = CH2,
e X = (CH2)2, f X = (CH2)3, h X = CH2N–Ph; 2 a, b Y = Cl, a R1 = MeCO, b R1 = CN;
c, d Y = Br, c R1 = 4-ClC6H4CO, d R1 = 4-NO2C6H4CH2; 4 a–h R = 4-MeOC6H4,
a–c R1 = COMe, a X = CH2, b X = (CH2)2, c X = OCH2, d R1 = CN, X = CH2,
e–g R1 = 4-ClC6H4CO, e X = CH2, f X = (CH2)2, g X = OCH2, h R1 = 4-NO2C6H4, X = OCH2;
i–l R = Ph, R1 = 4-ClC6H4CO, i X = CH2, j X = (CH2)2, k X = OCH2,
l X = (CH2)3, R = Ph, R1 = 4-ClC6H4CO, m R = Ph, R1 = 4-ClC6H4CO, X = Ph–NCH2
We have found that the oxidation of the 3-amino-4-aryl-5-tert-cycloalkylaminothiophenes 4e–g,i–m in
pyridine in the presence of copper acetate with heating to 80ºC gives the 1H-thieno[3,4-d]-1,2,3-triazoliumolates
5a–h, the structure of which was confirmed by spectroscopic methods and elemental analytical data.
The mass spectra of the bicyclic zwitterionic compounds 5a–h show a molecular ion peak differing by 2
units from the molecular weight of the starting compounds. When compared with the thiophenes 4 the 1H NMR
spectra of the triazoliumolates 5a–h have lost the NH2 group signals and the signals for the protons in the ortho-
position of the aromatic rings of the R substituent is shifted by 0.5 ppm to low field. The IR spectra of the
thieno[3,4-d]-1,2,3-triazoliumolates 5a–h show the absence of the corresponding amino group NH bond
absorption band seen in the spectra of the starting thiophenes 4. The stretching vibration band of the carbonyl
CO bond is seen at 1575–1604 cm–1.
Cu(OAc)2
R1
S
–
H
30 h
N
Pyridine, 80oC
R1
S
+
R
H2N
N
N
N
N
R
N
M(OAc)n
N
X
X
55–90%
5a–h
4e–g,i–m
M = Hg2+, Ag+ n = 1, 2
5 a–h R1 = 4-ClC6H4CO, a–c R = 4-MeOC6H4, a X= CH2, b X = (CH2)2, c X = OCH2,
d–h R = Ph, d X= CH2, e X = (CH2)2, f X = OCH2, g X = (CH2)3, h X = PhNCH2
565

TABLE 1. Effect of the Ratio of Substrate to Cu(OAc)2 on the Reaction
Time and Yield of the Thieno[3,4-d]-1,2,3-triazolate 5f
Experiment No.
4g : Сu(OAc)2
Reaction time, h
Yield of 5f, %
1
2
3
1 : 2
1 : 1
20
25
30
63
55
46
10 : 1
The UV spectra of the thieno[3,4-d]-1,2,3-triazoliumolates 5a–h have three absorption maxima at 272–
290, 360–370, and 482–540 nm. A marked bathochromic shift of the long wavelength maximum of 100 nm is
observed when compared with the UV spectra of the starting 4-arylazo-5-tert-cycloalkylaminothiophenes 4.
The use of different ratios of copper(II) acetate and arylhydrazonothiophene and also heating in the ab-
sence of Cu(OAc)2 showed that the copper(II) salt acts as a catalyst in this reaction (Table 1).
Heating the arylazoaminothiophenes 4 in the presence of Hg(II) or silver(I) acetates did not lead to for-
mation of novel products.
The use of the thiophenes 4d,h (containing a cyano or 4-nitrophenyl group in position 5 of the thiophene
ring) as the starting compounds in the oxidation involving Cu(OAc)2 also did not yield novel compounds. This
fact allows us to propose that the presence of a carbonyl group at position 2 of the heterocycle is an important
feature in achieving the oxidative cyclization of the 3-amino-4-arylazothiophenes 4. The activation mechanism
for compounds 4e–g,i–m may be connected to a catalytic effect of the C=O group via formation of a hydrogen
bond with the amino group and also an increase in the stability of the bicyclic triazoliumolates 5a–h through
involvement of the carbonyl group at ring position 4 in the delocalization of negative charge.
–
O
–
O
R1
R1
O
O
R1
R1
–
–
N
N
N
N
N
+
N
S
+
N
S
R
N
R
N
R
N
S
S
R
N
N
+
N
N
N
N
+
D
A
B
C
The appearance of charges on the nitrogen and oxygen atoms is confirmed by the shift of signals in the
1H NMR spectra, the bathochromic shift of the long wavelength maximum in the UV spectra, and also the shift
of the absorption band for the carbonyl group in the IR spectra of the thieno[3,4-d]-1,2,3-triazoliumolates 5a–h.
Given investigation demonstrated that the reaction of the 2-arylhydrazono-2-cyanothioacetamides 1 with
-halocarbonyl compounds and 4-nitrobenzyl bromide is a convenient method for the preparation of poly-
functional thiophenes. These can be used in the synthesis of novel condensed heterocyclic derivatives which
include this cyclic fragment.
EXPERIMENTAL
IR spectra were taken on a Bruker Alpha Fourier Spectrometer (ATR, ZnSe). UV spectra were taken on
1
a Perkin-Elmer Lambda 45 spectrometer using THF. H and 13C NMR spectra were recorded on a Bruker
AVANCE II 400 instrument (400 and 100 MHz respectively) using DMSO-d6 (compounds 4a–m), pyridine-d5
(compounds 5a,c,d,h), or 1,4-dioxane-d8 (compounds 5b,e–g) with TMS as internal standard. Mass spectra were
recorded on a Varian MAT 311A instrument with ionization energy 70 eV. Monitoring of the reaction course
566

and purity of the compounds prepared was performed by TLC on Sorbfil UV-254 plates in the systems ethyl
acetate–hexane (1:1), chloroform–acetone (30:1), or chloroform–hexane–acetone (5:4:1).
The arylhydrazonocyanoacetamides were prepared by the previously reported method [10].
Reaction of the arylhydrazonothioacetamides 1a–h with the halocarbonyl compounds (2a–d).
(General Method). Compound 2 (1 mmol) and t-BuOK (0.23 g, 2 mmol) were added to a solution of the
arylhydrazonocyanothioacetamide 1 (1 mmol) in DMF (5 ml). The reaction product was held at 80ºC until the
starting material had disappeared (TLC, poured into water, and the precipitate formed was filtered off and
recrystallized from ethyl alcohol).
1-[3-Amino-4-(4-methoxyphenylazo)-5-(pyrrolidin-1-yl)thiophen-2-yl]ethanone (4a). Yield 47%;
mp 238–239ºC. IR spectrum, , cm–1: 1581 (CO), 2830, 2850, 2900, 2940, 2970 (C–H); 3350, 3400 (N–H). UV
spectrum, max, nm (log ): 350 (6.86), 445 (6.38). 1H NMR spectrum, , ppm (J, Hz): 2.09–2.12 (4H, m, 2CH2);
2.21 (3H, s, COCH3); 3.79–3.85 (4H, m, 2CH2); 3.86 (3H, s, OCH3); 6.94 and 7.55 (4H, AA'XX', J = 8.8, Ar);
8.76 (1H, br. s, NH); 9.01 (1H, br, s, NH). Mass spectrum, m/z (Irel, %): 344 [M]+ (29). Found, %: C 59.49;
H 6.05; N 16.35; S 9.23. C17H20N4O2S. Calculated, %: C 59.28; H 5.85; N 16.27; S 9.31.
1-[3-Amino-4-(4-methoxyphenylazo)-5-piperidinothiophen-2-yl]ethanone (4b). Yield 55%; mp
236–237ºC. IR spectrum, , cm–1: 1578 (CO), 2835, 2970 (C–H), 3355, 3440 (N–H). 1H NMR spectrum, , ppm
(J, Hz): 1.76–1.82 (6H, m, 3CH2); 2.09 (3H, s, COCH3); 3.83 (3H, s, OCH3); 3.85–3.90 (4H, m, 2CH2); 6.95 and
7.56 (4H, AA'XX', J = 9.2, Ar); 8.60 (1H, br. s, NH); 8.72 (1H, br. s, NH). Mass spectrum, m/z (Irel, %): 358
[M]+ (17). Found, %: C 60.19; H 6.28; N 15.48. C18H22N4O2S. Calculated, %: C 60.31; H 6.19; N 15.63.
1-[3-Amino-4-(4-methoxyphenylazo)-5-morpholinothiophen-2-yl]ethanone (4c). Yield 49%; mp
243–244ºC. IR spectrum, , cm–1: 1596 (CO), 2850, 2975 (C–H), 3350, 3400 (N–H). 1H NMR spectrum, , ppm
(J, Hz): 2.12 (3H, s, COCH3); 3.82–3.87 (4H, m, 2CH2); 3.84 (3H, s, OCH3); 3.87–3.89 (4H, m, 2CH2); 7.58 and
7.97 (4H, AA'XX', J = 9.2, Ar); 8.57 (1H, s, NH); 8.63 (1H, s, NH). Mass spectrum, m/z (Irel, %): 360 [M]+ (22).
Found, %: C 56.89; H 5.68; N 15.66. C17H20N4O3S. Calculated, %: C 56.65; H 5.59; N 15.54.
3-Amino-4-(4-methoxyphenylazo)-5-(pyrrolidin-1-yl)thiophene-2-carbonitrile (4d). Yield 60%; mp
1
240–241ºC. IR spectrum, , cm–1: 2166 (C≡N), 2832, 2863, 2965, 2982 (C–H), 3300, 3370 (N–H). H NMR
spectrum, , ppm (J, Hz): 2.11–2.14 (4H, m, 2CH2); 3.75–3.78 (4H, m, 2CH2); 3.87 (3H, s, OCH3); 6.77 (2H, br.
s, NH2); 6.95–7.00 (2H, m, Ar); 7.55–7.58 (2H, m, Ar). Mass spectrum, m/z (Irel, %): 327 [M]+ (18). Found, %:
C 56.43; H 5.39; N 21.53. C16H17N5OS. Calculated, %: C 58.70; H 5.23; N 21.39.
[3-Amino-4-(4-methoxyphenylazo)-5-(pyrrolidin-1-yl)thiophen-2-yl](4-chlorophenyl)methanone
(4e). Yield 75%; mp 270–271ºC. IR spectrum, , cm–1: 1600 (CO), 2830, 2850, 2900, 2940, 2960 (C–H), 3450
(NH). UV spectrum, max, nm (log ): 378 (6.68), 436 (6.48). 1H NMR spectrum, , ppm (J, Hz): 2.03–2.14 (4H,
m, 2CH2); 3.82 (3H, s, OCH3); 4.63–4.82 (4H, m, 2CH2); 7.00 and 7.61 (4H, AA'XX', J = 8.8, Ar); 7.48 and
7.63 (4H, AA'XX', J = 8.3, Ar); 9.14 (1H, s, NH); 9.16 (1H, s, NH). Mass spectrum, m/z (Irel, %): 440 [M]+ (9).
Found, %: C 60.25; H 5.14; N 12.43. C22H21ClN4O2S. Calculated, %: C 59.92; H 4.80; N 12.71.
[3-Amino-4-(4-methoxyphenylazo)-5-piperidinothiophen-2-yl](4-chlorophenyl)methanone (4f). Yield
51%; mp 202–203ºC. IR spectrum, , cm–1: 1595 (CO), 2963 (C–H), 3320 (N–H). 1H NMR spectrum, , ppm (J,
Hz): 1.73–1.79 (6H, m, 3CH2); 3.84 (3H, s, OCH3); 3.85–4.00 (4H, m, 2CH2); 6.97 and 7.59 (4H, AA'XX',
J = 8.8, Ar); 7.43 and 7.60 (4H, AA'XX', J = 8.4, Ar); 9.14 (2H, br. s, NH2). Mass spectrum, m/z (Irel, %): 454
[M]+ (8). Found, %: C 61.13; H 5.28; N 11.99. C23H23ClN4O2S. Calculated, %: C 60.72; H 5.10; N 12.31.
[3-Amino-4-(4-methoxyphenylazo)-5-(morpholinothiophen-2-yl](4-chlorophenyl)methanone (4g).
1
Yield 63%; mp 204–205ºC. IR spectrum, , cm–1: 1601 (CO), 2852, 2924, 2953 (C–H), 3433 (N–H). H NMR
spectrum, , ppm (J, Hz): 3.80–3.82 (4H, m, 2CH2); 3.85 (3H, s, OCH3); 3.87–3.91 (4H, m, 2CH2); 6.98 and
7.60 (4H, AA'XX', J = 8.8, Ar); 7.44 and 7.62 (4H, AA'XX', J = 8.4, Ar); 9.07 (2H, br. s, NH2). Mass spectrum,
m/z (Irel, %): 456 [M]+ (18). Found, %: C 57.66; H 4.81; N 12.47. C22H21ClN4O3S. Calculated, %: C 57.83;
H 4.63; N 12.26.
4-(4-Methoxyphenylazo)-5-morpholino-2-(4-nitrophenyl)thiophene-3-amine (4h). Yield 49%; mp
238–239ºC. IR spectrum, , cm–1: 1585 (CO), 2840, 2969 (C–H), 3248, 3462 (N–H). 1H NMR spectrum, , ppm
567

(J, Hz): 3.79 (3H, s, OCH3); 3.80–3.92 (8H, m, 4CH2); 7.00 (2H, d, J = 8.8, Ar); 7.55–7.60 (4H, m, Ar); 8.12
(2H, br. s, NH2); 8.19 (2H, d, J = 9.2, Ar). Mass spectrum, m/z (Irel, %): 439 [M]+ (22). Found, %: C 57.15;
H 4.95; N 15.83. C21H21N5O4S. Calculated, %: C 57.39; H 4.82; N 15.94.
[3-Amino-5-(pyrrolidin-1-yl)-4-phenylazothiophen-2-yl](4-chlorophenyl)methanone (4i). Yield
65%; mp 225–226ºC. IR spectrum, , cm–1: 1580 (CO), 2918, 2937, 2997 (C–H), 3430 (N–H). UV spectrum,

max, nm (log ): 365 (6.24), 430 (5.83). 1H NMR spectrum, , ppm (J, Hz): 1.11–1.18 (2H, m, CH2); 1.20–1.28
(2H, m, CH2); 2.05–2.13 (4H, m, 2CH2); 7.33 (1H, t, J = 7.2, Ph); 7.48–7.57 (4H, m, Ph); 7.64–7.70 (4H, m,
Ar); 9.24 (1H, s, NH); 9.32 (1H, s, NH). Mass spectrum, m/z (Irel, %): 410 [M]+ (23). Found, %: C 61.60;
H 4.80; N 13.75. C21H19ClN4OS. Calculated, %: C 61.38; H 4.66; N 13.63.
[3-Amino-5-piperidino-4-phenylazothiophen-2-yl](4-chlorophenyl)methanone (4j). Yield 57%; mp
180–181ºC. IR spectrum, , cm–1: 1579 (CO), 2854, 2943 (C–H); 3352 (N–H). UV spectrum, max, nm (log ):
366 (6.22), 445 (5.69). 1H NMR spectrum, , ppm (J, Hz): 1.75–1.82 (6H, m, 3CH2); 3.94–3.97 (4H, m, 2CH2);
7.32 (1H, t, J = 7.2, Ar); 7.42–7.45 (4H, m, Ar); 7.60–7.62 (4H, m, Ar); 9.20 (2H, s, NH2). Mass spectrum, m/z
(Irel, %): 424 [M]+ (12). Found, %: C 61.92; H 5.50; N 13.26. C22H21ClN4OS. Calculated, %: C 62.18; H 4.98;
N 13.18.
[3-Amino-5-morpholino-4-phenylazothiophen-2-yl](4-chlorophenyl)methanone (4k). Yield 75%;
mp 220–221ºC. IR spectrum, , cm–1: 1580 (CO), 2856, 2922, 3029 (C–H); 3265, 3378 (N–H). UV spectrum,

max, nm (log ): 360 (6.49), 450 (5.80). 1H NMR spectrum, , ppm (J, Hz): 3.78–3.81 (4H, m, 2CH2); 3.92–3.95
(4H, m, 2CH2); 7.40 (1H, t, J = 7.2, Ar); 7.40–7.57 (4H, m, Ar); 7.65–7.70 (4H, m, Ar); 9.15 (2H, br. s, NH2).
Mass spectrum, m/z (Irel, %): 426 [M]+ (20). Found, %: C 59.22; H 4.61; N 13.20. C21H19ClN4O2S. Calculated,
%: C 59.08; H 4.49; N 13.12.
[3-Amino-5-(azepan-1-yl)-4-phenylazothiophen-2-yl](4-chlorophenyl)methanone (4l). Yield 60%;
mp 208–209ºC. IR spectrum, , cm–1: 1575 (CO), 2924, 2939, 2941 (C–H), 3260 (N–H). 1H NMR spectrum, ,
ppm (J, Hz): 1.55–1.67 (4H, m, 2CH2); 1.78–1.96 (4H, m, 2CH2); 3.94–3.96 (4H, m, 2CH2); 7.30 (1H, t, J = 7.4,
Ar); 7.41–7.46 (4H, m, Ar); 7.55–7.63 (4H, m, Ar); 9.26 (1H, s, NH); 9.36 (1H, s, NH). Mass spectrum, m/z (Irel,
%): 438 [M]+ (12). Found, %: C 63.19; H 5.41; N 12.88. C23H23ClN4OS. Calculated, %: C 62.93; H 5.28;
N 12.76.
[3-Amino-4-phenylazothiophen-2-yl-5-(4-phenylpiperazin-1-yl)](4-chlorophenyl)methanone (4m).
1
Yield 68%; mp 213–214ºC. IR spectrum, , cm–1: 1596 (CO), 2839, 2850 (C–H), 3430 (N–H). H NMR
spectrum, , ppm (J, Hz): 3.40–3.42 (4H, m, 2CH2); 4.11–4.13 (4H, m, 2CH2); 6.79 (1H, t, J = 7.6, Ar); 6.92
(2H, d, J = 7.2, Ar); 7.21 (2H, t, J = 7.2, Ar); 7.37 (1H, t, J = 7.2, Ar); 7.49–7.51 (4H, m, Ar); 7.62–7.67 (4H, m,
Ar); 9.16 (2H, br. s, NH2). Mass spectrum, m/z (Irel, %): 501 [M]+ (16). Found, %: C 64.38; H 4.95; N 13.88.
C27H24ClN5OS. Calculated, %: C 64.60; H 4.82; N 13.95.
Oxidation of 3-Amino-4-arylazo-5-tert-cycloalkylaminothiophenes 4. Cu(OAc)2 (0.364 g, 2 mmol)
was added to a solution of the 3-amino-4-arylazothiophene 4 (1 mmol) in pyridine and held with stirring at 80ºC
for 20 h (TLC). The reaction product was poured onto ice and the precipitate formed was filtered off and washed
with water.
[2-(4-Methoxyphenyl)-6-(pyrrolidin-1-yl)-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chloro-
phenyl)methanolate (5a). Yield 90%; mp 266–267ºC. IR spectrum, , cm–1: 1575 (CO), 2943 (C–H). UV
1
spectrum, max, nm (log ): 275 (6.25), 348 (6.39), 478 (5.92). H NMR spectrum, , ppm (J, Hz): 2.03–2.17
(4H, m, 2CH2); 4.63–4.82 (4H, m, 2CH2); 3.82 (3H, s, OCH3); 6.99 and 8.04 (4H, AA'XX', J = 8.8, Ar); 7.45
and 8.15 (4H, AA'XX', J = 8.4, Ar). Mass spectrum, m/z (Irel, %): 438 [M]+ (100). Found, %: C 60.35; H 4.23;
N 12.84. C22H19ClN4O2S. Calculated, %: C 60.20; H 4.36; N 12.76.
[2-(4-Methoxyphenyl)-6-piperidino-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophe-
1
nyl)methanolate (5b). Yield 63%; mp 242–243ºC. IR spectrum, , cm–1: 1575 (CO), 2860, 2943 (C–H). H
NMR Spectrum, , ppm (J, Hz): 1.90–2.02 (6H, m, 3CH2); 3.85 (3H, s, OCH3); 3.87–3.94 (2H, m, CH2); 4.15–
4.22 (2H, m, CH2); 7.05 and 8.05 (4H, AA’XX’, J = 9.2, Ar); 7.40 and 8.10 (4H, AA’XX’, J = 8.8, Ar). Mass
568

spectrum, m/z (Irel, %): 452 [M]+ (100). Found, %: C 60.73; H 4.56; N 12.25. C23H21ClN4O2S. Calculated, %:
C 60.99; H 4.67; N 12.37.
[2-(4-Methoxyphenyl)-6-morpholino-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophe-
1
nyl)methanolate (5c). Yield 56%; mp 260–261ºC. IR spectrum, , cm–1: 1590 (CO), 2860, 2940 (C–H). H
NMR spectrum, , ppm (J, Hz): 3.87 (3H, s, OCH3); 3.84–3.91 (4H, m, 2CH2); 3.92–3.99 (4H, m, 2CH2); 7.08
and 8.04 (4H, AA'XX', J = 9.2, Ar); 7.49 and 8.05 (4H, AA'XX', J = 8.4, Ar). Mass spectrum, m/z (Irel, %): 454
[M]+ (100). Found, %: C 58.22; H 4.32; N 12.53. C22H19ClN4O3S. Calculated, %: C 58.08; H 4.21; N 12.32.
[6-(Pyrrolidin-1-yl)-2-phenyl-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophenyl)me-
thanolate (5d). Yield 94%; mp 220–221ºC. IR spectrum, , cm–1: 1604 (CO). UV spectrum, max, nm (log ):
272 (6.44), 360 (6.14), 482 (6.07). 1H NMR spectrum, , ppm (J, Hz): 1.82–1.93 (4H, m, 2CH2); 3.23–3.81 (4H,
m, 2CH2); 7.21–7.58 (3H, m, Ar); 7.65 (2H, d, J = 8.4, Ar); 8.30 and 8.63 (4H, AA'XX', J = 8.0, Ar). Mass
spectrum, m/z (Irel, %): 408 [M]+ (100). Found, %: C 61.53; H 4.02; N 13.81. C21H17ClN4OS. Calculated, %:
C 61.68; H 4.19; N 13.70.
[6-Piperidino-2-phenyl-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophenyl)methanolate
(5e). Yield 52%; mp 198–199ºC. IR spectrum, , cm–1: 1595 (CO), 2858, 2939 (C–H). UV spectrum, max, nm
(log ): 272 (6.34), 370 (5.99), 523 (5.92). 1H NMR spectrum, , ppm (J, Hz): 1.62–1.84 (6H, m, 3CH2); 3.57–
3.71 (2H, m, CH2); 3.96–3.99 (2H, m, CH2); 7.45–7.60 (5H, m, Ar); 8.03 (1H, t, J = 8.8, Ar); 8.15–8.21 (3H, m,
Ar). Mass spectrum, m/z (Irel, %): 422 [M]+ (100). Found, %: C 62.57; H 4.65; N 13.10. C22H19ClN4OS.
Calculated, %: C 62.48; H 4.53; N 13.25.
[(6-Morpholino)-2-phenyl-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophenyl)metha-
nolate (5f). Yield 63%; mp 210–211ºC. IR spectrum, , cm–1: 1589 (CO). UV spectrum, max, nm (log ): 280
1
(6.53), 360 (6.25), 540 (6.04). H NMR spectrum, , ppm (J, Hz): 3.63–3.73 (2H, m, CH2); 3.87–3.93 (6H, m,
3CH2); 7.43–7.58 (7H, m, Ar); 8.14 (2H, d, J = 8.4, Ar). Mass spectrum, m/z (Irel, %): 424 [M]+ (100). Found,
%: C 59.15; H 4.12; N 13.34. C21H17ClN4O2S. Calculated, %: C 59.36; H 4.03; N 13.19.
[2-Phenyl-6-(4-phenylpiperazin-1-yl)-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophe-
1
nyl)methanolate (5g). Yield 94%; mp 219–220ºC. IR spectrum, , cm–1: 1589 (CO), 2854, 2943 (C–H). H
NMR spectrum, , ppm (J, Hz): 3.40–3.42 (2H, m, CH2); 3.42–3.45 (2H, m, CH2); 3.63–3.83 (2H, m, CH2);
3.83–3.90 (2H, m, CH2); 6.80–7.00 (4H, m, Ar); 7.20–7.28 (2H, m, Ar); 7.46–7.55 (6H, m, Ar); 8.17–8.22 (2H,
m, Ar). Mass spectrum, m/z (Irel, %): 499 [M]+ (54). Found, %: C 64.87; H 4.75; N 14.15. C27H22ClN5OS.
Calculated, %: C 64.73; H 4.63; N 13.98.
[6-(Azepan-1-yl)-2-phenyl-4H-thieno[3,4-d]-1,2,3-triazol-2-ium-4-ylidene](4-chlorophenyl)metha-
1
nolate (5h). Yield 53%; mp 230–231ºC. IR spectrum, , cm–1: 1596 (CO), 2855, 2960 (C–H). H NMR
spectrum, , ppm (J, Hz): 1.47–1.49 (4H, m, 2CH2); 1.70–1.80 (4H, m, 2CH2); 3.42–3.60 (2H, m, CH2); 4.09–
4.22 (2H, m, CH2); 7.46 (1H, t, J = 7.2, Ar); 7.53–7.60 (2H, m, Ar); 7.68 (2H, d, J = 8.4, Ar); 8.33 and 8.65 (4H,
AA'XX', J = 8.0, Ar). Mass spectrum, m/z (Irel, %): 436 [M]+ (100). Found, %: C 63.35; H 4.73; N 13.02.
C23H21ClN4OS. Calculated, %: C 63.22; H 4.84; N 12.82.
This work was carried out with the financial support of the Russian Fund for Basic Research
(RFFI 10-03-96084_p_урал-a).
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