Synthesis of novel bis-thiadiazoles, bis-triazoles and polypyrazole derivatives based on hydrazonoyl halides

Article abstract of DOI:10.1016/j.tet.2013.04.137

A series of novel bis-thiadiazoles and bis-triazoles derivatives were synthesized via the reaction of hydrazonoyl halides with different moieties. Also, the synthesis and mechanism for polypyrazole formation are described via reaction of bis-hydrazonoyl w

Full text of DOI:10.1016/j.tet.2013.04.137

Tetrahedron 69 (2013) 5293e5298
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Synthesis of novel bis-thiadiazoles, bis-triazoles and polypyrazole
derivatives based on hydrazonoyl halides
,b,
Abdelwahed R. Sayed a
*
a Department of Chemistry, Faculty of Science, KFU, Saudi Arabia
b Department of Chemistry, Faculty of Science, University of Beni Suef, Egypt
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 March 2013
Received in revised form 18 April 2013
Accepted 30 April 2013
Available online 7 May 2013
A series of novel bis-thiadiazoles and bis-triazoles derivatives were synthesized via the reaction of
hydrazonoyl halides with different moieties. Also, the synthesis and mechanism for polypyrazole for-
mation are described via reaction of bis-hydrazonoyl with p-benzoquinone. Synthesized compounds
were elucidated by elemental analysis and spectral data.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Hydrazonoyl halides
Bis-thiadiazole
Bis-triazole
Polypyrazole
1. Introduction
Several pyrazoles are important as pharmaceuticals, and have
been found to possess analgetic,22 antipyretic22,23 and antimicro-
The interest in the chemistry of hydrazonoyl halides is a conse-
quence of the fact that they undergo a wide variety of reactions,
which provide routes to a myriad of both heterocyclic and acyclic
compounds. In addition, diverse biological activities, such as an-
thelmintic, antiviral, antiarthropodal, antimicrobial, fungicidal,
herbicidal, antisarcoptic, insecticidal, pesticidal, acaricidal, miti-
cidal, etc., have been found to be associated with hydrazonoyl
halids.1e6 Also, bis-hydrazonoyl dichlorides7e10 are highly versatile
and useful building blocks for the synthesis of a wide variety of
heterocyclic. They have also been used as subunits in molecular
hosts, such as macrocycles and supermolecular species.11 Moreover,
some bis-heterocycles, such as 2,20-bis-1,3,4-thiadiazole de-
rivatives exhibit interesting photoluminescence and electrolumi-
nescence and are used as thermotropic liquid crystals.12,13 In
addition, 3,30-bis-1,2,4-triazoles have proved to possess bacteri-
cidal, fungicidal and anthelmintic activities.14 Triazolopyrimidines
possess a wide variety of biological activities. For instance,
they exhibit in vivo activity against the amastigate stage of leish-
maniadonovani,15,16 have cardiovascular activity,17e19 are active
against Aspergillus and Penicillium species,20 and have been tested
as bioregulator agents.21
bial22,24 properties. They are also useful as biodegradable agro-
chemicals25 and as intermediate in the dye industry.26
Herein the synthesis of novel bis-thiadiazoles, bis-triazoles and
polypyrazole based on bis-hydrazonoyl dichlorides is reported.
2. Results and discussion
A new access to one-pot synthesis of bis-thiadiazoles, bis-
triazoles and polypyrazole via reactions of bis-hydrazonoyl
dichlorides 1 with thiourea 2, methylhydrazine-carbodithioate 5,
2-methylthioketene-N,S-acetal 12, 2-methylthiopyrimidine 15aec
or 2-methylthiobenzimidazole 15d and also reaction of 20 with
p-benzoquinone 19 as shown in Chart 1.
Treatment of bis-hydrazonoyl dichlorides 1 with thiourea 2 in
DMF under heating to give a single isolated 1,4-bis(3-phenyl-3H-
[1,3,4]thiadiazol-5-imino) benzene 3 via elimination of HCl and
ammonia as shown in Scheme 1.
Benzene-1,4-dicarbaldehyde 4 was reacted with methyl hydra-
zinecarbodithioate 5 to give dihydrazone 6, which was reacted with
C-phenyl-N-phenylhydrazonoyl chloride 7 in DMF to give bis-1,3,4-
thiadiazoline derivative 10 in a good yield (Scheme 2). Structure 10
was confirmed by elemental analysis, spectra and alternative syn-
thesis; benzene-1,4-dicarbaldehyde 4 was reacted with bis-2,3-
dihydro-1,3,4-thiadiazole27 11 in DMF affording product identical
in all respects (mp, mixed mp and spectra) with 10.
* Corresponding author. E-mail addresses: arashad_2003@yahoo.com. arsayed@
kfu.edu.sa.
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.04.137

5294
A.R. Sayed / Tetrahedron 69 (2013) 5293e5298
Cl
H
N
S
Ph
N
Ph
NC
NC
SCH3
NHPh
S
N
H
Ph
N
H2N
NH2
Cl
H2NHN
N
Ph
SCH3
N
H
7
2
5
Cl
12
1
O
O
O
N
Ph
H
Cl
H
NH
H
N
N
N
C2H5OOC
H3C
NH
SR
N
Ph
NH
SR
SR
N
Ph
N
H
H3C
N
Cl
Ph
N
SR
O
15b
15a
15d
19
20
15c
Where R = H or CH3
Chart 1. Starting reagents.
Cl
N
Ph
N
Ph
N
N
S
S
DMF, Heat
H
S
N
Ph
HN
N
NH
H2N
NH2
- 2HCl
- 2NH3
H
N
Cl
N
1
2
3
Ph
Scheme 1. 1,4-Bis-(3-phenyl-3H-[1,3,4]thiadiazol-2-imino) benzene 3.
H3CS(S)CHNN=HC
2-propanol
Heat
OHC
NH2NHC(S)SCH3
5
CH=NNHC(S)SCH3
6
CHO
PhC(Cl)=NNHPh
4
7
Ph
N
CH=NN=C{SC(Ph)=NNHPh}SCH3
N
H
N
Ph
SCH3
NH
S
S
Ph
N
HN
H3CS
N
N
CH=NN=C{SC(Ph)=NNHPh}SCH3
H
Ph
9
8
- 2 CH3SH
Ph
N
S
N
H
Ph
Ph
N
N
N
S
OHC
S
N
NH2
Ph
2
N
N
DMF
N
N
N
CHO
H
Ph
Ph
10
11
4
Scheme 2. Synthesis of dihydrazone 7 and bis-1,3,4-thiadiazoline 10.

A.R. Sayed / Tetrahedron 69 (2013) 5293e5298
5295
The formation of bis-thiadiazoline 10 can be explained via
elimination of methanethiol from cycloadduct 9, which is assumed
to be formed via the 1,3-dipolar cycloaddition of nitrile imide
(generate in situ by treatment of 1 with triethylamine) to the C]S
double bond of 5 or by a stepwise path involving substitution via
1,3-addition of thiol 5 to nitrile imide to give a cyclic hydrazone 8,
which is then transformed to cyclic intermediate 9. Cyclization of
the latter is achieved by elimination of methanethiol to afford
the final product 10. All attempts to isolate either intermediate
hydrazine 8 or cycloadduct 9 were unsuccessful (Scheme 2).
The required 2-cyano-3-methylthio-3-phenylaminoacrylon-
itrile 12 was prepared by the reaction of malononitrile with phe-
nyl isothiocyanate in DMF in the presence of potassium hydroxide
and the resulting thiolate was methylated with methyl iodide to
give 2-cyano-3-methylthio-3-phenylaminoacrylonitrile 12.28 Re-
cently, the synthesis of bis-triazoles29 from reactions of hydrazo-
noyl halides with ketene-N,S-acetal was reported. These principles
were extended to the reaction of bis-hydrazonoyl dichlorides 1
with 2 mol equiv of 12 in refluxing DMF/EtOH in the presence of
triethylamine proceeded smoothly to give a product that was
identified as 3,30-bis(1,2,4-triazole) derivative 14 (Scheme 3). The
structure of the latter product was elucidated on the basis of its
microanalysis and spectra as shown in Scheme 3 (see Experimental
section).
to afford 17aed. The mass spectral and the elemental analysis data
of the isolated products showed that they are free of sulfur (Scheme
4). 13C NMR spectra for 17bed could not be recorded. This was due
to the poor solubility of the isolated products in the NMR solvents
trialled.
The 1,3-dipolar cycloaddition, also known as the Huisgen cy-
cloaddition31 is a classic reaction in organic chemistry consisting of
the reaction of a dipolarophile with a 1,3-dipolar compound that
allows the production of various five-membered heterocycles. Most
of dipolarophiles are alkenes, alkynes and molecules possessing
related heteroatom functional groups (such as carbonyls and
nitriles).
Polypyrazoles based on p-benzoquinone 20 were formed from
1,3-dipolar cycloaddition polymerization reactions where bis-
nitrilimine 18 intermediates, generated in situ by the action of
excess triethylamine, with the corresponding bis-hydrazonoyl
dichlorides 20, which cycloadd to p-benzoquinone 19 to afford
final polymer 21 as shown in Schemes 5 and 6. Chemical Shifts
of pyrazoline32,33 rings disappear because should be appear
at 4.64e4.7. Polymer molecular weights for 21 approached
22,000 g/mol with polydispersity indices of approximately 2.34.
The structure of the polypyrazole 21 was elucidated on the basis of
spectral data.
Cl
H
N
N
NC
CN
Ph
NC
CN
- 2HCl
N
Ph
H3CS
H
N
H
N Ph
PhHN
SCH3
Cl
N
Ph
N
1
12
N
Ph
N
H
N
SCH3
CN
Ph
NC
13
- 2CH3SH
NC
CN
Ph
N
N Ph
CN
N
Ph
N
N
NC
Ph
N
14
Scheme 3. Synthesis of 1,4-di[(1,4-diphenyl)-5-dicyanomethylene-1,2,4-triazole)]benzene 14.
The reactions of hydrazonoyl halides with thioxo or
2-methylthio derivatives have been previously reported.30 Using
these principles, the reactions of bis-hydrazonoyl halides 1 with
2-thioxo or 2-methylthio derivatives 15aed in 1:2 molar ratios
were carried out in DMF/pyridine at reflux. Methanethiol gas
evolved during the course of the reaction, accordingly the reaction
mixture was refluxed until such a gas ceased to evolve. Bis-(1,2,4-
triazoles) 17 formed via N-atom 17aed attacks on the bis-hydra-
zonoyl dichlorides 1 to give the bis-amidazone intermediate
16aed, which in turn undergo intermediate intramolecular cycli-
zation via addition of the hydrazone NH group to C]N double bond
followed by elimination of hydrogen sulfide or methanethiol gases
3. Conclusion
In summary, the synthesis of novel bis-thiadiazoles, bis-tri-
azoles and polypyrazole derivatives based on hydrazonoyl halides
is reported.
4. Experimental
4.1. General
All melting points were determined on an electrothermal ap-
paratus and are uncorrected. IR spectra were recorded (KBr discs)

5296
A.R. Sayed / Tetrahedron 69 (2013) 5293e5298
R'
N
N
Cl
H
N
SR
R'
X
NH
R''
N
Ph
N
H
2
- 2HCl
X
N
N
Ph
Ph
R''
N
SR
N
H
Ph
N
N
Cl
N
H
15a-d
R''
R'
N
1
X
RS
16a-d
Ph
N
N
R"
N
N
R'
N
N
X
- 2RSH
X
R'
R"
N
N
Ph
17a-d
Where R = H or CH3
15-17
a
c
d
b
O
O
R'
O
Ph
H
H3CH2C
O
X
R''
H3C
Ph
H3C
Scheme 4. Synthesis of bis-{[1,2,4]triazolo[4,3-a]-5(1H)-pyrimidinone} 17aec and bis-{[1,2,4]triazolo[4,5-a]benzimidazole} 17d.
Cl
O
O
H
N
O
20
Ph
N
O
N
H
N
Ph
Ph
N
N
N
N
Ph
Triethylamine
N
Cl
N
20
Ph
n
18
21
Scheme 5. Synthesis of poly(pyrazole-p-benzoquinone) 21.
O
O
OH
H
Ph
Ph
N
N
Ph
N
N
N
N
Cl
H
N
H
N
N
2-Oxidation
O
1,3-dipolar
cycloadtion
19
Ph
N
1-Tautomerism
O
OH
Ph
N
N
N
Ph
N
H
N
N
Cl
Ph
Ph
20
18
O
O
Ph
N
N
N
N
Ph
O
O
O
O
Ph
1-Tautomerism
2-Oxidation
N
N
N
N
N
N
Ph
n
Ph
21
Scheme 6. 1,3-Dipolar cycloaddition mechanism of bis-nitrilimine 18 with, p-benzoquinone 19.

A.R. Sayed / Tetrahedron 69 (2013) 5293e5298
5297
on a Shimadzu FT-IR 8201 PC spectrophotometer. 1H NMR spectra
were recorded in CDCl3 and (CD3)2SO solutions on a Varian Gemini
300 MHz spectrometer and chemical shifts are expressed in d units
sulfoxide-d6): 6.98e7.43 (m, 24H, ArHs) ppm; m/z (%)¼644
(Mþ, 56) Anal. Calcd for C40H24N10 (644.22): C, 74.52; H, 3.75; N,
21.73. Found: C, 74.60; H, 3.79; N, 21.65%.
using TMS as an internal reference. Mass spectra were recorded on
a GCeMS QP 1000 EX Shimadzu. Elemental analyses were carried
out at the Microanalytical Canter of the Cairo University.
The starting reagents 1,34 5,35 7,36 15a,37 15bc,38 15d39 and 2040
were prepared as previously described.
4.1.5. General procedure for the preparation of bis{[1,2,4]triazolo[4,3-
a]-5(1H)-pyrimidinone} (17aec) and bis{[1,2,4]triazolo[4,5-a]benz-
imidazole} (17d). A mixture of the thioxo or 2-methylthio de-
rivatives (10 mmol) 15aed and 4-[N,N0-diphenyl(bis-hydrazonoyl
dichlorides)]benzene (1.92 g, 5 mmol) 1 were refluxed in DMF/
pyridine till hydrogen sulfide or methanthiol ceased to evolve
(12e14 h) and cooled. The cold reaction mixture was then poured
onto ice-cold hydrochloric acid with stirring. The solid that pre-
cipitated was collected, washed with water several times; dried and
recrystallized from DMF/EtOH to give final products 17aed as
shown in Scheme 4.
4.1.1. 1,4-Bis-(3-phenyl-3H-[1,3,4]thiadiazol-2-imino)benzene (3). A
mixture of 4-[N,N0-diphenyl(bis-hydrazonoyl dichlorides)]benzene
(1.92 g, 5 mmol) 1 and the appropriate of thiourea (0.76 g, 10 mmol)
2 in DMF(20 mL) was boiled under reflux for 5 h. The cold reaction
mixture was then poured onto ice-cold hydrochloric acid with
stirring. The solid that precipitated was collected. The resulting
solids filtered, washed with water several times, and crystallized
from DMF/EtOH; Yellow brown solid; Yield (69%); mp 320 ꢀC; IR:
4.1.6. Ethyl 3-(4-(6-(ethoxycarbonyl)-1,7-dihydro-5-methyl-1,7-
diphenyl-[1,2,4]triazolo[4,3-a]pyrimidin-3-yl)phenyl)-1,5-dihydro-7-
methyl-1,5-diphenyl-[1,2,4]triazolo[4,3-a]pyrimidine-6-carboxylate
(17a). Brown solid from DMF/EtOH; Yield (43%); mp 248 ꢀC; IR:
695 (CeSeC), 1612 (C]N), 3316 (NH) cmꢁ1 1H NMR (dimethyl
;
sulfoxide-d6): 7.01e8.13 (m, 16H, ArHs and ]NH). 13C NMR (di-
methyl sulfoxide-d6): at 122.7, 126.9, 129.7, 132.1, 133.9, 140.1, 147.9
and 156.2 ppm. m/z (%)¼428 (Mþ, 15). Anal. Calcd for C22H16N6S2
(428.53): C, 61.66; H, 3.76; N, 19.61. Found: C, 61.49; H, 3.87; N,
19.57%.
1733 (C]O), 1611 (C]N) cmꢁ1 1H NMR (dimethyl sulfoxide-d6):
;
1.23 (t, 6H, 2OCH2CH3), 2.37 (s, J¼7 Hz, 6H, 2CH3), 4.12 (q, J¼7 Hz,
4H, 2OCH2CH3); 5.36 (s, 2H, two pyrimidineeH) and 6.96e8.18
(m, 24H, ArHs) ppm. 13C NMR (dimethyl sulfoxide-d6): 13.9, 25.05,
57.95, 59.97, 99.54, 113.06, 119.98, 126.09, 128.06, 128.97, 129.54,
130.12, 133.45, 138.32, 142.01, 143.99, 150.01, 160.11, 167.59 ppm.
m/z (%)¼794 (Mþ, 14) Anal. Calcd for C48H42N8O4 (794.9); C, 72.53;
H, 5.33; N, 14.10. Found: C, 72.41; H, 5.26; N, 13.89%.
4.1.2. 1,4-Bis-(methyl hydrazonecarbodithioate)benzene (6). Benzene-
1,4-dicarbaldehyde (0.67 g, 5 mmol) 4 and methyl hydrazinecarbo-
dithioate (1.22 g,10 mmol) 5 in 2-propanol (40 mL) were refluxed for
30 min. The reaction mixture was cooled and solid formed was
collected and recrystallized from DMF/EtOH; Yellow; Yield (85%);
mp 226 ꢀC; IR: 3098 (]NH), 1595 (C]N), 1316 (CH3) cmꢁ1. 1H NMR
(dimethyl sulfoxide-d6): 2.55 (s, 6H, 2CH3); 7.81 (d, J¼8 Hz, 4H,
ArHs); 8.26 (s, 2H, ]CH) and 10.05 (s, 2H, NH) ppm. 13C NMR (di-
methyl sulfoxide-d6): at 18.0, 130.1, 138.1, 146.1 and 199.6 ppm. m/z
(%)¼342 (Mþ, 68); Anal. Calcd for C12H14N4S4 (342.01): C, 42.08; H,
4.12; N, 16.36. Found: C, 42.11; H, 4.30; N, 16.23%.
4.1.7. 3-(4-(1,7-Dihydro-5-methyl-7-oxo-1-phenyl-[1,2,4]triazolo
[4,3-a]pyrimidin-3-yl)phenyl)-7-methyl-1-phenyl-[1,2,4]triazolo[4,3-
a]pyrimidin-5(1H)-one (17b). Pale yellow solid from DMF/EtOH;
Yield 25%; mp >300 ꢀC; IR: 1693 (C]O), 1605 (C]N) cmꢁ1 1H
;
NMR (dimethyl sulfoxide-d6): 2.31 (s, 6H, 2CH3); 6.18 (s, 2H, two
pyrimidineeH); 7.01e8.43 (m, 14H, ArHs) ppm. m/z (%)¼526
(Mþ, 61) Anal. Calcd for C30H22N8O2(526.55); C, 68.43; H, 4.21; N,
21.28. Found: C, 68.39; H, 4.19; N, 21.31%.
4.1.3. 1,4-Bis-{1-benzylidene-2-(3,5-diphenyl-1,3,4-thiadiazol-
2(3H)-ylidene)hydrazine} (10). Method A. The appropriate of
C-phenyl-N-phenylhydrazonoyl chlorides (2.31 g, 10 mmol) 7 and
dihydrazone (1.71 g, 5 mmol) 6 in DMF (40 mL) was refluxed till no
odour of methanthiol was detected by lead acetate (methanthiol is
toxic by inhalation). The reaction mixture was cooled and solid
formed was collected and recrystallized from DMF/EtOH to give 10.
Method B. A mixture of benzene-1,4-dicarbaldehyde (0.67 g,
5 mmol) 4 and 2-hydrazino-3,5-diphenyl-1,3,4-thiadiazoline 11
(2.68 g, 10 mmol) 2 in DMF(20 mL) was boiled under reflux for 5 h.
The solid that precipitated was collected. The resulting solids
filtered, washed with water several times and crystallized from
DMF/EtOH to give 10.
4.1.8. 3-(4-(1,7-Dihydro-7-oxo-1,5-diphenyl-[1,2,4]triazolo[4,3-a]
pyrimidin-3-yl)phenyl)-1,7-diphenyl-[1,2,4]triazolo[4,3-a]pyrimidin-
5(1H)-one(17c). Brown solid from DMF/EtOH; Yield 36%; mp
>300 ꢀC; IR: 1698 (C]O), 1611 (C]N) cmꢁ1 1H NMR (dimethyl
;
sulfoxide-d6): 6.58 (s, 2H, two pyrimidineeH); 7.13e8.69 (m, 24H,
ArHs) ppm. m/z (%)¼650 (Mþ, 42) Anal. Calcd for C40H26N8O2
(650.69); C, 73.83; H, 4.03; N, 17.22. Found: C, 73.79; H, 4.10; N,
17.19%.
4.1.9. 1,4-Bis{1-phenyl-[1,2,4]triazolo[4,5-a]benzimidazole}benzene
(17d). Brown from DMF/EtOH; Yield 68%; mp >300 ꢀC; IR: 1608
(C]N) cmꢁ1; 1H NMR (dimethyl sulfoxide-d6): 7.19e8.23 (m, 22H,
ArHs) ppm. m/z (%)¼542 (Mþ, 74) Anal. Calcd for C34H22N8
(542.59); C, 75.26; H, 4.09; N, 20.65. Found: C, 75.21; H, 4.13; N,
21.01%.
Yellow brown solid; Yield (56%); mp 176 ꢀC; IR: 1632 (C]N),
1587 (C]C) cmꢁ1 1H NMR (dimethyl sulfoxide-d6): 6.72e7.83
.
(m, 24H, ArHs) and 8.43 (s, 2H, ]CH) ppm. 13C NMR (dimethyl
sulfoxide-d6): at 113.0, 119.2, 126.1, 129.1, 129.6, 130.2, 131.7, 132.1,
133.1, 134.2, 136.0, 137.6, 146.3 and 162.6 ppm. m/z (%)¼634
(Mþ, 34); Anal. Calcd for C36H26N8S2 (634.17): C, 68.12; H, 4.13; N,
17.65. Found: C, 68.24; H, 4.02; N, 17.71%.
4.1.10. Synthesis of poly{1-phenyl-3-phenylpyrazoline-1,4-benzoqui-
none} (21). To an oven-dried round bottom flask were added
p-benzoquinone (0.54 g, 5 mmol) 19 and bis-hydrazonoyl dichlor-
ides (1.54 g, 5 mmol) 20 and 20 mL dry chloroform and 4 mL DMF in
the presence of excess triethylamine (1.52 g, 15 mmol). The round
bottom flask was attached to a reflux condenser. The reaction
mixture solution was heated to reflux for 12 h. The cold reaction
mixture was then poured onto ice-cold hydrochloric acid with
stirring. The solid that precipitated was collected, washed with
water several times to give final product 21, dried to open air. The
structure of the polypyrazole 21 was elucidated on the basis of
spectral data. Polymer molecular weights approached 22,000 g/mol
4.1.4. Synthesis 1,4-di[(10,40-diphenyl)-50-dicyanomethylene-10,20,40-
triazole]benzene (14). To a mixture ketene N,S-acetal (2.15 g,
10 mmol) 12 and bis-hydrazonoyl dichlorides 1 (1.92 g, 5 mmol) in
ethanol (30 mL) and DMF (10 mL) was added triethylamine
(5 mmol) and the mixture was refluxed till methanethiol ceased to
evolve (4e6 h). The precipitate that was formed was filtered off and
crystallized from DMF/EtOH mixture to give, respectively, yielded
3,30-bis(1,2,4-triazole) derivative 14. Brown solid; Yield (42%); mp
>300 ꢀC. IR: 2221 (CN), 2199 (CN) cmꢁ1 1H NMR (dimethyl
;

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A.R. Sayed / Tetrahedron 69 (2013) 5293e5298
19. Tsuda, N.; Mishina, T.; Obata, M.; Araki, K.; Inui, A.; Nakamura; T. Jpn. Kokai Pat.
61,227,584, 1986.
20. Mawad, E. B.; Yousif, M. Y.; Metwaly, M. A. Pharmazie 1989, 44, 820.
21. Khalil, Z. H.; Abdel Hafez, A. A.; Abdo, A. A. Phosphorus, Sulfur Silicon Relat. Elem.
1989, 45, 81.
with polydispersity indices of approximately 2.379. Deep green
solid; Yield (55%); IR: 1674 (C]O), 1594 (C]N) cmꢁ1 1H NMR
.
(CDCl3): 6.82e8.01 (m, ArHs) ppm. 13C NMR (CDCl3): 113.12, 124.01,
125.93, 128.14, 130.16, 132.11, 139.15, 143.51 and 174.16 ppm.
22. Windholzed, M. The Merck Index, 9th ed.; Merck: Rahway, New Jersey, NJ, 1976;
and references cited therein.
23. Voronin, V. G.; Shramova, Z. I.; Shachilova, S. Y.; Kulikova, L. D.; Emakov, A. I.;
Zaks, A. S.; Suslina, M. L. Khim. Farm. Zh. 1985, 19, 1208.
24. Secor, H. V.; De Bardeleben, J. F. J. Med. Chem. 1971, 14, 997.
25. Crosscurt, A. C.; Van, H. R.; Wellinga, K. J. Agric. Food Chem. 1979, 27, 406.
26. Lubs, H. A. The Chemistry of Synthetic Dyes and Pigments; American Chem. Soc:
Washington, 1970.
References and notes
1. Perronnet, J.; Girault, P.; Grandadam, J. A. Fr. Demande 2,175,566, 1973.
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