Journal of Advanced Research (2010) 1, 255–290

Cairo University

Journal of Advanced Research

REVIEW

Synthesis and tautomerism of aryl- and hetaryl-azo

derivatives of bi- and tri-heterocycles
Ahmad S. Shawali

Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt

Received 29 September 2009; revised 25 November 2009; accepted 2 March 2010

Available online 16 September 2010

KEYWORDS Abstract This review summarizes results from the literature concerning synthesis and azo-hydra-
Heterocycles; zone tautomerism of arylazo- and hetarylazo-derivatives of various bi- and tri-heterocycles reported
Azodyes; by us and other research groups from 1981 to mid 2009.
Azocoupling; ª 2010 Cairo University. Production and hosting by Elsevier B.V. All rights reserved.
Tautomerism;
Hydrazonoyl halides

Introduction laser technology, data storage and solar energy conversion

Aryl- and hetaryl-azo colouring matters have been in use since
prehistoric times [1]. The interest in such colouring materials is
due to the fact that many derivatives were found useful in the
fields of material sciences and theoretical chemistry [2]. For
example, many such azo dyes have been extensively used as
dyes in various fields such as dyeing of textile fibers, coloured
plastics, biological-medical studies and advanced applications
in organic synthesis [3]. Recently, applications of such colour-
ing materials to high technology have been attracting much
attention. Dyes are used in various fields such as printing, elec-
tronic photography, colour formers, liquid crystal displays,
E-mail address: as_shawali@mail.com
2090-1232 ª 2010 Cairo University. Production and hosting by
Elsevier B.V. All rights reserved.
Peer review under responsibility of Cairo University.
doi:10.1016/j.jare.2010.07.002
Production and hosting by Elsevier
[4]. Also, some of such dyes have found use as non-linear opti-
cal (NLO) materials. Such compounds have potential use in
optical communications, information processing, frequency
doubling and integrated optics [5]. In recent years, arylazo
derivatives of various heterocyclic systems have been the sub-
ject of intense research by organic chemists [6] and dye manu-
facturers [7].
It is worth mentioning that azo-hydrazone tautomerism is
not only of importance to dyestuff manufacture but also to
other areas of chemistry. Also, azo-hydrazone tautomers have
different tinctorial strengths (and economics) and different
properties, e.g. light fastness. The intention of this review is
to focus mainly on publications dealing with the synthesis
and azo-hydrazone tautomerism of arylazo derivatives of var-
ious bi- and tri-heterocycles that have appeared in Chemical
Abstracts during the period 1981–2008. Literature prior to
1981 will not be included unless it is felt essential to use the rel-
evant information to put the problem into a common perspec-
tive. Emphasis is only given to the latest developments in the
area.
In this literature survey, the arylazo-heterocycles are re-
ported in order of the increase of (i) the number of rings, (ii)
the size of such rings and (iii) the number of heteroatoms
256 A.S. Shawali

present. The sequence of heteroatoms followed is: nitrogen, Also, it has been reported that ethyl N-arylhydrazonochlo-
oxygen, sulfur, selenium and other elements if there are any. roacetate 1E reacted with 3-phenyl-5-aminopyrazole 2 to give
The site of fusion in fused heterocycles is indicated by numbers a product to which structure 8 was assigned (Scheme 3) [8,9].
and letters and the numbering of the heterocyclic ring systems The isomeric structure 9 was discarded on the basis that the
is that reported by chemical abstracts. isolated product was recovered unchanged after being sub-
jected to oxidation treatment. Structures of type 9 are expected
Arylazo dyes of bi-heterocycles to be oxidized by analogy with 1-methyl-3-phenylhydrazono-
1,4-dihydroquinoxalin-2-one 10 which was reported to give
Arylazo derivatives of 5,5-biheterocycles 3-phenylazoquinoxaline derivative 11 upon oxidation (Scheme
4) [17–19].
1H-Imidazo[1,2-b]pyrazoles Contrary to the foregoing reports, it was indicated that
reaction of 3-phenyl-5-aminopyrazole 2 with each of the
Shawali et al. [8,9] reported that 5-amino-3-phenyl-pyrazole 2
hydrazonoyl chlorides 1A, B, C, D yielded the respective 3-
reacted readily with 2-oxohydrazonoyl halides 1A–D in etha-
substituted-1-aryl-4-phenyl-1H,6H-pyrazolo[3,4-c]pyrazoles 13
nol and yielded the respective 3-arylazo-2-substituted-1H-imi-
instead of the expected arylazo imidazopyrazole 130 or its iso-
dazo[1,2-b]pyrazoles 3 (Scheme 1). The spectral data of the
meric arylazo pyrrolopyrazole 1300 (Scheme 5) [20,21]. Such
latter were reported to be consistent with the depicted arylazo
tautomeric structure [9]. Latterly other authors applied the
same reaction for synthesis of other derivatives of 3-arylazo Ph
Ph
derivatives of 1H-imidazo[1,2-b]pyrazole 3 using other hyd-
EtOCOC(Cl)=NNHAr + N H
razonoyl bromides as precursors [10–15]. N - HCl, - EtOH N N
N NH2
Similar reaction of N-aryl 2-oxo-2-phenylethanehydrazo- 1E
2 H ArNHN O
noyl bromides 1B with 3-methyl-5-aminopyrazole 4 was re-
ported, however, to give a mixture of 5 and 6 [16] (Scheme Ph 8
3). Treatment of 5 with acid resulted in the elimination of
N H
water to give the respective 1H-3-arylazoimidazo[1,2-b]pyra- N N
zole derivative 7 (Scheme 2) [16]. The product 6 was recovered
O NNHAr
unchanged upon similar treatment with acid.
9

Scheme 3
Ph Ph
RCOC(X)=NNHAr + N N H
N NH2 N N H
1A-D
H 2 N NNHPh N N=NPh
N [O]
Ar N R
3 N O
N O
Me Me
S
R : A, Me; B, C 6H5; C, ; D, 10 11
O N
Scheme 4
Scheme 1

Ph
Me +
RCOC(Cl)=NNHAr N
+ 1A, E-G N NH2
PhCOC(Br):NNHAr N
N NH2 H -HCl
2
1B
4 H
COR
Ph COR Ph
NNHAr
N N N
N N - NH3 N NH2
Me Me
H Ar H
N PhCO N 13 12
N NH2 N NH2 Ph
Ph N=N-Ar
NNHAr
ArNHN COPh N
6 N N N
Me N N R
5 H
+ N H R H
H N N 13' ArNHN 13"
- H 2O
N
Ar N Ph
7
R : A, Me; E, EtO; F, PhNH; G, O N-

Scheme 2 Scheme 5
Synthesis and tautomerism of heterocyclic azo compounds 257

Me Ph Me Ph

CH3COC(Cl)=NNHPh + N N H
N NH2 -HCl, -H2 O N N
1A
H N
Ar N CH3
14
15

Scheme 6

finding needs further evidence to account for such a suggested 2-oxopropanehydrazonoyl chloride 1A yielded the 2-pheny-
pathway. lazo derivative 21 and not the expected 3-phenylazo derivative
The reaction between 2-oxopropanehydrazonoyl chloride 22 (Scheme 8) [25]. The latter isomer is to be the expected
1A and 3-methyl-4-phenyl-5-aminopyrazole 14 led, as ex- product of such a reaction as the pyrazole N(1)H is more basic
pected, to 1H-3-arylazo-imidazo[1,2-b]pyrazole derivative 15 than the exocyclic 5-amino group and thus the structure of the
(Scheme 6) [22]. product isolated from such reaction seems to need further
Also, it was claimed that reaction of 5-amino-3,4-disubsti- investigation.
tuted pyrazoles 16 with N-phenyl 2-oxopropanehydrazonoyl Reaction of 3-amino-4,5-dihydropyrazol-5-one 23 with N-
chloride 1A afforded the amidrazone derivative 17 (Scheme phenyl 2-oxopropanehydrazonoyl chloride 1A was reported
7) [22]. In another report [23], reactions of 5-amino-3-phenyl- to yield 3-phenylazo-2-methyl-5,6-dihydro-6-oxo-1H-imi-
4-bromopyrazole 16 with the hydrazonoyl halides 1A and 1B dazo[1,2-b]-pyrazole 25 via dehydrative cyclization of the ini-
were reported to yield the respective 2-phenylazoimidazo[1,2- tially formed amidrazone derivative 24 (Scheme 9) [22].
b]pyrazole derivative 18 which, upon treatment with sodium Recently, Shawali et al. [2] reported that when equimolar
sulfide, was converted into 19 (Scheme 7) [24]. No rationaliza- quantities of N-aryl 2-oxo-2-phenylethanehydrazonoyl bro-
tion, however, was offered. mide 1B (Ar = Ph) and each of the azo derivatives 27a–g were
A similar contradiction was also reported, indicating that refluxed in ethanol in the presence of triethylamine, the respec-
reaction of ethyl 3,5-diaminopyrazole-4-carboxylate 20 with tive 3,7-bis(arylazo)-2,6-diphenyl-1H-imidazo[1,2-b]pyrazoles
28 were formed. Similar reactions of 27 (Ar = Ph) with each
R' R" of N-aryl 2-oxo-2-phenylethane-hydrazonoyl bromides 1Ba–h
RCOC(X):NNHPh CH3COC(Cl)=NNHPh
1A, B R'/R" = Ph / Br N 1A
N NH2
NH2
H
16 + CH3COC(Cl)=NNHPh
N 1A - HCl
Ph Br N O
R' R"
23 H H
N H
N N N NH H3C N
N NH2 O
R N=N-Ph N N
PhNHN COCH3 CH3 N O - H2 O
N N O
18
Ph SH 17 N H H
PhNH N
Na2S
Ph
N H R'/R" : Ph / Br; Ph / CN; 24 25
N N H2N / PhN=N-
R N=N-Ph Scheme 9
R: A, Me; B, Ph 19

Scheme 7 KCN Ph N NHAr NH2NH2

PhCOC(Br):NNHAr
-KBr O CN - H 2O
1B
26
NH2 COOEt
Ph N Ar
+ CH3COC(Cl)=NNHPh Ar N
N Ph N PhCOC(Br):NNHAr' 1E
1A N N
N NH 2 N NH
20 N -HBr , - H 2O
H N NH2 N Ph
H
Ar
27
Ph N
N Ar' N
28
NH2 COOEt N
NH2 COOEt N NH
N
N H N H Ph N Ar'
N N N N
29
Ar / Ar' : XC6H4 / C6H5 ; C H / XC H
N CH3 N=N-Ph 6 5 6 4
Ph N CH3
X : a, 4-MeO; b, 4-Me; c, H; d, 4-Cl; e, 3-Cl; f, 3-NO2;
22
21 g, 4-NO2; h, 4-EtOCO

Scheme 8 Scheme 10
258 A.S. Shawali

also yielded the respective bis-arylazo derivative 28 (Scheme afforded the respective 6-arylazoimidazo[2,1-b]thiazoles 31
10). The other regioisomeric structures namely 2,7-bis(ary- (Scheme 11) [29]. The other isomeric structure 32 was excluded
lazo)-2,6-diphenyl-1H-imidazo[1,2-b]pyrazoles 29 were dis- for the isolated products on the basis that reaction of 2-amino-
carded on the basis that reaction of 5-amino-3-phenyl thiazoles with a-halo ketones gives 5-substituted imidazo[2,1-
pyrazole with 2-oxohydrazonoyl halides was reported to afford b]thiazoles [30] and alternate synthesis of 31 by coupling of
in all cases examined the respective 3-arylazo-2,6-diaryl-1H- diazonium salts with 3,5-diphenyl imidazo[2,1-b]thiazoles 33
imidazo[1,2-b]pyrazoles and not the isomeric 2-arylazo-3,6-dia- (Scheme 11) [30].
ryl-1H-imidazo[1,2-b]pyrazoles [2,8,9,16,22,26,27] In another report [31], it was indicated that reaction of
Although, four possible tautomeric structures A–D can be other 2-amino-4-methylthiazole derivatives 34 with the 2-
written for each of the compounds 28 (Fig. 1), they were found oxohydrazonoyl halides 1A, B led to the formation of the
to exist predominantly in the tautomeric form A on the basis of respective 5-arylazoimidazo[2,1-b]thiazoles 35 (Scheme 12).
their electronic absorption spectra and correlations of their The other expected regioisomers 36, however, were not
acid dissociation constants in both ground and excited states, formed.
pK and pK*, respectively, with Hammett equation. For exam- Reaction of 2-amino-4-phenylthiazole 30 with ethyl N-(aryl-
ple, their electronic absorption pattern in dioxane revealed in hydrazono)chloroacetate 1B in the presence of triethylamine
each case two characteristic intense absorption bands in the re- was reported to give one product that was assigned the struc-
gions 600–400 and 350–290 nm, similar to that reported for the ture 37 (Scheme 13) [9]. The other isomeric structure 38 was dis-
azo chromophore [28]. Also, the electronic spectra of 28 carded and although the isolated products 37 can have two
(Ar = Ar0 = C6H5), in solvents of different polarities showed tautomeric forms (37 and 370 ), they were assigned the ketohyd-
little, if any, shift. This result indicates that the studied com- razone tautomeric structure 37 on the basis that their IR spec-
pounds exist in one tautomeric form, namely the bis(arylazo) tra revealed CO and NH bands near 1710 and 3360 cm1,
form A (Fig. 1). Furthermore, the results of the correlations respectively. Similar reaction of 4-methyl-2-aminothiazole
of their acid dissociation constants by Hammett equation to- derivatives 34 with ethyl N-(arylhydrazono)chloroacetate 1B
gether with the spectral data provided evidence that indicates
that such compounds exist predominantly in the 1H-bis(ary-
lazo) structure, namely the tautomeric form A in both ground Ph
and excited states (Fig. 1). RCOC(X)=NNHAr + N
1A, B, H S NH2
Imidazo[2,1-b]thiazoles 30
- HX - H 2O
6-Arylazoimidazo[2,1-b]thiazoles 31 were first synthesized by
Shawali et al. [9] by reaction of the appropriate 2-aminothia-
zole derivatives with hydrazonoyl halides. Thus, reaction of
4-phenyl-2-aminothiazole 30 with 2-oxoalkanehydrazonoyl Ph R Ph N N
Ar
halides 1A, B, H were reported to give, in each case, a mixture N N
of three products, namely the hydrohalide salt of the starting N
S N N Ar S N R
2-aminothiazole, tetrazine derivative and 6-arylazo-3,5-disub- 31 32
stituted imidazo[2,1-b]thiazoles 31 [9]. However, when equiva-
ArN2Cl
lent amounts of hydrazonoyl halide and 2-amino-4-
phenylthiazole 30 were refluxed in ethanol in the presence of Ph R NC
N R : A, Me; B, Ph ; H,
triethylamine, only the respective azo-products 31 were ob- N
tained in 80% yields. Similar reaction of 2-heteroaryl-2- S N Ph N
oxohydrazonoyl bromides 1H with 2-amino-4-phenylthiazole 33 C6H4Me-p

Ar Scheme 11
Ar
N H N
N N
7 7a N N
1 Me
6 Ph N
Ph 4 2 Ph Ph RCOC(X)=NNHAr +
5
N 3 N
N N 1A, B R' S NH2
A N N H
N B N
- HX - H 2O 34
Ar Ar' Ar'
Ar
N
H N N N
N N Me R Ar
Me N N
Ph Ph Ph N N
Ph
N N N
N N Ar
R' S N N R' S N R
N H N
N N
36
C Ar' D Ar' R : A, Me; B, Ph 35
R' = H, Me, Ph
Fig. 1 Possible tautomeric structures for 3,7-bis(arylazo)-2,6-
diphenyl-1H-imidazo[1,2-b]pyrazoles. Scheme 12
Synthesis and tautomerism of heterocyclic azo compounds 259

R H
N RCOC(X):NNHAr N RCOC(Cl):NNHAr
EtOCOC(Cl)=NNHAr +
1B 1A, E, H 1B, C
R' S NH2 -HX N S
- HCl
H
30: R / R' = Ph / H - HCl,H2O 44
N COR
N COR
34: R' = Me N S NNHAr
R O Ar N S NNHAr
N H R N N H
H 45 47 - HR
N
N H
R' S N N Ar - H2O
R' S N O OH
R N Ar
37 38 N Ar N N
N N
R N=N-Ar S
R OH S N
N N N 48
46
R' N R' S N OH
S N N Ar
NC
38'
37'
R : A, Me ; B, EtO; C, PhNH;E, Ph; H, N
R' = a, H; b, Me; c, Ph
Ph N
Scheme 13 C6H4 Me -

Scheme 15

Ph H 1H-Pyrazolo[5,1-c][1,2,4]triazoles
RCOC(Cl):NNHAr N RCOC(X):NNHAr
N-Phenyl benzenecarbohydrazonoyl chloride 1I reacted with
1B, C - HCl -HX 1A, E
Ph N S 3-amino-4-(arylhydrazono)-pyrazolin-5-ones 49 in refluxing
H 39 ethanol to yield the respective 7-arylazo-1H-pyrazolo[5,1-
Ph Ph c][1,2,4]triazoles 50 (Scheme 16) [35].
N COR N COR
Similar reaction of N-phenyl benzenecarbohydrazonoyl
Ph N S NNHAr Ph N S NNHAr chloride 1I with 3,5-diamino-4-phenylazopyrazole 51 was re-
H H ported to yield 53 probably via elimination of ammonia from
42 40
- RH - H2O the intermediate amidrazone 52 (Scheme 17) [36,37]. However,
OH R reactions of the same diaminopyrazole 51 with 2-oxohydrazo-
Ph N Ar Ph N Ar noyl chlorides 1A and 1C were reported to give the respective
N N N N
amidrazones 54 (Scheme 17) [21,37]. No attempts to cyclize the
S S
Ph N Ph N latter, however, were reported.
43 41
R : A, Me; B, EtO; C, PhNH; E, Ph
Imidazo[1,2-b][1,2,4]triazoles
Scheme 14 Reaction of 3-amino-1,2,4-triazole 55 with 2-oxohydrazonoyl
halides 1A, E in ethanol was first reported by Shawali et al.
[9] to yield the respective 5-arylazo-imidazo[1,2-b][1,2,4]tria-
was reported by Shawali et al. [32] to yield, however, the other zoles 56 (Scheme 18). Similar reaction of the same aminotria-
isomeric products 38 (Scheme 13) [31]. zole 55 with the other hydrazonoyl bromides 1G was latterly
2-Mercaptoimidazole 39 was reported to react with each reported by others [15] to afford the respective 56. The other
of N-aryl 2-oxoalkanehydrazonoyl halides 1A, E in the pres- isomeric 6-arylazo derivatives 57 were not produced.
ence of triethylamine to give the respective thiohydrazonate Similar reaction of 3-amino-1,2,4-triazole 55 with ethyl N-
esters 40 [21,33,34]. Treatment of the latter with polyphos- arylhydrazonochloroacetate 1B was reported by Shawali
phoric acid resulted in their cyclization to afford 41 (Scheme et al. [9] to give 58 (Scheme 19). The other two isomeric struc-
14) [33]. tures namely 59 and 60 were discarded [9]. Structure 60 was
Similar reactions of 2-mercaptoimidazole 39 with either discarded on the basis that the product isolated was recovered
ethyl N-(arylhydrazono) chloroacetate 1B or N-(arylhydrazon- unchanged upon treatment with oxidizing agents.
o)-chloroacetanilide 1C yielded one and the same product, NH2 NNHAr
namely 43. The intermediate thiohydrazonate esters 42 were PhC(Cl)=NNHPh +
not isolated (Scheme 14) [21,34]. However, in one report [21] - HCl
1I 49 N N O
such intermediates were said to be the end products.
H
Reactions of 2-mercapto-4,5-dihydroimidazole 44 with Ph
each of N-aryl 2-oxoalkanehydrazonoyl halides 1A, E [23] Ph NH NH NNHAr
N=N-Ar
N
and 1H [29] yielded the respective products 46 (Scheme 15). N
N N - NH
Similar reactions of the 2-mercapto-4,5-dihydroimidazole 44 N O 3 N
Ph N O
with either ethyl N-arylhydrazonochloroacetate 1B or N-phe- Ph H
50 H
nyl 2-oxo-2-phenylaminoethanehydrazonoyl chloride 1C
afforded a single product, namely 48 (Scheme 15) [23]. Scheme 16
260 A.S. Shawali

NH2 N=N-Ph tives 61. Addition of the latter to preheated polyphosphoric

RCOC(Cl)=NNHPh PhC(Cl)=NNHPh acid at 80 C yielded the corresponding 2-arylazoindoles 62
N (Scheme 20) [38,39].
1A, C N NH2 1I
H Similar treatment of the amidrazones 63 (R00 = H or Me),
51
prepared from the hydrazonoyl chloride 1J and N-methylani-
NH2 N=N-Ph
NH2 N=N-Ph line, was reported to yield the isatin derivatives 65 and 66
N (Scheme 21) [39,40]. The formation of the latter products
N NH2 N was considered to result from atmospheric oxidation of the cy-
N NH2
PhNHN COR clized intermediates 64, followed, in the case of 66, by
Ph NNHPh hydrolysis.
54 52
NH2 N=N-Ph
Benzofurans
R : A, Me; C, PhNH N Ph 2-Arylazo-3-methyl benzofuran 68 were synthesized by reac-
N N - NH
3 tion of 2-oxoalkanehydrazonoyl halides 1A with phenols in
N
Ph the presence of base catalyst such as triethylamine or ethoxide
53 anion and cyclization of the resulting aryl hydrazonate esters
67 via treatment with polyphosphoric acid (Scheme 22) [38].
Scheme 17

NNHAr R"
R"
N N COR O R
RCOC(X)=NNHAr + N N + RCOC(X):NNHAr
NH2 R" NHR' - HX
1A, E, G 55 N N NH2 1A, E R" N NNHAr
H 61 R'
N=N-Ar
R"
R R
N N PPA
R
N - HO R: A, Me; E, Ph
N H N=N-Ar 2 R" N N=N-Ar R' = H, Me
N N R' R" = H, Me
56 N 62
N H
57 Scheme 20
N
R : A, Me; E, Ph; G,
S
R"
Scheme 18 R"
O H O H
+
R" NHMe
Cl NNHAr R" N NNHAr
Arylazo derivatives of 5,6-biheterocycles
1J Me
63
R" R"
Indoles OH
PPA H [O] O
Reaction of N-aryl 2-oxoalkanehydrazonoyl halides 1A, E - HO +
2 R" N NNHAr R" N NNHAr
each with aniline or N-methylaniline in ethanol in the presence Me Me
of triethylamine afforded the respective amidrazone deriva- 64 65
Me
O
R" = H, Me
N N Ar = Ph Me N O
EtOCOC(Cl)=NNHAr + Me
N NH2 66
1B
NNHAr H 55
N N Scheme 21
COOEt
N N
N NH2 EtOCO
N N NNHAr
N NH2 R
ArNHN COOEt N R
N H O Me O Me
+
H R OH
O Cl NNHAr R O NNHAr
NNHAr
NNHAr 1A
O N N N N 67
N N R
H N Me
N N N N H PPA
N H
- HO
58 60 2 R O N=N-Ar
ArNHN O R = H, Me
59 68

Scheme 19 Scheme 22
Synthesis and tautomerism of heterocyclic azo compounds 261

R' O R R' O R
+
SH X NNHAr S NNHAr
1A, E 69 R' = H
PPA
R / X : A, Me / Cl; E, Ph / Br R = H, Me, Ph
- H 2O
+
R' R RCO 2 S-Ph Ph
3
1 RCO S
S N=N-Ar N +
R' = H H 1
NH
70 2
N
R = Me, Ph H NH2
3

4
R 5
S-R S-Ph

N
N + RCOCN +
H2N
71 72

Scheme 23

Benzothiophenes
2-Arylazo-3-substituted-benzothiophenes 70 were obtained Br Et3 N MeOCO COOMe
N +
from the reactions of thiophenol with 2-oxoalkanehydrazonoyl NNHAr N
73
halides 1A, E in the presence of base catalyst and treatment of 1K N-N-Ar
-
the resulting aryl thiohydrazonate esters 69 with polyphospho-
ric acid (Scheme 23) [38]. COOMe
N
It is worth mentioning that treatment of some phenyl thi- N=N-Ar
N + N
ohydrazonate ester 69 (Ar = Ph, R = H) with PPA was re- N COOMe
MeOOC COOMe
ported to give the 3-(phenylthio) cinnolines 71 as the main Ar
product, with an 18% yield. On the other hand, similar treat- 74 75
ment of the esters 69 (Ar = Ph, R = Me, Ph) afforded the
respective products 71 (27–35% yield) together with 4-amino- Scheme 24
phenyl sulfide 72 (32–60% yield) and acylcyanide (Scheme 23)
[39]. The formation of 72 was considered to result through a
cyclodehydration path involving the aromatic ring of the Ethyl N-(arylhydrazono)chloroacetates 1B reacted similarly
hydrazone moiety. The mechanism suggested to account for with 2-aminopyridine 76 and afforded 82 which was shown to
the formation of 72 involves a rather unprecedented [3,5] rear- have the keto-hydrazone structure (Scheme 25) [9]. The other
rangement in which the sulfur atom is one of the termini, as possible regioisomeric structure 83 was discarded on the basis
depicted in Scheme 23 [39]. that reactions of 2-aminopyridine 76 with a-halo-esters were
reported to give 84 (Scheme 25) [9,17,18].
Pyrrolo[1,2-a]pyridines Similar reactions of 2-aminopyridine 76 with N-(pyrazol-5-
Reaction of N-aryl 2-pyridinecarbohydrazonoyl bromide 1K yl) 2-oxohydrazonoyl halides 1M, N in refluxing ethanol in the
with dimethyl acetylene-dicarboxylate 73 was reported to af- presence of triethylamine or piperidine were reported not to
ford a mixture of 1-arylazopyrrolo[1,2-a]pyridine 74 and the give the respective arylazo derivatives 87 [44,45]. They yielded
usual 1,3-dipolar cycloadduct 75 (Scheme 24) [41]. instead pyrazolotriazoles 86 probably via cyclization of the nit-
rilimine intermediates (Scheme 27). In this case it seems that 2-
Imidazo[1,2-a]pyridines aminopyridine 76 acted as a base catalyst.
In 1983 Shawali et al. [9] reported that reactions of 2-oxohyd-
razonoyl halides 1A, E–G and 1L each with 2-aminopyridine Thieno[2,3-b]pyridines
76 in ethanol under reflux gave the respective 3-arylazo-2- 5-Arylazothieno[2,3-b]pyridines 89 were obtained by reaction
substitutedimidazo[1,2-a]pyridine 78 (Scheme 25) [9]. The of phenacyl bromide with 3-arylazopyridine-6(1H)-thiones 88
other regioisomeric products 80 were discarded on the basis (Scheme 28) [46].
that 2-aminopyridine 76 has been known to react with a-halo 4,6-Dimethyl-2-arylhydrazonothieno[2,3-b]pyridin-3-ones
ketones to give 85 (Scheme 26) [8,9,13–15,42,43]. Further- 91 were prepared by coupling 4,6-dimethyl-thieno[2,3-b]pyri-
more, the assigned structure 78 was confirmed by the fact din-3-one 90 with diazotized anilines in ethanol in the presence
that coupling of 2-substitutedimidazo[1,2-a]pyridine 79 with of sodium acetate (Scheme 29) [47]. On the basis of their IR
N-nitrosoacetanilide or diazotized aniline in ethanol was (vCO 1680, vNH 3350) and 1H NMR spectra (dNH 11.2–
found to yield a product identical in all respects with 78 13.2), such products were assigned the indicated ketohydraz-
(Ar = Ph) [9,14]. one tautomeric structure 91.
262 A.S. Shawali

EtOCOC(Cl):NNHAr RCOC(X)=NNHA
1B 1A, E-G, L
N NH2
- HCl - HX
76

N NH N NH
OEt R
ArNHN ArNHN
O O
81 77
- H 2O

N N
H N N N N
R N=N-Ar
N 80 N N R
Ar N O Ar
82 78
ArN 2Cl
N N

O NNHAr
83 N N
N N
N N 79
Ar OH R
82'

N ; L,
R : A, Me; E, XC6 H4 ; F, ; G,
O S

Scheme 25

RCOCH2 X Me NH2
RCH(Cl)COOEt
Me Ar-N=N
N NH2 Ar-N=N CN PhCOCH 2 Br
76 COPh
R N S R N S
H 89
N N N N 88
R = Me; Ph
R R O
85 84 Scheme 28

Scheme 26

Pyrazolo[3,4-b]pyridines
Hydrazinolysis of either 92 or 93, each in refluxing ethanol Me Me O
O
containing a catalytic amount of triethylamine, was reported ArN2Cl
to give 5-arylazo derivatives of 1H-pyrazolo[3,4-b]pyridine 94 NNHAr
(Scheme 30) [46]. Such azo dyes were assigned the azo tauto- S EtOH / AcONa Me N S
Me N
meric structure as their 1H NMR spectra showed signal at d 90
91
5.5 assignable to NH2 protons and a broad signal at d 12.0
assignable to pyrazole NH proton. Scheme 29

Ph Me Ph Me
N NH2 + -
76
RCOC(Cl)=NNH N R-CO-C=N-N N
N N
1M, N - HCl
H H
Ph Me

H N
N N N N
N N
COR Het N 87 R
86
R: M, CH3 ; N, EtO

Scheme 27
Synthesis and tautomerism of heterocyclic azo compounds 263

Me Me NH2 X CHO N
Ar-N=N CN NH2 NH2 NMe 2 i N
Ar-N=N ArN2Cl N
N NNHAr
X X = CHO
R N SCH2COPh R N N 96 97 98
H N=N-Ar
92 94
Me i N
N NH
Ar-N=N CN i= N X = EtOCO
NH2NH2 N NH2
O
H
R = Me, Ph N=N-Ar
R N Cl X : A, CHO; B, EtOCO 99
93
Scheme 32
Scheme 30

A study of the electronic absorption spectra of 3-(2,4-dihy-

O OH
droxy-1-naphthylazo)-4,6-dimethylpyrazolo[3,4-b]pyridine 95a H
and 3-(2-hydroxy-1-naphthylazo)-4,6-dimethylpyrazolo-[3,4- N Ar-N=N N
N ArN2Cl N
b]pyridine 95b in a number of organic solvents indicated that O OH
they exist in basic solvents as azo-hydrazone tautomeric equi- Me N Me N
librium. However, in acetone, acetonitrile and carbon tetra-
100 OH 101
chloride, they exist mainly in the arylazo tautomeric form OH
95A (Scheme 31) [48]. N Ar-N=N
N N
N
OH OH
Pyrazolo[1,5-a]pyrimidines Me N Me N
Coupling of enaminal 96A and enamino ester 96B each with N=N-Ar N=N-Ar
102 103
diazonium salts gave the respective hydrazones 97A and 97B,
respectively (Scheme 32). Condensation of the latter hydra-
Scheme 33
zones each with aminopyrazole yielded the respective arylazo
derivatives of pyrazolo[1,5-a]pyrimidines 98 and 99, respec-
tively (Scheme 32) [49,50]. No discussion of the tautomerism
of products 99, however, was presented. OH OH
Three series of mono-arylazo- and bis-arylazo- derivatives H
N ArN2Cl N
of pyrazolo[1,5-a]pyrimidine ring system 101–103 were N N
NH2 NH2
prepared via coupling of the respective diazotized anilines
with 2-methyl-pyrazolo[1,5-a]pyrimidin-2,7(1H,7H)-dione Me N Me N
O N=N-Ar
100 (Scheme 33) [51]. Such derivatives were reported to exist 104 105
predominantly in the indicated arylazohydroxy tautomeric N
N
form. NH2
Similarly, a series of 2-amino-3-arylazo-7-hydroxy-5- Me N
methyl-pyrazolo[1,5-a]pyrimidines 105 was prepared via NNHAr
105'
coupling the respective diazotized anilines with 2-amino-7-hy-
droxy-5-methyl-pyrazolo[1,5-a]pyrimidine 104 (Scheme 34) Scheme 34
[52]. Their electronic spectra in different solvents indicated that
they exist mainly in the azo tautomeric form 105.
Also, hydrazinolysis of 106 gave 5-amino-4-phenylpyrazole Another synthetic strategy for 3-arylazopyrazolo[1,5-
107. Cyclization of the latter with diethylmalonate afforded a]pyrimidine dyes involves condensation of 5-amino-4-arylazo-
108 which, upon coupling with diazotized anilines, afforded pyrazole derivatives with various reagents. For example,
the respective 6-arylazo derivatives 109 [53]. Treatment of reaction of 5-amino-4-arylazopyrazole derivatives 112 with
the latter with Phosphorusoxy chloride gave 110 which, upon enaminones 113 afforded the respective 3-arylazopyrazol-
reaction with secondary amines, yielded 111 (Scheme 35) [53]. o[1,5-a]pyrimidine dyes 114 (Scheme 36) [26,54,55].

Me Me N=N-Ar Me
N=N-Ar NNHAr

N N N
Me N N Me N N N
H H Me N
95C 95A 95B

Ar : a, 2,4-(HO)2-1-naphthyl ; b, 2-HO-1-naphthyl

Scheme 31
264 A.S. Shawali

Ph Ph
N 2H4.H2O
PhCH(CN)CHO N
N
N NH2 N NH
106
H
107
Ph O O
Ph Ph 108
N ArN2Cl
N N ii N i N
N N N NH
R2N NR 2
Cl Cl O O
N=N-Ar
111 110 N=N-Ar NNHAr 109

R 2N = (CH2)5 N , O(CH2CH 2)2 N i = POCl3 , ii = R 2 NH

Scheme 35

R N=N-Ar
R N=N-Ar R N=N-Ar R N=N-Ar
R N=N-Ar
Ar'COCH=CHNMe2 b a N
N N N N
N N N
N 113 N N NH2
NH2 N
N Ar' H Me Me
H O Me 112
112 114 119
120 c
R N=N-Ar
R = Ph, 4-pyridyl, H2 N
Ar' = 2-naphthyl a = MeCOCH 2 COMe
N
N NH b = MeCOCH 2 COOEt
Scheme 36
c = (EtOCO)2 CH 2
O O

Reaction of enaminonitrile 115 with 3,5-diamino-4-pheny- 121

lazopyrazole 117 was reported to follow different regiochemist-
ry and gave 2-amino-3-phenylazo-pyrazolo[1,5-a]pyrimidin-
7(4H)-one 118 (Scheme 37). The latter product was also
obtained by refluxing the same pyrazole derivative 117 with ethyl
propiolate 116 in pyridine [54]. This product, although it can
have two possible tautomeric forms, was assigned the azo
tautomeric form 118A (Scheme 37). No interpretation for this
or the change in regiochemistry was given.
Similar condensation of 5-amino-4-arylazopyrazole deriva-
tives 112 with ß-diketones, ß-keto esters and diester afforded
the respective 3-arylazopyrazolo[1,5-a]pyrimidine dyes 119–
121 (Scheme 38) [36,56].
Reaction of [bis(methylthio)methylene]malononitrile and
ethyl 2-cyano-3,3-bis(methylthio)acrylate each with 3,5-
diaminopyrazole 117 in refluxing ethanol in the presence of
catalytic amount of piperidine gave the corresponding
Scheme 38
7-(methylthio)pyrazolo[1,5-a]pyrimidine 122. Treatment of
the latter with aromatic amines yielded the respective aniline
derivatives 123 (Scheme 39) [57].
Reaction of ethyl arylhydrazonocyanoacetate 124 with 3-
amino-4-arylazo-5-substituted pyrazoles 112 afforded the bis-
arylazo derivatives 125 (Scheme 40) [58].
Also, reaction of cyanoacetic hydrazide with arylhydrazon-
omalononitrile 126 yielded 3,5-diamino-4-arylazopyrazole 117.
Treatment of the latter with arylhydrazonomalononitrile affor-
ded the corresponding 2,5,7-triamino-3,6-bis-arylazopyrazol-
o[1,5-a]pyrimidines 127 (Scheme 41) [55,59,60].
In a similar manner, heating a mixture of each of 5-ami-
no-3-methyl-4-arylazopyrazoles 112 with 2-arylhydrazono-3-
ketiminobutyronitriles 128 yielded the respective bis-arylazo

H2 N N=N-Ph
H2 N N=N-Ph
NC-CH=CH-NR 2
N
115 N NH
N or
N NH2
H HC C-COOEt O H2 N NNHPh
116
117 118A
N
N N
R2 N = N
O
118B

Scheme 37
Synthesis and tautomerism of heterocyclic azo compounds 265

H2N N=N-Ar NH
Me N=N-Ar
(MeS)2C=C(CN)Z NC
H2N N=N-Ar N + Me
N N N N
N NH2 NH
N H
N NH2
MeS z Ar 128
H 112
CN 122 Me N=N-Ar
117
R N=N-Ar
N
RNH2 N N
N
N N
129 H2 N Me
RNH z N=N-Ar
Z = CN, EtOCO
CN
123 Scheme 42

Scheme 39
Reaction of 2-aminopyrimidine 130 with the hydrazonoyl
chloride 1B afforded 132 and not 133 (Scheme 44) [9]. The lat-
H2 N N=N-Ar ter structure was rejected on the basis that reactions of haloest-
EtOCOC-CN ers with 2-aminopyrimidine 130 were reported to give 134 and
+
N N-NHAr not 135 (Scheme 44) [9].
N R
124
112 H
[1,2,4]Triazolo[4,3-a]pyrimidines
R N=N-Ar Recently, Shawali et al. [63] reported one-pot synthesis of a
series of 3-arylazo-[1,2,4]triazolo[4,3-a]pyrimid-5(1H)-ones
N
N NH
141 via reactions of 2-thiouracil derivatives 136 (R0 = H) with
N-aryl arylazomethanehydrazonoyl chlorides 1O in chloro-
H2 N O form in the presence of triethylamine at reflux. Although the
125 N=N-Ar studied reactions can lead to the formation of products that

Scheme 40

- HX N
N
H2 N N=N-Ar RCOC(X)=NNHAr + N NH
NC CN N NH2 R
NC-CH2CONHNH 2 1A, E, G ArNHN
130
N N O
NHAr NH2
N - H 2O N N
126 117 H
N N N N
N N R R N=N-Ar
H2 N N=N-Ar Ar
(NC)2C=N-NHAr 131 131A
N
N N N
R: A, Me; E, XC6 H4 ; G,
S
127 H2 N NH2
N=N-Ar Scheme 43

Scheme 41

NNHAr
derivatives of pyrazolo[1,5-a]pyrimidines 129 (Scheme 42) Cl NNHAr N
N
[58]. +
COOEt N N O
N NH2
Imidazo[1,2-a]pyrimidines 1B 132
130 O
Reactions of 2-aminopyrimidine 130 with 2-oxohydrazonoyl N
halides 1A, G were first studied by Shawali et al. [9] and were ClCH 2 COOEt N N NNHAr
reported to yield the respective 3-arylazoimidazo[1,2-a]pyrimi- 133
dines 131 (Scheme 43). The other regioisomers 131A were dis- O
N N
carded on the basis that reactions of 2-aminopyrimidine with
a-halo ketones give 2-substituted imidazo[1,2-a]pyrimidines N N O N N
[9]. Other substituted 2-oxohydrazonoyl halides namely 1E 134 135
were reported to react similarly with 2-aminopyrimidine 130
to give the respective 131 (Scheme 43) [15,43]. Scheme 44
266 A.S. Shawali

O and afforded the same products 141. This finding was consid-
ArN=N-C(X):NNHAr + NH ered by the authors [63] to indicate that route (a) in (Scheme
45) is the most possible mechanism for the reactions of 1O
1O R N SR'
with both 2-thiouracil 136 and its 2-methylthio derivative.
136
Reaction of 5-phenylhydrazono-2-thioxopyrimidin-
4,6(1H,3H)-dione or its methylthio analog 142 with various
R' = H R' = H or Me hydrazonoyl halides was reported to give the respective 6-
O O N=N-Ar phenylazo derivatives of 1H-[1,2,4]triazolo[4,3-a]pyrimidin-
NH 5(4H)-one that were assigned the tautomeric structure 143A
N N-NHAr (Scheme 46) [67].
R N S-C=NNHAr R N SR'
137 N=N-Ar
140 [1,2,4]Triazolo[1,5-a]pyrimidines
O Ar Reaction of arylhydrazonomalononitrile 144 with 3-amino-
O N 1,2,4-triazole 145 afforded the respective 6-arylazo derivatives
NH N
N of 1,2,4-triazolo[1,5-a]pyrimidine 146 (Scheme 47) [59,60].
R N N(Ar)NHCS-N=NAr
R N N
N Recently, it was reported that condensation of 3-amino-
138 H Ar 1,2,4-triazole 145 with each of arylhydrazonals 97 yielded the
(b) (a) SR' respective 6-arylazo derivatives of [1,2,4]triazolo[1,5-a]pyrimi-
dines 148 and 149, respectively, (Scheme 48) [49].
O Similarly, reaction of 3-amino[1,2,4]triazole 145 with
O HS 2-arylhydrazono-3-oxo-butanoate 970 in absolute ethanol
N N=N-Ar
R N N Ar N afforded also the respective arylazo derivative of 1,2,4-triazol-
NH
Ar-N=N R N N o[1,5-a]pyrimidines 1460 [50] (Scheme 48A).
NH
HS Ar
Pyrazolo[3,4-c]pyridazines
O Azocoupling of diazotized 3-aminopyrazolo[3,4-c]pyridazine
O N=N-Ar 150 with various aromatic amines and phenols afforded the
N
Ar N
N - R'SH
respective azo derivatives 151 (Scheme 49) [68].
R N N R N N
Ar-N=N N H2 N
Ar CN N NH2
N N
139 141 +
ArNHN N
CN
Scheme 45 144 N N N N=N-Ar
H
145 NH2 146
can have either structure 139 or 141 (Scheme 45), the isolated
products were assigned structure 141. Such structural assign- Scheme 47
ment was based on 13C NMR and IR spectral data. For exam-
ple, the 13C NMR spectra of the products 141 revealed their
carbonyl carbon resonance at d 161.7–162.8 and their IR H2N
X = CHO CHO N X = EtOCO
spectra showed the CO bands at 1680–1700 cm1 [63]. These +
ArNHN N
values, while they are similar to those reported for the ‘‘ring- X N 145
acylated’’ [1,2,4]triazolo[4,3-a]pyrimidin-5-one derivatives (d 97 H
161–164 and mCO 1690 cm1), are different from those reported
for the isomeric ‘‘acylimino’’ [1,2,4]triazolo[4,3-a]pyrimidin-7- N N
N
one analogues (d 170–175 and 1660 cm1) [64–66]. N N
N
N
N N N HN
3-Chloroformazans 1O were also reported by Shawali et al. N
[63] to react similarly with 2-methylthiouracils 136 (R0 = Me)
O
O
O O 148 N=N-Ar NNHAr 149
R' N=N-Ar
PhNHN ArNHN
NH R'C(X)=NNHAr N Scheme 48
N
O N SR O N N
Ar
142
143A Me
H2N N
COMe N N
O R'
ArNHN + N
Ar-N=N COOEt HN N
N N N N
N Ar HO
97' 145
R = H, Me HO N N 146'
Ar Ar = 4-MeC6H4
143B

Scheme 46 Scheme 48A

Synthesis and tautomerism of heterocyclic azo compounds 267

+ O O
Ph N2 Ph N=N-Ar H
Me N ArN 2Cl Me N NNHAr
Ar-H N N
N N N
N N N
N N N N O N O N
150 151 Me Me 156A
155
O
Ar = 4-Me2 NC6 H4 ; 2-amino-1-naphthyl; H
2-hydroxy-3-(RNHCO)-1-naphthyl Me N N=N-Ar
N
R = Ph, 2,5-(MeO)2 , 4-ClC6 H4
N
O N
Scheme 49
Me 156B
Imidazo[3,2-d]pyrimidines
Scheme 51
Reaction of guanine 152 with diazonium salts was first re-
ported to give 153 [69]. Later it was shown that this conclusion
is erroneous and the actual structure of the products is 154 O
Ph SH
(Scheme 50) [70]. In 1991 Slouka et al. [71] prepared a series X
+ R
of 154 and showed that they have the arylazo tautomeric struc- N N
N NH2 NH
ture 154B on the basis of their 13C and 15N NMR spectra. H 1A, E Ph
Similar reactions of aromatic diazonium salts with theoph- 157 X = Cl; Br
ylline 155 were reported to give 8-arylazotheophylline deriva-
tives 156 (Scheme 51) [72]. The results of electronic
absorption spectra and quantum chemical calculations of such Ph SH
compounds revealed that they exist in the hydrazone form
Ph S N Ph Ph S R
N
156A. Electron withdrawing substituents and polar solvents fa- N N N H
N N R N N N N N
vour the azo form 156B. H H H H N Ph N
R
N Ph
158 159 160
7H-Pyrazolo[4,3-b][1,4]thiazines
Reaction of 5-amino-4-mercapto-3-phenylpyrazole 157 with R: A, Me; E, Ph
N-phenyl 2-oxohydrazonoyl halides 1A, E in ethanol in the
Scheme 52
presence of triethylamine yielded 2-(phenylazo)-3-substituted-
7-phenylpyrazolo[4,3-b]-1,4-thiazines 158 (Scheme 52) [23].
The other regioisomeric product 159, as well as the imidazopy- Imidazo[1,2-b][1,2,4]triazines
razole derivative 160, were not formed [23]. N-aryl 2-aryl-2-oxo-ethanehydrazonoyl bromides 1E was
reported to react with 3-amino-1,2,4-triazine 164 to afford 3-
Pyrazolo[1,5-a][1,3,5]triazines arylazo-imidazo[1,2-b][1,2,4]triazine 165 via dehydrative cycli-
When compound 161 was coupled with diazotized 4- zation of the initially formed amidrazone (Scheme 54) [74].
methoxyaniline in pyridine, it afforded the hydrazone deriva-
tive 162. When the latter compound 162 was treated with [1,2,4]Triazolo[3,4-b][1,3,4]thiadiazines
aqueous 5% potassium hydroxide, it underwent intramolecu- Recently, Shawali et al. [75] reported that reaction of 4-amino-
lar cyclization to furnish the respective 8-arylazo-2-phenyl-4- 3-phenyl-1H-1,2,4-triazole-5-thiol 166 with 2-aryl-2-oxoetha
thioxo-3,4-dihydropyrazolo[1,5-a][1,3,5]triazine 163 (Scheme nehydrazonoyl bromides 1E in ethanol in the presence of so-
53) [73]. dium ethoxide afforded the respective thiohydrazonates 167.

O
N ArN 2Cl
ArN 2Cl HN
NH
H2 N N
O N=N-Ar 152 O
N N=N-Ar
N HN
HN
N NH
O H2 N N
H2 N N
N NNHAr 154B
153 HN
N
H2 N N
154A

Scheme 50
268 A.S. Shawali

O O
NC NHCSNHCOPh ArN2Cl NC NHCSNHCOPh
N N
H H
161 NNHAr 162

KOH

Ar-N=N N Ph ArNHN NH

N NH - HOH N
O N O N CSNHCOPh
H H
S
163

Scheme 53

hydrazono-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-3-yl)ethane
R 171 (Scheme 56). The direct formation of 171 indicates that the
N
+ ArCOC(Br)=NNHAr' initially formed bis-thiohydrazonates 170 undergo in situ
N - HBr
N NH2 1E dehydrative cyclization under the employed reaction condi-
164 tions to give 171 as end products (Scheme 56). The intermedi-
R R acy of 170 was confirmed by their isolation and conversion
N N
N into 171. For example, reaction of 1A (Ar = Ph), taken as a
N - H 2O
N NH N N typical example of the series studied, with two molar equiva-
Ar'NHN COAr N lents of 1,2-bis(4-amino-5-mercapto-4H-1,2,4-triazol-3-yl)eth-
Ar' N Ar
ane in benzene in the presence of triethylamine at room
165
temperature afforded 170 (Ar = Ph) in 92% yield. When the
Scheme 54 latter ester 170 was refluxed in acetic acid for 1 h, it yielded
the respective 1,2-bis(7-phenylhydrazono-7H-[1,2,4]triazol-
o[3,4-b][1,3,4]thiadiazin-3-yl)-ethane 171 (Ar = Ph) in 90%
yield (Scheme 56) [76].
H Reaction of the bis-triazolethione with one mole equivalent
N N EtONa / EtOH
+ ArCOC(Br):NNHAr' of N-(p-chlorophenyl) 2-oxopropanehydrazonoyl chloride 1A
Ph N S 1E - HBr (Ar = 4-ClC6H4) in ethanol in the presence of sodium ethox-
166 NH2 ide yielded one product which was identified as 172 (Scheme
+ N N 56). This product was used as precursor for synthesis of a series
N N COAr H
of 1-(7-(4-chlorophenylhydrazono)-7H-[1,2,4]triazolo[3,4-b][1,
- HO Ph N S
Ph N S NNHAr' 2 3,4]thiadiazin-3-yl)-2-(7-arylhydrazono-7H-[1,2,4]triazolo[3,4-
N b][1,3,4]thiadiazin-3-yl)ethanes 171. Thus, treatment of 172
NH2 NNHAr'
Ar with N-aryl 2-oxopropanehydrazonoyl chlorides 1A in ethanol
167 168 in the presence of sodium ethoxide gave after workup the corre-
Ar' =XC6H4
sponding 171 in an overall good yield (72–92%) (Scheme 56) [76].
X:: a, 4-MeO; b, 4-Me; c, 3-Me; d, H; e, 4-Cl;
f, 3-Cl; g, 4-NO2; h, 4-MeCO; i, 4-EtOCO; j, 4-NO2
Arylazo derivatives of 6,6-biheterocycles
Scheme 55
Quinolines

Similar reacions of the 4-amino-1,2,4-triazole-4(1H)-thione A series of 3-arylazo-1-methylquinolines 174 was prepared by

with the hydrazonoyl bromide having electron-withdrawing
substituents in the N-aryl moiety directly afforded, however,
the respective 7-arylhydrazono-3,6-diaryl[1,2,4]triazolo[3,4-
b][1,3,4]thiadiazines 168 as end products probably via in situ
dehydrative cyclization of the respective thiohydrazonates
167 [75]. The isolated thiohydrazonates 167 were converted
into the respective triazolothiadiazines 168 by treatment with
acetic acid (Scheme 55) [75].
Also, reaction of 1,2-bis(4-amino-5-mercapto-4H-1,2,4-tria-
zol-3-yl)ethane 169 with two molar equivalents of each of N-
aryl 2-oxopropanehydrazonoyl chlorides 1A in ethanol in the
presence of sodium ethoxide at room temperature gave in each
case a single product proved to be the respective 1,2-bis(7-aryl-
reaction of the respective diazotized anilines with 1-methyl-
quinoline derivative 173 in ethanol in the presence of sodium
acetate (Scheme 57) [77,78]. The IR spectra indicate that such
dyes exist predominantly in the ketohydrazone form 174B.
Isoquinolines
A series of 4-arylazo-1-ethylthio-3(4H)-isoquinolinones 176
was prepared by reaction of the respective diazotized anilines
with 1-ethylthio-3(4H)-isoquinolinone 175 in ethanol in the
presence of sodium acetate (Scheme 58) [79]. The IR spectra
and the polarographic reduction data indicate that such dyes
in aqueous solution and in solid state exist predominantly in
the azo form 176C.
Synthesis and tautomerism of heterocyclic azo compounds 269

H
CH3 COC(Cl)=NNHAr N N 2 CH3 COC(Cl)=NNHAr
1A ( CH )2 1A
2
N S
- 2 HCl
- HCl NH2
169 H
N N N
N Ar
H ( CH2 )2
N N N N N S COCH3
CH2CH2 NH2
S N N S H 170
+
NH2 N N H -2HO
N Ar 2
172 CH3

N N N N
1A CH3 COC(Cl)=NNHAr' CH2CH2
H S N N S H
- HCl , - H2O N N N N
Ar' N N Ar
CH3 CH3
171
Ar = XC6H4

X : a, 4-CH3 ; b, 3-CH3 ; c, H; d, 4-Cl; e, 3-Cl; f, 4-EtOCO;

g, 4-CH 3 CO; h, 3-NO2 ; i, 4-NO2

Scheme 56

O
O O
N=N-Ar
NNHAr
ArN 2Cl
N O
N O N O
Me
Me Me
173 174A 174B

Scheme 57

Coumarins N=N-Ar
NNHAr
Shawali et al. [28] studied the 1H NMR, IR and UV spectra of O
O O
the diazonium coupling products of 4-hydroxycoumarin 177. ArN 2Cl
The results of such study indicated that such dyes exist in N
N
N
the keto hydrazone form 178B both in solid and solution states
176A SEt 176B
(Scheme 59). 175 SEt SEt
N=N-Ar
Quinoxalines
OH
Reactions of o-phenylenediamine 179 with the various hyd-
razonoyl chlorides 1A, E, F, P were reported to yield the N
respective 2-arylazo-1,2-dihydroquinoxaline derivatives 180
SEt
(Scheme 60) [14,80–82]. The salts of the latter products are 176C
deep coloured substances similar to compounds described as
Scheme 58
dyes [80], and the free bases of 180 were reported to be unsta-
ble in contact with air oxygen and to easily undergo oxidation
to the red quinoxaline derivatives 181 [80]. Reduction of the
formed azo derivative 181 with sodium dithionite afforded In contrast to the foregoing established findings, it was
the aminoquinoxaline derivative 182 (Scheme 60) [80]. reported that reactions of o-phenylenediamine 179 with ethyl
Reaction of o-phenylenediamine 179 with ethyl N-(arylhyd- N-(arylhydrazono)chloroacetate 1B afforded ethyl 1-aryl-4H-
razono)chloroacetates 1B was reported by several authors to benzo[c][1,2,4]triazine-3-carboxylate 185 via elimination of
yield 3-arylhydrazono-1,2,3,4-tetrahydroquinoxalin-2-ones the aromatic amino group as ammonia from the initially
184 [81–83] (Scheme 60). Such products were said to exist as formed amidrazone intermediate 183 (Scheme 60) [20]. This
a mixture of two tautomeric forms as their 1H NMR spectra unexpected result needs further investigation.
revealed the presence of six protons that exchange with deute- 1-Alkylbenzimidazole 186 reacted with hydrazonoyl chlo-
rium oxide [81]. rides 1B and gave the corresponding salts 187. The latter
270 A.S. Shawali

OH
OH O
N=N-Ar
NNHAr
ArN 2Cl
O O
O O O O

177 178A 178B

O
N=N-Ar

O OH
178C

Scheme 59

EtOCOC(Cl):NNHAr NH2 RCOC(X):NNHAr

1A, E, F, P NH2 RCOC(X)=NNHAr N R AcONH4
1B Z=H
Z = H, NO2 NH2 - HX
Z - H 2O
OH O NNHAr
179 N R
H 189 190
N NNHAr H
N NNHAr N R N R
COOEt H 180
NH2
Z 183 [O] N N=N-Ar
N NNHAr
H H
Na2S2O7 N R 191A 191B
H
H N N=N-Ar Scheme 62
N N
N COOEt NHAr
181
N N O N R
N
Z H Treatment of 2-arylhydrazonobenzo-1,4-oxazines 190 with
Z Ar
N NH2 ammonium acetate was reported to give the respective 2-ary-
185 184 182 lazoquinoxaline derivatives 191 (Scheme 62) [84,85].

R : A, Me; E, XC6 H4 ; F, benzofuran-2-yl; P, MeOCO(CH 2 )3 - 4H-1,4-Benzoxazines

o-Aminophenol 189 was reported to react with the hydrazo-
Scheme 60 noyl halides in ethanol in the presence of sodium ethoxide to
yield the respective 2-arylhydrazonobenzo-1,4-oxazine 192A
or their 2-arylazo-tautomers 192B (Scheme 63) [14,23,43,83,
N 84].
ROCOC(Cl)=NNHPh +
In contrast to the foregoing literature reports, it was
1B N
186 R' indicated that reaction of 2-aminophenol 189 with ethyl
COOR
+ NNHPh CHO N-(arylhydrazono) chloroacetate 1B afforded 2-substituted
N HO- N NNHPh 1,3,4-oxadiazines 193 (Scheme 64) [20]. This reaction requires
N Cl further confirmation.
R' N O Reaction of 2-aminophenol 189 with the 2-oxohydrazonoyl
187 R'
CHO 188A bromide 1R was reported to afford the tricyclic compound 194
N N
N Ph
N OH
R' 188B

NH2 RCOC(X)=NNHAr N R
Scheme 61

OH O NNHAr
189 H 192A
N R
yielded the 3,4-dihydroquinoxalin-2-one derivatives 188
when treated with aqueous sodium hydroxide in ethanol
(Scheme 61) [19]. HOMO calculations of the bonding ener- O N=N-Ar
gies of the two possible tautomeric forms indicated that 192B
the ketohydrazone structure 188A is more stable than the
azo form 188B [83]. Scheme 63
Synthesis and tautomerism of heterocyclic azo compounds 271

as the sole end product and no arylazo-1,4-oxazine was pro-
duced (Scheme 64) [20].
4H-1,4-Benzothiazines
Reactions of o-aminothiophenol 195 with the hydrazonoyl ha-
lides were studied by several groups of authors in ethanol in
the presence of base catalyst and in all cases they were reported
to give the respective 2-arylazo-1,4-benzothiazine 196 (Scheme
65) [14,29,43,80,83,85–89].
In contrast to the foregoing results, it was indicated that
reactions of 2-aminothiophenol 195 with N-aryl 2-oxopropane
hydrazonoyl chloride 1A and ethyl N-(arylhydrazono)chloro-

Het-CH(CN)COC(Br):NNHAr NH2
EtOCOC(Cl):NNHAr
1R OH 1B
189
H NHAr NH2
N N NNHAr
O COOEt
COCH(CN)Het
OH - NH3

H H
N NNHAr Ar
N N Ar N
N N
CN
O NH O
Het O COOEt
Het
194 193

R = Me, Ph, EtOCO, N SO2 , ,

O

O O CN
O N
Ar = XC6 H4 , N Het =
N Ph S
C6H4 Me-p

Scheme 64

NH2
RCOC(Cl):NNHAr RCOC(X):NNHAr
1A, B SH 1E, F, P, Q
195 -HX,
Het-CH(CN)COC(Br):NNHAr - H2 O

NH2 N R
NNHAr
S COR S NNHAr
- NH3 H NHAr 196A
N N
Ar COCH(CN)Het H
N SH N R
N
S COR S N
197 N
196B Ar

H H
N Ar N NNHAr
N
N
CN
S NH S
Het Het
198

R: A, Me ; B, EtO; E, XC6 H4 ; F, ; P, MeOCO(CH2 )3 -

O
; Q,
O O
CN
O N
Ar = XC6 H4 , N Het =
N Ph S
C6H4 Me-p

Scheme 65
272 A.S. Shawali

acetate 1B afforded the respective 2-substituted 1,3,4-thiadia- corresponding 2-arylazo-3-phenyl-4-methylbenzothiazines 200

zines 197 (Scheme 65) [20,21]. Such reactions need further rein- (Scheme 67) [86].
vestigation to confirm such ambiguous results.
In another report, it was indicated that reaction of 2-amino- Pyridazino[4,3-c]pyridazines
thiophenol 195 with the hydrazonoyl bromide 1A, B afforded Treatment of 201 with methylhydrazine was reported to give
no arylazobenzothiazine; instead it yielded the tricyclic com- 2,6-dimethyl-3-oxo-2,3,4,6,7,8-hexahydropyridazino[4,3-c]pyr-
pound 198 as the sole product (Scheme 65) [90]. idazine-4-arylhydrazone 202. The structure of the latter was
Treatment of 2-arylazobenzo-1,4-oxazines 190 with phos- based on its IR and 1HNMR spectra together with X-ray anal-
phorus pentasulfide was reported to give the respective 2-ary- ysis (Scheme 68) [91].
lazo-1,4-benzothiazine derivatives 196 (Scheme 66) [84,85].
2-Methylaminothiophenol 199 reacted similarly with N-aryl
Arylazo derivatives of 5,5,6-triheterocycles
2-oxo-2-phenylethanehydrazonoyl bromides 1E and gave the
Indeno[2,1-b]thiophenes
Recently three series of 2-(4-substituted-phenylazo)-3-cyano-
NH2
8-substituted-indeno[2,1-b]thiophenes 204 were prepared by
RCOC(X)=NNHAr N R P2S5
coupling diazotized 2-amino-3-cyano-8-substituted-inde-
no[2,1-b]thiophene 203 with dialkylaminobenzene (Scheme
OH O NNHAr 69) [92].
189 190
H Pyrrolo[2,1-b]benzothiazoles
N R N R
2-Cyanomethylbenzothiazole 205 was reported to react with
S N=N-Ar
the bis-hydrazonoyl chlorides 1S in ethanol in the presence
S NNHAr
of sodium ethoxide to give the respective bis-hydrazone deriv-
ative 206. Oxidation of the latter with lead tetraacetate (LTA)
196A 196B
afforded 1,2-bis-(arylazo)-3-cyanopyrrolo[2,1-b]benzothiazoles
Scheme 66 207 (Scheme 70) [93].

Imidazo[1,2-a]benzimidazoles
Me When the hydrazonoyl bromide 1G was refluxed with 2-ami-
NHMe nobenzimidazole 208 in ethanol, it furnished 3-arylazo-2-(ben-
O Ph NH
+ COPh zothiazol-2-yl)-1H-imidazo[1,2-a]benzimidazoles 209 (Scheme
SH - HBr
Br NNHAr S 71) [15].
NNHAr
199 1E
Me
N Ph
Imidazo[2,1-b]benzothiazoles
- HO Reactions of 2-aminobenzothiazole 210 with N-aryl 2-
2 S N=N-Ar oxopropanehydrazonoyl chloride 1A and N-aryl 2-oxo-2-
200 phenylethanehydrazonoyl bromides 1E were reported to give
the respective 3-arylazoimidazo[1,2-a]benzothiazoles 211
Scheme 67 (Scheme 72) [31]. In another report, it was indicated, however,
that reaction of the hydrazonoyl chloride 1A with 2-aminoben-
zothiazole yielded the unexpected amidrazone derivative 214
O NNHPh N Me which was not cyclized. No rationalization, however, was gi-
MeNHNH2 N ven [22].
N When N-phenyl 2-oxo-2-(pyrazol-3-yl)ethanehydrazonoyl
AcOCH2-CH O O Me N O
bromide 1H was used in reaction with 2-aminobenzothiazole
NNHPh 210, it was claimed that it gave rise to the formation of 2-
201 202
phenylazoimidazo[1,2-a]benzothiazoles 213 (Scheme 72) [29].
Scheme 68

CN CN
1) NaNO2 / HCl
NH2 N
S 2) RR'NC6 H5 S N NRR'
X 203 X
204
X = O, (CN)2 C

R/R' = Me / Me, Et / Et, Et / HOCH2 CH2 , HOCH2 CH2 / HOCH2 CH2

Scheme 69
Synthesis and tautomerism of heterocyclic azo compounds 273

N No rationalization was given to account for this different reg-

+ ArNHN=C(Cl)-C(Cl)=NNHAr iochemical result.
S CH2CN - HCl
1S Similar reaction of 2-aminobenzothiazole 210 with ethyl N-
205 NNHAr (arylhydrazono)chloroacetate 1B afforded 212 via cyclization
NNHAr
NNHAr NNHAr of the initially formed respective amidrazone (Scheme 72) [31].
N N
Cl - HCl
S CH-CN S CN Thiazolo[3,2-a]benzimidazoles
206 2-Mecrapto-1H-benzimidazole 215 was reported to react with
N=N-Ar ethyl (N-arylhydrazono)chloroacetate 1B and 2-phenylamino-
N=N-Ar 2-oxoethanehydrazonoyl chloride 1C in the presence of base
LTA N catalyst and yielded the corresponding thiohydrazonate esters
S CN 216 (Scheme 73) [23]. Acid treatment of the latter products re-
207 sulted in their cyclization to give 2-arylhydrazono-thiazolo[3,2-
a]benzimidazol-3-one 217 (Scheme 73) [23].
Scheme 70 Similar reaction of 2-oxopropanehydrazonoyl chloride 1A
[23] and 2-oxo-2-(hetaryl)ethanehydrazonoyl bromide 1T
[23,29,89,94] each with 215 afforded the respective thiohydraz-
onate esters 216 that cyclized upon heating to give the corre-
sponding arylazo thiazolobenzimidazoles 218 (Scheme 73).
N
+ Het-COC(Br):NNHAr 1H-Imidazo[1,2-c]pyrazolo[4,3-e]pyrimidines
- HBr
N NH2 4-Aminopyrazolo[3,4-d]pyrimidine 219 was reported by Shaw-
1G Ar
H 208 ali et al. [95,96] to react readily with 2-oxoalkanehydrazonoyl
N
N halides 1A and 1U to give the respective 3-arylazo-1H-imi-
NNHAr
N
R dazo[10 ,20 -c]pyrazolo[4,3-e]pyrimidines 220 (Scheme 74). When
N COR ethyl N-(arylhydrazono)chloroacetates 1B was employed in lieu
- H 2O N
N NH N of 1A or 1U, the reaction gave 221 (Scheme 74).
H
H 209
N 1H-Dipyrazolo[1,5-a:4’,3’-e]pyrimidines
R =
S When compounds 222 were treated with hydrazine hydrate,
the initially formed hydrazino derivatives 223 underwent
Scheme 71 in situ cyclization to give the respective 1H-Dipyrazolo[1,5-

N
+ RCOC(X)=NNHAr
- HX S NH2 - HX
1A, B, E, H
NNHAr 210
N COR N

S NH S NH
R = EtO
Ar - EtOH ArNHN COR
- H 2O
N 214
N NNHAr
R O
N N - H2O R= Het
N N
S S Het
211 212A N=N-Ar
N
N=NAr N
S
OH 213
N
N
S
X = Cl, Br
212B CN

R : 1A, Me ; B, EtO ;E, Ph; H, N

N Ph
C6H4 Me-4

Scheme 72
274 A.S. Shawali

RCOC(Cl):NNHAr N COR
N
1 H
N
N SH TEA N S N Ar
H - HCl H
215 216

R = EtO, PhNH
- H 2O R = Me, Het
- RH
O
R
N
N=N-Ar N N Ar
N H
S
S N
N
218 217A

R : A, Me; B, EtO; C, PhNH; E, Ph; OH

NC Me N=N-Ar
N
H, ; T,
N N S S
Ph N N
217B
C6H4-Me-p Ph

Scheme 73

NH2
R' a:40 ,30 -e]pyrimidine derivatives 224. Although two possible
RCOC(X)=NNHAr N EtOCOC(Cl)=NNHAr tautomeic structures can be written for such products, their
1B 1
1A, U N H NMR data were consistent with the hydrazone structure
N N
O 224B (Scheme 75) [57].
Ph N
219
R Ph
N N NNHAr Arylazo derivatives of 5,6,6-triheterocycles
R' N
N N=N-Ar N N Pyrrolo[2,1-a]isoquinolines
N Ph 221A
N N Recently, reactions of 2-(6,7-diethoxy-3,4-dihydroisoquinolin-
OH 1-yl)acetonitrile 225 with each of the 2-oxohydrazonoyl halides
Ph 220 N
Ph 1A, E, L, U have been examined in tetrahydrofuran in the pres-
N N=NAr ence of triethylamine and found to result in the formation of
R' = Ph, PhCH=CH
N the respective 2-(arylazo)pyrrolo[2,1-a]isoquinoline derivatives
R: A, Me; U, 2-theinyl N N
Ph 221B 226 (Scheme 76) [97]. Similar reaction of the same acetonitrile
derivative with ethyl N-(arylhydrazono)chloroacetate 1B affor-
Scheme 74

H2 N H2 N N=N-Ar H2 N
N=N-Ar N=N-Ar

N N N
N N N N N N

MeS X NH2 NH X X
HN
CN CN N 224A
222 223 NH2
H2 N NNHAr
X = NH2 , OH
N
N N

N X
N
NH2
224B

Scheme 75
Synthesis and tautomerism of heterocyclic azo compounds 275

R' RCOC(X):NNHAr
EtOCOC(Cl):NNHAr
N 1A, E, L, U
1B R'
NC R'
R'
225
N
N R'
R'
COR
COOEt NC
NC
NNHAr
NNHAr

R' R'
N O N R
R' R'
NC NNHAr NC N=NAr
227 226
R' = MeO, EtO
R: A, Me; E, Ph; L, 2-naphthyl; U, 2-thienyl

Scheme 76

MeO MeO NH). In solid state such compounds were reported to exist
ArN2 Cl only in the azo tautomeric form 233A (Scheme 79) because
N N N=N-Ar
MeO MeO their IR spectra showed bands at v 3434–3420 and 3395–
NC Ph 3371 cm1. A study of the effect of substituent on their elec-
NC Ph
229
tronic spectra revealed that some of these dyes exist in a single
228 Ar = Ph, 4-MeC6 H4 tautomeric form and some others as an equilibrium mixture of
the azo and hydrazone forms, according to the nature of the
Scheme 77
substituent [100].
Reaction of arylhydrazonomalononitrile 126 with 2-amino-
ded 2-(arylhydrazono)pyrrolo[2,1-a]isoquinolin-1-carbonitrile benzimidazole 208 yielded 1,3-diamino-2-arylazo-pyrimi-
227 (Scheme 76) [97,98]. do[1,2-a]benzimidazoles 234 (Scheme 80) [59].
Recently it was reported that 3-(arylazo)pyrrolo[2,1-a]iso- Similarly, condensation of 2-aminobenzimidazole 208
quinoline derivatives 229 can also be prepared by coupling 2- with each of ethyl 2-arylhydrazono-3-oxo-butanoate 126A
phenyl-pyrrolo[2,1-a]isoquinoline-1-carbonitrile 228 with the [50] and 2-arylhydrazono-3-oxopentanal 126B [60] in reflux-
appropriate diazonium salts (Scheme 77) [99]. ing ethanol afforded the respective 3-arylazo derivative of
pyrimido[1,2-a]benzimidazole 234A and 234B. The isomeric
Pyrido[1,2-a]benzimidazoles structure of the latter, namely 234C, was discarded on the
Reaction of arylhydrazonomalononitrile 126 with 2-cyanom-
ethylbenzimidazole 230 was reported to give the respective
NH2
1,3-diamino-2-arylazo-4-cyano-pyrido[1,2-a]benzimidazoles
231 (Scheme 78) [62]. N

Pyrimido[1,2-a]benzimidazoles N N O
232 H
A series of 4-amino-3-arylazo-1H-benzo[4,5]imidazo[1,2-a]pyr- NH ArN 2Cl NH2
imidin-2-ones 233A was prepared by coupling of the respective NNHAr N=N-Ar
diazotized anilines with 4-amino-1H-benzo[4,5]imidazo[1,2- N N
a]pyrimidin-2-one 232 (Scheme 79) [100]. Their 1H NMR in N N O N N O
DMSO-d6 indicated that such azo derivatives exist as a mix- H H
ture of the azo and hydrazone tautomeric forms as such spec- 233B 233A
tra showed two signals in the regions d 10.2–10.1 (N1–H),
Scheme 79
11.94–10.76 (NH2) and 10.2–8.81 (imine NH and hydrazone

N CN

CN N N
ArNHN + NH2
CN N CN
H H2 N N=N-Ar
126 231
230

Scheme 78
276 A.S. Shawali

CN N N
ArNHN + N
NH2
CN N N
NH2
126 H
208 234 H2 N N=N-Ar

Scheme 80

Et-COC(=NNHAr)CHO N
EtOCOC(=NNHAr)COMe
NH2
N
H
208
N N
N N
N N
Me
N
234B 234A HO
Et N N N
N N N
Et
Ar Ar
Ar = XC6H4 Ar = 4-MeC6H4
N
X = H, 4-NO2 234C N
Ar

Scheme 80A

S
N
N
S + PhNHNH2
EtOCOC(=NNHAr)COMe N N NHN=C(Cl)COOEt
NH2 Me
N
H
1V
O N NNHPh . HCl
N
EtOCO O
Ar N
N NHNHPh N
Scheme 80B N N
N N N
H H 236
basis of NOE difference that revealed that the ethyl group -EtOH
235
and benzimidazole-H are spatially proximal (Scheme 80A)
O O
[60].
NHNHPh N=N-Ph
N N
[O]
Pyrimido[2,1-a]benzothiazoles N
N N N
Condensation of 2-aminobenzothiazole with ethyl 2-arylhyd- N N
H 237 H
razono-3-oxobutanoate was reported to give the respective 3- 238
arylazo derivatives of pyrimido[1,2-a]benzimidazole (Scheme
80B) [61]. Scheme 81

Triazino[4,3-a]benzimidazoles
Reaction of phenylhydrazine with ethyl N-((benzimidazol-
2-yl)hydrazono)chloroacetate 1V was reported to give the
hydrochloride salt of 4-phenylhydrazono-3-oxo-[1,2,4]triazi-
no[4,3-a]benzimidazole 236 (Scheme 81) [48]. This result
requires further investigation as the expected product from
cyclization of the initially formed intermediate 235 is expected
to have the isomeric structure 237 or its oxidation product 238
(Scheme 81).
Furo[2,3-b]quinoxalines
El-Ashry et al. [101] reported that reaction of 5-phenylfuran-
2,3,4-(5H)-trione 239 with o-phenylenediamine gave 240
(Scheme 82). Treatment of the latter with arylhydrazine gave
a mixture of the azo derivative 241 and the hydrazide 242.
The 1H NMR spectra of 241 in DMSO-d6 revealed that
such dyes exist as a mixture of the iminohydrazone 241A
and azo-enamine forms 241B in a ratio of 3:2, respectively.
For example, the spectra showed in each case three different
NH proton signals at d 10.47 (NNH), 10.63 (N4-H) and
11.47 (N1-H). Attempting to acetylate 241 with acetic anhy-
dride in pyridine at room temperature or in refluxing acetic
anhydride gave 243 [101]. The 1H NMR spectra of the latter
revealed that each of such dyes exist as an equilibrium
mixture of the tautomeric forms 243A and 243B (Scheme
82).
Synthesis and tautomerism of heterocyclic azo compounds 277

O O O N
NH2
+ H2 N 240
Ph O O NH2 Ph O O
239 ArNHNH2
NNHAr
N CONHNHAr
N
+ CH(OH)Ph
N CH(OH)Ph
N O
242 H
241A
N=N-Ar N=N-Ar
H H
N Ph N
Ac2O CH(OH)Ph
O
N N O
H
243A 241B
NNHAr
N Ph

O
N

243B

Scheme 82

Pyrazolo[5,1-c]benzo[1,2,4]triazines H2 N N=N-Ar H2 N N N=N-Ar

Reaction of resorcinol with diazotized 3-amino-4-phenylhyd-
2 CH2=CHCN
razino-1H-pyrazolin-5-one 244 was reported to give 245. The N N
NH2 N NH
latter was assigned the indicated hydroxyazo tautomeric form N 246
H 16
245B although no spectral data were given to confirm this O
assignment (Scheme 83) [102]. H2 N N=N-Ar

Dipyrimido[1,2-b:20 ,10 -e]pyrazoles N

N NH CH2=CHCN
The arylazo derivatives 246 were prepared by either heating CH2=CHCN
247 with one molar equivalent of acrylonitrile or heating 16 247 O
with two molar equivalents of acrylonitrile (Scheme 84)
[36]. Scheme 84

1H-Pyrazolo[3,4-d]pyrimido[1,6-b][1,2,4]triazines When ethyl N-(arylhydrazono)chloroacetate 1B was used in

1-Phenyl-3-substituted-5-amino-4-imino-1H-pyrazolo[3,4-d]- this reaction, it gave 250 (Scheme 85) [96,103].
pyrimidine 248 was reported to react with each of N-aryl-2-
oxoalkanehydrazonoyl halides 1A, E, U to give the respective Arylazo derivatives of 6,6,6-triheterocycles
6-arylazo-pyrazolo[3,4-d]pyrimido[1,6-b][1,2,4]triazines 249.
[1,2,4,5]Tetrazino[3,2-b]quinazolines
N-Aryl arylazomethanehydrazonoyl chlorides 1O have been
ArNHN N N reported to react with 3-amino-2-thioxo-4(1H)quinazolinone
OH ArNHN N 2Cl 251a or its methylthio derivative 251b in refluxing ethanol in
+ N the presence of triethylamine (Scheme 86) [104]. Such reactions
N O N afforded the respective 3-arylazo-6H-[1,2,4,5]tetrazino[3,2-
O N H
OH
H b]quinazolin-6-ones 252 via elimination of hydrogen sulphide
245A O and methanethiol respectively from the initially formed amid-
244
razone intermediates (Scheme 86).
Ar-N=N Ar-N=N N N
N N
Hetarylazo- of Bi- and Tri-heterocycles
N
O N HO N
N 2-[(4-Pyrazolyl)azo]indazoles
H
245B OH
245C OH Reaction of diazotized 2-aminoimidazole 253 with 3-methyl-1-
phenyl-5(4H)-pyrazolone 254 yielded the respective azo dye
Scheme 83
278 A.S. Shawali

NH
R' NH2
RCOC(X)=NNHAr N EtOCOC(Cl)=NNHAr
N 1B
1A, E, U N N
O
R Ph 248
NNHAr
N=N-Ar N
N R' N
Ph N N H
N H N
N N N 250A
N N Ph OH
Ph
249 N=NAr
N
R' N
R' = 2-thienyl, 2-thenoyl, Ph, PhCH=CH N H
R / X: A, Me / Cl; E, Ph / Br; U, 2-thienyl / Br N
N N
Ph 250B

Scheme 85

O priate 5-pyrazolone derivatives 254. Such dyes were considered

NH2 to have the indicated hydrazone structure 259A (Scheme 89)
N TEA
+ ArN=N-C(Cl):NNHAr [105].
N SR 1O - HCl Coupling of diazotized 2-aminobenzothiazole derivative
251
258 with the enaminonitrile yielded the coupling product
O N=NAr O H
NH-C
260. Hydrazinolysis of the latter with hydrazine or phen-
N N N=NAr
NNHAr N ylhydrazine yielded the respective azo dyes 261 (Scheme 90)
N SR - RSH N [107].
N N
Ar
252
3-[(5-Thiazolyl)azo]pyrazolo[3,4-b]pyridines
R = a, H; b, Me

Scheme 86 Reaction of 2-amino-4-substituted-thiazole 263 with 4,6-dim-

ethylpyrazolo[3,4-b]pyridine-3-diazonium nitrate 262 afforded
the respective azo dye 264. The latter products were assigned
255. Although the latter can have three tautomeric structures the azo tautomeric structure although four possible tautomeric
255A–C, it was assigned the indicated ketohydrazone tauto- structures can be written for each of such dyes (Scheme 91) [108].
meric structure 255A (Scheme 87) [105].
H2 N
2-[(4-Pyrazolyl)azo]benzothiazoles N NH2 NH2
N NH
NHN=C(CN)2 N
S N N
Hydrazinolysis of 2-benzothiazolylhydrazonomalononitrile S
256 was reported to give the azo dye 257 (Scheme 88) [106]. 256 257 H2 N
Other dyes of this series 259 were prepared by coupling the
respective 2-benzothiazole-diazonium salts 258 with the appro- Scheme 88

Me
N + N
N
O N Me
N
H
N 2Cl
N N N
Ph H H
N
253 254 255A O N
Ph
N
Me N
N N N Me
H
N N N N
H
255C HO N 255B NH
Ph O N
Ph

Scheme 87
Synthesis and tautomerism of heterocyclic azo compounds 279

3-[(3-Isoxazolyl)azo]pyrazolo[5,1-c][1,2,4]triazines the corresponding diazonium salt. Treatment of the latter with

Diazotization of 5-amino-3-methyl-pyrazole derivative 265
and coupling the resulting diazonium salt with each of
malononitrile and ethyl cyanoacetate yielded the respective
coupling products that cyclized in situ to give 4-amino-7-
methyl-8-(3-isoxazolylazo)pyrazolo[5,1-c][1,2,4]-triazines 266.
FT-IR spectra of such dyes revealed also that they exist pre-
dominantly in the indicated azo-enamine tautomeric form
266 (Scheme 92) [109].
3-[(2-Thiazolyl)azo]pyrazolo[5,1-c][1,2,4]triazines
Diazotization of 5-amino-3-methyl-4-(thiazolylazo)-1H-pyra-
zole 267 with sodium nitrite in sulfuric acid in acetic acid gave
each of malononitrile and ethyl cyanoacetate yielded the
respective coupling products that cyclized in situ to give 4-ami-
no-7-methyl-3-substituted-8-(2-thiazolylazo)pyrazolo[5,1-c][1,
2,4]triazines 268. FT-IR spectra of such dyes revealed that they
exist predominantly in the indicated azo-enamine tautomeric
form (Scheme 93) [109].
3-[(3-Pyrazolyl)azo]quinolines
Coupling of diazotized 3-amino-pyrazole derivatives 269 with
2,4-dihydroxyquinoline 270 yielded the corresponding azo
dye 271 (Scheme 94) [3]. The IR spectrum of such a dye
showed no C‚O bands and its 1H NMR spectrum revealed
NH proton signals at d 13.98–13.85 and in addition two OH

Me
X X
N N Me
+
N N
S N 2Cl O S N
N H N
R N
O
258 254 259A R

X = H, 6-Me, 6-O2N, 6-MeO

X Me
N
N
S N
N
N N
R = Ph, N
259B HO
N N N R

Scheme 89

N NC-CH=C(NH2)Me
N
S N 2Cl
S NHN=C(CN)-C(Me)=NH
258 260

N Me
RNHNH2
N
S N
N
N
261 H2 N
R

Scheme 90

An N
NRR'
Me N 2 NO3 S
An Me N N
+ N
N
N N
Me N RR'N S
H Me N N
H
262 263 264

R/ R' : H/ H, H/ Me, H/ Ph, Ph/ Ph

An = 1-phenyl-2,3-dimethyl-dihydro-5-pyrazolon-4-yl

Scheme 91
280 A.S. Shawali

Me OH
Me N O
O +
O Me N N N ClN 2 Me
N N OH
Me N N O
270 272 N Me
i N
N N N OH
N NH2 ii N
H N N
H2 N
265 266
R
N OH
i = NaNO2 / H2 SO4 / AcOH
273
ii = NC-CH2 R, R = CN, EtOCO
Scheme 95
Scheme 92
3-[(5-Methyl-isoxazol-3-yl)azo]coumarins

3-[(5-Methyl-isoxazol-3-yl)azo]coumarin 277 was prepared by

signals at d 10.41 and 19.97. On the basis of these data such
coupling 4-hydroxy-coumarin 276 with diazotized 3-amino-5-
dyes were assigned the indicated azo-hydroxy tautomeric
structure [3]. methylisoxazole 272 (Scheme 97). This dye, on the basis of
its IR (tCO 1740 cm1) and 1H NMR (d 14.7) spectral data,
was assigned the keto-hydrazone form 277B [111].
3-[(3-Isoxazolyl)azo]quinolines
3-[(5-Thiazolyl)azo]quinolines
The title azo dye 273 was prepared by coupling 2,4-dihydroxy-
quinoline 270 with diazotized 3-amino-5-methylisoxazole 272
The 3-(2-methyl-5-thiazolylazo)quinoline-2,4-dione dye 278
(Scheme 95). This dye was proved on the basis of its IR (no
was prepared by coupling diazotized 2-amino-5-methylthiazole
tCO) and 1H NMR (d 10.84, OH) and was assigned the indi-
derivative with 4-hydroxy-2(1H)quinolinone 270 (Scheme 98).
cated azo-hydroxy tautomeric form 273 [3].
In solution, this dye 278 may exist in four possible tautomeric
Also, diazotized 3-amino-5-methyl-isoxazole 272 was cou-
structures. However, its FT-IR spectra showed no carbonyl
pled with 8-hydroxyquinoline 274 and gave the respective
band and its 1H NMR spectrum in DMSO-d6 did not show
azo dye 275 (Scheme 96) [110].
NH signal. These findings were considered as evidence that it
has the indicated azo-hydroxy form in solid state and in solu-
N tion [3].
N R'
Me N N S
Me N N S R' 3-[(5-Thiazolyl)azo]coumarins
i N
N N N The 3-(2-thiazolylazo)coumarin dyes 279 were prepared by
N NH2 ii
H N coupling diazotized 2-aminothiazole derivatives in nitrosyl sul-
H2 N furic acid with coumarin derivative 276 (Scheme 99) [111].
267 268
R = CN, EtOCO R Although four possible tautomeric structures can be written
for such dyes, they were assigned the azo-hydroxy forms
i = NaNO2 / H2 SO4 / AcOH R' = H, Me 279A and 279B according to the nature of the substituent R.
ii = NC-CH2 R For example, the 1H NMR spectra revealed that dye 279
(R = H) exists in one tautomeric form whereas dye 279
Scheme 93
(R = Me) exists as a mixture of two tautomers [111].

3-[(1,2,4-Triazol-3-yl)azo]quinolines
OH
H
N N Similar coupling of diazotized 3-amino-1,2,4-triazole deriva-
+
ClN2 tives 280 with quinoline derivative 270 afforded the respective
N OH coupling products 281 (Scheme 100) [111]. On the basis of
R H their 1H NMR spectral data such dyes were assigned the
270 269 N
N two azo-hydroxy tautomeric forms 281A and 281B according
OH to the substituent present. For example, compound 281a
N N (R = H) exists in one tautomeric form, namely 281A,
R = H, MeS R whereas, compound 281b (R = MeS) exists as a mixture of
azo-hydroxy and keto hydrazone forms 281A and 281B,
N OH respectively [111].
271 Recently a series of 8-hydroxy-5-[(1,2,4-triazol-3-yl)azo]
quinolines 282 were prepared by the coupling of diazotized
Scheme 94
Synthesis and tautomerism of heterocyclic azo compounds 281

O
N Me

N N
N O
+
ClN 2 Me
N
N
OH 275
274 272 OH

Scheme 96

OH
N O
+
ClN 2 Me
O O
272
276
O O
N Me N Me
OH O
N N N N
H

O O O O

277A 277B

Scheme 97

OH
N 3-amino-1,3,4-triazoles 280 with 8-hydroxyquinoline 274
+
ClN2 Me (Scheme 101) [110].
S
N O
H
N 3-[(1,2,4-Triazol-3-yl)azo]coumarins
270 Me
OH
S Coupling of diazotized 3-amino-1,2,4-triazole derivatives 280
N N with 4-hydroxy-coumarin 276 afforded the respective cou-
pling products 283 [111] (Scheme 102). On the basis of their
1
N OH
H NMR spectral data such dyes were reported to have one
of the two tautomeric forms 283A and 283B according to
278 the substituent present. For example, compound 283a
(R = H) exists in one tautomeric form, namely 283A,
Scheme 98
whereas compound 283b (R = MeS) exists as a mixture of

OH
N
+
ClN2 S R
O O
276
N R N R
OH O
S S
N N N N

O O O OH

279A R = H, Me 279B

Scheme 99
282 A.S. Shawali

OH
H
N N
+
ClN 2 N R
N O
H 280
270
N N
N R N R
OH O
N N
N N H N N H
H

N O N O
H H
281A R = a, H; b, MeS 281B

Scheme 100

azo-hydroxy and keto hydrazone forms 283A and 283B, 3-[(3-Isoxazolyl)azo]pyrimido[1,2-a]benzimidazoles

respectively [111].
Reaction of diazotized 2-amino-5-methyl-isoxazole 272 with
3-[(1,3,4-Thiadiazol-2-yl)azo]quinolines
4-amino-2-oxopyrimido[1,2-a]benzimidazole 286 yielded the
respective 3-[(3-isoxazolyl)azo]-pyrimido[1,2-a]benzimidazole
Coupling of diazotized 3-amino-1,3,4-thiadiazole derivative 287, which was considered to exist as a mixture of the two
with 2,4-dihydroxyquinoline 270 afforded the respective azo tautomeric forms 287A and 287B (Scheme 105) [112].
dye 284 [111]. On the basis of its IR spectrum, which showed
HO and C‚O bands, such a dye was considered to exist as 3-[(2-Thiazolyl)azo]pyrimido[1,2-a]benzimidazoles
a mixture of the four tautomeric forms 284A–D (Scheme
103) [111].
Coupling of diazotized 2-amino-5-substituted-thiazole with 4-
Also, diazotized 2-amino-1,3,4-thiadiazoles couples with 8-
amino-2-oxopyrimido[1,2-a]benzimidazole 286 yielded the
hydroxyquinoline 274 to give the respective thiadiazolylazo
respective 3-[(2-thiazolyl)azo]-pyrimido[1,2-a]benzimidazoles
derivatives 285 (Scheme 104) [110].
288, which were considered to exist as a mixture of the two
tautomeric forms 288A and 288B (Scheme 106) [112].

N
N N=N
N N
+
ClN 2 R N
N R H
N H
OH 274 280
N
R = H, HS-, MeS-, Et 282
OH

Scheme 101

OH
H
N N
+
ClN 2 N R
O O
276 280
N N
N R N R
OH O
N N
N N H N N H
H

O O O O
283A R = a, H; b, MeS 283B

Scheme 102
Synthesis and tautomerism of heterocyclic azo compounds 283

OH imidazoles 289, which were also considered to exist as a mix-

N N ture of the two tautomeric forms 289A and 289B (Scheme
+ 107) [112].
ClN 2 S
N O
H
2-[(5-Pyrimidinyl)azo]benzothiazoles
270
N N
N N
OH O Diazotized 2-aminobenzothiazole was reported to couple with
S S
N N N N
4-hydroxy-6-methyl-2-thiouracil 136 to give the respective azo
H dyes 290, which were assigned the indicated azo-tautomeric
structure (Scheme 108) [113].
N OH N O Recently, it was reported that diazotized 3-aminopyridine
H
291 was coupled with 8-hydroxyquinoline 274 and gave the
284A 284B
N N respective azo dye 292 (Scheme 109) [110].
N N
OH O
S S 3-[(2-Benzothiazolyl)azo]pyrazolo[5,1-c][1,2,4]triazines
N N N N
H
Similar reaction of the diazonium salt, which derived from
N O N OH 5-aminopyrazole derivative 293, with each of malononitrile
H
284C 284D and ethyl cyanoacetate yielded the respective coupling prod-
ucts that cyclized in situ to give 4-amino-7-methyl-8-(2-ben-
Scheme 103 zothiazolylazo)pyrazolo[5,1-c][1,2,4]triazines 294. FT-IR
spectra of such dyes revealed that they exist predominantly
in the indicated azo-enamine tautomeric form 294 (Scheme
110) [109].
N N
+
ClN 2 R 3-[(2-Benzimidazolyl)azo]quinolines
S
N
OH 274 N 3-[(2-Benzimidazolyl)azo]-2,4-dihydroxyquinoline 296 was
N N=N prepared by coupling 2,4-dihydroxyquinoline 270 with diazo-
S tized 2-aminobenzimidazole 295 (Scheme 111). The 1H NMR
R of this dye in DMS-d6 revealed signals at d 13.98 (NH) and
R = H, HS-, MeS-, Et
10.41 (OH), which indicate that such a dye exists as the azo-
285 N enol form [3].
OH
3-[(2-Benzothiazolyl)azo]quinolines
Scheme 104
3-[(2-Benzothiazolyl)azo]quinolines 297 were prepared by cou-
pling 2,4-dihydroxyquinoline 270 with diazotized 2-amin-
3-[([1,2,4]Triazol-3-yl)azo]pyrimido[1,2-a]benzimidazoles obenzothiazoles. The 1H NMR of this dye in DMS-d6
revealed a broad signal at d 10.37–10.93 (OH) and its IR spec-
Similar coupling of diazotized 2-amino-5-substituted-[1,2,4]tri- trum showed no carbonyl absorption band. Such data indicate
azole with 4-amino-2-oxopyrimido[1,2-a]benzimidazole 286 that such a dye exists in the indicated azo-enol form 297
yielded the respective 3-[(3-triazolyl)azo]-pyrimido[1,2-a]benz- (Scheme 112) [3].

NH2
Me
N
+
O
N N N N 2Cl
O
H 272
286 Me Me

NH2 NH
O O
N N N N N N
N N H

N N O N N O
H H

287A 287B

Scheme 105
284 A.S. Shawali

NH2

N N
+
N N R S N 2Cl
O
H
286 N N
NH2 NH
S R
N N S R
N N N
N H

N N O N N O
H H
288A 288B
R = a, H; b, Me

Scheme 106

NH2
R
H
N N
+
N
N N N N 2Cl
O
H R
286 H R
N H
NH2 N
N NH
N N
N N N
N N N
N H
N N O
H N N O
H
289A R = a, H; b, MeS 28 9B

Scheme 107

3-[(2-Benzimidazolyl)azo]coumarins
OH

N N 3-[(2-Benzimidazolyl)azo]coumarin 298 was prepared by cou-

+
N 2Cl
pling 4-hydroxycoumarin 276 with diazotized 2-aminobenzim-
S Me N SR
HO idazole in nitrosyl sulfuric acid. The 1H NMR of this dye in
136 DMS-d6 revealed signals at d 12.5 (OH), 14.8 (NH) and 15.3
N
R = a, H; b, Me N N (NH), which indicate that such a dye exists as an equilibrium
N SR mixture of azo-enol and keto-hydrazone tautomeric forms
N
S Me 298A and 298B, respectively (Scheme 113) [3].
290
3-[(2-Benzothiazolyl)azo]coumarins
Scheme 108
A series of 3-[(2-benzothiazolyl)azo]coumarins 299 was pre-
pared by coupling 4-hydroxycoumarin 276 with diazotized
2-aminobenzothiazoles. The 1H NMR of this dye in DMS-
d6 revealed two broad signals at d 13.6–13.7 (OH) and
14.7–14.8 (NH), which indicate that each of such dyes exists
as an equilibrium mixture of azo-enol and keto-hydrazone
tautomeric forms 299A and 299B in DMSO-d6 (Scheme
N 114) [111].
N N
3-[(2-Benzimidazolyl)azo]pyrimido[1,2-a]benzimidazoles
N 2Cl
+
Diazotized 2-amino-benzimidazole coupled with 4-amino-2-
N N N oxopyrimido[1,2-a]benzimidazole 288 and yielded the respec-
OH tive 3-[(2-benzimidazolyl)azo]-pyrimido[1,2-a]benzimidazole
274 OH
291 292 300, which was reported to exist as a mixture of the two tau-
tomeric amino-azo form 300A and the imino-hydrazone
Scheme 109 form 300B (Scheme 115) [112]. For example, its 1H NMR
Synthesis and tautomerism of heterocyclic azo compounds 285

N R'
N
R' S
Me N N
Me N N S
i N
N N N
N NH2 ii N
H
H2 N 294
293 R

i = NaNO2 / H2 SO4 / AcOH R' = H, MeO

ii = NC-CH2 R, R = CN, COOEt

Scheme 110

OH
N
revealed signals at d 12.45 (NH2), 11.93 (NHCO) and 9.78
+ (=NH).
ClN 2 N
N OH H
3-[(2-Benzthiazolyl)azo] pyrimido[1,2-a]benzimidazoles
270 295
N
OH Similarly, three series of 3-[(2-benzthiazolyl)azo] pyrimido[1,
N 2-a]benzimidazoles 301 were prepared by coupling diazotized
N N H
2-amino-benzothiazole with 4-amino-2-oxopyrimido[1,2-a]
benzimidazole 286. Such dyes were found to exist as equilib-
N OH rium mixture of the two tautomeric amino-azo form 301A
296 and the imino-hydrazone form 301B (Scheme 116) [112]. For
example, its 1H NMR revealed signals at d 12.50–12.40
Scheme 111 (NH2), 10.3–10.32 (NHCO) and 9.60–9.63 (=NH) [112].

OH
N
+ R
ClN 2 S
N OH R
270
N
OH
S
N N

R = Cl, MeO, O2 N
N OH 297

Scheme 112

OH
N
+
ClN 2 N
O O H
276

N N
OH O
N N
N N H N N H
H

O O O O

298A 298B

Scheme 113
286 A.S. Shawali

OH
N
+ R
ClN 2 S
O O
276 R R

N N
OH O
S S
N N N N
H

O O O O

299A 299B
R = H, MeO, O 2 N

Scheme 114

NH2

N N
+
N N O N N 2Cl
H H
286

N N
NH2 NH
N N N N N N
N H N H H

N N O N N O
H H
300A 300B

Scheme 115

NH2

N N
+ R
N S N 2Cl
N O
H
286
N N
R NH R
NH2
S N N S
N N N H
N

N N N O
N O H
H

301A 301B
R = H, EtO, O2 N

Scheme 116

Conclusion and prospects application of such colouring compounds in industry. For

The literature survey presented herein indicates that the synthe-
sis and tautomerism of aryl- and hetaryl-azo derivatives of the
various heterocycles have attracted the interest of many re-
search groups all over the world. Such colouring compounds
seem to be promising dyes. However, the author feels that there
are still several problems that need further clarification before
example, it should be pointed out that the observation of more
than one form in the 1H NMR spectra of some compounds
could be more probably explained by E/Z isomerism e.g. on
the moiety C‚N–NH–Ar. A similar case of the E/Z isomerism
has been recently reported by Simunek et al. [114], where the
isomerism has been proved by means of multinuclear magnetic
resonance using isotopically labeled compounds. Also, in most
Synthesis and tautomerism of heterocyclic azo compounds
literature reports covered herein, the quantification of the posi-
tion of azo-hydrazone equilibria is determined by means of
NMR based on comparison of relevant NMR parameters of
the equilibrium mixture with the parameters of standards. As
the azo-hydrazone equilibrium mixture of a single compound
proceeds only through the very fast intramolecular rearrange-
ment of the proton between two atoms (N or O), it seems that
the application of N-15 NMR spectroscopy seems to be the best
method available for this purpose [115,116]. Furthermore, the
literature survey revealed that there are several aspects of such
colorants that still need further study. For example, the role of
solvent polarity, temperature and other factors that control the
existence of such tautomeric mixtures could be elaborated.
Also, the tautomerism-coloristic properties correlations of such
dyes need to be explored. Finally, it is hoped that this review
will encourage many researchers to shed light on such prob-
lems, which will facilitate the utility of such azo colouring com-
pounds in industry.
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