Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties: Dye synthesis, product characterization and properties

Article abstract of DOI:10.1007/s00706-011-0658-4

Two synthesis strategies were used for the generation of azulene-1-yl diazenes substituted at C-3 with a phenyl-chalcogenyl moiety, the synthesis of azulenes substituted at C-3 followed by azo-coupling and azulene substitution at C-3 in azulene-azo dyes.

Full text of DOI:10.1007/s00706-011-0658-4

Monatsh Chem (2011) 142:1271–1282
DOI 10.1007/s00706-011-0658-4
ORIGINAL PAPER
Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene
moieties: dye synthesis, product characterization and properties
•
Alexandru C. Razus Liviu Birzan
•
•
•
Mihaela Cristea Eugenia Andreea Dragu
Anamaria Hanganu
Received: 20 September 2010 / Accepted: 8 September 2011 / Published online: 20 October 2011
Ó Springer-Verlag 2011
Abstract Two synthesis strategies were used for the
generation of azulene-1-yl diazenes substituted at C-3 with
a phenyl-chalcogenyl moiety, the synthesis of azulenes
substituted at C-3 followed by azo-coupling and azulene
substitution at C-3 in azulene-azo dyes. The last synthetic
route seems to give more satisfactory results for the syn-
thesis of the desired chalcogenic derivatives. Another
target of this study was to investigate the changes induced
by the phenyl-chalcogenic substitution on the NMR and
UV-vis spectra, and also to compare this effect with the
one exerted by halogen atoms and by strongly electron
donating groups such as AcNH or PhCOO. Whereas the
latter groups exhibit a strong influence on the NMR and
UV-vis spectra, PhS, PhSe, or PhTe groups as well as
halogen atoms produce only a small effect because of the
moderate change in electron distribution over the entire
molecule.
with phenyl or phenylene as aromatic groups (compounds
I–III) are represented. The synthesis of these dyes and
several physico-chemical properties as well as the NLO [9,
10] and electrochemical [11, 12] behavior of the com-
pounds were investigated. These studies proved the
importance of the position of the N=N groups in the
molecules and of the alkyl substitution at the azulenyl
fragment for the properties of the compounds, e.g., on
UV-vis or NMR spectra.
The goal of this study was to investigate the influence on
the properties of the resulting products induced by the
coupling of the five-member ring of the azulenyl moiety in
compounds I–III with an electron-donating or -releasing
group such as PhS, PhSe, PhTe, CH3CONH or PhCOO.
Our interest was sustained by the fact that a single piece of
information is available so far on azulenic compounds
containing the chalcogenic elements selenium or tellurium:
1-(selenocyanato)azulene and 1-(tellurocyanato)azulene
were obtained in the reaction of azulene with KXCN
(X = Se, Te) in the presence of Cu2? ions (yields 42 and
7%, respectively) [13].
Keywords Dyes ꢀ Chalcogenides ꢀ
Electrophilic substitutions ꢀ Azulene ꢀ Diazenes
Introduction
Results and discussion
In our studies on aromatic azo-dyes containing an azulenyl
group, we were able to obtain several such compounds with
one [1–6] or two diazenyl [7, 8] groups, as well as with one
or two azulenyl moieties. In Scheme 1, such compounds
Dye synthesis
For the generation of the azulenyl substituted compounds
I–III, two synthetic routes are available, namely substitu-
tion of the azulene followed by the azo coupling with
the corresponding diazotized anilines or the preparation of
the compounds I–III and subsequently substitution of the
azulenyl moiety. The first route involved electrophilic
substitution at C-1 of the azulene for the formation of the
compounds represented in Scheme 2. Compounds 1 [14], 2
A. C. Razus ꢀ L. Birzan (&) ꢀ M. Cristea ꢀ
E. A. Dragu ꢀ A. Hanganu
Institute of Organic Chemistry ‘‘C.D. Nenitzescu’’
of the Romanian Academy, Spl. Independentei 202B,
PO Box 35-108, 060023 Bucharest, Romania
e-mail: lbirzan@cco.ro
123

1272
A. C. Razus et al.
Scheme 1
I
II
III
Rn = H or alkyl
X = different substituents
meta- andpara- isomers
Rn, Rn(a), Rn(b) = H, alkyl
substitution of the azulenyl moiety with a PhSe group, we
have tried to use the commercially available reagent
PhSeBr. The obtained reaction mixture contained nearly
equal amounts of the products substituted with PhSe and
Br, 24 and 27, respectively, and a high amount of polymer.
The introduction of the PhTe group was more difficult
because the PhTeX reagents (X = Cl or Br) are not com-
mercially available and they must be generated in situ. We
tried to obtain PhTeX by oxidation of diphenyl ditelluride.
The oxidation with bromine was unsuccessful; however,
the use of SO2Cl2 as oxidant afforded the PhTeCl reagent,
and hence, compound 25 was generated in 28% yield. The
expected chlorinated by-product 26 was not detected in the
reaction mixture.
R
AcNH PhCOO PhS PhSe PhTe
Azulene
1
2
3
4
5
1-5
Scheme 2
[15], and 3 [16, 17] were already obtained following this
route and were fully characterized. The last compound was
obtained in good yields in the reaction of azulene with
PhSCl, although some problems arose in product isolation.
However, our attempts to synthesize the corresponding
selenium and tellurium compounds 4 and 5 using a similar
reaction pathway encountered difficulties. Therefore, we
have used only compounds 1–3 as starting reagents for the
first reaction route.
The same reaction route was used starting from the meta
and para mono-azulenyl bis-diazenes 28 and 29
(Scheme 4). When PhSeBr was used, the diazene conver-
sion was about 50%, and the reaction afforded the dyes 30
and 32 along with the 3-bromo derivatives 34 and 35.
Replacing PhSeBr with PhSeCl, the reaction occurred more
cleanly, and only the phenylseleno derivatives 30 and 32
were obtained in comparable yields (35 and 32%, respec-
tively). For the synthesis of the corresponding compounds
containing PhTe as substituent, a mixture of Ph2Te2 and
SO2Cl2 was used, and the products 31 and 33 were formed
in lower yields. It is interesting to note that when com-
pounds 28 or 29 were treated with PhSCl, the products 10
and 13 were obtained in higher yields as compared with the
first reaction route described above (results shown in
Scheme 4 vs. Scheme 3). Due to the same reactivity of
both azulenyl moieties in the bis-diazenes 36 and 37, a
complex composition of the reaction mixture generated by
the substitution of these groups is expected. For the sub-
stitution with PhSe both PhSeBr and PhSeCl were used as
starting reagents, and the results are shown in Scheme 5.
The reaction with PhSeBr afforded a very complex
reaction mixture. Thus, along with the compounds with one
or two PhSe groups (38–41), the mixture contained also the
Synthesis starting from substituted azulenes 1–3
The coupling reaction between azulenes 1–3 and diazo-
nium salts obtained from (phenylazo)anilines 6 and 7 or
(azulenylazo)anilines 14 and 15 occurred smoothly in
moderate yields as shown in Scheme 3.
The yields were influenced to a small extent by the
reciprocal position of amino and azo functions. Because of
the poor results obtained starting from compound 3, for the
synthesis of the compounds substituted with PhS the
second preparation route was also taken into account.
Synthesis starting from the diazenes I–III
Investigation of the second reaction route started by
introduction of the phenyl-chalogene group at the easily
accessible dye 1-(4-methoxyphenylazo)azulene (22) [18],
and the encouraging results are outlined in Scheme 4.
Treatment of compound 22 with PhSCl at room tempera-
ture gave the desired compound 23 in good yield. For the
123

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties
1273
Scheme 3
1"
1
1'
1.NaNO2/CCl2HCO
2.NaOAc
OH
R
AcNH PhCOO PhS
6 1,3-Isomer
7 1,4-Isomer
1,3-Isomer
Yield (%): 39
8
9
41
10
20
1,4-Isomer 11
Yield (%): 31
12
46
13
22
1-3
1.NaNO2/CCl2HCO
2.NaOAc
OH
1'
1
1"
R
AcNH PhCOO PhS
1,3-Isomer 16
17
18
Yield (%): 29
20
13
14 1,3-Isomer
15 1,4-Isomer
1,4-Isomer 19
Yield (%): 37
20
25
21
12
Scheme 4
1'
1
R
PhS
23
PhSe
24
30
PhTe
25
28
26 X = Cl
27 X = Br
22
Comp.
Yield (%) 50
28 1,3-Isomer
29 1,4-Isomer
R
PhS
10
40
13
42
PhSe
PhTe
1,3-Isomer
Yield (%)
1,4-Isomer
Yield (%)
30
31
19
33
29
32*
32
for both reactions
R = PhS, reagent PhSCl
18**
R = PhSe, reagent PhSeBr
R = PhTe, reagent Ph2Te2 + SO2 Cl2
* 30% compound with R = Br34
**50% compound with R = Br35
123

1274
A. C. Razus et al.
Scheme 5
1
1"
(a) PhSeBr
(b) PhSeCl
1'
36 1,3-Isomer
37 1,4-Isomer
Resulted products using reagent (b) and yields (%)
R1; R2
PhSe; H Yield
PhSe; PhSe Yield
1,3-Isomer
1,4-Isomer
38
40
32
26
39
41
21
15
Brominated by-products resulted using reagent (a)
R1; R2
1,3-Isomer
1,4-Isomer
PhSe; Br Br; H Br; Br
-
42
45
43
46
44
by-products substituted with PhSe and Br (44) or only with
Br (42, 43, and 45). The isolation and characterization of
the obtained compounds were difficult because of the high
number of generated products. However, for the structure
assignment of the brominated products, these compounds
were obtained by bromination of diazene 36 and 37. The
diazene 36 was brominated (55% conversion) to afford the
compounds 42 (20%) and 43 (10%), while from 37 the
compounds 45 (31%) and 46 (31%) (38% conversion)
resulted. When PhSeCl was used as substitution reagent,
only the phenylselenyl compounds 38–41 were generated
in moderate yields (Scheme 5). Any attempts to introduce
the phenyltelluro group at bis-diazenes 36 and 37 failed
despite the successful substitution of mono-azulenyl
diazenes 31 and 33.
Table 1 1H NMR spectra of 3-substituted 1-(4-methoxyphenyl-
azo)azulenes (d in ppm)
3-Substituent (compound) Azulenyl protons
2
4
5
6
7
8
Cla (26)
PhS (23)
Bra (27)
PhSeb (24)
Ia (47)
8.18 8.38 7.28 7.71 7.33 9.22
8.37 8.59 7.30 7.70 7.40 9.27
8.28 8.33 7.30 7.71 7.35 9.19
8.52 8.68 7.48 7.78 7.38 9.35
8.46 8.28 7.33 7.77 7.39 9.22
8.69 8.68 7.49 7.80 7.41 9.35
8.15 8.20 7.20 7.64 7.26 9.22
PhTeb (25)
Mec (48)
a
NMR spectra at 300 MHz [21]
b
c
NMR spectra at 400 MHz
NMR spectra at 300 MHz [1]
The influence on NMR spectra of diazenes
by substitution with PhTe, PhSe, or PhS
the dH values of the same azulene protons are comparable
and are slightly deshielded relative to the protons belon-
ging to the corresponding compound 48 with a methyl
group at C-3 (Table 1). As an exception, the proton at C-2
in the azulenyl moiety is deshielded by C-3 substitution in
the order Cl \ Br \ I due to a superposition of the aniso-
tropic, steric, and electronic effects of these atoms [20].
The azulenyl protons of the chalcogene compounds 23–25
are deshielded in comparison with the similar ones belonging
to the halogenated diazenes. The phenyl-chalcogene group
deshields the proton at C-2 more strongly in the order
PhS \ PhSe \ PhTe. The same tendencies as described
above were observed for the azulenyl protons of more
complicated compounds with structures II or III substituted
at C-3 in the azulene.
The influence of the several substituents (as AcNH or
–OCOR) at C-3 in 1-(phenylazo)azulenes with formula
I [19] as well the general aspects of the NMR spectra
recorded for the compounds with the structures II and III
have already been detailed by us [7, 8]. Therefore, we have
turned our attention mainly on the influence exerted on the
proton chemical shifts dH by the chalcogene substituents
because of the novelty of these compounds. We have
focused our attention mainly on compounds 23–25 with
more simple structure. The obtained data were compared
with those of similar compounds substituted with halogen
atoms (26, 27, and 47, Table 1), namely the atoms
belonging to the same period of elements that contains the
chalcogene elements. Thus, for the C-3 halogenated dyes
As expected, the dH values of the phenyl and phenylene
protons in the studied molecules were only little influenced
123

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties
1275
Table 2 Absorption maxima of the main visible band (kmax in nm) of 3-substituted mono-azulenyl bis-diazenes and bis-azulenyl bis-diazenes in
MeOH
Isom.
Substituent at C-3 in azulenyl moiety
Mono-azulenyl bis-diazene
Bis-azulenyl bis-diazene
Ha
NHAc
BzO
PhS
PhSe
PhTe
Br
Ha
NHAc
BzO
PhSe
1,3
1,4
a
428
469
460 (8)
440 (9)
429 (10)
475 (13)
431 (22)
472 (32)
430 (23)
474 (33)
434 (26)
471 (35)
442
520
462 (30)
538 (19)
448 (31)
520 (20)
444 (38)
523 (40)
504 (11)
483 (12)
Data from Ref. [7, 8]
by the change in azulenyl substituents because they are too
far from the substitution center. Several aspects regarding
the dH values of the protons belonging to the compounds II
and III were discussed in our previous papers [7, 8].
Se, or Te), namely the synthesis of azulenes substituted at
C-3 followed by azo-coupling and the substitution of
azulene at C-3 in the azulene-azo dyes I–III. The last
synthetic route seems to be more satisfactory for the
synthesis of the desired chalcogenic derivatives. Unfortu-
nately, the products were obtained in modest yields
because of the high amount of by-products. However, the
novelty of these compounds and the change that could
result in their redox and other properties compensated this
disadvantage. Another target of this study was to investi-
gate the changes produced by phenyl-chalcogenic
substitution at C-3 belonging to the azulen-1-yl group on
the NMR and UV-vis spectra and to compare this effect
with the one exerted by halogens and also by strongly
electron-donating groups such as AcNH or PhCOO.
Whereas the last groups exhibit a strong influence on the
NMR and UV-vis spectra, PhS, PhSe, or PhTe groups as
well as halogen atoms produce only a small effect because
of moderate changes in the electron distribution over the
molecule. Studies regarding the acido-basic behavior and
several aspects on the redox properties of the synthesized
diazenes are in progress.
UV-vis spectra
The absorption maximum kmax of the main visible band of
1-(4-methoxyphenylazo)azulene (22) showed a small
bathochromic shift (6–8 nm) by substitution of the azulene
at C-3 with PhTe, PhSe, or PhS as well as with halogen
atoms [21]. However, the value was almost independent of
the nature of the introduced substituent.
The modification of the kmax values for mono-azulenyl
bis-diazenes or bis-azulenyl bis-diazenes by the azulenyl
substitution at C-3 with PhS, PhSe, PhTe, or halogens was
also not significant (Table 2). As expected, the batho-
chromic effect exerted by the change in the position of the
N=N groups from 1,3 to 1,4, observed in the parent com-
pounds, was also maintained in all studied substituted
compounds. The higher mobility of nonbonding electrons
of the nitrogen or oxygen atoms in AcNH or PhCOO
groups induced a bathochromic effect of over 30 nm for
AcNH, whereas in the case of PhCOO it was limited to
about 10 nm (Table 2).
Experimental
In the visible region of the spectrum, a great number of
small, poorly defined bands are also present between 500
and 700 nm. Due to their multitude and their low intensi-
ties, although they contribute to the final color of the
compounds (brownish in solutions), these bands are diffi-
cult to interpret correctly.
Melting points were measured on a Kofler apparatus (Reich-
ert Austria). UV-vis spectra were recorded in methanol on a
Varian Cary 100 spectrophotometer. 1H and 13C NMR
spectra were obtained on Bruker Avance DRX instruments
(1H: 400 MHz, 13C: 75 MHz and 100.62 MHz); J values are
given in Hz. COSY correlation experiments were used for
the assignment of proton positions; the numbering of atom
positions is shown in Schemes 3–5. Mass spectra were
recorded on a Varian 1200L Quadrupole/MS/MS spec-
trometer by direct injection in ESI or APCI. Elemental
analyses were obtained on a Perkin Elmer CHN 240B device
and agreed satisfactorily ( 0.2%) with calculated values.
Column chromatography was carried out using silica gel.
Dichloromethane (DCM) was distilled over CaH2. Small
samples from the compounds were crystallized for melting
Conclusions
Years after Nefedov’s report [13] on the azulene deriva-
tives substituted with SeCN and TeCN, to our knowledge,
this is the first investigation on the synthesis and charac-
terization of azulen-1-yl selenyl and telluryl derivatives.
Two synthetic strategies were tried for the generation of
azulene-1-yl diazenes substituted at C-3 with PhX (X = S,
123

1276
A. C. Razus et al.
(E)-1-[3-(Acetylamino)azulen-1-yl]-2-[3-[(E)-
phenyldiazenyl]phenyl]diazene (8, C24H19N5O)
points from petroleum ether. 4-Aminoazobenzene, 1-(4-
methoxyphenylazo)azulene, 3- and 4-(azulen-1-ylazo)azo-
benzenes, and compounds I (Rn=H) and II (Rn=H) were
obtained as described in the literature [1–8].
Dark brown crystals; m.p.: 208 °C; UV-vis (MeOH): kmax
(log e) = 231 (4.34), 296 (4.44), 337 (sh, 4.33), 461
(4.25) nm; 1H NMR (400 MHz, CDCl3): d = 2.34 (s, 3 H,
Me), 7.21 (t, 3J = 9.7 Hz, 1 H, 5-H), 7.34 (t, 3J = 9.8 Hz,
Syntheses routes
3
1 H, 7-H), 7.53 (t, J = 7.1 Hz, 2 H, 300-H, 500-H), 7.55 (t,
3
3J = 7.3 Hz, 1 H, 400-H), 7.64 (t, J = 7.7 Hz, 1 H, 50-H),
Azocoupling reactions
7.71 (t, 3J = 9.2 Hz, 1 H, 6-H), 7.93 (d, 3J = 7.0 Hz, 1 H,
To a stirred solution of aromatic amines (2 mmol) in 8 cm3
dichloroacetic acid at 0 °C a solution of 140 mg sodium
nitrite (2 mmol) in 1 cm3 water was added slowly, main-
taining the temperature below 5 °C. After 10 min the
mixture was added at 0 °C to a very well-stirred solution of
azulene 1–3, 28, or 29 (2 mmol), and 12 g potassium
acetate in 100 cm3 methanol. If the potassium acetate was
not completely dissolved, the yields decreased signifi-
cantly. The mixture was stirred at 0 °C for 1 h. The pH of
the mixture was adjusted to neutral with sodium hydroxide
solution, which was carefully added. The products were
repeatedly extracted with DCM. The organic layers were
washed with water, dried over sodium sulfate, and the
solvent was removed in vacuum. The residue was frac-
tionated by column chromatography on silica gel with a
mixture n-hexane/DCM (gradient in DCM from 33 to
100% in volume). Sometimes the products were contami-
nated by oily by-products, and for purification they were
washed several times with n-hexane.
3
40-H), 7.97 (d, J = 7.2 Hz, 2 H, 200-H, 600-H), 8.06 (d,
3
3J = 7.6 Hz, 1 H, 60-H), 8.13 (d, J = 9.6 Hz, 1 H, 4-H),
8.49 (s, 1 H, 20-H), 8.63 (s, 1 H, 2-H), 9.31 (d, 3J = 9.4 Hz,
1 H, 8-H) ppm; 13C NMR [75 MHz, CDCl3 ? TFA (5%)]:
d = 23.55, 110.9, 114.0, 121.6, 123.5, 124.2, 130.3, 131.7,
134.9, 138.9, 139.0, 140.0, 140.2, 142.1, 142.4, 142.5,
147.2, 147.3, 150.3, 151.3, 150.6, 174.1 ppm; MS (ESI):
m/z = 394 [M ? 1].
(E)-1-[3-(Benzoyloxy)azulen-1-yl]-2-[3-[(E)-
phenyldiazenyl]phenyl]diazene (9, C29H20N4O2)
Dark brown crystals; m.p.: 106 °C; UV-vis (MeOH): kmax
1
(log e) = 235 (4.53), 321 (4.41), 440 (4.38) nm; H NMR
3
(400 MHz, CDCl3): d = 7.28 (t, J = 9.7 Hz, 1 H, 5-H),
7.42 (t, J = 9.8 Hz, 1 H, 7-H), 7.52 (t, J = 7.1 Hz, 1 H,
3
3
3
400-H), 7.56 (t, J = 6.6 Hz, 2 H, 300-H, 500-H), 7.58 (d,
3J = 7.8 Hz, 2 H, 3000-H, 5000-H), 7.65 (t, 3J = 7.9 Hz, 1 H,
3
50-H), 7.70 (t, J = 7.4 Hz, 1 H, 4000-H), 7.77 (t,
3
3J = 9.9 Hz, 1 H, 6-H), 7.96 (d, J = 7.9 Hz, 1 H, 40-H),
3
7.99 (d, J = 7.0 Hz, 2 H, 200-H, 600-H), 8.09 (d,
3
3J = 7.8 Hz, 1 H, 60-H), 8.34 (d, J = 7.2 Hz, 2 H, 2000-
Phenylselenation
3
H, 6000-H), 8.40 (d, J = 9.3 Hz, 1 H, 4-H), 8.43 (s, 1 H,
The diazene 14, 20, 21, 36, or 37 (1 mmol) dissolved in
5 cm3 DCM was treated with phenylselenyl bromide or
chloride in small portions under stirring and nitrogen, and
the stirring was continued for 1 h. The mixture was poured
into a stirred mixture of 10 cm3 DCM and 10 cm3 20%
Na2CO3 solution, and the layers were separated in a
separatory funnel. The organic layer was washed with
water and then dried over sodium sulfate. After removal of
solvent the residue was fractionated by column chroma-
tography on silica gel using a mixture of n-hexane/DCM.
After removal of the solvent the residues were triturated
with n-hexane for the elimination of oily by-products.
When it was necessary the products were filtered on a silica
gel pad.
3
2-H), 8.51 (bs, 1 H, 20-H), 9.41 (s, J = 9.8 Hz, 1 H, 8-H)
ppm; 13C NMR (100 MHz, CDCl3): d = 115.0, 116.0,
122.9, 123.0, 123.1, 125.5, 125.9, 126.6, 128.8, 129.2,
129.5, 130.3, 131.1, 133.8, 134.1, 140.1, 140.9, 143.9,
153.6, 154.9, 155.6, 164.2 ppm; MS (ESI): m/z = 457
[M ? 1].
(E)-1-[3-[(E)-Phenyldiazenyl]phenyl]-2-[3-(phenylthio)-
azulen-1-yl]diazene (10, C28H20N4S)
Dark brown crystals; m.p.: 125 °C; UV-vis (MeOH): kmax
1
(log e) = 234 (4.39), 304 (4.39), 431 (4.21) nm; H NMR
(400 MHz, CDCl3): d = 7.13 (t, 3J = 7.4 Hz, 1 H, 4000-H),
3
7.14 (d, J = 7.2 Hz, 2 H, 2000-H, 6000-H), 7.20 (t,
3
3J = 7.8 Hz, 2 H, 3000-H, 5000-H), 7.42 (t, J = 9.8 Hz, 1
H, 5-H), 7.52 (t, 3J = 8.8 Hz, 1 H, 400-H), 7.54 (m, 2 H, 300-
H, 500-H), 7.56 (t, 3J = 9.8 Hz, 1 H, 7-H), 7.66 (t,
Phenyltelluration
3
3J = 7.9 Hz, 1 H, 50-H), 7.83 (t, J = 9.8 Hz, 1 H, 6-H),
Under nitrogen atmosphere to 66 mg sulfuryl chloride
(0.48 mmol), 164 mg diphenylditelluride (0.4 mmol) was
added under stirring in small portions to avoid overheating,
and the reaction mixture was stirred for 1 h. Then a solu-
tion of azo-azulene 20 or 21 (2 mmol) in 10 cm3 DCM was
added and the mixture was stirred for further 6 h, after
which the reaction was worked up as above.
7.97 (ddd, 3J = 8.0 Hz, 4J = 1.9 Hz, 4J = 1.0 Hz, 1 H, 40-
3
H), 7.99 (dd, J = 6.9 Hz, 4J = 1.5 Hz, 2 H, 200-H, 600-H),
8.10 (ddd, 3J = 7.9 Hz, 4J = 1.9 Hz, 4J = 1.1 Hz, 1 H, 60-
3
H), 8.50 (s, 1 H, 2-H), 8.51 (t, J = 1.9 Hz, 1 H, 20-H),
8.71 (d, 3J = 9.4 Hz, 1 H, 4-H), 9.44 (d, 3J = 9.8 Hz, 1 H,
8-H) ppm; 13C NMR (100 MHz, CDCl3): d = 116.0,
123

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties
1277
123.0, 123.3, 125.4, 125.5, 126.7, 127.2, 127.8, 128.2,
129.0, 129.4, 129.6, 131.3, 137.6, 139.6, 140.2, 140.7,
142.8, 143.8, 144.1, 152.8, 153.4, 154.8, 155.1 ppm; MS
(ESI): m/z = 445 [M ? 1].
(100 MHz, CDCl3): d = 120.4, 123.0, 123.1, 123.9, 125.7,
127.3, 128.0, 128.3, 129.0, 129.1, 131.1, 136.1, 137.7,
140.6, 140.9, 143.2, 144.1, 152.8, 152.9, 155.4 ppm; MS
(ESI): m/z = 445 [M ? 1].
(E)-1-[3-(Acetylamino)azulen-1-yl]-2-[4-[(E)-
phenyldiazenyl]phenyl]diazene (11, C24H19N5O)
(E)-1-[3-(Acetylamino)azulen-1-yl]-2-[3-[(E)-
phenyldiazenyl]phenyl]diazene (16, C28H21N5O)
Dark brown crystals; m.p.: 270 °C; UV-vis (MeOH): kmax
(log e) = 230 (4.40), 297 (4.38), 364 (4.37), 504 (4.51) nm;
1H NMR (400 MHz, CDCl3): d = 2.14 (s, 3 H Me), 7.21
(t, 3J = 9.6 Hz, 1 H, 5-H), 7.35 (t, 3J = 9.8 Hz, 1 H, 7-H),
7.45 (t, 3J = 6.7 Hz, 1 H, 400-H), 7.49 (t, 3J = 7.2 Hz, 2 H,
300-H, 500-H), 7.73 (t, 3J = 9.7 Hz, 1 H, 6-H), 7.85 (d,
Dark brown crystals; m.p.: 227 °C; UV-vis (MeOH): kmax
(log e) = 232 (4.60), 281 (4.55), 339 (4.46), 415 (sh, 4.54),
462 (4.63) nm; 1H NMR (400 MHz, acetone-d6): d = 2.28
3
(s, 3 H, Me), 7.31 (t, J = 10.0 Hz, 1 H, 5-H), 7.47 (t,
3
3J = 9.6 Hz, 1 H, 7-H), 7.53 (d, J = 9.8 Hz, 1 H, 50-H),
7.58 (d, 3J = 4.6 Hz, 1 H, 30-H), 7.68 (t, 3J = 9.8 Hz, 1 H,
3
3
3J = 7.8 Hz, 2 H, 200-H, 600-H), 7.98 (d, J = 9.0 Hz, 2 H,
70-H), 7.71 (t, J = 7.9 Hz, 1 H, 500-H), 7.84 (t,
20-H, 60-H), 8.04 (d, 3J = 9.0 Hz, 2 H, 30-H, 50-H), 8.48 (d,
3J = 9.3 Hz, 1 H, 4-H), 8.74 (s, 1 H, 2-H), 9.23 (d,
3J = 9.9 Hz, 1 H, 8-H) ppm; 13C NMR [100 MHz,
CDCl3 ? TFA (5%)]: d = 23.83, 113.5, 118.5, 123.1,
130.1, 130.2, 133.7, 133.8, 139.8, 140.0, 140.5, 143.6,
147.6, 148.2, 148.8, 151.1, 173.8 ppm; MS (ESI):
m/z = 394 [M ? 1].
3J = 9.9 Hz, 1 H, 6-H), 7.96 (t, J = 9.8 Hz, 1 H, 60-H),
3
3
8.04 (ddd, J = 7.0 Hz, J = 1.9 Hz, J = 1.0 Hz, 1 H,
4
4
3
4
4
400-H), 8.06 (ddd, J = 7.0 Hz, J = 1.9 Hz, J = 1.0 Hz,
3
1 H, 600-H), 8.36 (d, J = 4.6 Hz, 1 H, 20-H), 8.54 (d,
3J = 1.8 Hz, 1 H, 200-H), 8.57 (d, J = 9.2 Hz, 1 H, 4-H),
3
3
8.60 (d, J = 9.8 Hz, 1 H, 40-H), 8.92 (s, 1 H, 2-H), 9.38
3
3
(d, J = 9.7 Hz, 1 H, 8-H), 9.49 (d, J = 9.7 Hz, 1 H, 80-
H) ppm; 13C NMR [75 MHz, CDCl3 ? TFA (5%)]:
d = 23.38, 106.9, 114.6, 117.4, 117.9, 127.9, 132.3,
134.3, 137.8, 138.9, 139.9, 140.1, 140.2, 140.3, 141.6,
142.0, 142.8, 143.7, 146.5, 147.3, 147.5, 150.9, 152.4,
156.4 ppm; MS (ESI): m/z = 444 [M ? 1].
(E)-1-[3-(Benzoyloxy)azulen-1-yl]-2-[4-[(E)-
phenylazo]phenyl]diazene (12, C29H20N4O2)
Dark brown crystals; m.p.: 73 °C; UV-vis (MeOH): kmax
(log e) = 230 (4.53), 295 (4.37), 354 (4.29), 483 (4.54) nm;
3
1H NMR (400 MHz, CDCl3): d = 7.30 (t, J = 9.7 Hz, 1
H, 5-H), 7.47 (t, 3J = 9.8 Hz, 1 H, 7-H), 7.53 (t,
(E)-1-[3-[(E)-Azulen-1-yldiazenyl]phenyl]-2-[3-
3
3J = 7.6 Hz, 1 H, 400-H), 7.54 (t, J = 7.6 Hz, 2 H, 300-
(benzoyloxy)azulen-1-yl]diazene (17, C33H22N4O2)
Dark brown crystals; m.p.: 110 °C; UV-vis (MeOH): kmax
(log e) = 231 (4.63), 281 (4.53), 332 (4.43), 448 (4.66) nm;
H, 500-H), 7.59 (d, 3J = 7.7 Hz, 2 H, 3000-H, 5000-H), 7.70 (t,
3
3J = 7.4 Hz, 1 H, 4000-H), 7.76 (t, J = 9.9 Hz, 1 H, 6-H),
3
3
7.97 (d, J = 7.2 Hz, 2 H, 200-H, 600-H), 8.08 (d,
1H NMR (400 MHz, CDCl3): d = 7.26 (t, J = 9.8 Hz, 1
3
3
3J = 8.9 Hz, 2 H, 20-H, 60-H), 8.12 (d, J = 8.9 Hz, 2 H,
H, 5-H), 7.33 (t, J = 9.8 Hz, 1 H, 50-H), 7.40 (t,
3
3
30-H, 50-H), 8.35 (d, J = 7.2 Hz, 2 H, 2000-H, 6000-H), 8.41
3J = 9.8 Hz, 1 H, 7-H), 7.45 (d, J = 4.6 Hz, 1 H, 30-H),
3
(d, J = 9.4 Hz, 1 H, 4-H), 8.44 (s, 1 H, 2-H), 9.41 (d,
7.48 (t, 3J = 9.8 Hz, 1 H, 70-H), 7.58 (t, 3J = 7.7 Hz, 2 H,
3J = 9.7 Hz, 1 H, 8-H) ppm; 13C NMR [100 MHz,
CDCl3 ? TFA (5%)]: d = 114.6, 123.0, 123.1, 123.9,
127.7, 128.3, 128.8, 129.1, 129.5, 130.3, 131.0, 133.8,
134.2, 136.6, 141.0, 143.1, 145.6, 149.6, 149.9, 153.0,
164.2 ppm; MS (ESI): m/z = 457 [M ? 1].
3000-H, 5000-H), 7.64 (t, J = 7.8 Hz, 1 H, 500-H), 7.69 (t,
3
3
3J = 7.4 Hz, 1 H, 4000-H), 7.75 (t, J = 9.9 Hz, 1 H, 6-H)
3
3
7.76 (t, J = 9.9 Hz, 1 H, 60-H) 8.02 (ddd, J = 7.0 Hz,
4J = 1.8 Hz, 4J = 1.0 Hz,
3J = 7.0 Hz, 4J = 1.8 Hz, J = 1.0 Hz, 1 H, 600-H),
1
H, 400-H), 8.04 (ddd,
4
8.35–8.37 (m,
3
H, 2000-H, 6000-H, 4-H), 8.38 (d,
(E)-1-[4-[(E)-Phenyldiazenyl]phenyl]-2-[3-(phenylthio)-
azulen-1-yl]diazene (13, C28H20N4S)
3J = 9.3 Hz, 1 H, 40-H), 8.40 (d, J = 4.8 Hz, 1 H, 20-
3
4
H), 8.47 (s, 1 H, 2-H), 8.57 (t, J = 1.8 Hz, 1 H, 200-H),
Dark brown crystals; m.p.: 129 °C; UV-vis (MeOH): kmax
(log e) = 237 (4.49), 289 (4.34), 353 (4.29), 475 (4.49) nm;
1H NMR (400 MHz, CDCl3): d = 7.13–7.15 (m, 3 H, 3000-
H, 4000-H, 5000-H), 7.20 (d, 3J = 7.3 Hz, 2 H, 2000-H, 6000-H),
3
9.43 (s, J = 9.8 Hz, 2 H, 8-H, 80-H) ppm; 13C NMR
(100 MHz, CDCl3): d = 115.0, 116.0, 120.0, 122.9, 123.1,
125.4, 125.7, 126.4, 126.6, 126.7, 126.8, 128.8, 129.3,
130.3, 133.8, 134.0, 134.5, 135.7, 136.6, 138.5, 139.0,
139.5, 140.1, 140.6, 140.8, 144.0, 144.1, 155.0, 155.1,
164.2 ppm; MS (ESI): m/z = 507 [M ? 1].
3
3
7.44 (t, J = 10.0 Hz, 1 H, 5-H), 7.58 (t, J = 10.0 Hz, 1
3
H, 7-H), 7.51 (t, J = 7.0 Hz, 1 H, 400-H), 7.53 (t,
3J = 6.9 Hz, 2 H, 300-H, 500-H), 7.85 (t, J = 9.8 Hz, 1
3
3
H, 6-H), 7.97 (d, J = 6.9 Hz, 2 H, 200-H, 600-H), 8.08 (d,
(E)-1-[3-[(E)-Azulen-1-yldiazenyl]phenyl]-2-[3-
3J = 8.7 Hz, 2 H, 20-H, 60-H), 8.12 (d, J = 8.4 Hz, 2 H,
(phenylthio)azulen-1-yl]diazene (18, C32H22N4S)
Dark brown crystals; m.p.: 80 °C; UV-vis (MeOH): kmax
(log e) = 232 (4.64), 281 (4.54), 332 (4.38), 434 (4.62) nm;
3
3
30-H, 50-H), 8.71 (d, J = 9.5 Hz, 1 H, 4-H), 8.48 (s, 1 H,
2-H), 9.43 (d, 3J = 9.9 Hz, 1 H, 8-H) ppm; 13C NMR
123

1278
A. C. Razus et al.
3
1H NMR (400 MHz, CDCl3): d = 7.11 (t, J = 7.0 Hz, 1
H, 4000-H), 7.13 (d, 3J = 7.0 Hz, 2 H, 2000-H, 6000-H), 7.20 (t,
3J = 7.2 Hz, 2 H, 3000-H, 5000-H), 7.35 (t, 3J = 9.5 Hz, 1 H,
2-H), 9.39 (d, 3J = 9.8 Hz, 1 H, 8-H), 9.40 (d, 3J =
9.5 Hz, 1 H, 80-H) ppm; 13C NMR (100 MHz, CDCl3):
d = 115.0, 120.4, 122.8, 123.1, 123.2, 125.9, 126.5, 126.8,
128.8, 129.3, 130.3, 132.7, 133.8, 134.0, 136.6, 137.1,
139.6, 140.9, 144.0, 152.2, 152.2, 164.2 ppm; MS (ESI):
m/z = 507 [M ? 1].
50-H), 7.43 (t, 3J = 9.5 Hz,
1
3
H, 5-H), 7.46 (d,
3J = 4.6 Hz, 1 H, 30-H), 7.49 (t, J = 9.8 Hz, 1 H, 70-H),
3
3
7.58 (t, J = 9.7 Hz, 1 H, 7-H), 7.65 (t, J = 7.9 Hz, 1 H,
500-H), 7.77 (t, 3J = 9.8 Hz, 1 H, 60-H), 7.84 (t,
3J = 9.8 Hz,
1
H, 6-H), 8.02 (ddd, 3J = 8.0 Hz,
(E)-1-[4-[(E)-Azulen-1-yldiazenyl]phenyl]-2-[3-
(phenylthio)azulen-1-yl]diazene (21, C32H22N4S)
4J = 1.9 Hz, 4J = 1.0 Hz,
1
H, 400-H), 8.05 (ddd,
3J = 7.9 Hz, J = 1.9 Hz, J = 1.1 Hz, 1 H, 600-H), 8.39
4
4
Dark brown crystals; m.p.: 129 °C; UV-vis (MeOH): kmax
(log e) = 230 (4.43), 284 (4.43), 338 (4.11), 464 (4.53) nm;
1H NMR (400 MHz, CDCl3): d = 7.10–7.14 (m, 3 H, 3000-
H, 4000-H, 5000-H), 7.19 (dd, 3J = 7.2 Hz, 4J = 1.0 Hz, 2 H,
3
3
(d, J = 9.8 Hz, 1 H, 40-H), 8.40 (d, J = 4.5 Hz, 1 H, 20-
4
H), 8.53 (s, 1 H, 2-H), 8.57 (t, J = 1.8 Hz, 1 H, 200-H),
8.72 (d, 3J = 9.4 Hz, 1 H, 4-H), 9.42 (d, 3J = 9.7 Hz, 1 H,
3
80-H), 9.48 (d, J = 9.7 Hz, 1 H, 8-H) ppm; 13C NMR
3
2000-H, 6000-H), 7.34 (t, J = 9.7 Hz, 1 H, 50-H), 7.35 (t,
3
3J = 9.6 Hz, 1 H, 5-H), 7.46 (d, J = 4.6 Hz, 1 H, 30-H),
(100 MHz, CDCl3): d = 115.8, 116.0, 120.1, 123.0, 123.3,
125.4, 125.5, 126.5, 126.6, 126.7, 127.2, 127.6, 127.9,
129.0, 129.4, 131.3, 135.5, 135.7, 136.1, 137.6, 138.5,
139.6, 140.1, 140.7, 142.8, 143.8, 144.0, 144.1, 154.9,
155.1 ppm; MS (ESI): m/z = 495 [M ? 1].
7.49 (t, 3J = 9.7 Hz, 1 H, 70-H), 7.56 (t, 3J = 9.5 Hz, 1 H,
3
7-H), 7.77 (t, J = 10.0 Hz, 1 H, 60-H), 7.84 (t,
3J = 10.0 Hz, 1 H, 6-H), 8.13 (bs, 4 H, 200-H, 600-H, 300-
3
H, 500-H), 8.35 (d, J = 10.0 Hz, 1 H, 40-H), 8.37 (d,
3J = 4.6 Hz, 1 H, 20-H), 8.50 (s, 1 H, 2-H), 8.71 (d,
(E)-1-[3-(Acetylamino)azulen-1-yl]-2-[4-[(E)-azulen-1-yl-
diazenyl]phenyl]diazene (19, C28H21N5O)
Dark brown crystals; dec. without melting; UV-vis
3
3J = 9.4 Hz, 1 H, 4-H), 9.39 (d, J = 9.7 Hz, 1 H, 80-H),
9.44 (d, 3J = 9.8 Hz, 1 H, 8-H) ppm; MS (ESI): m/z = 495
[M ? 1].
(MeOH): kmax (log e) = 232 (4.49), 285 (4.47), 355
(4.08), 426 (4.16), 538 (4.60) nm; H NMR (400 MHz,
1
(E)-1-[4-(Methoxyphenyl)]-2-[3-(phenylthio)azulen-1-
yl]diazene (23, C23H18N2OS)
CDCl3): d = 2.22 (s, 3 H, Me), 7.30 (t, 3J = 10.0 Hz, 1 H,
5-H), 7.45 (t, 3J = 9.8 Hz, 1 H, 50-H), 7.52 (t, 3J = 9.6 Hz,
Green crystals; m.p.: 159 °C; UV-vis (MeOH): kmax (log
e) = 230 (4.42), 278 (4.33), 341 (4.07), 428 (4.28), 446
(sh, 4.24) nm; 1H NMR (400 MHz, CDCl3): d = 3.99 (s, 3
3
1 H, 7-H), 7.57 (d, J = 4.6 Hz, 1 H, 30-H), 7.64 (t,
3J = 9.6 Hz, 1 H, 70-H), 7.83 (t, J = 10.2 Hz, 1 H, 6-H),
3
3
7.95 (t, 3J = 9.6 Hz, 1 H, 60-H), 8.15 (bs, 4 H, 200-H, 300-H,
H, OMe), 7.03 (d, J = 9.0 Hz, 2 H, 30-H, 50-H), 7.00 (t,
3
3J = 7.1 Hz, 1 H, 400-H), 7.09 (d, J = 7.3 Hz, 2 H, 200-H,
3
500-H, 600-H), 8.34 (d, J = 4.5 Hz, 1 H, 20-H), 8.56 (d,
3
3J = 9.0 Hz, 1 H, 4-H), 8.58 (d, J = 9.0 Hz, 1 H, 40-H),
3
600-H), 7.17 (t, J = 8.6 Hz, 2 H, 300-H, 500-H), 7.38 (t,
3
3J = 9.8 Hz, 1 H, 5-H), 7.48 (t, J = 9.8 Hz, 1 H, 7-H),
3
8.88 (s, 1 H, 2-H), 9.35 (d, J = 10.3 Hz, 1 H, 8-H), 9.45
7.78 (t, 3J = 9.8 Hz, 1 H, 6-H), 7.97 (d, 3J = 9.0 Hz, 2 H,
(d, J = 9.9 Hz, 1 H, 80-H) ppm; 13C NMR [75 MHz,
3
3
20-H, 60-H), 8.45 (s, 1 H, 2-H), 8.67 (d, J = 9.5 Hz, 1 H,
CDCl3 ? TFA (5%)]: d = 23.48, 114.6, 120.0, 120.4,
127.4, 134.4, 138.8, 138.9, 140.1, 140.4, 140.7, 141.1,
141.5, 141.6, 141.7, 142.0, 142.1, 142.5, 143.8, 146.7,
147.0, 147.6, 150.7, 152.2, 156.3 ppm; MS (ESI):
m/z = 444 [M ? 1].
4-H), 9.35 (d, 3J = 9.9 Hz, 1 H, 8-H) ppm; 13C NMR
(100 MHz, CDCl3): d = 55.7, 114.3, 118.9, 124.0, 125.4,
127.0, 127.1, 127.2, 128.9, 131.2, 135.8, 137.3, 138.8,
139.2, 140.4, 142.8, 143.3, 148.3, 161.1 ppm; MS (ESI):
m/z = 371 [M ? 1].
(E)-1-[4-[(E)-Azulen-1-yldiazenyl]phenyl]-2-[3-
(E)-1-[4-(Methoxyphenyl)]-2-[3-(phenylseleno)azulen-1-
yl]diazene (24, C23H18N2OSe)
(benzoyloxy)azulen-1-yl]diazene (20, C33H22N4O2)
Dark brown crystals; m.p.: 130 °C; UV-vis (MeOH): kmax
(log e) = 234 (4.55), 281 (4.43), 337 (4.07), 418 (sh, 4.07),
Green crystals; m.p.: 178 °C; UV-vis (MeOH): kmax (log
e) = 227 (4.40), 248 (sh, 4.35), 283 (4.33), 340 (4.13), 426
(4.32), 447 (sh, 4.28) nm; H NMR (400 MHz, CDCl3):
1
520 (4.52) nm; H NMR (400 MHz, CDCl3): d = 7.26 (t,
1
3
3J = 9.7 Hz, 1 H, 5-H), 7.34 (t, J = 9.7 Hz, 1 H, 50-H),
3
7.41 (t, 3J = 9.7 Hz, 1 H, 7-H), 7.45 (d, 3J = 4.8 Hz, 1 H,
d = 3.90 (s, 3 H, OMe), 7.03 (d, J = 9.0 Hz, 2 H, 30-H,
3
50-H), 7.11–7.17 (m, 3 H, 300-H, 400-H, 500-H), 7.18 (dd,
30-H), 7.48 (t, J = 9.8 Hz,
1
H, 70-H), 7.59 (t,
4
3J = 7.9 Hz, J = 1.6 Hz, 2 H, 200-H, 600-H), 7.38 (t,
3J = 7.6 Hz, 2 H, 3000-H, 5000-H), 7.70 (td, J = 7.3 Hz,
4J = 1.3 Hz, 1 H, 4000-H), 7.76 (t, 3J = 10.0 Hz, 2 H, 6-H,
60-H), 8.13 (bs, 4 H, 200-H, 600-H, 300-H, 500-H), 8.34 (d,
3
3
3J = 9.8 Hz, 1 H, 5-H), 7.48 (t, J = 9.8 Hz, 1 H, 7-H),
7.78 (t, 3J = 9.8 Hz, 1 H, 6-H), 7.97 (d, 3J = 9.0 Hz, 2 H,
3
3J = 9.0 Hz,
1
H, 4-H), 8.35 (dd, 3J = 8.4 Hz,
20-H, 60-H), 8.52 (s, 1 H, 2-H), 8.68 (d, J = 9.5 Hz, 1 H,
4-H), 9.35 (d, 3J = 9.8 Hz, 1 H, 8-H) ppm; 13C NMR
(100 MHz, CDCl3): d = 55.6, 114.3, 116.0, 124.0, 126.1,
4J = 1.4 Hz, 2 H, 2000-H, 6000-H), 8.36 (d, J = 4.5 Hz, 1
3
3
H, 20-H), 8.37 (d, J = 9.1 Hz, 1 H, 40-H), 8.44 (s, 1 H,
123

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties
1279
3
4
127.0, 127.1, 129.1, 129.6, 132.5, 135.5, 139.0, 140.2,
143.2, 143.9, 148.4, 161.1 ppm; MS (ESI): m/z = 419
[M ? 1]; isotopic composition: 413 (17.3%), 414 (9.2%),
415 (25.5%), 416 (23.4%), 417 (50.0%), 418 (10.0%), 419
(100%), 420 (30.7%), 421 (23.1%).
5000-H), 7.46 (dd, J = 8.2 Hz, J = 1.3 Hz, 2 H, 2000-H,
6000-H), 7.47 (t, 3J = 9.4 Hz, 1 H, 5-H), 7.52 (t,
3J = 7.0 Hz, 1 H, 400-H), 7.56 (t, J = 7.5 Hz, 2 H, 300-
3
H, 500-H), 7.56 (t, 3J = 9.4 Hz, 1 H, 7-H), 7.66 (t,
3J = 7.8 Hz, 1 H, 50-H), 7.86 (t, J = 9.8 Hz, 1 H, 6-H),
3
7.97 (ddd, 3J = 7.9 Hz, 4J = 1.1 Hz, 1 H, 40-H), 7.99 (dd,
(E)-1-[4-(Methoxyphenyl)]-2-[3-(phenyltelluro)azulen-1-
yl]diazene (25, C23H18N2OTe)
3J = 8.1 Hz, J = 1.3 Hz, 2 H, 200-H, 600-H), 8.10 (ddd,
4
3J = 7.9 Hz, J = 1.9 Hz, J = 1.1 Hz, 1 H, 60-H), 8.52
4
4
Green crystals; m.p.: 188 °C; UV-vis (MeOH): kmax (log
e) = 225 (4.34), 287 (4.33), 336 (4.07), 426 (4.29), 445
(sh, 4.25) nm; 1H NMR (400 MHz, CDCl3): d = 3.90 (s, 3
4
3
(t, J = 1.9 Hz, 1 H, 20-H), 8.73 (d, J = 9.5 Hz, 1 H,
3
4-H), 8.75 (s, 1 H, 2-H), 9.45 (d, J = 9.9 Hz, 1 H, 8-H)
ppm; 13C NMR (75 MHz, CDCl3): d = 102.8, 116.2,
117.4, 123.1, 123.5, 125.5, 127.3, 127.8, 128.2, 129.3,
129.5, 129.7, 131.3, 135.4, 135.6, 137.7, 140.3, 142.7,
144.9, 152.9, 153.7, 155.0 ppm; MS (ESI): m/z = 541
[M ? 1]; isotopic composition: 535 (13.2%), 536 (6.6%),
537 (19.0%), 538 (45.6%), 539 (57.3%), 540 (21.0%), 541
(100.0%), 542 (34.0%), 543 (84.6%), 544 (22.3%).
3
H, OMe), 7.03 (d, J = 9.0 Hz, 2 H, 30-H, 50-H), 7.08 (t,
3
3J = 7.2 Hz, 2 H, 300-H, 500-H), 7.14 (t, J = 7.3 Hz, 1 H,
400-H), 7.41 (t, 3J = 9.7 Hz, 1 H, 5-H), 7.42 (dd,
4
3J = 7.2 Hz, J = 1 Hz, 2H, 200-H, 600-H), 7.49 (t,
3
3J = 9.8 Hz, 1 H, 7-H), 7.79 (t, J = 9.9 Hz, 1 H, 6-H),
7.98 (d, 3J = 9.0 Hz,
2
H, 20-H, 60-H), 8.68 (d,
3J = 9.8 Hz, 1 H, 4-H), 8.69 (s, 1 H, 2-H), 9.35 (d,
3J = 9.8 Hz, 1 H, 8-H) ppm; 13C NMR (100 MHz,
CDCl3): d = 55.7, 102.1, 114.4, 124.1, 127.1, 127.2,
129.5, 135.1, 135.3, 137.6, 139.2, 140.0, 142.4, 144.8,
146.6, 161.2 ppm; MS (ESI): m/z = 467 [M ? 1]; isotopic
composition: 461 (9%), 462 (4.7%), 463 (21.9%), 464
(18.6%), 465 (67.8%), 466 (11.5%), 467 (100.0%), 468
(16.2%), 469 (92.0%), 470 (22.6%), 471 (4.1%).
(E)-1-[4-[(E)Phenyldiazenyl]phenyl]-2-[3-(phenyl-
seleno)azulen-1-yl]diazene (32, C28H20N4Se)
Dark brown crystals; m.p.: 126 °C; UV-vis (MeOH): kmax
(log e) = 233 (4.60), 284 (4.38), 354 (4.27), 475 (4.52) nm;
1H NMR (400 MHz, CDCl3): d = 7.13–7.20 (m, 3 H, 3000-
3
4
H, 4000-H, 5000-H), 7.27 (d, J = 7.2 Hz, J = 2.4 Hz, 2 H,
3
2000-H, 6000-H), 7.45 (t, J = 9.7 Hz, 1 H, 5-H), 7.57 (t,
3J = 9.8 Hz, 1 H, 7-H), 7.51 (t, J = 7.0 Hz, 1 H, 400-H),
3
(E)-1-[3-[(E)-Phenyldiazenyl]phenyl]-2-[3-(phenyl-
seleno)azulen-1-yl]diazene (30, C28H20N4Se)
7.55 (t, 3J = 7.7 Hz,
2
H, 300-H, 500-H), 7.84 (t,
H, 6-H), 7.97 (dt, 3J = 7.0 Hz,
3J = 9.8 Hz,
1
Dark brown crystals; m.p.: 120 °C; UV-vis (MeOH): kmax
4J = 1.8 Hz, 2 H, 200-H, 600-H), 8.08 (d, J = 8.6 Hz, 2
H, 20-H, 60-H or 30-H, 50-H), 8.12 (d, 3J = 8.9 Hz, 2 H, 30-
H, 50-H or 20-H, 60-H), 8.55 (s, 1 H, 2-H), 8.71 (d,
3
1
(log e) = 230 (4.42), 306 (4.43), 431 (4.25) nm; H NMR
(400 MHz, CDCl3): d = 7.13–7.18 (m, 3 H, 3000-H, 4000-H,
5000-H), 7.24–7.28 (m, 2 H, 2000-H, 6000-H), 7.44 (t,
3J = 9.5 Hz, 1 H, 4-H), 9.42 (d, J = 9.8 Hz, 1 H, 8-H)
3
3
3J = 9.8 Hz, 1 H, 5-H), 7.52 (t, J = 7.0 Hz, 1 H, 400-H),
ppm; 13C NMR (100 MHz, CDCl3): d = 117.4, 123.0,
123.1, 123.9, 126.3, 127.9, 128.2, 129.1, 129.2, 129.9,
131.1, 132.6, 133.1, 135.8, 139.3, 140.5, 140.6, 143.7,
144.7, 152.8, 152.9, 155.4 ppm; MS (ESI): m/z = 493
[M ? 2]; isotopic composition: 489 (19%), 490 (9%), 491
(52%), 493 (100%), 494 (24%), 495 (15%), 496 (8%), 497
(3%).
7.56 (t, 3J = 7.5 Hz,
2
H, 300-H, 500-H), 7.56 (t,
3
3J = 9.6 Hz, 1 H, 7-H), 7.66 (t, J = 8.0 Hz, 1 H, 50-H),
3
7.84 (t, J = 9.8 Hz, 1 H, 6-H), 7.98 (ddd, J = 8.0 Hz,
3
4J = 1.9 Hz, 4J = 1.1 Hz,
1
H, 40-H), 7.99 (dd,
4
3J = 7.3 Hz, J = 1.5 Hz, 2 H, 200-H, 600-H), 8.10 (ddd,
4
4
3J = 7.9 Hz, J = 1.9 Hz, J = 1.1 Hz, 1 H, 60-H), 8.52
4
(t, J = 1.9 Hz, 1 H, 20-H), 8.56 (s, 1 H, 2-H), 8.72 (d,
3J = 9.4 Hz, 1 H, 4-H), 9.45 (d, J = 9.8 Hz, 1 H, 8-H)
(E)-1-[4-[(E)Phenyldiazenyl]phenyl]-2-[3-(phenyl-
telluro)azulen-1-yl]diazene (33, C28H20N4Te)
3
ppm; 13C NMR (75 MHz, CDCl3): d = 116.0, 116.9,
123.0, 123.4, 125.4, 126.3, 127.7, 128.0, 129.1, 129.2,
129.5, 129.8, 131.3, 132.6, 135.8, 139.3, 140.2, 140.5,
143.2, 144.4, 152.7, 153.5, 154.8 ppm; MS (ESI):
m/z = 493 [M ? 2]; isotopic composition: 489 (17%),
490 (8%), 491 (54%), 493 (100%), 494 (23%), 495 (17%),
496 (7%), 497 (3%).
Dark brown crystals; m.p.: 134 °C; UV-vis (MeOH): kmax
(log e) = 290 (4.37), 343 (4.28), 475 (4.48); 1H NMR
3
(400 MHz, CDCl3): d = 7.10 (t, J = 7.3 Hz, 2 H, 3000-H,
3
5000-H), 7.17 (t, J = 7.3 Hz, 1 H, 4000-H), 7.46 (d,
3J = 7.6 Hz, 2 H, 2000-H, 6000-H), 7.50 (t, J = 9.7 Hz, 1
3
3
H, 5-H), 7.52 (t, J = 7.9 Hz, 1 H, 400-H), 7.54 (t,
3J = 7.9 Hz, 2 H, 300-H, 500-H), 7.59 (t, J = 9.7 Hz, 1
3
H, 7-H), 7.86 (t, 3J = 9.7 Hz, 1 H, 6-H), 7.97 (d,
(E)-1-[3-[(E)-Phenyldiazenyl]phenyl]-2-[3-(phenyl-
telluro)azulen-1-yl]diazene (31, C28H20N4Te)
3J = 8.0 Hz, 2 H, 200-H, 600-H), 8.08 (d, J = 8.8 Hz, 2
3
H, 20-H, 60-H or 30-H, 50-H), 8.13 (d, 3J = 8.7 Hz, 2 H, 30-
Dark brown crystals; m.p.: 128 °C; UV-vis (MeOH): kmax
1
3
H, 50-H or 20-H, 60-H), 8.72 (d, J = 9.9 Hz, 1 H, 4-H),
(log e) = 226 (4.42), 309 (4.48), 431 (4.16) nm; H NMR
3
8.73 (s, 1 H, 2-H), 9.42 (d, J = 9.9 Hz, 1 H, 8-H) ppm;
(400 MHz, CDCl3): d = 7.10–7.16 (m, 3 H, 3000-H, 4000-H,
123

1280
A. C. Razus et al.
3
13C NMR (100 MHz, CDCl3): d = 103.3, 123.1, 123.3,
124.0, 127.3, 128.0, 128.4, 129.3, 129.5, 131.2, 135.4,
135.6, 137.7, 140.4, 140.6, 142.7, 145.3, 147.4, 152.9,
153.0, 155.6 ppm; MS (ESI): m/z = 541 [M ? 1]; isotopic
composition: 535 (10.5%), 536 (6.2%), 537 (17.0%), 538
(38.7%), 539 (55.6%), 540 (13.2%), 541 (100.0%), 542
(34.8%), 543 (91.1%), 544 (29.4%).
3J = 9.8 Hz, 1 H, 60-H), 7.83 (t, J = 9.8 Hz, 1 H, 6-H),
3
8.02 (ddd, J = 8.0 Hz, J = 1.6 Hz, J = 0.8 Hz, 1 H,
4
4
3
4
4
400-H), 8.05 (ddd, J = 7.9 Hz, J = 1.6 Hz, J = 0.8 Hz,
3
1 H, 600-H), 8.36 (d, J = 9.3 Hz, 1 H, 40-H), 8.40 (d,
3J = 4.5 Hz, 1 H, 20-H), 8.57 (d, 4J = 1.8 Hz, 1 H, 200-H),
8.60 (s, 1 H, 2-H), 8.72 (d, 3J = 9.4 Hz, 1 H, 4-H), 9.42 (d,
3
3J = 9.7 Hz, 1 H, 80-H), 9.47 (d, J = 9.9 Hz, 1 H, 8-H)
ppm; 13C NMR (100 MHz, CDCl3): d = 116.2, 116.8,
120.1, 123.1, 123.4, 124.9, 125.5, 126.3, 126.8, 127.6,
127.9, 129.0, 129.3, 129.5, 129.9, 131.1, 132.8, 135.8,
135.9, 138.6, 139.3, 139.7, 140.1, 140.5, 143.4, 144.2,
144.5, 155.0, 155.2 ppm; MS (ESI): m/z = 543 [M ? 2];
isotopic composition: 539 (24.7%), 540 (21.9%), 541
(50.2%), 542 (12.8%), 543 (100%), 544 (34.1%), 545
(17.9%), 546 (6.5%), 548 (2.2%).
(E)-1-[3-(Bromoazulen-1-yl)]-2-[3-[(E)-phenyldiaze-
nyl]phenyl]diazene (34, C22H15BrN4)
Dark brown crystals; m.p.: 139 °C; UV-vis (MeOH): kmax
(log e) = 233 (4.41), 288 (4.37), 326 (4.40), 434 (4.39) nm;
3
1H NMR (400 MHz, CDCl3): d = 7.43 (t, J = 9.8 Hz, 1
H, 5-H), 7.51 (t, 3J = 10.1 Hz, 1 H, 7-H), 7.54 (t,
3
3J = 7.3 Hz, 1 H, 400-H), 7.56 (t, J = 7.5 Hz, 2 H, 300-
3
H, 500-H), 7.66 (t, J = 7.8 Hz, 1 H, 50-H), 7.82 (t,
(E)-1-[3-[(E)-[3-(Phenylseleno)Azulen-1-yl]-
diazenyl]phenyl]-2-[3-(phenylseleno)azulen-1-yl]diazene
(39, C38H26N4Se2)
3J = 9.8 Hz,
1
H, 6-H), 7.97 (ddd, 3J = 7.9 Hz,
4J = 1.8 Hz, 4J = 1.1 Hz,
1
H, 40-H), 7.99 (dd,
3J = 8.1 Hz, J = 1.5 Hz, 2 H, 200-H, 600-H), 8.08 (ddd,
4
Dark brown crystals; m.p.: 167 °C; UV-vis (MeOH): kmax
(log e) = 230 (4.67), 283 (4.58), 336 (4.39), 445 (4.52); 1H
NMR (400 MHz, CDCl3): d = 7.11–7.19 (m, 6 H, 3Ph-H,
3J = 7.8 Hz, J = 1.8 Hz, J = 1.1 Hz, 1 H, 60-H), 8.37
4
4
3
(s, 1 H, 2-H), 8.44 (d, J = 9.5 Hz, 1 H, 4-H), 8.49 (t,
4J = 1.8 Hz, 1 H, 20-H), 9.35 (d, J = 9.8 Hz, 1 H, 8-H)
3
3
4
4Ph-H, 5Ph-H), 7.26 (dd, J = 7.6 Hz, J = 1.6 Hz, 4 H,
3
ppm; 13C NMR (100 MHz, CDCl3): d = 109.4, 116.0,
123.0, 123.5, 125.4, 126.3, 126.9, 127.3, 129.2, 129.6,
131.2, 136.0, 138.1, 138.3, 138.3, 139.5, 140.9, 142.3,
153.5, 154.7 ppm; MS (ESI): m/z = 415 [M ? 1], 417
[M ? 3].
2Ph-H, 6Ph-H), 7.45 (t, J = 9.8 Hz, 2 H, 5-H and 50-H),
3
7.57 (t, J = 9.8 Hz, 2 H, 7-H and 70-H), 7.65 (t,
3
3J = 7.8 Hz, 1 H, 500-H), 7.85 (t, J = 9.8 Hz, 2 H, 6-H
3
4
and 60-H), 8.04 (dd, J = 7.9 Hz, J = 1.7 Hz, 2 H, 400-H,
4
600-H), 8.56 (t, J = 1.6 Hz, 1 H, 200-H), 8.59 (s, 2 H, 2-H
3
and 20-H), 8.73 (d, J = 9.5 Hz, 2 H, 4-H and 40-H), 9.47
(E)-1-[3-(Bromoazulen-1-yl)]-2-[4-[(E)-phenyl-
diazenyl]phenyl]diazene (35, C22H15BrN4)
(d, J = 9.7 Hz, 2 H, 8-H and 80-H) ppm; 13C NMR
3
Dark brown crystals; m.p.: 160 °C; UV-vis (MeOH): kmax
(log e) = 232 (4.42), 288 (4.24), 354 (4.28), 471 (4.50) nm;
(100 MHz, CDCl3): d = 116.2, 123.5, 126.4, 127.7, 128.0,
129.5, 129.6, 130.0, 132.8, 133.5, 136.0, 139.4, 140.6,
143.4, 144.5, 155.1 ppm; MS (ESI): m/z = 699 [M ? 3];
isotopic composition: 691 (6.0%), 692 (1.8%), 693
(19.8%), 694 (6.6%), 695 (46.1%), 696 (36.1%), 697
(67.8%), 698 (3.5%), 699 (100%), 700 (32.6%), 701
(19.3%), 702 (9.1%), 703 (2.4%), 704 (1.9%).
3
1H NMR (400 MHz, CDCl3): d = 7.44 (t, J = 9.8 Hz, 1
H, 5-H), 7.48–7.56 (m, 4 H, 7-H, 300-H, 400-H, 500-H), 7.82
3
3
(t, J = 9.8 Hz, 1 H, 6-H), 7.96 (d, J = 7.4 Hz, 2 H, 200-
H, 600-H), 8.07 (d, 3J = 8.9 Hz, 1 H, 20-H, 60-H or 30-H, 50-
H), 8.10 (d, J = 8.9 Hz, 1 H, 30-H, 50-H or 20-H, 60-H),
3
8.36 (s, 1 H, 2-H), 8.44 (d, 3J = 9.2 Hz, 1 H, 4-H), 9.33 (d,
3J = 9.6 Hz, 1 H, 8-H) ppm; 13C NMR (100 MHz,
CDCl3): d = 104.8, 123.0, 123.9, 126.3, 127.2, 127.5,
129.1, 131.1, 136.0, 138.1, 139.2, 141.0, 142.8, 152.8,
152.9, 154.6 ppm; MS (ESI): m/z = 415 [M ? 1], 417
[M ? 3].
(E)-1-[4-[(E)-Azulen-1-yldiazenyl]phenyl]-2-[3-
(phenylseleno)azulen-1-yl]diazene (40, C32H22N4Se)
Dark brown crystals; m.p.: 146 °C; UV-vis (MeOH): kmax
(log e) = 232 (4.49), 281 (4.45), 340 (4.07), 523 (4.53) nm;
1H NMR (400 MHz, CDCl3): d = 7.12–7.19 (m, 3 H, 3000-
H, 4000-H, 5000-H), 7.24–7.28 (m, 2 H, 2000-H, 6000-H), 7.35 (t,
3
3J = 9.8 Hz, 1 H, 50-H), 7.43 (t, J = 9.6 Hz, 1 H, 5-H),
(E)-1-[3-[(E)Azulen-1-yldiazenyl]phenyl]-2-[3-
7.46 (d, 3J = 4.5 Hz, 1 H, 30-H), 7.48 (t, 3J = 9.8 Hz, 1 H,
70-H), 7.55 (t, 3J = 9.7 Hz, 1 H, 7-H), 7.77 (t, 3J = 9.8 Hz,
(phenylseleno)azulen-1-yl]diazene (38, C32H22N4Se)
Dark brown crystals; m.p.: 160 °C; UV-vis (MeOH): kmax
(log e) = 230 (4.60), 280 (4.55), 336 (4.43), 444 (4.61) nm;
1H NMR (400 MHz, CDCl3): d = 7.12–7.19 (m, 3 H, 3000-
H, 4000-H, 5000-H), 7.26 (dd, 3J = 7.6 Hz, 4J = 2.0 Hz, 2 H,
3
1 H, 60-H), 7.83 (t, J = 9.8 Hz, 1 H, 6-H), 8.13 (bs, 4 H,
200-H, 300-H, 500-H, 600-H), 8.34 (d, 3J = 9.8 Hz, 1 H, 40-H),
8.37 (t, 3J = 3.0 Hz, 1 H, 20-H), 8.57 (s, 1 H, 2-H), 8.70 (d,
3
3
3J = 9.5 Hz, 1 H, 4-H), 9.38 (d, J = 9.8 Hz, 1 H, 80-H),
2000-H, 6000-H), 7.35 (t, J = 9.6 Hz, 1 H, 50-H), 7.43 (t,
3
3J = 9.7 Hz, 1 H, 5-H), 7.46 (d, J = 4.1 Hz, 1 H, 30-H),
9.42 (d, 3J = 9.7 Hz, 1 H, 8-H) ppm; 13C NMR (75 MHz,
CDCl3): d = 117.1, 120.6, 123.2, 123.4, 125.4, 126.3,
127.0, 127.1, 127.8, 128.0, 129.3, 129.9, 132.7, 135.8,
7.48 (t, 3J = 9.8 Hz, 1 H, 70-H), 7.56 (t, 3J = 9.7 Hz, 1 H,
7-H), 7.64 (t, 3J = 7.8 Hz,
1
H, 500-H), 7.77 (t,
123

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties
1281
135.9, 138.7, 139.2, 139.3, 139.8, 140.2, 140.6, 143.9,
144.4, 144.6, 144.7, 154.3, 154.8 ppm; MS (ESI):
m/z = 545 [M ? 2].
NMR [100 MHz, CDCl3 ? TFA (5%)]: d = 108.9, 117.5,
125.8, 128.4, 132.4, 139.3, 139.6, 141.6, 142.2, 142.3,
142.8, 147.2, 150.9, 151.9 ppm; MS (ESI): m/z = 543
[M ? 1], 545 [M ? 3], 547 [M ? 5].
(E)-1-[4-[(E)-[(3-Phenylseleno)azulen-1-yl]diaze-
nyl]phenyl]-2-[(3-phenylseleno)azulen-1-yl]-diazene
(41, C38H26N4Se2)
(E)-1-[4-[(E)-(3-Bromoazulen-1-yl)diazenyl]phenyl]-2-[3-
(phenylseleno)azulen-1-yl]diazene (44, C32H21BrN4Se)
Dark brown crystals (in mixture); 1H NMR (400 MHz,
CDCl3): d = 7.15–7.17 (m, 3 H, 3Ph-H, 4Ph-H, 5Ph-H),
Dark brown crystals; m.p.: 237 °C; UV-vis (MeOH): kmax
1
(log e) = 227 (4.72), 281 (4.55), 531 (4.47) nm; H NMR
3
(400 MHz, CDCl3): d = 7.14–7.17 (m, 3 H, 3Ph-H, 4Ph-H,
5Ph-H), 7.24–7.28 (m, 2 H, 2Ph-H, 6Ph-H), 7.44 (t,
7.25–7.27 (m, 2 H, 2Ph-H, 6Ph-H), 7.45 (t, J = 9.7 Hz, 1
3
H, 5-H or 50-H), 7.46 (t, J = 9.6 Hz, 1 H, 50-H or 5-H),
3
3
3J = 9.6 Hz, 1 H, 5-H and 50-H), 7.57 (t, J = 9.7 Hz, 1
7.52 (t, J = 9.7 Hz, 1 H, 7-H or 70-H), 7.59 (t,
H, 7-H and 70-H), 7.84 (t, 3J = 9.8 Hz, 1 H, 6-H and 60-H),
3J = 9.5 Hz, 1 H, 70-H or 7-H), 7.83 (t, J = 10.0 Hz, 1
3
3
8.13 (bs, 4 H, 200-H, 300-H, 500-H, 600-H), 8.57 (s, 2 H, 2-H
H, 6-H or 60-H), 7.86 (t, J = 10.0 Hz, 1 H, 60-H or 6-H),
3
and 20-H), 8.71 (d, J = 9.5 Hz, 1 H, 4-H and 40-H), 9.44
8.12 (bs, 4 H, 200-H, 300-H, 500-H, 600-H), 8.37 (s, 1 H, 20-H),
3
3
(d, J = 9.7 Hz, 1 H, 8-H and 80-H) ppm; 13C NMR
8.45 (d, J = 9.4 Hz, 1 H, 40-H), 8.55 (s, 1 H, 2-H), 8.72
3
3
[75 MHz, CDCl3 ? TFA (5%)]: d = 119.7, 125.5, 127.0,
130.2, 130.6, 135.3, 139.3, 140.6, 140.7, 140.8, 141.5,
141.8, 142.0, 146.3, 152.4, 153.3 ppm; MS (ESI):
m/z = 699 [M ? 3].
(d, J = 9.5 Hz, 1 H, 4-H), 9.35 (d, J = 9.8 Hz, 1 H, 80-
H), 9.43 (d, J = 9.8 Hz, 1 H, 8-H) ppm; ppm; 13C NMR
3
(100 MHz, CDCl3): d = 109.2, 117.1, 117.9, 119.5, 126.1,
126.3, 127.7, 127.8, 127.9, 128.2, 129.5, 130.0, 132.8,
133.1, 135.8, 136.0, 138.1, 139.2, 139.3, 140.5, 140.6,
141.0, 142.2, 142.9, 143.7, 144.7, 151.0, 153.6 ppm; MS
(ESI): m/z = 623 [M ? 3], 625 [M ? 5].
(E)-1-[3-[(E)-Azulen-1-yldiazenyl]phenyl]-2-[3-
bromoazulen-1-yl]diazene (42, C26H17BrN4)
Dark brown crystals; m.p.: 213 °C; UV-vis (MeOH): kmax
(log e) = 225 (4.60), 281 (4.54), 331 (4.43), 443 (4.57) nm;
(E)-1-[4-[(E)-Azulen-1-yldiazenyl]phenyl]-2-
(3-bromoazulen-1-yl)diazene (45, C26H17BrN4)
3
1H NMR (400 MHz, CDCl3): d = 7.36 (t, J = 9.6 Hz, 1
H, 50-H), 7.43 (t, 3J = 9.8 Hz, 1 H, 5-H), 7.46 (d,
Dark brown crystals; m.p.: 193 °C; UV-vis (MeOH): kmax
(log e) = 232 (4.48), 283 (4.41), 333 (4.10), 415 (sh, 4.04),
3
3J = 4.6 Hz, 1 H, 30-H), 7.49 (t, J = 9.8 Hz, 1 H, 70-H),
3
3
1
7.50 (t, J = 9.9 Hz, 1 H, 7-H), 7.64 (t, J = 7.8 Hz, 1 H,
500-H), 7.78 (t, 3J = 9.8 Hz,
H, 6-H), 7.82 (t,
3J = 9.8 Hz, H, 60-H), 8.01 (ddd, 3J = 7.9 Hz,
4J = 1.8 Hz, 4J = 1.1 Hz, H, 400-H), 8.05 (ddd,
521 (4.53) nm; H NMR (400 MHz, CDCl3): d = 7.33 (t,
3
1
3J = 9.8 Hz, 1 H, 50-H), 7.42 (t, J = 9.6 Hz, 1 H, 5-H),
1
7.46 (d, 3J = 4.5 Hz, 1 H, 30-H), 7.49 (t, 3J = 9.7 Hz, 2 H,
3
2
7-H, 70-H), 7.75 (t, J = 9.8 Hz, 1 H, 60-H), 7.82 (t,
4
4
3J = 7.8 Hz, J = 1.8 Hz, J = 1.0 Hz, 1 H, 600-H), 8.37
3J = 9.8 Hz, 1 H, 6-H), 8.13 (bs, 4 H, 200-H, 300-H, 500-H,
600-H), 8.36 (d, 3J = 9.8 Hz, 1 H, 40-H), 8.38 (s, 1 H, 20-H),
8.44 (d, 3J = 9.5 Hz, 1 H, 4-H), 8.38 (s, 1 H, 2-H), 9.35 (d,
3
3
(d, J = 9.3 Hz, 1 H, 4-H), 8.39 (d, J = 4.6 Hz, 1 H, 20-
3
H), 8.40 (s, 1 H, 2-H), 8.45 (d, J = 9.8 Hz, 1 H, 40-H),
4
3
3
8.55 (d, J = 1.9 Hz, 1 H, 200-H), 9.39 (d, J = 9.8 Hz, 1
3J = 9.8 Hz, 1 H, 8-H), 9.39 (d, J = 9.8 Hz, 1 H, 80-H)
H, 8-H), 9.43 (d, J = 9.8 Hz, 1 H, 80-H) ppm; 13C NMR
ppm; 13C NMR (100 MHz, CDCl3): d = 109.6, 120.5,
123.1, 123.3, 125.4, 126.3, 126.9, 127.0, 127.2, 135.7,
136.0, 138.0, 138.1, 138.6, 139.5, 139.7, 141.0, 142.9,
143.1, 144.4, 150.7, 151.6 ppm; MS (ESI): m/z = 465
[M ? 1], 467 [M ? 3].
3
(100 MHz, CDCl3): d = 109.4, 116.2, 120.3, 123.1, 123.4,
125.2, 125.5, 126.4, 126.9, 127.3, 129.5, 135.8, 136.1,
137.9, 138.2, 138.7, 139.4, 139.7, 140.7, 141.0, 143.2,
145.9, 154.1, 154.9 ppm; MS (ESI): m/z = 465 [M ? 1],
467 [M ? 3].
Acknowledgments The financial support of this research, received
from the Romanian Ministry of Education and Research, program
PN-II no. 115/2007, is gratefully acknowledged.
(E)-1-[3-[(E)-(3-Bromoazulen-1-yl)diazenyl]phenyl]-2-
(3-bromoazulen-1-yl)diazene (43, C26H16Br2N4)
Dark brown crystals; m.p.: 245 °C; UV-vis (MeOH): kmax
(log e) = 226 (4.57), 283 (4.52), 335 (4.42), 446 (4.55) nm;
1H NMR (400 MHz, CDCl3): d = 7.43 (t, J = 9.8 Hz, 2
3
References
H, 5-H and 50-H), 7.51 (t, 3J = 9.8 Hz, 2 H, 7-H and 70-H),
7.64 (t, 3J = 7.9 Hz, 2 H, 500-H), 7.82 (t, 3J = 9.9 Hz, 2 H,
1. Razus AC (2000) J Chem Soc Perkin Trans 1:981
2. Razus AC, Nitu CJ (2000) J Chem Soc Perkin Trans 1:989
3. Razus AC, Birzan L, Nae S, Razus SA, Cimpeanu V, Stanciu C
(2002) Synth Commun 32:825
4. Razus AC, Birzan L, Nae S, Cristian L, Chiraleu F, Cimpeanu V
(2003) Dyes Pigm 57:223
3
4
6-H and 60-H), 8.02 (dd, J = 7.9 Hz, J = 1.9 Hz, 2 H,
400-H, 600-H), 8.39 (s, 2 H, 2-H and 20-H), 8.46 (d,
3J = 9.5 Hz, 2 H, 4-H and 40-H), 8.56 (t, 4J = 1.9 Hz, 1 H,
3
200-H), 9.38 (d, J = 9.8 Hz, 2 H, 8-H and 80-H) ppm; 13C
123

1282
A. C. Razus et al.
5. Razus AC, Birzan L, Nae S, Surugiu MN, Cimpeanu V (2003) J
Heterocycl Chem 40:995
6. Razus AC, Birzan L, Surugiu NM, Corbu AC, Chiraleu F (2007)
Dyes Pigm 74:26
7. Razus AC, Birzan L, Cristea M, Tecuceanu V, Blanariu L,
Enache C (2009) Dyes Pigm 80:337
8. Razus AC, Birzan L, Cristea M, Popa B (2009) Dyes Pigm
82:216
13. Nefedov VD (1968) Zh Obshch Khim 38:2191
14. Hafner K, Stephan A, Bernhard C (1961) Anal Chem 650:42
15. Replogle LL (1964) J Org Chem 29:2805
16. Replogle LL, Arluck RM, Maynard JR (1965) J Org Chem
30:2715
17. Shoji T, Higashi J, Ito S, Toyota K, Asao T, Yasunami M, Fu-
jimori K, Morita N (2008) Eur J Org Chem 34:1242 and
references therein
9. Lacroix PG, Malfant I, Iftime G, Razus AC, Nakatani K, Delaire
JA (2000) Chem Eur J 6:2599
18. Anderson AG, Nelson JA, Tazuma JJ (1953) J Am Chem Soc
75:4980
10. Cristian L, Sasaki I, Lacroix PL, Donnadieu B, Asselberghs I,
Clays K, Razus AC (2004) Chem Mater 16:3543
11. Ungureanu EM, Birzan L, Razus AC, Cretu MS, Buica GO
(2008) Electrochim Acta 53:7089
19. Razus AC, Birzan L, Nae S, Cristian L, Chiraleu F, Maganu M,
Cimpeanu V, Tarko L (2003) Rev Roum Chim 48:455
20. Abraham RJ, Mobli M, Smith RJ (2004) Magn Reson Chem
42:436
12. Razus AC, Birzan L, Cristea M, Ungureanu EM, Cretu MS
(2010) Dyes Pigm 86:1
21. Razus AC, Birzan L, Razus SA, Horga V (1999) Rev Roum Chim
44:235
123