Insertion reaction of azidosulfonyl azo dye with model alicyclic and heterocyclic compounds

Article abstract of DOI:10.1134/S1070428008100102

Thermal reactions of 4-(2-hydroxynaphthalen-1-yldiazenyl)benzenesulfonyl azide with cyclohexane, benzene, toluene, anisole, p-xylene, mesitylene, dihydropyran, and pyridine were studied. Structures of the resulting azo dyes were confirmed by FT-IR, UV, ¹H and ¹³C NMR, and mass spectra and elemental analyses, and their solvatochromic properties were examined. Probable mechanisms of nitrene insertion were discussed.

Full text of DOI:10.1134/S1070428008100102

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 10, pp. 1464–1470. © Pleiades Publishing, Ltd., 2008.
Published in Russian in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 10, pp. 1488–1494.
Insertion Reaction of Azidosulfonyl Azo Dye with Model
Alicyclic and Heterocyclic Compounds*
H. A. Dabbagha and A. Teimourib
a Department of Chemistry, Isfahan University of Technology, Isfahan, 8415483111, Iran
e-mail: dabbagh@cc.iut.ac.ir
b Payame Noor University, Isfahan, Iran
Received October 16, 2006
Abstract—Thermal reactions of 4-(2-hydroxynaphthalen-1-yldiazenyl)benzenesulfonyl azide with cyclo-
hexane, benzene, toluene, anisole, p-xylene, mesitylene, dihydropyran, and pyridine were studied. Structures of
1
the resulting azo dyes were confirmed by FT-IR, UV, H and 13C NMR, and mass spectra and elemental
analyses, and their solvatochromic properties were examined. Probable mechanisms of nitrene insertion were
discussed.
DOI: 10.1134/S1070428008100102
The chemistry of azo dyes was discussed in detail
by Zollinger [1]. Thermal decomposition of sulfonyl
azides and their reactions with monosubstituted ben-
zenes [2] and other aromatic compounds were reported
[3]. Reactions of sulfonyl azides with olefins, [4] some
hydrocarbons [5–10], benzo-fused cyclic β-keto esters
[11, 12], alkyl radicals [13], and vinyl ethers [14], as
well as addition of sulfonyl azides to dihydropyran,
were also described [14, 15]. Abramovitch et al.
[16, 17] studied thermolysis of benzene-1,2-disulfonyl
azide in benzene and cyclohexane and addition of
aromatic sulfonyl azides to simple acyclic and cyclic
dienes. Both aliphatic and aromatic sulfonyl azides
were found to insert into carbon–hydrogen bond of
saturated hydrocarbons [18]. The mechanism of fixa-
tion of reactive azide dyes containing an azidosulfonyl
Scheme 1.
SO2Cl
SO2N3
SO2N3
NaN3
HCl, NaNO2
AcNH
AcNH
Cl– N2
I
II
III
SO2N3
SO2X
2-Naphthol, H2O, KOH
Va–Vh, Δ
N
N
N
N
OH
OH
VIa–VIh
IV
Me
OMe
Me
Me
Me
Me
Me
O
N
Va
Vb
Vc
Vd
Ve
Vf
Vg
Vh
X = cyclo-C6H11NH (a), PhNH (b), 2-MeC6H4NH (c), 2-MeOC6H4NH (d), 2,5-Me2C6H3NH (e), 2,4,6-Me3C6H2NH (f), tetrahydro-
2H-pyran-2-ylideneamino (g), pyridin-1-ioimino (h).
* The text was submitted by the authors in English.
1464

INSERTION REACTION OF AZIDOSULFONYL AZO DYE
1465
group on nylon and polyesters was proposed in [19].
Thermal decomposition of imidoyl azides in the pres-
ence of various substituted benzenes was studied by us
in [20]. We recently reported on the synthesis of a new
group of reactive azo dyes containing an azido group
[21] and proposed a new method for the preparation of
azo dyes using clay catalysts [22].
a macroradical. Next follows either recombination of
the two radicals to form the same product as in the
reaction of singlet nitrene or abstraction of a proton
from another hydrocarbon to give primary sulfonamide
(Scheme 4).
Scheme 4.
O
S
O
S
In the present work we examined thermal reactions
of a reactive azidosulfonyl azo dye, 4-(2-hydroxynaph-
thalen-1-yldiazenyl)benzenesulfonyl azide with some
model compounds (cyclohexane, benzene, toluene,
anisole, p-xylene, mesitylene, dihydropyran, and pyri-
dine) with a view to get a deeper insight into the mech-
anism of its insertion reactions.
·
·
··
N
·
·
R
+
H
R'
R
NH + R'
O
O
O
O
·
·
R
S
NH
+
+
R'
R
S
NHR'
O
O
Initial 4-(2-hydroxynaphthalen-1-yldiazenyl)ben-
zenesulfonyl azide (IV) was prepared starting from
4-acetylaminobenzenesulfonyl chloride (I). Compound
I was converted into sulfonyl azide II by treatment
with sodium azide, deprotection of the amino group in
II and subsequent diazotization gave azidosulfonyl-
benzenediazonium salt III, and the latter was brought
into azo coupling with β-naphthol (Scheme 1). Ther-
mal decomposition of azide IV in the presence of
model compounds Va–Vh led to the formation of new
azo dyes VIa–VIh whose structure was established on
the basis of their elemental analyses and spectral data.
O
S
·
·
R
NH
H
+
R''
RSO2NH2
+
R''
O
·
·
R'
R''
R' R''
Another possible reaction path involves loss of the
sulfonyl azide moiety with formation of SO2. This path
was observed in the thermal decomposition of various
sulfonyl azides in mineral oil and organic solvents
[18, 23]. Presumably, the formation of SO2 is in some
way catalyzed by nitrenes or substances formed in
reactions involving nitrenes. The reaction is likely to
involve radical species, but the origin of the latter has
not been determined, and it could depend on the re-
action system (possible radical sources are nitrenes in
the triplet state). There are many puzzling features
concerning the formation of SO2. A probable reaction
path is shown in Scheme 5 [18, 23].
Thermal decomposition of sulfonyl azides in or-
ganic solvents and mineral oil was studied in detail
[18–23]. Generally, sulfonyl azides decompose at ele-
vated temperatures to form sulfonyl nitrene as shown
in Scheme 2.
Scheme 2.
O
S
O
S
Δ
··
··
N
·
Scheme 5.
·
RSO2N3
R
N
R
–N2
·
·
O
O
R'
+
R
SO2N3
R
SO2
+ R' N3
·
·
R
SO2
R
+
SO2
The nitrene can exist in both singlet and triplet
states that are capable of reacting with hydrocarbons in
different ways. The reaction involving the singlet
nitrene occurs as insertion into C–H bond to give
N-substituted sulfonamide (Scheme 3).
·
·
R
+
R'
H
R
H + R'
It is also important that oxygen should be absent
since it easily reacts with nitrenes to form nitroso
compounds according to Scheme 6 [24]. Other un-
desirable reactions are formation of azo dimers from
Scheme 3.
O
H–R'
··
R
S
N
RSO2NHR'
Scheme 6.
O
O
S
O
S
··
2 R
N
+ O2
2 R
N
O
The triplet nitrene reacts via abstraction of a proton
from hydrocarbon resulting in the formation of
O
O
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

DABBAGH, TEIMOURI
1466
two nitrenes and nitrene coupling with the initial azide
(Scheme 7). These reactions are more likely to occur
in pure sulfonyl azides or in highly concentrated
solution [25].
IV in benzene (or other aromatic compound) occurs
slowly at 170–178°C; nitrene addition gives benzo[b]-
aziridine intermediate B, and the subsequent cleavage
of the three-membered ring produces N-substituted
sulfonamides VIb–VIf (Scheme 9).
Scheme 7.
Scheme 9.
O
S
O
S
O
S
··
R1
2 R
N
R
N
N
R
O
O
O
Ar SO2N3
+
O
S
O
O
S
R5
R3
··
R
N
+
R
SO2N3
R
S
N
N
R
–N2
R4
O
O
O
IV
Vb–Vf
Model substrates studied in the present work con-
tained both Csp3–H and Csp2–H bonds. Aromatic com-
pounds Vb–Vf reacted with azide IV via formation of
nitrene intermediate which inserted into the Csp2–H
bond. By contrast, the reaction of IV with dihydro-
pyran Vg did not involve nitrene formation. Insofar as
the azido group is an 1,3-dipole, azides are capable of
reacting with many unsaturated compounds, especially
with electron-rich olefins, following the 1,3-dipolar
cycloaddition pattern. The reaction of azide IV with
dihydropyran Vg was complete at room temperature.
Presumably, the primary adduct, pyranotriazole A,
decomposed with elimination of nitrogen molecule,
and the subsequent 1,2-H shift gave the final product
(Scheme 8). This mechanism resembles that proposed
previously [15].
R1
H
Δ
ArSO2
N
R3
R5
R4
B
R1
ArSO2NH
R5
R3
R4
VIb–VIf
Analogous patter was observed by us previously
while studying thermal decomposition of imidoyl
azides in the presence of various substituted benzenes
[21]. Here, the major products were the corresponding
ortho-substituted derivatives. Isolation of minor prod-
ucts (para- and meta-substituted) was difficult because
of formation of other by-products (see Schemes 4–7).
Scheme 8.
N
Δ
Ar SO2N3
+
N
N
O
O
NHSO2Ar
Vg
IV
A
In the reaction with cyclohexane at 175°C under
pressure, insertion into the Csp3–H bond occurred
(Scheme 10), as in the reactions of sulfonyl azides with
aliphatic hydrocarbons reported previously [6, 10]
N2
N
~1,2-H
–N2
SO2Ar
O
O
N
H
SO2Ar
VIg
Scheme 10.
N
N
H
N
Δ
SO2Ar
Ar SO2N3
+
OH
Ar =
.
IV
Va
VIa
The reactions with substituted benzenes were pre-
sumed to involve nitrene addition, followed by rear-
rangement. Thermal decomposition of sulfonyl azide
We recorded the electronic absorption spectra of
azo dyes VIa–VIg in different solvents; the results are
summarized in Table 1. Compounds VIa–VIg charac-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

INSERTION REACTION OF AZIDOSULFONYL AZO DYE
1467
Table 1. Electronic absorption spectra of azo dyes VIa–VIh in different solvents
λmax, nm
Compound
no.
ethanol
acetone
dimethylformamide methylene chloride
acetonitrile
VIa
VIb
VIc
VId
VIe
VIf
210, 323, 474
210, 321, 477
211, 323, 477
213, 324, 478
211, 322, 476
211, 323, 477
211. 321, 477
211, 320, 477
210, 323, 474
210, 321, 478
212, 323, 477
213, 324, 478
211, 324, 477
211, 324, 477
211, 322, 475
211, 323, 476
210, 324, 478
210. 323. 480
212, 325, 480
213, 326, 482
211, 327, 481
211, 327, 480
211, 323, 479
211, 325, 480
211, 324, 477
210, 321, 478
212, 324, 476
212, 323, 479
211, 323, 478
212, 325, 478
211, 322, 476
211, 323, 475
210, 323, 475
210, 321, 476
211, 324, 477
213, 324, 476
211, 322, 476
211, 323, 476
211, 323, 474
211, 322, 475
VIg
VIh
teristically displayed absorption maxima in the regions
λ 210–213, 320–327, and 475–480 nm. The first two
bands originate from the aromatic rings, and the long-
wave absorption maximum was assigned to π–π* type
transition involving the whole conjugated system con-
sisting of naphthyl and phenyl rings and azo group.
The long-wave maximum was located at λ 475–
478 nm in ethanol, 474–479 nm in acetone, 478–
482 nm in dimethylformamide (DMF), 476–479 nm in
methylene chloride, and 474–477 nm in acetonitrile. It
is seen that these dyes show weak solvatochromism:
the red shift in going from weakly to strongly polar
solvents does not exceed 6 nm.
ination of the sulfonyl group from the molecular ion
and cleavage of the naphthylazophenyl fragment.
Thus the thermal reaction of 4-(2-hydroxynaph-
thalen-1-yldiazenyl)benzenesulfonyl azide (IV) with
cyclohexane, benzene, toluene, anisole, p-xylene, and
mesitylene gives the corresponding N-substituted sul-
fonamides as a result of insertion of intermediate
nitrene into the C–H bond of the substrate. In the
reaction with pyridine, nitrene addition at the nitrogen
atom occurs, while the reaction with dihydropyran fol-
lows 1,3-dipolar cycloaddition pattern with subsequent
elimination of nitrogen from intermediate pyrano-
triazole with formation of N-(tetrahydro-2H-pyran-2-
ylidene) sulfonamide.
The IR spectra of azo dyes VIa–VIh lacked azide
absorption but contained absorption bands due to
stretching vibrations of the OH (3427–3553 cm–1), NH
(3218–3308 cm–1), N=N (1343–1565 cm–1), and SO2
EXPERIMENTAL
1
groups (1162–1398 cm–1). The H NMR spectra of
The IR spectra were recorded in KBr on a JASCO
1
VIa–VIh are given in Experimental. The most abun-
dant ions in the mass spectra of dyes VIa–VIh had m/z
values 247, 171, and 143. They were formed via elim-
FT/IR-680 PLUS spectrometer. The H NMR spectra
were measured on a Bruker 500 Ultrashield spectrom-
eter (500 MHz) using DMSO-d6 as solvent. The mass
Table 2. Elemental analyses of azo dyes VIa–VIh
Found, %
Calculated, %
Formula
Compound
no.
C
H
N
C
H
N
VIa
VIb
VIc
VId
VIe
VIf
64.32
65.37
66.09
63.53
66.61
67.25
61.42
62.13
5.50
4.11
4.46
4.30
4.77
5.11
4.73
4.31
10.12
10.28
09.91
09.49
09.63
09.29
10.07
14.10
C22H23N3O3S
C22H17N3O3S
C23H19N3O3S
C23H19N3O4S
C24H21N3O3S
C25H23N3O3S
C21H19N3O4S
C21H16N4O3S
64.53
65.50
66.17
63.73
66.80
67.40
61.60
62.36
5.66
4.25
4.59
4.42
4.91
5.20
4.88
3.99
10.26
10.42
10.07
09.69
09.74
09.43
10.26
13.85
VIg
VIh
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

DABBAGH, TEIMOURI
1468
spectra (electron impact, 70 eV) were obtained on
a Fisons Trio 1000 spectrometer (UK). The UV spectra
were recorded on a JASCO V-570 UV/VIS/NIR
spectrophotometer. The elemental compositions were
determined at the Research Institute of Petroleum
Industry (Pazhouheshgah Bld., Qom Road, Tehran,
Iran). The melting points were determined on a Gallen-
kamp apparatus and are uncorrected. Analytical TLC
was performed on silica gel F254 plates (Merck) and
silica gel 60 (40–63 μm, Merck) was used for column
chromatography. 4-Acetylaminobenzenesulfonyl
chloride, cyclohexane, toluene, anisole, mesitylene,
3,4-dihydro-2H-pyran, and pyridine were commercial
products (Merck) which were used without further
purification. The elemental analyses of azo dyes VIa–
VIh are listed in Table 2.
174°C. IR spectrum, ν, cm–1: 3545, 2110, 1379.
1H NMR spectrum, δ, ppm: 15.6 s (1H, OH), 8.04 d
(2H, C6H4, J = 8.83 Hz), 7.98 d (2H, C6H4, J =
8.83 Hz), 6.66–8.37 m (6H, C10H6). 13C NMR spec-
trum, δC, ppm: 117.4, 122.9, 126.7 (2C), 128, 129,
129.6, 129.9 (2C), 130.2, 132.4, 133.4, 134.1, 144.0,
148.4, 180.7. UV spectrum (CH2Cl2), λmax, nm: 224,
313, 479. Mass spectrum: m/z 353 [M]+.
N-Cyclohexyl-4-[2-(2-hydroxynaphthalen-1-yl)-
diazenyl]benzenesulfonamide (VIa). A stainless steel
high-pressure reactor was charged with a degassed
solution of 0.653 g (1.8 mmol) of azo dye IV in 20 ml
(0.185 mol) of anhydrous cyclohexane, and the mix-
ture was heated for 3 h at 170–175°C, the progress of
the reaction being monitored by TLC. The mixture was
treated with acetone, the resulting solution was evap-
orated to dryness, and the residue was subjected to
chromatography on silica gel using cyclohexane–ethyl
acetate (80:20) as eluent to isolate an orange–red solid
whose IR spectrum lacked azide band. Yield 52%,
mp 192–194°C. IR spectrum, ν, cm–1: 3548, 3308,
N-(4-Azidosulfonylphenyl)acetamide (II). A solu-
tion of 48.6 g (208 mmol) of 4-acetylaminobenzene-
sulfonyl chloride in 500 ml of acetone was cooled to
0°C, a cold solution of 20 g (312 mmol) of sodium
azide in 200 ml of water was added dropwise under
stirring over a period of 1 h, and the mixture was
stirred for 1 h at 0°C. The mixture was then poured
into 1.5 l of an ice–water slurry, and the precipitate
was filtered off, washed with ice water, and dried
under reduced pressure. The product can be used in the
next step directly or recrystallized from aqueous ace-
tone. Yield 75%, colorless crystals, mp 108–110°C. IR
1
3065, 2966, 1613, 1565, 1385, 1178. H NMR spec-
trum, δ, ppm: 15.77 s (1H, OH), 8.46 d (1H, J =
9.63 Hz), 7.94 d (1H, J = 7.87 Hz), 7.94 d (2H, J =
8.5 Hz), 7.88 d (2H, J = 5.56 Hz), 7.65 d (1H, J =
7.92 Hz), 7.59 t (1H, J = 7.72 Hz), 7.46 t (1H, J =
7.53 Hz), 6.78 d (1H, J = 9.56 Hz). 13C NMR spec-
trum, δC, ppm: 23.23 (2C), 28.43, 33.54 (2C), 42.84,
118.60 (2C), 122.19, 126.13, 127.62, 128.45, 129.39,
129.42 (2C), 129.74, 131.12, 132.57, 132.59, 143.63,
148.34, 178.98. Mass spectrum: m/z 409 [M]+.
1
spectrum (KBr), v, cm–1: 2125, 1674, 1160. H NMR
spectrum, δ, ppm; 8.4 s (1H, NH), 7.82 d.d (4H, J =
13.58, 8.3 Hz, Harom), 2.23 s (3H, CH3). 13C NMR
spectrum, δC, ppm: 169.5, 144.1, 132.3, 128.9, 119.6,
24.7. Mass spectrum: m/z 240 [M]+.
4-[2-(2-Hydroxynaphthalen-1-yl)diazenyl]-
N-phenylbenzenesulfonamide (VIb) was obtained in
a similar way from 0.790 g (2.2 mmol) of azide IV and
20 ml (0.226 mol) of anhydrous benzene. Yield 41%,
orange–red solid, mp 256–258°C. IR spectrum, ν,
cm–1: 3551, 3228, 3075, 1623, 1563, 1343, 1182.
1H NMR spectrum, δ, ppm: 15.83 s (1H, OH), 8.41 d
(1H, J = 8.2 Hz), 7.92 d (1H, J = 9.72 Hz), 7.88 d (2H,
J = 8.79 Hz), 7.80 d (2H, J = 8.39 Hz), 7.67 d (1H, J =
10.45 Hz), 7.56 t (1H, J = 8.42 Hz), 7.45 t (1H, J =
6.82 Hz), 7.21 t (2H, J = 7.44 Hz), 7.01 t (1H, J =
8.06 Hz), 6.92 d (1H, J = 8.43 Hz), 6.73 d (1H, J =
8.70 Hz). 13C NMR spectrum, δC, ppm: 116.80 (2C),
117.76, 118.66, 123.14, 126.12, 127.71, 128.21,
128.41, 129.29, 129.38 (2C), 131.11, 132.51, 132.59,
137.52, 143.54, 148.02, 170.13. Mass spectrum:
m/z 403 [M]+.
4-(2-Hydroxynaphthalen-1-yldiazenyl)benzene-
sulfonyl azide (IV). A mixture of 2.4 g (10 mmol) of
sulfonyl azide II and 9 ml of concentrated hydro-
chloric acid was heated for 35 min under reflux. The
resulting solution was cooled to 0°C in an ice–salt
bath, a solution of 0.76 g (11 mmol) of sodium nitrite
in 20 ml of water was added dropwise under stirring,
maintaining the temperature below 5°C, and the mix-
ture was stirred for an additional 30 min on cooling.
The solution was then neutralized with a saturated
solution of sodium hydrogen carbonate, 1.44 g
(10 mmol) of 2-naphthol was slowly added under stir-
ring to the resulting suspension of diazonium salt III
(10 mmol), the mixture was stirred for 30 min, neutral-
ized with a saturated solution of sodium carbonate, and
stirred until complete precipitation (1–3 h). The precip-
itate was filtered off with suction, dried, and recrystal-
lized from toluene. Yield 87%, red plates, mp 172–
4-[2-(2-Hydroxynaphthalen-1-yl)diazenyl]-N-(2-
methylphenyl)benzenesulfonamide (VIc) was ob-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

INSERTION REACTION OF AZIDOSULFONYL AZO DYE
1469
tained in a similar way from 0.664 g (1.9 mmol) of
azide IV and 20 ml (0.188 mol) of anhydrous toluene.
The mixture was dissolved in hot acetonitrile, the solu-
tion was evaporated to dryness, and the residue was
subjected to chromatography on silica gel using cyclo-
hexane–ethyl acetate (80:20) as eluent. Yield 53%,
orange–red solid, mp 198–200°C. IR spectrum, ν,
cm–1: 3547, 3219, 3060, 2951, 1613, 1565, 1382, 1181.
1H NMR spectrum, δ, ppm: 15.65 br.s (1H, OH),
9.34 br.s (1H), 8.36 d (1H, J = 7.75 Hz), 7.90 d (1H,
J = 9.50 Hz), 7.81 d (2H, J = 8.59 Hz), 7.65 d (1H, J =
7.63 Hz), 7.73 d (2H, J = 8.87 Hz), 7.49 t (1H, J =
8.75 Hz), 7.12 t (1H, J = 7.83 Hz), 6.93 d (1H, J =
8.84 Hz), 6.85 t (1H, J = 9.16 Hz), 6.77 d (1H, J =
8.78 Hz), 6.71 d (1H, J = 8.77 Hz), 2.25 s (3H, CH3).
13C NMR spectrum, δC, ppm: 27.33, 114.15, 116.59,
117.65, 118.21, 121.35 122.19 (2C), 126.10, 127.81,
128.14, 128.35, 129.36, 129.45 (2C), 130.02, 131.25,
132.56, 132.95, 143.66, 145.30, 149.09, 177.87. Mass
spectrum: m/z 417 [M]+.
2.35 s (3H each, CH3). 13C NMR spectrum, δC, ppm:
16.30, 25.36, 115.72, 117.68, 119.77, 122.13 (2C),
126.13, 126.24, 127.39, 128.51, 129.39 (2C), 129.76,
129.88, 130.93, 131.11, 132.53, 132.59, 136.01, 136.31,
143.45, 148.06, 178.33. Mass spectrum: m/z 431 [M]+.
4-[2-(2-Hydroxynaphthalen-1-yl)diazenyl]-
N-(2,4,6-trimethylphenyl)benzenesulfonamide (VIf)
was obtained in a similar way from 0.511 g (1.4 mmol)
of azide IV and 20 ml (0.144 mol) of anhydrous
mesitylene. Yield 61%, mp 216–218°C. IR spectrum,
ν, cm–1: 3553, 3263, 3061, 2919, 1615, 1561, 1393,
1186. 1H NMR spectrum, δ, ppm: 15.75 br.s (1H, OH),
12.50 br.s (1H), 8.45 d (1H, J = 7.93 Hz), 7.91 d (1H,
J = 7.87 Hz), 7.89 d (2H, J = 8.53 Hz), 7.86 d (2H, J =
8.51 Hz), 7.71 d (1H, J = 7.75 Hz), 7.56 t (1H, J =
7.53 Hz), 7.41 t (1H, J = 7.51 Hz), 6.79 d (1H, J =
7.95 Hz), 6.79 d (1H, J = 7.95 Hz), 2.51 s (6H, CH3),
13
2.35 s (3H, CH3). C NMR spectrum, δC, ppm: 16.35,
25.75, 118.11, 123.44 (2C), 124.15, 126.36, 127.12,
127.25, 127.30, 128.24, 128.44, 129.13, 129.55 (2C),
130.43, 132.12, 142.31, 147.22, 149.10, 150.06, 175.20.
Mass spectrum: m/z 445 [M]+.
4-[2-(2-Hydroxynaphthalen-1-yl)diazenyl]-N-(2-
methoxyphenyl)benzenesulfonamide (VId) was ob-
tained in a similar way from 0.650 g (1.8 mmol) of
compound IV and 20 ml (0.184 mol) of anhydrous
anisole. Yield 44%, red solid, mp 186–188°C. IR spec-
trum, ν, cm–1: 3432, 3266, 3055, 2926, 1609, 1566,
4-[2-(2-Hydroxynaphthalen-1-yl)diazenyl]-N-
(tetrahydro-2H-pyran-2-ylidene)benzenesulfon-
amide (VIg). A thoroughly degassed solution of
0.747 g (2.1 mmol) of azide IV in 20 ml (0.211 mol)
of anhydrous dihydropyran was stirred at a moderate
rate for 3 days at room temperature. When the reaction
was complete (TLC), the mixture was washed with
acetone and evaporated to dryness, and the residue was
subjected to chromatography on silica gel using cyclo-
hexane–ethyl acetate (80:20) as eluent to isolate com-
pound VIg as an orange–red solid. Yield 37 %,
mp 264–266°C. IR spectrum, ν, cm–1: 3549, 3062,
1
1398, 1162. H NMR spectrum, δ, ppm: 15.70 br.s
(1H), 9.30 br.s (1H), 8.42 d (1H, J = 7.55 Hz), 7.92 d
(1H, J = 9.57 Hz), 7.87 d (2H, J = 8.62 Hz), 7.75 d
(1H, J = 8.74 Hz), 7.72 d (2H, J = 8.53 Hz), 7.45 t
(1H, J = 8.74 Hz), 7.09 t (1H, J = 7.88 Hz), 6.97 d
(1H, J = 8.89 Hz), 6.87 t (1H, J = 9.18 Hz), 6.79 d
(1H, J = 8.78 Hz), 6.72 d (1H, J = 8.78 Hz), 3.64 s
(3H, CH3). 13C NMR spectrum, δC, ppm: 65.83,
114.23, 116.61, 117.70, 118.11, 121.31, 122.17 (2C),
126.13, 127.61, 128.12, 128.41, 129.37, 129.38 (2C),
129.77, 131.11, 132.50, 132.58, 143.54, 145.41,
148.03, 178.13. Mass spectrum: m/z 433 [M]+.
1
2897, 1613, 1557, 1382, 1184. H NMR spectrum, δ,
ppm: 15.79 br.s (1H), 8.46 d (1H, J = 8.11 Hz), 7.94 d
(1H, J = 7.95 Hz), 7.93 d (1H, J = 8.70 Hz), 7.90 d
(1H, J = 8.74 Hz), 7.73 d (1H, J = 7.74 Hz), 7.59 t
(1H, J = 7.51 Hz), 7.46 t (1H, J = 7.57 Hz), 6.78 d
(1H, J = 8.15 Hz), 4.55 m (2H), 2.75 m (1H), 0.89 m
(4H). 13C NMR spectrum, δC, ppm: 21.37, 35.35,
68.42, 118.31, 123.10 (2C), 126.13, 128.42, 129.37
(2C), 129.77, 131.11, 132.50, 132.57, 143.55, 148.04,
170.11. Mass spectrum: m/z 409 [M]+.
N-(2,5-Dimethylphenyl)-4-[2-(2-hydroxynaph-
thalen-1-yl)diazenyl]benzenesulfonamide (VIe) was
obtained in a similar way from 0.572 g (1.6 mmol) of
sulfonyl azide IV and 20 ml (0.162 mol) of anhydrous
p-xylene. Yield 56 %, red solid, mp 210–212°C. IR
spectrum, ν, cm–1: 3427, 3265, 3072, 2969, 1635,
1
1558, 1388, 1169. H NMR spectrum, δ, ppm: 15.57 s
(1H, OH), 12.50 br.s (1H), 8.45 d (1H, J = 7.93 Hz),
7.93 d (1H, J = 9.53 Hz), 7.88 d (2H, J = 8.45 Hz),
7.72 d (2H, J = 7.95 Hz), 7.70 d (2H, J = 8.53 Hz),
7.57 t (1H, J = 7.70 Hz), 7.44 t (1H, J = 7.53 Hz),
7.06 d (1H, J = 8.17 Hz), 6.95 d (1H, J = 8.09 Hz),
6.84 q (1H), 6.77 d (1H, J = 2.31 Hz), 2.45 s and
4-[2-(2-Hydroxynaphthalen-1-yl)diazenyl]-N-
pyridiniobenzenesulfonimide (VIh). A thoroughly
degassed solution of 0.871 g (2.5 mmol) of sulfonyl
azide IV in 20 ml (0.247 mol) of anhydrous pyridine
was heated for 3 h at 170–175°C in a stainless steel
high-pressure reactor. When the reaction was complete
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

DABBAGH, TEIMOURI
1470
8. Yamamoto, I., Tokanou, H., Uemura, H.-a., and
Gotoh, H., J. Chem. Soc., Perkin Trans. 1, 1977, no. 11,
p. 1241.
(TLC), the mixture was treated as described above to
isolate compound VIh as an orange–red solid. Yield
40%, mp 246–248°C. IR spectrum, ν, cm–1: 3477,
1
9. Merkx, R., Brouwer, A.J., Rijkers, D.T.S., and Lis-
2979, 1635, 1508, 1379, 1176. H NMR spectrum, δ,
kamp, R.M.J., Org. Lett., 2005, vol. 7, p. 1125.
10. Sloan, M.F., Renfrow, W.B., and Breslow, D.S., Tetra-
hedron Lett., 1964, vol. 5, no. 39, p. 2905.
11. Benati, L.. Calestani, G., Nanni, D., and Spagnolo, P.,
J. Org. Chem., 1998, vol. 63, p. 4679.
12. Benati, L., Nanni, D., and Spagnolo, P., J. Org. Chem.,
ppm: 15.74 br.s (1H), 8.54 d (1H, J = 8.26 Hz), 8.22 d
(2H, C6H4, J = 8.83 Hz), 8.16 d (2H, J = 8.81 Hz),
7.95 d (1H, J = 9.31 Hz), 7.86 t (2H, J = 8.13 Hz),
7.78 d (1H, J = 7.87 Hz), 7.60 t (1H, J = 7.77 Hz),
7.55 t (2H, J = 7.66 Hz), 7.45 t (1H, J = 7.48 Hz),
7.37 d (1H, J = 7.33 Hz), 6.92 d (1H, J = 8.37 Hz).
13C NMR spectrum, δC, ppm: 119.72 (2C), 122.77,
126.13, 127.63 (2C), 128.31, 129.37, 129.48, 129.78,
131.10, 132.50, 132.57, 142.78, 143.55, 145.53, 148.03,
176.33. Mass spectrum: m/z 404 [M]+.
1999, vol. 64, p. 5132.
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The authors thank Isfahan University of Tech-
nology for financial support (Research Council Grant
IUT-84/500/9143).
15. Franz, J.E., Dietrich, M.W., and Henshall, A., J. Org.
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