Novel covalently linked pyrene-aryl azide systems: synthesis of 1-(4-azidobenzoyloxy)pyrene

Article abstract of DOI:10.1016/j.mencom.2015.07.008

Lead tetraacetate oxidation of pyrene followed by hydrolysis affords 1-hydroxypyrene whose esterification with 4-azidobenzoic acid gives a new bifunctional luminophore characterized by UV and luminescence spectroscopy.

Full text of DOI:10.1016/j.mencom.2015.07.008

Mendeleev
Communications
Mendeleev Commun., 2015, 25, 260–261
Novel covalently linked pyrene–aryl azide systems:
synthesis of 1-(4-azidobenzoyloxy)pyrene
a
a
a,b
Igor I. Barabanov,* Alexander V. Polukhin, Valerii V. Korolev,
a,b
b,c
Leonid V. Kuibida and Andrey A. Nefedov
a
V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of
Sciences, 630090 Novosibirsk, Russian Federation. Fax: +7 383 330 7350; e-mail: barabanov@kinetics.nsc.ru
Novosibirsk State University, 630090 Novosibirsk, Russian Federation
b
c
N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,
6
30090 Novosibirsk, Russian Federation
DOI: 10.1016/j.mencom.2015.07.008
Lead tetraacetate oxidation of pyrene followed by hydrolysis affords 1-hydroxypyrene whose esterification with 4-azidobenzoic acid
gives a new bifunctional luminophore characterized by UV and luminescence spectroscopy.
The bridged pyrene–aryl azide systems, a narrow and poorly
investigated group of compounds,1 can be interesting for studying
photoaffinity labeling of biopolymers by binary reagents.
hydrocarbons with lead tetraacetate.10,11 It was reported12–14 that
such an oxidation of pyrene 4 furnished 1­acetoxypyrene 5 and
isomeric 1,6­ and 1,8­diacetoxypyrenes, however, detailed proce­
dures, product yields and approval of their structure were not given.
In our hands, pyrene 4 was fully oxidized with a ~10% molar
,2
3
–6
Binding of the pyrenyl and azidoaryl groups by bridges (X) of
various lengths and structures allows one to vary the rate con­
stants of elementary processes and investigate their dynamics
excess of Pb(OAc) in a boiling (3 h) mixture of benzene and
4
1
and mechanism. Recently, we have synthesized the first esters
acetic acid (9:1 v/v). According to TLC and the chromatomass­
spectrometric analysis, the reaction affords 1­acetoxypyrene 5
and diacetoxypyrene (Scheme 1). After a preparative chromato­
graphic separation, compound 5 was obtained in 49% yield.†
The structure of the target 1­acetoxypyrene 5 was identified
by melting point, IR and mass spectra. The IR spectrum of 5
demonstrates a characteristic absorption band of an ester carbonyl
of pyren­1­ylalkanols with 4­azido­2,3,5,6­tetrafluorobenzoic
acid. Primary physical and chemical processes that occur upon
photoexcitation of these molecules have been studied using pico­
second and nanosecond absorption and luminescence spectro­
scopy, and quantum chemistry.1 Quenching of the local pyrene
fluorescence by the azidoaryl moiety was revealed to occur by
the electron and energy transfer mechanisms. Here, we report the
synthesis and spectroscopic properties of previously unknown
,7
–
1
group at 1763 cm , and the mass spectrum contains the signal
of molecular ion at m/z 260.
1
­(4­azidobenzoyloxy)pyrene 1.
The esterification of 4­azidobenzoic acid 2 with 1­hydroxy­
In the IR spectrum of diacetoxypyrene (yield 13%), the
absorption bands for the carbonyl groups appear at 1763 cm .
8
–1
9
(a),(b)
pyrene 3
was supposed to be the optimal access to com­
Its mass spectrum exhibits the molecular ion at m/z 318. How­
ever, as compared with acetoxyarene 5, diacetate looks in the
chromatospectrogram as a broadened peak. These data along
pound 1. Despite a simple structure of the 1­hydroxypyrene 3, all
known ways of its synthesis from pyrene 4 are very complicated
and require the use of special reagents and conditions. In this study,
we used a direct acetoxylation of condensed polycyclic aromatic
9
1
with H NMR spectrum testify to the presence of isomers. The
1
H NMR spectrum contains double set of neigboring singlets for
the protons of the methyl groups at ~2.5 ppm and the well­
separated doublet signals from all protons of the pyrene nucleus
in the 7.76–8.24 ppm region of close intensity. Most probably,
this material is a mixture of 1,6­ and 1,8­diacetoxypyrenes in a
Me
N
I–
O
O
i
N3
COOH
N3
~
1:1 molar ratio.
2
4
3
6
1
­Acetoxypyrene 5 was hydrolyzed in a boiling aqueous­
ethanol NaOH solution. The following evaporation of organic
solvent from the reaction mixture and its acidification afforded a
white fine­crystalline precipitate of high­purity pyrenol 3, which
ii
iii
†
was identified by its melting point, IR and mass spectra.
OAc
The esterification on using 2­chloro­1­methylpyridinium iodide
5
1
5
(the Mukaiyama reagent) was the method of choice to access
N3
1
1
­(4­azidobenzoyloxy)pyrene 1 (see our previous related studies ).
1
5
iv
Although Mukaiyama works present no reactions of aromatic
carboxylic acids with phenols, we anticipated that this method
may be used for condensation of the chemically labile 4­azido­
benzoic acid 2 with pyrenol 3 into ester 1 under similar condi­
OH
O
O
1
†
The course of reactions and the purity of products were controlled by TLC
Scheme 1 Reagents and conditions: i, 2­chloro­1­methylpyridinium iodide,
Et N; ii, Pb(OAc) , PhH–AcOH; iii, NaOH, EtOH–H O; iv, 2, 2­chloro­
monitoring on Silufol UV 254 plates under UV light (eluents: benzene,
dichloromethane, a mixture of benzene or dichloromethane and hexane).
3
4
2
1
­methylpyridinium iodide, Et N, CH Cl , room temperature, 4 h.
3 2 2
©
2015 Mendeleev Communications. Published by ELSEVIER B.V.
–
260 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2015, 25, 260–261
tions, the salt 6 being an intermediate. In fact, 1­hydroxypyrene
readily reacted with acid 2 in the presence of pyridine salt and
triethylamine at room temperature to give the expected ester 1
36% yield after chromatographic separation) and by­products.
1
3
1
0
.0
.5
3
(
1
The structure of ester 1 was fully confirmed by the IR and H NMR
2
†
spectra as well as by the HRMS data. The mass spectra of 1,
obtained by the methods of electron and laser ionization, display
the signals of molecular ion at m/z 363. The mass spectrum of 1,
recorded using the method of laser ionization, contains a charac­
teristic signal with m/z 335, whose value corresponds to the
molecular mass of 4­(pyren­1­yloxycarbonyl)phenylnitrene.
3
13 nm
4
0.0
3
00
350
400
450
We also recorded the UV­VIS and luminescence spectra of
l/nm
‡
1
­(4­azidobenzoyloxy)pyrene 1 (Figure 1). The structure and
positions of the absorption bands of compound 1 were found to
be practically independent of the solvent polarity (hexane and
acetonitrile), only small bathochromic shift of the long­wavelength
bands (about 5 nm) was observed. The efficiency of compound 1
Figure 1 (1, 2) UV­VIS and (3, 4) luminescence spectra of (1, 3) pyrene 4
and (2, 4) (azidoaroyl)pyrene 1 in deoxygenated acetonitrile solution at room
temperature; spectra (3, 4) detected upon 313 nm photoexcitation.
fluorescence is negligible compared to that of pyrene 4 (see
Figure 1). This is due to very efficient intramolecular quenching
of the local pyrene fluorescence by the aryl azide group. The
1
-Acetoxypyrene 5 and diacetoxypyrenes. A solution of 0.30 g (1.48 mmol)
of pyrene 4 and 0.73 g (1.65 mmol) of Pb(OAc) in a mixture of 1.2 ml of
glacial AcOH and 10.8 ml of anhydrous benzene was stirred under reflux
for 3 h. The mixture was cooled, diluted with 25 ml of benzene and washed
with H O (3×25 ml). The organic layer was evaporated in vacuo. The oily
4
quantum yield of pyrene 4 fluorescence is about 0.3 and its singlet
16,17
state lifetime is about 300 ns.
Thus, the quantum yield of
2
compound 1 fluorescence could be estimated to be less than
residue was chromatographed on silica gel with benzene to give a fraction,
–
4
5
×10 and the singlet state lifetime to be less than 1 ns. A similar
containing monoacetoxypyrene 5, yield 0.19 g (49%), mp 104–105°C
benzene–hexane, lit.,12 104–105°C). IR (CHCl , n/cm ): 1763 (C=O).
–1
situation was observed for hexane solutions of 1.
(
3
+
Note that UV irradiation of 1­(4­azidobenzoyloxy)pyrene 1
solutions leads to its rapid photodestruction accompanied by an
increase of the structureless absorption in the 200–600 nm region.
Thus, we have prepared the new bifunctional compound
MS, m/z (%): 260 (12, M ), 218 (100), 189 (61), 163 (4), 95 (5), 43 (8). Then
benzene was replaced by chloroform and finally, diacetoxypyrenes were
eluted, yield 0.06 g (13%), mp 179–180°C (benzene–hexane). H NMR
CDCl ), d: 2.54 and 2.55 (2s, 6H, Me), 7.80 (d, 2H, J 8.3 Hz), 8.05
1
(
3
and 8.09 (2d, 4H, J 8.1 Hz), 8.18 and 8.19 (2d, 2H, J 8.3 Hz). IR (CHCl ,
3
1
­(4­azidobenzoyloxy)pyrene whose spectral data demonstrate
–1
+
n/cm ): 1763 (C=O). MS, m/z (%): 318 (10, M ), 276 (12), 234 (100),
05 (15), 176 (28), 150 (5), 43 (14).
-Hydroxypyrene 3. A solution of 0.19 g (0.73 mmol) of 1­acetoxy­
very efficient intramolecular quenching of local pyrene fluore­
scence. This compound seems promising for further studies of
the photoaffinity labeling mechanisms.
2
1
pyrene 5 and 0.19 g (4.75 mmol) of NaOH in a mixture of 8.1 ml of EtOH
and 5.4 ml of H O was heated under reflux for 2.5 h. EtOH was distilled
2
off in vacuo and the small portions of 2.7 ml of conc. HCl were added
dropwise on cooling and stirring. The precipitate of 3 was filtered, washed
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8
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3
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Received: 6th August 2014; Com. 14/4440
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–