Synthesis of crowned triazolephthalocyanines

Article abstract of DOI:10.1002/1099-0690(200008)2000:15<2767::aid-ejoc2767>3.0.co;2-2

The synthesis of triazolephthalocyanines bearing crown ether and aza-crown ether substituents is described. Different substituents have been introduced on the nitrogen atom of the aza-crown moiety to improve the solubility and the intrinsic amphiphilic character of these macrocycles. The crowned triazolephthalocyanines described have been prepared by a statistical procedure, and also by different variations of a stepwise method. Preliminary studies of the aggregation properties of one representative of this new family of compounds have also been carried out. An exhaustive study of the synthesis of the corresponding dicyano derivative precursors of the triazolephthalocyanines is displayed. Two different approaches have been used for this goal: The first one inserts the cyano groups prior to the synthesis of the crown ether moiety, while the second one builds the crown ether part of the molecule in advance of the cyanation process. The incompatibility of the Rosemund-von-Braun cyanation conditions and the presence of nitrogen atoms in the molecule is the main difficulty of the synthesis of these pre-cursors.

Full text of DOI:10.1002/1099-0690(200008)2000:15<2767::aid-ejoc2767>3.0.co;2-2

FULL PAPER
Synthesis of Crowned Triazolephthalocyanines
[a]
[a]
[a]
[a]
´
´
Beatriz Cabezon, Ernesto Quesada, Sagrario Esperanza, and Tomas Torres*
Keywords: Phthalocyanines / Triazole macrocycles / Noncentrosymmetric compounds / Crown ether compounds /
Aggregation properties
The synthesis of triazolephthalocyanines bearing crown
ether and aza-crown ether substituents is described. Differ-
ent substituents have been introduced on the nitrogen atom
of the aza-crown moiety to improve the solubility and the
intrinsic amphiphilic character of these macrocycles. The
study of the synthesis of the corresponding dicyano derivat-
ive precursors of the triazolephthalocyanines is displayed.
Two different approaches have been used for this goal: The
first one inserts the cyano groups prior to the synthesis of the
crown ether moiety, while the second one builds the crown
crowned triazolephthalocyanines described have been pre- ether part of the molecule in advance of the cyanation pro-
pared by a statistical procedure, and also by different vari- cess. The incompatibility of the Rosemund-von-Braun cyan-
ations of a stepwise method. Preliminary studies of the ag-
gregation properties of one representative of this new family
of compounds have also been carried out. An exhaustive
ation conditions and the presence of nitrogen atoms in the
molecule is the main difficulty of the synthesis of these pre-
cursors.
Introduction
shown liquid-crystal behaviour.[17] Moreover, these com-
pounds can be self-assembled by the LangmuirϪBlodgett
technique, to afford in-plane organised films[18,19] with
semiconducting properties, and can be applied as gas-
sensor devices.[20]
Two synthetic methodologies have been developed for
obtaining Tpcs: a single-step metal template method, and a
two-step method.[21,22] The former, in which the corres-
ponding 1,3-diiminoisoindoline and the 3,5-diamino-1,2,4-
triazole (guanazole) are allowed to react in a 3:1 molar ratio
in the presence of a metal salt, which acts as template, al-
lows for the preparation of Tpcs bearing the same substitu-
ents in the three isoindole moieties.[21] The latter represents
a good strategy for the preparation of unsymmetrically sub-
stituted Tpcs.[22,23]
Noncentrosymmetrical phthalocyanines[1Ϫ4] and related
compounds[5,6] have attracted a great deal of attention due
to their unusual second-order nonlinear optical
properties.[7Ϫ9] The special characteristics of these com-
pounds make them suitable for applications as molecular
organic materials, for example in opto-electronics.[8] How-
ever, the selective synthesis of these systems by classical
statistical cyclotretamerization employing two differently
substituted phthalonitriles is not easy, especially con-
sidering the difficulties in restraining a thermodynamically
controlled reaction such as the synthesis of the phthalocy-
anine macrocycle. Most of the synthetic effort has focused
on the preparation of unsymmetrically substituted phthalo-
cyanines with different groups at the periphery of the aro-
matic system.[10Ϫ12] Another approach, which is less de-
veloped, involves the preparation of noncentrosymmetrical
phthalocyanine analogues, formally obtained by the substi-
tution of one isoindole subunit in a phthalocyanine by an-
other conjugated heterocyclic moiety.[4,13]
As a consequence of our interest in the synthesis of non-
centrosymmetrical phthalocyanines with high second-order
nonlinear optical responses, we prepared, for the first time,
the so-called ‘‘triazolephthalocyanine’’ (Tpc),[14] a phthalo-
cyanine analogue in which one 1,2,4-triazole subunit has
formally replaced an isoindole subunit of the phthalocyan-
ine core. These unsymmetrical macrocycles display import-
ant second- and third-order nonlinear optical properties in
solution,[15] and high thermal stability,[16] similar and even
higher to those shown by phthalocyanines. Triazolephthalo-
cyanines bearing peripheral lipophilic substituents have
A wide variety of triazolephthalocyanines differing in the
number and type of substituents have been characterised,
but to the best of our knowledge, no examples of crown
ethers containing triazolephthalocyanines have been de-
scribed. On the contrary, crowned Pcs have been extensively
studied.[24Ϫ31] The introduction of crown ethers in the peri-
phery of the Tpc will be of great interest because of the
strong and selective capability of complexation of these
moieties that would improve the applications of these mac-
rocycles as molecular materials. As an example, depending
on the size of the cation complexed in the crown ether it is
possible to control the stacking degree of the macro-
cycles.[32] Nevertheless, the synthesis of the appropriate 1,2-
dicyanobenzene precursors is not obvious, due to the lim-
ited synthetic approaches available for introducing cyano
subunits on a benzene ring, and the incompatibilities be-
tween functional groups.
[a]
In the present paper, we describe for the first time, the
synthesis of triazolephthalocyanines bearing crown ether
substituents that could allow the application of these sys-
tems as ion-electronic devices.[28] The introduction of aza-
´
Organic Chemistry Department (CϪI), Autonoma University
of Madrid Cantoblanco
28049 Madrid, Spain
Fax: (internat.) ϩ 34-91/397-3966
E-mail: tomas.torres@uam.es
Eur. J. Org. Chem. 2000, 2767Ϫ2775
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ193X/00/0815Ϫ2767 $ 17.50ϩ.50/0
2767

´
B. Cabezon, E. Quesada, S. Esperanza, T. Torres
FULL PAPER
crown substituents is especially suitable, since it allows the the Rosenmund-von-Braun reaction starting from 4,5-di-
introduction of long aliphatic chains in the crown through bromocatechol (1) conveniently protected as an acetal de-
its nitrogen atom, thus improving the intrinsic amphiphilic rivative.[38,39] However, attempts to reproduce the described
character of the Tpcs and supporting their organisation in yields were unsuccessful, probably due to partial cleavage of
LangmuirϪBlodgett films.[18,19] Preliminary studies of their the acetal under the cyanation conditions. For this reason, a
aggregation properties in solution have also been per- different hydroxy group protection, namely benzylic ethers,
formed.
was essayed. Thus, 4,5-dibenzyloxy-1,2-dibromobenzene (2)
was prepared by reaction of 4,5-dibromocatechol (1) with
an excess of benzyl chloride in the presence of potassium
carbonate as base. The synthesis of the 4,5-dicyano derivat-
ive 3 was carried out by the Rosenmund-von-Braun reac-
tion, with an excess of CuCN in boiling DMF in good yield
(60%). The cleavage of the benzylic groups was carried out
by hydrogenolysis. Thus, bubbling hydrogen through a sus-
pension of 3, palladium/10% activated carbon, and ethyl
acetate afforded 1,2-dicyanocatechol (4) in high yield (91%).
However, the alkylation of 4 with 2-(2-chloroethoxy)-
ethanol was unsuccessful. Although different solvents, reac-
tion conditions, and alkylating agents were attempted, only
traces of monoalkylation and dialkylation products were
detected by NMR (estimated yield 5%). The main compon-
ent of the crude mixture was the starting dicyano derivative
4. The unworkable amounts of dialkylated compound ob-
tained because of the low reactivity of 4 due to the electron-
withdrawing effect of the cyano groups eliminated this strat-
egy for preparing dicyanobenzo-aza-crowns.
Results and Discussion
Bekarouglu and co-workers have previously described
aza-crown-substituted phthalocyanine derivatives.[33Ϫ35]
However, the synthetic route described for preparing the
corresponding dicyanobenzene precursors is not convergent
enough to allow the introduction of a wide variety of sub-
stituents on the amino function of the aza-crown at an ad-
vanced step of the synthesis. In an attempt to develop a
more versatile procedure for the preparation of N-substi-
tuted aza-crown derivatives, two different approaches for
obtaining 1,2-dicyanobenzo-aza-crown derivatives were
studied. The first one introduces the cyano groups prior to
the crown ether synthesis (Scheme 1), while the second one
builds the crown ether moiety in advance of the cyanation
process (Scheme 2). Both procedures employ 4,5-dibromo-
catechol (1)[36,37] as starting material.
The second proposed route (Scheme 2) requires the pro-
tection of the amino function (NH group of compound
8,[33] Scheme 3), since the high nucleophilic character of the
cyanide anions produces undesirable side reactions on this
group during further cyanation processes.[33] In this strat-
egy, the key compound is the dibromo compound 7, since
it affords the possibility of substituting the benzyl group by
a
wide variety of carbamate and amide functions
(Scheme 2). Compound 7 was prepared in a three-step
route. Alkylation of 4,5-dibromocatechol (1) as previously
described by Nolte afforded 5.[37] The aza-crown ring clos-
ure from 5 required the conversion of the hydroxy functions
into an appropriate leaving group, and for this reason, 6
was synthesised in high yield by dropwise addition of a so-
lution of mesyl chloride to a cooled (0 °C) solution of 5.
Further condensation of 6 with benzylamine yielded 7.
However, the cyanation of 7 employing the Rosemund-
von-Braun conditions did not provide the corresponding di-
cyano derivative, probably because of the localised electron
pair of the secondary amine in the aza-crown subunit,
which gives rise to undesired side reactions. In order to
overcome this problem, we decided to introduce an elec-
tron-delocalising substituent on the aza-crown ether.
Scheme 1
To synthesise the dicyanobenzo-aza-crown 10 from 7
(Scheme 3), the cleavage of the benzyl group and the intro-
duction of the amide function before cyanation were neces-
sary. The delocalisation of the electron pair of the nitrogen
atom by the amide function enables the cyanation process
to proceed in this case. Compound 8, prepared by bubbling
hydrogen gas through a suspension of 7 and palladium/10%
Scheme 2
In the first route (Scheme 1) the key compound is 1,2- activated carbon, was allowed to react with stearoyl chlor-
dicyanocatechol (4), which has already been prepared by ide to provide 9 in high yield. The synthesis of the 4,5-
2768
Eur. J. Org. Chem. 2000, 2767Ϫ2775

Synthesis of Crowned Triazolephthalocyanines
FULL PAPER
Scheme 4
treated (Scheme 5, route a) with equimolar amounts of
18[41] to afford the triazolephthalocyanine 24.
To synthesise compound 25, a two-step one-pot reaction
was employed.[22] In this strategy, the three-unit metal com-
plex was prepared in the same way described above, but it
was not isolated. The appropriate amount of the 1,3-diimin-
oisoindoline 20 was added to the reaction mixture produced
in the first step, once it had reached the temperature re-
quired for the second one (40 °C) (Scheme 5, route b).
Another efficient modification based on this approach
was used to prepare 27 and 28 (Scheme 6). The method
involves the one-step reaction of equimolar amounts of the
three-unit ligands 22a or 22b, nickel(II) acetate, and the cor-
responding 1,3-diiminoisoindoline 21 or 18, respectively[15]
(Scheme 6, route c).
Recently, we have discovered that dicyano derivatives are
also able to react with the three-unit ligand 22a in the pres-
ence of the nickel(II) and copper(II) salts to afford the cor-
Scheme 3
dicyano derivative 10 was carried out as described above, responding triazolephthalocyanine employing the same
by the Rosenmund-von-Braun reaction with an excess of general conditions described above.[42] Triazolephthalocy-
CuCN in boiling DMF.
anine 26 was prepared by this methodology (Scheme 6,
Compounds 11, 12, and 13, bearing a benzyl, ethyl, and route d).
octadecyl carbamate moiety, respectively (Scheme 3), were
Finally, triazolephthalocyanine 29 (Scheme 7), bearing
prepared by reaction of 7 in the presence of an excess of the the same substituents in the three isoindole subunits, was
corresponding chloroformate. Again, the cyanation process prepared in a very low yield following a statistical proced-
affords the corresponding dicyano precursors 14, 15, and 16 ure. This was done by heating stoichiometric amounts of
in good yields due to the presence of a carbamate function. 5,6-(1,4,7,10,13-pentaoxatridecamethylene)-1,3-
Compounds 14 and 15 are not only precursors to the diiminoisoindoline (18), guanazole, and nickel(II) acetate in
triazolephthalocyanines described below, but can also be 2-ethoxyethanol to reflux (Scheme 7).
hydrolysed to yield 17. This versatile compound 17 allows
Yields of the cyclocondensation reaction mentioned
the preparation of dicyanobenzo-aza-crown derivatives with above are relatively lower than those obtained for related
a wide variety of substituents, such as compounds 10 and alkoxytriazolephthalocyanines.[15,17,19] One reason of this
16 described above, by reaction with the corresponding acid behaviour could be the ease with which crown ethers form
chloride or chloroformate, respectively. Compound 17 is aggregates, thereby reducing the reactivity of the 1,3-diimin-
also especially suitable for preparing dicyanobenzo-aza- oisoindoline precursors and also resulting in the difficulties
crown derivatives alkylated on the amino group that cannot in the purification process. This trend is justified, since the
be easily prepared by another way.
lowest isolated yield corresponds to the triazolephthalocy-
1,3-Diiminoisoindolines 18Ϫ21 (Scheme 4) were pre- anine 29 bearing three crown ethers.
pared following the standard procedure, bubbling ammonia
All compounds were characterised by elemental analysis,
gas through a solution of the corresponding dicyano deriv- IR, and UV/Vis spectroscopies, mass spectrometry, and
ative in dry methanol in the presence of catalytic amounts NMR techniques.
of sodium methoxide.
UV/Vis spectroscopy might be a useful tool for studying
To prepare the triazolephthalocyanines, different routes aggregation phenomena in phthalocyanines and related
have been employed (Scheme 5). Compound 24 was pre- compounds in solution.[43] It is well known, that crowned
pared in a two-step reaction[22] from the three-unit ligand Pcs aggregate in the presence of alkaline metal ions.[24,44]
22a, which was treated with equimolar amounts of
The electronic absorption spectrum of the monocrown-
nickel(II) acetate to isolate its mononickel(II) complex 23a triazolephthalocyanine 24 in a chloroform/methanol (10:1)
as previously described by us.[40] This complex was then solution (ca. 5 ϫ 10Ϫ5 ) shows two strong absorption
Eur. J. Org. Chem. 2000, 2767Ϫ2775
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B. Cabezon, E. Quesada, S. Esperanza, T. Torres
FULL PAPER
Scheme 5
Scheme 6
bands in the near UV region at 260 and 370 nm, together
Unfortunately, compound 29 bearing three crown ether
with several weaker absorptions in the UV/Vis region at subunits could not be studied due to its low solubility in
525, 570, and 625 nm (Q-band).[14] The addition of potas- chloroform/methanol mixtures. Further studies will be de-
sium acetate to the solution of 24 mentioned above gives veloped with more soluble derivatives related to 29.
rise to notable changes in the UV/Vis spectrum. Spectra
were taken at three different molar ratios of macrocycle/
salt, namely 1:0.5, 1:1 and 1:10.
Summary and Conclusion
On increasing the concentration of the salt, the absorp-
We have described for the first time, the synthesis of tria-
tions corresponding to the bands in the 250Ϫ370 nm region zolephthalocyanines bearing crown ether and aza-crown su-
increase in intensity, whereas the absorptions corresponding bunits. Different substituents have been introduced on the
to the bands in the visible region decrease slightly. Similar nitrogen atom of the aza-crown moiety to improve the solu-
qualitative results were obtained with a larger ion like Rbϩ. bility and the intrinsic amphiphilic character of the Tpcs. It
These facts may be rationalised according to our previous will allow us to study the influence of the different func-
experience[43,45] in related compounds, in terms of aggrega- tional groups on the organisation properties of the triazo-
tion of the crowned triazolephthalocyanine indicated by al- lephthalocyanine at a supramolecular level. The crowned
kali metal ions, which coordinate the crown ether ring. This triazolephthalocyanines have been prepared, not only by a
fact was observed for the first time in triazolephthalocyan- statistical procedure, but also by different variations of a
ine compounds.
stepwise method.
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Synthesis of Crowned Triazolephthalocyanines
FULL PAPER
Synthesis: Compounds 1,[36,37] 4,[38] 5,[37] 8,[33] 18,[41] and 22,[17,46]
have been previously described. Starting materials were purchased
from Aldrich Chemical Co. and used as received without further
purification. Solvents were either employed as purchased or dried
according to procedures described in the literature.
1,2-Dibenzyloxy-4,5-dibromobenzene (2):
A
mixture of 1[36,37]
(5.00 g, 18.66 mmol), benzyl chloride (7.10 g, 56.00 mmol), K2CO3
(15.50 g, 112.00 mmol), and ethanol (75.0 mL) was stirred under
reflux for 8 h. After cooling to room temperature, the solvent was
removed and the crude extracted in a mixture water/CH2Cl2. The
organic solution was dried with anhydrous Na2SO4 and the solvent
was removed. Washing in methanol afforded 6.5 g of 2. Yield 78%.
M.p. 138Ϫ140 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ 7.5Ϫ7.3
(m, 10 H, H Ar), 7.17 (s, 2 H, H Ar), 5.11 (s, 4 H, 2·CH2 Bz). Ϫ
13C NMR (CDCl3, 75 MHz): δ ϭ 148.9 (C-1), 136.3 (C-1Ј), 128.6
(C-3Ј), 128.1 (C-4Ј), 127.4 (C-2Ј), 119.5 (C-2), 115.5 (C-3), 71.7
(CH2 Bz). Ϫ EM-EI; m/z: 448 [Mϩ], 181. Ϫ IR (KBr): ν˜ ϭ 3040,
2930, 2870, 1556, 1490, 1464, 1350, 1240, 1190, 1000, 755, 700
cmϪ1. Ϫ C20H16Br2O2 (448.1524) : C 53.60, H 3.60; found C 53.52,
H 3.41.
Scheme 7
1,2-Dibenzyloxy-4,5-dicyanobenzene (3): A mixture of 2 (5.00 g,
11.20 mmol), CuCN (7.00 g, 78.10 mmol), and dry DMF (100 mL)
was heated under reflux for 21 h under argon. After cooling to
room temperature, ammonium hydroxide was added and air was
bubbled through the mixture for 8 h. After filtration of the crude
mixture, the residue was purified by recrystallisation in methanol
to afford 2.28 g of 3 as a white solid. Yield 60%. M.p. Ͼ 200 °C.
An exhaustive study of the synthesis of the corresponding
dicyano derivative precursors of the triazolephthalocyan-
ines has been carried out. Different routes have been de-
veloped and several interesting key compounds (4, 7, and
17) have been synthesised. Compound 7 is a good target for
preparing dicyanobenzo-aza-crown derivatives where the
Ϫ
1H NMR (CDCl3, 200 MHz): δ ϭ 7.5Ϫ7.3 (m, 10 H, H Ar),
electron pair of the nitrogen atom is delocalised. The in- 7.19 (s, 2 H, H Ar), 5.13 (s, 4 H, CH2 Bz). Ϫ 13C NMR (CDCl3,
75 MHz): δ ϭ 152.8 (C-1), 135.2 (C-1Ј), 129.6 (C-3Ј), 129.3 (C-4Ј),
127.9 (C-2Ј), 117.9 (C-2), 116.3 (CN), 109.7 (C-3), 72.1 (CH2 Bz).
Ϫ EM-EI; m/z: 340 [Mϩ], 249, 181. Ϫ IR (KBr): ν˜ ϭ 3126, 3060,
2940, 2880, 2230 (CN), 1590, 1530, 1360, 1290, 1230, 1080, 960,
885, 705, 692 cmϪ1. Ϫ C22H16N2O2 (340.3798) : C 77.63, H 4.74,
N 8.23; found C 77.03, H 4.91, N: 8.10%.
compatibility between the Rosemund-von-Braun cyanation
and the presence of nitrogen atoms bearing a localised elec-
tron pair makes compound 17 an interesting target for pre-
paring N-alkyl-dicyanobenzo-aza-crown derivatives. Unfor-
tunately, the most versatile compound, dicyanocatechol 4,
does not allow for the preparation of this kind of systems
due to its low reactivity.
4,5-Dihydroxyphthalonitrile (4):[38]
A solution of 3 (3.40 g,
10.10 mmol) in ethyl acetate (100 mL) was added to a suspension
of Pd/10% activated C, 475.00 mg) in ethyl acetate (100 mL). After
the addition, hydrogen was bubbled through at room pressure and
temperature for 4 h. The crude mixture was filtered through Celite
to isolate 1.47 g of compound 4 (recrystallisation from CCl4 or
hexane/AcOEt, 3:1). Yield 91%. M.p. Ͼ 200 °C (ref.[38] 285 °C).
Preliminary aggregation studies carried out on triazo-
lephthalocyanine 24 show the formation of aggregates in
solution in the presence of potassium and rubidium salts,
with promising results, and will be reported at due course.
Studies for preparing films from crowned triazolephthalo-
cyanines based on the LangmuirϪBlodgett technology are
also being carried out.
Ϫ
1H NMR (CDCl3, 200 MHz): δ ϭ 7.27 (s, 2 H). Ϫ 1H NMR
([D6]acetone, 200 MHz):
([D6]DMSO, 200 MHz):
δ
ϭ
7.40 (s,
7.16 (s,
2
H).
H).
Ϫ
1H NMR
δ
ϭ
2
Ϫ
13C NMR
([D6]DMSO, 50 MHz): δ ϭ 154.7 (C-1), 123.8 (C-2), 120.5 (CN),
109.3 (C-3). Ϫ EM-EI; m/z: 160 [Mϩ], 114, 100. Ϫ IR (KBr): ν˜ ϭ
3500Ϫ2600 (OH), 2240 (CN),1610, 1590, 1530, 1450, 1337, 1090,
Experimental Section
900, 840 cmϪ1
.
Techniques: UV/Vis and IR spectra were recorded with
PerkinϪElmer Model Lambda 6 and PU 9716 Philips spectro-
meters, respectively. Ϫ Melting points were determined with a
Büchi melting-point apparatus and are uncorrected. Ϫ NMR spec-
tra were recorded with a Bruker WM-200-SY spectrometer with
either the solvent as reference or TMS as the internal standard. All
chemical shifts are quoted on the δ scale. All coupling constants
are expressed in Hertz (Hz). Ϫ Fast atom bombardment mass spec-
tra (FAB-MS) were obtained from a VG AutoSpec. Samples of the
molecules were dissolved in a small volume of m-nitrobenzyl alco-
hol and loaded on to a stainless steel probe tip. Microanalyses were
4,5-Dibromo-1,2-bis{2Ј-[2ЈЈ(methylsulfonyloxy)ethoxy]ethoxy}-
benzene (6): Mesyl chloride (0.53 g, 4.6 mmol) was added dropwise
to a solution of 5[37] (822 mg, 1.85 mmol), CH2Cl2 (10 mL), and
Et3N (840 mg, 8.35 mmol) under stirring at 0° C. After addition,
the mixture was stirred for 2 h at 0 °C and then allowed to reach
room temperature. The crude was washed with water (50 mL), satd.
aq. NaCl (50 mL), 5% HCl (100 mL), satd. aq. NaHCO3 (50 mL),
and water (50 mL). The organic phase was dried with anhydrous
magnesium sulfate and the solvent removed under reduced pressure
to afford 6 (999 mg) as a brown oil that could be used without
further purification. Yield 90% (recrystallisation from hexane/Ac-
OEt, 7:3). M.p. 50Ϫ51 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ
´
performed by the Universidad Autonoma de Madrid University
Microanalytical Service.
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B. Cabezon, E. Quesada, S. Esperanza, T. Torres
FULL PAPER
7.12 (s, 2 H, H Ar), 4.41 (t, 4 H, CH2OMs), 4.16 (t, 4 H, CH2OAr), 4,5-Dicyano-1,2-(7-heptadecylcarbonyl-7-aza-1,4,10,13-tetraoxa-
3.8Ϫ3.9 (m, 8 H, CH2OCH2), 3.09 (s, 6 H, CH3). Ϫ 13C NMR
tridecamethylene)benzene (10): A mixture of 9 (500 mg, 0.72 mmol),
(CDCl3, 50 MHz): δ ϭ 149.2 (C-1), 119.3 (C-2), 116.1 (C-3), 70.2 CuCN (194 mg, 2.17 mmol), and dry DMF (4.5 mL) was heated to
(CH2OAr), 70.0 (CH2O), 69.9 (CH2OCH2OMs), 38.4 (CH3). Ϫ
reflux for 18 h under argon. After cooling to room temperature,
EM-EI; m/z: 600 [Mϩ], 293, 167. Ϫ C16H24Br2O10S2 (600.2836) : C ammonium hydroxide was added and air was bubbled through the
32.01, H 4.03, S 10.68; found C 32.34, H 3.85, S 10.86.
mixture for 8 h. After filtration of the crude mixture, the residue
was purified by column chromatography (Al2O3, hexane/AcOEt,
1:1) to afford 63 mg of 10 as a white solid. Yield 15%. M.p.
1,2-(7-Benzyl-7-aza-1,4,10,13-tetraoxatridecamethylene)-4,5-di-
bromobenzene (7): A mixture of 6 (12.93 g, 21.54 mmol), benzylam-
ine (2.31 g, 21.54 mmol), Na2CO3 (12.4 g, 120 mmol), and dry ace-
tonitrile (150 mL) was stirred under reflux for 3 d. After cooling to
room temperature, the solvent was removed and the crude mixture
extracted with a water/CH2Cl2 mixture. The organic solution was
dried with anhydrous MgSO4 and the solvent was removed. The
crude product was further purified by column chromatography
(Al2O3, hexane/AcOEt, 3:1) to afford 5.25 g of 7 as a white solid.
Yield 47%. M.p. 100Ϫ102 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ
7.4Ϫ7.2 (m, 5 H, H Ar), 7.05 (s, 2 H, H Ar), 4.10 (t, 4 H, CH2OAr),
3.86 (t, 4 H, OCH2) 3.70 (t, 4 H, CH2O), 3.67 (s, 2 H, CH2 Bz),
2.81 (t, 4 H, NCH2). Ϫ 13C NMR (CDCl3, 50 MHz): δ ϭ 149.5
(C-1), 140.2 (C-1Ј), 129.3 (C-2Ј), 128.7 (C-3Ј), 127.4 (C-4Ј), 118.5
(C-2), 115.6 (C-3), 71.5 (CH2OAr), 70.3 (CH2O), 69.6 (OCH2), 61.0
(CH2N), 55.0 (NCH2 Bz). Ϫ EM-EI; m/z: 515 [Mϩ], 458, 293, 190,
162. Ϫ IR (KBr): ν˜ ϭ 2880, 2820, 2790, 1580, 1500, 1450, 1350,
1
108Ϫ110 °C. Ϫ H NMR (CDCl3, 200 MHz): δ ϭ 7.14, 7.13 (2 s,
2 H, H Ar), 4.18 (m, 4 H, ArOCH2), 3.95 (m, 4 H, CH2O), 3.9Ϫ3.7
(m, 4 H, OCH2), 3.6 (m, 4 H, CH2N), 2.4 (t, 2 H, NCOCH2), 1.62
(m, 2 H, CH2 β), 1.25 (s, 28 H, CH2), 0.88 (t, 3 H, CH3). Ϫ 13C
NMR (CDCl3, 50 MHz): δ ϭ 173.5 (CO), 152.2, 152.1 (C-1), 115.5
(C-2, CN), 109.1 (C-3), 71.3, 70.5 (ArOCH2), 70.4, 69.8 (CH2O),
69.1, 68.4 (OCH2), 50.4, 49.5 (CH2N), 33.1, 31.9, 29.7, 29.5, 29.3,
25.4, 22.7 (CH2), 14.1 (CH3). Ϫ EM-EI; m/z: 583 [Mϩ], 540, 359,
318, 289, 260. Ϫ C34H53N3O5 (583.8078): C 69.95, H 9.15, N 7.20;
found C 69.60, H 9.18, N 6.86.
1,2-(7-Benzyloxycarbonyl-7-aza-1,4,10,13-tetraoxatrideca-
methylene)-4,5-dibromobenzene (11): A solution of benzyl chloro-
formate (1.04 g, 6.10 mmol), N-benzyldibromo derivative 7 (1.57 g,
3.05 mmol), and dry THF (50 mL) was heated to reflux for 6 h.
After extraction with water/CH2Cl2, the organic solution was dried
with anhydrous MgSO4 to afford 1.36 g of 11 as a white solid. Yield
80%. M.p. 99Ϫ101 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ
7.4Ϫ7.3 (m, 5 H, H Ar), 7.05, 7.04 (2 s, 2 H, H Ar), 5.14 (s, 2 H,
COOCH2), 4.05 (m, 4 H, ArOCH2), 3.9Ϫ3.7 (m, 8 H, CH2OCH2),
3.52 (t, 4 H, CH2N). Ϫ 13C NMR (CDCl3, 50 MHz): δ ϭ 156.0
(CO), 148.6 (C-1), 136.7 (C-1Ј), 128.5 (C-2Ј), 127.9 (C-3Ј), 127.8
(C-4Ј), 117.4 (C-2), 114.9 (C-3), 70.9, 70.3 (ArOCH2), 69.9, 69.3
(CH2O), 69.3, 69.1 (OCH2), 67.1 (COOCH2), 50.5, 49.8 (CH2N).
Ϫ EM-EI; m/z: 560 [Mϩ], 154, 136, 107. Ϫ IR (KBr): ν˜ ϭ 3058,
2942, 2872, 2366, 1957, 1698, 1594, 1498, 1475, 1455, 1412, 1370,
1250, 1204, 1157, 1117, 1093, 981, 858, 740, 700 cmϪ1. Ϫ
C22H25Br2NO6 (559.2482): C 47.40, H 4.52, N 2.51; found C 47.58,
H 4.75, N 2.57.
1250, 1200, 1135, 1110, 1080, 1040, 850, 740 cmϪ1
C21H25Br2NO4 (515.2392): C 48.95, H 4.89, N 2.72; found C 48.99,
H 4.87, N 2.69.
. Ϫ
1,2-(7-Aza-1,4,10,13-tetraoxatridecamethylene)-4,5-dibromobenzene
(4,5-Dibromobenzomonoaza-15-crown-5) (8):[33] A solution of 7
(2.38 g, 4.62 mmol) in ethyl acetate (25 mL) was added to a suspen-
sion of Pd/10% activated C (475 mg) in ethyl acetate (25 mL). After
the addition, hydrogen was bubbled through at room pressure and
temperature for 48 h. The crude mixture was filtered through Celite
and purified by chromatography (Al2O3, AcOEt/MeOH, 10:1) af-
fording 606 mg of compound 8. Yield 31%. M.p. 143 °C (ref.[33]
142Ϫ144 °C). Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ 7.03 (s, 2 H,
H Ar), 4.1 (t, 4 H, CH2OAr), 3.86 (t, 4 H, CH2O), 3.73 (t, 4 H,
CH2O), 2.84 (t, 4 H, NCH2), 2.30 (br. s, 1 H, NH). Ϫ 13C NMR
(CDCl3, 50 MHz): δ ϭ 148.5 (C-1), 116.6 (C-2), 114.5 (C-3), 70.2
(CH2OAr), 68.5 (CH2O), 67.9 (CH2O), 49.0 (NCH2). Ϫ IR (KBr):
ν˜ ϭ 3300, 2950, 2920, 2850, 1570, 1490, 1440, 1350, 1250Ϫ1210,
1070, 1040, 960 cmϪ1. Ϫ C14H19Br2NO4 (425.1148) : C 39.55, H
4.50, N 3.29; found C 39.53, H 4.56, N 3.21.
4,5-Dibromo-1,2-(7-ethoxycarbonyl-7-aza-1,4,10,13-tetraoxa-
tridecamethylene)benzene (12): Ethyl chloroformate (217 mg,
2.00 mmol) was added dropwise to a solution of 7 in dry THF
(5 mL) and heated to reflux. After 2 h, the mixture was cooled to
room temperature and extracted with water and CH2Cl2. The or-
ganic solution was dried with anhydrous MgSO4 and the solvent
was removed. The crude mixture was further purified by column
chromatography (Al2O3, hexane/AcOEt, 3:1) to afford 415 mg of
12 as a white solid which was recrystallised from AcOEt/hexane.
Yield 86%. M.p. 103Ϫ104 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ
7.05 (s, 2 H, H Ar), 4.16 (q, 3 H, COOCH2), 4.09 (t, 4 H, ArOCH2),
3.9Ϫ3.7 (m, 8 H, CH2OCH2), 3.52 (t, 4 H, CH2N), 1.25 (t, 3 H,
CH3). Ϫ 13C NMR (CDCl3, 50 MHz): δ ϭ 156.2 (CO), 148.6 (C-
1), 117.4 (C-2), 115.0 (C-3), 70.9, 70.4 (ArOCH2), 69.8, 69.3
(CH2O), 69.3, 69.1 (OCH2), 61.2 (COOCH2), 50.3, 49.6 (CH2N),
14.7 (CH3). Ϫ EM-EI; m/z: 497 [Mϩ], 466, 418, 381, 293, 186, 158,
114. Ϫ C17H23Br2NO6: C 41.07, H 4.66, N 2.32; found C 41.03, H
4.75, N 2.25.
4,5-Dibromo-1,2-(7-heptadecylcarbonyl-7-aza-1,4,10,13-tetraoxa-
tridecamethylene)benzene (9): Stearoyl chloride (470 mg,
1.55 mmol) was added to a mixture of 8[33] (600 mg, 1.41 mmol),
Et3N (290 mg, 2.82 mmol), and CH2Cl2 (10 mL) stirred at room
temperature. After 8 h, the crude mixture was washed with water
(3 ϫ 10 mL) and NaCl successively, and the organic solution was
dried with anhydrous MgSO4. The solution was filtered through
Al2O3, and the removal of CH2Cl2 gave 810 mg of 9 as a white
solid, which was recrystallised from hexane/ethyl acetate. Yield
1
83%. M.p. 67Ϫ68 °C. Ϫ H NMR (CDCl3, 200 MHz): δ ϭ 7.06,
7.05 (2 s, 2 H, H Ar), 4.09 (m, 4 H, ArOCH2), 3.90 (m, 4 H,
CH2O), 3.8Ϫ3.7 (m, 4 H, OCH2), 3.57 (m, 4 H, CH2N), 2.33 (t, 2 4,5-Dibromo-1,2-(7-octadecyloxycarbonyl-7-aza-1,4,10,13-tetraoxa-
H, NCOCH2), 1.62 (m, 2 H, CH2 β), 1.25 (s, 28 H, CH2), 0.88 (t, tridecamethylene)benzene (13): A solution of octadecyl chloro-
3 H, CH3). Ϫ 13C NMR (CDCl3, 50 MHz): δ ϭ 173.7 (CO), 148.7, formate[47](960 mg, 2.89 mmol), the N-benzyl derivative 7 (1.49 g,
148.7 (C-1), 117.7 (C-2), 115.5, 115.3 (C-3), 71.3, 70.5 (ArOCH2),
2.89 mmol), and dry THF (40 mL) was heated to reflux for 8 h.
70.4, 69.8 (CH2O), 69.1 (OCH2), 50.5, 49.6 (CH2N), 34.7, 33.2, After removal of the solvent, the crude mixture was purified by
31.9, 29.7, 29.5, 29.4, 27.6, 25.4, 22.7, 14.1 (CH2).
C32H53Br2NO5 (691.5804): C 55.58, H 7.72, N 2.03; found C 55.41,
H 7.90, N 2.32%.
Ϫ
column chromatography (Al2O3, hexane/AcOEt, 3:1) to afford
1.10 g of 13. Yield 53%. M.p. 64Ϫ68 °C. Ϫ 1H NMR (CDCl3,
300 MHz): δ ϭ 7.04 (s, 2 H, H Ar), 4.07 (m, 8 H, ArOCH2,-
2772
Eur. J. Org. Chem. 2000, 2767Ϫ2775

Synthesis of Crowned Triazolephthalocyanines
FULL PAPER
COOCH2), 3.9Ϫ3.7 (m, 8 H, CH2OCH2), 3.48 (t, 4 H, CH2N), 1.62 (KBr): ν˜ ϭ 3122, 3051, 2918, 2850, 2228, 1693, 1591, 1524, 1470,
(m, 2 H, CH2 β), 1.25 (s, 30 H, CH2), 0.88 (t, 3 H, CH3). Ϫ 13C
1414, 1366, 1290, 1235, 1165, 1135, 1095, 895 cmϪ1
NMR (CDCl3, 75 MHz): δ ϭ 156.3 (CO), 148.7, 148.7 (C-1), 117.5, C35H55N3O6: C 68.47, H 9.04, N: 6.85; found C 68.26, H 8.57,
.
Ϫ
117.5 (C-2), 115.1, 115.0 (C-3), 70.9, 70.5 (ArOCH2), 69.9, 69.3
(CH2O), 69.3, 69.3 (OCH2), 65.5 (COOCH2), 50.3, 49.7 (CH2N),
35.3, 31.9, 29.7, 29.6, 29.3, 29.3, 29.0, 25.9, 22.6 (CH2) 14.1 (CH3).
Ϫ EM-EI; m/z: 722 [Mϩ], 426, 294, 136, 114.Ϫ IR (KBr): ν˜ ϭ
2940, 2850, 1693, 1496, 1454, 1410, 1377, 1357, 1350, 1316, 1254,
1203, 1161, 1120, 1056, 981, 860 cmϪ1. Ϫ C33H55Br2NO6: C 55.06,
H 7.71, N 1.95; found C 55.28, H 7.85, N 1.99.
N 6.83.
1,2-(7-Aza-1,4,10,13-tetraoxatridecamethylene)-4,5-dicyanobenzene
(4,5-Dicyanobenzomonoaza-15-crown-5) (17). ؊ Method A: Equim-
olar amounts of 15 (100 mg, 0.26 mmol) and trimethylsilyl iodide
(TMSI), in CHCl3 (3 mL), were heated to reflux under an inert gas.
Additional molar amounts of TMSI were added after 6 h and 12 h.
After 18 h, MeOH (10 mL) was added and the crude mixture was
extracted in water/CH2Cl2. After removal of the organic solvent,
the crude mixture was purified by column chromatography (Al2O3,
hexane/AcOEt, 1:1 and AcOEt/MeOH, 10:1) to afford 36 mg of 17
1,2-(7-Benzyloxycarbonyl-7-aza-1,4,10,13-tetraoxatrideca-
methylene)-4,5-dicyanobenzene (14):
A mixture of 11 (1.36 g,
2.42 mmol), CuCN (694 mg, 7.75 mmol), and dry DMF (20 mL)
was heated to reflux for 21 h under argon. After cooling to room
temperature, ammonium hydroxide was added and air was bubbled
through the mixture for 8 h. After filtration of the crude mixture,
the residue was purified by column chromatography (Al2O3, hex-
ane/AcOEt, 1:1) to afford 319 mg of 14 as a white solid. Yield 30%.
M.p. 164Ϫ166 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ 7.4Ϫ7.3
(m, 5 H, H Ar), 7.11 and 7.10 (2 s, 2 H, H Ar), 5.14 (s, 2 H,
COOCH2), 4.14 (m, 4 H, ArOCH2), 3.9Ϫ3.7 (m, 8 H, CH2OCH2),
3.52 (t, 4 H, CH2N). Ϫ 13C NMR (CDCl3, 75 MHz): δ ϭ 156.0
(CO), 152.2 (C-1), 136.7 (C-1Ј), 128.5 (C-2Ј), 128.0 (C-3Ј), 127.8
(C-4Ј), 115.7 (CN), 115.6 (C-2), 108.9 (C-3), 71.2, 70.5 (ArOCH2),
69.9, 69.6 (CH2O), 68.9, 68.7 (OCH2), 67.1 (COOCH2), 50.5, 49.8
(CH2N). Ϫ C23H25N3O6: C 62.86, H 5.73, N 9.56; found C 62.78,
H 6.03, N 9.43.
1
as a white solid. Yield 30%. M.p. Ͼ 200 °C. Ϫ H NMR (CDCl3,
200 MHz): δ ϭ 7.08 (s, 2 H, H Ar), 4.16 (m, 4 H, ArOCH2), 3.92
(m, 4 H, CH2O), 3.78 (m, 4 H, OCH2), 2.86 (t, 4 H, CH2N), 2.1
(br. s, 1 H, NH). Ϫ 13C NMR (CDCl3, 75 MHz): δ ϭ 152.2 (C-1),
115.8 (CN), 115.2 (C-2), 108.7 (C-3), 70.5 (ArOCH2), 68.3 (CH2O),
68.1 (OCH2), 49.1 (CH2N). Ϫ EM-EI; m/z: 318 [Mϩ], 154, 136,
121, 107. Ϫ C16H11N3O4: C 62.14, H 3.58, N 13.59; found C 62.02,
H 3.45, N 13.83. Ϫ Method B: A solution of 14 (43.2 mg,
0.096 mmol) in ethyl acetate (4 mL) was added to a suspension of
Pd/10% activated C (475 mg) in ethyl acetate (4 mL). After the ad-
dition, hydrogen was bubbled through at room pressure and tem-
perature for 12 h. The crude mixture was filtered through Celite
and removal of the solvent afforded 28 mg of compound 17.
Yield 80%.
1,3-Diiminoisoindolines 19, 20 and 21. ؊ General Procedure:[48]
A
4,5-Dicyano-1,2-(7-ethoxycarbonyl-7-aza-1,4,10,13-tetraoxatri-
decamethylene)benzene (15): A mixture of 12 (1.66 g, 3.34 mmol),
CuCN (0.96 g, 10.70 mmol), and dry DMF (35 mL) was heated to
reflux for 10 h under argon. After cooling to room temperature,
ammonium hydroxide was added and air was bubbled through the
mixture for 8 h. After filtration of the crude mixture, the residue
was purified by column chromatography (Al2O3, hexane/AcOEt,
1:1) to afford 0.73 g of 15 as a white solid. Yield 56%. M.p.
solution of the corresponding dicyanobenzo-crown (10, 15, and 16,
respectively) in methanol was treated with ammonia gas in the pres-
ence of a catalytic amount of sodium methoxide and heated to
reflux for 6Ϫ12 h. After filtration of the crude mixture, the solid
was washed with NH4Cl to afford the corresponding 1,3-diimin-
oisoindoline as a white solid. The compounds were used without
further purification in the next reaction step.
1
172Ϫ175 °C. Ϫ H NMR (CDCl3, 200 MHz): δ ϭ 7.13 (s, 2 H, H
5,6-(7-Heptadecylcarbonyl-7-aza-1,4,10,13-tetraaoxatrideca-
Ar), 4.16 (q, 3 H, COOCH2), 4.15 (t, 4 H, ArOCH2), 3.9Ϫ3.7 (m,
8 H, CH2OCH2), 3.49 (t, 4 H, CH2N), 1.25 (t, 3 H, CH3). Ϫ 13C
NMR (CDCl3, 50 MHz): δ ϭ 156.2 (CO), 152.2 (C-1), 115.6 (CN),
115.5 (C-2), 108.9 (C-3), 71.1, 70.6 (ArOCH2), 69.9, 69.6 (CH2O),
68.9, 68.6 (OCH2), 61.3 (COOCH2), 50.3, 49.7 (CH2N), 14.7
(CH3). Ϫ EM-EI. m/z: 389 [Mϩ], 346, 332, 318, 286, 260, 231, 186,
171. Ϫ IR (KBr): ν˜ ϭ 3437, 2227, 1698, 1590, 1566, 1523, 1413,
1294, 1160, 1136, 1094, 892 cmϪ1. Ϫ C19H23N3O6: C 58.60, H 5.95,
N 10.79; found C 58.41, H 6.12, N 10.39.
methylene)-1,3-diiminoisoindoline (19): Yield: 90%. M.p. 150 °C (de-
comp.). Ϫ H NMR ([D1]TFAA, 200 MHz): δ ϭ 7.92 (br. s, 2 H,
1
H Ar), 4.4Ϫ4.1 (m, 8 H, ArOCH2CH2), 3.94 (m, 4 H, OCH2), 3.84
(m, 4 H, CH2N), 2.52 (t, 2 H, COCH2 ), 1.49 (m, 2 H, CH2 β),
1.23 (br. s, 28 H, CH2), 0.92 (t, 3 H, CH3). Ϫ 13C NMR
([D1]TFAA, 50 MHz): δ ϭ 184.3 (CO), 168.9, 168.9 (C-1), 159.5,
158.9 (C-5), 124.9, 124.4 (C-3a), 112.6, 112.5 (C-4), 74.0, 72.6 (Ar-
OCH2), 72.4, 72.1 (CH2O), 72.0, 70.2 (OCH2), 56.7, 54.9 (CH2N),
35.2, 34.8, 32.5, 32.5, 32.5, 32.2, 32.0, 31.9, 28.5, 25.3 (CH2), 15.6
(CH3). Ϫ IR (KBr): ν˜ ϭ 3300Ϫ3200, 2930, 2850, 1634, 1600, 1550,
4,5-Dicyano-1,2-(7-octadecyloxycarbonyl-7-aza-1,4,10,13-tetraoxa-
1523, 1464, 1443, 1423, 1292, 1195, 1137, 1059 cmϪ1
.
tridecamethylene)benzene (16):
A
mixture of 13 (800 mg,
1.11 mmol), CuCN (298 mg, 3.33 mmol), and dry DMF (12 mL)
was heated to reflux for 11 h under argon. After cooling to room
temperature, ammonium hydroxide was added and air was bubbled
through the mixture for 8 h. After filtration of the crude mixture,
the residue was purified by column chromatography (Al2O3, hex-
ane/AcOEt, 3:1) to afford 285 mg of 16 as a white solid. Yield 42%.
5,6-(7-Ethoxycarbonyl-7-aza-1,4,10,13-tetraaoxatridecamethylene)-
1,3-diiminoisoindoline (20): Yield: 91%. M.p. 180 °C (decomp.). Ϫ
1H NMR ([D1]TFAA, 200 MHz): δ ϭ 8.19 (br. s, 2 H, H Ar), 4.58
(m, 2 H, COOCH2), 4.49 (m, 4 H, CH2OAr), 4.39 (m, 4 H, CH2O),
4.19 (m, 4 H, CH2O), 3.9 (m, 4 H, CH2N), 1.42 (t, 3 H, CH3). Ϫ
13C NMR ([D1]TFAA, 50 MHz): δ ϭ 163.8 (C-1), 157.3 (CO),
154.6 (C-5), 119.7 (C-4), 108.2 (C-3a), 68.3 (ArOCH2), 67.9
(CH2O), 67.4 (OCH2), 62.7 (CH2N), 47.2 (COOCH2), 11.1 (CH3).
Ϫ EM-EI; m/z: 407 [Mϩ], 307, 289, 139, 136, 123. Ϫ IR (KBr):
ν˜ ϭ 3250Ϫ3125, 2925, 2870, 1702, 1587, 1442, 1413, 1305, 1223,
1
M.p. 116Ϫ118 °C. Ϫ H NMR (CDCl3, 300 MHz): δ ϭ 7.11, 7.10
(2 s, 2 H, H Ar), 4.16 (t, 4 H, ArOCH2), 4.08 (t, 2 H, COOCH2),
3.92 (dd, 4 H, CH2O), 3.8 (dd, 4 H, OCH2), 3.48 (dd, 4 H, CH2N),
1.62 (m, 2 H, CH2 β), 1.25 (s, 30 H, CH2), 0.88 (t, 3 H, CH3). Ϫ
13C NMR (CDCl3, 75 MHz): δ ϭ 156.3 (CO), 152.3 (C-1), 115.9
(C-2), 115.7 (CN), 108.6 (C-3), 71.2, 70.7 (ArOCH2), 69.9, 69.5
(CH2O), 68.9, 68.6 (OCH2), 65.6 (COOCH2), 50.4, 49.8 (CH2N),
1130, 1058 cmϪ1
.
1,3-Diimino-5,6-(7-octadecyloxycarbonyl-7-aza-1,4,10,13-tetraoxa-
35.3, 31.9, 29.7, 29.6, 29.3, 29.0, 26.0, 22.7 (CH2) 14.1 (CH3). Ϫ tridecamethylene)isoindoline (21): Yield: 86%. M.p. 150 °C (de-
EM-EI; m/z: 614 [Mϩ], 362, 344, 318, 154, 138, 114, 107. Ϫ IR
comp.). Ϫ 1H NMR ([D1]TFAA, 200 MHz): δ ϭ 8.2 (br. s, 2 H, H
Eur. J. Org. Chem. 2000, 2767Ϫ2775
2773

´
B. Cabezon, E. Quesada, S. Esperanza, T. Torres
FULL PAPER
Ar), 4.6Ϫ4.4 (m, 6 H, COOCH2, 2·CH2OAr), 4.4 (m, 4 H, CH2O),
Ϫ IR (KBr): ν˜ ϭ 3500Ϫ3200, 2921, 2851 (CϪH), 1644 (NϪCO),
4.2 (m, 4 H, CH2O), 3.9 (m, 4 H, CH2N), 1.8 (m, 2 H, CH2 β), 1.5 1600, 1500, 1468, 1438 (CϭN), 1360, 1289, 1117, 1072, 727 cmϪ1
(br. s, 30 H, CH2), 0.9 (t, 3 H, CH3). Ϫ 13C NMR ([D1]TFAA, (CϪH). Ϫ UV/Vis (CHCl3): λ (log ε/dm3 molϪ1 cmϪ1) ϭ 261
50 MHz): δ ϭ 164.3 (C-1), 157.3 (CO), 154.7 (C-5), 119.7 (C-4),
(4.30), 282 (4.30), 371 (4.10), 435 (sh), 530 (3.67), 576 (3.61),
107.7 (C-3a), 68.6 (ArOCH2), 68.0 (CH2O), 62.7 (CH2N), 47.3, 631 nm (3.70). Ϫ C53H63N11NiO5·4 H2O: C 59.78, H 6.72, N 14.47;
47.1 (COOCH2), 30.1, 27.8, 27.4, 27.3, 26.8, 23.9, 20.6 (CH2), 10.9
found C 59.48, H 7.19, N: 14.02.
(CH3). Ϫ IR (KBr): ν˜ ϭ 3278, 3231, 2949, 2848, 1702, 1536, 1470,
{9,10-(7-Octadecyloxycarbonyl-7-aza-1,4,10,13-tetraoxatri-
decamethylene)-7,12:21,24-diimino-5,26:14,19-dinitrilotribenzo-
[f,k,p][1,2,4,9,14,19]hexaazacycloicosinato(2؊)-N27,N28,N29,N30}-
1435, 1418, 1301, 1217, 1239, 1067, 885 cmϪ1
.
{7,12:21,24-Diimino-5,26:14,19-dinitrilo-9,10-(1,4,7,10,13-pentaoxa-
tridecamethylene)tribenzo[f,k,p][1,2,4,9,14,19]hexaazacycloicosinato- nickel(II) (27): Equimolar amounts of 3,5-bis(3Ј-imino-1Ј-isoindoli-
(2؊)-N27,N28,N29,N30}nickel(II) (24): A mixture of the corresponding nylidenamino)-1,2,4-triazole
(22a) (41 mg, 0.12 mmol),
[3,5-bis(3Ј-imino-1Ј-isoindolinylidenamino)-1,2,4-triazolato]-
nickel(II) (23a)[40] (73.30 mg, 0.21 mmol), 1,3-diimino-5,6-
Ni(OAc)2·4H2O (28.9 mg, 0.12 mmol), 1,3-diimino-5,6-(7-octade-
cyloxycarbonyl-7-aza-1,4,10,13-tetraaoxatridecamethylene)-
(1,4,7,10,13-pentaoxatridecamethylene)isoindoline (18) (69.20 mg, isoindoline (21) (71 mg, 0.12 mmol), and 2-ethoxyethanol (20 mL)
0.21 mmol), and 2-ethoxyethanol (15 mL) was stirred at 50 °C for
3 d. After filtration, the crude mixture was triturated with methanol
and the triazolephthalocyanine was extracted with chloroform. Fi-
nally, after vacuum evaporation of the solvent, the residue was
washed with methanol and filtered to yield 36 mg of 24. Yield:
25%. M.p. Ͼ 200 °C. Ϫ 1H NMR (CDCl3, 200 MHz): δ ϭ 7.4Ϫ6.5
(br. signal, 10 H), 3.7Ϫ3.5 (m, 8 H, OCH2), 3.5 .(s, 8 H, OCH2).
were stirred at 50 °C for 3 d. The solid was isolated by filtration and
it was treated as described above. Further purification by column
chromatography (silica gel, CH2Cl2/MeOH, 20:1) was required to
yield 28 mg of 27. Yield: 24%. M.p. Ͼ 200 °C. Ϫ 1H NMR (CDCl3,
200 MHz): δ ϭ 7.4Ϫ6.5 (br. signal, 10 H), 4.5Ϫ3.4 (3·m, 18 H,
OCH2), 1.29 (m, 32 H, CH2), 0.92 (m, 3 H, CH3). Ϫ MS-FAB (3-
NBA, CDCl3); m/z: 1008, 1010 (M ϩ Hϩ). Ϫ IR (KBr), ν˜:
Ϫ MS-FAB (3-NBA, CDCl3); m/z: 713, 715 [M ϩ Hϩ]. Ϫ IR 3600Ϫ3000, 2922, 2851 (CϪH), 1699 (NϪCOϪO), 1598, 1468,
(KBr): ν˜ ϭ 3600Ϫ3200, 2924, 2854 (CϪH), 1600, 1500, 1470, 1440
1413 (CϭN), 1351, 1289, 1129, 1067, 772, 754, 723 cmϪ1 (CϪH).
(CϭN), 1350, 1290, 1120, 1075, 1050, 760 cmϪ1 (CϪH). Ϫ UV/Vis Ϫ UV/Vis (CHCl3): λ (log ε/dm3 molϪ1 cmϪ1) ϭ 260 (4.52), 355
(CHCl3): λ (log ε/dm3 molϪ1 cmϪ1) ϭ 259 (4.57), 370 (4.42), 530
(4.00), 628 nm (4.12). Ϫ C34H26N10NiO5·H2O: C 55.84, H 3.86, N
19.15; found C 55.58, H 3.71, N 19.21.
(4.21), 571 (sh), 619 nm (3.54). Ϫ C53H63N11NiO6·4 H2O: C 58.89,
H 6.62, N 14.25; found C 58.55, H 6.82, N 13.85.
{2(3),16(17)-Dioctyloxy-9,10-(1,4,7,10,13-pentaoxatride-
camethylene)-7,12:21,24-diimino-5,26:14,19-dinitrilotribenzo-
{9,10-(7-Ethoxycarbonyl-7-aza-1,4,10,13-tetraaoxatridecameth-
ylene)-7,12:21,24-diimino-5,26:14,19-dinitrilotribenzo[f,k,p]- [f,k,p][1,2,4,9,14,19]hexaazacycloicosinato(2؊)-N27,N28,N29,N30}-
[1,2,4,9,14,19]hexaazacycloicosinato(2؊)-N27,N28,N29,N30}- nickel(II) (28): A mixture of 3,5-bis(3Ј-imino-5Ј(6Ј)-octyloxy-1Ј-iso-
nickel(II) (25): A mixture of 3,5-bis(3Ј-imino-1Ј-isoindolinyliden-
amino)-1,2,4-triazole (22a) (0.13 g, 0.37 mmol), and Ni(OAc)2
(93 mg, 0.37 mmol) in 2-ethoxyethanol (10 mL) was heated at 80
°C for 2 h. After cooling to 55 °C, 5,6-(7-ethoxycarbonyl-7-aza-
1,4,10,13-tetraaoxatridecamethylene)-1,3-diiminoisoindoline (20)
indolinylidenamino)-1,2,4-triazole (22b) (0.10 g, 0.16 mmol) and
Ni(OAc)2 (41 mg, 0.16 mmol) in 2-ethoxyethanol (20 mL) was
heated at 80 °C for 2 h. After cooling to 55 °C, 1,3-diimino-5,6-
(1,4,7,10,13-pentaoxatridecamethylene)isoindoline (18) (55 mg,
0.16 mmol) in 2-ethoxyethanol (10 mL) was added and the mixture
(0.15 g, 0.37 mmol) in 2-ethoxyethanol (10 mL) was added and the was stirred for 3 d at this temperature. The solid was isolated by
mixture was stirred for 3 d at this temperature. The solid was isol- filtration and it was treated as described above. Further purification
ated by filtration and it was treated as described above affording by column chromatography (silica gel, CH2Cl2/MeOH, 15:1) was
1
96 mg of 25. Yield: 29%. M.p. Ͼ 200 °C. Ϫ 1H NMR (CDCl3, required to yield 15 mg of 28. Yield: 10%. M.p. Ͼ 200 °C. Ϫ H
200 MHz): δ ϭ 7.4Ϫ6.5 (br. signal, 10 H), 4.5Ϫ3.0 (m, 18 H,
NMR (CDCl3, 200 MHz): δ ϭ 7.6Ϫ6.5 (3 m, 8 H), 4.0Ϫ3.3 (2 m,
OCH2), 0.88 (m, 3 H, CH3). Ϫ MS-FAB (3-NBA, CDCl3); m/z: 20 H, OCH2), 1.7 (m, 4 H, OCH2CH2), 1.33 (s, 20 H, CH2), 0.92
784, 786 [M ϩ Hϩ]. Ϫ IR (KBr): ν˜ ϭ 3600Ϫ3000, 2928, 2870 (t, 6 H, CH3). Ϫ MS-FAB (3-NBA, CDCl3); m/z: 969, 971 (100)
(CϪH), 1679 (NϪCOϪO), 1600, 1500, 1471, 1449 (CϭN), 1383, [M ϩ H]ϩ, 857, 855 (24) [M Ϫ C8H16 ϩ H]. Ϫ IR (KBr): ν˜ ϭ
1352, 1290, 1120, 1069, 754, 725 cmϪ1 (CϪH). Ϫ UV/Vis (CHCl3): 3600Ϫ3200, 2920, 2850 (CϪH), 1610, 1490, 1470, 1440 (CϭN),
λ (log ε/dm3 molϪ1 cmϪ1) ϭ 259 (4.23), 364 (3.99), 517 (sh), 562
1370, 1330, 1290, 1245, 1120, 1075, 1040, 830, 765 cmϪ1 (CϪH).
(3.58), 626 nm (3.52). Ϫ C37H31N11NiO6·4 H2O: C 51.89, H 4.59, Ϫ UV/Vis (CHCl3): λ (log ε/dm3 molϪ1 cmϪ1) ϭ 279 (4.20), 366
N 17.99; found C 51.51, H 4.35, N 17.88.
(3.90), 400 (sh), 529 (3.50), 572 (3.40), 637 nm (3.22). Ϫ
C50H58N10NiO5·3 H2O: C 64.36, H 6.91, N 15.01; found C 64.21,
H 7.13, N 14.85.
{9,10-(7-Heptadecylcarbonyl-7-aza-1,4,10,13-tetrataoxatri-
decamethylene)-7,12:21,24-diimino-5,26:14,19-dinitrilotribenzo-
[f,k,p][1,2,4,9,14,19]hexaazacycloicosinato(2؊)-N27,N28,N29,N30}- {7,12:21,24-Diimino-5,26:14,19-dinitrilo-2,3:9,10:16,17-tris-
nickel(II) (26): Equimolar amounts of 3,5-bis(3Ј-imino-1Ј-isoindoli-
nylidenamino)-1,2,4-triazole (22a) (59 mg, 0.17 mmol),
(1,4,7,10,13-pentaoxatridecamethylene)tribenzo[f,k,p][1,2,4,9,14,19]-
hexaazacycloicosinato(2؊)-N2 7,N2 8 ,N2 9,N3 0 }nickel(II)
(29): 1,3-Diimino-5,6-(1,4,7,10,13-pentaoxatridecamethylene)iso-
indoline (18) (0.50 g, 1.49 mmol), 3,5-diamino-1,2,4-triazole
(0.05 g, 0.50 mmol), Ni(OAc)2 4H2O (0.12 g, 0.50 mmol), and 2-
ethoxyethanol (20 mL) were stirred under reflux for 48 h. After fil-
tration, the crude material was triturated with methanol and the
triazolephthalocyanine was extracted with chloroform. Finally,
Ni(OAc)2·4H2O (41 mg, 0.17 mmol), 4,5-dicyano-1,2-(7-heptade-
cylcarbonyl-7-aza-1,4,10,13-tetraaoxatridecamethylene)benzene
(10) (100 mg, 0.17 mmol), and 2-ethoxyethanol (5 mL) were stirred
at 50 °C for 3 d. The solid was isolated by filtration and was treated
as described above. Further purification by column chromato-
graphy (silica gel, CH2Cl2/MeOH, 15:1) was required to yield
43 mg of 26. Yield: 26%. M.p. Ͼ 200 °C. Ϫ 1H NMR (CDCl3, after vacuum evaporation of the solvent, the residue was washed
200 MHz): δ ϭ 7.8Ϫ6.5 (br. signal, 10 H), 4.0Ϫ3.3 (m, 16 H,
with hot methanol and filtered to yield 20 mg of 29. Yield: 4%.
M.p. Ͼ 200 °C. Ϫ H NMR ([D1]TFAA, 200 MHz): δ ϭ 8.5Ϫ7.5
1
OCH2), 2.4 (m, 2 H, NCOCH2), 1.29 (s, 35 H, CH2), 0.92 (m, 3
H, CH3). Ϫ MS-FAB (3-NBA, CDCl3); m/z: 992, 994 [M ϩ Hϩ]. (br. signal, 6 H), 4.8Ϫ4.0 (3·m, 48 H, OCH2). Ϫ MS-FAB (3-NBA,
2774
Eur. J. Org. Chem. 2000, 2767Ϫ2775

Synthesis of Crowned Triazolephthalocyanines
FULL PAPER
[20]
[21]
[22]
[23]
TFAA); m/z: 1093, 1095 [M ϩ Hϩ]. Ϫ IR (KBr): ν˜ ϭ 3600Ϫ3200,
2920, 2880 (CϪH), 1600, 1500, 1485, 1460 (CϭN), 1355, 1290,
1120, 1085, 1055, 840, 765 cmϪ1 (CϪH). Ϫ UV/Vis (CHCl3): λ (log
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[O00062]
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