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Synthesis and Properties of Macroheterocyclic Compounds of ABAB-Type with ieri-Butylpyrrolepyrazine Fragments®
Mikhail G. Stryapan, Svetlana V. Efimova, Oscar I. Koifman, and Mikhail K. Islyaikin@
Ivanovo State University of Chemistry and Technology, Friedrich Engels Pr-t, 7, Ivanovo, 153000, Russia @Corresponding author E-mail: [email protected]
New representatives of macroheterocyclic compounds of ABAB-type were synthezised by condensation of m-phenylenediamine or 2,6-diaminopyridine (A) with 5-tert-butyl-2,3-dicyanopyrazine (B) in "BuOH. These compounds were characterizised by UV-vis, IR, 1HNMR spectroscopies, mass-spectrometry and elemental analysis.
Keywords: Macroheterocyclic compounds, m-phenylenediamine, 2,6-diaminopyridine, 5-tert-butyl-2,3-dicyanopyrazine, hemiporphyrazine.
Introduction
Macroheterocyclic compounds (Mc) of ABAB-type can be represented as structural analogues ofphthlocyanine, where two opposite isoindole moieties (B) are replaced by aromatic rings (A) derived from aromatic diamines. Since their discovery,[1] these compounds called by Campbel "hemiporphyrazines"[2] are the objects of continuous interest due to their structure particularities[3,4] as well as attractive properties revealed recently: optical limiting, fluorescence, catalysis, devices for keeping information and so on.[5-7]
For the moment a number of representatives of this series was synthesized,[8,9] but macrocycles containing pyrazine fragments (B) and those of six-membered aromatic diamines (A) are studied not enough completely. The first two representatives of nonsubstituted macroheterocyclic compounds of this type were described earlier.[10] These compounds were characterized by IR and UV-vis spectroscopies as well as elemental analysis data. Their serious imperfection is a low solubility in common organic solvents, what makes their refinement to be little tedious and constricts a number of methods which could be applied to study their structures and properties. It was established that introduction of bulky tert-butyl groups led to increase of solubility of Mc. [11] Hence the subject of this work is synthesis of Mc of ABAB-type bearing tert-butylpyrazine rings incorporated into macrocyclic core as units (B).
Experimental
General procedure. A mixture of 5-tert-butyl-2,3-dicyanopyrazine (1 mmol) and m-phenylenediamine or 2,6-diaminopyridine (1 mmol) in butanol (10 ml) was stirred at
® This contribution is dedicated to professor Vasilij Fedorovich Borodkin on the occasion of his 100th Anniversary. ® Статья посвящена 100-летнему юбилею профессора Василия Фёдоровича Бородкина.
80 0C for 6 h and then refluxed for 23 h. The solvent was removed under vacuum, and the crude product was washed with MeOH and then extracted with CHCl3 in Soxhlet's apparatus. After solvent evaporation, the product was purified by column chromatography on silica gel (CHCl3:MeOH:C6H14 = 10:1:5). The solvents were removed and the solids were dried under vacuum.
2,15-Di(tert-butyl)-5,26:13,18-diimino-7,11:20,24-di-metheno-fc, n]-dipyrazmo-[1,6,12,17]-tetraazacyclodocose"-[1,3,5,7,9,12,14,16,21,23], 1. It was synthesized following the general procedure by interaction of 5-tert-butyl-2,3-dicyanopyrazine with m-phenylenediamine as a dark orange powder. Yield: 36 mg (26 %). UV-vis (CHCl3) Xmax nm (lg s): 361 (3.82), 383 (3.82). IR (KBr) v cm-1: 3424, 2922, 2852, 1636, 1464, 1254, 1157. MS (MALDI-TOF) m/z: 555 [(M+H)+]. Found: C 68.51, H 5.34, N 25.17 %. C32H30N10 requires C 69.30, H 5.45, N 25.25 %.
2,15-Di(tert-butyl)-5,26:13,18-diimino-7,11:20,24-di"itrilo-[c,"]-dipyrazi"o-[1, 6,12,17]-tetraazacyclodocose"-[1,3,5,7,9,12,14,16,21,23], 2. It was synthesized following the general procedure by interaction of 5-tert-butyl-2,3-dicyanopyrazine with 2,6-diaminopyridine. The target product represents a dark red powder. Yield: 13 mg (9 %). UV-vis (CHCl3) Xmax nm (lg s): 379 (3.96), 425 (3.96). IR (KBr) v cm-1: 3327, 2927^2856, 1746, 1640, 1465, 1250, 1165. 1H NMR (CDCl3) 5 ppm: 15.09 (s., 2H), 8.9 (s., 2H), 7.6 (tr., 2H), 7.1 (d., 2H), 6 3 (d., 2H), 1.55, (18H, -CH3). MS (MALDI-TOF) m/z: 556 [(M+H)+]. Found: C 64.41, H 4.89, N 29.63 %. C30H28N12 requires C 64.72, H 5.03, N 30.21 %.
Results and Discussion
A general way to gain access to the Mc of ABAB-type is the interactions of alkoxy- or diiminoisoindolines with aromatic diamines. But phthalonitrile itself and substituted phthalonitriles are able to react directly with diamines without previous transformation into corresponding isoindoline derivatives.[12,13] It is worthy to note that presence of nitrogen atoms in dicyanoconstituent makes this reaction easier to go.13 So we succeed in synthezising of Mc 1, 2 by direct condensation of 5-tert-butyl-2,3-dicyanopyridine with 1.3-phenylenediamine or 2,6-diaminopyridine in nBuOH.
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M. K. Islyaikin et al.
/-Bu. N^
+ 2
n cn
h2
A
buoh
nh2
X: CH(1) N(2)
204000
2922
such low field shows that these compounds have no aromatic macrocycles at the base of their sceletons.
UV-vis spectra of 1 and 2 in chloroform contain the broad bands of absorbance with maxima located at 383 and 425 nm, correspondingly. A longer wavelength shift observed on going from 1 to 2 is most probably due to more plane structure of the central core of Mc 2 if compared with 1.
IR-specra of compounds 1 and 2 (Figure 1) are very similar to each other. So, the strong bands at 2925 and 2855 cm-1 are due to the symmetric and asymmetric valance vibrations of C-H bonds belonging to tert-butyl groups. The bands at 1640 and 1465 cm-1 can be put in concordance with deformations of C=C and C=N bonds, correspondingly.
Conclusions
2856
1165
1640
1465
1500 cm"1
tert-Butylsubstituted azaanalogues of hemiporphy-razines were obtained by direct condensation of 5-tert-butyl-2,3-dicyanopyridine with m-phenylenediamine or 2,6-diaminopyridine in boiling n-butanol. Sufficiently high solubility in organic solvents allows to apply the column chromatography for their purification. Their structures were established on the base of UV-vis, IR, 'H NMR spectrosco-pies, mass-spectrometry and elemental analisys data.
Acknowledgements. This work was supported by Federal Principal Program "Research and research-pedagogical staffs of innovative Russia for 2009-2013" (№ 02.740.11.0106).
Figure 1. IR spectra of compounds 1 and 2.
References
1
2
The reactions were monitored by TLC along with NH3 separation. After solvent elimination, the residues were purified by extraction of topic products by CHCl3 in Soxhlet extractor with following column chromatography using silica-gel.
The compounds 1, 2 were characterized by UV-vis, IR, *H NMR spectroscopies, mass-spectrometry, and elemental analisys.
The signals at 555 and 556 m/z which are in good agreement with molecular ions [M+H]+ of 1 and 2 correspondingly were detected in MALDI-TOF. There are three groups of signals in the *H NMR spectra of 1 and 2. So, in spectrum of 2, two series of signals located at 0.8 - 1.8 and 6.0 - 9 ppm are induced by resonance of the protons of tert-butyl groups and those of aromatic systems correspondingly. The signals (~15 ppm) of 1 and 2 are due to the resonance of iminogroup protons and their position at a
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Macroheterocycles of ABAB-Type with Pyrrolepyrazine Fragments
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Received 10.11.2009 Accepted 15.03.2010 First published on the web 20.03.2010
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