CC BY
8Олигогетероциклы_ МакрОГЭТЭрОЦИКЛЫ_Статья
Oligoheterocycles http://macroheterocycles isuct ru Paper
DOI: 10.6060/mhc2011.4.04
Highly Versatile Synthetic Approach to Oligopyridines and Derivatives by Krohnke-Type Ring-Closure Reactions
Daniel Caterbow and Ulrich Ziener@
Dedicated to Professor Michael Hanack on the occasion of his 80th birthday
University of Ulm, Institute of Organic Chemistry III, Albert-Einstein-Allee 11, D-89081 Ulm, Germany @Corresponding author E-mail: [email protected]
The synthesis of a large variety of different conjugated oligopyridines and derivatives with electron poor and/or rich peripheral substituents and with pyridine and other (hetero)aromatic cores by the highly versatile Krohnke-type synthesis is described. Simple electronic and steric considerations of the participating unsaturated ketones (chalcones) allow a rough estimation of the synthetic accessibility of the desired compounds.
Keywords: Pyridine, ring-closure reaction.
Introduction
The control over structures on the nanoscale is a central issue in the field of nanosciences. The highly attractive bottom-up approach to nanostructures requires carefully tailored building blocks, which self-assemble into the desired architectures. The properties of the self-assembled arrays emerge from the functionalities delivered by the functional molecular building blocks. Thus, there is a need for highly versatile molecules, which fulfill all the requirements as self-assembling building blocks. The class of oligopyridines is predestined for these purposes.[1] Such compounds are synthetically easily accessible, structurally variable, chemically and thermally stable, can planarize upon adsorption on flat surfaces, and act as ligands for metal complexation and as hydrogen bond donors and acceptors.
There is a vast variety of synthetic strategies to access oligopyridines either by metal catalyzed coupling or by ring-closure reactions. Despite the high versatility of the (cross) coupling reactions, especially the longer oligomers are hardly accessible through this route as intermediate compounds in the course of the reaction suffer sufficient solubility. In contrast, non-cyclic precursor molecules for ring-closure reactions offer good solubilities in combination with accessibility and variability. Several strategies were described in the literature from which a few shall be presented in the following. The reaction of pyridyl substituted glyoxyl aldehyde with pyridineamidrazones leads to the formation of 1,2,4-triazines, which are transformed in a [4+2] cycloaddition by the elimination of nitrogen to the corresponding oligopyri-dines.[2] Potts and coworkers developed a synthetic route of alkylthio substituted oligopyridines by the reaction of acetyl pyridines with a-oxoketene dithioacetals.[1d3] Already in the sixties of the last century Krohnke reported the synthesis of oligopyridines from pyridinium salt activated methyl ketones and a,B-unsaturated ketones or related compounds.[4]
In the past ten years we have described the synthesis and self-assembly properties of C2v symmetric bis(terpyridine) derived oligopyridines with a pyrimidine core, the so-called BTPs (Figure 1a).[5] These BTPs are formed from a double Krohnke-type reaction of the bispyridinium salt of bisacetyl phenylpyrimidine with (hetero)aromatic unsaturated ketones (chalcones). In total there are five isomers of the BTPs known (2,3'-, 2,4'-, 3,3'-, 4,3'-, and 2,2'-BTP).[5] These compounds possess an internal (hetero)aromatic ring system and four peripheral pyridine rings. While the central moiety determines the symmetry and relative orientation of the peripheral pyridine rings, the peripheral units display highly specific[6] intermolecular C-H- N hydrogen bonding interactions with neighboring molecules in, e.g., two-dimensional (2D) arrays. The different isomers self-assemble into a broad variety of different 2D structures on various substrates like highly ordered pyrolytic graphite (HOPG) or Au111 at the liquid|solid and gas|solid interface, respectively.[5a,5c,7] The number of synthetically accessible BTP isomers via the double Krohnke-like ring-closure reaction is limited because of the limited number of dipyridylchalcones. These limitations could be mostly bypassed by substituting the central pyri-midine core of the BTPs with a corresponding pyridine unit resulting phenylseptipyridines (PhSpPys). By this strategy further isomers with self-assembly behavior corresponding to three missing BTP isomers could be obtained.[5d] The rich 2D phase behavior makes this class of C2v symmetric oligopyridines highly attractive and rises the question if further structural modification of the molecules is possible to even extend that class.
In the following, we show that the Kohnke-like approach can be quite generally exploited by introducing other substituents in the periphery than pyridine and by substitution of the core unit by other (hetero)aromatic moieties, respectively. Such compounds display different shapes, symmetries and peripheral functionalities by keeping
the coplanarity and mostly the hydrogen bonding capability with the perspective of forming highly ordered 2D arrays.
Results and Discussion
The already described synthesis of oligopyridines in a double Krohnke-type reaction with a pyrimidine[5a,5c] and a pyridine[5d] core (Figure 3), respectively, can be extended to obtain further C2v symmetric (hetero)aromatic compounds (Figure 1). On one side, the peripheral ring systems can be broadly varied but also the core moiety can be exchanged by further (hetero)aromatic units. The periphery of those molecules determines the intermolecular interactions in self-assembled arrays like 2D monolayers whereas the core unit steers the overall geometry of the molecules. By changing the pyrimidine core by a pyridine unit the relative orientation of the coupled pyridine rings is inverted because of the energetically favourable N-N transoid conformation
(Figure 3). In both systems the relative orientation of the pyridine units formed by ring closure is 120° whereas />ara-substitution[4] forces the rings in a 180° alignment resulting the so-called bar-bell compounds (BBC). If the central moiety of the BBCs contains nitrogen atoms like in pyrazine the planarization of the whole system is favoured with the peripheral rings in transoid conformation whereas pyridazine as core unit favours the cisoid conformation (Figure 4). In addition, further substituents at the core units like phenyl rings enhance the solubility but affect also the self-assembly properties of the resulting oligomers by, e.g., n-n stacking. Thus, a subtle interplay between intramolecular constitution and conformation influence the molecular and supramolecular structures.
Besides those structural effects the synthetic feasibility of these compounds is crucial for their application as (self-assembling) materials. The success of the Krohnke pyridine synthesis strongly depends on the substituents of the
R1 R2
(2N,Ph'-BTP) 2-py Ph
(2N,3S--BTP) 2-py 3-th
(3S,2N'-BTP) 3-th 2-py
(2N,sty,-BTP) 2-py sty
(3N,sty,-BTP) 3-py sty
R1 R2 A A" A"'
(2N,Ph'-Ph-BBC) 2-py Ph CH CH CH
(Ph,3N'-Ph-BBC) Ph 3-py CH CH CH
(3,3'-Ph-BBC) 3-py 3-py CH CH CH
(2,3'-Ph-BBC) 2-py 3-py CH CH CH
(4,3'-Ph-BBC) 4-py 3-py CH CH CH
(Ph,Ph'-Pdz-BBC) Ph Ph N N CH
(2,2'-Pdz-BBC) 2-py 2-py N N CH
(Ph,Ph'-Pyz-BBC) Ph Ph N CH N
(3,3'-Pyz-BBC) 3-py 3-py N CH N
R1 R2
(2,3'-SpPy) 2-py 3-py
(2,4'-SpPy) 2-py 4-py
(4,3'-SpPy) 4-py 3-py
(2,5,3'-SpPy) Pyz 3-py
(2N,3S'-SpPy) 2-py 3-th
(3S,2N'-SpPy) 3-th 2-py
(2N,2S'-SpPy) 2-py 2-th
(3N,3S"-SpPy) 3-py 3-th
(3S,3N'-SpPy) 3-th 3-py
(3S, Ph'-SpPy) 3-th Ph
(Ph,3S-SpPy) Ph 3-th
(30H,2N'-SpPy) 3-hy 2-py
(30H,4N'-SpPy) 3-hy 4-py
(BiPh,BiPh'-SpPy) BiPh BiPh
(Ph,Bi Ph'-SpPy) Ph BiPh
(4Br,Ph'-SpPy) 4-Br Ph
(4F,Ph'-SpPy) 4-F Ph
(2N,4F'-SpPy) 2-py 4-F
(2S,2S,-SpPy) 2-th 2-th
(2S,3S,-SpPy) 2-th 3-th
(3S,2S'-SpPy) 3-th 2-th
(3S,3S--SpPy) 3-th 3-th
(BiPh,Ph'-SpPy) BiPh Ph
(2N,Sty"-SpPy) 2-py sly
(3,Sty*-SpPy) 3-py sty
(Ph.Sty'-SpPy) Ph sly
(3N,P-SpPy) 3-py P
Figure 1. Overview on the oligopyridine systems newly synthesized: a) bis(terpyridine) derived oligopyridines (BTPs), b) septipyridines (SpPys, R3 = H), and c) bar-bell compounds (Ph-BBC, A1 = A2 = A3 = CH; Pdz-BBC, A1 = A2 = N, A3 = CH; Pyz-BBC, A' = A''' = N, A'' = CH) (for abbreviations see footnote of Table 1).
^O+
Figure 2. Mechanism of the Krohnke pyridine synthesis.[4]
0 0 0 i00rWSei0 R'^W
N^ N^N .N.
W
I0 R^^
R2
R = H,Ph R
Figure 3. Synthetic pathway to the bis(terpyridine) (BTP, top), the phenylseptipyridine (PhSpPy, bottom) and the septipyridine (SpPy, bottom) based backbone systems in the preferred and less preferred conformation (R1, R2 see Figure 1).
Cl'
a
O v^
Cl
(Ph,Ph-ch) pi = Y = CH) (2,2'ch) (X = Y = N)
(Ph,Ph'-Pdz-BBC) (X = Y = CH) (2,2-Pdz-BBC) (X = Y = N)
KM t
'oci
^ N
(Ph,Ph'-ch) (X = Y = CH) (3,3'-ch) (X = Y = N)
(Ph, Ph' -Pyz-BBC) (X = Y = CH) (3,3' Pyz-BBC) (X = Y = N)
Figure 4. Synthetic pathway to pyridazine (Pdz-BBC, top) and pyrazine (Pyz-BBC, bottom) bar-bell compounds in the preferred and less preferred conformation.
pyridinium salt and the a,p-unsaturated ketone (chalcone) (Figures 2-4). In the first key step the pyridinium activated methylene group attacks the double bond of the chalcone in a Michael addition and in the second step aza ring closure is provided by ammonium acetate.[4] Those steps require sufficient nucleophilicity of the methylene group and
electrophilicity at the carbonyl C and the p-C atom of the chalcone.
Efficient synthesis requires high purity compounds in acceptable yields. Furthermore, the yields may give some insight to the reactivity of the involved components. In the present report they fluctuate between almost 80% and below
1% depending on the different chalcones and bispyridinium salts (Table 1). It should be noted that the ring closure has to take place twice for each compound, i.e., the yields for the single ring closure step vary between 88 and 5% assuming independent reaction steps in the molecules. Furthermore, the values after workup are given, thus, different losses not related to reactivity but, e.g., to solubility will have a significant influence on the yields, too.
The average yields of the different bispyridinium salts are found in three groups with 40-50% (BTP, Ph-BBC), around 20% (PhSpPy, SpPy, Pdz-BBC), and 5% yield (Pyz-BBC). We assume that those differences are caused by the stability of the respective salts, i.e., the decrease of the yields in the row py-rimidine > pyridazine > pyrazine could originate from decomposition of the starting materials or intermediate products under
the reaction conditions. As the byproducts were not further analyzed we do not have a clear proof of this assumption.
In order to derive a statistically more reliable relation between the yields and the substituents of the participating chalcones a maximum number of reactions between different chalcones with a certain bispyridinium salt should be investigated. As seen in Table 1, the reactions of the SpPy bispyridinium salt led to 28 oligomers, which will be looked at more in detail. In the low yield region below 10% mainly thienyl, phenyl, biphenyl, styryl, hydroxyphenyl, and pyrenyl are employed as substituents whereas higher yields are obtained for 2-pyridyl, 4-pyridyl, and pyrazinyl containing chalcones. Especially, the 2-pyridyl substituent guarantees high yields in the Krohnke-type reaction. This finding is attributed to the withdrawing effect of the electron
Table 1. Yields of the ring closure reactions with the different bispyridinium salts.
R1 a Yield /% 1 a Yield /%
R BTP R R SpPy
3py sty 2 3th 3py 10
3py 3py 13[5c] 3th Ph 10
2РУ 3th 15 4F Ph 11
2РУ Ph 18 3th 2th 14
Ph Ph 24 2py 3py 18
2py sty 43 2py sty 28
2py 2py 62[5d] 3th 3th 31
4py 3py 69[5c] 4py 3py 32
2py 3py 70[5c] pyz 3py 33
2py 4py 71 [5c] 3hy 2py 35
3th 2py 71 3th 2py 35
avg. yield 42 2py 3th 35
PhSpPy 2py 4F 36
2py 4py 11[5d] 2py 4py 53
2py 3py 16[5d] 2py 2th 53
3py 3py 17[5d] BiPh BiPh 58
pyz 3py 20 avg. yield 19
2py 2py 26[5d] Ph-BBC
4py 3py 38[5d] 3py 3py 18
avg. yield 21 2py 3py 35
SpPy 2py Ph 54
2th 2th 0.3 Ph 3py 74
3th sty 0.9 4py 3py 79
2th 3th 0.9 avg. yield 52
Ph 3th 1.2 Pdz-BBC
3py P 2 Ph Ph 20
3py 3th 3 2py 2py 27
3hy 4py 5 avg. yield 24
Ph sty 5 Pyz-BBC
4Br Ph 6 Ph Ph 3
3py sty 7 3py 3py 6
BiPh Ph 8 avg. yield 5
Ph BiPh 9
a 2py: 2-pyridyl, 3py: 3-pyridyl, 4py: 4-pyridyl, 2th: 2-thienyl, 3th, 3-thienyl, Ph, phenyl, pyz: pyrazinyl, 3hy: 3-hydroxyphenyl, P: pyrenyl, 4Br: 4-bromophenyl, 4F: 4-fluorophenyl, BiPh: biphenyl.
poor nitrogen comprising heteroaromatics, which favor the nucleophilic attack in the Michael addition and in the ring closure. Interestingly, 3-pyridyl substituted chalcones display rather poor yields not only for the SpPys but also for the BTPs and BBCs. Here, the relatively higher electron density in 3-position of the pyridine ring disfavors the desired nucleophilic reaction as already found for the synthesis of the chalcones.[5d] The comparably high yields of the bis(3-thienyl) and bis(biphenyl) substituted oligomers are regarded as exception, which might be caused by solubility effects in the workup. Corresponding results are found for the other bispyridinium salts, too, including the oligopyridines, which we have prepared recently[5c,5d] (Table 1).
It shall be noted that besides electronic effects sterics play an important role, too. Thus, further sterically demanding chalcones with anthracene and/or pyrene substituents were prepared (see experimental section). Attempts to convert those chalcones with the aforementioned bispyridinium salts to the corresponding oligomers were not successful.
Conclusion
We have shown that a broad variety of different chalcones can be reacted with bispyridinium salts to yield oligopyridines with different electron poor and/or rich substituents. The accessibility of those compounds can be fairly predicted by simple electronic considerations at the chalcones. Further investigations on the two-dimensional self-assembly properties of these compounds are ongoing.
Experimental
General
The used chemicals were obtained from commercial sources, all at least with a purity of 96% and they were used without further purification.
The following chalcones and bispyridinium salts were synthesized according to the literature: bisphenyl chalcone (ch), 2-pyridyl-2'-thienyl chalcone (2N,2S'-ch), 2-pyridyl-3'-thienyl chalcone (2N,3S'-ch), 3-pyridyl-3'-thienyl chalcone (3N,3S'-ch), 2-thienyl-2'-thienyl chalcone (2S,2S'-ch), and 2-thienyl-3'-thienyl chalcone (2S,3S'-ch),[8] 2-pyridyl-2'-pyridyl chalcone (2,2'-ch), 2-pyridyl-phenyl chalcone (2N,Ph'-ch), and phenyl-3'-pyridyl chalcone (Ph,3N'-ch),[9] 2-pyridyl-3'-pyridyl chalcone (2,3'-ch),
2-pyridyl-4'-pyridyl chalcone (2,4'-ch), 3-pyridyl-3'-pyridyl chalcone (3,3'-ch), and 4-pyridyl-3'-pyridyl chalcone (4,3'-ch),[10]
3-thienyl-2'-pyridyl chalcone (3S,2N'-ch), 3-thienyl-3'-pyridyl chalcone (3S,3N'-ch), 3-thienyl-phenyl chalcone (3S,Ph'-ch), 3-thienyl-2'-thienyl chalcone (3S,2S'-ch), and 3-thienyl-3'-thienyl chalcone (3S,3S'-ch),[11] phenyl-3-thienyl chalcone (Ph,3S'-ch),[12] 3-hydroxyphenyl-2'-pyridyl chalcone (3OH,2N'-ch),[13] 3-hydroxyphenyl-4'-pyridyl chalcone (3OH,4N'-ch),[14] phenyl-biphenyl chalcone (Ph,BiPh'-ch),[15] biphenyl-phenyl chalcone (BiPh,Ph'-ch), (BiPh,BiPh'-ch),[16] phenyl-styryl chalcone (Ph,Sty'-ch),[17] 2-pyridyl-styryl chalcone (2N,Sty'-ch),[18] 3-pyridyl-styryl chalcone (3N,Sty'-ch),[19] phenyl-4'-bromophenyl chalcone (Ph,4Br'-ch), (Ph,4F'-ch),[20] phenyl-4'-fluorophenyl chalcone (2N,4F'-ch),[21] pyridazyl-3'-pyridyl (2,5,3'-ch),[22] phenylpyridine bispyridinium salt (PhSpPy-salt),[5d] pyridine bispyridinium salt (SpPy-salt), phenylene bispyridinium salt (Ph-BBC-salt),[4] phenylpyrimidine bispyridinium salt (BTP-salt).[5a]
The NMR data were obtained on a Bruker DRX 400 and DRX 500 spectrometer, respectively, calibrated against the solvent signal (CDCl3: 'H NMR: 5 = 7.27; 13C NMR: 5 = 77.0; DMSO-d6: 'H NMR: 5 = 2.50; tetrachloroethane-d2: 'H NMR: 5 = 6.00; 13C NMR: 5 = 74.2) and are given in ppm.
Mass specrometry was performed on a Finnigan Mat SSQ 7000 (CI) and a Bruker Reflex III (MALDI-TOF), respectively. Elemental analyses were measured on an Elementar Vario EL.
Synthesis
3-Thienyl-styryl' chalcone. To 3-acetylthiophene (3acth) (1.45 g, 12.0 mmol) in MeOH (30 mL) cinnamone aldehyde (cinal) (1.57 g, 11.9 mmol) and 2M KOH (5.0 mL) were given and refluxed for 1 d. After cooling to r.t. and the addition of aqua destillata (12 mL) a solid was filtered, washed with MeOH and dried under vacuum. Yield 21.0% (603 mg, 2.50 mmol). 1H NMR (400 MHz, CDCl3): 5 = 8.12 (1H, dd, 4J = 3.2 Hz, 4J = 1.2 Hz, H1), 7.65 (1H, dd, 3J = 5.2 Hz, 4J = 1.2 Hz, H2), 7.62 (1H, dt, 3J = 14.8 Hz, 3J = 5.2 Hz, H3), 7.53-7.50 (2H, m, H8 and H12), 7.41-7.36 (1H, m, H10), 7.39 (1H, d, 3J = 14.8 Hz, H4 or H5), 7.37 (1H, d, 3J = 16.0 Hz, H6 or H7), 7.36 (1H, d, 3J = 16.0 Hz, H6 or H7), 7.04-7.01 (2H, m, H9 and H11), 6.99 (1H, d, 3J = 14.8 Hz, H4 or H5). 13C NMR (500 MHz, CDCl3): 5 = 184.0, 144.1, 143.1, 141.8, 136.1, 131.7, 129.2, 128.8, 127.4, 127.2, 126.8, 126.4, 126.1. MS (CI): calculated m/z for C15H12OS: 241.28 [M+H]+, found: 240.90. Elemental analysis: calculated: %C 74.97, %H 5.03; found: %C 75.24, %H 4.72.
3-Pyridyl-pyrene-1-yl' chalcone. 3-Acetylpyridine (3acpy) (265 mg, 2.19 mmol) and pyrene-1-carbaldehyde (P1al) (513 mg, 2.22 mmol) in MeOH (35 mL) and 1M NaOH (5 mL) were refluxed for 24 h. The resulting precipitate was filtered and washed with MeOH. Yield: 28.4% (208 mg, 0.623 mmol). 1H NMR (400 MHz, TCE-d2): 5 = 9.34 (1H, d, 4J = 2.0 Hz, H1), 9.02 (1H, d, 3J = 15.2 Hz, H5 or H6), 8.85 (1H, d, 3J = 4.8 Hz, H2), 8.55 (1H, d, 3J = 9.2 Hz, Hey™), 8.46 (1H, d, 3J = 8.0 Hz, Hp™'), 8.40 (1H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H4), 8.30-8.27 (2H, m, Hpy™), 8.24 (1H, d, 3J = 9.2 Hz, Hp™'), 8.23 (1H, d, 3J = 8.4 Hz, №^"<9, 8.19 (1H, d, 3J = 9.2 Hz, Hpy™), 8.12 (1H, d, 3J = 8.8 Hz, №^"<9, 8.09 (1H, t, 3J = 7.6 Hz, Hpy™), 7.78 (1H, d, 3J = 15.6 Hz, H5 or H6), 7.53 (1H, dd, 3J = 4.8 Hz, 3J = 8.0 Hz, H3). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MS (CI): calculated m/z for C24H15NO: 334.38 [M+H]+, found: 334.12. Elemental analysis: calculated: %C 86.46, %H 4.54, %N 4.20; found: %C 86.42, %H 4.58, %N 4.36.
Phenylene-4-(pyrid-3-yl)' chalcone. Acetophenone (ac) (68.0 mg, 0.566 mmol), 4-(pyrid-3-yl)benzaldehyde (4(3py)bal) (103 mg, 0.562 mmol) in MeOH (18 mL) and 2 M NaOH (3 mL)
were stirred at r.t. for 2 d. The resulting solid was filtered, washed with MeOH and dried under vacuum. Yield: 37.4% (60.0 mg, 0.210 mmol). 'H NMR (400 MHz, CDCl3): 5 = 8.90 (1H, d, 4J = 2.0 Hz, H1), 8.63 (1H, dd, 4J = 1.6 Hz, 3J = 43.8 Hz, H4), 8.07-8.04 (2H, m, 3J = 8.4 Hz, H5), 7.92 (1H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H2), 7.86 (1H, d, 3J = 15.6 Hz, H7 or H8), 7.77 (2H, d, 3J = 8.0 Hz, H9), 7.66 (2H, d, 3J = 8.4 Hz, H6), 7.63-7.58 (1H, m, H11), 7.60 (1H, d, 3J = 15.6 Hz, H7 or H8), 7.53 (2H, t, 3J = 8.0 Hz, H10), 7.40 (1H, dd, 3J = 4.8 Hz, 3J = 8.0 Hz, H3). 13C NMR (400 MHz, CDCl3): 5 = 190.3, 149.0, 148.2, 143.9, 139.8, 138.0, 135.6, 134.6, 134.2, 132.9, 129.2, 128.6, 128.5, 127.6, 123.6, 122.4. MS (CI): calculated m/z for C20H15NO: 286.34 [M+H]+, found: 286.22. Elemental analysis: calculated: %C 84.19, %H 5.30, %N 4.91; found: %C 84.37, %H 5.20, %N 4.72.
Pyrene-1-yl-anthracen-9-yV chalcone. The synthesis was carried out according to 3-pyridyl-pyrene-1-yl chalcone (3py-P1-ch) with 1-acetylpyrene (1acP) (528 mg, 2.16 mmol), 9-anthraldehyde (9antal) (498 mg, 2.41 mmol), MeOH (25 mL) and 1M NaOH (5 mL). Yield: 89.8% (839 mg, 1.94 mmol). 1H NMR (400 MHz, CDCl3): 5 = 8.90 (1H, d, 3J = 9.2 Hz, H™at), 8.68 (1H, d, 3J = 16.0 Hz, H1 or H2), 8.46 (1H, s, Haromat), 8.41 (1H, d, 3J = 8.0 Hz, Haromat ), 8.33 (2H, d, 3J = 8.0 Hz, Haromat ), 8.29-8.21 (4H, m, H™at), 8.21 (1H, d, 3J = 8.8 Hz, H™at), 8.10-8.07 (2H, m, H™at), 8.02 (2H, d, 3J = 8.0 Hz, H™at), 7.55-7.48 (4H, m, H™at), 7.52 (1H, d, 3J = 16.0 Hz, H1 or H2). 13C NMR (400 MHz, CDCl3): 5 = 194.9, 142.9, 135.9, 135.5, 133.1, 131.2, 131.1, 130.6, 129.7, 129.6, 129.5, 129.4, 129.3, 128.9, 128.6, 127.1, 126.6, 126.5, 126.4, 126.2, 126.0, 125.4, 125.2, 124.9, 124.8, 124.3, 124.1. MS (CI): calculated m/z for C33H20O: 433.50 [M+H]+, found: 433.09. Elemental analysis: calculated: %C 91.64, %H 4.66; found: %C 91.92, %H 4.51.
Pyren-1-yl-4-biphenyl' chalcone. The synthesis was carried out according to 3py-P1-ch with 1-acetylpyrene (1acP) (500 mg, 2.05 mmol), 4-biphenyl carboxaldehyde (4BiPhal) (381 mg, 2.09 mol), MeOH (25 mL) and 1M NaOH (5 mL). Yield: 92.0% (770 mg, 1.88 mmol). 1H NMR (400 MHz, CDCl3): 5 = 8.64 (1H, d, 3J = 9.2 Hz, Haromat), 8.30-8.24 (4H, m, Haromat), 8.21 (2H, d, 3J = 9.2 Hz, Haromat), 8.14 (1H, d, 3J = 8.8 Hz, H™at), 8.09 (1H, t, 3J = 8.0 Hz, Haromat), 7.70 (1H, d, 3J = 16.0 Hz, H1 or H2), 7.72-7.62 (6H, m, Haromat), 7.52 (1H, d, 3J = 16.0 Hz, H1 or H2), 7.50-7.45 (2H, m, Haromat), 7.42-7.37 (1H, m, Haromat). 13C NMR (400 MHz, CDCl3): 5 = 195.8, 145.5, 143.3, 139.9, 133.8, 133.5, 133.2, 131.0, 130.6, 129.3, 129.1, 129.04, 128.96, 128.9, 127.9, 127.5, 127.2, 127.1, 127.0, 126.3, 126.2, 126.0, 125.9, 124.8, 124.7, 124.3, 124.0. MS (CI): calculated m/z for C31H20O: 409.48 [M+H]+, found: 409.22. Elemental analysis: calculated: %C 91.15, %H 4.93; found: %C 91.07, %H 5.03.
mmol), MeOH (25 mL) and 1M NaOH (5 mL).Yield: 94.0% (1.96 g, 4.79 mmol). 1H NMR (400 MHz, CDCl3): 5 = 9.07 (1H, d, 3J = 15.6 Hz, H1 or H2), 8.60 (1H, d, 3J = 9.2 Hz, Haromat), 8.48 (1H, d, 3J = 8.4 Hz, H™at), 8.27-8.21 (6H, m, Haromat), 8.16 (1H, d, 3J = 9.2 Hz, H™at), 8.10 (1H, d, 3J = 8.8 Hz, H™at), 8.06 (1H, t, 3J = 7.6 Hz, H™at), 7.89 (1H, d, 3J = 15.6 Hz, H1 or H2), 7.81-7.78 (2H, m, Haromat.), 7.72-7.69 (2H, m, Haromat.), 7.54-7.49 (2H, m, Haromat.), 7.46-7.41 (1H, m, Haromat). 13C NMR (500 MHz, CDCl3): 5 = 189.6, 145.5, 141.3, 139.9, 137.0, 132.9, 131.2, 130.7, 130.3, 129.2, 128.9, 128.70, 128.69, 128.67, 128.2, 127.31, 127.28, 126.3, 126.0, 125.9, 125.0, 124.9, 124.5, 124.2, 123.8, 122.6. MS (CI): calculated m/z for C31H20O: 409.48 [M+H]+, found: 409.19. Elemental analysis: calculated: %C 91.15, %H 4.93; found: %C 91.24, %H 4.96.
Anthracen-9-yl-4-biphenyl' chalcone. The synthesis was carried out according to 3py-P1-ch with 4-biphenyl carboxaldehyde (4BiPhal) (419 mg, 2.30 mmol), 9-acetylanthracene (9acant) (503 mg, 2.28 mmol), MeOH (25 mL) and 1M NaOH (5 mL). Yield: 96.1% (844 mg, 2.20 mmol). 1H NMR (400 MHz, CDCl3): 5 = 8.58 (1H, s, Haromat), 8.10-8.07 (2H, m, Haromat), 7.97-7.94 (2H, m, Haromat), 7.60-7.57 (4H, m, Haromat), 7.54-7.49 (6H, m, Haromat), 7.487.43 (2H, m, Haromat), 7.39-7.35 (1H, m, Haromat), 7.36 (1H, d, 3J = 15.6 Hz, H1 or H2), 7.28 (1H, d, 3J = 15.6 Hz, H1 or H2). 13C NMR (400 MHz, CDCl3): 5 = 200.2, 147.5, 143.7, 139.9, 134.5, 133.1, 131.1 129.2, 128^3, 128.90, 128.6, 128.4, 128.0, 127.5, 127.0, 126.6, 125.5, 125.3. MS (CI): calculated m/z for C29H20O: 385.46 [M+H]+, found: 385.12. Elemental analysis: calculated: %C 90.60, %H 5.24; found: %C 90.44, %H 5.27.
Anthracen-9-yl-pyrene-1-yl' chalcone. The synthesis was carried out according to 3py-P1-ch with P1al (534 mg, 2.32 mmol), 9acant (499 mg, 2.27 mmol), MeOH (25 mL) and 1M NaOH (5 mL). Yield: 93.4% (916 mg, 2.12 mmol). 1H NMR (400 MHz, CDCl3): 5 = 8.63 (1H, s, Haromat), 8.49 (1H, d, 3J = 15.6 Hz, H1 or H2), 8.28 (1H, d, 3J = 8.0 Hz, H™at), 8.16-8.04 (8H, m, Haromat), 7.97-7.95 (1H, m, H™at), 7.96 (1H, d, 3J = 15.6 Hz, H1 or H2), 7.87 (1H, d, 3J = 9.6 Hz, Haromat), 7.81 (1H, d, 3J = 9.2 Hz, H™at), 7.58-7.51 (5H, m, H™at). 13C NMR (400 MHz, CDCl3): 5 = 199.7, 144.2, 134.9, 133.1, 131.2, 131.1, 130.6, 130.4, 130.1, 128.9, 128.74, 128.65, 128.61, 128.5, 127.8, 127.2, 126.7, 126.2, 126.1, 125.9, 125.6, 125.4, 125.0, 124.7, 124.3, 121.9. MS (CI): calculated m/z for C33H20O: 433.50 [M+H]+, found: 433.14. Elemental analysis: calculated: %C 91.64, %H 4.66; found: %C 91.60, %H 4.67.
4-Biphenyl-pyrene-1-yl'chalcone. The synthesis was carried out according to 3py-P1-ch with pyrene-1-carbaldehyde (P1al) (1.20 g, 5.23 mmol), 4-acetylbiphenyl (4acBiPh) (1.00 g, 5.10
Ph,Ph'-BTP. NH4OAc (1.20 g, 15.6 mmol), chalcone ch (139 mg, 0.668 mmol), and phenylpyrimidine bispyridinium iodine salt (BTP-salt) (203 mg, 0.312 mmol) were suspended in MeOH (5 mL) and refluxed for 24 h. A solid was filtered and dried under vacuum. Yield: 24% (47 mg, 0.076 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.87 (1H, s, H5), 8.95 (2H, d, 4J = 1.5 Hz, H3' or H5''), 8.84-8.82 (2H, m, H2' and H6'), 8.45-8.43 (4H, m, H2''' and H6'''), 8.17 (2H, d, 4J = 1.5 Hz, H3' or H5''), 7.93 (4H, m, HPhen>"), 7.66-7.62 (11H, m, HPheny'), 7.59-7.56 (4H, m, HPhen>"). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 164.8, 157.6, 155.3, 150.9, 139.4, 139.1, 138.6, 130.8, 129.6, 129.41, 129.38, 129.0,128.88, 128.81, 128.7, 127.5, 127.4, 119.8, 118.5, 112. MALDI-TOF: calculated m/z for C44H30N4: 615.70 [M+H]+, found: 616.05. Elemental analysis: calculated: %C 85.97, %H 4.92, %N 9.11; found: %C 86.11, %H 4.91, %N 9.03.
1,M
4'
2,Ph'-BTP. The synthesis was carried out according to Ph,Ph'-BTP with NH4OAc (1.13 g, 14.7 mmol), chalcone 2N,Ph'-ch (135 mg, 0.646 mmol) and BTP-salt (200 mg, 0.308 mmol), MeOH (5.0 mL). Yield: 18% (36 mg, 0.058 mmol). 1H NMR (500 MHz, 100°C, TCE-d2): 5 = 9.81 (1H, s, H5), 9.04 (2H, d, 4J = 2.0 Hz, H3'' or H5''), 8.95 C2H, d, 4J = 1.5 Hz, H3'' or H5''), 8.92 (2H, d, 3J = 7.5 Hz, H6'''), 8.84-8.82 (4H, m, H2'', H6'' and H3'''), 8.00-7.97 (4H, m, HPhe"y'), 7.95 (2H, dd, 4J = 2.0 Hz, 3J = 7.5 Hz, HPhe"y'), 7.65-7.61 (7H, m, H4', H5''' and HPhe"y'), 7.59-7.55 (2H, m, HPhe"y'), 7.46-7.43 (2H, ddd,4J = 1.0 Hz, 3J = 5.0, 3J = 5.0 Hz, H4'''). 13C NMR (500 MHz, 100°C, TCE-d2): 5 = 164.5, 164.4, 156.4, 156.1, 154.5, 150.9, 149.6, 138.6, 138.1, 137.1, 131.2, 129.7, 129.5, 129.0, 128.9, 127.7, 124.5, 121.7, 120.9, 120.9, 112.3. MALDI-TOF: calculated m/z for C42H28N6: 617.73 [M+H]+, found: 618.08. Elemental analysis: calculated: %C 81.52, %H 4.62, %N 13.65; found: %C 81.80, %H 4.58, %N 13.63.
■I"
A'
2N,3S'-BTP The synthesis was carried out according to Ph,Ph'-BTP with chalcone 3S,2N'-ch (217 mg, 1.01 mmol), BTP-salt (300 mg, 0.461 mmol), NH4OAc (623 mg, 8.09 mmol) and MeOH. Yield 14.8% (43 mg, 0.0684 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.76 (1H, s, H5), 8.98 (2H, d, 4J = 1.5 Hz, H3' or H5''), 8.89 (2H, d, 4J = 1.5 Hz, H3' or H5''), 8.87 (2H, d, 4J = 0.5 Hz, 4J = 1.0 Hz, 3J = 7.5 Hz, H6'''), 8.84-8.83 (2H, m, (H2' and H6') or (H4''' and H6''')), 8.83-8.81 (2H, m, (H2' and H6') or (H4''' and H6''')), 8.01 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2''''), 7.94 (2H, dt, 4J = 1.5 Hz, 3J = 7.5 Hz, H4'''), 7.78 (2H, d, 4J = 1.5 Hz, 3J = 5.0 Hz, H5''''), 7.68-7.62 (3H, m, H3', H4' and H5'), 7.58 (2H, dd, 4J = 2.5 Hz, 3J =
5.0 Hz, H4""), 7.44 (2H, ddd, 4J = 1.0 Hz, 4J = 1.5 Hz, 3J = 7.5 Hz, H4"). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C38H24N6S2: 630.59 [M+2H]+, found: 630.95. Elemental analysis: calculated: %C 72.59, %H 3.85, %N 13.37; found: %C 72.30, %H 3.88, %N 13.58.
-t1
3S,2N'-BTP The synthesis was carried out according to Ph,Ph'-BTP with chalcone 2N,3S'-ch (278 mg, 1.29 mmol), BTP-salt (300 mg 0.461 mmol), NH4OAc (839 mg, 1.09 mmol) and MeOH (5mL). Yield 70.7% (205 mg, 0.326 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.76 (1H, s, H5), 9.18 (2H, d, 4J = 1.5 Hz, H3' or H5' ), 8.90 (2H, ddd, 4J = 1.0 Hz, 4J = 1.5 Hz, 3J = 5.0 Hz, H3'), 8.87-8.84 (2H, m, H2' and H6'), 8.54 (2H, d, 4J = 1.5 Hz, H3' or H5' ), 8.30 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2'''), 8.10 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5'''), 8.09 (2H, d, 'J = 8.0 Hz, H5''''), 7.99-7.92 (2H, m, H4 '), 7.69-7.65 (3H, m, H4' and H6 '), 7.64-7.60 (2H, m, H3' and H5'), 7.57 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4'''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C38H24N6S2: 630.59 [M+2H]+, found: 630.81. Elemental analysis: calculated: %C 72.59, %H 3.85, %N 13.37; found: %C 72.85, %H 3.92, %N 12.97.
2N,Sty'-BTP. The synthesis was carried out according to Ph,Ph'-BTP with chalcone 2N,Sty'-ch (329 mg, 1.40 mmol), BTP-salt (411mg, 0.632 mmol), NH4OAc (1.63 g, 21.1 mmol) and MeOH (20 mL). Yield: 42.5% (180 mg, 0.269 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.73 (1H, s, H5), 8.88-8.79 (8H, m, H2', H6', H5', H3' and H6'), 7.94 (2H, td, 4J = 1.5 Hz, 3J = 7.5 Hz, H5 '), 7.71-7.62 (9H, m, i.a. H4'), 7.69 (2H, d, 3J = 16.0 Hz, H7 or H8), 7.51-7.47 (4H, m), 7.45-7.41 (4H, m), 7.37 (2H, d, 3J = 16.0 Hz, H7 or H8), the remaining unassigned peaks belong to H3' and HPhe"y'. 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C46H32N6: (570.84 [M+2H]+, found: 670.75. Elemental analysis: calculated: %C 82.61, %H 4.82, %N 12.57; found: %C 82.81, %H 4.73, %N 12.69.
3N,Sty'-BTP. The synthesis was carried out according to Ph,Ph'-BTP with chalcone 3N,Sty'-ch (146 mg, 0.621 mmol), BTP-salt (202 mg, 0.311 mmol), NH4OAc (1.74 g, 22.6 mmol)
and MeOH (20 mL). Yield: 2.02% (4.20 mg, 0.00627 mmol). 'H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.67 (1H, s, H5), 9.52 (2H, d, 4J = 1.0 Hz, H2'''), 8.87-8.84 (4H, m, (H2' and H6'), H4''' or H6'''), 8.82-8.80 (2H, m, (H2' and H6'), H4''' or H6'''), 8.72-8.69 (2H, m, (H2' and H6'), H4''' or H6'''), 8.05 (2H, d, 4J = 1.5 Hz, H3''), 7.72-7.60 (11H, m), 7.62 (2H, d, 3J = 16.5 Hz, H7 or H8), 7.52-7.48 (4H, m), 7.43 (2H, t, 3J = 7.5 Hz), 7.36 (2H, d, 3J = 16.0 Hz, H7 or H8), the remaining unassigned peaks belong to H5'', H5' and Hphenyl. 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C46H32N6: 521.61 [M-2C6H6+7H]+, found: 521.83. Elemental analysis: not enough material.
2,5,3'-PhSpPy. 2,5,3'-Azachalcone (2,5,3'-ch) (72.7 mg, 0.342 mmol), phenylpyridine bispyridinium iodine salt (PhSpPy-salt) (103 mg, 0.159 mmol) and NH4OAc (600 mg, 7.79 mmol) were refluxed in MeOH (7 mL) for 24 h. The resulting solid was filtered, washed with MeOH and dried under vacuum. Yield 20.3% (20.0 mg, 0.0323 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 10.00 (2H, d, 4J = 1.5 Hz, H3' , H5' , H2' or H6 '), 9.20 (2H, d, 4J = 2.0 Hz, H3' , H5' , H2 ' or H6''''), 9.07 (2H, s, H3 and H5), 9.05 (2H, d, 4 J = 1.5 Hz, H3' , H5' , H2' or H6''''), 8.81 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H4'''), 8.80 (2H, d, 4J = 2.0 Hz, H3' , H5' , H2' or H6'), 8.74 (2H, dd, 4J = 1.5 Hz, 4 J = 2.0 Hz, H3' or H4'), 8.71 (2H, d,4J = 2.5 Hz, H3"' or H4''''), 8.23 (2H, ddd,4J = 2.0 Hz, 4J = 2.0 Hz, 3J = 8.0 Hz, H5'''), 8.04-8.02 (2H, m, (H2' and H6') or (H3' and H5')), 7.70-7.66 (2H, m, (H2' and H6') or (H3' and H5')), 7.62-7.59 (1H, m, H4'), 7.55 (2H, ddd, 5 J = 0.5 Hz, 3J = 5.0 Hz, 3J = 8.0 Hz, H5'''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C39H25N9: 621.63 [M+2H]+, found: 622.03. Elemental analysis: calculate d: %C 75.59, %H 4.07, %N 20.34; found: %C 75.19, %H 4.13, %N 20.53.
2,3'-SpPy. 2,3'-Dipyridylchalcone (2,3'-ch) (103 mg, 0.490 mmol), pyridine bispyridinium iodine salt (SpPy-salt) (140 mg, 0.244 mmol) and NH4OAc (375 mg, 4.87 mmol) were refluxed in MeOH (7 mL) for 3 d4. The filtered solid was washed with MeOH and dried under vacuum. Yield: 18.1% (24.0 mg, 0.0443 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.19 (2H, d, 4J = 2.5 Hz, H5', H2' or H6'), 8.95 (2H, d, 4J = 2.0 Hz, H5', H2' or H6''), 8.84 (2H, d, 4J = 2.0 Hz, H5', H2' or H6'), 8.81-8.73 (8H, m, H3, H4', H3' and H6'), 8.22 (2H, td, 4 J = 2.0 Hz, 3J = 8.0 Hz, H6''), 8.15 (1H, t, 3J = 8.0 Hz, H4), 7.95 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5'''), 7.53 (2H, dd, 3J = 4.5 Hz, 3J = 7.5 Hz, H5''), 7.42 (2H, ddd, 4J = 1.0 Hz, 3J = 4.5 Hz, 3J= 7.5 Hz, H4'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too
low. MALDI-TOF: calculated m/z for C35H23N7: 543.58 [M+2H]+, found: 543.17. Elemental analysis: calculated: %C 77.62, %H 4.28, %N 18.10; found: %C 77.58, %H4.51, %N 17.81. -N,
2,4'-SpPy. The synthesis was carried out according to 2,3'-SpPy with 2,3'-dipyridylchalcone (2,3'-ch) (353 mg, 1.68 mmol), SpPy-salt (400 mg, 0.698 mmol) and NH4OAc (818 mg, 10.6 mmol). Yield: 52.9% (200 mg, 0.369 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.00 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.88 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.85 (4H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H3' ), 8.81 (2H, ddd, 4J = 1.0 Hz, 4J = 1.5 Hz, 3J = 4.5 Hz, H6'''), 8.79 (2H, d, 3J = 8.0 Hz, H3'''), 8.75 (2H, td, 4J = 1.0 Hz, 3J = 8.0 Hz, H3 and H5), 8.15 (1H, t, 3J = 7.5 Hz, H4), 7.95 (2H, dt, 4J = 2.0 Hz, 3J = 7.5 Hz, H5'''), 7.84 (4H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H2''), 7.43 (2H, ddd, 4J = 1.5 Hz, 3J = 4.5 Hz, 3J = 7.5 Hz, H4'''). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 157.1, 156.8, 156.2, 155.6, 150.9, 149.6, 147.7, 146.5, 137.0,124.2, 122.0, 121.8, 121.6, 120.6, 119.2, 119.0. MALDI-TOF: calculated m/z for C35H23N7: 543.58 [M+2H]+, found: 543.40. Elemental analysis: calculated: %C 77.62, %H 4.28, %N 18.10; found: %C 77.62, %H 4.29, %N 17.94.
4"
5" fPi
(I J
I ill r n
J* Jl ... X X
4,3'-SpPy. The synthesis was carried out according to 2,3'-SpPy with 4,3'-dipyridylchalcone (4,3'-ch) (203 mg, 0.966 mmol), SpPy-salt (275 mg, 0.480 mmol) and NH4OAc (705 mg, 9.14 mmol). Yield: 32.2% (84.0 mg, 0.155 mmol). « NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.13 (2H, d, 4J = 1.5 Hz, H3' or H2''), 8.94 (2H, d, 4J = 1.0 Hz, H3' or H2' ), 8.86 (4H, dd, 4J = 2.0 Hz, 3J = 4.5 Hz, H3 "), 8.81 (2H, dd, 4J = 2.0 Hz, 3J = 5.0 Hz, H4"), 8.80 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.16 (4H, dd, 4J = 2.0 Hz, 3J = 4.5 Hz, H3"), 8.19-8.14 (3H, m, H4 and H6' ), 8.09 (2H, d, 4J = 1.5 Hz, H5'), 7.55 (2H, dd, 3J = 4.5 Hz, 3J = 7.5 Hz, H5'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C35H23N7: 543.58 [M+2H]+, found: 543.62. Elemental analysis: calculated: %C 77.62, %H 4.28, %N 18.10; found: %C 77.73, %H 4.28, %N 17.!
2,5,3'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 2,5,3'-ch (253 mg, 1.20 mmol), SpPy-salt
(286 mg, 0.499 mmol), NH4OAc (2.00 g, 25.9 mmol) and MeOH (20 mL). Yield: 33.1% (90.0 mg, 0.165 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.96 (2H, d, 4J = 1.5 Hz, H3', H5', H2' or H6'''), 9.18 (2H, d, 4J = 2.5 Hz, H3', H5', H2 ' or H6'''), 9.00 (2H, d, 4J = 1.5 Hz, H3', H5', H2' or H6'), 8.82-8.79 (4H, m, H3, H4' , H3' or H4'), 8.77 (2H, 4J = 1.5 Hz, H3', H5', H2 ' or H6'''), 8.74-8.70 (4H, m, H3, H4' , H3 ' or H4 '), 8.21 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H6''), 8.19 (1H, t, 3J = 8.0 Hz, H4), 7.54 (2H, ddd, 5J = 0.5 Hz, 3J = 5.0 Hz, 3J = 8.0 Hz, H5'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N9: 545.55 [M+2H]+, found: 545.62. Elemental analysis: calculated: %C 72.92, %H 3.89, %N 23.19; found: %C 73.20, %H 3.72, %N 22.95.
2N,3S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 2N,3S'-ch (303 mg, 1.41 mmol), SpPy-salt (400 mg, 0.698 mmol), NH4OAc (752 mg, 9.76 mmol) and MeOH (8 mL). Yield: 35.3% (136 mg, 0.246 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.97 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.81 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.80 (2H, ddd, 4J = 1.0 Hz, 4J = 1.5 Hz, 3J = 5.0 Hz, H3' or H6'''), 8.75 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.73 (2H, d, 3J = 7.5 Hz, H3 ' or H6'''), 8.11 (1H, t, 3J = 8.0 Hz, H4), 7.99 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2''), 7.94 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5'''), 7.78 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5' ), 7.58 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4''), 7.40 (2H, ddd, 4J = 1.0 Hz, 3J = 5.0 Hz, 3J = 7.5 Hz, H4'''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 553.52 [M+2H]+, found: 553.31. Elemental analysis: calculated: %C 71.84, %H 3.84, %N 12.69; found: %C 71.88, %H 3.83, %N 12.55.
3S,2N'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3S,3N'-ch (441 mg, 2.05 mmol), SpPy-salt (588 mg 1.03 mmol), NH4OAc (1.61 g, 2.09 mmol) and MeOH (18 mL). Yield 35.3% (201 mg, 0.364 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.23 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.88 (2H, ddd, 4J = 1.0 Hz, 4J = 1.5 Hz, 3J = 4.5 Hz, H3''), 8.74 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.43 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.20 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2'''), 8.11 (1H, t, 3J = 8.0 Hz, H4), 8.09 (2H, d, 3J = 8.0 Hz, H6''), 7.99 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H5'''), 7.91 (2H, td, 4J = 1.5 Hz, 3J = 8.0 Hz, H5''), 7.52 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4'''), 7.43 (2H, ddd, 4J = 1.0 Hz, 4J = 4.5 Hz, 3J = 7.5 Hz, H4'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 553.52 [M+2H]+, found: 553.34. Elemental analysis: calculated: %C 71.84, %H 3.84, %N 12.69; found: %C 71.61, %H 3.82, %N 12.57.
2N,2S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 2N,2S'-ch (210 mg, 0.976 mmol), SpPy-salt (240 mg, 0.419 mmol), NH4OAc (1.20 g, 15.6 mmol) and MeOH (10 mL). Yield: 52.7% (122 mg, 0.221 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.04 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.82-8.80 (2H, m, (H3 and H5), H3' or H6'), 8.81 (2H, d, 4J = 2.0 Hz, H3' or H5'), 8.75 (2H, d, 3J = 8.0 Hz, (H3 and H5), H3 ' or H6'''), 8.73-8.71 (2H, m, (H3 and H5), H3' or H6'), 8.11 (1H, t, 3J = 7.5 Hz, H4), 7.94 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5'''), 7.87 (2H, dd, 4J = 1.0 Hz, 3J = 4.0 Hz, H3' ), 7.56 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H5''), 7.41 (2H, ddd, 4J = 1.0 Hz, 3J = 5.0 Hz, 3J = 7.5 Hz, H4'''), 7.28 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H4'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 553.52 [M+2H]+, found: 553.25. Elemental analysis: calculated: %C 71.84, %H 3.84, %N 12.69; found: %C 72.05, %H 3.74, %N 12.!
3N,3S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3N,3S'-ch (377 mg, 1.75 mmol), SpPy-salt (450 mg, 0.816 mmol), NH4OAc (1.20 g, 15.6 mmol) and MeOH (10 mL). Yield: 2.66% (12.0 mg, 0.0218 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.48 (2H, dd, 4J = 1.0 Hz, 4J = 2.5 Hz, H2'''), 8.93 (2H, d, 4J = 1.5 Hz, H3'), 8.76 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H4'''), 8.74 (2H, d, 3J = 7.5 Hz, H3 and H5), 8.57 (2H, ddd, 4J = 2.0 Hz, 4J = 2.5 Hz, 3J = 8.0 Hz, H6'''), 8.11 (1H, t, 3J = 8.0 Hz, H4), 8.04 (2H, d, 4J = 1.5 Hz, H5'), 7.93 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2''), 7.71 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5''), 7.60 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4' ), 7.51 (2H, ddd, 4J = 1.0 Hz, 3J = 5.0 Hz, 3J = 8.0 Hz, H5'''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 553.52 [M+2H]+, found: 553.03. Elemental analysis: not enough material.
3S,3N'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3S,3N'-ch (210 mg, 0.975 mmol), SpPy-salt (250 mg, 0.436 mmol), NH4OAc (1.20 g, 15.6 mmol) and MeOH (10 mL). Yield: 10.3% (25.0 mg, 0.0453 mmol). 1H NMR (500 MHz, 100 °C, TCE-dJ: 5 = 9.12-9.10 (2H, m, H2"), 8.79 (2H, d, 4J = 1.5 Hz,
H3), 8.78 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H4"), 8.75 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.17 (2H, dd, 4J = 1.5 Hz, 4J = 3.0 Hz, H2"), 8.15-8.12 (2H, m, H6"), 8.11 (1H, t, 3J = 8.0 Hz, H4), 7.93 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5 "), 7.90 (2H, d, 4J = 1.5 Hz, H5 ), 7.54-7.50 (4H, m, H5" and H4"). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 553.52 [M+2H]+, found: 553.08. Elemental analysis: calculated: %C 71.84, %H 3.84, %N 12.69; found: %C 71.92, %H 3.77, %N 12.79.
3S,Ph'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3S,Ph'-ch (289 mg, 1.34 mmol), SpPy-salt (352 mg, 0.614 mmol), NH4OAc (1.37 g, 17.8 mmol) and MeOH (10 mL). Yield: 10.3% (35.0 mg, 0.0636 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.90 (2H, d, 4J = 2.0 Hz, H3'), 8.73 (2H, d, 3J = 7.5 Hz, H3 andH5), 8.16 (2H, dd, 4J = 1.5 Hz, 4J = 3.0 Hz, H2'"), 8.09 (1H, t, 3J = 7.5 Hz, H4), 7.95-7.89 (8H, m, H5', H5' and HPheny'), 7.62-7.58 (4H, m, HPheny'), 7.56-7.54 (2H, m, HPheny'), 7.52 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 550.53 [M+H]+, found: 550.47. Elemental analysis: calcul3a3te2d1: %5 C2 76.47, %H 4.22, %N 7.64; found: %C 76.29, %H 4.37, %N 8.00.
Ph,3S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone Ph,3S'-ch (287 mg, 1.34 mmol), SpPy-salt (362 mg, 0.631 mmol), NH4OAc (1.37 g, 17.8 mmol) and MeOH (10 mL). Yield: 1.21% (4.20 mg, 0.00764 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.89 (2H, d, 4J = 1.5 Hz, H3'), 8.76 (2H, d, 3J = 7.5 Hz, H3 and H5), 8.29-8.27 (4H, m, H2''' and H6'''), 8.10 (1H, t, 3J = 7.5 Hz, H4), 8.04 (2H, d, 4J = 1.5 Hz, H5'), 7.92 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2''), 7.71 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5''), 7.62-7.57 (6H, m, H4'' and HPhen^'), 7.55-7.51 (2H, m, HPhen^'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C33H21N5S2: 551.53 [M+H]+, found: 551.27. Not enough material for an elemental analysis.
mmol), SpPy-salt (203 mg, 0.354 mmol), NH4OAc (732 mg, 9.50 mmol) and MeOH (10 mL). Yield: 35.0% (71.0 mg, 0.124 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.29-9-28 (2H, m, H3'), 8.89-8.80 (2H, m, H3''), 8.77 (2H, d, 3J = 7.5 Hz, H3 and H5), 8.55-8.54 (2H, m, H5'), 8.13-8.10 (2H, m, H5' , H2' or H6'), 8.11 (1H, t, 3J = 7.5 Hz, H4), 7.94-7.88 (6H, m, H5' , H6' , H2' or H6'), 7.49-7.42 (4H, m, H4' and H5'), 7.03-7.00 (2H, m, H4 '), 4.85 (2H, s (br), H3 '). MALDI-TOF: calculated m/z for C37H25N5O2: 572.60 [M+H]+, found: 572.67. Elemental analysis: calculated: %C 77.74, %H 4.41, %N 12.25; found: %C 77.55, %H 4.34, %N 12.36.
3OH,4N'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3OH,4N'-ch (180 mg, 0.799 mmol), SpPy-salt (223 mg, 0.389 mmol), NH4OAc (814 mg, 10.6 mmol) and MeOH (10 mL). Yield: 5.4% (12.0 mg, 0.0209 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.90 (2H, d, 4J = 1.5 Hz, H3'), 8.85 (4H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H3' ), 8.79 (2H, d, 3J = 8.0 Hz, H3), 8.14 (1H, t, 3J = 8.0 Hz, H4), 8.04 (2H, d, 4J = 1.5 Hz, H5'), 7.85-7.83 (4H, m, H2 ' and H6 '), 7.77 (4H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H2''), 7.48 (2H, t, 3J = 8.0 Hz, H5'''), 7.05-7.02 (2H, m, H4'''), 4.91 (2H, s (br), H3 '). MALDI-TOF: calculated m/z for C37H25N5O2: 573.60 [M+2H]+, found: 573.44. Not enough material for an elemental analysis.
S"'
3OH,2N'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3OH,2N'-ch (164 mg, 0.728
BiPh,BiPh'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone BiPh,BiPh'-ch (186 mg, 0.516 mmol), SpPy-salt (150 mg, 0.261 mmol), NH4OAc (830 mg, 10.8 mmol) and MeOH (10 mL). Yield: 57.6% (127 mg, 0.150 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.07 (2H, d, 4J = 1.5 Hz, H3'), 8.82 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.41 (4H, d, 3J = 8.5 Hz, H11 and H12), 8.18 (2H, d, 4J = 1.5 Hz, H5'), 8.15 (2H, t, 'J = 7.5 Hz, H4), 8.05 (4H, d, 3J = 8.5 Hz, HPhe"y'), 7.88-7.85 (8H, m, HPhe"y'), 7.77 (4H, d, 3J = 7.5 Hz, HPhe"y'), 7.73 (4H, d, 3J = 7.5 Hz, HPhe"y'), 7.56-7.50 (8H, m, HPhe"y'), 7.47-7.42 (4H, m, HPhe"y'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low; MALDI-TOF: calculated m/z for C63H43N3: 842.96 [M+2H]+, found: 843.28. Elemental analysis: calcu6ated: %C 89.86, %H 5.15, %N 4.99; found: %C 89.80, %H 5.10, %N 5.07.
Ph,BiPh'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone Ph,BiPh'-ch (299 mg, 1.05 mmol), SpPy-salt (306 mg, 0.534 mmol), NH4OAc (1.37 g, 17.8 mmol) and MeOH (10 mL). Yield: 9.0% (33.1 mg, 0.0480 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.06 (2H, d, 4J = 1.5 Hz, H3'), 8.79 (2H, d, 3J = 8.0 Hz), 8.34-8.32 (4H, m, H2 ' and H6'''), 8.13 (2H, d, 4J = 1.5 Hz, H5'), 8.12 (1H, t, 3J = 8.0 Hz, H4), 8.03 (4H, d, 3J = 8.5 Hz, Hphenyl), 7.86 (4H, d, 3J = 8.0 Hz, HPhe"yl), 7.74-7.71 (4H, m, HPhe"yl), 7.64-7.60 (4H, m, HPhe"yl), 7.56-7.49 (6H, m, HPhe"yl), 7.47-7.42 (2H, m, HPhe"yl). MALDI-TOF: calculated m/z for C51H35N3: 691.80 [m+2H]+, found: 691.30. Elemental analysis: calculated: %C 88.79, %H 5.11, %N 6.09; found: %C 88.94, %H 5.22, %N 6.15.
4Br'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone Ph,4Br'-ch (301 mg, 1.05 mmol), SpPy-salt (305 mg, 0.532 mmol), NH4OAc (1.37 g, 17.7 mmol) and MeOH (10 mL). Yield: 5.5% (20.4 mg, 0.0293 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.84 (2H, d, 4J = 1.5 Hz, H3'), 8.77 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.29-8.28 (4H, m, H2' and H6'), 8.11 (1H, t, 3J = 8.0 Hz, H4), 8.02 (2H, d, 4J = 2.0 Hz, H5'), 7.78-7.73 (8H, m, HPhe"yl), 7.62-7.58 (4H, m, HPhe"yl), 7.55-7.51 (2H, m, H4'''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C39Br2H25N3: 697.03 [M+2H]+, found: 696.91. Elemental analysis: calculated: %C 67.36, %H 3.62, %N 6.04; found: %C 67.20, %H 3.55, %N 6.13.
4F'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone Ph,4F'-ch (233 mg, 1.03 mmol), SpPy-salt (297 mg, 0.518 mmol), NH4OAc (1.26 g, 16.4 mmol) and MeOH (10 mL). Yield: 10.8% (32.2 mg, 0.0561 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.87 (2H, d, 4J = 1.5 Hz, H3'), 8.78
(2H, d, 3J = 7.5 Hz, H3 and H5), 8.30-8.28 (4H, m, H2" and H6 "), 8.11 (1H, t, 3J = 7.5 Hz, H4), 8.02 (2H, d, 4J = 1.5 Hz, H5), 7.917.87 (4H, m, H™at), 7.62- 7.58 (4H, m, H™at), 7.55-7.51 (2H, m, H4"), 7.32-7.27 (4H, m, Haromat). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 156.9, 155.8, 149.3, 139.7, 137.9, 135.5, 129.40, 129.38, 129.2, 129.1, 129.0, 127.4, 121.9, 120.63, 120.60, 118.4, 117.7, 116.4, 116.2. MALDI-TOF: [M+H]+, found: 574.94.
calculated m/z for C39H25F2N3:
574.61
2N,4F'-SpPy.The synthesis was carried out according to 2,3'-SpPy with chalcone 2N,4F'-ch (378 mg, 1.66 mmol), SpPy-salt (421 mg, 0.735 mmol), NH4OAc (1.47 g, 19.1 mmol) and MeOH (20 mL). Yield: 35.7% (151 mg, 0.262 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.98 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.82 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.83-8.81 (2H, m, H3'''), 8.79 (2H, d, 3J = 8.0 Hz, H3 or H6'), 8.76 (2H, d, 3J = 8.0 Hz, H3 or H6'), 8.15 (1H, t, 3J = 8.0 Hz, H4), 8.00-7.96 (6H, m, H2'', H6' and H5'''), 7.45-7.41 (2H, m, H4'), 7.34-7.29 (4H, m, H3' and H5'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C37H23F2N5: 576.58 [M+H]+, found: 576.94.
2S,2S'-SpPy.The synthesis was carried out according to 2,3'-SpPy with chalcone 2S,2S'-ch (452 mg, 2.05 mmol), SpPy-salt (587 mg, 1.02 mmol), NH4OAc (1.95 g, 25.4 mmol) and MeOH (20 mL). Yield: 0.260% (1.50 mg, 0.00267 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.86 (2H, d, 4J = 1.5 Hz, H3'), 8.69 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.09 (1H, t, 3J = 8.0 Hz, H4), 7.92 (2H, d, 4J = 1.5 Hz, H5'), 7.83 (2H, dd, 4J = 1.0 Hz, 3J = 3.5 Hz, H5"), 7.77 (2H, dd, 4J = 1.0 Hz, 3J = 3.5 Hz, H5"), 7.56 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H3' or H3"), 7.51 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H3' or H3'), 7.28 (2H, dd, 3J = 5.0 Hz, 3J = 5.0 Hz, H4"), 7.24 (2H, dd, 3J = 5.0 Hz, 3J = 5.0 Hz, H4 "). MALDI-TOF: calculated m/z for C31H19N3S4: 562.53 [M+2H]+, found: 562.58. Not enough material for an elemental analysis.
2S,3S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 2S,3S'-ch (407 mg, 1.85 mmol), SpPy-salt
(516 mg, 0.900 mmol), NH4OAc (1.87 g, 24.3 mmol) and MeOH (20 mL). Yield: 0.860% (4.3 5 mg, 0.00774 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.79 (2H, d, 4J = 1.5 Hz, H3'), 8.69 (2H, d, 3J = 7.5 Hz, H3 and H5), 8.09 (1H, t, 3J = 7.5 Hz, H4), 7.92 (2H, d, 4J = 1.5 Hz, H5'), 7.89 (2H, dd, 4J = 1.5 Hz, 4J = 3.0 Hz, H2' ), 7.83 (2H, dd, 4J = 1.0 Hz, 3J = 3.5 Hz, H5'''), 7.68 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5''), 7.58 (2H, dd, 4J = 3.0 Hz, J = 5.0 Hz, H4' ), 7.51 (2H, dd, 4J = 1.0 Hz, J = 5.0 Hz, H3'''), 7.23 (2H, dd, 4J = 3.5 Hz, 3J = 5.0 Hz, H4'''). MALDI-TOF: calculated m/z for C31H19N3S4: 562.53 [M+H]+, found: 563.02. Not enough material for an elemental analysis.
3" 4"
4" 4
3S,2S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3S,2S'-ch (440 mg, 2.00 mmol), SpPy-salt (502 mg,0.88 mmol), NH4OAc (2.08 g, 27.0 mmol) and MeOH (20 mL). Yield: 13.6% (67.2 mg, 0.119 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.89 (2H, d, 4J = 1.5 Hz, H3'), 8.70 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.15 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2'''), 8.07 (1H, t, 3J = 8.0 Hz, H4), 7.91 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H5'''), 7.90 (2H, d, 4J = 1.5 Hz, H5'), 7.77 (2H, dd, 4J = 1.0 Hz, 3J = 3.5 Hz, H5''), 7.55 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H3' or H4'''), 7.52 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H3' or H4'''), 7.27 (2H, dd, 3J = 3.5 Hz, 3J = 5.0 Hz, H4''). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 157.0,
155.5, 153.9, 143.4, 142.7, 142.5, 137.9, 128.6, 127.2, 126.9, 126.4,
125.6, 124.2, 121.7, 120.6, 116.7, 116.2. MALDI-TOF: calculated m/z for C31H19N3S4: 562.53 [M+H]+, found: 563.14. Elemental analysis: calculated: %C 68.28, %H 3.41, %N 7.48; found: %C 68.23, %H 3.51, %N 7.42.
4"
4'" 4
3S,3S'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3S,3S'-ch (618 mg, 2.81 mmol), SpPy-salt (804 mg, 1.40 mmol), NH4OAc (1.68 g, 21.7 mmol) and MeOH (20 mL). Yield: 30.8% (243 mg, 0.432 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.82 (2H, d, 4J = 1.5 Hz, H3'), 8.71 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.14 (2H, dd, 4J = 3.0 Hz, 4J = 1.5 Hz, H2'''), 8.08 (1H, t, 3J = 8.0 Hz, H4), 7.92 (2H, dd, 4J = 3.0 Hz, 4J = 1.0 Hz, H2''), 7.91 (2H, d, 4J = 1.5 Hz, H5'), 7.89 (2H, dd, 3J = 3.0 Hz, 4J = 1.0 Hz, H5 '), 7.69 (2H, dd, 3J = 5.0 Hz, 4J = 1.5 Hz, H5''), 7.58 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4' or H4'''), 7.52 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4' or H4'). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 157.0, 155.8, 153.9, 144.7, 142.9, 140.7, 137.8, 127.2, 126.9, 126.4, 126.3, 124.1, 123.3, 121.7, 120.6, 117.6, 117.0. MALDI-TOF: calculated m/z for C31H19N3S4: 562.53 [M+H]+, found: 563.05. Elemental analysis: calculated: %C 66.28, %H 3.41, %N 7.48; found: %C 66.39, %H 3.59, %N 7.19.
5"
BiPh,Ph'SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone BiPh,Ph'-ch (493 mg, 1.73 mmol), SpPy-salt (496 mg, 0.865 mmol), NH4OAc (1.71 g, 22.1 mmol) and MeOH (20 mL). Yield: 7.62% (45.5 mg, 0.0659 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.98 (2H, d, 4J = 1.5 Hz, H3 ), 8.82 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.41-8.38 (4H, m, H7 and H8), 8.134 (1H, t, 3J = 8.0 Hz, H4), 8.127 (2H, d, 4J = 1.5 Hz, H5), 7.97-7.94 (4H, m, HPhe"y'), 7.86-7.83 (4H, m, HPhe"y'), 7.78-7.75 (4H, m, HPhe"y'), 7.64-7.60 (4H, m, HPhe"y'), 7.58-7.52 (6H, m, HPhe"y'), 7.46-7.42 (2H, m, HPhe"y'). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 157.1, 156.9, 155.9, 150.3, 142.1, 140.9, 139.3, 138.8, 137.9, 129.4, 129.3, 129.0, 127.8, 127.7, 127.4, 127.3, 121.8, 120.6, 118.4, 118.0. MALDI-TOF: calculated m/z for C51H35N3: 690.79 [M+H]+, found: 691.17. Elemental analysis: calculated: %C 88.79, %H 5.11, %N 6.09; found: %C 88.61, %H 5.15, %N 6.20
4"
3S,Sty'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3S,Sty'-ch (494 mg, 2.01 mmol), SpPy-salt (588 mg,1.03 mmol), NH4OAc (1.63 g, 21.1 mmol) and MeOH (20 mL). Yield: 0.874 % (5.40 mg, 0.00897 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.77 (2H, d, 4J = 1.0 Hz, H3), 8.70 (2H, d, 3J = 8.0 Hz, H3 and H5), 8.14 (2H, dd, 4J = 1.0 Hz, 4J = 3.0 Hz, H2"), 8.07 (1H, t, 3J = 7.5 Hz, H4), 7.92 (2H, dd, 4J = 1.5 Hz, 3J = 5.0 Hz, H5 "), 7.79 (2H, d, 4J = 1.5 Hz, H5 ), 7.66 (4H, d, 3J = 7.5 Hz, H2" and H6"), 7.59 (2H, d, 3J = 16.0 Hz, H7 or H8), 7.52 (2H, dd, 4J = 3.0 Hz, 3J = 5.0 Hz, H4"), 7.44 (4H, t, 3J = 7.5 Hz, H3" and H5"), 7.41-7.39 (2H, m, H4"), 7.32 (2H, d, 3J = 16.0 Hz, H7 or H8). MALDI-TOF: calculated m/z for C39H27N3S2: 603.59 [M+2H]+, foimd: 603.29. Not enough material for an elemental analysis.
¥
2N,Sty'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 2N,Sty'-ch (468 mg, 1.99 mmol), SpPy-salt
(570 mg, 0.994 mmol), NH4OAc (1.96 g, 25.4 mmol) and MeOH (20 mL). Yield: 28.0% (165 mg, 0.278 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.89 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.82-8.81 (2H, m, H3'''), 8.75 (2H, d, 3J = 8.0 Hz, (H3 and H5) or H6'''), 8.72 (2H, d, 3J = 8.0 Hz, (H3 and H5) or H6'''), 8.69 (2H, d, 4J = 1.5 Hz, H3' or H5'), 8.11 (1H, t, 3J = 8.0 Hz, H4), 7.93 (2H, td, 3J = 8.0 Hz, 4J = 2.0 Hz, H5'), 7.70-7.66 (4H, m, H2'' and H6''), 7.68 (2H, d, 3J = 16.0 Hz, H7 or H8), 7.47-7.43 (4H, m, H3' and H5'), 7.42-7.40 (4H, m, H4' and H4'), 7.40 (2H, d, 3J = 16.0 Hz, H7 or H8). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C41H29N5: 592.67 [M+H]+, found: 593.08. Elemental analysis: calculated: %C 83.22, %H 4.94, %N 11.84; found: %C 83.12, %H 4.80, %N 12.01
3N,Sty'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3N,Sty'-ch (438 mg, 1.86 mmol), SpPy-salt (536 mg, 0.935 mmol), NH4OAc (1.70 g, 22.1 mmol) and MeOH (20 mL). Yield: 6.86% (38.0 mg, 0.0642 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.48-9.47 (2H, m, H2'''), 8.87 (2H, d, 4J = 1.5 Hz, H3'), 8.76 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H6''), 8.74 (2H, d, 3J = 7.5 Hz, H3 and H5), 8.57 (2H, td, 4J = 2.0 Hz, 3J = 8.0 Hz, H4'), 8.10 (1H, t, 3J = 8.0 Hz, H4), 7.93 (2H, d, 4J = 1.0 Hz, H5'), 7.67-7.66 (4H, m, H2 ' and H6' ), 7.62 (2H, d, 3J = 16.0 Hz, H7 or H8), 7.52 (2H, dd, 3J = 4.5 Hz, 'J = 8.0 Hz, H5'''), 7.47-7.39 (6H, m, H3', H4' and H5'), 7.35 (2H, d, 3J = 16.0 Hz, H7 or H8). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low; MALDI-TOF: calculated m/z for C41H29N5: 593.67 [M+2H]+, found: 593.41. Elemental analysis: calculated : %C 83.22, %H 4.94, %N 11.84; found: %C 83.08, %H 4.76, %N 12.09
Ph,Sty'-SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone Ph,Sty'-ch (457 mg, 1.95 mmol), SpPy-salt (559 mg, 0.975 mmol), NH4OAc (1.76 g, 22.8 mmol) and MeOH (20 mL). Yield: 4.69% (27.0 mg, 0.0457 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.83 (2H, d, 4J = 1.0 Hz, H3'), 8.76 (2H, d, 3J = 7.5 Hz, H3 and H5), 8.29-8.27 (4H, m, H2' and H6'), 8.09 (1H, t, 3J = 8.0 Hz, H4), 7.93 (2H, t, 4J = 1.0 Hz, H5'), 7.68-7.66 (4H, m, HPhenyl), 7.62-7.58 (4H, m, HPhenyl), 7.61 (2H, d, 3J = 16.0 Hz, H7 or H8), 7.54-7.52 (2H, m, HPhe"y'), 7.47-7.43 (4H, m, HPhe"y'), 7.41-7.39 (2H, m, HPhe"y'), 7.35 (2H, d, 3J = 16.0 Hz, H7 or H8). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C43H31N23 591.70 [M+2H]+, found: 591.35. Elemental analysis: calculated %C 87.58, %H 5.30, %N 7.13; found: %C 87.55, %H 5.25 %N 7.19.
3N,P'SpPy. The synthesis was carried out according to 2,3'-SpPy with chalcone 3N,P'-ch (150 mg, 0.450 mmol), SpPy-salt (130 mg, 0.227 mmol), NH4OAc (1.13 g, 14.7 mmol) and MeOH (20 mL).Yield: 1.95 % (3.50 mg, 0.0044 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.85 (2H, d, 4J = 2.0 Hz, H3'), 8.48 (2H, d, 3J = 9.5 Hz, H3 and H5), 8.32 (2H, d, 'J = 8.0 Hz, H4 ' or H6 '), 8.27 (2H, d, 3J = 8.0 Hz, H4 ' or H6'''), 8.23-8.19 (6H, m, H4', H6' and H^™1), 8.15-8.11 (4H, m, HPy™), 8.09-8.05 (7H, m, H4 and HPyren), 7.70 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5'''), 6.78 (2H, dd, 3J = 5.0 Hz, 3J = 8.0 Hz, H6''), 6.36 (2H, dd, 3J = 7.0 Hz, 3J = 10.5 Hz, H4' or H5' ), 5.52 (2H, dd, 3J = 7.0 Hz, 3J = 10.5 Hz, H4 ' or H5''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C57H33N5: 788.83 [M+H]+, found: 788.84. Not enough material for an elemental analysis.
4' i-
2,Ph'-Ph-bar-bell-compound. 2-Pyridylchalcone 2N,Ph'-ch (382 mg, 1.83 mmol), NH4OAc (3.20 g, 41.5 mmol), and phenyl bispyridinium iodine salt (Ph-BBC-salt) (491 mg, 0.858 mmol) were suspended in MeOH (15.0 mL) and refluxed for 24 h. A beige solid was filtered and washed with MeOH (20 mL). A yellow-greenish solid was recrystallized from MeOH (30 mL). Yield: 54.3% (251 mg, 0.465 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 8.79 (2H, m, 4J = 1.5 Hz, 4J = 2.0 Hz, 3J = 4.5 Hz, H6''), 8.76 (2H, d, 3J = 8.0 Hz, H3' ), 8.75 (2H, d, 4J = 1.5 Hz, H5'), 8.44 (4H, s, H2, H3, H5 and H6), 8.12 (2H, d, 4J = 1.5 Hz, H3'), 7.95-7.89 (6H, m, H5' and HPhe"y'), 7.617.58 (4H, m,HPhe"y'), 7.54 (2H, tt, 4J = 1.5 Hz, 3J = 7.5 Hz, HPhe"y'), 7.39 (2H, ddd, 4J = 1.0 Hz, 3J = 4.5 Hz, 3J = 7.5 Hz, H4''). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 156.7, 156.6, 156.4, 150.6, 149.5, 140.2, 138.9, 137.3, 129.5, 129.4, 127.8, 127.6, 124.3, 121.8, 118.8, 118.2. MALDI-TOF: calculated m/z for C38H26N4: 539.62 [M+H]+, found: 539.83. Elemental analysis: calculated: %C 84.73, %H 4.87, %N 10.40; found: %C 84.80, %H 4.91, %N 10.54.
4'" 5"
Ph,3'-Ph-bar-bell-compound. 3'-Pyridylchalcone (Ph,3N'-ch) (200 mg, 0.956 mmol) NH4OAc (1.70 g, 22.1 mmol) and Ph-
BBC-salt (300 mg, 0.524 mmol) were suspended in MeOH (9 mL) and refluxed for 24 h. A solid was filtered, washed with MeOH and dried under vacuum. Yield: 74.4% (210 mg, 0.389 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.03 (2H, d, 4J = 2.0 Hz, H2'''), 8.75 (2H, dd, 4J = 1.0 Hz, 3J = 5.0 Hz, H4'''), 8.42 (4H, s, H2, H3, H5 and H6), 8.27 (4H, d, 3J = 7.0 Hz, H2' and H6''), 8.11 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H6'''), 7.99 (2H, s, H3 or H5'), 7.93 (2H, s, H3 or H5'), 7.59 (4H, t, 3J = 7.0 Hz, H3 ' and H5''), 7.54-7.52 (2H, m, H4' and H5'). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 158.0, 157.3,
150.4, 148.4, 147.4, 140.1, 139.3, 135.0, 134.8, 129.8, 129.2, 127.8,
127.5, 124.3, 120.6, 117.5, 117.3, 99.8. MALDI-TOF: calculated m/z for C38H26N4: 540.63 [M+2H]+, found: 540.80. Elemental analysis: calcu6ated: %C 84.73, %H 4.87, %N 10.40; found: %C 84.84, %H 4.92, %N 10.58.
4" 5'
4" 5"
3,3'-Ph-bar-bell-compound. The synthesis was carried out according to Ph,3'-Ph-bar-bell-compound (Ph,3N'-Ph-BBC) with 3,3'-dipyridylchalcone (3,3'-ch) (190 mg, 0.904 mmol), NH4OAc (2.10 g, 27.2 mmol) and Ph-BBC-salt (242 mg, 0.423 mmol). Yield: 17.7% (40.5 mg, 0.0749 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.48 (2H, d, 4J = 1.5 Hz, H2''), 9.08 (2H, d, 4J = 2.0 Hz, H2), 8.80 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H4 ' or H6''), 8.76 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H4' or H6''), 8.57 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H4'''), 8.43 (4H, s, H2, H3, H5 and H6), 8.10 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H6'''), 8.06 (2H, d, 4J = 1.0 Hz, H3' or H5'), 7.96 (2H, d, 4J = 1.5 Hz, H3' or H5'), 7.54-7.50 (4H, m, H5 ' and H5'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C36H24N6: 540.59 [M+H]+, found: 540.86. Elemental analysis: calculated: %C 79.98, %H 4.47, %N 15.55; found: %C 80.09, %H 4.36, %N 15.81.
4" 5"
4- 5"
2,3'-Ph-bar-bell-compound. The synthesis was carried out
according to Ph,3N'-Ph-BBC with 2,3'-dipyridylchalcone (2,3'-ch)
(200 mg, 0.951 mmol), Ph-BBC-salt (270 mg, 0.472 mmol) and NH4OAc (1.70 g, 22.1 mmol). Yield: 35.2% (90.0 mg, 0.166 mmol).
1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.14 (2H, d, 4J = 2.0 Hz, H5'), 8.81-8.75 (8H, m, H3', H6', H2' and H4'), 8.45 (4H, s, H2, H3, H5
and H6), 8.18 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H6'''), 8.10 (2H, d, 4J = 2.0 Hz, H3'), 7.95 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5''), 7.52 (2H, dd,
3J = 4.5 Hz, 3J = 8.0 Hz, H5'''), 7.42 (2H, ddd, 4J = 1.0 Hz, 3J = 4.5 Hz,
3J = 8.0 Hz, H4''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C36H24N6: 541.59 [M+H]+,
found: 541.94. Elemental analysis: calculated: %C 79.98, %H 4.47,
%N 15.55; found: %C 80.14, %H 4.38, %N 15.57.
4" I
4,3'-Ph-bar-bell-compound. The synthesis was carried out according to Ph,3N'-Ph-BBC with 4,3'-dipyridylchalcone (4,3'-ch) (200 mg, 0.951 mmol), Ph-BBC-salt (270 mg, 0.472 mmol) and NH4OAc (1.70 g, 22.1 mmol). Yield: 78.7% (201 mg, 0.371 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.09 (2H, dd, 4J = 1.0 Hz, 4J = 2.0 Hz, H2'''), 8.85 (4H, dd, 4J = 2.0 Hz, 3J = 5.0 Hz, H3' and H5'), 8.81 (2H, dd, 4J = 2.0 Hz, 3J = 5.0 Hz, H4'''), 8.45 (4H, s, H2, H3, H5 and H6), 8.17 (4H, dd, 4J = 2.0 Hz, 3J = 5.0 Hz, H2' and H6'), 8.12-8.09 (2H, m, H6'), 8.10 (2H, d, 4J = 2.0 Hz, H3' or H5'), 8.01 (2H, d, 4J = 1.5 Hz, H3' or H5'), 7.54 (2H, ddd, 4J = 1.0 Hz, 3J = 5.0 Hz, 3J = 8.0 Hz, H5'''). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C36H24N6: 542.60 [M+H]+, found: 542.63. Elemental analysis: calculated: %C 79.98, %H 4.47, %N 15.55; found: %C 80.08, %H 4.37, %N 15.69.
О NTN О
Pyridazine bispyridinium iodine salt. 3,6-Diacetylpyridazine (0.35 g, 2.1 mmol) and iodine (1.2 g, 4.7 mmol) were refluxed in dry pyridine (10 mL) for 4 h. After stirring another 20 h at r.t. a black solid was filtered and washed with MeOH (30 mL), till the washing liquid was colorless. The solid was dried under vacuum. Yield: 34% (0.41 g, 0.71 mmol). 'H NMR (400 MHz, DMSO-d6): 5 = 9.09-9.07 (4H, m, H3), 8.80-8.75 (4H, m, H4), 8.52 (2H, s, H1), 8.18-8.12 (2H, m, H5), 6.73 (4H, s, H2). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. Elemental analysis for C18H16I2N4O2: calculated: %C 37.65, %H 2.81, %N 9.76; found: %C 38.02, %H 3.01, %N 9.95.
O6" 2" \ 2
' 5-( "V-f^
3" yj «r
4*' 5'1
Ph,Ph'-Pyridazine-bar-bell-compound. Chalcone ch (72.5 mg, 0.350 mmol), pyridazine bispyridinium iodine salt (Pyz-BBC-salt) (100 mg, 0.174 mmol) and NH4OAc (405 mg, 5.25 mmol) were refluxed in MeOH (8 mL) for 24 h. A solid was filtrated, washed with MeOH and dried under vacuum. Yield: 19.7 % (18.5 mg, 0.0343 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.06 (2H, d, 4J = 2.0 Hz, H3 ), 9.00 (2H, s, H2), 8.31-8.28 (4H, m, H2" and H6"), 8.15 (2H, 4J = 2.0 Hz, H5'), 7.95-7.92 (4H, m, H^'), 7.64-7.59 (8H, m, Hphenyi), 7.57-7.54 (4H, m, HPhe"y'). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C38H26N4:
539.62 [M+H]+, found: 539.70. Elemental analysis: calculated: %C 84.73, %H 4.87, %N 10.40; found: %C 84.50, %H 4.86, %N 10.62.
4" 5"'
2,2'-Pyridazine-bar-bell-compound. 2,2'-Dipyridylchalcone (2,2'-ch) (0.15 g, 0.71 mmol), Pyz-BBC-salt (0.20 g, 0.34 mmol) and NH4OAc (1.4 g, 18 mmol) were refluxed in MeOH (8.0 mL) for 3 d. A solid was filtrated, washed with MeOH and dried under vacuum for 6 h at 180 °C. Yield: 27% (51 mg, 0.092 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.03 (2H, d, 4J = 1.5 Hz, H3' or H5), 8.89-8.87 (2H, m, H3" , H6" or H3"), 8.82-8.80 (2H, m, H3", H6" or H3"), 8.79-8.76 (2H, m, H3", H6" or H3"), 8.61-8.60 (2H, d, 4J = 1.5 Hz, H3' or H5), 8.49 (2H, s, H2), 8.09-8.08 (2H, m, H6"), 7.94 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5" or H5 "), 7.92 (2H, dt, 4J = 2.0 Hz, 3J = 8.0 Hz, H5" or H5"), 7.43 (2H, ddd, 4J = 1.0 Hz, 3J = 5.0 Hz, 3J = 8.0 Hz, H4" or H4"), 7.41 (2H, ddd, 4J = 1.0 Hz, 3J = 5.0 Hz, 3J = 8.0 Hz, H4" or H4"). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C34H22N8: 543.57 [M+H]+, found: 543.49. Elemental analysis: calculated: %C 75.26, %H 4.09, %N 20.65; found: %C 75.09, %H 4.17, %N 20.73.
Pyrazine bispyridinium iodine salt. 1,4-Diacetylpyrazine (330 mg, 2.01 mmol) and iodine (1.02 g, 4.02 mmol) were suspended in dry pyridine (5.2 mL) and refluxed for 3 h in an Ar-atmosphere. After stirring 20 h at r.t. a solid was filtrated, washed with EtOH (30 mL) and air-dried for 1 h to yield a golden brown product. Yield: 91.8% (1.06 g, 1.85 mmol). 1H NMR (400 MHz, DMSO-d6): 5 = 9.49 (2H, s, H1), 9.03 (4H, m, H3), 8.78 (2H, m, H5), 8.33 (4H, m, H4), 6.54 (4H, s, H2). 13C NMR (400 MHz, DMSO-d6): 5 = 190.2, 147.8, 146.6, 146.2, 142.2, 127.7, 66.4. MS (CI): calculated m/z for C18H16I2N4O2: 165.15 [M-2C6H5N-2I+H]+, found: 164.87. Elemental analysis: calculated for C18H16I2N4O2: %C 37.65, %H 2.81, %N 9.76; found: %C 37.91, %H 2.99, %N 9.90.
Ph,Ph'-Pyrazine-bar-bell-compound. Chalcone ch (221 mg, 1.07 mmol), NH4OAc (1.92 g, 24.9 mmol) and pyrazine bispyridinium iodine salt (Pdz-BBC-salt) (300 mg, 0.523 mmol) were suspended in MeOH (8.5 mL) and reflluxed for 20 h. A dark
solid precipitated, was centrifuged and dried under vacuum. Yield: 3.0% (8.5 mg, 0.015 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 10.00 (2H, s, H2), 8.74 (2H, d, 4J = 1.0 Hz, H3 ), 8.31 (4H, d, 3J = 7.5 Hz, H2" and H6"), 8.10 (2H, d, 4J = 1.5 Hz, H5), 7.89 (4H, d, 3J = 7.0 Hz, HPhe"y'), 7.62-7.53 (12H, m, HPhe"y'). 13C NMR (500 MHz, 100 °C, TCE-d2): 5 = 157.7, 155.0, 151.1, 150.8, 142.6, 139.4, 138.7, 129.5, 129.4, 129.3, 129.0, 127.45, 127.39, 119.0, 118.4. MALDI-TOF: calculated m/z for C39H25N9: 539.62 [M+H]+, found: 539.82. Not enough material for an elemental analysis.
3,3'-Pyrazine-bar-bell-compound. 3,3'-Dipyridylchalcone (3,3'-ch) (225 mg, 1.07 mmol), NH4OAc (1.92 g, 24.9 mmol), and Pdz-BBC-salt (300 mg, 0.523 mmol) were suspended in MeOH (8.5 mL) and refluxed for 20 h. A dark solid precipitated, was centrifuged and dried under vacuum. Yield: 6.41% (18.2 mg, 0.0335 mmol). 1H NMR (500 MHz, 100 °C, TCE-d2): 5 = 9.98 (2H, s, H2), 9.49 (2H, d, 4J = 2.0 Hz, H3', H2" or H2"), 9.13 (2H, d, 4J = 2.0 Hz, H3', H2" or H2"), 8.81 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H4" or H4 "), 8.80 (2H, d, 4J = 2.0 Hz, H3', H2" or H2"), 8.79 (2H, dd, 4J = 1.5 Hz, 3J = 4.5 Hz, H4" or H4"), 8.58 (2H, dt, 3J = 8.0 Hz, 4J = 2.0 Hz, H6"), 8.17 (2H, dt, 3J = 8.0 Hz, 4J = 2.0 Hz, H6 "), 8.09 (2H, d, 4J = 2.0 Hz, H5 ), 7.55-7.52 (4H, m, H5" and H5"). 13C NMR (500 MHz, 100 °C, TCE-d2): Solubility too low. MALDI-TOF: calculated m/z for C34H22N8: 543.57 [M+H]+, found: 543.76. Elemental analysis: calculated: %C 75.26, %H 4.09, %N 20.65; found: %C 74.81, %H 4.22, %N 20.51.
Acknowledgement. We thank the German Science Foundation ("Deutsche Forschungsgemeinschaft") for financial support within the framework of the Collaborative Research Center 569 ("Sonderforschungsbereich") at the University of Ulm.
References
1. a) Fallahpour R.A. Curr. Org. Synth. 2006, 3, 19-39; b) Constable E.C. In: Prog. Inorg. Chem. Vol. 42 (Karlin K.D., Ed.), Wiley-Interscience, 1994, pp. 67-138; c) Constable E.C. In: Advances in Inorganic Chemistry and Radiochemistry Vol. 30 (Emeleus H.J., Sharpe A.G., Eds.), Academic Press: New York, 1986, pp. 69-121; d) Potts K.T. Bull. Soc. Chim. Belg. 1990, 99, 741-768.
2. a) Pabst G.R., Schmid K., Sauer J. Tetrahedron Lett. 1998, 39, 6691-6694; b) Pabst G.R., Sauer J. Tetrahedron Lett. 1998, 39, 6687-6690.
3. Potts K.T., Cipullo M.J., Ralli P., Theodoridis G. J. Org. Chem. 1982, 47, 3027-3038.
4. Kröhnke F. Synthesis 1976, 1-24.
5. a) Ziener U., Lehn J.-M., Mourran A., Möller M. Chem.-Eur. J. 2002, 8, 951-957; b) Ziener U. J. Phys. Chem. B 2008, 112, 14698-14717; c) Meier C., Ziener U., Landfester K., Weihrich P. J. Phys. Chem. B 2005, 109, 21015-21027; d) Caterbow D., Künzel D., Mavros M.G., Groß A., Landfester K., Ziener U. Beilstein J. Nanotechnol. 2011, 2, 405-415.
6. a) Caterbow D., Ziener U. Chem. Commun. 2011, 9366-9368; b) Caterbow D., Roos M., Hoster H.E., Behm R.J., Landfester K., Ziener U. Chem.-Eur. J. 2011, 17, 7831-7836.
7. a) Meier C., Roos M., Künzel D., Breitruck A., Hoster H., Landfester K., Gross A., Behm R.J., Ziener U. J. Phys. Chem. C 2010, 114, 1268-1277; b) Meier C., Landfester K., Ziener U. J. Phys. Chem. C 2009, 113, 1507-1514; c) Meier C., Landfester K., Ziener U. J. Phys. Chem. C 2008, 112, 15236-15240; d) Meier C., Landfester K., Künzel D., Markert T., Groß A., Ziener U. Angew. Chem., Int. Ed. 2008, 47, 3821-3825; e) Hoster H.E., Roos M., Breitruck A., Meier C., Tonigold K., Waldmann T., Ziener U., Landfester K., Behm R.J. Langmuir 2007, 23, 1157011579; f) Dai Y., Meier C., Ziener U., Landfester K., Täubert C., Kolb D.M. Langmuir 2007, 23, 11058-11062.
8. Jahng Y., Zhao L.-X., Moon Y.-S., Basnet A., Kim E.-K., Chang H.W., Ju H.K., Jeong T.C., Lee E.-S. Biorg. Med. Chem. Lett. 2004, 14, 2559-2562.
9. Zhang Z., Dong Y.-W., Wang G.-W. Chem. Lett. 2003, 32, 966967.
10. Durinda J., Szucs L., Krasnec L., Heger J., Springer V., Kolena J., Keleti J. ActaFac. Pharm. Bohem. 1966, 12, 89-129.
11. Basnet A., Thapa P., Karki R., Na Y., Jahng Y., Jeong B.-S., Jeong T.C., Lee C.-S., Lee E.-S. Bioorg. Med. Chem. 2007, 15, 4351-4359.
12. Mihailovic M.L.J., Tot M. J. Org. Chem. 1957, 22, 652-654.
13. Krasnec L., Durinda J., Szücs L. Chem. Zvesti 1961, 15, 558562.
14. Ullah A., Ansari F.L., Ihsan-ul-Haq, Nazir S., Mirza B. Chem. Biodivers. 2007, 4, 203-214.
15. Crommwell N.H., Cahoy R.P., Franklin W.E., Mercer G.D. J. Am. Chem. Soc. 1957, 79, 922-925.
16. Robinson T. P., Hubbard IV R.B., Ehlers T.J., Arbiser J.L., Goldsmith D.J., Bowen J.P. Bioorg. Med. Chem. 2005, 13, 4007-4013.
17. Xin Y., Zang Z.-H., Chen F.-L. Synth. Commun. 2009, 39, 4062-4068.
18. Kadjane P., Charbonnière L., Camerel F., Lainé P.P., Ziessel R. J. Fluoresc. 2008, 18, 119-129.
19. Cussac M., Boucherie A. Chim. Ther. 1967, 2, 101-105.
20. Stroba A., Schaeffer F., Hindie V., Lopez-Garcia L., Adrian I., Fröhner W., Hartmann R. W., Biondi R. M., Engel M. J. Med. Chem. 2009, 52, 4683-4693.
21. Mamolo M.G., Zampieri D., Falagiani V., Vio L., Banfi E. Farmaco 2001, 56, 593-600.
22. Meier C., Dissertation thesis, University of Ulm (Ulm), 2008.
Received 16.08.2011 Accepted 20.09.2011
