Synthesis and hydroxylation of 1-alkyl- and 7-alkyl- 1,3,7-triazapyrenium salts

Article abstract of DOI:10.1007/s10593-009-0295-6

The regioselectivity of quaternization of 1,3,5-triazapyrenes by alkyl halides has been studied. Oxidative hydroxylation of 1-alkyl- and 7-alkyl-1,3,7-triazapyrenium salts gives 1-alkyl-1,2-dihydro-1,3,7-triazapyren- 2-ones or 7-alkyl-6,7-dihydro-1,3,7-tr

Full text of DOI:10.1007/s10593-009-0295-6

Chemistry of Heterocyclic Compounds, Vol. 45, No. 5, 2009
SYNTHESIS AND HYDROXYLATION
OF 1-ALKYL- AND 7-ALKYL-
1,3,7-TRIAZAPYRENIUM SALTS
S. V. Pisarenko1, O. P. Demidov1, A. V. Aksenov1, and I. V. Borovlev1*
The regioselectivity of quaternization of 1,3,5-triazapyrenes by alkyl halides has been studied. Oxidative
hydroxylation of 1-alkyl- and 7-alkyl-1,3,7-triazapyrenium salts gives 1-alkyl-1,2-dihydro-1,3,7-
triazapyren-2-ones or 7-alkyl-6,7-dihydro-1,3,7-triazapyren-6-ones respectively. In the absence of an
oxidant the hydroxylation of the 1-alkyl-1,3,7-triazapyrenium salts leads to a hydrolytic cleavage of the
heterocycle.
Keywords: 1,3,7-triazapyrenes, 1,3,7-triazapyrenium salts, hydroxylation, quaternization.
Virtually nothing was known up to this time regarding the preparation and properties of 1,3,7-triaza-
pyrenes. We have recently developed a series of synthetic methods for these compounds from perimidines,
including the parent of the series [1-4]. The aim of our work was to study the regioselectivity of the
quaternization process for 1,3,7-triazapyrenes and to investigate hydroxylation reactions for the 1,3,7-triaza-
pyrenium salts obtained.
R
R
2
3
N
N
1
8
N
N
4
5
10
9
R1X
6
+
–
R
N
7
X
R
N
R1
1a,b
2a–d
1 а R = H, b R=Ph; 2 a R = H, R1 = Me, X = I; b R = H, R1 = Et, X = I;
c R = H, R1 = PhCOCH2, X = Br; d R = Ph, R1 = Me, X = I
_______
* To whom correspondence should be addressed, e-mail: k-biochem-gcs@stavsu.ru.
1Stavropol State University, Stavropol 355009, Russia.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 735-742, May, 2009. Original
article submitted January 17, 2008.
580
0009-3122/09/4505-0580©2009 Springer Science+Business Media, Inc.

A priori it can be proposed that the nucleophilicity (and basicity) of the N-7 atom of the 1,3,7-triaza-
pyrene (1a) will be greater than the N-1 and N-3 atoms due to their acceptor properties. Indeed, quaternization
of the unsubstituted compound 1a and of 2,6-diphenyl-1,3,7-triazapyrene (1b) using an excess of alkyl halides
in acetonitrile occurs readily to give the 7-alkyl-1,3,7-triazapyrenium salts 2a-d.
However, in the case of the 6,8-dimethyl- (1c) and 6,8-diphenyl-1,3,7-triazapyrene (1d) the
regioselectivity of the reaction changes and only the 1-alkyl-1,3,7-triazapyrenium salts 3a-c are formed.
R1
N
N
N
N
+
–
I
R1I
MeCN
R
N
R
R
R
N
3a–c
1c,d
1c R = Me, d R = Ph; 3 a R = R1 = Me; b R = Ph, R1 = Me; c R = Ph, R1 = Et
Evidently, the change in reaction route is due to steric hindrance from the substituents in positions 6 and 8.
We have also studied another possible method for the synthesis of the salts 3 i.e. by reaction of 1-R-peri-
midines with sym-triazines in PPA*. As in the case of the unsubstituted perimidine [1], the reaction of the
1-methylperimidine (4) with 1,3,5-triazine results in formation of a salt which could be separated as the chloride
3d. However, the yield of the 1-methyl-1,3,7-triazapyrenium chloride (3d) was only 45% due to problems in
separation.
Me
Me
N
N
N
N
N
N
–
+
1.
Cl
,
PPA
N
2. H2O, CaCO3
3. HCl
4
N
3d
Quaternization of 6-phenyl-1,3,7-triazapyrene (1e) with methyl iodide resulted in the formation of a
mixture of the three possible salts 2e, 3e, 3f in the ratio 4: 3:3 (from 1H NMR spectroscopic data).
2,6,8-Trimethyl- and 2,6,8-tripenyl-1,3,7-triazapyrenes did not take part in the quaternization reaction,
even upon prolonged refluxing in acetonitrile with a large excess of methyl iodide or dimethyl sulfate.
2
Thus substituents in the 6 and 8 positions block SN -quaternization at atom N-7 and substituents at
position 2 at atoms N-1 and N-3 . It should be noted in particular that, in contrast to 4,9- [6] and 2,7-diaza-
pyrenes [7, 8], the products of a double quaternization of the 1,3,7-triazapyrenes 1a-e were not observed.
The 1H NMR spectra of the salts 2 and 3 show a series of features. In particular, when compared with the
starting triazapyrenes, the signals of all of the protons are shifted to low field, in greatest degree relating to the
protons in positions 2 and 6(8). The signals for the phenyl groups in positions 2, 6, and 8 in the triazapyrenes
appear as two multiplets since the ortho protons fall in the deshielding area of the pyridine ring atoms and are
shifted to low field, although by a markedly different degree. Thus for 2,6,8-triphenyl-1,3,7-triazapyrene the signal
at 7.95 corresponds to the o-H of the 6(8)-Ph and that at 8.84 ppm to the o-H of the 2-Ph [1]. In contrast
_______
* PPA with an 86% content of P2O5 was used as obtained in the method [5].
581

to the salts 3b,c,e,f, where rotation of the 6(8)-phenyl substituent is not hindered, the main conformations of the
benzene rings in the 6-phenyl-substituted salts 2d and 2e are placed perpendicularly to the triazapyrene ring
plane and so their protons appear as a sharp multiplet without separation of the ortho protons to low field. The
signals for the methyl group and the H-5 proton fall in the shielding region of the benzene ring and are shifted
by 0.4 and 0.53 ppm to high field respectively when compared with 7-methyl-1,3,7-triazapyrenium iodide (2a).
These features permit an unambiguous assignment of the signals for the protons in the mixture of salts 2e, 3e
and 3f.
Me
Me
N
N
N
N
N
N
+
+
N
N
–
I
–
I
MeI
+
+
MeCN
+
N
–
I
Ph
N
Ph
Ph
N
Ph
N
1e
Me
3f
3e
2e
An increased π-deficiency of salts 2 and 3 suggested a ready reaction with nucleophilic reagents. In fact,
treatment of salts 2b,d with aqueous alkali in the presence of K3[Fe(CN)6] gave the products of oxidative
hydroxylation, i.e. 7-ethyl-6,7-dihydro-1,3,7-triazapyren-6-one (6a) and 7-methyl-2,8-diphenyl-6,7-dihydro-
1,3,7-triazapyren-6-one (6b) in 59 and 53% yields respectively.
R
R
N
N
N
N
K3[Fe(CN)6]
KOH, H2O
2b,d
H
OH
R
N
R1
O
R
N
R1
6a,b
5
6 a R = H, R1 = Et; b R = Ph, R1 = Me
The reaction takes place via a stage of formation of the pseudobase 5 and its subsequent oxidation.
Salts 3b,c react similarly under these conditions to give the 1-methyl- (7a) and 1-ethyl-6,8-diphenyl-
1,2-dihydro-1,3,7-triazapyren-2-ones (7b) in 60 and 58% yields respectively.
O
R
N
N
KOH, H2O
3b,c
K3[Fe(CN)6]
Ph
Ph
N
7a,b
7 a R = Me; b R = Et
582

In the absence of oxidant, however, the reaction of salts 3b,c with aqueous alkali occurs differently. The
pseudobase 8 formed in the first step undergoes hydrolytic cleavage of the heterocycle and the corresponding
N-methyl- (9) and N-ethyl-9-amino-4,6-diphenyl-5-azaphenalenone-1-imine (10) can be separated.
–
O
H
OH
N
H
R
R
N
N
N
–
KOH
H2O
OH
3b,c
–H2O
Ph
Ph
N
Ph
Ph
N
8
OHC
N
OHC
H
R
R
R
–
N
NH
N
HN
9
N
–
1
4
H2O
H2O, OH
8
7
2
–
–
–OH
3
–HCOO
6
N
N
5
Ph
Ph
Ph
Ph
N
Ph
Ph
9, 10
9 R = Me; 10 R = Et
H
H
R
R
H
9
H
N
N
N
N
1
9
8
7
1
2
8
2
3
7
3
6
4
6
4
N
5
Ph
N
5
A
Ph
Ph
Ph
B
R
H
H
Me
N
N
N
N
H
9
1
9
8
7
1
2
8
2
3
3
7
4
6
6
4
N
5
Ph
N
H
Ph
Ph
Ph
5
C
D
9 R = Me; 10 R = Et
583

In principle, compounds 9 and 10 can exist in CDCl3 solution as an equilibrium mixture of four non-
degenerate tautomers A-D. In our opinion the main tautomers are A and B since transfer between them involves
migration of a hydrogen bridge and rebuilding of the π-electron system while formation of C has to include
cleavage of a hydrogen bond and synchronous inversion of a nitrogen atom. The possibility of the further
tautomer D seems unlikely due to disturbance to the aromaticity of the system.
1
The H NMR spectra of the amino imines 9 and 10 in CDCl3 show two NH proton signals, one
intramolecularly hydrogen bonded at about 12.8 and one unbonded at about 7.9 ppm and these are lost on
addition of D2O. Characteristic features of the spectra of 9 and 10 are their non-symmetry, not only with respect
to their chemical shifts but also to their spin-spin couplings for the aromatic protons at positions 2,3 and 7,8
(9.50 and 9.80 Hz). In our view, this indicates that they exist mainly in a single tautomeric form. Since an
unambiguous choice of this form is difficult the recorded spectra of compounds 9 and 10 are reported arbitrarily
as the B tautomers (see Experimental).
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker-200 instrument (200 MHz) using DMSO-d6 (compounds
2a-c, 3a-f, and 6a,b) or CDCl3 (compounds 7a,b, 9, and 10) with TMS as internal standard. Mass spectra were
taken on an MX-1321A instrument with direct introduction of the sample into the ionizing chamber at 50-100ºC
and with an ionization intensity of 70 eV.
Quaternization of 1,3,7-Triazapyrenes (General Method). A solution of the corresponding
1,3,7-triazapyrene (3 mmol) and the alkyl halide (9 mmol) in acetonitrile (20 ml) was refluxed for 4 h, the
solution was evaporated to 3 ml, and benzene (10 ml) was added. The precipitate was filtered off, washed with
benzene and petroleum ether, and dried. Further purification was not carried out.
7-Methyl-1,3,7-triazapyrenium Iodide (2a). Yield 1.1 g (96%). Orange crystals, mp 285-287ºC. 1H NMR
spectrum, δ, ppm (J, Hz): 4.87 (3H, s, CH3); 8.65 (2H, d, J = 9.5, H-4,10); 9.06 (2H, d, J = 9.5, H-5,9); 10.15 (1H, s,
H-2); 10.27 (2H, s, H-6,8). Found, %: C 48.12; H 3.06; N 12.23. C14H10IN3. Calculated, %: C 48.44; H 2.90.
N 12.10.
7-Ethyl-1,3,7-triazapyrenium Iodide (2b). Yield 0.92 g (85%). Cherry-red crystals, mp 260-262ºC.
1H NMR spectrum, δ, ppm (J, Hz): 1.88 (3H, t, J = 7.3, CH3); 5.22 (2H, q, J = 7.3, CH2); 8.57 (2H, d, J = 9.3,
H-4,10); 9.08 (2H, d, J = 9.3, H-5,9); 10.04 (1H, s, H-2); 10.52 (2H, s, H-6,8). Found, %: C 50.11; H 3.40;
N 11.32. C15H12IN3. Calculated, %: C 49.88; H 3.35; N 11.63.
7-Phenacyl-1,3,7-triazapyrenium Bromide (2c). Yield 1.47 g (82%). Dark-brown crystals, mp
1
282-284ºC. H NMR spectrum, δ, ppm (J, Hz): 7.13 (2H, s, CH2); 7.72 (5H, m, Ph); 8.60 (2H, d, J = 9.3,
H-4,10); 9.13 (2H, d, J = 9.3, H-5,9); 10.06 (1H, s, H-2); 10.43 (2H, s, H-6,8). Found, %: C 62.07; H 3.55;
N 10.23. C21H14BrN3O. Calculated, %: C 62.39; H 3.49; N 10.39.
7-Methyl-2,6-diphenyl-1,3,7-triazapyrenium Iodide (2d). Yield 1.16 g (78%). Pale-yellow crystals,
mp 256-258ºC. 1H NMR spectrum, δ, ppm (J, Hz): 4.44 (3H, s, CH3), 7.68 (3H, d, 2-Ph, H-m and -p); 7.84 (5H,
d, 6-Ph); 8.18 (1H, d, J = 9.5, H-4); 8.54 (1H, d, J = 9.5, H-5); 8.69 (1H, d, J = 9.5, H-10); 8.81 (2H, m, 2-Ph,
H-o); 9.05 (1H, d, J = 9.5, H-9); 10.35 (1H, s, 8-H). Found, %: C 62.29; H 3.72; N 8.60. C26H18IN3. Calculated,
%: C 62.54; H 3.63; N 8.41.
7-Methyl-6-phenyl-1,3,7-triazapyrenium Iodide (2e) was prepared as a mixture with isomers 3e and
1
3f: overall yield 81%. H NMR spectrum, δ, ppm (J, Hz): 4.48 (3H, s, CH3); 7.84 (5H, m, Ph); 8.21 (1H, d,
J = 9.5, H-4); 8.53 (1H, d, J = 9.5, H-5); 8.70 (1H, d, J = 9.5, H-10); 9.11 (1H, d, J = 9.5, H-9); 10.15 (1H, s,
H-2); 10.50 (1H, s, H-8).
1,6,8-Trimethyl-1,3,7-triazapyrenium Iodide (3a). Yield 1.4 g (80%). Red crystals, mp above 350ºC.
1H NMR spectrum, δ, ppm (J, Hz): 3.38 (3H, s, 6-CH3); 3.40 (3H, s, 8-CH3); 4.70 (3H, s, NCH3); 8.43 (1H, d,
584

J = 9.3, H-9); 8.68 (1H, d, J = 9.5, H-10); 9.46 (1H, d, J = 9.3, H-5); 9.58 (1H, d, J = 9.5, H-9); 10.10 (1H, s,
H-2). Found, %: C 51.34; H 3.66; N 11.44. C16H14IN3. Calculated, %: C 51.22; H 3.76; N 11.20.
1-Methyl-6,8-diphenyl-1,3,7-triazapyrenium Iodide (3b). Yield 1.06 g (71%). Red crystals, mp
286-288ºC. 1H NMR spectrum, δ, ppm (J, Hz): 4.69 (3H, s, NCH3); 7.75 (6H, m, 6- and 8-Ph, H-m and -p); 8.05
(4H, m, 6- and 8-Ph, H-o); 8.61 (1H, d, J = 9.5, H-4); 8.76 (1H, d, J = 9.5, H-10); 9.26 (1H, d, J = 9.5, H-5);
9.34 (1H, d, J = 9.5, H-9); 10.13 (1H, s, H-2). Found, %: C 62.88; H 3.49; N 8.31. C26H18IN3. Calculated, %:
C 62.54; H 3.63; N 8.41.
1-Ethyl-6,8-diphenyl-1,3,7-triazapyrenium Iodide (3c). Yield 1.07 g (69%). Red crystals, mp
293-295ºC. 1H NMR spectrum, δ, ppm (J, Hz): 1.77 (3H, t, J = 7.2, CH3); 5.28 (2H, q, J = 7.2, CH2); 7.76 (6H,
m, 6- and 8-Ph, H-m and -p); 8.04 (4H, d, 6- and 8-Ph, H-o); 8.56 (1H, d, J = 9.3, H-4); 8.94 (1H, d, J = 9.3,
H-10); 9.24 (1H, d, J = 9.3; H-5); 9.33 (1H, d, J = 9.3, H-9); 10.27 (1H, s, H-2). Found, %: C 62.99; H 4.07;
N 7.98. C27H20IN3. Calculated, %: C 63.17; H 3.93; N 8.18.
1-Methyl-6-phenyl-1,3,7-triazapyrenium Iodide (3e) was obtained as a mixture with isomers 2e and
3f. 1H NMR spectrum, δ, ppm (J, Hz): 4.73 (3H, s, CH3); 7.76 (3H, m, Ph, H-m and -p); 8.01 (2H, m, Ph, H-o);
8.77 (1H, d, J = 9.8, H-4); 8.87 (1H, d, J = 9.1, H-10); 9.31 (1H, d, J = 9.8, H-5); 9.59 (1H, d, J = 9.1, H-9);
10.19 (1H, s, H-2); 10.32 (1H, s, H-8).
1-Methyl-8-phenyl-1,3,7-triazapyrenium Iodide (3f) was obtained as a mixture with isomers 2e and
3e. 1H NMR spectrum, δ, ppm (J, Hz): 4.70 (3H, s, CH3); 7.76 (3H, m, Ph, H-m and -p); 8.01 (2H, m, Ph, H-o);
8.61 (1H, d, J = 9.3, H-4); 8.66 (1H, d, J = 9.1, H-10); 9.24 (1H, d, J = 9.3, H-5); 9.46 (1H, d, J = 9.1,m H-9);
10.19 (1H, s, H-2); 10.32 (1H, s, H-6).
1-Methyl-1,3,7-triazapyrenium Chloride (3d). A mixture of 1-methylperimidine (1 mmol),
1,3,5-triazine (1.5 mmol), and PPA (86%, 3 g) was stirred for 4 h at 100-105ºC, cooled to 50ºC, poured into
water (20 ml), neutralized with potassium carbonate, and filtered. The mother liquor was evaporated to dryness
in vacuo and the residue was dissolved in methanol. The insoluble admixture was filtered off and the solution
was evaporated to dryness in vacuo. The residue was treated with a solution of hydrochloric acid and the
solution was evaporated to dryness in vacuo, and washed with ethyl acetate. Yield 0.11 g (45%). Brown crystals
1
with mp 344-346ºC (decomp. with flash). H NMR spectrum, δ, ppm (J, Hz): 4.76 (3H, s, NCH3); 8.59 (1H, d,
J = 9.1, H-4); 8.86 (1H, d, J = 9.3, H-10); 9.41 (1H, d, J = 9.1, H-5); 9.55 (1H, d, J = 9.3, H-9); 10.20 (2H, s,
H-6,8); 10.21 (1H, s, H-2). Found, %: C 65.66; H 3.78; N 16.50. C14H10CIN3. Calculated, %: C 65.76; H 3.94;
N 16.43.
Oxidative Hydroxylation of the 7-Alkyl- and 1-Alkyl-1,3,7-triazapyrenium Salts (General Method).
An aqueous solution containing KOH (0.216 g, 4 mmol) and K3[Fe(CN)5] (0.67 g, 2 mmol) was added dropwise
with stirring and heating to 80ºC over 10 min to a solution of the corresponding 1,3,7-triaza-pyrenium salt
(1 mmol) in water (20 ml). The mixture was stirred at the same temperature for 1 h, water (30 ml) was added,
and the precipitate formed was filtered off after 30 min.
7-Ethyl-6,7-dihydro-1,3,7-triazapyren-6-one (6a). Yield 0.146 g (59%). Dark-orange crystals, mp
338-340ºC (ethyl acetate). 1H NMR spectrum, δ, ppm (J, Hz): 1.58 (3H, t, J = 7.0, CH3); 4.42 (2H, q, J = 7.0, CH2);
7.61 (1H, d, J = 9.2, H-9); 7.97 (1H, d, J = 9.2, H-10); 8.14 (1H, d, J = 8.9, H-4); 8.31 (1H, s, H-8); 8.92 (1H, d,
J = 8.9, H-5); 9.49 (1H, s, H-2). Found, %: C 72.09; H 4.67; N 16.52. C15H11N3O. Calculated, %: C 72.28; H 4.45;
N 16.86.
7-Methyl-2,8-diphenyl-6,7-dihydro-1,3,7-triazapyren-6-one (6b). Yield 0.205 g (53%). Yellow-green
1
crystals, mp 275-277ºC (ethyl acetate). H NMR spectrum, δ, ppm (J, Hz): 3.63 (3H, s, CH3); 7.42 (2H, br. s,
H-9,10); 7.47 (3H, m, 8-Ph, H-m and -p); 7.54 (3H, m, 2-Ph, H-m and -p); 7.67 (2H, m, 8-Ph, H-o); 8.14 (1H, d,
J = 9.2, H-4); 8.72 (2H, m, 2-Ph, H-o); 8.90 (1H, d, J = 9.2, H-5). Found, %: C 80.48; H 4.56; N 10.49.
C26H17N3O. Calculated, %: C 80.60; H 4.42; N 10.85.
1-Methyl-6,8-diphenyl-1,2-dihydro-1,3,7-triazapyren-2-one (7a). Yield 0.233 g (60%). Yellow-green
1
crystals, mp above 350ºC (DMSO). H NMR spectrum, δ, ppm (J, Hz): 4.04 (3H, s, CH3); 7.62 (6H, m, 6- and
585

8-Ph, H-m and -p); 7.66 (1H, d, J = 9.6, H-9); 7.76 (1H, d, J = 9.3, H-5); 7.88 (4H, m, 6- and 8-Ph, H-o); 8.43
(1H, d, J = 9.6, H-10); 8.74 (1H, d, J = 9.3, H-4). Found, %: C 80.76; H 4.33; N 10.90. C26H17N3O. Calculated,
%: C 80.60; H 4.42; N 10.85.
1-Ethyl-6,8-diphenyl-1,2-dihydro-1,3,7-triazapyren-2-one (7b). Yield 0.233 g (58%). Yellow crystals,
1
mp 316-318ºC (DMSO). H NMR spectrum, δ, ppm (J, Hz): 1.55 (3H, t, J = 7.0, CH3); 4.62 (2H, q, J = 7.0,
CH2); 7.60 (6H, m, 6- and 8-Ph, H-m and -p); 7.69 (1H, d, J = 9.5, H-9); 7.76 (1H, d, J = 9.2, H-5); 7.87 (4H, m,
6- and 8-Ph, H-o); 8.43 (1H, d, J = 9.5, H-10); 8.73 (1H, d, J = 9.2, H-4). Found, %: C 80.98; H 4.96; N 10.22.
C27H19N3O. Calculated, %: C 80.78; H 4.77; N 10.47.
Hydroxylation of Salts 3b,c without Oxidant (General Method). A mixture of potassium hydroxide
(4 mmol) and the corresponding 1,3,7-triazapyrenium salt (1 mmol) was dissolved in ethanol (96%, 30 ml) and
heated at 80ºC for 40 min. The product was diluted threefold with water and the precipitate formed was filtered
off, washed with water, and dried.
N-Methyl-9-amino-4,6-diphenyl-5-azaphenalenone-1-imine (9, tautomer B). Yield 0.342 g (95%).
1
Yellow crystals, mp 173-175ºC (ethyl acetate and petroleum ether). H NMR spectrum, δ, ppm (J, Hz): 3.34
(3H, s, CH3); 6.85 (1H, d, J = 9.5, H-8); 7.20 (1H, d, J = 9.8, H-3); 7.49 (6H, m, 4- and 6-Ph, H-m and -p); 7.67
(1H, d, J = 9.5, H-7); 7.73 (4H, m, 4- and 6-Ph, H-o); 7.90 (1H, br. s, NH); 8.07 (1H, d, J = 9.8, H-2); 12.80
(1H, br. s, NH···N). The signals at 7.90 and 12.80 ppm disappeared upon addition of D2O. Mass spectrum, m/z
(Irel, %): 361 [M]+ (100), 362 [M++1] (28), 343 (93), 329 (35), 207 (22), 44 (45). Found, %: C 82.82; H 5.26;
N 11.43. C25H19N3. Calculated, %: C 83.08; H 5.30; N 11.63.
N-Ethyl-9-amino-4,6-diphenyl-5-azaphenalenone-1-imine (10, tautomer B). Yield 0.348 g
1
(93%). Yellow crystals, mp 149-151ºC (ethyl acetate and petroleum ether). H NMR spectrum, δ, ppm (J, Hz):
1.46 (3H, t, J = 7.2, CH3); 3.63 (2H, q, J = 7.2, CH2); 6.72 (1H, d, J = 9.6, H-8); 7.18 (1H, d, J = 9.6, H-3); 7.50
(6H, m, 4- and 6-Ph, H-m and -p); 7.62 (1H, d, J = 9.3, H-7); 7.73 (4H, m, 4- and 6-Ph, H-o); 7.92 (1H, br. s,
NH); 8.02 (1H, d, J = 9.3, H-2); 12.75 (1H, br. s, NH···N). The signals at 7.92 and 12.75 ppm disappeared upon
addition of D2O. Found, %: C 83.02; H 5.76; N 11.31. C26H21N3. Calculated, %: C 83.17; H 5.64; N 11.19.
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