Investigation in the field of quinazolines. 8*. New reaction of N-alkylation of 4,4-diphenyl-3,4-dihydroquinazolines

Article abstract of DOI:10.1007/s10593-020-02848-5

[Figure not available: see fulltext.] The reaction of substituted 4,4-diphenyl-3,4(1,4)-dihydroquinazolines with various alkylating agents in DMSO–KOH leads (depending on the structure of the alkylating agent) to the formation of the corresponding N¹

Full text of DOI:10.1007/s10593-020-02848-5

DOI 10.1007/s10593-020-02848-5
мChemistry of Heterocyclic Compounds 2020, 56(12), 1548–1553
Investigation in the field of quinazolines. 8*. New reaction
of N-alkylation of 4,4-diphenyl-3,4-dihydroquinazolines
Elena V. Gromachevskava1, Elena A. Kaigorogova2, Alexander V. Bespalov3,
Oleg P. Demidov4, Gennady D. Krapivin1*
1 Kuban State Technological University,
2 Moskovskaya St., Krasnodar 350072, Russia; e-mail: krapivingd@mail.ru
2 Kuban State Agrarian University,
13 Kalinina St., Krasnodar 350044, Russia; e-mail: e_kaigorodova@mail.ru
3 Kuban State University,
149 Stavropol’skaya St., Krasnodar 350040, Russia; e-mail:bespalov_alex@mail.ru
4 North Caucasus Federal University,
1a Pushkina St., Stavropol 355009, Russia; e-mail:odemidov@gmail.com
Submitted September 8, 2020
Accepted October 14, 2020
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2020, 56(12), 1548–1553
The reaction of substituted 4,4-diphenyl-3,4(1,4)-dihydroquinazolines with various alkylating agents in DMSO–KOH leads (depending
on the structure of the alkylating agent) to the formation of the corresponding N1-monoalkyl-substituted 1,4-dihydroquinazolines or, in
the reaction with ethyl bromoacetate, to N-{[5-bromo-2-(methylamino)phenyl]diphenylmethyl}benzamide with opening of the
heterocyclic ring. The molecular structures of 1-ethyl-2,4,4-triphenyl-1,4-dihydroquinazoline and 1-ethyl-2-(7-methoxy-1,3-benzodioxol-
5-yl)-4,4-diphenyl-1,4-dihydroquinazoline were investigated and proven by X-ray structural analysis.
Keywords: N-{[5-bromo-2-(methylamino)phenyl]diphenylmethyl}benzamide, dimethyl sulfoxide, 4,4-diphenyl-3,4-dihydroquinazolines,
N1-substituted 4,4-diphenyl-1,4-dihydroquinazolines, alkylation, molecular structure.
This work is a continuation of our research on 3,4-di-
hydroquinazoline derivatives and the study of their
properties. We have previously developed a method for the
preparation of 2,4-substituted 3,4-dihydroquinazolines by
the reaction of (2-aminophenyl)diphenylmethanol with
nitriles via the corresponding perchlorates.2,3 The existence
of 3,4-dihydroquinazolines in equilibrium with the
tautomeric 1,4-dihydro form in solution was revealed.4 The
possibility of prototropic rearrangement into tetrahydro-
quinazolines was found for a number of structures
containing an active methylene unit directly bonded with
the heterocyclic ring.2,4,5
The expediency of continued research in the field of
quinazolines is determined by the discovery of derivatives
with pharmacological activity among them.6–16 We have
also shown that the search for antidotes to the action of the
herbicide 2,4-D17,18 used in agriculture among quinazoline
derivatives shows promise. Therefore, the goal of this work
was, on the one hand, to study the direction of the
heterocycle alkylation process and, on the other hand, to
introduce functional groups with a potential for high
biological activity as a result of alkylation at a certain
position of the quinazoline ring.
To expand the number of investigated structures,
6-bromo-2,4,4-triphenyl-3,4-dihydroquinazoline (3е) was
synthesized via the corresponding perchlorate 2е from
* For Communication 7, see 1.
0009-3122/20/56(12)-1548©2020 Springer Science+Business Media, LLC
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Chemistry of Heterocyclic Compounds 2020, 56(12), 1548–1553
Scheme 1
(2-amino-5-bromophenyl)diphenylmethanol (1b) according
to a previously developed method2,3 (Scheme 1). An
attempt to obtain 2-chloromethyl-4,4-diphenyl-3,4-dihydro-
quinazoline by the reaction of (2-aminophenyl)diphenyl-
methanol (1а) with chloroacetonitrile under the same
conditions2,3 led to the previously described19 phenyl-
acridine (4) in 75% yield.
Scheme 2
It was shown in our previous reports1–5 that alkylation of
3,4-dihydroquinazolines with highly active Me2SO4 always
proceeds as dimethylation at both nitrogen atoms of the
heterocycle with the formation of the corresponding
quinazolinium salts which decompose upon treatment with
H2O with opening of the heterocyclic ring to give the
corresponding aminoamides. The use of the less active MeI
(in Me2CO in the presence of solid KOH) made it possible
to obtain the products of monomethylation at the N-1
nitrogen atom. However, attempts to use other alkyl halides
as alkylating agents were unsuccessful. Replacing the
Me2CO solvent with the more ionizing and nucleophile-
activating DMSO makes it possible to obtain mono-
alkylation products 5a–d, 6, 7 using a variety of alkylating
agents (Scheme 2).
The reaction of 6-bromo-2-phenyl-3,4-dihydroquinazo-
line (3е) with ethyl bromoacetate is an exception. Instead
of the expected ethyl (6-bromo-2,4,4-triphenylquinazolin-
1(4H)-yl)acetate, N-{[5-bromo-2-(methylamino)phenyl]di-
phenylmethyl}benzamide (8) was obtained according to IR
spectroscopy, NMR spectroscopy, and mass spectrometry.
A possible route for the formation of compound 8 is
shown in Scheme 3 as a working hypothesis and involves
the hydrolysis of the ester group, decarboxylation, and
opening of the heterocycle during the isolation of the
product in an alkaline aqueous medium. The question of
the sequence of the steps of hydrolysis of the ester group
and opening of the heterocycle remains open so far.
1
In the H and 13C NMR spectra of compound 8, no signals
of the ethoxycarbonyl group are present, but there are
signals of the NCH3 group and two singlet signals of
protons not bonded to carbon atoms (according to the
1Н–13C HSQC spectrum). In the high-resolution mass
spectrum, a peak of the radical cation [M–CH3OH]+ can be
observed formed as a result of one of the two classical
processes of molecular ion fragmentation, a rearrangement
process with extrusion of a neutral small molecule, in this
case MeOH.
The IR spectra of compounds 5a–d, 6, 7 contain
absorption bands at 1590–1630 cm–1, which are characte-
ristic of stretching vibrations of the azomethine group,
which indicates that the heterocyclic ring remains intact. In
the 1H NMR spectra, there are signals of the protons of the
NCH2 groups in the range of 3.60–3.75 ppm in the form of
quartets for dihydroquinazolines 5a–d and singlets at 4.75
and 4.85 ppm for dihydroquinazolines 6, 7, respectively.
Scheme 3
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Chemistry of Heterocyclic Compounds 2020, 56(12), 1548–1553
Table 1. Results of heteronuclear correlation experiments
(1Н–13C HSQC and 1Н–13C HMBC spectra) for compound 5d
Signals of 13C nuclei that have cross peaks,
Signals of
δ, ppm
Proton
1Н nuclei,
δ, ppm
1Н–13C HSQC
1Н–13C HMBC
spectrum
spectrum
CH2CH3
NCH2
OCH3
2'-CH2
H-8
0.58
3.69
3.92
5.99
6.66
6.73
6.73
13.2
41.8
41.8
155.6; 138.0
143.4
56.7
101.8
128.8
109.4
103.8
136.5; 148.7
138.0; 127.3; 67.6
155.6; 148.7; 143.4
136.5; 130.5
Figure 2. Molecular structures of compounds 5c,d with atoms
represented as thermal vibration ellipsoids of 50% probability.
H-6'
H-4'
C(8a)–N(1)–C(2) deviate from the plane of the ''bottom'' of
the boat by approximately the same angles 20.3 and 19.6°,
respectively. The geometry of ring B of molecule 5d is
almost identical to that described above. The nitrogen atom
N(1) of both molecules has a planar environment: the sum
of the bond angles for this nitrogen atom is 360°. The
lengths of the N(1)–C(8a) and N(1)–C(2) bonds differ
markedly: the N(1)–C(2) bond is by 0.02 Å shorter than the
N(1)–C(8a) bond, that is, the conjugation of the lone pair of
nitrogen atoms N(1) is more directed toward the electron-
withdrawing azomethine unit.
The mutual arrangement of the benzene ring A and
phenyl substituents C and D at the C(4) atom resembles
that of the triphenylmethane molecule.20–24 In this case, the
conformation is most easily characterized by the rotation of
rings A, C, and D relative to the planes N(3)–C(4)–C(5),
N(3)–C(4)–C(1'C), and N(3)–C(4)–C(1'D), respectively.
The angles of rotation of ring A relative to the plane
N(3)–C(4)–C(5) are 41.4° in molecule 5c and 41.1° in
molecule 5d. Ring C is rotated relative to plane
N(3)–C(4)–C(1'C) by 48.9 and 49.1°, ring D is rotated
relative to plane N(3)–C(4)–C(1'D) by 40.1 and 37.4° in
molecules 5c and 5d, respectively. In the latter case, the
rotation of ring D is possibly influenced by a change in the
volume of the substituent at the C-7' atom. On the whole,
both molecules have a conformational arrangement of rings
A, C, and D called the "distorted propeller".21–24
The bicyclic system EF of molecule 5d is planar, the
average deviation from the plane does not exceed 0.0089 Å.
The oxygen atom of the methoxy group is located in this
plane, the methoxy group itself is turned in the opposite
direction from the ethyl substituent toward ring D.
The positions of the aryl substituents E (compound 5c)
and EF (compound 5d) at the C(2) atom are most easily
characterized by the values of the torsion angles
N(3)–C(2)–C(1'E)–C(2'E) and N(3)–C(2)–C(5'EF)–C(6EF),
which are 47.9 and 70.8°, respectively. And again, in the
latter case, the change in the angle is obviously associated
with a change in the volume of the substituent and its
contact with the phenyl substituent D.
Ph Ph
67.6
127.3
N
155.6
138.0
O
O
N
6.66H
H
Me
3.69
OMe
Figure 1. Structurally significant correlations in the
1H–13C HMBC spectrum of compound 5d.
The presence in the IR spectrum of product 8 of
characteristic vibration bands of the amide group at 1640
and 3100 cm–1 and broadened singlets of the NH protons of
the amine and amide groups (at 1.80 and 6.18 ppm,
respectively) in the 1H NMR spectrum indicates the
opening of the heterocycle.
In the H–13C HMBC correlation spectrum (Table 1) of
1
compound 5d, a characteristic cross peak can be observed
at 3.69/138.0 ppm confirming the spin interaction of the
methylene group protons with the C-8а carbon atom, which
is possible when the ethyl group is located at the N-1 atom
but not at the N-3 atom (Fig. 1).
Earlier1 and in the present study, we have shown by
NMR spectroscopy that methylation and ethylation of
2-aryl-4,4-diphenylquinazolines occurs at the N-1 nitrogen
atom. To unambiguously prove the direction of the
alkylation process of compounds 3a–d and the spatial
structure of the alkylation products 5a–d, 6, 7, X-ray
structural analysis of single crystals of 1-ethyl-2,4,4-tri-
phenyl-1,4-dihydroquinazoline (5c) and 1-ethyl-2-(7-meth-
oxy-1,3-benzodioxol-5-yl)-4,4-diphenyl-1,4-dihydroquina-
zoline (5d) was carried out (Fig. 2). As can be seen,
alkylation actually occurs at position 1 of the quinazoline
ring, apparently due to steric hindrances during
electrophilic attack at position 3.
In both molecules, ring B is not planar – it has a twist-
boat conformation. Atoms N(1) and C(4) exit the plane of
the benzene ring A in different directions (atom N(1) by
–0.17 and atom C(4) by 0.17 Å), the C (2) and N (3) atoms
exit in the direction of atom C(4) by about 0.7 Å. For
molecule 5c, the ''bottom'' of the boat of ring B formed by
the atoms C(2), N(3), C(4a), and C(8a) is an almost ideal
plane (the average deviation of atoms from the plane is
0.0065 Ǻ). The ''walls'' of the boat N(3)–C(4)–C(4a) and
To conclude, new conditions have been developed for
the preparation of N1-monoalkyl-substituted 1,4-dihydro-
quinazolines based on 3,4-dihydroquinazolines and various
alkylating agents in DMSO.
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Chemistry of Heterocyclic Compounds 2020, 56(12), 1548–1553
Experimental
Н2О (20–25 ml) was added to the reaction mixture. The
formed precipitate was extracted with CH2Cl2 (3×10 ml),
the organic extracts were combined and dried over
anhydrous Na2SO4. After filtration and distillation of the
solvent, the solid residues were recrystallized from EtOH.
1-Ethyl-2-methyl-4,4-diphenyl-1,4-dihydroquinazoline
(5а). Yield 53 mg (51%), colorless crystals, mp 136–138°C,
IR spectra were registered on
a
PerkinElmer
SpectrumTwo spectrometer using the attenuated total
1
reflectance (ATR) accessory. H and 13C NMR spectra
were acquired on an Agilent 400/54 spectrometer (400 and
100 MHz, respectively) in DMSO-d6 and CDCl3, using
TMS as internal standard. High-resolution mass spectra
were recorded on a Bruker maXisTM Impact UHR/Q-TOF
mass spectrometer (electrospray ionization). Elemental
analysis was performed on a Hewlett-Packard HP-185B
CHN-analyzer. Melting points were determined on a Stuart
SMO 30 apparatus. Monitoring of the reaction progress
was done by TLC on Silufol UV-254 plates (PhH–Me2CO,
9:1 for compounds 5а–d and PhH for compounds 2e, 3e,
6–8), visualization with iodine vapor.
1
Rf 0.11. IR spectrum, ν, cm–1: 1630 (C=N). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.09 (3H, t, J = 6.6,
CH3); 2.31 (3H, s, 2-CH3); 3.75 (2H, q, J = 6.6, CH2); 6.63
(1H, dd, J = 7.2, J = 1.2, H-8); 6.93–6.97 (2H, m, H-5,7);
7.13–7.39 (11H, m, H Ph, H-6). 13C NMR spectrum
(CDCl3), δ, ppm: 13.5 (CH2CH3); 21.6 (2-CH3); 39.9
(CH2); 66.2 (C-4); 111.4 (C Ar); 122.2 (C Ar); 126.3
(2C Ar); 127.3 (C Ar); 127.4 (4C Ar);127.8 (C Ar); 128.8
(4C Ar); 129.1 (2C Ar); 137.3 (C Ar); 148.1 (C Ar); 152.6
(C-2). Found, %: C 84.52; H 6.79; N 8.53. C23H22N2.
Calculated, %:C 84.63; H 6.79; N 8.58.
The starting compounds 3a–e were obtained according
to published methods,3,4 their physicochemical characte-
ristics correspond to those described earlier.2,5
2-Benzyl-1-ethyl-4,4-diphenyl-1,4-dihydroquinazoline
(5b). Yield 58 mg (45%) colorless crystals, mp 172–174°C,
6-Bromo-2,4,4-triphenyl-3,4-dihydroquinazolinium
perchlorate (2e) was synthesized according to a literature
method3 from (2-amino-5-bromophenyl)diphenylmethanol
(1b) (0.283 g, 0.8 mmol), PhCN, and HClO4. Yield 0.315 g
(72%), light-yellow crystals, mp 245–250°C. IR spectrum,
1
Rf 0.41. IR spectrum, ν, cm–1: 1610 (C=N). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 0.86 (3H, t, J = 7.3,
CH3); 3.60 (2H, q, J = 7.3, NCH2); 4.00 (2H, s, CH2);
6.63 (1H, dd, J = 8.2, J = 2.0, H-8); 6.91–6.98 (1H, m,
H Ar); 6.98–7.00 (2H, m, H Ar); 7.15–7.20 (5H, m,
H 2-CH2Ph); 7.26–7.28 (10H, m, H Ar). 13C NMR
spectrum (CDCl3), δ, ppm: 13.5 (CH3); 39.5 (CH2); 41.3
(NCH2); 67.0 (C-4); 111.6 (C Ar); 122.6 (C Ar); 126.4
(2C Ar); 127.4 (2C Ar); 127.5 (4C Ar); 127.7 (C Ar); 127.9
(2C Ar); 128.5 (2C Ar); 129.0 (4C Ar); 129.1 (2C Ar);
137.2 (C Ar); 137.4 (C Ar); 147.8 (C Ar); 154.0 (C-2).
Found, %: C 86.50; H 6.41; N 6.71. C29H26N2. Calculated,
%: C 86.53; H 6.51; N 6.96.
–
–
1
ν, cm–1: 1075 (ClO4 ), 1110 (ClO4 ), 1650, 3220. H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 6.76 (1Н, d, J = 7.8,
Н-8); 7.16–7.30 (4H, m, Н Ar); 7.37–7.58 (6H, m, H Ar);
7.60–7.82 (5H, m, H Ar); 7.90–7.95 (2H, m, Н-2,6 2-Ph);
11.92 (1Н, s, NH); 12.80 (1Н, br. s, NH). 13C NMR
spectrum (DMSO-d6), δ, ppm: 67.1 (C-4); 119.4 (C-6);
120.2 (C Ar); 126.6 (C Ar); 127.1 (C Ar); 128.6 (4C Ar);
129.2 (C Ar); 129.3 (4C Ar); 129.5 (2C Ar); 130.1 (2C Ar);
131.2 (C-8); 131.5 (C Ar); 132.7 (C Ar); 133.2 (2C Ar);
135.0 (C Ar); 142.8 (C-8a); 157.3 (C-2). Found, m/z:
439.0828. [M+H]+. C26H20BrN2. Calculated, m/z: 439.0804.
6-Bromo-2,4,4-triphenyl-3,4(1,4)-dihydroquinazoline
(3e) was obtained by deprotonation of salt 2e. Salt 2е (390 mg,
0.73 mmol) was mixed with an excess of 5% aqueous
NaOH (10–15 ml), and the mixture was heated under reflux
for 10 min. Then the mixture was cooled, the precipitate
was filtered off, washed with H2O, dried, and recrystallized
from EtOH. Yield 158 mg (49%), colorless crystals, mp 220–
222°C, Rf 0.17. IR spectrum, ν, cm–1: 1620 (C=N), 3352
(NH). 1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 3.35
(1Н, br. s, NH); 6.70 (1Н, d, J = 7.2, Н-8); 7.20–7.33 (5H,
m, Н Ph); 7.35–7.42 (7H, m, H Ph, H-5,7); 7.62–7.64 (3H,
m, H-3,4,5 2-Ph); 7.93–7.95 (2H, m, Н-2,6 2-Ph).
13C NMR spectrum (DMSO-d6), δ, ppm: 67.3 (C-4); 115.2
(C-6); 117.5 (C Ar); 126.7 (2C Ar); 127.1 (C Ar); 127.4
(C Ar); 127.9 (4C Ar); 128.2 (2C Ar); 128.9 (4C Ar); 129.3
(2C Ar); 129.6 (2C Ar); 130.3 (C Ar); 131.2 (C Ar); 135.0
(C-4a); 144.3 (C-8a); 157.4 (C-2). Found, m/z: 439.0817
[M+Н]+. C26H20BrN2. Calculated, m/z: 439.0804.
1-Ethyl-2,4,4-triphenyl-1,4-dihydroquinazoline (5c).
Yield 67 mg (54%), colorless crystals, mp 208–210°C,
1
Rf 0.79. IR spectrum, ν, cm–1: 1600 (C=N). H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 0.38 (3Н, t, J = 6.8,
CН3); 3.67 (2H, q, J = 6.8, NCH2); 6.55 (1H, dd, J = 6.5,
J = 1.2, H-8); 7.04–7.29 (12H, m, H Ph, Н-5,7); 7.38 (1H,
ddd, J = 6.6, J = 6.5, J = 1.2, H-6); 7.46–7.58 (5H, m,
Н Ph). 13C NMR spectrum (DMSO-d6), δ, ppm: 13.9
(CН3); 41.7 (CH2); 67.3 (C-4); 107.0 (C Ar); 114.2 (C Ar);
123.1 (C Ar); 126.8 (2C Ar); 127.8 (4C Ar); 128.0 (2C Ar);
128.8 (4C Ar); 129.6 (2C Ar); 129.8 (C Ar); 130.3 (C Ar);
135.0 (C Ar); 137.1 (C Ar); 138.4 (C Ar); 148.2 (C Ar);
152.2 (C Ar); 156.1 (C-2). Found, m/z: 389.2028 [M+Н]+.
C28H25N2. Calculated, m/z: 389.2012.
1-Ethyl-2-(7-methoxy-1,3-benzodioxol-5-yl)-4,4-diphe-
nyl-1,4-dihydroquinazoline (5d). Yield 37 mg (25%),
colorless crystals, mp 185–187°C, Rf 0.72. IR spectrum,
1
ν, cm–1: 1046–1138 (ОCН2О); 1630 (C=N). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 0.58 (3Н, t, J = 6.0,
CН3); 3.69 (2H, q, J = 6.0, NCH2); 3.92 (3H, s, ОCН3);
5.99 (2Н, s, OCН2O); 6.66 (1H, d, J = 7.5, H-8); 6.73 (2Н,
s, Н-4',6'); 7.05–7.35 (13H, m, H Ph, Н-5,6,7). 13C NMR
spectrum (CDCl3), δ, ppm: 13.7 (CН3); 41.8 (NCH2); 56.7
(ОCН3); 67.6 (C-4); 101.8 (C-2'); 103.8 (C-4'); 109.4
(C-6'); 113.1 (C-5); 122.9 (C-7); 126.4 (2C Ar); 127.3
(C-6); 127.4 (4C Ar); 128.8 (C-8); 128.9 (4C Ar); 130.3
Synthesis of compounds 5а–d, 6–8 (General method).
The corresponding 3,4(1,4)-dihydroquinazoline 3a–e
(0.32 mmol) and alkylating agent (0.64 mmol) were
successively added with stirring to a mixture of KOH
powder (72 mg, 1.3 mmol) and DMSO (5 ml). The reaction
was carried out at 30–40°C for 2–3 h (TLC control). Then,
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Chemistry of Heterocyclic Compounds 2020, 56(12), 1548–1553
(2C Ar); 130.5 (C-5'); 136.5 (C-7a'); 138.0 (C-8a); 143.4
software (Sheldrick, 2015),26 molecular graphics and
preparation of the material for publication were performed
with the software package Olex2 ver 1.2.10.27
(C-7'); 148.0 (C-4a); 148.7 (C-3a'); 155.6 (C-2). Found,
m/z: 463.2020 [M+Н]+. C30H27N2O3. Calculated, m/z:
463.2016.
Crystals of compound 5c (C28H24N2, М 388.49) are
monoclinic, space group P21; a 7.8330(2), b 10.6310(3), c
12,8832(4) Å; β 93.420(3)°; V 1070.91(5) Å3; Z 2; T 293
(2) K; μ(CuKα) 0.538 mm–1; dcalc 1.205 g/cm3. A total of
22347 reflections were collected (6.874° ≤ 2Θ ≤ 152.586°), of
which 4478 were unique (Rint 0.0461, Rσ 0.0274), which
were used in all calculations. The final probability factors
were R1 0.0347 (I > 2σ(I)), wR2 0.0945.
1-Benzyl-6-bromo-2,4,4-triphenyl-1,4-dihydroquina-
zoline (6). Yield 89 mg (53%), colorless crystals, mp 203–
205°C, Rf 0.31. IR spectrum, ν, cm–1: 1610 (C=N).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 4.75 (2H, s,
CH2); 6.47–6.49 (2Н, m, Н-2,6 1-CH2Ph); 6.76 (1Н, s,
Н-5); 6.82 (1H, dd, J = 6.5, J = 1.2, H-8); 6.92–6.94 (2H,
m, Н-3,5 1-CH2Ph); 6.98–7.11 (1H, m, Н-4 1-CH2Ph); 7.16–
7.34 (11H, m, H Ph, Н-7); 7.37–7.44 (3H, m, Н-3,4,5 2-Ph);
7.45–7.50 (2H, m, Н-2,6 2-Ph). 13C NMR spectrum
(CDCl3), δ, ppm: 51.2 (NCH2); 67.4 (C-4); 114.7 (C-8);
115.5 (C-6); 126.6 (2C Ar); 126.9 (2C Ar); 127.1 (C Ar);
127.9 (4C Ar); 128.3 (2C Ar); 128.5 (2C Ar); 128.8
(2C Ar); 128.9 (4C Ar); 129.6 (C Ar); 130.3 (2C Ar); 131.1
(C Ar); 131.5 (2C Ar); 136.4 (C Ar); 137.0 (C Ar); 147.3
(C Ar); 155.5 (C-2). Found, m/z: 529.1271 [M+Н]+.
C33H26BrN2. Calculated, m/z: 529.1274.
Crystals of compound 5d (C30H26N2O3, М 462.53)
are monoclinic, space group P21/c; a 8,81360(10),
b
16.8898(2),
c
16.3417(2) Å;
β
92.7960(10)°;
V 2429.73(5) Å3; Z 4; Т 293(2) K; μ(CuKα) 0.654 mm–1;
dcalc 1.264 g/cm3. A total of 25125 reflections were
collected (7.532° ≤ 2Θ ≤ 152.354°), of which 5045 were
unique (Rint 0.0334, Rσ 0.0189), which were used in all
calculations. The final probability factors were R1 0.0385
(I > 2σ(I)), wR2 0.1024.
3-[(6-Bromo-2,4,4-triphenylquinazolin-1(4H)-yl)methyl]-
isoxazole (7). Yield 23 mg (14%), colorless crystals,
mp 117–120°C, Rf 0.23. IR spectrum, ν, cm–1: 1590, 1630
The full set of X-ray structural data for compounds 5c,d
were deposited at the Cambridge Crystallographic Data
Center (deposits CCDC 1922709 and CCDC 1922710,
respectively).
1
(C=N). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 4.85
(2H, s, NCH2); 6.85 (1Н, d, J = 6.0, Н-8); 7.10–7.22 (2H,
m, H-5,7); 7.24–7.36 (10H, m, H Ph); 7.39–7.48 (5H, m,
2-Ph); 7.85–7.88 (2H, m, H-4'',5''). 13C NMR spectrum
(CDCl3), δ, ppm: 43.0 (NCH2); 66.1 (C-4); 102.5 (C Ar);
114.6 (C-6); 126.9 (2C Ar); 127.0 (C Ar); 127.8 (2C Ar);
127.9 (2C Ar); 128.3 (4C Ar); 128.4 (C Ar); 128.7 (C Ar);
128.8 (4C Ar); 129.0 (C Ar); 130.2 (C Ar); 131.1 (C Ar);
131.5 (C Ar); 134.5 (C Ar); 145.0 (C Ar); 147.2 (C Ar);
158.5 (C-2); 167.2 (C=N). Found, m/z: 520.1012 [M+Н]+.
C30H23BrN3О. Calculated, m/z: 520.1019.
The authors are grateful to the Ministry of Science and
Higher Education of the Russian Federation for financial
support (project FZEZ-2020-0004).
References
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1
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