ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ
The rearrangement patterns of new 1,3-benzoxazines derivatives obtained by condensation of substituted salicylamides with cyclic ketones under the influence of Vilsmeier-Haack reagent has been studied. The influence of angel strain in a 4-membered spirocycle prevents the rearrangement of spiro [1,3-...
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| Дата: | 2020 |
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| Мова: | Англійська |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2020
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465409401585664 |
|---|---|
| author | Farat, Oleg Varenichenko, Svetlana Zaliznaya, Ekaterina Markov, Victor |
| author_facet | Farat, Oleg Varenichenko, Svetlana Zaliznaya, Ekaterina Markov, Victor |
| author_institution_txt_mv | [
{
"author": "Oleg Farat",
"institution": "Department of Pharmacies and Technology of Organic Substances, Ukrainian State Chemical Technology University, Dnipro, Ukraine"
},
{
"author": "Svetlana Varenichenko",
"institution": "Associate Professor Department of Pharmacies and Technology of Organic Substances, Ukrainian State Chemical Technology University, Dnipro, Ukraine"
},
{
"author": "Ekaterina Zaliznaya",
"institution": "Department of Pharmacies and Technology of Organic Substances, Ukrainian State Chemical Technology University, Dnipro, Ukraine"
},
{
"author": "Victor Markov",
"institution": "Department of Pharmacies and Technology of Organic Substances, Ukrainian State Chemical Technology University, Dnipro, Ukraine"
}
] |
| author_sort | Farat, Oleg |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:42Z |
| description | The rearrangement patterns of new 1,3-benzoxazines derivatives obtained by condensation of substituted salicylamides with cyclic ketones under the influence of Vilsmeier-Haack reagent has been studied. The influence of angel strain in a 4-membered spirocycle prevents the rearrangement of spiro [1,3-benzoxazine-2,1'-cyclobutan]-4(3H)-one under the action of a formylating agent. 1,3-Benzoxazines derivatives with ring sizes from 5- to 8-membered under the action of a formylating agent have formed formylxanthene derivative. Their formation reaction rate depends on the presence of electronegativity substituents at positions C-6 and C-8 of the aromatic cycle, as well as in the spiroring. In this work, we presented an effective method for the synthesis of formyl derivatives of xanthenes based on readily available salicylamide. It was found that (spiro[1,3-benzoxazine-2,1'-cyclobutan]-4(3H)-one) does not rearrange even under prolonged heating due to the spirocycle strain. The presence of bromine or iodine atoms at positions C-6 and C-8 of the aromatic cycle of 1,3-benzoxazines makes the reaction more difficult, which requires more harsh synthesis conditions. |
| doi_str_mv | 10.33609/0041-6045.86.2.2020.111-122 |
| first_indexed | 2025-09-24T17:43:23Z |
| format | Article |
| fulltext |
Органічна хімія
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2 111
УДК 547.867. doi: 10.33609/0041-6045.86.2.2020.111-122
O. K. Farat, S. A. Varenichenko*, E. V. Zaliznaya, V. I. Markov
REARRANGEMENT OF SUBSTITUTED 1,3-BENZOXAZINES INTO
XANTHENE-TYPE COMPOUNDS
Ukrainian State University of Chemical Technology, 49005 Dnipro, Ukraine
*е-mail: svetlanavarenichenko@gmail.com
The rearrangement patterns of new 1,3-benzoxazines derivatives obtained by condensa-
tion of substituted salicylamides with cyclic ketones under the influence of Vilsmeier-
Haack reagent has been studied. The influence of angel strain in a 4-membered
spirocycle prevents the rearrangement of spiro [1,3-benzoxazine-2,1'-cyclobutan]-
4(3H)-one under the action of a formylating agent. 1,3-Benzoxazines derivatives with
ring sizes from 5- to 8-membered under the action of a formylating agent have formed
formylxanthene derivative. Their formation reaction rate depends on the presence of
electronegativity substituents at positions C-6 and C-8 of the aromatic cycle, as well as
in the spiroring.
K e y w o r d s: rearrangement, Vilsmeier–Haack reagent, condensation, 1,3-
benzoxazine, xanthene derivatives.
Introduction. One of the urgent tasks of
synthetic chemists is the development of
effective synthetic approaches, which allow
constructing complex heterocyclic systems
from simple and affordable reagents. In the
study of formylation, we first showed the
possibility of using spiro derivatives of
pyrimidines for the synthesis of previously
inaccessible derivatives of hydroacridines [1,
2]. To obtain new examples of structurally
complex heterocycles, taking into account
the concept of molecular diversity, we stud-
ied rearrangement to benzothiazine,
quinoline [3] and formyl derivatives of
xanthenes with various substituents [4-6].
The synthesized formyl derivatives of
xanthenes exhibit fluoresce in solutions with
large Stokes shifts and moderate quantum
yields [6, 7]. In [6], the effect of the annulat-
ed aliphatic rings on the photophysical prop-
erties was studied. It was found that a de-
crease in the size of this cycle led to an in-
crease in the quantum yield of fluorescence.
Modification of the formyl group in the
products of rearrangement of 1,3-
benz(naphth)oxazines by reaction with aro-
matic amines, despite the extending of the
conjugated chain, does not lead to an in-
crease in fluorescence [8, 9]. The reaction of
the formyl derivative of xanthene with hy-
drazine resulted in a previously unknown
aldazine [8]. The interest in these com
© O. K. Farat, S. A. Varenichenko, E. V. Zaliznaya, V. I. Markov, 2020
mailto:svetlanavarenichenko@gmail.com
Rearrangement of substituted 1,3-benzoxazines into xanthene-type compounds
112 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2
pounds is due to the fact that with a decrease
in pH an intense color change is observed,
which allows them to be positioned as pH
analyzers [10-12]. The initial benzoxazines
attract attention not only due to rearrange-
ments under the action of the formulating
agent but also due to their biological activi-
ty. In particular, we found the presence of
antimicrobial activity among derivatives of
1,3-benzoxazines [13].
Given the novelty of the results ob-
tained and the prospects for their practical
application, the continuation of research in
this direction is an urgent task. This work
presents the results of the influence of the
size of spirocycle and electronegativity of
the substituents on the course of rearrange-
ment.
Results and Discussion. New deriva-
tives of 1,3-benzoxazines 5–10 were ob-
tained by condensation of salicylamides 1–4
with cyclic ketones in toluene in the pres-
ence of p-TsOH with water removal with a
Dean–Stark trap according to the procedure
[14] (Scheme 1).
p-TsOH
PhMe
6-111-4
R'
O
O
N H
R
OR'
O H
CONH 2R
+
Scheme 1. 1 – R=R′=H; 2 – R=Br, R′=H; 3 –
R=R′=Br; 4 – R=R′=H
When the reaction is carried out in ace-
tic acid with propionic anhydride and sul-
furic acid the compound 5 is formed
(Scheme 2).
In the case of compound 11, pyrroli-
dine was used as a catalyst, and the reaction
time was increased to 16 hours. The struc-
tures of the synthesized compounds were
established by a complex of spectral meth-
ods. Compounds 7–9 were obtained as a
mixture of two stereoisomers, which were
reacted with a Vilsmeier-Haack reagent
without prior separation.
The reaction of spiro derivatives 6–11
with a formylating agent yielded compounds
12–17 (Scheme 3). The reaction products
were isolated as intermediate perchlorate
salts, which were further subjected to hy-
drolysis with NaOH solution to obtain rele-
vant formyl derivatives. The structures of the
synthesized compounds were confirmed by
1H NMR, 13C NMR spectroscopy and mass
spectrometric data. The 1H and 13C NMR
spectra of these compounds have a charac-
teristic signal of the formyl group at ~10.3
ppm and ~187 ppm, respectively
Benzoxazine 5, during prolonged heating at
100 °C under the conditions of the
Vilsmeier-Haack reaction, did not undergo a
similar rearrangement, and after alkalizing
the reaction mixture, unreacted compound 5
was isolated.
The key stage of the reaction is the
electrophilic disclosure of the oxazine cycle,
which flew through the intermediate salt of
imidoyl chloride A. The electron lone pair of
oxygen atom attacks σ*-orbital of C–N
bond, which leads to breaking of this bond
and formation of oxonium cation B (scheme
4). Scheme 3 shows the initial stages of the
reaction using compound 6 as an example.
For the complete rearrangement mechanism,
see [4].
The lack of rearrangement for com-
pound 5 is explained by the strain of the
cyclobutane cycle.
O. K. Farat, S. A. Varenichenko, E. V. Zaliznaya, V. I. Markov
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2 113
Pr2O, AcOH
H2SO4
5
1
O
O H
CONH 2
+
5 6 7 8
9 10 11
C
13
C
11
C
2
N H
O
N
O
N H
O
O
I
N H
O
O
I
I
N H
O
O
I
Br
N H
O
O
Br
Br
N H
O
O
N H
O
O
Scheme 2
POCl3/DMF
12-17
6-11
CHO
R
N
N
O
R'
N
+
R
N
N
O
R'
R'
O
O
N H
R H 2 O
NaOH
ClO 4
-
12 13 14
15 16 17
CHOOHCCHO
CHOCHOCHO
O
N
N
N
O
N
N
I
O
N
N
I
I
O
N
N
I
Br
O
N
N
Br
Br
O
N
N
Scheme 3
Rearrangement of substituted 1,3-benzoxazines into xanthene-type compounds
114 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2
other steps
of the reaction
A B
6
8
-H
+
POCl 3 /DMF
O
+
NHN
+
Br
NH
O
Cl
Br
Cl
Br
O
H
Cl
Br
N H
O
O
Scheme 4
In compound 5, the C11–C2–C13 va-
lence angle was 90°, which was a 19.5° de-
viation from the perfect tetrahedron angel. In
the case of opening of the oxazine cycle, this
angle would still be 90°, but hybridization at
the C-2 atom would change from sp3 to sp2,
and as a result, the strain of the 4-membered
cycle would increase, since in this case the
deviation of the valence angle from ideal
trigonal would already be 30º. Such a transi-
tion of hybridization of the C-2 atom in
compound 5 would be energetically disad-
vantageous.
In this regard, compound 5 was not
subjected to electrophilic rearrangement un-
der the conditions of the Vilsmeier-Haack
reaction even under conditions of prolonged
heating at 100°C.
The increase in reaction time for com-
pounds 7–9 is explained by the influence of
the electronegativity of the substituents at
positions C-6 and C-8 of the benzoxazine
ring. The presence of a bromine atom at po-
sition C-6 of spiro compound 6 did not af-
fect the stability of the intermediate cation
B, so the reaction proceeded under relatively
mild conditions (1.5 hours at 75°C). The
bromine and iodine atoms in the C-8 posi-
tion of compounds 7–9, because of their
negative inductive effect, destabilized cation
B, which required more harsh reaction con-
ditions (11 h at 100°C for compound 7). Due
to the negative inductive effect, but of the
nitrogen atom presence in the spiro ring, the
rearrangement of the spiran 11 was also
passing within 11 hours, as in the case of the
dibromo-substituted spiran 7.
The next step in our research was the
study of the formylation of compounds 19–
23, with aliphatic substituents instead of a
spiro ring. Compounds 19–23 were obtained
by condensation of salicylamide derivatives
1, 18 with aliphatic ketones by prolonged
boiling for 16–18 h in benzene with the
azeotropic distillation of water in the pres-
ence of p-TsOH (Scheme 5).
However, the reaction of compounds
19–23 with the Vilsmeier-Haack reagent did
not proceed selectively with the formation of
resinous products, which were difficult to
separate and identify.
The formation of vinyl ethers with dif-
ferent arrangements of double bonds and
substituents after the opening of the oxazine
cycle is a probable reason for the formation
of а complicated mixture of the products.
Some of these intermediates react similarly
to the previous scheme, others cannot cy-
clize into the pyran cycle (trans vinyl ethers)
and reacted in a different way, which leads
to a multicomponent mixture of products
with close Rf values.
Experimental part. 1H and 13C NMR
spectra were recorded on a Bruker Avance II
O. K. Farat, S. A. Varenichenko, E. V. Zaliznaya, V. I. Markov
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2 115
19-231, 18
R'
O
R2
R1
O
N H
R
O
R2R1
R'
O H
CONH 2R
H
+
+
19 20 21
22 23
O
N H
OO
N H
O
O
N H
O
O
N H
OO
O
N H
1 – R=R′=H; 18 – R=R′=i-Pr
Scheme 5
400 spectrometer (400 and 101 MHz, re-
spectively) or a Bruker Avance 600 spec-
trometer (600 and 151 MHz, respectively;
compound 5) in CDCl3 or DMSO-d6 with
TMS as internal standard. The 1H and 13C
NMR spectra for compounds 7–9 are pre-
sented for the predominant isomer. The EI
mass spectra were recorded on a Kratos MS
30 instrument with direct injection of the
sample, ionization chamber temperature
250°C, ionization energy 70 eV. Elemental
analysis was performed on a LECO CHN-
900 instrument. Melting points were deter-
mined using an Electrothermal 9100 Digital
Melting Point apparatus and were uncorrect-
ed. Completion of the reactions and purity of
the obtained compounds were monitored by
TLC on Merck Silica gel 60 F-254 plates,
eluent CHCl3–МеOH, 9:1.
All reagents of analytical grade were
purchased from commercial suppliers and
used without any further purification, unless
stated otherwise. Compounds 2 [15], 3 [16],
4 [17] and 18 [5, 18] were obtained by
known procedures.
Synthesis of spiro[1,3-benzoxazine-
2,1'-cyclobutan]-4(3H)-one (5): Conc.
H2SO4 (1 ml) was added to glacial acetic
acid (3 ml), cooled in ice and left for several
minutes. A solution of compound 1 (1.37 g,
0.01 mol), cyclobutanone (0.84 g, 0.012
mol), and propionic anhydride (1.5 ml) in
glacial acetic acid (3 ml) was prepared sepa-
rately. The first solution of H2SO4 and
AcOH was slowly added to the latter mix-
ture with stirring and cooling with ice,
stirred for 12 h at room temperature. Then
neutralized to pH ~7 using sodium carbonate
solution. The precipitate formed was filtered
off and recrystallized from aqueous MeOH.
Yield 47%, white powder, mp 158–161˚C.
1H NMR spectrum (CDCl3), δ, ppm (J, Hz):
δ = 8.43 (1H, s, NH), 7.92 (1H, d, 3J=7.5,
Ar), 7.46 (1H, t, 3J=7.4, Ar), 7.08 (1H, t,
3J=7.5, Ar), 7.00 (1H, d, 3J=8.2, Ar), 2.52–
2.56 (2H, m, CH), 2.38–2.43 (2H, m, CH),
1.92–1.99 (1H, m, CH), 1.83–1.90 (1H, m,
CH). 13C NMR spectrum (CDCl3), δ, ppm: δ
= 163.1, 155.3, 133.9, 127.2, 121.5, 117.2,
116.7, 88.1, 35.1, 11.4. Mass spectrum, m/z
(Irel, %): 189 [M]+ (3). Found, %: C 69.90;
H 5.90; N 7.45. C11H11NO2. Calculated, %:
C 69.83; H 5.86; N 7.40.
Synthesis of spirans 6–10 (General
method). A mixture of the corresponding
salicylamide 1-4 (0.01 mol), ketone (0.012
mol), and p-TsOH·H2O (0.03 mol) in PhMe
(45 ml) was refluxed for 8 h with continuous
removal of water with a Dean–Stark trap.
Rearrangement of substituted 1,3-benzoxazines into xanthene-type compounds
116 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2
Then solvent was evaporated to dryness un-
der reduced pressure, the solid residue was
washed with 5% aqueous NaOH solution,
water and filtered off.
6-Bromospiro[1,3-benzoxazine-2,1'-
cyclopentan]-4(3H)-one (6):Yield 68%,
white powder, mp 195–196˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
8.20 (1H, br. s, NH); 8.00 (1H, s, H-5 Ar);
7.50 (1H, d, 3J=8.6, H-7 Ar); 6.83 (1H,
d, 3J=8.6, H-8 Ar); 2.07–2.16 (2H, m, CH);
1.65–1.85 (6H, m, CH). 13C NMR spectrum
(CDCl3), δ, ppm: δ = 162.2; 154.9; 137.3;
130.4; 119.2; 114.2; 96.3, 37.4, 22.4. Mass
spectrum, m/z (Irel, %): 283 [M (81Br)]+ (25),
281 [M(79Br)]+ (24). Found, %: C 51.21; H
4.45; N 5.05. C12H12BrNO2. Calculated, %:
C 51.09; H 4.29; N 4.96.
6,8-Dibromo-4'-tert-butylspiro[1,3-
benzoxazine-2,1'-cyclohexan]-4(3H)-one (7):
Yield 88%, white powder, mp 253–257˚C
(DMF). 1H NMR spectrum (CDCl3), δ, ppm:
δ = 7.98 (1H, s, NH), 7.80 (1H, s, Ar), 7.28
(1H, s, Ar), 2.31–2.33 (2H, m, CH), 1.55–
1.71 (6H, m, CH), 1.13–1.16 (1H, m, CH),
0.91 (9H, s, t-Bu). 13C NMR spectrum
(CDCl3), δ, ppm: δ = 161.6, 154.7, 142.8,
142.6, 132.6, 117.2, 115.1, 92.1, 49.2, 33.3,
35.6, 30.4, 25.9. Mass spectrum, m/z (Irel,
%): 431 [M]+ (55). Found, %: C 47.51; H
5.05; N 3.38. C17H21Br2NO2. Calculated, %:
C 47.36; H 4.91; N 3.25.
4'-tert-Butyl-6,8-diiodospiro[1,3-
benzoxazine-2,1'-cyclohexan]-4(3H)-one (8):
Yield 88%, white powder, mp 228–234˚C
(DMF). 1H NMR spectrum (CDCl3), δ, ppm:
δ = 8.34 (1H, s, NH), 8.14 (2H, s, Ar), 2.22–
2.29 (2H, m, CH), 1.59–1.70 (6H, m, CH),
1.13–1.16 (1H, m, CH), 0.91 (9H, s, t-Bu).
13C NMR spectrum (CDCl3), δ, ppm: δ =
161.6, 155.0, 150.8, 136.6, 119.8, 89.5, 86.3,
84.6, 46.4, 36.3, 32.6, 27.8, 22.8. Mass spec-
trum, m/z (Irel, %): 525 [M]+ (45). Found, %:
C 39.05; H 4.15; N 2.82. C17H21I2NO2. Cal-
culated, %: C 38.88; H 4.03; N 2.67.
4'-(1,1-Dimethylpropyl)-6,8-
diiodospiro[1,3-benzoxazine-2,1'-
cyclohexan]-4(3H)-one (9): Yield 90%,
white powder, mp 218–223˚C (DMF). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
8.15 (2H, s, Ar), 8.02 (1H, br s, NH), 2.22–
2.29 (2H, m, CH), 1.55–1.70 (6H, m, CH),
1.26–1.31 (3H, m, CH), 0.87 (6H, s, 2CH3),
0.82 (3H, t, 3J=6.8, CH3). 13C NMR spec-
trum (CDCl3), δ, ppm: δ = 160.5, 154.0,
149.9, 135.6, 118.8, 88.5, 85.3, 83.6, 42.7,
35.5, 33.9, 31.9, 21.4, 18.9, 7.3. Mass spec-
trum, m/z (Irel, %): 539 [M]+ (35). Found, %:
C 40.25; H 4.40; N 2.71. C18H23I2NO2. Cal-
culated, %: C 40.10; H 4.30; N 2.60.
Spiro[1,3-benzoxazine-2,1'-
cyclooctan]-4(3H)-one (10): Yield 88%,
white powder, mp 158–160˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
7.89 (1H, d, 3J=7.4, Ar); 7.61 (1H, br. s,
NH); 7.42 (1H, t, 3J=7.5, Ar); 7.03 (1H,
t, 3J=7.4, Ar); 6.89 (1H, d, 3J=8.1, Ar);
2.20–2.28 (2H, m, CH); 1.96–2.04 (2H, m,
CH); 1.51–1.78 (10H, m, 5CH2). 13C NMR
spectrum (CDCl3), δ, ppm: δ = 161.2; 154.4;
137.0; 130.0; 119.0; 114.3; 92.1; 39.5; 28.2;
21.2; 20.1. Mass spectrum, m/z (Irel, %): 245
[M]+ (10). Found, %: C 73.51; H 7.89; N
5.77. C15H19NO2. Calculated, %: C 73.44; H
7.81; N 5.71.
Synthesis of 1'-propylspiro[1,3-
benzoxazine-2,4'-piperidin]-4(3H)-one (11):
A mixture of the salicylamide 1 (1.37 g, 0.01
mol), 1-propylpiperidin-4-one (1.69 g, 0.012
mol), and pyrrolidine (2.13 g, 0.03 mol) in
O. K. Farat, S. A. Varenichenko, E. V. Zaliznaya, V. I. Markov
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2 117
PhMe (45 ml) was refluxed for 16 h with
continuous removal of water with a Dean–
Stark trap. Then solvent was evaporated to
dryness under reduced pressure, the solid
residue was washed with 5% aqueous NaOH
solution, water and filtered off. Yield 68%,
white powder, mp 150–152˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
7.89 (1H, d, 3J=6.6, Ar); 7.67 (1H, br. s,
NH); 7.43 (1H, t, 3J=7.1, Ar); 7.05 (1H,
t, 3J=7.5, Ar); 6.94 (1H, d, 3J=8.2, Ar);
2.62–2.72 (2H, m, CH2); 2.43–2.50 (2H, m,
CH); 2.32–2.38 (2H, m, CH); 2.17–2.21
(2H, m, CH); 1.90–2.00 (2H, m, CH); 1.44–
1.56 (2H, m, CH2), 0.89 (3H, t, 3J=7.3,
CH3). 13C NMR spectrum (CDCl3), δ, ppm:
δ = 161.1; 154.3; 137.0; 130.0; 119.0;
114.1; 89.1; 39.5; 38.2; 37.8; 28.6; 20.1.
Mass spectrum, m/z (Irel, %): 260 [M]+ (2).
Found, %: C 69.41; H 7.89; N 10.87.
C15H20N2O2. Calculated, %: C 69.20; H
7.74; N 10.76.
Synthesis of compounds 12–17 (Gen-
eral method). The Vilsmeier–Haack reagent
was prepared from POСl3 (2.75 ml, 0.03
mol) and DMF (4.61 ml, 0.06 mol) with ice-
cooling. Compound 6 (2.82 g, 0.01 mol) was
added to the Vilsmeier–Haack reagent. The
reaction mixture was heated and stirred on a
water bath at 80°C for 1.5 h. Then the reac-
tion mixture was cooled to 10°C and treated
with an ice-cold 15% aqueous NaClO4 solu-
tion (10 ml). The precipitate of the organic
salt was filtered off, dried, and washed with
PhMe. The organic salt was dissolved in hot
DMF (5 ml). To the obtained solution, an
aqueous 15% NaOH solution (1.5 ml) was
added, and the mixture was stirred vigorous-
ly at 60–75°C for 5 min. The precipitated
solid of compound 12 was filtered off. If no
solid precipitated, the solution was cooled to
the room temperature and water was added.
For compounds 8 and 9, the reaction time
was increased to 8 h. Compounds 7, 11 were
obtained at 100°C for 11 h.
N'-(7-Bromo-3-formyl-1,2-
dihydrocyclopenta[b]chromen-9-yl)-N,N-
dimethylimidoformamide (12): Yield 67%,
yellow powder, mp 173–175˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
10.21 (1H, s, CHO); 7.61 (1H, d, 4J=2.4, H-
8 Ar); 7.38 (1H, s, CH); 7.37 (1H,
dd, 3J=8.6, 4J=2.4, H-6 Ar); 6.95 (1H,
d, 3J=8.6, H-5 Ar); 3.10 (3H, s, CH3); 3.07
(3H, s, CH3); 2.75–2.85 (2H, m, CH2), 2.50–
2.55 (2H, m, CH2). 13C NMR spectrum
(CDCl3), δ, ppm: δ = 186.6; 162.7; 153.8;
151.4; 145.5; 132.5; 126.5; 123.1; 116.8;
115.7; 113.4; 111.1; 39.5, 33.5, 23.2, 22.5.
Mass spectrum, m/z (Irel, %): 348 [M (81Br)]+
(96), 346 [M(79Br)]+ (94). Found, %: C
55.45; H 4.40; N 8.05. C16H15BrN2O2. Cal-
culated, %: C 55.35; H 4.35; N 8.07.
N'-(5,7-Dibromo-2-tert-butyl-4-formyl-
2,3-dihydro-1H-xanthen-9-yl)-N,N-
dimethylimidoformamide (13): Yield 57%,
yellow powder, mp 184–186˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm: δ = 10.33
(1H, s, CHO); 7.57 (1H, s, Ar); 7.54 (1H, s,
Ar); 7.37 (1H, s, CH); 3.10 (3H, s, CH3);
3.07 (3H, s, CH3); 2.75–2.84 (2H, m, CH2);
1.87–1.93 (2H, m, CH2); 1.77–1.80 (1H, m,
CH); 0.94 (9H, s, t-Bu). 13C NMR spectrum
(CDCl3), δ, ppm: δ = 187.2; 161.6; 153.6;
148.1; 144.4; 135.0; 125.7; 124.0; 115.5;
113.7; 112.0; 109.6; 41.5; 40.0; 34.0; 32.0;
27.2; 26.1; 22.4. Mass spectrum, m/z (Irel,
%): 496 [M]+ (100). Found, %: C 51.02; H
8.01; N 5.77. C21H24Br2N2O2. Calculated,
%: C 50.83; H 4.87; N 5.65.
Rearrangement of substituted 1,3-benzoxazines into xanthene-type compounds
118 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2
N'-(2-tert-Butyl-4-formyl-5,7-diiodo-
2,3-dihydro-1H-xanthen-9-yl)-N,N-
dimethylimidoformamide (14): Yield 48%,
yellow powder, mp 165–168˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm: δ = 10.44
(1H, s, CHO), 7.98 (1H, s, Ar), 7.73 (1H, s,
Ar), 7.34 (1H, s, CH), 3.12 (3H, s, CH3);
3.08 (3H, s, CH3); 2.77–2.85 (2H, m, CH2);
1.87–1.95 (2H, m, CH2); 1.77–1.80 (1H, m,
CH); 0.95 (9H, s, t-Bu). 13C NMR spectrum
(CDCl3), δ, ppm: δ = 187.5; 161.6; 153.4;
150.8; 146.0; 144.4; 132.5; 123.7; 113.4;
111.0; 86.5; 83.5; 41.6; 40.0; 34.0; 32.1;
27.2; 26.0; 22.5. Mass spectrum, m/z (Irel,
%): 590 [M]+ (65). Found, %: C 42.90; H
4.15; N 4.85. C21H24I2N2O2. Calculated, %:
C 42.73; H 4.10; N 4.75.
N'-[2-(1,1-Dimethylpropyl)-4-formyl-
5,7-diiodo-2,3-dihydro-1H-xanthen-9-yl]-
N,N-dimethylimidoformamide (15): Yield
60%, yellow powder, mp 155–158˚C
(EtOH). 1H NMR spectrum (CDCl3), δ, ppm:
δ = 10.43 (1H, s, CHO), 7.96 (1H, s, Ar),
7.72 (1H, s, Ar), 7.33 (1H, s, CH), 3.11 (3H,
s, CH3); 3.07 (3H, s, CH3); 2.73–2.84 (2H,
m, CH2); 1.85–1.93 (2H, m, CH2); 1.75–
1.80 (1H, m, CH); 1.32–1.40 (2H, m, CH2);
0.84 (6H, s, 2Me), 0.79 (3H, t, 3J=7.5
Hz, Me). 13C NMR spectrum (CDCl3), δ,
ppm: δ = 187.4; 161.5; 153.3; 150.7; 146.0;
144.3; 132.4; 123.6; 113.3; 111.0; 86.4;
83.4; 40.1; 39.2; 34.6; 34.3; 32.5; 25.7;
24.2; 23.9; 22.2. Mass spectrum, m/z (Irel,
%): 604 [M]+ (95). Found, %: C 43.95; H
4.45; N 4.65. C22H26I2N2O2. Calculated, %:
C 43.73; H 4.34; N 4.64.
N'-(6-Formyl-8,9,10,11-tetrahydro-7H-
cycloocta[b]chromen-12-yl)-N,N-
dimethylimidoformamide (16): Yield 47%,
yellow powder, mp 113–116˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
10.25 (1H, s, CHO); 7.48 (1H, d, 3J=7.0,
Ar); 7.35 (1H, s, CH); 7.27–7.32 (1H, m,
Ar); 7.04–7.08 (2H, m, Ar); 3.10 (3H, s,
CH3); 3.07 (3H, s, CH3); 2.60–2.63 (4H, m,
2CH2); 1.73–1.85 (6H, m, 3CH2). 13C 1H
NMR spectrum (CDCl3), δ, ppm: δ = 187.4;
167.3; 153.1; 152.4; 150.3; 130.1; 124.3;
122.6; 120.8; 116.0; 115.0; 110.5; 40.1;
34.3; 28.0; 25.9; 25.3; 19.9; 19.7. Mass
spectrum, m/z (Irel, %): 310 [M]+ (100).
Found, %: C 73.72; H 7.27; N 9.17.
C19H22N2O2. Calculated, %: C 73.52; H
7.14; N 9.09.
N'-(4-Formyl-2-propyl-2,3-dihydro-
1H-chromeno[3,2-c]pyridin-10-yl)-N,N-
dimethylimidoformamide (17): Yield 52%,
yellow powder, mp 127–130˚C (EtOH). 1H
NMR spectrum (CDCl3), δ, ppm (J, Hz): δ =
10.23 (1H, s, CHO); 7.44 (1H, d, 3J=7.0,
Ar); 7.33 (1H, s, CH); 7.27–7.30 (1H, m,
Ar); 7.02–7.06 (2H, m, Ar); 3.16–3.19 (1H,
m, CH); 3.12 (3H, s, CH3); 3.09 (3H, s,
CH3); 2.91–2.94 (1H, m, CH); 2.82–2.89
(1H, m, CH); 2.60–2.65 (1H, m, CH); 2.55–
2.59 (2H, m, CH2); 1.48–1.58 (2H, m, CH2),
0.91 (3H, t, 3J=7.5, CH3). 13C NMR spec-
trum (CDCl3), δ, ppm: δ = 185.2; 155.5;
153.5; 148.1; 144.2; 135.0; 125.5; 124.1;
115.3; 112.9; 112.1; 109.6; 45.5; 44.8; 43.8;
41.5; 40.0; 26.1; 22.4. Mass spectrum, m/z
(Irel, %): 325 [M]+ (5). Found, %: C 70.28;
H 7.20; N 13.06. C19H23N3O2. Calculated,
%: C 70.13; H 7.12; N 12.91.
Synthesis of compounds 19–23 (Gen-
eral method). A mixture of the correspond-
ing salicylamide 1, 18 (0.01 mol), aliphatic
ketone (0.012 mol), and p-TsOH·H2O (0.03
mol) in benzene (45 ml) was refluxed for 16-
18 h with continuous removal of water with
O. K. Farat, S. A. Varenichenko, E. V. Zaliznaya, V. I. Markov
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2 119
a Dean–Stark trap. Then solvent was evapo-
rated to dryness under reduced pressure, the
solid residue was washed with 5% aqueous
NaOH solution, water, and filtered off.
2-Methyl-2-propyl-2,3-dihydro-4H-1,3-
benzoxazin-4-one (19): Yield (85 %), mp
94–95ºC. 1H NMR spectrum (DMSO-d6), δ,
ppm (J, Hz): 8.62 (1H, s, NH); 7.73 (1H, d,
3J=7.3, H Ar); 7.46 (1H, t, 3J=7.3, H Ar);
7.04 (1H, t, 3J=7.3, H Ar); 6.93 (1H, d,
3J=7.8, H Ar); 1.71–1.73 (2H, m, CH2); 1.46
(3H, s, CH3); 1.36–1.38 (2H, m, CH2); 0.83
(3H, t, 3J=6.8, CH3). 13C NMR spectrum
(DMSO-d6), δ, ppm: 161.1; 155.4; 134.4;
126.9; 117.2; 116.8; 89.1; 41.5; 25.4; 16.5;
13.9. Mass spectrum, m/z (Irel, %): 205 [М]+
(20), 121 (100). Found, %: C 70.22; H 7.37;
N 6.82. C12H15NO2. Calculated, %: C 70.33;
H 7.26; N 6.69.
6,8-Diisopropyl-2-methyl-2-propyl-2,3-
dihydro-4H-1,3-benzoxazin-4-one (20):
Yield (70 %), mp 52–54ºC. 1H NMR spec-
trum (CDCl3), δ, ppm (J, Hz): 8.15 (1H, s,
NH); 7.67 (1H, s, H Ar); 7.25 (1H, s, H Ar);
3.25 (1H, sept, 3J=6.9, CH(CH3)2); 2.94 (1H,
sept, 3J=6.9, CH(CH3)2); 1.91-1.93 (2H, m,
CH2); 1.63 (3H, s, CH3); 1.56–1.58 (2H, m,
CH2); 1.28–1.30 (12H, m, CH(CH3)2); 0.98
(3H, t, J=6.8, CH3). 13C NMR spectrum
(CDCl3), δ, ppm: 163.9; 151.2; 141.5; 136.3;
129.8; 122.1; 116.3; 88.7; 42.3; 33.6; 27.1;
25.5; 23.9; 22.6; 22.3; 16.9; 14.0. Mass
spectrum, m/z (Irel, %): 289 [М]+ (9). Found,
%: C 74.70; H 9.40; N 4.84. C18H27NO2.
Calculated, %: C 74.66; H 9.26; N 4.95.
2,2-Dipropyl-2,3-dihydro-4H-1,3-
benzoxazin-4-one (21): Yield (70 %), mp
63–65ºC (mp 61–63ºC [19]). 1H NMR spec-
trum (CDCl3), δ, ppm (J, Hz): 8.61 (1H, s,
NH); 7.94 (1H, d, 3J=8.1, H Ar); 7.41 (1H, t,
3J=7.3, H Ar); 7.03 (1H, t, 3J=7.3, H Ar);
6.91 (1H, d, 3J=8.1, H Ar); 1.86–1.88 (4H,
m, 2CH2); 1.47–1.49 (4H, m, 2CH2); 0.91
(6H, m, CH3). 13C NMR spectrum (CDCl3),
δ, ppm: 163.3; 156.0; 134.3; 127.3; 121.2;
116.7; 91.2; 40.2; 16.5; 13.9. Mass spec-
trum, m/z (Irel, %): 233 [М]+ (14) 190 (100).
Found, %: C 72.07; H 8.21; N 6.00.
C14H19NO2. Calculated, %: C 72.01; H 8.34;
N 6.15.
6,8-Diisopropyl-2,2-dipropyl-2,3-
dihydro-4H-1,3-benzoxazin-4-one (22):
Yield (72 %), mp 125–126ºC. 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.74 (1H,
s, NH); 7.63 (1H, s, H Ar); 7.22 (1H, s, H
Ar); 3.22 (1H, sept, 3J=6.9, CH(CH3)2); 2.89
(1H, sept, 3J=6.9, CH(CH3)2); 1.80-1.89
(4H, m, CH2); 1.47–1.49 (4H, m, CH2);
1.25–1.27 (12H, m, CH(CH3)2); 0.92 (6H, t,
J=6.8, CH3). 13C NMR spectrum (CDCl3), δ,
ppm: 163.7; 151.2; 141.3; 136.1; 129.7;
122.1; 116.2; 90.7; 40.1; 33.6; 26.9; 24.0;
22.5; 16.7; 14.1. Mass spectrum, m/z (Irel,
%): 317 [М]+ (1). Found, %: C 75.67; H
9.84; N 4.41. C20H31NO2. Calculated, %: C
75.78; H 9.96; N 4.25.
2,2-Diethyl-6,8-diisopropyl-2,3-
dihydro-4H-1,3-benzoxazin-4-one (23):
Yield (82 %), mp 80–82ºC. 1H NMR spec-
trum (CDCl3), δ, ppm (J, Hz): 7.63 (1H, s,
NH); 7.56 (1H, s, H Ar); 7.22 (1H, s, H Ar);
3.24 (1H, sept, 3J=6.9, CH(CH3)2); 2.89 (1H,
sept, 3J=6.9, CH(CH3)2); 1.90–1.95 (4H, m,
CH2); 1.23–1.26 (12H, m, CH(CH3)2); 1.00
(6H, t, J=6.8, CH3). 13C NMR spectrum
(CDCl3), δ, ppm: 163.8; 151.2; 141.5; 136.2;
129.8; 122.1; 116.2; 91.3; 33.6; 30.3; 26.9;
24.0; 22.6; 7.7. Mass spectrum, m/z (Irel, %):
289 [М]+ (33), 260 (100). Found, %: C
74.70; H 9.40; N 4.84. C18H27NO2. Calculat-
Rearrangement of substituted 1,3-benzoxazines into xanthene-type compounds
120 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 86, No 2
ed, %: C 74.78; H 9.26; N 4.95.
Conclusion. In this work, we presented
an effective method for the synthesis of
formyl derivatives of xanthenes based on
readily available salicylamide. It was found
that (spiro[1,3-benzoxazine-2,1'-
cyclobutan]-4(3H)-one) does not rearrange
even under prolonged heating due to the
spirocycle strain. The presence of bromine
or iodine atoms at positions C-6 and C-8 of
the aromatic cycle of 1,3-benzoxazines
makes the reaction more difficult, which
requires more harsh synthesis conditions.
ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-
БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАН-
ТЕНОВОГО ТИПУ
Олег К. Фарат, Катерина В. Залізна, Світлана
А. Варениченко*, Віктор І. Марков
Український державний хіміко-
технологічний університет, 49005, Дніпро,
Україна
*е-mail: svetlanavarenichenko@gmail.com
Вивчено закономірності перегрупування но-
вих похідних 1,3-бензоксазинів, які отримано
конденсацією заміщених саліциламідів з ци-
клічними кетонами, під дією реагенту Вільс-
майєра-Хаака. Вплив кутового напруження у
4х членному спіроциклі перешкоджає пере-
групуванню спіро[1,3-бензоксазин-2,1-
циклобутан]-4(3Н)-ону під дією формілюю-
чого агенту. Похідні 1,3-бензоксазинів з роз-
мірами циклів від 5-ти до 8-и членних під
дією формілюючого агенту утворюють фор-
мілпохідні ксантенів, у яких швидкість реак-
ції залежить від наявності електронегативних
замісників у положеннях С-6 і С-8 ароматич-
ного циклу, а також у спіроциклі.
К л ю ч о в і с л о в а: перегрупування, реа-
гент Вільсмаєйра-Хаака, конденсація, 1,3-
бензоксазини, формілпохідні ксантенів.
ПЕРЕГРУППИРОВКА ЗАМЕЩЁННЫХ
1,3-БЕНЗОКСАЗИНОВ В СОЕДИНЕНИЯ
КСАНТЕНОВОГО ТИПА
Олег К. Фарат, Екатерина В. Зализная, Свет-
лана А. Варениченко*, Виктор И. Марков
Украинский государственный химико-
технологический университет, 49005, Днепр,
Украина
*е-mail: svetlanavarenichenko@gmail.com
Изучены закономерности перегруппировки
новых производных 1,3-бензоксазинов, кото-
рые получены кондесацией замещенных са-
лициламидов с циклическими кетонами, под
действием Вильсмайера-Хаака. Влияние уг-
лового напряжения в 4х членном спироцикле
препятствует перегруппировке спиро[1,3-
бензоксазин-2,1-циклобутан]-4(3Н)-она под.
действием формилирующего агента. Произ-
водные 1,3-бензоксазинов с размерами цик-
лов от 5-ти до 8-и членних под. действием
формилирующего агента образуют формил-
производные ксантенов, в которых скорость
реакции зависит от наличия электроотрица-
тельных заместителей в положеннях С-6 и С-
8 ароматического цикла, а также в спироцик-
ле.
К л ю ч е в ы е с л о в а: перегруппировка,
реагент Вильсмайера-Хаака, конденсация,
1,3-бензоксазины, формилпроизводные ксан-
тенов.
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mailto:svetlanavarenichenko@gmail.com
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Received 31.01.2020
https://www.ncbi.nlm.nih.gov/pubmed/13357338
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-124 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:01:34Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/40/d5424fa1412c54d9f1d038463fa3a840.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1242026-07-22T08:23:42Z REARRANGEMENT OF SUBSTITUTED 1,3-BENZOXAZINES INTO XANTHENE-TYPE COMPOUNDS ПЕРЕГРУППИРОВКА ЗАМЕЩЁННЫХ 1,3-БЕНЗОКСАЗИНОВ В СОЕДИНЕНИЯ КСАНТЕНОВОГО ТИПА ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ Farat, Oleg Varenichenko, Svetlana Zaliznaya, Ekaterina Markov, Victor rearrangement, Vilsmeier–Haack reagent, condensation, 1,3-benzoxazine, xanthene derivatives. The rearrangement patterns of new 1,3-benzoxazines derivatives obtained by condensation of substituted salicylamides with cyclic ketones under the influence of Vilsmeier-Haack reagent has been studied. The influence of angel strain in a 4-membered spirocycle prevents the rearrangement of spiro [1,3-benzoxazine-2,1'-cyclobutan]-4(3H)-one under the action of a formylating agent. 1,3-Benzoxazines derivatives with ring sizes from 5- to 8-membered under the action of a formylating agent have formed formylxanthene derivative. Their formation reaction rate depends on the presence of electronegativity substituents at positions C-6 and C-8 of the aromatic cycle, as well as in the spiroring. In this work, we presented an effective method for the synthesis of formyl derivatives of xanthenes based on readily available salicylamide. It was found that (spiro[1,3-benzoxazine-2,1'-cyclobutan]-4(3H)-one) does not rearrange even under prolonged heating due to the spirocycle strain. The presence of bromine or iodine atoms at positions C-6 and C-8 of the aromatic cycle of 1,3-benzoxazines makes the reaction more difficult, which requires more harsh synthesis conditions. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-02-05 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/124 10.33609/0041-6045.86.2.2020.111-122 Ukrainian Chemistry Journal; Vol. 86 No. 2 (2020): Ukrainian Chemistry Journal; 111-122 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 2 (2020): Украинский химический журнал; 111-122 Український хімічний журнал; Том 86 № 2 (2020): Український хімічний журнал; 111-122 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/124/79 Copyright (c) 2020 Oleg Farat, Svetlana Varenichenko, Ekaterina Zaliznaya, Victor Markov https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Farat, Oleg Varenichenko, Svetlana Zaliznaya, Ekaterina Markov, Victor ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ |
| title | ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ |
| title_alt | REARRANGEMENT OF SUBSTITUTED 1,3-BENZOXAZINES INTO XANTHENE-TYPE COMPOUNDS ПЕРЕГРУППИРОВКА ЗАМЕЩЁННЫХ 1,3-БЕНЗОКСАЗИНОВ В СОЕДИНЕНИЯ КСАНТЕНОВОГО ТИПА |
| title_full | ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ |
| title_fullStr | ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ |
| title_full_unstemmed | ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ |
| title_short | ПЕРЕГРУПУВАННЯ ЗАМІЩЕНИХ 1,3-БЕНЗОКСАЗИНІВ В СПОЛУКИ КСАНТЕНОВОГО ТИПУ |
| title_sort | перегрупування заміщених 1,3-бензоксазинів в сполуки ксантенового типу |
| topic_facet | rearrangement Vilsmeier–Haack reagent condensation 1,3-benzoxazine xanthene derivatives. |
| url | https://ucj.org.ua/index.php/journal/article/view/124 |
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