Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних
This investigation focuses on the synthesis of spiropyranoneoflavones and the modification of obtained compounds at the exocyclic oxygen atom. Kabbe cyclization of 6-acetyl-7‑hydroxy-8-methyl-4-phenyl-2H-chromene-2-one with cyclohexanone or cyclopentanone in the presence of pyrrolidine provided 10-m...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2021
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Ukrainica Bioorganica Acta| _version_ | 1871193554739527680 |
|---|---|
| author | Moskvina, Viktoria S. Turov, Olexander V. Shokol, Tetyana V. Khilya, Volodymyr P. |
| author_facet | Moskvina, Viktoria S. Turov, Olexander V. Shokol, Tetyana V. Khilya, Volodymyr P. |
| author_institution_txt_mv | [
{
"author": "Viktoria S. Moskvina",
"institution": "Taras Shevchenko National University of Kyiv, 60 Volodymyrska St., Kyiv, 01601, Ukraine; V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the NAS of Ukraine, 1 Murmanska St., Kyiv, 02094, Ukraine"
},
{
"author": "Olexander V. Turov",
"institution": "Taras Shevchenko National University of Kyiv, 60 Volodymyrska St., Kyiv, 01601, Ukraine"
},
{
"author": "Tetyana V. Shokol",
"institution": "Taras Shevchenko National University of Kyiv, 60 Volodymyrska St., Kyiv, 01601, Ukraine"
},
{
"author": "Volodymyr P. Khilya",
"institution": "Taras Shevchenko National University of Kyiv, 60 Volodymyrska St., Kyiv, 01601, Ukraine"
}
] |
| author_sort | Moskvina, Viktoria S. |
| baseUrl_str | https://bioorganica.com.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-19T14:56:53Z |
| description | This investigation focuses on the synthesis of spiropyranoneoflavones and the modification of obtained compounds at the exocyclic oxygen atom. Kabbe cyclization of 6-acetyl-7‑hydroxy-8-methyl-4-phenyl-2H-chromene-2-one with cyclohexanone or cyclopentanone in the presence of pyrrolidine provided 10-methyl-4-phenyl-2H-spiro[cyclohexane(cyclopentane)-1’,8-pyrano[3,2-g]chromene]-2,6(7H)-diones. Their new functionalized derivatives with thiosemicarbazide residues were synthesized. Acetylation of obtained thiosemicarbazones with acetic anhydride proceeded via cyclization of thiosemicarbazide fragment into 1,3,4-thiadiazole ring to give corresponding N-[3'-acetyl-10-methyl-8-oxo-6-phenyl-3'H,8H-dispiro[cyclohexane-1,2’-pyrano[3,2-g]chromene-4,2'-[1,3,4]thiadiazol]-5'-yl]acetamide and N-[3'-acetyl-10-methyl-8-oxo-6-phenyl-3'H,8H-dispiro[cyclopentane-1,2’-pyrano[3,2-g]chromene-4,2'-[1,3,4]thiadiazol]-5'-yl]acetamide. The structure of the obtained compounds was confirmed by NMR spectroscopy |
| doi_str_mv | 10.15407/bioorganica2021.02.018 |
| first_indexed | 2025-07-17T12:19:30Z |
| format | Article |
| fulltext |
ISSN 1814-9758. Ukr. Bioorg. Acta, 2021, Vol. 16, N 2
UDC 547.813+547.814+547.794.3
DOI: https://doi.org/10.15407/bioorganica2021.02.018
18
Ukrainica Bioorganica Acta
www.bi oorgan ica .org .ua
RESEARCH ARTICLE
Synthesis and NMR spectroscopy investigations of functionalized
spiropyranochromenediones and their spirothiadiazole derivatives
Viktoria S. Moskvina1,2*, Olexander V. Turov1, Tetyana V. Shokol1, Volodymyr P. Khilya1
1 Taras Shevchenko National University of Kyiv, 60 Volodymyrska St., Kyiv, 01601, Ukraine
2 V. P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the NAS of Ukraine, 1 Murmanska St., Kyiv, 02094, Ukraine
Abstract: This study discusses the synthesis of spiropyranoneoflavones and the modification of obtained compounds at the exocyclic
oxygen atom. Kabbe cyclization of 6-acetyl-7-hydroxy-8-methyl-4-phenyl-2H-chromene-2-one with cyclohexanone or cyclopentanone in
the presence of pyrrolidine provided 10'-methyl-6'-phenyl-8'H-spiro[cyclohexane(cyclopentane)-1,2'-pyrano[3,2-g]chromene]-4',8'(3'H)-
diones. Their new functionalized derivatives with thiosemicarbazide residues were synthesized. Acetylation of obtained thio-
semicarbazones with acetic anhydride proceeded via cyclization of thiosemicarbazide fragment into 1,3,4-thiadiazole ring to
give corresponding N-[3''-acetyl-10'-methyl-8'-oxo-6'-phenyl-3'H,3''H,8'H-dispiro[cyclohexane-1,2'-pyrano[3,2-g]chromene-4',2''-[1,3,4]-
thiadiazol]-5''-yl]acetamide and N-[3''-acetyl-10'-methyl-8'-oxo-6'-phenyl-3'H,3''H,8'H-dispiro[cyclopentane-1,2'-pyrano[3,2-g]chromene-
4',2''-[1,3,4]thiadiazol]-5''-yl]acetamide. The structure of the obtained compounds was confirmed by NMR spectroscopy.
Keywords: spiro compounds; neoflavones; spiropyranochromenediones; NMR spectroscopy; heteronuclear correlation.
Introduction
Derivatives of 4-phenylcoumarin, also known as
neoflavones, are a research topic of significant interest.
Neoflavones are common in plants – as of today, more than
160 compounds of this class have been obtained from
natural sources [1] - and both natural neoflavones and their
synthetic analogs demonstrate a wide range of biological
activities, including antitumor [2], cytotoxic [3], antioxidant
[4], antibacterial [5, 6], insecticidal [7], and many others.
In this study, we discuss the synthesis of
spiropyranoneoflavone derivatives, the modification of
obtained compounds at the exocyclic oxygen atom, and the
confirmation of their structure with NMR spectroscopy
data.
Received:
Revised:
Accepted:
Published online:
08.09.2021
22.09.2021
04.11.2021
30.12.2021
Corresponding author. Tel.: +380-66-791-0921;
e-mail: v.moskvina@gmail.com (V. S. Moskvina)
ORCID: 0000-0001-5556-9147
Two common synthetic approaches to the synthesis of
pyranocoumarins exist: coumarin ring formation in a pyran
system, and pyran ring formation in a coumarin system.
Earlier, we have obtained spirodihydropyranocoumarins via
Pechmann condensation of 3,4-dihydrospirocyclohexane-
chomane-7-ol [8]. 4-Phenylcoumarin with a fused
dimethylpyran ring was synthesized through Kabbe
cyclization of 6-acetyl-7-hydroxy-8-methylneoflavone with
acetone [9].
Results and Discussion
In this study, we used Kabbe cyclization of 6-acetyl-7-
hydroxy-8-methyl-4-phenyl-2H-chromene-2-one (1) with
cyclohexanone and cyclopentanone in the presence of
pyrrolidine to obtain the corresponding linear
spiropyranoneoflavones 2 and 3 (Scheme 1).
The subsequent heating of compounds 2, 3 with thio-
semicarbazide led to thiosemicarbazones 4, 5. The substi-
tution takes place at the exocyclic oxygen atom of the
spiropyran ring, and not the benzopyran-2-one system, even
in the presence of a threefold excess of the nucleophilic
reagent. Acetylation of thiosemicarbazones 4, 5 proceeds
via cyclization of thiosemicarbazide fragment into
© Moskvina V. S. et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and source are credited.
V. S. Moskvina, O. V. Turov et al.
19
Scheme 1. The synthesis of linear spiropyranoneoflavones 2 and 3.
Scheme 2. The synthesis of spirothiadiazole derivatives of spiropyranoneoflavones 6 and 7.
Table 1. 1H chemical shifts (δ/ppm) of compounds 2-7 in DMSO-d6.
No H-3'a H-5'a 7'-CH2 8'-(CH2)n
c 10'-CH3
a H-2′', 6''b H-3′', 4'', 5''c Other signals
2 6.22 7.69 2.72a 1.56-1.96j 2.35 7.44 7.57 –
3 6.22 7.57 2.86a 1.69-2.01i 2.29 7.45 7.46 –
4 6.17 7.94 2.88a 1.61-1.83j 2.31 7.51 7.57 7.06 (s, NH), 8.22 (s, NH), 10.52 (s, NH)
5 6.18 7.95 3.00a 1.73-1.90i 2.26 7.51 7.55 7.08 (s, NH), 8.21 (s, NH), 10.48 (s, NH)
6 6.23 7.26 2.55d,
3.16e,f
1.48-1.88j 2.25 7.39 7.53 2.06 (s, AcN-TDA), 1.99 (s, AcNH-TDA),
11.64 (s, NH)
7 6.13 7.25 2.40d,
3.55e,f
1.75-1.85i 2.25 7.40 7.55
2.00 (s, AcN-TDA), 2.08 (s, AcNH-TDA),
11.50 (s, NH)
a s.; b d., J = 8.8 Hz; c m.; d pro-S; e pro-R; f 2×d., J = 14.0 Hz; j n = 5; i n = 4
Table 2. 13C chemical shifts (δ/ppm) of compounds 2-7 in DMSO-d6.
No C-2' C-3' C-4' C-4a' C-5' C-5a' C-6' C-7' C-8' C-9a' C-10' C-10a'
2 160.8 112.7 155.4 111.6 123.2 116.9 196.8 49.8 78.4 156.4 119.0 155.4
3 160.4 112.6 155.2 111.4 123. 116.7 196.5 49.5 78.6 156.1 119.1 155.4
4 159.9 112.8 155.4 111.8 123.6 113.9 146.5 36.1 78.3 156.8 119.2 153.4
5 150.0 112.7 155.4 111.6 123.9 112.9 146.5 34.6 78.1 153.3 119.2 153.4
6 160.4 112.4 155.3 113.5 123.4 122.7 74.2 44.9 77.6 153.7 113.5 152.8
7 160.8 112.5 155.4 111.6 123.8 121.7 74.2 44.8 77.4 153.5 118.9 153.2
No 8'-(CH2)n 10'-CH3 C-1'' C-2'',6'' C-3'',5'' C-4'' Other signals
2 37.7, 34.5, 23.8, 22.4, 21.2 8.6 140.0 126.4 129.5 130.1 –
3 37.9, 34.5, 23.6, 21.9 8.6 140.0 126.6 128.9 130.1 –
4 37.3, 35.6, 24.1, 22.6, 21.3 8.9 134.2 128.9 128.7 130.4 181.3 (C=S)
5 38.4, 36.5, 24.6, 21.1 8.6 136.1 128.4 128.6 130.3 181.3 (C=S)
6 37.8, 33.3, 24.7, 22.0, 21.1 8.8 135.6 129.1 129.5 130.6 23.0, 167.8 (Ac), 22.0, 170.2
(AcNH), 143.7 (TDA-C-5)
7 38.6, 34.1, 23.6, 21.3 8.9 136.3 129.1 129.7 130.4 23.1, 168.3 (Ac), 22.7, 171.4
(AcNH), 144.3 (TDA-C-5)
ISSN 1814-9758. Ukr. Bioorg. Acta, 2021, Vol. 16, N 2
20
1,3,4-thiadiazole ring, and gives corresponding N-[3''-
acetyl-10'-methyl-8'-oxo-6'-phenyl-3'H,3''H,8'H-dispiro[cy-
clohexane-1,2'-pyrano[3,2-g]chromene-4',2''-[1,3,4]thiadia-
zol]-5''-yl]acetamide (6) and N-[3''-acetyl-10'-methyl-8'-
oxo-6'-phenyl-3'H,3''H,8'H-dispiro[cyclopentane-1,2'-pyra-
no[3,2-g]chromene-4',2''-[1,3,4]thiadiazol]-5''-yl]-acetamide
(7) (Scheme 2).
Table 3. Heteronuclear correlation data for compound 6.
1H
NMR
signal,
δ/ppm
13C NMR signals which correlate with 1H
NMR signal, δ/ppm
HMQC HMBC
1.55 21.7
1.48-1.65 22.0 24.7, 44.9, 77.6, 153.7
24.7
1.65-1.88 33.3 143.7, 170.2
37.8
1.99 22.0 170.2, 143.7
2.06 23.0 167.8
2.25 8.8 153.7, 152.8, 123.4, 113.5
2.55 44.9 123.4, 74.2
3.16 44.9 77.6, 74.2, 37.8, 33.3
6.23 112.4 160.4, 135.6, 112.4, 123.4
7.26 123.4 155.3, 153.7, 152.8, 123.4, 113.5, 74.2
7.39 129.1 155.3, 130.6, 129.1
7.53 129.5, 130.6 135.6, 129.5, 129.1
11.64 – 170.2, 143.7
1H and 13C NMR spectra were measured to confirm the
structures of obtained compounds. 1H NMR spectra (Table
1) of compounds 2-7 match the assumed structures;
however, due to their relative complexity and instability of
lactone derivatives toward nucleophilic reagent, 13C NMR
spectra were measured (Table 2).
In 13C NMR spectra of compounds 2, 3, signals at 196.8-
196.5 ppm are attributed to the C-6 atom; this carbon atom
is observed at 146.5 ppm for compounds 4, 5, and at 77.4-
78.6 ppm for compounds 2-7, which is typical for a
spirocarbon (C-8). The second spirocyclic carbon in
compounds 6, 7 gives a signal at 74.2 ppm. Cyclohexane or
cyclopentane ring gives a wide signal in 1H NMR spectra at
1.48-2.01 ppm. A less expressed correlation of C-7 atom's
chemical shift with the nature of the exocyclic substituent at
C-6 can also be observed (Table 2). 1H and 13C NMR
spectra of remaining elements of molecules 2-7 are only
slightly affected by the substituent at C-6, but even though
the spectra do not contradict the proposed structures, a
reliable correlation of signals cannot be established. It
becomes possible after 2D heteronuclear 1H-13C correlation
experiments: via one bond (HMQC) and 2-3 bonds
(HMBC). Table 3 summarizes cross-peak coordinates,
found in HMQC and HMBC spectra of the compound 6.
A scheme below shows the assignments and the most
important HMBC correlations upon which the assignments
were based (Figure 1).
Figure 1. The principal HMBC correlations for compound 6.
Conclusions
To summarize, we have demonstrated an easy and
effective approach to the synthesis of 10-methyl-4-phenyl-
2H-spiro[cyclohexane(or cyclopentane)-1',8-pyrano-[3,2-
g]chromene]-2,6(7H)-diones via condensation of 6-acetyl-
7-hydroxyneoflavone with cyclohexanone and cyclo-
pentanone. The further reaction of spiropyranoneoflavones
with thiosemicarbazide led to the obtainment of
thiosemicarbazones. It is worth noting that only C-6
position, and not C-2 position, was affected in the course of
the reaction. Acetylation of thiosemicarbazones led to the
synthesis of dispiro[cyclohexane(or cyclopentane)-1',8-
pyrano[3,2-g]chromene-4',6-[1,3,4]thiadiazol]-5'-yl]aceta-
mides. The structure of obtained compounds was confirmed
by 1H and 13C NMR spectra data of two-dimensional 1H-13C
shift correlation experiments via one bond and multiple
bonds.
Experimental section
Reaction flow and identity of obtained compounds were
controlled with TLC on Merck F254 plates using
chloroform:methanol (9:1, v/v) and (95:5, v/v) systems as
eluents. Melting points were determined using a Kofler-type
Leica Galen III micro hot stage microscope. NMR spectra
were recorded on a Mercury-400 spectrometer
(spectrometer frequency for 1H: 400 MHz, 13C: 100 MHz)
from DMSO-d6 solutions. The TMS signal was used as an
internal standard. HMQC spectra were acquired as 128×32
data matrices with spectral ranges: for 1H – 4 kHz, for 13C –
21 kHz; mixing time corresponds to 1JCH = 140 Hz. HMBC
spectra were acquired as 400×32 data matrices with spectral
ranges: for 1H – 4 kHz, for 13C – 21 kHz; mixing time
corresponds to 2-3JCH = 8 Hz. Spectra were measured with
detection on protons and gradient selection of signals.
V. S. Moskvina, O. V. Turov et al.
21
Elemental analyses for C, H, and N were conducted using
Perkin-Elmer C, H, N Analyzer. Their results were found to
be in good agreement (± 0.2%) with the calculated values.
Mass spectra were recorded on Agilent 1100 LC/MSD
instrument with chemical ionization (CI).
6-Acetyl-7-hydroxy-8-methyl-4-phenyl-2H-chromene-2-
one (1) was synthesized earlier [10].
General procedure for the preparation of
spiropyranoneoflavones (2, 3).
To a solution of 2.94 g of 1 (10 mmol) in 20 ml
acetonitrile, 2.0 ml pyrrolidine (25 mmol) and 7 mmol of a
corresponding ketone (cyclohexanone, 7.2 ml; cyclopenta-
none, 5.8 ml) were added. The reaction mixture was kept at
45 °C for 8 h (the reaction completeness was monitored
with TLC). The resulting solution was diluted with ice H2O,
acidified to pH 5 and filtered. Recrystallization from
acetonitrile afforded the product.
10'-Methyl-6'-phenyl-8'H-spiro[cyclohexane-1,2'-pyra-
no[3,2-g]chromene]-4',8'(3'H)-dione (2, C24H22O4).
Yield 2.93 g (78.2%), mp 246-248 °C.
1H NMR spectra are shown in Table 1.
13C NMR spectra are shown in Table 2.
MS m/z 375.4 [M+H]+.
10'-Methyl-6'-phenyl-8'H-spiro[cyclopentane-1,2'-
pyrano[3,2-g]chromene]-4',8'(3'H)-dione (3, C23H20O4).
Yield 1.56 g (43.3%), mp 201-202 °C.
1H NMR spectra are shown in Table 1.
13C NMR spectra are shown in Table 2.
MS m/z 361.4 [M+H]+.
General procedure for the preparation of 10-methyl-
4-phenyl-2H-spiro[cyclohexane(cyclopentane)-1’,8-pyrano-
[3,2-g]chromene]-2,6(7H)-dione thiosemicarbazones (4, 5).
To a solution of a corresponding compound 2 or 3
(3 mmol) in 10 ml ethanol, an alcoholic solution of 3.5
mmol of a thiosemicarbazide with 1 ml HCl was added
dropwise. The reaction mixture was kept on a water bath for
3-5 h. The formed precipitate was filtered and crystallized
from propan-2-ol.
(E/Z)-2-(10'-methyl-8'-oxo-6'-phenyl-8'H-spiro[cyclo-
hexane-1,2'-pyrano[3,2-g]chromen]-4'(3'H)-ylidene)-hyd-
razine-1-carbothioamide (4, C25H25N3O3S).
Yield: 1.24 g (86.8%), mp 258-259 °C.
1H NMR spectra are shown in Table 1.
13C NMR spectra are shown in Table 2.
MS m/z 448.6 [M+H]+.
(E/Z)-2-(10'-methyl-8'-oxo-6'-phenyl-8'H-spiro[cyclo-
pentane-1,2'-pyrano[3,2-g]chromen]-4'(3'H)-ylidene)-hyd-
razine-1-carbothioamide (5, C24H23N3O3S).
Yield: 1.14 g (93.4%), mp 244-246 °C.
1H NMR spectra are shown in Table 1.
13C NMR spectra are shown in Table 2.
MS m/z 434.5 [M+H]+.
General procedure for the preparation of N-[3'-
acetyl-10-methyl-2-oxo-4-phenyl-3'H,2H-dispiro[cyclo-
hexane(cyclopentane)-1’,8-pyrano[3,2-g]chromene-4’,6-
[1,3,4]thiadiazol]-5'-yl]acetamides (6, 7).
A solution of 1 mmol of a corresponding thiosemi-
carbazone 4, 5 in 10 ml acetic anhydride was refluxed at a
water bath for 6-7 h. The reaction mixture was left to cool
to room temperature and then poured on ice. The formed
precipitate was filtered and crystallized from aqueous
propan-2-ol (20:80, v/v).
N-(3''-acetyl-10'-methyl-8'-oxo-6'-phenyl-3'H,3''H,8'H-
dispiro[cyclohexane-1,2'-pyrano[3,2-g]chromene-4',2''-
[1,3,4]thiadiazol]-5''-yl)acetamide (6, C29H29N3O5S).
Yield: 0.45 g (80.8%), mp 204-206 °С.
1H NMR spectra are shown in Table 1.
13C NMR spectra are shown in Table 2.
MS m/z 532.6 [M+H]+.
N-(3''-acetyl-10'-methyl-8'-oxo-6'-phenyl-3'H,3''H,8'H-
dispiro[cyclopentane-1,2'-pyrano[3,2-g]chromene-4',2''-
[1,3,4]thiadiazol]-5''-yl)acetamide (7, C28H27N3O5S).
Yield: 0.16 g (42.0%), mp 196-198 °C.
1H NMR spectra are shown in Table 1.
13C NMR spectra are shown in Table 2.
MS m/z 518.5 [M+H]+.
Notes
Acknowledgments and finances. This work has been
supported by Ministry of Education and Science of Ukraine:
Grant of the Ministry of Education and Science of Ukraine
for perspective development of a scientific direction
"Mathematical sciences and natural sciences" at Taras
Shevchenko National University of Kyiv.
The authors declare no conflict interest.
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Синтез та дослідження ЯМР спектроскопії функціоналізованих
спіропіранохромендіонів та їх спіротіадіазольних похідних
В. С. Москвіна1, 2*, О.В. Туров1, Т. В. Шокол1, В. П. Хиля1
1 Київський національний університет імені Тараса Шевченка, вул. Володимирська, 60, Київ, 01601, Україна
2 Інститут біоорганічної хімії та нафтохімії ім. В. П. Кухаря НАН України, вул. Мурманська, 1, Київ, 02094, Україна
Резюме: Дослідження присвячено синтезу спіропіранонеофлавонів та проведенню модифікації отриманих сполук за екзоциклічним атомом
Оксигену. Циклізація Каббе 6-ацетил-7-гідрокси-8-метил-4-феніл-2Н-хромен-2-ону з циклогекссаноном або циклопентаноном в присутності
піролідину завершувалась отриманням 10'-метил-6'-феніл-8'H-спіро[циклогексан(циклопентан)-1,2'-пірано-[3,2-g]хромен]-4',8'(3'H)-діонів. Також
отримані їх нові функціоналізовані похідні з залишком тіосемікарбазиду. Наступне ацетилювання отриманих тіосемікарбазонів в оцтовому
ангідриді супроводжувалось циклізацією тіосемікарбазидного фрагменту в 1,3,4-тіадіазольний цикл та завершувалось отриманням N-[3''-ацетил-
10'-метил-8'-оксо-6'-феніл-3'H,3''H,8'H-диспіро[циклогексан-1,2'-пірано[3,2-g]хромен-4',2''-[1,3,4]тіадіазол]-5''-іл]ацетаміду та N-[3''-ацетил-10'-
метил-8'-оксо-6'-феніл-3'H,3''H,8'H-диспіро[циклопентан-1,2'-пірано[3,2-g]хромен-4',2''-[1,3,4]тіадіазол]-5''-іл]ацетаміду відповідно. Будова
отриманих сполук доведена методами ЯМР спектроскопії.
Ключові слова: спіропохідні; неофлавоноїди; спіропіранохромендіони; спектроскопія ЯМР; гетероядерна кореляція.
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| id | oai:ojs2.bioorganica.com.ua:article-22 |
| institution | Ukrainica Bioorganica Acta |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-20T01:00:34Z |
| publishDate | 2021 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | bioorganicacomua/30/77aad4c08da7f4d4b545835f9bc74430.pdf |
| spelling | oai:ojs2.bioorganica.com.ua:article-222026-07-19T14:56:53Z Synthesis and NMR spectroscopy investigations of functionalized spiropyranochromenediones and their spirothiadiazole derivatives Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних Moskvina, Viktoria S. Turov, Olexander V. Shokol, Tetyana V. Khilya, Volodymyr P. spiro compounds neoflavones spiropyranochromenediones NMR spectroscopy heteronuclear correlation спіропохідні неофлавоноїди спіропіранохромендіони спектроскопія ЯМР гетероядерна кореляція This investigation focuses on the synthesis of spiropyranoneoflavones and the modification of obtained compounds at the exocyclic oxygen atom. Kabbe cyclization of 6-acetyl-7‑hydroxy-8-methyl-4-phenyl-2H-chromene-2-one with cyclohexanone or cyclopentanone in the presence of pyrrolidine provided 10-methyl-4-phenyl-2H-spiro[cyclohexane(cyclopentane)-1’,8-pyrano[3,2-g]chromene]-2,6(7H)-diones. Their new functionalized derivatives with thiosemicarbazide residues were synthesized. Acetylation of obtained thiosemicarbazones with acetic anhydride proceeded via cyclization of thiosemicarbazide fragment into 1,3,4-thiadiazole ring to give corresponding N-[3'-acetyl-10-methyl-8-oxo-6-phenyl-3'H,8H-dispiro[cyclohexane-1,2’-pyrano[3,2-g]chromene-4,2'-[1,3,4]thiadiazol]-5'-yl]acetamide and N-[3'-acetyl-10-methyl-8-oxo-6-phenyl-3'H,8H-dispiro[cyclopentane-1,2’-pyrano[3,2-g]chromene-4,2'-[1,3,4]thiadiazol]-5'-yl]acetamide. The structure of the obtained compounds was confirmed by NMR spectroscopy Дослідження присвячено синтезу спіропіранонеофлавонів та проведенню модифікації отриманих сполук за екзоциклічним атомом Оксигену. Циклізація Каббе 6-ацетил-7-гідрокси-8-метил-4-феніл-2Н-хромен-2-ону з циклогекссаноном або циклопентаноном в присутності піролідину завершувалась отриманням 10'-метил-6'-феніл-8'H-спіро[циклогексан(циклопентан)-1,2'-пірано-[3,2-g]хромен]-4',8'(3'H)-діонів. Також отримані їх нові функціоналізовані похідні з залишком тіосемікарбазиду. Наступне ацетилювання отриманих тіосемікарбазонів в оцтовому ангідриді супроводжувалось циклізацією тіосемікарбазидного фрагменту в 1,3,4-тіадіазольний цикл та завершувалось отриманням N-[3''-ацетил-10'-метил-8'-оксо-6'-феніл-3'H,3''H,8'H-диспіро[циклогексан-1,2'-пірано[3,2-g]хромен-4',2''-[1,3,4]тіадіазол]-5''-іл]ацетаміду та N-[3''-ацетил-10'-метил-8'-оксо-6'-феніл-3'H,3''H,8'H-диспіро[циклопентан-1,2'-пірано[3,2-g]хромен-4',2''-[1,3,4]тіадіазол]-5''-іл]ацетаміду відповідно. Будова отриманих сполук доведена методами ЯМР спектроскопії V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2021-12-27 Article Article application/pdf https://bioorganica.com.ua/index.php/journal/article/view/22 10.15407/bioorganica2021.02.018 Ukrainica Bioorganica Acta; Vol. 16 No. 2 (2021): Ukrainica Bioorganica Acta; 18-22 Ukrainica Bioorganica Acta; Том 16 № 2 (2021): Ukrainica Bioorganica Acta; 18-22 1814-9766 1814-9758 10.15407/bioorganica2021.02 en https://bioorganica.com.ua/index.php/journal/article/view/22/26 Copyright (c) 2021 Viktoria S. Moskvina, Olexander V. Turov, Tetyana V. Shokol, Volodymyr P. Khilya https://creativecommons.org/licenses/by/4.0 |
| spellingShingle | спіропохідні неофлавоноїди спіропіранохромендіони спектроскопія ЯМР гетероядерна кореляція Moskvina, Viktoria S. Turov, Olexander V. Shokol, Tetyana V. Khilya, Volodymyr P. Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| title | Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| title_alt | Synthesis and NMR spectroscopy investigations of functionalized spiropyranochromenediones and their spirothiadiazole derivatives |
| title_full | Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| title_fullStr | Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| title_full_unstemmed | Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| title_short | Синтез та дослідження ЯМР спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| title_sort | синтез та дослідження ямр спектроскопії функціоналізованих спіропіранохромендіонів та їх спіротіадіазольних похідних |
| topic | спіропохідні неофлавоноїди спіропіранохромендіони спектроскопія ЯМР гетероядерна кореляція |
| topic_facet | spiro compounds neoflavones spiropyranochromenediones NMR spectroscopy heteronuclear correlation спіропохідні неофлавоноїди спіропіранохромендіони спектроскопія ЯМР гетероядерна кореляція |
| url | https://bioorganica.com.ua/index.php/journal/article/view/22 |
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