Synthesis of Cyclic Derivatives of Carbonyl Compounds of Furan Series

Article abstract of DOI:10.1134/S1070363219120028

Cyclic acetals of furan aldehydes (furfural, 5-hydroxymethylfuran-2-carbaldehyde and furan-2,5-dicarbaldehyde) and alcohols (ethylene glycol and 2-sulfanylethanol) were synthesized. The effect of the ratio of the starting reagents on the yield of acetals obtained was studied.

Full text of DOI:10.1134/S1070363219120028

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 12, pp. 2341–2344. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 12, pp. 1816–1819.
Synthesis of Cyclic Derivatives of Carbonyl Compounds
of Furan Series
a,
a
a
a
G. Z. Raskildina *, Yu. G. Borisova , Sh. Sh. Dzhumaev , and S. S. Zlotsky
a
Ufa State Petroleum Technical University, Ufa, 450062 Russia
*
e-mail: graskildina444@mail.ru
Received June 8, 2019; revised June 8, 2019; accepted June 13, 2019
Abstract—Cyclic acetals of furan aldehydes (furfural, 5-hydroxymethylfuran-2-carbaldehyde and furan-2,5-
dicarbaldehyde) and alcohols (ethylene glycol and 2-sulfanylethanol) were synthesized. The effect of the ratio of
the starting reagents on the yield of acetals obtained was studied.
Keywords: cyclic acetals, furfural, 5-hydroxymethylfuran-2-carbaldehyde, furan-2,5-dicarbaldehyde, ethylene
glycol, 2-sulfanylethanol
DOI: 10.1134/S1070363219120028
Furfural, 5-hydroxymethylfuran-2-carbaldehyde and
their derivatives are formed as the main products of the
pentosans processing. They are widely used in small-scale
chemistry, fine organic synthesis and for the production
of polymeric materials and drugs [1–6]. The synthesis
of biodegradable oligoesters and polyesters as well as
amides based on 5-hydroxymethylfuran-2-carbaldehyde
and furan-2,5-dicarboxylic acid has been described earlier
6-fold molar excess of glycol 4 (80°C) in the presence of
p-toluenesulfonic acid, 90% conversion of the starting
dialdehyde 3 was achieved in 3.5 h, the maximum yield
of monoacetal 7 (75%) was observed after 2 h. For the
formation of diacetal 8 with a yield of more than 70%,
at least 6 h are required.
Condensation of dialdehyde 3 with 2-sulfanyl ethanol
9 at an equimolar reagent ratio led to the formation of
mono- (10) and bicyclic (11) reaction products (Scheme 2).
The maximum yield (90%) of compound 11 was achieved
with a molar ratio of reactants 3 : 9 = 1 : 4 for 5 h.
[7]. Furan-2,5-dicarbaldehyde is used to obtain various
bisamines and polyamides [8, 9]. The use of 5-hydroxy-
methylfuran-2-carbaldehyde and furan-2,5-dicarbalde-
hyde for the alkylation of aromatic hydrocarbons makes
it possible to obtain polycyclic compounds important in
the synthesis of biologically active preparations [10].
We compared the activity of glycol 4 and 2-sulfa-
nyl ethanol 9 in the reaction with dialdehyde 3 by the
method of competitive reactions. At the initial stages,
when mainly mono derivatives 7 and 10 are formed,
judging by their yields, ethylene glycol 4 is 1.5 times
Herein, we reported the synthesis of cyclic acetals of
some carbonyl compounds of the furan series. The acid-
catalyzed reaction of furfural 1 and 5-hydroxymethylfu-
ran-2-carbaldehyde 2 with an excess of ethylene glycol 4
in non-polar solvents (with water removal by the Dean–
Stark method) led to the formation of the corresponding
1
,3-dioxolanes 5, 6 with quantitative yield (Scheme 1).
Furan-2,5-dicarbaldehyde 3 reacted with an equimo-
lar amount of glycol 4 to form mono- (7) and diacetal
8) in a 6 : 1 ratio. When using a 6-fold excess of diol
, compound 8 was isolated as the main condensation
product. The Figure shows the kinetic curves of the con-
sumption of the starting dialdehyde 3 and the accumula-
tion of mono- (7) and diacetal (8). Thus, when using a
(
4
Time, h
The kinetic curves of the consumption of furan-2,5-dicarb-
aldehyde 3 (1) and the accumulation of mono- 7 (2) and
diacetal 8 (3) in the reaction with glycol 4 (molar ratio 3 : 4 =
1
: 6, 80°C).
2
341

2342
RASKILDINA et al.
Scheme 1.
R
O
O
O
HO
O
+
H
O
H+
R
OH
5, 6
O
O
1
–3
4
R
O
O
O
O
O
O
7
8
R = H (1, 5), CH OH (2, 6), CHO (3, 7).
2
Scheme 2.
O
O
HS
H
H
O
O
+
S
O
OH
O
H
3
4
10
S
O
O
S
O
11
more active than 2-sulfanyl ethanol 9 (initial reagent ratio
diyl-1,3-dioxolane was the main product, when using a
6-fold excess of 1,2-ethanediol with respect to dialdehyde.
Ethylene glycol was shown to be 1.5 times more active
than mercaptoethanol with respect to 2,5-diformylfuran.
3
: 4 : 9 = 0.3 : 1 : 1).
Structure of acetals of ethylene glycol 5–8 and 2-sulfa-
nyl ethanol 10, 11 was confirmed by NMR spectroscopy
and chromatography-mass spectrometry methods.
EXPERIMENTAL
In conclusion, cyclic acetals of some furanaldehydes
and ethylene glycol, and mercaptoethanol were syn-
thesized. The effect of the ratio of the starting reagents
on the yield of acetals obtained was revealed. The re-
action between 2,5-diformylfuran with an equimolar
amount of ethylene glycol resulted in the formation of
NMR spectra were recorded on a BrukerAVANCE-500
spectrometer (500.13 MHz) from CDCl solutions
3
relative to internal tetramethylsilane. Chromatographic
analysis of the reaction products was performed on a
HRGS 5300 Mega Series Carlo Erba chromatograph
with a flame ionization detector (carrier gas – helium,
flow rate 30 mL/min, column length 25 m, temperature
50–280°С, programmed heating at a rate of 8 deg/min,
5-(1,3-dioxolan-2-yl)-2-furylaldehyde and 2,2-furan-2,5-
diyl-1,3-dioxolane in the ratio of 6 : 1. 2,2-Furan-2,5-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019

SYNTHESIS OF CYCLIC DERIVATIVES OF CARBONYL COMPOUNDS
2343
detector temperature 250°С, evaporator temperature
00°С). Chromatography-mass spectra were recorded on
3.1 Hz), 5.82 s (2Н, СН), 6.53 d (1Н, СН=, J = 3.0 Hz),
1
3
3
7.10 s (1Н, СН=). С NMR spectrum, δ , ppm: 65.33
С
a Chromatek-Crystal 5000.2 instrument (capillary quartz
column 30 m, analysis time 20 min, ion source tempera-
ture 260°С, transition line temperature 300°С, scanning
range of 30–300 Da, pressure 37–43 mTorr, carrier gas—
helium, heating rate of 20 deg/min). To obtain mass
spectra of the compounds, the electron impact ionization
method was used.
(СН О), 97.54 (СН), 128.27 (СН=), 151.83 (С=). Mass
2
spectrum, m/z (I , %): 212 (5), 139 (5), 123 (100), 95
rel
(20), 73 (50).
5-(1,3-Oxathiolan-2-yl)furan-2-carbaldehyde (10).
Yield 78%, bp 149–150°C (3 mmHg), a colorless liquid
1
that gradually crystallizes upon cooling. Н NMR spec-
trum, δ, ppm: 3.70 t (2Н, СН S, J = 6.2 Hz), 4.00 d (2Н,
2
General procedure for the synthesis of acetals of
the furan series. A mixture of 0.06 mol (0.12 mol in the
case of dialdehyde 3) of alcohol, 0.02 mol of aldehyde,
СН О, J = 6.2 Hz), 5.88 s (1Н, СН), 6.50 d (1Н, СН=,
2
13
J = 4.9 Hz), 7.10 s (1Н, СН=), 9.50 s (1Н, СНО). С
NMR spectrum, δ , ppm: 32.77 (СН S), 71.55 (СН О),
С
2
2
0
.2 g of p-TsOH and 40 mL of benzene (or toluene) was
87.54 (СН), 109.54 (СН=), 154.04 (С=), 178.01 (СНО).
stirred at 80°С for 3–8 h with a Dean–Stark trap until
the calculated amount of water was isolated. After the
reaction completed, the mixture was dried with calcined
calcium chloride, and the filtrate was evaporated. The
reaction products were isolated by vacuum distillation.
Mass spectrum, m/z (I , %): 184 (22), 183 (70), 155 (8),
95 (25), 89 (100).
rel
2
,2'-Furan-2,5-diylbis(1,3-oxathiolane) (11). Yield
8
0%, bp 159–161°C (2 mmHg), a colorless liquid that
1
gradually crystallizes upon cooling. Н NMR spectrum,
δ, ppm: 3.90 t (4Н, СН S, J = 6.1 Hz), 4.10 d (4Н, СН О,
2
-(Fur-2-yl)-1,3-dioxolane (5). Yield 92%, bp 100–
01°С (7 mmHg). The physico-chemical characteristics
match those reported in [11].
5-(1,3-Dioxolan-2-yl)fur-2-yl]methanol (6). Yield
2
2
1
J = 6.1 Hz), 5.82 s (2Н, СН), 6.53 d (1Н, СН=, J =
13
4
.0 Hz), 7.10 s (1Н, СН=). С NMR spectrum, δ , ppm:
С
1
[
33.45 (СН S), 72.20 (СН О), 87.77 (СН), 110.38 (СН=),
2 2
9
0%, bp 150–151°С (3 mmHg), a colorless liquid that
151.05 (С=). Mass spectrum, m/z (I , %): 244 (20), 183
(60), 155 (25), 95 (5), 89 (100).
rel
1
gradually crystallizes upon cooling. Н NMR spectrum, δ,
ppm: 3.88 t (2Н, СН О, J = 3.1 Hz), 4.03 d (2Н, СН О, J =
3
2
2
FUNDING
.1 Hz), 4.50 s (2Н, СН ОН), 5.95 s (1Н, СНО), 6.45 d
2
13
This work was supported by the Russian Foundation for
Basic Research (Competition mol_ev_a, Eureka! Idea, contract
no. 19-33-80002\19 from 12.07.2018).
(1Н, СН=, J = 3.0 Hz), 6.50 d (1Н, СН=, J = 3.0 Hz). С
NMR spectrum, δ , ppm: 56.73 (СН ОН), 65.82 (СН О),
С
2
2
9
1
5.77 (СН), 113.44 (СН=), 120.98 (СН=), 151.01 (С=),
62.05 (С=). Mass spectrum, m/z (I , %): 170 (20), 139
rel
CONFLICT OF INTEREST
(20), 125 (100), 95 (35), 73 (73).
No conflict of interest was declared by the authors.
5
-(1,3-Dioxolan-2-yl)furan-2-carbaldehyde (7).
Yield 75%, bp 149–150°C (3 mmHg), a colorless liquid
that gradually crystallizes upon cooling. Н NMR spec-
REFERENCES
1
1
. Chernyshev, V.M., Kravchenko, O.A., andAnanikov, V.P.,
Russ. Chem. Rev., 2017, vol. 86, no. 5, p. 357.
https://doi.org/10.1070/RCR4700
trum, δ, ppm: 3.90 t (2Н, СН О, J = 3.1 Hz), 4.00 d (2Н,
2
СН О, J = 3.1 Hz), 5.88 s (1Н, СН), 6.50 d (1Н, СН=, J =
2
1
3
3
.0 Hz), 7.10 s (1Н, СН=), 9.50 s (1Н, СНО). С NMR
2
. Klushin, V.A., Kashparova, V.P., Kravchenko, O.A.,
Smirnova, N.V., Chernyshev, V.M., Ananikov, V.P.,
Galkin, K.I., and Krivodaeva, Е.A., J. Org. Chem.,
2016, vol. 52, no. 6, p. 767.
spectrum, δ , ppm: 65.33 (СН О), 97.54 (СН), 128.27
С
2
(СН=), 148.84 (С=), 151.83 (С=), 178.01 (СНО). Mass
spectrum, m/z (I , %): 168 (5), 139 (10), 123 (100), 95
rel
(25), 73 (15).
https://doi.org/10.1134/S1070428016060014
2
,2'-Furan-2,5-diylbis(1,3-dioxolane) (8). Yield
3. van Putten, R.-J., de Jong, E., van der Waal, J.C.,
and Rasrendra, C.B., Chem. Rev., 2013, vol. 113, no. 3,
p. 1499.
8
0%, bp 159–161°C (3 mmHg), a colorless liquid that
gradually crystallizes upon cooling. Н NMR spectrum, δ,
ppm: 3.92 t (4Н, СН О, J = 3.1 Hz), 4.00 t (4Н, СН О, J =
1
https://doi.org/10.1021/cr300182k
2
2
4
. Maximov, A.L., Nekhaev, A.I., and Ramazanov, D.N.,
Petroleum Chem., 2015, vol. 55, no. 1, p. 1.
1
Physico-chemical characteristics coincide with those for commercial
sample (https://www.abcr.de/ru/).
https://doi.org/10.1134/S0965544115010107
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019

2344
RASKILDINA et al.
5
. Lange,J.P.,vanderHeide,E.,Buijtenen,J.V.,andPrice,R.,
ChemSusChem, 2012, vol. 5, no. 1, p. 66.
https://doi.org/10.1002/cssc.201100648
9. Le, N.T., Byun,A., Han,Y., Lee, K.-I., and Kim, H., Green
Sust. Chem., 2015, vol. 5, no. 3, p. 115.
https://doi.org/10.4236/gsc.2015.53015
6
7
8
. Raskil’dina,G.Z.,Borisova,Yu.G.,andZlotskii,S.S.,Russ.
J. Gen. Chem., 2018, vol. 88, no. 8, p. 1601.
https://doi.org/10.1134/S107036321808008X
. Zhang, Z. and Deng, K., ACS Catal., 2015, vol. 5,
no. 11, p. 6529.
https://doi.org/10.1021/acscatal.5b01491
. Delidovich,I.,Hausoul,P.J.C.,Deng,L.,Pfutzenreuter,R.,
Rose, M., and Palkovits, R., Chem. Rev., 2015, vol. 116,
no. 3, p. 1540.
1
0. Ryabukhin, D.S., Zakusilo, D.N., Kompanets, M.O., Tara-
kanov, A.A., Boyarskaya, I.A., Artamonova, T.O., Kho-
hodorkovskiy, M.A., Opeida, I.O., and Vasilyev, A.V.,
Beilstein J. Org. Chem., 2016, vol. 12, p. 2125.
https://doi.org/10.3762/bjoc.12.202
1
1. Khlebnikova, T.D., Khamidullina, I.V., Khusainov, M.A.,
and Kantor, E.A., Bash. Khim. Zh., 2010, vol. 19, no. 1,
p. 190.
https://doi.org/10.1021/acs.chemrev.5b00354
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019