Interaction of triols with formaldehyde and acetone: Experimental and theoretical study

Article abstract of DOI:10.1002/jccs.201900401

Experimental and theoretical aspects of the condensation of glycerol and its homologs (1,2,3- and 1,2,4-butanetriols) with formaldehyde and acetone are studied under conditions of acid catalysis. Calculation of the thermodynamic parameters of the resulting products by the composite method CBS-QB3 shows that the six-membered heterocycles, the products of the interaction of triols with formaldehyde, are thermodynamically more stable than the five-membered acetals, while the reaction of the same triols with acetone is preferable for the formation of the five-membered acetals. This is due to the fact that the regioselectivity of the studied reactions is determined by the structural features and reactivity of the carbocations formed in a condensed medium during the course of the reaction. According to the theoretical data obtained experimentally, during the condensation of glycerol and 1,2,4-butanetriol with formaldehyde in the most stable form of the six-membered cyclic carbocation, intramolecular hydrogen bonding and anomeric stabilization due to the axially oriented hydroxyl group take place. As a result, cation 1b–1 is 1.2–1.6 kJ/mol more stable than its five-membered isomers (1a–1 and 1b–2). It leads to the predominant formation of 1,3-dioxane (3b). However, upon condensation of butanetriol-1,2,3 with formaldehyde, the intermediate cation 4a–1 turns out to be significantly more stable than the other isomers due to the strong intramolecular hydrogen bond in the six-membered ring with the participation of the hydroxyl group of the substituent and the hydroxyl group of the cationic center, leading to the predominant formation of the dioxolane 6a.

Full text of DOI:10.1002/jccs.201900401

Received: 19 September 2019
DOI: 10.1002/jccs.201900401
Revised: 13 January 2020
Accepted: 16 January 2020
A R T I C L E
Interaction of triols with formaldehyde and acetone:
Experimental and theoretical study
Rimma Sultanova1
| Sophia Borisevich1 | Gulnara Raskil'dina2
|
Julianna Borisova2 | Irina Baykova1 | Leonid Spirikhin1 | Sergey Khursan1
Simon Zlotsky2
|
1Ufa Federal Scientific Centre, Ufa
Abstract
Institute of Chemistry of the Russian
Academy of Sciences, Ufa, Russia
Experimental and theoretical aspects of the condensation of glycerol and its
2Department of General Chemistry,
Faculty of Humanities and Social
Sciences, Ufa State Petroleum
homologs (1,2,3- and 1,2,4-butanetriols) with formaldehyde and acetone are stud-
ied under conditions of acid catalysis. Calculation of the thermodynamic parame-
ters of the resulting products by the composite method CBS-QB3 shows that the
six-membered heterocycles, the products of the interaction of triols with formalde-
hyde, are thermodynamically more stable than the five-membered acetals, while
the reaction of the same triols with acetone is preferable for the formation of the
five-membered acetals. This is due to the fact that the regioselectivity of the stud-
ied reactions is determined by the structural features and reactivity of the
carbocations formed in a condensed medium during the course of the reaction.
According to the theoretical data obtained experimentally, during the condensa-
tion of glycerol and 1,2,4-butanetriol with formaldehyde in the most stable form
of the six-membered cyclic carbocation, intramolecular hydrogen bonding and
anomeric stabilization due to the axially oriented hydroxyl group take place. As a
result, cation 1b–1 is 1.2–1.6 kJ/mol more stable than its five-membered isomers
(1a–1 and 1b–2). It leads to the predominant formation of 1,3-dioxane (3b). How-
ever, upon condensation of butanetriol-1,2,3 with formaldehyde, the intermediate
cation 4a–1 turns out to be significantly more stable than the other isomers due to
the strong intramolecular hydrogen bond in the six-membered ring with the par-
ticipation of the hydroxyl group of the substituent and the hydroxyl group of the
cationic center, leading to the predominant formation of the dioxolane 6a.
Technological University, Ufa, Russia
Correspondence
Rimma Sultanova, Ufa Institute of
Chemistry of the Russian Academy of
Sciences, Ufa Federal Scientific Centre,
71 prosp., Oktyabrya, 450054 Ufa,
Russian.
Email: sultanova_rm@anrb.ru
K E Y W O R D S
acetals, DFT calculations, polyols
1 | INTRODUCTION
of organic molecules from the action of bases, Grignard
reagents, lithium aluminum hydride, oxidizers),[1,2] in
The products of interaction of alcohols with carbonyl
compounds—acetals—are a type of ethers that are widely
used in organic synthesis (to protect the carbonyl groups
perfumery as fragrant substances,[3] as additives to
beverages and food products (emulsifiers),[4] and in
pharmaceuticals as a solvent.[5] Recently, acetals of
© 2020 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J Chin Chem Soc. 2020;1–8.
http://www.jccs.wiley-vch.de
1

2
SULTANOVA ET AL.
polyols—glycerol and sugars—have been proposed as
additives to improve the properties of motor fuels.[6–10]
Ethers are in many respects more preferred compo-
nents of fuels than alcohols. The main advantages are their
higher oxidative stability, heat of combustion, as well as a
more favorable interphase distribution in the water–fuel
system. An important property of a variety of ethers (ace-
tals) is the possibility of obtaining them from renewable
sources (biomass, agricultural and forestry waste, food
industry, etc.). The presence of oxygen esters in the compo-
sition can significantly improve the environmental perfor-
mance of engines operating on these alternative motor
fuels. It should be noted that some ethers have very high
octane and cetane numbers,[11] have a low pour point,
have good lubricating properties, and also reduce harmful
emissions from the combustion of motor fuels.[12] Conve-
nient polyols for the production of acetals are glycerol and
its homologs (1,2,3- and 1,2,4-butanetriols).
The process of acetalization of polyols proceeds under
conditions of acid catalysis and relates to the proton trans-
fer (PT) reaction, one of the most important transforma-
tions in chemistry and biology, which contributes to the
foundation of science. That is why the PT reaction has
been very actively studied recently, including using the
methods of quantum chemistry. Most of current reports
on excited-state proton transfer (ESIPT) process are mainly
the excited-state intramolecular or intermolecular PT reac-
tion along with one hydrogen-bonding wire. That is to say,
the ESIPT process incorporating the transfer of two or
more protons should be of paramount interest. Such mul-
tiple PT compounds are rare and usually involve molecu-
lar self-assembly or solvent assistance.[13–16]
2 | RESULTS AND DISCUSSION
The thermodynamic parameters of the products of inter-
action of triols 1, 4, and 7 with formaldehyde and acetone
were calculated using the CBS-QB3 composite
method[17,18] in order to establish the general regularities
of the transformations under study (Scheme 1).
The theoretical results presented in Scheme 1 show
that the products of interaction of triols 1, 4, and 7 with
acetone—the five-membered acetals 2a, 5a, 5c, and 8a—
are thermodynamically more stable than the six-
membered acetals 2b, 5b, and 8b. On the contrary, in the
reaction of the same triols with formaldehyde, the forma-
tion of the six-membered heterocycles 3b, 6b, and 9b is
preferred. When carrying out the reactions, it was noted
that glycerol 1 under acid catalysis conditions selectively
reacts with acetone to form (2,2-dimethyl-1,3-dioxolan-
4-yl) methanol 2a (solketal) in quantitative yield, and
with a solution of formaldehyde with similar conditions
to the formation of
a mixture of two isomers
1,3-dioxolan-4-yl-methanol 3a and 1,3-dioxan-5-ol 3b
(yield 95%, Scheme 1, Equation 1) in the ratio 3a/
3b = 1:1.5 according to the spectra of nuclear magnetic
resonance (NMR spectroscopy). The ratio of isomeric het-
erocycles 3a and 3b was determined by the signal inten-
sity of methylene protons of the C(2) atom of the
1
heterocyclein H NMR spectra.[19] The above results are
consistent with the generally accepted concepts outlined
in a review[20] of the predominant formation of five- and
six-membered ring compounds in the condensation reac-
tion of alcohols and carbonyl compounds. We note that
in the cited work, a conclusion was drawn on the kinetic
control of the formation of five-membered cycles,
whereas the formation of dioxanes is due to their greater
thermodynamic stability.
In this work, the experimental and theoretical aspects
of the acetalization/ketalization of glycerol and its homo-
logs under conditions of acid catalysis are considered.
SCHEME 1 Transformations
studied and the Gibbs free energy (ΔGꢀ,
kJ/mol) for the condensation reactions
of triols 1, 4, and 7 with formaldehyde
and acetone

SULTANOVA ET AL.
3
Condensation of 1,2,3-butanthriol 4 with acetone
leads to a mixture of five-membered ketals 2,2-dimethyl-
4-α-hydroxyethyl-1,3-dioxolane 5a and 2,2,4-trimethyl-
5-hydroxyethyl-1,3-dioxolane 5c in the form of cis/trans
isomers in 1:1 ratio (according to NMR) with a predomi-
nant (90%) content of compound 5a, whereas
2,2,4-trimethyl-5-hydroxy-1,3-dioxane 5b was not
detected in the reaction mass (Scheme 1, Equation 2).
The interaction of this triol 4 with formaldehyde also pro-
ceeds with the predominant formation of five-membered
formals, despite the fact that, from the point of view of
thermodynamics, compound 6b is more stable than struc-
tures 6a and 6c. Three cyclic isomers, 4-α-hydroxyethyl-
1,3-dioxolane 6a, 4-methyl-5-hydroxyethyl-1,3-dioxolane
6c (cis/trans ratio 1:1 ratio) and 4- methyl 5-hydroxy-1,-
3-dioxane 6b (cis/trans ratio 1:1), are in the ratio of 6a/
6b/6c = 3:1: 0.5 (according to NMR spectroscopy). Most
likely, the observed correspondences are explained by dif-
ferent reaction mechanisms: namely, for the case
described, the kinetic control of the reaction is essential.
The homolog of glycerol, 1,2,4-butanetriol 7, in reactions
with formaldehyde and acetone, behaves similarly to
glycerol.[19] In the case of acetone, 2,2-dimethyl-
4-hydroxyethyl-1,3-dioxolane 8a is selectively formed
with a yield of 90%, and the condensation of triol 7 with
formaldehyde leads to the formation of a mixture of five-
and six-membered formals 1,3-dioxolane 9a and
1,3-dioxane 9b, in which 1,3-dioxane 9b prevails (the
ratio 9a/9b = 1:4 according to NMR spectroscopy). It
should be noted that the formation of 1,3-dioxepan-5-ol
9c is observed in trace amounts (Scheme 1, Equation 3).
Analyzing the results obtained as a whole, one can
note the good agreement between theory and experiment
for the case of the interaction of triols with acetone. At
the same time, the evaluation of only the thermodynamic
parameters of the reaction products cannot describe all
the experimentally observed features of the condensation
of triols with formaldehyde. We assumed that the expla-
nation of the observed contradictions lies in the specific
features of the structure and reactivity of the carbocations
formed in the condensed medium during the course of
the studied reactions. When the studied triols react with
formaldehyde in nonpolar solvents and acidic medium,
one should take into account the possible transformation
of primary and/or secondary hydroxyl groups of a triol
into the corresponding cations (Schemes 2–4).
SCHEME 2 Cationic intermediates of acid-catalyzed
condensation of glycerol with formaldehyde. The Gibbs free
energies (ΔGꢀ, kJ/mol) of cyclic intermediates formed
spontaneously as a result of the free rotation of cations 1a and 1b
around the C─C bond axes are given
SCHEME 3 Cationic intermediates of acid-catalyzed
condensation of butanetriol-1,2,3 with formaldehyde. The Gibbs
free energies (ΔGꢀ, kJ/mol) of the cyclic intermediates formed
spontaneously as a result of the free rotation of cations 4a–c around
the C─C bond axes are given
SCHEME 4 Acyclic cationic intermediates of acid-catalyzed
condensation of butanetriol-1,2,3 with formaldehyde
cation causes the existence of a set of states whose energy
is determined by the conformational potential typical of
aliphatic alcohols. In addition, some conformations will
be further stabilized by the formation of intramolecular
hydrogen bonds. However, the main factor in the
extrastabilization of conformers 1a and 1b is the Cou-
lomb interaction of the cationic center with the lone elec-
tron pairs of one of the neighboring oxygen atoms. These
2.1 | Glycerol
The condensation of glycerol with formaldehyde pro-
ceeds through the formation of cations 1a and 1b
(Scheme 2). The presence of several single bonds in the

4
SULTANOVA ET AL.
TABLE 1 Main geometrical parameters and relative Gibbs free energies of rotation isomers of cations 1a and 1b
Initial conformation
1a
φ1 (º)
φ2 (º)
r(O1-C) Å
r(O-C) Å
ΔGꢀ,a kJ/mol
Cycle on Scheme 2
ap,ap
174.9
−145.6
−148.9
53.4
150.6
46.9
4.20
1.59
1.59
4.61
4.62
4.70
3.97
2.65
4.15
1.61
3.97
4.54
1.59
3.88
4.42
1.59
3.70
4.61
−1.9
−7.5
−2.7
−1.0
23.4
30.5
−7.5
7.7
1a–1
1a–1
1a–1
1a–1
ap,+sc
ap,−sc
−57.2
148.0
56.5
+sc,ap
+sc,+sc
+sc,−sc
−sc,ap
63.9
52.9
−78.0
145.6
46.8
−46.8
−74.1
−42.4
1a–1
−sc,+sc
−sc,−sc
1b
−47.0
23.1
ap,ap
−176.8
−179.5
−172.2
55.7
177.3
60.2
5.14
5.24
5.25
4.99
1.64
1.64
3.37
1.61
4.82
2.60
4.07
4.41
2.53
4.12
4.12
1.57
3.52
4.50
0.0
20.4
24.5
1.1
ap,+sc
ap,−sc
−67.3
174.3
−22.8
−22.8
138.6
55.5
+sc,ap
+sc,+sc
+sc,−sc
−sc,ap
62.5
−2.3
−2.4
−9.0
−8.8
16.0
1b–1
1b–1
1b–2
1b–1
62.5
−50.6
−52.2
−61.9
−sc,+sc
−sc,−sc
−65.8
aStandard Gibbs energies of conformers with respect to ap,ap-form of cation 1b. The calculated values correspond to local minima on conformational PES. The
values of ΔGꢀ for global minima of cyclic cations are shown on Scheme 2.
factors form the distribution of conformers by relative
stability and explain the patterns of product formation.
Table 1 contains the results of calculations of geomet-
ric parameters and Gibbs energies of conformers 1a and
1b, which are formed during the free rotation along the
φ1 and φ2 axes. In some conformations, the carbocation
is favorably oriented with respect to the lone electron pair
of one of the oxygen atoms of the triol, which leads to
spontaneous cyclization. At the same time, some rela-
tively stable conformers of cations are not capable of
spontaneously cyclizing and play the role of “reservoirs”
of cationic states. Cyclic forms of cations can either
undergo a reversible opening of the cycle or be addition-
ally stabilized by intramolecular hydrogen bonds or an
anomeric effect, or they can split off a proton to form
molecular reaction products. In particular, during the
intramolecular hydrogen bond and anomeric stabiliza-
tion take place due to an axially oriented hydroxyl group
in the most stable form of a six-membered cyclic carbo-
cation. As a result, the cation 1b–1 is 1.2–1.6 kJ/mol
more stable than its five-membered isomers (1a–1 and
1b–2). Apparently, this fact explains the predominant for-
mation of 1,3-dioxane (3b) (Scheme 1).
2.2 | Butanetriol-1,2,3
When butanetriol-1,2,3 condenses with formaldehyde, the
formation of three types of cations is possible (Scheme 3).
The result of free rotation through two single C─C bonds
is the formation of various heterocyclic cations, the relative
energies of which are listed in Table 2. As in the previous
case, conformational rotation can lead to a set of cation
condensation
of
glycerol
with
formaldehyde,

SULTANOVA ET AL.
5
TABLE 2 The main geometrical parameters and relative Gibbs free energies of rotation isomers of cations 4a-c
Initial conformation
4a
φ1 (ꢀ)
φ2 (ꢀ)
r(O1-C) Å
r(O-C) Å
ΔGꢀ,a kJ/mol
Cycle on Scheme 3
ap,ap
174.9
−145.4
−150.8
57.9
147.0
48.5
4.19
1.59
1.59
4.64
4.66
4.42
3.96
1.50
4.18
1.57
3.94
4.52
1.55
3.76
4.58
1.56
2.96
4.43
−4.5
0.4
4a–2
4a–1
4a–1
4a–2
ap,+sc
ap,−sc
+sc,ap
+sc,+sc
+sc,−sc
−sc,ap
−sc,+sc
−sc,−sc
4b
−54.2
144.5
58.7
6.3
−4.4
33.2
40.5
−10.5
−22.6
38.2
64.8
80.9
−55.6
143.5
46.4
−48.5
−78.3
−53.9
4a–2
4a–1
−64.0
ap,ap
−172.4
−177.0
−167.4
56.0
174.9
58.8
5.07
5.18
5.30
4.99
1.60
1.60
4.34
1.58
4.35
2.57
4.07
4.27
2.56
4.08
4.08
2.43
3.53
4.57
5.5
28.6
33.5
11.8
2.6
ap,+sc
ap,−sc
+sc,ap
+sc,+sc
+sc,−sc
−sc,ap
−sc,+sc
−sc,−sc
4c
−77.8
178.0
−29.5
−29.5
173.5
56.6
60.9
4b–2
4b–2
60.9
2.6
−49.4
−51.6
−42.3
7.2
−12.3
33.2
4b–2
−56.0
ap,ap
−172.6
177.6
−176.2
62.7
174.5
57.2
5.08
5.10
5.93
5.36
1.68
1.65
3.35
1.62
5.08
2.56
4.10
4.40
1.60
4.10
4.12
1.57
3.51
4.47
0.0
18.8
25.0
0.7
ap,+sc
ap,−sc
+sc,ap
+sc,+sc
+sc,−sc
−sc,ap
−sc,+sc
−sc,−sc
−68.3
144.6
15.6
4c–1
4c–2
4c–1
4c–1
4c–2
42.5
4.7
64.5
−23.2
137.8
56.6
3.4
−51.6
−53.9
−74.5
−8.2
−7.8
20.1
−67.0
aStandard Gibbs energies of conformers with respect to ap,ap-form of cation 4c. The calculated values correspond to local minima on conformational PES. The
values of ΔGꢀ for global minima of cyclic cations are shown on Scheme 3.
states that differ in the presence or absence of stabilization
factors: the formation of a C─O bond with a ring closure, a
six-membered cycle of “chair” or “bath” conformation,
hydrogen bonding, anomeric stabilization, etc.
It is interesting to note that no conformations capable
of spontaneous cyclization into the dioxolane structure
were found in the case of cation 4b. In general, the con-
formational potential of 4a–c is expectedly similar to that
of cations generated from glycerol. A significant differ-
ence was found for cation 4a–1, which turned out to be
significantly more stable than other isomers due to the
strong intramolecular hydrogen bond in the five-

6
SULTANOVA ET AL.
membered cycle with the participation of the hydroxyl
group of the substituent (hydrogen bond acceptor) and
the hydroxyl group of the cationic center (hydrogen bond
donor). Apparently, this type of specific stabilization of
cations causes excessive accumulation of dioxolane 6a in
the spectrum of the condensation products of
butanetriol-1,2,3 with formaldehyde (Scheme 1), despite
the lower thermodynamic stability of this compound
compared to the derivative of 1,3-dioxane.
residue was distilled in vacuum (85ꢀC, 8 Torr). Yield
5.5 g (90%).
3.3 | Synthesis of 1,2,3-butanetriol
formals 6a–c
A mixture of 5 g (0.04 mol) of 1,2,3-butanetriol, 1 g
(0.03 mol) of paraform, 30 ml of anhydrous benzene, and
1% by weight of sulfuric acid was boiled until the calcu-
lated amount of water (0.7 ml) was separated. After com-
pletion of the reaction (3–4 hr), the solution was cooled
and evaporated. The residue was distilled under vacuum
(83ꢀC, 10 Torr). Yield 3.5 g (70%).
2.3 | Butanetriol-1,2,4
When butanetriol-1,2,4 condenses with formaldehyde, it
is also possible to form three types of carbocations
(Scheme 4). Free rotation in carbocations 7a–c can lead
to structures capable of spontaneous cyclization, with the
formation of five-, six-, and seven-membered heterocyclic
cations. The presence of the third axis of rotation at a sin-
gle C─C bond significantly complicates the conforma-
tional analysis, since there are 27 possible rotation
isomers for each cation.
3.4 | NMR analysis
1H, 13C NMR spectra were acquired on a Bruker Avance
III spectrometer (500 and 125 MHz, respectively) in
CDCl3. TMS (0.05%) was used as the internal standard
1
for H and 13C NMR spectra. The assignment of signals
However, it should be noted that, first, there is a good
agreement between the relative yields of reaction prod-
ucts 9a–c and their thermodynamic stability (Scheme 1),
which indicates the thermodynamic control of the reac-
tion. Second, the formation of a seven-membered cycle is
associated with significant entropy losses compared with
the formation of five- and six-membered cycles. For this
reason, a conformational analysis of the cations 7a–c
appears redundant and was not performed.
in the NMR spectra was based on 1Н–1Н (COSY), 1H–13C
(HSQC, HMBC) 2D correlations. 13С NMR spectra were
registered in DEPT-90, DEPT-135, and complete proton
suppression modes.
3.5 | Mass spectroscopy
Chromato-mass spectra were recorded on a “Chromatek
Crystal 5000.2” instrument with a capillary quartz col-
umn of 30 m, an analysis time 20 min, an ion source tem-
perature 260ꢀC, a transition line temperature 300ꢀC, a
scan range 30–300, pressure 37–43 mTorr, temperature
80–300ꢀC, temperature of the input port 320ꢀС, carrier
flue gas helium, and heating rate 20º/min. To obtain the
mass spectra of the compounds, electron impact ioniza-
tion method was used.
3 | EXPERIMENTAL
3.1 | 3.1 Materials
In the work, we used commercially available reagents
glycerol 1,2,3-butanetriol, 1,2,4-butanetriol, acetone, and
benzene. The method of synthesis and the physico-
chemical characteristics of ketals, glycerol
1 and
1,2,4-butanetriol 7 are described elsewhere.[19,21]
3.6 | Calculation procedures
All theoretical calculations were performed using the
GAUSSIAN 09 software. Revision C1.[22] To optimize the
structural parameters of reagents, intermediates, and
products of the condensation of triols with acetone and
formaldehyde, as well as to perform frequency calcula-
tions, the composite method CBS-QB3 was used.[17,18]
Thermodynamic parameters of the reactions studied were
calculated for the experimental conditions of temperature
298.15 K and pressure 1 atm. The effect of solvents
3.2 | Synthesis of 1,2,3-butanetriol
ketals 5a–c
A mixture of 5 g (0.04 mol) of 1,2,3-butanthriol, 2.5 g
(0.04 mol) of acetone, and 10 wt% p-toluenesulfonic acid
was stirred at room temperature for 5 hr. Then 4 g (anhy-
drous) K2CO3 was added and continued stirring for 1 hr.
The mixture was filtered and concentrated, and the

SULTANOVA ET AL.
7
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4 | CONCLUSIONS
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A theoretical analysis of the formation patterns of con-
densation products of triols with acetone and formalde-
hyde allowed us to draw the following conclusions. First,
the correspondence between the calculations and experi-
ment points to the thermodynamic control of the reac-
tion, during which a set of equilibrium transformations
involving cationic intermediates leads to the thermody-
namically most stable reaction products. Second, the con-
densation of triols with formaldehyde proceeds less
unambiguously. In particular, during the transformation
of butanetriol-1,2,3, it is necessary to take into account
the spectrum of possible cationic states that differ in their
reactivity and stability, which ultimately leads to the pref-
erential accumulation of product 6a instead of the deriva-
tive of 1,3-dioxane expected by thermodynamic stability.
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ACKNOWLEDGMENTS
The spectral analysis and the quantum chemical calcula-
tions were carried out using the equipment of the Center
for collective use “Khimiya” (Chemistry) at Ufa Institute
of Chemistry, Ufa Federal Research Centre of the Russian
Academy of Sciences. The work was performed within
the framework of the State assignment on research
study
topics
AAAA-A17-117011910028-7,
АААА-
А17-117011910025-6, and АААА-А17-117011910027-0 for
UfICh UFRC RAS.
ORCID
Rimma Sultanova https://orcid.org/0000-0001-6719-
2359
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How to cite this article: Sultanova R,
Borisevich S, Raskil'dina G, et al. Interaction of
triols with formaldehyde and acetone:
Experimental and theoretical study. J Chin Chem
Soc. 2020;1–8. https://doi.org/10.1002/jccs.
201900401
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