UDC:547.426.251+547.426.21
MODIFICATION OF DIGLYCEROL WITH ACETALS, DI-KETALS AND POLYOLS
Sharipov F.N., Ikromov M.S., Rajabzoda S.I.
Scientific and Research Institute of the National University of Tajikistan
Linear acetals, mostly obtained on the basis of vinyl or orthoethers, are present in most organic substances and are widely used as semi-products [1-5]. The method of obtaining linear acetal is obtained by condensation of choriataldehyde and triethyl orthoformate (reaction scheme 1) in the presence of PTSA catalyst at T=70 °C for 6 hours. The yield of the reaction product is 82% [6-10].
Reaction scheme 1
The interaction of other 2,3-diphenyldichlorocyclopropanes with absolute ethanol alcohol and butanol in the presence of NaOH alkali resulted in the formation of 57-72% of the reaction product (reaction scheme 2), which was completed in 15-18 hours and resulted in specific acetals.
2 Reaction scheme 2
Methods of production of cyclic acetals of 2,3-butanediol and 1,2-propanediol were studied. The resulting product is considered as a potential environmentally friendly solvent and gasoline ingredient.
Reaction scheme 3
The mechanism of interaction between glycerol and acetaldehyde is proposed (reaction scheme 4). As a result of condensation, the formation of four isomeric products is observed: cis- and trans-5-hydroxy-2-methyl-1,3-dioxane and cis- and trans-4-hydroxymethyl-2-methyl-1,3-dioxolane..
Reaction scheme 4
Linear acetals of 1,1,1-trioxymethylalkanes and pentaerythritol are used as polymer materials and coatings in the polymer industry [11-15].
Therefore, we studied the reaction between polyols - dipentaerytriol 1, dietriol 2 with carbonyl derivatives (reaction scheme 5). The experiment showed that the product of the reaction leads to changes in heterocyclic alcohols 5.
Reaction scheme 5
The interaction of polyols 1, 2 with ketenes and aldehydes 4-6 in the solvent of hexane, DMF in the presence of zeolite-720 catalysts, sulfuric acid and p-toluenesulfonic acid at t=80°C led to the formation of formals and ketels with different yields (Table 1).
Table 1
Types of catalysts and their effect on the yield of reaction products
(0–5 °C, 3 hours).
|
Primary substances |
Types of catalysts |
|||
|
Zeolite-720 |
Sulfuric acid |
p-toluene-sulpho-acid |
||
|
1 |
4 |
22 |
82 |
77 |
|
5 |
37 |
92 |
82 |
|
|
6 |
42 |
87 |
82 |
|
|
2 |
4 |
17 |
82 |
72 |
|
5 |
32 |
96 |
92 |
|
|
6 |
37 |
83 |
82 |
|
Using paraform 4 with the method of mutual reaction, we compared and revealed the activity of polyglycols 1 and 2 in the condensation reaction.
Thus, the analysis of HBE spectrometry and PMA spectroscopy showed that heterocycles 5 and 6 are a mixture of isomers 5a,b and 6a,b, respectively, 3:1 and 6:5. Therefore, it can be concluded that the product of the reaction exists in 4 isomer forms (Fig. 1).
Table 2
NMR signal of dipentaerythritols 5a, b and ditriols 6a, b
|
№ |
||||||||
|
1Н |
13С |
1Н |
13С |
1Н |
13С |
1Н |
13С |
|
|
2 |
4.58 с |
95.1 |
4.58 с |
95.0 |
4.66 д 4.86 д J = 6 |
95.1 |
4.61 д 4.81 д J = 4 |
95.1 |
|
4 |
3.42-3.45 м |
68.7 |
3.42-3.45 м |
68.3 |
3.41-3.51 м |
73.3 |
3.41-3.51 м |
73.3 |
|
5 |
||||||||
|
6 |
- |
40.7 |
- |
40.7 |
- |
38.3 |
- |
38.4 |
|
7 |
3.67 с |
63.1 |
3.71 с |
64.2 |
1.31 кв J = 4 |
25.1 |
1.26 кв J = 7 |
24.0 |
|
8 |
||||||||
|
9 |
- |
40.8 |
- |
40.7 |
- |
38.4 |
- |
38.5 |
|
10 |
3.42-3.43 м |
68.7 |
3.42-3.45 м |
68.5 |
3.41-3.51 м |
73.3 |
3.41-3.51 м |
73.3 |
|
11 |
||||||||
|
13 |
4.77 с |
96.1 |
4.81 с |
96.0 |
4.67 д 4.87 д J = 6 |
96.1 |
4.62 д 4.82 д J = 4 |
96.1 |
|
14 |
3.53 c |
70.8 |
3.55 с |
68.3 |
3.81 с |
67.2 |
3.78 с |
67.1 |
|
15 |
||||||||
|
16 |
- |
- |
0.86 т J = 7 |
7.2 |
0.86 т J = 7 |
7.6 |
||
|
17 |
- |
- |
||||||
|
ОН |
2.94 с |
- |
2.88 / 2.86 с |
- |
- |
- |
||
As can be seen from Fig. 1, the isomers 5a,b and 6a,b are from the direction of the R substituent (CH2OH for 5a,b and C2H5 for 6a,b) in the 5th position of the rings - the diaxial position for 5a and 6a is axial-equatorial and are different for 5b and 6b. The presence of two intramolecular hydrogen bonds with the diaxial orientation of CH2OH groups explains the superiority (threefold) of isomer 5a over 5b. There is no intramolecular interaction in the ditriol derivative 6, so the ratio of stereoisomers is related to the diaxial orientation of the C2H5 groups, but in 6a and to the axial-equatorial orientation of the substituents in 6b, it is almost the same.
We proved and confirmed the structure, composition and physicochemical properties of the synthesized heterocycles 5a,b and 6a,b using 1H and 13C NMR spectroscopy and mass spectrometry (Table 2-3).
The results of the mass spectrum and fragmentation of substances 4-7 and 11, 12 of the main types of ions and their relative intensity (e, % of the maximum) are shown in table 3.
Table 3
Relative intensity of substances 4-7 and 11, 12 and main types of ions (e, % of maximum)
|
Compounds |
Type of ion, or (%) |
||||||
|
4 |
1 |
6 |
19 |
11 |
- |
- |
100 |
|
5 |
5 |
6 |
- |
14 |
100 |
- |
- |
|
6 |
1 |
31 |
69 |
46 |
- |
- |
100 |
|
7 |
5 |
54 |
- |
59 |
100 |
- |
- |
|
11 |
15 |
81/64/27 |
- |
100/71/34 |
- |
59/19 |
70 |
|
12 |
5 |
91/59/34 |
- |
100/59/34 |
34 |
39/15 |
- |
As can be seen from Table 2, in the 13C NMR spectra of the obtained substances and dipentaerythritol 5a,b and ditriol 6a,b, the C(2) and C(3) atoms are in the range of 30.48–37.28 ppm, which is typical for cis-2,3-disubstituted cyclopropanes. Thus, the position of the C(1) signal is in the range of 58.53–68.51 ppm. This confirms the existence of the fourth carbon atom.
As can be seen from the image of the mass spectrum, the molecular intensity of the radical ion m = 197/199/201 leads to the formation of the ion m = 161/163/165 z = 91/56/11.
Fig 3. Mass spectrum of a dichlorocyclopropane derivative.
In this part of the work, we paid attention to the modification of diglycerol and its condensation with various carbonyl compounds (benzene, t = 70°C). This allowed us to obtain a dicyclic product, the reaction product of which depends primarily on the type or choice of catalyst (reaction scheme 6).
Reaction scheme 6
The course of the reaction was monitored by HBE spectrometry and PMA spectroscopy. According to the results of HBE and RMYA, compound 11 was determined in the form of two diastereomers in the ratio (erythro-) : (trio-) = 5:4 (Fig. 2).
Fig 2. HBE - continuous 11.
Table 4
Type of catalysts and their effect on the yield of the reaction product
(0–5 °C, 7 hours).
|
First compounds |
Types of catalysts |
|||
|
Zeolite-720 |
Sulfuric acid |
p-toluene-sulpho-acid |
||
|
3 |
4 |
22 |
83 |
76 |
|
5 |
36 |
91 |
82 |
|
|
6 |
42 |
88 |
83 |
|
Physico-chemical studies, including the nuclear magnetic resonance spectrum, showed that in the 1H NMR spectrum of diglycerol forms, the chemical propensity and multiplet signals of C4H and C8H proton groups of compounds are in the (δH 3.41 – 3.43 ppm) and (δH 4.11 -4.14 h.m.) show the existence of stereoisomers with the configuration of chiral centers for the molecule (RS, RS) – erythroisomer and for the molecule (RS, SR) – threoisomer. In this way, the protons of the C2H2 group from the 1,3-dioxolane part for the erythroisomer are in the form of two doublets in the range of δH 4.62 h.m. appear and in the area of 4.79 h.m. with the interaction of spin-spin constants 2.7 Hertz (Table 5).
Table 5
Nuclear magnetic resonance signals of compounds 11a, b
|
№ |
||||
|
1Н |
13С |
1Н |
13С |
|
|
2 |
4.62 / 4.79 д 2.7 Hz |
93.4 |
4.79 / 4.92 д 3.1 Hz |
94.2 |
|
4 |
3.41 – 3.43 м |
70.4 |
4.11 - 4.14 м |
73.3 |
|
5 |
3.48 – 3.55 м |
69.5 |
3.48 – 3.55 м |
70.7 |
|
6 |
3.57 – 3.99 м |
66.3 |
3.57 – 3.99 м |
68.8 |
|
7 |
||||
|
8 |
3.41 – 3.43 м |
70.4 |
4.11- 4.14 м |
73.1 |
|
9 |
3.48 – 3.55 м |
69.5 |
3.48 – 3.55 м |
70.5 |
|
11 |
4.62 / 4.79 д 2.7 Hz |
93.4 |
4.79 / 4.92 д |
94.2 |
The experiment showed that protons of the C5H2 group from the 1,3-dioxolane part for the erythroisomer as a multiplet in the range of δH from 3.48 - 3.55 ppm. was revealed. Protons of the C2H2 group of the 1,3-dioxolane part for the teroisomer are in the form of two doublets in the area of δH 4.79 h.m. are observed and in the area of 4.92 h.m. using the interaction of spin-spin constants 3.1 Hers. Protons of the C5H2 group from the 1,3-dioxolane fragment for the teroisomer as a multiplet in the range of δH from 3.48 - 3.55 h.m. such as erythroisomer signals appear.
In the C4H group, the ratio of erythro- and treoisomers in the reaction mixture is equal to 6:5, which depends on the integrated intensity of the protons of the studied molecules.
Chemical inclination in 13C NMR spectra of diglycerol derivatives for chiral centers C-4 and C-8 in the range of δc 70.4 ppm. were revealed and for erythro- and in the range of δc 74.3 h.m. revealed for tri configuration.
REVIEWER: Ruziev J.R.,
Doctor of Technical Sciences, Professor
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MODIFICATION OF DIGLYCEROL WITH ATSETALS, KETALS DI-AND POLYOLS
In recent years, the attention of organic chemistry researchers to aliphatic cyclic substances, on the basis of which carbo- and heterocyclic reagents are obtained, has been increasing. This is due to the fact that a large number of primary reagents, such as propanetriols and diglycerols, chlorohydrins, dichloroarenes, amino acids, diene hydrocarbons and their analogs, organic ligands, catalysts, α-oxides, ketone substances, aliphatic aldehydes, etc., can be produced . Substances obtained from this class of organic compounds have found practical application as biologically active compounds, corrosion inhibitors, and additives for motor oils. Therefore, research aimed at obtaining mono-, di- and multi-substituted acetals, including gem-dichlorocyclopropanes of glycerol, nitrogenous derivatives of glycerol, diglycerol and their analogues, is important from a scientific point of view and is among the most promising. The priority areas of science in the Republic of Tajikistan are considered. The purpose of the study is to develop a method for the synthesis, modification of mono-, di- and multi-substituted acetals, including gem-dichlorocyclopropanes of glycerol, diglycerol and their nitrogenous derivatives, and to determine their reactivity. The object of study is mono-, di- and multi-substituted acetals, including gem-dichlorocyclopropanes of glycerol, diglycerol and their nitrogenous derivatives.
Key words: glycerol, epichlorohydrin, monochlorohydrin glycerol, dichlorohydrin glycerol, α and γ-aminobutanate, diglycerol, heme-dichlorocyclopropane glycerol
Information about the author: Sharipov Firdavs Nurallievich – Research Institute of the Tajik National University, junior researcher. Address: 734025, Tajikistan, Dushanbe, Rudaki Ave., 17. Tel.: (+992) 900-54-05-36. E-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.
Ikromov Meniddin – Research Institute of the Tajik National University, junior researcher. Address: 734025, Tajikistan, Dushanbe, Rudaki Ave., 17.
Rajabzoda Sirojiddin Ikrom – Research Institute of the Tajik National University, Doctor of Chemical Sciences, Professor, Chief Researcher. Address: 734025, Dushanbe, Tajikistan, Rudaki Ave. 17. Tel.: (+992) 904-60-04-60. E mail: This email address is being protected from spambots. You need JavaScript enabled to view it.
Article received 09.03.2024
Approved after review 08.06.2024
Accepted for publication 30.09.2024