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AZERBAIJAN CHEMICAL JOURNAL № 4 2022 ISSN 2522-1841 (Orira)
ISSN 0005-2531 (Print)
UDC 547.541:542.913
SYNTHESIS OF SOME DERIVATIVES OF 2-HYDROXYPROPYL-1,3-B/S-ESTER-SULPHOIMIDE OF SACCHARIN-6-CARBOXYLIC ACID
E.T.Aslanova, M.N.Rashidova, A.A.Garayeva, S.Y.Heydarova, V.O.Atakishiyeva
Institute of Polymer Materials, NAS of Azerbaijan
Received 19.05.2022 Accepted 26.07.2022
In order to synthesize new reactive monomers to obtain new heat-resistant polymers and epoxyimide resins, 2-hydroxypropyl-1,3-bis-hydroxyethylester-sulphoimide and 2-hydroxypropyl-1,3-bis-carboxy-methylester-sulphoimide of saccharin-6-carboxylic acid were synthesized. Monomers were synthesized based on 2-hydroxypropyl-1,3-bis-ester-sulphoimide of saccharin-6-carboxylic acid. The resulting products were characterized by elemental analysis and IR spectroscopy. The yield of target products was 83% and 78.6%, respectively. It was found that the synthesized compounds are readily soluble in polar aprotic solvents.
Keywords: monomer, 2-hydroxypropyl-1,3-bis-ester-sulphoimide of saccharin-6-carboxylic acid, polyatomic alcohol.
doi.org/10.32 73 7/0005-2531-2022-4- 78-82
Introduction
It is known that highly branched polymers are often called new generation polymers, they are predicted to have a great future as special purpose materials [1]. Such polymers have a low viscosity of solutions and melts, which means a reduction in energy consumption during the processing of polymers into a finished product, the possibility of producing more environmentally friendly materials with a reduced content of solvents [2]. The regular structure of some highly branched polymers and the ability to control their physicochemical properties stimulate considerable interest in their further study and application in practice. The choice of peripheral groups makes it possible to change the chemical, physical, and biological functionality of macro-molecules [3, 4].
There are data in the literature that monomers with ester, acid, anhydride, amide, and hy-droxyl functional groups are usually used as monomers to obtain heterocyclochain heat-resistant polymers and oligomers of various structures [5-10]. Previously, we have obtained anhydride, dianhydride, and esters of sulpho-imides of mono- and disaccharincarboxylic acids, which were used as monomers in the preparation of epoxyimide resins and polymeric
materials [11-13]. There is also information on the synthesis of diester disulphoimides by transesterification of the methyl ester of saccharin-monocarboxylic acids with aliphatic and aromatic glycols [14].
Therefore, based on the foregoing, in order to obtain new heat-resistant polymers of a linear and highly branched structure, as well as ep-oxyimide resins, we developed methods for the synthesis of reactive monomers based on 2-hydr-oxypropyl-1,3-bis-ester-sulphoimide of saccharin-6-carboxylic acid.
The aim of this work is the synthesis of new monomers based on 2-hydroxypropyl-1,3-bis-ester-sulphoimide of saccharin-6-carboxylic acid for their further use in the preparation of epoxyimide resins and heat-resistant polymers, as well as as hardeners-plasticizers for industrial epoxy resins.
Experimental part
Synthesis of 2-hydroxypropyl-1,3-6is-hydroxyethylester-sulphoimide of saccharin-6-
carboxylic acid. In a three-necked round bottom flask, a mixture consisting of 25.5 g (0.05 mol) of 2-hydroxypropyl-1,3 -bis-ester-sulphoimide of saccharin-6-carboxylic acid, 8.5 g (0.1 mol) of ethylene chlorohydrin and 10 g of KJ was dissolved in 120 ml DMAA. The mixture was
heated to 1100C for 1 hour with stirring. Then, the reaction temperature was raised to 125-1300C and heated for another 2 hours. The resulting mass was acidified with hydrochloric acid to a neutral medium, filtered, washed with cold distilled, dried in air at room temperature, then in vacuum to constant weight.
Synthesis of 2-hydroxypropyl-1,3-6is-carboxymethylester-sulphoimide of saccharin-6-carboxylic acid. In a three-necked round bottom flask, a mixture of 25.5 g (0.05 mol) 2-hydroxypropyl-1,3-bis-ester-sulphoimide of sac-charin-6-carboxylic acid, 14 g (~0.1 mol) powdered potassium carbonate, 9.5 g (~0.1 mol) of monochloroacetic acid and 50 g of KJ were dissolved in 260 ml of DMAA and boiled for 8 hours. Upon completion of the reaction, the resulting mass was cooled to room temperature, the precipitated crystals were washed twice with DMAA and filtered through a glass filter. The synthesized substance was dried at room temperature and then in vacuum to constant weight.
HN
/OC-.
n
\ O-CH2-CH-CH2- o-
The physicochemical properties of the solvents corresponded to the literature data [15, 16].
Infrared spectra were recorded on IR-Fourier spectrometers LUMOS and ALPHA (BRUKER Germany) in the wave frequency range 600-4000 cm-1, using an FTIR attachment with a ZnSe crystal. Crystal diameter 1 sm. Number of sample scans 24, measurement duration 30 sec.
Elemental analysis was carried out according to the method [17] based on the pyro-lytic combustion of organic matter in an oxygen flow using a Pregl apparatus.
Result and discussion
In order to obtain new reactive monomers, as a result of the interaction of 2-hydroxypropyl-1,3-bis-ester-sulphoimide of sac-charin-6-carboxylic acid with ethylene chloride, a new polyatomic alcohol was synthesized - 2-hydroxypropyl-1,3 -bis-hydroxyethylester-sulpho-imide of saccharin-6-carboxylic acid according to the following scheme:
I C0^NH+2CHCH2)2OH -Î
'—SO,/ -2HCI
o
OH
HO(H2C)2_N
x^-C- O—CH2— CH—CH2— o-
o
I
OH
.-CO-'-SO./
N-(CH2)2OH
The yield of the target product is 83%.
The synthesized substance is a grayish-white powder, melting at 1850C and soluble in aprotic solvents, as well as in dioxane and m-xylene.
The composition and structure of the resulting compound were determined by elemental analysis and IR spectroscopy.
It was found that in the IR spectra (Figure 1) of this compound there are absorption bands in the region of 1406, 1436 cm-1 bending and in the region of 2882, 2936cm-1 of the stretching vibrations of the C-H bond of the CH2 group;
stretching vibrations of the amide C=O bond in the region of 1627 cm-1; stretching vibrations in the region of 1283 cm-1 C-N-bond; stretching vibrations of C-O- and O-H-bonds of alcohol in the region of 1032 cm-1 and 3289 cm-1; stretching vibrations of the SO2 bond in the region of 1245 cm-1; stretching vibrations of the C-O bond of the ester in the region of 1107 cm-1; stretching vibrations of the C=O bond of the ester in the region of 1721 cm-1; bending vibrations of the C-H bond (751.853 cm-1) of the substituted benzene ring [1-20].
Table 1. Physical constants of 2-hydroxypropyl-1.3-b/.s--hydroxyethylester-sulphoimide of saccharin-6-carboxylic acid
Compound Chemical formula Found % MM T i m? c Yield %
Calculated %
2 -hydro xypropyl -1,3-b/s-hydr-oxyethylester-sul-phoimide of saccharin-6-carboxylic acid C23H22°13N2S2 C H N S 598 185 83
45.05 46.15 3.54 3.68 4.61 4.68 10.0 10.7
~î—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—;—r 3900 3700 3500 3300 3100 2900 2700 2500 2300 2100 1900 1700 1500 1300 1100 900 700
Wavenumber cm-1
Fig. 1. IR spectrum of2-hydroxypropyl-1,3-b/s-hydroxyethylester-sulphoimide of saccharin-6-carboxylic acid.
The synthesis of 2-hydroxypropyl-1,3-fe-carboxymethylester-sulphoimide of saccharin- 6-
carboxylic acid was carried out according to the following scheme:
HN
/oc-1 \ o,s—
n
—C- O-CHn—CH-CH,- o-
o
I
OH
I C0 ^NH + 2C1—CH2COOH-Î
'-SO,/ —2HCI
-
HOOCH,C-Nv _ || I
/OC-.1
\ o2s—L^-C- 0-H2C-CH-CH2-o-c
o
OH
,—CO
;]s^ch2cooh
The resulting product was found to be a light coffee powder, soluble only in aprotic solvents such as DMF, DMAA, DMSO, etc.
The yield of the target product is 78.6%.
The composition and structure of 2-hydr-oxypropyl -1,3 -è/5-carboxymethylester- sulpho-imide of saccharin-6-carboxylic acid was determined by elemental analysis and IR spectroscopy.
Fig. 2. IR spectrum of 2-hydroxypropyl-1.3-b/v-carboxymethylester-sulphoimide of saccharin-6-carboxylic acid.
Table 2. Physical constants of 2-hy dro\> prop> l-1,3-^/.v-carbo\> methylester-sulphoimide of saccharin-6-carboxylic acid
Compound Chemical formula Found % MM T 0C ± m; ^ Yield %
Calculated %
2 -hydro xypropyl -1,3-biv-carb-oxymethyl-ester-sulphoimide of saccharin-6-carboxylic acid C23H18015N2S2 C H N S 626 190 78.6
57.95 58.79 2.14 2.87 1.61 2.24 9.81 10.22
It was found that in the IR spectra (Figure 2) of this compound there are absorption bands in the region of 1355, 1413, 1459 cm-1 of the bending vibrations of the C-H bond of the CH2 group; stretching vibrations of C=O bonds of acid groups in the region of 1721 cm-1; stretching vibrations of COOH groups in the region of 2851, 2917 cm-1; stretching vibrations of the amide C = O bond in the region of 1679 cm-1; stretching vibrations in the region of 1243, 1298 cm-1 C-N bonds; stretching vibrations of C-O- and O-H- bonds of alcohol in the region of 1043 cm-1 and 3217 cm-1; stretching vibrations of the SO2 bond in the region of 1150, 1185 cm-1; bending vibrations of the CH bond (739, 861, 890 cm-1) of the substituted benzene ring.
Thus, on the basis of the research carried
out, the following conclusions can be drawn. Methods for the synthesis of 2-hydroxypropyl-1,3-fe-hydroxyethylester-sulphoimide and 2-hy-droxypropyl -1,3 -¿z's-carboxymethyl estersulpho-imide of saccharin-6-carboxylic acid have been developed; the synthesized compounds are of interest for their use as monomers in the preparation of heat-resistant sulfoimide-containing polymers and epoxy resins, and also as hardeners-plas-ticizers for industrial epoxy resins.
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SAXARÍN-6-KARBON TUR§USUNUN 2-HÍDROKSÍPROPÍL-1,3-B/S'-EFÍROSULFOÍMÍDÍNÍN BOZÍ
tóromolorínín síntezí
E.T.Aslanova, M.N.Ra^idova, A.0.Qarayeva, S.Y.Heydarova, V.O.Ataki^iyeva
Yeni reaksiyaya qabil monomerlarin sintezi maqsadila istiliyadavamli polimerlar va epoksimid qatranlan alda etmak ügün saxarin-6-karbon tur§unun 2-hidroksipropil-1,3-¿is-hidroksietilefirosulfoimid va 2-hidroksipropil-1,3-bis-karbok-simetilefirosulfonimidi sintez edilmi§dir. Monomerlar saxarin-6-karbon tur§usu 2-hidroksipropil-1,3-¿is-efirosulfoimidi asasinda sintez edilmi§dir. Ahnmi§ mahsullar elementar analizi va ÍQ -spektroskopiya ila xarakteriza edilmi§dir. Maqsadli mahsullarin mahsuldarligi müvafiq olaraq 83 va 78.6% olmu§dur. Müayyan edilmi§dir ki, sintez edilmi§ birla§malar polyar aproton halledicilarda asanliqla hall olunur.
Agar sozlzr: monomer, saxarin-6-karbon tur§usunun 2-hidroksipropil-1,3-bis-efirosufomidi, goxatomlu spirt.
СИНТЕЗ НЕКОТОРЫХ ПРОИЗВОДНЫХ 2-ГИДРОКСИПРОПИЛ-1,3-£#С-ЭФИРОСУЛЬФОИМИДА
САХАРИН-6-КАРБОНОВОЙ КИСЛОТЫ
Э.Т.Асланова, М.Н.Рашидова, А.А.Гараева, С.Я.Гейдарова, В.О.Атакишиева
С целью синтеза новых реакционноспособных мономеров для получения новых термостойких полимеров и эпоксиимидных смол были синтезированы 2-гидроксипропил-1,3-бис-гидроксиэтилэфиросульфоимид и 2-гидроксипропил-1,3-бис-карбоксиметилэфиросульфоимид сахарин-6-карбоновой кислоты. Синтез мономеров производился на основе 2-гидроксипропил-1,3-бис-эфиросульфоимидасахарин-6-карбоновой кислоты. Полученные продукты охарактеризованы элементным анализом и ИК-спектроскопией. Выход целевых продуктов составил соответственно 83% и 78,6%. Выяснено, что синтезированные соединения хорошо растворяются в полярных апротонных растворителях.
Ключевые слова: мономер, 2- гидроксипропил-1,3-бис-эфиросульфоимид сахарин-6-карбоновой кислоты, многоатомный спирт.
