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ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
AZ9RBAYCAN KIMYA JURNALI № 4 2018
45
UDC 547.54;583.2
SYNTHESIS OF 2-HYDROXYPROPYL-1,3-6is-ESTEROSULPHOIMIDES OF SACCHARIN-5- AND -6-CARBOXYLIC ACID
E.T.Aslanova, T.A.Aslanov, A.A.Mammadova, B.A.Mammadov, D.R.Nurullayeva
Institute of Polymer Materials of Azerbaijan National Academy of Sciences
[email protected] Received 14.02.2017
The interesterification reaction of the ethyl (I) and isopropyl (II) ethers of sulphoimides of saccharin-5-and -6-carboxylic acids with glycerine has been studied. The corresponding 2-hydroxypropyl-1,3-bis-esterosulphoimides of saccharin-5-and-6-carboxylic acids have been synthesized. They have been characterized by elemental analysis and method of the IR spectroscopy. It has been elucidated that in use of 10% PbO catalyst per mass of glycerine a yield of purposeful product reaches its greatest value - 82 and 85% depending on used saccharin: (-5-) or (-6-).
Keywords: alkyl ethers, saccharin-carboxylic acids, sulphoimide, glycerine.
Introduction
It is known that the ethers of trimellitic and pyromellitic acids are the monomers for preparation of thermo- and radiation-resistant polymers [1].
In the literature there are data about synthesis of diesterodisulphoimides by interesteri-fication of the methyl ether of sulphoimides of saccharin-monocarboxylic acids by aliphatic and aromatic glycols [2, 3].
In this paper the interesterification reaction of the ethyl and isopropyl ethers of sulphoimides of saccharin-5- and -6-carboxylic acid with glycerine is described.
The aim of this work is the synthesis of new monomers on the basis of sulphoimides of saccharin-5- and -6-carboxylic acids for their further application during preparation of thermostable polymers.
Experimental
Synthesis of the alkyl ethers (ethyl- and isopropyl-) of sulphoimides of saccharin-5- and -6-carboxylic acids. The synthesis of the ethyl or isopropyl ethers of saccharin-5- and -6-carboxylic acids was carried out by heating of mixture consisting of 22.7 (0.1 mol) saccharin-5- and -6-carboxylic acid, 240 ml of absolute ethanol or isopropyl alcohol and 18 ml concentrated sulphuric acid. It was boiled with reflux condenser equipped with chlorocalcium tube to complete water separation and preparation of homogeneous transparent solution, which was cooled and poured into 600 ml distilled ice water. For ethyl
ethers: Tmdt (I) =1290C. Tmelt (II) =139-1400C. For isopropyl ethers: Tmelt (I') =1450C. Tmelt (II') =153-1540C.
Synthesis of 2-hydroxypropyl-1,3-6is-esterosulphoimides of saccharin-5-(a) and -6-(6) carboxylic acids. The mixture of 25.4 g (0.1 mol) of the ethyl ether of sulphoimide of saccharin-5- and -6-carboxylic acids and 4.9 g PbO in 49.6 g (0.5 mol) of 1,2,3-propantriol (glycerine) at mixing was heated to 124-1260C for 3-4 h. The reaction mass was dissolved in acetone and isolated by distilled water.
The prepared grayish-white crystalline product was dried at room temperature and brought to constant mass in vacuum. The product on the basis of sulphoimide of saccharin-5-carboxylic acid have Tmelt (a) =149-1510C.
The product on the basis of sulphoimide of saccharin-6-carboxylic acid corresponded to Tmelt (b) =158-1600C.
There have been analogously synthesized the above-mentioned compounds on the basis of isopropyl ether of sulphoimides of saccharin-5-and -6-carboxylic acids.
The boiling temperature of glycerine and solvents corresponded to the literary data [4].
The IR spectra were taken on IR-Fourier microscope LUMOS (firm BRUKER Germany) in the range of wave frequencies 600-4000 cm on the crystal diamond.
-1
Results and discussion
With the aim of synthesis of the new reaction ability monomers in the first stage there
46
SYNTHESIS OF 2-HYDROXYPROPYL-L3-fe-ESTEROSULPHOIMroES.
have been prepared the alkyl ethers (ethyl- and acids on scheme: isopropyl-) of saccharin-5- and -6-carboxylic
HOOC-t
-con
so,
\ (H2SO4) .nh+ r-oh -2 4 » rooc-i
-ho
-COn
-so9
.nh ,
r—c2h5, —с3н7.
In the second stage by interesterification of 1,3-bis-esterosulphoimides of saccharin-5- and -6-the prepared ethers by glycerine 2-hydroxypropyl- carboxylic acids have been prepared:
2ROOC
_ГТС%
СН2—СН—СН2 NH + I II
PbO
oh oh oh —2 ROH
/ОС-^^ ^^i-co-
hnC -гС-0-СН2-СН-СН2-0-С-г- I
с 2 i ii
^^ o oh o
;nh
—so,
R--С2Н5> —С3Н7 .
As a result of interesterification there have been prepared 2-hydroxypropyl-1,3-bis-esterosulphoimides of saccharin-5-(a) and -6-(b) carboxylic acids having ester and sulphoimide groups in their composition [5].
During carrying out of interesterification of the alkyl ethers of saccharin-5- and -6-carboxylic acids with glycerine PbO has been used as the catalyst. It has been elucidated from obtained data that a yield of the purposeful products mainly depends on quantity of the used catalyst. It has been established by test way that in use of 10% PbO catalyst per mass of glycerine a yield of 2-hydroxypropyl--1,3-bis-esterosulphoimides of saccharin-5- and -6-carboxylic acids reaches its greatest value - to 82% (a) and 85% (b).
It has been established that with increase of a number of hydrocarbons in ether group of sulphoimides of saccharin-5 and 6-carboxylic
acids the interesterification reaction occurs at lower temperatures.
The composition and structure of 2-hydroxypropyl-1,3-bis-esterosulphoimides of saccharin-5-(a) and -6-(b)carboxylic acids have been determined by elemental analysis and IR spectroscopy.
The physical constants of the products (a) and (b) are presented in Table. It has been detected that in the IR spectra of these compounds there are the absorption bands in the fields of 1300-1250 cm-1 and 1100 cm-1 corresponding to the valence vibrations of C-O-C ester group, and also the absorption bands in the field of 1720 cm-1 characteristic for >C=O- group in esters. In addition, there are the absorption bands in the fields of 1730, 1370, 1180 and 3000-2840 cm-1 characteristic respectively for >C=O groups of SO2 and >NH saccharin cycle [6].
Physical constants of 2-hydroxypropyl-1,3-b;s-esterosulphoimides of saccharin-5-(fl) and -6-(b) carboxylic acids
Brutto formula Found, % ^melt , 0С Yield, %
Compound Calculated, % М
C H N S
a C19H14°11N2S2 43.85 2.60 5.45 12.07 510 149-151 82
b 44.74 2.74 5.49 12.57 158-160 85
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 4 2018
ETASLANOVA et al.
47
Conclusions
1. The interesterification reaction of the ethyl and isopropyl ethers of sulphoimides of saccharin-5- and -6-carboxylic acids with glycerine has been studied. The corresponding 2-hydroxypropyl-1,3-bis-esterosulphoimides of saccharin-5- and -6-carboxylic acids have been synthesized.
2. It has been established that at use of 10% PbO catalyst for mass of glycerine a yield of the purposeful product reaches its greatest value - to 82 and 85% depending on used saccharin: (-5-) or (-6-).
3. The synthesized 2-hydroxypropyl-1,3-bis-esterosulphoimides of saccharin-5-(a) and -6-(b) carboxylic acids are of interest for their use as the monomers at preparation of linear and highly branched sul-phoimide-containing polymers and also as
the hardener-plasticizer of epoxy diene resins.
References
1. Suvorov B.V., Zhubanov B.A., Mashkevich S.A. Trimellitovaia kislota i polimery na ee osnove. Alma-Ata: Nauka, 1975. 288 s.
2. Babe S.G., de Abajo J., Fontan J. Ordered copol-yamide-imides and copolyester-imides // Angew. Makromol. Chem. 1972. V. 21. No 205. P. 65-67.
3. Aslanov T.A., Mamedli U.M., Guliev A.M. Sin-tez diefirodisulfimidov na osnove saharin mono-karbonovykh kislot s aromaticheskimi diolami // Zhurn. pricl. himii. 2005. T. 78. № 3. S. 444-446.
4. Gordon A., Ford R. Sputneyk himika. M.: Mir, 1976. 546 s.
5. Aslanov T.A., Aslanova E\T., Mamedalieva F.M., Ishchenko N.Ia. Sintez imida 4-suTfoizoftalevoi kislotyi ee nekotorykh amidnykh proizvodnykh // Azerb. him. zhurn. 2015. № 3. S. 54-58.
6. Kazitcina L.A., Coopletskaia N.B. Primenenie UF-, IK-, IAMR- i mass spektroskopii v orga-nicheskoi himii. M.: Izd-vo MGU, 1979. 236 s.
SAXARiN-5- УЭ -6-KARBON TUR§ULARININ 2-HiDROKSiPROPiL-1,3-Ais-EFiROSULFiMiDLORiNiN SiNTEZi
E.T.Aslanova, T.A.Aslanov, A.A.Mamm3dova, B.A.Mamm3dov, D.N.Nurullayeva
Saxarin-5- va -6-karbon tur§ularinin etil va izopropil efirosulfimidlarinin qliserinla yenidan efirla§masi reaksiyasi oyranilmi§dir. Saxarin-5- va -6-karbon tur§ularinin muvafiq 2-hidroksipropil-1,3-ftis-efirosulfimidlari sintez edilmi§dir. Onlar element analizi va iQ spektroskopiya usulu ila xarakteriza edilmi§dir. Malum olmu§dur ki, qliserin kutlasina nisbatan 10% PbO katalizatoru istifada etdikda alinan mahsulun giximi tarkibindan asili olaraq an yuksak hadda - 82% va 85%-a gatir.
Agar sozlar: alkil efirbri, saxarin-karbon tur§ulari, sulfmid, qliserin.
СИНТЕЗ 2- ГИДРОКСИПРОПИЛ-1,3-6ис-ЭФИРОСУЛЬФОИМИДОВ САХАРИН-5- И -6-КАРБОНОВЫХ КИСЛОТ
Э.Т.Асланова, Т.А.Асланов, А.А.Мамедова, Б.А.Мамедов, Д.Р.Нуруллаева
Изучена реакция переэтерификации этиловых и изопропиловых эфиров сульфоимидов сахарин-5- и -6-карбоновых кислот с глицерином. Синтезированы соответствующие 2-гидроксипропил-1,3-бис-эфиросуль-фоимиды сахарин-5- и -6-карбоновых кислот. Они охарактеризованы элементным анализом и методом ИК-спектроскопии. Выяснено, что при использовании 10% катализатора РЬО на массу глицерина выход целевого продукта достигает в зависимости от использования сахарина (-5-) или (-6-) своего наибольшего значения - до 82 и 85% соответственно.
Ключевые слова: алкиловые эфиры, сахарин-карбоновые кислоты, сульфоимид, глицерин.
