SYNTHESIS AND POLYMERIZATION OF N,N-DI(β-CHLOR)ALLYLAMINOETHANIC ACID Текст научной статьи по специальности «Химические науки»

ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)

AZERBAIJAN CHEMICAL JOURNAL № 2 2023

13

UDC 547.466.226, 233.3, 315.3

SYNTHESIS AND POLYMERIZATION OF N,N-DI(P-CHLOR)ALLYLAMINO-

ETHANIC ACID

A.M.Garamanov, R.A.Akhmedova, N.Kh.Gusiev, B.A.Mamedov, A.F.Mamedova,

M.Sh.Gurbanov

Institute of Polymer Materials, Ministry of Science and Education of the Republic ofAzerbaijan

[email protected]

Received 28.10.2022 Accepted 22.12.2022

Amino acids are chiral compounds that make up proteins and play an important role in biochemical processes in living organisms. They are widely used as building blocks in organic synthesis, components of asymmetric synthesis catalysts, separating agents, etc. To this end, we found that the interaction of 1 mol aminoethanic acid with 2 mol of (P-chlor)allyl chloride in an aqueous solution of sodium hydroxide leads to the formation of a new monomer - N,N-di(P-chlor)allylamino ethanic acid (BEA) with a yield of ~45%. When carrying out the polymerization of BEA in an aqueous solution in the presence of ammonium persulfate with an initiator concentration of 4 10-4-5 10-3 mol/l , water-soluble polymers with sufficiently high values of reduced viscosity ([n] = 0.16-0.18 dl/q) for the indicated amino acid were obtained. It was found that polymerization proceeds along the double bonds of diallyl groups according to the cyclolinear mechanism with a pyrrolidine structure.

Keywords: aminoethanic acid, (fi-chlor)allyl chloride, initiator, aqueous solution of sodium hydroxide, N,N-di(P-chlor)allylamino ethanic acid.

doi.org/10.32737/0005-2531-2023-2-13-18

Introduction

Amino acids play a central role in chemistry and biology. Their availability is important for basic research as well as in industry. They can be completely synthetic. Synthetic amino acids are often used in more and more complex structures of new pharmaceutical agents. These factors stimulated the development of a methodology for the synthesis of amino acids using stereoselective, constructive synthetic reactions [1-6].

Amino acid-based electrically conductive polymers are a relatively new class of polymers. In recent years, this direction in polymer chemistry has been rapidly developing. Ion exchange sorbents, coagulants, flocculants, separating membranes, soil structurator, biopolymer models, polymeric carriers of various kinds of functional fragments - this is not a complete list of their practical applications.

There are types of polymeric materials that enhance soil fertility, regulate moisture supply to plants, reduce wind erosion of soils, stimulate plant growth and development, in-

crease plant resistance to negative temperatures, salinity, etc. [7-17].

At present, much attention is paid to the synthesis of diallyl monomers, as well as polymers based on them, due to the wide range of applications water-soluble polymers; therefore, the synthesis of soluble polyelectrolyte polymers, which would have complexes of valuable properties, in particular, amphophilic properties, is relevant.

In work [18] we studied the synthesis and polymerization of N-allyl-N-(P-chlor)allylami-noethanic acid (By the way, this compound is named erroneously without "amino"). This paper will consider the method of preparation, structure, properties and synthesis of polymers based on N,N-di(P-chlor)allylaminoethanic acid (BEA) [19, 20].

Experimental part

Recrystallization aminoethanic acid: molecular weight 75.57, density 1.6 g/cm3, melting point 232-2360C. Freshly distilled (P-chlor)allyl chloride - boiling point 940C, 1.4600, 1.2080. Ammonium persulfate (AP)

(NH4)2S2O8 products of the "chemical for analyses" brand. In all experiments, bidistilled water was used. The solvents used correspond to the table specifications.

Syntheses of N,N-di(P-chlor)allylami-noethanic acid (BEA). Into a two-liter four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, stir 7.55 g (0.1 mol) aminoethanic acid, and while cooling (not higher than 50C) add 7.65 g 22.2 g (0.2 mol) (P-chlor)allyl chloride in within an hour and then a 50% aqueous solution of 12 g (0.3 mol) of sodium hydroxide. The reagent feed rate is adjusted so that the temperature in the reaction mass does not exceed 300C. An ice water bath is used to remove excess heat. After adding sodium hydroxide solution, the reaction mass is slowly heated to 700C. The reaction mixture was neutralized (pH=7.0) and diluted with hydrochloric acid. After the end of the reaction, the reaction mixture is gradually poured into dry acetone in portions. The light yellow amino acid flocculated on the surface of the acetone. The flakes are filtered on a Buech-ner funnel, washed thoroughly with dry acetone, then dried in a desiccator over P2O5 to constant weight. The monomer melts with decomposition (at - 287±0.20C). With a yield of 50-55%, essential BEA is obtained. Found, %: C 42.73, H 5.02, N 6.18, Cl 31.88. C8HnO2NCl2, Calculated, %: C 42.69, H 4/92, N 6.22, Cl 31.95.

Polymerization of BEA. An aqueous solution (0.2 mol) of the monomer in the presence

of an initiator (4-10-4-5 • 10-3mol/l) was placed in a special ampoule, evacuated, and sealed. The ampoules were placed in a thermostat at a temperature of 60 - 70°C and kept for 14-24 hours. After the completion of the reaction mixture was gradually poured into dry acetone in portions. The resulting flakes were filtered, washed thoroughly with dry acetone, and dried over P2O5 to constant weight ~45% yield. The reduced viscosity is 0.16-0.18 dl/g. Found, %: C 42.53, H 4.83, N 6.27, Cl 31.79. C8H11O2NCl2, Calculated, %: C 42.68, H 4.83, N 6.27, Cl 31.95.

Results and discussions

It is known from the literature that it is rather difficult to obtain alkylated a-amino acids. In work [9], the authors showed that basic and acidic amino acids do not react with allyl bromide and do not from substitution products. The difficulties associated with the alkylation of amino acids are apparently associated with the fact that a-amino acids are amphoteric (bipolar) compounds and correspond to the general formula:

© ©

H3N-CH2-COO

For the alkylation of an a-amino acid, it must be converted to its anionic form.

In an aqueous solution, depending on the pH of the medium, the molecule takes on the following forms:

©

-H ©

© -H.

H,N-CH,-CHOOH H3N-CHrCOO ^r H2N-CH2COO

©

©

+ H

©

+ H

Deprotonation of the amino acid leads to the formation of the anionic form of the a-amino

acid:

© +NaOH, pH >12 ©

H3N-CH2-COO -► H2N-CH2COO

SYNTHESIS AND POLYMERIZATION OF N,N-DI(P-CHLOR)

In which the basic properties of the NH2-group are enhanced, as a result of which the al-kylation reaction is possible.

To synthesize BEA, a diallyle monomer,

15

the molecule of which would contain both positively and negatively charged functional groups, we carried out the alkylation reaction of a-amino acid with (P-chlor)allyle chloride:

CH2=CC1CH2C1 + 2 NaOH CH2=CC1-CH^ 0 H2N-CH2-COOH + CH2=CC1CH2C1 ^¡^ CHrCCl-CH^f 0

-2 H20 CH2-COO

The identification of the resulting product was carried out by comparing the absorption bands of the characteristic groups of the IR spectra. The amino acid contains two functional groups - NH2 and COO-, which are characterized by absorption bands in the region of 3100-3400 cm-1 for the associated group NH2; in the region of 1725-1680 cm-1 for the carbox-yl group - COO-.

In the case of the formation of BEA, the analytical signal confirming the alkylation reaction is the presence of an intense absorption spectrum in the 1625 cm-1 region, which is characteristic of the presence of the C=C group. No absorption band is observed in the 17501735 cm-1 region, which indicates the absence of the ester COO group, and there is an intense absorption band in the 1485 cm-1 region charac-

teristic of bending vibrations of the R3N+ -group.

Thus, from the analysis of the IR spectra, it can be concluded that the alkylation reaction at the amino group is proceeding to obtain the diallyl monomer in the protonated form.

The structure of the carbon skeleton of the synthesized monomer - BEA was confirmed by H1 NMR spectroscopy (Figure 3), the data of which is consistent with the results of IR spectroscopy.

The radical polymerization BEA was carried out in aqueous solutions under conditions of radical initiation. Carrying out the polymerization reaction without radical initiators has shown that the reaction practically does not proceed. The reaction of radical polymerization of BEA proceeds according to the following scheme:

n H2C=CC1 CC1=CH — CÄ ® CH2

y/ ch2coo

CH,—CC1— CC1— CH2-

CH2 ® CH2

y/ ch2coo

n

The results of polymerization are shown in the table.

Results of the reaction of radical polymerization of BEA

Monomer, [M]=2 mol/l Initiator, [I]=5x10-3 mol/l Polymerization medium Temperature, 0C Yield, % Reduced viscosity (nred.), dl/g

AEA AP Water 60 45 0.16

AP Water 70 48 0.18

AP Water-alcohol 60 30 0.06

AP Water-alcohol 70 35 0.08

Fig. 1. IR spectrum of aminoethanic acid.

Fig. 2. IR spectrum of N,N-di(P-chlor)allylaminoethanic acid.

4 3 2

Fig. 3. Spectrum NMR :H of N,N-di(P-chlor)allylaminoethanic acid.

SYNTHESIS AND POLYMERIZATION OF N,N-DI(P-CHLOR)

17

As can be seen from the table, the highest values of the reduced viscosity were obtained in an aqueous solution as a AP initiator at a temperature of 700C.

Conclusions

1. The interaction of 1 mol aminoethanic acid with 2 mol of (P-chlor)allyl chloride in an aqueous solution of sodium hydroxide (pH>12) leads to the formation of a new monomer N,N-di(P-chlor)allylaminoethanic acid (BEA) with a yield ~45%.

2. During the polymerization of BEA (T=60-700C) in an aqueous solution in the presence of AP with an initiator 4-10-4-5-10-3 mol/l, water-soluble polymers with sufficiently high values of reduced viscosity ([n]=0.16-

0.18.dl/g) for the indicated amino acid were obtained.

3. It was found that polymerization proceeds along the double bonds of diallyl groups according to the cyclo linear mechanism with the formation of a polymer with a pyrroli-dine structure.

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20. Garamanov A.M., Gusiev N.H., Ahmedova R.A., Ibragimova M.M., Gurbanov M.SH. Sintez i po-limerizaciya N,N-di(ß-hlor)allilaminoetanovyj kisloty. Akademik Oli Musa oglu Nagiyevin 110 illik yubleyina hasr olunmu§ Respub. Elmi Kon-fransi. A§qarlar Kimyasi institutu. Baki. 2022. S. 194-195.

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19. Garamanov A.M., Ahmedova R.A., Mamedova A.A. Polimerizaciya N,N-di(ß-hlor)allilamino-etanovoj kisloty. Beynalxalq Elmi konfrans. Müasir tabiat va iqtisad elmlarinin aktual problem-

N,N-Di(ß-XLOR)ALLiLAMiNOETAN TUR§USUNUN SÍNTEZÍ УЭ POLÍMERLOSMOSÍ

O.M.Qaramanov, R.O.Ohmadova, N.X.Hüsiyev, B.O.Mammadov, A.F.Mamm3dova, M.§.Qurbanov

Aminoturjular zülallarin tarkibina daxil olan va canli orqanizmlarda biokimyavi proseslarda mühüm rol oynayan xiral birla§malardir. Onlar üzvi sintezda qurucu bloklar, asimmetrik sintezlarda katalizatorlarin komponentlari, ayrici agentlar va b. kimi geni§ istifada olunurlar. Bu maqsadla, tarafimizdan müayyan edilmi§dir ki, 1 mol aminoetan tur§usunun 2 mol (ß-xlor)allilxlorid va artiqlamasi ila götürulmü§ natrium hidroksidin suda mahlulunda (pH > 12) qar§iliqli tasirindan ~45% giximla yeni monomer - N,N-di(ß-xlor)allilaminosirka tur§usu (BET) alinir.. Sintez edilmi§ BET-nin su mühitinda ammonim persulfat (AP) i§tiraki ila, inisiatorun 410-4-5 10-3 mol/l qatiliginda, polimerla§ma reaksiyasi (Т= 60-700C) zamani suda hall olan kifayat qadar yüksak özlülüklü ([ngatir.] = 0.16-0.18 dl/q) polimer alinmiijdir. Müayyan edilmi§dir ki, polimerla§ma diallil qruplarinin ikiqat rabitalari hesabina tsikloxatti mexanizm üzra pirrolidin strukturlu polimerlarin amalagalmasi ila ba§ verir.

Agar sözlzr: aminoetan tur§usu, (ß-xlor)allilxlorid, inisiator, natrium hidroksidin suda m3hlulu, N,N-di(ß-xlor)allilaminoetan tur§usu.

СИНТЕЗ И ПОЛИМЕРИЗАЦИЯ ^^диф-ХЛОР)АЛЛИЛАМИНОЭТАНОВОЙ КИСЛОТЫ

А.М.Гараманов, Р.А.Ахмедова, Н.Х.Гусиев, Б.А.Мамедов, А.Ф. Мамедова, М.Ш.Гурбанов

Аминокислоты являются хиральными соединениями, входящими в состав белков и играющими важную роль в биохимических процессах в живых организмах. Они широко используются в качестве строительных блоков в органическом синтезе, компонентов катализаторов асимметрического синтеза, разделяющих агентов и др. С этой целью нами установлено, что взаимодействия 1 моля аминоэтановой кислоты и с 2 моля хлористый (ß-хлор)аллилом в водном растворе едкого натрия (pH > 12) приводит к образованию нового мономера N,N^^ß-хлор)аллиламиноэтановую кислоту (БЭК) с выходом ~45%. При проведении полимеризации БЭК (Т= 60-700C) в водном растворе в присутствии персульфат аммония (ПА) с концентрацией инициатора 4 10-4-5 10-3 моль/л были получены растворимые в воде полимеры с достаточно высокими значениями приведенной вязкости ([Лпртвед.] = 0.16-0.18 дл/г) для указанного аминокислоты. Установлено, что полимеризация протекает по двойным связям диаллильных групп по циклолинейному механизму с образованием полимера пирролидиновой структурой.

Ключевые слова: аминоэтановая кислота, хлористый (ß-хлор)аллил, инициатор, водный раствор едкого натрия, N,N-диф-хлор)аллиламиноэтановая кислота.