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

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CHEMICAL PROBLEMS 2021 no. 4 (19) ISSN 2221-8688

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UDC 547.466.22b, 233.3, 315.3

SYNTHESIS AND POLYMERIZATION OF N-ALLYL-N-(ß-CHLOR)ALLYL ETHANIC

ACID

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

Institute of Polymer Materials of the National Academy of Sciences of Azerbaijan S. Vurgun str., 124, Sumgait, AZ5004, Azerbaijan Republic; e-mail: [email protected]

Received 25.09.2021 Accepted 01.12.2022

Abstract: The interaction of 1 mol aminoethane acid with 1 mol of allyl chloride and 1 mol of (fi-chlor)allyl chloride in an aqueous solution of sodium hydroxide (pH>12) leads to the synthesis of the new monomer -N-allyl-N(l3-chlor)allylethanic acid (AEA) with a yield of ~50%. During polymerization of AEC (T=60-70) in aqueous solution in the presence of ammonium persulfate (PA) initiator with a concentration of 4x10-4-5x10-3 mol/L, water-soluble polymers with rather high values of reduced viscosity ([nprid] = 0.18-0.20 dl/g) for the above mentioned amine were obtained. It was established that the polymerization proceeded on the double bonds of diallyl groups according to the cycle-linear mechanism with pyrrolidine stucture. Keywords: aminoethane acid, allyl chloride, (fi-chlor) allyl chloride, initiator, aqueous solution of sodium hydroxide, N-allyl-N(fi-chlor)allylethanic acid. DOI: 10.32737/2221-8688-2021-4-250-255

Introduction

The electro-active polymers on the basis amino acid are a new class of polymers that emerged comparatively recently. In recent years, this direction in polymer chemistry has been rapidly developing. The ion exchange sorbents, coagulants, flocculants, separating membranes, soil structurators, 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 which raise the soil fertility, regulate moisture supply to plants, decrease wind erosion of soils, stimulate plant growth and development, increase plant resistance to the effect of negative

temperatures, salinity, etc. [1-7].

At present, much attention has been paid to the synthesis of diallyl monomers, as well as polymers based on them owing to the wide range of application of water-soluble polymers; therefore, the synthesis of soluble polyelectrolyte polymers which are notable for complexes of valuable properties, in particular, amphophilic properties.

Developing the field of synthesis and studying properties of tertiary ammonium derivatives of diallyl nature [8] in this paper the method of preparation, structure, properties and synthesis of polymers based on N-allyl-N-(P-chlor)allylethanic acid will be considered.

Experimental part

Recrystallization aminoethane acid: molecular weight 75.57, density 1.6 g/cm3, melting point 232-236*C. Freshly distilled allyl

chloride - boiling point 45 °G, ^1.4154,

1^0.9379. Freshly distilled (ß-chlor)allyl chloride - boiling point 94°G, ^1.4600, (if 1.2080. Ammonium persulfate (AP)

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

Syntheses of N-allyl-N-(P-chlor) allylethanic acid. 7.55 g (0.1 mol) of aminoethane acid is placed in a two-liter four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and in cooling (not higher than 5°G ) is added dropwise 7.65 g (0.1 mol) of allyl chloride and 11.1 g (0.1 mol) of (P-chlor) allyl chloride for 1 h and then 50% of 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 30°C. An ice water bath is used to remove excess heat. Following the addition of sodium hydroxide solution, the reaction mass is slowly heated to 70°C. The reaction mixture was neutralized

(pH=7.0) with diluted hydrochloric acid. After the completion of the reaction, the reaction mixture is gradually poured into dry acetone in portions. The light yellow amino-acid as flakes is collected on the surface of the acetone. The

flakes are filtered on Buchner funnel, washed thoroughly with dry acetone, and then dried in an exicator over P2O5 to constant weight. The monomer melts with decomposition (at -287±0.2°C). The dried N-allyl-N-(P-chlor) allylethanic acid is obtained with a yield of 5055%. Found %: C 50.72, H 6.43, N 7.22, Cl 18.59. C8H12O2NCI Calculated, %: C 50.67, H

6.38, N 7.39, Cl 18.69.

Polymerization of N-allyl-N-(P-chlor) allylethanic acid. An aqueous solution (0.2 mol) of the monomer in the presence of initiator (4x10"4-5x10"3mol/l) was placed in a special ampoule, vacuumized and sealed. The ampoules were placed in a thermostat at a temperature 60 -70*C and kept for 14-24 h. After the

completion of the reaction, the reaction mixture was gradually poured into dry acetone in portions. The obtained flakes were filtered, washed thoroughly with dry acetone, and dried over P2O5 to constant weight. Yield - ~50%. The reduced viscosity is 0.18-0.20 dl/g. Found, %: C 50.82, H 6.47, N 7.41, Cl 18.67. C8H12O2NCI Calculated, %: C 50.67, H 6.38, N

7.39, Cl 18.69.

Results and discussion

It is known from the literature that it is sufficiently difficult to obtain N-alkylated a-amino acids. In the work [9], the authors showed that the basic and acidic amino acids did not react with allyl bromide nor formed the substitution products. The difficulties connected

H3N-

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

In an aqueous solution, depending on the

with carrying out of alkylation of a-amino acids are apparently associated with the fact that a-amino acids are amphoteric (bipolar) compounds and correspond to the general formula:

CH2-cooe

pH of the medium, the molecule takes the following form:

© ©

® -H © © -H ©

H3N-CH2-CHOOH H3N-CHrCOO H2N-CH2COO

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

H,N-CH,-COO

© + NaOH, pH > 12

HoN-CH,COO

in which the basic properties of NH2- group are enhanced, as a result of which the alkylation reaction is possible.

For synthesis of N-allyl-N-(P-chloro) allylethanic acid - diallyl monomer, the

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

H2N-CH2-COOH +

CH2=CHCH2C1 + 2 NaOH CH2=CC1CH2C1

-2 NaCl -2 H20

CHo=CH-CHo\ ©

" /N-H

CH2=CC1-CH2

CHo-COO

©

The identification of the product was characterized by absorption bands in the field of

carried out by comparison of the absorption 3100-3400 cm-1 for the associated group NH2;

bands of the characteristic groups of the IR in the field of 1725-1680 cm-1 for the carboxyl

spectra. The amino acid contains two functional group - COO- (figure 1). groups - NH2 and COO-, which are

Figure 1. IR spectrum of aminoethanic acid

In the case of the formation of N-allyl-N-(P-chloro) allylethanic acid with the analytical signal confirming the alkylation reaction is the presence of spectrum of an intensive absorption in the field of 1620 cm-1 which is characteristic for the presence of C=C group (figure 2). No absorption band was observed in the field of 1750-1735 cm-1 which indicates the absence of the ester COO- group,

and there was an intense absorption band in the field of 1485 cm-1 characteristic for deformation vibrations of R3N+ - group.

Thus, it can be concluded from the analysis of IR spectra that the alkylation reaction proceeds on the amino group with preparation of the diallyl monomer in the protonated form.

Fig. 2. IR spectrum of N-allyl-N-(ß-chlor)allylethanic acid

The radical polymerization of N-allyl-N-(P-chloro) allylethanic acid was carried out in aqueous solutions under conditions radical initiation [10]. It was experimentally shown that the polymerization reaction of the above-

n H2C=CH

CCl=CH2

CH2 © ^CH2

H

/

N

/

©

CH2COO

mentioned monomer without initiators of radical nature practically did not proceed.

The reaction of radical polymerization of N-allyl-N-(P-chloro) allylethanic acid proceeded according to the following scheme:

ch2—CH— CCI—CH2

CH2 © CH2

/N\ © H' CH2COO

n

Results of polymerization are shown in Table.

Table. Results of the radical polymerization reaction of N-allyl-N-(P-chloro) allylethanic acid

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

AEA AP Water 60 50 0.18

AP Water 70 62 0.20

AP Water-alcohol 60 40 0.08

AP Water-alcohol 70 44 0.10

As can be seen from Table, the highest temperature 70°C. The reduced viscosity values values of the reduced viscosity were obtained in of the synthesized samples of polymer are an aqueous solution as an AP initiator at a 0.18^0.20 dl/g.

Conclusions

1. The interaction of 1 mol aminoethane acid with 1 mol of allyl chloride and 1 mol of (P-chloro) allyl chloride in an aqueous solution of sodium hydroxide (pH> 12) leads to the formation of a new monomer of N-allyl-N-(P-chloro) allylethanic acid (AEA) with a yield -50%.

2. During the carrying out of AEA polymerization (T=60-70°G) in an aqueous solution in the presence of AP with an

initiator 4x10-4-5x10-3 mol/l, the water-soluble polymers with sufficiently high values of reduced viscosity ([n]= 0.18^0.20 dl/g) for the indicated amine were obtained.

3. It was established that the polymerization proceeded on the double bonds of diallyl groups according to the cyclo-linear mechanism with the formation of a polymer with pyrrolidine structure.

References

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2. Keiji M. Catalytic asymmetric synthesis of a-amino acid derivatives and peptides using chiral phase-transfer catalysts. Proceedings of the Japan Academy, Series B. 2003, vol. 79B, no. 7, pp. 181-189. DOI: 10.2183/pjab.79B.181.

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6. Patterson D.E., Xie S., Jones L.A., Osterhout M.H., Henry C.G., Roper T.D. Synthesis of 4-fluoro-ß-(4-fluorophenyl)-L-phenylalanine by an asymmetric phasetransfer catalyzed alkylation: Synhesis on scale and catalyst stability. Organic Process Research & Development. 2007, vol. 11, no. 3, pp. 624-627. DOI: 10.1021/op060190j.

7. Pat. RU2145978C1 (publ. 2000). Leather production method.

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9. Kanao S., Sakaeri Ya. N-alkylaminoacids. Yakugaku zasshi. 1966, vol. 86, no. 11, pp. 1105-1108. DOI: 10.1248/yakushi1947.86.11_1105.

10. Pat. RU 2439086C1 (publ. 2012). Poly N,N-diallylaminoethane acid.

N-ALLiL-N-(ß-XLOR)ALLiLETAN TUR§USUNUN SÍNTEZÍ V9 POLÍMERLa§M9SÍ

Э.М. Qaramanov, R.9. 9hmadova, В.Э. Mammadov, A.F. Mammadova,

N.X. Hüsiyev, M.§. Qurbanov

Azarbaycan Milli Elmlar Akademiyasinin Polimer Materiallari institutu S. Vurgun küfasi, 124, AZ 5004, Sumqayit e-mail: [email protected]

1 mol aminoetan tur§usunun 1 mol allilxlorid, 1 mol (ß-xlor)allilxlorid va artiqlamasi ila götürulmü? natrium hidroksidin suda mohlulunda (pH >12) qarsiliqli tosirindon ™50% ciximla yeni monomer - N-allil-N-(ß-xlor)allilaminosirka tur§usu (AET) sintez edilmi§dir. Sintez edilmi§ AET -nin su mühitinda ammonim persulfat (AP) i§tiraki ila, inisiatorun 4х10-4-5х10-3 mol/l qatiliginda, polimerla§ma reaksiyasi (Т=60-70 0C) zamani suda hall olan kifayat qadar yüksak özlülüklü ([^gatir] = 0.18-0.20 dl/q) polimer alinmi§dir. Müayyan edilmi§dir ki, polimerla§ma diallil qruplarinin ikiqat rabitalari hesabina tsikloxatti mexanizm üzra pirrolidin strukturlu polimerlarin amalagalmasi ila ba§ verir.

A^ar sözlar: aminoetan tur§usu, allilxlorid, (ß-xlor)allilxlorid, inisiator, N-allil-N-(ß-xlor)allilaminoetan tur§usu.

СИНТЕЗ И ПОЛИМЕРИЗАЦИЯ ^АЛЛИЛ-^ф-ХЛОР)АЛЛИЛЭТАНОВОЙ

КИСЛОТЫ

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

Институт Полимерных Материалов Национальной АН Азербайджана улица С. Вургуна, 124, AZ 5004, Сумгаит, Азербайджан; e-mail: [email protected]

Взаимодействием 1 моля аминоэтановой кислоты с 1 молем хлористого аллила и 1 молем хлористого (Р-хлор)аллила в водном растворе едкого натрия (pH >12) синтезирован новый мономер - 1М-аллил-1\[-(Р-хлор)аллилэтановая кислота (АЭК) с выходом ™50%. При проведении полимеризации АЭК (Т= 60-70°С) в водном растворе в присутствии инициатора - персульфата аммония (ПА) с концентрацией 4х10"4-5х10"3 моль/л получены растворимые в воде полимеры с достаточно высокими значениями приведенной вязкости ([^привед] = 0.18— 0.20 дл/г) для указанного амина. Установлено, что полимеризация протекает по двойным связям диаллильных групп по циклолинейному механизму с образованием полимера с пирролидиновой структурой.

Ключевые слова: аминоэтановая кислота, хлористый аллил, хлористый ф-хлор)аллил, инициатор, ^аллил-К-ф-хлор)аллилэтановая кислота.