Научная статья на тему 'Methods of synthesis of maleinimidoethyl ether of acetic acid'

Methods of synthesis of maleinimidoethyl ether of acetic acid Текст научной статьи по специальности «Химические науки»

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Ключевые слова
N-(2-HYDROXYETHYL-)MALEAMIC ACID / β-HYDROXYETHYLMALEIMIDE / β-CHLOROETHYLMA-LEIMIDE / MALEIC ANHYDRIDE / N-(2-ACETOXYETHYL)MALEIMIDE

Аннотация научной статьи по химическим наукам, автор научной работы — Turaeva Khurshida Kamalbaevna, Yuldasheva Mukhabbat Razzoqberdievna, Khaydarova Sadokat

New methods of obtaining N-(2-acetoxyethyl) maleimide using β-hydroxyethylmaleimide, reaction of β-chlorethylmaleimide with acetic acid and its sodium salt have been elaborated. The effect of solvent and temperature on the course of the reaction was determined. The structure of the syntheses substances was analyzed using physic-chemical research methods.

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Текст научной работы на тему «Methods of synthesis of maleinimidoethyl ether of acetic acid»

https://doi.org/10.29013/AJT-19-9.10-52-57

Turaeva Khurshida Kamalbaevna, National university of Uzbekistan, the Faculty of Chemistry

E-mail: torayevah@mail.ru Yuldasheva Mukhabbat Razzoqberdievna, National university of Uzbekistan, the Faculty of Chemistry

E-mail: ymuxabbat@bk.ru Khaydarova Sadokat, National university of Uzbekistan, the Faculty of Chemistry

METHODS OF SYNTHESIS OF MALEINIMIDOETHYL ETHER OF ACETIC ACID

Abstract.Newmethods ofobtainingN-(2-acetoxyethyl)maleimideusingP-hydroxyethylmaleimide, reaction of ^-chlorethylmaleimide with acetic acid and its sodium salt have been elaborated. The effect of solvent and temperature on the course of the reaction was determined. The structure of the syntheses substances was analyzed using physic-chemical research methods.

Keywords: N-(2-hydroxyethyl-)maleamic acid, ^-hydroxyethylmaleimide, ^-chloroethylma-leimide, maleic anhydride, N-(2-acetoxyethyl)maleimide.

Maleic acid derivatives are among the com- In the literatures, homo-polymerization reactions pounds with a high practical using maleic acid de- of N-(2-acetoxyethyl) maleinimide were synthesized

rivatives have been used various fields. In fact, in the production of different adhesives, the leaguer paint industry, rubber and polymers are received also, their derivatives are used as sewing agents [1; 2; 3; 4; 5]. Furthermore, maleimid group had been drugs used widely in the pharmaceutical industry [6].

In obtaining copolymers resistant to corrosion, the importance of maleimide monomers is considered to be great in the production of bis-ma-leimide derivatives, heat-resistant aviation carbon fibers, bis-maleimide derivatives, machine-isolating agents, adhesives for road bitumen, materials [7; 8; 9; 10; 11; 12].

We carried out a scientific investigation by finding new methods of obtaining (3-chlorethylmaleimide and N-(2-acetoxyethyl) maleimide. The methods proposed in the work were included reactions that can be carried out under normal laboratory conditions.

and obtained by microwave irradiation (microwave (MW) irradiation) in acetic acid and dehydrated sodium acetate catalysis [13].

Initially, N-(2-hydroxyethyl-)maleamic acid was synthesized from maleic angiotensin and ethanol-amine. This reaction was carried out by two methods. At the first the equimolar amounts of maleic anhydride with ethanolamine was carried out. Purified (T(bo )=169-171 °C) ethanolamine maleic anhydride poured into the cooled state for 30-40 minutes in an ice bath. Then the reaction is carried out by a ring reaction through the decomposition of the reaction mixture. The reaction mixture was heated in a water bath during 1 hour at 55-60 °C stirring. The resulting substance was purified by re-crystallizing in 70% ethyl alcohol.

In the second method of obtaining N-(2-hy-droxyethyl-)maleamic acid, the reaction was carried out in an acetone as solvent, the yield in this

reaction was 65%. The conditions of obtain ins of N-(2-hydroxyethyl-)maleamic acid are presented in

the (table 1).

Table 1.- Conditions of reaction of maleic anhydride with ethanolamine

Name and structure of the resulting substance

Temperature, °C

Solvent

Reaction time

Mole ratio Maleic anhydride: monoetha-nolamine

Yield,%

20-25: 50-55: 0

30-40 min

0: 50-55: 0

Ethanol

60 min

0: 50-55: 0

Acetone

150 min

0: 50-55: 0

Acetone

1day

0: 50-55: -12

Acetone

150 min

53

55

58

60

65

Based on the results of the conducted experiment, it can be said that with a decrease in temperature, additional reactions decrease, and with high yields, the possibility of taking N-(2-hydroxyethyl-)maleamic acid increases. With an increasing of reaction time, the yield of the product also has increased sharply. The nature of the solvents were used in the reactions also has effect the yield of the product and the course of the reaction [14]. Known polarity values of solvents:

Solvent Polar Et (30), kcall/moll 1

Acetone 0.355

Ethanol 0.654

During the synthesis of N-(2-hydroxyethyl-) maleamic acid was carried out in acetone, we saw that the reaction was easy on the low carbohydrate and went with a high yield. The main reason for this was the good melting of the substances obtained for the reaction in this solvent and the room temperature, the for the formed product was melted easy reactions were carried out in polar solvents and yield of reaction was lower, the higher the solubility of the formed product. Data of IR-spectrum of N-(2-hydroxyethyl-)maleamic acid are presented in (table 2).

Table 2.- Areas of self-absorption, cm-

v(O-H) carboxyl v(C=0) carboxyl v(N-H) amide v(C=O) amide v(CH=CH) v(-C-OH) v(CH2)

3309 1736 1539 1647 1628-1646 1174 2868-2960

The course of the reaction can be explained using ethanolamine to strongly polarized maleic acid with the following scheme. The reaction begins with an formation of a corresponding N-(2-hydroxyethyl-) attack of amino group with a high nucleophilicity of maleamic acid:

o

+ h2n-ch2-ch2-o-h

s-

£o

O'

o

c-h2n-ch2-ch2-o-h

£os- "

O-H

vc—hn-ch2-ch2-o-h ^o

The next stage is the process of dehydration. De- vent DMFA was used, cyclization were carried out hydration agents were P2O5/H2SO4(cons) and as, sol- temperature of 70 °C:

s-

O_H

—HN-CH2-CH2-O-H

P2O5, H2SO4

DMFA, 70 C

\

I

/

N—CH2-CH2-OH

oh Pyridine

+ SOCl2 ur-1*

O r

„O~S N- - /

In subsequent reactions, ^-chlorethylmaleimide was synthesized from ^-hydroxyethylmaleimide. In this method tionyl chloride was used to halogenize alcohols. The hydrophobicity of tionyl chloride and the presence of an active additive of maleimide make the one-side course of the reaction more difficult. The reaction was carried out at temperature of 0 0C at the same time. With a low temperature of the reaction, it is possible to ensure that the double bond in maleimide does not break: the of obtained light yellow sediment was participation with yield 55%:

^-Chlorethylmaleimide can also be obtained in the presence ofhydrogen chloride, CuCl and sulfuric acid:

N—CH2—CH2—OH -

CuCl HCl + H2SO4

- H2O

N—CH2—CH2—Cl O

areas

Following specific absorption areas of ^-chlorethylmaleimide in IR-spectrum were observed (sm-1, v): 1660 (C=0), 1423 (imide), 2864 (CH2), 644 (-Cl).

When the acetic acid reaction of the obtained (3-hydroxyethylmaleimide was carried out with the participation of sulfuric acid, the compound ether made up 40% of the yield:

N—CH2—CH2—OH + CH3—COOH >O

N-(2-acetoxyethyl)maleimide is white crystalline substance, T, 80-81 oC, Rf = 0.47 (silo-

1 liquid 1 v

fol, cystema benzene-ethylacetate 3:1). One more method obtaining complex ethers the effect ofhalo-gen alkanes on the salts of carbonic acids. With this method, it was possible to obtain ethers of acids, which are difficult to synthesize from space site.

Dipolar aproton solvents-DMPA, DMSO, GMP-TA, acetone, DMAA and others with anions do not bind hydrogen bonds. The interaction ofthese solvents with anions occur mainly on account ofion-dipole. The iondipole forces are formed from the interaction of anions and solvent molecules. For this reason, the dipolar aproton solvent solution dissolves small solid anions much weaker than proton solvents. Solvation of anions decreases in solvents ofdifferent nature in the following range:

h2o > CH3OH > C2H5OH > hconh2 > ch3no2 > >CH3CN > DMFA > DMSO > GMFTA > methylpyr-rolidine-2

o

H2SO4 -H2O

O

II

N—CH2—CH2—O—C—CH3

O

The nucleophilic properties of anions has increased at passage from water or methane to DMSO and GMFTA. If the reaction of acid salt (RCOOMe) with halogen alkane is carried out in a solution of GMFTA, the compound ether is dressing with a high was yield.

GMPTA

R—COONa + RCH2X -► RCOOCH2R + NaX

We were carried out at the reaction of ^-chlore-thylmaleimide with acetic acid sodium salt in dimeth-ylsulfoxide yield of product was 60%:

O

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+ CH3COONa O

if

O

This means that the structure ofthe carbonic acids obtained for the reaction to the course of the etheri-fication reaction, in which ^-chlorethylmaleimide goes with the participation of aliphatic carbonic acid

O

N

-SO

O

O

O

-HO

O

O

O

salts, also affects the nature of the solvent and the Data of IR-spectrum are presented in (table 3) temperature of the reaction. of maleimidoethyl ether of synthesized acetic acid.

Table 3.- N-(acetoxyethyl)maleimide areas of self-absorption in the IR-spectrum, cm-1

° v(C=0) v(imide) v(CHj v(C(O)OC)

1651 1419 2856 1271

In general, the rate of the etherification reaction and the yield of the product have been depended on the nature of carbonic acid and alcohol, and also temperature and nature of catalyst

Experimental part:

Infrared Fourier spectrometer "IRTracer-100" (SHIMADZU CORP., Japan 2017) in complete with the prefix broken total internal reflection (NIP) MIRacle-10 c prism diamond/ZnSe (spectral range on the scale ofwave numbers-4000^400 cm1; resolution - 4 cm1, sensitivity signal-to-noise ratio-60,000:1; scanning speed-20 spectra per second); PMR1H-spec-trometer the Unity 400plus (Varian) ICPS AS RUz spectrometer in (CD3OD). Have been used purity of obtained compounds was carried out on the was determined on thin-layer chromatography (TLC) with plates (Pre-coated TLC sheets ALUGAM® Xtra SIL G/UV254), mobile phase-benzene: methanol 3:1.

Synthesis of N-(2-hydroxyethyl-)maleamic acid:

A) On a water ice bath tub put 3 g(0.03 mole) of maleic anhydride into the round tube, slowly drip 1.85 g (0.03 mole) of ethanolamine was added. After mixing with the mixture, water vapor was formed as a result of thermal decomposition. Then we heated the formed glue in a water bath, after 30 hours we put 15 ml of ethyl alcohol on the mixture and crystallize again. The purity of the thin layer was determined in chromatography. (silofol, benzene to the system: methanol 3:1, Rf = 0.38). T^ = 116-117 °C.

B) Synthesis of N-(2-hydroxyethyl-)maleamic acid: 9.8 g (0.1 mole) of maleic anhydride and 6.1 g (0.1 mole) of ethanolamine were dissolved in 15 ml of acetone solution. Both solutions were mixed for 2

hours in an ice water bath, drip 1 and 2 drops into the tube. In a colander with a reverse refrigerator, the reaction mixture was heated for 50-55 °C in water bath during 1-1,5 hours. Then, in a low temperature was cooled with ice water and left for 1 day. The fallen white sediment was filtered and dried in a room cart. 10.4 g (65%) ofyield. It was recrystallized again in ethanol.

T=116-117 0C. 1H-NMR (CD3OD S.m.d) 3.24 slH, OH), 3.54-4.25 t (2H, 2CH2), 4.87 s (H, NHCO), 6.19-6.41 d (H, CH=CH), 6.30 s (H, COOH). 13C-NMR (CD3OD-49.00 ppm S.m.d) 39.7 s (-N-CH2-), 63.9 s (-O-CH2-), 131.5-130.7 d (-CH=CH-), 167.1-168.6 d (C=O).

Synthesis of ^-hydroxyethylmaleimide: The mechanical stirrer is furnished with dropper, funnel and reverse cooler. N-(2-hydroxyethyl-)maleamic acid (9.81 g 0.1 mole) was solved in 30 g of DMPA solution and on to its solution 7.4 g of P2O5 and 1 ml of H2SO4 were put and need to mix. The reaction was held for about 8-9 hours at 70 °C. Then the reaction mixture was cooled, the reduced sediment was filtered, the substance was washed several times in cold water. 55% of yield it was cleaned again with ethyl alcohol has been crystallized. Then CaCl2 was dried on a laid-out extractor. T =71-72 °C1H-NMR

liquid

(DMSO, S.m.d) 2.87-3.6 m (2H, 2CH2), 7.82-7.89 d (2H, -HC=CH-), 5,99 s (H, -OH).

Synthesis of ^-chlorethylmaleimide:

A) The mechanical stirrer is furnished with dropper, funnel and reverse cooler. 15.9g of ^-HEMI were put to three-mouth tuber on 30 ml of pyridine was added. The reaction was carried out in a bath of ice water, in chilled conditions. A reagent mixture was mixed while the dropper was injected into the fun-

nel with tionyl chloride. During the reaction, the extracting SO2 and HCl gases were lowered into the mining KOH solution through a tube connected to the reverse refrigerator, and in every 10 minutia pH value was checked with the indicator paper. The reaction was being lasted for 2 hours. Going to the end of the reaction, the temperature raised to 50-60 °C and to be continued for 30 minutes. Receiving mixture was cooled, poured ice water and separated from the fallen sediment and dried in a room cart. 55% of yield (silofal, benzene to the system: methanol 3:1, Rf = 0.27). T, = 184-185 °C.

' liquid

B) Mechanical stirrer is furnished with dropper, funnel and a reverse cooler. Mechanical 4 g of (3-HEMIwere put on 10 ml of HCl(cons) and 0.5 g of CuCl were added. The reaction was carried out in an ice water bath with a cooled solution. At drip funnel 2.5 ml of H2SO4(cons.) was initially injected and then 1 ml was added, then the remaining part of the amount was poured into 50-60 °C. It was lasting 2.5 hours. Then the reaction mixture was cooled, put ice water on it, separated by a filter of the fallen white sediment and washed several times in cold water. Dried in the open air. Our reputation was 27%. T, = 184-185 °C.

liquid

Synthesis of N-(2-acetoxyethyl) maleimide ether. A tube equipped with a refrigerator, cooker

and mechanical agitator was added 141 g (0.01 mole), ^-hydroxyethylmaleimide and 0.3 g sulfuric acid 1.2 g (0.02 moles)and toluol were collected on top, putting the acid in the iceberg. The reaction was carried out for 3 hours. At the end of the reaction, 10 ml of distilled water was poured into the reaction mixture. The fallen precipitation was filtered out. the substance was washed several times by cold water. Obtained with hydrochloric acid ^-hydroxyethylmaleimide of acetic acid 48% of yield

B) Tube mixed with magnetic (mixer)into a flat tube, N-(chlorethyl)maleimide (1.5 g, 0.01 mole), 0.82 g crushed sodium acetate and DMSO 15 ml. The reaction lasted 2.5 hours. At the end of the reaction, the reaction mixture was cooled and poured into a container with ice water, the obtained was filtered. The substance was washed several times in cold water. 60% ofyield, ethyl acetate re-crystallized purified. Then CaCl2was dried on a laid-out extractor. Tliquid=80-81 °C. 1H-NMR (DMSO, S.m.d): S = 7.01 (s, 2H, HC=CH), 4.43 (t, 2H, -CH2-O-), 3.61 (t, 2H, CH2-N-), 1.98 (s, 3H, -CH3). 13C-NMR (DMSO, S.m.d): S = 171.49 (C=o), 170.21 (O=C-O), 134.87 (-CH=CH-), 60.12 (-O-CH2-), 38.1 (N-CH2-), 20.70 (-CH3).

References:

1. Pat. 31,301,826. Vulcanizate of sulfur vulcanizable rubber with N-maleimide deriva tives. O. Tawney, Filed Apr. 24,1964, Ser. No. 363,067 5 Claims. (Cl. 260-78).

2. Pat. 4,048,146 Radiation sensitive polymers of oxygen-substituted maleimides and elements containing same, John Charles Wilson, No.: 752,229, Sept. 13, 1977.

3. Pat. 4,954,637 Certan maleimide-N-alkylenecarboxylate ortho-nitrobenzenesulfonic acid esters and dervarves useful for coupling biological materials, Danute E. Nitecki, Berkeley, Sep. 4, 1990.

4. Pat. US6,921,765 B2 1-Azabicyclo2.2.2octan-3-one dervatives and maleimide dervatives and their use for treating cancertumiors, Vladimir Byko, Jul. 26, 2005.

5. Pat.US2005/0014924 A1 Maleimide group-containing polymer particles and method of producing the same, Yoshihiro Inaba, Jan. 20, 2005.

6. КоАямшин О. А. Малеинимиды: синтез, свойства, биологическая активность / О. А. Колямшин, В. А. Данилов, С. Ю. Васильева.- М., 2010.- 75 с.- Деп. в ВИНИТИ, № 250-В 2010 от 06.05.2010.

7. Колямшин О. А., Данилов В. А., Кольцов Н. И. Синтез новых бис-малеинимидов на основе алки-лароматических диаминов. Вестник Казанского технологического университета. 2011.- Т. 14.-№ 4.- С. 46-48.

8. Исаев P. H. Методы количественного определения малеинимидов Монография, Барнаул 2001.-C. 3-4.

9. Колямшин О. А., Афанасьев Е. С., Данилов В. А., Кольцов Н. И. Имиды малеиновой кислоты и их производные. Бутлеровские сообщения. Казань. Республика Татарстан. Россия. 2012.- Т. 30.- № 4.-С. 68-70.

10. Михайлин Ю. А. Термоустойчивые полимеры и полимерные материалы. СПб.: Профессия. 2006.-С. 528-623.

11. Михайлин Ю. А., Мийченко И. П. Малеинимидные связующие (обзор). Пластические массы. 1992.- № 5.- С. 56-64.

12. Светличный В. М., Кудрявцев В. В. Полиимиды и проблема создания современных конструкционных композиционных материалов. Высокомолекулярные соединения. Серия Б. 2003.- Т. 45.- № 6.-С. 984-1036.

13. Philipp Eckstein & Helmut Ritter. Microwave-assisted synthesis, transesterification and polymerization of N-(2-acetoxy-ethyl-)maleimide, Designed Monomers and Polymers, (2005) 8:6, 601-607.

14. Райхардт К. Растворители и эффекты среды в органической химми Пер. с анг. под ред.д.х. н.., проф. В. С. Петросяна.- М.: Мир, 1991.- С. 584-587.

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