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AZERBAIJAN CHEMICAL JOURNAL № 2 2023 ISSN 2522-1841 (Online)
!SSN 0005-2531 (Print)
UDC 547.867.3:547.566
STUDY OF THE CONDENSATION REACTION OF 2-ALLYLPHENOL WITH FORMALDEHYDE AND METHYLAMINE AND THE FUNCTIONAL PROPERTIES OF
THE OBTAINED PRODUCTS
G.M.Mehdiyeva, M.R.Bayramov, M.A.Agayeva
Baku State University [email protected]
Received 27.01.2023
Accepted 24.02.2023
By triple condensation of 2-allylphenol with formaldehyde and methylamine (at a ratio of 1:1:1 and 1:2:1 mol, at 800C for 3 hours) a number of compounds (I-III) of various structures was prepared. !t has been established that, depending on the ratio of the taken reagents, compounds of various structures are formed. By the reaction of compound I - 8-allyl-substituted 1,3-benzoxazine with HBr quaternary ammonium salt (IV) was obtained. Antimicrobial activity of 8-allyl-substituted 1,3-benzoxazine (I) and ammonium salt (IV) against microorganisms: Staphylococcus aureus NCTC 6571, Staphylococcus aureus ATCC®25923, Escherichia coli ATCC®25922, Candida dbicans NSTC-3255/ATCC2091, Shigella flexneri ATCC®12022, Salmonella enterica ATCC®13076, and Aspergillus niger (aquatic isolate) was studied. It was found that compounds I and IV at a concentration of 30 mg/L in comparison with the references (amoxicillin and fluconazole) have the highest bactericidal and fungicidal properties. By thermal treatment of compound I cross-linked copolymer V was synthesized. While studying the thermal properties of copolymer V their sufficient thermal stability (up to ~4500C) was established. Copolymer V also has a sorption property for the extraction of uranyl ions from aqueous systems (the degree of extraction at pH 7 is ~70%, the sorption capacity - 178 mg/g). The structures of the obtained compounds were confirmed by IR and NMR spectroscopy.
Keywords: 2-allylphenol, methylamine, benzoxazines, copolymers, bactericides.
doi.org/10.32737/0005-2531-2023-2-30-39 Introduction
Phenol derivatives containing various functional groups and heteroatoms in their structures are relevant and promising both in theoretical and applied terms [1-5]. They can be used in various fields of technology as antioxidant, an-ticorrosive, antimicrobial additives to oils and fuels, stabilizers of polymeric materials, analytical reagents, etc. [6-12].
Despite various studies in the field of chemistry of phenolic compounds, in recent decades researches devoted to the study of their natural and synthetic functionally substituted derivatives are continued [13-16].
A very convenient way to obtain nitrogen-containing compounds in organic synthesis is the triple condensation of a substrate (a compound containing an active hydrogen atom) with formaldehyde and amines, known in scientific and technical literature as the Mannich reaction [17, 18].
Although the Mannich reaction has been studied for a long time, interest in it does not
wane [7-11]. This is especially true for Mannich reactions with primary amines. In this case, by regulating the ratio of the initial reagents, a series of compounds with completely different properties can be obtained. For example, when using ammonia and primary amines, the presence of the initially formed Mannich base makes it possible to participate in further chemical transformations, often with obtaining of valuable products [19-21].
Therefore, the continuation of such studies in the field of obtaining nitrogen-containing organic compounds of various structures is very appropriate. For example, on the basis of phenols and their various derivatives with formaldehyde and primary amines of various structures, heter-ocyclic compounds, 1,3-benzoxazines, have been obtained, which have a number of valuable properties [22-26]. They can be used as biologically active compounds in medicine and other areas [27-33] and precursors in polymerization reactions [34-39].
The aim of this work is to study the reac-
tion of triple condensation of 2-allylphenol with formaldehyde and methylamine, as well as study the products obtained on their basis. The presence of a multiple bond in the structure of 2-allyl-phenol makes it possible to carry out the structuring process on the basis of the reaction products.
Experimental part
1H and 13C NMR spectra of the compounds were recorded using NMR spectrometer (AVANCE 300) (Bruker). The solvent was CDCl3 (99.8%, 151831, Sigma-Aldrich). The IR spectra of the compounds were recorded on a Varian 640 FT-IR spectrophotometer in the frequency range 4000-400 cm-1 at room temperature.
As starting reagents were used: 2-allylphenol (98%, Sigma-Aldrich, bp = 220-2210C, d20 = 1.028 g/cm3, n^0 =1.578), methylamine (40% aqueous solution, chemically pure, ZAO Vekton), anhydrous calcined Na2SO4 (analytical grade, ZAO Vekton), and formalin (37%
aqueous formaldehyde solution) (Karmalab). Dried and distilled benzene (analytical grade, ZAO Vekton) was used in the reaction and extraction (as a solvent).
The triple condensation reaction of 2-allylphenol with formaldehyde and methylamine was carried out according to the method [19] at a ratio of 2-allylphenol, formaldehyde and methylamine 1:2:1 (mol) and 1:1:1 (mol) respectively, at a temperature 800C for 3 hours.
1) As was established by spectral studies, with a ratio of reagents of 1:2:1 (mol), the reaction proceeds as follows (with the formation of three compounds I, II and III) (Scheme 1).
Syntheses were carried out as follows.
Calculated amounts of formalin (37% aqueous solution of formaldehyde) and methylamine (40% aqueous solution) were added into a three-necked reaction flask equipped with a stirrer, thermometer, and reflux condenser, and the mixture was stirred at a temperature of 0-50C for 0.5 hour.
o n-ch2
CH2-NH-CH3
II v III
Scheme 1. Triple condensation products at a ratio of 2-allylphenol, formaldehyde and methylamine 1:2:1 (mol)
Fig.1. 1H NMR spectra of a mixture of products I, II and III.
Then, the calculated amount of 2-allylphenol was added to the reaction mixture, and the reaction was carried out at a temperature of 800C for 3 hours. It is important to note that in the first case, when the reaction was carried out at a ratio of the initial reagents of 1:2:1 (mol), the resulting mixture was repeatedly washed with a 10% aqueous solution of potassium hydroxide in order to separate compounds II, III with phenolic hydroxyl) (as the corresponding phenolates) from compound I. It was found that compound I can be obtained with a yield of 48%. So, by triple condensation of 13.4 g (0.1 mol) of 2-allylphenol with 17 ml of formalin and 7.8 ml of a 40% aqueous solution of methylamine at a temperature of 800C and a time of 3 h, compound I was obtained -8-allyl-3-methyl-3,4-dihydro-2H-benzo[e][1,3]-oxazine. Yield 48%. Tbp.= 110-1150C/5 mm, n
20
= 1.5355, d20 = 1.020 g cm-3.1H NMR-spectra
(CDCls; 5, ppm) (Figure 1) : 2.5 (3H, c, CH3); 3.45 (2H, d, J=6 Hz, =CH-CH2-Ar); 4.0 (2H, s, N-CH2-Ar); 4.85 (2H, s, O-CH2-N); 5.05-5.18 (2H, m, CH2=CH-); 5.96-6.15 (1H, m, CH2=CH-); 6.73-
7.12 (3H, m, arom). 13C NMR-spectra (CDCls; 5, ppm): 33.91; 40.0; 52.33; 54.62; 59.89; 84.69; 115.65; 120.06; 125.69; 127.64; 136.97; 152.04. IR (cm-1) (Figure 2): 749 (three substituted aromatic ring); 3071 (C-H-arom), 1456, 1335, 2909 (CH2CH3); 1637 (C=C-allyl); 1595 (C=C-arom); 2845, 994 (C-H of double bond of allyl fragment); 1221 (C-O); 1143 (C-N).
2) At a ratio of reagents 1:1:1 (mol) under identical conditions, the reaction proceeds with the formation of products II and III (Scheme 2) (Figure 3).
Preparation of a quaternary salt based on compound I. Reaction of compound I with HBr for 0.5 h at room temperature quaternary ammonium compound IV - 8-allyl-3-methyl-3,4-dihydro-2H-benzo[e] [1,3] oxazinium bromide was prepared according to the scheme 3. o"
%^ 1 V
HBr ---^ ' Br"
vHf N—
IV
Scheme 3. Preparing of salt IV.
™l-1-1-r-
3800 3&00 3400 3200 3000 2300 2600 2400 2200 2000 1800 1600 140C 1200 1000 300 600
Wavenumber cm-1
Fig 2. IR spectra of compound I
oh
+ ch2o + ch3nh2
- h,o
oh
CH2-nh-CH3 II
?h ch3 n
ch2-oh
III
Scheme 2. Triple condensation products at a ratio of 2-allylphenol, formaldehyde and methylamine 1:1:1 (mol).
Fig.3. 1H NMR spectra of compounds II and III at equimolar ratio of initial reagents
HBr was obtained by reacting KBr with H2SO4. The resulting salt IV is a straw-yellow solid compound. Yield IV 88%. Tm. 1110C. IR spectrum of compound IV, cm-1 (Fig. 4): 749 (trisubstituted aromatic ring); 1463, 1376, 2920 (CH2, CH3); 1635 (C=C-allyl); 2850, 913 (CH of the short bond of the allyl moiety); 1261 (SO); 1190(C-N); 3210 (N+H); 525 (Br-).
Antimicrobial properties of compounds I and IV. The antimicrobial properties of compounds I and IV were studied by the diskdiffusion method [40, 41].
The following microorganisms were used in the work: Staphylococcus aureus NCTC 6571,
Staphylococcus aureus ATCC®25923, Escherichia coli ATCC®25922, Candida albicans NSTC-3255/ATCC2091, Shigella flexneri ATCC®12022, Salmonella enterica ATCC®13076, and Aspergillus niger (isolate, niger derived from water). The control museum strains of cultures used in the work were obtained at the Republican Sanitary and Quarantine Center under the Ministry of Health of the Republic of Azerbaijan.
Equal volumes of microbial flora, 1 ml each, were layered on Petri dishes with a selective medium for each pathogen using a standard
55
50 45 40 35 30 25 20 1510 5
(14)
913.257 152.670
1190.064 41.018 1261.357 8.024 019 5.239
2163.303 554.329 2363.759 138.041
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 16'
Wavenumber
1400 1200 1000
Fig.4. IR spectra of IV.
4
inoculum corresponding to a density of 0.5 according to the McFarland standard and containing approximately 1.5x106CFUml"1. Antifungal activity was determined in Sabouraud liquid nutrient medium and on Sabouraud Dextrose Agar (Himedia). The agar plates were dried at room temperature for 15 min. Then, discs with solutions of the test compounds at concentrations of 20, 30, and 50 mg/L in DMSO (for I) and in water (for IV) were prepared under laboratory conditions and added to agar media with sterile tweezers. The degree of sensitivity of the test microorganism was determined by the diameter of its growth suppression (in mm). Petri dishes were incubated for 24 hours (for bacteria at 370C, and for fungi at 280C) in a TC1 / 80 CITY thermostat (Russia). For comparison, amoxicillin (for bacteria) and fluconazole (for fungi) at a concentration of 50 mg/L were used as standards.
Sorption studies of a crosslinked copo-lymer V obtained on the basis of compound I. To study the sorption properties of crosslinked copolymers, we used a model system obtained by dissolving certain amounts of uranyl nitrate (Karmalab) in distilled water.
For the experiment, 50 mg of the cross-linked copolymer and the test aqueous solution containing uranilions were loaded into a 100 mL Teflon cup. Next, 10 ml of a buffer solution was introduced into the system, and the volume of the mixture was adjusted to 50 mL by dilution with distilled water. The system was kept in static mode at room temperature for 24 hours. Upon completion of exposure, the solution was filtered and the activity of 235U and 238U isotopes (Bq/L) was determined in it.
The efficiency of extraction of uranyl ions by copolymers was judged by the decrease in the concentration of these isotopes in the solution before and after sorption, and on their basis the degree of extraction of uranyl ions (R)
2 CH20 + RNH2
HO.
R
I
-N.
and the sorption capacity of the sorbent (CEC) were calculated using the following formulas (1) and (2):
C - C R = ^^^^ x 100%(1)
Co
C - C CEC = . V
m
sorb
(2)
sorb
where R is the degree of sorption (%), CEC is the sorption capacity of the sorbent (mg/g), C0 is the initial concentration of uranyl ions (mg/L), C is the equilibrium concentration of uranyl ions (mg/L), Vsorb is the volume of the sorption medium (mL), msorb is the mass of the sorbent (mg).
Using an ammonia solution (Karmalab) and acetic acid (Karmalab) (in certain ratios), we adjusted the pH of the medium, on which the behavior of uranyl ions and the efficiency of the sorbent largely depend.
To evaluate the sorption properties of crosslinked copolymers, an HPGe y spectrometer (with a germanium detector, manufactured by Canberra, USA) was used.
Results and its discussion
As can be seen from Scheme 1, the triple condensation reaction at a molar ratio of 2-allyl-phenol with formaldehyde and methylamine 1:2:1 mol, the reaction proceeds in three directions (Scheme 1) (Figure 1).
The synthetic Mannich condensation procedure for the synthesis of benzoxazine in a solvent proceeds primarily by adding an amine to formaldehyde at lower temperatures (0-100C) to form an N,N-dihydroxymethylamine derivative, which then reacts with the labile hydrogen of the hydroxyl group and the ortho position of the phenol at elevated temperature with the formation of an oxazine ring [22, 23]:
,OH
R
It should be noted that the NMR and IR spectra clearly show signals and absorption bands related to the multiple bond of the allyl fragment (Fig. 1-4). Thus, in the NMR spectra, the multiplet found at 6.2 ppm and protons of the CH2 group at a multiple bond at 5.2 ppm, and in the IR spectra, the absorption bands at 1637, 1595, 838 cm-1 clearly indicate the absence of reactions involving a double bond.
The mixture was treated with an aqueous solution of alkali to isolate heterocyclic product I, 8-allyl-substituted-1,3-benzoxazine, which was further converted into a quaternary salt by treatment with HBr.
The antimicrobial activity of compounds I and IV was studied. The research results are shown in Table 1.
As can be seen from the results of studies (Table 1) compounds I and IV have bactericidal and fungicidal activity. In comparison with the taken references, the compounds synthesized by us surpass them in antimicrobial properties. Compound IV possesses the highest antimicrobial activity, which, in addition to a multiple allyl bond and a benzoxazine ring, also contains a bromine anion in its structure. In addition, said compound is also highly soluble in water.
It is known from scientific and technical literature that 1,3-benzoxazines are thermally
stable (up to temperatures of 130°C and more) [42]. And depending on their structure at high temperatures, the oxazine ring opens and, as a result, oligomeric and polymeric products can form.
Thus, during the distillation of the synthesized compound I, it was found that the thermal transformation of the product occurs with the opening of the oxazine ring and copol-ymerization occurs at the oxazine ring and the multiple bond of the allyl group (Scheme 4).
In the absence of a multiple bond, linear copolymers are obtained [39]. However, in the presence of an 8-substituted multiple bond (in our case, an allyl group) in 1,3-benzoxazine (Scheme 4), cross-linked structures (V) are obtained. The resulting crosslinked copolymer was purified by washing it repeatedly in dimethyl sulfoxide and dried under vacuum to constant weight. The resulting copolymer is a dark brown solid compound. Its structure is confirmed by IR spectroscopy data (Figure 5). Comparing the spectra of compound I with spectra V, it can be said that the area related to the multiple bond is changed, the absorption bands of the OH group are also revealed, which confirms the opening of the benzoxazine ring, as well as the crosslinking of the multiple bond.
Table 1. Results of studies of the antimicrobial activity of compounds I, IV in comparison with references (amoxicillin
and fluconazole) at a concentration of 30 mg/L
Compound Microbial growth inhibition zone (mm)
S.aureus E.coli Salmonella enteridis Candida Albicans A.niger
I 28 30 26 32 22
IV 33 36 31 38 28
Amoxicillin 14 15 13 - -
Fluconazole - - - 14 10
O N-
A
Scheme 4. Obtaining of cross-linked polymer V based on I.
However, the remaining absorption bands can be said to coincide.
The thermal properties of the resulting copolymer V were studied. The results are shown in Figure 6. As can be seen from Figure 6, the weight loss of the copolymer is observed from a temperature of 400, and at 4470C, the maximum energy release is observed, which is confirmed by the peak formed. From this temperature, an endothermic peak is also detected. Complete weight loss occurs at a temperature of 5670C. The results of thermal analysis confirm sufficient stability of the obtained cross-linked copolymer V.
Polymeric materials based on benzoxa-zines began to be used as sorbents for sorption of heavy metals, in particular, for sorption
Pb(II), Fe(II), Mn(II), Cu(II), Zn(II), Cd(II ) and, especially, Hg(II) [43].
Therefore, in addition to sorption of heavy metals, the goal was to investigate the obtained copolymer also as a sorbent for trapping radioactive metals, in particular, uranyl ions. The results of studies of structured polymer V as a sorbent for the extraction of uranyl ions from model aqueous systems are given in Table 2.
Table 2 shows the results of studies of structured copolymer V as a sorbent for extracting uranyl ions from model aqueous systems.
As can be seen from the results of the tests (Table 2), the pH of the aqueous solution has a significant impact on the degree of extraction of uranyl ions and CES.
3( 2f 26 24 22 2( 1f 16 1 12
(3)
3489.446 0.602
907.670 120.523
3084.421 39.333
961.281 1.110
2400 2200 2000 Wavenumber
Fig. 5. IR spectra of the crosslinked polymer V.
Fig. 6. Thermal studies of polymer V.
1200
1000
4
Table 2. Results of sorption studies of 30 mg of polymer V at 25°C, time 24 hours (initial concentration of uranyl ions
in solution 154.3 mg/l)
pH cpegbi Content of uranyl ions in aqueous solution after sorption, mg/l The degree of extraction of uranyl ions (R, %) CEC, Mr/r
1 153.1 0.8 2.0
2 150.1 2.7 7.0
3 140.5 8.9 23.0
4 124.6 19.2 49.5
5 95.8 37.9 97.5
6 59.6 61.4 157.8
7 47.3 69.3 178.3
8 12.5 91.9 236.3
9 99.2 35.7 91.8
10 108.1 29.9 77.0
11 115.2 25.3 65.2
12 129.7 15.9 41.0
13 133.1 13.7 35.3
14 121.6 21.2 54.5
The best results are achieved at pH 8, however, in this case, in addition to the sorption process, hydrolysis also occurs. Therefore, the maximum degree of sorption is ~ 69% at pH 7. In the process of sorption of uranyl ions by a cross-linked sorbent, the OH group, the amine fragment, etc., can mainly participate.
Conclusions
The interaction of 2-allylphenol, formaldehyde, and methylamine under Mannich conditions yielded products of various structures, mainly with the formation of 8-allyl-substituted 1,3-benzoxazine (comp. I) (48%). By treating of compound I with hydrogen bromide, a quarter-nary ammonium salt (IV) was obtained and its antimicrobial activity against bacteria and fungi was revealed. Thermal treatment of compound I resulted in a cross-linked copolymer V, which has sorption properties with respect to uranyl ions in aqueous solutions (the degree of extraction is 69%). The resulting crosslinked copolymer has sufficient thermal stability (up to ~5 600C).
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2-ALLILFENOLUN FORMALDEHID VO METILAMINLO KONDENSLO§MO REAKSIYASININ VO ALINMI§ MOHSULLARIN FUNKSiONAL XASSOLORInIN TODQiQi
G.M.Mehdiyeva, M.R.Bayramov, M.A.Agayeva
2-Allilfenolun formaldehid va metilaminla ûçqat kondenslaçmasi naticasinda (1:1:1 va 1:2:1 mol nisbatinda, 800C tem-peraturda va 3 saat müddatinda) müxtalif quruluçlu birlaçmalar (I-III) sintez olunmuçdur. Müayyan edilmiçdir ki, alinan reagentlarin nisbatindan asili olaraq müxtalif strukturlu birlaçmalar amala galir. I birlaçmanin, 8-allil avazli 1,3-benzoksazinin HBr ila reaksiyasindan dördlü ammonium duzu (IV) sintez edilmiçdir. 8-Allil avazli 1,3-benzoksazinin (I) va ammonium duzunun (IV) Staphylococcus aureus NCTC 6571, Staphylococcus aureus ATCC®25923, Escherichia coli ATCC®25923, CantCan25912, Shigella flexneri ATCC®12022, Salmonella enterica ATCC®13076 va Aspergillus niger (su izolyasiyasi) mikroorqanizmlarina qarçi antimikrobiyal aktivliyi tadqiq edilmiçdir. Müayyan olunmuçdur ki, I va IV birlaçmalar 30 mq/l qatiliqda standartlarla (amoksisillin va flukonazol) müqayisada daha yüksak bakterisid va funqisid xüsusiyyatlara malikdir. I birlaçmasinin termiki emali naticasinda tikili polimer IX sintez edilmiçdir. IX polimerinin istilik xassalari öyranilarkan kifayat qadar termiki davamliligi (~4500C-a qadar) gôstarilmiçdir. Elaca da, alinmiç polimerin sulu sistemlardan uranil ionlarinin çixarilmasi üçün sorbsiya xassasina malikdir (pH 7-da sorbsiya daracasi ~70%, sorbsiya tu-tumu isa 178 mq/q taçkil edir). Alinan birlaçmalarin quruluçlari iQ va NMR spektroskopiyasi vasitasila tasdiq edilmiçdir.
Açar sözlzr: 2-allilfenol, metilamin, benzoksazinbr, sopolimerbr, bakterisidbr
ИССЛЕДОВАНИЕ РЕАКЦИИ КОНДЕНСАЦИИ 2-АЛЛИЛФЕНОЛА С ФОРМАЛЬДЕГИДОМ И МЕТИЛАМИНОМ И ФУНКЦИОНАЛЬНЫХ СВОЙСТВ ПОЛУЧЕННЫХ ПРОДУКТОВ
Г.М.Мехтиева, М.Р.Байрамов, М.А.Агаева
Тройной конденсацией 2-аллилфенола с формальдегидом и метиламином (при соотношении 1:1:1 и 1:2:1 моль, при температуре 800С и времени 3 час) получен ряд соединений (I-III) различной структуры. Установлено, что в зависимости от соотношения взятых реагентов образуются соединения различной структуры. Реакцией соединения I - 8-аллилзамещенного 1,3-бензоксазина с HBr получена четвертичная аммонийная соль (IV). Исследована антимикробная активность 8-аллилзамещенного 1,3-бензоксазина (I) и аммонийной соли (IV) по отношению к микроорганизмам: Staphylococcus aureus NCTC 6571, Staphylococcus aureus ATCC ®25923, Escherichia coli ATCC®25922, Candida albicans NSTC-3255/ATCC2091, Shigella flexneri ATCC®12022, Salmonella enterica ATCC®13076, а также Aspergillus niger (изолят, полученный из воды). Выявлено, что соединения I и IV в концентрации 30 мг/л в сравнении с эталонами (амоксициллин и флюконазол) обладают наиболее высокими бактерицидными и фунгицидными свойствами. При термической обработке соединения I получен сшитый сополимер IX. При исследовании термических свойств сополимера IX, показано, что они обладают достаточной термической устойчивостью (до ~4500C). Также они обладают сорбционным свойством для извлечения уранил ионов из водных систем (степень извлечения при рН 7 составляет ~70%, сорбционная емкость - 178 мг/г). Структуры полученных соединений подтверждены данными ИК- и ЯМР-спектроскопии.
Ключевые слова: 2-аллилфенол, метиламин, бензоксазины, сополимеры, бактерициды.
