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CHEMICAL PROBLEMS 2020 no. 2 (18) ISSN 2221-8688
151
UDC 547.425:547.464:547.569
SOME PECULiARiTiES OF P-[1(3)-METHYLCYCLOALKYL]PHENOLS INTERACTION REACTIONS WITH PIPERIDINE
G.A. Huseynova
Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences, Baku, AZ1025, Khojaly av. 30, e-mail: [email protected]
Received 24.02.2020 Accepted 04.04.2020
Abstract: The article explores the synthesis of 2-piperidinomethyl-4-methylcycloalkylphenols as a result of aminomethylation reactions of p-[1(3)-methylcycloalkyl]phenols obtained by catalytic cycloalkylation reactions of phenol and 1-methylcyclopentene, 1- and 3-methylcyclohexenes with piperidine. Aminomethylation reactions were carried out through the interaction of p-cycloalkylphenols with 30% of formaldehyde and piperidine in the presence of a solvent. The reaction was realized at 30 C for 2 hours. Following results of the studies, it revealed that yields of the obtained target products amounted to 68.875.6% on p-(methylcycloalkyl). Chemical structures of 2-piperidinomethyl-4-methylcycloalkylphenols were confirmed by IR, 1H and 13C NMR spectroscopies, and physicochemical properties determined as well.
Keywords: phenol, 1(3)-methylcycloalkenes, cycloalkylation, p-[1(3)-methylcycloalkyl]-phenols, piperidine, aminomethylation, 2-piperidinomethyl-4-methylcycloalkyl-phenols DOI: 10.32737/2221-8688-2020-2-151-157
Introduction
Last decade's research into literary sources shows that alkylphenols-based chemical additives are widely used in different areas of industry [1-5]. In particular, they are used as antioxidants, additives, stabilizers, oxygenators of high efficiencies for oils, fuels, polymer materials, simultaneously with a ligand for catalytic precursors in olefins oligomerization processes, medicinal
preparations to fight plant diseases; as
pesticides in agriculture [6-11].
The article deals with the synthesis of
2-piperidinomethyl-4-
methylcycloalkylphenols by aminomethylation reactions of p-[1(3)-methylcycloalkyl]-phenols obtained due to catalytic cycloalkylation reactions of phenol with 1-methylcyclopentene (1-MCP), 1 -methylcyclohexene (1-MCH) and
3-methylcyclohexene (3-MCH) with piperidine.
Experimental part
p-(1-Methylcyclopentyl)phenol, p-(1-
methylcyclohexyl)phenol, p-(3-
methylcyclohexyl)phenol, formaline and piperidine have been used as primary raw materials in aminomethylation reactions.
p-[1(3)-Methylcycloalkyl]phenols were obtained by catalytic cycloalkylation of phenol with 1-methylcyclopentene, 1- and 3-methylcyclohexenes [12, 13] and their physicochemical properties as shown in Table 1.
Chromatographic analysis of the p-(methylcycloalkyl) phenols used for the
reaction was carried out using LXM-72 chromatograph.
Chromatographic analyses of the reaction and rectification products were realized on LXM-72M chromatograph. The column length was 2 m, 0.2±0.25 mm of the chromatone N-AW-/JMC silanated with dimethylchlorosilane washed by an acid was taken as a solid carrier, 5% of SE-30 methylcyloxane elastomer - as an inactive phase. The column initial temperature was 50°C, final temperature - 280 °C, programming rate - 10 °C/min., helium gas
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CHEMICAL PROBLEMS 2020 no. 2 (18)
rate - 50 ml/min., evaporator temperature - diagramme tape rate - 60 mm/h. 355°C, detector temperature - 300°C,
Table 1. Physicochemical properties of p-[1(3)-methylcycloalkyl]phenols
N Boiling point, °C/mm Hg Melting point, °C Mol. mass Elemental composition, %
Calc. Found
C H C H
1. 147-148 88 176 81.8 9.1 81.8 9.2
2. ■o 161-164 96 190 82.1 9.5 82.4 9.7
3. r> 158-160 91 190 82.1 9.5 82.7 10.0
30 20
Piperidine boiling point - 106 °G; n -1.4530; p -0.861; molecular mass-85.
In both cases, total 100% of the general peaks areas were taken for calculation of the amount of the initial and final products compositions by percent.
Aminomethylation reactions of p-methylcycloalkylphenols with formaldehyde and piperidine were studied in a three-necked flask. Calculated amounts of p-methylcycloalkylphenol, piperidine and the solvent (benzene) were added to the flask and heated. 30% formaline in a certain amount was added to the flask through dropping funnel within 45 min. when the temperature reached 30°C. Formaline addition was followed by increasing temperature up to 80°C and stirring for further 2 hours. At the end of the reaction, the mixture was washed by water for releasing unreacted formaldehyde. The amine compound was converted into the acid salt for purifying from alkylphenol. Then, the amine was treated by solid NH4 - an aqueous solution of acid salt and free amine compound was extracted. The amine obtained was released from water by means of extraction.
After purification from benzene, the residue was rectified at low pressure; the obtained 2-piperidinomethyl-4-methylcycloalkylphenols chemical structures and physicochemical properties were determined.
The reaction products spectra were drawn on ALPHA IR-Furye spectrometer of "BRUKER" company in the range of 6004000 cm-1 on Se/Zn crystal.
NMR spectra of the compounds obtained were drawn in NMR spectrometer (AFR) of 300 mHs speed. Chemical shifts of the signals (ppm) were taken in comparison to tetramethylsilane. Relative compositions of the protons of different structural fragments were determined by integration of peak areas on appropriate bands of spectra. Synthesis of 2-piperidinomethyl-4)1-methylcyclopentyl-phenol
The equation of p-(1-methylcyclopentyl)phenol aminomethylation reaction with formaldehyde and piperidine is given below:
+ CH
o + ffl/
A flask was filled with 44.0 g (0.25 mol) of p-(1-methylcyclopentyl)phenol, 7.5 g (0.25 mol) of formaldehyde, 44.0 g of benzene and heated. 21.3 g (0.25 mol) of piperidine was added to the mixture at 40°C by drops. After the addition of piperidine, temperature was raised up to 80°C and stirred within 2 hours. Then, the mixture was released from benzene, water and unreacted formaldehyde. The reaction residue underwent rectification in a Claisen flask, the target product was separated and its physicochemical properties and chemical structure determined.
42.5 g of 2-piperidinomethyl-4(1-methylcyclopentyl)phenol was obtained as a result of rectification and proved 72.4% of the the yield amount.
IR and 1H NMR spectra of the synthesized 2-piperidinomethyl-4(1-
methylcyclopentyl)phenol were drawn. Results of IR, 1H and 13C NMR spectra of the substance are presented below.
The following absorption bands were observed on IR spectrum of the sample: mathematical vibration of C-H bond of CH2 group at 745 cm-1; deformation and valence vibrations of C-H bond of CH2 and CH3 groups additionally at 1313, 1362, 1383, 1454, 1477, 2869, 2929, 2954 cm-1; 1,2,4-substituted benzene nucleus at 818, 873 cm-1, benzene
ring at 1503 cm-1; C=C bond of benzene nucleus at 1619 cm-1; =C-H bond at 1619 cm-1; absorption band of tert-nitrogen atom at 1193 cm-1, C- O-C bond at 1097, 1123 cm-1; deformation and valence bonds referring to OH group O-H bond at 1248, 3291, 3370 cm-1.
The following absorption signals are observed on NMR 1H spectrum of 2-piperidinomethyl-4(1-
methylcyclopentyl)phenol: proton in CH2 group of cyclopentyl radical at 5=1.45 ppm (in a singlet state), hydrogens in cyclopentyl group at 5=1.6-1.9, hydrogens in N(C№)2 group at 5=2.5 (in singlet states), protons in O(CH2)2 and CH2N group at 5=3.62-3.7 (in multiplet states), and protons in aromatic nucleus at 5=6.75-7.2 (in multiplet states).
The following absorption signals are observed on NMR 13C spectrum of 2-piperidinomethyl-4(1-
methylcyclopentyl)phenol: carbon atoms in CH3 group at 5=25 ppm (in singlet states), carbon atoms in cyclopentyl group at 5 = 27 ppm, in N(CH2)2 group at 5=52-61.5 ppm (in singlet states), carbon atoms in CH2N group at 5=59 ppm (in singlet states), in O(CH2)2 group 5=67.5 ppm (in singlet states), and carbon atoms in aromatic nucleus at 5=115, 122, 126.5, 130, 141.5, 155.5 ppm (in singlet states).
Synthesis of 2-piperidinomethyl-4(1-methylcyclohexyl)phenol
The aminomethylation reaction runs on the equation below:
(^fj + ch2O + m/ y>
1/
A flask was filled with 47.5 g (0.25 mol) of p-(1-methylcyclohexyl)phenol, 7.5 g (0.25 mol) of formaldehyde and 47.5 of benzene and heated. 21.3 g (0.25 mol) piperidine was added to the mixture by drops at 40°C. After addition of piperidine, temperature rose up to 80°C and the mixture was stirred within 2 hours at this temperature. Then, the mixture was processed in line with the above-mentioned methodics and underwent rectification.
54.3 g of 2-piperidinomethyl-4(1-methylcyclohexyl)phenol was obtained as a result of rectification and revealed that the yield of the target product amounted to 75.6% on the taken p-(1-methylcyclohexyl)phenol.
Physicochemical properties and chemical structures of the synthesized 2-piperidinomethyl-4(1-methylcyclohexyl)phenol were determined.
Results of IR, 1H and 13C NMR spectral analyses of the substance are given below.
The following absorption bands were observed on IR spectrum of 2-piperidinomethyl-4(1-
methylcyclohexyl)phenol: mathematical
vibration of CH2 group C-H bond at 746 cm-1, deformation and valence vibrations of C-H bond of CH2 and CH3 groups, at 1313, 1362, 1383, 1454, 2868, 2928, 2953 cm-1, correspondingly; 1,2,4-substituted benzene nucleus at 818, 873 cm-1; benzene ring at 1503 cm-1; C=C bond of benzene nucleus at 1615
cm-1; deformation and valence vibrations of OH group O-H bond at 1192 cm-1 referring to tertiary nitrogen atom.
The following absorption bands were observed on NMR 1H spectrum of 2-piperidinomethyl-4(1-
methylcyclohexyl)phenol: hydrogen in CH3 group of cyclopentyl radical at 5= 1.42 ppm (in a singlet state), hydrogens in cyclohexyl group at 5=1.75-2.24 ppm, hydrogens in N(CH2)2 group at 5=2.84 ppm (in singlet states), O(CH2)2 and CH2N (in multiplet states), hydrogen atoms in aromatic nucleus at 5=6.95, 7.12 and 7.39 ppm (in multiplet states).
The following absorption signals were recorded on NMR 13C spectrum of 2-piperidinomethyl-4(1-
methylcyclohexyl)phenol: carbon atom in CH3 group at 5=26, 30.4, 36.4, 37 ppm, in N(C№> group at 5=51.7 ppm (in a singlet state), carbon atom in CH2N group at 5=61.8 ppm (in a singlet state), carbon atoms in O(CH2)2 group at 5=65 ppm (in singlet states), and carbon atoms in aromatic nucleus at 5=115, 119.5, 124, 125, 139, 154 ppm (in singlet states).
Synthesis of 2-piperidinomethyl-4(3-methylcyclohexyl)phenol
P-(3-methylcyclohexyl)phenol aminomethylation reaction with formaldehyde and piperidine is shown in the equation below:
+ ch2O + ro/
+ h,o
The quantities of the primary components taken for aminomethylation reaction - p-(3-methylcyclohexyl)phenol, formaldehyde and piperidine and the reaction conditions were consistent with quantities of primary components and reaction conditions of the previous experiment.
It resulted in obtaining 49.4 g of 2-piperidinomethyl-4(3-methylcyclohexyl)
phenol and 68.8% of the target product yield in the (3-methylcyclohexyl) phenol.
Chemical structure, physicochemical properties of the synthesized 2-piperidinomethyl-4(3-
methylcyclohexyl)phenol were found out. It revealed that integral curves of the substance IR, 1H and 13C NMR spectra were consistent
with previously presented integral curves of 2-piperidinomethyl-4(3-ethylcyclohexyl)phenol. Physicochemical properties of the
synthesized 2-piperidinomethyl-4[1(3)-
methylcycloalkyl]phenols are shown in Table 2.
Table 2. Physicochemical properties of 2-piperidinomethyl-4[1(3)-methylcycloalkyl]phenols
OH Boiling point, 0C/mm Hg Melting point, 0C Mol.mass Elemental composition, %
Calc. Found
C H N C H N
168-171 63 273 79.1 9.9 5.1 78.6 9.5 4.5
O 191-193 78 287 79.4 10.1 4.9 78.8 9.7 4.4
182-186 72 287 79.4 10.1 4.9 78.7 9.6 4.6
As is evident from Table, calculated methylcycloalkyl]phenols are consistent with mol masses and elemental compositions of properties identified. synthesized 2-piperidinomethyl-4[1(3)-
CONCLUSION
1. P-[1(3)-methylcycloalkyl]phenols amino-methylation reactions were carried out. 2-piperidinomethyl-4[1(3)-methylcyclo-alkyl]phenols of 68.8-75.5% yield synthesized as a result of the researches carried out.
2. Chemical structures of the 2-piperidinomethyl-4[1(3)-methylcyclo-alkyl]phenols synthesized by IR, and 13C NMR spectral analyses were confirmed and physicochemical properties determined.
References
1. Shakhmuradov S.T., Agamaliev Z.Z., Mejidov E.A., Rasulov Ch.K., Catalytic cycloalkylation of para-chlorophenol with 1-methylcycloalkenes. Mir nefteproduktov -World of Petroleum Products, 2018, no. 2, pp. 13-18. (In Russian).
2. Shakhmuradov S.T., Mirzoev V.G., Dzhafarov R.P., Rasulov Ch.K. Optimization of the alkylation of para-chlorophenol with 1-methylcycloalkenes. Mir nefteproduktov - World of Petroleum
Products. 2017, no. 12, pp. 20-24. (In Russian).
3. Shakhmuradov S.T., Rasulov Ch.K., Aliyev R.V., Bagirova Sh.R., Khamiev M.D., Huseynova M.B. Synthesis and study of 2-(1-methylcyclohexyl)-4-chlorophenol as a thermal stabilizer of polypropylene. Neftepererabotka i neftehimija - Oil refining and petrochemistry. 2018, no. 5, pp. 18-22. (In Russian).
4. Shahmuradov S.T. Some features of cycloalkylation reaction of p-chlorophenol
with 1-methylcycloalkenes. Chemical problems, 2019, vol.17, № 4, pp. 607-612
5. Bayramov M.R., Yusubov N.N., Mamedova Z.A. et al. Aminomethylation of alkyl phenols. Khimiya i khimicheskaya tekhnologiya - Chemistry and Chemical Technology. 2008, vol.51, no. 6, pp. 24-26. (In Russian).
6. Zeng H., Li H., Shao H. One-pot three-component Mannich-type reactions using Sulfamic acid catalyst under ultrasound irradiation. Ultrasonics Sonochemistry, 2009, vol.16, pp. 758-762.
7. Zhao G., Jiang T., Gao H. et. al. Mannich reaction using acidic ionic liquids as catalysts and solvents. Green Chemistry , 2004, vol. 6, pp. 75-77.
8. Zhong X.L., Gao F., Wang Q. et.al. Excited state intramolecular proton transfer of novel conjugated derivatives containing hydroxy and imino groups. Chinese Chemical Letters, 2010, vol. 21, pp. 1195— 1198.
9. Fomin V.N., Kotova N.S., Tarasov A.V. et al. Alkylation of phenol with ethylene oligomers. Neftepererabotka i neftehimija -Oil refining and petrochemistry. 2010, no. 9, pp. 14-17. (In Russian).
10. Khusunutdinov R.I., Shchadneva N.A., Khisamova L.F. Alkylation of aromatic compounds with 1-bromadamantane under the influence of metallocomplex catalysts. Russian Journal of Organic Chemistry. 2015, vol. 51, no.11, pp. 1576-1581.
11. Chukicheva I.Yu., Spirikhin L.V., Kuchin A.V. Molecular tandem rearrangement during the alkylation of phenol with camphene. Russian Journal of Organic Chemistry. 2008, vol. 44, no.1, pp. 69-73.
12. Mirzayev V.H., Ch.K.Rasulov, S.G.Aliyeva, E.M.Kuliyeva. Synthesis and study of antioxidative properties of aminomethylated derivatives of p-(cyclohexene-3-yl-ethyl-phenol). Chemical problems, 2019, № 3, pp. 386392
13. Abasov V.M., Rasulov Ch.K., Mirzoyev V.H., Agamaliyev Z.Z., Bagirzade R.Z,, Majidov E.A. Selektive catalytic alkylation and bcycloalkylation of phenol with alkyl-and alkenylcyclohexenes. Processes of petrochemistry and oil refining, 2017, no.4, pp. 341-350.
p-[ 1(3)-METiLTSiKLOALKiL] FENOLLARIN PiPERIDiNLd QAR$ILIQLI TdSiR REAKSiYALARININ BdZi XUSUSiYYOTLdRI
G.A. Huseynova
AMEA Neft-Kimya Prosesldri institutu AZ1025, Baki, Xocali pr., 30, e-mail: [email protected]
Mdqalddd fenolun 1-metiltsiklopentenld, 1- vd 3- metiltsikloheksenldrld katalitik tsikloalkilld§md reaksiyalari ndticdsindd alinmi§ p-[1(3)-metiltsikloalkil] fenollarin piperidinld aminometilld§md reaksiyalari ndticdsindd 2-piperidinometil-4-metiltsikloalkilfenollarin sintezinddn bdhs edilir. Aminometilld^md reaksialari p-tsikloalkilfenollarin hdlledici i§tirakinda 30%-li formaldehid vd piperidinld qar§iliqli tdsiri ild aparilmi§dir. Reaksiya 30°C-dd 2 saat mudddtindd hdyata kegirilmi§dir. Aparilan elmi tddqiqatlar ndticdsindd alinmi§ mdqsddli mdhsullarin giximlarinin goturuldn p-(metiltsikloalkil) fenollara gord 68.8-75.6% td§kil etdiyi mudyydn edilmi§dir. 2-Piperidinometil-4-metiltsikloalkilfenollarin kimydvi qurlu§lari iQ, 1H vd 13C NMR spektroskopiya usullari ild subuta yetirilmi§, fiziki-kimydvi xassdldri tdyin edilmi§dir. Agar sozlw. fenol, 1(3)-metiltsikloalkenldr, tsikloalkilld§md, p-[1(3)-metiltsikloalkil]fenollar, piperidin, aminometilld§md, 2-piperidinometil-4-metiltsikloalkilfenollar.
НЕКОТОРЫЕ ОСОБЕННОСТИ РЕАКЦИЙ ВЗАИМОДЕЙСТВИЯ п-[1(3)-МЕТИЛЦИКЛОАЛКИЛ]ФЕНОЛОВ C ПИПЕРИДИНОМ
Г.А. Гусейнова
Институт Нефтехимических Процессов Национальной АН Азербайджана AZ1025, Баку, пр.Ходжалы, 30, e-mail: [email protected]
В статье приводится синтез 2-пиперидинометил-4-метилциклоалкилфенолов, полученных в результате аминометилирования п-[1(3)-циклоалкил]фенолов пиперидином, п-[1(3)-циклоалкил] фенолы получают в ходе каталитического циклоалкилирования фенола 1-метилциклопентеном, 1- и 3-метилциклогексенами. Реакции аминометилирования п-циклоалкилфенолов проводили взаимодействием 30%-го формальдегида и пиперидина в присутствии растворителя. Реакция осуществлялась при 30°С, в течение 2 часов. Было установлено, что выходы полученных целевых продуктов составили 68.8-75.6% по взятому п-(метилциклоалкил)фенолу. Химические структуры 2-пиперидинометил-4-метилциклоалкилфенолов были подтверждены методами ИК, 1H и 13C ЯМР-спектроскопией, определены физико-химические характеристики. Ключевые слова: фенол, 1 (3)-метилциклоалкены, циклоалкилирование, п- [1(3)-метилциклоалкил] фенолы, пиперидин, аминометилирование, 2-пиперидинометил-4-метилциклоалкилфенолы.
