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CHEMICAL PROBLEMS 2019 no. 4 (17) ISSN 2221-8688
607
UOT 547.425:547.464:547.569
SOME FEATURES OF CYCLOALKYLATION REACTION OF P-CHLOROPHENOL WITH 1-METHYLCYCLOALKENES
S.T. Shahmuradov
Acad. Y. Mammadaliyev Institute of Petrochemical Processes National Academy of Sciences of Azerbaijan 30, Khojali ave., AZ1025, Baku, Azerbaijan e-mail: shahmuradov_samir@mail.ru
Received 01.11.2019
Abstract: 2(1-methylcyclopentyl)- and 2(1-methylcyclohexyl)-4-chlorophenols were synthesized by the interaction of p-chlorophenol with 1-methylcyclopentene and 1-methylcyclohexene in the presence of zeolite-Y catalyst impregnated on ortho-phosphoric acid in a continuously operating installation. It revealed that the yield of the desirable products - 2(1-methylcycloalkyl)-4-chlorophenols was 72.5-74.7% according to the calculation amount of p-chlorophenol at 110-120°C reaction temperature, molar ratio of p-chlorophenol to cyclene of 1:1 and 0.5 h -1 vol. rate. The selectivity was 93.0-96.3% according to the target product.
Keywords: p-chlorophenol, 1-methylcyclopentene, 1-methylcyclohexene, zeolite Y containing phosphorus, cycloalkylation, 2 (1-methylcycloalkyl)-4-chlorophenol DOI: 10.32737/2221-8688-2019-4-607-612
Introduction
Due to their low toxicity, alkyl phenols are used primarily in medical supplies, in the production of food packaging etc. Spatially hindered phenols are widely used as food additives, which have a number of advantages from the point of view of food technology: high antioxidant effects with relative high thermal stability, low toxicity, and low cost [16].
Successful practices of the use of antioxidants in the polymer, rubber, food, and cosmetic industries testify to good prospects of the use of these compounds in materials which contacted with humans. Chemical additives containing halide fragments are important among these compounds. They raise fire resistance of polyolefins' service life by preventing destruction from external factors' impact (temperature, light, etc.) [7-12].
Chlorophenol antioxidants are studied until now and described in the literature they are extremely diverse in their structure Well-known alkylchlorophenols are mainly obtained by alkylation of chlorophenols with aliphatic hydrocarbons; however, they are not fully combined with polyolefin and unstable at high temperatures. In this regard cycloalkyl chlorophenols dissolve well and they are combined with polyolefin and they are thermo stable.
The article presents the results of research into the interaction of p-chlorophenol (PChPh) with 1-methylcyclopentene (1-MCP) and 1-methylcyclohexene (1-MCH) in the presence of a Zeolite-Y catalyst impregnated with orthophosphoric acid on a continuously operating installation.
Experimental section
To obtain 2(1-methylcycloalkyl)-4-chlorophenols freshly distilled p-chlorophenol, 1-methylcyclopentene with bp = 74-75 ° C, = 1.4347, pf = 0.7782, with 98% purity
and 1-methylcyclohexene with bp = 110-111 °
C, < = 1.4500, pf = 0.8200, 99.8% purity
were used.
The orthophosphoric acid was impregnated with Zeolite-Y and used as a catalyst. The catalyst was prepared by means
of vigorous mixing of the alumo gel with the zeolite Y type of catalyst of cracking (SiO2/Al2O3 4.8, the degree of exchange of Na+ ions for H+ ions 97%). The obtained product was molded through filter (1.6 mm diameter), then granulated and calcined.
Then the catalyst was impregnated with 10% solution of phosphoric acid (according to the calculated amount of P2O5), evaporated and dried in the oven at 100 °C temperature and calcined with a continuously rising temperature from 200 °C to 600 °C.
Cycloalkylation of para-chlorophenol with 1-methylcycloalkenes was carried out in a laboratory setup.
p-Chlorophenol and cyclene were supplied to the mixer from the tank in the desired ratio. The temperature of p-chlorophenol was maintained at 40°C. After PChPh mixing with cyclen, the mixer was fed into the reactor bottom. A mixture of components passed through a layer of catalyst, cooled in a refrigerator and collected in a container.
If rectified at atmospheric pressure, cyclene and PChPh (up to 200°C) were distilled off, and then the desired reaction product was isolated under vacuum (10 mm Hg), its purity and physico-chemical parameters determined. The composition and
Results
the structure of the obtained products were determined via the chromatography and spectral analysis methods.
Chromatographic analysis of the alkylation product was analyzed on LCM-72 chromatograph with a thermal conductivity detector. Column length is 2 m, solid carrier -chromanized N-AW-DMC, washed acid and salinized with dimethyldichlorosilane, fr. 0.20.25 mm. The stationary phase is 5% methyl siloxane elastomer SE-30. Intake and final temperatures of the column were 50oC and 270oC respectively. Programmed speed is 10°C/min, helium carrier gas speed is 50 ml/min., temperature of the source is 365°C, detector temperature is 300°C and the speed of the chart tape is 60 mm/h. For calculation, internal normalization method was used on the basis of conversion to 100% of total peak areas.
The structure of the synthesized product was determined via IR- and ^ NMR spectroscopy. IR spectrum of the samples was recorded on ALPHA Furye spectrometer (company BRUKER, Germany) in the interval of 600-4000 sm-1. ^ NMR spectrum was recorded on «Bruker-300» (Germany) at a room temperature and CCl4 with internal standart - tetramethylsiloxane.
and discussion
Interaction of p-chlorophenol with 1-methylcyclopentene and 1-methylcyclohexene the presence of Zeolite-Y catalyst
in
impregnated with orthophosphoric acid proceeds with the formation of 2(1-methylcycloalkyl)-4-chlorophenols:
+
OH
CH3
OH
à
CH,
CH3
+
O
OH
CH
a
In order to identify the optimal conditions for ensuring of the maximum yield of 2(1-methylcycloalkyl)-4-chlorophenols, an effect of temperature, molar ratio of PChPh to 1-methylcycloalkene and vol. rate on the yield and composition of reaction products were studied.
The reaction temperature varied from 80 to 140 ° C, the molar ratio of PChPh to 1-methylcycloalkene ranged from 0.5: 1 to 1: 0.5 mol/mol, and the vol. rate was from 0.2 to 0.8 h-1. Figure 1 shows the results of experiments
on the cycloalkylation of p-chlorophenol with 1-methylcyclopentene in the presence of a catalyst.
100
90
80
ïS 70
>■- 60 x
50 40
30
,,1 y •— ...... ^ 2
!
b) 0
80 100 120 140 0,5:! 1:1 ] : 0,5 0-2 0.6 °>8
Temperature , °C PChPh : 1-MCP, mol
(PChFh : l-MCP - mol/mol: vol. rate - 0.5 h'> 'Tomp, - llCCi vol. rate - 0.5 h">
vol. rate. h1
(Temp. - U0«C; PC hPh : 1-MCF = mol/mol )
Fig. 1. Dependence of the yield X (%) (1) and the selectivity of Y (%) (2) 2(1-methyl-cyclopentyl)-4-chlorphenol from the temperature (a), molar ratio of the initial components (b)
and the vol. rate (c).
At 110°C temperature the highest yield of the desirable product of 2(1-methylcyclopentyl) -4-chlorophenol is achieved - 72.5%; increasing the temperature prior to 140°C leads to a decrease the yield and selectivity of the product to 61.8% and 84.2%, respectively. The yield of 2(1-methylcyclopentyl)-4-chlorophenol was 72.5% at the the molar ratio of p-chlorophenol to 1-MCP is equaled to 1: 1 and the further CH
0
il Cl
When increased the volume rate of the reaction from 0.2 to 0.5 h-1 cause an increase the yield of 2(1-methylcyclopentyl)-4-chlorophenol from 44.5 to 72.5%. Also a further increasing the flow rate does not lead to an increase the yield of the target product.
Thus, optimal conditions for obtaining 2 (1-methylcyclopentyl) -4-chlorophenol were revealed: a reaction temperature was 110°C, molar ratio of p-chlorophenol: 1-MCP = 1: 1, vol. rate was 0.5 h-1. Under these conditions, the yield of the desired product was 72.5% (according to the calculation), and the selectivity of the target product was 93.0%.
The similar results were obtained for 2
increasing the amount of p-chlorophenol or cyclene does not give positive results, and the yield of the whole product remains at the same level. The prolonged staying of 2-monosubstituted p-chlorophenol in the reaction zone creates the conditions for joining the second cyclene molecule that resulting in the production of the disubstituted product, which is confirmed by experimental dates.
CH
CH3 ™ CH3
(1-methylcyclohexanol) -4-chlorophenol.
Analysis of the obtained results made it possible to establish the optimal conditions for the interaction of PCP with 1-MCH in the presence of zeolite containing phosphorus: temperature 120° C, molar ratio of PCP:1-MCH of 1:1 mol/mol, vol. rate - 0.5 h-1. In this condition the yield of 2 (methyl-cyclohexyl) -4-chlorophenol was 74.7% according to the calculation of taken PCP, and selectivity was 96.3% for the desired product.
The IR spectrum results for 2 (1-methylcyclohexyl) -4-chlorophenol are given in Table 1.
+
+
Table 1. Results of IR analysis of the 2(1- methyl cyclohexyl)-4-chlorphenol
Absorption band Location in the structure
654, 705 sm-1 C- Cl bond
809, 879 sm-1 1, 2, 4 substituted benzene ring
973 sm-1 C - H bonds of cyclohexane ring
1114, 1171 sm-1 C - O bond
1245 cm-1 , 3555 sm-1 deformation and valence vibration corresponding to the O - H bond on the OH group
1322, 1400, 1450, 1489 sm-1 deformation vibration of C - H bond for CH3 and CH2 groups
2856, 2923 sm-1 valence vibration of CH3 and CH2 groups
1597 sm-1 C - H bonds of benzene ring
1698 sm-1 C - H bonds of benzene ring
Below-cited are H NMR analysis results of 2 (1-methylcycloalkyl) -4-chlorophenols.
Table 2. Results of the 1H NMR spectroscopic analysis of 2(1-methylcycloalkyl)-4-_chlorophenols_
№ Chemical name and structure type of proton chemical shift, ppm
1. 2(1-methyl cyclopentyl)-4-chlorophenol CH3 OH 3 OPo Cl CH3 - singlet 0.95
CH2 (cycle) - wide signal 1.4-1.5
OH - singlet 6.0
Hi,H2 and H3 protons of the benzene ring as multiplete 6.8-7.0
2. 2( 1 -methylcyclohexyl)-4-chlorophenol oh ch3 № ci CH3 - singlet 0.873
CH2 (cycle) - wide signal 1.3-1.4
OH - singlet 6.0
H1,H2 h H3 (benzene ring ) multiplete 6.8-7.2
In the spectrum of 13C NMR of 2 (1-methylcyclohexyl) -4-chlorophenol, the carbon atom of the CH3 group at 5 = 62 ppm (singlet), carbon atoms of the aromatic ring 5 = 117.85; 123.7; 126; 127.65; 129; 137.5; 154.8 ppm (singlet), carbon atoms of cyclohexene 5 = 24.87; 26.4; 29.0; 36.3; 38.0 ppm (singlet) were observed.
Table 3 presents physical and chemical indicators of 2(1-methylcycloalkyl)-4-chlorphenol. According to Table 3, the revealed element composition of synthesized compounds complied with the calculated amount of elements.
Conclusion
The interaction reaction of p-chlorophenol with 1-methyl cyclopentenyl and 1-methyl cyclohexene was studied in the presence of
Zeolite-Y impregnated orthophosphoric acid impregnated with ortho-phosphoric acid on a continuously operating installation.
Table 3. Physical and chemical indicators of 2(1-methylcycloalkyl)-4-chlorphenol
OH Cl boiling point at 10 Hg. n20 d pT molar mass element composition, %
calcu ated found
C H C H
CH3 r = -Jo 198-202 1.5025 1.0095 210 68.6 7.1 68.3 6.9
ch3 207-211 1.5176 1.0308 224 69.6 7.6 69.4 7.3
It was determined that at 110-120 reaction temperature, molar ratio of p-chlorphenol to cyclene of 1:1 mol/mol and at vol. rate 0.5 h-1 the yield of the desirable
product- 2(1-methylcycloalkyl)- 4-chlorphenol was 72.5 - 74.7 % according to the taken PCP and the selectivity was - 93.0 -96.3 % for target product.
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P-XLORFENOLUN1-METiLTSiKLOALKENLdRLd TSiKLOALKiLLd^Md REAKSiYALARININ BdZi XUSUSiYYdTLdRi
S.T. §ahmuradov
AMEA Neft-kimya proseslari instititutu
AZ1025, Baki, Xocalipr., 30 e-mail: shahmuradov samir@mail.ru
p-Xlorfenolun orto-fosfat turçusu hopdurulmuç seolit Y katalizatoru içtirakinda fasilasiz içlayan qurguda 1-metiltsiklopenten va 1-metiltsikloheksenla qarçiliqli tasirindan 2(1-metiltsiklopentil)- va 2(1-metiltsikloheksil)-4-xlorfenollarin sintezi hayata keçirilmiçdir. Muayyan edilmiçdir ki, 110-120oC temperaturda, p-xlorfenolun tsiklena 1 : 1 mol nisbatinda, 0.5 saat-1 hacmi suratinda maqsadli mahsullarin - 2(1-metiltsikloalkil)-4-xlorfenolun çiximi goturulan p-xlorfenola gora 72.5-74.7%, seçicilik maqsadli mahsula gora 93.0-96.3% taçkil edir.
Açar sôzfor: p-xlorfenol, 1-metiltsiklopenten, 1-metiltsikloheksen, fosfor tarkibli seolit Y, tsikloalkillaçma, 2(1 -metiltsikloalkil)-4-xlorfenol
НЕКОТОРЫЕ ОСОБЕННОСТИ РЕАКЦИИ ЦИКЛОАЛКИЛИРОВАНИЯ П-ХЛОРФЕНОЛА С1 - МЕТИЛЦИКЛОАЛКЕНАМИ
С. Т. Шахмурадов
Институт нефтехимических процессов Национальной АН Азербайджана
АХ 1025, Баку, пр. Ходжалы 30 е-таП: shahmuradov_samir@mail. ги
Осуществлен синтез 2(1-метилциклопентил)- и 2(1-метилциклогексил)-4-хлорфенолов, взаимодействием п-хлорфенола с 1-метилциклопентеном и 1-метилциклогексеном в присутствии катализатора цеолита Y, пропитанного орто-фосфорной кислотой, на непрерывно действующей установке. Установлено, что при температуре 110-120°С, мольном соотношении п-хлорфенола к циклену 1:1 моль/моль и объемной скорости 0,5 час'1 выход целевых продуктов - 2(1-метилциклоалкил)-4-хлорфенолов составил 72.5-74.7 % от теории на взятый п-хлорфенол, а селективность 93.0-96.3 % по целевому продукту.
Ключевые слова: п-хлорфенол, 1-метилциклопентен, 1-метилциклогексен, фосфорсодержащий цеолитциклоалкилирование, 2(1-метилциклоалкил)-4-хлорфенол
