CC BY
53
y^K 541.128
G. Z. Raskildina1, N. G. Grigor'eva2, B. I. Kutepov2, S. S. Zlotsky3
Hydratation of alkenes in the presence of the H-beta zeolite catalysts
1 Technology and Research of Herbicides and Plants Growth Regulation Institute of the Academy Sciences of the Republic of Bashkortostan 65, Ulyanovih Str, 450029, Ufa, Russia; ph. (347) 2420854, e-mail: graskildina444@mail.ru 2Institute of Petrochemistry and Catalysis of RAS 141, pr. Oktyabria, 450075, Ufa, Russia; ph. (347) 2842750, e-mail: ngg-ink@mail.ru
3Ufa State Petroleum Technological University 1, Kosmonavtov Str., 450062 Ufa, Russia; ph. (347) 2420854, e-mail: nocturne@mail.ru
The obtaining of alcohols by hydratation of olefins widespread in petrochemical synthesis 1-3. Recently was shown hydratation over mineral (sulphuric, phosphoric) and organic (toluene sulfonic) acids and over a cationite KU-2-8 in H+-form 4-7.
The hydratation of model alkenes (nor-bornene 2 and 2-vinyl-2-methil-gem-dichloro-cyclopropane 3) over zeolite catalyst H-Beta, which is widely used in industrial scale 8-10, we investigated.
The corresponding alcohols (4,5) is obtained at 10 oC (under atmospheric pressure) in water solvent. Conversion of more active norbornene 2 is 90% for 2h (yield of alcohol is 50%), while less active 2-vinyl-2-methil-gem-dichlorocyclopropane 3 gives alcohol 5 (yield 24%) in an autoclave at 150 oC, 6 bar gauge autoclave pressure for 4 h is shown in Table 1.
We have been investigated the reactions of commercially available alkenes (norbornene and 2-vinyl-2-methil-gem-dichlorocyclopropane) with water in the presence of the H-Beta zeolites catalyst. The results of this reactions are formation of correspond alcohols. It was determined that norbornene is hydrated easier (T=10 oC, under atmospheric pressure) than 2-vinyl-2-methil-gem-dichlorocyclopropane (T=150 oC, 6 bar gauge autoclave pressure). The results have reported that the heterogeneously-catalytic addition of water to olefins is interest as an effective and cheap method of obtaining of corresponding alcohols.
Key words: norbornene; 2-vinyl-2-methil-gem-dichlorocyclopropane; alkene; zeolite; hetero-geneously-catalytic reactions.
5
Scheme 1. Hydratation of olefins
Experimental Section
An HRGS 5300 Mega Series «Carlo Erba» chromatograph was used for the qualitative and quantitative analysis of reaction products. The chromatograph was equipped with a thermo-conductivity were registered using the Bruker AM-300 spectrometer (300.13 and 75.47 MHz,
Дата поступления 15.04.13
Table 1
The interaction of olefins 2,3 with water 1
Mole ratio olefins : water = 1 : 240; 20 wt% of catalyst H-Beta (to mixture)
Reagents Temperature (°C) Time (h) К, % Selectivity (%)
2 10 2 90 4 (50)
1 3 80 24 26 5 (24)
150* 2 48 5 (25)
Ка — conversion of olefin. *Autoclave
respectively) in CDCl3 solvent, where Me4Si was used as an internal standard.
Alcohols were identified by their mass-to-charge ratio (m/z), and the fragmentation patterns which were matched with compounds libraries. Mass-spectra were recorded using the Focus instrument, equipped with a Finnigan DSQ II detector (70 eV, ionization cell temperature 200 oC, injector temperature 50— 270 oC, with a velocity of the temperature rise 10 oC/min).
*H and 13C NMR spectra were collected on a Bruker AVANCE 400 spectrometer, (1H, 400.13 MHz; 13C, 100.62 MHz, Me4Si) in CDCl3. High-resolution mass spectra were measured on a Fisons Trio 1000 instrument equipped with a DB-560 quarts column (50 m); the temperature of the column was increased from 50 to 320 oC with a programmed heating of 4 oC min-1; the electron impact was 70 eV. GLC analysis was carried out on a HP-1090 chromatograph with a refractometric detector
o
and a Plgel 100 A polystyrene column using toluene as an eluent flow rate of 0.8 mL min-1, and a tape of velocity of 1.5 cm min-1.
IR spectra were recorded on a Shimadzu 8300 Fourier spectrometer with a resolution of 4 cm-1 and 50 spectral acquisitions.
Catalyst
Zeolite NH4-Beta was produced by the public corporation Angarsk Factory of Catalysts and Organic Synthesis. Zeolite NH4-Beta was transferred into H-Beta form by calcinations at 540 0C for 4h before all experiments.
The interaction of norbornene 2 with water over H-Beta zeolite. The zeolite H-Beta (0.28 g) was added to a mixture of norbornene 2 (1.22 g, 0.013 mmol) and water 1 (50 g, 3.13 mmol) at 10 0C and stirred for 2h. After the catalyst was filtered and the reaction mass was extraction with ether. The latter was removed at
the reduced pressure. The alcohol 4 (72 oC/20 mm Hg) were isolated under vacuum. The mixture of exo-2-norborneol 4 and di-norbornyl ether of this mixture was (% w/w): 50/50% accordingly. Compounds were identified by NMR-spectroscopy.
exo-2-norborneol (4)
OH
1H NMR, 8: 1.02-1.05 (m, 3H, C6Ha, C7Ha, C5Ha), 1.12-1.18 (m, 2 H, C3Ha, C5Hb), 1.36-1.51 (m, 2H, C7Hb, C6Hb), 1.62-1.67 (m, 1H, C3Hb), 2.12-2.35 (m, 2H, C4H, C1H), 3.68 (d, 1H, C2H). 13C NMR, 8: 24.39 C6, 29.27 C5, 34.38 C7, 35.40 C4, 42.37 C3, 44.34 C1, 74.95 C2. IR-spectrum: 2851-2954 (C-H, CH2), 3437 (-OH); m/z: 122 M+ (30), 107 (100), 79 (93), 77 (52), 43 (30), 51 (21), 105 (10), 50 (10), 80 (7); Kovae index Ik 1065.
The interaction of 2-vinyl-2-methil-gem-dichlorocyclopropane 3 with water over H-Beta zeolite. The zeolite H-Beta (0.43 g) was added to a mixture of 2-vinyl-2-methil-gem-dichlorocyclopropane 3 (1.96 g, 0.013 mmol) and water 1 (50 g, 3.13 mmol) at 80 oC/150 oC* and stirred for 24/2*h. After the catalyst was filtered and the reaction mass was extraction with ether. The latter was removed at the reduced pressure. The alcohol 5 (95 oC/25 mm Hg) were isolated under vacuum. The mixture of 1,1-dichloro-2-methyl-2-(hydroxyethyl-1)cyclo-propane 5 of this mixture was 24%. Compound was identified by NMR-spectroscopy.
After the completion of the reaction mass was separated from the catalyst by filtration. The conversion of initial olefins and the quantitative composition of the alcohol fraction were determined using gas-liquid chromato-
* Autoclave
3
2
graphy (GLC). The chemical stricter of alcohols (4, 5) was established by means of GC/MS spectrometry and NMR spectroscopy.
1,1-dichloro-2-methyl-2-(hydroxyethyl-1)cyclopropane (5)
6 5
CH3 CH
3
V
cl Ъ
4 \
OH
1.
1H NMR, 8: 1.23-1.24 2H (d, cyclC3H2), 1.42 3H (s, C5H3), 1.70 1H (s, OH), 1.92 3H (s, C6H3), 4.01-4.06 1H (m, C4H 2J=12.8, 3J=6). 13C NMR, 8: 20.71 C6, 23.39 C5, 34.66 C3, 44.70 C2, 66.39 C4, 77.26 C1. IR-spectrum: 2877-2972 (C-H, CH2), 3418 (-OH); m/z: 169 M+ (0.6), 45 (100), 124/126/128 (35/22/4), 87/89/91 (6/ 35/11), 53 (14), 53 (14), 43 (13), 51 (11). Kovae index 1^=1123.
Conclusions. Based on this result suggest that the zeolite H-Beta successfully is used for hydratation of different kinds of olefins.
3.
4.
5.
6.
7.
8.
References
Patent 2,345,573, US / Herman A. Bruson // http:/ / www.freepatentsonline.com/ 2345573.html. 1944.- #4.
Xulai Yang, Sabornie Chatterjee, Zhijun Zhang, Xifeng Zhu, and Charles U. Pittman. Jr. // Ind. Eng. Chem. Res.- 2010.- V.49.- P.2003. Brown H., Kawakami J. // J. Amer. Chem. Soc.- 1990.- V.92.- 1970.
Butlerov A. M. Selected Works in Organic Chemistry. M.: Publishing House of the Academy of Sciences of the USSR, 1951.- P.333. Azinger Ph. Chemistry and Technology of monoolefins.- M.: Gostoptehidat, 1960.- P.467. Sumio A. Chem. Engng.- 1973.- V.56.- P.80. Menjajlo A. T. Synthesis of alcohols and organic compounds from oils. Tr. NIISa.- M.: Goschi-mizdat, 1960.- pp.226.
Yilmaz B., Muller U. // Catalytic Applications of Zeolites in Chemical Industry. Top. Catal. -2009.- V.52.- P.
10.
Kubasov A. A. // Zeolites are in catalysis today and tomorrow. Soros Educational Journal.-2000.- V.6, № 6.- P.44.
Valencia S., Corma A., Cambor M. // Characterization of nanocrystalline zeolite Beta. Microporous and mesoporous materials.- 1998.-V.25.- P.59.
2
3
9
