Asian Journal of Chemistry; Vol. 26, No. 4 (2014), 1212-1214
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Synthesis of 1-Bromooctane Catalyzed by Solid Super Acid SO
/ZrO -ZnO
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*
GUOQIN HU , LIUYANG TAN, LEIMING CUI and PEIPEI WU
School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou, Henan Province, P.R. China
Corresponding author: Tel/Fax: +86 371 67781712; E-mail: huguoqin@zzu.edu.cn; tanliuyangp@126.com
*
Received: 18 September 2013;
Accepted: 12 November 2013;
Published online: 15 February 2014;
AJC-14731
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The solid super acid catalyst SO /ZrO -ZnO was prepared by impregnation and characterized by infrared spectroscopy, X-ray diffraction,
different scanning calorimetric and thermogravimetric analysis. Their performances were evaluated by the synthesis of 1-bromooctane.
Under the condition of n-octanol/hydrobromic acid molar ratio of 1:3, a catalyst amount of 8 wt. %, reaction time of 7 h, temperature of
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30 °C, produce 1-bromooctane (yield 70.22 %).
Keywords: Solid super acid, Impregnation, 1-Bromooctane.
INTRODUCTION
EXPERIMENTAL
1-Bromooctane is an important intermediate in organic
synthesis. It is soluble in ethanol and ether, slightly toxic and
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narcotic . The atom of bromine can be substituted by hydroxy,
Sulfuric acid (98 %), aqueous ammonia (25-28 %),
hydrobromic acid (40% ), sodium bicarbonate (A.R) were
purchased from Kermel, Tianjin Chemical Reagent Co., Ltd.
amino, alkoxy to generate corresponding alcohols, amines and
ether. It is widely used for synthesis of pesticides, organic dyes,
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Zirconium(VI) oxychloride octahydrate (ZrOCl ·8H O), N-
octyl alcohol (99 %) and Silver nitrate (A.R) were purchased
from Sinopharm Chemical Reagent Co., Ltd., Sanmenxia
AOKE Chemical Co., Ltd. and Beijing chemical plant respec-
tively.
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surfactants, ultraviolet absorbers, etc. . Due to its broad spec-
trum of activity, the compound has received a great deal of
attention in connection with their synthesis. Several methodo-
logies of preparation of 1-bromooctane have been reported in
Preparation of catalyst: 2:1 of the molar ratio of
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the literatures .
The bromine-phosphorus method causes environmental
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ZrOCl ·8H O and Zn(NO ) was dissolved in distilled water.
To this solution, aqueous concentrated ammonia (25-28 %)
was added drop-wise from a burette with vigorous stirring
until the pH of the solution reached 10 and then left for 24 h.
The obtained precipitate was washed several times with deion-
ized water and filtrated by pump until a neutral filtrate and the
pollution because of the volatility and toxicity of bromine and
the corrosivity and flammability of phosphorus. Some by-
products are produced by sodium bromide-sulfuric acid
method because of the dehydration and oxidation of concen-
trated sulfuric acid. Another hydrobromic aqueous solution
method has long reaction time, too much raw material consum-
ption and low yield.
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absence of chlorine ion, detected by AgNO (0.1 mol/L). The
cake after filtration was dried at 110 °C for 16 h. The sample
thus obtained was ground into powder under 120 mesh. To
prepare the targeted catalyst, the powdered complex oxides
were impregnating with sulfuric acid of 0.5 M for 6 h
followed by filtration. The sample was oven dried at 110 °C
Recently considerable attention has been devoted to the
super solid acids. Generally, these catalysts offer several
advantages, such as strong acid sites, nontoxicity, noncorro-
sive-ness, easily handling, mild reaction conditions, high
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for 12 h then calcined at 650 °C for 4 h to obtain SO /ZrO -
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selectivity, low cost and easy to recover and recycling . In this
ZnO
Characterization of catalyst: Infrared spectroscopy
spectrogram of the sample showed the support of H SO on
ZrO -ZnO. X-ray diffraction (XRD) analysis revealed the pres-
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work, a kind of solid super catalyst sulfated zirconia and zinc
oxide was prepared and its performance applying in synthesis
of 1-bromooctane was investigated. The solid base catalyst
showed a good performance during the synthesis process, with
a high purity and yield of 1-bromooctane product in a rela-
tively short time.
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ence of zirconia crystal phases and zincoxide crystal phases.
DSC-TG measurements indicated temperature from the tetra-
gonal phase to the monoclinic phase of zirconia rises.