The Proceedings of the 3rd International Conference on Functional Molecules

Study on the Condensation Reaction of preparing Vanillin from Guaiacol and Glyoxylic Acid by a novel Catalyst
WEI Guo-feng1LIU Nai-qing2
1.CNPC Jilin Chemical Vanillin Plant,Jilin 132021, P.R.China; 2.CNPC Jilin Chemical Fine Chemistry Technology Center,Jilin 132021, P.R.China) Abstract: As an intermediate for preparing vanillin derived from glyoxylic acid, 3-methoxy-4-hydroxymandelic acid (MHMA) was synthesized based on condensation of guaiacol with glyoxylic acid in the presence of a novel catalyst. The influence of the novel catalyst on the condensation reaction was investigated. The experimental results showed that the novel catalyst was suitable for the formation of 3-methoxy-4-hydroxymandelic acid from guaiacol and glyoxylic acid, and the conversion of glyoxylic acid and the selectivity of MHMA reached over 95% and 85%, respectively. Keywords: Vanillin3-methoxy-4-hydroxymandelic acidGlyoxylic acidCatalyst

1. Introduction
Vanillin (3-hydroxy-4-methoxybenzaldehyde) is a known and valuable synthetic perfume in the world, which is widely used in food, drink, tobacco, cosmetics, and medicine. As an intermediate, it is used in organic synthesis field, too. Among the methods employed for the preparation of vanillin, Glyoxylic acid method was better than the others. So research on the synthesis of preparing vanillin from guaiacol and glyoxylic acid was very necessary and important to the development of vanillin. In this paper, the condensation reaction of preparing vanillin from guaiacol and glyoxylic acid in the presence of a novel catalyst was investigated.

were used without further purification. Catalyst was homemade. 2.2 Procedures Firstly, guaiacol, glyoxylic acid and catalyst were put in the 4-necked round-bottomed flask equipped with a condenser, a stirrer and device for measuring the temperature. Then, the mixture was heated to the reaction temperature, and the reaction was carried out with stirring for four hours under an atmosphere of nitrogen. Finally, the reaction mixture consisting of resultants, unreacted guaiacol that can be recycled and unreacted glyoxylic acid was obtained from the reaction and was analyzed by means of liquid chromatography. The conversion of glyoxylic acid and the selectivity of 3-methoxy-4-hydroxymandelic acid were calculated from liquid chromatogram of the mixture. 2.3 Instrumentation A LC-6A liquid chromatography analyzer (SHIMADZU CORPORATION) was used for analyzing the resultants obtained from the condensation reaction of guaiacol with glyoxylic acid. Methanol was moving phase.
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2. Experimental
2.1 Reagents Guaiacol(99%) and glyoxylic acid(40%) were commercial products and were supplied by Jilin Chemical Group Corporation. Sodium hydroxide(96%) was analytical pure reagent and was supplied by Beijing Chemical Plant. They

WEI Guo-feng et al.

Study on the Condensation Reaction of preparing Vanillin from Guaiacol and Glyoxylic Acid

3. Results and Discussion

3.1 Condensation reaction The condensation reaction of preparing Vanillin derived from Guaiacol and Glyoxylic acid was considered to be a reversible nucleophilic addition reaction, and under reported conditions a mixture comprising a 3-methoxy-4-hydroxymandelic acid, a 2-hydroxy-3-methoxyphenylglycolic acid, a 4-hydroxy-5-methoxy-1,3-phenyldiglycolic acid ,a glycolic acid, oxalic acid and so on was obtained in the condensation reaction. It may be represented by the following equation:
OH OCH3 CHO OH

1. The peak of MHMA was recorded in 2.171 min; 2. The peak of Guaiacol was recorded in 8.236 min; 3. The others were the peaks of by-product

Fig. 1 Liquid chromatogram of the mixture obtained from

OCH3

cat

the condensation reaction in the solution of sodium hydroxide

COOH CHOHCOOH OH OH OCH3 HOOCHOHC OCH3

HOOCHOHC

+
CHOHCOOH

CHO COOH

CHO

NaOH

CHOH COOH

COOH

COOH

COOH

3.2 Effect of Catalyst

The condensation reaction of guaiacol with glyoxylic acid that was reported in some arts was only carried out in the basic solution. Under reported experimental conditions, plenty of by-products were easily formed in the condensation reaction, and those by-products were detected by means of liquid chromatography (see Fig. 1). In this paper, a novel catalyst was introduced into the condensation reaction preparing vanillin derived from guaiacol and glyoxylic acid. The effect of the novel catalyst on the condensation was investigated under optimal conditions, and the better results were observed in Fig. 2 and Tab. 1.

1. The peak of MHMA was recorded in 2.168 min; 2. The peak of Guaiacol was recorded in 8.465 min; 3. The others were the peaks of by-product

Fig. 2 Liquid chromatogram of the mixture obtained from the condensation reaction by the novel catalyst Tab. 1 Effect of the novel catalyst on consentration reaction of guaiacol with glyoxylic acid
Glyoxylic acid conversion(%) MHMA selectivity(%) 93.2 64.3 95.8 85.3

: The reaction was carried out in the solution of sodium hydroxide : The reaction was carried out by the novel catalyst

Fig. 2 and Tab. 1 showed that the novel homemade catalyst has higher activity and

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The Proceedings of the 3rd International Conference on Functional Molecules

selectivity to the condensation reaction of guaiacol with glycoxylic acid. It was suitable for the condensation reaction preparing vanillin derived from glyoxylic acid, and can effectively restrain the formation of by-products such as a 2-hydroxy-3-methoxyphenylglycolic acid, a 4-hydroxy-5-methoxy-1,3-phenyldiglycolic acid, a glycolic acid, oxalic acid and so on.
3.3 Effect of Catalyst Concentration

4. Conclusion
It has now been found that 3-methoxy-4hydroxymandelic acid as an intermediate for preparing vanillin derived from glyoxylic acid could be prepared based on condensation of guaiacol with glyoxylic acid in the presence of the novel catalyst, in a rapid reaction and with a good selectivity. Under optimal conditions and in presence of the novel catalyst, the conversion of glyoxylic acid and the selectivity of MHMA can reached over 95% and 85%, respectively.

The dependence of the conversion of reactant and the selectivity of resultants on the novel catalyst concentration within a range from 1% to 8% was investigated under optimal conditions(see Tab. 2).
Tab. 2 Effect of catalyst concentration on condensation reaction of guaiacol with glyoxylic acid
No. 1 2 3 4 Catalyst concentration (wt%) 1 2 4 8 Glyoxylic acid conversion (%) 91.9 93.4 95.8 96.1 MHMA selectivity (%) 73.3 78.2 85.3 75.7

References
[1] LI Jian-sheng, ZHANG Shu-yun. Research on the Preparation of Vanillin using Guaiacol and Glyoxylic acid[J]. Jiangsu Chemical Industry, 1993, 21(3): 13-16. [2] LI Yao-xian, MA An-jie, NA Chong-wu, et al. Synthesis of Vanillin and Ethyl-vanillin by Glyoxylic Acid Method[J]. Fine Chemicals, 1999, 16: 362-365. [3] WANG Jian-xin, JIN Bao-de, PENG Qi-jun, et al. Research on the Synthesis of Vanillin from Guaiacol and Glyoxylic Acid[J]. Fine Chemicals, 2000, 17(9): 512-514. [4] HUANG Xiao-xiong, XIAO Yu-min. Advances in Productive Technology of Vanillin[J]. Chemical Technology Market, 2003, 26(4): 28-29. [5] DUN Jing-bin, WANG Tao, ZHANG Li-xin. Synthesis of 3-Ethoxy-4-hydroxymandelic Acid[J]. Fine and Specialty Chemicals, 2004, 12(11): 24-25.

The results of these experiments could be observed in Tab. 2. With the increase in the catalyst concentration, the conversion of glyoxylic acid in the condensation reaction was enhanced. However, the selectivity of 3-methoxy-4-hydroxymandelic acid reached maximum (85.3%), when the catalyst concentration was 4%, and further increased catalyst concentration, the selectivity of MHMA began to decrease. The above results showed that the optimal catalyst concentration using in the condensation reaction was 4%.

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