To enhance the yield of the one-step synthesis of terpinyl acetate from α-pinene and acetic acid, this study evaluated α-hydroxycarboxylic acid (HCA)-boric acid composite catalysts based on orthogonal experimental design. The most important factor affecting the terpinyl acetate content in the product was the HCA content. The catalytic performance of the composite catalyst was related to the pKa1 of HCA. The tartaric acid-boric acid composite catalyst showed the highest catalytic activity. The α-pinene conversion reached 91.8%, and the terpinyl acetate selectivity reached 45.6%. When boric acid was replaced with B2O3, the HCA composite catalyst activity was enhanced, which reduced the use of HCA. When the lactic acid and B2O3 content accounted for 10% and 4% of the α-pinene mass content, respectively, the α-pinene conversion reached 93.2%, and the terpinyl acetate selectivity reached up to 47.1%. In addition, the presence of water was unfavorable to HCA-boric acid composite catalyst. However, a water content less than 1% of the α-pinene mass content improved the catalytic activity of HCA-B2O3. When the tartaric acid-B2O3 was used as catalyst, and the water content was 1% of the α-pinene mass content, the α-pinene conversion was 89.6%, and the terpinyl acetate selectivity was 47.5%.
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