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Investigations on different efficient strategies for the selective synthesis of jasminaldehyde over HRhCO(PPh3)3–hexagonal mesoporous silica and chitosan catalysts

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Abstract

Various strategies are investigated for the synthesis of jasminaldehyde over heterogeneous catalysts. The jasminaldehyde synthesis via conventional cross-aldol condensation of heptanal with benzaldehyde using heterogeneous catalyst with a heptanal:benzaldehyde ratio of 1:4 was performed. Even with 100% conversion of heptanal with 100% selectivity, only 25% benzaldehyde reacts and 75% of benzaldehyde has to remain unreacted as the heptanal:benzaldehyde ratio is 1:4. So here, a strategy was applied in which, addition of heptanal in regular intervals to the reaction mixture was performed by keeping the ratio of heptanal:benzaldehyde as ~ 1:4. This could afford to convert 62% of benzaldehyde to jasminaldehyde with 69% selectivity in 20 h. Heptanal can be obtained by hydroformylation of 1-hexene. Hence in the next strategy, the investigations had been performed for the synthesis of jasminaldehyde via a tandem reaction by individually carrying out hydroformylation and aldol condensation. Hydroformylation of 1-hexene to heptanal and further condensation of this product mixture with benzaldehyde to jasminaldehyde, using heterogeneous catalysts HRh(CO)(PPh3)3 encapsulated HMS (HF-1) and amino functionalized chitosan (CH-1) respectively were studied. The study was also extended to perform a single-pot hydroformylation and aldol condensation using heterogeneous catalysts (HF-1) and (CH-1) together. All the strategies were found to be effective for selective synthesis for jasminaldehyde, however the performance for addition of heptanal in regular intervals to the reaction mixture was remarkable due to being capable to consume 62% benzaldehyde.

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Acknowledgements

CSMCRI communication No. IMC 03, CSIR-CSMCRI—128/2021. Authors thank Council of Scientific and Industrial Research (CSIR), New Delhi, India for the financial support through Network Project on the Development of Specialty Inorganic Materials for Diverse Applications. The authors also acknowledge Analytical Division and Central Instrumentation Facility for providing instrumental analysis.

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  1. Inorganic Materials and Catalysis Division, Council of Scientific and Industrial Research, Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar, Gujarat, 364 002, India

    N. Sudheesh & Ram S. Shukla

  2. Department of Chemistry, N.S.S. College, K.R. Puram, Cherthala, Alappuzha, Kerala, 688 541, India

    N. Sudheesh

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Sudheesh, N., Shukla, R.S. Investigations on different efficient strategies for the selective synthesis of jasminaldehyde over HRhCO(PPh3)3–hexagonal mesoporous silica and chitosan catalysts. Reac Kinet Mech Cat 135, 1485–1502 (2022). https://doi.org/10.1007/s11144-022-02196-9

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