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Progress in Chemistry 2023, Vol. 35 Issue (8): 1191-1198 DOI: 10.7536/PC221209 Previous Articles   Next Articles

• Review •

Selective Oxidative Lactonization of 1,6-Hexanediol into ε-Caprolactone

Xiaoyu Shen1, Zhongtian Du1(), Bairui Guo1, Zhongxu Guo1, Changhai Liang1,2()   

  1. 1 School of Chemical Engineering, Dalian University of Technology,Panjin 124221, China
    2 State Key Laboratory of Fine Chemicals, Dalian University of Technology,Dalian 116023, China
  • Received: Revised: Online: Published:
  • Contact: *e-mail: duzhongtian@dlut.edu.cn(Zhongtian Du);changhai@dlut.edu.cn(Changhai Liang)
  • Supported by:
    National Natural Science Foundation of China(22172010); Fundamental Research Funds for the Central Universities(DUT2021TD103)
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ε-Caprolactone is a key monomer for the synthesis of poly(ε-caprolactone) (PCL) with good biocompatibility and biodegradability, and relevant polymer materials could be applied in pharmaceutical, medicinal, and packaging applications. Green and economic synthesis of ε-caprolactone is vital to popularize such eco-friendly polymers, and selective oxidative lactonization of 1,6-hexanediol into ε-caprolactone remains to be developed. In this review, different routes for the synthesis of ε-caprolactone such as Baeyer-Villiger oxidation of cyclohexanone and oxidative lactonization of 1,6-hexanediol are comparatively analyzed. According to whether electron acceptors (oxidants) are added to the reaction systems, the related advances of oxidative lactonization of 1,6-hexanediol are summarized, and the advantages and disadvantages of the corresponding reaction systems and catalysts are reviewed. The development trend of oxidative lactonization of 1,6-hexanediol into ε-caprolactone is also proposed.

Contents

1 Introduction

2 Catalytic oxidation processes

2.1 Carbonyl compounds act as electron acceptors

2.2 Molecular oxygen acts as the electron acceptor

2.3 H2O2 acts as the oxidant

3 Catalytic dehydrogenation

3.1 Homogeneous catalysts

3.2 Heterogeneous catalysts

4 Conclusion and outlook

Fig. 1 Oxidation of cyclohexanone into ε-caprolactone via Baeyer-Villiger oxidation
Fig. 2 The preparation routes of ε-caprolactone from 1,6-hexadiol and cyclohexanone compared from the perspective of structure and composition
Fig. 3 Reaction pathway from 1,6-hexanediol to ε-caprolactone
Fig. 4 [{Ru(cymene)Cl2}2]/DPPF catalyzed oxidation of 1,6-hexanediol to ε-caprolactone[26,27]
Fig. 5 The coupled oxidation of 1,6-hexanediol and cyclohexanone to produce ε-caprolactone[32]
Fig. 6 Preparation of ε-caprolactone from 5-hydroxymethylfurfural[37]
Fig. 7 Biomimetic aerobic oxidation of 1,6-hexanediol into ε-caprolactone[39]
Fig. 8 Co@C-N(800) catalyzed oxidative lactonization of 1,6-hexanediol into ε-caprolactone[43]
Fig. 9 Cetylpyridinium chloride/tungstophosphate-catalysed 1,6-hexanediol to ε-caprolactone[45]
Fig. 10 Catalytic dehydrogenative lactonization of 1,6-hexanediol
Fig. 11 Fe-MACHO-BH catalyzed dehydrogenative lactonization of 1,6-hexanediol to ε-caprolactone[47]
Table 1 Comparison of atom economy, theoretical by-products, and possible safety hazards in oxidative lactonization of 1,6-hexanediol into ε-caprolactone1)
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