Synthesis from (–)-α-Pinene of an Optically Active Macrocyclic Diesterdihydrazide with 2,6-Pyridinedicarboxylic and Adipic Acid Moities

Ishmuratov, G. Yu.; Выдрина, В. А.; Denisova, K. S.; Yakovleva, M. P.; Gazetdinov, R. R.; Vyrypaev, E. M.; Tolstikov, A. G.

doi:10.1007/s10600-017-1912-8

Cited by 7 publications

(9 citation statements)

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“…In our endeavor to synthesize biobased polyesters, the diol 5 was obtained on a 50 g scale by the oxidative cleavage of the double bond of (−)-α-pinene by ozonolysis ( Materials and Methods ). The use of ozone for the cleavage of the double bond was previously reported, 54 still the resulting diol has to the best of our knowledge never been reported in the scope of polyester synthesis. The diol 5 is of particular interest as it allows the synthesis of a variety of biobased polyesters and polyurethanes by reacting it with different diacids or diisocyanides via polyaddition.…”

Section: Resultsmentioning

confidence: 94%

“…Briefly, HHDC 5 was synthesized by oxidative cleavage of the (−)-α-pinene double bond, following the procedure of Tolstikov et al 54 The crude product was further purified using MPLC, affording the diol 5 as transparent oil with a yield of 65% ( Figure 3 a).…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of HHDC 5 was performed as previously published. 54 (−)-α-Pinene was dissolved in a 1:1 mixture of MeOH and CH 2 Cl 2 , stirred at −76 °C, purged with an O 3 /O 2 mixture, and stirred until 1 equiv of O 3 had reacted. The reaction was afterward purged with oxygen, treated with NaBH 4 , and stirred for 4 h at room temperature.…”

Section: Materials and Methodsmentioning

confidence: 99%

“…The synthesis of HHDC 5 was performed as previously published . (−)-α-Pinene was dissolved in a 1:1 mixture of MeOH and CH 2 Cl 2 , stirred at −76 °C, purged with an O 3 /O 2 mixture, and stirred until 1 equiv of O 3 had reacted.…”

Section: Methodsmentioning

confidence: 99%

“…To present its versatility as a monomer to generate biobased polyesters with different properties, we performed the synthesis of four different polyester compositions, their film formation, and further application as versatile coating materials. Briefly, HHDC 5 was synthesized by oxidative cleavage of the (−)-α-pinene double bond, following the procedure of Tolstikov et al 54 The crude product was further purified using MPLC, affording the diol 5 as transparent oil with a yield of 65% (Figure 3a).…”

Section: Jacs Aumentioning

confidence: 99%

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Pinene-Based Oxidative Synthetic Toolbox for Scalable Polyester Synthesis

Stamm

Öhlin

Mosbech

et al. 2021

JACS Au

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Generation of renewable polymers is a long-standing goal toward reaching a more sustainable society, but building blocks in biomass can be incompatible with desired polymerization type, hampering the full implementation potential of biomaterials. Herein, we show how conceptually simple oxidative transformations can be used to unlock the inherent reactivity of terpene synthons in generating polyesters by two different mechanisms starting from the same α-pinene substrate. In the first pathway, α-pinene was oxidized into the bicyclic verbanone-based lactone and subsequently polymerized into star-shaped polymers via ring-opening polymerization, resulting in a biobased semicrystalline polyester with tunable glass transition and melting temperatures. In a second pathway, polyesters were synthesized via polycondensation, utilizing the diol 1-(1′-hydroxyethyl)-3-(2′-hydroxy-ethyl)-2,2-dimethylcyclobutane (HHDC) synthesized by oxidative cleavage of the double bond of α-pinene, together with unsaturated biobased diesters such as dimethyl maleate (DMM) and dimethyl itaconate (DMI). The resulting families of terpene-based polyesters were thereafter successfully cross-linked by either transetherification, utilizing the terminal hydroxyl groups of the synthesized verbanone-based materials, or by UV irradiation, utilizing the unsaturation provided by the DMM or DMI moieties within the HHDC-based copolymers. This work highlights the potential to apply an oxidative toolbox to valorize inert terpene metabolites enabling generation of biosourced polyesters and coatings thereof by complementary mechanisms.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Materials and Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Jacs Aumentioning

confidence: 99%

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