Synthesis and X-ray structural analysis of an acyclic bifunctional vicinal triketone, its hydrate, and its ethanol-adduct

Yonekawa, Morio; Furusho, Yoshio; Sei, Yoshihisa; Takata, Toshikazu; Endo, Takeshi

doi:10.1016/j.tet.2013.03.065

Cited by 16 publications

(13 citation statements)

References 30 publications

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“…1723 cm −1 and ca. 1675 cm −1 ) as well as the hemiketal structure (ca. 1674 cm −1 ; Supporting Information Fig.…”

Section: Resultsmentioning

confidence: 99%

“…1674 cm −1 ; Supporting Information Fig. S2) . The glass transition temperature ( T g ) of the crosslinked PHEMA 6 was 84 °C (Supporting Information Fig.…”

Section: Resultsmentioning

confidence: 99%

“…No peaks were detected in the aromatic region unambiguously, indicating a complete dissociation of the bistriketone moiety from the polymer chain. Moreover, the bistriketone 4 was also recovered from the filtrate by evaporating volatile components followed by precipitation from water and subsequent heating at 100 °C in vacuo in an isolated yield of 54% . The complete decrosslinking was also supported by SEC analysis.…”

Section: Resultsmentioning

confidence: 99%

“…We carried out crosslinking of the polystyrenes through hemiketal linkages by using α,ω‐diols, and the crosslinked polymer could be decrosslinked by treatment with water‐containing solvents to give the original polystyrenes in high yields . Recently, we have also reported the facile synthesis of an acyclic bifunctional vicinal tricarbonyl compound, 1,4‐phenylenebis(phenylpropanetrione) 4 , and revealed by single X‐ray crystallographic analysis that water and ethanol molecules covalently attached to the central carbonyl carbon atoms of 4 to form its hydrate 5a and its ethanol adduct 5c , respectively . These three species could be reversibly converted to one another in a facile manner [Scheme (b)].…”

Section: Introductionmentioning

confidence: 99%

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Reversible crosslinking and decrosslinking of polymers containing alcohol moiety using an acyclic bifunctional vicinal triketone

Yonekawa

Furusho

Takata

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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In this article, we report reversible crosslinking and decrosslinking systems of commercially available alcoholic polymers, using a bifunctional vicinal triketone (bistriketone) as a crosslinking reagent. A small amount of the bistriketone (0.2 equiv of the tricarbonyl moiety relative to the OH group of the polymer) was added to a solution of poly(2-hydroxyethyl methacrylate) (PHEMA) in dimethyl sulfoxide (DMSO). After 4 days, the networked polymer was obtained as a yellow-colored gel in 97% yield. Conversely, the resulting gel could be decrosslinked by treatment with MeOH for 4 days to recover the original PHEMA in 94% yield as well as the bistriketone in 54% yield. The network formation and dissociation behaviors were investigated in detail by 1 H NMR and size exclusion chromatography experiments. Similarly to PHEMA, reversible crosslinking and decrosslinking of poly(vinyl alcohol) were achieved by addition of the bistriketone and by treatment of the resulting gel with H 2 O/DMSO (1/9, v/v), respectively. V C 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 921-928

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“…1723 cm −1 and ca. 1675 cm −1 ) as well as the hemiketal structure (ca. 1674 cm −1 ; Supporting Information Fig.…”

Section: Resultsmentioning

confidence: 99%

“…1674 cm −1 ; Supporting Information Fig. S2) . The glass transition temperature ( T g ) of the crosslinked PHEMA 6 was 84 °C (Supporting Information Fig.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reversible crosslinking and decrosslinking of polymers containing alcohol moiety using an acyclic bifunctional vicinal triketone

Yonekawa

Furusho

Takata

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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“…the adjacent two carbonyl groups in the three contiguous carbonyl groups. They are highly sensitive to water 9 and can be hydrated easily by residual moisture in solvents or air during the isolation processes to form hydrates. We isolated them in most cases by Kugelrohr distillation to avoid hydration of VTCs.…”

Section: Syn Thesismentioning

confidence: 99%

Direct Synthesis of Vicinal Tricarbonyl Amides by Coupling of α-Oxo Acid Chlorides with Carbamoylsilanes

Han

et al. 2019

Synthesis

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A convenient synthetic method for vicinal tricarbonyl amides by the cross-coupling reaction of α-oxo acid chlorides with carbamoylsilanes is developed. The reaction tolerates a broad range of substituents on the amido nitrogen of carbamoylsilanes, and directly affords good yields of vicinal tricarbonyl amides under mild conditions without use of oxidants. The reaction of carbamoylsilanes with oxalyl chloride has also been explored, and is accompanied by decarbonylation to give vicinal tricarbonyl amides.

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Synthesis of polymers containing vicinal tricarbonyl moiety and construction of reversible crosslinking–decrosslinking polymer system

Endō

Yonekawa

Sudo

2021

Polymer International

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Vicinal tricarbonyl compounds, in which three carbonyl groups are consecutively connected, are intriguing reactive molecules with a highly electrophilic nature. The center carbonyl group activated by two adjacent electron‐withdrawing carbonyl groups reacts efficiently with weak nucleophiles such as water, alcohols, thiols and aromatic amines to afford the corresponding adducts. In addition, because the reactions of the center carbonyl group with nucleophiles are intrinsically in equilibrium, the adducts undergo dissociation into the corresponding tricarbonyl compounds and nucleophiles under the appropriate conditions. Based on the reversible nature of vicinal tricarbonyl compounds with nucleophiles, a reversible crosslinking–decrosslinking system can be constructed where appropriately designed polymers and crosslinkers bearing vicinal tricarbonyl compounds are effectively used. © 2021 Society of Chemical Industry

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Synthesis and X-ray structural analysis of an acyclic bifunctional vicinal triketone, its hydrate, and its ethanol-adduct

Cited by 16 publications

References 30 publications

Reversible crosslinking and decrosslinking of polymers containing alcohol moiety using an acyclic bifunctional vicinal triketone

Reversible crosslinking and decrosslinking of polymers containing alcohol moiety using an acyclic bifunctional vicinal triketone

Direct Synthesis of Vicinal Tricarbonyl Amides by Coupling of α-Oxo Acid Chlorides with Carbamoylsilanes

Synthesis of polymers containing vicinal tricarbonyl moiety and construction of reversible crosslinking–decrosslinking polymer system

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