Sulfur‐containing polymers. XVI. Oxidative coupling of dithiols with various diacyl disulfides

Kobayashi, Norio; Osawa, Akiko; Fujisawa, Tamotsu

doi:10.1002/pol.1975.170131223

Cited by 10 publications

(3 citation statements)

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“…It has been reported that thiols would react with tetra- alkylthiuram disulfides to yield dialkylammonium dialkyldithiocarbamate and the disulfide derivative (derived from the thiol) quantitatively under mild conditions. 39 As expected, after MCE and TDS were mixed for 5 min, the disulfide derivative, 2-hydroxyethyl disulfide (HEDS), and diethylammonium diethyldithiocarbamate (DDDC), rather than TDS and MCE themselves, were observed in the 1 H NMR and highperformance liquid chromatography−mass spectrometry (HPLC-MS) measurements (SI Figure S3), indicating a rapid, complete oxidation reaction. Since the reaction was too fast for NMR and HPLC to monitor, we employed UV− vis absorption spectroscopy to investigate the reaction kinetics (SI Figure S4) and calculated the rate constant of thiol oxidation (k 1 ) using the well-known kinetic eq (SI eq S3c).…”

Section: Resultssupporting

confidence: 54%

“…The 2-mercaptoethanol (MCE) and TDS were selected to study the oxidation reaction. It has been reported that thiols would react with tetra-alkylthiuram disulfides to yield dialkylammonium dialkyldithiocarbamate and the disulfide derivative (derived from the thiol) quantitatively under mild conditions . As expected, after MCE and TDS were mixed for 5 min, the disulfide derivative, 2-hydroxyethyl disulfide (HEDS), and diethylammonium diethyldithiocarbamate (DDDC), rather than TDS and MCE themselves, were observed in the 1 H NMR and high-performance liquid chromatography–mass spectrometry (HPLC-MS) measurements (SI Figure S3), indicating a rapid, complete oxidation reaction.…”

Section: Resultsmentioning

confidence: 79%

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Programming Hydrogels with Complex Transient Behaviors via Autocatalytic Cascade Reactions

Zhang

Liu

et al. 2022

ACS Appl. Mater. Interfaces

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It is challenging to design complex synthetic life-like systems that can show both autoevolution and fuel-driven transient behaviors. Here, we report a new class of chemical reaction networks (CRNs) to construct life-like polymer hydrogels. The CRNs are constituted of autocatalytic cascade reactions and fuel-driven reaction networks. The reactions start with only two compounds, that is, thiol of 4-arm-PEG-SH and thiuram disulfides, and undergo thiol oxidation (k 1), disulfide metathesis (k 2), and thionate hydrolysis-coupling reactions (k 3) subsequently, leading to a four-state autonomous transition of sol(I) → soft gel → sol(II) → stiff gel. Moreover, thiuram disulfides can be applied as a fuel to drive the repeated occurrence of metathesis and hydrolysis-coupling reactions, generating dissipative stiff gel → sol(II) → stiff gel cycles. Systematic kinetics studies reveal that the event and lifetime of every transient state could be delicately tailored-up by varying the thiuram disulfide concentration, pH of the system, and thiuram structures. Since the consecutive transient behaviors are precisely predictable, we envision the strategy’s potential in guiding the molecular designs of autonomous and adaptive materials for many fields.

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Section: Resultssupporting

confidence: 54%

Section: Resultsmentioning

confidence: 79%

Programming Hydrogels with Complex Transient Behaviors via Autocatalytic Cascade Reactions

Zhang

Liu

et al. 2022

ACS Appl. Mater. Interfaces

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“…Bis(oxycarbonyl)disulfide reacts with dithiols in the presence of triethylamine to give disulfide polymers [173]: Other than bis(oxycarbonyl) disulfides, compounds such as thiuram disulfides, dixanthogens and bis(carbomyl) disulfides were also used to prepare disulfide polymers [174]. Alternating as well as random copolymers have also been prepared using this method [175,176].…”

Section: Oxidative Coupling Of Dithiols With Diaeyl Disulfidesmentioning

confidence: 99%

Polymers containing disulfide, tetrasulfide, diselenide and ditelluride linkages in the main chain

Kishore

Ganesh

Polymer Synthesis/Polymer Engineering

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The present review articulates the syntheses and properties of industrially important disulfide and tetrasulfide polymers. The diselenide and ditelluride polymers have also been reviewed, for the first time, so that a comprehensive view on the polymers containing group VIA elements can be obtained. The latter two polymers are gaining considerable current attention due to their semi-conducting properties. The emphasis has been made to sift through the developments in the last ten years or so to get the latest flavour in these rapidly developing polymers. We have also attempted to bring to the fore several contradicting results, like, for example, the crystallinity of ditelluride polymers, to clear the mist in such reports. We hope that this review will help those working in the field to assess the progress achieved in this area and that it may also provide useful orientation for those who wish to become involved.

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Crystallographic Data and Melting Points for Various Polymers

Miller

1999

The Wiley Database of Polymer Properties

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Sulfur‐containing polymers. XVI. Oxidative coupling of dithiols with various diacyl disulfides

Abstract: Previously we have reported' that bis(oxycarbony1) disulfides (I) react with dithiols in the presence of triethylamine to give disulfide polymers in accord with eq. (1).

Cited by 10 publications

References 3 publications

Programming Hydrogels with Complex Transient Behaviors via Autocatalytic Cascade Reactions

Programming Hydrogels with Complex Transient Behaviors via Autocatalytic Cascade Reactions

Polymers containing disulfide, tetrasulfide, diselenide and ditelluride linkages in the main chain

Crystallographic Data and Melting Points for Various Polymers

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