Dimethyl Trithiocarbonate Research Articles

Closed-loop recycling of sulfur-rich polymers with tunable properties spanning thermoplastics, elastomers, and vitrimers

The development of closed-loop recycling polymers that exhibit excellent performance is of great significance. Sulfur-rich polymers possessing excellent optical, thermal, and mechanical properties are promising candidates for chemical recycling but lack efficient synthetic strategies for achieving diverse structures. Herein, we report a universal synthetic strategy for producing polytrithiocarbonates, a class of sulfur-rich polymers, via the polycondensation of dithiols and dimethyl trithiocarbonate. This strategy has excellent compatibility with a wide range of monomers, including aliphatic, heteroatomic, and aromatic dithiols enabling the synthesis of polytrithiocarbonates with diverse structures. The present synthesis strategy offers a versatile platform for the construction of thermoplastics, elastomers, and vitrimers. Notably, these polytrithiocarbonates can be easily depolymerized via solvolysis into the corresponding monomers, which can be repolymerized to virgin polymers without changing the material properties.

Selective Bond Cleavage in RAFT Agents Promoted by Low-Energy Electron Attachment.

Radical polymerization with reversible addition‐fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well‐defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side‐reactions and high spatio‐temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low‐energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C−S bond is induced upon low‐energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group (.CH3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment.

One-pot synthesis of functionalized benzo[b]thiophenes and their hetero-fused analogues via intramolecular copper-catalyzed S-arylation of in situ generated enethiolates.

An efficient one-pot synthesis of highly functionalized multisubstituted benzo[b]thiophenes and their hetero-fused analogues, such as thieno[2,3-b]thiophenes, indolo[2,3-b]thiophenes, and pyrazolo[3,2-c]thiophenes, has been reported. The overall strategy involves sequential base-mediated condensation of 2-bromohet(aryl)acetonitrile precursors with (het)aryl/alkyl dithioesters or other thiocarbonyl species such as dimethyl trithiocarbonate, S-methyl xanthates, methyl N-imidazolyl dithioate, N-alkyl dithiocarbamate, and phenyl isothiocyanate, followed by intramolecular copper-catalyzed arylthiolation of in situ generated enethiolates, furnishing a broad range of 2-functionalized 3-cyanobenzo[b]- and/hetero-fused thiophenes in high yields.

Abiotic Synthesis of Organic Compounds from Carbon Disulfide Under Hydrothermal Conditions

Abiotic formation of organic compounds under hydrothermal conditions is of interest to bio, geo-, and cosmochemists. Oceanic sulfur-rich hydrothermal systems have been proposed as settings for the abiotic synthesis of organic compounds. Carbon disulfide is a common component of magmatic and hot spring gases, and is present in marine and terrestrial hydrothermal systems. Thus, its reactivity should be considered as another carbon source in addition to carbon dioxide in reductive aqueous thermosynthesis. We have examined the formation of organic compounds in aqueous solutions of carbon disulfide and oxalic acid at 175 degrees C for 5 and 72 h. The synthesis products from carbon disulfide in acidic aqueous solutions yielded a series of organic sulfur compounds. The major compounds after 5 h of reaction included dimethyl polysulfides (54.5%), methyl perthioacetate (27.6%), dimethyl trithiocarbonate (6.8%), trithianes (2.7%), hexathiepane (1.4%), trithiolanes (0.8%), and trithiacycloheptanes (0.3%). The main compounds after 72 h of reaction consisted of trithiacycloheptanes (39.4%), pentathiepane (11.6%), tetrathiocyclooctanes (11.5%), trithiolanes (10.6%), tetrathianes (4.4%), trithianes (1.2%), dimethyl trisulfide (1.1%), and numerous minor compounds. It is concluded that the abiotic formation of aliphatic straight-chain and cyclic polysulfides is possible under hydrothermal conditions and warrants further studies.

The 13C Chemical Shift Tensor Principal Values and Orientations in Dialkyl Carbonates and Trithiocarbonates

The 13C chemical shift tensor principal values for the trigonal carbonate and thiocarbonate carbon atoms in the dialkyl carbonates, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate, and in the trithiocarbonates, ethylene trithiocarbonate and dimethyl trithiocarbonate, respectively, were measured in various solid-state one-dimensional and two-dimensional nuclear magnetic resonance experiments. Furthermore, the chemical shift tensor principal values and orientations were calculated for the corresponding isolated molecules with quantum mechanically fully optimized geometries. Proton-optimized X-ray geometries of ethylene carbonate, ethylene trithiocarbonate, and diphenyl carbonate were used in embedded ion method (EIM) calculations and in calculations on the isolated molecules to obtain the theoretical principal values and to assign the chemical shift tensor orientations in these three compounds. Considerable improvement in the correlation between the experimental and calculated principal values is obtained when the electrostatic crystal potentials are included in EIM calculations. The chemical shift tensor orientations and principal values obtained for the dialkyl compounds in this study complement the previous data on a series of ionic potassium carbonates and thiocarbonates.

ChemInform Abstract: A New Application of Dimethyl Trithiocarbonate. Methylthiothiocarbonylation of 2,4‐Pentanedione and Some β‐Oxoesters.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A New Application of Dimethyl Trithiocarbonate. Methylthiothiocarbonylation of 2,4-Pentanedione and Some β-Oxoesters

2,4-Pentanedione, ethyl acetoacetate, benzoyl acetate and diethyl malonate 1a-d react with sodium acetate and dimethyl trithiocarbonate in dimethylformamide to afford methyl-β,β′-dicarbonyldithiocarboxylate derivatives 2a-d in moderate yield.

ChemInform Abstract: Synthetic Application of Tris(methylthio)methyl Salts. An Efficient Route to Trithioorthocarboxylic Esters from Strongly Activated Aromatic and Heteroaromatic Systems.

AbstractThe reaction of the electron‐rich aromatic and heteroaromatic compounds (IV) with the tris(methylthio)methyl salts (III), easily prepared from dimethyl trithiocarbonate (I), yields the trithioorthocarboxylic esters (V).

Dynamic NMR study of dimethyl trithiocarbonate

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDynamic NMR study of dimethyl trithiocarbonateMasood Garahi, Felicia Badelle, and Eric A. NoeCite this: J. Org. Chem. 1987, 52, 17, 3941–3942Publication Date (Print):August 1, 1987Publication History Published online1 May 2002Published inissue 1 August 1987https://doi.org/10.1021/jo00226a048RIGHTS & PERMISSIONSArticle Views118Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (280 KB) Get e-Alerts Get e-Alerts

Reactions of S-alkyl-NN-disubstituted thioamide salts. Part 3. Thiocarbamoyl cyanide derivatives

Two tetrahedrally substituted thiocarbamoyl cyanide derivatives have been found to undergo rearrangement on heating with morpholine. Bis(methylthio)-4-morpholinoacetonitrile (7) and methylthio-4-morpholinomalononitrile (8) were synthesised from SS′-dimethyl-N-(3-oxapentamethylene)dithiocarbamidium iodide (4), and, with morpholine gave tris-(3-oxapentamethylene)guanidinium thiocyanate (5; X = SCN) and reduction componds. The salt (4) also reacted with morpholine to give the guanidinium iodide (5; X = I) and with hydrogen sulphide giving dimethyl trithiocarbonate.

Réactions de condensation avec des carbanions de sulfonyl cétones. Propriétés chimiques des composés d'addition

AbstractThe dianions from a number of α‐sulfonyl ketones have been obtained using sodium hydride and n‐butyllithium. The dianions can produce with carbon disulfide, S‐dimethyl dithiocarbonate or dimethyl trithiocarbonate different addition compounds. The chemical reactions of these compounds with phosphorus pentasulfide, phenylhydrazine and methanol (in acid medium) have been investigated.

ChemInform Abstract: THE REACTION OF CHLORODITHIOFORMATES WITH GRIGNARD REAGENTS

AbstractIm Gegensatz zu den Formiaten ergeben die Dithioester (I) bei ihrer Umsetzung mit den Grignardverbindungen (II) bei ‐20°C nicht die erwarteten Dithioester, sondern die Thioketone (III).

The reaction of chlorodithioformates with Grignard reagents

AbstractEthyl and phenyl chlorodithioformate have been reacted at −20°C with phenylmagnesium bromide and p‐tolylmagnesium bromide to give substituted thioketones 4 in acceptable yields. The reaction between methyl chlorodithioformate and methylmagnesium iodide at −40°C gave dimethyl trithiocarbonate and 3,3,7,7‐tetrakis(methylthio)‐1,2,4,6‐tetrathiepane‐5‐thione (8). When the reaction took place at 0°C other compounds also were isolated in small yields.

Oxidative-addition across a carbon-sulfur bond: Platinum(0) complexes with ethylene trithiocarbonate and trimetylene trithiocarbonate

Platinum(0) phosphine complexes PtL 4 (where L = PPh 3 or PMePh 2) undergo oxidative addition reactions with ethylene trithiocarbonate, C 2H 4CS 3, to give cis- PtCS 2CH 2CH 2S (L) 2 and with trimethylene trithiocarbonate, (CH 2) 3CS 3, to give cis- PtCS 2CH 2CH 2CH 2S (PPh 3) 2. These bidentate ligands are displaced by CS 2 giving the free trithiocarbonates and the known CS 2 complex Pt(CS 2) (PPh 3) 2. Dimethyl trithiocarbonate, (CH 3S) 2CS, does not undergo the same type of oxidative-addition reaction with Pt(PPh 3) 4, and ethylene carbonate shows no reactivity toward Pt(PPh 3) 4.

Studies on Organo Sulfur Compounds. VI. The Reaction of S-Methyl-O-α-acetylenyl Xanthates and Metal Xanthates

Dimethyl trithiocarbonate (4), which was formed as one of by-products in the preparation of α-acetylenyl xanthate (3), was obtained by treating 2-propynyl xanthate (10) or 3-phenyl-2-propynyl xanthate (18) with potassium xanthate (17). The reaction pathway for the formation of 4 from 18 was studied in detail, and the mechanism of the formation of dimethyl trithiocarbonate (4) and other by-products were consequently clarified.

Studies on Derivatives of Substituted Benzenesulfonyl Carbamic Acid. V.

It was found that methyl N-substituted benzenesulfonyl-dithiocarbamate (2) and ethyl N-substituted benzenesulfonyl-thiocarbamate (3) were synthesized from the corresponding benzene-sulfonamide (1) and dimethyl trithiocarbonate or methyl ethylxanthate. The R. Gommper's method, which is applicable for the synthesis of (2) containing a p-methyl-or a p-chloro-substituent from the corresponding (1), failed to give the p-acetyl analog. In contrast, (2) as well as (3) containing a p-acetyl group could readily be obtained by this new method. Condensation reactions between (1) and sodium trithiocarbonate or potassium ethylxanthate did not take place.

Physical properties of organic thiones: Part IV. The basicity of the thiocarbonyl group in various thiones

AbstractThe basicities of four N,N‐dimethylthioamides, of thiourea and all the N‐methylated thioureas, of ethylenethiourea, N,N′‐dimethylethylenethiourea and trimethylenethiourea, of S‐methyl N,N‐dimethyldithiocarbamate and ‐dimethyl trithiocarbonate, were determined. Measurements were made spectrophotometrically in aqueous sulphuric acid of various strengths and attempts were made to correct the absorption values for solvent effects. In methylated thioureas both electronic and steric effects influence the acidity constants. These effects appear to be of comparable magnitude. The results on the dithiocarbamate and trithiocarbonate show that in these compounds the basicity is determined by the negative inductive rather than by the positive mesomeric effect of the methylmercapto group. The amino group exerts a strong mesomeric action as expected.

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Platinum(0) phosphine complexes PtL4 (where L = PPh3 or PMePh2) undergo oxidative addition reactions with ethylene trithiocarbonate, C2H4CS3, to give cis-PtCS2CH2CH2S(L)2 and with trimethylene trithiocarbonate, (CH2)3CS3, to give cis-PtCS2CH2CH2CH2S(PPh3)2. These bidentate ligands are displaced by CS2 giving the free trithiocarbonates and the known CS2 complex Pt(CS2) (PPh3)2. Dimethyl trithiocarbonate, (CH3S)2CS, does not undergo the same type of oxidative-addition reaction with Pt(PPh3)4, and ethylene carbonate shows no reactivity toward Pt(PPh3)4.