26504-29-0

Usage

Uses

Used in Polymer Science:
Bis(benzylsulfanyl)methanethione is used as a Reversible Addition Fragmentation Chain Transfer (RAFT) agent in polymerization processes. It offers excellent control over the polymerization of various vinyl monomers, such as styrene, methacrylate, and acrylamide, allowing for the production of polymers with well-defined structures and properties.
Used in Pharmaceutical Industry:
As a trithiocarbonate-based RAFT agent, bis(benzylsulfanyl)methanethione is utilized as a bifunctional Chain Transfer Agent (CTA) in the RAFT polymerization of block copolymers. This application is particularly relevant in the field of drug delivery, where it helps in the development of advanced drug delivery systems with improved control over the release and targeting of therapeutic agents.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C15H14S3/c16-15(17-11-13-7-3-1-4-8-13)18-12-14-9-5-2-6-10-14/h1-10H,11-12H2

Upstream product

• 100-39-0 benzyl bromide 
• 584-10-1 potassium trithiocarbonate 
• 100-44-7 benzyl chloride 
• 75-15-0 carbon disulfide 
• 56-23-5 tetrachloromethane 
• 594-42-3 chlorothio-trichloro-methane 
• 100-53-8 phenylmethanethiol 
• 6160-65-2 1,1'-Thiocarbonyldiimidazole 
• 66728-36-7 trithiocarbonic acid monobenzyl ester 
• 1024-41-5 benzyl tosylate 
• 100-42-5 styrene 
• 62907-90-8 potassium benzyl carbonotrithioate 
• 1422636-47-2 tetrabenzyl (1,3-dithietane-2,2,4,4-tetrayl)tetracarbonotrithioate 
• 288-32-4 1H-imidazole 

Downstream Products

• 13046-51-0 tetrakis(benzylthio)ethylene 
• 113090-84-9 N'-phenyl-dithiocarbonohydrazonic acid dibenzyl ester 
• 188055-10-9 1,1-bis(phenylmethylthio)-1-sulfinylmethane 
• 35345-26-7 Oxalsaeure-bisthiolbenzylester 
• 98-83-9 isopropenylbenzene 
• 26504-28-9 dithiocarbonic acid S,S'-dibenzyl ester 
• 10606-38-9 tris(phenylmethylthio)methane 
• 32779-85-4 S-phenylmethyl thioformate 

Relevant academic research and scientific papers

Controlled radical polymerization of acrylonitrile in the presence of trithiocarbonates as reversible addition-fragmentation chain transfer agents

Specific features of pseudo-living radical polymerization of acrylonitrile in dimethyl sulfoxide solution in the presence of low-molecular-weight and polymeric trithiocarbonates as reversible addition-fragmentation chain transfer agents were studied.

Influence of the microstructure of acrylic acid-n-butyl acrylate copolymers prepared by pseudoliving radical polymerization by the reversible addition-fragmentation chain transfer mechanism on their surface activity in aqueous solutions

The influence of the microstructure of acrylic acid-n-butyl acrylate copolymers prepared by pseudoliving radical polymerization by the reversible addition-fragmentation chain transfer mechanism on their surface activity in aqueous solutions was studied. The mechanisms of adsorption of polymer macromolecules on the phase boundary, accounting for the difference in the behavior of the random and block copolymers, were suggested. The dependence of the surface activity on the chain flexibility was elucidated. This dependence is very significant for the random copolymers and insignificant for the block copolymers.

Selective one-pot synthesis of trithiocarbonates, xanthates, and dithiocarbamates for use in RAFT/MADIX living radical polymerizations

We report a facile route for the production of chain transfer agents for reversible addition fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations, via a one-pot reaction. 1,1′-Thiocarbonyl diimidazole (TCDI) undergoes controlled monosubstitution when reacted with secondary thiols or alcohols. The intermediate S/O-esters of imidazole-N-thionocarboxylic acid react efficiently with a range of primary thiols, alcohols, and amines to form asymmetrical dithiocarbonates, trithiocarbonates, and dithiocarbamates, respectively. The synthesis provides a facile approach to the controlled radical polymerization of vinyl monomers through the reversible addition-fragmentation chain transfer (RAFT) mechanism.

Thermoresponsive PS-b-PNIPAM-b-PS Micelles: Aggregation behavior, segmental dynamics, and thermal response

We have studied the thermal behavior of amphiphilic, symmetric triblock copolymers having short, deuterated polystyrene (PS) end blocks and a large poly(N-isopropylacrylamide) (PNIPAM) middle block exhibiting a lower critical solution temperature (LCST) in aqueous solution. A wide range of concentrations (0.1-300 mg/mL) is investigated using a number of analytical methods such as fluorescence correlation spectroscopy (FCS), turbidimetry, dynamic light scattering (DLS), small-angle neutron scattering (SANS), and neutron spin-echo spectroscopy (NSE). The critical micelle concentration is determined using FCS to be 1 μM or less. The collapse of the micelles at the LCST is investigated using turbidimetry and DLS and shows a weak dependence on the degree of polymerization of the PNIPAM block, SANS with contrast matching allows us to reveal the core-shell structure of the micelles as well as their correlation as a function of temperature. The segmental dynamics of the PNIPAM shell are studied as a function of temperature and are found to be faster in the collapsed state than in the swollen state. The mode detected has a linear dispersion in q2 and is found to be faster in the collapsed state as compared to the swollen state. We attribute this result to the averaging over mobile and immobilized segments.

Norbornene-containing dithiocarbamates for use in reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)

Two new dithiocarbamate chain transfer agents (CTAs) with norbornene-containing Z-groups were prepared for use in reversible addition-fragmentation chain transfer (RAFT) polymerization. CTA 1b, which contains an electron deficient norbornene imide Z-group, was found to effectively mediate RAFT polymerization of 2° more activated monomers (MAMs) but did not facilitate RAFT of 3° MAMs or less activated monomers (LAMs). In contrast, CTA 2, derived from a norbornene amine, was well suited for the polymerization of LAMs, but did not control RAFT of MAMs. Poly(vinyl acetate) (PVAc), prepared by RAFT polymerization mediated by CTA 2, possessed the expected CTA-derived α- and ω-end groups. Ring-opening metathesis polymerization (ROMP) of 2 was carried out, and full conversion to polymer was achieved within 20 min. Based on this result, ROMP grafting-through of a PVAc macromonomer derived from CTA 2 was carried out, resulting in the formation of a well-defined PVAc bottlebrush polymer with a narrow molecular weight distribution.

End group polarity and block symmetry effects on cloud point and hydrodynamic diameter of thermoresponsive block copolymers

Thermoresponsive block copolymers are of interest for delivery vehicles in the body. Often an interior domain is designed for the active agent and the exterior domain provides stability in the bloodstream, and may carry a targeting ligand. There is still much to learn about how block sequence and chain end identity affect micelle structure, size, and cloud points. Here, hydrophilic oligo(ethylene glycol) methyl ether acrylate and more hydrophobic di(ethylene glycol) methyl ether methacrylate monomers were polymerized to give amphiphilic block copolymers with amphiphilic chain ends. The block sequence and chain end identity were both controlled by appropriate choice of RAFT chain transfer agents to study the effect of 'matched' and 'mismatched' chain end polarity with amphiphilic block sequence. The affect of matching or mismatching chain end polarity and block sequence was studied on the hydrodynamic diameter, cloud point, and temperature range of the chain collapse on linear di- and triblock copolymers and star diblock polymers. The affects of matching or mismatching chain end polarity were significant with linear diblock copolymers but more complex with triblock and star copolymers. Explanations of these results may help guide others in designing thermoresponsive block copolymers.

Controlled (Co)polymerization of methacrylates using a novel symmetrical trithiocarbonate raft agent bearing diphenylmethyl groups

Herein, we report a novel type of symmetrical trithiocarbonate chain transfer agent (CTA) based diphenylmethyl as R groups. The utilization of this CTA in the Reversible Addition-Fragmentation chain Transfer (RAFT) process reveals an efficient control in the polymerization of methacrylic monomers and the preparation of block copolymers. The latter are obtained by the (co)polymerization of styrene or butyl acrylate using a functionalized macro-CTA polymethyl methacrylate (PMMA) previously synthesized. Data show low molecular weight dispersity values (D 1.5) particularly in the polymerization of methacrylic monomers. Considering a typical RAFT mechanism, the leaving groups (R) from the fragmentation of CTA should be able to re-initiate the polymerization (formation of growth chains) allowing an efficient control of the process. Nevertheless, in the case of the polymerization of MMA in the presence of this symmetrical CTA, the polymerization process displays an atypical behavior that requires high [initiator]/[CTA] molar ratios for accessing predictable molecular weights without affecting the D. Some evidence suggests that this does not completely behave as a common RAFT agent as it is not completely consumed during the polymerization reaction, and it needs atypical high molar ratios [initiator]/[CTA] to be closer to the predicted molecular weight without affecting the D. This work demonstrates that MMA and other methacrylic monomers can be polymerized in a controlled way, and with “living” characteristics, using certain symmetrical trithiocarbonates.

A convenient one-pot method for the synthesis of symmetrical dialkyl trithiocarbonates using NH4OAc under mild neutral conditions

A facial, new, one-pot method for the preparation of symmetrical organic trithiocarbonates from various alkyl halides and carbon disulfide is described. This is a convenient, clean, and mild procedure, which involves the use of the neutral, nontoxic, commercially available, and inexpensive reagent NH4OAc in the preparation of the trithiocarbonate ion from carbon disulfide.

Investigations of the Thermal Responsiveness of 1,4,2-Oxathiazoles

The first systematic study of the thermal rearrangement/fragmentation of 5,5-disubstituted 1,4,2-oxathiazoles into isothiocyanates is reported. Structure-activity relationships reveal that the choice of substituent at the 5-position of the 1,4,2-oxathiazoles is the predominant factor to influence the ease of fragmentation.

Superbasic system CsOH/DMSO as a reagent for a fast one-step synthesis of symmetrical dialkyl trithiocarbonates

Symmetrical dialkyl trithiocarbonates were readily synthesized in excellent yields by one-step reaction of carbon disulfide and various alkyl halides under mild reaction conditions in the presence of cesium hydroxide as a super basic system. This method provides a synthesis of symmetrical dialkyl trithiocarbonates in short reaction times without the use of highly toxic starting materials.