Carbon Tetrabromide Promoted Reaction of Amines with Carbon Disulfide: Facile and Efficient Synthesis of Thioureas and Thiuram Disulfides

Liang, Fushun; Tan, Jing; Piao, Chengri; Li, Qun

doi:10.1055/s-0028-1083199

Cited by 36 publications

(24 citation statements)

References 10 publications

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“…Indeed, one-electron oxidation of sodium dithiocarbamate affords thiuram disulfide 7 in excellent yields with various oxidants such as iodine (see SI). 34 …”

Section: Resultsmentioning

confidence: 99%

Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers

et al. 2017

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The mechanism of the recently reported photocontrolled cationic polymerization of vinyl ethers was investigated using a variety of catalysts and chain-transfer agents (CTAs) as well as diverse spectroscopic and electrochemical analytical techniques. Our study revealed a complex activation step characterized by one-electron oxidation of the CTA. This oxidation is followed by mesolytic cleavage of the resulting radical cation species, which leads to the generation of a reactive cation–this species initiates the polymerization of the vinyl ether monomer–and a dithiocarbamate radical that is likely in equilibrium with the corresponding thiuram disulfide dimer. Reversible addition–fragmentation type degenerative chain transfer contributes to the narrow dispersities and control over chain growth observed under these conditions. Finally, the deactivation step is contingent upon the oxidation of the reduced photocatalyst by the dithiocarbamate radical concomitant with the production of a dithiocarbamate anion that caps the polymer chain end. The fine-tuning of the electronic properties and redox potentials of the photocatalyst in both the excited and the ground states is necessary to obtain a photocontrolled system rather than simply a photoinitiated system. The elucidation of the elementary steps of this process will aid the design of new catalytic systems and their real-world applications.

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“…Indeed, one-electron oxidation of sodium dithiocarbamate affords thiuram disulfide 7 in excellent yields with various oxidants such as iodine (see SI). 34 …”

Section: Resultsmentioning

confidence: 99%

Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers

et al. 2017

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“…Without further purification, the (presumed) intermediate dithiocarbamic acid was oxidised to the required thiuram disulfide in low to moderate yields as previously described using either aqueous iodine/potassium iodide22 (compounds 3a and 3b ) or hydrogen peroxide23 in acetic acid (compound 3c ). More recently an efficient synthesis of thiuram disulfides has been reported using carbon tetrabromide to promote reaction of amines with carbon disulfide and subsequent disulfide bond formation 24. Alternative methods for the chemical oxidation of thiols to disulfides are also available, for example the use of bromine on hydrated silica 25.…”

Section: Chemistrymentioning

confidence: 99%

Exploring the Structural Requirements for Inhibition of the Ubiquitin E3 Ligase Breast Cancer Associated Protein 2 (BCA2) as a Treatment for Breast Cancer

Brahemi

Kona²,

Fiasella³

et al. 2010

J. Med. Chem.

144

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The zinc-ejecting aldehyde dehydrogenase (ALDH) inhibitory drug disulfiram (DSF) was found to be a breast cancer-associated protein 2 (BCA2) inhibitor with potent antitumor activity. We herein describe our work in the synthesis and evaluation of new series of zinc-affinic molecules to explore the structural requirements for selective BCA2-inhibitory antitumor activity. An N(C=S)S-S motif was found to be required, based on selective activity in BCA2-expressing breast cancer cell lines and against recombinant BCA2 protein. Notably, the DSF analogs (3a and 3c) and dithio(peroxo)thioate compounds (5d and 5f) were found to have potent activity (submicromolar IC50) in BCA2 positive MCF-7 and T47D cells but were inactive (IC50 >10 μM) in BCA2 negative MDA-MB-231 breast cancer cells and the normal breast epithelial cell line MCF10A. Testing in the isogenic BCA2 +ve MDA-MB-231/ER cell line restored antitumor activity for compounds that were inactive in the BCA2 negative MDA-MB-231 cell line. In contrast, structurally related dithiocarbamates and benzisothiazolones (lacking the disulfide bond) were all inactive. Compounds 5d and 5f were additionally found to lack ALDH-inhibitory activity, suggestive of selective E3 ligase-inhibitory activity and worthy of further development.

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“…[8] More recently, carbon tetrabromide has been found to mediate the formation of carbon-sulfur bond [9] and thioureas. [10] As a catalyst, CBr 4 offers the advantages that the reaction conditions are generally mild, and the reactions are often chemo- [11] as well as regioselective. [8] On the other hand, CBr 4 is an irritant and a toxic substance (IVN-MUS LD 50 : 56 mgkg…”

Section: Introductionmentioning

confidence: 99%

“…Because of the ready solubility of CBr 4 in many organic solvents, the separation and recovery of CBr 4 from the reaction mixture usually require chromatography. [1][2][3][4][5][6][7][8][9][10] In here, we describe a catalytic system of CBr 4 which is stable, functions under mild conditions, is easily recoverable from the reaction mixture, and reusable for acetalization and tetrahydropyranylation reactions.…”

mentioning

confidence: 99%

Carbon Tetrabromide/Sodium Triphenylphosphine‐m‐sulfonate (TPPMS) as an Efficient and Easily Recoverable Catalyst for Acetalization and Tetrahydropyranylation Reactions

Huo¹,

Chan²

2009

Adv Synth Catal

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Carbon Tetrabromide Promoted Reaction of Amines with Carbon Disulfide: Facile and Efficient Synthesis of Thioureas and Thiuram Disulfides

Cited by 36 publications

References 10 publications

Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers

Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers

Exploring the Structural Requirements for Inhibition of the Ubiquitin E3 Ligase Breast Cancer Associated Protein 2 (BCA2) as a Treatment for Breast Cancer

Carbon Tetrabromide/Sodium Triphenylphosphine‐m‐sulfonate (TPPMS) as an Efficient and Easily Recoverable Catalyst for Acetalization and Tetrahydropyranylation Reactions

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