1677-27-6Relevant articles and documents
Use of dimethyldioxirane for the oxidation of 1,2-dithiolan-3-ones to 1- oxides or 1,1-dioxides. Preparation of 3H-1,2-benzodithiol-3-one 1,1-dioxide (Beaucage sulfurizing reagent)
Marchan, Vicente,Gibert, Mariona,Messeguer, Angel,Pedroso, Enrique,Grandas, Anna
, p. 43 - 45 (1999)
Quantitative oxidation of 3H-1,2-benzodithiol-3-one to 3H-1,2- benzodithiol-3-one 1, 1-dioxide (Beaucage sulfurizing reagent) is achieved by reaction of the dithiolanone with a fourfold molar excess of dimethyldioxirane for 2-4 hours at room temperature. A one- or twofold molar excess of reagent affords the 1-oxide as the main product.
1,2-Dithiolan-3-ones and derivatives structurally related to leinamycin. Synthesis and biological evaluation
Salvetti, Raul,Martinetti, Giovanni,Ubiali, Daniela,Pregnolato, Massimo,Pagani, Giuseppe
, p. 995 - 998 (2003)
Leinamycin, an antitumor antibiotic isolated from Streptomyces sp., shows a 1,2-dithiolan-3-one 1-oxide heterocycle that appears to be involved in the biological activity. Several derivatives related to 1,2-dithiolan-3-one 1-oxide have been prepared and their activity as antineoplastic agents have been investigated. The synthesized compounds did not display a significative antitumor or cytotoxic activity in vitro.
Understanding Reactivity and Assembly of Dichalcogenides: Structural, Electrostatic Potential, and Topological Analyses of 3 H-1,2-Benzodithiol-3-one and Selenium Analogs
Shukla, Rahul,Dhaka, Arun,Aubert, Emmanuel,Vijayakumar-Syamala, Vishnu,Jeannin, Olivier,Fourmigué, Marc,Espinosa, Enrique
, p. 7704 - 7725 (2020)
Molecular assembly and reactivity have been investigated with a series of 3H-1,2-benzodithiol-3-(thi)one derivatives and their (mixed) selenated analogs. Electrostatic potential calculations on monomers show three σ-hole regions around the dichalcogenide Ch-Ch bond (Ch = S, Se), one side-on and two along the bonding direction. The topological analysis of the electron density ρ(r) points to the weak nature of the Ch-Ch bond. σ-Hole and lone-pair regions are described in terms of charge depletion (CD) and charge concentration (CC) sites found in the valence shell of chalcogen atoms. Whereas CD and CC sites are characterized by the topological critical points of L(r) = -2ρ(r), their electrophilic and nucleophilic powers are measured by the corresponding L/ρ magnitudes. In crystal structures, each chalcogen bond (ChB) involves a σ-hole region and shows a CD?CC interaction that aligns with the internuclear direction of the atoms the CD and CC sites belong. The alignment holds simultaneously for all of the ChB interactions in each crystal structure, indicating that CD?CC interactions drive molecular orientation in molecular assembly. Strength of ChB is measured in terms of the topological properties of ρ(r), whereas the intensity of the electrophilic?nucleophilic interaction is monitored by [(L/ρ)CC - (L/ρ)CD]/dCC?CD2. The σ-hole in side-on conformation forms the strongest ChB interactions in molecular assembly. Reactivity of molecules against nucleophilic attack has been investigated along each of the three σ-hole regions by using fluoride as a probe. Adducts formed along the Ch-Ch bonding direction are energetically more favorable than in side-on conformation. At optimized geometries, the F?Ch bond (Ch = S, Se) exhibits a partial covalent character, while it weakens concomitantly the Ch?Ch bond that also becomes of partial covalent character. In the reactivity process, the significant reorientation of the plane containing the chalcogen lone pairs, along with the opening, shrinking, and splitting of reactivity surfaces 2ρ(r) = 0, is the signature of the charge redistribution that involves the nucleophilic attack.
Reaction of n-propanethiol with 3H-1,2-benzodithiol-3-one 1-oxide and 5,5-dimethyl-1,2-dithiolan-3-one 1-oxide: Studies related to the reaction of antitumor antibiotic leinamycin with DNA
Behroozi,Kim,Gates
, p. 3964 - 3966 (1995)
We have studied the reaction of n-propanethiol with 3H-1,2-benzodithiol-3-one 1-oxide and 5,5-dimethyl-1,2-dithiolan-3-one 1-oxide. The major products isolated from these reactions are the corresponding dithio carboxylic acids. In the case of 3H-1,2-benzodithiol-3-one 1-oxide, an unstable hydrodisulfide that decomposes to polysulfides under the reaction conditions is formed. A mechanism involving an unstable oxathiolanone intermediate is proposed for these reactions. We believe that these reactions may serve as useful models for some aspects of the thiol-activated DNA-cleavage chemistry of the antitumor antibiotic leinamycin, a natural product that contains a 1,2-dithiolan-3-one 1-oxide heterocycle.
“Turn-on” fluorescent probe for detection of H2S and its applications in bioimaging
Zhao, Qi,Kang, Jin,Wen, Ying,Huo, Fangjun,Zhang, Yongbin,Yin, Caixia
, p. 8 - 12 (2018)
A novel fluorescent probe (named YQ-1) containing disulfide-bond coumarin derivative was developed for H2S. In response to H2S, YQ-1 showed remarkable fluorescent emission enhancement at 462?nm. Besides, YQ-1 exhibited higher selectivity, faster response rate, low cytotoxicity and low detection limit (0.052?μM). Further, YQ-1 was used to detect the presence of H2S level in living A549 cells, indicating YQ-1 has good membrane permeability and fluorescence properties.
Fluorescent probe for detecting hydrogen sulfide based on disulfide nucleophilic substitution-addition
Huo, Fangjun,Wang, Junping,Wu, Qing,Yin, Caixia
, (2020/05/08)
In view of the importance of hydrogen sulfide (H2S) in the organism, a fast, noninvasive method for the detection of H2S in situ is needed. Fluorescent probes based on disulfide-bond nucleophilic substitution-addition can selectively detect H2S in vivo, which is very popular because it allows quick response for H2S, thus it will be a useful tool for monitoring H2S in the vivo. We developed a dicyanoisopentanone-based H2S fluorescent probe (EW-H) that used a disulfide group as a self-destructive linker reaction site. Under the nucleophilic substitution of H2S, the disulfide bond of EW-H was cleaved, and then nucleophilic addition took place intramolecularly to release the fluorophore (at 580 nm). The response to H2S, EW-H had high sensitivity (86 nM of the detection limit), large Stokes shift (155 nm) and a fast response time. More importantly, the probe was also applied for bioimaging in HepG2 cells, indicating its potential applications in biological organism.
Switchable Copper-Catalyzed Approach to Benzodithiole, Benzothiaselenole, and Dibenzodithiocine Skeletons
Huang, Meng-Qiao,K?rk?s, Markus D.,Li, Tuan-Jie,Liu, Jian-Quan,Shatskiy, Andrey,Wang, Xiang-Shan
supporting information, p. 3454 - 3459 (2020/04/30)
A copper-catalyzed reaction between 2-bromo-benzothioamides and S8 or Se involving sulfur rearrangement is reported, enabling access to benzodithioles 2 and benzothiaselenoles 6 in the presence of Cs2CO3. In the absence of S8 or Se, the reaction affords dibenzodithiocines 7 via two consecutive C(sp2)-S Ullmann couplings.
Preparation method of benzodithiole skeleton compounds
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Paragraph 0029-0066, (2020/04/17)
The invention discloses a preparation method of benzodithiole skeleton compounds. The preparation method comprises the following steps: adding a 2-bromothiobenzamide derivative and S8 into an organicsolvent, adding a ligand and an alkali, performing a reaction in an inert atmosphere under the action of a copper catalyst, and carrying out suction filtration and acidic hydrolysis treatment on the reaction system to obtain the benzodithiole skeleton compounds. The method has the advantages of simplicity in operation, easily available raw materials and reagents, mild conditions, green and environmentally-friendly reaction system, and easiness in separation and purification of the product, is suitable for synthesis of a plurality of benzodithiole skeleton compounds, is especially suitable forlarge-scale industrial production, can prepare high-purity benzodithiole skeleton compounds at high efficiency and high yield, and has a highest product yield of 91%.
The Development of Fluorescent Probes for Visualizing Intracellular Hydrogen Polysulfides
Chen, Wei,Rosser, Ethan W.,Matsunaga, Tetsuro,Pacheco, Armando,Akaike, Takaaki,Xian, Ming
supporting information, p. 13961 - 13965 (2016/01/25)
Endogenous hydrogen polysulfides (H2Sn; n>1) have been recognized as important regulators in sulfur-related redox biology. H2Sn can activate tumor suppressors, ion channels, and transcription factors with higher potency than H2S. Although H2Sn are drawing increasing attention, their exact mechanisms of action are still poorly understood. A major hurdle in this field is the lack of reliable and convenient methods for H2Sn detection. Herein we report a H2Sn-mediated benzodithiolone formation under mild conditions. This method takes advantage of the unique dual reactivity of H2Sn as both a nucleophile and an electrophile. Based on this reaction, three fluorescent probes (PSP-1, PSP-2, and PSP-3) were synthesized and evaluated. Among the probes prepared, PSP-3 showed a desirable off/on fluorescence response to H2Sn and high specificity. The probe was successfully applied in visualizing intracellular H2Sn.
Fluorescent probes based on nucleophilic substitution-cyclization for hydrogen sulfide detection and bioimaging
Peng, Bo,Chen, Wei,Liu, Chunrong,Rosser, Ethan W.,Pacheco, Armando,Zhao, Yu,Aguilar, Hector C.,Xian, Ming
, p. 1010 - 1016 (2014/02/14)
The design, synthesis, properties, and cell imaging applications of a series of 2-pyridyl disulfide based fluorescent probes (WSP1, WSP2, WSP3, WSP4 and WSP5) for hydrogen sulfide detection are reported. The strategy is based on the dual-nucleophilicity of hydrogen sulfide. A hydrogen sulfide mediated tandem nucleophilic substitution-cyclization reaction is used to release the fluorophores and turn on the fluorescence. The probes showed high sensitivity and selectivity for hydrogen sulfide over other reactive sulfur species, including cysteine and glutathione. Copyright
