629-45-8Relevant articles and documents
Synthesis and Characterization of "atlas-Sphere" Copper Nanoclusters: New Insights into the Reaction of Cu2+ with Thiols
Cook, Andrew W.,Jones, Zachary R.,Wu, Guang,Teat, Simon J.,Scott, Susannah L.,Hayton, Trevor W.
, p. 8739 - 8749 (2019)
Thiolates are a widely used ligand class for the stabilization of M(0)-containing gold and silver nanoclusters. Curiously, though, very few thiolate-stabilized Cu nanoclusters are known. Herein, we report an examination of the reactivity of RSH (R = CH2CH2Ph, n-Bu, n-C12H25) with Cu2+ under anhydrous conditions. These reactions result in the formation of fluorescent "Atlas-sphere"-type copper thiolate nanoclusters, including [Cu12(SR′)6Cl12][(Cu(R′SH))6] (2, R′ = nBu) and [H(THF)2]2[Cu17(SR′′)6Cl13(THF)2(R′′SH)3] (3, R′′ = CH2CH2Ph), which were characterized by X-ray crystallography, electrospray ionization mass spectrometry, NMR spectroscopy, as well as X-ray absorption near-edge structure and extended X-ray absorption fine structure (EXAFS) spectroscopies. Consistent with our X-ray crystallographic results, the edge energies of 2 and 3 suggest they are constructed exclusively with Cu(I) ions. Similarly, EXAFS of 2 and 3 reveals long Cu-Cu pathlengths, which is also consistent with their X-ray crystal structures. Given these results, as well as past work on Cu2+/thiol reactivity, we suggest that Cu(0) is unlikely to be formed by the reaction of Cu2+ with a thiol and that previous reports of Cu(0)-containing nanoclusters synthesized by reaction of Cu2+ with thiols are likely erroneous.
METAL COMPLEXES OF TETRAPYRAZINOPORPHYRAZINES - EFFECTIVE CATALYSTS OF THE OXIDATION OF MERCAPTANS
Maizlish, V. E.,Korzhenevskii, A. B.,Klyuev, V. N.
, p. 1031 - 1033 (1984)
The catalytic activity of the tetrapyrazinoporphyrazine complexes of cobalt and iron have been studied in the oxidation of aliphatic mercaptans by molecular oxygen. n-Butyl mercaptan was used as the model compound.The metallotetrapyrazinoporphyrazines tested exhibited a considerably higher catalytic activity than cobalt phtalocyanine.
Rearrangement of radicals with migration of the chlorine atom from sulfur to carbon during the reaction of thiols with vinylsulfonyl chloride
Kandror,Freidlina
, p. 1814 - 1816 (1975)
1. A study was made of the reaction of n-butanethiol and thiophenol with vinylsulfonyl chloride at ～20° in an argon atmosphere. The reaction products are, respectively, β-chloroethyl butyl sulfide and β-chloroethyl phenyl sulfide (8-12% yields), and SO2 is liberated. The other reaction products are, respectively, the dibutyl and diphenyl disulfides (60-70% yields), HCl, and H2O. 2. Apparently, the formation of β-chloroethyl butyl sulfide and β-chloroethyl phenyl sulfide is associated with the addition of the thiyl radical to the double bond of vinylsulfonyl chloride and subsequent rearrangement of the RSCH2CHSO2Cl radicals, with the migration of chlorine from sulfur to the adjacent carbon atom.
Synergistic Effect of Iodine and Neighboring Amine Groups on Thioester Deacylation
Doi, Joyce Takahashi,Carpenter, Tracy Louise,Olmstead, Marylin M.,Musker, W. Kenneth
, p. 4684 - 4689 (1983)
The synergistic effect of a Lewis acid (I2) and an intramolecular Lewis base facilitates the deacylation of thioesters.When iodine is added to aqueous slution of S-3-(dimethylamino)propylthioacetate (I), deacylation is accelerated by a factor of 103-104.A severafold acceleration is observed for S-2-(2-pyridyl)ethyl thioacetate (II), and no rate enhancement is observed in the reaction of S-n-butyl thioacetate (III).The rate of iodine consumption at invariant pH and thioseter and iodine concentrations is zero order in iodine when III reacts and the first order in iodine when I reacts.Both kinetic orders are observed when II reacts.The effect of pH and iodine concentration on the rates of I and II is explaned by an intramolecular interaction between an iodine-thioester complex and the neighboring amine.The product of the reaction of the unsubstituted thioester III is the disulfide.However, overoxidation is observed in the reactions of I and II, and the sulfonic acids were the isolated products.The product from the oxidation of I has been confirmed to be (CH3)2+NH(CH2)3SO3- (IV) by single-crystal X-ray crystallography.
Visible-light-responsive lanthanide coordination polymers for highly efficient photocatalytic aerobic oxidation of amines and thiols
An, Shuyi,Guo, Zhifen,Liu, Xin,Che, Yan,Xing, Hongzhu,Chen, Peng
, p. 15767 - 15775 (2021/09/22)
Development of visible-light-induced photocatalytic reactions using molecular oxygen as the terminal oxidant is intriguing in view of the current environmental and energy issues. We report herein the synthesis and characterization of a series of novel pho
T BuOK-triggered bond formation reactions
Xu, Yulong,Shi, Xiaonan,Wu, Lipeng
, p. 24025 - 24029 (2019/08/13)
Recently, inexpensive and readily available tBuOK has seen widespread use in transition-metal-free reactions. Herein, we report the use of tBuOK for S-S, S-Se, NN and CN bond formations, which significantly extends the scope of tBuOK in chemical synthesis. Compared with traditional methods, we have realized mild and general methods for disulfide, azobenzenes imine etc. synthesis.
Trisulfides over disulfides: Highly selective synthetic strategies, anti-proliferative activities and sustained H2S release profiles
Bhattacherjee, Debojit,Sufian, Abu,Mahato, Sulendar K.,Begum, Samiyara,Banerjee, Kaustav,De, Sharmistha,Srivastava, Hemant Kumar,Bhabak, Krishna P.
supporting information, p. 13534 - 13537 (2019/11/14)
Temperature-and solvent-induced selective synthesis of trisulfides and disulfides is demonstrated. A remarkable selectivity was achieved using Na2S as a sulfur-Transfer agent under mild, greener, catalyst-free and additive-free conditions. This study reveals trisulfides as a better model than disulfides in general for a sustained release of H2S and potent anti-cancer activities.
Laccase-catalyzed in situ generation and regeneration of N-phenyltriazolinedione for the aerobic oxidative homo-coupling of thiols to disulfides
Khaledian, Donya,Rostami, Amin,Zarei, Seyed Amir
, p. 75 - 78 (2018/06/26)
The first report on aerobic in situ generation and regeneration of N-phenyltriazolinedione, a valuable oxidizing agent, from a catalytic amount of N-phenyl urazole in the presence of a laccase enzyme is presented. The application of a 4-phenyl urazole/Laccase/O2 as a new cooperative catalytic oxidation system is reported for a transition-metal-free and halogen free oxidative homo-coupling reaction of structurally diverse thiols to their corresponding disulfides with good to excellent yields in a phosphate buffer solution under mild reaction conditions.
A rapid, efficient and green procedure for transformation of alkyl halides/ tosylates to organochalcogens in water
Soleiman-Beigi, Mohammad,Yavari, Issa,Sadeghizadeh, Fatemeh
, p. 41 - 44 (2017/09/25)
A one-pot and efficient synthesis of dialkyl dichalcogenides (S, Se) in aqueous media under catalyst-free conditions using benzylic, allylic and primary halides with elemental sulfur and selenium has been developed. Also, this procedure was extended to preparation of trisulfides and triselenides from secondary and tertiary halides in same condition. In all cases, products can be obtained in good to excellent yield in short reactions time.
Oxidative dimerization of thiols to disulfide using recyclable magnetic nanoparticles
Masnabadi, Nasrin,Ghasemi, Mohammad Hadi,Beyki, Mostafa Hossein,Sadeghinia, Mohammad
, p. 1609 - 1618 (2017/02/15)
Abstract: Dimerization of thiol groups to disulfide is an important transformation in chemical processes. In this study, magnetic ion exchanged Montmorillonite-k10 was synthesized and characterized using FTIR, X-ray diffraction and scanning electron microscope techniques. Then, the application of the synthesized catalyst as an efficient oxidizing agent was evaluated in oxidative dimerization of different thiols to corresponding disulfides under optimal reaction conditions. The reaction was easily performed with aromatic, aliphatic and heterocyclic thiols. The magnetic catalyst was easily recovered by applying an external magnet and, further, was reused in successive reactions. Graphical Abstract: [Figure not available: see fulltext.]
