Dimethylthiocarbamoyl Chloride Research Articles

Carbon-sulfur double bond electrolyte additives as redox mediator for lithium-oxygen batteries

Lithium-oxygen battery (LOB) has extremely high theoretical energy density (about 5–10 times as that of lithium-ion battery), which is being studied widely. At present, LOB still face many severe challenges such as low energy conversion efficiency, poor rate performance and short cycling life, which seriously restricts its development and practical applications. This paper proposed a type of carbon-sulfuric electrolyte additive: thioacetamide (TTA) and dimethyl thiocarbamoyl chloride (DMTCC) for LOB. With the strong electronegativity of the carbon-nitrogen bond and the carbon-sulfur double bond, Li2O2 grows in liquid phase easily on the electrode surface, which significantly reduced the reaction potential. Both of the additives result in the good performance at a specific concentration, with lower charging potential and improved cycling properties. It is believed that the carbon-sulfuric electrolyte additive will benefit a homogeneous catalytic mode, which accelerates the decomposition of Li2O2 and realizes the reduction of the oxygen evolution reactions (OER) reaction potential and the improvement of comprehensive performance.

Deoxygenation of Sulfoxides with Dimethylthiocarbamoyl Chloride in the Absence of Additional Solvent

Deoxygenation of Sulfoxides with Dimethylthiocarbamoyl Chloride in the Absence of Additional Solvent

A naphthalimide–rhodamine chemodosimeter for hypochlorite based on TBET: High quantum yield and endogeous imaging in living cells

A naphthalimide-rhodamine fluorescent turn-on probe RHSNO with red emission for hypochlorous acid based on dual reaction linkage induce through-bond energy transfer (TBET) system was designed and synthesized. Rhodamine B thiohydrazide and naphthalimide-N,N-dimethylthiocarbamate (DMTC) were linked to form a structure of monothio-bishydrazide. In addition, introduce dimethylthiocarbamoyl chloride as another reaction site of ClO−, and it acts to quench the fluorescence of naphthalimide. In the presence of ClO−, RHSNO exhibits high selectivity toward ClO− at trace levels over other anions/ROS based on ClO−-triggered intramolecular desulfurization cyclization of rhodamine-thiohydrazide, the spiro ring of rhodamine was opened and meanwhile desulfurization hydrogenation happened at DMTC of naphthalimide moiety. These dual linkage reaction happened simultaneously made a typical TBET process took place from naphthalimide donor to rhodamine acceptor, an obvious increase of rhodamine emission at 590 nm and enhanced up to 260-fold gradually after adding ClO− with the increase of the concentrations. The efficiency of energy transfer was calculated to be 86%. And the quantum yield of rhodamine moiety is 0.64. Besides, the chemodosimeter RHSNO for ClO− with high sensitivity, a dramatic color change from colorless to brightly pink among 2 s after the addtion of ClO−. The detection limit was determined to be 22.1 nM and works excellently within a wide pH range of 5–10. Moreover, RHSNO had been employed for endogenous imaging in MCF-7 cell for ClO−. The results indicated that the probe could permeated into the cells and reacted with the intracellular ClO−. It is excellent to design fluorescence sensor RHSNO as a quick and effective method for detecting excess ClO− in living cell, for maintaining the balance of hypochlorite in the body and ensure normal life activities.

Copper catalyzed synthesis of benzoxazoles and benzothiazoles via tandem manner

A useful protocol for the preparation of substituted 2-aminobenzoxazoles and 2-aminobenzothiazoles was presented. Under the catalysis of copper, 2-aminophenols or 2-aminothiophenols reacted with thiocarbamoyl chlorides via a tandem manner, furnishing a series of 17 benzoheterocycles smoothly with good to excellent yields (70–91%). The broad substrate scope, short reaction time, mild react conditions, easy performance and nice yields make this approach attractive, showing its practical synthetic value for the preparation of some biologically or pharmaceutically active compounds.

Copper-catalyzed tandem reaction of 2-haloanilines with thiocarbamoyl chloride: Synthesis of 2-aminobenzothiazoles

ABSTRACTA simple and efficient protocol for the synthesis of 2-aminobenzothiazoles by a ligand-free copper-catalyzed tandem reaction has been developed. In the presence of CuBr and t-BuOK, a variety of 2-haloanilines (halogen = Br, I) underwent the reaction with thiocarbamoyl chloride efficiently to afford the corresponding 2-aminobenzothiazoles in good yields (83–94%). The features of this method include good yield, cheap catalyst, mild reaction conditions, and broad substrate scope, which make the protocol practical and attractive in the preparation of some potential pharmaceutically active compounds.

Palladium-catalyzed Tandem Synthesis of 2-Aminobenzothiazoles Starting from Unreactive 2-Chloroanilines

A simple and efficient protocol for the synthesis of 2-aminobenzothiazole derivatives is described. 2-Chloroanilines were treated with thiocarbamoyl chloride in the presence of Pd(dba)2 and t-BuOK to afford the corresponding 2-aminobenzothiazoles in good to excellent yield via a tandem manner.

ChemInform Abstract: Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds

AbstractReview: 88 refs.

Influence of sulfur for oxygen substitution in the solvolytic reactions of chloroformate esters and related compounds.

The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°. N,N-Disubstituted carbamoyl halides favor the ionization pathway as do also the considerably faster reacting thiocarbamoyl chlorides. The tendency towards ionization increases as, within the three contributing structures of the resonance hybrid for the formed cation, the atoms carrying positive charge (other than the central carbon) change from oxygen to sulfur to nitrogen, consistent with the relative stabilities of species with positive charge on these atoms.

Pre-organized oligomodified resorcinarene ligands. Preparation, structure, and complex formation

Interaction of various conformations of resorcinarenes with carbamoyl chloride, thiocarbamoyl chloride, and trifluoromethanesulfonic acid anhydride has resulted in a series of derivatives with certain pre-organization of the macrocyclic scaffold and the immobilized electron-donating groups. Complex formation of the selected prepared compounds towards Pd(II) derivatives has been studied.

Synthesis and Characterization of Dimethylthiocarbamoyl-Modified Thiacalix[n]arenes for Selective Pd(II)-Ion Extraction

In this study, two extractants, hexakis[(dimethylthiocarbamoyl)oxy]thiacalix[6]arene (1) and tetrakis[(dimethylthiocarbamoyl)oxy]thiacalix[4]arene (2), were synthesized by the reaction of dimethylthiocarbamoyl chloride with p-tert-butylthiacalix[n]arenes (n = 6 and 4) and characterized using 1H NMR and FT-IR spectroscopies, elemental analysis, and fast-atom-bombardment mass spectrometry (FAB-MS). These compounds were extensively evaluated for the extraction of Pd(II) ions from HCl media and solutions of platinum-group metals from automotive catalyst residues, using various solvents. Compounds 1 and 2 were found to have higher Pd(II)-ion extraction abilities (0.57 and 0.48 g/L, respectively) than the native p-tert-butylthiacalix[6]arene (3) and p-tert-butylthiacalix[4]arene (4) (0.46 and 0.20 g/L, respectively), using 1 mM extractant and 9.4 mM Pd(II)-ion solutions in HCl media. The extractant–Pd(II) complexes were characterized using FT-IR spectroscopy, elemental analysis, XRD, Job’s continuous method, an...

A Mild and Efficient Procedure for the N-Functionalization of S-Perfluoroalkylated Aryl Sulfoximines

N-Acylated perfluoroalkylated sulfoximines are synthesized easily from the corresponding free NH-sulfoximines on reaction with acid chlorides. This mild procedure is extended to diacid chlorides for the preparation of dimeric N-bridged sulfoximines and to reactions with chloroformates, carbamoyl chlorides, chlorothio­noformates and thiocarbamoyl chlorides as electrophiles.

ChemInform Abstract: New Deoxygenation Method for Amine N‐Oxides Using Dimethylthiocarbamoyl Chloride.

A facile and efficient deoxygenation method for various amine N-oxides to their corresponding amines is described. The experimental procedure is quite simple and the products are obtained in excellent yields.

Synthesis of a Thiocarbamoyl Alkylidyne Complex and Caveats Associated with the Use of [Mo(≡CLi)(CO)2(Tp*)] (Tp* = Hydrotris(3,5-dimethylpyrazol-1-yl)borate)

The successive reactions of [Mo(≡CBr)(CO)2(Tp*)] (1; Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with nBuLi and N,N′-dimethylthiocarbamoyl chloride provides as intended, via formation of [Mo(≡...

New Deoxygenation Method for Amine N-Oxides Using Dimethylthiocarbamoyl Chloride

A facile and efficient deoxygenation method for various amine N-oxides to their corresponding amines is described. The experimental procedure is quite simple and the products are obtained in excellent yields.

Deoxygenation of Pyridine N‐Oxides with Dimethylthiocarbamoyl Chloride.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Alkali Metal and Trimethylsilyl Carbamoselenothioates – Synthesis, Structure, and some Reactions

AbstractThis paper describes the synthesis and some reactions of potassium, rubidium, cesium and trimethylsilyl carbamoselenothioates. The potassium salts were synthesized in 70–80 % yields by reacting the corresponding thiocarbamoyl chlorides with potassium selenide in acetonitrile. Furthermore, the rubidium and cesium salts were obtained in good yields by treating the trimethylsilyl esters with the corresponding metal fluorides. The crystal structure of acetonitrile‐solvated potassium N,N‐dimethylcarbamoselenothioate consisted of dimeric units, featuring μ‐carbamoselenothioate anions associated with potassium cations that are located on the upper and lower sides of a plane involving two opposing carbamoselenothioate groups. These heavier alkali metal salts readily reacted with alkyl halides to give both S‐ and Se‐alkyl esters. The reaction of the potassium salts with trimethylsilyl chlorides forms S‐ and Se‐trimethylsilyl carbamoselenothioates which are in equilibrium. The reaction of the salts and silyl esters with organo Group‐14 and ‐15 elements halides gave exclusively the corresponding Se‐substituted products in good yields.

Deoxygenation of pyridine N‐oxides with dimethylthiocarbamoyl chloride

Abstractmagnified imageTreatment of pyridine N‐oxides with dimethylthiocarbamoyl chloride in boiling acetonitrile effects chemoselective deoxygenation to pyridines.

Fluorous dimethylthiocarbamate ( FDMTC) protecting groups for alcohols

N, N-Bis(perfluoroalkyl)thiocarbamoyl chlorides ( FDMTC-Cls) were synthesized as reagent for the protection of alcohols. Using the crystalline FDMTC-Cls, the FDMTC groups were introduced into the alcohol molecules in excellent yields in the presence of sodium hydride in THF at room temperature. The products were separated from the excess alcohols by solid-phase extraction with a fluorous reverse-phase silica gel column (Fluorous Solid Phase Extraction; FSPE). The FDMTC groups were readily removed by oxidation with m-chloroperbenzoic acid ( m-CPBA) and subsequent hydrolysis with KHCO 3.

SYNTHESIS OF DITHIOCARBAMATES AND SELENOTHIOCARBAMATES

Several dithiocarbamates and selenothiocarbamates were synthesized by the reaction of N N -dimethylthiocarbamoyl chloride with the corresponding thiolates and selenolates.

Dimethylthiocarbamate (DMTC): an alcohol protecting group.

Dimethylthiocarbamates (DMTCs), prepared from the corresponding alcohols using commercial dimethylthiocarbamoyl chloride, are spectrally simple, achiral, and nonpolar. DMTCs are moderately to highly stable to a wide range of reagents and conditions including metal hydrides, hydroboration, ylides, NaOH, HCl, organolithiums, Grignards, DDQ, PCC, Swern, n-Bu(4)NF, CrCl(2), heat, and Lewis acids. They are readily removed by NaIO(4) or H(2)O(2) in the presence of other common alcohol protecting groups. [structure: see text]