Reaction Of Thiocyanate Research Articles

Synthesis of CuSCN particles in deep eutectic solvents and its application in the thermal decomposition of ammonium perchlorate

ABSTRACTCuSCN particles were successfully synthesized by a simple, mild reaction of copper sulfate, copper powder, and potassium thiocyanate at 70°C in deep eutectic solvents (DES). The as-prepared products were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TG). The catalytic performance of the CuSCN particles was investigated by TG. It was found that the higher decomposition temperature of ammonium perchlorate (AP) can be decreased by over 100°C via adding a small amount CuSCN particles in AP.

Three-Component Reaction between Kojic Acid and Aroyl Chlorides with Ammonium Thiocyanate: Synthesis of 2-Aryl-6-Hydroxymethyl-4-Thioxo-4H-Pyrano[2,3-e][1,3]Oxazin-8-Ones

A novel method for oxazine ring formation is established using the reaction of ammonium thiocyanate and aroyl chlorides with kojic acid in the presence of N-methylimidazole to afford 2-aryl-6-hydroxymethyl-4-thioxo-4 H-pyrano[2,3- e][1,3]oxazin-8-ones in excellent yields.

Gas-phase reactions of methyl thiocyanate with aliphatic carbanions - A mass spectrometry and computational study.

Methyl thiocyanate, like other organic thiocyanates, is a molecule with many electrophilic reactive sites and it has many synthetic applications. For better understanding of the intrinsic reactivity of alkyl thiocyanates against nucleophiles it was important to study gas-phase reactions of methyl thiocyanate with carbanions differing by structure and proton affinity values. All experiments were performed using a modified API 365 triple quadrupole mass spectrometer equipped with a TurboIonSpray electrospray ionization (ESI) source. Carbanions were generated in the ESI source by decarboxylation of the respective carboxylic acid anions. Methyl thiocyanate was delivered as a vapor with nitrogen used as a collision gas to the collision cell where the reactions take place. Mass spectra recorded for the gas-phase reactions of five aliphatic carbanions with methyl thiocyanate showed a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. The pathways considered are: SN 2 nucleophilic substitution, cyanophilic reaction, thiophilic reaction and proton transfer, followed in some instances by subsequent transformations. The proposed reaction pathways are supported by density functional theory (DFT) calculations. Our preliminary experiments showed that mass spectrometry together with quantum chemical calculations is a good tool for studying gas-phase reactions of alkyl thiocyanates with carbanions. In the gas phase all four theoretically possible products can be observed and their formation can be rationalized by the results of the modelling of the reaction energy profiles. Copyright © 2016 John Wiley & Sons, Ltd.

ChemInform Abstract: Synthesis of 2‐Aryl‐7‐methyl‐4‐thioxo‐4H‐pyrano[3,4‐e][1,3]oxazin‐5‐one by Three‐Component Condensation.

A novel method for oxazine ring formation is established though the reaction of ammonium thiocyanate and aroyl chlorides with 4-hydroxy-6-methyl-2H-pyran-2-one in the presence of N-methylimidazole to afford 2-aryl-7-methyl-4-thioxo-4H-pyrano[3,4-e][1,3]oxazin-5-one in excellent yields.

A facile one-pot synthesis of substituted N-{[2-(aminocarbonyl)phenylamino]thioxomethyl}benzamides and 2-aryl-quinazolin-4(3H)-ones

The substituted N-{[2-(aminocarbonyl)phenylamino]thioxomethyl}benzamides and 2-arylquinazolin-4(3H)-ones are synthesized by the reaction of ammonium thiocyanate and aroyl chlorides with 2-amino-benzamide under solvent-free conditions or under reflux in MeCN.

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH4SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition.

Reaction of benzyl and ethyl allenoates with TMSX (X = I, Br, Cl) and with NH4SCN were investigated in MeCN, DMF, and in imidazolium ionic liquids [BMIM][NTf2] and [BMIM][PF6] as solvent, in the presence and absence of Selectfluor. Comparative product analysis studies demonstrate that the ability of Selectflour to promote oxidative/electrophilic dihalogenation/dithiocyanation with TMSX/NH4SCN (as observed previously for 1-arylallenes) is diminished in allenoates, most significantly in reactions with TMSCl, and essentially disappearing in reactions with NH4SCN, in favor of nucleophilic/conjugate addition. The study underscores the contrasting reactivity patterns in 1-arylallenes and allenoates toward electrophilic and nucleophilic additions in halofunctionalization with TMSX/Selectfluor and thiocyanation reactions with NH4SCN/Selectfluor. These competing pathways are influenced by the nature of the anion, allene structure, and the choice of solvent.

One-pot synthesis of 1-Methylimidazol-2-yl N-Aroyldithiocarbamates from 2-Mercapto-1-Methylimidazole, Ammonium Thiocyanate and Aroyl Chlorides

A novel method for 1-methylimidazol-2-yl N-aroyldithiocarbamates formation is established using the reaction of ammonium thiocyanate and aroyl chlorides with 2-mercapto-1-methylimidazole in good yields.

Synthesis of 2-Aryl-7-Methyl-4-Thioxo-4H-Pyrano[3,4-e][1,3]Oxazin-5-One by Three-Component Condensation

A novel method for oxazine ring formation is established though the reaction of ammonium thiocyanate and aroyl chlorides with 4-hydroxy-6-methyl-2H-pyran-2-one in the presence of N-methylimidazole to afford 2-aryl-7-methyl-4-thioxo-4H-pyrano[3,4-e][1,3]oxazin-5-one in excellent yields.

A new two-dimensional anionic cadmium(II) polymer constructed through thiocyanate coordination bridges.

A new cadmium-thiocyanate complex, poly[4-(dimethylamino)pyridin-1-ium [di-μ-thiocyanato-κ(2)N:S;κ(2)S:N-thiocyanato-κN-cadmium(II)]], {(C7H11N2)[Cd(NCS)3]}n, was synthesized by the reaction of cadmium thiocyanate and 4-(dimethylamino)pyridine hydrochloride in aqueous solution. In the crystal structure, each Cd(II) ion is square-pyramidally coordinated by three N and two S atoms from five different thiocyanate ligands, four of which are bridging. The thiocyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd2(NCS)2] building blocks, while the other links the building blocks and cations via N-H···S hydrogen bonds. The N-H···S hydrogen bonds and weak π-π stacking interactions are involved in the formation of both a two-dimensional network structure and the supramolecular network.

Thermodynamically metastable thiocyanato coordination polymer that shows slow relaxations of the magnetization.

Reaction of cobalt thiocyanate with 4-acetylpyridine leads to the formation of [Co(NCS)2(4-acetylpyridine)2]n (3/I). In its crystal structure the Co cations are connected by pairs of μ-1,3-bridging thiocyanato ligands into dimers that are further connected into layers by single anionic ligands. DTA-TG measurements of Co(NCS)2(4-acetyl-pyridine)4 (1) led to the formation of 3/I. In contrast, when the hydrate Co(NCS)2(4-acetyl-pyridine)2(H2O)2 (2) is decomposed, a mixture of 3/I and a thermodynamically metastable form 3/II is obtained. Further investigations reveal that thermal annealing of 2 leads to the formation of 3/II, that contains only traces of the stable form 3/I. DSC and temperature dependent X-ray powder diffraction (XRPD) measurements prove that 3/II transforms into 3/I on heating. The crystal structure of 3/II was determined ab initio from XRPD data. In its crystal structure the Co cations are linked by pairs of bridging thiocyanato anions into a 1D coordination polymer, and thus, 3/II is an isomer of 3/I. Magnetic measurements disclose that the stable form 3/I only shows paramagnetism without any magnetic anomaly down to 2 K. In contrast, the metastable form 3/II shows ferromagnetic behavior. The phase transition into ordered state at Tc = 3.8 K was confirmed by specific heat measurements. Alternating current susceptibility measurements show frequency dependent maxima in χ' and χ″, which is indicative for a slow relaxation of the magnetization.

ChemInform Abstract: One‐Pot Three‐Component Reaction Between 8‐Hydroxyquinoline, Ammonium Thiocyanate and Aroyl Chlorides in the Presence of N‐Methylimidazole under Solvent‐Free Conditions.

Good yields of five 2-aryl-4H-[1,3]oxazino[5,6- h]quinoline-4-thiones were obtained via the reaction of ammonium thiocyanate and aroyl chlorides with 8-hydroxyquinoline in the presence of N-methylimidazole under solvent-free conditions. The important features of this new procedure are cleaner reaction profiles with simple experimental and work-up procedures.

Thermolysis preparation of ZnS nanoparticles from a nano-structure bithiazole zinc(II) coordination compound

Nano-scale and single crystals of a new tris-chelate Zn(II) compound, {[Zn(DADMBTZ)3](SCN)2⋅4H2O}n, (1), {DADMBTZ=2,2′-diamino-5,5′-dimethyl-4,4′-bithiazole} have been synthesized by the reaction of zinc(II) sulfate, ammonium thiocyanate and DADMBTZ using sonochemical and branched tube methods, respectively. The new nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and FT-IR spectroscopy. Compound (1) was structurally characterized by single crystal X-ray diffraction. Compound (1) form a tris-chelate complex with nearly C3 symmetry. The coordination number of zinc atom in the compound is six with coordinated environments of distorted octahedral, ZnN6. In reaction with DADMBTZ, the ligand DADMBTZ acts as bidentate in compound to form five-membered chelate rings with the same internal angles in coordination polyhedron. The crystal packing is mainly stabilized by N–H----N hydrogen bonding interactions. The thermal stability of compound (1) was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). ZnS nanostructures were obtained by direct thermolyses of compound (1) at 400°C under argon atmosphere. The ZnS nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy.

Nano ZnO Promoted Synthesis of 1,3-Oxazoline-2-Thione Derivatives

The synthesis of 2-thioxo-1,3-oxazoles in the presence of zinc oxide nanoparticles (ZnO NPs, ca 21 nm) and under solvent-free conditions has been achieved through reaction of ammonium thiocyanate, acid chlorides, phenacyl bromide or its derivatives, and a catalytic amount of N-methylimidazole. The catalyst was recycled and reused six times with minor decrease in its catalytic activity. High yields, simple experimental procedure and short reaction times are advantages of this reaction.

One-Pot Three-Component Reaction between 8-Hydroxyquinoline, Ammonium Thiocyanate and Aroyl Chlorides in the Presence of N-Methylimidazole Under Solvent-Free Conditions

Good yields of five 2-aryl-4 H-[1,3]oxazino[5,6- h]quinoline-4-thiones were obtained via the reaction of ammonium thiocyanate and aroyl chlorides with 8-hydroxyquinoline in the presence of N-methylimidazole under solvent-free conditions. The important features of this new procedure are cleaner reaction profiles with simple experimental and work-up procedures.

Synthesis, Structures, Polymorphism, and Magnetic Properties of Transition Metal Thiocyanato Coordination Compounds

Reaction of manganese, iron, and nickel thiocyanate with 4-ethylpyridine leads to the formation of single crystals of compounds with composition M(NCS)2(L)4 (1), M(NCS)2(L)2(H2O)2 (2-Mn), and M(NCS)2(L)2 (3) with M = Mn, Fe, and Ni and L = 4-ethylpyridine. For most compounds, different polymorphic modifications are observed, and their transition behavior and thermodynamic stability was investigated. Additionally, compounds of composition M(NCS)2(L)2 (M = Mn or Ni) were prepared from solution and by thermal decomposition of compounds 1 and 2, which lead to different stable and metastable modifications. The crystal structures of most compounds were determined by single crystal X-ray diffraction and some of them by Rietveld refinements. Compounds 1 and 2 consist of octahedrally coordinated discrete complexes with terminal N-bonded thiocyanato anions. In compounds 3, the metal cations are linked by pairs of μ-1,3-bridging thiocyanato anions into chains. Surprisingly, thermal decomposition of Ni(NCS)2(4-ethylpyridine)4 leads to the formation of a new compound of composition Ni(NCS)2(4-ethylpyridine) (4-Ni). Magnetic measurements reveal that 3-Mn/II and 3-Mn/III show antiferromagnetic ordering at TN = 21.5 and 23.9 K and that 4-Ni is a metamagnet with a critical field of 1.4 kOe at 2 K. All other compounds show Curie or Curie–Weiss behavior with no magnetic anomalies.

ChemInform Abstract: Three‐Component and One‐Pot Synthesis of 1,2,4‐Triazole‐3‐thione Derivatives under Solvent‐Free Conditions.

A novel method for 1,2,4-triazole-3-thiones formation is established using the reaction of ammonium thiocyanate and aroyl chlorides with acylhydrazides under solvent-free conditions to afford triaz...

Combined capillary electrophoresis and high performance liquid chromatography studies on the kinetics and mechanism of the hydrogen peroxide–thiocyanate reaction in a weakly alkaline solution

The hydrogen peroxide-thiocyanate reaction has been reinvestigated by means of capillary electrophoresis and high performance liquid chromatography under weakly alkaline conditions at 25.0±0.1 °C. Concentration-time series of thiocyanate, sulfate and cyanate have been followed by capillary electrophoresis as well as that of thiocyanate and hydrogen peroxide by HPLC. It has been clearly demonstrated that OxSCN(-) (where x=1, 2 and 3) cannot be accumulated in detectable amount in contrast to the results of Christy and Egeberg, hence these species can only be regarded as short-lived intermediates. It has been shown that the overall rate law is first-order with respect to both reactants, but no pH-dependence was observed within the pH range of 8.86-10.08. A simple kinetic model has been proposed to fit all the concentration-time curves simultaneously at five different pHs demonstrating the powerful combination of the experimental techniques CE and HPLC with simultaneous evaluation of kinetic curves. It is also enlightened that the quality of the buffer strongly affects the rate of the overall reaction that increases in the order of application of ammonia, phosphate, carbonate and borate, respectively at a constant ionic strength and pH.

Assembly, crystal structures, and luminescent properties of three new thiocyanate-bridging mercury(II) coordination polymers

Two ligands, 2-{5,5-dimethyl-3-[2-(pyridin-3-yl)-ethenyl]cyclohex-2-enylidene}propanedinitrile (L1) and 2-{5,5-dimethyl-3-[2-(pyridin-2-yl)-ethenyl]cyclohex-2-enylidene}propanedinitrile (L2), were synthesized. By reaction of mercury thiocyanate with L1 and L2, respectively, coordination polymers [Hg(L1)(μ1,3-SCN)2]n (1), [Hg(L1)2(μ1,3-SCN)2]n (2), and [Hg(L2)(μ1,3-SCN)(SCN)]n (3) with different structures and topologies were obtained. In 1, the thiocyanate shows μ1,3-SCN bridging coordination, and adjacent Hg(II) ions are bridged by two μ1,3-SCN ions to form an infinite chain with the remaining position of five-coordinate Hg(II) occupied by L1. In 2, the thiocyanate has the same coordination as 1. However, Hg(II) has octahedral coordination with two L1 involved in coordination. An unusual feature of 3 is the presence of two types of thiocyanates, one has a S-terminal ligand and the other has a μ1,3-SCN bridge. The mercury(II) in 3 is four-coordinated by L2 and three thiocyanates. Luminescent properties and thermal stabilities of 1–3 were studied.

Microwave-Assisted Synthesis, Crystal Structures, and In Vitro Antibacterial Studies of Cobalt(III) and Vanadium(V) Complexes Derived From N,N’-1,2-propylene-bis(3-methylsalicylideneimine)

The syntheses of a mononuclear cobalt(III) complex [CoL(NCS) (OH2)] and a mononuclear vanadium(V) complex [VOL(NCS)] (H2L = N,N′-1,2-propylene-bis(3-methylsalicylideneimine)), by a one-step sequence from the reaction of H2L, ammonium thiocyanate and metal salts under microwave irradiation are described. The newly prepared complexes were characterized by a combination of elemental analyses and IR spectra. Their structures were determined by single-crystal X-ray crystallography. Both complexes with octahedral metal centers have similar structures. The crystal of the cobalt complex is stabilized by hydrogen bonds, while there are no such interactions in the crystal of the vanadium complex. In order to evaluate the biological activity of H2L and to evaluate the role of cobalt and vanadium ions on biological activity, the free ligand and the complexes have been studied in vitro antibacterial against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Pseudomonas aeruginosa.

Synthesis and Structural Characterization of Cation-Induced Complex: [Cd4(SCN)6(BPB)]n With One-Dimensional Double Helix

In this study, colorless crystals of the title inorganic-organic hybrid compound were obtained from the solution-phase reaction of cadmium thiocyanate with BPB·Br2 in MeOH/DMF(BPB·Br2 = 1,4-bis(pyridinium)butane dibromine). And single-crystal X-ray diffraction analysis revealed that this polymer crystallized in triclinic, space group P–1 with unit cell parameters a = 5.8855(5) Å, b = 9.5996(8) Å, c = 11.4358(9) Å, α = 69.9710(10)°, β = 75.1100 (10)°, γ = 75.8180(10)°. In this compound, each cadmium atom is octahedrally coordinated in 2S4N geometry and doubly bridged infinite one-dimensional double helix cadmium thiocyanate chains act as inorganic moiety with dication discretely surrounded. Supplemental materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.