Masateru Mizuta

Infrared and raman spectra of (thioacetoxythio)triorgano derivatives of silicon, germanium, tin and lead

Abstract The IR and Raman spectra of (thioacetoxythio)trimethyl-Group IVb metals were recorded and an attempt was made to elucidate the structures by spectra. It is concluded that the bonding is similar to that of organic dithio acetates and that intramolecular coordination of the thiocarbonyl sulfur to Group IVB metals is small or negligible. Characteristic absorption bands of C(S)S groups are found near 880–860 cm −1 .

The preparation of ferrocenedithiocarboxylic acid derivatives and their spectral properties

Abstract Ferrocenethiocarboxylic acid (FcCOSH) has been synthesized by the reaction of ferrocenecarboxylic acid chloride with sodium hydrogen sulfide. Treatment of this thioic acid and its ammonium salts with electrophiles gave derivatives such as phenylcarbamoyl ferrocenethiocarboxylate, methyl ferrocenethiocarboxylate, bis(ferrocenecarbonyl) disulfide and bis(ferrocenecarbonyl) sulfide in good yields.

The preparation and reactions of {[α-(trimethyl- and triphenyl)stannyl]phenacyl} triphenylphosphonium salts and ylides

Several {p-substituted [α-(trimethyl- or triphenyl)stannyl]phenacyl} triphenylphosphonium salts, [Ph3P+CH(SnR3)COPh]Cl− (R = Me and Ph), have been prepared by the reaction of p-substituted phenacylidenetriphenylphosphoranes with trimethyl- or triphenyltin chlorides. Extremely low carbonyl stretching frequencies in the infrared spectrum of these compounds suggested strong coordination of the carbonyl oxygen to the trimethyltin moiety. [α-(Trimethylstannyl)phenacyl]triphenylphosphonium chloride gave the corresponding ylide by reaction with n-butyllithium.

The preparation of di- and tri-phenylstannyl esters of aromatic dithio acids, and some of their reactions

Some crystalline di- and tri-phenylstannyl esters [ArCS2SnPh3 and (ArCS2)2SnPh2] of aromatic dithio acids have been prepared in good yields and characterized. Preferential cleavage of the SnS bond of the ester was observed by treating them with primary and secondary amines as well as with phenacylidenetetramethylenesulfurane.

Properties of α-bromovaleric acid as extracting agent for copper(II)

Abstract Copper(II) was extracted with α-bromovaleric acid in benzene from 0.1 mol dm −3 (Na, H)ClO 4 aqueous solution at 25°C. The acid dissociation constant of the extracting agent was determined to be K a = 10 −2.79 in aqueous solution at 25°C. The partition constant of the acid (HA) between the aqueous phase and benzene, and the dimerization constant of the acid in benzene were evaluated to be 2.6 and 56 in molarity, respectively. The dimeric copper(II) α-bromovalerate is responsible for the extraction: 2Cu 2+ +3(HA) 2, o ⇌ K ex Cu 2 A 4 (HA) 2, o +4H 3 O + , (subscript o = organic phase) with log K ex = −7.87. The complex formation of cupric ion with the acid anion observed in the aqueous phase was taken into consideration for calculation of the extraction constant. It was proved that the formation of dimeric copper(II) species is not prevented by the bromine at the α-position in the valeric acid.

A Convenient Preparation Method of Anhydrous Lithium, Potassium, Rubidium and Cesium Dithiocarboxylates

It has been found that a series of anhydrous alkali metal dithiocarboxylates are readily obtained in good yields by the reaction of dithio acid with metal hydride (LiH, NaH, KH), n-butyl lithium, or rubidium or cesium acetates, respectively. Their spectral data were compared.

Dimerization of copper(II) decanoate in 1,4-dioxane-water mixed solvents

Abstract Complex formation of copper(II) with decanoic acid (HA) has been studied by potentiometric measurement in 1,4-dioxane-water mixtures at a constant ionic concentration of 0.1 mol dm−3 (Na, H)ClO4 and at 25°C. The experimental data can be interpreted with the formation of CuA+, CuA2 and Cu2A4. The dimerization constant formulated as: was found to be log Kdim = 3.75, 4.02 and 4.26 for 0.3, 0.4 and 0.5 mole fractions of dioxane, respectively. Absorbances at 373 and 670 nm are interpreted with the aid of the formation constants determined by potentiometry. Solvent effect on the dimerization of the monomeric copper(II) decanoate is discussed on the basis of selective solvation of CuA2 and Cu2A4 with water molecules.

Notizen:The Reaction of Dithiocarboxylic Acids with Imines

Abstract Aromatic dithiocarboxylic acids 1 react with imines 4 to give the corresponding adducts 5, aminomethyl dithiocarboxylates, in good yields. The adducts 5 react with phenacyl bromide to give the corresponding phenacyl dithiocarboxy-lates 6.

Preparation and Some Reactions of Phenylmercury Thio- and Dithiocarboxylates

Abstract It has been found that the reaction of diphenylmercury with an equimolar amount of thio- or dithio acids gave the corresponding phenylmercury thio- (1) or dithiocarboxylates (2), quantitatively, which further react with thio- or dithio acids to give mercury bis (thio-) (3) or bis(dithiocarboxylates) (4). The phenylmercury dithio salts (2) were found to be the very useful thioacylating agents for primary and secondary amines. The reaction of mercury bis(thiocarboxylates) (3) with dithiocarboxylic acids gave the unsymmetrical thio- and dithiocarboxylic acid mercury salts [RC(O)SHgS(S)CR′]j (5) in good yields.

An Improved of α-(Thioaeylthio)methylphenyl-Ketones using Caesium Dithioates and a Convenient Synthesis of 2,4-Disubstituted 1,3-Thiazoles via the Ketones

Abstract α-(Thiocylthio)methylphenylketones, 2,4-Disubstituted 1,3-Thiazoles, Caesium Dithioates α-(Thioacylthio)methylphenylketones were found to be obtained in almost quantitative yields from caesium dithioates and a-phenacyl bromide. Refluxing of these ketones with ammonium acetate in gracial acetic acid affords the corresponding 2,4-disubstituted 1,3-thiazoles. While, the similar reaction of α-(thioisobutyrylthio)methylphenylketone gives the dithiafulvene (4).