Acetylenic Sulphides

Sukhai and L. Brandsma, Reel. Trav. Chim. Pays-Bas, 1979, 98, 55. 

Prochazka, and V. Bakos, Collect. Czech. Chem. Commun., 1978, 43, 2619. H. Okamura and H. Takei, Tetrahedron Lett., 1979, 3425. 

Tanaka, S. Shiraishi, T. Nakai, and N. Ishikawa, Tetrahedron Lett., 1978, 3103. 

Turecek and M. Prochazka, Coll. Czech. Chem. Comm., 1974, 39, 2073. 

CuCl and hydroquinone to MeSC C—C=CPr to give cis,cis- and cis trans-MeSCCl=CHCCl=CHPr in 1 2 ratio and formation of EtC=C—C CPr by the reaction of MeSC C—C=CEt with Pr Li.  

Phenylthio-ynamines, e.g. PhSCsECNEt2, are in a class apart, and the formation of the cyclobutadiene (24) by treatment with BFs is notable.  

---

The stepwise approaches used for the syntheses of acetylenic sulphides (62) illustrate some general methods. The elimination of MeSH from an... 

Acetylenic sulphoxides and sulphones are obtained by oxidation of the more readily available acetylenic sulphides using w-chloroperbenzoic acid at -20 °C in chloroform. Alternatively, the sulphoxides may be prepared by dehydrohalogenation of chlorovinylsulphoxides (25). A useful preparative... 

Acetylene, fulminic acid (produced in ethanol - nitric acid mixtures), ammonia Acetic acid, acetone, alcohol, aniline, chromic acid, hydrocyanic acid, hydrogen sulphide, flammable liquids, flammable gases, or nitratable substances, paper, cardboard or rags Inorganic bases, amines Silver, mercury... 

Reaction of adsorbed inhibitors In some cases, the adsorbed corrosion inhibitor may react, usually by electro-chemical reduction, to form a product which may also be inhibitive. Inhibition due to the added substance has been termed primary inhibition and that due to the reaction product secondary inhibition " . In such cases, the inhibitive efficiency may increase or decrease with time according to whether the secondary inhibition is more or less effective than the primary inhibition. Some examples of inhibitors which react to give secondary inhibition are the following. Sulphoxides can be reduced to sulphides, which are more efficient inhibitorsQuaternary phosphonium and arsonium compounds can be reduced to the corresponding phosphine or arsine compounds, with little change in inhibitive efficiency . Acetylene compounds can undergo reduction followed by polymerisation to form a multimolecular protective film . Thioureas can be reduced to produce HS ions, which may act as stimulators of... 

ETHYLENE GLYCOL ETHYL MERCAPTAN DIMETHYL SULPHIDE ETHYL AMINE DIMETHYL AMIDE MONOETHANOLAMINE ETHYLENEDIAMINE ACRYLONITRILE PROPADIENE METHYL ACETYLENE ACROLEIN ACRYLIC ACID VINYL FORMATE ALLYL CHLORIDE 1 2 3-TRICHLOROPROPANE PROPIONITRILE CYCLOPROPANE PROPYLENE 1 2-DICHLOROPROPANE ACETONE ALLYL ALCOHOL PROPIONALDEHYDE PROPYLENE OXIDE VINYL METHYL ETHER PROPIONIC ACID ETHYL FORMATE METHYL ACETATE PROPYL CHLORIDE ISOPROPYL CHLORIDE PROPANE... 

METHYL ETHYL SULPHIDE N-PROPYL AMINE ISOPROPYL AMINE TRIMETHYL AMINE MALEIC ANHYDRIDE VINYL ACETYLENE... 

Acetylene 195 Ammonia 197 Chlorine 200 Hydrogen 203 Hydrogen sulphide 203 Sulphur dioxide 205... 

Chlorine dioxide Copper Fluorine Hydrazine Hydrocarbons (benzene, butane, propane, gasoline, turpentine, etc) Hydrocyanic acid Hydrofluoric acid, anhydrous (hydrogen fluoride) Hydrogen peroxide Ammonia, methane, phosphine or hydrogen sulphide Acetylene, hydrogen peroxide Isolate from everything Hydrogen peroxide, nitric acid, or any other oxidant Fluorine, chlorine, bromine, chromic acid, peroxide Nitric acid, alkalis Ammonia, aqueous or anhydrous Copper, chromium, iron, most metals or their salts, any flammable liquid, combustible materials, aniline, nitromethane... 

The reagent is highly selective, as demonstrated by the inertness of several sensitive functionalities such as amino, hydroxyl, azo, hydrazo, phenol, sulphide, disulphide, sulphoxide, aldehyde moieties, and olefmic and acetylenic carbon-carbon bonds. The ability of the reagent to differentiate thiols may be used to prepare unsymmetrical disulphides. 

Type 4A sieves. The pore size is about 4 Angstroms, so that, besides water, the ethane molecules (but not butane) can be adsorbed. Other molecules removed from mixtures include carbon dioxide, hydrogen sulphide, sulphur dioxide, ammonia, methanol, ethanol, ethylene, acetylene, propylene, n-propyl alcohol, ethylene oxide and (below -30°) nitrogen, oxygen and methane. The material is supplied as beads, pellets or powder. 

For example, carbon dioxide from air or ethylene nitrogen oxides from nitrogen methanol from ethyl ether. In general, carbon dioxide, carbon monoxide, ammonia, hydrogen sulphide, mercaptans, ethane, ethylene, acetylene, propane and propylene are readily removed at 25°. In mixtures of gases, the more polar ones are preferentially adsorbed). 

Binary compounds with less electronegative elements include hydrides, nitrides, sulphides and phosphides. They are decomposed by water and can provide convenient routes for the preparation of non-metal hydrides. The anions may be polyatomic or polymerised, as with CaC2, which contains C22- and reacts with water to give acetylene (ethyne) C2H2. 

Ion cyclotron resonance (i.c.r.) spectroscopy has allowed Buttrill (1970) to observe the ion-molecule reaction between hydrogen sulphide and acetylene (acetylene-d2). The products are HCS+(DCS+) and C2HsS+ (C2D2HS+). For the latter ion, the structure consistent with the labelling experiments is that of the thiirenium ion ... 

---