Xanthogenates

Xanthates (or xanthogenates), t.g., CS(OR)SK, are formed by the reaction between carbon disulphide and an alcoholic solution of potassium hydroxide, for example ... 

Cellulose acids, cellulose esters, cellulose nitrates, cellulose ethers, cellulose xanthogenates... 

Many other routes to produce thioglycohc acid have been iavestigated (9). To try to minimise by-products, nucleophilic agents other than alkah sulfhydrates have been claimed, eg, thiosulfates, sodium disulfides, thiourea, xanthogenic acid derivatives, and sodium trithiocarbonates (10). These alternative methods, which require reduction of the disulfides or hydrolysis of carboxymethylthio derivatives, seem less competitive than those usiag alkah sulfhydrates. 

The alkyl chloroformates react with cold ethereal dispersions of the xanthates to give the fairly stable xanthogen formates. 

The reaction of chloroformates with sodium xanthates results in the formation of alkyl xanthogen formates that are useful as flotation agents in extraction of metals from their ores (48). 

The extent of the long-chain branching of a series of ethyl xanthogen disulfide modified polymers carried to increasing conversion is shown in Table 1. No branches are found until 56% conversion. The gel point is a Htfle over 82%. Polymer rheology deteriorates between 56 and 82% conversion. 

Upon thermolysis of xanthates (xanthogenates) 1 olefins 2 can be obtained, together with gaseous carbon oxysulfide COS 3 and a thiol RSH 4. This decomposition process is called the Chugaev reactionanother common transcription for the name of its discoverer is Tschugaejf. 

Xantho-gensaure, /, xanthogenic acid, xanthic acid. -kobaltchlorid, n, xanthocobaltic chloride, nitropentamminecobalt(III) chloride. -proteinsaure, /. xanthoproteic acid. 

To a solution of 60 g of potassium xanthogenate in 240 cc of water there is added dropwise, while being cooled with ice, a solution of 42 g of 3,4-bis-bromomethyl-4-hydroxy-5-methyl-pyridinium-bromide In 1 liter of water so that the temperature remains between 2°C and 5°C. After stirring for 1 hour at the same temperature, the water is decanted off and the residue is triturated with acetone. Yield 25 g of 4-hydroxymethyl-5-hydroxy-6-methyl-pyridyl-(3)-methy I xanthogenate melting point 170°C to 171°C (alcohol, decomposition). 

In the past chemical cure linings have been employed on a wide scale. These linings, usually based on natural rubber or acrylonitrile-butadiene rubber consist of a standard lining compound with a chemical activator such as dibenzylamine incorporated in the formulation. Prior to the application of the lining to the substrate, the individual sheets of rubber are dipped or brush coated with carbon disulphide or a solution of a xanthogen disulphide in a solvent. The carbon disulphide or xanthogen disulphide permeates the rubber and combines with the dibenzylamine to form an ultra-fast dithiocar-bamate accelerator in situ, and thus the rubber rapidly vulcanises at ambient temperature. 

Compounds with a thiocarbonyl a to the S-S bond such as the dithiuram (e.g. 8f2Al and xanthogen disulfides (e.g. 9)M have transfer constants that are much higher than other disulfides. In part, this may be due to the availability of another mechanism for induced decomposition (Scheme 6.9) involving addition to the C S double bond and subsequent fragmentation. Thiocarbonyl double bonds are very reactive towards addition and an addition-fragmentation mechanism has been demonstrated for related compounds (Section 6.2.3.5). 

Changing the carbon disulfide trapping agent from copper acetate and diethylamine solution to methanolic potassium hydroxide to produce a xanthogenate increases the method s reproducibility and sensitivity. " ... 

---