Hydrocarbons through Sulfurated Methanes

The ready availability of carbon disulfide from methane and sulfur in oxide-catalyzed reactions484 [Eq. (3.59)] and its further transformation over zeolites485 [Eq. (3.60)] or other catalysts offer an alternative way to the production of hydrocarbons from methane  

It is also significant that the direct oxidative condensation of methane to higher hydrocarbons takes place in the presence of S8 over superacidic catalysts, such as TaF5 and the like.357 

---

For the analysis of sulfur hexafluoride an electron capture detector must be used. Analysis time for halothane, acetone, ether, cyclopropane, acetylenes, ethane, methane, and sulfur hexafluoride, under normal conditions, will average 8 min. Since the two detectors operate under different conditions samples containing both the hydrocarbons and sulfur hexafluoride are run through the gas chromatograph twice. By simultaneous use of separate ovens, the FID and ECD measurements can be made concurrently. Otherwise, the separate in jections must be made after switching the detectors. 

Carbon tetrachloride represents an example of the change to petroleum raw materials in this field. The traditional source of this widely used product has been the chlorination of carbon disulfide, either directly or through the use of sulfur dichloride. Military requirements in World War II caused an increase in demand, and in addition to expansion of the older operations, a new process (28) was introduced in 1943 it involved direct chlorination of methane at 400° to 500° C. and essentially atmospheric pressure. This apparently straight-forward substitution of halogen for hydrogen in the simplest paraffin hydrocarbon was still a difficult technical accomplishment, requiring special reactor construction to avoid explosive conditions. There is also the fact that disposal of by-product hydrochloric acid is necessary here, though this does not enter the carbon disulfide picture. That these problems have been settled successfully is indicated by the report (82) that the chlorination of methane is the predominant process in use in the United States today, and it is estimated that more than 100,000,000 pounds of carbon tetrachloride were so produced last year. 

C-H o-bond activation of hydrocarbons by transition metal complexes is of considerable importance in modern organometallic chemistry and catalytic chemistry by transition-metal complexes [1], because a functional group can be introduced into alkanes and aromatic compounds through C-H o-bond activation. For instance, Fujiwara and Moritani previously reported synthesis of styrene derivatives from benzene and alkene via C-H o-bond activation of benzene by palladium(ll) acetate [2]. Recently, Periana and his collaborators succeeded to activate the C-H o-bond of methane by the platinum(ll) complex in sulfuric acid to synthesize methanol [3], Both are good examples of the reaction including the C-H o-bond activation. 

---