Halogenation methane

Methane Halogen Halo- Dihalo- Trihalo- Tetrahalo-Hydrogen... 

Chloroform, CHCI3, and carbon tetrachloride, CCI4, are familiar products of the chlorination of methane. Halogenated hydrocarbons are intermediates in the production of many other types of organic compounds. 

The mechanisms of methane-halogen reactions are chain radical processes. Carbon tetrachloride Is also prepared from carbon disulfide and chlorine. Sulfur is formed in this reaction, but it is recovered and used for the regeneration of CS3. Carbon disulfide is obtained from the elements, but is also formed from methane and sulfur (see Section 1,1.5.4). 

This allylic bromination with NBS is analogous to the methane chlorination reaction discussed in Section 6.3 and occurs hy a similar radical chain reaction mechanism. As in methane halogenation, Br- radical abstracts an allylic hydrogen atom of the alkene, thereby forming an allylic radical plus HBr. This allylic radical then reacts with Br2 to yield the product and a Br-radical, which cycles hack into the first step and carries on the chain. The Br2 results from reaction of NBS with the HBr formed in the first step. 

Chlorination of methane and halogenation of alkanes generally proceed by way of free radical intermediates Alkyl radicals are neutral and have an unpaired electron on carbon... 

Methane has also been used in aerobic bioreactors that are part of a pump-and-treat operation, and toluene and phenol have also been used as co-substrates at the pilot scale (29). Anaerobic reactors have also been developed for treating trichloroethylene. Eor example, Wu and co-workers (30) have developed a successful upflow anaerobic methanogenic bioreactor that converts trichloroethylene and several other halogenated compounds to ethylene. 

Methane is also used for the production of several halogenated products, principally the chloromethanes. Due to environmental pressures, this outlet for methane is decreasing rapidly. 

Iodine reacts with hydrocarbons to form iodine compounds, but compared to the other halogens, the equiUbria are unfavorable because the displacement step with the iodine atom is endothermic, requiring 4066.3 J (971.9 cal) for methane and 799.9 J (191.2 cal) for toluene. Hydrogen iodide can be used to reduce an alkah iodide to hydrocarbon plus molecular iodine. 

This cycle is terrninated by the reaction of chlorine atoms with methane Cl + CH — HCl + CH3. The importance of this cycle depends on the avadabiLity of oxygen atoms and varies with altitude as well as the time of year it accounts for only 5% of the halogen-controUed loss at 15 km, but increases to 25% at 21 km. 

In the known absence of bromoform, iodoform, chloral, and other halogenated methanes, the formation of phenyhsonitrile with aniline provides a simple and faidy sensitive but nonspecific test for the presence of chloroform, the carbylamine test. Phenyhsonitrile formation is the identification test given in the British Pharmacopoeia. A small quantity of resorcinol and caustic soda solution (10% concentration) added to chloroform results in the appearance of a yellowish red color, fluorescing yeUow-green. When 0.5 mL of a 5% thymol solution is boiled with a drop of chloroform and a small quantity of potassium hydroxide solution, a yellow color with a reddish sheen develops the addition of sulfuric acid causes a change to brilliant violet, which, diluted with water, finally changes to blue (33). 

The unique combination of properties associated with certain fluonnated methanes and ethanes has led to their widespread use in fire suppression systems The three halogenated fire suppression agents in general use today are bromo-trifluoromethane (CF Br, Halon 1301), bromochlorodifluoromethane (CF2BtCl, Halon 1211) and, in small volumes, primarily in the republics of the former Soviet Union and Eastern European nations, 1,2-dibromotetrafluoroethane (BrCF2Cp2Br, Halon 2402)... 

The reaction of methane tricarboxylate with indoline 342 gave the tricyclic derivative 361 which can be transformed to the amide derivatives 362 (97JHC969). Alkylation of the iV-benzyl indoline 360 with pentafluor-oacetone gave 363 which upon debenzylation and subsequent acylation with diketene followed by cyclization gave 364. Other haloacetones were used to prepare different halogenated derivatives (79BEP872311) (Scheme 63). 

In refrigerating systems, halogen derivatives of methane and ethane marketed under the trade names of Arctons and Freons are without action on pure aluminium and its copper-free alloys in dry conditions, but in wet conditions monochlorodi-, dichloromono-and trichloromonofluoromethanes can hydrolyse to produce slight attack on the aluminium. 

Although interesting from a mechanistic point of view, alkane halogenation is a poor synthetic method for preparing alkyl halides because mixtures of products invariably result. For example, chlorination of methane does not stop cleanly at the monochlorinated stage but continues to give a mixture of dichloro, trichloro, and even tetrachloro products. 

Azo-Halogen Derivatives of Methane 1,1,1-Trifluoroazomethane,F3CH NCH3, mw... 

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