Ethylene from methyl halides

Acid Amides can be produced by acylating ammonia with esters, acid anhydrides, or the acids themselves (above 100 °C) an important product is formamide from methyl formate. Alternatively acid amides can be synthesized by reacting acid halides with ammonia. Catalytic hydrogenation converts the acid amides to primary amines. Ammonia and aldehydes or ketones are the basis for different stable products. With formaldehyde hexamethylenetetramine (urotropine) is obtained with acetaldehyde, ammono acetaldehyde with benzaldehyde, hydrobenzamide with ethylene and propylene oxides, aqueous ammonia reacts to form ethanol- or propanolamine. 

The feasible selective catalytic preparation of methyl halides and methyl alcohol from methane also allows subsequent condensation to ethylene and higher hydrocarbons. This can be accomplished by the Mobil Corp. ZSM-5 zeolite catalysts but also over non-shape selective acidic-basic bifunctional catalysts, namely WO3/AI2O3. 

Reaction of 2-benzo[6]thienyllithium (and its 7-methyl derivative 90) with aldehydes 486,5fl4, 620 or ketones 467 483 affords a secondary or tertiary alcohol, respectively. Treatment of 2-benzo[6]thienyl-lithium with acetyl chloride gives mainly l,l-di(2-benzo[6]thienyl)-ethylene.132 Side-chain alcohols in positions other than the 2-position are most easily prepared by reaction of the appropriate benzo[6]-thienylmagnesium halide with aldehydes 460,471 or ketones,186,3o9, 349, 4 7,466,479,498 or foy reaction of a benzo[fe]thiophene aldehyde, ketone, or ester with an alkylmagnesium halide.358,427 465 The preparation of alcohols from 2- and 3-benzo[6]thienylmethyl-magnesium chloride485,528 is discussed in Section VI, D, 4. 

Photodimerization and cross-cycloaddition of coumarins are improved by Lewis acids [74]. Similarly, photochemical [2-1-2] cycloadditions [75] of 1- and 2-naphthols [76] with ethylene are promoted by aluminum halides yielding the [2-1-2] adduct from the (complexed) enone form. According to the structure, substitution (e. g., methyl) vicinal to the OH group in 1-naphthol gives rise to ring-contracted indanone products. The formation of (ring-contracted) benzo-bicyclo[3.1.0]bicyclohexenone was already observed by irradiation (AICI3) of 1-naphthol without ethylene (Scheme 6) [77],... 

In the case of hydrobromic and hydriodic acids and such olefins as isobutylene and tri methyl ethylene, the rate of alcohol formation may become such that it approaches the rate of hydrolysis of the corresponding alkyl halides, thus supporting the theory that halides are the necessary intermediate product.04 The greater activity of the hydrobromic and hydriodic acids compared with hydrochloric acid toward ethylene is shown by the experiments of Swann, Snow and Keyes.00 At 800 pounds per square inch pressure and a temperature of 150° C. no alkyl chlorides were detected when hydrochloric acid of from 5 to 25 per cent concentration was used. On the other hand, considerable yields of alkyl iodides were obtained under the same conditions when hydriodic acid was used, and alkyl bromides formed in the presence of 40 per cent concentration hydrobromic acid. Alcohol yields were very small. When using propene at 600 to 800 pounds per square inch pressure at 135° C. in the presence of 5 per cent hydrochloric acid solutions and solutions of silver nitrate, yields of alcohol several times that obtained from ethylene were found. The yields were still very low, however, even with times of reaction as long as one hour. 

Alkyl and arylmagnesium halides react with 2-methylquinoxaline by addition of one mole of reactant to the 3,4-bond. After hydrolysis the 2-alkyl- or 2-aryl-l,2-dihydro-3-methylquinoxalines (52) are obtained. When ethylmagnesium bromide is used a dimeric by-product (53) is also isolatedReaction of 2,3-dimethylquinoxaline with benzonitrile and lithium amide gives l-amino-l-phenyl-2-(3-methyl-2-quinoxalinyl)-ethylene (54). The mono- and dilithium salts of 2,3-dimethylquinoxaline have been generated from the quinoxaline by reaction with one or two equivalents of lithium diisopropylamide (LiNPr, respectively. These salts have been reacted with a variety of electrophilic reagents such as alkyl halides, aryl ketones, esters, and nitriles. " ... 

Further, formation of quaternary salts can interfere in the ready removal of hydrogen halide by tertiary amines such as dimethylaniline, pyridine, or quinoline.58 To overcome this, Hiinig and Kiessel59 successfully applied sterically hindered tertiary amines, e.g., ethyldiisopropylamine and 7V-ethyldi-(cyclohexyl)amine for instance, removing hydrogen bromide from 1,2-di-bromo-2-methylpropane by potassium hydroxide in ethylene glycol60 gave unsatisfactory yields of l-bromo-2-methyl-l-propene ... 

---