Reduction alkanes

Alkenes. See also Nitroalkene reduction alkane reduction, 32-45... 

In most studies on zeolites, alkanes and alkenes are used as the reductant alkanes are less active than alkenes. Gopalakrishnan et al. [70] studied the reduction of NO by propane over copper-exchanged zeohtes, namely mordenite, X-type and Y-type, at temperatmes ranging from 473 to 873 K. The following overall reaction occurs ... 

Direct Borohydride Reduction of Alcohols to Alkanes with Phosphonium Anhydride Activation N-Proovlbenzene. To a solution of 5.56 g (20 mmol) of triphenylphosphine oxide in 30mL of dry methylene chloride at CfC was added dropwise a solution of 1.57 mL (10 mmol) of triflic anhydride in 30mL of dry methylene chloride. After 15 min when the precipitate appeared, a solution of 1.36g (10 mmol) of 3-phenyl-1-propanol in 10 mL of dry methylene chloride was added and the precipitate vanished in 5 min. An amount of 1.5g (40 mmol) of sodium borohydride was added as a solid all at once and the slurry was stirred at room temperature for... 

The coupling of alkyl Grignard reagents with alkyl iodides to afford alkanes by use of dppf as a ligand has been reported[449], but re-examination of the reaction has shown that only reduction takes place, and no coupling was observed[450]. 

Although essentially inert m acid-base reactions alkanes do participate m oxidation-reduction reactions as the compound that undergoes oxidation Burning m air (combus tion) IS the best known and most important example Combustion of hydrocarbons is exothermic and gives carbon dioxide and water as the products... 

As we have just seen the reaction of alkanes with oxygen to give carbon dioxide and water IS called combustion A more fundamental classification of reaction types places it m the oxidation—reduction category To understand why let s review some principles of oxidation-reduction beginning with the oxidation number (also known as oxidation state)... 

Combustion of alkanes is an example of oxidation-reduction Although It IS possible to calculate oxidation numbers of carbon m organic mole cules It IS more convenient to regard oxidation of an organic substance as an increase m its oxygen content or a decrease m its hydrogen content... 

The nitro alcohols can be reduced to the corresponding alkan olamines (qv). Commercially, reduction is accompHshed by hydrogenation of the nitro alcohol in methanol in the presence of Raney nickel. Convenient operating conditions are 30°C and 6900 kPa (1000 psi). Production of alkan olamines constitutes the largest single use of nitro alcohols. 

In certain cases, alkanolamines function as reduciag agents. For example, monoethanolamine reduces anthraquiaone to anthranols, acetone to 2-propanol, and azobenzene to aniline (17). The reduction reaction depends on the decomposition of the alkan olamine iato ammonia and an aldehyde. Sinulady, diethan olamine converts o-chloronitrobenzene to 2,2 -dichloroazobenzene and y -dinitrobenzene to 3,3 -diamiQoazobenzene. 

By-Products. Almost all commercial manufacture of pyridine compounds involves the concomitant manufacture of various side products. Liquid- and vapor-phase synthesis of pyridines from ammonia and aldehydes or ketones produces pyridine or an alkylated pyridine as a primary product, as well as isomeric aLkylpyridines and higher substituted aLkylpyridines, along with their isomers. Furthermore, self-condensation of aldehydes and ketones can produce substituted ben2enes. Condensation of ammonia with the aldehydes can produce certain alkyl or unsaturated nitrile side products. Lasdy, self-condensation of the aldehydes and ketones, perhaps with reduction, can lead to alkanes and alkenes. 

A catalyst, usually acid, is required to promote chemoselective and regioselective reduction under mild conditions. A variety of organosilanes can be used, but triethylsilane ia the presence of trifiuoroacetic acid is the most frequendy reported. Use of this reagent enables reduction of alkenes to alkanes. Branched alkenes are reduced more readily than unbranched ones. Selective hydrogenation of branched dienes is also possible. 

Precious Meta.1 Ca.ta.lysts, Precious metals are deposited throughout the TWC-activated coating layer. Rhodium plays an important role ia the reduction of NO, and is combiaed with platinum and/or palladium for the oxidation of HC and CO. Only a small amount of these expensive materials is used (31) (see Platinum-GROUP metals). The metals are dispersed on the high surface area particles as precious metal solutions, and then reduced to small metal crystals by various techniques. Catalytic reactions occur on the precious metal surfaces. Whereas metal within the crystal caimot directly participate ia the catalytic process, it can play a role when surface metal oxides are influenced through strong metal to support reactions (SMSI) (32,33). Some exhaust gas reactions, for instance the oxidation of alkanes, require larger Pt crystals than other reactions, such as the oxidation of CO (34). 

N,N -linked synthesis, 5, 269 6,6 -Biazulenes synthesis, 1, All Bibenzimidazolyls 3-oxides synthesis, 5, 412 1,1 - Bibenzimidazolyls synthesis, 5, 459 2,2 -Bibenzo[b]selenienyl synthesis, 4, 947 2,2 -Bibenzothiazolyl reduction, 6, 260 4,4 -Bichromenyl synthesis, 3, 743 Bicyclo[n. 1.0]alkanes retro-cycloaddition reactions, 1, 668 Bicyclo[5.3.0]decane synthesis, 1, 420 Bicyclo[4.1,0]diheteroheptanes synthesis, 3, 977... 

Scheme 7.5. BusSnH-catalyzed reduction of nitroalkanes to alkanes...

Table 7.2. BujSiiH-catalyzcd reduction of iiitroalkaiie to alkanes...

A second hydrogen is transferred from the metal to the second carbon, giving the alkane product and regenerating the catalyst. Because both hydrogens are transferred to the same face of the alkene, the reduction has syn stereochemistry. 

Alkenes are reduced by addition of H2 in the presence of a catalyst such as platinum or palladium to yield alkanes, a process called catalytic hydrogenation. Alkenes are also oxidized by reaction with a peroxyacid to give epoxides, which can be converted into lTans-l,2-diols by acid-catalyzed epoxide hydrolysis. The corresponding cis-l,2-diols can be made directly from alkenes by hydroxylation with 0s04. Alkenes can also be cleaved to produce carbonyl compounds by reaction with ozone, followed by reduction with zinc metal. 

Complete reduction to the alkane occurs when palladium on carbon (Pd/C) is used as catalyst, but hydrogenation can be stopped at the alkene if the less active Lindlar catalyst is used. The Lindlar catalyst is a finely divided palladium metal that has been precipitated onto a calcium carbonate support and then deactivated by treatment with lead acetate and quinoline, an aromatic amine. The hydrogenation occurs with syn stereochemistry (Section 7.5), giving a cis alkene product. 

Alkynes can be reduced to yield alkenes and alkanes. Complete reduction of the triple bond over a palladium hydrogenation catalyst yields an alkane partial reduction by catalytic hydrogenation over a Lindlar catalyst yields a cis alkene. Reduction of (he alkyne with lithium in ammonia yields a trans alkene. 

---