Alcohol, alkenes => aldehydes

Br0nsted-Lowry acids and bases (Chapter 6, Sections 6.2-6.4) Lewis bases and Lewis acids (Chapter 6, Section 6.5) the acid-base properties of alcohols, alkenes, aldehydes, and ketones (Chapter 6, Sections 6.3-6.S)... 

Peroxomonosulfuric acid oxidi2es cyanide to cyanate, chloride to chlorine, and sulfide to sulfate (60). It readily oxidi2es carboxyflc acids, alcohols, alkenes, ketones, aromatic aldehydes, phenols, and hydroquiaone (61). Peroxomonosulfuric acid hydroly2es rapidly at pH <2 to hydrogen peroxide and sulfuric acid. It is usually made and used ia the form of Caro s acid. 

Vinyllithium [917-57-7] can be formed direcdy from vinyl chloride by means of a lithium [7439-93-2] dispersion containing 2 wt % sodium [7440-23-5] at 0—10°C. This compound is a reactive intermediate for the formation of vinyl alcohols from aldehydes, vinyl ketones from organic acids, vinyl sulfides from disulfides, and monosubstituted alkenes from organic halides. It can also be converted to vinylcopper [37616-22-1] or divinylcopper lithium [22903-99-7], which can then be used to introduce a vinyl group stereoselectively into a variety of a, P-unsaturated systems (26), or simply add a vinyl group to other a, P-unsaturated compounds to give y, 5-unsaturated compounds. Vinyllithium reagents can also be converted to secondary alcohols with trialkylb o r ane s. 

Methods of synthesis for carboxylic acids include (1) oxidation of alkyl-benzenes, (2) oxidative cleavage of alkenes, (3) oxidation of primary alcohols or aldehydes, (4) hydrolysis of nitriles, and (5) reaction of Grignard reagents with CO2 (carboxylation). General reactions of carboxylic acids include (1) loss of the acidic proton, (2) nucleophilic acyl substitution at the carbonyl group, (3) substitution on the a carbon, and (4) reduction. 

Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes frorm Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). 

Examples of the protection of alkynes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also indexed on p. xvii. Section (designated with an A 15A, 30A, etc.) with protecting group reactions are located at the end of pertinent chapters. 

For the oxidation of allylic alcohols to alkene aldehydes, also see Section 48 (Aldehydes from Alcohols). 

In the hydroformylation of lower alkenes using a modified cobalt catalyst complex separation is achieved by distillation. The ligands are high-boiling so that they remain with the heavy ends when these are removed from the alcohol product. Distillation is not possible when higher alcohols or aldehydes are produced, because of decomposition of the catalyst ligands at the higher temperatures required. Rhodium complexes can usually also be removed by distillation, since these complexes are relatively stable. 

In Section 3.5 on alkene isomerization, it was mentioned that Li and co-workers reported a RuCl2(PPh3)3-catalyzed shuffling of functional groups of allylic alcohols in water (Eq. 3.35).140 Since the reaction proceeds through an enol intermediate, allyl alcohols can thus be considered as enol equivalents.203 This has been developed into an aldol-type reaction by reacting allyl alcohols with aldehyde (Scheme 3.11).204 The presence of In(OAc)3 promoted the aldol reaction with a-vinylbenzyl alcohol and aldehyde.205... 

The readsorption and incorporation of reaction products such as 1-alkenes, alcohols, and aldehydes followed by subsequent chain growth is a remarkable property of Fischer-Tropsch (FT) synthesis. Therefore, a large number of co-feeding experiments are discussed in detail in order to contribute to the elucidation of the reaction mechanism. Great interest was focused on co-feeding CH2N2, which on the catalyst surface dissociates to CH2 and dinitrogen. Furthermore, interest was focused on the selectivity of branched hydrocarbons and on the promoter effect of alkali on product distribution. All these effects are discussed in detail on the basis... 

In Fischer-Tropsch synthesis the readsorption and incorporation of 1-alkenes, alcohols, and aldehydes and their subsequent chain growth play an important role on product distribution. Therefore, it is very useful to study these reactions in the presence of co-fed 13C- or 14 C-labeled compounds in an effort to obtain data helpful to elucidate the reaction mechanism. It has been shown that co-feeding of CF12N2, which dissociates toward CF12 and N2 on the catalyst surface, has led to the sound interpretation that the bimodal carbon number distribution is caused by superposition of two incompatible mechanisms. The distribution characterized by the lower growth probability is assigned to the CH2 insertion mechanism. 

Oxidation is the first step for producing molecules with a very wide range of functional groups because oxygenated compounds are precursors to many other products. For example, alcohols may be converted to ethers, esters, alkenes, and, via nucleophilic substitution, to halogenated or amine products. Ketones and aldehydes may be used in condensation reactions to form new C-C double bonds, epoxides may be ring opened to form diols and polymers, and, finally, carboxylic acids are routinely converted to esters, amides, acid chlorides and acid anhydrides. Oxidation reactions are some of the largest scale industrial processes in synthetic chemistry, and the production of alcohols, ketones, aldehydes, epoxides and carboxylic acids is performed on a mammoth scale. For example, world production of ethylene oxide is estimated at 58 million tonnes, 2 million tonnes of adipic acid are made, mainly as a precursor in the synthesis of nylons, and 8 million tonnes of terephthalic acid are produced each year, mainly for the production of polyethylene terephthalate) [1]. 

The alcohol and aldehyde are in equilibrium with the hemiacetal. Coordination of Hg(II) to the alkene is followed by attack of the hemiacetal O on the alkene to give, after loss of AcOH, the product. 

In organic chemistry, reduction is defined as a reaction in which a carbon atom forms fewer bonds to oxygen, O, or more bonds to hydrogen, H. Often, a C=0 bond or C=C bond is reduced to a single bond by reduction. A reduction that transforms double C=C or C=0 bonds to single bonds may also be classified as an addition reaction. Aldehydes, ketones, and carboxylic acids can be reduced to become alcohols. Alkenes and alkynes can be reduced by the addition of H2 to become alkanes. 

It is a useful oxidant for hydrocarbons, alkenes, alcohols and aldehydes. Permanganate reacts with carbon-carbon double bonds to form a cyclic manganate(V) diester. The nature of the products is determined by subsequent rapid processes. 

Alcohols can be made from monohaloalkanes, alkenes, aldehydes and ketones. 

As stoich. [Ru(0)((N 0)p7CH3CN it oxidised primary alcohols to aldehydes, secondary alcohols to ketones, alkenes to aldehydes, tetrahydrofuran to y-butyrolactone. Styrene, cis- and tran -stilbenes gave benzaldehyde and adamantane gave 1-adamantol exclusively, while cyclohexanol gave cyclohexanone, suggesting that the complex is an effective oxidant for unactivated C-H bonds [636]. Immobilisation of the catalyst within Nation films on a basal plane pyrohtic graphite electrode was achieved, but the... 

Abstract The purpose of this chapter is to present a survey of the organometallic chemistry and catalysis of rhodium and iridium related to the oxidation of organic substrates that has been developed over the last 5 years, placing special emphasis on reactions or processes involving environmentally friendly oxidants. Iridium-based catalysts appear to be promising candidates for the oxidation of alcohols to aldehydes/ketones as products or as intermediates for heterocyclic compounds or domino reactions. Rhodium complexes seem to be more appropriate for the oxygenation of alkenes. In addition to catalytic allylic and benzylic oxidation of alkenes, recent advances in vinylic oxygenations have been focused on stoichiometric reactions. This review offers an overview of these reactions... 

Primary alcohol and aldehydes are produced from butene through the Oxo process. The Oxo process involves the addition of carbon monoxide and hydrogen to an alkene under elevated temperature and pressure in the presence of a catalyst. 

The ready formation of benzylic hydroperoxides is used in industrial oxidations, as in the synthesis of propylene oxide and phenol (see Sections 9.5.2 and 9.5.4, respectively). In contrast with autoxidation of alkenes, where various secondary processes may follow, autoxidation of arenes is less complicated. Chain termination of 99 may lead to an alcohol and aldehyde [Eq. (9.151)], and the rapid autoxidation of the latter may produce the corresponding carboxylic acid [Eq. (9.152)] ... 

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