Alcohols and Carboxylic Acids

Some materials such as water, alcohols, carboxylic acids and primary and secondary amines may be able to act simultaneously as proton donors and acceptors. Cellulose and poly(vinyl alcohol) are two polymers which also function in this way. 

Epoxy plastics Group of plastics composed of resins produced by reactions of epoxides or oxiranes with compounds such as amines, phenols, alcohols, carboxylic acids, and anhydrides, and unsaturated compounds. 

Recent mechanistic studies have shown that the many combinations of alcohols, carboxylic acids and solvents cannot be correctly described by a uniform mechanism. In certain cases the reaction appears to involve a pentavalent dialkoxyphos-phorane 10 as an intermediate, which is in equilibrium with oxyphosphonium salt 8 4 ... 

The hydrocarbons are the basic framework for all organic compounds. Different classes of organic compounds have one or more of the hydrogen atoms replaced by other atoms or groups of atoms. All we need to be aware of at this stage are the three classes of compounds known as alcohols, carboxylic acids, and haloalkanes ... 

Hydrogen bonding 5, occurs when a proton-acceptor molecule (primary and secondary amines, and sulfoxides) interacts with a proton-donor molecule (alcohols, carboxylic acids, and phenols). 

In this section the photoaddition of water, alcohols, carboxylic acids, and miscellaneous other small molecules to various substrates will be considered. 

Most ruthenium-initiated ROMP studies have been performed using (233) and strained cyclo-olefinic monomers such as norbornene688 and cyclobutenes,689 although several reports on the polymerization of 8-membered rings have also appeared.690-692 A wide range of functionalities are tolerated, including ethers, esters, amines, amides, alcohols, carboxylic acids, and ketones. 

It is in many ways unfortunate that the study of cationic polymerization has, from its very start, been so intimately linked with the very complicated and ill-understood chemistry of the metal halides. This connection is largely fortuitous and there is the promise of much progress in this field when these two problems can be attacked independently. On the one hand, we need to know much more about the complex acids and esters which are formed when water, alcohols, carboxylic acids, and alkyl halides react with metal halides on the other hand, a study of olefin polymerizations catalysed by simple acids such as HBr [14], HC104 [25], and H2S04 [26] should be rewarding, because they would presumably be unobscured by the complications and uncertainties accompanying the formation of the initiating species when this involves a metal halide. 

The additional interesting part of Fig. 1.12 is the biorefinery, which uses biomass and waste, produces waste products C02 and ash, both to be recycled for the production of biofuels, heat and electricity and biomaterials. These biomaterials are highly oxygen functionalized for products such as alcohols, carboxylic acids and esters. A currently produced bioplastic is poly(lactic acid). A main cost factor is separation. 

Aldehydes themselves are of little commercial interest, but they open a way to alcohols via hydrogenation, to carboxylic acids via oxidation, and to amines via reductive amination. Aldolization is the starting point for branched alcohols, carboxylic acids, and amines with a double carbon number. As an example of co-aldolization, the route to polyols is shown. All... 

Mateja Pogorevc, M. and Faber, K., Biocatalytic resolution of sterically hindered alcohols, carboxylic acids and esters containing fiiUy substituted chiral centers by hydrol)4ic enzymes. J. Mol. Catal. B, 2000,10, 357-376 and references cited therein. 

Alcohols, carboxylic acids, and esters are oxygen-containing molecules that play multiple roles in living organisms. Oxygen-centered radicals are thought to contribute to the aging process. 

Oxygen is a defining element in several classes of the molecnles of life. These inclnde alcohols, carboxylic acids, and esters. 

G.A. Olah, M. Nojima, I. Kerekes, Synthetic methods and reactions. I. Seleniuum tetrafluoride and its pyridine complex. Convenient fluorinating agents for fluorination of ketones, aldehydes, amides, alcohols, carboxylic acids, and anhydrides, J. Am. Chem. Soc. 96 (1974) 925-927. 

Organometallics are generally strong nucleophiles and bases. They react with weak acids, e.g. water, alcohol, carboxylic acid and amine, to become protonated and yield hydrocarbons. Thus, small amounts of water or moisture can destroy organometallic compounds. For example, ethylmag-nesium bromide or ethyllithium reacts with water to form ethane. This is a convenient way to reduce an alkyl halide to an alkane via Grignard and organolithium synthesis. 

Table 2. Fluorination of Various Alkanes, Alcohols, Carboxylic Acids and Ketones with Fluorine44...

The related reaction foro-nttrobenzyl esters results in hydrolysis of the ester, and this has been developed for use in the protection of alcohols, carboxylic acids and amines. For example, the C-1 hydroxyl group in carbohydrates can be protected as its o-njtrobenzyl ester, and the ester group removed under the very mild conditions of irradiation in neutral solution (5.51). Similarly, the carboxylic acid... 

The rationale of classification by reaction types is that different functional groups may show the same kinds of reactions. Thus, as we have just seen, alcohols, carboxylic acids, and amines all can accept a proton from a suitably strong acid. Fortunately, there are very few different types of organic reactions — at least as far as the overall result that they produce. The most important are acid-base, substitution, addition, elimination, and rearrangement reactions. Some examples of these are given below, and you should understand that these are descriptive of the overall chemical change and nothing is implied as to how or why the reaction occurs (also see Section 1-11). 

Isocyanates are liquids or solids which are highly reactive and undeigo addition reactions across the C=N double bond of the NCO group. Reactions with alcohols, carboxylic acids, and amines have been widely exploited in developing a variety of commercial products. Cydoaddition reactions involving both the C=N and the C=0 double bond of the NCO group have been extensively studied and used for product development (1—9). 

The use of polar solvents, such as N,N-dimethylformamide [68-12-2% is noted to result in extensive trimer formation. However, if the isocyanate is trapped using compounds such as alcohols, carboxylic acids, and amines which contain active hydrogen, high yields are obtained (93). 

Alcohols are at a fairly low oxidation level compared to other oxygen-containing functional groups and consequently are readily prepared by reduction. Large numbers of reductive methods have been reported for the preparation of alcohols. Carboxylic acids and esters react vigorously with lithium aluminum hydride (LAH) to produce primary alcohols. Carboxylic acids, but not esters, are also reduced easily by borane, which is die only reducing agent diat reacts faster widi carboxylic acids dian widi esters or odier acid derivatives. 

Diphenyl diselenide is an especially useful co-reagent with [bis(acetoxy)-iodo]benzene. For example, the BAIB/PhSeSePh (2 1) combination has been employed for trans, Markovnikov additions of PhSeOAc and PhSeOH to alkenes [35]. Such formal additions appear to be regulated by seleniranium intermediates, and were extended to intramolecular cyclizations of olefinic alcohols, carboxylic acids, and / -dicarbonyl compounds (Scheme 12). 

The strong electronegativity of the fluorinated substituents is reflected in the effect that this group has upon the acidity of alcohols, carboxylic acids, and sulfonic acids, as well as the effect it has on the basicity of amines (Tables 1.3-16).1,26... 

Proteins contain a variety of functional groups that can bind them to mineral surfaces carbonyl, alcoholic, carboxylic acid, and amine. Studies have shown that protein adsorption to clays is rapid at a pH below the isoelectric point of the protein (e.g., McLaren, 1954 Armstrong and Chesters, 1964). Conversely, then, protein should be extracted by a solvent system with a pH above the protein s isoelectric point. There are also hydrophobic regions on some proteins that create the possibility for hydrophobic interactions between the sorbed protein and the mineral surface (Quiquampoix, 2000). 

The functional groups of heparin suitable for formation of a covalent bond include the alcohol, carboxylic acid, and amino groups. The structure of heparin is shown in Figure 1. The amino groups readily react with... 

Starch complexes with aromas and flavoring agents are usually synthetic in origin. In nature, starch sometimes includes some aroma- and flavor-genic components that generate flavor and aroma on processing (see, for instance, ref. 678). Such agents include mainly aldehydes, ketones, and carboxylic esters however, hydrocarbons, alcohols, carboxylic acids, and haloalkanes have also been used. 

Fig. 2-4. Flomo-intermolecular hydrogen bonds in alcohols, carboxylic acids, and amides (the hydrogen bonds are denoted by dotted lines).

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