Carboxylic acids halogen substitution

Firedamp-proof Detonators. Firedamp-proof detonators have net received tht attention that firedamp-proof expls have, possibly because the expln of the, detonator is lost in the immediately succeeding expln of the main charge. Treatment of the detonator charge in caps follows similar lines to treatment of Dynamites in the addition of cooling additives, such as salts or wax (Ref 1), BuOAc (butyl acetate) (Ref 2), or poly car boxy lie acids, oxygenated poly carboxylic acids, halogen substituted poly carboxylic and oxygenated polycarboxylic acids, and the neutral and acid salts of these (Ref 4)... 

The Perkin reaction is capable of numerous modifications, since in place of benzaldehyde, its homologues, its nitro- and oxy-derivatives, etc., may be used. On the other hand, the homologues of sodium acetate may be used as has been pointed out. The condensation in these cases always takes place at the carbon atom adjoining the carboxyl group. Halogen substituted aliphatic adds will also react thus from benzaldehyde and chloracetic add, chlordnnamic acid is obtained ... 

Listing of triorganotin carboxylates of halogen substituted carboxylic acids concludes in Table 201. 

As with other groups, halogens can substitute hydrogen in organic compounds containing additional functional moieties such as carboxylic acids to form acid chlorides, e.g. acetyl chloride CH3COCI. These are reactive acidic compounds liberating hydrochloric acid on contact with water. 

An electronegative substituent, particularly if it is attached to the a carbon, increases the acidity of a carboxylic acid. As the data in Table 19.2 show, all the rnono-haloacetic acids are about 100 times more acidic than acetic acid. Multiple halogen substitution increases the acidity even more trichloroacetic acid is 7000 times more acidic than acetic acid ... 

Nucleophilic substitution by ammonia on a-halo acids (Section 19.16) The a-halo acids obtained by halogenation of carboxylic acids under conditions of the Hell-Volhard-Zelinsky reaction are reactive substrates in nucleophilic substitution processes. A standard method for the preparation of a-amino acids is displacement of halide from a-halo acids by nucleophilic substitution using excess aqueous ammonia. 

Because inductive effects operate through cr bonds and are dependent on distance, the effect of halogen substitution decreases as the substituent moves farther from the carboxyl. Thus, 2-chlorobutanoic acid has p/chlorobutanoic acid has p/chlorobutanoic acid has p/C., = 4.52, similar to that of butanoic acid itself. 

Acid halides are among the most reactive of carboxylic acid derivatives and can be converted into many other kinds of compounds by nucleophilic acyl substitution mechanisms. The halogen can be replaced by -OH to yield an acid, by —OCOR to yield an anhydride, by -OR to yield an ester, or by -NH2 to yield an amide. In addition, the reduction of an acid halide yields a primary alcohol, and reaction with a Grignard reagent yields a tertiary alcohol. Although the reactions we ll be discussing in this section are illustrated only for acid chlorides, similar processes take place with other acid halides. 

An aqueous solution containing 0.10 mole/liter of chloroacetic acid, ClH2CCOOH, is tested with indicators and the concentration of H (aq) is found to be 1.2 X 10 2 M. Calculate the value of Ka (if necessary, refer back to Section 11-3.2). Compare this value with KA for acetic acid—the change is caused by the substitution of a halogen atom near a carboxylic acid group. 

If the pyrrole is substituted with an electron-withdrawing group, then more vigorous halogenation conditions are required, but the products are usually more stable than simple halogenated pyrroles. For example, the bromination of pyrrole-2-carboxylic acid (12) yields the 4,5-dibromo isomer (13) in excellent yield [22]. Similarly, the bromination of 4-chloropyrrole-2-carboxylic acid furnishes 5-bromo-4-chIoropyrrole-2-carboxylic acid in 90% yield [23]. 

Solvents can be classified into three categories according to their polarity namely, polar protic, dipolar aprotic and non-polar. Most of the common solvents fall under one of following chemical classes Aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids, esters, halogen-substituted hydrocarbons, amines, nitriles, nitro-derivatives, amides and sulfur-containing solvents (Marcus, 1998). In certain cases a mixture of two or more solvents would perform better than a single solvent. 

The loosening influence of the carboxyl group on adjacent hydrogen is much smaller. Hence, in carboxylic acids substitution by halogen proceeds with much more difficulty but can be accelerated by illumination and by catalysts (carriers). The point of entry of the halogen is here also always at the carbon atom adjacent to the carboxyl group, the a-carbon atom. 

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]. 

Alcohols can react in several ways, depending on the reactants and on the conditions of the reaction. For example, alcohols can undergo substitution with halogen acids, elimination to form alkenes, and oxidation to form aldehydes, ketones, or carboxylic acids. 

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

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