ACID CHLORIDES OF ALIPHATIC CARBOXYLIC ACIDS

The conversion of aliphatic acids Into their acid chlorides is usually accomplished with — 

Phosphorus trichloride. The reaction is not quite quantitative, for example  

---

If an ortho-substituted benzene ring is attached to the nitrogen, the self-condensation is minimized due to steric hindrance and the yield of imidoyl chlorides increases in this order CH3 < Cl < Br ( ). Likewise, lowering of the basicity of the nitrogen prevents condensation. For example, N-sulfonimidoyl chlorides of aliphatic carboxylic acids are obtained in excellent yield ( ). The carboxylic acid amides of a,j8-unsaturated acids also do not undergo tautomerization, because the formation of allenes is not favored under mild conditions... 

Imidoyl chlorides of aliphatic carboxylic acids To the solution of... 

Electrofluorination of aliphatic carboxylic and sulfonic acid chlorides or fluorides to perfluorinated products [31]. 

The use of sulfuryl chloride for free radical chlorination of aliphatic carboxylic acids gives mixtures of positional isomers.7 However, with the cyclobutane ring, the attack is much more selective. The present method provides a procedure for free radical halogenation of a cyclobutane ring. 

Acetonitrile, 407 Acetophenone, 725,729,730 phenylhydrazone, 852 p-Acetotoluidide, 593, 605 Acetoxime, 343 Acetylacetone, 861, 862, 863 Acetylation, reductive, 749 Thiele, 749 Acetyl chloride, 367 2-Acetylcyciohexanone, 862, 864 Acetylene, 245, 897 reactions of, 245, 246 Acetylenic compounds, synthesis of, 467-469, 895-902 Acetylglycine, 909 Acetylmethylurea, 968, 969 Acetylsalicylio acid, 996 Acetyl-o-toluidide, 578 2-Acetylthiophene, 837 Acid anhydrides of aliphatic carboxylic acids, 371... 

The use of aliphatic carboxylic acid anhydrides in place of the corresponding acid chlorides offers many advantages these include ... 

Vinyl chloride can be copolymerized with a series of monomers Vinylidene chloride, trans-dichloroethylene, vinylesters of aliphatic carboxylic acid (C2-C18), acrylic acid esters, methacrylic and/or maleic acid as well as fumaric acid with mono-functional aliphatic saturated alcohols (Cj-C18), mono-functional aliphatic unsaturated alcohols (C8—C18), vinyl ethers from mono-functional aliphatic saturated alcohols (C i-Cis), propylene, butadiene, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid (total < 8 %) and N-cyclohexylmaleinimide (< 7 %). 

A large number of stable /e-organo tellurocarboxylates were prepared from tellurolates and aliphatic1,2 or aromatic2 carboxylic acid chlorides or aliphatic carboxylic acid anhydrides . The tellurolates were obtained by reduction of diorgano ditelluriums with sodium borohydride. 

Aromatic carboxylic acids show many properties that parallel those of aliphatic carboxylic acids. Thus acyl chlorides are formed on treatment with thionyl chloride and esters are obtained on treatment with the alcohol and an add catalyst. Benzoate and 3,5-dinitrobenzoate esters are used in the characterization of alcohols and are prepared using the reaction of the acyl halide with the alcohol. 

Tertiary aliphatic amines cannot be acylated by the chlorides of simple carboxylic acids. When reaction occurs, the chlorides lose hydrogen halide, affording ketenes588 which readily undergo further reaction in individual cases of, / -unsaturated acyl chlorides, acyltrialkylammonium salts can be... 

Aliphatic compounds also react with chlorosulphonic acid, but the yields of sulphonyl chlorides are usually very low5. However, it has been found that the reaction of aliphatic carboxylic acids with chlorosulphonic acid, in the presence of POCl3526, gives excellent yields of disulphonyl chlorides (with concomitant loss of carbon dioxide), as shown in equation 137. 

Aliphatic imidoyl chlorides react faster than the N-alkyl imidoyl chlorides of aromatic carboxylic acids, and arylimidoyl chlorides react the slowest. Electron-withdrawing groups attached to the aryl moieties retard the reaction while electron-donating groups attached to the aryl groups increase the rate of reaction. Likewise, a carbonyl group adjacent to the C=N bond decreases the rate of hydrolysis. Cyclic imidoyl chlorides react rather slowly with water, as evidence by the fact that 2-chloro-A -pyrroline can be recrystallized from aqueous acetone... 

The halogenation of imidoyl chlorides and iminium chlorides occurs readily, provided that an a-hydrogen is present. Thus, a simple method of dihalogenation of aliphatic carboxylic acid amides is provided by the addition of halogen to imidoyl chlorides and iminium chlorides. 

A suitable substitution of the aromatic nucleus of benzoyl chloride (nitration, bromination), or the use of chlorides of naphthalene-carboxylic adds, or, especially, anthraquinone-carboxylic acids, results in their esters being solid substances, even when prepared from aliphatic alcohols. The most popular derivatives for the identification of alcohols are, however, the esters of 3,5-dinitrobenzoic acid. 

Dimsyl anion 88 reacts with esters of aromatic carboxylic acids and aliphatic acids which do not have a readily transferable proton, to give /5-ketosulfoxides114,133,138-141. There are not many cases in which acyl chlorides were used142,143. However, the reaction... 

---