Acid chloride reaction with alcohols

The reactions of Grignard reagents with aldehydes and ketones give alcohols, reaction with acid chlorides and esters give tertiary alcohols, reaction with carbon dioxide to give carboxylic acids, reaction with nitriles give ketones, and reaction with epoxides give alcohols. 

An ethereal solution of diazomethane free from alcohol may be prepared as follows such a solution is required, for example, in the Amdt-Eistert reaction with acid chlorides (compare Section VI,17). In a 100 ml. longnecked distilling flask provided with a dropping funnel and an efficient downward condenser, place a solution of 6 g. of potassium hydroxide in... 

Normal Fischer esterification of tertiary alcohols is unsatisfactory because the acid catalyst required causes dehydration or rearrangement of the tertiary substrate. Moreover, reactions with acid chlorides or anhydrides are also of limited value for similar reasons. However, treatment of acetic anhydride with calcium carbide (or calcium hydride) followed by addition of the dry tertiary alcohol gives the desired acetate in good yield. 

The reaction with carboxylic acid and acid anhydride is carried out in the presence of a small amount of concentrated sulphuric acid. The reaction is reversible, and therefore, water is removed as soon as it is formed. The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to neutralise HCl which is formed during the reaction. It shifts the equilibrium to the right hand side. The introduction of acetyl (CH3CO) group in alcohols or phenols is known as acetylation. Acetylation of salicylic acid produces aspirin. 

Reaction XXH. (c) Action of Zinc Alkyl on Acyl Chlorides in certain proportions.—The preparation of alcohols by this method has already been discussed (Reaction XV.). By using only 1 mol. of zinc alkyl to 2 mols. of acid chloride, the reaction can be stopped at the intermediate ketone stage. In the Grignard reaction with acid chlorides, it has not been found possible to do this owing to the greater reactivity of the Grignard compounds. 

Phenols can be converted into esters by reaction with acid chlorides or acid anhydrides and into ethers by reaction with alkyl halides in the presence of base (Following fig.). These reactions can be done under milder conditions than those used for alcohols due to the greater acidity of phenols. Thus phenols can be converted to phenoxide ions with sodium hydroxide rather than metallic sodium. 

Acid chlorides react rapidly and quantitatively with most nucleophiles, and they are hydrolyzed by the moisture in air. Reaction of an acid chloride with an alcohol gives an ester. Reaction with acid chlorides readily converts amines into amides. 

Why are the esters of tertiary alcohols prepared by reaction with acid chlorides rather than by the Fischer esterification method ... 

One of the first examples of the grafting to approach was published by Sun et al. in 2001 [32]. In this work carboxylic acid groups on the nanotube surface were converted into acyl chlorides by refluxing the samples in thionyl chloride. Then the acid chloride functionalized carbon nanotubes were reacted with hydroxyl groups of dendritic PEG polymers via esterification reactions. Similarly, many polymers terminated with amino or hydroxyl moieties have been used in amidation and esterification reactions with acid chloride modified NTs poly(propionylethylenimine-co-ethylenimine) (PPEI-EI) [33], poly(styrene-co-aminomethylstyrene) (PSN) [34], poly-(amic acid) containing bithiazole rings [35], monoamine-terminated poly(ethylene oxide) (PEO) [36], poly(styrene-co-hydroxymethylstyrene) (PSA) [37], poly(styrene-co-p-[4-(4 -vinylphenyl)-3-oxabutanol]) (PSV) [38], poly(vinyl alcohol) (PVA) [39], poly(vinyl acetate-co-vinyl alcohol) (PVA-VA) [40] or poly[3-(2-hydroxyethyl)-2,5-thienylene] (PHET) [41]. 

Mechanism of Action. Under photolysis, acidic, and electron bombardment conditions, the transformation of o-nitrobenzyl alcohol or its derivatives involves an internal redox reaction sequence followed by liberation of the deprotected alcohol or amine (eq 1). Analogously, the photorearrangement of esters of o-NBA, obtained through its reaction with acid chlorides or anhydrides, also induces an internal redox reaction (eq 2). 

Reduction of a nitro compound to a primary amine. In a 50 ml. round-bottomed or conical flask fitted with a reflux condenser, place 1 g. of the nitro compound and 2 g. of granulated tin. Measure out 10 ml. of concentrated hydrochloric acid and add it in three equal portions to the mixtiue shake thoroughly after each addition. When the vigorous reaction subsides, heat under reflux on a water bath until the nitro compound has completely reacted (20-30 minutes). Shake the reaction mixture from time to time if the nitro compound appears to be very insoluble, add 5 ml. of alcohol. Cool the reaction mixture, and add 20-40 per cent, sodium hydroxide solution imtil the precipitate of tin hydroxide dissolves. Extract the resulting amine from the cooled solution with ether, and remove the ether by distillation. Examine the residue with regard to its solubility in 5 per cent, hydrochloric acid and its reaction with acetyl chloride or benzene-sulphonyl chloride. 

The alcohol groups of carbohydrates undergo chemical reactions typical of hydroxyl functions They are converted to esters by reaction with acyl chlorides and carboxylic acid anhydrides... 

Other Reactions. Primary amyl alcohols can be halogenated to the corresponding chlorides by reaction with hydrogen chloride in hexamethylphosphoramide (87). Neopentyl chloride [753-89-9] is formed without contamination by rearrangement products. A convenient method for preparing / f/-amyl bromide and iodide involves reaction of / f/-amyl alcohol with hydrobromic or hydroiodic acid in the presence of Li or Ca haUde (88). The metal haUdes increase the yields (85 —95%) and product purity. 

The choice of which reactions to include is not an easy one. First there are the well known "Name Reactions", that have appeared in various monographs or in the old Merck index. Some of these are so obvious mechanistically to the modern organic chemistry practitioner that we have in fact omitted them for instance esterification of alcohols with acid chlorides - the Schotten-Baumann procedure. Others are so important and so well entrenched by name, like the Baeyer-Villiger ketone oxidation, that it is impossible to ignore them. In general we have kept older name reactions that are not obvious at first glance. 

Other methods for the preparation of esters are the action of alcohol on the acid chloride or anhydride (see Reactions, p. 75), or by boiling up the dry powdered silver salt of the acid with the alkyl iodide,... 

The most important group of derivatives for the amino function (Fig. 7-4) is the carbamate group, which can be formed by reactions with acids, acid chlorides or acid anhydrides. A series of chlorides as 2-chloroisovalerylchloride [1], chrysanthe-moylchloride [2] and especially chloride compounds of terpene derivatives (cam-phanic acid chloride [3], camphor-10-sulfonyl chloride [4]) are used. The a-methoxy-a-trifluoromethylphenylacetic acid or the corresponding acid chloride introduced by Mosher in the 1970s are very useful reagents for the derivatization of amines and alcohols [5]. 

Conversion of Acid Halides into Amides Aminolysis Acid chlorides react rapidly with ammonia and amines to give amides. As with the acid chloride plus alcohol method for preparing esters, this reaction of acid chlorides with amines is the most commonly used laboratory method for preparing amides. Both monosubstituted and disubstituted amines can be used, but not trisubstituted amines (R3N). 

Reaction of Acid Chlorides with Organometallic Reagents Grignard reagents react with acid chlorides to yield tertiary alcohols in which two of the substituents are the same. 

Acid anhydride-diol reaction, 65 Acid anhydride-epoxy reaction, 85 Acid binders, 155, 157 Acid catalysis, of PET, 548-549 Acid-catalyzed hydrolysis of nylon-6, 567-568 of nylon-6,6, 568 Acid chloride, poly(p-benzamide) synthesis from, 188-189 Acid chloride-alcohol reaction, 75-77 Acid chloride-alkali metal diphenol salt interfacial reactions, 77 Acid chloride polymerization, of polyamides, 155-157 Acid chloride-terminated polyesters, reaction with hydroxy-terminated polyethers, 89 Acid-etch tests, 245 Acid number, 94 Acidolysis, 74 of nylon-6,6, 568... 

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