Acetylation, alcohol with acetyl chloride

Esters of diphenylacetic acids with derivatives of ethanol-amine show mainly the antispasmodic component of the atropine complex of biologic activities. As such they find use in treatment of the resolution of various spastic conditions such as, for example, gastrointestinal spasms. The prototype in this series, adiphenine (47), is obtained by treatment of diphenyl acetyl chloride with diethylaminoethanol. A somewhat more complex basic side chain is accessible by an interesting rearrangement. Reductive amination of furfural (42) results in reduction of the heterocyclic ring as well and formation of the aminomethyltetrahydro-furan (43). Treatment of this ether with hydrogen bromide in acetic acid leads to the hydroxypiperidine (45), possibly by the intermediacy of a carbonium ion such as 44. Acylation of the alcohol with diphenylacetyl chloride gives piperidolate (46). ... 

The reactions of alcohols with acid chlorides and with acid anhydrides are the most important ways of making esters, but not the only ways. We shall see later how carboxylic acids can be made to react directly with alcohols. Remember the convenient organic element symbol for acetyl , Ac Cyclohexyl acetate can be represented by OAc but not just Ac . 

Benzalacetone has been obtained in small yield by drv distillation of a mixture of calcium acetate and calcium cinnamate (1) by heating the sodium derivative of cinnamaldehyde with methyl iodide (2) by heating cinnamaldehyde and methyl alcohol with zinc chloride (2) by heating acetone and benzaldehyde with acetic anhydride or zinc chloride (3). It is also formed when styrene and acetyl chloride are condensed by means of stannic chloride and the product is treated with diethylaniline (4) and when the vapors of cinnamic acid and acetic acid are passed together over ferric oxide at 470-490° (5). The only practical method, however, consists in condensing benzaldehyde and acetone by means of dilute aqueous alkali (6). 

On acetylation it gives acetanilide. Nitrated with some decomposition to a mixture of 2-and 4-nitroanilines. It is basic and gives water-soluble salts with mineral acids. Heating aniline sulphate at 190 C gives sulphanilic add. When heated with alkyl chlorides or aliphatic alcohols mono- and di-alkyl derivatives are obtained, e.g. dimethylaniline. Treatment with trichloroethylene gives phenylglycine. With glycerol and sulphuric acid (Skraup s reaction) quinoline is obtained, while quinaldine can be prepared by the reaction between aniline, paraldehyde and hydrochloric acid. 

Reflux 1 g. of the sulphonamide with 2-5 ml. of acetyl chloride for 30 minutes if solution is not complete within 5 minutes, add up to 2-5 ml. of glacial acetic acid. Remove the excess of acetyl chloride by distillation on a water bath, and pour the cold reaction mixture into water. Collect the product, wash with water and dissolve it in warm sodium bicarbonate solution. Acidify the Altered solution with glacial acetic acid Alter oflF the precipitated sulphonacetamide and recrystaUise it from aqueous alcohol. 

Acetyl chloride reacts vigorously with primary and secondary alcohols to yield esters it also reacts readily with any water present to form acetic acid ... 

Acetyl chloride test. In a small, dry test-tube treat 0 -5 ml. of the compound with 0-3-0-4 ml. of redistUled acetyl chloride and note whether reaction occurs. Add 3 ml. of water and neutralise the aqueous layer with solid sodium bicarbonate. Look for a product different from the original alcohol. 

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. 

A mixture of 0.30 mol of the tertiairy acetylenic alcohol, 0.35 mol of acetyl chloride (freshly distilled) and 0.35 mol of /V/V-diethylaniline was gradually heated with manual swirling. At 40-50°C an exothermic reaction started and the temperature rose in a few minutes to 120°C. It was kept at that level by occasional cooling. After the exothermic reaction had subsided, the mixture was heated for an additional 10 min at 125-130°C, during which the mixture was swirled by hand so that the salt that had been deposited on the glass wall was redissolved. After cooling to below 50°C a mixture of 5 ml of 36% HCl and 200 ml of ice-water was added and the obtained solution was extracted with small portions of diethyl ether. The ethereal solutions were washed with water and subsequently dried over magnesium sulfate. The solvent was removed by evaporation in a water-pump vacuum... 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

Acetophenone. Acetophenone [98-86-2] (methyl phenyl ketone) is a colorless Hquid that forms laminar crystals at low temperature (mp 20°C). It has a characteristic sweet orange blossom odor, and is soluble in alcohols and ethers. It is found in nature in oil of casatoreum, obtained from beavers oil of labdanum, recovered from plants and in buds of balsam poplar. It can be prepared by the Friedel-Crafts reaction (qv) of acetyl chloride with benzene in the presence of aluminum chloride however, this route is of Htde commercial significance. 

Deoxygenative autoaromatization was reported to occur in the reaction of 3-amino-1,2,4-triazine 2-oxides 42 with alcohols in the presence of HCl or acetyl chloride. In this case the intermediate cr -adducts undergo elimination of water or acetic acid, resulting in 6-alkoxy-3-amino-l,2,4-triazines 75 (77JOC3498). 1,2,4-Triazine 1-oxides do not react with alcohols under these conditions (77JOC3498). 

In an attempt to study the behavior and chemistry of coal in ionic liquids, 1,2-diphenylethane was chosen as a model compound and its reaction in acidic pyri-dinium chloroaluminate(III) melts ([PyHjCl/AlCb was investigated [69]. At 40 °C, 1,2-diphenylethane undergoes a series of alkylation and dealkylation reactions to give a mixture of products. Some of the products are shown in Scheme 5.1-40. Newman also investigated the reactions of 1,2-diphenylethane with acylating agents such as acetyl chloride or acetic anhydride in the pyridinium ionic liquid [70] and with alcohols such as isopropanol [71]. 

The addition of acetic acid anhydride or acetyl chloride was found to accelerate the reaction. In certain instances other solvents are also used. Phosphates of higher molecular weight alcohols was formed by reaction with P4O10 or POCl3 in the presence of benzene [18-20]. Specific examples describe the reaction of P4O10 with diglycerides from vegetable oil in the presence of isopro-... 

Imidates 60 were prepared in two steps by first reacting nitrile derivatives with various alcohols. The condensation of the obtained iminoester with appropriate acetyl chloride resulted in the formation of the title compounds 60a-c (Scheme 12). The structures of the products 60 were elucidated by means of spectroscopic analysis. 

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