Acetyl chloride reaction with alcohols

Reaction with alcohols gives the corresponding acetate esters. Acetyl chloride will add across unsaturated bonds in the presence of suitable catalysts 10 give halogenated ketunes ... 

Similarly, a-acetoxyrhenacyclobutadiene complexes, generated in situ by the reaction of acetyl chloride with rhenacyclobutanone 14, undergo substitution upon reaction with alcohols (Equation 3), giving a-alkoxyrhenacyclo-butadiene complexes 15 <2004JOM2000>. 

Acyl halides such as acetyl chloride react with water to regenerate the starting acid and they react with alcohols to yield esters. The reaction is often facilitated by the presence of a tertiary amine catalyst. Although this may function purely as a base to neutralize the hydrochloric acid which is formed in the reaction, bases such as dimethylaminopyridine can also activate the carboxyl group via the formation of the intermediate shown in Scheme 3.66. 

The conclusive proof that in acetone there are two methyl groups present is in the synthesis of acetone from acetic acid and acetyl chloride, reactions which we shall soon study. With this conclusive proof our formula, as we have written it, must be correct and our ideas in regard to the oxidation of compounds containing hydrogen linked to carbon are probably correct also. The steps in the oxidation are probably as we have indicated, viz., that hydrogen is first converted into hydroxyl and when as a result of such oxidation, two hydroxyls are linked to one carbon the compound loses water, leaving one oxygen doubly linked to the carbon. This enables us to understand the facts that only primary alcohols on oxidation yield aldehydes, secondary alcohols yield ketones, while tertiary alcohols yield neither aldehydes nor ketones. 

Tris(trimethylsilyl)phosphine is a colorless compound with a melting point near room temperature. Characteristic NMR data for a DME solution are 5,ih) 0.30 Jp = 4.4 cps 5,3ip,-251. In reactions with alcohols and water bis(trimethylsilyl) and (trimethylsilyl)phosphine can be synthesized acetyl chloride in a molar ratio of 1 3 gives triacetylphosphine. For the important reaction with 2,2-dimethylpropionyl chloride see Section 49. 

As already mentioned under acetyl chloride, add-chlorides react with alcohols, phenols, primary and secondary amines, the chlorine atom uniting with the hydrogen of the hydroxyl-, amido-, or imido-group, with the elimination of hydrochloric add, while the residues combine to form an ester or a substituted amide. The value of the Schotten-Baumann reaction depends on the fact that this reaction is so essentially facilitated by the presence of sodium hydroxide or potassium hydroxide- that even in the presence of water the decomposition takes place, which in the absence of alkalies is not possible ... 

CH3 —C —Cl. Acetyl chloride reacts with water and forms acetic acid and hydrochloric acid, and with methyl alcohol to form methyl acetate and hydrochloric acid. The equations for the reactions are as follows —... 

The synthesis of 2-acylamino-2-deoxy-/3-D-glucopyranosides can be effected from the acetylated glycosyl acetates by reaction with alcohols in the presence of iron(lll) chloride. The procedure is satisfactory with primary, secondary, or tertiary alcohols, and with a range of A-acyl substituents. It is believed that the... 

Now let s draw the forward scheme. Hydrolysis of the nitrile to the carboxylic acid, followed by reaction with thionyl chloride, produces the acid chloride. Reaction with excess methyl magnesium bromide, followed by water work-up, results in the formation of a tertiary alcohol, with the incorporation of two new methyl groups. The tertiary alcohol can then serve as a nucleophile in an acetylation reaction (upon treatment with acetyl chloride) to give the desired ester. 

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 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. 

Chloroform can be manufactured from a number of starting materials. Methane, methyl chloride, or methylene chloride can be further chlorinated to chloroform, or carbon tetrachloride can be reduced, ie, hydrodechlorinated, to chloroform. Methane can be oxychlorinated with HCl and oxygen to form a mixture of chlorinated methanes. Many compounds containing either the acetyl (CH CO) or CH2CH(OH) group yield chloroform on reaction with chlorine and alkali or hypochlorite. Methyl chloride chlorination is now the most common commercial method of producing chloroform. Many years ago chloroform was almost exclusively produced from acetone or ethyl alcohol by reaction with chlorine and alkali. 

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-... 

Not only water and alcohols, but also other oxygen compounds, are able to react covalently with acylium ions. In the case of hydroxy compounds the product is stabilized by loss of the proton from the hydroxyl group, but certain ethers give an analogous reaction in which the product is stabilized by loss of a carbonium ion.288 Using acetyl chloride with silver perchlorate in nitromethane as the source of acetyl... 

Aldono-1,5-lactones and free aldonic acids react with alcohols in the presence of hydrogen chloride to give the corresponding alkyl aldonates (84). The reaction is slower with 1,4-lactones. Because esterification takes place very slowly in the absence of an acidic catalyst, aldonic acids and their lactones may be recrystallized from boiling alcohols without appreciable esterification (85). However, in some instances, alkyl esters are formed under these conditions. For example, essentially pure ethyl L-mannonate was isolated (6.4% yield) from the mother liquors of crystallization L-man-nono-1,4-lactone, obtained by Kiliani synthesis from L-arabinose (86). Similarly, repeated recrystallization from ethanol of crude 2,3,4,6-tetra-O-acetyl-D-glucono- 1,5-lactone afforded the corresponding ethyl gluconate derivative (87). 

Acid chlorides were also shown to be reactive electrophiles. B-Allenyl-9-BBN affords tertiary bis-homopropargylic alcohols in satisfactory yields upon reaction with acetyl or benzoyl chloride (Eq. 9.23). 

---