Aliphatic acid chlorides hydrolysis

The acylation of enamino ketones can take place on oxygen or on carbon. While reaction at nitrogen is a possibility, the N-acylated products are themselves acylating agents, and further reaction normally takes place. The first reported acylation of enamino ketones (72) was that of 129, prepared by acylation of the enamine (113), which was shown to have undergone O acylation because on mild hydrolysis the enol ester (130) could be isolated. A similar reaction took place with other aliphatic acid chlorides (80) and with dibasic acid chlorides [e.g., with succinyl chloride to give 118 above]. 

The MEMED technique has been used to study the hydrolysis of aliphatic acid chlorides in a water/l,2-dichloroethane (DCE) solvent system [3]. It was shown unambiguously that the reaction proceeds via an interfacial process and shows saturation kinetics as the concentration of acid chloride in the DCE increases the data were well fitted to a model based on a pre-equilibrium involving Langmuir adsorption at the interface. First-order rate constants for interfacial solvolysis of CH3(CH2) COCl were 300 150(n = 2), 200 100(n = 3) and 120 60 s-1( = 8). 

This reaction was initially reported by Reissert in 1905 and extended by Grosheintz and Fischer in 1941 It is the synthesis of aldehyde involving the formation of 1 -acyl-2-cyano-1,2-dihydroquinoline derivatives from acyl chlorides, quinoline, and potassium cyanide and the subsequent hydrolysis of said dihydroquinoline derivatives under acidic conditions to produce quinaldic acid and aldehydes. The original procedure occurs smoothly for aroyl or cinnamoyl chloride in liquid SO2 but not in benzonitrile, ether, dioxane, acetone, or CHCb. However, the modification from Grosheintz and Fischer using hydrogen cyanide and 2 eq. quinoline in absolute benzene is also adaptable for aliphatic acid chlorides. This is one of the methods that converts acyl chlorides into aldehydes and is found to be superior to the normal Rosenmund Reduction. For example, o-nitrobenzoyl chloride has been converted into o-nitrobenzaldehyde in 60% yield by the current reaction, whereas the Rosenmund Reduction is not suitable for such conversion. Therefore, this reaction is referred to as the Grosheintz-Fischer-Reissert aldehyde synthesis or Reissert aldehyde synthesis. ... 

Early measurements established79 80,113 that electron-withdrawing substituents increased the rate of hydrolysis, alcoholysis or aminolysis114 of the acid chloride RCOC1, and that in the aliphatic series the rate decreased with... 

The familiar substitution reactions of derivatives of carboxylic acids with basic reagents illustrate nucleophihc substitution at aliphatic sp carbons. (Substitution reactions of carboxylic acids, and their derivatives, with acidic reagents are covered in Chapter 4.) The mechanisms of these reactions involve two steps (1) addition of the nucleophile to the carbonyl group and (2) elimination of some other group attached to that carbon. Common examples include the basic hydrolysis and aminolysis of acid chlorides, anhydrides, esters, and amides. 

Thietanones also have been obtained by treatment of aliphatic ketones with an a-methylene group with thionyl chloride, usually in the presence of a base as shown for the synthesis of 359. A 3-thietanone was suggested as a possible structure for the product obtained by the acid-catalyzed hydrolysis of the bis-thioglycolic thioacetal of substituted benzaldehydes, but an elemental analysis was the only evidence. Treatment of l-diazo-3-phenylthio-2-propanone with acid gives the -phenyl salt of 3-thietanone (Section VII.1.). Similar 5-alkyl salts may be intermediates, but they readily decompose either by loss of the 5-alkyl group or... 

The hydrolysis of acyl chlorides to a carboxylic acid and hydrogen chloride is rapid and violent in the lower aliphatic acyl chlorides. With increase in the complexity of the radical there is a corresponding increase in stability. Aryl acyl chlorides are only slowly hydrolyzed at low temperatures. In general, however, the halogen attached to the acyl group is very much more reactive than a halogen attached to other organic radicals. 

Hydroxymethyl ketones. Preparation of ketones of this type by reaction of acid chlorides and diazomethane followed by hydrolysis of the diazo ketone is not practical for large scale work. The desired transformation can be carried out with the new reagent 1, a derivative of ketene. A typical example is formulated in equation (I). Aromatic acid chlorides react more slowly with 1 than aliphatic acid... 

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... 

Polysulfonate co-polymer (sulfonate-car-boxylate co-polymer) n. A family of transparent, thermoplastic polyesters, moldable at 250-300°C, and formed by reaction of a diphenol, generally bisphenol A, with an aromatic disulfonyl chloride and an aliphatic disulfonyl chloride or carboxylic acid chloride. These co-polymers have good electrical and mechanical properties, and excellent resistance to hydrolysis and aminolysis. 

Lactones are formed predominantly from y-, (5-, and e-hydroxy acids. Most lactones of the aliphatic series are converted easily under the influence of water to corresponding hydroxy acids. For the hydrolysis of aromatic lactones heating with alkalies is necessary. The reactions of lactones with ammonia and phenylhydrazine, which can be used in certain cases for identification purposes, are described in greater detail in a special monograph (134). Aliphatic y-lactones react in benzene solution with thionyl chloride, with the formation of hydroxy acid chlorides, from which suitable derivatives can be prepared (135). 

Sulfonamides (R2NSO2R ) are prepared from an amine and sulfonyl chloride in the presence of pyridine or aqueous base. The sulfonamide is one of the most stable nitrogen protective groups. Arylsulfonamides are stable to alkaline hydrolysis, and to catalytic reduction they are cleaved by Na/NH3, Na/butanol, sodium naphthalenide, or sodium anthracenide, and by refluxing in acid (48% HBr/cat. phenol). Sulfonamides of less basic amines such as pyrroles and indoles are much easier to cleave than are those of the more basic alkyl amines. In fact, sulfonamides of the less basic amines (pyrroles, indoles, and imidazoles) can be cleaved by basic hydrolysis, which is almost impossible for the alkyl amines. Because of the inherent differences between the aromatic — NH group and simple aliphatic amines, the protection of these compounds (pyrroles, indoles, and imidazoles) will be described in a separate section. One appealing proj>erty of sulfonamides is that the derivatives are more crystalline than amides or carbamates. 

Of the primary monoamines, some, such as. aniline, o-toluidine, xylidine, are colourless liquids. Others, such as p-toluidine, pseudo-cumidine and the naphthylamines, are solids. They can be distilled without decomposition and are volatile with steam. In water they are rather sparingly soluble—a 3 per cent solution of aniline can be made. The di- and polyamines are usually solids, not volatile in steam and much more soluble in water than the monoamines. The amines are basic in character, but, as a result of the negative nature of the phenyl-group, the aromatic amines are considerably weaker bases than are the aliphatic amines. Consequently aqueous solutions of the (stoicheio-metrically) neutral aniline salts are acid to litmus because of the hydrolysis which they undergo. For the same reason a small amount of the free base can be extracted with ether from an aqueous solution of an aniline salt. (Test with a solution of hydrogen chloride in ether or, after evaporation of the ether, by the reaction with bleaching powder.)... 

The preferred industrial method of carvone synthesis utilizes the selective addition of nitrosyl chloride to the endocyclic double bond of limonene. If a lower aliphatic alcohol is used as solvent, limonene nitrosochloride is obtained in high yield. It is converted into carvone oxime by elimination of hydrogen chloride in the presence of a weak base. Acid hydrolysis in the presence of a hydroxylamine acceptor, such as acetone, yields carvone [88]. 

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