Hydrolyses

In the hydrolysis of benzyl chloride, the leaving group is chloride anion. When benzyl fluoride is hydrolyzed in alkaline or neutral media, the leaving group is fluoride anion, which is a worse leaving group than chloride anion because the carbon-fluorine bond is much stronger than the carbon-chlorine bond 443 kJ (106 kcal/mol) vs. 328 kJ (78 kcal/ mol), respectively. 

Rate of Hydrolysis in 10% Aq. Acetone at 50° (1(q x 106 sec 1) Concentration of HCIO4 Benzyl Chloride Benzyl Fluoride 

Hydrolysis of co-fluoronitriles in alkaline media is an SN2 reaction, which is very slow. In contrast, co-fluorocarboxylic acids are hydrolyzed by an SNi mechanism because in alkaline media, five- and six-membered lactones are temporarily formed. The driving force is the strong tendency to close six- and especially five-membered rings [55], 

The first step in the hydrolysis in tert-butyl alcohol is probably nucleophilic displacement of fluorine in the reactive allylic position. Spontaneous elimination of hydrogen fluoride from the geminal fluorohydroxy compound yields perfluorocyclopent-2-en-l-one. 

The next stage is an attack by hydroxide at the carbonyl carbon, followed by breaking of the bond between the carbonyl and the double bond. This reaction takes place in aqueous tert-butyl alcohol. (Primary and secondary alcohols as solvents would give different compounds, ethers.) The final product of the reaction is 5H-perfluoro-4-pentenoic acid (compound G) [56]. 

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Hydrolysed by dilute acids and alkalis to aniline. It chlorinates more slowly than aniline to o-and p-chloroacetanilides. 

Antimony peniachloride, SbCls. M.p. TC, b.p. 79 C (Sb or SbCIa plus CI2). Readily hydrolysed by water, forms complexes, e.g. [SbClft]". Mixed antimony(III)/(V) complexes occur as salts M2SbCl6. SbCls is used extensively as a chlorinating agent. 

M.p. 234-235 C. Hydrolyses to aspartic acid. L-asparagine can be prepared from lupin seedlings, and DL-asparagine is synthesised from ammonia and maleic anhydride. L-asparagine is very widely distributed in plants, being found in all the Leguminosae and Gramineae, and in many other seeds, roots and buds. 

Prepared by the dehydration of benzamide. Hydrolysed by dilute acids and alkalis to benzoic acid. Good solvent. benzopheDone,C]3HioO,PhC(0)Ph. Colourless rhombic prisms, m.p. 49 C, b.p. 306°C. Characteristic smell. It is prepared by the action of benzoyl chloride upon benzene in the presence of aluminium chloride (Friedel-Crafts reaction) or by the oxidation of di-phenylmethane. It is much used in perfumery. Forms a kelyl with sodium. 

Boron trichloride, BCI3. Colourless mobile liquid, m.p. — 107°C, b.p. 12-5°C. Obtained directly from the elements or by heating B2O3 with pels in a sealed tube. The product may be purified by distillation in vacuo. It is extremely readily hydrolysed by water to boric acid. TetrachJoroborates containing the BCJ4 " ion are prepared by addition of BCI3 to metal chlorides. 

CgHijClNjOj. Colourless, hygroscopic, m.p. 2I0-212 C (decomp.). Prepared from fi-chloroethyl carbamate and trimethylamine. It has a physiological action similar to that of acetylcholine, but more prolonged, as it is less readily hydrolysed. It is used for intestinal atony following operations, and can be given orally. 

Strong acids completely hydrolyse cellulose to glucose very mild hydrolysis gives hydrocelluloses with shorter chains and lower viscosity and tensile strength. Under special conditions a large yield of cellobiose is obtained. 

H0S(CI)02. Colourless liquid m.p. -80°C, b.p. 158" C (SO3 plus HCl or H2SO4 plus PCIj or POCI3). Hydrolysed by water. Used as a chlorinating and sulphonating agent. 

Chromates(V), (CrO ) ". Dark green species which hydrolyse and disproportionate to Cr III) and Cr(VI) (K2Cr04 plus KOH in melt). 

The higher chromium fluorides, CrFstrong oxidizing agents, immediately hydrolysed by water,... 

H02CC(H)(NH2)(CH2)3C(H)(NH2)C02H. M.p. at least 305"C. The o, l and meso forms are all isolated from hydrolysates of bacterial proteins. It is an intermediate in the biosynthesis of lysine in many bacteria. 

C4H6N2O2. Sublimes 260"C sparingly soluble in water hydrolysed by alkalis or mineral acids to glycylglycine. It and substituted dike-topiperazines are formed by the condensation of amino-acids, and are obtained in small quantities on the hydrolysis of proteins. 

C2He04S, Et0)(H0)S02. Oily acidic liquid. Soluble in water and slowly hydrolysed by it to ethanol and sulphuric acid. Prepared by passing ethene into concentrated sulphuric acid or by heating ethanol and sulphuric acid. Gives ethene when heated alone, and diethyl sulphate when heated with ethanol at 140 C. Forms crystalline metallic salts which are soluble in water. 

Fats are hydrolysed to glycerol and fatty acids by boiling with acids and alkalis, by superheated steam and by the action of lipases. If alkalis are used for hydrolysis, the fatty acids combine with the alkalis to form soaps. Alkaline hydrolysis is therefore sometimes called saponification. 

Sodium fluoroacetate, which is not volatile and not irritating to the skin, is used as a rodenticide. It is made from CH2ClC02Et and KF, which react to give ethyl fluoroacetate, which is then hydrolysed with NaOH in methyl alcohol. 

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