Hydrolysis acetonitrile

By the action of concentrated hydrochloric acid at about 40° upon aryl-acetonitriles hydrolysis is arrested at the arylacetamide stage (see Section IV, 160 for the preparation of phenylacetamide by this method) ... 

Nitroxyl mediated electro-oxidation of primary amines also leads to formation of the imine and the further oxidation to the nitrile. In anhydrous acetonitrile containing 2,6-lutidine as a base, the nitrile is formed. In aqueous acetonitrile, hydrolysis of the imine intermediate is fast and good yields of the aldehyde result... 

Table 2. (i-Acetylamino Mercury(n) Chlorides by Reaction of Alkenes with Hg(NOs)2 and Acetonitrile, Hydrolysis and Treatment with Sodium Chloride32... 

Laboratory studies have provided evidence that photochemical and photocatalytic (Section 6.8) steps might play an important role in the formation of amino acids or various heterocyclic compounds from very simple molecules. For example, UVC irradiation of acetonitrile ammonia water mixture produces hexamethylenetetramine, a potential precursor of amino acids, via two-step photoinitiated fragmentation of acetamide (formed by acetonitrile hydrolysis) to give carbon oxide, which undergoes further photochemical and dark reactions (Scheme 6.184).1183... 

Hydrolysis of Acetonitrile. Nitriles, like acid amides, undergo hydrolysis to give the corresponding carboxylic acid and ammonia. Consequently... 

Boil a mixture of 5 ml. (4 g.) of acetonitrile and 75 ml. of 10% aqueous sodium hydroxide solution in a 200 ml. flask under a refluxwater-condenser for 30 minutes, when hydrolysis will be complete. Detach the condenser and boil the solution in the open flask for a few minutes to drive off ull free ammonia. Then cool the solution, and add dilute sulphuric acid (i volume of concentrated acid 2 volumes of water)... 

For practice, the student should carry out both alkaUne (compare Section 111,83) and acid hydrolysis of acetonitrile, n-valeronitrile (n-butyl cyanide) and n-capronitrile (n-amyl cyanide). 

Allylalion of the alkoxymalonitrile 231 followed by hydrolysis affords acyl cyanide, which is converted into the amide 232. Hence the reagent 231 can be used as an acyl anion equivalent[144]. Methoxy(phenylthio)acetonitrile is allylated with allylic carbonates or vinyloxiranes. After allylation. they are converted into esters or lactones. The intramolecular version using 233 has been applied to the synthesis of the macrolide 234[37]. The /i,7-unsaturated nitrile 235 is prepared by the reaction of allylic carbonate with trimethylsilyl cyanide[145]. 

Fig. 12. Tryptic map of it-PA (mol wt = 66,000) showing peptides formed from hydrolysis of reduced, alkylated rt-PA. Separation by reversed-phase octadecyl (C g) column using aqueous acetonitrile with an added acidic agent to the mobile phase. Arrows show the difference between A, normal, and B, mutant rt-PA where the glutamic acid residue, D, has replaced the normal arginine residue, C, at position 275.

Adamantylamine is prepared from the corresponding alcohol or bromide by bridgehead cation generation in the presence of acetonitrile (49). Selective hydrolysis of the resultant acetamide to the rigid cycloahphatic amine by acid or base is difficult. 

Hydrolysis of TEOS in various solvents is such that for a particular system increases directiy with the concentration of H" or H O" in acidic media and with the concentration of OH in basic media. The dominant factor in controlling the hydrolysis rate is pH (21). However, the nature of the acid plays an important role, so that a small addition of HCl induces a 1500-fold increase in whereas acetic acid has Httie effect. Hydrolysis is also temperature-dependent. The reaction rate increases 10-fold when the temperature is varied from 20 to 45°C. Nmr experiments show that varies in different solvents as foUows acetonitrile > methanol > dimethylformamide > dioxane > formamide, where the k in acetonitrile is about 20 times larger than the k in formamide. The nature of the alkoxy groups on the siHcon atom also influences the rate constant. The longer and the bulkier the alkoxide group, the lower the (3). 

Hydrolysis of esters and amides by enzymes that form acyl enzyme intermediates is similar in mechanism but different in rate-limiting steps. Whereas formation of the acyl enzyme intermediate is a rate-limiting step for amide hydrolysis, it is the deacylation step that determines the rate of ester hydrolysis. This difference allows elimination of the undesirable amidase activity that is responsible for secondary hydrolysis without affecting the rate of synthesis. Addition of an appropriate cosolvent such as acetonitrile, DMF, or dioxane can selectively eliminate undesirable amidase activity (128). 

Glycine ethyl ester hydrochloride has been prepared by the action of absolute alcohol and hydrogen chloride on glycine from glycyl chloride and alcohol by the action of ammonia or hexamethylenetetramine on chloroacetic acid, and subsequent hydrolysis with alcoholic hydrochloric acid and by the action of hydrogen chloride and alcohol on methyleneamino-acetonitrile. ... 

The formation of ethyl cyano(pentafluorophenyl)acetate illustrates the intermolecular nucleophilic displacement of fluoride ion from an aromatic ring by a stabilized carbanion. The reaction proceeds readily as a result of the activation imparted by the electron-withdrawing fluorine atoms. The selective hydrolysis of a cyano ester to a nitrile has been described. (Pentafluorophenyl)acetonitrile has also been prepared by cyanide displacement on (pentafluorophenyl)methyl halides. However, this direct displacement is always aecompanied by an undesirable side reaetion to yield 15-20% of 2,3-bis(pentafluoro-phenyl)propionitrile. 

Hydrolysis of 2-perfluoroalkylethyl iodides in the presence of nitrites also gives 2-perfluoroalkylethanols [5/] (equation 51). A variety of solvents can be used, but acetonitrile appears the most effective. Solvents can be avoided by using a betaine surfactant as a phase-transfer catalyst. 

By using imidazole catalysis, it is possible to get a better understanding of the active forms that water takes in enzymatic processes Thus, at low concentrations m the presence of an enzyme, the water may not be fully hydrogen bonded and therefore more reactive [61] The rate of hydrolysis of p-nitrotrifluoroacetanilide in acetonitrile shows a strong dependence on water concentration at low levels in the presence of imidazole The imidazolium complex is the approximate transition state (equation 60)... 

The kinetics of alkaline hydrolysis of phenyl cinnamate were studied at 25°C, in solutions containing 0.8% acetonitrile ionic strength, 0.3 M initial ester, 8.19 X 10- M reaction followed spectrophotometrically in 5-cm cells at 295 nm. For studies at three pH values, these absorbance data were obtained. The pH was established with sodium hydroxide of the normality specified in the heading of the table (as titrimetrically determined). 

Figure 6-8. pH-rate profile for the hydrolysis of p-nitrophenyl acetate at 25°C in aqueous solution containing 1% acetonitrile. Ionic strength = 0.1 M except at pH 0. 

Thus, simple ketones or aliphatic aldehydes may be successfully used as starting materials in the CSIC (Carbanion mediated Sulfonate Intramolecular Cyclization) reaction. Ai-alkylsulfonamides could be also cyclized under CSIC conditions (99T(55)7625) affording the spiroisothiazoline 79. By treatment with TMSCl, Nal in acetonitrile at r.t., hydrolysis of the enamine and formation of the corresponding keto derivative 80 was obtained. 

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