Acids, aqueous

SchifT s bases A -Arylimides, Ar-N = CR2, prepared by reaction of aromatic amines with aliphatic or aromatic aldehydes and ketones. They are crystalline, weakly basic compounds which give hydrochlorides in non-aqueous solvents. With dilute aqueous acids the parent amine and carbonyl compounds are regenerated. Reduction with sodium and alcohol gives... 

For chemical processes, some examples are the elimination of aromatics by sulfonation, the elimination of olefins by bromine addition on the double bond (bromine number), the elimination of conjugated diolefins as in the case of the maleic anhydride value (MAV), and the extraction of bases or acids by contact with aqueous acidic or basic solutions. 

The data in Tables 4.2 and 4.3 refer to ions in aqueous acid solution for cations, this means effectively [MlHjO), ]" species. However, we have already seen that the hydrated cations of elements such as aluminium or iron undergo hydrolysis when the pH is increased (p. 46). We may then assume (correctly), that the redox potential of the system... 

Convert iron(ll) to iron(lll) in aqueous acid solution. 

Tin(IV) in aqueous acid gives a yellow precipitate with hydrogen sulphide, and no reaction with mercury(II) chloride. 

Oxygen is unaffected by aqueous acids unless they have powerful reducing properties when the acid is oxidised. For example... 

Hence the strength of the acid goes up as sulphur trioxide is dissolved in it. The acidity of pure and fuming sulphuric acids is not so apparent as in ordinary aqueous acids because it is masked by the oxidising and other properties moreover, the conductivity... 

The oxide MnO is obtained by heating the earbonate MnCOj, Oxidation of manganesedli in aqueous acid solution requires a strong oxidising agent, for example... 

Nickel is a moderately lustrous, silvery metal, and is extensively used in alloys (for example coinage, stainless steel) and for plating where a durable resistant surface is required. It is also used as an industrial catalyst, for example in the hydrogenation of unsaturated organic compounds. It is attacked by dilute aqueous acids but not by alkalis it combines readily with many non-metals on heating. 

Gently warm a mixture of 32 g. (32 ml.) of ethyl acetoacetate and 10 g. of aldehyde-ammonia in a 400 ml. beaker by direct heating on a gauze, stirring the mixture carefully with a thermometer. As soon as the reaction starts, remove the heating, and replace it when the reaction slackens, but do not allow the temperature of the mixture to exceed 100-no the reaction is rapidly completed. Add to the mixture about twice its volume of 2A -hydrochloric acid, and stir the mass until the deposit either becomes solid or forms a thick paste, according to the quality of the aldehyde-ammonia employed. Decant the aqueous acid layer, repeat the extraction of the deposit with more acid, and again decant the acid, or filter off the deposit if it is solid. Transfer the deposit to a conical flask and recrystallise it twice from ethanol (or methylated spirit) diluted with an equal volume of water. The i,4-dihydro-collidine-3,5-dicarboxylic diethyl ester (I) is obtained as colourless crystals, m.p. 130-131°. Yield 12 5 g,... 

Aqueous acid solution (R,). Render alkaline with 10-20% NaOH and distil. 

More information has appeared concerning the nature of the side reactions, such as acetoxylation, which occur when certain methylated aromatic hydrocarbons are treated with mixtures prepared from nitric acid and acetic anhydride. Blackstock, Fischer, Richards, Vaughan and Wright have provided excellent evidence in support of a suggested ( 5.3.5) addition-elimination route towards 3,4-dimethylphenyl acetate in the reaction of o-xylene. Two intermediates were isolated, both of which gave rise to 3,4-dimethylphenyl acetate in aqueous acidic media and when subjected to vapour phase chromatography. One was positively identified, by ultraviolet, infra-red, n.m.r., and mass spectrometric studies, as the compound (l). The other was less stable and less well identified, but could be (ll). 

Cydopentane reagents used in synthesis are usually derived from cyclopentanone (R.A. Ellison, 1973). Classically they are made by base-catalyzed intramolecular aldol or ester condensations (see also p. 55). An important example is 2-methylcydopentane-l,3-dione. It is synthesized by intramolecular acylation of diethyl propionylsucdnate dianion followed by saponification and decarboxylation. This cyclization only worked with potassium t-butoxide in boiling xylene (R. Bucourt, 1965). Faster routes to this diketone start with succinic acid or its anhydride. A Friedel-Crafts acylation with 2-acetoxy-2-butene in nitrobenzene or with pro-pionyl chloride in nitromethane leads to acylated adducts, which are deacylated in aqueous acids (V.J. Grenda, 1967 L.E. Schick, 1969). A new promising route to substituted cyclopent-2-enones makes use of intermediate 5-nitro-l,3-diones (D. Seebach, 1977). 

The cyclic carbonate of benzoin (4,5-diphenyl-l,3-dioxol-2-one, prepared from benzoin and phosgene) blocks both hydrogen atoms of primary amines after dehydration acid stable, easily crystallizable Sheehan oxazolinones are formed, which are also called Ox derivatives. The amine is quantitatively deblocked by catalytic hydrogenation in the presence of 1 equiv. of aqueous acid (J.C Sheehan, 1972, 1973 M.J. Miller, 1983). An intelligent application to syntheses of acid labile -lactams is given in the previous section (p. 161). 

Halogenation of 2-aminothiazole and derivatives has been reported under a wide variety of experimental conditions in water (161, 405. 406) in aqueous acids (16. 172, 407, 408) in solvents such as chloroform (27. 172), carbon disulfide (162, 166. 320. 409). benzene (165), acetic acid (410-413, 1580). or hydrochloric acid (414) or in 20% sulfuric acid (415-417). 

Attack on the halogen is probably the starting point of the reaction between A-4-thiazoline-2-thione and chlorine in aqueous acid solution to yield thiazole-2-sulfonylchloride. which then gives 2-chlorothjazole (153). 

The cyclization of a-thiocyanatoketones (183) in aqueous acid, concentrated sulfuric acid in acetic acid and water, or alkaline solution leads to 2-hydroxythiazoles after dilution in water. 

The yields with the lower alkyls rarely exceed 50%. For example, with R, =R2 = Me, the yield is 20% in an aqueous acidic solution (219) or 40% in an acetic solution acidified with sulfuric acid (369). 

Addition of water to the double bond of an alkene takes place in aqueous acid Addition occurs according to Mar kovnikov s rule A carbocation is an in termediate and is captured by a mole cule of water acting as a nucleophile... 

Step 1 The enol is formed in aqueous acidic solution The first step of its transformation to a ketone is proton transfer to the carbon-carbon double bond... 

The ketone is not isolated but reacts rapidly with the Grignard reagent to give after adding aqueous acid a tertiary alcohol Ketones are more reactive than esters toward... 

The mechanism of enolization involves two separate proton transfer steps rather than a one step process m which a proton jumps from carbon to oxygen It is relatively slow m neutral media The rate of enolization is catalyzed by acids as shown by the mechanism m Figure 18 1 In aqueous acid a hydronium ion transfers a proton to the carbonyl oxygen m step 1 and a water molecule acts as a Brpnsted base to remove a proton from the a car bon atom m step 2 The second step is slower than the first The first step involves proton transfer between oxygens and the second is a proton transfer from carbon to oxygen... 

Once the cyano group has been introduced the nitrile is subjected to hydrolysis Usually this is earned out m aqueous acid at reflux... 

On standing in dilute aqueous acid compound A is smoothly converted to mevalonolactone... 

Ester hydrolysis is the most studied and best understood of all nucleophilic acyl sub stitutions Esters are fairly stable in neutral aqueous media but are cleaved when heated with water m the presence of strong acids or bases The hydrolysis of esters m dilute aqueous acid is the reverse of the Eischer esterification (Sections 15 8 and 19 14)... 

Nitriles are classified as carboxylic acid derivafives because fhey are convened fo car boxylic acids on hydrolysis The condifions required are similar fo fhose for fhe hydrol ysis of amides namely healing m aqueous acid or base for several hours Like fhe hydrolysis of amides nilrile hydrolysis is irreversible m fhe presence of acids or bases Acid hydrolysis yields ammonium ion and a carboxylic acid... 

The ease with which amines are extracted into aqueous acid combined with their regeneration on treatment with base makes it a simple matter to separate amines from other plant materials and ni trogen containing natural products were among the earliest organic compounds to be studied Their basic... 

The product of this reaction is an imide (Section 20 16) a diacyl derivative of an amine Either aqueous acid or aqueous base can be used to hydrolyze its two amide bonds and liberate the desired primary amine A more effective method of cleaving the two amide bonds is by acyl transfer to hydrazine... 

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