Aqueous alkali

Cobaltilll) oxide is obtained as a brown precipitate Co Oj.aq when cobalt(II) hydroxide is oxidised in alkaline conditions (or when a cobalt(III) is decomposed by aqueous alkali). On heating it gives the black mixed oxide C03O4. 

This method has the great advantage over method (A) in that it can be applied in particular to those aromatic nitriles in which the aryl group is readily sulphonated clearly, it can also be applied to nitriles in which the alkyl or aryl portion contains groups which are in any other way affected by concentrated sulphuric acid, or by concentrated aqueous alkalis. 

Feebly basic amines, e.g., the nitroanilines, generally react so slowly with benzenesulphonyl chloride that most of the acid chloride is hydrolysed by the aqueous alkali before a reasonable yield of the sulphonamide is produced indeed, o-nitroaniline gives little or no sulphonamide under the conditions of the Hinsberg test. Excellent results are obtained by carrying out the reaction in pyridine solution ... 

Claisen-Schmidt reaction. Aromatic aldehydes condense with aliphatic or mixed alkyl-aryl ketones in the presence of aqueous alkali to form ap-unsaturated ketones ... 

The above are examples of the Claisen - Schmidt reaction. The formation of p-nitrostyrenes by reaction of nitroalkanes with aromatic aldehydes in the presence of aqueous alkali may be included under the Claisen- hmidt condensation ... 

Clalsen aldol condensation. This consists in the condensation of an aromatic aldehyde and an ester R—CHjCOOCjHj in the presence of finely divided sodium and a trace of alcohol at a low temperature. The catalyst is the alkoxide ion aqueous alkalis caimot be employed since they will hydrolyse the resulting ester. The product is an ap-unsaturated ester, for example ... 

Aromatic nitriles are generally liquids or low melting point solids, and usually have characteristic odours. They give no ammonia with aqueous sodium hydroxide solution in the cold, are hydrolysed by boiling aqueous alkali but more slowly than primary amides ... 

Dimethylpyrazole (III) may be prepared from acetylacetone (I) and hydrazine (II) (produced from hydrazine sulphate and aqueous alkali). The reaction may be represented as ... 

Aromatic aldehydes, and also aliphatic aldehydes containing no a-hydrogen atom, undergo the Cannizzaro reaction (see Section IV,123) when treated with aqueous alkali, for example ... 

The alkyl esters of sulphonlc acids exhibit properties similar to those of the alkyl sulphates, and are hydrolysed, by boiling with aqueous alkalis, to the alcohols and sulphonates. Thus with ethyl p-toluenesulphonate ... 

The reactivity of sulfathiazoles has been reviewed (65). Methylation in alkaline solution with dimethyl sulfate gives only the ring methylated derivative (85). Mixtures of products are obtained with diazomethane as alkylating agent (see p. 37). Other alkyl halides in aqueous alkali lead also to ring-alkylated products (85. 251, 650. 669-671). 

The reactions are carried out by warming the ester in an inert solvent such as chloroform or benzene with PjSj on the steam bath for 8 to 10 hr (Scheme 106). Products are isolated by ether extraction of the aqueous alkali-treated reaction mixture. 

Even small spills and leaks (<0.45 kg) require extreme caution. Unless the spill is contained in a fume hood, do not remain in or enter the area unless equipped with full protective equipment and clothing. Self-contained breathing apparatus should be used if the odor of acrolein or eye irritation is sensed. Small spills may be covered with absorbant, treated with aqueous alkalies, and flushed with water. 

Aqueous mineral acids react with BF to yield the hydrates of BF or the hydroxyfluoroboric acids, fluoroboric acid, or boric acid. Solution in aqueous alkali gives the soluble salts of the hydroxyfluoroboric acids, fluoroboric acids, or boric acid. Boron trifluoride, slightly soluble in many organic solvents including saturated hydrocarbons (qv), halogenated hydrocarbons, and aromatic compounds, easily polymerizes unsaturated compounds such as butylenes (qv), styrene (qv), or vinyl esters, as well as easily cleaved cycHc molecules such as tetrahydrofuran (see Furan derivatives). Other molecules containing electron-donating atoms such as O, S, N, P, etc, eg, alcohols, acids, amines, phosphines, and ethers, may dissolve BF to produce soluble adducts. 

Properties. HydroxyethjIceUulose [9004-62-0] (HEC), is a nonionic polymer. Low hydroxyethyl substitutions (MS = 0.05-0.5) yield products that are soluble only in aqueous alkali. Higher substitutions (MS > 1.5) produce water-soluble HEC. The bulk of commercial HEC falls into the latter category. Water-soluble HEC is widely used because of its broad compatibiUty with cations and the lack of a solution gel or precipitation point in water up to the boiling point. The MS of commercial HEC varies from about 1.8 to 3.5. The products are soluble in hot and cold water but insoluble in hydrocarbon solvents. HEC swells or becomes pardy to mosdy soluble in select polar solvents, usually those that are miscible with water. 

Physical properties of hexachloroethane are Hsted in Table 11. Hexachloroethane is thermally cracked in the gaseous phase at 400—500°C to give tetrachloroethylene, carbon tetrachloride, and chlorine (140). The thermal decomposition may occur by means of radical-chain mechanism involving -C,C1 -C1, or CCl radicals. The decomposition is inhibited by traces of nitric oxide. Powdered 2inc reacts violentiy with hexachloroethane in alcohoHc solutions to give the metal chloride and tetrachloroethylene aluminum gives a less violent reaction (141). Hexachloroethane is unreactive with aqueous alkali and acid at moderate temperatures. However, when heated with soHd caustic above 200°C or with alcohoHc alkaHs at 100°C, decomposition to oxaHc acid takes place. 

When large groups, such as phenyl, bromo, ethoxycarbonyl or nitro are attached at position 3, the principal products are l-alkylcinnolin-4(l/f)-ones. Cyanoethylation and acetylation of cinnolin-4(l/f)-one takes place exclusively at N-1. Phthalazin-l(2/f)-ones give 2-substituted derivatives on alkylation and acylation. Alkylation of 4-hydroxyphthala2in-l(2/f)-one with an equimolar amount of primary halide in the presence of a base leads to 2-alkyl-4-hydroxyphthalazin-l(2/f)-one and further alkylation results in the formation of 4-alkoxy-2-alkylphthalazinone. Methylation of 4-hydroxy-2-methyl-phthalazinone with dimethyl sulfate in aqueous alkali gives a mixture of 4-methoxy-2-methylphthalazin-l(2/f)-one and 2,3-dimethylphthalazine-l,4(2//,3//)-dione, whereas methylation of 4-methoxyphthalazin-l(2/f)-one under similar conditions affords only 4-methoxy-2-methylphthalazinone. 

The phenomenon of 5-hydroxymethylation is a standard case of electrophilic attack. Thus uracil (83 R = H) and paraformaldehyde in aqueous alkali furnish 5-hydroj(ymethyl-pyrimidine-2,4(l//,3//)-dione (83 R = CH20H) in good yield (59JA2521). Aromatic aldehydes react differentiy to yield 5-benzylidene derivatives of, for example, 1-methylbar-bituric acid (78CC764). 

Unlike simple alkyl halides, ethyl chloroformate appears to react with primary and secondary amino groups in any position to give directly the corresponding urethane, e.g. (258) (64JMC364). Such alkylations proceed in pyridine, aqueous alkali or even warm benzene (62JOC982). 

Most diaziridines are not sensitive towards alkali. As an exception, diaziridines derived from 2-hydroxyketones are quickly decomposed by heating with aqueous alkali. Acetaldehyde, acetic acid and ammonia are formed from (162). This reaction is not a simple N—N cleavage effected intramolecularly by a deprotonated hydroxy group, since highly purified hydroxydiaziridine (162) is quite stable towards alkali. Addition of small amounts of hydroxybutanone results in fast decomposition. An assumed reaction path — Grob fragmentation of a hydroxyketone-diaziridine adduct (163) — is in accord with these observations (B-67MI50800). 

A piperidinyl carbamate, stable to aqueous alkali and to cold acid (30% HBr, 25°. several hours), is best cleaved by reduction. 

Removal of acids from water-immiscible solvents by washing with aqueous alkali, sodium carbonate or sodium bicarbonate. 

Liquid carboxylic acids are first freed from neutral and basic impurities by dissolving them in aqueous alkali and extracting with diethyl ether. (The pH of the solution should be at least three units above the pKg of the acid, see pK in Chapter 1). The aqueous phase is then acidified to a pH at least three units below the pK of the acid and again extracted with ether. The extract is dried with magnesium sulfate or sodium sulfate and the ether is distilled off The acid is fractionally distilled through an efficient column. It can be further purified by... 

Ethyl p-nitrobenzoate [99-77-4] M 195.2, m 56 . Dissolved in diethyl ether and washed with aqueous alkali, then the ether was evaporated and the solid recrystd from EtOH. 

Ethyl trifluoromethanesulfonate [425-75-2] M 178.1, b 115 /atm, 118-120 /atm, d 1.378, Hp 1.336. The ester reacts slowly with H2O and aqueous alkali. If its IR has no OH bands (-3000 cm" ) then purify by redistillation. If OH bands are present then dilute with dry Et20 and shake (carefully) with aqueous NaHC03 until effervescence ceases, then wash with H2O and dry (MgSOa), filter, evaporate and distil the residue under slight vacuum then at atmospheric pressure in a N2 atmosphere. IT IS A POWERFUL ALKYLATING AGENT, AND THE FUMES ARE VERY TOXIC - CARRY ALL OPERATIONS IN AN EFFICIENT FUME CUPBOARD. [Gramstad and Hazeldine J Chem Soc 173 7956 Howells and McCown Chem Rev 77 69 1977.]... 

Isopropyl p-nitrobenzoate [13756-40-6] M 209.2, m 105-106 . Dissolved in diethyl ether, washed with aqueous alkali, then water and dried. Evapn of the ether and recrysln from EtOH gave pure material. 

Nitroso-l-napbthol-4-sulfonic acid (3H2O) [3682-32-4] M 316.3, m 142-146°(dec), pK ,t -6.3 (OH). Crystd from dilute HCl soln. Crystals were dried over CaCl2 in a vacuum desiccator. Also purified by dissolution in aqueous alkali and pptn by addition of water. Reagent for cobalt. 

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