Bases aqueous

Phosphorous acid is water soluble and may be removed by washing the alkyl halide with water or with dilute aqueous base... 

In spite of S—H bonds being less polar than O—H bonds thiols are stronger acids than alcohols This is largely because S—H bonds are weaker than O—H bonds We have seen that most alcohols have pA s of 16-18 The corresponding value for a thiol IS about 10 The significance of this difference is that a thiol can be quantitatively con verted to its conjugate base (RS ) called an alkanethiolate, by hydroxide Conse quently thiols dissolve m aqueous base... 

Section 15 13 Thiols are compounds of the type RSH They are more acidic than alco hols and are readily deprotonated by reaction with aqueous base Thiols can be oxidized to sulfemc acids (RSOH) sulfimc acids (RSO2H) and sulfonic acids (RSO3H) The redox relationship between thiols and disul tides IS important m certain biochemical processes... 

Unlike Its acid catalyzed counterpart a halogenation m base cannot normally be limited to monohalogenation Methyl ketones for example undergo a novel polyhalo genation and cleavage on treatment with a halogen m aqueous base... 

Unlike Its acid catalyzed counterpart ester hydrolysis m aqueous base is irreversible O O... 

In aqueous base hydroxide ion abslracls a proton from Ihe carboxylic acid Isolalmg Ihe acid requires a subsequenl acidilicalion step... 

Section 20 17 Like ester hydrolysis amide hydrolysis can be achieved m either aque ous acid or aqueous base The process is irreversible m both media In base the carboxylic acid is converted to the carboxylate anion m acid the amine is protonated to an ammonium ion... 

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... 

The starting material for this process 24 5 trichlorophenol is made by treating 1 2 4 5 tetra chlorobenzene with aqueous base Nucleophilic... 

Carbohydrates undergo a number of isomerization and degradation reactions under both laboratory and physiological conditions For example a mixture of glucose fructose and mannose results when any one of them is treated with aqueous base This reaction can be understood by examining the consequences of enohzation of glucose... 

Cleavage reactions of carbohydrates also occur on treatment with aqueous base for prolonged periods as a consequence of base catalyzed retro aldol reactions As pointed out m Section 18 9 aldol addition is a reversible process and (3 hydroxy carbonyl com pounds can be cleaved to an enolate and either an aldehyde or a ketone... 

The p nitrophenol formed as a byproduct in this reaction is easily removed by extrac tion with dilute aqueous base Unlike free ammo acids and peptides protected peptides are not zwitteriomc and are more soluble m organic solvents than m water... 

Haloform reaction (Section 18 7) The formation of CHX3 (X = Br Cl or I) brought about by cleavage of a methyl ketone on treatment with Br2 CI2 or I2 in aqueous base... 

Soaps (Section 19 5) Cleansing substances obtained by the hydrolysis of fats m aqueous base Soaps are sodium or potassium salts of unbranched carboxylic acids having 12-18 carbon atoms... 

Fig. 28. Traditional duv-resist design using derivatives of polyhydroxystyrene. Monomer (a) contributes hydrophilic character to the polymer, and its acidic phenol group enhances aqueous base solubiUty monomer (b) provides acid-labile pendent groups.

The properties of SAN are significantly altered by water absorption (16). The equiUbrium water content increases with temperature while the time requited decreases. A large decrease in T can result. Strong aqueous bases can degrade SAN by hydrolysis of the nittile groups (17). 

Chlorendic Acid. Chlorendic acid [115-28-6] and its anhydride [115-27-5] are widely used flame retardants. Chlorendic acid is synthesized by a Diels-Alder reaction of maleic anhydride and hexachlorocyclopentadiene (see CyclopentadlENE and dicyclopentadiente) in toluene followed by hydrolysis of the anhydride using aqueous base (60). The anhydride can be isolated directly from the reaction mixture or can be prepared in a very pure form by dehydration of the acid. The principal use of chlorendic anhydride and chlorendic acid has been in the manufacture of unsaturated polyester resins. Because the esterification rate of chlorendic anhydride is similar to that of phthalic anhydride, it can be used in place of phthalic anhydride in commercial polyester... 

Triaryl phosphates are produced from the corresponding phenols (usually mixtures) by reaction with phosphoms oxychloride, usually in the presence of a catalyst (94—96). They are subsequently distilled and usually washed with aqueous bases to the desired level of purity. Tricresyl phosphate was originally made from petroleum-derived or coal-tar-derived cresyflc acids, ie, cresols, variously admixed with phenol and xylenols. Discovery of the toxicity of the ortho-cresyl isomers led manufacturers to select cresols having very Httle ortho-isomer. 

In aqueous solution, OF2 oxidizes HCl, HBr, and HI (and thek salts), Hberating the free halogens. Oxygen difluoride reacts slowly with water and a dilute aqueous base to form oxygen and fluorine. The rate of this hydrolysis reaction has been determined (23). 

Difluoroethanol is prepared by the mercuric oxide cataly2ed hydrolysis of 2-bromo-l,l-difluoroethane with carboxyHc acid esters and alkaH metal hydroxides ia water (27). Its chemical reactions are similar to those of most alcohols. It can be oxidi2ed to difluoroacetic acid [381-73-7] (28) it forms alkoxides with alkaH and alkaline-earth metals (29) with alkoxides of other alcohols it forms mixed ethers such as 2,2-difluoroethyl methyl ether [461-57-4], bp 47°C, or 2,2-difluoroethyl ethyl ether [82907-09-3], bp 66°C (29). 2,2-Difluoroethyl difluoromethyl ether [32778-16-8], made from the alcohol and chlorodifluoromethane ia aqueous base, has been iavestigated as an inhalation anesthetic (30,31) as have several ethers made by addition of the alcohol to various fluoroalkenes (32,33). Methacrylate esters of the alcohol are useful as a sheathing material for polymers ia optical appHcations (34). The alcohol has also been reported to be useful as a working fluid ia heat pumps (35). The alcohol is available ia research quantities for ca 6/g (1992). 

Protonolysis. Simple trialkylboranes are resistant to protonolysis by alcohols, water, aqueous bases, and mineral acids. In contrast, carboxyUc acids react readily with trialkylboranes, removing the first alkyl group at room temperature and the third one at elevated temperatures. Acetic and propionic acids are most often used. The reaction proceeds with retention of configuration of the alkyl group via a cycHc, six-membered transition state (206). 

The reaction of dihalocarbenes with isoprene yields exclusively the 1,2- (or 3,4-) addition product, eg, dichlorocarbene CI2C and isoprene react to give l,l-dichloro-2-methyl-2-vinylcyclopropane (63). The evidence for the presence of any 1,4 or much 3,4 addition is inconclusive (64). The cycloaddition reaction of l,l-dichloro-2,2-difluoroethylene to isoprene yields 1,2- and 3,4-cycloaddition products in a ratio of 5.4 1 (65). The main product is l,l-dichloro-2,2-difluoro-3-isopropenylcyclobutane, and the side product is l,l-dichloro-2,2-difluoro-3-methyl-3-vinylcyclobutane. When the dichlorocarbene is generated from CHCl plus aqueous base with a tertiary amine as a phase-transfer catalyst, the addition has a high selectivity that increases (for a series of diolefins) with a decrease in activity (66) (see Catalysis, phase-TRANSFEr). For isoprene, both mono-(l,2-) and diadducts (1,2- and 3,4-) could be obtained in various ratios depending on which amine is used. 

The bimodal profile observed at low catalyst concentration has been explained by a combination of two light generating reactive intermediates in equihbrium with a third dark reaction intermediate which serves as a way station or delay in the chemiexcitation processes. Possible candidates for the three intermediates include those shown as "pooled intermediates". At high catalyst concentration or in imidazole-buffered aqueous-based solvent, the series of intermediates rapidly attain equihbrium and behave kineticaHy as a single kinetic entity, ie, as pooled intermediates (71). Under these latter conditions, the time—intensity profile (Fig. 2) displays the single maximum as a biexponential rise and fall of the intensity which is readily modeled as a typical irreversible, consecutive, unimolecular process ... 

Various types of surface coating materials can be used with sohd fiber paperboard to achieve desired package properties. The coatings and treatments described for cormgated paperboard apply to sohd fiber paperboard as weU. Various solvent and aqueous-based polymeric emulsion coatings are also commonly used (see Emulsions). 

Hydrolysis is accelerated in the presence of strong acids. However, in the presence of aqueous bases such as sodium hydroxide, the rate of decomposition increases with increasing pH and teaches a maximum at the of the petoxycatboxyhc acid (ca 8.25), then decreases at higher pH (169,170). The basic decomposition products include the parent catboxyhc acid and singlet oxygen (171,172). Because the maximum rate of decomposition occurs at the p-K, the petoxycatboxyhc acid and its anion ate involved in the transition state (169). 

Methyl formate and propylene oxide have close boiling poiats, making separation by distillation difficult. Methyl formate is removed from propylene oxide by hydrolysis with an aqueous base and glycerol, followed by phase separation and distillation (152,153). Methyl formate may be hydrolyzed to methanol and formic acid by contacting the propylene oxide stream with a basic ion-exchange resia. Methanol and formic acid are removed by extractive distillation (154). 

N-Acylation is readily carried out by reaction of the alkaU metal salts with the appropriate acid chloride. C-Acylation of pyrroles carrying negative substituents occurs in the presence of Friedel-Crafts catalysts. Pyrrole and alkylpyrroles can be acylated noncatalyticaHy with an acid chloride or an acid anhydride. The formation of trichloromethyl 2-pyrryl ketone [35302-72-8] (20, R = CCI3) is a particularly useful procedure because the ketonic product can be readily converted to the corresponding pyrrolecarboxyUc acid or ester by treatment with aqueous base or alcohoHc base, respectively (31). 

A number of improvements have been made in these syntheses. For example, the use of ethanoHc ferric chloride and zinc chloride produces a good yield of 2-isopropylquinoline [17507-24-3] from isovaleraldehyde (46). The purification of 2-methylquinoline is facHitated through precipitation. A cmde quinaldine—hydrochloride and zinc chloride complex is prepared and then treated with aqueous base (47). 

Redox initiator systems are normally used in the emulsion polymerization of VDC to develop high rates at low temperatures. Reactions must be carried out below - 80° C to prevent degradation of the polymer. Poly(vinyHdene chloride) in emulsion is also attacked by aqueous base. Therefore, reactions should be carried out at low pH. 

Aqueous bases or nucleophiles have Httie impact on VDC polymers, primarily because the polymer is not wetted or swollen by water. However, these polymers do slowly degrade in hot concentrated aqueous sodium hydroxide solution (116). 

In general, the tetracyclines are yellow crystalline compounds that have amphoteric properties (Fig. 2) (15). They are soluble in both aqueous acid and aqueous base. The acid salts tend to be soluble in organic solvents such as 1-butanol, dioxane, and 2-ethoxyethanol In fact, 1-butanol is used to extract the salts from aqueous solution. 

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