With Aqueous Base

Bis[4-dimethylaminophenyl] Tellurium Oxide 21.9 g (50 mmol) of thoroughly ground bis[4-dimethylaminophenyl] tellurium dichloride are slowly added to a stirred solution of 6.4 g (0.12 mol) of potassium hydroxide in 60 ml of water. The mixture is heated at 80°, stirred for some time, and cooled to 0 . The precipitate is filtered, washed several times with ice/water, dried over anhydrous calcium chloride for 48 h, and recrystallized from isopropanol/water (1/1) yield 13.2 g (69%) m.p. 217°. 

5-hydroxy-4-octyl phenyl tellurium oxide HjO (NaHCOj) decyl phenyl tellurium oxide Hp (NaHCOj)  

2-methoxycycloheptyl phenyl tellurium oxide H O (NaHCOj) diphenyl tellurium oxide (NaOH) bis[2-methylphenyl] tellurium oxide (NaOH) his[2,4,6-trimethylphenyl] tellurium oxide (nh,) bis[4-methoxyphenyl] tellurium oxide (KOH) bis[2-ethoxyphenyl] tellurium oxide (nHj) bis[3-chlorophenyl] tellurium oxide (KOH) bis[4-bromophenyl] tellurium oxide (KOH) bis[l-naphthyl] tellurium oxide (nHj) bis[4-hydroxyphenyl] tellurium oxide bis[4-hydroxy-3-methylphenyl] tellurium oxide (NaOH)  

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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... 

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... 

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. 

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). 

Metal- Working and Hydraulic Fluids. In the preparation of fluids for metal-working and hydrauflcs, the trend has been to replace organic-based materials with aqueous-based materials. Neodecanoic acid has found apphcation in these newer fluids as a corrosion inhibitor and a viscosity improver. For example, neodecanoic acid is used in an aqueous hydrauflc fluid concentrate for corrosion inhibition and improved antiwear properties (101), in the preparation of a thickened aqueous hydrauflc fluid to reduce viscosity loss (102), and in a water-soluble metal working oil to reduce corrosion (103). In a similar vein, neodecanoic acid has been used in antifreeze concentrates for corrosion inhibition (104). 

Oxygen ortho esters are readily cleaved by mild aqueous acid (TsOH Pyr, H20 NaHS04, 5 1 DME, H2O, 0°, 20 min ) to form esters that are then hydrolyzed with aqueous base to give the acid. Note that a trimethyl ortho ester is readily hydrolyzed in the presence of an acid-sensitive ethoxyethyl acetal. The order of acid stability is... 

These can be purified by extracting acidic and basic impurities with aqueous base or acid, respectively. However, they are somewhat sensitive to strong alkali which slowly cleaves the disulfide bond. TTie lower-melting members can be fractionally distilled under vacuum. The high members can be recrystallised from alcohol, toluene or glacial acetic acid. 

Hexafluoro-2-phenyl-2-propanol may be recovered from mother liquors, recovered solvent, and the KBr salt cake by extracting the mixture with aqueous base. Neutralization of the aqueous phase gives the alcohol (13-23 g.) which is purified by distillation. 

The mixture was stirred for 2 hours, heated at 60° to 70°C for 1 hour and poured into 2 liters of H O. The resulting suspension was extracted with ether, the ether layer separated and the ether removed under vacuum. A gummy mass remained which was dissolved in decalin and the solution was partly distilled to remove excess chlorobromide. After removal of most of the decalin under vacuum, the residue was treated with a large excess of N-( -hydroxyethyl)-piperazine and heated on a steam bath for 2 hours. This material was extracted with dilute aqueous HCI, this acid layer neutralized with aqueous base and the resulting oil extracted into ether. The ether layer was washed with water until the washings were neutral and dried over anhydrous potassium carbonate. On treatment with maleic acid in ether a yellow solid separated which was recrystallized from isopropanol. This yellow solid had MP 175° to 177°C. 

The reaction often works poorly unless an excess of the nucleophile is used because the product thiol can undergo a second S 2 reaction with alkyl halide to give a sulfide as a by-product. To circumvent this problem, thiourea, (NH2J2C=S, is often used as the nucleophile in the preparation of a thiol from an alkyl halide. The reaction occurs by displacement of the halide ion to yield an intermediate alkyl isothiourea salt, which is hydrolyzed by subsequent reaction with aqueous base. 

The biogenetic scheme for endiandric acids also predicts the plausible existence in nature of endiandric acids E (5), F (6), and G (7). Even though they are still undiscovered, their synthesis has been achieved (Scheme 6). For endiandric acids E and F, key intermediate 24 is converted, by conventional means, to aldehyde 35 via intermediate 34. Oxidation of 35 with silver oxide in the presence of sodium hydroxide results in the formation of endiandric acid E (5) in 90 % yield, whereas elaboration of the exo side chain by standard olefination (85 % yield) and alkaline hydrolysis (90 % yield) furnishes endiandric acid F (6). The construction of the remaining compound, endiandric acid G (7), commences with the methyl ester of endiandric acid D (36) and proceeds by partial reduction to the corresponding aldehyde, followed by olefination and hydrolysis with aqueous base as shown in Scheme 6. 

In the Payne rearrangement, a 2,3-epoxy alcohol is converted to an isomeric one, by treatment with aqueous base ... 

Cobalt catalysts such as HCo(CO)4 are widely used for hydroformyla-tion of higher alkenes, despite the higher temperatures and pressures required. The main reason for this is that these catalysts are also efficient alkene isomerization catalysts, allowing a mix of internal and terminal alkenes to be used in the process. Catalyst recovery is more of a problem here, involving production of some waste and adding significantly to the complexity of the process. A common recovery method involves treating the catalyst with aqueous base to make it water soluble, followed by separation and subsequent treatment with acid to recover active catalyst (4.3). 

C15-0016. When the reaction of methyl bromide with aqueous base was studied under isolation conditions, the following data were collected ... 

Triphenylsilanol is one of several products obtained in the thermally induced decarbonylation of Ph3SiC02H (129). Acylsilanes react readily with aqueous base for example, Ph3SiC(0)Ph affords Ph3SiOH and PhC(0)H when treated with aqueous sodium hydroxide solution (130). Similarly, hydrolysis of the allenyl silane 22 leads to the formation of 23 via the acylsilane 24 [Eq. (24)] (131). (For further examples of acylsilane chemistry, see Refs. 132-134.)... 

An aqueous base is the least expensive vehicle and poses no toxicity problems. A solution of the drug in water or water and cosolvent is made. Glycerin, glycols, natural and synthetic gums, and/or polymers are used to increase viscosity, cohesiveness, and plasticity. To overcome syneresis, or water separation in the gel, a common problem with aqueous bases, one can use absorbing materials such as microcrystalline cellulose, kaolin, colloidal silicon dioxide, starch, etc. 

Compound 56 is the first branch point intermediate in the analog syntheses, furnishing 90 upon oxidative cyclization with MnC>2 and deprotection with Mgl2. Intermediate 56 was also benzylated to protect the C5,C5 -naphthols in preparation for ester hydrolysis, which provided the next key branch point intermediate, bisacid 91. Ester hydrolysis here with aqueous base was surprising facile relative to intermediate 62, en route to (+)-calphostin D (Scheme 7.14). Presumably, the smaller C7,C7 -groups alleviate the steric gearing that hinders the reactivity of the C3,C3 -esters. 

Hydrolysis of isofervenulins 268 with aqueous base occurred at the C2—N3 bond to give A -carboxy-TV-methylcarbamoyltriazines 301, which were transformed to 268 by acidification of the reaction mixture. On the other hand, base-catalyzed hydrolysis of 268 gave imidazo[4,5-< ][l,2,4]tri-azines 302 (87KGS1555). Hydrolysis of the pyrimidotriazine derivatives with alkali gave the triazines 303 and 304 (77JPR522 87JPR290). 

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