With Alkali Metal Hydroxides

The carbon-tellurium bond linking tellurium to the perfluoroalkyl groups in perfluoroalkyl telluriums is cleaved by potassium hydroxide liberating fluorohydrocarbons.  

Butyl lithium, sec-butyl lithium, tert-butyl lithium, and phenyl lithium cleave Te-phenyl and Te-alkyl bonds in tetrahydrofuran at — 78°. These reactions, in which on organic group bonded to tellurium is exchanged for the organic group associated with the organic lithium compound, are useful for the preparation of organic lithium compounds that are otherwise available only with difficulty or not at all. 

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With alkali metal hydroxides, both N2O and N2 are formed in addition to the nitrite ... 

Solid super bases, prepared by successive treatment of y-alumina with alkali metal hydroxide and alkali metal, are highly active catalysts for reactions involving reactive carbanions, and have been commercialised by Sumitomo (Suzukamo et al, 1997). For example, t.vobutylbenzene, the. starting material for ibuprofen (see earlier) is produced by side-chain alkylation of toluene with propylene over a K/KOH/AI2O3 catalyst (Eqn. (14)). 

Interaction with alkali-metal hydroxides or carbonates may be explosive. Ammonia... 

The treatment of hydantoin derivatives (1293) with alkali metal hydroxide in boiling aqueous ethanol for 1 -2 hr gave orotic acid derivatives (1294) in good yields (82EUP52341). 

A further possibility for side-chain alkylation of toluene is oxidative methylation with methane. Catalysts with occluded alkali metal oxides, prepared by impregnating zeolites with alkali metal hydroxides followed by calcination, usually exhibit better performance.441 Further enhancement was achieved by impregnating ion-exchanged zeolites 442 Significant improvements in stability and the yields of Cg hydrocarbons were also observed when NaX was impregnated with 13% MgO which was found to increase the amounts of active sites.443... 

The primary and secondary alcohol functionalities have different reactivities, as exemplified by the slower reaction rate for secondary hydroxyls in the formation of esters from acids and alcohols (8). 1,2-Propylene glycol undeigoes most of the typical alcohol reactions, such as reaction with a free acid, acyl halide, or acid anhydride to form an ester reaction with alkali metal hydroxide to form metal salts and reaction with aldehydes or ketones to form acetals and ketals (9,10). The most important commercial application of propylene glycol is in the manufacture of polyesters by reaction with a dibasic or polybasic acid. 

Table VT contains a comprehensive list of known alkali metal hydroxide adducts. Complexes prepared by the interaction of carbohydrates or acetates of carbohydrates with alkali metal hydroxide in anhydrous alcoholic...

Adducts of Carbohydrates with Alkali Metal Hydroxides... 

In summary, the reaction between an alkali metal alkoxide and a poly-hydroxy compound in hot alcoholic media produces an alcoholate and, possibly, a small proportion of alkoxide adduct however, the conditions governing the ratio of alcoholate to adduct have not yet been well defined. Reactions with alkali metal hydroxides and cyanides produce mixtures (of alcoholate and adduct) that consist mainly of alcoholate. Occurrence of reactions between alkaline-earth metal hydroxides and polyhydroxy compounds in anhydrous alcoholic media has not been reported. 

Iodine dissolves without reaction in concentrated sulfuric acid and with concentrated nitric acid it reacts to form iodine pentoxide (47). Iodine reacts with alkali metal hydroxide solutions to form the corresponding hypoiodite and the rate of the reaction increases with the alkali concentration and temperature. At 50°C, the reaction is almost instantaneous ... 

Lactams or related cyclic, conformationally fixed amides are more readily N-alkylated than acyclic amides [96], As illustrated by the examples in Scheme 6.23, structurally elaborate alkylating agents can be used to alkylate lactams. During the workup of such reactions it should be kept in mind that four- and six-membered lactams are readily hydrolyzed by aqueous base (Scheme 3.8), and most lactams are also readily hydrolyzed by aqueous acids. Prolonged treatment of lactams with alkali metal hydroxides or acids during the work-up should therefore be avoided. 

Dihydrogen telluride is an acid in aqueous solution and is comparable in strength with phosphoric acid. Tellurols, especially arenetellurols, are expected to be at least as acidic as dihydrogen telluride. Therefore, tellurols should react easily with alkali metal hydroxides to form alkali metal tellurolates. Because tellurols are difficult to prepare, alkali metal tellurolates are best obtained by methods which avoid the tellurols. Sodium and lithium tellurolates are the most frequently used tellurolates. Although the tellurolates are not as sensitive to oxidation as the tellurols, tellurolates are almost always used in situ and are prepared and stored under nitrogen. Sodium benzenetellurolate was isolated as a moisture-and air-sensitive, grey powder. Its solutions in tetrahydrofuran or acetone were found to be stable for months when kept under nitrogen6. 

The water-gas shift reaction has also been studied under high pH with metal carbonyls as catalysts. The catalytic cycle with Fe(CO)5 as the precatalyst is shown in Fig. 4.6. This reaction with low turnover is carried out at 130-180°C, under 10-40 bar of CO, with alkali metal hydroxide as a promoter. 

The reduction of neutral carbonyls with alkali metal hydroxides or carbonates is an important route to HNCC dianions. In a few instances reduction of rhodium clusters has been reported to proceed further with oxidation of another CO. Examples are the formation of [Rh6(CO)i4] from [Rh6(CO)i5] 170) (Scheme 16) and the reduction of the dicarbide [Rhi2(C)2(CO)24] to give [Rhi2(C)2C023] 213). In the latter case, the unstable paramagnetic intermediate [Rh 12(0)2(00)23] has also been isolated upon slight alteration of the reaction conditions [Eqs. (32) and (33)]. 

The reactions in the decomposition of 13,6-trimethyl-2-oxo-l, 2-dihydropyrazine methiodide with alkali metal hydroxide to give 1,4,6-trimethyl-3-methylene-2-oxo-1,2,3,4-tetrahydropyrazine (1105) and its reaction with benzenediazonium chloride or phenylhydrazine to give l,4,6-trimethyl-2-oxo-3-phenylazomethylene-l,2,3,4-tetrahydropyrazine (1105,1132) have been described. 

The quinazolinepropionitrile 3-oxides 125 were cyclized with alkali metal hydroxide in aqueous alcohol to the pyrrolo[l,2-a]pyrimidine 4-oxides 126. ... 

A solid superbase whose basicity (H ) is higher than 37 has been prepared by the successive treatment of y -alumina with alkali metal hydroxide and alkali metal at 200-600t under nitrogen. The solid base has been found to be highly effective in the catalytic isomerization of olefinic double bonds and in the side-chain alkylation of alkylbenzenes with olefins. 

If we have a solution of pure carbonate then the consumption of strong acid at each titration stage is the same, whereas a carbonate solution polluted with alkali metal hydroxide is characterized by a higher consumption of acid for the first stage of the neutralization than for the second one the bicarbonate admixtures result in the inverse consumption of the acid for the stages mentioned. 

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