Water reactions with organometallic

The reaction of isocyanates with alcohols and with water can be catalyzed by amines and by organometallic compounds. Tertiary amines, such as l,4-diazo-[2.2.2]-bicyclooctane (DABCO) or triethylamine, are particularly effective in promoting the isocyanate-water reaction, while organometallic complexes, such as dibutyltin dilaurate or stannous octoate, are very useful for catalyzing isocyanate-alcohol reactions. Numerous articles have been written on various aspects of the catalysis of isocyanate reactions and representative examples are cited in refs. 8-10. 

Acidity of Amides, Imides, and Sulfonamides Characteristic Reactions Reaction with Water Hydrolysis Reaction with Alcohols Reactions with Ammonia and Amines Reaction of Acid Chiorides with Salts of Carboxylic Acids Interconversion of Functional Derivatives Reactions with Organometallic Compounds 18.10 Reduction... 

Zirconium tetrachloride is instantly hydrolyzed in water to zirconium oxide dichloride octahydrate [13520-92-8]. Zirconium tetrachloride exchanges chlorine for 0x0 bonds in the reaction with hydroxylic ligands, forming alkoxides from alcohols (see Alkoxides, METAl). Zirconium tetrachloride combines with many Lewis bases such as dimethyl sulfoxide, phosphoms oxychloride and amines including ammonia, ethers, and ketones. The zirconium organometalLic compounds ate all derived from zirconium tetrachloride. 

Reaction of Nitriles with Organometallic Reagents Grignard reagents add to a nitrile to give an intermediate imine anion that is hydrolyzed by addition of water to yield a ketone. 

White phosphorus (15.5 g, 0.5 g-atom) was cut into approximately 0.1-g pieces under water, washed with acetone followed by ether, and then added in one portion to the reaction mixture. The reaction mixture consisted of 1.0 mol of phenyl lithium in 750 ml of diethyl ether. The exothermic reaction was continued by heating at reflux for 3 h. Water was then added to hydrolyze the remaining organometallic this resulted in the precipitation of a yellow solid. The solid was removed by filtration, and the two phases of the remaining liquid portion were separated. The aqueous portion was extracted with three 50-ml portions of diethyl ether, which were combined with the organic layer, dried over anhydrous sodium sulfate, and evaporated to give the product phenylphosphine in 40% yield. 

After isolation, the intermediate products were reacted with zinc in acetonitrile or a glyme solvent to provide the trifluorovinyl ether monomers. This reaction with zinc is also sensitive to the presence of protic substances in the reaction mixture, and forms the same tetrafluoroethyl ether by-product in an undesirable side reaction. The reaction of the 2-bromotetrafluoroethyl ether reactants with zinc involves the formation of zinc organometallic species as an intermediate, and this species is sensitive to hydrolysis by water or acidic substances (Figure 3.6). 

Water, alcohols, ethers, or amines can cause inhibition of ionic polymerization. However, these substances can act in different ways according to their concentration. For example, in polymerizations initiated by Lewis acids (BF3 with isobutylene) or organometallic compounds (aluminum alkyls), water in small concentrations behaves as a cocatalyst, but in larger concentrations as an inhibitor (reaction with the initiator or with the ionic propagating species). 

Alcohols, water and even acetic acid are useful solvents for some radical reactions. However, they cannot be employed with organometallics that are basic. Conversely, halocarbon solvents are popular for many types of ionic reactions but they are not generally useful for radical reactions. Chloroform and carbon tetrachloride (and to a lesser extent, dichloromethane) can interfere by donating either hydrogen or halogen atoms to intermediate radicals and they are used only in atom transfer reactions where the solvent is also a reagent. 

The Grignard reaction is often one of the first reactions encountered for the preparation of organometallic compounds. As such it provides a method for the conversion of an alkyl bromide to an alkane. From the example shown below it is seen that the overall oxidation level change from the organic reactants to the products is from 0 to —2, so a reduction has occurred. Magnesium is the reductant and is itself oxidized from 0 to +2 oxidation state. The actual reduction takes place in the first step of the process in which the C-Br bond is converted to a C-Mg-Br bond. The reaction with water is merely a hydrolysis that does not change the oxidation state of carbon. 

Unless otherwise known, the toxicides of lithium organometallic compounds should be regarded as those of lithium compounds and of organometallic compounds in general. The latter were discussed in Section 12.4. Lithium oxide and hydroxide are caustic bases, and they may be formed by the combustion of lithium organometallic compounds or by their reaction with water. 

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