Organometallic compounds with nitriles

Several other preparative methods, involving the condensation of (i) N-(trimethylsUyl)phosphinimines and carbonyl compounds and (ii) organometallic reagents with nitriles followed by quenching with chlorotrimethylsilane, have been used for the preparation of other aldehyde- and ketone-derived... 

The most general synthetic route to ketones uses the reaction of carboxylic acids (or their derivatives) or nitriles with organometallic compounds (M.J. Jorgenson, 1970). Lithium car-boxylates react with organolithium compounds to give stable gem-diolates, which are decom-... 

The classes listed in Table 1-12 are families which exhibit the same regularity of boiling points, melting points, densities, and other properties seen in the hydrocarbon families we have already studied. Some of the families are named with characteristic suffixes while others have prefixes, or even separate words-in the names. For instance, alcohols are named with the suffix -ol. Ketones are named with the suffix -one. Amine and nitriles are named with the full suffix according to the family name. Ethers and halides usually have the full family name as a separate word, and nitro- and organometallic compounds have the prefix nitro- or the prefix corresponding to the hydrocarbon part of the organometallic molecule. 

Not only alkenes and arenes but also other types of electron-rich compound can be oxidized by oxygen. Most organometallic reagents react with air, whereby either alkanes are formed by dimerization of the metal-bound alkyl groups (cuprates often react this way [80]) or peroxides or alcohols are formed [81, 82]. The alcohols result from disproportionation or reduction of the peroxides. Similarly, enolates, metalated nitriles, phenolates, enamines, and related compounds with nucleophilic carbon can react with oxygen by intermediate formation of carbon-centered radicals to yield dimers (Section 5.4.6 [83, 84]), peroxides, or alcohols. The oxidation of many organic compounds by air will, therefore, often proceed faster in the presence of bases (Scheme 3.21). 

The aryl unit of these species shows carbanionic properties and consequently reacts with electrophiles. As a result, these organometallic reagents are of great value for the synthesis of a wide range of aromatic compounds. In particular, reaction with carbon electrophiles such as carbonyl compounds and nitriles results in the formation of a new carbon-carbon bond. 

Transition-metal hydrides react with nitrogen compounds to form N—H bond-containing organometallic products. The [HFe3(CO),J cluster anion reacts with nitriles to form a coordinated RCNH species, along with the RCHN-coordinated isomer ... 

Complexes of organotin with amidines have been found to be excellent catalysts for the preparation of polyurethane foams, which do not have the disadvantage of any amine odor and, in addition, delayed onset of the isocyanate-hydroxyl reaction An example of a mercapto-delayed organotin catalyst is 2,2,4,4-tetrakis(alkyl)- l,3,2,4-dithia-stannetane.55 Amine salts of amino acids, tertiary amino acids, and tertiary amino acid-nitrile compositions, have been found to be effective as delayed action catalysts for polyurethane synthesis. They are particularly effective when used in combination with an organometallic compound, such as an organotin. ... 

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