Compounds Containing Other Functional Groups

Compounds containing the hydroxo group exhibit (OH), 6(MOH), and t (MO) at 3760-3000, 1200-700, and 900-300 cm respectively. As expected, these frequencies depend heavily on the strength of the hydrogen bond involved. References br typical hydroxo compounds are as follows [(CHj)2GaOHU (130), (CHj),SiOH (131), (CHjl SnOH (132), (CHj)4SbOH (133), and [(CHj)3PtOH]4 (108,134). The vibrational spectra of aquo com- 

As discussed in Sec. 111-18, metal hydrido complexes exhibit sharp v(MH) in the 2200-1700 cm region. Table lV-9 lists p(MH) and (/(MC) of typical 

Vibrational spectra of r-bonded complexes of alkenes and alkynes with transition metals have been reviewed by Davidson. In contrast to c-bonded complexes (Sec. lV-2), the C=C and C=C stretching bands of jr-bonded complexes show marked shifts to lower frequencies relative to those of free ligands. 

Ethylene and other olehns form r Complexes with transition metals. The simplest and best-studied complex is Zeise s salt, KtPt(C3H4)Clj] HjO. Several 

The assignments of the low-frequency modes of Zeise s salt have been controversial. According to Chatt et al., two types of bonding are involved 

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Since A,A -disubstituted hydrazines are readily available from a variety of sources (see Volume I, Chapter 14), their dehydrogenation constitutes a widely applicable route to both aliphatic and aromatic azo compounds. Such oxidative procedures are of particular value in the aliphatic series because so many of the procedures applicable to aromatic compounds, such as the coupling with diazonium salts, have no counterpart. The oxidation reactions permit the formation not only of azoalkanes, but also of a host of azo compounds containing other functional groups, e.g., a-carbonyl azo compounds [83], a-nitrile azo compounds [84], azo derivatives of phosphoric acid [85], phenyl-phosphoric acid derivatives [86],... 

Q Propose single-step and multistep syntheses of ketones and aldehydes from compounds containing other functional groups. 

By selective saponification of carboalkoxyl groups in the a- and other positions of the quinuclidine molecule it was possible to obtain for example a monoester (XX), e.g. by treatment of the diethylester of 3-carboxymethyl-quinuclidine-2-carboxylic acid (XIX) with water at room temperature. The same method was used in the S3mthesis of compounds containing other functional groups in positions 2 and 3 [95]. 

In compounds containing other functional groups of higher precedence, the presence of —OH is indicated by the prefix hydroxy-. 

The ozonolysis of cyclohexene to 1,6-dioxygenated compounds is shown in Figure 17.28. Other cycloalkenes similarly afford other l,y-dioxygenated cleavage products. With the three methods for workup (Figure 17.27), this ozonolysis provides access to 1,6-hexanediol, 1,6-hexanedial, or to 1,6-hexanedicarboxylic acid. Each of these compounds contains two functional groups of the same kind. 

However, good yields of ketones can be obtained for an equivalent quantity of acid halide per group attached to copper. Suitable conditions exist for the coupling of dialkylcuprates with acid chlorides which contain other functional groups (233), such as carbonyl, carboxy, and cyano. The order of reactivity of these groups towards organocopper compounds is CHO > CO > COgR > CN. Benzoyl fluoride reacts very slowly with lithium dimethylcuprate. 

Gilman reagents can even replace halogens in compounds that contain other functional groups. 

With the platinum-metal catalysts, this reaction can be suppressed by conducting the hydrogenation in acid solution or in acetic anhydride, which removes the amine from the equilibrium as its salt or as its acetate. For reactions with Raney nickel, where acid cannot be used, secondary amine formation is prevented by addition of ammonia. Hydrogenation of nitriles containing other functional groups may lead to cyclic compounds. For example, indoUzidine and quinoUzidine derivatives have been obtained in certain cases (7.21). 

Addition of a stabilizing entity into a chain will dramatically change molecular ion intensity. The aromatic nucleus and other conjugate systems are particularly notable in this respect as the radical site may be dispersed by conjugation over an extended part of the ion. Stabilization is also found in compounds containing unsaturated functional groups such as carbonyl, nitro, nitrite, and sulfonyl. 

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