Functional group patterns

When the target molecule has a carbonyl, always look to the alpha carbon for a potential disconnection site. The enolate nucleophile (alpha carbon) can react with a variety of electrophiles (ketone, aldehyde, ester, or a,P-unsaturated C=0) to give a variety of functional group patterns. 

Another technique is to use pattern recognition routines. Whereas QSAR relates activity to properties such as the dipole moment, pattern recognition examines only the molecular structure. It thus attempts to find correlations between the functional groups and combinations of functional groups and the biological activity. 

Arylthiazoles substituted by functional groups follow the same pattern as aromatic hydrocarbons. 

The value of alkyl halides as starting materials for the preparation of a variety of organic functional groups has been stressed many times In our earlier discussions we noted that aryl halides are normally much less reactive than alkyl halides m reactions that involve carbon-halogen bond cleavage In the present chapter you will see that aryl halides can exhibit their own patterns of chemical reactivity and that these reac tions are novel useful and mechanistically interesting... 

Figure 3.1 The reactions of ethylene and menthene with bromine. In both molecules, the carbon-carbon doublebond functional group has a similar polarity pattern, so both molecules react with Br2 in the same way. The size and complexity of the remainders of the molecules are not important.

The polarity patterns of some common functional groups are shown in Table 5.1. Carbon is always positively polarized except when bonded to a metal. 

Table 5.1 Polarity Patterns in Some Common Functional Groups...

An example of how information from fragmentation patterns can be used to solve structural problems is given in Worked Example 12.1. This example is a simple one, but the principles used are broadly applicable for organic structure determination by mass spectrometry. We ll see in the next section and in later chapters that specific functional groups, such as alcohols, ketones, aldehydes, and amines, show specific kinds of mass spectral fragmentations that can be interpreted to provide structural information. 

In the stochastic theory of branching processes the reactivity of the functional groups is assumed to be independent of the size of the copolymer. In addition, cyclization is postulated not to occur in the sol fraction, so that all reactions in the sol fraction are intermolecular. Bonds once formed are assumed to remain stable, so that no randomization reactions such as trans-esterification are incorporated. In our opinion this model is only approximate because of the necessary simplifying assumptions. The numbers obtained will be of limited value in an absolute sense, but very useful to show patterns, sensitivities and trends. 

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