Functional group, carbon

If the functional group is a carbon species [i.e. —C=C—, —C=N, —CHO, —COR, —C02H(R)], then a possible disconnection point would be the bond uniting the a-carbon to the functional group carbon, as is found with alkynes (Section 5.3), aldehydes (Section 5.7), ketones (Section 5.8), carboxylic acids (Section 5.11) or their derived esters (Section 5.12.3, p. 695). Alternative disconnection points which would be worth considering are the a, / - and / , y-carbon bonds, in for example aldehydes or ketones. 

Molecular formula, functional groups, carbon skeleton. 

Where and what are Where is the primary How many the substituents functional group carbons ... 

The oxidation states of the functional group carbon (indicated in bold) are ... 

CNTs contain many types of defects and impurities [45]. These may include (but are not limited to) NP catalyst impurities, other carbon allotrope impurities, oxygen-containing functional groups, carbon vacancies, Stone-Wales defects, and other kinds of odd-numbered rings in sidewalls causing... 

Next, an attempt was made to evaluate the quantitative importance of the various reaction schemes [19]. To this effect, a printed compilation of 1900 reactions dealing with the introduction of one carbon atom bearing a functional group [20] was analyzed and each reaction assigned manually to a corresponding reaction scheme. The results are Hsted in Table 3-3. 

Structural keys describe the chemical composition and structural motifs of molecules represented as a Boolean array. If a certain structural feature is present in a molecule or a substructure, a particular bit is set to 1 (true), otherwise to 0 (false). A bit in this array may encode a particular functional group (such as a carboxylic acid or an amidelinkage), a structural element (e.g., a substituted cyclohexane), or at least n occurrences of a particular element (e.g., a carbon atom). Alternatively, the structural key can be defined as an array of integers where the elements of this array contain the frequency of a specific feature in the molecule. 

The success of the last reaction depends upon the inertness of the ester carbonyl groups towards the organocadmium compound with its aid and the use of various ester acid chlorides, a carbon chain can be built up to any reasonable length whilst retaining a reactive functional group (the ester group) at one end of the chain. Experimental details are given for l-chloro-2-hexanone and propiophenone. The complete reaction (formation of ketones or keto-esters) can be carried out in one flask without isolation of intermediates, so that the preparation is really equivalent to one step. 

This reference work differs from Beilstein in that it is baaed upon structural formulae and compounds are grouped according to the carbon skeleton rather than the functional group the latter system has the advantage that closely related compounds are grouped together. The volumes are not published in numerical order but rather on the basis of fields of current interest. They are a valuable supplement to Beilstein. The volumes which have been published to date (1955) are ... 

Have you noticed that the disconnections involving H" are simply redox reactions and do not alter the carbon skeleton of the molecule They are not then reaUy discoimections at all but Functional Group Interconversions or FGI for short. 

The next example uses another carbon electrophile how can you use the relationship of the two functional groups in TM 249 to design a synthesis of the molecule ... 

In order for the transferability of parameters to be a good description of the molecule, force fields use atom types. This means that a sp carbon will be described by different parameters than a. sp - carbon, and so on. Usually, atoms in aromatic rings are treated differently from sp atoms. Some force fields even parameterize atoms for specific functional groups. For example, the carbonyl oxygen in a carboxylic acid may be described by different parameters than the carbonyl oxygen in a ketone. 

There is one semiempirical program, called HyperNMR, that computes NMR chemical shifts. This program goes one step further than other semiempiricals by defining different parameters for the various hybridizations, such as sp carbon vs. sp carbon. This method is called the typed neglect of differential overlap method (TNDO/1 and TNDO/2). As with any semiempirical method, the results are better for species with functional groups similar to those in the set of molecules used to parameterize the method. 

In the synthesis of molecules without functional groups the application of the usual polar synthetic reactions may be cumbersome, since the final elimination of hetero atoms can be difficult. Two solutions for this problem have been given in the previous sections, namely alkylation with nucleophilic carbanions and alkenylation with ylides. Another direct approach is to combine radical synthons in a non-polar reaction. Carbon radicals are. however, inherently short-lived and tend to undergo complex secondary reactions. Escheirmoser s principle (p. 34f) again provides a way out. If one connects both carbon atoms via a metal atom which (i) forms and stabilizes the carbon radicals and (ii) can be easily eliminated, the intermolecular reaction is made intramolecular, and good yields may be obtained. 

Before we start with a systematic discussion of the syntheses of difunctional molecules, we have to point out a formal difficulty. A carbonmultiple bond is, of course, considered as one functional group. With these groups, however, it is not clear, which of the two carbon atoms has to be named as the functional one. A 1,3-diene, for example, could be considered as a 1,2-, 1,3-, or 1,4-difunctional compound. An a, -unsaturated ketone has a 1.2- as well as a 1,3-difunctional structure. We adhere to useful, although arbitrary conventions. Dienes and polyenes are separated out as a special case. a, -Unsaturated alcohols, ketones, etc. are considered as 1,3-difunctional. We call a carbon compound 1,2-difunctional only, if two neighbouring carbon atoms bear hetero atoms. 

Regioselectivity of C—C double bond formation can also be achieved in the reductiv or oxidative elimination of two functional groups from adjacent carbon atoms. Well estab llshed methods in synthesis include the reductive cleavage of cyclic thionocarbonates derivec from glycols (E.J. Corey, 1968 C W. Hartmann, 1972), the reduction of epoxides with Zn/Nal or of dihalides with metals, organometallic compounds, or Nal/acetone (seep.lS6f), and the oxidative decarboxylation of 1,2-dicarboxylic acids (C.A. Grob, 1958 S. Masamune, 1966 R.A. Sheldon, 1972) or their r-butyl peresters (E.N. Cain, 1969). 

Mono and oligocyclic carbon compounds are listed in order of increasing ring size. The lists are further subdivided in the same order of functional groups as described in section 3.1.2. 

Another feature of the Pd—C bonds is the excellent functional group tolerance. They are inert to many functional groups, except alkenes and alkynes and iodides and bromides attached to sp carbons, and not sensitive to H2O, ROH, and even RCO H. In this sense, they are very different from Grignard reagents, which react with carbonyl groups and are easily protonated. 

---