Electron release

Carbocations are stabilized by alkyl substituents attached directly to the positively charged carbon Alkyl groups are electron releasing sub stituents Stability increases in the order... 

Section 5 6 Electron release from alkyl substituents stabilizes a double bond In gen eral the order of alkene stability is... 

In general alkyl substituents increase the reactivity of a double bond toward elec trophilic addition Alkyl groups are electron releasing and the more electron rich a dou ble bond the better it can share its tt electrons with an electrophile Along with the observed regioselectivity of addition this supports the idea that carbocation formation rather than carbocation capture is rate determining... 

As shown m Table 6 4 electron releasing alkyl groups on the double bond increase the rate of epoxidation This suggests that the peroxy acid acts as an electrophilic reagent toward the alkene... 

A vinyl group is an extremely effective electron releasing substituent Resonance of the type shown delocalizes the rr electrons of the double bond and disperses the pos itive charge... 

A methyl group is an electron releasing substituent and activates all of the ring carbons of toluene toward electrophilic attack The ortho and para positions are activated more than the meta positions The relative rates of attack at the various positions m toluene compared with a single position m benzene are as follows (for nitration at 25°C)... 

Unlike a methyl group which is slightly electron releasing a trifluoromethyl group is a powerful electron withdrawing substituent Consequently a CF3 group destabilizes a car bocation site to which it is attached... 

Sections How substituents control rate and regioselectivity m electrophilic aro 12 10-12 14 matic substitution results from their effect on carbocation stability An electron releasing substituent stabilizes the cyclohexadienyl cation inter mediates corresponding to ortho and para attack more than meta... 

The carbonyl carbon of a ketone bears two electron releasing alkyl groups an aldehyde carbonyl group has only one Just as a disubstituted double bond m an alkene is more stable than a monosubstituted double bond a ketone carbonyl is more stable than an aldehyde carbonyl We 11 see later m this chapter that structural effects on the relative stability of carbonyl groups m aldehydes and ketones are an important factor m then rel ative reactivity... 

The mechanism for formation of benzaldehyde diethyl acetal which proceeds m two stages is presented m Figure 17 9 The first stage (steps 1-3) involves formation of a hemiacetal m the second stage (steps 4-7) the hemiacetal is converted to the acetal Nucleophilic addition to the carbonyl group characterizes the first stage carbocation chemistry the second The key carbocation intermediate is stabilized by electron release from oxygen... 

Both parts of the Lapworth mechanism enol formation and enol halogenation are new to us Let s examine them m reverse order We can understand enol halogenation by analogy to halogen addition to alkenes An enol is a very reactive kind of alkene Its carbon-carbon double bond bears an electron releasing hydroxyl group which makes it electron rich and activates it toward attack by electrophiles... 

Electron release from the substituent X not only stabilizes the carbonyl group it decreases the positive character of the carbonyl carbon and makes the carbonyl group less electrophilic... 

Electron release from nitrogen stabilizes the carbonyl group of amides and decreases the rate at which nucleophiles attack the carbonyl carbon... 

Electron releasing substituents attached to the ring have a negligible effect on the acidity of phenols Strongly electron withdrawing groups increase the acidity The compound 4 nitro 3 (tnfluoromethyl)phenol for example is 10 000 times more acidic than phenol... 

Impact of excited atoms onto the cathode (similar to the electron release caused by ions)... 

The electron-releasing R group helps stabilize this cation. As with anionic polymerization, the separation of the ions and hence the ease of monomer insertion depends on the reaction medium. The propagation reaction may be written as... 

Aromatics containing electron releasing groups such as phenols, dim ethyl am in oben 2en e and indole are formylated by 2-ethoxy-l,3-dithiolane in the presence of boron trifluoroetherate, followed by hydrolysis (114). The preformed dithiolanium tetrafluoroborate also undergoes Friedel-Crafts reaction with aromatics such as dim ethyl am in oben 2en e and indole (115), and was used to generate dithiolanium derivatives (formyl precursors) from the enoltrimethylsilyl ether derivatives (116). 

The following rules pertain to electrophilic substitution in pyrroles (35) (/) an electron-withdrawing substituent in the a-position directs substitution to the P and a -positions, (2) an electron-releasing substituent in the a-position directs substitution to the neighboring -position or to the a -position, (J) an electron-withdrawing substituent in the -position leads to substitution in the a -position, and (4) an electron-releasing substituent in the P-position tends to direct substitution into the neighboring a-position. 

Fig. 4. Schematic of a multisequence biosensor in which the target glucose is first converted to glucose-6-phosphate, G6P, in the test solution by hexokinase. G6P then reacts selectively with glucose-6-phosphate dehydrogenase immobilized on the quartz crystal surface. Electrons released in the reaction then chemically reduce the Pmssian blue film (see Fig. 3), forcing an uptake of potassium ions. The resulting mass increase is manifested as a...

In general, electron-releasing substituents cause a bathochromic shift of the n band... 

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