The document discusses reaction intermediates and carbocations. Carbocations are carbon atoms with a positive charge that are formed when a carbon atom gains electrons from a more electronegative atom. Carbocations are stabilized by electron-donating groups, resonance, and planar configurations that allow for charge delocalization. The stability of carbocations increases in the order of tertiary > secondary > primary and tropylium is the most stable carbocation.
Copyright:
Attribution Non-Commercial (BY-NC)
Available Formats
Download as DOCX, PDF, TXT or read online from Scribd
The document discusses reaction intermediates and carbocations. Carbocations are carbon atoms with a positive charge that are formed when a carbon atom gains electrons from a more electronegative atom. Carbocations are stabilized by electron-donating groups, resonance, and planar configurations that allow for charge delocalization. The stability of carbocations increases in the order of tertiary > secondary > primary and tropylium is the most stable carbocation.
The document discusses reaction intermediates and carbocations. Carbocations are carbon atoms with a positive charge that are formed when a carbon atom gains electrons from a more electronegative atom. Carbocations are stabilized by electron-donating groups, resonance, and planar configurations that allow for charge delocalization. The stability of carbocations increases in the order of tertiary > secondary > primary and tropylium is the most stable carbocation.
Copyright:
Attribution Non-Commercial (BY-NC)
Available Formats
Download as DOCX, PDF, TXT or read online from Scribd
The document discusses reaction intermediates and carbocations. Carbocations are carbon atoms with a positive charge that are formed when a carbon atom gains electrons from a more electronegative atom. Carbocations are stabilized by electron-donating groups, resonance, and planar configurations that allow for charge delocalization. The stability of carbocations increases in the order of tertiary > secondary > primary and tropylium is the most stable carbocation.
Copyright:
Attribution Non-Commercial (BY-NC)
Available Formats
Download as DOCX, PDF, TXT or read online from Scribd
Download as docx, pdf, or txt
You are on page 1/ 5
REACTION INTERMEDIATES Introduction Majority of organic reactions take place via the formations of intermediates.
These intermediates are of transitory existence and take part in the reaction as soon as they are formed. Being very reactive, these cannot be isolated under normal reaction conditions. However, their structures are established by indirect means either chemically or spectroscopically, or sometimes by isolating them at very low temperature. For a clear understanding of the reaction mechanism, a thorough knowledge and understanding of the reaction intermediates is essential. CARBOCATIONS It is a common knowledge that in the heterolytic fission of a C-X bond in an organic molecule, if X is more electronegative than carbon atom, the takes away the bonding electron pair and becomes negatively changed (:X ).In this case an ion bearing a positive charge isalso produced. -
This positively changed species is a carbocation. For many these species were called carbonium ion. However, now they are referred to as carbocations. A carbocation is also defined as a carbon atom which is trivalent, contains an even number of electrons and carries a positive chang. The carbon atom in a carbocation is sp2 hybridized and it uses all its three hybridized orbitals for forming bonds with other atoms. The remaining pz, orbital is empty and is perpendicular to the plane of other three bonds. Acarbocation may be described as plant (trigonal coplanar) with bond angle of 120.Because carbocation assumes
a planar structure, its formation is inhibited in compounds which do not permit attainment of a planar geometry as in bridge head compounds.
Stability of carbocations If an electron releasing group such as alkyl group is resent adjacent to the carbon atom bearing positive change, then the stability of the carbocation increases. This explains why a tertiary carbocation is more stable then a secondary carbocation which in turn is more stable than a primary carbocation. Thus, ethyl carbocation(CH3CH2 )is more stable than methyl carbocation (CH3 ). + +
Two factors are deemed to play a role in this case:(i) electron-donating inductive effect of alkyl group, the more alkyl groups attached to the C, the greater is the stabilizing effect and (ii) by hyperconjugation some change delocalization occurs between the p orbital of positively charged carbon and o bond of the b C-H. However, the presence of electron attacting group the carbocation less stable. Thus, O2NCH2CH2 is less stable than CH3CH2CH2+ The stability of a carbocation can aiso be explained by resonance. By resonance the positive change on the carbocation. The more the canonical structures for a +
carbocation, the more stable it wil be. The explains why benzyl carbocation (C6H5CH2+)and carbocations are more stable than propyl carbocation (CH3CH2CH2+)
The basic requirement for a carbocation to be stable is it should be planer, as it is only in this configuration that effective delocalization can occur. Also on basis of quantum mechanical calculations for simple alkyl carbocations it has been found that the planer (sp2) configuration is more stable than the pyramidal (sp3)configuration by about 84 KJ (20kcal)mol-1. The difficulty in the formation of carbocations increases as the attainment of planarity is inhibited. As an
illustration, 1-bromotritycene is very resistance to SN1 attack. This is attributed to the assume planar configuration of carbocation. The planr configuration of simple carbications has been confirmed by NMR analysis and ir spectra.
Some carbocations are very stable and so can be isolated and studied. The stability of such carbications is explained in terms of resonance, i.e, the positive change on the carbon is distributed uniformly throughout a number of structures.
In other words a number of canonical strures are possible. The most common example is of triarylmethyl carbocarion (e.g., triphenylmethyl carbocation). In certain cases, the carbocations are so stable that their solid salts have been isolated. For example, triphenylmethyl perchlorate exists as crystalline solid and tropylium bromide has been isolated as a yellow solid. The tropylium bromide stabilized by aromatization. The tropylium cation is planar 6 electrons like benzene.
The order of some carbocations is viven below: Tropylium > (c6H5)3c+ < c6H5+cH2 > ch2=Ch-c+H2
Tertiary butyl > lsopropyl > Ethyl > methyl Carbocation caebocation carbocation carbocation The stability of carbocations is increased due to or more of following reasons.
(i)
When the positrive carbon is in conjugation with a double bond the stability of carbocation is grater due to increased delocalization of positive change, which spreads over two atoms instead of being concentrated on one. Conjugated dienes in concentrated sulfuric give stable allyice type carbocations.
(ii)The carbocation stability is also increased due to the presence of heteroatom having an unshared pair of electrons, e.g., oxygen nitrogen or halogen, adjacent to the cationic centre. Such carbocations are stabilized by resonance.
The methoxymethyl cation is obtained as stable solid MeOCH2 +SbF4
