Aromaticity, Hรผckel's Rule & Craig's Rule for UGC CSIR-NET GATE IIT JAM/ Aromatic, Antiaromatic, Nonaromatic, homoaromaticity Quasi-aromatic compounds

Aromaticity explain by Hรผckel's Rule and Craig's Rule for UGC CSIR-NET GATE IIT JAM TIFR DRDO BARC Chemistry. 
    Application of Aromatic, Nonaromatic, Antiaromatic, Homoaromaticity & Quasi-aromatic compounds for competitive examination. 
    Application of Aromaticity with PDF file.


 


Basic Concepts
of Aromaticity // 
Aromatic, Nonaromatic, Antiaromatic compounds. 
Quasi-aromatic & homoaromaticity. 
Aromaticity Based on Hรผckel's Rule. 
Application of Aromaticity. 






๐ŸŽฆ  Aromaticity  ๐Ÿ‘‰ Part 1
๐ŸŽฆ Aromaticity  ๐Ÿ‘‰ Part 2

๐Ÿ“š  PDF File also available ๐Ÿ‘‰๐Ÿ‘‰ Click Here 

  Order  Stability and Resonance Energy:-  Aromatic > Homoaromatic > Antiaromatic > Nonaromatic



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   Aromaticity:- in Organic Chemistry, the Aromaticity is a property of Cyclic, planar structure with a ring of resonance bonds that gives the increased stability compared to other geometric with the same set of atoms. Aromatic compounds are very stable, and they do not break apart easily to react with other compounds. 

 Antiaromatic:- it is also a Cyclic molecule with a pi-electron system but there has higher energy due to the presence of 4n delocalized electrons in it. And Antiaromatic compounds are highly unstable and highly reactive in nature.

 Nonaromatic:- nonaromatic are every other molecules that fails one of these conditions (i.e., Cyclic, planar, conjugation and 4n or (4n+2) number of delocalized electrons, so anyone of these conditions is not fulfill, then the molecule is called non Aromatic compound).
 Note:- "All Quasi-aromatic compounds are aromatic but all aromatic compounds are not Quasi-aromatic compounds"


Quasi-aromatic:- Quasi-aromatic compounds are those in which the charges are present on the ring/molecule, and they take a part of Aromaticity of the compound.

Homoaromaticity:- in Organic Chemistry, it refers to a special type of Aromaticity in which conjugation is interrupted by a single sp³ hybridized carbon atom. 










๐ŸŽฆ For watch these videos for ๐Ÿ‘‰๐Ÿ‘‰ Full Concepts 

    Hรผckel's Rule for Aromaticity:- In 1931, German chemist and physicist Erich Hรผckel proposed a theory to determine if a planar ring molecule would have Aromatic properties. His rule states that if a Cyclic, planar molecules has (4n+2) number of ฯ€ electrons, then it is considered as an Aromatic compound. This rule come to be known as Hรผckel's Rule for Aromaticity.

   Four Criteria for Aromaticity:-  When we deciding a compound is Aromatic, then go through the following criteria. If the compound doesn't meet all the following four criteria , then it is called  not Aromatic compound.
    1. The molecule should be Cyclic.
    2. The molecule should be planar.
    3. The molecule should be maintain conjugation.
    4. The molecule has (4n+2)ฯ€ number of  electrons. (n= 0, 1,2,3....)



๐Ÿ“š✔️  In the given molecule Pyrene , the ฯ€ bond shown in green is in cross conjugation (shown in green in figure 1). This bond( figure 2) is excluded from interaction with rest of conjugated system. Hence , the central C=C isn't hosted by the largest p orbital loop, so it's not counted towards Hรผckel's rule for aromaticity.
          The outer periphery (shown in blue in figure 3), is a loop of 14ฯ€ electrons , therefore aromatic. This may be possible hรผckel double bond you are referring to.

          The ฯ€ bond in cross-conjugation (shown in green) maybe non-hรผckel double bond. 




๐Ÿ“š๐Ÿ‘‰๐Ÿ‘‰ PDF file for Wolff Rearrangement/ Arndt Eistert Synthesis of higher homologous acid

 


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At a glance :- The Wolff rearrangement is a reaction of Organic Chemistry where an alpha-diazocarbonyl compound is converted into a ketene by the loss of dinitrogen with accompanying 1,2-rearrangement.
     The reaction was discovered by  Ludwig Wolff in 1902.


Arndt Eistert reaction involves a series of chemical reactions and finally it synthesise a carboxylic acid from its homologue with one fewer carbon atoms. The Arndt Eistert Synthesis is a popular method for producing ฮฒ- amino acids from ฮฑ- amino acids.
    The reaction named after the German chemists Fritz Arndt and Bernd Eistert.


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๐ŸŽฆ Full Video Link ๐Ÿ‘‰๐Ÿ‘‰ Click Here 

At a glance:- In organic chemistry, the Diels Alder reaction is a Chemical reaction of conjugated diene and substituted alkene, commonly known as dienophile. And finally it gives a substituted cyclohexene derivative. It is the photo typical example of a pericyclic reaction with Cyclic concerted mechanism.



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    Organic Chemistry:- it is a student-friendly book about the complex subject of Organic Chemistry written by Jonathan Clayden, Nick Greeves, Stuart Warren.



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    Someone give us a review on our Facebook page about the Organic Chemistry written by Clayden, “ I have no words to do a review on that particular book but I want to say, without learning that book your subject knowledge can't be complete. So must learn Organic Chemistry, reaction and mechanism like a story.

     This book is really helps students for draw mechanism and molecules realistically , in order to understand the fundamentals of Chemistry concepts.


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At a glance:- the Michael Addition is the nucleophilic Addition of a carbanion bor another nucleophile to an alpha, beta-unsaturated carbonyl compound. It belongs to the larger class of conjugate addition. This one is the one of the most useful methods for the formation of mild C-C bonds.

 In Organic Chemistry, a carbonyl group is a functional group composed of a carbon atom doubly bonded with oxygen atom i.e., C=O. It is common to several classes of Organic compounds, as part of many larger functional groups. A compound containing a carbonyl group is often referred to as a carbonyl compound.


๐Ÿ“š๐Ÿ‘‰๐Ÿ‘‰ PDF of Mannich Reaction with Application




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At a glance:-  the Mannich Reaction is an organic reaction which consists of an amino alkylation of an acidic proton placed next to a carbonyl functional group by formaldehyde and a primary amine or a secondary amine or ammonia. And the final product is a beta-amino-carbonyl compound also known as a Mannich base.
    The reaction named after the chemist Carl Mannich.

  Mannich Base:- it is a beta-amino-ketone, which is formed by the reaction of an amine, formaldehyde (or aldehyde) and a carbon acid. The Mannich base is an end product of the Mannich Reaction, which undergo nucleophilic Addition Reaction of a non-enolizable aldehyde and any primary or secondary amine, and finally it produce resonance stabilized imine (iminium ion or imine salt)






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๐Ÿ“š๐Ÿ‘‰๐Ÿ‘‰ PDF of Aromaticity || Study Material of Career Endeavor


Order  Stability and Resonance Energy:-  Aromatic > Homoaromatic > Antiaromatic > Nonaromatic

   Aromaticity:- in Organic Chemistry, the Aromaticity is a property of Cyclic, planar structure with a ring of resonance bonds that gives the increased stability compared to other geometric with the same set of atoms. Aromatic compounds are very stable, and they do not break apart easily to react with other compounds. 



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 Antiaromatic:- it is also a Cyclic molecule with a pi-electron system but there has higher energy due to the presence of 4n delocalized electrons in it. And Antiaromatic compounds are highly unstable and highly reactive in nature.

 Nonaromatic:- nonaromatic are every other molecules that fails one of these conditions (i.e., Cyclic, planar, conjugation and 4n or (4n+2) number of delocalized electrons, so anyone of these conditions is not fulfill, then the molecule is called non Aromatic compound).

Quasi-aromatic:- Quasi-aromatic compounds are those in which the charges are present on the ring/molecule, and they take a part of Aromaticity of the compound.

Homoaromaticity:- in Organic Chemistry, it refers to a special type of Aromaticity in which conjugation is interrupted by a single sp³ hybridized carbon atom. 

_____________________________________________

๐Ÿ“š✔️  In the given molecule Pyrene , the ฯ€ bond shown in green is in cross conjugation (shown in green in figure 1). This bond( figure 2) is excluded from interaction with rest of conjugated system. Hence , the central C=C isn't hosted by the largest p orbital loop, so it's not counted towards Hรผckel's rule for aromaticity.
          The outer periphery (shown in blue in figure 3), is a loop of 14ฯ€ electrons , therefore aromatic. This may be possible hรผckel double bond you are referring to.
          The ฯ€ bond in cross-conjugation (shown in green) maybe non-hรผckel double bond. 





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๐Ÿ‘‰๐Ÿ‘‰ Chemist make first-ever ring of pure carbon,  Nature 572, 426 (2019) ||
  PDF file also available


Elusive 18-atom ‘cyclocarbon’ could be a step towards molecule-scale transistors. 

     

     Elusive 18-atom ‘cyclocarbon’ could be a step towards molecule-scale transistors.

    
     Long after most chemists had given up trying, a team of researchers has synthesized the first ring-shaped molecule of pure carbon — a circle of 18 atoms.


A 3D-image of the carbon-18
molecule made with an atomic
force microscope (AFM)
The chemists started with a triangular molecule of carbon and oxygen, which they manipulated with electric currents to create the carbon-18 ring. Initial studies of the properties of the molecule, called a cyclocarbon, suggest that it acts as a semiconductor, which could make similar straight carbon chains useful as molecular-scale electronic components.
๐Ÿ‘‰๐Ÿ‘‰ PDF ||. Chichibabin Reaction for IIT jam CSIR NET

 All applications are collection from international journal/ research papers


At a glance:-   The Chichibabin Reaction is an organic reaction for producing 2- aminopyridine derivatives by the reaction of pyridine with sodium amide. 
    It is substitution type reaction
    It was reported by Aleksei Chichibabin in 1914. 
   


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Mechanistic- The direct amination of pyridine with sodium amide takes place in liquid ammonia. Following the addition elimination mechanism first a nucleophilic NH2−   is added while a Hydride  (H) is leaving from the system.  
    Ciganek describe an example of an intramolecular Chichibabin Reaction in which a nitrile group that are present in a fused ring is the source of nitrogen in amination.  

Chichibabin Reaction for Quinoline & Isoquinoline :- 
Chichibabin Amination


2-Aminopyridine is an organic compound with the Chemical formula  H2NC5H4N. It has one of three isomeric aminopyridines.  

   Sodium amide :- It is commonly called as sodamide, is the inorganic compound with the Chemical formula NaNH2. It is a salt which are composed of the sodium cation and the azanide anion. 





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PDF || Favoriskii Rearrangement all applications are collection from journal papers   

 Official video tutorial :- Click here






Chemistry of rearrangement, Favorskii Rearrangement.

     At a glance:- the Favoriskii rearrangement of Cyclopropanation and alpha-halo ketones which leads to carboxylic acid derivative. In the case of Cyclic alpha- halo ketones, the Favoriskii rearrangement can take place and it constitutes a ring contraction.

    The Favoriskii rearrangement, it is named for the Russian Chemist Alexei Yevgrafovich Favoriskii.

    Alpha-halo ketones:- A haloketone in Organic Chemistry is a functional group consisting of a ketone group or carbonyl group with an alpha halogen substituent.

    Cyclopropanation:- it is an organic compound with the molecule formula C3H4O. It consisting of a  Cyclopropane carbon framework having one ketone functional group.




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๐Ÿ‘‰๐Ÿ‘‰ PDF || Shapiro Reaction //application are collection from research papers

 Full tutorial video :- Click here


 At a glance:- 
The Shapiro reaction is an organic reaction in which a ketone or aldehyde is converted to an alkene through the formation of an intermediate hydrazone in the presence of 2 equivalent of organolithium reagent.
     The reaction was first discovered by Robert H. Shapiro in 1967.

    This reaction is similar to the Bamford-Stevens reaction, which also involves the basic decomposition of tosyl hydrazones.


    Organolithium reagents:- they are organometallic compounds having carbon-carbon bonds. Ther are important reagents in organic synthesis.and they are frequently used to transfer the organic group or the lithium atom to the substrates in various synthetic steps, like nucleophilic addition or simple deprotonation.

Hydrazone:- hydrazones are a class of Organic compounds with the structure R
1R
2
C
=NNH
2
.  They are actually related to the ketones and aldehyde by the replacement of the oxygen with the NNH2 functional group.


    PDF || Vilsmeyer Haack Reaction













    at a glance :
    The Vilsmeier-Haack reaction is an organic reaction used to convert an electron rich aromatic ring to an aryl aldehyde by thge treatment with DMF, an acid chloride, and aqueous work-up. The mechanism begins with the reaction of DMF with the acid chloride to form an iminium salt known as the "Vilsmeier reagent''.
    


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     DMF:  
    Dimethylformamide is an organic compound with the formula C3H7NO. Commonly abbreviated as DMF (although this initialism is sometimes used for dimethylfuran or dimethyl fumarate, this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions. 
    
       Vilsmeier Reagent : 
Vilsmeier reagent is the active intermediate in the formylation reactions. The Vilsmeier-Haack reaction that use mixtures of dimethylformamide and phosphorus oxychloride to generate the Vilsmeier reagent, which in turn attacks a nucleophilic substrate and eventually hydrolyzes to give formyl.




๐Ÿ“š๐Ÿ‘‰๐Ÿ‘‰    Pdf  || Wagner MeerweinRearrangement || PDF for CSIR NET GATE IIT JAM  Applications are collection from international journals / research papers 


Wagner Meerwein Rearrangement

Application for Wagner Meerwein Rearrangement ( Only demo view) :-








Mechanism :- The Wagner-Meerwein rearrangement is an organic reaction used to convert an alcohol to an olefin by the treatment an acid catalyst.


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 The mechanism begins with protonation of the alcohol by the acid which is then released as water to forms a carbocation species. A 1,2-shift then occurs to form a more substituted and stabilized carbo-cation species. A final deprotonation with water produces the final olefin product and regenerates the acid catalyst. 


             For complete video tutorial :- Click here 
Wagner Meerwein Rearrangement
At a glance:- 
A Wagner–Meerwein rearrangement is a class of carbocation 1,2-rearrangement reactions in which a hydrogen, alkyl or aryl group migrates from one carbon to a neighboring carbon. They can be described as cationic [1,2]-sigmatropic rearrangements, proceeding suprafacially and with stereochemical retention. 

Wagner Meerwein Rearrangement with full mechanism, scope and  application ; for all in details; click here ๐Ÿ‘‡๐Ÿ‘‡๐Ÿ‘‡


     
       The reaction is named after the Russian Chemist Yegor Yegorovich Vagner, he had German origin and published in German journals as Georg Wagner and Hans Meerwein.
      
        The rearrangement was first discovered in bicyclic terpenes for example the conversion of Isoborneol to camphen, which are mention on the image box and PDF file for details mechanism also.



     

Full PDF Book of Organic Chemistry written by Clayden, 2nd edition

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