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Wednesday, January 1, 2020

DDT- DichloroDiphenylTrichloroethane:

DDT, the abbreviation for dichlorodiphenyltrichloroethane, is a colorless, tasteless, and almost odorless crystalline chemical compound, an organochlorine.  DDT use as pesticide and also called “miraculous” by Winston Churchill because of the many lives it saved by killing disease carrying mosquitoes.
DDT was first synthesized in 1874 by the Austrian chemist Othmar Zeidler. DDT's insecticidal action was discovered by the Swiss chemist Paul Hermann Müller in 1939. DDT was used in the second half of World War II to control malaria and typhus among civilians and troops. DDT use is now banned in the United States and many developed countries because it is a nonspecific insecticide that persists in the environment

Reactivity order of Pyrrole, Furan and Thiophene towards Electrophilic substitution :


Pyrrole, furan and thiophene undergo electrophilic substitution reactions like nitration, sulphonation, halogenation etc. characteristic of aromatic rings. That carbons in 5-membered heterocyclic rings have higher electron density compared to benzene and hence undergo electrophilic substitution more readily than benzene.The electrophilic substitution takes place preferentially at 2-position (C-2).
The attack of an electrophile on pyrrole, for example, will lead to formation of 2- and 3-substitution products by way of carbocations (1) and (2) respectively.The substitution occurs preferably at C-2 position because the intermediate obtained by attack at this position is more stable than the intermediate obtained by attack at C-3. The positive charge in intermediate (1) is more delocalized than intermediate (2) and hence is more stable and preferred intermediate.
The electrophilic substitution at C-2 in furan and thiophene can also be accounted in the same manner. Furan is not as reactive as pyrrole in electrophilic substitution reactions because the oxygen in furan is more electronegative than nitrogen in pyrrole and therefore does not enhance the electron density of carbons as much as pyrrole. Thiophene is less reactive than furan towards electrophilic substitution because the p-electrons of sulphur are in 3p orbital which overlaps less effectively than the 2p orbital of nitrogen or oxygen with 2p orbitals of carbon. The relative reactivities towards electrophilic substitution follows the order:

Bredt's rule:

SIR effect:
Dancing Resonance:
Inversion of Amines:

Tuesday, December 31, 2019

Imidazole is more basic than pyridine? Why?


Imidazole and its derivatives form an interesting and important class of heterocyclic aromatic amines.
The basic strength of imidazole is approximately 100 times more basic than pyridine. Because protonation of imidazole yields an ion that is stabilized by the electron delocalization represented in the resonance structures given as below:
As seen in above figure the electrostatic potential map of the conjugate acid of imidazole (imidazolium ion) is consistent with the resonance description that shows both nitrogens as equivalent.
Related Questions:

Biological Important of Imidazole and structure:


Imidazole and its derivatives form an interesting and important class of heterocyclic aromatic amines.
An imidazole ring is a structural unit in two biologically important compounds, histidine and histamine. 
Histidine is one of the amino acid building blocks of proteins and is directly involved in key proton-transfer processes. The drop in blood pressure associated with shock is a result of the formation of histamine, which stimulates the dilation of blood vessels.

Related Questions:

Pyridine is almost 1 million times less basic than piperidine? Why?


We know that if nitrogen is part of an aromatic ring, however, its basicity decreases markedly.  So in pyridine nitrogen is part of an aromatic ring hence its basicity is much more less than piperidine. The difference between the two lies in the fact that the nitrogen lone pair occupies an sp3- hybridized orbital in piperidine versus an sp2-hybridized one in pyridine. As we have noted on several occasions, electrons in orbitals with more s character are more strongly held than those with less s character. For this reason, nitrogen holds on to its unshared pair more strongly in pyridine than in piperidine and is less basic.