Problem 1: Draw the product of nucleophile substitution , and determine the likely mechanism ( SN' or SN? ): H3C° `CH3 Br a- CH3OH b- H2O + Br H,c~YCH, CH, с- CH,ОН + Problem 2: What is likely mechanism of nucleophilic substitution for each halide ? Br H3C
Reactive Intermediates
In chemistry, reactive intermediates are termed as short-lived, highly reactive atoms with high energy. They rapidly transform into stable particles during a chemical reaction. In specific cases, by means of matrix isolation and at low-temperature reactive intermediates can be isolated.
Hydride Shift
A hydride shift is a rearrangement of a hydrogen atom in a carbocation that occurs to make the molecule more stable. In organic chemistry, rearrangement of the carbocation is very easily seen. This rearrangement can be because of the movement of a carbocation to attain stability in the compound. Such structural reorganization movement is called a shift within molecules. After the shifting of carbocation over the different carbon then they form structural isomers of the previous existing molecule.
Vinylic Carbocation
A carbocation where the positive charge is on the alkene carbon is known as the vinyl carbocation or vinyl cation. The empirical formula for vinyl cation is C2H3+. In the vinyl carbocation, the positive charge is on the carbon atom with the double bond therefore it is sp hybridized. It is known to be a part of various reactions, for example, electrophilic addition of alkynes and solvolysis as well. It plays the role of a reactive intermediate in these reactions.
Cycloheptatrienyl Cation
It is an aromatic carbocation having a general formula, [C7 H7]+. It is also known as the aromatic tropylium ion. Its name is derived from the molecule tropine, which is a seven membered carbon atom ring. Cycloheptatriene or tropylidene was first synthesized from tropine.
Stability of Vinyl Carbocation
Carbocations are positively charged carbon atoms. It is also known as a carbonium ion.
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Polar protic solvents such as water favor SN' reactions, which produce both a cation and an
anion during reaction. These solvents are capable of stabilizing the charges on the ions formed
during solvation. Because SN² reactions occur via a concerted mechanism (a mechanism which
takes place in one step, with bonds breaking and forming at the same time) and no ions form,
polar protic solvents would have little effect upon them. Solvents with low dielectric constants
tend not to stabilize ions and thus favor SN² reactions. Conversely, solvents of high dielectric
constants stabilize ions, favoring SN' reactions.
In general, good leaving groups are those capable of forming stable ions or molecules upon
displacement from the original molecule. Conversely, poor leaving groups form ions of
moderate stability.
poor to
bases, such as OH , NH2 , and RO ¯, make poor leaving groups.
Water, which is less basic than a hydroxide ion, is a better leaving group. Poor bases usually
make good leaving groups. A poor base is an ion or group in which the electrons are tightly
bound to the molecule due to high electronegativity or resonance.
Problem 1:
Draw the product of nucleophile substitution , and determine the likely mechanism ( SN' or
SN² ):
H3C
CH3
a- CH3OH
+
Cl
b- H2O
+
Br
-CH,
CH,
H,C
с- CН,ОН +
Problem 2:
What is likely mechanism of nucleophilic substitution for each halide ?
Br
H3C
17
133
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