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1,2 and 1,4- Addition To Dienes

Description:  Conjugated dienes treated with strong acids (e.g. HCl, HBr)
may result in either “1,2-addition” products (top) or “1,4-addition” products,
depending on temperature.

Notes: “HX” here is often HCl or HBr.

Examples:

Notes: 

The key factor in whether the 1,2- product or the 1,4-product is favored
depends on temperature. Low temperatures will favor the product in which
the most stable carbocation is favored (usually the 1,2-) and higher
temperatures will favor the product which has the most substituted alkene
(often the 1,4-).
See: Additions to dienes: 1,2- vs 1,4- addition
The first example gives two disubstituted alkenes, which should be about
equal in stability. The second example has a 1,2-product with a
trisubstituted alkene and a 1,4-product with a tetrasubstituted alkene, so the
1,4- should be favored under thermodynamic conditions. The third example
has a disubstituted alkene (1,2) vs. tetrasubstituted alkene (1,4). The fourth
example uses DBr instead of HBr, resulting in deuterated products (recall
that D is the heavy isotope of hydrogen). In this case there isn’t a significant
difference between the stability of the two products.
 
Mechanism: The “1,2-addition” product simply results from the protonation
of the alkene in ordere pto epa
formed
a new, resonance-stabilized
o you st dte carbocation (Step
1, arrows A and B) followed
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attack of the carbocation
our summary PDFs by the anion at the
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position adjacent to the carbon which was protonated (Step 2, arrows C
and D).

Here’s the mechanism for the 1,4 product. The alkene is protonated by H-Br
(Step 1, arrows A and B) resulting in a new resonance-stabilized carbocation.
In this case, the bromide anion attacks not at the position adjacent to the
new C-H (carbon 2) but instead carbon 4, which you can imagine as the
resonance form below (Step 2, arrows C and D).

Notes: Although it’s helpful to draw out the two resonance forms and to
draw the 1,4-attack at the bottom resonance form, keep in mind that
resonance forms don’t equilibrate between each other – the “true” form is a
hybrid between the two resonance forms.
 

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