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Which of the following is the most stable radical?

Rank the following alkyl radicals in order of increasing stability (least < < <most).

1<3<2<4

What is the product of the following reaction?

Predict the product of the following reaction. 1-methylcyclohexene + HBr/H2O2 ?


Br

Identify the reagent(s) that will promote the following transformation.

A) HBr, tetrahydrofuran p B) HBr, peroxides C) Br2, CCl4 D) Br2, H2O

Conjugation occurs whenever p orbitals can overlap on three or more adjacent atoms.

The four p orbitals on adjacent atoms make a 1,3-diene a conjugated system.

Having three or more p orbitals on adjacent atoms allows p orbitals to overlap and electrons to delocalize.

1,4-Pentadiene is an isolated diene. The T bonds in 1,4-pentadiene are too far apart to be conjugated.

Which of these compounds have delocalized electron density?

The allyl carbocation is another example of a conjugated system.

Conjugation stabilizes the allyl carbocation.

Drawing resonance structures for the allyl carbocation is a way to see how to use Lewis structures to illustrate how conjugation delocalizes electrons.

The true allyl cation is a hybrid of the two resonance forms. In the hybrid, the positive charge is delocalized over the two terminal carbons. Delocalizing electron density lowers the energy of the hybrid, thus stabilizing the allyl carbocation and making it more stable than a normal 1 carbocation.

What are the resonance structures of these compounds?

Experimental data show that the stability of the allyl cation is comparable to a more highly substituted 2 carbocation.

Common Examples of Resonance


1. The Three Atom Allyl System, X=Y-Z*

Examples are the allyl cation and the acetate anion. The two resonance structures differ in the location of the double bond, and either the charge, the radical, or the lone pair, generalized by [*].

2. Conjugated Double Bonds


Cyclic completely conjugated rings like benzene have two resonance structures, drawn by moving the electrons in a cyclic manner around the ring. Three resonance structures can be drawn for other conjugated dienes, two of which involve separation of charge.

3. Cations Having a Positive Charge Adjacent to a Lone Pair

The overall charge is the same in both resonance structures. Based on formal charge, a neutral X in one structure must bear a (+) charge in the other.

4. Double Bonds Having One Atom More Electronegative Than the Other

Draw the resonance structures?

The resonance hybrid more closely resembles the major contributor

Draw the other resonance structure and predict which is more stable.
H3C C
+

NH2

H3C

NH2

H3C

C CH3

NH2

CH3

CH3
-

O
O O NH H3C NH

H3C

NH

H 3C

Draw the three resonance structures of CH3CO2H and rank their stability.
O H3C OH
H 3C
-

O OH H3C

O
+

OH

1
-

3
O O OH H3C

H3C

OH

Electron Delocalization, Hybridization, and Geometry


Consider the two Lewis structures (A and B) for the resonance stabilized anion (CH3COCH2).

Based on structure A, the indicated carbon is sp3 hybridized, with the lone pair of electrons in an sp3 hybrid orbital. Based on structure B, however, it is sp2 hybridized with the unhybridized p orbital forming the T portion of the double bond.

The electron pair on the carbon atom adjacent to the C=O can only be delocalized if it has a p orbital that can overlap with two other p orbitals on two adjacent atoms. Thus, the terminal carbon atom is sp2 hybridized with trigonal planar geometry. Three adjacent p orbitals make the anion conjugated.

Determien the hybridization of the indicated atoms.

O
p

O p O CH
o

All three are sp2 hybridized.

Conjugated Dienes
Conjugated dienes are compounds having two double bonds joined by one W bond. Conjugated dienes are also called 1,3-dienes. 1,3-Butadiene (CH2=CH-CH=CH2) is the simplest conjugated diene. Three stereoisomers are possible for 1,3-dienes with alkyl groups bonded to each end carbon of the diene.

Two possible conformations result from rotation around the CC bond that joins the two double bonds.

Note that stereoisomers are discrete molecules, whereas conformations interconvert.

Draw the three possible stereoisomers of 2,4-octadiene. Pick which one is (2E,4E) 2,4-octadiene.

Draw the s-cis and s-trans conformations of (3Z,5Z)-4,5-dimethyl -3,5-octadiene

s-trans

s-cis

The CarbonCarbon W Bond Length in 1,3-Butadiene


Four features distinguish conjugated dienes from isolated dienes.
1. The CC single bond joining the two double bonds is unusually short. 2. Conjugated dienes are more stable than similar isolated dienes. 3. Some reactions of conjugated dienes are different than reactions of isolated double bonds. 4. Conjugated dienes absorb longer wavelengths of ultraviolet light.

The CarbonCarbon W Bond Length in 1,3Butadiene


The observed bond distances can be explained by looking at hybridization.

A resonance argument can also be used to explain the shorter CC W bond length in 1,3-butadiene. Based on resonance, the central CC bond in 1,3butadiene is shorter because it has partial double bond character.

Finally, 1,3-butadiene is a conjugated molecule with four overlapping p orbitals on adjacent atoms. Consequently, the T electrons are not localized between the carbon atoms of the double bonds, but rather delocalized over four atoms. This places more electron density between the central two carbon atoms of 1,3-butadiene than would normally be present. This shortens the bond.

Using hybridization, compare the C-C bonds of the following three compounds.
H3C CH3 H2C CH2 HC CH

sp3 25% s character

sp2 33% s character

sp 50% s character

Using resonance, why are the two CO bonds the same length?
O
-

O
-

O O H3C O

H3C

H3C

The two resonance structures show how the electron density is delocalized over 3 atoms.