CHM 1321A Sample Mid-Term 1

1) a) Give brief explanations for the following. Use structures when possible. bonding orbital (3 points) in phase mixing of atomic orbitals electron density between atoms lower energy
+

b) -

antibonding orbital (3 points) out of phase mixing of atomic orbitals node between atoms higher energy
+

2) Draw the following as Lewis and line structures: (12 points)

a) CH3CH2CHCHCH2COCH3

H H H H H O H H C C C C C C C H H H H H 2

b) CH3CH2CH(CH2CH3)CH2OH H H H H H C C C C O H H H H H C H H C H H 2

OH 2

c) NCCH2CH(OCH3)CH(CH3)CH2CH2OH H H C H H H H H N C C C C C C O H H H H H O H C H H 2

OH O 2

3) For the following compound:

Cl C C Cl

a) What is the hybridization of the carbon and chlorine atoms? (2 points) C : sp 1 Cl : sp3 1 b) Show the structure of the molecule using the LCAO method. (10 points)
p 2 electrons 1 Cl 1 p 1 p 1 sp

p 1

Cl

sp3

sp 1 sp3

1 linear

c) Label the orbitals used and the bonds formed in part b. (6 points) d) What is the geometry of the carbon and chlorine atoms? (2 points) C : linear 1 Cl : tetrahedral 1 e) What is overall the geometry of the molecule? (1 point) Linear 1 4) Give IUPAC names for the following: (6 points)
a) 7-ethyl-2-methydecane 2

OH b) trans-3-methylcyclohexanol 2

OH c) 5-ethylcyclodecanol

5) Draw the important resonance forms for the following. Identify the major and minor forms and show the resonance hybrid structure. (10 points)
O 1 2 O O 2 O 2

minor

insignificant

major

6) For 1-hydroxycyclohexane a) Draw one chair form of the compound showing all axial hydrogens. (4 points)
H H H OH H H H 2 Axial H's 2 Chair with OH

b) Re-draw the same chair, showing all the equatorial hydrogens (do not draw axial hydrogens). (4 points)
H H H H H OH 2 2 Same chair with OH Equitorial H's

c) Draw the other chair form of the compound (no hydrogens except on O). (3 points)
OH 2 1 Chair "flipped" OH "flipped"

d) Indicate which chair form is the most stable (part a or c). Briefly justify your choice. (2 points) The form with the OH equatorial is most stable (a or c will depend on which chairs where drawn). Substituents in axial positions are sterically crowded. 2 e) When the chair forms interconvert, draw and name the high-energy intermediate structure. (2 points)
HO 1 structure with OH

Boat

7) For the following compounds a) show the stereogenic centre(s) by labeling them with a star (*)(3 points) b) determine the priorities of the substituents on each stereogenic centre. For compounds with more than one centre, make sure you clearly indicate which priorities refer to which centre. (re-drawing the structure helps) (6 points) c) Determine the configuration of each stereocentre (3 points)
1

(i)
4H

Cl

*
2

CH3 CO2H

(ii)

CCl3 H * OH Cl * CH3 H OH H

CCl3 R 1 H OH Cl 3 CH3 H OH H
4

CCl3 H 2 OH 4 1 Cl CH3 H 3 OH H

8) For each compound shown below, convert the structure to the Fischer projection. (8 points)
(a) H Cl CH3 CO2H H Cl CO2H CH3 2 1 Fischer Configuration correct

H (b) Br

CH3 Br H

CH3 Br H Br H

3 1 1

Fischer Configuration correct Configuration correct

9) Show two types of eclipsed, one anti and one gauche staggered conformation of butane. Clearly identify each conformer. Indicate the relative energy of each conformer. (13 points).
2 H CH3 H H3C H H H3C CH3 H H 1 3.6 kcal-mol
-1

2 H H H H

CH3 2 CH3 H3C H H H CH3 1 H H H

eclipsed

eclipsed 1 4.9 kcal-mol-1

anti staggered 0 kcal-mol-1

gauche staggered 1 0.9 kcal-mol-1 1

10) Arrange the following in order of increasing boiling point. Briefly justify your choice. (4 points)
CH3 N H N

CH3 N

H N 1 highest 4 ranking justification

lowest van der waals only

van der waals dipole-dipole van der waals only van der waals cyclic packs better dipole-dipole H-bonded