Chem 112A Fall 2012 Homework D (Problems related to lectures 9/4, 9/6, 9/11, and 9/13) Suggested Problems

ms from Loudon: Electron-pushing arrows, nucleophiles, and electrophiles: 3.2, 3.3, 3.8, 3.9, 3.10, 3.24, 3.25, 3.26, 3.27, 3.28, 3.30, 3.32, 3.33, 3.35, 3.49 Acidity: 3.14, 3.15, 3.19, 3.20, 3.21, 3.39, 3.40 Relationship between free energy and equilibrium: 3.16, 3.17, 3.18, 3.38 Alkanes: Constitutional Isomers and Nomenclature: 2.6, 2.7, 2.8, 2.9, 2.12, 2.13, 2.29, 2.30, 2.33 Alkanes: Newman projections and Conformational Analysis: 2.35, 2.37, 2.38, 2.39, 2.40

Guidelines for drawing electron-pushing arrows to generate resonance structures: a. A lone pair of electrons becomes a bond to an adjacent atom. b. A pair of electrons in a bond moves to become a lone pair on one atom in that bond. c. A pair of electrons in a bond moves to become a bond to an adjacent atom.

1. Only one structure below has a correct set of curved arrows to show generation of an alternate resonance structure. Each of the other structures has at least one incorrect use of curved arrows for this purpose. Cross out any incorrect arrow, and explain why that arrow would not lead to a valid resonance structure.

2. For each of the following molecules or ions, draw as many significant resonance structures as you can, with electron-pushing arrows to show interconversion between your structures. Label them "major contributor" and "minor contributor" based on their relative importance in describing the overall electron distribution for the molecule or ion. The bond connectivity is implied by the condensed structural formaulas. Make sure your answers are all resonance stuctures of each other (not constitutional isomers). (Note: Resonance structures are considered "not signif icant" if they meet any of the f ollowing criteria: (a) have an empty orbital (unf illed octet) on an electronegative atom (N, O, F) or (b) have more than one atom with unf illed octets or (c) have more than one positive f ormal charge and/ or more than one negative f ormal charge. Condensed structural formulas (all H's are explicitly indicated) [H2COH] [H2CCN]

[H2CNO2]

[(CH3)C(OH)2]

Bond-line structures (implied H's are missing, start by adding them)

H2N

NH2

O H

O H

3. Acidity, Basicity, and Resonance a) For each of the molecules below, identify the most acidic site and draw an arrow-pushing mechanism for reaction with a base, B:. Next, estimate the pKa of each starting molecule. Y ou may wish to consult one or more of the resources listed in the recent bSpace announcement. If you can't f ind enough inf ormation to make a reasonable estimate, propose a reason why the inf ormation you looked f or is not available. NH2 HO O O O O

OH

b) For each of the molecules below, identify the most basic site and draw an arrow-pushing mechanism for reaction with a generic acid, H-A. Next, estimate the pKa of each of the products that you drew (the conjugate acids of the starting molecules). Consult a pKa table as needed. NH2 HO O O O O

OH

c) For each of the following molecules, draw as many significant resonance structures as you can, with electron-pushing arrows to show interconversion between your structures. NH2 OH HO O O O N O

d) Consider the resonance structures you drew in part c and the reactions that you drew in part a. For each molecule below, predict whether is it more acidic or less acidic than the analogous molecule from part a. Does this correspond to a higher pKa or a lower pKa? (Limit your answer to the same site of reactivity - if the correponding reaction with a base is not possible, state why ) NH2 OH HO O O O N O

e) Consider the resonance structures you drew in part c and the reactions that you drew in part b. For each molecule below, predict whether is it more basic or less basic than the analogous molecule from part a. Does this correspond to a higher pKa (of its conjugate acid) or a lower pKa (of its conjugate acid)? (Limit your answer to the same site of reactivity - if the correponding reaction with an acid is not possible, state why ) NH2 OH HO O O O N O

f) Consider the resonance structures you drew in part c. Do any of the molecules have an alternate acidic site and/or and alternate basic site that can be predicted based on these resonance structures? If so, draw the corresponding arrow-pushing mechanisms for reaction with an acid or base.

NH2

OH

HO

4. Consider the following pKa data collected in different solvents: acid NH4+ NC CN pKa (H2O) 9.2 pKa (DMSO) 10.5

O S DMSO

11

11.1

CH3OH H2O

15.5 15.7

27.9 31.2

Propose an explanation for the strong solvent-dependance of the pKa of methanol and water, while the other two acids listed here show a much smaller solvent dependance.

(Hint: think about what intermolecular interactions can take place with the acid and/ or it's conjugate base and each solvent, and how those interactions af f ect stability)

Conformational analysis with Newman projections practice

1. Draw the Newman Projection along the bond indicated by the "eyeball".

Br H Cl Cl H MeO H

O H D

2. Draw the bond line notation of the molecules exactly as they are represented by the following Newman Projections. Use wedges and dashes. Draw in an eyeball to clarify which orientation you've drawn.
A. H H B. H Cl Br H

C. H H

D.

O H

H H H

3. Draw the bond line notation of the molecules exactly as they are represented by the following Newman Projections. Use wedges and dashes. Draw in an eyeball to clarify which orientation you've drawn. Then label the conformations as staggered or eclipsed. Next, rank the staggered conformations in order from lowest in energy (S1) to highest in energy (S3). If two conformations are the same in energy, say so (you won't use S3). Do the same for the eclipsed conformations (E1 through E3). Label the types of gauche interactions as well as the eclipsing interacctions.
H Cl Cl H A Cl H Cl Cl B C H H Cl HH Cl Cl H H Cl Cl Cl D E F H H Cl

4. Please label the conformations as staggered or eclipsed. Next, rank the staggered conformations in order from lowest in energy (S1) to highest in energy (S3). If two conformations are the same in energy, say so (you won't use S3). Do the same for the eclipsed conformations (E1 through E3). Label the types of gauche interactions as well as the eclipsing interactions.

H H HO 0 H H

H H OH 60

OH H H H

HO H H H H H

OH OH H H H H

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300

Rank:

Interactions:

Please draw a potential energy diagram for the above rotation. Do not worry about absolute energy differences, only relative differences.

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5. A.The following problem will use the compound 1-chloro-2-cyclohexyl-propane below. Please draw a Newman Projection of the molecule along the line indicated. Next, draw five more Newman Projections where the BACK CARBON is rotated 60 CLOCKWISE. To save room, you may use the shorthand "Cy" for the cylohexyl ring.
Cl

5B. Label each gauche interaction and each eclipsing interaction. Interactions for A: Interactions for B: Interactions for C: Interactions for D: Interactions for E: Interactions for F: 5C. Draw a potential energy diagram for the rotation described above. Do not worry about getting the absolute energy differences correct, only the relative differences.

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6. A.The following problem will use the compound 2,3,4-trimethylhexane below. Please draw a Newman Projection of the molecule along the line indicated. Next, draw five more Newman Projections where the BACK CARBON is rotated 60 COUNTERCLOCKWISE. To save room, you may use abbreviations for common substituents.
H H

6B. Label each gauche interaction and each eclipsing interaction. Interactions for A: Interactions for B: Interactions for C: Interactions for D: Interactions for E: Interactions for F: 6C. Draw a potential energy diagram for the rotation described above. Do not worry about getting the absolute energy differences correct, only the relative differences.

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300