Winter 2014

118A Midterm 1 Page 2

Initials_________

1. (12 pts) Name each compound below, using systematic nomenclature. (a) 3-ethyl-1-methoxy-4-methylpentane
CH3O

(b) 3-chloro-4-ethyl-2,7-dimethyloctane
Cl

(c)
I

trans-1-ethyl-4-iodocyclohexane

2. (16 pts) Lewis structures and resonance forms. For each species below (1) write a good Lewis structure. You can show bonds with either dots or lines. Include all non-bonding electrons as dots and don't forget formal charges. (Hint: the atoms are attached as shown.) (2) Each of these is stabilized by resonance. Using curved arrows to show the electron movement, convert each Lewis structure into another good resonance form. (c) CIRCLE the best (most important) contributing resonance form for each species. (If both are equally good, don't circle either one.) (a) Carbon monoxide, CO

(C lacks an octet) :C

O:

..

:C

O:

(both atoms have octets)

(b) Propynyl cation, [HCCCH2]+

H H C C C+ H H C H

C H

no obvious reason for you to prefer one resonance form over the other

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3. (28 pts) Multiple choice. CIRCLE the correct answer. (a) Best description of the hybridization of nitrogen in HCON(CH3)2. sp3 sp2 sp none

(b) The central carbon atom in (CH3)3CCl (bold) would be expected to show what kind of reactivity?

strongly basic

nucleophilic

radical

electrophilic

(c) Trans- and cis-1,2-dimethylcyclohexane, both in chair conformations, are chemically identical stereoisomers a pair of conformers geometrically similar

(d) Approximate bond angle around nitrogen in (CH3)3N 90 105 120 180

(e) Best description of the geometry at the central carbon atom in H2C=C=CH2 (bold) linear trigonal planar tetrahedral

(f) The molecule CH3CH(SH)CH2COCH3 contains

a C=O double bond

a C=S double bond

two CS single bonds

two CO single bonds

(g) Contains a nucleophilic carbon atom.

OCH3 OH

MgCl O

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3. (continued) (h) Shows proper use of arrows in the reaction between ammonia and hydrogen chloride
Cl H

.. NH3

Cl H

.. NH3

Cl H

.. NH3

(i) Most reactive towards bromine atoms CH4 (j) Main reason for 'i' resonance (k) Most stable (l) Typical for a slow, endothermic process Late transition state Early transition state Intermediate transition state conformation hyperconjugation electronegativity CH3CH3 CH3CH2CH3

(m) Best example of a synthetically useful alkane halogenation reaction

Cl2 +

Cl2 + CH3CH2CH3

Cl2 +

(n) Contains all perfectly staggered conformations of CC bonds

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4. (24 pts) This problem deals with the possible reaction between iodine and methylpropane (isobutane). Use the bond strength data below to answer the questions that follow. (CH3)3CH + I2
methylpropane (isobutane) I H any C

heat

C4H9I + HI

96.5 kcal.mol CH bond strengths in methylpropane H3C 101 kcal/mol H C CH3 CH3

I, 36 kcal/mol I, 71 kcal.mol I, 56 kcal/mol

(a) If this reaction were to proceed as shown in the equation above, what would you expect the structure of its major organic product to be, based on the bond-strength data you have been given above? Write the structure below. Hint: as the equation above indicates, the composition of the product is C4H9I.
I C H3C CH3 CH3

(b) Write a likely pair of propagation steps for this reaction. Give !H for each of these propagation steps in the spaces provided to the right. 96.5 71 = +25.5 kcal/mol !H

(CH3)3CH + I

(CH3)3C + HI

(CH3)3C + I2

(CH3)3CI + I

36 56 = 20 kcal/mol !H

(c) Determine the overall !H for the reaction: + 5.5 Based on this result, does this reaction proceed in !H No the direction written (yes or no)?_______ (d) Based on your answer to part (c) above and the bond strength data provided, write a likely initiation step for the reaction in the direction that it is thermodynamically favored to go. Determine !H for this initiation step. Favored direction is reverse direction, so initiation must involve breaking the weakest bond between (CH3)3CI and HI to give a relevant radical. Has to be 56 kcal/mol the CI bond, based on the bond strengths, DH = 56 kcal/mol heat !H (CH ) CI (CH ) C + I
3 3 3 3

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Initials_________

5. (10 pts) Multiple choice. Conformations. CIRCLE the correct answer. (a) Most stable
H CH3CH2 H H CH(CH3)2 CH3 CH3CH2 H3C H H CH(CH3)2 H CH3CH2 H H CH3 CH(CH3)2 H

(b) Most stable

H CH3CH2 CH3CH2 H CH3 CH3 CH3CH2 H3C H O C CH3 CH3 O C CH3 Data: !H (axeq) for CH3 = 1.7 kcal/mole and for CH3C=O = 1.4 kcal/mole H3C C CH3 CH2CH3 CH3 H CH3 CH3CH2 H H CH3 CH2CH3

(c) Most stable

H3C

6. (10 pts) Ethanal (also known as acetaldehyde) has the formula CH3CHO. (a) Draw a good Lewis structure for acetaldehyde.
H H C H :O: C H

(b) Acetaldehyde is slightly acidic. Draw the Lewis structures for the anions (conjugate bases) that result from (1) removal of H+ from the CH3 group and (2) removal of H+ from the CHO group. Only one of these anions is stabilized by a second resonance form. Draw this second resonance form next to the initial .. _ Lewis structure. :O: _ :O:
H C

..

C H H C

H H H H (1) removal of H+ from CH3 group in CH3CHO gives _______________________________ :O: C:

H (2) removal of H+ from CHO group in CH3CHO gives_______________________________

(c) You can tell which are the most acidic hydrogens in a molecule: they are the ones whose removal gives the most stable conjugate base. With that in mind, which hydrogen(s) in CH3CHO are most acidic? The hydrogens on the CH3 group are more acidic.