Name_______KEY_____________________ Date___________________________

CHEM 213 Exam I Summer 2010

Time limit = 60 minutes Part 1: Multiple Choice: 4 pt. @ Directions: Answer ALL questions from this part (#1 15) on the answer sheet below. Responses marked elsewhere will not be evaluated. Circle or darken the letter that corresponds to the BEST answer. There is only one BEST answer for each question. 1 2 3 4 5 6 7 a b a b a b a b a b c d c d c d c d c d c d c d 9 10 11 12 13 14 15 a b a b a b c d c d c d c d c d c d c d

a b a b a b a b

a b a b

8 a b c d __________________________________________________________________________ Part 1 Part 2 No. correct ______ x 4 16 17 18 19 = = = = = __________ / 60 __________ / 20 __________ / 10 __________ / 10 __________ / 10

TOTAL

__________ / 110

Name_______KEY_____________________ Date___________________________

Name_______KEY_____________________ Date___________________________ : 1 Which compound is (2Z,4E)-3,4-dimethyl-2,4-octadiene? All structures are 3,4-dimethyl-2,4-octadiene (a) (2E,4E) (c) (2Z,4Z)
H3C H C H3C C CH3 C C H
H

CH2CH2CH3
H3C C

H3C C C CH3 C

CH2CH2CH3

(b)
6 1
H3C H3C

(d) (2E,4Z)
7 8
H C H CH3 H3C C CH3 H3C C C CH2CH2CH3 H CH2CH2CH3

4
C

5
C

2
C

3
C

For the 2,3 double bond, on C2 the methyl group (dark blue) has a higher priority than H (cyan) and on C3 the alkene chain C4-C8 (C4 is blue) has a higher priority than methyl (cyan). The high priority groups are on the same side so the C2-C3 bond is labeled as Z (German: zusammen = together). For the 4,5 double bond, on C4 the alkene chain C1-C3 (C3 is green) has a higher priority than methyl (lime) and on C5 the propyl group (green) has a higher priority than H (lime). The high priority groups are on opposite sides so the C4-C5 bond is labeled as E (German entgegen = against). 2 In the reaction below, water serves as a(n)
H3C C H3C CH2
+ + H , H2O

CH3 H3C C OH CH3

(Hint: Think of the reaction mechanism.) (a) base only (c) both base and nucleophile (b) nucleophile only (d) neither base nor nucleophile When water serves as a nucleophile, a base is required to remove a proton to make the oxygen electrically neutral. 3 The Cl-C-Cl bond angle of dichlorocarbene (:CCl2) is most nearly (a) 90 (b) 109 (c) 120 (d) 180 Three groups (lone pair, Cl, Cl) around a central atom = trigonal = 120

Name_______KEY_____________________ Date___________________________ In the BH3-THF molecule, the hydrogen atoms on boron behave chemically as
H H B O H

BH3-THF (a) H+ (b) H(c) H (d) H2 In BH3, B is in group 3 so its cation has a charge of +3. In order to balance the charge, H needs a charge of -1. It will act, therefore as H-.

Which carbocation will not undergo rearrangement? (Which is the most stable cation?) (a) 3 (c) 2

(b) 1

(d) 2

Name_______KEY_____________________ Date___________________________ Which of the compounds below cannot serve as a Diels-Alder diene? Which diene cannot assume an s-cis conformation? (a) s-cis (c)
rotate

(b) s-cis

s-trans but the single bond can rotate to make it s-cis (d) stuck as s-trans by the ring

Which cation is more stable? (a) 3

H H C CH3 C CH3 H O

(c) 1
H H C CH3 H C CH2 H O

resonance stabilized by lone pair of electrons on O (b) 1

H H C CH2 H C CH3 H O

(d) 2
H H C CH3 C CH3 H O

Name_______KEY_____________________ Date___________________________ Ozonolysis of an alkene gives the following products.

O O

What is the structure of the original alkene? Make the C=Os face each other and connect them as a C=C

(a)

(c)

(b)

(d)

Which of the following reactions does NOT involve a three-centered bond or a three membered ring? (a) Addition of Br2, H2O to an alkene (bromonium ion = 3-centered bond)) (b) Hydrolysis of an epoxide (epoxide = 3 membered ring) (c) Hydroboration-oxidation of an alkene (1. BH3-THF, 2. H2O2, -OH) (4 membered ring) (d) Oxymercuration-reduction of an alkene (1. Hg(OAc)2 THF, H2O, 2. NaBH4) (3-centered ring w/ Hg)

Name_______KEY_____________________ Date___________________________ Which of the following represents the curved arrow notation for the first step in the addition of H-Cl to 1-propene? (a) has H- as the leaving group
H Cl

10

(c) forms 2 cation

H Cl

H3C

CH
H

CH2
Cl

H3C

CH
H

CH2
Cl

(b) forms 1 cation

(d) has H- as the leaving group

H3C

CH

CH2

H3C

CH

CH2

11

Which of the following represents the highest occupied molecular orbital (HOMO) of 1,3-butadiene? The HOMO looks like the double bond single bond pattern in the molecule. There are 4 p electrons in 1,3-butadiene (2 e- per p bond x 2 p bonds) (a) 2 2 e- = HOMO (c) 3 (no electrons)

(b) 1 2 e- (lowest energy)

(d) 4 (no electrons)

Name_______KEY_____________________ Date___________________________ In the reaction below, the thermodynamically favored product is

+
H Cl

12

products

(a)

(c)

Cl

Cl

(b)

(d)

Cl
Cl

Find the more stable alkene = more highly substituted C=C 13 Which of the following is the best dienophile in a Diels-Alder reaction? Generally, dienophiles should be electron poor. Alkyl groups are electron donating and C=O groups are electron withdrawing. (a) (c)
H C C H CH3 CH3

O H CH3

CH3
H

(b)
O H CH3 CH3 H O

(d)
H

Name_______KEY_____________________ Date___________________________ What is the enol of the ketone shown below?

O

14

(a)
OH

(c)
OH

(b)
OH

(d)
OH

The ketone sp2 carbon is also the enol sp2 carbon. 15 What alkene would be best as starting material for the synthesis of 2-bromopentane?
Br

(a)

(c)

Markovnikov addition of H-Br gives only 2-bromopentane. Protonation of C1 gives a more stable 2 cation on C2 than protonation on C2 giving a 1 cation. (b)

There is no obvious help from Markovnikovs rule. Protonation of either C2 or C3 gives 2 cations. Both 2bromopentane and 3-promopentane will be produced (d)All will give 2-bromopentane as the major product.

There is no obvious help from Markovnikovs rule. Protonation of either C2 or C3 gives 2 cations. Both 2bromopentane and 3promopentane will be produced.

Name_______KEY_____________________ Date___________________________ Part 2: Short Answer: Directions: Answer the questions below to the best of your ability. Bear in mind that not all questions are of equal point value or of equal difficulty. 16 Provide a reagent or product as needed for the reactions below: Stereochemistry is important! Show it! (4 pt. @) Anti-Markovnikov addition and syn addition of H-OH
CH3

+ 1. BH3-THF 2. H2O2, -OH

H OH

B
H3CH2C C H C H CH2CH3

Epoxidation (stereospecific)
+ CH3CO3H
H3CH2C C H O C H CH2CH3

C
H3C C H C CH3 CH3 C H3C C CH2CH3 H

(:CH2 addition) CH2N2 or CH2I2, Zn(Cu) +

(stereospecific)
CH2 CH3 H CH3

D
H3CH2C

+ 1. OsO4 2. Na2SO3

Syn hydroxylation (stereospecific)

OH C OH C

E
H3C C C CH2 CH3

Syn addition of H2 (H2, Lindlars catalyst) +

H3CH2C H3C H3C

C H

CH2 C H

CH3 CH2CH3 CH3

Name_______KEY_____________________ Date___________________________ Use curved arrows to indicate electron flow in the stepwise mechanism for the reaction below. Be sure to account for the formation of both products. (6 pt.)
H H3C H H3C C H C CH3 H3C CH2 C CH3
H H3C C H H3C C H H Cl H H CH3 C CH3 C C H H3C C C H H H Cl H C C H C CH3 Cl H H3C CH2 C CH3 H C C C H H H3C CH2 C Cl CH3 Cl C H H H C C H H

17a

H C C H CH3

H C C H

CH2

C Cl

+ H

Cl

+
H C

Cl C

Name_______KEY_____________________ Date___________________________ One might argue that it is also possible to form the products below. Why are they not formed in appreciable amounts? (4 pt.)
Cl H3C H H3C C H C CH3 C C H H Cl H3C C C H CH3 CH CH3

17b

+ H H

+
CH C

CH3

Does NOT occur to a large extent.

Cl

CH3

Protonation of the other double bond gives a 2 cation with a resonance structure of another 2 cation. The products in 17 a form a more stable 3 cation and its resonance structure a 1 cation.
Cl H Cl H H3C C H C CH3 C C H H H3C C H C CH3 H H H H3C C C CH3 H Cl C H C H Cl H H3C CH C CH3 C CH3 Cl C H C H H H H3C C C CH3 CH CH3

Name_______KEY_____________________ Date___________________________ The hard insecticide heptachlor is (banned because of its toxicity and slow decomposition in the environment), shown below, is made by a Diels-Alder reaction. What diene and dienophile are required for that synthesis? (5 pt.)
Cl Cl Cl Cl H Cl Cl H Cl

18a

Cl Cl Cl

Cl Cl

Cl H Cl Cl

Cl

Cl Cl

Cl Cl Cl H

Cl Cl Cl Cl H Cl Cl H Cl

Name_______KEY_____________________ Date___________________________ What would be the product of the diene and dienophile below? (5 pt.)
O

18b

Name_______KEY_____________________ Date___________________________ In the reaction coordinate graph below, which product is the kinetic product and why? (4 pt.)

19a

By definition, the kinetic product is the one formed fastest (has the lowest activation energy). In the reactions above, product 1 has the lower activation energy.

19b

What reaction conditions favor the formation of the kinetic product? (6 pt.)

Kinetic products are favored by short reaction times under cold reaction conditions.