B-1:00-2:00 pm

Feb. 27, 2012

Name:

ID # (last 4 digits)

I. Each of the questions is followed by four suggested answers. Select the one that is best in each case and write down your answer in the face page. (5 points each, 90 points/18 questions) (1) Which of the following has the highest boiling point?
(A) (B) (C) OH (D) OH

OH

OH

(2) Which functional group is not present in anti-HIV drug Crixivan?

(A) amide

(B) ketone

(C) 2o alcohol

(D) 3o amine

(3) The bond angle for the C-C-N bonds in acetonitrile (CH3CN) would be expected to be approximately: (A) 90o (B) 180o (C) 109.5o (D) 120o

(4) Which is the longest of the carbon-carbon single bonds indicated by arrows in the following compounds?

(5) Which is the best base to use to prepare C6H5CCT?

C6H5 C C H base T2O C6H5 C C T

(A) NaOMe

(B) NaNH2

(C) NaOAc

(D) NaOH

(6) What is the hybridization for the central carbon of DCC?

N C N (DCC)

hybridization

(7) Which of the following compounds has the highest boiling point?
N (A) (B) N N (C) N (D) N N

(8) Which of the following is not a resonance structure of the others?

N N N (B) N (C) H N N N N

(A)

(D)

(9) How many sp2-hybridized carbons are there in Lipitor?

C33H35FN2O5

A) 21

B) 22

C) 23

D) 24

(10) Which of the following pairs that are reasonable resonance forms?
(A) NH2 and NH2 (B) NH3 and NH2

(C)

NH2

and

NH3

(D)

NH2

and

NH

(11) For the following transformation, what significant change(s) would be expected by IR (ignoring C-H absorptions)?
O reduction OH

(A) A peak around 2150 cm-1 would disappear and a new peak around 3300-3500 cm-1 would appear. (B) A new peak around 2150 cm-1 would appear and a peak around 1715 cm-1 would disappear. (C) A new peak around 3300-3500 cm-1 would appear and a peak around 1715 cm-1 would disappear. (D) No change would be observed. (12) Compound A has a formula C6H10. It has a sharp IR absorption at 2100 cm-1. What is the possible structure for A?
(A) (B) (C) (D)

(13) The IR spectrum of an unknown compound is shown below, which of the following is the most likely structure for the unknown?

O (A) OH (B) OH (C)

O (D) O

(14) Which of the following has the longest C-O bond?

c O Me O O

(A) a

(B) b

(C) c

(D) d

(15) Which of the following compounds is the strongest acid? (A) ClCH2CO2H (B) FCH2CO2H (C) BrCH2CO2H (D) CH3CO2H

(16) A molecule with formula HCNO has two double bonds and no formal charges. Which of the following shows the correct connectivity of atoms for this molecule? (A) H-C-N-O (B) H-O-N-C (C) H-N-C-O (D) H-O-C-N

(17) Which curved-arrow notation in the following mechanisms is incorrect?

O (A) BF3 O BF3

(B)

Cl

AlCl3

Cl Cl Al Cl Cl + O

(C)

H O

(D)

BF3

O BF3

(18) Which of the following molecules has a dipole moment?

(A) CCl4 H (B) Cl H Cl (C) Cl Cl (D) H Cl C C C Cl H

II. (5 points) Ascorbic acid (a.k.a. Vitamin C) is a hydrophilic antioxidant. It is found in most citrus fruits. The pKa1 of ascorbic acid is 4.2 (lower than that of acetic acid). Please circle the most acidic OH in ascorbic acid shown below. Briefly explain your choice.

!
ascorbic acid

HO

OH O O O OH

HO

OH O O O OH

HO

OH O O O OH

The anion is in conjugation with the electron withdrawing carbonyl group. It can be stabilized by the resonance structures.

III. (5 points) Explain ortho-nitrophenol has lower boiling point than para-nitrophenol.
OH NO2 ortho-nitrophenol b.p. 214-217 oC NO2 OH para-nitrophenol b.p. 279 oC

O H N O O

or

O H N O O

orth-nitrophenol can easily form intramolecular H-bond, which makes it harder to form intermolecular H-bond. O O N O O O N O

para-nitrophenol can only form intermolecular H-bond, which leads to a higher boiling point since breaking this bonding needs extra energy (from liq. to gas).

Bonus: For a hypothetical molecule CH2XY, if carbon uses sp3 hybridization to form CH bond and sp5 to form C-X bond, what hybridization does carbon use to form C-Y bond? (5 points)
X C Y H H

1) two sp3 C-H bonds take 2x 1/4=1/2 s orbital and 2x3/4 =3/2 p orbital 2) one sp5 C-X bond takes 1/6 s and 5/6 p 3) CH2X take 1/2 + 1/6=2/3 s and 3/2 + 5/6=7/3 p 4) Carbon has one s orbital and three p orbitals 5) For C-Y: 1-2/3=1/3 s and 3-7/3=2/3 p s/p=1/2 sp2 hybridization

Chemistry 222 Spring 2012 Professor Zheng Hour Exam #1B 1:00-2:00 pm Feb. 27, 2012 Name: ID #(last 4 digits) This exam booklet contains 7 pages (including this face page). The total number of points is 100. Do not open your exam until you are told to do so. You can tear off this page when the exam starts. I. (Put your choice here) 1. 6. 11. 16. A A C C 2. 7. 12. 17. B B A D 3. 8. 13. 18. B C C D 4. 9. 14. D D A 5. 10. 15. B A B

II. (Dont put answer here) III. (Dont put answer here) Bonus. (Dont put answer here) TOTAL _________________________