Chem 222 Exam 3 (Sample) Section A (5 points each; 70 points total) 1.

For which of the following compounds will E- and Z- isomers not exist?

A) a only 2.

B) b only

C) c and d only

D) d only

E) a and c only

Which alkene has the smallest heat of hydrogenation?

A) a 3.

B) b

C) c

D) d

What is the structure of the major alkene product?

A) a 4.

B) b

C) c

D) d

Which reagents (and in what order) would you use to achieve the transformation shown?

A) a then c

B) b then c

C) a then d

D) b then d

5.

The major alkene product expected is?

A) a 6.

B) b

C) c

D) d

What is the structure of the major organic product from the following sequence of reactions?

A) a 7.

B) b

C) c

D) d

Which reagent(s) would be most appropriate for the transformation shown?

A) a 8.

B) b

C) c

D) d

Which alcohol undergoes acid-catalyzed dehydration at the fastest rate?

A) a

B) b

C) c

D) a,b and c undergo dehydration at equal rates

9.

Which reagent is most suitable for the transformation shown?

A) Hg(OAc)2/H2O then NaBH4 B) OSO4/pyridine then NaHSO3/H2O C) BH3.THF/H2O then H2O2/OHD) cold, dilute KMnO4/OH-/H2O 10. What is the major product expected?

A) a 11.

B) b

C) c

D) d

How many distinct signals are expected in the 13C NMR spectrum of the molecule shown?

Br

Br

A) 4

B) 5

C) 6

d) 8

12. How is the signal for the proton indicated (arrow) in ultrapure 2,4-dimethylpentan-3-ol best described?

A) 3.20, 1H, quartet C) 6.00, 1H, triplet

B) 3.20, 1H, triplet D) 3.30, 1H, doublet

13. Protons A and B are ________________. They will occur at __________________ chemical shifts in the 1H NMR spectrum.

A) enantiotopic / identical C) diastereotopic/identical

B) enantiotopic/different D) diastereotopic/different

14. Compound A has molecular formula C5H10O4. NMR data for A is shown below. What is the structure of A? 3.3, 6H, singlet 3.7, 3H, singlet 5.0, 1H, singlet

A) a

B) b

C) c

D) d

15. [2 X 3 pts] Provide detailed arrow-pushing mechanisms that account for formation of the product shown in the following transformations. a)

b)

16. a) Compound A with molecular formula C12H22 reacts with two moles of hydrogen in the presence of platinum catalyst to give compound C. Treatment of A with hot basic KMnO4, followed by acidification gives compound B (shown below) and acetone as the only organic products. Provide a structure for A and C and a scheme showing the above transformations [3 pts].

b) Provide the missing starting materials, products or reagents (boxes) in the reactions below. i) [2 pts]

ii) [3 pts]

iii) [5 pts]

iv) [2 pts]

17.

[2 + 3 pts]

Provide efficient synthetic routes by which the following transformations may be achieved. More than one step will be necessary in each case. You may use any organic or inorganic reagents necessary. a)

b)

18. [4 pts] Treatment of Q (C5H11Br) with a base X and heat, gives compound R with molecular formula C5H10 as the major product. The 1H NMR spectrum of R is shown below. Identify Q, R and X. Show your reasoning. Indicate which signal in the spectrum corresponds to which proton(s) in R.