CHE 332 Final Review

1. True or false

Name________________________

_______ CHF3 is a polar molecule. ________Electronegativity general increases from left to right on the periodic table. ________ Elements in row 3 of the periodic table may have more than 8 electrons in their Lewis dot structures. ________P is more electronegative than N, based on its position in the periodic table. _______ PH3 will act as a Lewis base. _______AlH3 will act as a Lewis base.(Al is in Group III of the periodic table). _______If BH3 were to behave as a base, its conjugate acid would be BH4+1 . _______CH3-1 and NH3 are Lewis acids. ______ Bicarbonate can function as a Bronsted-Lowry acid and base. _____ All Lewis acids are proton donors. ______ When comparing strengths of acids, the stronger acid has the smaller value of Ka. ______ If octanoic acid has a pKa = 4.9, it will exist predominantly in the carboxylate ion form at physiological pH (7.4). _______ If articaine has a pKa = 7.7, it will exist predominantly in the amine (base) form at physiological pH (7.4). _______ At a pH = 2.3, there will be 10 molecules of benzocaine (pKa = 3.3)in the amine form for every one molecule in the ammonium ion form. _______ At a pH = 6.3, there will be 1000 molecules of benzocaine (pKa = 3.3)in the amine form for every one molecule in the ammonium ion form. _______Attack of an electrophile on the C of an epoxide ring results in opening of the ring. _______Sulfhydryl groups can act as Bronsted-Lowry acids. _______ Ethers have higher boiling points than alcohols of the same molecular weight. _______A dehydration reaction of an epoxide results in a cis configuration product. _______Combiningf a primary alcohol with chromic acid results in a ketone product. _______Combining a secondary alcohol with PCC results in a carboxylic acid product. 1

_______Combining a tertiary alcohol with PCC results in no reaction. _____ An E-2 reaction will be preferred over a Sn-2 if HBr is used. _____ Iodide is a good nucleophile, but a poor base. _____Hydroxide is a good base, but a poor leaving group. _____Tertiary butyl alcohol readily undergoes a substitution by an Sn-2 mechanism. 2.Give the electronic geometry and type of orbital hybridization on the center atom of geometry a) CH4 _______________ hybridization ______________

b) N2H4

________________

_____________

c) NO2+1 _________

________________

d) OCN-1 ______________

_______________

e) SO2 _____________

_______________

3.Circle any molecules below which do NOT have a net dipole moment NO2+1 OCN-1 SO2

4. Draw 3 resonance structures for each of the following molecules, showing arrows showing the rearrangement of the electrons as one goes from resonance form to another.

5. Write the acid-base equation for the reaction of sodium bicarbonate(NaHCO3) with sodium dihydrogen phosphate(NaH2PO4) .

In the above reaction, the acid in the reactants is ____________________ The conjugate base in the products is ___________________ Why is this reaction important in baking powder?

6. Write the equation for the acid base reaction that occurs when phenol reacts with sodium ethoxide (NaOCH2CH3) (pKa of phenol = 9.95; pKa of ethanol = 15.9).

Given the pKa values, will the equilibrium favor the reactants or the products?_________ 7. Given the three acids: A)alphachlorobutyric acid, B)betachlorobutyic acid, and C) gammachlorobutyric acid.

Answer the questions below with letters A, B, or C. Which would you predict would be the strongest acid?___________________ Which conjugate base of the above acids will be the strongest base?___________ Which of the above acids will have the smallest pKa?______________________ Which of the above acids will have the smallest Ka?___________________ 8.Draw the possible resonance structures (showing all electrons, including non-bonding) of a) NO3-1 and
3

b) NO2-1 ion

Which will be a stronger acid nitric or nitrous acid and why?

9. Draw the structure of a)isopropylbenzene b) sec-butylcyclohexane c) 2,6 di(tert-butyl)toluene.

10. Draw the Newman projection of 1,2-difluoroethane a) in the least stable eclipsed conformation b) ina more stable eclipsed conformation

c) b) in the most stable staggered conformation

11.Draw the 2 conformations of trans-1,3-dichlorocyclohexane, label axial and equatorial Cl atoms, and indicate which of the 2 conformations is more stable, or if they are equally stable.

12.Do the same for the 2 conformations of cis 1,4-dichlorocyclohexane.

13. Label each C=C double bond in molecules below as .

14Label R or S for each chiral center in the large ring of carmine, a common red dye made from insects.

15. Show the complete reaction pathway for the 2 successive reactions of methanol to form formic acid in the human body

16.Show all the products that can result from the elimination reaction of 1-bromo 1-methyl cyclohexane with t-butoxide. Show the structure of t-butoxide. Circle the most stable product.

______________ Rule predicts the most stable product in the above type reactions. 17. Show the reaction pathway for the reaction of peroxyacetic acid with 1-fluoro-1cyclopentene with an acid water chaser to form a diol. Make sure stereochemistry of product is clear!

Label chiral centers in the product as R or S.

18.(2)Explain why rearranging bonds.

forms a reasonably stable carbocation without

19. (4)Two alternate terms for thiol group:_____________________ and ______________. One of these names refers to the affinity of sulfhydryls for the element_______________

20.(4)Show the product(if any) formed from a) cyclohexanol + H2CrO4 ( CrO3)

________

>

b) ) 1-methylcyclohexanol + H2CrO4( CrO3)

________

>

c) ethylene glycol+ H2CrO4( CrO3)

________

>

d)ethylene glycol + PCC ____>

NaNH2

________

>

+ (H2O) + H2SO4

__________

> HgSO4

____

>

+ H2

___

Lindlars catalyst

___

>

+ 2 NH3 + 2 Li ____>

BH3 followed by alkaline H2O2 ____>

+ ozone (O3) ______> (See Chapter 5.6)

21.

________

>

b)Show the product for the reaction of stereochemistry of product is clear!

with NH3 under alkaline conditions. Make sure

Label chiral centers in the product as R or S.

22. Indicate which of the molecule below are aromatic. ( Dont forget to add non-bonding electrons where needed!)

histidine

23. The long pair electrons of both pyridine and pyrrole can gain a hydrogen ion to form a positive charged cation, but pyridine has a pKa = 5.2 while pyrrole has a pKa of -4. Explain! 9

Pyridine

pyrrole

24. Show the complete reaction pathway for the reaction of Cl2 with toluene, with a FeCl3 catalyst.

25. Show the complete reaction pathway for a)benzaldehyde +

___

AlCl3 _________>

Show the complete reaction pathway for the reaction of

b) nitrobenzene +

___

AlCl3

___

>

26. Explain why X-rays or free radical initiators preferentially removes a H atom from the C # 3 ( allylic C) of 1,4 pentadiene.

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27. Using resonance structures explain why phenol has a pKa ~ 10 and cyclo hexanol has a pKa ~ 16.

28. Show how a phenol can react with a hydroxyl free radical (neutral OH radical) to form a more stable free radical molecule. Why will vitamin E free radical be even more stable?

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