Use the following molecule for questions 1 - 2.
(1) Carbon #2
             A. is sp3 hybridized
  B. is sp2 hybridized
  C. is sp hybridized
  D. has three p bonds and one s bond
  E. is a tetrahedral center
   
(2) Carbon #1
             A. is sp3 hybridized
  B. is sp2 hybridized
  C. is sp hybridized
  D. has three p bonds and one s bond
  E. is a trigonal planar center
     
(3) Which acid is strongest?
             A. HF
  B. HCN
  C. H2O
   
(4) Which base is strongest?
             A. HF
  B. HCN
  C. H2O
   
(5) Given the following reaction, which is the conjugate base according to Brønsted-Lowry Acid/Base Theory?
             A. I
  B. II
  C. III
  D. IV
   
(6) An alkane, C6H14 , reacts with Cl2 in the presence of UV light to produce FIVE constitutional isomers with the formula C6H13Cl. The structure of the parent alkane is:
             A.
  B.
  C.
  D.
  E.
   
(7) The folded conformation that unsubstituted cyclic alkanes (4 to 6 carbons) takes on is caused by

I. strained bond angles
II. destabilizing eclipsing interactions
III. destabilizing 1,3-diaxial interactions

             A. I and II
  B. I and III
  C. II and III
  D. all of these important
  E. none of these important
   
(8) Baeyer correctly predicted small cycloalkane rings would be highly strained and reactive. He also incorrectly predicted that larger rings would be impossible to synthesize due to instability. What did his model leave out?
             A. He did not understand reduced eclipsing interactions.
  B. He assumed that the molecules were flat.
  C. He neglected steric strain.
  D. He neglected orbital expansion.
  E. More than one of the above.
   
(9) In reference to the conformers defined by the C2 to C3 bond axis in butane and pentane, the energy difference between the anti and gauche conformers for pentane is larger than it is for butane. Which of the following best explains this?
             A. Enhanced eclipsing interactions.
  B. Orbitals are off-center.
  C. Enhanced steric strain.
  D. None of the above.
  E. More than one of the above.
   

(Use the following information for questions 4-8.) Again, considering the polar reaction we used in class for an example of reaction mechanisms and the following reaction profile:

(10) The energy of the reaction is the difference between points
             A. 2 and 1
  B. 3 and 1
  C. 5 and 1
  D. 4 and 1
  E. 4 and 3
   
(11) The energy of the rate-determining step is the difference between points
             A. 2 and 1
  B. 3 and 1
  C. 5 and 1
  D. 4 and 1
  E. 4 and 3
   
(12) As drawn, the diagram shows that the overall reaction is
             A. exothermic
  B. endothermic
  C. sterically hindered
  D. polar
  E. radical
   

(13) Which is the proper name for the following compound?
             A. 2-pentene
  B. cis - 2-pentene
  C. trans -2-pentene
  D. E -2-pentene
  E. Z - 2-pentene
   
The following general reaction will be used for Questions 14 — 15. Different reagents and sets of conditions will be supplied. Choose the correct product from the choices listed.

a.
b.
c.
d.
e. No reaction

(14) Reagent: KMnO4 Conditions: aqueous acid
             A.
  B.
  C.
  D.
  E.
   
(15) Reagent: 1. O3; 2. Zn, HOAc
             A.
  B.
  C.
  D.
  E.
   
(16) If Lindlar’s Catalyst is used to hydrogenate 2-pentyne, which of the following products will be produced?
             A. n-pentane
  B. 1,3-pentadiene
  C.
  D.
   
(17) Propyne is reacted with mercuric sulfate in aqueous acid. Which of the following products is isolated from the reaction mixture?
             A.
  B.
  C.
  D.
   

(18) Consider the following reaction:

The resulting solution from the above reaction does NOT rotate plane-polarized light. The correct explanation for this is that

             A. none of the product(s) possess a chiral center.
  B. the carbocation intermediate is pyramidal in geometry.
  C. a racemic mixture is formed.
  D. achiral reactants produce chiral products.
  E. no reaction occurs.
   
(19) How many stereogenic centers are present in the following molecule.

             A. 3
  B. 4
  C. 5
  D. 6
  E. more than 6
   
(20) Which of the following best accounts for the stability of the allyl radical?

             A. Steric hindrance in the primary alkyl radical is at a minimum
  B. The balance between R groups and H’s is ideal in the secondary radical.
  C. Tertiary alkyl groups are the most stable.
  D. Resonance effects stabilize this form.
  E. It's one of the great mysteries of nature...
   
(21) Which of the following are unusual about the Grignard reagent and serves to make it a useful reactant?
             A. The chloride anion is stable.
  B. A carbocation (C electrophile) is produced.
  C. A carbanion (C nucleophile) is produced.
  D. The metal has empty d-orbitals that promote reactivity.
  E. Given differing reaction conditions, all of these are true.
   
(22) What would be the predominant product from the following reaction, and which mechanism would be preferred?

             A. propene, E1
  B. propene, E2
  C. 2-propanol, SN2
  D. 1-propanol, SN1
  E. 2,2-propanediol, oxidation
   
(23) An INCREASE in which of the three effects noted below leads a particular substrate to react via the SN1 pathway rather than the SN2 pathway?

I. steric hindrance
II. leaving group stability
III. carbocation stability
             A. I
  B. II
  C. III
  D. None of these has the desired effect.
  E. More than one of the above.
   
(24) A compound of the formula C2H5ON has a strong IR peak at 1700 cm-1 and a medium strength narrow peak at 3300 cm-1. It is likely a(n)
             A. carboxylic acid
  B. amide
  C. alcohol
  D. enol
  E. diazonium salt
   
(25) Peaks are observed in the IR spectra for a compound at 1750, 2850, 2900, 2925, and 3400 wavenumbers. Which of the following is the most likely structure for this compound>
             A.
  B.
  C.
  D.
  E. None of the above.
   
(26) Which of the following analytical techniques used in organic chemistry is primarily used to identify functional groups?
             A. Mass spectroscopy
  B. IR
  C. elemental analysis
  D. NMR
  E. UV-Visible spectroscopy
   
(27) How many 1H NMR signals would you expect from p-dimethoxybenzene?

             A. 2
  B. 3
  C. 4
  D. 5
  E. >5
   
(28) How many 13C NMR signals would you expect from p-dimethoxybenzene?
             A. 2
  B. 3
  C. 4
  D. 5
  E. >5
   
(29) Which of the following correctly describes the NMR experiment?
             A. NMR light is passed through the sample and an absorbance spectrum is collected.
  B. A solid sample is rotated in a radio frequency field and magnetic signal is noted.
  C. A radio frequency field is applied and magnetic field is tuned.
  D. A magnetic field is applied and radio frequency radiation is tuned.
  E. A magnetic field is applied and microwave radiation is tuned.
   
(30) On monoaddition of HCl to 1,3-cyclohexadiene, multiple products are formed. Select the products from the choices provided below.
             A. 3-chlorocyclohexene
  B. 4-chlorocyclohexene
  C. 2-chlorocyclohexene
  D. a and b only
  E. a, b, and c
   
(31) Match the 3 steroid structures shown below to the following lmax values respectively: 257 nm, 304 nm, 356 nm.

             A. A, B, C
  B. A, C, B
  C. B, A, C
  D. C, A, B
  E. C, B, A
   
(32) Which of the following are characteristics of benzene that differentiate it from other organic compounds?

I. Benzene undergoes substitution rather that addition.
II. Benzene is easily hydrogenated.
III. Benzene has no characteristic aroma.

             A. I and II only
  B. II and III only
  C. III only
  D. I
  E. all of the above
   
(33) What rule can be used to determine in a species is aromatic?
             A. Hund’s Rule
  B. Frosts’s Circle
  C. Huckel’s 4n+2
  D. "neutral, flat and conjugated"
  E. Le Chatelier’s Principle
   
(34) Ortho/para-directing groups for aromatic electrophilic substitution always have
             A. a negative charge
  B. activating effect on ring
  C. a lone-pair of electrons
  D. a positive charge
  E. none of the above
   
(Use the following information for questions 35 and 36.) A Friedel-Crafts acylation is carried out on phenol:
(35) Which of the following sets of reagents are used for this procedure?
             A. AlCl3 / Cl2
  B. KMnO4 / H+
  C. HNO3 / H2SO4
  D. AlCl3 / RCOOH
  E. AlCl3 / RCOCl
   
(36) Which of the following is the correct product for this reaction?

             A. I and II only
  B. II and III only
  C. I and III only
  D. none of the above
  E. all of the above
   
(37) Which of the following compounds is the most oxidized C compound?
             A. primary alkane
  B. alcohol
  C. aldehyde
  D. carboxylic acid
  E. alkene
   
(38) Which of the following is true of the IR spectra of compounds containing an —OH group.
             A. The position O-H stretch can be used to differentiate between phenols, alkyl alcohols, and carboxylic acids
  B. the C—O stretching frequency is altered by H-bonding
  C. H-bonding has no effect on the -OH stretching frequency
  D. the alcoholic proton is shifted downfield from alkyl protons.
  E. the shape of a peak in the spectrum can be altered by dilution.
   
(39) Mild oxidation of thiols lead to
             A. sulfides
  B. thioacetamides
  C. sulfonic acids
  D. sulfonates
  E. disulfides
   
(40) Nucleophilic addition reactions to carbonyl groups can be catalyzed by either bases or acids. Base catalyzes these reactions by
             A. making the C of the carbonyl group more electrophilic.
  B. making the C of the carbonyl group more nucleophilic.
  C. shifting the equilibrium of the reaction.
  D. being a powerful nucleophile itself.
  E. none of these.
   
(41) Which of the following is the most predominant product from the reaction of cyclohexanone with excess methanol in the presence of HCl?
             A. an alcohol
  B. an aldehyde
  C. a cleaved ring with aldehyde on one end and ketone on the other
  D. an acetal
  E. a hemiacetal
   
(42) For most carboxylic acids, the pKa is in the range
             A. 1-2
  B. 4-5
  C. 6-7
  D. 10-11
  E. 15-16
   
(43) Why are nitriles grouped with carboxylic acid derivatives based on reactivity?
             A. The N resonance stabilizes the C atom so that it acts like a carbonyl center.
  B. There is back-donation of electron density from the N lone pairs.
  C. They possess three bonds between C and an electronegative element.
  D. They are sterically hindered in the same fashion.
  E. c and d
   
(44) Which of the following statements is (are) true?
             A. Enols are more reactive than enolate anions.
  B. Enolates are more reactive than enols.
  C. Enols are easily isolated in basic solutions.
  D. Enolates are easily isolated in acidic solutions.
  E. More than one of the above is true.
   
(45) An aldehyde is placed in a solution of sodium hydroxide and Cl2 is added. The solution is then neutralized with acid. Which of the following products is observed?
             A. CHCl3
  B. alcohol
  C. acid anhydride
  D. acid halide
  E. alkyl halide
   
(Use the following information for questions 46 and 47.) Two different aldehydes reacting via the aldol condensation usually form four products.
(46) Which of the following best explains this observation?
             A. One aldol is formed, which can rearrange into the other products upon heating
  B. As the reaction proceeds, some of the intermediates are esters, so some Claisen products are also formed.
  C. Aldols reversibly rearrange into conjugated enones, so significant amounts of both enone and aldol are present in most cases.
  D. Each of the aldehydes will act both as electrophile and nucleophile giving four different combinations.
  E. The reaction generates diastereomeric pairs of compounds.
   
(47) Some aldehyde combinations do NOT form four products. Which of the following aldehydes would lead to only ONE product in combination with formaldehyde?
             A.
  B.
  C.
  D.
   
(Use the following compounds for Questions 48 and 49.)

(48) Which of these is a quaternary amine?
             A. I
  B. II
  C. III
  D. IV
  E. None of these.
   
(49) Which is the LEAST basic?
             A. I
  B. II
  C. III
  D. IV
   
(50) Benzenediazonium bisulfate salts are primarily used
             A. to produce mixed nitro/amine groups.
  B. to couple two nitroarene systems together.
  C. to make a nitro group attached to a ring reactive.
  D. to replace an arylamine group with another functional group.
  E. to cleave benzene rings.