Organic Chemistry Prelim Exam Part 1

A. Formal charges. Draw the Lewis dot structures of the following molecules/ions 4) Reaction of potassium hydroxide and tertiary butanol
and calculate the formal charge of the atoms inside the parenthesis.
1) Hypochlorite ion (Cl, O) pKa of H2O = 15.7 pKa of tert-butanol = 17
2) Nitrogen monoxide (N, O)
5) Reaction of tert-butyllithium with ammonia
B. Brønsted acidity. Draw the structure of the strongest Brønsted acid, and arrange
the following in order of INCREASING Brønsted acidity. Use "<" ('less than’) sign to
assign the lower vs. higher (e.g. A < B < C < D). + Li+
1) A. Benzoic acid, B. p-nitrobenzoic acid, C. m-nitrobenzoic acid, D. o-nitrobenzoic acid pKa of tert-butane = 53 pKa of NH3= 38
2) A. Ethyne, B. ethylene (ethene), C. ethane, D. benzene

C. Brønsted basicity. Draw the structure of the strongest Brønsted base, write the G. Resonance structures.
pKa of its conjugate acid, and arrange the following in order of increasing Brønsted 1) Draw the resonance structures of nitrobenzene. (5 pts.)
basicity. (Refer to Evan's pKa table if applicable). Use "<" sign. 2) Draw the resonance structures of phenol. (5 pts.)
1) A. NaOMe, B.tBuOK, C. NaOH, D. NaNH2
2) A. NaNH2, B. KHMDS, C. LDA, D. tBuLi
H. Molecular orbital
D. Lewis acidity. Draw the structure of the strongest Lewis acid, and arrange the Draw the molecular orbital diagram of ethene (H2C=CH2).
following in order of increasing Lewis acidity. Use "<" sign.
1) A. NaCl, B. CaCl2, C. AlCl3, D. TiCl4
2) A. BCl3, B. AlCl3, C. GaCl3, D. InCl3 Bonus question: Which of the following has the highest Lewis acidity (partial positive
charge)? Why? BF3, BCl3, BBr3, BI3
E. Lewis basicity. Draw the structure of the strongest Lewis base, and arrange the
following in order of increasing Lewis basicity. Use "<" sign.
1) A. NaOH, B. LiHMDS, C. tBuOK, D. LDA
2) A. Acetone, B. hexafluoroacetone, C. 1,1-difluoroacetone, D. bromoacetone

F. Indicate whether the given reaction PROCEEDS COMPELETELY, PROCEEDS

PARTIALLY, or DOES NOT PROCEED. (10 pts.)

1) Reaction of carbonate with methanol

pKa of HCO3– = 10 pKa MeOH = 15.5

2) Reaction of methoxide with bicarbonate

pKa MeOH = 15.5 pKa of HCO3– = 10

3) Reaction with propyne and sodium amide

pKa = 25 pKa of NH3 = 38

Note: 1) Use "<" sign for arranging compounds in order of increasing Brønsted/Lewis acidity or basicity, or boiling point. (e.g. EtOH < H2O < AcOH)
2) KHMDS = potassium hexamethyldisilazide, LDA = lithium N,N-diisopropylamide, DMAP = dimethyl aminopyridine, DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene, DABCO = 1,4-
diazabicyclo[2.2.2]octane, Cy2NEt = dicyclohexylethylamine, iPr2NEt = diisopropylethylamine