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90

Chapter 2

Structure and Reactivity

27. (i) Determine whether each species in the following equations is acting as a Brnsted acid or base, and label it. (ii) Indicate whether the equilibrium lies to the left or to the right. (iii) Estimate K for each equation if possible. (Hint: Use the data in Table 2-2.) (a) (b) (c) (d) (e) (f) H2O 1 HCN 34 H3O1 1 CN2 CH3O2 1 NH3 34 CH3OH 1 NH22 HF 1 CH3COO2 34 F2 1 CH3COOH CH32 1 NH3 34 CH4 1 NH22 H3O1 1 Cl2 34 H2O 1 HCl CH3COOH 1 CH3S2 34 CH3COO2 1 CH3SH

28. Use curved arrows to show electron movement in each acid-base reaction in Problem 27. 29. Identify each of the following species as either a Lewis acid or a Lewis base, and write an equation illustrating a Lewis acid-base reaction for each one. Use curved arrows to depict electron-pair movement. Be sure that the product of each reaction is depicted by a complete, correct Lewis structure. (a) CN2 (d) MgBr2 (b) CH3OH (e) CH3BH2 (c) (CH3)2CH1 (f ) CH3S2

30. For each example in Table 2-3, identify all polarized covalent bonds and label the appropriate atoms with partial positive or negative charges. (Do not consider carbon hydrogen bonds.) 31. Characterize each of the following atoms as being either nucleophilic or electrophilic. (a) (b) (c) (d) (e) (f ) Iodide ion, I2 Hydrogen ion, H1 Carbon in methyl cation, 1CH3 Sulfur in hydrogen sulfide, H2S Aluminum in aluminum trichloride, AlCl3 Magnesium in magnesium oxide, MgO

32. Circle and identify by name each functional group in the compounds pictured.
OH O

(a)

(b)

(c)

(d)

O H

(e)
O

(f )

(g)

O O

(h)

(i)
HO

O OH

( j)

O O

33. On the basis of electrostatics (Coulomb attraction), predict which atom in each of the following organic molecules is likely to react with the indicated reagent. Write no reaction if none seems likely. (See Table 2-3 for the structures of the organic molecules.) (a) Bromoethane, with the oxygen of HO2; (b) propanal, with the nitrogen of NH3; (c) methoxyethane, with H1; (d) 3-hexanone, with the carbon of CH32; (e) ethanenitrile (acetonitrile), with the carbon of CH31; (f ) butane, with HO2. 34. Use curved arrows to show the electron movement in each reaction in Problem 33. 35. Name the following molecules according to the IUPAC system of nomenclature.
CH3CH2CHCH3 CH3 CH3CHCH2CH3

(a)
H 3C

CH CH3

(b) CH3CHCH2CH2C CH2CH2CH2CH3


CH3CHCH3

Problems

Chapter 2

91

CH3 CH2 H CH3 C CH2 CH3 CH3 C CH2 CH CH3 CH3 CH2CH2CH2CH2CH3

(c) CH3CH2C CH2 CH3


CH2 CH3

(d) CH3

C CH2 CH3

(e) CH3CH(CH3)CH(CH3)CH(CH3)CH(CH3)2

CH3CH2 (f) CH2CH2CH2CH3


(i) (j)

(g)

(h)

36. Convert the following names into the corresponding molecular structures. After doing so, check to see if the name of each molecule as given here is in accord with the IUPAC system of nomenclature. If not, name the molecule correctly. (a) 2-methyl-3-propylpentane; (b) 5-(1,1-dimethylpropyl)nonane; (c) 2,3,4-trimethyl-4-butylheptane; (d) 4-tert-butyl-5isopropylhexane; (e) 4-(2-ethylbutyl)decane; (f) 2,4,4-trimethylpentane; (g) 4-sec-butylheptane; (h) isoheptane; (i) neoheptane. 37. Draw the structures that correspond to the following names. Correct any names that are not in accord with the rules of systematic nomenclature. (a) (b) (c) (d) 4-Chloro-5-methylhexane 3-Methyl-3-propylpentane 1,1,1-Trifluoro-2-methylpropane 4-(3-Bromobutyl)nonane

38. Draw and name all possible isomers of C7H16 (isomeric heptanes). 39. Identify the primary, secondary, and tertiary carbon atoms and the hydrogen atoms in each of the following molecules: (a) ethane; (b) pentane; (c) 2-methylbutane; (d) 3-ethyl-2,2,3,4tetramethylpentane. 40. Identify each of the following alkyl groups as being primary, secondary, or tertiary, and give it a systematic IUPAC name.
CH3 CH3 CH2 CH2 CH CH2 CH3 CH3 CH2 CH CH CH3 CH2 CH3 CH CH2 C CH3

(a)

CH2

CH CH3

(b) CH3

CH CH3

(c) CH3

CH CH3

(d) CH3

CH2

(e) CH3

CH2

(f) CH3

CH2

41. Rank the following molecules in order of increasing boiling point (without looking up the real values!): (a) 3-methylheptane; (b) octane; (c) 2,4-dimethylhexane; (d) 2,2,4trimethylpentane. 42. Using Newman projections, draw each of the following molecules in its most stable conformation with respect to the bond indicated: (a) 2-methylbutane, C2 C3 bond; (b) 2,2-dimethylbutane, C2 C3 bond; (c) 2,2-dimethylpentane, C3 C4 bond; (d) 2,2,4-trimethylpentane, C3 C4 bond. 43. Based on the energy differences for the various conformations of ethane, propane, and butane in Figures 2-10, 2-11, and 2-13, determine the following: (a) (b) (c) (d) The energy associated with a single hydrogen hydrogen eclipsing interaction The energy associated with a single methyl hydrogen eclipsing interaction The energy associated with a single methyl methyl eclipsing interaction The energy associated with a single methyl methyl gauche interaction

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Chapter 2

Structure and Reactivity

44. At room temperature, 2-methylbutane exists primarily as two alternating conformations of rotation about the C2 C3 bond. About 90% of the molecules exist in the more favorable conformation and 10% in the less favorable one. (a) Calculate the free energy change (DG 8, more favorable conformation 2 less favorable conformation) between these conformations. (b) Draw a potential-energy diagram for rotation about the C2 C3 bond in 2-methylbutane. To the best of your ability, assign relative energy values to all the conformations on your diagram. (c) Draw Newman projections for all staggered and eclipsed conformers in (b) and indicate the two most favorable ones. 45. For each of the following naturally occurring compounds, identify the compound class(es) to which it belongs, and circle all functional groups.
NH2 H C O B HCCHCH2OH OH
2,3-Dihydroxypropanal
(The simplest sugar)

HC HC

HSCH2CHCOH B O
Cysteine
(In proteins)

CH CH

O B CH3CHCH2CH2OCCH3
3-Methylbutyl acetate
(In banana oil)

CH3

C H

CH3CHP CHCqCCq CCHP CHCH2OH


Matricarianol
(From chamomile)

Benzaldehyde
(In fruit pits)

O CH 3 H3CE C ECH3 C H2C CH2 CH H2C CH2


Cineole
(From eucalyptus)

CH3 A C H2C CH H2 C CH A C D M CH2 CH3


Limonene
(In lemons)

CH2

H2C H2C H2C

H C N

CH3 A CH CH2 CH2

H3C

CH3 f CH C H

CH3 f

OP C

CH CH2

Heliotridane
(An alkaloid)

Chrysanthenone
(In chrysanthemums)

46. Give IUPAC names for all alkyl groups marked by dashed lines in each of the following biologically important compounds. Identify each group as a primary, secondary, or tertiary alkyl substituent.
H3C CH H3C CH2 CH2 CH CH CH3 CH3 CH2 HO
Vitamin D4 Cholesterol

H3C CH CH H3

CH2 CH2 CH2 CH CH3 CH3

HO H3C CH3 O

HO CH3 CH3

(A steroid)

CH3

CH3

CH2CH2CH2CH CH2CH2CH2CH CH2CH2CH2CH CH3


Vitamin E

H3C H3C CH NH2 CH


Valine
(An amino acid)

CH3 CH CH2 H3C CH CO2H NH2 CH

CH3 CH2 CO2H

CH3 CO2H NH2

CH
Leucine

Isoleucine
(Still another amino acid)

(Another amino acid)