Beruflich Dokumente
Kultur Dokumente
Chapter 2
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
Problems
Chapter 2
91
CH3 CH2 H CH3 C CH2 CH3 CH3 C CH2 CH CH3 CH3 CH2CH2CH2CH2CH3
(d) CH3
C CH2 CH3
(e) CH3CH(CH3)CH(CH3)CH(CH3)CH(CH3)2
(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
92
Chapter 2
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
Benzaldehyde
(In fruit pits)
CH2
H C N
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
HO H3C CH3 O
HO CH3 CH3
(A steroid)
CH3
CH3
CH
Leucine
Isoleucine
(Still another amino acid)