CHEMISTRY 40 Problem Set Aromatic Compounds I. Indicate whether each of the following compounds or ions is aromatic or not: + a. c.

.. O ..

b.

d.

2.

Write the structures of the products formed from the reaction of the following reagents with (i) benzene, (ii) ethylbenzene and (iii) benzoic acid. If no reaction occurs, write NR. a. b. c. d. e. fuming sulfuric acid cold, dilute KmnO4 CH3 COCl, AlCl3 hot KMnO4 Br2/CCl4, light f. g. h. i. CH3Cl, AlCl3 H2O, H+ HNO3, H2SO4 Cl2, FeCl3

3.

Predict the major product(s) that will be obtained upon monobromination of each of the following compounds. Indicate whether the reaction will be faster or slower than the bromination of benzene. a. nitrobenzene b. benzaldehyde c. aniline

4.

Arrange the following compounds in the order of increasing reactivity towards ring nitration. a. benzene, iodobenzene, aniline, toluene b. O
C H OCH3 Cl CH3

5.

Suggest a scheme for the preparation of each of the following compounds from benzene. a. p-bromobenzenesulfonic acid b. 2,5-dichloronitrobenzene c. p-chlorobenzoic acid d. o-nitrotoluene e. benzyl alcohol f. styrene

CHEMISTRY 40 Problem Set CARBONYL COMPOUNDS, CARBOXYLIC ACIDS AND DERIVATIVES I. II. Draw the structural formulas and give the IUPAC names of three carbonyl compounds with molecular formulas C4H8O. Give the products of the reaction (if any) of i) benzaldehyde and ii) acetone with the following reagents: 1. 2. 3. 4. 5. 1. 2. 3. 4. Ag(NH3)2NO3 NaBH4, ethanol NaCN, dil H+ 2,4 DNP CH3CH2MgCl in ether, then H+/H2O SOCl2 CH3CH2OH, H+, heat heat, -H2O CH3NH2, -H2O, heat 6. CH3CHO, dil NaOH 7. CH3OH, H+ 8. I2, NaOH 9. Zn(Hg), HCl 10. NH2OH, H+ 5. 6. 7. 8. SOCl2, then CH3COOH PCl3, then CH3OH NaHCO3 PCl3, then aniline

III. Give the product(s) for the reaction of benzoic acid with the following reagents:

IV. Give a simple chemical test that can differentiate between the following pairs of compounds. Indicate: a) the reagents needed; b) the visible results of a positive test; and c) the equation for a positive reaction. 1. 2. 3. 4. 5. benzaldehyde and acetone 2-hexanone and 3-hexanone phenol and p-hydroxybenzaldehyde cyclohexanol and cyclohexanone acetaldehyde and 3-pentanone 6. acetophenone and benzoic acid 7. phenol and benzoic acid 8. acetic acid and propyl acetate 9. hexanoic acid and N-methyl hexanamide 10. benzamide and aniline

V. Complete the following reactions or sequences of reactions by providing the missing inorganic reagent or drawing the structure(s) of the missing reactant or product.
OCH3 OCH3 ? C O CH2CH3

1.

NH2NH2 KOH

O C

2.

CH3CHO, dil NaOH -H2O

? O C OH

O O

3.

CH3CH2

1. 2. H+, H2O

MgBr

CH2CH3

O O ? O H ? CH3CH2CH2 C OH 1. SOCl2 2. (CH3)2NH heat -H2O CH3CH2CH2 ? ? C OCH3

4.

CH3CH2CH2

5.

O O

H+, H2O heat

6.
?

SOCl2

H+, H2O heat

7.

SOCl2

H+, H2O heat

O O O

O O O H+, H2O heat

8.

O polyethylene terephthalate
O O NH CH C NH O CH2 C OH H2N CH C CH3 H+, H2O heat ?

9.

a tripeptide

CHEMISTRY 40 Problem Set ALKYL HALIDES 1. Complete the following chemical equations by supplying the major organic product:
CH3 CH3 CH3 Cl + KOH alcohol

a.

b. c.

CH3I

NaOH
Br + NaCN

CH3CH2CH2CH2
CH3 Br

d.

CH3

C H

CH

CH3 + KOH

alcohol heat

CH3

e.
Br

CH3OH

2. 3.

Give the IUPAC name of the organic substrate in nos. 1a 1e. Draw the structures of all the possible elimination products of 3-iodo-3,4-dimethylhexane. Rank the products in the order of increasing stability. Identify the major product. Draw the reaction intermediates for the reaction shown below:
CH3 Br CH3 C C CH3 CH3 H NH3 CH3 NH2 CH3 C C CH3 + CH3 CH3 H CH3 CH3 C C CH3 NH2 H

4.

Identify the more stable reaction intermediate and the major product.

CHEMISTRY 40 Problem Set Alkenes, Dienes, Alkynes & Arenes I. Write the equation for the reactions of (1) 1,2-dimethylcyclohexene and (2) 2-methyl 2butene with each of the following reagents. If there is no reaction, write NR. a. dilute H2SO4 d. HBr, peroxide h. conc H2SO4 b. cold dilute neutral e. Br2, H2O i. H2, Ni KMnO4 f. Cl2, CH3OH j. O3, then Zn/H+ c. HBr g. Br2, CCl4 II. Write the equation for the reaction of (1) 4-methyl-2-pentyne and (2) cyclopentylacetylene with each of the following reagents. Write NR if there is no reaction. a. 2 Br2, CCl4 b. 2 HCl c. H2O, H2SO4, HgSO4 d. excess H2, Pd/C e. Na, liq NH3 f. O3, then Zn, H+ g. warm KMnO4 h. Ag(NH3)2+ i. NaNH2

III. Write the equation for the reactions of 2,5-dimethyl-2,4-hexadiene with each of the following reagents: a. 1 mol HBr b. 1 mol Br2 c. 1 mol H2O, H+ d. excess O3, Zn/H+ e. excess H2, Pd/C

IV. Complete the following equations by drawing the structure of the major product. Show at least three repeating units for the polymerization reactions.

1.

1. O3 2. Zn, H+

2.

CH2CH2CH2 CH

CH2

1. O3 2. Zn, H+

3.

n H2C

CCl2

ROOR light or heat

ROOR light or heat

4.

n CH3CH

CHCH3

5.

n F2 C
n H2C

CF2
CH

ROOR light or heat

CH CH2

?
ROOR light or heat ?

6.

V. Propose a structure that would fit the given molecular formula and properties. Hint: Consider all types of hydrocarbons. 1. C4H6: reacts with Baeyers Reagent, Br2/CCl4 and Ag(NH3)2+ 2. C8H10: does not react with Baeyers reagent; decolorizes Br2/CCl4 only in the presence of light; produces benzoic acid upon treatment with warm KMnO 4 followed by an acidic workup. 3. C6H12: reacts with Baeyers reagent and Br2/CCl4; produces 2 equivalents of CH3CH2CHO upon ozonolysis 4. C5H8: reacts with Baeyers reagent and Br2/CCl4 but not with Ag(NH3)2+; produces CH3COOH and CH3CH2COOH upon ozonolysis CHEMISTRY 40 Problem Set: BIOMOLECULES 1. Raffinose, whose structure is shown below, is the most abundant trisaccharide in nature.
OH CH2 OH HO OH O CH2 HO HO HOH2 C O OH O HO O O

CH2 OH HO

a. b. c. d. e.

Name the three monosaccharide units in raffinose. Identify the two glycosidic linkages in raffinose. Is raffinose a reducing sugar? Does it undergo mutarotation? Does it form an osazone?

2. Alginic acid from seaweed is used as a thickening agent in ice cream and other food products. Alginic acid is a polymer consisting of D-mannuronic acid units linked together by -1,4-glycosidic bonds. From the structure of D-mannuronic acid shown below, propose a possible structure for a segment of alginic acid showing three monosaccharide units.
O H HO HO H H C H H OH OH

COOH D-mannuronic acid

3. Provide the structure of the product in the following reactions:

Cu2+ tartrate H H HO H CH2 OH OH OH O H dil HNO3 ? OH?

4. Give a simple chemical test that would serve to differentiate between maltose and sucrose. 5. Write the structure that fits the following descriptions using the aldohexose D-mannose as the reference:
O H HO HO H H H H OH OH

CH2 OH mannose

a. b. c. d. e. f. g.

a ketose isomer of D-mannose an enantiomer of D-mannose an epimer of D-mannose -D-mannopyranose a diastereomer of D-mannose a trisaccharide linked by -1,4-glycosidic linkages a non-reducing disaccharide of -D-mannose

6. Write the structure(s) of the major organic product(s) of D-mannose with a. phenylhydrazine b. HNO3 c. Br2, H2O 7. Complete the following reaction:

8. Write the structures of the following amino acids as a) zwitterion; b) at high pH; c) at low pH: a. alanine c. aspartic acid e. tyrosine b. lysine d. cysteine 9. Draw all the isomeric tripeptides that can be synthesized from glycine, alanine and tyrosine. 10. Draw the structural formula for aspartylalanyllysine. 11. What products are expected from the complete hydrolysis of the tripeptide in no. 10?