Chem31 - Villaseor 3rd Long Examination

I. Identification. Draw the following. (3 pts. each)

1. most reactive isomer of C 4H8O towards nucleophilic addition.
2. most acidic isomer of C 4H8O2.
3. isomer of C 4H8O2 with the highest boiling point.
4. most basic isomer of C 4H11N.
5. isomer of C 4H11N that gives an unstable diazonium salt.
6. isomer of C 4H11N that is unreactive towards nitration.
7. the acetal formed from pentan-2-one and propane-1,3-diol.
8. the fatty acid (18:3; 3, 9, 12).
9. Fischer structure of L-glucose.
10. the alditol formed from D-glucose.
11. the product formed from the reaction of D-glucose with HNO3.
12. the Ruff Degradation product of D-glucose.
13. Fischer structure of D-fructose (ketose form of D-glucose).
14. Haworth structure of -D-fructofuranose.
15. Haworth structure of -D-glucopyranose.
16. chair configuration of sucrose (a disaccharide of nos. 14 and 15).
17. more reactive compound towards nucleophilic addition: 4-nitrobenzaldehyde or
4-methoxybenzaldehyde. Draw the compound. (6 pts.)
18. a triglyceride that gives the following fatty acids upon hydrolysis: 12:0 18:2;
3,15 18:3;6,9,15.

II. Reaction Mechanisms. Draw the following (include stereochemistry) and

indicate the mechanism. No mechanism, no point. (3 pts. each)
3-methylbutanal + HCN, H+(aq) 19
3-methylaniline + acetyl chloride 20
2-ethyl-4-methylpentanal + H2O, H+(aq) 21
benzylamine + CH3I 22
2,2-dimethylhexanamide + NaOH(aq) 23
4-chloropentan-2-one + CH3NH2 24
25 + SOCl2 propanoyl chloride + cyclohexanol 26
dimethyl carbonate (diester) + excess CH3MgBr, H+(aq) 27
N,N-dimethylaniline + NaNO2, HCl 28
4-methylbenzoic acid + LiAlH4, H+(aq) 29
pentan-2,4-dione (active methylene) + NaOH(aq) 30 31
30 + acetaldehyde 32 + conc. H2SO4 33 + H2(g), Pt 34
acetic anhydride + benzylamine 35

III. Synthesis. Synthesize the following compounds. (3 pts. each)

36. 1-methylcyclohexene from cyclohexanone
37. toluene (methylbenzene) from aniline
38. n-pentamine from n-butanol

TOTAL PTS.: 120/100 pts.

ANSWER KEY:
I. Identification. Draw the following. (3 pts. each)
1. most reactive isomer of C 4H8O towards nucleophilic addition.
reactivity: aldehyde > ketone; steric hindrance slows down reaction.
O

H3C H

2. most reactive isomer of C 4H8O2 towards nucleophilic acyl substitution.

reactivity: carboxylic acids > esters; steric hindrance slows down reaction.
O

H3C OH

3. isomer of C 4H8O2 with the highest boiling point.

boiling point: carboxylic acids > ester; branching decreases b.p.
O

H3C OH

4. most basic isomer of C 4H11N.

basicity: 1o < 2o > 3o; Any secondary amine will do.
H3C NH CH3

5. isomer of C 4H11N that gives a sulphonamide that is soluble in base but insoluble
in acid.
In Hinsberg Test, primary amines gives a sulphonamide that is soluble in base
but insoluble in acid. Any primary amine will do.
H3C NH2

6. isomer of C 4H11N that is unreactive towards nitration.

Tertiary alkyl amines are unreactive towards nitrosation.
CH3

H3C N
CH3

7. the acetal formed from pentan-2-one and propane-1,3-diol.

Intramolecular nucleophilic addition.
 O
Nu Addn OH
+ HO OH
H3C CH3

O O
HO O

H3C
H3C
CH3 CH3

8. the fatty acid (18:3; 9, 12, 15).

The notation means that there are 18 carbons and three double bonds (located
at carbon 9, 12 and 15) in the carbon chain. Carbon 1 always starts at the acyl
carbon and do not forget to put the double bond in cis-form.
O

CH3
HO

9. Fischer structure of L-glucose.

L-glucose is just the mirror image of D-glucose. D-glucose is the only
carbohydrate that is required to be memorized.
O

HO H
H OH
HO H
HO H

HO

10. the alditol formed from D-glucose.

An alditol is the redox product of the reaction between the carbohydrate and
NaBH4. The carbonyl carbon is reduced to an alcohol.
 OH

H OH
HO H
H OH
H OH

OH

11. the product formed from the reaction of D-glucose with HNO3.
An aldaric acid is formed from the reaction of a carbohydrate and HNO 3. Both the
carbonyl and hydroxyl ends are oxidized to a carboxylic acid.
HO O

H OH
HO H
H OH
H OH

HO O

12. the Ruff Degradation product of D-glucose.

-
O HO O O O

O
H OH H OH H OH

HO H HO H HO H
Br2 in H2O CaCO3(s) Fe3+ HO H
H OH H OH H OH H OH
H2O2
H OH H OH H OH H OH

OH OH OH OH

13. Fischer structure of D-fructose (ketose form of D-glucose).

OH

O
HO H
H OH
H OH

OH
14. Haworth structure of -D-fructofuranose.
HO O HO

H OH
H OH

OH H

15. Haworth structure of -D-glucopyranose.

HO

O
H H
H

OH H
OH OH

H OH

16. Haworth structure of sucrose (a reducing disaccharide of nos. 14 and 15).

HO

O
H H
H

OH H
OH

H OH O

HO O

H OH
H OH

OH H
 17. more reactive compound towards nucleophilic addition: 4-nitrobenzaldehyde or
4-methoxybenzaldehyde. Draw the compound. (6 pts.)
EDG decreases the electrophilicity of the carbonyl carbon. The methoxy group is
an EDG while the nitro group is an EWG.
H O

N
O O
4-nitrobenzaldehyde

18. a triglyceride that gives the following fatty acids upon hydrolysis: 12:0 18:2;
3,15 18:3;6,9,15.
O

O CH3
O

O CH3
O

CH3
O

II. Reaction Mechanisms. Draw the following (include stereochemistry) and

indicate the mechanism. No mechanism, no point. (3 pts. each)
3-methylbutanal + HCN, H+(aq) 19
H CH3 NC CH3
Nu Addn
+

O CH3
+ HCN, H (aq)
OH CH3

19

3-methylaniline + acetyl chloride 20

O

NH2
H3C NH
O
NuAcS
+
CH3 H3C Cl
CH3

20
2-ethyl-4-methylpentanal + H2O, H+(aq) 21
CH3 CH3
CH3 CH3
Nu Addn
H + HO
CH3 + H2O, H (aq)
CH3

O OH
21

benzylamine + CH3I 22
NH2 NH
CH3

SN2
+ CH 3I

22

2,2-dimethylhexanamide + NaOH(aq) 23
H3C CH3 H
-3
C CH3
H2N CH3 O CH3
+ NaOH(aq) + NH3

O O
23
*NuAcS, then Acid-Base.

4-chloropentan-2-one + CH3NH2 24
H3C
O Cl N Cl
Nu Addn
+ CH 3NH 2
H3C CH3 H3C CH3
24

25 + SOCl2 propanoyl chloride + cyclohexanol 26

OH

OH Cl O
NuAcS NuAcS H3C
H3C H3C
+ SOCl2 + O
O O

25 26
dimethyl carbonate (diester) + excess CH3MgBr, H+(aq) 27
O O OH
NuAcS Nu Addn
H3C
O O
CH3 + CH 3MgBr
H3C CH3
+ CH3MgBr H3C CH3

CH3

27

N,N-dimethylaniline + NaNO2, HCl 28

H3C CH3 H3C CH3 H3C CH3
N N N
EArS NO
+ NaNO2, HCl +

NO
major product (p ara-)
28
You get extra points if you put all the possible products and indicated the major one.
So for this item, you can get 6/3 points.

4-methylbenzoic acid + LiAlH4, H+(aq) 29

HO O H O OH

+ NuAcS + Nu Addn
+ LiAlH4, H (aq) + LiAlH4, H (aq)

CH3 CH3 CH3

29

pentan-2,4-dione (active methylene) + NaOH(aq) 30 31

-
O O O O O O
acid-base
+ NaOH(aq)
-
H3C CH3 H3C CH CH3 H3C CH3

30 31
 30 + acetaldehyde 32 + conc. H2SO4 33 (major only) + H2(g), Pt 34
H3C OH
O O O
Nu Addn

-
+ H3C CH3
H3C CH CH3 H3C H

O O

32
H3C OH H3C H3C
+
CH
E1 Zaitsev
H3C CH3 + H2SO4 H3C CH3
Rule
H3C CH3

O O O O O O
33
H3C H3C

E Addn
H3C CH3 + H2, Pt H3C CH3

O O OH OH
34

acetic anhydride + benzylamine 35

O O O O
NH2 NuAcS
+ +
H3C O CH3 H3C OH H3C NH

35

III. Synthesis. Synthesize the following compounds. (3 pts. each)

36. 1-methylcyclohexene from cyclohexanone
CH3 O

from

O H3C OH CH3 CH3

+
C
+
Nu Addn E1 Zaitsev
+ CH3MgBr, H (aq) + H2SO4
Rule
37. toluene (methylbenzene) from aniline
CH3 NH2

from

N
NH2 NH2 +
N
EArS NuArS
+ CH3Cl, AlCl3 + NaNO2, HCl + H3PO2

CH3
CH3 CH3

38. n-pentamine from n-butanol

NH2
H3C from H C OH
3
H
[O] +
H3C OH + PCC
H3C O + HCN, H (aq)

Nu Addn

O OH
[O]
H3C CN KMnO4 + H3C CN

+
NH 2NH 2, KOH

[R]

E Addn NH2
H3C CN + H2, Pt H3C