Chem 128B, Winter 2010, Exam #2 KEY 1.

(12 points total) Please provide the appropriate IUPAC name for the following compounds. Please put your final answer in a box. a.
O HO

Cl

3-Chloro-1-hydroxyhept-3(Z)-en-2-one

b.
O

H OH

4(S)-Hydroxy-2-methylpent-2(E)-enal

c.
Br OH

2(R)-Bromo-4-phenylbut-3(Z)-enoic acid

2. (8 points total) Please show all of the possible hydrogen bonds between H2O molecules and the compound shown below.
H O H H O Br OH O H O H O H H H H

O O H H

O H H

3.

(21 points total) Please provide structures for the organic products for the following reactions. Show stereochemistry as appropriate.

a.
O 1.
ether

OH

MgBr

2. HCl, H2O

b.
Cl +
2

CuLi
ether

Cu

c.
H O

O + CH2I2 Zn(Cu)
ether

racemic

d.
H Br
+ CHBr3 K O-t-Bu

Br H meso

e.
O 1. Na+ C 2. neutralize C
racemic

OH

f.
Br OH O +
PTSA cat.

racemic

Br

g.
O H +
predominantly Z

H
PPh3

Ph

4.

(29 points total) Please provide structures for the products of each step in the reaction sequences given below. Show stereochemistry as appropriate.
a. O + Br H OH HO
H+ cat. removal of H2O

H Br

O 1. Mgo, THF 2. O 3. HCl, H2O, warm

O Br + P(OEt)3 EtO O OEt H O

b. PBr3 Br

OH

1. Mgo, ether 2. CO2 3. neutralize

OCH3

HCl gas in CH3OH O

OH

c.

1. BH3 2. H2O2 / NaOH OH

PCC CH2Cl2

H N

NH2

O NaBH3CN

5. (15 points total) Please interpret the spectral information shown below and show your work. Summarize your interpretation by drawing a structural formula that is consistent with all of the information and put a box around the structure.

70

60

50

40 PPM

30

20

10

The peak at 16 ppm is pointing down in the APT

2 PPM

Integration: 2H, 2H, 2H, 3H from left to right for the 4 multiplets

IR: shows a strong peak at 1130 cm-1 for C-O stretching suggesting an ether since there is no peak for OH stretching or for C=O stretching; C-H stretching only between 2800-3000 cm-1 indicating only alkane C-H
13

C-NMR: peaks for 4 different types of carbons; APT 3 peaks pointing up are CH2- or C-, 1 peak pointing down is for CH- or CH3; peaks at 69 and 67 ppm have the appropriate chemical shift for C-O- for the 2 carbons on either side of the ether, peak at 43 ppm indicates attachment to an electron withdrawing group, thus C-O-C- + -C-X + -C
1

H-NMR: integration and splitting patterns show 4 peaks which match the 4 different types of carbons in the 13C-NMR; peaks at 3.65, 3.55, and 3.4 ppm integrating for 2H each have a chemical shift appropriate for CH2attached to O- or other electron withdrawing group such as a halogen; the peaks at 3.65 and 3.55 ppm have complementary splitting patterns suggesting that they are neighboring CH2-; the peak at 3.41 ppm is a quartet with complementary splitting to the triplet for 3H at 1.1 ppm, these two together indicate CH2-CH3, thus X-CH2-CH2-O-CH2-CH3 MS: Molecular ion at m/z 108 and 110 with height ratio of 3:1 indicating the presence of Cl Summary: putting it all together gives 1-chloro-2-ethoxyethane
O Cl

6. (15 points total) Please interpret the spectral information shown below and show your work. Summarize your interpretation by drawing a structural formula that is consistent with all of the information and put a box around the structure.

IR: very strong peak at 1710 cm-1 for C=O stretching plus the very broad peak between 3600-2300 cm-1 for the OH stretching of a carboxylic acid; no indication of C=C- or C=C-; thus -COOH
13

C-NMR: peaks for 6 different types of carbons; APT 5 peaks pointing up are for CH2- or C-, 1 peak pointing down for CH- or CH3; peaks at 209 and 179 ppm have the chemical shift appropriate for C=O, either two COOH or one COOH and one aldehyde or ketone; peaks at 42, 33, and 30 ppm have chemical shifts that indicate C- attached to something electron withdrawing such as C=O; peak at 19 ppm indicates less influence of the C=O; thus -C-(C=O)-C- + -C-C=O + -C1

H-NMR: integration and splitting indicates 5 peaks with 2 peaks together in the multiplet at about 2.5 ppm; there is only 1H that is exchangeable with D 2O at 9.1 ppm indicating only one COOH; the 4H in the multiplet at 2.5 ppm and the 3H singlet at 2.2 ppm have chemical shifts appropriate for CH-C=O and the 3H singlet indicates a CH3; the multiplet at 1.9 ppm does not have enough chemical shift to be directly next to the C=O; the peaks at 2.5 and 1.9 ppm are the only peaks with splitting indicating that they are neighbors; thus CH3-(C=O)-CH2-CH2CH2-COOH MS: weak molecular ion at m/z 130; base peak at m/z 43 for [CH3-C=O]+ resulting from alpha-cleavage Summary: putting it all together gives 5-oxo-hexanoic acid
O O

OH