Practice EXAM

Chemistry 605 (Reich)

FIRST HOUR EXAM Fri, March 6, 2009

Question/Points

R-08A R-08B R-08C R-08D R-08E

/12 /25 /18 /30 /15

Total

/100

Name

If you place answers anywhere else except in the spaces provided, (e.g. on the spectra or on extra pages) clearly indicate this on the answer sheets.

Problem R-08A. Consider the 20 MHz 13C NMR spectrum below, measured in CDCl 3.

47.3

38.4

36.1

28.4

F E D C B CH3-CH-CH2-CH2-CH-NH2 CH3 CH3 G A

23.0 24.3 28.4 35.9 38.2 47.3

t t d

100

80

60 ppm

40

24.3 23.0

20

(a) Calculate the 13C chemical shifts of the carbon C in the compound. Show your work.

(b) Calculate the 13C chemical shifts of the carbon D in the compound. Show your work.

(c) Assign the carbons by putting the appropriate letter over each peak in the spectrum.

Problem R-08B. For each of the labelled sets of peaks (A - E) identify the type of pattern (e.g. AB 2 or AA'BB'), calculate the exact chemical shifts and couplings for each of the protons involved using the line positions in Hz given, and report the result in the blanks provided. If you use first order analysis, justify it. Put appropriate letters on the structure assigning the protons. (Source: Hart 10/23) E MeO Type: Problem R-08B (C37H33NO6) MeO OMe 1 250 MHz H NMR Spectrum in CDCl3 Value(s): Expansion of 2.6-5.4 region. J value(s): (Source: Hart/OSU 10/23) Assign these peaks O N Ph O O

1332.6

1320.9

1300.8

1287.9

1152.7 1147.7 1143.3 1137.8

1049.3 1042.9 1033.4 1026.0

809.8 799.8 794.6 784.9

C Type: Value(s): J value(s): A Type: Value(s): J value(s): Assign these peaks B Type: Value(s): J value(s):
2.02 2.28

704.9 699.7 689.0 684.0

6.85

Assign these peaks

D Type: Value(s):
4.06

J value(s): Assign these peaks

Assign these peaks

1.00

A 5.4 5.2 5.0 4.8

B 4.6 4.4

C 4.2 4.0 ppm 3.8 3.6 3.4

D 3.2 3.0 2.8

E 2.6

Problem R-08C. You are given the 300 MHz 1H NMR spectrum of a disubstituted naphthalene. (a) Identify the two substituents, and summarize the NMR evidence that leads to that conclusion.

(b) What does the leaning of the peaks between 7.7 and 7.9 tell you?

(c) What does the leaning of the peaks between 7.1 and 7.25 tell you?

(d) For each of the 8 positions on the naphthalene as defined below, give either the substituent at that position, or the NMR signal (, multiplicity and J values). If there is more than one plausible structure asignment, draw the alternative structure, and indicate your preference. You may assume that naphthalene NMR properties are similar to those of benzene. 1 2 3 4 5 6 7 8

8 7 6 5

1 2 3 4

55.4

200.3

159.6

137.2 132.3 131.1 129.3 127.8 127.0 124.5

119.5

Problem R-08C (C14H14O2) 75 MHz 13C NMR Spectrum in CDCl3 (Source: ASV/Reich 03/38)

200

180

160

140

120

105.6

ppm

100

80

60

40

31.6

20

8.5

Problem R-08C (C14H14O2) 300 MHz 1H NMR Spectrum in CDCl3 (Source: ASV/Reich 03/38)

30

20

10

Hz

8.0

7.9

7.8

7.7

7.6

7.5

7.4

7.3

CHCl3

7.2

7.1

2.91 2.00 2.09 2.17

3.13

8.4

8.3
0.96 0.97

3.10 3.05 10 9 8 7 6 5 4 3 2

1.30 1.25 1 0

ppm

Problem R-08D. (C13H16O2). Determine the structure (or part structure) of R-08D from the 1H NMR, 13C NMR and IR spectra provided. (30 points) (a) DBE (b) What information can you obtain from the IR spectrum? List the data, and any conclusions you drew from it.

(b) Analyze the 1H NMR signals. For each group of signals listed below report integration, multiplicity and coupling constants to the extent the signals are amenable to first order analysis, and the part structure each corresponds to. Use the standard reporting method (eg. 3.42, qd, J = 7,2, 1H) 1.2 6.2

2.4

6.4

4.1

7.2

(c) Interpret the 13C NMR spectrum. Identify what kind of carbon each signal corresponds to, and write possible part structures. No 1 2 3 4 5 6 7 8 9 10 11 ppm 172.5 (s) 137.3 (s) 130.8 (d) 128.3 (d) 127.8 (d) 126.6 (d) 125.7 (d) 59.8 (t) 33.6 (t) 27.9 (t) 13.9 (q) Type and number of C (e.g. sp3 CH2) and/or part structures (e.g. N-CH 2)

M c C

(d) Determine the structure of R-08D. If more than one structure is possible, show them, and circle your best choice.

Problem R-08D (C13H16O2) 270 MHz 1H NMR Spectrum in CDCl3 (Source: J. Ringer/Reich 10/23) Hz

30

20

10

6.40 6.35

6.25 6.20 6.15 6.10

2.55 2.50 2.45 2.40

5.29

7.30 7.25 7.20 7.15 7.10 4.15 4.10 4.05

4.07

1.25 1.20 1.15

2.89

1.96

2.00

ppm

Problem R-08D (C13H16O2) 125.76 MHz 13C NMR Spectrum in CDCl3 (Source: J. Ringer/Reich 10/23)
59.8 33.6 28.0 172.5 137.3 130.8 128.3 127.8 126.6 125.7 13.9

136 134 132 130 128 126 124 ppm

200

180

160

140

120 ppm

100

80

60

40

20

Problem R-08D (C13H16O2) IR spectrum (neat) (Source: J. Ringer/Reich 10/23)

Problem R-08E. You are given the 300 MHz 1H NMR spectrum of a mixture of stereoisomers. The full spectrum is on the next page, but you only need to deal with the expansion on this page.
1 3 4

MeO

3 4

MeO

MeO

OMe

MeO

OMe

(a) Identify which is the major and which the minor isomer, and place assignments (E-1, E-2, Z-3, Z-4, etc ) over the appropriate peaks in the expansion below.

40 30 20 10 0

Hz

6.9

6.8

6.7

6.6

6.5

6.4

6.3

6.2

6.1

6.0

5.9

5.8

5.7

(b) Explain specifically how you made the E/Z assignment. Describe the multiplets you used (eg. td J=7, 3 Hz at 3.4) for each isomer.

Problem R-08E (C12H16O3) 300 MHz NMR spectrum in CDCl 3 Sourse: ASV

40 30 20 10 0

Hz

S
MeO

7.0

6.9

6.8

6.7

6.6

6.5

6.4
9.53

6.3

6.2

6.1

6.0

5.9

5.8

5.7

MeO + MeO

OMe

MeO

OMe
2.94

1.69 1.00 0.31 0.28 0.81

3.9

3.8

1.9

1.8

5 ppm