Chemistry 605 (Reich)

FIRST HOUR EXAM Thur, March 3, 2011

Question/Points

R-10A R-10B R-10C R-10D R-10E

/7 /15 /23 /25 /30 AB BC CD 82 55 40 Hi Average Median 87 74 79

Total

/100

Distribution from grade list (average: 74.5; count: 43) 4 3 Number 2 1 0 0 10 20 30 40 50 Grade 60 70 80 90 100

Grading Copy
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.

7 Problem R-10A (C6H8O). Below are given the 13C NMR spectra of two stereoisomers of 3-methyl-pent-2-ene-4-yn-1-ol. Assign structures, and assign the signals by writing the values next to the appropriate carbons on each structure (Source: Aldrich Spectra Viewer). -effect, CH3 should be upfield
17.4 119.6 85.9 75.4 137.1 22.9

OH
58.9 119.4 81.8 82.2

137.5

OH -effect, CC should be upfield Z-isomer R-02G- 2

61.1

E-isomer 1 R-02G137.1

2 c (w w e

R-10A-1

119.6

17.4

20 m m st ve

180

160

140

120

100 ppm

80

60

40

20

82.2 81.8

61.1

137.5

R-10A-2

180

160

140

120

119.4

100 ppm

80

60

40

22.9

20

Briefly explain the basis for your assignment. Be specific. 4 -Interaction across double bonds causes upfield shifts (vs H at one of the positions). Thus in the E-isomer the CH 3 would be upfield ca 5 ppm compared to the Z-isomer. SImilarly, the first CC carbon would be upfield in the Z-isomer compared to the E For some reason the terminal acetylene carbon also moves a lot between isomers, but this is not a predictable -effect.

15

Problem R-10B (C9H20O). Identify the compound whose Problem R-10B (C9H20O). 75 MHz 13C NMR Spectrum in CDCl3. Source: ASV/Reich 10/41

13

C NMR spectrum is given below.

HINT: the longest chain is 6 carbons (it is a substituted hexane)

OH

There are three "terminating" groups (A-Me, C-tBu, G-CH2OH), the branch point is a CH carbon (B). So, basically, you have to fit two CH2 groups (E and F) into the framework below:
Me t-Bu C H CH2OH Only 4 ways to do this and still have a hexane

t s

D CBA

200

180

160

140

120

100 ppm

80

60

40

20

(a) DBE

0 . What functional groups might be present?

C-OH or C-O-C (alcohol, ether)

(b) What does the signal at 61.1 tell you about the structure? From the H-count (only 19 H on carbon), we know we have an alcohol (also absence of two downfield carbons) The shift really requires: 4 -CH2-CH2-OH O
62.6

70.1 OH OH

62.6 - 2.5 = 60.1

67

OH

(c) Plausible structures? Circle your choice. Assign the signals by placing the appropriate letters (A-G) on the structure. -2.1 + 2 + 4 + 2C + 2(4) + 2(2) -2.1 + 2 + 3 + 3C + OH 2(3) + 2(2) = -2.1 + 2(9.1) + 4(9.4) - 2(2.5) - 7.5 - 0 = 41.2 Obs: 51.3 A Pieces: 6 -CH2-CH2-OH -C(CH3)3 -CH3 -CH
23.9 C G D F B

OH

= -2.1 + 2(9.1) + 3(9.4) - 3(2.5) - 5 - 0 = 31.8 Obs: 51.3 70.1 + = 67.6 Obs: 61.1
28.9

OH

OH

OH

-2.1 + 2 + 3 + 3C + OH + 2(3) + 2(2) = -2.1 + 2(9.1) + 3(9.4) -3(2.5) - 5 - 2.5 - 0 = 29.3

Calc F: -2.1 + 2 + 5 + + OH + 2(3) + 2(4) + OH = -2.1 + 2(9.1) + 5(9.4) -2.5 - 5 - 2.5 - 7.5 = 45.6 (d) Do a chemical shift calculation for the carbon to which you have assigned the signal F ( 51.3) using the Grant-Cheney parameters. Calc F: -2.1 + 2 + 5 + + 2(3) + 2(4) + OH = -2.1 + 2(9.1) + 5(9.4) -2.5 - 2.5 - 7.5 = 50.6 Obs: 51.3 Calc B: -2.1 + 3 + 2 + 3 + OH + 3(2) + 3(2) = -2.1 + 3(9.1) + 2(9.4) - 3(2.5) - 5 - 2(3.7) = 24.1 Obs: 25.9

23 Problem R-10C (C23H34O2SSi) A 500 MHz 1H spectra is provided. (a) The structure of R-10C is given below. All of the important signals in the 1H NMR spectrum are labeled (A, B, C etc). Assign the proton signals by placing appropriate labels on the structure. For parts (b), (c) and (d), identify the couplings (e.g. for (b): JGX = 22 Hz, JGY = 32 Hz) m-Me -0.12 o-SPh -0.06 -0.16 o-Me -0.20 m-SPh -0.09 -0.29 K D Me3Si H C J H H F L H G CH3 I A H S O E O H Common errors: switch A/B, H/J, E/F. Decide between A and B with broadening of B by 4J to CH3. Select H for a better match with coupling to G, and leaning (weak). Select E for matched coupling with G, and size of coupling. To make assignments use: 1. Chemical shifts (type of proton 2. Integrations 3. Multiplicity 4. J-values = 23 Hz End-to-end = 23 Hz -3 for no J ID 4Draw a G JGH = 9 Hz JGH = 7 Hz JGE = 6 Hz JGF = 1 Hz

(b) The multiplet at 2.9 (G) is shown above. How many other protons are coupled to this one? coupling tree for G and report the coupling constants
Hz

16 lines - therefore coupled to 4 protons 0 H JHH = 17 Hz J J

80

70

60

50 H

40

30

20

10

JHH = 17 Hz JHG = 7 Hz JHG = 9 Hz JJJ = 13 Hz JJC = 7 Hz JJD = 1 Hz This is AB of ABXY, AB coupled equally to X and Y

(c) What kind of pattern is the multiplet at 2.5 (H)? and report J values. -3 for no J ID

ABX (AMX) Draw a coupling tree on the multiplet, label it,

5 _

(d) 5 Pt. BONUS question (don't do unless you have spare time): What kind of pattern is the multiplet at 2.2 (J)? AB of ABXY Draw a coupling tree on the multiplet, label it, and report J values with assignments.

This is basically an AB pattern (diastereotopic CH 2), each peak of which is split into a dd from coupling to C and D

Problem R-10C (C23H34O2SSi) 500 MHz 1H NMR Spectrum in CDCl3 (Source: Margaret K. Jones/Burke 10/19)
30 20 10 0

Hz
9.67

5.51

2.95 CH3 I

2.90

2.55

2.50

2.45

2.40

6.20

J B A HE O S D Me3Si M H J C H L 2.20
0.98 1.08 1.15 1.10 1.09

5.30

2.26

2.10

O H

HG H F 2.15
1.98

2.89

A 7.5

B 7.0 6.5

C 6.0

E F 5.5 5.0 4.5 4.0 ppm 3.5

G 3.0

H I J 2.5 2.0

K 1.5

L 1.0 0.5

M 0.0

25 Problem R-10D (C8H7NO2). Determine the structure of R-10D from the 1H NMR spectrum provided. 2 (a) DBE 6

(b) Analyze the 1H NMR signals. For each of the signals listed below report multiplicity and coupling constants to the extent the signals are amenable to first order analysis, and the part structure each corresponds to. H A B 5.43, 1H, d, J = 10 5.88, 1H, d, J = 17 H H C 6.75, 1H, dd, J = 17, 10 H H H These together require a vinyl group (CH=CH2) with no other coupling H The coupling between the gem-vinyl protons is too small to resolve

10

7.48, 1H, t, J = 8

7.69, 1H,dt, J = 8, ca 1 These together require a meta-substituted benzene

8.07 1H, ddd, J = 8, 2, 1

8.22 1H, t, J = 1.5 (probably dd)

(c) Give the structure of R-10D. If more than one structure is possible, circle your best choice. HG NO2 HE HD HF

13

Problem R-03D (C8H7NO2) Assign proton signals 300 MHz 1H NMR Spectrum in CDCl3 Source: Aldrich Spectral Viewer/Reich H Y X Y H H H H H H
30 20 10 0

H Hz Y X

H X

H H

H dd, J = 17, 10 Hz

8.2 G

8.1 F

8.0

7.9

7.8

7.7 E

7.6

7.5 D

7.4

6.8

6.7

H H H d, J = 10 Hz d, J = 17 Hz

5.9
2.00 2.18

5.8 B

5.7

5.6

5.5 A

5.4

1.15 1.02

1.04

G F 10 9 8

D 7

C 6

A 5 ppm 4 3 2 1 0

Problem R-10E (C8H16O3). Determine the structure of R-10E from the 1H NMR, 13C NMR and IR spectra provided. 1 (a) DBE (b) What information can you obtain from the IR spectrum (give frequency and peak 2 assignment). 3 3500-3600 cm-1 OH stretch 1730 cm-1 Carbonyl stretch - probably an ester

30

(c) Interpret the 13C NMR spectrum, showing any part structures that can be identified, and the corresponding values. 14.13 17.68 19.76 5 22.40 46.98 60.65 72.47 177.80 Very likely 4 CH3 4* carbon (not bearing an O) disappears in DEPT must be -CH2-OR OH Must be a O

H OR (d) The signal at 2.7 in the 1H NMR spectrum disappears when the sample is shaken with D 2O, and the signal 3.9 becomes a 1:3:3:1 quartet. What does this tell you about the structure? D H 2.7 H 2.7 O D2O O O Also possible: 4 CH3 CH3 CH2 HC H H H 3.9 Quartet Pentet 3.9 (e) Analyze the 1H NMR spectrum. For each of the groups of signals marked on the spectrum, report the multiplet structure in the standard format (e.g., 0.0 , dtd, J = 0.0, 0.0, 0.0 Hz, 2H) and any part structure you could obtain from the signal(s). H 1.15, 1H, d, J = 7Hz A 6 B C D E CH3-C 1.17, 1.18 - possible two methyl singlets, or isopropyl (J = 5 Hz - a little small) 1.27, 3H, t, J = 7Hz CH3-CH2 2.70, 1H, t, J = 7 Hz -O-H 3.86, 1H, pentet, J = 7 Hz H CH3-C-OH

4.17, 2H, q, J = 7 Hz -O-CH2-CH3

(f) Give your answer below. If more than one structure fits the data, draw them, but indicate your best choice by circling the structure O 10
10

OH

OH

O O

DEPT 135 Problem R-10E (C8H16O3). 13 C NMR Spectrum in CDCl3. Source: Kevin Jantzi/Reich 10/31

14.13 17.68 19.76 22.40 46.98 60.65 72.47 177.80

Normal

200

180

160

140

120

100 ppm

80

60

40

20

Problem R-10E (C8H16O3). IR Spectrum Neat Source: Nicolet FT-IR

3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800

600

Problem R-10E ((C8H16O3). 1 H NMR Spectrum in CDCl3. Source: Joe Langenhan/Gellman 10/31
30 20 10 0

Hz
13.44

O O

OH

x x E
4.20 4.15 ppm 4.10 3.90

x D
3.85 ppm 3.80

x B

x A

C
2.70 ppm 1.30

1.25

1.20 ppm

1.15

1.10

2.33

x
1.00 1.05

x x

B A

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0 ppm

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

20

This one from EX-2-10/11 Problem R-10G (C8H8Br2). This problem requires you to analyze the signals at 4.1 and 5.2. You are given the structure. (a) Do a "first order" analysis of the two multiplets shown below. Draw a coupling tree, and estimate couplings. What type of pattern is this?
1228.7 1223.4 1218.3 1212.8 1202.9 1548.1 1542.9 1538.0 1532.4 1192.6

Br HX Br HB HA

Hz

X JBX JAX

"AMX" solution (approximate Solution 1) JAB

B A JAB 6 3 5 4 1 JBX 8 2

5 JAX 7

5.15 5.10 4.10 4.05 4.00 3.95 ppm ppm (b) Do an accurate (quantitative) analysis. Use the frequencies shown above. If more than one solution is possible, show them both, and draw the proper coupling tree on the spectra below. Use appropriate criteria to distinguish the two. Show your work, and tabulate your data in an easily readable form.

5.20

1 2 3 4 5 6 7 8 15

1202.9 1192.6 1212.8 1202.9 1218.3 1212.8 1228.7 1223.4 Solution 1 Solution 2

JAX
1221.5 1216.6 1209.6

JBX
1199.1

JBX JAX A B

JAB JAX JBX A B AB i10 = i11 A B

9.90 to 10.6 +4.93 (-) -6.99 (+) +10.47 (-) +22.39 (-) 1219.04 1213.09 1204.36 1210.31 14.69 2.77 0.995 0.322 4.063 4.015 4.044 4.034

Solution 1

Solution 2 c+ = (6+4)/2 = 1207.85 ab+ = + = sqrt((8-2)(6-4)) = 17.5 c+ +/2 = 1216.6, 1199.1

c- = (5+3)/2 = 1215.55 ab- = - = sqrt((7-1)(5-3)) = 11.9 c- -/2 = 1221.5, 1209.6

Solution 1 is correct: 1. Solution 2 has one negative 3J, which never happens 2. Intensity calculation fits better for Solution 1

Problem R-10G (C8H8Br2) 300 MHz 1H NMR Spectrum in CDCl3 (Source: Wayne Goldenberg/Reich 11/31)

30

20
Hz

10

1228.7

1223.4 1218.3

1212.8

1202.9

1548.1

1542.9 1538.0

4.99

5.20

5.15 ppm

1532.4

5.10

4.10

4.05 4.00 ppm

1192.6

3.95

2.00

0.95

4 ppm