Organic Chemistry Lab II Experiment 1 Problem Set

Name ______________________________

Instructions: This is a take-home assignment. You are to work individually. Do not discuss your work with other members of

the course. If you need assistance consult your professor. You may use any resources available to you, e.g.,
notes, textbook, library, Internet, journals, etc. Answers to each question must be neatly written and clear. It is
strongly advised that you work out your answers on scrap paper before completing your final answers here.

1. (6 pts) Estimate the chemical shifts of the protons indicated below using the parameters in Table 21.3 in
Techniques in Organic Chemistry, 3rd ed., by J. R. Morhig, et al.
Proton Est. (ppm)

CH2 CH2 CH3

Cl

________

________

________

2. (6 pts) Estimate the chemical shifts of the protons indicated below using the parameters in Tables 21.3 and
21.5 in Techniques in Organic Chemistry, 3rd ed., by J. R. Morhig, et al.
Proton Est. (ppm)

Ha
C
Hb

C(CH3)3
c

C
H

________

________

________

3. (6 pts) Estimate the chemical shifts of the protons indicated below using the parameters in Tables 21.4 and
21.5 in Techniques in Organic Chemistry, 3rd ed., by J. R. Morhig, et al.

Hb

Proton Est. (ppm)

Hc

Ha
HO

________

________

________

4. (8 pts) Indicate the number of different kinds of protons in each compound.

Number of different kinds of protons
2,2-dimethylbutane

______

2,3-dimethylbutane

______

1-bromo-4-methylbenzene

______

1-bromo-2-methylbenzene

______

5. (6 pts) Predict the multiplicity (the number of peaks as a result of coupling) for each of the protons indicated
below.

Ha

Proton Multiplicity

Hb

CH3
c

___

___

___

6. (17 pts) The 1H NMR spectrum of a compound of molecular formula C5H8O2 is shown below.

(a) Calculate the DBE: _______

(b) Complete the data table below.
(ppm)

H type

integration

splitting

(c) Deduce the structure of the compound and assign its NMR signals.

possible structure fragments

7. (17 pts) A compound with the molecular formula C3H8O produces the 1H NMR spectrum below.

When this compound is treated with D2O, the 1H NMR signal at 2.0 ppm disappears and another signal at 4.6
ppm appears. Moreover, when the compound is highly purified and care is taken to remove all traces of acid in
the NMR solution, the singlet at 2.0 ppm is replaced by a doublet. Finally, the chemical shift of the 2.0 ppm
signal is highly concentration dependent; an increase in concentration in the NMR sample results in a downfield
shift of this signal.
(a) Deduce the structure of the compound and assign its NMR signals.

(b) Explain why the 2.0 ppm signal changes upon addition of D 2O, removal of acid, and change in
concentration.

8. (17 pts) In solution, dimedone (5,5-dimethylcyclohexan-1,3-dione) is a mixture of keto (A) and enol (B & C)
isomers. The 1H NMR is shown below. In the sample, the two enol isomers are equilibrating very fast compared
to the NMR time scale. Furthermore, the enol isomers are indistinguishable by 1H NMR.

(a) Assign the signals in the spectrum that correspond to the keto form.

(b) Assign the signals in the spectrum that correspond to the enol form.

(c) Use the integrations to determine the percent of keto form present in the mixture.

9. (17 pts) A compound of molecular formula C8H14O produces the 1H NMR spectrum below.

Its infrared spectrum shows a strong carbonyl stretching peak, which indicates that C 8H14O is either an
aldehyde or a ketone. Deduce the structure of the compound; estimate the chemical shifts of the different
types of protons using the parameters in Tables 21.3-21.5 in Techniques in Organic Chemistry, 3rd ed., by J. R.
Morhig, et al., and assign all the NMR signals.