4-Bromophenyl methyl ketoxime

Beckmann rearrangement

Introduction
A rearrangement reaction is one where the carbon skeleton of a molecule is
rearranged to give a structural isomer of the original molecule.
The Beckmann rearrangement involves a ketoxime which is converted into an
amide using acid as a catalyst.
Oximes are compounds that contain the group C=NOH and are derived from
ketones or aldehydes by condensing them with hydroxylamine. There are two
types of oxime, one derived from aldehydes and hydroxylamine, these are
called ‘Aldoximes’ [1] The other oxime derives from ketones and
hydroxylamine and are called ‘Ketoximes’[1] This experiment concentrates on
Ketoximes and the mechanism that occurs when polyphosphoric acid is
added. The resulting rearrangement is known as a ‘Beckmann rearrangement’
and the product is an acid-amide. This experiment uses an asymmetric
[2]
ketone, ‘4-bromoacetophenone’
O

CH3

Br

Fig.1. 4-bromoacetophenone
There is a possibility of two stereoisomers of the oxime.

OH HO
N N

CH3 CH3

Br Br

Fig.2.. Two possible isomers of 4-bromoacetophenone-oxime

The Beckmann rearrangement in this experiment will be performed using this
oxime.
The acid catalyst converts the oxime OH group into a leaving group (H 2O) in
the Beckmann rearrangement. As the leaving group departs an alkyl group
 [3]
that is trans to the OH migrates on to the nitrogen. The cation is then
‘trapped by water’[3] to give an amide. In this experiment the phenyl group or
the methyl group could migrate depending on the original structure of the
oxime.
The two possible products of this experiment are i) 4-bromophenyl acetamide
with the phenyl group migration and ii) 4-bromo-methylbenzamide with the
methyl group migration in the oxime.

NH CH3 CH3
NH

O
Br Br

Fig.4) N –(4-bromophenyl) acetamide 4-bromo-N-methylbenzamide.

A mixture of the two possible products will result, but the ratio of products will
be exactly the same as the ratio of isomers in the starting material. [3]
In this experiment the melting point of the product will be recorded and
compared to literary values to determine the product made. IR spectroscopy
will also be used.

Procedure
As lab script:

5.05g of oxime was used. Polyphosphoric acid was weighed out previous to
lab practical. Washings with cold water were in excess of 1500ml to raise the
pH to neutral.

After completing the recrystallisation procedure the yield was very low. After
inspection of the apparatus used, the flasks and beakers had a lot of white
residue in them. Washings from the apparatus were taken with excess
ethanol and collected. The washings were the placed in a rotary evaporator to
evaporate the excess ethanol . This mixture was then filtered and the product
weighed. This will be known as ‘Sample 2’
Results

Sample bottle with lid = 53.03g

Sample bottle with lid and sample = 53.83g
Mass of sample = 0.8g (wet)

Sample bottle 2 with lid = 51.73g

Sample bottle 2 with lid and sample = 55.37g
Mass of sample = 3.64g (wet)

The samples were then placed in a drying oven and dried for 24hours. They
were then re-weighed.
Mass of sample 1 = 0.68g
Mass of sample 2 = 3.33g

The melting points of each of the samples were then taken.

Sample Melting point 1 Melting point 2 Melting point 3 Mean

Sample 1 168°C 167.6°C 168.2°C 167.9°C
Sample 2 164°C 163.8°C 164.2 164°C
Table 1. Melting points of product formed.

The literary melting points of the two possible products, N –(4-bromophenyl)

acetamide and 4-bromo-N-methylbenzamide were then compared to the
experimental melting points found:

Compound M.P range (°C) Reference

N-(4-Bromophenyl)acetamide 166-170 www.chemexper.com[4]
4-Bromo-N-methylbenzamide
Table 2- literary melting point values.

Sample 1 was then analysed using infrared spectrometry (appendix 1) to

identify that an amide was produced from the reaction and that a Beckmann
rearrangement had been performed. Sample 2 was not analysed with
infrared as the sample was not entirely dry

Reaction mechanism
Discussion

After completing the recrystallisation process, the yield was very low. After
inspection of the beakers and flasks, it was discovered that a significant
amount of the product was left behind. The beakers and flasks were washed
with ethanol and the washing collected was then put on a rotary evaporator to
evaporate the excess ethanol. Once most of the ethanol had evaporated, the
solution was then filtered. Sample 2 was not recrystallised.

The infrared spectrum confirmed that an amide had been produced from the
experiment, and that a Beckmann rearrangement has occurred. Frequency
peaks of the infrared spectra of sample 1 were compared with reference
values from the book ‘Modern infrared spectroscopy’ [5] Literary values for an
amide analysed with infrared should have values of:
C=O stretching 1700-1640cm-1
N-H stretching 3500-3100cm-1
The infrared spectrum for sample 1 had the characteristic peaks at or around
these wavelengths, signifying that an amide had been produced. Sample 2
was not dry enough to perform infrared spectroscopy.

The melting points of the samples were then taken and compared to literary
values for the 2 possible products (tables 1 &2) Sample 1 had a melting point
within the literary values for N-(4-Bromopenyl)acetamide. This suggests that
the product made was N-(4-Bromopenyl)acetamide and that the phenyl group
was the group that migrated. Sample 2 had a lower melting point by about
3.9°C. This could possibly be due to impurities within the sample and because
it wasn’t recrystallised correctly. The results from Sample 2 are therefore
invalid for this experiment.
Further possible experiments could include acid hydrolysis of the product
amide. This could also help determine which group has migrated during the
rearrangement. The 2 possible products of the Beckmann rearrangement give
different products when hydrolysed with acid. The products from the acid
hydrolysis can then be tested for their solubility in acid or base. This will give
an indication as to which group migrated and hence give the product.

Conclusion
A Beckmann rearrangement occurred during the reaction, this is apparent
because an amide was produced from an oxime. The group that migrated
during the rearrangement was the phenyl group giving the compound N-(4-
Bromopenyl)acetamide. Testing the melting point on the final product helped
to distinguish which compound was made during the reaction.

References.

[1] Oximes, [WWW] http://www.1911encyclopedia.org/Oximes, (6/10/2008)

[2] [ CITATION Har99 \l 2057 ](1999) Experimental organic chemistry 2nd

edtion . Blackwell scienceLtd.

[3[ CITATION Cla01 \l 2057 ][ CITATION Stu96 \l 2057 ].(2001) Organic

Chemistry. Oxford university press.

[4] N-(4-Bromophenyl)acetamide [WWW] Chemexper.com. (7/10/2008)

[5] Stuart.B (1996) Modern Infrared Spectroscopy. John Wiley & sons Ltd.