Synthesis and Characterization of Butyl Acetate

Andrew Cooke

Organic Chemistry - Lab C

Professor Mei

November 30th, 2021

Introduction

In this experiment, butyl acetate was synthesized from acetic anhydride and 1-butanol by

a procedure involving a series of reactions1. The chemical equation of the reaction is:

Butyl acetate was characterized and tested using the hydroxamic tests, Jones tests, determining

the boiling point, and using spectral characterization. The hydroxamic and Jones tests were done

to determine the purity of the butyl acetate by comparing the results with that of 1-butanol and

ethyl acetate. NMR, IR, gas spectrometry, and mass chromatography were also performed on the

final product to confirm the chemical composition of the product to be butyl acetate. Butyl

acetate actually has a lot of useful properties that are utilized on a daily basis. It is used as a

solvent for many oils, waxes, etc; and is also a synthetic fruit flavoring used in candy, ice cream

and other various foods. It is also found naturally in fruits, like the common red apple.

Experimental

To synthesize the butyl acetate, acetic anhydride (15 mL, 0.159 mol) was added to

1-butanol (15 mL, 0.164 mol) along with 2 drops of 18M sulfuric acid (which acted as a

catalyst). The reaction temperature was recorded at one minute intervals after the mixture was

created and 6 minutes and 37 seconds after the sulfuric acid was added, the mixture reached a

temperature of 110 ºC. The mixture was then added to an ice bath (where it reaches a high temp

of 113 ºC before cooling down to room temperature. The solution was then washed twice with

reverse osmosis water and dried with the addition of anhydrous magnesium sulfate. The mixture

was filtered and purified by distillation and was collected between 119-124 ºC (124-126 °C lit.)2,

with the first drip occurring at 122°C. This process helped to determine the boiling point of the
product and was used to compare to the literature boiling point of butyl acetate.The final product

obtained was very clear with a strong smell of alcoholic substances (nail polish, clear liquor,

etc.), as well as being colorless. The mass of the product was 11.9g, which was 64% of the

expected mass. 1H-NMR (CDCl3, 400MHz) δ 0.94 (t, 3HE, J=7.4 Hz,), 1.38 (sext., 2HD, J=7.6

Hz,), 1.61 (quin., 2HC, J= 8.08 Hz,), 2.05 (s, 3HA,), 4.07 (t, 2HB, J= 6.72) ppm; FT-IR (neat thin

layer, NaCl, vmax): 2962, 2875 (s, CH stretch), 1741 (s, C=O stretch), 1242 (s, sp2 C-O stretch),

1035 (s, sp3 C-O stretch) cm-1; GC/MS (tr = 3.7 min): MS m/z (% rel. int.): 115 (0.13, M+) 43

(100, CH3CO+).

In the hydroxamic test, the product produced a very dark color all around, that is

reminiscent of a mixture between black, brown, and red. The starting compound, 1-butanol,

looked fairly lighter, being yellow/orange, and seemed fairly diluted and next mixed in as well as

the product. The Ethyl acetate created a very similar result to the final product, despite being

slightly more red. When treated with the Jones test, the product had a fairly clear orange color

that was also similar to the reaction of the ethyl acetate. The butanol on the other hand, had an

opaque slightly dark green color to it. The ethyl acetate with traces of alcohol had a clear

separation with the black not mixing in and going to the bottom while the top contained an

opaque yellow coloring.

For comparison, the IR spectrum was obtained for the 1-butanol; FT-IR (neat thin layer,

NaCl) 3331 (s, br. OH stretch), 2960, 2934 and 2872 (s, CH stretch), 1077, 1044 (s, sp3 C-O

stretch) cm-1.

Discussion

The initial temperature of the alcohol was 22 ºC which decreased to 15 ºC after the

addition of the acetic anhydride. This decrease is due to the enthalpy of the two solutions mixing,
in which the addition of the acetic anhydride to the 1-butanol caused the -7 ºC change. The

temperature of the mixture then slowly increased for roughly 10 minutes, in which it reached

19.5 ºC. This temperature increase is likely due to the enthalpy between the temperature of the

mixture and the air around.At this point, the reaction had yet to occur. This was due to the

reactants not having enough free Gibbs energy to overcome the activation energy, therefore two

drops of 18M sulfuric acid were added to the mixture at the 10 minute mark to act as a catalyst.

The sulfuric acid, since it is a catalyst, lowered the activation energy of the reaction which

allowed for the reaction to begin to occur. So after the addition of the sulfuric acid, the

temperature again started to rise. The reaction between the 1-butanol and the acetic anhydride

seemed to start at around the 11 minute mark as the solution started to boil. Soon after, the

temperature of the solution began to increase rapidly. This rapid temperature increase is

explained by the process of auto-acceleration, which is when the reaction dramatically increases

its rate of the reaction once a certain obstacle is removed from the reaction process. Specifically

between the 5 and 7 minute mark the temperature of the solution rose from 37ºC to 113ºC in

under 2 minutes. The release of heat, seen through the rapid rise in temperature, helps to

conclude that the overall reaction is exothermic. Due to the rise in temperature, before and after

the addition of the sulfuric acid, the reaction between 1-butanol and acetic anhydride displays

exothermicity.

Butyl acetate was successfully synthesized with a percent yield of 64%. The success of

the synthesis was also signified by the odor of the product which was reminiscent of fruit and

nail polish remover, which butyl acetate is known to give off a fruity odor (like bananas). The

hydroxamic acid test should be able to test for ether groups in the solution The test supported

that our final product was successfully synthesised as an ester since the product and the ethyl
acetate had the same characteristics when the test was performed and both reacted with the ferric

chloride solution. Both the product and the ethyl acetate produced a clear black/red/brown color

when tested whereas 1-butanol formed a yellow/orange color that wasn’t very clear at all. The

formation of the Black/Red/Brown color indicated the formation of a ferric complex. The

similarities between the results of ethyl acetate and the final product supports that butyl acetate

was successfully synthesized. The chemical equation observed by the butyl acetate and the ethyl

acetate in the hydroxamic test is:

The chemical equations observed by the ethyl acetate in the hydroxamic test is:

The Jones test results also proved the solution was very pure. The pure ethyl acetate and

the final product both created a clear orange color when reacted. The 1-butanol produced a very

cloudy green color, and the ethyl acetate with alcohol showed a clear separation, with the bottom

part being almost black and the top part being yellow-ish, opaque color. This signifies that the

product was butyl acetate and was fairly pure as if it had alcohol in it, it would have been more

similar to the ethyl acetate with alcohol, and not the pure ethyl acetate. The chemical equation of

the Jones test on the starting alcohol is

 The product first began collecting at 122 ºC and the temperature then stayed constant at

around 124 ºC ((124-126 °C lit.)2. The collection point at 122 ºC (which is <5 ºC away from the

boiling point) seems to signify the purity of the product as there most likely no residual water or

other impurities. The Jones test backs up this statement as it proved the product was very pure

with no alcohol. The product also was clear and colorless which furthermore indicates good

purity. This also means that the distillation process was fairly successful as the collection process

seemed to work as intended.

The presence of a C=O bondat 1741 cm-1, which was determined by using IR

spectroscopy, shows that the product contains an acetate (Figure 3). Along with the discovery of

a C=O bond, two C-O bonds at 1242 and 1035 cm-1 also are characteristic of an acetate being

present. Around 3634, 3552, and 3464 cm -1 (Figure 3) there are 3 very weak peaks that show

some presence of an O-H bond. O-H bonds are characteristic of an alcohol, not an acetate, so this

means a slight amount of alcohol is also present in the product. However, when compared to the

IR of the 1-butanol (starting alcohol), the product’s O-H peak in the IR is significantly weaker

and actually contains C=O bonds unlike the 1-butanol IR (Figure 2).

The mass spectrometry also confirmed that an acetate is present in the product because

the base peak ion contains 100% abundance with an m/z of 43 (Figure 4). This base peak ion at

43 m/z is CH3CO+, which is the most common ion of all acetates1. The molecular ion peak at

115 m/z had a much smaller abundance, as low weight acetates tend to fracture, which explains

why the peak seemed to be so low (Figure 4).

The results of the H NMR of the product also comes to the conclusion that an acetate was

formed in the reaction. HA is a three proton singlet that has a chemical shift of 2.05, while HB on

the other hand is a two proton singlet that has a chemical shift of 4.07, which is due to it being
very close in distance to the electronegative Oxygen that is present in Butyl Acetate (Figure 5).

Both HA and HB have higher chemical shifts than the other groups because they are the only two

that are deshielded by the oxygen. HC is a two proton quartet with a chemical shift of 1.61ppm

and HD is a two proton sextet with a chemical shift of 1.38ppm. This information discovered in

the H NMR is also in proper accordance with the chemical structure of Butyl Acetate (Figure 5).

Lastly, the HE Signal is a three proton triplet with a chemical shift of 0.94 ppm., which also

correlates with the chemical structure as HE is the farthest CH3 group away from the oxygen

group. The coupling constants of the protons was deemed to range from 6.70 to 8.07 Hz, which

is within the range for allylic protons, this confirms that all of the carbon bonds in the product

are alkanes. Overall, when using the information obtained from the IR spectrometry and H

NMR, it is clear to say that the chemical structure of the product is that of Butyl Acetate.

The product yield of 64% is pretty good for a novice scientist, compared to 50-60% on

average. This procedure would not give yields of 80-95% most likely because of the many steps

in the process of purification to obtain the butyl acetate. There are many points where the

product could have been lost. One major possibility for the loss of product would be due to the

1-butanol not completely reacting with the acetic anhydride. This incomplete reaction would

result in a lot of the solution to be lost in the distillation to obtain butyl acetate.

The synthesis of butyl acetate from 1-butanol and acetic anhydride was seemingly

successful with a percent yield of 64%. Due to the results of the Hydroxamic test, as well as the

IR spectrometry, GC/MS spectrometry and 1H NMR it was successfully shown that the original

1-butanol had undergone a reaction to become Butyl Acetate. Based on the Jones test, as well as

the qualitative date of the product, the final butyl acetate was very pure. Despite the Jones test

results, the IR spectrometry did show very small presence of OH meaning the product was not
100% pure. However, no noticeable impurities were found during these tests and the distillation

went as expected with no excess products being produced, since the temperature of the first drip

was in correlation with the boiling point of butyl acetate.

Figures

Figure 1. Temperature of mixture (°C) versus time (minutes). The initial temperature of the

1-butanol, before the acetic anhydride addition, was at 21°C. At 0 minutes, the acetic anhydride

was then added which caused a sudden drop in temperature to 15°C. The temperature of the

mixture steadily increased to 19.5°C by the 10th minute in which 2 drops of 18M sulfuric acid

were then added. After the addition of 18M sulfuric acid, the temperature of the mixture began to

increase rapidly, reaching 113ºC at the 17 minute and 37 second mark. At this point, the mixture

was placed in an ice bath.

 Infrared Radiation Spectroscopy of 1-Butanol

Figure 2. IR of 1-butanol. No peak is present at 1700 cm, which indicates no C=O bond is

present in the molecule. Peak at 1072 cm-1indicates that a C-O bond is present. There are 3 peaks

at 2960, 2934, and 2872 cm-1 which signify the presence of a sp3 C-H bond. There is a very

broad peak at 3331 cm-1 which indicates there is an O-H bond in the molecule
 Infrared Radiation Spectroscopy of Product

Figure 3. IR of product. At 3634, 3552, and 3464 cm, there are 3 fairly weak peaks, indicating

the presence of OH bonds. Presence of C-H sp3 bonds observed at the 2962, 2875 cm-1 marks.

The peak at 1741 cm-1 indicates the presence of a C=O bond in the product, which helps to

confirm that an acetate has formed. There are also peaks at 1242 and 1035 cm-1 which signify

sp2 and sp3 C-O bonds (respectively).

 Gas Chromatography and Mass Spectrometry of Product

Figure 4. Gas chromatography and mass spectrometry of the product. The Gas Chromatogram

indicated that the retention time was 3.7 minutes. The m/z of the molecular ion peak was

determined to be 115 with a relative abundance of this is 0.13%. The m/z of 43 indicates the base

peak with a relative abundance of 100%, the ion identity of the base peak is CH3CO+.
 Nuclear Magnetic Resonance of Product

Figure 5. 1H NMR of product. The above NMR signifies that the final product is Butyl Acetate.

This is proven by the HA and HB protons which are deshielded, proving they are near the

oxygens. The other proton groups fit the corresponding chemical structure of Butyl Acetate

according to their placement and the number of peaks.

 References

1. Jue, P. K., editor. “Experiment III Part B”; Chemistry 263 Laboratory Manual: Fall 2021,

Colgate University Print services: Hamilton NY, 2021, Pages 53-62.

2. Butyl acetate. Butyl acetate | 123-86-4. (n.d.). Retrieved October 15, 2021, from

https://www.chemicalbook.com/ChemicalProductProperty_EN_CB6671615.htm.