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Synthesis of 3,5-dimethylpyrazole

1. Introduction:
3,5-dimethylpyrazole is used as a masking agent for isocyanate group when manufacturing
an intermediate of dyestuff.
Rothenberg1 synthesized 3,5-dimethylpyrazole by reacting hydrazine hydrate and
2
acetylacetone in ethanol, but due to violent reactivity of hydrazine, Rosengarten acquired the
substance by reacting hydrazine sulfate and acetylacetone in aqueous alkali. Since then,
Morgan3, Zimmerman4 and others synthesized 3,5-dimethylpyrzaole using the same materials.
But this method makes use of hydrazine sulfate and sodium hydroxide, thus producing much
inorganic byproduct which is not beneficial to environment. Therefore, in our experiment, we
reacted hydrazine hydrate and acetylacetone in water, skipping the production of the
byproduct.

2. Experimental
1) Materials
Hydrazine sulfate(98.0 %) were purchased from Junsei Chemical Co., Japan, and
hydrazine hydrate(55 % N2H4) and acetylacetone(99 %) were purchased from Aldrich Co.

2) Reaction of hydrazine sulfate and acetylacetone


After dissolving Hydrazine sulfate 26.1 g (0.20 mole) in 160 mL of 10% NaOH aqueous
solution, we put this solution in water bath at a constant temperature of 15 oC. The reaction
proceeded by dropping acetylacetone 20.2 g (0.20 mole) drop by drop. The duration of the
reaction was 3 hours and the temperature was kept constant at 15 oC throughout the
experiment. To dissolve solid inorganic salt produced from the reaction, we added 50 mL of
water and conducted extraction three times using ethyl ether; then, we removed moisture in
ethyl ether with anhydrous potassium carbonate. By evaporating ethyl ether, we acquired 3,5-
dimethylmpyrazole.

3) Reaction of hydrazine hydrate and acetylacetone


After dissolving Hydrazine hydrate 11.8 g (0.20 mole N2H4) in the amount of water,
indicated in Table 1, we put this solution in a water bath kept at a constant temperature of 15
o
C. The reaction proceeded by dropping acetylacetone 20.2 g (0.20 mole) drop by drop. The
duration of the reaction was indicated in Table 1 and the temperature was kept constantly at
15 oC. After the reaction, we extracted three times using 50 mL of ethyl ether and removed
moisture in ethyl ether with anhydrous potassium carbonate. By evaporating ethyl ether, we
acquired 3,5-dimethylmpyrazole.

Table 1. Feed composition for the synthesis of 3,5-dimethylpyrazole and the yield
Acetyl 10%
Experimen Hydrazine Hydrazine H2 O Reaction Yield
acetone NaOH
t hydrate(g) sulfate(g) (mL) time(hr) (%)
(g) (g)

1 26.1 20.2 3 160 82.3

2 11.8 20.0 40 1 93.0

3 11.8 20.0 40 2 95.0

4 11.8 20.0 40 3 94.4

5 11.8 20.1 80 3 84.2

6 11.8 20.0 120 3 85.7

7 11.8 20.1 40 3 0.8 94.6

3. Results and discussion


IR and NMR of product in Experiment 4 is on Figure 1 and 2, respectively, and the yield of
produced 3,5-dimethylpyrazole is on Table 1. First, on IR spectrum in Figure 1, Carbonyl
band of acetylacetone, originally appeared around 1710 cm-1 and 1620 cm-1, disappeared and
instead, the band of C=C double bond of 3,5-dimethylpyrazole appeared on 1594 cm-1. Also,
on NMR spectrum in Figure 2, the peak of CH3- appeared on 3.4 ppm, and the band of –CH=
on 2.5 ppm and the peak of NH on 8.3 ppm confirms that 3,5-dimethylpyrazole has been
synthesized.
Figure 1. IR spectrum of the product from Experiment 4.

Figure 2. NMR spectrum of the product from Experiment 4.

Next, by looking at the yield of the product depending on the condition of reaction, we can
see that yield from using hydrazine sulfate is lower than that from using hydrazine hydrate.
Also, when using hydrazine sulfate, Na2SO4 is formed as a byproduct; however, when we use
hydrazine hydrate, the amount of byproduct decreases and only little amount of unreactive
substances and product from side reaction are formed.
Therefore, in this experiment, the reactants are hydrazine hydrate and acetylacetone, and we
observed the difference in yield by changing reaction time, amount of water used, and
catalyst.
First of all, the yield slightly increased in 2 hours of reaction time than that in an hour of
reaction time. By looking at this result, we know that most of the reaction occurs within an
hour of reaction time.
Also, the yield was greatest when the amount of water was 40 mL. As the amount of water
increased, the yield decreased.
Lastly, to see the effect of catalyst, we added little amount of NaOH; the yield from adding
NaOH did not differ much from the yield without catalyst. We think that because hydrazine
itself is basic, NaOH, a strong base, has little effect on the reaction.

4. Conclusion
When synthesizing 3,5-dimethylpyrazole, it is better to use hydrazine hydrate than to use
hydrazine sulfate because the yield is greater and the reaction is ecofriendly. Also, using
40mL of water is optimal in terms of yield, and the yield differs if the reaction time was
longer than an hour. Because hydrazine is basic, NaOH catalyst didn’t have any effect on
reaction.

Reference

1. Rothenberg, J. Prakt. Chem., [2] 52, 50 (1895); Ber., 27, 1097 (1894).
2. Rosengarten, Ann., 279, 237 (1894).
3. Morgan and Ackerman, J. Chem. Soc., 123, 1308 (1923).
4. Zimmerman and Lochte, J. Am. Chem. Soc., 60, 2456 (1938).