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Synthesis of 3 - 5-Dimethylpyrazole
Synthesis of 3 - 5-Dimethylpyrazole
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.
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)
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).