_ 3,030,376

nite Sttes Patent " IC Patented Apr. 17, rsez

1 2
with the present reaction, for example chloride and
3,030,376 sulfate ions, and which is soluble in ammonia. Numer
PREPARATION OF 4-METHYLIMIDAZOLE FROM ous attempts were made to compound a zinc hydroxide
' GLUCOSE suited to use in the reaction of the invention. Noneof
Robert W. Liggett, Mountain Brook, and Harmon L the various zinc hydroxides that were compounded gave
Hoffman, Jr., Homewood, Ala., assignors to Atlas consistent yields of 4-methylimidazole, whereas the use
Chemical Industries, Inc., a corporation of Delaware
No Drawing. Filed Mar. 21, 1960, Ser. No. 16,167 of zinc carbonate gives a consistent and dependable yield
2 Claims. (Cl. 260-309) of between about 40 and about 60% of the zinc-4-meth
ylimidazole complex based on the weight of dextrose
This invention relates to an improved method for the 10 starting material.
production of 4-methylimidazole. More speci?cally, the The preferred mol ratio of the reactants is about 30
invention concerns a process wherein 4-methylimidazole mols of ammonium ions, to 2 mols of zinc carbonate,
is produced from dextrose. to 3 mols of formaldehyde, to 2 mols of dextrose. Con
The product of the present invention is useful as a sistent high yields of 4-methylimidazole are obtained
curing agent for epoxy resins and as a convenient source 15 when the foregoing preferred ratio is utilized. Slightly
of starting material for the production of various imida lower percentage yields of the zinc-4-methylimidazole
zole derivatives useful as curing agents and stabilizers complex, based on the weight of dextrose, are obtained
for epoxy resins. ' when the amounts of dextrose or dextrose and formalde
In general, the present invention relates to a process hyde in the preferred ratio are doubled. The weight
for producing 4-methylimidazole in good yield by react 20 increase of the zinc-4-methylimidazole product that may
ing together a mixture of dextrose, formaldehyde, am be obtained in the foregoing cases is often not economi- '
monium ions and zinc carbonate at a temperature of at cally justi?ed because of yield-decreasing side reactions
least 60 C. In the initial reaction, the dextrose start of the increased dextrose component or because of the,
ing material is decomposed and a complex zinc salt of increased quantity of reactants which must be expended.
4-methylimidazole is precipitated from the reaction mix 25 The initial reaction of this invention may be carried
ture. The zinc is then removed from the zinc 4-meth out at temperatures ranging from about 60 C. to about
ylimidazole complex leaving free 4-rnethylimidazole. A 115 C._and appears to be substantially independent of
method of removing the zinc, which has been found to pressure conditions. In the preferred embodiment of the
be satisfactory in carrying out the present invention, is invention, the initial reactants are heated together at
by forming a slurry of the zinc-4-methylimidazole com 30 atmospheric pressure to a temperature of 60 C. over a
plex with water and treating the resultant slurry with time period of about 1 hour. The temperature is then
hydrogen sul?de. The zinc salt precipitate is thereby de permitted to rise at the same rate to about 70 C- and
composed rendering a solution of free 4-methylimidazole this temperature held constant for approximately 3 hours. -
and a zinc sul?de precipitate. The 4-methylimidazole At the end of that time the formed zinc complex is de
solution is then separated from the zinc sul?de by me 35 composed by treatment with hydrogen sul?de; the formed
chanical means, the solution condensed and the 4-meth zinc sul?de separated from the solution by ?ltration; and
ylimidazole product recovered by known methods, such the solution condensed. The resultant solution of 4
as extraction with a suitable water immiscible solvent, methylimidazole is then puri?ed and concentrated by ex- '
and puri?ed by vacuum distillation. traction with a suitable solvent such as chloroform and
The quality of the dextrose starting material employed 40 separated by a vacuum distillation.
in the present invention may vary from reagent to com For the purpose of illustrating the invention more
mercial grade. It has been found that a comparatively fully, the following example is given:
wide variation of dextrose purity in the starting material Example
results in substantially no difference in the quality or
quantity of the product. - 45 76 g. of zinc carbonate (0.6 mol) were added to an
In carrying out the invention, it has been found that aqueous solution of 600 ml. of ammonium hydroxide
formaldehyde in the form of formalin may ably be utilized (8.9 mols) and the mixture stirred until the zinc car
in the reaction. If it is desired, formaldehyde in other bonate was substantially entirely dissolved. With con
concentrations or precursors of formaldehyde such as stant stirring of the mixture 85 ml. of formalin (37%)
paraformaldehyde or hexamethylene tetramine may be 50 (0.95 mol) were added to the zinc carbonate-ammonium
utilized to carry out the invention. hydroxide mixture. The reaction mixture was then com
Ammonium ions in the reaction of this invention, pleted by the addition of 100 g. of dextrose (0.55 mol).
are preferably supplied in the reaction in the form of Gentle heating of the reaction mixture was started as
aqueous ammonia. If it is desired, other sources of am soon as the dextrose was dissolved. With constant stir
monium ions such as mixtures of ammonium carbonate, 55 ring the reaction mixture was heated to 60 C. over a
or ammonium acetate, with ammonium hydroxide may be time period of 1 hour. It was noted that a zinc salt
' utilized to carry out the process of the present invention. complex began to precipitate out of the reaction mixture
Although the zinc carbonate material suited to use at about this point. Once the precipitation started, it
in the present invention may be a reagent grade, it has appeared to be complete in approximately 10-20 minutes.
been found that materials readily available from the usual 60 With constant stirring, the reaction temperature was al
chemical sources of supply and known as zinc carbonate lowed to increase at the previous rate until a temperature
or basic zinc carbonate are eminently satisfactory. of 70 C. was reached. This temperature was then main
1Prior art methods of producing 4-methylirnidazole from tained for 5 hours, and the reaction mixture constantly
dextrose utilize zinc hydroxide in the reaction. Windaus,
A., and Knoop, F., Ber. 38, 1166 (1905); Weidenhagen, 65 stirred over this period. The zinc salt complex was
then separated by ?ltration, dried and weighed. The
R., and Hermann, R., Z. Wintschafts Zuckerind, 85, 126 dried zinc salt complex was found to weigh 38.7 g. and
(1935); Parrod, 1., Bull Soc. Chim. France,(4), 53, 196 represented a yield, based on the Weight of the dextrose
(1933), and Bernhauer, K., Z. Physiol. Chem., 183, 67
(1929). Zinc hydroxide is not available as an article starting material of 60.5%.
of commerce. It is a compound that is most difficult to 70 The above procedure was repeated using twice the
prepare. Particularly it is di?icult to prepare a zinc amount of each of the reactants. The weight of the
hydroxide which does not contain ions which interfere dried zinc salt complex wasv found to be 73.5 g. and
 3,030,376
3 Aa
represented a yield, based on the weight of the dextrose complex, treating the complex to remove the zinc, and
starting material, of 57.4%. recovering 4-methylimidazole, the improvement of using
The above described procedure was again repeated, zinc carbonate as the zinc compound and carrying out
ths time using 8 times the amount of each of the re the said reaction at a temperature between about 60 C.
actants plus 800 g. additional of dextrose. The reactants 5 and about 115 C.
were heated together overa period of 6.5 hours. The 2. The process described in claimpl wherein the pro
weight of" the dried zinc salt complex was found to be portions of the reagents are suchv that for each mol of
545.0 g. and represented a yield, based on the weight dextrose there is used about 7.5 to about 15 mols of
of the dextrose starting material of 53.3%. ammonium ions,v about 1.5 mols of formaldehyde and
The zinc salt complex from each of the abovere 10 from'about 0.5 to about 1.0 mol of zinc carbonate.
actions was combined and the mixture slurried with water.
The slurry was then saturated with hydrogen sul?de for References Cited in the ?le of this patent
approximately 3 hours at a temperature of 65-70? C. UNITED STATES PATENTS
The resulting product was allowed to cool and the formed 2,728,763 Mamalis et al _________ __ Dec. 27, 1955
zinc sul?de was separated by ?ltration. The ?ltrate, con- 15
taining free 4-methylimidazole in an aqueous solution FOREIGN PATENTS
was then evaporated under a vacuum for approximately 2
hours to remove any dissolved hydrogen sul?de remain 183,588 Germany ____________ _.. Apr. 15, 1907
ing in the solution. The 4-methylimidazole was then ex OTHER REFERENCES
tracted from the aqueous mixture with chloroform. The 20
chloroform-4-methylimidazole' product was then distilled Windaus et al.: Ber. Dent. Chem, vol. 38, pagesll66
at 0.2 mm. of mercury at 120130 C. pot temperature. 70 (1905).
4-methylimidazole of high purity. was recovered. Windaus: Ber. Deut. Chem, vol. 40, pages 7994301
What is claimed is: _ V (1907). '
1. In a process of preparing 4-methylimidazole by re Parrodz' Chem. Absts., vol. 27, page 2955 (1933).
acting dextrose with ammonium ions and formaldehyde Elder?eld: Heterocyclic Compounds, vol. 5, pages 211
in the presence of a zinc compound to produce a zinc 12 (1957);