Patent DE468895
IG Farben 1925
translated as good as possible by ORGANIKUM
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It was found that the formation of CO2 whilst the production of mono or dimethylamine can be mostly or completely avoided by the addition of alcohol to the reaction mixture. Practically 1 mol alcohol or more to 2 mol of aldehyde are used. There is then the formate of the added alcohol formed besides the salt of the amine.
The reaction of formaldehyde and ammoniumchloride in presence of alcohol proceeds after this formula:
2HCOH + NH4Cl + C2H5OH = CH2NH2.HCl + H2O + HCOOC2H5
The produced ethylformate can be distilled out during or whilst the reaction. Besides the fact that the oxidation of formaldehyde to CO2 is avoided the addition of alcohol has the advantage that the reaction temperatur is diminished as the reaction proceeds already at 75°C whereby without alcohol the reaction starts over 90°C, also the the reaction proceeds faster this way. The tendency to form higher methylated amines is strongly reduced.
According to the reaction conditions it is possible to produce methylamine or dimethylamine. An excess of ammoniumsalts favors usually the formation of the primary amine, a excess of formaldehyde the formation of the secondary amine. Aquaous formaldehyde, polymeres of the aldehyde or alcoholic solutions of formaldehyde can be used.
Example:
17 parts of 40% formaldehyde, 7 parts of 96% alcohol and 8 parts of ammoniumchloride are heated up to the boilingpoint of the mixture (about 75°C). The reaction proceeds mostly during the heating up, the NH4Cl goes into solution and a mostly of ethylformate consisting upper layer forms, which is removed by destillation.
After the excess of ammoniumchloride is removed and the water is destilled away a product remains which consists almost exclusivl< from monomethylamine.
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Interesting points to reaction conditions and else I think.
Eleusis wasnt so wrong - if not in the theory but in the practice at least.