It has been voiced that people wish to move past the mercury aluminum amalgam reduction of the church of Bright Star and Osmium. The Leuckart is feasible with similar equipment. Leuckart net legend tells of 70% yields. The reaction conditions of these high yield reactions are sketchy at best which leads one to doubt their validity. What is beyond doubt is the volume of information on the Leuckart from real scholarly journals.
In these journals one will find most published reactions, at one mole ketone for clarity, using from four to six moles formate or formamide, one to three additional moles of 90% formic or glacial acetic acid and the big gun, 6.3g anhydrous magnesium chloride(someone has stated calcium chloride as well but I haven't seen the ref). The additional acid and magnesium chloride are said to help the reaction with magnesium chloride being an effective catalyst. The use of a nitrogen atmosphere is said to help.
Problems with this reaction are many. Issues appear to stem from water, although the old school running of this in a distillation rig should help this automatically. Reaction procedures and temperatures vary quite a bit although there seems to be a consensus that lower temps and longer cooks are better.
Most of the refs are written using formamide for primary amines and n-methyl formamide for the methyl. This isn't a good starting point for most underground chemists because good luck sourcing n-methyl formamide.
Starting from the beginning and with what is available to the average aspiring chemist, formic and methylamine, one can look to form the formate and then choose whether to continue the heated dehydration to n-methyl formamaide, if I have it correct. The refs seem to say that the formate salt is more reactive and higher yielding. Perhaps adding cold methylamine in water to cold stirring formic, gentle distillation then finish with another means such as silica gel or toluene azeotrope(my new favorite chem trick). Perhaps the easily available and dirt cheap magnesium chloride hexahydrate could be in this mix and dehydrated at the same time.
Where is the line between formate and formamide? The refs that state heat amine and formic to 160C as long as water distills seem to be stopping there for a reason, perhaps to maximize the formate, while others heat to 180-190C as long as water distills which seems to be looking for the dehydrated formamide.
After their formate/formamide is in hand, the ref doctors then add 90% formic, glacial acetic acid or anhydrous MgCl2 if they are used, right before the ketone is added.
Having no first hand experience with these substances I can't say how they "mingle". Some refs say they start out two phase then upon heating and distillation become a single phase, while returning any ketone that distills over. If this works then it stands to reason that as long as the heating was gradual and the ketone that had distilled over was returned to the reaction flask, then the whole water issue should be regulated automatically. Problems are with the additional formic or acetic. With their boiling points far below the minimal 155C, shouldn't they distill out of the mix at the same time as any water making their addition questionable?
Local chemwaster researcher is pondering adding cold aq. methylamine to cold formic and MgCl2*6H2O, runing the temp to 160C for as long as water distills then coolin to 100 or so, adding dry ketone and slowly ramping the temp up to 155C, all the while keeping it at the "little CO2 bubbles" level of activity, then once at 155C, changing the distillation rig to reflux and letting it run for 24hrs.
If anyone sees any problems or has insights to share, chemwaster would love to hear about it.
In these journals one will find most published reactions, at one mole ketone for clarity, using from four to six moles formate or formamide, one to three additional moles of 90% formic or glacial acetic acid and the big gun, 6.3g anhydrous magnesium chloride(someone has stated calcium chloride as well but I haven't seen the ref). The additional acid and magnesium chloride are said to help the reaction with magnesium chloride being an effective catalyst. The use of a nitrogen atmosphere is said to help.
Problems with this reaction are many. Issues appear to stem from water, although the old school running of this in a distillation rig should help this automatically. Reaction procedures and temperatures vary quite a bit although there seems to be a consensus that lower temps and longer cooks are better.
Most of the refs are written using formamide for primary amines and n-methyl formamide for the methyl. This isn't a good starting point for most underground chemists because good luck sourcing n-methyl formamide.
Starting from the beginning and with what is available to the average aspiring chemist, formic and methylamine, one can look to form the formate and then choose whether to continue the heated dehydration to n-methyl formamaide, if I have it correct. The refs seem to say that the formate salt is more reactive and higher yielding. Perhaps adding cold methylamine in water to cold stirring formic, gentle distillation then finish with another means such as silica gel or toluene azeotrope(my new favorite chem trick). Perhaps the easily available and dirt cheap magnesium chloride hexahydrate could be in this mix and dehydrated at the same time.
Where is the line between formate and formamide? The refs that state heat amine and formic to 160C as long as water distills seem to be stopping there for a reason, perhaps to maximize the formate, while others heat to 180-190C as long as water distills which seems to be looking for the dehydrated formamide.
After their formate/formamide is in hand, the ref doctors then add 90% formic, glacial acetic acid or anhydrous MgCl2 if they are used, right before the ketone is added.
Having no first hand experience with these substances I can't say how they "mingle". Some refs say they start out two phase then upon heating and distillation become a single phase, while returning any ketone that distills over. If this works then it stands to reason that as long as the heating was gradual and the ketone that had distilled over was returned to the reaction flask, then the whole water issue should be regulated automatically. Problems are with the additional formic or acetic. With their boiling points far below the minimal 155C, shouldn't they distill out of the mix at the same time as any water making their addition questionable?
Local chemwaster researcher is pondering adding cold aq. methylamine to cold formic and MgCl2*6H2O, runing the temp to 160C for as long as water distills then coolin to 100 or so, adding dry ketone and slowly ramping the temp up to 155C, all the while keeping it at the "little CO2 bubbles" level of activity, then once at 155C, changing the distillation rig to reflux and letting it run for 24hrs.
If anyone sees any problems or has insights to share, chemwaster would love to hear about it.