Sciencemadness Discussion Board

Ethylamine Synthesis

Waffles SS - 19-1-2012 at 22:45
Quote:




Ethylamine is an organic compound with the formula CH3CH2NH2. This colourless gas has a strong ammonia-like odor. It is miscible with virtually all solvents and is considered to be a weak base, as is typical for amines. Ethylamine is widely used in chemical industry and organic synthesis.
Ethylamine is produced on a large scale by two processes. Most commonly ethanol and ammonia are combined in the presence of an oxide catalyst:

CH3CH2OH + NH3 → CH3CH2NH2 + H2O

In this reaction, ethylamine is coproduced together with diethylamine and triethylamine. In aggregate, approximately 80M kilograms/year of these three amines are produced industrially. It is also produced by reductive amination of acetaldehyde.

CH3CHO + NH3 + H2 → CH3CH2NH2 + H2O

Ethylamine can be prepared by several other routes, but these are not economical. Ethylene and ammonia combine to give ethylamine in the presence of an sodium amide or related basic catalysts.

H2C=CH2 + NH3 → CH3CH2NH2

Hydrogenation of acetonitrile, acetamide, and nitroethane affords ethylamine. These reactions can be effected stoichiometrically using lithium aluminium hydride. In another route, ethylamine can be synthesized via nucleophilic substitution of a haloethane (such as chloroethane or bromoethane) with ammonia, utilizing a strong base such as potassium hydroxide. This method affords significant amounts of byproducts, including diethylamine and triethylamine.

CH3CH2Cl + NH3 + KOH → CH3CH2NH2 + KCl + H2O

http://en.wikipedia.org/wiki/Ethylamine

I am looking for easier method but It seems making Ethylamine is more difficult than making Methylamine.Anyone know easier method?

Anyone has more info about ethylamine?like boiling poit?decompose temp?
Solubility of ethylamine and its chloride salt in acetone ,Ethanol(and in what solvent is insoluble)?




[Edited on 20-1-2012 by Waffles SS]

Organikum - 20-1-2012 at 08:43

The internet has all the physical properties of ethylamine, you know?

Making the acetamide looks not very demanding to me.

Reducing it, ok all are calling for LiAH but thats spoilsport, with LiAH everybody can.

So we know that HI rips virtually all Oxygen out of a molecule (and takes Nitrogen next if conditions are harsh enough). And we have an "O" to much here.

Suggestion: NaI + NaH2PO2 + conc. HCl + H3PO4, heat until something starts to happen in the flask, add amide and reflux for some hours.
Does ethylamine form such a nice azeotrope with ethanol as methylamine does with methanol? Anyways, basify and distill the amine, it is not a gas like meam at RT so thats a cake.

Waffles SS - 20-1-2012 at 10:18

Thanks, but i searched it in google and found nothing about solubility of it chloride salt in acetone and alcohol also nothing about decompose temp
Does amalgam method is effective in hydrogenation step?(instead of LiAH)

[Edited on 20-1-2012 by Waffles SS]

Organikum - 20-1-2012 at 11:12

Quote: Originally posted by Waffles SS  
Thanks, but i searched it in google and found nothing about solubility of it chloride salt in acetone and alcohol also nothing about decompose temp
Does amalgam method is effective in hydrogenation step?(instead of LiAH)

[Edited on 20-1-2012 by Waffles SS]


In a pipe bomb with serious heat and pressure who knows? But not just so AFAIK. The HI is the only way I know which doesn´t require hydrides, silanes or alltogether. And it is usually high-yielding too, but I know, HI reactions are so yesterday, Unobtainiumhydride thats hip! :D

entropy51 - 20-1-2012 at 12:30

Posted somewhere on the forum is an old paper that says heating ethyl iodide, ethanol and ammonia in a sealed tube gives ethylamine with less than 10% of higher substitution products. I can't immediately find the post, but it's here somewhere.

It does require heating in a sealed tube however.

tube

Organikum - 20-1-2012 at 12:51

There is always a price to pay....

A tube made from soft steel, welded shut and on one end a sufficient threaded bore for a nice fat screw, maybe a safety bow, done. A thermocouple to show the temp. from some distance and a big old iron bucket over all as the only danger is fluids spraying around if it breaks open. Soft steel will not defragment, in the worst case there might be a leak. Wrap the threads of the screw with teflon tape, you might to want to open it oneday :)

For large scale one of these ball-like propanetanks - 2 or 3l. Don´t know if you have them, here they are cheap, rated to 10atm and come with a minimum of 10-fold safety marge (kind a law).

Isn´t there some damned catalyst for this amination? I remember something like triethylamine together with something else to catalyse this reaction in a way that for iodine roomtemperature almost suffices.
Just cannot remember ..

entropy51 - 20-1-2012 at 17:30

Quote: Originally posted by Organikum  
There is always a price to pay....

A tube made from soft steel, welded shut and on one end a sufficient threaded bore for a nice fat screw, maybe a safety bow, done. A thermocouple to show the temp. from some distance and a big old iron bucket over all as the only danger is fluids spraying around if it breaks open. Soft steel will not defragment, in the worst case there might be a leak. Wrap the threads of the screw with teflon tape, you might to want to open it oneday :)

For large scale one of these ball-like propanetanks - 2 or 3l. Don´t know if you have them, here they are cheap, rated to 10atm and come with a minimum of 10-fold safety marge (kind a law).

Isn´t there some damned catalyst for this amination? I remember something like triethylamine together with something else to catalyse this reaction in a way that for iodine roomtemperature almost suffices.
Just cannot remember ..
I used thick Pyrex combustion tubing sealed in the Oxy-propane blast lamp. The sealed tube was enclosed in a pipe bomb much as you describe. It only has to be heated in a boiling water bath for ethylamine.

I've never had one of these thick Pyrex tubes explode, but they scare my shirtless. The best catalyst in my opinion is several hits of Courvoisier to give the chemist sufficient nerve to start heating the sucker.

Several of the old chemistry lab manuals in the forum library have detailed instructions for heating in sealed tubes and I recommend that anyone contemplating an attempt at this method read ALL of them and follow the directions carefully.

I can't recall the details of the catalyst, but I think you are correct. Adding NH4NO3 increases the proportion of primary amine formed, but slows down the reaction and is not necessary for ethylamine.

Ephoton - 20-1-2012 at 18:18

calcium propionate can be brought as a bread preservative E282.

ammonium propionate made form this can be rearranged thermally to propionamide very easily.

hoffman of propionamide gives ethylamine.

:) easy

you should be able to produce a few kilo's in a day this way
and the price per kilo would be around $20 too $50 (probably
cheaper than buying the shit)

no dangerous reductions or flamable solvents needed

just calcium propionate, aqua ammonia, aqua HCl, Bleach and caustic.

Ethyl amine could then be solvent extracted or boiled out of
hoffman turned to Hydrochloride with HCl and then freebased with
caustic to be distilled pure.

of course an excess of caustic when freebasing would be a good idea as it would hold onto most of the water created from the basing of a hydrochloride with caustic.


on second thoughts sulfate would probably be less hygroscopic
and would let you boil the water off it easier than the hydrochloride.

[Edited on 21-1-2012 by Ephoton]

Waffles SS - 20-1-2012 at 22:41

@Ephoton,Yes Hofmann Rearrangement is really interesting


I think we can customize below route for Ethylamine .
This method for making ethylamine is easier than methylamine because ethylamine boil at ~16c( I have access to calcium propionate :D)
But i think ammonium propionate can easily be made from ammonium sulfate and calcium propionate.but i dont know what temp needed for making ammonium propionamide from ammonium propionate.
Quote:

Synthesis of Methylamine/Methylamine HCl via Hofmann Rearrangement
There are two approaches to producing an amine from an amide using the Hofmann rearrangement reaction. One way is to react the primary amide with an alkaline-halide solution (eg - Sodium Hydroxide and Bromine). The other method is to use an alkaline-hypohalite solution (eg - Sodium Hydroxide and Calcium Hypochlorite). The astute observer will notice that there is no chemical difference in the two processes. One produces the Hypohalite in situ, the other uses the Hypohalite itself. Substitution of various halogens/halides/hypohalites/hydroxides is acceptable, but I feel I have picked the best combination of maximal yield and ease of availability. Feel free to prove me wrong ;-). Also, at least one text specifies that Sodium Hypochlorite produces much higher yields than Sodium Hypobromite. This delicious vindication is expected since Chlorine is a more reactive halogen than Bromine. Now, we are going to use Calcium Hypochlorite, in the form of powdered pool shock, because concentrated Sodium Hypochlorite is a rare, unstable creature indeed. Our yield will not suffer in the slightest because of this.

The main example presented will be the alkaline-hypohalite method as it is the easiest to acquire the necessary chemicals. It is of interest to note that the alkaline-halide method is much easier to perform, processwise, in that it is more forgiving of sloppy technique.

The general theory behind the process is that the hypohalite will convert the amide to a haloamide. This then spontaneously changes to the isocyanate when heated and decomposes to the amine from the water present. In effect, all that happens is that a Carbonyl (CO) group is stripped off the starting amide to yield the corresponding amine. Yields pre-purification are around 80%, post-purification average around 65%. Certain uses of the resulting amine will not require purification, though, so it will be left up to you whether or not to perform those steps.

To make methylamine we start with Acetamide. The general, unbalanced reaction process is thus:

CH3CONH2 + Ca(OCl)2 ----> (CH3CONCl)2Ca++ + H2O
then
(CH3CONCl)2Ca++ + NaOH ----> CH3NH2 + Na2CO3
CAUTION Methylamine is a poisonous, noxious inflammable gas. It has a strong ammonia/rotting fish-like odor. It's not as bad as Chlorine gas, though, which can be produced if one is careless in the beginning!


You can scale these reactions up or down within reason. What is reasonable? I can't say, but I have done batches from .01 to 1 mole with no difficulty. The key problems in scaling this reaction have to do with heat gradients in the flask and inadequate stirring. Use your own judgement, keeping in mind that this is not an industrial process.

One reference to keep in mind (Thanks to J.W. Smith for sending this one) concerns the first step of the reaction.

Whitmore and Thorpe, J. of the Amer. Chemical Society, Vol 63, April 1941, p1118
"It was necessary to allow several hours for the formation of the N-chloroamide before heating to degradation temperature. With this modification it was possible to prepare methylamine...consistently in 78% yield."
In my experience, this is a true statement. Please remember to keep the reactants well iced, though. Now, to begin:
In a large mixing bowl which can contain a smaller stainless steel mixing bowl, prepare an ice bath with water and salt to bring the temperature down to -10C or so. Setup your glassware for simple distillation with magnetic stirring beforehand because certain steps need to be performed quickly. Use a vacuum adapter to connect to the receiver flask, and attach some rubber or polypropylene tubing to the vaccum nipple to connect to a bubbler setup (a funnel inverted in a beaker, or a plastic aquarium aerator tube). The distilling flask should be sitting in in a stainless steel bowl with nothing in it (you will add pre-heated oil to the bowl).

NOTE In order to make this as painless as possible, please observe the following recommendations: 1) Keep the mixing bowl temperature as close to 0C or less as possible; 2) Keep the Hypochlorite solution as it is being added as close to 0C or less as possible; 3) After half the Hypochlorite solution has been added, place a plastic bag with 50-100g ice/salt/water mix into the bowl to help keep temperatures low (use this instead of directly adding ice to the reactants, which adds a considerable volume of water making the process less volumetrically efficient); 4) Purchase an 8lb bag of ice ahead of time!


Next you will prepare three solutions.

10g of Acetamide in 20mL of distilled water.
16.4g of Calcium Hypochlorite (Pool shock) in 50mL of hot distilled water
24g of Sodium Hydroxide (Lye) in 40mL of cold distilled water
This last solution should be prepared slowly as it is quite exothermic. Set all three aside in a freezer. Now prepare the mixing apparatus which will be a stainless steel "mixing bowl" suspended in the ice/salt bath made earlier. We use a stainless steel bowl here so that heat transfer will be maximal, while preventing any corrosive interaction. A glass bowl will not be sufficient for larger scale preparations as it will not conduct heat fast enough to prevent the reactants from going over 10C (at which point the Haloamide will decompose and you'll have to start over). Take the Sodium Hydroxide solution out of the freezer once it is cool, but not cold.
After the bowl has been sitting in the ice bath for a few minutes, add the Acetamide solution. Stir well until the solution has cooled to -10C. Now, slowly add the Hypochlorite solution to the mixing bowl in bursts of no more than a couple mL while stirring vigorously. If you do this perfectly, there will be no fizzing or bubbling at all. This depends on how cold you keep the mixture, and how slowly you add the pool shock! Realistically, the considerable heat evolution of the reaction will make adding the last few mL a trying task! Keep an additional 50g of ice on hand to throw directly into the mixture if necessary. This solution may evolve Chlorine gas so you should obviously perform this step under a fume hood or outside). Keep stirring until it has calmed down and turned a turbid colorless to light green Let it sit for 2 hours, stirring occasionally and making sure that it never gets warmer than 5C.

After the 2 hours is up, add the Sodium Hydroxide solution quickly with stirring. The solution should immediately turn a chalky, milk white. That's because a lot of Sodium Carbonate just got generated. You no longer need be concerned over it's temperature, so you can leave the solution in this state overnight if perhaps the hours have passed by too quickly and you've suddenly realized it's 2:00am.

Preheat a water bath on the stove (or wherever) to about 80C and place the stainless steel mixing bowl in it. Once the temperature of the solution hits about 65C, take the bowl out and set aside while stirring all the while. This is where it rearranges, and the reaction is exothermic enough to sustain it's temperature nicely. If you find the temperature climbing past 80C, immerse the bowl into some cold water briefly. After about 15 minutes the temperature will start to fall, at which point you should transfer the whole mess to the distilling flask. Before you continue you need to choose whether you want to make the hydrochloride salt or the aqueous solution of Methylamine, though.

Heat the flask using an oil bath to 100C after adding this solution to effect gentle boiling which will drive off the Methylamine as a gas. In my experience, misbehavior is likely to occur at this point. One particular problem to watch out for is the sucking back of bubbler solution (be it plain water or 6N HCl) into the receiver flask. I don't know why the pressure in the distilling flask would go below atmospheric, and therefore cause this to happen, but it has several times with me. Needless to say, this results in a serious mess and botches the whole process (I have found a cure for this by using an automotive one-way vacuum valve, like a PCV).

Continue heating the flask contents until you have collected around 100mL of distillate in the receiver.

For the aqueous solution: Place 18mL of cool distilled water into your bubbler setup. The expected, not theoretical, yield of Methylamine from this amount of reactants is 7 grams. I have used a plastic aquarium aerator tube as the bubbler with excellent results. Sure beats using an inverted funnel.

For the HCl salt: Do exactly as above except use 6N Hydrochloric Acid. 6N HCl may be produced by diluting 60.4mL of "Muriatic Acid" to 100mL with distilled water. Evaporate the bubbler solution to dryness then add 15ml of water, 10mL 10% NaOH soln. and heat gently to a boil with constant motion until dense white fumes appear. This will remove the Ammonium Chloride. Remove from heat while stirring as it cools down. Pulverize the dry residue, then reflux with absolute Ethanol for several minutes. Filter the refluxed soln. on a heated Buchner or Hirsch funnel, then distill the alcohol off the filtrate until crystals just begin to form. Allow the soln. to cool naturally to room temperature, then cool further in an ice bath. Filter the solution on a chilled Buchner funnel with suction. The yield of Methylamine Hydrochloride should be around 55% of the theoretical.

To clean the white residue off of your glassware, dump some muriatic acid straight from the jug onto them and swirl.

References:

Journal of Chemical Education, v14, pg542
Organic Reactions volume 3
Vogels Elementary Practical Organic Chemistry, pg574



Do you know decompose temp of chloride salt of Ethylamine ?and solubility in acetone and EtOH?




[Edited on 21-1-2012 by Waffles SS]

mario840 - 20-1-2012 at 23:55

Hahahahaha i knew it, on this forum are only google-amateur-chemists, to my thread no one can answer because they know nothing more than goole , in this thread as always some useless method and theorizing bla bla bla bla , ethylamine is produced in good yields by reduction of nitroethane in many methods for example : zinc/ammonium formate, Al/Hg etc. , reduction of nitrile gives a amine with one carbon more so reduction acetonitrile gives ethylamine , acetonitrile is common solvent, cheap, and easy to buy, reduction cheapest al/hg. Cya

D. Gowda, B. Mahesh, & G. Shankare, Ind. J. Chem. Sect. B, 40, 75-77 (2001)
Syn Comm, Vol 33, No 2, pp 281-289 (2003)

AndersHoveland - 21-1-2012 at 00:09

There is not really any easy way for the hobbyist to make ethylamine. The most feasible route would probably be partial oxidation of ethanol to acetaldehyde, then distillation with NH4Cl (or possibly (NH4)2SO4 fertilizer). The procedure would be similar to that used for making methylamine:
Quote:

Methylamine Hydrochloride from Ammonium Chloride and Formaldehyde
In a 5 liter round-bottomed flask, fitted with a stopper holding a condenser set for downward distillation and a thermomether which will extend well into the liquid, are placed 4 kg (3711 ml, 47-53 moles) of technical formaldehyde (35-40 percent; d 1.078 at 20°C) and 2 kg (37 moles) of technical ammonium chloride. The mixture is heated on the steam bath until no more distillate comes over and then over a flame until the temperature of the solution reaches 104°C. The temperature is held at this point until no more distillate comes over (four to six hours). The distillate, which consists of methylal (bp 42-43°C), methylformate and water may be treated with NaOH solution to recover methylal and sodium formate. The contents of the reaction flask are cooled too room temp and the ammonium chloride which separates is filtered off. The mother liquor is concentrated on the steam bath under reduced pressure to 2500 ml, and again cooled to room temp, whereupon a second crop of ammonium chloride separates. The total recovery of ammonium chloride up to this point amounts to 780-815 grams. The mother liquor is again concentrated under reduced pressure until crystals begin to form on the surface of the solution (1400-1500 ml). It is then cooled to room temperature, and a first crop of methylamine hydrochloride, containing some ammonium chloride is obtained by filtering the cold solution. At this point 625-660 grams of crude product is obtained. The mother liquor is now concentrated under reduced pressure to about 1000 ml, and cooled, and a second crop of methylamine hydrochloride (170-190 grams) is then filtered off. This crop of crystals is washed with 250 cc of cold chloroform, and filtered to remove most of the dimethylamine hydrochloride which is present. After the washing, the product weighs 140-150 grams. The original mother liquor is then evaporated under reduced pressure, as far as possible, by heating on a steam bath, and the thick syrupy solution (about 350 ml) which remains is poured into a beaker and allowed to cool, with occasional stirring, in order to prevent the formation of a solid cake, and the crystals obtained are washed with 250 ml of cold chloroform, the solution is filtered yielding 55-65 grams of product. There is no advantage in further concentrating the mother liquor, which contains mostly tetramethylmethylenediamine hydrochloride, but no trimethylamine hydrochloride. The total yield of methylamine hydrochloride is 830-850 grams. The product contains water, ammonium chloride and some dimethylamine hydrochloride. In order to obtain a pure product, the impure methylamine hydrochloride is recrystallized from absolute ethanol (solubility 0.6g/100ml at 15°C), or preferably butyl alcohol (even less soluble). The recovery of ammonium chloride amounts to 100-150 grams, making the total recovery 850-950 grams. The yield of recrystallized methylamine hydrochloride is 600-750 grams (45-51 percent of theory, based on the used up ammonium chloride).
A standard run, from 250 grams ammonium chloride and 500g 37% formaldehyde (containing 15% methanol), gives 100-134 grams methylamine hydrochloride, 27 grams dimethylamine hydrochloride and 81 grams of recovered ammonium chloride. The distillate contains methylal (formaldehyde dimethyl acetal) and methyl formate, which after treatment with NaOH can yield 25g of sodium formate and 30 grams of methylal, as the compound cannot be separated by fractional distillation, neutralization is the way to go. Ammonium chloride is very sparingly soluble in a concentrated solution of methylammonium chloride, making the separation of the compounds pretty sharp.

Similarly, Hexamine and HCl may be used as the reactants instead, illustrating that the order of reaction of CH2O, NH3, and acid does not matter.
Quote:

Acetaldehyde

Place 260mL of 23% sulfuric acid in a 1500-mL flask. Connect an addition funnel to the flask, and set it up for vacuum distillation with a 500-mL receiving flask. The receiving flask should be immersed in a salt-ice bath to cool the distillate when it comes over. Although a setup for vacuum distillation is used, it is not necessary to apply a vacuum; the vacuum adapter merely provides a means of equalizing pressure. Prepare a solution of 100 g of sodium dichromate in 200 mL of water and 127 mL of ethyl alcohol. Factor in the amount of water that is already in the ethyl alcohol when making the solution, i.e. 100 mL of 95% alcohol has 5 mL of water in it already. Place this solution in the addition funnel, position the stem of the funnel such that it is about 3 cm above the surface of the acid. Heat the acid until it just begins to boil, then add the mixture in the funnel in a steady stream to the acid. It will not be necessary to heat the flask during the addition because it will generate its own heat. The heat will be sufficient to distill over the acetaldehyde along with some alcohol and waste acetal. If acetaldehyde vapors begin to escape from the flask, regulate the distillation by decreasing the amount of dichromate solution being added. If the reaction flask does not boil on its own, gently heat it for a short time until boiling begins.
The acetaldehyde thus obtained is difficult to distill from the alcohol and acetal mixed with it. It is therefore converted to aldehyde-ammonia, then back to pure aldehyde. Place the crude acetaldehyde in a Florence flask of suitable volume to contain no more than two thirds of the liquid. Attach a reflux condenser to the flask. Fill the condenser jacket with 30 °C water. It is only necessary to have the warm water in the jacket, not flowing. Stop up the lower connecter to prevent water from leaking out. To the top of the condenser, attach a glass tube connected to a wash bottle filled with 50 mL of ethyl ether. This wash bottle is then connected to another wash bottle filled with 50 mL of ether. After all connections have been made, the crude aldehyde is heated to a gentle boil for 5-10 minutes. The ether will absorb the acetaldehyde as it boils off. If the ether begins to rise up into the connecting tube from the condenser to the wash bottle, increase the heating.

Combine the ether into a 150-mL beaker immersed in a salt-ice bath. Bubble dry ammonia gas into the ether through an inverted funnel or wide tube immersed near the bottom of the beaker. Add ammonia until the ethereal solution smells strongly of ammonia. After about an hour, pure ‘ammonia-aldehyde’ should have separated out. Scrape the crystals from the beaker and collect them by suction filtration. Wash the crystals with a small amount of ether, and allow them to dry in a closed drying heater, with the air constantly circulated through baked-dried CaCl2. The yield is about 30 g.

To obtain pure acetaldehyde, dissolve 10 g of aldehyde-ammonia in 10 mL of water in a 50-mL flask. Add 28 mL of cold 29% sulfuric acid to the flask and set it up for simple distillation. Heat the flask on a water bath to distill over the aldehyde. Place the receiving flask in a salt-ice bath to cool the volatile acetaldehyde. Acetaldehyde is extremely volatile and cannot be stored satisfactorily unless it is refrigerated or sealed in glass ampoules (not just capped), therefore it is necessary to prepare acetaldehyde each time it is needed. There is, however, an easier solution. A quick and easy way to store acetaldehyde is to polymerize it to paraldehyde, which can be handled and stored easily, then depolymerize when it is to be used. To polymerize acetaldehyde for storage, place it in a dry test tube and cautiously add 1 drop of concentrated sulfuric acid per 2 mL of acetaldehyde in the tube. Mix thoroughly, the polymerization will begin to take place. Some gentle warming can hasten the reaction. After some minutes add 3-4 mL of water per 2 mL of acetaldehyde, an insoluble precipitate of paraldehyde will form. Paraldehyde has anaesthetic and sedative properties. To depolymerize paraldehyde back into acetaldehyde, place the paraldehyde into a round-bottom 200-mL Florence flask. Add 4-5 drops of concentrated sulfuric acid for every 20 g (20 mL) of paraldehyde in the flask. Set the flask up for fractional distillation, use glass in the fractionating column. Use a 125-mL Erlenmeyer flask as the receiver; keep it cool by immersing in an ice water (but not salt-ice) bath. Place a loose plug of cotton into the Erlenmeyer flask to help reduce evaporation loss; it must be loose. Care must be taken to prevent the cotton from coming into contact with the distillate. After setting up, heat the flask gently. The temperature of the distillate must not be allowed to rise above 35 °C as it will only re-polymerize. The acetaldehyde thus prepared may then serve as a reactant for other procedures.


Both these procedures were archived from "The Hive".

Waffles SS - 21-1-2012 at 08:53

Quote: Originally posted by AndersHoveland  
There is not really any easy way for the hobbyist to make ethylamine. The most feasible route would probably be partial oxidation of ethanol to acetaldehyde, then distillation with NH4Cl (or possibly (NH4)2SO4 fertilizer).

Thanks,
I think Hofmann Rearrangement is cheaper and easier method also there is better ways for producing Acetaldehyde
I tried vinyl acetate + aceic acid +catalyst(H2SO4) and got lot of pure acetaldehyde

smaerd - 21-1-2012 at 13:35

I was at one point really interested in preparing my own triethylamine seeing as how all tertiary amine proton scavengers are really expensive and darn near unobtainable.

What about the gassing dry ammonia into 90% ethanol solution then adding EtBr?(see attached articles)

I posted before asking for advice on gassing ammonia into ethanol solution and no one cared to lend any tips iirc... My best advice should you try this route is do not use a glass pipet, and find some sort of gas dispersion tube. Not sure how well the inverted funnel trick would work. Unless of course you have at your disposal a dewar style condenser and dry-ice/acetone. Unfortunately I do not.

Attachment: A MODIFIED METHOD FOR THE PREPARATION OF TRIETHYLAMINE.pdf (263kB)
This file has been downloaded 2875 times

Attachment: The Preparation of Ethylamine and Diethylamine.pdf (253kB)
This file has been downloaded 1838 times

[Edited on 21-1-2012 by smaerd]

Ephoton - 21-1-2012 at 16:46

Quote: Originally posted by mario840  
Hahahahaha i knew it, on this forum are only google-amateur-chemists, to my thread no one can answer because they know nothing more than goole , in this thread as always some useless method and theorizing bla bla bla bla , ethylamine is produced in good yields by reduction of nitroethane in many methods for example : zinc/ammonium formate, Al/Hg etc. , reduction of nitrile gives a amine with one carbon more so reduction acetonitrile gives ethylamine , acetonitrile is common solvent, cheap, and easy to buy, reduction cheapest al/hg. Cya

D. Gowda, B. Mahesh, & G. Shankare, Ind. J. Chem. Sect. B, 40, 75-77 (2001)
Syn Comm, Vol 33, No 2, pp 281-289 (2003)


Are you alright in the head or what ?

google amatures nice one dude.

Hope you know your posting missinformation when you say that
you can reduce a nitrile with Al/Hg amalgums.

Anyway google doesnt work with tar button so I think you will find
a lot of us dont even use google anymore.

If we could reduce nitriles with amalgums PEA's would be a different kettle of fish.

Waffles SS - 23-1-2012 at 08:56
Quote:

Alcoholysis of sulfamic acid produces ammonium akyl sulfates. On page 629 of the attached article it discusses an example where methanol refluxed with sulfamic acid for several hours yields ammonium methyl sulfate. Ammonium methyl sulfate rearranges at high temperature to methylamine sulfate.

See ammonium.methyl.sulfate.pdf here
http://psychedelichosting.info/Ionium/Rhodium/pdf
or http://80.244.243.200/archive/rhodium/pdf/index.html

http://www.sciencemadness.org/talk/viewthread.php?tid=1261&a...


What about ammonium ethyl sulfate?it should produce ethyl amine sulfate. isnt it?

Sedit - 23-1-2012 at 18:05

No it undergoes an elimination reaction releasing Ethane with no formation of Ethylamine. Since its an Ethylating reagent I am curious weather it can be used to Ethylate an amine so that Ethylamine can be produced but under normal conditions such as that which create methylamine it will not work.

Arsole - 7-2-2012 at 23:32

Could you make Ethyl Bromide and bubble Ammonia gas through that to create a mixture of Ethylamine, Diethylamine, and Triethylamine.

Separate the 3

Ethylamine: BP 16.6 C Miscible in water
Diethylamine: BP 55-56 C Miscible in water
Triethylamine: BP 89-90 C Solubility in water 5.5% at 20°C (So not much)

Could you Distill off the Ethylamine and use the differences in solubility between Diethylamine and Triethylamine to separate the two.
You could probably distill the Di and Tri as they are greater than 25C BP difference.

Am I wrong?

ScienceSquirrel - 8-2-2012 at 04:53

Quote: Originally posted by Arsole  
Could you make Ethyl Bromide and bubble Ammonia gas through that to create a mixture of Ethylamine, Diethylamine, and Triethylamine.

Separate the 3

Ethylamine: BP 16.6 C Miscible in water
Diethylamine: BP 55-56 C Miscible in water
Triethylamine: BP 89-90 C Solubility in water 5.5% at 20°C (So not much)

Could you Distill off the Ethylamine and use the differences in solubility between Diethylamine and Triethylamine to separate the two.
You could probably distill the Di and Tri as they are greater than 25C BP difference.

Am I wrong?



In principal you are right but the reaction would probably require sodium amide in liquid ammonia to proceed at a decent rate. Separating the product would be hard as well.
OK if you have an industrial plant with 50m fractionating towers but tough in a lab.
Ethylamine is a bit of a bugger to handle when pure as it boils below average room temperature in most labs.
For a lot of purposes an aqueous solution is adequate and a lot cheaper.
If I had to make it I would go for the Gabriel synthesis.
http://en.wikipedia.org/wiki/Gabriel_synthesis

Dr.Bob - 8-2-2012 at 07:38

Quote: Originally posted by Arsole  

Could you Distill off the Ethylamine and use the differences in solubility between Diethylamine and Triethylamine to separate the two.


I don't think you could use water solubility to separate them, as once you add diethylamine to water, you create a new mixture, which would readily dissolve triethylamine. Remember solubilities are determined with single, pure compounds, and most impure chemicals are much more soluble, as well as the effect of adding a new chemical to the solvent changes its solvent properties, and almost always makes a better solvent. For example, many paint strippers are a mix of non-polar and polar solvents, as that will dissolve much faster and much more stuff than any one solvent would do. So purification of mixtures of liquids by solubility generally does not work well.

However, A decent still with even a moderate distillation column can separate liquids of different BPs quite well, if the distillation is done slowly and carefully controlled. I have distilled Freon isomers from each other which only had a 1-3 C difference in BP, using a 3' fractionating column, but for over 10C, it is not hard to distill compounds apart to a reasonable purity. Plus, if you want diethylamine, having a trace of triethylamine would generally not hurt, is it is mostly non-reactive. Same way, you could remove traces of DEA from TEA by reacting the DEA with a chemical that would form a new compound and then distill off the TEA. It would be a pain, but I have done such things before in a pinch.

Waffles SS - 9-2-2012 at 03:31

Quote: Originally posted by ScienceSquirrel  

In principal you are right but the reaction would probably require sodium amide in liquid ammonia to proceed at a decent rate. Separating the product would be hard as well.
OK if you have an industrial plant with 50m fractionating towers but tough in a lab.
Ethylamine is a bit of a bugger to handle when pure as it boils below average room temperature in most labs.
For a lot of purposes an aqueous solution is adequate and a lot cheaper.
If I had to make it I would go for the Gabriel synthesis.
http://en.wikipedia.org/wiki/Gabriel_synthesis










Thanks ScienceSquirrel ,
This is really interesting method
Also In the final step we can use basic solution instead of hydrazine(due to Toxicity of hydrazine)
Ethyl chloride easily can be made by ethanol and hydrochloric acid.
Do you know ratio or Instructions (example) for this method?
I think this method is easier than Hofmann Rearrangement method.I want to test this method


[Edited on 9-2-2012 by Waffles SS]

Nicodem - 9-2-2012 at 14:46

Quote: Originally posted by Waffles SS  
Ethyl chloride easily can be made by ethanol and hydrochloric acid.

Easily? Please post the reference or the experimental data so we can judge by our selves.

entropy51 - 9-2-2012 at 18:06

Quote: Originally posted by Waffles SS  

Thanks ScienceSquirrel ,
This is really interesting method
Also In the final step we can use basic solution instead of hydrazine(due to Toxicity of hydrazine)
Ethyl chloride easily can be made by ethanol and hydrochloric acid.
Do you know ratio or Instructions (example) for this method?
I think this method is easier than Hofmann Rearrangement method.I want to test this method
Ethyl bromide is more easily made than ethyl chloride. Different members have reported preps for EtBr on the forum. Basically it just requires the distillation of a mixture of ethanol, NaBr and H2SO4 with very cold water in the condenser.

I believe the protocol for the Gabriel synthesis of primary amines is in Vogel's textbook of practical organic chemistry in the forum library. It is not a trivial exercise, but is not too difficult, especially if you can get phthalimide.

There are several threads pertaining to the preparation of ethyl chloride. Here is one of them: https://www.sciencemadness.org/whisper/viewthread.php?tid=13...

[Edited on 10-2-2012 by entropy51]

Waffles SS - 9-2-2012 at 21:12

Quote: Originally posted by Nicodem  
Quote: Originally posted by Waffles SS  
Ethyl chloride easily can be made by ethanol and hydrochloric acid.

Easily? Please post the reference or the experimental data so we can judge by our selves.


In below topic you can find it:
http://www.sciencemadness.org/talk/viewthread.php?tid=2726
Ethanol + hydrochloric acid + ZnCl2(catalyst)
Yield is low but this is possible.
I think this method is cheaper , easier and safer than EthylBromide route and it doesnt need special equipment
this mean for me Easily
Quote:

The successful conversion of methyl and ethyl iodides
into the N-alkylphthalimides by reaction with potassium
phthalimide at 150°C was reported by Craebe and
Pictet in 1884. It was already known that N-alkylphthalimides
could be hydrolyzed to phthalic acid and
the primary amine, but it was Gabriel who appreciated
the significance of these reactions and formulated the
Synthesis which bears his name.

The Gabriel Synthesis of Primary Amines
Prof. M. S. Gibson1,
Dr. R. W. Bradshaw2,*
Article first published online: 17 DEC 2003
DOI: 10.1002/anie.196809191


The biggest problem is boiling point of ethyl halide(<100c)
This reaction happen near 150c and ethyl chloride or ethyl bromide boil below 100c.
I think i should gases ethyl halide into warm(150C) potassium phthalimide




[Edited on 10-2-2012 by Waffles SS]

Waffles SS - 12-2-2012 at 21:54

What about reduction of Nitroethane by(Sn/HCl)?
Quote:

2 CH3NO2 + 6 Sn + 12H+ 2 CH3NH2 + 3 Sn(IV) + 4 H2O

Cognate procedure: Setup a flask with reflux condenser in which .25 mol of nitromethane, .38 mol of granulated tin metal and a stirrer magnet have been added. Carefully pour 115mL of 31.45% hydrochloric acid (muriatic acid) down the reflux condenser in 10-15mL increments, waiting for the reaction to settle down before pouring the next aliquot. If the reaction seems to get out of hand (excessive frothing, vapor escaping the reflux condenser, etc...) then quickly slide an ice bath in place until it slackens back down. Once all the HCl has been added, heat the mixture to reflux with an electric mantle for 1hr. At the end of this time, allow to cool, preferably in an ice bath, then add, carefully, a chilled solution of 75g sodium hydroxide in 125mL of water. If the flask contents start to bubble violently you will watch your yield go out the window, so add slowly! Since methylamine readily dissolves in water, you will need to distill the reaction contents carefully to first liberate the 40% constant boiling solution (bp: 53°C) and then the gas itself. The product is best captured by bubbling the distillation vapor into a beaker of hydrochloric acid (use a slight molar excess of HCl to insure no loss). Proceed as above by evaporating the bubbler solution to yield the crystals (take care when evaporating HCl solutions, as the excess acid will vaporize into the air, corroding ovens, lungs, etc...). [Vogel's, pg 892]

We can use Nitroethane instead of nitrimethane in above procedure

Nitro ethane can be prepared by below method:

Nitroethane from ethylsulfate, Desseigne variation.
http://www.sciencemadness.org/talk/viewthread.php?tid=15837#...

aliced25 - 13-2-2012 at 00:52

Yep, nitroethane is the simplest of materials to access:o Ain't no issues with the synthesis of that shit...

If monoethylamine, without di- and tri-ethylamine, is the target might I suggest the Hoffman is probably the best option for the amateur chemist. Fucking around with phthaloyl groups for a low value intermediate would appear to be overkill.

Waffles SS - 13-2-2012 at 10:50

Someone know what pressure neede for reducing Acetonitrile to ethylamine(Raney nickel)?i think it should be below 10atm

entropy51 - 13-2-2012 at 10:59

Quote: Originally posted by Waffles SS  
Someone know what pressure neede for reducing Acetonitrile to ethylamine(Raney nickel)?i think it should be below 10atm
If you have Raney Ni it might be possible to reduce it with NaBH4 and avoid a hydrogenation.

Waffles SS - 13-2-2012 at 11:32

Thanks entropy but I have Roth autoclave and also i have access to hydrogen gas but now i dont have Sodium borohydride
I think reduction is possible at ~4atm
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv3...

S.C. Wack - 13-2-2012 at 15:51

IIRC Hofmann and Stoll used Raney at STP in an LSD article...this is well known to give a mixture, maybe a little more diethylamine.
There are some claims that this and that is more selective for one, for instance if you had NaBH4, Ni/B could be made instantly; it's been claimed to be more selective for ethylamine.

There are also condition hints around for the RX that are said to make it more selective for the primary amine.

PS: Got sodium? Good use here.
PPS: That's just for example, you know, maybe you have some not doing anything. Feel free to experiment. Urushibara? In situ?

[Edited on 14-2-2012 by S.C. Wack]

Waffles SS - 13-2-2012 at 22:02

This is my autoclave(right side)


Unfortunately i dont have a NaBH4 and LiAlH4
I tried Hofmann rearrangement but i was unsuccessful.I like to try another possible method.
I want to try Acetonitrile reduction method.I read some where that this reduction happen at 400k and at gas phase.

[Edited on 14-2-2012 by Waffles SS]

Ephoton - 14-2-2012 at 16:11

I am often unsuccessfull on a first attempt of a synth that is new to me.

Trust me hofmann works and works very very well for low weight amides.

propionamide will turn easily too ethylamine and in very high yeilds with hofmann.

this is one of the routes that Bee's have been using to make methylamine for years it
is tried and tested and does not produce any dimethylamine :)

I believe that it was probably your amide that was at fault if you had problems with this reaction
as it is truly one of the easists reactions there is.

you just add the amide to the bleach at temps around 5 C and stir like mad.

after it all turns into a milk shake add caustic and heat till you hit 70 C

reaction should be over with in an hour or two.

If you havent come up with a way to collect your goods you will be breathing them
very hard to miss.

Nice autoclave by the way wish I had one like that.

how much did that cost you :)

Waffles SS - 15-2-2012 at 22:46

Dear Ephoton ,
I think my Propionamide is impure.i made it by heating ammonium propionate like orgsyn site method for making acetamide(Ammonium Sulfate + calcium calcium propionate)

I keeped temp at 0-5C but it seems the reaction goes run away
Did you try this method for making primary amine?

This is my lab autoclave, it cost 10000$(with full Accessories),i like my pilot autoclave(it made of Titanium/Tantalum)It has 100lit capacity


[Edited on 16-2-2012 by Waffles SS]

Ephoton - 16-2-2012 at 06:28

I have never made the amide the way you have state but rather made the ammonium salt then heated till I got
amide distilling over :)

If you look at the wiki page on propionamide you will see it has a boiling point of 213C
http://en.wikipedia.org/wiki/Propionamide

If we look at this msds entry we can see that ammonium propionate has a melting point of 45C
http://unionbiotechnology.en.alibaba.com/product/252355078-2...

I was not making propionamide but other alphatic amides for solvent (formamide)

the synthesis should run the same though.


this is a great way to get the amide I think as you have a solid that will not boil anywere near the
brake down point needed to rearrange to amide and a very definative boiling point to check purity of
amide.

I have always gone from free acid with ammonia/amine gassed into it.

the orgsyn reaction you have linked too does not use calcium propionate but rather the free acid
it also does not use the sulfate of ammonia but rather the carbonate.
(that is if we consider acetic acid propionic for our purpouses)

I think what your trying to do is form calcium sulfate and ammonium propionate from the salts your using.

It may be better to use the compounds direct both ammonia and propionic acid.

It does work as can be seen by the methyamine synth and the luckart reaction posted on
rhodium.

well no wonder I dont have one of those wonderfull machines at that price :D

still very nice I can understand your wishing to use it to reduce acetonitrile.

It would seem from this post and this patent that you will need to dope your nickel cat or you will end up
with aldehyde or other reduction products of this kind.

Having said that all I have done is use a search engine I have not played with nickel cats as I can not get them.
http://www.sciencemadness.org/talk/viewthread.php?tid=17075
http://www.freepatentsonline.com/5777166.html

If you got a liquid distill from your mix at the right temp it should be propionamide I would think.

I can not think of anything else that would come from ammonium propionate that would boil at such a high
temp.

Xylene is a great recrystalisation solvent for amides. just add amide to boiling xylene till it will disolve no more.
and let cool.

you should get very very pure amide from this method I would think well from other amides I and others have
and the orgsyn article you linked to uses benzene and ethylacetate.

I have not worked with propionamide but the thought of ethylamine lithium reductions makes me wonder
why I never did (maby becouse I was never into benzylic alcohols of course ethylamine has many other uses)




[Edited on 17-2-2012 by Ephoton]

Waffles SS - 16-2-2012 at 09:13

Thanks dear Ephoton ,
I made my ammonium propionate by calcium propionate + ammonium sulfate and then i heated ammonium propionate for making propionamide.like orgsyn method for making acetamid(i used ammonium propionamide instead of ammonium acetate)
It seems something happening At 160-170. lot of smoke Appear and Yellow/Orrange liquid start to come over. i think this Yellow/Orange liquid is Impurities.i didnt Distill my final product again and i used it directly in Hofman reaction

Maybe I try another method for making Propionamide. i think This method is easier( i will make Propanoic acid by H2SO4 + Calcium propionate)

2 H3C-CH2-COONH4 + NH2CONH2 = 2 H3C-CH2-CONH2 + (NH4)2CO3

Also i found this:
Hydrogenation of Basic Nitriles with Raney Nickel
Wolfgang Huber
J. Am. Chem. Soc., 1944, 66 (6), pp 876–879
DOI: 10.1021/ja01234a009
Publication Date: June 1944
http://pubs.acs.org/doi/abs/10.1021/ja01234a009

[Edited on 16-2-2012 by Waffles SS]

Ephoton - 16-2-2012 at 16:34

As I said I have no experiance with nickel cats.

Good luck though it would seem you have the equipment.

ye amides are normally white in color and this one should be solid at room temp this might explain why it was not working properly.

If you decide to try it again I would recrystalise the product after distillation from xylene.

I am not sure about ammonium propionate but with the urea hofmann even traces of some ions
will screw it up (hence the use of gelitin to capture and hold these ions)

This is not the case though for all amides when put through hofmann.

Waffles SS - 16-2-2012 at 21:58

Do you know solubility of Propionamide in xylen and another solvent?(I know its very soluble in water)

mightywingman4 - 19-2-2012 at 23:05

Quote: Originally posted by Dr.Bob  
Quote: Originally posted by Arsole  

Could you Distill off the Ethylamine and use the differences in solubility between Diethylamine and Triethylamine to separate the two.


I don't think you could use water solubility to separate them, as once you add diethylamine to water, you create a new mixture, which would readily dissolve triethylamine. Remember solubilities are determined with single, pure compounds, and most impure chemicals are much more soluble, as well as the effect of adding a new chemical to the solvent changes its solvent properties, and almost always makes a better solvent. For example, many paint strippers are a mix of non-polar and polar solvents, as that will dissolve much faster and much more stuff than any one solvent would do. So purification of mixtures of liquids by solubility generally does not work well.

However, A decent still with even a moderate distillation column can separate liquids of different BPs quite well, if the distillation is done slowly and carefully controlled. I have distilled Freon isomers from each other which only had a 1-3 C difference in BP, using a 3' fractionating column, but for over 10C, it is not hard to distill compounds apart to a reasonable purity. Plus, if you want diethylamine, having a trace of triethylamine would generally not hurt, is it is mostly non-reactive. Same way, you could remove traces of DEA from TEA by reacting the DEA with a chemical that would form a new compound and then distill off the TEA. It would be a pain, but I have done such things before in a pinch.


What if you only had triethylamine? Would you somehow be able to reduce it down to diethylamine? What would it take if it's possible?

weiming1998 - 20-2-2012 at 05:02

I have no sources for this, but maybe the reaction between an amine/amide and ethanol will generate ethylamine? I have tried to isolate glucosamine from glucosamine HCl with ethanol as a solvent before. When I boiled the crushed glucosamine HCl pill with sodium hydroxide in the ethanol, a thick white vapour that smells somewhat like ammonia had begun to collect. Soon it ignited my container with a yellow flame. I extinguished the flame with a wet cloth, then filtered the liquid. More of this vapour collected and boiled out, even as I was filtering this. Soon the vapour stopped evolving, and I was left with a brown solution of what I thought was glucose.

Maybe you could give this a try with a distillation setup, with the end that receives the ethylamine cooled by some ice in a box around, but not in the receiving flask.

S.C. Wack - 20-2-2012 at 15:49

Ehh...........I'd try distilling alanine and baryta first.

weiming1998 - 21-2-2012 at 01:37

Quote: Originally posted by S.C. Wack  
Ehh...........I'd try distilling alanine and baryta first.


Are you sure that creates ethylamine and not a barium salt of this amino acid? Or some other decomposition product when heated?

[Edited on 21-2-2012 by weiming1998]

mightywingman4 - 21-2-2012 at 15:43

I heard there was a way to do it with light...but can't really find the correct reference on the web. Can anybody direct me to a source? Of this or something similar?

...Or just tell me how if you know? =) Would be much appreciated, thanks!

Waffles SS - 21-2-2012 at 20:53

Quote: Originally posted by weiming1998  
I have no sources for this, but maybe the reaction between an amine/amide and ethanol will generate ethylamine? I have tried to isolate glucosamine from glucosamine HCl with ethanol as a solvent before. When I boiled the crushed glucosamine HCl pill with sodium hydroxide in the ethanol, a thick white vapour that smells somewhat like ammonia had begun to collect. Soon it ignited my container with a yellow flame. I extinguished the flame with a wet cloth, then filtered the liquid. More of this vapour collected and boiled out, even as I was filtering this. Soon the vapour stopped evolving, and I was left with a brown solution of what I thought was glucose.

Maybe you could give this a try with a distillation setup, with the end that receives the ethylamine cooled by some ice in a box around, but not in the receiving flask.

I think That is Ammonia not Ethylamine

[Edited on 22-2-2012 by Waffles SS]

Ephoton - 22-2-2012 at 05:34

ye not sure on the solubility and as it has a low melting point it would probably end up as the solvent that
disolves the xylene if you get what I mean.

but if you put enough in there and put it in the freezer it would crystalise out nicely.

no way your going to get ethylamine from ammonia and ethanol distillation.

another way would be to go through acetaldehyde oxime and reduce it but that would take
synthesis of both acetaldehyde and the oxime.

if you wished to go through ethanol maby forming ethylbromide first then reacting with ammonia might
be the go.

anhydrous conditions is needed for this reaction if my memory serves correctly.

the delepine reaction should work as well I think so you could use hexamine in stead of ammonia which
would have to be bubbled into an alcohol.

I think your talking about adding an amine onto an alkene mightywingman4.
http://www.devileye.net/catalog/winding_machine/light-cataly...

I have yet to hear of some one pull this off at home though it has been discussed in the past for synthesis
of other amines.

"18.2 moles of ammonia was charged into a reactor system consisting of a one-liter stainless steel reservoir, a quartz reactor for admitting the actinic light to the solution, and a circulating pump. External to the quartz reactor was an ultraviolet light source. Both reactor and light source were enclosed in a reflecting stainless steel cylinder. Ethylene was then charged into the system until the pressure reached 260 psig and 2.3 moles of ethylene were dissolved in the ammonia. Before the lamp was turned on, the solution was circulated for approximately one-half hour to ensure proper mixing and to cool the reactant mixture to 7.degree.-8.degree. C. No reaction was observed in this period. The circulating high pressure (autogenous) liquid reactant mixture was then exposed to ultraviolet lamps for the time periods given in Table 1. Analyses of the final mixture by gas chromatography are also shown in the Table. Conversations are given for ethylene, and yields are to mixed mono-, di- and tri-ethylamines. The high-energy xenon flash lamp of Table 1 discharges 25 joules over a 10 cm. path through a 1 mm. bore; the spectral output peaks at 3000 .ANG. and a large proportion of the radiation falls in the range of 1800-2200 .ANG.. "

weiming1998 - 23-2-2012 at 03:34

Quote: Originally posted by Waffles SS  
Quote: Originally posted by weiming1998  
I have no sources for this, but maybe the reaction between an amine/amide and ethanol will generate ethylamine? I have tried to isolate glucosamine from glucosamine HCl with ethanol as a solvent before. When I boiled the crushed glucosamine HCl pill with sodium hydroxide in the ethanol, a thick white vapour that smells somewhat like ammonia had begun to collect. Soon it ignited my container with a yellow flame. I extinguished the flame with a wet cloth, then filtered the liquid. More of this vapour collected and boiled out, even as I was filtering this. Soon the vapour stopped evolving, and I was left with a brown solution of what I thought was glucose.

Maybe you could give this a try with a distillation setup, with the end that receives the ethylamine cooled by some ice in a box around, but not in the receiving flask.

I think That is Ammonia not Ethylamine

[Edited on 22-2-2012 by Waffles SS]


Probably not ammonia, because there is no water in the system. To have ammonia evolution, you need water and the only possible reaction that forms ammonia without water in this case is that the NaOH exchanges the OH- for the NH2- ion, which will make sodium amide, which will then react with ethanol to form ammonia and sodium ethioxide. But C2H5+ would be a much stronger acid than Na+, and the NH2 will be attracted to the stronger acid, forming ethylamine.

Waffles SS - 23-2-2012 at 05:41

Your Ethanol was anhydrous?Did you try to condense it?

weiming1998 - 24-2-2012 at 00:50

I think I have made a mistake. I tried to test my methylated spirits for water by putting dry, white (with a hint of green) copper sulfate into the alcohol. after some swirling, it went green, so there are traces of water. I will try and completely eliminate the water, then repeat later.

I have repeated my experiment with anhydrous alcohol (the methylated spirits is treated with anhydrous copper sulfate thoroughly first. If it has water, it will be in very, very minute quantities that wouldn't contribute much. But still the same thick vapours and the same distinct smell of ammonia.

[Edited on 24-2-2012 by weiming1998]

Waffles SS - 24-2-2012 at 10:47

I am doubtful! Ethylamine is little difference in smell than ammonia.

Today i found out: I did mistake and i didnt make ammonium propionate from ammonium sulfate + calcium propionate.
Yesterday i tried this reaction again and i became surprise.nothing happened after adding calcium propionate solution to ammonium sulfate solution,it was clear without sediment :o




[Edited on 24-2-2012 by Waffles SS]

weiming1998 - 25-2-2012 at 02:45

Quote: Originally posted by Waffles SS  
I am doubtful! Ethylamine is little difference in smell than ammonia.

Today i found out: I did mistake and i didnt make ammonium propionate from ammonium sulfate + calcium propionate.
Yesterday i tried this reaction again and i became surprise.nothing happened after adding calcium propionate solution to ammonium sulfate solution,it was clear without sediment :o




[Edited on 24-2-2012 by Waffles SS]


Exactly! The vapours smelled much the same as ammonia.

Google Heads

cal - 27-2-2012 at 06:46

Quote: Originally posted by Waffles SS  

Quote:

Alcoholysis of sulfamic acid produces ammonium akyl sulfates. On page 629 of the attached article it discusses an example where methanol refluxed with sulfamic acid for several hours yields ammonium methyl sulfate. Ammonium methyl sulfate rearranges at high temperature to methylamine sulfate.

See ammonium.methyl.sulfate.pdf here
http://psychedelichosting.info/Ionium/Rhodium/pdf
or http://80.244.243.200/archive/rhodium/pdf/index.html

http://www.sciencemadness.org/talk/viewthread.php?tid=1261&a...


What about ammonium ethyl sulfate?it should produce ethyl amine sulfate. isnt it?

WELL SAID

cal - 27-2-2012 at 08:56

Quote: Originally posted by Waffles SS  
@Ephoton,Yes Hofmann Rearrangement is really interesting


I think we can customize below route for Ethylamine .
This method for making ethylamine is easier than methylamine because ethylamine boil at ~16c( I have access to calcium propionate :D)
But i think ammonium propionate can easily be made from ammonium sulfate and calcium propionate.but i dont know what temp needed for making ammonium propionamide from ammonium propionate.
Quote:

Synthesis of Methylamine/Methylamine HCl via Hofmann Rearrangement
There are two approaches to producing an amine from an amide using the Hofmann rearrangement reaction. One way is to react the primary amide with an alkaline-halide solution (eg - Sodium Hydroxide and Bromine). The other method is to use an alkaline-hypohalite solution (eg - Sodium Hydroxide and Calcium Hypochlorite). The astute observer will notice that there is no chemical difference in the two processes. One produces the Hypohalite in situ, the other uses the Hypohalite itself. Substitution of various halogens/halides/hypohalites/hydroxides is acceptable, but I feel I have picked the best combination of maximal yield and ease of availability. Feel free to prove me wrong ;-). Also, at least one text specifies that Sodium Hypochlorite produces much higher yields than Sodium Hypobromite. This delicious vindication is expected since Chlorine is a more reactive halogen than Bromine. Now, we are going to use Calcium Hypochlorite, in the form of powdered pool shock, because concentrated Sodium Hypochlorite is a rare, unstable creature indeed. Our yield will not suffer in the slightest because of this.

The main example presented will be the alkaline-hypohalite method as it is the easiest to acquire the necessary chemicals. It is of interest to note that the alkaline-halide method is much easier to perform, processwise, in that it is more forgiving of sloppy technique.

The general theory behind the process is that the hypohalite will convert the amide to a haloamide. This then spontaneously changes to the isocyanate when heated and decomposes to the amine from the water present. In effect, all that happens is that a Carbonyl (CO) group is stripped off the starting amide to yield the corresponding amine. Yields pre-purification are around 80%, post-purification average around 65%. Certain uses of the resulting amine will not require purification, though, so it will be left up to you whether or not to perform those steps.

To make methylamine we start with Acetamide. The general, unbalanced reaction process is thus:

CH3CONH2 + Ca(OCl)2 ----> (CH3CONCl)2Ca++ + H2O
then
(CH3CONCl)2Ca++ + NaOH ----> CH3NH2 + Na2CO3
CAUTION Methylamine is a poisonous, noxious inflammable gas. It has a strong ammonia/rotting fish-like odor. It's not as bad as Chlorine gas, though, which can be produced if one is careless in the beginning!


You can scale these reactions up or down within reason. What is reasonable? I can't say, but I have done batches from .01 to 1 mole with no difficulty. The key problems in scaling this reaction have to do with heat gradients in the flask and inadequate stirring. Use your own judgement, keeping in mind that this is not an industrial process.

One reference to keep in mind (Thanks to J.W. Smith for sending this one) concerns the first step of the reaction.

Whitmore and Thorpe, J. of the Amer. Chemical Society, Vol 63, April 1941, p1118
"It was necessary to allow several hours for the formation of the N-chloroamide before heating to degradation temperature. With this modification it was possible to prepare methylamine...consistently in 78% yield."
In my experience, this is a true statement. Please remember to keep the reactants well iced, though. Now, to begin:
In a large mixing bowl which can contain a smaller stainless steel mixing bowl, prepare an ice bath with water and salt to bring the temperature down to -10C or so. Setup your glassware for simple distillation with magnetic stirring beforehand because certain steps need to be performed quickly. Use a vacuum adapter to connect to the receiver flask, and attach some rubber or polypropylene tubing to the vaccum nipple to connect to a bubbler setup (a funnel inverted in a beaker, or a plastic aquarium aerator tube). The distilling flask should be sitting in in a stainless steel bowl with nothing in it (you will add pre-heated oil to the bowl).

NOTE In order to make this as painless as possible, please observe the following recommendations: 1) Keep the mixing bowl temperature as close to 0C or less as possible; 2) Keep the Hypochlorite solution as it is being added as close to 0C or less as possible; 3) After half the Hypochlorite solution has been added, place a plastic bag with 50-100g ice/salt/water mix into the bowl to help keep temperatures low (use this instead of directly adding ice to the reactants, which adds a considerable volume of water making the process less volumetrically efficient); 4) Purchase an 8lb bag of ice ahead of time!


Next you will prepare three solutions.

10g of Acetamide in 20mL of distilled water.
16.4g of Calcium Hypochlorite (Pool shock) in 50mL of hot distilled water
24g of Sodium Hydroxide (Lye) in 40mL of cold distilled water
This last solution should be prepared slowly as it is quite exothermic. Set all three aside in a freezer. Now prepare the mixing apparatus which will be a stainless steel "mixing bowl" suspended in the ice/salt bath made earlier. We use a stainless steel bowl here so that heat transfer will be maximal, while preventing any corrosive interaction. A glass bowl will not be sufficient for larger scale preparations as it will not conduct heat fast enough to prevent the reactants from going over 10C (at which point the Haloamide will decompose and you'll have to start over). Take the Sodium Hydroxide solution out of the freezer once it is cool, but not cold.
After the bowl has been sitting in the ice bath for a few minutes, add the Acetamide solution. Stir well until the solution has cooled to -10C. Now, slowly add the Hypochlorite solution to the mixing bowl in bursts of no more than a couple mL while stirring vigorously. If you do this perfectly, there will be no fizzing or bubbling at all. This depends on how cold you keep the mixture, and how slowly you add the pool shock! Realistically, the considerable heat evolution of the reaction will make adding the last few mL a trying task! Keep an additional 50g of ice on hand to throw directly into the mixture if necessary. This solution may evolve Chlorine gas so you should obviously perform this step under a fume hood or outside). Keep stirring until it has calmed down and turned a turbid colorless to light green Let it sit for 2 hours, stirring occasionally and making sure that it never gets warmer than 5C.

After the 2 hours is up, add the Sodium Hydroxide solution quickly with stirring. The solution should immediately turn a chalky, milk white. That's because a lot of Sodium Carbonate just got generated. You no longer need be concerned over it's temperature, so you can leave the solution in this state overnight if perhaps the hours have passed by too quickly and you've suddenly realized it's 2:00am.

Preheat a water bath on the stove (or wherever) to about 80C and place the stainless steel mixing bowl in it. Once the temperature of the solution hits about 65C, take the bowl out and set aside while stirring all the while. This is where it rearranges, and the reaction is exothermic enough to sustain it's temperature nicely. If you find the temperature climbing past 80C, immerse the bowl into some cold water briefly. After about 15 minutes the temperature will start to fall, at which point you should transfer the whole mess to the distilling flask. Before you continue you need to choose whether you want to make the hydrochloride salt or the aqueous solution of Methylamine, though.

Heat the flask using an oil bath to 100C after adding this solution to effect gentle boiling which will drive off the Methylamine as a gas. In my experience, misbehavior is likely to occur at this point. One particular problem to watch out for is the sucking back of bubbler solution (be it plain water or 6N HCl) into the receiver flask. I don't know why the pressure in the distilling flask would go below atmospheric, and therefore cause this to happen, but it has several times with me. Needless to say, this results in a serious mess and botches the whole process (I have found a cure for this by using an automotive one-way vacuum valve, like a PCV).

Continue heating the flask contents until you have collected around 100mL of distillate in the receiver.

For the aqueous solution: Place 18mL of cool distilled water into your bubbler setup. The expected, not theoretical, yield of Methylamine from this amount of reactants is 7 grams. I have used a plastic aquarium aerator tube as the bubbler with excellent results. Sure beats using an inverted funnel.

For the HCl salt: Do exactly as above except use 6N Hydrochloric Acid. 6N HCl may be produced by diluting 60.4mL of "Muriatic Acid" to 100mL with distilled water. Evaporate the bubbler solution to dryness then add 15ml of water, 10mL 10% NaOH soln. and heat gently to a boil with constant motion until dense white fumes appear. This will remove the Ammonium Chloride. Remove from heat while stirring as it cools down. Pulverize the dry residue, then reflux with absolute Ethanol for several minutes. Filter the refluxed soln. on a heated Buchner or Hirsch funnel, then distill the alcohol off the filtrate until crystals just begin to form. Allow the soln. to cool naturally to room temperature, then cool further in an ice bath. Filter the solution on a chilled Buchner funnel with suction. The yield of Methylamine Hydrochloride should be around 55% of the theoretical.

To clean the white residue off of your glassware, dump some muriatic acid straight from the jug onto them and swirl.

References:

Journal of Chemical Education, v14, pg542
Organic Reactions volume 3
Vogels Elementary Practical Organic Chemistry, pg574



Do you know decompose temp of chloride salt of Ethylamine ?and solubility in acetone and EtOH?




[Edited on 21-1-2012 by Waffles SS]



Derivative Type: Hydrochloride
CAS Registry Number: 557-66-4
Molecular Formula: C2H7N.HCl
Molecular Weight: 81.55.
Percent Composition: C 29.46%, H 9.89%, N 17.18%, Cl 43.47%
Properties: Crystals from ethanol + water, mp 110°. d 1.22. Soluble in 0.4 part water; freely sol in alcohol; slightly sol in chloroform or acetone. Practically insol in ether. Keep well closed.
Melting point: mp 110°
Density: d 1.22

ChemistryGhost - 5-7-2012 at 14:51

Making a primary amine

The reaction happens in two stages. In the first stage, a salt is formed - in this case, ethylammonium bromide. This is just like ammonium bromide, except that one of the hydrogens in the ammonium ion is replaced by an ethyl group.


There is then the possibility of a reversible reaction between this salt and excess ammonia in the mixture.

What do you actually get if you react bromoethane with ammonia?

Whatever you do, you get a mixture of all of the products (including the various amines and their salts) shown on this page.

To get mainly the quaternary ammonium salt, you can use a large excess of bromoethane. If you look at the reactions going on, each one needs additional bromoethane. If you provide enough, then the chances are that the reaction will go to completion, given enough time.

On the other hand, if you use a very large excess of ammonia, the chances are always greatest that a bromoethane molecule will hit an ammonia molecule rather than one of the amines being formed. That will help to prevent the formation of secondary (etc) amines - although it won't stop it entirely.


Basically use as much ammonia as possible or a very large excess of ammonia and react with bromoethane. I don't know much of the details or conditions of the reaction

The ammonia removes a hydrogen ion from the ethylammonium ion to leave a primary amine - ethylamine.

The more ammonia there is in the mixture, the more the forward reaction is favoured.



--------------------------------------------------------------------------------
Note: You will find considerable disagreement in textbooks and other sources about the exact nature of the products in this reaction. Some of the information you'll come across is simply wrong!

You can read the arguments about the products of this reaction by following this link.

Warning! That page is in the mechanism section of the site. Return to the current page using the BACK button on your browser. If you use the links at the bottom of that page, you could get seriously lost!



--------------------------------------------------------------------------------



Making a secondary amine

The reaction doesn't stop at a primary amine. The ethylamine also reacts with bromoethane - in the same two stages as before.

In the first stage, you get a salt formed - this time, diethylammonium bromide. Think of this as ammonium bromide with two hydrogens replaced by ethyl groups.

There is again the possibility of a reversible reaction between this salt and excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the diethylammonium ion to leave a secondary amine - diethylamine. A secondary amine is one which has two alkyl groups attached to the nitrogen.



ChemistryGhost - 5-7-2012 at 14:58

Wait! There's more!
What do you actually get if you react bromoethane with ammonia?

Whatever you do, you get a mixture of all of the products (including the various amines and their salts) shown on this page.

To get mainly the quaternary ammonium salt, you can use a large excess of bromoethane. If you look at the reactions going on, each one needs additional bromoethane. If you provide enough, then the chances are that the reaction will go to completion, given enough time.

On the other hand, if you use a very large excess of ammonia, the chances are always greatest that a bromoethane molecule will hit an ammonia molecule rather than one of the amines being formed. That will help to prevent the formation of secondary (etc) amines - although it won't stop it entirely.



Basically, use a large excess of ammonia and react it to bromoethane. I don't know much of the details of the reaction.
http://www.chemguide.co.uk/organicprops/amines/preparation.h...
:cool:


01AAA.png - 11kB

ChemistryGhost - 5-7-2012 at 15:01

Hooray for ethylamine!:D

01E.png - 11kB

Random - 18-7-2012 at 02:21

Methyl Ethyl Ketone ----haloform---> sodium (calcium) propionate -----> propionic acid ---urea----> propanamide ----Hofmann rearrangement---> ethylamine

ChemistryGhost - 7-9-2012 at 10:00

Can ethylamine be obtained from reacting hydroxylamine with ethyllithium?

ChemistryGhost - 7-9-2012 at 10:55

Acetaldehyde reacts with Hydroxylamine to produce ethylidenehydroxylamine.
CH3CHO + NH2OH ==> CH3CH=NOH
It might have nothing to do with ethylamine though. :D

zed - 8-9-2012 at 12:00

Jeeze, buy some Platinum, produce some catalyst, and hydrogenate Acetonitrile.

Some of the guys get gallons of Acetonitrile for free. Under some conditions, Diethylamine may be produced, when the imine intermediate condenses with already formed Ethylamine.

I'll try to produce a reference.

ChemistryGhost - 13-9-2012 at 14:08

Quote: Originally posted by zed  
Jeeze, buy some Platinum, produce some catalyst, and hydrogenate Acetonitrile.

Some of the guys get gallons of Acetonitrile for free. Under some conditions, Diethylamine may be produced, when the imine intermediate condenses with already formed Ethylamine.

I'll try to produce a reference.

I think that may involve having the reactants in the gas phase.

ChemistryGhost - 13-9-2012 at 14:10

What about ethylamine dissolved in acetonitrile and using an amalgamation type reaction with Al/Mg (Aluminum and Mercury). :cool:

Nicodem - 24-9-2012 at 10:28

LXXXII.—The preparation of ethylamine and of diethylamine
Emil Alphonse Werner
J. Chem. Soc., Trans., 1918, 113, 899-902.
DOI: 10.1039/CT9181300899

Attachment: The preparation of ethylamine and of diethylamine.pdf (136kB)
This file has been downloaded 1248 times

zed - 29-9-2012 at 17:16

I don't have access to the full article, but I was thinking of something more along these lines.

http://www.deepdyve.com/lp/elsevier/liquid-phase-hydrogenati...


www.springerlink.com/content/t2004w4m2418n779/

https://docs.google.com/viewer?a=v&q=cache:CYh-nxTSnJEJ:...

[Edited on 30-9-2012 by zed]

[Edited on 30-9-2012 by zed]

ChemistryGhost - 4-10-2012 at 13:22

Maybe ethylamine can be obtained via ethanol and a tosyl chloride intermediate. Then reacting the intermediate with ammonia. Maybe there will be ethylamine without diethylamine or triethylamine. :cool:
Here's the reference.
http://www.erowid.org/archive/rhodium/chemistry/mdma.tosylat...


Ethylamine synthesis.png - 3kB

triskelion - 6-10-2012 at 07:47

Try the decarboxilation of alanine in high boiling solvent with ketone catalyst.
In this article, the authors made it with tryptophan obtaining tryptamine:

S. Takano, T. Nishimura, K. Ogasawara "Heterocycles 6(8), 1167-71 (1977) ".

Waffles SS - 14-10-2012 at 12:36


Decarboxylation of amino acids
Quote:

Methylamine from glycine
10 g glycine and 15 g urethane (molar excess) were dissolved in 50 ml 0.25M Ba(OH)2 and heated for 2 hours. After precipitating the baryta as the carbonate by passing CO2 through the solution, the filtrate was acidified with a couple of drops of HCl and the solution was evaporated. The hydantoin was not isolated, yet 50 ml conc HCl was added and this was refluxed for 10 hours, after which the major part of the solution was evaporated.
This caused the hydantoin to completely transform into methylamine, so that by addition of ethanol no hydantoin was precipitated, and the characteristic reaction (2) of amines with sodium nitroprusside and acetone was obtained.
The solution was decolorised with animal charcoal and picric acid was added. After evaporation the picrate was obtained as brightly yellow plates with mp 215°C. Yield: 29 g picrate (84%)

M. Wada - Biochem. Z. 260, 47, 1933
http://www.sciencemadness.org/talk/viewthread.php?tid=9915&a...

I think replacing alanine with glycine should lead to Ethylamine





[Edited on 15-10-2012 by Waffles SS]

zed - 20-10-2012 at 14:18

OK, I'd probably try hydrogenating acetonitrile over CoB on Carbon, in Isopropyl alcohol saturated with NH3.

Worked extremely well for reducing Propionitrile to Propylamine. As in example 7.29

http://www.scribd.com/doc/73915503/Handbook-of-Heterogeneous...


The whole of "The Handbook for Heterogeneous Hydrogenation for Organic Synthesis" , now seems to be available online, for free perusal. Courtesy of Wiley.

[Edited on 20-10-2012 by zed]

ChemistryGhost - 26-10-2012 at 14:59

Ammonium chloride condenses with formaldehyde to form methyleneimine. Can a grignard reaction be done with the grignard reagent of methyl chloride to form ethylamine?



Ethylamine QM.jpg - 7kB

[Edited on 26-10-2012 by ChemistryGhost]

Nicodem - 26-10-2012 at 23:05

Quote: Originally posted by ChemistryGhost  
Ammonium chloride condenses with formaldehyde to form methyleneimine.

Seriously? Please give us a reference for a preparative reaction of methyleneimine.

triskelion - 28-10-2012 at 15:09

to chemistryghost:
the reaction between formaline and ammonium chloride goes on and lead to methyl, dimethyl, trimethylamine hydrochloride.
The Grignard reaction to methyleneimine should works, but it's very difficult to obtain it.
Impossible by the reaction you proposed.

zed - 1-11-2012 at 14:24

Well, I don't like your chances. Polymerization is more likely, and of course the H20 formed via the condensation of formaldehyde and ammonia, is probably more reactive than the imine.

In fact, the DOJ has reported regrets that such reactions usually do not work.

During several raids on novice labs trying to produce Methamphetamine, they found zero product.

The reaction sequence of condensation of Acetaldehyde with Methylamine, followed by Sodium Sulfate drying, and reaction with Benzyl-Magnesium Chloride....Does not work well.

More stable imines can reportedly be used in such reactions,
Methyleneimine is probably not a good prospect.


Sydenhams chorea - 1-11-2012 at 16:14

Quote: Originally posted by Waffles SS  

Decarboxylation of amino acids


Quote:

Methylamine from glycine
10 g glycine and 15 g urethane (molar excess) were dissolved in 50 ml 0.25M Ba(OH)2 and heated for 2 hours. After precipitating the baryta as the carbonate by passing CO2 through the solution, the filtrate was acidified with a couple of drops of HCl and the solution was evaporated. The hydantoin was not isolated, yet 50 ml conc HCl was added and this was refluxed for 10 hours, after which the major part of the solution was evaporated.
This caused the hydantoin to completely transform into methylamine, so that by addition of ethanol no hydantoin was precipitated, and the characteristic reaction (2) of amines with sodium nitroprusside and acetone was obtained.
The solution was decolorised with animal charcoal and picric acid was added. After evaporation the picrate was obtained as brightly yellow plates with mp 215°C. Yield: 29 g picrate (84%)

M. Wada - Biochem. Z. 260, 47, 1933
http://www.sciencemadness.org/talk/viewthread.php?tid=9915&a...

I think replacing alanine with glycine should lead to Ethylamine
[Edited on 15-10-2012 by Waffles SS]


I think not. Had you used the search engine, you would have found that the Wada article is complete bullshit, and that hydrolysis of the hydrantoin will just give back the original amino acid.

link to the pdf: An Investigation of Wada’s method of Converting alpha-Amino acids into 2-Substituted Ethylamines
Quote:
The reaction (Wada, Biochem. Z., 1933, 260, 4T), whereby an a-amino-acid is converted into a 2-substituted ethylamine by hydrolytic decarboxylation of the corresponding hydantoin, could not be repeated: the amino-acid was regenerated in each case. Some observations on the Rimini reaction for primary amines are recorded.

Waffles SS - 3-11-2012 at 02:25

@Sydenhams chorea ,
You are right,it seems this is bullshit article

But what about :
Amino Acid DecarboxylationCatalyzed by 2-Cyclohexen-1-One

http://www.erowid.org/archive/rhodium/chemistry/trp.decarbox...

This is bullshit too?

ChemistryGhost - 1-1-2021 at 09:01

I think propionitrile hydration with hydrochloric acid to propionamide, then sodium hypochlorite Hoffman rearrangement to ethylamine could work.

Boffis - 1-1-2021 at 12:45

Feasible but your source of propionitrile is..?

karlos³ - 2-1-2021 at 09:41

Quote: Originally posted by ChemistryGhost  
I think propionitrile hydration with hydrochloric acid to propionamide, then sodium hypochlorite Hoffman rearrangement to ethylamine could work.

You again with the proposing of noneconomical routes, Blue Dex?

Fantasma4500 - 13-7-2022 at 13:40

ok so- in my hunt for ethylamine, - chloroethane

"The advantage of use of an emulsifying agent is shown by shaking an alkyl clfioride, say ethylene chloride, with 19% ammonia solution. Where no emulsifying agent is used the heavy chloride separates to form a colorless layer within half a minute but Where a small amount of ammonium oleate is present no such separation occurs until after many ,hours."

https://patents.google.com/patent/US2113640

"Thus, about 20 parts ethylene dichloride, containing small amounts of oleic acid, for example, 0.5% (or 0.1 part by volume after aqua ammonia has been added) which will give an ammonium soap"
they mention.. 10psi to 300 may be used, 10 psi is 0.68 bar, so below atmospheric pressure? does this reaction form gasses- could it maybe be put in a plastic bottle and just be contained for a week to keep it a slight bit pressurized?

"The reaction is effected at a temperature of about 100 C. to about 200 C. and preferably about 125 C. and is about complete in about 40 minutes at about 125 pounds per square inch gauge pressure."

for every 10*C reaction speed is doubled, 40 minutes.
can we assume it will actually happen at room temperature?


i did also have success with theanine- i just mixed that up with 20% H2SO4 and reacted at maybe 60*C for 6 hours or so, then NaOH into that, theanine is rather costly however, 100g cost me about 20 euros or was it just 10?
it was same price for 250g alanine - as im attempting to turn it into nitroethane i tried briefly to oxidize alanine with H2CrO4, no luck it seemed - amine to nitro is typically done with manganate of even KHSO5+acetone
anyhow the alanine was reacted at about 160*C with 1g copper chromite per 50g, it was powdered well first. this however turns into a rather diabolic chunk in a glass flask, HCl seems to take care of it, it seems HCl must then be reacted with NaOH to free more amine from the mixture- but also to free the bottle- high boiling solvent can maybe fix this?

some amine was acquired from the decarboxylation of alanine with copper chromite to assist it, milk heated with NaOH and suspected amine will typically tell if you have an amine, methylamine turned the mixture pink after some minutes of heating, ammonia wont do this. iirc it turns brown or yellow instead?

ErgoloidMesylate - 18-8-2022 at 09:08

Will sodium and absolute ethanol reduce acetamide?

https://en.wikipedia.org/wiki/Bouveault%E2%80%93Blanc_reduct...

[Edited on 18-8-2022 by ErgoloidMesylate]

Texium - 19-8-2022 at 17:12

No

ErgoloidMesylate - 21-8-2022 at 17:13

Looks like heating acetamide with sodium borohydride makes acetonitrile, which can be reduced with sodium and alcohol to ethylamine

Edit

Heat at 150 c for 6 hours, evolves ammonia, makes alcohol, and acetonitrile in theory.

But that is ridiculous.

I think a better idea is just to reduce nitroethane and be done with it.

[Edited on 22-8-2022 by ErgoloidMesylate]

clearly_not_atara - 21-8-2022 at 19:27

There are less silly ways to dehydrate acetamide, like simply refluxing over alumina. And acetonitrile is useful enough that it can be worth it to make/buy for its own sake. Polar, aprotic, low boiling. In fact buying acetonitrile is probably the easier option — it's much less of a pain to purchase than nitroethane!

But the reduction is a shitshow. You have to make sodium in an inefficient thermochemical reaction or an elaborate electrochemical setup. Four moles of sodium for one mole of EtNH2 theoretical, more in practice.

However, cobalt-on-nitrogen-doped-carbon catalysts can catalyze the efficient reduction of nitriles with hydrogen:
https://www.sciencedirect.com/science/article/pii/S187853522...
Unfortunately, the paper's interpretation of "mild" conditions refers to 7 bar hydrogen at 110 C. If this were a salsa, it would make children cry.

The Co@CNx catalysts can also be made from sucrose and melamine and can utilize formic acid as a reducing agent:
https://doi.org/10.1002/cssc.201802163

I am not aware of a nitrile reduction using Co@CNx with formic acid, but I also don't know that it doesn't work.

[Edited on 22-8-2022 by clearly_not_atara]

ErgoloidMesylate - 3-5-2023 at 11:45

Quote: Originally posted by ErgoloidMesylate  

I think a better idea is just to reduce nitroethane and be done with it.

[Edited on 22-8-2022 by ErgoloidMesylate]


Getting ready to publish a better book on the topic, having looked up an old method of concentrated ammonia dissolved in ethanol and adding ethyl halide, I believe I have found the preferred method to accomplish this, which will be put in my new book coming out.

Anhydrous ammonia in anhydrous ethanol and adding ethyl halide. Boiling off the ethanol, and freebasing the amine salts to distill and separate and dry.

Should do the trick nicely and be the way it is done even here on this site.

clearly_not_atara - 3-5-2023 at 17:45

http://archives.njit.edu/vol01/etd/1960s/1964/njit-etd1964-0...

According to this MS thesis from 1964, ethyl bromide reacts with urea at 100 C in DMF.

ErgoloidMesylate - 4-5-2023 at 15:53

Quote: Originally posted by clearly_not_atara  
http://archives.njit.edu/vol01/etd/1960s/1964/njit-etd1964-0...

According to this MS thesis from 1964, ethyl bromide reacts with urea at 100 C in DMF.


The availability of DMF becomes a huge issue. Perhaps you can include it in your book.

My method involves easily obtainable items.

clearly_not_atara - 4-5-2023 at 18:44

Solvents are usually replaceable. DMSO would react with the substrate, but other polar solvents might do the trick.

The thesis mentions other rxn conditions as well, but mostly I thought the alkylation of urea was just really interesting.

Good luck writing the book, I hear that takes a while.

SplendidAcylation - 7-5-2023 at 13:16

I haven't read the whole thread so I apologise if I am repeating what others have said, but has the Delepine reaction been considered?

I noticed the Hofmann rearrangement and Gabriel synthesis were mentioned...

For the preparation of propionamide for the former, propionic acid + urea would work.

ErgoloidMesylate - 7-5-2023 at 13:39

Quote: Originally posted by ErgoloidMesylate  

... having looked up an old method of concentrated ammonia dissolved in ethanol and adding ethyl halide, I believe I have found ...
Anhydrous ammonia in anhydrous ethanol and adding ethyl halide. Boiling off the ethanol, and freebasing the amine salts to distill and separate and dry.



May have to add hcl to ensure it is all converted to salt, before distilling off the ethanol.

[Edited on 7-5-2023 by ErgoloidMesylate]