Sciencemadness Discussion Board

Nitroethane from ethylsulfate, Desseigne variation.

Antoncho - 21-3-2011 at 10:07

The search engine here doesn't show much on the topic of kitchen synthesis of this useful substance, so i'd thought i'd let you know about this recent success of ours at HyperLab.

1. Ethylsulfate preparation (unoptimized).

600 mls 95% EtOH was combined with 300 mls 92% H2SO4. 600 mls of this mixture were slowly dripped into an excess of Ca(OH)2 (amount of lime is determined by titration). Solids were filtered off thru a piece of dense cloth and then filtered clean on Buchner. Filtrations are easy, calcium salts act as celite for themselves.

A sample of thus obtained Ca(EtSO4)2 solution is reacted with an excess Na2CO3, the chalk is filtered and weighed to determine the amount of Na2CO3 needed for neutralization. In this case it was 0.7 mole. The calculated amount of carbonate (made by heating baking soda in the frying pan) solution is added to the reaction and some more carbonate is added until the solution develops an intense blue color on a strip of universal indicator paper (not just bluish tint under the precipitate's spot, intensely blue -- otherwise there's not enough carbonate added yet) .

The solution is again filtered thru cloth and then -- vaccum filtered thru Buchner. Filtering is again not hard at all. Total volume of solution was 1300 mls.

The remaining liquor is placed in a large enameled bowl, on the inner side of which there's drawn a mark of the desired final volume of the liquid. Desseigne's figure is 56% NaEtSO4, density = 1.36 g/cm3, so for 0.7 mole it would bee ~130 mls.

The bowl is put on a electric heater which is turned at FULL THROTTLE (the one in question is 1,8 kilowatt :) ) and a hair dryer is fixed above the bowl so that the stream of hot air is directed at 45 deg. angle to the liquid's surface and towards the open window (unless you want your kitchen to resemble a sauna, that is :P).

This treatment allows one to evaporate ~2 liters of water per hour :o and does not hurt the ethylsulfate a least bit.

When water is removed, the solution is retutrned to RT at filtered from precipiteted salts, mostly carbonate in this case. The authors have gotten 150 mls of solution with sp. gravity of 1.335 g/cm3, which should contain 52% of NaEtSO4, judging by Desseigne's figures.




2. Nitroethane.

A 500 ml 3-necked flask (3 necks is NOT enough for this synthesis, so you'll have to drill two wholes in the central cork: one for the mech. stirrer's faucet, the other -- for the dripper) is equipped with a mechanical dtirrer, an addition funnel, a thermometer protruding to almost the bottom and a straight distillation condenser.

Inside there's placed:

- 32 mls water
- 6.2 g K2CO3 (stirred until dissolution)
- 75 g NaNO2
- 7 g of any hair conditioner (its chief component is cetyl alcohol, serves as a foam killer)

The apparatus is immerged into an oil bath which is also equipped wtih a thermometer. Temperature control is the royal key to success in this synthesis, so both thermometers are mandatory. (The other essential key to success is the quiality of ethylsulfate, but if you do it properly with 'hands growing not out of your ass', as Russian saying goes, you have that already).

The bath temperature is brought to 150-160 C and kept there thru the reaction. The inner temperature, likewise, must bee kept at 120-130 C the whole way.

The NaEtSO4 solution is dripped in during about an hour -- the rate is determined by the speed of distillation / inner temperature. The distillate consists of water and clearly visible driplets of EtNO2 which soon form large yellow globules in the receiveng flask.

When the addition is finished, some water is dropped in to remove the residually remaining product, which presence is easily detected in the distillate visually. In this case 100 mls were needed (in the original procedure that would bee 30 mls, but then again there was obtained a yield better than in the original procedure, so ... :P )

The distillate is chilled well and 100 g CaCl2 is added. The layers separate, the aq. layer is extracted with 50 mls DCM, combined xtracts washed w/brine abd dried overnight with 10 g CaCl2 (for most part of that time the product was kept in the freezer for the fear that EtONO would ruin the EtNO2).

The solution was decanted from the CaCl2 granules into 100 mls RBF, to it there was added a pinch of Zn dust and 200 mg urea. The flask was equipped with a 30 cm column, thermically isolated as well as possible and distillation on an oil bath is commenced. At 50 C bath temp. the mxtr foams heavily, but soon all ethyl nitrite is removed and foaming stops. DCM is then removed slowly and after that heating was brought up to distill off at 108 C 26 mls (51% on NaEtSO4) of clear colorless oil of nitroethane.

A 2 ml sample of this oil was condensed with 2 ml bitter almond essential oil and 0.4 ml MeNH2*AcOH at 70 C for 1 hr. Synchronously there was carried out another condensation -- in all terms identical save for EtNO2 was taken lab grade pure (Acros, 98%+). The yield for both reactions amounted to 1.92 g of nitropropene and was equal to the centimal digit at least (the scale's precision is 10 mg only ;) )


The preparation of NaEtSO4 described here is by no means looked forward to as there is already posted at HyperLab at least two much better yielding reports starting from EtOH and either H2SO4 or sulfamic acid yielding 45% and 80% NaEtSO4 respectively.

The original article by Desseigne and Giral, (which was originally posted on The Hive by Lugh, BTW :cool: :) ) is attached below.





Antoncho

Attachment: EtNO2_desseigne.djv (52kB)
This file has been downloaded 2198 times


[Edited on 22-3-2011 by Antoncho]

Magic Muzzlet - 21-3-2011 at 10:59

Great, thanks for this. This seems much better than the route with EtBr/NaNO2, or anything else for that matter.

Thank you for posting it here :)

Sedit - 21-3-2011 at 19:20

I smell.... I dont care, he writes in a manner acceptable and clear and to me thats all I care about as should you unless you desire to help him. Unless your willing to imput data that may aid him in his synthesis it should be no concern to you as to his intentions. Other then that its just as simple to say nothing and walk away like when a crackhead ask for spare change and you just roll your eyes and walk away.

Anywho,

Antoncho ... You mention Sulfamic acid, could you please elaborate a bit as well PM me for a direction on a current topic elseware in attempts on Ammonium Ethylsulfate in this synthesis. Also have you considered Simethacone as an antifoming agent as its readily avalible as baby gas drops and more then likely a higher purity then hair conditioner.

mnick12 - 21-3-2011 at 19:55

Im not sure if anyone is interested but I will post anyway.

There is some patent floating around here in one of the older threads on producing ethylsulfuric acid from refluxing ethanol and sodium bisulfate,and ethylsulfuric acid can be easily converted to the sodium salt.
I have had mediocre results producing ethylsulfuric acid from sodium bisulfate and ethanol, but both are super cheap and the process is pretty simple. All you do is reflux ethanol and sodium bisulfate until all of it dissolves (never completely dissolves), cool and filter out the sodium sulfate hydrate. What you are left with is a mix of ethanol ethylsulfuric acid and some dissolved salts. Anyway I have found drying and finely powdering the NaHS04 really helps.

Polverone - 21-3-2011 at 20:46

Antoncho is welcome here. This is a nice gift of knowledge he brings, and he has already modified the style of his post to match local customs. If you have a problem with this thread please write to me directly rather than commenting in this thread. I have split off the non-technical content.

Antoncho - 21-3-2011 at 20:56

1st of all, excuse my using 'SWIM', i haven't realized that this manner of speaking was inappropriate here. I edited my post to exclude all of its occurences in the text.

Quote:
I smell drug cook...


Well i guess after 10 years of being affiliated first with The Hive and later on -- HyperLab.info, it would look ridiculous if i pretended to make nitroethane for rocket fuelling purposes :D:D:D

Still, we at HyperLab are doing what we are doing beecause of scientific interest, not for getting tons of cheap high or - worse yet - monetary profit, as you could've thought.

That's why this synth was performed at all -- its author had a lot of lab grade EtNO2 on hands, but it was not interesting for him to use nitroethane from Acros :)

That's also the reason why the outcome of its reaction with almond oil was immediately after weighing flushed -- honest to goodness -- down the toilet :D The author just needed it to test the obtained EtNO2 on something cheap, otherwise making amphetamine is not interesting for him :)

So please reserve the term 'cook' to some other occasion, we are talking about chemistry here ;)

Antoncho - 21-3-2011 at 21:55

Quote:
There is some patent floating around here in one of the older threads on producing ethylsulfuric acid from refluxing ethanol and sodium bisulfate,and ethylsulfuric acid can be easily converted to the sodium salt.


Oh great, you're the first one to have tried this to my knowledge. Did you ever measure the yields?

I'm asking beecause the much talked of way of making HEtSO4 - by dehydration of EtOH+H2SO4 mix with Na2SO4 -- doesn't seem to work as advertised, there have been some cohesive experimentation to prove this. All you get is usually the plain 40-50% conversion (which is obtained without any drying anyways). And much of the Na2SO4 seems to bee converted into busulfate, not vice versa.

Anyway, the best way of making NaEtSO4 is yet to bee reported -- i have no idea why we got so low yield in this case, the other accounts say that if you plainly neutralize EtOH+H2SO4 mix with Na2CO3 you get about 40% conversion. Na2SO4 and Na2CO3 are insoluble in conc. NaEtSO4 solution, so with a careful mode of operation you can get a very clean separation.

Unfortunately, these other reports are nowhere as specific in terms of figures and details as i'd wish from a scientific procedure, so i didn't post them here.

If anyone does it the proper way and reports everything in exact detail, it would be a great piece of knowledge, IMO.


starman - 21-3-2011 at 22:25

I too am interested in what information you can present on the sulfamiic route.No need for 'cloak and dagger' type communication these reagents have many legitimate uses.Post what you have and I'm sure at least a couple here will do some practical experiments.
Thats what we do here ;)

Ephoton - 22-3-2011 at 00:03

very nice antoncho :)

nice to see you return to your old name as well.

I tried this once but used sodium carbonate rather than potassium.

not the best result.

I do love the way you have not isolated the sulfate.

truly making that stuff anhydrous was a true pain in the ass.

Antoncho - 22-3-2011 at 01:54

Originally posted by bwz at https://www.hyperlab.info/inv/index.php?act=ST&f=17&...

Quote:


200 g sulfaminic acid pulverized w/a coffee grinder (Note 1) and 300 mls anhydrous EtOH (which was grudged) was refluxed for 3 hrs in a 2 l flask (Note 2). The most part of HSO3NH2 dissolved and a pool of melted NH4EtSO4 is formed on the flask's bottom under the layer of alcohol. EtOH is then removed - first with an aid of slight vacuum, then - at 15 mmHg. The residue of melted NH4EtSO4 crystallized slowly, one has to catch the moment when it gets completely solid, but is still soft. After ir crytallizes fully, it is very hard to recover from the flask. Finally it was obtained 270 g of white crystalline agregates.

295-270=25 g -- EtOH not reacted with sulfamic acid = 52 g unreacted acid
52/270*100=19,3% -- sulfamic acid content in the final product
(270-52)/295*100=73,9% - the yield of ammonium ethyl sulfate.

The product was then neutralized with Na2CO3 and evaporated to sp. gravity of 1,34 g/cm3. It still had a weak smell of ammonia due to the present ammonium sulfamate. After filtering out the crystallized salts the volume of the solution constituted 275 mls.

It was reacted with :

60 mls water
12 g K2CO3
137 g NaNO2
1 mls polymethylsiloxane

...to yield 29 g (34% on NaEtSO4) of clear colorless liquid.


Note 1. It's probably not necessary to pulverize the acid since almost all of it dissolves anyway.

Note 2. The flask should have a bottom surface as large as possible since beecause of the alcohol economy there's a layer of NH4EtSO4 on the bottom that partially retains sulfamic acid. The author had to stir it with a knitting needle occasionally. Using a stirrer would allow to avoid this problem.




So.... As you can see, the most interesting question now is whether it is possible to use regular 95% EtOH in this preparation and how successfully it can bee used. Anyone willing to find that out?

Antoncho - 22-3-2011 at 01:57

And oh yeah... Hi guys :hi: , thank you for the warm welcome, i'm glad to see you again as well, old chaps ;)

[Edited on 22-3-2011 by Antoncho]

mnick12 - 22-3-2011 at 13:13

Im sorry I dont remember the yields from the reaction of NaHSO4 with ethanol, but if I remember correctly they were so so. But both the materials are very cheap and can be purchased at any hardware store, thats why this method looked so appealing to me. I am however willing to repeat the experiment and optimize the procedure. This time I will carefully document my results and give a number. But just so you know it might be a while I already have alot stuff going on.

Sedit - 22-3-2011 at 14:16

Thanks Antoncho thats just what I suspected, I wanted to perform the experiment to product Sodium Methylsulfate but never got around to it and now just have yet another Flask of Ammonium Methylsulfate probably going to shit right now. The slight smell of ammonia could be produced from the decomposition of formed Ammonium carbonate which will release NH3 as a decomposition product at a relatively low temperature.

Hexagon - 22-3-2011 at 19:10

Just tried that NaHSO4 synth. and all I obtained was an horrible Na2SO4 (?) chunk sticking to the bottom of the flask from witch I could not filter anything... May be next time I'll try to add a large excess of ethanol (used 1 mole NaHSO4 to 1 mole H2O and 0,55 mole of ethanol, water was used because NaHSO4 was anydrous)

mnick12 - 22-3-2011 at 20:15

Yea its a good idea to use a large excess of ethanol, it makes stirring easier, and the end product is much easier to filter. Im wondering how long did you reflux the mixture for? Also im not sure the water is necessary for the reaction and it may be that your "chunk" of solids is a hydrated for of sodium bisulfate. If you do try the reaction again I would recommend not adding water directly to the mix, using a large excess of ethanol, and longer refluxing.

Attachment: US1411215 (1).pdf (173kB)
This file has been downloaded 1308 times

http://www.sciencemadness.org/talk/viewthread.php?tid=12034#...

heres the patent I was thinking of and the thread to go with it

Hexagon - 23-3-2011 at 07:16

Quote: Originally posted by mnick12  
Yea its a good idea to use a large excess of ethanol, it makes stirring easier, and the end product is much easier to filter. Im wondering how long did you reflux the mixture for? Also im not sure the water is necessary for the reaction and it may be that your "chunk" of solids is a hydrated for of sodium bisulfate. If you do try the reaction again I would recommend not adding water directly to the mix, using a large excess of ethanol, and longer refluxing.


The mixture was refluxed for something like half an hour, after reading the patent again I think that the cooling process used wasn't convenient too. Yeah next time I'll use a larger excess of ethanol and try to run the rxn anhydrous. I added a mole of water to the bisulfate because it was anhydrous, it's pool grade, tested in a test tube inside a boiling cup of water, didn't melted.

[Edited on 23-3-2011 by Hexagon]

Hexagon - 23-3-2011 at 18:30

Ok, first of all sorry for the double post and if antoncho or another one thinks this is off-topic on this synth. of nitroethane, just let me know.

Did another run with the same ammount of NaHSO4 and an excess of ethanol. The bisulfate is pool grade. The MSDS only lists 100% sodium bisulfate, it's slightly yellowish and comes as very tiny pearls, some of them are clumped but it's easy to break them. Axton brand bought at Leroy Merlin, 2kg for 8€. The ethanol is 96º carrefour brand, lists only 99,9% partialy denatured alcohol and 0,1% benzalkonium chloride, 1,05€ for half a liter.

Added 120 grams of bisulfate (1 mol) to a 600 ml erlenmeyer, then added enough ethanol to cover the bisulfate (75 mls, 0,85 mole) On top of this I put an improvised reflux apparatus made with a big glass funnel and a glass bowl on top with water and ice cubes, at any moment there was ice up there (just changed the ice one time). Yes I know a liebig is superior, but I was too lazy to sep it up :D

So, all this hovering in side of a water bath, stirring with a big magnet. The water was nearly boiling most of the time, and this was left at reflux for an hour. After it, I took it out of the water bath and inmersed it on an ice water bath (with stirring too) for half an hour (until it's cold).

After this I filter the resulting milky solution trough a buchner funnel, with the aid of a fridge pump. Some sulfate ends up at the filtrate and settles to the bottom of the kitasato, so I filter it again trough a coffee filter.

This results on a yellow alcoholic solution weighing 54,2 grams. It gives a red response to litmus paper, with a pH around 1-2 (cant find the colour table right now). Take out of it 10 mililiters with a pipete and weight it, 10,25 grams, so the density of the alcoholic solution is 1,025 g/ml

Taking in account that the density of alcohol is 0,79 g/ml and that of sulfovinic acid (EtHSO4) is of 1,46 g/cm. If it's a solution of only azeotropic ethanol and EtHSO4, the given density corresponds to aproximately a 35% of EtHSO4, or 19g of EtHSO4.

From a mole of bisulfate one can expect max. half a mole of EtHSO4, so that 19 grams are a 30% yield of sulfovinic acid based on sodium bisulfate. In theory one can recover around 45 mililiters of ethanol from that solution.

Any toughts on how this synth. can be optimized? Appart from using a less sloppy technique, may be adding more ethanol since it's so cheap, or increasing the reflux time (or heating, since it looked like it only refluxed at 75% or so...)

The neutralization with sodium carbonate goes for another day, now I've got to clean this mess. Have a nice day :)

Sedit - 23-3-2011 at 19:47

It don't mean much right now but I tossed Some of my Ammonia methylsulfate formed thru the solvalysis of Sulfamic acid in Methanol on to Sodium Carbonate and nothing happened at first. Then slowly it started to fizz like mad meaning indeed the Ammonia methylsulfate was being converted into Sodium Methylsulfate just as I suspected and Antonchos report suggested.

Just a quick an dirty test I know but it gives a good amount of information that would allow easy access to anhydrous Sodium Ethylsulfate thru a simular process.

Chordate - 23-3-2011 at 22:00

Hmm. I have been wrestling with making nitrobutane by the NaNO<sub>2</sub> method since monday. Three days later i finally have enough pure sample to keep moving on a project, but my yields were pretty atrocious. 3 grams from some 20 grams of starting butyl bromide. Probably my own fault for being somewhat loose with the reaction timing on a number of runs (I was testing a few things. Result: failure). I should try this with a bit of dibutyl sulfide and see if it plays nice. Thankee much antoncho.

Panache - 23-3-2011 at 23:50

Some input mentioned another time concerning the use of antifoam.
The trouble usually with antifoams is the tendency for the effect to stop suddenly, this can be somewhat mitigated by being prepared for this eventuality and having further agent ready to dispense immediately into the reaction, also by simply using a small nylon cable tie on the stirrer shaft quite high near the neck. This acts like a small whipper snipper on the encroaching foam and its effect increases with increased stirring rate. Note that this works best when your stirrer and condenser are connected to your flask via a claisen head so that the exiting foam has to get through the stirrer shaft thing.
Beware of using the polyethylene cable ties as they will fail when you really need them at these temperatures.

atomicfire - 24-3-2011 at 05:49

Why do you go though the calcium step? Why not use straight sodium carbonate or sodium hydroxide after mixing the ethanol and sulfuric acid?

DJF90 - 24-3-2011 at 07:11

Solubility issues. I'll let you read into it yourself...

atomicfire - 24-3-2011 at 08:23

So is the Ca(EtSO4)2 not soluble in water whereas the NaEtSO4 is?

DJF90 - 24-3-2011 at 09:05

Nope. Both are soluble in water. The reaction mixture is neutralised with CaCO3, the soluble ethylsulfate remains in solution whilst the insoluble calcium sulfate (from the unreacted sulfuric acid) precipitates out. Double decomposition of the resulting solution with Na2CO3 yields the sodium ethylsulfate by precipitation of calcium carbonate. Essentially this workup removes any sulfate from the ethylsulfate, providing a pure product.

Sedit - 26-3-2011 at 20:16

Quote: Originally posted by Antoncho  
Originally posted by bwz at https://www.hyperlab.info/inv/index.php?act=ST&f=17&...

Quote:


200 g sulfaminic acid pulverized w/a coffee grinder (Note 1) and 300 mls anhydrous EtOH (which was grudged) was refluxed for 3 hrs in a 2 l flask (Note 2). The most part of HSO3NH2 dissolved and a pool of melted NH4EtSO4 is formed on the flask's bottom under the layer of alcohol. EtOH is then removed - first with an aid of slight vacuum, then - at 15 mmHg. The residue of melted NH4EtSO4 crystallized slowly, one has to catch the moment when it gets completely solid, but is still soft. After ir crytallizes fully, it is very hard to recover from the flask. Finally it was obtained 270 g of white crystalline agregates.

295-270=25 g -- EtOH not reacted with sulfamic acid = 52 g unreacted acid
52/270*100=19,3% -- sulfamic acid content in the final product
(270-52)/295*100=73,9% - the yield of ammonium ethyl sulfate.

The product was then neutralized with Na2CO3 and evaporated to sp. gravity of 1,34 g/cm3. It still had a weak smell of ammonia due to the present ammonium sulfamate. After filtering out the crystallized salts the volume of the solution constituted 275 mls.

It was reacted with :

60 mls water
12 g K2CO3
137 g NaNO2
1 mls polymethylsiloxane

...to yield 29 g (34% on NaEtSO4) of clear colorless liquid.


Note 1. It's probably not necessary to pulverize the acid since almost all of it dissolves anyway.

Note 2. The flask should have a bottom surface as large as possible since beecause of the alcohol economy there's a layer of NH4EtSO4 on the bottom that partially retains sulfamic acid. The author had to stir it with a knitting needle occasionally. Using a stirrer would allow to avoid this problem.




So.... As you can see, the most interesting question now is whether it is possible to use regular 95% EtOH in this preparation and how successfully it can bee used. Anyone willing to find that out?


There are a couple things that bug me about this synthesis of Ammonium Ethyl Sulfate.

First off he used a little over 2 mols of Sulfamic acid where as he used a little less then 10 mols of EtOH yet he reports that some Sulfamic acid remained after the reflux.

This is just not so. This is a Solvolysis reaction. As the reactant is taken up into solution that is when it reacts to form the desired product. What he had in the bottom of the flask left over was unreacted Sulfamic acid... NOT Ammonium Ethylsulfate.

When forming the Methyl variation I have noted that it only takes around a 3-1 molar ratio at most EtOH to Sulfamic acid to ensure that SIX hours into it there will be nothing more then a slightly yellow solution remaining and no solids at all. With stirring the solvolysis can be accomplished in under 3-4 hours with only a 2-1 ratio and a clear colorless solution is obtained which will precipitate long clear needles on cooling when 1/3 of the solution is distilled.



You ask about 95% EtOH being used but its just not going to work. It is sensitive to hydrolysis and a drying tube should be employed during reflux in the first place when using anhydrous reagents. Using wet EtOH will damage the synthesis from the ground up. Deicing solution in the states anyway is Ethylene Glycol and EtOH. MgSO4 and a distill should yeild a rather clean anhydrous EtOH for the synthesis as its what I use for EtBr synthesis in the past and that went rather smooth.

Hope this helps a bit.

UnintentionalChaos - 26-3-2011 at 20:41

Quote: Originally posted by Sedit  

You ask about 95% EtOH being used but its just not going to work. It is sensitive to hydrolysis and a drying tube should be employed during reflux in the first place when using anhydrous reagents. Using wet EtOH will damage the synthesis from the ground up. Deicing solution in the states anyway is Ethylene Glycol and EtOH. MgSO4 and a distill should yeild a rather clean anhydrous EtOH for the synthesis as its what I use for EtBr synthesis in the past and that went rather smooth.

Hope this helps a bit.


Indeed, I can confirm the moisture sensitivity of the ammonium alkylsulfate. A few crystals of the methylsulfate dissolved in a few drops of water yield no precipitate with SrCl2 initially but forms a cloudy solution after sitting for only a few minutes at room temperature. The decomposition is self-promoting as the acidic ammonium bisulfate product promotes hydrolysis of more methylsulfate as long as water is available. Heating can only make it worse. Consider using anhydrous reaction conditions if possible.

[Edited on 3-27-11 by UnintentionalChaos]

small research for NaEtSO4 routes

no_dream - 15-8-2011 at 09:35

Optimization of sodium ethylsulfate synthesis

Some experiments were conducted on this problem.
Materials used: acid - 96% pure sulfuric acid, alcohol - 99% ethanol with 0,1% MEK and bitrex, CaCO3 - technical grade., Na2SO4 - anhydrous., Na2SO4 - ordinary soda, decahydrate

The scale was 0,3 mol and five samples were prepared.

Sample 1: according to US 3,047,604
17ml acid was added to 18,5ml of alcohol with shaking. After cooling, 8g of dry sodium sulfate was added. The mixure was slowly added with good stirring to an excess of calcium carbonate suspended in water(approx. 25g in 150ml). The solution was vacuum filtered to obtain a clear, neutral liquid. Some phenolphtalein indicator was added and the calcium ethylsulfate was converted to the sodium salt. The formed calcium carbonate was weigted to determine HEtSO4 content. Saturated soda was added until slightly alkaline - pink. PH approx 9 to 11. The suspension was again filtered, and a 25ml sample evaporated to determine the mass of dry NaEtSO4:Na2CO3 mixture. Another sample (25ml) from this mixture was treated with an excess of calcium chloride solution to determine the carbonate content in the liquid. The purity and concentration of final product was calculated..

Sample 2: as per sample 1 but without the sulfate

Sample 5: 3:1 alcohol to acid with sodium sulfate
17ml acid to 55,5ml of alcohol. After cooling 10g sodium sulfate added with occasional shaking. Neutralization as before.

Sample 4: according to sample 5 but without sulfate

Sample 3: according to [1]
55,5 ml alcohol was added to 17ml acid, then refluxed in a water bath two hours. After cooling, the liquid was diluted with 100ml water and CaCO3 suspension was added in excess until neutral and no gas evolved. The neutralization produced much foam and aerosol. A small loss was due to overfoaming.


Results:
No.1:56,5% HEtSO4 of theory, sample purity 69% NaEtHSO4 - error due to splattering when evaporation. 13,3 % of theory of NaEtSO4 calculated from dry mass
No.2:54,6% HEtSO4 of theory, purity 71,7%, 12% of theory of NaEtSO4
No.3:73% HEtSO4 of theory, purity 81%, 36% of theory of NaEtSO4
No.4:76,3% HEtSO4 of theory, purity 53,5%, 10% of theory of NaEtSO4
No.5:86% HEtSO4 of theory, purity 68,7%, 24% of theory of NaEtSO4

The dry weight of the samples was less than the calculated NaEtHSO4 content, so there must be an error in the process
The best method according to EtHSO4 yield was 5, for the total NaEtSO4 yield method 3.

Notes:

a) The best purity product of archieved if the neutralisation, or at least the last part is conducted using calcium carbonate. The resulting liquid is neutral and contains only the soluble Ca(EtSO4)2.

b) Only a slight excess of soda to phenolphtalein is required during evaporation to keep the solution alkaline. Too much soda added makes product impure with sodium carbonate.

c) An excess of alcohol is preffered during the HEtSO4 production. Good stirring is required. Exernal cooling is not needed, some of the alcohol boils off. The alcohol should be added fast. Acid and alcohol cooled in a freezer are preferable. It is not needed to notice the exothermical nature of the reaction. The neutrallization produces only slightly heat.

d) All samples above were leaved overnight before neutralization except No.1.

e) Sodium sulfate produced no temperature rise opposed to the patent. The mixture was shaken occasionaly and then leaved. A cake formed on the bottom, easing decanting the liquid. Some losses are inevitable.

Ethanol recovery is possible, but was not practised because of the volumes of solutions.

Full scale 3mol test of method 5:
170ml acid added to 555ml alcohol. After cooling to slightly warm to hand, 100g anhydrous sodium sulfate added, strirring continued until cold. This was about 4 hours. Then the stirring was discontinued and sulfate let settle. The whole mix was vacuum filtered to minimize losses, but decanting would suffice.
The combined neutralization was proved not to be good, because of delay in ph change. First about 70g slaked lime was suspended in a liter of water, then about 100mls of mixed acid added. Then the mixture become slightly acidic, so about 150g of CaCO3 was added. All of the acid mixture was slowly added with high power stirring with a hand blender (motor with a stick and a blade on the end). Then another half liter H2O added and everything filtered through a cloth and then with vacuum. The gas evolution from the neutralization proved no problem as stirring was vigorous.

The amount of soda was determined and an solution was added to the calcium ethylsulfate. After filtering, a calculated amount of 1,84 mole of ethylNa sulfate was in 2625ml solution. This is 61 per cent of theory. After evaporation and cooling crystal formed, probably of soda. They were filtered ant thrown away. Total volume 360ml, density 1,3.

A test run - 142g NaNO2, 17,6g K2CO3, 90ml H2O, some silicone antifoaming agent and the solution obtained above was made. At the end water was added too.

Temperature was controlled 130-125C, but sometimes it went to 120-115 after adding too much solution.

Workup: distilate (approx. 500ml) was half saturated with salt and CaCl2 (foaming!). After separation, extraction of aqueous with DCM, drying on CaCl2 and adding charcoal, a fractional distillation was run.

Result: 44mls of EtNO2, distilled 112-116degC. Last drops made distillate little cloudy.

0,618 mol from 1,84 mol ethylNasulfate = 33,6%.

20,6% of theory overall yield to acid, 6,86% on alcohol.

Compared to an earlier attempt with 1:1 EtOH:H2SO4 and sodium sulfate, where from 2mol

acid and alcohol the yield was 17ml, 226mmol, 22,6% on NaEtSO4.

Calculated 11,3% total yield to acid or alcohol.


Not much improvement.


Conclusion: It seems the yields cannot be raised much. The desseigne process has a maximum of about 50%, so better methods must be tried for the NaEtSO4. Some research was made and it might be useful to research deeper. Also the sodium bisulfite and direct neutralization(HEtSO4+Na2CO3) should be examined more.

References:
US patent 3,047,604
[1] S. LEVY, Anleitung zur Darstellung organisch-chemischer Praeparate., Stuttgart 1895

Thor - 25-9-2011 at 13:24

Can anyone explain the use of the Potassium Carbonate in the final reaction step? Writing out the equation, I can't see it taking part in the reaction. The only reason I can think of is to adjust the pH?

The reference posted is in French, and i'm a bit rusty..., google also turns up lots of examples of the reaction, but nothing on the use of the carbonate.

Edit: Possibly to hydrolyse the Sulfuric ester?

[Edited on 25-9-2011 by Thor]

Hexagon - 27-9-2011 at 13:05

Quote: Originally posted by Thor  
Can anyone explain the use of the Potassium Carbonate in the final reaction step? Writing out the equation, I can't see it taking part in the reaction. The only reason I can think of is to adjust the pH?

The reference posted is in French, and i'm a bit rusty..., google also turns up lots of examples of the reaction, but nothing on the use of the carbonate.

Edit: Possibly to hydrolyse the Sulfuric ester?

[Edited on 25-9-2011 by Thor]


AFAIK, the potassium is there to make some kind of euthetic and help lower te melting point of the mixture.

chucknorris - 2-5-2012 at 18:14

Ok I did make some half a kilo of ethyl sulfate recently.

What I did was that I measured about 1:1 in weight sodium bisulfate(pool grade is ok, if it wont melt at 60C, add 1:10 ratio of water and heat up to 110c or until it is fully liquified) and ethanol(95% commercial denatured grade goes well, I explain this later) and heated up them both in different pots. The bisulfate should be heated up to 70C and make it fully liquid, same temp is good for ethanol.

Then one should slowly drip the ethanol into the liquid bisulfate. It will instantly turn into white cake of sodium sulfate and the reaction is so exothermic it will cause the ethanol to boil and vaporize so a reflux column is a good one.

One MUST shake or stir the reaction vessel vigorously to avoid formation of sodium sulfate cake. If it is left untouched, it WILL form a layer in the reaction vessel between the ethanol and the liquid bisulfate and this can lead into major catastrophy which happened to me once. When there is ethanol in the flask and the cake layer is carefully broken, the two will mix up instantly, causing large amounts of ethanol being vaporized so that this volcano eventually reached the roof of my laboratory measuring 3 meters of height. A metallic stirrer rod or something ultra-heavy duty is mandatory for this project, or then just after every 5ml addition of ethanol, take the reaction vessel and shake it in your hands violently in order to break the cake before it gets too heavy to be broken without steel rod.

Ok then, when all the ethanol is mixed, heat the vessel for about 15mins for full power with reflux on, and then carefully insert it into cool bath and wait for the core temperature to decrease below 30 degrees. Then you can add 100-200ml of extra ethanol just in case to wash the formed ethyl sulfate residue from the sodium sulfate cakes, and then pour everyting into filter and acquire a slightly yellow liquid.

Then boil up this liquid up to 130 degrees of temperature maximum, and wait for the boiling to cease so that all ethanol is evaporated, a yellow oily liquid is being left in the flask. All unreacted ethanol will be retrieved if reflux condenser is succesfully used, usually with 1:1 ratio this is around 1:4-1:3 of used ethanol in return. The ethanol acts as an solvent for the ethyl sulfate, so do not try to scale it down, you will only lose ethyl sulfate.

Ok now you will understand what makes the denatured ethanol OK for this project.

Measure the weight of the ethyl sulfate freebase and get 1:1 ratio of sodium bicarbonate or baking soda and dump it into, vigorously stirring. The stuff will hiss and it will swoll up so use at least 5 times larger vessel than the volume of the liquid. CO2 is formed in large amounts. This reaction takes some 10-15 minutes, and then you shall just leave the stuff there and come back after 1 day and you will see that a fine white paste has formed in the bottom, and there is yellow oily layer on the top.

This oily layer is the residue of the denaturing agents and other random goo and shit that is left from the reaction. We do not want this garbage in future, so do this: add at least 2 times the volume of anhydrous acetone(water is bad, it dissolves the sodium ethyl sulfate and you will lose it) and pour the stuff into filter. After everything has been filtered, add 1 times the volume more acetone. The acetone will dissolve and wash all the liquid shit off from the sodium ethyl sulfate, and only a pure sodium ethyl sulfate and possibly residues of sodium bicarbonate are left in the filter. Let the mass dry and scrape it into container. You should have pure white fine powder.

If the sodium bicarbonate must be avoided and only 99% sodium ethyl sulfate is wanted and the actual amount of denaturing agents is not known, a pure anhydrous ethanol must be used. Other way, which will cause about 5% yield loss but can be done with commercial detanhol is to add 5-10% LESS sodium bicarbonate by weight into the ethyl sulfate freebase. This will leave some freebase unreacted and it will go through the filter into the waste acetone denatured goo shit, but that way you'll get absolutely no sodium bicarbonate residues into your sodium ethyl sulfate.

Oh, and the yields? Of course. For 4 different runs with only minor differences in the process(no cold dumping, vigorous additon of ethanol(and huge losses of ethanol by vaporization), I managed to get around 45% yield from the sodium bisulfate by weight. So 1kg of bisulfate equals to about 450 grams of ethyl sulfate freebase.

[Edited on 3-5-2012 by chucknorris]

Amy Winehouse - 5-5-2012 at 23:33

Some words about the Sulfamic Acid route:

Marvelous! Riveting! wurks gud.

Alcohol and sulfamic acid are cheap as dirt and the alcohol I used was between 96-98% ethanol, thats right - not anhydrous. I've run this reaction 5-6x, and heres some logistics to keep in mind/things that might have gotten lost in translation if anyone is interested and wants to try this route, which I highly recommend doing.

1) A drying tube with CaCl2 must be used during the entire duration of the alcohol/sulfamic acid reflux period as even slightly hydrated alcohol will become anhydrous as the reaction proceeds (at the cost of some product) and it will suck up water and ruin everything(my first few fuckups, et al; 2012)

2) Don't wait for everything to crystallize before neutralizing, a)you won't get it all b) hydrolysis tick tock tick tock; just add a little less solution than theory (0.5 eq versus sulfamic acid) directly to the RM after the alcohol is gone and proceed from there, its fine if you overshoot

3) When evaporating to spg, put in the freezer and let sit for 20 min or so and gravity filter, collecting a sample of these droplets when testing. Even if it's not hot, there could still be dissolved solids giving you incorrect density reading(and that will clog up your addition funnel later on). I don't think it can go past 1.35 g/ml, any evaporation passed that and you're precipitating product.

4) Just use regular old NaCl to separate EtNO2 from H2O, CaCl2 will cause it to foam up nasty-like.

5) I think Russian conditioners must be different than other places, but please don't use random conditioner as an anti-foaming agent. Simethicone(polydimethylsiloxane) is cheap and won't make you're distillate smell fruity or tropical.

Good luck!

roamingnome - 31-7-2012 at 19:59

hashing out this ammonium ethyl sulfate situation and i believe the nomenclature is a miss.

Sulfamic acid reacted with ethanol will potentially form ethylsulfamate, or sulfamic acid ethyl ester ,

the ammonium is not a free moving ion as in typical salts. this doesn't really matter i suppose as long as the isolate effects the reaction of nitrite the same.


It seems isolating the dry compound is not favored but the compound is left in alcohol of a certain s/g
Is this then mixed with the carbonate and nitrite like that?


US patent 2785196 actually gives the melting point of
of ethyl sulfamic acid as 170 C


does it react similar?
im struggeling to separate the the ethyl from unreacted sulfamic acid .

$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$&$
And now time for a special update

United States Patent 4469841
"During baking, of the order of about 121° C, the ethyl N,N-dimethylsulfamate ##STR1## sequentally undergoes the following reactions. The sulfamate undergoes a molecular rearrangement in which the ethyl radical of the ester migrates to the nitrogen atom, forming a betaine ##STR2## The betaine adsorbs water to form a trialkyl ammonium bisulfate salt ##STR3## It subsequently decomposes to volatile dimethyl ethyl amine and sulfuric acid. "


Well its seems a similar ester does lose the ethyl as a radical which is good i think.
Now what is the temperature of reaction of nitrite, carbonate, and ethyl sulfate?

Attachment: US2785196.pdf (158kB)
This file has been downloaded 2173 times

[Edited on 1-8-2012 by roamingnome]

[Edited on 2-8-2012 by roamingnome]

anomolous - 24-3-2013 at 10:24

Can someone explain why Antoncho first neutralized the ethylsulfate with Lime and then with sodium carbonate? Couldn't the sodium ethyl sulfate be formed by neutralizing ethylsulfate with sodium carbonate and skipping the calcium hydroxide step? Based on my trenslation of the original French article, this is exactly what they do. What is the purpose of using the Lime?

I've been trying a bunch of nitroethane synths out. I did repeat this process with some success but it needs to be streamlined to improve yields as I did not get as much as Antoncho. Check out my posts in the Nitroalkane thread if interested in my attempts using 2-bromoproprionic acid. I definitely need help there. If Antoncho is around I'd love your opinion.

Peace.

no_dream - 29-3-2013 at 10:24

Because the French article uses oleum for the esterification of ethanol. So the free SO3 reacts with the water formed in the reaction and the yield of ethyl-sulfuric acid is close to theoretical.
But when using sulfuric acid and 1,6eq of ethanol, the conversion is about 50%. Don't believe it can get better using sodium sulfate.

Direct neutralization will produce an mixture of Na ethyl-sulfate and Na sulfate. Maybe too much sodium sulfate will interfere with the reaction. Much sodium sulfate is produced by the final reaction with nitrite, but maybe it could work. Try it out.

Using an calcium salt (carbonate is better than hydroxide) for neutralization gives calcium ethyl-sulfate and CaSO4. The filtered liquid contains only the ethyl-sulfate. Reacting with sodium carbonate precipitates calcium carbonate and leaves practically pure Na ethyl-sulfate in the solution.

anomolous - 30-3-2013 at 20:56

Ah, thanks. I did try to neutralize with only Na2CO3 and did get some nitroethane but, you're right, yields weren't as good as when I neutralized with Ca(OH)2 (all I have on hand). If anyone is interested I will post the results.

anomolous - 2-4-2013 at 11:41

Experimental 1: 300 mL of 96% H2SO4 was carefully added to 600 mL of ~95% ethyl alcohol in a 1000 mL Erlenmeyer. 250 g of anhy. NaSO4 was added and the mixture placed into the fridge and then into the freezer to cool to about 10C. The hydrated sodium sulfate was filtered leaving ~800 mL of ethylsulfate/alcohol solution . The solution was treated with sodium carbonate until a neutral pH of 7 was reached. Blue indicator paper turned slightly pink and red paper turned slightly blue at this pH. The neutral solution was cooled to near 0C and the precipated salt (mostly sodium sulfate) was filtered. The filtered solution was distilled and about 200 mL of alcohol was collected. The residue was filtered again and evaporated in a pyrex dish until a skin began to form, at which time the heat was turned off and the solution allowed to cool on the hotplate. A lot of salt, consisting of a mixture of sodium sulfate, carbonate, and ethyl sulfate, precipitated. This salt was saved to be analyzed and possibly used to produce more nitroethane. The filtered liquid, about 292g/240 mL, and a density of 1.21 g/mL was further distilled and more salts filtered yielding 210 g/155 mL (= Density of 1.35 g/mL). This close to the density of a 50-55% solution of ethyl sulfate, according to the Antonch and Desseigne figures. Upon sitting further, overnight, the solution crystalized further, leaving 164 g/123 mL (Density = 1.33) of sodium ethylsulfate sol. A 55% (by weight) solution of 210 g ethylsulfate sulfate sol. would contain 210 g * .55 = 115.5 g. The molar mass of ethyl sulfate is 148.12, which means we hypothetically had about 0.77 moles of ethyl sulfate in solution. I will react this solution with a molar ratio of sodium nitrate—about 53 g. 7 g of potassium carbonate (~6.9% based on 210 g sodium ethylsulfate sol.) will be used and 6 g of cetyl alcohol hair-conditioner. e
6 g of hair-conditioner was added to a 500 mL flask equipped for distillation, followed by 7g of potassium carbonate dissolved into 27 mL of water. Stirring is activated and 53 g of sodium nitrite is added. The oil bath is heated to 155C and the sodium ethylsulfate sol is added dropwise. The addition was stopped because it took some time for distillate to occur then continued at the rate of distillation. After the addition 100 mL of water was added dropwise and the distillation continued to make sure all of the nitroethane distilled over. About 150 mL of distillate, a mixture of water and yellow globules of nitroethane, was collected. This was extracted with ether (3 x 50 mL). The ether was removed by distillation, and the residue, maybe 15 mL, was saved to be further purified once more is collected.

Experimental 2: 600 mL of 95% ethyl alcohol was carefully mixed with 300 mL of 96% sulfuric acid. A titration was done showing it was a 9.26 molar solution. 840 mL required 7.78 mole Ca(OH)2 is required to neutralize this solution so 575 g of Ca(OH)2 was mixed with 2000 mL of water in a large pitcher and the 840 mL of ethylsulfate/alcohol solution was carefully added to this with stirring. After the the ethylsulfate solution had been reacted with the Ca(OH)2 another 500 mL of water was added to assist in extraction and filtering as the mixture was very thick. The CaSO4 formed was filtered through clothe and then through filters until the solution was clear, resulting in 1970 mL of CaEtHSO4 solution. 100 mL of this solution was reacted with an excess of Na2CO3 and the chalk vacuum filtered, dried in an oven, and weighed (4.4 g) to determine the amount of Na2CO3 needed for neutralization. In this case 0.87 mol or 91 g of Na2CO3 (4.4 g/100 = 0.044 mol; 0.044 mol x 19.7 = 0.87 mol; 0.87 * 106 = 91 g). I used 92 g as an excess was recommended. The resulting solution had a pH of 9.4 and turned red indicator paper a vibrant blue. The mixture was vacuum filtered. Do not try to filter all of the CaCO3 all at once unless you have a gigantic filter because it will not fit. I had a fairly large Buchner and did half of the mixture; I rinsed the chalk, emptied the Buchner funnel, changed the filter, and then did the other half. The filtrate was refiltered by gravity filtration until clear and then evaporated on a pyrex cakepan with a fan blowing over it overnight. CaCO3/NaEtHSO4 salts precipitated during the evaporation. These were filtered and saved for further experimentation and the filtrate, 256 g/200 mL (Density: 1.28), was used in the next step. It will be assumed that 0.87 mol or 124 g of sodium ethyl sulfate is in solution and this will be reacted in a molar ratio to sodium nitrate (58 g). To a 500 mL flask with three-neck adapter, equipped with mechanical stirring, for distillation, and with an addition funnel, was added a squirt (5-7 g) of cetyl alcohol hair-conditioner, 30 mL of water, and 8 g of potassium carbonate. This was mixed, placed into an oil-bath and the oil-bath heated quickly to 155C with occasional stirring. Once the oilbath reached 155C the addition funnel was charged with the NaEtHSO4 solution and the addition began. The addition was carried out very slowly at first and then accidently nearly all of the NaEtHSO4 was added within 20 min.I allowed this mixture to distill for a long time before adding the last 20-30 mL. The distillate, water with yellow oil globules present was extracted with ether and the ether removed by distillation. The residue (12 mL) was saved to be purified further when more nitroethane has been collected.

Experimental 3: The sodium ethylsulfate sol. was prepared as above, except the titrations and sample reactions were not done; the ethylsulfate sol. made by reacting 600 mL 95% ethyl alcohol and 300 mL 96% H2SO4 was reacted with amounts as above (i.e. 575 g Ca(OH)2, 92 g Na2CO3) and then evaporated to a manageable amount (125 mL). The NaEtHSO4 solution was reacted with 60 g of NaNO2 in 30 mL of H2O with 10 g of K2CO3 and a squirt of cetyl alcohol hair conditioner. After the addition 50 mL of water was added. About 400 mL of distillate was collected. The yellow globules of nitroethane were apparent. This was extracted with ether (2 x 50 mL). The ether removed by distillation and the residue (22 mL) was added to the previously collected nitroethane.

don't think you done any of these 3 exprience or either you done it wrong!

FJS - 15-4-2013 at 04:41

Quote: Originally posted by anomolous  
Experimental 1: 300 mL of 96% H2SO4 was carefully added to 600 mL of ~95% ethyl alcohol in a 1000 mL Erlenmeyer. 250 g of anhy. NaSO4 was added and the mixture placed into the fridge and then into the freezer to cool to about 10C. The hydrated sodium sulfate was filtered leaving ~800 mL of ethylsulfate/alcohol solution . .....


Hope no offense taken but that's my feeling! coz doing chem is not my pro. but always following! ;) mainly coz I'm doing something relates to solvents.

Anyway regards the EtS initially I considered that very simple but after many (over 5 attempts) find out there's a few trick involved that none told in initial post or guide. and I do not know why :( hope I find time and make it very simple and stright forward. I mean Ets. not the nitro part. I never done nitro part.

aliced25 - 2-6-2013 at 02:11

Water will probably not be promoting hydrolysis of methyl sulfate (see attached paper), but is probably releasing it from the ammonia (I'm not sure of the reaction between ammonia and sulfamic acid, but I'm guessing there is one). I've also attached the Sartori reference that is often talked about, with the high-temperature (well -150-160C might seem like high temperature to some) decomposition of methyl hydrogen sulfate to dimethyl sulfate. Could be useful indeed.

With ammonium methyl sulfate, surely acidification would release the methyl sulfate, which could then be trialed as a source of DMS?

Attachment: Guzowski.etal.Understanding.and.Control.of.Dimethyl.Sulfate.in.a.Manufacturing.Process.Kinetic.Modeling.of.a.Fischer.Est (1.5MB)
This file has been downloaded 1501 times

Attachment: Sartori.MethylSulfuric.DimethylSulfate.pdf (432kB)
This file has been downloaded 1020 times


Akira990 - 16-9-2014 at 10:41

I recently googled way to sodium ethyl sulfate. I am posting it here cause i want someone with a bit (a lot) more experience than myself to see if it is possible or not.
Maybe i shouldnt post it considering last post on this topic was more than a year ago but i will give it a shot and hope someone can explain it to me..

Procedure.
In 500 ml RB Flask was added 100 ml EtOH (97% is high enough ? ) 96% Sulphuric acid 100 ml (180g) in small portions was added carefully with cooling. Na2SO4 60 grams were then added and the mixture heated to 120C and kept at that temp for 1 hour. Na2SO4 was filtered off and gave 130 ml of pink ethylsulphuric acid.
In a 500 ml RB flask in 300 ml EtOH (its essential to use not less alcohol, you'll se why if you wont) were added 66g unhydrous K2CO3. 75 ml of ethylsulphuric acid were added dropwise with mixing. The ethanol is then distilled off. The wet salt was heated on a plate standing on a water bath removing the remants of ethanol . Yield approx 85g.

What i do not understand is what for we add K2CO3 in this procedure when we know K2CO3 is insoluble with alcohol.

So i am asking here that someone with experience elaborate this procedure to me (ofc if procedure itself is good)

Metacelsus - 16-9-2014 at 13:22

I've always wanted to try making sodium ethyl sulfate, but I'm worried about forming diethyl sulfate and giving myself cancer. What's the risk of forming toxic amounts of diethyl sulfate in this procedure (reaction of sulfuric acid, ethanol, and sodium sulfate)?

If it's safe then I will probably try it this weekend.

Also, 120 C seems a bit high in the above procedure. Wouldn't you be making ether at that temperature?

[Edited on 16-9-2014 by Cheddite Cheese]

Akira990 - 17-9-2014 at 00:40

If i am not wrong (pls correct me if i am) everything under 140 C is ok and ether wont form...

But my problem is procedure itself cause i am not sure that end product in this procedure is really sodium ethyl sulfate, thats why i asked for someone with more experience to elaborate procedure...

BTW i can see many answers but they seems to be deleted by admins, pls respond accordingly to forum rules..

[Edited on 17-9-2014 by Akira990]

Akira990 - 18-9-2014 at 03:04

After some brainstorming i think i have cracked it.

First part of procedure we have ethanol and sulfuric acid, Na2SO4 is absorbing agent (correct me if i am wrong ) its purpose is to collect any water left so ethyl hydrogen sulfate not react with water..

Second part of procedure, which also confused me is adding K2CO3 to ethanol. After that we add ethyl hydrogen sulfate (in procedure it is named ethyl sulfuric acid) dropwise with mixing. My thoughts about this, ethanol in second part is used as solvent and added ethyl hydrogen sulfate will react with K2CO3 to produce potassium ethyl sulfate (not sodium which we need) and potassium bicarbonate (KHCO3)

I also think there are some problems in this procedure, we use ethanol in second part as solvent but even if it is 97% it still have some water in it so adding ethyl hydrogen sulfate dropwise might result in hydrolysis instead of reaction with K2CO3 (Na2CO3 for sodium ethyl sulfate instead of potassium ethyl sulfate)

Last problem is i found some references which says you can do it at 25 C and this procedure says refluxing for 1 hour on 120 C (ethanol, sulfuric acid and Na2SO4)

Only reason i am posting this here and asking for some kind of help is because i dont want to end up with diethyl sulfate which is toxic. Ofc i can find myself with few experiments results of each procedure but in case i might end up with deithyl sulfate i would avoid it by any means if possible




[Edited on 18-9-2014 by Akira990]

Oxirane - 19-9-2014 at 12:15

I have made ethyl sulfate many times and attempted to make nitroethane with different methods without confirmed success. My story:

I heated sodium bisulfate and with reflux on and vigorous stirring, added small amounts of ethanol and exothermic reaction took place. Mixing was essential because hard layer of sodium sulfate formed which prevented the reaction on going. I cracked two glass vessels during my many syntheses because of this and made one geysir when the formed cake cracked and very exothermic reaction took place between sodium bisulfate and ethanol.

When the reaction was complete, ethanol was added in excess. All solids were crushed and the mixture was filtered and washed with excess ethanol and then ethanol was distilled off to leave yellow, oily residue. I tried to vacuum this oil, but it decomposed into something that stung my breath very severly when I later washed off the carbonic residues from the flask. The ethyl sulfate was reacted with sodium bicarbonate to form sodium ethyl sulfate, which was washed with excess of acetone and dried to form slightly yellow mass.

I attempted to make nitroethane with direct nitrifying with sodium nitrite, and then in another batch which for I made ethyl bromide via sulfuric acid, ethanol and sodium bromide. From the first reaction I never managed to obtain any residue, but from the later I got about 25ml of oily liquid by distillation. I dont have equipment to test out what it really was, but boiling range was close to nitroethane. I used continuous flow of CO2 inert gas for every step just in case because some ppl told NE and side produced ethyl nitrite could cause spontaneous detonations upon contact with air oxygen.

Templar - 27-9-2014 at 06:17

Quote: Originally posted by Sedit  
I smell.... I dont care, he writes in a manner acceptable and clear and to me thats all I care about as should you unless you desire to help him.


Wait isnt sedit a member of various websites dedicated to that certain field of synthesis?

Ethyl nitrite is not explosive last time I checked. Maybe you mean ethyl nitrate?

[Edited on 27-9-2014 by Templar]

Akira990 - 20-10-2014 at 05:18

I have tried sodium bisulfate / ethanol method according to US patent..

I used 138g of sodium bisulfate (mix of powdered bisulfate and larger parts just to check if there is any difference) i made myself... Use powdered bisulfate, larger parts not good..

46g ethanol, i have used 96%

In US patent i mentioned it is not said how long reflux should last neither it is given any temperature..

I refluxed it for 25 minutes on ~100C.. After that was done i put all in beaker (which is in ice water) cooled it <32C with a lot of stirring... Than i filtered it few times (more times cause i use coffee filters) with adding ethanol (here it is used as solvent, easier to filter), i was left with yellow liquid, after that i evaporated ethanol on temperature 90-100 C and final product is ~40 ml ethyl sulfate. At least i hope it is, i am sure its not ether cause it would evaporate quickly.

I think low yield i have is cause i was too careful with refluxing (was afraid i make ether) and maybe short reflux time..

For first time i am satisfied with the results and next time i will reflux it on little higher temperature for little longer (45 mins probably)

I am going to make 126g of ethyl sulfate (1 mole) only problem is i am not sure which is better for obtaining sodium salt of ethyl sulfate, sodium carbonate or sodium bicarbonate...

Metacelsus - 20-10-2014 at 07:05

Was the bisulfate anhydrous or the monohydrate?

That yield of ethylsulfuric acid isn't low; it's great compared to anything I've been able to attain. What was the yield of actual sodium ethyl sulfate?

Akira990 - 20-10-2014 at 07:47

I never made sodium ethyl sulfate... I intend to store all ethylsulfuric acid till i get 1 mole (126g) after that i will try to obtain salt form, sodium ethyl sulfate ( problem is i cant decide which sodium to use, carbonate or bicarbonate, any suggestion)

Metacelsus - 20-10-2014 at 09:06

Use carbonate. Bicarbonate will produce more carbon dioxide (and also water) on neutralization.

Ethylsulfuric acid can decompose in the presence of water, so don't store it for too long.

S.C. Wack - 20-10-2014 at 12:17

90 g. of anhydrous sodium sulfate is placed in a dry 1 L flask connected with a condenser and receiver arranged for vacuum distillation. The flask is heated by means of an oil-bath kept at a temperature of 155-165°. The apparatus is exhausted as nearly as possible by means of a filter pump [20-45 mm.], and a mixture of 50 g. of alcohol and 104.5 g. of concd. sulfuric acid is allowed to drop through a capillary tube upon the sodium sulfate at a rate of about 120-150 drops per minute. The distillation of this mixture requires about one and one-half hours for completion. The distillate, which consists of alcohol and diethyl sulfate in two layers, is separated by means of a funnel. The alcohol thus recovered may be used in subsequent operations. The diethyl sulfate is washed with a dilute solution of sodium carbonate and then several times with cold water, dried over anhydrous sodium sulfate and filtered. The product thus obtained is neutral to litmus and analysis proves it to be almost pure diethyl sulfate: yield, 32.6 g.

Other dehydrating agents such as sodium pyrosulfate or anhydrous magnesium sulfate were used but the yield was lower in each case. Increasing or decreasing the amount of sulfuric acid causes a lower yield. Absolute alcohol does not have any advantage over 95% alcohol nor does fuming sulfuric acid have any advantage over the ordinary concentrated acid.

JACS 46, 999 (1924)

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

4 mol. sulfuric acid was added, with ice bath cooling, to 8 mol. ethanol, over 30 min., keeping temp. under 30C.

Heated to 45C and maintained for 30 min., cooled to room temp., added to addition funnel.

500 ml. water and 291 g. powdered sodium carbonate were mixed, and the addition funnel contents were added with shaking while keeping temp. below 40C with bath. It's important that the product is neutral to slightly alkaline. Poured into beaker and allowed to crystallize at 0C. Filtered sodium sulfate which was then washed with 40 ml. icewater.

Filtrate fractionated until the distillate reached 100C, distillate is ethanol. Vacuum distilled residue until 530 ml. remained, d 1.36. Put in addition funnel.

26.5 g. potassium carbonate was dissolved in 137 ml. water. 320 g. sodium nitrite and 6 ml. castor oil was added. Added condenser and receiver, heated to 130C with stirring, adding 750 ml. of the above sodium ethylsulfate solution over 1 hour to maintain 125-130C pot temp. Nitroethane started to distill immediately, and noncondensable gas. Heavy stirring was necessary, sodium sulfate started to crystallize, then foam started to happen at 30 min. 100 ml. water was added over 10 minutes to drive over the last nitroethane.

The entire receiver contents (2 layers) were fractionated. A small amount distilled below 74C and was discarded. Much came over at 87C. Distillation was stopped with distillate at 100C. Two layers in receiver, lower layer 104 g. nitroethane, ethanol, water; containing 91.6 g nitroethane. Upper layer 96.1 g., water, ethanol, nitroethane; 4.4 g. nitroethane. Fractionation of lower layer gave pure anhydrous nitroethane.

===========================

Sodium methylsulfate made the same way from 8 mol. methanol and 4 mol. sulfuric acid, with the 30 min. of heating at 50C. 253 g. sodium carbonate was added to neutralize and make slightly alkaline. Fractionated to 100C as before, but not concentrated in vacuo or otherwise like before. 850-1000 ml. remained, d 1.3.

Next, same as before but 155 ml. water was mixed with the potassium carbonate, the heating was at 120C, and 150 ml. water was added over 15 min. to drive over the last nitromethane. Noncondensable gas evolution ended with the end of the sodium methylsulfate addition. Condensable gas gave 20 g. condensate in a dry ice trap, it was 85% methyl nitrite and 15% nitrous anhydride.

The fractionation of the 2 layers in the receiver gave a distillate to discard, starting between 65 and 79C. 85% of the nitromethane distilled as the azeotrope at 83.5C. Continued to 100C as before. Receiver lower layer nitromethane, methanol, water, HCN(!!!): 124 g, 118.4 g. nitromethane. Upper layer same, 68.3 g., 8 g. nitromethane. Fractionated lower layer, 1st fraction 64.5-83C 6 g., 2nd 83-101C (2 layers) 13 g., 3rd 101C, 103 g. pure nitromethane.

Desseigne and Giral, Cliff's notes


[Edited on 20-10-2014 by S.C. Wack]

CuReUS - 6-6-2015 at 07:55

the success of this reaction depends on the purity and ease of production of ethyl sulphate.Since the ethanol and sulphuric acid method isn't so good,why can't ethyl sulphate be directly made by passing ethene through conc sulphuric acid.Ethene is sold as ripening gas,so it shouldn't be difficult to get

byko3y - 6-6-2015 at 12:10

Because ethylene reacts reeally slugishly with sulfuric acid at normal conditions, being insoluble in the acid.
US3024263 declares 87% yield from bisulfate and ethanol, sulfamic acid also gives 80%, I'm pretty sure sodium sulfate giving more than 70% if done correctly. Anything below 70% should be considered useless or poorly optimized method.
And EtBr-NaNO2 method gives essentially the same yields: 90% for EtBr step, 50-60% for EtNO2 step, total 45-55%, compared to 40 via alkali ethyl sulfate.

CuReUS - 9-6-2015 at 03:17

Quote: Originally posted by byko3y  
Because ethylene reacts reeally slugishly with sulfuric acid at normal conditions, being insoluble in the acid.

have you done the reaction.Because I can't find any reference on the rate of the reaction
I found a patent where they say that alcohol is prepared by hydrolysing the sulphate ester of ethylene,but I couldn't get the second patent
http://www.google.com/patents/US1339947
Quote:
It is known that alcohol may be synthesized from ethylene by a process involving the successive steps of absorbing ethylene in concentrated sulfuric acid (98100%) to form ethyl hydrogen sulfate, and then hydroly'zing this ester with formation of alcohol and dilute sulfuric acid.

byko3y - 9-6-2015 at 09:08

http://www.google.com.ar/patents/US4296261
Quote:
(a) treating ethylene in an absorption zone in admixture with ethyl hydrogen sulfate at a temperature of from about 70° to about 80° C. and at a pressure of from about 250 to about 350 psig.;
(b) treating the resulting diethyl sulfate serially in a multiple-stage hydrolysis zone with a measured amount of water at a temperature of from about 50° to about 90° C., the water concentration in each of said stages being insufficient to hydrolyze all of the diethyl sulfate contained therein to ethyl hydrogen sulfate and ethanol, a substantial portion of said ethanol being stripped from each of said stages prior to further hydrolysis of said diethyl sulfate in ensuing stages; and,
(c) recycling the ethyl hydrogen sulfate to said absorption zone and treating said ethylene in admixture therewith in accordance with step (a).


[Edited on 9-6-2015 by byko3y]

CuReUS - 10-6-2015 at 02:44

I also found the patent that you linked.They make diethyl sulphate,not ethyl hydrogen sulphate.And the pressure isn't that high.It could be done easily in an autoclave filled with silica,alumina or glass beads.

byko3y - 10-6-2015 at 03:12

The kwesching is where are you gonna obtain the ethylene? Something like dis http://www.praxairdirect.com/Product2_10152_10051_10457_-1_1... ?
Because for me it seems much more easier and cheaper to obtain yeasts, sugar and a big vessel.

CuReUS - 10-6-2015 at 05:13

yes,that's exactly where I would get the ethene from
your idea for making ethanol might be cheap,but it is definitely not easy.you would have to use an air tight vessel(as the oxygen will oxidise the ethanol formed to acetic acid),it would take atleast a month and last but not the least,you would have to distill the whole mess,and remember you wouldn't get much alcohol since yeasts poison themselves to death if the concentration of alcohol in the slurry exceeds 13%

byko3y - 10-6-2015 at 05:38

This is why i was walking about a BIG vessel. This is pretty much the only requirement. There would always be an excess pressure inside the vessel, so it can be not perfectly air-tight. 40 L vessel is a cheap and common one in my region, it allows you to make something like 5 L of pure alcohol in just 2-3 days.
Yes, you will have to distill the mess, but the needed content is just ~15% of the whole volume, you can perform the distillation using something like 5-10 L flask with ground glass joint, distilling the whole product in a half of a day.

S.C. Wack - 19-3-2016 at 13:41

All things considered, is the sulfate removal step worth doing, over D&G's process?

BTW the missing part of my last post (the yield is worse, that first part should have been edited out too), FWIW to complete the condensed version of Desseigne and Giral's nitroethane:

214 g. NaNO2 (3 mol) was added to 12 g. K2CO3 in 92 ml water and 4 ml of oleyl alcohol antifoamer, and heating was maintained between 130-140C with strong stirring while 154 g (1 mol) diethyl sulfate was added over 15 minutes. The rest was as before, from sodium ethylsulfate. Yield 27% based on both ethyls. [40 g.]

sulfuric acid is the king - 19-10-2017 at 07:56

Please help about detection.
I have synthesized something like from the first page of this topic,but without water,powder on powder!.
Little flies,i think fruit flies were extremely atracted to that destillate...
Destillate was clear,with little flies in it,it had gasoline like smell...
It was hope for me until i added water,and then disappointment happened...
There was no two layers!
What have i synthesized,any idea??
And yeah in the boiling flask was too much NOx...

[Edited on 19-10-2017 by sulfuric acid is the king]

Melgar - 19-10-2017 at 19:05

Quote: Originally posted by sulfuric acid is the king  
Please help about detection.
I have synthesized something like from the first page of this topic,but without water,powder on powder!.
Little flies,i think fruit flies were extremely atracted to that destillate...
Destillate was clear,with little flies in it,it had gasoline like smell...
It was hope for me until i added water,and then disappointment happened...
There was no two layers!
What have i synthesized,any idea??
And yeah in the boiling flask was too much NOx...

[Edited on 19-10-2017 by sulfuric acid is the king]

Homemade ethanol that you distilled yourself, I take it? You probably need to use a better reflux condenser, or do a better job keeping air out, since my best guess is that there's a lot of acetaldehyde in your distillate.

sulfuric acid is the king - 20-10-2017 at 05:37

Thanks for the answer,you are probably right.
Reflux condenser and atmosphere without oxygen,why?
I didn't found that in the original procedure,so i've done it without.
I checked now,the content in the flask was acidic...

So how is Et formed,from decomposition of NaEtHSO4? Right?
Can NaEtHSO4 be decomposed to Et and H2SO4,and then H2SO4 react with NaNO2 giving off NOx fumes?
I don't know what happened exactly and why...

JJay - 20-10-2017 at 05:53

I think ethyl nitrite is said to be a side product of this reaction. Also, sodium ethyl sulfate can combine with water to form sodium bisulfate and ethanol in the presence of water at elevated temperatures. Sodium bisulfate could react with sodium nitrite and water to form nitrogen oxides.

I haven't personally tried it, so I'm afraid I can't be much help here.

sulfuric acid is the king - 20-10-2017 at 06:41

I think exactly that happened.
Maybe i need to try lower temperature...
Any suggestions?
The temperature was maximum from 1500 W hot plate.

sulfuric acid is the king - 9-2-2018 at 13:24

Does nitroethane make azeotrope with diethyl ether?

Boffis - 28-2-2018 at 12:37

I have a silly question!

Since nitromethane reacts with formaldehyde in a base catalyzed system to give 2-nitroethanol, could you react it with say iodomethane under similar conditions to get nitroethane?

clearly_not_atara - 1-3-2018 at 07:30

Wouldn't you get t-butyl nitryl?

Boffis - 1-3-2018 at 08:00

@clear_not_atara;? do you mean tert-nitrobutane? I don't know. If the reaction works once then I suppose in the presence of an excess of base you could get multiple substitution. (but not a nitryl ie cyano group).

However, I was thinking about the reaction between the sodium salt of nitromethane and methyl iodide say, to give methyl substituted nitromethane ie nitroethane an sodium iodide so the base is consumed.

Crowfjord - 1-3-2018 at 08:34

Quote: Originally posted by Boffis  
I have a silly question!

Since nitromethane reacts with formaldehyde in a base catalyzed system to give 2-nitroethanol, could you react it with say iodomethane under similar conditions to get nitroethane?


I have wondered this myself and did some research into the question several years ago, when I still had access to Scifinder. I couldn't find any examples in the literature of such a reaction at the time. I did find here on sciencemadness (link) that nitromethane reacts with benzyl chloride under basic conditions to give benzaldehyde, but I'm not sure if this is a special case of benzyl carbon reactivity or if it would also apply to other alkyl halides.

There are conditions in which 2-nitropropane can be made to alkylate at C rather than O with benzyl halides (see attached paper). This of course is pretty separate to the question of whether nitromethane could be made to form a C-C bond with an aliphatic haloalkane, but maybe could provide some hints as to whether it could be made to work. Maybe it could work with appropriate solvent selection. Someone should do some experiments!

Attachment: kornblum1963.pdf (358kB)
This file has been downloaded 320 times

[Edited on 1-3-2018 by Crowfjord]

Boffis - 2-3-2018 at 09:53

@Crowfjord. Thankyou very much for the reference and your comments. I think they pretty much rule out the formation of nitroalkane via alkyl halide -nitromethane condensation; at least under base catalyzed conditions. The formation oximes and aldehydes though is interesting and potentially useful. I wonder why Kornblum used the lithium salt? Is it more soluble in the solvent used perhaps?

I need to read this paper again and digest the information.

This raises my next question. What sort of reaction result in the formation of C-C bound rather than O-C bond with nitroalkane with a n H on the same carbon atom as the nitrogroup?


monolithic - 23-5-2018 at 10:23

Quote: Originally posted by Antoncho  
Originally posted by bwz at https://www.hyperlab.info/inv/index.php?act=ST&f=17&...

Quote:


200 g sulfaminic acid pulverized w/a coffee grinder (Note 1) and 300 mls anhydrous EtOH (which was grudged) was refluxed for 3 hrs in a 2 l flask (Note 2). The most part of HSO3NH2 dissolved and a pool of melted NH4EtSO4 is formed on the flask's bottom under the layer of alcohol. EtOH is then removed - first with an aid of slight vacuum, then - at 15 mmHg. The residue of melted NH4EtSO4 crystallized slowly, one has to catch the moment when it gets completely solid, but is still soft. After ir crytallizes fully, it is very hard to recover from the flask. Finally it was obtained 270 g of white crystalline agregates.

295-270=25 g -- EtOH not reacted with sulfamic acid = 52 g unreacted acid
52/270*100=19,3% -- sulfamic acid content in the final product
(270-52)/295*100=73,9% - the yield of ammonium ethyl sulfate.

The product was then neutralized with Na2CO3 and evaporated to sp. gravity of 1,34 g/cm3. It still had a weak smell of ammonia due to the present ammonium sulfamate. After filtering out the crystallized salts the volume of the solution constituted 275 mls.




So.... As you can see, the most interesting question now is whether it is possible to use regular 95% EtOH in this preparation and how successfully it can bee used. Anyone willing to find that out?


I'm having trouble understanding this procedure. Sulfamic acid is refluxed with ethanol and then the excess ethanol is driven off. This leaves molten NH4EtSO4. To this is added Na2CO3, presumably in a saturated aqueous solution? I don't understand what it means by evaporating to a specific gravity of 1.34g/ml, filtering out the crystallized salts, volume of the solution, etc. Can someone explain this a bit more? I take it the addition of K2CO3 is doing a double displacement reaction and forming NaEtSO4 and (NH4)2CO3, both of which are solids at room temperature? How is the NaEtSO4 being separated from this mixture?

carbon85 - 25-5-2018 at 00:11

May i ask why Nicodems proposed route involving sodium pyruvate and hydroxylamine was never perused further or even amount to a discussion as it seams to be quite an ingenious method in theory or the oxidation of the corresponding amine apart from published literature ?

Are we just set in our ways ?

Regards

[Edited on 25-5-2018 by carbon85]

monolithic - 25-5-2018 at 05:42

Quote: Originally posted by carbon85  
May i ask why Nicodems proposed route involving sodium pyruvate and hydroxylamine was never perused further or even amount to a discussion as it seams to be quite an ingenious method in theory or the oxidation of the corresponding amine apart from published literature ?

Are we just set in our ways ?

Regards

[Edited on 25-5-2018 by carbon85]

Do you have a link to this? I searched but I can't seem to find it.

carbon85 - 25-5-2018 at 06:16

Quote: Originally posted by monolithic  
Quote: Originally posted by carbon85  
May i ask why Nicodems proposed route involving sodium pyruvate and hydroxylamine was never perused further or even amount to a discussion as it seams to be quite an ingenious method in theory or the oxidation of the corresponding amine apart from published literature ?

Are we just set in our ways ?

Regards

[Edited on 25-5-2018 by carbon85]

Do you have a link to this? I searched but I can't seem to find it.


Here : http://www.sciencemadness.org/talk/viewthread.php?tid=909

clearly_not_atara - 23-5-2019 at 23:23

So I had a thought.

Instead of dissolving sodium nitrite in water with other stuff, consider heating the powder in a flask with an oven to 150 C, well below the decomposition temperature of sodium nitrite. Then add diethyl sulfate also at 150 C dropwise, using an optical thermometer or other means to ensure the reaction does not become too vigorous. The reaction chamber should probably be purged with nitrogen or at least carbon dioxide. The condensate will probably contain some ethyl nitrite, but there is no nitrite anion present and the ester should be easy to remove.

EDIT: btw, rxn of NH2OH with sodium pyruvate is an excellent way to make acetonitrile ;)

[Edited on 24-5-2019 by clearly_not_atara]

draculic acid69 - 26-5-2019 at 05:48

I think the secret to this rxn is buy a 4l of metho and a 3kilo bucket of sodium bisulfate and a 6litre non stick teflon coated pot at Kmart. Do the rxn in 500g batches until a full bucket is used up then work it up and turn it into nitroethane in 3-4 larger batches.with the yeilds everyone is getting this seems to be the way to 1/2 liter batches rather than making little batches for a shotglass full.nux vomicas yt channel has a good video on it from start to finish.just needs to be done on a larger scale.

[Edited on 27-5-2019 by draculic acid69]

gravityzero - 24-9-2020 at 09:26

Curious in making the ethyl sulfate from ethanol and sodium sulfate. Tried this not long ago, but my setup was all wrong.
I like Chuck Norris' approach on page two and that is what I followed.

500ml 3 neck RBF. Center neck has a mechanical stirrer and an addition funnel attached using a Claisen adapter.
one side has a thermometer, the other side has a reflux.

Put in 150g of pool sodium bisulfate. Into the addition funnel was placed 150g 95% ethanol.
The sodium sulfate melts at low temps, so it is warmed on mantle until it liquifies.
As soon as the ethanol drip is started, it reacts, very exothermic.

My problem last time was the ethanol was dripped from one of the side necks, which cause the salt formed to stick to side of flask.
This time, I will drop from center of flask in hopes to prevent the formed salts from sticking to side of flask.

My understanding is once the ethanol is added, I should gently reflux for 30 minutes.
Place the flask in the freezer to bring to 0C, then filter off ethyl sulfuric acid and any unreacted ethanol.

The ethanol will be removed via rotovap, leaving the ethyl hydrogen sulfate behind.
This sound about right?