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Author: Subject: Nitroethane from ethylsulfate, Desseigne variation.
byko3y
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[*] posted on 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.
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[*] posted on 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.
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byko3y
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[*] posted on 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]
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CuReUS
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[*] posted on 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.
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byko3y
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[*] posted on 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.
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[*] posted on 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%
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byko3y
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[*] posted on 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.
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[*] posted on 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.]




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sulfuric acid is the king
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[*] posted on 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]
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[*] posted on 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.




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[*] posted on 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...
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[*] posted on 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.




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[*] posted on 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.
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[*] posted on 9-2-2018 at 13:24


Does nitroethane make azeotrope with diethyl ether?
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[*] posted on 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?
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[*] posted on 1-3-2018 at 07:30


Wouldn't you get t-butyl nitryl?



[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 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.
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[*] posted on 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 41 times

[Edited on 1-3-2018 by Crowfjord]
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[*] posted on 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?

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[*] posted on 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?
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[*] posted on 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]
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monolithic
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[*] posted on 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.
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[*] posted on 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
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