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byko3y
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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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CuReUS
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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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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).
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[Edited on 9-6-2015 by byko3y]
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CuReUS
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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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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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CuReUS
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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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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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S.C. Wack
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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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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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Melgar
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| 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.
The first step in the process of learning something is admitting that you don't know it already.
I'm givin' the spam shields max power at full warp, but they just dinna have the power! We're gonna have to evacuate to new forum software!
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sulfuric acid is the king
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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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JJay
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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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sulfuric acid is the king
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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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sulfuric acid is the king
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Does nitroethane make azeotrope with diethyl ether?
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Boffis
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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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clearly_not_atara
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Wouldn't you get t-butyl nitryl?
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Boffis
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@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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Crowfjord
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| 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 499 times
[Edited on 1-3-2018 by Crowfjord]
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Boffis
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@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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monolithic
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| 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.
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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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carbon85
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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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| 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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carbon85
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| 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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clearly_not_atara
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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]
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draculic acid69
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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]
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