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PHILOU Zrealone
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Better do butane and dilluted HNO3 vapour at arround 350°C...you will get nitrobutanes, nitropropanes, nitroethane and nitromethan.
Butane NO2 mix may be explosive...
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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PHILOU Zrealone
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The high pressure is not needed...but you need a good solvent for both CH3-CH2-I and NaNO2 (DMF or DMSO)...also you will get more ethyl nitrite ester
than nitro ethane with NaNO2...better use dry AgNO2 .
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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sulfuric acid is the king
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@PHILOU Zrealone
Thanks for the answers.
Can you explain me how high pressure is not needed when ethyl iodide has lower boilng point than nitroethane,i thought to react it in closed
vessel,and then release vapor.
About butane...Yea it would be nice with acid way,but i need more vessels,acid needs to be heated etc etc...
[Edited on 23-2-2017 by sulfuric acid is the king]
[Edited on 23-2-2017 by sulfuric acid is the king]
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byko3y
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PEG is another solvent for both the EtI and NaNO2. Ratio of nitroethane:ethyl nitrite is somewhere at 3:2 or maybe even 2:1 for best known procedures.
It's a good idea to distill nitrite ester as fast as it is formed.
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sulfuric acid is the king
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You both think about "cold reaction"?Can it work that way?
[Edited on 24-2-2017 by sulfuric acid is the king]
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sulfuric acid is the king
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Can i use diethylether as a solvent?
What about ethyl chloride is it better than iodide?
I do not have silver nitrite,it's to expensive to disolve silver in nitric acid and then futher process to nitrite 
Name me some other metal nitrites better than sodium?
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byko3y
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You should really try to stick to performing experiments someone already extensively developed, because you have no idea what you talk about.
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sulfuric acid is the king
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Quote: Originally posted by byko3y  | | You should really try to stick to performing experiments someone already extensively developed, because you have no idea what you talk about.
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I expected more constructive answer from organic chemistry Ph.D. ,IQ160...
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clearly_not_atara
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It seems that overall the less polar the solvent is, the higher the ratio of nitro:nitrite. From what I've seen, PEG > DMF > DMSO > alkylene
carbonates > alcohols > water as far as nitro compound formation is concerned.
https://en.wikipedia.org/wiki/Lithium_nitrite#Crystallizatio...
According to Wikipedia, lithium nitrite is significantly more soluble in dry alcohol than potassium nitrite, which hints that it may also be more
soluble in other organic solvents than sodium nitrite. LiNO2 may be a cheaper alternative to AgNO2: not quite as soluble in organics, but better than
NaNO2 or KNO2, which is consistent with what we know about other lithium salts.
It's possible that lithium nitrite in absolute ethanol would be enough for a good yield of nitroalkane, but if not it might work in one of the other
solvents listed above.
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sulfuric acid is the king
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How long can nitroalkanes be stored,what are degradation factors?
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sulfuric acid is the king
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Hmm,can i do something with ethyl chloride?
I know boiling point is lower than room temperature,but some pressurized one pot method or some solvent,what YOU members of the forum think about this
idea,any suggestions?
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Melgar
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If less polar solvents produce more of the nitro compound, this would seem to be an ideal use case for phase-transfer catalysts. Sodium nitrite in the
aqueous phase, then ethyl bromide in DCM, with TBAB as the PTC?
I think that for this type of substitution reaction, you need an organobromide at minimum. If you have ethyl chloride, you can convert it to the
bromide in anhydrous conditions by bubbling HBr through it in the presence of an aluminum catalyst. AlBr3 converts alkyl chlorides to alkyl
bromides, producing AlCl3. And HBr reacts with AlCl3 to produce AlBr3.
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clearly_not_atara
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It appears you've got the right idea:
http://www.tandfonline.com/doi/pdf/10.1080/00304948809356305
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RosarioHeis
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Why nitroethane can not be fractional distilled directly from dmf/NaNO2 solution? And what about extracting nitroeth from dmf with petroleum ether?
The last is not soluble in it.
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byko3y
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Nitroethane boiling poing is much higher than boiling point of any ethyl halide (12°C, 38-39°C, 72-73°C for Cl, Br, and I).
DMF is soluble in pet. ether, but not miscible with it. Nitroethane is polar and acidic, thus alcohols, ethers are the best solvents
for this compound (miscible). I know that 1-nitropropane is miscible with sulfolane, and methanol is not miscible with hexane below 25°C.
This gives me some signs that nitroethane is much more soluble in DMF than in the pet. ether. To fix the problem, water should be added to the mixture
- which is the workup you all know.
[Edited on 20-3-2017 by byko3y]
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Waffles SS
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I found interesting methods for synthesis Nitroethane
Reaction of Ethyl Tosylate + NaNO2 = EtNO2
Rodionow - Bulletin de la Societe Chimique de France, 1926, vol. <4> 39, p. 318,
Bulletin de la Societe Chimique de France, 1929, vol. <4> 45, p. 119
and
Triethyl Borate + HNO3 = EtNO2
Schiff, H.; Liebigs Ann. Suppl.-Bd.; vol. 5; (1867); p. 154 - 182 ; (from Gmelin)
(thanks S.C .Wak for finding reference)
https://babel.hathitrust.org/cgi/pt?id=uva.x002457974;view=1...
It seems Borate ester is interesting and cheap method if it work !
[Edited on 1-9-2018 by Waffles SS]
Chemistry = Chem + is + Try
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LabRatNW
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I don't think nitroethane would be soluble in petroleum ether at all. True ethers, definitely.
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clearly_not_atara
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That method from ethyl tosylate might go well with Loptr's synthesis of tosylates:
https://www.sciencemadness.org/whisper/viewthread.php?tid=91...
Not clear if a nitrite scavenger (resorcinol) is needed. Someone will have to do the forensics to find that old-ass paper.
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Boffis
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@waffles, it that a typo error or did you really mean HNO3 ie nitric acid rather than nitrous acid. If you do mean nitric acid what is the reaction?
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Waffles SS
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| Quote: Originally posted by Boffis |
@waffles, it that a typo error or did you really mean HNO3 ie nitric acid rather than nitrous acid. If you do mean nitric acid what is the reaction?
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[Edited on 20-9-2018 by Waffles SS]
Chemistry = Chem + is + Try
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byko3y
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The equation appears to
be incorrect. At p. 168 author states "B(C2H5)3O3 + 3 NHO3 = BH3O3 + 3 N(C2H5)O3", thus the product is ethyl nitrate - same as the one made by
reacting nitric acid and ethanol directly.
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Waffles SS
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| Quote: Originally posted by byko3y | | The equation appears to be incorrect. At p. 168 author states "B(C2H5)3O3 + 3 NHO3 = BH3O3 + 3 N(C2H5)O3", thus the product is ethyl nitrate - same as
the one made by reacting nitric acid and ethanol directly. |
Interesting point.Thanks
I didnt see this equation so far. It seems we cant trust to all of the reaxys result
[Edited on 21-9-2018 by Waffles SS]
Chemistry = Chem + is + Try
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Mush
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| Quote: Originally posted by anomolous | The reason I was attracted to this route was its apparent simplicity. I may try vacuum distilling instead of extracting with a solvent. But I don't
understand why a solvent extraction wont work? Has anyone dealt with DMSO before? It seems to have strange characteristics. Is there something I'm
missing? Do you think vacuum distillation is the answer or is there some other method of extracting the nitroethane you'd recommend?
Another method using 2-bromoproprionic acid was mentioned on the Rhodium archive. Nitroethane Synthesis: A Compilation, method 7. It is the
destructive distillation of 2-bromoproprionic acid. It occurs in a solution of K2CO3 with NaNO2. Follows is the reference: V. Auger. Bull Soc. Chim.
France Post no 3,23,333 (1900). If you can find it please share. Though the yields are so-so (50%) I may give this method a try. But the patent method
still haunts me.
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V. Auger. Bull Soc. Chim. France Post no 3, 23, 333 (1900)
https://gallica.bnf.fr/ark:/12148/bpt6k5774483h/f396.image.r...
Attachment: V. Auger. - Bull Soc. Chim. France no3, vol 23, p.333-336 (1900).rar (1.5MB)
This file has been downloaded 556 times
Rây, P. C., & Neogi, P. (1906).
CLXXXIV.—The interaction of the alkylsulphates with the nitrites of the alkali metals and metals of the alkaline earths.
J. Chem. Soc., Trans., 89(0), 1900–1905.
doi:10.1039/ct9068901900
CCXXI.—Interaction of alkali alkyl sulphates and alkali nitrites: theories of the formation of aliphatic nitro–compounds
Panchānon Neogi
J. Chem. Soc., Trans., 1914,105, 2371-2376
doi.org/10.1039/CT9140502371
Attachment: J. Chem. Soc., Trans., 1906,89, 1900-1905.pdf (415kB)
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Attachment: J. Chem. Soc., Trans., 1914,105, 2371-2376.pdf (382kB)
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From ethyalmine with peroxymonosulfuric acid
Ueber die Oxydation des Aethylamins
Eug. Bamberger
doi.org/10.1002/cber.19020350480
Chemische Berichte; vol. 35; (1902); p. 4294
Sulfomonopersäure als Mittel zur Structurbestimmung bei Aminen
Chemische Berichte; vol. 36; (1903); p. 711
Eug. Bamberger
10.1002/cber.190303601145
Attachment: Bamberger_Chemische Berichte vol. 35 (1902) p. 4294.pdf (390kB)
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Attachment: Bamberger_Chemische Berichte vol. 36 (1903) p. 711.pdf (269kB)
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[Edited on 9-12-2018 by Mush]
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S.C. Wack
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THE RELATIONSHIP OF THE CONSTITUTION OF CERTAIN ALKYL HALIDES TO THE FORMATION OF NITROPARAFFINS AND ALKYL NITRITES
BY ROBERT B . REYNOLDS AND HOMER ADKINS
1929, with AgNO2 and no solvent.
The Reaction of Silver Nitrite with Primary Alkyl Halides
BY NATHAN KORNBLUM, BERNARD TAUB, AND HERBERT E. UNGNADE
1954, different instructions, in ether.
Attachment: jacs_51_279_1929.pdf (576kB)
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Attachment: jacs_76_3209_1954.pdf (389kB)
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