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Author: Subject: Nitroalkane syntheses ?
PHILOU Zrealone
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[*] posted on 22-2-2017 at 15:34


Quote: Originally posted by sulfuric acid is the king  
If i try to do nitration of butane with NO2 in regular steel pipes can they sustain that for just one time?

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...




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[*] posted on 22-2-2017 at 15:36


Quote: Originally posted by sulfuric acid is the king  
What about ethyl iodide and sodium nitrite under high pressure?

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 .




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[*] posted on 22-2-2017 at 16:12


@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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[*] posted on 23-2-2017 at 14:01


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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[*] posted on 23-2-2017 at 15:41


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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[*] posted on 23-2-2017 at 15:55


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 :D
Name me some other metal nitrites better than sodium?
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byko3y
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[*] posted on 23-2-2017 at 20:22


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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[*] posted on 24-2-2017 at 05:18


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.

I expected more constructive answer from organic chemistry Ph.D. ,IQ160...
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clearly_not_atara
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[*] posted on 24-2-2017 at 13:20


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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[*] posted on 3-3-2017 at 17:52


How long can nitroalkanes be stored,what are degradation factors?
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[*] posted on 7-3-2017 at 16:05


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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[*] posted on 10-3-2017 at 09:00


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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[*] posted on 11-3-2017 at 00:48


It appears you've got the right idea:

http://www.tandfonline.com/doi/pdf/10.1080/00304948809356305
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[*] posted on 19-3-2017 at 22:20


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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[*] posted on 20-3-2017 at 10:12


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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[*] posted on 1-9-2018 at 04:30


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]




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[*] posted on 18-9-2018 at 09:24


I don't think nitroethane would be soluble in petroleum ether at all. True ethers, definitely.
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[*] posted on 18-9-2018 at 09:52


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.




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 20-9-2018 at 09:15


Quote: Originally posted by Waffles SS  
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]


@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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[*] posted on 20-9-2018 at 09:30


Quote: Originally posted by Boffis  
Quote: Originally posted by Waffles SS  
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]


@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?



Untitled.jpg - 72kB

[Edited on 20-9-2018 by Waffles SS]




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[*] posted on 20-9-2018 at 12:00


Quote: Originally posted by Waffles SS  

Triethyl Borate + HNO3 = EtNO2
Schiff, H.; Liebigs Ann. Suppl.-Bd.; vol. 5; (1867); p. 154 - 182 ; (from Gmelin)
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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[*] posted on 20-9-2018 at 22:30


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]




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[*] posted on 9-12-2018 at 08:57


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.


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)
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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

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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

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[Edited on 9-12-2018 by Mush]
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[*] posted on 16-2-2019 at 21:04


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.

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