Sciencemadness Discussion Board

1,2,3 propyl trinitrite (glyceryl trinitrite)

pbmineral - 30-5-2009 at 00:04

Hello

I just wondered if it was possible to make 1,2,3 propyl trinitrite (glyceryl trinitrite) by the normal way.
I mean using NaNO2 in water and put in an additory funnel the alcool (glycerol) mixed with H2SO4.

What do you think of ?

I'm first afraid of losing glycerol making acrolein, will it occur ?
Then due to atom congestion (sterical congestion I don't know the english for that) I'm not sure the reaction will affect the 3 alcools.

Then we can wonder if we have to proceed like toluene polynitration tits get the mono derivative and nitrate it one more and so ...

Please what do you think of
Thank you for answering!

pbmineral

497 - 30-5-2009 at 11:52

Yes its possible, although fairly unstable, especially in the presence of water. No it won't make acrolein. Yes, it will be sequential, so you will end up with some incompletely nitrited(sp?) depending on the conditions. Using separate steps for a sequential nitrition(sp?) might be possible but seems unnecessary.

I have wondered if it would be explosive, since it has a reasonable oxygen balance. I have never seen any mention of it's explosive properties or any detonation danger, so I would assume it to be fairly insensitive if detonable at all.

Look here. http://www.google.com/patents?id=3TpNAAAAEBAJ
It seems they found it best to mix the nitrite, polyol, and water, add hydrochloric acid to the mixture.

I have made isopropyl nitrite on several occasions. I can tell you right now, don't use H2SO4 as your acid. It can work, but it causes lots of problems because it forms the marginally soluble sodium sulfate which in the presence of the polyol forms a sort of foamy gel that makes it very hard to stir or cool effectively. Without good stirring, much larger amounts of NOx are inevitably formed and yields are lower. So use HCl, it has none of these problems. Any other acid that's stronger than HNO2 and forms soluble salts should also work.

pbmineral - 30-5-2009 at 12:17

Hello

Thank you for your answer.
Indeed I fear for an explosion as I would like to distillate the product at the end !
What do you think of ?

Would it be suitable as poppers ? :D
lol

Please tell me

497 - 30-5-2009 at 12:53

I wouldn't try distilling it. Pretty sure it would decompose unless you had pretty good vacuum, and even then it might not be possible. It separates into its own layer in the reaction mixture. Just decant, wash quickly with NaHCO3 solution and dry well with something like MgSO4 or CaSO4. It should be pretty pure, only a small amount of partially nitrited contaminants should be present.

Hahahh... Glycerol trinitrite as a popper... that made me laugh. You could try it, probably wouldn't hurt you, but I can assure you it will be about as fun as inhaling glycerol trinitrate.. maybe you really enjoy headaches?

pbmineral - 30-5-2009 at 12:56

I thought that if one raised the n° of nitroso in the same molecule it would be stronger ?

Why don't you think of ?

497 - 30-5-2009 at 13:01

Yes, it might be stronger. But not better!

Actually, IIRC the active dose of amyl nitrite is found to be smaller than that of butyl or propyl. So having more -ONO per C may not make it stronger, I don't know.

smuv - 30-5-2009 at 22:08

alkyl nitrites are carcinogens, oxidize hemoglobin making your lips/skin under fingernails purple and can cause a dangerously low drop in your blood pressure. Why are you trying to make an ultra potent one? Your saving grace is this nitrite would not be very volatile which would make it harder to kill yourself with.

But yeah you are probably right, per mol it would probably be very potent as in vivo the NO formed is what induces the bulk of the effects (if i understand these drugs correctly...).

497 - 31-5-2009 at 04:51

Quote:
alkyl nitrites are carcinogens


Never heard that. Any refs for it? Seems doubtful considering they still prescribe amyl nitrite... Maybe the polynitrites are worse because they're less stable/stronger nitriting agents?

smuv - 31-5-2009 at 07:46

Quote:
Seems doubtful considering they still prescribe amyl nitrite.


Don't kid yourself, Tylenol is a carcinogen.
Quote:

GENETIC TOXICOLOGY

Isobutyl nitrite was found to be mutagenic in vitro and in vivo. It induced base-pair substitution mutations in Salmonella typhimurim strains TA100 and TA1535 and sister chromatid exchanges and chromosomal aberrations in cultured Chinese hamster ovary cells. Positive responses in the S. typhimurium tests required S9 activation, but isobutyl nitrite induced chromosomal effects in cultured Chinese hamster ovary cells with and without S9. In vivo, no induction of sex-linked recessive lethal mutations was noted in the germ cells of male Drosophila melanogaster exposed to isobutyl nitrite via feeding or injection. However, significant increases in micronucleated normochromatic erythrocytes were observed in the peripheral blood of male and female mice treated with isobutyl nitrite for 90 days by inhalation.
CONCLUSIONS

Under the conditions of these 2-year inhalation studies, there was clear evidence of carcinogenic activity of isobutyl nitrite in male and female F344/N rats based on the increased incidences of alveolar/bronchiolar adenoma and alveolar/bronchiolar adenoma or carcinoma (combined). There was some evidence of carcinogenic activity of isobutyl nitrite in male and female B6C3F1 mice based on the increased incidences of alveolar/bronchiolar adenoma and alveolar/bronchiolar adenoma or carcinoma (combined) in males and females. The increased incidence of thyroid gland follicular cell adenoma in male mice may have been related to isobutyl nitrite exposure.


from: http://ntp.niehs.nih.gov/?objectid=070A37EF-AD43-E81D-A97101...



Nicodem - 2-6-2009 at 03:45

An old reference for the synthesis and properties of glycerol trinitrite is:

XLVII.—The action of nitrous anhydride on glycerol
Orme Masson
J. Chem. Soc., Trans., 43 (1883) 348 - 351. DOI: 10.1039/CT8834300348

497 - 2-6-2009 at 21:16

Thanks for the reference. That's by far the most detailed information I've seen yet. Polverone graciously supplied it, here is a link.

There seems to be many routes to alkyl nitrites. Usually they either use a nitrite salt with an acid, or bubble in N2O3. Less often (and more interestingly) I've seen where they use N2O4 instead. This is interesting because it seems much simpler/cheaper to produce N2O4 than N2O3. By using N2O4 you produce HNO3 as a byproduct, which can lead to some formation of alkyl nitrates. Depending on your use for the nitrites, nitrate contamination may or may not be a problem.. Conveniently, there is no need to exclude water, and actually larger water content may help reduce nitrate formation by diluting the HNO3. Here is a good example.

pbmineral - 3-6-2009 at 00:45

Thank you very much for those answers.
I guess one must prepare gylceryl trinitrite with no water. What do you suggest to produce N2O4 or N2O3 ?
Do I only have to bubble it into alcool ?
Will it work with all kind of alcools ?


Thank you


Peter

497 - 3-6-2009 at 01:51

For making N2O3 which seems like a better choice for a small scale synth where bulk cost is not an issue, I would heat some NaNO2 and concentrated H2SO4 together to produce N2O3. If you don't want to screw with conc. H2SO4, you could probably heat NaNO2 and NaHSO4 together and get similar results.

Bubble it into the polyol in a cooling bath. The reaction is exothermic and if allowed to get hot will decompose the GTN.

As far as I know the same process will work on most alcohols.

[Edited on 3-6-2009 by 497]

woelen - 4-6-2009 at 23:14

At room temperature, "N2O3" is nothing else than a mix of NO and NO2. You simply can make this mix by adding copper metal to moderately concentrated nitric acid (40% or so). The brown gas mix contains a lot of NO and NO2 and this mix then has to be bubbled into the acidified solution of the alcohol in water.

I myself made nitrites of varying alcohols, simply by pouring a solution of NaNO2 in water into a solution of the alcohol in 10% HCl. When this is done in the cold, then the nitrite separates (as gas for methyl nitrite, as droplets of liquid for isopropyl and butyl). I, however, found that with polyols (I tried CH2OHCH2OH), the separation is not nearly as good. Probably one of the -OH's is converted to -O-N=O while the other is not. The resulting mixed alcohol/nitrite still is soluble in water quite well. I found that adding much more nitrite just leads to formation of a lot of gas (NO?, CO2?).