Sciencemadness Discussion Board - Glucose Nitroureide Tetranitrate

Glucose Nitroureide Tetranitrate

Rosco Bodine - 25-6-2011 at 00:27

Here is an obscure energetic material for which I can find no additional information. It is a very interesting energetic material because of the inexpensive precursors and relatively simple synthesis along with the additional interesting fact that a lead salt derived from the compound can act as an initiator for the material which reportedly is sufficiently energetic and sufficiently stable for use in a compound detonator. It would also seem likely that this nitrated aldose derivative would likely form binary or tertiary eutectics, gells or plastiques with nitrated sugars or nitrated polyols.

US2969354 Glucose Nitroureide Tetranitrate

US2612497 Glucose Ureide from Glucose and Urea

Attachment: US2969354_ALDOHEXOSE_NITROUREIDE_TETRANITRATE.pdf (142kB)
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Attachment: US2612497_PROCESS_FOR_MANUFACTURE_OF_HEXOSE.pdf (135kB)
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[Edited on 25-6-2011 by Rosco Bodine]

gnitseretni - 25-6-2011 at 03:48

Eh, kinda like the next ETN, only better, since you can make both a primary and secondary HE from it. I love it

Great find Rosco :cool:

Rosco Bodine - 25-6-2011 at 08:53

Yes indeed this is very interesting, and evidently GNT is obscure, as nothing comes up about it in searches. By virtue of it being acidic there are numerous salts or combined salts which could have interesting properties. Lately guanyl azide is one of the energetic salt formers which has been contemplated to form sensitive primary explosive salts, along with less sensitive secondary explosives from the isomerized form of guanyl azide that is 5-aminotetrazole. Candidate
explosive acidic energetic compounds such as this Glucose Nitroureide Tetranitrate
might possibly form useful energetic salts with guanyl azide and 5-aminotetrazole,
with two of each being required for neutralization of the GNT. Perhaps would also be possible combined or bridged salts using one of each of the guanyl azide
and 5-aminotetrazole with GNT. Azobisformamidine is dibasic and might also form an interesting salt with GNT. Such possibilities would suggest novel experiments perhaps leading to several novel new explosive compounds.
Energetic GNT esters could also be possible. An interesting
blast from the past is this patent US2969354 from fifty years ago and it is obscure enough to definitely qualify as experimental. It looks like I sort of started something with posting about ETN here a few years ago, which is another obscure and experimental compound. There aren't really any "experts" on such little known and EXPERIMENTAL energetic materials, so danger is always present because of the unknowns. Please be safety conscious and careful and thoughtful when any experiments are done particularly with obscure and experimental energetic materials.

[Edited on 26-6-2011 by Rosco Bodine]

freedompyro - 25-6-2011 at 13:16

Very interesting... Well look at it this way... If you get caught pissing in sugar people are just going to think your crazy!!! LoL! Jk...

Looks like I found a use for my confectioners sugar leftover from rocketry. Not going to mess with the mess with the metal salts... You guys have fun. The teranitrate looks promising though... Might have enough brisance to be useful.

Converted the patent into a easy to read synthesis... Please confirm these numbers are correct.
Hexose Ureides
1020g Sugar
340g Urea
30g H2SO4 (98%) + 30g H2O

1. Mix 102g Sugar + 85g H2O at 60C
2. Add 340g Urea.
3. Solution stabalized at 60C.
4. Subsequently 918g Sugar is then added in 102g portions.
5. The H2SO4 Solution is slowly added over an hour maintaining 60C.

The mixture is then reacted at 60C for eight hours.

Edit: Fixed synthesis

[Edited on 26-6-2011 by freedompyro]

freedompyro - 25-6-2011 at 17:26

Either this reaction needs (16.5mL)30g H2SO4 or it needs (148.5mL) 270g... Can't figure out this guys wording!

[Edited on 26-6-2011 by freedompyro]

franklyn - 25-6-2011 at 18:06

Condensation product with formaldehyde should be a reasonably dense polymer resin.

.

gnitseretni - 25-6-2011 at 18:07

It needs 16.5ml of 98% H2SO4.

BTW, how did you get at 85g water in step 1? They used 300ml water with the glucose and 550ml water when they used cane sugar. So divided by ten you'd need 30ml water if using glucose and 55ml water if using cane sugar. So how did you came up with 85ml?

freedompyro - 25-6-2011 at 23:32

Quote: Originally posted by gnitseretni

It needs 16.5ml of 98% H2SO4.

BTW, how did you get at 85g water in step 1? They used 300ml water with the glucose and 550ml water when they used cane sugar. So divided by ten you'd need 30ml water if using glucose and 55ml water if using cane sugar. So how did you came up with 85ml?

Sorry man... Read the patent again. Your wrong. I have it printed out... Here is what it says exactly.

", while the quantity of water was increased by 550 grams in order to bring about the hydrolysis."

"increased by" are the key words.

It doesn't say "increased to"

Now we just need someone to actually make the stuff and verify the yield... The last thing I am confused about is how to deacidify it... If it's water soluable thats going to be a pain in the neck. If you use sodium bicarbonate won't the sodium stay in the water through the evaporation? Meh...

Oh wait, I have barium carbonate on me... Doh!

[Edited on 26-6-2011 by freedompyro]

gnitseretni - 26-6-2011 at 03:59

@freedompyro: Yes, you're right. My bad!

I found a paper that gives a different way to make glucose ureide. I don't care if that method is better or not because the process takes much longer than the one in the patent Rosco provided. However, in it are mentioned some solubilities of glucose ureide urea, not glucose ureide, but they said the solubilities "closely parallel those of glucose ureide".

Code:

http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1251697/pdf/biochemj01152-0221.pdf

Readily soluble in water.
Very sparingly soluble in ethyl, methyl alcohol.
Practically insoluble in acetone, and quite insoluble in ether, chloroform and non-hydroxy solvents.

diglucose ureide patent US2967859

Rosco Bodine - 26-6-2011 at 09:33

Quote: Originally posted by franklyn

Condensation product with formaldehyde should be a reasonably dense polymer resin.

Please elucidate, elaborate. I have wondered about this myself. The glucose ureide could make a cheap and useful binder and fuel for pyrotechnics. Also a 10% excess of the theoretical requirement of urea is used in the described process for producing the glucose ureide, so the residual liquor from the reaction would contain the unreacted urea.
There are patents noting the usefulness of urea-formaldehyde resin as a very good sensitizer and fuel for ammonium nitrate. And urea is a known sensitizer fuel itself
as well as good for lowering the melting point of AN. It would seem likely then that the entire reaction mixture from
the production of the glucose ureide could be useful as a
fuel sensitizer for AN as well as having potential for further
reaction involving polymerization via reaction with an added
formaldehyde component. A melt cast and polymer bindered
AN based composition having useful properties could be the
ultimate result.

Attached is US2967859 for Diglucose Ureide which may also lead to an interesting energetic material upon nitration.

Attached also is the article linked above by gnitseretni which describes an adduct of glucose ureide with urea. In the first patent a 10% excess of the theoretical requirement of urea is used beyond what is needed to form glucose ureide, so the excess urea must react further to form the adduct of urea with the glucose ureide already formed ....and the adduct probably remains in solution in the mother liquor from which the main product the glucose ureide crystallizes.

Attachment: US2967859_PROCESS_FOR_DIGLUCOSE_UREIDE.pdf (166kB)
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Attachment: Glucose Ureide Urea adduct biochemj01152-0221.pdf (490kB)
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With regards to monoglucose ureide here is additional information

Name: Glucosylurea
Name english (2nd lang): Glucosylurea
Molecular Formula: C7H14N2O6

IUPAC: [(3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]urea
CAS: 5962-14-1

Molecular Weight: 222.196 g/mol
Exact Mass: 222.085 g/mol
Monoisotopic Mass: 222.085 g/mol

SYNONYMS

Glucosylurea
Glucose ureide
Glucosyl urea
Urea, glucosyl-
Urea, D-glucopyranosyl-
AIDS022743
AIDS-022743
CID151391
5962-14-1

Elemental composition: C7H14N2O6
Element Symbol Atomic Mass # of Atoms Mass %
Carbon C 12.01078 7 37.84%
Hydrogen H 1.007947 14 6.35%
Nitrogen N 14.00672 2 12.61%
Oxygen O 15.99943 6 43.20%

[Edited on 26-6-2011 by Rosco Bodine]

Rosco Bodine - 26-6-2011 at 12:37

I don't really need to plan it because I already have everything on hand.
I would like to do the synthesis when time and opportunity permits.
But that may not happen for awhile, so I am basically sharing what I found
at this point for anybody else who may get to it before I do.

gnitseretni - 26-6-2011 at 12:54

Yeah, I'm a bit short on time as well. Making the GNT is no problem, it's the ureide that's the problem due to the long reaction time. But the precursors are cheap, so when you do find time to perform the synth, it makes sense to make enough so you don't have to do it again anytime soon.

freedompyro - 26-6-2011 at 13:28

Quote: Originally posted by gnitseretni

Readily soluble in water.
Very sparingly soluble in ethyl, methyl alcohol.
Practically insoluble in acetone, and quite insoluble in ether, chloroform and non-hydroxy solvents.

I don't really think we need to worry about purifying it. Just deacidification.

We can purify it properly after it's nitrated.

Probably a LOT easier...

Rosco Bodine - 26-6-2011 at 16:55

Quote: Originally posted by holmes1880

Matt, you should stop moving my posts. I have a legitimate concern that Bodine is refusing to synth shit he digs up, but tries to sell others on making it.

@holmes1880 I am not selling anything. I am sharing some interesting information I found while looking for something else. Your concern here may seem legitimate to you, but like your concern about some other things your concern lacks validity. I am not "refusing" to synthesize anything. I said I would like to experiment with this when I have time. If you don't accept that or don't like that, I really don't care. If you can't contribute useful information to a thread then you should refrain from posting anything at all until you have something useful to contribute. Avoid being a compulsive poster. Nobody likes it, and it will likely get you banned.

Polverone - 26-6-2011 at 17:30

Holmes, I wish everyone could and would try out every interesting idea that they come across. But I know that's not practical. Nobody here is my employee and I can't demand that they do work. I would rather read about an interesting untried idea than require only completed research be posted here. As an example, people had started posting about the patented production of potassium metal from KOH and Mg in solution years before Pok got it to work. There was a lot of talk and not a lot of action, but without the talk here and on related forums I don't know if Pok would have come across the idea when he did.

The_Davster - 26-6-2011 at 20:25

Or calcium cyanamide from cyanurate. Rosco's idea but I was the first to try it, and it worked.

freedompyro - 26-6-2011 at 23:37

What we need now is for someone to get a RE/Brisance estimation done by cross comparing the performance of GNT with well researched HE's. It will probably be a couple weeks until I can do full testing on GNT. Probably will just cross compare it with Nitrourea. If it outperforms... Continued testing.

My gut hunch is that Glucose Nitroureide Tetranitrate will give some respectable performance with a greater than 1.0 RE and detonation speed greater than 6500m/s. NitroUrea detonates at greater than 5400m's when compressed to around 1.1 g/cm3 with a RE of 0.94 according to my documents.

I am going to be very disappointed if this doesn't have substantially higher performance than NitroUrea. First to do testing please tell us your results.

Rosco Bodine - 27-6-2011 at 09:14

Glucose Pentanitrate has nitrogen content of 17.29%
PETN has nitrogen content of 17.71%
Glucose Nitroureide Tetranitrate has nitrogen content of 21.9%
Nitrourea NO2-NH-CO-NH2 , CH3N3O3 has nitrogen content about 40%``

Stability for the Glucose Nitroureide Tetranitrate is reportedly okay at normal storage temperatures. I am guessing, but I would expect density around 1.7
and an RE around 120%.

franklyn - 29-6-2011 at 11:36

@ Rosco Bodine
" Please elucidate, elaborate. I have wondered about this myself."

In regard to polymer formation I have no insight beyond the observation that
as stated in US 2512497
" In general the process according to my invention aims at the preparation
of such derivatives of hexoses and the nitrogen compounds referred to
as do not polycondense in vitro to insoluble macromolecules in the presence
of formaldehyde and an acid catalyst, as for instance urea itself would do
within a few moments with formaldehyde;"

However as stated in US 2969354
" The esters so obtained are acidic in nature and readily form metallic salts."

Whether the non reactive nature to polycondensation of the ureide precursor
carries onto the tetranitro product is unclear to me. The material being acidic
however does imply it must react with aldehydes generally, though not perhaps
with the amine functional group. Urea formaldehyde comparatively is comprised
of a mix of different products dependent on reaction conditions.

Attachment: Urea Formaldehyde.pdf (142kB)
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___________________________________________________

I have investigated comparative products obtained from cyanuric acid

Cyanuric acid exists almost exclusively in the tri-keto form in acid solution.
Isocyanuric or tri-keto structure exists in acidic solutions, below pH 6.
The di-keto structure predominates in the range from pH 7 to 10.5,
and the mono-keto structure above pH 11. In very strongly basic solution,
it is probably almost completely enolized (OH).
Cyanuric acid is only slightly soluble in water, 0.125%, or about
1 part in 800 parts of water at room temperature and 4% in boiling
water. It is even less soluble in alcohol.

In reactions of 1 mol of isocyanuric acid with 3 mol of formaldehyde one obtains
1,3,5-tris(hydroxymethyl) isocyanurate (THMIC)
also known as 1,3,5-tris(hydroxymethyl)-s-triazine-2,4,6-trione
and Tris(hydroxymethyl) isocyanurate or Trimethylol isocyanurate
1,3,5-Trimethylol-1,3,5-Triazine-2,4,6-Trione

See this excerpt => Attachment: Trimethylol Isocyanurate.pdf (141kB)
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from Chemistry and Technology of Polyols for Polyurethane http://ifile.it/kthzvaw
and British patent => Attachment: Trimethylol Cyanurate GB420525.pdf (542kB)
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From Kirk Othmer
Cyanuric acid readily dissolves in aqueous formaldehyde forming tris(hydroxymethyl)isocyanurate (THMIC) CAS 1047-40-6
which can be isolated by evaporation. [11] The Chemistry of Heterocyclic compounds vol 13 , 17-146
here => http://ifile.it/r3l7n8b

on Pg 48
Resinous condensation products are prepared by heating cyanuric acid
with formaldehyde With [148] or without [149] a diluent ; a clear resin
forms. Acid condensation agents such as hydrogen chloride may be
used to promote the reaction.

My note : this should be nearly quantitative yield, and the trinitrate readily made from it.
My initial interest waned as the projection of performance is disappointing.
The Trazine Trione skeleton has a high heat of formation which evidently degrades
the heat of explosion of what is essentially three attached Methyl Nitrates.

___________________________________________________

A variation on this theme requires glyoxal which is relatively expensive although
required starting materials are available over the counter. The tetranitrate of
compound [ 20 ] is oxygen balanced and should compare favorably with PETN.

____________________________________________________

Finally the condensation product with hydrazine is a base which can form
nitrate or perchlorate salts.

2,4,6-Trihydrazone-1,3,5(1H,3H,5H)-Triazine
1,3,5-Triazine, 2,4,6-trihydrazinyl
2,4,6-Trihydrazino-1,3,5-triazine
Trihydrazino-s-triazine
Cyanuric trihydrazide CAS 10105-42-7

http://webbook.nist.gov/cgi/cbook.cgi?ID=C10105427&Units...
http://cdb.ics.uci.edu/cgibin/ChemicalDetailWeb.psp?chemical...
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=6627...

.

Rosco Bodine - 30-6-2011 at 00:21

The first variation which I thought might be possible is a peroxide at the keto oxygen of the (tetranitro ester substituted) nitrourea.

Polydextrose nitroureide polynitrate polymer possible??

Rosco Bodine - 10-7-2011 at 11:04

@franklyn
Generally on the topic of polymerization, not with regards to the GNT, but with regards to the dextrose itself which is a precursor reacted with urea to form the intermediate for nitration, the question is raised whether or not urea would also react with polydextrose to form a polydextrose ureide
which could then be nitrated to a polydextrose nitroureide polynitrate ? It is unknown whether or not the polymerized dextrose would react with urea to form a ureide as does the monomeric dextrose. If it does react to form a nitratable intermediate then the resulting nitroureide would contain less of the nitrourea moiety and would be expected to be more stable yet as well as being more mildly acidic.

There is nothing I have found in the literature about this hypothetical compound derived from polydextrose and urea.

Polydextrose has been identified as a useful material for nitration and the nitrated product has good energy and stability. See US2495868 attached.

The polydextrose precursor is easily made by a number of methods involving heating the dextrose with a dry catalyst such as boric acid which appears to have a similar dehydrating and polymerizing effect upon dextrose as
is involved in the formation of dextrins from starch.
See US2375564 attached and US2400423 attached and
US2436967 attached

Attachment: US2495868_Nitrated Dextrose Polymer.pdf (154kB)
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Attachment: US2375564_Dextrose Polymerization Boric Acid Catalyst.pdf (819kB)
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Attachment: US2400423_POLYMERIZATION_OF_MALTOSE.pdf (487kB)
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Attachment: US2436967_POLYMERIZATION_OF_SUGARS.pdf (413kB)
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franklyn - 15-7-2011 at 05:05

A neat fibre such as nitocellulose would be desirable , a pasty product like caramel
would not be , hampering it's solubility and processing with acid. The field as you
observed has not been investigated and appears is quite extensive. Linear or ring
structured sugars provide varing physical attributes and the eventual oxygen balance
will determine what performance can be expected.

Carbamide derivatives of Sugars - Abstract
http://books.google.com/books?id=yfI4AAAAMAAJ&lpg=PA258&...

Carbohydrate Based Condensation Resin - Patent
www.taeus.com/patent_attorney_tracker/profile.php?sub=downlo...

Glycosyl Ureides , Irving Goodman , pages 215 - 236
Advances in Carbohydrate Chemistry & Biochemistry Vol 13
http://books.google.com/books?id=NDnNCOG6RWcC&lpg=PA215&...

Nitro Sugars , H. H. Baer , pages, 67 - 138
Advances in Carbohydrate Chemistry & Biochemistry Vol 24
http://ifile.it/i2oyqw8

http://en.wikipedia.org/wiki/Caramel
http://www.museumstuff.com/learn/topics/caramel::sub::Chemis...

Mechanism for the formation of sugars from formaldehyde
http://ia700503.us.archive.org/15/items/nasa_techdoc_1968001...

The Technology of Sugar
http://ia600407.us.archive.org/33/items/cu31924003619909/cu3...

P.S.
I had cited this in another post
Low Melting Sugar – Urea - Salt Mixtures as Solvents for Organic Reactions
www.rsc.org/suppdata/CC/b4/b414515a/b414515a.pdf

Some are liquid at less than 70 ºC , indicating condensation to a ureide
is not clearcut and higher reaction temperature is needed.

.

[Edited on 15-7-2011 by franklyn]

Rosco Bodine - 17-7-2011 at 21:54

I believe these dextrose polymers are similar to an oligosaccharide intermediate between sugar and dextrin, an indigestible soluble fiber type of material, but shorter chained, as is dextrin related to microcrystalline cellulose, but the soluble "fiber" characterization is something of a misnomer because the character of these lower polymers is more distinctly crystalline or granular than fibrous. Likewise the nitrated forms should or would be expected at least some them to inherit the gritty consistency of the precursor material. Compare to fructo-oligosaccharide and inulin.

[Edited on 18-7-2011 by Rosco Bodine]

Rosco Bodine - 8-9-2011 at 10:10

Quote: Originally posted by Rosco Bodine

Yes indeed this is very interesting, and evidently GNT is obscure, as nothing comes up about it in searches. By virtue of it being acidic there are numerous salts or combined salts which could have interesting properties. Lately guanyl azide is one of the energetic salt formers which has been contemplated to form sensitive primary explosive salts, along with less sensitive secondary explosives from the isomerized form of guanyl azide that is 5-aminotetrazole. Candidate
explosive acidic energetic compounds such as this Glucose Nitroureide Tetranitrate
might possibly form useful energetic salts with guanyl azide and 5-aminotetrazole,
with two of each being required for neutralization of the GNT. Perhaps would also be possible combined or bridged salts using one of each of the guanyl azide
and 5-aminotetrazole with GNT. Azobisformamidine is dibasic and might also form an interesting salt with GNT. Such possibilities would suggest novel experiments perhaps leading to several novel new explosive compounds.
Energetic GNT esters could also be possible. An interesting
blast from the past is this patent US2969354 from fifty years ago and it is obscure enough to definitely qualify as experimental. It looks like I sort of started something with posting about ETN here a few years ago, which is another obscure and experimental compound. There aren't really any "experts" on such little known and EXPERIMENTAL energetic materials, so danger is always present because of the unknowns. Please be safety conscious and careful and thoughtful when any experiments are done particularly with obscure and experimental energetic materials.

[Edited on 26-6-2011 by Rosco Bodine]

An error has been discovered in my post above that the
Glucose Nitroureide Tetranitrate has a dibasic character for neutralization which I should correct now realizing from checking the molecular weight and nitrogen analysis for the sodium salt reported indicates the Glucose Nitroureide Tetranitrate is neutralized by 1 sodium rather than two.

The molecular weight for
Glucose Nitroureide Tetranitrate is 447.15 corresponding with the patents reported theoretical Nitrogen content of 21.9%

A monosodium salt of Glucose Nitroureide Tetranitrate
would have a molecular weight of 469.14 and a Nitrogen content of 20.88% which is more in agreement with the patents reported theoretical Nitrogen content of 20.8%
than would be the theoretical Nitrogen content of a disodium salt which would be 19.95% based upon a molecular weight
of a disodium salt of 491.15

Therefore a bit of computational analysis shows that the
Glucose Nitroureide Tetranitrate is a monobasic acid.

Further computational analysis shows that the nitration accomplished by using the 7 parts of 50/50 nitration acids
as was used for preparation of the Glucose Nitroureide Tetranitrate precursor for the lead salt increased the yield for the nitration from the 60% yield gotten by 10 parts used in the first example, to a yield of 76.75% of Glucose Nitroureide Tetranitrate, based upon the reported yield of the lead salt of 19 grams, the molecular weight for the lead salt calculated to be 1099.5 by one mole Pb and 2 moles Glucose Nitroureide Tetranitrate (less two hydrogens)

The nitrogen content for the lead salt should be 17.8%

[Edited on 8-9-2011 by Rosco Bodine]

quicksilver - 8-9-2011 at 11:32

It's a damn interesting patent and certainly (superficially) commercially viable. I checked a bit and except for some material Franklyn already found I couldn't find much. The ISEE's text had nothing, etc. I wonder why this was not commercially popular? Perhaps there are shelf life limitations..... It seems odd that such a thing that demands so little did not have a commercial following. It appears Atlas Powder Company bought or subsidized the patent in '61 yet so little is known about it.

Phenolic Sugar Alcohol nitration candidate

Rosco Bodine - 8-9-2011 at 12:53

Yeah it is very interesting. The polydextrose is also interesting. Fructosan Trinitrate gotten from nitration of fructose is also reportedly stable. Several of these sugar derived energetics would seem to be of interest but there is very little information on them to be found.

Here's the latest thing I have been looking at along the same general lines Phenolic Sugar Alcohols as candidates for nitration, especially interesting is the reported condensation product of glucose and aspirin, and not specificially but generally mentioned other possible condensations of glucose with salicylic acid, and methyl salicylate. What might be gotten from nitrations of these condensation products is unknown and could be useful. What the disclaimer attached to the patent is about I am not sure,
whether the disclaimer means the claimed compound is misidentified or if it was discovered a prior art already claimed these compounds.

Attached also is the British patent by the same inventor which has some added information GB518586

It would be interesting to learn what is the reaction product of glucose and resorcinol and what may result upon nitration.

Attachment: US2252725_PHENOLIC_SUGAR_ALCOHOLS.pdf (334kB)
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Attachment: Fructose Trinitrate from Nitrocellulose_industry.pdf (183kB)
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Attachment: GB518586_Phenolic Sugar Alcohols.pdf (532kB)
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[Edited on 9-9-2011 by Rosco Bodine]

vaslop - 1-12-2011 at 10:16

Im surprised that this compound hasn't taken off, has anyone tried making any glucose ureide?

I tried the synthesis as follows

10.2g of glucose hydrate dissolved in 3g of water at 60c.
34g of urea is added and stirred in.
When the temperature is 60c again, 91.8g of glucose hydrate is added and also stirred in.
Afterwards, once the mass is mostly melted, a mixture of 3g of water and 3g (~1.6ml) of sulphuric acid are added slowly.
The mixture reacts at 60c for 8 hours.

Here, no solid glucose ureide was noticed, however the black viscous mass was obtained, but I continued with the synthesis as is written in the patent.

The mix was dissolved in very little water and neutralised with barium carbonate.
This was then filtered and evaporated, however no precipitate was obtained.

I have repeated this procedure but allowing a reaction time of 16hours, but with the same result.

Has anyone managed to make any glucose ureide yet?

Rosco Bodine - 4-12-2011 at 12:20

There have been no experiments done by me on this yet but here is some food for thought in added references.

The monoglucosyl ureides are vulnerable to hydrolysis so precipitation using alcohol may be helpful. Isolation of the hydrolysis sensitive monoglucosyl ureide in pure form may be most practical by first forming the hydrolytically stable glucosyl ureide - urea adduct which may be isolated by crystallization from water, and then thermally decompsed by long refluxing in alcohol to yield the desired monoglucosyl ureide. This method for isolation was described in an article attached earlier in the thread which reviewed the original work of Schoorl. The formation of the ureides is favored by the presence of a dehydrating material or vacuum conditions and only moderately warm temperature. See GB653775 attached. Recent work has shown the monglucosyl ureide forms in high yield from a melt using Amberlyst 15 as a catalyst. Possibly other acidic and dehydrating systems may also be useful. A pyrophosphate and silica gel or the thermal dehydration product of ammonium bisulfate would seem to be candidate catalyst / dehydration materials for a glucose and urea melt.

Attachment: GB653775 Glucose Ureide and Sugar Ureides.pdf (319kB)
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Attachment: Glucose Ureide Urea adduct biochemj01152-0221.pdf (490kB)
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Attachment: Glucose Ureide using Amberlyst 15 acidic catalyst.pdf (191kB)
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Attachment: Pages from handbookofsugara00browrich.pdf (139kB)
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Rosco Bodine - 5-12-2011 at 13:30

Something which may be a worthwhile experiment is to see if the glucose ureide would form via reaction of anhydrous glucose with the anhydrous Calcium Nitrate and Urea adduct Ca(NO3)2 - 4(NH2CONH2) perhaps with some catalytic acidity provided by glacial acetic acid. The formation of the glucose ureide is a dehydration type of condensation reaction favored by the presence of something which can remove the byproduct H2O and anhydrous Calcium Nitrate is capable of absorbing H2O and can form a tetrahydrate which would precisely absorb the byproduct H2O from formation of the ureide. Perhaps some eutectic melt system having added nitrates or other materials would be advantageous for the reaction scheme. Using alcohol or perhaps DMSO as a solvent may also help. Urea nitrate is acidic and might also serve as an acidic catalyst.

US1911580 Example #2 shows a Calcium Nitrate / Calcium Nitrate - Urea adduct low melting point mixture which is of particular interest as it can be vacuum dehydrated at 112C
to 0.7% H2O without decomposition of the urea to biuret or cyanuric acid. It seems possible that addition of anhydrous glucose or perhaps even glucose monohydrate to such a melt, possibly with or without an acidic catalyst could form the glucose ureide adduct.

Interesting also is the Magnesium Nitrate - Urea addition compound which is commonly a dihydrate but may occur also as an anhydrous form. I am looking for more references on this. Attached is one reference and a link for a synthesis
of the dihydrate in alcohol as well as from water.
http://pubs.acs.org/doi/abs/10.1021/ja01282a040

It may be feasible to form the glucose ureide in a nitrate melt and then to nitrate in situ by addition of sulfuric acid.
If such a scheme is workable the process would be greatly simplified. In such regard, the magnesium nitrate adduct
would be interesting due to the soluble sulfate byproduct
which would not complicate isolation of the nitrated organic material.

Attachment: US1911580 Calcium Nitrate Urea Adduct.pdf (118kB)
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Attachment: Thermal Stability of Urea Magnesium Nitrate Complexes.pdf (210kB)
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[Edited on 6-12-2011 by Rosco Bodine]

Rosco Bodine - 10-12-2011 at 20:11

Quote: Originally posted by vaslop

Im surprised that this compound hasn't taken off, has anyone tried making any glucose ureide?

I tried the synthesis as follows

10.2g of glucose hydrate dissolved in 3g of water at 60c.
34g of urea is added and stirred in.
When the temperature is 60c again, 91.8g of glucose hydrate is added and also stirred in.
Afterwards, once the mass is mostly melted, a mixture of 3g of water and 3g (~1.6ml) of sulphuric acid are added slowly.
The mixture reacts at 60c for 8 hours.

Here, no solid glucose ureide was noticed, however the black viscous mass was obtained, but I continued with the synthesis as is written in the patent.

The mix was dissolved in very little water and neutralised with barium carbonate.
This was then filtered and evaporated, however no precipitate was obtained.

I have repeated this procedure but allowing a reaction time of 16hours, but with the same result.

Has anyone managed to make any glucose ureide yet?

I have been further studying the literature and doing some checking of the stoichiometry have discovered what I am reasonably certain is an error in the patent which could account for the crystallization difficulty you have reported.

The quantities of glucose which you used are a scaled down proportion of the quantity reported in the Meijer patents US2612497 and GB653775, but the patent has evidently a typographical error in the text portion which misidentifies the glucose as the hydrate or monohydrate when the weight quantity indicates an equimolar stoichiometry for the stated weight corresponding with the anhydrous glucose. The same error appears in the US and the GB patents where the glucose is misidentified as being the hydrate but the weight stated would match use of anhydrous glucose. This error could have also been a transcription or translation error from the Dutch inventor, because the correction amount of additional glucose monohydrate which would balance the equation stoichiometry is coincidentally a second portion of 1020 grams, which would have likely been "lost in translation" as a second added individual portion ...if all of the glucose is indeed taken to be the monohydrate which is the commonly available form. To be clear, there would be required three additions total of Glucose Monohydrate, portion 1=1020 grams, portion 2=1020 grams, and portion 3=9180 grams which would be equimolar to 3400 grams of Urea. This would make the total glucose monohydrate needed 11.220 Kg. which is 56.66 moles.

For example 2 of the Meijer patents where sucrose is inverted in situ to provide glucose, considering an inversion effciency of 100%, 9.7 Kg of sucrose is the correct amount
which would upon hydrolysis to glucose give 56.66 moles glucose.

Doing the stoichiometry it is discovered that the weight figures in the Meijer patents do not reconcile with the text.
These adjusted figures would seem logical as a place to
begin troubleshooting the process. What should be a
good indicator of success is a crystallizing out of the desired product and at some combination of proportions and conditions that should occur since this is reported by many different sources for variations on generally similar conditions.

See example 1 of GB467749 attached as a comparison patent for earlier work / prior art, where the inventor is a German chemist with a phd, Dr. Kurt Quehl, who identifies the same glucose ureide gotten from a simple fusion at water bath temperature of an equimolar mixture of glucose and urea. There is some discrepancy however about the melting point determination of 117C for glucose ureide. Hynd reported a decade earlier the mp of 207C for glucose ureide. What accounts for the vast difference in melting points between the two studies is unknown and mysterious.
Dr. Quehl describes the difficult crystallization of the glucose ureide so it is probably safe to presume an impure glucose ureide of depressed melting point is obtained as the initial product. The 117C mp value reported by Dr. Quehl differs considerably from the earlier researcher Hynd's reported melting point of 207C, (See Alexander Hynd article January 1926). The US2116640 patent by the same Dr. Quehl and concerning the same subject matter is also attached. Also attached is US1979121 which is referenced within these patents and regards the formation of adducts of urea with metal salts. The formation of adducts of urea with metal salts is also a dehydration type reaction, and the analogy being recognized is precisely what has caused me to speculate that these reactions may be possible to be combined as a precursor to nitration.

Earlier in this thread a link was posted by franklyn to an article by Irving Goodman which tends to bear out the results of Hynd as being accurate with a mp of 207C or 208C
for the pure compound glucose ureide.

Here again is the link
http://books.google.com/books?id=NDnNCOG6RWcC&lpg=PA215&...

See footnote #13 on page 216 of the Irving Goodman article.

Better sense is now possible to be made concerning the discrepancy in melting points as the compound of Dr. Quehl is identified as being a simple molecular addition product of glucose and urea, absent the dehydration which leads to
glucose ureide.

Attached is a more recent article describing a variation on the Hynd synthesis which first forms the adduct of urea with the glucose ureide in order to facilitate crystallization, followed by boiling with alcohol to decompose the adduct and yield the desired glucose ureide in pure form mp 207C.

An excerpt from CA670146 which describes a variation on the Meijer synthesis using precipitation by methanol of the glucose ureide is also attached. The product identified by its optical and melting point properties appears to be the desired monoglucose ureide. Perhaps adjusting the proportions to equimolar would be an improvement as well as incorporating the precipitation using methanol. This synthesis can probably be further optimized with some fine tuning of the process, which is better understood after a study of these references.

Attachment: GB467749 Glucose Ureide by Fusion of Glucose and Urea.pdf (266kB)
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Attachment: US2116640 Glucose Ureide by fusion of Glucose and Urea.pdf (159kB)
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Attachment: US1979121 Metal Salt Urea Adducts.pdf (94kB)
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Attachment: Glucose Ureide Synthesis.pdf (751kB)
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Attachment: Pages 10-11 from CA670146 Example 1 Glucose Ureide Synthesis.pdf (95kB)
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[Edited on 11-12-2011 by Rosco Bodine]

Rosco Bodine - 11-12-2011 at 22:32

After considering the Example 1 of CA670146 attached above, which describes a synthesis of Glucose Ureide derived from the Meijer patent, further thought has been given to the discrepancy of weights which I first believed may be a translation issue with the Meijer patents. I no longer believe that such issue necessarily exists and the weights and description by Meijer may be valid as given. What appears to be an equimolar excess of urea with regards to the glucose is offset by the sulfuric acid which ties up the excess of urea as urea sulfate. When that neutralization of the sulfuric acid by the urea is taken into account, there is actually a 1 mole excess of glucose with respect to the available urea, so the weights given by Meijer in the patents are reasonable and in fact do reconcile. The CA670146 Canadian patent excerpt which was attached in the preceding post seems to be the most straightforward method found thus far for producing the Glucose Ureide.

In an earlier post I had mentioned the possibility that Urea Nitrate being acidic may suffice as an acidic catalyst, so I should have been more aware of this function being produced in the reaction conditions described by Meijer where
the urea sulfate and possibly some urea acid sulfate is formed in situ. Earlier
I speculated it may also be possible other acidic salts such as bisulfates or pyrosulfates or pyrophosphates may also work as the acidic catalyst.

The additional process details supplied by the York patent CA670146 along with identifying the urea proportions must account for a neutralization equivalent
of urea used to form in situ the urea salt of the acid catalyst provides confidence
that the process issue reported by vaslop who followed the incomplete description
of the Meijer patents can be resolved, and a crystalline product of high purity
should be obtainable.

The inventor who describes further details for the Meijer patents is the same William C. York as is inventor in the Diglucose Ureide patent which was posted on the first page of this thread, and is inventor with several related patents assigned to W.R. Grace Company concerning derivatives which are useful as detergents. York references the Meijer patents in his own patents which seem to be reliable, so it is reasonable to place confidence in the process described
by York in example 1 of CA670146.

Worth noting is that Yorks observation of experiments more involved with Diglucose Ureide rather than Monoglucose Ureide as is our interest, is that a minimum presence of H2O was required for the reaction to proceed .....and this may also hold true for the Monoglucose Ureide as well, which would seem to contradict the expected reaction dynamic for a reaction that is a dehydration type of condensation.
As counterintuitive as this may seem it could be true that
an optimal amount of water is best also for the Monoglucose Ureide synthesis. In whatever case, the process as described by York in CA670146 should resolve the issue
reported by vaslop.

[Edited on 12-12-2011 by Rosco Bodine]

Rosco Bodine - 13-12-2011 at 11:48

Some further indication has been found in a reference which tends to point to the circa 1963 York patent CA670146 as likely being a valid method. Attached is a circa 1960 article which describes the circa 1960 already published methods being tested, including the Meijer patent method upon which the later York patent method is modeled very closely. The Meijer and York related work is more conforming with the economics of process chemistry for bulk industrial needs of textile and detergent product applications, where the absolute purity and precison is lower than for biochemical or pharmaceutical preparations. However, the absence of any significant depression of melting point below 207C tends to
indicate acceptable purity for the more direct methods such as the York - Meijer processes which avoid the long reaction times and the isolation of a urea adduct as a precursor which
must be further processed to obtain the desired glucose ureide. It would seem then that the York patent CA670146 example 1 is likely the best published method among the methods which I have reviewed, based upon the literature which I have found.

Attachment: Glycosylureas. Part I. Preparation and some reactions of D-glucosylureas and D-ribosylureas.pdf (496kB)
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