Anhydroenneaheptitol pentanitrate?

This seems very intresting energetic material. Supposedly similar to PETN, little less sensitive and bit more brisant. It also needs not too exotic chems (nor expensive) like acetone, formaline and Ca(OH)2 for anhydroenneaheptite and nitric acid to nitrate it (obviously, duh). There is old thread on it at E&W forum http://www.roguesci.org/theforum/archive/index.php/t-111.htm... but no-one has reported any success making it. it seems there maybe little problem getting crystallised anhydroenneaheptite but discussion stops there. I found it mentioned here too a few times but nothing useful. I also had a look at PATR 2700 (vol1, A404) but it didnt give much details - On anhydroenneaheptitol - wh crystals (from alc) with mp 156.
On pentanitrate - 137% TNT, sensitivity in drop test with 2kg weight is 30 cm vs. 16 for PETN
PATR gives few refs though but I cant find these texts . is there particular reason why its so unpopular? (It sounds good to me )
Does anyone have any related information on the subject or have someone tried to make it?

Thaks for help!

Newer synth...

This one is better.
A lot of work for a good yield though.
But...100% OTC

Exhaustive hydroxymethylation of acetone. Synthesis of anhydroenneaheptose. Olsen, Sigurd. Univ. Oslo, Norway. Chemische Berichte (1955), 88 205-12. CODEN: CHBEAM ISSN: 0009-2940. Journal language unavailable. CAN 49:42646 AN 1955:42646 CAPLUS

Abstract

Me, methylene, or methine groupings adjacent to the carbonyl in ketones can be exhaustively hydroxymethylated to 3,5-substituted tetrahydro--pyrones. The reaction is illustrated on acetone. Tollens [Ber. 27, 1089(1894)] and Mannich (C.A. 17, 728) in condensing Me2CO with HCHO in presence of CaO, obtained enneaheptitol and by dehydration anhydroheptitol (I). I is formed in greatly improved yield when the condensation is carried out in HOAc-H2SO4. I has been recognized as 4-hydroxy-3,3,5,5-tetrakis(hydroxymethyl)tetrahydropyran. Paraformaldehyde(600 g.), 400 mL. HOAc, concd. 80 mL. H2SO4, and 40 mL. Me2CO are carefully mixed and then refluxed 3 h. The resulting dark red soln. is refluxed 1 h. with 800 mL. 20% HCHO. The bis(methylene) ether (II) of anhydroenneaheptose is obtained on cooling; crystn. from 50% EtOH yields 235 g. colorless crystals, m. 152, sapon. no. 0. The tetraacetate (III) of anhydroenneaheptose (32 g.), obtained by distg. 30 g. II with 200 mL. HOAc and 5 cc. concd. H2SO4, m. 101 (from EtOAc). Anhydroenneaheptose (IV) (12 g.) is obtained by hydrolysis of III (25 g.) with MeOH-HCl, m. 127. IV reduces Tollens soln., but does not react with carbonyl reagents. IV with Me2CO contg. HCl gives bis(isopropylidene)anhydroenneaheptose, m. 19. The bis(methylene)ether of I, m. 222, has been prepd. by reducing II with HCHO in aq. KOH and also by reducing II with Na in EtOH. Both were identical with the bis(methylene) ether prepd. by direct condensation of IV with HCHO. The bis(methylene) ether of anhydroenneaheptitol monoacetate, m. 174; bis(anhydroenneaheptitol) triacetate, m. 106; bis(anhydroenneaheptitol), m. 172.




[Edited on 17-10-2005 by BASF]

Anhydro-enneaheptitol attempts

A long time ago I attempted to make some, and gleaned some insights from US patent 2885408 and the orgsyn prep for pentaerythritol.

I attempted several things, including using NaOH as a base.

The one attempt that produced a very syrupy, almost solid product (about 20 ml), that couldnt be concentrated further without decomposing (noticed by a sugary smell and darkening of the colour).

Ba(OH)2 was used here.

I calculated the molar ratios from the patent, and adapted them here.

Preparation

A 1.4 molar excess of CH2O (in the form of paraformaldehyde) was used with respect to the acetone, when it is assumed that all is converted to the final product.

Thus 100 g paraformaldehyde and 19.7 g acetone were mixed into 500 ml water.

To this suspension, 80.4 g of Ba(OH)2 *8H2O was added slowly. The temperature rises.

This was allowed to sit for 1 week at RT, with occasional shaking.

Then it was boiled down to 300 ml, filtered, and 25.0 g of H2SO4 (98%) was added to precipated the base as BaSO4. This was centrifuged/filtered, it's a pain but figured that's the only way to get rid of the base. pH after neutralisation was 6.4, so it was all good.


The final solution was boiled down to like 30 ml, until decomposition began. The syrup was initially clear until I overdid it and it started to acquire a yellow/brown colour due to decomposition.

Tried to dissolve it in EtOH, to no avail, or dry it in ether, but dissolution wasn't really possible. Nonethelless, i think the water content of the final product is very low, so one day this might be nitrated. Maybe someone else would like to try?

It certainly looked promising! If you look at the patent, the purification is not quite doable here.....



I also attempted the very same with 24% formaldehyde, and interestingly, this initial solution turned orange-red after day. Not sure what to make of it, never followed it up further.

While with NaOH/24% formaldehyde, the solution remains clear, but also never followed that one up. Strange that the base would produce such a difference.


Anyway, I definitley think there remains a lot of potential work to be done - reagents are cheap and accessible (at least more so that acetaldehyde in the case of pentaerythritol).


[Edited on 17-10-2005 by chemoleo]

Thaks for input guys!

dear BASF, do you have the whole text. It does use more chemicals and isnt maybe practical but just for sakes of chemical curiousity.
chemelo, that patent looks very interesting. I have some n-butyl acetate (at least I think I have - found it from old farm and loand some ). Is there an any easy way to "convert" it to n-butanol? Then I could maybe try that purification step as described in patent.
Axt, that text looks like worth to read, too bad I cant speak german . I am getting little pissed off by myself now not choosing germany as my second foreign language in school, because there are probably many more great texts out there that would be very interesting to read

And anhydroenneaheptitols OHs seem to be very hydroscopic.
maybe some good desiccating agent helps to do the final job, dehydrating that damn syrupy anhydroenneaheptite. like CaCl2 - would be easyer an cheaper too

Apparently there is also patent on that pentanitrate witch I would like read (to see how well it nitrates) but cant find. At E&W they give gb 28657 (1913) but in PATR gb 856,527 (1913), nether will give any results (at least not at http://v3.espacenet.com)
Well, I´ll do some experiments myself if I get the chance and see what happens.

In my opinion, the included method of using glacial acetic acid/H2SO4 gives a substantially improved yield and purity and is more likely be able to prevent the trouble with the syrup. I think the syrupy consistency in the tollens´method is rather a consequence of impurities than of hygroscopicity.

I´d not waste time with the historical tollens´method waiting months or so for the syrup to crystallize on porous dishes

Ok, the aforementioned method uses lots of precious glacial acetic acid, maybe there is a way of recycling it...

I have to look up the library for the "Chemische Berichte", to find out wether there is more information.

[Edited on 20-10-2005 by BASF]

[Edited on 20-10-2005 by BASF]

Quote:

Originally posted by BASF waiting months or so for the syrup to crystallize on porous dishes

If you are correct it sounds quite good actually. I alaways thought that its the hygroscopicity of AhE that f***s things up and that it decoposes before all water could evaporate when heating. Both tollens and olsen method produce aqueous solution of AhE, if I am correct, unless dry HCl is used in olsens (" Anhydroenneaheptose (IV) (12 g.) is obtained by hydrolysis of III (25 g.) with MeOH-HCl,". So I figured that those other methods would be better. But lot of things are still unclear here! (to me at least )
I am looking fovard of your findings at library!.

Translation of the first part(the second concerns analysis of the anhydroenneaheptite)

XLVI. About the anhydro-enneaheptite from formaldehyde and aceton

from Dr.M.Apel and B.Tollens

1. Preparation and Properties(not included)

Some years ago Dr. F. Mayer obtained, by bringing acetone, formaldehyde, lime and water together, removal of the lime(not CaCO3 but CaO) with oxalic acid and boiling to dryness, a syrup, in which the one of us after two years found several crystals.
This caused us to bring the abovementioned materials together again, to possibly obtain more of the mentioned crystals.

60g acetone, 240g formaldehyde(600g 40% solution), 6000g water, 65g previously prepared milky dispersion of lime (Ca(OH)2 here) was left stood in a bigger flask for a long time - up to 4 weeks- under repeated shaking.
In later preparations the flask was left stood at a 35°C warm place.

Subsequently, the flask with the mixture was heated in a boiling water-bath for some time, the liquid was decanted from the settled solid and filtered and freed from the lime, still boiling, by accurate precipitation with oxalic acid(ca. 115g).
The filtrates were concentrated to the syrup under stirring in the water bath.

These syrups crystallized upon seeding with the previously obtained substance, therefor they had become crystal pulps after 8 or 10 days, but sometimes the crystallization took weeks and months using exactly the same preparation method and was less complete.

Treatment of the syrup with alcohol and ether, through which a part was dissolved, another part stayed undissolved, offered no advantage, because the obtained fractions at good products (?) crystallized both, at not easily crystallizing products both yielded hardly any crystals.

As good as possible crystallized pulps were brought onto porous dishes made of clay and yielded dark, sometimes nearly white, dry, sometimes dark soft products, which had to be applied onto new dishes repeatedly.

The crystals were then dissolved in few water or alcohol and dissolved by heating, upon which they crystallized better and faster; multiple recrystallization with activated charcoal from alcohol completed the purification.

(...)


[Edited on 21-10-2005 by BASF]

Here it is. Thanks to myself for typing ...

I decided not to leave out the introduction, because it refers to the drawbacks of the tollens´method compared to olsens´ procedure.

32. Sigurd Olsen: About the exhaustive oxymethylation of acetone. Synthesis of an anhydro-ennea-heptose

(...)

The condensation of acetone with formaldehyde in excess in the presence of calcium hydroxide was conducted by B.Tollens and coworkers for the first time, who managed the isolation of the substance C9H18O6 with the MP 156°C during very time-consuming work.

(...)

Later it was repeatedly tried to oxymethylate aceton with numerous alkaline condensation-agents in polycondensation-conditions, but these attempts as well as the attempts of J.R.Roach, H.Wittcoff and S.E.Miller ("per"oxymethylation coupled with alkylation) are only of peripheral interest, as they show the possibility of partial oxymethylation in alkaline medium -thus generally under tollens´reaction conditions- without simultaneous reduction of the carbonyl group (...)

Such a simultaneous reduction can act already against the starting material itself as well as against all intermediates to the "per"oxymethylation final product, and prevents further condensation with formaldehyde by the formation of alcohols.

The formation of the "per"methylation-product would then only be possible with the few molecules escaping the hydrogenating side-reaction.
Under these sircumstances a very complex mixture of substances is generated by the tollens´reaction, which would serve as a satisfying explanation for the formation of the "crystallization-lame" syrups described by tollens and other authors, on the other hand also gives an explanation for the bad yields and the difficult isolation of the reduced "per"oxymethylation product.
Maybe this is the reason why the tollens´reaction was not able to establish itself as preparative method.

The biggest disadvantage of the tollens´reaction is the difficult to conduct reduction in the last phase, in which the carbonyl group of the "per"oxymethylation product is reduced to the carbinol group by reagent in excess, which causes the replacement of the precious ß-keto-alcohol of sugar-character by the less precious correspondent multi-valent alcohol.

In some cases it was managed to catch the "per"oxymethylation-product before the reduction by the application of stoicheometric amounts of formaldehyde 4)
(C.Mannich and W.Brose and others); still these methods are considered inferior (...)

The abovementioned drawbacks of the tollens´reaction now are obsolete when using glacial acetic acid /sulfuric acid instead of alkaline solution. (note of the authors: This cannot strictly be considered an acid catalyzed reaction, because it fails without addition of glacial acetic acid when only using aqueous sulfuric acid alone)
(...) no reduction of the carbonyl group occurs under these conditions, even when formaldehyde is in excess.
(...)
The advantages of the condensation in glacial acetic acid/sulfuric acid as opposed to alkaline condensation are as follows:
1.)short reaction time
2.)no undesired side-reactions
3.)ease of isolation of the non-reduced "per"oxymethylation-product
4.)its easily and seperately conducted reduction to the corresponding alcohol

Preparation:

1.exhaustive hydroxymethylation of acetone in glacial acetic acid/sulfuric acid:

A mixture of 600g paraformaldehyde, 400ml glacial acetic acid, 80ml conc. sulfuric acid and 140ml pure acetone was heated carefully til the beginning of the reaction.
When the reaction subsided, the mixture was boiled 3 hours under reflux. The dark red liquid then was mixed with 800ml 20% formalin solution and boiled for 1 hour for the saponification of acetates. After cooling down colourless needles crystallized and where vacuum filtered and recrystallized from 50% ethanol. yield: 235g; MP 152°C
Bismethylene ether of anhydro-ennea-heptose (VI)
C11H16O6 (244,2)

2. Tetraacetate of anhydro-enneaheptose (V):
30g of (VI) was distilled with 200ml glacial acetic acid and 5ml sulfuric acid under dropwise addition of glacial acetic acid, taking care to keep a constant volume of liquid in the flask.
After 500ml distillate have gone over, no formaldehyde could be observed using 2,4-diphenylhydrazine/HCl.
After cooling down, water was added to the flask. Yield was 32g of a light brown substance, which got colourless after recrystallization from ethyl acetate and melted at 101°C.
C17H24O10(388,4)

3.Anhydro-enneahepatose (IV):

25g of the above described tetraacetate yielded after reesterification with methanolic hydrochloric acid and redissolving from ethyl acetate 12g of a completely colorless substance of sweet taste, which reduces tollens´solution, melts at 127°C and is unreactive with carbonyl-reagents.
C9H16O6(220,1)


That´s it..... i deserve a break right now....





[Edited on 22-10-2005 by BASF]

Thanks for the scan Axt .

Here the translation of the one important part i really did not want to miss. ... the synth is comprehensive only to the anhydro-anneaheptose, which is only the precursor to anhydro-anneaheptite. forgive me ...

Anhydro-enneaheptite(II):

20g Anhydro-enneaheptose were dissolved in 100ml hot formalin and 50g cryst. barium hydroxide in 100ml water were added within a few minutes, which caused the solution to react vigorously under boiling.
The liquid reacted neutral to litmus and, but still had a strong formaline-smell and was boiled a further 10mins, filtered hot and boiled nearly to dryness.
As this residue still had a smell of formaldehyde, a solution of 10g sodium hydrogensulfite in 40ml water was added and the reaction mixture was boiled til a sticky mixture of salt resulted.
After thoroughly mixing ("verreiben" "anreiben" what does it equal in english??) with anhydrous sodium sulfate it was extracted 6 hours with 300ml dry ethyl acetate in a soxhlet extractor(i hate this part, further complicating a complicated procedure).
In the extraction big quantities of a colorless substance already solidified.
After vacuum filtration(better transl for "absaugen", anyone?) 17g of the abovementioned substance of MP 135-146°C were obtained. The MP did not vary much after recrystallization from various different solvents.

The substance did not reduce Tollens´ solution, thus the contained impurity cannot be the starting material. For save identification, a sample of the substance was taken up with a small quantity of warm ethanol, then acetone and a few drops of HCl were added and heated for a moment to dissolve the substance. Upon cooling a big quantity of colorless lamella ("blättchen" crystallized, sharp MP at 230°C and gave no melting point lowering with bis-isopropylideneether (p.a. purity).

[Edited on 29-10-2005 by BASF]

[Edited on 29-10-2005 by BASF]