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Author: Subject: Biguanide plus Biuret
Engager
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[*] posted on 13-7-2008 at 16:18
Biguanide plus Biuret


Reading Inorg. Syn. Journal i've found interesting and simple synth of biguanide by melting dicyandiamide and ammonium chloride at 160-165C. So i wonder if one can condense biguanide with biuret, will it result in formation of 2,4,6,8-tetrazacyclooctane-1,3,5,7-tetramine? On scheme it looks good... Biurete can be simply made by melting of urea and keeping temp about 160C until melt solidifies.

Will it work? At least is there any worth to try this? And if yes, whitch reaction conditions will be needed, and how to not allow polymerisation to start?

Scheme:



[Edited on 14-7-2008 by Engager]




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franklyn
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[*] posted on 14-7-2008 at 21:05


Just curious, what becomes of the oxygen during the intermediate octagonal molecule.

.
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[*] posted on 14-7-2008 at 23:39


I'm curious to know the use of the product? Its 8 membered melamine. The nitration product of melamine (DNAM) has good oxygen nbalance and high density though the structure doesnt lend itself to a direct analogy with an 8 membered ring.

[Edited on 15-7-2008 by Axt]
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Sauron
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[*] posted on 15-7-2008 at 03:33


I'm personally very familiar with biguanide (guanylguanidine) since I am obliged to swallow a gram of it every day (as Glucophage 500 mg, twice a day after meals.) For type 2 diabetes management.

The metabolites reek.




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Rosco Bodine
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[*] posted on 16-7-2008 at 21:43
biguanide / biguanidine


I am still trying to sort this out :P

The difference apears to be an extra amino....
and reactions potentially producing each are similar,
perhaps allowing for each product simultaneously.

Anyway, here's a couple of patents of possible interest.

Attachment: US1409963 Biguanide Nitrate from 140C melt NH4NO3 plus Dicyanamide.pdf (177kB)
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Rosco Bodine
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biggrin.gif posted on 16-7-2008 at 21:45
biguanide diperchlorate PETN substitute


Here's the second patent for a more thermally stable
equivalent substitute for PETN.

Attachment: US4340755 Biguanide_diperchlorate_PETN substitute.pdf (52kB)
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[*] posted on 16-7-2008 at 22:17


Quote:
Originally posted by Rosco Bodine
Here's the second patent for a more thermally stable
equivalent substitute for PETN.


Excellent finds, but the example 2 of 70% HClO4 in ethanol sounds like a death wish.
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Rosco Bodine
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[*] posted on 16-7-2008 at 22:44


There's probably an easier way.

Like heating guanidine chloride at 180-185C converts
it to biguanide bichloride ( I think:P )

and then mix warm saturated aqueous solution
of that with ammonium perchlorate, for a double decomposition, thereby precipitating (hopefully:D) the
desired bangmaker :D

Interesting old text here....
http://books.google.com/books?id=eDs3AAAAMAAJ&pg=PA414&a...

[Edited on 17-7-2008 by Rosco Bodine]
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[*] posted on 16-7-2008 at 23:59


Quote:
Originally posted by Rosco Bodine
There's probably an easier way.

Like heating guanidine chloride at 180-185C converts
it to biguanide bichloride ( I think:P )


There's various ways to get biguanide.

Quote:
and then mix warm saturated aqueous solution
of that with ammonium perchlorate, for a double decomposition, thereby precipitating (hopefully:D) the
desired bangmaker :D


Maybe either that, or use example 1 instead.
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Rosco Bodine
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[*] posted on 17-7-2008 at 00:16


And what about the extra amino for the "bi" guanidine
versus biguanide, is that another compound entirely?
Is there something I am missing about the analogue
being described in the tetrazole thread.
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[*] posted on 17-7-2008 at 00:57


Yes actualy you are missing something, biguanide and biguanidine are entirely different compounds, i attached picture to show you a difference.






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[*] posted on 17-7-2008 at 01:13


Preparation of biguanide sulphate. 25.2g of dicyandiamide and 40.1g of ammonium chloride are ground to the fine state and intimately mixed. Mixture is placed to oil or parafin bath heated to 160C-165C, and held at this temperature until liquid melt is obtained (1-1.5 hour). Note: Higher temps cause mixture to melt way faster but result in formation of guanidine instead of biguanide, biguanide present only in trace ammounts in this case, so tempereture interval of 160-165 makes synth relatevely slow but is essential to formation of biguanide. After liquid melt is obtained mixture is held in bath for more 10-15 minutes, and then cooled to room temperature. Solid is crushed to small lumps and dissolved in 150 ml of hot water (90-100C), and solution is filtered to remove insoluble product - ameline. The filtrate is next treated with a slight excess of ammoniacal copper (II) sulfate solution (the excess is noted by the appearance of a slight purple coloration). The precipitated rose-red copper biguanide sulfate is filtered, washed with water, and dissolved in 35 ml. of hot 10% sulfuric acid (the temperature should not exceed 90°). The resulting solution is then cooled by immersion in an ice bath. The crude crystals which form are separated and dissolved in 25 ml. of boiling water and the solution is cooled in ice. Again the crystals which form are dissolved in 25 ml. of boiling water and the solution is cooled in ice. The resulting colorless crystals of biguanide sulfate 2-hydrate are filtered, washed first with 10 ml. of cold water and then with 10 ml. of absolute ethanol, and dried at 110° for about 15 hours. The yield of anhydrous biguanide sulfate is 9.2 g. (15.4%); m.p. 231 to 232°.



[Edited on 17-7-2008 by Engager]




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Rosco Bodine
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[*] posted on 17-7-2008 at 01:58


The article you mentioned in the other thread for the biguanidine should be
Annalen der Chemie vol. 273, 140 (1893)
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[*] posted on 17-7-2008 at 02:12


This article is attached below. Justus Liebig's Annalen der Chemie, Volume 273, Issue 2-3 (p 133-144). J.Thiele "Uber Nitrosoguanidin"

[Edited on 17-7-2008 by Engager]

Attachment: Uber Nitrosoguanidin.PDF (477kB)
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[*] posted on 17-7-2008 at 02:16


This article contains synth of biguanidine nitrate. Justus Liebig's Annalen der Chemie, Volume 270, Issue 1-2 (p 1-63) J.Thiele "Uber Nitro And Amidoguanidine"

[Edited on 17-7-2008 by Engager]

Attachment: Uber Nitro And Amidoguanidin.PDF (2.5MB)
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Rosco Bodine
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[*] posted on 17-7-2008 at 02:17


Also found a later synthesis reference in English
JACS 1959, 81, 6017

Edit: Looks more like some condensation reactions
associated with the biguanidine rather than a synthesis thereof

[Edited on 17-7-2008 by Rosco Bodine]
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[*] posted on 17-7-2008 at 02:28


English translation of theese J.Thiele aricles can be downloaded for free by following links:

http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleFo...
page 389 J. Thiele Nitrosoguanidine

http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleFo...
page 1295 J.Thiele Nitro and Amidiguanidin




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[*] posted on 17-7-2008 at 02:45


Synthesis of biguanide and biguanide sulphate (English).

[Edited on 17-7-2008 by Engager]

Attachment: biguanide.pdf (99kB)
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[*] posted on 17-7-2008 at 02:47


Reference synth procedure on German.

Attachment: Zur Kenntniss des Biguanids.pdf (197kB)
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[*] posted on 18-7-2008 at 01:25


Quote:
Originally posted by Engager
So i wonder if one can condense biguanide with biuret, will it result in formation of 2,4,6,8-tetrazacyclooctane-1,3,5,7-tetramine? On scheme it looks good...
Will it work? At least is there any worth to try this? And if yes, whitch reaction conditions will be needed, and how to not allow polymerisation to start?
[Edited on 14-7-2008 by Engager]


I have doubt it would work in significant amount...because eather you will have linear polymerisation, or cyclisation into the stablest melamine (aromatic hexaring)...so tetrazacyclooctane ring might be tricky..Also aromaticity is broken because out of the plane and so octaring with all insaturation inside will not be favourised ...better expect a mix of the two structures

Regarding the unsoluble copper sulfate complex...might be interesting to investigate bis-biguanide copper diperchlorate...as explosive initiator. Also melamine triperchlorate should be interesting in comparison with the properties of benzene triamine triperchlorate...denser, more energy stocked in N=C bond than in C=C, positive OB...sole problem will be acidic and must be kept away from metals...




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