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[*] posted on 10-10-2012 at 09:37
dicyanoacetylene


I've been interested in this compound for some time now but have no clue how to synthesize it with anything I could actually acquire.

Also, I've been contemplating the best oxidizer to mix it with. Preferably it would have no hydrogen in it, and no solids either. A non-polar compound would also be preferable to a polar compound, since it might dissolve in the dicyanoacetylene.

So, the ideal additive would be a non-polar compound with no metals and with a positive oxygen balance.

Any thoughts?
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[*] posted on 10-10-2012 at 11:43


Dicyanoacetylene isn't the kind compound you can take home to meet the parents and it's a bitch to make and handle.

Pyrolysis of acetylenedicarboxamide (2-butynediamide) at 0.2 Torr and 210-215 C is the original procedure of preparation but is useful for only small amounts, yield is 30-40% (Ann. Chim. [Paris] [9] 14 [1920] 5/46, 7/16; Compt. rend. 150 [1910] 225/7). A more recent example using this is in J. Org. Chem., 1957, 22 (10):1171-1175. This route uses P2O5.

Pyrolysis of 2-oxo-4,5-dicyano-[1,3]dithiolane at 800 C, yield is 59-76% (J. Org. Chem. 33 [1968] 541/4).

Gas phase pyrolysis of 1,2-dichloro-1,2-dicyanoethylene gets a good yield (USP 3070622).

Dicyanoacetylene is a clear, colorless liquid (at 20.5 to 21 C) which has an odor like cyanogen. It also is a lacrimator like cyanogen. In combustion experiments it did not give vigorous decomposition even in the presence of a flame (the experiments are described in J. Phys. Chem. 64 [1960] 1776/8). In the absence of oxygen the crystalline material can be stored at -78 C for an unlimited amount of time.
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[*] posted on 10-10-2012 at 22:29


I wanted to add considering its reactivity to oxygen, mixing it with an oxidizing agent could cause violent polymerization or reaction. Even liquid oxygen could be risky. But I've not read anything specifically about this.
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[*] posted on 12-10-2012 at 10:52


Unbelievable! These guys want 43 bucks for this article
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[*] posted on 5-11-2012 at 10:52


http://en.wikipedia.org/wiki/Dicyanoacetylene
Note the very high combustion temperature 4990°C!
And of course its density, quite high for such a short, low MW volatile organic molecule.

Also of interest...
http://en.wikipedia.org/wiki/Diacetylene

http://en.wikipedia.org/wiki/Cyanoacetylene

Thus triple linkages are good ways to store energy...but it also induce endothermicity and unstability...that is why they enter into the list of explosophoric groups.

[Edited on 5-11-2012 by PHILOU Zrealone]




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[*] posted on 5-11-2012 at 18:23


Isomers of paracyanogen are quite similar and easier to work with.
http://www.sciencemadness.org/talk/viewthread.php?tid=23&...

From Molecular Building Blocks to Condensed Carbon Nitride Networks:Structure and Reactivity
http://edoc.ub.uni-muenchen.de/6492/1/Lotsch_Bettina_V.pdf

Carbon Nitrogen Polymers US patent 3057808

I imagine this could be the basis for an sprengel explosive formulation , similar to
Boron Nitride as described here _
http://www.sciencemadness.org/talk/viewthread.php?tid=1970&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=1970&a...

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[*] posted on 5-11-2012 at 21:42


Why don't they use like boron hydrides for high temperature, precision cutting and such? How can carbon based composition beat that?
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[*] posted on 6-11-2012 at 01:43


What about the salts of trinitromethyl acetylene (3,3,3-trinitropropyne)?:cool:
H-C#C-C(NO2)3 would make interesting primaries with near perfect OB, high densities and heat output thanks to the stored energy in the acetylenic triple linkage.
Its acidity must be close to that of nitroformic acid (trinitromethane).

It may form a dimer via copper catalysis 1,1,1,6,6,6-hexanitrohexa-2,4-diyne. :cool::cool:
2 H-C#C-C(NO2)3 --> (O2N)3C-C#C-C#C-C(NO2)3
A linear rigid molecule generating an explosive with perfect OB, no hydrogen and two triple linkages (thus will display a very high energy and heat output), and for sure quite dense!
Its VOD must be quite high.

[Edited on 6-11-2012 by PHILOU Zrealone]




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[*] posted on 6-11-2012 at 09:57


I think the best way to a really wickedly energetic compound would be to react dicyanoacetylene with sodium azide to see if it would produce 1,2 bis(5-tetrazolyl) acetylene. There are presidences for this reaction, sodium dicyanamide yields bis(5-terazolyl)amine, cyanogen yield 5,5 bistetrazole and malononitriles yields bis(5-tetrazolyl)methane.

See "Azole-Based Energetic Salts, Haixiang Gao and Jean'ne M Shreeve, Chem Reviews, 2011, p7377 to 7436; specifically pages 7399 to 7405 which deals with bridged tetrazole systems.

Actually digging a little deeper this reaction may not work; while it is possible to produce 5-vinyltetrazole attempts to react cyanoacetylene with azide resulted in attack of the triple bond by the azide and the results was a mixture of triazole derivative. So it seem unlike that dicyano-acetylene would fair better.

See "Preparation of vinyl tetrazole, C. Arnold & D. N. Thatcher, J. Org. Chem. 1969 v34 pp1141-1142"
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[*] posted on 9-11-2012 at 12:26


http://chemspider.com/Chemical-Structure.13449.html

NΞC-CΞC-CΞN
http://en.wikipedia.org/wiki/Dicyanoacetylene ( 2-Butynedinitrile )
CAS 1071-98-3
Index of Refraction: 1.481
Density: 1.176 g/cm3
Melting point: 20.5 °C
Enthalpy of Vaporization: 31.76 kJ/mol
Boiling Point: 76.5 °C at 760 mmHg
Vapour Pressure: 101 mmHg at 25 °C

ΔHf +500.4 kJ/mol / +119.6 kcal/mol


At the foot of page 1
Progress Report of the Explosives Group - Sept Nov 1958
http://www.osti.gov/bridge/servlets/purl/459856-APvtjU/webviewable/459856.pdf
" A small sample of dicyanoacetylene has been prepared and its compatibility
with tetranitromethane is being determined." ( no further info or comment )
note * Dicyanoacetylene itself is an entropic explosive yielding carbon powder and nitrogen gas.

Preparation of Dicyanoacetylene and it's polymerization on pdf page 21
Synthesis and Evaluation of Polymers for Use in Early Warning Fire Alarm Devices
http://www.dtic.mil/dtic/tr/fulltext/u2/a307285.pdf

Poly(cyanoacetylene): a conjugated polymer with a rich phase diagram
http://144.206.159.178/ft/162/35529/609809.pdf

Cyanoacetylene and Its Derivatives:XXXIV.* Nucleophilic Addition of Tetrazole to Cyanoacetylenes
http://www.springerlink.com/content/l0641327121tt167/fulltext.pdf

New polynitrogen hyperbranched polymers
http://www.springerlink.com/content/0125435600651205/fulltext.pdf

Cyanoalkynes: Magic wands for the preparation of novel aromatic compounds
http://iupac.org/publications/pac/65/1/0047/pdf

Carbocyclic & Heterocyclic Cage Compounds
http://www.dtic.mil/dtic/tr/fulltext/u2/a364287.pdf

Free-Radical Polymerization of Dicyanoacetylene ( In references section )
http://www.sciencemadness.org/talk/files.php?pid=192254&...

Syntheses of Dicyanoacetylene ( In references section )
http://www.sciencemadness.org/talk/files.php?pid=191948&...

Dicyano acetylene Prep US patent 3070622
Dicyanoacetylene Prep US patent 3322816
Dicyanoacetylene Hi Temp Synth US patent 3336359
Dicyanoacetylene Polymers US patent 3419537

Attachment: α-Cyano acetylenes.pdf (1.8MB)
This file has been downloaded 843 times
Related thread _
http://www.sciencemadness.org/talk/viewthread.php?tid=9164

________________________________________________


Possible approach to making Dicyanoacetylene NΞC-CΞC-CΞN

Dichloroacetylene (DCA) is a highly reactive compound that decomposes rapidly
in contact with air into a series of chlorinated aliphatic hydrocarbons ( Phosgene ,
Trichloroacetyl Chloride , Trichloroacryloyl Chloride & Hexachlorobutadiene).
For this reason it is not available commercially and one has to make it. Be wary
of the hazards as told by The WiZard is In here _
http://www.sciencemadness.org/talk/viewthread.php?tid=2063#p...
http://cameochemicals.noaa.gov/chemical/25019

In this old thread Polverone disclosed a serendipidous way to produce it
http://www.sciencemadness.org/talk/viewthread.php?tid=2063
Related thread _
http://www.sciencemadness.org/talk/viewthread.php?tid=4915
garage chemist outlines the preparation _
http://www.sciencemadness.org/talk/viewthread.php?tid=4915#p...
Thanks to kazaa81 for these _
http://www.sciencemadness.org/talk/viewthread.php?tid=4915#p...
http://www.sciencemadness.org/talk/viewthread.php?tid=4915#p...
Conducting Polymer - Synthesis & Properties of an Unsymetrical Disubstituted Polyacetylene Polyiodocyanoacetylene
http://proj3.sinica.edu.tw/~chem/servxx6/files/paper_12893_1273756507.pdf
http://www.youtube.com/watch?v=OcSdcXBUhBM


The solvent 1,1,2-Trichloroethylene is being phased out of commerce and is
increasingly hard to find as a technical grade retail product. Here is a list of sources
http://www.zorotools.com/g/00098471/k-G1039315
http://www.hisco.com/products/view/Chemicals-Cleaners/Cleaners/Chem026
http://www.all-spec.com/products/ES2279.html
http://www.all-spec.com/products/ES179.html
http://www.techni-toolcatalog.com/lg_display.cfm/catalog/135/page/260
http://www.chemtronics.com/products/product.asp?r=1&m=2&id=436
Try looking first at your local auto parts store for degreasers.
Note * will not be shipped to California , other states may be restricted also
Connecticut , District of Columbia , Delaware , Illinois , Massachusetts , Maryland ,
Maine , Michigan , New Hampshire , New Jersey , New York , Ohio , Pennsylvania ,
Rhode Island , Virginia.


A possible reaction scheme would involve replacing the labile Chlorine of C2Cl2
in solution as it is formed before it can escape as a gas. Of course the reactivity
of NΞC-CΞC-CΞN must be addressed at the same time. Here ( X ) is the anion
Formatik dicusses some of the ideas below _
http://www.sciencemadness.org/talk/viewthread.php?tid=4915&a...


1. CHCl=CCl2 + NaOH => NaCl + H2O + C2Cl2 / / => + 2 Na( X ) => 2 NaCl + C2( X )2

Other possible products employing this possible scheme.

2. CHCl=CCl2 + NaOH + 2 NaCN => 3 NaCl + H2O + C2(CN)2

2. CHCl=CCl2 + NaOH + 2 NaN3 => 3 NaCl + H2O + C2(N3)2

2. CHCl=CCl2 + NaOH + 2 NaNO2 => 3 NaCl + H2O + C2(NO2)2

NaNO2 Solubility in Water: 850 grams / liter , @ 20 ºC

_______________________________________________________


So , how to proceed , first lets examine mutual solubility of the materials to be used

Trichloroethylene ( TCE )
solubility in the following
H2O : < 1 mg/ml @ 21 ºC
DMSO : > 100 mg/ml @ 22 ºC
source - http://books.google.com/books?id=cjX2gB9MKi4C&pg=PA413&lpg=PA413
- Inorganic ionic sodium salts are not soluble with TCE
Trichloroethylene in DMSO - MSDS , DMSO permeates through skin bringing with it whatever it solvates.
http://www.usp.org/pdf/EN/referenceStandards/msds/1601827.pdf


DimethylSulfoxide ( DMSO )
solubility in the following
H2O : soluble in all proportions ( DMSO is very hygroscopic )
- Inorganic salts - to a limited extent but less than in H2O , also see _
http://books.google.com/books?id=7IFx-qhJbWkC&pg=PA232&lpg=PA243
Solubility of Alkali & Alkaline Pseudohalides http://www.nist.gov/data/PDFfiles/jpcrd643.pdf
DMSO Reaction solvent guide , see pages 30 to 37 , & 43
http://www.gaylordchemical.com/uploads/images/pdfs/literature/105B.pdf
source - http://www.sciencemadness.org/talk/viewthread.php?tid=18244#...


Density of TCE is 1.46 gm/ml , density of DMSO is about that of H2O very slightly more.
The two are somewhat miscible , DMSO is to be gradually mixed into TCE until no more
dissolves and it forms an oily appearing film on the surface.

Density of the TCE DMSO solution is more than the water salt solutions and
will comprise the lower phase of the reaction setup.

The way to go it seems is first to dissolve NaOH and Na( X ) separately
using only the distilled water necessary to completely dissolve each one
in the stoichiometric quantity according to the balanced formulas above.
It may be advantages to use slightly less water than is necessary to
dissolve the salt by slightly warming the solution 20 ºC above room
temperature. This way as it cools some salt will precipitate down into
the lower phase of TCE. ( Distilled water is cheap ~ $ 2 gal. )

Mix together the two separate salt water solutions in the same container.
Having allowed enough water for each to dissolve there should not be any
settling out due to common ion effect of sodium.
Carefully pour this salted water solution onto the TCE DMSO mixture so
that it floats on top. One can later add DMSO to this top phase to see if
the expected reaction is enhanced by this.

One can provide some light agitation with a sound source as a radio
or speaker right next to the container. Waves should be visible on the
surface.

Reaction should occur at the interphase as the formed Dichloroacetylene
percolates into the upper salted water phase.

I expect that NaCN will form Dicyanoacetylene
and that NaN3 will form Diazidoacetylene
The nitro variant derived from NaNO2 may require some muriatic acid HCl
to promote the required reaction.

Take precautions against spontaneous detonation particularly for the
second two , these are not known compounds I believe.

Dinitroacetylene
http://handle.dtic.mil/100.2/ADA128954
You must append ( .pdf ) to the file to read it.

1,2,3,4-Tetrazines, 1,2,3,4-Tetrazine Di-N-oxides, Pentazole Derivatives, Pentazine Poly-N-oxides, and Nitroacetylenes
http://www.dtic.mil/dtic/tr/fulltext/u2/a430332.pdf

Chemistry of Polynitroethane Derivatives
http://www.dtic.mil/dtic/tr/fulltext/u2/a197044.pdf

Nitroacetylene
https://www.thieme-connect.de/ejournals/pdf/10.1055/s-2002-34387.pdf

En route to Dinitroacetylene
http://www.ncbi.nlm.nih.gov/pubmed/22532431

.

[Edited on 10-11-2012 by franklyn]
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[*] posted on 11-11-2012 at 10:10


http://www.sciencemadness.org/talk/viewthread.php?tid=20857#...

According to woelens experience the phases stratify inversely to what I have
assumed in my outline. This I find curious since water floats on Trichloroethylene.
I did not account for the lessening of the density of TCE from 1.46 when some
DMSO which has a density of 1.1 is mixed in so the mixture may be perhaps 1.3

Accounting for the density of the water salt solutions

density of NaCN is 1.6 , solubility 60 gm/100 ml
( 60/160 = 0.375 ) X 1.6 = 0.6
( 100/160 = 0.625 ) X 1 = 0.625
total is 1.225

density of NaN3 is 1.85 , solubility 40 gm/100 ml
( 40/140 = 0.285 ) X 1.85 = 0.527
( 100/140 = 0.715 ) X 1 = 0.715
total is 1.242

density of NaNO2 is 2.16 , solubility 80 gm/100 ml
( 80/180 = 0.44 ) X 2.16 = 0.95
( 100/180 = 0.56 ) X 1 = 0.56
total is 1.51

density of NaOH is 2.13 , solubility 110gm/100 ml
( 110/210 = 0.52 ) X 2.13 = 1.11
( 100/210 = 0.48 ) X 1 = 0.48
total is 1.59

It remains now to estimate the density of the combined lye and salt solution
in the stoichiometric amounts. We can see immediately without further study
that any mixture of water solutions of NaOH and NaNO2 will sink displacing
the Trichloroethylene DMSO solution to the upper phase. The others may
actually become close in density to TCE / DMSO and make a turbid mixture.

.
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[*] posted on 11-11-2012 at 10:14


What about tetrakis(cyanoethynyl)methane?

And I know this last one is pie-in-the-sky, but what about 1,2,3,4,5,6,7,8-octa(cyanoethynl)cubane? Mixed with nitrosyl perchlorate, I imagine it could break the 5000 Celsius mark.
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[*] posted on 11-11-2012 at 11:09


Problem is those would not remain as is for long as you conjure them , and will
isomerize or polymerize into something else that can be obtained more easily in
other ways. Hard to envision what you will finally get , but probably not worth the
effort just for fuel compared to more prosaic unsaturated strained compounds.

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[*] posted on 30-11-2012 at 03:05


Cyanogen produces a 4,525 °C flame with oxygen. First, let us remember that the carbon-nitrogen triple bond is almost as strong as the triple bond in elemental nitrogen.

N≡N 946 kJ/mol
C≡N 866 kJ/mol
C≡O 1073 kJ/mol (in carbon monoxide)

I think one reason why the flame temperature of cyanogen is so hot is because the presence of nitrogen means less oxygen is required, so there can be a greater ratio of carbon. In solid carbon, however, there are more carbon bonds to break, and no N2 formed to compensate for the initial breakage of bonds.

An all-carbon cylic acetylene (which have been sythesised) would probably make an even hoter flame temperature.




I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
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[*] posted on 19-12-2012 at 06:50


I was wondering if DCA can be synthesized from copper acetylide somehow.

Cu2C2 + 2 ClCN ----> 2 CuCl + C4N2

Or from dihaloacetylene:

C2X2 + 2 NaCN ----> 2 NaX + C4N2




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[*] posted on 23-12-2012 at 14:02


Maybe:
H-C#C-H (g) + 2 I2 (aq) -base-> I-C#C-I (s) + 2 HI(g)
I-C#C-I + 2 Ag-C#N -solvent-> N#C-C#C-C#N + 2 AgI(s) ?

H-C#C-H (g) + 2 Na-NH2 -solvent-> Na-C#C-Na + 2 NH3(g)
Na-C#C-Na + 2 Cl-C#N -solvent-> N#C-C#C-C#N + 2 NaCl ?




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[*] posted on 23-12-2012 at 14:27


Quote: Originally posted by PHILOU Zrealone  
Maybe:
H-C#C-H (g) + 2 I2 (aq) -base-> I-C#C-I (s) + 2 HI(g)
I-C#C-I + 2 Ag-C#N -solvent-> N#C-C#C-C#N + 2 AgI(s) ?

H-C#C-H (g) + 2 Na-NH2 -solvent-> Na-C#C-Na + 2 NH3(g)
Na-C#C-Na + 2 Cl-C#N -solvent-> N#C-C#C-C#N + 2 NaCl ?


Maybe it would work with less expensive reagents too. :D




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[*] posted on 21-10-2018 at 14:53


Hello, I'm new here found you after researching dicyanoacetylene.
Anyone know if it can be used as an additive to rocket fuels to raise the flame temp or is it too unstable for anything outside the fume hood?
Also wouldn't it be easy to synthesize by an electric carbon arc in a nitrogen stream?
Thanks,
Ken
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