killswitch
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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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Formatik
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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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Formatik
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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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killswitch
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Unbelievable! These guys want 43 bucks for this article
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PHILOU Zrealone
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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]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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franklyn
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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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Ral123
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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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PHILOU Zrealone
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What about the salts of trinitromethyl acetylene (3,3,3-trinitropropyne)?
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.
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]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Boffis
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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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franklyn
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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 1377 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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franklyn
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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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killswitch
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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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franklyn
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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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AndersHoveland
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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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Adas
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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
Rest In Pieces!
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PHILOU Zrealone
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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 ?
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Adas
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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 ?
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Maybe it would work with less expensive reagents too. 
Rest In Pieces!
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ken mason
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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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