Sciencemadness Discussion Board - Methyl Acetylides

Methyl Acetylides

Axt - 27-9-2004 at 22:42

Something thats been sitting under everyones noses, yet hasn't made mention. MAPP gas (methyl acetylene - propyne) is more readily available then acetylene and will also form acetylides with silver, maybe the others as well but I havnt seen any mention of the methyl acetylides before, maybe MAPP wasnt commonly used back in the days of Fedoroff etc.. Silver methyl acetylide (SMA) can be made by bubbling MAPP gas through a silver nitrate solution.

<center><img src="http://www.sciencemadness.org/scipics/axt/silvermethylacetylide.jpg"></center>
5g AgNO3 was dissolved into 75ml distilled water, into this was bubbled MAPP, within minutes the solution had turned white with a large crop of crystals, was filtered and dried.

<center><img src="http://www.sciencemadness.org/scipics/axt/smapics.jpg"></center>

On ignition small amounts of SMA explode with a thump, flame and thick cloud of black smoke.

<center><img src="http://www.sciencemadness.org/scipics/axt/smaignite.jpg">
<a href="http://geocities.com/roguemovies7/">MOVIE AVAILABLE</a></center> 

[Edited on 9-12-2005 by Axt]

Axt - 28-9-2004 at 01:26

Sorry, methyl acetylene - propyne should be propadiene, propyne is another name for methyl acetylene.

JohnWW - 28-9-2004 at 01:43

You seem to have got them mixed up. Propyne, or methylacetylene, C3H4, is H-C(triplebond)C-CH3. It is isomeric with propadiene, or allene, H2C=C=CH2.

BTW How come propyne is "more readily available than acetylene"? In view of the manner in which acetylene can be made on an industrial scale via CaC2 by reaction of Ca metal, or of CaO or CaCO3, with carbon, I would have thought the opposite.

John W.

Axt - 28-9-2004 at 02:00

Quote:

Originally posted by JohnWW
You seem to have got them mixed up. Propyne, or methylacetylene, C3H4, is H-C(triplebond)C-CH3. It is isomeric with propadiene, or allene, H2C=C=CH2.

Errr yeh as I just said. I assume the propadiene is formed as a byproduct on forming MA.

Quote:

BTW How come propyne is "more readily available than acetylene"?

Because we (or at least I) arn't talking about industry, Im talking about walking into a hardware store and buying a bottle of gas, without the need, hastle or cost of hiring a whole tank of acetylene. MAPP is much more readily available to the common man. 

[Edited on 4-11-2007 by Axt]

vulture - 28-9-2004 at 09:50

Quote:

BTW How come propyne is "more readily available than acetylene"? In view of the manner in which acetylene can be made on an industrial scale via CaC2 by reaction of Ca metal, or of CaO or CaCO3, with carbon, I would have thought the opposite.

Making acetylene through CaC2 is very uneconomical because of the huge energy cost for producing CaC2. Therefore this method has been largely abandoned by the industry. But let's keep this on topic and prevent another I-know-more-than-you showoff, shall we?

[Edited on 28-9-2004 by vulture]

Im dumb

TomThumb - 28-9-2004 at 16:23

Ok, excuse my stupidness but how would you make a silver nitrate solution.
Iv never even made ng.

Thanks

The_Davster - 28-9-2004 at 16:50

Fitting title tomthumb :mad:

A solution is what results when a solute is disolved in a solvent.
In this case the solute is silver nitrate and the solvent is water.
So you just dissolve silver nitrate in water.
It was even stated in the post "5g AgNO3 was dissolved into 75ml distilled water", guess what that makes? Thats right, a solution.

jeez :mad:

EDIT: Axt; Did you weigh your yield?

[Edited on 29-9-2004 by rogue chemist]

Axt - 28-9-2004 at 17:45

No, I never weighed the yield, but I expect it depends more on your ability to get it out filter & dry it without loss, as it should go to near 100% (It wont create a double salt will it??).

Drop test was 0-5cm (same as acetone peroxide). Though it only fires after being struck numerous times at that height. 10-15 to guarantee first hit detonation. This is due to it being a fine powder, has to have any "give" pushed out of it before it will fire. Need a lighter weight on the rig to get decent results on the sensitive primaries.

The_Davster - 28-9-2004 at 18:05

Yes, that was why I was wondering if you knew the yield, to calculate if there was a possibility of a double salt.

I hope to try this in the near future once I get some MAPP gas. I always wanted to try acetylides but was never able to get calcum carbide without huge hazmat charges.

Any tests on what it takes for silver methyl acetylide to DDT yet?

When I go to get MAPP, does that attachment on your bottle come with it, or does it cost extra? Thanks

Axt - 28-9-2004 at 19:38

Quote:

Any tests on what it takes for silver methyl acetylide to DDT yet?

Nup

Quote:

When I go to get MAPP, does that attachment on your bottle come with it, or does it cost extra?

It'll cost extra, I have a couple and I think both were over $50, then $20 for the gas! (AUS $'s). Make sure you can easily add a tube to it, for some its not that easy without leaks.

JohnWW - 28-9-2004 at 21:38

This is a bit off-topic, but the other major industrial process for making acetylene is by heating CH4, usually from natural gas, at 1,500ºC briefly (0.1 to 0.01 sec.): 2CH4 --> C2H2 + 3H2. This is obviously a lot quicker and requiring less energy (in terms of Ca reduction) than the CaC2 method, although the CH4 raw material may in the future be in short supply, and the C2H2 has to be separated from the H2 byproduct e.g. by gas chromatography or liquefaction.

As for methylacetylene, there do not appear to be any methods for preparing it directly or from a precursor 3-carbon compound, and without being mixed with allene (propadiene). The only methods appear to be from acetylene by adding a CH3, e.g. by using just enough NaNH2 and CH3Br with C2H2 for monomethylation (dimethylation can also occur).

A reference I have, T.W. Solomons' Organic Chemistry, says that silver (I) alkylacetylides, as an insoluble covalent compound, can be made by bubbling or mixing the alkylacetylene into an aqueous solution of ammoniacal silver hydroxide, [Ag(NH3)2]OH, with NH3 byproduct. Cu(I) acetylides can be made in the same way. The reaction is a qualitative test for terminal alkynes, and a method for separating terminal alkynes from alkynes in which the triple bond is internal.

John W.

The_Davster - 29-9-2004 at 19:46

Well, I had a go at it tonight.
2g silver was dissolved in 2.5mL 70% nitric(yes I know thats a huge excess) and once disolved the volume was increased to 40mL by addition of distilled water. Propyne was then bubbled through.

I was intending to do this as an analytical experiment to figure out if SMA formed a double salt but I made a few very stupid mistakes.
-I did not wait long enough for the silver to dissolve
-I did not bubble propyne through long enough, evidenced by after filtering out the SMA, adding NaCl to the filtrate caused silver chloride to precipitate.

Also, Axt, I only paid 10$(CDN) for my pound of propyne :cool:

, but that is probally because I am in a province with a lot of petrochemical resources/industries. I also managed to get around paying for a 50$ adaptor by just using the cheap burner head from my propane torch, unscrewing the flame adjuster off and attaching tubing to what was left of the burner assembly.

And finally, Axt, did your propyne smell terrible, mine did

, I was expecting it to smell something like propane which I find has a semi-pleasant smell.

I will definatly be repeating this experiment, so I can determine if SMA forms a double salt.

[Edited on 30-9-2004 by rogue chemist]

Axt - 29-9-2004 at 23:31

Quote:

Originally posted by rogue chemist
And finally, Axt, did your propyne smell terrible, mine did

, I was expecting it to smell something like propane which I find has a semi-pleasant smell.

I believe the the last P in MAPP is "petroleum gas" (LPG). Probably has additives to give it the awful smell.

Quote:

Also, Axt, I only paid 10$(CDN) for my pound of propyne

Same "benzomatic" cylinder? I think they would be the most common in N. America, US company. The benzomatic plastic torches wont work for feeding gas. I had to buy the brass one shown, which could have the "air inlet" screwed off.

Anyway, all attempts to make an acetylide from cupric salts (sulphate,TACN,hydroxide) and Ni(NH4)2(S2O4)2 have failed, amminated or not.

chemoleo - 30-9-2004 at 01:47

Did you try Cu I (cuprous)? IIRC this works better with normal acetylene too - and is more stable.
By failing I presume no precipitate could be found?

rikkitikkitavi - 30-9-2004 at 12:25

rouge chemist, foul smelling components are typically present in C2H2 made from CaC2. The latter also contains CaP forming phosphine in contact with water.

It would not be a surprise if C2H2 made by other processes has foulsmelling additives too, to distinguish it from other gases (and give it the "traditional C2H2 smell) and make leaks noticable . C2H2 has a very wide explosion range in air and is very dangerous because of that. But not under this conditions.

It is great fun to drop a few pieces of CaC2 into water while keepiing igniting the gas bubbles forming, especially if soap is added

the soot makes the flames very bright!

/rickard

Some results

The_Davster - 30-9-2004 at 16:11

My SMA dried into large plates on the filter paper that were grey unlike the SMA after it first precipitated. I do not like how it created those plates as they must be broken up in order to use the primary, which is always nerve wracking.
Does anyone have an idea on why SMA darkens after a while?

SMA does not seem to DDT that easily. Into a 3mm diameter straw was pressed 10mm column of lightly pressed SMA. This was then taped to a nickel and electrically ignited under some sand. I was rewarded with a small bang, obviously not a detonation, too quiet, and the nickel was not deformed in the slightest, just blackened by silver. I hope to try again with a better casing and possibly a bit more SMA.

BromicAcid - 30-9-2004 at 16:24

Probably darkens from photosensitivity to light, like many silver compounds. As the light strikes it the silver is reduced to the free element and in turn probably releases something like CH3CC-CCCH3

Axt - 1-10-2004 at 18:20

Quote:

Originally posted by chemoleo
Did you try Cu I (cuprous)?

I had a half-arsed attempt. Dissolved CuO in HCl, then Cu into that until clear. Using varying amounts of ammonia (from none to a lot) I couldnt get an explosive precip. If ammonia was added until the purple complex (from residual cupric) just started to form, bubbling the MAPP resulted in a non-explosive mass of yellowy-green precip. Cu(OH)Cl ? Whatever the case, cuprous isn't easy.

Below is the result 0.1g Ag salt lightly pressed in a .22 Khornet case, doesnt mean much but at best looks to be a weak detonation.

<center><img src="http://www.sciencemadness.org/scipics/axt/smacasing.jpg"></center>

[Edited on 9-12-2005 by Axt]

The_Davster - 1-10-2004 at 19:01

Axt, what are the benzomatic plastic torches? My gas cylinder of propyne is "BernzOmatic" brand and is brass.

I attached a picture of the cylinder and my way around paying for a 50$ attachment; a disposable pipette withthe end removed, taped to the main body of the propane burner attachment. Coincidently, the other end of the pipette happens to fit perfectly into the inside of a piece of my glass tubing.

EDIT: "burnzOmatic"changed to "BernzOmatic"

[Edited on 2-10-2004 by rogue chemist]

methylacetylene.bmp - 900kB

Axt - 1-10-2004 at 19:27

OK, now that I look mine is "bernzomatic" as well, stange that I've always read it at "benzomatic", but then, your reading it as "burnzomatic"

. Sounds like yours is a different formulation to me, I dont know what MPS gas is.

<center><img src="http://www.sciencemadness.org/scipics/axt/torches.jpg"></center>

[Edited on 9-12-2005 by Axt]

Rosco Bodine - 1-10-2004 at 19:39

Axt ,

Have you tried acidifying the AgNO3 solution with nitric acid , to see if you
get the double salt ? I'll check some references I have for the usual acetylide
double salt and get back on this . The
reaction is pH dependent and different
products may result for the usual acetylide , so this reaction may be similar .

The_Davster - 1-10-2004 at 19:43

To quote the label;
"MPS* GAS
Methylacetylene Propadiene, Stabilized"
56% CAS 68476-85-7
44% CAS 59355-75-8

I think is about the same thing as MAPP but with a stabilizer of sorts. I do get the same product as you but mine has absolutly no noticable flame once ignited, just the cloud of silver dust( Damn my fingertips are black

)

EDIT: Rosco when I made mine I disolved my silver in an (large)excess of nitric acid then bubbled gas through and my product was very similar to Axt's

EDIT2: googled the CAS numbers and found out it is 44% MAPP and 56% "A fuel mixture of propane, propylene, butanes & butylenes"

[Edited on 2-10-2004 by rogue chemist]

Axt - 1-10-2004 at 19:54

Rosco, No I havn't, and I wont get a chance to try now, won't make it home again for a couple months. Maybe the strange greeny precip was a double salt of the chloride, it only formed in mass when MAPP was bubbled through it. It was completely non-energetic, but it gave a brilliant blue when hit with the flame.

EDIT: RC, thats sounds like the same stuff, 44% MA-P 56% P --> MAPP.

[Edited on 2-10-2004 by Axt]

Rosco Bodine - 1-10-2004 at 19:57

US2483440 describes some of the different concentrations and pH conditions which produce quite different
compounds . The concentration of the
solution of AgNO3 should be kept below 10% and other references say slightly acid , IIRC , in order to produce the
double salts . PATR may have some
information on these details .
See PATR vol. 1 page A-80

[Edited on 2-10-2004 by Rosco Bodine]

Axt - 2-10-2004 at 01:50

Seems that the patent reference provided shows that straight AgNO3 should create the double salt, since HNO3 is created during the reaction. PATR mentions the ammonia soluton to give the straight acetylide.

It also says the high concentrations of AgNO3 will give higher complexes, that while non-explosive with the acetylide may be beneficial with the methyl acetylide as to even up the oxygen balance. Bloody expensive but it would be a good idea to try highly concentrated AgNO3 solutions.

The difference in weight of the SMA and the complex wouldnt be much, so you would have to create quite a batch to confirm any differences, but luckily the complex will weigh more, so if you achieve higher then theoretical yields its a near certainty that you have a complex.

PATR gives the cuprous chloride complex of acetylide as being non-explosive, so its possible that it was what I got with a simular solution.

[Edited on 2-10-2004 by Axt]

Rosco Bodine - 2-10-2004 at 06:33

What I found most interesting about the patent is that it provides a way of controlled crystallization of the usual double salt , by varying the concentration .
Any residual solution may be concentrated
and reused .

The description in PATR indicates that the
double salt is formed in nearly 100% yield
and is a quite good initiator , not light sensitive nor unduly friction or impact sensitve , storage stable at normal temperatures , but responsive to flame .
Initiating properties compare favorably
with MF and LA . The technical difficulty
for manufacture is low , so the only negative seems to be the cost of the silver , and the double salt is otherwise
a good initiator if the reported data is correct .

A thought I have is that it seems possible
that the methyl acetylene is possibly being
cleaved and the product is actually the same as the usual double salt from ordinary acetylene . This could be determined by comaparing the properties and weight and solubility of the product
with the properties of the usual double salt . Even if it is the same double salt ,
it would still be very useful if MAPP gas
could substitute for regular acetylene .

Another interesting detail mentioned in the patent is that a small amount of
Fe(NO3)3 in the solution prevents any precipitation of free silver which should increase the purity of the product .

[Edited on 2-10-2004 by Rosco Bodine]

Axt - 2-10-2004 at 19:10

Igniting a larger amount of the copper product up today resulted in a self sustaining combustion, smoldered as the black ash fell away from it. I take this as being good evidence that it has indeed formed a chloride complex and not some sort of basic chloride. But the colour, a very bright fluorescent green doesnt match the chloride complex of acetyline, Cu2C2.CuCl.H2O, which is dark violet (PATR).

Conclusion, I think it is a methyl acetylide, and it will form complexes. But the evidence could also be explained by a non-explosive CuCCCH3, as noone knows what its properties are, or cleaving & forming higher chloride complexes of Cu2C2, as we dont know what they look like.

<center><img src="http://ww1.altlist.com/~58717/pulse.altlist.com/images/chloridecomplex.jpg"></center>

[Edited on 3-10-2004 by Axt]

Possible evidence for existance of multiple forms of SMA, possibly double salts

The_Davster - 14-10-2004 at 19:56

I have prepared SMA twice since this thread started. Both batches were made within 2 days of each other. As mentioned on the first page of this thread, I prepared my SMA by dissolving 2g of silver in 2.5mL of nitric acid, adding water to increase the volume to 40-50mL, then bubbling propyne through.
The first batch the propyne was only bubbled through for under five minuits, where as the second batch the propyne was bubbled through for around 20min.

Well, here is the evidence, The SMA from both batches has been lying around for a couple weeks. The SMA from the first batch has now turned a dark grey where as the SMA from the second batch has only turned slightly light grey, only off-white. Both samples still deflagrate identically with the same appearance as when fresh. I am assuming that the different colour changes indicate different photosensitivities, and therefore are different compounds.

Thoughts?

chemoleo - 15-10-2004 at 09:54

Well, if you think there' s a double salt with AgNO3 in one case but not the other, you could always take each and analyse it for the presence of the nitrate ion.
I am sure there are specific tests for it, isn't the Na-prussid a specific one?
Anyway - this might be a way to go about it.

(i.e. you could subject a certain amount of each batch to NaOH, to precipitate the Ag as Ag2O (i guess), while then analysing the remaining solution for NO3-)

[Edited on 15-10-2004 by chemoleo]

Formatik - 14-5-2008 at 00:18

Although it will explode from a hammer blow (but less sensitive than Ag2C2.AgNO3), silver methylacetylide (C3H3Ag) is a feeble explosive. This feeble property is not really redeemed when it is mixed with several strong oxidizing agents (like KClO3 or KMnO4). Beilstein says the decomposition temperature is about 150 deg. It can also be destroyed like silver acetylide, by forming a water suspension of it and then adding concentrated HCl, which will release the alkyne gas.

Axt - 14-5-2008 at 03:26

Even though the Ag salt is quite a weak explosive, resembles blackpowder in its effect. I'd be interested if anyone can form the Cu salt of MA. Though I've failed in my attempts, it can be done. I searched for preparations but all are less then convenient (though they also give long winded routes to the Ag salts).

Copper and silver ethynyl co.ovrddot.ordination complexes. Blake, D.; Calvin, G.; Coates, G. E. Univ. Durham, UK. Proc. Chem. Soc. (1959), 396-7. http://dx.doi.org/10.1039/PS9590000377
Abstract
The Cu and Ag salts of substituted acetylenes are considered to be co.ovrddot.ordination polymers in which there is substantial back co.ovrddot.ordination from filled d orbitals of the metal to at least 2 acetylene groups. It was found that, although CuC2Me is insol. in N bases, it is readily sol. in a toluene soln. of Et3P to form yellow, cryst. Et3PCuC2Me. In addn., the complexes Et3PCuC2Ph, m.p. 138.5-139.5; Et3PAgC2Ph, m.p. 77.5-78.5; and Et3As-AgC2Ph, m.p. 89, were prepd. from the phenylethynyl salts. AgC2Ph is sol. in various amines. The degree of assocn. of Et3PCuC2Ph is 3 in PhNO2 and between 3.3 and 3.8 in C6H6, while that of the corresponding Ag complex is 2 in PhNO2 and 2.6-2.7 in C6H6.

Alkynyl compounds of transition metals. V. Alkynyl complexes with copper. Nast, Reinhard; Pfab, Wolfgang. Tech. Hochschule, Munich, Germany. Chemische Berichte (1956), 89 415-21. CODEN: CHBEAM ISSN: 0009-2940. Journal language unavailable. CAN 50:77632 AN 1956:77632 CAPLUS
Abstract
cf. C.A. 50, 9200c. When alkali salts of acetylenes in liquid NH3 are treated with suitable Cu compds. alkynylocuprates of the type M2[Cu(CCR)3] and M[Cu(CCR)2] are obtained. Adding 2.07 g. CuI in liquid NH3 to 2.54 g. KCCMe in 80 cc. NH3, filtering off the ppt., and washing it with NH3 give the ammoniate of K2[Cu(CCMe)3] (I) which, kept 2 hrs. in a high vacuum, loses the NH3 to give I. K2[Cu(CCH)3] (II) is prepd. similarly in 75% yield. A magnetic measurement in a high vacuum using the cylinder method gives a susceptibility of Xg = -0.7 10-6 for II. "Boiling" 2.94 g. KCCPh with 1.5 g. CuCCPh (III) in 130 cc. NH3 0.5 hr., filtering off the soln., concg. it to 80 cc., and cooling it 2 hrs. at -78 give 45% K2[Cu(CCPh)3].2NH3, cm.-long pale yellow needles, losing NH3 in a high vacuum at 20 in 3 hrs. Boiling 0.4 g. KCCMe and 0.6 g. CuCCMe in 100 cc. NH3 0.5 hr. gives 100% K[Cu(CCMe)2]. III (7.29 g.) and 5.08 g. NaCCPh in 400 cc. NH3 give 25% Na[Cu(CCPh)2].2NH3 (IV), long needles. Treating 6 g. IV in 60 cc. NH3 with 4.2 g. [Ni(NH3)6](SCN)2 in 60 cc. NH3 and cooling the violet soln. 1 hr. to -75 give [Ni(NH3)6][Cu(CPh)2]2.2NH3 which, 3 hrs. in a high vacuum, changes to a black C6H6-sol. compd. (60%) of the compn. NiCu2(CCPh)4.4NH3. Treating 0.58 g. IV in 70 cc. NH3 with 0.37 g. CuI in 70 cc. NH3 gives 80% CuCCPh.NH3, also formed from 1.23 g. CuI and 2.2 cc. HCCPh in NH3. Treating 2.16 g. CuI in 60 cc. NH3 at -75 with 0.71 g. NaCCMe in 100 cc. NH3 gives 80% CuCCMe, orange powder. Treating 0.486 g. KCCH in 80 cc. NH3 with 0.97 g. [Cu(NH3)4](NO3)2 (V) in 25 cc. NH3, distg. the NH3, taking up the residue the next day with 150 cc. NH3, and evapg. the filtered soln. give 99% black CuC2, highly explosive. Adding slowly 1.84 g. V in NH3 to 1.12 g. KCCMe in 100 cc. NH3, evapg. the NH3, and subliming the residue in a high vacuum at 20 give CHCCCH, m. 64.5, and 0.714 g. yellow CuCCMe. Boiling 5 min. a mixt. of 3.05 g. V and 1.75 cc. (CH2NH2)2 in 60 cc. NH3 and 2.79 g.
NaCCPh in 50 cc. NH3 and filtering the ppt. give PhCCCCPh (VI), m. 87; evapg. the mother liquor to 50 cc. and cooling it to -78 give [Cu(H2NCH2CH2NH2)2][Cu(CCPh)2]2.12NH3, violet crystals which, in a high vacuum at 20, lose NH3 with the formation of the green-yellow [Cu(H2NCH2CH2NH2)2] [Cu(CCPh)2]2.2NH3; on further standing in a high vacuum it loses (CH2NH2)2 and NH3 with the formation of VI and III.

Oxidation of copper(I), silver(I), and mercury(II) methylacetylides in aqueous solutions. Hoan, Huynh Manh; Brailovskii, S. M.; Temkin, O. N. Mosk. Gos. Akad. Tonkoi Khim. Tekhnol., Moscow, Russia. Kinetika i Kataliz (1994), 35(6), 889-92. Publisher: MAIK Nauka, CODEN: KNKTA4 ISSN: 0453-8811. Journal written in Russian.
Abstract
The primary product from oxidn. of Cu(I) and Ag(I) methylacetylides with copper halides is a dialkyne (MeCCCCMe), whereas the Hg(II) deriv. gives a haloalkyne. Reactivities of various oxidants in reactions with Cu(I) or Ag(I) methylacetylides are reported. The mechanism is discussed for oxidative conversions of metal ethynyl complexes.

Polyacetylenes. Schlubach, Hans Heinrich; Wolf, Viktor; Justus, Walter; Kohncke, Carl Heinz. Univ., Hamburg, Germany. Justus Liebigs Annalen der Chemie (1950), 568 141-59.
Abstract
In attempting to prep. CuCCH by treating H2O satd. at 0 with C2H2 with 500 cc. H2O contg. 10 g. CuSO4, 40 cc. NH4OH, and 30 g. HONH2.HCl, the sole product was Cu2C2 (which was also obtained whenever the conditions were varied); the mono-Cu deriv. was never isolated. In an expt., described in detail, NaCCH (I) (prepd. from 8 g. Na) in 300 cc. liquid NH3 and 2.5 g. Fe2O3 treated 4 hrs. with a rapid stream of O gave 0.45 g. (HCC)2, isolated as the hexabromide (II) (cf. Straus and Kollek, C.A. 21, 50). To I (from 2 g. Na) in 250 cc. NH3 at -40, 8.22 g. KMnO4 was added gradually, followed by 11.2 g. dry NH4Cl and, with vigorous stirring, 22.4 g. Mn(NO3)2; the soln. was then treated with O as described above, yielding 35.35% II. The accompanying, regenerated C2H2 (isolated as Cu2C2) was 46.5% (based on I used). The black residue (0.4 g.) in the reaction vessel failed to burn in the Bunsen flame. In this reaction, 9.04 g. NH2OH.HCl could be used to replace Mn(NO3)2. At -70 under dry N, I (from 20 g. Na) in NH3 was shaken 2 days with 23 g. CH2Cl2 at about 23 (under 10-12 atm. pressure), the reaction vessel opened at a low temp., the NH3 evapd. at room temp., and the cooled mixt. shaken 10 min. with 150 cc. PhCH2OH, cooled, and treated with 125 cc. 80% AcOH, then with 50 cc. H2O, and distd. in vacuo; the distillate (collected at -70), treated with CaCl2 and redistd., gave 8% (1.4 g.) MeCCCCH (III), b. 75-5.5, m. -45 to -35, nD20 1.4717 (also given as 1.4817), d204 0.7926 (also given as 0.7909). By a modification of this procedure in which NH4Cl was added in the later stages of the reaction, the yield of crude III was increased to 23.6% (but almost 1/2 of this was lost in purification). BrCH2CCH (IV) (17.7 g.) added dropwise to I (from 10 g. Na) in NH3, followed by addn. (after 5.5 hrs.) of 26 g. NH4Cl at -34, gave 16.3% III, or, when 90 cc. PhCH2OH and 30 g. AcOH were used in place of NH4Cl, 17.9% III (based on IV used).
By-products of this reaction were 44% of a Br-free polymer and 35% CHCCH2NH2. The following derivs. of III were prepd.: C5H3Cu, dark yellow, exploding under shock or when rubbed; C5H3Ag, yellowish-brown, highly explosive, even when treated with concd. HNO3 (formed from aq. AgNO3 in NH4OH); AgC5H3.AgNO3 (formed from AgNO3 and III in alc.). III with Adams catalyst in EtOH added somewhat less then 8 atoms H, forming C5H12, indicating, however, that partial polymerization had also occurred. Br in CHCl3 with 2 g. III formed C5H4Br4, colorless oil, nD 1.555. Freshly distd. III (3.2 g.) in 4 vols. Et2O added to EtMgBr (from 15.9 g. EtBr) at -50 and treated gradually with dry CO2, followed by treatment at -15 with ice and satd. aq. NaHSO4, extn. with Et2O, drying of the ext. with CaCl2, and treatment with EtOH-NH3 gave a reddish NH4 salt, which, when decompd. with 20% H2SO4 and extd. with Et2O and petr. ether, gave 0.52 g. of a monocarboxylic acid, C6H4O2.H2O, needles (rapidly darkening at 35) and losing H2O only with the greatest difficulty. III, treated with NaNH2 in NH3 at 60 and with MeI at -65, yielded (CCMe)2 (V), m. 64.5. The reaction leading to V gave exptl. evidence that III was 1,3- and not a 1,4-pentadiyne. Evidently "methyldiacetylene" prepd. by Pr.acte.evost (C.A. 20, 2146) by the action of KOH in alc. on MeCHBrCHBrCHBrCH2Br was not identical with III. MeCCH was prepd. in quantity as the Cu compd. (VI) by Nov.acte.ak's method (C.A. 5, 39) from Mg2C3, which was formed by heating Mg in (O-free) H with an appropriate hydrocarbon at 700. The best yields (50%) of VI were obtained with C2H4; C3H7, paraffin oil, and petr. ether gave 34-42% VI, whereas PhMe failed to react. VI (50 g.) shaken 2 days with O, followed by acidification with aq. H2SO4, gave 14.1 g. (crude) V, purified by steam distn., m. 68.5. I was treated with (CH2Br)2 in NH3 at -60 and shaken 1.5 days at 20; after shaking 0.5 hr.
with NH4Cl, removal of the NH3, evacuation of the reaction vessel, heating at 100, neutralization of the resulting distillate with aq. H2SO4, treatment with CaCl2, and redistn. in vacuo, there was formed 2.1 g. (HCCCH2)2 (VII), b760 84-9. (In the presence of PhCH2OH and AcOH this yield decreased to 1.3 g.) The reaction temp. appears to be critical, because at 40, only polymerization products were obtained. I in NH3 reacting 10 hrs. with 100 g. liquid CH2.CH2.O at -34, followed by evapn. at 40, treatment with abs. alc. under N, and, after 12 hrs., acidification below 50 with dry HCl (with dimethyl yellow as indicator), filtration, neutralization with dry Na2CO3, and fractionation gave about 52% HCCCH2CH2OH, b760, 128.5-30, which, with PBr3 and pyridine at -30, gave about 32% HCCCH2CH2Br (VIII), b760 109-10. By the usual condensation method I (from 8.2 g. Na) and 14 g. VIII gave 0.4 g. VII. In the presence of 1 kg. Cu2Cl2, 400 g. NH4Cl, 100 g. Cu powder, 420 cc. H2O, and 24 cc. HCl within 5 days, 70 g. C2H2 reacted with 60 g. MeCCH, giving, after distn. and fractionation in the presence of p-C6H4(OH)2, 6 g. pure MeCCCH:CH2, b. 59.2-60.1, nD20 1.4494 (cf. Jacobson and Carothers, C.A. 27, 2419).

Axt - 14-5-2008 at 03:34

The attachment contains the preparation of the mercury "salt" of methylacetylene. Its not a salt rather an organo-mercury compund. Its precipitated from K2HgI4, which is formed by mixing HgCl2, KI and NaOH.

Theres no mention of it being explosive, rather "After a crystallization from methyl alcohol the pure dipropinyl-mercury
melted at 203-204' (uncorr.) with slight darkening."

[Edited on 14-5-2008 by Axt]

Attachment: mercury methylacetylide.pdf (565kB)
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stygian - 14-5-2008 at 05:27

Regarding synthesis of methylacetylene-propadiene from acetone, see http://www.freepatentsonline.com/4301319.html

Formatik - 14-5-2008 at 10:39

Quote:

Originally posted by Axt
Even though the Ag salt is quite a weak explosive, resembles blackpowder in its effect. I'd be interested if anyone can form the Cu salt of MA. Though I've failed in my attempts, it can be done. I searched for preparations but all are less then convenient (though they also give long winded routes to the Ag salts).

I've even tried ammonicial Cu(NO3)2. But below we'll know why no precipitate formed. Beilstein says hydrocarbons of the type C(n)H2(n)-2, which have two carbon atoms in a triple bond react with aqueous or even acidic solutions of HgCl2, HgSO4, or mercury acetate to build non-explosive salts.

Concerning the mercury salts, Beilstein says propyne easily reacts when shaken with aqueous solutions of HgCl2, HgSO4, or mercury acetate, with more difficulty HgBr2, and not with HgI2. What results (from HgCl2, etc) Beil says are precipitates from the propyne, non-explosive mercury salts, which easily solubilize in HCl, forming acetone. If propyne is led into a solution of HgI2 in KI, which has KOH, added, a crystalline precipitate of (C3H3)2Hg results (Ber. 17, 13).

(C3H3)2Hg also results from leading propyne through water-containing mercury oxide. This compound is fine glancing needles (from hot alcohol). Unsol. in water, almost insol. in cold alcohol. Sol. in HCl, forming propyne. It does not explode when heated. With alcoholic mercuric chloride it gives a crystalline precipitate, which gives off acetone with acids.

2 C3H4.3HgO.3HgCl2:

is a fine crystalline precipitate, obtained from leading propyne into a cold mercuric chloride solution. If mercuric chloride solution is hot (90-95°C) acetone forms immediatley, and this same amount of salt can continously convert propyne into acetone. The complex is insoluble in water, cold alcohol. Sol. in HCl, forming HgCl2 and acetone. It decomposes quietly when heated. Decomposed by bromine without forming acetylene bromide. 3 C3H4.5 HgO.HgSO4 + 7 H2O - Precipitate. Barely soluble in dilute H2SO4, easily in hydrochloric acid. 2 C3H4.3 HgO.Hg(C2H3O2)2. Amorphous precipitate, easily decomposed by hydrochloric or acetic acid.

The copper salt, which might have the formula of (C3H3)2.Cu, is said to glow and smolder out when heated. It forms propyne with HCl. It is soluble in a mixture of NH3 and NH4Cl, so that's why HCl solubilized Cu2Cl2 which is saturated with NH3 that then absorbs propyne, does not form a precipitate.

[Edited on 14-5-2008 by Schockwave]

Axt - 14-5-2008 at 11:16

Very interesting Schockwave, with both mercury and copper methylacetylides being non-explosive. Quite a contrast to the acetylides.

So it was likely the methylacetylide that I obtained from a cuprous solution, though that would make it CuCCCH3. The image I attached above has gone dead so I'll re-attach it. Indeed it glowed and smouldered as in the description you gave. Does it mention a colour?

chloridecomplex.jpg - 7kB

MagicJigPipe - 14-5-2008 at 12:12

I would like to comment that while MAPP gas is more expensive than propane, it is less than $10 a bottle in the US. Even the "self striking" attachment is only $20 and it comes with a bottle of MAPP. I mean, I bought a kit that came with MAPP gas and an oxygen cylinder plus a plastic hose type adapter with a bunsen burner type tip. The O2 and gas flows could be adjusted, as well, to give varying flame types. It was only $40 and it is very easy to attach a rubber hose to the tip of the torch for the purpose of bubbling through a liquid.

Also, MAPP gas does contain LPG (propane and butane mostly) which usually has a warning chemical (usually a thiol like ethanethiol).

Formatik - 14-5-2008 at 13:10

Quote:

Originally posted by Axt Does it mention a colour?

No color is mentioned.

There's also more on silver methylacetylide in Gmelin Ag [B 5], p. 14: they also say deflagration at 150 deg., but also mention that it can be dried at 60 to 70 deg. They say the white compound turns yellow-red in light and later grey. They also mention its preparation from AgNO3 in aq. NH3 (probably precipitates much faster). They also say it is not "contact-sensitive". Mineral acids, HS-, and heating with acetic acid releases propyne. But with Br2, PCl5, and SbCl5 it reacts with ignition. With solutions of I2, AgI and CH3C:.CI (methyliodoacetylene) result, solutions of Br2 react analogously [C.Liebermann - Liebigs Ann. Chem. 135 [1865] 266/90, 268/71].

And other silver acetylides (p.12-17), these following are just the ones specifically mentioned to be energetic:

AgC:.CC:.CCH3 ( = AgC5H3) is made by reaction of aqueous ammonicial solution of AgNO3 with CH3C:.CC:.CH, where it precipitates. It is yellow-brown, and extremely shock- and friction-sensitive compound. With conc. HNO3 an explosive decomposition results (H.H. Schlubach, V. Wolf - Liebigs Ann. Chem. 568 [1950] 141/59, 155). The same reference also mentions AgC:.CC:.CCH3.AgNO3 (= AgC5H3.AgNO3) which results from an alcoholic solution of AgNO3 and CH3C:.CC:.CH. Though nothing was mentioned in Gmelin about its properties.

AgC:.CCF3 (= AgC3F3) is obtained as a white precipitate by shaking a solution of aqueous ammonicial AgNO3 solution with CF3C:.CH. In light it turns bright brown, with mild warming it eventually decomposes to Ag. But by quick heating it deflagrates violently. It's soluble in organic solvents (R.N. Haszeldine - J. Chem. Soc. 1951 588/91; Nature 165 [1950] 152/3).

2 AgC:.CCR'R"OH.AgCH3COO (where R' = C2H5, R" = CH3; R' = R" = C2H5; R' = i-C3H7, R" = H), with the sum formulas being AgC:.CCR'R"OH:AgC6H9O, AgC7H11O or AgC6H9O. The compounds result from alkinols CH:.CCR'R"OH and double the mole amount of AgCH3COO in aqueous solution, where they precipitate as colorless amorphous solids. They can be dried next to H2SO4, they are explosive and solubilize in dilute HNO3 (Ber., 64 [1931] 2371/5).

Alkoxyalkinyl silver compounds: an Ag-deriative of CH:.COC2H5 precipitates from its interaction with a solution of ammonicial AgNO3 in C2H5OH as a colorless crystalline solid. It discolors in light forming Ag, but it detonates violently from mild heating. Insoluble in H2O and organic solvents. The analogous Ag-deriative of CH:.COC3H7 is darker than the ethoxy compound (Zh. Obshch. Khim. 15 [1945] 394/400, 397/8; C.A. 1946, 4657).

Formatik - 26-5-2008 at 14:34

A dirty grey precipitate results from a solution containing mercuric chlorate and saltpeter and MAPP. I'm not sure about the formula or properties, though it could be a compound analogous to chloratotrimercuraldehyde. In small amounts it deflagrates vigorously from a flame, confined in Al-foil it will pop and puff very mildly, even if mixed with KClO3. A real hard hammer blow will cause it to snap. Although this doesn't show that interesting energetic properties an analogue of far more dangerous chloratodimercuraldehyde might.

[Edited on 26-5-2008 by Schockwave]

Formatik - 26-12-2008 at 01:01

I've found corroboration for the color of the copper salt. The Journal für praktische Chemie (1866), Vol. 2, p. 177 says that leading propyne into ammonicial CuCl yields the "well-known" yellow precipitate of copper methylacetylide. It also decomposes from dilute HCl to give off the alkyne. Then the Handbuch der Chemie (1867), p. 529 says it is siskin yellow. Leading propyne into 2KCl.CuCl (or the iodide analogue) it is richly absorbed and colors the solution yellow and precipitates bright yellow crystals which are complexates of the copper (I) halide with the methylacetylide.

The latter ref also mentions gold methylacetylide. Made by leading propyne into an ammonicial solution of "unterschwefligsaures Goldoxydul-Natron", which is just sodium aurothiosulfate Na3Au(S2O3)2 made from mixing aq AuCl with aq Na2S2O3, or made from AuOH mixed with Na2S2O3. For AuOH: precipitate cold from SO2-decolorized gold salt solution using aq KOH, it's darkviolet and freshly precipitated it is soluble in cold water with blue color.

Silverpropyne also complexes with sulfate or chloride. But for one that can't be found in the literature that is the silver chlorate methylacetylide complex, the likley structure is as shown below and which is similar to the chloride analogue mentioned in Annalen 157, 242, possibly as a hydrate. A perchlorate also likley exists.

It is made by leading propyne into aq. solution of AgNO3 which had KClO3 dissolved into it. It is a whitish solid similar to the AgC3H3, but less light-sensitive. The dangerous thing is the salt tends to clump even after washing with anhydrous ether. It is shock sensitive (but less than Ag2C2 or AgN3), over >0.03 Nm. In small amounts exposed to open flame reacts similar to AgC3H3 giving large amount of soot, but if it is under light moderate confinement it will detonate with quite some brisance and a loud report, unlike the AgC3H3 which puffs lightly with a pop and low brisance. The reason for the violent reaction may be due to the gases formed on its decomposition including ClO2, in addition to the triple bond energy source. Added to conc. HCl, it is destroyed giving a Cl2-like odor (probably various gases).

silv complex.jpg - 2kB

Axt - 6-1-2009 at 23:46

You digging up and posting these references is much appreciated Formatik. I assume the chlorate complex you mentioned is one of your own experimentation? Sounds like an interesting one to try as an initiating explosive.

Formatik - 7-1-2009 at 12:12

Right, and I suspect it has initiator properties also, but it might be inferior to silver acetylide and azide. The regular Cu and Ag salts can also be oxidized to yield dialkynes.

carbonfeind - 4-6-2010 at 18:17

I realize that I have yet again revived a year old thread, but I thought it would be better to post this here instead of making a new thread. I hope that is OK.

I have done a bit of work with the chlorate complex of silver methylacetylide.
It was synthesized as follows:

In a 100ml beaker 2.5 grams of AgNO3 and 1.5 grams KClO3 were dissolved in 39ml of room temperature distilled water.
This solution was then poured into a 100ml graduated cylinder.

MAPP gas from a "bernzomatic" cylinder was led into the solution via a glass tube for about 5 minutes.
The precipitate was allowed to settle at the bottom and as much water was decanted as possible.
It was then filtered and rinsed several times with cool acetone and allowed to dry in the dark.
The silver methyl acetylide-chlorate has an extreme affinity for clumping so care should be taken as to not allow it to dry in large chucks.

The silver methylacetylide-chlorate complex deflagrates in a quick crackling/hissing flash with evolution of black smoke. It appears to deflagrate slower than the straight methyl acetylide.
If there are lumps present, or the otherwise loose powder is even slightly compacted, it will not deflagrate, but detonate. this gave me quite a fright once when I first made this compound as I was expecting a "thump" but instead got a sharp "bang". So much care must be taken when attempting to observe the deflagration.

As you would imagine, little confinement is needed for DDT.

This compound appears to have initiating capability on par with silver acetylide, but no really proper test were done. However, when equal amounts of equal densities are detonated on a thin aluminum sheet, the dent created by the silver methyl acetylide chlorate is much more pronounced than silver acetylide.

Friction and impact sensitivity appear to be relatively equal, but once again, no proper testing was done.

I also tried to form the perchlorate complex, but I appeared to be unsuccessful. Both ammonium and potassium perchlorate were tried, maybe a dilute solution of HClO4 would fare better?

Formatik - 8-6-2010 at 00:48

It's possible I could have underestimated the propyne complex, since it was not as flame and impact sensitive as acetylide-nitrate and azide. The chlorate gives it obvious extra energy and probably sensitivity. Silver chlorate itself has some energetic properties, i.e. Sodeau found silver chlorate explodes easily by a hammer blow. Heating AgClO3 to about 350 deg. also caused explosion. With combustibles, AgClO3 also detonates more easily than KClO3 through shock.

-=HeX=- - 9-6-2010 at 04:56

Carbonfiend: Email me at d.martyn@live.ie

Anyways... As for the silver one. Here is an idea... Use Carbonfiends synth for the chlorate double salt, with an excess of silver nitrate. Then add, with stirring, a mixed basic solution of alkaline sodium picrate and sodium azide. It should form a nice complex...

OT but making a serious excess of AgNO3, adding C2H2 with rapid stirring and heat while also dropping in NaN3 makes what appears to be at least a very good coprecipitate of Silver Azide-Acetylide. I plan to try this with chlorate soon-ish - I am in the middle of exams - and examine the PPT under microscopy.
IIRC for good clathrate/co-ppt, we need to keep the cauldron hot, the addition slow, and the stirring fast

quicksilver - 9-6-2010 at 05:52

One of the production elements in azide materials is to keep precipitate cold (5C) to prevent production of needle crystals. ANY time azide is utilized, microscopic examination is prescribed to determine if needles are present. If so; the batch should be destroyed. This is from a German & British patent & SOP from plant production techniques. The microscope should show round-ish particulate of inconsistent shape (even in clathrates) and any needles are deemed too dangerous to maintain in yield.

-=HeX=- - 11-6-2010 at 15:04

That is true, however I find that it forms fine material - I have not 'scoped it yet, but when I get half a chance I shall. It may well form micro-needles, but it felt like fine salt to handle. Not quite granular, not powder, just in between. A lot like the Azo Clathrate (4/12) is to handle. Also, I was thinking of it as 'clathrate' and the rule there is heep it hot and stirred while adding slowly!

I am thinking that Rosco could illuminate us here, but I had an idea (OT again but kinda relavent).
Regarding his Basic Lead Picrate-Chlorate-Nitrate mixture he referred to as a good 'Primary Flash Ignitor' and it is a clathrate material. Would replacing the Chlorate with Perchlorate, having a huge excess of Lead Nitrate, and then dropping in slowly Sodium Azide under heating and stirring be the way to form the mysterious 4/16 or 4/17 perchlorate based azo chlathrate?

I wish to test that material, as I have an idea for it to be mixed with DPNA or DPB in a matrix of NC to form small 'cylinders' of 'cast primary' which would have a bridgewire assembly inserted into them, and then be used as part of the CLD project. DPNA or DPB are both excessively hot - 2.5mg to initiate PETN! Microtek or PDB can confirm this.

The idea of using the hottest clathrate there is is to help with unequivocal initiatiory performance - i.e. to shorten the DDT in order to enhance efficiency.

I was thinking, for the testing of interesting primaries, could we devise a 'critical diametre' method of testing? Or some such method...
I already have a test-method devised (a series of 'benchmarks' however to test a range of primaries, and repeat each test 3-5 times as required by proper scientific method, would be an undertaking similar to that of a Masters thesis or PhD. Perhaps I will do it for my Masters or PhD

There are literally tens of thousands of potential tests - and they would all help fill in the fragmented picture of how these interesting materials function!

pdb - 22-6-2010 at 07:16

Talking about needles and DPNA, I obtained very regular micro-crystals by adding NaNO2 as powder iso aqueous solution (which leads to bigger crystals, irregular both in size and shape). From a macro viewpoint, the product prepared this way is easier to handle, although still not really free flowing.

(I'm puzzled by your "DPB".. what does it stand for ?)

-=HeX=- - 27-6-2010 at 13:12

I will find the other name for DPB, but basically DPNA except replace the 3-nitroaniline with 2,4-nitroaniline. IIRC you made something of the sort. INCREDIBLY potent primary, and I thank you for introducing me to DPNA and such.

More on the topic, today I found interesting article about making double salt of Ag2C2:AgClO4. The article is moreso about the crystal structures but I think it is giving me ideas that Ag2C2 could be used as a basis for a clathrate type mixture.

I will try attach article now...

Attachment: acetylide-perchlorate double salt.pdf (94kB)
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