Sciencemadness Discussion Board

para DDNP!

KABOOOM(pyrojustforfun) - 22-5-2004 at 00:07

I got the spark from <a href="" target="_blank"></a>it defines diazooxides as: Diazocyclohexadienones, which may also be considered as dipolar diazonio phenoxides, obtained by diazotizing aromatic primary amines having a hydroxy group in an ortho or <font size=6>PARA</font> position. Also known as diazophenols.
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the only diazooxide of importance in the energetic materials field is DDNP. which is among the ortho diazophenols I became curious to know if a para isomer of DDNP could be made. to do so we need to prepare 4-amino 2,6-dinitrophenol (let's call this p-picramic acid for short) and then diazotating it to diazo 2,6-dinitrocyclohexadienone.
for preparation of p-picramic acid, nitration of p-aminophenol isn't an option 'cause the HO- and H<sub>2</sub>N- in para position most likely makes it prone to oxidation (converting it to quinone further oxidizing it may even lead to ring destruction) one way to protect the amino group in aromatic nitrations is acylating it. thus N-acetyl p-aminophenol (active ingredient in acetaminophen/tylenol tablets) should resist toward oxidation better than p-aminophenol does. both hydroxy and acetylamino are activating groups the former being the strongest so a mild nitration should produce 4-acetylamino 2,6-dinitrophenol which upon hydrolyzation should yield our desired compound "p-picramic acid"
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another method again starting with OTC materials would be:
mononitration of p-dichlorobenzene (some mothballs) followed by hydrolyzation (boiling the nitro p-dichlorobenzen in a solution of NaOH in water) resulting in formation of NaCl and the sodium salt of 4-chloro 2-nitrophenol. acidify the solution to obtain the 4-chloro 2-nitrophenol.
nitrate 4-chloro 2-nitrophenol to 4-chloro 2,6-dinitrophenol. dissolve the product in hot EtOH and pass NH<sub>3</sub> through the solution hoping to get p-picramic acid (along with ammonium chloride byproduct)
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[Edited on 22-5-2004 by KABOOOM(pyrojustforfun)]

KABOOOM(pyrojustforfun) - 2-9-2004 at 11:43

when I made this thread I didn't have encylopedia of explosives and related items....
2,6-Dinitrobenzene-4-diazo 1-oxide or 2,6-Dinitro-4-diazophenol [ called 2,6-Dinitro-p-chinon-diazid-(4) in Ger] ,
flakes(from w), mp- expl violently ca 190°. Can be prepd by diazotizing 2,6-dinitro-4-aminophenol or its methyl ether by NaNO<sub>2</sub> in acid solns(Refs 2 & 4). The thermal decompn of these dinitrobenzenediazooxides, in a vacuum, has been studied betw 50 & 120° by Vaughan & PhiHips(Ref 15).Under these conditions, 4,6-dinitrobenzene-2-diazo-1-oxide appears to be less stable than the 2,6-dinitrobenzene-4-diazo-1-oxide
<i>Analytical.</i> Schaefer & Becker(Ref 13) developed a new method for detg diazo N in stable diazo compds. This method consists in treating a sample with a large excess of Ti chloride and measuring the amt of evolved gas. A method for detg nitro N in stable diazo compds, provided the diazo N is known, consists of slowly adding a soln of the sample in acetic acid, with swirling, to a measured vol of Ti chloride
<i>Refs:</i> l)Beil 16,524 & [287] 2)Beil 16,531 3)P.Griess,Ann 113,205(1860) 4)R.Meldola & F. G. Stephens, JCS 87, 1204-5(1905) 5)L.V.Clark, IEC 25,663-9 (1933)& CA 27,3611(1933) 6)R.S. Hancock & L. C. Pritchett,USP 1952591( 1934) & CA 28,3426(1934) 7)H.B.Alexander, USP 2103926 (1938) & CA 32,1714(1938) 8)L.W.Babock,USP 2155579(1939) &CA 33,5869(1939) 9)Davis(1943) 443-6 10)Blatt,OSRD 20141940 ll)R.L.Grant& J .E .Tiffany,IEC 37,661-6(1945) & CA 39,3671 (1945) 12)A.F.Belyaev &A. E. Belyaeva,Dokl AkadN52,503-5(1946) &CA 41,4310(1947) 13)W. E. Shaefer &W. W. Becker, AnalChem 19,307-10& CA 41,4062(1947) 14)G.F.Roland,USP 2422043 (1947) &CA 41,5725(1947) 15)J.Vaughan &L. Phillips,JCS 1947,1560-5 &CA42,357U1948) 16)H.FicherouHe & A. Kovkche,Mp 31,7-27(1949) &CA 46,1186-7(1952) 17)H.Henkin &R. McGill, IEC ‘i4, 1391-5(1952) & CA 46,8857-8(1952) 18)-4. Suzuki, JIndExplSocJapan 14, 142-63(1953) & CA 49,1 1281(1955) 19)A.G.Schuricht, USP 2662818 (1953) & CA 48,3692(1954) 2@H.subJIndEwl-SocJapan 15,277-81(1954) & CA 49,11283(1955) 21)T.Tsukii & S. Kichuchi,JapP 4443(1954) & CA 49,10628(1955) 22)W.A.Gey & H. L. Bennet, JChem- Phys 23, 1979-80(1955)& CA 50,2174(1956) 23)H. Rosenwasser,OakRidgeNatlLab(ORNL)Rept 1720 (1955) & CA 50,14229(1956) 24)Sax(1957),547 25)PATR 1740, Rev 1(1958 ),101-5

2,6-Dinitro-4-aminophenol, 4-Amino-2,6-dinitro-phenol or Isopicramic Acid (lsopikraminsaure in Ger). Yel-bm ndls(from w), mp 170° with sl decompn. Sl sol in w(0.082 g/100 g at 22° and 0.812 g at 100°), very sol in alc and less sol in benz. It expl on heating above the mp. Was first prepd in 1883 by C. W. Dabney(Ref l,p 528). Reverdin et al(Ref 2) prepd it by treating 2,6-dinitro- 4-acetamidophenol, CH<sub>3</sub>CO.NH.C<sub>6</sub>H<sub>2</sub>(NO<sub>2</sub>;)<sub>2</sub>OH, with HCl. It forms salts, some of them expl, eg potassium isopicramate, (O<sub>2</sub>N)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>(NH<sub>2</sub>;)OK, bluish-black ndls(from alc) v sol in w or alc (Ref 1,p 528)
<i>Refs: </i> l)Beil 13,527, (190) & [293] 2) F. Reverdin et al Bet 37, 4452(1905); 38,1598(1906) & 39, 126(1907)

I think I would invent it if it wasn't already done:D

[Edited on 2-9-2004 by KABOOOM(pyrojustforfun)]

Turel - 2-9-2004 at 11:56

Step 1 will be quite messy and low yielding.
Step 2 very likely will not occur with NaOH, you will need a stronger base and solvent combination to have any results.
Step 3 works fine.
Step 4 is VERY likely to make a mess with your desired product being but one of many produced.
Step 5 does not happen.


madscientist - 3-9-2004 at 14:44

I think step five can be accomplished using a catalyst of some sort, I believe it was CuCl...

Esplosivo - 3-9-2004 at 21:47

I am not sure if this applies in the case of aromatic compounds, but in aliphatic compounds the substitution of a halogen by ammonia is carried out by heating the mixture of the reactants (ammonia must be dissolved in alcohol) in a 'bomb' - reaction under high temperature and pressure. The resultant products would vary in composition though, since the subsituted amine formed would continue to react with more of the halogenalkane. Concentratrations of the ammonia must be equal to or slightly higher than that of the halogenoalkane to obtain a good yield of the expected product.

Well anyway, if this works out for aromatic too it sure would be a messy procedure, recquiring fractional distillation and the 'bomb' container, which at least in my case is not easy to obtain.

[Edited on 4-9-2004 by Esplosivo]

Unequal Halogens

Turel - 4-9-2004 at 22:02

It would work with Br and I, but not with F and Cl. Not so linear a relationship. The mechanisms are different. If it could be made to work, it would not be practical, as the yields would be horrendous and the reaction times long.

mick - 5-9-2004 at 04:31

Many years ago I prepared an amino, nitro, chloro substituted benzene from a dinitro chlorobenzene (I think it might have been 1-chloro-2,4 dinitro because I got 2 isomers but I am not certain now) on a commercial scale with ammonia + ethanol. The ammonia displaces a nitro group rather than the chloro group.The ref was from an old chem. abs. when they gave all the weighs and reaction conditions. I found out the by-product was ammoniun nitrite when I tried to recover some of the ethanol for re-use. When I took the vac of the still the residue when like rocket fuel., I sure if I had evaporated a bit more of solvent it would have detonated.

When I left the company the 45 gallon drum of ethanol + ammonium nitrite had been left in the corner of the yard for a few years. Wonder what happened to it.

[Edited on 5-9-2004 by mick]

KABOOOM(pyrojustforfun) - 5-9-2004 at 11:05

as turel said it's quite possible for that step not to work. the hydroxy and nitro groups are about in their worst position (for activating the Cl for nucleophilic substitution I mean. in such reaction nitro activates it whilst the hydroxy deactivates it. also keeping in mind that functional groups have their least effect on meta position)
mick: 1-chloro 2,4-dinitro benzene can react with ammonia (in EtOH) to form 2,4-dinitroaniline. ammonia replaces the nitro specially when there are multi electron donor groups on the ring and a nitro group (or other electron donor group?) at it's neighborhood (ortho). eg both chloropicric acid and tetranitrophenol yield aminopicric acid upon action of ammonia on em. the chloro and nitro group being relpaced respectively. other examples are HexaNitroBenzene or PentaNitroAniline to TriAminoTrinitroBenzene and tetranitroaniline to DiAminiTrinitroBenzene.
btw my guess is the initial compound you were dialing with was 1-chloro 2,3-dinitrobenzene or 1-chloro 2,5-dinitrobenzene or 4-chloro 1,2-dinitrobenzene.

[Edited on 5-9-2004 by KABOOOM(pyrojustforfun)]

Organic Synthesis To The Rescue

Turel - 6-9-2004 at 00:53

All is not lost. O-Syn methods can fabricate any molecule via constructive strategies. A myriad of simple and cheap feedstocks could be used to synthesize this product. There are far too many individual valide routes to detail from several similar feedstocks, so I will simply use a similar starting compound to the one originally indicated. Suffice to say, this is not the only feasable route, I'm confident there are at least 20+ similar others to suit personal tastes and on-hand reagents.

If anyone wants further elaboration on any methods indicated below, just ask. For now:

1. p-hydroxyaniline + phthalic anhydride ----> phthalimide-protected derivative
2. Reimer-Tiemann to produce phthalimide-protected 2-hydroxy-5-aminobenzaldehyde
3.Kolbe-Schmitt to phthalimide-protected 5-amino-3-formyl-2-hydroxybenzoic acid.
4.Oxidize the formyl to the carboxylic acid to produce phthalimide-protected 2-hydroxy-5-amino-isophthalic acid
5.Amidate the carboxyls with urea.
6.Hoffmann Hypohalite Degradation to produce the 5-phthalimide-protected 1,3-diaminophenol
7.Oxidize both free NH2 functions using DMDO in acetone to NO2 functions.
8.Hydrolize the phthalimide protecting agent to produce the final product.

A bit lengthy eh? I would be inclined to agree, and I'm sure there are shorter/better paths, but it is nearly 3am here, so cut me some slack. :P



Turel - 6-9-2004 at 00:59

I forgot to mention, step two in the original post cannot be accomplished with the recommended stronger base and solvent, because of the benzyne mechanism's predominance.

The compound will be deprotonated at the site between the NO2 and meta Cl functions, not ortho to the ortho/para Cl. This will cause immediate extrusion of the nearby Cl in the form of the leaving group Cl- ion, giving rise to transient bond formation (benzyne) which will undergo further reactions with itself and the hydroxide ions present, and the products produced, producing a vicious chain reaction polymerization.

Neat stuff.

mick - 7-9-2004 at 01:38

Must have been the 4-chloro-1,2-dinitrobenzene

I like the method above

[Edited on 7-9-2004 by mick]


KABOOOM(pyrojustforfun) - 7-9-2004 at 11:06

why not nitrating the product of the first stage? the phthalimido group should have less activating power on the ring than the acetylamino group which means higher % of our desired isomer will result from its nitration than the nitration of acetaminophen.

and what about :
<i>p</i>-hydroxy benzoic acid =(NA&SA)=> 3,5-dinitro 4-hydroxybenzoic acid =(esterification with alcohol)=> the ester =(hydrazine)=> 3,5-dinitro 4-hydroxybenzoyl hydrazide =(nitrosation followed by nitrogen loss and hydrolyzation)=> isopicramic acid

<i>p</i>-hydroxy benzoic acid is a "common" chemical and there are many ways of obtaining or synthesizing it.<!--

[Edited on 8-9-2004 by KABOOOM(pyrojustforfun)]

PerFecTioNisT - 24-1-2005 at 11:36

OK I.m very interesting about this PE.I heard that he's one of the best PE and I want to make it.But nobody for yours didnt say how to make it.I will be very thankless ,if somebody tell how to make this primary.Thank you

[Edited on 24-1-2005 by PerFecTioNisT]