Diazodinitrophenol

Other well-known initiating explosives are lead trinitroresorcinate (lead styph-nate), diazodinitrophenol (DDNP), tetrazene andmercuric-5-nitrotetrazole (MNT). 

Normal lead styphnate (LS) [Structure (2.10)] was first reported by Von Herze in 1914, although its basic salt, that is, basic LS was prepared by Griess [7] way back in 1874, by the reaction of acidified magnesium styphnate with lead nitrate/acetate in hot aqueous solution. It is precipitated as mono hydrate and consists of reddish-brown rhombic crystals. It is filtered off, washed with water, sieved through a stainless steel sieve and dried. Like other initiatory explosives, it is kept in wet conditions until used. 

Diazodinitrophenol (DDNP or Dinol) [Structure (2.11)] or 4,6-dinitrobenzene-2-diazo-l-oxide was first prepared by Griess [9] in 1858 but was developed commercially as a detonating agent 70 years later. It is prepared by the diazotization of 

It has good storage properties and is a preferred initiating explosive particularly in the USA and Japan as it is relatively insensitive to impact and friction compared with other initiating explosives. Its VOD is 6900ins 1 at a density of 1.58gem 3. 

The 2-diazo-4,6-dinitrophenol (dinol, diazol, DDNP, DDNPh, or DADNPh) is the first-ever synthesized diazonium compound. Its synthesis is attributed to Griess [1] who prepared it by introducing nitric oxides into an alcoholic solution of 2-amino-4,6-dinitrophenol (picramic acid) [1,2]. Its explosive character was, however, first reported more than 30 years later in 1892 by Lenze [3]. 

Although DDNP has been known for almost 150 years, its structure is still debated and general consensus does not exist. The most obsolete suggested structures are not mentioned here but may be found in [4]. 

The properties (chemical, physical, and spectral) of general ortho (structure I, benzo [d][l,2,3]oxadiazole) and para (structure II, 2-oxa-3,4-diazabicyclo[3.2.2] nona-l(7),3,5,8-tetraene) isomers of diazophenols are very similar indicating that the structures should also be similar. Even though the cyclization and formation of two rings does not seem to be unreasonable for the ortho-isomer, it definitely does not look probable for the para-isomer. It is therefore assumed that the structures I and II are rather improbable for diazophenols [5]. This assumption was confirmed when structure I was prepared and shown to be unstable even in a solid argon matrix. The meta-(3-diazo) isomer has not been reported [5, 6]. 

The possible cyclization of the diazo structure III of DDNP and formation of cyclic isomer IV is improbable based on the property-related assumption mentioned above. The theoretical studies employing the AMI level of theory further support this conclusion [6]. 

X-ray diffraction of DDNP was first carried out by Lowe-Ma et al. [5] and later confirmed by Holl et al. [6]. The bonding of DDNP has been discussed on the basis of theoretical calculations and compared to the results of X-ray diffraction, IR, and NMR [5, 6]. 

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Lead Azide. The azides belong to a class of very few useflil explosive compounds that do not contain oxygen. Lead azide is the primary explosive used in military detonators in the United States, and has been intensively studied (see also Lead compounds). However, lead azide is being phased out as an ignition compound in commercial detonators by substances such as diazodinitrophenol (DDNP) or PETN-based mixtures because of health concerns over the lead content in the fumes and the explosion risks and environmental impact of the manufacturing process. 

Diazodinitrophenol," Enyclopedia of Explosives and Relateditems, Vol. 5 D1160, PATR 2700, ARDEC, Dover, N.J., 1972. 

Trinitroresorcinol 6% 2) PbDNAzP 15, Ba nitrate 25, Pb dioxide 12, Diazodinitrophenol 17, Trinitroresorcinol 8, ground glass 22, gum arabic 1%... 

Sodium Dinitroazidophenolate (called Sodium Dinitrophenylazide by McNutt). Na0.N3.C6H2(N02)2. Prepd from diazodinitrophenol and Na azide as an intermediate in the prepn of Pb Dinitroazidophenolate, which is obtained on addition of Pb nitrate to the Na salt (see above). No mention is made in the ref about using this salt in expl mixts... 

Diazodinitrophenol is a yellow powder, almost insoluble in cold water. It does not detonate when unconfined, but when confined has a velocity of 6900 m s-1 and a density of 1-58 g ml-1. For an initiating explosive it is relatively insensitive to friction and impact, but still is powerful when confined. DDNP has good properties of storage and has found application in detonators, particularly in the U.S.A. 

Tetrazene is a light yellow crystalline substance, insoluble in water and most organic solvents. The density is low under normal conditions, but on pressing can reach approximately 1 g ml-1. Tetrazene is weak as an initiating explosive, and is therefore not used alone. It has no advantages to commend it for use in commercial detonators, but does find application in the manufacture of military and other percussion caps. Like diazodinitrophenol, tetrazene does not detonate when ignited in the open, but only when ignited under confinement. 

The original initiating explosive used by Nobel and all manufacturers for many years was mercury fulminate. This had the disadvantage of decomposing slowly in hot climates, particularly under moist conditions. For this reason mercury fulminate is no longer widely used. In most countries it has been replaced by a mixture of dextrinated lead azide and lead styphnate. In the U.S.A. some detonators are made containing diazodinitrophenol. 

The initiating explosive used must ignite with certainty from the spit of a safety fuse. It must be remembered that the intensity of the spit can be reduced if the safety fuse is not cut squarely and also that the fuse may in practice not always be fully inserted into the detonator. Lead azide by itself is not sufficiently easily ignited to give a satisfactory plain detonator and it is therefore used in admixture with lead styphnate, which is very readily ignited by flame. The proportions of such mixtures vary from 25 to 50% of lead styphnate. Mercury fulminate and diazodinitrophenol are sufficiently sensitive to flame not to require such additives. 

Bleitrinitroresorcinat-Gemisch, auch mit Tetrazen fur Anzundhiit-chen. Diazodinitrophenol, als schwermetallfreie Anztindsatzkom-ponente. 

Wenig loslich in Wasser, etwas loslich in Methanol und Alkohol, loslich in Aceton, Nitroglycerin, Nitrobenzol, Anilin, Pyridin und Essigsaure. Diazodinitrophenol dunkelt im Sonnenlicht schnell. 

Aus Pikraminsaure kann durch Diazotieren -> Diazodinitrophenol her-gestellt werden. 

Als - Initialsprengstoffe werden - Diazodinitrophenol Oder das neu entwickelte Strontiumdiazodinitroresorcinat eingesetzt. Als Oxidati-onsmittel dienen spezielle Formen des Zinkperoxids. Daneben konnen die Anzundsatze Metallpulver, z. B. Titan, enthalten. Teilweise wird - Tetrazen als Sensibilisator benotigt. 

Primary explosives differ from secondary explosives in that they undergo a rapid transition from burning to detonation and have the ability to transmit the detonation to less sensitive (but more powerful) secondary explosives. Primary explosives have high degrees of sensitivity to initiation through shock, friction, electric spark, or high temperature, and explode whether confined or unconfined. Some widely used primary explosives include lead azide, silver azide, tetrazene, lead styphnate, mercury fulminate, and diazodinitrophenol. Nuclear weapon applications normally limit the use of primary explosives to lead azide and lead styphnate. 

Diazodinitrophenol (CgH Oj) has been used as an initiator in industrial blasting caps. It is less sensitive to impact, friction, and electrostatic energy than other primary explosives. It is orange-yellow in color and is sparingly soluble in water.11... 

For the terrorist, TATP and HMTD offer easy sources of primary explosives. Consulting the do-it-yourself literature, it can be seen that there are two other commonly recommended primary explosives—lead azide Pb(N3)2 and mercury fulminate Hg(ONC)2, but these are difficult to prepare cleanly. The synthesis of diazodinitrophenol (DDNP) (Fig. 2.5), common in commercial detonators, is reported in such publications, but apparently is rarely attempted by clandestine chemists. Typically, the brisance of a primary is less than TNT, but the efficacy is the fact that a shock wave can result from a relatively mild insult. 

Some unconfined high expls can also be ignited to deflagration especially if they are in a molten condition (such as TNT), or spread in a thin layer (such as MF or Diazodinitrophenol). In many cases deflagration develops into detonation [See also Detonation (and Explosion), Initiation of] Refs 1) F.P. Bowden, "The Initiation of Explosion and Its Growth to Detonation , PrRoySoc 204A, 20 ff (1950) la) A.F. Belyaev, ZhPraktKhim 23, 432 ff (1950). 

Ethyl Nitrate 2572, Diazodinitrophenol 3087 and 1,1-Dinitropropane 2543 C Note In the report (as well as in many other papers and reports) these temps are called "explosion temperatures . As this term can be confused with temp to which.an expl must be heated to induce expln, we prefer "temperature of explosion when it. concerns "temperature developed on explosion ... 

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