Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2002-07-10
2004-01-06
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C544S180000, C544S196000, C544S195000, C514S241000, C514S246000, C149S056000, C149S076000, C149S119000
Reexamination Certificate
active
06673924
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to novel fused ring structures useful for providing a platform for novel explosive and pyrotechnic compounds, particularly high nitrogen content, low carbon content energetic compounds, dyes, pharmaceutical and other compositions. The present invention includes a precursor compound pertaining to a 1,2,4-Triazolo[4,3-a][1,3,5]Triazine compound, particularly a 1,2,4-Triazolo[4,3-a][1,3,5]Triazine-3,5,7-Triamine, and novel fused ring structures such as triazolyl-tetrazinyl-aminotriazine compounds, and complexes and salts thereof, and other such chemical structures as detailed herein.
2. Brief Description of the Related Art
Development of specialized chemical compounds requires proper precursor chemical structures.
Current methods that purport to synthesize 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine all involve heating dicyandiamide and hydrazine dihydrochloride at elevated temperatures (100° C. or higher) for significant amounts of time in order to condense the dicyandiamide. This method was described by Kaiser et al. in a paper published in the Journal of Organic Chemistry, Vol. 18, 1953, page 1610.
Using this synthesis method theoretically provides for two possible isomeric structures of triazolotriazinetriamine (see I and II below). The first structure is the [4,3-a]triazolotriazinetriamine, pictured below as I. The second structure is the [1,5-a]triazolotriazinetriamine, pictured below as II. The product by Kaiser et al., resulting from the method above, was assigned the structure of I based upon degradation/oxidation studies of the product. However, these types of studies provide for a large degree of uncertainty as to structure.
Recently, product derived from the above process was tested using X-ray diffraction, an extremely reliable technique, and, rather than the expected product I as originally reported, it was found that the actual structure of the product was that of II. The commercial product based upon the above method, sold under the names 3,5,7-triamino-s-triazolo[4,3-a]-s-triazine or 3,5,7-triamino-1,2,4-triazolo[4,3-a]-1,3,5-triazine, has also been tested via X-ray diffraction and found to be the structure of II. Because of the above error, prior to the present invention, there is, therefore, no known process of synthesizing product I. Additionally, patents such as U.S. Pat. No. 3,939,084 to Sullivan purport to use a 3,5,7-Triamino-s-trizazolo(4,3-a)-s-triazine, as well as articles such as “New Synthesis of Dyes of the Triazine”, Series II. VAT Dyes of the Triazolo-Triazine Series by A. Titkov and I. D. Pletnev, Scientific Research Institute of Intermediates and Dyes, translated from Zhurnal Obshchel Khimil, Vol. 33, No. 4, pp. 1355-1357, April 1963 (see also Maeda et al. Japan Kokai 74 24,226 and 74 27,287), which are apparent mislabelings of the 3,5,7-Triamino-s-trizazolo(1,5-a)-s-triazine).
The effects of the structural difference between these two products on the chemical and physical properties are of interest in any application of monotriazolotriazine ring systems. Of particular interest for energetic uses of these products would be the energy release in detonation, which correlates to the density of the materials. An analysis of densities and potential energy releases of the products reveals that the product I has a higher potential energy release value than product II that is significant in defense related energetic systems. The product II has also been investigated for use in the dye industry as a chromophore coupled to anthraquinones and indoles, and, therefore, product I should have similar potential uses. Other aromatic structure systems also are of interest.
Due to the discovery that the chemical sold as product I is actually product II, and the chemical and physical properties of the two products are significant for many uses, it would be desirable to derive product I, and like compounds, provide for synthesis such compounds, as well as developing compounds from processes using product I and like compounds as a precursor.
SUMMARY OF THE INVENTION
The present invention includes a novel compound structure having the formula:
wherein R
1
is —NH
2
, and R
2
and R
3
are independently electron donating groups, preferably where R
1
, R
2
and R
3
are —NH
2
.
The present invention further includes a novel fused ring structure having the formula:
wherein R
4
is a substituent being or replacing the —NH
2
of the precursor, preferably being an electron donating group, and more preferably being —NH
2
, and R
5
is a ring having greater than five atoms within the ring, preferably where R
4
is —NH
2
and R
5
forms a six-member or seven-member ring, more preferably with such ring having three or more nitrogen atoms. The ring may include substituents thereon.
The present invention also includes a pyrotechnic composition comprising a compound having the chemical structure:
wherein Z
+
comprises H
+
or a cation; R comprises a complexing component; and,
wherein m=1, 2 or 3; n=0, 1, 2 or 3; x=0, 1, 2 or 3; and t=0 or 1. The structure provides the complex and salt forms of triazolyl-tetrazinyl-aminotriazine. The present invention further includes a method of making a pyrotechnic composition comprising a triazolyl-tetrazinyl-aminotriazine compound comprising the steps of providing a triazolyl-triaminotriazine precursor and diazotizing the precursor to form the triazolyl-tetrazinyl-aminotriazine, or derivative thereof. Additionally, the present invention further includes a pyrotechnic composition comprising a triazolyl-tetrazinyl-aminotriazine compound.
The present invention further includes a dye comprising a formula of:
wherein R
2
and R
3
independently comprise electron donating groups, and Rx comprises an elongated conjugation sufficient to create a chromogen, with Rx preferably a chromophore, including azo dyes, having a (—N═N—) linkage or an imino dyes having a (—N═CR
a
R
b
—) linkage, such as (—N═CR
a
Ar
x
—), where R
a
and R
b
represent additional dye forming substituents, such as aryl groups, e.g., multiple and/or fused aryl groups (Ar
x
).
Preferably the dye comprises the formula of:
wherein R
9
, R
6
, R
7
, and R
8
are electron donating groups, more preferably with R
6
and R
7
being —NH
2
, and most preferably with R
9
, R
6
, R
7
, and R
8
are —NH
2
; and R
y
is —N═N—.
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes a process for making a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, acid salt, particularly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt and a process for neutralizing the acid salt to make a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, particularly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, as well as the product of this process (the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, including the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine is referred to herein as the “precursor”). Because of the reactive properties of the precursor, this precursor is useful in deriving compounds for ingredients in propellants, explosives, pyrotechnics, gas generators, ultraviolet absorbers, pharmaceuticals, and colorants, as later described.
The general process involves ring closure of a 2,4-substituted diamino-6-hydrazino-s-triazine with an acid and a chemical of the general formula RCN where the R comprises a leaving group, and then neutralizing said acid. Because the hydrazine nitrogen atoms that form the triazole ring are already in place on the 2,4-substituted-6-hydrazino-s-triazine, the final product formed is the desired [4,3-a] isomer, rather than the [1,5-a] isomer produced by the conventional dicyandiamide/hydrazine dihydrochloride m
Koppes William M.
Sitzmann Michael E.
Balasubramanian Venkataraman
Homer Mark
Raymond Richard L.
The United States of America as represented by the Secretary of
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