Organic compounds -- part of the class 532-570 series – Organic compounds – Silicon containing
Reexamination Certificate
1999-10-07
2001-07-03
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Silicon containing
C564S107000, C564S108000, C564S109000, C149S092000
Reexamination Certificate
active
06255512
ABSTRACT:
TECHNICAL FIELD
The present invention relates generally to energetic materials, and more particularly relates to novel chemical compounds useful, inter alia, as high energy oxidizing agents. Methods for using the novel compounds as oxidizing agents in energetic compositions are also provided, as are energetic compositions containing the compounds. In addition, the invention relates to use of the present compounds as pharmaceutical agents, e.g., as vasodilating agents.
BACKGROUND
“Energetic” compounds are used extensively in a wide variety of applications, e.g., in explosive formulations, propellants, gas-generating compositions, and the like. It is generally preferred that such materials have a high energy content yet be relatively insensitive to impact, such that accidents are avoided and energy is released only when intended. The requirements of insensitivity and high energy are in conflict, making the development of new energetic materials a difficult and challenging synthetic problem.
In developing new energetic compounds, a number of factors come into play. For example, heats of formation, density, melting and decomposition temperatures, carbon content and, generally, nitrogen content, are properties which must be considered. Energetic compounds should display good thermal and shock properties, have high heats of formation, and be straightforward to synthesize in bulk. It is generally preferred that an energetic compound have a melting point above about 100° C., an exothermic heat of combustion and a positive heat of formation &Dgr;H
f
, and a high decomposition temperature, with a relatively large separation between melting point and decomposition temperature preferred such that an energetic composition may be melt cast from the selected compound. Finally, it is of course preferred that an energetic compound be relatively simple and straightforward to synthesize in high yield.
A number of energetic compounds are known as useful as oxidizers, explosives and the like. Energetic compounds have also been disclosed as useful to inflate automobile and aircraft occupant restraint bags. However, previously known materials are generally limited in one or more ways, e.g., they are overly impact-sensitive, difficult to synthesize on a large scale, not sufficiently energetic, or the like. In addition, energetic compositions used to inflate occupant restraint bags in automobiles and aircraft typically contain potentially toxic heavy metal igniter materials, e.g., mercury compounds, Pb(N
3
)
2
or the like.
The present invention provides a new class of compounds which overcomes the aforementioned limitations in the art. The energetic compounds to which the invention pertains are commonly referred to as “secondary” explosives, i.e., compounds whose energy is released after activation by initiator compounds, also termed “primary” explosives. The compounds now provided herein meet all of the above-mentioned criteria, and outperform conventional energetic compounds in a number of ways. For example, higher O
2
density is provided than obtained with conventional secondary explosives such as ammonium perchlorate. In addition, the novel compounds are highly energetic while not overly impact-sensitive, and are straightforward to synthesize in high yield.
In addition, the compounds of the invention undergo denitration in the body, releasing nitric oxide (NO); the compounds may accordingly be used as pharmaceutical agents, i.e., as so-called “NO-donors.” NO donors are useful as vasodilating agents, insofar as NO activates guanylyl cyclase, increasing intracellular levels of cyclic guanosine 3′, 5′-monophosphate (cGMP), and cGMP brings about smooth muscle relaxation. Previously known NO donors include, for example, nitroglycerin (glyceryl trinitrate), isosorbide dinitrate, isosorbide-5-mononitrate, erythrityl tetranitrate, pentaerythritol tetranitrate, sodium nitroprusside, S-nitroso-N-acetylpenicillamine (SNAP), linsidomine chlorohydrate (also known as SIN-1), and the so-called “NONOates,” complexes of nitric oxide and nucleophiles that contain the N
2
O
2
−group and release NO upon heating or hydrolysis without need for activation. The pharmacological application of many known NO donors is limited, however, as a result of unwanted side effects, an undesirable NO release profile, or the like. Thus, there is a continuing need in the art for improved pharmaceutical agents useful as vasodilators.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to address the above-mentioned need in the art by providing novel compounds that are useful as energetic materials, e.g., as high energy oxidizing agents.
It is another object of the invention to provide methods for using the novel compounds as high energy oxidizing agents.
It is still another object of the invention to provide energetic compositions containing one or more of the novel compounds.
It is yet another object of the invention to provide such energetic compositions in the form of propellant formulations, explosive compositions, and the like.
It is a further object of the invention to provide gas-generating compositions containing one or more of the novel compounds.
It is still a further object of the invention to provide methods and compositions for using a compound of the invention as a pharmaceutical agent.
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention.
In a first embodiment, the invention relates to novel compounds of formula (I)
wherein:
R is either (a) C
1
-C
24
hydrocarbyl, optionally substituted with one or more substituents and optionally containing one or more non-hydrocarbyl linkages, e.g., —O—, —S—, —NH—, —N(alkyl)—, —N(NO
2
)—, —C(O)—, or —C(O)O—, and optionally containing one or more nonhydrogen, noncarbon atoms, e.g., S, Si, B, Al, or the like, (b) —L—R
1
, where L and R
1
are as defined below, or (c) polymeric;
L comprises a divalent hydrocarbylene linking group;
R
1
is aromatic, nitrogen-containing heterocyclic, —ONR
2
R
3
, —O—[NR
2
R
3
R
4
]
+
Y
−
, —ON═CR
5
R
6
or —O—[N═CR
5
R
6
]H
+Y
−
wherein R
2
, R
3
and R
4
are independently hydrogen, alkyl, aryl or aralkyl, if alkyl, aryl or aralkyl, optionally substituted with —NO
2
, —NH
2
and/or —NF
2
substituents, or wherein R
2
and R
3
are linked to provide an optionally substituted cyclic moiety, Y
−
is an oxidizing anion or a nitrogen-containing heterocyclic anion, and R
5
and R
6
are independently H, —NH
2,
—NF
2,
—NR
7
—NH
2
or —NR
7
(NO
2
) wherein R
7
is hydrogen, alkyl, aryl or aralkyl, if alkyl, aryl or aralkyl, optionally substituted with —NO
2
, —NH
2
and/or —NF
2
substituents, or R
5
and R
6
can be linked together to form an optionally substituted cycloalkyl ring; and
n is an integer indicating the number of —N(NO
2
)—L—R
1
groups bound to R and is thus in the range of 1 to n
max
wherein n
max
is the maximum number of substituents that can be bound to R through single covalent bonds.
In another embodiment of the invention, energetic compositions are provided containing one or more of the novel compounds as secondary explosives. These energetic compositions may take any number of forms and have a variety of uses, such as in rocket propellant formulations, including both solid and solution propellants, in liquid monopropellants, in bipropellant and tripropellant compositions, in pyrotechnics, firearms, and the like. In addition, the compounds of the invention are useful in energetic, gas-generating compositions for inflating automotive or aircraft occupant restraint devices. As will be appreciated by those skilled in the art, the aforementioned uses are exemplary in nature and not intended to represent a comprehensive list of possibilities.
In an additional embodiment of the invention, the novel compounds are used as pharmaceutical a
Bottaro Jeffrey C.
Penwell Paul E.
Petrie Mark A.
Schmitt Robert J.
Raymond Richard L.
Reed Dianne E.
Reed & Associates
SRI - International
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