Chemistry of hydrocarbon compounds – Alicyclic compound synthesis – Adamantane or derivative
Reexamination Certificate
2001-12-12
2004-12-14
Wood, Elizabeth D. (Department: 1755)
Chemistry of hydrocarbon compounds
Alicyclic compound synthesis
Adamantane or derivative
C585S016000, C585S021000, C585S800000, C585S802000, C585S803000, C117S068000, C117S069000, C117S070000
Reexamination Certificate
active
06831202
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is directed to novel compositions comprising one or more octamantanes. This invention is also directed to novel processes for the separation and isolation of octamantane components into recoverable fractions from a feedstock containing one or more octamantane components.
REFERENCES
The following publications and patents are cited in this application as superscript numbers:
1
Lin, et al., Natural Occurrence of Tetramantane (C
22
H
28
), Pentamantane (C
26
H
32
) and Hexamantane (C
30
H
36
) in a Deep Petroleum Reservoir, Fuel, 74(10):1512-1521 (1995)
2
Alexander, et al., Purification of Hydrocarbonaceous Fractions, U.S. Pat. No. 4,952,748, issued Aug. 28, 1990
3
McKervey, Synthetic Approaches to Large Diamondoid Hydrocarbons, Tetrahedron, 36:971-992 (1980).
4
Wu, et al., High Viscosity Index Lubricant Fluid, U.S. Pat. No. 5,306,851, issued Apr. 26, 1994.
5
Chung et al., Recent Development in High-Energy Density Liquid Fuels, Energy and Fuels, 13, 641-649 (1999).
6
Sandia National Laboratories (2000), World's First Diamond Micromachines Created at Sandia, Press Release, (Feb. 22, 2000) www.Sandia.gov.
7
Balaban et al., Systematic Classification and Nomenclature of Diamondoid Hydrocarbons-I, Tetrahedron. 34, 3599-3606 (1978).
8
Chen, et al., Isolation of High Purity Diamondoid Fractions and Components, U.S. Pat. No. 5,414,189 issued May 9, 1995.
All of the above publications and patents are herein incorporated by reference in their entirety to the same extent as if each individual publication or patent was specifically and individually indicated to be incorporated by reference in its entirety.
2. State of the Art
Octamantanes are bridged-ring cycloalkanes. They are the face-fused octamers of adamantane (tricyclo[3.3.1.1
3,7
]decane) or C
10
H
16
. The compounds have a “diamondoid” topology, which means their carbon atom arrangement is superimposable on a fragment of the diamond lattice (FIG.
1
). Octamantanes possess eight of the “diamond crystal units” and therefore, it is postulated that there are hundreds of possible octamantane structures which exist in different molecular weight core structures. Among them, 18 have the molecular formula C
34
H
38
(molecular weight 446). Octamantanes also have the molecular formulas: C
38
H
44
(molecular weight 500), C
37
H
42
(molecular weight 486), C
36
H
40
(molecular weight 472) and C
33
H
36
(molecular weight 432).
Little or no published work is available for octamantanes and higher molecular weight diamondoids. Octamantane compounds have not been artificially synthesized or isolated and these higher diamondoids along with hexamantane and heptamantane compounds have been recently thought only to have a theoretical existence.
7
Academic chemists have primarily focused research on the interplay between physical and chemical properties in lower diamondoids such as adamantane, diamantane and triamantane. Adamantane and diamantane, for instance, have been studied to elucidate structure-activity relationships in carbocations and radicals.
3
Process engineers have directed efforts toward removing lower diamondoids from hydrocarbon gas streams.
2
These compounds cause problems during the production of natural gas by solidifying in pipes and other pieces of equipment.
The literature contains little information regarding practical applications of higher diamondoids and even less, if any information regarding octamantanes. This fact is probably due to extreme difficulties encountered in their isolation and due to failed synthesis attempts. Lin and Wilk, for example, discuss the possible presence of pentamantanes in a gas condensate and further postulate that hexamantane may also be present.
1
The researchers postulate the existence of these compounds contained within petroleum solely based on a mass spectrometric selected ion monitoring (SIM) and mass spectral fragmentation patterns. They did not, however, report the isolation of a single pentamantane, hexamantane nor mention heptamantane or octamantane. Nor were they able to separate non-ionized components during their spectral analysis. McKervey et al. discuss an extremely low-yielding synthesis of anti-tetramantane.
3
The procedure involves complex starting materials and employs drastic reaction conditions (e.g., gas phase on platinum at 360° C.). Although one isomer of tetramantane, i.e. anti-, has been synthesized through a double homologation route, these syntheses are quite complex reactions with large organic molecules in the gas phase and have not led to the successful synthesis of other tetramantanes. Similar attempts using preferred ring starting materials in accordance with the homologation route, have likewise failed in the synthesis of pentamantanes. Likewise, attempts using carbocation rearrangement routes employing Lewis acid catalysts, useful in synthesizing triamantane and lower diamondoids have been unsuccessful in synthesizing other tetramantanes or pentamantanes. No attempt to synthesize or isolate octamantanes has been reported.
Among other properties, diamondoids have by far the most thermodynamically stable structures of all possible hydrocarbons that possess their molecular formulas due to the fact that diamondoids have the same internal “crystalline lattice” structure as diamonds. It is well established that diamonds exhibit extremely high tensile strength, extremely low chemical reactivity, electrical resistivity greater than aluminum trioxide (Al
2
O
3
), excellent thermal conductivity, and superb optical properties.
In addition, based on theoretical considerations, the octamantanes have sizes in the nanometer range and, in view of the properties noted above, the inventors contemplate that such compounds would have utility in micro- and molecular-electronics and nanotechnology applications. In particular, the rigidity, strength, stability, variety of structural forms and multiple attachment sites shown by these molecules makes possible accurate construction of robust, durable, precision devices with nanometer dimensions. The various octamantanes are three-dimensional nanometer sized units showing different diamond lattice arrangements. This translates into a variety of rigid shapes and sizes for the octamantane components. For example, [1212121]octamantane is rod shaped, [1234(1)23]octamantane is “S”-shaped, while [12132(1)3] is a wedge-shaped structure. A variety of other shapes exist among the octamantanes which may serve in applications which depend upon specific geometries. It has been estimated that MicroElectroMechanical Systems (MEMs) constructed out of diamond should last 10,000 times longer then current polysilicon MEMs, and diamond is chemically benign and would not promote allergic reactions in biomedical applications.
6
Again, the inventors contemplate that the various octamantanes would have similar attractive properties. Furthermore, most of the octamantanes would possess chirality, offering opportunities for making nanotechnology objects of great structural specificity and ones which have useful optical properties.
FIG. 2
illustrates examples of symmetric and asymmetric octamantane structures. Applications of these octamantanes include molecular electronics, photonics and production of nanomechanical devices, and other materials.
Notwithstanding these advantages of octamantanes, the art, as noted above, fails to provide for compositions comprising octamantanes or for processes that would lead to these compositions. In view of the above, there is an ongoing need in the art to provide for compositions comprising one or more octamantanes.
SUMMARY OF THE INVENTION
This invention is directed to novel compositions comprising one or more octamantanes and/or octamantane components.
Accordingly, in one of its composition aspects, this invention is directed to a composition comprising one or more octamantane components wherein said composition comprises at least about 25 weight percent octamantane components based on the total weight of th
Carlson Robert M.
Dahl Jeremy E.
Burns Doane Swecker & Mathis L.L.P.
Chevron U.S.A. Inc.
Wood Elizabeth D.
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