CZ20031975A3 - Compositions comprising higher diamondoids and processes for their separation - Google Patents

Description

Compositions containing higher diamondoids and methods for their separation

Technical field

The present invention relates to isolated or enriched higher diamondoid components and compositions comprising one or more higher diamondoid components. The present invention also relates to novel methods of separating and isolating higher diamondoid components into recoverable fractions from a feedstock comprising one or more higher diamondoid components.

BACKGROUND OF THE INVENTION

In this patent application, the following publications and patents are cited based on their following numbers:

^ Fort, Jr. et al., Adamantane: Consequences of the Diamanthoid Structure, Chem. Rev., 277-300 (1964)

² Sandia National Laboratories (2000), World's First Diamond Micromachines Created at Sandia, Press Release, (2/22/2000) wv7w.Sandia.gov., ³ Lin et al., Natural Occurrence of Tetramantane (CH), Pentamantane (CH ) and Hexamantane (CH) in a Deep Petroleum Reservoir, Fuel (10), 1512-1521 (1995), ⁴ Chen et al., Isolation of High Purity Diamondoid

Fractions and Components, U.S. Pat.

May 1995 ⁵ Alexander, et al., Removal of Diamondoid Compounds «· ··· · from Hydrocarbonaceous Fractions, U.S. Pat. No. 4,952,747, issued August 28, 1990, ^and Alexander et al., Purification of Hydrocarbonaceous Fractions, U.S. Patent No. 4,952,748, issued August 28, 1990, to Alexander et al., Removal of Diamondoid Compounds from Hydrocarbonaceous Fractions, U.S. Patent No. 4,952,749, issued August 28, 1990 to Alexander et al., Purification of Hydrocarbonaceous Fractions, U.S. Pat. No. 4,982,049, issued January 1, 1991 ⁹ Swanson, Method for Diamondoid Extraction Using a Solvent System, U.S. Pat. No. 5,461,184, issued October 24, 1995, ^XO Partridge et al., Shape- Selective Process for Concentrating Diamondoid-Containing Hydrocarbon Solvents, US Patent No. 5,019,665, issued May 28, 1991, ^{x: L} Dahl et al., Diamondoid Hydrocarbons as Indicators of Natural Oil Cracking, Nature, 54-57 (1999) , ^x2 McKervey, Large Diamondoid Hydrocarbons, Synrahetic Approaches, Tetrahedron 971-992 (198 0), ^x3 Wu et al., High Viscosity Index Lubricant Fluid, US Patent No. 5,306,851, issued April 26, 1994, ^X4 Chung et al., Recent Development in High-Energy Density Liquid Fuels, Energy and Fuels, 641 -649 (1999), • · · · · · · · · · · · ····· ·· ·· ^ls Balaban et al., Systematic Classification and Nomenclature of Diamond-1 Hydrocarbons, Tetrahedron, 34, 3599-3609 .

All publications and patents cited above are incorporated herein by reference in their entirety as if each individual publication or patent were specifically and individually intended to be incorporated by reference in their entirety.

Diamantoids are hydrocarbon molecules showing extremely rigid structures containing skeletons of carbon atoms that can be superimposed on a diamond crystal lattice ³ (see Figure 1). Adamantane, a ten carbon molecule, is the smallest member of a series of diamondoids made up of a single polyhedral crystal subunit of diamond. Adamantane is commercially available and is widely used as a chemical intermediate. It can be prepared artificially and can be obtained from oil. Diamantane contains two diamond subunits connected by faces and triamantane contains three. These three substances can be prepared and isolated from oil and are of interest to research. Adamantane, diamantane and triamantane are considered lower diamondoids. Tetramantane, pentamantanes, etc. exhibit characteristics (including multiple isomers, chirality, and higher than tetramantane also multiple forms of different molecular weights) that distinguish them from lower diamondoids and rank them as higher diamondoids. Although only one of the higher diamondoids can be artificially prepared, there are considerations regarding their structures and hypothetical properties.

It should be appreciated that while adamantane, diamantane and triamantane have no isomers, there may be four different isomeric tetramantanes, four different shapes containing four

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Ed • Φ ot, ΦΦ ΦΦ polyhedral diamond subunits that can be superimposed in different ways on the diamond crystal lattice. Two of these isomers are enantiomers (representing each other's mirror images). Since each of the four tetramantanes has ten surfaces to which a diamond polyhedral subunit can be attached, the number of pentamantanes increases compared to the number of tetramantanes. The number of possible isomers increases rapidly with each higher member of the diamondoid series. Since the diamondoid crystal units may share more than one surface for some of the higher diamondoids, the variation of the hydrogen to carbon number ratios, i.e. the degree of condensation, also increases, leading to increasing molecular weight variability of each other member of the diamondoid family (Figure 1). Figure 2 provides a table showing different series of molecular weights calculated for higher diamondoids from tetramantanes to undecamantanes.

Indeed, lower diamontoids can be found in every oil (oil and gas condensate) as well as in oil rock extracts ¹¹ . The natural diamondoid concentrations in the oil vary in the order of magnitude. For example, the concentrations of methyldiamantane in relatively young crude oils from the Central Valley of California are of the order of several ppm (pg / g). Young oil from the Smackover Formation of Juras, Gulf Coast, USA has methyldiamantane concentrations of 20 to 30 ppm (gg / g). Because diamondoids exhibit much higher stability than other petroleum hydrocarbons, deep-stored oils that are subjected to a cracking process due to intense heat exposure can have methyldiamantane concentrations of thousands of ppm (pg / g). It is now clear how diamondoids can form in natural systems, but this can mean processes lasting millions of years.

Higher diamondoids including tetramantanes, pentamantanes

I * 9999 etc. has so far received relatively little attention. Prior to the work of the inventors Dahl and Carlson described in U.S. Patent Application No. 60 / 262,242 filed January 19, 2001 and in numerous other applications, these compounds were actually hypothetical and only one compound was artificially prepared and several others were provisionally identified (but not isolated) . More specifically, McKervey et al. describes the preparation of anti-tetramanatin in low yields using a laborious multi-step process ¹² . Higher diamondoids cannot be prepared by the carbocation isomerization methods used for lower diamondoids. Lin et al. consider the possibility of the presence of tetramantane, pentamantane and hexamantane in deep oil deposits on the basis of mass spectrometry alone and without attempting to isolate these substances ² . The possible presence of tetramantane and pentamantane in the residue after distillation of the diamondoid-containing feedstock is discussed in Chen et al. ⁴ . They also do not attempt to isolate these substances from these residues.

As a further basic experience, it is pointed out that the present inventors have independently separated the higher diamondoid cyclohexamantane, the most condensed substance of the hexamantane series, and have made this invention subject to their own patent application.

In summary, higher diamondoids have not been identified or isolated or otherwise provided except as follows: isotetramantane - preparation ¹² and unsubstituted cyclohexamantane - independent disclosure of the present inventors.

SUMMARY OF THE INVENTION

The present invention provides higher diamondoids as enrichment.

or isolated compounds. It also provides individual higher diamondoid isomers (described as higher diamondoid components) in the form of enriched or isolated compounds. Further, the present invention provides methods by which enriched and isolated higher diamondoids and higher diamondoid components can be obtained.

According to the present invention, the present inventors isolate in the form of crystals a number of previously unavailable higher diamondoids including tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes and even decamantane. The isolation of higher molecular weight diamantoids is particularly unexpected in light of the inventors finding that the relative incidence of each member of the diamondoid group (tetra vs. penta etc.) decreases by about 10x for each crystal subunit added to the structure. That is, the decamantane isolated within the scope of the present invention has an occurrence of 10 of any of the tetramantanes in the base feedstock, including ingredients prepared by prior methods.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the polyhedral structure of diamondoids and their correlation with diamond crystal lattice subunits. In particular, it shows the correlation of diamondoid structures with diamond crystal lattice subunits.

Figure 2 is a table showing the different molecular weights for each of the higher members of the diamondoid series.

Figure 3 shows the structure of tetramantanes provided by the present invention.

Figure 4 shows that the four tetramantanes have carbon skeletons that correlate with the diamond grid and can be displayed to the grid plane 100 (Figure 4A), the grid plane 110 (Figure 4B), and the diamond grid plane 111 (Figure 4C).

Figure 5 shows the structure of the pentamantanes provided by the present invention.

Figures 6A, 6B, 6C and 6D show the structure of hexamantanes provided by the present invention.

Figures 7A, 7B and 7C illustrate the structure of the heptamantanes provided by the present invention. Only one enantiomer is shown for each.

Figure 8 shows the structure of octamantanes provided by the present invention. Only examples of 500, 486, 472 and 432 molecular weights are shown.

Figure 9 shows the structure of nonamantanes provided by the present invention. Only examples of each moiety of a given molecular weight are shown.

Figure 10 shows the structure of decamantanes provided by the present invention. Only examples from each moiety of a given molecular weight are provided.

Figure 11 shows the structure of undecamantanes provided by the present invention. Only examples of each moiety of a given molecular weight are shown.

Figure 12 provides a flow chart showing the different steps used to isolate the higher diamondoid-containing fractions and the individual higher diamondoid components.

It will be appreciated that in some cases these steps may be used in a different order or possibly skipped as discussed in the examples.

Figures 13A and 13B summarize the characteristics of gas chromatography / mass spectrometry and high performance liquid chromatography for the various higher diamondoids included in the present application.

Figure 14 shows a two-column high performance liquid chromatography method for isolation of individual tetramantanes and pentamantanes.

Figure 15 shows the size and shape of selected higher diamondoids relative to C _go (buckminsterfulleren) and a representative carbon nanotube used in the development of molecular electronic devices. The carbon skeleton structures of selected diamondoids can be found in Figures 5, 6, 8, 9 and 10.

Figure 16 shows a gas chromatogram of a gas condensate feedstock, one of the original feedstocks used in the Examples (feedstock A), showing low concentrations of higher diamondoids (not detectable at this scale).

Figure 17 shows the high temperature simulated distillation profile of feedstock B using distillation residues from atmospheric distillation up to 340 ° C as feedstock. This figure also shows the targeted fraction points (1 to 10) used to isolate higher diamondoids.

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9 9 ·

Figures 18A and 18B show gas chromatograms (FID) of the distillate # 6 fraction (Table 3B, Figure 18) of raw material B 340 ° C + distillation residues and the resulting pyrolytic treatment product. These figures show that the non-diamondoid components are decomposed by pyrolytic treatment and that the higher diamondoids, in particular hexamantanes, are concentrated to be useful for isolation.

Figures 19 and 20 are diagrams showing the elution sequences of a series of individual higher diamondoids (hexamantanes) on two different high performance liquid chromatography chromatographic columns: ODS and Hypercarb, as discussed in Examples 1 and 7.

Figures 21A and 21B show preparative capillary gas chromatography data for tetramantane isolations performed in Examples 3 and 5. Figure 21A shows fractions prepared from distillation fraction # 33 of raw material A. Semi-fat numbers refer to the peaks of tetramantanes. Figure 21B shows the isolated peaks passing to the traps. The numbers in the ring (2, 4 and 6) are tetramantane. It will be appreciated that these peaks contain both enantiomers of optically active tetramantanes.

Figures 22A, 22B and 22C show micrographs of tetramantane crystals isolated from raw material A by preparative gas chromatography (Figure 21). Figure 22A represents the recovered fraction # 2, Figure 22B the recovered fraction # 4, and Figure 22C the recovered fraction # 6. Since the two enantiomeric tetramantanes have identical gas chromatography retention times in Figure 21, it contains one of the crystals both enantiomers.

·· ····

Figure 23A shows a gas chromatogram of the retained fraction from the atmospheric distillation of feedstock B described in Example 1, which is used as a starting material in pyrolytic treatment. The hold fraction is the substance obtained from the distillation column after distillation of feedstock B at a temperature of about 340 ° C. Tetramantanes Nos. 1 to 3 are illustrated.

Figure 23B shows a gas chromatogram of the pyrolytic product from the starting material shown in Figure 23A, i.e. the fraction of the feedstock B fraction at atmospheric distillation at 340 ° C + of the distillation residues, showing degradation of non-diamondoid components.

Figures 24A and 24B compare gas chromatographs - starting mixtures containing tetramantane injected onto a Vydac ODS HPLC column and HPLC slice 6 enriched with a tetramantane component.

Figure 25 shows preparative isolation by high performance liquid chromatography on an ODS (ODS HPLC) column of the atmospheric distillation of feedstock B at 340 ° C + residues and shows fractions collected at different retention times and elution order of tetramantane components and fraction # 12 time used in fraction # 12. further insulation steps. Figure 23 above shows a gas chromatograph of this feedstock.

Figure 26 shows a chromatogram from high performance liquid chromatography of fraction 12 (Figure 25) performed on a stationary phase of Hypercarb with acetone mobile phase to obtain isolation of tetramantane # 2.

Figures 27A and 27B show total ion chroma99 9

gas chromatography / mass spectrometry (GC / MS) togram (TIC) and tetramantane # 1 mass spectrum isolated by high performance liquid chromatography using two different columns.

Figures 28A and 28B depict gas chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and mass spectra of tetramantane # 2 isolated by high performance liquid chromatography using two different columns.

Figures 29A and 29B depict gas chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and mass spectra of tetramantane # 3 isolated by high performance liquid chromatography using two different columns.

Figures 30A and 30B depict gas ion chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and mass spectra of methyltetramantane isolated by high performance liquid chromatography on a Hypercarb column.

Figures 31A and 31B show preparative capillary gas chromatography data for the isolation of pentaraantanes. Figure 31A shows a cut-out of a first column containing one of the pentamantanes from the heat treated feedstock B. The excised material is separated on a second column. Figure 31B shows the top of the second column that exits into the trap. Pentamantane No. 1, the first pentamantane which eluted in gas chromatography / mass spectrometry analysis, was isolated in template 6.

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Figures 32A and 32B show the total ion chromatogram of gas chromatography / mass spectrometry and the mass spectrum of pentamantane # 1 isolated by preparative capillary gas chromatography.

Figure 33A is a photomicrograph of pentamantane No. 1 crystals isolated from raw material B by preparative gas chromatography (Figures 31 and 32). Figure 33B shows a pentamantane mixed crystal.

Figure 34 shows refractive index tracking in preparative HPLC (negative polarity) of the saturated hydrocarbon fraction of distillate B pyrolysis product showing the HPLC performance fractions obtained using octadecylsilane columns and acetone mobile phase. The pentamantanes are numbered in the order of elution in gas chromatography / mass spectrometry analyzes.

Figure 35 shows a chromatogram of fraction 11 of high performance liquid chromatography on the ODS column (Figure 34) performed with a stationary Hypercarb phase and a mobile acetone phase to obtain isolation of pentamantane # 1.

Figures 36A and 36B depict gas chromatographic / mass spectrometry (GC / MS) total ion chromatogram (TIC) and mass spectrum of pentamantane # 1 isolated by high performance liquid chromatography using two different columns.

Figures 37A and 37B show the total ion chromatography (TIC) gas chromatography / mass spectrometry (GC / MS) and the mass spectrum of pentamantane # 2 isolated

9999 9999 high performance liquid chromatography using two different columns.

Figures 38A and 38B depict gas chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and pentamantane # 3 mass spectra isolated by high performance liquid chromatography using two different columns.

Figures 39A and 39B depict gas chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and mass spectra of pentamantane # 4 isolated by high performance liquid chromatography using two different columns.

Figures 40A and 40B depict gas chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and pentamantane # 5 mass spectrum isolated by high performance liquid chromatography using two different columns.

Figures 41A and 41B depict gas chromatographic / mass spectrometry (GC / MS) total ion chromatogram (TIC) and pentamantane # 6 mass spectrum isolated by high performance liquid chromatography using two different columns.

Figures 42A and 42B show preparative capillary gas chromatography data for the isolation of hexamantane. Figure 42A shows the first column fractions containing two of the hexamantanes of feedstock B. Figure 42B shows the peaks of the second column isolated and passing to the scavengers. In this way, pure hexamantanes (Figures 43 and 44), hexa 0, 00 00, e, 0, m, manthanum 2, the second hexamantane eluting in this gas chromatography / mass spectrometry analysis are isolated. whereas hexamantane # 8 elutes as the eighth.

Figures 43A and 43B depict gas ion chromatography / density spectroscopy (GC / MS) total ion chromatogram (TIC) and mass spectrum of hexamantane # 2 isolated by preparative capillary gas chromatography.

Figures 44A and 44B depict the total ion chromatography gas chromatography / mass spectrometry and hexamantane # 8 mass spectrum of highly concentrated preparative capillary gas chromatography. A smaller amount of methylheptamantane (molecular weight 408) is present in this sample.

Figure 45 shows a photomicrograph of hexamantane No. 2 crystals isolated from raw material B by preparative gas chromatography (Figures 42 and 44).

Figure 46 shows a micrograph of hexamantane # 8 crystals isolated from raw material B by preparative gas chromatography (Figures 45 and 47).

Figures 47A and 47B depict gas chromatographic / mass spectrometry (GC / MS) total ion chromatogram (TIC) and hexamantane # 8 mass spectra in fraction # 39 from high performance liquid chromatography on the ODS column.

Figures 48A and 48B depict gas chromatography / mass spectrometry total ion chromatogram (TIC) and hexamantane # 10 mass spectrum in high performance liquid chromatography (ODS) fraction # 48 on the ODS column.

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Figures 49A and 49B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and hexamantane # 6 mass spectrum in fraction # 63 from high performance liquid chromatography on the ODS column.

Figures 50A and 50B depict the total ion chromatograph of gas chromatography / mass spectrometry and the hexamantane No. 2 mass spectra highly enriched in fraction No. 53 from high performance liquid chromatography on a Hypercarb column.

Figures 51A and 51B depict gas chromatography / mass spectrometry (GC / MS) total ion chromatogram (TIC) and hexamantane # 13 mass spectrum isolated by high performance liquid chromatography using two different columns.

Figures 52A and 52B depict gas chromatographic / mass spectrometry (GC / MS) total ion chromatogram (TIC) and hexamantane # 7 mass spectrum isolated by high performance liquid chromatography using two different columns.

Figures 53A and 53B show reconstructed gas chromatography / mass spectrometry ion chromatograms, m / z from 382, and the mass spectrum of condensed irregular hexamantane (molecular weight 382) in the saturated hydrocarbon fraction of the pyrolytic treatment of distillation fraction 6 of feedstock B.

Figures 54A and 54B depict the reconstructed ion chromatogram, m / z 382, and the mass spectrum of irregular hexamantane (MW 382) of Fraction No. 36 from high performance liquid chromatography on an ODS column.

Figures 55A and 55B show the total ion chromatography (TIC) of gas chromatography / mass spectrometry and the mass spectrum of methylhexamantane (molecular weight 410) isolated in fraction # 55 from high performance liquid chromatography on an ODS column.

Figure 56 shows the total ion chromatography (TIC) of gas chromatography / mass spectrometry of pooled fractions # 23-26 of high performance liquid chromatography on an ODS column containing cyclohexamantane and methylcyclohexamantane.

Figures 57A and 57B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of methylcyclohexamanatan No. 1 (molecular weight 356) isolated using a multi-column stationary phase high performance liquid chromatography (ODS and then Hypercarb).

Figures 58A and 58B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and mass spectrum of methylcyclohexamanatan # 2 (molecular weight 356) isolated using a multi-column stationary phase high performance liquid chromatography (ODS and then Hypercarb).

Figures 59 and 60 show micrographs of methylcyclohexamantane # 1 and methylcyclohexamantane # 2 crystals isolated using two different high performance liquid chromatography columns.

Figures 6IA and 61B show preparative capillary gas chromatography data for the isolation of heptamantanes. Figure 61A shows fractions of the first column containing two of the heptamantanes from feedstock B. Figure 61B shows the peaks of the second column isolated and passing to the scavengers. In this method, pure heptamantanes (Figures 8 and 9) are isolated, heptamantane # 1 is eluted first using the gas chromatography / mass spectrometry method, and heptamantane # 2 elutes second.

Figures 62A and 62B depict the total ion chromatogram of gas chromatography / mass spectrometry and the mass spectrum of Heptamantanes No. 1 isolated by preparative capillary gas chromatography.

Figures 63A and 63B show the total ion chromatogram of gas chromatography / mass spectrometry and the mass spectrum of heptamantanes # 2 -highly concentrated preparative capillary gas chromatography.

Figure 64 shows photomicrographs of crystals of heptamantane No. 1 isolated from raw material B by preparative gas chromatography (Figures 61 and 62).

Figure 65 shows photomicrographs of crystals of heptamantane # 2 isolated from raw material B by preparative gas chromatography (Figures 61 and 63).

Figures 66A and 66B show the total ion chromatography (TIC) of gas chromatography / mass spectrometry and the mass spectrum of the heptamantane component # 1 in fraction # 45 from the high performance liquid chromatography column.

ODS.

Figures 67A and 67B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of heptamantane component # 2 in fraction # 41 from high performance liquid chromatography on the ODS column.

Figures 68A and 68B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of heptamantane component # 9 in fraction # 61 from high performance liquid chromatography on the ODS column.

Figures 69A and 69B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of the heptamantane component # 10 in fraction # 87 from high performance liquid chromatography on the ODS column.

Figures 70A and 70B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of # 1 heptamantanes highly enriched in fraction # 55 by high performance liquid chromatography on a Hypercarb column.

Figures 7TA and 71B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of heptamantanes # 2 isolated using two different columns of high performance liquid chromatography. Heptamantane # 2 was isolated from the high performance liquid chromatography (ODS) # 41 fraction (Figure 67) using a high performance liquid chromatography system.

Hypercarb.

Figure 72 shows reconstructed gas chromatography / mass spectrometry ion chromatograms, m / z 420, showing the partially condensed heptamantane component (molecular weight 420) in fraction # 61 from high performance liquid chromatography on the ODS column.

Figure 73 shows the mass spectrum of heptamantane of molecular weight 420 of Figure 72.

Figures 74A and 74B depict gas chromatography / mass spectrometry total ion chromatography (TIC) and mass spectra of the methylheptamantane component (molecular weight 408) isolated in fraction # 51 of high performance liquid chromatography on the ODS column.

Figures 75A and 75B show the total ion chromatogram of gas chromatography / mass spectrometry and the octamantane mass spectrum δ. 1 highly concentrated by high performance liquid chromatography.

Figure 76 is a photomicrograph of octamantane # 1 crystals isolated from raw material B by high performance liquid chromatography.

Figures 77A and 77B show the total ion chromatogram (TIC) of gas chromatography / mass spectrometry and the mass spectrum of mixed crystals of octamantanes # 3 and octamantanes # 5 (Figure 78) grown from fraction # 1.

high performance liquid chromatography on ODS column.

Figures 78A and 78B show photomicrographs of mixed octamantane crystals of No. 3 to No. 5, respectively. 5, crystal B is dissolved in cyclohexane and analyzed by gas chromatography / mass spectrometry (Figure 77).

Figures 79A and 79B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and mass spectra of fraction # 80 from high performance liquid chromatography on an ODS column containing octamantane # 1.

and octamantane # 10.

Figures 80A and 80B depict gas chromatographic / mass spectrometry (TIC) total ion chromatogram (TIC) and mass spectrometry fraction No. 92 from high performance liquid chromatography (ODS) column containing 500 molecular weight octamantane.

Figures 81A and 81B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and mass spectra of fraction No. 94 from high performance liquid chromatography on an ODS column containing 460 molecular weight methyloctamantane.

Figures 82A and 82B depict gas ion chromatography (TIC) gas chromatography / mass spectrometry and nonamantane mass spectra concentrated by high performance liquid chromatography.

Figures 83A and 83B show the total ion chromatography (TIC) gas chromatography / mass spectrometry and the mass spectrum of nonamantane concentrated using two different high performance liquid chromatography columns.

• · ··· ·

Figures 84A and 84B show a photomicrograph of a nonamantane crystal and a dissolved crystal mass spectrum.

Figures 85A and 85B depict gas ion chromatography / mass spectrometry total ion chromatogram (TIC) and methylnonamantane mass spectrum (molecular mass 512).

Figures 86A and 86B depict gas chromatography / mass spectrometry total ion chromatogram (TIC) and mass spectrum [1231241 (2) 31, molecular weight 456, of decamantane concentrated by high performance liquid chromatography.

Figures 87A and 87B depict the total ion chromatogram (TIC 3 gas chromatography / mass spectrometry and mass spectrum [1231241 (2) 3], molecular weight 456, of decamantane isolated by high performance liquid chromatography on two different columns.

Figures 88A and 88B depict a micrograph of [1231241 (2) 3], a molecular weight of 456, a decamantane crystal, and a mass spectra of a dissolved crystal.

Figures 89A and 89B show the selected gas chromatography / mass spectrometry (TIC) ion chromatograph (TIC) and decamantane mass spectrum (MW 496).

Figures 90A and 90B depict the total ion chromatography (TIC) gas chromatography / mass spectrometry of two methyldecamantanes (MW 470) and the mass spectrum of one eluting at 18.84 min.

for gas chromatography / mass spectrometry.

Figures 91A and 91B show a selective ion chromatogram of gas chromatography / mass spectrometry (m / z 508) and a mass spectrum of the pyrolysis product of fraction no.

from atmospheric distillation of raw material B (Table 3) concentrating undecamantanes.

Figures 92A and 92B and 92C show selective ion chromatography gas chromatography / mass spectrometry (m / z 508) and mass spectra of undecamantane component (molecular weight 508) eluting at 21.07 min, and mass spectrometry of methylenedecamantane component (molecular weight) 522), which eluted at 21.30 min.

Figure 93 is a diagram depicting distillation fractions of a higher diamondoid containing feedstock (raw material B, residue after atmospheric distillation) showing fraction choices for the advantageous enrichment of specific higher diamondoid groups.

Figure 94 shows helical structures (right-handed and left-handed) of hexamantane [12341].

A detailed description of the invention follows.

This detailed description is presented in the following sub-sections.

Definition

Higher diamondoids

Raw materials

Methods of insulation

Use

Examples

Definition

The terms used herein have the following meanings.

The term diamantoid refers to substituted and unsubstituted compounds having a polyhedral structure of the adamantane series including adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, undecamantane and the like, and also the isomers thereof. The substituted diamondoids preferably comprise from 1 to 10, preferably from 1 to 4, alkyl substituents.

The term lower diamondoid components or adamantane, diamantane and triamantane components refer to any or all of the unsubstituted or substituted derivatives of adamantane, diamantane and triamantane.

The term higher diamondoid component refers to any of the substituted or unsubstituted diamondoids or all of these corresponding to tetramantanes and higher components including tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes, decamantanes, decamantanes, undecamantanes and the like, all of them.

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Preferably, these higher diamondoids include substituted and unsubstituted tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes, decamantanes and undecamantanes. Figure 2 is a table providing representative higher diamondoids together with their molecular weights. The term diamondoid group, tetramantane group and the like is used to define a group such as diamondoid components having the same number of polyhedral diamond crystal lattice units.

The term tetramantane components refers to any of the substituted or unsubstituted diamondoids of the corresponding tetramantanes or all of these components.

The term pentamantane components refers to any of the substituted or unsubstituted diamondoids of the corresponding pentamantanes or all of these components.

The term unionized diamondoid components refers to higher diamondoid components that do not carry an electrical charge, such as a positive electrical charge generated during mass spectral analysis, wherein the association of the higher diamondoid component corresponds to the definition described herein.

The term unionized tetramantane components refers to tetramantane components that do not carry an electrical charge, such as a positive electrical charge generated during mass spectral analysis.

The term non-ionized pentamantane components and diamondoid components higher than pentamantane refers to pentamantane components and higher diamondoid components larger than pentamantane which do not carry an electrical charge, such as a positive electrical charge generated during mass spectral analysis.

The term selected higher diamondoid components and the like refers to one or more substituted or unsubstituted higher diamondoids whose isolation or enrichment in the product is desired.

The term unselected higher diamondoid components and the like refers to those higher diamondoid components that are not selected higher diamondoid components.

The term enriched when used to describe the purity state of one or more diamondoid components refers to substances at least partially separated from the feedstock and, in the case of enriched individual higher diamondoid components, refers to enrichment at least 25 fold and preferably at least 100 fold over the original concentration in the feedstock. Preferably, the enriched higher diamondoid or enriched higher diamondoid component is in an amount of at least 25%, in particular at least 50% (i.e., 50 to 100%) more preferably at least 75% and even more preferably at least 95% or at least 99% (w / w). which occurs or in other words has a purity by weight of at least 25%, 50%, 75%, 95% or 99% of the substance.

The term feedstock or hydrocarbon feedstock refers to hydrocarbon materials containing the amount of higher diamondoids that can be obtained. Preferably, these raw materials include oil, gas condensates, refinery material streams, oils derived from porous rocks, oil shales, tar sands and raw materials, and the like. These components usually, but not necessarily, include one or more lower

<4 diamondoid components as well as non diamondoid components. These are typically characterized by containing components having a boiling point lower or higher than the lowest boiling point of tetramantane which boils at about 350 ° C at atmospheric pressure. Conventional feedstocks may also contain impurities such as sediment, metals including nickel, vanadium, and other inorganic components. They may also contain heteromolecules containing sulfur, nitrogen and the like. All of these non-diamondoid substances are included in the non-diamondoid components as defined herein.

The term unselected substances refers to a set of raw material ingredients that are not selected higher diamondoid ingredients and include non-diamondoid ingredients, lower diamondoid ingredients, and unselected higher diamondoid ingredients as defined by these terms.

The term removal or removal refers to methods of removing non-diamamantoid components and / or lower diamondoid components and / or unselected higher diamondoid components from the feedstock. Such methods include, for example, dimensional separation, distillation, normal or reduced pressure evaporation, the use of wellheads, sorption, chromatography, chemical extraction, crystallization and the like. Chen et al. ^4, for example, disclose distillation methods for removing adamantane, substituted adamantane, diamantane, substituted diamantane, and triamantane from a hydrocarbon feedstock. Dimension separation methods include membrane separations, molecular sieves, gel permeation methods, size exclusion chromatography and the like.

The terms distillation or distillation refer to tails

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444 · 4 ·

4 4 · 4 <44 • 44> 4 4 »4« 4 4 «44 4 * 4 4 4

4 4 cation processes in which the substances are separated on the basis of the vapor pressure differences, where the high vapor pressure substances pass into the front fraction. Distillation may be carried out with the hydrocarbon feedstocks and fractions obtained otherwise during the processing of the hydrocarbon feedstocks. In this context, distillation under reduced pressure is most commonly carried out, but can also be carried out under atmospheric or even elevated pressure.

The terms fractionation and fractionation refer to processes in which the substances in the mixture are separated from one another in a manner other than by different solubility, different vapor pressure, different chromatographic affinities, and the like.

The term pyrolysis and heat treatment to effect pyrolysis and the like refer to heating the feedstock at atmospheric, reduced or elevated pressure or fraction of the feedstock to thermally degrade the proportion of one or more components in the feedstock.

The term nondiamantoid feedstock components refers to feedstock components or feedstock fractions that are non-diamondoid in nature, where the term diamondoid is defined herein.

The term retention refers to the retention of at least a portion of the higher diamondoid components found in the feedstock compared to the amount of these diamondoid materials present in the feedstock. In one preferred embodiment, at least about 10% by weight, more preferably at least about 50% by weight, and more preferably at least about 90% by weight, of the treated feedstock is retained in the feedstock prior to processing.

• ·

Chromatography refers to any number of well known chromatographic methods, including but not limited to; limitation, column or gravity chromatography (either normal or reverse phase), gas chromatography, high performance liquid chromatography, and the like.

The term alkyl refers to straight or branched chain saturated aliphatic groups having usually 1 to 20 carbon atoms, more preferably 1 to 6 atoms (lower alkyl groups) as well as cyclic saturated aliphatic groups having usually 3 to 20 carbon atoms, preferably from 3 to 6 carbon atoms (also lower alkyl groups). The term alkyl and lower alkyl may be exemplified by groups such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Higher diamondoids

As shown in Figure 1, higher diamondoids are cycloalkanes having a bridged ring whose carbon atom skeleton can be superimposed on the diamond crystal lattice (Figs. 1a and 4). They are the tetramers, pentamers, hexamers, heptameters, octamers, nonamer, decamers etc. of adamantane (tricyclo [3.3.1.1 ^{3 '7]} decane), or in which various adamantane the Drive bonded area. Higher diamondoids may contain a number of alkyl substituents.

These compounds have extremely rigid structures and the highest stability of any of the compounds of their formula. There are four tetramantane structures (Figures 2 and 3),

isotetramantane 11 (2) 3], antitetramantane [121] and the two enantiomers of cross-linked tetramantane [123] (Figure 3), and the more general nomenclature described for these diamondoids in square brackets is in accordance with the convention of Balabana et al. ^{15 Dec} There are ten pentamantanes (Figure 5), nine of which have the general formula C ₂₆ H ₃₃ (molecular weight 344) and among these nine are three pairs of enantiomers shown as [12 (1) 3], [1234], [1213] and the non-enantiomeric the pentamantanes shown [12 (3) 4], [1 (2,3) 43, [1212]. There is also a more deformed pentamantane described by the molecular formula CH (molecular weight 330), see Figure 4.

53 0

Hexamantanes exist in 39 different structures (Figure 6), 28 of which have the molecular formula C ₃₀ H _3e (molecular weight 396) and six of them are achiral, ten more deformed hexamantanes have the molecular formula C _2a H (molecular weight 382) and the remaining hexamantane [ 12312] has the molecular formula C ₂₅ H ₃₀ (molecular weight 342), which is also called cyclohexamantane because of its highly condensed ring structure. It is believed that heptamantanes exist in the form of 160 possible structures, of which 85 have the molecular formula C ₃ H (molecular weight 448) (Figure 7) and of which seven are achiral, which have no enantiomers. Figure 7 shows only one of the two enantiomeric structures of chiral heptamantanes. Of the remaining heptamantanes, 67 has the molecular formula C ₃₃ H _3s (molecular weight 434) and six of them have the molecular formula CH (molecular weight 420). These two groups of heptamantanes have structures exhibiting greater internal deformation of the bond with correspondingly lower stability and are not shown in Figure 7. The remaining two have molecular formula C ₃ H ₃₄ (molecular weight 394) (Figure 7). Octamantanes have eight polyhedral diamond crystal units and exist within five groups of different molecular weight core structures (Figure 9).

2). Among octamantanes, eighteen of them have the molecular formula C ₃₄ -H _3a (molecular weight 446). Figure 8 shows each of the isomers of octamantane having a molecular weight of 446. Other octamantanes have a molecular formula of C (molecular weight 500). The remaining groups of octamantanes, C ₃₇ H ₄₂ (MW 486), CH (MW

6 4 0

472) and C ₃₃ H _3e (molecular weight 432) show greater bond deformation and correspondingly lower stability. Nonamantanes exist within six groups of different molecular weights with the following molecular formulas: C ₄₂ ^H 4e (molecular weight 552), 0 _4ΐ Η _4β (molecular weight 538), C _4Q H ₄₄ (molecular weight 524), (molecular weight 498) , CH (molecular weight 484) and CH (molecular weight 444). In addition, tetramantane exists in groups of seven different molecular weights. Among decamantanes there is one decamantane of molecular formula C ₃₅ H ₃ (molecular weight 456), which is structurally compact compared to other decamantanes and has little internal deformation of the bond. Other groups of decamantanes have molecular formulas: CH (molecular weight 604), CH

4652 4550 (molecular weight 590), C ₄₄ H _4e (molecular weight 576), C ₄₂ H _{4 S} (molecular weight 550), (molecular weight 536) and CH (molecular weight 496).

S 4 O

Undecamantanes (Figure 11) there, with molecular formula _of C _H (molecular weight 656), C ₄ H ₅₄ (molecular weight 642), CH (molecular weight 628), CH

Q Ξ 2 4650 (MW 602), C H (MW

48

588), C ₄₂ H ₄₄ (molecular weight 534), C _{3s (} H _{4 O} (molecular weight 508). More preferred and less preferred diamondoids (Figure 2) are considered based on their internal bond deformation and corresponding stability, which is reflected in relative concentrations in different raw materials.

·> · · · • · · · •

Raw materials

The higher diamondoids provided by this invention exist only in dilute concentrations in solutions in petroleum feedstocks.

In the methods of the present invention, the feedstock is selected in such a way that it contains acceptable amounts of one or more selected higher diamondoid components. Preferably, such feedstock comprises at least 1 ppb of one or more higher diamondoid components, more preferably at least 25 ppb and more preferably at least about 100 ppb. It will be appreciated, however, that raw materials with higher concentrations of higher diamondoid components facilitate the recovery of these components.

Preferred feedstocks include, for example, natural gas condensates and material streams in refineries with high concentrations of higher diamondoids. In the latter case, these refinery streams include hydrocarbon streams obtainable from cracking processes by distillation, coking and the like. Particularly preferred feedstocks include gas condensates from Norphlet Formation in the Gulf of Mexico and LeDuc Formation in Canada.

In one embodiment, the raw materials used in the methods of the present invention typically comprise non-diamondoid components with melting points lower and higher than the lowest melting point of the higher diamondoid component selected to obtain the same as one or more lower diamondoid components. These raw materials will usually contain a mixture of higher diamondoid components. Depending on which higher diamondoid components are selected, these higher diamondoid components may have boiling points below the boiling point of the selected higher diamondoid. · · · · · · · · · · · · · · · · · · · · · · · · ··· ···· · · · · · · Typically, the lower boiling point of the higher diamondolate component selected for recovery will exceed about 335 ° C. In conventional feedstocks, the concentration of the lower diamondoid components relative to the higher diamondoid components is generally about 250: 1 or higher. Further, as shown in Figure 18, conventional raw materials containing higher diamondoid components also contain non-diamondoid components.

In these feedstocks, often the selected higher diamontoid components cannot be obtained directly from the feedstock due to their low concentrations relative to the non-selected components.

Accordingly, the methods of the invention may include removing sufficient of these contaminants from the feedstock under conditions providing the processed feedstock from which the selected higher diamondoid components may be recovered.

Methods of insulation

The general methods for isolating higher diamondoids are shown in Figure 12.

In one embodiment, removing contaminants comprises distilling the feedstock to remove non-diamondoid components as well as lower diamondoid components and, in some cases, other non-selected higher diamondoid components having boiling points lower than the lowest boiling point of the higher diamondoid component to be recovered.

In a particularly preferred embodiment, the feedstock is distilled to provide fractions above and below about 335 ° C, at atmospheric equivalent boiling point, and more preferably above and below about 345 ° C at atmospheric boiling point. In all cases, the lower fractions enriched with the lower diamondoid components and other than the low boiling diamondoid components pass to the front fractions and are discarded and the higher boiling fraction enriched with the higher diamondoids is maintained. It should be understood, however, that the fraction temperature during distillation is a function of pressure and that higher temperatures are related to atmospheric pressure. The reduced pressure will result in a lower distillation temperature reaching the same fractions, while the increased pressure will result in a higher distillation temperature while maintaining the same fractions. The correlation between pressure and temperature in the transition from atmospheric distillation to reduced or elevated pressure distillation is within the skill of the art.

Distillation can be conducted to fractionate the raw materials and provide several fractions within a given temperature range with the initial enrichment of selected higher diamondoids or groups of selected higher diamondoids. Fractions that are enriched in one or more selected diamondoids or a given diamondoid component are retained and may require further purification. The following table shows representative fractionation temperatures that can be used to enrich various higher diamondoids in the front fractions. In practice, it may be advantageous to provide fractions with a wider temperature range which could contain higher diamondoid groups that could be separated together in further separation steps.

Fractionation points Most preferred Preferred Temperature Temperature Temperature Temperature lower higher lower v v higher fractions fractions fractions fractions (° C) (° C) (° C) (° C)

Higher diamondoids ··································

- 34 - • · · · «· • · · · ·· ·· Tetramantanes 349 382 330 400 Pentamantanes 385 427 360 450 Cyclohexamantanes 393 466 365 500 Hexamantanes 393 466 365 500 Heptamantanes 432 504 395 540 Octamantanes 454 527 420 560 Nonamantany 463 549 425 590 Dekamantany 472 571 435 610 Undecamantans 499 588 455 625

Useful

Temperature lower fractions (° C) Temperature higher fractions (° C) Higher diamondoids Tetramantanes 300 430 Pentamantanes 330 490 Cyk1ohexamantany 330 550 Hexamantanes 330 550 Heptamantanes 350 600 Octamantanes 375 610 Nonamantany 380 650 Dekamantany 390 660 Undekamant any 400 675 It will be appreciated that substituted higher diamondoids may have these preferred fraction temperatures, respectively

shifted to higher temperatures due to the presence of substituents. Further refinement of the temperatures will allow higher purity of the fractions relative to the desired diamondoid. Figure 93 provides a further illustration of how fractionation can provide a fraction

98 99 9 9 9 9

999 999 9999

999 99 99 9 99 99 ce enriched with one or more higher diamondoid components.

It will further be appreciated that fractionation can be stopped prior to removal of the selected higher diamondoid. In this case, the higher diamondoid component can be isolated from fractionation residues.

Other methods for removing lower diamondoids, other than selected higher diamondoids, if present, and / or hydrocarbon non-diamondoid components include, by way of example only, methods of separation on different dimensions, evaporation under normal or reduced pressure, crystallization, chromatography, orifice separators , using reduced pressure and the like. Removal methods may utilize larger diameters of higher diamondoids to exert their separation from lower diamondoids. For example, methods based on dimensional differences using membranes will allow the raw material membrane to selectively pass through the lower diamondoid membrane barrier with the proviso that the size of the membrane barrier dimension is selected to differentiate compounds having a larger diamondoid component dimension than a lower diamontoid component. The pore size of molecular sieves such as zeolites and the like can also be used to effect dimensional separation.

In one preferred embodiment, the removal method for the processed feedstock provides a ratio of lower diamondoid components to higher diamondoid components not exceeding 9: 1, more preferably 2: 1, and even more preferably a ratio not greater than 1: 1. Even more preferably, after removing the lower diamondoid component (s) from the feedstock, at least 10%, preferably at least 50%, and even more preferably at least 90% of the higher diamondoid component are retained in the feedstock.

9999 • 99

9 9

99

9 9

9 9

999 99

9 ·

9 9

9

4 9

9 9 • · · · · · ···

From the amount present in the raw material before disposal.

If it is desired to obtain hexamantane and higher diamondoid components, and if the feedstock contains non-diamondoid contaminants, the feedstock will also generally be pyrolyzed to remove at least a portion of the hydrocarbon non-diamondoid components from the feedstock. This pyrolysis effectively concentrates the amount of higher diamondoids in the pyrolytically processed feedstock and thus enables their recovery (Fig. 18).

The pyrolysis is carried out by heating the feedstock under vacuum conditions or under an inert atmosphere at a temperature of at least about 390 ° C and preferably from about 400 to about 550 ° C, more preferably from about 400 to about 450 ° C, and in particular from 410 to 430 ° C. followed by pyrolysis of at least a portion of the non-diamondoid components in the feedstock. The specific conditions to be used are selected so as to maintain the amount of selected higher diamondoid compounds in the feedstock. The choice of such conditions is within the skill of the art.

Preferably, the pyrolysis proceeds for a sufficient time and at a sufficiently high temperature for the thermal degradation of at least 10% of the non-diamamantoid components (preferably at least 50% and even more preferably at least about 90%) of the pyrolytically treated feedstock.

In another preferred embodiment, after pyrolysis of the feedstock, at least about 10%, preferably at least about 50%, and even more preferably at least about 90% of the higher diamondoid components in the feedstock after pyrolysis are retained from the amount present in the feedstock prior to pyrolysis.

In one preferred embodiment, the removal of the lower diamondoid components and the low boiling hydrocarbon non-diamondoid components from the feedstock precedes the pyrolytic treatment. It will be appreciated, however, that the order of these processes can be reversed so that pyrolysis occurs prior to removal of the lower diamondoid components from the feedstock.

Pyrolysis, which is a preferred embodiment, is not always necessary. This is because the concentration of the higher diamondoid components may be sufficiently high in certain feedstocks so that the processed feedstock (after removal of the lower diamondoid components) can be directly used in purification processes such as chromatography, crystallization, etc. to obtain higher diamondoid components. However, if the concentration or purity of the higher diamondoid components in the feedstock is not at a level permitting such recovery, then a pyrolysis step is required.

Although pyrolysis is used, it is preferred to further purify the treated feedstock using one or more purification methods such as chromatography, crystallization, thermal diffusion methods, zone refining, progressive recrystallization, size separation and the like. In a particularly preferred method, the treated feedstock is first subjected to gravity column chromatography using silver nitrate impregnated silica gel followed by high performance liquid chromatography using different columns of different selectivities to isolate selected diamondoids and crystallize to obtain crystals of highly concentrated higher target diamondoids. If the concentrations of the higher diamondoids are not high enough for crystallization, further concentration may be necessary, for example preparative capillary gas chromatography.

In chromatographic methods, enantioselective (chiral) stationary phases are used to carry out further separations. High performance liquid chromatography methods also offer the possibility of using chiral solvents or additives to distinguish enantiomers.

For example, separation of enantiomeric forms of higher diamondoids can be achieved using several methods. One such method is spontaneous crystallization with resolution and mechanical separation. This method of resolution of enantiomers can be improved by preparing derivatives or by using chiral solvent additives or various types of seed crystals. Another possibility of differentiation is chemical separation under kinetic or thermodynamic control. Other suitable methods of resolution of enantiomers include chiral separations that can be performed by gas chromatography (GC), see Chiral Chromatography, TE Beesley et al., Wiley Johnson and Sons, January 1998, which is incorporated herein by reference, high performance liquid chromatography (HPLC) and the like. Chromatographic Supercritical Fluid Methods (SFC), see Supercritical Fluids in Chromatography and Extraction, RM Smith, Elsevier Science, December 1997, which is incorporated herein by reference.

Use

The methods of the invention provide compositions enriched in higher diamondoids. Higher diamondoids are useful in microelectronics and molecular electronics and in nanotechnology applications. In particular, rigidity, strength, stability, thermal conductivity, a variety of structural forms, and numerous attachment points allow these molecules to provide • · · ·

I * · • · · 94 9 1 9 • 19 19

9 1 9 9 9 9

4 9 ·· · · 9 precision construction of robust, durable precision nanometer devices. Figure 15 shows the size and shapes of selected higher diamondoids relative to the molecular components (buckminsterfullerene and carbon nanotubes) used in the development of molecular electronic elements.

Higher diamondoids are three-dimensional nanometer units with different ways of arranging a diamond grid. This means a considerable range of shapes and dimensions of these extremely rigid nanostructures, for example [121 (3) 4] hexamantane is T-shaped, [12134] L-shaped and [1 (2) 3 (1) 2] is flat with four lobes. Heptamantane [12 (3,4) 12] has a cross-shaped structure while [121234] is L-shaped. Hexamantane [12312] has a disk-like structure. Heptamantane [121321] is disk-shaped with one coplanar lobe, while [1213 (1) 21] octamantane is disk-shaped with two opposite coplanar lobes. Octamantane [1232 (1) 3] is wedge-shaped. Nonamantane [121 (2) 32 (1) 3] has a triangular plate-like structure. Decamantane [1231241 (2) 3] is a perfect octagon, while decamantane [121231212] has a rectangular plate-like structure. Undecamantane [123 (1,2) 42143] is in the shape of an elongated pyramid. Among the higher diamondoids, there are a number of other shapes that can serve in nanotechnology and nanostructured fabric applications that depend on specific geometric configurations. The structures of the carbon skeleton of tetramantanes to undecamantanes are also shown in Figures 3 to 11.

Higher diamondoids also include a series of rod-shaped structures of varying lengths. Tetramantane with sequence 121 is the first member of this rod-like structural series, pentamantane [1212] is next, followed by hexamantane [12121] and so on. Each added polyhedral diamond unit increases the rod length by about 0.3 nm and pentamantane [1212] has a length of about 0.3 nm. · It

1.1 nm.

Tetramantane [1 (2) 3] initiates a more compact series, a flat peak pyramidal structure (Figure 3). Pentamantane [1 (2,3) 4] follows in this direction and is a perfect tetrahedral pyramid (Figure 5).

Higher diamondoids also include helical structures of various lengths. The first chiral diamondoid is tetramantane with sequence 123. We specify two enantiomers of tetramantanes 123 as A and B. Their structures can also be implicated by sequences 123 and 124 by modification of the Balaban nomenclature. The two diamondoids have a left-handed helix structure (counterclockwise), i.e. a tetramantane A structure and a right-handed helix structure (clockwise) (tetramantane B structure). Unfortunately, Balaban's nomenclature does not provide a way of specifying left-handed and right-handed helical forms, but merely demonstrates the existence of these two forms. This sequence continues 1234 and 1243 (i.e., A and B) for pentamantane (Figure 5), 12341 and 12431 (again A and Β), for hexamantane (Figure 6} etc. Hexamantanes complete the full revolution of the right-handed and left-handed helix for these helical nanostructures (Figure 94).

These particular structural characteristics place diamondoids outside of acyclic molecules, outside of fused ring systems and even outside of bridged ring counterparts. The high stability, nanometer dimension, variable yet rigid geometrical arrangement, well-defined distances for connection points and unplanar bridge ends lead to their unique properties. Due to the stiffness, special geometry, three-dimensional shape and nanometer size of the higher diamondoid components, it is expected that the molecular aggregates and the 44

4 4 «

4

The retrofit units containing them will allow the construction and preparation of an unexpected range of required materials that will find applications in molecular electronic computing devices, in scale machines such as molecular robots, and in self-replicating production systems. Alternatively, higher diamondoids can be used as novel materials for constructions with particular chemical, optical, electrical and thermal conductivity properties for coatings, film coating and other applications using diamond-like properties and the like. New applications of higher diamondoid materials in the field of microelectronics have been described. Embodiments include, but are not limited to, thermally conductive films in ICs, low permittivity layers at multilevel ICs, thermally conductive adhesive films, thermally conductive films in thermoelectric refrigeration devices, passivation films for ICs and cathodes emitting field.

In addition, these higher diamondoids can also be used in a high quality lubricant fluid having a high viscosity index and a very low pour point ¹³ . When used in this manner, these liquids include a liquid having a lubricant viscosity and containing 0.1-10% by weight of diamondoids.

These higher diamondoids can further be used as high density fuels as described by Chung et al. ¹⁴ , which is incorporated herein by reference.

The following examples are intended to illustrate the invention and should not be construed as limiting its content. Unless otherwise stated, all temperatures are in degrees Celsius.

DETAILED DESCRIPTION OF THE INVENTION

Φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ • • φ φ φ φ φ φ φ φ φ φ φ

42:

The following abbreviations, as used herein and in the drawings, have the following meanings. Any abbreviation not defined below has its generally accepted meaning.

API = American Petroleum Institute atm eqv = atmospheric equivalent btms = distillation residues EOR Traps = end templates f id = flame ionization detector G = grams GC = gas chromatography GC / MS ⁼ Gas Chromatography / Mass Spectrometry h = hour HPLC with: high performance liquid chromatography HYD RDG = reading the hydrometer L = liter min = minute ml = milliliters mmol = millimoles N = normal Bye = pikoampéry PPb = parts of a trillion ppm = parts out of a million Rl = refractive index SIM DIS = simulated distillation ST = start TIC = total ionic current TLC = thin layer chromatography VLT = line temperature par VOL PCT = % by volume

V / v = volume / volume wt = weight

WT PCT = weight percent

Introduction

The steps used in the various examples are also shown schematically in Figure 12.

Example 1 describes the most versatile method of isolating higher diamondoid components that can be applied to all raw materials. This method uses high performance liquid chromatography (step 7, figure 12) as its final isolation step.

Example 2 describes a modification of the method of Example 1 in which preparative gas chromatography (step 7 ', Figure 12) is used as the final isolation step instead of high performance liquid chromatography.

Example 3 describes a deviation from the method of Example 1 in which pyrolysis is omitted (step 5, figure 12). As shown in Figure 12, the liquid chromatography step can also be omitted (step 6, Figure 12). These variations are generally applicable only to selected raw materials and generally in cases where the target higher diamondoids are tetramantanes, pentamantanes and cyclohexamantanes.

Example 4 describes a further deviation from the embodiment in which the end products of Examples 1 and 3 are subjected to preparative gas chromatography purification to obtain further separation of the higher diamondoid components (step 8, Figure 12).

· · Φ..

Μ Φ · »· ·.

Example. 5 describes the enrichment and isolation of tetramantane components.

Example 6 describes the enrichment and isolation of pentamantane components.

Example 7 describes the enrichment and isolation of hexamantane components.

Example 8 describes the enrichment and isolation of heptamantane components.

Example 9 describes the enrichment and isolation of octamantane components.

Example 10 describes the enrichment and isolation of nonamantane components.

Example 11 describes the enrichment and isolation of decamantane components.

Example 12 describes the enrichment and isolation of undecamantane components.

It will be appreciated that the order of the various distillation, chromatography and pyrolysis steps can be varied, although the order described in Example 1 gives the best results.

Example 1

This example has seven steps (see flow diagram in Figure 12).

··· «· · ···

Step 1. Selection of raw material

Step 2. Development of gas chromatography / mass spectrometry analysis

Step 3. Atmospheric distillation of the feedstock

Step 4. Vacuum fractionation of atmospheric distillation residue

Step 5. Pyrolysis of isolated fractions

Step 6. Removal of the aromatic and polar non-diamintoid components

Step 7. Isolation of higher diamondoids by multi-column high performance liquid chromatography

The first column of first selectivity provides fractions enriched with specific higher diamondoids.

A second column of different selectivity provides isolated higher diamondoids.

This example is described in terms of isolating several hexamantanes. As can be seen in Examples 5 to 12, it can easily be adapted to isolate other higher diamondoids.

Step 1 - Selection of raw material

Appropriate starting materials are obtained. These substances include gas condensate, raw material A (Figure 16) and gas condensate containing crude oil components, raw material Β. Although other condensates, petroleum or fractions and refinery products may be used, these two materials are chosen because of their high diamondoid concentration, about 0.3 weight percent higher diamondoids by gas chromatography and gas chromatography / mass spectrometry. Both raw materials are light colored and have a specific gravity according to API (American Petroleum Institute) between 19 and 20 ° API.

Step 2 - Development of gas chromatography / mass spectrometry analysis

Raw material A is analyzed by gas chromatography / mass spectrometry to verify the presence of target higher diamondoids and to obtain gas chromatography retention times for these substances. This information is used to track down individual target higher diamondoids during sequential isolation steps. Figure 13A is a table providing a list of conventional gas chromatography / mass spectrometry information for hexamantanes (gas chromatography retention times, mass spectral molecular ion (M +) and baseline). This table (Figure 13A) also contains similar gas chromatographic / mass spectrometry information for other higher diamondoids. While the relative retention times of gas chromatography are roughly constant, the GC retention without reference varies with time. It is recommended that the gas chromatography / mass spectrometry data be routinely updated, especially when the gas chromatographic retention time drift is detected.

Step 3 - Atmospheric distillation of the raw material

The sample of raw material B is distilled into a number of fractions based on boiling points to separate the lower boiling components (other than diamondoids and lower diamondoids) and to further concentrate and enrich the higher diamondoids in the various fractions. The yields of the atmospheric distillation fractions for two separate samples of feedstock B are shown in Table 1 below in comparison to the simulated distillation yields. As Table 1 shows, the simulated distillation data is in line with the actual distillation data. The simulated distillation data is used to plan further distillation steps.

Table 1

Yields from atmospheric distillation fractions from two independent distillations of raw material B

Fractions (° F) Simulated distillation yield estimation (wt%) Raw material B (distillation 2) yields (wt.%) Difference to 349 8.0 7.6 0.4 349 až 491 57.0 57.7 -0.7 491 až 643 31.0 30.6 0.4 643 and more 4.0 4.1 -0.1 Fractions (° F) Simulated distillation yield estimation (wt%) Raw material B (distillation 1) yields (wt.%) Difference to 477 63.2 59.3 3.9 477 až 515 4.8 7.3 -2.5 515 to 649 28.5 31.2 -2.7 649 and more 3.5 2.1 1.4

Step 4 - Fractionation of the atmospheric distillation residue va48 • 00 00 ······· »000 ·· 0 ·· 0

00 000 000 00 000 00 · 0 0 0 000 000 000

00000 00 0 00 00 by distillation

The resulting atmospheric residue from feedstock B from step 3 (containing 2-4% by weight of the feedstock) is distilled to fractions containing higher diamondoids as shown in Figures 17 and 93). The feed for this high temperature distillation contains an atmospheric distillation fraction of 650 ° F (340 ° C) + distillation residue. Complete reports on the distillation of raw material B are given in Tables 2A and 2B. Tables 3Ά and 3B report the distillation of the raw material B fraction 650 ° F (340 ° C) + distillation residue.

Table 2A

Report on distillation of raw material

Raw material B

Column used: internal dim. 23 x 3.6 cm overlapping, filled

Distillation record Normaliz. Skuteč.

Frak- Tepl. ce par zah. con. Weight- nost G Order no. ml at 15.4 Noc: 2 ° C API Hust. at 15.4 Noc: 2 ° C Hm. % Order no. % Hm. O, O Order no. Ό 1 226-349 67.0 80 38.0 0.8348 7.61 8.54 7.39 8.26 2 349-491 507.7 554 22.8 0.9170 57.65 59.12 55.98 57.23 3 491-643 269.6 268 9.1 1,0064 30.62 28.60 29.73 27.69 Stop 0.2 0 6.6 1,0246 0.02 0.00 0.02 0.00 columns Rain. 643+ 36.1 35 6.6 1,0246 4.09 3.74 3.98 3.62

remn.

• ·· fr · · • fr • frfrfrfr • · • frfr • • frfrfr • • frfr fr fr · • • • frfrfr • • fr • • fr fr Fr frfr • · • • · • »

Conc. master 0.0 0 0.00 0.00 0.00 Total 880.6 937 100, 0 100.0 97.09 96.80 Loss 26.4 31 2.91 3.20 Injection 907.0 968 19.5 0.9371 100.0 100.0

Back. API and density calculation 19.1 0.9396

Table 2B

Report on distillation of raw material

Raw material B

Column used: internal dim. 23 x 3.6 cm overlapping, filled

Temp. Steam , ° F D. container Pressure Torr Reflux Ratio Fractions in C. Order no. ml at 45 ° c Weight API G Attention. 61 ° F T. Atm. Thu Pulse. lines eq. hyd- ° F few ro- met- ru 93 225.8 262 50,000 3 - 1 Zah. before.

fractions

198 349.1 277 50,000 3 - 1 1 80 67.0 39.6 80.0 38.0 321 490.8 376 50,000 3 - 1 2 554 24.1 80.0 22.8

Fraction 2, lactic acid, formation of white crystals in descending tube. A heat lamp is used for the drip tube. Cooling for transfer dest. the rest into a smaller flask.

Zah.

before.

208,437.7 323

10,000 3: 1 fractions

378,643.3 550 10.000 3: 1 3,268 269.6 9.9 75.0 9.1

Shutdown when the dest. containers

End templates 0 0.0 Oddestil. volume 902 Stop the column 0 0.2 0.0 0.0 6.6 Rain. residue 35 36.1 7.2 72.0 6.6 F Amount obtained 937 880, 6 Injection 968 907.0 20.7 80.0 19.5 Loss 31 26.4

Table 3A

Report on vacuum distillation of raw material

Raw material B - 650 ° I fraction Column used: Sarnia Hi ? (440 ° C + residue from Vac atm. distillation Temp. ° F Pressure Ref 1. Fr • Art. Hm. API Steam D. na- Torr after- C. ml G Attention. 61 ° F time measure VLT ATM 61 ° F Thu Pulse. EQV. hyd- ° F rog.

315 601.4 350 5,000 Zah. before. fr. 344 636.8 382 5,000 300 reading 342 644.9 389 4,000 500 reading 344 656.3 395 3,300 1 639 666.4 7.8 138.0 4.1 353 680.1 411 2,500 400 reading 364 701.6 430 2,100 2 646 666.9 9.4 138.0 5.6 333 736.0 419 0.400 200 reading

336 751.9 432 0,300 3 330 334.3 12.4 139.0 8.3 391 799.9 468 0,500 4 173 167.7 19.0 139.0 14.5 411 851, 6 500 0,270 5 181 167.3 26.8 139.0 21.7 460 899.8 538 0,360 6 181 167.1 27.0 139.0 21, 9 484 950.3 569 0,222 7 257 238.4 26.2 139.0 21.2 Weaning < distillation to verify temp. between containers at the customer (deleted) 5.3 g) 472 935.7 576 0.222 Zah. before. fr. 521 976.3 595 0,340 8 91 85.4 23.7 139.0 18.9 527 999.9 610 0,235 9 85 80.8 23.0 139.0 18.2 527 1025.6 624 0,130 10 98 93.8 21.6 139.0 16.9 Deletion 16.5 g of the remaining substance from (<4 < g of water) Koncové předl. 20 May 17.8 (matem, comb.) Oddestil. volume 2701 Stop the column 4 4.0 0.0 0.0 3.4 Rain. residue 593 621.8 11.0 214.0 3.4 Amount obtained 3298 3311.7 Injection 3298 3326,3 18.0 234.0 8.6 Loss -5 14.6

Table 3B

Report on distillation of distillation residues of raw material

Raw material B - 650 ° F (440 ° C) + Atm. distillation Column used: Sarnia Hi Vac

Temp. par Hm. Zah.-Kon. G

Order no. API ml 60/60 at

15.4 ° C

Hust. Hm at% 15.4 ° C

Order no. Hm. Order no.

601 - 656 666.4 639

4.1

1.0435 20.12 19.38 20.03 19.40 99 99 99 9

99,999,999

999 999 9999

999 99 99 99 99

2 656 - 702 666.9 646 5.6 1,0321 20.14 19.59 20.05 19.62 3 702 - 752 334.3 330 8.3 1,0122 10,09 10.01 10,05 10,02 4 752 - 800 167.7 173 14.5 0.9692 5.06 5.25 5.04 5.25 5 800 - 852 167.3 181 21.7 0.9236 5,05 5.49 5.03 5.50 6 852 - 900 167.1 181 21.9 0.9224 5,05 5.49 5.02 5.50 7 900 - 950 238.4 257 21.2 0.9267 7.25 7.79 7.17 7.80 8 950 - 976 85.4 91 18.9 0.9408 2.58 2.76 2.57 2.76 9 976 - 1000 80.8 85 18.2 0.9452 2.44 2.58 2.43 2.58 10 1000 - 1026 93.8 98 16.9 0.9535 2.83 2.97 2.82 2.98 Stop 4.0 4 3.4 1,0489 0.12 0.12 0.12 0.12 columns D. 1026 + 621, 8 593 3.4 1,0489 18, 78 17.98 18.69 18.01 remnants Ending 17.8 20 May 0.54 0.61 0.54 0.61 master Total 3311.7 3298 100.00 100.00 99.56 100, 1 Loss 14.6 -5 0.44 -0.15 Injection 3326,3 3293 8.6 1.0100 100.00 100.0 Reverse calculation of API and density 9.4 1,0039

Table 4

Elementary composition of raw material

Analysis of raw material B 650 ° F (440 ° C) + residue Element Contents

Nitrogen 0,991 wt. Sulfur 0.863 wt. Nickel 8.61 ppm Vanad <0.2 ppm

·· ·· «· ·« 9 ·· ·

Table 4 shows the partial elemental composition of the atmospheric distillation residue (650 ° F - 440 ° C) including some unidentified impurities. Table 4 shows the weight percent nitrogen, sulfur, nickel and vanadium in the residue after atmospheric distillation of feedstock B. The following steps remove these substances.

Step 5 - Pyrolysis of isolated fractions

A high temperature reactor is used for pyrolysis and degradation of the proportion of non-diamamantoid components in the various distillation fractions obtained in step 4 (Figure 12), thereby enriching the residue of diamontoide. The pyrolysis process is carried out at 450 ° C for 19.5 h. Gas chromatogram (FID) of fraction # 6 (Table 3B) is shown in Figure 18A. Figure 18B is a chromatogram of the pyrolysis product. A comparison of these chromatograms shows that pyrolysis removes the major non-diamondoid hydrocarbons and significantly increases the concentration of higher diamondoids, particularly hexamantanes. A PARR ^R 500 ml reactor from PARR Instrument Company, Moline, Illinois is used in this pyrolysis step.

Step 6 - Removal of the aromatic and polar non-diamintoid components

The pyrolysate obtained in step 5 is passed through a silica gel column for gravity chromatography (using a cyclohexane elution solvent) to remove polar compounds and asphaltenes (step 6, Figure 12). The use of silver nitrate impregnated silica gel (10% silver nitrate by weight) provides purer diamondoid-containing fractions by removing free aromatic and polar components.

* «999 ♦ ·· ·« ·· •·· 9 9 9 ·

- »······························

While it is not necessary to use this chromatographic method to separate flavorings, it facilitates the following steps.

Step 7 - Isolation of higher diamondoids by multi-column high performance liquid chromatography

One excellent way of isolating higher diamondoids of high purity utilizes two or more high performance liquid chromatography columns of different selectivities in succession

The first high performance liquid chromatography system uses Whatman M20 10/50 ODS columns operated in series with acetone as the mobile phase at a flow rate of 5.00 ml / min. A series of high performance liquid chromatography fractions were collected (see Figure 19). Fractions 36 and 37 are combined and collected for further purification on a second high performance liquid chromatography system. This pooled fraction (36 and 37) contains hexamantanes Nos. 7, 11 and 13 (Figure 19, see also Figure 13B).

Further purification of this pooled high performance liquid chromatography fraction on an ODS column is obtained using a high performance liquid chromatography column that has a different selectivity in the separation of different hexamantanes than the above-described ODS column. Figure 20 shows the elution times for individual hexamantanes on a Hypercarb high performance liquid chromatography column (with acetone as mobile phase).

Differences in elution times and elution order of hexamantanes on ODS and Hypercarb high performance liquid chromatography columns show two figures 19 and 20, for example. Hexamantanes Nos. 11 and 13 are eluted together by the high performance liquid chromatography ODS system together (Figure 19) but φ * φφφφ « The Hyperearb system separates in separate fractions (fractions 32 and 27, respectively) (Figure 20). obrázek φ · φ φ φ φ φ

The different elution order and times of selected higher diamondoids on these two systems can be used to separate higher diamondoids that co-elute. They can also be used to remove dirt. Using this method on the combined high performance liquid chromatography (ODS) fractions 36 and 37, the appropriate high performance liquid chromatography fractions on the Hypercarb column are collected to give high purity hexamantane # 13 (Figures 51A and 51B). Additional high performance liquid chromatography on the ODS column and high performance liquid chromatography fraction times on the Hyperearb column can be used to isolate the remaining hexamantanes. This isolation method is also applicable to other higher diamondoids, although the composition of the elution solvent may vary.

The ODS and Hyperearb columns can also be used in reverse order for these insulations. Using a method similar to the above, i.e. fractionation of hexamantane-containing ODS fractions using a Hyperearb column or other suitable column and collection at appropriate elution times, may result in the isolation of the remaining high purity hexamantanes. This also applies to other higher diamondoids from tetramantanes to undecamantanes, including substituted forms.

Example 2

Steps 1, 2, 3, 4, 5 and 6 of Example 1 are repeated (Figure 12). The following step 7 is then modified.

Step 7 '

4440

4444

444

4 ··

4 4

4 ·· ·

4 • 4 • 4 45

4

4 * 4 4

4 4 9

4 4

Preparative capillary gas chromatography on two columns is used to isolate hexamantanes from the product of Example 1, step 6. Fraction times for hexamantanes are determined for the first column of preparative capillary gas chromatography, methylsilicone DB - 1 equivalent at retention times and gas chromatography / mass spectrometry assay methods. (Example 1, Step 2). The results are shown in Figure 42A. Two fractions, defined as peak fractions leaving column 2, are collected, containing two of the hexamantane components of feedstock B. The capillary gas chromatography apparatus used is from Gerstel, Inc, Baltimore, Maryland, USA.

The first column is used to concentrate higher diamondoids, such as hexamantanes, by collecting fractions that are passed to the second column (see Figure 42B showing hexamantanes Nos. 2 and 8). The second column, phenylmethylsilicone, equivalent to DB 17, further separates and purifies hexamantanes and is used to isolate given peaks and maintain them in individual traps (traps 1 to 6). Gas Chromato Trap Fraction 1 contains hexamantane No. 2 crystals. Gas Chromato Trap 3 Fraction 3 contains hexamantane No. 8 crystals. The following gas chromatographic / mass spectrometry analysis of the Gas Trap 1 (Figure 43A and B) shows high hexamantane No. 2 high. purity based on gas chromatography / mass spectrometry analysis of step 2. Similarly, gas chromatography analysis of the trap 3 substance (Figure 44A and B) shows that this substance is primarily hexamantane No. 8. Micrographs of hexamantane No. 2 and 8 crystals (analyzed as see Figures 43 and 44) are shown in Figures 45 and 46. This process can be repeated to isolate other hexamantanes. This also applies to other higher diamondoids.

· * * * «« «« «« «« ««

A 4 «O O 4 4 · 4 * 4 4 4 4 4 4 4 4 4 4

Example 3

Steps 1, 2, 3 and 4 (Figure 12} of Example 1 are repeated with feedstock A. Feedstock A has a particularly low diamondoid content in the fraction of the atmospheric distillation residue obtained in step 4. The pyrolysis step (5) of Example 1 can be omitted in particular if higher diamondoids tetramantanes, pentamantanes and cyclohexamantane, in which case the fractions collected in step 4 go directly to steps 6 and 7 in Example 1 or directly to step 7 of Example 2 (Figure 12). However, pyrolysis is highly desirable when non-diamintoid components are present.

The fraction corresponding to the removal of fraction 1 of step 4 (see Table 3 on distillation, Example 1 and Figure 17) is taken from this raw material. The first fraction is further fractionated by preparative capillary gas chromatography, similar to the treatment shown in Step 7 'of Example 2 (Figure 12).

A two column preparative capillary gas chromatography is then used to isolate the target tetramantanes from the distillation fraction purified by column chromatography (step 6, Figure 12). Using retention times and gas chromatography / mass spectrometry analysis methods (from step 2 of Example 1), fraction times for target diamondoids (e.g., tetramantanes) are set for the first column of preparative capillary gas chromatography, methylsilicone equivalent to DB-1. The results are shown in the upper part of Figure 21, identifying fractions 1, 2 and 3.

The first column is used to concentrate the target

Diamondoids (for example tetramantanes) by collecting fractions that are passed to the second column (phenylmethylsilicone, equivalent to DB-17) (see bottom of Figure 21). The second column further separates and purifies the target diamondoids and then passes them to individual traps (traps 1 to 6). Gas chromatography traps 2, 4 and 6 contain selected tetramantanes (Figure 21).

Highly concentrated tetramantane higher diamondoids are allowed to crystallize in a trap or dissolve and recrystallize from solution. Under a microscopic magnification of 30x, tetramantanes are visible in preparative gas chromatography traps 2, 4 and 6 (see Figure 22). If the concentrations are not sufficient for crystallization, further concentration by preparative high performance liquid chromatography is necessary. This method would also be applicable to the isolation of higher diamondoids from raw material A.

Example 4

Preparative gas chromatography of high performance liquid chromatography fractions

It may be appropriate to carry out, with heptamantanes, octamantanes and higher diamondoids, etc., further fractionation of the high performance liquid chromatography products obtained in Example 1, step 2. This may be performed by preparative capillary gas chromatography as described in Example 2, step 7 '.

The following higher diamondoid components are isolated and crystallized: all of the tetramantanes from both raw materials A and B, all pentamantanes (molecular weight 344) isolated from raw material B, two crystalline hexamantanes (molecular weight) · · · · · · · · · · · · · · ·

396) isolated from raw material B and two crystalline heptamantanes (molecular weight 394) isolated from raw material B, crystalline octamantane (molecular weight 446) isolated from raw material B as well as crystalline nonamantane (molecular weight 498) and crystalline decamantane (molecular weight 456) isolated Other higher diamondoid components can also be isolated using the methods shown in these examples.

Example 5A

Isolation of tetramantanes

The general methods of Examples 1 and 2 are used to enrich and isolate tetramantanes.

In this example, the pyrolytic step 5 (Figure 12) is not used and the product of step 4 is passed directly to the column chromatography (step 6 of Example 1). The column chromatography product was worked up as follows.

The eluate from column 6 of the analysis step is gas chromatography / mass spectrometry to determine the appropriate gas chromatography retention times for the tetramantane isomers. Individual tetramantanes are assigned a number according to their order of elution when analyzed by gas chromatography / mass spectrometry. This reference number is used to identify each tetramantane in the following steps. It will be appreciated that enantiomeric pairs are not distinguished in this analysis, so that a single number is assigned to these enantiomers (racemic mixtures). The gas chromatography retention times are varied as the gas chromatography columns and conditions change, and tables of new retention times are prepared as needed using this method. Below is a table used in the methods of Example 5D below.

Tetramantan

Ref. No. 123

Gas retention times. chrom./hm.

spectrom. (min) 11.28 11.84 12.36

Two column preparative capillary gas chromatography is then used to isolate tetramantane from the distillate fractions purified by column chromatography. The results are shown in Figure 21 with identification as fractions 1, 2 and 3.

The first column is used to concentrate the tetramantanes by collecting fractions that are converted to the second column (see Figure 21). The second column, phenylmethylsilicone, equivalent to DB-17, further separates and purified the tetramantanes and converts them into individual vessels (traps 1 to 6). The gas chromatography scavenger fractions 2, 4 and 6 are collected and further processed.

The highly concentrated tetramantanes are then allowed to crystallize from solution. Under a microscopic magnification of 30x, the crystals are visible in fractions 2, 4 and 6 of the gas chromatographic scavenger (see Figure 22). If the concentrations are not high enough for crystallization, further concentration by preparative gas chromatography is necessary. Figures 22A,

B and C show photomicrographs of tetramantane crystals isolated from raw material in traps Nos. 2, 4 and 6 corresponding to tetramantane Nos. 1, 2 and 3, respectively.

• Μ ·

- 61 -.....

· · * 4 € 4 9 4 9 9 9 9 9 9 9 9

After obtaining crystals of appropriate size, the substance can be used for structural determination using X-ray diffraction. The enantiomeric tetramantanes may be subjected to further separations to distinguish their two components as discussed above.

Example 5B

Tetramantane enrichment by pyrolysis

This example shows that pyrolysis (step 5, example 1, figure 12) can be used to isolate tetramantanes.

Prior to pyrolysis, non-diamintoid components are present in the fraction containing tetramantane (Figure 23A) (distillation fraction similar to that of Fraction 1, Figure 17). Pyrolysis degrades the non-diamintoid components into an easily removable gas and a coke solid. As shown in Figure 23B, the peaks of the non-diamintoid substances disappear after pyrolysis.

Pyrolysis is carried out by heating the tetramantane-rich distillation fraction in a reactor at 450 ° C for 20.4 h under vacuum.

Example 5C

Isolation of tetramantanes by simple high performance liquid chromatography system

Isolation of diamondoids by high performance liquid chromatography

In addition to the chromatographic and pyrolysis methods described

It> <

· Above, high performance liquid chromatography also provides sufficient enrichment for tetramantanes to allow their crystallization. Columns suitable for this use are well known to one of ordinary skill in the art. In some cases, reverse-phase high performance liquid chromatography, with acetone as the mobile phase, can be used to perform this purification. Preparative high performance liquid chromatography of raw material A, gas condensate, distillation fraction corresponding to fraction 1 (Figure 17) is performed and the high performance liquid chromatography chromatogram is recorded. 9 fractions were obtained during this chromatography. Two columns of 25 cm high performance liquid chromatography with an inner diameter of 10 mm are used. Vydac octadecylsilane columns run in series (Vydac columns are from The Separations Group, Inc, CA, USA). A sample of a 55 mg / ml tetramantane fraction containing 20 µl was injected onto the column. The columns are put into operation using acetone at a flow rate of 2.00 ml / min as the mobile phase support.

Figure 24 (A, B) compares the starting gas chromatogram (Figure 24A) and the high performance liquid chromatography fraction 6. The high performance liquid chromatography fraction 6 is significantly enriched in tetramantane (Figure 24B compared to the starting material (Figure 24A)). Tetramantane 2 in the high performance liquid chromatography fraction 6 approaches a concentration sufficient to effect crystallization.

Example 5D

Isolation of single isomers of tetramantanes by high performance liquid chromatography using multiple columns with different selectivities · · · · · · · ·

As shown in Example 5C, tetramantanes can be isolated by high performance liquid chromatography methods. In this example, high performance liquid chromatography columns of different selectivities are used to isolate the individual tetramantane isomers. Figure 25 shows the preparative separation of tetramantanes by an octadecylsilane (ODS) high performance liquid chromatography column with acetone as the mobile phase. The distillation product used as starting material in Example 5B is a raw material. In particular, fractionation is carried out by preparative high performance liquid chromatography of atmospheric distillation fractions of feedstock B collected at about 650 ° F (340 ° C). The first column contains two Wjatman M20 10/50 (x2) columns operated in series using acetone at a flow rate of 5.00 ml / min as mobile phase (4070 kPa), 0.500 ml feed containing 56 mg / ml of the acetone containment fraction. The resulting chromatogram is shown in Figure 25. Tetramantane 1 is eluted first, tetramantane 3 is eluted second, and tetramantane 2 is eluted last on a high performance liquid chromatography system (Figure 25). The detector used is a differential refractometer. From this step, fraction 12 (Figure 25) is obtained for further purification.

Further purification of fraction 12 is achieved by a Hypercarb-S high performance liquid chromatography column having a different specificity than the ODS columns above for the isolation of tetramantane 2 (Figure 26). Two Hypercarb-S columns (manufactured by Thermo Hypersil, Penn, USA), 4.6 mm ID x 250 mm are run in series using acetone at a flow rate of 1.00 mL / min as the mobile phase (1240 kPa), injection 50 μΐ 4 mg / ml in acetone, also using a differential refractometer. Tetramantane 3 is eluted first, tetramantane 1 is eluted second, and tetramantane 2 is eluted last on this Hypercarb high performance ka64 high performance chromatography system (Figure 14). Tetramantane 2 is removed from this high performance liquid chromatography step (Figure 26) and its purity is shown in Figures 28A and B. The high performance liquid chromatography steps on the ODS Hypercarb column result in isolation of all tetramantanes (enantiomers can be separated by chiral high performance liquid chromatography methods).

Figure 27A shows the total ion chromatography (TIC) gas chromatography / mass spectrometry fraction of the high performance liquid chromatography fraction containing tetramantane 1 and below in Figure 27B is its mass spectrum. Figure 29A shows the total ion chromatography (TIC) gas chromatography / mass spectrometry of the high performance liquid chromatography fraction containing the isolated tetramantane 3, and Figure 29B below shows the mass spectrum.

Example 5E

Isolation of substituted tetramantanes

The alkyl tetramantanes can be purified by the methods described for the unalkylated tetramantanes of Examples 5A to 5D. Figure 30 shows a monomethylated tetramantane of molecular weight 306 providing a molecular ion of m / z 306 on mass spectrometry and showing a mass spectrometric loss of the methyl group, obtaining m / z 291 mass spectrometric ion fragment (pointing to the tetramantane residue). This alkylated compound is isolated on a Hypercarb high performance liquid chromatography column and exhibits a retention time of 11.46 min in the gas chromatography / mass spectrometry system used herein (FIG. 1).

9 4

30). It may be necessary to use further high performance liquid chromatography or preparative gas chromatography separations (as in Examples 3 and 4) to isolate some alkyl tetramantanes.

Example 6A

Isolation of pentamantanes by preparative gas chromatography

Steps 1 to 4 of Example 1 (Figure 12) are repeated.

In step 5, raw material B, distillation fraction 650 ° F (340 ° C) + residue (Table 3, Figure 18) is pyrolyzed under vacuum at 450 ° C for 16.7 h. The product is processed in accordance with Example 1, step 6.

The eluent from the column chromatography (step 6) is analyzed by gas chromatography / mass spectrometry to determine the retention times of the gas chromatography of the pentamantane isomers. Individual pentamantane components having a molecular weight of 344 will receive a number according to their elution order in this gas chromatography / mass spectrometry analysis.

A two-column preparative capillary gas chromatography chromatography apparatus is then used to isolate the pentamantanes from the products of step 6 above. An example of the result shows for pentamantane 1 in Figure 31. The gas chromatography peak containing pentamantanes on the first column is identified as peak cut out and converted to column 2 in Figure 31A.

The first column is used to concentrate pentamantane using a fraction that is converted to a second column.

· · · · · · · · · · · · · · · · · · · · · · ·

The second column, phenylmethylsilicone, DB-17 equivalent, further separates pentamantane 1 from the other substances. This substance identified at the peak identified as the trapped peak is passed to a gas chromatography fraction 6 trap where pentamantane 1 crystals accumulate (see Figure 31B). Gas Chromatography / Mass Spectrometry analysis of Trap 6 (Figure 32) shows that it is pentamantane 1 (in reference to the gas chromatography retention time / mass spectrometry found for this preparative gas chromatography method, it shows pentamantane 1 which elutes first, retention time 16.233 min). Figures 32A and B show the high purity of pentamantane 1 taken from the gas chromatography trap 6. This process can be repeated to isolate four additional pentamantanes and three enantiomeric pairs that can be separated by chiral high performance liquid chromatography or other resolution methods.

Highly concentrated pentamantanes crystallize either directly in the trap or from solution. Under a microscopic magnification of 30x, the crystals of pentamantane 1 are visible in a preparative gas chromatography trap (see Figure 33A). These crystals are perfectly clear and show a high refractive index. Pentamantane 1 crystals never existed before this isolation. If the concentrations are not high enough for crystallization, further concentration by preparative gas chromatography may be necessary. Figure 33B is a photomicrograph of two pentamantanes co-crystallizing in a preparative gas chromatography trap.

After obtaining crystals of appropriate size, the nonenantiomeric pentamantane materials can be transferred to the structure by X-ray diffraction. The enantiomeric pentamantanes may be subjected to further separations to distinguish their two components.

• * 9 • · · • * * 9 9 9 99 9 • • ·· Φ 9 • 9 9 9 9 9 • 9 9 9 9 9 · 9 9 • 9 9 9 9

• · φ 9

Example 6Β

Isolation of pentamantanes by high performance liquid chromatography

Steps 1 to 6 of Example 6A are repeated. The reference number of the gas chromatography / mass spectrometry analysis and the retention times for the 344 pentamantanes are as follows.

Reference no.

pentamantane 12345 6

Retention times

GC / MS * (min) 13.68 15.26 15.31 15.72 15.85 16.06 * (HP-5MS film 0.25 gm, 0.25 mm ID x 30 m, helium gas carrier)

Pentamantane 1 containing the ODS fractions shown in Figure 34 is further purified by Hypercarb high performance liquid chromatography (Figure 35) for the isolation of pentamantane 1. Figure 14 shows how the high performance liquid chromatography on the ODS column and the high performance liquid chromatography on the column can be used together. Hypercarb for isolation of the remaining pentamantanes. The ODS and Hypercarb columns can be used in reverse order for this insulation. Figure 36 shows the total ion chromatogram (TIC) of gas chromatography / mass spectrometry of isolated pentamantane 1. The lower half of Figure 36 shows the mass spectrum of pentamantane 1 peak in gas chromatography / mass spectrometry. As shown in Figures 14 and 34, they contain the remainder

- 69 - .....

• ·· ·

high performance liquid chromatography fraction on ODS column with additional pentamantanes. In a similar manner as above, i.e. fractionation of the pentamantane-containing ODS fractions using a Hypercarb column (as shown in Figure 14) on another suitable column and collection at appropriate elution times, isolation of the remaining high purity pentamantanes as shown in Figures 37 to 41 is achieved. Figure 37 illustrates the total ion chromatography (TIC) gas chromatography / mass spectrometry and mass spectrum of pentamantanes 2 isolated by two different high performance liquid chromatography columns. Figure 38 shows the total ion chromatogram (TIC) of gas chromatography / mass spectrometry and the mass spectrum of pentamantanes 3 isolated using two different high performance liquid chromatography columns. Figure 39 shows the total ion chromatography (TIC) of gas chromatography / mass spectrometry and the mass spectrum of pentamantanes 4 isolated using two different columns of high performance liquid chromatography. Figure 40 shows the total ion chromatogram (TIC) of gas chromatography / mass spectrometry and the mass spectrum of pentamantanes 5 isolated using two different high performance liquid chromatography columns. Figure 41 shows the total ion chromatogram (TICj of gas chromatography / mass spectrometry and the mass spectrum of pentamantanes 6 isolated using two different high performance liquid chromatography columns. Enantiomeric pentamantanes are not distinguished by gas chromatography / mass spectrometry and therefore these enantiomeric pairs are described with the same number. In addition, as noted above, a condensed isomer of molecular weight pentamantanes 330, which is more spherically deformed and appears at significantly lower concentrations, is present. 99

The manthanum component is evident in the gas chromatography / mass spectrometry analyzes of the pyrolysis product of the distillation fraction 5 purified by step 6 of Example 1 (Figure 12). This pentamantane component elutes at 14.4 min for the analysis of Example 1, Step 4, and can be isolated by the methods of this Example.

Example 6C

Purification of substituted pentamantanes

Raw materials A and B contain substituted pentamantanes. Substituted pentamantanes from these raw materials can be enriched and purified according to the methods described for the non-alkylated pentamantanes in Examples 1-4. The monomethylated pentamantane enriched in this case has a molecular weight of 358 (providing molecular ion m / z 358 by mass spectrometry and showing a methyl group mass spectrometric loss) This alkylated compound is enriched in the high-performance liquid chromatography fraction on ODS No. 31 and can be further purified by crystal formation by further high-performance liquid chromatography separation or alternatively by preparative gas chromatography ( as in Example 3).

Example 7A

Isolation of hexamantane components

The purpose of this example is to show methods that can be used to enrich and isolate 39 hexamantane components. The method of Example 1 is repeated with the following changes. In step 5, the distillation fraction 6 of the distillation residue of raw material B 650 ° F (340 ° C) (Table 3, Figure 18) is pyrolyzed under vacuum at 450 ° C for 17.3 h.

The column chromatography eluent (step 6) was analyzed by gas chromatography / mass spectrometry to determine the retention times of hexamantanes in gas chromatography. Individual hexamantane components with a molecular weight of 396 are numbered according to the order of elution in this gas chromatography / density spectroscopy analysis. For convenience, the hexamantanes most commonly used are selected. Similar assays can be performed for other molecular weights. The elution times of hexamantanes are between 17.88 min (hexamantane 1) and 19.51 min (hexamantane 7) in this gas chromatography / mass spectrometry analysis. Retention times vary with changes in gas chromatography columns and conditions, which requires retention times to be measured again. Figure 13A describes another result of gas chromatography / mass spectrometry analysis for hexamantane components.

Preparative two-column capillary gas chromatography is used to isolate hexamantanes from distillate fractions purified by column chromatography. Fraction times for hexamantanes are set for the first column of preparative capillary gas chromatography, methylsilicone, DB-1 equivalent, using retention times and methods from gas chromatography / mass spectrometry analysis. The results are shown in Figure 42A, identified as peak peaks and converting the day to a column 2 containing two hexamantane fractions.

The first column is used to concentrate hexamantanes by removing fractions that are converted to the second column (see Figure 42 for hexamantane 2 and 8). The second column, phenyl, methyl silicone, equivalent to DB-17, further separates and purifies hexamantanes and is then used to isolate the peaks and retain them in individual traps (traps 1 to 6). The gas chromatography trap 1 is further processed to separate hexamantanes 2. Fraction 3 of the gas chromatography trap is collected and further processed to separate hexamantanes 8. Further analysis by gas chromatography / mass spectrometry from the trap 1 (Figure 43) shows that it is hexamantane 2 based on previous gas chromatography / mass spectrometry analysis. Similarly, the analysis of the gas chromatographic trap 3 (Figure 44) shows that it is primarily hexamantane 8. This process can be repeated to isolate further hexamantanes.

The highly concentrated hexamantanes are then allowed to crystallize either directly in the trap or from the solution. Under a microscopic magnification of 30x, the crystals in the Fraction 1 trap of preparative gas chromatography are visible (see Figure 45). These crystals are perfectly clear and show a high refractive index. Hexamantane 2 crystals never existed before this isolation. If the concentrations are not high enough for crystallization, further concentration by preparative gas chromatography may be necessary. Figure 46 is a photomicrograph of hexamantanes 8 that crystallized in the preparative gas chromatography trap 3. Hexamantane crystals 8 never existed before this isolation.

After obtaining crystals of appropriate size, the non-enantiomeric hexamantane components can be converted for structural determination by X-ray diffraction. The enantiomeric hexamantanes must be subjected to further separations to distinguish the two components.

Example 7B in "" in ""

Isolation of hexamantanes by simple high performance liquid chromatography system

The high performance liquid chromatography columns used are two 50 cm x 20 mm internal diameter columns. Whatman octadecylsilane (ODS) columns are run in series (Whatman columns are from Whatman Inc, USA). A sample of a 500 μΐ solution of the pyrolysis product of saturated hydrocarbon fraction 6 (54 mg), the product of Example 1, step 6, was injected onto the columns. The columns are run with acetone at a flow rate of 5.00 ml / min as the mobile phase. Some high performance liquid chromatography fractions achieve the purity necessary to crystallize individual hexamantanes, as shown by hexamantane 8 in fraction 39 of high performance liquid chromatography on the ODS column (Figure 47) for hexamantane 10 in fraction 48 of high performance liquid chromatography on ODS column (Figure 48) and hexamantane 6 in fraction 63 of high performance liquid chromatography on an ODS column. Alternatively, a Hypercarb column (manufactured by Thermo Hypersil, Penn, USA) or another suitable column can be used to purify hexamantanes to concentrations necessary for their crystallization. Preparative separation was performed by high performance liquid chromatography on a Hypercarb column of the saturated hydrocarbon fraction of the pyrolysis product of Fraction 6 of the distillate of raw material B and the chromatogram of the high performance liquid chromatography was recorded using a differential refractometer. Fractions (e.g., Figure 50) are collected during this run and show that most hexamantanes exhibit different elution times (verified by gas chromatography / mass spectrometry analysis) on the Hypercarb high performance liquid chromatography system (Figure 20).

·· ·· «·« · ···

Example 7C

Isolation of hexamantanes using multiple columns of high performance liquid chromatography of different selectivities

The high performance liquid chromatography fractions on the Hyperearb column are collected to obtain the high purity hexamantanes 13 shown in Figure 51. Additional high performance liquid chromatography fractions on the ODS column and high performance liquid chromatography on the Hyperearb column can be used to isolate the remaining hexamantanes. The ODS and Hyperearb columns can also be used for this insulation in reverse order. Figure 52 shows the total ion chromatography (TIC) gas chromatography / mass spectrometry of the high performance liquid chromatography fraction on a Hyperearb column containing hexamantane 7. The lower half of Figure 52 shows the mass spectrum of a gas chromatography / mass spectrometry showing high purity of isolated hexamantane 7.

The different remaining high performance liquid chromatography fractions on the ODS column (Figure 19) containing additional hexamantanes can be separated in a similar manner using a similar method as above, ie fractionating hexamantane-containing ODS fractions using a Hyperearb column or other suitable column and collecting at appropriate elution times. This also applies to 382 hexamantanes, irregular hexamantanes having a much lower incidence in the raw materials used than 396 hexamantanes. Figures 53 and 54 are reconstructed ion chromatograms for m / z 382 pointing to hexamantanes that pass at 18,30 min and 18,07 min respectively Pictures • t ·· # «• * · ··« <

♦ 99 «<

And 99 also show the corresponding mass spectra for these peaks of 18.30 min and 18.07 min, respectively. which show the presence of 382 hexamantanes in the saturated hydrocarbon fraction of the pyrolytic treatment product of Fraction 6 from the distillation of raw material B. The 382 hexamantanes exhibit internal bond deformation, lower stability and correspondingly lower concentrations than the 396 molecular weight hexamantanes, so 382 are less preferred.

Enantiomeric hexamantanes are not distinguished by gas chromatography / mass spectrometry and therefore these enantiomeric pairs are reported under one number. These enantiomers can be isolated by chiral separation methods.

Example 7D

Isolation of substituted hexamantanes

Substituted hexamantanes, including alkylhexamantanes, also occur in raw materials A and B. These natural substituted hexamantanes have similar uses as unsubstituted hexamantanes, can act as useful intermediates in various hexamantane applications (e.g., polymer production) and can be dealkylated to yield the corresponding non-derivatized hexamantanes. Accordingly, methods for isolating individual substituted hexamantanes are described and exemplified by isolating alkyl-substituted components. Substituted hexamantanes, including alkylhexamantanes, can be isolated of high purity using simple high performance liquid chromatography separation of the distillation fractions, as shown in Figure 55. Figure 55 shows that fraction 55 from high performance liquid chromatography separation on the ODS column from pyrolysis of distillation fraction 6 feedstock B contains high purity methylated hexamantane. The monomethylated hexamantanes have a molecular weight of 410 (obtaining a mass spectrometric molecular ion of m / z 410 and exhibit a mass spectrometric loss of the methyl group to give an ion fragment 395 (Figure 55B)). Isolation of substituted hexamantane components by high performance liquid chromatography may require multiple columns of different selectivities. For example, high performance liquid chromatography columns ODS and Hypercarb are used in sequence to isolate the methylcyclohexamantane components (methyl substituted hexamantane, molecular weight 342) of the saturated hydrocarbon fraction of the pyrolysis product of fraction 6 from the distillation. Fractions 23-26 are combined from the first run of high performance liquid chromatography on an ODS column and collected for further purification on a second high performance liquid chromatography system. The pooled fractions (Figure 56) contain a mixture of hexamantane (molecular weight 342, considered as cyclohexamantane), which elutes on this gas chromatography / mass spectrometry system at 12.31 min and three methylcyclohexamantanes (1-3) that elute at times 12.56, 12.72 and 13.03 min. Further purification of this mixture (i.e., combined fractions 23 to 26 of high performance liquid chromatography on an ODS column is accomplished using a Hypercarb stationary phase high performance liquid chromatography column. A sample of 50 μΐ, about 1 mg of this combined acetone fraction is injected onto a 10 mm internal diameter 250 mm operated using acetone at a flow rate of 3.00 ml / min as a mobile phase (3300 kPa) using a differential refractometric detector In this Hypercarb system, methylcyclohexamantane 1 elutes predominantly in fractions 18 to 22 and methylcyclohexamantane 2 elutes predominantly in Fractions 23 to 25. Methylcyclo76 hexamantane 1 and 2 are isolated with sufficient purity to form crystals The total ion chromatogram of gas chromatography / mass spectrometry and the mass spectrum of these substances is shown in Figures 57 and 59 and the crystals are shown in Figures 59 and 60. Figure 5 9 shows a methylcyclohexamantane crystal precipitated from Hypercarb high performance liquid chromatography fractions 19 to 21, and FIG. 60 shows a methylcyclohexamantane crystal precipitated from Hypercarb high performance liquid chromatography fraction 23.

To separate the two components, the enantiomeric pairs must be subjected to further separations. After obtaining crystals of appropriate size, nonenantiomeric alkylhexamantanes may be subjected to structure determination by X-ray crystallography.

Example 8A

Isolation of heptamantane components

The eluent from the column chromatography (step 6, figure 12) is analyzed by gas chromatography / mass spectrometry to determine the retention times of heptamantanes in gas chromatography. Individual heptamantane components with molecular weights 394 and 448 will receive numbers according to their elution order in this gas chromatography / mass spectrometry analysis (see Figure 13A for representative assay values). Heptamantanes of molecular weight 448, the most frequent group of heptamantanes, were chosen for simplicity in this example. Similar assays can be prepared for heptamantanes with different molecular weights.

A two column capillary gas chromatography apparatus is then used to isolate heptamantanes from the distillate fractions purified by column chromatography. Fraction times for heptamantanes are set for the first preparative gas chromatography capillary column, methylsilicone, DB-1 equivalent, using retention times and methods from gas chromatography / mass spectrometry analysis (from step 2 above, Figure 12). An example of the result is shown at the top of Figure 61, identified as a peak cut out and converted to column 2 and containing two of the heptamantanes from raw material B.

The first column is used to concentrate the heptamantanes by collecting fractions that are passed to the second column (see Figure 61 showing heptamantanes 1 and 2). The second column, phenylmethylsilicone, equivalent to DB-17, further separates and purified the heptamantane components and then is used to isolate the peaks and trap them in individual vials (traps 1 to 6). Fraction 2 gas chromatography trap is collected and further processed to separate heptamantanes 1. Fraction 4 gas chromatography trap is collected and further processed to separate heptamantanes 2. Subsequent analysis of the material from the trap 2 by gas chromatography / mass spectrometry (Figure 62) shows that this is heptamantane 1 based on an earlier gas chromatography / mass spectrometry analysis of step 4. Similarly, gas chromatography analysis shows that the substance from the scavenger 4 (Figure 63) is hexamantane 2. This process can be repeated to isolate the other heptamantane components.

The highly concentrated heptamantanes are then allowed to crystallize either directly in the trap or from the solution. Under a microscopic magnification of 30x, the crystals in the gas chromatographic fraction trap 2 are visible (see Figure 64). These crystals are perfectly clear and show a high refractive index. Crystals 4 9 9

9 4 4 4 4 4 9 4 5

No. 4,944,444,444 component 1 of heptamantane never existed prior to this isolation. If the concentrations are not high enough for crystallization, further concentration by preparative gas chromatography may be necessary. Figure 65 is a photomicrograph of heptamantane component 2 that crystallizes in the trap 4 of preparative gas chromatography. Crystals of heptamantane component 2 never existed before this isolation.

Once crystals of the appropriate size have been obtained, the heptamantane materials can be used to determine the structure by X-ray diffraction. The enantiomeric heptamantanes may be subjected to further separations to distinguish their two components.

Example 8B

Purification of individual heptamantane isomers

High performance liquid chromatography also provides sufficient enrichment for some heptamantanes to crystallize them.

The same high performance liquid chromatography columns were used as in the other examples (ODS and Hypercarb). A sample of 500 μΐ of the saturated hydrocarbon fraction 7 pyrolysis product (step 6 product, Figure 12) is injected onto the ODS columns. Pyrolysis of fraction 7 uses 25.8 g heated at 450 ° C for 16 h. Some of the high performance liquid chromatography fractions on the ODS column achieve the purity necessary to crystallize individual heptamantanes, as shown in Figure 66 for heptamantane 1 in fraction 45 -high performance liquid chromatography on the ODS column. Others, such as heptamantane 2 in fraction 41 of the high performance liquid chromatography on the ODS column (Figure 67), heptamantane 9 in 9

99 fraction 61 of the high performance liquid chromatography on the ODS column (Figure 68) and heptamantane 10 in fraction 87 of the high performance liquid chromatography on the ODS column (Figure 69) may require further separation on high performance liquid chromatography systems with other selectivities. Chromatographic separation of fractions from the ODS column (Figure 13B) on the Hypercarb column results in the purity necessary for crystallization of the individual heptamantane components, as shown for the heptamantane component 1 in fraction 55 of high performance liquid chromatography on the Hypercarb column (Figure 70) and heptamantane 2 (Figure 71). ). Higher diamondoids in different high performance liquid chromatography fractions could be separated using other chromatographic methods including preparative gas chromatography and other high performance liquid chromatography separations using columns with different selectivity as described below. In addition, other methods known in the art of crystallization, including, but not limited to, fractional sublimation, crystallization, or zone refining can be used to purify heptamantanes.

Using methods similar to the above, i.e., fractionation of fractions from the ODS column containing heptamantane using a Hypercarb column or other suitable columns and collection at appropriate elution times, recovery of the remaining heptamantanes can be achieved. This is also true for 420 and 434 heptamantanes, which are much lower in the raw materials used than 394 and 448 heptamantane components. The 420-heptamantane component exhibits ODS fraction 61 in fraction 61 (Figure 73A). very strong molecular ion in the mass spectrum (in this case m / z 420, Figure 73B) for the m / z 420 component at 16.71 min. Mass spectrum with its expression80

molecular ion and low number and presence of fragments characterizes the diamondoid component.

Example 8C

Isolation of substituted heptamantanes

Substituted heptamantanes, including alkylheptamantanes, also occur in raw materials A and B. Alkylheptamantanes can be purified by removal of non-diamintoid impurities from the raw materials by pyrolysis as described above. Certain alkylheptamantanes persist after the pyrolysis process, as is the case for the heptamantane components identified above. Substituted heptamantanes, including alkylheptamantanes, can be isolated in high purity by single separation by high performance liquid chromatography as shown in Figure 74. Monomethylated heptamantanes have a molecular weight of 408 (yield a mass spectrometric molecular ion of m / z 408 and exhibit a mass spectrometric loss of the methyl group by providing fragment m / z 393, which points to the rest of the heptamantanes) (Figure 74B).

Example 9A

Isolation of octamantane components

The fraction of step 6 enriched in octamantanes is subjected to reverse phase high performance liquid chromatography.

In some cases, reverse-phase high performance liquid chromatography with acetone can be used as the mobile phase to carry out this purification. Preparative high performance liquid chromatography of raw material B on the ODS column The pyrolysis product of the saturated hydrocarbon fraction 7 (used in Example 8A) is performed and the chromatogram is recorded using a differential refractometer. The high performance liquid chromatography fractions were analyzed by gas chromatography / mass spectrometry to determine the octamantane elution times in high performance liquid chromatography and to monitor purity (see Figure 13A for representative assay values). The high performance liquid chromatography columns are the same ODS and Hypercarb columns as used in the previous examples. A sample of 500 μΐ of the acetone solution of the pyrolysis product of fraction 7 of saturated hydrocarbons (25 mg) is injected onto ODS columns. Using this high performance liquid chromatography system, some octamantanes achieve the purity necessary to crystallize individual octamantanes. For example, Figure 75 shows the total ion chromatogram of gas chromatography / mass spectrometry and the mass spectra of the high performance liquid chromatography fraction in which octamantane 1 was purified to form crystals (see Figure 76). Fraction 63 together provides octamantane 3 and 5 (Figure 77) which co-crystallize from this fraction (Figure 78).

Multiple columns such as Hypercarb can be used to isolate other high purity octamantane components (e.g., Figs. 79 and 80).

Example 9B

Isolation of substituted octamantane components

Alkyloctamantanes can be purified according to the methods described for the unalkylated octamantanes in Examples 1 and 3. Figure 81 (A / B) shows that high performance liquid chromium fraction 94 is present. The ODS column contains high purity methylated octamantane. The monomethylated octamantanes have a molecular weight of 460 (providing a molecular ion of m / z 460 at mass spectrometry and exhibiting a methyl group loss at mass spectrometry with a fragment ion at m / z 445 mass spectrometry indicating a octamantane residue (Figure 81B)). Where more alkyloctamantanes are present in the high performance liquid chromatography fraction on an ODS or Hypercarb column than one, further separation by high performance liquid chromatography of this fraction or by gas chromatography method (as in Example 3) can provide high purity alkyloctamantanes.

Example 10A

Isolation of nonamantane components

Preparative high performance liquid chromatography was performed on the ODS column of the pyrolysis product of saturated hydrocarbon fraction 7 from distillation of raw material B (substance described in Example 8A) and the high performance liquid chromatography fractions were analyzed by gas chromatography / mass spectrometry to determine nonamantane elution times in high performance liquid chromatography (Figure 82). ) and purity monitoring. A sample of 500 μΐ acetone solution of pyrolysis products of fraction 7 of saturated hydrocarbons (25 mg) is injected onto the columns. These columns are run with acetone at a flow rate of 500 ml / min as the carrier for the mobile phase.

Multiple high performance liquid chromatography columns may be used to isolate high purity nonamantane components.

High performance liquid chromatography columns of various ODS and Hy selectivity were used to illustrate this method. Sloup * Hy Hy Hy Hy S Hy S S S S Hy S S S S S S Percarb (as described in the previous examples) one after the other to isolate a single nonamantane. Fractions 84-88 (Figure 13B) containing nonamantane from high performance liquid chromatography on an ODS column were combined for further purification on a high performance liquid chromatography system with Hypercarb columns.

Inject a 50 μΐ sample of about 1 mg of combined fraction 84 to 88 from high performance liquid chromatography on an ODS column in methylene chloride on two Hypercarb columns, two 4.6 mm ID x 200 mm, operated serially using methylene chloride at a flow rate of 1.30 ml / min as mobile phase.

Figure 38 shows the total ion chromatography (TIC) gas chromatography / mass spectrometry for the high performance liquid chromatography fraction on a Hypercarb column containing nonamantane. The lower half of Figure 83 shows the mass spectrum of a gas chromatographic peak / mass spectrometry. Nonamantane was isolated by a third high performance liquid chromatography step using the same Hypercarb stationary phase column but with a methylene chloride / acetone solvent mixture (70:30 v / v, flow rate 1.00 mL / min). The resulting isolated nonamantane crystal and the corresponding mass spectrum is shown in Figure 84.

Using a method similar to the above, i.e. fractionating nonamantane-containing fractions from high performance liquid chromatography on an ODS column using columns with different selectivities such as Hypercarb or other suitable columns, high purity nonamantane 498 is isolated. This method can be repeated to isolate nonamantanes having a molecular weight of 552 and nonamantanes with moles of 538, 484 and 444, which are present in minor amounts in the described raw materials. It will be appreciated that enantiomeric nonamantanes do not distinguish in gas chromatography / mass spectrometry, but these enantiomers may be isolated by chiral separation methods.

Example 10B

Isolation of substituted nonamantanes

Substituted nonamantanes also occur in raw materials A and B. Alkylnonamantanes can be purified by methods described for nonalkylated nonamantanes. Figure 85 (A / B) shows methylated nonamantane in distillation fraction 7 of the pyrolysis product. One type of monomethylated nonamantane has a molecular weight of 512 (providing a molecular ion of m / z 512 at mass spectrometry) and exhibits a methyl group loss at mass spectrometry, yielding an ion fragment of m / z 497 at mass spectrometry indicating a nonamantane residue (Figure 85B). there are more alkylnonamantanes than one and can be isolated on ODS or Hypercarb columns, further separated by high performance liquid chromatography or preparative gas chromatography to give high purity alkylnonamantanes.

Example 11A

Isolation of decamantane components

Preparative high performance liquid chromatography on the ODS column of the pyrolysis product of the distillation fraction 7 of saturated hydrocarbon feedstock B was performed and the high performance liquid chromatography fractions were analyzed by gas chromatography / mass spectrometry to determine elution times by high performance chromatography (Figure 86) and purity monitoring. Two 50 cm x 20 mm internal diameter high performance liquid chromatography columns are used. Whatman Octadecylsilane Columns (ODS) are run in series. A sample of 500 μΐ of the pyrolysis product of fraction 7 of saturated hydrocarbons (25 mg) is injected onto the columns. The columns were run with acetone at a flow rate of 5.00 ml / min as the carrier for the mobile phase.

High performance liquid chromatography on multiple columns can be used to isolate high purity decamantane components. To illustrate this process, high performance liquid chromatography columns of various selectivities in succession are used to isolate a single decamantane. The first high performance liquid chromatography system comprises the same ODS columns as described above. Fractions 74 to 83 containing decamantane for further purification on a second high performance liquid chromatography system were combined from this HPLC. Five of these divisions were performed and all fractions containing decamantane were pooled. This combined fraction contains decamantane having a molecular weight of 456 and various impurities.

For purification of the ODS column 74-83 combined fractions 74 to 83, a sample of 50 μΐ of about 1 mg of the ODS column in an acetone / methylene chloride solvent (70:30 v / v) solvent mixture is injected onto two Hypercarb, 4, 6 mm ID x 200 mm operated in series using an acetone / methylene chloride mixture (70:30 volume ratio) at a flow rate of 1.00 ml / min as the mobile phase (at a pressure of 3312 kPa).

·· ·· «·

- 87 - ··· «* ·. ...

9 9

Figure 87 shows the total ion chromatography (TIC) gas chromatography / mass spectrometry of the concentrated fraction containing decamantane from high performance liquid chromatography on a Hypercarb column at 18.55 min. The lower half of Figure 87 shows the mass spectrum of a gas chromatography / mass spectrometry peak with a significant peak at m / z 456. The resulting decamantane crystal [1231241 (2) 3] of molecular weight 456 and the mass spectrum is shown in Figure 88. prior to pentamantane 3 on a Hypercarb high performance liquid chromatography system due to its compact, small surface structure (Figure 10). This property of decamantanes having a molecular weight of 456 allows it to be isolated in very high purity.

Using a method similar to the above, i.e., fractionation of high performance liquid chromatography fractions on an ODS column containing decamantane using columns with other selectivities such as Hypercarb or other suitable columns, high purity molecular weight 456 decamantane is isolated. This process can be repeated to isolate the 496 molecular weight decamantanes (shown in Figure 89 for the saturated fraction of the distillation fraction 7 pyrolysis product) as well as the 550 or 604 molecular weights and the 536, 576 and 590 molecular weight decamantanes found therein. lower raw materials. It will be appreciated that enantiomeric decamantanes do not distinguish by gas chromatography / mass spectrometry, but can be isolated by chiral separation methods.

Example 11B

Isolation of substituted decamantanes ·· «·

Substituted decamantanes also occur in raw materials A and B. Alkyldecamantanes can be purified by methods described for unalkylated decamantanes. Figure 90 shows that the saturated fraction of pyrolysis products of Distillate Fraction 7 contains methylated decamantanes. One type of monomethylated decamantanes has a molecular weight of 470 (providing molecular ion m / z 470 at mass spectrometry). If more than one alkyldecamantane is present in any high performance liquid chromatography fraction on an ODS or Hypercarb column, further separation of this fraction by high performance liquid chromatography may be performed, or alternatively may provide gas chromatography of high purity alkyldecamantanes.

Example 12

Isolation of undecamantane components

High performance liquid chromatography on multiple columns can be used to isolate high purity undecamantane components. This method can be demonstrated using high performance liquid chromatography columns used for decamantane of various selectivities which are used sequentially to isolate a single decamantane (Example 11). The corresponding starting material, pyrolysis product of distillation fraction 7 of feedstock B, appears to contain undecamantanes (Figure 91).

Concentrated undecamantane from the high-performance liquid chromatography fraction on the ODS 100+ column (Figure 13B) is shown in Figure 92. This fraction can be purified on a Hypercarb high-performance liquid chromatography column using a system similar to that described in Example • «9 9 9999 ···· 9 9 9 9 99 999 9

for the isolation of undecamantane. This process can be repeated to isolate undecamantane with molecular weights of 656 and / or

602 as well as 642, 628 molecular weights,

588, 548 or 534, the presence of which is less likely to be present in these raw materials.

Claims (134)

PATENT CLAIMS 1. An enriched selected higher diamondoid component which includes neither enriched unsubstituted antitetramantane nor enriched cyclohexamantane. An enriched selected higher diamondoid component according to claim 1 having a purity of at least 25% by weight. 3. A composition which is enriched in one or more selected higher diamondoid components, provided that when there is only one selected higher diamondoid component, said component is neither unsubstituted antitetramantane nor unsubstituted cyclohexamantane. 4. The composition of claim 3 wherein one or more of the selected higher diamondoid components represents at least 1% by weight of the composition. 5. The composition of claim 3 wherein the one or more selected higher diamondoid components represent at least 10% by weight of the composition. 6. The composition of claim 3 wherein the one or more selected higher diamondoid components comprise from 50 to 100% by weight of the composition. 7. The composition of claim 3 - 90 ~ »ft ft ··· ·· β ft ··. wherein one or more of the selected higher diamondoid components is from 70 to 100% by weight of the composition. 8. The composition of claim 3 wherein the one or more selected higher diamondoid components comprise from 95 to 100% by weight of the composition. The composition of claim 3, wherein the one or more selected higher diamondoid components comprise from 99 to 100% by weight of the composition. The composition of claims 3 to 9, wherein the one or more selected higher diamondoid components is or represents a single selected higher diamondoid component. 11. A composition comprising diamondoids enriched with one or more selected higher diamondoids in relation to the total amount of diamondoids, provided that when there is only one selected higher diamondoid component, said component is neither unsubstituted antitetramantane nor cyclohexamantane. 12. The composition of claim 11 wherein at least 25% by weight of the diamondoids is one or more selected higher diamondoids. 13. The composition of claim 12, wherein the one or more selected higher diamontoid components represent a plurality of components within one. 0 ·· 0 · • «« 0 00 <· · 0 • 0 0 0 0 0 0 · 0 0 • 0 0 0 0 0 0 0 0 0 0 0 • «0 000 0 « 00 0 00 0 « groups of diamondoids. 14. The composition of claim 12, wherein the or more selected higher diamondoid components are one selected higher diamontoid component. 15. The composition of claims 1-14, wherein the selected higher diamontoid component comprises one or more tetramantane components. 16. The composition of claim 15, wherein the one or more tetramantane components are a single tetramantane component. 17. The composition of claim 16, wherein the one tetramantane component is isotetramantane. 18. The composition of claim 16 wherein the one tetramantane component is skewtetramantane. 19. The composition of claim 16, wherein the one tetramantane component is a single skewtetramantane isomer. 20. The composition of claim 15, wherein the tetramantane components include substituted tetramantane components. 21. Enriched isotetramantane. • · ···· ·· · · · · Enriched enantiomer A of skewtetramantane. 23. Enriched enantiomer B of skewtetramantane. 24. An enriched tetramantane component according to claims 21 to 23 having a purity of at least 25%. The enriched tetramantane component of claims 21 to 23 in crystalline form. 26. The composition of claims 1-14, wherein the selected higher diamondoid components comprise one or more pentamantane components. 27. The composition of claim 26, wherein the one or more pentamantane components are a single pentamantane component. 28. The composition of claim 26, wherein the one or more pentamantane components are isolated optical isomers. 29. The composition of claim 26 wherein said one or more pentamantane components are isomeric pentamantane components. The composition of claim 26, wherein the one or more pentamantane components is a non-isomeric pentamantane component represented by the formula ^C 25 ^H 30 31. Enriched pentamantane component. 0 «0« ·········· · · · · 00 · 32. The enriched pentamantane component of claim 31 having a purity of at least 25% by weight. The enriched pentamantane component of claim 31, which is in crystalline form. The enriched pentamantane component of claim 31, wherein the pentamantane component is pentamantane [1231]. The enriched pentamantane component of claim 31, wherein the pentamantane component is the pentamantane enantiomer A [1213]. The enriched pentamantane component of claim 31, wherein the pentamantane component is the pentamantane enantiomer B [1213]. The enriched pentamantane component of claim 31, wherein the pentamantane component is the pentamantane enantiomer A [1234]. The enriched pentamantane component of claim 31, wherein the pentamantane component is the pentamantane enantiomer B [1234]. The enriched pentamantane component of claim 31, wherein the pentamantane component is the pentamantane enantiomer A [12 (1) 3]. The enriched pentamantane component of claim 31, wherein the pentamantane component is the pentamantane enantiomer B [12 (1) 3]. • 99 • · · · · · 99 9999 9 9 9 9 9 · 9 9 9 • · · 9 9 9 9 • · · · • 9 9 9 The enriched pentamantane component of claim 31, wherein the pentamantane component is pentamantane [1212]. The enriched pentamantane component of claim 31, wherein the pentamantane component is pentamantane [1 (2,3) 4]. The enriched pentamantane component of claim 31, wherein the pentamantane component is pentamantane [12 (3) 4]. The enriched pentamantane component of claim 31, wherein the pentamantane component is an unsubstituted pentamantane component. The enriched pentamantane component of claim 31, wherein the pentamantane component is a substituted pentamantane component. The composition of claims 1 to 14, wherein the selected higher diamondoid components comprise one or more hexamantane components. 47. The composition of claim 46, wherein the one or more hexamantane components are a single hexamantane component. 48. The composition of claim 46, wherein the one or more hexamantane components are isolated optical isomers. 49. The composition of claim 46, wherein the one or more hexamantane components are isomeric hexamantane components. • 44 44 4444 44 4444 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 • 4 4 4 44 4 4 4 4 4 50. The composition of claim 46, wherein the T m s that the one or more components hexamantanových is represented by the formula C ₃₀ H _36th 51. The composition of claim 46, wherein the T m s that the one or more components hexamantanových is represented by the formula C _{2 g} H _34th 52. An enriched hexamantane component having the formula ^C 30 ^H 36 ^not to ° ^C 39 ^H 34 ' ^with or without substitution. An enriched hexamantane component according to claim 52 having a purity of at least 25% by weight. 54. Enriched hexamantane component according to claim 52 v crystalline form. 55. Enriched hexamantane component according to claim 52, which is represented by the formula C ₂₉ ^h 36 ' The enriched hexamantane component of claim 52, which is represented by the formula C ₃₀ H ₃₆ . The enriched hexamantane enantiomer of claim 56, which is selected from the group consisting of hexamantane enantiomer A [1 (2) 314] hexamantane enantiomer B [1 (2) 314] hexamantane enantiomer A [12 (1) 32] hexamantane enantiomer B hexamantane enantiomer A hexamantane enantiomer B hexamantane enantiomer B hexamantane enantiomer B hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer A hexamantane enantiomer 4 44 • · · • ·· * r « • · ♦ ·· 4 4 4 • 4 4 4 4 4 4 • · • · • • 4 4 4 • • · 4 4 4 4 4 9 4 · ·· • 44 4 4 [12 (1) 32] [12 (1) 34] [12 (1) 33] [12 (3) 14] [12 (3) 14] [121 (2) 3] [121 (2) 3] [ 12123] [12123] [12131] [12131] [12134] [12134] [12324] [12324] Hexamantane Enantiomer A Hexamantane Enantiomer A [12341] φ φ φ φ φ φ φ φ φ φ φ φ • - 97 hexamantane enantiomer Β [12341] hexamantane [1 (2) 3 (1) 2] hexamantane [12 (3) 12] hexamantane [121 (3) 4] hexamantane [12121] hexamantane [12321] hexamantane enantiomer A [1 ( 2) 3 (1) 4] hexamantane enantiomer B [1 (2) 3 (1) 4]. The enriched hexamantane component of claim 52, which is an unsubstituted hexamantane component. The enriched hexamantane component of claim 52, which is a substituted hexamantane component. 60. Enriched substituted cyclohexamanthine component. 61. The composition of claims 1-14, wherein the selected higher diamondoid components comprise one or more heptamantane components. 62. The composition of claim 61, wherein the one or more heptamantane components are a single heptamantane component. ** · · · · · · · · · · 63. The composition of claim 61, wherein the one or more heptamantane components are optical isomers. 64. The composition of claim 61, wherein the one or more heptamantane components are isomeric heptamantane components. 65. The composition of claim 61, wherein the one or more heptamantane components are one or more isomeric heptamantane components represented by the formula C ₃ qH ₃₄ . 66. The composition of claim 61, wherein the at least one heptamantane component is one or more isomeric heptamantane components represented by the formula C ₃₂ H ₃₆ . 67. The composition of claim 61, characterized in that the at least one heptamantanové component comprises one or more isomeric heptamantanových component represented by the formula C ₃₃ H _3g. 68. The composition of claim 61, wherein the at least one heptamantane component is one or more isomeric heptamantane components represented by the formula C ₃₄ H ₄₀ . 69. Enriched heptamantane component. 70. The enriched heptamantane component of claim 69 having a purity of at least 25% by weight. • · · · The enriched heptamantane component of claim 69 in crystalline form. The enriched heptamantane component of claim 69 having a molecular weight of 394. The enriched heptamantane component of claim 69, which is heptamantane [121321]. The enriched heptamantane component of claim 69, which is heptamantane [123124]. The enriched heptamantane component of claim 69, which is an unsubstituted component. The enriched heptamantane component of claim 69, which is a substituted component. 77. The composition of claims 1-14, wherein the selected higher diamondoid components comprise at least one octamantane component. 78. The composition of claim 77 wherein the at least one octamantane component is a single octamantane component. 79. The composition of claim 77 wherein the at least one octamantane component is isolated optical isomers. 80. The composition of claim 77 wherein the at least one octamantane component is at least one octamantane component. · ··· · · · ··· 100 represent the isomeric octamantane components. 81. The composition of claim 77, wherein the at least one octamantane component is one or more isomeric octamantane components represented by the formula C ₃₃ H ₃₆ . 82. The composition of claim 77 wherein the at least one octamantane component is one or more isomeric octamantane components represented by the formula C ₃₄ H ₃₈ 83. The composition of claim 77, wherein t is in that the at least one component oktamantanovou represents one or more isomeric oktamantanových component represented by the formula C ₃₆ H _40th 84. The composition of claim 77, wherein t is in that the at least one component oktamantanovou represents one or more isomeric oktamantanových component represented by the formula C ₃₇ H _42nd 85. The composition of claim 77, wherein t is in that the at least one component oktamantanovou represents one or more isomeric oktamantanových component represented by the formula C ₃₈ H _44th 86. Enriched octamantane component. 87. The enriched octamantane component of claim 86 having a purity of at least 25% by weight. 88. The enriched octamantane component of claim 86 in claim 86. 101 in a crystalline form. 89. The enriched octamantane component of claim 86 which is an unsubstituted octamantane component. The enriched octamantane component of claim 86, which is a substituted octamantane component. 91. The composition of claims 1-14, wherein the selected higher diamondoid components comprise at least one nonamantane component. 92. The composition of claim 91, wherein the at least one nonamantane component is a single nonamantane component. 93. The composition of claim 91, wherein the at least one nonamantane component is isolated optical isomers. 94. The composition of claim 91, wherein the at least one nonamantane component is an isomeric nonamantane component. 95. The composition of claim 91, wherein the at least one nonamantane component is an isomeric nonamantane component as defined by formula ^C 34 ^H 36 *. 96. The composition of claim 91, wherein t is in that the at least one component nonamantanovou represents one or more isomeric nonamantanových component represented by the formula C ₃₇ H ₄₀ · - 102 • · • 0 · 0 0 0 0 0 97. The composition of claim 91, wherein the at least one nonamantane component is one or more isomeric nonamantane components represented by the formula ^c 38 ^h 42. 98. The composition of claim 91, wherein t is in that the at least one component nonamantanovou represents one or more isomeric nonamantanových component represented by the formula C ₄₀ H ₄₄ · 99. The composition of claim 91, wherein t is in that the at least one component nonamantanovou represents one or more isomeric nonamantanových component represented by the formula C ₄₁ H _46th 100. The composition of claim 91, wherein t is in that the at least one component nonamantanovou represents one or more isomeric nonamantanových component represented by the formula C ₄₂ H _48th 101. Enriched nonamantane component. 102 showing The enriched nonamantane component according to claim a purity of at least 25% by weight. 101, 103 crystalline Enriched nonamantane component according to form. claim 101 v 104. The enriched nonamantane component of claim which is an unsubstituted nonamantane component. 105. The enriched nonamantane component of claim 101, 101, 103 which is a substituted nonamantane component. 106. The composition of claims 1 to 14 wherein the selected higher diamondoid components comprise one or more decamantane components. 107. The composition of claim 106, wherein the one or more decamantane components are a single decamantane component. 108. The composition of claim 106, wherein the one or more decamantane components are isolated optical isomers. 109. The composition of claim 106, wherein the one or more decamantane components are isomeric decamantane components. 110. The composition of claim 106, wherein t is in that said one or more components is dekamantanovými neisomerní dekamantanová component defined by the formula C ₃₅ H ₃ g. 111. The composition of claim 106, wherein t is in that said one or more dekamantanovými component is at least one isomer dekamantanová component defined by the formula C H _{Q3 40th} 112. The composition according to claim 106, characterized in that said one or more dekamantanovými component is at least one isomer dekamantanová component defined by the formula C ₄₁ H _44th 113. The composition of claim 106, wherein the composition is 9. 104, wherein the one or more decamantane components are at least one isomeric decamantane component defined by Formula C ₄₂ H ₄₆ ; 114. A composition according to claim 106, characterized in that said one or more dekamantanovými component is at least one isomer dekamantanová component defined by the formula C ₄₄ H _48th ' 115. The composition of claim 106, wherein the one or more decamantane components is at least one non-isomeric decamantane component defined by the formula 116. The composition of claim 106, wherein the one or more decamantane components is at least one isomeric decamantane component defined by formula C ₄₆ H ₅₂ . 117 Enriched decamantane component. 118 reporting The enriched decamantane component has a purity of at least 25% by weight. claim 117, 119 crystalline Enriched form. decamantane component according to claim 117 v 120. Enriched decamantane component according to claim 117, wherein the decamant component is decamantane [1231241 (2) 3]. 121. The enriched decamantane component of claim 117, wherein the component is an unsubstituted decamantane component. 105 122. The enriched decamantane component of claim 117, wherein the decamantane component is a substituted decamantane component. 123. The composition of claims 1-14, wherein the selected higher diamondoid components comprise at least one undecamantane component. 124. The composition of claim 123, wherein the at least one undecamant component is a single undecamantane component. 125. The composition of claim 123, wherein the at least one undecamant component is isolated optical isomers. 126. The composition of claim 123, wherein the at least one undecamant component is an isomeric undecamant component. 127. The composition of claim 123, wherein the at least one undecamantane component is one or more isomeric undecamantane components represented by the formula C ₃₉ H ₄₀ . 128. The composition of claim 123, wherein the one or more undecamantane components are one or more isomeric undecamantane components represented by the formula ^C 41 ^H 42. 129. The composition of claim 123, wherein the one or more undecamantano- The 106 components represent one or more non-isomeric undecamantane components represented by the formula ^C 42 ^H 44 · 130. The composition of claim 123, characterized in that that one or more of the ingredients throughout undecamantanes represents one or more neisomerních undekamantanových component represented by the formula C ₄₅ H _48th 131. The composition of claim 123, characterized in that that one or more of the ingredients throughout undecamantanes represents one or more neisomerních undekamantanových component represented by the formula ^C 46 ^H 50 · 132. The composition according to claim 123, characterized in that that one or more of the ingredients throughout undecamantanes represents one or more neisomerních undekamantanových component represented by the formula C ₄₈ H ₅₂ · 133. The composition of claim 123, characterized in that that one or more of the ingredients throughout undecamantanes represents one or more neisomerních undekamantanových component represented by the formula C _{4 g} H _54th 134. The composition of claim 123, characterized in that that one or more of the ingredients throughout undecamantanes represents one or more neisomerních undekamantanových component represented by the formula C ₅₀ H ₅ g. 135. Enriched undecamantane component. 136. The enriched undecamantane component of claim 135 having a purity of at least 25% by weight. 137. Enriched undecamantane component 135 in crystalline form. 107 according to claim 135, 138. The enriched undecamantane component of claim 1, which is an unsubstituted undecamantane component. 139 135, which The enriched undecamantane component of the claim is a substituted undecamantane component. 140. A method of obtaining a composition enriched in higher diamondoid components, comprising the steps of: a. a choice of raw material containing acceptable amounts of the higher diamondoid components; b. removing sufficient components from the feedstock of a boiling point lower than the lowest boiling point of said higher diamondoid component under conditions providing a processed feedstock from which higher diamondoid components can be obtained; and c. obtaining higher diamondoid components from the treated feedstock by separation methods selected from the group consisting of chromatographic methods, thermal diffusion methods, zone refining, progressive recrystallization, and size difference separation methods. 141. The method of obtaining the enriched higher diamondoid component of claim 1, comprising the steps of: a. a choice of raw material containing acceptable quantities higher 108 of the diamondoid component or components selected for recovery, the non-diamondoid components and components having a boiling point lower than the lowest boiling point of the higher diamondoid component selected for recovery; b. removing a sufficient amount of the components of the raw material having a boiling point lower than the lowest boiling point of the higher diamondoid component under conditions ensuring that acceptable quantities of the selected higher diamondoid component (s) are maintained in the processed raw material; c. heat treating the feedstock obtained in step b) above for pyrolyzing at least a sufficient amount of non-diamondoid components to obtain the selected higher diamondoid component or components from the pyrolytically treated feedstock, wherein the pyrolysis is carried out under conditions ensuring this processed raw material, d. recovering selected higher diamondoid components from said treated feedstock by separation methods selected from the group consisting of chromatographic methods, thermal diffusion methods, zone refining, progressive recrystallization, and size difference separation methods.