WO2004009577A1 - Heterodiamondoids - Google Patents
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- WO2004009577A1 WO2004009577A1 PCT/US2003/022483 US0322483W WO2004009577A1 WO 2004009577 A1 WO2004009577 A1 WO 2004009577A1 US 0322483 W US0322483 W US 0322483W WO 2004009577 A1 WO2004009577 A1 WO 2004009577A1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
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- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/18—Polycyclic halogenated hydrocarbons
- C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/28—Unsaturated compounds polycyclic
- C07C61/29—Unsaturated compounds polycyclic having a carboxyl group bound to a condensed ring system
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/22—Bridged ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/10—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
Definitions
- heteroatom-containing diamondoids i.e., "heterodiamondoids” which are compounds having a diamondoid nucleus in which one or more of the diamondoid nucleus carbons has been substitutionally replaced with a noncarbon such as a group IIJJB, noncarbon group IVB, group VB or VIB atom.
- a noncarbon such as a group IIJJB, noncarbon group IVB, group VB or VIB atom.
- heteroatom substituents impart desirable properties to the diamondoid.
- the heterodiamondoids can be functionalized affording compounds carrying one or more functionalization groups covalently pendant therefrom. Functionalized heterodiamondoids having polymerizable functional groups are able to form polymers containing heterodiamondoids.
- the diamondoid nuclei are triamantane and higher diamondoid nuclei.
- the heteroatoms are selected to give rise to diamondoid materials which can serve as n- and p-type materials in electronic devices.
- Diamondoids are cage-shaped hydrocarbon molecules possessing rigid structures which are tiny fragments of a diamond crystal lattice.
- Adamantane is the smallest member of the diamondoid series and consists of a single cage structure of the diamond crystal lattice.
- Diamantane contains two adamantane subunits face-fused to each other, triamantane three, tetramantane four, and so on. While there is only one isomeric form of adamantane, diamantane and triamantane, there are four different isomeric tetramantanes (i.e., four different shapes containing four adamantane subunits). Two of the isomeric tetramantanes are enantiomeric. The number of possible isomers increases rapidly with each higher member of the diamondoid series.
- heterodiamondoids are those diamondoids in which at least one cage carbon atom is replaced by a heteroatom.
- the following references describe more details about heteroadamantanes and heterodiamantanes.
- the invention provides heterotriamantanes and hetero higher diamondoids.
- Heteroatoms are selected from atoms of group III B elements such as B or Al; noncarbon group IV B elements such as Si; group V B elements such as N, P or As, and particularly N or P; and group VI B elements such as O, S, or Se.
- group III B elements such as B or Al
- noncarbon group IV B elements such as Si
- group V B elements such as N, P or As, and particularly N or P
- group VI B elements such as O, S, or Se.
- group VB elements are generally classed as electron-donating (hole- accepting) or "electropositive” atoms
- the group III B elements are generally classed as electron-accepting (hole-donating) or "electronegative” atoms.
- heterodiamondoids of the invention are a triamantane or a higher diamondoid nucleus with 1 or more (for example 1 to 20 and especially 1 to 6) of its cage carbons replaced by a heteroatom.
- the heterodiamondoids can also be substituted with up to 6 alkyl groups per diamondoid unit.
- This invention is further directed to functionalized heterodiamondoids.
- the heterotriamantanes and higher heterodiamondoids contain at least 1 and, preferably 1 to 6 functional group(s) covalently bonded to cage carbons, presented as Formula I:
- G is a heterotriamantane or a higher heterodiamondoid nucleus with one or more heteroatoms as described; and, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from a group consisting of hydrogen and covalently bonded functional groups, provided that there is at least 1 functional group. More preferably, the functionalized heterodiamondoids contain either 1 or 2 functional groups and from 1 to 6 heteroatoms.
- heterodiamondoids and functionalized heterodiamondoids can exist as discrete individual molecules. They can also exist as crystalline aggregates. These crystalline structures can be pure heterodiamondoids or pure functionalized heterodiamondoids or can, intentionally or inadvertendly, be a mixture of more than one diamondoid with or without functionalization, with heterodiamondoid and/or functionalized heterodiamondoid. [00053] Some of these functionalized heterodiamondoids can be prepared from heterodiamondoids in a single reaction step.
- heterodiamondoids include, for example, heterodiamondoids of Formula I wherein the functionalizing groups are halogens (such as -bromos, and -chloros), -thios, -oxides, -hydroxyls, and -nitros, as well as other derivatives formed in one reaction from a heterotriamantane or a higher heterodiamondoid.
- the functionalizing groups are halogens (such as -bromos, and -chloros), -thios, -oxides, -hydroxyls, and -nitros, as well as other derivatives formed in one reaction from a heterotriamantane or a higher heterodiamondoid.
- Representative "secondary functionalized heterodiamondoid" functional groups include haloalkyl, haloalkenyl, haloalkynyl, hydroxyalkyl, heteroaryl, alkylthio, alkoxy; aminoalkyl, aminoalkoxy, heterocycloalkoxy, cycloalkyloxy, aryloxy, and heteroaryloxy.
- the functional group on the functionalized heterodiamondoid is is alkyl, aryl, or aralkyl; - COR 17 , wherein R 17 is alkyl, aryl, or heteroalkyl; -NHNH 2 ; -R 18 NHCOR 19 wherein R 18 is absent or selected from alkylene, arylene, or aralkylene, R 19 is hydrogen, alkyl, -N 2 , aryl, amino, or -NHR 20 wherein R 20 is hydrogen, -SO 2 -aryl, -SO 2 -alkyl, -SO 2 - aralkyl or -CONHR 21 wherein R 21 is hydrogen, alkyl, aralkyl, or -CSNHR 21 wherein R 21 is as defined above; and -NR 22 -(CH 2 ) n -NR 23 R 24 , wherein R 22 , R 23 , R 24 are independantly selected from hydrogen, alkyl, aryl, or aral
- one or more of the functional groups on the functionalized heterodiamondoids may be of the formula:
- the functionalizing group may form a covalent bond to two or more of these heterodiamondoids and thus serve as a linking group or polymerizable group between the two or more heterodiamondoids. This provides functionalized heterodiamondoids of formula II:
- G-L-(G) n or G-L-(D) disturb or G-(L-G) protest or G-(L-D) n or (G-L) n or the like
- D is a diamondoid nucleus
- G is a heterotriamantane or a higher heterodiamondoid nucleus
- L is a linking group and n is 1 or more such as 2 to 1000 and especially 2 to 500.
- R 28 , R 29 , R 30 , R 31 , R 32 , R 33 are independently hydrogen or alkyl, and n and m are independently from 2 to 20;
- R 28 , R 29 , R 30 , R 31 , R 32 , and R 33 are hydrogen or alkyl;
- R 34 , R 35 , R 36 , and R 37 are independently absent or hydrogen or alkyl with the proviso that at least one of R 34 ,
- R , R , and R is present; and n and m are independently from 2 to 20 or the like.
- the present invention relates to functionalized heterodiamondoids of formula III:
- G and G' are each independently a heterodiamondoid nucleus and R' and R" are substituents on the heterodiamondoid nucleus and are independently hydrogen or a functionalizing group
- n and m are 1 or more such as 1 to 10 and preferably 1 to 6. More preferably the material contains either 1 or 2 functional groups.
- R' and R" are halo; cyano; aryl; arylalkoxy; aminoalkyl; or -COOR 40 wherein R 40 is hydrogen or alkyl.
- heterodiamondoids and functionalized heterodiamondoids of the present invention are useful in for instance, nanotechnology, drugs, drug carriers, pharmaceutical compositions, precursors for the synthesis of biologically active compounds, photoresist materials and/or photoresist compositions for far UV lithography, synthetic lubricants, heat resist materials and solvent-resistant resins, and so on.
- these heterodiamondoid derivatives may have desirable lipophilic properties, which may improve the bioavailability of pharmaceutically active groups attached thereto.
- These heterodiamondoids and derivatives may also be useful as chemical intermediates for the synthesis of further functionalized heterodiamondoids to form a variety of useful materials.
- Such materials include composite matrix resins, structural adhesives and surface files that are used for aerospace structural applications. Furthermore, coating layers or molded products with excellent optical, electrical or electronic and mechanical properties are produced for use in optical fibers, photoresist compositions, conduction materials, paint compositions and printing inks. In addition, these heterodiamondoid derivative- containing materials will have high thermal stability making them suitable for use in environments requiring such stability including for example, devices such as semiconductors, coatings for refractory troughs or other high temperature applications.
- the heteroatoms introduced into the triamantane of higher diamondoid nucleus are electron-donating or electron- accepting.
- the semiconducting heterodiamondoids that result have utility in a variety of transistor and other electronic and microelectronic settings.
- FIG. 1 shows the numbering of four tetramantanes and points out representative secondary, tertiary and quaternary carbon atoms.
- FIG. 2 presents exemplary computer modeling calculations that illustrate the feasibility of the synthesis of heterodiamondoids.
- FIG's. 3-5 illustrate reaction routes for introducing an oxygen heteroatom into a diamondoid.
- FIG. 6 illustrates routes for introducing a sulfur heteroatom into a diamondoid.
- FIG's. 7-8 illustrate routes for introducing a nitrogen heteroatom into a diamondoid.
- FIG's. 9-23 illustrate representative routes for functionalizing heterodiamondoids.
- FIG's. 24-33 illustrate representative polymers containing heterodiamondoids and routes to prepare them.
- FIG. 34 shows the total ion chromatogram (TIC) of the photohydroxylated mixture of Example 2 containing hydroxylated tetramantanes including hydroxylated alkyl tetramantanes.
- FIG. 35 is the m/z 308 ion chromatogram showing the presence of monohydroxylated tetramantanes in the TIC of the reaction mixture of Example 2.
- FIG. 36 is the mass spectrum of a monohydroxylated tetramantane with GC/MS retention time of 19.438 minutes from FIG. 35. The base peak in this spectrum is the m/z 308 molecular ion.
- FIG. 37 is the m/z 322 ion chromatogram showing the presence of monohydroxylated methyltetramantanes in the TIC of the reaction product of Example 2.
- FIG. 38 is the mass spectrum of monohydroxylated methyltetramantane from FIG. 37 with GC MS retention times of 19.998 minutes.
- FIG. 39 shows the total ion chromatogram (TIC) of the oxa tetramantane- containing reaction mixture also produced in Example 2.
- FIG. 40 is the m/z 294 ion chromatogram showing the presence of oxa tetramantanes in the TIC of the reaction product of Example 2.
- FIG. 41 is the mass spectrum of an oxa tetramantane with GC/MS retention time of 17.183 minutes from FIG. 40.
- FIG. 42 shows the total ion chromatogram (TIC) of the azahomo tetramantane-ene-containing reaction mixture of Example 3.
- FIG. 43 is the m/z 305 ion chromatogram showing the presence of azahomo tetramantane-enes in the TIC of the reaction mixture of Example 3.
- FIG. 44 is the mass spectrum of an azahomo tetramantane-ene with GC/MS retention time of 18.062 minutes from FIG. 43.
- FIG. 45 is the m/z 319 ion chromatogram showing the presence of azahomo methyltetramantane-enes in the TIC of the reaction product.
- FIG. 46 is the mass spectrum of an azahomo methyltetramantane-ene with GCMS retention time of 18.914 minutes from FIG. 45.
- FIG. 47 shows the total ion chromatogram (TIC) of the epoxy azahomo tetramantane-containing reaction mixture produced in Example 3.
- FIG. 48 is the m/z 321 ion chromatogram showing the presence of epoxy azahomo tetramantanes in the TIC of the reaction product of Example 3.
- FIG. 49 is the mass spectra of an epoxy azahomo tetramantane with GC/MS retention times of 21.929 from FIG. 48.
- FIG. 50 is the m/z 335 ion chromatogram showing the presence of epoxy azahomo methyltetramantanes in the TIC of a reaction product of Example 3.
- FIG. 51 is the mass spectrum of an epoxy azahomo methyltetramantane with GC/MS retention time of 21.865 minutes from FIG. 50.
- FIG. 52 shows the total ion chromatogram (TIC) of the N-formyl aza tetramantane-containing reaction mixture of Example 3.
- FIG. 53 is the m/z 321 ion chromatogram showing the presence of N-formyl aza tetramantanes in the TIC of the reaction product of Example 3.
- FIG. 54 is the mass spectrum of a N-formyl aza tetramantanes with GC/MS retention time of 21.826 minutes from FIG. 53.
- FIG. 55 is the m/z 335 ion chromatogram showing the presence of the N- formyl aza methyltetramantanes in the TIC of a reaction product of Example 3.
- FIG. 56 is the mass spectrum of a N-formyl aza methyltetramantane with GC/MS retention time of 21.746 minutes from FIG. 55.
- FIG. 57 shows the total ion chromatogram (TIC) of the aza tetramantane- containing reaction mixture produced in Example 3.
- FIG. 58 is the m/z 293 ion chromatogram showing the presence of the aza tetramantanes in the TIC of the reaction product shown in Example 3.
- FIG. 59 is the mass spectrum of an aza tetramantane with GC/MS retention time of 19.044 minutes.
- FIG. 60 is the m/z 307 ion chromatogram showing the presence of the aza methyltetramantanes in the TIC of a reaction product of Example 3.
- FIG. 61 is the mass spectrum of an aza methyltetramantane with GC/MS retention time of 22.936 minutes.
- FIG. 62 is the m/z 321 ion chromatogram showing the presence of the aza dimethyltetramantanes in the TIC of a reaction product of Example 3.
- FIG. 63 is the mass spectrum of an aza dimethylteframantane with GC/MS retention time of 22.742 minutes from FIG. 62.
- diamondoid refers to substituted and unsubstituted caged compounds of the adamantane series beginning with triamantane and including, in addition, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, undecamantane and dodecamantane.
- a higher diamondoid is tetramantane or higher.
- Substituted diamondoids preferably comprise from 1 to 10 and more preferably 1 to 4 substituents independently selected from the group consisting of alkyl, including linear (i.e., straight chain) alkyl, branched alkyl or cycloalkyl groups.
- heteroatom refers to an atom selected from HIB, non-C IVB, VB and VIB elements in the Periodic Table of the Elements, e.g. B, Al, Si, N, P, As, O, S, etc.
- hetero diamondoid refers to diamondoid (as specifically defined) in which at least one cage carbon atom is replaced by a heteroatom.
- Heterodiamondoids include heterotriamantane, heterotetramantane, heteropentamantane, heterohexamantane, heteroheptamantane, heterooctamantane, heterononamantane, heterodecamantane, heteroundecamantane, heteroundecamantane and heterododecamantane.
- Substituted heterodiamondoids preferably comprise from 1 to 10 and more preferably 1 to 4 substituents independently selected from the group consisting of alkyl, including linear (i.e., straight chain) alkyl, branched alkyl or cycloalkyl roups.
- the terms “functionalized heterodiamondoid” and “derivatized heterodiamandoid” refer to a heterodiamondoid which has at least one covalently bonded functional group.
- alkyl refers to a linear saturated monovalent hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; or a branched saturated monovalent hydrocarbon group having 3 to 40 carbon atoms, preferably from 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.
- This term is exemplified by groups such as methyl, ethyl, ⁇ z-propyl, ⁇ o-propyl, ra-butyl, iso-butyl, n-hexyl, ⁇ -decyl, tetradecyl, and the like.
- the term "functional group” refers to halos, hydroxyls, oxides, nitros, aminos, thios, sulfonyl halides, sulfonates, phosphines and the like, as well as such groups attached to hydrocarbyl materials such as alkyls, alkenyls, alkyaryls and aryls with or without substitution.
- FIG's. 3-5 illustrate three different synthesis pathways to oxadiamondoids.
- FIG. 6 shows two different pathways to thiadiamondoids.
- FIG's 7 and 8 show different ways to prepare azadiamondoids. It is understood that while in the FIG's 3-8 only wo-tetramantane is shown as the starting diamondoid, triamantane and other higher diamondoids may also be used.
- Nitrogen heterodiamondoids may be synthesized by the method of T. Sasaki et al., Synthesis of adamantane derivatives. 39. Synthesis and acidolysis of 2 ⁇ azidoadamantanes. A facile route to 4-azahomoadamant-4-enes, Heterocycles Vol. 7, No. 1, p. 315 (1977). The procedure consists of a substitution of a hydroxyl group with an azide function via the formation of a carbocation, followed by acidolysis of the azide product.
- a l-hydroxy-2-azaadamantane may be synthesized from 1,3- dibromoadamantane, as reported by A. Gagneux et al. in 1 -Substituted 2- heteroadamantanes. Tetrahedron Letters No. 17. pp. 1365-1368 (1969). This is a multiple-step process, wherein first the di-bromo starting material is heated to a methyl ketone, which subsequently undergoes ozonization to a diketone.
- the diketone is heated with four equivalents of hydroxylamine to produce a 1:1 mixture of cis and trans-dioximes; this mixture is hydro genated to the compound l-amino-2- azaadamantane dihydrochloride. Finally, nitrous acid transforms the dihydrochloride to the hetero-adamantane l-hydroxy-2-azadamantane.
- a 2-azaadamantane compound may be synthesized from a bicyclo[3.3.1]nonane-3,7-dione, as reported by J.G. Henkel and W.C. Faith, in Neighboring group effects in the ⁇ -halo amines. Synthesis and solvolytic reactivity of the anti-4-substituted 2-azaadamantyl system, in J. Org. Chem. Vol. 46, No. 24, pp. 4953-4959 (1981).
- the dione may be converted by reductive amination (although the use of ammonium acetate and sodium cyanoborohydride produced better yields) to an intermediate, which may be converted to another intermediate using thionyl choloride. Dehalogenation of this second intermediate to 2-azaadamantane was accomplished in good yield using LiAlH 4 in DME.
- FIG. 7 An exemplary reaction pathway for synthesizing a nitrogen-containing hetero tsO-tetramantane is illustrated in FIG. 7. It will be known to those of ordinary skill in the art that the reaction conditions of the pathway depicted in FIG. 7 will be substantially different from those of Eguchi due to the differences in size, solubility, and reactivities of tetramantane in relation to adamantane.
- FIG. 8 A second pathway available for synthesizing nitrogen-containing heterodiamondoids is illustrated in FIG. 8.
- a phosphorus-containing heterodiamondoid may be synthesized by adapting the pathway outlined by J. J. Meeu Giveaway et. al in Synthesis of 1-phosphaadamantane, Tetrahedron Vol. 39. No. 24, pp. 4225-4228 (1983). It is contemplated that such a pathway may be able to synthesis heterodiamondoids that contain both nitrogen and phosphorus atoms substitutionally positioned in the diamondoid structure, with the advantages of having two different types of electron- donating heteroatoms in the same structure.
- heterodiamondoids After preparing the heterodiamondoids, they may be functionalized with at least one functional group. Representative pathways are provided in the Examples. Additional disclosure of derivatization methods is provided below and in Figs. 9-23.
- Table 3 provides a representative list of heterodiamondoid derivatives.
- Example 1 describes a most universal route for isolating higher diamondoids components which can be applied to all feedstocks used herein. This process uses HPLC as its final isolation step.
- Example 2 describes methods that could be used to prepare a oxadiamondoid from a diamondoid-containing feedstock.
- Example 3 describes methods that could be used to prepare a azadiamondoid from a diamondoid-containing feedstock.
- Examples 4-10 describe methods that could be used to prepare heterodiamondoids (e.g. oxa-, thia-, aza-diamondoids, etc.) from diamondoids.
- heterodiamondoids e.g. oxa-, thia-, aza-diamondoids, etc.
- Examples 11-46 describe methods that could be used to prepare heterodiamondoid derivatives.
- Examples 47-64 describe methods that could be used to prepare heterodiamondoid-containing polymers .
- This Example has seven steps.
- Step 1 Feedstock selection
- Step 6 Removal of aromatic and polar nondiamondoid components [000148] Step 7. Multi-column HPLC isolation of higher diamondoids
- Step 1 Feedstock Selection
- Suitable starting materials were obtained. These materials included a gas condensate, Feedstock A, and a gas condensate containing petroleum components, Feedstock B. Although other condensates, petroleums, or refinery cuts and products could have been used, these two materials were chosen due to their high diamondoid concentration, approximately 0.3 weight percent higher diamondoids, as determined by GC and GC/MS. Both feedstocks were light colored and had API gravities between 19 and 20° API.
- Feedstock A was analyzed using gas chromatography/mass spectrometry to confirm the presence of target higher diamondoids and to provide gas chromatographic retention times for these target materials. This information is used to track individual higher diamondoids through subsequent isolation procedures.
- Step 3 Feedstock Atmospheric Distillation
- Feedstock B was distilled into a number of fractions based on boiling points to separate the lower boiling point components (nondiamondoids and lower diamondoids) and for further concentration and enrichment of particular higher diamondoids in various fractions.
- Step 4 Fractionation of Atmospheric Distillation Residue by Vacuum Distillation
- the Feedstock B atmospheric residium from Step 3 (comprising 2-4 weight percent of the original feedstock) was distilled into fractions containing higher diamondoids.
- a high-temperature reactor was used to pyrolyze and degrade a portion of the nondiamondoid components in various distillation fractions obtained in Step 4 thereby enriching the diamondoids in the residue.
- the pyrolysis process was conducted at 450 °C for 19.5 hours.
- the pyrolysate produced in Step 5 was passed through a silica-gel gravity chromatography column (using cyclohexane elution solvent) to remove polar compounds and asphaltenes.
- An excellent method for isolating high-purity higher diamondoids uses two or more HPLC columns of different selectivities in succession.
- the first HPLC system consisted of two Whatman M20 10/50 ODS columns operated in series using acetone as mobile phase at 5.00 mL/min. A series of HPLC fractions were taken.
- an azahomo tetramantane-ene may be produced from the above hydroxylated tetramantanes, or from photooxidized tetramantanes.
- methanesulfonic acid 1.5 mL
- dichloromethane 3.5 ml
- solid sodium azide 1.52 g, 8.0 mmol
- To that mixture was added the hydroxylated tetramantanes (2) as prepared in Example 2 above. To this resulting mixture was added in small increments sodium azide (1.04 g, 16 mmol) over a period of about 0.5 h.
- an epoxy azahomo tetramantane was made from the azahomo tetramantane-enes.
- the above mixture was treated with -CPBA (1.1 eq.) in CH Cl 2 -NaHCO 3 at a temperature of about 20°C for about 12 h, and the reaction mixture was then worked up with a CH C1 extraction to afford a crude product that was characterized by GC/MS (Figs. 47-51) to show the presence of epoxy azahomo tetramantane.
- N-formyl aza tetramantanes by mixing the N-formyl aza teframantanes with 10 mL of
- Photohydroxylated iso-tetramantane containing a mixture of C-2 and C-3 hydroxylated iso-tetramantanes dissolved in acetone is prepared as set out in Example 2.
- the oxygenated components go into the solution but not all of the unreacted iso- tetramantane.
- Chromic acid-sulfuric acid solution is added dropwise to the solution until an excess is present, and the reaction mixture is stirred overnight.
- the acetone solution is decanted from the precipitated chromic sulfate and the unreacted iso- tetramantane, and is dried with sodium sulfate.
- the unreacted iso-tetramantane is recovered by dissolving the chromium salts in water and filtering. Evaporation of the acetone solution affords a white solid.
- This crude solid is chromatographed on alumina with standard procedures eluting first with 1:1 (v/v) benzene/light petroleum ether followed by ethyl ether or a mixture of ethyl ether and methanol (95:5 v/v) to collect the unreacted iso-tetramantane and the keto compound 1 (Fig. 3), respectively. Further purification by recrystallization from cyclohexane affords a pure product 1.
- tso-tetramantane is directly oxidized to keto compound 1 according to the procedures of McKervey et al. (J. Chem. Soc. Perkin Trans. 1, 1972, 2691).
- the keto compound 1 is reduced with lithium aluminum hydride (a little excess) in ethyl ether at low temperatures to prepare C-2 hydroxylated iso-tetramantane 2a.
- the reaction mixture is worked up by adding saturated Na 2 SO 4 aqueous solution to decompose excess hydride at low temperature. Decantation from the precipitated salts gives a dry ether solution, which, when evaporated, affords a crude monohydroxylated iso- tetramantane substituted at the secondary carbon, i.e. C-2 tetramantan-ol which is purified by recrystallization from cyclohexane.
- C-2 methyl hydroxyl iso-tetramantane 2b (6.02 mmol) is added to a solution of TFPAA (trifluoroperacetic acid) in TFAA (trifluoroacetic acid) (13 g, 48.5 mmol) at 0 °C. After being stirred for about 15 min. at 0 °C, the reaction mixture is allowed to warm to r.t, stirring for about 1 h, and then poured into a solution of 15% NaOH (50 mL) with ice. The mixture is extracted with CH 2 C1 2 (3x15 mL). The combined extract is then washed with water and 5% aqueous Na 2 SO 3 . The organic layer is dried over Na 2 SO 4 and the solvent evaporated. The residue is separated on a silica column eluting with a mixture of hexane-ether to afford the preduct oxa iso-tetramantane 3.
- Lactone 4 of Fig. 4 is prepared according to the general procedure of [Udding et al, Tetrahedron Lett.. 1968, 5719].
- the ether layer then is separated, washed several times with water and once with saturated sodium bicarbonate, and dried over anhydrous sodium sulfate. Removal of the ether gives an oily material from which a mixture of the two isomers (exo- and endo-) of compound 10 is obtained. Further purification and separation of the stereochemical isomers (exo- and endo-) can be achieved by distillation under vacuum.
- a solution of the carboxylic acid 9 (4.59 mmol) in 15 mL of dry THF is stirred under dry argon and cooled to 0 °C.
- a solution of 1.5 g (13.76 mol) of lithium diisopropylamide in 25 mL of dry THF under argon is added through a syringe to the solution of 9 at such a rate that the temperature does not rise above 10 °C.
- the resulting solution of the dianion of 9 is stirred at 0 °C for about 3 h. It is then cooled to -78 °C with a dry ice-acetone bath, and dry oxygen is bubbled slowly through the solution for about 3 more.
- Compound 6b is prepared as described in a previous example. To a solution of compound 6b (0.78 mmol) in dry carbon tetrachloride (4 mL) is added to iodotrimethylsilane (312 mg, 1.56 mmol) at room temperature and the mixture is stirred for about 4 h. Water (20 mL) is then added and the mixture is extracted with ether (2x30 L). The organic extract is washed with 5% sodium thiasulfate (20 mL), water, and saturated sodium chloride solution (30 mL) and is dried with sodium sulfate. The solvent is evaporated to give the crystalline product 7, which decomposes upon heating above about 90 °C.
- Compound 12 is prepared as described in a previous example starting from iso-tetramantone 1. Hydrogen sulfide is passed continuously for 2 days through a solution of compound 12 (1.06 mmol) in 15 mL of absolute ethanol. The solution is kept acidic by passing hydrogen chloride during every other 12-h period. The reaction mixture is kept at 0 °C during the passage of the gases. The resulting orange solution is extracted with 50 mL of ether in portions. The ether extracts are washed twice with water, dried over anhydrous sodium sulfate, and stripped to yield an orange semisolid. No further purification is needed and the material is used directly in the following reaction.
- an aza wo-teframantane is prepared from a single tetramantane isomer, ⁇ o-tetramantane, as shown in FIG's. 7-8.
- this synthetic pathway begins with the photo-hydroxylation of wo-tetramantane using the method of Example 2 or chemical oxidation/reduction to the hydroxylated compound 2a shown in FIG. 7.
- the azahomo iso-tetramantane-ene 14 is prepared from the hydroxylated compound 2 using the general method set out in Example 3.
- N-acyl aza t_r ⁇ -tetramantane 16b is prepared from the epoxy azahomo tso-tetramantane 15b by irradiating the epoxy azahomo iso- tetramantane 15b in cyclohexane for about 0.5 hours with a UV lamp. The radiation passes through a quartz filter and the reaction is carried out under an argon atmosphere. Generally speaking, a single product is formed when the reaction is allowed to proceed for only a short time: longer periods gives a complex mixture of products. Products may be isolated by chromatographic techniques.
- N-formyl aza tsO-tetramantane 16a can be similarly prepared from the epoxy azahomo zso-tetramantane 15a.
- the aza z ' so-tetramantane 17 is prepared from N-acyl aza- isotetramantane 16b by heating the N-acyl aza wo-tetramantane 16b (5 mmol) to reflux for about 5 hours with a solution of 2 g powdered sodium hydroxide in 20 mL diethylene glycol. After cooling, the mixture is poured into 50 mL water and extracted with ethyl ether. The ether extract is dried with potassium hydroxide. The ether is distilled off to afford the product aza tso-tetramantane 17.
- the hydrochloride salt is generally prepared for analysis.
- dry hydrogen chloride is passed into the ether solution of the amine, whereby the salt separates out as a crystalline compound.
- the salt may be purified by dissolving it in ethanol, and precipitating with absolute ether. Typically, the solution is left undisturbed for several days to obtain complete crystallization.
- the aza ⁇ o-tetramantane 17 may be prepared from the N- formyl aza tso-tetramantane 16a by mixing the N-formyl aza ⁇ -tetramantane 16a (2.3 mmol) with 10 mL of 15% hydrochloric acid as shown in Example 3.
- the aza iso-tetramantane 17 is prepared from compound 18 by the dropwise addition of a solution of compound 18 (0.98 mmol) in 25 mL of anhydrous ether to a stirred suspension of 250 mg (6.58 mmol) of lithium aluminum hydride in 25 mL of anhydrous ether. The mixture is stirred at reflux for about 2 days. Excess lithium aluminum hydride is destroyed with water, and the precipitated lithium and aluminum hydroxides are dissolved in excess 25% sodium hydroxide. The resulting basic solution is extracted twice with ether, and the combined extracts are then washed with 10% HCl.
- a heterodiamondoid (7.4 mmol) is mixed with anhydrous bromine (74 mmol) in a 150 mL round bottom flask. While stirring, the mixture is heated in an oil bath for about 4.5 h, whereby the temperature is gradually raised from an initial 30 °C to 105 °C. After cooling, the product monobrominated heterodiamondoid dissolved in excess bromine is taken up with 100 mL carbon tetrachlori.de and poured into 300 mL ice water. The excess bromine is then removed with sodium hydrogen sulfide while cooling with ice water.
- the aqueous solution is extracted once more with carbon tetrachloride.
- the combined extracts are washed three times with water.
- the solvent is distilled off and the last residues are removed under vacuum. The residue is dissolved in a small amount of methanol and crystallized in a cold bath. Further purification of the crystals is carried out by sublimation under vacuum.
- a heterodiamondoid (37 mmol) is heated to 150 °C for about 22 h with anhydrous bromine (0.37 mol) in a pressure vessel.
- Usual work- up and recrystallization of the reaction product from methanol is performed as described above.
- the crystals are sublimated in vacuum.
- the sublimate is recrystallized several times from a very small amount of n-hexane affording a dibrominated derivative.
- a mixture of a suitable hydroxylated heterodiamondoid and excess 48% hydrobromic acid is heated to reflux for a few hours (which can be conveniently monitored by GC analysis), cooled, and extracted with ethyl ether. The extract is combined and washed with aqueous 5% sodium hydroxide and water, and dried. Evaporation and normal column chromatography on alumina eluting with light petroleum ether, hexane,, or cyclohexane or their mixtures with ethyl ether affords the bromide with reasonable high yields.
- a solution of a suitable monobrominated heterodiamondoid G-Br (0.046 mole) in 15 mL 7t-hexane in a 150-mL three-necked flask equipped with a stirrer, a gas inlet tube and a gas discharge tube with a bubble counter is cooled to -20 to -25 °C in a cooling bath. While stirring one introduces 4.0 g powdered freshly pulverized aluminum bromide of high quality, and ethylene is conducted in such a way that the gas intake can be controlled with the bubble counter. The reaction starts with a slight darkening of the color and is completed after about 1 h. The reaction solution is decanted from the catalyst into a mixture of ether and water.
- the ether layer is separated off, and the aqueous phase is extracted once more with ether.
- the combined ether extracts are washed with water and dilute sodium carbonate aqueous solution. After they have been dried over calcium chloride, the solvent is distilled off. Recrystallizing from methanol affords the pure heterodiamondoid ethyl bromide G- CH 2 CH 2 -Br.
- G-CH CH-Br from G-Br
- Step 1 in a 150-mL two-necked flask with a stirrer and a drying tube, a mixture of 0.069 mole of a suitable monobromonated heterodiamondoid G-Br and 20 L vinyl bromide is cooled to -65 °C in a cooling bath. While stirring, 4.5 g powdered aluminum bromide is added in portions and the mixture is stirred for an additional about' 3 hours at the same temperature. Then the reaction mixture is poured into a mixture of 30 mL water and 30 mL ethyl ether. After vigorously stirring, the ether layer is separated and the aqueous layer is extracted once more with ether. The combined ether extracts are washed with water and dilute sodium carbonate solution. After it has been dried with calcium chloride and the solvent has been distilled off, the residue is distilled under vacuum.
- Step 2 a solution of 0.7g fine powdered potassium hydroxide and the above compound (0.012 mole) in 10 mL diethylene glycol is heated to 220 °C in the oil bath for 6 hours. After cooling down the mixture is diluted with 30 mL water and exacted with ethyl ether. The ether extract is washed twice with water and dried over calcium chloride. The residue left behind after the ether has been distilled off is sublimated in vacuum, and if necessary, the compound can be recrystallized from methanol.
- G-C ⁇ C-Br can also be formed from G-Br using this method and appropriate starting materials.
- G-C ⁇ H Brfrom G-Br 1.1 g sublimated iron(ffl) chloride and high pure C 6 H 5 Br (excess) are placed in a 150-mL three-necked flask, which is equipped with a stirrer, a reflux condenser and a dropping funnel. While stirring and heating in the steam bath, a suitable monobrominated heterodiamondoid G-Br (0.018 mole) is slowly added to the above flask over about 30 minutes. The reaction mixture is heated for about an additional 3 hours until the production of hydrogen bromide drops off. The mixture is kept standing over night and poured onto a mixture of ice and hydrochloric acid.
- a solution of 0.074 mole of a heterodiamondoid and 10 mL (8.5 g, 0.092 mole) of tert-butyl chloride in 40 mL of anhydrous cyclohexane is prepared in a 0.1 L, three-necked, round-bottom flask fitted with a thermometer, a stirrer, and a gas exhaust tube leading to a bubbler submerged in water.
- the catalyst, aluminum chloride (total 0.46 g, 0.006 mole) is added in batches of 0.05g at regular intervals over a period of about 8 hours. Progress of the reaction is followed conveniently by the rate of escaping isobutane gas.
- a solution of 11.0 mmol of a heterodiamondoid in 18.7 g of methylene chloride is mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) of peracetic acid in ethyl acetate. While being stirred vigorously, the solution is irradiated with a 100- watt UV light placed in an immersion well in the center of the solution. Gas evolution is evident from the start. The temperature is maintained at 40-45 °C for an about 21- hour irradiation period. At the end of this time, about 95% of the peracid had been consumed. The solution is concentrated to near dryness, treated twice in succession with 100-mL portions of toluene and reevaporated to dryness.
- a suitable monobrominated heterodiamondoid (0.066 mol) is heated to reflux for about 1 h in a round bottom flask, which is equipped with a stirrer and a reflux condenser, while stirring and adding 35 mL water, 3.5 mL tetrahydrofuran, 2.0 g potassium carbonate and 1.3 g silver nitrate.
- the reaction product which has crystallized out, is separated out and is extracted with tetrahydrofuran.
- the extract is diluted with water and the precipitate is suctioned off, dried and purified by sublimation under vacuum.
- a suitable G-CH 2 CH 2 -Br (0.066 mol) is heated to reflux for about 1 h in a round bottom flask, which is equipped with a stirrer and a reflux condenser, while stirring and adding 35 mL water, 3.5 mL tefrahydrofuran, 2.0 g potassium carbonate and 1.3 g silver nitrate. After cooling, the reaction product is separated out and is extracted with chloroform. Evaporating the solvent affords the product after purification by column chromatography.
- the reaction mixture is worked up by adding saturated Na 2 SO 4 aqueous solution to decompose excess hydride at low temperature. Decantation from the precipitated salts gives a dry ether solution, which, when evaporated, affords a crude C-2 monohydroxylated heterodiamondoid substituted at the secondary carbon, i.e. C- 2 G-OH. Further recrystallization from cyclohexane gives an analytically pure sample.
- a solution of 11.0 mmol of a suitable heterodiamondoid in 18.7 g of methylene chloride is mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) of peracetic acid in ethyl acetate. While being stirred vigorously, the solution is irradiated with a 100-watt UV light placed in an immersion well in the center of the solution. Gas evolution is evident from the start. The temperature is maintained at 40- 45 °C for an about 21-hour irradiation period. At the end of this time, about 95% of the peracid had been consumed.
- the solution is concentrated to near dryness, treated twice in succession with 100-mL portions of toluene and reevaporated to dryness. Final drying in a desiccator affords a crude white solid.
- the crude hydroxylated heterodiamondoid mixture is then partially dissolved in acetone.
- the oxygenated components go into the solution but not all of the unreacted heterodiamondoid.
- Chromic acid-sulfuric acid solution is added dropwise until an excess is present, and the reaction mixture is stirred overnight.
- the acetone solution is decanted from the precipitated chromic sulfate and the unreacted heterodiamondoid, and is dried with sodium sulfate.
- the unreacted heterodiamondoid is recovered by dissolving the chromium salts in water and filtering. Evaporation of the acetone solution affords a white solid.
- This crude solid is chromatographed on alumina with standard procedures elutmg first with 1 : 1 (v/v) benzene/light petroleum ether followed by ethyl ether or a mixture of ethyl ether and methanol (95:5 v/v) to collect the unreacted heterodiamondoid and the heterodiamondoidone, respectively. Further purification by recrystallization from cyclohexane affords a pure heterodiamondoidone.
- a flask is charged with a mixture of a heterodiamondoidone (0.026 mole), phenol (16.4 g, 0.17 mole), and butanethiol (0.15 L). Heat is applied and when the reaction mixture becomes liquid at about 58 °C, anhydrous hydrogen chloride is introduced until the solution becomes saturated. Stirring is continued at about 60 °C for several hours, during which period a white solid begins to separate out from the reddish-orange reaction mixture. The solid obtained is filtered off, washed with dichloromethane and dried to afford the bisphenol heterodiamondoid product. It is purified by sublimation after recrystallization from toluene.
- a mixture of a 2,2-bis(4-hydroxyphenyl) heterodiamondoid (0.01 mole), »-fluoronitrobenzene (3.1 g, 0.022 mole), potassium carbonate (3.31 g, 0.024 mole) and NN-dimethylacetamide (DMAc, 10 mL) is refluxed for about 8 hours.
- the mixture is then cooled and poured into a ethanol/water mixture (1 : 1 by volume).
- the crude product is crystallized from DMF to provide yellow needles of the 2,2-bis[4-(4- nitrophenoxy)phenyl] heterodiamondoid.
- a mixture of 0.05 mole of a heterodiamondoid and 50 mL of glacial acetic acid is charged to a stirred stainless 100 mL autoclave which is pressurized with nitrogen to a total pressure of 500 p.s.i.ga. After the mixture is then heated to 140 °C, 9.0 g (0.1 mole) of concentrated nitric acid is introduced into the reaction zone by means of a feed pump at a rate of 1-2 mL per minute. When the acid feed is completed, the reaction temperature is maintained at 140 °C for 15 minutes, after which time the reaction mixture is cooled down to room temperature and diluted with an excess of water to precipitate the products.
- the filtered solids are slurried with a mixture of 10 mL of methanol, 15 mL of water, and 1.7 g of potassium hydroxide for 18 hours at room temperature. After dilution with water, the alkali-insoluble material is extracted by light petroleum ether. The petroleum ether extracts are washed by water and dried over anhydrous magnesium sulfate. Concentration of this solution affords a white solid. The aqueous alkali solution from which the alkali-insoluble material had been extracted is cooled to 0-3 °C and neutralized by the dropwise addition of an aqueous acetic acid-urea mixture to regenerate some more products. GC analysis shows that the alkali-insoluble sample is mainly mononitro heterodiamondoid.
- a mixture of 29.6 g (0.4 mole) tert-butanol and 55 g (1.2 mole) 99% formic acid is added dropwise over about 3 hours to a mixture of 470 g 96% sulfuric acid and 0.1 mole heterodiamondoid dissolved in 100 mL cyclohexane while stirring vigorously at room temperature. After decomposing with ice, the acids are isolated and purified by recrystallization from methanol/water giving the monocarboxylated heterodiamondoid.
- a mixture of a suitable monobrominated heterodiamondoid G-Br (0.012 mole) and 9.0 g trichloroethylene CHCr ⁇ CCk is added dropwise in the course of about 4 hours into 24 L 90% sulfuric acid at 103-106 °C while stirring. After the addition is completed, the mixture is stirred for about an additional 2 hours at the specified temperature, then cooled down and hydrolyzed with ground ice.
- the precipitated product can be freed from the neutral fraction by dissolution in dilute sodium hydroxide solution and extraction with ethyl ether. When acidified with dilute hydrochloric acid solution, the carboxylic acid precipitates out of the alkaline solution.
- a suitable monobrominated heterodiamondoid G-Br (0.093 mole) is dissolved in 150 mL acetonitrile. While stirring, 30 mL concentrated sulfuric acid is slowly added to the above solution, whereby the mixture heats up. After it has been left standing for about 12 hours, the solution is poured into 500 mL ice water, whereby the monoacetamino heterodiamondoid separates out in high purity.
- G-CH CH 2 from G-Br
- Step 1 a solution of a suitable monobrominated heterodiamondoid G-Br
- the combined ether extracts are washed with water and dilute sodium carbonate aqueous solution. After they have been dried over calcium chloride, the ether is distilled off. The residue is separated by distillation under vacuum. Recrystallizing from methanol affords crystals of the heterodiamondoidyl ethyl bromide G-CH 2 CH 2 Br.
- Step 2 a solution of 0.7 g fine powdered potassium hydroxide and the above heterodiamondoidyl ethyl bromide G-CH 2 CH 2 Br (0.012 mole) in 10 mL diethylene glycol is heated to 220 °C in the oil bath for 6 hours. After cooling down the mixture is diluted with 30 mL water and exacted with ethyl ether. The ether extract is washed twice with water and dried over calcium chloride. The residue left behind after the ether has been distilled off is sublimated in vacuum, and if necessary, the compound can be recrystallized from methanol.
- Step 1 in a 150-mL two-necked flask with a stirrer and a drying tube, a mixture of 0.069 mole of a suitable monobromonated heterodiamondoid and 20 mL vinyl bromide is cooled to -65 °C in a cooling bath. While stirring, 4.5 g powdered aluminum bromide is added in portions and the mixture is stirred for an additional about 3 hours at the same temperature. Then the reaction mixture is poured into a mixture of 30 mL water and 30 mL ethyl ether. After vigorously stirring, the ether layer is separated and the aqueous layer is extracted once more with ether. The combined ether extracts are washed with water and dilute sodium carbonate solution. After it has been dried with calcium chloride and the solvent has been distilled off, the residue is distilled under vacuum.
- Step 2 15 g powdered potassium hydroxide in 30 mL diethylene glycol is heated to reflux with 0.046 mole of the above product for about 9 hours in the oil bath. Compound monoethynylated heterodiamondoid which is formed is then sublimated in the condenser and must be returned to the reaction mixture from time to time. At the end of the reaction time, the reaction mixture is distilled until no more solid particles go over. The distillate is extracted with ethyl ether and the ether phase is washed with water and dried over calcium chloride. A short time after the ether has been distilled off, the residue solidifies. It is sublimated under vacuum and, if necessary, recrystallized from methanol.
- Heterodiamondoidyl acetic acid e.g. G-COOH is prepared as shown in Example 29.
- the corresponding acid chloride G-COC1 is obtained by stirring a mixture of the acid and thioyl chloride diluted with petroleum ether at room temperature for about 50 hours.
- Treatment of the acid chloride G-COC1 with an excess amount of ethereal diazomethane gives the heterodiamondoidyl acetyl diazomethane G-COCHN 2 .
- Reactions of the acid chloride G-COC1 with such amines as ammonia and aniline give the corresponding amides, in those cases G-CONH 2 and G-CONHC 6 H 5 respectively.
- the reaction mixture is filtered and the filtrate is poured into ice water and shaken in a separatory funnel.
- the organic layer is dried with sodium sulfate and concentrated to about one-fifth of its original volume under reduced pressure at room temperature, and the concentrated solution is stored in a freezer.
- the yield may be considered essentially quantitative for the purpose of synthetic use of the solution.
- a suitable amino acid (5 mmoles) is suspended in water (about 20 mL).
- the combined extracts are dried over sodium sulfate and the solvent is removed in vacuo.
- the residue is recrystallized from a suitable solvent, e.g. ether-petroleum ether, ethyl acetate or ethyl acetate-petroleum ether.
- G-Br 0.1 mole of G-Br, 40 g (0.15 mol) of AlBr 3 and 200 mL of PC1 3 are heated for about 5 hours under reflux while being stirred. After cooling down and filtration, the residue is washed with 100 mL of benzene, suspended in 300 mL of CC1 4 and decomposed carefully with water while cooling with ice. The organic phase is separated out, washed with water, dried over CaCl 2 and concentrated in vacuum. Separation and purification of the product G-POCl 2 can be conducted by distilling the residue and recrystallization from acetone. Please note that G-POCl 2 does not reaction with ethanol in pyridine or piperidine in benzene.
- G-PC1 0.01 mole of G-PC1 is stirred in 50 mL water intensively for about 10 hours at room temperature. Then the mixture is filtered and the residue is recrystallized several times from acetonitrile to yield the product G-P(OH) 2 .
- a monobrominated heterodiamondoid G-Br (50 mmole) is dissolved in 30 mL of xylene and heated to reflux in a three-necked flask fitted with thermometer, nitrogen inlet, stirrer, and reflux condenser, under a slow stream of nitrogen. Then a total of 1.15 g of small pieces of sodium metal is added to the stirred reaction mixture over a period of about 4 hours. After all sodium has been added, the mixture is refluxed for about an additional hour and then filtered in the hot state. On cooling to room temperature, the product G-G is crystallized from the filtrate. This G-G product can itself be di brominated and thereafter converted to dicyano, decarboxyl diamino and diacetamido derivatives as desired.
- Polymers such as polyamides, polyimides, polyesters, polycarbonates which are easily processed soluble, mechanically strong and thermally stable are very important materials in a wide range of industries, such as the microelectronics industry.
- Introduction of different pendant groups such as heterodiamondoid groups along the polymer backbone can impart greater solubility and enhanced rigidity as well as better mechanical and thermal properties of the resulting polymers.
- heteroatom-containing cage hydrocarbons are introduced into the polymer chain because such cardo groups show significant characteristics such as high cardo/hydrogen ratio, high thermal and oxidative stability, rigidity, hydrophobicity, and transparency. They also can impart desired electrical and optical properties to the polymers.
- compositions are subjected to polymerization: diacrylated heterodiamondoid; monoacrylated heterodiamondoid; a 50:50 mixture by weight of monoacrylated heterodiamondoids and methyl methacrylate; and, a 50:50 mixture by weight of monoacrylated heterodiamondoid and diethylene glycol bis allylcarbonate.
- a photo-polymerization initiator benzophenone
- the mixture is applied to a glass plate and photo- polymerized by irradiation with ultraviolet light.
- a sample of a diethynylated heterodiamondoid (275 mg) is sealed in a glass tube and heated to 200 °C for 14 hours and at 250 °C for 48 hours. The tube is cooled to room temperature and opened to afford a polymeric resin.
- a 2,2-bis(4-hydroxyphenyl) heterodiamondoid (0.005 mole) is mixed with pyridine (2 mL) at room temperature for about 20 minutes.
- Terephthaloyl chloride (1.015 g, 0.005 mole) in nitrobenzene (20 mL) is added to the above solution at room temperature for about 5 minutes and then the mixture is heated to about 150 °C for about 10 hours.
- the resulting polymer solution is poured into methanol to precipitate the polymer.
- the polymer is washed with hot methanol, collected on a filter, and dried in vacuo at about 60 °C for about 24 hours.
- a flask is charged with a mixture of a 2,2-bis[4-(4-aminophenoxy)phenyl] heterodiamondoid (0.9 mmol), terephthalic acid (0.149 g, 0.9 mmol), triphenyl phosphite (0.7 mL), pyridine (0.6 mL), N-methyl-2-pyrrolidone ( ⁇ MP, 2 mL) and calcium chloride (0.25 g). It is refluxed under argon for about 3 hours.
- reaction mixture After cooling, the reaction mixture is poured into a large amount of methanol with constant stirring, producing a precipitate that is washed thoroughly with methanol and hot water, collected on a filter, and dried to afford a polyamide containing heterodiamondoid components along the polymer chain.
- the polymerization is performed under a gentle nitrogen stream to remove the water produced during imidization. Work-up is done by pouring the resulting solution into excess methanol and filtering. The precipitated polymer is washed several times with water and methanol, and then the polymer is dried at about 100 °C for around 12 hours in vacuo.
- the reaction mixture is then immersed in an oil bath maintained at 100-110 °C for about 100 hours to polymerize.
- the resulting polymer is isolated by pouring the viscous reaction mixture into excess ethanol under vigorous stirring.
- the polymer precipitate is collected by filtration and washed thoroughly with ethanol and extracted with hot ethanol using a Soxhlet extractor and subsequently dried in a vacuum oven at 70 °C for about 24 hours.
- a suitable brominated heterodiamondoid (0.046 mole), resorcinol (5.51 g, 0.05 mole), and benzene (50 mL) are combined in a reaction flask equipped with a nitrogen inlet, a condenser fitted with a caustic scrubber, and a stirrer. This mixture is heated to reflux and for about 72 hours to allow for reaction under a constant nitrogen purge to assist in the removal of HBr formed. The reaction mixture is cooled to ambient temperature and the hetero diamondoidyl substituted resorcinol is crystallized from solution.
- Residual resorcinol is removed by precipitating a solution of the product in methanol into warm water followed by filtrating and washing with water. Subsequent purification to a polymerization quality monomer is accomplished by vacuum drying to remove residual water, recrystallizing from toluene, and finally subliming to afford the product which is used in the following reactions.
- a flask is charged with 1.73 mmol of a 4-(l-heterodiamondoidyl)-l,3- bis(4-aminophenoxy)benzene, 0.68 g (3.54 mmol) of trimellitic anhydride, and 5 mL of DMAc.
- the mixture is stirred at room temperature for about 5 hours under argon atmosphere. While continuing to maintain agitation and room temperature, 2.4 mL of acetic anhydride and 1.5 mL of pyridine are added incorporating for about 1 hour. Afterwards the mixture is heated at 100 °C for about 4 hours and then cooled and poured into methanol.
- the precipitate is filtered off and is purified by exfraction with hot ethanol using a Soxhlet extractor and subsequently dried in a vacuum oven at 70 °C for 24 hours to afford diimide-dicarboxylic acid: 4-(l-hetero diamondoidyl)- 1,3- bis(4-trimellitimidophenoxy)benzene.
- reaction mixture is poured into a large amount of methanol with constant stirring, producing a precipitate that is washed thoroughly with hot water and methanol, collected on a filter, and dried at 100 °C under vacuum for 24 hours to afford a pure polyamide- imide containing heterodiamondoid components in the polymer backbone.
- a 4-(l-heterodiamondoidyl)-l ,3-benzenediol (20.5 mmol) and 4,4'- difluorobenzophenone (4.468 g, 20.5 mmol) mixture is dissolved in 35 mL DMAc and 10 mL toluene in a reaction flask fitted with a nitrogen blanket, mechanical stirrer, and a Dean-Stark trap.
- K 2 CO 3 2.969 g, 21.48 mmol
- Reflux is held at around 130 °C for about 1 hour followed by the gradual removal of toluene from the reaction flask until the flask temperature reaches around 160 °C (ca. 1 hours).
- the reaction mixture is maintained at 160 °C for 10 hours and then cooled to ambient temperature.
- the polymer solution is diluted with chloroform, filtered to remove the inorganic salts, acidified, and then precipitated into methanol. Filfration and drying of the product at about 120 °C under vacuum gives the homopolymer.
- Co-polymerizations are carried out with different molar ratios of co- monomers (2,2-bis(4-hydroxyphenyl)propane and a 4-(l-heterodiamondoidyl)-l,3- benzenediol) using either DMAc or teframethylene sulfone (sulfolane) as solvent.
- a 4-(l-hetero diamondoidyl)- 1,3 -benzenediol (10.25 mmol) and 2,2-bis(4- hydroxyphenyl)propane (10.25 mmol) and 4,4'-difluorobenzophenone (4.468 g, 20.5 mmol) can be dissolved in 35 mL DMAc and 10 mL toluene in a reaction flask fitted with a nifrogen blanket, mechanical stirrer, and a Dean-Stark trap. To this mixture K 2 CO 3 (2.969 g, 21.48 mmol) is added while stirring and heating to reflux.
- Reflux is held at around 130 °C for about 1 hour followed by the gradual removal of toluene from the reaction flask until the flask temperature reaches around 160 °C (ca. 1 hours).
- the reaction mixture is maintained at 160 °C for 10 hours and then cooled to ambient temperature.
- the polymer solution is diluted with chloroform, filtered to remove the inorganic salts, acidified, and then precipitated into methanol. Filtration and drying of the product at about 120 °C under vacuum gives the copolymer. If sulfolane is used as the solvent, the co-polymers are Soxhlet extracted with methanol to remove solvent and salts from the insoluble polymer.
- a flask is charged with a mixture of 3-benzyloxypropylmalolactonate (85 mol%), ethyl heterodiamondoidyl malolactonate (15 mol%) and tetraethylammonium benzoate (IO '3 eq. per mole of total moles of the co-monomers, acting as an initiator of the anionic ring-opening co-polymerization) under nifrogen.
- the mixture is then well stirred and warmed to 37 °C under nifrogen atmosphere and is maintained at this temperature for 15 days. After completion of the co-polymerization reaction, the co- polymers are collected and washed with small amount of water, ethanol, and dried in vacuum for about 24 hours.
- Phenyl Heterodiamondoid-Modified PEGs [Poly(ethylene glycol)s] from Alcoholate ofHeterodiamondoidylphenol
- PEGs poly(ethylene glycol)s
- heterodiamondoid hydrocarbon compounds at their OH terminal ending(s).
- These hydrophobic groups may be selected based upon their potentially strong interactions with other groups in "cavities" formed in PEG polymer chains and thus can help deliver the drugs which have low solubility in water. Examples are shown in FIG. 28. EXAMPLE 63
- FIG. 29 shows the design of a carbon-rich cyclopolymer incorporating both imageable functionalities (tert-butyl esters) for chemical amplification, and high etch-resistance moieties (heterodiamondoids based on tetramantanes, pentamantanes, hexamantanes and the like).
- imageable functionalities tert-butyl esters
- etch-resistance moieties heteromondoids based on tetramantanes, pentamantanes, hexamantanes and the like.
- polyarylates derived from bisphenol and iso/terephthalic acid are well accepted as highly thermally stable materials.
- polyarylates are generally difficult to process because of their limited solubility in organic solvents and their high melting temperatures or high T g 's by virtue of their rigid structures.
- incorporation of bulky pendant cardo groups, such as adamantyl groups, into polymer backbones results in enhanced thermal properties of the polymers compared with polymers containing aromatic bisphenols.
- FIG. 26 shows the design of such polyesters.
- Aromatic polyamides attract much interest because of their high- temperature resistance and mechanical strength.
- the applications of polyamides are limited by processing difficulties arising from their low solubility in organic solvents and their high glass transition or melting temperature.
- a number of successful approaches to increasing the solubility and processability of polyamides, without sacrificing their thermal stability, employ the introduction of flexible or non- symmetrical linkages into the polymer backbone or the incorporation of bulky substituents, such as pendant groups, into the polymer backbone.
- the inter-chain interaction of the polymers can be decreased by the introduction of bulky pendant groups, resulting in improved solubility of the polymers.
- the incorporation of pendant groups results in amorphous materials with increased solubility in common organic solvents.
- FIG. 27 presents an example of this design which incorporates heterodiamondoid groups in the polyamide backbone.
- aromatic polyimides such as excellent thermo-oxidative stability and superior chemical resistance
- polyimides in many applications such as insulating materials for electronics, semipermeable membranes for gas separations, and high-temperature adhesives and coatings
- aromatic polyimides are insoluble and intractable and are, only processable under extreme conditions.
- heterodiamondoid groups can be placed in polyimide polymer backbone (FIG. 28), and in polyaspartimides (FIG. 29).
- Aromatic polyimides are recognized as a class of high performance materials because of their remarkable thermal and oxidative stabilities and their excellent electrical and mechanical properties, even during long periods of operation. Unfortunately, strong interactions between polyimide chains and their rigid structure make them intractable. Poor thermoplastic fluidity and solubility are the major problems for wide applications of polyimides.
- polyamides have the advantage of good solubility and processability, as do polyetherimides. Therefore, polyamide-imide or polyetherimide might be the most useful materials, combining the advantages of both polyimides (such as high-temperature stability) and polyamides (such as good processability).
Abstract
Description
Claims
Priority Applications (4)
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CA002492857A CA2492857A1 (en) | 2002-07-18 | 2003-07-17 | Heterodiamondoids |
EP03765723A EP1542983A1 (en) | 2002-07-18 | 2003-07-17 | Heterodiamondoids |
AU2003252028A AU2003252028A1 (en) | 2002-07-18 | 2003-07-17 | Heterodiamondoids |
JP2004523563A JP2006506334A (en) | 2002-07-18 | 2003-07-17 | Hetero diamondoid |
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US39736702P | 2002-07-18 | 2002-07-18 | |
US60/397,367 | 2002-07-18 | ||
US60/397,368 | 2002-07-18 |
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PCT/US2003/022483 WO2004009577A1 (en) | 2002-07-18 | 2003-07-17 | Heterodiamondoids |
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US (4) | US7049374B2 (en) |
EP (2) | EP1997816A1 (en) |
JP (1) | JP2006506334A (en) |
KR (1) | KR20050042133A (en) |
CN (1) | CN1668608A (en) |
AU (1) | AU2003252028A1 (en) |
CA (1) | CA2492857A1 (en) |
WO (1) | WO2004009577A1 (en) |
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- 2003-07-17 AU AU2003252028A patent/AU2003252028A1/en not_active Abandoned
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WO2004010512A2 (en) * | 2002-07-18 | 2004-01-29 | Chevron U.S.A. Inc. | Heteroatom-containing diamondoid transistors |
WO2004010512A3 (en) * | 2002-07-18 | 2004-10-28 | Chevron Usa Inc | Heteroatom-containing diamondoid transistors |
US7402835B2 (en) | 2002-07-18 | 2008-07-22 | Chevron U.S.A. Inc. | Heteroatom-containing diamondoid transistors |
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US7402716B2 (en) | 2003-12-31 | 2008-07-22 | Chevron U.S.A. Inc. | Hybrid cubic/hexagonal diamondoids |
JP2007522333A (en) * | 2004-02-17 | 2007-08-09 | ペン ステート リサーチ ファウンデイション | Telechelic polymers containing reactive functional groups |
JP2006233128A (en) * | 2005-02-28 | 2006-09-07 | Fuji Photo Film Co Ltd | Polymer with cage structure, composition for film forming containing the same, insulating film and electric device |
JP4516857B2 (en) * | 2005-02-28 | 2010-08-04 | 富士フイルム株式会社 | Polymer having cage structure, film-forming composition containing the same, insulating film and electronic device |
US8314119B2 (en) | 2006-11-06 | 2012-11-20 | Abbvie Inc. | Azaadamantane derivatives and methods of use |
US8987453B2 (en) | 2006-11-06 | 2015-03-24 | Abbvie Inc. | Azaadamantane derivatives and methods of use |
US9464078B2 (en) | 2010-09-23 | 2016-10-11 | Abbvie Inc. | Monohydrate of azaadamantane derivatives |
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AU2003252028A1 (en) | 2004-02-09 |
JP2006506334A (en) | 2006-02-23 |
EP1542983A1 (en) | 2005-06-22 |
US20100094012A1 (en) | 2010-04-15 |
KR20050042133A (en) | 2005-05-04 |
US7981975B2 (en) | 2011-07-19 |
CN1668608A (en) | 2005-09-14 |
US8013078B2 (en) | 2011-09-06 |
AU2003252028A8 (en) | 2004-02-09 |
US20040059145A1 (en) | 2004-03-25 |
CA2492857A1 (en) | 2004-01-29 |
US20060183870A1 (en) | 2006-08-17 |
US7649056B2 (en) | 2010-01-19 |
US20100190985A1 (en) | 2010-07-29 |
US7049374B2 (en) | 2006-05-23 |
EP1997816A1 (en) | 2008-12-03 |
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