WO2012121354A1 - カーボンナノチューブの製造方法 - Google Patents
カーボンナノチューブの製造方法 Download PDFInfo
- Publication number
- WO2012121354A1 WO2012121354A1 PCT/JP2012/056033 JP2012056033W WO2012121354A1 WO 2012121354 A1 WO2012121354 A1 WO 2012121354A1 JP 2012056033 W JP2012056033 W JP 2012056033W WO 2012121354 A1 WO2012121354 A1 WO 2012121354A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- reaction
- mol
- cycloparaphenylene
- group
- Prior art date
Links
- 0 CC(C)(*)c1ccc(C(*)(CC2)CCC2c2ccc(*)cc2)cc1 Chemical compound CC(C)(*)c1ccc(C(*)(CC2)CCC2c2ccc(*)cc2)cc1 0.000 description 12
- NJXUWONHNYJPMY-UHFFFAOYSA-N CC1(C)COB(c(cc2)ccc2-c2ccc(B3OCC(C)(C)CO3)cc2)OC1 Chemical compound CC1(C)COB(c(cc2)ccc2-c2ccc(B3OCC(C)(C)CO3)cc2)OC1 NJXUWONHNYJPMY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/75—Single-walled
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
- Y10S977/843—Gas phase catalytic growth, i.e. chemical vapor deposition
Definitions
- the present invention relates to a method for producing a carbon nanotube (CNT) using a cyclic compound formed by connecting a plurality of aromatic rings and holding a ⁇ -electron conjugated system as a template.
- a carbon nanotube having a structure in which a two-dimensional graphene sheet is wound in a cylindrical shape is known.
- carbon nanotubes have properties such as high conductivity, high mechanical strength, excellent elasticity, heat resistance, and lightness, they can be used in various fields such as chemistry, electronics, and life science. Application is expected.
- a method for producing a carbon nanotube for example, an arc discharge method, a laser fanes method, a chemical vapor deposition method (CVD method), and the like are known.
- CVD method chemical vapor deposition method
- Non-Patent Document 1 discloses a method for producing a mixture of cycloparaphenylene compounds having a ring structure in which 9, 12, or 18 benzene rings are linked using 1,4-diiodobenzene and benzoquinone as raw materials. Is described.
- Non-Patent Documents 2 and 3 describe a method for producing a cycloparaphenylene compound having a ring structure in which 12 benzene rings are regularly connected using 1,4-cyclohexanedione and 1,4-diiodobenzene. Is described.
- Non-Patent Document 4 describes a method for producing a cycloparaphenylene compound having a cyclic structure in which eight benzene rings are regularly connected by reductive elimination of a square biphenylene platinum complex with bromine.
- the cycloparaphenylene compound disclosed in the above non-patent document has a ring-shaped chemical structure in which a plurality of phenylene groups are linked by a single bond, and is the smallest structural unit of an armchair-type single-walled carbon nanotube (CNT).
- CNT carbon nanotube
- An object of the present invention is to provide a method for selectively producing carbon nanotubes having a desired diameter (hereinafter referred to as “CNT”).
- the present inventors used a cyclic compound in which a plurality of aromatic rings are connected and held a ⁇ -electron conjugated system as a template. It has been found that single-walled carbon nanotubes (SWCNTs) in which the diameter of the template ring is maintained can be produced by heat treatment with a carbon source.
- SWCNTs single-walled carbon nanotubes
- a typical template includes a cyclic compound formed by connecting divalent aromatic hydrocarbon groups. This is expressed as “carbon nanoring”.
- carbon nanoring includes “cycloparaphenylene compound” (see Non-Patent Documents 1 to 4), which is the shortest skeleton of an armchair single-walled carbon nanotube, and at least one phenylene group of the cycloparaphenylene compound.
- modified cycloparaphenylene compounds in which is substituted with a divalent condensed polycyclic aromatic hydrocarbon group (for example, a 2,6-naphthylene group, etc.).
- a graphene sheet is grown in the central axis direction of the cyclic compound by using the template (cyclic compound) and causing a carbon source to act on the template.
- Carbon nanotubes (CNT) having substantially the same size can be selectively produced. Therefore, the method of the present invention is a very innovative manufacturing method capable of selectively manufacturing CNTs having a substantially constant diameter.
- FIG. 1 shows a schematic diagram in which an armchair single-walled carbon nanotube is formed by reacting a carbon source with a cycloparaphenylene compound ([n] CPP) in which n paraphenylenes are linked.
- the present invention provides the following carbon nanotube (CNT) manufacturing method and carbon nanotube (CNT).
- Item 1 A method for producing a carbon nanotube, comprising reacting a carbon source with a cyclic compound formed by connecting a plurality of aromatic rings.
- Item 2 The production method according to Item 1, wherein the reaction is performed by supplying a gaseous carbon source and heating under reduced pressure.
- Item 3. The production method according to Item 1 or 2, wherein the cyclic compound formed by connecting a plurality of aromatic rings is a cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups.
- Item 4 The cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups is a cycloparaphenylene compound, or at least one phenylene group of the cycloparaphenylene compound is a divalent condensed polycycle.
- Item 4. The production method according to Item 3, which is a modified cycloparaphenylene compound substituted with an aromatic hydrocarbon group.
- a represents an integer of 6 or more.
- at least one phenylene group of the cycloparaphenylene compound represented by the general formula (1) is represented by the general formula (2):
- Item 5 (In the formula, b represents an integer of 1 or more.)
- Item 5 The production method according to Item 4, which is a modified cycloparaphenylene compound substituted with a group represented by the formula:
- Item 6 The production method according to Item 5, wherein the cycloparaphenylene compound is a compound in which a in the general formula (1) is an integer of 6 to 100.
- Item 7. The production method according to Item 5 or 6, wherein the cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups is a cycloparaphenylene compound represented by the general formula (1). .
- R 2 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group
- R 4 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon Group is the same or different, and each is an integer of 0 or more
- n is the same or different and each represents an integer of 1 or more.
- Item 4 (Wherein R 7 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13)
- Item 3 The production method according to Item 3, which is a cyclic compound represented by:
- Item 9 The production method according to any one of Items 1 to 8, wherein the carbon source is at least one selected from the group consisting of hydrocarbon compounds, alcohol compounds, ether compounds and ester compounds.
- Item 10 The production method according to any one of Items 1 to 9, wherein the reaction is performed by heat treatment at 400 to 1200 ° C. under a pressure of 10 ⁇ 4 to 10 5 Pa while supplying a gaseous carbon source.
- Item 11 A carbon nanotube obtained by reacting a carbon source with a cyclic compound formed by connecting a plurality of aromatic rings.
- Item 12. The carbon nanotube according to Item 11, wherein the reaction is conducted by supplying a gaseous carbon source and heating under reduced pressure.
- Item 13 The carbon nanotube according to Item 11 or 12, which is a single-walled carbon nanotube.
- SWCNTs can be manufactured.
- a cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups such as a cycloparaphenylene compound and a modified cycloparaphenylene compound can be used.
- Various templates can be selected and can be easily manufactured based on a known method and a method described in the present specification.
- various CNTs such as an armchair type and a chiral type can be produced from the structure of this template.
- a cycloparaphenylene compound is used as a template, an armchair CNT having a certain diameter can be selectively produced.
- a modified cycloparaphenylene compound is used as a template, chiral CNTs having a certain diameter can be selectively produced.
- the production method of the present invention it is not necessary to use a catalyst that is indispensable in the conventional CNT production method, so that the separation work of the CNT obtained after the reaction and the catalyst is unnecessary.
- the conventional method there are a large number of impurities due to the catalyst or the like used, but in the method of the present invention, highly pure CNT can be produced.
- the manufacturing method of this invention since it can implement by comparatively low-temperature heat processing, there is no restriction
- the method of the present invention is an epoch-making method capable of selectively and efficiently producing CNTs having a desired diameter.
- FIG. 1 The schematic diagram in which an armchair type single-walled CNT is formed from a cycloparaphenylene compound ([n] CPP) in which n paraphenylenes are linked is shown.
- 2 is a transmission electron micrograph of the CNT obtained in Example 1.
- 2 is a transmission electron micrograph of the CNT obtained in Example 1.
- 2 is a graph showing a distribution of diameters measured with a transmission electron microscope of the CNTs obtained in Example 1.
- the relationship between the excitation wavelength of the laser by the Raman spectroscopy of CNT obtained in Example 1 and a Raman spectrum is shown.
- the relationship between the excitation wavelength of the laser by the Raman spectroscopy of CNT obtained in Example 2 and a Raman spectrum is shown.
- the method for producing CNTs of the present invention is characterized in that a cyclic compound formed by connecting a plurality of aromatic rings is reacted with a carbon source.
- Cyclic compound (template) formed by connecting multiple aromatic rings In the CNT production method of the present invention, a cyclic compound formed by connecting a plurality of aromatic rings can be used as a production raw material. In other words, the cyclic compound can be used as a template (template) for CNT.
- a cyclic compound in which a plurality of aromatic rings are linked means a compound in which a plurality of aromatic rings are linked in a ring shape while maintaining a ⁇ -electron conjugated system.
- Examples of the cyclic compound formed by connecting aromatic rings include a cyclic compound (carbon nano ring) formed by connecting a plurality of divalent aromatic hydrocarbon groups.
- Examples of the cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups include, for example, a cycloparaphenylene compound and at least one phenylene group of the cycloparaphenylene compound is divalent condensed poly. And modified cycloparaphenylene compounds substituted with a ring aromatic hydrocarbon group.
- cycloparaphenylene compound examples include cycloparaphenylene compounds having 6 or more phenylene groups. Specifically, the general formula (1):
- a represents an integer of 6 or more.
- the compound represented by these is mentioned.
- a is preferably an integer of 6 to 100, more preferably 8 to 50, still more preferably 8 to 30, even more preferably 9 to 20, and particularly preferably 10 to 18.
- a includes 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., and in particular, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 etc. are mentioned.
- the diameter of the ring in the compound represented by the general formula (1) is about 1.2 to 1.7 nm when a is 9 to 12, and 1.8 to 2 when a is 13 to 16. .4 nm, and when a is 13-18, it is about 1.8-2.5 nm.
- the diameter of the cyclic compound that is a starting material is almost transferred to the diameter of the CNT, so that a CNT having a substantially uniform diameter can be manufactured.
- the modified cycloparaphenylene compound is a divalent condensed polycyclic ring in which at least one (preferably 1 to 4, more preferably 1 to 2, particularly preferably 1) phenylene group of the above cycloparaphenylene compound is used. It is a compound substituted with an aromatic hydrocarbon group.
- Examples of the divalent condensed polycyclic aromatic hydrocarbon group include two or more (2 to 7, more preferably 2 to 4) such as naphthalene, anthracene, phenanthrene, naphthacene, triphenylene, pyrene, chrysene, pentacene, hexacene, and perylene. And especially a divalent group obtained by removing two hydrogen atoms from a hydrocarbon condensed with a benzene ring.
- the position of the two bonds of the condensed polycyclic aromatic hydrocarbon group is not particularly limited as long as the modified cycloparaphenylene compound can form a ring.
- b represents an integer of 1 or more.
- the group represented by these is mentioned.
- b is preferably an integer of 1 to 6, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
- cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups include, for example, the general formula (3):
- R 2 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group
- R 4 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon Group is the same or different, and each is an integer of 0 or more
- n is the same or different and each represents an integer of 1 or more.
- R 7 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13) And the like, and the like.
- the phenylene groups represented by R 2 and R 4 may be the same or different, but a 1,4-phenylene group is preferred.
- the divalent condensed polycyclic aromatic hydrocarbon groups represented by R 2 and R 4 may be the same or different, but two or more (2-7, Further, a divalent group obtained by removing two hydrogen atoms from a hydrocarbon condensed with 2 to 4, particularly 2) benzene rings. Specifically, it is as having mentioned above, Preferably group represented by the said General formula (2) is mentioned.
- m may be the same or different, but is an integer of 0 or more.
- the integer is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 1 or 2.
- m is 2 or more, a plurality of R 4 are directly bonded. In this case, R 4 directly bonded may be the same or different.
- n may be the same or different, but is an integer of 1 or more.
- the integer is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 1 or 2.
- n is 2 or more, a plurality of R 2 are directly bonded. In this case, R 2 directly bonded may be the same or different.
- R 2 and R 4 when at least one of R 2 and R 4 is a divalent condensed polycyclic aromatic hydrocarbon group (particularly, a group represented by the general formula (2)), Can be. Furthermore, by using this carbon nanoring as a template for the production method of the present invention described later, chiral CNTs that substantially retain the diameter derived from this carbon nanoring can be produced.
- d is preferably an integer of 1 to 3, more preferably 1 or 2.
- Carbon source As the carbon source used in the production method of the present invention, various carbons or carbon-containing compounds can be used. From the template (cyclic compound), a graphene sheet of CNT is grown in the central axis direction of the ring. There is no particular limitation as long as it can be used. For example, carbon, a hydrocarbon compound, an alcohol compound, an ether compound, an ester compound, and the like can be given. One of these or two or more of them can be used.
- hydrocarbon compound examples include saturated or unsaturated aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds.
- saturated aliphatic hydrocarbon compound examples include linear, branched or cyclic alkanes having C1 to 100 (preferably C1 to 10, more preferably C1 to 4). Specific examples include methane, ethane, propane, butane, pentane, hexane, heptane and the like.
- Examples of the unsaturated aliphatic hydrocarbon compound include linear, branched or cyclic C2-100 (preferably C2-10, more preferably C2-6) having 1 to 3 double bonds.
- Alkenes are mentioned. Specific examples include ethylene, propene, 1-butene, 2-butene, butadiene and the like, preferably ethylene.
- a linear or branched alkyne of C2 to 100 preferably C2 to 10, more preferably C2 to 4) having 1 to 3 triple bonds can be given.
- Specific examples include acetylene and propyne, and acetylene is preferred.
- aromatic hydrocarbon compound examples include monocyclic or polycyclic aromatic hydrocarbons, and specifically include benzene, toluene, xylene, naphthalene, cumene, ethylbenzene, phenanthrene, anthracene, and the like.
- Examples of the alcohol compound include C1-50 (preferably C1-10, more preferably C1-4) linear, branched, or cyclic mono- or polyalcohol. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, ethylene glycol and the like. Preferred are methanol, ethanol, propanol and the like.
- ether compound examples include C2-50 (preferably C2-10, more preferably C2-4) linear, branched, or cyclic ethers. Specific examples include dimethyl ether, diethyl ether, diisopropyl ether, diisobutyl ether, tetrahydrofuran, dioxane and the like.
- ester compound examples include those represented by the formula: R 5 —C ( ⁇ O) O—R 6 (wherein R 5 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- R 6 represents an alkyl group having 1 to 10 carbon atoms.
- the compound represented by this is shown.
- the C1-10 alkyl group represented by R 5 and R 6 may be the same or different, and may be a straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or the like.
- a branched alkyl group is exemplified. Specific examples include methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and the like.
- a carbon source that can become a gas under reduced pressure is preferable, for example, C1-6 linear, branched or cyclic monoalcohol such as methanol, ethanol, propanol, etc .; methane C1-6 linear, branched or cyclic alkane such as ethane; C2-4 alkene such as ethylene; C2-4 alkyne such as acetylene, etc. are preferable.
- the CNT production method of the present invention is characterized in that a cyclic compound (template) formed by linking a plurality of aromatic rings is reacted with a carbon source. Specifically, it is preferable to supply a gaseous carbon source and heat under reduced pressure.
- the production method of the present invention can be carried out, for example, by chemical vapor deposition (CVD) in the presence of a carbon source using the cyclic compound as a template.
- CVD chemical vapor deposition
- a CNT is produced by placing a template on a suitable carrier and subjecting the template to chemical vapor deposition (CVD) using a source gas containing a carbon source under reduced pressure and heating conditions. Can do.
- a CNT can be produced by expanding a graphene sheet from a template (expanding a ⁇ -electron conjugated system) without using a catalyst (metal catalyst or the like) used in a conventional CVD method. (See, for example, FIG. 1).
- the obtained CNTs are single-walled CNTs (SWCNTs).
- the carrier for placing the template is not particularly limited as long as it is a material that can carry the template and does not adversely affect the process of producing CNTs.
- silica, alumina, magnesia, ceria, porous zeolite, mesoporous silica, etc. Can be mentioned.
- the shape of the carrier is not particularly limited, and examples thereof include various shapes such as powder, particles, and flat plate.
- a substrate may be used as a carrier.
- the substrate include a sapphire single crystal substrate, a silicon substrate, a quartz glass substrate, a porous silicon substrate, and a porous alumina substrate, and a sapphire single crystal substrate is preferable.
- the method for disposing the template on the substrate is not particularly limited.
- the template can be disposed by coating the substrate with a solution obtained by dissolving the template in an appropriate solvent.
- the solvent is not particularly limited as long as it can dissolve the template.
- alcohols for example, methanol, ethanol, propanol, etc.
- ethers for example, diethyl ether, tetrahydrofuran, dioxane, etc.
- aromatic carbonization etc.
- hydrogens for example, benzene, toluene, xylene and the like
- esters for example, ethyl acetate and the like
- the concentration of the solution containing the template can be appropriately changed depending on the solubility of the template, the size of the substrate, and the like. Usually, the concentration is preferably low so that the template molecules can be arranged in a single molecule state without overlapping on the substrate. For example, 0.00001 to 0.01% by weight, preferably 0.0001 to 0.005% by weight can be mentioned.
- the method for coating the substrate-containing solution on the substrate is not particularly limited, and examples thereof include spin coating, spray coating, dip coating, and the like, preferably spin coating.
- spin coating the number of rotations is, for example, about 1000 to 10,000 rpm, and the rotation time is about 10 to 30 seconds.
- the template can then be placed on the substrate by drying and removing the solvent.
- the reaction is carried out at an appropriate temperature and pressure after evacuating the reactor containing the carrier and supplying or supplying a gas containing a carbon source.
- the reaction is preferably carried out while stabilizing the temperature, pressure, and supply amount of the carbon source.
- the atmosphere gas for the reaction is not particularly limited as long as it does not react with the template or CNT under the reaction conditions and is inactive, and examples thereof include helium, argon, hydrogen, nitrogen, neon, krypton, or a mixed gas thereof. .
- helium, argon and the like are preferable.
- the supply of the carbon source can usually be a carbon source in a gaseous state.
- the supply amount of the carbon source is not particularly limited, and in the case of a gaseous carbon source, it may usually be 5 to 2000 mL / min.
- a mixed gas diluted with a gaseous carbon source and the above atmospheric gas may be supplied.
- the pressure in the reactor is usually preferably reduced under pressure (atmospheric pressure or less), for example, about 10 ⁇ 4 to 10 5 Pa, preferably about 10 ⁇ 3 to 10 5 Pa, more preferably 10 2 to 10 4 Pa. Degree.
- the temperature in the reactor is usually 400 to 1200 ° C, preferably 450 to 700 ° C, more preferably 450 to 500 ° C.
- the reaction time is, for example, 5 to 30 minutes, preferably 10 to 15 minutes.
- the structure of the obtained CNT can be evaluated by Raman spectroscopy and transmission electron microscope (TEM) observation.
- FIG. 4 shows the result of the CNT diameter distribution measured with a transmission electron microscope for the CNT produced from [12] cycloparaphenylene in Example 1.
- a vibration mode called breathing mode appears when one graphene sheet is seamlessly wound into a cylindrical shape. Since it is known that the frequency of this vibration mode is inversely proportional to the diameter of the tube, the distribution of the diameter of the CNT can be known by measuring the frequency of the breathing mode by Raman scattering.
- the ratio of the spectral intensity of the G band, which is a Raman band unique to CNT, and the intensity of the spectrum of the D band derived from amorphous carbon is used to determine the purity of the single-walled carbon nanotube after synthesis.
- G / D ratio the intensity of the spectrum of the D band derived from amorphous carbon
- the detected CNT differs depending on the laser wavelength used in Raman spectroscopy
- the physical properties of the CNT can be evaluated using lasers having different wavelengths.
- semiconductor CNT is detected at laser excitation wavelengths of 514 nm and 488 nm
- metal CNT is detected at an excitation wavelength of 633 nm.
- the production method of the present invention can produce CNTs that faithfully reproduce the diameter of the cyclic compound of the template. Therefore, it has a feature that the distribution of diameter is extremely small as compared with CNTs manufactured by a conventional general CVD method.
- CNTs manufactured by a conventional general CVD method For example, in Example 1, when [12] cycloparaphenylene (ring diameter: 1.65 nm) in which 12 phenylene groups are linked was used as a template, the obtained CNT had a diameter of 1.4 to 1.6 nm. [12] It almost coincides with that of CPP (FIG. 4). Therefore, the production method of the present invention is useful as a method for producing CNTs with a controlled diameter using a template.
- the production method of the present invention does not require a catalyst or a high temperature, and can be carried out under relatively low mild conditions. This is presumably because a graphene sheet can be formed (pi-conjugated system grows) under milder conditions without using a catalyst or high temperature because a template is used as a starting material.
- the obtained CNT does not contain impurities derived from the catalyst. Therefore, high-purity CNT can be obtained without going through a troublesome purification process.
- the metal fine particles of the catalyst are not included, the obtained CNTs can be used without problems in applications such as devices, transistors, integrated circuits, memories, sensors, and wiring.
- Cyclic compounds more aromatic rings formed by connecting used as a template in the method for manufacturing a template for manufacturing the present invention can be prepared, for example, in the following manner.
- the cycloparaphenylene compound (particularly the compound represented by the general formula (1)) can be produced, for example, according to or according to the methods described in Non-Patent Documents 1 to 4.
- Carbon nanorings (cycloparaphenylene compounds and / or modified cycloparaphenylene compounds) can also be produced, for example, by the production methods shown in Reaction Formulas 1 to 3.
- R 1 is the same or different and each represents a hydrogen atom or hydroxyl protecting group
- R 2 is the same or different and each represents a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group
- m ′ is the same or different, each is an integer of 1 or more
- n is the same or different, each is an integer of 1 or more
- Y is the same or different and each has the general formula (9):
- R 3 is the same or different and each represents a hydrogen atom or a C1-10 alkyl group, and R 3 may be bonded to each other to form a ring with the adjacent —O—B—O—.
- the group shown by is shown.
- R 1 is a hydrogen atom or a protecting group for a hydroxyl group.
- the hydroxyl-protecting group include an alkoxyalkyl group (for example, methoxymethyl group (—CH 2 —O—CH 3 , hereinafter sometimes referred to as “-MOM”)), an alkanoyl group (for example, acetyl group).
- silyl group eg, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, etc.
- tetrahydropyranyl group THP
- alkyl group eg, methyl group, ethyl group etc.
- aralkyl Group for example, benzyl group etc.
- it is an alkoxyalkyl group, especially a methoxymethyl group.
- R 2 and R 4 are as described above.
- M ′ is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, still more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 2.
- halogen atom represented by X examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- a bromine atom and an iodine atom are preferable, and a bromine atom is particularly preferable.
- the alkyl group represented by R 3 is preferably C1-8. More preferably, it is a C1-5 alkyl group, which may be linear or branched.
- R 3 is an alkyl group, the carbon atoms constituting each alkyl group may be bonded to each other to form a ring together with a boron atom and two oxygen atoms.
- Y for example, the following formulas (9a) to (9c):
- Compounds (5) and (6) can be synthesized according to Non-patent Document 3, Synthesis Examples 1 to 5 of the present specification, or the like.
- Compound (7a) can be produced by reacting compound (5) with compound (6).
- a Suzuki-Miyaura coupling reaction can be used for the reaction between the compound (5) and the compound (6).
- the Suzuki-Miyaura coupling reaction is a carbon-carbon bond reaction in which an aryl halide compound and an organic boron compound are coupled.
- the compound (5) is a halogenated aryl compound having a halogen atom
- the compound (6) is an organoboron compound having a boronic acid or an ester group thereof.
- the amount of compound (6) used in the above reaction is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.4 mol, still more preferably 0.001 mol, per 1 mol of compound (5). 08-0.2 mol.
- a palladium catalyst is usually used.
- the palladium-based catalyst include Pd (PPh 3 ) 4 (Ph is a phenyl group), PdCl 2 (PPh 3 ) 2 (Ph is a phenyl group), Pd (OAc) 2 (Ac is an acetyl group), Tris ( Dibenzylideneacetone) dipalladium (0) (Pd 2 (dba) 3 ), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphine) (Fino) palladium (0), (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and the like.
- Pd (PPh 3 ) 4 , Pd 2 (dba) 3 and the like are preferable.
- the amount of the palladium-based catalyst used is usually 0.0001 to 0.1 mol, preferably 0.0005 to 0.02 mol, based on 1 mol of the starting compound (5), from the viewpoint of yield.
- the amount is preferably 0.001 to 0.01 mol.
- a phosphorus ligand capable of coordinating with the palladium atom, which is the central element of the palladium catalyst can be used as necessary.
- the phosphorus ligand include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (2,6-dimethoxyphenyl) phosphine, tris [2- (Diphenylphosphino) ethyl] phosphine, bis (2-methoxyphenyl) phenylphosphine, 2- (di-t-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, tri-t-butylphosphine, bis (diphenylphosphine, tri
- the amount used is usually 0.001 to 1.0 mol, preferably 0.01 to 1.0 mol, based on 1 mol of the above compound (5) as a raw material, from the viewpoint of yield.
- the amount is 0.8 mol, more preferably 0.05 to 0.3 mol.
- a base boron atom activator
- the base is not particularly limited as long as it is a compound that can form an art complex on a boron atom in the Suzuki-Miyaura coupling reaction.
- cesium fluoride, cesium carbonate, and potassium phosphate are preferred.
- the amount of the base used is usually 0.01 to 10 mol, preferably 0.1 to 5.0 mol, more preferably 0.5 to 1.0 mol, relative to 1 mol of the starting compound (5). It is.
- the above coupling reaction is usually performed in the presence of a reaction solvent.
- the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; cyclic ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diisopropyl ether; Halogenated hydrocarbons such as methyl chloride, chloroform, dichloromethane, dichloroethane, dibromoethane; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; methanol, ethanol, isopropyl alcohol, and the like Alcohols; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. Of these, t
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- a purification step can be provided as necessary.
- this purification step it can be subjected to general post-treatments such as solvent (solvent) removal, washing, chromatographic separation, and the like.
- the number of aromatic rings of the compound (7a), that is, the length of the molecule can be designed freely and accurately by appropriately selecting the number n of R 2 in the compound (6). Can do.
- the halogen atom X contained in the compound (7a) is substituted with the boronic acid contained in the boron compound or its ester group Y.
- a boronic acid-derived boronic acid or a compound (8) having an ester group Y thereof is formed.
- the reaction to form this compound (8) is a borylation reaction.
- boron compound used in the above reaction examples include 2-phenyl-1,3,2-dioxaborinane, (4,4,5,5) -tetramethyl-1,3,2-dioxaborolane, 4 , 4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi [1,3,2-dioxaborolane] (bispinacolatodiboron), 5,5,5' , 5′-tetramethyl-5,5 ′, 6,6′-tetrahydro-2,2′-bi [4H-1,3,2-dioxaborin], 1,1,2,2-tetrahydroxy-1, 2-Diboraethane and the like.
- the amount of the boron compound used in the above reaction is preferably 1 to 10 mol, more preferably 1.5 to 7 mol, still more preferably 2 to 5 mol, per 1 mol of compound (7a). .
- the above reaction is usually carried out in the presence of a catalyst, and preferably a palladium catalyst is used.
- a palladium catalyst the palladium-based catalyst shown in the description of the coupling reaction can be used.
- Pd 2 (dba) 3 , Pd (PPh 3 ) 4 and the like are preferable.
- the amount used is usually 0.001 to 1 mol, preferably 0.005 to 0.1 mol, relative to 1 mol of the starting compound (7a), from the viewpoint of yield. More preferably, it is 0.01 to 0.05 mol.
- a phosphorus ligand can be used together with the catalyst.
- the phosphorus ligand those shown in the description of the coupling reaction can be used.
- 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount used is usually 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (7a) from the viewpoint of yield. 0.5 mol, more preferably 0.08 to 0.2 mol.
- a base may be used as necessary.
- the base to be used the base shown in the description of the coupling reaction can be used.
- the amount of the base to be used is generally about 0.1 to 5.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of the starting compound (7a).
- This reaction is usually performed in the presence of a reaction solvent.
- a reaction solvent those shown in the above description of the coupling reaction can be used.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- the compound (8) having the boronate group may be produced and then hydrolyzed to be converted into a boronic acid group.
- the boronic acid or its ester group Y contained in the compound (8) is substituted with — [R 4 ] m ′ —X.
- size of a carbon nanoring can be adjusted suitably.
- the amount of compound (10) to be used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, still more preferably 0.8 to 2 mol, per 1 mol of compound (8). Is a mole.
- This reaction is usually performed in the presence of a catalyst, and a palladium-based catalyst is preferably used.
- a palladium-based catalyst the palladium-based catalyst shown in the description of the coupling reaction can be used.
- (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II), Pd 2 (dba) 3 , Pd (PPh 3 ) 4 and the like are preferable.
- the amount used is usually 0.001 to 1 mol, preferably 0.005 to 0.2 mol, relative to 1 mol of the starting compound (8), from the viewpoint of yield. More preferably, it is 0.01 to 0.1 mol.
- a phosphorus ligand can be used together with the catalyst.
- the phosphorus ligand those shown in the description of the coupling reaction can be used.
- 1,1′-bis (diphenylphosphino) ferrocene, 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-tri-isopropyl-1,1′-biphenyl (X-Phos) and the like are preferable. .
- the amount used is usually 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (8) from the viewpoint of yield. 0.5 mol, more preferably 0.08 to 0.2 mol.
- a base may be used as necessary.
- the base to be used the base shown in the description of the coupling reaction can be used.
- Preferred bases are sodium carbonate, potassium phosphate and the like.
- the amount of the base to be used is generally about 0.1 to 5.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of the starting compound (8).
- This reaction is usually performed in the presence of a reaction solvent.
- a reaction solvent those shown in the above description of the coupling reaction can be used.
- toluene, 1,4-dioxane, water, a mixed solvent thereof and the like are preferable.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- This step is a step of forming the compound (11) from the compound (7) and the compound (8).
- the compound (7) is a compound obtained by combining the compound (7a) and the compound (7b).
- Compound (11) is obtained through a coupling step in which compound (7) and compound (8) are subjected to a coupling reaction to form a ring-shaped compound. Since both compound (7) and compound (8) have a U-shaped shape, compound (11) can be obtained efficiently.
- the amount of compound (8) used in the above coupling reaction is preferably 0.8 to 3.0 mol, more preferably 1.0 to 2.0 mol, relative to 1 mol of compound (7). More preferably, it is 1.2 to 1.8 mol.
- This reaction is usually performed in the presence of a catalyst, and a palladium-based catalyst is preferably used.
- a palladium-based catalyst the palladium-based catalyst shown in the description of the coupling reaction can be used.
- Pd 2 (dba) 3 , Pd (PPh 3 ) 4 and the like are preferable.
- the amount used is usually 0.001 to 1 mol, preferably 0.005 to 0.1 mol, based on 1 mol of the starting compound (7), from the viewpoint of yield. More preferably, it is 0.01 to 0.05 mol.
- a phosphorus ligand can be used together with the catalyst.
- the phosphorus ligand those shown in the description of the coupling reaction can be used.
- 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount used is usually 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (7) from the viewpoint of yield. 0.5 mol, more preferably 0.08 to 0.2 mol.
- a base may be used as necessary.
- the base to be used the base shown in the description of the coupling reaction can be used.
- Preferred bases are cesium fluoride, cesium carbonate, potassium phosphate and the like.
- the amount of the base to be used is generally about 0.1 to 5.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of the starting compound (7).
- This reaction is usually performed in the presence of a reaction solvent.
- a reaction solvent those shown in the above description of the coupling reaction can be used.
- tetrahydrofuran or the like is preferable.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- the cyclic compound (3) is obtained by converting the cyclohexane ring part of the compound (11) into a benzene ring (aromatic cyclization).
- a general oxidation reaction may be performed.
- Specific examples thereof include, for example, a method of heating (acid treatment) compound (11) in the presence of an acid, a method of heating in the presence of oxygen (air atmosphere, oxygen atmosphere, etc.), quinones, and metal oxidizer.
- the method of making it react with etc. is also mentioned.
- dehydrogenation reaction etc. are applied normally and the cyclohexane ring part which compound (11) has can be chemically changed to a benzene ring (aromatic cyclization), and a cyclic compound (3) is compoundable. That is, OR 1 in the cyclohexane ring part of the ring-shaped compound before conversion is also eliminated, and the dehydrogenation reaction proceeds to obtain the cyclic compound (3).
- the specific method and the like are not particularly limited. For example, the following method and the like are preferable.
- the acid is not particularly limited, but a strong acid used for a catalyst or the like is preferable.
- a strong acid used for a catalyst or the like is preferable.
- sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, boron trifluoride ethylate, tin tetrachloride and the like can be mentioned. These can be used alone or in combination of two or more.
- the amount of the acid used varies depending on the production conditions and the like, but in the case of the above method (A), it is preferably 0.01 to 100 moles, more preferably 0.5 to 50 mole equivalents per mole of compound (11). 1 to 20 mol is more preferable.
- the amount of acid used is preferably 0.01 to 100 mol, more preferably 0.5 to 50 mol, and more preferably 1 to 20 mol, relative to 1 mol of compound (11). The equivalent is more preferable.
- the solvent used in the acid treatment reaction may be a nonpolar solvent or a polar solvent.
- alkanes such as hexane, heptane, and octane
- haloalkanes such as methylene chloride, chloroform, carbon tetrachloride, and ethylene chloride
- benzenes such as benzene, toluene, xylene, mesitylene, and pentamethylbenzene
- Halobenzenes ethers such as diethyl ether and anisole; dimethyl sulfoxide and the like.
- the said solvent can be used individually by 1 type or in combination of 2 or more types.
- the reaction intermediate from the raw material to the cyclic compound (3) may have low solubility in one solvent used.
- the other solvent is used in advance or It may be added in the middle of the reaction.
- the amount of the solvent to be used is appropriately selected depending on the production conditions and the like, but is preferably 100 to 100,000 parts by mass, more preferably 1000 to 10,000 parts by mass with respect to 100 parts by mass of the compound (11).
- the heating temperature in the above methods (A) to (B) is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher.
- it selects from the range below the boiling point temperature of the said solvent.
- the heating means includes an oil bath, an aluminum block thermostatic bath, a heat gun, a burner, and microwave irradiation.
- a known microwave reaction apparatus used for microwave reaction can be used.
- reflux cooling may be used in combination.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- a purification step can be provided as necessary. That is, it can be subjected to general post-treatment such as solvent (solvent) removal (when a solvent is used), washing, chromatographic separation and the like. Since the obtained cyclic compound (3) is usually amorphous (non-crystalline), it can be crystallized using a known recrystallization method. In the crystallized product, the organic solvent used in the recrystallization operation may be included in the ring constituting the molecule.
- a cyclic compound in which 14 or more divalent aromatic rings are linked can be obtained by appropriately adjusting the numbers of m and n.
- a cyclic compound in which 14 divalent aromatic rings are connected can be obtained in the case of a compound in which m is 1 and 0 and n is 1, a cyclic compound in which 15 divalent aromatic rings are connected can be obtained in the case of a compound in which both m is 1 and n is 1, a cyclic compound in which 16 divalent aromatic rings are connected can be obtained.
- d represents an integer of 1 or more.
- R 1 and X are the same as above.
- Synthesis of compound (12) In this reaction, a plurality of compounds (5) are combined (homocoupled) to form a ring-shaped compound (12).
- Compound (5) has two halogen atoms, and by using a nickel compound, the carbon atoms to which the halogen atoms are bonded, that is, the carbon bonded to the halogen atoms in one compound (5).
- bonded with the halogen atom in another compound (5) can be combined. Thereby, the coupling reaction of the compounds (5) can be continuously carried out, and the carbon atoms can be bonded to each other to obtain the ring-shaped compound (12).
- Compound (5) is bonded to a benzene ring at two positions, 1-position and 4-position, and this benzene ring is in an axial or equatorial arrangement, thereby forming a compound having an L-shaped structure. Can do.
- a compound having a structure such as an L-shaped structure as the compound (5), formation of the compound (12) having a ring structure can be facilitated.
- nickel compounds are usually used.
- the nickel compound is not particularly limited, but a zero-valent Ni salt or a divalent Ni salt is preferable. These can be used alone or in combination of two or more. These complexes mean both those charged as reagents and those produced in the reaction.
- the zero-valent Ni salt is not particularly limited, and examples thereof include bis (1,5-cyclooctadiene) nickel (0), bis (triphenylphosphine) nickel dicarbonyl, nickel carbonyl and the like.
- divalent Ni salt examples include nickel acetate (II), nickel trifluoroacetate (II), nickel nitrate (II), nickel chloride (II), nickel bromide (II), nickel (II) acetyl. Acetonate, nickel (II) perchlorate, nickel (II) citrate, nickel (II) oxalate, nickel (II) cyclohexanebutyrate, nickel (II) benzoate, nickel (II) stearate, nickel stearate ( II), nickel sulfamine (II), nickel carbonate (II), nickel thiocyanate (II), nickel trifluoromethanesulfonate (II), bis (1,5-cyclooctadiene) nickel (II), bis (4- Diethylaminodithiobenzyl) nickel (II), nickel cyanide (II), fluoride Neckel (II), nickel boride (II), nickel borate (II),
- the zero-valent Ni salt and the divalent Ni salt a compound in which a ligand is coordinated in advance may be used.
- the amount of nickel compound used is usually 0.01 to 50 mol, preferably 0.1 to 10 mol, more preferably 0.1 to 10 mol of the nickel compound charged as a reagent with respect to 1 mol of the above compound (5) as a raw material.
- the amount is 0.5 to 5 mol, particularly preferably 1 to 3 mol.
- a ligand capable of coordinating to nickel can be used together with the nickel compound.
- the ligand include carboxylic acid, amide, phosphine, oxime, sulfonic acid, 1,3-diketone, Schiff base, oxazoline, diamine, carbon monoxide, and carbene.
- a ligand can be used alone or in combination of two or more.
- Coordination atoms in the above ligand are a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, and the like.
- These ligands include a monodentate ligand having only one coordination atom and a polydentate having two or more. There are bidentate ligands.
- carbon monoxide and carbene are ligands having a carbon atom as a coordination atom.
- Monodentate ligands include triphenylphosphine, trimethoxyphosphine, triethylphosphine, tri (i-propyl) phosphine, tri (tert-butyl) phosphine, tri (n-butyl) phosphine, tri (isopropoxy) phosphine, Tri (cyclopentyl) phosphine, tri (cyclohexyl) phosphine, tri (ortho-tolyl) phosphine, tri (mesityl) phosphine, tri (phenoxy) phosphine, tri- (2-furyl) phosphine, bis (p-sulfonate phenyl) phenyl Examples include phosphine potassium, di (tert-butyl) methylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, triethylamine, pyridine and the like.
- Bidentate ligands include 2,2′-bipyridyl, 4,4 ′-(tert-butyl) bipyridyl, phenanthroline, 2,2′-bipyrimidyl, 1,4-diazabicyclo [2,2,2] octane 2- (dimethylamino) ethanol, tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, 2-aminomethylpyridine, or (NE) -N- (pyridin-2-ylmethylidene) aniline, 1,1′-bis (diphenylphosphino) ferrocene, 1,1′-bis (tert-butyl) ferrocene, diphenylphosphinomethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenyl) Phosphino) propane, 1,5-bis (diphenylphosphin
- the amount used is generally 0.01 to 50 mol, preferably 0.1 to 10 mol, more preferably 0.5 to 0.5 mol, relative to 1 mol of the starting compound (5). 5 moles, particularly preferably 1 to 3 moles.
- reaction solvent examples include aliphatic hydrocarbons (hexane, cyclohexane, heptane, etc.), aliphatic halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc.), aromatic hydrocarbons (benzene, toluene, Xylene, chlorobenzene, etc.), ethers (diethyl ether, dibutyl ether, dimethoxyethane (DME), cyclopentyl methyl ether (CPME), tert-butyl methyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, ethyl propionate, etc.) ), Acid amides (dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (1-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-
- the amount of the solvent in the above reaction is usually 1 to 1000 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the compound (5) as a raw material.
- the reaction temperature in the above reaction is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- Synthesis of compound (4) The conversion from the compound (12) to the compound (4) can be carried out in the same manner as the method for converting from the compound (11) to the compound (3) in the above ⁇ Reaction formula 2>.
- R 7 is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13) It is also possible to synthesize a cyclic compound represented by
- a cyclic compound in which various numbers of divalent aromatic rings are linked can be obtained by using the following raw materials and employing the following method 1, method 2, and the like.
- This method includes a method using the above reaction formulas 1 to 3.
- Y ′ is the same as above.
- a raw material a compound obtained by reacting one compound selected from the group consisting of the compounds represented by the above or two or more compounds is used.
- the halogen atom (indicated by Y ′) is not particularly limited. Specifically, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. In the present invention, a bromine atom and an iodine atom are preferable, and a bromine atom is particularly preferable.
- Y ′ (when Y ′ is a halogen atom) may be the same or different.
- Compound (Ib) can be obtained by converting halogen atoms at both ends of compound (5) into boronic acid or an ester group thereof by, for example, a borylation reaction using a boron compound.
- Examples of the boron compound include those described above.
- the amount of the boron compound used is preferably 1 to 10 mol, more preferably 1.5 to 7 mol, relative to 1 mol of compound (5).
- the reaction is usually performed in the presence of a catalyst, and a palladium-based catalyst is preferably used.
- a palladium-based catalyst examples include those described in the method using the above reaction formulas 1 to 3.
- Pd 2 (dba) 3 , Pd (PPh 3 ) 4 , (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and the like are preferable.
- the amount used is preferably 0.001 to 1 mole, and preferably 0.005 to 0.00 moles per mole of the starting compound (5) from the viewpoint of yield. 1 mole is more preferred.
- a phosphorus ligand capable of coordinating with the palladium atom which is the central element of the palladium-based catalyst, can be used together with the catalyst.
- the phosphorus ligand include those described in the method using the above reaction formulas 1 to 3.
- 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount thereof used is usually preferably 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (5) from the viewpoint of yield. More preferred is 5 moles.
- a base boron atom activator
- examples of the base include those described in the method using the above reaction formulas 1 to 3. Of these, potassium acetate is preferred.
- the amount of the base used is usually preferably about 0.1 to 5.0 mol, more preferably 0.5 to 1.0 mol, per 1 mol of the starting compound (5).
- the reaction is usually performed in the presence of a reaction solvent.
- the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, dimethyl sulfoxide and the like are preferable in this step.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- the boron compound when it is a compound having a cyclic boronic acid ester group, it may be converted to a boronic acid group by hydrolysis after producing the compound having the boronic acid ester group.
- a compound obtained by reacting two or more compounds of compound (I) and compound (II) is, for example, general formula (14):
- Compound (14) can be obtained, for example, by a reaction using compound (I). More specifically, using the compound (5) and the compound (Ib), the terminal halogen atom of the compound (5) is reacted with the boronic acid at the terminal of the compound (Ib) compound or its ester group. The compound (14) is obtained by trimerization.
- the compound (14) can be obtained as a C-shaped chain compound by utilizing the bent portion of the cyclohexane ring.
- the amount of compound (5) and compound (Ib) used is preferably adjusted as appropriate according to the target compound (14).
- compound (5) is preferably used in excess.
- the amount of compound (Ib) to be used is preferably 0.05 to 0.2 mol, more preferably 0.075 to 0.15 mol, per 1 mol of compound (5).
- the compound (Ib) is preferably used in an excessive amount.
- the amount of compound (Ib) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (5).
- the above reaction is usually performed in the presence of a catalyst, and a palladium catalyst is preferably used.
- a palladium catalyst is preferably used.
- the palladium-based catalyst include those described in the method using the above reaction formulas 1 to 3.
- Pd (PPh 3 ) 4 , Pd 2 (dba) 3 and the like are preferable.
- the amount used is usually 0.001 to 1 mol with respect to 1 mol of the starting compound (5) and the compound (Ib), whichever is smaller, from the viewpoint of yield. Is preferable, and 0.005 to 0.5 mol is more preferable.
- a phosphorus ligand capable of coordinating with the palladium atom which is the central element of the palladium-based catalyst, can be used together with the catalyst.
- the phosphorus ligand include those described in the method using the above reaction formulas 1 to 3.
- 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount used is usually 0.01 to 1 mol per mole of the starting compound (5) and compound (Ib), from the viewpoint of yield. 1.0 mol is preferable, and 0.05 to 0.5 mol is more preferable.
- a base boron atom activator
- the base include those described in the method using the above reaction formulas 1 to 3. Of these, cesium fluoride, cesium carbonate, silver carbonate, potassium phosphate and the like are preferable.
- the amount of the base used is usually preferably about 0.1 to 5.0 moles, preferably 0.5 to 4 moles per mole of the starting compound (5) and compound (Ib), which is the smaller of the compounds. More preferred is 0.0 mole.
- the reaction is usually performed in the presence of a reaction solvent.
- the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, cyclic ethers (such as tetrahydrofuran) are preferred in this step.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- the compound (15) is obtained by obtaining the compound (7a) according to the reaction formula (1) as described above, and further, the halogen atom at the terminal of the compound (7a) and the boronic acid at the terminal of the compound (Ib) or its ester group. It is obtained by reacting.
- the compound (15) can be obtained as a C-shaped chain compound by utilizing the bent portion of the cyclohexane ring.
- the Suzuki-Miyaura coupling reaction is preferably used.
- the compound (Ib) or the compound (5) is in an excess amount.
- the amount of compound (Ib) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (7a).
- the amount of compound (5) used is preferably 5 to 20 mol, more preferably 7 to 15 mol, relative to 1 mol of compound (8).
- a palladium-based catalyst is usually used.
- the palladium-based catalyst include those described in the method using the above reaction formulas 1 to 3. Of these, Pd (PPh 3 ) 4 and the like are preferable.
- the amount of the palladium catalyst used is usually preferably 0.001 to 1 mol, preferably 0.005 to 0.5 mol per mol of the starting compound (7a) or compound (8). Mole is more preferred.
- a phosphorus ligand capable of coordinating with a palladium atom which is a central element of the palladium catalyst can be used.
- the phosphorus ligand include those described in the method using the above reaction formulas 1 to 3. Of these, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount used is usually preferably 0.001 to 1.0 mol with respect to 1 mol of the starting compound (7a) or compound (8) from the viewpoint of yield. 0.01 to 0.8 mol is more preferable.
- a base boron atom activator
- the base include those described in the method using the above reaction formulas 1 to 3. Preferred are sodium carbonate, silver carbonate and the like.
- the amount of the base (the activator) used is usually preferably 0.01 to 10 mol, preferably 0.1 to 5.0 mol, per 1 mol of the starting compound (7a) or compound (8). More preferred.
- the reaction is usually performed in the presence of a reaction solvent.
- the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, aromatic hydrocarbons (toluene and the like) are preferable in this step.
- the system containing water may be sufficient.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- Compound (16) can be obtained, for example, by a reaction using compound (I) and compound (II). More specifically, it is obtained by reacting the terminal halogen atom of compound (5) or compound (10) with the terminal boronic acid of compound (6) or compound (Ib) or its ester group.
- the compound (16) can be obtained as an L-shaped chain compound by utilizing the bent portion of the cyclohexane ring.
- the Suzuki-Miyaura coupling reaction is preferably used.
- the compound (6) or the compound (10) is in an excessive amount.
- the amount of compound (6) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (5).
- the amount of compound (10) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (Ib).
- a palladium-based catalyst is usually used.
- the palladium-based catalyst include those described in the method using the above reaction formulas 1 to 3. Of these, Pd (PPh 3 ) 4 and the like are preferable.
- the amount of the palladium catalyst used is usually preferably from 0.0001 to 0.5 mol, preferably from 0.0005 to 0, per 1 mol of the starting compound (5) or compound (Ib). More preferred is 2 moles.
- a phosphorus ligand capable of coordinating with a palladium atom which is a central element of the palladium catalyst can be used.
- the phosphorus ligand include those described in the method using the above reaction formulas 1 to 3. Of these, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount used is preferably 0.001 to 1.0 mol with respect to 1 mol of the starting compound (5) or compound (Ib) from the viewpoint of yield. 0.01 to 0.8 mol is more preferable.
- a base boron atom activator
- the base include those described in the method using the above reaction formulas 1 to 3.
- it is silver carbonate or the like.
- the amount of the base (the activator) used is usually preferably 0.01 to 10 mol, preferably 0.1 to 5.0 mol, per 1 mol of the starting compound (5) or compound (Ib). More preferred.
- reaction is usually performed in the presence of a reaction solvent.
- reaction solvent include those described in the method using the above reaction formulas 1 to 3.
- cyclic ethers such as tetrahydrofuran are preferred.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- Cyclic compounds in which 9 to 13 (especially 9, 11 or 13) aromatic rings are linked are, for example, Formula (III): XR 9 -X (Wherein R 9 represents 3 to 4 general formulas (17):
- R 1 is the same as defined above.
- X is the same as defined above.
- a ring-shaped compound is obtained from the compound (III) by an intramolecular ring-closing reaction.
- compound (III) is obtained by making it react using the raw material demonstrated above.
- Compound (III) is a concept including compounds (14) and compounds (15) in which both ends are halogen atoms among the compounds described above. Therefore, other compounds of compound (III) can also be obtained by the same method as the compound (14) and compound (15) in which both ends are halogen atoms.
- the terminal atoms of the compound (III) are bonded to form a ring-shaped compound.
- Compound (III) has two halogen atoms.
- the halogen atoms can be bonded to each other to cause an intramolecular ring-closing reaction.
- the number of rings of the compound (III) becomes the number of rings of the cyclic compound (especially carbon nanorings) as it is. From this, it is possible to freely design the number of aromatic rings to be linked by suitably selecting the compound (III), and to efficiently produce a cyclic compound in which a desired number of aromatic rings are linked in a short process. Can be manufactured well.
- nickel compound In the intramolecular ring closure reaction, a nickel compound is used.
- the nickel compound include those described in the method using the above reaction formula 3.
- the amount of the nickel compound used varies depending on the raw material used, but usually the amount of the nickel compound charged as a reagent is usually 0.01 to 50 mol, preferably 0, relative to 1 mol of the raw material compound (III). .1 to 10 moles.
- a ligand capable of coordinating with nickel can be used together with the nickel compound.
- Examples of the ligand include those described in the method using the above reaction formula 3.
- the amount used is generally 0.01 to 50 mol, preferably 0.1 to 10 mol, per 1 mol of compound (III).
- the reaction is usually performed in the presence of a reaction solvent.
- the reaction solvent include those described in the method using the above reaction formula 3. Of these, cyclic ethers (such as tetrahydrofuran) are preferred in this step.
- the concentration of compound (III) is preferably 0.1 to 5 mmol / L, more preferably 0.2 to 3 mol / L.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- R 2 is a 1,4-phenylene group, and n is 1 is used as a raw material in the compound (15), the general formula (18):
- a cyclic compound in which 10 to 13 (particularly 10) aromatic rings are linked is, for example, Formula (IV-1): Y'-R 10a -Y ' (Wherein R 10a represents three structural units represented by the general formula (17), 6 or more (especially 6 to 9) phenylene groups or divalent condensed polycyclic aromatic hydrocarbon groups; A divalent group comprising: Y ′ is the same as defined above.)
- R 11a represents two structural units represented by the general formula (17), 4 or more (particularly 4 to 8) phenylene groups or a divalent condensed polycyclic aromatic hydrocarbon group
- a divalent group consisting of: Y ′ is the same as defined above.
- R 11b represents one structural unit represented by the general formula (17), two or more (especially 2 to 6) phenylene groups or a divalent condensed polycyclic aromatic hydrocarbon group, A divalent group consisting of: Y ′ is the same as defined above.
- a ring-shaped compound is obtained by the reaction between the compound (IV-1) and the compound (IV-2) or the reaction between the compound (V-1) and the compound (V-2).
- Compound (IV-1) includes compound (14), and compound (IV-2) includes compound (II), compound (6), compound (10) and the like.
- Compound (V-1) includes compound (8), and compound (V-2) includes compound (I), compound (Ib), compound (5), compound (16) and the like.
- reaction is not limited to the above reaction, and various combinations of compound (IV-1) and compound (IV-2), and combinations of compound (V-1) and compound (V-2) may be employed.
- both ends of one of the compounds (IV-1) and (IV-2) are halogen atoms and both ends of the other compound are boronic acid or an ester group thereof.
- both ends of one of the compounds (V-1) and (V-2) are halogen atoms and both ends of the other compound are boronic acid or an ester group thereof.
- the amount of compound (IV-2) to be used is preferably 0.01 to 5.0 mol, more preferably 0.05 to 3.0 mol, per 1 mol of compound (IV-1).
- the amount of compound (V-2) to be used is preferably 0.01 to 5.0 mol, more preferably 0.05 to 3.0 mol, per 1 mol of compound (V-1).
- a palladium-based catalyst is usually used.
- the palladium-based catalyst include those described in the method using the above reaction formulas 1 to 3.
- Pd (OAc) 2 Ac is an acetyl group
- bis (dibenzylideneacetone) palladium (0) bis (tri-t-butylphosphino) palladium (0), and the like are preferable.
- the amount of the palladium catalyst used is usually preferably from 0.0001 to 1.0 mol based on 1 mol of the starting compound (IV-1) or compound (V-1). More preferred is .0005 to 0.5 mol.
- a phosphorus ligand capable of coordinating with a palladium atom which is a central element of the palladium catalyst can be used.
- the phosphorus ligand include those described in the method using the above reaction formulas 1 to 3. Of these, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.
- the amount used is usually 0.001 to 1. mol per mol of the starting compound (IV-1) or compound (V-1) from the viewpoint of yield. 0 mol is preferable, and 0.01 to 0.8 mol is more preferable.
- a base boron atom activator
- examples of the base include those described in the method using the above reaction formulas 1 to 3. Preferred are sodium hydroxide and potassium phosphate.
- the amount of the base (the activator) used is usually preferably 0.01 to 10 moles, preferably 0.1 to 5 moles per mole of the starting compound (IV-1) or compound (V-1). More preferred is 0.0 mole.
- the reaction is usually performed in the presence of a reaction solvent.
- the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Among these, in this step, cyclic ethers (dioxane and the like) are preferable. Moreover, it is good also as a system containing water.
- the concentration of the raw material is preferably 0.1 to 5 mmol / L, more preferably 0.2 to 3 mol / L.
- the concentration of the compound (8) is preferably 0.1 to 5 mmol / L, more preferably 0.2 to 3 mol / L.
- the reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.
- the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.
- the ring-shaped compound thus obtained has 3 to 4 general formulas (17):
- R 1 is the same as defined above.
- a cyclic compound is obtained by converting the cyclohexane ring portion into a benzene ring.
- the method can be carried out in the same manner as the method for converting the compound (11) in the above ⁇ Reaction formula 2> into the compound (3).
- TLC thin layer chromatography
- E. Merck silica gel 60 F254 precoated plates (0.25 mm thick) were used. The chromatogram was analyzed using a UV lamp (254 nm). Flash column chromatography (FCC) was performed using E. Merck silica gel 60 F254 (230-400 mesh).
- FCC Flash column chromatography
- PTLC a Wakogel B5-F silica-coated plate (0.75 mm thick) was prepared and used.
- GPC preparative gel permeation chromatography
- JAI LC-9204 type preparation column JAIGEL-1H / JAIGEL-2H, chloroform
- Mass spectra are Waters Micromass LCT Premier (electrospray ionization time-of-flight mass spectral analysis, ESI-TOFMS), JEOL JMS700 (fast atom bombardment mass spectrometer, FAB-MS) Bruker Daltonics Ultraflex III TOF / TOF (MALDI-TOF-MS) ) was used. Elemental analysis was performed using Yanako MT-6. Melting
- Synthesis Example 2 Formation of MOM protection of hydroxyl group of compound (5a)
- a 200 mL round bottom flask containing a stir bar 4.69 g (11 mmol) of compound (5a) obtained in Synthesis Example 1 above and dry dichloromethane 44 mL of (CH 2 Cl 2 ) and 7.7 mL (44 mmol) of diisopropylethylamine were added, and the flask was immersed in an ice bath. And after stirring the mixture in a flask for 30 minutes at 0 degreeC, chloromethyl methyl ether 3.5 mL (46 mmol) was put.
- Synthesis Example 5 Production of compound (6c) having boronic acid or its ester group Into a 20 mL round bottom flask containing a stirring bar, 115.4 mg (0.40 mmol) of 2,6-dibromonaphthalene, bis (neopentylglycol) diboron Add 273.3 mg (1.2 mmol), (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) 10.3 mg (13 ⁇ mol), and potassium acetate (KOAc) 244.8 mg (2.5 mmol). Filled into flask.
- Synthesis Example 7 Production of Compound (7a-2) In a 50 mL round bottom flask containing a stir bar, 165 mg (1.1 mmol) of cesium fluoride and 521.3 mg of Compound (5b) obtained in Synthesis Example 2 (1 mmol), the above compound (6b) 75.5 mg (0.2 mmol), and [Pd (PPh 3 ) 4 ] 6.8 mg (6 ⁇ mol) were added, and argon gas was charged into the flask. Thereto, 60 mL of dry THF was introduced to form a mixture, and this mixture was reacted at 65 ° C. for 26 hours while stirring.
- Synthesis Example 9 Production of Compound (8a) (Borylation Reaction Product) In a 50 mL round bottom flask containing a stirrer, 285.4 mg of Compound (7a-1) obtained in Synthesis Example 6 or Synthesis Example 26 described later was added.
- Synthesis Example 11 Production of 14-ring organic compound (11a): 19.7 mg (21 ⁇ mol) of compound (7a-1) obtained in Synthesis Example 6 was added to a 50 mL round bottom flask containing a stirring bar. 29.1 mg (28 ⁇ mol) of the compound (8a) obtained in 9, 9 [Pd (OAc) 2 ] 0.9 mg (4.0 ⁇ mol), and X-Phos 2.0 mg (4.2 ⁇ mol) were charged, and argon gas was filled in the flask. did. 10 mL of dried 1,4-dioxane and 18 mL (0.18 mmol) of 10 M aqueous sodium hydroxide (NaOH) were introduced to form a mixture.
- NaOH aqueous sodium hydroxide
- Synthesis Example 12 Production of carbon nanoring (3a) composed of cycloparaphenylene containing 14 benzene rings (part 1) In a 2 mL glass vial containing a stir bar, 9.1 mg (5.0 ⁇ mol) of the ring-shaped compound (11a) obtained in Synthesis Example 11, 50 ⁇ L (5.0 ⁇ mol) of 0.1 M p-toluenesulfonic acid aqueous solution, and dry m -1 mL of xylene was added to make a mixture. This vial was placed in a microwave reactor (Initiator Synthesis System, manufactured by Biotage), and reacted at 150 ° C. for 30 minutes while stirring.
- a microwave reactor Initiator Synthesis System, manufactured by Biotage
- Synthesis Example 13 Production of carbon nanoring (3a) composed of cycloparaphenylene containing 14 benzene rings (part 2)
- 7.9 mg (5.0 ⁇ mol) of the annular compound (11a) obtained in Synthesis Example 11 7.9 mg (11.3 ⁇ mol) of sodium hydrogensulfate monohydrate, dry m-xylene 1 mL and 1 mL of dried dimethyl sulfoxide (DMSO) were added to prepare a mixture.
- the mixture was reacted at 150 ° C. for 48 hours with stirring.
- the mixture (reaction solution) in the Schlenk tube was cooled to room temperature, and the mixture (reaction solution) was extracted with CHCl 3 .
- Synthesis Example 15 Production of carbon nanoring (3b) composed of cycloparaphenylene containing 15 benzene rings (part 1) In a 2 mL glass vial containing a stir bar, 9.8 mg (6.0 ⁇ mol) of the ring-shaped compound (11b) obtained in Synthesis Example 14, 120 ⁇ L (12 ⁇ mol) of 0.1 M p-toluenesulfonic acid aqueous solution, and dry m-xylene 1 mL was added to make a mixture. The vial containing the mixture was placed in a microwave reactor in the same manner as in Synthesis Example 12, and reacted at 150 ° C. for 30 minutes while stirring.
- Synthesis Example 16 Production of carbon nanoring (3b) composed of cycloparaphenylene containing 15 benzene rings (part 2)
- a 20 mL Schlenk tube containing a stir bar 7.4 mg (4.5 ⁇ mol) of the ring-shaped compound (11b) obtained in Synthesis Example 14, 14.7 mg (10.6 ⁇ mol) of sodium hydrogen sulfate monohydrate, dry m-xylene 1 mL and 1 mL of dry dimethyl sulfoxide (DMSO) were added to prepare a mixture.
- the mixture was reacted at 150 ° C. for 48 hours with stirring.
- the mixture (reaction solution) in the Schlenk tube was cooled to room temperature, and the mixture (reaction solution) was extracted with CHCl 3 .
- Synthesis Example 17 Production of 16-ring organic compound (11c) In a 50 mL round flask containing a stirrer, 42.8 mg (38.0 ⁇ mol) of the compound (7a-2) obtained in Synthesis Example 7 was synthesized. Compound (8b) 26.7 mg (26.2 ⁇ mol) [Pd (OAc) 2 ] 1.3 mg (5.7 ⁇ mol) obtained in 10 and X-Phos 6.9 mg (14.4 ⁇ mol) were charged, and argon gas was charged into the flask. did. After introducing 13.5 mL of dry 1,4-dioxane and 27.0 ⁇ L (270 ⁇ mol) of 10 M NaOH aqueous solution to make a mixture, the mixture was reacted at 80 ° C.
- Synthesis Example 18 Production of carbon nanoring (3c) composed of cycloparaphenylene containing 16 benzene rings A 20 mL Schlenk tube containing a stirrer was charged with 12.5 mg (7.26) of the cyclic compound (11c) obtained in Synthesis Example 17. ⁇ mol), 20.0 mg (145 ⁇ mol) of sodium hydrogensulfate monohydrate, 1.2 mL of dry m-xylene, and 1.2 mL of dry dimethyl sulfoxide (DMSO) were added to form a mixture. The mixture was reacted at 160 ° C. for 48 hours with stirring. Next, the mixture (reaction solution) in the Schlenk tube was cooled to room temperature, and the mixture (reaction solution) was extracted with CHCl 3 .
- DMSO dry dimethyl sulfoxide
- Synthesis Example 22 Production of carbon nanoring (3d) consisting of 14 organic rings containing a naphthylene ring Into a 20 mL Schlenk tube containing a stirrer and a condenser, a ring compound (11d) obtained in Synthesis Example 19 or 21 16.2 mg (10.0 ⁇ mol), sodium hydrogen sulfate monohydrate (NaHSO 4 ⁇ H 2 O) 27.2 mg (197 ⁇ mol), dry DMSO 1 mL and m-xylene 2.0 mL were added. The mixture was heated at 150 ° C. for 24 hours with stirring under an air atmosphere. The mixture was cooled to room temperature and the solvent was removed by passing through a silica gel layer (CHCl 3 ).
- a silica gel layer CHCl 3
- Synthesis Example 23 Production of [9] cycloparaphenylene and [12] cycloparaphenylene (1) Production of annular compounds (12a) and (12b-1) A glass round bottom flask equipped with a 200 mL stirrer was charged with bis. (1,5-cyclooctadiene) nickel (zero valent) 452 mg (1.64 mmol), compound (5b) obtained in Synthesis Example 2 423 mg (823 ⁇ mol), 2,2′-bipyridyl 257 mg (1.65 mmol) Housed. Here, 166 mL of THF was added by a syringe. The mixture was then stirred under reflux for 24 hours.
- the cyclized trimer represented by (95.5 mg) was obtained. Yields were 23% for cyclized tetramer and 32% for cyclized trimer, respectively. These materials were analyzed by 1 H NMR and 13 C NMR.
- the reaction mixture was cooled to room temperature, then filtered through a silica gel layer, washed with ethyl acetate (EtOAc), and then the solvent was removed under reduced pressure.
- Example 1 ([12] cycloparaphenylene ⁇ CNT) A toluene solution (0.001 wt%) of [12] cycloparaphenylene ([12] CPP) (4a) obtained in Synthesis Example 23 (3) was applied on a sapphire single crystal substrate (C surface) by spin coating. did. The spin coating conditions were a rotation speed of 4000 rpm and a rotation time of 60 seconds.
- the prepared [12] CPP-coated sapphire single crystal substrate was placed at the end of a quartz reaction tube, and then the inside of the reaction tube was evacuated (final ultimate pressure was about 0.01 torr (about 1.33 Pa)) . Subsequently, ethanol was supplied to the reaction tube (pressure 7 torr (933.25 Pa)), and the central portion was heated to 500 ° C. with an electric furnace. After waiting for the temperature and ethanol supply to stabilize, the sapphire substrate coated with [12] CPP was quickly moved to the center of the reaction tube to start nanotube growth by chemical vapor deposition (CVD). 15 minutes after the start of the reaction, the growth of the nanotube was terminated by moving the sapphire single crystal substrate from the central part of the reaction tube at 500 ° C. to the end part at room temperature.
- CVD chemical vapor deposition
- the formation and structure of carbon nanotubes were evaluated by transmission electron microscope (TEM) observation and Raman spectroscopy.
- the transmission electron microscope was a JEOL JEM-2100F / HR, and the Raman spectrometer was a Horiba Jobin Yvon von LabRAM HR-800.
- FIGS. 4 The observation results of the transmission electron microscope are shown in FIGS. When the diameters of the CNTs obtained from these figures were measured, it was confirmed that CNTs having a substantially uniform diameter were obtained (FIG. 4). From FIG. 4, it was confirmed that CNTs having a diameter of 1.5 to 1.6 nm were selectively generated from [12] cycloparaphenylene as a raw material.
- the physical properties of CNT were measured by Raman spectroscopy.
- Raman spectroscopy the detected CNT differs depending on the excitation wavelength of the laser used for excitation.
- FIG. 5 shows the results of evaluating CNTs using lasers having excitation wavelengths of 488 nm, 514 nm, and 633 nm. The diameter of the synthesized CNT was about 1.6 nm.
- the excitation wavelengths were 488 nm and 514 nm, semiconducting CNT was detected, and when the excitation wavelength was 633 nm, metallic CNT was detected. From FIG. 5, Raman bands peculiar to CNT were observed when 488 and 633 nm were used as excitation wavelengths. That is, it was confirmed that the CNT obtained this time has a property in which both characteristics of semiconductor property and metallic property are mixed.
- Example 2 ([9] cycloparaphenylene ⁇ CNT) A toluene solution (0.001 wt%) of [9] cycloparaphenylene ([9] CPP) (4b) obtained in Synthesis Example 23 (2) was applied on a sapphire single crystal substrate (C surface) by spin coating. did. The spin coating conditions were a rotation speed of 4000 rpm and a rotation time of 60 seconds.
- the prepared [9] CPP-coated sapphire single crystal substrate was placed at the end of a quartz reaction tube, and then the inside of the reaction tube was evacuated (final ultimate pressure was about 0.01 torr (about 1.33 Pa)) . Subsequently, ethanol was supplied to the reaction tube (pressure 7 torr (933.25 Pa)), and the central portion was heated to 500 ° C. with an electric furnace. After waiting for the temperature and ethanol supply to stabilize, the sapphire substrate coated with [9] CPP was quickly moved to the center of the reaction tube to start nanotube growth by chemical vapor deposition (CVD). 15) 15 minutes after the start of the reaction, the sapphire single crystal substrate was moved from the central part of the reaction tube at 500 ° C. to the end part at room temperature to complete the growth of the nanotubes.
- CVD chemical vapor deposition
- the formation of carbon nanotubes and their structure were evaluated by Raman spectroscopy.
- the Raman spectroscope used was a LabRAM HR-800 manufactured by Horiba Jobin Yvon.
- FIG. 6 shows the results of evaluating CNTs using lasers having excitation wavelengths of 488 nm, 514 nm, and 33633 nm.
- the excitation wavelength was 488 nm and 514 nm, semiconducting CNT was detected, and when the excitation wavelength was 633 nm, metallic CNT was detected. From FIG. 6, Raman bands peculiar to CNTs were observed when 488, 14514, and 633 nm were used as excitation wavelengths.
- Example 3 ([14] cycloparaphenylene ⁇ CNT) CNT obtained by treating [14] cycloparaphenylene (3a) obtained in Synthesis Example 12 or 13 in the same manner as in Example 1.
- Example 4 ([15] cycloparaphenylene ⁇ CNT) CNT obtained by treating [15] cycloparaphenylene (3b) obtained in Synthesis Example 15 or 16 in the same manner as in Example 1.
- Example 5 ([16] cycloparaphenylene ⁇ CNT) CNT obtained by treating [16] cycloparaphenylene (3c) obtained in Synthesis Example 18 in the same manner as in Example 1.
- Example 6 ([14] cycloparaphenylene ⁇ CNT containing one naphthylene) CNT which processed the compound (3d) obtained by the synthesis example 22 like Example 1.
- FIG. 6 [14] cycloparaphenylene ⁇ CNT containing one naphthylene
- Example 7 ([10] cycloparaphenylene ⁇ CNT) CNT obtained by treating [10] cycloparaphenylene (13a) obtained in Synthesis Example 35 in the same manner as in Example 1.
- Example 8 ([11] cycloparaphenylene ⁇ CNT) CNT obtained by treating [11] cycloparaphenylene (13b) obtained in Synthesis Example 36 in the same manner as in Example 1.
- Example 9 ([13] cycloparaphenylene ⁇ CNT) CNT obtained by treating [13] cycloparaphenylene (13c) obtained in Synthesis Example 37 in the same manner as in Example 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
で表されるシクロパラフェニレン化合物、又は、当該一般式(1)で表されるシクロパラフェニレン化合物の少なくとも1個のフェニレン基が、一般式(2):
で表される基で置換された修飾シクロパラフェニレン化合物である、項4に記載の製造方法。
で表される環状化合物、一般式(4):
で表される環状化合物、又は一般式(13):
で示される環状化合物である、項3に記載の製造方法。
本発明のCNTの製造方法において、複数の芳香族環が連結してなる環状化合物を製造原料として用いることができる。換言すれば、当該環状化合物を、CNTの鋳型(テンプレート)として用いることができる。
で表される化合物が挙げられる。aは好ましくは6~100、より好ましくは8~50、さらに好ましくは8~30、さらに好ましくは9~20の整数、特に好ましくは10~18である。具体的には、aは6、7、8、9、10、11、12、13、14、15、16、17、18、19、20等が挙げられ、特に9、10、11、12、13、14、15、16、17、18等が挙げられる。
で表される基が挙げられる。bは好ましくは1~6、より好ましくは1~3、さらに好ましくは1又は2の整数であり、特に好ましくは1である。
で表される環状化合物、又は、一般式(4):
で表される環状化合物、一般式(13):
で示される環状化合物等が挙げられる。
本発明の製造方法で用いる炭素源としては、種々の炭素又は炭素含有化合物を用いることができ、上記のテンプレート(環状化合物)から、その輪の中心軸方向にCNTのグラフェンシートを成長させることができるものであれば特に限定はない。例えば、炭素、炭化水素化合物、アルコール化合物、エーテル化合物、エステル化合物等が挙げられる。これらの1種又はその2種以上を用いることができる。
本発明のCNTの製造方法は、上記の複数の芳香族環が連結してなる環状化合物(テンプレート)を炭素源と反応させることを特徴とする。具体的には、気体状の炭素源を供給して減圧下で加熱することが好ましい。本発明の製造方法は、例えば、該環状化合物をテンプレートとして用いて、炭素源の存在下に化学気相成長(CVD)法により実施することができる。典型的には、適当な担体上にテンプレートを配置して、該テンプレートに、減圧及び加熱条件下、炭素源を含む原料ガスを用いて化学気相成長(CVD)させることによりCNTを製造することができる。本発明の製造方法では、従来のCVD法で用いられる触媒(金属触媒等)を使用すること無く、テンプレートからグラフェンシートを拡張させて(π電子共役系を広げて)CNTを製造することができる(例えば、図1を参照)。得られるCNTは単層CNT(SWCNTs)である。
本発明の製造方法におけるテンプレートとして用いる複数の芳香族環が連結してなる環状化合物は、例えば以下の様にして製造することができる。
で示される基を示す。)
化合物(5)及び(6)は、非特許文献3、本願明細書の合成例1~5等に従い又はこれらに準じて合成できる。
化合物(5)と化合物(6)とを反応させることにより、化合物(7a)を製造することができる。化合物(5)と化合物(6)との反応は、鈴木・宮浦カップリング反応を用いることができる。鈴木・宮浦カップリング反応は、炭素-炭素結合の反応であり、ハロゲン化アリール化合物と有機ホウ素化合物とをカップリングさせる反応である。化合物(5)はハロゲン原子を有するハロゲン化アリール化合物であり、上記化合物(6)はボロン酸又はそのエステル基を有する有機ホウ素化合物である。
この反応は、化合物(7a)と、ボロン酸又はそのエステル基(-B(OR3)2;R3は前記に同じ)を有するホウ素化合物(以下、単に「ホウ素化合物」と言うこともある。)とから、化合物(8)を形成する工程である。
この工程は、化合物(8)と化合物(10)から、化合物(7b)を形成する工程である。
この工程は、化合物(7)と化合物(8)から、化合物(11)を形成する工程である。ここで、化合物(7)は上記化合物(7a)と化合物(7b)を併せた化合物である。
環状化合物(3)は、化合物(11)が有するシクロヘキサン環部をベンゼン環に変換(芳香環化)することにより得られる。
(A)化合物(11)と酸とを溶媒に溶解させた後、得られた溶液を加熱して反応させる方法。
(B)化合物(11)を溶媒に溶解させた後、得られた溶液と酸とを混合して得られた混合物を加熱して反応させる方法。
この反応では、複数の化合物(5)が、結合(ホモカップリング)して輪状の化合物(12)が形成される。化合物(5)は2つのハロゲン原子を持っており、ニッケル化合物を用いることにより、そのハロゲン原子が結合している炭素原子同士、即ち、1の化合物(5)におけるハロゲン原子に結合している炭素原子と、他の化合物(5)におけるハロゲン原子に結合している炭素原子と、を結合させることができる。それにより、連続的に、化合物(5)同士のカップリング反応を進め、炭素原子同士を結合させ、輪状の化合物(12)を得ることができる。
化合物(12)から化合物(4)への変換は、前記<反応式2>の化合物(11)から化合物(3)に変換する方法と同様にして実施することが出来る。
で示される環状化合物を合成することも可能である。
ここでは、原料として、一般式(I):
で示される化合物、及び
一般式(II):
で示される化合物
よりなる群から選ばれる1種の化合物、又は2種以上の化合物を反応させて得られる化合物を原料として用いる。
で示される化合物、化合物(10)、及び化合物(6)
よりなる群から選ばれる1種の化合物、又は2種以上の化合物を反応させて得られる化合物を用いて、環状化合物を製造することができる種々様々な化合物の組合せ及び反応を用いることで、環状化合物を得ることができる。
で示される化合物、
一般式(15):
で示される化合物、化合物(7a)、化合物(8)、一般式(16):
で示される化合物等が挙げられる。
化合物(14)は、例えば、化合物(I)を用いた反応により得ることができる。より具体的には、化合物(5)と、化合物(Ib)を用いて、化合物(5)の末端のハロゲン原子と、化合物(Ib)化合物の末端のボロン酸又はそのエステル基とを反応させて、三量体化することで、化合物(14)が得られる。
この反応では、シクロヘキサン環の屈曲部を利用して、C字型の鎖状化合物として、化合物(14)を得ることができる。
化合物(15)は、上記のように反応式(1)に従って化合物(7a)を得た後、さらに化合物(7a)の末端のハロゲン原子と、化合物(Ib)の末端のボロン酸又はそのエステル基を反応させることで得られる。
化合物(16)は、例えば、化合物(I)及び化合物(II)を用いた反応により得ることができる。より具体的には、化合物(5)又は化合物(10)の末端のハロゲン原子と、化合物(6)又は化合物(Ib)の末端のボロン酸又はそのエステル基とを反応させて得られる。
9~13個(特に9個、11個又は13個)の芳香族環が連なった環状化合物は、例えば、
一般式(III):
X-R9-X
(式中、R9は、3~4個の一般式(17):
で示される構造単位と、6個以上(特に6~9個)のフェニレン基又は2価の縮合多環芳香族炭化水素基と、からなる2価の基;Xは前記に同じである。]
で示される鎖状化合物の末端原子同士(特にハロゲン原子同士)を、分子内閉環反応により反応させて輪状の化合物を得る工程
を備える。
で示される化合物が得られる。
で示される化合物が得られる。
で示される化合物等も得られる。
10~13個(特に10個)の芳香族環が連なった環状化合物は、例えば、
一般式(IV-1):
Y’-R10a-Y’
(式中、R10aは、3個の一般式(17)で示される構造単位と、6個以上(特に6~9個)のフェニレン基又は2価の縮合多環芳香族炭化水素基と、からなる2価の基;Y’は前記に同じである。)
で示される化合物と、
一般式(IV-2):
Y’-R10b-Y’
(式中、R10bは、1個以上(特に1~4個)のフェニレン基又は2価の縮合多環芳香族炭化水素基からなる2価の基;Y’は前記に同じである。)
で示される化合物とを反応させて輪状の化合物を得る工程か、
一般式(V-1):
Y’-R11a-Y’
[式中、R11aは、2個の一般式(17)で示される構造単位と、4個以上(特に4~8個)のフェニレン基又は2価の縮合多環芳香族炭化水素基と、からなる2価の基;Y’は前記に同じである。]
で示される化合物と、
一般式(V-2):
Y’-R11b-Y’
[式中、R11bは、1個の一般式(17)で示される構造単位と、2個以上(特に2~6個)のフェニレン基又は2価の縮合多環芳香族炭化水素基と、からなる2価の基;Y’は前記に同じである。]
で示される化合物とを反応させて輪状の化合物を得る工程
を備える。
により輪状の化合物が得られる。
により輪状の化合物が得られる。
で示される構造単位と、
6~9個のフェニレン基又は2価の縮合多環芳香族炭化水素基と、
からなり、且つ、
一般式(17)で示される構造単位とフェニレン基又は2価の縮合多環芳香族炭化水素基とを合計で10、11又は13個有する、輪状の化合物である。
上記のようにして輪状の化合物を得た後、シクロヘキサン環部をベンゼン環に変換することにより、環状化合物が得られる。
内容積1 Lの丸底フラスコに、塩化リチウム1.68 g(33 mmol)と、セリウム(III)トリクロリド・七水和物14.4 g(0.33 mol)とを入れ、このフラスコをオイルバスに浸し、真空下、90℃で、2時間加熱し乾燥させた。得られた反応剤混合物を粉末状に砕いた後、その粉末状の反応剤混合物を再びフラスコに入れた。更に、フラスコをオイルバスに浸し、真空下、90℃で、1時間加熱した。このフラスコに攪拌子を入れ、フラスコを再びオイルバスに浸し、攪拌しながら、真空下、150℃で、3時間加熱した。フラスコ内の内容物が冷めないうちに、アルゴンガスをフラスコ内に充填した。ここに乾燥テトラヒドロフラン(THF)200 mLを入れて懸濁させ、生じた懸濁液を、室温(約23℃、以下同様)で、8時間程度攪拌した。この懸濁液に、1,4-シクロヘキサンジオン1.68 g(15 mmol)のTHF溶液15 mLをキャニュラを用いて入れて、室温で、2時間攪拌した後、-78℃に冷却して、懸濁液Aを得た。
攪拌子を入れた200 mL丸底フラスコに、上記の合成例1により得られた化合物(5a)4.69 g(11 mmol)と、乾燥ジクロロメタン(CH2Cl2)44 mLと、ジイソプロピルエチルアミン7.7 mL(44 mmol)とを入れて、フラスコを氷浴に浸した。そして、フラスコ内の混合物を0℃で30分間攪拌した後、クロロメチルメチルエーテル3.5 mL(46 mmol)を入れた。次いで、その混合物を、撹拌しながら、室温で18時間反応させた後に、飽和NH4Cl水溶液20 mLを加え、反応を停止させた。生成物をCH2Cl2(20 mL×3)で抽出し、抽出後の有機層を無水Na2SO4で乾燥し溶液を得た。その溶液をエバポレーターで濃縮し、残渣(濃縮物)をシリカゲルクロマトグラフィー(CH2Cl2)で精製し、無色固体物質5.48 gを得た。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この無色固体物質を解析した結果、下記式(5b):
攪拌子を入れた50 mL丸底フラスコにp-フェニレンビスボロン酸(1,4-Benzenediylbisboranic acid)125 mg(0.75 mmol、1当量)、ネオペンチルグルコール250 mg(2.4 mmol、3当量)、p-トルエンスルホン酸50 mg及び乾燥ベンゼン(benzene)10 mLを収容した。その後、その混合物を、70℃で、12時間還流し反応させた。フラスコ内の混合物(反応物)を室温まで冷却した後に、目的の生成物をCH2Cl2で抽出した。抽出後の有機層を飽和NaHCO3水溶液で洗浄した後に、溶媒を減圧留去し、生成物226.9 mgを得た。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この生成物を解析した結果、下記式(6a):
適当な原料化合物を用いて合成例3と同様にして化合物(6b):
攪拌子を入れた20 mL丸底フラスコに、2,6-ジブロモナフタレン115.4 mg(0.40 mmol)、ビス(ネオペンチルグリコール)ジボロン273.3 mg(1.2 mmol)、(1,1’-ビス(ジフェニルホスフィノ)フェロセン)ジクロロパラジウム(II)10.3 mg(13μmol)、及び酢酸カリウム(KOAc)244.8 mg(2.5 mmol)を入れ、アルゴンガスをフラスコ内に充填した。そこに、乾燥ジメチルスルホキシド2 mLを導入し、混合物とした後に、混合物を撹拌しながら、80℃で21時間反応させた。次いで、フラスコ内の混合物(反応物)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液からエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をヘキサンで再結晶し、白色固体物質47.8mgを得た。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(6c):
攪拌子を入れた200 mL丸底フラスコに、フッ化セシウム(Cesium fluoride)400 mg(2.6 mmol)、合成例2で得られた化合物(5b)2.07 g(4 mmol)、合成例3で得られた化合物(6a)151.2 mg(0.5 mmol)、及び[Pd(PPh3)4]30.1 mg(0.026 mmol)を入れ、アルゴンガスをフラスコ内に充填した。そこに、乾燥THF60 mLを導入し、混合物とした後に、この混合物を撹拌しながら、65℃で26時間反応させた。次いで、フラスコ内の混合物(反応液)を室温に冷却し、その混合物(反応液)をセライトでろ過した。得られたろ液からエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(hexane/EtOAc)で精製し、白色固体物質319.9 mgを得た。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(7a-1):
攪拌子を入れた50 mL丸底フラスコにフッ化セシウム(Cesium fluoride)165 mg(1.1 mmol)、合成例2で得られた化合物(5b)521.3 mg(1 mmol)、上記の化合物(6b)75.5 mg(0.2 mmol)、及び[Pd(PPh3)4]6.8 mg(6μmol)を入れ、アルゴンガスをフラスコ内に充填した。そこに、乾燥THF60 mLを導入し、混合物とした後に、この混合物を撹拌しながら、65℃で26時間反応させた。次いで、フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をセライトでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(hexane/EtOAc)で精製し、白色固体物質126.5 mgを得た。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(7a-2):
攪拌子を入れた50 mL丸底フラスコにフッ化セシウム80.2 mg(0.53 mmol)、合成例2で得られた化合物(5b)349.7 mg(0.68 mmol)、合成例5で得られた化合物(6c)32.0 mg(84μmol)、及び[Pd(PPh3)4]4.7 mg(4μmol)を入れ、アルゴンガスをフラスコ内に充填した。そこに、乾燥THF60 mLを導入し、混合物とした後に、この混合物を撹拌しながら、60℃で24時間反応させた。次いで、フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をセライトでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(hexane/EtOAc)で精製し、白色固体物質66.1 mgを得た。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(7a-3):
攪拌子を入れた50 mL丸底フラスコに、合成例6、又は後述の合成例26で得られた化合物(7a-1)285.4 mg(0.30 mmol)、[Pd2(dba)3]6.0 mg(6.6μmol)、2-(ジシクロヘキシルホスフィノ-2',4',6'-トリ-イソプロピル-1,1'-ビフェニル(以下、「X-Phos」ともいう)13.3 mg(28μmol)、ビスピナコレートジボロン227.5 mg(0.9 mmol)、及び酢酸カリウム(KOAc)180.1 mg(1.8 mmol)を入れ、アルゴンガスをフラスコ内に充填した。そこに、乾燥ジオキサン(1,4-dioxane)15 mLを導入し、混合物とした。この混合物を撹拌しながら、90℃で5時間反応させた。フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をゲル浸透クロマトグラフィー(クロロホルム)で精製し、白色固体物質271.7 mgを得た。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(8a):
撹拌子を入れた50 mL丸型フラスコに、合成例7で得られた化合物(7a-2)137 mg(134μmol)、[Pd2(dba)3]2.8 mg(3.1μmol)、ビスピナコレートジボロン106 mg(419μmol)、及び酢酸カリウム(KOAc)75.7 mg(771μmol)を入れ、アルゴンガスをフラスコ内に充填した。そこに、乾燥ジオキサン(1,4-dioxane)5 mLを導入し、混合物とした。この混合物を撹拌しながら、90℃で5時間反応させた。フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した(EtOAc)。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をゲル浸透クロマトグラフィーで精製し、白色固体物質119 mgを得た。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(8b):
攪拌子を入れた50 mL丸底フラスコに、合成例6で得られた化合物(7a-1)19.7 mg(21μmol)、合成例9で得られた化合物(8a)29.1 mg(28μmol)、[Pd(OAc)2]0.9 mg(4.0μmol)、及びX-Phos2.0 mg(4.2μmol)を入れ、アルゴンガスをフラスコ内に充填した。乾燥させた1,4-ジオキサン10 mLと、10 Mの水酸化ナトリウム(NaOH)水溶液18 mL(0.18 mmol)を導入し、混合物とした。この混合物を撹拌しながら、80℃で24時間反応させた。その後、フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(CHCl3/EtOAc=1/1)で精製し、白色固体物質を得た(14.6 mg)。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(11a):
攪拌子を入れた2 mLガラスバイアルに、合成例11により得られた輪状の化合物(11a)9.1 mg(5.0μmol)、0.1 Mのp-トルエンスルホン酸水溶液50μL(5.0μmol)、及び、乾燥m-キシレン1 mLを入れ、混合物とした。このバイアルをマイクロ波反応装置(Initiator Synthesis System, Biotage社製)に入れ、撹拌しながら、150℃で30分間反応させた。次いで、バイアル内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(CH2Cl2/hexane)で精製し、白色固体物質を得た(1.1 mg)。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(3a):
撹拌子を入れた20 mLシュレンク管に、合成例11で得られた輪状の化合物(11a)7.9 mg(5.0μmol)、硫酸水素ナトリウム一水和物15.4 mg(11.3μmol)、乾燥m-キシレン1 mL、及び、乾燥させたジメチルスルホキシド(DMSO)1 mLを入れ、混合物とした。この混合物を撹拌しながら、150℃で48時間反応させた。次いで、シュレンク管内の混合物(反応液)を室温まで冷却し、混合物(反応液)をCHCl3で抽出した。抽出後の有機層をNa2SO4で乾燥した後に、減圧下、溶媒留去して粗生成物を得た。粗生成物をシリカゲル分取薄層クロマトグラフィー(CH2Cl2/hexane)で精製し、白色固体物質を得た(2.0 mg)。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析)によって、この白色固体物質を解析した結果、上記式(3a)で示される、ベンゼン環14個からなる[14]シクロパラフェニレン(アモルファス)であった。この[14]シクロパラフェニレンの収率は37%であった。
攪拌子を入れた50 mL丸底フラスコに、合成例7で得られた化合物(7a-2)20.0 mg(20μmol)、合成例9で得られた化合物(8a)285.4 mg(29μmol)、[Pd(OAc)2]1.0 mg(4.4μmol)、及びX-Phos2.2 mg(4.6μmol)を入れ、アルゴンガスをフラスコ内に充填した。乾燥1,4-ジオキサン20 mLと、10 MのNaOH水溶液19 mL(0.19 mmol)を導入し、混合物とした。この混合物を撹拌しながら、80℃で24時間反応させた。その後、フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(CHCl3/EtOAc=1/1)で精製し、白色固体物質を得た(10.4 mg)。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(11b):
攪拌子を入れた2 mLガラスバイアルに、合成例14で得られた輪状の化合物(11b)9.8 mg(6.0μmol)、0.1 Mのp-トルエンスルホン酸水溶液120μL(12μmol)、及び乾燥m-キシレン1 mLを入れ、混合物とした。この混合物を入れたバイアルを、上記合成例12と同様にマイクロ波反応装置に入れ、撹拌しながら、150℃で30分間反応させた。次いで、バイアル内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(CH2Cl2/hexane)で精製し、白色固体物質を得た(0.5 mg)。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(3b):
撹拌子を入れた20 mLシュレンク管に、合成例14で得られた輪状の化合物(11b)7.4 mg(4.5μmol)、硫酸水素ナトリウム一水和物14.7 mg(10.6μmol)、乾燥m-キシレン1 mL、及び、乾燥ジメチルスルホキシド(DMSO)1 mLを入れ、混合物とした。この混合物を撹拌しながら、150℃で48時間反応させた。次いで、シュレンク管内の混合物(反応液)を室温まで冷却し、混合物(反応液)をCHCl3で抽出した。抽出後の有機層をNa2SO4で乾燥した後に、減圧下、溶媒留去して粗生成物を得た。粗生成物をシリカゲル分取薄層クロマトグラフィー(CH2Cl2/hexane)で精製し、白色固体物質を得た(2.2 mg)。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、上記式(3b)で示される、ベンゼン環15個からなる[15]シクロパラフェニレン(アモルファス)であった。この[15]シクロパラフェニレンの収率は43%であった。
撹拌子を入れた50 mL丸型フラスコに、合成例7で得られた化合物(7a-2)42.8 mg(38.0μmol)、合成例10で得られた化合物(8b)26.7 mg(26.2μmol)[Pd(OAc)2]1.3 mg(5.7μmol)、及びX-Phos6.9 mg(14.4μmol)を入れ、アルゴンガスをフラスコ内に充填した。乾燥1,4-ジオキサン13.5 mLと、10 MのNaOH水溶液27.0μL(270μmol)を導入し、混合物とした後に、混合物を撹拌しながら、80℃で24時間反応させた。その後、フラスコ内の混合物(反応液)を室温まで冷却し、混合物(反応液)をシリカゲルでろ過した(EtOAc)。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲル分取薄層クロマトグラフィー(CHCl3:EtOAc=1:1)で精製し、白色固体物質を得た(15.5 mg)。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(11c):
撹拌子を入れた20 mLシュレンク管に、合成例17で得られた輪状化合物(11c)12.5 mg(7.26μmol)、硫酸水素ナトリウム一水和物20.0 mg(145μmol)、乾燥m-キシレン1.2 mL、及び、乾燥ジメチルスルホキシド(DMSO)1.2 mLを入れ、混合物とした。この混合物を撹拌しながら、160℃で48時間反応させた。次いで、シュレンク管内の混合物(反応液)を室温まで冷却し、混合物(反応液)をCHCl3で抽出した。抽出後の有機層をNa2SO4で乾燥した後に、減圧下、溶媒留去して粗生成物を得た。粗生成物をシリカゲル分取薄層クロマトグラフィー(CH2Cl2/hexane)で精製し、白色固体物質を得た(2.5 mg)。そして、核磁気共鳴分析(1H NMR、13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(3c):
攪拌子を入れた50 mL丸底フラスコに、合成例8で得られた化合物(7a-3)20.0 mg(20μmol)、合成例9で得られた化合物(8a)29.4 mg(28μmol)、[Pd(OAc)2]0.9 mg(4.0μmol)、及びX-Phos2.0 mg(4.2μmol)を入れ、アルゴンガスをフラスコ内に充填した。乾燥1,4-ジオキサン10 mLと、10 Mの水酸化ナトリウム(NaOH)水溶液10μL(0.10 mmol)を導入し、混合物とした後に、混合物を撹拌しながら、80℃で24時間反応させた。その後、フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)をシリカゲルでろ過した。得られたろ液をエバポレーターで溶媒を減圧留去した後に、残渣(濃縮物)をシリカゲルクロマトグラフィー(CHCl3/EtOAc=1/1)で精製し、白色固体物質を得た(4.0 mg)。そして、核磁気共鳴分析(1H NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(11d):
攪拌子を入れた100 mL丸底フラスコに合成例2で得られた化合物(5b)を2.49 g(4.84 mmol)、合成例5で得られた化合物(6c)を190 mg(500μmol)、Pd(PPh3)4を15.0 mg(13.0μmol)、炭酸ナトリウム(Na2CO3)を268 mg(2.53 mmol)、臭化テトラn-ブチルアンモニウム(n-Bu4NBr)を555 mg(499μmol)、乾燥THFを20 mL、アルゴンガスをバブリングした水を5 mL入れた。混合物を撹拌しながら、60℃で24時間反応させた。次いで、フラスコ内の混合物(反応液)を室温に冷却し、混合物(反応液)を減圧下でろ過した。残渣(濃縮物)をEtOAcで抽出し、Na2SO4で乾燥し、減圧下でろ過した。粗生成物をシリカゲルクロマトグラフィー(hexane/EtOAc=8:1~2:1)で精製し、白色固体物質359 mgを得た。そして、核磁気共鳴分析(1H NMR及び13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(7a-3):
攪拌子を入れた50 mLシュレンク管に、合成例20で得られた化合物(7a-3)を40.1 mg(40.3μmol)、合成例9で得られた化合物(8a)を50.2 mg(48.3μmol)、Pd2(dba)3を3.6 mg(3.9μmol)、X-Phosを3.7 mg(7.8μmol)、K3PO4を85.0 mg(400μmol)入れた。その後、フラスコを脱気し、アルゴンガスで3回充填した。このフラスコにアルゴンガスをバブリングした1,4-ジオキサン20 mL及びアルゴンをバブリングした水80μLをアルゴン気流下で添加した。80℃で24時間攪拌した後、シリカゲル層を通過させて溶媒を除去した(EtOAc)。その後、減圧下に減圧下に溶媒留去して粗生成物を得た。粗生成物をゲル浸透クロマトグラフィー及び分取薄層クロマトグラフィー(CHCl3/EtOAc=1:1)で精製し、白色固体物質22.6 mgを得た。そして、核磁気共鳴分析(1H NMR及び13C NMR)及び質量分析によって、この白色固体物質を解析した結果、下記式(11d):
攪拌子及び冷却器を入れた20 mLシュレンク管に、合成例19又は21で得られた輪状化合物(11d)16.2 mg(10.0μmol)、硫酸水素ナトリウム一水和物(NaHSO4・H2O)27.2 mg(197μmol)、乾燥DMSO1 mL及びm-キシレン2.0 mLを入れた。空気雰囲気下で攪拌しながら混合物を150℃で24時間加熱した。混合物を室温まで冷却し、シリカゲル層を通過させて溶媒を除去した(CHCl3)。その後、減圧下に溶媒留去して粗生成物を得た。粗生成物を薄層クロマトグラフィー(CH2Cl2/hexane)で精製し、淡黄色固体物質を得た(2.8 mg)。そして、核磁気共鳴分析(1H NMR及び13C NMR)及び質量分析によって、この淡黄色固体物質を解析した結果、下記式(3d):
(1)輪状の化合物(12a)及び(12b-1)の製造
200 mLの攪拌機つきの、ガラスの丸底フラスコに、ビス(1,5-シクロオクタジエン)ニッケル(0価)452 mg(1.64 mmol)、合成例2で得られた化合物(5b)423 mg(823μmol)、2,2'-ビピリジル257 mg(1.65 mmol)を収容した。ここに、THF166 mLをシリンジで添加した。次いで、混合物を還流下に24時間攪拌した。室温まで冷却した後、シリカゲル層を通過させ、EtOAc/CHCl3の混合溶媒で洗浄した。その後、減圧下に、溶媒を除去した。粗生成物をシリカゲルカラムクロマトグラフィー(ヘキサン/EtOAc)で精製し、下記式(12a):
1H NMR (400 MHz CDCl3) δ 2.16 (brs, 16H), 2.37 (brs, 16H), 3.42 (s, 16H), 4.45 (s, 16H), 7.50 (s, 32H).
環化三量体(12b-1):
1H NMR (600 MHz, 50 ℃, CDCl3) δ 2.07 (brs, 12H), 2.28-2.34 (m, 12H), 3.43 (s, 18H), 4.58 (s, 12H), 7.40 (d, J = 8 Hz, 12H), 7.46 (d, J = 8 Hz, 12H); 13C NMR (150 MHz, 50 ℃, CDCl3) δ 33.3 (CH2), 55.9 (CH3), 78.1 (4°), 92.4 (CH2), 126.8 (CH), 127.3 (CH), 139.4 (4°), 141.2 (4°); HRMS (FAB) m/z calcd for C66H78NaO12[M・Na]+: 1085.5391, found: 1085.538; mp : 182.3-187.0℃.
20 mLの攪拌機及び冷却器つきシュレンク管に、上記式(12b-1)で表される環化三量体、又は後述の合成例30で得られた化合物(12b-1)26.6 mg(25μmol)、硫酸水素ナトリウム・一水和物69.1 mg(400μmol)、乾燥ジメチルスルホキシド1.5 mL及び乾燥m-キシレン5 mLを収容し、攪拌しながら150℃で48時間加熱した。室温まで冷却した後、混合物(反応液)をCHCl3で抽出した。抽出後、Na2SO4で乾燥した後に、減圧下、溶媒留去して粗生成物を得た。その後、TLC(CH2Cl2/ヘキサン)により、黄色固体4.2 mgを単離した。そして、1H NMR及び13C NMRによって、この物質を解析した結果、下記式(4b):
上記(1)で得られた化合物(12a)を、上記(2)と同様に処理して、下記式(4a):
サファイア単結晶基板(C面)上に、合成例23(3)で得られた[12]シクロパラフェニレン([12]CPP)(4a)のトルエン溶液(0.001wt%)をスピンコートにて塗布した。スピンコートの条件は、回転数が4000rpm、回転時間は60secであった。
サファイア単結晶基板(C面)上に、合成例23(2)で得られた[9]シクロパラフェニレン([9]CPP)(4b)のトルエン溶液(0.001wt%)を スピンコートにて塗布した。スピンコートの条件は、回転数が4000rpm、回転時間は60secであった。
合成例12又は13で得られた[14]シクロパラフェニレン(3a)を実施例1と同様に処理したCNT。
合成例15又は16で得られた[15]シクロパラフェニレン(3b)を実施例1と同様に処理したCNT。
合成例18で得られた[16]シクロパラフェニレン(3c)を実施例1と同様に処理したCNT。
合成例22で得られた化合物(3d)を実施例1と同様に処理したCNT。
合成例35で得られた[10]シクロパラフェニレン(13a)を実施例1と同様に処理したCNT。
合成例36で得られた[11]シクロパラフェニレン(13b)を実施例1と同様に処理したCNT。
合成例37で得られた[13]シクロパラフェニレン(13c)を実施例1と同様に処理したCNT。
Claims (13)
- 複数の芳香族環が連結してなる環状化合物に炭素源を反応させることを特徴とするカーボンナノチューブの製造方法。
- 前記反応が、気体状の炭素源を供給して減圧下で加熱して反応させる、請求項1に記載の製造方法。
- 前記複数の芳香族環が連結してなる環状化合物が、複数の2価の芳香族炭化水素基が連結してなる環状化合物(カーボンナノリング)である、請求項1又は2に記載の製造方法。
- 前記複数の2価の芳香族炭化水素基が連結してなる環状化合物(カーボンナノリング)が、シクロパラフェニレン化合物、又は当該シクロパラフェニレン化合物の少なくとも1個のフェニレン基が2価の縮合多環芳香族炭化水素基で置換された修飾シクロパラフェニレン化合物である、請求項3に記載の製造方法。
- 前記シクロパラフェニレン化合物が、一般式(1)におけるaが6~100の整数である化合物である、請求項5に記載の製造方法。
- 前記複数の2価の芳香族炭化水素基が連結してなる環状化合物(カーボンナノリング)が、一般式(1)で表されるシクロパラフェニレン化合物である、請求項5又は6に記載の製造方法。
- 前記複数の2価の芳香族炭化水素基が連結してなる環状化合物(カーボンナノリング)が、一般式(3):
で表される環状化合物、一般式(4):
で表される環状化合物、又は一般式(13):
で示される環状化合物である、請求項3に記載の製造方法。 - 前記炭素源が、炭化水素化合物、アルコール化合物、エーテル化合物及びエステル化合物からなる群より選ばれる少なくとも1種である、請求項1~8のいずれかに記載の製造方法。
- 前記反応が、気体状の炭素源を供給しながら、10-4~105Paの圧力下で400~1200℃で加熱処理して反応させる、請求項1~9のいずれかに記載の製造方法。
- 複数の芳香族環が連結してなる環状化合物に炭素源を反応させることにより得られたカーボンナノチューブ。
- 前記反応が、気体状の炭素源を供給して減圧下で加熱して反応させる、請求項11に記載のカーボンナノチューブ。
- 単層カーボンナノチューブである、請求項11又は12に記載のカーボンナノチューブ。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012800121541A CN103415465A (zh) | 2011-03-08 | 2012-03-08 | 碳纳米管的制备方法 |
KR1020137026510A KR20140014224A (ko) | 2011-03-08 | 2012-03-08 | 카본 나노 튜브의 제조 방법 |
EP12755349.3A EP2684844A4 (en) | 2011-03-08 | 2012-03-08 | METHOD FOR PRODUCING CARBON NANOTONES |
JP2013503617A JP6086387B2 (ja) | 2011-03-08 | 2012-03-08 | カーボンナノチューブの製造方法 |
US14/003,289 US9527737B2 (en) | 2011-03-08 | 2012-03-08 | Carbon nanotube manufacturing method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-050398 | 2011-03-08 | ||
JP2011050398 | 2011-03-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012121354A1 true WO2012121354A1 (ja) | 2012-09-13 |
Family
ID=46798307
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/056033 WO2012121354A1 (ja) | 2011-03-08 | 2012-03-08 | カーボンナノチューブの製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9527737B2 (ja) |
EP (1) | EP2684844A4 (ja) |
JP (1) | JP6086387B2 (ja) |
KR (1) | KR20140014224A (ja) |
CN (1) | CN103415465A (ja) |
WO (1) | WO2012121354A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013133386A1 (ja) * | 2012-03-08 | 2013-09-12 | 国立大学法人名古屋大学 | 官能基含有又は非含有環状化合物及びこれらの製造方法 |
JP2016032083A (ja) * | 2014-07-30 | 2016-03-07 | コニカミノルタ株式会社 | 有機エレクトロニクス素子用材料、有機エレクトロニクス素子及び有機エレクトロニクスデバイス |
JP2017518945A (ja) * | 2014-04-15 | 2017-07-13 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオMax−Planck−Gesellschaft zur Foerderung der Wissenschaften e.V. | 予め規定されたカイラリティのシングルウォールカーボンナノチューブの製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10654780B2 (en) * | 2017-04-11 | 2020-05-19 | University Of Oregon | Halogenated nanohoop compounds and methods of making and using the same |
US11555820B2 (en) | 2017-07-21 | 2023-01-17 | University Of Oregon | Nanohoop compounds for use in biotechnology and methods of making and using the same |
MY201583A (en) | 2017-08-22 | 2024-03-02 | Ntherma Corp | Vertically aligned multi-walled carbon nanotubes |
SG11202001517SA (en) | 2017-08-22 | 2020-03-30 | Ntherma Corp | Graphene nanoribbons, graphene nanoplatelets and mixtures thereof and methods of synthesis |
US11142500B2 (en) | 2018-07-09 | 2021-10-12 | University Of Oregon | Nanohoop compound embodiments comprising meta-substitution and molecular systems comprising the same |
US11739178B2 (en) | 2019-09-27 | 2023-08-29 | University Of Oregon | Nanohoop-functionalized polymer embodiments and methods of making and using the same |
US11505644B2 (en) | 2019-09-27 | 2022-11-22 | University Of Oregon | Polymer embodiments comprising nanohoop-containing polymer backbones and methods of making and using the same |
CN111986834B (zh) * | 2020-07-29 | 2022-03-22 | 北海惠科光电技术有限公司 | 一种碳纳米管导电薄膜的制作方法、显示面板和显示装置 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005097014A (ja) * | 2003-09-22 | 2005-04-14 | Fuji Xerox Co Ltd | カーボンナノチューブの製造装置および製造方法、並びにそれに用いるガス分解器 |
JP2009538809A (ja) * | 2006-03-29 | 2009-11-12 | ハイピリオン カタリシス インターナショナル インコーポレイテッド | 金属層から単層カーボンナノチューブを製造する方法 |
JP2009280450A (ja) * | 2008-05-23 | 2009-12-03 | Nagoya Institute Of Technology | カーボンナノチューブの製造方法及び製造装置 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1176014C (zh) * | 2002-02-22 | 2004-11-17 | 清华大学 | 一种直接合成超长连续单壁碳纳米管的工艺方法 |
WO2008048227A2 (en) * | 2005-08-11 | 2008-04-24 | Kansas State University Research Foundation | Synthetic carbon nanotubes |
-
2012
- 2012-03-08 JP JP2013503617A patent/JP6086387B2/ja active Active
- 2012-03-08 WO PCT/JP2012/056033 patent/WO2012121354A1/ja active Application Filing
- 2012-03-08 US US14/003,289 patent/US9527737B2/en active Active
- 2012-03-08 CN CN2012800121541A patent/CN103415465A/zh active Pending
- 2012-03-08 KR KR1020137026510A patent/KR20140014224A/ko not_active Application Discontinuation
- 2012-03-08 EP EP12755349.3A patent/EP2684844A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005097014A (ja) * | 2003-09-22 | 2005-04-14 | Fuji Xerox Co Ltd | カーボンナノチューブの製造装置および製造方法、並びにそれに用いるガス分解器 |
JP2009538809A (ja) * | 2006-03-29 | 2009-11-12 | ハイピリオン カタリシス インターナショナル インコーポレイテッド | 金属層から単層カーボンナノチューブを製造する方法 |
JP2009280450A (ja) * | 2008-05-23 | 2009-12-03 | Nagoya Institute Of Technology | カーボンナノチューブの製造方法及び製造装置 |
Non-Patent Citations (3)
Title |
---|
BRIAN D.STEINBERG ET AL.: "New Strategies for Synthesizing Short Sections of Carbon Nanotubes", ANGEW.CHEM.INT.ED., vol. 48, no. 30, 2009, pages 5400 - 5402, XP055124250 * |
KENTARO SATO: "Graphene kara Nanotube made Kagaku Gosei de Shin Tanso Zairyo ni Idomu", GENDAI KAGAKU, vol. 461, 1 August 2009 (2009-08-01), pages 16 - 20, XP008170718 * |
See also references of EP2684844A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013133386A1 (ja) * | 2012-03-08 | 2013-09-12 | 国立大学法人名古屋大学 | 官能基含有又は非含有環状化合物及びこれらの製造方法 |
US9266909B2 (en) | 2012-03-08 | 2016-02-23 | National University Corporation Nagoya University | Cyclic compound containing functional group or containing no functional group, and method for producing same |
JP2017518945A (ja) * | 2014-04-15 | 2017-07-13 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオMax−Planck−Gesellschaft zur Foerderung der Wissenschaften e.V. | 予め規定されたカイラリティのシングルウォールカーボンナノチューブの製造方法 |
JP2016032083A (ja) * | 2014-07-30 | 2016-03-07 | コニカミノルタ株式会社 | 有機エレクトロニクス素子用材料、有機エレクトロニクス素子及び有機エレクトロニクスデバイス |
Also Published As
Publication number | Publication date |
---|---|
EP2684844A1 (en) | 2014-01-15 |
KR20140014224A (ko) | 2014-02-05 |
EP2684844A4 (en) | 2014-09-03 |
JP6086387B2 (ja) | 2017-03-01 |
US9527737B2 (en) | 2016-12-27 |
JPWO2012121354A1 (ja) | 2014-07-17 |
US20140030183A1 (en) | 2014-01-30 |
CN103415465A (zh) | 2013-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6086387B2 (ja) | カーボンナノチューブの製造方法 | |
TWI552953B (zh) | 石墨烯奈米帶前驅物及適用於製備彼等之單體 | |
JP6032664B2 (ja) | カーボンナノリング及びその製造方法、並びに該カーボンナノリングの製造原料として好適な化合物及びその製造方法 | |
WO2008059771A1 (fr) | Procédé de production d'un dérivé du fullerène | |
JP5971656B2 (ja) | シクロポリアリーレン化合物及びそれらの製造方法 | |
WO2012169635A1 (ja) | アリール基で置換された多環性芳香族化合物の製造方法 | |
EP2907791A1 (en) | Graphene nanoribbons with controlled zig-zag edge and cove edge configuration | |
Gao et al. | Two anionic [CuI6X7] nn−(X= Br and I) chain-based organic–inorganic hybrid solids with N-substituted benzotriazole ligands | |
KR20210141970A (ko) | 그래핀 나노리본 및 그 제조 방법 | |
JP5713324B2 (ja) | カーボンナノリング及びその製造原料として好適な輪状の化合物の製造方法 | |
JP6449014B2 (ja) | 官能基含有又は非含有環状化合物及びこれらの製造方法 | |
Dzyuba et al. | Synthesis and structure of lipophilic dioxo-molybdenum (VI) bis (hydroxamato) complexes | |
Dannenberg et al. | Synthesis, structure and thermolysis of oxazagermines and oxazasilines | |
Sarkar et al. | Palladium nanoparticles supported on reduced graphene oxide (Pd@ rGO): an efficient heterogeneous catalyst for Suzuki–Miyaura, Heck–Matsuda and Double Suzuki–Miyaura cross-coupling reactions | |
Ye et al. | Homoleptic dirhodium tetraoctanoate and its pyridine adduct: synthesis and crystal structures | |
CN114181220B (zh) | 一种螺线管状磁性碳纳米材料及其制备方法 | |
Naeimi et al. | Inorganic–organic hybrid nano magnetic based nickel complex as a novel, efficient and reusable nanocomposite for the synthesis of biphenyl compounds in green condition | |
Yang | Synthesis of Novel Polydiacetylenes Towards Topochemical Polymerization | |
WO2014132467A1 (ja) | カーボンナノケージ及びその中間体、並びにこれらの製造方法 | |
CN111233598A (zh) | 一种制备4-炔酮/酯类化合物的方法及其应用 | |
JP2017001962A (ja) | シクロポリアリーレン化合物及びその製造方法 | |
MacKinnon | Synthesis of novel π-systems containing two pyrene units |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12755349 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013503617 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137026510 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2012755349 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012755349 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14003289 Country of ref document: US |