WO2021120767A1 - 环带芳烃䓬类化合物及其制备方法和用途 - Google Patents

环带芳烃䓬类化合物及其制备方法和用途 Download PDF

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WO2021120767A1
WO2021120767A1 PCT/CN2020/117641 CN2020117641W WO2021120767A1 WO 2021120767 A1 WO2021120767 A1 WO 2021120767A1 CN 2020117641 W CN2020117641 W CN 2020117641W WO 2021120767 A1 WO2021120767 A1 WO 2021120767A1
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formula
compound
compound represented
optionally substituted
methylbenzyl
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French (fr)
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王梅祥
张艳娥
张乾
佟硕
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清华大学
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/52—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of six-membered aromatic rings being part of condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
    • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present disclosure relates to the field of organic chemistry.
  • the present disclosure relates to cyclic [n] aromatic hydrocarbons [n] Alkene, cyclic belt [4] Aromatic hydrocarbon [4] Compounds, Annular Zone [4] Aromatics [4-m] Alkene [m] dicarbonyl compound, ring zone [4] aromatic hydrocarbon [4-m] Ene [m] benzo Olefin compounds, ring belt [4] aromatic hydrocarbon [4-m] benzo Alkene [m] dicarbonyl compound and its preparation method and use.
  • Multicyclic compounds have the characteristics and advantages of good molecular structure designability and physical and chemical properties adjustable, and have been widely used in many fields of chemistry, materials science and life science.
  • synthetic macrocyclic compounds can recognize anions, cations and neutral guest molecules, so that they can be used in separation, sensing and detection.
  • functionalized macrocyclic compounds are used in the construction of functional assemblies and nanomaterials and molecular machines. Macrocyclic compounds also provide unique research methods and approaches for exploring chemical reaction mechanisms and supramolecular catalysis.
  • the present disclosure aims to solve one of the technical problems in the related art at least to some extent. For this reason, one purpose of the present disclosure is to propose ring-shaped aromatic hydrocarbons Compounds and preparation methods and uses thereof.
  • This type of compound has a barrel-shaped cavity structure, the volume of the cavity is variable, and the polarity of the inner wall of the cavity is adjustable, and has broad application prospects.
  • the present disclosure proposes a compound. According to the embodiments of the present disclosure, it is a compound represented by formula (I) or a stereoisomer of a compound represented by formula (I),
  • n 4 or 6;
  • R 1 is a hydrogen atom, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 2-12 alkenyl, optionally substituted C 5-24 cycloalkane Group or optionally substituted C 5-24 heterocyclic group.
  • This type of compound has a barrel-shaped cavity structure, the volume of the cavity is variable, and the polarity of the inner wall of the cavity is adjustable.
  • As a new type of artificially synthesized macrocyclic molecules it can selectively recognize organic molecules from mixed solutions and form inclusion complexes with them, which can be used as materials for the selective separation of small organic molecules; this type of compound has good fluorescence properties and can be Applied to the preparation of organic optoelectronic materials; in addition, this type of compound can also be used in the "bottom-up" synthesis strategy to synthesize carbon nanorings and other heterogeneous carbon nanotube precursors.
  • R 1 is a hydrogen atom, C 1-6 alkyl, C 1-6 heteroalkyl, C 2-6 alkenyl, C 5-12 cycloalkyl, C 5-12 hetero Cycloalkyl.
  • R 1 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • the compound has one of the following structures:
  • the present disclosure proposes a compound.
  • the compound is a compound represented by formula (II) or a stereoisomer of a compound represented by formula (II),
  • n 4 or 6;
  • R 2 is a hydrogen atom, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 2-12 alkenyl, optionally substituted C 5-24 cycloalkane Group or optionally substituted C 5-24 heterocyclic group.
  • This type of compound has a barrel-shaped cavity structure, the volume of the cavity is variable, and the polarity of the inner wall of the cavity is adjustable.
  • As a new type of artificially synthesized macrocyclic molecules it can selectively recognize organic molecules from mixed solutions and form inclusion complexes with them, which can be used as materials for the selective separation of small organic molecules; this type of compound has good fluorescence characteristics and can be used as a material for selective separation of small organic molecules.
  • this type of compound can also be used in the "bottom-up" synthesis strategy to synthesize carbon nanorings and other heterogeneous carbon nanotube precursors.
  • R 2 is a hydrogen atom, C 1-6 alkyl, C 1-6 heteroalkyl, C 2-6 alkenyl, C 5-12 cycloalkyl, C 5-12 hetero Cycloalkyl.
  • n is 4;
  • R 2 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • the compound has one of the following structures:
  • the present disclosure proposes a compound.
  • the compound is a compound represented by formula (V) or a stereoisomer of a compound represented by formula (V),
  • n 1, 2 or 3
  • m and m' are independently 1, 2, 3 or 4 respectively;
  • R 3 is a hydrogen atom, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 2-12 alkenyl, optionally substituted C 5-24 cycloalkane Group or optionally substituted C 5-24 heterocyclic group.
  • the compound represented by formula (V) is also called cyclic band [4] aromatic hydrocarbon [4-m] En [m] dicarbonyl compound.
  • This type of compound has a barrel-shaped cavity structure, the volume of the cavity is variable, and the polarity of the inner wall of the cavity is adjustable.
  • As a new type of artificially synthesized macrocyclic molecules it can selectively recognize organic molecules from mixed solutions and form inclusion complexes with them, which are used as materials for the selective separation of small organic molecules; this type of compound has good fluorescence characteristics and can be Applied to the preparation of organic optoelectronic materials; in addition, this type of compound can also be used in the "bottom-up" synthesis strategy to synthesize carbon nanorings and other heterogeneous carbon nanotube precursors.
  • n is 1, 2 or 3
  • m and m' are independently 1, 2, 3 or 4 respectively
  • R 3 is a hydrogen atom, an optionally substituted C 1-12 alkyl group, An optionally substituted C 1-12 heteroalkyl group, an optionally substituted C 2-12 alkenyl group, an optionally substituted C 5-24 cycloalkyl group or an optionally substituted C 5-24 heterocyclic group.
  • R 3 is a hydrogen atom, C 1-6 alkyl, C 1-6 heteroalkyl, C 2-6 alkenyl, C 5-12 cycloalkyl, C 5-12 hetero Cycloalkyl.
  • R 3 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • the compound has one of the following structures:
  • the present disclosure proposes a compound.
  • the compound represented by the formula (VI), the compound represented by the formula (VIII) or the compound represented by the formula (IX), or its stereoisomers or its stereoisomers,
  • n 1, 2 or 3
  • m and m' are independently 1, 2, 3 or 4 respectively;
  • R 4 is a hydrogen atom, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 2-12 alkenyl, optionally substituted C 5-24 cycloalkane Group or optionally substituted C 5-24 heterocyclic group;
  • Ar 1 is X is N or C-CN.
  • connection position of Ar 1 in the formula (VI) Ar 1 is shown in The 2 and 3 positions of and form a ring with the parent.
  • the compound represented by the formula (VI), the compound represented by the formula (VIII), or the compound represented by the formula (IX) are also called ring band [4] aromatic hydrocarbon [4-m] Ene [m] benzo Olefin compounds.
  • This type of compound has a barrel-shaped cavity structure, the volume of the cavity is variable, and the polarity of the inner wall of the cavity is adjustable.
  • As a new type of artificially synthesized macrocyclic molecules it can selectively recognize organic molecules from mixed solutions and form inclusion complexes with them, which can be used as materials for the selective separation of small organic molecules; this type of compound has good fluorescence characteristics and can be used as a material for selective separation of small organic molecules.
  • this type of compound can also be used in the "bottom-up" synthesis strategy to synthesize carbon nanorings and other heterogeneous carbon nanotube precursors.
  • R 4 is a hydrogen atom, C 1-6 alkyl, C 1-6 heteroalkyl, C 2-6 alkenyl, C 5-12 cycloalkyl, C 5-12 hetero Cycloalkyl.
  • R 4 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • R 4 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • R 4 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • R 4 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • R 4 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • the compound has one of the following structures:
  • the present disclosure proposes a compound.
  • the compound is a compound represented by formula (VII) or a stereoisomer of a compound represented by formula (VII),
  • n, m and m' are independently 1, 2, 3, or 4 respectively;
  • R 5 is a hydrogen atom, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 2-12 alkenyl, optionally substituted C 5-24 cycloalkane Group or optionally substituted C 5-24 heterocyclic group;
  • Ar 2 is X is N or C-CN.
  • connection position shown Ar 2 in Formula (VII) is the Ar 2 The 2 and 3 positions of and form a ring with the parent.
  • the compound represented by formula (VII) is also known as the ring zone [4] aromatic hydrocarbon [4-m] benzo En [m] dicarbonyl compound.
  • This type of compound has a barrel-shaped cavity structure, the volume of the cavity is variable, and the polarity of the inner wall of the cavity is adjustable.
  • As a new type of artificially synthesized macrocyclic molecules it can selectively recognize organic molecules from mixed solutions and form inclusion complexes with them, which can be used as materials for the selective separation of small organic molecules; this type of compound has good fluorescence characteristics and can be used as a material for selective separation of small organic molecules.
  • this type of compound can also be used in the "bottom-up" synthesis strategy to synthesize carbon nanorings and other heterogeneous carbon nanotube precursors.
  • R 5 is a hydrogen atom, C 1-6 alkyl, C 1-6 heteroalkyl, C 2-6 alkenyl, C 5-12 cycloalkyl, C 5-12 hetero Cycloalkyl.
  • R 5 is a hydrogen atom, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl , N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, benzyl, p-methylbenzyl, o-methylbenzyl, or m-methylbenzyl.
  • the compound has one of the following structures:
  • the present disclosure proposes a method for preparing the above-mentioned compound. Specifically, it includes preparing the compound represented by (I), the compound represented by formula (II), the compound represented by formula (V), the compound represented by formula (VI), the compound represented by formula (VII), the compound represented by formula (VIII), Method for the compound represented by formula (IX).
  • the method for preparing the compound represented by formula (I) includes: causing the compound represented by formula (III) to undergo an intramolecular olefin ring-closing metathesis reaction in the presence of a Grubbs catalyst to obtain the compound represented by formula (I) Shows the compound,
  • R 1 is as described above.
  • the compound represented by formula (III) can undergo an intramolecular olefin ring-closing metathesis reaction under the action of Grubbs catalyst to obtain the compound represented by formula (I) under mild reaction conditions and the resulting product It is stable in the air and easy to separate and purify, and has good practicability and application prospects.
  • the above-mentioned Grubbs catalyst includes a catalyst selected from the group consisting of Grubbs I-generation catalyst, Grubbs II-generation catalyst, Grubbs III-generation catalyst, and Grubbs-Hovida (Grubbs-Hoveyda) catalyst and at least one of Schrock catalyst.
  • Grubbs III-generation catalysts can be obtained by referring to the literature Immobilisation of the Grubbs III Olefin Metathesis Catalyst with Polyvinyl Pyridine (PVP), Synlett 2005, No. 19, 2948-2952.
  • the above-mentioned contact is performed in a first solvent
  • the first solvent may include selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1 , At least one of 2,2-tetrachloroethane, benzene, toluene, benzotrifluoride, chlorobenzene, fluorobenzene, nitrobenzene, bromobenzene, o-xylene, meta-xylene, p-xylene and tetralin One;
  • the first solvent is preferably dichloromethane.
  • the above-mentioned contact can be completed at -40 to 150°C for 0.1 to 96 hours, preferably at 40 to 120°C for 24 to 96 hours.
  • the yield and selectivity of the product can be further improved.
  • the amount ratio of the compound represented by the above formula (III) to the Grubbs catalyst may be 0.01-1 mmol: 0.01-100 mmol, preferably 0.1-1 mmol: 1-10 mmol. As a result, the yield and selectivity of the product can be further improved.
  • the compound represented by formula (III) is prepared by cross-coupling the compound represented by formula (IV) under the action of a metal catalyst,
  • the above-mentioned metal catalyst may include selected from the group consisting of palladium acetate, tetrakistriphenylphosphine palladium, tris(dibenzylideneacetone)dipalladium, palladium chloride and [1,1'-bis(diphenyl) Phosphine) ferrocene) palladium dichloride, nickel acetylacetonate, bis(1,5-cyclooctadiene) nickel, 1,3-bis(diphenylphosphino) ethane nickel dichloride, 1, 3-bis(diphenylphosphino)propane nickel dichloride, 1,3-bis(diphenylphosphino)butane nickel dichloride, 1,3-bis(diphenylphosphino)ferrocene At least one of the nickel dichlorides is preferably 1,3-bis(diphenylphosphino)ethane nickel dichloride.
  • the upper cross-coupling reaction is carried out in a second solvent
  • the second solvent may include N,N-dimethylformamide, N,N-dimethylaniline, N,N -At least one of dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, water and dimethylsulfoxide, preferably N,N-dimethylformamide.
  • the above-mentioned cross-coupling reaction is carried out under the action of additives and alkenylation reagents.
  • the additives may include those selected from the group consisting of potassium carbonate, cesium carbonate, lithium carbonate, sodium carbonate, sodium chloride, and lithium chloride.
  • alkenylation reagent may include selected from vinylmagnesium bromide, isopropenyl magnesium bromide, tributylvinylene, tributylisopropenylene, isopropenylboronic acid pinacol ester and vinylboronic acid At least one of pinacol esters; the preferred additive is lithium chloride, and the preferred alkenylation reagent is tributyl vinyl tin.
  • the above-mentioned cross-coupling reaction can be completed at 0-140°C for 6-72 hours.
  • the reaction temperature may be 0°C, 20°C, 40°C, 90°C, 120°C, 140°C, etc.
  • the reaction time can be 6h, 12h, 24h, 36h, 72h, etc.
  • the cross-coupling reaction is completed at 90°C for 24 hours.
  • a better yield can be obtained.
  • the method for preparing the compound represented by the formula (II) includes: contacting the compound represented by the formula (I) with a reduction catalyst and hydrogen to obtain the compound represented by the formula (II).
  • R 1 and R 2 are as described above.
  • the aforementioned reduction catalyst may include at least one selected from platinum black, platinum dioxide, palladium black, palladium carbon, platinum carbon, rhodium carbon, and ruthenium carbon, preferably rhodium carbon.
  • platinum black platinum dioxide, palladium black, palladium carbon, platinum carbon, rhodium carbon, and ruthenium carbon, preferably rhodium carbon.
  • the above-mentioned contact is performed in a third solvent
  • the third solvent may include at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, tert-butanol, formic acid, acetic acid, and propionic acid.
  • the third solvent may include at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, tert-butanol, formic acid, acetic acid, and propionic acid.
  • One of them is preferably formic acid.
  • the above-mentioned contact is performed in a hydrogen atmosphere of 1-1000 atm; specifically, the hydrogen pressure may be 1 atm, 20 atm, 100 atm, 500 atm, 800 atm, 1000 atm, etc., preferably, 1 atm.
  • the hydrogen pressure may be 1 atm, 20 atm, 100 atm, 500 atm, 800 atm, 1000 atm, etc., preferably, 1 atm.
  • the above-mentioned contact is completed at -40 to 150°C for 0.1 to 96 hours.
  • the temperature can be -40°C, -20°C, 0°C, 20°C, 50°C, 80°C, 100°C , 150°C, etc.
  • the time can be 0.1h, 1h, 12h, 24h, 48h, 72h, 96h, etc.
  • the aforementioned contact is completed at 50°C for 48 hours.
  • a better yield can be obtained.
  • the dosage ratio of the compound represented by formula (I) to the reduction catalyst may be 0.01-1 mmol: 0.01-100 mmol.
  • the dosage of the compound represented by formula (I) may be 0.01 mmol, 0.05 mmol, 0.1mmol, 0.2mmol, 0.5mmol, 1mmol, etc.
  • the amount of reduction catalyst can be 0.01mmol, 0.1mmol, 0.2mmol, 1mmol, 5mmol, 20mmol, 40mmol, 80mmol, 100mmol, etc.
  • the amount ratio of the compound represented by formula (I) to the reduction catalyst is 0.01 mmol:0.2 mmol.
  • a method for preparing a compound represented by formula (V) includes: contacting a compound represented by formula (I) with a first oxidant to obtain a compound represented by formula (V),
  • R 1 and R 3 are as described above.
  • the above-mentioned first oxidant may include selected from the group consisting of benzoselenite anhydride, selenium dioxide, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and tetrachlorobenzene. At least one of the quinone and iodine is preferably benzoselenous acid anhydride.
  • the above-mentioned contact is carried out in a fourth solvent
  • the fourth solvent may include at least one selected from the group consisting of chlorobenzene, fluorobenzene, bromobenzene, and chloroform, preferably chloroform, which is carried out in the solvent
  • the reaction yield is higher and the reaction by-products are less.
  • the aforementioned contact can be completed at 50-150°C for 0.1-96 hours; specifically, the temperature can be 50°C, 70°C, 90°C, 120°C, 150°C, etc., and the time can be 0.1h, 1h, 12h, 24h, 48h, 72h, 96h, etc.
  • the above-mentioned contact is performed at 120°C, whereby the reaction rate is faster and the yield is higher.
  • the amount ratio of the compound represented by formula (I) to the first oxidizing agent may be 0.01-1 mmol:0.01-100 mmol.
  • the amount of the compound represented by formula (I) can be 0.01mmol, 0.05mmol, 0.1mmol, 0.2mmol, 0.5mmol, 1mmol, etc.
  • the amount of the first oxidant can be 0.01mmol, 0.1mmol, 0.2mmol, 1mmol, 5mmol, 20mmol, 40mmol, 80mmol, 100mmol, etc.
  • the amount ratio of the compound represented by formula (I) to the first oxidant is 0.01 mmol:0.2 mmol.
  • a better yield can be obtained.
  • the compounds represented by formula (VI), (VIII) and (IX) can be prepared by condensation reaction of the compound represented by formula (V) with a dual nucleophile.
  • the compound represented by formula (V) can be prepared by the condensation reaction of the compound represented by formula (V) with a dual nucleophile having two reaction sites, and the compound represented by formula (VI) can be prepared; Condensation reaction occurs between the dual nucleophiles at 4 reaction sites, and the compounds represented by formulas (VIII) and (IX) can be prepared.
  • the above-mentioned dual nucleophile is o-phthalonitrile, o-phenylenediamine, 1,2,4,5-tetraethylcyanobenzene or 1,2,4,5-tetraaminobenzene.
  • 1,2,4,5-tetraaminobenzene may be provided in the form of hydrochloride.
  • the above-mentioned contact is carried out in a fifth solvent
  • the fifth solvent may include selected from methanol, tetrahydrofuran, N,N-dimethylformamide ethanol, n-propanol, isopropanol, tert-butyl
  • At least one of the alcohols is preferably a mixed solvent of methanol and N,N-dimethylformamide ethanol in a volume ratio of 1:1.
  • the above-mentioned contact can be completed at 0-120°C for 0.1-96h.
  • the temperature may be 0°C, 35°C, 60°C, 100°C, 120°C, etc.
  • the time may be 0.1h, 1h, 12h, 24h, 48h, 72h, 96h, etc.
  • the above-mentioned contact is carried out at 35°C, whereby there are fewer side reactions and a higher reaction yield.
  • the dosage ratio of the compound represented by formula (I) to the amphinucleophile can be 1 mmol: (1-100) mmol.
  • the dosage ratio of the compound represented by the formula (I) to the dual nucleophile is 1 mmol:(2-8) mmol. Under this ratio, the reaction is fast, the system is clean, and the post-processing is convenient.
  • the preparation method of the compound represented by formula (VII) includes: contacting the compound represented by formula (VI) with a second oxidant to obtain the compound represented by formula (VII),
  • R 4 , Ar 1 , R 5 , and Ar 2 are as described above.
  • the above-mentioned second oxidant may include selected from benzoselenite anhydride, selenium dioxide, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachlorobenzene At least one of the quinone and iodine is preferably benzoselenous acid anhydride.
  • the above-mentioned contact is performed in a sixth solvent
  • the sixth solvent may include at least one selected from the group consisting of chlorobenzene, fluorobenzene, bromobenzene, and chloroform, preferably chloroform.
  • the above-mentioned contact can be completed at -40 to 150°C for 0.1 to 96 hours; specifically, the temperature can be -40°C, -20°C, 0°C, 20°C, 50°C, 80°C, 100°C. °C, 150°C, etc., the time can be 0.1h, 1h, 12h, 24h, 48h, 72h, 96h, etc. Preferably, the above-mentioned contact is performed at 140°C, whereby the reaction rate is faster and the yield is higher.
  • the amount ratio of the compound represented by formula (I) to the second oxidant may be 1 mmol: (1-100) mmol, preferably 1 mmol: (6-8) mmol. As a result, the reaction rate is faster and the yield is higher.
  • the present disclosure proposes the use of the compounds of the above-mentioned embodiments in the selective inclusion of organic molecules, and the compounds are used to identify and selectively include organic molecules from a mixed solution.
  • the compounds of the foregoing embodiments can be used as macrocyclic host molecules to selectively recognize and include small organic molecules, thereby being applied to the separation of small organic molecules.
  • Figure 1 is the hydrogen nuclear magnetic spectrum of the compound represented by formula (Ia);
  • Figure 2 is the NMR spectrum of the compound represented by formula (Ia);
  • FIG. 3 is a diagram of the crystal structure of the compound represented by formula (Ia);
  • FIG 4 is the hydrogen nuclear magnetic spectrum of the compound represented by formula (Id);
  • FIG. 5 is a nuclear magnetic carbon spectrum of the compound represented by formula (Id);
  • Figure 6 is a diagram of the crystal structure of the compound represented by formula (Id);
  • FIG. 7 is a hydrogen nuclear magnetic spectrum of the compound represented by formula (Vd);
  • FIG 8 is a nuclear magnetic carbon spectrum of the compound represented by formula (Vd);
  • FIG. 9 is a single crystal structure diagram of the compound represented by formula (Vd);
  • FIG 10 is a hydrogen nuclear magnetic spectrum of the compound represented by formula (VIe);
  • FIG 11 is a nuclear magnetic carbon spectrum of the compound represented by formula (VIe);
  • FIG 12 is a single crystal structure diagram of the compound represented by formula (VIe);
  • Figure 13 is a hydrogen nuclear magnetic spectrum of the compound represented by formula (IX);
  • Figure 14 is a single crystal structure diagram of the compound represented by formula (IX);
  • FIG. 15 is a structure diagram of a single crystal structure of a 1:1 inclusion compound formed by the compound represented by formula (Ib) and the guest molecule acetonitrile and chloroform;
  • Figure 16 is a single crystal structure diagram of the compound represented by formula (X2).
  • the specific preparation method is: in a 500mL three-necked flask, add 10mmol (4.9g) of methylene bridged calix[4] Rexarene, after pumping three times, add 250mL of dry dichloroethane and 160mmol (12.9 mL), after stirring uniformly, slowly add 120mmol of trifluoromethanesulfonic anhydride (20.1mL), and stir at 50°C for 24h. Then it was poured into 250 mL of 2M hydrochloric acid aqueous solution for quenching, the organic phase was retained, and the aqueous phase was extracted twice with 200 mL of dichloromethane.
  • the specific preparation method is: in a 500mL three-necked flask, add 10mmol (6.6g) of propyl calix[4] Rexarene, extract three times, add 250mL of dry dichloroethane and 160mmol (12.9mL) of pyridine, stir After uniformity, 120mmol of trifluoromethanesulfonic anhydride (20.1mL) was slowly added, and the mixture was stirred at 50°C for 24h. Then it was poured into 250 mL of 2M aqueous hydrochloric acid for quenching, the organic phase was retained, and the aqueous phase was extracted twice with 200 mL of dichloromethane.
  • the specific preparation method is: add 10mmol (8.5g) benzyl calix[4] Rexarene in a 500mL three-necked flask, after pumping three times, add 250mL of dry dichloroethane and 160mmol (12.9mL) of pyridine, stir After uniformity, 120mmol of trifluoromethanesulfonic anhydride (20.1mL) was slowly added, and the mixture was stirred at 50°C for 24h. Then it was poured into 250 mL of 2M hydrochloric acid aqueous solution for quenching, the organic phase was retained, and the aqueous phase was extracted twice with 200 mL of dichloromethane.
  • the specific preparation method is: add 5mmol (4.5g) of the compound represented by formula (IVd) into a 1L three-necked flask, extract 3 times, and then add 500mL of dry 1,2-dichloroethane, 120mmol (9.7mL) Dry pyridine, 90mmol (15.1mL) trifluoromethanesulfonic anhydride (added slowly), reflux for 24h. After cooling to room temperature, it was poured into 500 mL of 2M hydrochloric acid-saturated sodium chloride aqueous solution for extraction.
  • the specific derivatization method is: take 0.1mmol (46mg) of the compound represented by formula (Ia) and 10% rhodium carbon equivalent to 5% of its mass, place it in a 10mL Shrek tube, add 5mL formic acid, and extract 5-6 times. After the hydrogen atmosphere, use a hydrogen balloon to maintain the hydrogen atmosphere. After that, it was magnetically stirred at 50°C for 48 hours, cooled to room temperature and released hydrogen, filtered to remove palladium-carbon, and retained the filtrate. The filter cake was washed 3 times with 10 mL of dichloromethane and combined into the filtrate.
  • the specific derivatization method is: take 0.1mmol (62mg) of the compound represented by formula (Ib) and 10% rhodium carbon equivalent to 5% of its mass, place it in a 10mL Shrek tube, add 5mL formic acid, and extract 5-6 times. After the hydrogen atmosphere, use a hydrogen balloon to maintain the hydrogen atmosphere. After that, it was magnetically stirred at 50°C for 48 hours, cooled to room temperature and released hydrogen, filtered to remove palladium-carbon, and retained the filtrate. The filter cake was washed 3 times with 10 mL of dichloromethane and combined into the filtrate.
  • the combined organic phase was washed successively with 30 mL saturated brine, 30 mL saturated sodium carbonate solution and 30 mL saturated brine, dried over sodium sulfate, and spin-dried.
  • the specific preparation method is: add 2.0mmol (912mg) of the compound represented by formula (Ia), 4.0mmol (1.44g) benzoselenite anhydride (BSA), and 8mL chlorobenzene into a 50mL dry Shrek bottle, 120°C oil bath Under heating and magnetic stirring for 24h, it can be observed that the system changes from a white turbid liquid to a yellow solution.
  • BSA benzoselenite anhydride
  • 8mL chlorobenzene After cooling to room temperature, spin dry, dissolve with 100ml of dichloromethane, add 230-400 mesh silica gel, spin dry to prepare samples.
  • the stationary phase is 230-400 mesh silica gel, and the mobile phase is from pure petroleum ether to dichloromethane, and column chromatography is performed to separate and purify the compound. 594 mg of the compound shown in (Va) can be obtained as a yellow powder solid with a yield of 61%.
  • the specific preparation method is: add 2.0mmol (912mg) of the compound represented by formula (Ia), 8.0mmol (2.88g) benzoselenite anhydride (BSA), and 12mL of chlorobenzene, 120°C oil bath into a 50mL dry slater bottle Under heating and magnetic stirring for 10 hours, it can be observed that the system changes from a white turbid liquid to a yellow turbid liquid. After cooling to room temperature, spin dry, dissolve with 100ml of dichloromethane, add 230-400 mesh silica gel, spin dry to prepare samples.
  • BSA benzoselenite anhydride
  • the stationary phase is 230-400 mesh silica gel
  • column chromatography is carried out to separate and purify, and a mixture of formula (Vb) and (Vc) compounds can be obtained.
  • the indicated compound is 413 mg, a yellow powdery solid, and the yield is 40%.
  • the specific preparation method is: add 2.0mmol (912mg) of the compound represented by formula (Ia), 12.0mmol (4.32g) benzoselenite anhydride (BSA), and 14mL of chlorobenzene to 50mL dry three mouthpieces, heated in an oil bath at 120°C After 3 days of magnetic stirring reaction, it can be observed that the system changes from a white turbid liquid to a yellow solution. After cooling to room temperature, spin dry, dissolve with 300ml of dichloromethane, add 230-400 mesh silica gel, spin dry to prepare samples.
  • BSA benzoselenite anhydride
  • the stationary phase is 230-400 mesh silica gel
  • column chromatography is carried out to separate and purify to obtain 547 mg of the compound represented by formula (Vd) as a yellow powdery solid.
  • the rate is 50%
  • the hydrogen nuclear magnetic spectrum is shown in Figure 7
  • the nuclear magnetic carbon spectrum is shown in Figure 8, and the crystal structure is shown in Figure 9.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane for three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50mL of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the compound represented by formula (VIa) can be obtained 1.067mg in the form of light yellow powder. Solid, the yield is 88%.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50ml of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the compound represented by formula (VIb) can be obtained 934mg as a pale yellow powdery solid. , The yield is 62%.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane for three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50mL of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the compound represented by formula (VIc) can be obtained 934mg, a pale yellow powdery solid. , The yield is 62%.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50ml of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the compound represented by formula (VId) can be obtained 671mg as a white powdery solid. The yield was 37%.
  • the specific preparation method is: add 1.0mmol (757mg) of the compound represented by formula (VIb), 8.0mmol (2.88g) benzoselenite anhydride (BSA), and 12mL of chlorobenzene into a 50mL dry slater flask, and stir magnetically under reflux After 10 days of reaction, it can be observed that the system changes from a white turbid liquid to a yellow turbid liquid. After cooling to room temperature, spin dry, dissolve with 100 mL of dichloromethane, add 230-400 mesh silica gel, spin dry to prepare samples.
  • the stationary phase is 230-400 mesh silica gel
  • column chromatography is carried out for separation and purification, and 433 mg of the compound represented by formula (VIIa) can be obtained as a yellow powdery solid.
  • the yield was 53%.
  • the specific preparation method is: add 1.0mmol (757mg) of the compound represented by formula (VIc), 8.0mmol (2.88g) benzoselenite anhydride (BSA), and 12mL chlorobenzene into a 50mL dry slater flask, and stir magnetically under reflux After 10 days of reaction, it can be observed that the system changes from a white turbid liquid to a yellow turbid liquid. After cooling to room temperature, spin dry, dissolve with 100 mL of dichloromethane, add 230-400 mesh silica gel, spin dry to prepare samples.
  • VIc the compound represented by formula (VIc)
  • BSA benzoselenite anhydride
  • the stationary phase is 230-400 mesh silica gel
  • column chromatography is carried out to separate and purify, and 424 mg of the compound represented by formula (VIIb) can be obtained as a yellow powdery solid.
  • the yield was 52%.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane for three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50mL of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the stationary phase is 230-400 mesh silica gel
  • column chromatography is carried out to separate and purify to obtain 634 mg of the compound represented by formula (VIe) as a white powdery solid
  • the yield is 60%
  • the hydrogen nuclear magnetic spectrum is shown in Figure 10
  • the nuclear magnetic carbon spectrum is shown in Figure 11
  • the crystal structure is shown in Figure 12.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane for three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50mL of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the stationary phase is 230-400 mesh silica gel
  • column chromatography is carried out to separate and purify to obtain 634 mg of the compound represented by formula (VIe) as a white powdery solid , The yield is 60%.
  • the specific preparation method is: add 1.0mmol (487mg) of the compound represented by formula (Va), 1.1mmol (119mg) o-phenylenediamine, 0.11mmol (17mg) p-toluenesulfonic acid (p- TSA), evacuate three times and replace with nitrogen atmosphere, then add 20mL dry chloroform, stir the reaction under reflux for 12h, cool to room temperature, spin-dry by rotary evaporator, dissolve with 50mL dichloromethane, add 230-400 mesh silica gel, spin-dry sample.
  • 536mg of the compound represented by formula (VIf) can be obtained as a white powdery solid. The yield was 96%.
  • the specific preparation method is: add 1.0mmol (517mg) of the compound represented by formula (Vb), 2.2mmol (238mg) o-phenylenediamine, 0.22mmol (38mg) p-toluenesulfonic acid, and drain into a 50mL two-necked round bottom flask. Replace it with nitrogen atmosphere three times, then add 20mL dry chloroform, stir the reaction under reflux for 12h, cool to room temperature, spin dry with a rotary evaporator, dissolve with 50mL dichloromethane, add 230-400 mesh silica gel, spin dry to prepare samples.
  • ethyl acetate 50:1.
  • the specific preparation method is: add 1.0mmol (517mg) of the compound represented by formula (Vc), 2.2mmol (238mg) o-phenylenediamine, 0.22mmol (38mg) p-toluenesulfonic acid (p- TSA), evacuate three times and replace with nitrogen atmosphere, then add 20mL dry chloroform, stir the reaction under reflux for 12h, cool to room temperature, spin-dry by rotary evaporator, dissolve with 50mL dichloromethane, add 230-400 mesh silica gel, spin-dry sample.
  • After column chromatography is carried out for separation and purification, 621 mg of the compound represented by formula (VIg) can be obtained as a white powdery solid. The yield was 94%.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane for three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50mL of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the compound represented by formula (VIII) can be obtained 353mg, orange powdery solid , The yield is 46%.
  • the specific preparation method is: add 1.0mmol (487mg) of the compound represented by formula (Va), 0.5mmol (113mg) 1,2,4,5-tetraaminobenzene tetrahydrochloride into a 100mL two-necked round bottom flask, and then add 30mL Ethanol and 0.1 mL of concentrated hydrochloric acid were stirred for 2 days under reflux with magnetic stirring. After cooling to room temperature, 10 mL of saturated sodium bicarbonate solution was added to quench the reaction.
  • Extract with 50mL of dichloromethane and 50mL of saturated brine wash the aqueous phase with dichloromethane for three times, combine the organic phases, dry with anhydrous sodium sulfate, spin-dry by rotary evaporator, dissolve with 50mL of dichloromethane, and add 230-400 mesh silica gel , Spin-dry sample preparation.
  • the yield is 43%, the proton nuclear magnetic spectrum is shown in Fig. 13, and the crystal structure is shown in Fig. 14.
  • the specific preparation method is: add 0.2mmol (97.3mg) of the compound represented by formula (Va) and 0.22mmol (97.4mg) of the compound represented by formula (P) into a 50mL dry two-necked round bottom flask, extract three times, and replace with N 2 Atmosphere, add 10 mL of dry tetrahydrofuran and 5 mL of dry methanol solution, add 3.5 ⁇ L of 5% (w/v) KOH methanol solution dropwise under stirring, and transfer to 60° C. oil bath for 6 hours after the addition.
  • the specific preparation method is: add 0.2mmol (178.6mg) of the compound represented by formula (X1), 0.2mmol (47.6mg) 1,2-bis(4-methoxyphenyl)acetylene into a 25mL dry Slater bottle, and pump Arrange three times, replace with N 2 atmosphere, add 1 mL of dry diphenyl ether and reflux overnight. After the reaction is complete, spin to dry on a rotary evaporator, dissolve with 25 mL of dichloromethane, add 230-400 mesh silica gel, and spin to dry to prepare samples.
  • the stationary phase is 230-400 mesh silica gel
  • the mobile phase petroleum ether: ethyl acetate 5:1 for column chromatography separation and purification
  • the compound represented by formula (X2) can be obtained 139mg, a white powdery solid, the yield is 63%, its crystals
  • the structure is shown in Figure 16.
  • Example 25 Selective inclusion of acetonitrile and chloroform by the compound represented by the macrocyclic formula (Ib)

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Abstract

本公开提供了环带[n]芳烃[n]䓬烯、环带[4]芳烃[4]䓬类化合物、环带[4]芳烃[4-m]䓬烯[m]二羰基化合物、环带[4]芳烃[4-m]䓬烯[m]苯并䓬烯化合物、环带[4]芳烃[4-m]苯并䓬烯[m]二羰基化合物及其制备方法和用途。其中，环带[n]芳烃[n]䓬烯类化合物具有如式（I）所示的结构。

Description

环带芳烃䓬类化合物及其制备方法和用途
优先权信息
本公开请求于2019年12月16日向中国国家知识产权局提交的、专利申请号为201911292912.X、申请名称为“环带芳烃
Figure PCTCN2020117641-appb-000002
类化合物及其制备方法和用途”的中国专利申请的优先权，并且其全部内容通过引用结合在本公开中。
技术领域
本公开涉及有机化学领域，具体而言，本公开涉及环带[n]芳烃[n]
Figure PCTCN2020117641-appb-000003
烯、环带[4]芳烃[4]
Figure PCTCN2020117641-appb-000004
类化合物、环带[4]芳烃[4-m]
Figure PCTCN2020117641-appb-000005
烯[m]二羰基化合物、环带[4]芳烃[4-m]
Figure PCTCN2020117641-appb-000006
烯[m]苯并
Figure PCTCN2020117641-appb-000007
烯化合物、环带[4]芳烃[4-m]苯并
Figure PCTCN2020117641-appb-000008
烯[m]二羰基化合物及其制备方法和用途。
背景技术
人工合成大环化合物具有良好的分子结构可设计性以及理化性能可调节性的特点和优势，在化学、材料科学和生命科学诸多领域得到广泛应用。作为主体化合物，人工合成的大环化合物能识别阴阳离子和中性客体分子，从而应用于分离、传感和检测。作为基元或模板，官能团化大环化合物用于功能组装体和纳米材料和分子机器的构建。大环化合物还为探究化学反应机理和超分子催化提供了独特的研究手段和途径。
迄今为止，文献中已经报道了大量的人工合成大环化合物，其中冠醚、球醚、化学修饰的环糊精衍生物、杯芳烃、杯雷琐芳烃、环三藜芦烃、杯吡咯、葫芦脲、杂杯芳烃、环对苯撑(CPPs)、柱芳烃、冠芳烃等正成为优势大环主体分子，得到比较深入和广泛的研究。由于不同的大环化合物具有不同的结构，其空腔大小、形状及电子特性均有差异，从而显示不一样的分子识别能力。因而，对于具有新结构和功能的大环化合物仍有待深入研究。
公开内容
本公开旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本公开的一个目的在于提出环带芳烃
Figure PCTCN2020117641-appb-000009
类化合物及其制备方法和用途。该类化合物具有桶状空腔结构、空腔体积尺寸可变、空腔内壁极性可调，具有广阔的应用前景。
在本公开的一个方面，本公开提出了一种化合物。根据本公开的实施例，为式(I)所示化合物或式(I)所示化合物的立体异构体，
Figure PCTCN2020117641-appb-000010
其中，
n为4或6；
R 1为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的 C 5-24环烷基或任选取代的C 5-24杂环基。
式(I)所示化合物也称为环带[n]芳烃[n]
Figure PCTCN2020117641-appb-000011
烯(n＝4,6)类化合物。该类化合物具有桶状空腔结构、空腔体积尺寸可变、空腔内壁极性可调。作为新型的人工合成大环分子，够从混合溶液中选择性识别有机分子，并与其形成包结复合物，应用于有机小分子的选择性分离材料；该类化合物有较好的荧光特性，可应用于有机光电材料的制备；另外该类化合物还可以用于“自下而上”合成策略合成碳纳米环等异性碳纳米管的前驱体。
另外，根据本公开上述实施例的化合物还可以具有如下附加的技术特征：
在本公开的一些实施例中，R 1为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
在本公开的一些实施例中，R 1为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，该化合物具有以下其中之一的结构：
Figure PCTCN2020117641-appb-000012
在本公开的另一方面，本公开提出了一种化合物。根据本公开的实施例，该化合物为式(II)所示化合物或式(II)所示化合物的立体异构体，
Figure PCTCN2020117641-appb-000013
其中，
n为4或6；
R 2为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基。
式(II)所示化合物也称为环带[n]芳烃[n]
Figure PCTCN2020117641-appb-000014
类化合物(n＝4,6)类化合物。该类化合物具有桶状空腔结构、空腔体积尺寸可变、空腔内壁极性可调。作为新型的人工合成大环分子，能够从混合溶液中选择性识别有机分子，并与其形成包结复合物，应用于有机小分子的选择性分离材料；该类化合物有较好的荧光特性，可应用于有机光电材料的制备；另外该类化合物还可以用于“自下而上”合成策略合成碳纳米环等异性碳纳米管的前驱体。
另外，根据本公开上述实施例的化合物还可以具有如下附加的技术特征：
在本公开的一些实施例中，R 2为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环 烷基。
在本公开的一些实施例中，n为4；R 2为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，该化合物具有以下其中之一的结构：
Figure PCTCN2020117641-appb-000015
在本公开的另一方面，本公开提出了一种化合物。根据本公开的实施例，该化合物为式(V)所示化合物或式(V)所示化合物的立体异构体，
Figure PCTCN2020117641-appb-000016
其中，
n为1、2或3，m和m’分别独立地为1、2、3或4；
R 3为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基。
式(V)所示化合物也称为环带[4]芳烃[4-m]
Figure PCTCN2020117641-appb-000017
烯[m]二羰基化合物。该类化合物具有桶状空腔结构、空腔体积尺寸可变、空腔内壁极性可调。作为新型的人工合成大环分子，能够从混合溶液中选择性识别有机分子，并与其形成包结复合物，应用于有机小分子的选择性分离材料；该类化合物有较好的荧光特性，可应用于有机光电材料的制备；另外该类化合物还可以用于“自下而上”合成策略合成碳纳米环等异性碳纳米管的前驱体。
另外，根据本公开上述实施例的化合物还可以具有如下附加的技术特征：
在本公开的一些实施例中，n为1、2或3，m和m’分别独立地为1、2、3或4；R 3为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基。
在本公开的一些实施例中，R 3为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
在本公开的一些实施例中，n＝1、m＝1、m’＝3，R 3为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝1、m＝3、m’＝1，R 3为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝1、m＝2、m’＝2，R 3为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝2、m＝1、m’＝1，R 3为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝2、m＝0、m’＝2，R 3为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，该化合物具有以下其中之一的结构：
Figure PCTCN2020117641-appb-000018
在本公开的另一方面，本公开提出了一种化合物。根据本公开的实施例，该化合物式(VI)所示化合物、式(VIII)所示化合物或式(IX)所示化合物，或其立体异构体，
Figure PCTCN2020117641-appb-000019
其中，
n为1、2或3，m和m’分别独立地为1、2、3或4；
R 4为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基；
Ar 1为
Figure PCTCN2020117641-appb-000020
X为N或C-CN。
需要说明的是，Ar 1在式(VI)所示结构中的具体连接位置为Ar 1中
Figure PCTCN2020117641-appb-000021
的2位和3位与母体形成并环。
式(VI)所示化合物、式(VIII)所示化合物或式(IX)所示化合物也称为环带[4]芳烃[4-m]
Figure PCTCN2020117641-appb-000022
烯[m]苯并
Figure PCTCN2020117641-appb-000023
烯化合物。该类化合物具有桶状空腔结构、空腔体积尺寸可变、空腔内壁极性可调。作为新型的人工合成大环分子，能够从混合溶液中选择性识别有机分子，并与其形成包结复合物，应用于有机小分子的选择性分离材料；该类化合物有较好的荧光特性，可应用于有机光电材料的制备；另外该类化合物还可以用于“自下而上”合成策略合成碳纳米环等异性碳纳米管的前驱体。
另外，根据本公开上述实施例的化合物还可以具有如下附加的技术特征：
在本公开的一些实施例中，R 4为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
在本公开的一些实施例中，n＝1、m＝1、m’＝3；R 4为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝1、m＝3、m’＝1；R 4为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝1、m＝2、m’＝2；R 4为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝2、m＝1、m’＝1；R 4为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝2、m＝0、m’＝2；R 4为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，该化合物具有以下其中之一的结构：
Figure PCTCN2020117641-appb-000024
Figure PCTCN2020117641-appb-000025
在本公开的另一方面，本公开提出了一种化合物。根据本公开的实施例，该化合物为式(VII)所示化合物或式(VII)所示化合物的立体异构体，
Figure PCTCN2020117641-appb-000026
其中，
n、m和m’分别独立地为1、2、3、或4；
R 5为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基；
Ar 2为
Figure PCTCN2020117641-appb-000027
X为N或C-CN。
需要说明的是，Ar 2在式(VII)所示结构中的具体连接位置为Ar 2中
Figure PCTCN2020117641-appb-000028
的2位和3位与母体形成并环。
式(VII)所示化合物也称为环带[4]芳烃[4-m]苯并
Figure PCTCN2020117641-appb-000029
烯[m]二羰基化合物。该类化合物具有桶状空腔结构、空腔体积尺寸可变、空腔内壁极性可调。作为新型的人工合成大环分子，能够从混合溶液中选择性识别有机分子，并与其形成包结复合物，应用于有机小分子的选择性分离材料；该类化合物有较好的荧光特性，可应用于有机光电材料的制备；另外该类化合物还可以用于“自下而上”合成策略合成碳纳米环等异性碳纳米管的前驱体。
另外，根据本公开上述实施例的化合物还可以具有如下附加的技术特征：
在本公开的一些实施例中，R 5为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
在本公开的一些实施例中，n＝1、m＝1、m’＝3，R 5为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，n＝2、m＝1、m’＝1，R 5为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
在本公开的一些实施例中，该化合物具有以下其中之一的结构：
Figure PCTCN2020117641-appb-000030
在本公开的另一方面，本公开提出了一种制备上述化合物的方法。具体包括制备(I)所示化合物、式(II)所示化合物、式(V)所示化合物、式(VI)所示化合物、式(VII)所示化合物、式(VIII)所示化合物、式(IX)所示化合物的方法。
根据本公开的实施例，制备式(I)所示化合物的方法包括：使式(III)所示化合物在格拉布斯催化剂存在条件下发生分子内烯烃关环复分解反应，得到式(I)所示化合物，
Figure PCTCN2020117641-appb-000031
其中，R 1为如前所述。
根据本公开是实施例，式(III)所示化合物可在格拉布斯(Grubbs)催化剂作用下发生分子内烯烃关环复分解反应，得到式(I)所示化合物，反应条件温和，所得产物在空气中稳定且易于分离纯化，具有很好的实用性和应用前景。
根据本公开的实施例，上述格拉布斯催化剂包括选自格拉布斯(Grubbs)I代催化剂、格拉布斯(Grubbs)II代催化剂、格拉布斯(Grubbs)III代催化剂、格拉布斯-霍维达(Grubbs-Hoveyda)催化剂、史洛克(Schrock)催化剂中的至少之一。由此可进一步提高产品的产率和选择性。其中，格拉布斯(Grubbs)III代催化剂可参考文献Immobilisation of the Grubbs III Olefin Metathesis Catalyst with Polyvinyl Pyridine(PVP)，Synlett 2005,No.19,2948–2952获得。
根据本公开的实施例，上述接触在第一溶剂中进行，所述第一溶剂可以包括选自二氯甲烷、三氯甲烷、四氯化碳、1,2-二氯乙烷、1,1,2,2-四氯乙烷、苯、甲苯、三氟甲苯、氯苯、氟苯、硝基苯、溴苯、邻二甲苯，间二甲苯，对二甲苯和四氢萘中的至少之一；根据本公开的优选实施例，第一溶剂优选为二氯甲烷。由此，可以为原料提供良好的溶解性。
根据本公开的实施例，上述接触可以在-40～150℃下进行0.1～96h完成，优选在40～120℃下进行24～96h完成。由此，可以进一步提高产品的产率和选择性。
根据本公开的实施例，上述式(III)所示化合物与格拉布斯催化剂的用量比可以为0.01～1mmol:0.01～100mmol，优选为0.1～1mmol:1～10mmol。由此，可以进一步提高产品的产率和选择性。
根据本公开的实施例，式(III)所示化合物通过使式(IV)所示化合物在金属催化剂的作用下发生交叉偶 联反应制备得到，
Figure PCTCN2020117641-appb-000032
根据本公开的实施例，上述金属催化剂可以包括选自醋酸钯、四三苯基膦钯、三(二亚苄基丙酮)二钯、氯化钯和[1,1’-双(二苯基膦基)二茂铁]二氯化钯、乙酰丙酮镍、二(1,5-环辛二烯)镍、1,3-双(二苯基膦基)乙烷二氯化镍、1,3-双(二苯基膦基)丙烷二氯化镍、1,3-双(二苯基膦基)丁烷二氯化镍、1,3-双(二苯基膦基)二茂铁二氯化镍中的至少之一，优选为1,3-双(二苯基膦基)乙烷二氯化镍。由此，可以获得更佳的产率。
根据本公开的实施例，上交叉偶联反应在第二溶剂中进行，所述第二溶剂可以包括选自N,N-二甲基甲酰胺、N,N-二甲基苯胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃、1,4-二氧六环、水和二甲基亚砜中的至少之一，优选为N,N-二甲基甲酰胺。由此，可以获得更佳的产率。
根据本公开的实施例，上述交叉偶联反应在添加剂和烯基化试剂的作用下进行，添加剂可以包括选自碳酸钾、碳酸铯、碳酸锂、碳酸钠、氯化钠和氯化锂中的至少之一；烯基化试剂可以包括选自乙烯基溴化镁、异丙烯基溴化镁、三丁基乙烯基烯、三丁基异丙烯基烯、异丙烯基硼酸频哪醇酯和乙烯基硼酸频哪醇酯中的至少之一；优选的添加剂为氯化锂，优选的烯基化试剂为三丁基乙烯基锡。由此，可以获得更佳的产率。
根据本公开的实施例，上述交叉偶联反应可以在0～140℃下进行6～72h完成，具体的，反应温度可以为0℃、20℃、40℃、90℃、120℃、140℃等，反应时间可以为6h、12h、24h、36h、72h等。优选地，交叉偶联反应在90℃下进行24h完成。由此，可以获得更佳的产率。
根据本公开的实施例，制备式(II)所示化合物的方法包括：使式(I)所示化合物与还原催化剂和氢气接触，得到式(II)所示化合物。
Figure PCTCN2020117641-appb-000033
其中，R 1、R 2为如前所述的。
根据本公开的实施例，上述还原催化剂可以包括选自铂黑、二氧化铂、钯黑、钯炭、铂炭、铑炭、钌碳中的至少之一，优选为铑炭。由此，可以获得更佳的产率。
根据本公开的实施例，上述接触在第三溶剂中进行，所述第三溶剂可以包括选自甲醇、乙醇、正丙醇、异丙醇、叔丁醇、甲酸、乙酸、丙酸中的至少之一，优选为甲酸。由此，可以获得更佳的产率。
根据本公开的实施例，上述接触在1～1000atm氢气气氛中进行；具体的，氢气压力可以为1atm、20atm、100atm、500atm、800atm、1000atm等，优选为，1atm。由此，可以获得更佳的产率。
根据本公开的实施例，上述接触在-40～150℃下进行0.1～96h完成，具体的，温度可以为-40℃、-20℃、0℃、20℃、50℃、80℃、100℃、150℃等，时间可以为0.1h、1h、12h、24h、48h、72h、96h等。优选地，上述接触在50℃下进行48h完成。由此，可以获得更佳的产率。
根据本公开的实施例，式(I)所示化合物与还原催化剂的用量比可以为0.01～1mmol:0.01～100mmol，具体的，式(I)所示化合物的用量可以为0.01mmol、0.05mmol、0.1mmol、0.2mmol、0.5mmol、1mmol等，还原催化剂的用量可以为0.01mmol、0.1mmol、0.2mmol、1mmol、5mmol、20mmol、40mmol、80mmol、100mmol等。优选地，式(I)所示化合物与还原催化剂的用量比为0.01mmol:0.2mmol。由此，可以获得更佳的产率。
根据本公开的实施例，制备式(V)所示化合物的方法包括：使式(I)所示化合物与第一氧化剂接触，得到式(V)所示化合物，
Figure PCTCN2020117641-appb-000034
其中，R 1、R 3为如前所述的。
根据本公开的实施例，上述第一氧化剂可以包括选自苯并亚硒酸酐、二氧化硒、2,3-二氯-5,6-二氰基-1,4-苯醌、四氯苯醌、碘单质的至少之一，优选为苯并亚硒酸酐，采用该氧化剂，可以进一步减少反应中生成的副产物，提高产物产率，且后处理方便。
根据本公开的实施例，上述接触在第四溶剂中进行，所述第四溶剂可以包括选自氯苯、氟苯、溴苯、氯仿中的至少之一，优选为氯仿，在该溶剂中进行反应产率更高，反应副产物更少。
根据本公开的实施例，上述接触可以在50～150℃下进行0.1～96h完成；具体的，温度可以为50℃、70℃、90℃、120℃、150℃等，时间可以为0.1h、1h、12h、24h、48h、72h、96h等。优选地，上述接触在120℃下进行，由此，反应速率更快，且产率更高。
根据本公开的实施例，式(I)所示化合物与第一氧化剂的用量比可以为0.01～1mmol:0.01～100mmol。具体的，式(I)所示化合物的用量可以为0.01mmol、0.05mmol、0.1mmol、0.2mmol、0.5mmol、1mmol等，第一氧化剂的用量可以为0.01mmol、0.1mmol、0.2mmol、1mmol、5mmol、20mmol、40mmol、80mmol、100mmol等。优选地，式(I)所示化合物与第一氧化剂的用量比为0.01mmol:0.2mmol。由此，可以获得更佳的产率。
根据本公开的实施例，式(VI)、(VIII)、(IX)所示化合物可以通过使式(V)所示化合物与双亲核试剂发生缩合反应制备得到。具体的，通过使式(V)所示化合物与具有2个反应位点的双亲核试剂发生缩合反应，可以制备得到式(VI)所示化合物；通过使使式(V)所示化合物与具有4个反应位点的双亲核试剂发生缩合反应，可以制备得到式(VIII)、(IX)所示化合物，
Figure PCTCN2020117641-appb-000035
根据本公开的实施例，上述双亲核试剂为邻苯二乙腈、邻苯二胺、1,2,4,5-四乙氰基苯或1,2,4,5-四氨基苯。在一些实施例中，1,2,4,5-四氨基苯可以以盐酸盐的形式提供。
根据本公开的实施例，上述接触在第五溶剂中进行，所述第五溶剂可以包括选自甲醇、四氢呋喃、N,N-二甲基甲酰胺乙醇、正丙醇、异丙醇、叔丁醇中的至少之一，优选为甲醇与N,N-二甲基甲酰胺乙醇体积比1:1的混合溶剂。由此，反应产率高，反应副产物少。
根据本公开的实施例，上述接触可以在0～120℃下进行0.1～96h完成，具体的，温度可以为0℃、35℃、60℃、100℃、120℃等，时间可以为0.1h、1h、12h、24h、48h、72h、96h等。优选地，上述接触在35℃下进行，由此，副反应更少，且反应产率更高。
根据本公开的实施例，式(I)所示化合物与双亲核试剂用量比可以为1mmol:(1～100)mmol。优选地，式(I)所示化合物与双亲核试剂用量比为1mmol:(2～8)mmol，该比例下，反应快，且体系干净，后处理方便。
根据本公开的实施例，式(VII)所示化合物的制备方法包括：使式(VI)所示化合物与第二氧化剂接触，得到式(VII)所示化合物，
Figure PCTCN2020117641-appb-000036
其中，R 4、Ar 1、R 5、Ar 2为如前所述。
根据本公开的实施例，上述第二氧化剂可以包括选自苯并亚硒酸酐、二氧化硒、2,3-二氯-5,6-二氰基-1,4-苯醌、四氯苯醌、碘单质的至少之一，优选为苯并亚硒酸酐，采用该氧化剂，可以进一步减少反应中生成的副产物，提高产物产率，且后处理方便。
根据本公开的实施例，上述接触在第六溶剂中进行，所述第六溶剂可以包括选自氯苯、氟苯、溴苯、氯仿中的至少之一，优选为氯仿。由此，可以减少反应中生成的副产物，提高产物产率。
根据本公开的实施例，上述接触可以在-40～150℃下进行0.1～96h完成；具体的，温度可以为-40℃、-20℃、0℃、20℃、50℃、80℃、100℃、150℃等，时间可以为0.1h、1h、12h、24h、48h、72h、96h等。优选地，上述接触在140℃下进行，由此，反应速率更快，且产率更高。
根据本公开的实施例，式(I)所示化合物与所述第二氧化剂的用量比可以为1mmol:(1～100)mmol，优选为1mmol:(6～8)mmol。由此，反应速率更快，且产率更高。
在本公开的另一方面，本公开提出了上述实施例的化合物在在对有机分子选择性包合中的用途，所述化合物用于从混合溶液中识别并选择性包合有机分子。上述实施例的化合物能够作为大环主体分子，选择性识别和包合有机小分子，从而应用于有机小分子的分离。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
本公开的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1为式(Ia)所示化合物的核磁氢谱；
图2为式(Ia)所示化合物的核磁碳谱；
图3为式(Ia)所示化合物的晶体结构图；
图4为式(Id)所示化合物的核磁氢谱；
图5为式(Id)所示化合物的核磁碳谱；
图6为式(Id)所示化合物的晶体结构图；
图7为式(Vd)所示化合物的核磁氢谱；
图8为式(Vd)所示化合物的核磁碳谱；
图9为式(Vd)所示化合物的单晶结构图；
图10为式(VIe)所示化合物的核磁氢谱；
图11为式(VIe)所示化合物的核磁碳谱；
图12为式(VIe)所示化合物的单晶结构图；
图13为式(IX)所示化合物的核磁氢谱；
图14为式(IX)所示化合物的单晶结构图；
图15为式(Ib)所示化合物与客体分子乙腈，氯仿形成1:1包合物结构单晶结构图；
图16为式(X2)所示化合物的单晶结构图。
具体实施方式
下面详细描述本公开的实施例。下面描述的实施例是示例性的，仅用于解释本公开，而不能理解为对本公开的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1：制备化合物(Ia)(对应式(I)中n为4；R 1为H)
反应式如下：
Figure PCTCN2020117641-appb-000037
具体制备方法是：在500mL的三口瓶中，加入10mmol(4.9g)亚甲基桥连的杯[4]雷索芳烃，抽排三次后，加入250mL干燥的二氯乙烷以及吡啶160mmol(12.9mL)，搅拌均匀后，缓慢加入三氟甲磺酸酐120mmol，(20.1mL)，50℃下搅拌24h。之后倒入250mL的2M盐酸水溶液中淬灭，保留有机相，水相用200mL二氯甲烷萃取两次。合并有机相，并用200mL饱和食盐水洗涤两次，饱和硫酸钠干燥后旋干。残余物为式(IVa)所示化合物粗产品7.7g，粗产率50％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IVa)所示化合物0.5mmol(0.77g)、1,3-双(二苯基膦基)乙烷氯化镍0.25g(0.5mmol)、氯化锂0.84g(20mmol)，再加入20mL重蒸无氧的N,N-二甲基甲酰胺(DMF)，氮气保护下在90℃磁力搅拌24h。待反应冷却到室温，倒入50mL饱和氟化钾溶液、50mL纯水和50mL二氯甲 烷的混合物中，激烈搅拌后过滤，保留有机相，水相则用50mL二氯甲烷萃取两次。合并有机相，并先用50mL饱和氟化钾溶液和50mL 30％过氧化氢混合溶液洗涤一次，再用50mL饱和氟化钾溶液和50mL纯水混合溶液洗涤两次，无水硫酸钠干燥后旋干，残余物在230-400目硅胶上，用纯石油醚到石油醚：二氯甲烷＝8:1的比例进行柱色谱分离，可得到式(IIIa)所示化合物粗产品57mg，粗产率20％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IIIa)所示化合物0.1mmol(57mg)，格拉布斯三代催化剂(Grubbs-III)0.01mmol(8.8mg)，再加入10mL干燥无氧的1,2-二氯乙烷，在氩气气球保护下回流搅拌24h。冷却到室温后旋干，残余物在230–400目硅胶上，用石油醚:二氯甲烷＝5:1的比例进行柱色谱分离，可得产物式(Ia)所示化合物36mg，产率80％，其核磁氢谱如图1，核磁碳谱如图2，晶体结构如图3所示。
1H NMR(400MHz,CDCl 3)δ6.90(s,4H),6.84(s,8H),6.76(s,4H),3.66(d,J＝11.5Hz,4H),3.42(d,J＝11.9Hz,4H；
13C NMR(100MHz,CDCl 3)δ140.1,131.8,130.0,124.8,122.3,39.9；
HRMS(MALDI-FT)calcd for C 36H 24:[M] +456.1873.Found:456.1873.
由上可知，上述化合物结构正确，为式(Ia)所示化合物。
式(IVa)所示化合物的合成参考文献：Y.Nakamoto et al.Networkpolymer.2002,23,134–141.
实施例2：制备化合物(Ib)(对应式(I)中n为4；R 1为n-Pr)
反应式如下：
Figure PCTCN2020117641-appb-000038
具体制备方法是：在500mL的三口瓶中，加入10mmol(6.6g)丙基杯[4]雷索芳烃，抽排三次后，加入250mL干燥的二氯乙烷以及吡啶160mmol(12.9mL)，搅拌均匀后，缓慢加入三氟甲磺酸酐120mmol，(20.1mL)，50℃下搅拌24h。之后倒入250mL的2M盐酸水溶液中淬灭，保留有机相，水相用200mL二氯甲烷萃取两次。合并有机相，并用200mL饱和食盐水洗涤两次，饱和硫酸钠干燥后旋干。残余物为式(IVb)所示化合物粗产品8.6g，粗产率50％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IVb)所示化合物0.5mmol(0.86g)、1,3-双(二苯基膦基)乙烷氯化镍0.25g(0.5 mmol)、氯化锂0.84g(20mmol)，再加入20mL重蒸无氧的N,N-二甲基甲酰胺(DMF)，氮气保护下在90℃磁力搅拌24h。待反应冷却到室温，倒入50mL饱和氟化钾溶液、50mL纯水和50mL二氯甲烷的混合物中，激烈搅拌后过滤，保留有机相，水相则用50mL二氯甲烷萃取两次。合并有机相，并先用50mL饱和氟化钾溶液和50mL 30％过氧化氢混合溶液洗涤一次，再用50mL饱和氟化钾溶液和50mL纯水混合溶液洗涤两次，无水硫酸钠干燥后旋干，残余物在230-400目硅胶上，用纯石油醚到石油醚：二氯甲烷＝8:1的比例进行柱色谱分离，可得到式(IIIb)所示化合物粗产品74mg，粗产率20％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IIIb)所示化合物0.1mmol(74mg)，格拉布斯三代催化剂0.01mmol(8.8mg)，再加入10mL干燥无氧的1,2-二氯乙烷，在氩气气球保护下回流搅拌24h。冷却到室温后旋干，残余物在230–400目硅胶上，用石油醚:二氯甲烷＝5:1的比例进行柱色谱分离，可得产物式(Ib)所示化合物50mg，产率80％。
1H NMR(400MHz,CDCl 3)δ6.89(s,4H),6.85(s,8H),6.78(s,4H),3.14(t,J＝7.8Hz,4H),2.43(q,J＝7.6Hz,8H),1.58–1.54(m,8H),1.12(t,J＝7.3Hz,12H)；
13C NMR(100MHz,CDCl 3)δ142.2,131.8,129.8,124.3,113.3,43.2,30.0,20.9,14.5；
HRMS(MALDI-FT)calcd for C 48H 48:[M] +624.3751.Found:624.3744.
由上可知，上述化合物结构正确，为式(Ib)所示化合物。
式(IVb)所示化合物的合成参考文献：L.M.Tunstad,J.A.Tucker,D.Dalcanale,J.Weiser,J.A.Bryant,J.C.Sherman,R.C.Helgeson,C.B.Knobler,D.J.Cram,J.Org.Chem.1989,54,1305.
实施例3：制备化合物(Ic)(对应式(I)中n为4；R 1为Bn)
反应式如下：
Figure PCTCN2020117641-appb-000039
具体制备方法是：在500mL的三口瓶中，加入10mmol(8.5g)苄基杯[4]雷索芳烃，抽排三次后，加入250mL干燥的二氯乙烷以及吡啶160mmol(12.9mL)，搅拌均匀后，缓慢加入三氟甲磺酸酐120mmol，(20.1mL)，50℃下搅拌24h。之后倒入250mL的2M盐酸水溶液中淬灭，保留有机相，水相用200mL二氯甲烷萃取两次。合并有机相，并用200mL饱和食盐水洗涤两次，饱和硫酸钠干燥后旋干。残余物为式(IVc)所示化合物粗产品9.5g，粗产率50％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IVc)所示化合物0.5mmol(0.95g)、1,3-双(二苯基膦基)乙烷氯化镍0.25g(0.5 mmol)、氯化锂0.84g(20mmol)，再加入20mL重蒸无氧的N,N-二甲基甲酰胺(DMF)，氮气保护下在90℃磁力搅拌24h。待反应冷却到室温，倒入50mL饱和氟化钾溶液、50mL纯水和50mL二氯甲烷的混合物中，激烈搅拌后过滤，保留有机相，水相则用50mL二氯甲烷萃取两次。合并有机相，并先用50mL饱和氟化钾溶液和50mL 30％过氧化氢混合溶液洗涤一次，再用50mL饱和氟化钾溶液和50mL纯水混合溶液洗涤两次，无水硫酸钠干燥后旋干，残余物在230-400目硅胶上，用纯石油醚到石油醚:二氯甲烷＝8:1的比例进行柱色谱分离，可得到式(IIIc)所示化合物粗产品92mg，粗产率20％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IIIc)所示化合物0.1mmol(92mg)，格拉布斯三代催化剂0.01mmol(8.8mg)，再加入10mL干燥无氧的1,2-二氯乙烷，在氩气气球保护下回流搅拌24h。冷却到室温后旋干，残余物在230–400目硅胶上，用石油醚：二氯甲烷＝5:1的比例进行柱色谱分离，可得产物式(Ic)所示化合物57mg，产率70％。
1H NMR(400MHz,CDCl 3)δ7.32-7.16(m,24H),6.87(s,8H),6.80(s,4H),3.92(d,J＝7.3Hz,8H),3.78(t,J＝7.3Hz,4H)；
13C NMR(100MHz,CDCl 3)141.7,140.0,131.8,130.0,129.0,128.4,126.0,124.6,113.8,44.5,33.9；
HRMS(MALDI-FT)calcd for C 64H 48:816.3751[M] +.Found:816.3744.
由上可知，上述化合物结构正确，为式(Ic)所示化合物。
式(IVc)所示化合物的合成参考文献：L.M.Tunstad,J.A.Tucker,D.Dalcanale,J.Weiser,J.A.Bryant,J.C.Sherman,R.C.Helgeson,C.B.Knobler,D.J.Cram,J.Org.Chem.1989,54,1305.
实施例4：制备化合物(Id)(对应式(I)中n为6，R 1为Et)
反应式如下：
Figure PCTCN2020117641-appb-000040
具体制备方法是：在1L的三口瓶中加入式(IVd)所示化合物5mmol(4.5g)，抽排3次，然后依次加入500mL干燥的1,2-二氯乙烷，120mmol(9.7mL)干燥的吡啶，90mmol(15.1mL)三氟甲磺酸酐(慢速加入)，回流24h。冷却到室温后，倒入500mL的2M盐酸-饱和氯化钠水溶液中萃取。保留有机相，水相则用200mL1,2-二氯乙烷洗涤两次，合并有机相，200mL用饱和食盐水洗涤两次(使氯化钠饱和为状态以便保证氟苯分相)，无水硫酸钠干燥后旋干。可得产物式(IVd)所示化合物粗产品7.7g，粗产率62％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式((IVd)所示化合物0.5mmol(1.24g)、1,3-双(二苯基膦基)乙烷氯化镍0.5mmol(0.27g)、氯化锂30mmol(1.26g)，再加入30mL重蒸无氧的N,N-二甲基甲酰胺(DMF)，氮气保护下在90℃磁力搅拌48h。待反应冷却到室温，倒入50mL饱和氟化钾溶液、50mL纯水和50mL二氯甲烷的混合物中，激烈搅拌后过滤，保留有机相，水相则用50mL二氯甲烷萃取两次。合并有机相，并先用50mL饱和氟化钾溶液和50mL 30％过氧化氢混合溶液洗涤一次，再用50mL饱和氟化钾溶液和50mL纯水混合溶液洗涤两次，无水硫酸钠干燥后旋干，残余物在230-400目硅胶上，用纯石油醚到石油醚：二氯甲烷＝8:1的比例进行柱色谱分离，可得到产物式(IIId)所示化合物粗产品102mg，粗产率20％。该粗产物无表征数据，可直接进行下一步反应。
在史莱克管中，加入式(IIId)所示化合物0.05mmol(51mg)，格拉布斯三代催化剂8.8mg(0.01mmol)，再加入10mL干燥无氧的二氯乙烷，在氩气气球保护下回流搅拌24h。冷却到室温后，旋干，残余物在230–400目硅胶上，用石油醚：二氯甲烷＝5:1的比例进行柱色谱分离，可得产物式(Id)所示化合物26 mg，产率60％，其核磁氢谱如图4，核磁碳谱如图5，晶体结构如图6所示。
1H NMR(400MHz,CDCl 3)δ7.16(s,6H),7.09(s,6H),6.97(s,6H),6.66(s,6H),3.86(t,J＝7.8Hz,3H),3.13(t,J＝7.8Hz,3H),2.55(p,J＝7.3Hz,6H),1.77(p,J＝7.5Hz,6H),1.16(t,J＝7.1Hz,9H),0.69(t,J＝7.3Hz,9H)；
13C NMR(100MHz,CDCl 3)140.7,139.7,133.6,131.0,130.6,129.8,129.1,125.4,57.2,45.4,29.7,24.2,22.3,12.8；
HRMS(MALDI-FT)calcd for C 66H 60:853.4768[M+H] +.Found:853.4768.
由上可知，上述化合物结构正确，为式(Id)所示化合物。
式(IVd)所示化合物的合成参考文献：B.W.Purse,A.Shivanyuk,J.Rebek Jr.Chem.Commun.2002,2612.
实施例5：化合物(Ia)衍生化(对应式(II)中n为4；R 2为H)
Figure PCTCN2020117641-appb-000041
具体衍生化方法是：取0.1mmol(46mg)式(Ia)所示化合物和相当其质量5％的10％铑炭，置于10mL史莱克管中，加入5mL甲酸，抽排5-6次换为氢气气氛后，用氢气球保持氢气气氛。之后在50℃磁力搅拌48h，冷却到室温后放掉氢气，过滤除去钯炭，保留滤液，滤饼用10mL二氯甲烷洗涤3次，合并到滤液中。合并后的有机相依次用30mL饱和食盐水，30mL饱和碳酸钠溶液和30mL饱和食盐水洗涤，用硫酸钠干燥，旋干。残余物在230–400目硅胶上，用石油醚：二氯甲烷＝5:1的比例进行柱色谱分离，可得衍生化产物即如式(IIa)所示化合物43mg，产率92％。
1H NMR(400MHz,CDCl 3)δ6.74(s,4H),6.49(s,4H),4.16(d,J＝12.8Hz,4H),3.23(dd,J 1＝14.6Hz,J 2＝5.9Hz,8H),3.18(d,J＝12.6Hz,4H),2.65(dd,J 1＝15.5Hz,J 2＝6.0Hz,8H)；
13C NMR(100MHz,CDCl 3)140.6,133.9,131.9,125.9,39.3,30.2；
HRMS(MALDI-FT)calcd for C 48H 56:503.2136[M+K] +.Found:503.2134.
由上可知，上述化合物结构正确，为式(IIa)所示化合物。
实施例5：化合物(Ib)衍生化(对应式(II)中n为4；R 2为n-Pr)
Figure PCTCN2020117641-appb-000042
具体衍生化方法是：取0.1mmol(62mg)式(Ib)所示化合物和相当其质量5％的10％铑炭，置于10mL史莱克管中，加入5mL甲酸，抽排5-6次换为氢气气氛后，用氢气球保持氢气气氛。之后在50℃磁力搅拌48h，冷却到室温后放掉氢气，过滤除去钯炭，保留滤液，滤饼用10mL二氯甲烷洗涤3次，合并到滤液中。合并后的有机相依次用30mL饱和食盐水，30mL饱和碳酸钠溶液和30mL饱和食盐水洗涤，用硫酸钠干燥，旋干。残余物在230–400目硅胶上，用石油醚：二氯甲烷＝5:1的比例进行柱色谱分离，可得衍生化产物即如式(IIb)所示化合物60mg，产率95％。
1H NMR(400MHz,CDCl 3)δ6.78(s,4H),6.46(s,4H),4.17(t,J＝7.6Hz,4H),3.24(dd,J 1＝14.7Hz,J 2＝9.6Hz,8H),2.68(dd,J 1＝15.1Hz,J 2＝9.6Hz,8H),2.23(q,J＝7.6Hz,8H),1.53(hex,J＝7.4Hz,8H),1.10(t,J＝7.3Hz,12H)；
13C NMR(100MHz,CDCl 3)143.2,133.9,131.9,115.9,42.3,30.2,29.8,21.1,14.4；
HRMS(MALDI-FT)calcd for C 48H 56:632.4382[M] +.Found:632.4377.
由上可知，上述化合物结构正确，为式(IIb)所示化合物。
实施例6：制备化合物(Va)
反应式如下：
Figure PCTCN2020117641-appb-000043
具体制备方法是：向50mL干燥史莱克瓶中加入2.0mmol(912mg)式(Ia)所示化合物，4.0mmol(1.44g)苯并亚硒酸酐(BSA)，和8mL氯苯，120℃油浴加热下磁力搅拌反应24h，可观察到体系从白色浊液变化到黄色溶液。冷却到室温后，旋干，用100ml二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯石油醚到二氯甲烷，进行柱色谱分离纯化，可得到(Va)所示化合物594mg，黄色粉末状固体，产率61％。
1H NMR(400MHz,1,1,2,2-Tetrachlorethane-d 2)δ7.17(s,2H),7.03(s,2H),7.00(s,2H),6.99–6.95(m,4H),6.91(d,J＝11.4Hz,2H),6.86(s,2H),4.66(d,J＝13.2Hz,1H),3.79(d,J＝11.7Hz,2H),3.74(d,J＝11.9Hz,1H),3.53–3.40(m,4H).
13C NMR(101MHz,1,1,2,2-Tetrachlorethane-d 2)δ188.00,143.21,141.85,140.92,137.95,133.33, 132.43,131.93,131.47,131.31,130.29,129.02,124.45,123.78,123.46,40.05,39.49,38.18.
HRMS(APCI)cald for C 36H 22O 2 +487.16926.Found 487.16893
实施例7：制备化合物(Vb和Vc)
反应式如下：
Figure PCTCN2020117641-appb-000044
具体制备方法是：向50mL干燥史莱特瓶中加入2.0mmol(912mg)式(Ia)所示化合物，8.0mmol(2.88g)苯并亚硒酸酐(BSA)，和12mL氯苯，120℃油浴加热下磁力搅拌反应10h，可观察到体系从白色浊液变化到黄色浊液。冷却到室温后，旋干，用100ml二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯石油醚到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得到式(Vb)和(Vc)化合物的混合物，采用制备级薄层色谱，以二氯甲烷:乙酸乙酯＝50:1为流动相，进行纯化分离，可得式(Vb)所示化合物165mg，黄色粉末状固体，产率16％；式(Vc)所示化合物413mg，黄色粉末状固体，产率40％。
[Vb] 1H NMR(400MHz,1,1,2,2-Tetrachlorethane-d 2)δ7.48(s,1H),7.28(s,2H),7.11(s,1H),7.10–6.97(m,7H),6.88(s,1H),4.75(d,J＝13.2Hz,2H),3.83(d,J＝11.7Hz,2H),3.62(d,J＝13.3Hz,2H),3.51(d,J＝11.6Hz,2H).
13C NMR(101MHz,1,1,2,2-Tetrachlorethane-d 2)δ186.95,186.66,145.42,143.72,139.64,138.95,134.43,134.39,133.57,132.20,131.93,131.45,130.72,129.54,125.24,124.72,124.37,124.19,39.78,38.47.
HRMS(APCI)cald for C 36H 21O4 +517.14344Found 517.14319.
[Vc] 1H NMR(400MHz,1,1,2,2-Tetrachlorethane-d 2)δ7.20(s,4H),7.13(s,4H),6.98(s,4H),4.71(d,J＝13.2Hz,2H),3.87(d,J＝11.7Hz,2H),3.60(d,J＝13.3Hz,2H),3.47(d,J＝11.7Hz,2H).
13C NMR(101MHz,1,1,2,2-Tetrachlorethane-d 2)δ188.07,143.00,142.25,133.39,132.63,130.55,130.26,130.11,129.84,124.62,124.20,40.55,38.01.
HRMS(APCI)cald for C 36H 204 -516.13671Found 516.13611.
实施例8：制备化合物(Vd)
Figure PCTCN2020117641-appb-000045
具体制备方法是：向50mL干燥三口中加入2.0mmol(912mg)式(Ia)所示化合物，12.0mmol(4.32g)苯并亚硒酸酐(BSA)，和14mL氯苯，120℃油浴加热下磁力搅拌反应3d，可观察到体系从白色浊液变化到黄色溶液。冷却到室温后，旋干，用300ml二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯二氯甲烷到二氯甲烷:乙腈＝50:1，进行柱色谱分离纯化，可得到式(Vd)所示化合物547mg，黄色粉末状固体，产率50％，其核磁氢谱如图7，核磁碳谱如图8，晶体结构如图9所示。
1H NMR(400MHz,DMSO-d 6)δ7.47(s,2H),7.39(s,2H),7.26(s,2H),7.23(s,2H),7.15(s,2H),5.18(d,J＝12.8Hz,1H),5.09(d,J＝12.9Hz,2H),4.03(d,J＝11.5Hz,1H),3.84(d,J＝13.0Hz,1H),3.78(d,J＝13.1Hz,2H),3.28(d,J＝11.4Hz,1H).
13C NMR(101MHz,DMSO-d 6)δ186.27,186.08,185.16,146.14,145.84,142.75,141.06,134.29,133.92,133.71,133.37,133.30,130.46,129.79,127.08,126.08,36.97.
HRMS(APCI)cald for C 36H 18O 6 -546.11089Found 546.11127.
实施例9：制备化合物(Ve)
Figure PCTCN2020117641-appb-000046
具体制备方法是：向50mL干燥史莱特瓶中加入2.0mmol(912mg)式(Ia)所示化合物，16.0mmol(5.76g)苯并亚硒酸酐(BSA)，和16mL氯苯，120℃油浴加热下磁力搅拌反应5d，可观察到体系从白色浊液变化到黄色溶液。冷却到室温后，旋干，用500ml二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯二氯甲烷到二氯甲烷:乙腈＝25:1，进行柱色谱分离纯化，可得到式(Ve)所示化合物184mg，黄色粉末状固体，产率16％。
1H NMR(400MHz,DMSO-d 6)δ7.59(s,4H),7.33(s,4H),5.19(d,J＝12.8Hz,4H),3.88(d,J＝12.8Hz,4H).
13C NMR(101MHz,DMSO-d 6)δ185.82,146.59,134.71,134.05,128.28,55.45,37.78.
HRMS(APCI)cald for C 36H 16O 8 -576.08507Found 576.08514.
实施例10：制备化合物(VIa)
Figure PCTCN2020117641-appb-000047
具体制备方法是：向50mL两口圆底烧瓶中加入2.0mmol(973mg)式(Va)所示化合物，1.15mmol(180mg)邻苯二乙腈，2.3mmol(124mg)甲醇钠，抽排三次置换为氮气氛围，后加入20mL甲醇:N,N-二甲基甲酰胺＝1:1的干燥混合溶剂，35℃下磁力搅拌反应8h，加入5mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从石油醚:二氯甲烷＝1:1到纯二氯甲烷，进行柱色谱分离纯化，可得到式(VIa)所示化合物1.067mg，淡黄色粉末状固体，产率88％。
1H NMR(400MHz,1,1,2,2-Tetrachlorethane-d 2)δ8.44(dd,J＝6.4,6.4Hz,2H),7.89(dd,J＝6.4,6.4Hz,2H),7.32(s,2H),7.13(s,2H),7.04(s,2H),7.00(s,2H),6.99(d,J＝11.5Hz,2H),6.95(d,J＝11.5Hz,2H)6.84(s,2H),3.80(d,J＝11.8Hz,2H),3.76(d,J＝11.5Hz,1H),3.61(d,J＝12.4Hz,1H),3.56(d,J＝12.4Hz,1H),3.52(d,J＝11.8Hz,2H),3.47(d,J＝11.5Hz,1H).
13C NMR(101MHz,1,1,2,2-Tetrachlorethane-d2)δ144.85,142.41,141.17,141.02,138.57,132.13,131.72,131.61,131.24,130.92,130.41,130.20,130.08,129.56,129.15,126.14,124.19,123.03,122.89,116.91,112.76,39.80,39.56,38.74.
HRMS(APCI)cald for C 46H 27N 2 +607.21688Found 607.21741.
实施例11：制备化合物(VIb)
Figure PCTCN2020117641-appb-000048
具体制备方法是：向50mL两口圆底烧瓶中加入2.0mmol(1.033g)式(Vb)所示化合物，2.3mmol(359mg)邻苯二乙腈，4.6mmol(248mg)甲醇钠，抽排三次置换为氮气氛围，后加入20mL甲醇：N,N-二甲基甲酰胺＝1：1的干燥混合溶剂，35℃下磁力搅拌反应8h，加入10mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50ml二氯甲烷溶解，加入230-400目硅 胶，旋干制样。固定相为230-400目硅胶，流动相从石油醚:二氯甲烷＝1:1到纯二氯甲烷，进行柱色谱分离纯化，可得到式(VIb)所示化合物934mg，淡黄色粉末状固体，产率62％。
1H NMR(400MHz,Chloroform-d)δ8.58(dd,J＝6.8,6.4Hz,2H),8.45(dd,J＝6.4,6.8Hz,2H),7.88(dd,J＝6.4,6.8Hz,4H),7.66(s,1H),7.45(s,2H),7.23(s,1H),7.14(s,2H),7.08–6.99(m,5H),6.90(s,1H),3.80(d,J＝11.6Hz,2H),3.65(s,4H),3.55(d,J＝11.6Hz,2H).
13C NMR(101MHz,Chloroform-d)δ146.76,143.50,142.48,142.75,141.19,139.65,134.30,132.74,132.34,132.14,131.54,131.49,131.01,130.53,130.31,129.99,129.55,127.12,126.45,125.16,124.05,123.67,123.51,117.08,114.79,113.71,116.21,40.09,39.67.
HRMS(APCI)cald for C 56H 29N 4 +757.23867Found 757.23741.
实施例12：制备化合物(VIc)
Figure PCTCN2020117641-appb-000049
具体制备方法是：向100mL两口圆底烧瓶中加入2.0mmol(1.033g)式(Vc)所示化合物，2.3mmol(359mg)邻苯二乙腈，4.6mmol(248mg)甲醇钠，抽排三次置换为氮气氛围，后加入30mL甲醇:N,N-二甲基甲酰胺＝1:1的干燥混合溶剂，35℃下磁力搅拌反应8h，加入10mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从石油醚:二氯甲烷＝1:1到纯二氯甲烷，进行柱色谱分离纯化，可得到式(VIc)所示化合物934mg，淡黄色粉末状固体，产率62％。
1H NMR(400MHz,Methylene Chloride-d 2)δ8.45(dd,J＝6.4,6.4Hz,4H),7.90(dd,J＝6.4,6.4Hz,4H),7.33(s,4H),7.26(s,4H),7.04(s,4H),3.91(d,J＝12.0Hz,2H),3.69(d,J＝12.4Hz,2H),3.63(d,J＝12.3Hz,2H),3.56(d,J＝11.9Hz,2H).
13C NMR(100MHz,Methylene Chloride-d 2)δ146.06,142.81,140.84,132.74,131.91,130.91,130.49,130.45,130.10,126.60,124.05,116.99,113.32,40.41,39.21.
HRMS(APCI)cald for C 56H 29N 4 +757.23867Found 757.23755.
实施例13：制备化合物(VId)
Figure PCTCN2020117641-appb-000050
具体制备方法是：向50mL两口圆底烧瓶中加入2.0mmol(1.093g)式(Vd)所示化合物，3.45mmol(1.078g)邻苯二乙腈，6.9mmol(373mg)甲醇钠，抽排三次置换为氮气氛围，后加入20mL甲醇:N,N-二甲基甲酰胺＝1:1的干燥混合溶剂，35℃下磁力搅拌反应8h，加入10mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50ml二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从石油醚:二氯甲烷＝1:1到纯二氯甲烷，进行柱色谱分离纯化，可得到式(VId)所示化合物671mg，白色粉末状固体，产率37％。
1H NMR(400MHz,Chloroform-d)δ8.67–8.53(m,4H),8.52–8.41(m,2H),7.96–7.86(m,6H),7.77(s,2H),7.50(s,2H),7.34(s,2H),7.26(s,2H),7.18(s,2H),3.90(d,J＝11.7Hz,1H),3.79-3.69(m,6H),3.57(d,J＝11.6Hz,1H).
13C NMR(101MHz,Chloroform-d)δ147.06,145.66,144.09,141.14,141.01,140.67,134.25,132.49,131.92,131.79,131.65,131.44,130.95,130.73,130.64,130.39,130.37,129.61,126.93,126.76,126.26,124.18,116.87,116.54,116.05,114.73,114.59,113.02,39.90,39.74,39.27.
HRMS(APCI)cald for C66H30N6+907.26047Found 907.25940.
实施例14：制备化合物(VIIa)
Figure PCTCN2020117641-appb-000051
具体制备方法是：向50mL干燥史莱特瓶中加入1.0mmol(757mg)式(VIb)所示化合物，8.0mmol(2.88g)苯并亚硒酸酐(BSA)，和12mL氯苯，回流下磁力搅拌反应10d，可观察到体系从白色浊液变化到黄色浊液。冷却到室温后，旋干，用100mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯石油醚到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得式(VIIa)所示化合物433mg，黄色粉末状固体，产率53％。
1H NMR(400MHz,Methylene Chloride-d 2)δ8.63–8.54(m,2H),8.53–8.44(m,1H),7.96(d,J＝9.7 Hz,4H),7.93(s,2H),7.80(s,1H),7.52(s,1H),7.40(s,2H),7.39(s,1H),7.34(s,1H),4.90(d,J＝13.2Hz,2H),3.89(d,J＝12.5Hz,2H),3.85(d,J＝13.2Hz,2H),3.77(d,J＝12.5Hz,2H).
13C NMR(101MHz,Methylene Chloride-d 2)δ188.04,186.11,149.77,146.08,145.77,143.15,140.83,140.41,135.64,135.14,134.30,133.32,132.77,132.58,132.24,131.30,131.26,127.08,126.76,126.08,116.87,116.17,115.15,114.74,39.82.38.74.
HRMS(APCI)cald for C 56H 25O 4 +817.18703Found 817.18781.
实施例15：制备化合物(VIIb)
Figure PCTCN2020117641-appb-000052
具体制备方法是：向50mL干燥史莱特瓶中加入1.0mmol(757mg)式(VIc)所示化合物，8.0mmol(2.88g)苯并亚硒酸酐(BSA)，和12mL氯苯，回流下磁力搅拌反应10d，可观察到体系从白色浊液变化到黄色浊液。冷却到室温后，旋干，用100mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯石油醚到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得式(VIIb)所示化合物424mg，黄色粉末状固体，产率52％。
1H NMR(400MHz,)δ8.50(dd,J＝6.4,3.2Hz,4H),7.98(dd,J＝6.3,3.1Hz,4H),7.80(s,4H),7.40(s,4H),4.90(d,J＝13.8Hz,2H),3.87(d,J＝13.3Hz,2H),3.80(d,J＝15.0Hz,2H),3.75(d,J＝12.0Hz,2H).
13C NMR(101MHz,)δ186.11,148.33,142.35,140.01,134.29,134.08,133.73,131.72,131.47,130.90,130.64,126.51,126.25,125.46,115.40,113.65.
HRMS(APCI)cald for C 56H 25O 4 +817.18703Found 817.18752.
实施例16：制备化合物(VIe)
Figure PCTCN2020117641-appb-000053
具体制备方法是：向50mL两口圆底烧瓶中加入1.0mmol(817mg)式(VIIa)所示化合物，2.3mmol(359mg)邻苯二乙腈，4.6mmol(248mg)甲醇钠，抽排三次置换为氮气氛围，后加入20mL甲醇： N,N-二甲基甲酰胺＝1:1的干燥混合溶剂，35℃下磁力搅拌反应8h，加入10mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯二氯甲烷到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得到式(VIe)所示化合物634mg，白色粉末状固体，产率60％，其核磁氢谱如图10，核磁碳谱如图11，晶体结构如图12所示。
1H NMR(400MHz,)δ8.58(dd,J＝6.3,3.1Hz,8H),7.84(s,4H),7.51(s,4H),3.89(d,J＝12.5Hz,4H),3.82(d,J＝12.2Hz,4H).
13C NMR(101MHz,1,1,2,2-Tetrachlorethane-d2)δ145.84,140.34,133.38,133.14,132.00,131.29,130.48,130.21,126.61,126.38,115.64,114.27,39.50.
HRMS(APCI)cald for C 76H 33N 8 +1057.28227Fond 1057.28308.
实施例17：制备化合物(VIe)
Figure PCTCN2020117641-appb-000054
具体制备方法是：向50mL两口圆底烧瓶中加入1.0mmol(817mg)式(VIIb)所示化合物，2.3mmol(359mg)邻苯二乙腈，4.6mmol(248mg)甲醇钠，抽排三次置换为氮气氛围，后加入20mL甲醇：N,N-二甲基甲酰胺＝1：1的干燥混合溶剂，35℃下磁力搅拌反应8h，加入10mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯二氯甲烷到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得到式(VIe)所示化合物634mg，白色粉末状固体，产率60％。
实施例18：制备化合物(VIf)
Figure PCTCN2020117641-appb-000055
具体制备方法是：向50mL两口圆底烧瓶中加入1.0mmol(487mg)式(Va)所示化合物，1.1mmol(119mg)邻苯二胺，0.11mmol(17mg)对甲基苯磺酸(p-TSA)，抽排三次置换为氮气氛围，后加入20mL干燥氯仿，回流下磁力拌反应12h，冷却至室温，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从石油醚:二氯甲烷＝1:1到纯二氯甲烷，进行柱色谱分离纯化，可得到式(VIf)所示化合物536mg，白色粉末状固体，产率96％。
1H NMR(400MHz,Chloroform-d)δ8.21(dd,J＝8.0,8.0Hz,2H),7.79(dd,J＝8.0,8.0Hz,2H),7.36(s,2H),7.04(s,2H),6.98(s,2H),6.96(s,2H),6.92(d,J＝11.5Hz,2H),6.87(s,2H),6.81(s,2H),3.85(d,J＝12.5Hz,1H),3.76(d,J＝11.7Hz,2H),3.70(d,J＝11.5Hz,1H),3.62(d,J＝12.6Hz,1H),3.53(d,J＝11.6Hz,2H),3.45(d,J＝11.5Hz,1H).
13C NMR(101MHz,Chloroform-d)δ152.67,141.32,141.07,140.78,139.08,133.09,132.56,132.26,131.85,130.82,130.28,130.02,129.93,129.34,125.06,123.02,122.90,40.20,39.96,38.94.
HRMS(ESI)cald for C 42H 27N 2 +559.216877Found 559.216858.
实施例19：制备化合物(VIg)
Figure PCTCN2020117641-appb-000056
具体制备方法是：向50mL两口圆底烧瓶中加入1.0mmol(517mg)式(Vb)所示化合物，2.2mmol(238mg)邻苯二胺，0.22mmol(38mg)对甲基苯磺酸，抽排三次置换为氮气氛围，后加入20mL干燥氯仿，回流下磁力拌反应12h，冷却至室温，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯氯甲烷到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得到式(VIg)所示化合物621mg，白色粉末状固体，产率94％。
1H NMR(400MHz,CDCl 3)δ8.31–8.29(m,2H),8.23–8.20(m,2H),8.03(s,1H),7.81-7.79(m,4H),7.39(s,2H),7.15(s,1H),7.11(s,2H),7.06(s,1H),7.00(d,J＝11.4Hz,2H),6.94(d,J＝11.4Hz,2H),6.84(s,1H),3.96(d,J＝12.5Hz,2H),3.80(d,J＝11.6Hz,2H),3.72(d,J＝12.6Hz,2H),3.54(d,J＝11.5Hz,2H).
13C NMR(100MHz,CDCl 3)δ152.30,152.09,144.43,142.70,141.66,141.30,141.25,139.66,134.36,134.00,133.29,132.62,132.12,130.88,130.16,129.97,129.71,129.20,125.06,123.53,123.40,123.07,40.04,39.09.
HRMS(ESI)cald for C 48H 29N 4 +661.238673Found 661.238723.
实施例20：制备化合物(VIh)
Figure PCTCN2020117641-appb-000057
具体制备方法是：向50mL两口圆底烧瓶中加入1.0mmol(517mg)式(Vc)所示化合物，2.2mmol(238mg)邻苯二胺，0.22mmol(38mg)对甲基苯磺酸(p-TSA)，抽排三次置换为氮气氛围，后加入20mL干燥氯仿，回流下磁力拌反应12h，冷却至室温，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯氯甲烷到二氯甲烷:乙酸乙酯＝50:1，进行柱色谱分离纯化，可得到式(VIg)所示化合物621mg，白色粉末状固体，产率94％。
1H NMR(400MHz,CDCl 3)δ8.21(dd,J＝6.4,6.4Hz,4H),7.79(dd,J＝6.4,6.4Hz,4H),7.39(s,4H),7.14(s,4H),7.05(1s,4H),3.88(d,J＝12Hz,2H),3.87(d,J＝12Hz,2H),3.68(d,J＝12Hz,2H),3.61(d,J＝12Hz,2H).
13C NMR(100MHz,CDCl 3)δ152.56,144.18,141.34,140.66,133.15,132.84,130.67,130.14,130.08,130.02,129.35,126.65,123.51,123.44,77.17,40.33,38.87.
HRMS(ESI)cald for C 48H 29N 4 +661.238673Found 661.238463.
实施例21：制备化合物(VIII)
Figure PCTCN2020117641-appb-000058
具体制备方法是：向100mL两口圆底烧瓶中加入1.0mmol(487mg)式(Va)所示化合物，0.5mmol(113mg)1,2,4,5-四乙氰基苯，4.6mmol(248mg)甲醇钠，抽排三次置换为氮气氛围，后加入30mL甲醇:N,N-二甲基甲酰胺＝1:1的干燥混合溶剂，35℃下磁力搅拌反应12h，加入10mL的1M氯化氢溶液猝灭反应，可观察到体系变成白色浊液。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从石油醚:二氯甲烷＝1:1到纯二氯甲烷，进行柱色谱分离纯化，可得到式(VIII)所示化合物353mg，橘黄色粉末状固体，产率46％。
1H NMR(400MHz,Chloroform-d)δ9.54(s,2H),7.36(s,5H),7.10(s,4H),6.98(d,J＝4.5Hz,11H),6.92(s,4H),6.84(s,4H),3.82–3.65(m,8H),3.63–3.45(m,8H).
HRMS(MALDI)for C 86H 45N 4 +1133.363874Found 1133.364012.
实施例22：制备化合物(IX)
Figure PCTCN2020117641-appb-000059
具体制备方法是：向100mL两口圆底烧瓶中加入1.0mmol(487mg)式(Va)所示化合物，0.5mmol(113mg)1,2,4,5-四氨基苯四盐酸盐，后加入30mL乙醇和0.1mL浓盐酸，回流下磁力搅拌反应2d，冷却室温，加入10mL饱和碳酸氢钠溶液猝灭反应。用50mL二氯甲烷和50mL饱和食盐水萃取，水相用二氯甲烷洗涤三次，合并有机相，无水硫酸钠干燥，旋转蒸发仪旋干，用50mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相从纯二氯甲烷到二氯甲烷:乙酸乙酯＝50:1进行柱色谱分离纯化，可得到式(IX)所示化合物223mg，黄色粉末状固体，产率43％，其核磁氢谱如图13，晶体结构如图14所示。
1H NMR(400MHz,1,1,2,2-Tetrachlorethane-d 2)δ9.07(s,2H),7.45(s,4H),7.17–6.89(m,20H),6.84(s,4H),3.98(d,J＝14.1Hz,2H),3.86–3.64(m,9H),3.56(d,J＝11.8Hz,4H),3.45(d,J＝12.2Hz,2H).
HRMS(MALDI)for C 78H 47N 4 +1039.379524Found 1039.379714.
实施例23：制备化合物(X1)
Figure PCTCN2020117641-appb-000060
具体制备方法是：向50mL干燥两口圆底烧瓶中加入0.2mmol(97.3mg)式(Va)所示化合物，0.22mmol(97.4mg)式(P)所示化合物，抽排三次，置换为N 2氛围，加入10mL干燥四氢呋喃和5mL干燥甲醇溶液，搅拌下逐滴加入3.5μL的5％(w/v)KOH的甲醇溶液，滴加完毕转入60℃油浴反应6h。反应完毕，旋转蒸发仪旋干，用25mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相石油醚:乙酸乙酯＝20:1进行柱色谱分离纯化，可得到式(X1)所示化合物109mg，紫黑色粉末状固体，产率61％。
1H NMR(400MHz,Chloroform-d)δ6.93(s,2H),6.91(s,2H),6.89(s,2H),6.83(d,J＝11.5Hz,6.81(s,2H),6.66(s,2H),6.59(d,J＝11.5Hz,2H),6.50(d,J＝2.3Hz,4H),6.35(t,J＝2.3Hz,2H),4.55(d,J＝12.4Hz,1H),3.84–3.74(m,8H),3.684(d,J＝11.6Hz,2H),3.679(d,J＝11.6Hz,2H),3.43(d,J＝12.4Hz,2H),3.42(d,J＝12.4Hz,2H),3.40(d,J＝11.6Hz,2H),1.70(dt,J＝7.2Hz,8H),0.95(t,J＝7.4Hz,12H).
13C NMR(101MHz,Chloroform-d)δ199.99,159.59,152.69,141.48,140.50,139.86,138.04,132.88,132.30,131.94,131.39,130.33,129.92,129.40,129.36,128.20,124.74,123.88,122.71,122.23,108.44,101.51,69.30,39.53,40.03,39.95,22.22,10.21.
HRMS(APCI)cald for C 63H 57O 5 +893.42005Found 893.42059.
实施例24：制备化合物(X2)
Figure PCTCN2020117641-appb-000061
具体制备方法是：向25mL干燥史莱特瓶中加入0.2mmol(178.6mg)式(X1)所示化合物，0.2mmol(47.6mg)1,2-双(4-甲氧基苯基)乙炔，抽排三次，置换为N 2氛围，加入1mL干燥二苯醚，回流过夜。反应完毕，旋转蒸发仪旋干，用25mL二氯甲烷溶解，加入230-400目硅胶，旋干制样。固定相为230-400目硅胶，流动相石油醚:乙酸乙酯＝5:1进行柱色谱分离纯化，可得到式(X2)所示化合物139mg，白色粉末状固体，产率63％，其晶体结构如图16所示。
1H NMR(400MHz,Chloroform-d)δ7.24–7.19(m,2H),6.87(s,2H),6.86(s,2H),6.81(s,2H),6.72(s,2H),6.66(d,J＝11.5Hz,2H),6.55(dd,J＝8.4,2.7Hz,2H),6.44(s,3H),6.42(d,J＝1.9Hz,1H),6.35(d,J＝11.5Hz,2H),6.28(dd,J＝8.5,2.7Hz,2H),6.25(s,2H),6.00(t,J＝2.3Hz,2H),5.82(s,2H),3.93(d,J＝11.5Hz,1H),3.72(d,J＝22.9Hz,2H),3.62–3.43(m,15H),3.39(d,J＝11.5Hz,1H),3.25(d,J＝11.7Hz,2H),1.63(dt,J＝7.4Hz,4H),1.45(dt,J＝13.4,7.4Hz,4H),0.93(t,J＝7.4Hz,6H),0.83(t,J＝7.4Hz,6H).
HRMS(MALDI)for C 78H 70O 6 +1102.516691Found 1102.516473.
实施例25：大环分子式(Ib)所示化合物对乙腈，氯仿的选择性包合
取上述式(Ib)所示化合物1.5mg溶于0.5mL氯仿中，加入0.5mL乙腈缓慢挥发，可以得到透明块状的晶体。单晶X-衍射实验结果如图15所示，客体分子乙腈，氯仿与主体分子形成1:1包合物结构，乙腈分子以其C-H键的一端坐落于主体分子的碗状空腔中，并与另一客体分子氯仿有弱相互作用。维持该结构的主要作用力为客体分子对主体芳环的C-H…π相互作用。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (52)

  1. 一种化合物，其特征在于，所述化合物为式(I)所示化合物或式(I)所示化合物的立体异构体，
    Figure PCTCN2020117641-appb-100001
    其中，
    n为4或6；
    R 1为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基。
  2. 根据权利要求1所述的化合物，其特征在于，R 1为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
  3. 根据权利要求1所述的化合物，其特征在于，R 1为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
  4. 根据权利要求1所述的化合物，其特征在于，具有以下其中之一的结构：
    Figure PCTCN2020117641-appb-100002
  5. 一种化合物，其特征在于，所述化合物为式(II)所示化合物或式(II)所示化合物的立体异构体，
    Figure PCTCN2020117641-appb-100003
    其中，
    n为4或6；
    R 2为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基。
  6. 根据权利要求5所述的化合物，其特征在于，R 2为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、 C 5-12环烷基、C 5-12杂环烷基。
  7. 根据权利要求5所述的化合物，其特征在于，
    n为4；
    R 2为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
  8. 根据权利要求5所述的化合物，其特征在于，具有以下其中之一的结构：
    Figure PCTCN2020117641-appb-100004
  9. 一种化合物，其特征在于，所述化合物为式(V)所示化合物或式(V)所示化合物的立体异构体，
    Figure PCTCN2020117641-appb-100005
    其中，
    n为1、2或3，m和m’分别独立地为1、2、3或4；
    R 3为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基。
  10. 根据权利要求9所述的化合物，其特征在于，R 3为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
  11. 根据权利要求9所述的化合物，其特征在于，
    n＝1、m＝1、m’＝3；或者n＝1、m＝3、m’＝1；或者n＝1、m＝2、m’＝2；或者n＝2、m＝1、m’＝1；或者n＝2、m＝0、m’＝2；
    R 3为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
  12. 根据权利要求9所述的化合物，其特征在于，具有以下其中之一的结构：
    Figure PCTCN2020117641-appb-100006
  13. 一种化合物，其特征在于，所述化合物为式(VI)所示化合物、式(VIII)所示化合物或式(IX)所示化合物，或其立体异构体，
    Figure PCTCN2020117641-appb-100007
    其中，
    n为1、2或3，m和m’分别独立地为1、2、3或4；
    R 4为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基；
    Ar 1为
    Figure PCTCN2020117641-appb-100008
    X为N或C-CN。
  14. 根据权利要求13所述的化合物，其特征在于，R 4为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
  15. 根据权利要求13所述的化合物，其特征在于，
    n＝1、m＝1、m’＝3；或者n＝1、m＝3、m’＝1；或者n＝1、m＝2、m’＝2；或者n＝2、m＝1、m’＝1；或者n＝2、m＝0、m’＝2；
    R 4为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
  16. 根据权利要求13所述的化合物，其特征在于，具有以下其中之一的结构：
    Figure PCTCN2020117641-appb-100009
    Figure PCTCN2020117641-appb-100010
  17. 一种化合物，其特征在于，所述化合物为式(VII)所示化合物或式(VII)所示化合物的立体异构体，
    Figure PCTCN2020117641-appb-100011
    其中，
    n、m和m’分别独立地为1、2、3、或4；
    R 5为氢原子、任选取代的C 1-12烷基、任选取代的C 1-12杂烷基、任选取代的C 2-12烯基、任选取代的C 5-24环烷基或任选取代的C 5-24杂环基；
    Ar 2为
    Figure PCTCN2020117641-appb-100012
    X为N或C-CN。
  18. 根据权利要求17所述的化合物，其特征在于，R 5为氢原子、C 1-6烷基、C 1-6杂烷基、C 2-6烯基、C 5-12环烷基、C 5-12杂环烷基。
  19. 根据权利要求17所述的化合物，其特征在于，
    n＝1、m＝1、m’＝3；或者n＝2、m＝1、m’＝1；
    R 5为氢原子、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、苄基、对甲基苄基、邻甲基苄基或间甲基苄基。
  20. 根据权利要求17所述的化合物，其特征在于，具有以下其中之一的结构：
    Figure PCTCN2020117641-appb-100013
  21. 一种制备权利要求1～4任一项所述的化合物的方法，其特征在于，包括：使式(III)所示化合物在格拉布斯催化剂存在条件下发生分子内烯烃关环复分解反应，得到式(I)所示化合物，
    Figure PCTCN2020117641-appb-100014
    其中，R 1为权利要求1～3任一项所限定的。
  22. 根据权利要求21所述的方法，其特征在于，所述格拉布斯催化剂包括选自格拉布斯I代催化剂、格拉布斯II代催化剂、格拉布斯III代催化剂、格拉布斯-霍维达催化剂、史洛克催化剂(Schrock)中的至少之一。
  23. 根据权利要求21所述的方法，其特征在于，所述接触在第一溶剂中进行，所述第一溶剂包括选自二氯甲烷、三氯甲烷、四氯化碳、1,2-二氯乙烷、1,1,2,2-四氯乙烷、苯、甲苯、三氟甲苯、氯苯、氟苯、硝基苯、溴苯、邻二甲苯，间二甲苯，对二甲苯和四氢萘中的至少之一。
  24. 根据权利要求23所述的方法，其特征在于，所述接触在-40～150℃下进行0.1～96h完成。
  25. 根据权利要求23所述的方法，其特征在于，式(III)所示化合物与所述催化剂的用量比为0.01～1mmol:0.01～100mmol。
  26. 根据权利要求21所述的方法，其特征在于，式(III)所示化合物通过使式(IV)所示化合物在金属催化剂的作用下发生交叉偶联反应制备得到，
    Figure PCTCN2020117641-appb-100015
  27. 根据权利要求26所述的方法，其特征在于，所述金属催化剂包括选自醋酸钯、四三苯基膦钯、三(二亚苄基丙酮)二钯、氯化钯和[1,1’-双(二苯基膦基)二茂铁]二氯化钯、乙酰丙酮镍、二(1,5-环辛二烯) 镍、1,3-双(二苯基膦基)乙烷二氯化镍、1,3-双(二苯基膦基)丙烷二氯化镍、1,3-双(二苯基膦基)丁烷二氯化镍、1,3-双(二苯基膦基)二茂铁二氯化镍中的至少之一。
  28. 根据权利要求27所述的方法，其特征在于，所述交叉偶联反应在第二溶剂中进行，所述第二溶剂包括选自N,N-二甲基甲酰胺、N,N-二甲基苯胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃、1,4-二氧六环、水和二甲基亚砜中的至少之一。
  29. 根据权利要求27所述的方法，其特征在于，所述交叉偶联反应在添加剂和烯基化试剂的作用下进行，所述添加剂包括选自碳酸钾、碳酸铯、碳酸锂、碳酸钠、氯化钠和氯化锂中的至少之一；所述烯基化试剂包括选自乙烯基溴化镁、异丙烯基溴化镁、三丁基乙烯基烯、三丁基异丙烯基烯、异丙烯基硼酸频哪醇酯和乙烯基硼酸频哪醇酯中的至少之一。
  30. 根据权利要求27所述的方法，其特征在于，所述交叉偶联反应在0～140℃下进行6～72h完成。
  31. 一种制备权利要求5～8任一项所述的化合物的方法，其特征在于，包括：使式(I)所示化合物与还原催化剂和氢气接触，得到式(II)所示化合物。
    Figure PCTCN2020117641-appb-100016
    其中，R 1为权利要求1～3任一项所限定的，R 2为权利要求5～7任一项所限定的。
  32. 根据权利要求31所述的方法，其特征在于，所述还原催化剂包括选自铂黑、二氧化铂、钯黑、钯炭、铂炭、铑炭、钌碳中的至少之一。
  33. 根据权利要求31所述的方法，其特征在于，所述接触在第三溶剂中进行，所述第三溶剂包括选自甲醇、乙醇、正丙醇、异丙醇、叔丁醇、甲酸、乙酸、丙酸中的至少之一。
  34. 根据权利要求33所述的方法，其特征在于，所述接触在1atm～1000atm氢气气氛中进行。
  35. 根据权利要求33所述的方法，其特征在于，所述接触在-40～150℃下进行0.1～96h完成.
  36. 根据权利要求33所述的方法，其特征在于，式(I)所示化合物与还原催化剂的用量比为0.01～1mmol:0.01～100mmol。
  37. 一种制备权利要求9～12任一项所述的化合物的方法，其特征在于，包括：使式(I)所示化合物与第一氧化剂接触，得到式(V)所示化合物，
    Figure PCTCN2020117641-appb-100017
    其中，R 1为权利要求1～3任一项所限定的，R 3为权利要求9～11任一项所限定的。
  38. 根据权利要求37所述的方法，其特征在于，所述第一氧化剂包括选自苯并亚硒酸酐、二氧化硒、 2,3-二氯-5,6-二氰基-1,4-苯醌、四氯苯醌、碘单质的至少之一。
  39. 根据权利要求37所述的方法，其特征在于，所述接触在第四溶剂中进行，所述第四溶剂包括选自氯苯、氟苯、溴苯、氯仿中的至少之一。
  40. 根据权利要求39所述的方法，其特征在于，所述接触在50～150℃下进行0.1～96h完成。
  41. 根据权利要求39所述的方法，其特征在于，所述式(I)所示化合物与所述第一氧化剂的用量比为0.01～1mmol:0.01～100mmol。
  42. 一种制备权利要求13～16任一项所述的化合物的方法，其特征在于，包括：使式(V)所示化合物与双亲核试剂发生缩合反应，得到式(VI)、(VIII)、(IX)所示化合物，
    Figure PCTCN2020117641-appb-100018
    其中，R 3为权利要求9～11任一项所限定的，Ar 1为权利要求13所限定的，R 4为权利要求13～15任一项所限定的。
  43. 根据权利要求42所述的方法，其特征在于，所述双亲核试剂为邻苯二乙腈、邻苯二胺、1,2,4,5- 四乙氰基苯或1,2,4,5-四氨基苯。
  44. 根据权利要求42所述的方法，其特征在于，所述接触在第五溶剂中进行，所述第五溶剂包括选自甲醇、四氢呋喃、N,N-二甲基甲酰胺乙醇、正丙醇、异丙醇、叔丁醇中的至少之一。
  45. 根据权利要求44所述的方法，其特征在于，所述接触在0～120℃下进行0.1～96h完成。
  46. 根据权利要求44所述的方法，其特征在于，式(I)所示化合物与双亲核试剂用量比为1mmol:(1～100)mmol。
  47. 一种制备权利要求17～20任一项所述的化合物的方法，其特征在于，包括：使式(VI)所示化合物与第二氧化剂接触，得到式(VII)所示化合物，
    Figure PCTCN2020117641-appb-100019
    其中，R 4为权利要求13～15任一项所限定的，Ar 1为权利要求13所限定的，R 5为权利要求17～19任一项所限定的，Ar 2为权利要求17所限定的。
  48. 根据权利要求47所述的方法，其特征在于，所述第二氧化剂包括选自苯并亚硒酸酐、二氧化硒、2,3-二氯-5,6-二氰基-1,4-苯醌、四氯苯醌、碘单质的至少之一。
  49. 根据权利要求47所述的方法，其特征在于，所述接触在第六溶剂中进行，所述第六溶剂包括选自氯苯、氟苯、溴苯、氯仿中的至少之一；
  50. 根据权利要求49所述的方法，其特征在于，所述接触在-40～150℃下进行0.1～96h完成；
  51. 根据权利要求49所述的方法，其特征在于，所述式(I)所示化合物与所述第二氧化剂的用量比为1mmol:(1～100)mmol。
  52. 权利要求1～20任一项所述的化合物在对有机分子选择性包合中的用途，所述化合物用于从混合溶液中识别并选择性包合有机分子。
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