CN109574822B - Series of tetraaryl spiro-compounds, preparation method and application thereof - Google Patents
Series of tetraaryl spiro-compounds, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a series of tetraaryl spiro compounds, a preparation method and application thereof, and relates to a method for synthesizing a series of tetraaryl spiro compounds by directly carrying out cycloaddition reaction on aromatic tertiary amine and diaryl acetylene under the catalysis of palladium acetate. The preparation method comprises the following steps: mixing palladium acetate with corresponding aromatic tertiary amine, diaryl acetylene, copper acetate monohydrate, phenanthroline and silver tetrafluoroborate according to the molar ratio of 0.2:2:2: 0.25:0.3, adding a solvent methanol, filling argon into a reaction system, and controlling the reaction temperature to be 100-120-oAnd C, after 24 hours, draining the solvent from the reaction system, and separating by silica gel column chromatography to obtain a corresponding product. In the reaction, two molecules of diaryl acetylene are inserted into a para-C-H bond of tertiary amino to generate a spiro compound. The method has the advantages of simple operation, better substrate applicability, simple and easily obtained substrate structure and the like.
Description
The patent application is funded by national science funds (21102101, 21772118, 21472122).
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and relates to a method for synthesizing a series of tetraaryl spiro-compounds by directly carrying out cycloaddition reaction on aromatic tertiary amine and diaryl acetylene compounds under the catalysis of palladium acetate.
Background
The carbon-carbon triple bond of an alkyne is one of the important functional groups of organic chemistry, and acetylene chemistry has experienced a resurgence in the past decades because it not only appears in the leading-edge molecules of organic chemistry (e.g., biochemistry or materials science), but also as a radical of synthetic chemistryA basic module or a multifunctional intermediate (Stang p. j., Diederich F.Modern acetylene chemistry[M]VCH 1995, p 285 ℃ 319). Alkynes are also of widespread importance in nature, and as of the last two centuries, one thousand naturally occurring acetylenic compounds have been discovered and reported. Alkynes can undergo Cycloaddition and oxidation Reactions, terminal Alkynes can be readily converted to metallic acetylenes, and can be utilized in a variety of ways in Organic Synthesis (Schore N.E. ChemInform Abstract: Transition-Metal-Mediated Cycloaddition Reactions of Alkynes in Organic Synthesis [ J.]. Chem. Rev. 1988, 88 (7), 1081-1119. Ananikov V. P., Khemchyan L. L., Beletskaya I. P. The comparison of addition of molecules possessing P(V)-H bond to alkynes catalyzed with Pd and Ni complexes[J]. Russian Journal of Organic Chemistry 2010, 46 (9), 1269-1276. Le R. E., Liang Y., Storz M. P., et al. Intramolecular hydroamination/cyclization of aminoalkenes catalyzed by Ln[N(SiMe3)2]3 grafted onto periodic mesoporous silicas[J]. J. Chem. Soc. Chem.2010, 132 (46), 16368-16371.). The development of new synthetic methods based on transition metal catalysis has driven the development of alkyne chemistry, with transition metal palladium catalysis always dominating (Boyarsky V. P., Ryabukhin D. S., Bokach N. A., et al., alkylation of olefins and heterarylenes with Alkynes [ J. ]]. Chem. Rev. 2016, 116 (10), 5894.）。
Palladium-catalyzed alkyne arylation can be divided into three groups according to the reaction type and the monomer: (1) palladium-catalyzed Heck reaction of alkyne and aromatic halide; (2) arylation of alkyne and arylboronic acid under the catalysis of palladium; (3) palladium catalyzes the olefination of aromatic C-H with alkynes. The first and second types require, respectively, an aryl halide as the hydride source and an aryl boronic acid as the proton source. In The third category, readily available simple aromatic hydrocarbons can be converted with acetylenic compounds by direct functionalization into arylalkenes (Zuieveld M. A., Swennenhuis B.H.G., Boele M.D.K., et al, The coordination catalyst of large natural bit angle ligands) by direct functionalization methyl and 4-cyanophenylpalladium(II) complexes[J]. Journal of the Chemical Society Dalton Transactions 2002, 11 (11), 2308-2317.）。
Tertiary amines are important building blocks in pharmaceuticals, dyes, natural products, biologically active molecules and Organic functional Materials (Chen C.T. Evolution of Red Organic Light-Emitting Diodes: Materials and Devices [ J]. Chemistry of Materials 2004, 16 (23), 4389-4400. Liang M., Chen J. Arylamine organic dyes for dye-sensitized solar cells[J]. Chem. Soc. Rev.2013, 42 (8), 3453.). It is well known that the para-functional groups of aromatic tertiary amines are made possible by the electron-withdrawing properties and steric hindrance of tertiary amine groups, whereas the ortho-selective C-H functionalization of tertiary amines is relatively difficult (Yeung C. S., Dong V.M. Catalytic dehydrogenation Cross-Coupling: Forming Carbon-Carbon Bonds by oxygen Oxidizing Two Carbon-Hydrogen Bonds [ J]. Chem. Rev. 2011, 111 (3), 1215-92.）。
In general, the primary and secondary anilines can be conveniently converted into various Directing groups and can functionalize the adjacent site aryl groups C-H (library B. C., Kim S., Park Y., et al, Palladium-Catalyzed C-H aryl Using a Directing Group at Room Temperature [ J]. Org. Lett. 2013, 15 (11), 2692-2695.). Recently, Miura and Jiao et al reported that primary anilines can act as directing groups for ortho-olefination and azide reactions, respectively (Suzuki C., Hirano K., Satoh T., et al, Ruthenium-Catalyzed registered C-H alkylation Directed by a Free Amino Group [ J]. Org. Lett. 2013, 15 (15), 3990-3993. Jiao N., Tang C. Copper-Catalyzed C-H Azidation of Anilines under Mild Conditions[J]. Synthesis2013, 45 (3), A21-A22.). However, the field of C-H activation of transition metal-Catalyzed tertiary anilines still has disadvantages, only a few examples being directed to the ortho-para-Selective conversion (Mizuta Y., Obora Y., Shimizu Y., et al, para-Selective aqueous Oxidative C-H introduction of amino groups Catalyzed by Palladium/Molybdovanadophosphoric Acid/2,4, 6-Trimethylbenzoic Acid System [ J.J. ]]. Chemcatchem 2012, 4 (2), 187-191.). The development of the C-H activated synthesis reaction of the ortho-para tertiary aniline has high value and significance.
Therefore, we disclose herein the results of palladium acetate catalyzed reaction of tertiary aryl amines with diarylacetylene compounds in methanol to produce tetraarylspiro compounds. The tetraaryl spiro-compound prepared by the method can be applied to rechargeable lithium ion batteries.
Disclosure of Invention
The invention further provides a preparation method for producing the tetraaryl spiro-compound by using palladium acetate to catalyze the aromatic tertiary amine and diaryl acetylene to directly carry out cycloaddition reaction in methanol.
In order to achieve the purpose, the invention discloses the following technical contents:
the aromatic tertiary amine used in the invention has a structure of a general formula (I):
the diaryl acetylene used in the invention has a structure of a general formula (II):
（Ⅱ）
the tetraaryl spiro compound which can be prepared has a structure shown in a general formula (III):
（Ⅲ）
wherein R1-R9: a hydrogen atom; aliphatic substituents containing 1 to 20 carbons; an aromatic substituent having 1 to 20 carbons;
aliphatic substituent containing oxygen, nitrogen and sulfur heteroatom and having 1 to 20 carbon atoms or aromatic substituent containing oxygen, nitrogen and sulfur heteroatom and having 1 to 20 carbon atoms;
R1-R9 may form a ring with each other, and are aliphatic substituents having 1 to 20 carbons; an aromatic substituent having 1 to 20 carbons;
aliphatic substituent containing oxygen, nitrogen and sulfur heteroatom and having 1 to 20 carbon atoms or aromatic substituent containing oxygen, nitrogen and sulfur heteroatom and having 1 to 20 carbon atoms;
r1 to R9 may be the same or different;
wherein R1-R9 are aliphatic substituents containing 1 to 20 carbons, meaning: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, isopropyl, tert-butyl, cyclohexyl, vinyl or allyl; the aromatic substituent having 1 to 20 carbons means phenyl, tolyl, ethylphenyl, t-butylphenyl, cumyl, naphthyl, methylnaphthyl or t-butylnaphthyl; the aliphatic substituent containing 1 to 20 carbon atoms and containing oxygen, nitrogen and sulfur heteroatoms refers to methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, isopropoxy, tert-butoxy, cyclohexyloxymethyl, methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, isopropylamino, tert-butylamino, cyclohexylamino, methylthio, ethylmercapto, n-propylmercapto, n-butylmercapto, n-pentylmercapto, n-hexylmercapto, n-heptylthio, isopropylmercapto, tert-butylmercapto and cyclohexylmercapto.
Wherein R1-R9 are aromatic substituents of 1 to 20 carbons containing oxygen, nitrogen, sulfur heteroatoms, and refer to pyridyl, substituted pyridyl, quinolyl, substituted quinolyl, furyl, substituted furyl, thienyl, or substituted thienyl.
Wherein R1-R9 are annulated to each other as an aliphatic substituent containing 1 to 20 carbons and are referred to as cyclopentyl, cyclohexyl, substituted cyclopentyl or substituted cyclohexyl; the aromatic substituent having 1 to 20 carbons means phenyl, tolyl, ethylphenyl, t-butylphenyl, cumyl, naphthyl, methylnaphthyl or t-butylnaphthyl; aliphatic substituents of 1 to 20 carbons containing oxygen, nitrogen, sulfur heteroatoms refer to tetrahydrofuranyl, substituted tetrahydrofuranyl, piperidinyl, substituted piperidinyl, tetrahydropyrrolyl, substituted tetrahydropyrrolyl, tetrahydrothienyl, or substituted tetrahydrothienyl.
Wherein the aromatic substituent of 1 to 20 carbons containing oxygen, nitrogen, sulfur heteroatoms refers to pyridyl, substituted pyridyl, quinolyl, substituted quinolyl, furyl, substituted furyl, thienyl or substituted thienyl.
The method for synthesizing the tetraaryl spiro-compound by directly carrying out cycloaddition reaction on the aromatic tertiary amine and the diaryl acetylene compound under the catalysis of palladium acetate comprises the following steps: mixing palladium acetate with corresponding aromatic tertiary amine, diaryl acetylene, copper acetate monohydrate, phenanthroline and silver tetrafluoroborate according to the molar ratio of 0.2:2:2: 0.25:0.3, adding a solvent methanol, filling argon into a reaction system, and adding 100-120- oAnd C, performing oil bath at constant temperature, draining the solvent from the reaction system after 24 hours, and performing chromatographic separation on the solvent by using a silica gel column to obtain a corresponding product. The synthetic route is as follows:
1-20 are tetraarylspiro compounds synthesized by the above route, and are also structural formulae for the compounds of the examples:
wherein the chemical name of 1 is: 1,2,3, 4-tetraphenylspiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 2 is: 6-methyl-1, 2,3, 4-tetraphenylspiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 3 is: 7-methyl-1, 2,3, 4-tetraphenylspiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 4 is: 1,2,3, 4-tetra (p-methylphenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 5 is: 1,2,3, 4-tetrakis (4- (trifluoromethyl) phenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 6 is: 1,2,3, 4-tetrakis (3-bromophenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 7 is: 1,2,3, 4-tetrakis (3-chlorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 8 is: 1,2,3, 4-tetrakis (3-fluorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 9 is: 1,2,3, 4-tetrakis (2-fluorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 10 is: 1,2,3, 4-tetrakis (4-methoxyphenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 11 is: 1,2,3, 4-tetrakis (4-fluorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 12 is: (8-Carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -methyl tetraphenylbenzoate
Wherein 13 has the chemical name: 1,1',1' ',1' '' - ((8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) tetraphenylone
Wherein 14 has the chemical name: 6-methyl-1, 2,3, 4-tetrakis (4- (trifluoromethyl) phenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein 15 has the chemical name: 1,2,3, 4-tetrakis (4-bromophenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one
Wherein 16 has a chemical name: 7-bromo-1, 2,3, 4-tetraphenylspiro [4.5] dec-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 17 is: 7-nitro-1, 2,3, 4-tetraphenylspiro [4.5] decan-1, 3,6, 9-tetraen-8-one
Wherein the chemical name of 18 is: 8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5] decane-1, 3,6, 9-tetraene-7-carboxylic acid
Wherein 19 has a chemical name: 8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5] decane-1, 3,6, 9-tetraene-7-carboxylic acid methyl ester.
Wherein 19 has a chemical name: 8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5] decane-1, 3,6, 9-tetraene-7-carboxylic acid methyl ester.
Wherein 20 has a chemical name of: (8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -tetraphenecarboxylic acid.
The invention further discloses application of the series of tetraaryl spiro-compounds as a negative electrode material of a rechargeable lithium ion battery; the prepared tetraaryl spiro polyacid, a conductive agent (Super P) and a bonding agent (PVDF) are uniformly mixed in an NMP solution according to the weight ratio of 5:4:1, then the paste is coated on copper foil by using a scraper, the NMP is removed by drying at 100 ℃, a pole piece with the diameter of 16 mm is punched, and the pole piece is dried in vacuum at 100 ℃ for 12 hours and is used as the negative electrode of the rechargeable lithium battery. The experimental results prove that: the tetraaryl spiro-polyacid prepared by the method has the advantages of high charge-discharge capacity, high charge speed, stable charge-discharge cycle and the like.
In the experimental research, the invention finds that the conditions of catalyst, oxidant, solvent, ligand, reaction temperature and the ratio of reactants have great influence on the yield of the reaction, so that the invention carries out a great deal of investigation and screening on the conditions and finally screens out the optimal conditions of the reaction. Among them, the selection of N, N-diethyl aromatic amine as the tertiary amine for the reaction and the addition of silver tetrafluoroborate are the key points to improve the yield of the reaction. The method has the advantages that the reaction is completed in one step, the direct cycloaddition reaction of the aromatic tertiary amine and the diaryl acetylene is realized, the method is simple to operate, the applicability of a substrate is better, the structure of the substrate is simple and easy to obtain, and the like. The aromatic tertiary amine and diarylacetylene (2 +2+ 1) cycloaddition products can be prepared in a wide variety of ways.
Drawings
FIG. 1 is a graph of variation in discharge capacity and coulombic efficiency for compound 20 at different current densities;
fig. 2 shows the discharge capacity corresponding to the compound 20 with different current densities.
Detailed Description
The present invention is described below with reference to examples, which are not intended to limit the present invention, and those skilled in the art may make modifications and variations thereto in light of the spirit of the present invention, which should be construed as being within the scope of the present invention as defined in the appended claims; the diarylacetylenes described therein (Mio M. J., Kopel L. C., Braun J. B., et al. One-pot synthesis of symmetrical and unsymmetrical bisarylethynes by a modification of the Sonogashira coupling reaction[J]. Org. Lett. 2002, 4 (19), 3199. cndot. 3202.), a partially aromatic tertiary amine compound (Lei z., Li x., Li Y., et al. Synthesis of Sterically Protected Xanthene Dyes with Bulky Groups at C-3 ' and C-7 '[J]. J. Org. Chem. 2015, 80 (22), 11538 and 11543) were prepared according to literature methods. The remaining raw materials and various solvents, unless otherwise specified, are commercially available.
Example 1
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg(0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. After the reaction is completed, silica gel column chromatography is usedPurification (eluent: petroleum ether: ethyl acetate =20: 1) gave 37.2 mg of product as a white solid in 83% yield. (1, 2,3, 4-tetraphenylspiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 254 oC -256 oC。1H NMR (400 MHz, CDCl3) δ 7.19-7.01 (m, 16H), 6.90 (d, J = 6.9Hz, 4H), 6.82 (d, J = 9.9Hz, 2H) , 6.44 (d, J = 9.9Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 186.2, 147.9, 147.6, 141.2, 134.7, 134.5, 131.9, 130.0, 129.3, 128.0, 127.9, 127.5, 127.3, 66.2。
Example 2
A50 mL Schlenk reaction tube was charged with 35.5. mu.L (0.2mmol) of N, N-diethyl-m-methylaniline, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 14.8 mg of a white solid in a yield of 32%. (6-methyl-1, 2,3, 4-tetraphenylspiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 185 oC -187 oC。 1H NMR (400 MHz, CDCl3) δ 7.27-6.91 (m, 20H), 6.89-6.73 (m, 1H), 6.47 (d, J = 9.6 Hz, 1H), 6.39 (d, J = 15.4 Hz, 1H), 1.95 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 187.0, 156.6, 148.5, 148.4, 142.1, 134.8, 134.2, 131.4, 130.9, 129.9, 129.0, 128.1, 128.0, 127.5, 127.4, 68.6, 19.0; HRMS (ESI) m/z calcd for C35H26O [M+Na]+: 485.1876, found 485.1878。
Example 3
A50 mL Schlenk reaction tube was charged with 35.5. mu.L (0.2mmol) of N, N-diethylo-methylbenzylamine, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 13.0 mg of a white solid in 28% yield. (7-methyl-1, 2,3, 4-tetraphenylspiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 192oC -195 oC。1H NMR (400 MHz, CDCl3) δ 7.15 – 7.07 (m, 12H), 7.03 (dd, J = 7.6, 1.9 Hz, 4H), 6.93 – 6.87 (m, 4H), 6.79 (dd, J = 9.7, 2.8 Hz, 1H), 6.63 – 6.57 (m, 1H) 6.42 (d, J = 9.7 Hz, 1H), 1.89(s, 3H); 13C NMR (100 MHz, CDCl3) δ 186.8, 147.6, 147.1, 142.6, 141.5, 138.4, 134.8, 134.7, 131.4, 130.0, 129.3, 127.9, 127.8, 127.3, 127.2, 68.5, 16.2; HRMS (ESI) m/z calcd for C35H26O [M+H]+: 463.2056, found 463.2058.
Example 4
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 41.2 mg (0.2mmol) of 4,4' - (dimethyl) tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 36.3 mg of a white solid in a yield of 72%. (1, 2,3, 4-tetrakis (p-methylphenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 210 oC -212 oC。1H NMR (400 MHz, CDCl3) δ 6.94-6.91 (m, 12H), 6.82-6.76 (m, 6H), 6.42 (d, J = 10.0Hz, 2H), 2.25 (d, J = 9.6Hz, 3H); 13C NMR (100MHz, CDCl3) δ 186.4, 148.6, 147.4, 140.2, 136.9, 136.7, 132.0, 131.9, 131.6, 129.8, 129.1, 128.6, 128.6, 66.2, 21.3, 21.2。
Example 5
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 62.8 mg (0.2mmol) of 4,4' - (trifluoromethyl) tolane, Pd (OAc)2 4.5 mg (0.02mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =15: 1) to obtain 42.1 mg of a white solid in a yield of 58%. (1, 2,3, 4-tetrakis (4- (trifluoromethyl) phenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 262 oC -265 oC。1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.3Hz, 8H), 7.15 (d, J = 7.4Hz, 4H), 6.99 (d, J = 7.8Hz, 4H), 6.82-6.72 (m, 2H), 6.56-6.46 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 185.0, 146.6, 145.1, 142.9, 137.1, 137.0, 132.9, 130.0, 129.4, 125.5, 66.1; HRMS (ESI) m/z calcd for C38H20F12O [M+H]+: 721.1395, found 721.1398.
Example 6
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 67.2 mg (0.2mmol) of 4,4' - (dibromodiphenylacetylene, Pd (OAc))2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 51.2 mg of a white solid in a yield of 67%. (1, 2,3, 4-tetrakis (3-bromophenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 215 oC -218 oC。1H NMR (400 MHz, CDCl3) δ 7.38-7.30 (m, 4H), 7.183 (s, 2H), 7.08-6.95 (m, 8H), 6.81 (d, J = 7.7Hz, 2H), 6.70 (d, J = 9.9Hz, 2H), 6.50 (d, J = 9.9Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 185.3 , 145.8 , 141.5, 135.5, 132.7, 132.6, 132.0, 131.2, 131.1, 129.8, 128.4, 127.8, 122.2, 65.9; HRMS (ESI) m/z calcd for C34H20Br4O [M+Na]+: 782.8140, found 782.8190.
Example 7
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 49 mg (0.2mmol) of 3, 3' - (dichloro) tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 49.8 mg of a white solid in a yield of 85%. (1, 2,3, 4-tetrakis (3-chlorophenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 205 oC -208 oC。1H NMR (400 MHz, CDCl3) δ 7.22-7.14 (m, 4H), 7.10 (td, J = 7.9, 1.8Hz, 4H), 7.02 (s, 2H), 6.93 (d, J = 7.7Hz, 2H), 6.88 (s,2H), 6.77 (d, J = 7.6Hz, 2H), 6.71 (d, J = 9.7Hz, 2H) , 6.50 (d, J = 9.6Hz, 2H);13C NMR (100 MHz, CDCl3) δ 185.3, 146.3, 145.8, 141.6, 135.3, 134.2, 134.1, 132.6, 129.7, 129.6, 129.1, 128.3, 128.2, 127.9, 127.3, 65.9; HRMS (ESI) m/z calcd for C34H20Cl4O [M+H]+: 585.0341, found 585.0339.
Example 8
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 42.8 mg (0.2mmol) of 3, 3' - (difluoro) tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.0)25 mmol)，AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =15: 1) to obtain 24.1 mg of a white solid in a yield of 47%. (1, 2,3, 4-tetrakis (3-fluorophenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 221 oC -224 oC。1H NMR (400 MHz, CDCl3) δ 7.18-7.07 (m, 4H), 6.93-6.81 (m, 6H), 6.74 (d, J = 9.9Hz, 4H), 6.68 (d, J = 7.7Hz, 2H), 6.60 (d, J = 9.6Hz, 2H), 6.48 (d, J = 9.8Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 185.3, 163.6, 163.5, 161.2, 161.0, 146.4, 146.0, 141.6, 135.9, 135.8, 135.7, 132.5, 129.9, 129.8, 129.7, 125.5, 124.9, 116.7, 116.6, 116.2, 116.0, 115.2, 115.1, 115.0, 114.9, 65.9; HRMS (ESI) m/z calcd for C34H20F4O [M+H]+: 521.1523, found 521.1528.
Example 9
Under the protection of argon, a 50 mL Schlenk reaction tube was taken and added with 32. mu.L (0.2mmol) of N, N-diethylaniline, 52.4 mg (0.2mmol) of 2, 2' - (difluoro) tolane, 24.5 mg (0.02 mmol) of Pd (OAc), 2.H2O 40 mg (0.2mmol), 4.95 mg (0.025 mmol) of phenanthroline, 45.9 mg (0.03 mmol) of AgBF, methanol (1.0 mL), and an oil bath 100-120oC, stirring for 24 hours. The reaction was completed and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 16.7 mg of a white solid in a yield of 32%. (1, 2,3, 4-tetrakis (2-fluorophenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 245 oC -248 oC。1H NMR (400 MHz, CDCl3) δ 7.23-7.07 (m, 6H), 7.07-6.95 (m, 4H), 6.94-6.84 (m, 6H), 6.80 (t, J = 9.0Hz, 2H), 6.37 (d, J = 9.7Hz, 2H); 13C NMR (100 MHz, CDCl3) δ185.8, 160.9, 160.7, 158.5, 158.2, 145.4, 144.6, 138.8, 132.1, 131.3, 130.8, 130.2, 130.1, 129.8, 123.6, 123.5, 122.3, 122.1, 121.6, 121.4, 115.7, 115.5, 115.4, 115.1, 67.2; HRMS (ESI) m/z calcd for C34H20F4O [M+H]+: 521.1523, found 521.1531.
Example 10
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 48.6 mg (0.2mmol) of 4,4' - (dimethoxy) tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =10: 1) to obtain 15.3 mg of a white solid in a yield of 27%. (1, 2,3, 4-tetrakis (4-methoxyphenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 195 oC -198 oC。1H NMR (400 MHz, CDCl3) δ 6.98 (d, J = 8.9Hz, 4H), 6.84-6.74 (m, 6H), 6.65 (dd, J = 8.9, 7.2Hz, 8H), 6.42 (d, J = 10.0Hz, 2H), 3.74 (d, J = 7.8Hz, 12H); 13C NMR (100 MHz, CDCl3) δ 186.5, 158.5, 149.1, 146.6, 139.1, 131.5, 131.3, 130.9, 130.5, 128.9, 127.4, 127.3, 113.3, 65.6, 55.1。
Example 11
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 42.8 mg (0.2mmol) of 4,4' - (difluoro) tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =15: 1) to obtain 29.5 mg of a white solid in a yield of 57%. (1, 2,3, 4-tetrakis (4-fluorophenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 200 oC -203 oC。1H NMR (400 MHz, CDCl3) δ 7.01 (dd, J = 8.8, 5.4 Hz, 4H), 6.88–6.79 (m, 12H), 6.74 (d, J = 10.0 Hz, 2H), 6.45 (d, J = 10.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 185.6, 163.3, 160.8, 147.0, 146.3, 140.6, 132.2, 131.6, 131.5, 131.0, 130.9, 130.1, 130.0, 115.4, 115.2, 66.0; HRMS (ESI) m/z calcd for C34H20F4O [M+Na]+: 543.1342, found 543.1348.
Example 12
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 58.8 mg (0.2mmol) of 4,4' -di (methyl benzoate) acetylene, Pd (OAc)2 4.5mg (0.02mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =3: 1) to obtain 27.9 mg of a yellow solid in a yield of 41%. ((8-Spirocarbonyl [4.5]]Deca-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -methyl tetraphenylbenzoate)
Melting point: 216 oC -219 oC。1H NMR (400 MHz, CDCl3) δ 7.79 (dd, J = 8.3, 3.3 Hz, 8H), 7.10 (d, J = 8.3 Hz, 4H), 6.94 (d, J = 8.3 Hz, 4H), 6.77 (d, J = 9.9 Hz, 2H), 6.48 (d, J = 9.9 Hz, 2H), 3.86 (d, J = 2.6 Hz, 12H); 13C NMR (100 MHz, CDCl3) δ 185.1, 166.5, 166.4, 147.2, 145.7, 142.8, 138.3, 138.2, 132.6, 129.8, 129.6, 129.5, 129.1, 66.1, 52.2; HRMS (ESI) m/z calcd for C42H32O9 [M+H]+: 681.2119, found 681.2125.
Example 13
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 52.4 mg (0.2mmol) of 4,4' -di (acetophenone) acetylene, Pd (OAc)2 4.5 mg (0.02mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =1: 1), and the product was 35.8 mg as a yellow solid in 59% yield. (1, 1',1' ',1' '' - ((8-carbonylspiro [ 4.5)]Decyl-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) tetraphenyl ethanone)
Melting point: 238 oC -240 oC。 1H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 8.4, 1.8 Hz, 8H), 7.13 (d, J = 8.4 Hz, 4H), 6.97 (d, J = 8.4 Hz, 4H), 6.79 (d, J = 10.0 Hz, 2H), 6.49 (d, J = 10.0 Hz, 2H), 2.53 (d, J = 3.6 Hz, 12H); 13C NMR (100 MHz, CDCl3) δ 197.4, 197.3, 185.2, 147.2, 145.7, 142.9, 138.4, 138.3, 136.4, 132.7, 130.0, 129.3, 128.4, 128.3, 66.1, 26.6; HRMS (ESI) m/z calcd for C42H32O5 [M+Na]+: 639.2142, found 639.2147.
Example 14
A50 mL Schlenk reaction tube was charged with 35.5. mu.L (0.2mmol) of N, N-diethyl-m-methylaniline, 62.8 mg (0.2mmol) of 4,4' - (trifluoromethyl) tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =10: 1) to obtain 16.2 mg of a white solid in a yield of 22%. (6-methyl-1, 2,3, 4-tetrakis (4- (trifluoromethyl) phenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 226 oC -229 oC。 1H NMR (400 MHz, CDCl3) δ 7.43 (dd, J = 14.4, 8.2 Hz, 8H), 7. 10(d, J = 8.2 Hz, 4H), 7.01 (d, J = 8.1 Hz, 4H), 6.71 (d, J = 9.8 Hz, 1H), 6.51 (d, J = 9.8, 1.4 Hz, 1H), 6.40 (d, J = 1.2 Hz, 1H), 1.92 (d, J= 0.9 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 185.8, 153.8, 147.5, 145.7, 143.6, 137.1, 136.6, 132.2, 132.0, 130.0, 129.1, 125.6, 125.5, 68.6, 18.8; HRMS (ESI) m/z calcd for C39H22F12O [M+H]+: 735.1552, found 735.1558
Example 15
A50 mL Schlenk reaction tube was charged with 32. mu.L (0.2mmol) of N, N-diethylaniline, 67.2 mg (0.2mmol) of 1, 2-bis (4-bromobenzene) acetylene, Pd (OAc) under an argon atmosphere2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =10: 1) to obtain 16 mg of a white solid in a yield of 21%. (1, 2,3, 4-tetrakis (4-bromophenyl) spiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 230 oC -233 oC。 1H NMR (400 MHz, CDCl3) δ 7.29-7.24 (m, 10H), 6.89 (d, J = 8.3 Hz, 4H), 6.73 (d, J = 8.2 Hz, 4H), 6.45 (d, J = 9.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 185.4, 146.3, 146.2, 141.3, 132.7, 132.4, 131.6, 131.5, 131.4, 130.6, 128.9, 125.4, 122.3, 122.2, 65.8; HRMS (ESI) m/z calcd for C34H20Br4O [M+Na]+: 782.8140, found 782.8160.
Example 16
A50 mL Schlenk reaction tube was charged with 30. mu.L (0.2mmol) of 2-bromo-N, N-diethylaniline, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. After the reaction is completed, the reaction mixture is purified by silica gel column chromatography (washing)Removing the agent: petroleum ether: ethyl acetate =20: 1), product 15 mg as white solid, yield 29%. (7-bromo-1, 2,3, 4-tetraphenylspiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 243 oC -245 oC 1H NMR (400 MHz, CDCl3) δ7.27 (d, J = 2.6, 1H), 7.21 – 7.00 (16H), 6.93 – 6.87 (4H), 6.85 (dd, J = 9.7, 2.6, 1H), 6.50 (d, J = 9.7, 1H). 13C NMR (75 MHz, CDCl3) δ 178.9, 148.1, 148.0, 147.7, 140.2, 134.4, 134.1, 130.5, 129.9, 129.3, 128.2, 128.0, 127.8, 127.5, 126.5, 69.0. HRMS (EI) m/z calcd for C34H23OBr [M+H]+: 526.0927, found 526.0940.
Example 17
Under the protection of argon, a 50 mL Schlenk reaction tube was charged with 33. mu.L (0.2mmol) of 2-nitro-N, N-diethylaniline, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =20: 1) to obtain 20 mg of a white solid in a yield of 41%. (7-Nitro-1, 2,3, 4-tetraphenylspiro [4.5]]Dec-1, 3,6, 9-tetraen-8-one
Melting point: 209 oC -211 oC 1H NMR (400 MHz, CDCl3) δ7.60 (d, J= 2.6, 1H), 7.21 – 7.07 (12H), 7.06 – 6.96 (4H), 6.94 – 6.83 (5H), 6.50 (d, J = 9.8, 1H). 13C NMR (75 MHz, CDCl3) δ175.0, 149.7, 149.4, 147.1, 146.1, 140.0, 133.9, 133.4, 131.9, 129.9, 129.3, 128.5, 128.3, 128.1, 127.9, 66.0. HRMS (EI) m/z calcd for C34H23NO3 [M+H]+: 493.1672, found 493.1662.
Example 18
A50 mL Schlenk reaction tube was charged with 30. mu.L (0.2mmol) of 2-diethylamine benzoic acid, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =2: 1) to obtain 13.8 mg of a white solid in 28% yield. (8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5]]Deca-1, 3,6, 9-tetraene-7-carboxylic acid)
Melting point: 210oC -212 oC 1H NMR (300 MHz, acetone) d 8.28 (d, J = 2.8, 1H), 7.43 (dd, J = 2.8, 9.7, 1H), 7.26 – 7.01 (20H), 6.62 (d, J = 9.7, 1H). 13C NMR (75 MHz, acetone) δ 188.8, 163.6, 161.9, 152.5, 150.9, 140.0, 135.5, 134.9, 131.5, 130.7, 130.4, 129.7, 128.9, 128.7, 128.6, 128.4, 68.5. HRMS (ESI) m/z calcd for C35H24O3Na [M+Na]+: 515.1623, found 515.1613.
Example 19
A50 mL Schlenk reaction tube was charged with 31. mu.L (0.2mmol) of methyl 2-diethylamine benzoate, 35.6 mg (0.2mmol) of tolane, Pd (OAc)2 4.5 mg (0.02 mmol)，Cu(OAc)2 .H2O40 mg (0.2mmol), phenanthroline 4.95 mg (0.025 mmol), AgBF4 5.9mg (0.03 mmol), methanol (1.0 mL), oil bath 100-oC, stirring for 24 hours. The reaction was completed, and purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate =5: 1) to obtain 16.2 mg of a white solid in a yield of 32%. (8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5]]Decyl-1, 3,6, 9-tetraene-7-carboxylic acid methyl ester)
Melting point: 126oC -128 oC 1H NMR (300 MHz, CDCl3) d 7.61 (d, J = 2.8, 1H), 7.24 – 7.05 (12H), 7.05 – 6.98 (4H), 6.90 (dd, J = 8.0, 1.5, 4H), 6.80 (dd, J = 9.9, 2.9, 1H), 6.45 (d, J = 9.8, 1H), 3.82 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 181.7, 164.6, 155.0, 148.5, 145.7, 141.0, 134.4, 134.0, 133.4, 132.7, 129.9, 129.4, 128.2, 128.0, 127.8, 127.5, 66.1, 52.5。HRMS (EI) m/z calcd for C36H26O3 [M+H]+: 506.1882, found 506.1896。
Example 20
A50 mL Schlenk reaction tube was charged with 250.0 mg (0.37 mmol) of methyl ester of the compound 12 (8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -tetraphenecarboxylic acid prepared in example 12, 2.0 mL of a 3M NaOH solution, and stirred at 70 ℃ for 12 hours. After completion of the reaction, a 10% HCl solution was added dropwise with stirring, the pH = 1.0 was adjusted, and the mixture was filtered to obtain a white solid product (8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -tetrabenzoic acid 200.0 mg, with a yield of 87%.
Melting point:>300 °C。 1H NMR (400 MHz, CDCl3) δ 13.14 (s, 4H), 8.01 (d, J = 8.2 Hz, 5H), 7.82 - 7.64 (m, 9H), 7.19 (d, J = 8.2 Hz, 2H), 7.06 (d, J = 8.2 Hz, 3H), 6.42 (d, J = 9.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 184.8, 166.6, 146.7, 142.2, 138.3, 131.7, 130.9, 129.8, 129.7, 129.6, 129.3, 129.0, 126.1, 67.0; HRMS (ESI) m/z calcd for C38H24O9 [M-H]-: 623.1348, found 623.1345.
example 21
The compound 20 prepared in example 20 was uniformly mixed with a conductive agent (Super P) and a binder (PVDF) in a weight ratio of 5:4:1 in an NMP solution, then the paste was coated on a copper foil using a doctor blade, NMP was removed by drying at 100 ℃, a pole piece with a diameter of 16 mm was punched out, and vacuum-dried at 100 ℃ for 12 hours in preparation for battery assembly.
The assembly of the button cells was carried out in a glove box (Ar atmosphere protection, oxygen and water content less than 0.1 ppm), using metallic lithium as counter electrode, Celgard 2400 as separator, 1M LiPF6Solutions in EC/DEC (1: 1 by volume) were used as electrolytes to assemble CR2430 button cells for electrical performance testing.
FIG. 1 is a graph of the rate capability of compound 20 tested at different current densities, and when the current density is 50 mA/g (0.1C), the cycle performance curve of 22 times of charging and discharging is shown, and it can be seen from the graph that the discharge capacity is basically maintained at 700 mAh/g, and the coulomb efficiency is close to 100%; the current density is increased to 100 mA/g (0.2C), the discharge capacity is about 500 mAh/g, and the discharge capacity slightly declines along with the circulation; the current densities are increased continuously to 200 mA/g (0.4C), 500 mA/g (1.0C) and 1000 mA/g (2.0C), the stable circulating capacities correspond to 370 mAh/g, 300 mAh/g and 250 mAh/g, and the coulomb efficiency is basically kept to be close to 100%.
Fig. 2 is a comprehensive comparison graph of the discharge capacity of the compound 20 at different current densities, and it can be seen from the graph that the discharge capacity of the compound 20 is 370 mAh/g at a current density of 0.4C, which is equivalent to the discharge capacity (about 374 mAh/g) at a current density of 0.1C of the most commonly used graphite electrode material for the negative electrode of the current lithium ion battery, that is, the current density that can be achieved by the compound 20 is about 4 times that of the graphite electrode when the same discharge capacity is achieved, that is, the charging speed is 4 times that of the graphite electrode. And when the current density is the same as 0.1C, the discharge capacity of the compound 20 can reach 700 mAh/g, namely, the discharge capacity of the compound 20 is about 2 times of that of the graphite electrode under the same current density. Compound 20 possesses superior performance compared to the mainstream graphite electrode materials.
Claims (4)
1. A preparation method of a series of tetraaryl spiro-compounds is characterized in that palladium acetate, corresponding aromatic tertiary amine, diaryl acetylene, copper acetate monohydrate, phenanthroline and silver tetrafluoroborate are mixed according to the molar ratio of 0.2:2:2:2:0.25:0.3, solvent methanol is added, a reaction system is filled with argon, and the reaction temperature is controlled at 100-oC, after 24 hours, draining the solvent from the reaction system, and separating by silica gel column chromatography to obtain a corresponding product;
wherein said aromatic tertiary amine used has the structure of formula (I):
wherein said diarylacetylene is used having the structure of formula (II):
wherein the prepared tetraarylspiro compound has a structure of general formula (III):
（Ⅲ）
wherein R1-R9: a hydrogen atom; aliphatic substituents containing 1 to 20 carbons; an aromatic substituent having 1 to 20 carbons;
aliphatic substituent containing oxygen, nitrogen and sulfur heteroatom and having 1 to 20 carbon atoms or aromatic substituent containing oxygen, nitrogen and sulfur heteroatom and having 1 to 20 carbon atoms;
r1 to R9 may be the same or different.
2. The process of claim 1 wherein R1-R9 are aliphatic substituents containing 1 to 20 carbons and are defined as follows: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, isopropyl, tert-butyl, cyclohexyl, vinyl or allyl; the aromatic substituent having 1 to 20 carbons means phenyl, tolyl, ethylphenyl, t-butylphenyl, cumyl, naphthyl, methylnaphthyl or t-butylnaphthyl; the aliphatic substituent containing 1 to 20 carbon atoms and containing oxygen, nitrogen and sulfur heteroatoms refers to methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, isopropoxy, tert-butoxy, cyclohexyloxymethyl, methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, isopropylamino, tert-butylamino, cyclohexylamino, methylthio, ethylmercapto, n-propylmercapto, n-butylmercapto, n-pentylmercapto, n-hexylmercapto, n-heptylthio, isopropylmercapto, tert-butylmercapto and cyclohexylmercapto.
3. The process according to claim 1, wherein R1-R9 are each an aromatic substituent of 1 to 20 carbon atoms containing hetero atoms of oxygen, nitrogen and sulfur, and each represents a pyridyl group, a quinolyl group, a furyl group or a thienyl group.
4. The method of claim 1, wherein a typical tetraarylspiro compound product comprises:
(1) 1,2,3, 4-tetraphenylspiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(2) 6-methyl-1, 2,3, 4-tetraphenylspiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(3) 7-methyl-1, 2,3, 4-tetraphenylspiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(4) 1,2,3, 4-tetrakis (p-methylphenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(5) 1,2,3, 4-tetrakis (4- (trifluoromethyl) phenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(6) 1,2,3, 4-tetrakis (3-bromophenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(7) 1,2,3, 4-tetrakis (3-chlorophenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(8) 1,2,3, 4-tetrakis (3-fluorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one;
(9) 1,2,3, 4-tetrakis (2-fluorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one;
(10) 1,2,3, 4-tetrakis (4-methoxyphenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(11) 1,2,3, 4-tetrakis (4-fluorophenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one;
(12) (8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -methyl tetraphenylbenzoate;
(13) 1,1',1' ',1' '' - (8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) tetraphenylone;
(14) 6-methyl-1, 2,3, 4-tetrakis (4- (trifluoromethyl) phenyl) spiro [4.5] decan-1, 3,6, 9-tetraen-8-one;
(15) 1,2,3, 4-tetrakis (4-bromophenyl) spiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(16) 7-bromo-1, 2,3, 4-tetraphenylspiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(17) 7-nitro-1, 2,3, 4-tetraphenylspiro [4.5] dec-1, 3,6, 9-tetraen-8-one;
(18) 8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5] decane-1, 3,6, 9-tetraene-7-carboxylic acid;
(19) 8-carbonyl-1, 2,3, 4-tetraphenylspiro [4.5] decane-1, 3,6, 9-tetraene-7-carboxylic acid methyl ester;
(20) (8-carbonylspiro [4.5] dec-1, 3,6, 9-tetraene-1, 2,3, 4-tetrasubstituted) -4,4',4' ',4' '' -tetraphenecarboxylic acid.
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