CN103664499A - Synthesis method of tetracene and pentacene compounds - Google Patents

Abstract

The invention relates to a synthesis method of tetracene and pentacene compounds. Starting from the simple and easy-to-obtain o-phthalaldehyde compounds and aryl acetylene, a variety of bispropargyl carbonate compounds were prepared by addition reaction of alkynyllithium reagent; in the presence of catalytic amount of palladium reagent, bispropargyl Alcohol carbonates can be reacted in series with organic boronic acids to synthesize naphthacene and pentacene compounds in one step with good to excellent yields. The method has the characteristics of easy-to-obtain raw materials, simple operation, mild conditions, convenience and quickness, and excellent yield. The method can effectively introduce aryl groups and alkyl groups on the skeletons of tetracene and pentacene.

Description

Synthetic method of tetracene and pentacene compounds

technical field

The invention relates to a method for synthesizing substituted tetracene and pentacene by transition metal palladium catalysis, which is mainly used for synthesizing aryl-substituted or alkyl-substituted naphthacene and pentacene compounds simply and efficiently. the

Background technique

Aromatic chemistry is an important part of the whole organic chemistry, and it is also the main building block of molecular engineering, crystal engineering, drug design, molecular electronics, and inorganic and organometallic chemistry. With the continuous development of material science research, polycyclic aromatic hydrocarbons have gradually become a hot spot in the research of organic materials. Due to the high delocalization of π electrons in their conjugated systems, polyphenyl aromatic fused ring compounds show good performance in many functional materials, such as photoluminescent materials, photosensitizers, organic superconducting materials, and liquid crystal materials. Among them, tetracene and pentacene compounds are particularly noticeable. At present, this type of compound is mainly used in the following two electronic materials: 1. Field-effect transistors or thin-film semiconductor transistors (Field-effect transistors; FETs, also known as thin-film transistors, TFTs); 2. Organic light-emitting diodes (organic light -emitting diodes; OLEDs). Since different substitution forms of tetracene and pentacene compounds can regulate the interaction between molecules in the aggregated state, it is possible to further improve the optoelectronic performance of the overall device. Therefore, how to efficiently synthesize polytetracene and pentacene compounds has also become one of the hot areas that chemists pay attention to. At present, the common synthesis methods of this kind of compounds are the alternation method, Diels-Alder reaction, reduction and oxidation of polybenzoquinones, and nucleophilic addition of polybenzoquinones to alkynyl metals. However, most of the methods have disadvantages such as many steps, low yield, great limitation on substrates and difficulty in introducing specific substituents at multiple positions on tetracene or pentacene rings. (For the synthesis method of tetracene or pentacene compounds, see a) Lin, C.; Lin, K-H.; Pal, B.; Tsouz, L. Chem. Commun., 2009, 803-805.b) Takahashi,T.;Kitamura,M.;Shen,B.J.;Nakajima,K.J.Am.Chem.Soc.2000,122,12876-12877.c)Wan,Y.;Jing,G.;Yan,L.;Wei, J.;Simone,D.;Fabrizia,N.;Zhaohui,W.J.Am.Chem.Soc.2011,133,18054-18057.d)Mondal,R.;Shah,B.K.;Neckers,D.C.J.Org.Chem,2006, 71, 4085-4091. e) Jens, R.; Henning, H.; Andre, D. G.; Colette, B.; Henri, B. L.; Jean-Pierre, D. Org. Lett. 2005, 7, 971-974. f) Gribble ,G.W.; Perni,R.B.;Onan,K.D.J.Org.Chem.,1985,50,2934-2939.g)Miao,Q.;Chi,X.;Xiao,S.;Zeis,R.;Lefenfeld,M.; Siegrist, T.; Steigerwald, M.L.; Nuckolls, C.J. Am. Chem. Soc., 2006, 128, 1340-1345.h) Kuninobu, Y.; Seiki, T.; Kanamaru, S.; Nishina, Y.; Takai ,K.org.Lett.2010,12,5287-5289.i)Lin,Y-C.;Lin,C-H,Org.Lett.2007,9,2075-2078.) In view of the important application value of this kind of compound, so develop Simple and efficient synthetic methods of tetracene and pentacene compounds are very necessary. The present invention starts from simple and easy-to-obtain reagents such as o-phthalaldehyde and alkynyl metals, and first synthesizes a variety of bis-alkynyl biscarbonate compounds, and then couples rings with aryl or alkylboronic acids under the catalysis of palladium reagents. Naphthacene or pentacene compounds were obtained in high yield. The biggest feature of this reaction is that the reaction conditions are mild, the reaction speed is fast, the yield is high, and all the steps in series are completed in one pot. Such compounds are expected to be further applied in fields such as organic optoelectronic materials. the

Contents of the invention

The object of the present invention is to provide an efficient synthesis method of linear tetracene and pentacene compounds. the

The structural formula of polycyclic aromatic hydrocarbon compound of the present invention is as follows:

Wherein, R ¹ and R ² are H or R ¹ and R ² are connected to form a benzo ring;

R ³ is C _1-8 alkyl, tert-butyl, phenyl, Z-substituted phenyl, thienyl; said Z is C _1-8 alkyl, C _1-8 alkoxy, tri Fluoromethyl, phenyl, nitro, amino, ester, acyl or halide.

R ⁴ , R ⁵ , R ⁶ , R ⁷ are H, C _1-8 alkyl, C _1-8 alkoxy, trifluoromethyl, phenyl, nitro, amino, ester, acyl or halogen ;

^R is phenyl, phenyl substituted by Q; said Q is C _1-8 alkyl, C _1-8 alkoxy, trifluoromethyl, phenyl, nitro, amino, ester group, acyl or halogen.

The synthetic method and reaction formula of compound among the present invention are as follows:

1) Synthesis of raw material dicarbonates. the

Wherein, THF represents tetrahydrofuran, rt represents room temperature, priding represents pyridine, and R ¹ , R ² and R ⁸ are as described above.

In this reaction, a diol is obtained through the addition reaction of a traditional alkynyl lithium reagent and an aldehyde, and then a variety of phthalates can be synthesized conveniently and in high yield through an esterification reaction of the diol. In the method of the present invention, the molar ratio of the o-phthalaldehyde to the lithium alkynyl reagent is 1:4. In the second step reaction, the molar ratios of diol to methyl chloroformate, pyridine, and 4-(N,N-dimethylamino)pyridine (DMAP) are sequentially: 1:3:10-30:0.1-0.9. the

2) Efficient synthesis of polycyclic aromatic hydrocarbons

Wherein, cat represents a palladium catalyst, solvent represents an organic solvent, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above.

Starting from the above-prepared phthalate compounds, under the catalysis or promotion of palladium catalysts, naphthacene and pentacene compounds can be synthesized in one step with good to excellent yields. the

All reactions are carried out in organic solvents, such as benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide (DMA), tetrahydrofuran, diethylamine, triethylamine , dichloromethane, dichloroethane, chloroform, diethyl ether, 1,4-p-oxane, acetonitrile dimethyl sulfoxide, hexamethylphosphoramide or a mixed solvent of the above solvents and other organic solvents. the

The palladium catalyst is palladium chloride, palladium acetate, palladium bromide, palladium trifluoroacetate, bistriphenylphosphine palladium dichloride, tetrakistriphenylphosphine palladium, dichlorodiacetonitrile palladium, dichlorodibenzonitrile palladium, 5% palladium on carbon, 1,2-bis(diphenylphosphino)ethanepalladium dichloride, allylpalladium(II) chloride dimer, bis(dibenzylideneacetone)palladium, [1, 3-Bisdiphenylphosphinopropane]palladium chloride, bis(tricyclohexylphosphine)palladium, or diamminepalladium dichloride. the

The molar ratio of the dicarbonate compound to R ³ B(OH) ₂ and the palladium catalyst is: 1:1-6:0.001-1; the reaction time is 0.1 minutes to 100 hours; the recommended range is 0.1-100 minutes. The reaction temperature is from room temperature to 130°C.

The purification and separation of the product of the method of the present invention can be separated by methods such as recrystallization, thin layer chromatography, column chromatography and vacuum distillation. When using thin-layer chromatography and column chromatography, the developer used is a mixed solvent of polar solvent and non-polar solvent. The recommended developer can be diethyl ether-petroleum ether, ethyl acetate-petroleum ether, ethyl acetate-n-hexane or isopropanol-petroleum ether, etc. The recrystallization method is recommended. The solvent used for recrystallization is a mixed solvent of polar solvent and non-polar solvent. Recommended solvents are dichloromethane-n-hexane, ethyl acetate-petroleum ether, ethyl acetate-n-hexane, isopropanol-petroleum ether, ether-petroleum ether, etc. the

In the present invention, the initial dicarbonate compound is conveniently prepared by the addition reaction of the ortho-phthalaldehyde compound and the alkynyl metal reagent, which are readily available as raw materials, and then obtained efficiently and in high yield under the catalysis or promotion of the palladium catalyst. A variety of substituted naphthacene or pentacene compounds have mild reaction conditions, convenient operation and high yield, and the yield of cyclization reaction can generally reach 50-99%. The reaction is also easy to scale up the operation process and realize industrial production. The compounds of the present invention have good solubility and good thermal stability in organic solvents. the

Detailed ways

Will help to understand the present invention by following embodiment, but do not limit content of the present invention

Example 1: Synthesis of 5,12-diaryltetracene (5,12-diaryltetracene) from o-phthalaldehyde, phenylacetylene, and arylboronic acid

1) Synthesis of raw material bispropargyl carbonate 1a

Under the protection of argon, add phenylacetylene (120mmol, 13.2mL) and tetrahydrofuran (120mL) sequentially to a dry 250mL three-neck flask with a stirring bar, then cool to -78°C in a dry ice/acetone bath, and slowly add 2.5M n-Butyllithium/n-hexane solution (110mmol, 44mL), the dropwise addition was completed, and after stirring for 30 minutes, o-phthalaldehyde (50mmol, 6.71g) was added, and reacted for 2 hours, and TLC detected that the reaction was complete; saturated NH ₄ Cl solution quenched extinguished, extracted with ethyl acetate, dried with anhydrous Na ₂ SO ₄ , filtered, spin-dried, and separated by silica gel column chromatography, eluent: petroleum ether: acetone=5:1, to obtain 17.03 g of yellow viscous liquid, yield 100% .

Add the diol (5mmol, 1.7g), dichloromethane (30mL), pyridine (50mmol, 4mL), and DMAP (0.5mmol, 61mg) prepared above into a 100mL egg-shaped bottle with a stirrer, and cool in an ice-water bath To 0°C, add methyl chloroformate (30mmol, 2.35mL), stir for a few minutes, remove the ice-water bath, react at room temperature (rt) for 3h, and TLC detects that the reaction is complete; quench with NH ₄ Cl solution, extract with dichloromethane, Anhydrous Na ₂ SO ₄ dried, filtered, spin-dried, separated by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 5:1, to obtain 2.27g of bispropargyl carbonate 1a viscous liquid, the yield 100%. The ratio of the two diastereoisomers is 1:1, ¹ H NMR (CDCl ₃ , Me ₄ Si) two isomers: δ7.81-7.75(m), 7.46-7.41(m), 7.31- 7.25(m), 6.98(s, one isomer, 1H), 6.95(s, another isomer, 1H), 3.79(s, one isomer, 3H), 3.72(s, another isomer, 3H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) two isomers: δ154.55, 154.52, 134.76, 134.59, 131.93, 131.89, 129.72, 129.65, 129.43, 128.87, 128.85, 128.79, 128.15, 128.12 88.64,88.21,84.76,84.68,67.54,67.16,55.03,55.00.IR(neat):2958,2852,1751,1491,1441,1321,1258,1011,927,788,757,691cm ^-1 ;HRMS(ESI) calculated value(calcd for)C ₂₈ H ₂₂ O ₆ Na[M+Na ⁺ ]: 477.1314, found 477.1309.

2) Synthesis of 5,12-diphenyltetracene (5,12-diphenyltetracene)

Under argon protection, bispropargyl carbonate 1a (0.2mmol, 91mg), phenylboronic acid (0.8mmol, 97.5mg) and tetrahydrofuran (5mL) were successively added into a 25mL Schlenk reaction tube with a stirring bar to dissolve, and tetrahydrofuran (5mL) was added to dissolve it. Triphenylphosphine palladium (0.01mmol, 12mg), react at 80°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and separate by silica gel column chromatography , 68.5mg of yellow solid was obtained, the yield was 90%. Melting point, 185-186℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.31(s, 2H), 7.77(dd, J=6.6, 3.6Hz, 4H), 7.69-7.54(m, 12H), 7.28- 7.22(m,4H) ^.13C NMR(100.6MHz,CDCl ₃ )δ139.28,137.01,131.50,130.92,129.29,129.06,128.51,128.38,127.56,126.96,125.69,125.16,124.73.IR(neat 3026,2962, 2922,2855,1599,1496,1440,1393,1261,1099,1020,955,879,744,702cm ^-1 ; the NMR data of this compound have been reported in previous literature (O.Toshimichi.; K.Akihito. ; S. Michinori. Org. Lett. 2011, 13, 1238.)

Embodiment 2: the synthesis of 5-phenyl-12-(p-chlorophenyl) naphthacene (5-(4-Chlorophenyl)-12-phenyltetracene)

Under argon protection, bispropargyl carbonate 1a (0.2mmol, 91mg), p-chlorophenylboronic acid (0.8mmol, 125.1mg) and tetrahydrofuran (5mL) were sequentially added into a 25mL Schlenk reaction tube with a stirring bar to dissolve, Add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 100°C for 3h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and perform silica gel column chromatography After separation, 78.1 mg of yellow solid was obtained, with a yield of 94%. Melting point, 181-183℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.31(s,1H),8.26(s,1H),7.77-7.75(m,2H),7.68-7.59(m,7H), 7.53(d,J=6.0Hz,2H),7.47(d,J=8.0Hz,2H),7.29-7.20(m,4H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ139.11,137.73,137.47,135.40 ,133.65,132.88,131.44,131.07,130.95,129.30,129.23,129.00,128.93,128.86,128.54,128.40,128.29,127.65,127.08,126.54,125.86,125.39,125.27,125.25,125.04,124.77.IR(neat): 3053,2954,2925,2854,1597,1492,1392,1119,1088,1016,956,878,834,815,757,741,703cm ^-1 ; HRMS(EI) for C ₃₀ H ₁₉ Cl: calculated value 414.1175, measured value 414.1176.

Example 3: Synthesis of 5-phenyl-12-(p-trifluoromethylphenyl)naphthacene (5-phenyl-12-(4-(trifluoromethyl)phenyl)tetracene)

Under argon protection, bispropargyl carbonate 1a (0.2mmol, 91mg), p-trifluoromethylphenylboronic acid (0.8mmol, 152mg), tetrahydrofuran (5mL) were sequentially added to a 25mL Schlenk reaction tube with a stirring bar Dissolve, add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 100°C for 3h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, Separation by column chromatography gave 69.2 mg of a yellow solid with a yield of 77%. Melting point, 181-182℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.32(s,1H),8.18(s,1H),7.92(d,J=8.0Hz,2H),7.79-7.76(m, 2H),7.70-7.52(m,9H),7.30-7.23(m,4H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ143.37(q, ⁵ J _CF =1.1Hz),139.02,137.84,135.01 ^. _{_} ^_ _{_} 3.8Hz),125.51,125.35,125.27,125.00,124.43(q, ¹ J _CF =272.2Hz),124.81.IR(neat):3054,2925,2854,1616,1402,1324,1166,1127,1105,1066 ,1020,878,848,776,740,703cm ^-1 ; HRMS(EI) for C ₃₁ H ₁₉ F ₃ : calculated value 448.1439, measured value 448.1435.

Embodiment 4: Synthesis of 2-methoxy-5,12-diaryltetracene (2-methoxy-5,12-diaryltetracene) by o-phthalaldehyde and p-methoxyphenylacetylene, arylboronic acid

1) Synthesis of raw material bispropargyl carbonate 1b

Under the protection of argon, add p-methoxyphenylacetylene (4.8mmol, 634.4mg) and tetrahydrofuran 10mL sequentially into a dry 50mL Schlenk reaction tube with a stirring bar, then cool to -78°C in a dry ice/acetone bath, Slowly add 2.5M n-butyllithium/n-hexane solution (4.4mmol, 1.76mL) dropwise, after the dropwise addition is completed, make it react at -78°C for half an hour, add o-phthalaldehyde (2mmol, 268.3mg), and react After 1.5 hours, the reaction was detected by TLC; quenched with saturated NH ₄ Cl solution, extracted with ethyl acetate, dried with anhydrous Na ₂ SO ₄ , filtered, spin-dried, and separated by silica gel column chromatography, eluent: petroleum ether: acetone=3 : 1, 793.1 mg of yellow viscous liquid was obtained, and the yield was 100%.

Add the diol (2mmol, 796.9mg), dichloromethane (10mL), pyridine (40mmol, 3.2mL), DMAP (0.4mmol, 48.9mg) prepared above to a 100mL egg-shaped bottle with a stirrer, and ice Cool in a water bath to 0°C, add methyl chloroformate (12mmol, 0.93mL), stir for a few minutes, remove the ice-water bath, react at room temperature for 3h, and TLC detects that the reaction is complete; quenched with NH ₄ Cl solution, extracted with dichloromethane, no Water Na ₂ SO ₄ dried, filtered, spin-dried, silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 2:1, to obtain 843.1 mg of bispropargyl carbonate 1b light yellow solid, yield 82% . Melting point, 49-50°C; the ratio of the two diastereoisomers is 1:1, ¹ H NMR (CDCl ₃ , Me ₄ Si) two isomers: δ7.80-7.74 (m, 2H), 7.45-7.43 (m, 2H), 7.40-7.34 (m, 4H), 6.96 (s, one isomer, 1H), 6.93 (s, another isomer, 1H), 6.80-6.76 ( m,4H),3.78(s,6H),3.77(s,3H),3.74(s,3H); ¹³ C NMR(CDCl ₃ ,Me ₄ Si) two isomers: δ159.98,159.94,154.58,154.55 ,134.91,134.73,133.49,133.45,129.62,129.52,129.37,128.76,113.93,113.92,113.77,113.71,88.68,88.25,83.50,83.46,67.71,67.30,55.21,55.20,55.00,54.97；IR(neat): 2962,2839,2226,1749,1605,1509,1440,1321,1258,1173,1092,1028,923,800cm ^-1 ; HRMS (ESI) calculated value (calcd for)C ₃₀ H ₂₆ O ₈ Na[M+Na ⁺ ]:537.1525, the measured value is 537.1520.

2) Synthesis of 2-methoxy-5-phenyl-12-(p-methoxyphenyl)naphthacene (2-methoxy-12-(4-methoxyphenyl)-5-phenyltetracene)

Under argon protection, bispropargyl carbonate 1b (0.2mmol, 102.9mg), phenylboronic acid (0.8mmol, 97.5mg) and tetrahydrofuran (5mL) were successively added into a 25mL Schlenk reaction tube with a stirrer to dissolve, adding Tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 2h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and separate by silica gel column chromatography , 79.0mg of yellow solid was obtained, the yield was 90%. Melting point, 194-196℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.26(s,2H),7.81-7.75(m,2H),7.62–7.57(m,4H),7.53-7.51(m,2H ),7.45(d,J=8.4Hz,2H),7.27-7.24(m,2H),7.18(d,J=8.4Hz,2H),6.95(dd,J=9.8,2.6Hz,1H),6.86 (d,J=2.4Hz,1H),3.97(s,1H),3.70(s,1H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ158.88,156.28,139.29,137.03,134.14,132.44,131.66,131.42 ,131.03,130.55,130.32,129.90,128.83,128.46,128.37,128.27,128.16,127.53,126.46,125.82,125.10,124.84,124.68,120.34,114.10,101.81,55.32,54.97.IR(neat):3051,2999, 2954,2930,2834,1621,1512,1464,1433,1380,1285,1238,1206,1176,1115,1033,879,837,818,786,742,704cm ^-1 ; HRMS(EI) for C ₃₂ H ₂₄ O ₂ : calculated value 460, measured value 460,17 Value 440.1779.

Example 5: Synthesis of 2-methoxy-5,12-di-p-methoxyphenyl tetracene (2-Methoxy-5,12-bis(4-methoxyphenyl)tetracene). the

Under argon protection, bispropargyl carbonate 1b (0.2mmol, 102.9mg), p-methoxyphenylboronic acid (0.8mmol, 121.57mg), tetrahydrofuran (5mL ) was dissolved, tetrakistriphenylphosphine palladium (0.01mmol, 12mg) was added, reacted at 50°C for 3h, and the reaction was detected by TLC; the reaction solution was washed into a 100mL egg-shaped bottle with ethyl acetate, an appropriate amount of silica gel was added, and spin-dried. Separation by silica gel column chromatography gave 72.7 mg of a yellow solid with a yield of 77%. Melting point, 170-171℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.31(s,1H),8.25(s,1H),7.77(d,J=8.8Hz,2H),7.62(d,J= 9.6Hz, 1H), 7.42(t, J=8.8Hz, 4H), 7.26-7.24(m, 2H), 7.14(t, J=9.0Hz, 4H), 6.94(d, J=9.2Hz, 1H) ,6.84(s,1H),3.94(s,3H),3.92(s,3H),3.68(s,3H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ159.03,158.87,156.28,136.85,133.94,132.46 ,132.45,131.71,131.29,131.03,130.59,130.30,129.96,128.91,128.52,128.40,128.26,126.78,125.90,125.07,124.81,124.63,120.22,114.09,113.89,101.80,55.32,55.29,54.94.IR(neat ):2962,2907,2853,2834,1608,1511,1462,1259,1174,1016,878,796,740,702cm ^-1 ; calculated value of HRMS(EI) for C ₃₃ H ₂₆ O ₃ : 470.1882, measured value 470.1883.

Example 6: 2-methoxy-5-(p-chlorophenyl)-12-(p-methoxyphenyl)naphthacene (5-(4-Chlorophenyl)-2-methoxy-12-(4- Synthesis of methoxyphenyl)tetracene). the

Under the protection of argon, in a 25mL Schlenk reaction tube with a stirring bar, add bispropargyl carbonate 1b (0.2mmol, 102.9mg), p-chlorophenylboronic acid (0.8mmol, 125.1mg), tetrahydrofuran (5mL) to dissolve , add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and the silica gel Separation by column chromatography gave 83.3 mg of a yellow solid with a yield of 88%. Melting point, 203-204℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.26(s,1H),8.20(s,1H),7.78-7.76(m,2H),7.61-7.59(m,2H), 7.54(d,J=9.6Hz,1H),7.45-7.42(m,4H),7.28-7.26(m,2H),7.18-7.16(m,2H),6.96(dd,J=9.6,2.4Hz, 1H),6.86(d,J=2.4Hz,1H),3.97(s,3H),3.70(s,3H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ158.97,156.30,137.76,135.43,134.59,133.62 ,132.80,132.40,131.52,131.08,130.52,130.48,129.86,128.80,128.39,128.29,128.03,126.49,125.39,125.21,125.02,124.90,120.69,114.14,101.94,55.33,54.99.IR(neat):3048, 3000,2955,2833,1912,1622,1505,1464,1433,1381,1286,1240,1206,1175,1115,1088,1034,1016,878,826,741cm ^-1 ;HRMS(EI)for C ₃₂ H ₂₃ O ₂ Cl Calculated value: 474.1387, measured value: 474.1391.

Example 7: 2-methoxy-5-(p-trifluoromethylphenyl)-12-(p-methoxyphenyl)naphthacene (2-methoxy-12-(4-methoxyphenyl)-5- Synthesis of (4-(trifluoromethyl)phenyl)tetracene). the

Under argon protection, bispropargyl carbonate 1b (0.2mmol, 102.9mg), p-trifluoromethylphenylboronic acid (0.8mmol, 152mg), tetrahydrofuran (5mL ) was dissolved, added tetrakistriphenylphosphine palladium (0.01mmol, 12mg), reacted at 50°C for 2.5h, and TLC detected that the reaction was complete; washed the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, added an appropriate amount of silica gel, and spin-dried , silica gel column chromatography to obtain 72.2 mg of yellow solid, yield 71%. Melting point, 173-174℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.28(s,1H),8.13(s,1H),7.91(d,J=8.0Hz,2H),7.79-7.77(m, 2H),7.65(d,J=7.6Hz,2H),7.48-7.44(m,3H),7.30-7.27(m,2H),7.19(d,J=2.0Hz,2H),6.98(dd,J =9.6,2.4Hz,1H),6.88(d,J=2.4Hz,1H),4.00(s,3H),3.72(s,3H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ159.03,156.33,143.39 (q, ⁵ J _CF =1.2Hz), 135.06, 134.95, 132.39, 131.89, 131.44, 131.12, 130.58, 130.51, 129.88 (q, ² J _CF =32.5Hz), 129.82, 128.32, 128.26, 128.16, 127.83 ,125.54(q, ³ J _CF =3.62Hz),125.30,125.15,125.04,124.40(q, ¹ J _CF =272.0Hz),120.95,114.19,102.02,55.36,55.02.IR(neat):3048,3002, 2957,2933,2835,1619,1514,1464,1433,1322,1285,1238,1206,1165,1123,1104,1065,1032,878,832,817,740,620cm ^-1 ;HRMS(EI)for C ₃₃ H ₂₃ O ₂ F ₃ : The calculated value is 508.1650, and the measured value is 508.1647.

Example 8: 2-methoxy-5-(o-fluorophenyl)-12-(p-methoxyphenyl)naphthacene (5-(2-Fluorophenyl)-2-methoxy-12-(4- Synthesis of methoxyphenyl)tetracene). the

Under argon protection, bispropargyl carbonate 1b (0.2mmol, 102.9mg), o-fluorophenylboronic acid (0.8mmol, 112mg) and tetrahydrofuran (5mL) were sequentially added into a 25mL Schlenk reaction tube with a stirring bar to dissolve, Add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 3h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and perform silica gel column chromatography After separation, 82.8 mg of yellow solid was obtained, with a yield of 90%. Melting point, 131-133℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.29(s,1H),8.22(s,1H),7.78-7.76(m,2H),7.58-7.53(m,2H), 7.48-7.42(m,3H),7.40-7.36(m,2H),7.26-7.24(m,2H),7.16(d,J=9.2Hz,2H),7.00(dd,J=9.6,2.4Hz, 1H),6.88(d,J=2.4Hz,1H),3.93(s,3H),3.69(s,3H). ¹³ CNMR(100.6MHz,CDCl ₃ )δ160.90(d, ¹ J _CF =246.5Hz ),158.96,156.32,135.06,133.61(d, ³ J _CF =4.0Hz),132.48,132.36,131.52,131.15,130.63,130.59,130.18,129.97(d, ³ J _CF =7.0Hz),129.95,128. 128.29,128.13,128.07,126.90,126.45(d, ² J _CF =16.9Hz),125.20,125.13,124.96,124.90,124.32(d, ⁴ J _CF =3.2Hz),120.98,116.02(d, ² J _CF = 21.8Hz), 114.15, 114.07, 102.09, 55.29, 54.98. IR (neat): 3042, 2999, 2932, 2833, 1620, 1513, 1490, 1462, 1448, 1432, 1245, 1236, 1205, 1176, 1118, 1097 ,1033,877,835,819,779,759,743,651,590cm ^-1 ; HRMS(EI) for C ₃₂ H ₂₃ O ₂ F calculated value 458.1682, measured value 458.1686.

Example 9: 2-methoxy-5-(thienyl)-12-(p-methoxyphenyl)naphthacene (2-(2-Methoxy-12-(4-methoxyphenyl)tetracen-5-yl ) Synthesis of thiophene). the

Under argon protection, bispropargyl carbonate 1b (0.2mmol, 102.9mg), 2-thiophene boronic acid (0.8mmol, 102.4mg) and tetrahydrofuran (5mL) were successively added into a 25mL Schlenk reaction tube with a stirring bar to dissolve , add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 3h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and use silica gel column After chromatographic separation, 70 mg of yellow solid was obtained, with a yield of 78%. Melting point, 219-220℃; ¹ HNMR (400MHz, CDCl ₃ ) δ8.46(s,1H),8.25(s,1H),7.84-7.82(m,1H),7.80-7.77(m,2H),7.67 -7.65 (m,1H),7.45-7.43(m,2H),7.37-7.34(m,1H),7.30-7.27(m,3H),7.19-7.17(m,2H),7.03(dd,J= 9.8,2.4Hz,1H),6.84(d,J=2.4Hz,1H),3.98(s,3H),3.71(s,3H). ¹³ CNMR(100.6MHz,CDCl ₃ )δ158.97,156.34,139.48,135.59 ,132.33,131.44,131.13,130.62,130.50,129.80,129.62,129.44,128.60,128.55,128.43,128.38,128.29,127.22,126.79,125.50,125.22,124.97,124.94,120.94,114.12,101.84,55.34,55.02.IR (neat):3045,2999,2960,2928,2834,1620,1513,1463,1431,1372,1242,1176,1101,1031,878,830,800,747,701cm ^-1 ;HRMS(EI)for C ₃₀ H ₂₂ O ₂ S calculation Value: 446.1341, measured value 446.1336.

Example 10: Synthesis of 2-chloro-5,12-diaryltetracene (2-chloro-5,12-diaryltetracene) from o-phthalaldehyde, p-chlorophenylacetylene and arylboronic acid. the

1) Synthesis of raw material bispropargyl carbonate 1d

Under the protection of argon, add p-chlorophenylacetylene (4.8mmol, 655.6mg) and tetrahydrofuran 10mL sequentially into a dry 50mL Schlenk reaction tube with a stirring bar, then cool to -78°C in a dry ice/acetone bath, slowly drop Add 2.5M n-butyllithium/n-hexane solution (4.4mmol, 1.76mL), after the dropwise addition is completed, let it react at -78°C for half an hour, then remove the dry ice/acetone bath, and wait until the temperature of the reaction solution rises to room temperature, by After the turbidity became clear, o-phthalaldehyde (2mmol, 268.3mg) was added, reacted for 2 hours, and the reaction was detected by TLC; quenched with saturated NH ₄ Cl solution, extracted with ethyl acetate, dried over anhydrous Na ₂ SO ₄ , filtered, Spin-dried, separated by silica gel column chromatography, eluent: petroleum ether: acetone = 2:1, to obtain 815 mg of yellow viscous liquid, yield 100%.

Add the diol (2mmol, 814.6mg), dichloromethane (10mL), pyridine (40mmol, 3.2mL), and DMAP (0.4mmol, 48.9mg) prepared above to a 100mL egg-shaped bottle with a stirrer in sequence, and ice Cool in a water bath to 0°C, add methyl chloroformate (12mmol, 0.93mL), stir for a few minutes, remove the ice-water bath, react at room temperature for 2h, and TLC detects that the reaction is complete; quenched with NH ₄ Cl solution, extracted with dichloromethane, no Water Na ₂ SO ₄ dried, filtered, spin-dried, silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 4:1, to obtain bispropargyl carbonate 1d light yellow solid 866.8mg, yield 83% . Melting point, 50-51°C; the ratio of the two diastereoisomers is 1.3:1, ¹ H NMR (CDCl ₃ , Me ₄ Si) two isomers: δ7.77-7.72 (m, 2H), 7.47-7.44(m,2H),7.35-7.32(m,4H),7.26-7.22(m,4H),6.94(s, major isomer),6.92(s, minor isomer) , 3.80(s, major isomer), 3.74(s, minor isomer); ¹³ C NMR (CDCl ₃ , Me ₄ Si) two isomers: δ154.53, 154.49, 135.06, 135.01, 134.57,134.42,133.14,133.12,129.86,129.76,129.41,128.85,128.57,128.52,120.26,120.25,87.50,87.04,85.70,85.65,67.40,67.06,55.15,55.10；IR(neat):2956,2928,2853 ,1752,1490,1441,1321,1260,1092,1016,928,829,788,760cm ^-1 ; HRMS (ESI) calculated value (calcd for) C ₂₈ H ₂₀ Cl ₂ O ₆ Na[M+Na ⁺ ]: 545.0535, measured value 545.0529.

2) Synthesis of 2-chloro-5-phenyl-12-(p-chlorophenyl) tetracene (2-chloro-12-(4-chlorophenyl)-5-phenyltetracene)

Under argon protection, bispropargyl carbonate 1d (0.2mmol, 104.7mg), phenylboronic acid (0.8mmol, 97.5mg) and tetrahydrofuran (5mL) were successively added into a 25mL Schlenk reaction tube with a stirrer to dissolve, adding Tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and perform silica gel column chromatography After separation, 78.0 mg of yellow solid was obtained, with a yield of 87%. Melting point: 222-224℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.29(s,1H),8.23(s,1H),7.80-7.76(m,2H),7.67-7.59(m,7H), 7.51-7.44(m,4H),7.32-7.29(m,2H),7.14(dd,J=9.4,2.0Hz,1H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ138.56,138.06,137.02,134.66, 133.96,132.77,131.42,131.29,131.20,131.10,129.42,129.32,129.07,128.94,128.62,128.39,128.26,127.89,127.34,126.13,125.99,125.74,125.50,125.28,124.53.IR(neat):3051,2962 , 1606, 1493, 1441, 1378, 1260, 1088, 1016, 968, 877, 797, 741, 702cm ^-1 ; HRMS(EI) for C ₃₀ H ₁₈ Cl ₂ : calculated value 448.0786, measured value 448.0791.

Example 11: Synthesis of 2-chloro-5,12-di-p-chlorophenyl tetracene (2-Chloro-5,12-bis(4-chlorophenyl)tetracene). the

Under the protection of argon, in a 25mL Schlenk reaction tube with a stirring bar, add bispropargyl carbonate 1d (0.2mmol, 104.7mg), p-chlorophenylboronic acid (0.8mmol, 125.1mg), tetrahydrofuran (5mL) to dissolve , add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and the silica gel Separation by column chromatography gave 84.1 mg of a yellow solid with a yield of 87%. Melting point: 248-250℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.24(s,1H),8.23(s,1H),7.79(dd,J=6.6,3.2Hz,2H),7.64-7.57( m,6H),7.44(s,2H),7.42(s,2H),7.32(dd,J=6.8,3.2Hz,2H),7.17-7.14(m,1H). ¹³ CNMR(100.6MHz,CDCl ₃ )δ137.00,136.85,136.46,135.12,134.06,134.03,132.70,132.67,131.45,131.26,131.25,129.36,129.26,129.10,128.99,128.81,128.64,128.30,128.27,127.35,126.31,125.86,125.74,125.71,125.47 ,124.66.IR(neat):3048,2962,2924,2854,1594,1492,1324,1260,1088,1015,969,878,796,742,687cm ^-1 ; HRMS(EI) for C ₃₀ H ₁₇ Cl ₃ calculated value: 482.0396, measured Value 482.0395.

Example 12: 2-chloro-5-(p-trifluoromethylphenyl)-12-(p-chlorophenyl)naphthacene (2-chloro-12-(4-chlorophenyl)-5-(4-( Synthesis of trifluoromethyl)phenyl)tetracene). the

Under argon protection, bispropargyl carbonate 1d (0.2mmol, 104.7mg), p-trifluoromethylphenylboronic acid (0.8mmol, 152mg), tetrahydrofuran (5mL ) was dissolved, tetrakistriphenylphosphine palladium (0.01mmol, 12mg) was added, reacted at 50°C for 3h, and the reaction was detected by TLC; the reaction solution was washed into a 100mL egg-shaped bottle with ethyl acetate, an appropriate amount of silica gel was added, and spin-dried. Separation by silica gel column chromatography gave 88.8 mg of a yellow solid with a yield of 86%. Melting point: 233-234℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.25(s,1H),8.18(s,1H),7.93(d,J=8.0Hz,2H),7.82-7.79(m, 2H),7.66-7.61(m,5H),7.52(d,J=9.6Hz,1H),7.46-7.44(m,2H),7.35-7.33(m,2H),7.18(dd,J=9.2, ⁽ _{_} ^_ _{_} q, ² J _CF =32.6Hz), 129.32, 129.22, 129.15, 128.60, 128.40, 128.30, 128.28, 127.22, 126.56, 125.96, 125.87, 125.72 (q, ³ J _CF =3.72Hz), 125.67, 124. 124.30(q, ¹ J _CF =272.1Hz).IR(neat):3049,2926,2854,1610,1488,1403,1324,1166,1126,1105,1066,1018,968,878,832,742cm ^-1 ;HRMS(EI) for C ₃₁ H ₁₇ F ₃ Cl ₂ : calculated value 516.0659, found value 516.0654.

Example 13: 2-chloro-5-(2-thienyl)-12-(p-chlorophenyl)naphthacene (2-(2-Chloro-12-(4-chlorophenyl)tetracen-5-yl)thiophene )Synthesis. the

Under the protection of argon, in a 25mL Schlenk reaction tube with a stirring bar, add bispropargyl carbonate 1d (0.2mmol, 104.7mg), 2-thiophene boronic acid (0.8mmol, 102.4mg), tetrahydrofuran (5mL) to dissolve , add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 3h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and use silica gel column After chromatographic separation, 40.5 mg of a yellow solid was obtained, with a yield of 45%. Melting point: 238-239℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.49(s,1H),8.21(s,1H),7.86-7.78(m,3H),7.70-7.63(m,3H), 7.58(m,1H),7.44(dd,J=8.0,0.8Hz,2H),7.39-7.37(m,1H),7.35-7.32(m,2H),7.30-7.28(m,1H),7.28- 7.20(m,1H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ138.57,136.79,136.07,134.09,132.64,131.51,131.39,131.30,130.22,129.88,129.77,129.33,129.21,129.09,128.82,128.43,128.27 ^MS (EI) calculated for C ₂₈ H ₁₆ SCl ₂ : 454.0350, found 454.0352.

Example 14: Synthesis of 2-trifluoromethyl-5,12-diaryltetracene (2-trifluoromethyl-5,12-diaryltetracene) from o-phthalaldehyde, p-trifluoromethylphenylacetylene and arylboronic acid ). the

1) Synthesis of raw material bispropargyl carbonate 1e. the

Under the protection of argon, add p-chlorophenylacetylene (2.4mmol, 408.3mg) and tetrahydrofuran 10mL in sequence in a dry 50mL Schlenk reaction tube with a stirring bar, then cool to -78°C in a dry ice/acetone bath, slowly drop Add 2.5M n-butyllithium/n-hexane solution (2.2mmol, 0.88mL), after the dropwise addition is complete, let it react at -78°C for half an hour, then remove the dry ice/acetone bath, and wait until the temperature of the reaction solution rises to room temperature, by After the turbidity became clear, o-phthalaldehyde (1mmol, 134.1mg) was added, reacted for 1.5 hours, and the reaction was detected by TLC; quenched with saturated NH ₄ Cl solution, extracted with ethyl acetate, dried over anhydrous Na ₂ SO ₄ , filtered, Spin-dried, separated by silica gel column chromatography, eluent: petroleum ether: acetone = 3:1, to obtain 473.4 mg of yellow viscous liquid, yield 100%.

Add the diol (2mmol, 473.4mg), dichloromethane (10mL), pyridine (20mmol, 1.6mL), DMAP (0.2mmol, 24.4mg) prepared above to a 100mL egg-shaped bottle with a stirrer, and ice Cool in a water bath to 0°C, add methyl chloroformate (6mmol, 0.46mL), stir for a few minutes, remove the ice-water bath, react at room temperature for 2.5h, and TLC detects that the reaction is complete; quenched with NH ₄ Cl solution, extracted with dichloromethane, Dry over anhydrous Na ₂ SO ₄ , filter, spin dry, and separate by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 5:1, to obtain 525.9 mg of bispropargyl carbonate 1d light yellow solid, yield 91 %. Melting point, 51-52°C; the ratio of the two diastereomers is 2:1, ¹ H NMR (CDCl ₃ , Me ₄ Si) two isomers: δ7.80-7.74(m), 7.52- 7.47(m), 6.99(s, minor isomer), 6.97(s, major isomer), 3.82(s, minor isomer), 3.74(s, major isomer) isomer); ¹³ C NMR (CDCl ₃ , Me ₄ Si) two isomers: δ154.52, 154.48, 134.41, 134.26, 132.13, 132.08, 130.60(q, ² J _CF =32.6Hz), 130.63(q, ² J _CF =32.9Hz),129.99,129.90,129.43,128.94,125.52,125.50,125.16,125.06(q, ³ J _CF =4.3Hz),125.05,123.68(q, ¹ J _CF =270.3Hz),87.14,87.06, 86.98, 86.66, 67.24, 66.95, 55.19, 55.12; IR (neat): 2962, 1754, 1615, 1443, 1406, 1324, 1260, 1168, 1068, 1017, 931, 797cm ^-1 ; HRMS (ESI) calculated value (calcd for) C ₃₀ H ₂₀ F ₆ O ₆ Na [M+Na ⁺ ]: 613.1062, found 613.1056.

2) 2-trifluoromethyl-5-(p-chlorophenyl)-12-(p-trifluoromethylphenyl)naphthacene (5-(4-chlorophenyl)-2-(trifluoromethyl)-12-( Synthesis of 4-(trifluoromethyl)phenyl)tetracene)

Under the protection of argon, add bispropargyl carbonate 1e (0.2mmol, 118.1mg), p-chlorophenylboronic acid (0.8mmol, 125.1mg) and tetrahydrofuran (5mL) successively into a 25mL Schlenk reaction tube with a stirring bar to dissolve , add tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 50°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of silica gel, spin dry, and the silica gel Separation by column chromatography gave 78.6 mg of a yellow solid with a yield of 71%. Melting point: 218-220℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.32(s,1H),8.23(s,1H),7.96(d,J=8.0Hz,2H),7.90(s,1H) ¹³ C NMR(100.6MHz,CDCl ₃ )δ141.99(q, ⁵ J _CF =1.1Hz),137.79,136.85,136.78,134.24,132.65,131.79,131.76,131.60,130.54(q, ² J _CF =32.6Hz) ,129.62,129.11,129.04,129.03,128.45,128.36,128.31,127.25,126.87(q, ⁵ J _CF =32.0Hz),126.26,126.15,125.87(q, ³ J _CF =3.4Hz),125.826,124.7 (q, ¹ J _CF =272.6Hz),124.69(q, ³ J _CF =5.4Hz),124.12(q, ¹ J _CF =272.6Hz),120.00(q, ³ J _CF =2.8Hz).IR(neat ):3051,2927,1618,1490,1386,1324,1294,1163,1121,1066,1018,973,827,742cm ^-1 ; HRMS(EI) for C ₃₂ H ₁₇ F ₆ Cl: calculated value 550.0923, measured value 550.0924.

Example 15: 2-trifluoromethyl-5,12-bis(p-trifluoromethylphenyl)tetracene (2-(trifluoromethyl)-5,12-bis(4-(trifluoromethyl)phenyl)tetracene) Synthesis. the

Under argon protection, bispropargyl carbonate 1e (0.2mmol, 118.1mg), p-trifluoromethylphenylboronic acid (0.8mmol, 152mg), tetrahydrofuran (5mL ) was dissolved, tetrakistriphenylphosphine palladium (0.01mmol, 12mg) was added, reacted at 50°C for 3h, and the reaction was detected by TLC; the reaction solution was washed into a 100mL egg-shaped bottle with ethyl acetate, an appropriate amount of silica gel was added, and spin-dried. Separation by silica gel column chromatography gave 96.4 mg of a yellow solid with a yield of 82%. Melting point: 231-232℃; ¹ HNMR (400MHz, CDCl ₃ ) δ8.25(s,2H),7.97(dd,J=8.0,4.0Hz,4H),7.92(s,1H),7.84(dd,J =6.4,3.6Hz,2H),7.72-7.67(m,5H),7.40-7.37(m,3H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ142.38(q, ⁵ J _CF =0.9Hz) ,141.90(q, ⁵ J _CF =0.9Hz),138.17,136.44,131.91,131.76,131.74,131.65,130.63(q, ² J _CF =32.7Hz),130.46(q, ² J _CF =33.0Hz),129.41 ,129.01,128.92,128.39,128.29,128.22,128.14,127.22,126.94(q, ² J _CF =32.2Hz),126.40,126.24,125.91(q, ³ J _CF =3.7Hz),125.84(q, ³ J _CF =3.6Hz),125.631,124.78(q, ³ J _CF =5.2Hz),124.08(q, ¹ J _CF =271.7Hz),124.28(q, ¹ J _CF =271.5Hz),124.26(q, ¹ J _CF =272.2Hz),120.25(q, ³ J _CF =2.9Hz).IR(neat):3052,2962,2930,2855,1617,1324,1296,1164,1123,1067,1020,973,836cm ^-1 ;HRMS (EI) for C ₃₃ H ₁₇ F ₉ : calculated value 584.1187, measured value 584.1188.

Example 16: Synthesis of 5-alkyl-12-aryltetracene (5-alkyl-12-aryltetracene) from o-phthalaldehyde, phenylacetylene, and alkylboronic acid. the

1) Synthesis of raw material bispropargyl carbonate 1f

Under the protection of argon, add phenylacetylene (120mmol, 13.2mL) and tetrahydrofuran (120mL) sequentially to a dry 250mL three-neck flask with a stirring bar, then cool to -78°C in a dry ice/acetone bath, and slowly add 2.5M n-Butyllithium/n-hexane solution (110mmol, 44mL) was added dropwise, and allowed to react at -78°C for half an hour, then the dry ice/acetone bath was removed, and after the temperature of the reaction solution rose to room temperature and changed from cloudy to clear, Add o-phthalaldehyde (50mmol, 6.71g), react for 2 hours, TLC detects that the reaction is complete; quenched with saturated NH ₄ Cl solution, extracted with ethyl acetate, dried with anhydrous Na ₂ SO ₄ , filtered, spin-dried, silica gel column Chromatographic separation, eluent: petroleum ether: acetone = 5:1, 17.03 g of yellow viscous liquid (containing a small amount of ethyl acetate) was obtained, and the yield was 100%.

Add the diol (10mmol, 3.38g), dichloromethane (50mL), triethylamine (60mmol, 8.3mL), DMAP (2mmol, 244mg) prepared above to a 100mL egg-shaped bottle with a stirrer, and ice Cool in a water bath to 0°C, add Boc ₂ O (40mmol, 8.7g), stir for a few minutes, remove the ice-water bath, react at room temperature for 2 hours, and TLC detects that the reaction is complete; quenched with NH ₄ Cl solution, extracted with dichloromethane, anhydrous Na ₂ SO ₄ was dried, filtered, spin-dried, and separated by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 3:1, to obtain 5.21 g of bispropargyl carbonate 1f as a pale yellow solid, with a yield of 97%. The ratio of two diastereoisomers is 1.4:1, melting point: 51-52℃; ¹ H NMR (CDCl ₃ , Me ₄ Si) two isomers: δ7.82-7.80(m), 7.77- 7.74(m),7.44-7.40(m,6H),7.28-7.21(m,6H),6.96(s, minor isomer),6.94(s, major isomer),1.47(s , minor isomer), 1.45 (s, major isomer); ¹³ C NMR (CDCl ₃ , Me ₄ Si) two isomers: δ152.12, 135.00, 134.82, 131.82, 129.41, 129.25, 129.07 ,128.61,128.57,128.36,128.06,128.01,122.03,122.02,88.00,87.55,85.38,85.29,82.88,82.85,66.11,65.81,27.64,27.60. 1491,1370,1321,1248,1153,1072,1033,1009,994,944,860,790,755,691cm ^-1 ; HRMS (ESI) calculated value (calcd for) C ₃₄ H ₃₄ O ₆ Na[M+Na ⁺ ]: 561.2253, measured value 561.2248 .

2) Synthesis of 5-n-butyl-12-phenyltetracene (5-butyl-12-phenyltetracene). the

Under argon protection, bispropargyl carbonate 1f (0.2mmol, 108mg), n-butylboronic acid (0.8mmol, 82mg) and tetrahydrofuran (5mL) were successively added into a 50mL sealed tube with a stirrer to dissolve, and Tetrahydrofuran (4 Triphenylphosphine palladium (0.01mmol, 12mg) was reacted at 90°C for 3h, and the reaction was detected by TLC; the reaction solution was washed into a 100mL egg-shaped bottle with ethyl acetate, an appropriate amount of neutral alumina was added, spin-dried, and neutral Separation by alumina column chromatography yielded 53 mg of an orange-red solid, with a yield of 74%. Melting point, 127-128℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.94(s,1H),8.31(d,J=9.2,1H),8.27(s,1H),8.03(d,J=8.4 ,1H),7.76(d,J=8.4,1H),7.65-7.56(m,4H),7.48(dd,J=8.0,1.2,2H),7.43-7.22(m,4H),3.83(t, J=8.0,2H),1.98-1.94(m,2H),1.74-1.68(m,2H),1.10(t,J=7.2,3H). ¹³ CNMR(100.6MHz,CDCl ₃ )δ139.58,135.70,135.37 ,131.58,131.00,130.74,129.50,129.35,128.49,128.48,128.42,128.36,128.19,127.81,127.39,126.43,125.18,125.02,124.81,124.57,124.42,122.94,33.61,28.34,23.56,14.16.IR(neat ):3057,3029,2957,2927,2870,2857,1600,1493,1460,1374,1262,1031,802,751,703cm ^-1 ; HRMS(EI) for C ₂₈ H ₂₄ : calculated value 360.1878, measured value 360.1880.

Example 17: Synthesis of 5-methyl-12-phenyltetracene (5-methyl-12-phenyltetracene). the

Under the protection of argon, add bispropargyl carbonate 1f (0.2mmol, 108mg), methylboronic acid (0.8mmol, 48mg), tetrahydrofuran (5mL) to dissolve in a sealed 50mL tube with a stirrer, and add four three Phenylphosphine palladium (0.01mmol, 12mg), react at 90°C for 3h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of neutral alumina, spin dry, and neutralize Separated by aluminum column chromatography, 37.5 mg of orange-red solid was obtained, with a yield of 59%. Melting point, 178-180℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.93(s,1H),8.33-8.30(m,1H),8.26(s,1H),8.01(d,J=8.4,1H ),7.76(d,J=8.0,1H),7.64-7.56(m,4H),7.47-7.45(m,2H),7.41-7.23(m,4H),3.29(s,3H). ¹³ C NMR (100.6MHz,CDCl ₃ )δ139.51,135.60,131.62,130.94,130.76,130.08,129.40,129.12,129.01,128.88,128.45,128.42,128.36,127.68,127.41,126.28,125.23,125.05,124.77,124.72,124.44,123.23 , 14.63. IR(neat): 3007, 2989, 2923, 1275, 750cm ^-1 ; HRMS(EI) for C ₂₅ H ₁₈ : calculated value 318.1409, measured value 318.1408.

Example 18: Synthesis of 5-isobutyl-12-phenyltetracene (5-Isobutyl-12-phenyltetracene)

Under argon protection, bispropargyl carbonate 1f (0.2mmol, 108mg), isobutylboronic acid (0.8mmol, 82mg) and tetrahydrofuran (5mL) were successively added into a 50mL sealed tube with a stirrer to dissolve, and tetrahydrofuran was added to Triphenylphosphine palladium (0.01mmol, 12mg) was reacted at 90°C for 3h, and the reaction was detected by TLC; the reaction solution was washed into a 100mL egg-shaped bottle with ethyl acetate, an appropriate amount of neutral alumina was added, spin-dried, and neutral Separation by alumina column chromatography yielded 53 mg of an orange-red solid, with a yield of 74%. Melting point, 140-141℃; ¹ HNMR (400MHz, CDCl ₃ ) δ8.95(s, 1H), 8.33(d, J=9.2, 1H), 8.26(s, 1H), 8.01(d, J=8.4, 1H),7.76(d,J=8.4,1H),7.65-7.56(m,4H),7.49-7.46(m,2H),7.41-7.21(m,4H),3.74(d,J=7.2,2H ),2.45-2.35(m,1H),1.12(d,J=6.4,6H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ139.62,135.86,134.50,131.58,130.84,130.64,129.46,129.31,129.28, 128.90,128.54,128.43,128.31,127.76,127.39,126.35,125.20,125.15,125.04,124.61,124.34,123.66,36.81,31.23,23.26.IR(neat):3050,2963,2924,2853,1617,1456,1405 ,1388,1323,1295,1260,1164,1119,1065,1018,972,798,742cm ^-1 ; HRMS(EI) for C ₂₈ H ₂₄ calculated value: 360.1878, measured value 360.1879.

Example 19: Synthesis of 5-phenylethyl-12-phenyltetracene (5-Phenethyl-12-phenyltetracene)

Under the protection of argon, add bispropargyl carbonate 1f (0.2mmol, 108mg), phenethylboronic acid (0.8mmol, 120mg) and tetrahydrofuran (5mL) to dissolve in a sealed 50mL tube with a stirrer, and add four three Phenylphosphine palladium (0.01mmol, 12mg), react at 90°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of neutral alumina, spin dry, neutral Separation by alumina column chromatography gave 40.5 mg of an orange-red solid with a yield of 50%. Melting point, 137-138℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.97(s,1H),8.35(d,J=9.2Hz,1H),8.29(s,1H),8.03(d,J= 8.8Hz,1H),7.78(d,J=8.8Hz,1H),7.68-7.58(m,4H),7.51-7.36(m,8H),7.33-7.22(m,3H),4.13(dd,J =8.4Hz,2H),3.25(dd,J=8.4Hz,2H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ142.19,139.45,136.24,133.82,131.55,131.19,130.77,129.50,129.34,128.67,128.50 ,128.48,128.44,128.37,128.36,128.06,127.93,127.46,126.60,126.25,125.35,125.18,125.11,124.47,124.20,122.65,37.23,30.65.IR(neat):3059,3024,2957,2925,2853, 1742,1457,1378,1261,1089,1020,750,702,614cm ^-1 ; HRMS(EI) for C ₃₂ H ₂₄ calculated value: 408.1878, measured value 408.1875.

Example 20: Synthesis of 5,14-diarylpentacene (5,14-diarylpentacene) or 5-alkyl-14- Aryl pentacene (5-alkyl-12-arylpentacene)

1) Synthesis of raw material bispropargyl carbonate 3. the

Under argon protection, add phenylacetylene (12mmol, 1.32mL) and tetrahydrofuran (50mL) sequentially to a dry 100mL Schlenk reaction tube with a stirrer, then cool to -78°C in a dry ice/acetone bath, and slowly add 2.5M n-Butyllithium/n-hexane solution (11mmol, 4.4mL), after the dropwise addition is completed, let it react at -78°C for half an hour, then remove the dry ice/acetone bath, and wait until the temperature of the reaction solution rises to room temperature and changes from cloudy to clear , Add o-phthalaldehyde (5mmol, 921mg), react for 1.5 hours, TLC detects that the reaction is complete; quenched with saturated NH ₄ Cl solution, extracted with ethyl acetate, dried with anhydrous Na ₂ SO ₄ , filtered, spin-dried, silica gel column Chromatographic separation, eluent: petroleum ether: acetone = 5:1, 1.78 g of light yellow solid was obtained, yield 91%.

Add the diol (4.4mmol, 1.72g), dichloromethane (20mL), pyridine (44mmol, 3.5mL), and DMAP (0.44mmol, 53.8mg) prepared above in sequence in a 100mL egg-shaped bottle with a stirrer, Cool in an ice-water bath to 0°C, add methyl chloroformate (26.4mmol, 2mL), stir for a few minutes, remove the ice-water bath, react at room temperature for 1.5h, TLC detects that the reaction is complete; NH ₄ Cl solution is quenched, dichloromethane extraction , dried over anhydrous Na ₂ SO ₄ , filtered, spin-dried, separated by silica gel column chromatography, eluent: petroleum ether: ethyl acetate=3:1, to obtain 2.10 g of bispropargyl carbonate 3 yellow solid, yield 95 %. The ratio of two diastereoisomers is 1.5:1, melting point: 60-61℃; ¹ H NMR (CDCl ₃ , Me ₄ Si) two isomers: δ8.29(s, secondary isomer minor isomer), 8.26(s, major isomer), 7.90-7.88(m), 7.54-7.43(m), 7.30-7.24(m), 7.13(s, minor isomer), 7.10( s, major isomer), 3.80(s, minor isomer), 3.72(s, major isomer); ¹³ C NMR (CDCl ₃ , Me ₄ Si) two isomers :δ154.60,154.55,133.15,131.92,131.88,129.64,128.98,128.85,128.78,128.16,128.10,128.04,128.01,127.33,127.25,121.80,88.80,88.34,84.86,84.75,67.95,67.59,55.06,55.01.IR (neat):3058,2956,2852,2228,1752,1491,1441,1259,930,895,790,756,691cm ^-1 ; HRMS (ESI) calculated value (calcd for)C ₃₂ H ₂₄ O ₆ Na[M+Na ⁺ ]:527.1471 , the measured value is 527.1465.

2) Synthesis of 5,14-diphenylpentacene (5,14-diphenylpentacene). the

Under argon protection, bispropargyl carbonate 3 (0.2mmol, 100.9mg), phenylboronic acid (0.8mmol, 97.5mg) and tetrahydrofuran (5mL) were successively added into a 25mL Schlenk reaction tube with a stirring bar to dissolve, adding Tetrakistriphenylphosphinepalladium (0.01mmol, 12mg), react at 50°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of neutral alumina, spin dry, Separation by neutral alumina column chromatography gave 46.5 mg of dark purple solid, with a yield of 54%. Melting point: 229-231℃; ¹ HNMR (400MHz, CDCl ₃ ) δ8.60(s, 2H), 8.47(s, 2H), 7.82-7.80(m, 2H), 7.70-7.58(m, 12H), 7.26 -7.24(m,2H),7.19-7.16(m,2H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ139.32,136.91,131.56,131.54,129.56,129.28,129.23,128.59,128.35,127.64,127.05, ,126.07,125.05,124.72.IR(neat):3053,2954,2925,1599,1493,1440,1392,1323,1264,1169,1128,1070,1030,950,896,752,702,670cm ^-1 ;HRMS( _34I H)forC ₂₂ : The calculated value is 430.1722, and the measured value is 430.1721.

Example 21: Synthesis of 5-phenyl-14-(p-trifluoromethylphenyl)pentacene (5-phenyl-14-(4-(trifluoromethyl)phenyl)pentacene). the

Under argon protection, bispropargyl carbonate 3 (0.2mmol, 100.9mg), p-trifluoromethylphenylboronic acid (0.8mmol, 152mg), tetrahydrofuran (5mL ) was dissolved, added tetrakistriphenylphosphine palladium (0.01mmol, 12mg), reacted at 50°C for 2.5h, and the reaction was detected by TLC; the reaction solution was washed into a 100mL egg-shaped bottle with ethyl acetate, and an appropriate amount of neutral alumina was added , spin-dried, and separated by silica gel column chromatography to obtain 59 mg of dark purple solid, with a yield of 59%. Melting point, 239-241℃; ¹ HNMR(400MHz, CDCl ₃ )δ8.60(s,1H),8.46(s,2H),8.45(s,1H),7.94(d,J=8.4Hz,2H), 7.82-7.79(m,2H),7.71-7.62(m,6H),7.57-7.55(m,2H),7.52-7.49(m,1H),7.26-7.24(m,2H),7.20-7.17(m ,2H). ¹³ C NMR(100.6MHz,CDCl ₃ )δ143.40(q, ⁵ J _CF =1.0Hz),139.05,137.72,134.88,132.01,131.72,131.62,131.46,129.95(q,2JC-F= 32.4Hz), 129.67, 129.54, 129.12, 129.10, 129.08, 128.85, 128.63, 128.32, 127.77, 127.25, 126.62, 126.45, 126.39, 125.65 (q, ³ J _CF = 3.8, 8, 125.63, 2 125.20,124.77,124.45(q, ¹ J _CF =272.4Hz).IR(neat):3052,2926,2854,1616,1441,1401,1323,1166,1127,1105,1066,1020,895,842,761,738,703cm ^-1 HRMS(EI) for C ₃₅ H ₂₁ F ₃ : calculated value 498.1595, found value 498.1598.

Example 22: Synthesis of 5-n-butyl-14-phenylpentacene (5-butyl-14-phenylpentacene)

Under argon protection, bispropargyl carbonate 3 (0.2mmol, 100.9mg), n-butylboronic acid (0.8mmol, 82mg) and tetrahydrofuran (5mL) were added successively to dissolve in a sealed 50mL tube with a stirring bar, and added Tetrakistriphenylphosphine palladium (0.01mmol, 12mg), react at 90°C for 2.5h, TLC detects that the reaction is complete; wash the reaction solution into a 100mL egg-shaped bottle with ethyl acetate, add an appropriate amount of neutral alumina, spin dry, Separation by neutral alumina column chromatography yielded 56.1 mg of dark purple solid, with a yield of 68%. Melting point, 186-187℃; ¹ H NMR (400MHz, CDCl ₃ ) δ9.24(s,1H),8.70(s,1H),8.56(s,1H),8.45(s,1H),8.26(d, J=8.8Hz,1H),7.92(d,J=8.0Hz,1H),7.82(d,J=8.0Hz,1H),7.66-7.58(m,4H),7.52-7.50(dd,J=8.0 ,1.6Hz,2H),7.37-7.24(m,3H),7.18(dd,J=8.2,6.6Hz,1H),3.88-3.83(m,2H),2.04-1.98(m,2H),1.78- 1.72(m,2H),1.26(t,J=7.2Hz,3H) ^.13 CNMR(100.6MHz,CDCl ₃ )δ139.60,135.61,135.24,131.64,131.61,131.51,129.70,129.54,129.42,129.39,128.50 128.39,128.35,128.28,127.91,127.46,126.78,126.50,126.49,125.05,124.98,124.82,124.70,124.40,123.07,33.57,28.46,23.65,14.20.IR(neat):3052,2955,2926,2856,1441 , 1377, 1264, 952, 892, 756, 736, 703, 655 cm ^-1 ; HRMS (EI) for C ₃₂ H ₂₆ : calculated value 410.2035, measured value 410.2037.

Claims (6)

1. A synthetic method of tetracene or pentacene compounds, characterized in that in an organic solvent and at room temperature to 150 ° C, the molecular formula is The dicarbonate compound and R ³ B(OH) ₂ undergo a cyclization reaction in the presence of a catalytic amount of palladium catalyst for 0.1 minutes to 100 hours to obtain naphthacene or pentacene compound; the dicarbonate compound , R ³ B(OH) ₂ and the molar ratio of the palladium catalyst are: 1:1-6:0.001-1; The tetracene or pentacene compound has the following structural formula:

Wherein, R ¹ and R ² are H or R ¹ and R ² are connected to form a benzo ring; R ₃ is C _1-8 alkyl, tert-butyl, phenyl, Z-substituted phenyl, thienyl; said Z is C _1-8 alkyl, C _1-8 alkoxy, tri Fluoromethyl, phenyl, nitro, amino, ester, acyl or halide. R ⁴ , R ⁵ , R ⁶ , R ⁷ are H, C _1-8 alkyl, C _1-8 alkoxy, trifluoromethyl, phenyl, nitro, amino, ester, acyl or halogen ; ^R is phenyl, phenyl substituted by Q; said Q is C _1-8 alkyl, C _1-8 alkoxy, trifluoromethyl, phenyl, nitro, amino, ester group, acyl or halogen. 2. the synthetic method of tetracene and pentacene compound as claimed in claim 1 is characterized in that described tetracene and pentacene compound have following structural formula:

Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described in claim 1. 3. the synthetic method of naphthacene or pentacene compound as claimed in claim 1 is characterized in that described palladium catalyst is palladium chloride, palladium acetate, palladium bromide, palladium trifluoroacetate, ditriphenylene Phosphine dichloride palladium, tetrakistriphenylphosphine palladium, dichlorodiacetonitrile palladium, dichlorodibenzonitrile palladium, 5% palladium carbon, 1,2-bis(diphenylphosphino)ethane dichloride Palladium, allylpalladium(II) chloride dimer, bis(dibenzylideneacetone)palladium, [1,3-bisdiphenylphosphinopropane]palladium chloride, bis(tricyclohexylphosphine)palladium or palladium dichloride. 4. the synthetic method of naphthacene or pentacene compounds as claimed in claim 1, is characterized in that described organic solvent solvent is diethylamine, triethylamine, methylene dichloride, ethylene dichloride, chloroform , ether, 1,4-p-oxane, benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide (DMA), tetrahydrofuran, acetonitrile dimethyl sulfoxide , hexamethylphosphoramide or a mixed solvent of the above solvents. 5. The method for synthesizing naphthacene and pentacene compounds according to claim, characterized in that the reaction time is 0.1-1000 minutes. 6. the synthetic method of naphthacene or pentacene compound as claimed in claim 13 is characterized in that described reaction product adopts recrystallization, thin-layer chromatography, column chromatography or vacuum distillation method to carry out purification and separation .