CN105017302A - Bi(S,S-dioxo-dibenzothiophene) five-membered ring compound and preparation method and application thereof - Google Patents

Abstract

The invention discloses a bi(S,S-dioxo-dibenzothiophene) five-membered ring compound and a preparation method and application thereof. The existence of bi-sulfuryl in the bi(S,S-dioxo-dibenzothiophene) five-membered ring compound is more beneficial for improving the electron affinity of molecules. Alkyl chains are introduced on a five-membered ring, so that the solubility of monomers in an organic solvent can be obviously improved. The plane conjugacy of the compound is better, and is beneficial for the transmission of a current carrier. Higher D-A mutual effect existing in the molecules of the compound endows higher fluorescence of the material. The bi(S,S-dioxo-dibenzothiophene) five-membered ring compound is synthesized and obtained through common organic chemistry reactions such as substitution reactions, Suzuki coupling and ring-closure reactions and oxidation reactions. The compound has good solubility in the organic solvent, and is suitable for solution processing. The compound has wide application prospects in the fields of organic luminescence display, organic photovoltaic cells and organic field-effect tubes.

Description

Bis(S,S-dioxo-dibenzothiophene) five-membered ring compound and its preparation method and application

technical field

The invention belongs to the field of organic optoelectronics, and specifically relates to a bis(S,S-dioxo-dibenzothiophene) five-membered ring compound and a preparation method and application thereof.

Background technique

The earliest reports on organic electroluminescent diodes can be traced back to the 1960s. Pope et al. prepared organic electroluminescent devices with anthracene single crystals (Pope M.; Kallmann H.P.; Magnante P. Electroluminescence in Organic Crystals, The Journal of chemical physics, 1963, 38:2042–2043). Organic solar photovoltaic cell materials started in the 1990s. In 1995, Hegel et al. used the donor/acceptor blended bulk heterojunction structure for the first time to make organic polymer battery materials, and the device performance was greatly improved compared with the donor/acceptor bilayer structure. (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science 1995, 270, 178‐180). In terms of organic field effect transistors, in 1987, VanSlyke et al. introduced biphenyl diamine derivative materials into the device to improve the hole mobility of the device and obtained better results. (Appl. Phys. Lett., 51(12), 21 September 1987). The development of high-performance organic optoelectronic materials and devices has become the common goal of many scientific researchers, among which the development of materials is the key and the basic guarantee for the preparation of high-performance devices.

The bis-S,S-dioxo-dibenzothieno five-membered ring compound is an electron-deficient unit with many advantages. Compared with a single S,S-dioxo-dibenzothiophene unit, its electron-deficiency is stronger , which is more conducive to improving the electron affinity of the material, and the two sulfur atoms in it have reached the highest chemical valence state, and the structural stability is better. The fused ring structure increases the molecular conjugation plane, which is conducive to improving the carrier transport performance of the material. At the same time, the strong D-A interaction in the molecule increases the delocalization of the electron cloud in the molecule and enhances the fluorescence of the material. The poor solubility of a single S,S-dioxo-dibenzothiophene unit, while the solubility of the double S,S-dioxo-dibenzothieno five-membered ring with a fused ring structure has been greatly improved. From the perspective of chemical synthesis, the bis-S,S-dioxo-dibenzothiophene five-membered ring structure has more modification sites than a single S,S-dioxo-dibenzothiophene unit, and is more chemically modified. Strong, can introduce long alkyl chains to improve the solubility of compounds. For organic solar cell materials, the bissulfone group of this type of compound has a good electron-deficient unit and can be used as an acceptor unit in the battery material. At the same time, the bissulfone group can reduce the HOMO energy level of the material, which is beneficial to improve the open circuit of the device. Voltage, the planar conjugation of the compound is better, which is conducive to the separation and transport of charges. For organic field effect transistors, bis-S,S-dioxo-dibenzothieno five-membered ring compounds also have great application potential. The existence of the double sulfone group greatly enhances the rigidity of the molecule and enhances the stability of the molecular structure. At the same time, the material has a large planar conjugated structure, which is beneficial to the transport of holes and electrons, and most of these compounds have bipolar transport properties. characteristic. The invention develops a novel double S, S-dioxo-dibenzothieno five-membered ring compound with a condensed ring structure and a preparation method thereof. This type of compound has good solubility and is suitable for solution processing; it has good spectral emission when used as a luminescent material. Due to the existence of the double sulfone group, the electron mobility of the material is significantly improved, and the fused ring structure makes it have a larger conjugated plane. It is used as an electron acceptor material and a high-mobility organic semiconductor material in organic light-emitting diodes, organic solar cells and Organic field effect transistors will have great application potential.

Contents of the invention

The invention synthesizes a compound with double S,S-dioxo-dibenzothieno five-membered ring structure through rational molecular design.

The invention provides a class of organic small molecule optoelectronic materials based on double S,S-dioxo-dibenzothieno five-membered ring structure, and applies it to the field of organic optoelectronics.

A class of bis-S, S-dioxy-dibenzothieno five-membered ring compounds, the compound has the following structural formula:

In the formula, X is one of the following structures:

Wherein, R ₁ and R ₂ are alkyl groups with 1-30 carbon atoms.

Preferably, the specific structure of the compound is:

Wherein, R ₁ and R ₂ are alkyl groups with 1-30 carbon atoms.

Two S, the preparation method of S-dioxy-dibenzothieno five-membered ring compound is characterized in that comprising the steps:

1) Dissolve 2,7-dibromo-fluorene and its heteroatom-substituted derivatives in tetrahydrofuran solution respectively, add n-butyllithium in n-hexane solution dropwise at low temperature, keep warm for 1-3 hours; then add 2-iso Propyl-4,4,5,5-tetramethyl-1,3,2-dioxaborane, react the reaction solution at room temperature for 5 to 20 hours, after the reaction is completed, use extraction, drying and purification, The product (I)-2,7-diboronate-fluorene and its heteroatom-substituted derivatives were obtained respectively;

2) Mix the product (I) and 1-bromo-2-methanesulfinylbenzene in a molar ratio of 1:2~10, dissolve them in organic solvents respectively, and react under a palladium catalyst at 40~100°C for 8 ~80 hours; after the reaction is completed, extract, dry, and purify to obtain the product (II)—2,7-bis(2-methanesulfinylphenyl)-fluorene and its heteroatom-substituted derivatives;

3) react the product (II) in trifluoromethanesulfonic acid respectively, add phosphorus pentoxide at the same time, and react for 2 to 20 hours. Heating to reflux in medium temperature for 2 to 30 hours, extraction, drying and purification after the reaction to obtain the product (Ш)-bis(dibenzothiophene) pentacyclic compound;

4) Dissolve the product (Ш) in an organic solvent, add an oxidizing agent to react for 2 to 10 hours, after the reaction, extract, dry, and purify to obtain the product (IV)—bis(S,S-dioxo-diphenyl Dithiophene) five-membered rings (cyclopentadiene, silacyclopentadiene, germanol, stannocyclopentadiene, furan, pyrrole, phosphole, phosphoxole diene, thiophene, selenophene, borole) compounds.

In the above method, the heteroatom-substituted derivative is one of silafluorene, germanium fluorene, tin fluorene, dibenzofuran, carbazole, phosphine fluorene, phosphinoxyfluorene, thiofluorene, selenofluorene and borofluorene.

In the above method, the bis (dibenzothiophene) pentacyclic ring in step 3) is bis (dibenzothiophene) pentacyclopentadiene, bis (dibenzothiophene) silacyclopentadiene, bis ( Dibenzothiophene)germanol, bis(dibenzothiophene)stannol, bis(dibenzothiophene)furan, bis(dibenzothiophene)pyrrole, bis( Dibenzothiophene)phosphinolene, bis(dibenzothiophene)phosphoxole, bis(dibenzothiophene)thiophene, bis(dibenzothiophene)selenophene or Bis(dibenzothiophene)borole.

In the above method, the bis(S,S-dioxo-dibenzothiophene) pentacyclic ring in step 4) is bis(S,S-dioxo-dibenzothiophene)pentalene, bis(S ,S-Dioxy-dibenzothiophene)silacyclopentadiene, bis(S,S-dioxo-dibenzothiophene)germanocyclopentadiene, bis(S,S-dioxo- Dibenzothiophene) stannole, bis(S,S-dioxo-dibenzothiophene)furan, bis(S,S-dioxy-dibenzothiophene)pyrrole, ,S-Dioxy-dibenzothiophene)phosphine, bis(S,S-dioxo-dibenzothiophene)phosphoxole, bis(S,S-diox -Dibenzothiophene)thiophene, bis(S,S-dioxo-dibenzothiophene)selenophene, bis(S,S-dioxo-dibenzothiophene)borole.

In the above method, the catalyst in step 2) is Pd(PPh ₃ ) ₄ , Pd ₂ (dba) ₃ or Pd(OAc) ₂ ; the solvent is any one of tetrahydrofuran, toluene or a mixture thereof.

In the above method, the organic solvent in step 4) is one of dichloromethane, tetrahydrofuran, chloroform or a mixture thereof; the oxidant is one of hydrogen peroxide, 3-chloroperoxybenzoic acid or a mixture thereof.

Application of double S, S-dioxy-dibenzothieno five-membered ring compound in the preparation of organic electroluminescent devices, organic solar cells and organic field effect transistors.

The advantages and benefits that the present invention has are:

1) Provides a simple and effective method for the synthesis of bis-S,S-dioxo-dibenzothieno five-membered ring compound, the raw material is cheap, and is conducive to large-scale production; 2) The active site of the compound is more than a single S, S-dioxy-dibenzothiophene is more and more modified. Introducing an aliphatic alkyl chain with better solubility or some other groups with photoelectric properties at the active site helps to improve the solubility of the compound and the photoelectric properties of the material; 3) due to the double sulfone group Introduced, the electron transport performance of the material is further improved, the transport of holes and electrons of the material is more balanced, and the fused ring structure increases the thermal stability of the compound, and the strong D-A interaction in the molecule enhances the fluorescence characteristics of the material; 4) The material has good electricity deficiency and good planar conjugation, which is beneficial to the separation and conduction of charges. The existence of the bissulfone group can reduce the HOMO energy level of the compound. It can be used to prepare high open circuit voltage and 5) The plane conjugation of the compound is enhanced, and the rigidity is better, so that the compound can be used in organic field effect transistors, and materials with high mobility and high stability can be obtained.

Description of drawings:

Figure 1 is the differential scanning calorimetry curves of compounds FCSO and FNSO.

Figure 2 is the thermogravimetric curves of compounds FCSO and FNSO.

Figure 3 is the solid powder X-ray diffraction of compounds FCSO and FNSO.

Figure 4 is the cyclic voltammetry characteristic curves of compounds FCSO and FNSO.

Fig. 5 is the ultraviolet-visible absorption spectrum of compound FCSO and FNSO film.

Figure 6 is the photoluminescence spectra of compounds FCSO and FNSO thin films.

Fig. 7 is the fluorescence emission images of the compounds FNSO (left) and FCSO (right) in tetrahydrofuran solution (concentration: 10 ^-5 mol/L).

Detailed ways

The synthesis of S,S-dioxo-dibenzothiophene derivative monomers will be further described through examples below, but the present invention will not be limited to the listed examples.

Example 1

Synthesis of bis(S,S-dioxy-dibenzothiophene) pentadiene (FCSO) (Ghaemy M.,Barghamadi M.Synthesis and characterization of novel photoactive polyamide derived from substituted fluorene by copper(I)catalyst[ J].J.Appl.Polym.Sci.,2009,114(6):3464-3471.)

1) Synthesis of 2,7-dibromofluorene (1): Dissolve fluorene (20g, 120.5mmol) and iron filings (0.34g, 6mmol) in 150mL of chloroform, and stir in an ice bath (0-5°C) in the dark . Dilute liquid bromine (15.5mL, 301mmol) with 100mL of chloroform, and slowly add it dropwise to the reaction solution in the dark. After the addition, stir and react at room temperature for 10 hours. The tail gas generated by the reaction is treated with saturated aqueous sodium bisulfite. The reaction was stopped, and the reaction solution was slowly poured into an ice-saturated aqueous solution of sodium bisulfite and stirred, followed by suction filtration. The filter residue was washed successively with saturated aqueous sodium bisulfite solution, distilled water and ethanol. After air-dried, the filter residue was purified by recrystallization with chloroform, and a white solid (29.3 g, 75%) was obtained by filtration. MS(APCI): m/z(%): 325.0[M ⁺ ].

2) Synthesis of 2,7-dibromo-9,9-dioctyl fluorene (2): 2,7-dibromofluorene (20g, 61.7mmol), tetrabutylammonium bromide (1.9g, 6mmol ) was dissolved in 250 mL dimethyl sulfoxide, and stirred at room temperature under a nitrogen atmosphere. 12 mL of 50% sodium hydroxide aqueous solution was slowly added dropwise to the reaction solution. After 1 hour 1-bromooctane (29.8 g, 154.2 mmol) was added rapidly and allowed to react overnight. After stopping the reaction, the reaction solution was poured into water to quench, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, purified by column chromatography, using 200-300 mesh silica gel as the stationary phase, petroleum ether as the eluent, and then Recrystallization from acetone gave white needle crystals (30.4 g, 90%). MS(APCI): m/z(%): 549.4[M ⁺ ].

3) Preparation of 2,7-diboronate-9,9-dioctylfluorene (3): 2,7-dibromo-9,9-dioctylfluorene (5.6g, 10.2mmol) Dissolve in 130mL of anhydrous tetrahydrofuran, and add 1.6M n-butyllithium/n-hexane solution (20mL, 32mmol) dropwise at -78°C in an argon atmosphere. Reacted at -78°C for 2 hours, then quickly added 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethylenedioxy borate (25mL, 123mmol), The reaction was continued at -78°C for 1 hour. The reaction was then warmed to room temperature overnight. After the reaction, the reaction solution was poured into water to quench, extracted with dichloromethane, washed with aqueous sodium chloride, and dried over anhydrous magnesium sulfate. After concentration, it was recrystallized with tetrahydrofuran/methanol, and further purified by silica gel column chromatography (petroleum ether: ethyl acetate = 9:1 as eluent) to obtain a white solid (5.1 g, 80%). MS(APCI): m/z(%): 643.5[M ⁺ ].

4) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9,9-di-n-octylfluorene (4): 30 mL of 2M potassium carbonate aqueous solution, 2,7-bis(4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (3.86g, 6mmol) and 1-bromo-2-methyl Sulfinylbenzene (2.9 g, 13.2 mmol) was added to 60 mL of toluene and stirred under nitrogen atmosphere. When the reaction temperature rose to 90°C, 350 mg of tetrakistriphenylphosphine palladium and 190 mg of tetrabutylammonium bromide were added, and the reaction was carried out for 24 hours. Then stop the reaction and cool to room temperature, and extract with dichloromethane 1-3 times. After the organic layer was spin-dried, the chromatographic column was passed through 200-300 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (3:1), and finally a pale yellow liquid (3.6 g, 90%) was obtained. MS(APCI):m/z(%):668.0[M ⁺ ].

5) Preparation of bis(dibenzothiophene)pentadiene (5): 2,7-bis(2-methanesulfinylphenyl)-9,9-di-n-octylfluorene (0.8g, 1.2 mmol) was added into 4.2 mL of trifluoromethanesulfonic acid, stirred at room temperature for 22 hours, and then the reaction liquid was added dropwise into ice water. The reaction solution was suction filtered to obtain a light yellow solid powder and dried in the air. Add the pale yellow solid powder into 100 mL of pyridine, and heat to reflux for 12 hours in a nitrogen atmosphere. Stop the reaction and cool to room temperature, extract and neutralize the pyridine with hydrochloric acid. The chromatographic column was passed through petroleum ether and recrystallized from ethanol to obtain white powdery crystals (0.46g, 64%). MS(APCI):m/z(%):603.4[M ⁺ ].

6) Preparation of bis(S,S-dioxo-dibenzothiophene) pentadiene (FCSO): Bis(dibenzothiophene) pentadiene (120mg, 0.2mmol) and 3-chloro Peroxybenzoic acid (680 mg, 4 mmol) was dissolved in 10 mL of dichloromethane and stirred for 10 hours in an ice bath. After the reaction was completed, the reaction liquid was poured into a cold 10% mass concentration sodium hydroxide aqueous solution and stirred for 30 minutes. The organic layer was washed with water (150mL×3), concentrated and passed through a chromatographic column. The polarity of the eluent was dichloromethane/ethyl acetate (5:1), and then recrystallized with ethanol to obtain white flaky crystals (100mg, 90 %). ¹ H-NMR (600MHz, CDCl ₃ , δ) 8.19(s, 2H), 7.87(t, 4H), 7.71(m, 4H), 7.56(t, 2H), 2.13(t, 4H), 1.06(m ,20H),0.77(t,6H),0.58(s,4H). ¹³ C-NMR(150MHz,CDCl ₃ ,δ)157.37,141.58,138.39,137.64,133.88,132.03,131.66,130.45,122.35,121.70, MS(APCI):m/z(%):667.1[M ⁺ ].

Example 2

Synthesis of bis(S,S-dioxo-dibenzothiophene)silacyclopentadiene (FSiSO) (Ma Z., Chen Z.K., Lim S.L., et al. New p-type low bandgap polymers and their use :PCT Int.Appl.WO2012087243A1[P].2012-06-28; Dwyer M.P.,Keertikar K.M.,Zeng Q.,et al.Silyl-containing heterocyclic compounds and methods of use thereof for the treatment of viral diseases:PCT Int.Appl .WO 2013039876A1[P].2013-3-21.) 

1) Synthesis of 4,4'-dibromo-2,2'-dinitrobiphenyl (6): 1,4-dibromo-2-nitrobenzene (25g, 89mmol) and copper powder (12.5g , 197mmol) was added into 150mL N,N-dimethylformamide (DMF) and heated to 137°C for 2 hours. After the reaction was completed, it was cooled to room temperature and quenched with water. The reaction solution was extracted with ethyl acetate, and the organic layer was washed with brine and dried over sodium sulfate. Afterwards, it was subjected to column chromatography (n-hexane/ethyl acetate) to obtain solid powder (13.6 g, 38%). MS(APCI):m/z(%):403.0[M ⁺ ].

2) Synthesis of 4,4'-dibromo-1,1'-biphenyl-2,2'-diamine (7): 4,4'-dibromo-2,2'-dinitrobiphenyl (11g, 27.4mmol) was dissolved in 135mL of ethanol, and 78mL of 32% saturated hydrochloric acid was added. Tin powder (13g, 108.5mmol) was added to the reaction solution several times within 10 minutes, and then refluxed for 2 hours. After the reaction, the reaction solution was poured into ice water, and a 20% aqueous sodium hydroxide solution was added to bring the pH of the mixed solution to around 9.0. The product was extracted with ether, washed with brine, and dried over sodium sulfate. Filtration and concentration afforded a brown solid (8.25 g, 88%). MS(APCI):m/z(%):343.0[M ⁺ ].

3) Synthesis of 4,4'-dibromo-2,2'-diiodobiphenyl (8): 4,4'-dibromo-1,1'-biphenyl-2,2'-diamine ( 16g, 46.8 mmol) was dissolved in a mixture of 56mL hydrochloric acid and 64mL water, and stirred in an ice bath. Afterwards, 40 mL of an aqueous solution of sodium nitrite (8 g, 116 mmol) was slowly added dropwise to the reaction solution, and the temperature was kept constant at about 0° C. during the dropwise addition. After the dropwise addition was completed, the mixed solution was stirred for 30 minutes, and an aqueous solution of potassium iodide (77 g dissolved in 150 mL of water) was added dropwise to the reaction solution at -5°C, and then reacted at room temperature for 1 hour, then raised the temperature to 60°C for 3 hours, and the solution turned dark brown. After the reaction, the reaction solution was suction-filtered and purified by column chromatography (silica gel, n-hexane) to obtain a white solid (6.07 g, 23%). MS(APCI):m/z(%):564.8[M ⁺ ].

4) Synthesis of 2,7-dibromo-9,9-dioctylsilafluorene (9): 4,4'-dibromo-2,2'-diiodobiphenyl (2.8g, 4.9mmol) Dissolve in 90mL of anhydrous tetrahydrofuran solution, add 2.5M n-butyllithium n-hexane solution (7.8mL, 19.5mmol) at -78°C, keep the reaction for 1 hour, then quickly add dioctyldichlorosilane (1.8g ,5.4mmol). The reaction was incubated for 30 minutes, and then the reaction solution was raised to room temperature for overnight reaction. After the reaction was completed, the reaction was quenched with water, extracted, and the organic phase was washed with brine, dried, and purified by column chromatography to finally obtain a white solid (1.1 g, 40%). MS(APCI):m/z(%):565.4[M ⁺ ].

2) Preparation of 2,7-diboronate-9,9-dioctylsilafluorene (10): 2,7-dibromo-9,9-di-n-octylsilafluorene (0.58g, 1.02 mmol) was dissolved in 30 mL of anhydrous tetrahydrofuran. Under argon protection, 1.6M n-butyllithium/n-hexane solution (2 mL, 3.2 mmol) was added dropwise at -78°C, and the reaction was incubated for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (1 mL, 5 mmol) was added rapidly, and the reaction was continued for 2 hours. Afterwards, the reaction solution was raised to room temperature for 36 h. After the reaction, the reaction solution was poured into water to quench, extracted with dichloromethane, washed with saline, and dried over anhydrous magnesium sulfate. The solvent was evaporated, the residue was recrystallized from THF/methanol, and further purified by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1 as eluent) to obtain a white solid (0.5 g, 75%). MS(APCI):m/z(%):659.5[M ⁺ ].

3) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9,9-dioctylsilylfluorene (11): 30 mL of 2M potassium carbonate aqueous solution, 2,7-bis( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylsilafluorene (5.9g, 9mmol) and 1-bromo- 2-Methanesulfinylbenzene (4.4g, 19.8mmol) was added into a three-necked flask, 60mL of toluene was added and nitrogen was blown. When the reaction temperature rose to 80°C, 500 mg of tetrakistriphenylphosphine palladium and 300 mg of tetrabutylammonium bromide were added, and the reaction was carried out for 19 hours. Then stop the reaction and cool to room temperature, and extract with dichloromethane 1-3 times. After the organic layer was spin-dried, the chromatographic column was passed through 200-300 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (3:1), and a brownish-yellow liquid (5.5 g, 90%) was finally obtained. MS(APCI):m/z(%):684.0[M ⁺ ].

4) Preparation of bis(dibenzothiophene)silacyclopentadiene (12): 2,7-bis(2-methanesulfinylphenyl)-9,9-di-n-octylsilafluorene ( 8.2 g, 12 mmol) was added into 30 mL of trifluoromethanesulfonic acid, stirred at room temperature for 17 hours, and then the reaction liquid was added dropwise into ice water. Afterwards, the reaction solution was suction-filtered to obtain a light yellow solid powder and dried in the air. The light yellow solid powder was added into 300mL of pyridine, and heated to reflux under nitrogen for 10 hours. Stop the reaction and cool to room temperature, extract and neutralize the pyridine with hydrochloric acid. The chromatographic column was passed through petroleum ether, and recrystallized from ethanol to obtain a solid powder (4.8 g, 64%). MS(APCI):m/z(%):620.0[M ⁺ ].

5) Preparation of bis(S,S-dioxo-dibenzothiophene) silacyclopentadiene (FSiSO): Bis(dibenzothiophene) silacyclopentadiene (619mg, 1mmol) and 3-Chloroperoxybenzoic acid (3.4 g, 20 mmol) was dissolved in 100 mL of dichloromethane and stirred for 10 hours in an ice bath. Then the reaction solution was poured into a cold 10% aqueous sodium hydroxide solution and stirred for 25 minutes. The organic layer was washed with water (120mL×3), concentrated and passed through a chromatographic column, the polarity of the eluent was dichloromethane/ethyl acetate (5:1), and then recrystallized with ethanol to obtain a powder solid (615mg, 90%) . ¹ H-NMR (600MHz, CDCl ₃ , δ) 7.95(s, 2H), 7.83(t, 4H), 7.69(m, 4H), 7.55(t, 2H), 1.77(t, 4H), 1.07(m ,20H),0.77(t,6H),0.68(s,4H).MS(APCI):m/z(%):682.2[M ⁺ ].

Example 3

Synthesis of bis(S,S-dioxo-dibenzothiophene)germanocyclopentadiene (FGeSO) (Allard N., RB, Gendron D., et al. Germafluorenes: new heterocycles for plastic electronics [J]. Macromolecules, 2010, 43(5): 2328-2333.)

1) Synthesis of 2,7-dibromo-9,9-dioctylgermanium fluorene (13): 4,4'-dibromo-2,2'-diiodobiphenyl (5.6g, 9.8mmol) Dissolve in 150mL anhydrous tetrahydrofuran solution, add 2.5M n-butyllithium n-hexane solution (15.6mL, 39mmol) at -78°C, keep warm for 1 hour, then quickly add dioctyldichlorogermane (4.0g , 10.8mmol). Continue to incubate the reaction for 30 minutes, and then raise the reaction solution to room temperature for overnight reaction. After the reaction was completed, the reaction was quenched with water, extracted, and the organic phase was washed with brine, dried, and purified by column chromatography to finally obtain a powder solid (2.3 g, 38%). MS(APCI):m/z(%):610.1[M ⁺ ].

2) Preparation of 2,7-diboronate-9,9-dioctylgermanium fluorene (14): 2,7-dibromo-9,9-di-n-octyl germanium fluorene (1.22g, 2mmol ) was dissolved in 50 mL of anhydrous tetrahydrofuran. Under argon protection, 1.6M n-butyllithium/n-hexane solution (4 mL, 6 mmol) was added dropwise at -78°C, and reacted at -78°C for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (1.6 mL, 8 mmol) was added rapidly and the reaction was continued for 2 hours. Then the reaction mixture was raised to room temperature for 36 hours. After the reaction, the reaction solution was poured into water, extracted with ether, washed with aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was recrystallized from tetrahydrofuran/methanol, and further purified by silica gel column chromatography (petroleum ether: ethyl acetate = 6:1 as eluent) to obtain a solid powder (1.0 g, 75%). MS(APCI):m/z(%):704.2[M ⁺ ].

3) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9,9-dioctylgermanium fluorene (15): 50 mL of 2M potassium carbonate aqueous solution, 2,7-bis( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylgermaniumfluorene (7.0g, 10mmol) and 1-bromo- 2-Methanesulfinylbenzene (5.5g, 25mmol) was added to 100mL toluene, and nitrogen was blown. When the reaction temperature rose to 80° C., 500 mg tetraphenylphosphine palladium and 300 mg tetrabutylammonium bromide were added and reacted for 22 hours. Stop the reaction and cool to room temperature, and extract with dichloromethane 1-3 times. After the organic layer was spin-dried, the chromatographic column was passed through 200-300 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (2:1), and finally an oily liquid (5.1 g, 70%) was obtained. MS(APCI):m/z(%):728.6[M ⁺ ].

4) Preparation of bis(dibenzothiophene)germanocyclopentadiene (16): 2,7-bis(2-methanesulfinylphenyl)-9,9-di-n-octylgermanofluorene ( 3.6 g, 5 mmol) was added to 15 mL of trifluoromethanesulfonic acid, stirred at room temperature for 20 hours, then the reaction solution was added dropwise to ice water, and a yellow solid residue was obtained by suction filtration and dried in the air. The filter residue was added to 100 mL of pyridine, and heated to reflux for 12 hours in a nitrogen atmosphere. Stop the reaction and cool to room temperature, neutralize with hydrochloric acid, and extract with dichloromethane. The column was chromatographed with petroleum ether and recrystallized from ethanol to give a powder solid (1.7 g, 51%). Elemental analysis: C ₄₀ H ₄₆ GeS ₂ theoretical value: C72.40%, H 6.99%, S 9.66%; measured value: C72.88%, H 6.67%, S 9.58%.

4) Preparation of bis(S,S-dioxodibenzothiophene)germanol (FGeSO): Bis(dibenzothiophene)germanol (663mg, 1mmol) and 3 - Chloroperoxybenzoic acid (3.4 g, 20 mmol) was dissolved in 150 mL of dichloromethane and stirred for 10 hours under ice-bath conditions. Then, the reaction solution was poured into a cold 10% aqueous sodium hydroxide solution and stirred for 15 minutes. The organic layer was washed with water (200mL×3), concentrated and passed through a chromatographic column, the polarity of the eluent was dichloromethane/ethyl acetate (3:1), and then recrystallized with ethanol to obtain a powder solid (582mg, 80%) . ¹ H-NMR (600MHz, CDCl ₃ , δ) 8.03(s, 2H), 7.85(t, 4H), 7.73(m, 4H), 7.56(t, 2H), 1.60(t, 4H), 1.03(m ,20H),0.79(t,6H),0.67(s,4H).

Example 4

Synthesis of bis(S,S-dioxo-dibenzothiophene)stannocyclopentadiene (FSnSO) (Chen R.F., Fan Q.L., Zheng C., et al.A general strategy for the facile synthesis of 2, 7-dibromo-9-heterofluorenes[J].Org.Lett.,2006,8(2):203-205.)

1) Synthesis of 2,7-dibromo-9,9-dioctyltinfluorene (17): Dissolve 4,4'-dibromo-2,2'-diiodobiphenyl (0.56g, 0.98mmol) in In 20mL of anhydrous tetrahydrofuran solution, add 2.5M n-butyllithium n-hexane solution (1.6mL, 4mmol) at -78°C, keep the reaction solution for 1 hour, and then quickly add dioctyldichlorogermane (0.46 g, 1.1 mmol). Continue to incubate the reaction for 30 hours, and raise the reaction solution to room temperature for overnight reaction. After the reaction was completed, the reaction was quenched with water, extracted, and the organic phase was washed with brine, dried, and purified by column chromatography to obtain a powder solid (0.22 g, 35%). MS(APCI):m/z(%):656.1[M ⁺ ].

2) Preparation of 2,7-diboronate-9,9-dioctyltinfluorene (18): Dissolve 2,7-dibromo-9,9-dioctyltinfluorene (1.97g, 3mmol) in 70mL Anhydrous tetrahydrofuran. Under argon protection, 1.6M n-butyllithium/n-hexane solution (6 mL, 9 mmol) was added dropwise at -78°C, and the reaction was incubated for 2 hours. Then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethylenedioxy borate (2.5mL, 12mmol) quickly, and continue to incubate for 2 hours. The solution was raised to room temperature and reacted for 30 hours. After the reaction, the reaction solution was poured into water, extracted with dichloromethane, washed with aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was evaporated, the residue was recrystallized from tetrahydrofuran/methanol, and further purified by silica gel column chromatography (petroleum ether: ethyl acetate = 5:1 as eluent) to obtain a powdery solid (1.35g, 60%). MS(APCI):m/z(%):750.2[M ⁺ ].

2) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9,9-di-n-octyltinfluorene (19): 40 mL of 2M potassium carbonate aqueous solution, 2,7-bis(4, 4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctyltinfluorene (3.8g, 5mmol) and 1-bromo-2-methylidene Sulfonylbenzene (2.8g, 13mmol) was added into a three-necked flask, 60mL of toluene was added and nitrogen was blown. When the reaction temperature rose to 85° C., 250 mg tetrakistriphenylphosphine palladium and 150 mg tetrabutylammonium bromide were added and reacted for 24 hours. Stop the reaction and cool to room temperature, and extract with dichloromethane 1-3 times. After the organic layer was spin-dried, the chromatographic column was passed through 100-200 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (1:1) to obtain a brown liquid (2.3 g, 60%). MS(APCI):m/z(%):774.7[M ⁺ ].

3) Preparation of bis(dibenzothiophene)tin-pentacyclopentadiene (20): 2,7-bis(2-methanesulfinylphenyl)-9,9-di-n-octyltinfluorene (1.5g , 2 mmol) was added into 12 mL of trifluoromethanesulfonic acid, stirred at room temperature for 30 hours, and then the reaction liquid was added dropwise into ice water. A yellow powder residue was obtained by suction filtration and dried in the air. The filter residue was added to 70 mL of pyridine, and heated to reflux under nitrogen for 15 hours. Stop the reaction and cool to room temperature, neutralize pyridine with hydrochloric acid, and extract with dichloromethane. The column was chromatographed with petroleum ether and recrystallized from ethanol to give a powder solid (0.64 g, 45%). Elemental analysis: C ₄₀ H ₄₆ S ₂ Sn Theoretical value: C 67.70%, H 6.53%, S 9.04%; measured value: C 68.22%, H 6.99%, S 8.51%.

4) Preparation of bis(S,S-dioxo-dibenzothiophene) tin-pentacyclopentadiene (FSnSO): Bis(dibenzothiophene)-dibenzothiophene-stannocyclopentadiene (2.8g, 4mmol) and 3-chloroperoxybenzoic acid (13.8 g, 80 mmol) were dissolved in 250 mL of dichloromethane and stirred for 5 hours in an ice bath. After the reaction, the reaction solution was poured into 10% aqueous sodium hydroxide solution and stirred for 20 minutes. The organic layer was washed with water (300mL×3), concentrated and passed through a chromatographic column. The polar eluent was dichloromethane/ethyl acetate (2:1), and recrystallized from ethanol to obtain a powder solid (2.3g, 75%). ¹ H-NMR (600MHz, CDCl ₃ , δ) 8.01(s, 2H), 7.86(t, 4H), 7.73(m, 4H), 7.54(t, 2H), 1.85(t, 4H), 1.05(m , 20H), 0.83(t, 6H), 0.71(s, 4H). Elemental analysis: C ₄₀ H ₄₆ O ₄ S ₂ Sn Theoretical value: C 62.10%, H 5.99%, S 8.29%; Measured value: C 61.79 %, H 6.34%, S7.89%.

Example 5

Synthesis of bis(S,S-dioxy-dibenzothiophene)furans (FOSO) (Tidwell R.R., Hall J.E.Preparation of bis(amidino)dibenzofurans and thiophenes for treating Pneumocystis carinii pneumonia: PCT Int.Appl.WO 2000010990[ P].2000-03-02.)

1) Synthesis of 4,4'-dibromo-2-methoxy-2'-nitrobiphenyl (21): 4,4'-dibromo-2,2'-dinitrobiphenyl (6.58 g, 16.5mmol) was added into 50mL DMF and stirred to dissolve, and a methanol solution of sodium methoxide (4.4M, 4.5mL, 19.8mmol) was added under ice-bath conditions. The mixture was reacted at room temperature for 12 hours, and then quenched by pouring into ice water. Extracted with ethyl acetate, the organic phase was washed with brine and dried over sodium sulfate. Concentrate and recrystallize from formionitrile/methanol to give a green solid (3.76 g, 59%). MS(APCI):m/z(%):388.0[M ⁺ ].

2) Synthesis of 4,4'-dibromo-2'-methoxy-biphenyl-2-amine (22): 4,4'-dibromo-2-methoxy-2'-nitro Benzene (3.76g, 9.8mmol) and 5% ruthenium (catalyst, 400mg) were dissolved in 37mL of ethanol and heated to 65-70°C, and a solution of hydrazine (4.6mL, 59mmol) in ethanol (5mL) was slowly added dropwise. The reaction was refluxed for 7 hours, filtered through celite, and then the celite was washed with ethanol. The mixture was spun to dryness and co-evaporated with ethanol, ethyl acetate and dichloromethane to obtain a white solid powder (2.5 g, 71%). MS(APCI):m/z(%):358.0[M ⁺ ].

3) Synthesis of 3,7-dibromo-dibenzofuran (23): 4,4'-dibromo-2'-methoxy-biphenyl-2-amine (3.5g, 9.8mmol) in ice bath It was mixed with sulfuric acid (2.4g) and water (8.5mL), and an aqueous solution of sodium nitrite (682mg, 9.8mmol) was added slowly. The reaction was carried out under ice bath for 2 hours. Then urea (1.2 g, 20 mmol) was added and reacted for 12 hours. Then the reaction solution was diluted with water and heated to 70° C. for 24 hours. After the reaction, the reaction solution was cooled to room temperature and filtered with suction. The filter residue was recrystallized from benzene/methanol to give a beige solid (2.27 g, 72%). MS(APCI):m/z(%):326.9[M ⁺ ].

4) Preparation of 2,7-diboronate-benzofuran (24): 2,7-dibromo-benzofuran (0.65 g, 2 mmol) was dissolved in 20 mL of anhydrous THF. Under argon protection, 1.6M n-butyllithium/n-hexane solution (4 mL, 6 mmol) was added dropwise at -78°C, and the reaction was incubated for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (1.6 mL, 8 mmol) was added rapidly, and the reaction was continued for 2 hours. The reaction solution was raised to room temperature for 30 hours. The reaction mixture was poured into ice water, extracted with dichloromethane, washed with aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was evaporated, the residue was recrystallized from ethanol, and further purified by silica gel column chromatography (petroleum ether: ethyl acetate = 2:1 as eluent) to obtain a solid powder (0.55 g, 66%). MS(APCI):m/z(%):421.1[M ⁺ ].

5) Preparation of 2,7-bis(2-methanesulfinylphenyl)-benzofuran (25): 20 mL of 2M potassium carbonate aqueous solution, 2,7-bis(4,4,5,5 -Tetramethyl-1,3,2-dioxaborolan-2-yl)-benzofuran (2.5g, 6mmol) and 1-bromo-2-methanesulfinylbenzene (3.3g, 15mmol) were added To 40mL toluene, nitrogen. When the reaction temperature rose to 75° C., 300 mg of tetraphenylphosphine palladium and 180 mg of tetrabutylammonium bromide were added and reacted for 15 hours. The reaction was stopped and cooled to room temperature, extracted with dichloromethane 1 to 3 times, and the organic layer was spin-dried and passed through a chromatographic column with 200 to 300 mesh silica gel (petroleum ether/ethyl acetate=1:2) to obtain a solid powder ( 1.9g, 70%). MS(APCI):m/z(%):445.5[M ⁺ ].

6) Preparation of bis(dibenzothiophene)furan (26): 2,7-bis(2-methanesulfinylphenyl)-benzofuran (3.6g, 8mmol) was added to 15mL trifluoromethanesulfonate acid, stirred at room temperature for 20 hours, and added the reaction solution dropwise to ice water. The reaction solution was suction filtered, and the filter residue was air-dried. Afterwards, the filter residue was added into 150 mL of pyridine, and heated to reflux under nitrogen for 12 hours. Stop the reaction and cool to room temperature, neutralize pyridine with hydrochloric acid, and extract with dichloromethane. Purified by column chromatography using dichloromethane as eluent, and recrystallized from ethanol to obtain solid powder (2.2 g, 73%). MS(APCI):m/z(%):381.5[M ⁺ ].Elemental analysis: C ₂₄ H ₁₂ OS ₂ theoretical value: C 75.76%, H 3.18%, S 16.85%; measured value: C 75.11%, H 3.33%, S 17.11%.

7) Preparation of bis(S,S-dioxo-dibenzothiophene)furan (FOSO): Bis(dibenzothiophene)furan (760mg, 2mmol) and 3-chloroperoxybenzoic acid (6.8g , 40mmol) was dissolved in 150mL of dichloromethane and stirred for 10 hours under ice-bath conditions. After the reaction, the reaction solution was poured into 10% aqueous sodium hydroxide solution and stirred for 15 minutes. The organic layer was washed with water (120mL×3), concentrated and passed through a chromatography column with dichloromethane/ethyl acetate (1:3) as the polarity eluent, and recrystallized from ethanol to obtain a solid powder (710mg, 80%). MS(APCI):m/z(%):445.5[M ⁺ ].Elemental analysis: C ₂₄ H ₁₂ O ₅ S ₂ Theoretical value: C 64.85%, H 2.72%, S 14.43%; Measured value: C 65.13% , H 2.91%, S 13.89%.

Example 6

Synthesis of bis(S,S-dioxy-dibenzothiophene)pyrrole (FNSO) (Kerszulis J.A., Amb C.M., Dyer A.L., et al. Follow the yellow brick road: structural optimization of vibrant yellow-to-transmissive electrochromic conjugated polymers[J].Macromolecules,2014,47(16):5462-5469.)

1) Synthesis of 4,4-dibromo-2-nitrobiphenyl (27): Dissolve 4,4'-dibromobiphenyl (20g, 64mmol) in 200mL acetic acid, ice bath (0-5°C) Stir in the dark, take 30mL of fuming nitric acid and dilute it with 70mL of acetic acid, add it to the constant pressure dropping funnel, slowly drop it into the reaction solution under the dark condition, and slowly raise the reaction temperature to 100°C after the dropwise addition. Hours, observe the change of the reaction solution, stop the reaction when the reaction solution turns from turbid to transparent, and naturally cool to room temperature. The reaction solution was slowly poured into ice water to quench, the mixture was suction filtered, the filter residue was washed with water, saturated aqueous sodium bisulfite solution, water, and ice ethanol, and then the filter residue was dried to obtain a light yellow solid (13.7 g, 60%). MS(APCI): m/z(%): 358.0[M ⁺ ].

2) Synthesis of 2,7-dibromocarbazole (28): 4,4'-dibromo-2-nitrobiphenyl (17.85g, 50mmol) and triphenylphosphine (32.75g, 125mmol) were added to In 300 mL of N,N-dimethylacetamide (DME), heated and stirred overnight in an argon atmosphere. Stop the reaction and cool to room temperature, extract with dichloromethane and wash with water 4 to 5 times, purify by column chromatography, use 200 to 300 mesh silica gel as stationary phase, petroleum ether/dichloromethane (2:1) as washing After removing the solvent and passing through the column, it was recrystallized with ethanol to obtain gray powdery crystals (12 g, 73.8%). MS(APCI): m/z(%): 326.0[M ⁺ ].

3) Synthesis of 2,7-dibromo-N-(2-decyltetradecyl)carbazole (29): 2,7-dibromocarbazole (32.5g, 100mmol) and potassium hydroxide (28g , 500mmol) was dissolved in 200mL DMF, heated to 60°C under nitrogen, at this time, 2-decyl bromidetetradecane (62.55g, 150mmol) was slowly added, and reacted for 8 hours. After stopping the reaction and cooling to room temperature, the reaction solution was poured into water and extracted with dichloromethane. Purification was performed by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a white waxy solid (60 g, 91%). MS(APCI): m/z(%): 662.6[M ⁺ ].

4) Preparation of 2,7-diboronate-N-(2-decyltetradecyl)carbazole (30): 2,7-dibromo-N-(2-decyltetradecyl ) carbazole (13.2g, 20mmol) was dissolved in 120mL absolute dry tetrahydrofuran, stirred and dissolved at room temperature in an argon atmosphere, the reaction bottle was placed in a -80°C low-temperature reactor, and n-butyllithium (25mL ,60mmol) was slowly added dropwise to the reaction flask, the reaction solution was kept warm for 2 hours, and then 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborane was added quickly (16.3 mL, 80 mmol), followed by overnight reaction at room temperature. Stop the reaction, pour the reaction solution into water to quench, concentrate the reaction solution and extract it with dichloromethane, and purify it by column chromatography, using 200-300 mesh silica gel as the stationary phase, and the eluent is petroleum ether/dichloromethane ( 2:1), a light yellow transparent viscous liquid (9.8g, 65%) was obtained. MS(APCI): m/z(%): 756.8[M ⁺ ].

5) Preparation of 2,7-bis(2-methanesulfinylphenyl)-N-(2-decyltetradecyl)carbazole (31): 2,7-diboronate-N- (2-decyltetradecyl)carbazole (20g, 26.5mmol), 1-bromo-2-methanesulfinylbenzene (14.5g, 66mmol), tetrabutylammonium bromide (0.84g, 2.6mmol) and 130mL of potassium carbonate aqueous solution with a concentration of 2M were added to the reaction flask, and at the same time, 300mL of toluene was added to fully dissolve it, heated to reflux and stirred under argon atmosphere, and when the temperature was stabilized at 90°C, tetrakis(triphenylphosphine)palladium (1.5g, 1.3 mmol), sealed the reaction vial, and heated to reflux for overnight reaction. Stop the reaction and cool to room temperature, wash the reaction solution with water for 2 to 3 times, then concentrate the reaction solution through a silica gel chromatography column, and the eluent is petroleum ether/ethyl acetate (3:1) to obtain a light yellow oily liquid (16.5 g, 80%). MS(APCI): m/z(%): 781.2[M ⁺ ].

6) Preparation of bis(dibenzothiophene)pyrrole (32): 2,7-bis(2-methanesulfinylphenyl)-N-(2-decyltetradecyl)carbazole (5g , 6.4mmol) was added to 9mL of trifluoromethanesulfonic acid, and reacted under ice-bath conditions. Stop the reaction after reacting for 8 hours, add the reaction solution dropwise into ice water, and filter with suction to obtain a yellow powdery solid, which can be dried in the air. The filter residue was added to a 250mL three-neck round-bottomed flask and 100mL of pyridine was added, and heated to reflux for 8 hours under argon, the reaction was stopped and cooled to room temperature, the pyridine was neutralized with hydrochloric acid, extracted with dichloromethane, concentrated and passed through a chromatography column, The silica gel was 200-300 mesh, the eluent was petroleum ether/dichloromethane (5:1), and recrystallized with ethanol to obtain a yellow powdery solid (2.6g, 56%). MS (APCI): m/z (%): 716.5 [M ⁺ ]. Elemental analysis: C ₄₈ H ₆₁ NS ₂ , theoretical value: C 80.50%, H 8.59%, N 1.96%, S 8.96%; measured value: C 80.85%, H 8.23%, N 2.10%, S 8.75%.

7) Preparation of bis(S,S-dioxo-dibenzothiophene)pyrrole (FNSO): Dissolve bis(dibenzothiophene)pyrrole (1.5g, 2.1mmol) in dichloromethane, ice bath condition m-Chloroperoxybenzoic acid (7.2 g, 42 mmol) was added, and the reaction was stirred overnight in the dark. Stop the reaction after the reaction is over, pour the reaction solution into cold saturated sodium hydroxide aqueous solution and stir, then extract with dichloromethane and wash with water for 3 to 4 times, pass through the chromatographic column, silica gel 200 to 300 mesh, and the eluent is Dichloromethane, followed by recrystallization from tetrahydrofuran, finally gave a white flocculent solid (1.3 g, 81%). ¹ H-NMR (600MHz, CDCl ₃ , δ) 8.56(s, 2H), 7.71(d, 2H), 7.55(d, 2H), 7.35(t, 2H), 7.22(t, 2H), 7.20(s , 2H), 4.10 (d, 2H, N-CH ₂ ), 1.78 (s, 1H), 1.13 (m, 40H), 0.83 (t, 6H). ¹³ C-NMR (150MHz, CDCl ₃ , δ) 144.11, 138.43, 133.79, 131.38, 130.41, 130.18, 129.89, 122.89, 121.85, 121.70, 114.26, 102.53, 58.46, 47.76, 37.903, 39.8, 31.6 29.53, 29.31, 29.27, 26.44, 22.65, 18.44, 14.04. MS (APCI): m/z (%): 780.5 [M ⁺ ]. Elemental analysis: C ₄₈ H ₆₁ NO ₄ S ₂ , theoretical values: C 73.90%, H 7.88%, N 1.80%, S 8.22%; measured values: C 74.21%, H 7.65%, N 1.91%, S 8.10%.

Example 7

Synthesis of bis(S,S-dioxo-dibenzothiophene)phosphinocyclopentadiene (FPSO) (Chen R.F., Fan Q.L., Zheng C., et al. A general strategy for the facile synthesis of 2,7 -dibromo-9-heterofluorenes[J].Org.Lett.,2006,8(2):203-205.)

1) Synthesis of 2,7-dibromo-9-phenylphosphine fluorene (33): 4,4'-dibromo-2,2'-diiodobiphenyl (1.12g, 1.96mmol) was dissolved in 30mL Add 2.5M n-butyllithium n-hexane solution (3.2mL, 8mmol) to the water tetrahydrofuran solution at -78°C, keep the reaction solution warm for 1 hour, then quickly add phenyl dichlorophosphine (0.4g, 2.2mmol ). Continue to incubate the reaction for 50 minutes, and then slowly raise the reaction solution to room temperature for overnight reaction. After the reaction was completed, the reaction was quenched with water, extracted, and the organic phase was washed with brine, dried, and purified by column chromatography to finally obtain a powder solid (0.39 g, 48%). MS(APCI): m/z(%): 419.0[M ⁺ ].

2) Preparation of 2,7-diboronate-9-phenylphosphinefluorene (34): Dissolve 2,7-dibromo-9-phenylphosphinefluorene (2.3g, 5mmol) in 60mL dry tetrahydrofuran , stirring and dissolving at room temperature in an argon atmosphere, then put the reaction bottle into a low-temperature reactor at -80°C, slowly add n-butyllithium (8mL, 20mmol) with a concentration of 2.5M into the reaction bottle, and keep the reaction for 2 hours. Then 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborinane (6.1 mL, 30 mmol) was added quickly, and the reaction solution was raised to room temperature overnight. Stop the reaction, pour the reaction solution into water to quench, concentrate the reaction solution and extract it with dichloromethane, and purify it by column chromatography, using 200-300 mesh silica gel as the stationary phase, and the eluent is petroleum ether/dichloromethane ( 2:1), a solid powder (1.6g, 60%) was obtained. MS(APCI):m/z(%):513.2[M ⁺ ].

3) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9-phenylphosphine fluorene (35): 2,7-diboronate-9-phenylphosphine fluorene (5.5g, 10mmol), 1-bromo-2-methanesulfinylbenzene (5.5g, 25mmol), tetrabutylammonium bromide (0.32g, 1mmol) and 50mL concentration of 2M potassium carbonate aqueous solution were added to the reaction flask, and added 100mL of toluene was fully dissolved, heated to reflux and stirred under argon atmosphere, and when the temperature was stabilized at 90°C, tetrakis(triphenylphosphine)palladium (0.6g, 0.5mmol) was added, the reaction bottle was sealed, and heated to reflux overnight for reaction. Stop the reaction and cool to room temperature, wash the reaction solution twice with water, concentrate the reaction solution through a chromatographic column, silica gel 200-300 mesh, eluent is petroleum ether/ethyl acetate (2:1), and obtain a solid powder (2.4 g, 45%). MS(APCI):m/z(%):537.6[M ⁺ ].

4) Preparation of bis(dibenzothiophene)phosphine (36): 2,7-bis(2-methanesulfinylphenyl)-9-phenylphosphine fluorene (1.7g, 3mmol ) was added into 10 mL of trifluoromethanesulfonic acid, and reacted under ice-bath conditions. Stop the reaction after reacting for 10 hours, add the reaction solution dropwise into ice water, filter with suction to obtain a yellow solid, and dry it in the air. Add the solid powder into 50mL pyridine, heat and reflux in argon for 4 hours, stop the reaction and cool to room temperature, neutralize the pyridine with hydrochloric acid, extract with dichloromethane, concentrate and pass through the chromatography column, silica gel 200-300 mesh, wash The solvent used was petroleum ether/dichloromethane (3:1), and recrystallized from ethanol to obtain a solid powder (0.7g, 45%). Elemental analysis: C ₃₀ H ₁₇ PS ₂ theoretical value: C 76.25%, H 3.63%, S 13.57%; measured value: C 75.87%, H 3.81%, S 13.88%.

5) Preparation of bis(S,S-dioxo-dibenzothiophene) phosphinocyclopentadiene (FPSO): bis(dibenzothiophene) phosphinocyclopentadiene (1.0g, 2mmol) Dissolve in dichloromethane, add m-chloroperoxybenzoic acid (6.9 g, 40 mmol) under ice-bath conditions, and react overnight under dark conditions. Stop the reaction after the reaction is over, pour the reaction solution into cold saturated sodium hydroxide aqueous solution and stir, extract with dichloromethane and wash with water for 3 to 4 times, pass through the chromatographic column, silica gel 200 to 300 mesh, and the eluent is dichloromethane Chloromethane was recrystallized from tetrahydrofuran to finally obtain solid powder (0.86g, 75%). MS(APCI):m/z(%):537.5[M ⁺ ].Elemental analysis: C ₃₀ H ₁₇ O ₄ PS ₂ Theoretical value: C 67.15%, H 3.19%, S 11.95%; Measured value: C 66.69% , H 3.76%, S 12.11%.

Example 8

Synthesis of bis(S,S-dioxo-dibenzothiophene)phosphoryloxole (FPOSO) (Bruch A., Fukazawa A., Yamaguchi E., et al. Bis(phosphoryl)-Bridged Biphenyls by Radical Phosphanylation:Synthesis and Photophysical and Electrochemical Properties[J].Angew.Chem.Int.Edit.,2011,50(50):12094-12098.) 

1) Synthesis of 2,7-dibromo-9-phenylphosphinoxyfluorene (37): Dissolve 4,4'-dibromo-2,2'-diiodobiphenyl (1.12g, 1.96mmol) in 30mL In the anhydrous tetrahydrofuran solution, add 2.5M n-butyllithium n-hexane solution (3.2mL, 8mmol) at -78°C, keep the reaction solution at this temperature for 1.5 hours, then quickly add phenyl dichlorophosphine (0.43 g, 2.2 mmol). Continue to keep warm for 1 hour, and then slowly raise the reaction solution to room temperature for overnight reaction. After the reaction was completed, the reaction was quenched with water, extracted, and the organic phase was washed with brine, dried, and purified by column chromatography to obtain a solid powder (0.27 g, 32%). MS(APCI):m/z(%):435.0[M ⁺ ].

2) Preparation of 2,7-diboronate-9-phenylphosphinoxyfluorene (38): Dissolve 2,7-dibromo-9-phenylphosphinoxyfluorene (2.8g, 6mmol) in 60mL and dry In tetrahydrofuran, stir and dissolve at room temperature in an argon atmosphere, then put the reaction bottle into a low-temperature reactor at -80°C, and slowly add n-butyllithium (9.6mL, 24mmol) with a concentration of 2.5M into the reaction bottle dropwise, and the reaction solution Insulated reaction for 2 hours, then quickly added 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborane (7.3mL, 36mmol), after 40 minutes of incubation reaction The reaction solution was raised to room temperature overnight. Stop the reaction, pour the reaction solution into water to quench, concentrate the reaction solution and extract it with dichloromethane, and purify it by column chromatography, using 200-300 mesh silica gel as the stationary phase, and the eluent is petroleum ether/dichloromethane ( 1:3), a solid powder (1.0 g, 30%) was obtained. MS(APCI):m/z(%):529.2[M ⁺ ].

3) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9-phenylphosphinoxyfluorene (39): 2,7-diboronate-9-phenylphosphinoxyfluorene (5.6 g, 10mmol), 1-bromo-2-methanesulfinylbenzene (5.5g, 25mmol), tetrabutylammonium bromide (0.32g, 1mmol) and 50mL concentration of 2M aqueous potassium carbonate were added to the reaction flask, Add 100mL of toluene to dissolve, heat to reflux and stir under argon atmosphere, add tetrakis(triphenylphosphine)palladium (0.6g, 0.5mmol) when the temperature is stable at 90°C, and heat to reflux overnight for reaction. Stop the reaction and cool to room temperature, wash the reaction solution twice with water, then concentrate the reaction solution through a chromatography column, silica gel 200-300 mesh, eluent is dichloromethane/ethyl acetate (1:1), to obtain a solid powder (4.1 g, 69%). MS(APCI):m/z(%):553.6[M ⁺ ].

4) Preparation of bis(dibenzothiophene)phosphoxolene (40): 2,7-bis(2-methanesulfinylphenyl)-9-phenylphosphinoxolene (1.8g , 3mmol) was added to 10mL of trifluoromethanesulfonic acid and reacted under ice-bath conditions. After the reaction was carried out for 10 hours, the reaction was stopped, the reaction liquid was added dropwise into ice water, and the solid yellow powder was obtained by suction filtration, which was dried in the air. Add the solid powder to 100mL pyridine, heat and reflux for 12 hours under argon, stop the reaction and cool to room temperature, neutralize the pyridine with hydrochloric acid, extract with dichloromethane, concentrate and pass through the chromatography column, silica gel 200-300 mesh, The eluent was dichloromethane/ethyl acetate (2:1), and recrystallized from ethanol to give a powdery solid (0.4g, 25%). Elemental analysis: C ₃₀ H ₁₇ OPS ₂ theoretical value: C 73.75%, H 3.51%, S 13.13%; measured value: C 73.21%, H 3.87%, S 13.55%.

5) Preparation of bis(S,S-dioxo-dibenzothiophene) phosphinoxole (FPOSO): bis(dibenzothiophene) phosphoxole (2.6g, 5mmol) was dissolved in dichloromethane, m-chloroperoxybenzoic acid (17.2g, 100mmol) was added under ice-bath conditions, and the reaction was stirred overnight under dark conditions. Stop the reaction after the reaction is over, pour the reaction solution into cold saturated sodium hydroxide aqueous solution and stir, extract with dichloromethane and wash with water for 3 to 4 times, pass through the chromatographic column, silica gel 200 to 300 mesh, and the eluent is dichloromethane Chloromethane, followed by recrystallization from THF to give a solid powder (2.4 g, 80%). Elemental analysis: C ₃₀ H ₁₇ O ₅ PS ₂ theoretical value: C 65.21%, H 3.10%, S 11.61%; measured value: C 65.77%, H 2.98%, S 11.99%.

Example 9

Synthesis of bis(S,S-dioxo-dibenzothiophene)-S,S-dioxythiophene (FSOSO) (Hirose H., Igarashi R., Sato K. Image holding member for image forming apparatus, process cartridge , and image forming apparatus: U.S.Pat.20130164662[P].2013-06-27.) 

1) Synthesis of S,S-dioxy-dibenzothiophene (41): Dissolve thiofluorene (18.4 g, 100 mmol) in 200 mL of acetic acid and heat to reflux until dissolved. At this time, 30% hydrogen peroxide (14 mL, 125 mmol) was added, and after 1 hour, hydrogen peroxide (14 mL, 125 mmol) was added again, and heated to reflux overnight for reaction. After the reaction, the reaction solution was poured into water, filtered with suction, and the filter residue was recrystallized with chlorobenzene to obtain a white solid (19.4 g, 90%). MS(APCI):m/z(%):217.2[M ⁺ ].

2) Synthesis of 3,7-dibromo-S,S-dioxy-dibenzothiophene (42): Dissolve S,S-dioxy-dibenzothiophene (9.7g, 45mmol) in 300mL sulfuric acid, Stir in an ice bath. At this time, N-bromosuccinimide (NBS, 20 g, 112.5 mmol) was weighed and added to the reaction solution several times in batches, and reacted overnight. After the reaction, the reaction solution was poured into water, filtered with suction, and the filter residue was washed successively with aqueous sodium bicarbonate solution, ethanol, water, and ethanol, and then recrystallized with chlorobenzene to obtain a white solid (13.5 g, 40%). MS(APCI):m/z(%):375.0[M ⁺ ].

3) Synthesis of 3,7-dibromo-dibenzothiophene (43): Dissolve 3,7-dibromo-S,S-dioxo-dibenzothiophene (3.74g, 10mmol) in 50mL ether, and While stirring under bath conditions, lithium aluminum hydride (1.52 g, 40 mmol) was added rapidly at this time, and the reaction was stopped after 10 minutes. The reaction solution was quenched by pouring into hydrochloric acid, extracted with dichloromethane, washed with brine and dried, and passed through a column chromatography (petroleum ether) to finally obtain a white solid (2.3 g, 67%). MS(APCI):m/z(%):343.0[M ⁺ ].

4) Preparation of 3,7-diboronate-thiofluorene (44): 3,7-dibromo-thiofluorene (5.1 g, 15 mmol) was dissolved in 130 mL of anhydrous THF. Under argon protection, 1.6M n-butyllithium/n-hexane solution (28 mL, 45 mmol) was added dropwise at -78°C, and the reaction was incubated for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (12 mL, 60 mmol) was added rapidly, and the reaction was continued for 2 hours. The reaction mixture was gradually raised to room temperature for 15 hours. The reaction mixture was poured into water, extracted with dichloromethane, washed with brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was recrystallized from tetrahydrofuran/methanol, and further purified by silica gel column chromatography with petroleum ether/dichloromethane (3:1) as the eluent to obtain a white solid (4.7g, 72%). MS(APCI):m/z(%):437.2[M ⁺ ].

5) Preparation of 3,7-bis(2-methanesulfinylphenyl)-thiofluorene (45): 20 mL of 2M K ₂ CO ₃ solution, 3,7-diboronate-thiofluorene ( 2.61g, 6mmol) and 1-bromo-2-methanesulfinylbenzene (2.9g, 13.2mmol) were added to the reaction flask, 50mL of toluene was added to dissolve, and nitrogen gas was passed. When the reaction temperature rose to 80° C., 200 mg tetraphenylphosphine palladium and 90 mg tetrabutylammonium bromide were added and reacted for 13 hours. Stop the reaction and cool to room temperature, and extract with dichloromethane 1-3 times. After the organic layer was spin-dried, the chromatographic column was passed through 200-300 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (3:1) to obtain a beige solid (1.8 g, 65%). MS(APCI):m/z(%):461.6[M ⁺ ].

6) Preparation of bis(dibenzothiophene)thiophene (46): 3,7-bis(2-methanesulfinylphenyl)-thiofluorene (0.92g, 2mmol) was added to 5mL trifluoromethanesulfonic acid , reacted at room temperature for 22 hours. After the reaction was completed, the reaction solution was added dropwise into ice water, and the reaction solution was suction-filtered to obtain a light yellow solid powder, which was dried in the air. The light yellow solid powder was added to 20 mL of pyridine, and heated to reflux for 10 hours under nitrogen. Stop the reaction and cool to room temperature, neutralize pyridine with hydrochloric acid, and extract with dichloromethane. The column was chromatographed with petroleum ether and recrystallized from ethanol to obtain a white solid powder (0.60 g, 76%). MS(APCI):m/z(%):397.5[M ⁺ ].Elemental analysis: C ₂₄ H ₁₂ S ₃ theoretical value: C 72.69%, H 3.05%, S 24.26%; measured value: C 73.17%, H 2.79%, S24.01%.

7) Preparation of bis(S,S-dioxo-dibenzothiophene)-S,S-dioxythiophene (FSOSO): Bis(dibenzothiophene)thiophene (1.98g, 5mmol) and 3- Chloroperoxybenzoic acid (17.2g, 100mmol) was dissolved in 200mL of dichloromethane, and reacted for 10 hours under ice-bath conditions. After the reaction was completed, the reaction liquid was poured into a cold 10% mass concentration sodium hydroxide aqueous solution and stirred for 20 minutes. The organic layer was washed with water (300 mL×3), concentrated and recrystallized from ethanol/tetrahydrofuran to obtain a solid powder (1.48 g, 60%). Elemental analysis: C ₂₄ H ₁₂ O ₆ S ₃ theoretical value: C 58.52%, H 2.46%, S 19.53%; measured value: C 58.77%, H2.41%, S 19.33%.

Example 10

Synthesis of bis(S,S-dioxo-dibenzothiophene)-S,S-dioxyselenoxide (FSeOSO) (McCulla R.D., Jenks W.S.Deoxygenation and Other Photochemical Reactions of Aromatic Selenoxides[J].J.Am .Chem.Soc.,2004,126(49):16058-16065.)

1) Synthesis of 2-selenocyano-4,4-dibromobiphenyl (47): Mix 5mL sulfuric acid and 20mL water, then add 2-amino-4,4-dibromobiphenyl (9.62g, 29.4 mmol) was added therein, and 80 mL of water was added when the reaction dropped to 0°C. After stirring for 20 minutes, sodium nitrite (2.5 g, 36.2 mmol) was added, and the reaction was carried out under ice bath. When the reaction solution was dark yellow and weakly acidic, sodium acetate was added. Potassium selenocyanate (4.2 g, 29.1 mmol) was dissolved in 20 mL of water and slowly added dropwise to the reaction solution. After reacting for 1 hour, the mixed solution was poured into toluene, washed with water, dried over anhydrous magnesium sulfate, and the inorganic salt was removed by column chromatography, distilled under reduced pressure, and purified by column chromatography to obtain a solid powder (5.4 g, 44%). MS(APCI):m/z(%):416.9[M ⁺ ].

2) Synthesis of 2-biphenyl diselenium (48): Dissolve potassium hydroxide (1.56g, 27.8mmol) in 4mL of methanol, then add 2-selenocyano-4,4-dibromobiphenyl (3.5 g, 8.4mmol), the reaction was stirred for 50 minutes. After the reaction, the reaction solution was poured into toluene and saturated boric acid solution, washed with salt water, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and recrystallized from acetone to obtain a solid powder (3.1 g, 48%). MS(APCI):m/z(%):780.9[M ⁺ ].

3) Synthesis of 2,7-dibromo-selenofluorene (49): Dissolve 2-biphenylselenide (3.7g, 4.8mmol) in 15mL carbon tetrachloride, heat to reflux, then add liquid bromine (0.2 mL, 4.0mmol), after 4 hours of reaction, the temperature was lowered to 60°C for another 20 hours of reaction. After the reaction, the reaction solution was concentrated and purified by column chromatography (petroleum ether as eluent) to obtain solid powder (1.44 g, 77%). MS(APCI):m/z(%):389.9[M ⁺ ].

2) Preparation of 2,7-diboronate-selenofluorene (50): 3,7-dibromo-selenofluorene (3.89 g, 10 mmol) was dissolved in 80 mL of anhydrous THF. Under argon protection, 1.6M n-butyllithium/n-hexane solution (19 mL, 30 mmol) was added dropwise at -78°C, and the reaction was incubated for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (8 mL, 40 mmol) was added rapidly, and the reaction was continued for 1.5 hours. The reaction mixture was gradually raised to room temperature for 10 hours. The reaction mixture was poured into water, extracted with dichloromethane, washed with aqueous NaCl, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was recrystallized from tetrahydrofuran/methanol, and further purified by silica gel column chromatography with petroleum ether/dichloromethane (2:1) as the eluent to obtain a solid powder (2.7g, 55%). MS(APCI):m/z(%):484.1[M ⁺ ].

3) Preparation of 2,7-bis(2-methanesulfinylphenyl)-selenofluorene (51): 35 mL of 2M potassium carbonate aqueous solution, 3,7-diboronate-selenofluorene (2.9 g , 6mmol) and 1-bromo-2-methanesulfinylbenzene (2.9g, 13.2mmol) were added to a three-necked flask, 50mL of toluene was added to dissolve, and nitrogen was blown. When the reaction temperature rose to 75° C., 300 mg of tetraphenylphosphine palladium and 120 mg of tetrabutylammonium bromide were added and reacted for 15 hours. Stop the reaction after the reaction is over, cool to room temperature, and extract with dichloromethane for 1 to 3 times. After the organic layer was spin-dried, the chromatographic column was passed through 200-300 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (5:2) to obtain a solid powder (2.1 g, 68%). MS(APCI):m/z(%):508.5[M ⁺ ].

4) Preparation of bis(dibenzothiophene)selenophene (52): 3,7-bis(2-methanesulfinylphenyl)-selenofluorene (1.01g, 2mmol) was added to 5mL trifluoromethanesulfonate acid, reacted at room temperature for 18 hours. After the reaction, the reaction solution was added dropwise into ice water. The reaction solution was suction filtered to obtain a solid powder, which was dried in the air. The solid powder was added into 50 mL of pyridine, and heated to reflux under nitrogen for 10 hours. Stop the reaction and cool to room temperature, neutralize pyridine with hydrochloric acid, and extract with dichloromethane. The column was chromatographed with petroleum ether/dichloromethane (5:1) and recrystallized from ethanol to obtain a powdery solid (0.42g, 48%). MS(APCI):m/z(%):443.9[M ⁺ ].

5) Preparation of bis(S,S-dioxo-dibenzothiophene)-S,S-dioxyselenophene (FSeOSO): Bis(dibenzothiophene)selenophene (1.33g, 3mmol) and 3-Chloroperoxybenzoic acid (10.3g, 60mmol) was dissolved in 200mL of dichloromethane and reacted for 10 hours under ice-bath conditions. After the reaction, the reaction solution was poured into a cold 10% aqueous sodium hydroxide solution and stirred for 40 minutes. The organic layer was washed with water (80 mL×3), concentrated and then recrystallized from ethanol/tetrahydrofuran to obtain a powdery solid (1.42 g, 88%). Elemental analysis: C ₂₄ H ₁₂ O ₆ S ₂ Se theoretical value: C 53.44%, H 2.24%, S 11.89%; measured value: C 52.89%, H 2.57%, S 12.21%.

Example 11

Synthesis of bis(S,S-dioxo-dibenzothiophene)borole (FBSO) (Chen R.F., Fan Q.L., Zheng C., et al.A general strategy for the facile synthesis of 2, 7-dibromo-9-heterofluorenes[J].Org.Lett.,2006,8(2):203-205.)

1) Synthesis of 2,7-dibromo-9-phenylbororofluorene (53): 4,4'-dibromo-2,2'-diiodobiphenyl (2.24g, 3.92mmol) was dissolved in 50mL Add 2.5M n-butyllithium n-hexane solution (6.5mL, 16mmol) to the water tetrahydrofuran solution at -78°C, keep the reaction solution at this temperature for 2 hours, and then quickly add phenyl dichlorophosphine (0.66 g, 4.4 mmol). Continue to keep warm for 1 hour, and then slowly raise the reaction solution to room temperature for overnight reaction. After the reaction was completed, the reaction was quenched with water, extracted, and the organic phase was washed with brine, dried, and purified by column chromatography to finally obtain a powder solid (0.67 g, 43%). MS(APCI):m/z(%):398.9[M ⁺ ].

2) Preparation of 2,7-diboronate-9-phenylbororofluorene (54): 2,7-dibromo-9-phenylbororofluorene (0.8 g, 2 mmol) was dissolved in 100 mL of anhydrous tetrahydrofuran. Under argon protection, 1.6M n-butyllithium/n-hexane solution (4 mL, 6 mmol) was added dropwise at -78°C, and reacted at -78°C for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (1.6 mL, 8 mmol) was added rapidly, and the reaction was continued for 2 hours. The reaction mixture was gradually raised to room temperature for 21 hours. The reaction mixture was poured into water, extracted with dichloromethane, washed with aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was evaporated, the residue was recrystallized from methanol, and further purified by silica gel column chromatography (petroleum ether: ethyl acetate = 5:1 as eluent) to obtain a solid powder (0.49g, 62%). MS(APCI):m/z(%):493.0[M ⁺ ].

3) Preparation of 2,7-bis(2-methanesulfinylphenyl)-9-phenylbororofluorene (55): 30 mL of 2M potassium carbonate aqueous solution, 2,7-diboronate-9 -Phenylbororfluorene (3.0g, 6mmol) and 1-bromo-2-methanesulfinylbenzene (2.9g, 13.2mmol) were added to a three-necked flask, 60mL of toluene was added to dissolve, and nitrogen was blown. When the reaction temperature rose to 90° C., 350 mg tetraphenylphosphine palladium and 190 mg tetrabutylammonium bromide were added, and the reaction was carried out for 16 hours. Stop the reaction and cool to room temperature, and extract with dichloromethane 1-3 times. After the organic layer was spin-dried, the chromatographic column was passed through 200-300 mesh silica gel, and the polarity of the eluent was petroleum ether/ethyl acetate (3:2) to obtain a solid powder (2.38 g, 77%). MS(APCI):m/z(%):517.3[M ⁺ ].

4) Preparation of bis(dibenzothiophene)borole (56): 2,7-bis(2-methanesulfinylphenyl)-9-phenylbororene (0.62g, 1.2 mmol) was added into 7 mL of trifluoromethanesulfonic acid, reacted at room temperature for 20 hours, and the reaction solution was added dropwise to ice water. The reaction solution was suction filtered to obtain a solid powder, which was dried in the air. Add the light solid powder into 100 mL of pyridine, and heat to reflux under nitrogen for 6 hours. Stop the reaction and cool to room temperature, neutralize pyridine with hydrochloric acid, and extract with dichloromethane. Column chromatography was performed with petroleum ether/dichloromethane (10:1), and recrystallized with ethanol to obtain a solid powder (0.24 g, 44%). Elemental analysis: C ₃₀ H ₁₇ BS ₂ theoretical value: C 79.65%, H 3.79%, S 14.18%; measured value: C 80.01%, H 3.88%, S 13.77%.

5) Preparation of bis(S,S-dioxo-dibenzothiophene)borole (FBSO): Bis(dibenzothiophene)borole (0.45g, 1mmol) and 3-chloroperoxybenzoic acid (3.4g, 20mmol) were dissolved in 120mL of dichloromethane, and reacted for 5 hours under ice-bath conditions. After the reaction was completed, the reaction liquid was poured into a cold 10% mass concentration sodium hydroxide aqueous solution and stirred for 30 minutes. The organic layer was washed with water (100mL×3), concentrated and passed through a column chromatography, the polarity of the eluent was dichloromethane/ethyl acetate (1:2), and recrystallized from ethanol to obtain a solid powder (0.44g, 85%) . Elemental analysis: C ₃₀ H ₁₇ BO ₄ S ₂ Theoretical value: C 69.78%, H 3.32%, S 12.42%; measured value: C 69.22%, H 3.57%, S 12.88%.

Figure 1 shows the differential scanning calorimetry curves of compounds FCSO and FNSO, where the melting temperatures of FCSO and FNSO are close to or exceed 200°C, indicating that the dithiol group endows the compound with a better rigid structure and the compound has good thermal properties.

Figure 2 shows the thermal weight loss curves of compounds FCSO and FNSO. The thermal decomposition temperature (T _d , corresponding to the compound weight loss of 5wt.%) of the compounds exceeds 400°C. The compounds show good thermal stability and meet the needs of practical applications.

Figure 3 shows the solid powder X-ray diffraction of compounds FCSO and FNSO. It can be seen from the figure that the compounds have obvious Bragg angles, have the ability to crystallize, and have regular molecular structures and tight packing, which is conducive to the transport of carriers.

Figure 4 shows the cyclic voltammetry characteristic curves of compounds FCSO and FNSO. It can be seen from the figure that the compounds have deep HOMO energy levels and LUMO energy levels, indicating that the compound molecules have good electron affinity and stable molecular structure, which contributes to Preparation of efficient and stable light-emitting devices.

Figure 5 shows the ultraviolet-visible absorption spectra of the compound FCSO and FNSO thin films. It can be seen that the absorption of the compound molecules is mainly the π-π* transition absorption of the molecular condensed ring skeleton β valence band, and the presence of disulfide unit enhances the absorption characteristics of the compound.

Figure 6 shows the photoluminescence spectra of compounds FCSO and FNSO thin films. It can be seen from the figure that the compounds have achieved better blue light emission, among which FCSO has achieved deep blue light emission, indicating that such compounds have the potential to prepare deep blue light materials.

Fig. 7 is the fluorescence emission picture of compound FNSO (left) and FCSO (right) tetrahydrofuran solution (concentration is 10 ^-5 mol/L), it can be seen that the compound has better fluorescence emission, wherein FNSO is blue light fluorescence emission; FCSO is Dark blue fluorescent emission.

Claims (9)

1. pair S, S-dioxo-dibenzothiophene 5-membered ring compounds, it is characterized in that, described compound has following structural formula:

In formula, X is the one in having structure:

Wherein, R ₁, R ₂for carbonatoms is the alkyl of 1-30.

2. two S, S-dioxo-dibenzothiophene 5-membered ring compounds according to claim 1, it is characterized in that, the concrete structure of described compound is:

Wherein, R ₁, R ₂for carbonatoms is the alkyl of 1-30.

3. prepare according to claim 1 pair of S, S-dioxo-dibenzothiophene and the method for 5-membered ring compounds, it is characterized in that comprising the steps:

1) bromo-for 2,7-bis-fluorenes and heterosubstituted derivatives thereof are dissolved in tetrahydrofuran solution respectively, under low temperature, drip the hexane solution of n-Butyl Lithium, insulation reaction 1 ~ 3 hour; Add 2-sec.-propyl-4,4,5,5-tetramethyl--1 afterwards, 3,2-dioxaborinate, reacts reaction solution to 5 ~ 20 hours at ambient temperature, reaction terminates rear extraction, drying, purifies, and obtains product (I)-2,7-diborate-fluorenes and heterosubstituted derivatives thereof respectively;

2) by the ratio mixing of product (I) and 1-bromo-2-methylsulfinyl benzene 1:2 ~ 10 in molar ratio, be dissolved in respectively in the middle of organic solvent, reaction 8 ~ 80 hours under palladium catalyst, at 40 ~ 100 DEG C; After completion of the reaction, extraction, dry, purification, obtain product (II)-2,7-bis-(2-methylsulfinyl phenyl)-fluorenes and heterosubstituted derivatives thereof respectively;

3) product (II) is reacted respectively in trifluoromethayl sulfonic acid, add Vanadium Pentoxide in FLAKES simultaneously, react 2 ~ 20 hours, after reaction terminates reaction solution to be added drop-wise in water and suction filtration, after filter residue dries in pyridine reflux 2 ~ 30 hours, reaction terminates rear extraction, drying, purification, obtains product (Ш)-bis-(dibenzothiophene) respectively and 5-membered ring compounds;

4) product (Ш) is dissolved in organic solvent respectively, add oxidant reaction 2 ~ 10 hours, after reaction terminates, extraction, dry, purification, obtain product (IV)-bis-(S, S-dioxo-dibenzothiophene) respectively and 5-membered ring compounds.

4. preparation method according to claim 3, is characterized in that, described heterosubstituted derivatives is the one in silicon fluorenes, germanium fluorenes, tin fluorenes, diphenylene-oxide, carbazole, phosphine fluorenes, phosphine dibenzofuran, dibenzothiophen, selenium fluorenes and boron fluorenes.

5. preparation method according to claim 3, it is characterized in that, step 3) in two (dibenzothiophene) five-ring be pair (dibenzothiophene) pentalenes, two (dibenzothiophene) Silole, two (dibenzothiophene) germanium heterocyclic pentylene, two (dibenzothiophene) tin heterocyclic pentylene, two (dibenzothiophene) furans, two (dibenzothiophene) pyrroles, two (dibenzothiophene) phosphine heterocyclic pentylene, two (dibenzothiophene) phosphine oxole, two (dibenzothiophene) thiophthene, two (dibenzothiophene) selenophen or two (dibenzothiophene) boron heterocyclic pentylene.

6. preparation method according to claim 3, it is characterized in that, step 4) in two (S, S-dioxo-dibenzothiophene) and five-ring is two (S, S-dioxo-dibenzothiophene) pentalene, two (S, S-dioxo-dibenzothiophene) and Silole, two (S, S-dioxo-dibenzothiophene) and germanium heterocyclic pentylene, two (S, S-dioxo-dibenzothiophene) and tin heterocyclic pentylene, two (S, S-dioxo-dibenzothiophene) and furans, two (S, S-dioxo-dibenzothiophene) and pyrroles, two (S, S-dioxo-dibenzothiophene) and phosphine heterocyclic pentylene, two (S, S-dioxo-dibenzothiophene) and phosphine oxole, two (S, S-dioxo-dibenzothiophene) thiophthene, two (S, S-dioxo-dibenzothiophene) and selenophen, two (S, S-dioxo-dibenzothiophene) and boron heterocyclic pentylene.

7. preparation method according to claim 3, is characterized in that, step 2) described in catalyzer be Pd (PPh ₃) ₄, Pd ₂(dba) ₃or Pd (OAc) ₂; Described solvent is any one or its mixture in tetrahydrofuran (THF), toluene.

8. preparation method according to claim 3, is characterized in that, step 4) described in organic solvent be a kind of in methylene dichloride, tetrahydrofuran (THF), trichloromethane or its mixture; Described oxygenant is a kind of in hydrogen peroxide, 3-chloroperoxybenzoic acid or its mixture.

9. according to claim 1 pair of S, S-dioxo-dibenzothiophene 5-membered ring compounds is preparing the application in organic electroluminescence device, organic photovoltaic cell and organic field effect tube.