A five-coordinate phosphorus heterocyclic compound with fluorescent properties and a synthesis method thereof

Abstract

The invention discloses a five-coordinate phosphorus heterocyclic compound with fluorescent properties and a synthesis method thereof, wherein the compound is a novel phosphorus heterocyclic skeleton molecule having two phosphorus atoms with different coordination numbers in its parent core structure; the synthesis method is to use 2-(alkynyl) aromatic phenol (I), disubstituted phosphorus oxygen (II), and monosubstituted hypophosphorous acid (III) as raw materials, fully dissolve them in an organic solvent, then add anhydride and alkali to the reaction system, place under 25-100°C conditions to react for 0.5-1 hour, treat with an oxidant after the reaction is completed, extract with ethyl acetate, collect the organic phase, remove the solvent under reduced pressure, and separate by silica gel column chromatography to obtain a target compound (IV). The reaction has the characteristics of simple operation and easy availability of raw materials, and is a synthetic method with good application prospects. The synthesized target compound has strong fluorescent characteristics and is a molecular structure with potential application value.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a five-coordinated phosphorus heterocyclic compound with fluorescent properties and a synthesis method thereof. Background Art

[0002] Phosphorus heterocyclic compounds are widely used in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), organic photovoltaic cells (OPVs) and optical sensors. However, the application of this heterocyclic molecule is basically concentrated on phosphoryl compounds with tetracoordinate phosphorus, while the development of pentacoordinate phosphorus heterocyclic skeletons with unique electronic structures is relatively rare. Related studies have shown that due to the special chemical and electronic properties of pentacoordinate phosphorus, this type of phosphorus heterocyclic molecule is expected to show special applications in the field of functional materials. However, the lack of synthetic methods for pentacoordinate phosphorus heterocyclic compounds has led to a serious lack of diversity in this type of molecule. Currently, there are only two reports on the structure and synthesis of pentacoordinate phosphorus heterocyclics:

[0003] (1) In 1991, Professors Vedejs and Steck first reported a method for synthesizing the first condensed-ring pentacoordinated phosphorus heterocyclic compound skeleton by acyl transfer from o-acetoxy-o-diphenylphosphoryltoluene, but this report did not attract widespread attention (Angewandte Chemie International Edition. 1999, 38 (18), 2788-2791).

[0004]

[0005] (2) In 2017, Duan's group further reported a method for synthesizing similar pentacoordinated phosphorus heterocyclic compounds. This method only synthesized five different substituted target compounds, so the substrate applicability of this method is not wide enough to meet the needs of synthesizing a large number of such compounds. In addition, the optical and physical properties of this target compound have not been explored. (Org Lett., 2017, 19(21), 5814-5817).

[0006]

[0007] From the perspective of crystallographic analysis, condensed-ring penta-coordinated phosphorus heterocyclic compounds have high planarity and rigidity, among which the planarity and rigidity of the molecular structure are generally the key parameters leading to excellent photophysical properties. Therefore, condensed-ring penta-coordinated phosphorus heterocyclic compounds may have good fluorescence properties and are expected to have potential applications in the field of organic optoelectronic materials. However, there are currently very few reports on the structure and synthesis of penta-coordinated phosphorus heterocyclic compounds, and the two synthetic methods mentioned above have obvious shortcomings (such as poor substrate applicability, difficulty in synthesizing raw materials, high reaction temperature, etc.). Therefore, it is of great practical significance to develop a simple and practical synthetic method to prepare a new penta-coordinated phosphorus heterocyclic compound with special fluorescence properties. Summary of the invention

[0008] The purpose of the present invention is to provide a five-coordinate phosphorus heterocyclic compound with fluorescent properties and a synthesis method thereof. The present invention utilizes a three-component reaction of two electron-deficient phosphorus reagents with alkynes to prepare a biphosphorus ring compound with a five-coordinate phosphorus center.

[0009] The present invention provides a biphosphorus heterocyclic compound with fluorescent properties, the structure of which is as follows:

[0010]

[0011] In the structural formula of the bisphosphorus heterocyclic compound, R 1 ~R 2 Each is independently H, D, (CH2) n Any one of CH3, C(CH3)3, Ph, X, COOR, R 3 ~R 5 Each independently is (CH2) z Any one of CH3, C(CH3)3, Ph; wherein X is one of F, Cl, Br, I, R is one of H, (CH2)yCH3, C(CH3)3, and n, m, y, z are each independently a value of 0 to 8.

[0012] The present invention further provides a method for synthesizing the above-mentioned bisphosphorus heterocyclic compound, comprising the following synthesis steps: step 1, using 2-(alkynyl) aromatic phenol (I), disubstituted phosphorus oxide (II), monosubstituted hypophosphorous acid (III), acid anhydride and base as raw materials, adding an organic solvent at room temperature to fully dissolve; step 2, reacting at 25 to 100° C. for 0.5 to 1 hour; step 3, after the reaction is completed, the reaction solution is treated with an oxidant, and then separated and purified to obtain the target compound bisphosphorus heterocyclic compound (IV) with fluorescent properties.

[0013] The reaction formula of the reaction is as follows:

[0014]

[0015] In the above reaction formula, R 1 ~R 2 Each is independently H, D, (CH2) n Any one of CH3, C(CH3)3, Ph, X, COOR, R 3 ~R 5 Each independently is (CH2) z Any one of CH3, C(CH3)3, Ph; wherein X is one of F, Cl, Br, I, R is one of H, (CH2)yCH3, C(CH3)3, and n, m, y, z are each independently a value of 0 to 8.

[0016] Preferably, the organic solvent in step 1 is one or a mixture of the following: C1-C4 halogenated hydrocarbons, acetonitrile, tetrahydrofuran, benzene, toluene, DMF, and dioxane.

[0017] Preferably, the acid anhydride described in step 1 is one or more selected from phosphorus pentoxide, acetic anhydride, trifluoroacetic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, benzenesulfonic anhydride, and p-toluenesulfonic anhydride.

[0018] Furthermore, the mass (weight) of the organic solvent in step 1 is 10 to 50 times the mass of compound (I).

[0019] Preferably, the base in step 1 is one or more selected from DABCO, DBU, triethylamine, pyridine, and 2,6-lutidine.

[0020] Preferably, the oxidant described in step 3 is one or more selected from m-chloroperbenzoic acid, perbenzoic acid, di-tert-butyl peroxide, peracetic acid, and hydrogen peroxide.

[0021] Furthermore, the separation and purification in step 3 includes the following steps: extraction with ethyl acetate, washing the organic layer with saturated brine, drying with anhydrous sodium sulfate, evaporating the ethyl acetate solvent, and separating by silica gel column chromatography to obtain the target compound bisphosphorus heterocyclic compound (IV).

[0022] After the reaction is completed, the reaction solution is treated with an oxidant and then extracted with ethyl acetate. The organic layer is washed with saturated brine and dried over anhydrous sodium sulfate. After the ethyl acetate solvent is evaporated, the target compound (IV) is separated and purified by silica gel column chromatography.

[0023] The beneficial effects of the present invention are as follows: the present invention uses 2-(alkynyl) aromatic phenol, disubstituted phosphorus oxygen, and monosubstituted hypophosphorous acid as raw materials, and synthesizes a novel double phosphorus heterocyclic compound through a direct three-component one-pot method. The novel phosphorus heterocyclic compound has excellent fluorescence properties and has potential application value in the field of organic functional materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the ultraviolet absorption spectrum in Example 10;

[0025] Figure 2 is the fluorescence emission spectrum in Example 10. DETAILED DESCRIPTION

[0026] The present invention is further described in detail by the following examples, but the protection scope is not limited thereto.

[0027] Embodiment 1:

[0028] Preparation of 2,3,9,9-tetraphenyl-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetraene

[0029]

[0030] Representative implementation process: At room temperature, 2-(phenylethynyl)phenol compound I-1 (0.3881 g, 2 mmol), diphenylphosphine II-1 (0.4852 g, 2.4 mmol) and 10 mL of 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853 mL, 6 mmol), trifluoromethanesulfonic anhydride (1.3459 mL, 8 mmol) and phenylphosphine III-1 (0.5684 g, 4 mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, the mixture was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate. The ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.67 g of the target compound IV-1, with a total reaction yield of 65%.

[0031] Yellow solid; 31 P NMR(162MHz,Chloroform-d)δ22.02,-35.54; 1 H NMR (400MHz, Chloroform-d) δ8.29–8.21(m,2H),7.89–7.81(m,2H),7.54-7.21(m,13H),7.13–7.06(m,4H),6.96–6.85(m,2H),6.59(t,J=7.6Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ159.93(s,C),148.25(dd,J C-P =108.9,21.0Hz,C),138.30(dd,J C-P =138.4,10.4Hz,C),136.71(dd,J C-P=174.7,4.0Hz,C),134.49(d,J C-P =163.6Hz,C),133.77(d,J C-P =12.9Hz,2CH),133.34(s,CH),133.15(dd,J C-P =29.3,8.6Hz,C),132.10(d,J C-P =2.8Hz,2CH),131.99(d,J C-P =3.7Hz,2CH),131.84(d,J C-P =2.9Hz,CH),131.35(dd,J C-P =20.0,3.7Hz,2CH),130.08(dd,J C-P =144.8,2.3Hz,C),129.07(s,2CH),128.87(d,J C-P =1.6Hz,CH),128.45(d,J C-P =35.3Hz,2CH),128.45(s,CH),128.44(s,CH),127.98(d,J C-P =14.0Hz,2CH),127.76(d,J C-P =2.5Hz,2CH),124.84(d,J C-P =17.4Hz,CH),119.96(dd,J C-P =27.3,15.8Hz,C),119.81(s,CH),113.21(d,J C-P =1.7Hz,CH).

[0032] Embodiment 2:

[0033] Preparation of 2,9,9-triphenyl-3-(p-tolyl)-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetramethylene

[0034]

[0035] Representative implementation process: At room temperature, 2-(4'-tolueneethynyl)phenol compound I-2 (0.4162g, 2mmol), diphenylphosphine II-2 (0.4852g, 2.4mmol) and 10mL 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853mL, 6mmol), trifluoromethanesulfonic anhydride (1.3459mL, 8mmol) and phenylphosphine III-2 (0.5684g, 4mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.49g of the target compound IV-2, with a total reaction yield of 46%. Yellow solid; 31 PNMR(162MHz,Chloroform-d)δ22.22,-35.56; 1 H NMR(400MHz,Chloroform-d)δ8.29–8.19(m,2H),7.90–7.78(m,2H),7.57–7.38(m, 6H),7.33–7.01(m,11H),6.87(d,J=8.1Hz,1H),6.61(t,J=7.4Hz,1H),2.35(s,3H); 13 C NMR(101MHz,Chloroform-d)δ159.89(s,C),148.38(dd,J C-P =109.1,21.0Hz,C),138.97(d,J C-P =1.6Hz,C),137.79(dd,J C-P =138.4Hz,10.6Hz,C),136.82(dd,J C-P =173.7Hz,2.9Hz,C),135.43(s,C),133.75(d,J C-P =12.8Hz,2CH),133.22(s,CH),132.12(s,2CH),132.00(d,J C-P =2.3Hz,2CH),131.80(d,J C-P =2.0Hz,CH),130.03(dd,J C-P =19.5,3.5Hz,2CH),130.20(dd,J C-P =145.4Hz,2.0Hz,C),130.03(dd,J C-P=26.3,8.8Hz,C),129.80(s,2CH),128.61(s,CH),128.44(s,2CH),128.26(s,CH),127.98(d,J C-P =14.0Hz,2CH),127.71(d,J C-P =3.3Hz,2CH),124.84(d,J C-P =17.6Hz,CH),130.03(dd,J C-P =29.6,16.1Hz,C),119.76(s,CH),113.19(d,J C-P =1.2Hz,CH),21.43(s,CH3).

[0036] Embodiment 3:

[0037] Preparation of 2,9,9-triphenyl-3-(4-fluorophenyl)-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetramethylene

[0038]

[0039] Representative implementation process: At room temperature, 2-(4'-fluorophenylethynyl)phenol compound I-3 (0.4241g, 2mmol), diphenylphosphine II-3 (0.4852g, 2.4mmol) and 10mL 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853mL, 6mmol), trifluoromethanesulfonic anhydride (1.3459mL, 8mmol) and phenylphosphine III-3 (0.5684g, 4mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.83g of the target compound IV-3, with a total reaction yield of 77%. Yellow solid; 31 PNMR(162MHz,Chloroform-d)δ21.88,-35.33(d,J=3.9Hz); 1 H NMR(400MHz,Chloroform-d)δ8.30–8.18(m,2H),7.89–7.78(m,2H),7.56–7.38(m,7H),7.32–7.2 1(m,3H),7.13–7.02(m,6H),6.98(d,J=7.8Hz,1H),6.89(d,J=8.1Hz,1H),6.63(t,J=7.6Hz,1H); 13C NMR(101MHz,Chloroform-d)δ163.02(dd,J C-F =249.2,1.8Hz,C),159.98(s,C),146.98(dd,J C-P =109.5,21.7Hz,C),138.64(dd,J C-P =137.2,10.4Hz,C),136.57(dd,J C-P =173.8,3.2Hz,C),134.32(d,J C-P =163.6Hz,C),133.77(d,J C-P =12.9Hz,2CH),133.54(s,CH),132.08(d,J C-P =4.3Hz,2CH),131.97(d,J C-P =3.2Hz,2CH),131.95(s,CH),131.42(dd,J C-P =19.2,3.7Hz,2CH),129.92(dd,J C-P =145.44,2.3Hz,C),129.83(s,2CH),128.97(ddd,J C-P J C-F =26.8,9.0,3.5Hz,C),128.63(s,CH),128.46(s,2CH),128.29(s,CH),128.06(d,J C-P =14.0Hz,2CH),124.62(d,J C-P =17.3Hz,CH),119.89(s,CH),119.69(dd,J C-P =27.3,15.7Hz,C),116.41(s,CH),116.30(d,J C-P =21.7Hz,2CH),113.37(d,J C-P =1.7Hz,CH).

[0040] Embodiment 4:

[0041] Preparation of 2,9,9-triphenyl-3-(4-cyanophenyl)-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetramethylene

[0042]

[0043] Representative implementation process: At room temperature, 4-((2-hydroxyphenyl)ethynyl)benzonitrile compound I-4 (0.4381g, 2mmol), diphenylphosphine II-4 (0.4852g, 2.4mmol) and 10mL 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853mL, 6mmol), trifluoromethanesulfonic anhydride (1.3459mL, 8mmol) and phenylphosphine III-4 (0.5684g, 4mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.81g of the target compound IV-4, with a total reaction yield of 75%. Yellow solid; 31 P NMR(162MHz,Chloroform-d)δ21.09,-34.78; 1 H NMR(400MHz,Chloroform-d)δ8.31–8.19(m,2H),7.91–7.80(m,2H),7.66(d,J=7.5Hz,2H),7.58–7.38(m,8H ),7.37–7.27(m,2H),7.16–7.04(m,4H),6.91(d,J=8.2Hz,1H),6.81(d,J=7.8Hz,1H),6.64(t,J=7.6Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ160.17(s,C),145.53(dd,J C-P =108.3,22.5Hz,C),140.04(dd,J C-P =136.8,9.5Hz,C),138.42(dd,J C-P =26.8,8.8Hz,C),136.07(dd,J C-P =173.4,3.4Hz,C),134.20(s,CH),136.07(d,J C-P =163.62Hz,C),133.80(d,J C-P =12.9Hz,2CH),132.82(s,2CH),132.26(d,J C-P =2.8Hz,CH),132.06(d,J C-P =25.2Hz,2CH),132.05(s,2CH),131.64(dd,J C-P =18.3,3.7Hz,2CH),130.16(d,JC-P =2.3Hz,C),128.72(s,CH),128.72(s,2CH),128.56(s,2CH),128.28(d,J C-P =14.1Hz,2CH),128.17(s,CH),124.58(d,J C-P =17.4Hz,CH),120.18(s,CH),119.16(dd,J C-P =29.0,15.2Hz,C),118.34(s,C),113.64(d,J C-P =1.8Hz,CH),112.65(d,J C-P =1.8Hz,C).

[0044] Embodiment 5:

[0045] Preparation of 3-butyl-2,9,9-triphenyl-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetramethylene

[0046]

[0047] Representative implementation process: At room temperature, 2-(hexynyl)phenol compound I-5 (0.3482g, 2mmol), diphenylphosphine II-5 (0.4852g, 2.4mmol) and 10ml 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853mL, 6mmol), trifluoromethanesulfonic anhydride (1.3459mL, 8mmol) and phenylphosphine III-5 (0.5684g, 4mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.23g of the target compound IV-5, with a total reaction yield of 23%. Colorless solid; 31 P NMR (162MHz, Chloroform-d) δ24.23 (d, J = 6.4Hz), -36.27 (d, J = 6.5Hz); 1H NMR(400MHz,Chloroform-d)δ8.18–8.09(m,1H),7.81–7.72(m,1H),7.68(d,J=7.6Hz,1H),7.51–7.30(m,3H), 7.25–7.13(m,1H),6.94(dd,J=12.5,7.9Hz,1H),3.02–2.65(m,1H),1.74–1.27(m,1H),0.86(t,J=7.1Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ159.56(s,C),150.68(dd,J C-P =107.9,18.2Hz,C),136.97(dd,J C-P =173.7,3.6Hz,C),136.68(dd,J C-P =139.4,10.9Hz,C),135.11(d,J C-P =166.65Hz,C),133.36(d,J C-P =12.8Hz,2CH),132.64(s,CH),132.13(d,J C-P =4.9Hz,2CH),132.13(d,J C-P =18.2Hz,2CH),131.91(d,J C-P =2.7Hz,CH),131.13(t,J C-P =4.2Hz,2CH),130.75(dd,J C-P =142.4,2.4Hz,C),128.48(s,CH),128.31(s,2CH),128.13(s,CH),128.13(d,J C-P =14.0Hz,2CH),124.97(d,J C-P =18.9Hz,CH),120.64(dd,J C-P =30.6,17.3Hz,C),120.17(s,CH),113.16(d,J C-P =1.5Hz,CH),29.50(s,CH2),28.50(dd,J C-P =22.7,9.9Hz,CH2),23.15(s,CH2),13.65(s,CH3).

[0048] Embodiment 6:

[0049] Preparation of 2,9,9-triphenyl-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetramethylene

[0050]

[0051] Representative implementation process: At room temperature, 2-((trimethylsilyl)ethynyl)phenol compound I-6 (0.3802g, 2mmol), diphenylphosphine II-6 (0.4852g, 2.4mmol) and 10mL 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853mL, 6mmol), trifluoromethanesulfonic anhydride (1.3459mL, 8mmol) and phenylphosphine III-6 (0.5684g, 4mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.36g of the target compound IV-6, with a total reaction yield of 41%. Yellow solid; 31 P NMR (162MHz, Chloroform-d) δ21.98 (d, J = 4.3Hz), -32.74 (d, J = 4.2Hz); 1 H NMR(400MHz,Chloroform-d)δ8.26–8.11(m,1H),7.76(dd,J=16.0,8.0Hz,1H),7. 57(d,J=8.7Hz,1H),7.51–7.33(m,1H),7.28–7.14(m,1H),6.92(t,J=8.8Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ159.83(s,C),147.07(dd,J C-P =133.6,5.0Hz,C),135.76(dd,J C-P =170.9,3.5Hz,C),134.29(s,CH),133.80(d,J C-P =165.6Hz,C),133.71(d,J C-P =12.9Hz,2CH),132.22(d,J C-P =1.9Hz,C),132.13(s,CH),131.99(d,J C-P =3.6Hz,2CH),131.80(d,J C-P =11.5Hz,2CH),131.51(dd,J C-P =15.6,3.6Hz,2CH),130.09(dd,J C-P=114.1,19.1Hz,CH),128.63(s,CH),128.47(s,2CH),128.30(s,2CH),128.16(s,CH),123.98(d,J C-P =16.9Hz,CH),120.44(s,CH),119.49(dd,J C-P =29.4,16.4Hz,C),113.45(s,CH).

[0052] Embodiment 7:

[0053] Preparation of 6-bromo-2,3,9,9-tetraphenyl-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetraene

[0054]

[0055] Representative implementation process: At room temperature, 5-bromo-2-(phenylethynyl)phenol compound I-7 (0.5439 g, 2 mmol), diphenylphosphine II-7 (0.4852 g, 2.4 mmol) and 10 mL of 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853 mL, 6 mmol), trifluoromethanesulfonic anhydride (1.3459 mL, 8 mmol) and phenylphosphine III-7 (0.5684 g, 4 mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.75 g of the target compound IV-7, with a total reaction yield of 63%. Yellow solid; 31 PNMR(162MHz,Chloroform-d)δ21.93,-34.39; 1 H NMR (400MHz, Chloroform-d) δ8.27–8.15(m,2H),7.86–7.75(m,2H),7.57–7.28(m,13H),7.14–6.98(m,5H),6.77(d,J=8.7Hz,1H); 13 C NMR(101MHz,Chloroform-d)δ158.81(s,C),150.10(dd,J C-P =107.6,20.8Hz,C),136.92(dd,J C-P =139.4,10.8Hz,C),136.36(dd,J C-P=174.7,3.3Hz,C),135.88(s,CH),134.13(d,J C-P =164.6Hz,C),133.68(d,J C-P =13.0Hz,2CH),132.49(dd,J C-P =25.7,8.5Hz,C),132.07(d,J C-P =2.9Hz,CH),132.01(d,J C-P =1.7Hz,2CH),132.01(d,J C-P =25.3Hz,2CH),131.55(dd,J C-P =18.4,3.7Hz,2CH),129.70(dd,J C-P =146.5,2.3Hz,C),129.38(d,J C-P =1.4Hz,CH),129.26(s,2CH),128.72(s,CH),128.55(s,2CH),128.38(s,CH),128.10(d,J C-P =14.0Hz,2CH),127.53(s,2CH),127.35(d,J C-P =17.7Hz,CH),121.57(dd,J C-P =30.4,15.9Hz,C),115.00(s,CH),111.63(s,C).

[0056] Embodiment 8:

[0057] Preparation of 9,9-dimethyl-2,3-diphenyl-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]oltetramethylene

[0058]

[0059] Representative implementation process: At room temperature, 2-(phenylethynyl)phenol compound I-8 (0.5439 g, 2 mmol), dimethylphosphine oxide II-8 (0.1873 g, 2.4 mmol) and 10 mL of 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853 mL, 6 mmol), trifluoromethanesulfonic anhydride (1.3459 mL, 8 mmol) and phenylphosphite III-8 (0.5684 g, 4 mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, it was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate; the ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.24 g of the target compound IV-8, with a total reaction yield of 31%. Yellow solid; 31 P NMR (162MHz, Chloroform-d) δ20.92 (d, J = 1.2Hz), -19.46; 1 H NMR(400MHz,Chloroform-d)δ7.67–7.60(m,2H),7.50–7.44(m,1H),7.41–7.33(m,5H),7.29–7.19(m,3H),6.85 (d,J=7.7Hz,1H),6.75(d,J=8.1Hz,1H),6.55(t,J=7.6Hz,1H),2.28(d,J=16.2Hz,3H),2.22(d,J=16.3Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ159.95(s,C),146.36(dd,J C-P =109.4,21.2Hz,C),138.85(dd,J C-P =132.5,10.2Hz,C),133.27(dd,J C-P =25.3,8.5Hz,C),133.22(s,CH),132.03(d,J C-P =2.7Hz,2CH),131.94(s,CH),130.90(dd,J C-P =144.1,1.3Hz,C),129.09(s,2CH),128.74(d,J C-P =1.7Hz,CH),128.39(d,J C-P =13.7Hz,2CH),127.68(dd,J C-P =4.4,1.6Hz,2CH),124.70(d,J C-P=17.1Hz,CH),119.38(s,CH),119.26(dd,J C-P =30.3,15.8Hz,C),113.17(d,J C-P =0.7Hz,CH),22.80(d,J C-P =115.8Hz,CH3),21.33(dd,J C-P =121.9,4.2Hz,CH3).

[0060] Embodiment 9:

[0061] Preparation of 9,9-bis(3,5-dimethylphenyl)-2,3-diphenyl-2-oxo-1,8-dioxa-2,9-diphospha-benzo[e]phenene

[0062]

[0063] Representative implementation process: At room temperature, 2-(ethynyl)phenol compound I-9 (0.4178 g, 2 mmol), bis(3,5-dimethylphenyl)phosphine oxide II-9 (0.6199 g, 2.4 mmol) and 10 mL of 1,2-dichloroethane were added to the reaction bottle in sequence, and pyridine (0.4853 mL, 6 mmol), trifluoromethanesulfonic anhydride (1.3459 mL, 8 mmol) and phenylphosphite III-9 (0.5684 g, 4 mmol) were added to the reaction bottle under argon atmosphere and reacted at 80°C for 1 hour. TLC was used to track the progress of the reaction. After the reaction was completed, the mixture was oxidized with hydrogen peroxide and extracted with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate. The ethyl acetate solvent was evaporated, and then separated and purified by silica gel column chromatography to obtain 0.4592 g of the target compound IV-9, with a total reaction yield of 40%.

[0064] Yellow solid; 31 P NMR(162MHz,Chloroform-d)δ21.76,-33.86; 1 H NMR(400MHz,Chloroform-d)δ7.83(d,J=16.2Hz,2H),7.46–7.30(m,7H),7.29–7.20(m,2H),7.17–7.06 (m,6H),6.96(d,J=7.7Hz,1H),6.88(d,J=8.2Hz,1H),6.59(t,J=7.6Hz,1H),2.38(s,6H),2.29(s,6H); 13 C NMR(101MHz,Chloroform-d)δ160.02(s,C),147.91(dd,J C-P=108.9,20.8Hz,C),138.43(dd,J C-P =137.4,10.3Hz,C),138.11(s,2C),137.94(s,2C),136.18(dd,J C-P =170.9,3.2Hz,C),134.17(d,J C-P =161.6,Hz,C),133.37(dd,J C-P =25.3,8.6Hz,C),133.24(d,J C-P =3.7Hz,2CH),132.86(d,J C-P =3.7Hz,CH),132.18(d,J C-P =11.2Hz,2CH),131.73(d,J C-P =2.7Hz,CH),131.12(d,J C-P =12.8Hz,2CH),129.74(d,J C-P =2.2Hz,C),129.40(d,J C-P =12.0Hz,2CH),129.04(s,2CH),128.83(d,J C-P =1.0Hz,CH),127.99(s,CH),127.92(s,CH),127.85(s,2CH),124.84(d,J C-P =17.2Hz,CH),119.98(dd,J C-P =29.1,15.8Hz,C),119.60(s,CH),113.34(s,CH),21.56(d,J C-P =0.7Hz,2CH3),21.44(s,2CH3).

[0065] Example 10: This example is an example of photophysical properties implementation

[0066] 1) Compounds IV-1 to IV-9 were prepared at a concentration of 1×10 -5 mol / L dichloromethane solution;

[0067] 2) Pipette 3 mL of dichloromethane solution of compounds IV-1 to IV-9 into a cuvette, test the ultraviolet absorption spectra of compounds IV-1 to IV-9 in the wavelength range of 200 to 800 nm, and obtain the ultraviolet absorption spectra of compounds IV-1 to IV-9.

[0068] Maximum absorption wavelength of IV-9;

[0069] 3) Repeat the above steps to test the fluorescence emission spectra of compounds IV-1 to IV-9 at wavelengths of 374 nm, 375 nm, 379 nm, 375 nm, 359 nm, 369 nm, 384 nm, 370 nm, and 374 nm, respectively, with a scanning range of 380 to 800 nm.

[0070] Table 1 UV absorption and fluorescence emission data of target products

[0071]

[0072] The above results show that this type of five-coordinated diphosphorus heterocyclic compound not only exhibits excellent fluorescence properties, but also has a wide distribution of luminescent colors (from light blue to orange), and is a class of organic functional molecules with great potential application value.

Claims

1. A fluorescent biphosphorus heterocyclic compound, the structure of which is as follows: R 1 ~R 2 Each is independently H, D, (CH2) n Any one of CH3, C(CH3)3, Ph, X, COOR, R 3 ~R 5 Each independently is (CH2) z Any one of CH3, C(CH3)3, Ph; wherein X is one of F, Cl, Br, I, and R is H, (CH2) y One of CH3 and C(CH3)3, and n, y and z are each independently a value of 0 to 8.

2. The method for preparing the fluorescent bisphosphorus heterocyclic compound according to claim 1, comprising the following synthesis steps: Step 1, using 2-(alkynyl) aromatic phenol (I), disubstituted phosphorus oxide (II), monosubstituted hypophosphorous acid (III), acid anhydride and base as raw materials, adding an organic solvent to fully dissolve at room temperature; Step 2, reacting at 25-100° C. for 0.5-1 hour; Step 3, after the reaction is completed, the reaction solution is treated with an oxidant, and then separated and purified to obtain the target compound, a bisphosphorus heterocyclic compound (IV) having fluorescent properties; The reaction formula of the reaction is: In the above reaction formula, R 1 ~R 2 Each is independently H, D, (CH2) n Any one of CH3, C(CH3)3, Ph, X, COOR, R 3 ~R 5 Each independently is (CH2) z Any one of CH3, C(CH3)3, Ph; wherein X is one of F, Cl, Br, I, and R is H, (CH2) y One of CH3 and C(CH3)3, n, y and z are each independently a value of 0 to 8; The organic solvent is 1,2-dichloroethane, the acid anhydride is trifluoromethanesulfonic anhydride, the base is pyridine, and the oxidant is hydrogen peroxide.

3. The preparation method according to claim 2, characterized in that: The separation and purification in step 3 includes the following steps: extraction with ethyl acetate, washing the organic layer with saturated brine, drying over anhydrous sodium sulfate, evaporating the ethyl acetate solvent, and separating by silica gel column chromatography to obtain the target compound bisphosphorus heterocyclic compound (IV).

4. The preparation method according to claim 2, characterized in that: The mass of the organic solvent is 10 to 50 times the mass of the compound (I).

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