Phospholene metal salt compound and method for preparing the same

Abstract

The application provides a phospholane metal salt compound shown in formula (III) and a preparation method thereof. The phospholane metal salt compound is an organic phosphorus compound based on a phospholane structural unit, which is directly synthesized by using white phosphorus. The process method avoids the use of highly-polluting chlorine gas and subsequent emission problems in traditional phosphorus chemical production, and is a more environmentally-friendly production method. In addition, the method disclosed by the application has the advantages of mild reaction conditions, short reaction time, simple post-treatment and high yield.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic phosphorus chemical industry, in particular, to a phospholuenium metal salt compound and a preparation method thereof. BACKGROUND

[0002] Phosphafluorene refers to a class of compounds in which the carbon atom at position 9 of fluorene is replaced by a phosphorus atom, also known as dibenzophosphole. Since such a phosphafluorene compound has a heteroatom-phosphorus atom introduced therein, it can be used as a ligand in metal organic chemistry, for the synthesis of rare earth metal complexes or transition metal complexes (see Non-Patent Literature 1 and 2). In addition, the structure of the phosphafluorene compound belongs to a tricyclic π-conjugated structure, which has a rigid conjugated plane, so it still maintains the good photoelectric properties of fluorene compounds. Among them, the phosphorus atom can change the electronic structure of the material through the interaction between the d orbitals and the π-conjugated system, and can also be modified by oxidation and other methods, thereby effectively adjusting the photoelectric properties of the material, and is widely used in the manufacture of optoelectronic devices (see Non-Patent Literature 3 and 4).

[0003] Phospholuenium metal salt compound is an important intermediate in the synthesis of phosphafluorene compounds. In the prior art, it is mainly synthesized by reacting 9-phenyl-9-phosphafluorene with an alkali metal, and then further synthesized various organic phosphorus compounds containing phosphafluorene structural units by derivatization and other reactions (see Non-Patent Literature 2, 5, 6).

[0004] From the various preparation methods of the above-mentioned literatures, it can be seen that the reaction substrate 9-phenyl-9-phosphafluorene used is synthesized from the basic phosphorus chemical product aryl dichlorophosphine (ArPCl2). As is known, as the basic raw material of such compounds, it is currently prepared from white phosphorus (P4) in the phosphorus chemical industry, which requires the use of chlorine gas, which is not friendly to the environment and human body, and a large amount of waste gas, waste acid and the like is generated during the reaction process. In this way, the entire production process not only has high energy consumption, but also causes great environmental pollution (see Non-Patent Literature 7).

[0005] Therefore, it is urgent to seek a method for synthesizing phospholuenium metal salt compound without using chlorine gas and to replace the traditional synthesis method.

[0006] Prior art documents

[0007] Non-patent literature

[0008] Non-patent literature 1: N. and R. Louis, J. Organomet. Chem. 1994, 464, 149-154;

[0009] Non-patent document 2: S. Wolfdieter, S. Michael and H. Michael, J. Organomet. Chem. 1998, 560, 257-263;

[0010] Non-patent document 3: R.-F. Chen, R. Zhu, Q.-L. Fan, and W. Huang, Org. Lett. 2008, 10, 2913-2916;

[0011] Non-patent document 4: P. Hibner-Kulicka, J. Joule, J. Skalika and P. RSC Adv. 2017, 7, 9194-9236;

[0012] Non-patent document 5: Y. J. Ahn, R. J. Rubio, T. K. Hollis, F. S. Tham, B. Donnadieu, Organometallics 2006, 25, 1079-1083.

[0013] Non-patent document 6: P. Eisenberger, I. Kieltsch, N. Armanino, A. Togni, Chem. Commun. 2008, 1575-1577.

[0014] Non-patent document 7: Synthesis of Carbon-Phosphorus Bonds, 2nd edition, CRC Press, Boca Raton 2004. SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] The present invention was completed in view of the above problems, and an object thereof is to provide a phosphaphenanthrene metal salt compound which can be synthesized efficiently using a simple and readily available chemical material and greatly reduces environmental pollution caused in the production process.

[0017] MEANS FOR SOLVING THE PROBLEMS

[0018] The technical solution of the present invention is as follows:

[0019] One embodiment of the present invention is a phosphaphenanthrene metal salt compound, which is a compound containing a phosphaphenanthrene structural unit represented by the following formula (III), characterized in that,

[0020]

[0021] wherein R 1 and R 2 may be the same or different and each can be hydrogen, halogen, nitro, cyano, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl (including straight chain alkyl, branched alkyl and cyclic alkyl), C1-C6 alkoxy, substituted or unsubstituted phenyl, pyridyl, thienyl. M represents a metal, which can be an alkali metal or an alkaline earth metal. Sol represents a coordinating solvent, which can be THF, Et2O, DME, or TMEDA. n represents the number of coordinating solvents and is a positive integer or half integer greater than 0 and less than or equal to 3.

[0022] wherein the alkali metal is lithium, sodium, potassium, preferably lithium; and the alkaline earth metal is magnesium, calcium.

[0023] C1-C6 alkyl is preferably methyl, ethyl, propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, cyclohexyl.

[0024] Another aspect of the present application relates to a method for preparing a phospholuenium metal salt compound represented by formula (III),

[0025]

[0026] In formula (III), R 1 and R 2 may be the same or different and each can be hydrogen, halogen, nitro, cyano, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl (including straight chain alkyl, branched alkyl and cyclic alkyl), C1-C6 alkoxy, substituted or unsubstituted phenyl, pyridyl, thienyl. M represents a corresponding metal, which can be an alkali metal or an alkaline earth metal. Sol represents a coordinating solvent, which can be THF, Et2O, DME, or TMEDA. n represents the number of coordinating solvents and is a positive integer or half integer greater than 0 and less than or equal to 3.

[0027] wherein the alkali metal is lithium, sodium, potassium, preferably lithium; and the alkaline earth metal is magnesium, calcium.

[0028] The method comprises the following steps:

[0029] Step 1-1: reacting a compound of formula (I) with an organometallic reagent at low temperature to prepare a compound of formula (II).

[0030]

[0031] In formula (I), X can be chlorine, bromine, iodine, preferably bromine and iodine.

[0032] The organic metal reagent used in step 1-1 can be an organic lithium reagent, a Grignard reagent, a sodium reagent, a potassium reagent, a calcium reagent, preferably an organic lithium reagent, a Grignard reagent.

[0033] The organic lithium reagent is preferably n-butyllithium, tert-butyllithium.

[0034] M is lithium, sodium, potassium, calcium, magnesium, preferably lithium.

[0035] In this reaction step 1-1, the low temperature is -120°C to -60°C, preferably -90°C to -70°C; the reaction time: 0.5 to 3 hours at low temperature, and 2 to 6 hours, preferably 3 to 4 hours, at room temperature.

[0036] As the solvent used in the above reaction, there is no particular limitation as long as an organic solvent in which the reactants can be dissolved and which does not react with the organic metal reagent. For example, tetrahydrofuran (THF), diethyl ether (Et20), benzene, toluene, 1,4-dioxane, ethylene glycol dimethyl ether (DME), or tetramethyl ethylene diamine (TMEDA) and the like.

[0037] As for the ratio of the compound of formula (I) and the organic metal reagent, the ratio of the organic metal reagent used with respect to the compound of formula (I) is 2 to 3 times the molar equivalent, preferably 2.2 to 2.5 times the molar equivalent.

[0038] Step 1-2: reacting the compound of formula (II) with white phosphorus (P4) at a temperature above room temperature to prepare the compound of formula (III).

[0039]

[0040] In this reaction step 1-2, the reaction temperature is in the range of room temperature to 50°C, preferably 25°C to 40°C; the reaction time: 6 to 24 hours, preferably 10 to 20 hours.

[0041] As the solvent used in the above reaction, there is no particular limitation as long as an organic solvent in which the reactants can be dissolved and which does not react with the reactants; the solvent is a coordination solvent (Sol) of the metal M in the compound of formula (III), and can be tetrahydrofuran (THF), diethyl ether (Et20), ethylene glycol dimethyl ether (DME), or tetramethyl ethylene diamine (TMEDA), preferably tetrahydrofuran (THF), diethyl ether (Et20), more preferably tetrahydrofuran (THF).

[0042] n represents the number of coordination solvents, and is a positive integer or half integer greater than 0 and 3 or less.

[0043] The ratio of white phosphorus (P4) to the compound of formula (II) is 1 to 1.5 molar equivalents, preferably 1.1 to 1.45 molar equivalents.

[0044] The solvent used in the above-mentioned step 1-1 and step 1-2 can be the same or different. For the easiness of operation and post-treatment, it is preferred that the solvent in each step is the same; for the best yield and effect, it is also preferred that the solvent in each step is different.

[0045] Effects of the Invention

[0046] According to the present application, an organic phosphorus metal salt compound based on a phospholane structural unit and a preparation method thereof are provided. Since the phospholane metal salt compound is directly synthesized by using a biaryl bimetallic reagent and white phosphorus (P4) at low temperature in the reaction, there is no need to use aryl phosphorus dichloride (ArPCl2) or diaryl phosphorus chloride (Ar2PCl), thereby avoiding the use of chlorine gas which is extremely polluting in the traditional phosphorus chemical production, and there is also no problem of subsequent discharge, post-treatment, etc., and it is a more economical and environmentally friendly production method. In addition, the raw materials of the method disclosed in the present application are cheap and easy to obtain, and the reaction operation conditions are mild, the reaction time is relatively short, the post-treatment is simple, and a high yield can be obtained, so the reaction is an economical and practical reaction.

[0047] The phospholane metal salt compound provided by the present application is an important synthetic intermediate, and various organic phosphorus compounds containing a phospholane structural unit, such as phospholane phosphine oxide compounds and phospholane phosphine hydrogen compounds, etc., can be further synthesized according to needs. Compared with the prior art, the method provided by the present application has the characteristics of simple synthesis and high efficiency, and substitution group modification can be more conveniently carried out, thereby providing phospholane metal salt compounds with various substitution groups. DETAILED DESCRIPTION

[0048] The above invention content of the present application will be further described in detail through specific examples, but this should not be understood as any limitation on the protection scope of the present application. Any technical solution realized based on the above content of the present application belongs to the scope of the present application. The materials used in the test and the test method are generally and / or specifically described. It is clear to those skilled in the art that in the following text, if not specifically stated, the room temperature described in the present application has the technical meaning known in the art, which generally refers to 20-25℃; the chemicals are all from commercial purchase.

[0049] The phospholane metal salt compound of the present application is a compound containing a phospholane structural unit as shown in formula (III),

[0050]

[0051] In formula (III), R 1 and R 2 The radicals may be the same or different and may each be hydrogen, halogen, nitro, cyano, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl (including linear, branched, and cycloalkyl), C1-C6 alkoxy, substituted or unsubstituted phenyl, pyridyl, or thienyl. M represents a metal and may be an alkali metal or an alkaline earth metal.

[0052] Among them, the R 1 and R 2 Preferably, each of them is hydrogen, halogen, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl, C1-C6 alkoxy. Alkyl is preferably methyl, ethyl, tert-butyl; alkoxy is preferably methoxy, ethoxy; R 1 and R 2 More preferred are hydrogen, methyl, methoxy, tert-butyl, trifluoromethyl and fluoro.

[0053] The alkali metals are lithium, sodium, potassium, preferably lithium, and the alkaline earth metals are magnesium and calcium, preferably magnesium.

[0054] The coordinating solvent Sol is THF, Et2O, DME, or TMEDA. THF and Et2O are preferred; THF is more preferred. n represents the number of coordinating solvents and is a positive integer or half-integer greater than 0 and less than 3.

[0055] Preparation of compounds

[0056] The preparation method of the phosphafluorene metal salt compound of the present invention is a preparation method of a compound containing a phosphafluorene structural unit represented by formula (III), which comprises the following steps:

[0057] Step 1-1: The compound of formula (I) is reacted with an organometallic reagent at low temperature to prepare the compound of formula (II).

[0058]

[0059] In the compound of formula (I), X is chlorine, bromine or iodine, preferably bromine or iodine.

[0060] The organometallic reagent used in step 1-1 is an organolithium reagent, a Grignard reagent, a sodium reagent, a potassium reagent or a calcium reagent, preferably an organolithium reagent or a Grignard reagent; more preferably an organolithium reagent; the organolithium reagent is preferably n-butyllithium or tert-butyllithium.

[0061] In the reaction step 1-1, the low temperature is -120°C to -60°C, preferably -90°C to -70°C; the reaction time is: maintaining the reaction at the low temperature for 0.5 to 3 hours, and continuing the reaction at room temperature for 2 to 6 hours, preferably 3 to 4 hours.

[0062] As the solvent used in the above reaction, there is no particular limitation as long as an organic solvent in which the reactants can be dissolved and which does not react with the organometallic reagent. For example, tetrahydrofuran (THF), diethyl ether (Et20), benzene, toluene, 1,4-dioxane, ethylene glycol dimethyl ether (DME), or tetramethylethylenediamine (TMEDA) and the like.

[0063] As for the ratio of the compound of formula (II) to the white phosphorus (P4), the ratio of the white phosphorus used to the compound of formula (II) is 1 to 1.5 molar equivalents, preferably 1.1 to 1.45 molar equivalents.

[0064] Step 1-2: The compound of formula (II) is reacted with white phosphorus (P4) at a temperature above room temperature to produce the compound of formula (III).

[0065]

[0066] In this reaction step 1-2, the reaction temperature is in the range of room temperature to 50°C, preferably 25°C to 40°C; the reaction time: 6 to 24 hours, preferably 10 to 20 hours.

[0067] As the solvent used in the above reaction, there is no particular limitation as long as an organic solvent in which the reactants can be dissolved and which does not react with the reactants; the solvent is a coordination solvent (Sol) of the metal M in the compound of formula (III), and can be tetrahydrofuran (THF), diethyl ether (Et20), ethylene glycol dimethyl ether (DME), or tetramethylethylenediamine (TMEDA), preferably tetrahydrofuran (THF), diethyl ether (Et20), more preferably tetrahydrofuran (THF).

[0068] n represents the number of coordination solvents and is a positive integer or half-integer greater than 0 and 3 or less.

[0069] As for the ratio of the compound of formula (II) to the white phosphorus (P4), the ratio of the white phosphorus used to the compound of formula (II) is 1 to 1.5 molar equivalents, preferably 1.1 to 1.45 molar equivalents.

[0070] The solvents used in the above step 1-1 and step 1-2 can be the same or different. For the ease of operation and post-treatment, it is preferred that the solvents in each step are the same; for the best yield and effect, it is also preferred that the solvents in each step are not the same.

[0071] The above method for preparing the compound will be described in detail below by way of examples.

[0072] Synthesis of the compound of formula (II)

[0073] Example 1: Synthesis of 2,2'-dilithium-1,1'-biphenyl The above method for preparing the compound will be described in detail below by way of examples.

[0074]

[0075] Into a 50 mL flask, 2,2’-dibromo-1,1’-biphenyl 2.0 mmol was added, dissolved in 20 mL of ether, and n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C. After 1 hour of reaction at low temperature, the reaction system was a light yellow solution. After 3 hours of reaction at room temperature, the reaction was complete, as detected by GC-MS. The reaction solvent, ether, was removed under reduced pressure to obtain 2,2’-dilithium-1,1’-biphenyl (white solid).

[0076] Main NMR data: 1 H NMR (400 MHz, THF-d8): 6.87 (t, J = 6.9 Hz, 2H, CH), 7.12 (t, J = 7.8 Hz, 2H, CH), 7.96 (dd, J = 6.5, 1.8 Hz, 4H, CH).

[0077] Example 2: Synthesis of 4-methyl-2,2’-dilithium-1,1’-biphenyl

[0078]

[0079] Into a 50 mL flask, 4-methyl-2,2’-dibromo-1,1’-biphenyl 2.0 mmol was added, dissolved in 20 mL of ether, and n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C. After 1 hour of reaction at low temperature, the reaction system was a light yellow solution. After 3 hours of reaction at room temperature, the reaction was complete, as detected by GC-MS. The reaction solvent, ether, was removed under reduced pressure to obtain 4-methyl-2,2’-dilithium-1,1’-biphenyl (white solid).

[0080] Example 3: Synthesis of 4-methoxy-2,2’-dilithium-1,1’-biphenyl

[0081]

[0082] Into a 50 mL flask, 4-methoxy-2,2’-dibromo-1,1’-biphenyl 2.0 mmol was added, dissolved in 20 mL of ether, and n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C. After 1 hour of reaction at low temperature, the reaction system was a light yellow solution. After 3 hours of reaction at room temperature, the reaction was complete, as detected by GC-MS. The reaction solvent, ether, was removed under reduced pressure to obtain 4-methoxy-2,2’-dilithium-1,1’-biphenyl (white solid).

[0083] Example 4: Synthesis of 4,4'-Di-tert-butyl-2,2'-dilithio-1,1'-biphenyl

[0084]

[0085] Into a 50 mL reaction flask, 4,4'-Di-tert-butyl-2,2'-dibromo-1,1'-biphenyl 2.0 mmol was added, dissolved in 20 mL ether, n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C, the reaction system was a light yellow solution after keeping low temperature for 1 hour. After recovering room temperature and continuing to react for 3 hours, the reaction was complete by GC-MS detection, the reaction solvent ether was removed under reduced pressure to obtain 4,4'-Di-tert-butyl-2,2'-dilithio-1,1'-biphenyl (white solid).

[0086] Main NMR data: 1 H NMR (400 MHz, THF-d8): 1.27 (s, 18H, CH3), 7.16 (dd, J = 8.4, 2.5 Hz, 2H, CH), 7.91 (d, J = 8.4 Hz, 2H, CH), 8.09 (d, J = 2.4 Hz, 2H, CH). t Bu), 7.16 (dd, J = 8.4, 2.5 Hz, 2H, CH), 7.91 (d, J = 8.4 Hz, 2H, CH), 8.09 (d, J = 2.4 Hz, 2H, CH).

[0087] Example 5: Synthesis of 4-Trifluoromethyl-2,2'-dilithio-1,1'-biphenyl

[0088]

[0089] Into a 50 mL reaction flask, 4,4'-Di-tert-butyl-2,2'-dibromo-1,1'-biphenyl 2.0 mmol was added, dissolved in 20 mL ether, n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C, the reaction system was a light yellow solution after keeping low temperature for 1 hour. After recovering room temperature and continuing to react for 3 hours, the reaction was complete by GC-MS detection, the reaction solvent ether was removed under reduced pressure to obtain 4,4'-Di-tert-butyl-2,2'-dilithio-1,1'-biphenyl (white solid).

[0090] Example 6: Synthesis of 6-Fluoro-2,2'-dilithio-1,1'-biphenyl

[0091]

[0092] Into a 50 mL reaction flask, 6-fluoro-2,2'-dibromo-1,1'-biphenyl 2.0 mmol was added, dissolved in 20 mL of ether, n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C, the reaction system was a light yellow solution after 1 hour of reaction at low temperature. After 3 hours of reaction at room temperature, the reaction was complete by GC-MS detection, and the reaction solvent ether was removed under reduced pressure to obtain 6-fluoro-2,2'-dilithium-1,1'-biphenyl (white solid).

[0093] Example 7: Synthesis of 4-trifluoromethoxy-2,2'-dilithium-1,1'-biphenyl

[0094]

[0095] Into a 50 mL reaction flask, 4-trifluoromethoxy-2,2'-dibromo-1,1'-biphenyl 2.0 mmol was added, dissolved in 20 mL of ether, n-butyllithium 2.8 mL (4.4 mmol, concentration 1.6 M) was added at -78 °C, the reaction system was a light yellow solution after 1 hour of reaction at low temperature. After 3 hours of reaction at room temperature, the reaction was complete by GC-MS detection, and the reaction solvent ether was removed under reduced pressure to obtain 4-trifluoromethoxy-2,2'-dilithium-1,1'-biphenyl (white solid).

[0096] Main NMR data: 1 H NMR (400 MHz, THF-d8): 6.88 (m, 3H, CH), 7.09 (m, 1H, CH), 7.82 (s, 1H, CH), 7.96 (d, J = 6.7 Hz, 2H).

[0097] Synthesis of compound of formula (III)

[0098] Example 8: Synthesis of 9-phosphabicyclo[3.3.1]nonane lithium salt

[0099]

[0100] Into a 25 mL reaction flask, 2,2'-dilithium-1,1'-biphenyl 1.0 mmol was added, dissolved in 10 mL of tetrahydrofuran, then white phosphorus 1.1 mmol was added, the reaction system was a dark brown solution after 12 hours of reaction at room temperature. The reaction solvent tetrahydrofuran was removed under reduced pressure, and the remaining solid was extracted with ether several times to obtain an orange solution. The solvent ether was removed under reduced pressure again to obtain 9-phosphabicyclo[3.3.1]nonane lithium salt 366 mg (orange yellow solid), with a separation yield of 99%.

[0101] Main NMR data: 1H NMR (400 MHz, THF-d8): δ 1.76-1.79 (m, 8H, β-CH2, THF), 3.60-3.63 (m, 8H, α-CH2, THF), 6.79 (t, J = 6.9 Hz, 2H, CH), 6.86 (t, J = 7.1 Hz, 2H, CH), 7.75-7.85 (m, 2H, CH), 8.00 (d, J = 7.8 Hz, 2H, CH); 13 C NMR (126 MHz, THF-d8): δ 26.5 (s, β-CH2, THF), 68.4 (s, α-CH2, THF), 115.9 (s, CH), 120.5 (s, CH), 120.8 (d, J = 10.4 Hz; CH), 127.3 (d, J = 25.2 Hz; quat. C), 136.1 (s, CH), 158.3 (m, quat. C); 31 P{ 1 H} NMR (202 MHz, THF-d8): δ 9.63 (s).

[0102] Example 9: Synthesis of 2-methyl-9-phosphabicyclo[4.2.0]nona-2,4,6-triene lithium salt

[0103]

[0104] To a 25 mL reaction flask was added 2,2'-dilithio-4-methyl-1,1'-biphenyl 1.0 mmol, 10 mL of tetrahydrofuran was added to dissolve, then white phosphorus 1.1 mmol was added, the reaction system was a dark brown solution after reaction at room temperature for 12 hours. The solvent tetrahydrofuran was removed under reduced pressure, the remaining solid was extracted with ether several times to obtain an orange yellow solution. The solvent ether was removed again under reduced pressure to obtain 2-methyl-9-phosphabicyclo[4.2.0]nona-2,4,6-triene lithium salt 387 mg (yellow solid), separation yield 92%.

[0105] Main NMR data: 1 H NMR (400 MHz, THF-d8): δ 1.76-1.79 (m, 4H, β-CH2, THF), 2.35 (s, 3H, CH3), 3.60-3.63 (m, 4H, α-CH2, THF), 6.60 (dd, J = 8.0, 1.7 Hz, 1H, CH), 6.72 (ddd, J = 7.9, 6.6, 1.3 Hz, 1H, CH), 6.76-6.85 (m, 1H, CH), 7.54-7.63 (m, 1H, CH), 7.76 (ddt, J = 7.7, 4.1, 1.0 Hz, 1H, CH), 7.88 (d, J = 7.9 Hz, 1H, CH), 7.93 (d, J = 7.7 Hz, 1H, CH); 13C NMR (126 MHz, THF-d8): δ 22.4 (s, CH3) 26.5 (s, β-CH2, THF), 68.4 (s, α-CH2, THF), 115.7 (s, CH), 117.7 (s, CH), 120.1 (d, J = 3.6 Hz), 120.4 (d, J = 10.9 Hz), 127.0 (d, J = 6.4 Hz), 127.2 (d, J = 6.4 Hz), 128.8 (d, J = 11.2 Hz), 134.2 (d, J = 2.5 Hz), 136.2 (d, J = 2.3 Hz), 158.4 (d, J = 37.1 Hz), 159.0 (d, J = 36.9 Hz); 31 P{ 1 H}NMR (202 MHz, THF-d8): δ 7.87 (s).

[0106] Example 10: Synthesis of 2-methoxy-9-phosphabicyclo[4.2.0]nona-2,4,6-triene lithium salt

[0107]

[0108] To a 25 mL reaction flask was added 2,2’-dilithio-4-methoxy-1,1’-biphenyl 1.0 mmol, 10 mL tetrahydrofuran was added to dissolve, then white phosphorus 1.1 mmol was added, the reaction system was a dark brown solution after reaction at room temperature for 12 hours. The reaction solvent tetrahydrofuran was removed under reduced pressure, the remaining solid was extracted with ether several times to obtain an orange solution. The solvent ether was removed again under reduced pressure to obtain 2-methoxy-9-phosphabicyclo[4.2.0]nona-2,4,6-triene lithium salt 410 mg (orange solid), separation yield 92%. Main NMR data: 1 H NMR (400 MHz, THF-d8): δ 1.76-1.79 (m, 4H, β-CH2, THF), 3.60-3.63 (m, 4H, α-CH2, THF), 3.76 (s, 3H, OCH3), 6.44 (dd, J = 8.5, 2.4 Hz, 1H, CH), 6.81-6.68 (m, 2H, CH), 7.31 (dd, J = 4.4, 2.4 Hz, 1H, CH), 7.78-7.69 (m, 1H, CH), δ 7.90-7.82 (m, 2H, CH); 13C NMR(126MHz,THF-d8): δ26.5(s,β-CH2,THF),55.3(s,OCH3),68.4(s,α-CH2,THF),106.5 (s,CH),108.4(d,J=27.6Hz;CH),116.1(s,CH),119.6(s,CH),120.1(d,J=10.6Hz;quat.C ),120.9(s,CH),126.8(d,J=25.4Hz;CH),131.0(d,J=2.6Hz;CH),136.4(d,J=2.3Hz;CH), 156.3(d,J=12.2Hz; quat.C), 157.7(d,J=36.5Hz; quat.C), 160.1(d,J=37.1Hz; quat.C); 31 P{ 1 H}NMR(202MHz,THF-d8):δ9.02(s).

[0109] Example 11: Synthesis of 2,7-di-tert-butyl-9-phosphafluorene lithium salt

[0110]

[0111] At room temperature, 1.0 mmol of 2,2'-dilithium-4,4'-di-tert-butyl-1,1'-biphenyl was added to a 25 mL reaction flask. Dissolved in 10 mL of tetrahydrofuran, 1.1 mmol of white phosphorus was then added. After 12 hours of reaction at room temperature, the reaction system became a dark brown solution. The tetrahydrofuran solvent was removed under reduced pressure, and the remaining solid was extracted multiple times with ether to obtain a red solution. The ether solvent was again removed under reduced pressure to obtain 405 mg of 2,7-di-tert-butyl-9-phosphafluorene lithium salt (red solid), with an isolated yield of 90%.

[0112] Main NMR data: 1 H NMR(400MHz,THF-d8)δ1.37(s,18H, t Bu),1.76-1.79(m,4H,β-CH2,THF),3.60-3.63(m,4H,α-CH2,THF),6.89(dd,J= 8.3,2.0Hz,2H,CH),7.82(dd,J=5.0,1.9Hz,1H,CH),7.89(d,J=8.2Hz,1H,CH), 13 C NMR(101MHz,THF-d8)δ26.5(s,β-CH2,THF),32.7(s,CH3, t Bu),35.3(s,quat.C, tBu),68.4(s,α-CH2,THF),114.7(s,CH),120.0(s,CH),122.8(d,J=25.6Hz,CH),134 .4(d,J=2.0Hz,quat.C),142.3(d,J=10.5Hz,quat.C),158.1(d,J=35.2Hz,quat.C); 31 P{ 1 H}NMR(202MHz,THF-d8):δ0.87(s).

[0113] Example 12: Synthesis of 2-trifluoromethyl-9-phosphafluorene lithium salt

[0114]

[0115] At room temperature, 1.0 mmol of 2,2'-dilithium-4-trifluoromethyl-1,1'-biphenyl was added to a 25 mL reaction flask. Dissolved in 10 mL of tetrahydrofuran, followed by 1.1 mmol of white phosphorus. After 12 hours of reaction at room temperature, the reaction system became a dark brown solution. The tetrahydrofuran solvent was removed under reduced pressure, and the remaining solid was extracted multiple times with ether to obtain an orange solution. The ether solvent was again removed under reduced pressure to obtain 450 mg of 2-trifluoromethyl-9-phosphafluorene lithium salt as an orange solid, with an isolated yield of 95%.

[0116] Main NMR data: 1 H NMR(400MHz,THF-d8)δ1.76-1.79(m,8H,β-CH2,THF),3.60-3.63(m,8H,α-CH2,THF),6.80(ddd,J=7.9,6.6,1.2Hz,1H,CH ),6.97-6.85(m,2H,CH),7.89(ddt,J=7.9,4.2,1.0Hz,1H,CH),8.09(d,J=8.1Hz,2H,CH),8.14(dq,J=3.0,0.9Hz,1H,CH); 13 C NMR (126 MHz, THF-d 8)δ 26.5 (s, β-CH2, THF), 68.4 (s, α-CH2, THF), 110.4 (s, CH), 116.0 (s, CH), 120.2 (d, J = 2.1 Hz, quat. C), 121.0 (s, CH), 121.1 (s, CH), 121.3 (s, CH), 124.4 (dq, J = 27.2, 4.4 Hz, quat. C), 127.7 (d, J = 25.5 Hz, CH), 128.2 (q, J = 270.8 Hz, CF3), 134.5 (d, J = 4.1 Hz, quat. C), 136.7 (s, CH), 157.8 (d, J = 40.6 Hz, quat. C), 160.4 (d, J = 39.6 Hz, quat. C); 31 P{ 1 H} NMR (202 MHz, THF-d8): δ 28.33 (s); 19 F NMR (471 MHz, THF-d8): δ -60.32 (s).

[0117] Example 13: Synthesis of 4-fluoro-9-phosphabicyclo[4.2.0]non-4-ene lithium salt

[0118]

[0119] To a 25 mL reaction flask was added 2,2'-dilithio-6-fluoro-1,1'-biphenyl 1.0 mmol, 10 mL of tetrahydrofuran was added to dissolve, then white phosphorus 1.1 mmol was added, the reaction system was a dark brown solution after reaction at room temperature for 12 hours. The solvent tetrahydrofuran was removed under reduced pressure, the remaining solid was extracted with ether several times to obtain an orange yellow solution. The solvent ether was removed under reduced pressure again to obtain 4-fluoro-9-phosphabicyclo[4.2.0]non-4-ene lithium salt 403 mg (yellow solid), separation yield 95%.

[0120] Main NMR data: 1 H NMR (400 MHz, THF-d8) δ 1.76-1.79 (m, 6H, β-CH2, THF), 3.60-3.63 (m, 6H, α-CH2, THF), 6.34 (ddd, J = 12.8, 7.4, 0.9 Hz, 1H, CH), 6.78-6.68 (m, 2H, CH), 6.86-6.79 (m, 1H, CH), 7.57 (ddt, J = 7.8, 4.3, 1.2 Hz, 1H, CH), 7.82 (ddt, J = 8.0, 4.5, 1.0 Hz, 1H, CH), 8.30 (d, J = 8.0 Hz, 1H, CH); 13C NMR (126 MHz, THF-d8) δ 26.5 (s, β-CH2, THF), 68.4 (s, α-CH2, THF), 99.9 (d, J = 21.3 Hz, CH), 115.8 (s, CH), 119.7 (dd, J = 11.9, 8.0 Hz, CH), 120.1 (d, J = 11.8 Hz, CH), 122.9 (dd, J = 25.9, 2.5 Hz, CH), 124.9 (d, J = 10.7 Hz, CH), 126.9 (d, J = 25.9 Hz, CH), 133.1 (t, J = 4.4 Hz, quat. C), 158.8 (d, J = 38.7 Hz, quat. C), 161.2 (d, J = 2.2 Hz, quat. C), 162.8 (dd, J = 40.3, 4.9 Hz, quat. C), 163.2 (d, J = 2.2 Hz, quat. C); 31 P{ 1 H} NMR (202 MHz, THF-d8): δ 26.79 (s); 19 F{ 1 H} NMR (471 MHz, THF-d8): δ -121.69 (d, J = 4.2 Hz).

[0121] Availability of industry

[0122] The phospholane metal salt compound based on the phospholane structural unit of the present application can synthesize various phospholane compounds through derivatization reaction, and further be applied in the field of metal organic chemistry or the field of organic optoelectronic materials.

Claims

1. A phosphafluorene metal salt compound, which is a compound containing a phosphafluorene structural unit as shown in the following formula (III), characterized in that: Among them, R 1 and R 2 They may be the same or different, and each is hydrogen, halogen, trifluoromethyl, C1-C6 alkyl, or C1-C6 alkoxy; M is an alkali metal, and the alkali metal is lithium; Sol represents a coordinating solvent, and the Sol is THF or Et2O; n represents the number of coordinating solvents, and is a positive integer or half integer greater than 2 and less than 3.

2. The phosphafluorene metal salt compound according to claim 1, characterized in that R 1 and R 2 Each is hydrogen, halogen, methyl, methoxy, tert-butyl, trifluoromethyl.

3. A method for preparing a phosphafluorene metal salt compound, which is a method for preparing a compound containing a phosphafluorene structural unit as shown in the following formula (III): In formula (III), R 1 and R 2 may be the same or different, and each of them is hydrogen, halogen, trifluoromethyl, C1-C6 alkyl, C1-C6 alkoxy; M is an alkali metal, and the alkali metal is lithium; Sol represents a coordinating solvent, and the Sol is THF or Et2O; n represents the number of coordinating solvents, and is a positive integer or half integer of 2 or more and 3 or less; The preparation method comprises the following steps: Step 1-1: reacting the compound of formula (I) with an organometallic reagent at low temperature to prepare the compound of formula (II); In the compound of formula (I), X is chlorine or bromine; The organometallic reagent used in step 1-1 is an organolithium reagent, and the organolithium reagent is n-butyllithium or tert-butyllithium; The ratio of the organometallic reagent used to the compound of formula (I) is 2 to 3 times the molar equivalent; Step 1-2: Prepare the compound of formula (III) by reacting the compound of formula (II) with white phosphorus at room temperature or above, The ratio of white phosphorus used to the compound of formula (II) is 1 to 1.5 times the molar equivalent. In step 1-1, the low temperature is in the range of -120°C to -60°C, the reaction is carried out for 0.5 to 3 hours in this temperature range, and then the reaction is continued at room temperature for 2 to 6 hours.

4. The phosphafluorene metal salt compound according to claim 3, characterized in that In step 1-2, the reaction time is 6 to 24 hours.

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