Preparation method of tris (aryl ethynyl) phosphine compound

Abstract

The invention provides a preparation method of a tri (aryl ethynyl) phosphine compound, and the tri (aryl ethynyl) phosphine compound is a tri (aryl ethynyl) phosphine compound which is shown in a formula (II) and contains a triaryl ethynyl structural unit. The tri (aryl ethynyl) phosphine compound is directly synthesized from white phosphorus and an aryl acetylene compound under the action of alkali, an activating agent and an assistant, and the process avoids the problems of use of chlorine with great pollution and subsequent emission in the traditional phosphorus chemical production, and is a more environment-friendly production method. In addition, the method disclosed by the invention is mild in reaction condition, relatively short in reaction time and simple in post-treatment, and relatively high yield can be obtained.

Description

Technical Field

[0001] This invention relates to the field of organophosphorus chemistry and chemical engineering, and more specifically, to a method for preparing tri(arylethynyl)phosphine compounds containing triarylethynyl structural units. Background Technology

[0002] Organophosphorus compounds (OPCs) containing CP bonds have wide applications in industry and academia, such as materials science, medicinal chemistry, organocatalytic synthesis, and coordination chemistry. Among them, those containing C... sp -P-bonded alkynylphosphine derivatives are widely used as multifunctional synthetic precursors in organic and medicinal chemistry, and have attracted much attention due to their versatile applications. In particular, trivalent alkynylphosphine not only serves as a key precursor for the synthesis of functionalized alkenyl / alkylphosphine rings and phosphorus-containing heterocycles, but its ligand diversity also stems from a dual coordination mechanism: η 1 -P bonding and the synergistic effect between phosphorus lone pairs and alkyne π-systems in polydentate complexes.

[0003] Currently, there are two main known methods for synthesizing tris(arylethynyl)phosphine compounds: 1) obtaining the target product through a nucleophilic substitution reaction between a pre-synthesized arylethynylphosphine organometallic compound and phosphorus trichloride under mild conditions; 2) coupling reaction between a terminal alkyne and phosphorus trichloride under transition metal catalysis. However, despite these two methods significantly advancing the development of tris(arylethynyl)phosphine compounds, their application is still limited by the availability of raw materials and environmental requirements. For example, both methods are based on a multi-step chlorination pathway starting from white phosphorus (industrially known as yellow phosphorus): white phosphorus → phosphorus trichloride → tris(arylethynyl)phosphine compound. This process not only requires the use of highly toxic chlorine gas but also generates large quantities of difficult-to-recover chlorinated waste salts, leading to severe environmental pollution and significantly hindering the industrial-scale application of tris(arylethynyl)phosphine compounds (see Non-Patent Literature 1).

[0004] Therefore, developing a novel synthetic method that avoids this toxic chlorination process—while also being green, efficient, environmentally friendly, and easy to operate—is of significant practical importance. From the perspective of meeting the requirements of modern chemical processes, the objective of this invention is to provide an environmentally friendly and cost-effective method for synthesizing tris(arylethynyl)phosphine compounds that avoids the traditional chlorination process.

[0005] Existing technical documents

[0006] Non-patent literature

[0007] Non-patent literature 1: Donath, M.; et al. Nat. Chem. 2022, 14, 384-391. Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] The present invention was made in view of the above-mentioned problems, and its purpose is to provide a method for preparing tri(arylethynyl)phosphine compounds containing triarylethynyl structural units that is not only environmentally friendly, but also low in cost and easy to synthesize efficiently.

[0010] Solution for solving the problem

[0011] The technical solution of the present invention is as follows:

[0012] A tri(arylethynyl)phosphine compound, which is a tri(arylethynyl)phosphine compound containing a triarylethynyl structural unit as shown in formula (II), characterized in that:

[0013]

[0014] In formula (II), R can be one of hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, amino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, or benzo[a], and Ar can be phenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, or ferrocene.

[0015] Wherein, the alkyl group is preferably a C1-C10 alkyl group, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopropyl, hexyl, heptyl, etc.; the alkoxy group is preferably a C1-C10 alkoxy group, specifically methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, etc.; the amino group is specifically a primary amino group or a secondary amino group; the secondary amino group is dimethylamino or diethylamino; the primary amino group is methylamino or ethylamino.

[0016] In the above-mentioned substituted phenyl or substituted biphenyl, the substitution can be monosubstituted or polysubstituted, and the substituent is alkyl (specifically methyl, ethyl, propyl), alkoxy (specifically methoxy, ethoxy, propoxy, butoxy), halogen (specifically chlorine, bromine), nitro, or phenyl, etc.

[0017] Furthermore, in formula (II), R is one of hydrogen, fluorine, chlorine, bromine, allyl, nitro, cyano, trifluoromethyl, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, dimethylamino, phenyl, tolyl, trimethylphenyl, nitrophenyl, chlorophenyl, bromophenyl, biphenyl, methylbiphenyl, naphthyl, anthraceneyl, and phenanthrene, and the aryl Ar is phenyl, naphthyl, anthraceneyl, phenanthreneyl, thiopheneyl, or ferroceneyl.

[0018] A method for preparing tri(arylethynyl)phosphine compounds, comprising the method for preparing tri(arylethynyl)phosphine compounds containing triarylethynyl structural units as shown in formula (II) above, wherein,

[0019] The preparation method includes the following steps:

[0020]

[0021] Step 1: Add white phosphorus P4, activator, auxiliary agent and solvent to a reactor protected by nitrogen or argon, and wait for it to dissolve to obtain solution A. Then add compound of formula (I), base and solvent to another reactor protected by nitrogen or argon, and wait for it to dissolve to obtain solution B.

[0022] Step 2: Solution B was then slowly added dropwise to solution A, and the reaction was carried out by stirring at room temperature, thereby obtaining compound (II);

[0023] In step 1, the auxiliary agent used is an alkali metal halide, wherein the alkali metal is lithium, sodium, potassium, or cesium, and its halide is lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, lithium fluoride, sodium fluoride, potassium fluoride, or cesium fluoride.

[0024] In step 1, the alkali used is an alkali metal hydride, hydroxide, alkylate, or amino compound. The alkali metal is lithium, sodium, or potassium. Its hydrides are sodium hydride and potassium hydride, its hydroxides are sodium hydroxide and potassium hydroxide, its alkylates are n-butyllithium and tert-butyllithium, and its amino compounds are lithium bis(trimethylsilyl)amino, sodium bis(trimethyl)silylamino, and potassium bis(trimethyl)silylamino.

[0025] In both formulas (I) and (II), R can be one of hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, amino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, or benzo[a], and Ar can be phenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, or ferrocene.

[0026] The solvent used in the reaction can be any organic solvent that does not react with the compound of formula (I), the activator, or white phosphorus, such as 2-methyltetrahydrofuran (2-MeTHF), tetrahydrofuran (THF), hexane, diethyl ether (Et2O), toluene, or 1,4-dioxane, with tetrahydrofuran (THF) being the preferred solvent.

[0027] The activator is a diaryl diselenide or a diaryl disulfide, wherein the diaryl diselenide is specifically diphenyl diselenide, p-toluene diselenide, 4,4'-dichlorodiphenyl diselenide, bis(4-fluorophenyl)diselenide, bis(4-methoxyphenyl)diselide, bis(4-nitrophenyl)diselide, 3,3'-di-tert-butyldiphenyl diselenide, 2,2'-dimethoxydiphenyl diselenide, bis(2-anthrayl)diselenide, or bis(2-naphthyl)diselenide; and the diaryl disulfide is specifically diphenyl disulfide, p-toluene disulfide, 4,4'-dichlorodiphenyl disulfide, bis(4-methoxyphenyl)disulfide, bis(4-nitrophenyl)disulfide, 4,4'-dicarboxylated diphenyl disulfide, 4,4'-dihydroxydiphenyl sulfide, or 4,4'-diaminodiphenyl disulfide. The following compounds are used in this invention: bis(4-fluorophenyl)disulfide, 3,3'-dihydroxydiphenyl disulfide, 3,3'-difluorodiphenyl disulfide, 2,2'-diaminodiphenyl disulfide, 2,2'-dithiodibenzoic acid, dibenzothiazole disulfide, bis(2-naphthyl)disulfide, bis(1-naphthyl)disulfide, 2,2'-dithiodipyridine, and dibenzyl disulfide. Their role in this invention is as an activating agent in the reaction process. The mechanism (taking diphenyldiselenic ether as an example) is as follows: the activator can break P into PP bonds, generating the key tri(arylselenyl)phosphine (P(SePh)) intermediate in situ. This intermediate then undergoes a coupling reaction with compound (I) to obtain compound (II). Simultaneously, the released selenium compound is oxidized and regenerated into diphenyldiselenic ether, thus enabling recycling.

[0028] In step 2, the room temperature is in the range of 20°C to 30°C, and the reaction time is 1 to 3 hours. The preferred temperature range is 22 to 26°C, and the preferred reaction time is 1.5 to 2.5 hours.

[0029] In step 1, the proportions of the compound of formula (I) and the activator used relative to white phosphorus (P4) in terms of phosphorus atoms are 2.5 to 3.5 molar equivalents and 1.0 to 2.0 molar equivalents, respectively; the proportion of the auxiliary agent used relative to white phosphorus (P4) in terms of phosphorus atoms is 0.5 to 2.0 molar equivalents; and the proportion of the base used relative to white phosphorus in terms of phosphorus atoms is 2.5 to 3.5 molar equivalents. Preferably, the proportion of the compound of formula (I) used is 3.0 to 3.3 molar equivalents, the proportion of the activator used is 1.2 to 1.7 molar equivalents, the proportion of the auxiliary agent used is 0.8 to 1.2 molar equivalents, and the proportion of the base used is 3.0 to 3.3 molar equivalents.

[0030] The effects of the invention

[0031] According to the present invention, a method for synthesizing tris(arylethynyl)phosphine compounds from white phosphorus in a one-pot process is provided. Traditional synthesis methods require multiple complex reactions, such as reacting white phosphorus with chlorine to obtain a phosphorus trichloride intermediate, and then reacting phosphorus trichloride with an arylethynyl metal salt substrate to obtain triarylethynylphosphine. Needless to say, both chlorine and phosphorus trichloride are toxic and polluting substances. In contrast, the method of the present invention does not require the use of environmentally unfriendly raw materials such as phosphorus trichloride, and also avoids the problems of using highly polluting chlorine and generating large amounts of acid in traditional phosphorus chemical production. Therefore, it is a more environmentally friendly production method. Furthermore, the preparation method has simple reaction steps, requires no complex equipment, and is easy to operate. In addition, the raw materials used in the preparation process are relatively inexpensive and readily available; for example, diphenyldiselenes used can be recycled, thus reducing economic costs.

[0032] Furthermore, the tris(arylethynyl)phosphine compounds synthesized according to the method of the present invention have wide applications in the field of organic synthesis, especially in the field of transition metal catalytic synthesis, and are a class of compounds of great value. Moreover, compared with traditional synthetic routes, the method disclosed in this invention has mild reaction conditions, shorter reaction time, simpler post-processing, and can achieve higher yields. Detailed Implementation

[0033] The following specific embodiments further illustrate the above-described contents of the present invention in detail, but should not be construed as limiting the scope of protection of the present invention in any way. All technical solutions implemented based on the above-described contents of the present invention fall within the scope of the present invention. The present invention provides a general and / or specific description of the materials and test methods used in the experiments. Those skilled in the art will understand that, unless otherwise specified, the room temperature described in the present invention has a technically known meaning in the art, generally referring to 20–30°C; all chemicals mentioned are commercially available.

[0034] The present invention discloses a tri(arylethynyl)phosphine compound, which is a tri(arylethynyl)phosphine compound containing a triarylethynyl structural unit as shown in formula (II).

[0035]

[0036] In formula (II), R can be hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, amino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, or benzo[a]yl, and the aryl Ar can be phenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, or ferrocene.

[0037] Preparation of compounds

[0038] A method for preparing a tri(arylethynyl)phosphine compound, wherein the compound is a tri(arylethynyl)phosphine compound containing a triarylethynyl structural unit as shown in formula (II) above, the method comprising the following steps:

[0039]

[0040] Step 1: Add white phosphorus P4, activator, auxiliary agent and solvent to a reactor protected by nitrogen or argon, and wait for it to dissolve to obtain solution A. Then add compound of formula (I), base and solvent to another reactor protected by nitrogen or argon, and wait for it to dissolve to obtain solution B.

[0041] Step 2: Solution B is then slowly added dropwise to solution A, and the mixture is stirred at room temperature to carry out the reaction, thereby obtaining compound (II).

[0042] In the above compound formula (I), R can be hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, amino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, etc., and aryl Ar can be phenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, thiophene, ferrocene, etc.

[0043] The activator is a diaryl diselenide or a diaryl disulfide, wherein the diaryl diselenide is specifically diphenyl diselenide, p-toluene diselenide, 4,4'-dichlorodiphenyl diselenide, bis(4-fluorophenyl)diselenide, bis(4-methoxyphenyl)diselide, bis(4-nitrophenyl)diselide, 3,3'-di-tert-butyldiphenyldiselenide, 2,2'-dimethoxydiphenyldiselenide, bis(2-anthrayl)diselenide, or bis(2-naphthyl)diselenide, and the diaryl disulfide is specifically diphenyl disulfide, p-toluene disulfide, or 4,4'-dichlorodiphenyl Disulfide, bis(4-methoxyphenyl) disulfide, bis(4-nitrophenyl) disulfide, 4,4'-dicarboxylic diphenyl disulfide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-diaminodiphenyl disulfide, bis(4-fluorophenyl) disulfide, 3,3'-dihydroxydiphenyl disulfide, 3,3'-difluorodiphenyl disulfide, 2,2'-diaminodiphenyl disulfide, 2,2'-dithiodibenzoic acid, dibenzothiazole disulfide, di(2-naphthyl) disulfide, di(1-naphthyl) disulfide, 2,2'-dithiodipyridine, dibenzyl disulfide.

[0044] Wherein, the alkyl group is preferably a C1-C10 alkyl group, and the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, etc.; the alkoxy group is preferably a C1-C10 alkoxy group, and the alkoxy group is methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptoxy, etc.; the amino group is a primary amino group or a secondary amino group; the secondary amino group is a dimethylamino group or a diethylamino group; the primary amino group is a methylamino group or an ethylamino group; the aryl group is preferably phenyl, naphthyl, anthraceneyl, or phenanthrene.

[0045] In the above-mentioned substituted phenyl or substituted biphenyl, the substitution can be monosubstituted or polysubstituted, and the substituent in the substituted phenyl or substituted biphenyl is alkyl (specifically methyl, ethyl, propyl), alkoxy (specifically methoxy, ethoxy, propoxy, butoxy), halogen (specifically chlorine, bromine), nitro, phenyl, etc.

[0046] Furthermore, in formula (II), R is one of hydrogen, fluorine, chlorine, bromine, allyl, nitro, cyano, trifluoromethyl, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, dimethylamino, phenyl, tolyl, trimethylphenyl, nitrophenyl, chlorophenyl, bromophenyl, biphenyl, methylbiphenyl, naphthyl, anthraceneyl, and phenanthrene, and the aryl Ar is phenyl, naphthyl, anthraceneyl, phenanthreneyl, thiopheneyl, or ferroceneyl.

[0047] Furthermore, in formula (II), R is hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, dimethylamino, phenyl, tolyl, trimethylphenyl, chlorophenyl, bromophenyl, biphenyl, methylbiphenyl, naphthyl, anthracene;

[0048] The auxiliary agent used in the steps of the above reaction formula is an alkali metal halide, wherein the alkali metal is lithium, sodium, potassium and cesium, and its halide is lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, lithium fluoride, sodium fluoride, potassium fluoride and cesium fluoride; more preferably lithium chloride and lithium bromide.

[0049] The base used in the steps of the above reaction formula is a hydride, hydroxide, alkylate, or amino compound, and the alkali metal is lithium, sodium, or potassium. Its hydride is sodium hydride and potassium hydride, its hydroxide is sodium hydroxide and potassium hydroxide, its alkylate is n-butyllithium and tert-butyllithium, and its amino compound is bis(trimethylsilyl)aminolithium, bis(trimethylsilyl)aminosodium, and bis(trimethylsilyl)aminopotassium; more preferably, sodium hydride and n-butyllithium.

[0050] The solvent used in the reaction can be any organic solvent that does not react with the compound of formula (I), the activator, or white phosphorus, such as 2-methyltetrahydrofuran (2-MeTHF), tetrahydrofuran (THF), hexane, diethyl ether (Et2O), toluene, or 1,4-dioxane, with tetrahydrofuran (THF) being the preferred solvent.

[0051] In step 1, the proportions of the compound of formula (I) and the activator used relative to white phosphorus (P4) in terms of phosphorus atoms are 2.5 to 3.5 molar equivalents and 1.0 to 2.0 molar amounts, respectively. The proportion of the auxiliary agent used relative to white phosphorus (P4) in terms of phosphorus atoms is 0.5 to 2.0 molar equivalents, and the proportion of the base used relative to white phosphorus (P4) in terms of phosphorus atoms is 2.5 to 3.5 molar equivalents.

[0052] As can be seen from the above preparation method, the preparation method disclosed in this invention has very mild reaction conditions and a short reaction time. In addition, as can be seen from the reaction operation of the embodiments described later, the post-processing operation is also simple, and a high yield can be obtained.

[0053] The preparation method of the above compounds is described in detail below through examples.

[0054] Synthesis of compound (II)

[0055] Example 1: Synthesis of tris(phenylethynyl)phosphine

[0056]

[0057] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), diphenyldiselenoether (0.2 mmol), and lithium chloride (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, phenylacetylene (0.6 mmol), sodium hydride (0.6 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 1 in 80% separation yield (yield calculation based on phosphorus atoms).

[0058] The main NMR data of product 1: (CAS: 4547-77-7)1 H NMR (600MHz, CDCl3) δ: 7.35-7.32 (m, 9H), 7.55 (d, J = 6.6Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 79.4 (d, J = 6.3Hz), 105.6 (d, J = 11.4Hz), 120.1, 128.3, 129.4, 132.1 (d, J = 2.0Hz); 31 P{ 1 H}NMR(243MHz, CDCl3)δ:-88.3(s,1P).

[0059] Example 2: Synthesis of tris(4-methylphenylethynyl)phosphine

[0060]

[0061] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), p-toluene diselenide (0.3 mmol), and lithium bromide (0.3 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 4-methylphenylacetylene (0.5 mmol), potassium hydride (0.5 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 2 in a separation yield of 76% (yield calculation based on phosphorus atoms).

[0062] Key NMR data for product 2: (CAS:4319-05-5) 1 H NMR (600MHz, CDCl3) δ: 2.35 (s, 9H), 7.13 (d, J = 7.8Hz, 6H), 7.44 (d, J = 7.8Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 21.6, 78.9 (d, J = 7.2Hz), 105.8 (d, J = 11.4Hz), 119.1, 129.0, 132.1 (d, J = 2.1Hz), 139.7; 31 P{ 1H}NMR(243MHz, CDCl3)δ:-88.0(s,1P).

[0063] Example 3: Synthesis of tris(4-ethylphenylethynyl)phosphine

[0064]

[0065] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), p-toluene disulfide (0.4 mmol), and lithium iodide (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved, yielding solution A. Then, 4-ethylphenylacetylene (0.7 mmol), n-butyllithium (0.7 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved, yielding solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 3 in a separation yield of 75% (yield calculation based on phosphorus atoms).

[0066] Key NMR data for product 3: 1 H NMR (600MHz, CDCl3) δ: 1.22 (t, J = 7.8Hz, 9H), 2.65 (q, J = 7.8Hz, 6H), 7.16 (d, J = 7.8Hz, 6H), 7.46 (d, J = 7.8Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 15.2, 28.9, 78.9 (d, J = 7.1Hz), 105.8 (d, J = 11.6Hz), 119.3, 127.8, 132.2 (d, J = 2.1Hz), 145.9; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.0(s,1P).HRMS m / z:[M+H] + calcd for C 30 H 28 P + 419.1923; Found: 419.1927.

[0067] Example 4: Synthesis of tris(4-tert-butylphenylethynyl)phosphine

[0068]

[0069] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), 4,4'-dichlorodiphenyl disulfide (0.3 mmol), and potassium fluoride (0.4 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved, yielding solution A. Then, 4-tert-butylphenylacetylene (0.63 mmol), sodium hydroxide (0.63 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved, yielding solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 3 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 4 in a separation yield of 70% (yield calculation based on phosphorus atoms).

[0070] Key NMR data for product 4: 1 H NMR (600MHz, CDCl3) δ: 1.31 (s, 27H), 7.35 (d, J = 8.4Hz, 6H), 7.48 (d, J = 8.4Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 31.1, 34.9, 79.0 (d, J = 7.2Hz), 105.8 (d, J = 11.7Hz), 119.2, 125.3, 131.9 (d, J = 2.0Hz), 152.8; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-87.9(s,1P).HRMS m / z:[M+H] + calcd for C 36 H 40 P + 503.2862; Found: 503.2861.

[0071] Example 5: Synthesis of tris(4-phenylphenylethynyl)phosphine

[0072]

[0073] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), bis(4-methoxyphenyl)disulfide (0.25 mmol), and lithium chloride (0.1 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 4-phenylphenylacetylene (0.68 mmol), bis(trimethylsilylaminolithium) (0.68 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1.5 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 5 in a separation yield of 73% (yield calculation based on phosphorus atoms).

[0074] Key NMR data for product 5: 1 H NMR (600MHz, CDCl3) δ: 7.37 (t, J = 7.2Hz, 3H), 7.45 (t, J = 7.2Hz, 6H), 7.59 (t, J = 5.4Hz, 12H), 7.65 (d, J = 8.4Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 80.0 (d, J = 6.3Hz), 105.7 (d, J = 11.6Hz), 120.9, 127.0, 127.1, 127.8, 128.9, 132.6 (d, J = 2.1Hz), 140.1, 142.1; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-87.9(s,1P).HRMS m / z:[M+H] + calcdfor C 42 H 28 P + 563.1923; Found: 563.1915.

[0075] Example 6: Synthesis of tris(4-methoxyphenylethynyl)phosphine

[0076]

[0077] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), bis(4-nitro)disulfide (0.35 mmol), and lithium chloride (0.35 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved, yielding solution A. Then, 4-methoxyphenylacetylene (0.58 mmol), sodium bis(trimethylsilylamino)amine (0.58 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved, yielding solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 6 in a separation yield of 67% (yield calculation based on phosphorus atoms).

[0078] Key NMR data for product 6: 1 H NMR (600MHz, CDCl3) δ: 3.82 (s, 9H), 6.85 (d, J = 8.4Hz, 6H), 7.49 (d, J = 8.4Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 55.3, 78.3 (d, J = 8.0Hz), 105.7 (d, J = 11.7Hz), 113.9, 114.3, 133.9 (d, J = 2.4Hz), 160.4; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.0(s,1P).HRMS m / z:[M+H] + calcd for C 27 H 22 O3P + 425.1301; Found: 425.1300.

[0079] Example 7: Synthesis of tris(4-N,N-dimethylphenylethynyl)phosphine

[0080]

[0081] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), 4,4'-dichlorodiphenyldiselenes (0.4 mmol), and potassium iodide (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 4-N,N-dimethylphenylacetylene (0.7 mmol), sodium hydride (0.7 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 7 in a separation yield of 30% (yield calculation based on phosphorus atoms).

[0082] Key NMR data for product 7: 1 H NMR (600MHz, CDCl3) δ: 3.82 (s, 18H), 6.59 (d, J = 9.0Hz, 6H), 7.41 (d, J = 9.0Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 40.1, 77.9 (d, J = 10.0Hz), 106.8 (d, J = 12.3Hz), 109.1, 111.4, 133.5 (d, J = 2.0Hz), 150.5; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-87.5(s,1P).HRMS m / z:[M+H] + calcd for C 30 H 31 N3P + 464.2250; Found: 464.2260.

[0083] Example 8: Synthesis of tris(3-methylphenylethynyl)phosphine

[0084]

[0085] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), bis(4-fluorophenyl)diselenoether (0.35 mmol), and cesium fluoride (0.1 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 3-methylphenylacetylene (0.52 mmol), potassium hydride (0.52 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 3 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 8 in a separation yield of 71% (yield calculation based on phosphorus atoms).

[0086] Key NMR data for product 8: 1 H NMR (600MHz, CDCl3) δ: 2.24 (s, 9H), 7.08 (d, J = 7.2Hz, 3H), 7.13 (t, J = 7.8Hz, 3H), 7.27 (d, J = 7.2Hz, 3H), 7.29 (s, 3H); 13 CNMR (150MHz, CDCl3) δ: 21.2, 79.1 (d, J = 6.6Hz), 105.8 (d, J = 11.4Hz), 121.9, 121.9, 129.2 (d, J = 2.0Hz), 130.2, 132.6 (d, J = 2.1Hz), 138.0; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.1(s,1P).HRMS m / z:[M+H] + calcd for C 27 H 22 P + 377.1454; Found: 377.1450.

[0087] Example 9: Synthesis of tris(2-methylphenylethynyl)phosphine

[0088]

[0089] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), bis(4-methoxyphenyl)diselenide (0.36 mmol), and sodium fluoride (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 2 mL of the sample vial was taken and 2-methylphenylacetylene (0.60 mmol), sodium hydroxide (0.60 mmol), and THF (1.0 mL) were added. The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 2.5 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 9 in a separation yield of 63% (yield calculation based on phosphorus atoms).

[0090] Key NMR data for product 9: 1 H NMR (600MHz, CDCl3) δ: 2.50 (s, 9H), 7.15 (t, J = 7.8Hz, 3H), 7.21 (d, J = 7.8Hz, 3H), 7.28-7.25 (m, 4H) 7.50 (d, J = 7.8Hz, 3H); 13 C NMR (150MHz, CDCl3) δ: 20.6, 83.6 (d, J = 6.0Hz), 104.4 (d, J = 11.4Hz), 122.0, 125.5, 129.3, 129.5, 132.3 (d, J = 2.0Hz), 141.2; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.9(s,1P).HRMS m / z:[M+H] + calcd for C 27 H 22 P + 377.1454; Found: 377.1452.

[0091] Example 10: Synthesis of tris(3,5-dimethylphenylethynyl)phosphine

[0092]

[0093] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), bis(4-nitrophenyl)diselenide (0.3 mmol), and potassium fluoride (0.15 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 3,5-dimethylphenylacetylene (0.69 mmol), n-butyllithium (0.69 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 10 in a separation yield of 72% (yield calculation based on phosphorus atoms).

[0094] Key NMR data for product 10: 1 H NMR (600MHz, CDCl3) δ: 2.20 (s, 18H), 6.90 (s, 3H), 7.10 (s, 6H); 13 C NMR (150MHz, CDCl3) δ: 21.1, 78.9 (d, J = 7.1Hz), 105.9 (d, J = 11.4Hz), 121.9, 129.8 (d, J = 2.0Hz), 131.3, 137.9; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.0(s,1P).HRMS m / z:[M+H] + calcd for C 30 H 28 P + 419.1923; Found: 419.1919.

[0095] Example 11: Synthesis of tris(3,5-dimethoxyphenylethynyl)phosphine

[0096]

[0097] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), 4,4'-dicarboxylic acid diphenyl disulfide (0.2 mmol), and lithium bromide (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 3,5-dimethoxyphenylacetylene (0.56 mmol), potassium hydroxide (0.56 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 11 in a separation yield of 26% (yield calculation based on phosphorus atoms).

[0098] Key NMR data for product 11: 1 H NMR (600MHz, CDCl3) δ: 3.78 (s, 18H), 6.49 (t, J = 2.4Hz, 3H), 6.71 (d, J = 2.4Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 55.5, 78.7 (d, J = 5.9Hz), 103.2, 105.7 (d, J = 11.3Hz), 109.8 (d, J = 2.1Hz), 123.2, 160.5; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.3(s,P).HRMS m / z:[M+H] + calcd for C 30 H 28 O6P + 515.1618; Found: 515.1622.

[0099] Example 12: Synthesis of tris(2,4,6-trimethylphenylethynyl)phosphine

[0100]

[0101] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), 2,2'-dithiopyridine (0.4 mmol), and potassium chloride (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, 2 mL of the sample vial was taken and 2,4,6-trimethylphenylacetylene (0.62 mmol), bis(trimethylsilylaminolithium) (0.62 mmol), and THF (1.0 mL) were added. The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 12 in a separation yield of 65% (yield calculation based on phosphorus atoms).

[0102] Key NMR data for product 12: 1 H NMR (600MHz, CDCl3) δ: 2.19 (s, 9H), 2.35 (s, 18H), 6.77 (s, 6H); 13 C NMR (150MHz, CDCl3) δ: 20.8, 21.4, 87.6 (d, J = 6.8Hz), 103.0 (d, J = 11.6Hz), 119.2, 127.6, 138.7, 141.0 (d, J = 2.0Hz); 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-89.5(s,1P).HRMSm / z:[M+H] + calcd for C 33 H 34 P + 461.2393; Found: 461.2395.

[0103] Example 13: Synthesis of tris(naphthyl-2-ethynyl)phosphine

[0104]

[0105] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), dibenzyl disulfide (0.3 mmol), and lithium fluoride (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, naphthalene-2-phenylacetylene (0.66 mmol), potassium bis(trimethylsilylamino)amine (0.62 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 13 in a separation yield of 70% (yield calculation based on phosphorus atoms).

[0106] Key NMR data for product 13: 1 H NMR (600MHz, CDCl3) δ: 7.52-7.49 (m, 6H), 7.61 (d, J = 8.4Hz, 3H), 7.61 (d, J = 8.4Hz, 3H), 8.13 (s, 3H); 13 C NMR (150MHz, CDCl3) δ: 79.7 (d, J = 6.2 Hz), 106.2 (d, J = 11.4 Hz), 119.4, 126.7, 12 7.2,127.8,128.0,128.1,128.3(d,J=2.1Hz),132.7(d,J=8.4Hz),132.7,133.3; 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-87.6(s,1P).HRMS m / z:[M+H] + calcd for C 36 H 22 P + 485.1454; Found: 485.1455.

[0107] Example 14: Synthesis of tris(anthracene-9-ethynyl)phosphine

[0108]

[0109] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), 4,4'-dihydroxydiphenyl sulfide (0.35 mmol), and lithium iodide (0.25 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, anthracene-9-acetylene (0.69 mmol), sodium bis(trimethylsilylamino)amine (0.69 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 14 in a separation yield of 47% (yield calculation based on phosphorus atoms).

[0110] Key NMR data for product 14: 1 H NMR (600MHz, CDCl3) δ: 7.49 (t, J = 7.2Hz, 8H), 7.54 (t, J = 6.6Hz, 8H), 8.00 (d, J = 8.4Hz, 8H), 8.46 (s, 3H), 8.76 (d, J = 8.4Hz, 6H); 13 C NMR (150MHz, CDCl3) δ: 91.1 (d, J = 3.6Hz), 103.0 (d, J = 11.3Hz), 115.8, 125.8, 126.6, 127.3, 128.7, 129.1, 131.0, 133.3 (d, J = 2.1Hz); 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.1(s,1P).HRMSm / z:[M+H] + calcd for C 48 H 28 P + 635.1923; Found: 635.1932.

[0111] Example 15: Synthesis of tris(phenanthrene-9-ethynyl)phosphine

[0112]

[0113] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), p-toluene disulfide (0.2 mmol), and lithium chloride (0.4 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, phenanthrene-9-acetylene (0.65 mmol), potassium bis(trimethylsilylamino)amine (0.65 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 3 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 15 in a separation yield of 71% (yield calculation based on phosphorus atoms).

[0114] Key NMR data for product 15: 1 H NMR (600MHz, CDCl3) δ: 7.60 (t, J = 7.2Hz, 3H), 7.87 (d, J = 8.4Hz, 3H), 8.20 (s, 3H), 8.61 (d, J = 7.2Hz, 3H), 8.64 (d, J = 7.8Hz, 3H), 8.68 (d, J = 7.8Hz, 3H); 13 C NMR (150MHz, CDCl3) δ: 84.1 (d, J = 4.7Hz), 104.4 (d, J = 11.1Hz), 118.6, 122.7, 122.8, 127.0, 12 7.1,127.3,127.4,128.1,128.9,130.0,130.8,130.9,131.0(d,J=1.1Hz),133.4(d,J=2.4Hz); 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.0(s,1P).HRMS m / z:[M+H] + calcd for C 48 H 28 P + 635.1923; Found: 635.1928.

[0115] Example 16: Synthesis of tris(naphthyl-1-ethynyl)phosphine

[0116]

[0117] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), 4,4'-diaminodiphenyl disulfide (0.3 mmol), and potassium iodide (0.2 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, naphthalene-1-acetylene (0.56 mmol), sodium hydride (0.56 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 16 in a separation yield of 75% (yield calculation based on phosphorus atoms).

[0118] Key NMR data for product 16: 1 H NMR (600MHz, CDCl3) δ: 7.30 (t, J = 7.8Hz, 3H), 7.37 (t, J = 6.6Hz, 3H), 7.42 (t, J = 7.2Hz, 3H), 7.73-7.69 (m, 9H), 8.37 (d, J = 8.4Hz, 3H); 13 C NMR (150MHz, CDCl3) δ: 84.6 (d, J = 5.0H), 104.1 (d, J = 11.3Hz), 119.6, 125.1, 126.1, 12 6.6, 127.2 (d, J = 3.8Hz), 128.3, 130.0, 131.3 (d, J = 2.6Hz), 133.0, 133.4 (d, J = 1.8Hz); 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.2(s,1P).HRMS m / z:[M+H] + calcd for C 36 H 22 P + 485.1454; Found: 485.1450.

[0119] Example 17: Synthesis of tris(thiophene-3-ethynyl)phosphine

[0120]

[0121] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), diphenyldiselenoether (0.4 mmol), and sodium bromide (0.3 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, thiophene-3-acetylene (0.66 mmol), n-butyllithium (0.66 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 2.5 hours. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 17 in a 50% separation yield (yield calculation based on phosphorus atoms).

[0122] Key NMR data for product 17: 1 H NMR (600MHz, CDCl3) δ: 7.20 (dd, J = 5.4Hz, 5.4Hz, 3H), 7.27 (q, J = 2.4Hz, 3H), 7.62 (dd, J = 3Hz, 3Hz, 3H); 13 C NMR (150MHz, CDCl3) δ: 79.0 (d, J = 6.8Hz), 100.8 (d, J = 11.6Hz), 121.3, 125.5, 130.0 (d, J = 1.8Hz), 131.2 (d, J = 2.7Hz); 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-88.2(s,1P).HRMS m / z:[M+H] + calcd for C 18 H 10 PS3 + 352.9677; Found: 352.9673.

[0123] Example 18: Synthesis of tris(ferrocene-1-ethynyl)phosphine

[0124]

[0125] In a glove box filled with nitrogen or argon, white phosphorus (0.05 mmol), diphenyl disulfide (0.7 mmol), and lithium fluoride (0.3 mmol) were added sequentially to a 5 mL sample vial equipped with a stirrer, followed by the addition of THF (1.0 mL). The mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution A. Then, ferrocene-1-acetylene (0.66 mmol), lithium bis(trimethylsilylamino)amine (0.66 mmol), and THF (1.0 mL) were added to a 2 mL sample vial, and the mixture was stirred at room temperature for 2 min until all the solids were dissolved to obtain solution B. Solution B was slowly added dropwise to solution A, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the resulting mixture was quenched with saturated NH4Cl aqueous solution (20 mL), and the organic phase was extracted multiple times with ethyl acetate (3 × 20 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on 300-400 mesh silica gel (petroleum ether / ethyl acetate = 100:1) to give product 18 in a separation yield of 45% (yield calculation based on phosphorus atoms).

[0126] Key NMR data for product 18: 1 H NMR (600MHz, CDCl3) δ: 4.55 (t, J = 1.8Hz, 6H), 4.26 (s, 13H), 4.26-4.24 (m, 8H); 13 C NMR (150MHz, CDCl3) δ: 63.4, 69.4, 70.1 (d, J = 4.4Hz), 70.2, 72.1 (d, J = 2.0Hz), 76.6 (d, J = 9.5Hz), 105.3 (d, J = 12.0Hz); 31 P{ 1 H}NMR(243MHz,CDCl3)δ:-87.8(s,1P).HRMS m / z:[M+H] + calcd for C 36 H 28 Fe3P + 658.9971; Found: 658.9973.

[0127] Industry availability

[0128] The tri(arylethynyl)phosphine compounds containing triarylethynyl structural units of the present invention have potential application value as organophosphine ligands in transition metal catalysis.

Claims

1. A method for producing a tri(arylacetylenyl)phosphine compound, which is a method for producing a tri(arylacetylenyl)phosphine compound containing a triarylacetylenyl structural unit represented by the following formula (II), characterized by comprising the steps of: Step 1: adding white phosphorus P4, an activating agent, an auxiliary agent, and a solvent to a reactor under nitrogen or argon protection, dissolving them to obtain a solution A, and then adding a compound represented by the following formula (I), a base, and a solvent to another reactor under nitrogen or argon protection, dissolving them to obtain a solution B; Step 2: subsequently adding the solution B slowly dropwise to the solution A, and stirring to perform a reaction at room temperature, thereby obtaining a compound represented by the formula (II); wherein the formula (I) and the formula (II) are as follows: wherein R is one of hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthryl, phenanthryl, pyridyl, thienyl, or benzofuranyl, and Ar is phenyl, naphthyl, anthryl, phenanthryl, pyridyl, thienyl, or ferrocenyl. The method for producing a tri(arylacetylenyl)phosphine compound comprises the steps of: Step 1: adding white phosphorus P4, an activating agent, an auxiliary agent, and a solvent to a reactor under nitrogen or argon protection, dissolving them to obtain a solution A, and then adding a compound represented by the following formula (I), a base, and a solvent to another reactor under nitrogen or argon protection, dissolving them to obtain a solution B; Step 2: subsequently adding the solution B slowly dropwise to the solution A, and stirring to perform a reaction at room temperature, thereby obtaining a compound represented by the formula (II); The activating agent is a diaryl diselenide or a diaryl disulfide. Herein, in the compound represented by the formula (I) and the compound represented by the formula (II), R is one of hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthryl, phenanthryl, pyridyl, thienyl, or benzofuranyl, and Ar is phenyl, naphthyl, anthryl, phenanthryl, pyridyl, thienyl, or ferrocenyl.

2. The production method according to claim 1, wherein, The auxiliary agent used in Step 1 is a halide of an alkali metal.

3. The production method according to claim 2, wherein, The halide of an alkali metal is lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, lithium fluoride, sodium fluoride, potassium fluoride, or cesium fluoride.

4. The production method according to claim 1, wherein The base used in Step 1 is a hydride, a hydroxide, an alkylate, or an amide of an alkali metal.

5. The production method according to claim 4, wherein The hydride of an alkali metal is sodium hydride or potassium hydride, the hydroxide of an alkali metal is sodium hydroxide or potassium hydroxide, the alkylate of an alkali metal is n-butyllithium or tert-butyllithium, and the amide of an alkali metal is lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, or potassium bis(trimethylsilyl)amide.

6. The production method according to claim 1, wherein In Step 1, the room temperature is in the range of 20°C to 30°C, and the reaction time is 1 to 3 hours.

7. The production method according to claim 1, wherein The compound represented by the formula (I) used in Step 1 is used in a proportion of 2.5 to 3.5 times the molar equivalent of white phosphorus calculated based on the phosphorus atom. The auxiliary agent used is used in a proportion of 0.5 to 2.0 times the molar equivalent of white phosphorus calculated based on the phosphorus atom. The base used is used in a proportion of 2.5 to 3.5 times the molar equivalent of white phosphorus calculated based on the phosphorus atom. The activating agent used is used in a proportion of 1.0 to 2.0 times the molar equivalent of white phosphorus calculated based on the phosphorus atom.

8. The production method according to claim 1, wherein The diaryl diselenide is diphenyl diselenide, p-tolyl diselenide, 4,4'-dichlorodiphenyl diselenide, bis(4-fluorophenyl) diselenide, bis(4-methoxyphenyl) diselenide, bis(4-nitrophenyl) diselenide, 3,3'-di-tert-butyldiphenyl diselenide, 2,2'-dimethoxydiphenyl diselenide, di(2-anthryl) diselenide, or di(2-naphthyl) diselenide. The diaryl disulfides are diphenyl disulfide, p-tolyl disulfide, 4,4'-dichlorodiphenyl disulfide, bis(4-methoxyphenyl) disulfide, bis(4-nitrophenyl) disulfide, 4,4'-dicarboxydiphenyl disulfide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-diaminodiphenyl disulfide, bis(4-fluorophenyl) disulfide, 3,3'-dihydroxydiphenyl disulfide, 3,3'-difluorodiphenyl disulfide, 2,2'-diaminodiphenyl disulfide, 2,2'-dithiodibenzoic acid, dithiodibenzothiazole, di(2-naphthyl) disulfide, di(l-naphthyl) disulfide, 2,2'-dithiodipyridine, dibenzyl disulfide.

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