A method for preparing 3,3-diarylallyl-substituted organophosphonate compounds

Abstract

The application provides a method for efficiently and selectively synthesizing 3,3-diarylallyl-substituted organic phosphonate compounds containing different substituted functional groups, which uses zinc bromide as a catalyst, trimethylchlorosilane as a cocatalyst, water as an assistant, trialkyl / aryl phosphite or dialkyl phenyl phosphonate or alkoxydiaryl phosphine and 1,1-diaryl-2-propen-1-ol as reaction substrates, and an organic solvent is added to the reaction system. The method has the following advantages: the catalyst is cheap and easy to obtain; the substrate has high applicability; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is high. The method solves the problems of poor reaction selectivity, complicated reaction steps, low yield and the need to use harmful reagents to the environment in the traditional synthesis of 3,3-diarylallyl-substituted organic phosphonate compounds, and has a good industrial application prospect. The application also provides corresponding 3,3-diarylallyl-substituted organic phosphonate derivatives containing different substituted functional groups.

Description

Technical Field

[0001] This invention relates to the field of catalytic synthesis of 3,3-diarylallyl-substituted organophosphonates, and more specifically to a method for synthesizing 3,3-diarylallyl-substituted organophosphonates by efficiently reacting trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphines with 1,1-diaryl-2-propen-1-ols via the Michaelis-Arbuzov rearrangement. Background Technology

[0002] 3,3-Diarylallyl-substituted organophosphonates are an important class of organic synthetic intermediates. Due to their unique chemical structures, these compounds have wide applications in the preparation of pharmaceutical intermediates, biological agents, optoelectronic materials, high-efficiency flame retardants, and organic ligands.

[0003] In phosphorylation reactions, tricoordinate phosphorus reagents ultimately transform into tetracoordinate phosphorus compounds, especially those containing highly bonded phosphoryl groups (P=O). During these reactions, tricoordinate phosphorus reagents often present pentacoordinate phosphorus compounds as intermediates or transition states. It is precisely this interconversion between compounds of different coordination numbers that has enabled the widespread application of organophosphorus reagents in organic synthesis, such as the Michaelis-Arbuzov reaction, and they have gradually become an important component of organophosphorus chemistry, particularly organic synthetic chemistry.

[0004] The methods reported in the literature for synthesizing 3,3-diarylallyl-substituted organophosphonates mainly include: (1) PH bond-involved ring-opening cross-coupling reaction: using P(O)-H compounds and 1,1-diaryl-substituted-2-cyclopropene compounds to undergo a free radical ring-opening cross-coupling reaction under the catalysis of transition metals; (2) Cross-coupling reaction: using P(O)-H compounds to catalyze the cross-coupling reaction with 1,1-diaryl-substituted allyl halocarbon compounds in the presence of transition metals (iron, copper, nickel, palladium, etc.), organic ligands and bases; (3) Transition metal-catalyzed dehydration cross-coupling reaction: using P(O)-H compounds to catalyze the dehydration cross-coupling reaction with 1,1-diaryl-2-propene-1-ol compounds in the presence of transition metals (copper, etc.) and organic ligands. However, the above methods generally use expensive phosphorylation reagents (such as P(O)-H compounds) and transition metal catalysts, special ligands (such as ferrocene ligands and carbene ligands), and also have drawbacks such as complicated experimental procedures, expensive and difficult-to-recycle catalysts, harsh reaction conditions, overlapping substrate applicability, low yield, and significant environmental pollution.

[0005] To date, the efficient synthesis of 3,3-diarylallyl-substituted organophosphonates faces several challenges, including raw material quality, production safety, and product stability and purity. The synthesis technology is quite difficult, and currently only a few companies in countries such as the United States, Japan, and Germany are producing them. Meanwhile, my country's high-end organophosphonate products currently rely mainly on imports.

[0006] To address the shortcomings of existing synthetic processes for 3,3-diarylallyl-substituted organophosphonates, the industry is focusing on developing new methods for preparing corresponding 3,3-diarylallyl-substituted organophosphonates by using inexpensive transition metal catalysts for efficient catalysis. These methods utilize stable, inexpensive, and readily available trialkyl / aryl phosphites, dialkylphenyl phosphonates, or alkoxydiarylphosphine compounds as building blocks with 1,1-diaryl-2-propen-1-ols. Summary of the Invention

[0007] The purpose of this invention is to provide a novel method for the efficient and selective synthesis of corresponding 3,3-diarylallyl-substituted organophosphonates from inexpensive and readily available trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphine and 1,1-diaryl-2-propen-1-ol compounds, thereby overcoming the aforementioned deficiencies in the prior art.

[0008] This invention comprises the following steps: taking reactant amounts of trialkyl / aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine, 1,1-diaryl-2-propen-1-ol, catalyst, co-catalyst, auxiliaries and organic solvent, and mixing them in an air environment in a reaction vessel, and stirring at 25~120°C. o Reacting at step C for 5–12 hours yields the corresponding 3,3-diarylallyl-substituted organophosphonates containing different substituted functional groups. The specific reaction formulas are as follows: （I） in, The catalyst is zinc bromide, the co-catalyst is trimethylchlorosilane, the auxiliary agent is water, and the organic solvent is acetonitrile. Ar 1 Selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, and 4-bromophenyl; Ar 2 Selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3,4-dimethylphenyl, 4-phenylphenyl, 2-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 4-trifluoromethylphenyl; R is selected from methyl, ethyl, phenyl, butyl, and isopropyl. Z1 Selected from methoxy, ethoxy, phenoxy, butoxy, isopropoxy, phenyl, 4-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 3,5-dimethylphenyl, 2,5-dimethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 4-chlorophenyl, 4-phenylphenyl, 3-phenylphenyl, 2-naphthyl, 1-naphthyl; Z 2 Selected from methoxy, ethoxy, phenoxy, butoxy, isopropoxy, phenyl, 4-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 3,5-dimethylphenyl, 2,5-dimethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 4-chlorophenyl, 4-phenylphenyl, 3-phenylphenyl, 2-naphthyl, 1-naphthyl.

[0009] In the above method for synthesizing 3,3-diarylallyl-substituted organophosphonates from trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphines with 1,1-diaryl-2-propen-1-ols, the 1,1-diaryl-2-propen-1-ol is selected from 1,1-diphenyl-2-propen-1-ol, 1,1-di(4-methylphenyl)-2-propen-1-ol, 1,1-di(4-methoxyphenyl)-2-propen-1-ol, 1,1-di(4-fluorophenyl)-2-propen-1-ol, 1,1-di(4-chlorophenyl)-2-propen-1-ol, 1,1-di(4-bromophenyl)-2-propen-1-ol, 1-phenyl-1-(4-methylphenyl)-2-propen-1-ol, 1-phenyl-1-(4-methylphenyl)-2-propen-1-ol, 1-phenyl-1-(2 ... 1-Phenyl-1-(4-methoxyphenyl)-2-propen-1-ol, 1-Phenyl-1-(3,4-dimethylphenyl)-2-propen-1-ol, 1-Phenyl-1-(4-phenylphenyl)-2-propen-1-ol, 1-Phenyl-1-(4-fluorophenyl)-2-propen-1-ol, 1-Phenyl-1-(2-fluorophenyl)-2-propen-1-ol, 1-Phenyl-1-(4-chlorophenyl)-2-propen-1-ol, 1-Phenyl-1-(3-chlorophenyl)-2-propen-1-ol, 1-Phenyl-1-(4-bromophenyl)-2-propen-1-ol, 1-Phenyl-1-(3-bromophenyl)-2-propen-1-ol, 1-Phenyl-1-(4-trifluoromethylphenyl)-2-propen-1-ol.

[0010] In the above method for synthesizing 3,3-diarylallyl-substituted organophosphonates from trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphines with 1,1-diaryl-2-propen-1-ols, the trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphines are selected from trimethyl phosphite, triphenyl phosphite, tributyl phosphite, triisopropyl phosphite, diethylphenylphosphite, ethoxydiphenylphosphine, ethoxydi(4-methylphenyl)phosphine, ethoxydi(3-methylphenyl)phosphine, ethoxydi(4-... Ethylphenyl)phosphine, ethoxydi(4-butylphenyl)phosphine, ethoxydi(4-tert-butylphenyl)phosphine, ethoxydi(3,5-dimethylphenyl)phosphine, ethoxydi(2,5-dimethylphenyl)phosphine, ethoxydi(4-fluorophenyl)phosphine, ethoxydi(3-fluorophenyl)phosphine, ethoxydi(4-chlorophenyl)phosphine, ethoxydi(4-phenylphenyl)phosphine, ethoxydi(3-phenylphenyl)phosphine, ethoxydi(2-naphthyl)phosphine, ethoxydi(1-naphthyl)phosphine, ethoxyphenyl(4-fluorophenyl)phosphine, ethoxyphenyl(3-fluorophenyl)phosphine.

[0011] In the above method for synthesizing 3,3-diarylallyl-substituted organophosphonate compounds from trialkyl / aryl phosphite, dialkylphenylphosphonate, or alkoxydiarylphosphine with 1,1-diaryl-2-propen-1-ol, the molar ratio of 1,1-diaryl-2-propen-1-ol to trialkyl / aryl phosphite, dialkylphenylphosphonate, or alkoxydiarylphosphine is 1:[1.0~1.2]; the molar ratio of 1,1-diaryl-2-propen-1-ol to catalyst and co-catalyst is 1:[0.05~0.2]:[0.01-0.1]; and the molar ratio of 1,1-diaryl-2-propen-1-ol to auxiliaries is 1:[1.0~3.0].

[0012] This invention provides a highly efficient and selective method for synthesizing 3,3-diarylallyl-substituted organophosphonates from trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphites with 1,1-diaryl-2-propen-1-ols. The reaction process is mild and easily controlled. While achieving high yields and 100% selectivity, this method is simple and easy to implement, and the catalyst used is inexpensive and readily available. The preparation is simple and has good prospects for industrial application. Detailed Implementation

[0013] The present invention will be further described below with reference to embodiments thereof: I. Testing and Analysis In the following embodiments of the present invention, the structural analysis of the reaction products was performed using an Agilent GC / MS (6890N / 5973N) system equipped with an HP-5MS capillary column (30m × 0.45mm × 0.8μm) and a Bruker Avance-III 500 NMR analyzer. The selectivity and yield of the target products were analyzed using a Bruker Avance-III 500 NMR analyzer.

[0014] Example 1

[0015] Prepare a set of parallel reactions. Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and react at 25°C. o C, 40 o C, 60 o C, 80 o C, 100 o C, 120 o The reaction was stirred at temperature C for 5 hours. After the reaction was complete, gas chromatography analysis showed that the target product was detected at a reaction temperature of 100°C. o The highest yield was achieved at C, at 96% (gas chromatography yield, with dodecane as an internal standard, calculated using the normalization method).

[0016] Example 2

[0017] Prepare a set of parallel reactions. Weigh out 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water, and separately weigh out zinc bromide (0.025 mmol, 0.05 mmol, 0.1 mmol). Add these to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile. Reheat at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, gas chromatography analysis showed that the target product had the highest yield of 96% when the amount of zinc bromide was 0.05 mmol (gas chromatography yield, with dodecane as an internal standard, calculated using the normalization method).

[0018] Example 3

[0019] Prepare a set of parallel reactions. Weigh out 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, and 18 mg (1.0 mmol) of water, and separately weigh out trimethylchlorosilane (0.005 mmol, 0.025 mmol, 0.05 mmol). Add these to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile. Reheat at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, gas chromatography analysis showed that the target product had the highest yield of 96% when the amount of trimethylchlorosilane was 0.025 mmol (gas chromatography yield, with dodecane as an internal standard, calculated using the normalization method).

[0020] Example 4

[0021] 119 mg (0.5 mmol) of 1,1-bis(4-methylphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 94%.

[0022] Example 5

[0023] Add 135 mg (0.5 mmol) of 1,1-bis(4-methoxyphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 96%.

[0024] Example 6

[0025] 123 mg (0.5 mmol) of 1,1-bis(4-fluorophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 97%.

[0026] Example 7

[0027] Add 139 mg (0.5 mmol) of 1,1-bis(4-chlorophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 90%.

[0028] Example 8

[0029] 184 mg (0.5 mmol) of 1,1-bis(4-bromophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred at C for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 87%.

[0030] Example 9

[0031] 112 mg (0.5 mmol) of 1-phenyl-1-(4-methylphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air, followed by 2.0 mL of acetonitrile. The mixture was then dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 95%.

[0032] Example 10

[0033] 112 mg (0.5 mmol) of 1-phenyl-1-(2-methylphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 89%.

[0034] Example 11

[0035] Add 120 mg (0.5 mmol) of 1-phenyl-1-(4-methoxyphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 94%.

[0036] Example 12

[0037] 119 mg (0.5 mmol) of 1-phenyl-1-(3,4-dimethylphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air, followed by the addition of 2.0 mL of acetonitrile. The mixture was then dissolved at 100 °C. o The reaction was stirred at C for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 87%.

[0038] Example 13

[0039] Add 143 mg (0.5 mmol) of 1-phenyl-1-(4-phenylphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 94%.

[0040] Example 14

[0041] 143 mg (0.5 mmol) of 1-phenyl-1-(4-fluorophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 96%.

[0042] Example 15

[0043] 143 mg (0.5 mmol) of 1-phenyl-1-(2-fluorophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 91%.

[0044] Example 16

[0045] 122 mg (0.5 mmol) of 1-phenyl-1-(4-chlorophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 92%.

[0046] Example 17

[0047] 122 mg (0.5 mmol) of 1-phenyl-1-(3-chlorophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water were added to a Schlenk (25 mL) tube under air. Then, 2.0 mL of acetonitrile was added, and the mixture was dissolved at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 85%.

[0048] Example 18

[0049] Add 145 mg (0.5 mmol) of 1-phenyl-1-(4-bromophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 91%.

[0050] Example 19

[0051] Add 145 mg (0.5 mmol) of 1-phenyl-1-(3-bromophenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 79%.

[0052] Example 20

[0053] Add 139 mg (0.5 mmol) of 1-phenyl-1-(4-trifluoromethylphenyl)-2-propen-1-ol, 62 mg (0.5 mmol) of trimethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 84%.

[0054] Example 21

[0055] Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 83 mg (0.5 mmol) of triethyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 98%.

[0056] Example 22

[0057] Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 155 mg (0.5 mmol) of triphenyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 94%.

[0058] Example 23

[0059] Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 125 mg (0.5 mmol) of tributyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 91%.

[0060] Example 24

[0061] Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 104 mg (0.5 mmol) of triisopropyl phosphite, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 85%.

[0062] Example 25

[0063] Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 99 mg (0.5 mmol) of diethylphenylphosphonate, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 84%.

[0064] Example 26 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 115 mg (0.5 mmol) of ethoxydiphenylphosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 95%.

[0065] Example 27 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 129 mg (0.5 mmol) of ethoxybis(4-methylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C.o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 94%.

[0066] Example 28 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 129 mg (0.5 mmol) of ethoxybis(3-methylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 93%.

[0067] Example 29 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 143 mg (0.5 mmol) of ethoxybis(4-ethylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 96%.

[0068] Example 30 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 171 mg (0.5 mmol) of ethoxybis(4-butylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 97%.

[0069] Example 31 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 171 mg (0.5 mmol) of ethoxybis(4-tert-butylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 93%.

[0070] Example 32 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 143 mg (0.5 mmol) of ethoxybis(3,5-dimethylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 90%.

[0071] Example 33 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 143 mg (0.5 mmol) of ethoxybis(2,5-dimethylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 82%.

[0072] Example 34 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 133 mg (0.5 mmol) of ethoxybis(4-fluorophenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 90%.

[0073] Example 35 Add 105 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 133 mg (0.5 mmol) of ethoxybis(3-fluorophenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 88%.

[0074] Example 36 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 133 mg (0.5 mmol) of ethoxybis(4-chlorophenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 77%.

[0075] Example 37 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 191 mg (0.5 mmol) of ethoxybis(4-phenylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C.o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 95%.

[0076] Example 38 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 191 mg (0.5 mmol) of ethoxybis(3-phenylphenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 93%.

[0077] Example 39 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 165 mg (0.5 mmol) of ethoxybis(2-naphthyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 91%.

[0078] Example 40 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 165 mg (0.5 mmol) of ethoxybis(1-naphthyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air. Then add 2.0 mL of acetonitrile and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 90%.

[0079] Example 41 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 124 mg (0.5 mmol) of ethoxyphenyl(4-fluorophenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 83%.

[0080] Example 42 Add 155 mg (0.5 mmol) of 1,1-diphenyl-2-propen-1-ol, 124 mg (0.5 mmol) of ethoxyphenyl(3-fluorophenyl)phosphine, 11.3 mg (0.05 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, and 18 mg (1.0 mmol) of water to a Schlenk (25 mL) tube under air conditions, then add 2.0 mL of acetonitrile, and dissolve at 100 °C. o The reaction was stirred for 12 hours. After the reaction was completed, the product was purified by column chromatography, and the yield of the target product was 90%.

[0081] As can be seen from the above examples, the method of preparing 3,3-diarylallyl-substituted organophosphonates with different functional groups by reacting trialkyl / aryl phosphites, dialkylphenylphosphonates, or alkoxydiarylphosphines with 1,1-diaryl-2-propen-1-ols has the advantages of mild reaction conditions, inexpensive and readily available catalysts, and simple preparation. Furthermore, this method also has the advantages of wide substrate applicability and high yield, providing an efficient method for synthesizing 3,3-diarylallyl-substituted organophosphonates with different functional groups.

[0082] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A compound having the structural formula prepared by reacting a trialkyl / aryl phosphite, a dialkylphenylphosphonate, or an alkoxydiarylphosphine with a 1,1-diaryl-2-propen-1-ol. （I） The preparation method of 3,3-diarylallyl-substituted organophosphonate compounds, with specific reaction formulas as follows: （I） Its features are, Includes the following steps: Take the reaction amounts of trialkyl / aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine, 1,1-diaryl-2-propen-1-ol, catalyst, co-catalyst, auxiliaries and organic solvent, place them in a reaction vessel under air and mix them, stirring at 25~120℃. o The reaction proceeds for 5-12 hours at step C to obtain the corresponding 3,3-diarylallyl substituted organophosphonates containing different substituted functional groups. in, The catalyst is zinc bromide, the co-catalyst is trimethylchlorosilane, the auxiliary agent is water, and the organic solvent is acetonitrile. Ar 1 Selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, and 4-bromophenyl; Ar 2 Selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3,4-dimethylphenyl, 4-phenylphenyl, 2-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 4-trifluoromethylphenyl; R is selected from methyl, ethyl, phenyl, butyl, and isopropyl. Z 1 Selected from methoxy, ethoxy, phenoxy, butoxy, isopropoxy, phenyl, 4-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 3,5-dimethylphenyl, 2,5-dimethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 4-chlorophenyl, 4-phenylphenyl, 3-phenylphenyl, 2-naphthyl, 1-naphthyl; Z 2 Selected from methoxy, ethoxy, phenoxy, butoxy, isopropoxy, phenyl, 4-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 3,5-dimethylphenyl, 2,5-dimethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 4-chlorophenyl, 4-phenylphenyl, 3-phenylphenyl, 2-naphthyl, 1-naphthyl.

2. The preparation method according to claim 1, characterized in that, The 1,1-diaryl-2-propen-1-ol is selected from 1,1-diphenyl-2-propen-1-ol, 1,1-di(4-methylphenyl)-2-propen-1-ol, 1,1-di(4-methoxyphenyl)-2-propen-1-ol, 1,1-di(4-fluorophenyl)-2-propen-1-ol, 1,1-di(4-chlorophenyl)-2-propen-1-ol, 1,1-di(4-bromophenyl)-2-propen-1-ol, 1-phenyl-1-(4-methylphenyl)-2-propen-1-ol, 1-phenyl-1-(2-methylphenyl)-2-propen-1-ol, and 1-phenyl-1-(4-methoxyphenyl)-2-propen-1-ol. 1-Pheny-1-(3,4-dimethylphenyl)-2-propen-1-ol, 1-Pheny-1-(4-phenylphenyl)-2-propen-1-ol, 1-Pheny-1-(4-fluorophenyl)-2-propen-1-ol, 1-Pheny-1-(2-fluorophenyl)-2-propen-1-ol, 1-Pheny-1-(4-chlorophenyl)-2-propen-1-ol, 1-Pheny-1-(3-chlorophenyl)-2-propen-1-ol, 1-Pheny-1-(4-bromophenyl)-2-propen-1-ol, 1-Pheny-1-(3-bromophenyl)-2-propen-1-ol, 1-Pheny-1-(4-trifluoromethylphenyl)-2-propen-1-ol.

3. The preparation method according to claim 1, characterized in that, The trialkyl / aryl phosphite, dialkylphenyl phosphite, or alkoxydiaryl phosphite is selected from trimethyl phosphite, triphenyl phosphite, tributyl phosphite, triisopropyl phosphite, diethylphenyl phosphite, ethoxydiphenylphosphite, ethoxydi(4-methylphenyl)phosphite, ethoxydi(3-methylphenyl)phosphite, ethoxydi(4-ethylphenyl)phosphite, ethoxydi(4-butylphenyl)phosphite, ethoxydi(4-tert-butylphenyl)phosphite, ethoxydi(3,5-dimethylphenyl)phosphite, ethoxydi(2,5-dimethylphenyl)phosphite, ethoxydi(4-fluorophenyl)phosphite, ethoxydi(3-fluorophenyl)phosphite, ethoxydi(4-chlorophenyl)phosphite, ethoxydi(4-phenylphenyl)phosphite, ethoxydi(3-phenylphenyl)phosphite, ethoxydi(2-naphthyl)phosphite, ethoxydi(1-naphthyl)phosphite, ethoxyphenyl(4-fluorophenyl)phosphite, and ethoxyphenyl(3-fluorophenyl)phosphite.

4. The preparation method according to claim 1, characterized in that, The molar ratio of 1,1-diaryl-2-propen-1-ol to trialkyl / aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine is 1:[1.0~1.2]; the molar ratio of 1,1-diaryl-2-propen-1-ol to catalyst and co-catalyst is 1:[0.05~0.2]:[0.01-0.1]; the molar ratio of 1,1-diaryl-2-propen-1-ol to auxiliaries is 1:[1.0~3.0].

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