CN117362338A - Method for preparing 3, 3-diaryl allyl substituted organic phosphonate compound - Google Patents

Method for preparing 3, 3-diaryl allyl substituted organic phosphonate compound Download PDF

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CN117362338A
CN117362338A CN202311268120.5A CN202311268120A CN117362338A CN 117362338 A CN117362338 A CN 117362338A CN 202311268120 A CN202311268120 A CN 202311268120A CN 117362338 A CN117362338 A CN 117362338A
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mmol
propen
phosphine
phenyl
diaryl
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熊碧权
史崇浩
许卫凤
朱龙志
曹帆
唐课文
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Hunan Institute of Science and Technology
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Hunan Institute of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3882—Arylalkanephosphonic acids

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  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention provides a method for efficiently and selectively synthesizing 3, 3-diaryl allyl substituted organic phosphonate compounds containing different substituted functional groups, which adopts zinc bromide as a catalyst, trimethylchlorosilane as a cocatalyst, water as an auxiliary agent, trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and 1, 1-diaryl-2-propylene-1-alcohol compounds as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that: the catalyst is cheap and easy to obtain; the applicability of the substrate is high; 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 defects of poor reaction selectivity, complicated reaction steps, low yield, need of using environment-friendly reagents and the like of the traditional synthesis of the 3, 3-diaryl allyl substituted organic phosphonate compounds, and has good industrial application prospect. The invention also provides corresponding 3, 3-diaryl allyl substituted organic phosphonate derivatives containing different substituted functional groups.

Description

Method for preparing 3, 3-diaryl allyl substituted organic phosphonate compound
Technical Field
The invention relates to the field of catalytic synthesis of 3, 3-diaryl allyl substituted organic phosphonate compounds, in particular to a synthesis method for preparing 3, 3-diaryl allyl substituted organic phosphonate compounds by efficiently reacting trialkyl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine with 1, 1-diaryl-2-propylene-1-alcohol compounds and carrying out Michaelis-Arbuzov rearrangement.
Background
3, 3-diaryl allyl substituted organic phosphonate is an important class of organic synthesis intermediates. Because of the unique chemical structure, the compounds have wide application in the aspects of preparation of medical intermediates, biological agents, photoelectric materials, efficient flame retardants, organic ligands and the like.
The tridentate phosphorus reagent is eventually converted to a tetradentate phosphorus compound during the phosphorylating reaction, particularly a tetradentate phosphorus compound containing Gao Jian-capable phosphoryl groups (p=o). In the reaction process, often, a pentadentate phosphorus compound is used as an intermediate or a transition state, and the organic phosphorus reagent is widely applied to organic synthesis just due to the mutual conversion between compounds with different coordination numbers, such as Michaelis-Arbuzov reaction and the like, so that the reagent gradually becomes an important component of organic phosphorus chemistry, in particular organic synthesis chemistry.
The methods reported in the literature for synthesizing 3, 3-diaryl allyl substituted organic phosphonates mainly comprise: (1) the P-H bond participates in a ring-opening cross-coupling reaction: the P (O) -H compound and the 1, 1-diaryl substituted-2-cyclopropene compound are utilized to generate free radical type ring-opening cross coupling reaction under the catalysis of transition metal; (2) Cross-coupling reaction: the cross coupling reaction of the P (O) -H compound and the 1, 1-diaryl substituted allyl halohydrocarbon compound is catalyzed by the P (O) -H compound in the presence of reagents such as transition metal (iron, copper, nickel, palladium and the like), organic ligand, alkali and the like; (3) transition metal catalyzed dehydration cross-coupling reaction: the dehydration cross-coupling reaction of the P (O) -H compound and the 1, 1-diaryl-2-propylene-1-alcohol compound is catalyzed by the P (O) -H compound in the presence of reagents such as transition metal (copper and the like) and organic ligand and the like. However, the above methods generally employ expensive phosphorylating agents (P (O) -H compounds, etc.), transition metal catalysts, specific ligands (ferrocene ligands, carbene ligands, etc.), and have the disadvantages of complicated experimental procedures, expensive and difficult recycling of the catalysts, harsh reaction conditions, cross substrate applicability, low yield, and large environmental pollution.
To date, the efficient synthesis of 3, 3-diaryl allyl substituted organic phosphonate compounds has the problems of raw material quality, production safety, product stability, product purity and the like, the synthetic technology has great difficulty, and only few companies in the countries such as the United states, japan, germany and the like produce the 3, 3-diaryl allyl substituted organic phosphonate compounds at present, and the current situation of high-end organic phosphonate products in China mainly depends on import.
Aiming at the defects of the existing synthesis process of 3, 3-diaryl allyl substituted organic phosphonate compounds, the industry is focused on developing a novel method for preparing the corresponding 3, 3-diaryl allyl substituted organic phosphonate compounds by using stable, cheap and easily available trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and 1, 1-diaryl-2-propylene-1-alcohol compounds as synthesis blocks by using a cheap transition metal catalyst in high-efficiency catalysis.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing corresponding 3, 3-diaryl allyl substituted organic phosphonate compounds with high efficiency and high selectivity by taking trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and 1, 1-diaryl-2-propylene-1-alcohol compounds as raw materials, so as to overcome the defects in the prior art.
The invention comprises the following steps: taking the reaction amount of trialkyl/aryl phosphite or dialkyl phenylphosphonate or alkoxy diaryl phosphine, 1-diaryl-2-propylene-1-alcohol, catalyst, cocatalyst, auxiliary agent and organic solvent, placing the mixture in a reaction container under the air environment, mixing the mixture under the stirring condition at 25-120 o And C, reacting for 5-12 hours to obtain the corresponding 3, 3-diaryl allyl substituted organic phosphonate compound containing different substituted functional groups. The specific reaction formula is as follows:
（I）
wherein,
the catalyst is zinc bromide, the cocatalyst 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, 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.
In the method for synthesizing the 3, 3-diaryl allyl substituted organic phosphonate compound from trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and 1, 1-diaryl-2-propylene-1-alcohol compound, 1, 1-diaryl-2-propen-1-ol is selected from the group consisting of 1, 1-diphenyl-2-propen-1-ol, 1-bis (4-methylphenyl) -2-propen-1-ol, 1-bis (4-methoxyphenyl) -2-propen-1-ol, 1-bis (4-fluorophenyl) -2-propen-1-ol, 1-bis (4-chlorophenyl) -2-propen-1-ol, 1-bis (4-bromophenyl) -2-propen-1-ol, 1-phenyl-1- (4-methylphenyl) -2-propen-1-ol, 1-phenyl-1- (2-methylphenyl) -2-propen-1-ol, 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.
In the above method for synthesizing 3, 3-diaryl allyl substituted organic phosphonate compounds from trialkyl/aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine and 1, 1-diaryl-2-propen-1-ol compound, trialkyl/aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine is selected from trimethyl phosphite, triphenyl phosphite, tributyl phosphite, triisopropyl phosphite, diethylphenylphosphonate, 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-fluorophenyl) phosphine, and ethoxydi (1-fluorophenyl) phosphine.
In the method for synthesizing the 3, 3-diaryl allyl substituted organic phosphonate compound from trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and 1, 1-diaryl-2-propylene-1-alcohol compound, the molar ratio of the 1, 1-diaryl-2-propylene-1-alcohol to the trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine is 1: [1.0 to 1.2]; the molar ratio of the 1, 1-diaryl-2-propylene-1-alcohol to the catalyst and the cocatalyst is 1: [0.05 to 0.2]: [0.01-0.1]; the molar ratio of the 1, 1-diaryl-2-propylene-1-alcohol to the auxiliary agent is 1: [1.0 to 3.0].
The invention provides a method for synthesizing 3, 3-diaryl allyl substituted organic phosphonate compounds by trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and 1, 1-diaryl-2-propylene-1-alcohol compounds with high efficiency and high selectivity, and the reaction process is mild and easy to control. The method is simple and feasible while obtaining higher yield and 100% selectivity, and the catalyst used is cheap and easy to obtain, and the preparation is simple and has good industrial application prospect.
Detailed Description
The invention is further illustrated by the following examples in connection with the invention:
1. testing and analysis
Structural analysis of the reaction products in the following examples of the present invention was performed by using a gas-mass spectrometer combined with GC/MS (6890N/5973N) equipped with HP-5MS capillary chromatography column (30 m. Times.0.45 mm. Times.0.8 μm) manufactured by Agilent corporation, and Bruker Avance-III 500 nuclear magnetic resonance analyzer manufactured by Bruker corporation. The selectivity and yield of the target product were analyzed using a Bruker Avance-III 500 Nuclear magnetic resonance Analyzer manufactured by Bruker Corp.
Example 1
A set of parallel reactions was prepared, 105. 105 mg (0.5 mmol) of 1, 1-diphenyl-2-propen-1-ol, 62. 62 mg (0.5 mmol) of trimethyl phosphite, 11.3. 11.3 mg (0.05 mmol) of zinc bromide, 2.7. 2.7 mg (0.025 mmol) of trimethylchlorosilane, 18 mg (1.0 mmol) of water were introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0. 2.0 mL acetonitrile were further introduced into 25 portions of the tube o C、40 o C、60 o C、80 o C、100 o C、120 o The reaction was stirred for 5 hours. After the reaction is finished, the target product is analyzed by gas chromatography, and the reaction temperature is 100 o The highest yield at C was 96% (gas chromatography yield, dodecane as internal standard, calculated by normalization).
Example 2
A set of parallel reactions was prepared and 105. 105 mg (0.5 mmol) 1, 1-diphenyl-2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 2.7 mg (0.025 mmol) trimethylThe preparation method comprises the steps of weighing zinc bromide (0.025 mmol, 0.05 mmol and 0.1 mmol) respectively by using chlorosilane and 18. 18 mg (1.0 mmol) of water, adding the obtained mixture into a Schlenk (25 mL) tube under an air environment, adding 2.0 mL acetonitrile, and adding the obtained mixture into 100 o The reaction was stirred for 12 hours. After the reaction is finished, the yield of the target product is highest when the zinc bromide consumption is 0.05 mmol through gas chromatography analysis, and is 96% (the gas chromatography yield, dodecane is used as an internal standard and is calculated by adopting a normalization method).
Example 3
Preparing a group of parallel reactions, adding 105. 105 mg (0.5 mmol) of 1, 1-diphenyl-2-propen-1-ol, 62. 62 mg (0.5 mmol) of trimethyl phosphite, 11.3. 11.3 mg (0.05 mmol) of zinc bromide and 18 mg (1.0 mmol) of water, respectively weighing trimethylchlorosilane (0.005 mmol, 0.025 mmol and 0.05 mmol), adding the mixture into a Schlenk (25 mL) tube under an air environment, adding 2.0. 2.0 mL acetonitrile, and adding the mixture into the mixture to obtain a mixture of the mixture and the mixture, and adding the mixture to obtain a mixture o The reaction was stirred for 12 hours. After the reaction is finished, the yield of the target product is highest when the dosage of the trimethylchlorosilane is 0.025 mmol through gas chromatography analysis, and is 96% (the gas chromatography yield, dodecane is used as an internal standard and is calculated by adopting a normalization method).
Example 4
119 (mg) (0.5 mmol) 1, 1-bis (4-methylphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 5
135. 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, 18 mg (1.0 mmol) of water were introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile was further introduced into 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 6
123 mg (0.5 mmol) 1, 1-bis (4-fluorophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were added to a Schlenk (25 mL) tube under an air atmosphere, followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 97%.
Example 7
139 mg (0.5 mmol) 1, 1-bis (4-chlorophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 8
184. 184 mg (0.5 mmol) 1, 1-bis (4-bromophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were added to a Schlenk (25 mL) tube under an air atmosphere followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 9
112 mg (0.5 mmol) 1-phenyl-1- (4-methylphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 95%.
Example 10
112 mg (0.5 mmol) 1-phenyl-1- (2-methylphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water, and then put into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile is added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 11
120. 120 mg (0.5 mmol) 1-phenyl-1- (4-methoxyphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 12
119. 119 mg (0.5 mmol) 1-phenyl-1- (3, 4-dimethylphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile was further added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 13
143 mg (0.5 mmol) 1-phenyl-1- (4-phenylphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 14
143. 143 mg (0.5 mmol) 1-phenyl-1- (4-fluorophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water are added to Schl under an air atmosphereenk (25 mL) and 2.0 mL acetonitrile were added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 15
143 mg (0.5 mmol) 1-phenyl-1- (2-fluorophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were added to a Schlenk (25 mL) tube under an air atmosphere, followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 16
122 mg (0.5 mmol) 1-phenyl-1- (4-chlorophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 17
122 mg (0.5 mmol) 1-phenyl-1- (3-chlorophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 18
145 mg (0.5 mmol) 1-phenyl-1- (4-bromophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were added to a Schlenk (25 mL) tube under an air atmosphere followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating by column chromatographyPurification was carried out with a yield of 91% of the desired product.
Example 19
145 mg (0.5 mmol) 1-phenyl-1- (3-bromophenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were added to a Schlenk (25 mL) tube under an air atmosphere followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
Example 20
139. 139 mg (0.5 mmol) 1-phenyl-1- (4-trifluoromethylphenyl) -2-propen-1-ol, 62 mg (0.5 mmol) trimethyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 21
105. 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, 18 mg (1.0 mmol) of water were introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile was then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 98%.
Example 22
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile is then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 23
105 mg (0.5 mmol) of 1, 1-diphenyl1-propen-2-ol, 125 mg (0.5 mmol) tributyl phosphite, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water, and then introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile, at 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 24
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 25
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under air, 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 26
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 95%.
Example 27
105. 105 mg (0.5 mmol) 1, 1-diphenyl-2-propen-1-ol, 129 mg (0.5 mmol) ethoxybis (4-methylphenyl) phosphine, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water, in the absence of airAdding into Schlenk (25 mL) tube under gas atmosphere, adding 2.0 mL acetonitrile, and adding into 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 28
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 29
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 30
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 97%.
Example 31
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are added to 100 o The reaction was stirred for 12 hours. To be reactedAfter the completion of the purification by column chromatography, the yield of the target product was 93%.
Example 32
105. 105 mg (0.5 mmol) 1, 1-diphenyl-2-propen-1-ol, 143 mg (0.5 mmol) ethoxybis (3, 5-dimethylphenyl) phosphine, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under an air atmosphere, followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 33
105. 105 mg (0.5 mmol) 1, 1-diphenyl-2-propen-1-ol, 143 mg (0.5 mmol) ethoxybis (2, 5-dimethylphenyl) phosphine, 11.3 mg (0.05 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, 18 mg (1.0 mmol) water were introduced into a Schlenk (25 mL) tube under an air atmosphere, followed by 2.0 mL acetonitrile at 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 34
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 35
105. 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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 36
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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 77%.
Example 37
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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile are further added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 95%.
Example 38
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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile are further added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 39
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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, 2.0 mL acetonitrile are then added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 40
155 mg (0.5 mmol) of 1, 1-diphenyl-2-propen-1-ol, 165 mg (0.5 mmol) of ethoxybis (1-naphthalene)Radical) phosphine, 11.3. 11.3 mg (0.05 mmol) zinc bromide, 2.7. 2.7 mg (0.025 mmol) trimethylchlorosilane, 18. 18 mg (1.0 mmol) water, and then put into a Schlenk (25 mL) tube under air, then 2.0. 2.0 mL acetonitrile is added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 41
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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 42
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, 18 mg (1.0 mmol) of water are introduced into a Schlenk (25 mL) tube under an air atmosphere, and 2.0 mL acetonitrile are added to 100 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
As can be seen from the above examples, the method for preparing the corresponding 3, 3-diaryl allyl substituted organic phosphonate compound containing different substituted functional groups by utilizing the trialkyl/aryl phosphite or dialkyl phenyl phosphonate or alkoxy diaryl phosphine and the 1, 1-diaryl-2-propylene-1-alcohol compound has the advantages of mild reaction conditions, low cost and easiness in preparation of the catalyst, and the like. In addition, the method has the advantages of wide substrate applicability, high yield and the like, and provides a method for efficiently synthesizing the 3, 3-diaryl allyl substituted organic phosphonate compounds containing different substituted functional groups.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (4)

1. A trialkyl/aryl phosphite or dialkyl phenylphosphonate or alkoxy diaryl phosphine is reacted with 1, 1-diaryl-2-propylene-1-alcohol compound to prepare the compound with structural formula（I）The preparation method of the 3, 3-diaryl allyl substituted organic phosphonate compound comprises the following specific reaction formula:
（I）
the method is characterized by comprising the following steps of:
taking the reaction amount of trialkyl/aryl phosphite or dialkyl phenylphosphonate or alkoxy diaryl phosphine, 1-diaryl-2-propylene-1-alcohol, catalyst, cocatalyst, auxiliary agent and organic solvent, placing the mixture in a reaction container under the air environment, mixing the mixture under the stirring condition at 25-120 o C, reacting for 5-12 hours to obtain corresponding 3, 3-diaryl allyl substituted organic phosphonate compounds containing different substituted functional groups;
wherein,
the catalyst is zinc bromide, the cocatalyst 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, 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 method according to claim 1, wherein, the 1, 1-diaryl-2-propen-1-ol is selected from the group consisting of 1, 1-diphenyl-2-propen-1-ol, 1-bis (4-methylphenyl) -2-propen-1-ol, 1-bis (4-methoxyphenyl) -2-propen-1-ol, 1-bis (4-fluorophenyl) -2-propen-1-ol, 1-bis (4-chlorophenyl) -2-propen-1-ol, 1-bis (4-bromophenyl) -2-propen-1-ol, 1-phenyl-1- (4-methylphenyl) -2-propen-1-ol, 1-phenyl-1- (2-methylphenyl) -2-propen-1-ol, 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-chlorophenyl) -2-propen-1-ol, 1-fluorophenyl-2-propen-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.
3. The process according to claim 1, wherein the trialkyl/aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine is selected from the group consisting of trimethyl phosphite, triphenyl phosphite, tributyl phosphite, triisopropyl phosphite, diethylphenylphosphonate, ethoxydiphenyl phosphine, ethoxybis (4-methylphenyl) phosphine, ethoxybis (3-methylphenyl) phosphine, ethoxybis (4-ethylphenyl) phosphine, ethoxybis (4-butylphenyl) phosphine, ethoxybis (4-tert-butylphenyl) phosphine, ethoxybis (3, 5-dimethylphenyl) phosphine, ethoxybis (2, 5-dimethylphenyl) phosphine, ethoxybis (4-fluorophenyl) phosphine, ethoxybis (3-fluorophenyl) phosphine, ethoxybis (4-chlorophenyl) phosphine, ethoxybis (4-phenylphenyl) phosphine, ethoxybis (3-phenylphenyl) phosphine, ethoxybis (2-naphthyl) phosphine, ethoxybis (1-naphthyl) phosphine, ethoxyphenyl (4-fluorophenyl) phosphine, ethoxyphenyl (3-fluorophenyl) phosphine.
4. The process of claim 1, wherein the molar ratio of 1, 1-diaryl-2-propen-1-ol to trialkyl/aryl phosphite or dialkylphenylphosphonate or alkoxydiarylphosphine is 1: [1.0 to 1.2]; the molar ratio of the 1, 1-diaryl-2-propylene-1-alcohol to the catalyst and the cocatalyst is 1: [0.05 to 0.2]: [0.01-0.1]; the molar ratio of the 1, 1-diaryl-2-propylene-1-alcohol to the auxiliary agent is 1: [1.0 to 3.0].
CN202311268120.5A 2023-09-28 2023-09-28 Method for preparing 3, 3-diaryl allyl substituted organic phosphonate compound Pending CN117362338A (en)

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