Method for synthesizing allyl phosphorothioate
Through the reaction of elemental sulfur with allyl alcohol and P(O)-H-containing compounds under catalyst-free conditions, the problems of raw material toxicity and environmental pollution in existing phosphorothioate synthesis are solved, and high selectivity and high yield are achieved Allylphosphorus thioate preparation is suitable for industrial applications.
Patent Information
- Application Number
- CN202411274361.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-12
- Publication Date
- 2024-12-13
AI Technical Summary
In the existing phosphorothioate synthesis methods, raw materials with unpleasant smell, toxicity or high environmental pollution are often used, and transition metal catalysts are required, resulting in complex reaction conditions and high environmental pollution.
Elemental sulfur, allyl alcohol and P(O)-H-containing compounds (diarylphosphorus oxygen, alkyl phenylphosphate, dialkyl phosphite) are used to react under catalyst-free conditions, and stir between 40~140 Allylphosphorus thioate was prepared for 4 to 12 hours at °C.
It achieves high selectivity and mild reaction conditions, high yield and simple reaction, and the solvent used is cheap and easy to obtain, and has good industrial application prospects.
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Abstract
Description
Technical Field
[0001] The invention relates to the field of synthesis of allyl thiophosphate, and in particular to a method for preparing allyl thiophosphate by high-efficiency reaction of elemental sulfur with allyl alcohol and a compound containing a P(O)-H bond (diaryl phosphine oxide, alkyl phenyl phosphate, dialkyl phosphite) without the action of a catalyst. Background Art
[0002] Phosphorothioates are an important class of organic synthesis intermediates. Due to their special chemical structure, they are also widely used in the preparation of pharmaceutical intermediates, pesticides, functional materials and catalyst ligands. Therefore, it is of great significance to develop efficient synthesis methods for this class of compounds.
[0003] The methods for synthesizing thiophosphate derivatives reported in the literature mainly include: (1) Based on the Atherton-Todd reaction, thiophenol and diarylphosphoryl chloride are used for nucleophilic substitution reaction to construct SP(O) bonds ( J. Org. Chem. ,2010, 75, 3890; Tetrahedron , 2013, 69, 9373) (eq 1); or using sulfur halide compounds to react with compounds containing P(O)-H bonds to construct SP(O) bonds (eq 2). (2) Using transition metals to catalyze the reaction of disulfide, sulfonyl hydrazide, sulfonyl chloride or elemental sulfur with compounds containing P(O)-H bonds to construct thiophosphates ( Adv. Synth. Catal. , 2014, 356,2591; Chem. Commun. , 2014, 50, 8860; Org. Lett. , 2016, 18, 1266) (eq 3). In addition, in recent years, cross-dehydrogenation coupling reactions have also been used to efficiently construct SP(O) bonds (eq 4). For example, by peroxide induction ( Green Chem. , 2015, 17, 314), or transition metal catalysis ( J. Am. Chem. Soc. , 2016, 138,5825) and photocatalysis ( Org. Lett. , 2016, 18, 5114) and other methods have been used to efficiently synthesize thiophosphates.
[0004] However, the above methods generally use unpleasant-smelling thiophenols and disulfides, or toxic and humidity-sensitive phosphorus oxychloride, or pre-prepared sulfonyl hydrazides as raw materials, or have defects such as complicated experimental steps, the need for catalysts such as transition metals, and high environmental pollution.
[0005]
[0006] In view of the shortcomings of the existing methods for synthesizing thiophosphates, the industry is focusing on the use of mild reaction conditions to efficiently develop new methods for synthesizing the corresponding thiophosphates using stable, green and safe elemental sulfur and P(O)-H bond-containing compounds (diaryl phosphine oxides, alkyl phenyl phosphates, dialkyl phosphites) as building blocks. Summary of the invention
[0007] The object of the present invention is to provide a novel method for highly selectively synthesizing corresponding thiophosphates from elemental sulfur, allyl alcohol and a compound containing a P(O)-H bond (diarylphosphine oxide, alkyl phenyl phosphate, dialkyl phosphite) as raw materials, so as to overcome the above-mentioned defects in the prior art.
[0008] The present invention comprises the following steps: taking a reaction amount of an allyl alcohol compound, a diaryl phosphine compound, elemental sulfur and an organic solvent and placing them in a reaction container for mixing, and reacting them at 40-140° C. for 4-12 hours under stirring to obtain the corresponding thiophosphate containing different substituted functional groups. The specific reaction formula is as follows: （I） in, R 1 is selected from methyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3,4-dimethylphenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 1-naphthyl; R 2 is selected from methyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3,4-dimethylphenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 1-naphthyl; R 3 is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 4-methoxyphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 4-fluorophenyl, 2-methoxyphenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, benzyloxy; R 4 is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 4-methoxyphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 4-fluorophenyl, 2-methoxyphenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, benzyloxy.
[0009] In the above method, the allyl alcohol is selected from 1,1-dimethylallyl alcohol, 1,1-diphenylallyl alcohol, 1,1-bis(4-methylphenyl)allyl alcohol, 1,1-bis(4-methoxyphenyl)allyl alcohol, 1,1-bis(4-fluorophenyl)allyl alcohol, 1,1-bis(2-methylphenyl)allyl alcohol, 1,1-bis(4-chlorophenyl)allyl alcohol, 1,1-bis(4-bromophenyl)allyl alcohol, 1,1-bis(3,4-dimethylphenyl)allyl alcohol, 1,1-bis(4-trifluoromethylphenyl)allyl alcohol, 1,1-bis(2- Allyl alcohol, 1-(4-methylphenyl)-1-phenyl allyl alcohol, 1-(3,4-dimethylphenyl)-1-phenyl allyl alcohol, 1-(4-methylphenyl)-1-phenyl allyl alcohol, 1-(4-chlorophenyl)-1-phenyl allyl alcohol, 1-(4-bromophenyl)-1-phenyl allyl alcohol, 1-(4-trifluoromethylphenyl)-1-phenyl allyl alcohol, 1-(2-fluorophenyl)-1-phenyl allyl alcohol.
[0010] In the above method, the compound containing P(O)-H bond (diarylphosphine oxide, phenyl alkyl phosphate, dialkyl phosphite) is selected from diphenylphosphine oxide, bis(4-methylphenyl)phosphine oxide, bis(2-methylphenyl)phosphine oxide, bis(p-methoxyphenyl)phosphine oxide, bis(2,5-dimethylphenyl)phosphine oxide, bis(3,5-dimethylphenyl)phosphine oxide, bis(4-phenylbenzene)phosphine oxide, bis(4-fluorophenyl)phosphine oxide, bis(2-methoxyphenyl)phosphine oxide, bis(1-naphthalene)phosphine oxide, bis(2-naphthalene)phosphine oxide, phenyl(2-methylphenyl)phosphine oxide, phenyl(2-methoxyphenyl)phosphine oxide, dimethyl phosphite, diethyl phosphite, and dibenzyl phosphite.
[0011] In the above method, the solvent is acetonitrile, water, dimethyl sulfoxide, N , N -One of dimethylformamide, 1,4-dioxane, toluene, and tetrahydrofuran.
[0012] In the above method, the molar ratio of the allyl alcohol compound, elemental sulfur and diarylphosphine oxide compound is 1:1:1.
[0013] The method for synthesizing allyl thiophosphate by three-component reaction of allyl alcohol, elemental sulfur and a compound containing a P(O)-H bond (diaryl phosphorus oxide, phenyl alkyl phosphate, dialkyl phosphite) provided by the present invention has a mild and easy-to-control reaction process. While obtaining a high yield and 100% regioselectivity, the method is simple and easy to operate, and the organic solvent used is cheap and easily available, the preparation is simple, and the method has good industrial application prospects. DETAILED DESCRIPTION
[0015] The present invention will be further described below in conjunction with embodiments of the present invention: 1. Testing and Analysis The structural analysis of the reaction products in the following examples of the present invention was performed using a gas phase-mass spectrometer GC / MS (6890N / 5973N) equipped with an HP-5MS capillary chromatographic column (30m×0.45mm×0.8μm) produced by Agilent and a Bruker Avance-III 400 nuclear magnetic resonance analyzer produced by Bruker. The selectivity and yield of the target product were analyzed using a Bruker Avance-III 400 nuclear magnetic resonance analyzer produced by Bruker. 2. Embodiment
[0016] Example 1
[0017] Prepare a set of parallel reactions. Add 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 40.4 mg (0.2 mmol) of diphenylphosphine oxide into Schlenk tubes under nitrogen atmosphere. Then add different types of solvents (acetonitrile, water, dimethyl sulfoxide, N , N -dimethylformamide, 1,4-dioxane, toluene, tetrahydrofuran) 1 ml, at 120 o C and stirred for 12 hours. According to the nuclear magnetic phosphorus spectrum, when the solvent is acetonitrile, the yield of the target product is the highest, which is 95%. In the above parallel reaction, the yields of the target product in other solvents are as follows: water, 72%; dimethyl sulfoxide, 10%; N , N -Dimethylformamide, 15%; 1,4-dioxane, 52%; toluene, 55%; tetrahydrofuran, 75%.
[0018] Example 2 Prepare a set of parallel reactions. Add 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 40.4 mg (0.2 mmol) of diphenylphosphine oxide into a Schlenk tube under nitrogen atmosphere, and then add 1 mL of acetonitrile as solvent. o C. 60 o C. 80 o C. 100 o C. 120 o C and 140 oC. Stir the reaction for 12 hours. By gas chromatography analysis, when the temperature is 100 o C, the yield of the target product is the highest, which is 93%. In the above parallel reactions, the yields of the target products at other reaction temperatures are as follows: o C, 70%; 60 o C, 78%; 80 o C, 90%; 120 o C, 83%.
[0019] Example 3 17.2 mg (0.2 mmol) of 1,1-dimethylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 65%.
[0020] Example 4 46.7 mg (0.2 mmol) of 1,1-di(4-methylphenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0021] Example 5 54.6 mg (0.2 mmol) of 1,1-bis(4-methoxyphenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 92%.
[0022] Example 6 49.3 mg (0.2 mmol) of 1,1-bis(4-fluorophenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. oC and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 95%.
[0023] Example 7 46.7 mg (0.2 mmol) of 1,1-di(2-methylphenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 88%.
[0024] Example 8 55.8 mg (0.2 mmol) of 1,1-bis(4-chlorophenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 94%.
[0025] Example 9 73.6 mg (0.2 mmol) of 1,1-bis(4-chlorophenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0026] Example 10 53.3 mg (0.2 mmol) of 1,1-bis(3,4-dimethylphenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0027] Embodiment 11 69.3 mg (0.2 mmol) of 1,1-bis(4-trifluoromethylphenyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 86%.
[0028] Example 12 62.1 mg (0.2 mmol) of 1,1-di(1-naphthyl)allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 88%.
[0029] Embodiment 13 29.6 mg (0.2 mmol) of 1-methyl-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were added to a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 65%.
[0030] Embodiment 14 39.7 mg (0.2 mmol) of 1-methyl-1-naphthyl allyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 70%.
[0031] Embodiment 15 44.9 mg (0.2 mmol) of 1-(4-methylphenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. oC and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 94%.
[0032] Example 16 47.7 mg (0.2 mmol) of 1-(3,4-dimethylphenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 91%.
[0033] Embodiment 17 48.1 mg (0.2 mmol) of 1-(4-methoxyphenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 92%.
[0034] Embodiment 18 44.9 mg (0.2 mmol) of 1-(4-methylphenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 94%.
[0035] Embodiment 19 48.9 mg (0.2 mmol) of 1-(4-chlorophenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 87%.
[0036] Embodiment 20 57.8 mg (0.2 mmol) of 1-(4-bromophenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 88%.
[0037] Embodiment 21 55.7 mg (0.2 mmol) of 1-(4-trifluoromethylphenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0038] Embodiment 22 45.7 mg (0.2 mmol) of 1-(2-fluorophenyl)-1-phenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur and 40.4 mg (0.2 mmol) of diphenylphosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0039] Embodiment 23 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 46.1 mg (0.2 mmol) of bis(4-methylphenyl)phosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 95%.
[0040] Embodiment 24 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 46.1 mg (0.2 mmol) of bis(2-methylphenyl)phosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent.o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 85%.
[0041] Embodiment 25 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 52.4 mg (0.2 mmol) of bis(p-methoxyphenyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0042] Embodiment 26 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 51.7 mg (0.2 mmol) of bis(2,5-dimethylphenyl)phosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 92%.
[0043] Embodiment 27 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 51.7 mg (0.2 mmol) of bis(3,5-dimethylphenyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 83%.
[0044] Embodiment 28 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 70.9 mg (0.2 mmol) of bis(4-phenylbenzene)phosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 96%.
[0045] Embodiment 29 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 47.6 mg (0.2 mmol) of bis(4-fluorophenyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 96%.
[0046] Embodiment 30 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 52.4 mg (0.2 mmol) of bis(2-methoxyphenyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 85%.
[0047] Embodiment 31 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 60.5 mg (0.2 mmol) of bis(1-naphthyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 90%.
[0048] Embodiment 32 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 60.5 mg (0.2 mmol) of bis(2-naphthyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 92%.
[0049] Embodiment 33 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 43.2 mg (0.2 mmol) of phenyl (2-methylphenyl) phosphine oxide were placed in a Schlenk tube under a nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. oC and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 85%.
[0050] Embodiment 34 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 46.4 mg (0.2 mmol) of bis(2-methoxyphenyl)phosphine oxide were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 75%.
[0051] Embodiment 35 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 22.1 mg (0.2 mmol) of dimethyl phosphite were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 85%.
[0052] Embodiment 36 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 27.6 mg (0.2 mmol) of diethyl phosphite were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 88%.
[0053] Embodiment 37 42.1 mg (0.2 mmol) of 1,1-diphenylallyl alcohol, 6.4 mg (0.2 mmol) of elemental sulfur, and 52.4 mg (0.2 mmol) of dibenzyl phosphite were placed in a Schlenk tube under nitrogen atmosphere, and 1 mL of acetonitrile was added as solvent. o C and stirred for 12 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 88%.
[0054] It can be seen from the above examples that the method for preparing allyl thiophosphates by reacting allyl alcohol compounds, elemental sulfur and compounds containing P(O)-H bonds (diaryl phosphine oxides, alkyl phenyl phosphates, dialkyl phosphites) used in the present invention has the advantages of mild reaction conditions, cheap and readily available reaction solvents, and high regioselectivity. In addition, the method also has the advantages of wide substrate applicability and high yield, and provides a method for efficiently synthesizing thiophosphates containing different substituted functional groups.
[0055] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.
Claims
1. A method for preparing a compound having the structural formula by reacting an allyl alcohol compound, elemental sulfur and a compound containing a P(O)-H bond (diarylphosphine oxide, phenyl alkyl phosphate, dialkyl phosphite). （I） The preparation method of allyl thiophosphate is as follows: （I） It is characterized in that The following steps are included: Taking a reaction amount of an allyl alcohol compound, elemental sulfur, a compound containing a P(O)-H bond and an organic solvent, placing them in a reaction container and mixing them, reacting them at 40-140° C. for 4-12 hours under stirring, thereby obtaining the corresponding allyl thiophosphate containing different substituted functional groups; in, R 1 is selected from methyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3,4-dimethylphenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 1-naphthyl; R 2 is selected from methyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3,4-dimethylphenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 1-naphthyl; R 3 is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 4-methoxyphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 4-fluorophenyl, 2-methoxyphenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, benzyloxy; R 4 is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 4-methoxyphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 4-fluorophenyl, 2-methoxyphenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, benzyloxy.
2. The preparation method according to claim 1, characterized in that: The allyl alcohol is selected from 1,1-dimethylallyl alcohol, 1,1-diphenylallyl alcohol, 1,1-di(4-methylphenyl)allyl alcohol, 1,1-di(4-methoxyphenyl)allyl alcohol, 1,1-di(4-fluorophenyl)allyl alcohol, 1,1-di(2-methylphenyl)allyl alcohol, 1,1-di(4-chlorophenyl)allyl alcohol, 1,1-di(4-bromophenyl)allyl alcohol, 1,1-di(3,4-dimethylphenyl)allyl alcohol, 1,1-di(4-trifluoromethylphenyl)allyl alcohol, 1,1-di(2-fluorophenyl)allyl alcohol, ) allyl alcohol, 1,1-di(1-naphthyl)allyl alcohol, 1-methyl-1-phenylallyl alcohol, 1-methyl-1-naphthylallyl alcohol, 1-(4-methylphenyl)-1-phenylallyl alcohol, 1-(3,4-dimethylphenyl)-1-phenylallyl alcohol, 1-(4-methylphenyl)-1-phenylallyl alcohol, 1-(4-chlorophenyl)-1-phenylallyl alcohol, 1-(4-bromophenyl)-1-phenylallyl alcohol, 1-(4-trifluoromethylphenyl)-1-phenylallyl alcohol, 1-(2-fluorophenyl)-1-phenylallyl alcohol.
3. The preparation method according to claim 1, characterized in that: The phosphine hydrogen compound is selected from diphenylphosphine oxide, bis(4-methylphenyl)phosphine oxide, bis(2-methylphenyl)phosphine oxide, bis(p-methoxyphenyl)phosphine oxide, bis(2,5-dimethylphenyl)phosphine oxide, bis(3,5-dimethylphenyl)phosphine oxide, bis(4-phenylbenzene)phosphine oxide, bis(4-fluorophenyl)phosphine oxide, bis(2-methoxyphenyl)phosphine oxide, bis(1-naphthalene)phosphine oxide, bis(2-naphthalene)phosphine oxide, phenyl(2-methylphenyl)phosphine oxide, phenyl(2-methoxyphenyl)phosphine oxide, dimethyl phosphite, diethyl phosphite, and dibenzyl phosphite.
4. The preparation method according to claim 1, characterized in that: The solvent is acetonitrile, water, dimethyl sulfoxide, N , N -One of dimethylformamide, 1,4-dioxane, toluene, and tetrahydrofuran.
5. The preparation method according to claim 1, characterized in that: The molar ratio of the allyl alcohol compound, elemental sulfur and the compound containing a P(O)-H bond is 1:[1-2]:[1-2].