Substituted phenol compounds, methods of making and using the same
By preparing substituted phenol compounds and reacting them with dihalomethyl ethers and diarylphosphine salts, the problems of complex and high cost in the synthesis of existing bidentate phosphine ligands were solved, and high conversion and selectivity in efficient hydroformylation reactions were achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2022-06-02
- Publication Date
- 2026-06-12
AI Technical Summary
The synthesis of existing bidentate phosphine ligands is complex and costly. Furthermore, the hydroformylation reaction requires sophisticated equipment and consumes a lot of energy, which affects their usability and stereoselectivity.
By preparing substituted phenol compounds, a compound with the structure of formula (I) is subjected to a substitution reaction with a dihalomethyl ether, followed by contact with a diarylphosphine salt to prepare a phosphine ligand compound with a phenol group, which is then used for hydroformylation reaction.
A high-conversion and high-selectivity method for preparing 3,5-bis[(diarylphosphino)methyl]-phenolphosphine ligands was achieved for the hydroformylation of olefins and their derivatives, with conversion and aldehyde selectivity both exceeding 85%.
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Figure CN117209364B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic synthesis technology, and more specifically, to a substituted phenol compound, its preparation method, and its application. Background Technology
[0002] 3,5-bis(halomethyl)-2,4,6-trisubstituted phenyl compounds are important intermediates in the synthesis of bidentate phosphine ligands, so their synthesis is directly related to the overall yield and synthesis cost of bidentate phosphine ligands.
[0003] Currently, m-bis(halomethyl)benzene is a major raw material for the preparation of bidentate phosphine ligands. For example, 1,3-bis(bromomethyl)benzene can be reacted with triphenylphosphine to produce 1,3-bis[(diphenylphosphino)methyl]benzene [Wu, Qianhui et al, RSC Advances, 6(109), 107305-107309; 2016]. 1,3-bis(bromomethyl)benzene is generally prepared by bromination of m-xylene [Wei, Jianping et al, Australian Journal of Chemistry, 68(6), 919-925; 2015] or bromination of m-bis(hydroxymethyl)benzene [Radaram Bhasker and Levine Mindy, Tetrahedron Letters, 55(35), 4905-4908; 2014].
[0004] However, some of the currently known bidentate phosphine ligands have overly complex structures, making their synthesis difficult; others, once prepared as catalysts, require the hydroformylation reaction to be carried out under harsh temperature and pressure conditions, placing higher demands on equipment and consuming more energy, thus limiting their application. Therefore, finding new bidentate phosphine ligands is of great significance for improving the activity of hydroformylation catalysts, extending their effectiveness, and controlling the stereoselectivity of chemical synthesis. Summary of the Invention
[0005] The purpose of this invention is to overcome the technical problems existing in the prior art and to provide a substituted phenol compound, its preparation method, and its application.
[0006] To achieve the above objectives, a first aspect of the present invention provides a substituted phenol compound having the structure shown in formula (I):
[0007]
[0008] In formula (I), R1, R2 and R3 are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy;
[0009] X1 and X2 are each halogens independently.
[0010] A second aspect of the present invention provides a method for preparing a substituted phenol compound, the method comprising: subjecting a compound of formula (II) and a dihalomethyl ether of formula (III) to a substitution reaction;
[0011]
[0012] In Equation (II) or Equation (III), R1, R2, R3, X1, and X2 have the same definitions as in the first aspect mentioned above.
[0013] A third aspect of the present invention provides the use of the aforementioned compounds and / or the aforementioned methods in the preparation of phosphine ligand compounds, particularly in the preparation of phosphine ligand compounds for hydroformylation reactions.
[0014] A fourth aspect of the present invention provides a method for preparing a phosphine ligand compound having a phenol group, the method comprising: contacting a diarylphosphine salt of formula (IV) with a substituted phenol of formula (I) as described above;
[0015]
[0016] In equation (IV), m and n are each an independent integer from 1 to 4, and M is an alkali metal element;
[0017] In formula (IV), R1' and R2' are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy.
[0018] The fifth aspect of the present invention provides a phosphine ligand compound having a phenolic group prepared by the method described in the fourth aspect above.
[0019] The sixth aspect of the present invention provides the application of the phosphine ligand compound having a phenol group as described in the fifth aspect above in the hydroformylation reaction, particularly in the hydroformylation reaction of vinyl acetate.
[0020] Compared with existing technologies, this invention provides novel substituted phenolic compounds that can be used to prepare 2,4,6-substituted or unsubstituted 3,5-bis[(diarylphosphino)methyl]-phenolphosphine ligands. These phosphine ligands can be further applied to the hydroformylation of olefins and their derivatives, achieving high conversion rates of olefins and their derivatives and high aldehyde selectivity. In this invention, the conversion rates of olefins and their derivatives and the aldehyde selectivity can both reach 85% or higher, preferably 90% or higher. Detailed Implementation
[0021] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0022] A first aspect of the present invention provides a substituted phenol compound having the structure shown in formula (I):
[0023]
[0024] In formula (I), R1, R2 and R3 are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy;
[0025] X1 and X2 are each halogens independently.
[0026] According to some embodiments of the present invention, R1, R2 and R3 may each be independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C10 alkoxy, C6-C10 aryl, C7-C10 alkylaryl, C7-C10 aralkyl, C1-C6 acyl or C1-C6 acyloxy.
[0027] According to some embodiments of the present invention, R1, R2 and R3 are each independently selected from H, halogen, C1-C6 straight-chain or branched alkyl or C6-C10 aryl.
[0028] According to some embodiments of the present invention, X1 and X2 may each be independently one of F, Cl, Br and I. Preferably, Cl or Br.
[0029] According to some embodiments of the present invention, the compound has the following structure:
[0030]
[0031] A second aspect of the present invention provides a method for preparing a substituted phenol compound, the method comprising: subjecting a compound of formula (II) and a dihalomethyl ether of formula (III) to a substitution reaction;
[0032]
[0033] In Equation (II) or Equation (III), R1, R2, R3, X1, and X2 have the same definitions as in the first aspect mentioned above.
[0034] According to some embodiments of the present invention, the conditions for the substitution reaction may include: a temperature of -50°C to 100°C and a time of 1-48 hours.
[0035] According to some embodiments of the present invention, the molar ratio of the compound represented by formula (II) and the dihalomethyl ether represented by formula (III) can be 1:(1-10).
[0036] According to some embodiments of the present invention, the substitution reaction is carried out in the presence of a Lewis acid, the amount of which may be 0.01-1 mmol (e.g., any value between 0.01 mol, 0.02 mol, 0.05 mol, 0.1 mol, 0.15 mol, 0.2 mol, 0.5 mol, 1 mol or more) relative to 1 mmol of the compound represented by formula (II).
[0037] According to some embodiments of the present invention, the Lewis acid may be selected from at least one of tin halides, germanium halides, and zinc halides. More preferably, the Lewis acid is selected from at least one of tin chloride, tin bromide, tin iodide, tin sulfate, germanium chloride, and zinc chloride.
[0038] Preferably, relative to 1 mmol of the compound represented by formula (II), the rate of addition of the Lewis acid can be 0.01-1 mmol / h (0.01 mmol / h, 0.02 mmol / h, 0.03 mmol / h, 0.05 mmol / h, 0.08 mmol / h, 0.1 mmol / h, 0.2 mmol / h, 0.5 mmol / h, 0.8 mmol / h, 1 mmol / h or any value between the above).
[0039] According to some embodiments of the present invention, the substitution reaction can be carried out in the presence of a first solvent. The first solvent may be selected from at least one of C4-C8 alkanes, C6-C12 cycloalkanes, C6-C10 aromatics, C2-C6 ethers, and C4-C8 oxocyclic rings. Preferably, the first solvent is selected from at least one of n-hexane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, acetone, diethyl ether, methyl tert-butyl ether, and isopropyl ether.
[0040] The present invention does not impose any particular limitation on the amount of the first solvent, as long as it can meet the requirements of the present invention. For example, the amount of the first solvent is 1-150 mL relative to 1 g of the compound represented by formula (II).
[0041] This invention does not impose any particular restrictions on the post-processing of the reaction between the compound shown in formula (II) and the dihalomethyl ether shown in formula (III), as long as it meets the requirements of this invention. For example, after the reaction is completed, the crude product is separated by optional acidification (e.g., acidification to pH 1-2), extraction, optional alkali washing, water washing, drying and evaporation; the crude product is then purified by commonly used purification methods, such as distillation, crystallization, recrystallization, thin-layer chromatography or column chromatography, to obtain the pure product (the compound shown in formula (I)).
[0042] The method for preparing substituted phenol compounds provided by this invention has the advantages of high selectivity for meta-substituted phenols and high yield.
[0043] A third aspect of the present invention provides the use of the aforementioned compounds and / or the aforementioned methods in the preparation of phosphine ligand compounds, particularly in the preparation of phosphine ligand compounds for hydroformylation reactions.
[0044] A fourth aspect of the present invention provides a method for preparing a phosphine ligand compound having a phenol group, the method comprising: contacting a diarylphosphine salt of formula (IV) with a substituted phenol of formula (I) as described above;
[0045]
[0046] In equation (IV), m and n are each an independent integer from 1 to 4, and M is an alkali metal element;
[0047] In formula (IV), R1' and R2' are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy. "---m(R1')" indicates that the number of substituents R1' on the benzene ring is m, in any position, as does "---(R2')n".
[0048] According to some embodiments of the present invention, M may be selected from Li, Na and K.
[0049] According to some embodiments of the present invention, R1' and R2' are each independently selected from H, halogen, nitro, C1-C5 straight-chain or branched alkyl, C3-C10 alkoxy, C6-C10 aryl, C7-C10 alkylaryl, C7-C10 aralkyl, C1-C6 acyl or C1-C6 acyloxy.
[0050] According to some embodiments of the present invention, R1' and R2' are each independently selected from H, halogens, C1-C5 straight-chain or branched alkyl groups or C6-C10 aryl groups.
[0051] In this invention, the compound with the structure shown in formula (IV) can be selected from one of the following substances: lithium diphenylphosphine, sodium diphenylphosphine, potassium diphenylphosphine, lithium dinaphthylphosphine, potassium dinaphthylphosphine, and sodium dinaphthylphosphine, or derivatives of the above substances containing substituents on the aromatic ring. The substituents on the aromatic ring can be H, halogens, C1-C5 straight-chain or branched alkyl groups, C3-C10 alkoxy groups, C6-C10 aryl groups, C7-C10 alkylaryl groups, C7-C10 aralkyl groups, acyl groups, or acyloxy groups.
[0052] In this invention, the compound with the structure shown in formula (I) can be selected from one of the following substances: 3,5-bis(chloromethyl)-phenol, 3,5-bis(bromomethyl)-phenol, 3,5-bis(chloromethyl)-2,4,6-trimethylphenol, 3,5-bis(bromomethyl)-2,4,6-trimethylphenol; 3,5-bis(chloromethyl)-2,4,6-triethylphenol, 3,5-bis(bromomethyl)-2,4,6-triethylphenol; 3,5-bis(chloromethyl)-2,4,6-triphenylphenol, 3,5-bis(bromomethyl)-2,4,6-triphenylphenol; 3,5-bis(chloromethyl)-2,6-dimethyl-4-isopropylphenol, 3,5-bis(bromomethyl)-2,6-dimethyl-4-isopropylphenol, 3,5-bis(bromomethyl)-2,4,6-triisopropylphenol, etc.
[0053] Preferably, the compound with the structure shown in formula (I) can be selected from one of the following substances: 3,5-bis(chloromethyl)-2,4,6-trimethylphenol, 3,5-bis(chloromethyl)-2,4,6-triethylphenol, 3,5-bis(bromomethyl)-2,4,6-trimethylphenol, 3,5-bis(bromomethyl)-2,4,6-triethylphenol, 3,5-bis(chloromethyl)-phenol, 3,5-bis(chloromethyl)-2,4,6-triisopropylphenol, 3,5-bis(chloromethyl)-2,4,6-triphenylphenol, etc.
[0054] According to a preferred embodiment of the present invention, in formula (IV), R1' and R2' are both CH3, and in formula (I), R1, R2, and R3 are all CH3; or,
[0055] In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all CH2CH3; or,
[0056] In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all CH3; or,
[0057] In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all H; or,
[0058] In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all CH(CH3)2; or,
[0059] In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all Ph; or
[0060] In equation (IV), R1' and R2' are both F; in equation (I), R1, R2, and R3 are all CH3; or,
[0061] In formula (IV), R1' and R2' are both Cl; in formula (I), R1, R2, and R3 are all CH3; or,
[0062] In formula (IV), R1' and R2' are both Br, and in formula (I), R1, R2, and R3 are all CH3.
[0063] According to some embodiments of the present invention, the diarylphosphine salt represented by formula (IV) is sodium di-p-chloromethylphenylphosphine, and the substituted phenol of formula (I) is 3,5-bis(chloromethyl)-2,4,6-trimethylphenol; or,
[0064] The diarylphosphine salt shown in formula (IV) is potassium diphenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(chloromethyl)-2,4,6-triethylphenol; or,
[0065] The diarylphosphine salt shown in formula (IV) is potassium diphenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(bromomethyl)-2,4,6-trimethylphenol; or,
[0066] The diarylphosphine salt shown in formula (IV) is potassium di-p-bromophenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(bromomethyl)-2,4,6-trimethylphenol; or,
[0067] The diarylphosphine salt shown in formula (IV) is potassium diphenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(chloromethyl)-phenol; or,
[0068] The diarylphosphine salt shown in formula (IV) is potassium diphenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(chloromethyl)-2,4,6-triisopropylphenol; or,
[0069] The diarylphosphine salt shown in formula (IV) is lithium diphenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(chloromethyl)-2,4,6-triphenylphenol; or,
[0070] The diarylphosphine salt shown in formula (IV) is sodium di-p-methylphenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(chloromethyl)-2,4,6-trimethylphenol; or,
[0071] The diarylphosphine salt shown in formula (IV) is sodium dichlorophenylphosphine, and the substituted phenol in formula (I) is 3,5-bis(chloromethyl)-2,4,6-trimethylphenol.
[0072] According to some embodiments of the present invention, the contact conditions may include a temperature of -50°C to 100°C and a time of 1-48 hours. Preferably, the contact is carried out under an inert atmosphere. The inert atmosphere is preferably provided by nitrogen. Preferably, the contact is carried out under anhydrous conditions.
[0073] In this invention, the contact is preferably carried out in the following manner: at a temperature of -50°C to 30°C, the compound represented by formula (IV) is added to the system containing the substituted phenol represented by formula (I) at a rate of 1-5 mol / h, preferably 2-3 mol / h; or, at a temperature of -30°C to 30°C, the compound represented by formula (I) is added to the system containing the substituted phenol represented by formula (IV) at a rate of 1-5 mol / h, preferably 2-3 mol / h.
[0074] According to some embodiments of the present invention, the molar ratio of the diarylphosphine salt shown in formula (IV) to the substituted phenol shown in formula (I) can be (1.5-3):1.
[0075] According to some embodiments of the present invention, the contact can be carried out in the presence of a second solvent.
[0076] In this invention, the second solvent can be an aprotic solvent.
[0077] Preferably, the second solvent may be selected from at least one of C4-C8 alkanes, C6-C12 cycloalkanes, C6-C10 aromatics, C2-C6 ethers, and C4-C8 oxocyclic rings. More preferably, the second solvent may be selected from at least one of n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, acetone, diethyl ether, methyl tert-butyl ether, and isopropyl ether.
[0078] There is no particular limitation on the amount of the second solvent used, as long as it meets the requirements of the present invention. For example, relative to 1 mmol of the substituted phenol shown in formula (I), the amount of the second solvent can be 1-50 mL.
[0079] This invention does not impose any particular limitations on the post-processing of the reaction between the diarylphosphine salt shown in formula (IV) and the substituted phenol shown in formula (I), as long as it meets the requirements of this invention. For example, it can be carried out as follows: the solvent in the reaction system is removed to obtain the residue, which is then extracted with an extraction solvent (such as dichloromethane, ethyl acetate, etc.), retaining the organic phase. After drying and solvent removal, a crude product containing the target product is obtained, followed by further separation and purification (such as distillation, crystallization, recrystallization, thin-layer chromatography, column chromatography, etc.). There are no particular limitations on the specific operating conditions for separation and purification, as well as the type and amount of solvent used for purification, as long as it meets the requirements of this invention.
[0080] In this invention, the diarylphosphine salt represented by formula (IV) can be obtained commercially or prepared in-house. Taking the preparation of lithium diphenylphosphine as an example: diphenylphosphine is contacted with butyllithium at a temperature ranging from -80°C to 0°C. The molar ratio of diphenylphosphine to butyllithium can be 1:(1-5).
[0081] The fifth aspect of the present invention provides a phosphine ligand compound having a phenolic group prepared by the method described in the fourth aspect above.
[0082] The phosphine ligand compound has the structure shown in formula (1):
[0083]
[0084] In equation (1), n, m, p and q are each an independent integer from 1 to 4;
[0085] R1, R2, R3, R1', R2', R3' and R4' are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy.
[0086] According to some embodiments of the present invention, R1, R2, R3, R1', R2', R3' and R4' are each independently selected from H, halogen, nitro, C1-C5 straight-chain or branched alkyl, C3-C10 alkoxy, C6-C10 aryl, C7-C10 alkylaryl, C7-C10 aralkyl, C1-C6 acyl or C1-C6 acyloxy.
[0087] Preferably, R1, R2, R3, R1', R2', R3' and R4' can each be independently selected from H, C1-C5 straight-chain or branched alkyl or C6-C10 aryl.
[0088] According to some embodiments of the present invention, R1, R2, R3, R1', R2', R3' and R4' are all CH3.
[0089] According to some embodiments of the present invention, R1', R2', R3', and R4' are all H, and R1, R2, and R3 are all CH2CH3.
[0090] According to some embodiments of the present invention, R1', R2', R3', and R4' are all H, and R1, R2, and R3' are all CH3.
[0091] According to some embodiments of the present invention, R1', R2', R3', R4', R1, R2, and R3 are all H.
[0092] According to some embodiments of the present invention, R1', R2', R3', and R4' are all H, and R1, R2, and R3 are all CH(CH3)2.
[0093] According to some embodiments of the present invention, R1', R2', R3', and R4' are all H, and R1, R2, and R3 are all Ph.
[0094] According to some embodiments of the present invention, R1', R2', R3', and R4' are all F, and R1, R2, and R3 are all CH3.
[0095] According to some embodiments of the present invention, R1', R2', R3', and R4' are all Cl, and R1, R2, and R3 are all CH3.
[0096] According to some embodiments of the present invention, R1', R2', R3', and R4' are all Br, and R1, R2, and R3 are all CH3.
[0097] Specifically, the phosphine ligand compound having a phenolic group has the structure shown in formulas A-G:
[0098]
[0099] The aforementioned phosphine ligand compounds (bisphosphine ligands) of this invention are excellent ligands for catalytic reactions and can be applied in many metal-catalyzed reactions. They can catalyze cross-coupling reactions such as CC, CN, and CO with transition metals. For example, they can coordinate with Pd for CC coupling reactions, with Ru for olefin metathesis, amide synthesis, hydrogenation, etc., and with Rh for hydroformylation reactions, etc.
[0100] In particular, the sixth aspect of the present invention provides the use of the phosphine ligand compound with a phenol group described in the fifth aspect above in the hydroformylation reaction of olefins (such as 1-hexene, 1-decene, etc.) and their derivatives, especially in the hydroformylation reaction of vinyl acetate.
[0101] Specifically, the aforementioned phosphine ligand and rhodium complex provided by the present invention can form a catalyst system for hydroformylation reaction.
[0102] Therefore, the present invention also provides a method for hydroformylation of vinyl acetate, comprising the following steps:
[0103] In the presence of a rhodium complex and the aforementioned phosphine ligand, vinyl acetate is contacted with carbon monoxide and hydrogen to undergo a hydroformylation reaction.
[0104] According to some embodiments of the present invention, the rhodium complex is selected from at least one of acetylacetone triphenylphosphine carbonyl rhodium, acetylacetone carbonyl rhodium and triphenylphosphine hydrogen rhodium, preferably acetylacetone triphenylphosphine carbonyl rhodium.
[0105] In this invention, the conditions for the hydroformylation reaction may include: a temperature of 70-200℃, preferably 80-150℃; and a pressure of 1-10MPa, preferably 3-8MPa.
[0106] In this invention, the molar ratio of rhodium to phosphine ligand in the rhodium complex is 1:(1-5), preferably 1:(2-4).
[0107] In this invention, the molar ratio of vinyl acetate to rhodium in the rhodium complex is (1000-5000):1.
[0108] In this invention, the volume ratio of carbon monoxide to hydrogen in the hydroformylation reaction can be (0.1-10):1, preferably (0.2-5):1. This invention does not have special requirements regarding the source of carbon monoxide and hydrogen; preferably, the carbon monoxide and hydrogen are provided by syngas.
[0109] In this invention, the hydroformylation reaction can be carried out in the presence of a solvent or under solvent-free conditions. The solvent for the hydroformylation reaction can be selected from at least one of C5-C20 aliphatic hydrocarbons, C6-C12 aromatic hydrocarbons, C5-C20 ethers, and C5-C20 alcohols, more preferably from at least one of C5-C10 alkanes, C6-C8 aromatic hydrocarbons, C5-C10 ethers, and C5-C10 alcohols. For example, it can be selected from at least one of hexane (such as n-hexane), heptane, benzene, toluene, 1,3-xylene, 1,4-xylene, 1,3,5-trimethylbenzene, methyl tert-butyl ether, isopropyl ether, and isopentyl glycol, more preferably from at least one of toluene, cyclohexane, and methyl tert-butyl ether. The volume ratio of the solvent to vinyl acetate is preferably (0.01-10):1, more preferably (0.01-8):1.
[0110] The present invention will be described in detail below through embodiments.
[0111] In the following examples, unless otherwise specified, all starting materials, solvents, bases, catalysts, etc. are commercially available products.
[0112] The following preparation examples illustrate the preparation of substituted phenols.
[0113] Preparation Example 1
[0114] This preparation utilizes the instructions for the preparation of 3,5-bis(chloromethyl)-2,4,6-trimethylphenol.
[0115]
[0116] At -10℃, 1.36 g of 2,4,6-trimethylphenol, 2.76 g of dichloromethyl ether, and 100 mL of toluene were added sequentially to a three-necked flask. A 1 M dichloromethane solution of tin chloride was added dropwise, and the mixture was stirred for a certain period. After the reaction was complete, the mixture was acidified to pH 1 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali, washed with water, dried, and evaporated to separate the crude product. The crude product was then purified using conventional methods, with column chromatography yielding 2.02 g of purified product.
[0117] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 2.3 (s, 1H, OH), 2.44 (s, 9H, CH3), 4.76 (s, 4H, CH2).
[0118] Preparation Example 2
[0119] This preparation utilizes the instructions for the preparation of 3,5-bis(chloromethyl)-2,4,6-triethylphenol.
[0120]
[0121] At -10℃, 1.78 g of 2,4,6-triethylphenol, 2.76 g of dichloromethyl ether, and 100 mL of n-hexane were added sequentially to a three-necked flask. A 1 M dichloromethane solution of tin chloride was added dropwise, and the mixture was stirred for a certain period. After the reaction was complete, the mixture was acidified to pH 1 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali, washed with water, dried, and evaporated to separate the crude product. The crude product was then purified using conventional methods, including column chromatography, to obtain 2.26 g of purified product.
[0122] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 1.32 (m, 9H, CH3), 2.25 (s, 1H, OH), 2.46 (q, 2H, CH2), 2.63 (q, 4H, CH2), 4.55 (s, 4H, CH2).
[0123] Preparation Example 3
[0124] This preparation example illustrates the preparation of 3,5-bis(bromomethyl)-2,4,6-trimethylphenol.
[0125]
[0126] At -10℃, 1.36 g of 2,4,6-trimethylphenol, 5.69 g of dibromomethyl ether, and 100 mL of dried tetrahydrofuran were added sequentially to a three-necked flask. A 1 M dichloromethane solution of tin chloride was added dropwise, and the mixture was stirred for a certain period. After the reaction was complete, the mixture was acidified to pH 1 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali, washed with water, dried, and evaporated to separate the crude product. The crude product was then purified using conventional methods, with column chromatography yielding 2.64 g of purified product.
[0127] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 2.3 (s, 1H, OH), 2.44 (s, 9H, CH3), 4.76 (s, 4H, CH2).
[0128] Preparation Example 4
[0129] This preparation example illustrates the preparation of 3,5-bis(bromomethyl)-2,4,6-triethylphenol.
[0130]
[0131] At -10℃, 1.78 g of 2,4,6-triethylphenol, 5.69 g of dibromomethyl ether, and 100 mL of toluene were added sequentially to a three-necked flask. A 1 M dichloromethane solution of tin chloride was added dropwise, and the mixture was stirred for a certain period. After the reaction was complete, the mixture was acidified to pH 1 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali, washed with water, dried, and evaporated to separate the crude product. The crude product was then purified using conventional methods, with column chromatography yielding 3.07 g of purified product.
[0132] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 2.3 (s, 1H, OH), 2.44 (s, 9H, CH3), 4.76 (s, 4H, CH2).
[0133] Preparation Example 5
[0134] This preparation method is used to illustrate the preparation of 3,5-bis(chloromethyl)-phenol.
[0135]
[0136] At -10°C, 1.88 g of phenol, 4.60 g of dichloromethyl ether, and 100 mL of toluene were added sequentially to a three-necked flask. 1.5 mL of tin chloride solution (1 M dichloromethane solution) was added dropwise at a rate of 1 mmol / h, and the reaction was stirred for 12 h to allow the substitution reaction to proceed. After the reaction was complete, the mixture was acidified to pH 2 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali, washed with water, dried, and evaporated to separate the crude product. The crude product was then subjected to column chromatography (using a mixed solvent of dichloromethane and methanol, volume ratio 10:1) to obtain 2.1 g of pure product.
[0137] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 4.68 (s, 4H, CH2), 6.82 (s, 2H, CH), 6.89 (s, H, CH).
[0138] Preparation Example 6
[0139] This preparation example illustrates the preparation of 3,5-bis(chloromethyl)-2,4,6-triisopropylphenol.
[0140]
[0141] At -10°C, 2.25 g of 2,4,6-triisopropylphenol, 4.60 g of dichloromethyl ether, and 100 mL of n-hexane were added to a three-necked flask. 1.5 mL of zinc chloride solution (1 M dichloromethane solution) was added dropwise at a rate of 0.1 mmol / h, and the mixture was stirred to allow the substitution reaction to proceed for 24 h. After the reaction was complete, the mixture was acidified to pH 1 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali and water, dried, and evaporated to obtain the crude product. The crude product was further purified by recrystallization from n-hexane to obtain 3.07 g of pure product.
[0142] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 1.43 (m, 9H, CH3), 3.46 (q, 2H, CH), 3.82 (q, 1H, CH), 4.65 (s, 4H, CH2).
[0143] Preparation Example 7
[0144] This preparation example illustrates the preparation of 3,5-bis(chloromethyl)-2,4,6-triphenylphenol.
[0145]
[0146] At -10°C, 3.25 g of 2,4,6-triphenylphenol, 4.90 g of dichloromethyl ether, and 100 mL of toluene were added sequentially to a three-necked flask. 1.8 mL of germanium chloride solution (1 M dichloromethane solution) was added dropwise at a rate of 0.5 mmol / h, and the reaction was stirred for 48 h to allow for the substitution reaction. After the reaction was complete, the mixture was acidified to pH 1 with 18 mol / L hydrochloric acid, extracted three times with 30 mL of ethyl acetate, washed with alkali, washed with water, dried, and evaporated to separate the crude product. The crude product was then purified by recrystallization from cyclohexane to obtain 4.24 g of pure product.
[0147] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 4.47 (s, 4H, CH2), 7.44 (m, 15H, CH).
[0148] Example 1
[0149] This example illustrates 3,5-bis[(di-p-methylphenylphosphino)methyl]-2,4,6-trimethylphenol (in formula (1), R i Preparation of CH3=R2=R3=CH3=R1'=R2'=R3'=R4'=CH3, where n, m, p, and q are all 1.
[0150]
[0151] To a nitrogen-protected three-necked flask, add 2.49 g (10 mmol) of di-p-methylphenylphosphine chloride and 50 mL of dried diethyl ether. With mechanical stirring, lower the temperature inside the flask to below -78 °C using an acetone / liquid nitrogen bath. Slowly add 0.38 g (10 mmol) of lithium aluminum hydride in portions. After reacting for 1.5 hours, allow the mixture to slowly rise to room temperature and react for another 1.5 hours. Quench the reaction with a small amount of water and sodium hydroxide. Filter the mixture, wash the filter cake with a small amount of diethyl ether, combine the filtrates, and dry with anhydrous magnesium sulfate.
[0152] Magnesium sulfate was filtered off, and 0.5 g (22 mmol) of metallic sodium was added while cooling in an ice bath. The mixture was stirred continuously, and after 2 hours, it was removed from the ice bath and allowed to rise naturally to room temperature. The mixture was then stirred at room temperature for 5 hours.
[0153] Excess sodium was removed. Under nitrogen protection and in an ice bath, a solution of 1.2 g (5 mmol) of 3,5-bis(chloromethyl)-2,4,6-trimethylphenol and 50 ml of dried tetrahydrofuran was added dropwise over 2 hours. After the addition was complete, the solution was allowed to rise naturally to room temperature. The reaction was then carried out under nitrogen protection for 2 hours, followed by stirring overnight. The solvent was evaporated, and dichloromethane and water were added. After stirring, two layers separated. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off, and the yellow solution was evaporated to dryness to obtain a pale yellow solid. After purification by silica gel column chromatography, 2.2 g of the product was obtained.
[0154] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 2.08 (s, 6H, CH3), 2.18 (s, 3H, CH3), 2.34 (s, 12H, CH3), 3.60 (d, J=10Hz, 4H, CH2), 7.23-7.34 (m, 16H, aromatic CH), 7.38 (s, 1H, OH).
[0155] Example 2
[0156] This example illustrates the preparation of 3,5-bis[(diphenylphosphino)methyl]-2,4,6-triethylphenol (in formula (1), R1'=R2'=R3'=R4'=H, R1=R2=R3=CH3CH2, n, m, p and q are all 1).
[0157]
[0158] In a three-necked flask, 2 mmol of 3,5-bis(chloromethyl)-2,4,6-triethylphenol and 50 mL of dried n-hexane were added. Under mechanical stirring and nitrogen protection at room temperature, 8 mL of 0.5 M (4 mmol) diphenylphosphine potassium tetrahydrofuran solution was added dropwise over 2 hours. After the addition was complete, the reaction was stirred overnight. The solvent was evaporated, and the mixture was extracted with dichloromethane and water. The organic phase was washed with water and dried over anhydrous magnesium sulfate. The magnesium sulfate was removed by filtration, the solvent was evaporated, and the mixture was recrystallized from toluene to give a pale yellow solid (diphosphine ligand compound C) weighing 0.87 g.
[0159] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 1.22 (m, 9H, CH3), 2.37 (d, 4H, CH2), 2.82 (m, 6H, CH2), 7.20 (m, 8H, CH), 7.45 (m, 12H, CH).
[0160] Example 3
[0161] This example illustrates the preparation of 3,5-bis[(diphenylphosphino)methyl]-2,4,6-trimethylphenol (in formula (1), R1'=R2'=R3'=R4'=H, R1=R2=R3=CH3, and n, m, p, and q are all 1).
[0162]
[0163] In a three-necked flask, 0.64 g (2 mmol) of 3,5-bis(bromomethyl)-2,4,6-trimethylphenol was dissolved in 50 mL of dried tetrahydrofuran. Under mechanical stirring and nitrogen protection at room temperature, 8 mL of 0.5 M (4 mmol) potassium diphenylphosphine tetrahydrofuran solution was added dropwise over 2 hours. After the addition was complete, stirring continued for 8 hours. The solvent was evaporated, and dichloromethane and water were added. After stirring, two layers separated. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off, and the yellow solution was evaporated to dryness to obtain a pale yellow solid weighing 0.9 g.
[0164] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 2.08 (s, 6H, CH3), 2.18 (s, 3H, CH3), 3.45 (d, J=10Hz, 4H, CH2), 7.29 (s, 1H, OH), 7.38-7.50 (m, 20H, aromatic CH).
[0165] Example 4
[0166] This example illustrates 3,5-bis[(di-p-bromophenylphosphino)methyl]-2,4,6-trimethylphenol (in formula (1), R1' = R2' = R3' = R Preparation of 4'=Br, R1=R2=R3=CH3, and n, m, p and q are all 1)
[0167]
[0168] In a three-necked flask, 0.64 g (2 mmol) of 3,5-bis(bromomethyl)-2,4,6-trimethylphenol was dissolved in 50 mL of dried tetrahydrofuran. Under nitrogen protection and mechanical stirring at room temperature, 8 mL of 0.5 M (4 mmol) di-p-bromophenylphosphine potassium tetrahydrofuran solution was added dropwise over 2 hours. After the addition was complete, stirring continued for 8 hours. The solvent was evaporated, and dichloromethane and water were added. After stirring, two layers separated. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off, and the yellow solution was evaporated to dryness to obtain a pale yellow solid weighing 1.5 g.
[0169] 1 ¹H NMR (CDCl₃ / TMS, 300MHz) δ (ppm): 2.04 (s, 6H, CH₃), 2.12 (s, 3H, CH₃), 2.57 (d, 4H, CH₂), 7.17–7.22 (m, 8H, aromatic CH), 7.46–7.52 (m, 8H, aromatic CH).
[0170] Example 5
[0171] This example illustrates the preparation of 3,5-bis[(diphenylphosphino)methyl]-phenol (in formula (1), R1=R2=R3=R1'=R2'=R3'=R4'=H, and n, m, p and q are all 1).
[0172]
[0173] In a three-necked flask, 0.48 g (2.5 mmol) of 3,5-bis(chloromethyl)phenol was dissolved in 50 mL of dried tetrahydrofuran. Under mechanical stirring and nitrogen protection, 10 mL of 0.5 M (5 mmol) diphenylphosphine potassium tetrahydrofuran solution was added dropwise over 2 hours. The reaction temperature was controlled below -5 °C. After the addition was complete, stirring was continued at room temperature for 4 hours. The solvent was evaporated, and dichloromethane and water were added. After stirring, two layers separated. The organic layer was washed with water and dried with anhydrous sodium sulfate. The sodium sulfate was filtered off, and the solution was evaporated to dryness to obtain a yellow solid. The obtained solid was dissolved in a small amount of dichloromethane and eluted with a 100–200 mesh silica gel column using petroleum ether:dichloromethane (v / v) = 6:4 to obtain a yellow solid weighing 0.9 g.
[0174] 1H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 3.60 (d, J = 10Hz, CH2), 6.66 (s, 1H, aromatic CH), 6.78 (s, 2H, aromatic CH), 7.39-7.53 (m, 20H, aromatic CH), 9.43 (s, 1H, OH).
[0175] Example 6
[0176] This example illustrates the preparation of 3,5-bis[(diphenylphosphino)methyl]-2,4,6-triisopropylphenol (in formula (1), R1'=R2'=R3'=R4'=H, R1=R2=R3=CH(CH3)2, and n, m, p and q are all 1).
[0177]
[0178] 0.63 g (2 mmol) of 3,5-bis(chloromethyl)-2,4,6-triisopropylphenol and 50 mL of dried tetrahydrofuran were added to a three-necked flask. Under mechanical stirring and nitrogen protection at room temperature, 8 mL of 0.5 M (4 mmol) diphenylphosphine potassium tetrahydrofuran solution was added dropwise over 2 hours. After the addition was complete, stirring continued overnight. The solvent was evaporated, and dichloromethane and water were added. After stirring, two layers separated. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off, and the yellow solution was evaporated to dryness to give a pale yellow solid weighing 1.0 g. Recrystallization from hexane gave a white solid weighing 0.8 g.
[0179] 1H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 1.20 (d, 18H, CH3), 2.87 (m, 3H, CH), 3.65 (d, J=10Hz, 4H, CH2), 7.27 (s, 1H, OH), 7.38-7.52 (m, 20H, CH).
[0180] Example 7
[0181] This example illustrates the preparation of 3,5-bis[(diphenylphosphino)methyl]-2,4,6-triphenylphenol (in formula (1), R1'=R2'=R3'=R4'=H, R1=R2=R3=Ph, and n, m, p and q are all 1).
[0182]
[0183] To a nitrogen-protected five-necked flask, add 18.6 g of a 10% (10 mmol) hexane solution of diphenylphosphine and approximately 50 ml of dried tetrahydrofuran. With mechanical stirring, cool the flask to below -78°C using an acetone / liquid nitrogen bath. Then, add 12.5 ml of a 1.6 mol / L (20 mmol) hexane solution of butyllithium. The solution in the flask turns orange. After one hour, the addition is complete. Remove the acetone bath and allow the solution to naturally warm to room temperature.
[0184] Two hours later, the temperature inside the flask was lowered to below -50°C again using an acetone / liquid nitrogen bath. A solution of 2.1 g (5 mmol) of 3,5-bis(chloromethyl)-2,4,6-triphenylphenol and 50 ml of dried tetrahydrofuran was added dropwise over 2 hours. After the addition was complete, the solution was allowed to naturally rise to room temperature. The reaction was carried out under nitrogen protection for 2 hours, followed by stirring overnight. The solvent was evaporated, and dichloromethane and water were added. After stirring, two layers separated. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The magnesium sulfate was filtered off, and the yellow solution was evaporated to dryness to obtain a pale yellow solid. The obtained solid was dissolved in a small amount of dichloromethane and eluted with a 100–200 mesh silica gel column using petroleum ether:dichloromethane (v / v) = 6:4, yielding a product weighing 3.2 g.
[0185] 1 H NMR (CDCl3 / TMS, 300MHz) δ (ppm): 3.62 (d, J=10Hz, 4H, CH2), 7.41-7.56 (m, 35H, aromatic CH), 9.30 (s, 1H, OH).
[0186] The following test examples illustrate the application of the above-mentioned phosphorus ligand compounds in the hydroformylation of olefins or their derivatives (such as vinyl acetate).
[0187] Conversion rate of vinyl acetate = (A 0 -A) / A 0 Aldehyde selectivity = (B+C) / A 0 .
[0188] A 0 = The amount of substance of the alkene or its derivative added to the reaction;
[0189] A = The amount of olefin or its derivative remaining in the system after the reaction is complete;
[0190] B = the amount of 2-acetoxypropionaldehyde;
[0191] The amount of substance of C=3-acetoxypropionaldehyde.
[0192] Test Example 1
[0193] In a 100 ml high-pressure reactor, 6 ml (64.88 mmol) of vinyl acetate, 44 ml of cyclohexane, 7.1 mg (0.027 mmol) of rhodium carbonyl acetylacetone, and 33.6 mg (0.063 mmol) of 3,5-bis[(diphenylphosphino)methyl]-2,4,6-trimethylphenol were added, and the reactor was sealed. The reactor was purged three times with nitrogen, then three times with syngas (CO:H2 volume ratio 1:1), and pressurized to 4.0 MPa with syngas. The temperature was raised to 100 °C to initiate the hydroformylation reaction. The consumption of syngas was indicated by the pressure change in the gas storage tank; the reaction endpoint was reached when no more gas was consumed. The reactor was cooled to room temperature, unreacted gases were discharged, and the reactor was purged three more times with nitrogen. The reactor was then opened, and the composition of the reaction products was analyzed by gas chromatography, with quantification using the internal standard method. The conversion rate of vinyl acetate was 87%, and the selectivity for aldehydes was 94.1%.
[0194] Comparative test cases
[0195] In a 100 mL high-pressure reactor, 64.88 mmol of vinyl acetate was added as the raw material for the hydroformylation reaction, 44 mL of toluene was added as the solvent, and 0.025 mmol of acetylacetone triphenylphosphine carbonyl rhodium and 0.054 mmol of tributylphosphine were added as catalysts. The reactor was sealed. The reactor was purged three times with nitrogen, and then three times with syngas (CO:H2 volume ratio 1:1). The pressure was increased to 5 MPa with syngas, and the temperature was raised to the reaction temperature of 120 °C to initiate the hydroformylation reaction. The consumption of syngas was indicated by the pressure change of the gas storage tank, and the reaction endpoint was reached when no more gas was consumed. The reactor was cooled to room temperature, unreacted gases were discharged, and the reactor was purged with nitrogen three more times. The reactor was then opened, and the composition of the reaction products was analyzed by gas chromatography, with quantification using the internal standard method. The conversion rate of vinyl acetate was 80.2%, and the selectivity for aldehydes was 82.1%.
[0196] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. The application of a compound in the preparation of phosphine ligand compounds, characterized in that, The compound has the structure shown in formula (I): （I） In formula (I), R1, R2 and R3 are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy; X1 and X2 are each halogens independently.
2. The application according to claim 1, wherein, R1, R2 and R3 are each independently selected from H, halogen, nitro, C1-C5 straight-chain or branched alkyl, C3-C10 alkoxy, C6-C10 aryl, C7-C10 alkylaryl, C7-C10 aralkyl, C1-C6 acyl or C1-C6 acyloxy. And / or, X1 and X2 are each independently one of F, Cl, Br and I.
3. The application according to claim 2, wherein, R1, R2 and R3 are each independently selected from H, halogen, C1-C6 straight-chain or branched alkyl or C6-C10 aryl; And / or, X1 and X2 are each independently Cl or Br.
4. The application according to any one of claims 1-3, wherein, The compound has the following structure: (a)、 (b)、 (c)、 (d)、 (e)、 (f)、 (g)。 5. The application according to claim 1, wherein, The method for preparing the compound includes: subjecting the compound of formula (II) and the dihalomethyl ether of formula (III) to a substitution reaction; (II)、 (III)) In formula (II) or formula (III), R1, R2, R3, X1 and X2 have the same definitions as in claim 1.
6. The application according to claim 5, wherein, The conditions for the substitution reaction include: a temperature of -50°C to 100°C and a time of 1-48 hours; And / or, the molar ratio of the compound shown in formula (II) to the dihalomethyl ether shown in formula (III) is 1:(1-10). And / or, the substitution reaction is carried out in the presence of a Lewis acid, wherein the amount of the Lewis acid is 0.01-1 mmol relative to 1 mmol of the compound represented by formula (II); And / or, the substitution reaction is carried out in the presence of a first solvent.
7. The application according to claim 6, wherein, The Lewis acid is selected from at least one of tin halides, germanium halides, and zinc halides; And / or, the first solvent is selected from at least one of C4-C8 alkanes, C6-C10 aromatics, C2-C6 ethers, and C4-C8 heterocyclic compounds; And / or, relative to 1 g of the compound represented by formula (II), the amount of the first solvent is 1-150 mL.
8. The application according to claim 6, wherein, The Lewis acid is selected from at least one of tin chloride, tin bromide, tin iodide, tin sulfate, germanium chloride, and zinc chloride; And / or, the first solvent is selected from at least one of n-hexane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, acetone, diethyl ether, methyl tert-butyl ether, and isopropyl ether.
9. The application according to claim 1, wherein, The application of the compound in the preparation of phosphine ligand compounds for hydroformylation reactions.
10. A method for preparing phosphine ligand compounds having a phenolic group, characterized in that, The method comprises: contacting a diarylphosphine salt of formula (IV) with a substituted phenol of formula (I) as described in any one of claims 1-9; (IV); In equation (IV), m and n are each an independent integer from 1 to 4, and M is an alkali metal element; In formula (IV), R1' and R2' are each independently selected from H, halogen, nitro, C1-C10 straight-chain or branched alkyl, C3-C20 alkoxy, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl, acyl or acyloxy.
11. The method according to claim 10, wherein, M is selected from one of Li, Na, and K; And / or, R1' and R2' are each independently selected from H, halogen, nitro, C1-C5 straight-chain or branched alkyl, C3-C10 alkoxy, C6-C10 aryl, C7-C10 alkylaryl, C7-C10 aralkyl, C1-C6 acyl or C1-C6 acyloxy.
12. The method according to claim 11, wherein, R1' and R2' are each independently selected from H, halogens, C1-C5 straight-chain or branched alkyl groups, or C6-C10 aryl groups.
13. The method according to claim 11, wherein, In equation (IV), R1' and R2' are both CH3; in equation (I), R1, R2, and R3 are all CH3; or, In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all CH2CH3; or, In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all CH3; or, In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all H; or, In equation (IV), R1' and R2' are both H; in equation (I), R1, R2, and R3 are all CH(CH3)2; or, In equation (IV), R1' and R2' are both H, and in equation (I), R1, R2 and R3 are all Ph; or In equation (IV), R1' and R2' are both F; in equation (I), R1, R2, and R3 are all CH3; or, In formula (IV), R1' and R2' are both Cl; in formula (I), R1, R2, and R3 are all CH3; or, In formula (IV), R1' and R2' are both Br, and in formula (I), R1, R2 and R3 are all CH3.
14. The method according to any one of claims 10-13, wherein, The contact conditions include: a temperature of -50°C to 100°C and a time of 1-48 hours; And / or, the molar ratio of the diarylphosphine salt shown in formula (IV) to the substituted phenol shown in formula (I) is (1.5-3):1; And / or, the contact is carried out in the presence of a second solvent; the amount of the second solvent is 1-50 mL relative to 1 mmol of the substituted phenol of formula (I).
15. The method according to claim 14, wherein, The second solvent is an aprotic solvent.
16. The method of claim 14, wherein, The second solvent is selected from at least one of C4-C8 alkanes, C6-C12 cycloalkanes, C6-C10 aromatics, C2-C6 ethers, and C4-C8 oxoheterocycles.
17. The method of claim 14, wherein, The second solvent is selected from at least one of n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, acetone, diethyl ether, methyl tert-butyl ether, and isopropyl ether.
18. A phosphine ligand compound having a phenolic group prepared by the method of any one of claims 10-17.
19. The use of the phosphine ligand compound having a phenol group as described in claim 18 in a hydroformylation reaction.