CN112159313A - Preparation method of big steric-hindrance bi-phenol skeleton and phosphonite ligand thereof - Google Patents

Preparation method of big steric-hindrance bi-phenol skeleton and phosphonite ligand thereof Download PDF

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CN112159313A
CN112159313A CN202011192970.8A CN202011192970A CN112159313A CN 112159313 A CN112159313 A CN 112159313A CN 202011192970 A CN202011192970 A CN 202011192970A CN 112159313 A CN112159313 A CN 112159313A
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张润通
闫鑫
彭江华
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Huizhou Kailisi Technology Co ltd
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Abstract

The invention discloses a big steric-hindrance bi-phenyl tetraphenol skeleton and a phosphonite ligand 2,2 ', 6, 6' -tetra [ (1,
Figure DDA0002753240400000011
the hydroformylation reaction of 1, 3-butadiene and olefin with more than C5-C10 has better conversion rate and normal-to-iso ratio.

Description

Preparation method of big steric-hindrance bi-phenol skeleton and phosphonite ligand thereof
Technical Field
The invention relates to a preparation method of a big steric hindrance bi-phenyl tetraphenol skeleton and a phosphonite ligand 2,2 ', 6,6 ' -tetra [ (1,1 ' -biphenyl-2, 2 ' -diyl) phosphonite ] -3,3 ', 5,5 ' -tetra-tert-butyl-1, 1 ' -biphenyl thereof.
Background
Hydroformylation has found a very large industrial application since 1938 in professor Otto Roelen (Chem abstract, 1994, 38-550). Since aldehydes can be very easily converted into corresponding alcohols, carboxylic acids, esters, imines, and the like, which have important uses in organic synthesis, aldehydes synthesized by hydroformylation are synthesized on a large scale in industrial production. Aldehydes produced by hydroformylation in industrial production are now reaching 1000 ten thousand tons per year (adv. synth. catal.2009,351, 537-540).
In hydroformylation reactions, while bidentate and tetradentate phosphine ligands have been widely reported and patented by foreign large chemical companies such as BASF, Dow, Shell and Eastman and some research groups, multidentate phosphine ligands have rarely been reported (Org. Lett.2013,15,1048-. Therefore, the development of a novel efficient tetradentate phosphine oxide ligand and a preparation method thereof in the hydroformylation reaction have important significance.
Phosphites are industrially used mainly for antioxidants, heat stabilizers, flame retardants and the like in polymer materials such as plastics, rubbers and the like. It is a phosphorous acid hydroxy derivative, which can be classified into phosphorous acid monoester ROP (OH) according to the number of hydroxy groups in the molecule2Phosphorous acid diester (RO)2POH and Triphosphite (RO)3And P. Hydroxy or alkoxy radicals substituted by halogen atoms, formsTo form halogenated phosphite ester. Among the halophosphites, chlorophosphite is the most important intermediate of trivalent organophosphorus compounds. The most common method for industrially preparing phosphite ester is direct esterification, which means that halogenated material of trivalent phosphorus is used as raw material to react with alcohol by controlling certain reaction conditions.
Propylene is used as a raw material, and butyraldehyde which is a hydroformylation reaction product of the propylene is subjected to a series of reactions such as aldol condensation, hydrogenation and the like to obtain a plasticizer dioctyl phthalate (DEHP) which is widely applied in industry. DEHP yields in china are higher than 300 ten thousand tons per year, while annual yields in the world are as high as 1000 ten thousand tons. However, the price of propylene raw materials is increasing year by year, and the plasticizer DEHP has small molecular weight, is cracking and volatile, has large toxicity to human bodies, and has been prohibited from production and recycling by REACH regulation listed in European Union in 2015. The improved technology is to obtain valeraldehyde by hydroformylation of mixed/etherified butylene, and produce a novel plasticizer DPHP with high molecular weight through similar subsequent reaction. DPHP is not easily cracked and has low toxicity. At present, the technology is expected to gradually replace the traditional technology. Traditionally based on PPh3The technology can only realize the hydroformylation of 1-butene, the production cost of 1-butene is high, and the cheaper raw material is mixed butene or butene after ether. The domestic hydroformylation industrial device mainly uses PPh3And bidentate phosphonite ligands (Biphephos) used in Dow Chemical (Dow Chemical) are dominant. With foreign catalysts and processes, in addition to the high royalties and process package transfer costs that must be paid, the Biphephos ligand of dow chemistry is unstable in air for a long time, is easily hydrolyzed, acidolyzed and tends to block pipelines, and sporadically added ligands are required to ensure catalytic activity.
Compared with the bidentate phosphonite ligand Biphephos, the preparation of the biphenyl tetradentate phosphonite ligand and the derivative thereof developed by the invention has the characteristics of easy synthesis, amplified synthesis, high yield, good reaction activity, high yield of straight-chain aldehyde products, extremely stable water and oxygen, difficult decomposition and the like. Meanwhile, through preliminary industrial small-scale research and comparison of Biphephos and other bidentate phosphine ligands, the biphenyl tetradentate phosphonite ligand with large steric hindrance developed by the invention can realize higher conversion rate, normal-iso ratio and better activity and stability in the hydroformylation reaction of C3-C10 olefin, and has great potential and practical value.
Disclosure of Invention
The invention aims to develop a high-efficiency synthesis method of a big steric-hindrance bi-phenol skeleton and a phosphonite ligand thereof. It is especially easy to synthesize, high in yield and capable of being synthesized in large scale. The structures of the compound and its derivatives are shown below:
Figure BDA0002753240380000031
in formula I, R can be a cyclic phosphine structure of phosphite ester, as shown in the figure. The synthetic route of the biphenyl tetraphosphine ligand is as follows:
synthesis scheme 1：
Figure BDA0002753240380000041
Synthesis scheme 2：
Figure BDA0002753240380000042
Detailed Description
The above route of the present invention is described in detail by the following examples, which should be noted that the present invention is only for further illustration and not limited to the present invention. Those skilled in the art can make insubstantial modifications and adaptations to the present invention.
Drawings
FIG. 1 shows the NMR spectrum of ligand L1: (1H NMR)；
FIG. 2 shows NMR spectra of ligand L1: (31PNMR)；
FIG. 3 is a high resolution mass spectrum (UPLC APCI-TOF-MS) of ligand L1:
FIG. 4 is a high resolution mass spectrum (UPLC APCI-TOF-MS) of ligand L1.
Example 1
Preparation of 3-methoxyphenol:
Figure BDA0002753240380000051
compound 1(2.2g) and sodium bicarbonate (10.0g) were ground together into a powder, dimethyl sulfate (2.5g) was added to react for one hour at 60 ℃ with vigorous stirring, 50mL of water was added to wash out the base, the crude product was filtered and then recrystallized from ethyl acetate-n-hexane to give 1.98g of pure product in 79% yield.
Example 2
Preparation of 2, 4-di-tert-butyl-5-methoxy-phenol:
Figure BDA0002753240380000052
1(24.8g), toluene (200mL), and PTSA (p-toluenesulfonic acid) (5.16g) were charged in this order in a 1L three-necked flask, and after completion of the charge, the flask was heated to 95 ℃ to react for 12 hours while bubbling isobutylene gas into the solution. The solvent was spin dried under reduced pressure, 100mL of water was added, and extracted three times with ethyl acetate (100 mL each). The obtained organic phase is dried by anhydrous sodium sulfate, then is decompressed and dried by spinning, and 10.0g of target product is obtained by the residue through flash column chromatography, with the yield of 42%.
Example 3
Preparation of 4, 6-di-tert-butyl-1, 3-dihydroxybenzene:
Figure BDA0002753240380000053
1(26.3g), toluene (200mL), and PTSA (p-toluenesulfonic acid) (5.16g) were charged in this order in a 1L three-necked flask, and after completion of the charge, the flask was heated to 95 ℃ to react for 12 hours while bubbling isobutylene gas into the solution. The solvent was spin dried under reduced pressure, 100mL of water was added, and extracted three times with ethyl acetate (100 mL each). The obtained organic phase is dried by anhydrous sodium sulfate, then is decompressed and dried by spinning, and the residue is subjected to flash column chromatography to obtain 15.0g of target product with the yield of 56%.
Example 4
Preparation of 2, 4-di-tert-butyl-5-methoxymethyl ether-phenol:
Figure BDA0002753240380000061
in a 1L three-necked bottle, 2 is added’(15.0g) was dissolved in 200mL of a methylene chloride solution, and chloromethoxymethyl ether (5mL) and DIEA (10mL) were added in this order to conduct a reaction at room temperature for 12 hours. 250mL of saturated ammonium chloride was added to the system, the solvent was spin-dried under reduced pressure, 100mL of water was added, and extraction was performed three times with ethyl acetate (100 mL each). The obtained organic phase is dried by anhydrous sodium sulfate, then is decompressed and dried by spinning, and the residue is subjected to flash column chromatography to obtain 13.7g of target product with the yield of 71 percent.
Example 5
Preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-6, 6 ' -dimethoxy-2, 2 ' -dihydroxy-1, 1 ' -biphenyl:
Figure BDA0002753240380000062
in a 500mL single-necked round-bottomed flask, 3(6.0g), 100mL of methanol were sequentially added, potassium ferricyanide (8.37g) and potassium hydroxide (4.58g) were weighed and dissolved in 100mL of water, and this solution was dropwise added to the round-bottomed flask, and the resulting reaction system was reacted at room temperature for 2 hours. The resulting reaction mixture was concentrated, 200mL of water was added, and the mixture was extracted three times with ethyl acetate (100 mL each). The residue was dried to a negative pressure, heated at 100 ℃ for 2 hours and recrystallized from petroleum ether to give 2.9g of product with a yield of 50%.
Example 6
Preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-6, 6 ' -dimethoxymethyl ether-2, 2 ' -dihydroxy-1, 1 ' -biphenyl:
Figure BDA0002753240380000071
in a 500mL single neck round bottom flask, 3 were added sequentially’(5.5g) and 100mL of methanol, potassium ferricyanide (9.12g) and potassium hydroxide (5.36g) were weighed out and dissolved in 100mL of water, the solution was dropwise added to a round-bottomed flask, and the resulting reaction system was reacted at room temperature for 2 hours. The resulting reaction mixture was concentrated, 200mL of water was added, and the mixture was extracted three times with ethyl acetate (100 mL each). The residue was dried to a negative pressure, heated at 100 ℃ for 2 hours and recrystallized from petroleum ether to give 2.6g of product in 47% yield.
Example 7
Preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-2, 2 ', 6,6 ' -tetrahydroxy-1, 1 ' -biphenyl (scheme 1):
Figure BDA0002753240380000072
a dry 200mL Schlenk flask was charged with 4(2.0g), the reaction flask was replaced with a nitrogen atmosphere, and 50mL of dichloromethane were added at 25 ℃. Boron tribromide (2.34g) was added dropwise to the solution to react for 6 hours. After the reaction solution was quenched with water, 50mL of water was added and extracted three times with ethyl acetate (100 mL each). The obtained organic phase is dried by anhydrous sodium sulfate and then is dried by decompression and spin-drying to obtain a white solid, and the target product is obtained by column chromatography, wherein the yield is 96 percent and is 1.8 g.
Example 8
Preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-2, 2 ', 6,6 ' -tetrahydroxy-1, 1 ' -biphenyl (scheme 2):
Figure BDA0002753240380000073
in a 200mL round-bottomed flask, 4' (2.5g) was dissolved in 40mL of an isopropanol solution, and then 4 drops of concentrated hydrochloric acid were added dropwise thereto, followed by stirring at 55 ℃ for 10 hours or more, whereupon the starting material was completely reacted by TLC. Saturated sodium bicarbonate (25mL) was added and extracted three times with ethyl acetate (50 mL each). The obtained organic phase is dried by anhydrous sodium sulfate and then is dried by decompression and spin-drying to obtain a white solid, and the target product is obtained by column chromatography, wherein the yield is 2.0 g.
Example 9
Preparation of 1,1 '-biphenyl-2, 2' -dioxychlorophosphine:
Figure BDA0002753240380000081
20g of 2, 2' -biphenol was added to an excess of PCl3In (1), after refluxing under heating for 6 hours, excess PCl was distilled off under reduced pressure318g of 7 are obtained as yellow oil in 71% yield.
Example 10
Preparation of 2,2 ', 6,6 ' -tetrakis [ (1,1 ' -biphenyl-2, 2 ' -diyl) phosphonite ] -3,3 ', 5,5 ' -tetra-tert-butyl-1, 1 ' -biphenyl:
Figure BDA0002753240380000082
4.2g of 2,2 ', 6,6 ' -tetrahydroxy-3, 3 ', 5,5 ' -tetra-tert-butyl-1, 1 ' -biphenyl and 100mL of anhydrous tetrahydrofuran were sequentially added to a 2L Schlenk flask under nitrogen protection, and 15mL of 2.5M n-butyllithium was added dropwise at-78 ℃. The reaction mixture was warmed to room temperature and refluxed for 1 hour. Then, the reaction solution was dropped into 100mL of an anhydrous tetrahydrofuran solution of 1, 1' -dioxyphosphorochloridite (13g) at-78 ℃ and reacted at room temperature for 24 hours after completion of the dropping, the reaction solution was concentrated under a nitrogen atmosphere, and the residue was subjected to column chromatography to obtain 6.0g of the objective product with a yield of 46%.1H NMR(400MHz,CDCl3):＝7.74(s,2H),7.48–7.38(m,8H),7.19(td,J＝7.6,7.2,2.2Hz,8H),7.11(dd,J＝6.5,1.7Hz,16H),1.30(s,36H)。31PNMR(243MHz,CDCl3):＝140.62。APCI-TOF/MS:Calculated for C76H71O12P4[M+H]+:1299.3818；Found:1299.3891。
It is to be noted here that other biphenyl-type tetradentate phosphine ligands of L2-L26 of formula I can be prepared by using only different aryl-substituted phosphonium chloride derivatives as described in example 10.

Claims (10)

1. The preparation method of the big steric-hindrance bi-phenol skeleton and the phosphonite ligand thereof is characterized by comprising the following synthetic routes:
route 1:
Figure FDA0002753240370000011
route 2:
Figure FDA0002753240370000012
wherein, the structure of the large steric hindrance biphenyl tetradentate phosphite ligand represented by the general formula I is as follows:
Figure FDA0002753240370000021
2. the process for the preparation of the sterically hindered biphenyltetraphenol skeleton and its phosphonite ligand as claimed in claim 1, wherein the skeleton synthesis is carried out by the following reaction:
Figure FDA0002753240370000022
and (3) synthesizing 3-methoxy-phenol.
3. The process for the preparation of the sterically hindered biphenyltetraphenol skeleton and its phosphonite ligand as claimed in claim 1, wherein the skeleton synthesis is carried out by the following reaction:
Figure FDA0002753240370000031
preparation of 2, 4-di-tert-butyl-5-methoxy-phenol
Figure FDA0002753240370000032
Preparation of 2, 4-di-tert-butyl-resorcinol
The acid used in the above reaction may be one or more of an organic acid such as: formic acid, acetic acid, oxalic acid, dichloroacetic acid, trifluoroacetic acid, propionic acid, malonic acid, pyruvic acid, butyric acid, valeric acid, caproic acid, adipic acid, benzoic acid, p-nitrobenzoic acid, terephthalic acid, benzenesulfonic acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and the like; inorganic acids such as: hydrobromic acid, hydrochloric acid, hydrofluoric acid, sulfurous acid, sulfuric acid, perchloric acid, phosphonic acid, pyrophosphoric acid, nitric acid, nitrous acid, chromic acid, fluoroantimonic acid, and the like.
4. The process for the preparation of the sterically hindered biphenyltetraphenol skeleton and its phosphonite ligand as claimed in claim 1, wherein the skeleton synthesis is carried out by the following reaction:
Figure FDA0002753240370000033
preparation of 2, 4-di-tert-butyl-5-methoxymethyl ether-phenol
The hydroxyl protecting group used in the above reaction may be, but is not limited to, any of the following protecting groups, except chloromethoxymethyl ether (MOMCl):
Figure FDA0002753240370000041
Hydroxyl protecting groups：
Figure FDA0002753240370000042
common agents for protecting hydroxyl groups enumerated above include: 2-chlorotetrahydropyran, chlorotert-butane, allyl chloride, benzyl chloride, tert-butyldiphenylchlorosilane, acetyl chloride, trimethylacetyl chloride, benzoyl chloride or tert-butyldimethylchlorosilane.
5. The process for the preparation of the sterically hindered biphenyltetraphenol skeleton and its phosphonite ligand as claimed in claim 1, wherein the skeleton synthesis is carried out by the following reaction:
Figure FDA0002753240370000043
preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-6, 6 ' -dimethoxy-2, 2 ' -dihydroxy-1, 1 ' -biphenyl
Figure FDA0002753240370000044
Preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-6, 6 ' -dimethoxymethyl ether-2, 2 ' -dihydroxy-1, 1 ' -biphenyl.
6. The process for the preparation of the sterically hindered biphenyltetraphenol skeleton and its phosphonite ligand as claimed in claim 1, wherein the skeleton synthesis is carried out by the following reaction:
Figure FDA0002753240370000051
preparation of 3,3 ', 5,5 ' -tetra-tert-butyl-2, 2 ', 6 ' -tetrahydroxy-1, 1 ' -biphenyl.
7. The process for the preparation of the sterically hindered biphenyltetraphenol skeleton and its phosphonite ligand as claimed in claim 1, wherein the skeleton synthesis is carried out by the following reaction:
Figure FDA0002753240370000052
preparation of 2,2 ', 6,6 ' -tetrakis [ (1,1 ' -biphenyl-2, 2 ' -diyl) phosphonite ] -3,3 ', 5,5 ' -tetra-tert-butyl-1, 1 ' -biphenyl (L1)
Meanwhile, the ether solvent used in the above reaction may be any one of tetrahydrofuran, diethyl ether, 2-methyltetrahydrofuran or dioxane.
8. A process for preparing big-steric-hindrance biphenol skeleton and its phosphonite ligand used in the hydroformylation of olefin and gradually substituting bidentate phosphine ligand (Bisbi, Biphephos, etc) features that the big-steric-hindrance biphenol skeleton and its phosphonite ligand are prepared by the same method. The process is characterized in that the sterically hindered biphenyltetracarboxylic phosphonite ligands used can be as described in claim 1 having the general formula I.
9. A novel process for the preparation of sterically hindered biphenyltetraphenol skeletons and their phosphonite ligands as claimed in claim 8 for the hydroformylation of olefins with stepwise substitution of bidentate phosphine ligands (e.g. Bisbi, Biphephos, etc.). The method is characterized by being realized according to the following process steps and parameters.
(1) Under the protection of inert gas, sequentially adding a biphenyl type tetradentate phosphonite ligand and a rhodium catalyst in a certain proportion in a reaction device, wherein the molar ratio of phosphine to rhodium is about 1-5: 1, and stirring and complexing for 30 minutes at room temperature under an organic solvent.
(2) Then, under the protection of inert gas, under the switching of a two-position four-way valve, adding a certain proportion of liquid mixed C-C or C-C or cis-2-butene or trans-2-butene into the reaction kettle by using a plunger pump with a metering function, controlling the concentration of the rhodium catalyst to be about 50-200 ppm, and uniformly stirring at room temperature for 5-10 minutes.
(3) After stirring uniformly, filling CO and H with a certain pressure into the reaction device2The pressure ratio of hydrogen to carbon monoxide is between 1: 1 and 1: 5, and the total pressure is between 0.5MPa and 1 MPa; and stirring and reacting for 1-4 hours at the temperature of 40-80 ℃.
10. The reaction process according to claim 9,
the olefin is as follows: propylene (99 wt%), mixed C.sub.four (1-butene (25 wt%), cis-2-butene (40 wt%) and trans-2-butene (35 wt%), C.sub.four after ether (isobutane (52.1 wt%), 1-butene (16.6 wt%), cis-2-butene (15.3 wt%) and trans-2-butene (16.0 wt%)); the cis-2-butene, trans-2-butene and 1, 3-butadiene are all contained in more than 98.0 wt%; the content of the C5-C10 olefin is more than 95 wt%.
The organic solvent is any one of toluene, dichloromethane, dichloroethane, hexane, ethyl acetate, dioxane, tetrahydrofuran or n-valeraldehyde.
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