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CN116283501A - Preparation of novel biphenyl tetradentate phosphonite ligand and application of ligand in mixed/etherified carbon tetrahydroformylation reaction - Google Patents

Preparation of novel biphenyl tetradentate phosphonite ligand and application of ligand in mixed/etherified carbon tetrahydroformylation reaction Download PDF

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CN116283501A
CN116283501A CN202310302410.0A CN202310302410A CN116283501A CN 116283501 A CN116283501 A CN 116283501A CN 202310302410 A CN202310302410 A CN 202310302410A CN 116283501 A CN116283501 A CN 116283501A
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biphenyl
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张润通
彭江华
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Guangdong Oukai New Material Co ltd
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
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    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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    • B01J31/2438—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member and further hetero atoms as ring members, excluding the positions adjacent to P
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Abstract

The invention discloses a preparation method of a novel biphenyl tetradentate phosphonite ligand 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and derivatives thereof. The novel biphenyl tetradentate phosphonite ligand has a structure shown in a general formula I, wherein a substituent R in the general formula I can be a cyclic phosphine structure. Meanwhile, the invention discloses application in a novel mixed/etherified carbon four (butylene) hydroformylation reaction system with biphenyl tetradentate phosphonite ligand as a ligand.

Description

Preparation of novel biphenyl tetradentate phosphonite ligand and application of ligand in mixed/etherified carbon tetrahydroformylation reaction
The invention aims at the application of 2019, 08 and 02, the application number is CN201910712958.6, and the invention creates a divisional application of an application file of 'preparation of a novel biphenyl tetradentate phosphonite ligand and application of the ligand in a mixed/etherified carbon tetrahydroformylation reaction'.
Technical Field
The invention relates to a preparation method of novel biphenyl tetradentate phosphonite ligand 2,2', 6' -tetra [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and a hydroformylation reaction method in mixed carbon four.
Background
The hydroformylation reaction has found tremendous use in industry since 1938 as taught by Otto Roelen (Chem Abstr,1994, 38-550). Since aldehydes can be very easily converted into compounds having important uses in organic synthesis, corresponding alcohols, carboxylic acids, esters, imines, etc., aldehydes synthesized by hydroformylation are synthesized on a large scale in industrial production. The production of aldehydes by hydroformylation in industrial production per year has now reached 1000 ten thousand tons (adv. Synth. Catalyst. 2009,351, 537-540).
While bidentate phosphine ligands and tetradentate phosphine ligands have been widely reported and patented by large chemical companies such as BASF, dow, shell and Eastman and some research groups abroad, multidentate phosphine ligands have been rarely reported (org.lett.2013, 15, 1048-1052). Therefore, the development of the novel tetradentate phosphine oxide ligand with high efficiency in the hydroformylation reaction and the preparation method thereof have important significance.
The phosphite ester is mainly used in the industry for antioxidants, heat stabilizers and flame retardance in high polymer materials such as plastics, rubber and the likeAgents, and the like. It is a derivative of hydroxyl group of phosphorous acid, and can be classified into monoester of phosphorous acid ROP (OH) according to the number of hydroxyl groups in the molecule 2 Phosphorous acid diester (RO) 2 POH and phosphite triester (RO) 3 P. The hydroxyl or alkoxy groups are substituted with halogen atoms to form halophosphites. Among the halophosphites, chlorophosphite is the most important trivalent organophosphorus compound intermediate. The most common industrial phosphite ester preparation method is a direct esterification method, which is to take a halogenated compound of trivalent phosphorus as a raw material and react with alcohols by controlling certain reaction conditions.
Propylene is used as a raw material, and a hydroformylation reaction product butyraldehyde is subjected to aldol condensation, hydrogenation and other series of reactions to obtain the plasticizer dioctyl phthalate (DEHP) widely applied in industry. DEHP is produced in china with annual production of more than 300 ten thousand tons and world annual production of up to 1000 ten thousand tons. However, since the price of propylene raw materials increases year by year, and the plasticizer DEHP has a small molecular weight, is highly cleavable and volatile, and is highly toxic to human bodies, production and recycling are prohibited by the read regulations in the european union in 2015. Current improvement the current improved process is to obtain valeraldehyde by hydroformylation of mixed/ethered butenes, followed by a similar subsequent reaction to produce a high molecular weight novel plasticizer DPHP. DPHP is not easily cleaved and has low toxicity. Currently, this technology is expected to gradually replace the conventional technology. Traditional PPh-based 3 The technology can only realize the hydroformylation reaction of the 1-butene, the production cost of the 1-butene is high, and the cheaper raw material is mixed butene or ether-post-butene. Domestic hydroformylation industrial device mainly uses PPh 3 And bidentate phosphonite ligands (Biphephos) used in the Dow Chemical (Dow Chemical) are the dominant. In addition to the high patent and process package transfer costs required to be paid, the Biphephos ligand of the dow chemical is unstable in air for a long time, is easily hydrolyzed, acidolyzed and easily blocks a pipeline, and requires the addition of the ligand at random to ensure the catalytic activity.
Compared with the bidentate phosphonite ligand Biphephos, the preparation of the biphenyl tetradentate phosphonite ligand and the derivative thereof developed in the invention has the characteristics of easy synthesis, large-scale synthesis, higher yield, better reaction activity, high yield of linear aldehyde product, extremely stable water and oxygen, difficult decomposition and the like. Meanwhile, through preliminary industrial pilot researches and comparison of Biphephos and other bidentate phosphine ligands, the novel biphenyl tetradentate phosphonite ligand developed by the invention can realize higher conversion rate, positive-to-iso ratio and better activity and stability in the hydroformylation reaction of carbon four after mixing/ether, and has great potential and practical value.
Disclosure of Invention
The invention aims to develop a high-efficiency synthesis method of biphenyl tetradentate phosphonite ligand and derivatives thereof. The preparation is easy to synthesize, has higher yield and can amplify synthesis. The structure of the compound and its derivatives is shown below:
Figure SMS_1
in formula I, R may be a cyclic phosphine structure of a phosphite ester, as shown in the above formula. The synthetic route of the biphenyl tetraphosphine ligand is as follows:
Figure SMS_2
drawings
Fig. 1 is a flow chart and apparatus diagram of the present invention.
The accompanying drawing is an intermittent mixing/etherifying carbon four hydroformylation reaction device, wherein FC is a mass flowmeter, PI is a pressure sensor, TC is a temperature controller, TI is a temperature sensor, and TE is a thermocouple.
Detailed Description
The above route of the present invention will be specifically described by way of examples, which are provided for further illustration of the present invention, but are not to be construed as limiting the present invention in any way. Some insubstantial improvements and modifications in light of the teachings of this invention may occur to those skilled in the art.
Example 1
Preparation of 4, 6-di-tert-butyl-1, 3-dihydroxybenzene (schemes 1 and 2):
Figure SMS_3
to a 2L three-necked flask, 1 (55 g), t-butanol (92.5 g) and concentrated sulfuric acid (70 g) were successively added. After the addition was completed, the reaction flask was replaced with nitrogen atmosphere and heated to reflux for 24 hours. The solvent was dried under reduced pressure, 400mL of water was added, and extracted three times with ethyl acetate (500 mL each). The obtained organic phase is dried by anhydrous sodium sulfate and then dried under reduced pressure, and the residue is subjected to flash column chromatography to obtain 88g of target product with the yield of 80%. 1 H NMR(400MHz,CDCl 3 ):δ＝7.13(s,1H),6.09(s,1H),4.83(s,2H),1.38(s,18H)。
Figure SMS_4
Example 2
Preparation of 4, 6-di-tert-butyl-1, 3-dimethoxybenzene (scheme 1):
Figure SMS_5
into a 2L four neck round bottom flask was added 2 (31.5 g), methyl iodide (101 g), potassium carbonate (98.2 g) and 0.5L acetone in sequence. The resulting reaction system was heated to 30℃and reacted for 4 hours. After the resulting reaction mixture was concentrated, 400mL of water was added and extracted three times with ethyl acetate (600 mL each). The residue is subjected to column chromatography to obtain 30.5g of target product with 86% yield. 1 H NMR(400MHz,CDCl 3 ):δ＝7.17(s,1H),6.47(s,1H),3.83(s,6H),1.35(s,18H)。
Figure SMS_6
Example 3
Preparation of 2,2', 6' -tetramethoxy-3, 3', 5' -tetra-tert-butyl-1, 1' -biphenyl (scheme 1):
Figure SMS_7
a dry 1L Schlenk flask was charged with 25.0g of 4, 6-di-t-butyl-1, 3-dimethoxybenzene, the flask was replaced with nitrogen, and 100mL of tetrahydrofuran and TMEDA (14 g) were added at-78deg.C. To this was added dropwise a 2.5M solution of n-butyllithium (44 mL), followed by a further 100mL of a solution of ferric trichloride (39 g) in tetrahydrofuran. The resulting mixture was reacted at-78℃for 8 hours, and after the reaction solution was quenched with water, 300mL of water was added and extracted three times (400 mL each) with ethyl acetate. The obtained organic phase was dried over anhydrous sodium sulfate and then dried under reduced pressure to obtain a pale yellow oily substance, which was subjected to column chromatography to obtain 5.0g of the objective product in 21% yield. 1 H NMR(400MHz,CDCl 3 ):δ＝7.30(s,2H),3.41(s,12H),1.37(s,37H)。
Figure SMS_8
Example 4
Preparation of 2,2', 6' -tetrahydroxy-3, 3', 5' -tetra-tert-butyl-1, 1' -biphenyl (scheme 1):
Figure SMS_9
in a 1L Schlenk flask, 11g of 2,2', 6' -tetramethoxy-3, 3', 5' -tetra-tert-butyl-1, 1' -biphenyl, 500mL of anhydrous dichloromethane were added under nitrogen protection, and 35g of boron tribromide was added dropwise at-78 ℃. The resulting reaction mixture was allowed to warm to room temperature for 48 hours. Then 500mL of water was added thereto, and 500mL of ethyl acetate was added thereto to extract three times. The obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and the target product was obtained by column chromatography in 9.7g, with a yield of 91%. 1 H NMR(600MHz,CDCl 3 ):δ＝7.35(s,2H),4.89(s,4H),1.40(s,36H)。
Figure SMS_10
Example 5
Preparation of 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl (L1) (scheme 2):
Figure SMS_11
to a 2L three-necked flask, 2 (15 g), potassium dichromate (1.5 g), concentrated sulfuric acid and acetic acid (200 ml), and water (100 ml) were sequentially added. After the addition was completed, the reaction mixture was heated to reflux for 24 hours. The solvent was dried under reduced pressure, 400mL of water was added, and extracted three times with ethyl acetate (500 mL each). The obtained organic phase is dried by anhydrous sodium sulfate and then dried under reduced pressure, and the residue is subjected to flash column chromatography to obtain 5.1g of target product with 15% yield. 1 H NMR(600MHz,CDCl 3 ):δ＝7.35(s,2H),4.89(s,4H),1.40(s,36H)。
Example 6
Preparation of 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl (L1) (schemes 1 and 2): preparation of 1,1 '-biphenyl-2, 2' -dioxy chlorophosphine
Figure SMS_12
20g of 2,2' -biphenol was added to the excess PCl 3 After heating and refluxing for 6 hours, excess PCl was distilled off under reduced pressure 3 18g of yellow oily product 7 are obtained in 71% yield. 1 H NMR(400MHz,CDCl 3 ):δ＝7.41(dd,J＝7.5,1.9Hz,2H),7.36–7.25(m,4H),7.15(dt,J＝7.9,1.2Hz,2H)。 31 PNMR(162MHz,CDCl 3 ):δ＝179.54.
Figure SMS_13
Figure SMS_14
2,2', 6' -tetrakis [ (1, 1 '-biphenyl-2, 2' -diyl) phosphonite]3,3', 5' -tetra-tert-butyl-1, 1' -) Preparation of biphenyls
Figure SMS_15
2,2', 6' -tetrahydroxy-3, 3', 5' -tetra-tert-butyl-1, 1' -biphenyl 4.2g, anhydrous tetrahydrofuran 100mL were added in sequence under nitrogen protection in a 2L Schlenk flask, and 2.5M n-butyllithium 15mL was added dropwise at-78deg.C. The reaction mixture was allowed to warm to room temperature and then was refluxed for 1 hour. Then, the reaction solution was dropped into 100mL of an anhydrous tetrahydrofuran solution of 1,1' -dioxyphosphine chloride (13 g) at-78℃and reacted at room temperature for 24 hours after the dropping was completed, the reaction solution was concentrated under nitrogen atmosphere, and the target product was obtained by column chromatography of the residue in a yield of 6.0 g. 1 H NMR(600MHz,CDCl 3 ):δ＝7.43–7.35(m,12H),7.32(d,J＝8.1Hz,3H),7.22(tdd,J＝6.7,4.9,1.6 Hz,15H),6.88(dt,J＝7.2,1.5 Hz,5H),1.84–0.95(m,36H)。 31 PNMR(243 MHz,CDCl 3 ):δ＝144.35。APCI-TOF/MS:Calculated for C 76 H 71 O 12 P 4 [M+H] + :1299.3818；Found:1299.3891
Figure SMS_16
Figure SMS_17
Figure SMS_18
It is noted here that the other biphenyl tridentate phosphine ligands of the formula I L2-L26 can be prepared by using only the different aryl substituent phosphine chloride derivatives in example 6.
After obtaining the target biphenyl tetradentate phosphite ligand, we developed a batch pilot reaction apparatus (attached drawing in the specification) matched with the novel biphenyl tetradentate phosphite ligand, simulating the hydroformylation of carbon four after industrial mixing/ether. We used 2 kinds of carbon four raw materials, respectively, the first is mixed butene/carbon four (material 1), the component contents are (w/w): 1-butene (25%), cis-2-butene (40%) and trans-2-butene (35%); the second is carbon four after ether (material 2), the component contents are (w/w): isobutane (52.1%), 1-butene (16.6%), cis-2-butene (15.3%) and trans-2-butene (16.0%). In addition, to verify the isomerization activity of the ligand, we used pure cis-2-butene (feed 3, 98%) and trans-2-butene (feed 4, 99%) as reaction raw materials, respectively.
In order to ensure ligand activity and aldehyde products not to be oxidized, the materials pass through a raw material pretreatment device, and besides water removal, oxygen removal, sulfur removal (sulfide), chlorine removal (halide), nitrogen removal compounds (such as HCN) and the like, substances such as carboxylic acid, butadiene, allene, alkyne and the like which have an inhibition effect on rhodium catalysts in the four-carbon raw material are removed. To test the reactivity of the novel biphenyltetraphosphine in carbon four after mixing/ether, we compared other commercial and literature reported ligands under nearly identical reaction conditions, the ligands Ligand Ligand 1-12 used in the following examples had the following structure:
Figure SMS_19
Figure SMS_20
example 7
Adding a certain amount of Rh (acac) (CO) into 200ml stainless steel high-pressure reaction kettle equipped with pressure sensor, temperature probe, on-line sampling port and safety pressure release valve under argon atmosphere 2 (0.01 mmol,2.6 mg) and a certain amount of Ligand Ligand 1-12 (0.02-0.06 mmol), a certain volume of n-valeraldehyde and an internal standard n-decane were added, and the mixture was stirred and complexed with a magnet for 30 minutes to produce a catalytic complex of rhodium and Ligand. Subsequently, the first and second heat exchangers are connected,after the gas pipeline is connected and fully replaced, a certain proportion of liquefied mixed carbon four (material 1) is added into a reaction kettle by a plunger pump with a metering function under the switching of a two-position four-way valve, so that the concentration of the rhodium catalyst in the total solution is controlled to be about 159ppm, and then the mixture is uniformly stirred for 5 to 10 minutes at room temperature. After stirring uniformly, the mixed gas (1:1) of carbon monoxide and hydrogen is filled into the reaction device until the total pressure is 1.0MPa. The reaction kettle is raised to the required temperature (80-110 ℃) by a magnetic stirrer (heating the bottom of the kettle) and an electric heating sleeve (heating the kettle body), and the total pressure is kept constant at 1.0MPa by continuously supplementing air in the reaction. After 2-4 hours of reaction, the reaction kettle is connected into a cold sleeve at-40 ℃ for cooling, after the kettle temperature is reduced to normal temperature, an online sampling port is opened for sampling under the condition of not opening the kettle, and after the reaction kettle is diluted by chromatographic grade ethyl acetate, a Gas Chromatograph (GC) is used for measuring the normal-to-iso ratio (the ratio of n-valeraldehyde to 2-methyl butyraldehyde: l: b). After the kettle is opened, the gas in the high-pressure reaction kettle is completely released in a fume hood, and the sample is taken and weighed. The results are shown in Table 1.
TABLE 1
Figure SMS_21
a The reaction temperature of 40-80 ℃ means: 1-butene starts to react at about 40 ℃, and cis-2-butene and trans-2-butene start to react at about 80 DEG C
Example 8
Adding a certain amount of Rh (acac) (CO) into 200ml stainless steel high-pressure reaction kettle equipped with pressure sensor, temperature probe, on-line sampling port and safety pressure release valve under argon atmosphere 2 (0.01 mmol,2.6 mg) and a certain amount of Ligand Ligand 1-12 (0.02-0.06 mmol), a certain volume of n-valeraldehyde and an internal standard n-decane were added, and the mixture was stirred and complexed with a magnet for 30 minutes to produce a catalytic complex of rhodium and Ligand. Then, after connecting the gas pipeline and fully replacing, adding a certain proportion of liquefied ether carbon four (material 2) into the reaction kettle by a plunger pump with a metering function under the switching of a two-position four-way valve, controlling the concentration of the rhodium catalyst in the total solution to be about 159ppm, and uniformly stirring for 5-10 minutes at room temperature. After being stirred uniformlyThe reaction apparatus was charged with 5bar of each of carbon monoxide and hydrogen. The reaction kettle is raised to the required temperature (80-110 ℃) by a magnetic stirrer and an electric heating sleeve, and the total pressure is kept constant at 1.0MPa by continuously supplementing air in the reaction. After 2-4 hours of reaction, the reaction kettle is connected into a cold sleeve at-40 ℃ for cooling, after the kettle temperature is reduced to normal temperature, an online sampling port is opened for sampling under the condition of not opening the kettle, and after the reaction kettle is diluted by chromatographic grade ethyl acetate, the positive-to-negative ratio is measured by a Gas Chromatograph (GC). After the kettle is opened, the gas in the high-pressure reaction kettle is completely released in a fume hood, and the sample is taken and weighed. The results are shown in Table 2.
TABLE 2
Figure SMS_22
a The reaction temperature of 40-80 ℃ means: 1-butene starts to react at about 40 ℃, and cis-2-butene and trans-2-butene start to react at about 80 DEG C
Example 9
Adding a certain amount of Rh (acac) (CO) into 200ml stainless steel high-pressure reaction kettle equipped with pressure sensor, temperature probe, on-line sampling port and safety pressure release valve under argon atmosphere 2 (0.01 mmol,2.6 mg) and a certain amount of Ligand Ligand 1-12 (0.02-0.06 mmol), a certain volume of n-valeraldehyde and an internal standard n-decane were added, and the mixture was stirred and complexed with a magnet for 30 minutes to produce a catalytic complex of rhodium and Ligand. Then, after connecting the gas pipeline and fully replacing, adding a certain proportion of liquefied cis-2-butene (material 3) into the reaction kettle by a plunger pump with a metering function under the switching of a two-position four-way valve, controlling the concentration of the rhodium catalyst in the total solution to be about 159ppm, and uniformly stirring for 5-10 minutes at room temperature. After stirring uniformly, 5bar of carbon monoxide and hydrogen are respectively charged into the reaction device. The reaction kettle is raised to the required temperature (80-110 ℃) by a magnetic stirrer (heating the bottom of the kettle) and an electric heating sleeve (heating the kettle body), and the total pressure is kept constant at 1.0MPa by continuously supplementing air in the reaction. After 2-4 hours of reaction, the reaction kettle is connected with a cold sleeve at-40 ℃ for cooling, after the kettle temperature is cooled to normal temperature, an online sampling port is opened for sampling under the condition of not opening the kettle, and chromatographic grade is usedAfter dilution with ethyl acetate, the n-iso ratio (ratio of n-valeraldehyde/2-methylbutyraldehyde) was measured by Gas Chromatography (GC). After the kettle is opened, the gas in the high-pressure reaction kettle is completely released in a fume hood, and the sample is taken and weighed. The results are shown in Table 3.
TABLE 3 Table 3
Figure SMS_23
Example 10
Adding a certain amount of Rh (acac) (CO) into 200ml stainless steel high-pressure reaction kettle equipped with pressure sensor, temperature probe, on-line sampling port and safety pressure release valve under argon atmosphere 2 (0.01 mmol,2.6 mg) and a certain amount of Ligand Ligand 1-12 (0.02-0.06 mmol), a certain volume of n-valeraldehyde and an internal standard n-decane were added, and the mixture was stirred and complexed with a magnet for 30 minutes to produce a catalytic complex of rhodium and Ligand. Then, after connecting the gas pipeline and fully replacing, adding a certain proportion of liquefied trans-2-butene (material 4) into the reaction kettle by a plunger pump with a metering function under the switching of a two-position four-way valve, controlling the concentration of the rhodium catalyst in the total solution to be about 159ppm, and uniformly stirring for 5-10 minutes at room temperature. After stirring uniformly, 5bar of carbon monoxide and hydrogen are respectively charged into the reaction device. The reaction kettle is raised to the required temperature (80-110 ℃) by a magnetic stirrer (heating the bottom of the kettle) and an electric heating sleeve (heating the kettle body), and the total pressure is kept constant at 1.0MPa by continuously supplementing air in the reaction. After 2-4 hours of reaction, the reaction kettle is connected into a cold sleeve at-40 ℃ for cooling, after the kettle temperature is reduced to normal temperature, an online sampling port is opened for sampling under the condition of not opening the kettle, and after the reaction kettle is diluted by chromatographic grade ethyl acetate, a Gas Chromatograph (GC) is used for measuring the n-iso ratio (the ratio of n-valeraldehyde to 2-methyl butyraldehyde). After the kettle is opened, the gas in the high-pressure reaction kettle is completely released in a fume hood, and the sample is taken and weighed. The results are shown in Table 4.
TABLE 4 Table 4
Figure SMS_24

Claims (10)

1. A method for preparing novel biphenyl tetradentate phosphite ligand 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and derivatives thereof, which is characterized by having the following synthetic route:
Figure FDA0004145493790000011
or directly obtaining 2,2', 6' -tetrahydroxy-3, 3', 5' -tetra-tert-butyl-1, 1' -biphenyl (5) from 4, 6-di-tert-butyl resorcinol (2) by an oxidative coupling method, and then dropwise adding biphenyl tetraphenol (5) taking butyl lithium or organic weak base as an acid-binding agent into a solution of phosphine chloride R-Cl to obtain biphenyl tetraphosphine ligand:
Figure FDA0004145493790000012
wherein, the novel biphenyl tetradentate phosphite ligand represented by the general formula I has the following structure:
Figure FDA0004145493790000021
Figure FDA0004145493790000031
Figure FDA0004145493790000041
2. the process for the preparation of a novel biphenyl tetradentate phosphite ligand 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and derivatives thereof as defined in claim 1, wherein the backbone synthesis is effected by the following reaction, the preparation of 4, 6-di-tert-butyl-1, 3-dihydroxybenzene comprising:
Figure FDA0004145493790000051
3. the process for the preparation of a novel biphenyl tetradentate phosphite ligand 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and derivatives thereof as defined in claim 1, wherein the backbone synthesis is effected by the following reaction, the preparation of 4, 6-di-tert-butyl-1, 3-dimethoxybenzene comprising:
Figure FDA0004145493790000052
4. the process for the preparation of a novel biphenyl tetradentate phosphite ligand 2,2', 6' -tetrakis [ (1, 1 '-biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1 '-biphenyl and derivatives thereof as defined in claim 1, wherein the backbone synthesis is effected by the following reaction, the preparation of 2,2',6 '-tetramethoxy-3, 3',5 '-tetra-tert-butyl-1, 1' -biphenyl comprising:
Figure FDA0004145493790000053
5. the process for the preparation of a novel biphenyl tetradentate phosphite ligand 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and derivatives thereof according to claim 1, wherein the backbone synthesis is effected by the following reaction:
Figure FDA0004145493790000061
6. the process for the preparation of a novel biphenyl tetradentate phosphite ligand 2,2', 6' -tetrakis [ (1, 1' -biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1' -biphenyl and derivatives thereof according to claim 1, wherein the backbone synthesis is effected by the following reaction:
Figure FDA0004145493790000062
wherein the above reaction is characterized in that the ether solvent used in the reaction may be any one of anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methyl tertiary butyl ether, ethyl tertiary butyl ether, diethyl ether, isopropyl ether, butyl ether, 2-methyltetrahydrofuran or dioxane.
7. The process for the preparation of a novel biphenyl tetradentate phosphonite ligand 2,2', 6' -tetrakis [ (1, 1 '-biphenyl-2, 2' -diyl) phosphonite ] -3,3', 5' -tetra-tert-butyl-1, 1 '-biphenyl and derivatives thereof as defined in claim 1, wherein the backbone synthesis is effected by the following reaction, the preparation of 2,2',6 '-tetrakis [ (1, 1' -biphenyl-2, 2 '-diyl) phosphonite ] -3,3',5 '-tetra-tert-butyl-1, 1' -biphenyl (L1) comprising:
Figure FDA0004145493790000063
meanwhile, the ether solvent used in the above reaction may be any one of anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methyl tertiary butyl ether, ethyl tertiary butyl ether, diethyl ether, isopropyl ether, butyl ether, 2-methyltetrahydrofuran or dioxane.
8. A process for the hydroformylation of carbon after mixing/ether with a novel biphenyl tetradentate phosphonite as ligand, characterized in that the novel biphenyl tetradentate phosphonite ligand used may be as shown in claim 1 and have the general formula I.
9. The method for the mixed/etherified carbon four hydroformylation reaction using novel biphenyl tetradentate phosphonite as ligand according to claim 8, wherein the method is realized according to the following process steps and parameters:
(1) Sequentially adding a certain proportion of novel biphenyl tetradentate phosphonite ligand and rhodium catalyst in a reaction device under the protection of inert gas, 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 carbon tetra-or etherified carbon tetra-or cis-2-butene or trans-2-butene into a reaction kettle by a plunger pump with a metering function, controlling the concentration of rhodium catalyst to be about 50-200 ppm, and uniformly stirring for 5-10 minutes at room temperature;
(3) Uniformly stirring, and charging CO and H with a certain pressure into the reaction device 2 The pressure ratio of the hydrogen to the carbon monoxide is between 1:1 and 1:5, and the total pressure is between 0.5MPa and 1 MPa; the reaction is stirred for 1 to 4 hours at a temperature between 40 ℃ and 80 ℃.
10. The reaction process of claim 9, wherein the mixed carbon four and ether carbon four is: mixing carbon four (1-butene (25 wt%), cis-2-butene (40 wt%) and trans-2-butene (35 wt%), post-ether carbon four (isobutane (52.1 wt%), 1-butene (16.6 wt%), cis-2-butene (15.3 wt%) and trans-2-butene (16.0 wt%)); the content of cis-2-butene and trans-2-butene is above 98.0wt%.
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