CN113004326A - Phosphine ligand for butadiene hydroformylation reaction and preparation method thereof - Google Patents

Phosphine ligand for butadiene hydroformylation reaction and preparation method thereof Download PDF

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CN113004326A
CN113004326A CN202110260439.8A CN202110260439A CN113004326A CN 113004326 A CN113004326 A CN 113004326A CN 202110260439 A CN202110260439 A CN 202110260439A CN 113004326 A CN113004326 A CN 113004326A
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butadiene
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phosphine ligand
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bidentate phosphine
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CN113004326B (en
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杨勇
王召占
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Abstract

The invention discloses a bidentate phosphine ligand compound with a structure shown in a general formula 1, a synthetic method thereof and application of the phosphine ligand in promoting metal catalysis of 1, 3-butadiene hydroformylation reaction.

Description

Phosphine ligand for butadiene hydroformylation reaction and preparation method thereof
Technical Field
The invention belongs to the field of catalysis and fine chemical engineering, and particularly relates to a bidentate phosphine ligand compound, a synthesis method thereof and application of the phosphine ligand in promoting metal catalysis of 1, 3-butadiene hydroformylation reaction.
Background
The hexanedial (1, 6-hexanedial) can be directly used for synthesizing C6 compounds with higher application value and larger market demand as an important organic synthesis raw material, such as adipic acid (1, 6-adipic acid), hexamethylenediamine (1, 6-hexamethylenediamine), hexanediol (1, 6-hexanediol) and the like. These C6 compounds are key monomers for the industrial synthesis of polyester, polyamide (nylon 66 or nylon 610), polyurethane, and the like.
The synthesis of adipaldehyde is currently mainly prepared by the multi-step oxidation reaction of 1, 6-cyclohexanediol or cyclohexene. The methods generally have the problems that the sources of reaction raw materials and oxidants are not easy to obtain, the price is high, the oxidants are not easy to circulate, the method is not environment-friendly, the yield of the target product, namely the adipaldehyde is low, and the like. In principle, adipaldehyde can also be prepared by hydroformylation of butadiene. Under the action of catalyst, butadiene and synthetic gas are subjected to two-step carbonylation to obtain the target product hexanedial. Once the research route is broken through, the research route becomes a new innovation route and is expected to replace the current route for producing adiponitrile by butadiene hydrocyanation. In addition, China is a large world producing country of butadiene raw materials, develops new application and consumption fields of butadiene, extends an industrial chain, realizes refinement and high-end utilization of the butadiene, and has important economic and social benefits.
The key to the breakthrough of butadiene hydroformylation technology lies in the development of catalysts, and particularly in the design and synthesis of novel structural phosphine ligands. The phosphine ligand structure plays a decisive role in the activity of the catalytic reaction and the selectivity of the product. The research on the synthesis of hexanedial by butadiene hydroformylation reaction has been carried out for more than 60 years, but the research and exploration stages in laboratories are still in progress at present, and no industrial report is available. Early (1960-. In 1994, united states of america combined with carbonation chemicals and Plastics Technology Corporation (Union Carbide Chemical & Plastics Technology Corporation), phosphite bidentate ligand-rhodium catalyzed butadiene directional conversion reaction of hexanedial was developed, the reaction conditions were relatively mild, and the selectivity of hexanedial could reach 30%. The company applies for protection to the catalyst system from U.S. Pat. No. 5,5312996, world patent WO 97/40003, etc. Based on the breakthrough result, a series of phosphite ester ligands with novel structures are developed successively and applied to the hydroformylation of butadiene. Hofmann and its research group have made systematic research work in this regard, and developed a new class of phosphate ligands (Organometallics 2011,30, 3643-.
Despite over 60 years of research, the selectivity of adipaldehyde is still below 50%, which is far from the needs of industrial demonstration. Further improvement of the selectivity of the adipaldehyde is the key to realizing breakthrough of the process route early. In summary, the challenges of the directional preparation of adipaldehyde via hydroformylation reaction routes for butadiene are complex reaction schemes, slow reaction rates, and difficult regioselectivity control. Obviously, the development of a new structural ligand of the catalyst is a key for realizing directional preparation of the hexanedial by hydroformylation of the butadiene, and is directly related to whether the reaction route can be industrialized.
Disclosure of Invention
In view of the problems in the prior art described above, it is an object of the present invention to provide a bidentate phosphine ligand compound having a structure of formula 1,
Figure BDA0002969745780000021
wherein R is1Selected from the following structures:
Figure BDA0002969745780000022
Figure BDA0002969745780000023
wherein ". quadrature" denotes R1And (c) the connection location.
Preferably, R1Is selected from
Figure BDA0002969745780000024
R2And R3Each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, C6-C10 aryl, C1-C6 alkoxy substituted C6-C10 aryl, C1-C6 alkyl substituted C6-C10 aryl, C2-C6 alkenyl substituted C6-C10 aryl or C2-C6 alkylamino substituted C6-C10 aryl.
R2And R3Each independently selected from the following structures:
Figure BDA0002969745780000025
Figure BDA0002969745780000031
Figure BDA0002969745780000032
wherein ". quadrature" denotes R2And R3An upper connection location;
more preferably, R2And R3Each independently selected from:
Figure BDA0002969745780000033
R4and R5Are phosphine-containing groups and are each independently selected from the following structures:
Figure BDA0002969745780000034
Figure BDA0002969745780000041
preferably, R4And R5Each independently selected fromThe following structure:
Figure BDA0002969745780000042
Figure BDA0002969745780000051
preferably, the bidentate phosphine ligand is selected from the group consisting of L1 to L6:
Figure BDA0002969745780000052
Figure BDA0002969745780000061
according to another aspect of the present invention, it is another object of the present invention to provide a method for preparing the bidentate phosphine ligand, which comprises reacting a phosphine-chlorine compound with an ethereal solvent
Figure BDA0002969745780000062
Or
Figure BDA0002969745780000063
In the presence of a base, with a phosphine-chlorine compound
Figure BDA0002969745780000064
Or
Figure BDA0002969745780000065
The molar ratio of (1: 5) - (2: 1) is-78-150 ℃, and the time is 0.5-24 h;
wherein
Figure BDA0002969745780000066
Or
Figure BDA0002969745780000067
Substituent R in (1)1、R2And R3The definition of (a) is the same as in formula 1.
Preferably, the base is selected from one or more of triethylamine, Dimethylaminopyridine (DMAP), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), pyridine, sodium hydride (NaH), bis (trimethylsilyl) aminolithium (LiHMDS) and n-butyllithium (n-BuLi).
Preferably, the ethereal solvent is selected from tetrahydrofuran, diethyl ether, tert-butyl ether, methyl tert-butyl ether, preferably tetrahydrofuran and diethyl ether.
Preferably, the phosphine-chlorine compound is selected from the following structures:
Figure BDA0002969745780000071
said
Figure BDA0002969745780000072
The synthesis method comprises the following steps:
Figure BDA0002969745780000073
wherein compound C1 is reacted with a compound comprising R1Adding the corresponding alkene or alkyne into a solvent, and controlling the temperature to be 100-200 ℃; the time is 5h-48h, and the solvent is removed by reduced pressure distillation after the reaction is finished to obtain D1, substituent R1The definition of (a) is the same as in formula 1.
Preferably, the solvent is an aromatic hydrocarbon solvent, preferably toluene or xylene.
Preferably, said comprises R1The corresponding alkene or alkyne of (a) is selected from the following structures:
Figure BDA0002969745780000074
Figure BDA0002969745780000075
and the like.
The synthesis of compound C1 can be carried out according to methods disclosed in the prior art, for example, the synthesis method described in Dalton trans, 2019,48, 14777-.
Said
Figure BDA0002969745780000081
The synthesis method comprises the following steps:
Figure BDA0002969745780000082
1) a2 is reacted with benzyl bromide in DMF or acetone solvent at 60 ℃ by taking anhydrous potassium carbonate as alkali to obtain a compound B2;
2) b2 is reduced by zinc powder in NaOH solution at 100 ℃ to obtain a compound C2;
3) c2 with a solvent comprising R1Reacting the corresponding alkene or alkyne to obtain a compound D2 at the temperature of 100-200 ℃ for 5-48 h;
4) the debenzylation of D2 in methanol by catalytic reduction with Pd/C catalyst under hydrogen atmosphere gave E2.
Preferably, the solvent in step 3) is an aromatic hydrocarbon solvent, preferably toluene or xylene.
Preferably, said step 3) comprises R1The corresponding alkene or alkyne of (a) can be of the structure:
Figure BDA0002969745780000083
Figure BDA0002969745780000084
and the like.
It is another object according to the present invention to provide the use of said bidentate phosphine ligand to promote metal-catalyzed butadiene hydroformylation.
It is another object of the present invention to provide a method for preparing 1, 6-hexanedial by hydroformylation of butadiene, which is a process for converting butadiene into 1, 6-hexanedial under conditions of a suitable solvent, a bidentate phosphorus ligand, a metal precursor, temperature, mixed gas pressure and time, comprising the steps of:
adding a proper amount of the bidentate phosphine ligand into a reaction kettle, then adding a solvent, a metal precursor and butadiene, sealing the reaction kettle, and filling H with a certain pressure2And the mixed gas consisting of CO reacts for a certain time at a set temperature.
Preferably, the solvent is selected from aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents or ether solvents.
Preferably, the solvent is selected from one or more of n-hexane, cyclohexane, octane, benzene, toluene, xylene, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran and dioxane, preferably toluene.
Preferably, the metal precursor is a precursor of metal rhodium and cobalt, selected from: rh (CO)2(acac)、Rh(AcO)2、RhCl3、Rh(NO3)3、RhH(CO)(PPh3)3、[Rh(CO)2Cl]2、RhH(CO)(PPh3)3、[Rh2(m-Cl)2(cod)2]、[Rh(cod)2]BF4、Co(CO)2(acac)、Co(AcO)2、CoCl2、Co(acac)2Preferably Rh (CO)2(acac)。
Preferably, the molar ratio of metal precursor to bidentate phosphine ligand is from 2:1 to 1:10, preferably from 1:1 to 1:5, more preferably from 1:1 to 1: 3.
Preferably, the molar ratio of metal precursor to butadiene is from 1/50 to 1/5000, preferably from 1/100 to 1/1000.
Preferably, the butadiene is a butadiene hexane solution, a butadiene toluene solution, a butadiene tetrahydrofuran solution, a butadiene methanol solution, and pure butadiene, preferably a butadiene toluene solution.
Preferably, H in the mixed gas2And CO in a volume ratio of 1/2-3/1, preferably 1/1-2/1.
Preferably, the pressure of the mixed gas is 1MPa to 10MPa, preferably 2MPa to 5 MPa.
Preferably, the reaction temperature is from 50 ℃ to 200 ℃, preferably from 80 ℃ to 120 ℃.
Preferably, the reaction time is from 5h to 24h, preferably from 5h to 15 h. Preferably, the reaction concentration of butadiene is from 0.1mol/L to 10mol/L, preferably from 0.5mol/L to 3 mol/L.
Advantageous effects
The catalyst formed by the bidentate phosphine ligand and the active metal can catalyze the hydroformylation of 1, 3-butadiene to prepare the hexanedial, compared with other catalysts reported in literatures, the hexanedial content in the product is obviously increased, the selectivity is most preferably close to 60%, and the byproducts are relatively less. Therefore, the catalyst formed by the bidentate phosphine ligand and the active metal has good catalytic effect, and lays a foundation for further industrialization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a liquid nuclear magnetic hydrogen spectrum of Compound B2 in preparative example 1.
FIG. 2 is a liquid nuclear magnetic hydrogen spectrum of Compound C2 in preparation example 1.
FIG. 3 is a liquid nuclear magnetic hydrogen spectrum of Compound D21 in preparation example 1.
FIG. 4 is a liquid nuclear magnetic hydrogen spectrum of Compound F2 in preparation example 1.
FIG. 5 is a liquid nuclear magnetic hydrogen spectrum of Compound E21 in preparation example 1.
FIG. 6 is a liquid nuclear magnetic hydrogen spectrum of bidentate phosphine ligand L1 in preparative example 1.
FIG. 7 is a liquid nuclear magnetic phosphorus spectrum of bidentate phosphine ligand L1 in preparative example 1.
FIG. 8 is a liquid nuclear magnetic hydrogen spectrum of bidentate phosphine ligand L2 in preparative example 2.
FIG. 9 is a liquid nuclear magnetic phosphorus spectrum of bidentate phosphine ligand L2 in preparative example 2.
FIG. 10 is a liquid nuclear magnetic hydrogen spectrum of bidentate phosphine ligand L3 in preparative example 3.
FIG. 11 is a liquid nuclear magnetic phosphorus spectrum of bidentate phosphine ligand L3 in preparative example 3.
FIG. 12 is a liquid nuclear magnetic hydrogen spectrum of bidentate phosphine ligand L4 in preparative example 4.
FIG. 13 is a liquid nuclear magnetic phosphorus spectrum of bidentate phosphine ligand L4 in preparative example 4.
FIG. 14 is a liquid nuclear magnetic hydrogen spectrum of Compound G21 in preparation example 5.
Fig. 15 is a liquid nuclear magnetic hydrogen spectrum of compound H21 in preparative example 5.
FIG. 16 is a liquid nuclear magnetic hydrogen spectrum of bidentate phosphine ligand L5 in preparative example 5.
FIG. 17 is a liquid nuclear magnetic phosphorus spectrum of bidentate phosphine ligand L5 in preparative example 5.
FIG. 18 is a liquid nuclear magnetic hydrogen spectrum of bidentate phosphine ligand L6 in preparative example 6.
FIG. 19 is a liquid nuclear magnetic phosphorus spectrum of bidentate phosphine ligand L6 in preparative example 6.
Detailed Description
For better understanding of the present invention, the contents of the present invention are further illustrated below by referring to examples, which are only part of examples illustrating embodiments of the present invention and do not limit the present invention in any way, and those skilled in the art will understand that modifications within the scope not departing from the spirit and concept of the present invention fall within the protection scope of the present invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Material characterization instrumentation used:
(1) gas chromatograph: model GC-2010, manufacturer Shimadzu, Japan
(2) Gas chromatography-mass spectrometer: the model is GCMS-QP2010, and the manufacturer is Japanese SHIMADZU
(3) Liquid chromatography mass spectrometer: the model is Agilent1290-6430, and the manufacturer is Agilent in America
(4) Nuclear magnetic resonance spectrometer: the models are ASCEND 400MHz and AVANCE-III 600MHz, and the manufacturer is Bruker, Switzerland.
In specific embodiment, the metal precursor selected by the catalytic system is Rh (acac) (CO)2The bidentate phosphine ligand used has the following structure:
Figure BDA0002969745780000111
preparation example 1: synthesis of ligand L1
Figure BDA0002969745780000112
Figure BDA0002969745780000121
Step 1: synthesis of compound B2:
10g of 1, 8-dihydroxyanthraquinone (Compound A2) are introduced into a reactor, dissolved in 200ml of DMF and 17.2g of anhydrous K are added2CO3And 21.2g of benzyl bromide, and reacted at 60 ℃ overnight. After cooling to room temperature, the reaction solution was quenched by adding to 600ml of water to give a large amount of yellow precipitate, which was filtered, washed with water and dried under vacuum at 60 ℃ to give compound B2. The nuclear magnetic data are as follows:1H NMR(600MHz,CDCl3)δ7.86(d,J＝7.6Hz,2H),7.63(d,J＝7.4Hz,6H),7.59(t,J＝8.0Hz,2H),7.39(t,J＝7.5Hz,4H),7.33(d,J＝7.7Hz,4H),5.33(s,4H)。
step 2: synthesis of compound C2:
8.5g of Compound B2 were placed in a reactor, 170ml of a 10% NaOH solution and 13g of zinc powder were added, and the mixture was refluxed at 100 ℃ overnight. Cooling to room temperature, diluting with 200ml of water, extracting with 300ml of ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and purifying by column chromatography, wherein the eluent is petroleum ether and ethyl acetate is 5:1, and the pure compound C2 is obtained by separation. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ9.46(s,1H),8.33(s,1H),7.63-7.53(m,6H),7.37(m,J＝8.3,5.3Hz,8H),6.80(d,J＝7.4Hz,2H),5.32(s,4H)。
and step 3: synthesis of compound D21:
2g of compound C2 were introduced into a reactor, 20ml of xylene were added and 1.09g of dimethyl butynedioate were added and the reaction was refluxed overnight under nitrogen. Cooling to room temperature, adding into 50ml petroleum ether for precipitation, filtering, washing with petroleum ether, and vacuum drying to obtain compound D21. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.44(dd,J＝6.5,2.9Hz,4H),7.28(dd,J＝5.0,1.8Hz,6H),7.05(d,J＝7.2Hz,2H),6.94(d,J＝8.1Hz,2H),6.66(d,J＝8.1Hz,2H),6.60(s,1H),5.52(s,1H),5.11(s,4H),3.78(d,J＝6.1Hz,6H)。
and 4, step 4: synthesis of compound F2:
2.5g of the compound D21 was put into a reactor, 35ml of methanol was added, 3g of NaOH was dissolved in 35ml of deionized water, and the solution was added to the above reaction solution and reacted for 4 hours under reflux. Cooling to room temperature, adjusting pH to 2-3 with dilute hydrochloric acid, filtering, washing with water, and vacuum drying. The resulting product was added to 50ml of quinoline (quinoline), 1.4g of copper powder was added, and the reaction was carried out for 3 hours at 240 ℃ under nitrogen. After cooling to room temperature, dilution with 100ml of ethyl acetate, washing off of the quinoline with dilute hydrochloric acid and drying of the organic phase over anhydrous sodium sulfate, column chromatography is carried out to give the pure compound F2. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.49–7.40(m,4H),7.33–7.26(m,6H),7.07–7.01(m,1H),6.99(dd,J＝10.4,4.4Hz,3H),6.92–6.85(m,2H),6.64(d,J＝7.8Hz,2H),6.27(dd,J＝5.9,1.5Hz,1H),5.16(dd,J＝5.7,1.5Hz,1H),5.13–5.01(m,4H)。
and 5: synthesis of compound E21:
2.1g of compound F2 was charged into a reactor, dissolved in 20ml of tetrahydrofuran, diluted with 60ml of methanol, and 200mg of palladium on carbon was added to replace the gas in the reactor with hydrogen for 3 times, followed by addition of a hydrogen balloon and reaction at room temperature overnight. Filtering with diatomite, washing with tetrahydrofuran, decompression evaporating to eliminate solvent and vacuum drying to obtain compound E21. The nuclear magnetic data are as follows:1H NMR(600MHz,DMSO)δ9.20(s,2H),6.83(d,J＝7.8Hz,2H),6.73(d,J＝7.1Hz,2H),6.57(dd,J＝8.0,0.6Hz,2H),5.07(s,1H),4.21(d,J＝2.5Hz,1H),1.55–1.45(m,5H)。
step 6: synthesis of ligand L1:
250mg of dipyrrolyl phosphorus chloride P1 is added into a reactor, 2ml of dry tetrahydrofuran is added, the temperature is reduced to 0 ℃, 100mg of a compound E21 and 128mg of triethylamine are dissolved in 1ml of dry tetrahydrofuran, the mixed solution is dripped into the reactor at the temperature of 0 ℃, the temperature is naturally raised to the room temperature, and the reaction is carried out for 1 h. Quenching in 10ml water, extracting with 10ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain ligand L1. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.13–6.87(m,12H),6.63–6.55(m,2H),6.34–6.25(m,8H),4.91(s,1H),4.25(s,1H),1.58–1.49(m,2H),1.30–1.23(m,2H)。31P NMR(162MHz,CDCl3)δ108.25。
preparation example 2: synthesis of ligand L2
Figure BDA0002969745780000131
100mg of the compound E21 obtained in preparation example 1 was taken and added to a reactor, 2ml of dry DMF was added and dissolved, the temperature was reduced to 0 ℃, 36.8mg of NaH was added in portions and the reaction was carried out at room temperature for 30min, and 212mg of phosphorus chloride P2 was taken and dissolved in 0.5ml of dry DMF and slowly added dropwise to the reactor and reacted at room temperature overnight. Quenching in 10ml water, extracting with 10ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain ligand L2. The nuclear magnetic data are as follows:1H NMR(400MHz,C6D6)δ8.53(s,2H),7.75(t,J＝14.5Hz,1H),7.41(d,J＝7.8Hz,1H),7.34(dd,J＝8.0,2.9Hz,1H),7.03(dt,J＝25.3,7.6Hz,3H),6.87(dt,J＝12.9,7.4Hz,4H),6.64–6.53(m,2H),5.96(s,1H),4.12(s,1H),1.83–1.69(m,2H),1.54(dd,J＝13.2,6.0Hz,2H),1.34(d,J＝12.5Hz,9H),1.23(d,J＝12.5Hz,9H)。31P NMR(162MHz,C6D6)δ118.86,114.85。
preparation example 3: synthesis of ligand L3
Figure BDA0002969745780000141
578mg of phosphorus chloride P3 were charged into a reactor, 4ml of dry tetrahydrofuran was added, the temperature was lowered to 0 ℃ and 150mg of the compound E21 obtained in preparation example 1 and 334mg of triethylamine were dissolved in 2ml of dry tetrahydrofuran, and this mixture was added dropwise to the above reactor at 0 ℃ and allowed to warm to room temperature naturally, followed by reaction for 1 hour. Quenching in 10ml water, extracting with 10ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain ligand L3. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.04(dt,J＝8.6,2.0Hz,10H),6.92(d,J＝10.3Hz,4H),5.41(s,1H),4.37(s,1H),2.31(d,J＝5.3Hz,12H),2.22(d,J＝2.7Hz,12H),1.69(s,4H)。31P NMR(162MHz,CDCl3)δ141.03。
preparation example 4: synthesis of ligand L4
Figure BDA0002969745780000142
50mg of the compound E21 obtained in preparation example 1 are taken and added to a reactor, 2ml of dry tetrahydrofuran are added for dissolution, 50mg of pyridine (pyridine) are added, 132mg of phosphorus chloride P4 is taken and dissolved in 0.5ml of dry tetrahydrofuran, slowly added dropwise to the reactor, the temperature is raised to 50 ℃, and the nitrogen is protected for 3 hours. Cooling to room temperature, taking 63mg of dipyrrolyl phosphorus chloride P1, dissolving in 0.5ml of dry tetrahydrofuran, slowly dripping into the reactor, and reacting at room temperature for 2 h. Quenching with 10ml water, extracting with 10ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain ligand L4. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.17(d,J＝9.1Hz,2H),7.07–6.88(m,8H),6.83(d,J＝7.9Hz,1H),6.66(d,J＝8.1Hz,1H),6.21–6.09(m,4H),5.15(s,1H),4.31(t,J＝2.4Hz,1H),2.29(s,3H),2.14(s,3H),1.89(s,3H),1.82(s,3H),1.65–1.60(m,2H),1.53(s,2H),1.42(s,10H),1.32(s,10H)。31P NMR(162MHz,CDCl3)δ132.52,107.42。
preparation example 5: synthesis of ligand L5
Figure BDA0002969745780000151
Step 1: synthesis of compound G21:
400mg of the compound E21 obtained in preparation example 1 was charged into a reactor, dissolved in 8ml of DMF, and 613mg of NBS was dissolved in 1ml of DMF and added dropwise to the reactor at-20 ℃ and allowed to warm to room temperature naturally, followed by stirring overnight. Quenching with 30ml sodium sulfite solution, extracting with 30ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain compound G21. The nuclear magnetic data are as follows:1H NMR(400MHz,DMSO)δ9.68(s,2H),7.12(d,J＝8.6Hz,2H),6.60(d,J＝8.7Hz,2H),5.14(s,1H),5.01(s,1H),1.63-1.44(m,4H).
step 2: synthesis of compound H21:
150mg of compound G21, 168mg of p-vinylphenylboronic acid, 261mg of anhydrous potassium carbonate and 14mg of Pd (dppf) Cl were taken2Adding into a reactor, adding 3ml of 1, 4-dioxane (dioxane) and 1ml of deionized water, heating to 100 ℃ under the protection of argon, and stirring for reaction overnight. Diluting with 30ml of water, extracting with 30ml of ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain compound H21. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.17(d,J＝9.1Hz,2H),7.07–6.88(m,8H),6.83(d,J＝7.9Hz,1H),6.66(d,J＝8.1Hz,1H),6.21–6.09(m,4H),5.15(s,1H),4.31(t,J＝2.4Hz,1H),2.29(s,3H),2.14(s,3H),1.89(s,3H),1.82(s,3H),1.65–1.60(m,2H),1.53(s,2H),1.42(s,10H),1.32(s,10H)。31P NMR(162MHz,CDCl3)δ132.52,107.42。
and step 3: synthesis of ligand L5:
67.4mg of dipyrrolyl phosphorus chloride P1 was added to a reactor, 1ml of dry tetrahydrofuran was added, the temperature was reduced to 0 ℃ and 50mg of the compound H21 and 34.2mg of triethylamine were dissolved in 0.5ml of dry tetrahydrofuran, and this mixture was dropped into the above reactor at 0 ℃ and naturally warmed to room temperature, followed by reaction with stirring for 1 hour. Quenching in 10ml water, extracting with 10ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain ligand L5. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.23(d,J＝8.1Hz,4H),7.15–7.10(m,4H),7.09–6.99(m,10H),6.76–6.65(m,4H),6.39(dd,J＝5.2,3.1Hz,4H),6.37–6.33(m,4H),5.76(d,J＝17.6Hz,2H),5.28(d,J＝11.2Hz,2H),5.14(t,J＝2.5Hz,1H),4.91(t,J＝2.5Hz,1H),1.54(dd,J＝6.7,3.0Hz,2H),1.44–1.41(m,2H)。31P NMR(162MHz,CDCl3)δ108.34。
preparation example 6: synthesis of ligand L6
Figure BDA0002969745780000161
104mg of phosphorus chloride P3 was charged into a reactor, 1ml of dry tetrahydrofuran was added, the temperature was lowered to 0 ℃ and 50mg of the compound H21 obtained in preparation example 5 and 34.2mg of triethylamine were dissolved in 0.5ml of dry tetrahydrofuran, and this mixture was dropped into the above reactor at 0 ℃ and allowed to naturally warm to room temperature, followed by stirring for 1 hour. Quenching in 10ml water, extracting with 10ml ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and separating by column chromatography to obtain ligand L6. The nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)δ7.26(s,2H),7.25(s,2H),7.07(m,12H),6.94(d,J＝5.2Hz,4H),6.74(dd,J＝17.6,10.9Hz,2H),5.78(d,J＝17.6Hz,2H),5.58(t,J＝2.5Hz,1H),5.29(d,J＝10.5Hz,2H),4.99(t,J＝2.4Hz,1H),2.33(d,J＝6.9Hz,12H),2.26(d,J＝7.7Hz,12H),1.87–1.76(m,2H),1.69–1.60(m,2H)。31P NMR(162MHz,CDCl3)δ140.98。
test examples:
5.7. mu. mol of the bidentate phosphine ligand prepared in preparation examples 1 to 6 were each charged into a 25ml autoclave, 3ml of toluene was added to dissolve it, and 3.8. mu. mol of Rh (acac) (CO) was added2Finally, 1ml of 1, 3-butadiene toluene solution (3mol/L) is added, the reaction kettle is closed, and synthesis gas (H) with certain pressure is introduced2CO is 1:1), and the reaction is stirred for 5 to 24 hours at the temperature of between 60 and 150 ℃. Cooling, adding decane as an internal standard, detecting and analyzing by adopting GC7820 gas chromatography, wherein a chromatographic column is HP-5, and a third-order temperature rise program is as follows: the initial temperature was 45 ℃ for 2 minutes, then the temperature was raised to 90 ℃ at a rate of 5 ℃/min for 3 minutes, and then the temperature was increased toThe temperature was raised to 250 ℃ at a rate of 20 ℃/min and held for 10 minutes. The experimental conditions and results are shown in table 1 below.
Table 1:
examples Catalyst and process for preparing same Temperature of Pressure of Time Conversion rate Percentage of hexanedial Selectivity to hexanedial
Example 1 Rh/L1 90℃ 4MPa 5h 82.3％ 9.87％ 12.0％
Example 2 Rh/L1 80℃ 4MPa 12h 77.6％ 12.4％ 15.9％
Example 3 Rh/L2 90℃ 4MPa 5h 80.8％ 6.65％ 8.23％
Example 4 Rh/L2 80℃ 4MPa 12h 75.1％ 10.5％ 14.0％
Example 5 Rh/L3 90℃ 2MPa 12h 68.5％ 6.56％ 9.58％
Example 6 Rh/L3 90℃ 3MPa 5h 88.5％ 28.3％ 32.0％
Example 7 Rh/L3 90℃ 4MPa 5h 97.7％ 39.7％ 40.6％
Example 8 Rh/L3 80℃ 4MPa 12h 93.5％ 45.6％ 48.8％
Example 9 Rh/L4 90℃ 4MPa 5h 95.9％ 20.5％ 21.4％
Example 10 Rh/L4 80℃ 4MPa 12h 81.6％ 23.8％ 29.2％
Example 11 Rh/L5 90℃ 4MPa 5h 75.3％ 26.4％ 35.1％
Example 12 Rh/L5 80℃ 4MPa 12h 67.7％ 29.4％ 43.4％
Example 13 Rh/L6 90℃ 4MPa 5h 98.4％ 44.5％ 45.2％
Example 14 Rh/L6 80℃ 4MPa 12h 98.2％ 58.1％ 59.8％
As can be seen from the data in Table 1, the bidentate phosphine ligands prepared according to the present invention are effective in catalyzing the conversion of 1, 3-butadiene to adipaldehyde. The conversion rate of 1, 3-butadiene can reach more than 98%, and the selectivity of the hexanedial can reach 60%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A bidentate phosphine ligand compound having a structure of formula 1,
Figure FDA0002969745770000011
wherein R is1Selected from the following structures:
Figure FDA0002969745770000015
Figure FDA0002969745770000013
wherein ". quadrature" denotes R1An upper connection location;
R2and R3Each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, C6-C10 aryl, C1-C6 alkoxy substituted C6-C10 aryl, C1-C6 alkyl substituted C6-C10 aryl, C2-C6 alkenyl substituted C6-C10 aryl or C2-C6 alkylamino substituted C6-C10 aryl;
R4and R5Are phosphine-containing groups and are each independently selected from the following structures:
Figure FDA0002969745770000014
Figure FDA0002969745770000021
2. the bidentate phosphine ligand compound according to claim 1, characterized in that,
preferably, R1Is selected from
Figure FDA0002969745770000025
Or
Figure FDA0002969745770000026
Preferably, R2And R3Each independently selected from the following structures:
Figure FDA0002969745770000027
Figure FDA0002969745770000023
Figure FDA0002969745770000024
wherein ". quadrature" denotes R2And R3An upper connection location;
more preferably, R2And R3Each independently selected from:
Figure FDA0002969745770000034
Figure FDA0002969745770000032
preferably, R4And R5Each independently selected from the following structures:
Figure FDA0002969745770000033
3. the bidentate phosphine ligand compound of claim 1, wherein the bidentate phosphine ligand is selected from the group consisting of L1-L6:
Figure FDA0002969745770000041
4. a process for the preparation of a bidentate phosphine ligand according to any of claims 1-3, said process comprising reacting a phosphine-chlorine compound in an ethereal solvent with a bidentate phosphine
Figure FDA0002969745770000042
Or
Figure FDA0002969745770000043
In the presence of a base, with a phosphine-chlorine compound
Figure FDA0002969745770000044
Or
Figure FDA0002969745770000045
The molar ratio of (1: 5) - (2: 1) is-78-150 ℃, and the time is 0.5-24 h;
wherein
Figure FDA0002969745770000051
Or
Figure FDA0002969745770000052
Substituent R in (1)1、R2And R3The definition of (a) is the same as in formula 1.
5. The process for producing a bidentate phosphine ligand according to claim 4, characterized in that,
the base is selected from one or more of triethylamine, Dimethylaminopyridine (DMAP), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), pyridine, sodium hydride (NaH), bis (trimethylsilyl) aminolithium (LiHMDS) and n-butyllithium (n-BuLi);
preferably, the ethereal solvent is selected from tetrahydrofuran, diethyl ether, tert-butyl ether, methyl tert-butyl ether, more preferably tetrahydrofuran and diethyl ether;
preferably, the phosphine-chlorine compound is selected from the following structures:
Figure FDA0002969745770000053
6. the process for preparing a bidentate phosphine ligand according to claim 4, characterized in that said bidentate phosphine ligand is prepared as described above
Figure FDA0002969745770000054
The synthesis method comprises the following steps:
Figure FDA0002969745770000061
wherein compound C1 is reacted with a compound comprising R1Adding the corresponding alkene or alkyne into a solvent, and controlling the temperature to be 100-200 ℃; the time is 5h-48h, and the solvent is removed by reduced pressure distillation after the reaction is finished to obtain D1, substituent R1Is the same as in formula 1;
preferably, the solvent is an aromatic hydrocarbon solvent, more preferably toluene or xylene;
preferably, said comprises R1The corresponding alkene or alkyne of (a) is selected from the following structures:
Figure FDA0002969745770000062
Figure FDA0002969745770000063
7. the process for preparing a bidentate phosphine ligand according to claim 4, characterized in that said bidentate phosphine ligand is prepared as described above
Figure FDA0002969745770000064
The synthesis method comprises the following steps:
Figure FDA0002969745770000065
1) a2 is reacted with benzyl bromide in DMF or acetone solvent at 60 ℃ by taking anhydrous potassium carbonate as alkali to obtain a compound B2;
2) b2 is reduced by zinc powder in NaOH solution at 100 ℃ to obtain a compound C2;
3) c2 with a solvent comprising R1Reacting the corresponding alkene or alkyne to obtain a compound D2 at the temperature of 100-200 ℃ for 5-48 h;
4) in a hydrogen atmosphere, carrying out catalytic reduction debenzylation on D2 in methanol by using a Pd/C catalyst to obtain E2;
preferably, the solvent in step 3) is an aromatic hydrocarbon solvent, preferably toluene or xylene;
preferably, said step 3) comprises R1The corresponding alkene or alkyne of (a) can be of the structure:
Figure FDA0002969745770000071
Figure FDA0002969745770000072
8. use of a bidentate phosphine ligand according to any of claims 1-3, to promote metal-catalysed butadiene hydroformylation.
9. A method for preparing 1, 6-hexanedial by butadiene hydroformylation comprises the following steps:
adding a proper amount of the bidentate phosphine ligand of any one of claims 1-3 into a reaction kettle, then adding the solvent, the metal precursor and butadiene, sealing the reaction kettle, and filling H with a certain pressure2And the mixed gas consisting of CO reacts for a certain time at a set temperature.
10. The process for preparing 1, 6-hexanedial by hydroformylation of butadiene as claimed in claim 9, characterized in that,
preferably, the solvent is selected from aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents or ether solvents;
more preferably, the solvent is selected from one or more of n-hexane, cyclohexane, octane, benzene, toluene, xylene, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran and dioxane, more preferably toluene;
preferably, the metal precursor is a precursor of metal rhodium and cobalt, selected from: rh (CO)2(acac)、Rh(AcO)2、RhCl3、Rh(NO3)3、RhH(CO)(PPh3)3、[Rh(CO)2Cl]2、RhH(CO)(PPh3)3、[Rh2(m-Cl)2(cod)2]、[Rh(cod)2]BF4、Co(CO)2(acac)、Co(AcO)2、CoCl2、Co(acac)2More preferably Rh (CO)2(acac)；
Preferably, the molar ratio of metal precursor to bidentate phosphine ligand is from 2:1 to 1:10, preferably from 1:1 to 1:5, more preferably from 1:1 to 1: 3;
preferably, the molar ratio of metal precursor to butadiene is from 1/50 to 1/5000, preferably from 1/100 to 1/1000;
preferably, the butadiene is butadiene hexane solution, butadiene toluene solution, butadiene tetrahydrofuran solution, butadiene methanol solution and pure butadiene, preferably butadiene toluene solution;
preferably, H in the mixed gas2And CO in a volume ratio of 1/2-3/1, preferably 1/1-2/1;
preferably, the pressure of the mixed gas is 1MPa-10MPa, preferably 2MPa-5 MPa;
preferably, the reaction temperature is 50 ℃ to 200 ℃, preferably 80 ℃ to 120 ℃;
preferably, the reaction time is 5h-24h, preferably 5h-15 h;
preferably, the reaction concentration of butadiene is from 0.1mol/L to 10mol/L, preferably from 0.5mol/L to 3 mol/L.
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