CN113004326B - 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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CN113004326B
CN113004326B CN202110260439.8A CN202110260439A CN113004326B CN 113004326 B CN113004326 B CN 113004326B CN 202110260439 A CN202110260439 A CN 202110260439A CN 113004326 B CN113004326 B CN 113004326B
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butadiene
phosphine ligand
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bidentate phosphine
metal precursor
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CN113004326A (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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Abstract

The invention discloses a bidentate phosphine ligand compound with a structure of a general formula 1, a synthetic method thereof and application of the phosphine ligand in promoting metal catalysis 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 synthetic method thereof and application of the phosphine ligand in promoting metal catalysis 1,3-butadiene hydroformylation.
Background
Hexanedial (1,6-hexanedial), as an important organic synthesis raw material, can be directly used for the synthesis of C6 compounds with higher application value and larger market demand, 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 polyesters, polyamides (nylon 66 or nylon 610), polyurethanes, etc.
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 a catalyst, two C = C double bonds of butadiene and synthesis gas are subjected to two-step carbonylation to generate the target product of adipaldehyde. Once the research route realizes breakthrough, 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 the new application and consumption field of butadiene, extends the 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 (during 1960-1980) hydroformylation of butadiene to produce hexanedial using different alkyl or aryl monodentate or bidentate phosphine ligand-rhodium based catalytic systems suffered from severe reaction conditions (synthesis gas pressure >750 bar) with hexanedial product selectivity below 10% (e.g., tetrahedron lett.,1969,32,2721-2723, chemikezeitung,1975,99,452-458, j.mol.Cat., 1977,2,211-218, j.mol.Cat., 1980,8,329-337, j.mol.Cat., 1985,31,345-503; U.S. Pat. Nos. 4,507,508, 947,503. 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 more systematic work in this regard, developing a new class of structural phosphate ligands (Organometallics 2011,30,3643-3651 ACS Cat., 2014,4,3593-3604.
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 from 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 is 1 Selected from the following structures:
Figure BDA0002969745780000022
Figure BDA0002969745780000023
wherein ". Sup." denotes R 1 And (c) the connection location.
Preferably, R 1 Is selected from
Figure BDA0002969745780000024
R 2 And R 3 Each 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.
R 2 And R 3 Each independently selected from the following structures:
Figure BDA0002969745780000025
Figure BDA0002969745780000031
Figure BDA0002969745780000032
wherein ". Quadrature" denotes R 2 And R 3 A connection location on;
more preferably, R 2 And R 3 Each independently selected from:
Figure BDA0002969745780000033
R 4 and R 5 Are phosphine-containing groups and are each independently selected from the following structures:
Figure BDA0002969745780000034
Figure BDA0002969745780000041
preferably, R 4 And R 5 Each independently selected from the following structures:
Figure BDA0002969745780000042
Figure BDA0002969745780000051
preferably, the bidentate phosphine ligand is selected from the group consisting of L1 to L6 as follows:
Figure BDA0002969745780000052
Figure BDA0002969745780000061
according to another aspect of the invention, it is another object of the invention to provide a process for the preparation of the bidentate phosphine ligand, which process comprisesComprising reacting a phosphine-chlorine compound with an ethereal solvent
Figure BDA0002969745780000062
Or alternatively
Figure BDA0002969745780000063
In the presence of a base, with a phosphine-chlorine compound
Figure BDA0002969745780000064
Or alternatively
Figure BDA0002969745780000065
The molar ratio of 5:1-2:1, the temperature is-78-150 ℃, and the time is 0.5-24 h;
wherein
Figure BDA0002969745780000066
Or alternatively
Figure BDA0002969745780000067
Substituent R in (1) 1 、R 2 And R 3 The 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 R 1 Adding the corresponding alkene or alkyne into a solvent, and controlling the temperature to be 100-200 ℃; the time is 5h-48h, the solvent is removed by reduced pressure distillation after the reaction is finished, D1 is obtained, and the substituent R 1 The 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 R 1 The 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, inter alia, according to methods disclosed in the prior art, for example, the synthesis method described in Dalton trans, 2019,48,14777-14782, the contents of which are incorporated herein by reference.
Said
Figure BDA0002969745780000081
The synthesis method comprises the following steps:
Figure BDA0002969745780000082
1) Reacting A2 with benzyl bromide in a DMF or acetone solvent at 60 ℃ by taking anhydrous potassium carbonate as an 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 in a solvent with a compound containing R 1 Reacting the corresponding alkene or alkyne to obtain a compound D2 at the temperature of 100-200 ℃ for 5-48 h;
4) And under the hydrogen atmosphere, carrying out catalytic reduction debenzylation on the 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 R 1 The 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 process for the hydroformylation of butadiene to 1,6-hexanedial, which is a process for the conversion of butadiene to 1,6-hexanedial under the conditions of a suitable solvent, bidentate phosphorus ligand, 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 pressure 2 And reacting the mixed gas consisting of CO 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 、RhCl 3 、Rh(NO 3 ) 3 、RhH(CO)(PPh 3 ) 3 、[Rh(CO) 2 Cl] 2 、RhH(CO)(PPh 3 ) 3 、[Rh 2 (m-Cl) 2 (cod) 2 ]、[Rh(cod) 2 ]BF 4 、Co(CO) 2 (acac)、Co(AcO) 2 、CoCl 2 、Co(acac) 2 Preferably Rh (CO) 2 (acac)。
Preferably, the molar ratio of metal precursor to bidentate phosphine ligand is 2:1-1, 10, preferably 1:1-1:5, more preferably 1:1-1:3.
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 gas 2 And CO in a volume ratio of 1/2 to 3/1, preferably 1/1 to 2/1.
Preferably, the pressure of the mixed gas is 1MPa to 10MPa, preferably 2MPa to 5MPa.
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 15h. Preferably, the reaction concentration of butadiene is from 0.1mol/L to 10mol/L, preferably from 0.5mol/L to 3mol/L.
Advantageous effects
The catalyst formed by the bidentate phosphine ligand and the active metal can catalyze 1,3-butadiene hydroformylation to prepare the hexanedial, compared with other reported catalysts in documents, 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 a bidentate phosphine ligand L1 in preparation example 1.
FIG. 7 is a liquid nuclear magnetic phosphorus spectrum of a bidentate phosphine ligand L1 in preparation 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 a 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 a 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 a bidentate phosphine ligand L4 in preparative example 4.
Fig. 14 is a liquid nuclear magnetic hydrogen spectrum of compound G21 in preparative 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 a bidentate phosphine ligand L5 in preparation 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 a 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.
Materials 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 company in Switzerland.
In a specific embodiment, the metal precursor selected for the catalytic system is Rh (acac) (CO) 2 The 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:
1, 8-dihydroxyanthraquinone (Compound A2) (10g) was charged into the reactor, and 200ml of DMF was added thereto for dissolution, followed by addition of 17.2g of anhydrous K 2 CO 3 And 21.2g of benzyl bromide, and reacted at 60 ℃ overnight. Cooling to room temperature, adding the reaction solution into 600ml of water for quenching, generating a large amount of yellow precipitate, filtering, washing with water, and drying in vacuum at 60 ℃ to obtain the compound B2. The nuclear magnetic data are as follows: 1 H NMR(600MHz,CDCl 3 )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 the compound B2 was charged into a reactor, and 170ml of a 10% NaOH solution and then 13g of zinc powder were added thereto, followed by reflux reaction 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, the eluent being petroleum ether, ethyl acetate =5:1, and isolating to obtain pure compound C2. The nuclear magnetic data are as follows: 1 H 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 are introduced into a reactor, 20ml of xylene are added, and 1.09g of dimethyl butynedioate are added and the reaction is 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 the compound D21. The nuclear magnetic data are as follows: 1 H 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 is added into a reactor, 35ml of methanol is added, 3g of NaOH is dissolved in 35ml of deionized water and added into the reaction solution, and reflux reaction is carried out for 4 hours. 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)Then, 1.4g of copper powder was added and reacted at 240 ℃ for 3 hours under the protection of 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: 1 H 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:
adding 2.1g of compound F2 into a reactor, adding 20ml of tetrahydrofuran for dissolving, adding 60ml of methanol for diluting, adding 200mg of palladium-carbon, replacing gas in the reactor with hydrogen for 3 times, adding a hydrogen balloon, and reacting at room temperature overnight. Adding diatomite for filtration, washing with tetrahydrofuran, decompressing and evaporating the solvent, and drying in vacuum to obtain the compound E21. The nuclear magnetic data are as follows: 1 H 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 ℃, in addition, 100mg of 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 hour. Adding 10ml water for quenching, adding 10ml ethyl acetate for extraction, drying an organic phase by anhydrous sodium sulfate, and separating by column chromatography to obtain a ligand L1. The nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 )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)。 31 P NMR(162MHz,CDCl 3 )δ108.25。
preparation example 2: synthesis of ligand L2
Figure BDA0002969745780000131
100mg of the compound E21 obtained in preparation example 1 was taken out of the reactor, dissolved in 2ml of dry DMF, cooled to 0 ℃ and added with 36.8mg of NaH in portions, warmed to room temperature and reacted for 30min, and 212mg of phosphorus chloride P2 was taken out of the reactor, dissolved in 0.5ml of dry DMF and slowly added dropwise thereto and reacted at room temperature overnight. Adding 10ml water for quenching, adding 10ml ethyl acetate for extraction, drying an organic phase by anhydrous sodium sulfate, and separating by column chromatography to obtain a ligand L2. The nuclear magnetic data are as follows: 1 H NMR(400MHz,C 6 D 6 )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)。 31 P NMR(162MHz,C 6 D 6 )δ118.86,114.85。
preparation example 3: synthesis of ligand L3
Figure BDA0002969745780000141
578mg of phosphorus chloride P3 were introduced into a reactor, 4ml of dry tetrahydrofuran were added, the temperature was reduced 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 reactor at 0 ℃ and allowed to warm to room temperature naturally for 1 hour. Adding 10ml water for quenching, adding 10ml ethyl acetate for extraction, drying an organic phase by anhydrous sodium sulfate, and separating by column chromatography to obtain a ligand L3. The nuclear magnetic data are as follows: 1 H 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)。 31 P 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 placed in a reactor, 2ml of dry tetrahydrofuran are added and dissolved, 50mg of pyridine (pyridine) are added, 132mg of phosphorus chloride P4 are taken and dissolved in 0.5ml of dry tetrahydrofuran and slowly added dropwise into the reactor, the temperature is raised to 50 ℃, and the reaction is carried out for 3 hours under the protection of nitrogen. 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 2h. 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: 1 H NMR(400MHz,CDCl 3 )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)。 31 P NMR(162MHz,CDCl 3 )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 slowly added dropwise to the reactor at-20 ℃ to naturally warm to room temperature, 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: 1 H 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 the compound G21, 168mg of p-vinylphenylboronic acid, 261mg of anhydrous potassium carbonate and 14mg of Pd (dppf) Cl were weighed out 2 Adding into a reactor, adding 3ml of 1, 4-dioxane (dioxane) and 1ml of deionized water, heating to 100 ℃ under the protection of argon, stirring and reactingAnd (4) at night. 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 the compound H21. The nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 )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)。 31 P NMR(162MHz,CDCl 3 )δ132.52,107.42。
and step 3: synthesis of ligand L5:
67.4mg of dipyrrolyl phosphorus chloride P1 is added into a reactor, 1ml of dry tetrahydrofuran is added, the temperature is reduced to 0 ℃, in addition, 50mg of compound H21 and 34.2mg of triethylamine are dissolved in 0.5ml 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 stirring reaction is carried out for 1 hour. Adding 10ml water for quenching, adding 10ml ethyl acetate for extraction, drying an organic phase by anhydrous sodium sulfate, and separating by column chromatography to obtain a ligand L5. The nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 )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)。 31 P NMR(162MHz,CDCl 3 )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 naturally warmed 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 ligandAnd L6. The nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 )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)。 31 P NMR(162MHz,CDCl 3 )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 added 2 Finally, 1ml of 1, 3-butadiene toluene solution (3 mol/L) is added, the reaction kettle is closed, and synthesis gas (H) with certain pressure is introduced 2 CO = 1:1) and is stirred to react for 5-24h at 60-150 ℃. 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 ramped up to 90 ℃ at a rate of 5 ℃/min for 3 minutes, then ramped up to 250 ℃ at a rate of 20 ℃/min 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. 5363 the conversion rate of 1,3-butadiene can reach more than 98%, and the selectivity of 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 (8)

1. A bidentate phosphine ligand selected from the group consisting of L5 and L6 as follows:
Figure FDA0003866889900000011
2. a process for the preparation of a bidentate phosphine ligand according to claim 1, said process comprising reacting a phosphine-chlorine compound in an ethereal solvent with a phosphine-chlorine compound
Figure FDA0003866889900000012
In the presence of a base, with a phosphine-chlorine compound
Figure FDA0003866889900000013
The molar ratio of 5:1-2:1, the temperature is-78-150 ℃, and the time is 0.5-24 h;
wherein
Figure FDA0003866889900000014
Substituent R in (1) 1 、R 2 And R 3 Are as defined for the corresponding substituents in L5 or L6 in claim 1;
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);
the ether solvent is selected from tetrahydrofuran, diethyl ether, tertiary butyl ether and methyl tertiary butyl ether.
3. The process for producing a bidentate phosphine ligand according to claim 2, characterized in that,
the ether solvent is selected from tetrahydrofuran and diethyl ether;
the phosphine-chlorine compound is selected from the following structures:
Figure FDA0003866889900000021
4. use of a bidentate phosphine ligand according to claim 1, to promote metal-catalyzed butadiene hydroformylation.
5. A method for preparing 1,6-hexanedial by butadiene hydroformylation comprises the following steps:
adding a proper amount of the bidentate phosphine ligand of claim 1 into a reaction kettle, adding a solvent, a metal precursor and butadiene, sealing the reaction kettle, and filling H with a certain pressure 2 And the mixed gas consisting of CO reacts for a certain time at a set temperature.
6. The process of claim 5 for the hydroformylation of butadiene to produce 1,6-hexanedial,
the solvent is selected from one or more of n-hexane, cyclohexane, octane, benzene, toluene, xylene, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran and dioxane;
the metal precursor is a precursor of metal rhodium and cobalt, and is selected from the following group: rh (CO) 2 (acac)、Rh(AcO) 2 、RhCl 3 、Rh(NO 3 ) 3 、RhH(CO)(PPh 3 ) 3 、[Rh(CO) 2 Cl] 2 、RhH(CO)(PPh 3 ) 3 、[Rh 2 (m-Cl) 2 (cod) 2 ]、[Rh(cod) 2 ]BF 4 、Co(CO) 2 (acac)、Co(AcO) 2 、CoCl 2 、Co(acac) 2 One or more of;
the molar ratio of the metal precursor to the bidentate phosphine ligand is 2:1-1;
the molar ratio of the metal precursor to the butadiene is 1/50-1/5000;
the butadiene is butadiene hexane solution, butadiene toluene solution, butadiene tetrahydrofuran solution, butadiene methanol solution and pure butadiene;
h in the mixed gas 2 And CO in a volume ratio of 1/2 to 3/1;
the pressure of the mixed gas is 1MPa-10MPa;
the reaction temperature is 50-200 ℃;
the reaction time is 5-24 h;
the reaction concentration of butadiene is 0.1mol/L to 10mol/L.
7. The process of claim 5 for the hydroformylation of butadiene to produce 1,6-hexanedial,
the solvent is toluene;
the metal precursor is Rh (CO) 2 (acac)；
The molar ratio of the metal precursor to the bidentate phosphine ligand is 1:1-1:5;
the molar ratio of the metal precursor to butadiene is preferably 1/100 to 1/1000;
butadiene is butadiene toluene solution;
h in the mixed gas 2 And CO in a volume ratio of 1/1 to 2/1;
the pressure of the mixed gas is 2MPa-5MPa;
the reaction temperature is 80-120 ℃;
the reaction time is 5-15 h;
the reaction concentration of butadiene is 0.5mol/L to 3mol/L.
8. The method of claim 7 for preparing 1,6-hexanedial by hydroformylation of butadiene, wherein the molar ratio of metal precursor to bidentate phosphine ligand is 1:1-1:3.
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