CN114315895A - Ligand, preparation method and application thereof, and method for preparing linear dialdehyde - Google Patents
Ligand, preparation method and application thereof, and method for preparing linear dialdehyde Download PDFInfo
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- CN114315895A CN114315895A CN202210027359.2A CN202210027359A CN114315895A CN 114315895 A CN114315895 A CN 114315895A CN 202210027359 A CN202210027359 A CN 202210027359A CN 114315895 A CN114315895 A CN 114315895A
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- acetylacetonate
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- 239000003446 ligand Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 11
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- ATMPMEZIXCBUHT-UHFFFAOYSA-N cobalt;triphenylphosphane Chemical compound [Co].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ATMPMEZIXCBUHT-UHFFFAOYSA-N 0.000 claims description 10
- 150000002085 enols Chemical class 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 5
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 claims description 5
- 150000003003 phosphines Chemical class 0.000 claims description 5
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 claims description 5
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- DJZAABLAECNINV-UHFFFAOYSA-N 4-bromo-2,6-dimethylbenzoic acid Chemical compound CC1=CC(Br)=CC(C)=C1C(O)=O DJZAABLAECNINV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- HWVKIRQMNIWOLT-UHFFFAOYSA-L cobalt(2+);octanoate Chemical compound [Co+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HWVKIRQMNIWOLT-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- QUMSUJWRUHPEEJ-UHFFFAOYSA-N 4-Pentenal Chemical compound C=CCCC=O QUMSUJWRUHPEEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- USLRUYZDOLMIRJ-UHFFFAOYSA-N 5-Hexenal Chemical compound C=CCCCC=O USLRUYZDOLMIRJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IOXPXHVBWFDRGS-UHFFFAOYSA-N hept-6-enal Chemical compound C=CCCCCC=O IOXPXHVBWFDRGS-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OOLBRPUFHUSCOS-UHFFFAOYSA-N Pimelic dialdehyde Chemical compound O=CCCCCCC=O OOLBRPUFHUSCOS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- LREAZWJEBORMTB-UHFFFAOYSA-N bis(2-methylpropyl)phosphane Chemical compound CC(C)CPCC(C)C LREAZWJEBORMTB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WDIIYWASEVHBBT-UHFFFAOYSA-N di(propan-2-yl)phosphane Chemical compound CC(C)PC(C)C WDIIYWASEVHBBT-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a ligand for hydroformylation and a preparation method thereof, and the structure is shown as formula 1:
wherein R is1、R2Is C1‑C10Alkanes, aromatic hydrocarbons. The ligand has strong chelating ability with metal and high reaction activity. The invention also provides a preparation method of the linear dialdehyde, which has the advantages of simple process, low cost and energy consumption, good production safety, high quality of the obtained product and the like, and is particularly suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a bidentate phosphine ligand and a preparation method thereof, and also relates to an application of the bidentate phosphine ligand in preparation of linear dialdehyde.
Background
The nylon 66 is prepared by condensing hexamethylene diamine and adipic acid, and in recent years, because the adipic acid has a strong demand, domestic production cannot meet the market demand, and the production process of the adipic acid is only mastered by individual manufacturers and cannot replace monomers, so that the adipic acid has high profit.
In recent years, oxidation reaction has become a research hotspot due to easy availability of oxygen, abundant resources and environmental friendliness; meanwhile, the oxidation of 1, 6-hexanediol into adipic acid is a means with industrial prospect. At present, the methods for preparing 1, 6-hexanedial are not many, and patent CN109369356A proposes a method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene, but the method needs to prepare a cobalt complex catalyst separately, and has the disadvantages of complex preparation method, low yield and low selectivity; at present, cyclohexene is used as a raw material in industrial production and is obtained by oxidation, reduction and hydrolysis of ozone, but a large amount of toxic substances are used in the method, and the environment is seriously polluted.
Therefore, there is a strong need for an economical, stable ligand to make linear dialdehydes.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing linear dialdehyde by continuous reaction with enol as a raw material.
It is another object of the present invention to provide a ligand and a method for preparing the same, which have high reactivity and linear selectivity when used in hydroformylation.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of linear dialdehyde comprises the following steps:
(1) synthesizing olefine aldehyde from enol and acetylene;
(2) olefine aldehyde hydroformylation is carried out to prepare binary aldehyde.
In step (1) of the present invention, the raw material enol is C2-C10Enol of (4), preferablyIs allyl alcohol, 4-penten-1-ol, 3-buten-1-ol.
In step (1) of the present invention, the amount of acetylene added is 1.0 to 3.0 times, preferably 1.0 to 1.3 times, the molar amount of enol; the catalyst is metal alkali, preferably KOH or NaOH; the addition amount of the catalyst is 1 to 5 percent of the mol amount of the enol, preferably 1 to 2 percent; the reaction temperature is 100-150 ℃, and the preferable temperature is 110-130 ℃; the reaction time is 0.5-3.0h, preferably 1.5-2.0 h.
In the step (2), the olefine aldehyde, the catalyst and the ligand are dissolved in a solvent, the temperature is raised to the reaction temperature, the synthesis gas is introduced, and the reaction is carried out for a certain time to obtain the product
In the step (2), the catalyst is one or more of rhodium acetate, rhodium octanoate, rhodium acetylacetonate carbonyl, rhodium dicarbonyl acetylacetonate, triphenylphosphine rhodium acetylacetonate, cobalt acetate, cobalt octanoate, cobalt acetylacetonate carbonyl and triphenylphosphine cobalt acetylacetonate, and the preferable catalyst is rhodium dicarbonyl acetylacetonate and/or triphenylphosphine cobalt acetylacetonate; the amount of the catalyst added is 0.01 to 0.03 times, preferably 0.01 to 0.02 times the molar amount of the enal. The amount of ligand added is 30 to 100 times, preferably 50 to 80 times the molar amount of catalyst. The reaction pressure is 1.0 to 10.0MPaG, preferably 1.0 to 6.0 MPaG; the reaction temperature is 60 to 150 ℃, preferably 60 to 80 ℃, and the reaction time is 1.0 to 5.0 hours, preferably 1.0 to 2.0 hours. The solvent is one or more of N, N-Dimethylformamide (DMF), benzene, toluene and chloroform, and preferably benzene and/or DMF.
The bidentate phosphine ligand provided by the invention is used for catalyzing hydroformylation reaction in the step (2), and the structural general formula I is as follows:
wherein R is1、R2Is C1-C10Preferably phenyl, isopropyl, isobutyl; r1、R2The same or different, preferably the same.
The preparation method of the ligand comprises the following steps: 2, 6-diphenylethylamine and 5' -bromo-1, 1' -3 ', 1' -terphenyl-2 ' -carboxylic acid react to generate an intermediate I; the intermediate I reacts with the disubstituted phosphine to generate the final ligand, and the reaction equation is as follows:
the preparation method of the intermediate I comprises the following steps: the 2, 6-diphenylethylamine is added in an amount of 1.0 to 2.0 times, preferably 1.0 to 1.2 times, the molar amount of 5' -bromo-1, 1':3', 1' -terphenyl-2 ' -carboxylic acid. Catalyst triphenylphosphine acetylacetonatocarbonylrhodium, cobalt acetylacetonate, preferably triphenylphosphine acetylacetonatocarbonylrhodium. The amount of the catalyst added is 0.001 to 0.01 times, preferably 0.005 to 0.007 times the molar amount of 4-bromo-2, 6-dimethylbenzoic acid. The solvent is one of benzene, toluene and chlorobenzene; preferred are benzene and toluene. The reaction temperature is 80-140 deg.C, preferably 90-110 deg.C, and the reaction time is 1.0-5.0h, preferably 1.0-2.0 h.
The preparation method of the ligand comprises the following steps: the amount of the disubstituted phosphine added is 1.0 to 2.0 times, preferably 1.2 to 1.5 times the molar amount of the intermediate I. One of catalyst KOH and NaOH, preferably KOH, is added in an amount which is 1 to 5 times, preferably 3 to 4 times of the molar amount of the intermediate I. The solvent is one of benzene, toluene and N, N-Dimethylformamide (DMF); preferred is N, N-dimethylformamide. The reaction temperature is 80-140 deg.C, preferably 90-110 deg.C, and the reaction time is 1.0-5.0h, preferably 1.0-2.0 h.
The pressure referred to in the present invention is gauge pressure
The ligand of the invention has the principle that the space ductility of a flexible amide chain is combined with an upper benzene ring and a lower benzene ring to establish a pi-pi conjugated stereo space, during reaction, double bonds of olefine aldehyde are bound by large pi bonds of the upper benzene ring and the lower benzene ring, and aldehyde oxygen and hydrogen are respectively bound by H, N of an amide group and are stretched, so that reactants are accurately captured, the reaction rate is increased, the reaction temperature is reduced, and the generation amount of byproducts is reduced; the end group insertion is easier to carry out under the steric hindrance effect of the phosphine ligand, so that the selective generation of linear dialdehyde is ensured.
The ligand is used for obtaining linear dialdehyde, the catalytic activity is high, the linear selectivity is good (the selectivity can reach 95-98%), the ligand has stronger chelating capacity with metal, and the reaction activity is high. The method for preparing the linear dialdehyde has the advantages of simple and convenient process, low cost and energy consumption, good production safety, high quality of the obtained product and the like, and is particularly suitable for large-scale industrial production.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The sources of the raw materials of the reagents used in the examples and comparative examples of the present invention are as follows:
2, 6-diphenylethylamine, 5 '-bromo-1, 1':3',1 "-terphenyl-2' -carboxylic acid, allyl alcohol, 4-penten-1-ol, 3-buten-1-ol, rhodium dicarbonyl acetylacetonate, cobalt triphenylphosphine acetylacetonate, from Sigma-Adrich; acetylene, benzene, DMF were purchased from Shanghai national reagents, Inc.
The other raw materials of the reagents are all commercial products unless otherwise specified.
The above reagents were purchased and used directly.
The test methods used in the examples of the invention and the comparative examples are as follows:
the product structure was determined by elemental analyzer and nuclear magnetic analysis using a Vario EL cube analyzer from Elementar, Germany and a Bruker AVANCEIII 500MHz analyzer. The chromatographic analysis is Agilent 7890B gas chromatograph: agilent DB-5 chromatographic column, injection port temperature: 220 ℃; the temperature of the detector is 250 ℃; h2The flow rate is 40/min; the air flow rate is 360 ml/min. The temperature raising program of the column box is that the initial temperature is 20 ℃, the temperature raising rate is 20 ℃/min, and the temperature is kept for 4 min; 100 ℃ and 250 ℃, the heating rate is 15 ℃/min, and the temperature is kept for 10 min.
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
(1) Preparation of the catalyst
Preparation of MI: 3', 1' -terphenyl-2 ' -carboxylic acid (353.2g, 1mol), 2, 6-diphenylamine (273.4g, 1.0mol), triphenylphosphine rhodium acetylacetonate (2.46g, 0.005mol) were dissolved in 800mL of toluene and the temperature was raised to 90 ℃ for 1.0 hour to give M1(584.4g, 0.85mol) having the following structure:
elemental analysis: 76.95; h is 4.95; 2.33 of N; o is 2.63; br: 13.14
1H NMR(500MHz,Chloroform-d)δ8.14(s,2H),8.02(t,1H),7.76–7.70(m,4H),7.53–7.38(m,17H),7.41–7.34(m,2H),3.69(q,2H),3.20(t,2H)。
Preparation of the ligand: dissolving M1(584.4g, 0.85mol), diphenylphosphine (189.9g, 1.02mol) and KOH (2.55mol, 142.8g) in 600ml DMF, heating to 90 ℃ and reacting for 1.0h to obtain a ligand (0.8mol, 571.1g) with the following structure:
elemental analysis: c, 85.82; h is 5.68; n is 1.97; o is 2.25; p: 4.28
1H NMR(500MHz,Chloroform-d)δ7.69(d,2H),7.53–7.28(m,34H),3.69(q,2H),3.20(t,2H)。
(2) Preparation of hexanedial from allyl alcohol
Allyl alcohol (580.8g, 10mol), KOH (5.6g, 0.1mol) were added to the reaction vessel, and acetylene (260.4g, 10mol) was introduced to react at 110 ℃ for 1.5h to give 4-pentenal (706.7g, 9.8mol) as a 4-pentenal: triphenylphosphine cobalt acetylacetonate: adding catalyst and ligand into ligand M ═ 1:0.01:0.5, adding catalyst and ligand into the mixture, and adding catalyst into the mixture in the presence of CO/H2The molar ratio is 1:1, the pressure is 1MPa, the temperature is 90 ℃, the reaction is carried out for 1.0 hour, and the conversion rate is 98.1 percent; the linear product, adipaldehyde, was obtained by gas chromatography with a selectivity of 96.1%.
Example 2
(1) Preparation of the catalyst
Preparation of M1: 5' -bromo-1, 1':3', 1' -terphenyl-2 ' -carboxylic acid (353.2g, 1.0mol), 2, 6-diphenylethylamine (422.7g, 1.2mol), triphenylphosphine rhodium acetylacetonate (3.44g, 0.007mol) were dissolved in 800mL of toluene and the temperature was raised to 110 ℃ for 2.0 hours to give M1(591.3g, 0.86 mol).
Preparation of the ligand: m1(591.3g, 0.86mol), diisobutylphosphine (188.6g, 1.29mol), KOH (3.44mol, 192.6g) were dissolved in 600mL DMF, heated to 100 ℃ and reacted for 1.5h to give the ligand (0.8mol, 539.1g) with the following structure:
elemental analysis: 83.78; h is 7.20; 2.05 of N; o is 2.35; p: 4.62
1H NMR(500MHz,Chloroform-d)δ8.06(t,1H),7.63(d,2H),7.53–7.34(m,23H),3.69(q,2H),3.20(t,2H),2.25(dd,4H),1.68(dq,2H),0.84(d,12H).
(2) Preparation of octanediol from 4-penten-1-ol
Adding 4-penten-1-ol (861.3g, 10mol) and NaOH (8.0g, 0.2mol) into a reaction kettle, introducing acetylene (338.5g, 13mol), and reacting at 130 ℃ for 2.0h to obtain 5-hexenal (970.2g, 9.9 mol); with 5-hexenal: triphenylphosphine cobalt acetylacetonate: adding catalyst and ligand into ligand M ═ 1:0.02:1.6, adding catalyst and ligand into the mixture, and reacting in CO/H2The molar ratio is 1:1, the pressure is 6MPa, the temperature is 80 ℃, the reaction time is 2.0 hours, and the conversion rate is 97.8 percent; the linear product octanediol was obtained by gas chromatography with a selectivity of 96.6%.
Example 3
(1) Preparation of the catalyst
Preparation of M1: preparation of MI: 5' -bromo-1, 1':3', 1' -terphenyl-2 ' -carboxylic acid (353.2g, 1mol), 2, 6-diphenylethylamine (273.4g, 1.0mol), triphenylphosphine rhodium acetylacetonate carbonyl (2.95g, 0.006mol) were dissolved in 600mL of toluene and the temperature was raised to 100 ℃ for 1.5 hours to give M1(584.4g, 0.85 mol).
Preparation of the ligand: m1(584.4g, 0.85mol), diisopropylphosphine (241.0g, 2.04mol), KOH (3.0mol, 168.0g) were dissolved in 800mL DMF, heated to 1100 deg.C, and reacted for 2.0h to give the ligand (0.82mol, 529.6g) with the following structure:
elemental analysis: 83.70; h is 6.88; 2.19 of N; o is 2.50; p: 4.73
1H NMR(500MHz,Chloroform-d)δ8.06(t,1H),7.56(d,2H),7.53–7.34(m,23H),3.69(q,2H),3.20(t,2H),1.96(dq,2H),1.01(d,12H).
(2) Preparation of heptanedial from 3-butylene-1-alcohol
Adding 3-buten-1-ol (861.3g, 10mol) and NaOH (6.0g, 0.15mol) into a reaction kettle, introducing acetylene (312.5g, 12mol), and reacting at 120 ℃ for 2.0h to obtain 6-heptenal (1086.4g, 9.7 mol); with 6-heptenal: triphenylphosphine cobalt acetylacetonate: adding catalyst and ligand into ligand M ═ 1:0.02:1.6, adding catalyst and ligand into the mixture, and reacting in CO/H2The molar ratio is 1:1, the pressure is 3MPa, the temperature is 70 ℃, the reaction is carried out for 1.5 hours, and the conversion rate is 98.5 percent; the linear product, octoheptanedial, was obtained by gas chromatography with a selectivity of 97.1%.
Comparative example 1:
the weight ratio of butadiene: triphenylphosphine cobalt acetylacetonate: adding catalyst and ligand in the molar ratio of 1 to 0.01 to 0.5, adding catalyst and ligand in the presence of CO/H2The molar ratio is 1:1, the pressure is 1MPa, the temperature is 90 ℃, the reaction is carried out for 1.0 hour, and the conversion rate is 95.1 percent; the linear product, adipaldehyde, was obtained by gas chromatography with a selectivity of 68.2%.
Comparative example 2:
with 4-pentenal: triphenylphosphine cobalt acetylacetonate: adding catalyst and ligand in the molar ratio of 1 to 0.01 to 0.5, and adding catalyst and ligand in the presence of CO/H2The molar ratio is 1:1, the pressure is 1MPa, the temperature is 90 ℃, the reaction is carried out for 1.0 hour, and the conversion rate is 90.2 percent; the linear product, adipaldehyde, was obtained by gas chromatography with a selectivity of 48.3%.
Claims (11)
1. A ligand, characterized by satisfying the structure of formula 1:
wherein R is1、R2Is C1-C10Preferably phenyl, isopropyl, isobutyl; r1、R2The same or different, preferably the same.
2. The method for preparing a ligand according to claim 1, comprising the steps of: 2, 6-diphenylethylamine and 5' -bromo-1, 1' -3 ', 1' -terphenyl-2 ' -carboxylic acid react to generate an intermediate I; the intermediate I reacts with the disubstituted phosphine to generate the final ligand, and the reaction equation is as follows:
3. the process as claimed in claim 2, wherein 2, 6-diphenylethylamine is added in an amount of 1.0 to 2.0 times, preferably 1.0 to 1.2 times, the molar amount of 5 '-bromo-1, 1':3',1 "-terphenyl-2' -carboxylic acid in the reaction to form intermediate I; and/or the catalyst is triphenylphosphine acetylacetonatocarbonylrhodium and cobalt acetylacetonate, preferably triphenylphosphine acetylacetonatocarbonylrhodium; the adding amount of the catalyst is 0.001-0.01 time of the molar amount of the 4-bromo-2, 6-dimethylbenzoic acid, preferably 0.005-0.007 time; and/or the solvent is one of benzene, toluene and chlorobenzene; preferred are benzene or toluene; and/or the reaction temperature is 80-140 ℃, preferably 90-110 ℃, and the reaction time is 1.0-5.0h, preferably 1.0-2.0 h.
4. A process according to claim 2 or 3, characterized in that in the reaction of intermediate I with the disubstituted phosphine, the disubstituted phosphine is added in an amount of 1.0 to 2.0 times, preferably 1.2 to 1.5 times, the molar amount of intermediate I; and/or, the catalyst is one of KOH and NaOH, preferably KOH; the adding amount of the catalyst is 1 to 5 times of the molar amount of the intermediate I, and the preferable adding amount is 3 to 4 times; and/or the solvent is one of benzene, toluene and N, N-Dimethylformamide (DMF); preferred are N, N-dimethylformamide; and/or the reaction temperature is 80-140 ℃, preferably 90-110 ℃, and the reaction time is 1.0-5.0h, preferably 1.0-2.0 h.
5. Use of the ligand according to claim 1 or the ligand obtained by the preparation process according to any one of claims 2 to 4 as a catalyst ligand in hydroformylation reactions.
6. A method for preparing a linear dialdehyde comprising the steps of:
(1) reacting enol with acetylene to prepare olefine aldehyde;
(2) an enal hydroformylation reaction in which the ligand according to claim 1 or the ligand obtained by the production method according to any one of claims 2 to 4 is used to produce a dialdehyde.
7. The method of claim 6, wherein said enol is C2-C10The enol of (A) is preferably allyl alcohol, 4-penten-1-ol or 3-buten-1-ol.
8. The method according to claim 6 or 7, characterized in that acetylene is added in an amount of 1.0 to 3.0 times, preferably 1.0 to 1.3 times, the molar amount of enol; and/or, the catalyst is metal alkali, preferably KOH, NaOH; the addition amount of the catalyst is 1 to 5 percent of the mol amount of the enol, preferably 1 to 2 percent; and/or the reaction temperature is 100-150 ℃, preferably 110-130 ℃; the reaction time is 0.5-3.0h, preferably 1.5-2.0 h.
9. The method according to any one of claims 6 to 8, wherein the olefine aldehyde hydroformylation reaction is to dissolve olefine aldehyde, a catalyst and a ligand in a solvent, raise the temperature to a reaction temperature, introduce synthesis gas, and react for a certain time to obtain a product; the amount of ligand added is 30 to 100 times, preferably 50 to 80 times the molar amount of catalyst.
10. The process according to any one of claims 6 to 9, wherein the catalyst for the hydroformylation of the enal is one or more of rhodium acetate, rhodium octanoate, rhodium acetylacetonate carbonyl, rhodium dicarbonyl acetylacetonate, triphenylphosphine rhodium acetylacetonate, cobalt acetate, cobalt octanoate, cobalt acetylacetonate carbonyl, triphenylphosphine cobalt acetylacetonate, preferably rhodium dicarbonyl acetylacetonate and/or triphenylphosphine cobalt acetylacetonate; the amount of the catalyst added is 0.01 to 0.03 times, preferably 0.01 to 0.02 times the molar amount of the enal.
11. The process according to any one of claims 6 to 10, characterized in that the solvent used in the hydroformylation reaction is one or more of N, N-dimethylformamide, benzene, toluene, chloroform, preferably benzene and/or N, N-dimethylformamide; and/or the reaction pressure is 1.0-10.0MPaG, preferably 1.0-6.0 MPaG; the reaction temperature is 60 to 150 ℃, preferably 60 to 80 ℃, and the reaction time is 1.0 to 5.0 hours, preferably 1.0 to 2.0 hours.
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