CN112209788B - Method for preparing 4,4' -dialkyl biphenyl by reacting 5,5' -dialkyl-2, 2' -difurane with olefin - Google Patents

Method for preparing 4,4' -dialkyl biphenyl by reacting 5,5' -dialkyl-2, 2' -difurane with olefin Download PDF

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CN112209788B
CN112209788B CN201910617729.6A CN201910617729A CN112209788B CN 112209788 B CN112209788 B CN 112209788B CN 201910617729 A CN201910617729 A CN 201910617729A CN 112209788 B CN112209788 B CN 112209788B
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olefin
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CN112209788A (en
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张宗超
凯歇尔.拉曼尼
许占威
管西安
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2527/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • C07C2527/198—Vanadium
    • C07C2527/199—Vanadium with chromium, molybdenum, tungsten or polonium

Abstract

The invention provides a method for preparing 4,4' -dialkyl biphenyl by reacting 5,5' -dialkyl-2, 2' -difuran with olefin. The method adopts solid heteropoly acid as the catalyst, the yield of the product 4,4' -dialkyl biphenyl is high, the product is easy to separate from the catalyst, and the heteropoly acid catalyst has the advantages of low cost, no corrosiveness and recyclability.

Description

Method for preparing 4,4' -dialkyl biphenyl by reacting 5,5' -dialkyl-2, 2' -difurane with olefin
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a method for preparing 4,4 '-dialkyl biphenyl, wherein the 4,4' -dialkyl biphenyl obtained by the method can be used for producing biphenyl dicarboxylic acid derivatives, and the biphenyl dicarboxylic acid derivatives can be used for producing various high-performance polymers such as polyester or polyamide.
Background
4,4 '-dialkyl biphenyl is a compound with important application in the chemical field, such as 4,4' -dimethyl biphenyl which can be oxidized to obtain 4,4 '-biphenyl dicarboxylic acid and 4,4' -biphenyl dicarboxylic acid, and can be used for synthesizing high-performance polymers, such as polyester or polyamide. Properties such as melting point, crystallinity, glass transition point and modulus show higher performance than polymers produced from dibenzoic acid (Macromolecules2002,35, 5123-. Biphenyls are commonly produced during petroleum refining, but are currently commonly produced by coupling substituted aryl compounds.
Coupling of aryl halides is one of the known methods for preparing biaryls. Such as Heck reaction, Suzuki reaction, Stille coupling reaction, etc. (Applied Homogeneous Catalysis with Organometallic Compounds ", Vol.2, B.Fornis and W.A. Herman, 1996, VCH) but these coupling reactions require the use of metal organic reagents, such as organoboron Compounds, organotin Compounds, etc., which need to be synthesized from aryl halides, adding to the steps and cost of the reaction. The byproducts generated by the coupling reaction, such as boron and tin compounds, also cause a plurality of problems of difficult separation, difficult recovery and treatment, environmental pollution and the like, and are difficult to realize large-scale industrialization. An improved process is therefore the oxidative coupling of aryl compounds to produce biaryl compounds. R. van Helden et al (triv. chini.,1965,84,1263) reported a process for oxidizing biphenyl and substituted benzene to produce biphenyl compounds by palladium chloride and sodium acetate in acetic acid solution, but the reaction was carried out at high temperature, the palladium compound was a reactant rather than a catalyst, and after the reaction, metallic palladium was precipitated in the reaction system, and palladium could not be recycled. Oxidative coupling reactions of aryl compounds in the presence of Pd catalyst and trifluoroacetic acid with or without Cu promoter are reported in the literature (j.chem.soc., Perkin I,1974,1289). However, the reaction time is as long as 14 days, and the reaction product is a mixture of biphenyl compound isomers, such as 3,3 ', 3, 4' -or 4,4' -biphenyl compound, which is difficult to separate and purify, and cannot be industrialized on a large scale.
Heteropolyacids (HPAs) and their metal exchanges have been extensively studied as acid catalysts for many reactions and have been industrially applied (chem. Rev.1998,98, 171-. HPA is a solid acid with good application prospect and can replace liquid acid catalyst harmful to environment, such as H2SO4(Ind. Eng. chem. Res.1996,35, 2546-. In the solid state, HPAs display a hierarchical structure, with the structure being divided into three levels, one, two, and three (Current Catalysis,2018,7, 26-34). The structure of the heteropolyanion or polyoxoanion molecule itself is referred to as the primary structure. Based on the primary structure, different polyoxoanion structures exist, such as Keggin structures, Laconary Keggin anions, Dawson structures and Anderson structures. Keggin-type HPAs are generally represented by the formula Hr[Xm+MpOq]Wherein X is a heteroatom (e.g. P)5+、Si4+Etc.), r is any integer between 1 and 10, M is 2,3, 4, 5, 6 or 7, p is 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, q is any integer between 31 and 90, M is an additional atom (typically Mo) and M is an additional atom (typically Mo)6+Or W6+) The most used catalyst, especially H3PW12O40(PW)，H3PMo12O40(PMo) or H4SiW12O40(SiW)。
The heteropolyacid structure may also be modulated by proton-exchange cations (Applied Catalysis A: General,2015,502, 297-304), such as Na+、Cu2+The heteropoly acid formed after proton exchange has the characteristics of small specific surface area, water solubility and the like; cs+,Rb+The heteropoly acid formed after proton exchange has the characteristics of large specific surface area, insolubility in water solubility and the like. The thermal stability of the heteropolyacid is also altered after the protons have been exchanged with the metal cations, e.g. Cs+Exchange H3PW12O40Cs of proton formation2.5H0.5PW12O40Has high thermal stability and can keep the structure stable under the condition of 500 ℃. The effect of the metal cation on the thermal stability of the heteropoly acid is shown generally by Ba2+,Co2+<Cu2+,Ni2+<H+,Cd2+<Ca2+,Mn2+<Mg2+<La3+,Ce3+<NH4+<K+,Tl+,Cs+. Heteropolyacid supported palladium catalysts have been used for the Wacker oxidation reaction. Heteropolyacids such as palladium exchange are used for catalyzing the gas phase Wacker oxidation of 1-butene and show excellent catalytic performance (Journal of Catalysis,1995,154, 175-.
The invention adopts heteropolyacid acid catalyst to catalyze 5,5' -dialkyl-2, 2' -bifuran compound to react with olefin to prepare 4,4' -dialkyl biphenyl. Compared with the method for preparing the 4,4' -dialkyl biphenyl compound by the aryl compound through the coupling reaction, the method does not need to use a noble metal (such as a palladium catalyst required by the coupling reaction) catalyst; the reaction product has high selectivity, only generates 4,4' -dialkyl biphenyl compounds, and does not generate biphenyl compounds (such as 3,3 ', 3, 4' -biphenyl compounds) connected at other positions; the product 4,4' -dialkyl biphenyl compound and the heteropoly acid type catalyst are simple to separate, and the heteropoly acid type catalyst can be recycled.
Disclosure of Invention
The invention provides a method for preparing 4,4' -di-furan by reacting 5,5' -dialkyl-2, 2' -difurane with olefinThe method for preparing the alkyl biphenyl adopts a heteropoly acid type solid acid catalyst, takes 5,5' -dialkyl-2, 2' -difuran as a reaction raw material, and reacts with olefin in a solvent-free or solvent to generate the 4,4' -dialkyl biphenyl compound. Wherein the structural formula of the reaction raw material 5,5 '-dialkyl-2, 2' -difuran is as follows:
Figure BDA0002124518420000031
n is 0, 1, 2,3, 4, 5, 6, 7 or 8. The olefin is ethylene, 2-butylene or the structural formula
Figure BDA0002124518420000032
M is 0, 1, 2,3, 4, 5 or 6. The structural formula of the 4,4' -dialkyl biphenyl compound is as follows:
Figure BDA0002124518420000033
Figure BDA0002124518420000041
n is 0, 1, 2,3, 4, 5, 6, 7 or 8; m is 0, 1, 2,3, 4, 5 or 6.
The heteropoly acid type solid acid catalyst is as follows: the tungstic heteropoly acid or the molybdic heteropoly acid is loaded on the carrier. The tungstophosphoric acid anion has the formula: xm+WpOq(ii) a The chemical formula of the heteropoly molybdenum acid anion is as follows: xm+MopOq(ii) a m is 2,3, 4, 5, 6 or 7, P is 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, q is any integer between 31 and 90, and X is P, Si, Ni, Al, As, Ti, Ge, Sn, Zr, Be, Mn, Co, Fe, Ga, Cr, B, V or I. The cation structural formula of the tungstic heteropoly acid and the molybdic heteropoly acid is HrYsAnd Y is one or a mixture of more of the following cations: H. li, Na, K, Cs, Be, Mg, Ca, Si, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In, Sn, Pb, Zr, Nb, Mo, Tc, W, Re, or a lanthanide metal; r is a rational number between 0 and 8 and s is a rational number between 0 and 8. The carrier is a mixture of one or more solid materials including, but not limited to: carbon material, molecular sieve, clay, silicon oxide, titanium oxide,Cerium oxide, zirconium oxide, aluminum oxide, transition metal oxides, sulfates, phosphates, nitrates, carbonates, or silicates. The solvent is one or a mixture of several of the following solvents: water, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetonitrile, acetone, dioxane, diethyl ether, dichloromethane, tetrahydrofuran, N-methylpyrrolidone, chloroform, alcohols, carboxylic acids or esters.
The invention has the advantages that:
the method for preparing the 4,4' -dialkyl biphenyl compound has high selectivity, the heteropoly acid type solid acid catalyst and the product are easy to separate, the byproduct is water, the method has no pollution to the environment, and the heteropoly acid type solid acid catalyst has low corrosion to equipment and can be repeatedly utilized.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts; the product identification is shown in FIG. 1 and FIG. 2.
FIG. 1: process for preparing 4,4' -dimethylbiphenyl1H NMR
FIG. 2: process for preparing 4,4' -dimethylbiphenyl13C NMR
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
All the starting materials of the present invention are not particularly limited in purity, and the reagents used in the following examples are commercially available. Analytical purification is preferably used in the present invention.
Example 1
H5PMo10V2O40The synthesis process comprises the following steps: 3.63g of V2O50.3mol of H are added dropwise to 150ml of water2O2Stirring to V2O5And (3) completely dissolving, heating to 30-35 ℃, preserving the temperature for a period of time, and dropwise adding 0.003mol of phosphoric acid (85%) after no bubbles are generated to obtain a solution 1. 28.8g of MoO3And 1.95g of phosphoric acid (85%) in 300ml of water, and was condensed under reflux for 2 hours until the solution became yellow to give solution 2. The solution 1 is slowly added dropwise to the solution 2, and the condensation reflux state is maintained until the solid is completely dissolved. Evaporating the excess water to moderate water content, cooling to room temperature, and separating to obtain crystals H5PMo10V2O40。
Example 2
Preparation of SiO2(40STA/SiO 2) Supported Heteropolyacid (HPA) catalyst: 0.8 g of silicotungstic acid was dissolved in 10mL of water and the solution was added to 1.2g of silica support and stirring was continued for 12 hours. Excess water was removed and the catalyst was dried in an oven at 120 ℃ for 12 hours. Finally calcining the catalyst in the air at 300 ℃ for 2 hours to obtain the supported heteropolyacid catalyst 40STA/SiO2。
Example 3
5,5 '-dimethyl-2, 2' -difuran (1mmol) was added to a solution containing solvent (5mL) and catalyst 40STA/SiO2(100mg) in a reaction vessel, after replacing the air in the reaction vessel with nitrogen, ethylene gas (2.5MPa) was added and the reaction was carried out at 220 ℃ for 6 hours, whereby the yield of 4,4' -dimethylbiphenyl was 30%.
Example 4
5,5 '-dimethyl-2, 2' -difuran (1mmol) was added to a solution containing solvent (5mL) and catalyst 40STA/SiO2(100mg) in a reaction vessel, after replacing the air in the reaction vessel with nitrogen, ethylene gas (2.5MPa) was added and the reaction was carried out at 250 ℃ for 4 hours, whereby the yield of 4,4' -dimethylbiphenyl was 100%.
Example 5
5,5' -dimethyl-2, 2-The addition of bifuran (12mmol) to a solution containing solvent (60mL) and catalyst 40STA/SiO2(1.2g) in the reaction vessel, after replacing the air in the reaction vessel with nitrogen, ethylene gas (2.5MPa) was added and the reaction was carried out at 250 ℃ for 4 hours, whereby the yield of 4,4' -dimethylbiphenyl was 100%.

Claims (7)

1. A method for preparing 4,4 '-dialkyl biphenyl compound by 5,5' -dialkyl-2, 2 '-bifuran and alkene reaction is characterized in that a heteropoly acid type solid acid catalyst is adopted, 5' -dialkyl-2, 2 '-bifuran is used as a reaction raw material, and the reaction raw material reacts with alkene in a solvent-free or solvent to generate the 4,4' -dialkyl biphenyl compound;
the olefin is ethylene, 2-butylene or has a structural formula
Figure FDA0003096467350000011
0, 1, 2,3, 4, 5 or 6;
the heteropoly acid type solid acid catalyst is as follows: the tungstic heteropoly acid or the molybdic heteropoly acid is loaded on the carrier.
2. The process for producing 4,4' -dialkylbiphenyl compounds according to claim 1, wherein the reaction raw material 5,5' -dialkyl-2, 2' -difuran has the structural formula:
Figure FDA0003096467350000012
n is 0, 1, 2,3, 4, 5, 6, 7 or 8.
3. The process for preparing 4,4 '-dialkylbiphenyl compounds according to claim 1, wherein the 4,4' -dialkylbiphenyl compounds have the structural formula:
Figure FDA0003096467350000013
n is 0, 1, 2,3, 4, 5, 6, 7 or 8; m is 0, 1, 2,3, 4, 5 or 6.
4. The process for preparing 4,4' -dialkylbiphenyl compounds according to claim 1, wherein the tungstoheteropoly acid anion has the formula: xm+WpOq(ii) a The chemical formula of the heteropoly molybdenum acid anion is as follows: xm+MopOq(ii) a m is 2,3, 4, 5, 6 or 7, P is 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, q is any integer between 31 and 90, and X is P, Si, Ni, Al, As, Ti, Ge, Sn, Zr, Be, Mn, Co, Fe, Ga, Cr, B, V or I.
5. The process for producing 4,4' -dialkylbiphenyl compounds according to claim 1, wherein the cationic structures of the heteropoly tungstic acid and heteropoly molybdic acid are HrYsAnd Y is one or a mixture of more of the following cations: H. li, Na, K, Cs, Be, Mg, Ca, Si, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In, Sn, Pb, Zr, Nb, Mo, Tc, W, Re, or a lanthanide metal; r is a rational number between 0 and 8 and s is a rational number between 0 and 8.
6. The process of claim 1 for the preparation of 4,4' -dialkylbiphenyls by reacting 5,5' -dialkyl-2, 2' -difurane with an olefin, wherein the carrier is a mixture of one or more solid materials including but not limited to: carbon materials, molecular sieves, clays, silica, titania, ceria, zirconia, alumina, transition metal oxides, sulfates, phosphates, nitrates, carbonates, or silicates.
7. The process for preparing 4,4' -dialkylbiphenyl compounds by reacting 5,5' -dialkyl-2, 2' -difurane with olefin according to claim 1, wherein the solvent is one or a mixture of the following solvents: water, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetonitrile, acetone, dioxane, diethyl ether, dichloromethane, tetrahydrofuran, N-methylpyrrolidone, chloroform, alcohols, carboxylic acids or esters.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891633A (en) * 1970-01-07 1975-06-24 Alfred Anisimovich Berlin Method of producing dianhydrides of aromatic tetracarboxylic acids
WO2017111598A1 (en) * 2015-12-22 2017-06-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Preparation of phenyl compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891633A (en) * 1970-01-07 1975-06-24 Alfred Anisimovich Berlin Method of producing dianhydrides of aromatic tetracarboxylic acids
WO2017111598A1 (en) * 2015-12-22 2017-06-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Preparation of phenyl compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Palladium-Catalyzed C−H Homocoupling of Furans and Thiophenes Using Oxygen as the Oxidant;Li Na-Na et al.;《Org. Lett.》;20140507;第16卷(第10期);2732-2735 *

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