WO2020215812A1

WO2020215812A1 - Method for preparing 4,4'-dialkylbiphenyl from 2-alkyl furan

Info

Publication number: WO2020215812A1
Application number: PCT/CN2020/000074
Authority: WO
Inventors: 张宗超; 凯歇尔·拉曼尼; 管西安
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2019-04-25
Filing date: 2020-04-15
Publication date: 2020-10-29

Abstract

Provided in the present invention is a method for preparing 4,4'-dialkylbiphenyl from 2-alkyl furan. The method comprises a two-step reaction: (1) a 5,5'-dialkyl-2,2'-bifuran compound is prepared from 2-alkyl furan, a catalyst used for the reaction is a polyacid palladium or a hetero-polyacid palladium, the catalyst has the advantages of being simple to synthesize and reusable, the reaction conditions are mild, and the product yield is high; and, (2) 4,4'-dialkylbiphenyl is prepared from 5,5'-dialkyl-2,2'-bifuran, a solid hetero-polyacid is employed as a catalyst, the yield of the product 4,4'-dialkylbiphenyl is high, separation from the catalyst is easy, and the polyacid catalyst used provides the advantages of being inexpensive, noncorrosive, recyclable and reusable.

Description

一种2-烷基呋喃制4，4′-二烷基联苯的方法Method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran

技术领域Technical field

本发明属于精细化学品技术领域，具体涉及一种制备4，4′-二烷基联苯的方法，该方法得到的4，4′-二烷基联苯可用于生产联苯二甲酸衍生物，联苯二甲酸衍生物可用于生产各种高性能聚合物如聚酯或聚酰胺等。The invention belongs to the technical field of fine chemicals, and specifically relates to a method for preparing 4,4'-dialkylbiphenyl. The 4,4'-dialkylbiphenyl obtained by the method can be used to produce diphthalic acid derivatives. , Biphthalic acid derivatives can be used to produce various high-performance polymers such as polyester or polyamide.

背景技术Background technique

4，4′-二烷基联苯是化工领域的一种具有重要应用的化合物，如4，4′-二甲基联苯经氧化反应可得到4，4′-联苯二甲酸，4，4′-联苯二甲酸，可用于合成高性能的聚合物，例如聚酯或聚酰胺等。在熔点、结晶度、玻璃化转变点和模量等性质表现出比对二苯甲酸生产的聚合物具有更高的性能(Macromolecules 2002，35，5123-5130)。石油精炼过程中通产会产生联苯类化合物，但目前通常通过取代的芳基化合物的偶联来制备联苯类化合物。4,4'-Dialkylbiphenyl is a compound with important applications in the chemical industry. For example, 4,4'-Dimethylbiphenyl can be oxidized to produce 4,4'-diphthalic acid, 4, 4'-Biphthalic acid can be used to synthesize high-performance polymers, such as polyester or polyamide. The properties of melting point, crystallinity, glass transition point and modulus show higher performance than polymers produced by p-dibenzoic acid (Macromolecules 2002, 35, 5123-5130). Biphenyl compounds are commonly produced during petroleum refining, but currently biphenyl compounds are usually prepared by coupling of substituted aryl compounds.

芳基卤化物的偶联是用于制备联芳基的已知方法之一。如Heck反应、Suzuki反应、Stille偶联反应等(Applied Homogeneous Catalysis with Organometallic Compounds”，Vol.2，B.Fornis and W.A.Herman，1996，VCH)但这些偶联反应需要使用金属有机试剂，如有机硼化合物、有机锡化合物等，这些金属有机化合物需要由芳基卤化物合成，增加了反应的步骤和成本。偶联反应产生的副产物如硼和锡的化合物也造成了分离困难、回收处理困难、环境污染等诸多问题，难以大规模工业化。因此一种改进的方法是芳基化合物的氧化偶联反应来制备联芳基化合物。R.Van Helden等人(Triv.chini.，1965，84，1263)报道了氯化钯和乙酸钠在乙酸溶液中氧化偶联苯和取代苯，生成联苯类化合物的方法，但该反应在高温下进行，钯化合物是反应物而不是催化剂，反应后金属钯在反应体系中沉淀，不能循环使用钯。文献(J.Chem.Soc.，Perkin I，1974，1289)中报道了在Pd催化剂和三氟乙酸存在下，在添加或不添加Cu助催化剂的情况下，芳基化合物的氧化偶联反应。然而，该反应时间长达14天，而且反应产物是联苯类化合物异构体的混合物，例如3，3′，3，4′-或4，4′-联苯类化合物，难以分离提纯，不能实现大规模工业化。The coupling of aryl halides is one of the known methods for preparing biaryl groups. Such as Heck reaction, Suzuki reaction, Stille coupling reaction, etc. (Applied Homogeneous Catalysis with Organometallic Compounds", Vol. 2, B. Fornis and WA Herman, 1996, VCH), but these coupling reactions require the use of metal organic reagents, such as organic boron Compounds, organotin compounds, etc. These metal organic compounds need to be synthesized from aryl halides, which increases the steps and costs of the reaction. The by-products produced by the coupling reaction such as boron and tin compounds also cause difficulties in separation, recovery and processing. Many problems such as environmental pollution, it is difficult to large-scale industrialization. Therefore, an improved method is the oxidative coupling reaction of aryl compounds to prepare biaryl compounds. R. Van Helden et al. (Triv.chini., 1965, 84, 1263) ) Reported that palladium chloride and sodium acetate oxidatively couple benzene and substituted benzene in an acetic acid solution to generate biphenyl compounds, but the reaction is carried out at high temperature. Palladium compounds are reactants rather than catalysts. After the reaction, metallic palladium Precipitation in the reaction system, palladium cannot be recycled. Literature (J. Chem. Soc., Perkin I, 1974, 1289) reported in the presence of Pd catalyst and trifluoroacetic acid, with or without the addition of Cu promoter Next, the oxidative coupling reaction of aryl compounds. However, the reaction time is as long as 14 days, and the reaction product is a mixture of isomers of biphenyl compounds, such as 3,3',3,4'-or 4,4 '-Biphenyl compounds are difficult to separate and purify and cannot be industrialized on a large scale.

2-甲基呋喃是生物质基平台化合物糠醛的加氢产物之一。2-甲基呋喃自身氧化偶联合成5，5′-二甲基-2，2′-联呋喃的反应研究受到科学家的广泛关注。Kozhevnikov等人在(Reaction Kinetics and Catalysis Letters，1976，4，451-458)中首次研究了均相钯催化剂催化的2-甲基呋喃的氧化偶联反应，但偶联产物收率低。Li等人(Org.Lett.2014，16，2732-2735)报道了氧气作为氧化剂，三氟乙酸作为助催化剂，均相钯催化剂在室温下催化的呋喃和噻吩的氧化偶联反应。该方法使用10mol％的钯催化剂，并且钯不能循环再利用。以上报道的工作都使用均相钯配合物为催化剂，产物收率低，催化剂不能循环再利用；需要柱分离纯化产物，分离过程难以大规模工业化。2-Methylfuran is one of the hydrogenation products of the biomass-based platform compound furfural. The reaction of 2-methylfuran to synthesize 5,5'-dimethyl-2,2'-bifuran by self-oxidative coupling has attracted wide attention from scientists. Kozhevnikov et al. (Reaction Kinetics and Catalysis Letters, 1976, 4, 451-458) first studied the oxidative coupling reaction of 2-methylfuran catalyzed by a homogeneous palladium catalyst, but the yield of the coupling product was low. Li et al. (Org. Lett. 2014, 16, 2732-2735) reported the oxidative coupling reaction of furan and thiophene catalyzed by oxygen as an oxidant, trifluoroacetic acid as a cocatalyst, and a homogeneous palladium catalyst at room temperature. This method uses 10 mol% of palladium catalyst, and palladium cannot be recycled. The work reported above uses homogeneous palladium complexes as catalysts, the product yield is low, and the catalyst cannot be recycled; a column is required to separate and purify the product, and the separation process is difficult to industrialize on a large scale.

杂多酸(HPAs)及其金属交换作为许多反应的酸催化剂已被广泛研究，并已有工业应用(Chem.Rev.1998，98，171-198，Catalysis Reviews，2017，59，2，165-188)。HPA是一种很有应用前景的固体酸，可替代对环境有害的液体酸催化剂，如H ₂SO ₄(Ind.Eng.Chem.Res.1996，35，2546-2560)。在固态下，HPA显示分层结构，结构分为一级，二级和三级这三个级别(Current Catalysis，2018，7，26-34)。杂多阴离子或多氧阴离子分子本身的结构称为一级结构。基于一级结构，存在不同的多氧阴离子结构，如Keggin结构，Lacunary Keggin阴离子，Dawson结构和Anderson结构。Keggin型HPAs通常由式H _r[X ^m+M _pO _q]表示，其中X是杂原子(例如P ⁵⁺、Si ⁴⁺等)，r＝1到10之间的任意一个整数，m＝2、3、4、5、6或7，p＝6、7、8、9、10、11、12、13、14、15、16、17或18，q ＝31到90之间的任意一个整数，M是附加原子(通常是Mo ⁶⁺或W ⁶⁺)，是被使用最多的催化剂，尤其是H ₃PW ₁₂O ₄₀(PW)，H ₃PMo ₁₂O ₄₀(PMo)或H ₄SiW ₁₂O ₄₀(SiW)。 Heteropolyacids (HPAs) and their metal exchanges have been widely studied as acid catalysts for many reactions and have been industrially applied (Chem. Rev. 1998, 98, 171-198, Catalysis Reviews, 2017, 59, 2, 165- 188). HPA is a kind of solid acid with great application prospects, which can replace environmentally harmful liquid acid catalysts, such as H ₂ SO ₄ (Ind. Eng. Chem. Res. 1996, 35, 2546-2560). In the solid state, HPA shows a hierarchical structure, and the structure is divided into three levels: primary, secondary and tertiary (Current Catalysis, 2018, 7, 26-34). The structure of the heteropolyanion or polyoxoanion molecule itself is called the primary structure. Based on the primary structure, there are different polyoxoanion structures, such as Keggin structure, Lacunary Keggin anion, Dawson structure and Anderson structure. Keggin-type HPAs are usually represented by the formula H _r [X ^m+ M _p O _q ], where X is a heteroatom (such as P ⁵⁺ , Si ^4+, etc.), r=1 to any integer between 1 and 10, m=2 , 3, 4, 5, 6 or 7, p = 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, q = any integer between 31 and 90 , M is an additional atom (usually Mo ⁶⁺ or W ⁶⁺ ), which is the most used catalyst, especially H ₃ PW ₁₂ O ₄₀ (PW), H ₃ PMo ₁₂ O ₄₀ (PMo) or H ₄ SiW ₁₂ O ₄₀ (SiW).

杂多酸结构也可通过质子交换阳离子进行调变(Applied Catalysis A：General，2015，502，297-304)，如Na ⁺、Cu ²⁺等交换质子后形成的杂多酸具有比表面积小、水溶性等特点；Cs ⁺，Rb ⁺等交换质子后形成的杂多酸具有较大的比表面积、不溶于水溶性等特点。质子被金属阳离子交换后，杂多酸的热稳定性也发生了改变，如Cs ⁺交换H ₃PW ₁₂O ₄₀的质子形成的Cs _2.5H _0.5PW ₁₂O ₄₀，具有高的热稳定性，能在500℃条件下保持结构稳定。通常金属阳离子对杂多酸的热稳定性影响如下所示：Ba ²⁺，Co ²⁺＜Cu ²⁺，Ni ²⁺＜H ⁺，Cd ²⁺＜Ca ²⁺，Mn ²⁺＜Mg ²⁺＜La ³⁺，Ce ³⁺＜NH ⁴⁺＜K ⁺，Tl ⁺，Cs ⁺。杂多酸负载钯催化剂已被用于Wacker氧化反应。如钯交换的杂多酸用于催化1-丁烯的气相Wacker氧化反应，显示出了优异的催化性能(Journal of Catalysis，1995，154，175-186，Journal of Molecular Catalysis A：Chemical，1996，107，247-253)。 The structure of heteropoly acids can also be adjusted by proton exchange cations (Applied Catalysis A: General, 2015, 502, 297-304). For example, the heteropoly acids formed by the exchange of protons such as Na ⁺ and Cu ²⁺ have a small specific surface area, Water solubility and other characteristics; Cs ⁺ , Rb ⁺ and other heteropoly acids formed after proton exchange have the characteristics of large specific surface area, insoluble and water-soluble. After the proton is exchanged by the metal cation, the thermal stability of the heteropoly acid has also changed. For example, the Cs _2.5 H _0.5 PW ₁₂ O ₄₀ formed by the proton exchange of Cs ⁺ H ₃ PW ₁₂ O ₄₀ has high thermal stability and energy Keep the structure stable at 500℃. Generally, the effects of metal cations on the thermal stability of heteropoly acids are as follows: Ba ²⁺ , Co ²⁺ ＜Cu ²⁺ , Ni ²⁺ ＜H ⁺ , Cd ²⁺ ＜Ca ²⁺ , Mn ²⁺ ＜Mg ²⁺ ＜La ³⁺ , Ce ³⁺ ＜NH ⁴⁺ ＜K ⁺ , Tl ⁺ , Cs ⁺ . Heteropolyacid supported palladium catalyst has been used in Wacker oxidation reaction. For example, palladium-exchanged heteropolyacids are used to catalyze the gas phase Wacker oxidation reaction of 1-butene, showing excellent catalytic performance (Journal of Catalysis, 1995, 154, 175-186, Journal of Molecular Catalysis A: Chemical, 1996, 107, 247-253).

本发明提供了一种2-烷基呋喃制4，4′-二烷基联苯的新方法。该新方法包含了两步反应：(1)2-烷基呋喃制5，5′-二烷基-2，2′-联呋喃类化合物，该反应所用催化剂为杂多酸型钯或负载的杂多酸型钯催化剂，催化剂具有合成简单、可回收使用等优点，反应条件温和，产物产率高；(2)5，5′-二烷基-2，2′-联呋喃类化合物制4，4′-二烷基联苯，采用固体杂多酸作为催化剂，产物4，4′-二烷基联苯的收率高，与催化剂分离容易，使用杂多酸催化剂具有低成本、无腐蚀性及可回收再利用的优点。本发明所使用的催化剂均为非均相催化剂，可重复使用，并有利于产物和催化剂的分离和提纯。The present invention provides a new method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran. The new method includes two-step reactions: (1) Preparation of 5,5'-dialkyl-2,2'-bifurans from 2-alkylfurans. The catalyst used in this reaction is heteropolyacid palladium or supported Heteropolyacid palladium catalyst, the catalyst has the advantages of simple synthesis, recyclable use, mild reaction conditions, high product yield; (2) Preparation of 5,5'-dialkyl-2,2'-bifuran compounds 4 , 4'-dialkylbiphenyl, using solid heteropolyacid as the catalyst, the product 4,4'-dialkylbiphenyl has a high yield and is easy to separate from the catalyst. The use of heteropolyacid catalyst has low cost and no corrosion The advantages of sex and recyclability. The catalysts used in the present invention are all heterogeneous catalysts, which can be used repeatedly, and facilitate the separation and purification of products and catalysts.

发明内容Summary of the invention

本发明提供了一种2-烷基呋喃制4，4′-二烷基联苯的方法，采用2-烷基呋喃经过两步反应生成4，4′-二烷基联苯：(1)2-烷基呋喃制5，5′-二烷基-2，2′-联呋喃类化合物采用的催化剂为杂多酸型钯或负载的杂多酸型钯催化剂，反应原料为2-烷基呋喃，在氧化剂作用下，在无溶剂或溶剂中，生成5，5′-二烷基-2，2′-联呋喃类化合物；(2)5，5′-二烷基-2，2′-联呋喃与烯烃反应制备4，4′-二烷基联苯的催化剂为杂多酸型固体酸催化剂，反应原料为5，5′-二烷基-2，2′-联呋喃，在无溶剂或溶剂中，与烯烃反应生成4，4′-二烷基联苯类化合物。The present invention provides a method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran, which uses 2-alkylfuran to produce 4,4'-dialkylbiphenyl through a two-step reaction: (1) The catalyst used for preparing 5,5'-dialkyl-2,2'-bifuran compounds from 2-alkylfuran is heteropolyacid palladium or supported heteropolyacid palladium catalyst, and the reaction raw material is 2-alkyl Furan, under the action of oxidizing agent, in the absence of solvent or solvent, 5,5'-dialkyl-2,2'-bifuran compounds are generated; (2) 5,5'-dialkyl-2,2' -The catalyst for the reaction of bifuran and olefin to prepare 4,4'-dialkylbiphenyl is a heteropolyacid type solid acid catalyst, and the reaction raw material is 5,5'-dialkyl-2,2'-bifuran. In the solvent or solvent, it reacts with olefins to produce 4,4'-dialkyl biphenyl compounds.

2-烷基呋喃结构式为：

n＝0、1、2、3、4、5、6、7或8。 The structural formula of 2-alkylfuran is:

n=0, 1, 2, 3, 4, 5, 6, 7, or 8.

5，5′-二烷基-2，2′-联呋喃类化合物结构式为：

n＝0、1、2、3、4、5、6、7或8。 The structural formula of 5,5'-dialkyl-2,2'-bifuran compounds is:

n=0, 1, 2, 3, 4, 5, 6, 7, or 8.

烯烃为乙烯、2-丁烯或结构式为

的烯烃，m＝0、1、2、3、4、5或6。 The olefin is ethylene, 2-butene or the structural formula is

The olefin, m=0, 1, 2, 3, 4, 5 or 6.

4，4′-二烷基联苯类化合物的结构式为：

n＝0、1、2、3、4、5、6、7或8；m＝0、1、2、3、4、5或6。 The structural formula of 4,4'-dialkyl biphenyl compounds is:

n=0, 1, 2, 3, 4, 5, 6, 7 or 8; m=0, 1, 2, 3, 4, 5 or 6.

杂多酸型钯催化剂为：钨杂多酸型钯催化剂，分子式为[Pd _rY _s][X ^t+W _pO _q]或钼杂多酸型钯催化剂，分子式为[Pd _rY _s][X ^t+Mo _pO _q]；负载的杂多酸型钯为：杂多酸型钯催化剂负载到载体上；杂多酸型固体酸催化剂为：钨杂多酸，分子式为 [H _rY _s][X ^t+W _pO _q]或钼杂多酸，分子式为[H _rY _s][X ^t+Mo _pO _q]负载到载体上。[Pd _rY _s]和[H _rY _s]中的Y为以下阳离子的一种或几种的混合：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、或镧系金属；r为0到4之间的有理数，s为0到8之间的有理数。[X ^t+W _pO _q]和[X ^t+Mo _pO _q]中的t＝2、3、4、5、6或7，p＝6、7、8、9、10、11、12、13、14、15、16、17或18，q＝31到90之间的任意一个整数，X＝P、Si、Ni、Al、As、Ti、Ge、Sn、Zr、Be、Mn、Co、Fe、Ga、Cr、B、V或I。载体为一种或几种固体材料的混合，固体材料包括但不限于：碳材料、分子筛、粘土、氧化硅、氧化钛、氧化铈、氧化锆、氧化铝、过渡金属氧化物、硫酸盐、磷酸盐、硝酸盐、碳酸盐、或硅酸盐。合成杂多酸型钯或负载的杂多酸型钯的钯来自于以下一种或几种的掺杂：氯化钯、硝酸钯、醋酸钯、硫酸钯、高氯酸钯、溴化钯、乙酰丙酮钯、三(二亚苄基丙酮)二钯或钯的配合物。 The heteropoly acid type palladium catalyst is: tungsten heteropoly acid type palladium catalyst, the molecular formula is [Pd _r Y _s ][X ^t+ W _p O _q ] or the molybdenum heteropoly acid type palladium catalyst, the molecular formula is [Pd _r Y _s ][ X ^t+ Mo _p O _q ]; The supported heteropoly acid palladium is: the heteropoly acid palladium catalyst is supported on the carrier; the heteropoly acid solid acid catalyst is: tungsten heteropoly acid, the molecular formula is [H _r Y _s ] [X ^{t +} W _p O _q ] or molybdenum heteropoly acid, the molecular formula is [H _r Y _s ] [X ^{t +} Mo _p O _q ] is loaded on the carrier. Y in [Pd _r Y _s ] and [H _r Y _s ] is one or a mixture 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 lanthanide metals; r is 0 to 4 A rational number between 0 and 8. s is a rational number between 0 and 8. T=2, 3, 4, 5, 6 or 7, in [X ^t+ W _p O _q ] and [X ^t+ Mo _p O _q ], p=6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, or 18, q = any integer between 31 and 90, X = P, Si, Ni, Al, As, Ti, Ge, Sn, Zr, Be, Mn, Co, Fe , Ga, Cr, B, V, or I. The carrier is a mixture of one or several solid materials. The solid materials include but are not limited to: carbon materials, molecular sieves, clay, silica, titanium oxide, cerium oxide, zirconium oxide, aluminum oxide, transition metal oxides, sulfates, phosphoric acid Salt, nitrate, carbonate, or silicate. Palladium for the synthesis of heteropolyacid palladium or supported heteropolyacid palladium comes from one or more of the following doping: palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, palladium perchlorate, palladium bromide, Palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium or a complex of palladium.

杂多酸型钯或负载的杂多酸型钯中的杂多酸的含量为0.1wt％-100wt％；钯的含量为0.01wt％-50wt％。The content of heteropoly acid in the heteropoly acid type palladium or the supported heteropoly acid type palladium is 0.1wt%-100wt%; the content of palladium is 0.01wt%-50wt%.

氧化剂为以下一种或几种的混合：空气、氧气、双氧水、次氯酸钠或有机过氧化物。气体氧化剂的压力为0.1Mpa-10Mpa，液体或固体氧化剂的浓度为0.001wt％-100wt％。The oxidant is one or a mixture of the following: air, oxygen, hydrogen peroxide, sodium hypochlorite or organic peroxide. The pressure of the gas oxidant is 0.1Mpa-10Mpa, and the concentration of the liquid or solid oxidant is 0.001wt%-100wt%.

溶剂为以下一种或几种溶剂的混合：水、二甲基亚砜、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、乙腈、丙酮、二氧六环、***、二氯甲烷、四氢呋喃、N-甲基吡咯烷酮、氯仿、醇类、羧酸类或酯类。The solvent is one or a mixture of the following solvents: water, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, acetone, dioxane, ether , Dichloromethane, tetrahydrofuran, N-methylpyrrolidone, chloroform, alcohols, carboxylic acids or esters.

本发明提供了一种2-烷基呋喃制4，4′-二烷基联苯类化合物的新方法。该方法所用催化剂为杂多酸型钯或负载的杂多酸型钯催化剂，催化剂具有合成简单、可回收使用等优点，反应条件温和，产物5，5′-二烷基-2，2′-联呋喃类化合物产率高，通过过滤分离出催化剂，然后蒸发溶剂得到产物5，5′-二烷基-2，2′-联呋喃类化合物。5，5′-二烷基-2，2′-联呋喃类化合物制4，4′-二烷基联苯类化合物的选择性高，杂多酸型固体酸催化剂和产物易于分离，副产物为水，对环境无污染，杂多酸型固体酸催化剂对设备腐蚀性低，可重复利用。The present invention provides a new method for preparing 4,4'-dialkylbiphenyl compounds from 2-alkylfuran. The catalyst used in the method is a heteropolyacid palladium or a supported heteropolyacid palladium catalyst. The catalyst has the advantages of simple synthesis, recyclability, etc., mild reaction conditions, and the product 5,5′-dialkyl-2,2′- The yield of bifuran compounds is high. The catalyst is separated by filtration, and then the solvent is evaporated to obtain the product 5,5'-dialkyl-2,2'-bifuran compound. 5,5'-dialkyl-2,2'-bifuran compounds have high selectivity for preparing 4,4'-dialkylbiphenyl compounds, heteropoly acid type solid acid catalyst and product are easy to separate, and by-products It is water and has no pollution to the environment. The heteropoly acid type solid acid catalyst has low corrosion to equipment and can be reused.

附图说明Description of the drawings

为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。In order to explain the technical solutions of the embodiments of the present invention more clearly, the following will briefly introduce the drawings that need to be used in the embodiments. It should be understood that the following drawings only show certain embodiments of the present invention and therefore do not It should be regarded as a limitation of the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative work.

图1：5，5′-二甲基-2，2′-联呋喃的 ¹H NMR Figure 1: ¹ H NMR of 5,5'-dimethyl-2,2'-bifuran

图2：5，5′-二甲基-2，2′-联呋喃的 ¹³C NMR Figure 2: ¹³ C NMR of 5,5'-dimethyl-2,2'-bifuran

图3：4，4′-二甲基联苯的 ¹H NMR Figure 3: ¹ H NMR of 4,4′-dimethylbiphenyl

图4：4，4′-二甲基联苯的 ¹³C NMR。 Figure 4: ¹³ C NMR of 4,4'-dimethylbiphenyl.

具体实施方式Detailed ways

下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。本发明要求保护范围由所附的权利要求书及其等效物界定。The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

本发明所有原料，对其纯度没有特别限制，以下实施例中所用的试剂均为市售。本发明优选采用分析纯。All the raw materials of the present invention have no particular restrictions on their purity. The reagents used in the following examples are all commercially available. The present invention preferably uses analytical purity.

实施例1.Example 1.

H ₅PMo ₁₀V ₂O ₄₀的合成过程：3.63g的V ₂O ₅于150ml水中，滴加0.3mol H ₂O ₂，搅拌至V ₂O ₅完全溶解，升温至30-35℃保温一段时间，当无气泡产生后滴加0.003mol磷酸(85％)，得到溶液1。28.8g的MoO ₃和1.95g的磷酸(85％)于300ml水中，冷凝回流2h至溶液变黄，得到溶液2。将溶液1缓慢滴加到溶液2中，保持冷凝回流状态至固体完全溶解。蒸发多余的水至水量适中，冷却到室温分离得晶体为H ₅PMo ₁₀V ₂O ₄₀。 The synthesis process of H ₅ PMo ₁₀ V ₂ O ₄₀ : 3.63g of V ₂ O ₅ in 150 ml of water, add 0.3 mol of H ₂ O ₂ dropwise, stir until V ₂ O _{5 is} completely dissolved, heat up to 30-35 ℃ for a period of time When no bubbles are generated, 0.003 mol phosphoric acid (85%) is added dropwise to obtain a solution of 1. 28.8 g of MoO ₃ and 1.95 g of phosphoric acid (85%) in 300 ml of water, condensed and refluxed for 2 hours until the solution turns yellow, and solution 2 is obtained. Slowly add solution 1 dropwise to solution 2, keeping the reflux state until the solid is completely dissolved. Evaporate the excess water until the amount of water is moderate, and cool to room temperature to separate the crystals as H ₅ PMo ₁₀ V ₂ O ₄₀ .

实施例2.Example 2.

Pd _2.5PMo ₁₀V ₂O ₄₀/SiO ₂的合成过程：将硝酸钯溶解于稀硝酸溶液中，加入化学计量比的H ₅PMo ₁₀V ₂O ₄₀充分混合后，减压蒸馏得到固体，加适量水溶解再等体积浸渍二氧化硅得到Pd _2.5PMo ₁₀V ₂O ₄₀/SiO ₂。 Synthetic process of Pd _2.5 PMo ₁₀ V ₂ O ₄₀ /SiO ₂ : Dissolve palladium nitrate in dilute nitric acid solution, add stoichiometric ratio of H ₅ PMo ₁₀ V ₂ O _{40 and} mix thoroughly, then distill under reduced pressure to obtain a solid. Pd _2.5 PMo ₁₀ V ₂ O ₄₀ /SiO _{2 is} obtained by dissolving in water and impregnating silica in an equal volume.

实施例3.Example 3.

将硅钨酸(杂多酸的一个实例)(5g，1.73mmol)溶解在20mL去离子水中并在室温下剧烈搅拌得到溶液1。然后将所需量的PdSO ₄水溶液滴加到溶液1中，将得到的混合物在室温下过夜老化，并在旋转蒸发仪上除去水，将获得的固体物质在120℃下干燥12小时。相同方法制备不同Pd含量的催化剂Pd _xH ₄-2xSiW ₁₂O ₄₀(x＝0.5，1和2)。制备的不同Pd含量的催化剂分别表示为Pd _0.5STA，Pd ₁STA和Pd ₂STA。 Silicotungstic acid (an example of heteropoly acid) (5 g, 1.73 mmol) was dissolved in 20 mL of deionized water and stirred vigorously at room temperature to obtain solution 1. Then the required amount of PdSO ₄ aqueous solution was added dropwise to solution 1, the obtained mixture was aged at room temperature overnight, and the water was removed on a rotary evaporator, and the obtained solid matter was dried at 120° C. for 12 hours. The catalysts Pd _x H ₄ -2 _x SiW ₁₂ O ₄₀ (x = 0.5, 1 and 2) with different Pd contents were prepared in the same method. The prepared catalysts with different Pd content are denoted as Pd _0.5 STA, Pd ₁ STA and Pd ₂ STA, respectively.

实施例4.Example 4.

制备二氧化硅负载的PdxSTA(x＝0.5，1和2)催化剂：将所需量的PdxSTA溶解在微量的水中，浸渍到二氧化硅载体上，搅拌12小时，过滤后的固体催化剂放在120℃烘箱中干燥12小时，最后将催化剂在空气中于300℃下煅烧2小时。这些催化剂表示为40Pd _xSTA/SiO ₂(x＝0.5，1和2)。 Preparation of silica-supported PdxSTA (x = 0.5, 1 and 2) catalyst: Dissolve the required amount of PdxSTA in a small amount of water, immerse it on the silica support, and stir for 12 hours. The filtered solid catalyst is placed at 120 It was dried in an oven at ℃ for 12 hours, and finally the catalyst was calcined in air at 300 ℃ for 2 hours. These catalysts are expressed as 40Pd _x STA/SiO ₂ (x = 0.5, 1 and 2).

通过浸渍法制备了不同二氧化硅负载的不同负载量的Pd ₂STA催化剂。将一定量的Pd ₂STA溶解在微量的水中，将该溶液加入二氧化硅载体中，搅拌12小时，并将固体催化剂在120℃烘箱中干燥过夜，然后于330℃下煅烧2小时。这些催化剂表示为xPd ₂STA/SiO ₂(其中x＝10-60)。 Pd ₂ STA catalysts with different loadings on different silicas were prepared by impregnation method. A certain amount of Pd ₂ STA was dissolved in a trace amount of water, the solution was added to the silica carrier, stirred for 12 hours, and the solid catalyst was dried in an oven at 120°C overnight, and then calcined at 330°C for 2 hours. These catalysts are expressed as xPd ₂ STA/SiO ₂ (where x = 10-60).

实施例5.Example 5.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂40Pd _0.5STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为9％。通过GC-MS、 ¹H NMR和 ¹³C NMR鉴定产物(如图1、图2所示)。产物5，5′-二甲基-2，2′-联呋喃的核磁表征数据分析： ¹H NMR(400MHz，Chloroform-d)δ＝6.25(d，J＝2.5Hz，2H)，5.89(m，2H)，2.22(s，6H)ppm； ¹³C NMR(101MHz，Chloroform-d)δ＝151.22，145.28，107.24，106.09，13.52ppm。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 40Pd _0.5 STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 9%. The product was identified by GC-MS, ¹ H NMR and ¹³ C NMR (as shown in Figure 1 and Figure 2). Analysis of the nuclear magnetic characterization data of the product 5,5'-dimethyl-2,2'-bifuran: ¹ H NMR (400MHz, Chloroform-d) δ = 6.25 (d, J = 2.5 Hz, 2H), 5.89 (m , 2H), 2.22 (s, 6H) ppm; ¹³ C NMR (101 MHz, Chloroform-d) δ = 151.22, 145.28, 107.24, 106.09, 13.52 ppm.

实施例6.Example 6.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂Pd _2.5PMo ₁₀V ₂O ₄₀/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为87％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst Pd _2.5 PMo ₁₀ V ₂ O ₄₀ /SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 87%.

实施例7.Example 7.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂30Pd ₂STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为0.1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基2，2′-联呋喃，产率为54％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 30Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 0.1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl 2,2'-bifuran with a yield of 54%.

实施例8.Example 8.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂30Pd ₂STA/SBA-15(5.2mol％)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为0.1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为25％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 30Pd ₂ STA/SBA-15 (5.2 mol%). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 0.1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 25%.

实施例9.Example 9.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂40Pd ₁STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为29％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 40Pd ₁ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 29%.

实施例10.Example 10.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂40Pd ₂STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为87％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 40Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 87%.

实施例11.Example 11.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂40Pd ₂STA/H-ZSM-5(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为9％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 40Pd ₂ STA/H-ZSM-5 (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 9%.

实施例12.Example 12.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂40Pd ₂STA/SBA-15(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为25％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 40Pd ₂ STA/SBA-15 (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 25%.

实施例13.Example 13.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂10Pd ₂STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为14％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 10Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 14%.

实施例14.Example 14.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂20Pd ₂STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为61％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 20Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 61%.

实施例15.Example 15.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂30Pd ₂STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为71％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 30Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 71%.

实施例16.Example 16.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂50Pd ₂STA/SiO ₂ (300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为75％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 50Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 75%.

实施例17.Example 17.

将2-甲基呋喃(1mmol)加入到含有DMSO(1.5mL)和催化剂60Pd ₂STA/SiO ₂(300mg)的间歇式反应釜(10mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为66％。 2-Methylfuran (1 mmol) was added to a batch reactor (10 mL) containing DMSO (1.5 mL) and the catalyst 60Pd ₂ STA/SiO ₂ (300 mg). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 66%.

实施例18.Example 18.

将2-甲基呋喃(50mmol)加入到含有DMSO(50mL)和催化剂40Pd ₂STA/SiO ₂(10g)的间歇式反应釜(500mL)中。氮气吹扫去除高压釜反应器中的水分和杂质。氧气压力为1MPa，室温下搅拌反应24小时。过滤分离出催化剂，减压去除溶剂得到产物5，5′-二甲基-2，2′-联呋喃，产率为75％。分离的催化剂在烘箱中干燥，继续循环使用四次，第一次到第四次循环反应的产物收率分别为75％、71％、66％、66％。 2-Methylfuran (50 mmol) was added to a batch reactor (500 mL) containing DMSO (50 mL) and the catalyst 40Pd ₂ STA/SiO ₂ (10 g). Nitrogen purging removes moisture and impurities in the autoclave reactor. The oxygen pressure was 1 MPa, and the reaction was stirred at room temperature for 24 hours. The catalyst was separated by filtration, and the solvent was removed under reduced pressure to obtain the product 5,5'-dimethyl-2,2'-bifuran with a yield of 75%. The separated catalyst is dried in an oven and is continuously recycled for four times. The product yields of the first to fourth cycles of the reaction are 75%, 71%, 66%, and 66%, respectively.

实施例19Example 19

制备SiO ₂(40STA/SiO ₂)负载的杂多酸(HPA)催化剂：将0.8克硅钨酸溶解在10mL水中，并将该溶液加入到1.2g二氧化硅载体中持续搅拌12小时。除去过量的水，并将催化剂在烘箱中于120℃下干燥12小时。最后将催化剂在空气中在300℃下煅烧2小时得到负载型杂多酸催化剂40STA/SiO ₂。 Preparation of SiO ₂ (40STA/SiO ₂ ) supported heteropoly acid (HPA) catalyst: 0.8 g of silicotungstic acid was dissolved in 10 mL of water, and the solution was added to 1.2 g of silica support for continuous stirring for 12 hours. The excess water was removed, and the catalyst was dried in an oven at 120°C for 12 hours. Finally, the catalyst was calcined in air at 300°C for 2 hours to obtain a supported heteropolyacid catalyst 40STA/SiO ₂ .

实施例20Example 20

将5，5′-二甲基-2，2′-联呋喃(1mmol)加入到含有溶剂(5mL)和催化剂 40STA/SiO ₂(100mg)的反应釜中，氮气置换反应釜中的空气后，加入乙烯气体(2.5MPa)，220℃下反应6小时，产物4，4′-二甲基联苯的收率为30％。 Add 5,5'-dimethyl-2,2'-bifuran (1mmol) to the reactor containing solvent (5mL) and the catalyst 40STA/SiO ₂ (100mg), and after replacing the air in the reactor with nitrogen, Add ethylene gas (2.5MPa) and react at 220°C for 6 hours. The yield of the product 4,4'-dimethylbiphenyl is 30%.

实施例21Example 21

将5，5′-二甲基-2，2′-联呋喃(1mmol)加入到含有溶剂(5mL)和催化剂40STA/SiO ₂(100mg)的反应釜中，氮气置换反应釜中的空气后，加入乙烯气体(2.5MPa)，250℃下反应4小时，产物4，4′-二甲基联苯的收率为100％。通过GC-MS、 ¹H NMR和 ¹³C NMR鉴定产物(如图3、图4所示) Add 5,5'-dimethyl-2,2'-bifuran (1mmol) to the reactor containing solvent (5mL) and the catalyst 40STA/SiO ₂ (100mg), and after replacing the air in the reactor with nitrogen, Ethylene gas (2.5MPa) was added and reacted at 250°C for 4 hours. The yield of the product 4,4'-dimethylbiphenyl was 100%. Identify the product by GC-MS, ¹ H NMR and ¹³ C NMR (as shown in Figure 3 and Figure 4)

实施例22Example 22

将5，5′-二甲基-2，2′-联呋喃(12mmol)加入到含有溶剂(60mL)和催化剂40STA/SiO ₂(1.2g)的反应釜中，氮气置换反应釜中的空气后，加入乙烯气体(2.5MPa)，250℃下反应4小时，产物4，4′-二甲基联苯的收率为100％。 Add 5,5'-dimethyl-2,2'-bifuran (12mmol) to the reactor containing the solvent (60mL) and the catalyst 40STA/SiO ₂ (1.2g), after replacing the air in the reactor with nitrogen , Adding ethylene gas (2.5MPa), reacting at 250°C for 4 hours, the yield of the product 4,4'-dimethylbiphenyl is 100%.

Claims

一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于，2-烷基呋喃两步反应生成4，4′-二烷基联苯具体步骤如下：A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran, characterized in that, the specific steps of 2-alkylfuran reaction to produce 4,4'-dialkylbiphenyl are as follows:

(1)催化剂为杂多酸型钯或负载的杂多酸型钯催化剂，反应原料为2-烷基呋喃，在氧化剂作用下，在无溶剂或溶剂中，生成5，5′-二烷基-2，2′-联呋喃类化合物；(1) The catalyst is a heteropolyacid palladium or a supported heteropolyacid palladium catalyst, and the reaction raw material is 2-alkylfuran. Under the action of an oxidizing agent, in the absence of solvent or solvent, 5,5'-dialkyl is formed -2,2'-bifuran compounds;

(2)将步骤(1)得到的5，5′-二烷基-2，2′-联呋喃作为反应原料，催化剂为杂多酸型固体酸催化剂，在无溶剂或溶剂中，与烯烃反应生成4，4′-二烷基联苯类化合物。(2) The 5,5'-dialkyl-2,2'-bifuran obtained in step (1) is used as the reaction raw material, and the catalyst is a heteropolyacid type solid acid catalyst, which reacts with olefins without solvent or in solvent Generate 4,4'-dialkyl biphenyl compounds.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于所述2-烷基呋喃结构式为：
n＝0、1、2、3、4、5、6、7或8。 A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 1, wherein the structural formula of the 2-alkylfuran is:
n=0, 1, 2, 3, 4, 5, 6, 7, or 8.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于所述5，5′-二烷基-2，2′-联呋喃类化合物结构式为：
n＝0、1、2、3、4、5、6、7或8。 A method for preparing 4,4'-dialkylbiphenyls from 2-alkylfurans according to claim 1, characterized in that the 5,5'-dialkyl-2,2'-bifurans The compound structural formula is:
n=0, 1, 2, 3, 4, 5, 6, 7, or 8.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于烯烃为乙烯、2-丁烯或结构式为
的烯烃，m＝0、1、2、3、4、5或6。 A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 1, wherein the olefin is ethylene, 2-butene or the structural formula is
The olefin, m=0, 1, 2, 3, 4, 5 or 6.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于，4，4′-二烷基联苯类化合物的结构式为：

n＝0、1、2、3、4、5、6、7或8；m＝0、1、2、3、4、5或6。 A method for preparing 4,4'-dialkylbiphenyls from 2-alkylfurans according to claim 1, wherein the structural formula of 4,4'-dialkylbiphenyls is:

n=0, 1, 2, 3, 4, 5, 6, 7 or 8; m=0, 1, 2, 3, 4, 5 or 6.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于，所述杂多酸型钯为钨杂多酸型钯催化剂或钼杂多酸型钯催化剂；所述钨杂多酸型钯催化剂子式为[Pd _rY _s][X ^m+W _pO _q]，钼杂多酸型钯催化剂分子式为[Pd _rY _s][X ^m+Mo _pO _q]；所述负载的杂多酸型钯为：杂多酸型钯催化剂负载到载体上；所述杂多酸型固体酸催化剂为：钨杂多酸或钼杂多酸负载到载体上，其中钨杂多酸分子式为[H _rY _s][X ^t+W _pO _q]，钼杂多酸分子式为[H _rY _s][X ^t+Mo _pO _q]。 The method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 1, wherein the heteropoly acid palladium is a tungsten heteropoly acid palladium catalyst or a molybdenum hetero Polyacid palladium catalyst; the sub-formula of the tungsten heteropoly acid palladium catalyst is [Pd _r Y _s ][X ^m+ W _p O _q ], and the molecular formula of the molybdenum heteropoly acid palladium catalyst is [Pd _r Y _s ][X ^m+ Mo _p O _q ]; The supported heteropoly acid palladium is: a heteropoly acid palladium catalyst is supported on a carrier; the heteropoly acid solid acid catalyst is: a tungsten heteropoly acid or a molybdenum heteropoly acid supported On the carrier, the molecular formula of tungsten heteropoly acid is [H _r Y _s ][X ^t+ W _p O _q ], and the molecular formula of molybdenum heteropoly acid is [H _r Y _s ][X ^t+ Mo _p O _q ].
按照权利要求6所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于所述[Pd _rY _s]和[H _rY _s]中的Y为以下阳离子的一种或几种的混合：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、或镧系金属；r为0到4之间的有理数，s为0到8之间的有理数。 A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 6, wherein the Y in [Pd _r Y _s ] and [H _r Y _s ] is One or a combination 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 lanthanide metals; r is a rational number between 0 and 4, and s is a rational number between 0 and 8.
按照权利要求6所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于所述[X ^t+W _pO _q]和X ^t+Mo _pO _q]中的t＝2、3、4、5、6或7，p＝6、7、8、9、10、11、12、13、14、15、16、17或18，q＝31到90之间的任意一个整数，X＝P、Si、Ni、Al、As、Ti、Ge、Sn、Zr、Be、Mn、Co、Fe、Ga、Cr、B、V或I。 A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 6, characterized in that in the [X ^{t +} W _p O _q ] and X ^{t +} Mo _p O _q ] T = 2, 3, 4, 5, 6 or 7, p = 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, q = between 31 and 90 Any integer of X=P, Si, Ni, Al, As, Ti, Ge, Sn, Zr, Be, Mn, Co, Fe, Ga, Cr, B, V or I.
按照权利要求6所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于所述载体为一种或几种固体材料的混合，所述固体材料包括但不限于：碳材料、分子筛、粘土、氧化硅、氧化钛、氧化铈、氧化锆、氧化铝、过渡金属氧化物、硫酸盐、磷酸盐、硝酸盐、碳酸盐、或硅酸盐。A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 6, wherein the carrier is a mixture of one or more solid materials, and the solid materials include But not limited to: carbon material, molecular sieve, clay, silicon oxide, titanium oxide, cerium oxide, zirconium oxide, aluminum oxide, transition metal oxide, sulfate, phosphate, nitrate, carbonate, or silicate.
按照权利要求6所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于合成杂多酸型钯或负载的杂多酸型钯的钯来自于以下一种或几种的掺杂：氯化钯、硝酸钯、醋酸钯、硫酸钯、高氯酸钯、溴化钯、乙酰丙酮钯、三(二亚苄基丙酮)二钯或钯的配合物。A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 6, characterized in that the palladium for synthesizing heteropolyacid palladium or supported heteropolyacid palladium comes from the following One or more kinds of doping: palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, palladium perchlorate, palladium bromide, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium or palladium complex .
按照权利要求6所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于杂多酸型钯或负载的杂多酸型钯中的杂多酸的含量为0.1wt％-100wt％；钯的含量为0.01wt％-50wt％。A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 6, characterized in that the heteropolyacid type palladium or the heteropolyacid in the supported heteropolyacid type palladium The content is 0.1wt%-100wt%; the content of palladium is 0.01wt%-50wt%.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于氧化剂为以下一种或几种的混合：空气、氧气、双氧水、次氯酸钠或有机过氧化物。A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 1, wherein the oxidant is one or a mixture of the following: air, oxygen, hydrogen peroxide, sodium hypochlorite or Organic peroxides.
按照权利要求12所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于气体氧化剂的压力为0.1Mpa-10Mpa，液体或固体氧化剂的浓度为0.001wt％-100wt％。A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 12, wherein the pressure of the gas oxidant is 0.1Mpa-10Mpa, and the concentration of the liquid or solid oxidant is 0.001wt. %-100wt%.
按照权利要求1所述的一种2-烷基呋喃制4，4′-二烷基联苯的方法，其特征在于所述溶剂为以下一种或几种溶剂的混合：水、二甲基亚砜、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、乙腈、丙酮、二氧六环、***、二氯甲烷、四氢呋喃、N-甲基吡咯烷酮、氯仿、醇类、羧酸类或酯类。A method for preparing 4,4'-dialkylbiphenyl from 2-alkylfuran according to claim 1, wherein the solvent is a mixture of one or more of the following solvents: water, dimethyl Sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, acetone, dioxane, ether, dichloromethane, tetrahydrofuran, N-methylpyrrolidone, chloroform, alcohols , Carboxylic acid or ester.