CN104211559B - A kind of preparation method of tetramethyl biphenyl isomer - Google Patents
A kind of preparation method of tetramethyl biphenyl isomer Download PDFInfo
- Publication number
- CN104211559B CN104211559B CN201410476948.4A CN201410476948A CN104211559B CN 104211559 B CN104211559 B CN 104211559B CN 201410476948 A CN201410476948 A CN 201410476948A CN 104211559 B CN104211559 B CN 104211559B
- Authority
- CN
- China
- Prior art keywords
- methylene
- pyridine
- tetramethyl biphenyl
- preparation
- biphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method preparing tetramethyl biphenyl isomer, use boiling point 80oMore than C, low toxicity, non-water-soluble alkyl substituted tetrahydro furan are dicyandiamide solution, and halo o-Dimethylbenzene is raw material, and magnesium is reducing agent, the complex that the salt of transiting metal nickel, copper, ferrum, manganese or cobalt etc. or its auxiliary agent such as organophosphor, organic amine are formed is catalyst, prepares 3,3 ' by coupling reaction, 4,4 ' tetramethyl biphenyls, 2,3 ', 3,4 ' tetramethyl biphenyls and 2,2 ', 3,3 ' tetramethyl biphenyl isomers.The present invention realizes solvent cyclic utilization rate and reaches more than 90%, and tetramethyl biphenyl isomeric compound yield reaches 85 ~ 95%.
Description
Technical field
The present invention relates to synthetic organic chemical art, be specifically related to the preparation method of a kind of tetramethyl connection isomer.
Background technology
BPDA is called for short BPDA, is one of important dianhydride monomer of synthesis of polyimides material.Such as 3,3 ', 4,4 '-BPDA is widely used in heat-proof macromolecule material, and it is most widely used one of kind in terms of fire resistant polyimide material.In recent years, research worker finds, containing dissymmetrical structure 2,3 ', 3,4 '-biphenyl dianhydride polymer phase is than the 3 of symmetrical structure, 3 ', 4,4 '-biphenyl dianhydride polymer has higher vitrification point and lower melt viscosity, and this character is expected to thoroughly to change contradiction between composite property and difficult processing in decades.Due to 2,3 ', 3,4 '-biphenyl dianhydride is the property of the polymer composite of main preparation so that it is become remarkable material in military fields such as Aero-Space.Current 2,3 ', 3,4 '-biphenyl dianhydride is as production 3,3 ', 4, the by-product of 4 '-biphenyl dianhydride, separating-purifying difficulty, limits throughput, and therefore its price is 3, and 3 ', 4,10-20 times of 4 '-biphenyl dianhydride price, sufficiently expensive.Relevant 2,3 ', 3, the report of 4 '-biphenyl dianhydride synthetic method is little, is especially suitable for industrialization low cost synthesis 2,3 ', 3, and the method for 4 '-biphenyl dianhydride is less.Therefore developing low-cost synthesis 2,3 ', 3, the route of 4 '-biphenyl dianhydride, the development and application to improving polymer matrix composites has great importance.
Produce at present biphenyl dianhydride mainly use Metal Palladium (Pd) and salt thereof etc. as catalyst, it is generally required to high-temperature high-pressure craft process synthesis biphenyl dianhydride intermediate.Metal Palladium price is extremely expensive, it is low that biphenyl dianhydride intermediate productivity is prepared in palladium chtalyst coupling, the biphenyl dianhydride cost obtained is high, relevant research report such as patent JP7352749, JP80141417, JP8551151, JP8020705, US6914152, US5243067, US3636168, US7425650, US3895055, US4294976, US6103919, CN201310049837 etc..
The complex catalyst formed with Ni (0) or Pd (0) and organic phosphine or nitrogen compound, zinc powder is as reducing agent, by coupling halo o-Dimethylbenzene or the method for halophthalic acid dialkyl, then through hydrolysis, be acidified and biphenyl dianhydride is prepared in the reaction such as dehydration.The method subject matter of the research reports such as above-mentioned Patents US5081281, CN1189597, CN101481366, CN102020622B, CN201110202366 is: 1) needs the reducing agent of big excess and substantial amounts of catalyst, causes substantial amounts of industrial residue；2) solvent is water miscible high boiling point amide solvent such as dimethylformamide, dimethyl acetylamide, N-methylpyrrolidone etc., reclaims difficulty.Therefore such method is not suitable for commercial scale production.Nickel catalyst system solvent changing in patent CN 101016284 acetonitrile, but acetonitrile toxicity is relatively big, be dissolved in water, price is high, and is not easily recycled.
Aromatic halides is made Grignard reagent by patent CN201310234457, CN201310302428, CN201310050630, US7425650, JP61-22045, US7893306 etc., then prepare tetramethyl biphenyl by the method for coupling, reoxidize tetramethyl biphenyl.But during preparation Grignard reagent, said method all uses the oxolane of boiling point only 65 DEG C or the ether of 35 DEG C to be solvent.Moreover, patent US7425650 also needs the organic boronic of equimolar amounts costliness as another coupling reactant；It is catalyst that patent JP61-22045 uses with the equimolar copper of raw material, and catalyst efficiency is low；Patent US7893306 uses the alkyl Grignard reagent initiator as aromatic halogenated compound of equimolar amounts costliness.It is known that, improving reaction temperature is conducive to active relatively low fragrant halides to generate Grignard reagent, and oxolane or ether boiling point are on the low side, volatile, therefore, for large-scale industrial production, oxolane and ether toxicity are greatly and recovery is difficult to, and easily cause environmental pollution, ether is easily caused security incident, unfavorable to commercial production.The most above-mentioned related solvents system preparing biphenyl need to improve further.
Summary of the invention
The invention aims to overcome above-mentioned deficiency in biphenyl dianhydride preparation method, thering is provided a kind of is raw material by halo o-Dimethylbenzene, using than traditional oxolane and ether (boiling point is respectively 65 DEG C and 35 DEG C) boiling point higher alkyl substituted tetrahydro furan (boiling point is more than 80 DEG C) is dicyandiamide solution, realize high yield and prepare tetramethyl biphenyl, improve atom economy efficiency.
For realizing the object of the invention, concrete technology implementation scheme includes:
A kind of tetramethyl biphenyl isomer preparation method, method one comprises the following steps:
Halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard reagent, catalyst are directly mixed by the mol ratio of 2～10:1～5:1～40:0.0001～2:0.001～5, carry out reacting 0.5～24 hour under the conditions of inert atmosphere, 30 DEG C～150 DEG C, elimination inorganic salt precipitates, filtrate is through Distillation recovery substituted tetrahydrofuran solvent, distill under the conditions of 0.1-200mmHg, collect 100 DEG C～260 DEG C of fractions, obtain tetramethyl biphenyl compound.
A kind of tetramethyl biphenyl isomer preparation method, method two comprises the following steps:
By halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard reagent are by 2～10:1～5:1～the mixed in molar ratio of 40:0.0001～2, after lower 30 DEG C～the 150 DEG C reactions of inertia atmosphere all generate the Grignard reagent of halo o-Dimethylbenzene for 0.5-24 hour to magnesium metal, add catalyst (being 0.001～1:1 with the mol ratio of magnesium metal) continuation reaction and obtain tetramethyl biphenyl in 0.5-24 hour, elimination inorganic salt precipitates, filtrate is through Distillation recovery substituted tetrahydrofuran solvent, distill under the conditions of 0.1-200mmHg, collect 100 DEG C～260 DEG C of fractions, obtain tetramethyl biphenyl compound.
A kind of tetramethyl biphenyl isomer preparation method, method three comprises the following steps:
By 4-halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, catalytic amount iodine or alkyl Grignard reagent with 1～1.5:1～1.5:3～the mixed in molar ratio of 40:0.0001～1, at inertia atmosphere 30～150 DEG C, react the Grignard reagent all generating o-Dimethylbenzene for 0.5-24 hour to magnesium metal, add catalyst (catalyst and magnesium metal mol ratio are 0.001～1:1)；Be subsequently adding 3-halo o-Dimethylbenzene, its with added 4-halo o-Dimethylbenzene ratio be 0.8～2, carry out coupling reaction 0.5～24 hours at 30～150 DEG C, generate 2,3 ', 3,4 '-tetramethyl biphenyl compound；Elimination inorganic salt precipitates, and filtrate, through Distillation recovery substituted tetrahydrofuran solvent, is distilled under the conditions of 0.1-200mmHg, collected 100 DEG C～260 DEG C, obtain 2,3 ', 3,4 '-tetramethyl biphenyl compound.
A kind of preparation method of tetramethyl biphenyl isomer, described halo o-Dimethylbenzene is one or more mixture in compound as shown in following formula (1) or (2):
Wherein, X can be chlorine, bromine or iodine atom, and (1) formula is 3-halo o-Dimethylbenzene, and (2) formula is that 4-is for o-Dimethylbenzene.
A kind of preparation method of tetramethyl biphenyl isomer, described tetramethyl biphenyl be structural compounds shown in following formula (3)～(5) one or more:
Wherein, in above formula, (3) are 2,2 ', 3, and 3 '-tetramethyl biphenyl, formula (4) is 2,3 ', 3,4 '-tetramethyl biphenyl, formula (5) is 3,3 ', 4,4 '-tetramethyl biphenyl.
A kind of preparation method of tetramethyl biphenyl isomer, described alkyl substituted tetrahydro furan is one or more in the compound shown in following formula (6) or (7):
Wherein, substituent R1～R3Each stand alone as methyl, ethyl, n-pro-pyl or isopropyl.
Catalyst described in the preparation method of a kind of tetramethyl biphenyl isomer includes Palladous chloride., palladium bromide, nickel sulfate, palladium, carbonate palladium, oxalic acid palladium, Nickel Chloride, Nickel Bromide, tri-chlorination nickel, tribromide nickel, nickel sulfate, nickel acetate, nickelous carbonate, nickel oxalate, ferrous chloride, ferrous bromide, sulphation is ferrous, Ferrous acetate, carbonating is ferrous, Ferrox., ferric chloride, tribromide is ferrous, iron sulfate, manganese chloride, manganese carbonate, Manganese dibromide., manganese acetate, copper chloride, copper bromide, copper sulfate, Schweinfurt green, curpic carbonate, one or more in Cu-lyt. and cuprous bromide.
Catalyst described in the preparation method of a kind of tetramethyl biphenyl isomer also includes transition metal complex, and wherein transition metal salt and hetero atom organic additive mol ratio are 1:0～10；Described hetero atom organic additive can for compound shown in following formula (8)～(23) one or more:
Wherein, R in formula (8)～(10)4～R9It is independently selected from hydrogen, carbon number alkyl, aryl or substituted aryl less than 20；(11) R～in (23)10～R53It is independently selected from carbon number alkyl, aryl or substituted aryl less than 20；N1 and n2 is the integer between 0～20.
nullCatalyst described in the preparation method of a kind of tetramethyl biphenyl isomer，Wherein hetero atom organic additive preferably is selected from 2,2 '-bipyridyl、3,3 '-dimethyl-2,2 '-bipyridyl、4,4 '-dimethyl-2,2 '-bipyridyl、5,5 '-dimethyl-2,2 '-bipyridyl、Phen、2,9-dimethyl-1,10-Phen、3,8-dimethyl-1,10-Phen、(E) N-(pyridine-2-methylene) aniline、(E) 4-methyl-N-(pyridine-2 '-methylene) aniline、(E) 2-methyl-N-(pyridine-2 '-methylene) aniline、(E) 3-methyl-N-(pyridine-2 '-methylene) aniline、(E)3，4-dimethyl-N-(pyridine-2 '-methylene) aniline、(E)2，3-dimethyl-N-(pyridine-2 '-methylene) aniline、(E)2，4-dimethyl-N-(pyridine-2 '-methylene) aniline、(E) 4-isopropyl-N-(pyridine-2 '-methylene) aniline、(E) N-(pyridine-2-methylene) methylamine、(E) N-(pyridine-2-methylene) ethamine、(E) N-(pyridine-2-methylene) 2-aminopropane.、Acetylacetone,2,4-pentanedione、3，5-heptadione、N-methyl-N-(pyridine-2 '-methylene) methylamine、N-ethyl-N-(pyridine-2 '-methylene) ethamine、N-propyl group-N-(pyridine-2 '-methylene) propylamine、N-methyl-N-(pyridine-2 '-methylene) ethamine、N-methyl-N-(pyridine-2 '-methylene) propylamine、2-((dimethyl phosphorus)-methylene)-pyridine、2-((diethyl phosphorus)-methylene)-pyridine、2-((diphenylphosphine)-methylene)-pyridine、Triphenylphosphine、Triethyl phosphine、Tributylphosphine、Three (4-aminomethyl phenyl) phosphine、Three (3，4-3,5-dimethylphenyl) phosphine、2,2 '-two (dimethylamino)-1,1 '-dinaphthalene、2,2 '-two (dimethylamino)-1,1 '-dinaphthalene、2,2 '-two (dimethylamino)-biphenyl、2,2 '-two (diformazan phosphorio)-1,1 '-dinaphthalene、2,2 '-two (hexichol phosphorio)-1,1 '-dinaphthalene、2,2 '-two (diethyl phosphorio)-1,1 '-dinaphthalene、2,2 '-two (diformazan phosphorio)-1,1 '-biphenyl、2,2 '-two (hexichol phosphorio)-1,1 '-biphenyl、N,N,N’,N '-tetramethyl-1，2-ethylenediamine、N,N,N’,N '-tetramethyl-1，2-ethylenediamine、N,N,N’,N’,N "-pentamethyl-divinyl-triamine、N,N,N’,N’,N”,N "-hexamethyl-trivinyl-tetramine、Two (diphenylphosphine)-ethane、Two (dibutyl phosphorus)-ethane、2-lignocaine-2 '-diethyl phosphorio-1,1 '-dinaphthalene、2-dimethylamino-2 '-diformazan phosphorio-1,1 '-dinaphthalene、2-dimethylamino-2 '-diformazan phosphorio-biphenyl、2-lignocaine-2 ' one or more in-diethyl phosphorio-biphenyl.
Noble gas described in the preparation method of a kind of tetramethyl biphenyl isomer includes nitrogen, argon or heliumAtmosphere。
Substituted tetrahydrofuran solvent preferred 2-methyltetrahydrofuran and 2 described in the preparation method of a kind of tetramethyl biphenyl isomer, 5-dimethyl-tetrahydrofuran, after solvent recovery, dry cycle uses.
The purpose adding iodine or alkyl Grignard reagent described in the preparation method of a kind of tetramethyl biphenyl isomer is to shorten the induction period of reaction.
Compared with prior art, present invention have an advantage that
First, the alkyl substituted tetrahydro furan that during the reaction dissolvent system of the present invention selects water, dissolubility is little, it is achieved that the high recycle and reuse of solvent, beneficially environmental protection；
Secondly, the present invention uses alkyl substituted tetrahydro furan to be solvent, its boiling point is (such as 2-methyltetrahydrofuran boiling point 80 DEG C, 2,5-dimethyl-tetrahydrofuran boiling point 91 DEG C) higher than traditional preparation Grignard reagent solvent for use oxolane (boiling point 65 DEG C) and ether (boiling point 35 DEG C) boiling point, improve the temperature of grignard reaction, therefore response speed is accelerated, improve conversion ratio and the reaction yield of raw material, reduce the requirement to operating environment, the cost of production is greatly reduced；
The advantage of the present invention also resides in, owing to the boiling point of solvent improves, the method of the present invention can realize active relatively low chlorinated aromatic hydrocarbons raw material consistent with active higher aryl bromide coupling yield by improving temperature, and used catalyst realizes preparation in situ, consumption is few, and catalyst is cheap, and reaction condition is gentle, easily controllable, it is more suitable for industrialized production.
Detailed description of the invention
Below the technical scheme in embodiments of the invention is carried out clearly, complete description.The most described embodiment is only a part of content in the present invention rather than whole embodiment.Based on embodiments of the invention, the other embodiments that the common staff of this area is obtained on the premise of not making the work of novelty, belong to the protection domain of this patent.
Below in conjunction with embodiment, the present invention is illustrated, but the present invention is not limited only to scope of embodiments.
Embodiment 1
By 4-bromo o-Dimethylbenzene (36.8g, 0.2moL), magnesium ribbon (1.2g, 0.05moL), anhydrous 2-methyl substituted tetrahydrofuran (52g, 0.6moL), iodine (5mg, 0.02mmoL), anhydrous NiCl2(0.064g, 0.5mmoL), mix at nitrogen atmosphere, after 90 DEG C are reacted 8 hours, cooling, filters off magnesium bromide precipitation, and filtrate is through Distillation recovery 49g solvent 2-methyltetrahydrofuran, reclaiming the bromo o-Dimethylbenzene 18.5g of excess, 145～155 DEG C of fractions (pressure 1～4 millimetres of mercury) are collected in decompression distillation.Obtaining 3,3 ', 4,4 '-tetramethyl biphenyl 19.2g, yield 91% (calculating on the basis of magnesium), fusing point is 74～75 DEG C.
Embodiment 2
By 3-chloro-o-xylene (28g, 0.2moL), magnesium ribbon (1.2g, 0.05moL), anhydrous 2-methyl substituted tetrahydrofuran (43g, 0.5moL), isopropylmagnesium chloride (20.4mg, 0.2mmoL), anhydrous NiCl2(0.064g, 0.5mmoL), bipyridyl (0.078g, 0.5mmoL) mix at nitrogen atmosphere, after being heated to reflux (～115 DEG C) reaction 8 hours, cooling, filters off magnesium chloride sedimentation, and filtrate is through Distillation recovery 40g 2-methyl-tetrahydrofuran solvent, reclaim the 3-chloro-o-xylene 13.5g of excess, 130～145 DEG C of fractions (pressure 1～3 millimetres of mercury) are collected in decompression distillation, it is thus achieved that 2,2 ', 3,3 '-tetramethyl biphenyl 17.9g, yield 85% (calculating on the basis of magnesium), fusing point is 115～116 DEG C.
Embodiment 3
By 4-chloro-o-xylene (14g, 0.1moL), magnesium ribbon (2.4g, 0.1moL), anhydrous 2,5-dimethyl-tetrahydrofuran (50g, 0.5moL), iodine (2.5mg, (～the 110 DEG C) reaction that refluxes 0.01mmoL), under an argon atmosphere is all dissolved to magnesium metal, generates Grignard reagent the most completely, is subsequently adding the anhydrous NiCl of catalyst2(0.13g, 1mmoL) and triphenylphosphine (0.26g, 1mmoL), add 3-chloro-o-xylene (14g, 0.1moL),～110 DEG C carry out coupling reaction 7 hours, then cooling filters off inorganic salt precipitation, and filtrate is through Distillation recovery 2,5-dimethyl-tetrahydrofuran solvent 46g, 140～145 DEG C of fractions (pressure 1～3 millimetres of mercury) are collected in decompression distillation, it is thus achieved that 2,3 ', 3,4 '-tetramethyl biphenyl 18.5g, yield 88% (calculating on the basis of magnesium), fusing point is 45～46 DEG C.
Embodiment 4
By 4-chloro-o-xylene and 3-chloro-o-xylene mixture (ratio 55:45,210g altogether, 1.5moL), magnesium ribbon (12g, 0.5moL), anhydrous 2-methyltetrahydrofuran (340g, 4moL), iodine (0.25g, 1mmoL) mix at nitrogen atmosphere, be heated to reflux (～115 DEG C) reaction and all generate the Grignard reagent of o-Dimethylbenzene to magnesium metal, be subsequently adding anhydrous NiCl2(1.3g, 0.01moL) and bipyridyl (1.56g, after 0.01moL) continuing back flow reaction 8 hours as catalyst, cooling, filters off magnesium chloride sedimentation, and filtrate is through Distillation recovery 320g 2-methyl-tetrahydrofuran solvent, reclaim the chloro-o-xylene 70g of excess, 135～155 DEG C of fractions (pressure 1～2 millimetres of mercury) are collected in decompression distillation, it is thus achieved that tetramethyl biphenyl mixture 100g, yield 95% (calculating on the basis of magnesium).
Above the preparation method of a kind of tetramethyl biphenyl isomer that the present invention provides is described in detail; principle and the embodiment of the present invention are set forth by specific case used herein; the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention; it should be noted; for those skilled in the art; under the premise without departing from the principles of the invention; the present invention can also be carried out some improvement and modification, these improve and modify the scope falling within rights protection of the present invention.
Claims (14)
1. a preparation method for tetramethyl biphenyl isomer, including:
Method one: by halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard reagent,
Catalyst mixes by a certain percentage, prepares tetramethyl biphenyl through catalytic coupling one pot reaction under inert atmosphere；
Method two: by halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard reagent
Mix by a certain percentage, after forming the Grignard reagent of halo o-Dimethylbenzene under inertia atmosphere, add catalyst and carry out
Coupling reaction prepares tetramethyl biphenyl；
Method three: 4-halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard are tried
Agent mixes by a certain percentage, under inertia atmosphere, generate o-Dimethylbenzene Grignard reagent after, add catalyst with
3-halo o-Dimethylbenzene carries out coupling reaction, prepares 2,3 ', 3,4 '-tetramethyl biphenyl.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that method one
Reaction condition is: halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard reagent,
Catalyst molar ratio is 2～10:1～5:1～40:0.0001～2:0.001～5；Reaction temperature is 30 DEG C～150 DEG C；
Response time is 0.5～24 hour；Tetramethyl biphenyl compound method of purification is decompression distillation, at pressure
During 0.1-200mmHg, collect the fraction of 100～260 DEG C.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that method two
Reaction condition is: halo o-Dimethylbenzene, magnesium metal, substituted tetrahydrofuran, iodine or alkyl Grignard reagent mol ratio
It is 2～10:1～5:1～40:0.0001～2；The preparation Grignard reagent response time is 0.5～24 hour, reaction temperature
Degree is 30 DEG C～150 DEG C；Catalyst is 0.001～1:1 with the mol ratio of magnesium metal, and coupling reaction 0.5-24 is little
Time；Tetramethyl biphenyl compound method of purification is decompression distillation, when pressure 0.1-200mmHg, collects
The fraction of 100～260 DEG C.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that method three
Reaction condition is: 4-halo o-Dimethylbenzene, magnesium metal, alkyl substituted tetrahydro furan, iodine or alkyl Grignard examination
Agent mol ratio is 1～1.5:1～1.5:3～40:0.0001～1；The response time generating Grignard reagent is 0.5～24
Hour, reaction temperature is 30～150 DEG C；Catalyst and magnesium metal mol ratio are 0.001～1:1；Add 3-
Halo o-Dimethylbenzene, it is 0.8～2 with the mol ratio of 4-halo o-Dimethylbenzene；The coupling reaction time is 0.5～24
Hour, temperature is 30～150 DEG C；Gained 2,3 ', 3,4 '-tetramethyl biphenyl method of purification is decompression distillation,
When pressure 0.1-200mmHg, collect the fraction of 100～260 DEG C.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that described halogen
It is one or more in compound as shown in following formula (1) and (2) for o-Dimethylbenzene:
Wherein, X can be chlorine, bromine or iodine atom, and (1) formula is 3-halo o-Dimethylbenzene, and (2) formula is
4-is for o-Dimethylbenzene.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that described four
Methyl biphenyl is one or more in compound shown in following formula (3)～(5):
Wherein, formula (3) is 2,2 ', 3, and 3 '-tetramethyl biphenyl, formula (4) is 2,3 ', 3,4 '-tetramethyl biphenyl,
Formula (5) is 3,3 ', 4,4 '-tetramethyl biphenyl.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that described
Alkyl substituted tetrahydro furan is for can be for one or more in compound shown in following formula (6) or (7):
Wherein, substituent R1～R3Each stand alone as methyl, ethyl, n-pro-pyl or isopropyl.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that described catalysis
Agent is to include the transition metal complex catalysts that transition metal salt is formed with hetero atom organic additive, wherein transition gold
Belong to salt and hetero atom organic additive 1:0 in molar ratio～10 preparation in situ.
Tetramethyl biphenyl isomer preparation method the most according to claim 1, it is characterised in that described urges
Agent includes transition metal Palladous chloride., palladium bromide, nickel sulfate, palladium, carbonate palladium, oxalic acid palladium, dichloride
Nickel, Nickel Bromide, tri-chlorination nickel, tribromide nickel, nickel sulfate, nickel acetate, nickelous carbonate, nickel oxalate, chlorination
Ferrous iron, ferrous bromide, sulphation ferrous iron, Ferrous acetate, carbonating ferrous iron, Ferrox., ferric chloride,
Tribromide ferrous iron, manganese chloride, manganese carbonate, Manganese dibromide., manganese acetate, iron sulfate, copper chloride, copper bromide, sulfur
One or more in acid copper, Schweinfurt green, curpic carbonate, Cu-lyt. and cuprous bromide inorganic salt.
The preparation method of tetramethyl biphenyl isomer the most according to claim 1, it is characterised in that right is wanted
Ask hetero atom organic additive described in 8 can for compound shown in following formula (8)～(23) one or more:
Wherein, R in formula (8)～(10)4～R9Be independently selected from hydrogen, carbon number less than 20 alkyl,
Aryl or substituted aryl；R in formula (11)～(23)10～R53It is independently selected from the carbon number alkane less than 20
Base, aryl or substituted aryl；N1 and n2 is the integer between 0～20.
The preparation method of 11. tetramethyl biphenyl isomers according to claim 1, it is characterised in that right is wanted
Ask hetero atom organic additive described in 8 preferably to be selected from 2,2 '-bipyridyl, 3,3 '-dimethyl-2,2 '-bipyridyl, 4,4 '-two
Methyl-2,2 '-bipyridyl, 5,5 '-dimethyl-2,2 '-bipyridyl, Phen, 2,9-dimethyl-1,10-neighbour's Féraud
Quinoline, 3,8-dimethyl-1,10-Phen, (E) N-(pyridine-2-methylene) aniline, (E) 4-methyl-N-(pyrrole
Pyridine-2 '-methylene) aniline, (E) 2-methyl-N-(pyridine-2 '-methylene) aniline, (E) 3-methyl-N-(pyridine
-2 '-methylene) aniline, (E) 3,4-dimethyl-N-(pyridine-2 '-methylene) aniline, (E) 2,3-diformazan
Base-N-(pyridine-2 '-methylene) aniline, (E) 2,4-dimethyl-N-(pyridine-2 '-methylene) aniline, (E)
4-isopropyl-N-(pyridine-2 '-methylene) aniline, (E) N-(pyridine-2-methylene) methylamine, (E) N-(pyridine
-2-methylene) ethamine, (E) N-(pyridine-2-methylene) 2-aminopropane., acetylacetone,2,4-pentanedione, 3,5-heptadione, N-
Methyl-N-(pyridine-2 '-methylene) methylamine, N-ethyl-N-(pyridine-2 '-methylene) ethamine, N-propyl group-N-(pyridine
-2 '-methylene) propylamine, N-methyl-N-(pyridine-2 '-methylene) ethamine, N-methyl-N-(pyridine-2 '-methylene)
Propylamine, 2-((dimethyl phosphorus)-methylene)-pyridine, 2-((diethyl phosphorus)-methylene)-pyridine, 2-
((diphenylphosphine)-methylene)-pyridine, triphenylphosphine, triethyl phosphine, tributylphosphine, three (4-methyl
Phenyl) phosphine, three (3,4-3,5-dimethylphenyl) phosphine, 2,2 '-two (dimethylamino)-1,1 '-dinaphthalene, 2,2 '-two
(dimethylamino)-1,1 '-dinaphthalene, 2,2 '-two (dimethylamino)-biphenyl, 2,2 '-two (diformazan phosphorio)-1,1 '-
Dinaphthalene, 2,2 '-two (hexichol phosphorio)-1,1 '-dinaphthalene, 2,2 '-two (diethyl phosphorio)-1,1 '-dinaphthalene, 2,2 '-two
(diformazan phosphorio)-1,1 '-biphenyl, 2,2 '-two (hexichol phosphorio)-1,1 '-biphenyl, N, N, N ', N '-tetramethyl-1,
2-ethylenediamine, N, N, N ', N '-tetramethyl-1，2-diaminoethane, N, N, N ', N ', N "-pentamethyl-divinyl-triamine,
N, N, N ', N ', N ", N "-hexamethyl-trivinyl-tetramine, two (diphenylphosphine)-ethane, two (dibutyl phosphorus)
-ethane, 2-lignocaine-2 '-diethyl phosphorio-1,1 '-dinaphthalene, 2-dimethylamino-2 '-diformazan phosphorio-1,1 '-dinaphthalene,
One or more in 2-dimethylamino-2 '-diformazan phosphorio-biphenyl, 2-lignocaine-2 '-diethyl phosphorio-biphenyl.
The preparation method of 12. tetramethyl biphenyl isomers according to claim 1, it is characterised in that described inertia
Gas includes nitrogen, argon or helium.
13. the preparation method of tetramethyl biphenyl isomer according to claim 1, it is characterised in that described replacement
Tetrahydrofuran solvent preferred 2-methyltetrahydrofuran and 2,5-dimethyl-tetrahydrofuran.
The preparation method of 14. tetramethyl biphenyl isomers according to claim 1, it is characterised in that described alkane
Base Grignard reagent be carbon number be any Grignard reagent of 1～5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410476948.4A CN104211559B (en) | 2014-09-18 | 2014-09-18 | A kind of preparation method of tetramethyl biphenyl isomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410476948.4A CN104211559B (en) | 2014-09-18 | 2014-09-18 | A kind of preparation method of tetramethyl biphenyl isomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104211559A CN104211559A (en) | 2014-12-17 |
| CN104211559B true CN104211559B (en) | 2016-08-24 |
Family
ID=52093524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410476948.4A Active CN104211559B (en) | 2014-09-18 | 2014-09-18 | A kind of preparation method of tetramethyl biphenyl isomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104211559B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316745A (en) * | 2016-08-24 | 2017-01-11 | 苏州氟拓化工科技有限公司 | Preparing method of biphenyl compound |
| CN109053359B (en) * | 2018-06-29 | 2021-09-07 | 万华化学集团股份有限公司 | Preparation method of tetraalkyl substituted biphenyl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265201A (en) * | 2008-04-16 | 2008-09-17 | 浙江工业大学 | Method for synthesizing tramadol hydrochloride |
| CN103086838A (en) * | 2013-02-08 | 2013-05-08 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
| CN103288583A (en) * | 2013-06-14 | 2013-09-11 | 中国科学院长春应用化学研究所 | Preparation method of 2,3,3'4'-tetramethyl biphenyl |
| CN103319296A (en) * | 2013-07-18 | 2013-09-25 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
-
2014
- 2014-09-18 CN CN201410476948.4A patent/CN104211559B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265201A (en) * | 2008-04-16 | 2008-09-17 | 浙江工业大学 | Method for synthesizing tramadol hydrochloride |
| CN103086838A (en) * | 2013-02-08 | 2013-05-08 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
| CN103288583A (en) * | 2013-06-14 | 2013-09-11 | 中国科学院长春应用化学研究所 | Preparation method of 2,3,3'4'-tetramethyl biphenyl |
| CN103319296A (en) * | 2013-07-18 | 2013-09-25 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104211559A (en) | 2014-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104370685A (en) | Green synthesis method of tetramethyl biphenyl isomer compounds | |
| Wang et al. | Organometallic aspects of fluoroalkylation reactions with copper and nickel | |
| CN101445437B (en) | Improved process for the catalytic synthesis of diaryl ethers | |
| Liu et al. | Manganese‐Catalyzed Cross‐Coupling of Thiols with Aryl Iodides | |
| CN103086838B (en) | A kind of preparation method of tetramethyl biphenyl | |
| CN105198682B (en) | A kind of preparation method of substituted biphenyl | |
| CN104262234A (en) | Preparation method of biphenyl derivatives | |
| CN104341256A (en) | Low-cost and environment-friendly synthesis method of biphenyl derivatives | |
| CN110668913A (en) | Preparation method of trifluoroethyl compound | |
| CN104211559B (en) | A kind of preparation method of tetramethyl biphenyl isomer | |
| CN108017557A (en) | A kind of Process for the cyanation for preparing nitrile compounds | |
| CN103288583B (en) | A kind of 2,3, the preparation method of 3 ', 4 '-tetramethyl biphenyl | |
| Durgun et al. | Pd-loaded NaY zeolite as a highly active catalyst for ligandless Suzuki–Miyaura reactions of aryl halides at low Pd loadings under aerobic conditions | |
| CN102020622B (en) | Method for preparing 2,3,3',4'-biphenyltetracarboxylic di-anhydride | |
| Liu et al. | Bis (imino) pyridine palladium (II) complexes as efficient catalysts for the Suzuki–Miyaura reaction in water | |
| CN103319296B (en) | A kind of preparation method of tetramethyl biphenyl | |
| CN104557683A (en) | Preparation method of 2,3-dichloro-5-trifluoromethylpyridine | |
| CN105294492A (en) | Preparation method of substituted biphenyl | |
| Moglie et al. | Nanosized iron-or copper-catalyzed homocoupling of aryl, heteroaryl, benzyl, and alkenyl grignard reagents | |
| CN101143331B (en) | Non-palladium catalyst system used for coupling reaction | |
| CN101492340B (en) | Process for producing 1,3-enyne compounds | |
| CN102503748B (en) | Copper catalyst system for sonogashira coupling reaction | |
| CN103086834B (en) | Preparation method of biaryl indene compounds | |
| Ye et al. | Structural versatility of four coordination polymers based on 5-(1-oxoisoindolin-2-yl) isophthalic acid: Magnetic and luminescent properties | |
| CN111116285A (en) | Efficient preparation method of 1-aryl-4-butene compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230323 Address after: Room 204, Building 23, North Zone, Suzhou Nanocity, No. 99 Jinjihu Avenue, Suzhou Industrial Park, Suzhou Area, China (Jiangsu) Pilot Free Trade Zone, Suzhou City, Jiangsu Province, 215021 Patentee after: Yantian (Suzhou) New Energy Technology Co.,Ltd. Address before: 264209 No. 2, Wenhua West Road, Shandong, Weihai Patentee before: HARBIN INSTITUTE OF TECHNOLOGY (WEIHAI) |