CN104211559A - Preparation method of tetramethylbiphenyl isomers - Google Patents
Preparation method of tetramethylbiphenyl isomers Download PDFInfo
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Abstract
The invention discloses a preparation method of tetramethylbiphenyl isomers. By adopting an alkyl-substituted tetrahydrofuran with a boiling point of above 80 DEG C, low toxicity and non water solubility as a solvent system, halogenated o-xylene as a raw material, magnetism as a reducing agent, and a complex formed by salts of transition metals such as nickel, copper, iron, magnesium or cobalt, or additives such as organophosphorus and organic amine as a catalyst, 3,3'4,4'-tetramethylbiphenyl, 2,3'3,4'-tetramethylbiphenyl and 2,2'3,3'-tetramethylbiphenyl isomers are prepared by adopting a coupled reaction. According to the preparation method, the cyclic utilization rate of the solvent reaches above 90 percent, and the yield of compounds of the tetramethylbiphenyl isomers reaches 85-95 percent.
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 fire resistant polyimide material.In recent years, researchist finds, containing 2 of unsymmetrical structure, 3 ', 3,4 '-biphenyl dianhydride polymer phase is than 3 of symmetrical structure, 3 ', 4,4 '-biphenyl dianhydride polymkeric substance has higher second-order transition temperature and lower melt viscosity, this character be expected to thoroughly change composite property in decades and difficult process between contradiction.Due to 2,3 ', 3,4 '-biphenyl dianhydride is the property of the polymer composite of main preparation, makes it become remarkable material in military fields such as aerospace.Current 2,3 ', 3,4 '-biphenyl dianhydride is as production 3,3 ', 4, and the by product of 4 '-biphenyl dianhydride, separating-purifying difficulty, limits throughput, therefore its price is 3,3 ', 4, and the 10-20 of 4 '-biphenyl dianhydride price is doubly, very expensive.Relevant 2,3 ', 3, the report of 4 '-biphenyl dianhydride synthetic method is little, and be particularly suitable for industrialization low cost synthesis 2,3 ', 3, the method for 4 '-biphenyl dianhydride is less.Therefore developing low-cost synthesis 2,3 ', 3, the route of 4 '-biphenyl dianhydride, has great importance to the development and application improving polymer matrix composites.
Current production biphenyl dianhydride mainly adopts palladium metal (Pd) and salt thereof etc. as catalyzer, generally needs high-temperature high-pressure craft process to synthesize biphenyl dianhydride intermediate.Palladium metal price is extremely expensive, it is low that biphenyl dianhydride intermediate productive rate is prepared in palladium chtalyst coupling, the biphenyl dianhydride cost obtained is high, relevant research is reported as patent JP7352749, JP80141417, JP8551151, JP8020705, US6914152, US5243067, US3636168, US7425650, US3895055, US4294976, US6103919, CN201310049837 etc.
With Ni(0) or Pd(0) and the complex catalyst that formed of organic phosphine or nitrogen compound, zinc powder is as reductive agent, by the method for coupling halo o-Xylol or halophthalic acid dialkyl, then prepare biphenyl dianhydride through reactions such as hydrolysis, acidifying and dehydrations.The method subject matter of the research such as above-mentioned Patents US5081281, CN1189597, CN101481366, CN102020622B, CN201110202366 report is: 1) need reductive agent excessive greatly and a large amount of catalyzer, cause a large amount of industrial residues; 2) solvent be water miscible high boiling point amide solvent as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-methylpyrrolidone etc., reclaim difficulty.Therefore these class methods are not suitable for industrial-scale production.Change nickel catalyst system solvent into acetonitrile in patent CN 101016284, but acetonitrile toxicity is comparatively large, water-soluble, price is high, and not easily reclaims.
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 in the process preparing Grignard reagent, aforesaid method all uses boiling point to be only 65
othe tetrahydrofuran (THF) of C or 35
othe ether of C is solvent.Moreover, patent US7425650 also needs the organic boronic of equimolar amount costliness as another linked reaction thing; It is catalyzer that patent JP61-22045 uses with the equimolar copper of raw material, and catalyst efficiency is low; Patent US7893306 uses the initiator of alkyl Grignard reagent as aromatic halogenated compound of equimolar amount costliness.As everyone knows, improve temperature of reaction and be conducive to active lower aromatic halogenate generation Grignard reagent, and tetrahydrofuran (THF) or ether boiling point on the low side, volatile, therefore with regard to large-scale commercial production, tetrahydrofuran (THF) and ether toxicity are large and reclaim not easily, easily cause environmental pollution, ether easily causes security incident, unfavorable to industrial production.Therefore the above-mentioned related solvents system preparing biphenyl need further improvement.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency in biphenyl dianhydride preparation method, providing a kind of is raw material by halo o-Xylol, adopts than traditional tetrahydrofuran (THF) and ether that (boiling point is respectively 65
oc and 35
oc) (boiling point is greater than 80 to the alkyl substituted tetrahydro furans that boiling point is higher
oc) be solvent system, realize high yield and prepare tetramethyl biphenyl, improve atom economy efficiency.
For realizing the object of the invention, concrete technology implementation scheme comprises:
A kind of tetramethyl biphenyl isomers ofthe method one, comprises the following steps:
Halo o-Xylol, MAGNESIUM METAL, alkyl substituted tetrahydro furans (solvent), iodine or alkyl Grignard reagent, catalyzer are directly mixed by the mol ratio of 2 ~ 10:1 ~ 5:1 ~ 40:0.0001 ~ 2:0.001 ~ 5, at inert atmosphere, 30
oc ~ 150
ocarry out reaction 0.5 ~ 24 hour under C condition, elimination inorganic salt precipitate, and filtrate is through Distillation recovery substituted tetrahydrofuran solvent, and underpressure distillation collects 100
oc ~ 260
oc(0.1-200 mmhg) cut, obtain tetramethyl biphenyl compound.
A kind of tetramethyl biphenyl isomers ofthe method two, comprises the following steps:
By halo o-Xylol, MAGNESIUM METAL, alkyl substituted tetrahydro furans (solvent), iodine or alkyl Grignard reagent by the mixed in molar ratio of 2 ~ 10:1 ~ 5:1 ~ 40:0.0001 ~ 2, under inertia atmosphere 30
oc ~ 150
oc reaction 0.5-24 is little all generate the Grignard reagent of halo o-Xylol up to MAGNESIUM METAL after, add catalyzer (be 0.001 ~ 1:1 with the mol ratio of MAGNESIUM METAL) again to continue to react and obtain tetramethyl biphenyl in 0.5-24 hour, elimination inorganic salt precipitate, filtrate is through Distillation recovery substituted tetrahydrofuran solvent, and then underpressure distillation collects 100
oc ~ 260
oc(0.1-200 mmhg) cut, obtain tetramethyl biphenyl compound.
A kind of low cost prepares the method three of tetramethyl biphenyl isomer, comprises the following steps:
By 4-halo o-Xylol (or 3-halo o-Xylol), MAGNESIUM METAL, alkyl substituted tetrahydro furans (solvent), catalytic amount iodine or alkyl Grignard reagent with the mixed in molar ratio of 1 ~ 1.5:1 ~ 1.5:3 ~ 40:0.0001 ~ 1, at inertia atmosphere 30 ~ 150
ounder C, the little Grignard reagent all generating o-Xylol up to MAGNESIUM METAL of reaction 0.5-24, then add catalyzer (catalyzer and MAGNESIUM METAL mol ratio are 0.001 ~ 1:1); Then add 3-halo o-Xylol (or 4-halo o-Xylol), the mol ratio of itself and 4-halo o-Xylol (or 3-halo o-Xylol) is 0.8 ~ 2,30 ~ 150
oc carries out linked reaction 0.5 ~ 24 hour, generates 2,3 ', 3,4 '-tetramethyl biphenyl compound; Elimination inorganic salt precipitate, and filtrate is through Distillation recovery substituted tetrahydrofuran solvent, and underpressure distillation collects 100 ~ 260
oc(0.1-200 mmhg) cut, obtain 2,3 ', 3,4 '-tetramethyl biphenyl compound.
Halo o-Xylol described in preparation method one, method two or method three is as shown in the formula one or more mixtures in compound (1) or (2) Suo Shi:
Wherein, X can be chlorine, bromine or iodine atom, and (1) formula is 3-halo o-Xylol, and (2) formula is that 4-is for o-Xylol.
Preparation method one, method two or method three, described tetramethyl biphenyl be structural compounds shown in following formula (3) ~ (5) one or more:
Wherein, in above formula, (3) are 2,2 ', 3,3 '-tetramethyl biphenyl, and formula (4) is 2,3 ', 3,4 '-tetramethyl biphenyl, and formula (5) is 3,3 ', 4, and 4 '-tetramethyl biphenyl.
Preparation method one, method two or method three, described alkyl substituted tetrahydro furans is one or more in the compound shown in following formula (6) or (7):
Wherein, substituent R
1~ R
3respective is independently methyl, ethyl, n-propyl or sec.-propyl.
Preparation method one, described in method two or method three, transition metal salt catalyst comprises Palladous chloride, palladium bromide, single nickel salt, palladium, carbonate palladium, oxalic acid palladium, Nickel Chloride, Nickel Bromide, tri-chlorination nickel, tribromide nickel, single nickel salt, nickel acetate, nickelous carbonate, nickelous oxalate, iron protochloride, ferrous bromide, sulfation is ferrous, Iron diacetate, carbonating is ferrous, Ferrox, iron trichloride, tribromide is ferrous, ferric sulfate, Manganous chloride tetrahydrate, manganous carbonate, Manganese dibromide, manganese acetate, cupric chloride, cupric bromide, copper sulfate, neutralized verdigris, copper carbonate, one or more in cuprous chloride and cuprous bromide.
Transition metal complex catalysts described in preparation method one, method two or method three, wherein transition metal salt and heteroatoms organic additive mol ratio are 1:0 ~ 10; Heteroatoms organic additive described in the preparation method of transition metal complex catalysts can be compound shown in following formula (8) ~ (23) one or more:
Wherein, R in formula (8) ~ (10)
4~ R
9independently be selected from hydrogen separately, alkyl, aryl or substituted aryl that carbon number is less than 20; (11) R in ~ (23)
10~ R
53independently be selected from separately alkyl, aryl or substituted aryl that carbon number is less than 20; N1 and n2 is the integer between 0 ~ 20.
Catalyzer described in preparation method one, method two or method three, wherein heteroatoms organic additive is preferably from 2,2 '-dipyridyl, 3,3 '-dimethyl-2,2 '-dipyridyl, 4,4 '-dimethyl-2,2 '-dipyridyl, 5,5 '-dimethyl-2,2 '-dipyridyl, phenanthroline, 2,9-dimethyl-1,10-phenanthrolines, 3,8-dimethyl-1,10-phenanthroline, (E)
n-(pyridine-2-methylene radical) aniline, (E) 4-methyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 2-methyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 3-methyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 3,4-dimethyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 2,3-dimethyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 2,4-dimethyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 4-sec.-propyl-
n-(pyridine-2 '-methylene radical) aniline, (E)
n-(pyridine-2-methylene radical) methylamine, (E)
n-(pyridine-2-methylene radical) ethamine, (E)
n-(pyridine-2-methylene radical) Isopropylamine, methyl ethyl diketone, 3,5-heptadione,
n-methyl-
n-(pyridine-2 '-methylene radical) methylamine,
n-ethyl-
n-(pyridine-2 '-methylene radical) ethamine,
n-propyl group-
n-(pyridine-2 '-methylene radical) propylamine,
n-methyl-
n-(pyridine-2 '-methylene radical) ethamine,
n-methyl-
n-(pyridine-2 '-methylene radical) propylamine, 2-((dimethyl phosphorus)-methylene radical)-pyridine, 2-((diethyl phosphorus)-methylene radical)-pyridine, 2-((diphenylphosphine)-methylene radical)-pyridine, triphenylphosphine, triethyl phosphine, tributylphosphine, three (4-aminomethyl phenyl) phosphine, three (3,4-3,5-dimethylphenyl) phosphine, 2,2 '-two (dimethylin)-1,1 '-dinaphthalene, 2,2 '-two (dimethylin)-1,1 '-dinaphthalene, 2,2 '-two (dimethylin)-biphenyl, 2,2 '-two (diformazan phosphorus base)-1,1 '-dinaphthalene, 2,2 '-two (hexichol phosphorus base)-1,1 '-dinaphthalene, 2,2 '-two (diethyl phosphorus base)-1,1 '-dinaphthalene, 2,2 '-two (diformazan phosphorus base)-1,1 '-biphenyl, 2,2 '-two (hexichol phosphorus base)-1,1 '-biphenyl, N, N, N ', N '-tetramethyl--1，2-diaminoethane, 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-diethylin-2 '-diethyl phosphorus base-1,1 '-dinaphthalene, 2-dimethylamino-2 '-diformazan phosphorus base-1,1 '-dinaphthalene, 2-dimethylamino-2 '-diformazan phosphorus base-biphenyl, 2-diethylin-2 ' one or more in-diethyl phosphorus base-biphenyl.
Described in preparation method one, method two or method three, rare gas element comprises nitrogen, argon gas or helium atmosphere, is preferably argon gas.
The preferred 2-methyltetrahydrofuran of substituted tetrahydrofuran solvent described in preparation method one, method two or method three and 2,5-dimethyl-tetrahydrofuran, after solvent recuperation, dry recycle uses.
The object adding iodine or alkyl Grignard reagent described in preparation method one, method two or method three shortens the inductive phase of reaction.
Compared with prior art, advantage of the present invention is:
First, the alkyl substituted tetrahydro furans that reaction solvent system of the present invention selects solubleness in water little, achieves the high recycle and reuse of solvent, is beneficial to environmental protection;
Secondly, the present invention adopts alkyl substituted tetrahydro furans to be solvent, and its boiling point is (as 2-methyltetrahydrofuran boiling point 80
oc, 2,5-dimethyl-tetrahydrofuran boiling point 91
oc) Grignard reagent solvent for use tetrahydrofuran (THF) (boiling point 65 is prepared than traditional
oand ether (boiling point 35 C)
oc) boiling point is high, improves the temperature of grignard reaction, therefore accelerates speed of response, improves transformation efficiency and the reaction yield of raw material, reduces the requirement to operating environment, significantly reduce production cost;
Advantage of the present invention is also, because the boiling point of solvent improves, method of the present invention is consistent to the aryl bromide coupling yield that the chlorinated aromatic hydrocarbons raw material that activity is lower is higher with activity by improving temperature realization, and used catalyst realizes original position preparation, consumption is few, and catalyzer is cheap, and reaction conditions is gentle, be easy to control, be more suitable for suitability for industrialized production.
Embodiment
Carry out clearly with regard to the technical scheme in embodiments of the invention below, complete description.Obviously described embodiment is only a part of content in the present invention, instead of whole embodiment.Based on embodiments of the invention, other embodiment that the common staff of this area obtains under the prerequisite of work of not making novelty, all belongs 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-Xylol (36.8 g, 0.2 moL), magnesium ribbon (1.2g, 0.05 moL), anhydrous 2-methyl substituted tetrahydrofuran (THF) (52g, 0.6 moL), iodine (5 mg, 0.02 mmoL), anhydrous NiCl
2(0.064 g, 0.5 mmoL), in nitrogen atmosphere mixing, 90
oafter C reacts 8 hours, cooling, elimination magnesium bromide precipitates, and filtrate, through Distillation recovery 49 g solvent 2-methyltetrahydrofuran, reclaims excessive bromo o-Xylol 18.5g, and underpressure distillation collects 145 ~ 155
oc cut (pressure 1 ~ 4 mmhg).Obtaining 3,3 ', 4,4 '-tetramethyl biphenyl 19.2 g, yield 91 %(take magnesium as benchmark), fusing point is 74 ~ 75
oc.
embodiment 2:
By 3-chloro-o-xylene (28 g, 0.2 moL), magnesium ribbon (1.2g, 0.05 moL), anhydrous 2-methyl substituted tetrahydrofuran (THF) (43 g, 0.5 moL), isopropylmagnesium chloride (20.4 mg, 0.2 mmoL), anhydrous NiCl
2(0.064 g, 0.5 mmoL), dipyridyl (0.078 g, 0.5 mmoL) mixes at nitrogen atmosphere, reflux (~ 115
oc) react after 8 hours, cooling, elimination magnesium chloride sedimentation, filtrate, through Distillation recovery 40 g 2-methyl-tetrahydrofuran solvent, reclaims excessive 3-chloro-o-xylene 13.5g, and underpressure distillation collects 130 ~ 145
oc cut (pressure 1 ~ 3 mmhg), obtain 2,2 ', 3,3 '-tetramethyl biphenyl 17.9 g, yield 85%(take magnesium as benchmark), fusing point is 115 ~ 116
oc.
embodiment 3:
By 4-chloro-o-xylene (14 g, 0.1 moL), magnesium ribbon (2.4g, 0.1 moL), anhydrous 2,5-dimethyl-tetrahydrofurans (50 g, 0.5 moL), iodine (2.5 mg, 0.01 mmoL), reflux (~ 110 under an argon atmosphere
oc) reaction is all dissolved to MAGNESIUM METAL, namely generates Grignard reagent completely, then adds the anhydrous NiCl of catalyzer
2(0.13 g, 1 mmoL) and triphenylphosphine (0.26 g, 1 mmoL), then add 3-chloro-o-xylene (14 g, 0.1 moL), ~ 110
oc carries out linked reaction 7 hours, then cools elimination inorganic salt precipitation, and filtrate is through Distillation recovery 2,5-dimethyl-tetrahydrofuran solvent 46 g, and underpressure distillation collects 140 ~ 145
oc cut (pressure 1 ~ 3 mmhg), obtain 2,3 ', 3,4 '-tetramethyl biphenyl 18.5 g, yield 88%(take magnesium as benchmark), fusing point is 45 ~ 46
oc.
embodiment 4:
By 4-chloro-o-xylene and 3-chloro-o-xylene mixture (ratio 55:45, totally 210 g, 1.5 moL), magnesium ribbon (12g, 0.5 moL), anhydrous 2-methyltetrahydrofuran (340 g, 4 moL), iodine (0.25 g, 1 mmoL) nitrogen atmosphere mixing, reflux (~ 115
oc) reaction to MAGNESIUM METAL all generates the Grignard reagent of o-Xylol, then adds anhydrous NiCl
2(1.3 g, 0.01moL) and dipyridyl (1.56 g, 0.01 moL) continue back flow reaction after 8 hours as catalyzer, cooling, elimination magnesium chloride sedimentation, filtrate is through Distillation recovery 320 g 2-methyl-tetrahydrofuran solvent, reclaim excessive chloro-o-xylene 70 g, underpressure distillation collects 135 ~ 155
oc cut (pressure 1 ~ 2 mmhg), obtain tetramethyl biphenyl mixture 100g, yield 95 %(take magnesium as benchmark).
Above the preparation method of a kind of tetramethyl biphenyl isomer provided by the invention is described in detail; apply specific case herein to set forth principle of the present invention and embodiment; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; it should be noted; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify the scope also belonging to rights protection of the present invention.
Claims (14)
1. a preparation method for tetramethyl biphenyl isomer, comprising:
Method one: halo o-Xylol, MAGNESIUM METAL, alkyl substituted tetrahydro furans (solvent), iodine or alkyl Grignard reagent, catalyzer are mixed by a certain percentage, obtains tetramethyl biphenyl through catalytic coupling one pot reaction under inert atmosphere;
Method two: halo o-Xylol, MAGNESIUM METAL, alkyl substituted tetrahydro furans, iodine or alkyl Grignard reagent are mixed by a certain percentage, after forming the Grignard reagent of halo o-Xylol, then adds catalyzer and carries out linked reaction and obtain tetramethyl biphenyl under inertia atmosphere;
Method three: 4-halo o-Xylol (or 3-halo o-Xylol), MAGNESIUM METAL, alkyl substituted tetrahydro furans (solvent), iodine or alkyl Grignard reagent are mixed by a certain percentage, under inertia atmosphere, after generating the Grignard reagent of o-Xylol, add catalyzer again and 3-halo o-Xylol (or 4-halo o-Xylol) carries out linked reaction, obtained 2,3 ', 3,4 '-tetramethyl biphenyl.
2. tetramethyl biphenyl isomers ofthe method one according to claim 1, it is characterized in that, reaction conditions is: halo o-Xylol, MAGNESIUM METAL, alkyl substituted tetrahydro furans, iodine or alkyl Grignard reagent, catalyst molar ratio are 2 ~ 10:1 ~ 5:1 ~ 40:0.0001 ~ 2:0.001 ~ 5; Temperature of reaction is 30
oc ~ 150
oc; Reaction times is 0.5 ~ 24 hour; Tetramethyl biphenyl compound method of purification is underpressure distillation, collects temperature 100 ~ 260
oc cut (pressure is 0.1-200 mmhg).
3. tetramethyl biphenyl isomers ofthe method two according to claim 1, it is characterized in that, reaction conditions is: halo o-Xylol, MAGNESIUM METAL, substituted tetrahydrofuran, iodine or alkyl Grignard reagent mol ratio are 2 ~ 10:1 ~ 5:1 ~ 40:0.0001 ~ 2; Preparing the Grignard reagent reaction times is 0.5 ~ 24 hour, and temperature of reaction is 30
oc ~ 150
oc; The mol ratio of catalyzer and MAGNESIUM METAL is 0.001 ~ 1:1, linked reaction 0.5-24 hour; Tetramethyl biphenyl compound method of purification is underpressure distillation, collects temperature 100 ~ 260
oc cut (pressure is 0.1-200 mmhg).
4. tetramethyl biphenyl isomers ofthe method three according to claim 1, it is characterized in that, preparation 2,3 ', 3, the reaction conditions of 4 '-tetramethyl biphenyl is: 4-halo o-Xylol (or 3-halo o-Xylol), MAGNESIUM METAL, alkyl substituted tetrahydro furans, iodine or alkyl Grignard reagent mol ratio are 1 ~ 1.5:1 ~ 1.5:3 ~ 40:0.0001 ~ 1; The reaction times generating Grignard reagent is 0.5 ~ 24 hour, and temperature of reaction is 30 ~ 150
oc; Catalyzer and MAGNESIUM METAL mol ratio are 0.001 ~ 1:1; Add 3-halo o-Xylol (or 4-halo o-Xylol), the mol ratio of itself and 4-halo o-Xylol (or 3-halo o-Xylol) is 0.8 ~ 2; The linked reaction time is 0.5 ~ 24 hour, and temperature is 30 ~ 150
oc; Gained 2,3 ', 3,4 '-tetramethyl biphenyl method of purification is underpressure distillation, collects temperature 100 ~ 260
oc cut (pressure is 0.1-200 mmhg).
5. tetramethyl biphenyl isomers ofthe method one according to claim 1, method two or method three, is characterized in that, halo o-Xylol is as shown in the formula one or more in compound (1) and (2) Suo Shi:
Wherein, X can be chlorine, bromine or iodine atom, and (1) formula is 3-halo o-Xylol, and (2) formula is that 4-is for o-Xylol.
6. tetramethyl biphenyl isomers ofthe method one according to claim 1, method two or method three, is characterized in that, described tetramethyl biphenyl is one or more in compound shown in following formula (3) ~ (5):
Wherein, formula (3) is 2,2 ', 3,3 '-tetramethyl biphenyl, and formula (4) is 2,3 ', 3,4 '-tetramethyl biphenyl, and formula (5) is 3,3 ', 4,4 '-tetramethyl biphenyl.
7. tetramethyl biphenyl isomers ofthe method one according to claim 1, method two or method three, is characterized in that, alkyl substituted tetrahydro furans is for can be one or more in compound shown in following formula (6) or (7):
Wherein, substituent R
1~ R
3respective is independently methyl, ethyl, n-propyl or sec.-propyl.
8. tetramethyl biphenyl isomers ofthe method one according to claim 1, method two or method three, it is characterized in that, catalyzer is comprise the transition metal complex catalysts that transition metal salt and heteroatoms organic additive formed, wherein transition metal salt and heteroatoms organic additive in molar ratio 1:0 ~ 10 original position prepare.
9. tetramethyl biphenyl isomers ofthe method one according to claim 1, method two or method three, it is characterized in that, catalyzer comprises transition metal Palladous chloride, palladium bromide, single nickel salt, palladium, carbonate palladium, oxalic acid palladium, Nickel Chloride, Nickel Bromide, tri-chlorination nickel, tribromide nickel, single nickel salt, nickel acetate, nickelous carbonate, nickelous oxalate, iron protochloride, ferrous bromide, sulfation is ferrous, Iron diacetate, carbonating is ferrous, Ferrox, iron trichloride, tribromide is ferrous, Manganous chloride tetrahydrate, manganous carbonate, Manganese dibromide, manganese acetate, ferric sulfate, cupric chloride, cupric bromide, copper sulfate, neutralized verdigris, copper carbonate, one or more in cuprous chloride and cuprous bromide inorganic salt.
10. the preparation method one of transition metal complex catalysts, method two or method three according to claim 8, it is characterized in that, formed heteroatoms organic additive described in transition metal complex catalysts can be compound shown in following formula (8) ~ (23) one or more:
Wherein, R in formula (8) ~ (10)
4~ R
9independently be selected from hydrogen separately, alkyl, aryl or substituted aryl that carbon number is less than 20; R in formula (11) ~ (23)
10~ R
53independently be selected from separately alkyl, aryl or substituted aryl that carbon number is less than 20; N1 and n2 is the integer between 0 ~ 20.
11. transition metal complex catalysts preparation methods according to claim 8, it is characterized in that, described heteroatoms organic additive is preferably from 2,2 '-dipyridyl, 3,3 '-dimethyl-2,2 '-dipyridyl, 4,4 '-dimethyl-2,2 '-dipyridyl, 5,5 '-dimethyl-2,2 '-dipyridyl, phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthrolines, (E)
n-(pyridine-2-methylene radical) aniline, (E) 4-methyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 2-methyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 3-methyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 3,4-dimethyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 2,3-dimethyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 2,4-dimethyl-
n-(pyridine-2 '-methylene radical) aniline, (E) 4-sec.-propyl-
n-(pyridine-2 '-methylene radical) aniline, (E)
n-(pyridine-2-methylene radical) methylamine, (E)
n-(pyridine-2-methylene radical) ethamine, (E)
n-(pyridine-2-methylene radical) Isopropylamine, methyl ethyl diketone, 3,5-heptadione,
n-methyl-
n-(pyridine-2 '-methylene radical) methylamine,
n-ethyl-
n-(pyridine-2 '-methylene radical) ethamine,
n-propyl group-
n-(pyridine-2 '-methylene radical) propylamine,
n-methyl-
n-(pyridine-2 '-methylene radical) ethamine,
n-methyl-
n-(pyridine-2 '-methylene radical) propylamine, 2-((dimethyl phosphorus)-methylene radical)-pyridine, 2-((diethyl phosphorus)-methylene radical)-pyridine, 2-((diphenylphosphine)-methylene radical)-pyridine, triphenylphosphine, triethyl phosphine, tributylphosphine, three (4-aminomethyl phenyl) phosphine, three (3,4-3,5-dimethylphenyl) phosphine, 2,2 '-two (dimethylin)-1,1 '-dinaphthalene, 2,2 '-two (dimethylin)-1,1 '-dinaphthalene, 2,2 '-two (dimethylin)-biphenyl, 2,2 '-two (diformazan phosphorus base)-1,1 '-dinaphthalene, 2,2 '-two (hexichol phosphorus base)-1,1 '-dinaphthalene, 2,2 '-two (diethyl phosphorus base)-1,1 '-dinaphthalene, 2,2 '-two (diformazan phosphorus base)-1,1 '-biphenyl, 2,2 '-two (hexichol phosphorus base)-1,1 '-biphenyl, N, N, N ', N '-tetramethyl--1，2-diaminoethane, 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-diethylin-2 '-diethyl phosphorus base-1,1 '-dinaphthalene, 2-dimethylamino-2 '-diformazan phosphorus base-1,1 '-dinaphthalene, 2-dimethylamino-2 '-diformazan phosphorus base-biphenyl, 2-diethylin-2 ' one or more in-diethyl phosphorus base-biphenyl.
12. preparation method one of tetramethyl biphenyl isomer, method two or methods three according to claim 1, it is characterized in that, described rare gas element comprises nitrogen, argon gas or helium atmosphere, is preferably argon gas.
13. preparation method one of tetramethyl biphenyl isomer, method two or methods three according to claim 1, is characterized in that, the preferred 2-methyltetrahydrofuran of described substituted tetrahydrofuran solvent and 2,5-dimethyl-tetrahydrofuran.
14. preparation method one of tetramethyl biphenyl isomer, method two or methods three according to claim 1, is characterized in that, described alkyl Grignard reagent to be carbon number be 1 ~ 5 any Grignard reagent.
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| 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 |
| CN109053359A (en) * | 2018-06-29 | 2018-12-21 | 万华化学集团股份有限公司 | A kind of preparation method of tetraalkyl substituted biphenyl |
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| 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 |
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| 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 |
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