CN104370685A - Green synthesis method of tetramethyl biphenyl isomer compounds - Google Patents
Green synthesis method of tetramethyl biphenyl isomer compounds Download PDFInfo
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Abstract
The invention discloses a green synthesis method of tetramethyl biphenyl isomer compounds. By using a green environment-friendly solvent cycloalkyl methyl ether with the boiling point of higher than 106 DEG C, which is insoluble with water, as a reaction solvent, halogenated o-xylene as a raw material, magnesium metal as a reducer and transition metal nickel, cobalt, palladium, copper, iron, manganese salt or the like or complex thereof as a catalyst, 3,3',4,4'-tetramethyl biphenyl, 2,3',3,4'-tetramethyl biphenyl and 2,2',3,3'-tetramethyl biphenyl isomer compounds are prepared. The yield of the tetramethyl biphenyl isomer compounds is 85-95%, and the cyclic utilization ratio of the cycloalkyl methyl ether is up to higher than 90%.
Description
Technical field
The present invention relates to synthetic organic chemical art, be specifically related to the method for a kind of green syt tetramethyl-connection isomer.
Background technology
BPDA is one of important dianhydride monomer of synthesis of polyimides material.Such as 3,3 ', 4,4 '-BPDA.In recent years, researchist finds, containing 2,3 ', 3 of unsymmetrical structure, 4 '-biphenyl dianhydride polymkeric substance has than symmetrical 3,3 ', 4, and the second-order transition temperature that 4 '-biphenyl dianhydride polymkeric substance is higher, its melt viscosity then significantly reduces.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.At present about 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 method for 4 '-biphenyl dianhydride, has great importance to the unification of the processing and performance that realize performance resins based composites.
Current industrial main employing palladium metal (Pd) is as catalyzer, and the approach carrying out the derivative of coupling o-Xylol at high temperature under high pressure prepares biphenyl dianhydride.But this route feed stock conversion is low, and palladium metal belongs to rare metal, and price is extremely expensive, the biphenyl dianhydride cost obtained is high.Relevant patent has JP7352749, JP80141417, JP8551151, JP8020705, US6914152, US5243067, US3636168, US7425650, US3895055, US4294976, US6103919, CN201310049837 etc.
The report such as patent US 5081281, CN1189597, CN101481366, CN102020622B, CN201110202366 is by the complex catalysts such as transiting metal nickel and reducing metal zinc etc., approach through coupling halo o-Xylol and derivative thereof prepares biphenyl dianhydride, but the subject matter of these methods is: 1) reductive agent and catalyst levels are greatly and not easily reclaim, and easily cause a large amount of industrial residue; 2) with water miscible high boiling point amide solvent as dimethyl formamide, N,N-DIMETHYLACETAMIDEs etc. are solvent, recycle and reuse difficulty.Therefore these class methods are only applicable to laboratory preparation on a small scale, are not suitable for industrial-scale production.Change nickel catalyst system solvent into acetonitrile in CN101016284, but acetonitrile toxicity is comparatively large, water-soluble, price is high, and not easily reclaims.
Aromatic halides is made Grignard reagent, prepares tetramethyl biphenyl by the method for coupling, reoxidizing tetramethyl biphenyl is the another kind of approach preparing biphenyl dianhydride.But need to cause aromatic halogenated compound with the alkyl Grignard reagent with reaction raw materials equimolar amount costliness in patent US7893306 to react; Need in patent US7425650 with the organic boronic with reaction raw materials equimolar amount costliness as another linked reaction thing; Using with the equimolar copper of Grignard reagent in patent JP61-22045 is catalyzer, and catalyst levels is too large; Just synthesize with regard to required starting material, above-mentioned three kinds of method costs are very high.But comprising patent CN201310234457, CN201310302428, CN201310050630 etc., in interior various reaction system, all preferentially adopt the tetrahydrofuran (THF) that toxicity is large or ether to be solvent.As everyone knows, improve temperature favourable to the aromatic halogenate generation Grignard reagent that activity is lower, and as solvent prepared by Grignard reagent, tetrahydrofuran (THF) (b.p.=65
oc) with ether (b.p.=35
oc) boiling point is low, and volatility is high, easily causes security incident.Therefore, with regard to large-scale commercial production, no matter chemically reaction, or chemical engineering process itself, adopt easily recoverys, solvent system that environmental protection, boiling point are higher significant to the reduction of tetramethyl biphenyl compound preparation cost.
Summary of the invention
The object of the invention is to overcome above-mentioned in biphenyl dianhydride preparation method a large amount of deficiency using toxic and volatile solvent, provide a kind of adopt new green environment protection type solvent methyl cycloalkyl ether [
org. Process. Res. Dev,
2011,
15, 939] and as solvent, be the method that tetramethyl biphenyl prepared by raw material by halo o-Xylol.The method of a kind of green syt tetramethyl biphenyl isomer provided by the invention, reaction process environmental protection, atom economy efficiency is high and be suitable for suitability for industrialized production.
The object of the invention is to be reached by following measure to prepare tetramethyl biphenyl compound by halo o-Xylol.
The present invention is about a kind of method of green syt tetramethyl biphenyl isomer, and concrete technology implementation scheme step comprises:
A kind of low cost prepares tetramethyl biphenyl isomer method one, comprise the following steps: halo o-Xylol, MAGNESIUM METAL, iodine or alkyl Grignard reagent, methyl cycloalkyl ether and catalyzer are directly mixed by the mol ratio of 100:10 ~ 50:10 ~ 1000:0.01 ~ 20:0.01 ~ 100, under an inert atmosphere, 30
oc ~ 150
oc reaction 0.5 ~ 24 hour, i.e. one pot reaction.Through filtering or separatory removing inorganic salt after reaction terminates, through Distillation recovery methyl cycloalkyl ether, then underpressure distillation collects 100
oc ~ 290
oc(0.1-300 mmhg) cut, tetramethyl biphenyl compound yield 85 ~ 95%.
A kind of low cost prepares tetramethyl biphenyl isomer method two, comprises the following steps: by halo o-Xylol, MAGNESIUM METAL, methyl cycloalkyl ether, iodine or the alkyl Grignard reagent mixed in molar ratio by 100:10 ~ 50:10 ~ 1000:0.01 ~ 20, under inertia atmosphere 30
oc ~ 150
oc reaction 0.5 ~ 24 little all form the Grignard reagent of halo o-Xylol up to MAGNESIUM METAL after, add the catalyzer of MAGNESIUM METAL molar fraction 0.1 ~ 100%, 30
oc ~ 150
oc continues catalyzed coupling reaction 0.5-12 hour, and reaction terminates rear filtration or separatory removing inorganic salt, and through Distillation recovery methyl cycloalkyl ether solvents, then underpressure distillation collects 100
oc ~ 290
oc(0.1-300 mmhg) cut, tetramethyl biphenyl compound yield 85 ~ 95%.
A kind of low cost prepares the method three of tetramethyl biphenyl isomer, comprise the following steps: by 4-halo o-Xylol (or 3-halo o-Xylol), MAGNESIUM METAL, methyl cycloalkyl ether, iodine or alkyl Grignard reagent with the mixed in molar ratio of 100:100 ~ 150:300 ~ 4000:0.1 ~ 10, under inertia atmosphere 30 ~ 150
oc reaction all generates the Grignard reagent of o-Xylol to MAGNESIUM METAL, add the catalyzer of MAGNESIUM METAL molar fraction 0.1 ~ 100%, add the 3-halo o-Xylol (or 4 halo o-Xylols) of MAGNESIUM METAL molar fraction 100 ~ 200%, 30 ~ 150
oc carries out linked reaction 0.5 ~ 12 hour, and reaction terminates rear filtration or separatory removing inorganic salt, and through Distillation recovery methyl cycloalkyl ether solvents, then underpressure distillation collects 100
oc ~ 290
oc(0.1-300 mmhg) cut, 2,3 ', 3,4 '-tetramethyl biphenyl compound yield 85 ~ 95%.
Halo o-Xylol described in preparation method one, method two or method three 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 formula (1) is 3-halo o-Xylol, and formula (2) is 4-halo o-Xylol.
Preparation method one, method two or method three, described tetramethyl biphenyl compound is for 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.
Preparation method one, method two or method three, described methyl cycloalkyl ether is for can be one or more in the compound shown in following formula (6) and (7):
Wherein, substituent R
1for hydrogen atom or methyl.
Preparation method one, described in method two or method three, catalyzer comprises transition metal salt is 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, Manganese dibromide, manganese iodide, manganous sulfate, manganese acetate, cupric chloride, cupric bromide, copper sulfate, neutralized verdigris, copper carbonate, one or more in cuprous chloride and cuprous bromide.
Catalyzer described in preparation method one, method two or method three also comprises transition metal complex catalysts and is prepared for 1:0 ~ 10 original position in molar ratio by transition metal salt and heteroatoms organic ligand, described heteroatoms organic ligand can be compound shown in following formula (8) ~ (17) one or more:
Wherein, R in formula (8) ~ (10)
2~ R
7independently be selected from hydrogen separately, alkyl, aryl or substituted aryl that carbon number is less than 20; (11) R in ~ (17)
8~ R
29independently be selected from separately alkyl, aryl or substituted aryl that carbon number is less than 20; N1 and n2 is the integer between 0 ~ 100.
Transition metal complex catalysts described in preparation method one, method two or method three, wherein heteroatoms organic ligand 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, N, N, N ', N '-tetramethyl--1, 2-quadrol, N, N, N ', N '-tetramethyl--1, 2-quadrol, N, N, N ', N ', N ' '-pentamethyl--divinyl-triamine, N, N, N ', N ', N ' ', N ' '-hexamethyl-trivinyl-tetramine, two (diphenylphosphine)-ethane, one or more in two (dibutyl phosphorus)-ethane.
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 cyclopentyl methyl ether of solvent and cycloalkyl methyl ether, more preferably cyclopentyl methyl ether described in preparation method one, method two or method three.
The method of the removing inorganic salt described in preparation method one, method two or method three comprises direct filtration inorganic salt, collects organic phase; Or add a small amount of water and realize organic phase and inorganic phase layering, then separatory, collect organic phase.
The object adding iodine or alkyl Grignard reagent described in preparation method one, method two or method three shortens the inductive phase of reaction.
The present invention compared with prior art, it is advantageous that:
First, the methyl cycloalkyl ether that the present invention selects is environmental type reaction solvent, itself and water objectionable intermingling, therefore easy drying treatment, and achieve the solvent recovering rate of more than 90%, solvent cycle utilizes, and is beneficial to environmental protection;
Secondly, the present invention selects methyl cycloalkyl ether boiling point 106
omore than C, prepares Grignard reagent solvent for use tetrahydrofuran (THF) (boiling point 65 than traditional
oand ether (boiling point 35 C)
oc) boiling point is high by 40 respectively
oc and 70
omore than C, therefore temperature of reaction range of choice is wide, and the chloro-o-xylene low to active low price by improving the temperature way of grignard reaction, can improve transformation efficiency and the reaction yield of raw material, reduce the requirement of operating environment, realize significantly reducing production cost;
Again, method of the present invention reaction solvent used, also directly can being used as extraction agent after reaction terminates, without the need to using other extraction agents, reducing the consuming cost of solvent;
Meanwhile, the invention provides used catalyst range of choice wide, realize original position preparation, consumption is few, and catalyzer is cheap, and reaction conditions is gentle, is easy to control, is 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 embodiments that the common staff of this area obtains under the prerequisite of work of not making novelty, all 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-Xylol (36.8 g, 0.2 moL), magnesium ribbon (1.2g, 0.05 moL), anhydrous cyclopentyl methyl ether (60 g, 0.6 moL), iodine (5 mg, 0.02 mmoL), anhydrous NiCl
2(0.064 g, 0.5 mmoL), in argon gas atmosphere mixing, reflux (~ 115
oc) react after 8 hours, cooling, elimination magnesium bromide precipitates, and filtrate, through Distillation recovery 57 g cyclopentyl methyl ether, reclaims excessive bromo o-Xylol 18.5g, and underpressure distillation collects 145 ~ 155
oc cut (pressure 1 ~ 4 mmhg), obtain 3,3 ', 4,4 '-tetramethyl biphenyl 19.2 g, yield 91 %(calculates with magnesium), 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 cyclopentyl methyl ether (50 g, 0.5 moL), iodine (5 mg, 0.02 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, adds 5mL water, layering, and collect upper organic phase, organic phase, through Distillation recovery 48 g solvent cyclopentyl methyl ether, reclaims excessive 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%, 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 cyclopentyl methyl ether (50 g, 0.5 moL), tertiary butyl magnesium chloride (11 mg, 0.1 mmoL), reflux (~ 110 in a nitrogen 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 cyclopentyl methyl ether 46 g, and underpressure distillation collects 140 ~ 145
oc cut (pressure 1 ~ 5 mmhg), obtain 2,3 ', 3,4 '-tetramethyl biphenyl 18.5 g, yield 88%, fusing point is 45 ~ 46
oc.
embodiment 4
By 4-chloro-o-xylene and 3-chloro-o-xylene mixture (ratio is 55:45,210 g, 1.5 moL), magnesium ribbon (12 g, 0.5 moL), cyclopentyl methyl ether (400 g, 4 moL), iodine (0.25 g, 1 mmoL) nitrogen atmosphere mixing, reflux (~ 120
oc) reaction 4 is little all dissolves up to MAGNESIUM METAL, namely generates the Grignard reagent of o-Xylol, then adds the anhydrous NiCl of catalyzer
2(1.3 g, 0.01moL), organic additive dipyridyl (1.56 g, 0.01 moL) continue back flow reaction after 8 hours, cooling, elimination magnesium chloride sedimentation, filtrate, through Distillation recovery 390 g cyclopentyl methyl ether, reclaims excessive chloro-o-xylene 70 g, and underpressure distillation collects 135 ~ 155
oc cut (pressure 1 ~ 5 mmhg), obtains tetramethyl biphenyl mixture 100g, yield 95%, through gas Chromatographic Determination, and wherein 3,3 ', 4,4 '-tetramethyl biphenyl, 2,3 ', 3,4 '-tetramethyl biphenyl and 2,2 ', 3, the ratio of 3 '-tetramethyl biphenyl is 23.3:55.2:21.5.
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 (16)
1. a tetramethyl biphenyl isomers ofthe method one: halo o-Xylol, MAGNESIUM METAL, iodine or alkyl Grignard reagent, methyl cycloalkyl ether and catalyzer are pressed certain mol proportion mixing, i.e. one pot reaction, reacting by heating prepares tetramethyl biphenyl compound under an inert atmosphere, reaction terminates rear removing inorganic salt, and gained tetramethyl biphenyl compound is through underpressure distillation purifying.
2. a tetramethyl biphenyl isomers ofthe method two: halo o-Xylol, MAGNESIUM METAL, methyl cycloalkyl ether, iodine or alkyl Grignard reagent are pressed certain mol proportion mixing, after reacting by heating generates Grignard reagent under an inert atmosphere, add catalyzer again and prepare tetramethyl biphenyl compound through linked reaction, reaction terminates rear removing inorganic salt, and gained tetramethyl biphenyl compound is through underpressure distillation purifying.
3. a tetramethyl biphenyl isomers ofthe method three: 4-halo o-Xylol (or 3-halo o-Xylol), MAGNESIUM METAL, methyl cycloalkyl ether, iodine or alkyl Grignard reagent are pressed certain mol proportion mixing, after reacting by heating generates Grignard reagent under an inert atmosphere, add catalyzer and 3-halo o-Xylol (or 4-halo o-Xylol) again, 2 are prepared through linked reaction, 3 ', 3,4 '-tetramethyl biphenyl compound, reaction terminates rear removing inorganic salt, and gained tetramethyl biphenyl compound is through underpressure distillation purifying.
4. the preparation method of tetramethyl biphenyl isomer according to claim 1,2 or 3, it is characterized in that, described 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 formula (1) is 3-halo o-Xylol, and formula (2) is 4-halo o-Xylol.
5. the preparation method of tetramethyl biphenyl isomer according to claim 1,2 or 3, is characterized in that, described tetramethyl biphenyl is compounds 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, formula (5) 3,3 ', 4,4 '-be tetramethyl biphenyl.
6. the tetramethyl biphenyl isomers ofthe method according to claim 1,2 or 3, is characterized in that, described methyl cycloalkyl ether is one or more in compound shown in following formula (6) and (7):
Wherein, substituent R
1for hydrogen atom or methyl.
7. the preparation method of tetramethyl biphenyl isomer according to claim 1, it is characterized in that, the mol ratio of described halo o-Xylol, MAGNESIUM METAL, methyl cycloalkyl ether, iodine or alkyl Grignard reagent and catalyzer is 100:10 ~ 50:10 ~ 1000:0.01 ~ 20:0.01 ~ 100, and temperature of reaction is 30
oc ~ 150
oc, 0.5 ~ 24 hour reaction times; Tetramethyl biphenyl compound, through underpressure distillation purifying, collects pressure under 0.1-300 mmhg 100
oc ~ 290
oc cut.
8. the preparation method of tetramethyl biphenyl isomer according to claim 2, it is characterized in that, the mol ratio of described halo o-Xylol, MAGNESIUM METAL, methyl cycloalkyl ether, iodine or alkyl Grignard reagent is 100:10 ~ 50:10 ~ 1000:0.01 ~ 20; The temperature of reaction generating the Grignard reagent of halo o-Xylol is 30
oc ~ 150
oc, the reaction times is 0.5 ~ 24 hour; The catalyzer added and the mol ratio of MAGNESIUM METAL are 0.001 ~ 1:1, and the catalyzed coupling reaction time is 0.5-12 hour, and temperature of reaction is 30
oc ~ 150
oc; Tetramethyl biphenyl compound, through underpressure distillation purifying, collects pressure under 0.1-300 mmhg 100
oc ~ 290
oc cut.
9. the preparation method of tetramethyl biphenyl isomer according to claim 3, it is characterized in that, described 4-halo o-Xylol (or 3-halo o-Xylol), MAGNESIUM METAL, methyl cycloalkyl ether, iodine or alkyl Grignard reagent mol ratio 100:100 ~ 150:300 ~ 4000:0.1 ~ 10, the temperature of reaction generating halo o-Xylol Grignard reagent is 30
oc ~ 150
oc, the reaction times is 0.5 ~ 24 hour; The catalyzer added afterwards and the mol ratio of MAGNESIUM METAL are 0.001 ~ 1:1, and adding 3-halo o-Xylol (or 4-halo o-Xylol) with the mol ratio of MAGNESIUM METAL is 1:0.5 ~ 1, and the catalyzed coupling reaction time is 0.5-12 hour, and temperature of reaction is 30
oc ~ 150
oc; Gained 2,3 ', 3,4 '-tetramethyl biphenyl compound, through underpressure distillation purifying, collects pressure under 0.1-300 mmhg 100
oc ~ 290
oc cut.
10. the tetramethyl biphenyl isomers ofthe method according to claim 1,2 or 3, it is characterized in that, described catalyzer is the complex catalyst that transition metal salt or transition metal salt and heteroatoms organic ligand are formed, wherein transition metal salt and heteroatoms organic ligand in molar ratio 1:0 ~ 10 original position prepare.
11. according to claim 1, 2, or the tetramethyl biphenyl isomers ofthe method described in 3, it is characterized in that, described catalyzer 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, Manganese dibromide, manganese iodide, manganous sulfate, manganese acetate, cupric chloride, cupric bromide, copper sulfate, neutralized verdigris, copper carbonate, one or more in cuprous chloride and cuprous bromide.
The preparation method of 12. transition metal complex catalysts according to claim 10, is characterized in that, described heteroatoms organic ligand can be compound shown in following formula (8) ~ (17) one or more:
Wherein, R in formula (8) ~ (10)
2~ R
7independently be selected from hydrogen separately, alkyl, aryl or substituted aryl that carbon number is less than 20; (11) R in ~ (17)
8~ R
29independently be selected from separately alkyl, aryl or substituted aryl that carbon number is less than 20; N1 and n2 is the integer between 0 ~ 100.
13. according to claim 10 or 12 transition metal complex catalysts preparation method, it is characterized in that, described heteroatoms organic ligand 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, N, N, N ', N '-tetramethyl--1, 2-quadrol, N, N, N ', N '-tetramethyl--1, 2-quadrol, N, N, N ', N ', N ' '-pentamethyl--divinyl-triamine, N, N, N ', N ', N ' ', N ' '-hexamethyl-trivinyl-tetramine, two (diphenylphosphine)-ethane, one or more in two (dibutyl phosphorus)-ethane.
14. according to claim 1,2 or 3 preparation method of tetramethyl biphenyl isomer, it is characterized in that, described rare gas element comprises nitrogen, argon gas or helium, is preferably argon gas.
15. according to claim 1,2 or 3 preparation method of tetramethyl biphenyl isomer, it is characterized in that, the described preferred cyclopentyl methyl ether of cycloalkyl methyl ether and hexanaphthene methyl ether, more preferably cyclopentyl methyl ether, above-mentioned solvent recovery cycle uses.
16. according to claim 1,2 or 3 preparation method of tetramethyl biphenyl isomer, it is characterized in that, the method for described removing inorganic salt comprises direct filtration inorganic salt, collects organic phase; Or add a small amount of water and realize organic phase and inorganic phase layering, then extract separatory, collect organic phase.
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| RU2599987C1 (en) * | 2015-09-08 | 2016-10-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) | Method of producing 3, 3', 4, 4'-tetramethyldiphenyl |
| CN106083506A (en) * | 2016-06-03 | 2016-11-09 | 四川大学 | A kind of preparation method of 2,2 ' dimethyl diphenyls |
| CN106279216A (en) * | 2016-04-06 | 2017-01-04 | 海正化工南通股份有限公司 | A kind of synthesis way of o-chlorobenzyl magnesium chloride |
| 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 |
| CN113087590A (en) * | 2020-01-08 | 2021-07-09 | 浙江中欣氟材股份有限公司 | Synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl |
| CN113277926A (en) * | 2021-07-20 | 2021-08-20 | 山东冠森高分子材料科技股份有限公司 | Method for separating high-purity isomers of tetramethyl biphenyl by rectification-melt crystallization coupling |
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| RU2599987C1 (en) * | 2015-09-08 | 2016-10-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) | Method of producing 3, 3', 4, 4'-tetramethyldiphenyl |
| CN106279216A (en) * | 2016-04-06 | 2017-01-04 | 海正化工南通股份有限公司 | A kind of synthesis way of o-chlorobenzyl magnesium chloride |
| CN106083506A (en) * | 2016-06-03 | 2016-11-09 | 四川大学 | A kind of preparation method of 2,2 ' dimethyl diphenyls |
| 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 |
| 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 |
| CN113087590A (en) * | 2020-01-08 | 2021-07-09 | 浙江中欣氟材股份有限公司 | Synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl |
| CN113087590B (en) * | 2020-01-08 | 2022-05-03 | 浙江中欣氟材股份有限公司 | Synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl |
| CN113277926A (en) * | 2021-07-20 | 2021-08-20 | 山东冠森高分子材料科技股份有限公司 | Method for separating high-purity isomers of tetramethyl biphenyl by rectification-melt crystallization coupling |
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