CN103086838A - Preparation method of tetramethyl biphenyl - Google Patents
Preparation method of tetramethyl biphenyl Download PDFInfo
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- CN103086838A CN103086838A CN2013100506305A CN201310050630A CN103086838A CN 103086838 A CN103086838 A CN 103086838A CN 2013100506305 A CN2013100506305 A CN 2013100506305A CN 201310050630 A CN201310050630 A CN 201310050630A CN 103086838 A CN103086838 A CN 103086838A
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Abstract
The invention provides a preparation method of tetramethyl biphenyl, which comprises the following steps: mixing halogenated o-xylene, magnesium metal, iodine, ether and transition metal catalyst, and reacting to obtain the tetramethyl biphenyl, wherein the mol ratio of ether to magnesium metal is (0.5-3):1. Compared with the prior art of synthesizing tetramethyl biphenyl from halogenated o-xylene, the invention has the following advantages: by using the raw material halogenated o-xylene as the solvent, the preparation of the format reagent and the coupling reaction are carried out in the initial raw material, so that the addition of abundant anhydrous solvent as the reaction medium is not needed, thereby lowering the reaction cost and simplifying the production technique; the magnesium metal is directly added into the halogenated o-xylene to obtain the format reagent, so the process is simple and the conditions are mild and controllable; and the raw material, the concentration of which in the reaction system is high, is used as the solvent and participates in the oxidation-reduction process in the coupling reaction, no oxidizer is needed, so the reaction conditions are mild and controllable.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate in particular to a kind of preparation method of tetramethyl biphenyl.
Background technology
Polyimide is as a kind of high-performance polymer, there are high temperature resistant, anti-solvent, radiation hardness and good mechanical property and dielectric properties, wherein the heat decomposition temperature of biphenyl polyimide can reach 600 ℃, it is one of kind that in polymkeric substance, thermostability is the highest, in fields such as mechano-electronic, aerospace, large-size machine, hydrodynamic bearing, heat-resisting filter materials, be with a wide range of applications, but, because its preparation cost is higher, application is restricted.
The crucial monomer for preparing biphenyl polyimide is bibenzene tetracarboxylic dianhydride, the synthetic cost of this monomer has determined the cost of polyimide to a great extent, therefore, important approach that realizes of low-cost technology of preparing of pursuit polyimide is cheap bibenzene tetracarboxylic dianhydride technology of preparing.
The preparation method of bibenzene tetracarboxylic dianhydride is a lot, as: take chloro-benzoic anhydride as initiator, through processes such as esterification, coupling, hydrolysis, one-tenth acid anhydrides; The chloro-benzoic anhydride of perhaps take is collectively referred to as BPDA as raw material under Pd/C catalysis; The phthalic anhydride of perhaps take prepares bibenzene tetracarboxylic dianhydride as raw material oxidation in the presence of the Pd catalyzer.That the Chinese patent that application number is CN201010611991 discloses is a kind of 2,3,3 ', 4 '-the bibenzene tetracarboxylic dianhydride preparation method, it be take tetramethyl biphenyl and prepares bibenzene tetracarboxylic dianhydride, this preparation method's simple economy as raw material.
The existing synthetic technology of tetramethyl biphenyl mainly be take the halo o-Xylol and is collectively referred to as raw material, and the halo o-Xylol is to be replaced by o-Xylol to make, this has increased reaction cost and reaction process to a certain extent, and the separation difficulty of halo o-Xylol, and industrial cost is higher.The Chinese patent that the Chinese patent that application number is CN88107107 and application number are CN201010611991 all discloses takes the halo o-Xylol under the catalysis of the triaryl phosphorus title complex of excess zinc and nickel, the synthetic tetramethyl biphenyl that obtains, this method, owing to using a large amount of zinc powders, produces a large amount of waste residues containing zinc, zinc salt after reaction.Reaction process is as follows:
The Chinese patent that the Chinese patent that application number is CN200410089450 and application number are CN200780035615 all discloses and has carried out coupling with halo o-Xylol and halo o-Xylol Grignard reagent under the catalysis of transistion metal compound and obtain tetramethyl biphenyl, but this method need be used a large amount of anhydrous tetrahydro furans for solvent, increase the requirement of operating environment, also brought the increase of cost; The forming process of Grignard reagent need realize by the exchange of using commercially available Grignard reagent simultaneously, has also brought the raising of operational requirement and the increase of cost; On the other hand, also need to use to have dichloro-alkane that toxicity is higher as oxygenant, this type of oxygenant can cause vigorous reaction when adding reaction system, makes reaction be difficult to control.This reaction process is as follows:
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of tetramethyl biphenyl, and the method is simple and cost is lower.
The invention provides a kind of preparation method of tetramethyl biphenyl, comprising:
A) halo o-Xylol, MAGNESIUM METAL, iodine, ether are mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl; The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.
Preferably, described steps A) be specially:
A1) halo o-Xylol, MAGNESIUM METAL, iodine are mixed with ether, reacted, obtain Grignard reagent;
A2) described Grignard reagent is mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl;
The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.
Preferably, described steps A 2), also add additive; Described additive is for containing heteroatomic monodentate type ligand compound and/or containing heteroatomic two flute profile ligand compounds.
Preferably, described additive is with one or more in the compound shown in following formula (1) ~ formula (8):
Wherein ,-X
1~-X
6,-Y
1~-Y
5be selected from independently of one another-H or a kind of with in structure shown in following formula (9) ~ formula (12) ,-X
1with-Y
1in have at least one not to be-H ,-X
3with-Y
3in have at least one not to be-H ,-X
4with-Y
4in have at least one not to be-H ,-X
5with-Y
5in have at least one not to be-H;
Wherein, R
1~ R
10independently be selected from separately alkyl, phenyl or substituted-phenyl, n1 is 1 or 2, the n2 integer that is 1 ~ 100.
Preferably, described additive is selected from 2, 2 '-dipyridyl, phenanthroline, 3, 3 '-dimethyl-2, 2 '-dipyridyl, 4, 4 '-dimethyl-2, 2 '-dipyridyl, 5, 5 '-dimethyl-2, 2 '-dipyridyl, 1, the 10-phenanthroline, 2, 9-dimethyl-1, the 10-phenanthroline, N, N, N ', N '-tetramethyl--1, the 2-quadrol, N, N, N ', N '-tetramethyl--1, the 3-propylene diamine, glycol dimethyl ether, ethylene glycol diethyl ether, TRIGLYME, Polyethylene glycol dimethyl ether, two (2-dimethylamino) ethyl ether, 2, 2 '-dimethoxy-biphenyl, 2, 2 '-dimethoxy-1, 1 '-dinaphthalene, 2, 2 '-dimethylin-1, 1 '-dinaphthalene, 1, the 2-dimethoxy benzene, 1, the 2-Dimethylaminobenzene, 4-(N, the N dimethylamine base) pyridine, pyridine, diphenyl phosphate oxygen, triphenylphosphine, 2, 2 '-bis-(diphenylphosphine)-1, 1 '-dinaphthalene, 1, 2 '-bis-(diphenylphosphine) ethane, with 1, one or more in 2 '-bis-(diphenylphosphine) propane.
Preferably, described ether is tetrahydrofuran (THF) and/or ether.
Preferably, described transition-metal catalyst is one or more in Metallic iron and iron--containing compounds, metal Cobalt and compounds of cobalt, metallic nickel and compound, metallic copper and compound thereof and palladium metal and compound thereof.
Preferably, described transition-metal catalyst is selected from one or more in Anhydrous Ferric Chloride, anhydrous chlorides of rase ferrous iron, anhydrous ferrous bromide, Dehydrated nickel chloride, waterless cobaltous chloride, anhydrous acetylacetonate nickel and anhydrous ferric acetyl acetonade.
Preferably, the mol ratio of described MAGNESIUM METAL and halo o-Xylol is (0.1 ~ 0.4): 1.
Preferably, the mol ratio of described iodine and MAGNESIUM METAL is (0.0001 ~ 0.01): 1.
The invention provides a kind of preparation method of tetramethyl biphenyl, comprise halo o-Xylol, MAGNESIUM METAL, iodine, ether are mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl; The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.The halo o-Xylol of take with prior art is compared as raw material synthesizes tetramethyl biphenyl, at first, the present invention with raw material halo o-Xylol this as solvent, preparation and the linked reaction of grignard reagent are carried out in starting raw material, do not need to add a large amount of anhydrous solvents as reaction medium, reduce reaction cost, also simplified production technique; Secondly, in the halo o-Xylol, directly add MAGNESIUM METAL to obtain grignard reagent, process is easy, and mild condition is controlled; Again, owing to adopting raw material originally as solvent, reaction system Raw concentration is higher, and itself participates in the redox processes in linked reaction, does not need to add oxygenant, makes the reaction conditions gentleness controlled.
The accompanying drawing explanation
The gas chromatogram that Fig. 1 is the organic phase for preparing of the embodiment of the present invention 1;
Fig. 2 is 2,2 ', 3,3 '-gas chromatogram of tetramethyl biphenyl standard model;
The gas chromatogram that Fig. 3 is the organic phase for preparing of the embodiment of the present invention 8;
Fig. 4 is 3,3 ', 4,4 '-gas chromatogram of tetramethyl biphenyl standard model;
The gas chromatogram that Fig. 5 is the organic phase for preparing of the embodiment of the present invention 10;
Fig. 6 is 2,2 ', 3,3 '-tetramethyl biphenyl, 2,3,3 ', 4 '-tetramethyl biphenyl and 3,3 ', 4,4 '-gas chromatogram of tetramethyl biphenyl mixture standard model;
Fig. 7 be the embodiment of the present invention 11 prepare 3,3 ', 4,4 '-the hydrogen nuclear magnetic resonance spectrogram of tetramethyl biphenyl.
Embodiment
The invention provides a kind of preparation method of tetramethyl biphenyl, comprising: A) halo o-Xylol, MAGNESIUM METAL, iodine, ether are mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl; The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.
Wherein, described halo o-Xylol is that halo o-Xylol well known to those skilled in the art gets final product, can be 3-halo o-Xylol and also can be 4-halo o-Xylol, or both mixtures, there is no special restriction.Halogenic substituent in halo o-Xylol of the present invention can be chlorine or bromine, there is no special restriction.
Described MAGNESIUM METAL is that MAGNESIUM METAL well known to those skilled in the art gets final product, and can be the magnesium powder, magnesium is cut or magnesium rod, there is no special restriction.The consumption of described MAGNESIUM METAL is that the reaction system that maintains after grignard reagent forms well known to those skilled in the art is liquid any amount, there is no special restriction, and in the present invention, the mol ratio of described MAGNESIUM METAL and halo o-Xylol is preferably (0.1 ~ 0.4): 1.
Described iodine is that iodine well known to those skilled in the art gets final product, and there is no special restriction.The effect of iodine is the zone of oxidation of removing metallic magnesium surface, is conducive to the formation of grignard reagent.The consumption of described iodine is common usage quantity prepared by grignard reagent, there is no special restriction.The mol ratio of iodine described in the present invention and MAGNESIUM METAL is preferably (0.0001 ~ 0.01): 1.
Described ether is that ether well known to those skilled in the art gets final product, and there is no special restriction.Ether described in the present invention is preferably tetrahydrofuran (THF) and/or ether.The mol ratio of described ether and MAGNESIUM METAL is preferably (1 ~ 1.5): 1.Ether described in the present invention adds and uses with a mole metering, and it just promotes the formation of grignard reagent not as solvent.
Described transition-metal catalyst is that transition-metal catalyst well known to those skilled in the art gets final product, and there is no special restriction.Transition-metal catalyst described in the present invention is preferably one or more in Metallic iron and iron--containing compounds, metal Cobalt and compounds of cobalt, metallic nickel and compound, metallic copper and compound thereof and palladium metal and compound thereof.The compound of described above-mentioned each transition metal is preferably the transistion metal compounds such as muriate, bromide, iodide, fluorochemical, acetate, acetylacetonate, carbonate, oxyhydroxide or nitrate of transition metal.Transition-metal catalyst described in the present invention is one or more in iron(ic) chloride, iron protochloride, ferrous bromide, nickelous chloride, cobalt chloride, acetylacetonate nickel and ferric acetyl acetonade more preferably, then are preferably one or more in Anhydrous Ferric Chloride, anhydrous chlorides of rase ferrous iron, anhydrous ferrous bromide, Dehydrated nickel chloride, waterless cobaltous chloride, anhydrous acetylacetonate nickel and anhydrous ferric acetyl acetonade.The mol ratio of described transition-metal catalyst and MAGNESIUM METAL is preferably (0.001 ~ 0.1): 1, more preferably (0.01 ~ 0.1): 1.
According to the present invention, described steps A) be specially: A1) halo o-Xylol, MAGNESIUM METAL, iodine are mixed with ether, reacted, obtain Grignard reagent; A2) described Grignard reagent is mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl; The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.
Described steps A 1) be the forming process of grignard reagent, the order of addition(of ingredients) of wherein said halo o-Xylol, MAGNESIUM METAL, iodine and ether is that order of addition(of ingredients) well known to those skilled in the art gets final product, and there is no special restriction.Described steps A 1) in, the formation temperature of grignard reagent, for those skilled in the art's the temperature of reaction of knowing gets final product, can be 0 ℃ to reflux temperature, there is no special restriction, is preferably 90 ℃ ~ 150 ℃ in the present invention.
Described steps A 2) be linked reaction, the temperature of wherein said linked reaction is that temperature of reaction well known to those skilled in the art gets final product, and can be 20 ℃ to reflux temperature, there is no special restriction, is preferably 40 ℃ ~ 100 ℃ in the present invention.Till described reaction end can no longer increase by the gas chromatographic detection product, steps A described in the present invention 2) in, the time of reaction is preferably 10 ~ 15h.
The present invention originally as solvent, carries out the preparation of grignard reagent and linked reaction with raw material halo o-Xylol in starting raw material, does not need to add a large amount of anhydrous solvents as reaction medium, has reduced reaction cost, has also simplified production technique; And, in the halo o-Xylol, directly add MAGNESIUM METAL to obtain grignard reagent, process is simple, and mild condition is controlled; Owing to adopting raw material originally as solvent, reaction system Raw concentration is higher, and itself participates in the redox processes in linked reaction, does not need to add oxygenant, makes the reaction conditions gentleness controlled.
According to the present invention, described steps A 2) preferably also add additive in, described additive is for containing heteroatomic monodentate type ligand compound and/or containing heteroatomic two flute profile ligand compounds, and it has with the monodentate type ligand compound of magnesium coordination ability and/or containing heteroatomic two flute profile ligand compounds for well known to those skilled in the art.Additive described in the present invention is preferably with one or more in the compound shown in following formula (1) ~ formula (8).
Wherein ,-X
1~-X
6,-Y
1~-Y
5be selected from independently of one another-H or a kind of with in structure shown in following formula (9) ~ formula (12) ,-X
1with-Y
1in have at least one not to be-H ,-X
3with-Y
3in have at least one not to be-H ,-X
4with-Y
4in have at least one not to be-H ,-X
5with-Y
5in have at least one not to be-H;
Wherein, R
1~ R
10independently be selected from separately alkyl, phenyl or substituted-phenyl, n1 is 1 or 2, the n2 integer that is 1 ~ 100, is preferably 1 ~ 50 integer, 1 ~ 10 integer more preferably, then be preferably 1 ~ 4 integer.
Additive described in the present invention more preferably 2, 2 '-dipyridyl, phenanthroline, 3, 3 '-dimethyl-2, 2 '-dipyridyl, 4, 4 '-dimethyl-2, 2 '-dipyridyl, 5, 5 '-dimethyl-2, 2 '-dipyridyl, 1, the 10-phenanthroline, 2, 9-dimethyl-1, the 10-phenanthroline, N, N, N ', N '-tetramethyl--1, the 2-quadrol, N, N, N ', N '-tetramethyl--1, the 3-propylene diamine, glycol dimethyl ether, ethylene glycol diethyl ether, TRIGLYME, Polyethylene glycol dimethyl ether, two (2-dimethylamino) ethyl ether, 2, 2 '-dimethoxy-biphenyl, 2, 2 '-dimethoxy-1, 1 '-dinaphthalene, 2, 2 '-dimethylin-1, 1 '-dinaphthalene, 1, the 2-dimethoxy benzene, 1, the 2-Dimethylaminobenzene, 4-(N, the N dimethylamine base) pyridine, pyridine, diphenyl phosphate oxygen, triphenylphosphine, 2, 2 '-bis-(diphenylphosphine)-1, 1 '-dinaphthalene, 1, 2 '-bis-(diphenylphosphine) ethane, with 1, one or more in 2 '-bis-(diphenylphosphine) propane.
Additive can by with the transition-metal catalyst coordination, participate in the halo o-Xylol and react with the metal transfer between transition-metal catalyst, promote the regeneration of transition-metal catalyst in the catalytic cycle process, thereby the efficiency of raising linked reaction.
According to the present invention, described steps A 2) also comprise, after having reacted, in reaction system, add water or acidic aqueous solution cancellation reaction, be preferably acidic aqueous solution, by the organic layer underpressure distillation, obtain tetramethyl biphenyl.
Wherein, described acidic aqueous solution can be dilute hydrochloric acid, sal enixum, dilute sulphuric acid, dilute acetic acid or saturated ammonium chloride solution.Except saturated ammonium chloride solution, other acidic solutions can be any concentration that meets cancellation residual reaction solution containing grignard reagent, are preferably 0.5 ~ 2mol/L.The consumption of described water or acidic aqueous solution is 0.3 ~ 3.0 times of reaction raw materials halo o-Xylol volume, more preferably 0.5 ~ 2.0 times.Acidic aqueous solution is conducive to form the water of homogeneous, thereby is easy to separate organic layer.After more preferably having reacted, reaction system is down to room temperature, and then adds water or acidic aqueous solution cancellation reaction in reaction system.
Underpressure distillation described in the present invention is preferably removes a small amount of front-end volatiles, collect the 48 ℃ ~ cut of 55 ℃ (3 ~ 4mmHg), this is reaction raw materials halo o-Xylol recoverable, and underpressure distillation steams to no longer including cut, use pure crystalline residue, obtain tetramethyl biphenyl.
Described alcohol is that alcohol well known to those skilled in the art gets final product, and there is no special restriction.Alcohol described in the present invention is preferably methyl alcohol, ethanol, propyl alcohol, Virahol, butanols or the trimethyl carbinol.The consumption of described alcohol is 0.5 ~ 1 times of raw material halo o-Xylol volume, is preferably 0.6 ~ 0.8 times.The temperature of described crystallization is that Tc well known to those skilled in the art gets final product, and there is no special restriction.Be preferably in the present invention below 20 ℃ and carry out crystallization.
The resulting tetramethyl biphenyl of the present invention is preferably with one or more the mixture of arbitrary proportion in following formula (I) ~ three kinds of tetramethyl biphenyls of formula (III).
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of tetramethyl biphenyl provided by the invention is described in detail.
In following examples, reagent used is commercially available.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml3-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 0.123g(7.7 * 10
-4mol) Anhydrous Ferric Chloride, continue stirring reaction 12h, and reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stir 30min, minute water-yielding stratum, organic layer gas chromatographic analysis, obtain 2,2 ', 3,3 '-tetramethyl biphenyl, yield is 50%, its gas chromatogram is as shown in Figure 1, wherein, A is the 3-chloro-o-xylene, and Fig. 2 is 2,2 ', 3,3 '-gas chromatogram of tetramethyl biphenyl standard model.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 0.123g(7.7 * 10
-4mol) Anhydrous Ferric Chloride, continue stirring reaction 12h, and reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stirs 30min, minute water-yielding stratum, and the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 52%.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 0.123g(7.7 * 10
-4mol) Anhydrous Ferric Chloride and 2.01ml(0.0154mol) ethylene glycol diethyl ether, continue stirring reaction 13h, reaction system is down to room temperature, add the 20ml saturated ammonium chloride solution, stir 30min, divide water-yielding stratum, the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 59%.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 0.123g(7.7 * 10
-4mol) Anhydrous Ferric Chloride and 0.0154molN, N, N ', N '-tetramethyl--1，2-diaminoethane, continue stirring reaction 13h, reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stir 30min, divide water-yielding stratum, the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 64%.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 7.7 * 10
-4the anhydrous diacetyl acetone of mol nickel, continue stirring reaction 12h, and reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stirs 30min, minute water-yielding stratum, and the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 66%.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 7.7 * 10
-4the mol Dehydrated nickel chloride, continue stirring reaction 12h, and reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stirs 30min, minute water-yielding stratum, and the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 60%.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 7.7 * 10
-4the mol waterless cobaltous chloride, continue stirring reaction 12h, and reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stirs 30min, minute water-yielding stratum, and the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 53%.
Embodiment 8
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 10ml4-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 7.7 * 10
-4mol diacetyl acetone nickel and 0.0154molN, N, N ', N '-tetramethyl--1, the 2-quadrol, continue stirring reaction 13h, and reaction system is down to room temperature, adds the 20ml saturated ammonium chloride solution, stir 30min, minute water-yielding stratum, the organic layer gas chromatographic analysis, obtain 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 83%, as shown in Figure 3, wherein B is the 4-chloro-o-xylene to its gas chromatogram, and Fig. 4 is 3,3 ', 4,4 '-gas chromatogram of tetramethyl biphenyl standard model.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 5ml4-chloro-o-xylene, 5ml3-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 0.123g(7.7 * 10
-4mol) Anhydrous Ferric Chloride and 2.01ml(0.0154mol) ethylene glycol diethyl ether, continue stirring reaction 13h, reaction system is down to room temperature, add the 20ml saturated ammonium chloride solution, stir 30min, minute water-yielding stratum, organic layer gas chromatographic analysis, obtain 2,2 ', 3,3 '-tetramethyl biphenyl, 2,3,3 ', 4 '-tetramethyl biphenyl and 3,3 ', 4,4 '-mixture of tetramethyl biphenyl, its ratio is 0.82:0.91:1, yield is 60%.
Be furnished with the air in the 25ml reaction flask of reflux condensing tube with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 0.37g(0.0154mol) magnesium powder, 5ml4-chloro-o-xylene, 5ml3-chloro-o-xylene, 0.01g(3.6 * 10
-6mol) iodine and 1.41ml(0.0174mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 7.7 * 10
-4the anhydrous diacetyl acetone of mol nickel, continue stirring reaction 12h, reaction system is down to room temperature, add the 20ml saturated ammonium chloride solution, stir 30min, divide water-yielding stratum, the organic layer gas chromatographic analysis, obtain 2, 2 ', 3, 3 '-tetramethyl biphenyl, 2, 3, 3 ', 4 '-tetramethyl biphenyl and 3, 3 ', 4, 4 '-mixture of tetramethyl biphenyl, its ratio is 0.52:1.66:1, yield is 67%, its gas chromatogram as shown in Figure 5, Fig. 6 is 2, 2 ', 3, 3 '-tetramethyl biphenyl, 2, 3, 3 ', 4 '-tetramethyl biphenyl and 3, 3 ', 4, 4 '-gas chromatogram of tetramethyl biphenyl mixture standard model.
Embodiment 11
Be furnished with the air in the reflux condensing tube reaction flask with nitrogen replacement, under the atmosphere of nitrogen protection, in reaction flask, add successively 5.55g(0.231mol) magnesium powder, 150ml4-chloro-o-xylene, 0.15g(5.4 * 10
-5mol) iodine and 21.15ml(0.261mol) anhydrous tetrahydro furan, stir and be heated to 110 ℃, reaction 10h magnesium powder disappears, and reaction mixture is cooled to 60 ℃, adds 1.155 * 10
-2mol diacetyl acetone nickel and 0.231molN, N, N ', N '-tetramethyl--1，2-diaminoethane, continue stirring reaction 13h, reaction system is down to room temperature, adds the 300ml saturated ammonium chloride solution, stir 30min, divide water-yielding stratum, the organic layer dried over mgso, filter, the filtrate decompression distillation, collecting the 48 ℃ ~ cut of 55 ℃ (3 ~ 4mmHg), is the 4-chloro-o-xylene, can be directly again for linked reaction.In the residue of underpressure distillation, add 75ml methyl alcohol, stir, crystallize out after 1h, filter, a small amount of methanol wash, obtain white micro-bloom shape solid 20.3g, be 3,3 ', 4,4 '-tetramethyl biphenyl, yield is 51%, utilizes its purity of gas chromatographic analysis to be greater than 98.5%.
Utilize nucleus magnetic resonance in embodiment 11, obtain 3,3 ', 4,4 '-tetramethyl biphenyl analyzed, and obtains its hydrogen nuclear magnetic resonance spectrogram, as shown in Figure 7.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a tetramethyl biphenyl, is characterized in that, comprising:
A) halo o-Xylol, MAGNESIUM METAL, iodine, ether are mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl; The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.
2. preparation method according to claim 1, is characterized in that, described steps A) be specially:
A1) halo o-Xylol, MAGNESIUM METAL, iodine are mixed with ether, reacted, obtain Grignard reagent;
A2) described Grignard reagent is mixed with transition-metal catalyst, reacted, obtain tetramethyl biphenyl;
The mol ratio of described ether and MAGNESIUM METAL is (0.5 ~ 3): 1.
3. preparation method according to claim 2, is characterized in that, described steps A 2) in also add additive; Described additive is for containing heteroatomic monodentate type ligand compound and/or containing heteroatomic two flute profile ligand compounds.
4. preparation method according to claim 3, is characterized in that, described additive is with one or more in the compound shown in following formula (1) ~ formula (8):
Wherein ,-X
1~-X
6,-Y
1~-Y
5be selected from independently of one another-H or a kind of with in structure shown in following formula (9) ~ formula (12) ,-X
1with-Y
1in have at least one not to be-H ,-X
3with-Y
3in have at least one not to be-H ,-X
4with-Y
4in have at least one not to be-H ,-X
5with-Y
5in have at least one not to be-H;
Wherein, R
1~ R
10independently be selected from separately alkyl, phenyl or substituted-phenyl, n1 is 1 or 2, the n2 integer that is 1 ~ 100.
5. preparation method according to claim 3, is characterized in that, described additive is selected from 2,2 '-dipyridyl, phenanthroline, 3,3 '-dimethyl-2,2 '-dipyridyl, 4,4 '-dimethyl-2,2 '-dipyridyl, 5,5 '-dimethyl-2,2 '-dipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1, the 10-phenanthroline, N, N, N ', N '-tetramethyl--1，2-diaminoethane, N, N, N ', N '-tetramethyl-1,3-propane diamine, glycol dimethyl ether, ethylene glycol diethyl ether, TRIGLYME, Polyethylene glycol dimethyl ether, two (2-dimethylamino) ethyl ether, 2,2 '-dimethoxy-biphenyl, 2,2 '-dimethoxy-1,1 '-dinaphthalene, 2,2 '-dimethylin-1,1 '-dinaphthalene, 1,2-dimethoxy benzene, 1,2-Dimethylaminobenzene, 4-(N, the N dimethylamine base) pyridine, pyridine, diphenyl phosphate oxygen, triphenylphosphine, 2,2 '-bis-(diphenylphosphine)-1,1 '-dinaphthalene, 1,2 '-bis-(diphenylphosphine) ethane, with one or more in 1,2 '-bis-(diphenylphosphine) propane.
6. preparation method according to claim 1, is characterized in that, described ether is tetrahydrofuran (THF) and/or ether.
7. preparation method according to claim 1, it is characterized in that, described transition-metal catalyst is one or more in Metallic iron and iron--containing compounds, metal Cobalt and compounds of cobalt, metallic nickel and compound, metallic copper and compound thereof and palladium metal and compound thereof.
8. preparation method according to claim 1, it is characterized in that, described transition-metal catalyst is selected from one or more in Anhydrous Ferric Chloride, anhydrous chlorides of rase ferrous iron, anhydrous ferrous bromide, Dehydrated nickel chloride, waterless cobaltous chloride, anhydrous acetylacetonate nickel and anhydrous ferric acetyl acetonade.
9. preparation method according to claim 1, is characterized in that, the mol ratio of described MAGNESIUM METAL and halo o-Xylol is (0.1 ~ 0.4): 1.
10. preparation method according to claim 1, is characterized in that, the mol ratio of described iodine and MAGNESIUM METAL is (0.0001 ~ 0.01): 1.
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| 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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