The preparation method of high purity 2-bromine triphenyleneTechnical field
The present invention relates to a kind of preparation method, particularly relate to a kind of preparation method of high purity 2-bromine triphenylene.
Background technology
2-bromine triphenylene is important OLED luminescent material key intermediate, the main method adopted does starting raw material with triphenylene at present, NBS or bromine is utilized to do brominated reagent bromination gained, because triphenylene is a symmetrical structure, dibromo, three bromo by products will inevitably be formed during bromination, add unreacted raw material triphenylene completely, the principal product content of relative equilibrium is between 70%-80%.Due to principal product and by product character close, be difficult to purified by the method for normal recrystallization.The main method adopted is shown below at present:
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of high purity 2-bromine triphenylene, its economical and convenient, and reaction conditions is gentle, and good operational environment, yield is high.
The present invention solves above-mentioned technical problem by following technical proposals: a kind of preparation method of high purity 2-bromine triphenylene, and it is characterized in that, it comprises the following steps:
Step one, in a container, adds 2-bromo biphenyl, connection pinacol borate, potassium acetate, toluene and tetrakis triphenylphosphine palladium catalyzer, the lower back flow reaction of protection 2 hours, add water, layering, obtains the one the second intermediate-(biphenyl-2-bases)-4,4,5,5-tetramethyl--1,3,2-boron oxide, organic phase solution directly can drop into step 2;
Step 2, in another container, liquid in step one is added water, salt of wormwood, to bromo-iodobenzene and tetrakis triphenylphosphine palladium catalyzer, back flow reaction 3 hours, after reaction terminates, stratification, organic phase solution is concentrated into a large amount of solid and separates out, be cooled to 30 DEG C of filtrations, drying the second intermediate-(4-bromophenyl)-1,1 '-biphenyl;
Step 3, in a container again, adds the second intermediate-(4-bromophenyl)-1,1 '-biphenyl of step 2, Nitromethane 99Min. and iron trichloride, reacting by heating 3 hours, and cooling, adds water, layering; Organic phase is concentrated into dry, then adds alcohol reflux, after being down to room temperature, filters, dry, highly purified 2-bromine triphenylene product.
Preferably, described step one is the preparation process of preparation the one the second intermediate-(biphenyl-2-base)-4,4,5,5-tetramethyl--1,3,2-boron oxide.
Preferably, the material molar ratio of described preparation first intermediate is: 2-bromo biphenyl: connection pinacol borate: potassium acetate: tetrakis triphenylphosphine palladium is 1:1-1.2:2-4:0.5-1.
Preferably, the material molar ratio of described preparation second intermediate is: the first intermediate: to bromo-iodobenzene: salt of wormwood: tetrakis triphenylphosphine palladium=1:1-1.1:2-3:0.5-1.
Preferably, the material molar ratio of described preparation 2-bromine triphenylene: the second intermediate: iron trichloride 1:2-2.5.
Positive progressive effect of the present invention is: economical and convenient of the present invention, and reaction conditions is gentle, and good operational environment, yield is high, reduces cost, is conducive to suitability for industrialized production.
Accompanying drawing explanation
The present invention is further described below in conjunction with the drawings and specific embodiments:
Fig. 1 is HPLC collection of illustrative plates (HighPerformanceLiquidChromatography, the high performance liquid chromatography of the second intermediate-(4-bromophenyl)-1,1 '-biphenyl prepared by the present invention's (embodiment 4); Also known as " high pressure liquid chromatography ") schematic diagram;
Fig. 2 is HPLC collection of illustrative plates (HighPerformanceLiquidChromatography, the high performance liquid chromatography of the second intermediate-(4-bromophenyl)-1,1 '-biphenyl prepared by the present invention's (embodiment 5); Also known as " high pressure liquid chromatography ") schematic diagram;
Fig. 3 is HPLC collection of illustrative plates (HighPerformanceLiquidChromatography, the high performance liquid chromatography of product 2-bromine triphenylene prepared by the present invention's (embodiment 7); Also known as " high pressure liquid chromatography ") schematic diagram;
Fig. 4 is HPLC collection of illustrative plates (HighPerformanceLiquidChromatography, the high performance liquid chromatography of product 2-bromine triphenylene prepared by the present invention's (embodiment 8); Also known as " high pressure liquid chromatography ") schematic diagram.
Embodiment
Present pre-ferred embodiments is provided, to describe technical scheme of the present invention in detail below in conjunction with accompanying drawing.
Following three formulas (1) of chemical reaction route of the present invention are to (3):
………………（1）
……………（2）
………（3）
The preparation method of high purity 2-bromine triphenylene of the present invention comprises the following steps:
Step one, in a container, adds 2-bromo biphenyl, connection pinacol borate, potassium acetate, toluene and tetrakis triphenylphosphine palladium catalyzer, the lower back flow reaction of protection 2 hours, add water, layering, obtains the one the second intermediate-(biphenyl-2-bases)-4,4,5,5-tetramethyl--1,3,2-boron oxide, organic phase solution directly can drop into step 2; Step one is the preparation process of preparation the one the second intermediate-(biphenyl-2-base)-4,4,5,5-tetramethyl--1,3,2-boron oxide.The material molar ratio preparing the first intermediate is: 2-bromo biphenyl: connection pinacol borate: potassium acetate: tetrakis triphenylphosphine palladium is 1:1-1.2:2-4:0.5-1.
Step 2, in another container, liquid in step one is added water, salt of wormwood, to bromo-iodobenzene and tetrakis triphenylphosphine palladium catalyzer, back flow reaction 3 hours, after reaction terminates, stratification, organic phase solution is concentrated into a large amount of solid and separates out, be cooled to 30 DEG C of filtrations, drying the second intermediate-(4-bromophenyl)-1,1 '-biphenyl; The material molar ratio preparing the second intermediate is: the first intermediate: to bromo-iodobenzene: salt of wormwood: tetrakis triphenylphosphine palladium=1:1-1.1:2-3:0.5-1.
Step 3, in a container again, adds the second intermediate-(4-bromophenyl)-1,1 '-biphenyl of step 2, Nitromethane 99Min. and iron trichloride, reacting by heating 3 hours, and cooling, adds water, layering; Organic phase is concentrated into dry, then adds alcohol reflux, after being down to room temperature, filters, dry, highly purified 2-bromine triphenylene product.The material molar ratio of preparation 2-bromine triphenylene: the second intermediate: iron trichloride 1:2-2.5.
2-bromine triphenylene has following structural formula:
。
Embodiment 1
2-(biphenyl-2-base)-4; 4; 5,5-tetramethyl--1,3; being prepared as follows of 2-boron oxide: in a container; add 2-bromo biphenyl, connection pinacol borate, potassium acetate, toluene and tetrakis triphenylphosphine palladium catalyzer, the lower back flow reaction of protection 2 hours, cooling adds water; layering, organic phase solution directly can drop into next step.The mol ratio preparing the first intermediate is: 2-bromo biphenyl: connection pinacol borate: potassium acetate: tetrakis triphenylphosphine palladium=1:1:2:0.5.Wherein, charging capacity is as follows: 2-bromo biphenyl: 23.3kg; Connection pinacol borate: 25.4kg; Potassium acetate: 14.7kg; Tetrakis triphenylphosphine palladium: 0.1kg; Toluene: 100kg.Detailed step is as follows: suction 100kg toluene in 200L reactor, 2-bromo biphenyl 23.3kg(100mol is added) by manhole, connection pinacol borate 25.4kg(100mol), potassium acetate 147.kg(149.8mol), vacuum nitrogen filling gas 3 times, add tetrakis triphenylphosphine palladium 0.1kg again, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 2 hours, logical cold water is cooled to 30 DEG C.Stratification.Organic phase directly drops into next step.
Embodiment 2
2-(biphenyl-2-base)-4,4,5,5-tetramethyl--1, being prepared as follows of 3,2-boron oxide: suction 1000kg toluene in 200L reactor, adds 2-bromo biphenyl 23.3kg(100mol by manhole), connection pinacol borate 25.4kg(110mol), potassium acetate 147.kg(149.8mol), vacuum nitrogen filling gas 3 times, then add tetrakis triphenylphosphine palladium 1kg, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 2 hours, logical cold water is cooled to 30 DEG C.Stratification.Organic phase directly drops into next step.The material molar ratio preparing the first intermediate is: 2-bromo biphenyl: connection pinacol borate: potassium acetate: tetrakis triphenylphosphine palladium is 1:1.2:4:1.Wherein, charging capacity is as follows: 2-bromo biphenyl: 23.3kg; Connection pinacol borate: 27.9kg; Potassium acetate: 14.7kg; Tetrakis triphenylphosphine palladium: 0.1kg; Toluene: 100kg.Detailed step is as follows: suction 1000kg toluene in 200L reactor, 2-bromo biphenyl 23.3kg(100mol is added) by manhole, connection pinacol borate 25.4kg(110mol), potassium acetate 147.kg(149.8mol), vacuum nitrogen filling gas 3 times, add tetrakis triphenylphosphine palladium 1kg again, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 2 hours, logical cold water is cooled to 30 DEG C.Stratification.Organic phase directly drops into next step.
Embodiment 3
2-(biphenyl-2-base)-4,4,5,5-tetramethyl--1, being prepared as follows of 3,2-boron oxide: suction 1000kg toluene in 200L reactor, adds 2-bromo biphenyl 23.3kg(100mol by manhole), connection pinacol borate 25.4kg(110mol), potassium acetate 147.kg(149.8mol), vacuum nitrogen filling gas 3 times, then add tetrakis triphenylphosphine palladium 1kg, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 2 hours, logical cold water is cooled to 30 DEG C.Stratification.Organic phase directly drops into next step.The material molar ratio preparing the first intermediate is: 2-bromo biphenyl: connection pinacol borate: potassium acetate: tetrakis triphenylphosphine palladium is 1:1.1:3:0.7.Wherein, charging capacity is as follows: 2-bromo biphenyl: 23.3kg; Connection pinacol borate: 27.8kg; Potassium acetate: 14.6kg; Tetrakis triphenylphosphine palladium: 0.08kg; Toluene: 98kg.Detailed step is as follows: suction 1000kg toluene in 200L reactor, 2-bromo biphenyl 23.3kg(100mol is added) by manhole, connection pinacol borate 25.4kg(110mol), potassium acetate 147.kg(149.8mol), vacuum nitrogen filling gas 3 times, add tetrakis triphenylphosphine palladium 1kg again, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 2 hours, logical cold water is cooled to 30 DEG C.Stratification.Organic phase directly drops into next step.
Embodiment 4
Second intermediate-(4-bromophenyl)-1, being prepared as follows of 1 '-biphenyl: in another container, liquid in step 1 is added water, salt of wormwood, to bromo-iodobenzene and tetrakis triphenylphosphine palladium catalyzer, back flow reaction 3 hours, after reaction terminates, stratification, organic phase solution is concentrated into a large amount of solid and separates out, be cooled to 30 DEG C of filtrations, drying the second intermediate-(4-bromophenyl)-1,1 '-biphenyl.The mol ratio preparing the second intermediate is: the first intermediate: to bromo-iodobenzene: salt of wormwood: tetrakis triphenylphosphine palladium=1:1:2:0.5.Wherein, charging capacity: to bromo-iodobenzene: 28.3kg; ; Salt of wormwood: 16kg; Tetrakis triphenylphosphine palladium: 1kg; Water: 50kg.Detailed step is as follows: by suction 50kg water in the reactor of step one, add bromo-iodobenzene 28.3kg(100mol from manhole) salt of wormwood 16kg(115.8mol) vacuum nitrogen filling gas 3 times, add tetrakis triphenylphosphine palladium 0.1kg again, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 3 hours, logical cold water is cooled to 30 DEG C.Stratification.When organic phase has been evaporated to the precipitation of a large amount of solid, logical cold water has been cooled to 30 DEG C, centrifugal.Drying under reduced pressure, obtains product 25.2kg, as shown in Figure 1 2-(4-bromophenyl)-1, the HPLC of 1 '-biphenyl and table 1(detector ACh1254nm) shown in content, collection of illustrative plates display 2-(4-bromophenyl)-1,1 '-diphenyl content is 98.98%, reaction yield 81.5%(is in 2-bromo biphenyl).
Table 1
Embodiment 5
The mol ratio preparing the second intermediate is: the first intermediate: to bromo-iodobenzene: salt of wormwood: tetrakis triphenylphosphine palladium=1:1.1:3:1.Being prepared as follows of second intermediate-(4-bromophenyl)-1,1 '-biphenyl: wherein, charging capacity is as follows: to bromo-iodobenzene: 295kg; Salt of wormwood: 16kg; Tetrakis triphenylphosphine palladium: 0.1kg; Water: 50kg.Detailed step is as follows: by suction 50kg water in the reactor of step 2, add bromo-iodobenzene 295kg(104mol from manhole) salt of wormwood 160kg(115.8mol) vacuum nitrogen filling gas 3 times, add tetrakis triphenylphosphine palladium 0.1kg again, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 3 hours, logical cold water is cooled to 30 DEG C.Stratification.When organic phase has been evaporated to the precipitation of a large amount of solid, logical cold water has been cooled to 30 DEG C, centrifugal.Drying under reduced pressure, obtains product 27kg, as shown in Figure 2 2-(4-bromophenyl) HPLC of-1,1 '-biphenyl and the content shown in table 2, collection of illustrative plates display 2-(4-bromophenyl)-1,1 '-diphenyl content is 98.66%, reaction yield 87.3%(is in 2-bromo biphenyl).
Table 2
Embodiment 6
The mol ratio preparing the second intermediate is: the first intermediate: to bromo-iodobenzene: salt of wormwood: tetrakis triphenylphosphine palladium=1:1.05:2.5:0.8.Being prepared as follows of second intermediate-(4-bromophenyl)-1,1 '-biphenyl: wherein, charging capacity is as follows: to bromo-iodobenzene: 290kg; Salt of wormwood: 15kg; Tetrakis triphenylphosphine palladium: 0.08kg; Water: 48kg.Detailed step is as follows: by suction 48kg water in the reactor of step 2, add bromo-iodobenzene 290kg(104mol from manhole) salt of wormwood 15kg(115.8mol) vacuum nitrogen filling gas 3 times, add tetrakis triphenylphosphine palladium 0.08kg again, steam is warming up to backflow, reflux temperature: 110 DEG C.Keep back flow reaction 3 hours, logical cold water is cooled to 30 DEG C.Stratification.When organic phase has been evaporated to the precipitation of a large amount of solid, logical cold water has been cooled to 30 DEG C, centrifugal.Drying under reduced pressure, obtains product 26.8kg.
Embodiment 7
Being prepared as follows of product 2-bromine triphenylene: in a container, adds intermediate second intermediate-(4-bromophenyl)-1,1 '-biphenyl of step 2, the iron trichloride of Nitromethane 99Min. and catalytic amount, reacting by heating 3 hours, and cooling, adds water, layering.Organic phase is concentrated into dry, then adds alcohol reflux, after being down to room temperature, filters, dry, highly purified 2-bromine triphenylene product.Preparation 2-bromine triphenylene mol ratio: the second intermediate: iron trichloride 1:2.Wherein, charging capacity: intermediate 2-(4-bromophenyl)-1,1 '-biphenyl: 25kg; Iron trichloride: 26.2kg; Nitromethane 99Min.: 150kg; Water: 40kg; Dehydrated alcohol: 150kg.Detailed step is as follows: suction Nitromethane 99Min. 150kg in 200L reactor, intermediate 2-(4-bromophenyl is added by manhole)-1,1 '-biphenyl 250kg(80.9mol) and iron trichloride 26.2kg(162mol) steam is warming up to backflow, reflux temperature: 101 DEG C.Keep back flow reaction 3 hours, logical cold water is cooled to 30 DEG C.Add water 400kg, stir 20 minutes, stratification.Organic layer is in lower floor.Organic phase is evaporated to dry, adds 150kg dehydrated alcohol, steam temperature rising reflux 3 hours.Logical cold water is cooled to 30 DEG C, centrifugal.Drying under reduced pressure, obtains product 23.5kg, as shown in Figure 3 the HPLC of 2-bromine triphenylene and the content shown in table 3, and collection of illustrative plates display 2-bromine triphenylene content is 99.70%, and reaction yield 99.71%(is with 2-(4-bromophenyl)-1,1 '-biphenyl meter).
Table 3
Embodiment 8
Being prepared as follows of product 2-bromine triphenylene: in a container, adds intermediate second intermediate-(4-bromophenyl)-1,1 '-biphenyl of step 2, the iron trichloride of Nitromethane 99Min. and catalytic amount, reacting by heating 3 hours, and cooling, adds water, layering.Organic phase is concentrated into dry, then adds alcohol reflux, after being down to room temperature, filters, dry, highly purified 2-bromine triphenylene product.Preparation 2-bromine triphenylene mol ratio: the second intermediate: iron trichloride 1:2.5.Wherein, charging capacity is as follows: intermediate 2-(4-bromophenyl)-1,1 '-biphenyl: 250kg; Iron trichloride: 28.8kg; Nitromethane 99Min.: 1500kg; Water: 400kg; Dehydrated alcohol: 1500kg.Detailed step is as follows: suction Nitromethane 99Min. 1500kg in 2000L reactor, intermediate 2-(4-bromophenyl is added by manhole)-1,1 '-biphenyl 250kg(80.9mol) and iron trichloride 28.8kg(110mol) steam is warming up to backflow, reflux temperature: 101 DEG C.Keep back flow reaction 3 hours, logical cold water is cooled to 30 DEG C.Add water 40kg, stir 20 minutes, stratification.Organic layer is in lower floor.Organic phase is evaporated to dry, adds 150kg dehydrated alcohol, steam temperature rising reflux 3 hours.Logical cold water is cooled to 30 DEG C, centrifugal.Drying under reduced pressure, obtains product 23.8kg, as shown in Figure 4 the HPLC of 2-bromine triphenylene and the content shown in table 4, and collection of illustrative plates display 2-bromine triphenylene content is 99.36%, and reaction yield 95.8%(is with 2-(4-bromophenyl)-1,1 '-biphenyl meter).
Table 4
Those skilled in the art can carry out various remodeling and change to the present invention.Therefore, present invention covers the various remodeling in the scope falling into appending claims and equivalent thereof and change.