CN109912639A - A kind of bromo- 9,9- dimethyl silicon heterofluorene of 2- and its synthetic method - Google Patents
A kind of bromo- 9,9- dimethyl silicon heterofluorene of 2- and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of 2- bromo- 9,9- dimethyl silicon heterofluorene and its synthetic method, the following steps are included: step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein the molar ratio of o-dibromobenzene and n-BuLi is 1:0.48 ~ 0.55；2, the 2'- '-dibromobiphenyl and bromine that step 2 is generated using step 1) occur bromo-reaction and generate 2,2', 4-, tri- bromo biphenyl, wherein the molar ratio of 2,2'- '-dibromobiphenyls and bromine is 1:1 ~ 1.5；2,2', 4-, tri- bromo biphenyl and dichlorodimethylsilane that step 2 described in step 3) generates occur ring-closure reaction and generate bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane is 1:1 ~ 1.3.
Description
Technical field
The invention belongs to organic synthesis technical field more particularly to a kind of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- and its conjunctions
At method.
Background technique
Compound of fluorene class is due to high fluorescence quantum efficiency, the features such as high thermal stability, structure is easily modified, becomes blue light
Star molecule in material, but 9 carbon atoms of fluorene kind derivative are easily oxidized to Fluorenone at high temperature, and then cause long wave
Transmitting, reduces excitation purity and luminous efficiency.
9 C atoms that fluorenes is replaced using Si atom, can effectively be inhibited longwave transmissions, improve the stability of compound, obtain
To the silicon fluorene blue light material with high color purity.Bromo- 9, the 9- dimethyl silicon heterofluorene molecule of 2- is small, and dissolubility is good, and single bromination is closed
Object dissymmetrical structure allows compound flexibly to introduce different groups, has better performance, the at present change of this type
It is longer to close object synthetic route, higher cost.
Current existing production technology is only in the other research and development of gram-grade, can not expand as the other volume production of feather weight, below
Synthetic line in referenced patent CN103819455, the shortcomings that elaborate prior art:
The technique needs to restore in second step two nitros, is reducing agent with a large amount of glass putty, in acid condition
A large amount of hydrogen can be generated, inflammable and explosive, in industrialized production, risk is also greatly increased；It is diazonium in third step
Change reaction, Bisdiazonium salts can be generated, property is highly unstable, and reaction can be very violent, discharges a large amount of gas and energy, easily
Slug is even exploded, and is the leaving group of intermediate transfer with two iodine, and cost is very expensive；Five steps are reacted in total for this reaction,
Production cycle is long, at high cost, this is also the reason of technique cannot form large batch of production.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of bromo- 9,9- dimethyl silicon heterofluorene of 2- is provided
And its synthetic method, overcome in the prior art 1: current existing production technology is only in the other research and development of gram-grade, can not expand
The greatly other volume production of feather weight；2: reaction step is more, and the production cycle is long, at high cost；3: reaction process is dangerous, inflammable and explosive etc. asks
Topic.
In order to solve technical problem, the technical scheme is that a kind of synthesis side of bromo- 9, the 9- dimethyl silicon heterofluorene of 2-
Method, comprising the following steps:
Step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein adjacent dibromo
The molar ratio of benzene and n-BuLi is 1:0.48~0.55；
The 2,2'- '-dibromobiphenyl and bromine that step 2) is generated using step 1) occur bromo-reaction and generate 2,2', 4- tribromo
Biphenyl, wherein the molar ratio of 2,2'- '-dibromobiphenyls and bromine is 1:1~1.5；
The 2,2' that the step 3) step 2) generates, tri- bromo biphenyl of 4- and dichlorodimethylsilane occur ring-closure reaction and generate
Bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane is 1:1~1.3.
Preferably, the specific reaction step of the step 1) are as follows: in four-hole bottle lead to argon gas protection under, be added o-dibromobenzene and
Tetrahydrofuran, stirring is lower to be cooled to -78 DEG C using ethanol bath, starts that n-BuLi is added dropwise, -78 DEG C are maintained at after dripping off and is stirred
1h removes ethanol bath, is to slowly warm up to 0 DEG C, and hydrochloric acid is added dropwise, separates organic phase, organic phase is rotated solvent, residue second
Acetoacetic ester extracts, and washing is primary, and organic phase concentration is dry, and crude product carries out recrystallization purifying with n-hexane to get 2,2'- dibromo connection
Benzene.
Preferably, the molar ratio of the o-dibromobenzene and n-BuLi is 1:0.5.
Preferably, the specific reaction step of the step 2) are as follows: 2,2'- '-dibromobiphenyl, dichloroethanes are added into there-necked flask
And catalyst, it is warming up to 45~50 DEG C under stirring, bromine and dichloroethanes mixed liquor is added dropwise, drips off 45~50 DEG C of rear temperature control instead
It answers, using gas-chromatography tracking sampling, raw material reaction < 2% stops reaction, is cooled to 20 DEG C, reaction solution is poured slowly into saturation
Sodium hydrogensulfite aqueous solution in, stir 10 minutes, separate organic phase, organic phase rotates solvent, and residue crosses a silicon
It is recrystallized after rubber column gel column with n-hexane and dichloroethanes, wherein the weight ratio of n-hexane and dichloroethanes is 3:1, is obtained white solid
Tri- bromo biphenyl of body 2,2', 4-.
Preferably, the catalyst be iron powder, wherein the molar ratio of 2,2'- '-dibromobiphenyls and iron powder be 1:0.015~
0.03。
Preferably, the specific reaction step of the step 3) are as follows: under argon gas protection, 2,2', 4- tribromo is added into there-necked flask
System is cooled to -78 DEG C using ethanol bath, n-BuLi is slowly added dropwise by biphenyl and tetrahydrofuran, after dripping off keep -78 DEG C simultaneously
1h is stirred, dichlorodimethylsilane is added dropwise into reaction system, is slowly warming up to 25 DEG C after keeping the temperature 1h after dripping off, and stir 12h,
It is extracted with ethyl acetate reaction solution, and after being washed with water, dry organic phase, after then crossing silica column, with n-hexane and two
Chloroethanes is recrystallized, and wherein the weight ratio of n-hexane and dichloroethanes is 5:1 to get bromo- 9, the 9- dimethyl silicon heterofluorene of 2-.
Preferably, the molar ratio of 2,2', 4-, tri- bromo biphenyl and dichlorodimethylsilane is 1:1.1.
Preferably, bromo- 9, the 9- dimethyl silicon heterofluorene of a kind of 2-, bromo- 9, the 9- dimethyl silicon heterofluorene of 2- is by above-mentioned any
The synthesis of synthetic method described in one.
Compared with the existing technology, the present invention has the advantages that
(1) for the present invention using simple o-dibromobenzene as initial feed, intermediate auxiliary material is bromine, n-BuLi, dichloro two
Methyl-monosilane etc., the reaction of coupling, bromo and closed loop synthesis silicon fluorene bridged bond including o-dibromobenzene and etc., in o-dibromobenzene
Coupling reaction step in, 2- bromobenzene lithium reagent is prepared using ultralow temperature, and is coupled with o-dibromobenzene itself, selection is suitable
Equivalent material ratio, guarantee reaction smooth complete progress；In bromo-reaction, using iron powder catalyst, using bromine as bromine source into
Row bromo-reaction, bromo is selectively good, high income, and purification process is simple；In the anti-of final step closed loop synthesis silicon fluorene bridged bond
It answers, using ultralow temperature, closed loop is reacted with n-BuLi selective reduction and with dichlorodimethylsilane and generates silicon fluorene bridged bond, product
Content > 98%, gross production rate are greater than 49%；
(2) the invention discloses a kind of methods for preparing bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, from initial feed o-dibromobenzene
Starting, only needs three steps that can synthesize target product, reaction step is short, and easy to operate, with short production cycle, supplementary product consumption is less,
The whole cost of raw material is cheap, is suitably applied industrialized production；
(3) the invention avoids, with bis-diazotized reaction, improving the safety during experimental implementation in experimentation,
It ensure that production safety.
Specific embodiment
The specific embodiment of the invention is described below with reference to embodiment:
It should be noted that structure, ratio, size etc. that this specification is illustrated, only to cooperate specification to be taken off
The content shown is not intended to limit the invention enforceable qualifications, appoints so that those skilled in the art understands and reads
What modification of structure, the change of proportionate relationship or adjustment of size, is not influencing the effect of present invention can be generated and can reach
At purpose under, should all still fall in the range of disclosed technology contents can cover.
Meanwhile cited such as "upper" in this specification, "lower", "left", "right", " centre " and " one " term, also
Only being illustrated convenient for narration, rather than to limit the scope of the invention, relativeness is altered or modified, in nothing
Under essence change technology contents, when being also considered as the enforceable scope of the present invention.
Raw material o-dibromobenzene of the present invention, n-BuLi, bromine, dichlorodimethylsilane, tetrahydrofuran, ethyl alcohol, salt
Acid, ethyl acetate, n-hexane, dichloroethanes, sodium hydrogensulfite, iron powder etc. are commercial products, the non-reactor product in part it is dense
Degree and dosage be amount commonly used in the art, concentration and dosage on the application without influence, therefore omit.
Embodiment 1
The invention discloses a kind of synthetic methods of bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, comprising the following steps:
Step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein adjacent dibromo
The molar ratio of benzene and n-BuLi is 1:0.48~0.55；
The 2,2'- '-dibromobiphenyl and bromine that step 2) is generated using step 1) occur bromo-reaction and generate 2,2', 4- tribromo
Biphenyl, wherein the molar ratio of 2,2'- '-dibromobiphenyls and bromine is 1:1~1.5；
The 2,2' that the step 3) step 2) generates, tri- bromo biphenyl of 4- and that ring-closure reaction occurs with dichlorodimethylsilane is raw
At bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane be 1:1~
1.3。
Embodiment 2
The invention discloses a kind of synthetic methods of bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, comprising the following steps:
Step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein adjacent dibromo
The molar ratio of benzene and n-BuLi is 1:0.48~0.55；
The 2,2'- '-dibromobiphenyl and bromine that step 2) is generated using step 1) occur bromo-reaction and generate 2,2', 4- tribromo
Biphenyl, wherein the molar ratio of 2,2'- '-dibromobiphenyls and bromine is 1:1~1.5；
The 2,2' that the step 3) step 2) generates, tri- bromo biphenyl of 4- and that ring-closure reaction occurs with dichlorodimethylsilane is raw
At bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane be 1:1~
1.3。
Preferably, the specific reaction step of the step 1) are as follows: in four-hole bottle lead to argon gas protection under, be added o-dibromobenzene and
Tetrahydrofuran, stirring is lower to be cooled to -78 DEG C using ethanol bath, starts that n-BuLi is added dropwise, -78 DEG C are maintained at after dripping off and is stirred
1h removes ethanol bath, is to slowly warm up to 0 DEG C, and hydrochloric acid is added dropwise, separates organic phase, organic phase is rotated solvent, residue second
Acetoacetic ester extracts, and washing is primary, and organic phase concentration is dry, and crude product carries out recrystallization purifying with n-hexane to get 2,2'- dibromo connection
Benzene.
Preferably, the molar ratio of the o-dibromobenzene and n-BuLi is 1:0.5.
Embodiment 3
The invention discloses a kind of synthetic methods of bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, comprising the following steps:
Step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein adjacent dibromo
The molar ratio of benzene and n-BuLi is 1:0.48~0.55；
The 2,2'- '-dibromobiphenyl and bromine that step 2) is generated using step 1) occur bromo-reaction and generate 2,2', 4- tribromo
Biphenyl, wherein the molar ratio of 2,2'- '-dibromobiphenyls and bromine is 1:1~1.5；
The 2,2' that the step 3) step 2) generates, tri- bromo biphenyl of 4- and that ring-closure reaction occurs with dichlorodimethylsilane is raw
At bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane be 1:1~
1.3。
Preferably, the specific reaction step of the step 1) are as follows: in four-hole bottle lead to argon gas protection under, be added o-dibromobenzene and
Tetrahydrofuran, stirring is lower to be cooled to -78 DEG C using ethanol bath, starts that n-BuLi is added dropwise, -78 DEG C are maintained at after dripping off and is stirred
1h removes ethanol bath, is to slowly warm up to 0 DEG C, and hydrochloric acid is added dropwise, separates organic phase, organic phase is rotated solvent, residue second
Acetoacetic ester extracts, and washing is primary, and organic phase concentration is dry, and crude product carries out recrystallization purifying with n-hexane to get 2,2'- dibromo connection
Benzene.
Preferably, the molar ratio of the o-dibromobenzene and n-BuLi is 1:0.5.
Preferably, the specific reaction step of the step 2) are as follows: 2,2'- '-dibromobiphenyl, dichloroethanes are added into there-necked flask
And catalyst, it is warming up to 45~50 DEG C under stirring, bromine and dichloroethanes mixed liquor is added dropwise, drips off 45~50 DEG C of rear temperature control instead
It answers, using GC tracking sampling, raw material reaction < 2% stops reaction, is cooled to 20 DEG C, reaction solution is poured slowly into the sulfurous of saturation
In the aqueous solution of sour hydrogen sodium, stirs 10 minutes, separate organic phase, organic phase rotates solvent, after residue crosses a silicagel column
It is recrystallized with n-hexane and dichloroethanes, wherein the weight ratio of n-hexane and dichloroethanes is 3:1, white solid 2 is obtained,
Tri- bromo biphenyl of 2', 4-.
Preferably, the catalyst be iron powder, wherein the molar ratio of 2,2'- '-dibromobiphenyls and iron powder be 1:0.015~
0.03。
Embodiment 4
The invention discloses a kind of synthetic methods of bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, comprising the following steps:
Step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein adjacent dibromo
The molar ratio of benzene and n-BuLi is 1:0.48~0.55；
The 2,2'- '-dibromobiphenyl and bromine that step 2) is generated using step 1) occur bromo-reaction and generate 2,2', 4- tribromo
Biphenyl, wherein the molar ratio of 2,2'- '-dibromobiphenyls and bromine is 1:1~1.5；
The 2,2' that the step 3) step 2) generates, tri- bromo biphenyl of 4- and that ring-closure reaction occurs with dichlorodimethylsilane is raw
At bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane be 1:1~
1.3。
Preferably, the specific reaction step of the step 1) are as follows: in four-hole bottle lead to argon gas protection under, be added o-dibromobenzene and
Tetrahydrofuran, stirring is lower to be cooled to -78 DEG C using ethanol bath, starts that n-BuLi is added dropwise, -78 DEG C are maintained at after dripping off and is stirred
1h removes ethanol bath, is to slowly warm up to 0 DEG C, and hydrochloric acid is added dropwise, separates organic phase, organic phase is rotated solvent, residue second
Acetoacetic ester extracts, and washing is primary, and organic phase concentration is dry, and crude product carries out recrystallization purifying with n-hexane to get 2,2'- dibromo connection
Benzene.
Preferably, the molar ratio of the o-dibromobenzene and n-BuLi is 1:0.5.
Preferably, the specific reaction step of the step 2) are as follows: 2,2'- '-dibromobiphenyl, dichloroethanes are added into there-necked flask
And catalyst, it is warming up to 45~50 DEG C under stirring, bromine and dichloroethanes mixed liquor is added dropwise, drips off 45~50 DEG C of rear temperature control instead
It answers, using GC tracking sampling, raw material reaction < 2% stops reaction, is cooled to 20 DEG C, reaction solution is poured slowly into the sulfurous of saturation
In the aqueous solution of sour hydrogen sodium, stirs 10 minutes, separate organic phase, organic phase rotates solvent, after residue crosses a silicagel column
It is recrystallized with n-hexane and dichloroethanes, wherein the weight ratio of n-hexane and dichloroethanes is 3:1, white solid 2 is obtained,
Tri- bromo biphenyl of 2', 4-.
Preferably, the catalyst be iron powder, wherein the molar ratio of 2,2'- '-dibromobiphenyls and iron powder be 1:0.015~
0.03。
Preferably, the specific reaction step of the step 3) are as follows: under argon gas protection, 2,2', 4- tribromo is added into there-necked flask
System is cooled to -78 DEG C using ethanol bath, n-BuLi is slowly added dropwise by biphenyl and tetrahydrofuran, after dripping off keep -78 DEG C simultaneously
1h is stirred, dichlorodimethylsilane is added dropwise into reaction system, is slowly warming up to 25 DEG C after keeping the temperature 1h after dripping off, and stir 12h,
It is extracted with ethyl acetate reaction solution, and after being washed with water, dry organic phase, after then crossing silica column, with n-hexane and two
Chloroethanes is recrystallized, and wherein the weight ratio of n-hexane and dichloroethanes is 5:1 to get bromo- 9, the 9- dimethyl silicon heterofluorene of 2-.
Preferably, the molar ratio of 2,2', 4-, tri- bromo biphenyl and dichlorodimethylsilane is 1:1.1.
Preferably, bromo- 9, the 9- dimethyl silicon heterofluorene of a kind of 2-, bromo- 9, the 9- dimethyl silicon heterofluorene of 2- is by above-mentioned any
The synthesis of synthetic method described in one.
The reaction route of the bromo- 9,9- dimethyl silicon heterofluorene synthetic method of 2- of the present invention is as follows:
In above-mentioned reaction route 2-A be o-dibromobenzene, 2-B 2,2'- '-dibromobiphenyl, tri- bromo biphenyl of 2-C 2,2', 4-,
Compound 1 is the bromo- 9,9- dimethyl silicon heterofluorene of 2-.
Embodiment 5
Step 1): it the preparation of 2,2'- '-dibromobiphenyls (2-B): under argon gas protection, is added into the four-hole bottle of dry 5L
200g (0.85mol) o-dibromobenzene and dry 1600ml tetrahydrofuran, then cool to -78 DEG C, in the protection of argon gas
Under the n-BuLi of 205ml (0.41mol, 2mol/L) is added dropwise, stirred when being added dropwise, at -78 DEG C, the reaction was continued after dripping off 1
Hour, it is then to slowly warm up to 0 DEG C again, has reacted and the reaction of 420ml hydrochloric acid is added, be then extracted with ethyl acetate two to three
Time, ethyl acetate layer is taken, solvent is removed, obtains 2,2'- '-dibromobiphenyl crude material, be then recrystallized to give with n-hexane pure
2,2'- '-dibromobiphenyls (2-B) are white solid powder 108g, content 99.3%, yield 82%.
Step 2): the preparation of tri- bromo biphenyl of 2,2', 4- (2-C): being added 100g (0.32mol) 2-B in the there-necked flask of 2L,
600ml dichloroethanes, 0.3g iron powder (5mmol) are warming up to 50 DEG C under stirring, bromine 51.2gBr is added dropwise2(0.32mol) and
The dichloroethanes mixed liquor of 200ml is stirred when being added dropwise, and 50 DEG C are kept the temperature after dripping off and is reacted 8 hours, and gas-chromatography (GC) tracking is anti-
Process is answered, raw material reaction < 2% stops reaction, is cooled to 20 DEG C, and reaction solution is poured slowly into the sodium hydrogensulfite of 500ml saturation
Aqueous solution in, stir 10 minutes, stratification separates organic phase, and organic phase is washed 2 times, and organic phase is dry with anhydrous sodium sulfate
It is dry, desiccant is filtered off, filtrate removes solvent and obtains 2,2', 4- tribromo biphenyl crude product product, then crude product n-hexane: dichloro=
3:1 ratio is recrystallized, and faint yellow solid 2,2', tri- bromo biphenyl of 4- (2-C) 77.8g, content 98.6%, yield 62% are obtained.
Step 3): the preparation of bromo- 9, the 9- dimethyl silicon heterofluorene (compound 1) of 2-: under argon gas protection, to the three of dry 2L
50g (0.13mol) 2-C is added in mouth bottle, then dry 400ml tetrahydrofuran cools to -78 DEG C, in the guarantor of argon gas
The n-BuLi of 135ml (0.27mol, 2mol/L) is added dropwise under shield, is stirred when being added dropwise, continues instead after dripping off at -78 DEG C
It answers 1 hour, 19g (0.143mol) dichlorodimethylsilane is added dropwise into system, stirred when being added dropwise, -78 after dripping off
DEG C the reaction was continued 1 hour, is then to slowly warm up to room temperature again and stirs 12h, and water quenching is added into reaction solution and goes out, uses ethyl acetate
Reaction solution is extracted, stratification separates organic phase, and organic phase is washed 2 times, and organic phase is dry with anhydrous sodium sulfate, filters off drying
Agent, filtrate remove solvent and obtain bromo- 9, the 9- dimethyl silicon heterofluorene crude material of 2-, then crude product n-hexane: dichloroethanes=
5:1 be recrystallized to give bromo- 9, the 9- dimethyl silicon heterofluorene (compound 1) of 18.5g sterling white crystal 2-, content 98.5%,
Yield 50%.
Embodiment 6
Step 1): it the preparation of 2,2'- '-dibromobiphenyls (2-B): under argon gas protection, is added into the four-hole bottle of dry 10L
650g (2.75mol) o-dibromobenzene and 2200 dry tetrahydrofurans, then cool to -78 DEG C, under the protection of argon gas
The n-BuLi of 715ml (1.375mol, 2mol/L) is added dropwise, is stirred when being added dropwise, the reaction was continued at -78 DEG C after dripping off 1
Hour, it is then to slowly warm up to 0 DEG C again, has reacted and the reaction of 1400ml hydrochloric acid is added, be then extracted with ethyl acetate two and arrive
Three times, ethyl acetate layer is taken, solvent is removed, obtains 2,2'- '-dibromobiphenyl crude material, be then recrystallized to give with n-hexane pure
2,2'- '-dibromobiphenyl (2-B), be white solid powder 339g, content 98.8%, yield 79%.
Step 2): the preparation of tri- bromo biphenyl of 2,2', 4- (2-C): being added 275g (0.88mol) 2-B in the there-necked flask of 5L,
1700ml dichloroethanes, 1g iron powder (20mmol) are warming up to 50 DEG C under stirring, be added dropwise bromine 211gBr2 (1.32.mol) and
The dichloroethanes mixed liquor of 550ml is stirred when being added dropwise, and 50 DEG C are kept the temperature after dripping off and is reacted 8 hours, and gas-chromatography (GC) tracking is anti-
Process is answered, raw material reaction < 2% stops reaction, is cooled to 20 DEG C, and reaction solution is poured slowly into the sodium hydrogensulfite of 1400ml saturation
Aqueous solution in, stir 10 minutes, stratification separates organic phase, and organic phase is washed 2 times, and organic phase is dry with anhydrous sodium sulfate
It is dry, desiccant is filtered off, filtrate removes solvent and obtains 2,2', 4- tribromo biphenyl crude product product, then crude product n-hexane: dichloro=
3:1 ratio is recrystallized, and faint yellow solid 2,2', tri- bromo biphenyl of 4- (2-C) 230g, content 98.3%, yield 67% are obtained.
Step 3): the preparation of bromo- 9, the 9- dimethyl silicon heterofluorene (compound 1) of 2-: under argon gas protection, to the three of dry 3L
155g (0.4mol) 2-C is added in mouth bottle, then dry 1000ml tetrahydrofuran cools to -78 DEG C, in the guarantor of argon gas
The n-BuLi of 368ml (0.73mol, 2mol/L) is added dropwise under shield, is stirred when being added dropwise, continues instead after dripping off at -78 DEG C
It answers 1 hour, 51.6g (0.4mol) dichlorodimethylsilane is added dropwise into system, stirred when being added dropwise, -78 after dripping off
DEG C the reaction was continued 1 hour, is then to slowly warm up to room temperature again and stirs 12h, and water quenching is added into reaction solution and goes out, uses ethyl acetate
Reaction solution is extracted, stratification separates organic phase, and organic phase is washed 2 times, and organic phase is dry with anhydrous sodium sulfate, filters off drying
Agent, filtrate remove solvent and obtain bromo- 9, the 9- dimethyl silicon heterofluorene crude material of 2-, then crude product n-hexane: dichloroethanes=
5:1 be recrystallized to give bromo- 9, the 9- dimethyl silicon heterofluorene (compound 1) of 53.8g sterling white crystal 2-, content 98.3%,
Yield 57%.
Embodiment 7
Step 1): it the preparation of 2,2'- '-dibromobiphenyls (2-B): under argon gas protection, is added into the four-hole bottle of dry 2L
200g (0.33mol) o-dibromobenzene and dry 640ml tetrahydrofuran, then cool to -78 DEG C, under the protection of argon gas
The n-BuLi of 90ml (0.18mol, 2mol/L) is added dropwise, is stirred when being added dropwise, it is 1 small that the reaction was continued at -78 DEG C after dripping off
When, it is then to slowly warm up to 0 DEG C again, has reacted and the reaction of 160ml hydrochloric acid is added, be then extracted with ethyl acetate two to three
Time, ethyl acetate layer is taken, solvent is removed, obtains 2,2'- '-dibromobiphenyl crude material, be then recrystallized to give with n-hexane pure
2,2'- '-dibromobiphenyls (2-B) are white solid powder 39g, content 99.6%, yield 75%.
Step 2): the preparation of tri- bromo biphenyl of 2,2', 4- (2-C): being added 25g (0.08mol) 2-B in the there-necked flask of 1L,
150ml dichloroethanes, 0.13g iron powder (2.4mmol) are warming up to 50 DEG C under stirring, be added dropwise bromine 15.3gBr2 (0.096mol)
It with the dichloroethanes mixed liquor of 50ml, is stirred when being added dropwise, 50 DEG C is kept the temperature after dripping off and is reacted 8 hours, gas-chromatography (GC) tracking
Reaction process, raw material reaction < 2% stop reaction, are cooled to 20 DEG C, and reaction solution is poured slowly into the bisulfite of 500ml saturation
It in the aqueous solution of sodium, stirs 10 minutes, stratification, separates organic phase, organic phase is washed 2 times, organic phase anhydrous sodium sulfate
It is dry, desiccant is filtered off, filtrate removes solvent and obtains 2,2', 4- tribromo biphenyl crude product product, then crude product n-hexane: dichloro
=3:1 ratio is recrystallized, and faint yellow solid 2,2', tri- bromo biphenyl of 4- (2-C) 17.2g, content 99.1%, yield are obtained
55%.
Step 3): the preparation of bromo- 9, the 9- dimethyl silicon heterofluorene (compound 1) of 2-: under argon gas protection, to the three of dry 1L
17g (0.043mol) 2-C is added in mouth bottle, then dry 140ml tetrahydrofuran cools to -78 DEG C, in the guarantor of argon gas
The n-BuLi of 49ml (0.1mol, 2mol/L) is added dropwise under shield, is stirred when being added dropwise, the reaction was continued at -78 DEG C after dripping off 1
Hour, 7.2g is added dropwise into system
(0.056mol) dichlorodimethylsilane, while be added dropwise while stir, at -78 DEG C, the reaction was continued after dripping off 1 hour, then
It is to slowly warm up to room temperature again and stirs 12h, water quenching is added into reaction solution and goes out, is extracted with ethyl acetate reaction solution, stratification,
Organic phase is separated, organic phase is washed 2 times, and organic phase is dry with anhydrous sodium sulfate, filters off desiccant, and filtrate removes solvent and obtains 2-
Bromo- 9,9- dimethyl silicon heterofluorene crude material, then crude product n-hexane: dichloroethanes=5:1 carries out being recrystallized to give 6.2g
Bromo- 9, the 9- dimethyl silicon heterofluorene (compound 1) of sterling white crystal 2-, content 98.6%, yield 49%.
Above embodiments of the present invention are prepared into bromo- 98% or more 9, the 9- dimethyl silicon heterofluorene content of 2-, are important OLED
Material intermediate has expanded application of the silicon fluorene analog derivative as intermediate in organic photoelectrical material design synthesis, the present invention
Preparation step is short, and the cost of raw material is cheap, easy to operate, is suitably applied industrialized production.
For the present invention using simple o-dibromobenzene as initial feed, intermediate auxiliary material is bromine, n-BuLi, dichloro-dimethyl
Silane etc., the reaction of coupling, bromo and closed loop synthesis silicon fluorene bridged bond including o-dibromobenzene and etc., in the idol of o-dibromobenzene
Join in reaction step, 2- bromobenzene lithium reagent is prepared using ultralow temperature, and be coupled with o-dibromobenzene itself, select suitable work as
Amount material ratio, guarantees the smooth complete progress of reaction；In bromo-reaction, using iron powder catalyst, bromine is carried out by bromine source of bromine
Generation reaction, bromo is selectively good, high income, and purification process is simple；In the reaction of final step closed loop synthesis silicon fluorene bridged bond, adopt
With ultralow temperature, closed loop is reacted with n-BuLi selective reduction and with dichlorodimethylsilane and generates silicon fluorene bridged bond, product assay >
98%, gross production rate is greater than 49%.
The invention discloses a kind of methods for preparing bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, open from initial feed o-dibromobenzene
Begin, only needs three steps that can synthesize target product, reaction step is short, and easy to operate, with short production cycle, supplementary product consumption is less, whole
The body cost of raw material is cheap, is suitably applied industrialized production；The invention avoids, with bis-diazotized reaction, mention in experimentation
Safety during high experimental implementation, ensure that production safety.
The preferred embodiment for the present invention is explained in detail above, but the present invention is not limited to the above embodiments,
Those of ordinary skill in the art within the scope of knowledge, can also make various without departing from the purpose of the present invention
Variation.
Many other changes and remodeling can be made by not departing from the spirit and scope of the present invention.It should be appreciated that the present invention is not
It is limited to specific embodiment, the scope of the present invention is defined by the following claims.
Claims (8)
1. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2-, it is characterised in that: the following steps are included:
Step 1) undergoes coupling reaction to produce 2,2'- '-dibromobiphenyl using o-dibromobenzene and n-BuLi, wherein o-dibromobenzene with
The molar ratio of n-BuLi is 1:0.48 ~ 0.55；
2, the 2'- '-dibromobiphenyl and bromine that step 2 is generated using step 1) occur bromo-reaction and generate 2,2', 4-, tri- bromo biphenyl,
Wherein the molar ratio of 2,2'- '-dibromobiphenyl and bromine is 1:1 ~ 1.5；
The 2,2' that step 2 described in step 3) generates, tri- bromo biphenyl of 4- and dichlorodimethylsilane occur ring-closure reaction and generate 2-
Bromo- 9,9- dimethyl silicon heterofluorene, wherein the molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane is 1:1 ~ 1.3.
2. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- according to claim 1, which is characterized in that described
The specific reaction step of step 1) are as follows: lead under argon gas protection in four-hole bottle, o-dibromobenzene and tetrahydrofuran is added, stir lower utilize
Ethanol bath is cooled to -78 DEG C, starts that n-BuLi is added dropwise, -78 DEG C are maintained at after dripping off and stirs 1h, removes ethanol bath, slowly
It is warming up to 0 DEG C, hydrochloric acid is added dropwise, separates organic phase, organic phase is rotated into solvent, residue with Ethyl acetate extracts, washing one
Secondary, organic phase concentration is dry, and crude product carries out recrystallization purifying with n-hexane to get 2,2'- '-dibromobiphenyl.
3. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- according to claim 2, it is characterised in that: described
The molar ratio of o-dibromobenzene and n-BuLi is 1:0.5.
4. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- according to claim 1, which is characterized in that described
The specific reaction step of step 2 are as follows: 2,2'- '-dibromobiphenyl, dichloroethanes and catalyst are added into there-necked flask, stirs lower heating
To 45 ~ 50 DEG C, bromine and dichloroethanes mixed liquor is added dropwise, drips off 45 ~ 50 DEG C of rear temperature control reactions, is taken using gas-chromatography tracking
Sample, raw material reaction < 2% stop reaction, are cooled to 20 DEG C, reaction solution are poured slowly into the aqueous solution of the sodium hydrogensulfite of saturation,
Stirring 10 minutes separates organic phase, and organic phase rotates solvent, and residue uses n-hexane and dichloroethanes after crossing a silicagel column
It is recrystallized, wherein the weight ratio of n-hexane and dichloroethanes is 3:1, obtains white solid 2,2', tri- bromo biphenyl of 4-.
5. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- according to claim 4, it is characterised in that: described
Catalyst is iron powder, wherein the molar ratio of 2,2'- '-dibromobiphenyls and iron powder is 1:0.015 ~ 0.03.
6. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- according to claim 1, which is characterized in that described
The specific reaction step of step 3) are as follows: under argon gas protection, 2,2', 4-, tri- bromo biphenyl and tetrahydrofuran are added into there-necked flask, utilizes
System is cooled to -78 DEG C by ethanol bath, and n-BuLi is slowly added dropwise, and -78 DEG C are kept after dripping off and stirs 1h, into reaction system
Dichlorodimethylsilane is added dropwise, is slowly warming up to 25 DEG C after keeping the temperature 1h after dripping off, and stir 12h, is extracted with ethyl acetate reaction
Liquid, and after being washed with water, dry organic phase is recrystallized after then crossing silica column with n-hexane and dichloroethanes,
The weight ratio of middle n-hexane and dichloroethanes is 5:1 to get bromo- 9, the 9- dimethyl silicon heterofluorene of 2-.
7. a kind of synthetic method of bromo- 9, the 9- dimethyl silicon heterofluorene of 2- according to claim 6, it is characterised in that: described
The molar ratio of tri- bromo biphenyl of 2,2', 4- and dichlorodimethylsilane is 1:1.1.
8. a kind of bromo- 9,9- dimethyl silicon heterofluorene of 2-, it is characterised in that: bromo- 9, the 9- dimethyl silicon heterofluorene of 2- is wanted by right
The synthesis of synthetic method described in asking any one of 1 to 7.
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| CN102625819A (en) * | 2009-07-23 | 2012-08-01 | 罗门哈斯电子材料韩国有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN101693651A (en) * | 2009-10-17 | 2010-04-14 | 西北师范大学 | Synthetic method of 4-biphenylcarboxaldehyde |
| JP2011105718A (en) * | 2009-11-13 | 2011-06-02 | Doosan Corp | Anthracene derivative, and organic electroluminescent element by using the same |
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Application publication date: 20190621 |