CN108276300A - It is a kind of with carboxyl be oriented to base prepare the method for biphenyl type tri-arylamine group compound, intermediate and preparation method thereof - Google Patents
It is a kind of with carboxyl be oriented to base prepare the method for biphenyl type tri-arylamine group compound, intermediate and preparation method thereof Download PDFInfo
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- 0 Cc1cc(N(c(cc2)ccc2-c(cc2)ccc2N(c2cccc(C)c2)c2ccccc2*(C#C)=C)c2c(*)cccc2)ccc1 Chemical compound Cc1cc(N(c(cc2)ccc2-c(cc2)ccc2N(c2cccc(C)c2)c2ccccc2*(C#C)=C)c2c(*)cccc2)ccc1 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/56—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position
- C07C229/58—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of a six-membered aromatic ring, e.g. N-phenyl-anthranilic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
Abstract
It is to be oriented to base to prepare the method for biphenyl type tri-arylamine group compound, intermediate and preparation method thereof that the present invention relates to a kind of with carboxyl.The intermediate has the structure being shown below：
Description
Technical field
The invention belongs to the synthesis fields of biphenyl type tri-arylamine group compound, and in particular to one kind is the base system that is oriented to carboxyl
The method of standby biphenyl type tri-arylamine group compound, intermediate and preparation method thereof.
Background technology
In organic hole transport material, tri-arylamine group compound can form ammonium ion free radical under electric field action,
Make it have higher hole mobility and good hole transport performance.Current developed triarylamine analog hole transport materials
Mainly there are the three classes such as triaryl amine containing fluorenes ring in triphenylamine and its derivative, biphenyl type tri-arylamine group compound and molecule
Close object.Wherein alkyl-substituted biphenyls type tri-arylamine group compound not only has high hole mobility and stability, but also because dividing
So that it is had larger dissolubility in resin containing non-polar group as methyl in son, is not easy to ooze out from organic resin.
Low molecular symmetry can drop in the introducing of alkyl substituent simultaneously, increase the rotamer number of molecule, divide to change
The clustered pattern of son, is effectively prevented the crystallization trend of molecule, carries the thermal stability of high molecular film forming and film.In addition
Glass transition temperature (the T of this kind of compoundg) generally higher, it can be to avoid due to the low T of materialgCaused transport layer is soft
The problems such as change, hole transporting material are oozed out from organic resin and transmission performance declines.
As the research hotspot and emphasis of hole mobile material, the synthesis of biphenyl type tri-arylamine group compound, which receives always, grinds
The concern of hair personnel, traditional preparation methods mainly use Ullmann reaction methods and Buchwald-Hartwig reaction methods.But it is existing
The temperature for preparing the reaction system of biphenyl type tri-arylamine group compound in document by Ullmann reaction methods is higher, the time is longer,
Yield and purity are low, and efficient ligand, which will usually pass through complicated technique, to be synthesized；And Buchwald-Hartwig is anti-
Answer expensive catalyst used in method so that the biphenyl type tri-arylamine group compound cost of preparation is high, be unfavorable for its
The popularization and application in hole mobile material field.
The patent application of Publication No. CN1769369A discloses a kind of preparation method of triarylamine analog hole transport materials,
Its using aromatic secondary amine, fragrance iodine for object as reaction raw materials, under the catalyst system and catalyzing of metal halide/1,10- ferrosin/alkali into
Prepared by row reaction, to make reaction condition milder of the aromatic secondary amine with fragrance iodine for object, shorten the reaction time and improve and react
Yield.The preparation method prepare biphenyl type tri-arylamine group compound primary raw material be N, N '-diphenylbenzidines, the raw material
Industrial cost is higher, is unfavorable for promoting and applying in the industrialized production of biphenyl type tri-arylamine group compound.
Invention content
The purpose of the present invention is to provide a kind of intermediates being used to prepare biphenyl type tri-arylamine group compound, to solve
The high problem of industrial production cost existing for the technology path of existing synthesis biphenyl type tri-arylamine group compound.
Second purpose of the invention is to provide the preparation method of above-mentioned intermediate.
It is to be oriented to base to prepare biphenyl type tri-arylamine group compound that third object of the present invention is to provide a kind of with carboxyl
Method.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of intermediate being used to prepare biphenyl type tri-arylamine group compound has the structure as shown in formula (1)：
In formula (1), R is selected from the halogenated alkyl that hydrogen, the alkyl that carbon atom number is 1-10, carbon atom number are 1-5, carbon atom number
Alkoxy, aryl for 1-5.
Provided by the present invention for preparing the intermediate of biphenyl type tri-arylamine group compound, using raw material simple and easy to get
Synthesis is prepared, with the purity and high income of biphenyl type tri-arylamine group compound prepared by the intermediate, biphenyl can be significantly reduced
The production cost of type tri-arylamine group compound, is highly suitable for the industrialized production of biphenyl type tri-arylamine group compound.
Preferably, R H, methyl, butyl, trifluoromethyl, methoxyl group or phenyl.
Technical solution is used by the preparation method of the above-mentioned intermediate for being used to prepare biphenyl type tri-arylamine group compound：
A kind of preparation method for the intermediate being used to prepare biphenyl type tri-arylamine group compound, including：By substituted diphenylamine,
4,4 '-dihalo- biphenyl, metal carbonate, the first catalyst reacted at 150-200 DEG C in the first solvent to get；Institute
The structural formula for stating substituted diphenylamine is：Wherein R be selected from hydrogen, carbon atom number be 1-10 alkyl,
Alkoxy that halogenated alkyl that carbon atom number is 1-5, carbon atom number are 1-5, aryl.
In substituted diphenylamine, R is preferably H, methyl, butyl, trifluoromethyl, methoxyl group or phenyl.
The metal carbonate is one or more combinations in potassium carbonate, sodium carbonate, sodium bicarbonate, cesium carbonate.
First catalyst is copper and/or copper oxide.
Preferably, substituted diphenylamine, 4,4 '-dihalo- biphenyl, metal carbonate, the first catalyst the ratio between the amount of substance be
1：(0.4-0.5)：(2-4)：0.04.It is further preferred that first catalyst is mass ratio 1:1 copper and copper oxide composition
Mixture.The time reacted at 150-200 DEG C is 2-10h.
First solvent is N, one kind in accelerine, diethylene glycol ether, nitrobenzene, dimethyl sulfoxide.It is excellent
Choosing, substituted diphenylamine, 4,4 '-dihalo- biphenyl, metal carbonate, copper, copper oxide, the first solvent the ratio between the amount of substance be 1：
(0.4-0.5)：(2-4)：0.02：0.02：(3-10).
4,4 '-dihalo- biphenyl structural formulas are：Wherein X is one kind in Cl, Br, I.
The substituted diphenylamine can be reacted by Ullmann to be made, it is preferred that substituted diphenylamine is by including the following steps
Method is prepared：By substituted aniline, 0-chloro-benzoic acid, metal carbonate, the second catalyst in 100-120 in the second solvent
DEG C reacted to get；The structural formula of the substituted aniline is：The alkane that wherein R is selected from hydrogen, carbon atom number is 1-10
Alkoxy that halogenated alkyl that base, carbon atom number are 1-5, carbon atom number are 1-5, aryl.R is preferably H, methyl, butyl, trifluoro
Methyl, methoxyl group or phenyl.
Second catalyst is one or more combinations in copper, copper oxide, cuprous oxide.
Substituted aniline, 0-chloro-benzoic acid, metal carbonate, the second catalyst mass ratio be (0.5-0.8)：1：(1-
3.5)：(0.01-0.1).Second catalyst is preferably mass ratio 1:The mixture of 1 copper and copper oxide composition.
Second solvent is in dimethyl sulfoxide, N,N-dimethylformamide, water, DMAC N,N' dimethyl acetamide, cyclohexanone
One kind.The mass ratio of substituted aniline and the second solvent is (0.5-0.8)：(1-10).
The preparation method of the intermediate of the present invention is to be oriented to base with carboxyl so that substituted diphenylamine and halogenated biphenyl it is anti-
Condition is answered to reduce, used catalyst is simple and easy to get, the purity and high income of reaction product, reduces the industry system of intermediate
This is caused, the industrial production cost to reduce biphenyl type tri-arylamine group compound creates good condition.
The present invention is to be oriented to base to prepare technical solution used by the method for biphenyl type tri-arylamine group compound with carboxyl
It is：
A method of biphenyl type tri-arylamine group compound is prepared to be oriented to base with carboxyl, including：Intermediate, third are urged
Agent, ligand in third solvent in 140-200 DEG C carry out decarboxylic reaction to get.
The third catalyst is cuprous oxide.The ligand is N, and N'- lupetazins, Phen, take triethylamine
Phen, the N in generation, N, N', N'- tetramethylethylenediamines, N, accelerine or N, N- diisopropyl.Intermediate, third
The ratio between amount of substance of catalyst, ligand is 1：(0.01-0.1)：(0.01-0.05).
The third solvent is one kind in N-Methyl pyrrolidone, dimethyl sulfoxide.The substance of intermediate, third solvent
The ratio between amount is 1：(3-6).
The time of the decarboxylic reaction is 4-8h.
The present invention is the method for being oriented to base and preparing biphenyl type tri-arylamine group compound with carboxyl, using intermediate in catalyst
It is reacted under ligand existence condition, reaction process is gently easily-controllable, and the purity and high income of product significantly reduce biphenyl type
The industrial manufacturing cost of tri-arylamine group compound has good industrial application value.The product purity of the preparation method exists
99.5% or more, reaction yield up to 82% or more, synthesize substituted diphenylamine reaction can using environmental-friendly water as solvent, after
Processing is simple.
Specific implementation mode
Embodiments of the present invention are described further with reference to specific embodiment.
Embodiment 1
The intermediate for being used to prepare biphenyl type tri-arylamine group compound of the present embodiment, shown in structural formula such as formula (2)：
The present embodiment is the method for being oriented to base and preparing biphenyl type tri-arylamine group compound, the following institute of process route with carboxyl
Show：
It is as follows：
1) synthesis of intermediate
1. 4.00kg water is added in the reactor with thermometer and reflux, adjacent chlorobenzene is sequentially added while stirring
Formic acid 2.00kg, potassium carbonate 2.00kg, copper oxide 0.02kg and 3- methylaniline (1a) 1.00kg, 100 DEG C are warming up to by system
Reaction, TLC monitorings reaction to terminal, stop heating；System is cooled to 60 DEG C, and the activated carbon 0.16kg of decolorization has been added,
It continues stirring until system uniformly to filter afterwards, the concentrated hydrochloric acid that a concentration of 30-36% is then added adjusts the pH=1 of filtrate, at this time has
Product is precipitated, by precipitate filtering, washing, drying can obtain substituted diphenylamine 2a 2.83kg for use, yield 97.5%.
2. substituted diphenylamine 2a (2.83kg, 12.47mol), 4,4 '-diiodides are added in the reactor
(2.02kg.4.98mol), potassium carbonate (3.45kg, 24.96mol), copper powder (0.016kg, 0.25mol), copper oxide (0.02kg,
0.25mol), nitrobenzene (4.60kg, 37.36mol) installs oil water separator, 150 DEG C, insulation reaction 10h is warming up to after 1h,
TLC monitorings reaction is to terminal；Decompression steams nitrobenzene, adds water and the hydrochloric acid regulation system pH=2 of 3mol/L, pours out water phase, Gu
The centrifugation of body material dries water, and 2.5L chloroforms are added and are uniformly mixed (dissolved solid material), and it is 5% that mass concentration, which is then added,
It is colourless (washing removes 2a and impurity) that weak aqua ammonia washs organic phase to washing water phase repeatedly, and the organic phase after washing is higher than chlorine
Return stirring 2h at a temperature of imitative boiling point is cooled to 20-25 DEG C and stands 6h (process of the cooling crystallization of attaching most importance to of reflux), filters, do
It is dry, obtain intermediate 3a (2.75kg, 4.55mol), purity 96.0%, yield 91.4%.Solvent used in the step
It recycles.Characterization of The Products is：1H NMR (400MHz, CDCl3):δ7.91(d,2H),7.37(d,2H),7.32(m,4H),
7.19(m,2H),7.17(m,2H),7.08(m,2H),6.97(m,4H),6.69(m,6H),2.31(s,6H)。
2) bis- (3- the methyl)-N of target compound N, N ' -, the conjunction of N '-diphenyl -1,1 '-biphenyl -4,4 '-diamines (4a)
At：
Intermediate 3a 2.75kg, cuprous oxide 0.02kg are added in the reactor with thermometer and reflux
(0.14mol), o-phenanthroline 0.02kg (0.11mol), NMP 1.35kg (13.65mol) react 8h under conditions of 140 DEG C,
Nmp solvent is steamed after reaction, and 1.5L water is added and is uniformly mixed, black crude product is obtained by filtration, black crude product is tied again with hexamethylene
Brilliant bis- (3- the methyl)-N of white crystal N, N '-to obtain the final product, diphenyl -1 N ' -, 1 '-biphenyl -4,4 '-diamines (4a) 2.17kg, purity
It is 99.6%, yield 92.3%.Characterization of The Products is：1H NMR (400MHz, CDCl3):δ 7.49 (d, J=9.0Hz, 4H),
7.29 (dd, J=7.5Hz, 4H), 7.19 (dd, J=8.0Hz, 2H), 6.84-7.17 (m, 16H), 2.31 (s, 6H).
Embodiment 2
The intermediate for being used to prepare biphenyl type tri-arylamine group compound of the present embodiment, structural formula are same as Example 1.
The present embodiment is the method for being oriented to base and preparing biphenyl type tri-arylamine group compound, the following institute of process route with carboxyl
Show：
It is as follows：
1) synthesis of intermediate
1. 10.05kg water is added in the reactor with thermometer and reflux, adjacent chlorine is sequentially added while stirring
Benzoic acid 2.00kg, sodium carbonate 4.50kg, copper oxide 0.11kg and 3- methylaniline (1a) 1.30kg, 103 are warming up to by system
DEG C reaction, TLC monitoring reaction to terminal, stop heating；System is cooled to 70 DEG C, and activated carbon 0.20kg is added, continues stirring until
System uniformly filters afterwards, and pH value=1 of a concentration of 35% concentrated hydrochloric acid adjusting filtrate is then added, there is product precipitation at this time, will
Precipitate filtering, washing, drying can obtain substituted diphenylamine (2a) 2.80kg for use, yield 96.8%.
2. substituted diphenylamine (2a) 2.80kg (12.33mol), 4,4 '-diiodide 2.25kg are added in the reactor
(5.54mol), sodium carbonate 5.11kg (48.21mol), copper powder 0.016kg (0.25mol), copper oxide 0.02kg (0.25mol),
Nitrobenzene 9.86kg (80.09mol) installs oil water separator, 175 DEG C is warming up to after 1h, insulation reaction 6h, TLC monitoring reaction
To terminal；Decompression steams nitrobenzene, and the hydrochloric acid solution of water and 3mol/L is added to adjust pH=2, pours out water phase, and solid material centrifugation will
Water dries, and addition 2.5L chloroforms are uniformly mixed, and the weak aqua ammonia that mass concentration is 5% is then added and washs organic phase repeatedly to washing
Water phase is colourless, the organic phase return stirring 2h after washing, is cooled to 25 DEG C of standing 6h, filters, dry, obtains intermediate 3a
3.13kg, purity 99.5%, yield 93.4%.Recycled solvent used in the step.
2) bis- (3- the methyl)-N of target compound N, N ' -, the conjunction of N '-diphenyl -1,1 '-biphenyl -4,4 '-diamines (4a)
At：
Intermediate 3a 3.13kg (5.18mol), cuprous oxide are added in the reactor with thermometer and reflux
0.04kg (0.28mol), o-phenanthroline 0.037kg (0.21mol), NMP 2.56kg (25.86mol), under conditions of 170 DEG C
6h is reacted, nmp solvent is steamed after reaction, 1.5L water is added and is uniformly mixed, black crude product is obtained by filtration, by black crude product hexamethylene
Alkane recrystallizes up to bis- (3- the methyl)-N of white crystal N, N ' -, N '-diphenyl -1,1 '-biphenyl -4,4 '-diamines (4a)
2.43kg, purity 99.6%, yield 90.7%.Compound 4a characterize datas are the same as embodiment 1.
Embodiment 3
The intermediate for being used to prepare biphenyl type tri-arylamine group compound of the present embodiment, structural formula are same as Example 1.
The present embodiment is the method for being oriented to base and preparing biphenyl type tri-arylamine group compound, the following institute of process route with carboxyl
Show：
It is as follows：
1) synthesis of intermediate
1. 20.00kg water is added in the reactor with thermometer and reflux, adjacent chlorine is sequentially added while stirring
Benzoic acid 2.00kg, cesium carbonate 7.00kg, copper powder 0.10kg, copper oxide 0.10kg and 3- methylaniline (1a) 1.60kg, by body
System is warming up to 105 DEG C of reactions, and TLC monitorings reaction to terminal, stops heating；System is cooled to 80 DEG C, and activated carbon 0.24kg is added,
It continues stirring until system uniformly to filter afterwards, pH value=1 of a concentration of 36% concentrated hydrochloric acid adjusting filtrate is then added, there is production at this time
Object is precipitated, by precipitate filtering, washing, drying can obtain substituted diphenylamine (2a) 2.85kg for use, yield 98.3%.
2. substituted diphenylamine (2a) 2.85kg (12.55mol), 4,4 '-diiodide 2.55kg are added in the reactor
(6.28mol), cesium carbonate 16.36kg (50.21mol), copper powder 0.016kg (0.25mol), copper oxide 0.02kg (0.25mol),
Nitrobenzene 15.44kg (125.50mol) installs oil water separator, 200 DEG C is warming up to after 1h, insulation reaction 2h, TLC monitoring is anti-
It should to terminal；Decompression steams nitrobenzene, and the hydrochloric acid solution of water and 3mol/L is added to adjust pH=2, pours out water phase, solid material centrifugation
Water is dried, 2.5L chloroforms are added and are uniformly mixed, the weak aqua ammonia that mass concentration is 5% is then added and washs organic phase repeatedly to washing
It is colourless, the organic phase return stirring 1h after washing to wash water phase, is cooled to 25 DEG C of standing 6h, filters, dry, obtains intermediate
3a3.61kg, purity 96.0%, yield 95.0%.Recycled solvent used in the step.
2) bis- (3- the methyl)-N of target compound N, N ' -, the conjunction of N '-diphenyl -1,1 '-biphenyl -4,4 '-diamines (4a)
At：
Intermediate 3a 3.61kg (5.97mol), cuprous oxide are added in the reactor with thermometer and reflux
0.08kg (0.56mol), TMEDA 0.03kg (0.26mol), NMP 3.55kg (35.85mol) are anti-under conditions of 200 DEG C
4h is answered, nmp solvent is steamed after reaction, 1.5L water is added and is uniformly mixed, black crude product is obtained by filtration, by black crude product hexamethylene
It recrystallizes up to bis- (3- the methyl)-N of white crystal N, N ' -, diphenyl -1 N ' -, 1 '-biphenyl -4,4 '-diamines (4a) 2.88kg,
Purity is 99.6%, yield 93.5%.Compound 4a characterize datas are the same as embodiment 1.
Embodiment 4
The intermediate for being used to prepare biphenyl type tri-arylamine group compound of the present embodiment, shown in structural formula such as formula (3)：
The present embodiment is the method for being oriented to base and preparing biphenyl type tri-arylamine group compound, the following institute of process route with carboxyl
Show：
It is as follows：
1) synthesis of intermediate
1. 4.00kg water is added in the reactor with thermometer and reflux, adjacent chlorobenzene is sequentially added while stirring
Formic acid 1.56kg, sodium carbonate 3.12kg, copper powder 0.04kg, copper oxide 0.04kg and 4- methylaniline (1b) 1.09kg, by system
105 DEG C of reactions are warming up to, TLC monitorings reaction to terminal, stops heating；System is cooled to 70 DEG C, and activated carbon 0.16kg is added, holds
Continuous stirring is uniformly filtered afterwards to system, and pH value=1 of a concentration of 33% concentrated hydrochloric acid adjusting filtrate is then added, there is product at this time
It is precipitated, precipitate filtering, washing, drying can be obtained into substituted diphenylamine (2b) 2.22kg (9.78mol) for use, yield 97.9%.
2. substituted diphenylamine (2b) 2.22kg, 4,4 '-diiodide 1.79kg (4.41mol), carbon are added in the reactor
Sour sodium 3.11kg (29.34mol), copper powder 12.54g (0.196mol), copper oxide 15.68g (0.196mol), nitrobenzene 6.01kg
(48.82mol) installs oil water separator, 170 DEG C is warming up to after 1h, insulation reaction 10h, TLC monitoring reaction is to terminal；Decompression
Nitrobenzene is steamed, the hydrochloric acid solution of water and 3mol/L is added to adjust pH=2, pours out water phase, water is dried, is added by solid material centrifugation
2.5L chloroforms be uniformly mixed, then be added mass concentration be 5% weak aqua ammonia wash repeatedly organic phase to washing water phase be it is colourless,
Organic phase return stirring 2h after washing is cooled to 25 DEG C of standing 6h, filters, dry, obtains intermediate 3b 2.51kg, purity
It is 96.0%, yield 94.0%.Recycled solvent used in the step.Characterization of The Products is：1H NMR(400MHz,
CDCl3):δ8.0(d,2H)7.54(d,2H),7.32(m,4H),7.27(m,2H),7.23(m,2H),7.13(m,2H),6.95
(m,4H),6.80(m,6H),2.32(s,6H)。
2) bis- (4- the methyl)-N of target compound N, N ' -, the conjunction of N '-diphenyl -1,1 '-biphenyl -4,4 '-diamines (4b)
At：
Intermediate 3b 2.51kg (4.15mol), cuprous oxide are added in the reactor with thermometer and reflux
0.03kg (0.21mol), TMEDA 0.02kg (0.17mol), NMP 2.05kg (20.75mol) are anti-under conditions of 180 DEG C
4h is answered, nmp solvent is steamed after reaction, 1.5L water is added and is uniformly mixed, black crude product is obtained by filtration, by black crude product hexamethylene
It recrystallizes up to bis- (4- the methyl)-N of white crystal N, N ' -, N '-diphenyl -1,1 '-biphenyl -4,4 '-diamines (4b) 1.98kg
(3.83mol), purity 99.6%, yield 92.3%.Characterization of The Products is：1H NMR(400MHz,CDCl3):δ7.42(d,J
=8.8Hz, 4H), 7.21-7.24 (m, 4H), 7.02-7.12 (m, 16H), 6.98 (t, J=7.4Hz, 2H), 2.32 (s, 6H).
Embodiment 5-9
The intermediate of embodiment 5-9, structural formula is as shown in table 1, can use respectively Substituted aniline 1b is replaced as described in Example 4, synthesize successively in table 1 it is listed it is each in
Mesosome.
The structural formula of the intermediate of 1 embodiment 5-9 of table
On the basis of above-mentioned intermediate, corresponding biphenyl type tri-arylamine group chemical combination can be synthesized according to the method for embodiment 4
Object.
In other preparation embodiments of the intermediate of the present invention, this can be used in the first solvent, the second solvent, third solvent
Solvent type defined by invention is replaced, the type of ligand, and the dosage of each step reaction raw material and specific reaction condition can
To be adaptively adjusted in the framework of the present definition, can reach and the comparable effect of embodiment.
Claims (10)
1. a kind of intermediate being used to prepare biphenyl type tri-arylamine group compound, which is characterized in that have and tied as shown in formula (1)
Structure：
In formula (1), R is selected from the halogenated alkyl that hydrogen, the alkyl that carbon atom number is 1-10, carbon atom number are 1-5, carbon atom number 1-
5 alkoxy, aryl.
2. a kind of preparation method of intermediate as described in claim 1, which is characterized in that including：By substituted diphenylamine, 4,
4 '-dihalo- biphenyl, metal carbonate, the first catalyst reacted at 150-200 DEG C in the first solvent to get；It is described
The structural formula of substituted diphenylamine is：Alkyl, the carbon that wherein R is selected from hydrogen, carbon atom number is 1-10
Alkoxy that halogenated alkyl that atomicity is 1-5, carbon atom number are 1-5, aryl.
3. preparation method as claimed in claim 2, which is characterized in that the metal carbonate is potassium carbonate, sodium carbonate, carbonic acid
One or more combinations in hydrogen sodium, cesium carbonate.
4. preparation method as claimed in claim 2, which is characterized in that first catalyst is copper and/or copper oxide.
5. the preparation method as described in Claims 2 or 3 or 4, which is characterized in that substituted diphenylamine, 4,4 '-dihalo- biphenyl, gold
It is 1 to belong to the ratio between amount of substance of carbonate, the first catalyst：(0.4-0.5)：(2-4)：0.04.
6. preparation method as claimed in claim 5, which is characterized in that first catalyst is mass ratio 1:1 copper and oxygen
Change the mixture of copper composition.
7. preparation method as claimed in claim 2, which is characterized in that substituted diphenylamine is prepared by method comprising the following steps
It obtains：Substituted aniline, 0-chloro-benzoic acid, metal carbonate, the second catalyst are carried out instead in the second solvent in 100-120 DEG C
It should be to get；The structural formula of the substituted aniline is：Wherein R is selected from hydrogen, carbon atom number is the alkyl of 1-10, carbon original
Alkoxy that halogenated alkyl that subnumber is 1-5, carbon atom number are 1-5, aryl.
8. with carboxyl it is to be oriented to the base method for preparing biphenyl type tri-arylamine group compound a kind of, which is characterized in that including：It will be intermediate
Body, third catalyst, ligand in third solvent in 140-200 DEG C carry out decarboxylic reaction to get；The intermediate is wanted for right
Seek the intermediate described in 1.
9. being as claimed in claim 8 the method for being oriented to base and preparing biphenyl type tri-arylamine group compound with carboxyl, feature exists
In the ligand is N, N'- lupetazins, triethylamine, Phen, substituted Phen, N, N, N', N'- tetramethyls
Ethylenediamine, N, accelerine or N, N- diisopropyls.
10. it is as claimed in claim 8 or 9 the method for being oriented to base and preparing biphenyl type tri-arylamine group compound with carboxyl, it is special
Sign is, intermediate, third catalyst, ligand the ratio between the amount of substance be 1：(0.01-0.1)：(0.01-0.05).
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| CN111302952A (en) * | 2020-04-03 | 2020-06-19 | 郑州原理生物科技有限公司 | Refining method of 4-methyldiphenylamine |
| CN115057868A (en) * | 2022-07-04 | 2022-09-16 | 中原工学院 | Preparation method of thieno [2,3-b ] thiophene |
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| CN105175716A (en) * | 2015-09-02 | 2015-12-23 | 黑龙江大学 | Triphenylamino group-containing polyamide film, and production method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111302952A (en) * | 2020-04-03 | 2020-06-19 | 郑州原理生物科技有限公司 | Refining method of 4-methyldiphenylamine |
| CN111302952B (en) * | 2020-04-03 | 2023-06-20 | 郑州原理生物科技有限公司 | Refining method of 4-methyl diphenylamine |
| CN115057868A (en) * | 2022-07-04 | 2022-09-16 | 中原工学院 | Preparation method of thieno [2,3-b ] thiophene |
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| CN108276300B (en) | 2020-11-24 |
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