CN107325037A - A kind of preparation method of 1 bromine carbazole - Google Patents
A kind of preparation method of 1 bromine carbazole Download PDFInfo
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- CN107325037A CN107325037A CN201710374924.1A CN201710374924A CN107325037A CN 107325037 A CN107325037 A CN 107325037A CN 201710374924 A CN201710374924 A CN 201710374924A CN 107325037 A CN107325037 A CN 107325037A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
Abstract
The invention discloses a kind of preparation method of 1 bromine carbazole, belong to organic chemical synthesis field.The preparation method of 1 bromine carbazole provided by the present invention is specially：Using o-bromoaniline and adjacent bromo-iodobenzene as raw material, Liv Ullmann coupling reaction is carried out, intermediate two (2 bromophenyl) amine is made；(2 bromophenyl) amine of intermediate two carries out ring closure reaction under palladium catalyst effect and obtains 1 bromine carbazole.The method of the invention operation is simple, solvent energy recovery, and the cost of raw material is low, high income, is advantageously implemented industrialized production.In addition, the 1 bromine carbazole purity as made from the method for the invention is high, it can be used for the fields such as oled light electrical domain, medicine, dyestuff, agricultural chemicals, be a kind of important carbazoles intermediate, have broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of 1- bromines carbazole, belong to organic chemical synthesis field.
Background technology
Carbazole analog derivative is the intermediate that a major class has extensive use.Because the inductive effect of N atoms on carbazole is small
In its conjugation, thus it can be used for hole transmission layer in photoelectric field, and it has good photoelectric properties.Using carbazole as original
Other derivatives prepared by material are also widely used in the fields such as oled light electric material, medicine, dyestuff and agricultural chemicals.
1- bromine carbazoles are the important organic chemical industry's intermediates of a class, and other chemical products prepared using it as raw material are in OLED
There is relatively broad purposes in terms of photoelectric field, agricultural chemicals, medicine and dyestuff.
The synthetic method on 1- bromine carbazoles is broadly divided into two major classes both at home and abroad：One is carried out by raw material of nitro compound
After suzuki couplings, then obtain via triethyl phosphite or triphenylphosphine cyclization.Two be (or adjacent with cyclohexanone and bromophenyl hydrazine
Bromaniline) coupling rear oxidation dehydrogenation obtain.React mostly yield relatively low, and used triethyl phosphite smell it is big, it is difficult after
Processing, triphenyl phosphorus can produce substantial amounts of triphenylphosphinc oxide accessory substance again, and difficulty is brought to post processing purge process.Bromophenyl hydrazine
And oxidant feed is more expensive, oxidant and its accessory substance make it that the purifying difficulty of final products is larger again.At present need to be to 1- bromine clicks
The production technology of azoles is improved, to meet growing product demand.
The synthetic technology mainly used at present is as shown below：
Route one：
Route two：
In addition, China application CN 106397304A disclose a kind of method of synthesis 1- bromine carbazoles, this method is with 3,6- bis-
Tert-butyl carbazole is initiation material, bromo- 3, the 6- di-t-butyls carbazoles of 1- is synthesized by bromination reaction, in alchlor and isopropanol
Under the conditions of slough the tert-butyl group, through alkali process, purifying obtain 1- bromine carbazoles.
Either however, above-mentioned various synthetic method severe reaction conditions, or cost of material is high, it is difficult to realize extensive
Production.
The content of the invention
To solve the above problems, to provide a kind of simple operation, simple post processing purifying, high income, cost low by the present invention
The novel preparation method of 1- bromine carbazoles.
The preparation method of 1- bromines carbazole of the present invention, its synthetic route is as follows：
Methods described is specially：
O-bromoaniline and adjacent bromo-iodobenzene are subjected to Liv Ullmann coupling reaction and obtain intermediate two-(2- bromophenyls) amine；
The intermediate two-(2- bromophenyls) amine is subjected to ring closure reaction under palladium catalyst effect and obtains target product 1-
Bromine carbazole.
Preferably, the preparation method of 1- bromines carbazole of the present invention comprises the following steps：
(1) adjacent bromo-iodobenzene and o-bromoaniline are subjected to Liv Ullmann coupling instead in the presence of catalyst, part and organic base
Should, intermediate two-(2- bromophenyls) amine is made；
(2) it is the intermediate two-(2- bromophenyls) amine carries out cyclization in the presence of catalyst, part and inorganic base is anti-
Should, 1- bromine carbazoles are made.
Preparation method of the present invention, reaction condition (such as reaction temperature, the selection of solvent, point of product of each step
From etc.) the conventional available means of this area can be used, satisfaction can realize that 1- bromine carbazoles are made in the above-mentioned reaction mechanism mechanism of reaction.
Only for further improving the quality of syntheti c route, goal of the invention is better achieved, the present invention is to the preparation side
The actual conditions of method has carried out following optimization：
Method of the present invention, catalyst described in step (1) is three (dibenzalacetone) two palladium or [1,1'- is double
(diphenylphosphino) ferrocene] palladium chloride.
The part is one kind in tri-butyl phosphine or triphenylphosphine or tricyclohexyl phosphine.
The organic base is preferably sodium tert-butoxide, and the organic base has preferable solubility property, and reaction can be promoted to carry out.
Preferably：
In step (1), the molar feed ratio of the adjacent bromo-iodobenzene and the o-bromoaniline is 1:0.85-1, preferably 1:
1.Under the rate of charge, generation impurity and accessory substance that can be less have the advantages that to simplify subsequent treatment.
Meanwhile, the preferable molar feed ratio of the adjacent bromo-iodobenzene, the catalyst and the part is 1:0.003-
0.03:0.006-0.06, preferably 1:0.01:0.02.
The preferable mol ratio of the adjacent bromo-iodobenzene and organic base is 1:2-3, preferably 1:2.
In method of the present invention, step (1), the Liv Ullmann coupling reaction is carried out in a solvent；The solvent can
Selected from toluene or dimethylbenzene or diethylbenzene, preferably toluene.It is highly preferred that the adjacent bromo-iodobenzene and the solvent load (quality/
Volume) than being 1g:5-15mL.
Reaction temperature in method of the present invention, step (1) is 100-110 DEG C；Preferably 108 DEG C.
Preferably, step (1) also includes the organic phase for obtaining Liv Ullmann coupling reaction through being washed to neutrality, after drying,
Cross silicagel column and remove mechanical admixture, the processing of solvent is recovered under reduced pressure.
Method of the present invention, step (2) is by the intermediate two-(2- bromophenyls) amine in catalyst, part and nothing
Ring closure reaction is carried out in the presence of machine alkali, 1- bromine carbazoles are made；
Wherein, the ideal chose of the catalyst is palladium.
The ideal chose of the part is 2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl, triphenylphosphine or three rings
One kind in hexyl phosphine；Preferably 2- dicyclohexyls phosphorus -2', 4', 6'- tri isopropyl biphenyls.
The ideal chose of the inorganic base is one kind in potassium carbonate or sodium carbonate or cesium carbonate；Preferably cesium carbonate.Should
Inorganic base can improve reaction conversion ratio, have the advantages that to improve final products yield.
Preferably, in step (2), the intermediate two-(2- bromophenyls) amine, the palladium catalyst, the phosphorus part rub
That rate of charge=1:0.003-0.03:0.006-0.06, preferably 1:0.01:0.02.
Preferably, in step (2), molar feed ratio=1 of the intermediate two-(2- bromophenyls) amine and inorganic base:2-
3, preferably 1:2.
In method of the present invention, step (2), the ring closure reaction is carried out in a solvent；The solvent be selected from DMF or
One kind in NMP or DME, preferably DMF.It is highly preferred that the intermediate two-(2- bromophenyls) amine and the solvent load
(mass/volume) is than being 1g:5-15mL.
Reaction temperature in method of the present invention, step (2) is 130-140 DEG C；Preferably 135 DEG C.
Preferably, step (2) also includes the purification process of product, is specially：The 1- bromine carbazoles that ring closure reaction is obtained are thick
Product go out through elutriation, cross silicagel column, are then recrystallized with hexamethylene or normal heptane, produce 1- bromine carbazole fine work.
After above-mentioned separating-purifying step, the purity of present invention gained 1- bromine carbazole products may be up to more than 99%.
In addition, method of the present invention, Liv Ullmann coupling reaction described in step (1) and step (2) described cyclization are anti-
It should be carried out under the protection of inert gas；The inert gas is preferably nitrogen.
Specifically, the preparation method of 1- bromines carbazole of the present invention, preferably includes following steps：
(1) under inert gas shielding, by adjacent bromo-iodobenzene and o-bromoaniline catalyst, part and organic base presence
Under, Liv Ullmann coupling reaction is carried out in toluene, the intermediate two-(2- bromophenyls) amine is made；
The catalyst is three (dibenzalacetone) two palladium or [double (diphenylphosphino) ferrocene of 1,1'-] dichloride
Palladium；The part is one kind in tri-butyl phosphine or triphenylphosphine or tricyclohexyl phosphine；The organic base is sodium tert-butoxide；
The molar feed ratio of the adjacent bromo-iodobenzene and the o-bromoaniline is 1:0.85-1；The adjacent bromo-iodobenzene, described urge
The molar feed ratio of agent and the part is 1:0.003-0.03:0.006-0.06, preferably 1:0.01:0.02；It is described
The preferable mol ratio of adjacent bromo-iodobenzene and organic base is 1:2-3；
(2) under inert gas shielding, by the intermediate two-(2- bromophenyls) amine in catalyst, part and inorganic base
In the presence of, ring closure reaction is carried out in DMF, product produces 1- bromine carbazoles after separating-purifying；
The catalyst is palladium；The part is 2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl, triphen
One kind in base phosphine or tricyclohexyl phosphine；The inorganic base is one kind in potassium carbonate or sodium carbonate or cesium carbonate；
The intermediate two-(2- bromophenyls) amine, the palladium catalyst, phosphorus part molar feed ratio=1:0.003-
0.03:0.006-0.06；Molar feed ratio=1 of the intermediate two-(2- bromophenyls) amine and inorganic base:2-3；
It is preferred that the intermediate two-(2- bromophenyls) amine, the palladium catalyst, the phosphorus part and inorganic base rubs
Your rate of charge is 1:0.01:0.02:2.
The preparation method operation of 1- bromines carbazole of the present invention is simple, solvent energy recovery, the cost of raw material is low,
Mild condition, post processing purification process is easy, and yield significantly reduces production cost up to more than 80%, is advantageously implemented work
Industry metaplasia is produced, and the purity of gained 1- bromine carbazoles may be up to more than 99%, can be widely applied to oled light electric material, medicine, dye
The fields such as material, agricultural chemicals.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described.Raw materials, solvent and catalyst are conventional city
Sell product.Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method of 1- bromines carbazole, and specifically, methods described comprises the following steps：
(1) under nitrogen protection, adjacent bromo-iodobenzene 28.2g (molecular weight 282.9,0.1mol), o-bromoaniline 17.2g (are divided
Son amount 172.02,0.1mol), sodium tert-butoxide 19.2g (molecular weight 96.1,0.2mol), toluene 225.6mL be added to stirring
Mix, in the reaction bulb of condenser pipe, thermometer, be warming up to 55 DEG C, three (dibenzalacetone) two palladiums are quickly added into system
0.91g (molecular weight 915.72,0.001mol), tri-butyl phosphine (30% toluene solution) 1.35g (molecular weight 202.3,
0.002mol).108 DEG C of back flow reactions are warming up to, when gas-chromatography (GC) tracing detection raw material o-bromoaniline is without residue, are stopped anti-
Should.Obtained organic phase will be reacted through being washed to neutrality, filtered after being dried through 20g sodium sulphate, filtrate is concentrated to dryness to obtain brown color
Intermediate two-(2- bromophenyls) amine 32.6g (molecular weight 327,0.1mol)；MS(FAB)：m/z 327(M+)
(2) by intermediate two made from step (1)-(2- bromophenyls) amine, potassium carbonate 27.6g (molecular weight 138,
0.2mol), DMF 326mL, palladium 0.22g (molecular weight 224.29,0.001mol), 2- dicyclohexyl phosphorus -2', 4', 6'-
Tri isopropyl biphenyl 0.95g (molecular weight 476.7,0.002mol) is added to stirring, condenser pipe, the reaction bulb of thermometer
In, it is warming up to when 140 DEG C of reactions detect two-(2- bromophenyls) amine without residue to GC and stops reaction.Be concentrated under reduced pressure out about 163mL
DMF, 1630mL elutriations are added into remaining organic phase and go out after solid, suction filtration to wash filter cake, drying.By gained filter cake 500mL
Hexamethylene is dissolved by heating, and crosses the heat-insulation column (80 DEG C) equipped with 24.6g silica gel, is crossed post liquid when being concentrated under reduced pressure into residue about 246mL, is dropped
To crystallizing at room temperature, suction filtration, white solid 20.4g target product 1- bromine carbazoles are dried to obtain.
The yield that 1- bromine carbazoles are made in the present embodiment is 83.2%, and G/C content is 99.2%.
Product fusing point：123.3℃-124℃.MS(FAB)：m/z 246(M+).Elementary analysis C12H8BrN：Theoretical value C：
58.56%；H：3.28%；Br：32.47%；N：5.69%.Measured value C:58.53%；H：3.27%；Br：32.5%；N：
5.68%.
Embodiment 2
The present embodiment provides a kind of preparation method of 1- bromines carbazole, and specifically, methods described comprises the following steps：
(1) under nitrogen protection, adjacent bromo-iodobenzene 28.2g (molecular weight 282.9,0.1mol), o-bromoaniline 16.3g (are divided
Son amount 172.02,0.095mol), sodium tert-butoxide 19.2g (molecular weight 96.1,0.2mol), dimethylbenzene 225.6mL be added to band
Have in stirring, condenser pipe, the reaction bulb of thermometer, be warming up to 55 DEG C, [1,1'- double (diphenylphosphines are quickly added into system
Base) ferrocene] palladium chloride 0.73g (molecular weight 731.7,0.001mol), tricyclohexyl phosphine 0.56g (molecular weight 280.4,
0.002mol).110 DEG C of reactions are warming up to, when GC tracing detection raw material o-bromoanilines are without residue, stop reaction.Reaction is obtained
Organic phase through being washed to neutrality, filtered after being dried through 20g sodium sulphate, filtrate is concentrated to dryness to obtain brown color intermediate two-(2- bromines
Phenyl) amine 31g (molecular weight 327,0.095mol)；
(2) by intermediate two made from step (1)-(2- bromophenyls) amine, sodium carbonate 20.1g (molecular weight 105.9,
0.19mol), DME 310mL, palladium 0.42g (molecular weight 224.29,0.0019mol), triphenylphosphine 0.99g (molecular weight
262.3,0.0038mol) it is added to and carries in stirring, condenser pipe, the reaction bulb of thermometer, is warming up to 130 DEG C of reactions to GC inspections
Stop reaction when surveying two-(2- bromophenyls) amine without residue.Be concentrated under reduced pressure out about 155mL DME, is added into remaining organic phase
1550mL elutriations go out after solid, suction filtration to wash filter cake, drying.Gained filter cake is dissolved by heating with 500mL hexamethylenes, crosses and is equipped with
The heat-insulation column (80 DEG C) of 23.3g silica gel, when post liquid is concentrated under reduced pressure into residue about 233mL excessively, is down to crystallizing at room temperature, suction filtration, drying
Obtain white solid 20.19g target product 1- bromine carbazoles.
The yield that 1- bromine carbazoles are made in the present embodiment is 82.1%, and G/C content is 99.5%.
Embodiment 3
The present embodiment provides a kind of preparation method of 1- bromines carbazole, and specifically, methods described comprises the following steps：
(1) under nitrogen protection, adjacent bromo-iodobenzene 28.2g (molecular weight 282.9,0.1mol), o-bromoaniline 17.2g (are divided
Son amount 172.02,0.1mol), sodium tert-butoxide 19.2g (molecular weight 96.1,0.2mol), toluene 225.6mL be added to stirring
Mix, in the reaction bulb of condenser pipe, thermometer, be warming up to 55 DEG C, three (dibenzalacetone) two palladiums are quickly added into system
0.91g (molecular weight 915.72,0.001mol), tricyclohexyl phosphine 0.56g (molecular weight 280.43,0.002mol).It is warming up to
108 DEG C of back flow reactions, when GC tracing detection raw material o-bromoanilines are without residue, stop reaction.Obtained organic phase will be reacted through water
Neutrality is washed till, is filtered after being dried through 20g sodium sulphate, filtrate is concentrated to dryness to obtain brown color intermediate two-(2- bromophenyls) amine 32.6g
(molecular weight 327,0.1mol)；
(2) by intermediate two made from step (1)-(2- bromophenyls) amine, cesium carbonate 65.1g (molecular weight 325.82,
0.2mol), NMP326mL, palladium 0.22g (molecular weight 224.29,0.001mol), tricyclohexyl phosphine 0.56g (molecular weight
280.43,0.002mol) it is added to and carries in stirring, condenser pipe, the reaction bulb of thermometer, is warming up to 135 DEG C of reactions to GC inspections
Stop reaction when surveying two-(2- bromophenyls) amine without residue.Be concentrated under reduced pressure out about 163mL NMP, is added into remaining organic phase
1630mL elutriations go out after solid, suction filtration to wash filter cake, drying.Gained filter cake is dissolved by heating with 800mL normal heptanes, crosses and is equipped with
The heat-insulation column (80 DEG C) of 24.6g silica gel, when post liquid is concentrated under reduced pressure into residue about 246mL excessively, is down to crystallizing at room temperature, suction filtration, drying
Obtain white solid 20.3g target product 1- bromine carbazoles.
The yield that 1- bromine carbazoles are made in the present embodiment is 82.8%, and G/C content is 99.6%.
Embodiment 4
The present embodiment provides a kind of preparation method of 1- bromines carbazole, and specifically, methods described comprises the following steps：
(1) under nitrogen protection, adjacent bromo-iodobenzene 28.2g (molecular weight 282.9,0.1mol), o-bromoaniline 17.2g (are divided
Son amount 172.02,0.1mol), sodium tert-butoxide 19.2g (molecular weight 96.1,0.2mol), diethylbenzene 338.4mL be added to and carry
In stirring, condenser pipe, the reaction bulb of thermometer, 55 DEG C are warming up to, three (dibenzalacetone) two palladiums are quickly added into system
1.83g (molecular weight 915.72,0.002mol), tricyclohexyl phosphine 1.12g (molecular weight 280.43,0.004mol).It is warming up to 110
DEG C reaction, when GC tracing detection raw material o-bromoanilines are without residue, stop reaction.During obtained organic phase will be reacted through being washed to
Property, filtered after being dried through 20g sodium sulphate, filtrate is concentrated to dryness to obtain brown color intermediate two-(2- bromophenyls) amine 32.3g (molecules
Amount 327,0.098mol)；
(2) by intermediate two made from step (1)-(2- bromophenyls) amine, cesium carbonate 6.41g (molecular weight 325.82,
0.0197mol), NMP323mL, palladium 0.336g (molecular weight 224.29,0.0015mol), tricyclohexyl phosphine 0.84g (divide
Son amount 280.43,0.003mol) it is added to and reacts extremely with stirring, condenser pipe, the reaction bulb of thermometer, being warming up to 135 DEG C
Stop reaction when GC detects two-(2- bromophenyls) amine without residue.Be concentrated under reduced pressure out about 161mL NMP, adds into remaining organic phase
Enter 1610mL elutriations and go out after solid, suction filtration to wash filter cake, drying.Gained filter cake is dissolved by heating with 800mL normal heptanes, crosses and fills
There is the heat-insulation column (80 DEG C) of 24.6g silica gel, when post liquid is concentrated under reduced pressure into residue about 246mL excessively, be down to crystallizing at room temperature, suction filtration, baking
Do to obtain white solid 20.1g target product 1- bromine carbazoles.
The yield that 1- bromine carbazoles are made in the present embodiment is 81.9%, and G/C content is 99.4%.
Embodiment 5
The present embodiment provides a kind of preparation method of 1- bromines carbazole, and specifically, methods described comprises the following steps：
(1) under nitrogen protection, adjacent bromo-iodobenzene 28.2g (molecular weight 282.9,0.1mol), o-bromoaniline 15.5g (are divided
Son amount 172.02,0.09mol), sodium tert-butoxide 19.2g (molecular weight 96.1,0.2mol), toluene 282mL be added to stirring
Mix, in the reaction bulb of condenser pipe, thermometer, be warming up to 55 DEG C, three (dibenzalacetone) two palladiums are quickly added into system
1.37g (molecular weight 915.72,0.0015mol), tricyclohexyl phosphine 0.84g (molecular weight 280.43,0.003mol).It is warming up to
108 DEG C of back flow reactions, when GC tracing detection raw material o-bromoanilines are without residue, stop reaction.Obtained organic phase will be reacted through water
Neutrality is washed till, is filtered after being dried through 20g sodium sulphate, filtrate is concentrated to dryness to obtain brown color intermediate two-(2- bromophenyls) amine 29.4g
(molecular weight 327,0.09mol)；
(2) by intermediate two made from step (1)-(2- bromophenyls) amine, potassium carbonate 27.6g (molecular weight 138,
0.2mol), DMF 294mL, palladium 0.22g (molecular weight 224.29,0.001mol), tricyclohexyl phosphine 0.056g (molecular weight
280.43,0.002mol) it is added to in stirring, condenser pipe, the reaction bulb of thermometer, being warming up to 135 DEG C, reaction to GC is examined
Stop reaction when surveying two-(2- bromophenyls) amine without residue.Be concentrated under reduced pressure out about 147mL NMP, is added into remaining organic phase
1470mL elutriations go out after solid, suction filtration to wash filter cake, drying.Gained filter cake is dissolved by heating with 800mL normal heptanes, crosses and is equipped with
The heat-insulation column (80 DEG C) of 24.6g silica gel, when post liquid is concentrated under reduced pressure into residue about 246mL excessively, is down to crystallizing at room temperature, suction filtration, drying
Obtain white solid 19.8g target product 1- bromine carbazoles.
The yield that 1- bromine carbazoles are made in the present embodiment is 80.4%, and G/C content is 99.65%.
Comparative example 1
This comparative example provides a kind of preparation method of 1- bromines carbazole, compared with Example 1, only with four (triphenylphosphines)
Palladium catalyst replaces three (dibenzalacetone) two palladium in step (1), and other conditions, each raw material and its consumption are and embodiment
1 is identical.
The yield that 1- bromine carbazoles are made in this comparative example is 52%, and G/C content is 93.2%.
Comparative example 2
This comparative example provides a kind of preparation method of 1- bromines carbazole, compared with Example 1, replaces walking only with potassium acetate
Suddenly the sodium tert-butoxide in (1), other conditions, each raw material and its consumption are same as Example 1.
The yield that 1- bromine carbazoles are made in this comparative example is 26%, and G/C content is 85%.
Comparative example 3
This comparative example provides a kind of preparation method of 1- bromines carbazole, compared with Example 1, only with pi-allyl diphenyl
Phosphine ligands replace the tri-butyl phosphine in step (1), and other conditions, each raw material and its consumption are same as Example 1.
The yield that 1- bromine carbazoles are made in this comparative example is 72%, and G/C content is 98.2%.
Comparative example 4
This comparative example provides a kind of preparation method of 1- bromines carbazole, compared with Example 1, only with palladium chloride catalyst
Instead of the palladium in step (2), other conditions, each raw material and its consumption are same as Example 1.
The yield that 1- bromine carbazoles are made in this comparative example is 69%, and G/C content is 97.6%.
Comparative example 5
This comparative example provides a kind of preparation method of 1- bromines carbazole, compared with Example 1, only with methyldiphenyl base chlorine
Change Phosphine ligands replace step (2) in 2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyls, other conditions, each raw material and its
Consumption is same as Example 1.
The yield that 1- bromine carbazoles are made in this comparative example is 70.6%, and G/C content is 97.9%.
Comparative example 6
This comparative example provides a kind of preparation method of 1- bromines carbazole, and methods described is foregoing route two, using bromophenyl
Hydrazine and cyclohexanone be raw material via coupling, dehydrogenation reaction, be prepared into 1- bromine carbazoles, yield is 60.3%, and G/C content is 98.3%
Although above with general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of 1- bromines carbazole, it is characterised in that o-bromoaniline and adjacent bromo-iodobenzene are subjected to Liv Ullmann coupling anti-
Intermediate two-(2- bromophenyls) amine should be obtained；The intermediate two-(2- bromophenyls) amine is closed under palladium catalyst effect
Ring reaction obtains 1- bromine carbazoles.
2. according to the method described in claim 1, it is characterised in that methods described comprises the following steps：
(1) adjacent bromo-iodobenzene and o-bromoaniline are subjected to Liv Ullmann coupling reaction in the presence of catalyst, part and organic base, made
Obtain intermediate two-(2- bromophenyls) amine；
(2) intermediate two-(2- bromophenyls) amine is subjected to ring closure reaction in the presence of catalyst, part and inorganic base,
1- bromine carbazoles are made.
3. method according to claim 2, it is characterised in that in step (1)：
The catalyst is three (dibenzalacetone) two palladium or [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride；
And/or, the part is one kind in tri-butyl phosphine or triphenylphosphine or tricyclohexyl phosphine；
And/or, the organic base is sodium tert-butoxide.
4. according to the method in claim 2 or 3, it is characterised in that in step (1), the adjacent bromo-iodobenzene and the adjacent bromine
The molar feed ratio of aniline is 1:0.85-1；
And/or, the molar feed ratio of the adjacent bromo-iodobenzene, the catalyst and the part is 1:0.003-0.03:
0.006-0.06, preferably 1:0.01:0.02；
And/or, the preferable mol ratio of the adjacent bromo-iodobenzene and organic base is 1:2-3.
5. the method according to claim any one of 2-4, it is characterised in that in step (1), the Liv Ullmann coupling is anti-
It should carry out in a solvent；The solvent is selected from toluene, dimethylbenzene or diethylbenzene, preferably toluene；
It is further preferred that the adjacent bromo-iodobenzene is 1g with the solvent load ratio:5-15mL.
6. the method according to claim any one of 2-5, it is characterised in that in step (2)：The catalyst is acetic acid
Palladium；
And/or, the part is in 2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl, triphenylphosphine or tricyclohexyl phosphine
One kind；
And/or, the inorganic base is one kind in potassium carbonate or sodium carbonate or cesium carbonate.
7. the method according to claim any one of 2-6, it is characterised in that in step (2), the intermediate two-(2-
Bromophenyl) amine, the palladium catalyst, phosphorus part molar feed ratio=1:0.003-0.03:0.006-0.06；
And/or, molar feed ratio=1 of the intermediate two-(2- bromophenyls) amine and inorganic base:2-3.
8. the method according to claim any one of 2-7, it is characterised in that in step (2), the ring closure reaction is molten
Carried out in agent；The one kind of the solvent in DMF or NMP or DME, preferably DMF；
More preferably described intermediate two-(2- bromophenyls) amine is 1g with the solvent load ratio:5-15mL.
9. the method according to claim any one of 2-8, it is characterised in that obtain step (2) described ring closure reaction
1- bromine carbazole crude products go out through elutriation, cross silicagel column, are then recrystallized with hexamethylene or normal heptane, produce 1- bromines carbazole essence
Product.
10. according to the method described in claim 1, it is characterised in that methods described comprises the following steps：
(1) under inert gas shielding, by adjacent bromo-iodobenzene and o-bromoaniline in the presence of catalyst, part and organic base,
Liv Ullmann coupling reaction is carried out in toluene, the intermediate two-(2- bromophenyls) amine is made；
The catalyst is three (dibenzalacetone) two palladium or [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride；Institute
It is one kind in tri-butyl phosphine or triphenylphosphine or tricyclohexyl phosphine to state part；The organic base is sodium tert-butoxide；
The molar feed ratio of the adjacent bromo-iodobenzene and the o-bromoaniline is 1:0.85-1；The adjacent bromo-iodobenzene, the catalyst
And the molar feed ratio of the part is 1:0.003-0.03:0.006-0.06；The ideal of the adjacent bromo-iodobenzene and organic base
Mol ratio is 1:2-3；
(2) under inert gas shielding, the intermediate two-(2- bromophenyls) amine is deposited catalyst, part and inorganic base
Under, ring closure reaction is carried out in DMF, product produces 1- bromine carbazoles after separating-purifying；
The catalyst is palladium；The part is 2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl, triphenylphosphine
Or one kind in tricyclohexyl phosphine；The inorganic base is one kind in potassium carbonate or sodium carbonate or cesium carbonate；
The intermediate two-(2- bromophenyls) amine, the palladium catalyst, phosphorus part molar feed ratio=1:0.003-
0.03:0.006-0.06；Molar feed ratio=1 of the intermediate two-(2- bromophenyls) amine and inorganic base:2-3.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651232A (en) * | 2018-12-12 | 2019-04-19 | 河北华清光电材料有限公司 | The method for preparing 4- bromine carbazole and its derivative |
| JP2019137613A (en) * | 2018-02-06 | 2019-08-22 | 東ソー株式会社 | Method for producing (diarylamino) carbazole |
| CN111960989A (en) * | 2020-08-28 | 2020-11-20 | 中钢集团南京新材料研究院有限公司 | Preparation method of 4-bromocarbazole |
| CN113480470A (en) * | 2021-08-11 | 2021-10-08 | 山东瑞辰新材料有限公司 | Preparation method of 3-bromo-N-phenylcarbazole |
| CN113582910A (en) * | 2021-08-27 | 2021-11-02 | 中钢集团南京新材料研究院有限公司 | Synthesis method of 1-bromocarbazole by taking carbazole as raw material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102770981A (en) * | 2010-02-26 | 2012-11-07 | 新日铁化学株式会社 | Organic electroluminescent element |
| WO2013023292A1 (en) * | 2011-08-12 | 2013-02-21 | Uti Limited Partnership | Fluorescent dyes with large stokes shifts |
| WO2015088183A1 (en) * | 2013-12-13 | 2015-06-18 | 덕산네오룩스 주식회사 | Compound for organic electric element, organic electric element using same and electronic device thereof |
| KR20150098062A (en) * | 2014-02-19 | 2015-08-27 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| CN104396042B (en) * | 2012-06-28 | 2016-10-12 | 新日铁住金化学株式会社 | Material for organic electroluminescence device and organic electroluminescent device |
| CN106397304A (en) * | 2016-08-31 | 2017-02-15 | 河南省科学院化学研究所有限公司 | Production method of 1-bromocarbazole |
-
2017
- 2017-05-24 CN CN201710374924.1A patent/CN107325037B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102770981A (en) * | 2010-02-26 | 2012-11-07 | 新日铁化学株式会社 | Organic electroluminescent element |
| WO2013023292A1 (en) * | 2011-08-12 | 2013-02-21 | Uti Limited Partnership | Fluorescent dyes with large stokes shifts |
| CN104396042B (en) * | 2012-06-28 | 2016-10-12 | 新日铁住金化学株式会社 | Material for organic electroluminescence device and organic electroluminescent device |
| WO2015088183A1 (en) * | 2013-12-13 | 2015-06-18 | 덕산네오룩스 주식회사 | Compound for organic electric element, organic electric element using same and electronic device thereof |
| KR20150098062A (en) * | 2014-02-19 | 2015-08-27 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| CN106397304A (en) * | 2016-08-31 | 2017-02-15 | 河南省科学院化学研究所有限公司 | Production method of 1-bromocarbazole |
Non-Patent Citations (4)
| Title |
|---|
| CHING-YUAN LIU等: "Preparation of polyfunctional arylmagnesium reagents bearing a triazene moiety. A new carbazole synthesis", 《ORGANIC LETTERS》 * |
| LIN-SONG CUI等: "Controlling Singlet-Triplet Energy Splitting for Deep-Blue Thermally Activated Delayed Fluorescence Emitters", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| MASAKI NUMATA等: "High efficiency pure blue thermally activated delayed fluorescence molecules having 10H-phenoxaborin and acridan units", 《CHEMICAL COMMUNICATIONS》 * |
| YASUO KIKUGAWA等: "Synthesis of carbazoles from N-(N,N-diarylamino)phthalimides with aluminum chloride via diarylnitrenium ions", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019137613A (en) * | 2018-02-06 | 2019-08-22 | 東ソー株式会社 | Method for producing (diarylamino) carbazole |
| JP7142440B2 (en) | 2018-02-06 | 2022-09-27 | 東ソー株式会社 | Method for producing (diarylamino)carbazole |
| CN109651232A (en) * | 2018-12-12 | 2019-04-19 | 河北华清光电材料有限公司 | The method for preparing 4- bromine carbazole and its derivative |
| CN111960989A (en) * | 2020-08-28 | 2020-11-20 | 中钢集团南京新材料研究院有限公司 | Preparation method of 4-bromocarbazole |
| CN113480470A (en) * | 2021-08-11 | 2021-10-08 | 山东瑞辰新材料有限公司 | Preparation method of 3-bromo-N-phenylcarbazole |
| CN113480470B (en) * | 2021-08-11 | 2023-09-26 | 山东瑞辰新材料有限公司 | Preparation method of 3-bromo-N-phenylcarbazole |
| CN113582910A (en) * | 2021-08-27 | 2021-11-02 | 中钢集团南京新材料研究院有限公司 | Synthesis method of 1-bromocarbazole by taking carbazole as raw material |
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