CN107428688A - Efficient Synthesis of Carbazole Derivatives - Google Patents
Efficient Synthesis of Carbazole Derivatives Download PDFInfo
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- CN107428688A CN107428688A CN201680017970.XA CN201680017970A CN107428688A CN 107428688 A CN107428688 A CN 107428688A CN 201680017970 A CN201680017970 A CN 201680017970A CN 107428688 A CN107428688 A CN 107428688A
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- C07D209/56—Ring systems containing three or more rings
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Abstract
The invention relates to a synthesis method of a carbazole derivative, which comprises the following steps: a step 1) of substituting an amido group or a nitro group for an amino group by subjecting a compound represented by the following chemical formula 1 to acetylation reaction or oxidation; step 2), carrying out Ullmann coupling reaction on the compound comprising the acylamino or the nitro to synthesize a biphenyl compound; and step 3) adding phosphoric acid to the biphenyl compound to synthesize a carbazole derivative.
Description
Technical field
Being used as the present invention relates to one kind in Organic Light Emitting Diode (Organic Light Emitting Diode) is made
The synthetic method of two substitution -9H- carbazoles of the basic intermediate of carbazole derivates.
Background technology
Organic electronic material is used for the field of electronics industry includes the field for Organic Light Emitting Diode (OLED), use
It is used for organic FET in the field of organic solar batteries (organic photovoltaic battery) and as switching device (organic transistor) and has
Machine TFT field.
Wherein, the material when organic compound is excited by electric current is utilized to send out in Organic Light Emitting Diode (OLED) field
The characteristic of light.Organic Light Emitting Diode is as the cathode-ray tube when manufacturing existing flat panel display unit and liquid crystal display
Substitute causes concern, also, the device size including Organic Light Emitting Diode is small and low in energy consumption, therefore can be used for such as hand
The mobile devices such as machine, notebook computer, digital camera, MP3 player and illuminator etc..In Organic Light Emitting Diode field
In, as carbazole derivates, using the carbazole derivates with hole transport performance and with high-fire resistance structure, for use as electricity
Material of the charge transport material of sub- electrophotographic photoconductor or organic EL (electroluminescent) device etc..
On the other hand, in existing carbazole derivates preparation method, using 9H- carbazoles as parent material, by making
With bromination reaction and n-BuLi come to synthesize the reaction of 3,6- Dimethylcarbazoles be common (prior art literature 2), still, due to
It is the Synthetic Method of Carbazole using nBuLi and tBuLi, and used material price is more expensive, dangerous, therefore is a kind of uneconomical
And poorly efficient synthetic method.Also, the Synthetic Method of Carbazole disclosed in prior art literature 1 is to use the bromo- 9H- carbazoles of 3,6- bis-
As parent material and using the Synthetic Method of Carbazole of nickel, but yield is low, uneconomical.Prior art literature 3 is disclosed using three
The carbazole synthetic method of Phenylphosphine.However, be connected in R with 3 and 6, rather than when being connected with existing No. 2 and No. 7, Wu Fajin
Line position puts selective reaction, therefore the shortcomings that producing accessory substance be present.Method disclosed in prior art literature 4 also overall yield
Low, poorly efficient, used material price is more expensive, therefore is uneconomic synthetic method.
As described above, existing Synthetic Method of Carbazole can not carry out regioselectivity reaction, therefore accessory substance is produced, effect be present
The shortcomings that rate difference.
On the other hand, it is well known that Suzuki coupling reaction is that one kind utilizes halogenated aromatic compound and aryl boric acid chemical combination
Thing to synthesize the coupling reaction of asymmetric biaryl compound with one step.Generally, it is main in above-mentioned Suzuki coupling reaction
Phosphine palladium catalyst has been used, but has used such as various catalysis of palladium nano-particles, water-soluble phosphine ligand, nucleophilic carbene ligands recently
Agent, or for having carried out various researchs using microwave technology etc. to improve the method for the efficiency of catalyst.However, even in this
In the case of, there is also the problem of severe reaction conditions, for example, TBAB of quaternary ammonium salt high as unit price etc. is must be added to, and must
It must at very high temperatures react etc., also, also exist due to regioselectivity reaction can not be realized and produce a large amount of
Accessory substance the problem of.
Therefore, inventor developed a kind of novel carbazole derivates synthesis side suitable for Organic Light Emitting Diode
Method, it uses the material different from the parent material of existing carbazole derivates synthetic method.
The A1 of (patent document 1) 1.WO 2014021569
(non-patent literature 1) 2.Inorg.Chem., 2003,42 (11), the 3454-3465 pages, Britovsek, G.J.P.
Deng
(non-patent literature 2) 3.J.Org.Chem., 2005,70 (13), the 5014-5019 pages, Adam W.Freeman etc.
(non-patent literature 3) 4.J.Org.Chem., 2013,78 (13), the 6688-6701 pages, Benito Alcaide
Deng.
The content of the invention
Technical problem
It is an object of the invention to provide a kind of synthetic method of carbazole derivates.
Solution to problem
In order to reach the purpose, the present invention provides a kind of synthetic method of carbazole derivates, it is characterised in that including:
Step 1), taken by the compound for making to be represented by following chemical formula 1 by acetylization reaction or oxidation with amide groups or nitro
For amino;Step 2), the compound including the amide groups or the nitro is passed through into Liv Ullmann coupling reaction, synthesizes biphenyl
Compound;And step 3), phosphoric acid is added to the biphenol compound to synthesize carbazole derivates.
[chemical formula 1]
(in chemical formula 1, R1To R4Hydrogen atom, D-atom, substituted or unsubstituted C1~C25 alkane are represented independently of one another
Base, substituted or unsubstituted C2~C25 alkenyls, substituted or unsubstituted C1~C25 alkoxies, substituted or unsubstituted C6~
C30 aryl, substituted or unsubstituted C5~C25 heteroaryls, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl or fluoroform
Base, X are halogen atom.)
The whole preparation method of the present invention is not limited to this, and can be represented by following reaction equations 1 or reaction equation 2.Although
One R group is shown in following reaction equations 1 or reaction equation 2 to represent R1To R4, but this is only used for illustrating the present invention, and this hair
It is bright to be not limited to this.
[reaction equation 1]
[reaction equation 2]
In one particular embodiment of the present invention, the synthetic method of the carbazole derivates can include:Step 1), lead to
The compound for making to be represented by following chemical formula 1 is crossed by acetylization reaction come with amide groups substituted-amino;Step 2), institute will be included
The compound for stating amide groups passes through Liv Ullmann coupling reaction, synthesizes biphenol compound;And step 3), to the biphenol compound
Phosphoric acid is added to synthesize carbazole derivates.
[chemical formula 1]
(in chemical formula 1, R1To R4Hydrogen atom, D-atom, substituted or unsubstituted C1~C25 alkane are represented independently of one another
Base, substituted or unsubstituted C2~C25 alkenyls, substituted or unsubstituted C1~C25 alkoxies, substituted or unsubstituted C6~
C30 aryl, substituted or unsubstituted C5~C25 heteroaryls, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl or fluoroform
Base, X are halogen atom.)
In the specific embodiment, the compound represented by chemical formula 1 can be to be represented by following chemical formula 1a
Compound.
[chemical formula 1a]
(in chemical formula 1a, R is hydrogen atom, D-atom, substituted or unsubstituted C1~C25 alkyl, substitution or unsubstituted
C2~C25 alkenyls, substituted or unsubstituted C1~C25 alkoxies, substituted or unsubstituted C6~C30 aryl, substitution or not
Substituted C5~C25 heteroaryls, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl, X are halogen atom.)
In the specific embodiment, for example, the compound represented by chemical formula 1 can be the bromo- 4- methylbenzenes of 3-
Amine, but it is not limited to this.
" acetylation (Acetylation) reaction " of the present invention be hydroxyl (- OH) in organic compound or amino (-
NH2) etc. hydrogen atom by acetyl group (CH3CO-) substitution reaction general name.
Acetylization reaction in the step 1) can use chloroacetic chloride, acetic acid according to common acetylization reaction condition
Acid anhydride, acetic acid, ketenes, acetyl bromide etc. are carried out.Also, the acetylization reaction step can be in such as organic solvent equal solvent
Carry out.Specifically, the acetylization reaction can use chloroacetic chloride (Acetyl chloride) and triethylamine (Triethyl
Amine) carry out.
More specifically, the acetylization reaction can be by adding dichloro to the compound represented by chemical formula 1
Methane, triethylamine and chloroacetic chloride are simultaneously stirred to carry out.As the result of the acetylization reaction, amino is substituted by amide groups, from
And acetamide compound can be obtained, it is preferable that the acetamide compound represented by the chemical formula 2a can be obtained.
" the Liv Ullmann coupling " of the present invention refers to the coupling reaction between halogenated aryl compound, i.e. fixed under high-temperature
Measure the method that symmetrical biaryl compound is formed using copper catalyst etc..
Liv Ullmann coupling reaction in the step 2) can be according to common Liv Ullmann coupling reaction condition in methanol
Carried out in the presence of the alkali such as sodium, caustic alcohol or potassium methoxide.Also, the coupling reaction step can be in water or including the water-soluble of water
Carried out in agent.Preferably, the Liv Ullmann coupling reaction can in the presence of copper catalyst, 100~200 DEG C, 150~
Carried out at 200 DEG C or 160~180 DEG C.
In a particular embodiment of the present invention, it is preferable that the Liv Ullmann coupling reaction can be a small amount of by being added to DMF
Copper and iodine and stir, also add and carried out by the chemical formula 2a material represented and stirring.It is coupled as the Liv Ullmann
The result of reaction, biphenol compound can be obtained, specifically, biphenyl diacetyl amines can be obtained, it is preferable that can be with
Obtain the biphenyl diacetyl amines represented by the chemical formula 3a.
The step 3) is to biphenol compound, specifically, adds phosphoric acid to biphenyl diacetamide compound to close
The step of into carbazole derivates, it is preferable that the synthesis can synthesize (Tauber Carbazole by Tao Beier carbazoles
Synthesis) method is carried out.Wherein it is possible to it is used as solvent using diethylene glycol (DEG), but the invention is not restricted to this.Specifically, as most
The carbazole derivates of end-product can be dibasic carbazole derivates, can be that 1,8- bis- substitutes -9H- clicks more specifically
Zole derivatives, 2,7- bis- substitute -9H- carbazole derivates, 3,6- bis- to substitute -9H- carbazole derivates or 4,5- bis- to substitute -9H- clicks
Zole derivatives, it is preferable that can be that 3, the 6- bis- represented by the chemical formula 4 substitutes -9H- carbazole derivates, but be not limited to
This, according to R1To R4Type can be the carbazole derivates with various substituents.In this carbazole derivates synthesis step,
The carbazole ring of pentagon shape is formed on the carbon potential being connected with amino of the biphenol compound, therefore, can be selected with position
Synthesize carbazole derivates to property.
In the another specific embodiment of the present invention, the synthetic method of the carbazole derivates can include:Step 1), lead to
Crossing makes by the compound that following chemical formula 1 represents through peroxidating come with nitro substituted-amino;Step 2), by including the nitro
Compound passes through Liv Ullmann coupling reaction, synthesizes biphenol compound;And step 3), to the biphenol compound add phosphoric acid with
Synthesize carbazole derivates.
[chemical formula 1]
(in chemical formula 1, R1To R4Hydrogen atom, D-atom, substituted or unsubstituted C1~C25 alkane are represented independently of one another
Base, substituted or unsubstituted C2~C25 alkenyls, substituted or unsubstituted C1~C25 alkoxies, substituted or unsubstituted C6~
C30 aryl, substituted or unsubstituted C5~C25 heteroaryls, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl or fluoroform
Base, X are halogen atom.)
In the specific embodiment, the compound represented by chemical formula 1 can be to be represented by following chemical formula 1a
Compound.
[chemical formula 1a]
(in chemical formula 1a, R is hydrogen atom, D-atom, substituted or unsubstituted C1~C25 alkyl, substitution or unsubstituted
C2~C25 alkenyls, substituted or unsubstituted C1~C25 alkoxies, substituted or unsubstituted C6~C30 aryl, substitution or not
Substituted C5~C25 heteroaryls, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl, X are halogen atom.)
In the specific embodiment, for example, the compound represented by chemical formula 1 can be the iodo- 4- methylbenzenes of 3-
Amine, but it is not limited to this.
" oxidation (oxidation) reaction " of the present invention refers to that molecule, atom or ion lose electronics, with its oxidation number
(oxidation number) rises.In the method, oxidation reaction refers to the reaction into nitro by amino group.
The oxidation reaction of the step 1) can be carried out according to common oxidation reaction condition using known oxidant.
Also, the oxidation step can be carried out in such as organic solvent equal solvent.Specifically, the oxidation of the step 1) can
To use 3- chloroperoxybenzoic acids (meta-Chloroperoxybenzoic acid;M-CPBA) carry out.
More specifically, the oxidation reaction can be by adding m-CPBA to the compound represented by chemical formula 1
Carried out with toluene and stirring.As the result of the oxidation reaction, amino is substituted by nitro, it is thus possible to obtain containing nitro
Compound, it is preferable that can obtain by the chemical formula 2b represent the compound containing nitro.
The Liv Ullmann coupling reaction of the step 2) can be according to common Liv Ullmann coupling reaction condition in sodium methoxide, second
Carried out in the presence of the alkali such as sodium alkoxide or potassium methoxide.Also, the coupling reaction step can be in water or including in the aqueous solvent of water
Carry out.Preferably, the Liv Ullmann coupling reaction can in the presence of copper catalyst, at 100~200 DEG C, 100~150 DEG C
Or carried out at 110~130 DEG C.
In a particular embodiment of the present invention, it is preferable that the Liv Ullmann coupling reaction can be a small amount of by being added to DMF
Copper and iodine and stir, also add and carried out by the chemical formula 2b material represented and stirring.It is coupled as the Liv Ullmann
The result of reaction, biphenol compound can be obtained, specifically, dinitro biphenol compound can be obtained, it is preferable that can obtain
The dinitro biphenol compound represented by the chemical formula 3b-1.
After the step 2), step 2 may also include '), i.e. reduction biphenol compound, the step of nitro is substituted with amino
Suddenly.Preferably, the reduction can be realized using ammonium formate and Pd/C catalyst.Specifically, parent material:Ammonium formate:
Pd/C (10wt%) optimum mole ratio can be 1:19~20:0.01~0.2, can be 1 more specifically:19~20:
0.1.Wherein, as solvent, can use water and isopropanol with 1~20:The mixture that 1 volume ratio mixes, but this
Invention not limited to this, specifically, the volume ratio of water and isopropanol can be 5~15:1, can be 10 more specifically:1.
By the reaction, the nitro of dinitro biphenol compound is substituted by amino, excellent so as to prepare benzidine compound
Selection of land, the benzidine compound represented by the chemical formula 3b-2 can be prepared.
The step 3) is that specifically, benzidine compound adds phosphoric acid to synthesize click to biphenol compound
The step of Zole derivatives, it is preferable that the synthesis can be carried out by Tao Beier carbazoles synthetic method.It is wherein it is possible to sweet using two
Alcohol is used as solvent, but the invention is not restricted to this.Specifically, the carbazole derivates as final product can be dibasic click
Zole derivatives, more specifically, can be 1,8- bis- substitute -9H- carbazole derivates, 2,7- bis- substitute -9H- carbazole derivates,
3,6- bis- substitute -9H- carbazole derivates or 4,5- bis- to substitute -9H- carbazole derivates, it is preferable that can be by the chemical formula 4
3, the 6- bis- represented substitutes -9H- carbazole derivates, but is not limited to this, according to R1To R4Type can be with various substitutions
The carbazole derivates of base.In this carbazole derivates synthesis step, on the carbon potential being connected with amino of the biphenol compound
The carbazole ring of pentagon shape is formed, therefore, carbazole derivates can be synthesized with regioselectivity.
In a particular embodiment of the present invention, synthesized as the carbazole derivates used in Organic Light Emitting Diode
The 3,6- bis- of basic intermediate substitutes -9H- carbazoles.It is used as starting material using the bromo- 4- methylanilines of 2- or the iodo- 4- methylanilines of 2-
Material, is synthesized by acetylization reaction (or oxidation reaction), Liv Ullmann coupling reaction (reduction reaction), Tao Beier carbazoles synthetic method
Final 3,6- bis- substitutes -9H- carbazoles.The above method of the present invention is by using different from existing carbazole synthesis parent material
Material come the new synthesis method developed, due to realizing that regioselectivity reacts, and product yield is high.Also, due to as rise
The aniline compound of beginning material is cheap and is readily available in this area, has cost benefit, thus, it is expected that can give birth in batches
Production.
Unless otherwise defined, all technologies used herein and the implication of scientific terminology and technology of the art
Being generally understood that for personnel is identical.Generally, nomenclature used herein is well known in the art and generally use.
The effect of invention
The synthetic method of the present invention realizes that effective carbazole synthesizes by regioselectivity reaction, and product yield is high, has
Validity and economy.Also, the two substitution -9H- carbazoles as the final product of the present invention may be used as preparing organic hair
Basic intermediate during optical diode.Not only in this, parent material is readily available, cheap, it is therefore expected that can give birth in batches
Produce two substitution -9H- carbazoles.
Brief description of the drawings
Fig. 1 is the iodo- 4- nitrotoleunes of 3-1H-NMR spectrograms.
Fig. 2 is 5,5 '-dimethyl -2,2- dinitros -1,1 '-biphenyl1H-NMR spectrograms.
Fig. 3 is 5,5 '-dimethyl -2,2- dinitros -1,1 '-biphenyl13C-NMR spectrograms.
Fig. 4 is 5,5 '-dimethyl-[1,1 '-biphenyl] -2,2 '-diamines1H-NMR spectrograms.
Fig. 5 is 5,5 '-dimethyl-[1,1 '-biphenyl] -2,2 '-diamines13C-NMR spectrograms.
Fig. 6 is 3,6- dimethyl -9H- carbazoles1H-NMR spectrograms.
Fig. 7 is 3,6- dimethyl -9H- carbazoles13C-NMR spectrograms.
Fig. 8 is N- (the bromo- 4- aminomethyl phenyls of 2-) acetamide1H-NMR spectrograms.
Fig. 9 is N, N '-(5,5 '-dimethyl-[1,1 '-biphenyl] -2,2 '-diyl)-diacetamide1H-NMR spectrum
Figure.
Figure 10 is N, N '-(5,5 '-dimethyl-[1,1 '-biphenyl] -2,2 '-diyl)-diacetamide13C-NMR spectrum
Figure.
Figure 11 is 3,6- dimethyl -9H- carbazoles1H-NMR spectrograms.
Figure 12 is 3,6- dimethyl -9H- carbazoles13C-NMR spectrograms.
Embodiment
Hereinafter, the embodiment present invention detailed further is passed through.These embodiments are served only for illustrating the present invention, are not interpreted as
The invention of the present invention is claimed scope and is confined to these embodiments, this ordinary skill people for the technical field of the invention
It is obvious for member.
Embodiment 1:Prepare 3,6- dimethyl -9H- carbazoles (1)
Embodiment 1-1:Prepare the iodo- 4- nitrotoleunes of 3-
The 2mL compound (the iodo- 4- methylanilines of 2-) represented by chemical formula 1 and 13.9g is dissolved in 100mL toluene
3- chloroperoxybenzoic acids to obtain mixed liquor, the mixed liquor is added in 250mL round-bottomed flasks, in reflux temperature (120
DEG C) under stir 6 hours.After being cooled with an ice bath, filtered with washed with ether and to the solid of gained.Filtrate sodium hydroxide
(10%) it is neutralized to pH7.The filtrate of neutralization is transferred in separatory funnel, then extracted with saline solution.For separated
Organic layer, use MgSO4Residual water is removed, is then filtered with diatomite.Solvent is removed under reduced pressure from filtrate, uses post color
Compose separation product (hexane (hexane):EA=9:1).After vacuum drying, the iodo- 4- nitrotoleunes of 3- for obtaining 3.42g (are received
Rate:75%) (Fig. 1).
It is used as the nuclear magnetic resonance for the compound that target material obtains in each step according to the present embodiment by analyzing
(NMR) result that data obtain is shown in Fig. 1 to 12.Wherein, the condition determination of nuclear magnetic resonance (NMR) is as follows.
1. device:Nmr analysis (device:Brooker (Bruker) 400MHz)
2. measurement range:- 0.5~10.5ppm (1H);0~200ppm (13C)
3. scanning times:16(1H);50(13C)
Shown in the following reaction equation 3 of schematic reaction equation of the reaction.
[reaction equation 3]
Embodiment 1-2:Prepare 5,5 '-dimethyl -2,2- dinitros -1,1 '-biphenyl
After reflux condenser is set, under inert conditions, to 50mL dimethylformamide
(Dimethylformamide, DMF) adds 3.87g Cu and a small amount of I2, stir 5 minutes.To mixture addition 2.1g's
The prepared iodo- 4- nitrotoleunes of 3-, are then stirred 1 hour at 120 DEG C in the embodiment 1-2.After the completion of reaction, it is cold
But mixture, the 1g sodium acid carbonates that are dissolved in 20mL water are then slowly added to mixture in ice bath.Mixture is being subtracted
Pressure filtering filtrate be transferred in separatory funnel to remove sediment, then add 15mL dichloromethane and 15mL salt
The aqueous solution simultaneously shakes up, to be separated into water layer and dichloromethane layer.(15mL × 3 time) are extracted, until there is no product in water layer
Residual.Afterwards, dichloromethane layer is separated, uses MgSO4Go to remove water, be then filtered under diminished pressure, then, evaporate dichloromethane.So
Afterwards, column chromatography separation product (Hexane is passed through:EA=10:1).Finally, after vacuum drying, 1.8g conduct target is obtained
5,5 '-dimethyl -2,2- dinitros -1,1 '-biphenyl (5,5 '-dimethyl-2,2-dinitro- of the yellow solid of compound
1,1 '-biphenyl) (yield:85%) (Fig. 2,3).
Shown in the following reaction equation 4 of schematic reaction equation of the reaction.
[reaction equation 4]
Embodiment 1-3:Prepare 5,5 '-dimethyl-[1,1 '-biphenyl] -2,2 '-diamines
To 10mL isopropanols addition 0.03g Pd/C (10 weight % palladium/activated carbons).0.38g is dissolved in 2mL water
Ammonium formate, be added in the mixture and stir 2 minutes.The 0.08g implementation is dissolved in 10mL isopropanols
Prepared 5 in example 1,5 '-dimethyl -2,2- dinitro -1, after 1 '-biphenyl, second of mixture is added slowly to
In, stir the mixture obtained by 15 minutes.After the completion of reaction, mixture is filtered under diminished pressure with diatomite.In evaporation institute
After having filtrate, add 10mL dichloromethane and 10mL saline solution and shake up, to separate dichloromethane layer.Then, carry out
Extract (10mL × 2 time), until there is no product residual in water layer.Afterwards, dichloromethane layer is separated, uses MgSO4Go to remove water, then
It is filtered under diminished pressure, then, evaporates dichloromethane.Then, column chromatography separation product (hexane is passed through:EA=4:1).Most
Afterwards, after vacuum drying, 5 of 0.06g thick pale yellow thing i.e. as target compound, 5 '-dimethyl-[1,1 '-connection are obtained
Benzene] -2,2 '-diamines (- the diamine of 5,5 '-dimethyl- [1,1 '-biphenyl] -2,2 ') (yield:96%) (Fig. 4,5).
Similarly, also tested (table 1) twice by changing ammonium formate, isopropanol and Pd/C mol ratio.
【Table 1】
Use the NO of ammonium formate2Reduction reaction
The schematic reaction equation of the reduction reaction is as follows.
[reaction equation 5]
Embodiment 1-4:Prepare 3,6- dimethyl -9H- carbazoles
5,5 ' prepared-dimethyl in the embodiment 1-3 of diethylene glycol (DEG) addition 0.13g to 8mL-[1,1 '-connection
Benzene] -2,2 '-diamines and 1mL phosphoric acid.After reflux condenser is set, 24 hours are stirred at 200 DEG C, after the completion of reaction,
Mixture is cooled down at normal temperatures.Mixture is slowly added in ice bath 0.5g sodium acid carbonates being dissolved in what is formed in 10mL water
Solution, then extracted (10mL × 2 time) with 10mL dichloromethane.For separated dichloromethane layer, MgSO is used4Go
Water removal, is filtered under diminished pressure, then evaporates dichloromethane.Afterwards, column chromatography separation product (hexane is passed through:EA=5:
10).Finally, after vacuum drying, 3, the 6- dimethyl -9H- clicks of the 0.103g gold solid as target compound are obtained
Azoles (yield:85%) (Fig. 6,7).
The schematic reaction equation of the reduction reaction is as follows..
[reaction equation 6]
Embodiment 2:Prepare 3,6- dimethyl -9H- carbazoles (2)
Embodiment 2-1:Prepare N- (the bromo- 4- aminomethyl phenyls of 2-) acetamide
The compound represented by chemical formula 1 (the bromo- 4- methylanilines of 2-) is added in 50mL round-bottomed flasks, also added
20mL dichloromethane and 0.9mL triethylamine.In ice bath, 0.46mL chloroacetic chloride is slowly added, then removes ice bath simultaneously
Stir 10 minutes at normal temperatures.After the completion of reaction, the pH of mixture is adjusted to 7 to 8 with 1M sodium hydroxide solutions.Will mixing
Liquid is transferred in separatory funnel, is then added 20mL saline solution and is shaken up, to be divided into water layer and dichloromethane layer, is extracted
Take, until there is no product residual in water layer.Afterwards, from dichloromethane layer MgSO4Go to remove water, be filtered under diminished pressure, Ran Houtong
Pervaporation device evaporates dichloromethane.Afterwards, silica gel column chromatography separation product (Hexane is passed through:EA=8:1(v/v)).Finally,
After vacuum drying, N- (the bromo- 4- aminomethyl phenyls of 2-) acetamide (N- of 1.2g Baise solid as target compound is obtained
(2-bromo-4-methylphenyl) acetamide) (yield:100%) (Fig. 8).
Shown in the following reaction equation 7 of schematic reaction equation of the reaction.
[reaction equation 7]
Embodiment 2-2:Preparation N, N '-(5,5 '-dimethyl-[- 1,1 '-biphenyl] -2,2 '-diyl)-diacetamide
After reflux condenser is set, under inert conditions, 0.27g Cu is added to 7mL dimethylformamide and lacked
Measure I2, stir 5 minutes.To N- (the bromo- 4- methylbenzenes of 2- prepared in the mixture addition 0.47g embodiment 2-1
Base) acetamide, is then stirred 30 minutes at 170 DEG C.After the completion of reaction, mixture is cooled down, then to mixing in ice bath
Thing is slowly added to for sodium acid carbonate to be dissolved in the solution formed in 10mL water.Mixture is filtered under reduced pressure to remove precipitation
It thing, filtrate be transferred in separatory funnel, then add 15mL dichloromethane and 15mL saline solution and shake up, with separation
Into water layer and dichloromethane layer.Extracted, until there is no product residual in water layer.Afterwards, dichloromethane layer is separated, is used
MgSO4Go to remove water, be then filtered under diminished pressure, evaporate dichloromethane.Afterwards, column chromatography separation product (Hexane is passed through:EA
=1:1).Finally, after vacuum drying, the N of 0.23g Baise solid as target compound is obtained, N '-(5,5 '-diformazan
Base-[1,1 '-biphenyl] -2,2 '-diyl)-diacetamide (N, N '-(5,5 '-dimethyl- [1,1 '-biphenyl] -2,
2 '-diyl)-diacetamide) (yield:78%) (Fig. 9,10).
Shown in the following reaction equation 8 of schematic reaction equation of the reaction.
[reaction equation 8]
Embodiment 2-3:Prepare 3,6- dimethyl -9H- carbazoles
Prepared N in the embodiment 2-2 of diethylene glycol (DEG) addition 0.13g to 8mL, N '-(5,5 '-dimethyl-[1,
1 '-biphenyl] -2,2 '-diyl)-diacetamide and 0.39mL concentrated phosphoric acid.After reflux condenser is set, stirred at 200 DEG C
Mix 24 hours, after the completion of reaction, cool down mixture at normal temperatures.Mixture is slowly added to by 0.5g bicarbonates in ice bath
Sodium is dissolved in the solution formed in 10mL water, is then extracted (10mL × 2 time) with 10mL dichloromethane.For separated
Dichloromethane layer, use MgSO4Go to remove water, be filtered under diminished pressure, then evaporate dichloromethane.Afterwards, column chromatography point is passed through
From product (hexane:EA=8:10).Finally, after vacuum drying, the 0.05g gold solid as target compound is obtained
3,6- dimethyl -9H- carbazole (yields:78%) (Figure 11,12).
The schematic reaction equation of the reduction reaction is as follows.
[reaction equation 9]
Claims (11)
1. a kind of synthetic method of carbazole derivates, including:
Step 1), acetylization reaction or oxidation are passed through come with amide groups or nitre by the compound for making to be represented by following chemical formula 1
Base substituted-amino;
Step 2), the compound including the amide groups or the nitro is passed through into Liv Ullmann coupling reaction, synthesizes biphenyl chemical combination
Thing;And
Step 3), phosphoric acid is added to the biphenol compound to synthesize carbazole derivates,
[chemical formula 1]
In chemical formula 1, R1To R4Hydrogen atom, D-atom are represented independently of one another, substituted or unsubstituted C1~C25 alkyl, are taken
Generation or unsubstituted C2~C25 alkenyls, substituted or unsubstituted C1~C25 alkoxies, substituted or unsubstituted C6~C30 virtues
Base, substituted or unsubstituted C5~C25 heteroaryls, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl, X are
Halogen atom.
2. the synthetic method of carbazole derivates according to claim 1, it is characterised in that the acetyl in the step 1)
Change reaction by being realized using only chloroacetic chloride and triethylamine.
3. the synthetic method of carbazole derivates according to claim 1, it is characterised in that the oxidation in the step 1)
Realized by using 3- chloroperoxybenzoic acids.
4. the synthetic method of carbazole derivates according to claim 1, it is characterised in that the step 2) is in copper catalyst
In the presence of, carry out at 100~200 DEG C.
5. the synthetic method of carbazole derivates according to claim 1, it is characterised in that in the step 2), inciting somebody to action
When compound including nitro passes through Liv Ullmann coupling reaction, also include step 2 after the step 2) '):Reduce biphenyl
Compound, nitro is substituted with amino.
6. the synthetic method of carbazole derivates according to claim 5, it is characterised in that the reduction is by using formic acid
Ammonium and Pd/C catalyst are realized.
7. the synthetic method of carbazole derivates according to claim 5, it is characterised in that made in the reduction step
Solvent is the mixture of water and isopropanol.
8. the synthetic method of carbazole derivates according to claim 7, it is characterised in that the volume of the water and isopropanol
Than for 1~20:1.
9. the synthetic method of carbazole derivates according to claim 1, it is characterised in that the solvent in the step 3)
For diethylene glycol (DEG).
10. the synthetic method of carbazole derivates according to claim 1, it is characterised in that described to be represented by chemical formula 1
Compound is the bromo- 4- methylanilines of 2- or the iodo- 4- methylanilines of 2-.
11. the synthetic method of carbazole derivates according to claim 1, it is characterised in that the carbazole derivates are 3,
6- bis- substitutes -9H- carbazole derivates.
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Non-Patent Citations (5)
Title |
---|
LIVIO RACAN ET AL.: "New pentacyclic ring systems: intramolecular cyclization of o,o-disubstituted bibenzothiazoles", 《TETRAHEDRON》 * |
SARIKA GUPTA ET AL.: "Biphenyl ethers conjugated CdSe/ZnS core/shell quantum dots and interpretation of the mechanism of amyloid fibril disruption", 《BIOMATERIALS》 * |
TAKEHIKO YAMATO ET AL.: "Organic Reactions Catalyzed by Solid Superacids.10.1 Perfluorinated Sulfonic Acid Resin(Nafion-H) Catalyzed Ring Closure Reaction of 2,2-Diaminobiphenyle. A Preparative Route to Carbazoles", 《J.ORG.CHEM》 * |
Y.TSUNASHIMA ET AL.: "Methyl Migration and Demethylation in the 4,5-Dimethylcarbazole Synthesis by Tauber Method", 《CHEMISCHER INFORMATIONSDIENST》 * |
汪多仁,等: "《绿色农药与化肥中间体》", 30 April 2009 * |
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