CN109369509A - A kind of synthetic method of N- (6- hydroxyl hexyl) carbazole derivates and N- (6- hydroxyl hexyl) carbazole and its derivative - Google Patents
A kind of synthetic method of N- (6- hydroxyl hexyl) carbazole derivates and N- (6- hydroxyl hexyl) carbazole and its derivative Download PDFInfo
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- CN109369509A CN109369509A CN201811343397.9A CN201811343397A CN109369509A CN 109369509 A CN109369509 A CN 109369509A CN 201811343397 A CN201811343397 A CN 201811343397A CN 109369509 A CN109369509 A CN 109369509A
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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
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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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
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Abstract
The present invention discloses the synthetic method of a kind of N- (6- hydroxyl hexyl) carbazole derivates and N- (6- hydroxyl hexyl) carbazole and its derivative, by carbazole or derivatives thereof, transfer catalyst dissolves the alkaline solution and 6- bromine n-hexyl alcohol for adding saturation afterwards in organic solvent, react carbazole or derivatives thereof sufficiently with 6- bromine n-hexyl alcohol, separation obtains N- (6- hydroxyl hexyl) carbazole or derivatives thereof, one step of method provided by the invention has synthesized N- (6- hydroxyl hexyl) carbazole and its derivative, reaction efficiency is high, reaction cost is low, substrate adaptive height etc., it is highly suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to azaaromatics synthesis technical fields, and in particular to a kind of N- (6- hydroxyl hexyl) carbazole
The synthetic method of derivative and N- (6- hydroxyl hexyl) carbazole and its derivative.
Background technique
N- (6- hydroxyl hexyl) carbazole and its derivative are a kind of important azaaromatics, intramolecular contain compared with
Big conjugated system and stronger cyclic voltammetry method, it is excellent that this special rigid condensed cyclic structure has carbazole compound
Good chemical stability and electron mobility energy.Electron rich structure is easy to N- (6- hydroxyl hexyl) carbazole and its derivative
Nucleophilic substitution occurs on carbazole ring and is readily incorporated into various functional groups to adjust the photoelectric properties of molecule.More attach most importance to
What is wanted is the presence due to hydroxyl group sites, so that N- (6- hydroxyl hexyl) carbazole and its derivative are easy to the method by grafting
It is connected on main polymer chain in the case where not influencing molecule photoelectric properties itself, convenient for being made into the excellent device of photoelectric properties
Meets the needs of application.
With deepening continuously to N- (6- hydroxyl hexyl) carbazole and its derivative research, researcher discovery is existing
Synthetic method has been unable to meet in N- (6- hydroxyl hexyl) carbazole and its ever-increasing trend of derivative demand.Therefore, it opens
It is extremely urgent to send out a kind of fast and efficiently synthetic method.N- (6- hydroxyl hexyl) carbazole and its derivative synthesizing process master at present
If by carbazole and its derivative, 1,6- dibromo-hexane react under alkaline condition generation N- (6- bromo hexyl) carbazole and its
Derivative, N- (6- bromo hexyl) carbazole and its derivative generate N- (6- acetyl oxygen with acetic acid sodium reaction under the action of catalyst
Base hexyl) carbazole and its derivative, product occur in strong base solution hydrolysis finally obtain N- (6- hydroxyl hexyl) carbazole and its
Derivative.The synthetic method complex steps need the long reaction time, while the synthesis of three steps greatly reduces the production of final product
Rate leads to the increase of synthesis cost.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of N- (6- hydroxyl hexyl) carbazole derivates and N- (6- hydroxyl
Hexyl) carbazole and its derivative synthetic method, the synthetic method is rapidly and efficiently.
Technical solution is as follows:
A kind of N- (6- hydroxyl hexyl) carbazole derivates, key are that its general formula is as follows:
Wherein R is alkoxy.
The synthetic method of a kind of N- (6- hydroxyl hexyl) carbazole and its derivative, key are to sequentially include the following steps:
Carbazole or derivatives thereof and phase transfer catalyst is taken to be added in organic solvent, it is organic molten that stirring is dissolved in carbazole or derivatives thereof
Agent adds saturation alkaline solution and 6- bromine n-hexyl alcohol, and wherein carbazole or derivatives thereof and the molar ratio of 6- bromine n-hexyl alcohol are
1:1.02-1.5, being vigorously stirred at 45-85 DEG C reacts carbazole or derivatives thereof sufficiently with 6- bromine n-hexyl alcohol, then separates
To N- (6- hydroxyl hexyl) carbazole or derivatives thereof.
The reaction process of above-mentioned synthetic method is as shown in Figure 1, one step of this method has synthesized N- (6- hydroxyl hexyl) carbazole
And its derivative, reaction efficiency is high, and reaction cost is low, and substrate adaptive height etc. is highly suitable for industrialization large-scale production.With it is existing
There is synthetic method to compare, this synthetic method has the advantage that related reaction has extraordinary tolerance to functional group
And universality, it can be used for preparing medicine, pesticide, photoelectric material and the polymer-function material of various N- (6- hydroxyl hexyl) carbazole
Deng；Reaction environment involved in this method is friendly, substrate without pre- function dough, without protective group and reaction does not need nothing
Water oxygen free condition operates very simple；Product is single, and separating-purifying is very convenient, and product purity is high.
Phase transfer catalyst dosage is the 5-10% of carbazole or derivatives thereof dosage, and every 1mol carbazole or derivatives thereof need to add
Enter 1.5-2.5L organic solvent, 1.0-1.5L strong base solution.
The above-mentioned reaction time is 3.5-5h.
The general formula of above-mentioned carbazole derivates is as follows:
Wherein R is selected from hydrogen or alkoxy.Wherein alkoxy can be methoxyl group (- O-CH3) etc..Above-mentioned phase transfer catalysis (PTC)
Agent is quaternary ammonium salt phase transfer catalyst；
The organic solvent is dimethyl sulfoxide, n,N-Dimethylformamide or 1,3- dimethyl -3,4,5,6- tetrahydro -2-
Pyrimidone；
The alkaline solution is sodium hydroxide solution, potassium hydroxide solution or Strong oxdiative calcium solution.This synthetic reaction is to alkali
The purity of solution does not require particularly.The best organic solvent of reaction is dimethyl sulfoxide, and DMF is in basic conditions shakiness
It is fixed, especially high temperature when easily decompose, the yield of final product can be reduced.
Above-mentioned reaction temperature is 65 DEG C, reaction time 4h, and carbazole or derivatives thereof and the molar ratio of 6- bromine n-hexyl alcohol are
1:1.2.The dosage of 6- bromine n-hexyl alcohol is slightly larger than in carbazole or derivatives thereof, fully reacting is advantageously ensured that, if 6- bromine n-hexyl alcohol
It is excessive will cause again product with and 6- bromine n-hexyl alcohol further react, reaction yield highest when the ratio of the two is 1:1.2 is reacted
Four hourly outputs are up to 90% or more.
Above-mentioned quaternary ammonium salt is benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, tetrabutylammonium bromide, tetrabutyl chlorination
Ammonium, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
The utility model has the advantages that using the beneficial effects of the invention are as follows a steps to have synthesized N- (6- hydroxyl hexyl) carbazole and its derivative
Object, reaction efficiency is high, and reaction cost is low, and substrate adaptive height etc. is highly suitable for industrialization large-scale production.With existing synthesis side
Method is compared, and reaction involved in this synthetic method has extraordinary tolerance and universality to functional group, can be used for preparing each
The medicine, pesticide, photoelectric material and polymer-function material etc. of kind N- (6- hydroxyl hexyl) carbazole；Reaction involved in this method
It is environmental-friendly, substrate without pre- function dough, without protective group and reaction does not need anhydrous and oxygen-free condition, operate very simple
It is single；Product is single, and separating-purifying is very convenient, and product purity is high.
Detailed description of the invention
Fig. 1 is reaction process schematic diagram of the invention；
Fig. 2 is the synthetic route chart of embodiment 1；
Fig. 3 is the infared spectrum of N- (6- hydroxyl hexyl) carbazole；
Fig. 4 is the synthetic route chart of embodiment 3；
Fig. 5 is the infared spectrum of derivative N- (6- hydroxyl hexyl) methoxyl carbazole.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
A kind of embodiment 1, synthetic method of N- (6- hydroxyl hexyl) carbazole, sequentially includes the following steps: in single-necked flask
It sequentially adds carbazole 1.67g (10mmol), benzyltriethylammoinium chloride 150mg, dimethyl sulfoxide 20ml, is saturated sodium hydroxide
15ml, 6- bromine n-hexyl alcohol 1.57ml (12mmol), in 65 DEG C of reaction 4h under magnetic agitation.Deionized water 100ml, acetic acid second is added
Ester 100ml, liquid separation, organic phase are washed with water repeatedly until solution is in neutrality (general 3 times), and separation is organic to be added to anhydrous slufuric acid
Sodium dries, filters, and vacuum rotary steam removes ethyl acetate, and residue separates white through silica gel column chromatography (eluant, eluent: methylene chloride)
Color solid N- (6- hydroxyl hexyl) carbazole 2.54g, yield 95%.Synthetic route is as shown in Figure 2.
Product N- (6- hydroxyl hexyl) carbazole characterize data includes:
(1) infared spectrum is as shown in figure 3, IR (KBr, cm-1):3306(-OH)；3050,1625,1594,1484,1465
(carbazole)；2926(alkyl-H)；2858(methylene-H).
(2) nucleus magnetic hydrogen spectrum:
1HNMR(300MHZ,CDCl3):δ8.10(d,2H),7.45(t,2H),7.39(d,2H),7.23(q,2H),4.29
(t,2H),3.58(t,2H),1.88(m,2H),1.52(m,2H),1.39(m,4H)。
(3) nuclear-magnetism carbon is composed:
13CNMR (300MHZ, CDCl3):δ140.43,125,62,122.85,120.39,118.77,108.65,62.79,
42.98,32.59,28.97,27.11,25.57。
A kind of embodiment 2, synthetic method of N- (6- hydroxyl hexyl) carbazole, sequentially includes the following steps: in single-necked flask
It sequentially adds carbazole 1.67g (10mmol), tetrabutylammonium bromide 75mg, n,N-Dimethylformamide 15ml, is saturated potassium hydroxide
10ml, 6- bromine n-hexyl alcohol 10.02mmol, in 45 DEG C of reaction 3.5h under magnetic agitation.Deionized water 100ml, ethyl acetate is added
100ml, liquid separation, organic phase are washed with water repeatedly until solution is in neutrality (general 3 times), and separation is organic to be added to anhydrous sodium sulfate
It dries, filters, vacuum rotary steam removes ethyl acetate, and residue separates white through silica gel column chromatography (eluant, eluent: methylene chloride)
Solid N- (6- hydroxyl hexyl) carbazole 2.14g, yield 50%.
A kind of embodiment 3, synthetic method of N- (6- hydroxyl hexyl) methoxyl carbazole, sequentially includes the following steps:
It is sequentially added in single-necked flask methoxyl carbazole 1.97g (10mmol), benzyltriethylammoinium chloride 150mg, two
Methyl sulfoxide 20ml is saturated sodium hydroxide 15ml, 6- bromine n-hexyl alcohol 1.57ml (12mmol), is reacted under magnetic agitation in 65 DEG C
4h.It is added deionized water 100ml, ethyl acetate 100ml, liquid separation, organic phase is washed with water repeatedly until that solution is in neutrality is (general
3 times), it separates organic anhydrous sodium sulfate that is added to and dries, filters, vacuum rotary steam removes ethyl acetate, and residue is through silica gel column layer
Analysis (eluant, eluent: methylene chloride) separates to obtain white solid N- (6- hydroxyl hexyl) methoxyl carbazole 2.7g, yield 90%.Synthesize road
Line is as shown in Figure 4.
Product N- (6- hydroxyl hexyl) methoxyl carbazole characterize data includes:
(1) infared spectrum is as shown in Figure 5:
IR(KBr,cm-1):3389(-OH)；3049,1630,1601,1498,1463(carbazole)；2933(alkyl-
H)；
2857(methylene-H)。
(2) nucleus magnetic hydrogen spectrum:
1HNMR(300MHZ,(CD3)2SO):δ8.00(dd,2H),7.59(d,1H),7.35(t,1H),7.14(t,1H),
7.10(d,1H),6.80(dd,1H),4.38(t,1H),4.33(t,2H),3.88(s,3H),3.34(q,2H),1.75(m,
2H),1.36(m,2H),1.30(m,4H)。
(3) nuclear-magnetism carbon is composed:
13CNMR(300MHZ,CDCl3):δ158.97,141.73,140.54,124.31,122.98,121.02,
119.45,118.85,116.80,108.38,106.86,93.28,62.62,55.68,42.83,32.48,28.74,26.99,
25.49。
A kind of embodiment 4, synthetic method of N- (6- hydroxyl hexyl) methoxyl carbazole, sequentially includes the following steps:
It is sequentially added in single-necked flask methoxyl carbazole 1.97g (10mmol), dodecyl trimethyl ammonium chloride 90mg,
1,3- dimethyl -3,4,5,6- tetrahydro -2- pyrimidone 25ml are saturated sodium hydroxide 12ml, 6- bromine n-hexyl alcohol 15mmol, and magnetic force stirs
It mixes down in 85 DEG C of reaction 5h.Be added deionized water 100ml, ethyl acetate 100ml, liquid separation, organic phase be washed with water repeatedly until
Solution is in neutrality (general 3 times), is separated organic anhydrous sodium sulfate that is added to and is dried, filtered, and vacuum rotary steam removes ethyl acetate, residual
Object is stayed to separate to obtain white solid N- (6- hydroxyl hexyl) methoxyl carbazole 2.79g through silica gel column chromatography (eluant, eluent: methylene chloride),
Yield 75%.
Finally, it should be noted that foregoing description is only the preferred embodiment of the present invention, the ordinary skill people of this field
Member under the inspiration of the present invention, without prejudice to the purpose of the present invention and the claims, can make multiple similar tables
Show, such transformation is fallen within the scope of protection of the present invention.
Claims (8)
1. a kind of N- (6- hydroxyl hexyl) carbazole derivates, it is characterised in that its general formula is as follows:
Wherein R is alkoxy.
2. the synthetic method of a kind of N- (6- hydroxyl hexyl) carbazole and its derivative, it is characterised in that sequentially include the following steps: and take
Carbazole or derivatives thereof and phase transfer catalyst are added in organic solvent, and it is organic molten that stirring is dissolved in carbazole or derivatives thereof
Agent adds saturation alkaline solution and 6- bromine n-hexyl alcohol, and wherein carbazole or derivatives thereof and the molar ratio of 6- bromine n-hexyl alcohol are
1:1.02-1.5, being vigorously stirred at 45-85 DEG C reacts carbazole or derivatives thereof sufficiently with 6- bromine n-hexyl alcohol, then separates
To N- (6- hydroxyl hexyl) carbazole or derivatives thereof.
3. the synthetic method of N- (6- hydroxyl hexyl) carbazole according to claim 2 and its derivative, it is characterised in that: phase
Transfer catalyst dosage is the 5-10% of carbazole or derivatives thereof dosage, and 1.5-2.5L need to be added in every 1mol carbazole or derivatives thereof
Organic solvent, 1.0-1.5L strong base solution.
4. the synthetic method of N- (6- hydroxyl hexyl) carbazole according to claim 2 or 3 and its derivative, feature exist
In: the reaction time is 3.5-5h.
5. the synthetic method of N- (6- hydroxyl hexyl) carbazole according to claim 4 and its derivative, it is characterised in that institute
The general formula for stating carbazole derivates is as follows:
Wherein R is selected from hydrogen or alkoxy.
6. the synthetic method of N- (6- hydroxyl hexyl) carbazole according to claim 4 and its derivative, it is characterised in that: institute
Stating phase transfer catalyst is quaternary ammonium salt phase transfer catalyst；
The organic solvent is dimethyl sulfoxide, n,N-Dimethylformamide or 1,3- dimethyl -3,4,5,6- tetrahydro -2- pyrimidines
Ketone；
The alkaline solution is sodium hydroxide solution, potassium hydroxide solution or Strong oxdiative calcium solution.
7. the synthetic method of N- (6- hydroxyl hexyl) carbazole according to claim 4 and its derivative, it is characterised in that: institute
Stating reaction temperature is 65 DEG C, reaction time 4h, and the molar ratio of carbazole or derivatives thereof and 6- bromine n-hexyl alcohol is 1:1.2.
8. the synthetic method of N- (6- hydroxyl hexyl) carbazole according to claim 6 and its derivative, it is characterised in that: institute
Stating quaternary ammonium salt is benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylphosphine
Ammonio methacrylate, dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633708A (en) * | 2012-02-20 | 2012-08-15 | 武汉理工大学 | Synthesizing and purifying method of midbody 9-(2-ethoxy) carbazole |
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- 2018-11-13 CN CN201811343397.9A patent/CN109369509A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633708A (en) * | 2012-02-20 | 2012-08-15 | 武汉理工大学 | Synthesizing and purifying method of midbody 9-(2-ethoxy) carbazole |
Non-Patent Citations (4)
| Title |
|---|
| PING ZHAO等: "Polymethacrylates with pendant charge-transporting groups synthesized via RAFT polymerization", 《POLYMER BULLETIN》 * |
| ZHEN LI等: "Synthesis of polyphosphazenes as potential photorefractive materials", 《REACTIVE & FUNCTIONAL POLYMERS》 * |
| 屈玉峰，等: "聚双( 6-咔唑基己氧基) 磷腈的合成", 《合成化学》 * |
| 朱召进，等: "聚丙烯酸修饰咔唑的电化学聚合及表征", 《化学学报》 * |
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Application publication date: 20190222 |