CN109516947A - A method of N- phenylcarbazole compounds are synthesized with sulfur dioxide compound of fluorene class - Google Patents
A method of N- phenylcarbazole compounds are synthesized with sulfur dioxide compound of fluorene class Download PDFInfo
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- CN109516947A CN109516947A CN201811636738.1A CN201811636738A CN109516947A CN 109516947 A CN109516947 A CN 109516947A CN 201811636738 A CN201811636738 A CN 201811636738A CN 109516947 A CN109516947 A CN 109516947A
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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 invention belongs to technical field of organic synthesis, disclose a kind of synthetic method of novel N- phenylcarbazole compounds.Using sulfur dioxide compound of fluorene class as raw material, with hexamethyldisilazane and potassium tert-butoxide (sodium) for catalyst, react to obtain N- phenylcarbazole compounds with amino benzenes compounds.The present invention is at low cost compared with similar method, and applicability is wide.
Description
Technical field
The invention belongs to organic synthesis fields, disclose a kind of synthetic method of novel N- phenylcarbazole compounds.
Background technique
N- phenylcarbazole compounds containing various substituent groups, are used as pesticide or medicine and organic electroluminescence extensively
The intermediate of luminous (OLED) material；Its synthesis preparation method is also varied.
It is raw material that the synthetic method of most common N- phenyl substituted carbazole class compound, which is with carbazole, carries out various substitutions
Reaction；But because the N atom in carbazole group have strong ortho para position orientation effect, in this way can only be at 3 of carbazole
Or 6 introducing substituent groups.Other methods must be used in 2 of carbazole or 7 introducing substituent groups；And be currently known can
The cost of capable various methods is all very high, leads to the N- phenylcarbazole compounds rolled into a ball in 2 or 7 substds, and cost is high
It is expensive, limit the popularization and application of such compound.
Summary of the invention
The purpose of the present invention is using sulfur dioxide compound of fluorene class as Material synthesis N- phenylcarbazole compounds.
The technical scheme is that a kind of side with sulfur dioxide compound of fluorene class synthesis N- phenylcarbazole compounds
Method, it is characterised in that:
Using the sulfur dioxide compound of fluorene class on phenyl ring containing substituent group as one of raw material；
Using the amino benzenes compounds on phenyl ring containing substituent group as the two of raw material；
Using hexamethyldisilazane as one of catalyst or solvent；
Using potassium tert-butoxide or sodium tert-butoxide as the two of catalyst；
Synthetic product is the N- phenylcarbazole compounds containing substituent group on phenyl ring;
Specific synthetic reaction equation is as follows:
,
X in the above reaction equation, Y, Z are same or different substituent group, are hydrogen atom, alkyl, alkoxy, fragrance
Base, fragrant oxygroup, halogen, cyano, combination group one or more in amino.
2, a kind of sulfur dioxide compound of fluorene class synthesis N- phenylcarbazole compounds according to claim 1
Method, it is characterised in that:
Sulfur dioxide compound of fluorene class: amino benzenes compounds: hexamethyldisilazane: potassium tert-butoxide (or sodium tert-butoxide) feeds intake
Ratio is the amount of 1.0-1.1:1.0-3.0:1.5-10.0:1.0-3.0 times of substance；
When have in sulfur dioxide compound of fluorene class 2 or 2 or more need to participate in reaction sulfur dioxide groups；Or phenyl amines
When having 2 or 2 or more the amino for needing to participate in reaction in compound, the dosage of other several materials, it should also as needed
The group numbers that above-mentioned needs participate in reaction increase on year-on-year basis.
3, a kind of sulfur dioxide compound of fluorene class synthesis N- phenylcarbazole compounds according to claim 1
Method, it is characterised in that technical process below:
Under nitrogen protection, a certain number of hexamethyldisilazane and solvent are first added into reaction vessel, then be added portionwise one
The potassium tert-butoxide (or sodium tert-butoxide) of fixed number amount stirs 0.5-1 hours after adding;Then certain amount is added into reaction vessel
Sulfur dioxide compound of fluorene class and amino benzenes compounds, after all adding, stir under nitrogen protection, and control 50-150 DEG C
Reaction temperature, insulation reaction 2-20 hours, then reaction solution is hydrolyzed；The mode for using extraction or filtering again, from water
Solve the crude product that target product is obtained in liquid;
The technical process, ingredient proportion are sulfur dioxide compound of fluorene class: amino benzenes compounds: hexamethyldisilazane:
The ingredient proportion of potassium tert-butoxide (or sodium tert-butoxide) is the amount of 1.0-1.1:1.0-3.0:1.5-10.0:1.0-3.0 times of substance；
The technical process, when have in sulfur dioxide compound of fluorene class 2 or 2 or more need to participate in reaction sulfur dioxide
Group；Or when having 2 or 2 or more the amino for needing to participate in reaction in amino benzenes compounds, the dosage of other several materials,
It should also be as the group numbers that above-mentioned needs participate in reaction as needed to increase on year-on-year basis.
The technical process, the solvent of selection are the solvent that cannot participate in this reaction: toluene, dimethylbenzene, DMF, N- first
Base pyrrolidones, tetrahydrofuran, methyl tertiary butyl ether(MTBE), petroleum ether, one or more mixing in hexamethylene;
The technical process, the amount of solvents of addition are the mass ratio of 100%-1000% times of sulfur dioxide compound of fluorene class;
The technical process, the temperature of reaction are 50-120 DEG C;
The technical process, the time of reaction are 2-20 hours;
Specific synthetic reaction equation is as follows:
,
X in the above reaction equation, Y, Z are same or different substituent group, are hydrogen atom, alkyl, alkoxy, fragrance
Base, fragrant oxygroup, halogen, cyano, combination group one or more in amino.
It is raw material that the synthetic method of most common N- phenyl substituted carbazole class compound, which is with carbazole, carries out various substitutions
Reaction；But this method can only be in 3 of carbazole or 6 introducing substituent groups.
The cost of various methods being currently known, introducing substituent group at 2 of carbazole or 7 is all very high, causes 2
The N- phenylcarbazole compounds of position or 7 substds group are expensive, limit the popularization and application of such compound.
The present invention is using sulfur dioxide compound of fluorene class as raw material；What is had due to sulfur dioxide compound of fluorene class is that meta position is fixed
Position effect, so being mainly substituted in 2 or 7 when sulfur dioxide compound of fluorene class carries out substitution reaction；It is inverted again to obtain
Obtain the N- phenylcarbazole compounds rolled into a ball in 2 or 7 substds.
Before making the present invention, academic documents have studied the method similar with the present invention；But what these researchs used
Catalyst is bis- (trimethylsilyl) potassamides.Bis- (trimethylsilyl) potassamides need with metallic potassium or hydrofining come
Preparation, so expensive and preparation risk is big.In addition the alkalinity and reactivity of bis- (trimethylsilyl) potassamides
It is very strong, it is not only difficult to save, and in even 0 DEG C of room temperature hereinafter, can send out with substituent groups such as halogens on most phenyl ring
It is raw quickly, completely to react, so when raw material (sulfur dioxide compound of fluorene class or amino benzenes compounds) have common halogen
When equal substituent groups, target product cannot be synthesized using this method, limit the application range of this method.
The present invention uses hexamethyldisilazane and potassium tert-butoxide (or the tert-butyl alcohol compared with above-mentioned similar method
Sodium), to substitute bis- (trimethylsilyl) potassamides.The current city of hexamethyldisilazane and potassium tert-butoxide (or sodium tert-butoxide)
The sum of price, lower than the 10% of bis- (trimethylsilyl) potassamide current market prices of equivalent, reduce raw material at
This.Simultaneously for relatively bis- (trimethylsilyl) potassamides, hexamethyldisilazane and potassium tert-butoxide (or sodium tert-butoxide)
Stability is stronger, is easier to save；Under general reaction temperature, react slower with the halogenic substituent on most of phenyl ring,
It does not react even；Target product of the invention can be synthesized as catalyst when using the raw material for having halogenic substituent, increase
The big scope of application of the invention.
Specific example mode
Elaborate below to the embodiment of the present invention: the present embodiment carries out reality under the premise of the technical scheme of the present invention
It applies, the detailed implementation method and specific operation process are given.It should be pointed out that coming to those skilled in the art
It says, without departing from the inventive concept of the premise, several variations and modifications can also be made, these belong to present invention protection model
It encloses.
The invention discloses a kind of synthetic method of N- phenylcarbazole compounds, specific embodiment is as follows:
Example 1: the raw material and target product of use are as shown in following reaction equation:
。
Concrete operations are as follows: under nitrogen protection, the hexamethyl two of 161g (1mol) is added into three mouthfuls of vials of 500ml
The DMF of silazane and 20g, is added portionwise the potassium tert-butoxide of 0.1mol under stirring, holding is stirred at room temperature 0.5 hour.Nitrogen protection
Under, be added 27.5g(0.1mol) 2- bromo titanium dioxide dibenzothiophen) and 0.1mol aniline.After adding, 80 DEG C are slowly ramped to,
75-80 DEG C are maintained to be stirred to react 5 hours.Reaction solution is slowly added dropwise in the water of 500ml and is hydrolyzed.After hydrolysis, first
Steam distillation removes major part DMF, distills residue cooled and filtered, the ethyl alcohol of 2 times of quality of obtained filter cake, 2 times of quality
Toluene Mixed Solvent crystallization, obtain the N- phenyl -2- bromine carbazole of 23.3g, yield 72.3%.
Example 2: the raw material and target product of use are as shown in following reactive mode:
Concrete operations are as follows: under nitrogen protection, into three mouthfuls of vials of 500L be added 0.15mol hexamethyldisilazane and
The tetrahydrofuran of 200g；The sodium tert-butoxide of 0.13mol is added portionwise under stirring again, holding is stirred at room temperature 0.5 hour.Nitrogen protection
Under, the 4- aminoanisole of 2, the 7- bis- bromo sulfur dioxide fluorenes and 0.3mol of 0.1mol is added.After adding, it is slowly ramped to
It 50 DEG C, maintains 50-60 DEG C and is stirred to react 2 hours.Concentration steams most tetrahydrofuran；200g is added in distillation residue
Toluene and stirring, then toluene mixture liquid is slowly added dropwise in the water of 500ml and is hydrolyzed.Liquid separation after hydrolysis, has
Machine layer is washed time again, and then concentration removes toluene.The toluene Mixed Solvent of the ethyl alcohol of 2 times of quality of condensate residue, 2 times of quality
Crystallization, obtains the N-(4- methoxyl group of about 31.5g) phenyl -2,7- dibromo carbazole, yield 78.5%.
Example 3: the raw material and target product of use are as shown in following reactive mode:
Concrete operations are as follows: under nitrogen protection, the hexamethyldisilazane and 200g of 0.8mol are added into three mouthfuls of vials of 1L
DMF, be added portionwise the potassium tert-butoxide of 0.6mol under stirring, holding is stirred at room temperature 0.5 hour.Under nitrogen protection, it is added
The 2- bromo titanium dioxide dibenzothiophen of 0.22mol and 1, the 5- naphthylenediamine of 0.1mol.After adding, 110 DEG C are slowly ramped to, is maintained
110-120 DEG C are stirred to react 10 hours.Reaction solution is slowly added dropwise in the water of 500ml and is hydrolyzed.After hydrolysis, first
Steam distillation removes major part DMF, distills residue cooled and filtered, the ethyl alcohol of 2 times of quality of obtained filter cake, 4 times of quality
Toluene Mixed Solvent crystallization it is secondary, obtain 1,5- bis- (2- bromo carbazole -9- base) naphthalene of 42.2g, yield 68.5%.
Claims (4)
1. a kind of method with sulfur dioxide compound of fluorene class synthesis N- phenylcarbazole compounds, it is characterised in that:
Using the sulfur dioxide compound of fluorene class on phenyl ring containing substituent group as one of raw material；
Using the amino benzenes compounds on phenyl ring containing substituent group as the two of raw material；
Using hexamethyldisilazane as one of catalyst or solvent；
Using potassium tert-butoxide or sodium tert-butoxide as the two of catalyst；
Synthetic product is the N- phenylcarbazole compounds containing substituent group on phenyl ring;
Specific synthetic reaction equation is as follows:
,
X in the above reaction equation, Y, Z are same or different substituent group, are hydrogen atom, alkyl, alkoxy, fragrance
Base, fragrant oxygroup, halogen, cyano, combination group one or more in amino.
2. a kind of side with sulfur dioxide compound of fluorene class synthesis N- phenylcarbazole compounds according to claim 1
Method, it is characterised in that:
Sulfur dioxide compound of fluorene class: amino benzenes compounds: hexamethyldisilazane: potassium tert-butoxide (or sodium tert-butoxide) feeds intake
Ratio is the amount of 1.0-1.1:1.0-3.0:1.5-10.0:1.0-3.0 times of substance；
When have in sulfur dioxide compound of fluorene class 2 or 2 or more need to participate in reaction sulfur dioxide groups；Or phenyl amines
When having 2 or 2 or more the amino for needing to participate in reaction in compound, the dosage of other several materials, it should also as needed
The group numbers that above-mentioned needs participate in reaction increase on year-on-year basis.
3. a kind of side with sulfur dioxide compound of fluorene class synthesis N- phenylcarbazole compounds according to claim 1
Method, it is characterised in that technical process below:
Under nitrogen protection, a certain number of hexamethyldisilazane and solvent are first added into reaction vessel, then be added portionwise one
The potassium tert-butoxide (or sodium tert-butoxide) of fixed number amount stirs 0.5-1 hours after adding;Then certain amount is added into reaction vessel
Sulfur dioxide compound of fluorene class and amino benzenes compounds, after all adding, stir under nitrogen protection, and control 50-150 DEG C
Reaction temperature, insulation reaction 2-20 hours, then reaction solution is hydrolyzed；The mode for using extraction or filtering again, from water
Solve the crude product that target product is obtained in liquid;
The technical process, ingredient proportion are sulfur dioxide compound of fluorene class: amino benzenes compounds: hexamethyldisilazane:
The ingredient proportion of potassium tert-butoxide (or sodium tert-butoxide) is the amount of 1.0-1.1:1.0-3.0:1.5-10.0:1.0-3.0 times of substance；
The technical process, when have in sulfur dioxide compound of fluorene class 2 or 2 or more need to participate in reaction sulfur dioxide
Group；Or when having 2 or 2 or more the amino for needing to participate in reaction in amino benzenes compounds, the dosage of other several materials,
It should also be as the group numbers that above-mentioned needs participate in reaction as needed to increase on year-on-year basis.
4. technical process described in, the solvent of selection are the solvent that cannot participate in this reaction: toluene, dimethylbenzene, DMF, N- methyl
Pyrrolidones, tetrahydrofuran, methyl tertiary butyl ether(MTBE), petroleum ether, one or more mixing in hexamethylene;
The technical process, the amount of solvents of addition are the mass ratio of 100%-1000% times of sulfur dioxide compound of fluorene class;
The technical process, the temperature of reaction are 50-120 DEG C;
The technical process, the time of reaction are 2-20 hours;
Specific synthetic reaction equation is as follows:
,
X in the above reaction equation, Y, Z are same or different substituent group, are hydrogen atom, alkyl, alkoxy, fragrance
Base, fragrant oxygroup, halogen, cyano, combination group one or more in amino.
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| CN102439004A (en) * | 2010-04-20 | 2012-05-02 | 出光兴产株式会社 | Bicarbazole derivative, material for organic electroluminescent element, and organic electroluminescent element using same |
| CN104039778A (en) * | 2011-07-21 | 2014-09-10 | 罗门哈斯电子材料韩国有限公司 | 9H-carbazole compounds and electroluminescent devices involving them |
| CN109678648A (en) * | 2018-12-29 | 2019-04-26 | 江苏广域化学有限公司 | A method of thick cyclics of the synthesis containing biphenyl structural |
| CN109970668A (en) * | 2017-12-28 | 2019-07-05 | 普济生物科技（台州）有限公司 | A method of preparing the thio -1,2,4- triazole compound of 3- |
-
2018
- 2018-12-29 CN CN201811636738.1A patent/CN109516947A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102439004A (en) * | 2010-04-20 | 2012-05-02 | 出光兴产株式会社 | Bicarbazole derivative, material for organic electroluminescent element, and organic electroluminescent element using same |
| CN104039778A (en) * | 2011-07-21 | 2014-09-10 | 罗门哈斯电子材料韩国有限公司 | 9H-carbazole compounds and electroluminescent devices involving them |
| CN109970668A (en) * | 2017-12-28 | 2019-07-05 | 普济生物科技（台州）有限公司 | A method of preparing the thio -1,2,4- triazole compound of 3- |
| CN109678648A (en) * | 2018-12-29 | 2019-04-26 | 江苏广域化学有限公司 | A method of thick cyclics of the synthesis containing biphenyl structural |
Non-Patent Citations (3)
| Title |
|---|
| BHANUCHANDRA, M.; BARALLE, ALEXANDRE: "Palladium-Catalyzed ipso-Borylation of Aryl Sulfides with Diborons", 《ORGANIC LETTERS》 * |
| BHANUCHANDRA, M.; MURAKAMI, KEI: "Transition-Metal-Free Synthesis of Carbazoles and Indoles by an SNAr-Based "Aromatic Metamorphosis" of Thiaarenes", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
| NOGI, KEISUKE; YORIMITSU, HIDEKI: "Aromatic metamorphosis: conversion of an aromatic skeleton into a different ring system", 《CHEMICAL COMMUNICATIONS (CAMBRIDGE, UNITED KINGDOM》 * |
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