CN104974173B - A kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring 3,4:The preparation method of 9,10 perylene tetracarboxylic acid N-butyls - Google Patents
A kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring 3,4:The preparation method of 9,10 perylene tetracarboxylic acid N-butyls Download PDFInfo
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- CN104974173B CN104974173B CN201510308613.6A CN201510308613A CN104974173B CN 104974173 B CN104974173 B CN 104974173B CN 201510308613 A CN201510308613 A CN 201510308613A CN 104974173 B CN104974173 B CN 104974173B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/06—Peri-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/10—Spiro-condensed systems
Abstract
The invention discloses a kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring 3,4:The preparation method of 9,10 perylene tetracarboxylic acid N-butyls, comprises the following steps：Gulf position mono-nitration 3,4:9,10 perylene tetracarboxylic acid N-butyls are dissolved in N methyl pyrrolidones with obtaining the embedding pentatomic sulphur heterocycle 3,4 in intermediate product gulf position after sulphur powder reaction:9,10 perylene tetracarboxylic acid N-butyls；Intermediate product is further nitrified, and obtains gulf position mono-nitration list Liu Huan perylene tetracarboxylic acid N-butyls；It gulf position mono-nitration list Liu Huan perylene tetracarboxylic acids N-butyls and acid binding agent and can be formed after the nucleopilic reagent reaction of carbanion, obtain the embedding pentatomic sulphur heterocycle in target product gulf and hexa-atomic oxa- ring 3,4:9,10 perylene tetracarboxylic acid N-butyls.The gulf embedding pentatomic sulphur heterocycle in position prepared in the present invention and hexa-atomic Yang Za Huan perylene tetracarboxylic acid N-butyls, gulf position both sides use different annulations, significantly expand the conjugated system of molecule, planes of molecules is enhanced, the electric charge substep of intramolecular can be changed so as to tune electronic structure of molecule, photophysical property by choosing different substituents.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring -3,4:
The preparation method of 9,10- perylene tetracarboxylic acid N-butyls.
Background technology
Perylene tetracarboxylic acid N-butyl analog derivative has preferable electron acceptability, high fluorescence quantum yield, height
Photo and thermal stability, unique photoelectric property and redox property and be widely used in organic field effect tube,
The sciemtifec and technical spheres such as photochromic material, extinction array, organic solar batteries, light emitting diode and color liquid crystal filter,
It is the generally acknowledged organic dyestuff with high value of a class.Therefore Dui perylene tetracarboxylic acid N-butyl class compounds are performed the derivatization
Reaction becomes particularly important, and among these, ring expansion is capable of the conjugated pi system of Zeng great perylenes system derivative, so as to effectively adjust
The photoelectric properties of this humorous analog derivative, are a kind of important derivatization methods.Current , perylenes system derivative ring expansion basic need
It is cyclized under illumination condition or metal catalytic effect, both of which is relative complex.
The content of the invention
It is an object of the invention to provide a kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring -3,4:9,10- perylene tetracarboxylic acids
The preparation method of N-butyl, this method has the advantages that synthesis step is simple, raw material is easy to get, yield is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring -3,4:The preparation method of 9,10- perylene tetracarboxylic acid N-butyls, bag
Include following steps：
(1) by gulf position mono-nitration -3,4:9,10- perylene tetracarboxylic acid N-butyls are dissolved in solvent, add sulphur powder, and inert gas is protected
Shield, reaction obtains the embedding pentatomic sulphur heterocycle -3,4 in intermediate product gulf position:9,10- perylene tetracarboxylic acid N-butyls；
(2) by the embedding pentatomic sulphur heterocycle -3,4 in the gulf obtained in step (1) position:9,10- perylene tetracarboxylic acid N-butyls are nitrified,
Obtain gulf position mono-nitration list Liu Huan perylene tetracarboxylic acid N-butyls；
(3) gulf obtained in step (1) position mono-nitration list Liu Huan perylene tetracarboxylic acid N-butyls are dissolved in solvent, acid is tied up in addition
Agent, adds the nucleopilic reagent of carbanion, reacts 0.5~1 hour, obtains the target product gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxygen
Heterocycle -3,4:9,10- perylene tetracarboxylic acid N-butyls.
It is preferred that, in step (1), reaction process is tracked with thin-layered chromatography.Reaction process is tracked, is reacted by its judgement
Carry out degree, terminates reaction in time when reaction is completed.
It is preferred that, in step (1), the temperature of the reaction is 110~120 DEG C, and the time of reaction is 4~6 hours.
It is preferred that, in step (1), gulf position mono-nitration -3,4:The amount of the material of 9,10- perylene tetracarboxylic acids N-butyl and sulphur powder
Ratio is 1:10-30, the consumption of solvent is every gram of mono-nitration -3,4:9,10- perylene tetracarboxylic acids N-butyl uses 10-200 milliliters.
It is preferred that, in step (1), the solvent is that 1-METHYLPYRROLIDONE, DMF or dimethyl are sub-
Sulfone.
It is preferred that, in step (1), the inert gas is argon gas or nitrogen.
It is preferred that, in step (1), the purifying is isolated and purified by chromatographic column.
It is preferred that, in step (3), the acid binding agent is Anhydrous potassium carbonate, triethylamine or pyridine.
It is preferred that, in step (3), the described nucleopilic reagent that can form carbanion is nitropropane, dibromo fluorenes or third
Diethyl adipate.
It is preferred that, in step (3), the parent of gulf position mono-nitration list Liu Huan perylene tetracarboxylic acids N-butyl, acid binding agent and carbanion
The mol ratio that core reagent is added is 1:1-10:1-20.
It is preferred that, in step (3), every gram of mono-nitration list Liu Huan perylene tetracarboxylic acids N-butyl uses solvent 10-200 millis
Rise.
In step (2), the method for nitrification comprises the following steps：(70 milligrams, 0.1 milli are added in 50 milliliters of round-bottomed flasks
Mole) the embedding pentatomic sulphur heterocycle -3,4 in gulf position:9,10- perylene tetracarboxylic acid N-butyls, using 20 milliliters of dichloromethane as solvent, 30~
It is added dropwise 1 milliliter of fuming nitric aicd under the conditions of 35 DEG C dropwise, concentration 86%~97.5%), with thin-layered chromatography tracking reaction (product gulf
The position embedding pentatomic sulphur heterocycle -3,4 of mono-nitration:9,10- perylene tetracarboxylic acid N-butyls are in brownish red unstressed configuration, the embedding pentatomic sulphur in reactant gulf position
Heterocycle -3,4:9,10- perylene tetracarboxylic acid N-butyls have yellow-green fluorescence in yellow, and tracking reaction is can be very good with thin-layered chromatography
Progress).Reaction solution is added 10 milliliters of unsaturated carbonate aqueous solutions of potassium by reaction after terminating, and is separated organic layer, is removed solvent, obtains
Crude product.Crude product carries out silica gel column chromatography, and (leacheate is dichloromethane：Ethyl acetate=20:1) brown-red solid 63, is obtained
Milligram (yield is 85%).
The present invention synthetic route be：
The invention provides a class gulf embedding pentatomic sulphur heterocycle in position and the preparation method of hexa-atomic Yang Za Huan perylene tetracarboxylic acid N-butyls,
With gulf position mono-nitration 3,4:9,10 perylene tetracarboxylic acid N-butyls are raw material, obtain target product by three-step reaction, expand perylene four
There is provided an effective ring expansion method for synthesis class derivative reaction.
The present invention advantageous effects be：
(1) the gulf embedding pentatomic sulphur heterocycle in position prepared in the present invention and hexa-atomic Yang Za Huan perylene tetracarboxylic acid N-butyls, gulf position both sides
Using different annulations, the conjugated system of molecule is significantly expanded, planes of molecules is enhanced, can be by choosing not
Change the electric charge substep of intramolecular to tune electronic structure of molecule, photophysical property with substituent.The structure system is new simultaneously
It was found that structure, enriches the derivatization method of such compound；
(2) reaction condition is gentle, and reactions steps are simple；Yield is relatively up to more than 50%.
(3) advantage of each step reagent selection and processing method：The reaction of selection inert gas argon gas shielded, energy in step (1)
Effective isolation air, prevents the oxygen in air from impacting generation accessory substance to reaction at relatively high temperatures.
Selection is right using 1-METHYLPYRROLIDONE, DMF or dimethyl sulfoxide (DMSO) as solvent in step (1)
Such reaction parent and derivative dissolubility are good and post-process simple and convenient.
Nitration method described in step (2), the gentle yield of reaction condition is high, and with the middle of common single bromination reaction
Body phase compares, and mononitrated product yield is higher and subsequent reactions facilitate mild condition.
Described in step (3) using Anhydrous potassium carbonate, triethylamine or pyridine as acid binding agent, can be raw in neutralization reaction in time
Main reaction is not involved in into acid product；Described nucleopilic reagent can quickly form carbanion, and institute in the basic conditions
The carbanion compatibility of formation is strong, and reaction is fast.
Brief description of the drawings
Fig. 1 products A mass spectrum；
Fig. 2 products A nucleus magnetic hydrogen spectrum；
Fig. 3 products B mass spectrum；
Fig. 4 products B nucleus magnetic hydrogen spectrum；
Fig. 5 products C mass spectrum；
Fig. 6 products C nucleus magnetic hydrogen spectrum.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Described 3,4:9,10- perylene tetracarboxylic acid N-butyls pass through 3,4:9,10- perylenetetracarboxylic dianhydrides are with described in following documents
Method is synthesized.Xiong Mo,Min-Min Shi,Jia-Chi Huang,Mang Wang,Hong-Zheng
Chen.Synthesis,aggregation and photoconductive properties of alkoxycarbonyl
substituted perylenes.Dyes and Pigments 2008；76(1):236-242.
Perylenetetracarboxylic dianhydride and carbanion nucleopilic reagent (are purchased from：This biochemical technology Co., Ltd of Tianjin Skien).
Embodiment 1
(1) preparation of the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acid N-butyls in gulf position:
40 milligrams of (1.25 mMs) sulphur powders, 8 milliliters of 1-METHYLPYRROLIDONEs are added in 25 milliliters of round-bottomed flasks
(NMP), stir 10 minutes at 90 DEG C.Argon gas protection is lower to add 50 milligrams (0.073 mM) single Xiaoization perylene tetracarboxylic acid N-butyl,
Reacted 6 hours at 110 DEG C, tracked and reacted with thin-layered chromatography.Reaction solution is poured into 100 milliliters of water by reaction after terminating, and is separated out
Precipitation, stands, depressurizes suction filtration, filter cake is washed 2~3 times with 10% ethanol water, the solid being collected into is dried in vacuo, obtained
Crude product.Crude product carries out silica gel column chromatography, and leacheate is dichloromethane：Ethyl acetate=20:1.Obtain the milli of intermediate product 35
Gram (0.051 mM, 70%) yield is about.
(2) preparation of the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acid N-butyls in mono-nitration gulf position:
70 milligrams of (0.1 mM) gulfs position positive fourth of embedding pentatomic sulphur Za Huan perylene tetracarboxylic acids is added in 25 milliliters of round-bottomed flasks
Ester, 10 milliliters of dichloromethane are added dropwise 1 milliliter of fuming nitric aicd dropwise under the conditions of 30 DEG C, and concentration 86%~97.5%), room temperature is anti-
Answer 1 hour, tracked and reacted with thin-layered chromatography.Reaction adds 5 milliliters of unsaturated carbonate aqueous solutions of potassium terminating reactions after terminating, organic
Layer is washed with water rear magnesium sulfate and is dried overnight, and removes solvent and obtains crude product.Crude product carries out silica gel column chromatography, and leacheate is two
Chloromethanes：Ethyl acetate=20:1.Obtain mono-nitration gulf position embedding 63 milligrams of pentatomic sulphur Za Huan perylene tetracarboxylic acids N-butyl (0.085 milli
Mole, yield is 85%), following react to be carried out as raw material.
(3) product A preparation：
In 25 milliliters of round-bottomed flasks, by the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acids in 50 milligrams of (0.069 mM) mono-nitration gulfs position
Sour N-butyl is dissolved in 8 milliliters of NMP, adds 60 milligrams of (0.434 mM) Anhydrous potassium carbonates, and nitropropane 0.1 is added dropwise dropwise
Milliliter (about 0.7 mM), reacts at room temperature 1 hour, is tracked and reacted with thin-layered chromatography.Reaction solution is poured into by reaction after terminating
In 100 milliliter 10% of aqueous hydrochloric acid solution, precipitation is separated out, stands, depressurize suction filtration, filter cake washs 2~3 with 10% ethanol water
It is secondary, the solid being collected into is dried in vacuo, crude product is obtained, crude product carries out silica gel column chromatography, and leacheate is dichloromethane：Second
Acetoacetic ester=20:1.Obtaining 32 milligrams of product A (structural characterization is shown in Fig. 1 and Fig. 2), (0.044 mM, 64%) yield is about.Production
Thing A structural formula is：
Series derivates gulf position both sides use different annulations, significantly expand the conjugated system of molecule, increase
Strong planes of molecules, can change the electric charge substep of intramolecular so as to tuning the electronics knot of molecule by choosing different substituents
Structure, photophysical property.The structure system new discovery structure, enriches the derivatization method of such compound simultaneously.
Embodiment 2
(1) preparation of the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acid N-butyls in gulf position:
40 milligrams of (1.25 mMs) sulphur powders, 10 milliliters of DMFs are added in 25 milliliters of round-bottomed flasks,
Stirred 10 minutes at 90 DEG C.Nitrogen protection is lower to add 50 milligrams (0.073 mM) single Xiaoization perylene tetracarboxylic acid N-butyl, 120 DEG C
Lower reaction 5 hours, is tracked with thin-layered chromatography and reacted.Reaction solution is poured into 100 milliliters of water by reaction after terminating, and separates out precipitation,
Stand, depressurize suction filtration, filter cake is washed 2~3 times with 10% ethanol water, the solid being collected into is dried in vacuo, slightly produced
Product.Crude product carries out silica gel column chromatography, and leacheate is dichloromethane：Ethyl acetate=20:1.Obtain 35 milligrams of intermediate product
(0.051 mM, 70%) yield is about.
(2) preparation of the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acid N-butyls in mono-nitration gulf position:
70 milligrams of (0.1 mM) gulfs position positive fourth of embedding pentatomic sulphur Za Huan perylene tetracarboxylic acids is added in 25 milliliters of round-bottomed flasks
Ester, 10 milliliters of dichloromethane are added dropwise 1 milliliter of fuming nitric aicd dropwise under the conditions of 30 DEG C, and concentration 86%~97.5%), room temperature is anti-
Answer 1 hour, tracked and reacted with thin-layered chromatography.Reaction adds 5 milliliters of unsaturated carbonate aqueous solutions of potassium terminating reactions after terminating, organic
Layer is washed with water rear magnesium sulfate and is dried overnight, and removes solvent and obtains crude product.Crude product carries out silica gel column chromatography, and leacheate is two
Chloromethanes：Ethyl acetate=20:1.Obtain mono-nitration gulf position embedding 63 milligrams of pentatomic sulphur Za Huan perylene tetracarboxylic acids N-butyl (0.085 milli
Mole, yield is 85%), following react to be carried out as raw material.
(3) product B preparation：
In 25 milliliters of round-bottomed flasks, by the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acids in 50 milligrams of (0.069 mM) mono-nitration gulfs position
Sour N-butyl is dissolved in 10 milliliters of 1-METHYLPYRROLIDONEs (NMP), adds 60 milligrams of (0.434 mM) Anhydrous potassium carbonates, plus
Enter 200 milligrams of (about 0.7 mM) dibromo fluorenes, react at room temperature 0.5 hour, tracked and reacted with thin-layered chromatography.Reaction terminates
Reaction solution is poured into 100 milliliter 10% of aqueous hydrochloric acid solution afterwards, precipitation is separated out, stands, depressurize suction filtration, 10% ethanol of filter cake
The aqueous solution is washed 2~3 times, and the solid being collected into is dried in vacuo, and obtains crude product, and crude product carries out silica gel column chromatography, elution
Liquid is dichloromethane：Ethyl acetate=20:1.Obtain 40 milligrams of product B (structural characterization is shown in Fig. 3 and Fig. 4) (0.04 mM, production
58%) rate is about.Product B structural formula is：
Embodiment 3
(1) preparation of the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acid N-butyls in gulf position:
Add and stirred at 40 milligrams of (1.25 mMs) sulphur powders, 8 milliliters of dimethyl sulfoxide (DMSO)s, 90 DEG C in 25 milliliters of round-bottomed flasks
Mix 10 minutes.Reaction 4 at 50 milligrams (0.073 mM) single Xiaoization perylene tetracarboxylic acid N-butyls, 120 DEG C is added under argon gas protection small
When, tracked and reacted with thin-layered chromatography.Reaction solution is poured into 100 milliliters of water by reaction after terminating, and separates out precipitation, is stood, is depressurized
Suction filtration, filter cake is washed 2~3 times with 10% ethanol water, and the solid being collected into is dried in vacuo, crude product is obtained.Crude product
Silica gel column chromatography is carried out, leacheate is dichloromethane：Ethyl acetate=20:1.Obtain 35 milligrams of (0.051 mmoles of intermediate product
You, 70%) yield is about.
(2) preparation of the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acid N-butyls in mono-nitration gulf position:
70 milligrams of (0.1 mM) gulfs position positive fourth of embedding pentatomic sulphur Za Huan perylene tetracarboxylic acids is added in 25 milliliters of round-bottomed flasks
Ester, 10 milliliters of dichloromethane are added dropwise 1 milliliter of fuming nitric aicd dropwise under the conditions of 30~35 DEG C, and concentration 86%~97.5%), room
Temperature reaction 0.8 hour, is tracked with thin-layered chromatography and reacted.Reaction adds 5 milliliters of unsaturated carbonate aqueous solutions of potassium after terminating and terminated instead
Should, organic layer is washed with water rear magnesium sulfate and is dried overnight, and removes solvent and obtains crude product.Crude product carries out silica gel column chromatography, drenches
Washing lotion is dichloromethane：Ethyl acetate=20:1.Obtain embedding 63 milligrams of the pentatomic sulphur Za Huan perylene tetracarboxylic acids N-butyl in mono-nitration gulf position
(0.085 mM, yield is 85%), following react to be carried out as raw material.
(3) product C preparation：
In 25 milliliters of round-bottomed flasks, by the embedding pentatomic sulphur Za Huan perylene tetracarboxylic acids in 50 milligrams of (0.069 mM) mono-nitration gulfs position
Sour N-butyl is dissolved in 8~10 milliliters of DMFs, adds 60 milligrams of (0.434 mM) Anhydrous potassium carbonates, by
0.1 milliliter of diethyl malonate (about 0.7 mM) is added dropwise in drop, reacts at room temperature 0.8 hour, is tracked with thin-layered chromatography anti-
Should.Reaction solution is poured into 100 milliliter 10% of aqueous hydrochloric acid solution by reaction after terminating, and separates out precipitation, is stood, is depressurized suction filtration, filter
Cake is washed 2~3 times with 10% ethanol water, and the solid being collected into is dried in vacuo, and obtains crude product, and crude product carries out silica gel
Column chromatography, leacheate is dichloromethane：Ethyl acetate=20:1.Obtain 31 milligrams of product C (structural characterization is shown in Fig. 5 and Fig. 6)
(0.036 mM, 52%) yield is about.Product C-structure formula is：
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, not to invention protection domain
Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
Pay various modifications or deform still within the scope of the present invention that creative work can make.
Claims (9)
1. a kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring -3,4:The preparation method of 9,10- perylene tetracarboxylic acid N-butyls, including
Following steps：
(1) by gulf position mono-nitration -3,4:9,10- perylene tetracarboxylic acid N-butyls are dissolved in solvent, addition sulphur powder, inert gas shielding,
Reaction, obtains the embedding pentatomic sulphur heterocycle -3,4 in intermediate product gulf position:9,10- perylene tetracarboxylic acid N-butyls；
(2) by the embedding pentatomic sulphur heterocycle -3,4 in the gulf obtained in step (1) position:9,10- perylene tetracarboxylic acid N-butyls are nitrified, and are obtained
Gulf position mono-nitration list Liu Huan perylene tetracarboxylic acid N-butyls；
(3) gulf obtained in step (1) position mono-nitration list Liu Huan perylene tetracarboxylic acid N-butyls are dissolved in solvent, add acid binding agent,
The nucleopilic reagent of carbanion is added, is reacted 0.5~1 hour, the target product gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- is obtained
Ring -3,4:9,10- perylene tetracarboxylic acid N-butyls；
The gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring -3,4:The structural formula of 9,10- perylene tetracarboxylic acid N-butyls is：
In step (1), the temperature of the reaction is 110~120 DEG C, and the time of reaction is 4~6 hours.
2. preparation method according to claim 1, it is characterised in that：In step (1), gulf position mono-nitration -3,4:9,10- perylenes
The mol ratio of tetrabasic carboxylic acid N-butyl and sulphur powder is 1:10-30, the consumption of solvent is every gram of mono-nitration -3,4:9,10- perylene tetracarboxylic acids
N-butyl uses 10-200 milliliters.
3. preparation method according to claim 1, it is characterised in that：In step (1), the solvent is N- crassitudes
Ketone, N,N-dimethylformamide or dimethyl sulfoxide (DMSO).
4. preparation method according to claim 1, it is characterised in that：In step (1), the inert gas is argon gas or nitrogen
Gas.
5. preparation method according to claim 1, it is characterised in that：In step (1), the purifying is entered by chromatographic column
Row is isolated and purified.
6. preparation method according to claim 1, it is characterised in that：In step (3), the acid binding agent is Carbon Dioxide
Potassium, triethylamine or pyridine.
7. preparation method according to claim 1, it is characterised in that：In step (3), described can form carbanion
Nucleopilic reagent is nitropropane, dibromo fluorenes or diethyl malonate.
8. preparation method according to claim 1, it is characterised in that：In step (3), gulf position mono-nitration list Liu Huan perylene tetracarboxylic acids
The mol ratio that the nucleopilic reagent of sour N-butyl, acid binding agent and carbanion is added is 1:1-10:1-20.
9. preparation method according to claim 1, it is characterised in that：In step (3), every gram of mono-nitration list Liu Huan perylenes
Tetrabasic carboxylic acid N-butyl uses 10-200 milliliters of solvent.
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| CN106883242B (en) * | 2017-04-11 | 2019-02-19 | 山东师范大学 | A kind of preparation method of the embedding hexa-atomic oxa- ring diphenol generation -3,4,9,10- tetracarboxylic acid diimide in gulf position |
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| CN103613599B (en) * | 2013-12-04 | 2015-11-18 | 山东师范大学 | A kind of position, gulf of 3,4:9,10-perylene tetracarboxylic acid diimides becomes ring synthetic method |
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