CN109651370A - A kind of purine analog derivative free radical precursor molecule and preparation method thereof - Google Patents
A kind of purine analog derivative free radical precursor molecule and preparation method thereof Download PDFInfo
- Publication number
- CN109651370A CN109651370A CN201811545572.2A CN201811545572A CN109651370A CN 109651370 A CN109651370 A CN 109651370A CN 201811545572 A CN201811545572 A CN 201811545572A CN 109651370 A CN109651370 A CN 109651370A
- Authority
- CN
- China
- Prior art keywords
- reaction
- compound
- 4mmol
- 1mmol
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D473/00—Heterocyclic compounds containing purine ring systems
Abstract
The present invention provides a kind of structure of purine analog derivative free radical precursor molecule, such molecule is organic N type dopant small molecule material.The present invention also provides a kind of methods for preparing this purine analog derivative free radical precursor molecule.Organic N type dopant research for organic conductive or field of semiconductor materials provides a new developing way.
Description
Technical field
The present invention relates to the structures and preparation method of a kind of purine analog derivative free radical precursor molecule.
Background technique
In recent decades, since organic conductive or semiconductor material have many advantages, such as flexibility, diversity, low in cost etc.,
It is constantly subjected to the common concern of scientific circles and industrial circle, the research and development of this kind of material become global research hotspot.Currently, organic lead
Electricity or semiconductor material are widely used in various photoelectricity or electromechanical device, such as field effect transistor, Flexible Displays, the sun
Energy battery, light-emitting electrochemical cell, artificial skin and electroactive driver or detector etc..Realize that these low costs are flexible
The industrialization of device, most basic premise are exactly to develop the organic conductive or semiconductor material haveing excellent performance.
Other than design synthesizes new high-performance organic conductive or semiconductor material, doping is also to promote material and device
The important means of energy." hole " carrier concentration can be improved in dopant is known as p-type, and improve electron carrier density is then
N-type.The doping characteristic of organic N type dopant, which is derived from its molecule, has very strong ionizing power, is easy electronics of leaving away, and electronics turns
It moves on the conduction level of material of main part, the electron carrier density in material of main part can be effectively increased, improve conductivity, adjust
The whole density of states changes fermi level, the final performance for improving organic electro-optic device.
From the point of view of comprehensive literature, free radical precursor molecule is using the more organic N type dopant of one kind.Wherein, with benzo
For imidazolidine derivative, 2 carbon are tertiary carbon atoms, the electronics on the tertiary carbon can delocalization to coupled alkyl and benzene
On the carbon of ring, more stable free radical easily generated.Therefore benzimidazole alkane 2 carbon under the simple conditions such as illumination, heating just
Can leave away hydrogen atom, form the carbon radicals molecule (as follows) for easily providing electronics, that is, have lower ionization energy, to have
There is good n-type doping performance.It can be seen that aryl tertiary carbon (such as phenylmethane) structure is the easy frame for forming stabilized radical
Structure.Therefore, Molecular Design synthesizing aryl free radical precursor molecule can be passed through on the basis of aryl tertiary carbon.
Purine analog derivative is necessary organic matter in animal and plant body, in energy supply, Metabolism regulation and composition coenzyme etc.
Aspect plays very important effect, is widely used in biomedicine field.Purine itself is big pi-conjugated system, is had
Organic semiconductor property.Specific substituent group can be introduced on 2,6,8 on purine ring, so as to effectively adjust it partly
Conductor characteristics.Therefore, functional purine analog derivative can be synthesized by Molecular Design, developing high performance novel has
Machine optoelectronic semiconductor is applied to organic photoelectrical material field.
Summary of the invention
The object of the present invention is to provide the structures and preparation method of a kind of purine analog derivative free radical precursor molecule.This hair
It is bright to be achieved through the following technical solutions:
1, a kind of purine analog derivative free radical precursor molecule, structure are shown in formula I.The molecule is in 8 carbon-R4Position
The benzyl type free radical front body structure confirmed by document is remained, the tertiary carbon of this class formation is in the simple item such as illumination, heating
Can leave away hydrogen atom under part, form the carbon radicals molecule for easily providing electronics;Secondly as nitrogen-atoms is more on purine ring,
And the electronics of nitrogen-atoms is more than carbon, so that electron donation and reaction site activity on purine ring are all more than benzimidazole ring
By force, it is easier to carry out structural modification, the free radical of formation is easier to provide electronics;Finally, innovative by biomedicine field
In important organic matter purine, be applied to organic photoelectric dopant material, the molecular structure at present there is no literature reported on.
The purines derivative molecular R1And R2For hydrogen, alkyl, to/electron-withdrawing group or benzene, naphthalene, thiophene and other aromatic perfume (or spice) ring,
R3And R5For alkyl, and R4It is then aromatic rings, this will increase conjugated system length, and adjust molecular frontier orbital energy, and optimization is mixed
Miscellaneous dose of performance.In R4Corresponding position on aromatic rings, such as the position o, m, p of phenyl ring introduce and give (or suction) electron group or various
Functional group adjusts energy level under the premise of guaranteeing stability of molecule, optimizes molecular ionization energy, enhances molecular melting.
The alkyl is selected from methyl, ethyl, chain alkyl etc.;The electron donating group is selected from alkoxy, amido, alkane mercapto
The Electron rich aromatics rings such as base, halogen, phosphine base, thiphene ring;The electron-withdrawing group is selected from nitro, cyano, carbonyl, alkynyl, acyl
The electron-deficient aromatics ring such as imido;The aromatic rings is selected from the Electron rich aromatics rings such as benzene, naphthalene, thiophene, can connect hydrogen, alkane thereon
Base, to/electron-withdrawing group or aromatic rings.
2, the present invention also provides the preparation methods of formula (I) compound of the present invention as described above, including following two lines:
(1) 2,6- dichloropurine are raw material, are completely dissolved in dry anhydrous DMF solution, add potassium carbonate
Make catalyst, iodomethane reaction is added several times, product Compound 2 is made;
The reaction of the step (1) is as follows:
Route one: compound 2 and iodo aromatic rings (R will be made in (2) in step (1)4- I) it reacts, under inert atmosphere, with
DMF is solvent, and palladium acetate, cesium carbonate and cuprous iodide are that catalyst system reacts obtained product Compound 3;
According to the present invention, the reaction of the step (2) is with R4It is as follows for p-methoxyphenyl:
(3) with R1And R2It, will be in step (2) using the feature that 6 reactivity worth of purine are more active than 2 for phenyl
Be made compound 3 respectively with R1Aryl boric acid, R2Aryl boric acid, by Suzuki-Miyaura coupling reaction twice, first in purine
6 connection R of ring2, then in 2 connection R1Product Compound 4 is made;
According to the present invention, the reaction of the step (3) is as follows:
(4) compound 4 will be made in step (3) first in toluene solvant, under sodium ethoxide catalysis, is obtained with iodomethane reaction
After recrystallization, target product 5 is made with sodium borohydride reduction in ethanol solution in quaternary ammonium salt;
According to the present invention, the reaction of the step (4) is as follows:
Route two: (II) feature more active than 2 using 6 reactivity worth of purine, by chemical combination obtained in step (1)
Object 2 respectively with R1Aryl boric acid, R2Aryl boric acid, by Suzuki-Miyaura coupling reaction twice, first in 6 companies of purine ring
Meet R2, then in 2 connection R1Product Compound 6 is made;
The reaction of the step (II) is as follows:
(III) by compound obtained in step (II) 6 and paraiodoanisole reaction response, under inert atmosphere, it is with DMF
Solvent, palladium acetate are catalyst, mixed carbonic acid caesium, the obtained product Compound 4 of cuprous iodide reaction;
(IV) identical as (4) the step of route one that obtained compound 4 is first in toluene solvant, under sodium alkoxide catalysis, with iodine
Methane reaction obtains quaternary ammonium salt, and after recrystallization, target product 5 is made with sodium borohydride reduction in ethanol solution.
According to the present invention, in the step (1), the raw material (compound 1), potassium carbonate amount ratio be 1mmol:0.8-
1.2mmol, preferably 1mmol:1-1.2mmol;Wherein generate compound 2 reaction temperature be room temperature, preferably 25 DEG C.
According to the present invention, after step (1) reaction, the preferably described purification process is as follows: reaction system is poured into 60-
In 80mL (preferably 60-70mL) distilled water, after stirring 10min, with 120-160ml (preferably 130-150mL) methylene chloride point three
Secondary extraction merges organic phase, and anhydrous magnesium sulfate dries, filters, and is spin-dried for methylene chloride, removes solvent, column chromatography purification under reduced pressure
Obtain white solid product compound 2.
According to the present invention, in the step of scheme one (2), compound 2, cuprous iodide, palladium acetate, paraiodoanisole,
The amount ratio of cesium carbonate is 1mmol:2-4mmol:0.05-0.1mmol:1-3mmol:2-4mmol, preferably 1mmol:3-4mmol:
0.05-0.1mmol:1-2mmol:3-4mmol;Reaction temperature is 140-180 DEG C, preferably 155-165 DEG C;Reaction time is 50-
70h, preferably 55-65h.
According to the present invention, after step (2) reaction, reaction system is post-processed, the preferably described purification process is as follows
It is shown: reaction system is poured into 80-150mL (preferably 100-120mL) methylene chloride, it is (excellent with 80-120mL after stirring 5min
Selecting 90-100mL) moisture washs three times, and organic phase washed once with saturated salt solution, then be dried, filtered with anhydrous magnesium sulfate, rotation
Dry dichloromethane, removes solvent under reduced pressure, and column chromatography purifies to obtain brown color crystalline Compound 3.
According to the present invention, in the step (3), compound 3, phenyl boric acid, tetra-triphenylphosphine palladium, potassium carbonate amount ratio be
1mmol:3-4mmol:0.05-0.1mmol:2-5mmol, preferably 1mmol:3-4mmol:0.05-0.1mmol:3-4mmol;Instead
Answering temperature is 80-100 DEG C, preferably 90-95 DEG C;Reaction time is 8-12h, preferably 10h.
According to the present invention, after step (3) reaction, purification process is carried out to reaction system, the preferably described purification process is such as
Shown in lower: removing extra solvent under reduced pressure, product is dissolved in 130-180mL (preferably 140-160mL) methylene chloride, uses 80-
120mL (preferably 90-100mL) distilled water washs organic phase in three times, then washed once with saturated salt solution, and organic phase is with anhydrous
Magnesium sulfate is spin-dried for organic solvent after drying, filtering, column chromatography purifies to obtain yellow-brown solid compound 4.
According to the present invention, in the step (4), compound 4, dehydrated alcohol, sodium, iodomethane, sodium borohydride amount ratio
For 1mmol:20-30mmol:2-5mmol:8-10mmol:2-4mmol, preferably 1mmol:25-30mmol:3-4mmol:9-
10mmol:3-4mmol;Reaction temperature is 80-100 DEG C, preferably 90-95 DEG C;Reaction time is 8-12h, preferably 8h.
According to the present invention, after step (4) reaction, purification process is carried out to reaction system, the preferably described purification process is such as
Shown in lower: reaction system being poured into 200mL beaker, the dilute hydrochloric acid of 20mol/L is slowly added dropwise, keeps stirring to solution and is in
Property, it is spin-dried for solvent, product is dissolved in 100-150mL (preferably 130-140mL) methylene chloride, is steamed with 50-80mL (preferably 60-70mL)
Distilled water washs organic phase in three times, then washed once with saturated salt solution, and organic phase is spin-dried for after being dried, filtered with anhydrous magnesium sulfate
Organic solvent, column chromatography purify to obtain yellow compound 5.
According to the present invention, in the step of scheme two (II), compound 2, phenyl boric acid, tetra-triphenylphosphine palladium, potassium carbonate
Amount ratio be 1mmol:3-4mmol:0.05-0.1mmol:2-5mmol, preferably 1mmol:3-4mmol:0.05-0.1mmol:
3-4mmol;Reaction temperature is 80-100 DEG C, preferably 90-95 DEG C;Reaction time is 8-12h, preferably 10h.
According to the present invention, after step (II) reaction, purification process is carried out to reaction system, the preferably described purification process is such as
Shown in lower: removing extra solvent under reduced pressure, product is dissolved in 100-150mL (preferably 120-140mL) methylene chloride, uses 50-
80mL (preferably 60-80mL) distilled water washs organic phase in three times, then washed once with saturated salt solution, the anhydrous sulphur of organic phase
Sour magnesium is spin-dried for organic solvent after drying, filtering, column chromatography purifies to obtain yellow-brown solid compound 6.
According to the present invention, in the step (III), compound 6, cuprous iodide, palladium acetate, paraiodoanisole, cesium carbonate
Amount ratio is 1mmol:2-4mmol:0.05-0.1mmol:1-3mmol:2-4mmol, preferably 1mmol:3-4mmol:0.05-
0.1mmol:1-2mmol:3-4mmol;Reaction temperature is 140-180 DEG C, preferably 155-165 DEG C;Reaction time is 50-70h, excellent
Select 55-65h.
According to the present invention, after step (III) reaction, reaction system is post-processed, the preferably described purification process is as follows
It is shown: reaction system is poured into 80-150mL (preferably 100-120mL) methylene chloride, it is (excellent with 80-120mL after stirring 5min
Selecting 90-100mL) moisture washs three times, and organic phase washed once with saturated salt solution, then be dried, filtered with anhydrous magnesium sulfate, rotation
Dry dichloromethane, removes solvent under reduced pressure, and column chromatography purifies to obtain yellow-brown solid compound 4.
According to the present invention, the step (IV) is identical with above-mentioned steps (4).
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum that embodiment 6 prepares gained target product (compound 5).
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.Under
It states in method unless otherwise instructed, the method is conventional method, with R1And R2For phenyl, R3And R5For methyl, R4For to first
For phenyl.
Embodiment 1, preparation 9- methyl -2,6- dichloropurine (compound 2)
2,6- dichloropurine (0.453g, 2.41mmol) is dissolved in 10mlDMF, at room temperature be added potassium carbonate (0.375g,
2.71mmol), then it is added three times the iodomethane of 3ml, stirs 10h at room temperature.Reaction system is poured into 60mL distilled water, is stirred
It after mixing 10min, is extracted in three times with 150ml methylene chloride, merges organic phase, anhydrous magnesium sulfate dries, filters, and is spin-dried for dichloromethane
Alkane, removes solvent under reduced pressure, and column chromatography purifies to obtain white solid product compound 2.
Embodiment 2, preparation 9- methyl -8- p-methoxyphenyl -2,6- dichloropurine (compound 3)
By compound 2 (0.404g, 2mmol), Pd (OAc)2It is (0.022g, 0.1mmol), CuI (1.142g, 6mmol), right
Iodanisol (0.936g, 4mmol) and Cs2CO3(1.630g, 5mmol) is added in 100ml bottle with two necks, is added under nitrogen atmosphere
DMF20ml reacts 60 hours at 160 DEG C.After reaction, after reaction system being cooled to room temperature, it is added three times 150ml bis-
Chloromethanes is extracted, and organic phase is merged, and is washed respectively with water, saturation NaCl solution to organic phase.Organic phase is with anhydrous
Magnesium sulfate dries, filters, and is spin-dried for methylene chloride, removes solvent under reduced pressure, and column chromatography purifies to obtain brown color crystalline Compound 3.
Embodiment 3, preparation 9- methyl -2,6- diphenyl -8- p-methoxyphenyl purine (compound 4)
By compound 3 (0.308g, 1mmol), phenyl boric acid (0.128g, 1.05mmol), tetra-triphenylphosphine palladium,
(0..128g, 1.05mmol), potassium carbonate (0.415g, 3mmol) are added in the 100ml bottle full of argon gas, and 20ml first is added
Benzene makees solvent, reacts 8h at 95 DEG C.In the THF for the drying that phenyl boric acid (0..128g, 1.05mmol) is dissolved in 5ml again, argon gas is protected
The 10h that is added in reaction solution that the reaction was continued under shield.After reaction, it is spin-dried for solvent, 100ml methylene chloride is added and dissolves substrate,
Organic phase is washed in three times with 60ml distilled water, then organic phase is washed with saturation NaCl solution.The anhydrous sulphur of organic phase
Sour magnesium dries, filters, and is spin-dried for methylene chloride, removes solvent under reduced pressure, and column chromatography purifies to obtain yellow solid product.By the yellow
Solid product is as raw material, and repeatedly aforesaid operations (can replace other aryl boric acids in this step), can be prepared palm fibre again
Yellow crystalline compound 4.
Embodiment 4, preparation 9- methyl -2,6- diphenyl purine (compound 6)
By compound 2 (0.202g, 1mmol), phenyl boric acid (0.128g, 1.05mmol), tetra-triphenylphosphine palladium,
(0..128g, 1.05mmol), potassium carbonate (0.415g, 3mmol) are added in the 100ml bottle full of argon gas, and 20ml first is added
Benzene makees solvent, reacts 8h at 95 DEG C.In the THF for the drying that phenyl boric acid (0..128g, 1.05mmol) is dissolved in 5ml again, argon gas is protected
The 8h that is added in reaction solution that the reaction was continued under shield.After reaction, extra solvent is removed under reduced pressure, product is dissolved in 150ml bis-
Chloromethanes washs organic phase with 90ml distilled water in three times, then washed once with saturated salt solution, organic phase anhydrous magnesium sulfate
Organic solvent is spin-dried for after drying, filtering, column chromatography purifies to obtain faint yellow solid product.Using the faint yellow solid product as original
Material, repeatedly aforesaid operations (can replace other aryl boric acids in this step), can be prepared compound 6 again.
Embodiment 5, preparation 6- benzene -8- are to methoxybenzene -9- methyl purine (compound 5)
By compound 6 (0.572g, 2mmol), Pd (OAc)2(0.022g,0.1mmol)、CuI(1.142g,6mmo l)、
Paraiodoanisole (0.936g, 4mmol) and Cs2CO3(1.630g, 5mmol) is added in 100ml bottle with two necks, is added under nitrogen atmosphere
DMF20ml reacts 60 hours at 160 DEG C.After reaction, after reaction system being cooled to room temperature, it is added three times 150ml bis-
Chloromethanes is extracted, and organic phase is merged, and is washed respectively with water, saturation NaCl solution to organic phase.Organic phase is with anhydrous
Magnesium sulfate dries, filters, and is spin-dried for methylene chloride, removes solvent under reduced pressure, and column chromatography purifies to obtain brown color crystalline Compound 4.
Embodiment 6 prepares target product purine derivative molecule (compound 5)
25mL dehydrated alcohol is added in 250mL reaction flask, the cooling lower stirring of ice bath is slowly added to remove the new of oxide layer
Cut metallic sodium silk (2.8g, 20mmol), be cooled to room temperature after fully reacting, be added 60mL benzene, by compound 4 (0.392g,
It 1mmol) is added in reaction flask, is added three times iodomethane 4mL, be heated to reflux 10h, solvent is evaporated off after reaction, will react
Object is dissolved in 20mL dehydrated alcohol, and sodium borohydride (0.13g, 4mmol) is added under argon atmosphere, stirs 2 hours, will react at room temperature
System is poured into 200mL beaker, and the dilute hydrochloric acid of 20mol/L is slowly added dropwise, keeps stirring to solution and is in neutrality, and is spin-dried for solvent, is produced
Object is dissolved in 100m L methylene chloride, washs organic phase in three times with 50mL distilled water, then washed once with saturated salt solution, organic
It is spin-dried for organic solvent after mutually being dried, filtered with anhydrous magnesium sulfate, column chromatography purifies to obtain compound 5.
The structural characterization data of the product are as follows:
1H NMR(500MHz,CDCl3),9.24(d,2H),8.90(d,2H),7.88(d,2H),7.58–7.50(m,6H),
7.10(d,2H),4.00(s,6H),3.92(s,3H).
The nucleus magnetic hydrogen spectrum of the product is as shown in Figure 1.From the foregoing, it will be observed that the compound structure is correct.
Claims (2)
1. a kind of purine analog derivative free radical precursor molecule, structure are shown in formula I:
The purines derivative molecular R1And R2For hydrogen, alkyl, to/electron-withdrawing group or benzene, naphthalene, thiophene and other aromatic perfume (or spice) ring, R3With
R5For alkyl, and R4It is then aromatic rings, this will increase conjugated system length, and adjust molecular frontier orbital energy, optimize dopant
Performance.In R4Corresponding position on aromatic rings, such as the position o, m, p of phenyl ring are introduced to (or suction) electron group or various functions
Group adjusts energy level under the premise of guaranteeing stability of molecule, optimizes molecular ionization energy, enhances molecular melting.
The alkyl is selected from methyl, ethyl, chain alkyl etc.;The electron donating group is selected from alkoxy, amido, alkane sulfydryl, halogen
The Electron rich aromatics ring such as element, phosphine base, thiphene ring;The electron-withdrawing group is selected from nitro, cyano, carbonyl, alkynyl, imide etc.
Electron-deficient aromatic ring;The aromatic rings is selected from the Electron rich aromatics rings such as benzene, naphthalene, thiophene, can connect hydrogen, alkyl thereon, to/suction
Electron group or aromatic rings.
2. a kind of preparation method of purine analog derivative free radical precursor molecule, it is characterized in that: with R1And R2For phenyl, R3And R5For
Methyl, R4For p-methoxyphenyl, including following two lines;
(1) 2,6- dichloropurine are raw material, are completely dissolved in dry anhydrous DMF solution, add potassium carbonate and urge
Agent iodomethane reaction is added several times, product Compound (2) is made;
The reaction of the step (1) is as follows:
Route one: compound (2) and iodo aromatic rings (R will be made in (2) in step (1)4- I) it reacts, under inert atmosphere, with DMF
For solvent, palladium acetate, cesium carbonate and cuprous iodide are that catalyst system reacts obtained product Compound (3);
According to the present invention, the reaction of the step (2) is with R4It is as follows for p-methoxyphenyl:
(3) with R1And R2For phenyl, using the feature that 6 reactivity worth of purine are more active than 2, it will be made in step (2)
Compound (3) respectively with R1Aryl boric acid, R2Aryl boric acid, by Suzuki-Miyaura coupling reaction twice, first in purine ring
6 connection R2, then in 2 connection R1It is made product Compound (4);
According to the present invention, the reaction of the step (3) is as follows:
(4) compound (4) will be made in step (3) first in toluene solvant, under sodium ethoxide catalysis, obtains season with iodomethane reaction
After recrystallization, target product (5) are made with sodium borohydride reduction in ethanol solution in ammonium salt;
According to the present invention, the reaction of the step (4) is as follows:
Route two: (II) by compound (2) obtained in step (1) respectively with R1Aryl boric acid, R2Aryl boric acid, by twice
Suzuki-Miyaura coupling reaction, first in 2 connection R of purine ring1, then in 6 connection R2It is made product Compound (6);
The reaction of the step (II) is as follows:
It (III) is molten with DMF under inert atmosphere by compound (6) obtained in step (II) and paraiodoanisole reaction response
Agent, palladium acetate are catalyst, mixed carbonic acid caesium, the obtained product Compound 4 of cuprous iodide reaction;
(IV) identical as (4) the step of route one that obtained compound (4) is first in toluene solvant, under sodium alkoxide catalysis, with iodine first
Alkane reacts to obtain quaternary ammonium salt, and after recrystallization, target product (5) are made with sodium borohydride reduction in ethanol solution;
In the step (1), the raw material (compound 1), potassium carbonate amount ratio be 1mmol:0.8-1.2mmol, preferably
1mmol:1-1.2mmol;Wherein generate compound (2) reaction temperature be room temperature, preferably 25 DEG C;
After step (1) reaction, reaction system is post-processed, the preferably described purification process is as follows: by reaction system
It pours into 60-80mL (preferably 60-70mL) distilled water, after stirring 10min, with 120-160ml (preferably 130-150mL) dichloromethane
Alkane extracts in three times, merges organic phase, and anhydrous magnesium sulfate dries, filters, is spin-dried for methylene chloride, removes solvent, column color under reduced pressure
Spectrum purification obtains white solid product compound (2);
In the step of scheme one (2), compound (2), cuprous iodide, palladium acetate, paraiodoanisole, cesium carbonate amount ratio
For 1mmol:2-4mmol:0.05-0.1mmol:1-3mmol:2-4mmol, preferably 1mmol:3-4mmol:0.05-0.1mmol:
1-2mmol:3-4mmol;Reaction temperature is 140-180 DEG C, preferably 155-165 DEG C;Reaction time is 50-70h, preferably 55-
65h;
After step (2) reaction, reaction system is post-processed, the preferably described purification process is as follows: by reaction system
It pours into 80-150mL (preferably 100-120mL) methylene chloride, after stirring 5min, with 80-120mL (preferably 90-100mL) moisture
It washs three times, organic phase washed once with saturated salt solution, then be dried, filtered with anhydrous magnesium sulfate, be spin-dried for methylene chloride, depressurize
Solvent is evaporated off, column chromatography purifies to obtain brown color crystalline Compound (3);
In the step (3), compound (3), phenyl boric acid, tetra-triphenylphosphine palladium, potassium carbonate amount ratio be 1mmol:3-
4mmol:0.05-0.1mmol:2-5mmol, preferably 1mmol:3-4mmol:0.05-0.1mmol:3-4mmol;Reaction temperature is
80-100 DEG C, preferably 90-95 DEG C;Reaction time is 8-12h, preferably 10h;
After step (3) reaction, purification process is carried out to reaction system, the preferably described purification process is as follows: removing under reduced pressure
Extra solvent is removed, product is dissolved in 130-180mL (preferably 140-160mL) methylene chloride, with 80-120mL (preferably 90-
100mL) distilled water washs organic phase in three times, then washed once with saturated salt solution, and organic phase is dry with anhydrous magnesium sulfate, mistake
Organic solvent is spin-dried for after filter, column chromatography purifies to obtain yellow-brown solid compound 4;
In the step (4), compound (4), dehydrated alcohol, sodium, iodomethane, sodium borohydride amount ratio be 1mmol:20-
30mmol:2-5mmol:8-10mmol:2-4mmol, preferably 1mmol:25-30mmol:3-4mmol:9-10mmol:3-4mmol;
Reaction temperature is 80-100 DEG C, preferably 90-95 DEG C;Reaction time is 8-12h, preferably 8h;
After step (4) reaction, purification process is carried out to reaction system, the preferably described purification process is as follows: by reactant
System pours into 200mL beaker, and the dilute hydrochloric acid of 20mol/L is slowly added dropwise, keeps stirring to solution and is in neutrality, is spin-dried for solvent, product
It is dissolved in 100-150mL (preferably 130-140mL) methylene chloride, being washed in three times with 50-80mL (preferably 60-70mL) distilled water has
Machine phase, then washed once with saturated salt solution, organic phase is spin-dried for organic solvent, column chromatography after being dried, filtered with anhydrous magnesium sulfate
Purification obtains yellow compound 5;
In the step of scheme two (II), compound (2), phenyl boric acid, tetra-triphenylphosphine palladium, potassium carbonate amount ratio be
1mmol:3-4mmol:0.05-0.1mmol:2-5mmol, preferably 1mmol:3-4mmol:0.05-0.1mmol:3-4mmol;Instead
Answering temperature is 80-100 DEG C, preferably 90-95 DEG C;Reaction time is 8-12h, preferably 10h;
After step (II) reaction, purification process is carried out to reaction system, the preferably described purification process is as follows: removing under reduced pressure
Extra solvent is removed, product is dissolved in 100-150mL (preferably 120-140mL) methylene chloride, with 50-80mL (preferably 60-80mL)
Distilled water washs organic phase in three times, then washed once with saturated salt solution, and organic phase dries, filters back spin with anhydrous magnesium sulfate
Dry organic solvent, column chromatography purify to obtain compound (6);
In the step (III), compound (6), cuprous iodide, palladium acetate, paraiodoanisole, cesium carbonate amount ratio be
1mmol:2-4mmol:0.05-0.1mmol:1-3mmol:2-4mmol, preferably 1mmol:3-4mmol:0.05-0.1mmol:1-
2mmol:3-4mmol;Reaction temperature is 140-180 DEG C, preferably 155-165 DEG C;Reaction time is 50-70h, preferably 55-65h;
After step (III) reaction, reaction system is post-processed, the preferably described purification process is as follows: by reaction system
It pours into 80-150mL (preferably 100-120mL) methylene chloride, after stirring 5min, with 80-120mL (preferably 90-100mL) moisture
It washs three times, organic phase washed once with saturated salt solution, then be dried, filtered with anhydrous magnesium sulfate, be spin-dried for methylene chloride, depressurize
Solvent is evaporated off, column chromatography purifies to obtain yellow-brown solid compound (4);
The step (IV) is identical with above-mentioned steps (4).
Column chromatography described in above-mentioned steps purifies the mixed solvent that solvent for use is methylene chloride and petroleum ether, and ratio can basis
The polarity of product determines.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811545572.2A CN109651370A (en) | 2018-12-17 | 2018-12-17 | A kind of purine analog derivative free radical precursor molecule and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811545572.2A CN109651370A (en) | 2018-12-17 | 2018-12-17 | A kind of purine analog derivative free radical precursor molecule and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109651370A true CN109651370A (en) | 2019-04-19 |
Family
ID=66113735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811545572.2A Withdrawn CN109651370A (en) | 2018-12-17 | 2018-12-17 | A kind of purine analog derivative free radical precursor molecule and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109651370A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113201244A (en) * | 2021-04-30 | 2021-08-03 | 桂林理工大学 | Dopant, preparation method, application and functionalized emulsion paint thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4156778A (en) * | 1977-03-16 | 1979-05-29 | Hoechst Aktiengesellschaft | Substituted bis-benzimidazolyl compounds; preparation and use thereof |
EP0009163B1 (en) * | 1978-09-14 | 1982-06-30 | Hoechst Aktiengesellschaft | Substituted bisbenzimidazole derivatives, their preparation and antiprotozoic and antiviral agents |
JP2000280621A (en) * | 1999-03-30 | 2000-10-10 | Mitsui Chemicals Inc | Optical recording medium |
US20060234974A1 (en) * | 2003-01-24 | 2006-10-19 | Sumitomo Chemical Company, Limited | 2,6-Dihalogeno-8-substituent-purine compound and process for producing the same |
CN101093874A (en) * | 2006-03-21 | 2007-12-26 | 诺瓦莱德公开股份有限公司 | Method of manufacturing compound including matrix material and doping material, and layer including doped organic material |
CN104658731A (en) * | 2014-12-22 | 2015-05-27 | 中国科学院重庆绿色智能技术研究院 | Method for reducing square resistance of graphene film by stably doping |
CN107698588A (en) * | 2017-09-25 | 2018-02-16 | 长春海谱润斯科技有限公司 | Hot activation delayed fluorescence material and its organic electroluminescence device based on purine derivative |
CN108242508A (en) * | 2016-12-26 | 2018-07-03 | 昆山国显光电有限公司 | Electron transfer layer and preparation method thereof and organic luminescent device |
-
2018
- 2018-12-17 CN CN201811545572.2A patent/CN109651370A/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4156778A (en) * | 1977-03-16 | 1979-05-29 | Hoechst Aktiengesellschaft | Substituted bis-benzimidazolyl compounds; preparation and use thereof |
EP0009163B1 (en) * | 1978-09-14 | 1982-06-30 | Hoechst Aktiengesellschaft | Substituted bisbenzimidazole derivatives, their preparation and antiprotozoic and antiviral agents |
JP2000280621A (en) * | 1999-03-30 | 2000-10-10 | Mitsui Chemicals Inc | Optical recording medium |
US20060234974A1 (en) * | 2003-01-24 | 2006-10-19 | Sumitomo Chemical Company, Limited | 2,6-Dihalogeno-8-substituent-purine compound and process for producing the same |
CN101093874A (en) * | 2006-03-21 | 2007-12-26 | 诺瓦莱德公开股份有限公司 | Method of manufacturing compound including matrix material and doping material, and layer including doped organic material |
CN104658731A (en) * | 2014-12-22 | 2015-05-27 | 中国科学院重庆绿色智能技术研究院 | Method for reducing square resistance of graphene film by stably doping |
CN108242508A (en) * | 2016-12-26 | 2018-07-03 | 昆山国显光电有限公司 | Electron transfer layer and preparation method thereof and organic luminescent device |
CN107698588A (en) * | 2017-09-25 | 2018-02-16 | 长春海谱润斯科技有限公司 | Hot activation delayed fluorescence material and its organic electroluminescence device based on purine derivative |
Non-Patent Citations (4)
Title |
---|
CHE, XIN等: "Synthesis of 7,8,9-trisubstituted dihydropurine derivatives via a tert-amino effect cyclization", 《SYNLETT》 * |
ZHENGYANG BIN ET AL.,: ""Air Stable Organic Salt As an n Type Dopant for Efficient and Stable Organic Light-Emitting Diodes", 《ACS APPLIED MATERIALS & INTERFACES》 * |
孙朋等: "含m_氨基结构的有机分子掺杂型氮化碳光催化剂的研究", 《华南理工大学硕士学位论文》 * |
施薇: "基于生物材料的有机薄膜晶体管研究", 《电子科技大学博士学位论文》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113201244A (en) * | 2021-04-30 | 2021-08-03 | 桂林理工大学 | Dopant, preparation method, application and functionalized emulsion paint thereof |
CN113201244B (en) * | 2021-04-30 | 2022-07-01 | 桂林理工大学 | Dopant, preparation method, application and functionalized emulsion paint thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109666033B (en) | Conjugated small molecule based on nona-fused heterocycle and preparation method and application thereof | |
CN103288848B (en) | Benzo three thiophenes and its production and use | |
CN106748832B (en) | Hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells | |
CN112778327A (en) | Organic non-fullerene electron acceptor material and preparation method and application thereof | |
CN103554445B (en) | One contains the organic poromerics of hetero atom and preparation thereof and application | |
CN103087083A (en) | Diketopyrrolopyrrole derivative and preparation method and application thereof | |
CN106432265A (en) | Thiophene compound, preparation method and application thereof and perovskite solar battery | |
CN107141243A (en) | The nitrogenous cyclosubstituted bowl alkene molecule of one five yuan of class and derivative and its preparation and application | |
JP2013529227A (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
CN110078739A (en) | A kind of hole mobile material and preparation method thereof, perovskite solar battery | |
CN109641914A (en) | The design and synthesis of porphyrin material for high efficiency organic photovoltaic | |
CN108948026A (en) | One kind three and carbazole-phenyl hole mobile material and the preparation method and application thereof | |
CN110734451A (en) | semiconductor materials, preparation method thereof and organic light emitting diode | |
CN108148184A (en) | One kind contains acenaphthene simultaneously conjugated polymer of [1,2-b] quinoxaline imidodicarbonic diamide and its preparation method and application | |
CN110194778A (en) | A kind of multi-arm structure organic photovoltaic material and the preparation method and application thereof | |
CN109651370A (en) | A kind of purine analog derivative free radical precursor molecule and preparation method thereof | |
KR101595919B1 (en) | organinc semiconductor compound and organic solar cell having them | |
CN106554373B (en) | A kind of azepine trimethylene class [iron iron] hydrogenase activity center model object and its synthetic method containing Phosphine ligands | |
CN112961169A (en) | Imide compound, preparation method thereof and application of perovskite solar cell | |
CN106800556A (en) | A kind of structure of three-dimensional triphen amine hole mobile material, synthesis and application | |
CN109369612A (en) | A kind of aryl radical precursor molecule of symmetrical configuration and preparation method thereof | |
CN111807992B (en) | D-A type tetracyanoanthraquinone-dimethane photoelectric functional material, and preparation method and application thereof | |
CN103834190A (en) | Benzothiadiazole-cyanocinnamic acid receptor-containing organic dye and its use in dye-sensitized solar cell | |
CN105777666A (en) | Preparation method of iodine atom-substituted methylic fluorobenzene and heterocyclic compound | |
Peng et al. | Simultaneous enhancement of fluorescence and solubility by N-alkylation and functionalization of 2-(2-thienyl) imidazo [4, 5-f][1, 10]-phenanthroline with heterocyclic bridges |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190419 |