CN106892927B - A method of synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin - Google Patents
A method of synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin Download PDFInfo
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- CN106892927B CN106892927B CN201710145753.5A CN201710145753A CN106892927B CN 106892927 B CN106892927 B CN 106892927B CN 201710145753 A CN201710145753 A CN 201710145753A CN 106892927 B CN106892927 B CN 106892927B
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- C07—ORGANIC CHEMISTRY
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Abstract
The present invention relates to a kind of methods for synthesizing four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin, comprising the following steps: with 3,3- dimethyl-2-butanone is raw material, selenylation reaction is carried out with selenium dioxide, and 3,3- dimethyl -2- oxo butyraldehyde is obtained to product rectification；3,3- dimethyl -2- oxo butyraldehyde obtained in above-mentioned steps is heated under the conditions of 2,3- diamino -2- maleonitrile, urea and metal chloride are existing, purification of products is obtained into four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin.The present invention is only through selenizing and synthesis two-step reaction, then is simply purified, and four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin can be obtained, process is simple, and product is controllable；It is raw materials used simple, it is low in cost；And pilot process does not generate poisonous and hazardous waste products, greatly reduces the process of post-processing.Four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin yield produced by the present invention is high.
Description
Technical field
The present invention relates to organic chemical industry's synthesis technical fields, specifically a kind of four -2,3- of synthesis (5- tert-butyl pyrrole
Piperazine) metalloporphyrin method.
Background technique
In recent years, scientific worker replaces the research enthusiasm of porphyrin (TPyzPzs) to grow to even greater heights four pyrazines, this is derived from this
Potential practical application of the substance in various fields.Up to now, such TPyzPzs macrocyclic compound has frequently occurred on report
In road, for example as electronic element device materials (optical information imprinting, electrofax optical flame detector and photoconductor, organic transistor,
Liquid crystal film, electroluminescent cell), printing ink dyestuff and carbon dust colorant, Fresh Cutting flower preservative, polymer thermostable
The light activating agent of singlet oxygen and the fluorescence quencher for DNA detection in agent, luminous energy therapy.
Researcher's original research it is most be the peripheral unsubstituted most easily obtained nonmetallic TPyzPzsH2And its gold
Belong to porphyrin compound MTPyzPzs.But the TPyzPzs water solubility of unsubstituted is very poor, this greatly limits it in reality
The potential in, also therefore, the research emphasis of Recent study personnel are transferred to the various functional group's substituent groups of peripheral band
TPyzPzs and metalloporphyrin MTPyzPzs.It is higher molten in aqueous solution and organic solvent that peripheral substituent assigns TPyzPzs
Xie Xing, while also slightly changing spectrum and other physicochemical characteristics and bioactivity.Nearly ten years, large number of such
Macrocyclic compound is synthesized and is studied, and especially in medical domain, they are seen as multiple using luminous energy therapy
The most promising substance of tumor therapy, while also as the catalyst of oxidation-reduction process.
The structure of four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin is as follows:
Document (M.G.Gal'pern, E.A.Luk'yanets.TETRA-2,3- (5-TERT-BUTYLPYRAZINO) POR
PHYRAZINES.Chem.Heterocycl.Compd.8 (1972) 780.) report a kind of synthesis four -2,3- (5- tert-butyl pyrrole
Piperazine) metalloporphyrin method, the method use a large amount of potassium permanganate and organic solvent to make raw material, needs four steps that can just obtain mesh
Product is marked, process exception is cumbersome and needs strict control reaction condition, and yield is very low, and generates containing manganese residue and largely useless
Liquid, it is both uneconomical or not environmentally.The synthesis process of described four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin in document is such as
Under:
Summary of the invention
The object of the present invention is to provide a kind of processes, and simple, the at low cost, three wastes generate four few -2,3- (5- tert-butyl pyrrole
Piperazine) metalloporphyrin synthetic method.
To achieve the above object, the present invention provides a kind of following technical solutions: synthesis four -2,3- (5- tert-butyl-pyrazin)
The method of metalloporphyrin, comprising the following steps:
With 3,3- dimethyl-2-butanone for raw material, selenylation reaction is carried out with selenium dioxide, and 3,3- are obtained to product rectification
Dimethyl -2- oxo butyraldehyde；
By 3,3- dimethyl -2- oxo butyraldehyde obtained in above-mentioned steps 2,3- diamino -2- maleonitrile, urea and
It is heated under the conditions of metal chloride is existing, purification of products is obtained into four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin.
Preferably: the molar ratio of the selenium dioxide and 3,3- dimethyl-2-butanone is 1~1.5:1.
Preferably: the reflux temperature of the selenylation reaction is 50~80 DEG C；The time of the selenylation reaction is 4~5h.
Preferably: the rectification temperature is 112~115 DEG C.
Preferably: the 3,3- dimethyl -2- oxo butyraldehyde: 2,3- diamino -2- maleonitrile: metal chloride:
The molar ratio of urea is 1:1:0.5~1:4~6.
Preferably: the 3,3- dimethyl -2- oxo butyraldehyde, 2,3- diamino -2- maleonitrile, metal chloride and
The heating process of urea are as follows: first heating temperature reaches 130~140 DEG C, is further continued for heating up after keeping 15~20min, reach 190~
2~3h is kept sufficiently to react to raw material after 220 DEG C.
Preferably: the purification process includes repeatedly washing process and recrystallization process.
Preferably: the washing process repeatedly are as follows: first washed repeatedly using distilled water, diluted acid or dilute alkaline soln more
It is secondary, then washed repeatedly repeatedly with dehydrated alcohol or acetone colourless to filtrate.
Preferably: the solvent that the recrystallization process uses is N,N-dimethylformamide, dimethyl sulfoxide or dense sulphur
Acid.
The beneficial effects of the present invention are: the present invention with 3,3- dimethyl-2-butanone for raw material, through selenylation reaction and synthesis
Two steps are reacted, then are simply purified, four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin can be obtained, process is simple, and product can
Control；It is raw materials used simple, it is low in cost；And pilot process does not generate poisonous and hazardous waste products, greatly reduces at the later period
The process of reason.Four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin yield produced by the present invention is high, and method is worthy to be popularized.
Detailed description of the invention
Attached drawing 1 is the uv-vis spectra of four -2,3- (5- tert-butyl-pyrazin) Cobalt Porphyrin；
Attached drawing 2 is the uv-vis spectra of four -2,3- (5- tert-butyl-pyrazin) porphyrin copper；
Attached drawing 3 is the uv-vis spectra of four -2,3- (5- tert-butyl-pyrazin) zinc porphyrin.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
The present invention provides a kind of methods for synthesizing four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin, comprising the following steps:
With 3,3- dimethyl-2-butanone for raw material, selenylation reaction is carried out with selenium dioxide, and 3,3- are obtained to product rectification
Dimethyl -2- oxo butyraldehyde；
By 3,3- dimethyl -2- oxo butyraldehyde obtained in above-mentioned steps 2,3- diamino -2- maleonitrile, urea and
It is heated under the conditions of metal chloride is existing, purification of products is obtained into four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin.
Further, selenium dioxide and 3, the molar ratio of 3- dimethyl-2-butanone are 1~1.5:1.Selenium dioxide is a kind of
Oxidant, in order to keep selenylation reaction more complete, the amount of selenium dioxide can be appropriate more.
Further, the reflux temperature of selenylation reaction is 50~80 DEG C, at a temperature of this, reaction can be accelerated to carry out, simultaneously
Prevent target product volatilizing loss；The time of the selenylation reaction is 4~5h, so that raw material sufficiently reacts.
Further, rectification temperature is 112~115 DEG C.Because of the boiling point of intermediate product 3,3- dimethyl -2- oxo butyraldehyde
It is 112~115 DEG C, therefore the temperature range requirements of this distillation process are very narrow.
Further, 3,3- dimethyl -2- oxo butyraldehyde: 2,3- diamino -2- maleonitriles: metal chloride: urea
Molar ratio be 1:1:0.5~1:4~6.Wherein, the metal of metal chloride can be the transition metal such as cobalt, copper, zinc, nickel, iron
Element.
Further, 3,3- dimethyl -2- oxo butyraldehyde, 2,3- diamino -2- maleonitrile, metal chloride and urea
Heating process are as follows: first heating temperature reaches 130~140 DEG C, is further continued for heating up after keeping 15~20min, urea at a temperature of this
Start to melt, heating is further continued for after urea all melts and is conducive to raw material full utilization.When warming temperature reaches 190~220
2~3h is kept sufficiently to react to raw material after DEG C, it is finally completely solid that the mixture during this in container from liquid becomes muddy
Change, reaction terminates.
Further, purification process includes repeatedly washing process and recrystallization process.
Further, washing process are as follows: first washed repeatedly repeatedly using distilled water, diluted acid or dilute alkaline soln, then with anhydrous
Ethyl alcohol or acetone wash repeatedly colourless to filtrate repeatedly.
Further, the solvent that recrystallization purification process uses is n,N-Dimethylformamide, dimethyl sulfoxide or the concentrated sulfuric acid.
The reactional equation process that the present invention specifically occurs is as follows:
1. selenizing:
2. cyclization:
Q B band and 600~700nm at of the porphyrin compound there are two characteristic absorption band, at respectively 250~350nm
Band.
The present invention characterizes the product finally synthesized, whether to verify porphyrin cyclization, the specific steps are as follows:
1. 3- (5- tert-butyl-pyrazin) metalloporphyrin dissolves in 50ml n,N-Dimethylformamide, sufficiently by 0.01g tetra- -2
Stirring makes it completely dissolved；
2. the use of the general general TU-1901 type ultraviolet-uisible spectrophotometer of analysis being ginseng with n,N-Dimethylformamide (DMF)
According to and blank sample, 300~800nm of wave-length coverage, baseline calibration；
3. using the solution rinse cuvette in 1. three times after, add at cuvette 9/10；
4. sweep spacing 0.5nm is arranged, scanning speed is middling speed, obtains uv-vis spectra.
Synthetic test is carried out respectively using three kinds of chlorides as raw material below, and the present invention will be described in detail.
Embodiment 1
It accurately weighs 0.11mol (12.2g) selenium dioxide with balance to pour into three-neck flask, liquid-transfering gun pipettes 0.1mol
(12.5ml) 3,3- dimethyl-2-butanone is added in dropping funel.Oil bath pot temperature is maintained at 50 DEG C, and condenser pipe water flowing is started
Blender maintains revolving speed in 200r/min or so, opens dropping funel, is slowly dropped into 3,3- dimethyl-2-butanone, this process is
Exothermic reaction continuously stirs 5h.Entire reaction carries out in draught cupboard.
With reaction progress we can observe that, the colourless liquid in bottle gradually becomes yellow, and bottom of bottle solid is by white
Discoloration is grey black.After reaction, a moment is stood, supernatant liquid is poured into flask, is moistened with a small amount of 3,3- dimethyl-2-butanone
Wash slag, pours into flask together.Liquid is raw material 3,3- dimethyl-2-butanone, product 3,3- dimethyl -2- oxo in flask
The mixture of butyraldehyde and water.Rectifying is carried out to mixture using rectifying column, filler is done using glass spring, electricity is surrounded by outside rectifying column
The torrid zone steams yellow liquid under the conditions of 115 DEG C, be cooled to room temperature 10.1g white solid is 3,3- dimethyl -2- oxo fourth
Aldehyde, yield 45.5%.
Reaction raw materials 3,3- dimethyl -2- oxo butyraldehyde: 2,3- diamino -2- maleonitrile: hydrated cobalt chloride: urea
Molar ratio is 1:1:0.5:4.Electronic balance accurately weighs 3,3- dimethyl -2- oxo butyraldehyde 0.02mol (2.2828g), diamino
Base Maleic nitrile 0.02mol (2.162g), hydrated cobalt chloride 0.01mol (2.3793g) and urea 0.08mol (4.8048g) mixing
Three-neck flask is poured into after uniformly.Oil bath heating is to slowly warm up to 140 DEG C, this temperature is kept all to melt to urea, during which continuous
Stirring guarantees that raw material is sufficiently mixed uniformly.It is continuously heating to 200 DEG C and keeps 2h, reactant is expanded to rapidly mud state by liquid
Then it slowly shrinks until eventually becoming solid-state.It is cooled to room temperature, takes out that solid matter agate mortar is finely ground must to react thick
Product.Crude product is first washed with distilled water, and filters, vacuum oven 70 DEG C drying colourless to filtrate, the rear anhydrous second boiled
Alcohol washs colourless to filtrate repeatedly.It is finely ground after filter cake vacuum drying to be dissolved in DMF, it is filtered to remove inorganic impurity, to dissolved with four -2,3-
Distilled water is added in the DMF solution of (5- tert-butyl-pyrazin) Cobalt Porphyrin, and black-and-blue precipitating is precipitated, and filters, and filter cake distilled water is multiple
9.49g tetra- -2 obtained by drying after flushing, 3- (5- tert-butyl-pyrazin) Cobalt Porphyrin, yield 81.6%.
Above-mentioned product is characterized, the ultraviolet-visible spectrogram of four -2,3- (5- tert-butyl-pyrazin) Cobalt Porphyrin is obtained,
Referring to Fig. 1.From figure 1 it appears that occurring characteristic absorption band at two near 330nm and 620nm, meet porphyrin compound point
The requirement of B band and Q band is formed not at 250~350nm and at 600~700nm.Illustrate to have obtained four -2,3- through above-mentioned reaction
(5- tert-butyl-pyrazin) Cobalt Porphyrin.
Embodiment 2:
It accurately weighs 0.13mol (14.43g) selenium dioxide with balance to pour into three-neck flask, liquid-transfering gun pipettes 0.1mol
(12.5ml) 3,3- dimethyl-2-butanone is added in dropping funel.Oil bath pot temperature is maintained at 80 DEG C, and condenser pipe water flowing is started
Blender maintains revolving speed in 200r/min or so, opens dropping funel, being slowly dropped into 3,3- dimethyl-2-butanone, (heat release is anti-
Answer), continuously stir 4h.Entire reaction carries out in draught cupboard.With reaction progress we can observe that, it is colourless in bottle
Liquid gradually becomes yellow, and bottom of bottle solid becomes grey black from white.After reaction, a moment is stood, supernatant liquid is poured into
Flask pours into flask with a small amount of 3,3- dimethyl-2-butanone rinse dregs of a decoction together.Liquid is raw material 3,3- diformazan in flask
The mixture of base -2- butanone, product 3,3- dimethyl -2- oxo butyraldehyde and water.Rectifying is carried out to mixture using rectifying column, is adopted
Filler is done with glass spring, ribbon heater is surrounded by outside rectifying column, steams yellow liquid under the conditions of 115 DEG C, be cooled to room temperature to obtain 10.3g
White solid is 3,3- dimethyl -2- oxo butyraldehyde, yield 38.2%.
Reaction raw materials 3,3- dimethyl -2- oxo butyraldehyde: diaminomaleonitrile: Hydrated copper chloride: the molar ratio of urea is
1:1:1:5.Electronic balance accurately weighs 3,3- dimethyl -2- oxo butyraldehyde 0.02mol (2.2828g), diaminomaleonitrile
0.02mol (2.162g), Hydrated copper chloride 0.02mol (3.4096g) and urea 0.1mol (6.606g) are poured into after mixing
Three-neck flask.Oil bath heating is to slowly warm up to 130 DEG C, keeps this temperature all to melt to urea, it is former to be during which stirred continuously guarantee
Material is sufficiently mixed uniformly.It is continuously heating to 220 DEG C and keeps 2h, reactant is expanded to rapidly mud state by liquid and then slowly received
Contracting eventually becomes solid-state.It is cooled to room temperature, takes out and obtains reacting coarse product with agate mortar is finely ground.Crude product first uses 1mol/L's
The sodium hydroxide solution of dilute hydrochloric acid solution and 1mol/L alternately wash, and filter, vacuum oven 70 DEG C drying colourless to filtrate, after
It is washed repeatedly with acetone colourless to filtrate.It is finely ground after filter cake vacuum drying to be dissolved in DMF, it is filtered to remove inorganic impurity, to dissolved with four-
Distilled water is added in the DMF solution of 2,3- (5- tert-butyl-pyrazin) porphyrin coppers, and blue precipitate is precipitated, and filters, and filter cake distilled water is more
10.17g tetra- -2 obtained by drying after secondary flushing, 3- (5- tert-butyl-pyrazin) porphyrin copper, yield 70.3%.
Above-mentioned product is characterized, the ultraviolet-visible spectrogram of four -2,3- (5- tert-butyl-pyrazin) porphyrin copper is obtained,
Referring to fig. 2.From figure 2 it can be seen that occurring characteristic absorption band at two near 345nm and 625nm, meet porphyrin compound point
The requirement of B band and Q band is formed not at 250~350nm and at 600~700nm.Illustrate to have obtained four -2,3- through above-mentioned reaction
(5- tert-butyl-pyrazin) porphyrin copper.
Embodiment 3:
It accurately weighs 0.15mol (16.65g) selenium dioxide with balance to pour into three-neck flask, liquid-transfering gun pipettes 0.1mol
(12.5ml) 3,3- dimethyl-2-butanone is added in dropping funel.Oil bath pot temperature is maintained at 65 DEG C, and condenser pipe water flowing is started
Blender maintains revolving speed in 200r/min or so, opens dropping funel, is slowly dropped into pinacoline (exothermic reaction), continuously stirs
4.5h.Entire reaction carries out in draught cupboard.With reaction progress we can observe that, the colourless liquid in bottle gradually becomes
For yellow, bottom of bottle solid becomes grey black from white.After reaction, a moment is stood, supernatant liquid is poured into flask, with a small amount of
3, the 3- dimethyl-2-butanone rinse dregs of a decoction, pour into flask together.Liquid is raw material 3,3- dimethyl-2-butanone, produces in flask
The mixture of object 3,3- dimethyl -2- oxo butyraldehyde and water.Rectifying is carried out to mixture using rectifying column, is done using glass spring
Filler is surrounded by ribbon heater outside rectifying column, steams yellow liquid under the conditions of 115 DEG C, be cooled to room temperature 10.2g white solid is
3,3- dimethyl -2- oxo butyraldehyde, yield 35%.
Reaction raw materials 3,3- dimethyl -2- oxo butyraldehyde: diaminomaleonitrile: zinc chloride: the molar ratio of urea is 1:1:
0.8:6.Electronic balance accurately weighs 3,3- dimethyl -2- oxo butyraldehyde 0.02mol (2.2828g), diaminomaleonitrile
0.02mol (2.162g), zinc chloride 0.016mol (2.1808g) and urea 0.12mol (7.2072g) pour into three after mixing
Neck flask.Oil bath heating is to slowly warm up to 135 DEG C, keeps this temperature all to melt to urea, is during which stirred continuously guarantee raw material
It is sufficiently mixed uniformly.It is continuously heating to 220 DEG C and keeps 2h, reactant is expanded to rapidly mud state by liquid and then slowly shunk
Eventually become solid-state.It is cooled to room temperature, takes out and obtains reacting coarse product with agate mortar is finely ground.Crude product is first with distillation washing
Wash, filter it is colourless to filtrate, 70 DEG C of vacuum oven drying, after washed repeatedly with acetone it is colourless to filtrate.Filter cake vacuum drying
It is finely ground afterwards to be dissolved in DMF, it is filtered to remove inorganic impurity, to the DMF solution addition dissolved with four -2,3- (5- tert-butyl-pyrazin) zinc porphyrin
Black-and-blue precipitating is precipitated in distilled water, filtering, filter cake 11.06g tetra- -2 obtained by drying after repeatedly being rinsed with distilled water, 3- (the tertiary fourth of 5-
Base pyrazine) zinc porphyrin, yield 80%.
Above-mentioned product is characterized, the ultraviolet-visible spectrogram of four -2,3- (5- tert-butyl-pyrazin) zinc porphyrin is obtained,
Referring to Fig. 3.From figure 3, it can be seen that occurring characteristic absorption band at two near 325nm and 645nm, meet porphyrin compound point
The requirement of B band and Q band is formed not at 250~350nm and at 600~700nm.Illustrate to have obtained four -2,3- through above-mentioned reaction
(5- tert-butyl-pyrazin) zinc porphyrin.
Through above-mentioned reaction it is found that synthesizing four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin, process by means of the present invention
Simple and easy to control, raw material type is few, and cheap, and synthesis cost is low, and intermediate product is nontoxic, reduces the mistake of post-processing
Journey, and through test it is found that the yield of product is 70% or more, yield is high.
Claims (9)
1. the method for synthesizing four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin, comprising the following steps:
With 3,3- dimethyl-2-butanone for raw material, oxidation reaction is carried out with selenium dioxide, and 3,3- diformazan is obtained to product rectification
Base -2- oxo butyraldehyde；
By 3,3- dimethyl -2- oxo butyraldehyde obtained in above-mentioned steps in 2,3- diamino -2- maleonitrile, urea and metal
It is heated under the conditions of chloride is existing, purification of products is obtained into four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin.
2. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 1, it is characterised in that:
The molar ratio of the selenium dioxide and 3,3- dimethyl-2-butanone is 1~1.5:1.
3. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 1, it is characterised in that:
The reflux temperature of the oxidation reaction is 50~80 DEG C；The time of the oxidation reaction is 4~5h.
4. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 1, it is characterised in that:
The rectification temperature is 112~115 DEG C.
5. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 1, it is characterised in that:
3,3- dimethyl -2- oxo the butyraldehyde: 2,3- diamino -2- maleonitrile: metal chloride: the molar ratio of urea is 1:1:
0.5~1:4~6.
6. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 1, it is characterised in that:
The heating process of the 3,3- dimethyl -2- oxo butyraldehyde, 2,3- diamino -2- maleonitrile, metal chloride and urea are as follows:
First heating temperature reaches 130~140 DEG C, is further continued for heating up after keeping 15~20min, and 2~3h is kept after reaching 190~220 DEG C
It is sufficiently reacted to raw material.
7. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 1, it is characterised in that:
The purification process includes repeatedly washing process and recrystallization process.
8. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 7, it is characterised in that:
The washing process repeatedly are as follows: first washed repeatedly repeatedly using distilled water, diluted acid or dilute alkaline soln, then with dehydrated alcohol or third
Ketone washs repeatedly colourless to filtrate repeatedly.
9. the method for synthesis four -2,3- (5- tert-butyl-pyrazin) metalloporphyrin according to claim 7, it is characterised in that:
The solvent that the recrystallization process uses is N,N-dimethylformamide, dimethyl sulfoxide or the concentrated sulfuric acid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002034844A1 (en) * | 2000-10-27 | 2002-05-02 | Avecia Limited | Composition containing an azaphthalocyanine and use |
| CN1974577A (en) * | 2006-12-13 | 2007-06-06 | 辽宁大学 | Process of synthesizing copper phthalocyanine in ionic liquid |
| CN101812064A (en) * | 2009-07-13 | 2010-08-25 | 黑龙江大学 | Method for preparing acetamido metal naphthalene phthalocyanine |
| CN104830320A (en) * | 2015-05-24 | 2015-08-12 | 吉林大学 | Phenanthreneopyrazine derivative luminescent material and application thereof in electroluminescent device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100983533B1 (en) * | 2008-11-24 | 2010-09-24 | (주)제이피에스 마이크로텍 | Method for synthesising tetraazaporphyrin using superhigh frequency wave |
-
2017
- 2017-03-13 CN CN201710145753.5A patent/CN106892927B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002034844A1 (en) * | 2000-10-27 | 2002-05-02 | Avecia Limited | Composition containing an azaphthalocyanine and use |
| CN1974577A (en) * | 2006-12-13 | 2007-06-06 | 辽宁大学 | Process of synthesizing copper phthalocyanine in ionic liquid |
| CN101812064A (en) * | 2009-07-13 | 2010-08-25 | 黑龙江大学 | Method for preparing acetamido metal naphthalene phthalocyanine |
| CN104830320A (en) * | 2015-05-24 | 2015-08-12 | 吉林大学 | Phenanthreneopyrazine derivative luminescent material and application thereof in electroluminescent device |
Non-Patent Citations (3)
| Title |
|---|
| Acyloins from t-Butylglyoxal;REYNOLD C. FUSON，等;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》;19390805;第61卷;第1937-1940页 |
| Substituted tetra-2,3-pyrazinoporphyrazines. Part I. Angular annelation of tetra-2,3-quinoxalinoporphyrazine;Svetlana V. Kudrevich，等;《Can. J. Chem.》;19961231;第74卷;第508-515页 |
| TETRA-2,3-(5-TERT-BUTYLPYRAZINO)PORPHYRAZINES;M. G. Gal’pern，等;《Chem. Heterocycl. Compd.》;19721231;第8卷;第780页，尤其参见第780页第1-2段 |
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