CN102050782A - Preparation method of spirofluorene acridine intermediate - Google Patents
Preparation method of spirofluorene acridine intermediate Download PDFInfo
- Publication number
- CN102050782A CN102050782A CN 201010595132 CN201010595132A CN102050782A CN 102050782 A CN102050782 A CN 102050782A CN 201010595132 CN201010595132 CN 201010595132 CN 201010595132 A CN201010595132 A CN 201010595132A CN 102050782 A CN102050782 A CN 102050782A
- Authority
- CN
- China
- Prior art keywords
- acridine
- spiral shell
- fluorenes
- arylamine
- preparation
- 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.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
The invention relates to a preparation method of a spirofluorene acridine intermediate, relating to the fine organic synthesis field and the photoelectric material application field. The spirofluorene acridine material with the structure shown as below is used as an important organic intermediate in the new fields such as the organic electroluminescence, the photovoltaic cell, the organic electrical storage, the organic nonlinear optics and the organic laser. The invention relates to a novel preparation method of spirofluorene acridine monomer, in particular to a two-step tandem reaction adopting the one pot method. The preparation method comprises the following steps: heating arylamine, arylamine hydrochloride and fluorenone or a derivative of fluorenone to fully react and generate open-loop 9,9'-diaryl intermediate product; and (2) adding polyphosphoric acid and arylamine in the reaction tank to close the loop, alkalifying, stirring, filtering, and washing to obtain the high purity product. The preparation method of the spirofluorene acridine intermediate has the following characteristics: (1) the one pot method is adopted for the tandem preparation process, the middle separation step is not required, the raw materials are cheap and accessible, the yield is high, the product is easy to separate and purify; and (2) the method has mass production value and is environmental friendly.
Description
Technical field
The present invention is specifically related to the one-pot preparation thereof of spiral shell fluorenes acridine, and relates to step and raw material that these materials adopt in preparation process.
Technical background
From Tang research group of Kodak [Tang, C. W. in 1987; Van Slyke, S. A.
Appl. Phys. Lett.1987,
51, 913.] delivered with organic fluorescence materials make film-type organic electroluminescence device (Organic Light-emitting Diodes) and since, organic flat pannel display becomes the demonstration product of the another generation marketization after liquid-crystal display.Meanwhile other organic electronics and photoelectronic industry comprise that field such as organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing and laser and nonlinear optical material are also just moving towards the marketization.Organic and the advantage plastic electronic product is that the material preparation cost is low, technology simple, has the snappiness and the plasticity-of commodity polymer.Therefore, develop the novel organic photoelectric information material of market potential and attracted the scientist of the different subjects of many domestic and international universities and the concern and the input of research institution and company with practicality.Up to the present, high stability carrier transmission material of development of new and luminescent material become and improve organic electronic, electric light and photoelectric device efficient and life-span key factor.
Up to the present, spiral shell two fluorenes and spiral shell fluorenes xanthene structural motif make up photoelectric material as nuclear and show high thermostability and high second-order transition temperature, therefore become a class practical organic optoelectronic material likely, have formed suitable article and patent.Yet spiral shell fluorenes acridine is a kind of photoelectric material intermediate of novelty, yet there are no report, and its one kettle way series connection synthesis preparation method also has theory innovation and puts into practice dissemination on a large scale simultaneously.In fact spiral shell fluorenes acridine has spiral shell two fluorenes confers similar advantages, and high carrier mobility, is expected to become the characteristic organic photoelectric functional material that can substitute spiral shell two fluorenes, is applied to electroluminescent, field-effect transistor and organic solar batteries association area.Therefore, the present invention discusses by a series of intermediary material based on spiral shell fluorenes acridine of the nonmetal catalysis cascade reaction exploitation of simple one kettle way, has wide practical use in electronics or photoelectric material.
At present, fragrant spiral shell fluorenes class material is mainly by traditional adjacent halogen diaryl method, diaryl fluorene method, diaryl ketone method, and pairs of anion method and the one kettle way series process that receives publicity gradually recently are synthetic.Use right 4 desired aromatic ketones and right 5 desired arylaminess to obtain spiral shell fluorenes acridine intermediate polyphosphoric acid catalyzed the reaction down, wherein the method for design of one kettle way preparation feedback is from following document:
Xie,?L.?H.;?Liu,?F.;?Tang,?C.;?Hou,?X.?Y.;?Hua,?Y.?R.;?Fan,?Q.?L.;?Huang,?W.,?
Org.?Lett.,?2006,?
8,?2787-2790.?Liu,?F.;?Xie,?L.?H.;?Tang,?C.;?Liang,?J.;?Chen,?Q.?Q.;?Peng,?B.;?Wei,?W.;?Cao,?Y.;?Huang,?W.,?
Org.?Lett.,?2009,?
11,?3850-3853.
Summary of the invention
Technical problem:In order to overcome prior art, propose a kind of arylamine cheap and easy to get, arylamin hydrochloric acid salt, aromatic ketone of utilizing and obtain spiral shell fluorenes acridine intermediates preparation by a step cascade reaction simple to operation for direct material in the deficiency that realizes that the technical grade preparation is produced.This method overcome traditional adjacent halogen diaryl three one-step preparing methods adjacent halogen aryl reagent raw material costliness, the preparation loaded down with trivial details, the intermediate fragrance tertiary alcohol separates technical problems such as purification complexity, resulting intermediate product and spiral shell fluorenes acridine intermediate are all broad-spectrum important organic intermediate in the organic functional material, whole reaction system is simple, process is simple and direct, raw material is cheap and easy to get, and the productive rate height has environment friendly.
Technical scheme:Spiral shell fluorenes acridine intermediate preparation method of the present invention is included under the solid-state catalytic reaction condition, arylamine, arylamin hydrochloric acid salt and Fluorenone or derivatives thereof are mixed in 180 ℃ of reactions 7 hours, need not intermediate section from purification, after adding excessive polyphosphoric acid, continue reaction 20 hours, through alkalization, wash, extract, revolve boil off desolventize and column chromatography purification after obtain highly purified spiral shell fluorenes acridine intermediate, have following structure:
In the formula: R
1, R
2Identical or different, be hydrogen atom, halogen atom, phenyl, halogenophenyl, biphenyl group, fluorenyl, pentanoic, spiral shell two fluorenes, spiral shell fluorenes xanthene.
In the formula: Ar
1, Ar
2For phenyl, ortho para bromine substituted-phenyl, α, betanaphthyl or 1-to phenyl-naphthalene.Corresponding raw material arylamine is the following stated structure:
Described catalysis acid is polyphosphoric acid, and temperature of reaction is between 180-200 degree centigrade.
The amount of substance of described arylamin hydrochloric acid salt is a 3-8 times of equivalent of corresponding described arylamine, and the arylamine of arylamine and corresponding arylamin hydrochloric acid salt is the following stated structure:
Described Fluorenone or derivatives thereof has following structure:
In the formula: R
1, R
2Identical or different, be hydrogen atom, halogen atom, phenyl, halogenophenyl, biphenyl group, fluorenyl, pentanoic, spiral shell two fluorenes, spiral shell fluorenes xanthene.The Fluorenone or derivatives thereof is preferably as follows structure:
When arylamine and arylamin hydrochloric acid salt during at high temperature still for solid the reaction solvent for use be the analytical pure dichlorobenzene.
With
14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes] is an example,Reaction concrete steps (1) reaction conditions specifically is in reactor, add ketone, and with the ketone mol ratio be that the 1-arylamin hydrochloric acid salt of 1-arylamine, 1:4 of 1:1 is as catalyzer, then under the anhydrous and oxygen-free condition, heated and stirred, 120-200 ℃ of reaction are after 6 hours, and adding is the polyphosphoric acid of 1:10 with the ketone mol ratio in reaction system, keep temperature of reaction 120-200 ° C, the reaction times is 20 hours.Subsequently, with 5% aqueous sodium hydroxide solution cancellation reaction, dichloromethane extraction, dry vacuum rotary steam, obtain further purification of crude product and obtain corresponding spiral shell fluorenes acridine compound by the silicagel column separation.
Described spiral shell fluorenes acridine intermediate is preferably as follows structure:
The present invention is in conjunction with one kettle way series connection cyclization prepared in reaction, has characteristics such as raw material is easy to get, simple to operation, mild condition, environmental friendliness, obtains having in organic electronic plastics field the spiral shell fluorenes acridine intermediate of widespread use.
Beneficial effect:The present invention discusses the one kettle way cascade reaction by the Fluorenone or derivatives thereof of easy, high yield, can effectively reduce the production cost of spiral shell fluorenes acridine intermediate, thereby promote its broader applications in organic printing electronic industry and photoelectric functional material field.
Description of drawings
Fig. 1. 10-hydrogen-spiral shell [fluorenes-9,9'-acridine]: GCMS figure;
Fig. 2. 14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes]: GCMS figure;
Fig. 3. 14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes]:
1H NMR figure;
Fig. 4. 2 '-bromo-14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes]: GC-MS figure;
Fig. 5. 2 '-bromo-14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes]:
1H NMR figure;
Fig. 6. 2 ', 7 '-two bromo-14-hydrogen-spiral shells [dibenzo [c, h] acridine-7,9 '-fluorenes]: GC-MS figure;
Fig. 7. 2 ', 7 '-two bromo-14-hydrogen-spiral shells [dibenzo [c, h] acridine-7,9 '-fluorenes]:
1H NMR figure.
Embodiment
Further describe technical scheme of the present invention below in conjunction with embodiment, but these embodiment and unrestricted embodiments of the present invention.The present invention has multiple different embodiment, has more than to be limited to content described in this specification sheets.Those skilled in the art is under the situation of the present application spirit, and the scheme of being finished should be within the scope of the invention.
At first with arylamine, arylamin hydrochloric acid salt and Fluorenone or derivatives thereof at 120-200
oReaction is 3-8 hour under the C condition, removes pigment through alkalization, stirring, filtration, washing with alcohol, obtain purity high 9,9-diaryl-amine fluorenes intermediate product; Join again in methylene dichloride or the trichloromethane and under refluxad reacted 0.5-1 hour with alkyl nitrite, revolve and desolvate, remove by filter precipitation, water and the extraction of methylene dichloride system, pickling, alkali cleaning are respectively once collected organic phase, sherwood oil and methylene dichloride mixed solvent system recrystallization can obtain the high target intermediate of purity; After the alkalization rear filtrate adds the technical pure concentrated hydrochloric acid, leaves standstill some hrs, filter and obtain arylamin hydrochloric acid salt, reclaimed arylamine, have the atom economy benefit.
Embodiment 1:10-hydrogen-spiral shell [fluorenes-9,9'-acridine] is synthetic
Get two mouthfuls of flasks of an exsiccant 100 mL, add Fluorenone (0.5031 g, 2.79 mmol, 1 equiv), aniline (2.20 mL, 24.1 mmol, 8.64 equiv), anilinechloride (1.11 g, 14.3 mmol, 5.16 equiv), under the anhydrous and oxygen-free condition, be heated to 184 ℃ of reactions after 5 hours, add polyphosphoric acid (PPA) (3 mL), continue reaction 20 hours, after reaction end and the cooling, with suitable quantity of water cancellation reaction, CH
2Cl
2Extraction merges organic phase, drying, and vacuum rotary steam, obtain crude product with sherwood oil: methylene dichloride 5:1 is that eluent carries out column chromatography purification, obtains yellow powder solid 0.030 g, productive rate: 2 %.GC-MS?(EI-
m/z):331/?(M
+)
Synthesizing of embodiment 2:14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes]
Get two mouthfuls of flasks of an exsiccant 250 mL, add Fluorenone (5.024 g, 27.9 mmol, 1 equiv), naphthalidine (3.947 g, 27.6 mmol, 1 equiv), naphthalidine hydrochloride (16.89 g, 94 mmol, 3.37 equiv) is under the anhydrous and oxygen-free condition, heated and stirred, 180 ℃ of reactions added polyphosphoric acid after 6 hours in reaction system, continue reaction 20 hours.After reaction finished, cooling reaction, stirring added 5% aqueous sodium hydroxide solution and methylene dichloride, extraction down, dry vacuum rotary steam, obtain crude product with sherwood oil: methylene dichloride 5:1 column chromatography purification obtains being pale yellow powder 3.6g, yield is 30%, and purity is greater than 99%, and fusing point is higher than 300 ℃.
GC-MS?(EI-m/z):?431?(M
+).?
1H?NMR?(400?MHz,?CDCl
3):?
δ8.18-8.16?(d,?
J?=?8?Hz,?2H),?7.87-7.85?(d,?
J?=?8?Hz,?2H),?7.76-7.74?(d,?
J?=?8?Hz,?2H),?7.71?(s,?1H),?7.67-7.64?(t,
?J?=?7.6?Hz,?2H),?7.53-7.49?(t,
?J?=?7.2?Hz,?2H),?7.40-7.36?(t,?
J?=?7.6?Hz,
1H),?7.26-7.25?(d,?
J?=?8?Hz,?2H),?7.21-7.17?(t,?
J?=?7.6?Hz,?2H),?7.12-7.10?(d,?
J?=?7.6?Hz,?2H),?6.40-6.37?(d,?
J?=?8.8?Hz,?2H).?
13C?NMR?(100?MHz,?CDCl
3):?
δ157.83,?—5—
139.25,?133.22,?132.47,?128.90,?128.41,?127.67,?126.58,?126.55,?125.89,?125.83,?122.38,?120.96,?119.81,?119.02,?118.19,?57.16.?Anal.?Calcd.?for?C
33H
21N:?C,?91.85;?H,?4.91;?N,?3.25;?Found:?C,?91.65;?H,?5.16.
Embodiment 3:2's '-bromo-14-hydrogen-spiral shell [dibenzo [c, h] acridine-7,9 '-fluorenes] is synthetic
Get two mouthfuls of flasks of an exsiccant 250 mL, add 2-bromine Fluorenone (5.0 g, 19.3 mmol, 1 equiv), naphthalidine (2.75 g, 19.23 mmol, 1 equiv), naphthalidine hydrochloride (13.75 g, 76.8 mmol, 4 equiv) is under the anhydrous and oxygen-free condition, heated and stirred, 180 ℃ of reactions added polyphosphoric acid after 7 hours in reaction system, continue reaction 20 hours.After reaction finished, cooling reaction, stirring added 5% aqueous sodium hydroxide solution and methylene dichloride, extraction down, dry vacuum rotary steam, obtain crude product with sherwood oil: methylene dichloride 7:1 column chromatography purification obtains pale yellow powder 1.62g, yield is 18%, and purity is greater than 99%, and fusing point is higher than 300 ℃.
MALDI-TOF-MS?(MALDI-
m/z):?509/?(M
+);?
1HNMR?(400?MHz,?CDCl
3,?ppm):?
δ?8.19-8.17?(d,?
J?=?8.4?Hz,?1H),?7.84-7.82?(d,?
J?=?7.6?Hz,?1H),?7.78-7.76?(d,?
J?=?8?Hz,?2H),?7.74-7.70?(t,?
J?=?8.4?Hz,?2H),?7.70-7.65?(t,?
J?=?7.2?Hz,?2H),?7.55-7.51?(t,?
J?=?7.6?Hz,?2H),?7.50-7.48?(d,?
J?=?8?Hz,?1H),?7.42-7.39?(t,?
J?=?7.6?Hz,?1H),?7.37?(s,?1H),?7.26?(CDCl
3?peak),?7.25?(s,?1H),?7.25-7.21?(t,?
J?=?7.6?Hz,?1H),?7.15-7.13?(d,?
J?=?8.8?Hz,?2H),?
13C?NMR?(100?MHz,?CDCl
3,?ppm):?
δ?159.58,?157.42,?138.41,?138.03,?133.30,?132.47,?131.00,?129.82,?128.93,?127.92,?126.68,?126.31,?126.11,?126.00,?122.38,?121.98,?121.27,?121.13,?119.88,?119.06,?117.29,?57.30.
Embodiment 4:2 ', 7 '-two bromo-14-hydrogen-spiral shells [dibenzo [c, h] acridine-7,9 '-fluorenes] synthetic
Get two mouthfuls of flasks of an exsiccant 250 mL, add 2,7-bromine two Fluorenones (5.0 g, 14.7 mmol, 1 equiv), naphthalidine (2.10 g, 14.7 mmol, 1 equiv), naphthalidine hydrochloride (10.53 g, 58.8 mmol, 4 equiv) under the anhydrous and oxygen-free condition, heated and stirred, 180 ℃ of reactions are after 7 hours, add polyphosphoric acid in reaction system, 180 ℃ are continued reaction 20 hours.After reaction finishes, the cooling reaction, stir and add 5% aqueous sodium hydroxide solution and methylene dichloride down, extraction, dry vacuum rotary steam obtains crude product with sherwood oil: methylene dichloride 7:1 column chromatography purification, obtain yellow powder 1.22 g with the methylene dichloride recrystallization, yield is 14%, and purity is greater than 99%, and fusing point is higher than 300 ℃.
MALDI-TOF-MS?(MAlDI-
m/z):?589/?(M
+);?
1HNMR?(400?MHz,?CDCl
3,?ppm):
δ?8.19-8.17?(d,?
J?=?8.4?Hz,?2H),?7.80-7.60?(d,?
J?=?8?Hz,?2H),?7.76?(s,?1H),?7.70-7.67?(t,?2H),?7.70-7.68?(d,?
J?=?8?Hz,?2H),?7.57-7.53?(t,?2H),?7.52-7.50?(dd,?
J?=?8?Hz,?2H),?7.35
(sd,?
J?=?1.6?Hz,?2H),?7.17-7.15?(d,?
J?=?8.6?Hz,?2H),?6.36-6.34?(d,?
J?=?8.6?Hz,?2H).?
13C?NMR?(100?MHz,?CDCl
3,?ppm):?
δ?159.20,?137.17,?133.37,?132.46,?131.26,?129.93,?128.97,?126.33,?126.16,?126.10,?122.51,?122.37,?121.33,?119.09,?116.40,?57.41。
Claims (6)
1. spiral shell fluorenes acridine intermediates preparation, it is characterized in that arylamine, arylamin hydrochloric acid salt and Fluorenone or derivatives thereof are mixed in 120-220 ℃ of reaction 5-24 hour, need not intermediate section from purification, adding acid back continuation reaction 10-30 hour, obtain highly purified spiral shell fluorenes acridine intermediate, it is as follows to have a reaction expression:
In the formula: R
1, R
2Identical or different, be hydrogen atom, halogen atom, phenyl, halogenophenyl, biphenyl group, fluorenyl, pentanoic, spiral shell two fluorenes or spiral shell fluorenes xanthene;
In the formula: Ar
1, Ar
2For phenyl, ortho para bromine substituted-phenyl, α, betanaphthyl or 1-to phenyl-naphthalene; Corresponding raw material arylamine is the following stated structure:
2. spiral shell fluorenes acridine intermediates preparation as claimed in claim 1 is characterized in that described spiral shell fluorenes acridine intermediate has following structure:
3. a spiral shell fluorenes acridine intermediates preparation as claimed in claim 1 is characterized in that described acid is poly phosphorus.
4. spiral shell fluorenes acridine intermediates preparation as claimed in claim 1 is characterized in that described Fluorenone or derivatives thereof has following structure:
In the formula: R
1, R
2Identical or different, be hydrogen atom, halogen atom, phenyl, halogenophenyl, biphenyl group, fluorenyl, pentanoic, spiral shell two fluorenes or spiral shell fluorenes xanthene.
5. spiral shell fluorenes acridine intermediates preparation as claimed in claim 4 is characterized in that described Fluorenone or derivatives thereof is preferably as follows structure:
6. spiral shell fluorenes acridine intermediates preparation as claimed in claim 1, the amount of substance that it is characterized in that described arylamin hydrochloric acid salt is a 4-6 times of equivalent of corresponding described arylamine, the arylamine of arylamine and corresponding arylamin hydrochloric acid salt is the following stated structure:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010595132 CN102050782A (en) | 2010-12-20 | 2010-12-20 | Preparation method of spirofluorene acridine intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010595132 CN102050782A (en) | 2010-12-20 | 2010-12-20 | Preparation method of spirofluorene acridine intermediate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102050782A true CN102050782A (en) | 2011-05-11 |
Family
ID=43955632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010595132 Pending CN102050782A (en) | 2010-12-20 | 2010-12-20 | Preparation method of spirofluorene acridine intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102050782A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417458A (en) * | 2011-08-31 | 2012-04-18 | 常州市阳光药业有限公司 | Preparation method of 9,9-bis(4-aminophenyl)fluorene |
| CN109485605A (en) * | 2019-01-23 | 2019-03-19 | 石河子大学 | A kind of preparation method of 10H- spiral shell [acridine -9,9`- fluorenes] and its derivative |
| CN105924450B (en) * | 2016-05-03 | 2020-05-15 | 南京邮电大学 | Synthesis method of azafluorene spiro-aromatic hydrocarbon |
| CN113121442A (en) * | 2021-03-22 | 2021-07-16 | 深圳大学 | Synthesis method and application of spiro-substituted acridine compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006033564A1 (en) * | 2004-09-24 | 2006-03-30 | Lg Chem. Ltd. | New compound and organic light emitting device using the same(10) |
-
2010
- 2010-12-20 CN CN 201010595132 patent/CN102050782A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006033564A1 (en) * | 2004-09-24 | 2006-03-30 | Lg Chem. Ltd. | New compound and organic light emitting device using the same(10) |
Non-Patent Citations (1)
| Title |
|---|
| 《Chemische Berichte》 19841231 Tritschler, Wolfgang et al Synthesis and conformation of spiroacridans 2703-13 1－6 , 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417458A (en) * | 2011-08-31 | 2012-04-18 | 常州市阳光药业有限公司 | Preparation method of 9,9-bis(4-aminophenyl)fluorene |
| CN105924450B (en) * | 2016-05-03 | 2020-05-15 | 南京邮电大学 | Synthesis method of azafluorene spiro-aromatic hydrocarbon |
| CN109485605A (en) * | 2019-01-23 | 2019-03-19 | 石河子大学 | A kind of preparation method of 10H- spiral shell [acridine -9,9`- fluorenes] and its derivative |
| CN113121442A (en) * | 2021-03-22 | 2021-07-16 | 深圳大学 | Synthesis method and application of spiro-substituted acridine compound |
| CN113121442B (en) * | 2021-03-22 | 2022-12-16 | 深圳大学 | Synthesis method and application of spiro-substituted acridine compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2012118164A1 (en) | Novel compound, charge transport material, and organic device | |
| WO2009096202A1 (en) | Halogenated polycyclic aromatic compound and method for producing the same | |
| Talele et al. | Expeditious synthesis of helicenes using an improved protocol of photocyclodehydrogenation of stilbenes | |
| CN102627522B (en) | Synthesis method of indenofluorene derivatives, isotruxene and mono-substituted isotruxene derivatives | |
| CN101643381A (en) | Diarylfluorene intermediate preparation method | |
| CN103224436B (en) | The preparation method of the amino diaryl ketone compound of a kind of neighbour | |
| CN102050782A (en) | Preparation method of spirofluorene acridine intermediate | |
| CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
| WO2019138332A1 (en) | Process for the preparation of disubstituted diaryloxybenzoheterodiazole compounds | |
| CN113372293A (en) | Preparation method of 2-phenylbenzothiazole derivative | |
| CN109503547B (en) | Process for preparing benzodithiolane derivatives | |
| CN111825645A (en) | Naphtho-coumarin compound, preparation method and application of naphthocoumarin compound as photoluminescence material | |
| CN108440417B (en) | 1- methyl thio phenyl benzimidazole and its derivative synthesizing process | |
| CN101429131B (en) | Synthesis of N,N-di(4-methyl phenyl)-4-(2, 2-diphenylethyllene)aniline | |
| CN102775279A (en) | 2,7-dibromo-9-hydroxyl phenanthrene derivatives and preparation method thereof | |
| CN103113174B (en) | Preparation method of phenolic compounds | |
| JP5114901B2 (en) | Method for producing nitrogen-containing polycyclic heterocyclic compound | |
| CN105237379B (en) | Production method for 4-bromo fluorenone | |
| CN100554235C (en) | Preparation method to alkoxyl mandelic acid | |
| CN111362986B (en) | Thieno [2,3-d ] pyridazine cyclometalated iridium complex and preparation method thereof | |
| CN107814757A (en) | A kind of method for synthesizing polysubstituted pyrrole derivative | |
| CN110746462A (en) | Efficient synthesis method of dendritic cyclotriphosphazene compound | |
| CN101219967A (en) | Process for producing 2-nitryl substituted benzene ethane nitrile compounds | |
| JP5505450B2 (en) | Method for producing nitrogen-containing polycyclic heterocyclic compound | |
| CN108623593A (en) | One kind being based on acid imide C3Symmetrical spiral shell slurry alkane and its synthesis and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110511 |