CN101570490A - Method for synthesizing copper-catalyzed substituted diphenylamine - Google Patents
Method for synthesizing copper-catalyzed substituted diphenylamine Download PDFInfo
- Publication number
- CN101570490A CN101570490A CNA2009100529777A CN200910052977A CN101570490A CN 101570490 A CN101570490 A CN 101570490A CN A2009100529777 A CNA2009100529777 A CN A2009100529777A CN 200910052977 A CN200910052977 A CN 200910052977A CN 101570490 A CN101570490 A CN 101570490A
- Authority
- CN
- China
- Prior art keywords
- alkali
- reaction
- formula
- compound shown
- add
- 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
Abstract
The invention relates to a method for preparing substituted diphenylamine. The preparation method mainly comprises the following steps: heating a compound shown in a formula II and a compound shown in a formula III in an organic solvent in the presence of a catalytic amount of copper compounds, a nitrogen-containing ligand, and alkali, generating a coupling reaction, and using an acid or alkali for a hydrolysis reaction to obtain a target compound shown in a formula I. Compared with the prior method for preparing the substituted diphenylamine, the preparation method has the advantages of low cost, mild reaction conditions, high yield and easy industrialized production.
Description
Technical field
The invention relates to the organic synthesis intermediate preparing substituted diphenylamine, belong to the technology of preparing of organic synthesis intermediate.
Technical background
Substituted diphenylamine is the synthetic essential raw material that replaces triphenylamine and derivative thereof, as important hole mobile material N, N, N ', N '-four (4-aminomethyl phenyl)-[1,1 '-biphenyl]-4,4 '-diamines is exactly by 4,4 '-dimethyl pentanoic and 4,4 '-diiodobiphenyl reaction synthetic.And for example, 2-methyl-4-methoxy diphenylamine is the intermediate of synthetic light, heat sensitive dye 3-diethylin-6-methyl-7-anilino alkane.
Have patent (US2098039) to mention, aniline is put into the reactor that aluminum oxide is housed by certain speed, reaction promptly obtains pentanoic under 450 ℃ high temperature.This method can only be synthesized symmetrical substituent pentanoic, and as 4,4 ' dimethyl pentanoic, and temperature of reaction height have ammonia to generate, and raw material can not transform fully, causes difficulty to separation.Other has document (Eur.J.Org.Chem.2007,6084-6088) report, with iodobenzene and aniline under cuprous iodide catalysis, N, N '-dimethyl-ethylenediamine are part, and potassiumphosphate is an alkali, dioxane is that solvent heats 21 hours syntehsizing diphenylamines of 100 ℃ of reactions in tube sealing, productive rate can reach 84%, and our above-mentioned reaction of reflux under normal pressure has only the trace product.
Also have document (Tetrahedron Lett.1998,39,2933-2936) report, with phenyl-boron dihydroxide and aniline in methylene dichloride or pyridine, add neutralized verdigris and triethylamine at normal temperatures stirring reaction just can generate pentanoic.Yet to use the more expensive phenyl-boron dihydroxide of excessive price in this reaction, and the neutralized verdigris of equivalent, this makes and is unfavorable for scale operation by the production cost height.
In recent years, be applied in synthesizing of substituted diphenylamine with the catalytic C-N coupling of palladium (Pd) (Hartwig-Buchwald) reaction.Document (Chem.Commun.2004,11,1294-1295) report, under the catalysis of palladium compound, parachlorotoluene and to monomethylaniline in tetrahydrofuran solution, be that alkali reaction just can generate 4 with the potassium tert.-butoxide, 4 '-dimethyl pentanoic.Though this method reaction temperature and productive rate height, but will be with a special palladium compound in the reaction, this compound costs an arm and a leg and is difficult to obtain, and to the water and air sensitivity, so operation should be carried out under the anhydrous and oxygen-free condition, this brings difficulty for the industrialization of product.
Summary of the invention
The objective of the invention is to, provide a kind of reaction conditions gentle, no coupling product, the productive rate height is easy to industrialized preparing substituted diphenylamine.
The said substituted diphenylamine of the present invention, it has structure shown in the formula I:
R among the formula I
1And R
2Be respectively o, m, p-CH
3O, m, p-OCH
3O, m, p-NH
2Or o, m, a kind of in the p-halogen.
The method of compound shown in the said preparation formula I of the present invention, its key step is: in the presence of catalytic amount copper compound and containing n-donor ligand and alkali, in organic solvent, by compound shown in the formula II and the heating of the compound shown in the formula III linked reaction takes place, being hydrolyzed to react with acid or alkali then makes target compound (compound shown in the formula I).
R in formula II and the formula III
1And R
2With mentioned above identical, R is MeO, EtO, Ph, H, or a kind of among the Me.
Wherein, described copper compound is: CuO, Cu
2O, CuI, CuCl, CuBr.What wherein, copper compound was preferable is: CuI, CuCl.
Wherein, described containing n-donor ligand is: 1, and 10-phenanthroline, 1,2-cyclohexanediamine, N, N '-dimethyl-ethylenediamine, N, N '-dibenzyl-ethylenediamin.
Wherein, described alkali is: KOH, NaOH, K
2CO
3, Na
2CO
3, K
3PO
4, t-BuOK, t-BuONa, NaH, NaNH
2, Cs
2CO
3What wherein, alkali was preferable is: t-BuOK, CsCO
3, K
3PO
4, K
2CO
3.
Wherein, described solvent is: dioxane, toluene, dimethylbenzene.
Wherein, described II: III: alkali: copper compound: the mol ratio of containing n-donor ligand is: 1: 1-1.2: 2-3: 0.05-0.10: 0.10-0.20.
Wherein, the temperature of described linked reaction is: 110 ℃-160 ℃.
Wherein, the acid of described hydrolysis reaction is: sulfuric acid, hydrochloric acid; Described alkali is: KOH, the NaOH aqueous solution.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: the present invention has optimized reaction conditions, makes reaction to carry out at a lower temperature, and no coupling product produces, and the reaction times is shorter, and cost is low, and solvent toxicity is less, and yield is higher, easily is applied to suitability for industrialized production.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Embodiment 14,4 '-dimethyl pentanoic synthetic
In the 100ml reaction flask, add N-(p-methylphenyl) ethanamide 2.98g (20.0mmol) successively, toluene 30ml, to toluene iodide 5.23g (24.0mmol), fully add 4.49g (40.0mmol) potassium tert.-butoxide after the stirring and dissolving, add 198mg (2.0mmol) cuprous chloride (CuCl) and 792mg (4.0mmol) 1 again, 10-phenanthroline (1,10-phenanthroline), be heated to 130 ℃ of stirring reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, after reclaiming toluene, residue is dissolved in the 20ml concentrated hydrochloric acid, and back flow reaction 2 hours is with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, anhydrous sodium sulfate drying.Reclaim solvent, get crude product.The ethanol/water recrystallization obtains product 4,4 '-dimethyl pentanoic 3.25g, yield: 82.5%.mp:79-80℃。
Synthesizing of embodiment 2 4-methyl-4 '-methoxy diphenylamines
In the 100ml reaction flask, add N-(p-methylphenyl) ethanamide 2.98g (20.0mmol) successively, dimethylbenzene 30ml, to methoxyl group iodobenzene 5.62g (24.0mmol), fully add 10.65g (40.0mmol) three hypophosphite monohydrate potassium after the stirring and dissolving, add 381mg (2.0mmol) cuprous iodide (CuI) and 456.8mg (4.0mmol) cyclohexanediamine again, be heated to 160 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, after reclaiming dimethylbenzene, residue is dissolved in the 20ml concentrated hydrochloric acid, after the back flow reaction 2 hours, with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, reclaim solvent behind the anhydrous sodium sulfate drying, get crude product.The ethanol/water recrystallization obtains product 4-methyl-4 '-methoxy diphenylamine 3.60g, yield: 84.4%.mp:82-84℃。
Synthesizing of embodiment 3 4-methyldiphenylamines
In the 100ml reaction flask, add N-(p-methylphenyl) ethanamide 2.98g (20.0mmol) successively, dimethylbenzene 30ml, iodobenzene 4.90g (24.0mmol), fully add 4.49g (40.0mmol) potassium tert.-butoxide after the stirring and dissolving, add 381mg (2.0mmol) cuprous iodide (CuI) and 961.2mg (4.0mmol) N again, N '-dibenzyl-ethylenediamin, be heated to 160 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaims dimethylbenzene, and residue is dissolved in the 20ml concentrated hydrochloric acid, after the back flow reaction 2 hours, with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4-methyldiphenylamine 2.75g behind the recrystallization, yield: 75.1%.mp:88-89℃。
Synthesizing of embodiment 4 4-bromine pentanoic
In the 100ml reaction flask, add N-(to bromophenyl) methane amide 4.0g (20.0mmol) successively, toluene 30ml, iodobenzene 4.90g (24.0mmol), fully add 10.65g (40.0mmol) three hypophosphite monohydrate potassium after the stirring and dissolving, add 381mg (2.0mmol) cuprous iodide (CuI) and 353mg (4.0mmol) N again, N '-dimethyl-ethylenediamine, be heated to 130 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaim toluene, residue is dissolved in the 20ml concentrated hydrochloric acid, back flow reaction is after 2 hours, with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, merge organic phase, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4-bromine pentanoic 3.85g behind the recrystallization, yield: 77.6%.mp:86-87℃。
Embodiment 54,4 '-dimethoxy pentanoic synthetic
In the 100ml reaction flask, add N-(p-methoxyphenyl) ethanamide 3.31g (20.0mmol) successively, toluene 30ml, to methoxyl group iodobenzene 5.62g (24.0mmol), fully add 13.03g (40.0mmol) cesium carbonate after the stirring and dissolving, add 198mg (2.0mmol) cuprous chloride (CuCl) and 792mg (4.0mmol) 1 again, 10-phenanthroline (1,10-phenanthroline), be heated to 130 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaims toluene, residue is dissolved in the 20ml concentrated hydrochloric acid, back flow reaction 2 hours, stopped reaction is with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4 behind the recrystallization, 4 '-dimethoxy pentanoic 3.90g, yield: 85.1%.mp:101-103℃。
Synthesizing of embodiment 6 4-methoxy diphenylamines
In the 100ml reaction flask, add N-(p-methoxyphenyl) ethanamide 3.31g (20.0mmol) successively, toluene 30ml, iodobenzene 4.90g (24.0mmol), fully add 10.65g (40.0mmol) three hypophosphite monohydrate potassium after the stirring and dissolving, add 381mg (2.0mmol) cuprous iodide (CuI) and 456.8mg (4.0mmol) cyclohexanediamine again, be heated to 130 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaim toluene, residue is dissolved in the 20ml ethanol, added 1.60g (40.0mmol) sodium hydroxide back flow reaction again 2 hours, stopped reaction is with nitric acid neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4-methoxy diphenylamine 3.35g behind the recrystallization, yield: 84.1%.mp:105-106℃。
Synthesizing of embodiment 7 4-methyl-4 '-methoxy diphenylamines
In the 100ml reaction flask, add p-methylphenyl carboxylamine formicester 3.30g (20.0mmol) successively, dimethylbenzene 30ml, to methoxyl group iodobenzene 5.62g (24.0mmol), fully add 10.65g (40.0mmol) three hypophosphite monohydrate potassium after the stirring and dissolving, add 380mg (2.0mmol) cuprous iodide (CuI) and 456.8mg (4.0mmol) cyclohexanediamine again, be heated to 160 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaim dimethylbenzene, residue is dissolved in the 20ml ethanol, add 1.6g (40.0mmol) sodium hydroxide, back flow reaction 2 hours is with sulfuric acid neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4-methyl-4 '-methoxy diphenylamine 3.10g behind the recrystallization, yield: 72.7%.mp:82-84℃。
Embodiment 84,4 '-dimethoxy pentanoic synthetic
In the 100ml reaction flask, add N-(p-methoxyphenyl) benzamide 4.55g (20.0mmol) successively, toluene 30ml, to methoxyl group iodobenzene 5.62g (24.0mmol), fully add 13.03g (40.0mmol) cesium carbonate after the stirring and dissolving, add 198mg (2.0mmol) cuprous chloride (CuCl) and 792mg (4.0mmol) 1 again, 10-phenanthroline (1,10-phenanthroline), be heated to 130 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaims toluene, and residue is dissolved in the 20ml25% sulfuric acid, back flow reaction 2 hours, with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4 behind the recrystallization, 4 '-dimethoxy pentanoic 3.20g, yield: 69.8%.mp:101-103℃。
Embodiment 94,4 '-dimethyl pentanoic synthetic
In the 100ml reaction flask, add p-methylphenyl urethane fat 3.58g (20.0mmol) successively, toluene 30ml, to toluene iodide 5.23g (24.0mmol), fully add 4.49g (40.0mmol) potassium tert.-butoxide after the stirring and dissolving, add 198mg (2.0mmol) cuprous chloride (CuCl) and 792mg (4.0mmol) 1 again, 10-phenanthroline (1,10-phenanthroline), be heated to 130 ℃ of stirring and refluxing reactions 10 hours, reduce to room temperature, water (30ml * 3) is washed reaction solution to neutral, reclaims toluene, and residue is dissolved in the 20ml concentrated hydrochloric acid, back flow reaction 2 hours, with NaOH neutralization reaction liquid, use ethyl acetate (15mL * 3) extraction then, behind the anhydrous sodium sulfate drying, reclaim solvent, get crude product.Obtain product 4 behind the recrystallization, 4 '-dimethyl pentanoic 2.90g, yield: 73.6%.mp:79-80℃。
Claims (10)
1. the method for compound shown in the preparation formula I, it is characterized in that, said preparation method's key step is: in the presence of catalytic amount copper compound and containing n-donor ligand and alkali, in organic solvent, by compound shown in the formula II and the heating of the compound shown in the formula III linked reaction takes place, being hydrolyzed to react with acid or alkali then makes target compound.
R in the formula
1And R
2Be respectively o, m, p-CH
3O, m, p-OCH
3O, m, p-NH
2Or o, m, a kind of in the p-halogen; R is MeO, EtO, Ph, H, or a kind of among the Me.
2. the method for claim 1, it is characterized in that: described copper compound is: CuO, Cu
2O, CuI, CuCl, CuBr.
3. method as claimed in claim 2 is characterized in that: described copper compound is: CuI, CuCl.
4. the method for claim 1, it is characterized in that: described containing n-donor ligand is: 1,10-phenanthroline, 1,2-cyclohexanediamine, N, N '-dimethyl-ethylenediamine, N, N '-dibenzyl-ethylenediamin.
5. the method for claim 1, it is characterized in that: described alkali is: KOH, NaOH, K
2CO
3, Na
2CO
3, K
3PO
4, t-BuOK, t-BuONa, NaH, NaNH
2, Cs
2CO
3
6. method as claimed in claim 5 is characterized in that: described alkali is: KOH, K
3PO
4, t-BuOK, Cs
2CO
3
7. the method for claim 1, it is characterized in that: described solvent is: dioxane, toluene, dimethylbenzene.
8. the method for claim 1, it is characterized in that: described II: III: alkali: copper compound: the mol ratio of containing n-donor ligand is: 1: 1-1.2: 2-3: 0.05-0.10: 0.10-0.20.
9. the method for claim 1, it is characterized in that: the temperature of described linked reaction is: 110 ℃-160 ℃.
10. the method for claim 1, it is characterized in that: the acid of described hydrolysis reaction is: sulfuric acid, hydrochloric acid; Described alkali is: the aqueous solution of KOH, NaOH.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2009100529777A CN101570490A (en) | 2009-06-12 | 2009-06-12 | Method for synthesizing copper-catalyzed substituted diphenylamine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2009100529777A CN101570490A (en) | 2009-06-12 | 2009-06-12 | Method for synthesizing copper-catalyzed substituted diphenylamine |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101570490A true CN101570490A (en) | 2009-11-04 |
Family
ID=41229989
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2009100529777A Pending CN101570490A (en) | 2009-06-12 | 2009-06-12 | Method for synthesizing copper-catalyzed substituted diphenylamine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101570490A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102258979A (en) * | 2011-05-23 | 2011-11-30 | 扬州三友合成化工有限公司 | Porous crystalline material and preparation method and use thereof |
CN102701964A (en) * | 2012-05-09 | 2012-10-03 | 江西师范大学 | Method for synthesizing 4,4'-diphenic acid |
CN102850156A (en) * | 2012-10-11 | 2013-01-02 | 南京师范大学 | Method for synthesizing o-amino diaryl ether and o-amino diaryl sulfur ether |
CN102976966A (en) * | 2012-11-27 | 2013-03-20 | 浙江大学 | Synthetic method for high-steric-hindrance tertiary amides |
CN106362797A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院上海有机化学研究所 | Oxalic acid amide ligands, and use thereof in copper catalyzed aryl halide coupling reaction |
CN107827761A (en) * | 2017-11-07 | 2018-03-23 | 宿迁德威化工有限公司 | A kind of preparation method of organic aromatic amine compound |
CN111302952A (en) * | 2020-04-03 | 2020-06-19 | 郑州原理生物科技有限公司 | Refining method of 4-methyldiphenylamine |
CN114213256A (en) * | 2021-12-27 | 2022-03-22 | 苏州久显新材料有限公司 | Preparation method of di (4-biphenyl) amine |
CN115536536A (en) * | 2022-09-23 | 2022-12-30 | 常州大学 | Preparation method of m-dialkylaminophenol |
-
2009
- 2009-06-12 CN CNA2009100529777A patent/CN101570490A/en active Pending
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102258979A (en) * | 2011-05-23 | 2011-11-30 | 扬州三友合成化工有限公司 | Porous crystalline material and preparation method and use thereof |
CN102701964A (en) * | 2012-05-09 | 2012-10-03 | 江西师范大学 | Method for synthesizing 4,4'-diphenic acid |
CN102701964B (en) * | 2012-05-09 | 2014-01-01 | 江西师范大学 | Method for synthesizing 4,4'-diphenic acid |
CN102850156B (en) * | 2012-10-11 | 2015-12-16 | 南京师范大学 | A kind of method of synthesizing adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour |
CN102850156A (en) * | 2012-10-11 | 2013-01-02 | 南京师范大学 | Method for synthesizing o-amino diaryl ether and o-amino diaryl sulfur ether |
CN102976966A (en) * | 2012-11-27 | 2013-03-20 | 浙江大学 | Synthetic method for high-steric-hindrance tertiary amides |
CN102976966B (en) * | 2012-11-27 | 2015-01-28 | 浙江大学 | Synthetic method for high-steric-hindrance tertiary amides |
CN106362797A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院上海有机化学研究所 | Oxalic acid amide ligands, and use thereof in copper catalyzed aryl halide coupling reaction |
CN106362797B (en) * | 2015-07-20 | 2021-05-28 | 浙江中科创越药业有限公司 | Oxalic acid amide ligand and application thereof in copper-catalyzed aryl halide coupling reaction |
CN107827761A (en) * | 2017-11-07 | 2018-03-23 | 宿迁德威化工有限公司 | A kind of preparation method of organic aromatic amine compound |
CN111302952A (en) * | 2020-04-03 | 2020-06-19 | 郑州原理生物科技有限公司 | Refining method of 4-methyldiphenylamine |
CN111302952B (en) * | 2020-04-03 | 2023-06-20 | 郑州原理生物科技有限公司 | Refining method of 4-methyl diphenylamine |
CN114213256A (en) * | 2021-12-27 | 2022-03-22 | 苏州久显新材料有限公司 | Preparation method of di (4-biphenyl) amine |
CN115536536A (en) * | 2022-09-23 | 2022-12-30 | 常州大学 | Preparation method of m-dialkylaminophenol |
CN115536536B (en) * | 2022-09-23 | 2023-12-12 | 常州大学 | Preparation method of m-dialkylaminophenol |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101570490A (en) | Method for synthesizing copper-catalyzed substituted diphenylamine | |
JP2018522724A (en) | Oxalamide ligands and their use in copper-catalyzed aryl halide coupling reactions | |
CN108774189B (en) | Oxazine phenyl ether derivative and preparation method thereof | |
CN104016968A (en) | N1 substituted 1,2,3-triazole derivative for ligand of Cu(I) as well as preparation method and application of N1 substituted 1,2,3-triazole derivative | |
CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
CN101864003A (en) | Synthesis method of 6-deoxy thioether amino acid cyclodextrin derivative | |
CN108610278A (en) | A kind of synthetic method of 6- amino -5- acyl groups benzo [a] carbazole compound | |
CN111440207B (en) | Cuprous complex, preparation method thereof and application thereof in synthesis of 3-indolyl thioether | |
CN104447336B (en) | A kind of three dish ene derivatives and preparation method thereof | |
CN102249946B (en) | Preparation method of N-alkyloxy oxalyl alanine alkyl ester | |
CN101113138A (en) | Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex | |
CN102050782A (en) | Preparation method of spirofluorene acridine intermediate | |
CN105175373A (en) | Synthetic method of aryl ketone coumarin derivative | |
CN102144046A (en) | 2-benzyl-4-(3,4-dichlorophenyl)-5-methylimidazole compound | |
CN104774172B (en) | Method for synthesizing 3-cyanoindole compound | |
CN103992241B (en) | The preparation method of N-substituted-phenyl glycine | |
CN115385903A (en) | Preparation method of cyano-substituted benzoxazine-4-one derivative | |
CN109485550B (en) | Method for preparing styrene derivative by using ionic liquid | |
CN112174926B (en) | Preparation method of TADF material intermediate 4, 7-dibromo xanthone | |
CN109232380A (en) | A kind of synthetic method of 4- bromine carbazole | |
CN111892469B (en) | Aryl hydrazine and S 8 Method for synthesizing symmetrical disulfide compound by using raw material | |
CN111303117B (en) | Preparation method of nitrogen heterocyclic ring substituted indole thioether compound | |
CN101397291B (en) | Method for preparing 2-cyanoacet-5-substituted thiophenes compound | |
CN103387542B (en) | The preparation method of substituted pyrazolecarboxylic ether compound | |
KR101692593B1 (en) | Catalytic preparation of enamides from alkyl azides and acyl donors |
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: 20091104 |