CN106946800A - A kind of synthetic method of (1H, the 3H) diketone of quinazoline 2,4 and its derivative - Google Patents
A kind of synthetic method of (1H, the 3H) diketone of quinazoline 2,4 and its derivative Download PDFInfo
- Publication number
- CN106946800A CN106946800A CN201710169548.2A CN201710169548A CN106946800A CN 106946800 A CN106946800 A CN 106946800A CN 201710169548 A CN201710169548 A CN 201710169548A CN 106946800 A CN106946800 A CN 106946800A
- Authority
- CN
- China
- Prior art keywords
- amino
- quinazoline
- diketone
- reaction
- carbon dioxide
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a kind of quinazoline 2,4 (1H, 3H) the synthetic method of diketone and its derivative, be characterized in using o-amino benzonitride or 4, No. 5 substituted derivatives in positions be substrate with the diethanol amine aqueous solution as catalyst, carboxylic cyclization is carried out in carbon dioxide, it is (the 1H of quinazoline 2,4 that reaction solution obtains product after filtering, washing, drying, 3H) diketone and its derivative, the substrate are 3 ~ 8 with the mol ratio of the diethanol amine aqueous solution:1~3；The reaction temperature of the carboxylic cyclisation is 60 ~ 140 DEG C, and the reaction time is 6 ~ 18h；The pressure of the carbon dioxide is 0.5 ~ 2MPa.The present invention has catalyst with low cost, product yield high, selectivity good compared with prior art, is a kind of method of environment-friendly homogeneous catalysis synthesis (1H, 3H) diketone of quinazoline 2,4 and its derivative.
Description
Technical field
The present invention relates to medicine intermediate technical field, especially a kind of quinazoline -2,4 (1H, 3H)-diketone and its derivative
The synthetic method of thing.
Background technology
Quinazoline -2,4 (1H, 3H)-diketone is a kind of important medicine intermediate, is lived with very excellent bio-pharmaceutical
Property, diabetes medicament FK366 and heart disease specific drug the KF31327 chloro- quinazolines -2,4 of intermediate feed 7- (1H, 3H)-two
Ketone is exactly one of its derivative.6,7- Dimethoxy-quinazolins -2,4 (1H, 3H)-diketone is the weight for producing drug for hypertension
Intermediate is wanted, its prior synthesizing method is mainly ortho-aminobenzoic acid and urea or cyanic acid nak response, anthranilamide
Reacted with phosgene reaction and Anthranilate with isocyanates, the wherein poisonous examination such as phosgene, potassium cyanate and isocyanates
The use of agent and harsh reaction condition make its industrial applications increasingly be restricted.Earlier 2000s, carbon dioxide with
O-amino benzonitride method of reaction generation quinazoline -2,4 (1H, 3H)-diketone under strong alkali catalyst effect is developed
Come, cause the concern of numerous chemists, find a kind of catalyst system and catalyzing and the reaction one is efficiently catalyzed under conditions of milder
It is directly the direction that everybody makes great efforts.
Diethanol amine (DEA) is a kind of conventional commercial acid gas absorbent, in the field of gas purification of compound probability
It is widely used, its water solution system is stable, alkalescence is suitable, hydramine strong to gas sorption capabilities such as carbon dioxide, sulfur dioxide
On alcoholic extract hydroxyl group be also proved to be conducive to the absorption of carbon dioxide to activate.
Quinazoline -2,4 (1H, 3H)-diketone and its derivative complex process prepared by prior art, severe reaction conditions make
With toxic reagents such as phosgene, potassium cyanate and isocyanates, environmental pollution is more serious.
The content of the invention
The purpose of the present invention be in view of the shortcomings of the prior art and provide a kind of quinazoline -2,4 (1H, 3H)-diketone and
The synthetic method of its derivative, catalyst system and catalyzing, catalysis carbon dioxide and o-amino benzoyl are used as using the aqueous solution of diethanol amine
Nitrile carboxylic cyclization generation quinazoline -2,4 (1H, 3H)-diketone, synthesis can be carried out efficiently in a mild condition, and reduced
The use of machine solvent, product separating-purifying easily, meets the theory of Green Chemistry and the requirement of sustainable development, is adapted to industrialization
Implement.
Realizing the concrete technical scheme of the object of the invention is：A kind of quinazoline -2,4 (1H, 3H)-diketone and its derivative
Synthetic method, is characterized in o-amino benzonitride, 2- amino-5-fluorines benzonitrile, 2- amino -5- chlorobenzonitriles, 2- amino -5-
Bromobenzylcyanide, 2- amino -4- fluorobenzonitriles, 2- amino -4- chlorobenzonitriles, 2- amino -4- methyl benzonitriles, 2- amino -4,5-
Dimethoxybenzonitrile, 2- amino terephthalonitrile, 2- amino -4- trifluoromethylbenzonitriles or 2- amino -4- nitrobenzonitriles are
The diethanol amine aqueous solution that substrate is 0.33~1.33mol/L with concentration is catalyst, is carried out under carbon dioxide atmosphere as follows
The carboxylic cyclization of reaction structure formula：
Reaction terminate after, reaction solution through filtering, washing, drying after product be quinazoline -2,4 (1H, 3H)-diketone and its
Derivative, the substrate is 3~8 with the mol ratio of the diethanol amine aqueous solution:1~3；The reaction temperature of carboxylic cyclisation for 60~
140 DEG C, the reaction time is 6~18h；The pressure of the carbon dioxide is 0.5~2MPa.
The mol ratio of the substrate and the diethanol amine aqueous solution is preferably 5:3.
The concentration of the diethanol amine aqueous solution is preferably 1mol/L.
The reaction temperature of the carboxylic cyclisation is preferably 100 DEG C, and the time of reaction is preferably 12 hours.
The pressure of the carbon dioxide is preferably 1MPa.
The general structure of quinazoline -2,4 (1H, the 3H)-derovatives is as follows：
Wherein：X1=H, Y1=H；X2=F, Y2=H；X3=Cl, Y3=H；X4=Br Y4=H；X5=H, Y1=F；X6=H,
Y6=CH3；X7=OMe, Y7=OMe；X8=H, Y8=CN；X9=H, Y9=CF3；X10=H, Y10=NO2。
The present invention has that preparation method is simply controllable compared with prior art, and catalyst is with low cost, abundance and match somebody with somebody
It is made as preserving after the weak solution of catalyst system and catalyzing and is easily unlikely to deteriorate, product yield high, selectivity is good, the letter of synthetic method step
Single, equipment requirement is not high, reaction temperature pressure and general industry condition coupling, it is easy to industrialization promotion, is a kind of environment friend
Good homogeneous catalysis synthesis quinazoline -2,4 (1H, 3H)-diketone and its method for derivative.
By specific examples below, the present invention is described in further detail.
Embodiment 1
Weigh 0.59g (5mmol) o-amino benzonitride to be placed in the polytetrafluoroethyllining lining of stainless steel cauldron, add
3mL concentration is the 1mol/L diethanol amine aqueous solution, stir 2 minutes it is well mixed after, be passed through carbon dioxide and be warming up to 100
DEG C, pressure carbon dioxide is adjusted to the carboxylic cyclization under 1MPa progress stable conditions, the reaction time is 12 hours.Reaction terminates
Afterwards, reaction system is cooled to room temperature, slowly discharges unreacted carbon dioxide, add 10mL deionized waters and dispersed with stirring production
Thing, is filtrated to get precipitation and with a small amount of distillation water washing, then with 15mL/ washing of methyl tertiary butyl ether(MTBE) three times, in 100 DEG C of temperature
Dried under degree product be quinazoline -2,4 (1H, 3H)-diketone, its yield be 94%.
Embodiment 2
0.68g (5mmol) 2- amino-5-fluorine benzonitriles are weighed to be placed in the polytetrafluoroethyllining lining of stainless steel cauldron,
The diethanol amine aqueous solution that 3mL concentration is 0.33mol/L is added, is stirred after being well mixed within 2 minutes, is passed through carbon dioxide and heats up
To 100 DEG C, pressure carbon dioxide is adjusted to the carboxylic cyclization under 1MPa progress stable conditions, the reaction time is 12 hours.Instead
After should terminating, reaction system is cooled to room temperature, unreacted carbon dioxide is slowly discharged, 10mL deionized waters is added and stirs
Dispersion product, is filtrated to get precipitation and with a small amount of distillation water washing, then with 15mL/ washing of methyl tertiary butyl ether(MTBE) three times,
Dried at a temperature of 100 DEG C product be 6- Fluquinconazoles quinoline -2,4 (1H, 3H)-diketone, its yield be 94%.
Embodiment 3
0.763g (5mmol) 2- amino -5- chlorobenzonitriles are weighed to be placed in the polytetrafluoroethyllining lining of stainless steel cauldron,
The diethanol amine aqueous solution that 3mL concentration is 1.33mol/L is added, is stirred after being well mixed within 2 minutes, is passed through carbon dioxide and heats up
To 100 DEG C, pressure carbon dioxide is adjusted to the carboxylic cyclization under 1MPa progress stable conditions, the reaction time is 12 hours.Instead
After should terminating, reaction system is cooled to room temperature, unreacted carbon dioxide is slowly discharged, 10mL deionized waters is added and stirs
Dispersion product, is filtrated to get precipitation and with a small amount of distillation water washing, then with 15mL/ washing of methyl tertiary butyl ether(MTBE) three times,
Product 6- chloro-quinazolines -2,4 (1H, 3H)-diketone is dried to obtain at a temperature of 100 DEG C, its yield is 93%.
Embodiment 4
0.985g (5mmol) 2- amino -5- bromobenzylcyanides are weighed to be placed in the polytetrafluoroethyllining lining of stainless steel cauldron,
The diethanol amine aqueous solution that 3mL concentration is 1mol/L is added, is stirred after being well mixed within 2 minutes, is passed through carbon dioxide and is warming up to
100 DEG C, pressure carbon dioxide is adjusted to the carboxylic cyclization under 1MPa progress stable conditions, the reaction time is 12 hours.Reaction
After end, reaction system is cooled to room temperature, unreacted carbon dioxide is slowly discharged, 10mL deionized waters is added and stirs and divide
Scattered product, is filtrated to get precipitation and with a small amount of distillation water washing, then with 15mL/ washing of methyl tertiary butyl ether(MTBE) three times, 100
Product 6- bromines quinazoline -2,4 (1H, 3H)-diketone is dried to obtain at a temperature of DEG C, its yield is 88%.
Embodiment 5
0.763g (5mmol) 2- amino -4- chlorobenzonitriles are weighed to be placed in the polytetrafluoroethyllining lining of stainless steel cauldron,
The diethanol amine aqueous solution that 3mL concentration is 1.33mol/L is added, is stirred after being well mixed within 2 minutes, is passed through carbon dioxide and heats up
To 100 DEG C, pressure carbon dioxide is adjusted to the carboxylic cyclization under 1MPa progress stable conditions, the reaction time is 12 hours.Instead
After should terminating, reaction system is cooled to room temperature, unreacted carbon dioxide is slowly discharged, 10mL deionized waters is added and stirs
Dispersion product, is filtrated to get precipitation and with a small amount of distillation water washing, then with 15mL/ washing of methyl tertiary butyl ether(MTBE) three times,
Product 7- chloro-quinazolines -2,4 (1H, 3H)-diketone is dried to obtain at a temperature of 100 DEG C, its yield is 62%.
Embodiment 6
Weigh the polytetrafluoroethyllining lining that 0.66g (5mmol) 2- amino -4- methyl benzonitriles are placed in stainless steel cauldron
In, the diethanol amine aqueous solution that 3mL concentration is 1.33mol/L is added, stirs after being well mixed within 2 minutes, is passed through carbon dioxide simultaneously
100 DEG C are warming up to, pressure carbon dioxide is adjusted to the carboxylic cyclization under 1MPa progress stable conditions, the reaction time is 12 small
When.After reaction terminates, reaction system is cooled to room temperature, unreacted carbon dioxide is slowly discharged, 10mL deionized waters are added
And dispersed with stirring product, precipitation is filtrated to get and with a small amount of distillation water washing, then with 15mL/ washing three of methyl tertiary butyl ether(MTBE)
It is secondary, product 7- methylquinazolins -2,4 (1H, 3H)-diketone is dried to obtain at a temperature of 100 DEG C, its yield is 70%.
Embodiment 7
Weigh the polytetrafluoroethylene (PTFE) that 0.89g (5mmol) 2- amino -4,5- dimethoxybenzonitriles are placed in stainless steel cauldron
In liner, the diethanol amine aqueous solution that 3mL concentration is 0.5mol/L is added, stirs after being well mixed within 2 minutes, is passed through carbon dioxide
And it is warming up to 100 DEG C, pressure carbon dioxide is adjusted into 1MPa carries out carboxylic cyclization under stable condition, and the reaction time is 12 small
When.After reaction terminates, reaction system is cooled to room temperature, unreacted carbon dioxide is slowly discharged, 10mL deionized waters are added
And dispersed with stirring product, precipitation is filtrated to get and with a small amount of distillation water washing, then with 15mL/ washing three of methyl tertiary butyl ether(MTBE)
It is secondary, dry to obtain product 6 at a temperature of 100 DEG C, 7- dimethoxyquinazolines -2,4- (1H, 3H)-diketone, yield is 93%.
Various embodiments above is that the present invention will be further described, and is not used to limit patent of the present invention, and all is this hair
Within bright equivalence enforcement, the right for being intended to be limited solely by patent of the present invention.
Claims (5)
1. the synthetic method of a kind of quinazoline -2,4 (1H, 3H)-diketone and its derivative, it is characterised in that with o-amino benzoyl
Nitrile, 2- amino-5-fluorines benzonitrile, 2- amino -5- chlorobenzonitriles, 2- amino -5- bromobenzylcyanides, 2- amino -4- fluorobenzonitriles, 2-
Amino -4- chlorobenzonitriles, 2- amino -4- methyl benzonitriles, 2- amino -4,5- dimethoxybenzonitriles, 2- amino terephthalonitrile,
2- amino -4- trifluoromethylbenzonitriles or 2- amino -4- nitrobenzonitriles are substrate and concentration is the two of 0.33~1.33mol/L
Aqueous ethanolamine is catalyst, and the carboxylic cyclization of following reaction structure formula is carried out under carbon dioxide atmosphere：
After reaction terminates, it is quinazoline -2,4 (1H, 3H)-diketone and its derivative that reaction solution obtains product after filtering, washing, drying
Thing, the substrate is 3~8 with the mol ratio of the diethanol amine aqueous solution:1~3；The reaction temperature of the carboxylic cyclisation is 60~140
DEG C, the reaction time is 6~18h；The pressure of the carbon dioxide is 0.5~2MPa.
2. a kind of synthetic method of quinazoline -2,4 (1H, 3H)-diketone according to claim 1, it is characterised in that the bottom
The mol ratio of thing and the diethanol amine aqueous solution is preferably 5:3.
3. a kind of synthetic method of quinazoline -2,4 (1H, 3H)-diketone according to claim 1, it is characterised in that described two
The concentration of aqueous ethanolamine is preferably 1mol/L.
4. a kind of synthetic method of quinazoline -2,4 (1H, 3H)-diketone according to claim 1, it is characterised in that the carboxylic
The reaction temperature of cyclisation is preferably 100 DEG C, and the time of reaction is preferably 12 hours.
5. a kind of synthetic method of quinazoline -2,4 (1H, 3H)-diketone according to claim 1, it is characterised in that described two
The pressure of carbonoxide is preferably 1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710169548.2A CN106946800B (en) | 2017-03-21 | 2017-03-21 | A kind of synthetic method of -2,4 (1H, 3H)-diketone of quinazoline and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710169548.2A CN106946800B (en) | 2017-03-21 | 2017-03-21 | A kind of synthetic method of -2,4 (1H, 3H)-diketone of quinazoline and its derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106946800A true CN106946800A (en) | 2017-07-14 |
| CN106946800B CN106946800B (en) | 2019-11-15 |
Family
ID=59472656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710169548.2A Active CN106946800B (en) | 2017-03-21 | 2017-03-21 | A kind of synthetic method of -2,4 (1H, 3H)-diketone of quinazoline and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106946800B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863952A (en) * | 2018-08-23 | 2018-11-23 | 天津科技大学 | A kind of catalyst preparing 2,4 (1H, 3H)-quinazoline diones and its derivative |
| CN110711601A (en) * | 2019-10-30 | 2020-01-21 | 青岛科技大学 | In-situ conversion of CO2Process and catalyst for preparing quinazoline-2, 4(1H,3H) -diones and derivatives thereof |
| CN111454222A (en) * | 2020-02-28 | 2020-07-28 | 南京工业大学 | Synthetic method of 2,4- (1H, 3H) -quinazoline diketone and derivative thereof |
| CN114082442A (en) * | 2021-11-18 | 2022-02-25 | 河南大学 | Succinimidyl ionic liquid and method for catalytically synthesizing quinazoline-2, 4(1H,3H) -diketone by using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096360A (en) * | 2006-10-10 | 2008-01-02 | 北京理工大学 | Method for synthesizing 1H,3H-quinazoline-2,4-diketone compound |
| CN105153048A (en) * | 2015-07-31 | 2015-12-16 | 苏州大学 | Preparation method of benzoyleneurea compounds |
-
2017
- 2017-03-21 CN CN201710169548.2A patent/CN106946800B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096360A (en) * | 2006-10-10 | 2008-01-02 | 北京理工大学 | Method for synthesizing 1H,3H-quinazoline-2,4-diketone compound |
| CN105153048A (en) * | 2015-07-31 | 2015-12-16 | 苏州大学 | Preparation method of benzoyleneurea compounds |
Non-Patent Citations (6)
| Title |
|---|
| JUN MA,等: "Efficient synthesis of quinazoline-2,4(1H,3H)-diones from CO2 and 2-aminobenzonitriles in water without any catalyst", 《GREEN CHEMISTRY》 * |
| TAKUMI MIZUNO,等: "Highly efficient synthesis of 1H-quinazoline-2,4-diones using carbon dioxide in the presence of catalytic amount of DBU", 《TETRAHEDRON》 * |
| TAKUMI MIZUNO,等: "Synthesis of 2,4-dihydroxyquinazolines using carbon dioxide in the presence of DBU under mild conditions", 《TETRAHEDRON LETTERS》 * |
| TAKUMI MIZUNO,等: "The simple solvent-free synthesis of 1H-quinazoline-2,4-diones using supercritical carbon dioxide and catalytic amount of base", 《TETRAHEDRON LETTERS》 * |
| WENJING LU,等: "Choline hydroxide promoted chemical fixation of CO2 to quinazoline-2,4(1H,3H)-diones in water", 《RSC ADVANCES》 * |
| 慕玲玲: "绿色催化CO2合成喹唑啉-2,4-(1H,3H)-二酮的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863952A (en) * | 2018-08-23 | 2018-11-23 | 天津科技大学 | A kind of catalyst preparing 2,4 (1H, 3H)-quinazoline diones and its derivative |
| CN108863952B (en) * | 2018-08-23 | 2019-08-23 | 天津科技大学 | A kind of catalyst preparing 2,4 (1H, 3H)-quinazoline diones and its derivative |
| CN110711601A (en) * | 2019-10-30 | 2020-01-21 | 青岛科技大学 | In-situ conversion of CO2Process and catalyst for preparing quinazoline-2, 4(1H,3H) -diones and derivatives thereof |
| CN111454222A (en) * | 2020-02-28 | 2020-07-28 | 南京工业大学 | Synthetic method of 2,4- (1H, 3H) -quinazoline diketone and derivative thereof |
| CN114082442A (en) * | 2021-11-18 | 2022-02-25 | 河南大学 | Succinimidyl ionic liquid and method for catalytically synthesizing quinazoline-2, 4(1H,3H) -diketone by using same |
| CN114082442B (en) * | 2021-11-18 | 2024-01-19 | 河南大学 | Succinimidyl ionic liquid and method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by using same as catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106946800B (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106946800A (en) | A kind of synthetic method of (1H, the 3H) diketone of quinazoline 2,4 and its derivative | |
| CN103755588A (en) | Synthetic method and application of covalent organic framework (COF) material | |
| CN104844461A (en) | Synthetic process for amino aromatic hydrocarbon compound | |
| CN106632084B (en) | Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescent and its preparation method and application | |
| CN102898264B (en) | Catalytic preparation process for aromatic nitrile or heteroaromatic nitrile | |
| CN105601588B (en) | The synthetic method of N- hydroxyethyl piperazine coproduction piperazines | |
| CN103566949A (en) | Copper-based catalyst for preparing ethylene glycol and ethylene glycol monomethyl ether through hydrogenation of dimethyl oxalate and preparation method thereof | |
| CN106632073A (en) | Synthesis method of 3,4-dihydropyrimidin-2-ketone compounds catalyzed by ionic liquid at room temperature | |
| CN106892790B (en) | Method for preparing deuterated aniline compound by using microchannel reaction device | |
| CN106831643B (en) | The method for preparing rubber accelerator MBTS using micro-reaction device | |
| CN102744106A (en) | Palladium catalyst for catalyzing Suzuki coupling reaction, synthesis method, application and ligand | |
| CN101914042A (en) | Preparation method of nicarbazin midbody 4,4'- binitro sym-diphenylurea | |
| CN102174023B (en) | Preparation method of hydroxyl pyridine compound | |
| CN104876932B (en) | A kind of efficient catalytic synthesizes the method for 2H indole [2,1 b] phthalazines 1,6,11 (13H) triketone | |
| CN102993131B (en) | Method for preparing cyclohexene oxide by cyclization of o-chlorocyclohexanol | |
| CN107501338B (en) | Preparation method of 2, 6-diaminopyridine condensed 4-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN114716597B (en) | Solid ionic organic porous polymer and preparation method and application thereof | |
| CN102241654A (en) | Environmentally-friendly synthetic method of pyrimidine compound | |
| CN109134203A (en) | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation | |
| CN101602014B (en) | Load type carbon nano-fiber catalyst and application thereof | |
| CN105601523B (en) | A kind of method for synthesizing the chloroaniline of 2,5 dimethoxy 4 | |
| CN103373958A (en) | Preparation method of 5-ethylpyridine-2,3-diethyl diformate | |
| CN105152946B (en) | A kind of method for efficiently, quickly synthesizing o-Aminobenzaldehyde | |
| CN107513078B (en) | Preparation method of 2, 6-diaminopyridine condensed 3-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN105153048A (en) | Preparation method of benzoyleneurea compounds |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |