CN106748688A - A kind of preparation method of benzaldehyde and its derivative - Google Patents
A kind of preparation method of benzaldehyde and its derivative Download PDFInfo
- Publication number
- CN106748688A CN106748688A CN201611075647.6A CN201611075647A CN106748688A CN 106748688 A CN106748688 A CN 106748688A CN 201611075647 A CN201611075647 A CN 201611075647A CN 106748688 A CN106748688 A CN 106748688A
- Authority
- CN
- China
- Prior art keywords
- benzaldehyde
- derivative
- preparation
- cocatalyst
- catalyst
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides the preparation method of a kind of benzaldehyde and its derivative, and it is comprised the following steps：In the presence of an oxidizer, catalyst is added, toluene or first substituted benzene is added, a step is obtained benzaldehyde or benzaldehyde derivative；Wherein, catalyst includes metallic catalyst, cocatalyst I and cocatalyst II；Metallic catalyst is transition-metal catalyst；Cocatalyst I is alkaline containing n-donor ligand；Cocatalyst II is alkali compounds.The preparation method of a kind of benzaldehyde provided by the present invention and its derivative, by toluene one-step direct oxidation method producing benzaldehyde, and the synthesis comprising benzaldehyde derivative, cost of material is cheap and wide material sources, and reaction speed is fast, and production intensity is big, the features such as being suitable for automation, continuous prodution, and it is not chloride in method system, more suitable for industrialized production, have a good application prospect.
Description
Technical field
The present invention relates to a kind of benzaldehyde and its preparation method of derivative.
Background technology
Benzaldehyde is a kind of colourless or weak yellow liquid, with semen armeniacae amarae fragrance, is commonly called as almond oil.Benzaldehyde can be carried out
The serial reactions such as nucleophilic addition, aldol condensation, disproportionated reaction, nitrification and chlorination, derive many chemical products.It is used as important
Fine chemistry intermediate and raw material be widely used in the fields such as medicine, food, beverage, agricultural chemicals, dyestuff.
The demand of China's benzaldehyde was reached with every year about 7% increasing rate by the end of market demand in 2015
To more than 30kt.The industrial process of current benzaldehyde mainly has two kinds, and one is benzyl chloride Hydrolyze method, and two is toluene oxidation
Method.
The benzaldehyde major part of China is produced by benzyl chloride hydrolysis process, chloride is contained in its product, therefore limit
Application of the benzaldehyde in spices and medical industry.Benzyl chloride Hydrolyze method course of reaction is long and complex, and the difficult control of reaction, product contains
Chlorine and be corrosive gas and debirs are given off, contaminative is big, high to equipment requirement, do not meet Green Chemistry and sustainable
The requirement of development.
Although not chloride in the benzaldehyde of toluene oxidation method synthesis, benzaldehyde is the accessory substance of the technique, thus is produced
Amount is low, it is impossible to meet market needs.With the increasingly increase to benzaldehyde demand, domestic and foreign scholars are also to benzaldehyde synthesis technique
Substantial amounts of research is carried out.Current Rhone-Poulenc Company is using SNIA VISCOSA methods by toluene --- benzoic acid route
Production caprolactam, realizes the industrialized route of benzaldehyde synthesis.But current toluene oxidation method is primarily present toluene conversion
Can not selectively be taken into account simultaneously with benzaldehyde, the shortcomings of product separates difficulty.
The content of the invention
The invention provides a kind of benzaldehyde and its preparation method of derivative, the preparation method realizes toluene to benzene
The oxidation of formaldehyde, and the synthesis comprising benzaldehyde derivative, synthesized benzaldehyde or the yield of benzaldehyde derivative are higher, make
It is with larger industrial utilization.
To solve the above problems, the invention provides a kind of benzaldehyde and its preparation method of derivative, realize by toluene
And its homologue direct oxidation is benzaldehyde and its derivative, the preparation method includes following synthesis step：Exist in oxidant
Under, catalyst is added, toluene or first substituted benzene are added, a step is obtained the benzaldehyde or benzaldehyde derivative；
Wherein, the catalyst includes metallic catalyst, cocatalyst I and cocatalyst II；
The metallic catalyst is transition-metal catalyst；
The cocatalyst I is alkaline containing n-donor ligand；
The cocatalyst II is alkali compounds.
Further, the benzaldehyde derivative includes 4- tolyl aldehydes, 4- chlorobenzaldehydes, 4- bromos benzaldehyde, 4-
One kind in nitrobenzaldehyde, 3- fluorobenzaldehydes, 4- phenyl benzaldehyde, 4- acetylbenzaldehydes or 2- naphthyl aldehydes.
Further, the metallic catalyst include ferrous acetate, frerrous chloride, ferrous bromide, ferric nitrate, iron chloride,
One or more in copper nitrate, manganese acetate, manganese nitrate.
Further, the amount of the material of the metallic catalyst is the 1-5% of the oxidant.
Further, the cocatalyst I includes succinimide, N-hydroxy-succinamide, N- bromo succinyls
Imines, HP or 2, one or more in 2,6,6- tetramethyl piperidines-nitrogen-oxide.
Further, the amount of the material of the cocatalyst I is the 5-10% of the oxidant.
Further, the cocatalyst II includes potassium carbonate, sodium carbonate, cesium carbonate, KBr, sodium chloride, chlorination
Ammonium, ammonium acetate, sodium acetate, NaOH, calcium hydroxide, silica, alchlor orOne kind or many in molecular sieve
Kind.
Further, the amount of the material of the cocatalyst II is the 5-10% of the oxidant.
Further, described oxidant includes the one kind in oxygen or air.
Further, the reaction temperature of the preparation method is 80-140 DEG C, and the reaction time is 16-20h.
It should be noted that in the preparation method, toluene or first substituted benzene also serve as body both as the substrate of reaction
The solvent of system is present, therefore whole system is using the consumption of oxidant as calculating benchmark.
Beneficial effects of the present invention
A kind of benzaldehyde and its preparation method of derivative that the present invention is protected, relative to prior art, at least have
Advantages below：
1. the preparation method is that raw material passes through oxidant direct oxidation, one-step method system by by toluene or first substituted benzene
Benzaldehyde or benzaldehyde derivative, cost of material are cheap, and wide material sources, fast with reaction speed, and production intensity is big, is suitable for certainly
The features such as dynamicization, continuous prodution；
2. the yield relative to oxygen of benzaldehyde prepared by the preparation method and its derivative is higher, oxidant utilization
It is higher；
3. the preparation method prepares benzaldehyde and its derivative so that later separation purifying technique is simple, solves existing
The drawbacks of technology isolates and purifies difficulty；
4. catalyst used in the preparation method and co-catalyst be can be very good to recycle, and laboratory stage is repeated
Using three times, catalytic efficiency is not reduced significantly；
5th, in the preparation method, first Benzene and Homologues divide not only as the substrate of reaction but also as the solvent of reaction
Can be continued cycling through after and used；
6. not chloride in system where the preparation method, it is environmentally friendly, it is low for equipment requirements, meet Green Chemistry and
The requirement of sustainable development, has a good application prospect.
Brief description of the drawings
Fig. 1：Benzaldehyde1H-NMR characterizes collection of illustrative plates；
Fig. 2：The GC-MS of benzaldehyde characterizes collection of illustrative plates.
Specific embodiment
With reference to embodiment, specific embodiment of the invention is described in further detail.Following examples are used for
The present invention is illustrated, but is not limited to the scope of the present invention.
Embodiment 1
First, 0.004mmol ferrous acetates, 0.04mmol succinimides and 0.04mmol calcium hydroxides are accurately weighed,
Add in Young reaction tube, the volume of Young reaction tube is 10mL in the present embodiment, and has been put into magnetic stir bar in advance.So
Afterwards, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made to be carried out under the conditions of gaseous oxidant.
Then 1.5mL dry toluenes are added to accurate in Young reaction tube with syringe, and above-mentioned Young reaction tube is put
In on magnetic stirring apparatus, 20h is stirred at 140 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains benzaldehyde sterling
0.32g, yield is 78%.The yield of benzaldehyde herein is the yield relative to oxygen, as obtained by equation below is calculated：
Wherein, the molal volume of oxygen is 22.4L/mol；mwIt is benzaldehyde or the generation quality of benzaldehyde derivative, M is
The molecular weight of benzaldehyde or benzaldehyde derivative.
Characterization test has been done to benzaldehyde obtained above：
Fig. 1 show the H spectrums of benzaldehyde, it is therefore intended that determine structure and purity.1The characterize data of H-NMR is：1H-NMR
(400MHz, CDCl3)：δ (ppm)=7.51 (m, 2.0H), 7.63 (m, 1.0H), 7.88 (d, J=4.0Hz, 2.0H), 10.02
(s, 1.0H).
Fig. 2 show the mass spectrogram of benzaldehyde, it is therefore intended that determine the structure of benzaldehyde, and the characterize data of GC-MS is：m/
z[C7H6O]+：105.
Embodiment 2
First, 0.004mmol frerrous chlorides, 0.03mmolN- HOSu NHSs and 0.04mmol carbonic acid are accurately weighed
Sodium, adds in Young reaction tube, and the volume of Young reaction tube is 10mL in the present embodiment, and has been put into magnetic agitation in advance
Son.Then, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made to be carried out under the conditions of gaseous oxidant.
Then the anhydrous parachlorotoluenes of 1.5mL are added to accurate in Young reaction tube with syringe, and above-mentioned Young reaction tube is placed in magnetic
On power agitator, 18h is stirred at 120 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains chlorobenzaldehyde sterling
0.38g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 74%.
Embodiment 3
First, 0.01mmol copper nitrates, 0.03mmolN- NBSs and 0.03mmol sodium acetates are accurately weighed,
Add in Young reaction tube, the volume of Young reaction tube is 10mL in the present embodiment, and has been put into magnetic stir bar in advance.So
Afterwards, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made to be carried out under the conditions of gaseous oxidant.Then use
Syringe adds the anhydrous parabromotoluenes of 1.5mL to accurate in Young reaction tube, and above-mentioned Young reaction tube is placed in into magnetic agitation
On device, 19h is stirred at 140 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains bromobenzaldehyde sterling
0.45g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 67%.
Embodiment 4
First, 0.02mmol manganese acetates, 0.02mmolN- hydroxyphthalimides and 0.03mmol tri- are accurately weighed
Aluminum oxide, adds in Young reaction tube, and the volume of Young reaction tube is 10mL in the present embodiment, and has been put into magnetic force and stirs in advance
Mix son.Then, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made to enter under the conditions of gaseous oxidant
OK.Then the anhydrous para-nitrotoluene of 1.5mL is added to accurate in Young reaction tube with syringe, and above-mentioned Young reaction tube is put
In on magnetic stirring apparatus, 20h is stirred at 140 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains paranitrobenzaldehyde pure
Product 0.29g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 53%.
Embodiment 5
First, accurately weigh 0.01mmol ferrous bromides, 0.01mmol2,2,6,6- tetramethyl piperidines-nitrogen-oxide and
0.01mmol ammonium chlorides, add in Young reaction tube, and the volume of Young reaction tube is 10mL in the present embodiment, and has been put in advance
Enter magnetic stir bar.Then, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made in gaseous oxidant bar
Carried out under part.Then the anhydrous 3- fluorotoluenes of 1.5mL are added to accurate in Young reaction tube with syringe, and above-mentioned Young is anti-
Should pipe be placed on magnetic stirring apparatus, stir 20h at 120 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and is obtained to 3- fluorobenzene formaldehydes
Sterling 0.24g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 61%.
Embodiment 6
First, 0.01mmol ferric nitrates, 0.03mmol succinimides and 0.03mmol cesium carbonates are accurately weighed, is added
In Young reaction tube, the volume of Young reaction tube is 10mL in the present embodiment, and has been put into magnetic stir bar in advance.Then, to
Oxygen is passed through in Young reaction tube, and oxygen volume is 8mL, reaction is carried out under the conditions of gaseous oxidant.Then with injection
Device adds the anhydrous 4- methyl acetophenones of 1.5mL to accurate in Young reaction tube, and above-mentioned Young reaction tube is placed in into magnetic agitation
On device, 16h is stirred at 140 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains 4- acetylbenzaldehydes
Sterling 0.29g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 53%.
Embodiment 7
First, 0.02mmol iron chloride, 0.04mmolN- NBSs and 0.04mmol sodium chloride are accurately weighed,
Add in Young reaction tube, the volume of Young reaction tube is 10mL in the present embodiment, and has been put into magnetic stir bar in advance.So
Afterwards, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made to be carried out under the conditions of gaseous oxidant.Then use
Syringe adds the anhydrous 4- methyl acetophenones of 1.5mL to accurate in Young reaction tube, and above-mentioned Young reaction tube is placed in into magnetic force
On agitator, 18h is stirred at 100 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains 4- acetylbenzaldehydes
Sterling 0.29g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 53%.
Embodiment 8
First, accurately weigh 0.02mmol manganese nitrates, 0.02mmol2,2,6,6- tetramethyl piperidines-nitrogen-oxide andMolecular sieve, adds in Young reaction tube, and the volume of Young reaction tube is 10mL in the present embodiment, and in advance
First magnetic stir bar has been put into it.Then, to oxygen, and oxygen volume is passed through in Young reaction tube for 8mL, reaction is made in gas oxygen
Carried out under the conditions of agent.Then the anhydrous 2- methyl naphthalenes of 1.5mL are added to accurate in Young reaction tube with syringe, and by above-mentioned poplar
Family name's reaction tube is placed on magnetic stirring apparatus, and 18h is stirred at 80 DEG C.
After reaction terminates, it is acidity to adjust the pH of reaction solution, and reaction solution is post-processed, and obtains 2- naphthaldehyde sterlings
0.27g, can be obtained by the calculation of yield formula in embodiment 1, and yield is 47%.
The present invention is described in detail above, its object is to allow the personage for being familiar with this art to will appreciate that this
The content of invention is simultaneously carried out, and it is not intended to limit the scope of the present invention, all Spirit Essence institutes of the invention
The equivalent change or modification of work, should all cover within the scope of the present invention.
Claims (10)
1. the preparation method of a kind of benzaldehyde and its derivative, it is characterised in that：
It includes following synthesis step：In the presence of an oxidizer, catalyst is added, toluene or first substituted benzene, one is added
Step is obtained the benzaldehyde or benzaldehyde derivative；
Wherein, the catalyst includes metallic catalyst, cocatalyst I and cocatalyst II；
The metallic catalyst is transition-metal catalyst；
The cocatalyst I is alkaline containing n-donor ligand；
The cocatalyst II is alkali compounds.
2. the preparation method of a kind of benzaldehyde according to claim 1 and its derivative, it is characterised in that：The benzaldehyde
Derivative includes 4- tolyl aldehydes, 4- chlorobenzaldehydes, 4- bromos benzaldehyde, 4- nitrobenzaldehydes, 3- fluorobenzaldehydes, 4- phenyl
One kind in benzaldehyde, 4- acetylbenzaldehydes or 2- naphthyl aldehydes.
3. the preparation method of a kind of benzaldehyde according to claim 1 and its derivative, it is characterised in that：The metal is urged
Agent includes the one kind in ferrous acetate, frerrous chloride, ferrous bromide, ferric nitrate, iron chloride, copper nitrate, manganese acetate, manganese nitrate
Or it is various.
4. the preparation method of a kind of benzaldehyde according to claim 3 and its derivative, it is characterised in that：The metal is urged
The amount of the material of agent is the 1-5% of the oxidant.
5. the preparation method of a kind of benzaldehyde according to claim 1 and its derivative, it is characterised in that：The auxiliary is urged
Agent I include succinimide, N-hydroxy-succinamide, N-bromosuccinimide, HP or
One or more in 2,2,6,6- tetramethyl piperidines-nitrogen-oxide.
6. the preparation method of a kind of benzaldehyde according to claim 5 and its derivative, it is characterised in that：The auxiliary is urged
The amount of the material of agent I is the 5-10% of the oxidant.
7. the preparation method of a kind of benzaldehyde according to claim 1 and its derivative, it is characterised in that：The auxiliary is urged
Agent II includes potassium carbonate, sodium carbonate, cesium carbonate, KBr, sodium chloride, ammonium chloride, ammonium acetate, sodium acetate, NaOH, hydrogen
Calcium oxide, dioxy
One or more in SiClx, alchlor or 4A molecular sieves.
8. the preparation method of a kind of benzaldehyde according to claim 7 and its derivative, it is characterised in that：The auxiliary is urged
The amount of the material of agent II is the 5-10% of the oxidant.
9. the preparation method of a kind of benzaldehyde according to claim 1 and its derivative, it is characterised in that：Described oxidation
Agent includes the one kind in oxygen or air.
10. the preparation method of a kind of benzaldehyde according to claim 1 and its derivative, it is characterised in that：The preparation
The reaction temperature of method is 80-140 DEG C, and the reaction time is 16-20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611075647.6A CN106748688A (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of benzaldehyde and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611075647.6A CN106748688A (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of benzaldehyde and its derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106748688A true CN106748688A (en) | 2017-05-31 |
Family
ID=58898628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611075647.6A Pending CN106748688A (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of benzaldehyde and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106748688A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400453A (en) * | 2018-12-13 | 2019-03-01 | 河南师范大学 | A kind of preparation method of 2,6- dibromo benzaldehyde |
| CN109529895A (en) * | 2018-12-27 | 2019-03-29 | 南京工程学院 | A kind of high stability catalyst of toluene oxidation synthesizing benzaldehyde and preparation method thereof |
| CN109701567A (en) * | 2018-12-28 | 2019-05-03 | 南京工程学院 | A kind of high stability catalyst of toluene oxidation synthesizing benzaldehyde |
| CN109967120A (en) * | 2019-03-08 | 2019-07-05 | 浙江大学 | Zeolite molecular sieve supports the preparation method and applications of ferrum-based catalyst |
| CN110305091A (en) * | 2019-06-19 | 2019-10-08 | 江苏理工学院 | A kind of preparation method of Ba Luoshawei midbody compound |
| CN111606791A (en) * | 2020-06-08 | 2020-09-01 | 杭州医学院 | Synthetic method of aromatic benzyl ketone |
| CN112047823A (en) * | 2020-07-27 | 2020-12-08 | 南京延长反应技术研究院有限公司 | Preparation system and method of halogenated benzaldehyde |
| CN112574102A (en) * | 2020-12-24 | 2021-03-30 | 安道麦安邦(江苏)有限公司 | Novel method and device for synthesizing pymetrozine intermediate nicotinaldehyde |
| WO2021088123A1 (en) * | 2019-11-04 | 2021-05-14 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Catalyst for thermal degradation of carbon-fiber-and-resin-based composite material and application method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440028A (en) * | 2008-11-06 | 2009-05-27 | 浙江工业大学 | Process for synthesizing p-tertiary butyl benzaldehyde |
-
2016
- 2016-11-29 CN CN201611075647.6A patent/CN106748688A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440028A (en) * | 2008-11-06 | 2009-05-27 | 浙江工业大学 | Process for synthesizing p-tertiary butyl benzaldehyde |
Non-Patent Citations (4)
| Title |
|---|
| FENG WANG等: "Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper-Based Heterogeneous Catalysts", 《ADV. SYNTH. CATAL.》 * |
| WENCHAN MA等: "Aerobic oxidation of p-cresols to 4-hydroxy benzaldehydes catalyzed by cobaltous chloride/NHPI/salen-Cu(II) catalytic system", 《RES CHEM INTERMED》 * |
| YUECHENG ZHANG等: "Liquid-phase oxidation of 2-methoxy-p-cresol to vanillin with oxygen catalyzed by a combination of CoCl2 and N-hydroxyphthalimide", 《RES CHEM INTERMED》 * |
| 周蒙等: "NHPI/Co(Salen)复合催化液相氧化甲苯的工艺考察", 《化学反应工程与工艺》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400453A (en) * | 2018-12-13 | 2019-03-01 | 河南师范大学 | A kind of preparation method of 2,6- dibromo benzaldehyde |
| CN109400453B (en) * | 2018-12-13 | 2021-04-27 | 河南师范大学 | Preparation method of 2, 6-dibromobenzaldehyde |
| CN109529895A (en) * | 2018-12-27 | 2019-03-29 | 南京工程学院 | A kind of high stability catalyst of toluene oxidation synthesizing benzaldehyde and preparation method thereof |
| CN109701567A (en) * | 2018-12-28 | 2019-05-03 | 南京工程学院 | A kind of high stability catalyst of toluene oxidation synthesizing benzaldehyde |
| CN109967120A (en) * | 2019-03-08 | 2019-07-05 | 浙江大学 | Zeolite molecular sieve supports the preparation method and applications of ferrum-based catalyst |
| CN110305091A (en) * | 2019-06-19 | 2019-10-08 | 江苏理工学院 | A kind of preparation method of Ba Luoshawei midbody compound |
| CN110305091B (en) * | 2019-06-19 | 2021-05-18 | 江苏理工学院 | Preparation method of Barosavir intermediate compound |
| WO2021088123A1 (en) * | 2019-11-04 | 2021-05-14 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Catalyst for thermal degradation of carbon-fiber-and-resin-based composite material and application method therefor |
| CN111606791A (en) * | 2020-06-08 | 2020-09-01 | 杭州医学院 | Synthetic method of aromatic benzyl ketone |
| CN111606791B (en) * | 2020-06-08 | 2023-01-03 | 杭州医学院 | Synthetic method of aromatic benzyl ketone |
| CN112047823A (en) * | 2020-07-27 | 2020-12-08 | 南京延长反应技术研究院有限公司 | Preparation system and method of halogenated benzaldehyde |
| CN112574102A (en) * | 2020-12-24 | 2021-03-30 | 安道麦安邦(江苏)有限公司 | Novel method and device for synthesizing pymetrozine intermediate nicotinaldehyde |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106748688A (en) | A kind of preparation method of benzaldehyde and its derivative | |
| Nagaki et al. | Generation and reactions of oxiranyllithiums by use of a flow microreactor system | |
| CN102911096B (en) | Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene | |
| Alcántara et al. | Ethylbenzene oxidation with air catalysed by bis (acetylacetonate) nickel (II) and tetra-n-butylammonium tetrafluoroborate | |
| CN107445830A (en) | The method that ethyl glycolate oxidative dehydrogenation produces glyoxylic ester | |
| CN111393272A (en) | Synthetic method of 3' -methyl propiophenone | |
| CN113277942B (en) | Method for rapidly preparing 5-chloro-2-fluoro-4- (trifluoromethyl) benzoic acid based on microchannel reaction technology | |
| WO2003078372A1 (en) | Method for producing monocyclic ketones c4-c5 | |
| CN102875341A (en) | Synthetic method of benzaldehyde | |
| CN102796025B (en) | Synthesis method for stable isotope labeled malachite green | |
| Nishinaga et al. | Selective formation of peroxy-p-quinolato Co (III) complexes in the oxygenation of 4-alkyl-2, 6-di-t-butylphenols with Co (II)-Schiff's base complexes | |
| US7098344B2 (en) | Reaction of carbonyl compounds with organometallic reagents | |
| CN101580485A (en) | Method for producing methyl thioglycolate | |
| Kresge et al. | Vinyl ether hydrolysis. 10. Methyl. alpha.-cyclopropylvinyl ether. A search for a change in reaction mechanism | |
| CN103664631A (en) | Preparation method of naftifine hydrochloride | |
| CN109879806A (en) | A kind of isoquinolin indenes ether derivant and preparation method thereof | |
| Schlessinger et al. | A new protocol for the diastereoselective formation of lactones from either achiral or chiral vinylogous urethanes | |
| Vivekanand et al. | Kinetics of dichlorocyclopropanation of vinylcyclohexane catalyzed by a new multi-site phase transfer catalyst | |
| CN105348060B (en) | A kind of preparation method of 1,2 derovatives | |
| CN101417989B (en) | Anion receptor based on nitrofuran formyl hydrazone and phenolic hydroxyl and preparation and use of organagel thereof | |
| CN105294416B (en) | A kind of 1,5 Dicarbonyl derivatives and preparation method thereof | |
| CN101367715A (en) | Synthesis of substituted methyl benzylketone | |
| CN108129350A (en) | A kind of preparation method of 2,4 dichloro benzene nitrile | |
| CN104447293B (en) | A kind of method preparing 1-methylcyclopropyl groups formic acid | |
| CN101353332B (en) | Preparation of 3epoxy ethyl-7-oxabicyclo [4,1,0] heptane |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |