CN108456147A - A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide - Google Patents
A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide Download PDFInfo
- Publication number
- CN108456147A CN108456147A CN201810371871.2A CN201810371871A CN108456147A CN 108456147 A CN108456147 A CN 108456147A CN 201810371871 A CN201810371871 A CN 201810371871A CN 108456147 A CN108456147 A CN 108456147A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- nitrophenyl
- hydrazine hydrate
- carrier
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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 a kind of methods that catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide, belong to the catalysis reduction field of fine chemicals.This method is using hydrazine hydrate as reducing agent, using the Ni Co of titanium dichloride load as catalyst, intermittent single step reaction by p-nitrophenyl formamide high conversion, highly selective be reduced to Para Amino Benzamide.The reaction temperature of the restoring method is 55 65 DEG C, and the reaction time is 14 hours, and hydrazine hydrate is with material quality than 15:1.Catalyst system and catalyzing used can efficient catalytic p-nitrophenyl formamide, Para Amino Benzamide is selectively good, high income；Using hydrazine hydrate as reducing agent, by-product is mainly nitrogen and water, and reaction environmental pollution is less；Reaction condition is mild, and reduction process is low to appointed condition requirement, operating process is easy；Product separating-purifying process is easy, catalyst circulation is applied mechanically often.
Description
Technical field
The invention belongs to the catalysis of fine chemicals to restore field, be specifically related to a kind of catalysis reduction p-nitrophenyl formyl
The method that amine prepares Para Amino Benzamide, be it is a kind of providing hydrogen source with hydrazine hydrate, with titanium dioxide, silicon dioxide carried
Nickel, cobalt are catalyst, by intermittent liquid-phase catalysis selective hydrogenation reaction by the pairs of ammonia of p-nitrophenyl formamide selective reduction
Yl-benzamide.
Background technology
Para Amino Benzamide is important medicine, dyestuff intermediate, is mainly used to produce organic pigment Huang C.I
181#, 170# red pigment.
P-nitrophenyl carboxamide Starting material is relatively inexpensive to be easy to get, and Para Amino Benzamide can be prepared by selective reduction.Reduction
Technique there are many kinds of, at present apply more extensive iron powder and sodium sulfide reducing technique, product purity, yield are all relatively low,
And a large amount of " three wastes " are generated, it is unfavorable for the protection of environment, also about using Pd-C to be restored in water phase for catalyst
Reported in literature (Para Amino Benzamide Study of synthesis method prints 1998 (12) 7 when chemical industry), although being reacted in water phase
It is good for the environment, but it uses palladium carbon higher for catalyst cost.Use skeleton nickel for catalyst, in the condition of higher pressure hydrogen
Under restored, although compared to other techniques have the characteristics that more environmental protection, product yield it is high, it is to metalNicatalyst
Dosage it is also relatively high while more demanding using pressure-resistant condition of the high pressure hydrogen there are some potential safety problems and to equipment
(Chinese patent CN1869003A).Therefore, realize that p-nitrophenyl formamide highly effective hydrogenation prepares the key of Para Amino Benzamide
Being to develop has highly selective and high activity and the few catalyst system and catalyzing of active metal dosage.Between passing through the present invention provides one kind
Formula of having a rest catalytic hydrogenation reaction has the highly selective method for being converted into Para Amino Benzamide of p-nitrophenyl formamide important
Application value.
Invention content
The purpose of the present invention is to provide the sides that a kind of p-nitrophenyl formamide highly effective hydrogenation prepares Para Amino Benzamide
Method, this method is using hydrazine hydrate as reducing agent, and the high income of Para Amino Benzamide, reaction condition is mild, and catalyst circulation makes
With number height, product separation is simple, reaction process environmental protection, and at low cost.
Technical scheme of the present invention：
A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide, provides one kind and is with hydrazine hydrate
Reducing agent is reduced by intermittent liquid-phase hydrogenation reaction by p-nitrophenyl formamide is highly selective under the action of catalyst
The method of Para Amino Benzamide；Steps are as follows：
1) the p-nitrophenyl formamide solution that mass fraction is 5%~25% is prepared；
2) catalyst is first added into p-nitrophenyl formamide solution, hydrazine hydrate is then added, obtains mixed liquor；Catalyst
Mass ratio with p-nitrophenyl formamide is 0.05~0.3:1；The mass ratio of hydrazine hydrate and p-nitrophenyl formamide is 1~5:1；
3) mixed liquor is placed in constant temperature stirring water-bath, carries out intermittent liquid-phase catalysis selective hydrogenation under nitrogen protection
Reaction, reaction temperature maintain 55~65 DEG C, are stirred to mixed liquor in reaction process, and are carried out by phased manner to reaction solution
Thin-layer chromatographic analysis judges that reaction carries out situation；Stop reaction after hydrazine hydrate or complete p-nitrophenyl formamide consumption；It is described
Intermittent liquid-phase catalysis selective hydrogenation reaction reaction time be 1~4h；
4) separating catalyst and reaction solution place reaction liquid into and carry out heating distillation in oil bath pan, recycling design, and residue is solid
Body is Para Amino Benzamide.
The catalyst includes active component and carrier, and active component is nickel and cobalt, and carrier is titanium dioxide, titanium dioxide
One or more of silicon, diatomite mix；The mass ratio of nickel and cobalt is 1~4:1, the mass ratio of active component and carrier
It is 0.05~0.3:1.
The preparation method of the catalyst is immersion reduction method, and detailed process is：Take the mixing second of nickel chloride, cobalt chloride
Alcoholic solution is impregnated in carrier, obtains A liquid, dip time 8-12h, and the mass ratio of nickel chloride and carrier is 1:4-1:5, chlorination
The mass ratio of cobalt and carrier is 1:4-1:5；The sodium borohydride aqueous solution that mass fraction is 4.5%-9% is prepared, NaOH tune is used in combination
Section obtains B liquid to alkalinity；A liquid is placed in ice-water bath, B drops are added in A in the case of stirring, also into row metal
Original reaction；The metallic particles generated in reaction process is supported on carrier, while generating gas, until after being generated without gas,
Stop reaction；Catalyst is first washed with distilled water to neutrality, then is washed with absolute ethyl alcohol, catalyst is stored in absolute ethyl alcohol
In it is spare.
The solvent is one or two kinds of above mixing in methanol, ethyl alcohol, normal propyl alcohol, n-butanol, sec-butyl alcohol.
Beneficial effects of the present invention：Catalyst system and catalyzing used can while reducing metallic catalyst usage amount high activity
P-nitrophenyl formamide is restored, high conversion rate；Use hydrazine hydrate for reducing agent, by-product is nitrogen, environmentally protective and reaction
Mild condition, reduction process are low for equipment requirements, easy to operate；Product and catalyst convenient separation, the catalyst being recovered by filtration
Again reactor is put into, catalyst circulation access times are up to 10 times or more.
Specific implementation mode
The present invention is described in further details below in conjunction with specific implementation mode.
Embodiment 1
By 2g p-nitrophenyl formamides, 0.1gNi-Co/TiO2(Ni contents are 5wt%), 10ml absolute methanols are added to
In the single-necked flask of 50ml, 2g hydrazine hydrates are added.Then with air in nitrogen displacement flask, flask is positioned over water bath with thermostatic control
In pot, stirring increases temperature to 55 DEG C, 200-400 revs/min of mixing speed.In reaction process, hydrazine hydrate and p-nitrophenyl first
Amide is constantly consumed, and at interval of a period of time, is analyzed using thin-layered chromatography, judges to react progress.It is right after 4h
Nitrobenzamide is exhausted, and reaction terminates.Reaction solution is cooled down, filtration catalytic agent.A small amount of filtrate is taken to carry out liquid chromatogram
Analysis, p-nitrophenyl carboxamide rate are more than 99%, and Para Amino Benzamide is selectively more than 99%.It is gone by rotary evaporation
It removes the Para Amino Benzamide yield that absolute methanol obtains and is more than 98%.
Embodiment 2
By 2g p-nitrophenyl formamides, 0.1gNi-Co/TiO2(Ni contents are 20wt%), 50ml absolute methanols are added to
In the single-necked flask of 50ml, 10g hydrazine hydrates are added.Then with air in nitrogen displacement flask, flask is positioned over thermostatted water
In bath, stirring increases temperature to 65 DEG C, 200-400 revs/min of mixing speed.In reaction process, hydrazine hydrate and p-nitrophenyl
Formamide is constantly consumed, and at interval of a period of time, is analyzed using thin-layered chromatography, judges to react progress.After 2h
P-nitrophenyl formamide is exhausted, and reaction terminates.Reaction solution is cooled down, filtration catalytic agent.A small amount of filtrate is taken to carry out liquid phase color
Spectrum analysis, p-nitrophenyl carboxamide rate are more than 99%, and Para Amino Benzamide is selectively more than 99%.Pass through rotary evaporation
It gets rid of the Para Amino Benzamide yield that absolute methanol obtains and is more than 98%.
Embodiment 3
By 2g p-nitrophenyl formamides, 0.6gNi-Co/TiO2(Ni contents are 10wt%), 20ml absolute methanols are added to
In the single-necked flask of 50ml, 6g hydrazine hydrates are added.Then with air in nitrogen displacement flask, flask is positioned over water bath with thermostatic control
In pot, stirring increases temperature to 65 DEG C, 200-400 revs/min of mixing speed.In reaction process, hydrazine hydrate and p-nitrophenyl first
Amide is constantly consumed, and at interval of a period of time, is analyzed using thin-layered chromatography, judges to react progress.It is right after 1h
Nitrobenzamide is exhausted, and reaction terminates.Reaction solution is cooled down, filtration catalytic agent.A small amount of filtrate is taken to carry out liquid chromatogram
Analysis, p-nitrophenyl carboxamide rate are more than 99%, and Para Amino Benzamide is selectively more than 99%.It is gone by rotary evaporation
It removes the Para Amino Benzamide yield that absolute methanol obtains and is more than 98%.
Embodiment 4
The catalyst that will be recycled in embodiment 3,20ml absolute methanols are added in 50ml single-necked flasks, add 2g to nitro
Benzamide, 6g hydrazine hydrates replace air in reaction bulb with nitrogen, are stirred continuously down and are warming up to 65 DEG C, mixing speed 200-400
Rev/min, reaction progress is detected using thin-layered chromatography, when p-nitrophenyl formamide is exhausted, illustrates that reaction terminates,
Stop stirring, be cooled to room temperature, extracts reaction solution carry out liquid phase analysis, p-nitrophenyl carboxamide rate is more than 99%, to amino
Benzamide is selectively more than 99%.Recycled catalyst according to the method described above, concrete outcome see the table below.
As can be seen from the table, catalyst still has higher catalytic activity, illustrates that this is urged by 10 uses of catalytic cycle
Agent is with good stability.
Embodiment 5
By 2g p-nitrophenyl formamides, 0.6gNi-Co/TiO2(Ni contents are 10wt%), 20ml absolute ethyl alcohols are added to
In the single-necked flask of 50ml, 6g hydrazine hydrates are added.Then with air in nitrogen displacement flask, flask is positioned over water bath with thermostatic control
In pot, stirring increases temperature to 65 DEG C, 200-400 revs/min of mixing speed.In reaction process, hydrazine hydrate and p-nitrophenyl first
Amide is constantly consumed, and at interval of a period of time, is analyzed using thin-layered chromatography, judges to react progress.It is right after 2h
Nitrobenzamide is exhausted, and reaction terminates.Reaction solution is cooled down, filtration catalytic agent.A small amount of filtrate is taken to carry out liquid chromatogram
Analysis, p-nitrophenyl carboxamide rate are more than 99%, and Para Amino Benzamide is selectively more than 99%.It is gone by rotary evaporation
It removes the Para Amino Benzamide yield that absolute methanol obtains and is more than 98%.
Embodiment 6
By 2g p-nitrophenyl formamides, 0.1gNi-Co/TiO2(Ni contents are 20wt%), 20ml normal propyl alcohols are added to
In the single-necked flask of 50ml, 6g hydrazine hydrates are added.Then with air in nitrogen displacement flask, flask is positioned over water bath with thermostatic control
In pot, stirring increases temperature to 65 DEG C, 200-400 revs/min of mixing speed.In reaction process, hydrazine hydrate and p-nitrophenyl first
Amide is constantly consumed, and at interval of a period of time, is analyzed using thin-layered chromatography, judges to react progress.It is right after 2h
Nitrobenzamide is exhausted, and reaction terminates.Reaction solution is cooled down, filtration catalytic agent.A small amount of filtrate is taken to carry out liquid chromatogram
Analysis, p-nitrophenyl carboxamide rate are more than 99%, and Para Amino Benzamide is selectively more than 99%.It is gone by rotary evaporation
It removes the Para Amino Benzamide yield that absolute methanol obtains and is more than 98%.
Embodiment 7
By 2g p-nitrophenyl formamides, 0.1gNi-Co/TiO2(Ni contents are 20wt%), 20ml n-butanols are added to
In the single-necked flask of 50ml, 6g hydrazine hydrates are added.Then with air in nitrogen displacement flask, flask is positioned over water bath with thermostatic control
In pot, stirring increases temperature to 65 DEG C, 200-400 revs/min of mixing speed.In reaction process, hydrazine hydrate and p-nitrophenyl first
Amide is constantly consumed, and at interval of a period of time, is analyzed using thin-layered chromatography, judges to react progress.It is right after 1h
Nitrobenzamide is exhausted, and reaction terminates.Reaction solution is cooled down, filtration catalytic agent.A small amount of filtrate is taken to carry out liquid chromatogram
Analysis, p-nitrophenyl carboxamide rate are more than 99%, and Para Amino Benzamide is selectively more than 99%.It is gone by rotary evaporation
It removes the Para Amino Benzamide yield that absolute methanol obtains and is more than 98%.
Claims (4)
1. a kind of method that catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide, it is also to provide one kind with hydrazine hydrate
Former agent is reduced into pair by intermittent liquid-phase hydrogenation reaction by p-nitrophenyl formamide is highly selective under the action of catalyst
The method of aminobenzamide；It is characterized in that, steps are as follows：
1) the p-nitrophenyl formamide solution that mass fraction is 5%~25% is prepared；
2) catalyst is first added into p-nitrophenyl formamide solution, hydrazine hydrate is then added, obtains mixed liquor；Catalyst with it is right
The mass ratio of nitrobenzamide is 0.05~0.3:1；The mass ratio of hydrazine hydrate and p-nitrophenyl formamide is 1~5:1；
3) mixed liquor is placed in constant temperature stirring water-bath, it is anti-carries out intermittent liquid-phase catalysis selective hydrogenation under nitrogen protection
It answers, reaction temperature maintains 55~65 DEG C, is stirred to mixed liquor in reaction process, and is carried out by phased manner to reaction solution thin
Layer chromatography judges that reaction carries out situation；Stop reaction after hydrazine hydrate or complete p-nitrophenyl formamide consumption；Described
The reaction time of intermittent liquid-phase catalysis selective hydrogenation reaction is 1~4h；
4) separating catalyst and reaction solution place reaction liquid into and carry out heating distillation in oil bath pan, recycling design, and remaining solid is
For Para Amino Benzamide.
2. according to the method described in claim 1, it is characterized in that, the catalyst includes active component and carrier, activity
Group is divided into nickel and cobalt, and carrier is the mixing of one or more of titanium dioxide, silica, diatomite；The matter of nickel and cobalt
Amount is than being 1~4:1, the mass ratio of active component and carrier is 0.05~0.3:1.
3. according to the method described in claim 2, it is characterized in that, the preparation method of the catalyst be immersion reduction method,
Detailed process is：It takes the mixed ethanol solution of nickel chloride, cobalt chloride to be impregnated in carrier, obtains A liquid, dip time 8-12h,
The mass ratio of nickel chloride and carrier is 1:4-1:5, the mass ratio of cobalt chloride and carrier is 1:4-1:5；Preparing mass fraction is
The sodium borohydride aqueous solution of 4.5%-9%, is used in combination NaOH to be adjusted to alkalinity, obtains B liquid；A liquid is placed in ice-water bath, is being stirred
B drops are added in A in the case of mixing, carry out metal reduction reaction；The metallic particles generated in reaction process is supported on carrier
On, while gas is generated, until after being generated without gas, stop reaction；Catalyst is first washed with distilled water to neutrality, then is used
Absolute ethyl alcohol washs, and catalyst is stored in spare in absolute ethyl alcohol.
4. according to any methods of claim 1-3, which is characterized in that the solvent be methanol, ethyl alcohol, normal propyl alcohol,
One or more of n-butanol, sec-butyl alcohol mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810371871.2A CN108456147A (en) | 2018-04-17 | 2018-04-17 | A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810371871.2A CN108456147A (en) | 2018-04-17 | 2018-04-17 | A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108456147A true CN108456147A (en) | 2018-08-28 |
Family
ID=63235882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810371871.2A Withdrawn CN108456147A (en) | 2018-04-17 | 2018-04-17 | A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108456147A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116237059A (en) * | 2023-01-04 | 2023-06-09 | 沈阳化工研究院有限公司 | Modified hydrotalcite-loaded platinum ruthenium catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041623A (en) * | 2007-04-26 | 2007-09-26 | 上海华谊丙烯酸有限公司 | Method for preparation of (substituted radical containted) aminophenol by catalytic hydrogenation of (substituted radical containted) nitrophenol |
| CN106582832A (en) * | 2016-12-07 | 2017-04-26 | 南昌师范学院 | Catalyst for reduction of aromatic nitro in synthesis of triptan-based drug intermediate and preparation method of catalyst |
-
2018
- 2018-04-17 CN CN201810371871.2A patent/CN108456147A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041623A (en) * | 2007-04-26 | 2007-09-26 | 上海华谊丙烯酸有限公司 | Method for preparation of (substituted radical containted) aminophenol by catalytic hydrogenation of (substituted radical containted) nitrophenol |
| CN106582832A (en) * | 2016-12-07 | 2017-04-26 | 南昌师范学院 | Catalyst for reduction of aromatic nitro in synthesis of triptan-based drug intermediate and preparation method of catalyst |
Non-Patent Citations (4)
| Title |
|---|
| HAIGEN HUANG 等: "Highly chemoselective reduction of nitroarenes over non-noble metal nickel-molybdenum oxide catalysts", 《GREEN CHEMISTRY》 * |
| JIA-WEI ZHANG 等: "Chemoselective transfer hydrogenation of nitroarenes by highly dispersed Ni-Co BMNPs", 《CATALYSIS COMMUNICATIONS》 * |
| 喻素娟 等: "对氨基苯甲酰胺合成方法研究", 《化工时刊》 * |
| 鞠江月 等: "NiCoB/TiO2非晶态合金催化松节油加氢反应", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116237059A (en) * | 2023-01-04 | 2023-06-09 | 沈阳化工研究院有限公司 | Modified hydrotalcite-loaded platinum ruthenium catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1997010202A1 (en) | Method of hydrogenating aromatic compounds in which at least one amino group is bonded to an aromatic nucleus | |
| CN104974047B (en) | Method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene | |
| CN106543115B (en) | A method of preparing furfuryl alcohol using hydrogen transfer reaction catalysis furfural | |
| CN102070459B (en) | Method for preparing amino-compound through catalytic reduction of nitro-compound | |
| CN106582709B (en) | Catalyst for synthesizing aromatic primary amine by hydrogenation of aromatic nitrile and preparation method thereof | |
| Cui et al. | Ultrathin γ-Fe2O3 nanosheets as a highly efficient catalyst for the chemoselective hydrogenation of nitroaromatic compounds | |
| CN108067213A (en) | It is a kind of for catalyst of aniline rectification residue recycling and preparation method thereof | |
| Zou et al. | Catalyst-free hierarchical reduction of CO2 with BH3N (C2H5) 3 for selective N-methylation and N-formylation of amines | |
| CN100457698C (en) | Decahydronaphthalene continuous hydrogenation synthesis method | |
| CN108456147A (en) | A method of catalysis reduction p-nitrophenyl formamide prepares Para Amino Benzamide | |
| CN104557564A (en) | Preparation method of phenylmethylamine | |
| CN102050746A (en) | Method for preparing o-chloroaniline | |
| CN108686660B (en) | Catalyst for synthesizing isophorone diamine by reducing and aminating isophorone nitrile and preparation method and application thereof | |
| CN108273507B (en) | Method for reducing nitrile compound by catalytic hydrogenation | |
| Zhang et al. | Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2‐Responsive Support | |
| CN109422657B (en) | Method for separating methylamine mixed gas and co-producing formamide compound | |
| CN101265194B (en) | Catalytic hydrogenation method for preparing halogenated aromatic amine from halogenated arene nitro compounds | |
| CN101733103B (en) | Method for preparing supported nickel catalysts through carbonyl nickel | |
| CN108273538A (en) | A method of reduction N- heteroaryl hydrocarbon compounds prepare N- heterocycle compounds | |
| CN101182295B (en) | Method for synthesizing 2-amido-5-chlorobenzotrifluoride | |
| CN103664641A (en) | Method for preparing o-chloroaniline by virtue of solvent-free catalytic hydrogenation | |
| CN110054582A (en) | A kind of preparation method of 3- amino-N- ethyl carbazole | |
| CN102351714A (en) | Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene | |
| CN109678655B (en) | Application of nickel-iron hydrotalcite catalyst in preparation of benzyl alcohol | |
| CN108623493A (en) | With CO under a kind of temperate condition2For the N- formylated synthetic methods of carbon source |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180828 |