CN108752246A - A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids - Google Patents
A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids Download PDFInfo
- Publication number
- CN108752246A CN108752246A CN201810725288.7A CN201810725288A CN108752246A CN 108752246 A CN108752246 A CN 108752246A CN 201810725288 A CN201810725288 A CN 201810725288A CN 108752246 A CN108752246 A CN 108752246A
- Authority
- CN
- China
- Prior art keywords
- added
- nitryl
- benzoic acids
- efficient
- production method
- 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- Withdrawn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
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of organic synthesis, specially a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids, it can preferably improve reacts phenomenon difficult and that products collection efficiency is relatively low caused by molecular oxidation current potential is higher in 2- nitro -4- methylsulfonyltoluene oxidation process.Its preparation process includes mainly：After 2- nitro -4- methylsulfonyltoluenes are mixed with iron powder, bromine is added thereto, is uniformly mixed, Sodamide is added thereto later, it is made fully to react, final product liquid is used for subsequent reactions material；Product liquid is mixed with sulfuric acid, nitric acid, stirs, oxidation reaction is carried out under catalysts conditions；Water is added into the mixed liquor of above-mentioned preparation, reaction is hydrolyzed；Water is added into material obtained above, filtering, centrifugation respectively obtain crude product and mother liquor；Calcium nitrite and hydrochloric acid are added into crude product obtained above, stirring, the reaction was complete；Sodium hypophosphite is added thereto, stirs, the reaction was complete, obtains product.
Description
Technical field
The present invention relates to technical field of organic synthesis, specially a kind of production of efficient 2- nitryl-4-thiamphenicol benzoic acids
Industry production method.
Background technology
2- nitryl-4-thiamphenicol benzoic acids are a kind of important organic synthesis intermediates, are widely used in dyestuff, medicine
With the production of pesticide.Currently, the preparation of 2- nitryl-4-thiamphenicol benzoic acids is generally using 2- nitro -4- methylsulfonyltoluenes as raw material,
It is carboxyl by the methyl oxidation on its phenyl ring, corresponding acid is prepared with this.
Publication No. is that the Chinese invention patent of CN106432006A discloses a kind of 2- nitryl-4-thiamphenicol benzoic acids nitrification
Technological process stirs mainly by mixing methylsulfonyltoluene with nitric acid, sulfuric acid, prepares 2- nitro -4- methylsulfonyl benzene first
Acid.
But due to connecting on the phenyl ring of 2- nitro -4- methylsulfonyltoluenes, there are two electron-withdrawing groups so that 2- nitros -4-
The HOMO energy of methylsulfonyltoluene is relatively low, more difficult in electrochemical reaction to lose electronics, to molecular oxidation current potential and reduction electricity
Position is higher, finally, keeps the 2- nitryl-4-thiamphenicol benzoic acid products collection efficiencies prepared using above-mentioned technical proposal relatively low.
Invention content
The object of the present invention is to provide a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids,
It can preferably improve in 2- nitro -4- methylsulfonyltoluene oxidation process and react difficult caused by molecular oxidation current potential is higher,
And the phenomenon that products collection efficiency is relatively low.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids, includes the following steps：
S1：Itrated compound 2- nitro -4- methylsulfonyltoluenes are mixed with sulfuric acid, nitric acid, stirs, is carried out under catalysts conditions
Oxidation reaction；
S2：Water is added in the mixed liquor prepared to S1, reaction is hydrolyzed；
S3：Water is added into material made from S2, filtering, centrifugation respectively obtain crude product and mother liquor；
S4：Liquid caustic soda and clear water are added in the crude product obtained into S3, to crude product alkali soluble；
S5：Clear water washing is added in mixed liquor into S4, filtrate and unreacted 2- nitros -4- methyl sulfone are recycled in filtering
Base toluene；
S6：Hydrochloric acid is added in filtrate into S5, carries out acid out；
S7：Clear water washing is added in mixed liquor into S6, centrifugation removes sewage；
S8：Product drying after being centrifuged in S7, packaging and storage.
Further, before carrying out S1 steps, increase S1 '：After 2- nitro -4- methylsulfonyltoluenes are mixed with iron powder, to
Bromine is wherein added, is uniformly mixed, Sodamide is added thereto later, it is made fully to react, by final product liquid
For subsequent reactions material.
Further, increase S3 ' between S3 and S4：Calcium nitrite and hydrochloric acid are added into crude product made from S3, stirs
It mixes, the reaction was complete；Sodium hypophosphite is added thereto, stirs, the reaction was complete, centrifugation, after the solid product that centrifugation obtains is used for
Continuous alkali soluble reaction.
Further, the mother liquor obtained in S3 steps is distilled, water and sulfuric acid is separately recovered.
Further, the tail gas that oxidation reaction in S1 steps generates is passed through in the water of the distillation recovery of the mother liquor in S3, is inhaled
Finish up gas.
Further, catalyst described in S1 is vanadic anhydride.
Further, liquid caustic soda described in S4 is sodium hydroxide.
Further, in S1 sulfuric acid used be volume ratio 70% sulfuric acid, the nitric acid is the nitric acid of volume ratio 65%.
The invention has the advantages that：
1. the present invention first handles it, makes on its phenyl ring before being aoxidized to substrate 2- nitro -4- methylsulfonyltoluenes
Bromine group is connected, recycles Sodamide that bromine group is substituted by amino, makes to connect amino on phenyl ring, to make to increase in molecular product
Add electron-donating group amino, reduces molecular oxidation current potential；The methyl on phenyl ring is aoxidized again later, prepares corresponding acid,
Due to before oxidation reaction, increasing electron-donating group on 2- nitro -4- methylsulfonyltoluenes, oxidizing potential reduces, therefore,
Oxidation reaction difficulty reduces, and reaction is made to be more easy to carry out.
2. the catalyst for preparing the reaction of 2- nitryl-4-thiamphenicol benzoic acids using 2- nitro -4- methylsulfonyltoluenes is five
V 2 O, but vanadic anhydride is severe poisonous chemicals, dosage is bigger, bigger to the pollution of environment, to operating personnel's
The influence of health is also more serious；And after increasing amino on the phenyl ring of 2- nitro -4- methylsulfonyltoluenes, the oxidation of reaction is difficult
Degree reduces, and the dosage of catalyst can greatly reduce, and so as to alleviate the severity of environmental pollution, weakens operating personnel's building ring
The danger level in border improves working environment.
3. before obtaining finished product, using the amino on the phenyl ring of calcium nitrite, hydrochloric acid and sodium hypophosphite elimination products,
To obtain final product 2- nitryl-4-thiamphenicol benzoic acids.With Asia is directly used in the other application documents applied on the same day
Nitric acid is compared, and the nitrous acid that calcium nitrite and hydrochloric acid of the present invention generate when reacting is reacted with the amino on phenyl ring immediately, is avoided
Directly using nitrous acid, there is a phenomenon where nitrous acid to decompose.
4. the present invention obtains a large amount of mother liquors while obtaining crude product, mother liquor is distilled, water and sulfuric acid is separately recovered,
The water of recycling can be not only used for the hydrolysis in S2, and can be used for absorbing the tail gas in S1；The sulfuric acid of recycling can be used as in S1
Reactant sulfuric acid improves material utilization to reduce the wasting of resources.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, other are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1 is the industrialization production method embodiment 1 and reality of a kind of efficient 2- nitryl-4-thiamphenicol benzoic acids of the present invention
Apply the process flow chart of example 2.
Fig. 2 is the industrialization production method embodiment 3 and reality of a kind of efficient 2- nitryl-4-thiamphenicol benzoic acids of the present invention
Apply the process flow chart of example 4.
Specific implementation mode
Technical solution is clearly and completely described below in conjunction with specific embodiments of the present invention.Obviously, described
Embodiment be only the present invention a part of the embodiment, instead of all the embodiments.Based on the embodiment of the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
It is specific as follows the present invention discloses a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids
Shown in each embodiment.
Embodiment 1
S1：By itrated compound 2- nitros -4- methylsulfonyltoluenes 650kg and the sulfuric acid 2000kg of volume ratio 70%, volume ratio
65% nitric acid 430kg mixing, stirs evenly, and 2kg catalyst vanadic anhydrides are added thereto, stirring, aoxidize anti-
It answers；The tail gas nitric oxide generated in reaction process is absorbed with water.
S2：800kg water is added in the mixed liquor prepared to S1, reaction is hydrolyzed in stirring.
S3：300kg water, stirring are added into mixture made from S2, filtering, centrifugation respectively obtain about 600kg crude products
With 3447kg mother liquors.Mother liquor is distilled, water and sulfuric acid are respectively obtained, the water of recycling can be used to the hydrolysis in S2, and can
For absorbing the tail gas in S1；The sulfuric acid of recycling can be used as the reactant sulfuric acid in S1.
S4：Liquid caustic soda (40% sodium hydroxide) 220kg and clear water 1500kg is added in the crude product obtained into S3, to thick
Product alkali soluble.
S5：The washing of 100kg clear water is added in mixed liquor into S4, filtrate about 2370kg and unreacted is recycled in filtering
2- nitro -4- methylsulfonyltoluenes 50kg.
S6：25% hydrochloric acid 300kg is added in filtrate into S5, carries out acid out.
S7：Clear water 500kg washings, 8000rpm centrifugations, removal sewage 2650kg are added in mixed liquor into S6.
S8：Product 2- nitryl-4-thiamphenicol benzoic acids 520kg dryings after being centrifuged in S7, remove the steam of 20kg, will
Product packaging and storage after drying.
Embodiment 2
S1：By itrated compound 2- nitros -4- methylsulfonyltoluenes 650kg and the sulfuric acid 1500kg of volume ratio 70%, volume ratio
65% nitric acid 400kg mixing, stirs evenly, and 2kg catalyst vanadic anhydrides are added thereto, stirring, aoxidize anti-
It answers；The tail gas nitric oxide generated in reaction process is absorbed with water.
S2：1000kg water is added in the mixed liquor prepared to S1, reaction is hydrolyzed in stirring.
S3：300kg water, stirring are added into mixture made from S2, filtering, centrifugation respectively obtain about 550kg crude products
With 3300kg mother liquors.Mother liquor is distilled, water and sulfuric acid are respectively obtained, the water of recycling can be not only used for the hydrolysis in S2, and can
For absorbing the tail gas in S1；The sulfuric acid of recycling can be used as the reactant sulfuric acid in S1.
S4：Liquid caustic soda (sodium hydroxide of mass ratio 45%) 220kg and clear water are added in the crude product obtained into S3
1500kg, to crude product alkali soluble.
S5：The washing of 100kg clear water is added in mixed liquor into S4, filtrate about 2250kg and unreacted is recycled in filtering
2- nitro -4- methylsulfonyltoluenes 40kg.
S6：The hydrochloric acid 300kg of volume ratio 25% is added in filtrate into S5, carries out acid out.
S7：Clear water 500kg washings, 8000rpm centrifugations, removal sewage about 2500kg are added in mixed liquor into S6.
S8：Product 2- nitryl-4-thiamphenicol benzoic acids 450kg dryings after being centrifuged in S7, remove the steam of about 20kg,
By the product packaging and storage after drying.
Embodiment 3
S1'：It by itrated compound 2- nitros -4- methylsulfonyltoluenes 650kg and iron powder 10kg, mixes, stirring, and gradually thereto
Bromine 300kg is added, is uniformly mixed, after reaction, Sodamide 280kg is added thereto, reaction is abundant, and being retained in container has
Product liquid and iron powder precipitation.
S1：Product liquid in S1 is mixed with the sulfuric acid 2000kg of volume ratio 70%, the nitric acid 430kg of volume ratio 65%
It closes, stirs evenly, and 0.5kg catalyst vanadic anhydrides are added thereto, stirring carries out oxidation reaction；It is produced in reaction process
Raw tail gas nitric oxide is absorbed with water.
S2：800kg water is added in the mixed liquor prepared to S1, reaction is hydrolyzed in stirring.
S3：300kg water, stirring are added into mixture made from S2, filtering, centrifugation respectively obtain about 850kg crude products
With 3300kg mother liquors.Mother liquor is distilled, water and sulfuric acid are respectively obtained, the water of recycling can be used to the hydrolysis in S2, and can
For absorbing the tail gas in S1；The sulfuric acid of recycling can be used as the reactant sulfuric acid in S1.
S3'：Calcium nitrite 260kg, the hydrochloric acid 80kg stirrings of volume ratio 10%, reaction are added into crude product made from S3
Completely；Sodium hypophosphite 140kg is added thereto, stirring, the reaction was complete, and centrifugation, the solid product that centrifugation is obtained is for follow-up
Alkali soluble is reacted.
S4：Liquid caustic soda (sodium hydroxide of mass ratio 40%) 220kg and clear water are added in the crude product obtained into S3
1500kg, to crude product alkali soluble.
S5：The washing of 100kg clear water is added in mixed liquor into S4, filtrate about 2600kg and unreacted is recycled in filtering
2- nitro -4- methylsulfonyltoluenes 25kg.
S6：The hydrochloric acid 300kg of volume ratio 25% is added in filtrate into S5, carries out acid out.
S7：Clear water 500kg washings, 8000rpm centrifugations, removal sewage 2500kg are added in mixed liquor into S6.
S8：Product 2- nitryl-4-thiamphenicol benzoic acids 575kg dryings after being centrifuged in S7, remove the steam of about 25kg,
By the product packaging and storage after drying.
Embodiment 4
S1'：It by itrated compound 2- nitros -4- methylsulfonyltoluenes 600kg and iron powder 8kg, mixes, stirring, and gradually thereto
Bromine 280kg is added, is uniformly mixed, after reaction, Sodamide 280kg is added thereto, reaction is abundant, and being retained in container has
Product liquid and iron powder precipitation.
S1：Product liquid in S1 is mixed with the sulfuric acid 2000kg of volume ratio 70%, the nitric acid 430kg of volume ratio 65%
It closes, stirs evenly, and 0.3kg catalyst vanadic anhydrides are added thereto, stirring carries out oxidation reaction；It is produced in reaction process
Raw tail gas nitric oxide is absorbed with water.
S2：700kg water is added in the mixed liquor prepared to S1, reaction is hydrolyzed in stirring.
S3：250kg water, stirring are added into mixture made from S2, filtering, centrifugation respectively obtain about 800kg crude products
With 3000kg mother liquors.Mother liquor is distilled, water and sulfuric acid are respectively obtained, the water of recycling can be used to the hydrolysis in S2, and can
For absorbing the tail gas in S1；The sulfuric acid of recycling can be used as the reactant sulfuric acid in S1.
S3'：Calcium nitrite 200kg, the hydrochloric acid 90kg stirrings of volume ratio 10%, reaction are added into crude product made from S3
Completely；Sodium hypophosphite 100kg is added thereto, stirring, the reaction was complete, and centrifugation, the solid product that centrifugation is obtained is for follow-up
Alkali soluble is reacted.
S4：Liquid caustic soda (sodium hydroxide of mass ratio 40%) 220kg and clear water are added in the crude product obtained into S3
1500kg, to crude product alkali soluble.
S5：The washing of 100kg clear water is added in mixed liquor into S4, filtrate about 2150kg and unreacted is recycled in filtering
2- nitro -4- methylsulfonyltoluenes 25kg.
S6：The hydrochloric acid 300kg of volume ratio 25% is added in filtrate into S5, carries out acid out.
S7：Clear water 500kg washings, 8000rpm centrifugations, removal sewage 2500kg are added in mixed liquor into S6.
S8：Product 2- nitryl-4-thiamphenicol benzoic acids about 555kg dryings after being centrifuged in S7, remove the water of about 23kg
Vapour, by the product packaging and storage after drying.
Analysis of experimental results
By the various embodiments described above experimental result it is found that the experimental method of each embodiment can successfully utilize 2- nitro -4- first
Sulfuryl toluene is prepared in 2- nitryl-4-thiamphenicol benzoic acids, especially embodiment 3 and embodiment 4, first to itrated compound 2- nitros-
4- methylsulfonyltoluenes are handled, and are first made to connect bromine group on phenyl ring, then bromine group is substituted by amino, are made to connect ammonia on phenyl ring
Base reduces molecular oxidation current potential to make to increase in molecular product electron-donating group；Oxygen is carried out to the methyl on phenyl ring again later
Change, prepare corresponding acid, since before oxidation reaction, electron-donating group is increased on 2- nitro -4- methylsulfonyltoluenes, aoxidizes
Current potential reduces, and significantly less to the dosage of catalyst vanadic anhydride, vanadic anhydride is severe poisonous chemicals, and dosage subtracts
The severity for alleviating environmental pollution less reduces the danger level of operating personnel's working environment；Before obtaining finished product, utilize
Calcium nitrite, hydrochloric acid and sodium hypophosphite eliminate the amino on phenyl ring, to obtain final product 2- nitryl-4-thiamphenicol benzoic acids.
Not only the dosage of severe poisonous chemicals catalyst vanadic anhydride greatly reduces in embodiment 3 and embodiment 4, and its products collection efficiency phase
Embodiment 1 and embodiment 2 are promoted, the safety of entire operating environment makes moderate progress.
Claims (8)
1. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids, which is characterized in that including following step
Suddenly：
S1：Itrated compound 2- nitro -4- methylsulfonyltoluenes are mixed with sulfuric acid, nitric acid, stirs, is aoxidized under catalysts conditions
Reaction；
S2：Water is added in the mixed liquor prepared to S1, reaction is hydrolyzed；
S3：Water is added into material made from S2, filtering, centrifugation respectively obtain crude product and mother liquor；
S4：Liquid caustic soda and clear water are added in the crude product obtained into S3, to crude product alkali soluble；
S5：Clear water washing is added in mixed liquor into S4, filtrate and unreacted 2- nitros -4- methylsulfonyl first are recycled in filtering
Benzene；
S6：Hydrochloric acid is added in filtrate into S5, carries out acid out；
S7：Clear water washing is added in mixed liquor into S6, centrifugation removes sewage；
S8：Product drying after being centrifuged in S7, packaging and storage.
2. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 1, special
Sign is：Before carrying out S1 steps, increase S1 '：After 2- nitro -4- methylsulfonyltoluenes are mixed with iron powder, liquid is added thereto
Bromine is uniformly mixed, and Sodamide is added thereto later, it is made fully to react, by final product liquid for follow-up anti-
Answer material.
3. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 2, special
Sign is：Increase S3 ' between S3 and S4：Calcium nitrite and hydrochloric acid are added into crude product made from S3, stirring has been reacted
Entirely；Sodium hypophosphite is added thereto, stirs, the reaction was complete, centrifugation, and the solid product that centrifugation is obtained is anti-for follow-up alkali soluble
It answers.
4. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 1, special
Sign is：The mother liquor obtained in S3 steps is distilled, water and sulfuric acid is separately recovered.
5. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 4, special
Sign is：The tail gas that oxidation reaction in S1 steps generates is passed through in the water of the distillation recovery of the mother liquor in S3, absorbs tail gas.
6. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 1, special
Sign is：Catalyst described in S1 is vanadic anhydride.
7. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 1, special
Sign is：Liquid caustic soda described in S4 is sodium hydroxide.
8. a kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids according to claim 1, special
Sign is：Sulfuric acid used is the sulfuric acid of volume ratio 70% in S1, and the nitric acid is the nitric acid of volume ratio 65%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810725288.7A CN108752246A (en) | 2018-07-04 | 2018-07-04 | A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810725288.7A CN108752246A (en) | 2018-07-04 | 2018-07-04 | A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108752246A true CN108752246A (en) | 2018-11-06 |
Family
ID=63972193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810725288.7A Withdrawn CN108752246A (en) | 2018-07-04 | 2018-07-04 | A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108752246A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254456A (en) * | 2020-03-31 | 2020-06-09 | 青岛科技大学 | Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid |
-
2018
- 2018-07-04 CN CN201810725288.7A patent/CN108752246A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254456A (en) * | 2020-03-31 | 2020-06-09 | 青岛科技大学 | Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102399201A (en) | Method for preparing 5-hydroxymethylfurfural by solid acid catalysis | |
| CN103030232A (en) | Method for treating titanium-containing waste liquid produced by polyolefin catalyst | |
| CN109912413B (en) | Method for synthesizing butyl oleate by catalyzing oleic acid-based ionic liquid microemulsion | |
| CN108752246A (en) | A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids | |
| CN110862323A (en) | Synthesis method of diaminodiphenylethane compound | |
| CN108715580A (en) | A kind of industrialized preparing process of 2- nitryl-4-thiamphenicol benzoic acids | |
| CN108715581A (en) | A kind of preparation method of 2- nitryl-4-thiamphenicol benzoic acids | |
| CN110437056B (en) | Method for industrially preparing 2,3,4, 5-tetrafluorobenzoic acid | |
| CN106866399B (en) | Tetrachlorobenzoquinone and preparation method thereof | |
| CN114685253A (en) | Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone | |
| CN108752247A (en) | A kind of industrialized preparing process of the 2- nitryl-4-thiamphenicol benzoic acids of low stain | |
| CN104174436A (en) | Barium sulfonate catalyst and application thereof in synthesis of D,L-P-hydroxyphenyl hydantoin | |
| CN105439870A (en) | Method for recycling recycled N,N'-dicyclohexylurea | |
| CN113318730B (en) | δ-MnO2Catalyst, preparation method and application thereof | |
| CN113214145B (en) | Vitamin B6 production method | |
| CN108689821B (en) | Method for regenerating chloranil by oxidizing hydrogen peroxide | |
| CN101328113A (en) | Industrialized production method of hexafluoroacetone | |
| CN104557810A (en) | Method for producing furfuraldehyde from pentose solution by adopting impinging stream reactor | |
| CN110845302A (en) | Method for preparing ethylene glycol based on polyethylene carbonate | |
| CN106380429A (en) | Method for synthesizing 2-nitro-methylsulfonylbenzoic acid | |
| CN106146302B (en) | The preparation method of propionic ester | |
| CN113735746B (en) | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid | |
| CN103923056A (en) | Synthetic method of 3, 4-methylene dioxybenzaldehyde | |
| CN116924947B (en) | Process for synthesizing 4,4' -dichlorodiphenyl sulfone | |
| CN114890865B (en) | Preparation method of chloromethyl bromoethyl benzene |
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 |
Application publication date: 20181106 |
|
| WW01 | Invention patent application withdrawn after publication |