CN109456231A - A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide - Google Patents
A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide Download PDFInfo
- Publication number
- CN109456231A CN109456231A CN201811527560.7A CN201811527560A CN109456231A CN 109456231 A CN109456231 A CN 109456231A CN 201811527560 A CN201811527560 A CN 201811527560A CN 109456231 A CN109456231 A CN 109456231A
- Authority
- CN
- China
- Prior art keywords
- chlorobenzene
- nitro
- sulfonamide
- preparation
- added
- 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
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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 provides a kind of preparation methods of 2- nitro-chlorobenzene -4- sulfonamide, method includes the following steps: 2- nitro-chlorobenzene -4- sulfonic acid chloride and ammonium salt are added to the water, use turkey red oil as wetting agent, by the way that the pH value of inorganic base maintenance system is added in 7-9, control temperature carries out aminating reaction under conditions of 30-60 DEG C, obtains corresponding product 2- nitro-chlorobenzene -4- sulfonamide.The present invention replaces ammonium hydroxide using ammonium salt, avoids ammonium hydroxide volatilization bring adverse effect, environmental pollution is few, can effectively avoid the harm to human health.Meanwhile one step all raw materials are added, it is time-consuming and laborious to reduce batch charging, improves reaction condition, react reaction can under the conditions of lower ph, reduces 2- nitro-chlorobenzene -4- sulfonic acid chloride and decompose, reduce the generation of by-product, yield can be improved 10% or more.And since reaction temperature is higher, on the rocks, reduction energy consumption is not needed.
Description
Technical field
The present invention relates to a kind of preparation methods of 2- nitro-chlorobenzene -4- sulfonamide, belong to dyestuff intermediate synthetic technology neck
Domain.
Background technique
Ortho-Aminophenol -4- sulfonamide is a kind of important dyestuff intermediate, can be used for producing acid dyes, directly dye
Material and solvent dye.Such as: acid yellow 11 4,116:1,128,137,151；Acid orange 60,64,76,87,87:1,88,107,
139,162,173；Acid red 18 2,213,277,296,445；Acid violet 68,70,87；Blue VRS 68；Acid green 56；Directly
Red 98,181；Directly purple 46,66；Solvent red 102 etc..
And 2- nitro-chlorobenzene -4- sulfonamide is the critical materials of synthetic intermediate Ortho-Aminophenol -4- sulfonamide.It closes at present
Universal method at 2- nitro-chlorobenzene -4- sulfonamide is that 2- nitro-chlorobenzene -4- sulfonic acid chloride and ammonium hydroxide are condensed in a low temperature of 15 DEG C
Preparation, chemical equation are as follows:
Its synthesis technology are as follows: 2000 liters of water, 305 kilogram 26% of ammonium hydroxide, (ammonium hydroxide mole are added in 6000 liters of reaction kettles
Number 4.665mol, concentration 3.5%), with 4-5 hours addition 2- nitro-chlorobenzene -4- sulfonic acid chlorides, 100 kilograms are rolled over, (1.828mol,
Ammonia: sulphonyl cl molar ratio 2.55:1), condensation temp is no more than 20 degrees Celsius.Slurry is heated slowly to 35-38 degrees Celsius, protects
Temperature 3 hours.20 degrees Celsius are cooled back to, filtering, cold water washs, yield 85%.
This processing disadvantages is, reaction starts ammonia spirit pH close to 11, and in entire ammonifying process, material liquid pH is not less than
9.5, since -4 sulfonic acid chloride of 2- nitro-chlorobenzene is unstable under high pH conditions, it is easy to happen decomposition, generates by-product: 2- nitro
Chlorobenzene -4- sulfonic acid (see 1 equation of side reaction).The ammonium hydroxide of 2 molecules can occur under high ph-values simultaneously sulfonic acid chloride and a molecule is anti-
It answers, is formed two contracting things (see 2 equation of side reaction), cause amination steps by-product more, major product 2- nitro-chlorobenzene -4- sulfonamide is received
Rate is low.And the technique improves product yield and quality, generallys use for a long time, in batches to reduce the by-products of amination steps
2- nitro-chlorobenzene -4- sulfonic acid chloride is added, it is irritant to nose, larynx and lung after sucking since the volatility of ammonium hydroxide is very strong, cause cough
It coughs, shortness of breath and asthma etc.；Can due to laryngeal edema death by suffocation；Pulmonary edema can occur, cause death.Ammonium hydroxide is splashed into intraocularly, can
It causes serious harm, even results in blindness, skin contact can cause to burn.Chronic Effect: low concentration contacts repeatedly, can cause branch gas
Guan Yan.Skin contacts repeatedly, can cause dermatitis.Therefore long-time batch charging causes worker to be frequently exposed to ammonia environment for a long time
Under, very big harm is brought to industrial production environment and operator.
Since aminating reaction is exothermic reaction, in order to be maintained at less than 20 degrees Celsius of condensations, industrial processes are continuous
Cooling on the rocks, summer is especially true, so that reaction material liquid volume constantly increases, industrial production final products 2- nitroxyl chloride at present
The method of benzene -4- sulfonamide is ammonification, basic hydrolysis, reduction one kettle way, and intermediate each step does not separate, since ammonifying process volume is more come
Bigger, cause the reduction of final products 2- nitro-chlorobenzene -4- sulfonamide production capacity；Final products 2- nitro-chlorobenzene -4- sulfonamide simultaneously
There is certain solubility in water, the consequence that material liquid volume increases is that product yield reduces.
Summary of the invention
The present invention is directed to the above defect existing in the prior art, proposes a kind of more environmentally-friendly, efficient and high income 2-
The preparation method of nitro-chlorobenzene -4- sulfonamide.
The purpose of the present invention is what is be achieved by the following technical programs, a kind of system of 2- nitro-chlorobenzene -4- sulfonamide
Preparation Method, which is characterized in that method includes the following steps:
2- nitro-chlorobenzene -4- sulfonic acid chloride and ammonium salt are added to the water, use turkey red oil as wetting agent, by the way that nothing is added
The pH value of machine alkali maintenance system controls temperature and carries out aminating reaction under conditions of 30-60 DEG C, obtain corresponding product in 7-9
2- nitro-chlorobenzene -4- sulfonamide.
The present invention replaces ammonium hydroxide by using ammonium salt, can greatly reduce the volumetric usage of reaction material liquid, and react temperature
Degree do not need it is very low, be not required to however stop it is on the rocks so that reaction temperature is maintained reduced levels, production capacity can be effectively improved.And pass through
Using solid ammonium salt replace ammonium hydroxide, also can be avoided using the problem of existing high volatile, be more advantageous to when ammonium hydroxide reduce pair
The health hazard of human body improves production environment.Importantly, being carried out by using ammonium salt and 2- nitro-chlorobenzene -4- sulfonic acid chloride
Reaction does not need that 2- nitro-chlorobenzene -4- sulfonic acid chloride is added portionwise for a long time, greatly reduces the reaction time.Simultaneously as reaction
PH value is lower when comparing using ammonium hydroxide, the decomposition of 2- nitro-chlorobenzene -4- sulfonic acid chloride is reduced, to reduce the generation of by-product, most
Whole yield can be improved 10% or more.
In the preparation method of above-mentioned 2- nitro-chlorobenzene -4- sulfonamide, preferably, passing through during the aminating reaction
Inorganic base maintenance system pH value is added and maintains 7-8.By maintaining the pH value, is conducive to the more complete progress of reaction, improves and receive
The effect of rate.As a further preference, the ammonium salt is selected from one or more of ammonium bicarbonate, ammonium chloride and ammonium sulfate, described
Inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
In the preparation method of above-mentioned 2- nitro-chlorobenzene -4- sulfonamide, preferably, the 2- nitro-chlorobenzene -4- sulphonyl
The mass ratio 1:1-4 of chlorine and ammonium salt.
In the preparation method of above-mentioned 2- nitro-chlorobenzene -4- sulfonamide, preferably, the dosage of the turkey red oil is
The 0.5%-3% of the quality of 2- nitro-chlorobenzene -4- sulfonic acid chloride.Since turkey red oil can effectively moisten benzene sulfonyl chloride, make
Aminating reaction more favorably carries out, and has good effect to yield is improved.
In the preparation method of above-mentioned 2- nitro-chlorobenzene -4- sulfonamide, preferably, the temperature of the aminating reaction is
40-55℃.Reaction rate is most fast under the reaction temperature.
In the preparation method of above-mentioned 2- nitro-chlorobenzene -4- sulfonamide, preferably, this method specifically:
In water, 2- nitro-chlorobenzene -4- sulfonic acid chloride is first added and turkey red oil carries out after being beaten processing uniformly, adds
Ammonium salt is mixed, and then, the pH value that the aqueous solution maintenance system of inorganic base is added dropwise is 7-8, then controlled at 45-55 DEG C,
Aminating reaction terminates, and is post-processed, and corresponding 2- nitro-chlorobenzene -4- sulfonamide is obtained.
In conclusion compared with prior art, the present invention having the advantage that
The present invention replaces ammonium hydroxide using ammonium salt, avoids ammonium hydroxide volatilization bring adverse effect, environmental pollution is few, can
Effectively avoid the harm to human health.Meanwhile one step all raw materials are added, it is time-consuming and laborious to reduce batch charging, improves anti-
Condition is answered, react reaction can under the conditions of lower ph, 2- nitro-chlorobenzene -4- sulfonic acid chloride is reduced and decomposes, reduce by-product
Generation, yield can be improved 10% or more.And since reaction temperature is higher, on the rocks, reduction energy consumption is not needed.
Specific embodiment
Below by specific embodiment, the technical solutions of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
Add water 200g, 2- nitro-chlorobenzene -4- sulfonic acid chloride wet product 80g (mass fraction 61.2%) in clean there-necked flask,
2- nitro-chlorobenzene -4- sulfonic acid chloride 49g and turkey red oil 1g is converted into as wetting agent, stirring to pulp is handled 30 minutes, then
Solid ammonium chloride 40g is added, stirs 15 minutes, the sodium hydrate aqueous solution that mass fraction is 20%, the pH of regulation system is added dropwise
Value makes material liquid pH value be increased to 7-9, then, is warming up to 30-55 DEG C of heat preservation and carries out aminating reaction, divided in reaction process using quality
Number for 20% sodium hydrate aqueous solution maintenance system ammonification feed liquid pH value between 7-9, until aminating reaction terminal is complete,
Cooling that product is precipitated completely, filtering, filter cake is washed twice with cold water, wet product is dried under the conditions of 95 DEG C, obtains ammonification production
Product 2- nitro-chlorobenzene -4- sulfonamide 42g, yield 93.7%, purity reaches 99% or more.
Embodiment 2
Add water 300g, 2- nitro-chlorobenzene -4- sulfonic acid chloride wet product 80g (mass fraction 61.2%) in clean there-necked flask,
2- nitro-chlorobenzene -4- sulfonic acid chloride 49g and turkey red oil 0.5g is converted into as wetting agent, stirring to pulp is handled 30 minutes,
Solid ammonium chloride 64g is added, is stirred 30 minutes, the sodium hydrate aqueous solution that mass fraction is 10% is added dropwise, regulation system
PH value makes material liquid pH value be increased to 7 or so, then, is warming up to 60 DEG C of heat preservations and carries out aminating reaction 3 hours, use in reaction process
The pH value for the sodium hydrate aqueous solution maintenance system ammonification feed liquid that mass fraction is 15% is between 7-8, until aminating reaction end
Completely, cooling that product is precipitated completely, filtering, filter cake is washed twice with cold water, wet product is dried under the conditions of 90 DEG C, obtained point
Ammonification product 2- nitro-chlorobenzene -4- sulfonamide 38g, yield 84.7%, purity reaches 99% or more.
Embodiment 3
Add water 200g, 2- nitro-chlorobenzene -4- sulfonic acid chloride wet product 80g (mass fraction 61.2%) in clean there-necked flask,
2- nitro-chlorobenzene -4- sulfonic acid chloride 49g and turkey red oil 1.5g is converted into as wetting agent, stirring to pulp is handled 40 minutes,
Solid ammonium bicarbonate 49g is added, is stirred 30 minutes, the potassium hydroxide solution that mass fraction is 15%, the pH value of regulation system is added dropwise
So that material liquid pH value is increased to 8 or so, then, is warming up to 40 DEG C of heat preservations and carries out aminating reaction 3 hours, quality is used in reaction process
The pH value for the potassium hydroxide aqueous solution maintenance system ammonification feed liquid that score is 15% is between 7-9, until aminating reaction terminal is complete
Entirely, cooling that product is precipitated completely, filtering, filter cake is washed twice with cold water, wet product is dried under the conditions of 95 DEG C, obtains ammonification
Product 2- nitro-chlorobenzene -4- sulfonamide 41g, yield 91.4%, purity reaches 99.6% or more.
Embodiment 4
Add water 300g, 2- nitro-chlorobenzene -4- sulfonic acid chloride wet product 80g (mass fraction 61.2%) in clean there-necked flask,
It being converted into 2- nitro-chlorobenzene -4- sulfonic acid chloride 49g and turkey red oil 1.2g and makees wetting agent, stirring to pulp is handled 40 minutes, then
Solid ammonium sulfate 52g is added, stirs 30 minutes, the potassium hydroxide aqueous solution that mass fraction is 17%, the pH of regulation system is added dropwise
Value makes material liquid pH value be increased to 7 or so, then, is warming up to 55 DEG C of heat preservations and carries out aminating reaction 4 hours, matter is used in reaction process
The pH value for the potassium hydroxide aqueous solution maintenance system ammonification feed liquid that score is 17% is measured between 7-9, until aminating reaction terminal
Completely, cooling that product is precipitated completely, filtering, filter cake is washed twice with cold water, wet product is dried under the conditions of 95 DEG C, obtains ammonia
Change product 2- nitro-chlorobenzene -4- sulfonamide 39g, yield 87.0%, purity reaches 99.5% or more.
Embodiment 5
Add water 300g, 2- nitro-chlorobenzene -4- sulfonic acid chloride wet product 80g (mass fraction 61.2%) in clean there-necked flask,
It being converted into 2- nitro-chlorobenzene -4- sulfonic acid chloride 49g and turkey red oil 1.1g and makees wetting agent, stirring to pulp is handled 30 minutes, then
Solid ammonium chloride 196g is added, stirs 30 minutes, the sodium hydrate aqueous solution that mass fraction is 20%, the pH of regulation system is added dropwise
Value makes material liquid pH value be increased to 7 or so, then, is warming up to 50 DEG C of heat preservations and carries out aminating reaction 4.5 hours, use in reaction process
The pH value for the sodium hydrate aqueous solution maintenance system ammonification feed liquid that mass fraction is 20% is between 7-8, until aminating reaction end
Completely, cooling that product is precipitated completely, filtering, filter cake is washed twice with cold water, wet product is dried under the conditions of 95 DEG C, obtained point
Ammonification product 2- nitro-chlorobenzene -4- sulfonamide 39g, yield 89.2%, purity reaches 99.6% or more.
Specific embodiment described in the present invention only illustrate the spirit of the present invention by way of example.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (8)
1. a kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide, which is characterized in that method includes the following steps:
2- nitro-chlorobenzene -4- sulfonic acid chloride and ammonium salt are added to the water, use turkey red oil as wetting agent, by the way that inorganic base is added
The pH value of maintenance system controls temperature and carries out aminating reaction under conditions of 30-60 DEG C, obtain corresponding product 2- nitre to 7-9
Base chlorobenzene -4- sulfonamide.
2. the preparation method of 2- nitro-chlorobenzene -4- sulfonamide according to claim 1, which is characterized in that the aminating reaction
7-8 is maintained by the way that alkaline reagent control system pH value is added in the process.
3. according to claim 1-nitro-chlorobenzene-4- sulfonamide preparation method, which is characterized in that the ammonium salt is selected from chlorine
Change one or more of ammonium, ammonium bicarbonate and ammonium sulfate.
4. the preparation method of the according to claim 1 or 2 or 3 2- nitro-chlorobenzene -4- sulfonamide, which is characterized in that the nothing
Machine alkali is selected from one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
5. the preparation method of the according to claim 1 or 2 or 3 2- nitro-chlorobenzene -4- sulfonamide, which is characterized in that the 2-
The mass ratio 1:1-4 of nitro-chlorobenzene -4- sulfonic acid chloride and ammonium salt.
6. the preparation method of the according to claim 1 or 2 or 3 2- nitro-chlorobenzene -4- sulfonamide, which is characterized in that the soil
The dosage of its red oil of ear is the 0.5%-3% of the quality of 2- nitro-chlorobenzene -4- sulfonic acid chloride.
7. the preparation method of the according to claim 1 or 2 or 3 2- nitro-chlorobenzene -4- sulfonamide, which is characterized in that the ammonia
The temperature for changing reaction is 40-55 DEG C.
8. the preparation method of the according to claim 1 or 2 or 3 2- nitro-chlorobenzene -4- sulfonamide, which is characterized in that this method
Specifically:
In water, 2- nitro-chlorobenzene -4- sulfonic acid chloride is first added and turkey red oil carries out after being beaten processing uniformly, adds ammonium salt
It is mixed, then, the pH value that the aqueous solution regulation system of inorganic base is added dropwise is 7-8, then controlled at 45-55 DEG C, ammonification
Reaction terminates, and is post-processed, and corresponding 2- nitro-chlorobenzene -4- sulfonamide is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811527560.7A CN109456231A (en) | 2018-12-13 | 2018-12-13 | A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811527560.7A CN109456231A (en) | 2018-12-13 | 2018-12-13 | A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109456231A true CN109456231A (en) | 2019-03-12 |
Family
ID=65613164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811527560.7A Pending CN109456231A (en) | 2018-12-13 | 2018-12-13 | A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109456231A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163383A (en) * | 2021-12-24 | 2022-03-11 | 江苏丰山集团股份有限公司 | Green production process of nicosulfuron intermediate nicotinamide and sulfamide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB884206A (en) * | 1957-06-17 | 1961-12-06 | Du Pont | 4-alkoxymetanilamides and compositions containing them |
| CN101838225A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院成都生物研究所 | Sulfonylation methods of amine and derivative thereof |
| CN104592064A (en) * | 2014-12-30 | 2015-05-06 | 青岛双桃精细化工（集团）有限公司 | Synthetic method of 2-aminophenol-4-sulfonamide |
| CN104788347A (en) * | 2015-03-23 | 2015-07-22 | 大连奇凯医药科技有限公司 | Method for preparing 2-(trifluoromethoxy) benzene sulfonamide |
| CN105017098A (en) * | 2015-07-17 | 2015-11-04 | 大连奇凯医药科技有限公司 | Preparation technology of alkyloxybenzsulfamide and its derivatives |
| CN106699614A (en) * | 2015-07-20 | 2017-05-24 | 韶远科技（上海)有限公司 | Amplified synthesis method of 3-nitro-4-halogeno-benzenesulfonamide |
-
2018
- 2018-12-13 CN CN201811527560.7A patent/CN109456231A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB884206A (en) * | 1957-06-17 | 1961-12-06 | Du Pont | 4-alkoxymetanilamides and compositions containing them |
| CN101838225A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院成都生物研究所 | Sulfonylation methods of amine and derivative thereof |
| CN104592064A (en) * | 2014-12-30 | 2015-05-06 | 青岛双桃精细化工（集团）有限公司 | Synthetic method of 2-aminophenol-4-sulfonamide |
| CN104788347A (en) * | 2015-03-23 | 2015-07-22 | 大连奇凯医药科技有限公司 | Method for preparing 2-(trifluoromethoxy) benzene sulfonamide |
| CN105017098A (en) * | 2015-07-17 | 2015-11-04 | 大连奇凯医药科技有限公司 | Preparation technology of alkyloxybenzsulfamide and its derivatives |
| CN106699614A (en) * | 2015-07-20 | 2017-05-24 | 韶远科技（上海)有限公司 | Amplified synthesis method of 3-nitro-4-halogeno-benzenesulfonamide |
Non-Patent Citations (3)
| Title |
|---|
| ANDREW M. PETROS等: "Discovery of a Potent Inhibitor of the Antiapoptotic Protein Bcl-xL from NMR and Parallel Synthesis", 《J. MED. CHEM.》 * |
| HIROYUKI YASUI等: "N -Fluoro-(3,5-di-tert -butyl-4-methoxy)benzenesulfonimide (NFBSI): A sterically demanding electrophilic fluorinating reagent for enantioselective fluorination", 《JOURNAL OF FLUORINE CHEMISTRY 》 * |
| MARC Y. STEVENS等: "Synthesis of Sulfonyl Azides via Diazotransfer using an Imidazole-1-sulfonyl Azide Salt: Scope and 15N NMR Labeling Experiments", 《J. ORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163383A (en) * | 2021-12-24 | 2022-03-11 | 江苏丰山集团股份有限公司 | Green production process of nicosulfuron intermediate nicotinamide and sulfamide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105130858B (en) | A kind of process for cleanly preparing of sulfonated para-ester serving as dye intermediate | |
| CN107056663A (en) | The synthetic method of para-ester | |
| CN109456231A (en) | A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide | |
| CN111100044B (en) | Preparation method of alkyl zinc sulfinate series compounds | |
| CN103483230B (en) | Preparation method of sulfanilamide | |
| EP0077501B1 (en) | Process for the preparation of fluoroaromatic compounds substituted in the ortho position | |
| CN110903476B (en) | Preparation method of polyoxy alkenyl ether sulfate surfactant | |
| CN110143922A (en) | A kind of synthetic method of 1,1 '-dicaprolactam disulfides | |
| CN109651211A (en) | A method of preparing 2,3- sodium dimercaptopropane sulfonate | |
| CN111909061B (en) | Production process of 2-amino-3, 6, 8-naphthalene trisulfonic acid | |
| CN106752063A (en) | A kind of method of one pot process AZOpigments | |
| CN107986998A (en) | A kind of process for cleanly preparing of sulfonated para-ester serving as dye intermediate | |
| CN106831500A (en) | A kind of preparation method of G salt and its accessory substance R salt | |
| CN113603638A (en) | Synthetic method of 2, 3-pyridinedicarboxylic acid | |
| JPS63130129A (en) | Surfactant and its preparation | |
| CN107033044B (en) | A kind of preparation method of pair of trifluoromethylthio phenol | |
| CN103145593A (en) | Preparation method of 4,4'-diaminobenzenesulphonamide | |
| DK166965B1 (en) | METHOD FOR PREPARING DIMETHYLAMINOMETHYL COBPHERPHTHALOCYANINE WITH AVERAGE 1-4 DIMETHYLAMINOMETHYL GROUPS PR. MOLECULAR | |
| CN110156623B (en) | Method for preparing ioversol | |
| US2045475A (en) | Stable reduction compounds of the 4.7.4'.7'-tetra-alkyl-5.5'-dihalogenthioindigos and a process of preparing them | |
| CN107698503A (en) | A kind of preparation method of 8 fluorine quinoline and the preparation method of the fluorine quinoline of 3 iodine 8 | |
| CN108558712A (en) | It is a kind of using antifebrin as the method and P-aminobenzene-sulfonamide of Material synthesis high-purity P-aminobenzene-sulfonamide | |
| CN108003070A (en) | A kind of method of sulfonation in H acid production | |
| CN107216272A (en) | A kind of sour synthetic methods of environment-friendly type H | |
| JPS62111942A (en) | Production of 3,4,5,6-tetrafluorophthalic acid |
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: 20190312 |
|
| RJ01 | Rejection of invention patent application after publication |