CN109020915A - A method of improving the nitrification selectivity of 1,2- diazoxy naphthalene -4- sulfonic acid - Google Patents
A method of improving the nitrification selectivity of 1,2- diazoxy naphthalene -4- sulfonic acid Download PDFInfo
- Publication number
- CN109020915A CN109020915A CN201811096104.1A CN201811096104A CN109020915A CN 109020915 A CN109020915 A CN 109020915A CN 201811096104 A CN201811096104 A CN 201811096104A CN 109020915 A CN109020915 A CN 109020915A
- Authority
- CN
- China
- Prior art keywords
- sulfonic acid
- nitrification
- selectivity
- diazoxy naphthalene
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/12—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms condensed with carbocyclic rings or ring systems
Abstract
A kind of method for the nitrification selectivity improving 1,2- diazoxy naphthalene -4- sulfonic acid, method includes the following steps: (1) adds in organic acid anhydride injection reaction kettle 1,2- diazoxy naphthalene -4- sulfonic acid, be cooled to certain temperature；(2) it is slowly added to nitrating agent and is nitrified and carried out insulation reaction, add water dilution after completion of the reaction, product is filtered to obtain after standing still for crystals.Compared with previous reaction system, the reaction system of this method has the characteristics that more convenient operation, nitrification regioselectivity are higher, more environment-friendly.
Description
Technical field
The present invention relates to a kind of methods of nitrification selectivity for improving 1,2- diazoxy naphthalene -4- sulfonic acid.
Background technique
1,2- diazoxy naphthalene -4- sulfonic acid is the important intermediate for synthesizing 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid,
It is widely used in synthesizing the dyestuffs such as the pink B of acid complexing, acid mordant black R, acid complex salt GGN, Acid Chrome Bordeaux BN.
The traditional handicraft of compound de-nitrification unit reaction is to be nitrified with the nitration mixture that nitric acid-sulfuric acid forms to reactant, this method meeting
A large amount of acid waste waters are generated, serious pollution is all caused to water resource and atmosphere, in addition the polynitration side reaction of this method and area
Field selectivity is low, these are all the problems for perplexing industry always.In order to improve reaction yield, reduce by-product, researcher is in original
Have and have developed a variety of improved procedures on Process ba- sis, including organic solvent is added, or hydrogen peroxide and ferrous sulfate cooperation is added
Specific agitating mode etc. technique.But these improve technique still without the scope for being detached from sulfuric acid and nitric acid, trade waste
Seriously polluted problem is not solved at all, therefore nitrification highly selective for 1,2- diazoxy naphthalene -4- sulfonic acid is made
The R and D of standby 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid technique are not interrupted always.
Summary of the invention
Its purpose of the invention, which is that, provides a kind of side of nitrification selectivity for improving 1,2- diazoxy naphthalene -4- sulfonic acid
Method solves existing method and all causes serious pollution to water resource and atmosphere in the presence of that can generate a large amount of acid waste waters, and exists
Polynitration side reaction and the low problem of regioselectivity have more convenient operation, nitrification regioselectivity higher, more environment-friendly
The characteristics of.
It adopts the technical scheme that achieve the above object, a kind of nitrification improving 1,2- diazoxy naphthalene -4- sulfonic acid
The method of selectivity, method includes the following steps:
(1) organic acid anhydride is injected in reaction kettle, adds 1,2- diazoxy naphthalene -4- sulfonic acid, is cooled to certain temperature；
(2) it is slowly added to nitrating agent and is nitrified and carried out insulation reaction, dilution is added water after completion of the reaction, after standing still for crystals
Filter to obtain product.
The organic acid anhydride is the mixture of acetic anhydride or propionic andydride or both.
The ratio of the weight of the weight and 1,2- diazoxy naphthalene -4- sulfonic acid of the organic acid anhydride is 1.5: 1 ~ 3
: between 1.
The nitration reaction temperature is 20oC ~ 30 oBetween C.
The mixture that the nitrating agent is potassium nitrate and potassium acid sulfate weight is 1: 1.4.
Beneficial effect
The present invention has the following advantages that compared with prior art.
It is an advantage of the invention that the reaction condition of this method does not need the concentrated sulfuric acid and concentrated nitric acid, to more environment-friendly, nitre
The regioselectivity of change is high, and yield is preferable, and product is easy to purify etc..
Specific embodiment
A kind of method for the nitrification selectivity improving 1,2- diazoxy naphthalene -4- sulfonic acid, method includes the following steps:
(1) organic acid anhydride is injected in reaction kettle, adds 1,2- diazoxy naphthalene -4- sulfonic acid, is cooled to certain temperature；
(2) it is slowly added to nitrating agent and is nitrified and carried out insulation reaction, dilution is added water after completion of the reaction, after standing still for crystals
Filter to obtain product.
The organic acid anhydride is the mixture of acetic anhydride or propionic andydride or both.
The ratio of the weight of the weight and 1,2- diazoxy naphthalene -4- sulfonic acid of the organic acid anhydride is 1.5: 1 ~ 3
: between 1.
The nitration reaction temperature is 20oC ~ 30 oBetween C.
The mixture that the nitrating agent is potassium nitrate and potassium acid sulfate weight is 1: 1.4.
The present invention solves the technical problem of the systems for thoroughly getting rid of sulfuric acid and nitric acid, to environment close friend's relatively
The highly selective nitrification of 1,2- diazoxy naphthalene -4- sulfonic acid is synthesized 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid by nitrification system；
Its process conditions is using acid anhydrides as reaction dissolvent, and the potassium nitrate of macrocation radius is that nitrating agent nitrifies raw material, can
To obtain product 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid with high selectivity.
The highly selective nitrification of 1,2- diazoxy naphthalene -4- sulfonic acid of the invention synthesizes 6- nitro -1,2- diazoxy naphthalene -4-
The reaction equation of sulfonic acid is as follows:
In step of the present invention, after acid anhydrides is added in 1,2- diazoxy naphthalene -4- sulfonic acid, system temperature can rise a tentering
Degree, in order to obtain better reaction selectivity, it would be desirable to system is cooled to certain temperature, this temperature is 20oC ~ 30 oC
Between；
In step of the present invention, acid anhydrides is added in 1,2- diazoxy naphthalene -4- sulfonic acid, after system is cooled to certain temperature,
It is slowly added to nitrating agent to be nitrified, the group of nitrating agent becomes the mixture of potassium nitrate and potassium acid sulfate 1:1, after adding nitrating agent
It insulation reaction 45 minutes, is diluted with water, product 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid can be precipitated at this time.In crude product
The content of 6- nitro product is greater than 93%, the content much higher than in traditional handicraft 80% or so, and by-product is more friendly to environment
It is good.
Embodiment 1
It weighs in 50 kg acetic anhydrides investment reaction kettle, is slowly added to 1,2- diazoxy naphthalene -4- sulfonic acid, 25 kg, stirs to abundant
Dissolution, cools to 25 DEG C, is slowly added to the mixture of 10 kg potassium nitrate and 14 kg potassium acid sulfates, finish insulation reaction 45 and divide
Clock pours into 25 kg of cold water, crystallization to reaction solution, and filtering obtains 28.5 kg of 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid, produces
The HPLC purity of product is 93.4%, total recovery 95%.
Embodiment 2
It weighs in 50 kg acetic anhydrides investment reaction kettle, is slowly added to 1,2- diazoxy naphthalene -4- sulfonic acid, 25 kg, stirs to abundant
Dissolution, cools to 30 DEG C, is slowly added to the mixture of 10 kg potassium nitrate and 14 kg potassium acid sulfates, finish insulation reaction 45 and divide
Clock pours into 50 kg of cold water, crystallization to reaction solution, and filtering obtains 26.5 kg of 6- nitro -1,2- diazoxy naphthalene -4- sulfonic acid, produces
The HPLC purity of product is 95.1%, total recovery 90%.
Claims (5)
1. it is a kind of improve 1,2- diazoxy naphthalene -4- sulfonic acid nitrification selectivity method, which is characterized in that this method include with
Lower step:
Organic acid anhydride is injected in reaction kettle, 1,2- diazoxy naphthalene -4- sulfonic acid is added, is cooled to certain temperature；
It is slowly added to nitrating agent to be nitrified and carry out insulation reaction, adds water dilution after completion of the reaction, mistake after standing still for crystals
Filter to obtain product.
2. a kind of raising 1 according to claim 1, the method for the nitrification selectivity of 2- diazoxy naphthalene -4- sulfonic acid,
It is characterized in that, the organic acid anhydride is the mixture of acetic anhydride or propionic andydride or both.
3. a kind of method of nitrification selectivity for improving 1,2- diazoxy naphthalene -4- sulfonic acid according to claim 1, special
Sign is that the ratio of the weight of the weight and 1,2- diazoxy naphthalene -4- sulfonic acid of the organic acid anhydride is 1.5: 1 ~ 3:
Between 1.
4. a kind of method of nitrification selectivity for improving 1,2- diazoxy naphthalene -4- sulfonic acid according to claim 1, special
Sign is that the nitration reaction temperature is 20oC ~ 30 oBetween C.
5. a kind of method of nitrification selectivity for improving 1,2- diazoxy naphthalene -4- sulfonic acid according to claim 1, special
Sign is that the nitrating agent is the mixture that potassium nitrate is 1: 1.4 with potassium acid sulfate weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811096104.1A CN109020915B (en) | 2018-09-19 | 2018-09-19 | Method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811096104.1A CN109020915B (en) | 2018-09-19 | 2018-09-19 | Method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109020915A true CN109020915A (en) | 2018-12-18 |
| CN109020915B CN109020915B (en) | 2022-12-27 |
Family
ID=64617383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811096104.1A Active CN109020915B (en) | 2018-09-19 | 2018-09-19 | Method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109020915B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995594A (en) * | 2020-09-27 | 2020-11-27 | 恒升化工有限公司 | Continuous nitration method of 1, 2-diazoxynaphthalene-4-sulfonic acid and product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516195A (en) * | 2011-12-09 | 2012-06-27 | 江苏远征化工有限公司 | Production method of 6-nitro-1,2,4-sulfonic acid |
| CN104628670A (en) * | 2014-11-05 | 2015-05-20 | 九江善水科技有限公司 | 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid and preparation method thereof |
| CN104817516A (en) * | 2015-04-19 | 2015-08-05 | 李凤燕 | Method for preparing 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid |
| CN105732536A (en) * | 2016-03-14 | 2016-07-06 | 九江善水科技有限公司 | Solvent nitration method for 1,2-naphthoxydiazo-4-sulfonic acid |
-
2018
- 2018-09-19 CN CN201811096104.1A patent/CN109020915B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516195A (en) * | 2011-12-09 | 2012-06-27 | 江苏远征化工有限公司 | Production method of 6-nitro-1,2,4-sulfonic acid |
| CN104628670A (en) * | 2014-11-05 | 2015-05-20 | 九江善水科技有限公司 | 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid and preparation method thereof |
| CN104817516A (en) * | 2015-04-19 | 2015-08-05 | 李凤燕 | Method for preparing 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid |
| CN105732536A (en) * | 2016-03-14 | 2016-07-06 | 九江善水科技有限公司 | Solvent nitration method for 1,2-naphthoxydiazo-4-sulfonic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995594A (en) * | 2020-09-27 | 2020-11-27 | 恒升化工有限公司 | Continuous nitration method of 1, 2-diazoxynaphthalene-4-sulfonic acid and product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109020915B (en) | 2022-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20230044183A1 (en) | Purification method of progesterone | |
| CN109020915A (en) | A method of improving the nitrification selectivity of 1,2- diazoxy naphthalene -4- sulfonic acid | |
| CN111704578A (en) | Continuous production method of 2-methyl-5-nitroimidazole | |
| CN108129322B (en) | Synthetic method of 2-nitro-3-methylbenzoic acid | |
| CN108395381B (en) | Synthesis method of 1, 4-diamino anthraquinone leuco body | |
| CN102875435A (en) | Organic thiosulfuric acid derivative preparation method | |
| CN108358806A (en) | One inter-species acetaminophenol is continuously synthesizing to method | |
| CN109970163A (en) | A kind of recycling processing method of azo dye wastewater | |
| EP4148061A1 (en) | Post-treatment method of sucrose-6-carboxylic ester chlorination reaction liquid | |
| CN107200691B (en) | Preparation method of substituted p-phenylenediamine hydrochloride | |
| CN102627589A (en) | Method and technology for synthesizing and preparing 4-isopropylbenzenesulfonyl chloride through two steps | |
| CN113402379B (en) | Green production method of 1,1 '-binaphthyl-8,8' -dicarboxylic acid | |
| CN102936213B (en) | Clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid | |
| CN107827821B (en) | Continuous flow clean production process of pyrazolone series products | |
| CN108752230B (en) | Synthesis method of key intermediate of contrast agent iodixanol impurity E | |
| CN109053456B (en) | Method for refining Jina | |
| CN108191611B (en) | Continuous synthesis method of 2, 5-dimethylphenol | |
| CN110343046A (en) | A kind of production method improving paranitrochlorobenzene purity | |
| CN110407702A (en) | A kind of preparation method of eltrombopag olamine key intermediate 3 '-amino -2 '-xenol -3- carboxylic acid | |
| JPH0418062A (en) | Treatment of hydrochloric acid, sulfuric acid and aqueous mother liquor containing hydroxylammonium salt and ammonium salt thereof | |
| CN114920670B (en) | Preparation method of 5-chloro-2-aminobenzenesulfonamide | |
| CN112724089B (en) | Synthesis process of 2-amino-3-bromo-6-chloropyrazine | |
| CN114075258B (en) | Preparation method of hydrocortisone | |
| CN108358819B (en) | Method for recovering R salt from K acid production mother liquor | |
| US1314923A (en) | Chester e |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |