CN105130856B - The preparation method of diphenyl ether sulfonyl azide compound - Google Patents
The preparation method of diphenyl ether sulfonyl azide compound Download PDFInfo
- Publication number
- CN105130856B CN105130856B CN201510513687.3A CN201510513687A CN105130856B CN 105130856 B CN105130856 B CN 105130856B CN 201510513687 A CN201510513687 A CN 201510513687A CN 105130856 B CN105130856 B CN 105130856B
- Authority
- CN
- China
- Prior art keywords
- diphenyl ether
- acid
- alcohol
- preparation
- compound
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of diphenyl ether sulfonyl azide compound, with diphenyl ether sulfonyl hydrazines compound (I) for raw material, sodium nitrite in aqueous solution is added dropwise to after being reacted in the alcohol dissolved with the raw material-acid solution system, directly obtains diphenyl ether sulfonyl azide compound (II) target product.Alcohol in the alcohol-acid solution system is C1‑4At least one of alcohol, acid are at least one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid.Present method avoids the current sodium azide using severe toxicity, and the disadvantages of a large amount of high boiling solvent lignin amines need to be used and generate a large amount of waste acid waters, and due to being homogeneous reaction, have reaction speed fast, high income, low-boiling alcohols solvent are easily recycled apply Deng remarkable advantages.
Description
Technical field
The present invention relates to a kind of preparation methods of diphenyl ether sulfonyl azide compound.
Background technique
Diphenyl ether sulfonyl azide compound is the novel substitute products of diphenyl ether sulfohydrazide type blowing agent.Diphenyl ether
Sulphonyl hydrazine compound is widely used to the foaming agent of plastics, rubber materials, decomposition Shi Bufa wide with processing temperature range
It is smelly, do not generate conductive impurities, only generate nitrogen gas and water and sulfur-bearing aromatic polymer, the latter, which remains in foaming product, not to be polluted
Product, and there is anti-oxidant and plasticization, it is decomposed in foaming and generates imperceptible closed pore bubble, which has
(Chen Shijing novel C NOH foaming agent succeeds in developing " gas chemical industry " for good physical mechanical property and electrical insulation properties
The 6th phase of nineteen ninety).
But diphenyl ether sulfohydrazide compound blowing agents have the shortcomings that bad dispersibility and moisture absorption, there is water in decomposable process
It generates, which limits it the application in strict demand field in certain pairs of moisture controls.With diphenyl ether sulphonyl hydrazine compound
It compares, diphenyl ether sulfonyl azide compound then has that polarity is smaller, non-hygroscopic, and dispersibility is more preferable, and when decomposition does not generate water, hair
The advantages that bubble is had excellent performance and adaptive surface is wider.
Preparation to diphenyl ether sulfonyl azide compound, United States Patent (USP) US2518249 describe a kind of diphenyl ether and chlorine
Sulfonic acid reacts the technique for generating diphenyl ether sulfonyl azide after generating the double benzene sulfonyl chlorides of 4,4 '-oxos with aqueous sodium azide again.
The technique has excessive more, the big sodium azide of generation waste acid quantity of chlorosulfonic acid to belong to hypertoxic harmful influence, has in production and storage and transport process
The potential risk exploded.Sodium azide has high toxicity, wastewater treatment complexity, cost to water environment and aquatile simultaneously
High and be hard to reach environmental protection standard, long-term adverse effect may be generated to water body environment by dealing with improperly.
United States Patent (USP) US2741624 describe it is a kind of diphenyl ether sulfohydrazide is suspended in glacial acetic acid, be added solid nitrous
Sour sodium, the elutriation of addend times glacial acetic acid volume goes out the preparation method of diphenyl ether sulfonyl azide crystallization after reaction.The technique
It is big using acetic acid amount, spent acid enormous amount, waste acidity recovery difficulty are generated, wastewater discharge is huge and treatment cost is high, and equipment is rotten
Erosion is serious, thus causes that manufacturing cost is high, is not suitable for industrialized production.
Summary of the invention
In consideration of it, the present invention provides a kind of preparation method of diphenyl ether sulfonyl azide compound, it not only can be effective
It solves the problems, such as that the above method exists, and corresponding diphenyl ether sulfonyl azide chemical combination can be directly obtained by single step reaction
Produce product.
The preparation method of diphenyl ether sulfonyl azide compound of the invention is with diphenyl ether sulfonyl hydrazines compound (I)
For raw material, sodium nitrite in aqueous solution is added dropwise to after being reacted in the alcohol dissolved with the raw material-acid solution system, directly obtains institute
State diphenyl ether sulfonyl azide compound (II).After the reaction was completed, it is post-processed through conventional filtration washing etc. to get corresponding mesh is arrived
Mark product.The reaction process is as follows:
。
R in above formula1And R2Any the position of substitution in phenyl ring where can independently selecting and can be separately
The saturated fat containing 1-4 carbon atom selected from hydrogen atom, including methyl, ethyl, propyl, isopropyl, butyl, sec-butyl
The halogen elements such as fat alkyl or the fluorine, chlorine, bromine, the iodine that could generally have good flame-retardance energy.Wherein, R1And R2Preferably independently
Selected from H or CH3.For example, the diphenyl ether sulfonyl hydrazines raw materials of compound (I) can include but is not limited to diphenyl ether -4,
4 '-bis- sulfohydrazides, 2- methyl-diphenyl ether -4,4 '-bis- sulfohydrazides, 2- methyl -3 '-chloro- diphenyl ether -4,4 '-bis- sulfohydrazides, 3-
The chloro- diphenyl ether of methyl -3 '-chloro- diphenyl ether -4,4 '-bis- sulfohydrazides, 3- methyl -6- -4,4 '-bis- sulfohydrazides, 3- methyl -6- are bromo-
Diphenyl ether -4,4 '-bis- sulfohydrazides, 2,5- dimethyl-diphenyl ether -4,4 '-bis- sulfohydrazides, 2,6- dimethyl-diphenyl ether -4,4 ' -
Double sulfohydrazides, 2,2 '-dimethyl-diphenyl ether -4,4 '-bis- sulfohydrazides, 3,3 '-dimethyl-diphenyl ether -4,4 '-bis- sulfohydrazides, 4,
4 '-dimethyl-diphenyl ether -2,2 '-bis- sulfohydrazides etc..These raw material compounds can using it is currently reported and/use
Mode/approach obtains, for example including but be not limited to report referring in the documents such as CN1105663A, US2552065, US4329499
Method be prepared.
Alcohol in the alcohol-acid solution system can choose the fat containing 1-4 carbon atom such as methanol, ethyl alcohol, propyl alcohol
At least one of race's alkane alcohols, the alcohol in the alcohol-acid solution system, for the aliphatic alkane containing 1-4 carbon atom
At least one of alcohols.These, it is preferred to which methanol and/or ethyl alcohol, especially solubility property are good, low in cost, Yi Huishou
The methanol applied.
Acid in the alcohol-acid solution system, can choose at least one of inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid,
In preferably at low cost, good operability and the small hydrochloric acid of molecular weight.
On the basis of above-mentioned preparation method, the preferred embodiment that can also further be applied in combination individually or in any way
Include:
The molar ratio of the raw material diphenyl ether sulfonyl hydrazines compound (I) and sodium nitrite is 1:(2 ~ 5), preferably
Molar ratio is 1:(2 ~ 3), better molar ratio is close to 1:(2 ~ 2.3 of theoretical amount), it both can guarantee sulfohydrazide fully reacting,
The treating capacity of the waste water containing sodium nitrite is reduced, as far as possible again to achieve the purpose that reduce cost and reduce waste water；
Excessive concentration of the raw material diphenyl ether sulfonyl hydrazines compound (I) in the dicyandiamide solution, is unfavorable for
The yield of the mass-and heat-transfer of reaction, final product is lower, the too low volumetric efficiency for being unfavorable for reactor of concentration.Under normal circumstances, former
Expect that the w/w concentration of diphenyl ether sulfonyl hydrazines compound (I) in the dicyandiamide solution is controllable to 5% ~ 50%, can make to originate
Compound (I) is completely dissolved.Further preferred concentration can be 10% ~ 30% on this basis, better concentration can be used 15% ~
25%, to reach optimal economic benefit；
Sour molar ratio mistake in the raw material diphenyl ether sulfonyl hydrazines compound (I) and the alcohol-acid solution system
Low, the dissolution of raw material diphenyl ether sulfonyl hydrazines compound (I) is incomplete；The treating capacity of the excessively high then spent acid of molar ratio is too big.For
This, in diphenyl ether sulfonyl hydrazines compound (I) and the alcohol-acid solution system sour molar ratio may generally be 1:(2.0 ~
5.0), preferred molar ratio can be 1:(2.0 ~ 3.0), better molar ratio is 1:(2.1 ~ 2.3).Experiment display, it is appropriate to reduce
Acid usage ratio, such as with slightly larger than theoretical amount acid amount ratio when, can have better yield, and cost can be reduced；
Experiment display, the excessive concentration of sodium nitrite in aqueous solution used, it would be generally disadvantageous to intermediate product nitrous acid it is molten
Solution, and keep final production yield lower；And concentration is too low, will lead to that wastewater flow rate is too big, and is unfavorable for the volumetric efficiency of reaction.One
As in the case of, the w/w concentration of the sodium nitrite in aqueous solution is controllable to 5% ~ 50%, further preferred concentration can for 20% ~
30%, cost and the better effect of yield are reduced to obtain；
Under normal circumstances, the reaction temperature in above-mentioned preparation process is too low, reaction speed can be made slack-off, while increasing and setting
Energy consumption needed for standby freezing；Temperature is excessively high, and the decomposition of intermediate product nitrous acid is overflowed from reaction solution, influences final production yield.
Experiment display, the reaction temperature is all allowed within the scope of 0 ~ 50 DEG C, wherein preferred reaction temperature is 0 ~ 20 DEG C, more
Good reaction temperature is 0 ~ 5 DEG C, makes yield and purity that can obtain more satisfied effect.
The experimental results showed that the preparation method that the present invention is above-mentioned, not only efficiently avoids needing to make in current preparation method
With the sodium azide of severe toxicity, and/or using a large amount of organic acids and the disadvantages of generate a large amount of waste acid waters, and take diphenyl ether
After sulfohydrazide raw material is first dissolved in alcohol-acid solution, then the homogeneous reaction of sodium nitrite in aqueous solution is added dropwise, there can be reaction speed
Fastly, conversion is completely, high income, low-boiling alcohols solvent be easily recycled and the remarkable advantages such as apply.
Specific embodiment by the following examples is described in further detail above content of the invention.But no
The range that this should be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.The above-mentioned technical idea feelings of the present invention are not being departed from
Under condition, the various replacements or change made according to ordinary skill knowledge and customary means, should all include of the invention
In range.
Specific embodiment
By diphenyl ether -4,4 '-bis- sulfonyl hydrazines raw materials are put into 250-mL there-necked flasks, and selected solvent and acid, stirring is added
Solution is made in dissolution.The sodium nitrite in aqueous solution of suitable concentration is slowly added dropwise, the reaction was continued after being added dropwise 60 minutes until TLC
Until display is without raw material.Vacuum filter is washed with ordinary water, is dried under reduced pressure to constant weight, obtains white solid.It is produced if you need to further increase
Product purity can be purified with silica gel column chromatography.TLC purity assay, product structure is through 400MHz1HNMR(DMSO-d 6) analysis verifying.
Reaction process is as follows:
。
The starting material and inventory, reaction dissolvent, acid and sodium nitrite of each preparation embodiment operated according to the above method
Amount, the actual conditions such as the temperature of reaction and yield are as shown in table 1 respectively.Unless otherwise instructed, the % in table is w/w ratio
Example.
Claims (9)
1. the preparation method of diphenyl ether sulfonyl azide compound, it is characterized in that being original with diphenyl ether sulfonyl hydrazines compound (I)
Material, sodium nitrite in aqueous solution is added dropwise in the alcohol dissolved with the raw material-acid solution system and is reacted in 0~50 DEG C, and a step obtains
To diphenyl ether sulfonyl azide compound (II) target product, reaction process is as follows:
R in formula1For hydrogen atom, R2For hydrogen atom, the alcohol in the alcohol-acid solution system is methanol or ethyl alcohol, and the acid is
Hydrochloric acid or sulfuric acid；The molar ratio of diphenyl ether sulfonyl hydrazines compound (I) and sodium nitrite is 1: (2~5), diphenyl ether sulphonyl
W/w concentration of the hydrazine class compound (I) in the dicyandiamide solution is 10%~25%, diphenyl ether sulfonyl hydrazines compound (I)
Be 1 with molar ratio sour in the alcohol-acid solution system: (2~5), the w/w concentration of sodium nitrite in aqueous solution are 5%~50%.
2. preparation method as described in claim 1, it is characterized in that the raw material diphenyl ether sulfonyl hydrazines compound (I) with
The molar ratio of sodium nitrite is 1: (2~3).
3. preparation method as claimed in claim 2, it is characterized in that the raw material diphenyl ether sulfonyl hydrazines compound (I) with
The molar ratio of sodium nitrite is 1: (2~2.3).
4. preparation method as described in claim 1, it is characterized in that the raw material diphenyl ether sulfonyl hydrazines compound (I) exists
W/w concentration in the dicyandiamide solution is 15%~25%.
5. preparation method as described in claim 1, it is characterized in that the raw material diphenyl ether sulfonyl hydrazines compound (I) with
Sour molar ratio is 1 in the alcohol-acid solution system: (2.0~3.0).
6. preparation method as claimed in claim 5, it is characterized in that the raw material diphenyl ether sulfonyl hydrazines compound (I) with
Sour molar ratio is 1 in the alcohol-acid solution system: (2.1~2.3).
7. preparation method as described in claim 1, it is characterized in that the w/w concentration of the sodium nitrite in aqueous solution be 20%~
30%.
8. the preparation method as described in one of claim 1 to 7, it is characterized in that the reaction temperature is 0~20 DEG C.
9. preparation method as claimed in claim 8, it is characterized in that the reaction temperature is 0~5 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510513687.3A CN105130856B (en) | 2015-08-20 | 2015-08-20 | The preparation method of diphenyl ether sulfonyl azide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510513687.3A CN105130856B (en) | 2015-08-20 | 2015-08-20 | The preparation method of diphenyl ether sulfonyl azide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105130856A CN105130856A (en) | 2015-12-09 |
| CN105130856B true CN105130856B (en) | 2019-03-19 |
Family
ID=54716492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510513687.3A Active CN105130856B (en) | 2015-08-20 | 2015-08-20 | The preparation method of diphenyl ether sulfonyl azide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105130856B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11339272B2 (en) | 2016-11-30 | 2022-05-24 | Bridgestone Corporation | Additive for rubber, rubber composition, and tire using the same |
| CN109320686B (en) * | 2018-08-29 | 2021-06-08 | 华南理工大学 | Polyiso-urea polymer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2518249A (en) * | 1949-07-09 | 1950-08-08 | Monsanto Chemicals | Diphenyl-4, 4'-di (sulfonyl azide) |
| US2741624A (en) * | 1954-08-30 | 1956-04-10 | Us Rubber Co | p, p'-oxybis(benzenesulfonylazide) and process |
| CN1740179A (en) * | 2005-08-25 | 2006-03-01 | 山东大学 | N4-substituent pyrazolyl [4,5-e][1,2,4] thiadiazine derivative and its prepn process and medicine composition |
| CN101735144A (en) * | 2009-12-11 | 2010-06-16 | 西北农林科技大学 | Synthesizing method of isonicotinyl hydrazine azide |
-
2015
- 2015-08-20 CN CN201510513687.3A patent/CN105130856B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2518249A (en) * | 1949-07-09 | 1950-08-08 | Monsanto Chemicals | Diphenyl-4, 4'-di (sulfonyl azide) |
| US2741624A (en) * | 1954-08-30 | 1956-04-10 | Us Rubber Co | p, p'-oxybis(benzenesulfonylazide) and process |
| CN1740179A (en) * | 2005-08-25 | 2006-03-01 | 山东大学 | N4-substituent pyrazolyl [4,5-e][1,2,4] thiadiazine derivative and its prepn process and medicine composition |
| CN101735144A (en) * | 2009-12-11 | 2010-06-16 | 西北农林科技大学 | Synthesizing method of isonicotinyl hydrazine azide |
Non-Patent Citations (3)
| Title |
|---|
| "Free-radical azidation with g-15N-labeled phenylsulfonyl azide";Masterson Douglas等;《Synlett》;20070304(第8期);Scheme 2, 第1303页化合物1的制备 |
| "Synthesis and Characterization of Blowing Agents and Hypergolics";Alan R. Katrizzky等;《Journal of Energetic Materials》;20070322;第25卷;第87页，化合物14的合成 |
| "Synthesis and Reactions of Aryl-2:4-bis-sulphonyl Azides";N. A. Shams等;《J. Chem. Soc. Pak.》;19861231;第8卷(第2期);第210页图；第215页左栏 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105130856A (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105130856B (en) | The preparation method of diphenyl ether sulfonyl azide compound | |
| JP2010155814A (en) | Method for producing perfluoroalkyl sulfonic acid salt | |
| CN103360316A (en) | Preparation method of fipronil | |
| US9045411B2 (en) | Method for recovering anionic fluorinated emulsifier | |
| CN106588719A (en) | Method foe preparing high-purity 4,4'-dichlorodiphenyl sulfone | |
| CN107501059B (en) | Green and environment-friendly synthesis method of 4- (4' -alkylcyclohexyl) cyclohexanone | |
| US9550717B2 (en) | Method for recovering anionic fluorinated emulsifier | |
| CN109896942A (en) | A kind of preparation method of alpha-alcohol ketone photoinitiator | |
| CN108727297A (en) | A kind of hydrogen peroxide oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide | |
| CN105367442B (en) | A kind of method of the deaminizating of aromatic compound containing amino | |
| CN103232396A (en) | Three selective ionic liquids and synthesizing method thereof | |
| JP2014505654A5 (en) | ||
| CN108276439B (en) | Brominated phosphate flame retardant and preparation method thereof | |
| CN114163363A (en) | Aralkyl diene sulfonate ionic membrane compound capable of being densely crosslinked | |
| KR101995039B1 (en) | Brominated polyphenylenesulfide based by polyphenylenesulfide, method for producing the same, brominated and sulfonated polyphenylenesulfide and manufacturing method using the same | |
| CN106397828B (en) | The recycling and reusing method of polyethylene in superfine fibre preparation | |
| US9873666B2 (en) | Method for preparing oxysulphide and fluorinated derivatives by sulphination | |
| CN104262207B (en) | A kind of preparation method of sulfonic fluoropolymer compounds | |
| CN101234989A (en) | Method for preparing 4,4'-di(2,4-dinitrophenoxy)benzophenone | |
| CN104743722A (en) | Comprehensive treatment method for high-concentration sodium sulfate wastewater generated in dicumyl peroxide production | |
| CN101486652B (en) | Preparation of 4,4'-bis(4-nitro-2-trifluoromethyl phenoxy) biphenyl | |
| CN101503361B (en) | Preparation of 1,4-bis(2-trifluoromethyl-4-nitrophenoxy)-2,5-di-t-butylbenzene | |
| CN101234987A (en) | Method for preparing 4,4'-di(2,4-dinitrophenoxy)diphenyl ether | |
| CN101234990B (en) | Method for preparing 4,4'-di(2,4-dinitrophenoxy)diphenylmethane | |
| CN101503360B (en) | Preparation of 2- tertiary butyl-1,4-bis (4-nitro-2-trifluoromethyl phenoxy) benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201221 Address after: 22 Jiankang Road, Yuechi economic and Technological Development Zone, Guang'an City, Sichuan Province Patentee after: Guang'an runkang Pharmaceutical Co.,Ltd. Address before: Room 905, C1 building, Tianfu Life Science Park, 88 Keyuan South Road, high tech Zone, Chengdu, Sichuan 610041 Patentee before: CHENGDU ORGANOCHEM Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210531 Address after: No. 901 and 905, building 12, No. 88 Keyuan South Road, high tech Zone, Chengdu, Sichuan 610000 Patentee after: CHENGDU ORGANOCHEM Co.,Ltd. Address before: 22 Jiankang Road, Yuechi economic and Technological Development Zone, Guang'an City, Sichuan Province Patentee before: Guang'an runkang Pharmaceutical Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation of diphenyl ether sulfonyl azide compounds Effective date of registration: 20220125 Granted publication date: 20190319 Pledgee: Guang'an Shangxin Financing Guarantee Co.,Ltd. Pledgor: CHENGDU ORGANOCHEM Co.,Ltd. Registration number: Y2022510000027 |