CN105130856A - Preparation method for diphenyl ether serial sulfonyl azide compounds - Google Patents
Preparation method for diphenyl ether serial sulfonyl azide compounds Download PDFInfo
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- CN105130856A CN105130856A CN201510513687.3A CN201510513687A CN105130856A CN 105130856 A CN105130856 A CN 105130856A CN 201510513687 A CN201510513687 A CN 201510513687A CN 105130856 A CN105130856 A CN 105130856A
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Abstract
The invention discloses a preparation method for diphenyl ether serial sulfonyl azide compounds. The preparation method comprises taking a diphenyl ether sulfohydrazide compound (I) as a raw material, dropwise adding a sodium nitrite aqueous solution into an alcohol-acid solution system dissolving all of the raw materials, reacting, so as to directly obtain the corresponding diphenyl ether serial sulfonyl azide compound (II) target product. The alcohol in the alcohol-acid solution system is at least one of C1-4 alcohols, and the acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetate and propionic acid. The method avoids currently-used severely-toxic sodium azide and also avoids disadvantages of usage of a large amount of high-boiling-point organic acids, generation of a large amount of waste acid water, and the like. Because the reactions are all homogeneous reactions, the method possesses obvious advantages of being fast in reaction speed, high in yield, easy for recovery and recycling of low-boiling-point alcohol solvents, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of diphenyl ether sulfonyl azide compound.
Background technology
Diphenyl ether sulfonyl azide compound is the novel substitute products of diphenyl ether sulfohydrazide type blowing agent.Diphenyl ether sulfonyl hydrazide compound has been widely used in the whipping agent of plastics, rubber materials, have processing temperature wide ranges, decompose time not smelly, do not produce conductive impurities, only produce nitrogen, water and sulfur-bearing aromatic polymer, the latter residues in foaming product and does not pollute goods, and there is anti-oxidant and plastification, decompose when foaming and produce imperceptible closed pore bubble, this foaming product have good physical and mechanical properties and electrical insulation properties (Chen Shijing. novel C NOH whipping agent is succeeded in developing. the phase " gas chemical industry " nineteen ninety the 6th).
But diphenyl ether sulfonyl hydrazide compound blowing agents has the shortcoming of bad dispersibility and moisture absorption, have water to generate in decomposition course, which limits it has the application in strict demand field at some to moisture controlled.With diphenyl ether sulfonyl hydrazide Compound Phase ratio, it is less, non-hygroscopic that diphenyl ether sulfonyl azide compound then has polarity, dispersed better, do not produce the advantages such as the excellent and adaptive surface of water, foam performance is wider during decomposition.
To the preparation of diphenyl ether sulfonyl azide compound, US Patent No. 2518249 describes a kind of phenyl ether and chlorsulfonic acid generates 4, reacts the technique generating phenyl ether sulfonyl azide again after the two benzene sulfonyl chloride of 4 '-oxo with aqueous sodium azide.This technique have chlorsulfonic acid excessive many, to produce spent acid amount large. sodiumazide belongs to hypertoxic harmful influence, in production and storage and transport process, have the potential risk of blasting.Simultaneously sodiumazide has high toxicity to water surrounding and hydrobiont, and complicated, the with high costs and very difficult arrival environmental protection standard of wastewater treatment, deals with improperly and may produce long-term detrimentally affect to water body environment.
US Patent No. 2741624 describes one and is suspended in Glacial acetic acid by phenyl ether sulfonyl hydrazide, adds solid sodium nitrite, adds the preparation method that the elutriation being several times as much as Glacial acetic acid volume goes out the crystallization of phenyl ether sulfonyl azide after reaction terminates.This technique uses acetic acid amount large, and produce spent acid enormous amount, waste acidity recovery difficulty, wastewater discharge is huge and treatment cost is high, and equipment corrosion is serious, thus cause manufacturing cost high, be not suitable for suitability for industrialized production.
Summary of the invention
Given this, the invention provides a kind of preparation method of diphenyl ether sulfonyl azide compound, not only can effectively solve aforesaid method Problems existing, and can directly obtain corresponding diphenyl ether sulfonyl azide compound products by single step reaction.
The preparation method of diphenyl ether sulfonyl azide compound of the present invention, for raw material with phenyl ether sulfonyl hydrazines compound (I), sodium nitrite in aqueous solution is added dropwise to after reacting in the alcohol-acid solution system being dissolved with described raw material, directly obtains described diphenyl ether sulfonyl azide compound (II).After having reacted, through aftertreatments such as conventional filtration washings, namely obtain corresponding target product.Described reaction process is as follows:
。
R in above formula
1and R
2-independently can select the arbitrary the position of substitution in the phenyl ring of place and can separately be selected from hydrogen atom, comprise methyl, the saturated fatty alkyl containing 1-4 carbon atom of ethyl, propyl group, sec.-propyl, butyl, sec-butyl or usually can have the halogen element such as fluorine, chlorine, bromine, iodine of good flame-retardance energy.Wherein, R
1and R
2preferably independently selected from H or CH
3.Such as, described diphenyl ether sulfonyl hydrazines raw materials of compound (I) can include but not limited to phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 2-methyl-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 2-methyl-3 '-chloro-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 3-methyl-3 '-chloro-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, the chloro-phenyl ether-4 of 3-methyl-6-, 4 '-bis-sulfonyl hydrazide, the bromo-phenyl ether-4 of 3-methyl-6-, 4 '-bis-sulfonyl hydrazide, 2, 5-dimethyl-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 2, 6-dimethyl-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 2, 2 '-dimethyl-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 3, 3 '-dimethyl-phenyl ether-4, 4 '-bis-sulfonyl hydrazide, 4, 4 '-dimethyl-phenyl ether-2, 2 '-bis-sulfonyl hydrazides etc.These starting compounds can adopt mode/approach that is currently reported and/use to obtain, such as, include but not limited to that the method with reference to reporting in the documents such as CN1105663A, US2552065, US4329499 prepares.
Alcohol in described alcohol-acid solution system, methyl alcohol, ethanol, propyl alcohol etc. can be selected containing at least one in the aliphatic alkane alcohols of 1-4 carbon atom, alcohol in described alcohol-acid solution system, for containing at least one in the aliphatic alkane alcohols of 1-4 carbon atom.Wherein, the methyl alcohol that preferably methyl alcohol and/or ethanol, particularly solubility property are good, with low cost, easy to recovery of applied.
Acid in described alcohol-acid solution system, can select at least one in the mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, wherein preferably low, the good operability of cost and the little hydrochloric acid of molecular weight.
On the basis of above-mentioned preparation method, the optimal way that can also combinationally use separately or in any way further comprises:
Described raw material diphenyl ether sulfonyl hydrazines compound (I) is 1:(2 ~ 5 with the mol ratio of Sodium Nitrite), preferred mol ratio is 1:(2 ~ 3), better mol ratio is 1:(2 ~ 2.3 close to theoretical amount), can ensure that sulfonyl hydrazide reacts completely, reduce again the treatment capacity containing Sodium Nitrite waste water as far as possible, to reach the object reducing costs and reduce waste water;
Described raw material diphenyl ether sulfonyl hydrazines compound (I) excessive concentration in described solvent system, be unfavorable for the mass-and heat-transfer reacted, the yield of end product is lower, the too low volumetric efficiency being unfavorable for reactor of concentration.Generally, the w/w concentration of raw material diphenyl ether sulfonyl hydrazines compound (I) in described solvent system is controlled is made as 5% ~ 50%, and initial compounds (I) can be made to dissolve completely.Further preferred concentration can be 10% ~ 30% on this basis, and better concentration can adopt 15% ~ 25%, to reach best economic benefit;
Described raw material diphenyl ether sulfonyl hydrazines compound (I) is too low with the mol ratio of acid in described alcohol-acid solution system, and the dissolving of raw material diphenyl ether sulfonyl hydrazines compound (I) is incomplete; The treatment capacity of the too high then spent acid of mol ratio is too large.For this reason, diphenyl ether sulfonyl hydrazines compound (I) generally can be 1:(2.0 ~ 5.0 with the mol ratio of acid in described alcohol-acid solution system), preferred mol ratio can be 1:(2.0 ~ 3.0), better mol ratio is 1:(2.1 ~ 2.3).Experiment display, suitably reduces the usage ratio of acid, such as, time with the amount ratio of the acid slightly larger than theoretical amount, can have better yield, and can reduce costs;
Experiment display, the excessive concentration of sodium nitrite in aqueous solution used, is unfavorable for the dissolving of intermediate product nitrous acid usually, and makes final production yield lower; Concentration is too low, wastewater flow rate can be caused too large, and be unfavorable for the volumetric efficiency of reaction.Generally, the w/w concentration of described sodium nitrite in aqueous solution is controlled is made as 5% ~ 50%, and further preferred concentration can be 20% ~ 30%, reduces costs the better effect with yield to obtain;
Generally, the temperature of reaction in above-mentioned preparation process is too low, and speed of response can be made slack-off, the freezing required energy consumption of the equipment that simultaneously increases; Temperature is too high, and the decomposition of intermediate product nitrous acid is overflowed from reaction solution, affects final production yield.Experiment display, described temperature of reaction is all allow within the scope of 0 ~ 50 DEG C, and wherein preferred temperature of reaction is 0 ~ 20 DEG C, and better temperature of reaction is 0 ~ 5 DEG C, makes yield and purity can obtain more satisfied effect.
Experimental result shows, the preparation method that the present invention is above-mentioned, not only efficiently avoid in current preparation method the sodiumazide needing to use severe toxicity, and/or use a large amount of organic acid and produce the shortcomings such as a large amount of waste acid waters, and after taking that diphenyl ether sulfonyl hydrazide raw material is first dissolved in the solution of alcohol-acid, drip the homogeneous reaction of sodium nitrite in aqueous solution again, can have speed of response fast, transform completely, the alcoholic solvent of the high and low boiling point of yield is easy to the remarkable advantages such as recovery.
Embodiment is by the following examples described in further detail foregoing of the present invention.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should comprise within the scope of the invention.
Embodiment
Dropped in 250-mL there-necked flask by phenyl ether-4,4 '-bis-sulfonyl hydrazines raw material, add selected solvent and acid, stirring and dissolving makes solution.The sodium nitrite in aqueous solution of slow dropping suitable concn, dropwises rear continuation reaction 60 minutes till TLC display is without raw material.Vacuum filtration, with ordinary water washing, drying under reduced pressure to constant weight, obtain white solid.As product purity need be improved further, available purification by silica gel column chromatography.TLC purity assay, product structure is through 400MHz
1hNMR(DMSO-
d 6) analysis verification.Reaction process is as follows:
。
The amount of the starting raw material of each preparation embodiment operated as stated above and charging capacity, reaction solvent, acid and Sodium Nitrite, the actual conditionses such as the temperature of reaction and yield, as shown in table 1 respectively.If no special instructions, the % in table is w/w ratio.
Claims (9)
1. the preparation method of diphenyl ether sulfonyl azide compound, it is characterized in that with phenyl ether sulfonyl hydrazines compound (I) for raw material, sodium nitrite in aqueous solution is added dropwise in the alcohol-acid solution system being dissolved with described raw material and reacts, one step obtains described diphenyl ether sulfonyl azide compound (II) target product, and reaction process is as follows:
, the R in formula
1and R
2independently select the arbitrary the position of substitution in place phenyl ring and be separately selected from hydrogen atom, comprise methyl, the saturated fatty alkyl containing 1-4 carbon atom of ethyl, propyl group, sec.-propyl, butyl, sec-butyl or halogen element; Alcohol in described alcohol-acid solution system is at least one in the saturated fatty alcohols containing 1-4 carbon atom, and described acid is comprise at least one in the mineral acid of hydrochloric acid, sulfuric acid, phosphoric acid.
2. preparation method as claimed in claim 1, is characterized in that the R in described raw material diphenyl ether sulfonyl hydrazines compound (I)
1and R
2separately be selected from hydrogen atom or CH
3.
3. preparation method as claimed in claim 1, it is characterized in that described raw material diphenyl ether sulfonyl hydrazines compound (I) is 1:(2 ~ 5 with the mol ratio of Sodium Nitrite), be preferably 1:(2 ~ 3), be more preferably 1:(2 ~ 2.3).
4. preparation method as claimed in claim 1, it is characterized in that the described w/w concentration of raw material diphenyl ether sulfonyl hydrazines compound (I) in described solvent system is 5% ~ 50%, preferred concentration is 10% ~ 30%, and better concentration is 15% ~ 25%.
5. preparation method as claimed in claim 1, it is characterized in that described raw material diphenyl ether sulfonyl hydrazines compound (I) is 1:(2.0 ~ 5.0 with the mol ratio of acid in described alcohol-acid solution system), preferred 1:(2.0 ~ 3.0), be more preferably 1:(2.1 ~ 2.3).
6. preparation method as claimed in claim 1, it is characterized in that the w/w concentration of described sodium nitrite in aqueous solution is 5% ~ 50%, preferred concentration is 20% ~ 30%.
7. preparation method as claimed in claim 1, is characterized in that described reaction is at 0 ~ 50 DEG C, and preferably at 0 ~ 20 DEG C, optimum is at 0 ~ 5 DEG C.
8. the preparation method as described in one of claim 1 to 7, is characterized in that the alcohol in described alcohol-acid solution system is methyl alcohol.
9. the preparation method as described in one of claim 1 to 8, is characterized in that the acid in described alcohol-acid solution system is hydrochloric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320686A (en) * | 2018-08-29 | 2019-02-12 | 华南理工大学 | A kind of poly- isourea quasi polymer and its preparation method and application |
| CN110023398A (en) * | 2016-11-30 | 2019-07-16 | 株式会社普利司通 | Rubber additive, rubber composition and the tire using it |
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 |
|---|
| ALAN R. KATRIZZKY等: ""Synthesis and Characterization of Blowing Agents and Hypergolics"", 《JOURNAL OF ENERGETIC MATERIALS》 * |
| MASTERSON DOUGLAS等: ""Free-radical azidation with g-15N-labeled phenylsulfonyl azide"", 《SYNLETT》 * |
| N. A. SHAMS等: ""Synthesis and Reactions of Aryl-2:4-bis-sulphonyl Azides"", 《J. CHEM. SOC. PAK.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110023398A (en) * | 2016-11-30 | 2019-07-16 | 株式会社普利司通 | Rubber additive, rubber composition and the tire using it |
| US11339272B2 (en) | 2016-11-30 | 2022-05-24 | Bridgestone Corporation | Additive for rubber, rubber composition, and tire using the same |
| CN109320686A (en) * | 2018-08-29 | 2019-02-12 | 华南理工大学 | A kind of poly- isourea quasi polymer and its preparation method and application |
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