CN1009085B - Prepn. of sulfoxides - Google Patents
Prepn. of sulfoxidesInfo
- Publication number
- CN1009085B CN1009085B CN 85100440 CN85100440A CN1009085B CN 1009085 B CN1009085 B CN 1009085B CN 85100440 CN85100440 CN 85100440 CN 85100440 A CN85100440 A CN 85100440A CN 1009085 B CN1009085 B CN 1009085B
- Authority
- CN
- China
- Prior art keywords
- sulfoxide
- thioether
- oxidized
- acetic anhydride
- quantitatively
- 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.)
- Expired
Links
Abstract
The present invention relates to a new method for quantificationally oxidizing symmetrical and asymmetric alkyl (or aryl) thioether into sulfoxide in a medium of acetic anhydride at room temperature and under the protection of N2 with an oxidant being 30% of H2O2 and a catalyst being concentrated sulphuric acid. The method has the advantages of short reaction time, good specificity, high yield and high purity of obtained sulfoxide.
Description
The invention belongs to thioether and be oxidized to the method for sulfoxide quantitatively.
Sulfoxide is effective extraction agent of multiple metal, can extract precious metals such as gold and silver, also can extract rare earth metals such as uranium, thorium, and more valuable is that it can optionally extract molybdenum from sodium tungstate solution, reaches the purpose of deep purifying sodium tungstate solution.
Thioether is oxidized to sulfoxide and does not generate sulfone quantitatively is a difficult problem, and the key of problem is to select suitable oxygenant and oxidation system thereof.(so-called thioether is oxidized to sulfoxide quantitatively, means thioether and H
2O
2Under equimolar condition, thioether all is oxidized to sulfoxide and does not generate sulfone).
The present industrial method for preparing sulfoxide is continued to use hydrogen peroxide as oxidant always, and sulfide oxidation is become sulfoxide, but usually with the phenomenon of over oxidation, often has the impurity sulfone to be mixed in wherein in sulfoxide, has influenced selection of Extractant.For this reason, people are in the oxidizing process of seeking to improve thioether for a long time, and the expectation thioether only is oxidized to sulfoxide quantitatively and does not generate sulfone.That prior art such as patent J55038320A disclose is a kind of 2,2 '-preparation method of bis-phenol sulfoxide; Patent U.S3,996,295 disclose a kind of preparation method of dimethyl sulfoxide (DMSO); Chinese science B collects (1984 the 3rd phases) and discloses a kind of preparation method of alkyl sulfoxide, and this method is made solvent with the mixed solution of Glacial acetic acid and acetone, and two (2-ethylhexyl) thioethers and hydrogen peroxide at room temperature stirring reaction are produced sulfoxide.
But above-mentioned all methods all can not be oxidized to sulfoxide quantitatively with thioether, still there is the thioether of part not oxidized in the system, becoming " impurity " remains in the product, increased isolating difficulty, the sterically hindered bigger thioether (as t-butyl n-octyl thioether etc.) that particularly has unsymmetrical structure for those, above-mentioned all methods are stymied by especially, (is different because different sulfide oxidations becomes the difficulty of sulfoxide).When reactive system (or title system) inert-free gas is protected, owing to the influence of airborne oxygen and steam, still can not produce the over oxidation of thioether in addition, making to mix in the product has a spot of impurity sulfone with keeping away.
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, provide a kind of preparation method of sulfoxide, at thioether and H
2O
2Under the equimolar condition, symmetry or asymmetric alkyl (or aryl) thioether are oxidized to sulfoxide quantitatively and do not generate sulfone, to satisfy the needs of hydrometallurgy industry.
The present invention has done further improvement on the basis of previous work, the employing acetic anhydride is solvent, 30%H
2O
2Make catalyzer for oxygenant, the vitriol oil, thioether is oxidized to sulfoxide quantitatively, and does not generate sulfone with 98% under room temperature and nitrogen protection.
Wherein the effect of concentrated sulfuric acid catalyst is: drip the vitriol oil of catalytic amount, can realize thioether and H
2O
2Between reaction with same mole, and accelerated speed of response greatly, shorten the reaction times, its molecular balance mechanism is as follows:
Wherein the effect of acetic anhydride solvent is: except as the solvent, acetic anhydride and the water effect that reaction generates generate acetate, thereby the balance of the formula of making (1) move to helping generating the sulfoxide direction; And the small amount of acetic acid that reaction generates (relatively is in more H
2O
2Encirclement in) can be immediately and H
2O
2Reaction generates Peracetic Acid (a kind of strong oxygenant), and it can be effectively and thioether reactant, and sulfide oxidation is become sulfoxide.
In a word, because the combined effect that sulfuric acid catalyst and acetic anhydride solvent are risen in system, realized that the present invention is said thioether is oxidized to sulfoxide quantitatively (at thioether and H
2O
2Under the equimolar operating mode), even the thioether in the adding system (system) all changes into sulfoxide.
The effect of nitrogen protection wherein: nitrogen protection is the important measures that stop the thioether over oxidation.When whole system under the exsiccant nitrogen protection, stoped airborne oxygen and steam to enter reactive system, thereby avoided the generation of pair reaction effectively, so nitrogen protection is to realize that thioether only is oxidized to sulfoxide and does not generate the effective measure of sulfone.
Raw material of the present invention:
Alkyl (or aryl) thioether: can be by halohydrocarbon and sodium sulphite prepared in reaction:
Oxygenant: adopt chemical pure 30%H
2O
2;
Catalyzer: 98% chemical pure H
2SO
4;
Solvent: chemical pure acetic anhydride.
The present invention is in room temperature and nitrogen atmosphere, drips equimolar 30%H in the solution of thioether and acetic anhydride
2O
2, behind the stirring reaction several minutes, slowly splash into 0.1ml98% concentration H
2SO
4(in every 0.1mol thioether) can see obviously that the white solid sulfoxide produces, and then continues reaction and can stop in about 4 hours stirring.Standing demix is told organism, and through freezing, suction filtration, washing, oven dry promptly get the sulfoxide crude product.This crude product recrystallization in sherwood oil (60～90 ℃) is once promptly got the pure product of sulfoxide.As asymmetric " methyl tridecyl " sulfoxide, yield is a no this sulfoxide in the 82.2%(document behind recrystallizing and refining), its
Shape of product: white crystal,
Fusing point (m
0P
0): 58 ℃,
IR（cm
-1）：2950-2900，2850，1465，1070，1030，705。
Embodiment
The acetic anhydride of the dioctyl thioether of 0.29mol and 87.6ml placed agitator is housed, reflux condensing tube is in the 250ml there-necked flask of dropping funnel and nitrogen conduit, under room temperature, nitrogen protection and constant speed stir, with 30ml30%H
2O
2(0.29mol) slowly be added drop-wise in the there-necked flask, react after 10 minutes, drip the dense H of 2.9ml98% again
2SO
2Continuing stirring reaction can stop in 3.5 hours.Standing demix is told organism, promptly gets the sulfoxide crude product through freezing, suction filtration, washing, oven dry.This crude product recrystallization in sherwood oil (60～90 ℃) is once promptly got the pure product of sulfoxide, and the yield behind the recrystallization is 71.3% for the 84.6%(prior art).
Product: the white plates crystal, m.P.72 ℃,
Ultimate analysis: C
16H
34OS M.W.274.06.
Calculated value: C%, 70.07; H% 12.40.
Measured value: C%, 70.27; H% 12.21.
IR（cm
-1）：2950，2900-2850，1450，1069，1022，700。
M、S（m/e）：275（M+1、3.25），257（100），145（94.62），71（43.58），57（83.92）。
HNMR（δPPm）：0.83（3H，t，-CH
3），1.25（2H，S-CH
2-），2.45（2H，t，
）。
Owing to adopt method of the present invention can make thioether all change into sulfoxide, not only simplified the purge process of product, and improved the yield of sulfoxide effectively in a word, this has very big realistic meaning to industrialization.
Claims (2)
1, a kind of method for preparing sulfoxide promptly is solvent with the acetic anhydride, 30% H
2O
2Be oxygenant, symmetric and asymmetric alkyl (or aryl) thioether is oxidized to the method for sulfoxide quantitatively, it is characterized in that under room temperature and nitrogen protection, being catalyzer with the vitriol oil.
2,, it is characterized in that said catalyst consumption is the vitriol oil that every 0.1mol thioether drips 1ml98% according to the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100440 CN1009085B (en) | 1985-04-01 | 1985-04-01 | Prepn. of sulfoxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100440 CN1009085B (en) | 1985-04-01 | 1985-04-01 | Prepn. of sulfoxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100440A CN85100440A (en) | 1986-07-16 |
| CN1009085B true CN1009085B (en) | 1990-08-08 |
Family
ID=4791159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85100440 Expired CN1009085B (en) | 1985-04-01 | 1985-04-01 | Prepn. of sulfoxides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1009085B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070498A (en) * | 2011-01-12 | 2011-05-25 | 华东师范大学 | Preparation method of sulfoxide |
| CN105294516A (en) * | 2014-07-03 | 2016-02-03 | 阮建兵 | Method for preparing dodecyl methyl sulfoxide |
| CN106083666B (en) * | 2016-06-14 | 2017-11-07 | 岳阳蓬诚科技发展有限公司 | A kind of production technology of dimethyl sulfone |
| CN105884662B (en) * | 2016-06-14 | 2017-07-21 | 岳阳蓬诚科技发展有限公司 | A kind of production technology of dimethyl sulfone |
| CN105837477B (en) * | 2016-06-14 | 2017-07-21 | 岳阳蓬诚科技发展有限公司 | A kind of preparation method of dimethyl sulfone |
-
1985
- 1985-04-01 CN CN 85100440 patent/CN1009085B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100440A (en) | 1986-07-16 |
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