CN101037440A - Environment friendly oxygen heterocyclic compound synthesizing method by catalytic oxidation of 1,5-cyclooctadiene - Google Patents
Environment friendly oxygen heterocyclic compound synthesizing method by catalytic oxidation of 1,5-cyclooctadiene Download PDFInfo
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- CN101037440A CN101037440A CN 200710037203 CN200710037203A CN101037440A CN 101037440 A CN101037440 A CN 101037440A CN 200710037203 CN200710037203 CN 200710037203 CN 200710037203 A CN200710037203 A CN 200710037203A CN 101037440 A CN101037440 A CN 101037440A
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- cyclooctadiene
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Abstract
The invention relates to a method for catalyzing oxidating the octadiene to synthesize heterocyclic oxygen compound belonging to chemical engineering. The method has a given tungstenic acid, tungstophosphoric acid or tungstosilicic acid as catalyzer, tert-butyl alcohol as solvent and catalyzes and oxidates the octadiene to synthesize heterocyclic oxygen compound in a specific temperature. The inventive method uses the commercial octadiene as material, which can get a total yield of the heterocyclic oxygen compound to 97-99% in a gentle reaction condition. Meanwhile, because having the hydrogen peroxide water solution as oxidant, it avoids the environment pollution brought by traditional oxidation process such as potassium permanganate, peroxy acids and attains the purpose of catalytic conversion without pollution. The method has a low cost and can be applied for producing heterocyclic oxygen compound.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of eco-friendly aqueous hydrogen peroxide solution catalyzed oxidation 1 that utilizes, the method for 5-cyclooctadiene synthesizing heterocyclic oxygen compound.
Background technology
Prepare in the research field of high added value fine chemical product in the alkene selective oxidation, free of contamination hydrogen peroxide oxidant becomes numerous investigators' preferential selection naturally.Hydrogen peroxide is as a kind of eco-friendly oxygenant, and its product has only water, therefore is considered to a kind of environmental protection oxygenant with widespread use potentiality.But simple hydrogen peroxide can't make reaction carry out towards the direction of anticipation, must add special catalyst.It is oxygenant that the present invention has selected with the hydrogen peroxide, and wolframic acid, phospho-wolframic acid or tungstosilicic acid are catalyzer, attempts with 1, and the 5-cyclooctadiene is the synthetic high added value fine chemicals of material choice oxidation.The product 1,2 and 3 of gained (as shown 1) can be as the raw material of synthetic butyrolactone and derivative thereof, and gamma-butyrolactone and derivative thereof have very important pharmaceutical value, all have special biological activity because contain the derivative of this type of group.Gamma-butyrolactone has another name called the gamma-hydroxybutyric acid lactone, has active chemical property, uses very extensive.It is a kind of important organic synthesis raw material and the intermediate of pharmacy, and the production equipment and the consumption of ton all arranged the America and Europe.The demand of gamma-butyrolactone increases with average annual 7% speed in recent years, is a quite rising product.Therefore, study this reaction and have very important economic worth.
1, in the conventional oxidation of 5-cyclooctadiene, the synthetic method of this compounds of domestic and foreign literature report is a lot, generally all very complicated, used oxygenant is chemical oxidizing agent, generally is peroxy acid, potassium permanganate etc., there are some general shortcomings in these oxygenants, serious as environmental pollution, acid pollution is big, and quantity of three wastes is big, product is difficult to separate purification etc., is unfavorable for technical scale production.
The present invention discloses a kind of mild condition, environmental protection be oxygenant oxidation 1 with the aqueous hydrogen peroxide solution, the 5-cyclooctadiene synthesizes oxygen heterocyclic novel process, has significant industrial value.
Summary of the invention
The object of the present invention is to provide a kind of more environmental friendliness, efficient and practical catalyzed oxidation 1, the method for 5-cyclooctadiene synthesizing heterocyclic oxygen compound.
The present invention realizes by following measure:
Use the wolframic acid of toxicological harmless among the present invention, tungstophosphoric acid or tungstosilicic acid are catalyzer, aqueous hydrogen peroxide solution with 20～70% is an oxygenant, with the trimethyl carbinol is solvent, direct catalyzed oxidation 1 under 15～85 ℃, the 5-cyclooctadiene reacted 2～24 hours, the mol ratio of hydrogen peroxide and cyclooctadiene is 1～5: 1, and the volume ratio of the trimethyl carbinol and cyclooctadiene is 1: 2～20.
Catalyzer generally is directly to add or adopt in-situ synthetic method directly to obtain in reaction system in when beginning reaction.Tungstic acid catalyst is mainly yellow wolframic acid H
2WO
4NH
2O, wherein, n=1～4.With H
2WO
42H
2O and H
2WO
43H
2O is for well, and the amount ranges of tungstic acid catalyst is 1～11% of a benchmark with raw material cyclooctadiene mole number.When tungstophosphoric acid and tungstosilicic acid or its hydrate were made catalyzer, amount ranges was 0.01～2% of a benchmark with raw material cyclooctadiene mole number.
The catalyzer that the present invention uses, wherein the structural formula of tungstophosphoric acid catalyst is H
3PW
12O
40NH
2O, n=2～10.The structural formula of tungstosilicic acid catalyzer is H
4SiW
12O
40NH
2O, n=2～10.Also can use its heteropolyacid salt by obtaining tungstophosphoric acid or tungstosilicic acid catalyzer with strong acid (hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid) original position in reaction system.
Detailed process of the present invention is: add the wolframic acid or the heteropoly acid containing tungsten catalyzer of calculated amount earlier, add the aqueous hydrogen peroxide solution of whole consumptions again, stirred 0.5～5 hour under 20 ℃ of-60 ℃ of temperature, make catalyst dissolution.Then,, add the trimethyl carbinol, add 1 by above-mentioned usage ratio, the 5-cyclooctadiene, by the oil bath heating, 15～85 ℃ of temperature are bathed in control, hydrogen peroxide and 1, the mol ratio of 5-cyclooctadiene is 1～5: 1, reacts sampling analysis after 2～24 hours.
The inventive method uses commercial cyclooctadiene to be raw material, and under relatively mild condition, the oxygen helerocyclics total recovery can reach 97～99%.Because the employing aqueous hydrogen peroxide solution is an oxygenant, abandon the environmental issue that oxidation style such as traditional potassium permanganate, peroxy acid are brought simultaneously, realized the purpose of environmental friendliness catalytic conversion process.The inventive method is with low cost, can be used for the suitability for industrialized production oxa-compound.
Description of drawings
Fig. 1 is the product of cyclooctadiene selective oxidation.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1: the preparation of homogeneous phase wolframic acid: with 0.019g WO
3.H
2O is dissolved in 1.4mL 50%H
2O
2, stir 0.5h at 60 ℃, promptly get the homogeneous phase tungstic acid catalyst.Thereafter, add the trimethyl carbinol of 10.6mL, add 1.06mL 1, the 5-cyclooctadiene, by the oil bath heating, 35 ℃ of temperature are bathed in control, and the mol ratio of hydrogen peroxide and cyclooctadiene is 3: 1, reacts 24 hours.Note is made 1#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 2: with 0.032g WO
3.H
2O is dissolved in 2.6ml 27.5%H
2O
2, stir 2h at 50 ℃, promptly get the homogeneous phase tungstic acid catalyst.Other feeding quantity, operating process were reacted 12 hours all with embodiment 1, and note is made 2#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 3: with 0.059g WO
3.H
2O is dissolved in 2.0ml 35%H
2O
2, stir 5h at 40 ℃, promptly get the homogeneous phase tungstic acid catalyst.Other feeding quantity, operating process were reacted 4 hours all with embodiment 1, and note is made 3#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 4: with 0.108g WO
3.H
2O is dissolved in a certain amount of 20%H
2O
2, stir 1h at 20 ℃, promptly get the homogeneous phase tungstic acid catalyst, the mol ratio of hydrogen peroxide and cyclooctadiene is 1.85 ℃ of control reaction temperature, other feeding quantity, operating process were reacted 2 hours all with embodiment 1, and note is made 4#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 5: with 0.216g WO
3.H
2O is dissolved in a certain amount of 70%H
2O
2, stir 2.5h at 30 ℃, promptly get the homogeneous phase tungstic acid catalyst, the mol ratio of hydrogen peroxide and cyclooctadiene is 5: 1.15 ℃ of control reaction temperature, other feeding quantity, operating process were reacted 24 hours all with embodiment 1, and note is made 5#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
5 catalyzer of example 1～5 example are carried out active testing, and its active yield is as a result listed in table 1 respectively.
Embodiment 6: with 0.108g WO
3.H
2O is dissolved in the 50%H of certain volume
2O
2, stir 1h at 40 ℃, promptly get the homogeneous phase tungstic acid catalyst.The solvent 5.3mL trimethyl carbinol is joined in the tungstic acid catalyst, the 1.06mL cyclooctadiene is added in the reaction system again, 35 ℃ of temperature are bathed in control, and the mol ratio of hydrogen peroxide and cyclooctadiene is 3, reacts 3 hours.Note is made 6#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 7: the homogeneous phase tungstic acid catalyst prepares all with embodiment 6.The solvent 2.1mL trimethyl carbinol is joined in the tungstic acid catalyst, and other feeding quantity, operating process and reaction times are all with embodiment 6.Note is made 7#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 8: the homogeneous phase tungstic acid catalyst prepares all with embodiment 6.The solvent 15.9mL trimethyl carbinol is joined in the tungstic acid catalyst, and other feeding quantity, operating process and reaction times are all with embodiment 6.Note is made 8#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 9: the homogeneous phase tungstic acid catalyst prepares all with embodiment 6.The solvent 21.2mL trimethyl carbinol is joined in the tungstic acid catalyst, and other feeding quantity, operating process and reaction times are all with embodiment 6.Note is made 9#.Reaction is finished post analysis and be the results are shown in subordinate list 1.
4 catalyzer of example 6～9 examples are carried out active testing, and its active yield is as a result listed in table 1 respectively.
Embodiment 10～13:
12-tungstophosphoric acid consumption is respectively 0.009g (0.003 mmole), 1.79g (0.6 mmole); 12-tungstosilicic acid consumption is respectively 0.009g (0.003 mmole), 1.79g (0.6 mmole).All adopt 50% aqueous hydrogen peroxide solution to make oxygenant.45 ℃ of control reaction temperature, in 4～24 hours reaction times, other feeding quantity, operating process are all with implementation example 1.Note is made 10#, 11#, 12#, 13# respectively, and reaction is finished post analysis and be the results are shown in subordinate list 1.
Each catalyzer of table 1. is used for the result of cyclooctadiene oxidation synthesizing heterocyclic oxygen compound
| Catalyzer | Cyclooctadiene transformation efficiency (%) | Reaction times/hour | (1+2) yield (%) |
| 1# | 99.6 | 24 | 91.8 |
| 2# | 100 | 12 | 97.7 |
| 3# | 100 | 4 | 97.8 |
| 4# | 90.3 | 2 | 67.5 |
| 5# | 100 | 24 | 99.6 |
| 6# | 100 | 3 | 98.4 |
| 7# | 100 | 3 | 91.5 |
| 8# | 100 | 3 | 93.0 |
| 9# | 98.7 | 3 | 86.9 |
| 10# | 100 | 4 | 88.4 |
| 11# | 100 | 16 | 92.5 |
| 12# | 100 | 12 | 89.0 |
| 13# | 98.7 | 8 | 94.9 |
Claims (8)
1. catalyzed oxidation 1, the 5-cyclooctadiene prepares the method for oxygen helerocyclics, it is characterized in that with wolframic acid, tungstophosphoric acid or tungstosilicic acid be catalyzer, aqueous hydrogen peroxide solution with 20～70% is an oxygenant, with 1 trimethyl carbinol is solvent, generates oxa-compound at 15～85 ℃ of catalyzed oxidation cyclooctadiene, reacts 2～24 hours, the mol ratio of hydrogen peroxide and cyclooctadiene is 1～5: between 1, the volume ratio of the trimethyl carbinol and cyclooctadiene is 1: 2～20.
2. by the described method of claim 1, it is characterized in that the tungstic acid catalyst structure of using is H
2WO
4NH
2O, wherein n=1～4.
3. by the described method of claim 1, it is characterized in that the tungstophosphoric acid catalyst structure of using is H
3PW
12O
40NH
2O, wherein n=2～10.
4. by the described method of claim 1, it is characterized in that the tungstosilicic acid catalyst structure that uses is H
4SiW
12O
40NH
2O, wherein n=2～10.
5. by the described method of claim 1, it is characterized in that tungstic acid catalyst can adopt sodium wolframate and hydrochloric acid original position under reaction conditions synthetic.
6. by the described method of claim 1, the consumption that it is characterized in that tungstic acid catalyst is 1～11% of a raw material cyclooctadiene mole number.
7. by the described method of claim 1, the consumption that it is characterized in that tungstophosphoric acid catalyst is 0.01～2% of a raw material cyclooctadiene mole number.
8. by the described method of claim 1, it is characterized in that the tungstosilicic acid catalyst consumption is 0.01～2% of a raw material cyclooctadiene mole number.
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|---|---|---|---|---|
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
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| ATE56711T1 (en) * | 1987-03-25 | 1990-10-15 | Degussa | PROCESS FOR THE CATALYTIC EPOXYDATION OF OLEFINS WITH HYDROGEN PEROXIDE. |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
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Granted publication date: 20110504 Termination date: 20140206 |