CN1534033A - Preparation method of 3-methylfuran - Google Patents
Preparation method of 3-methylfuran Download PDFInfo
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- CN1534033A CN1534033A CNA031160875A CN03116087A CN1534033A CN 1534033 A CN1534033 A CN 1534033A CN A031160875 A CNA031160875 A CN A031160875A CN 03116087 A CN03116087 A CN 03116087A CN 1534033 A CN1534033 A CN 1534033A
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- preparation
- methyl
- molybdenum
- schiff bases
- complex compound
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- KJRRQXYWFQKJIP-UHFFFAOYSA-N 3-methylfuran Chemical compound CC=1C=COC=1 KJRRQXYWFQKJIP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002262 Schiff base Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- 150000004753 Schiff bases Chemical class 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 5
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BNYIQEFWGSXIKQ-UHFFFAOYSA-N 3-methylfuran-2-carboxylic acid Chemical compound CC=1C=COC=1C(O)=O BNYIQEFWGSXIKQ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A 3-methylfuran is prepared through the epoxilation reaction between isopentanediene and hydrogen peroxide under the existance of Mo-Schiff base complex as catalyst. Its advantages are low cost and high output rate.
Description
Technical field
The present invention relates to a kind of method of the 3-of preparation methyl furan, particularly relating to a kind of is raw material with isoprene, prepares the method for 3-methyl furan.
Technical background
In China Petroleum, by-product C
5Amount more, isoprene is one of wherein important by product.By-product C in 2000
5The ability of cut is about 5.5 * 10
4About ton/year, wherein isoprene containing 15%～20%.Isoprene is mainly used in synthetic rubber at present, and other purposes is very few, but because the rubber that synthesizes with isoprene has a certain distance with natural rubber in every index test, the scope of application is narrow relatively, now not high to its utilization ratio yet.The isoprene boiling point is low in addition, has extremely strong topsoil and to the hazardness of human body.Isoprene has the carbon atom of latent chirality, if it is carried out oxidation and becomes organic synthesis intermediate, will widen its range of application greatly.
The 3-methyl furan claims the Beta-methyl furans again, is a kind of organic solvent commonly used, also is a kind of important organic synthesis intermediate simultaneously.
3-methyl furan prior preparation method is:, be heated to 250 ℃ of decarboxylations and get under the catalysis of Cu powder by 3-methyl-pyromucic acid, main chemical reactions is:
This method raw material complexity, the temperature of reaction height is not a kind of good preparation method.
Summary of the invention
It is raw material that the object of the invention provides with isoprene, is that catalyzer and hydrogen peroxide are oxygenant with transition metal molybdenum-schiff bases complex compound, the preparation method of catalysis epoxidation 3-methyl furan.
The preparation method of 3-methyl furan provided by the invention, the principal reaction that relates to is:
The complex compound catalyst that above-mentioned reaction adopts transition metal molybdenum and schiff bases to form, temperature at 10～70 ℃, reaction times 1～24h, the content 0.05%～1% of catalyzer and isoprene/hydrogen peroxide ratio is in 0.25～4 the scope, isoprene is in the organic solvent of benzene, under the nitrogen atmosphere and hydroperoxidation, generate the 3-methyl furan.
The complex compound catalyst building-up process that above-mentioned transition metal molybdenum and schiff bases form is divided into three steps.
The first step: the parent complex compound of synthetic molybdenum-schiff bases is a raw material with oxide compound and the methyl ethyl diketone that crosses metal molybdenum, and molybdenum and methyl ethyl diketone are heated to certain temperature according to a certain percentage in oil bath, stirs, and refluxes 24 hours.
Second step: synthetic schiff bases part, salicylic aldehyde is dissolved in 95% ethanolic soln, add a certain proportion of quadrol again, there is the glassy yellow solids to separate out immediately, and then uses 95% ethyl alcohol recrystallization.
The 3rd step: synthetic molybdenum-schiff bases adds MoO in methyl alcohol
2(acac)
2Be suspension, add equimolar Schiff's base again, be heated to 80～90 ℃, refluxed 2 hours.
In the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases of the present invention, the oxide compound of described molybdenum is a molybdic oxide.
In the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases of the present invention, described molybdenum: methyl ethyl diketone is 1: 9 mol ratio.
In the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases of the present invention, described temperature is 135～145 ℃.
In the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases of the present invention, described salicylic aldehyde and quadrol mol ratio are 2: 1.
The preparation method of 3-methyl furan provided by the invention is at MoO
2(Salen) complex compound catalyst exists down, and isoprene obtains the 3-methyl furan of higher yields, simultaneously the temperature of reaction gentleness at certain medium neutralization of hydrogen peroxide effect epoxidation.
Catalyzer of the present invention is applicable to that the isoprene epoxidation prepares the 3-methyl furan, need not to carry out any processing before reaction, and technology is simple, easy to operate.It is simple that catalyzer has the preparation method, the characteristics of low price and higher catalytic activity.3-methyl furan selectivity can reach 93.9%, and productive rate can reach 72%.
Embodiment
Describe concrete implementation step of the present invention in detail below by some embodiment, these embodiment should be used as the restriction of the scope of the invention.
Embodiment 1: prepare complex compound catalyst of the present invention:
The first step: the parent MoO of synthetic molybdenum-schiff bases
2(acac)
2(acac=C
5H
7O
2) complex compound, concrete grammar is as follows: with molybdic oxide and methyl ethyl diketone is raw material, molybdenum and methyl ethyl diketone be (mol ratio 1: 9) according to a certain percentage, is heated to 135 ~ 145 ℃ in oil bath, stirs.Behind the backflow 24h, filtered while hot is removed unreacted molybdic oxide, and 1 ~ 2h is left standstill in the filtrate cooling, obtains orange-yellow solid.Wash 3 times to remove the methyl ethyl diketone of attachment removal with sherwood oil (30 ~ 60 ℃ of boiling ranges).
Synthetic Salen part of second step, synthetic method is as follows: salicylic aldehyde is dissolved in 95% ethanolic soln, adds quadrol (salicylic aldehyde and quadrol mol ratio are 2: 1) again, have the glassy yellow solids to separate out immediately, and then use 95% ethyl alcohol recrystallization.This part is called the Salen part, is the organic compound that contains N, O atom electronation group.Structural formula is:
Synthetic molybdenum of the 3rd step-schiff bases MoO
2(Salen), concrete steps are: add homemade MoO in methyl alcohol
2(acac)
2Be suspension, add equimolar Schiff's base again, be heated to 80～90 ℃, allow this solution reflux.Soon will see solids and separate out, continue backflow 2h, filtered while hot obtains orange-yellow crystal, uses the methanol wash secondary, desolvates to remove again with the ether washing, and with Rotary Evaporators.
Levy through analysis instrumentation tables such as elemental analyser, thermogravimetric instrument, Fourier infrared spectrograph, ultraviolet-visible pectrophotometer, nuclear magnetic resonance analyser, that determines this complex compound may consist of MoO
2(C
16H
14N
2O
2), possible structural formula as shown in the figure:
Embodiment 2: the catalytic perfomance under the top condition:
Method for preparing catalyst is with reference to the method for embodiment 1, get 0.1% (mol ratio, with the isoprene is standard) solid catalyst join in the two neck flasks, flask is vacuumized deoxygenation earlier, then feed nitrogen, so switch for several times in the flask of back under nitrogen atmosphere, add benzene successively with syringe again, hydrogen peroxide and isoprene are put into oil bath with flask and are heated, make to be reflected under 40 ℃ of temperature and carry out, react after 6 hours, reaction system is cooled to room temperature, takes out reaction liquid and analyzes, the result shows: the transformation efficiency of isoprene is 76.7%, and the productive rate of 3-methyl furan is 72%.
Embodiment 3: the catalytic perfomance of different catalysts content:
Repeat the operation steps of embodiment 2, just change the content of catalyzer in the reaction system, other reaction conditions is all constant, and reaction result is listed in table 1.
The reaction result of table 1 different catalysts content
| Catalyst content (%) | Transformation efficiency (%) | Selectivity (%) | Productive rate (%) |
| ??0.05 | ????72.17 | ????83.14 | ????60.00 |
| ??0.1 | ????76.72 | ????93.91 | ????72.05 |
| ??0.2 | ????76.78 | ????82.52 | ????63.36 |
| ??0.4 | ????68.01 | ????84.69 | ????57.59 |
| ??0.6 | ????67.42 | ????83.67 | ????56.41 |
| ??0.8 | ????64.16 | ????84.91 | ????54.47 |
| ??1 | ????59.96 | ????81.09 | ????48.62 |
Embodiment 4: the catalytic perfomance of distinct isoprene/hydrogen peroxide ratio:
Repeat the operation steps of embodiment 2, just change the mol ratio of isoprene and hydrogen peroxide, other reaction conditions is all constant, reaction result.The reaction result of table 2 distinct isoprene/hydrogen peroxide ratio
| Isoprene/hydrogen peroxide | Transformation efficiency (%) | Selectivity (%) | Productive rate (%) |
| ????0.25 | ????63.93 | ????80.44 | ????51.42 |
| ????0.5 | ????63.57 | ????78.64 | ????49.99 |
| ????1 | ????76.72 | ????93.91 | ????72.05 |
| ????2 | ????84.11 | ????81.41 | ????68.47 |
| ????4 | ????79.15 | ????73.51 | ????58.18 |
Implement 5: the catalytic perfomance of differential responses temperature:
Repeat the operation steps of embodiment 2, just change the temperature of reaction of reaction system, other reaction conditions is all constant, and reaction result is listed in table 3.
The reaction result of table 3 differential responses temperature
| Temperature of reaction (℃) | Transformation efficiency (%) | Selectivity (%) | Productive rate (%) |
| ????10 | ????36.55 | ????51.10 | ????18.68 |
| ????25 | ????69.12 | ????46.34 | ????32.03 |
| ????40 | ????76.72 | ????93.91 | ????72.05 |
| ????55 | ????65.00 | ????76.30 | ????49.60 |
| ????70 | ????82.07 | ????52.96 | ????43.46 |
Embodiment 6: the catalytic perfomance of differential responses time:
Repeat the operation steps of embodiment 2, just change the reaction times of reaction system, other reaction conditions is all constant, and reaction result is listed in table 4.
The reaction result of table 4 differential responses time
| Reaction times (h) | Transformation efficiency (%) | Selectivity (%) | Productive rate (%) |
| ??1 | ????48.69 | ????77.39 | ????37.68 |
| ??3 | ????48.05 | ????79.96 | ????38.42 |
| ??6 | ????76.72 | ????93.91 | ????72.05 |
| ??9 | ????69.69 | ????81.15 | ????56.55 |
| ??12 | ????65.29 | ????79.57 | ????51.95 |
| ??18 | ????77.00 | ????78.92 | ????60.76 |
| ??21 | ????75.01 | ????83.36 | ????62.52 |
| ??24 | ????78.20 | ????80.76 | ????63.16 |
Claims (7)
1, the present invention is a kind of preparation method of 3-methyl furan, and the principal reaction that relates to is:
It is characterized in that; The complex compound catalyst that adopts transition metal molybdenum and schiff bases to form, temperature at 10～70 ℃, reaction times 1～24h, the content 0.05%～1% of catalyzer and isoprene/hydrogen peroxide ratio is in 0.25～4 the scope, isoprene is in the organic solvent of benzene, under the nitrogen atmosphere and hydroperoxidation, generate the 3-methyl furan.
2, according to the preparation method of right 1 described 3-methyl furan, it is characterized in that: before adding reactant, earlier catalyzer is added in the reactor, carry out the deoxygenation operation, add solvent, hydrogen peroxide and isoprene when reaction system is nitrogen atmosphere more successively.
3, the preparation method of 3-methyl furan according to claim 1 is characterized in that: the preparation process of the complex compound catalyst of described transition metal molybdenum-schiff bases
The first step: the parent complex compound of synthetic molybdenum-schiff bases is a raw material with oxide compound and the methyl ethyl diketone that crosses metal molybdenum, and molybdenum and methyl ethyl diketone are heated to certain temperature according to a certain percentage in oil bath, stirs, refluxed 24 hours,
Second step: synthetic schiff bases part, salicylic aldehyde is dissolved in 95% ethanolic soln, add a certain proportion of quadrol again, there is the glassy yellow solids to separate out immediately, and then uses 95% ethyl alcohol recrystallization,
The 3rd step: synthetic molybdenum-schiff bases adds MoO in methyl alcohol
2(acac)
2Be suspension, add equimolar Schiff's base again, be heated to 80～90 ℃, refluxed 2 hours.
4, according to the preparation method of right 1 or 3 described 3-methyl furans, it is characterized in that: in the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases, the oxide compound of described molybdenum is a molybdic oxide.
5, according to the preparation method of right 1 or 3 described 3-methyl furans, it is characterized in that: in the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases, molybdenum: methyl ethyl diketone is 1: 9 mol ratio
6, according to the preparation method of right 1 or 3 described 3-methyl furans, it is characterized in that: in the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases, described temperature is 135～145 ℃.
7, according to the preparation method of right 1 or 3 described 3-methyl furans, it is characterized in that: in the preparation of the complex compound catalyst of transition metal molybdenum-schiff bases, described salicylic aldehyde and quadrol mol ratio are 2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031160875A CN1534033A (en) | 2003-03-28 | 2003-03-28 | Preparation method of 3-methylfuran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031160875A CN1534033A (en) | 2003-03-28 | 2003-03-28 | Preparation method of 3-methylfuran |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1534033A true CN1534033A (en) | 2004-10-06 |
Family
ID=34284580
Family Applications (1)
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|---|---|---|---|
| CNA031160875A Pending CN1534033A (en) | 2003-03-28 | 2003-03-28 | Preparation method of 3-methylfuran |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012485A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Acetylacetone shrinkage benzoyl hydrazine molybdenum complex and preparation method thereof |
| CN103012486A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103012325A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Method for producing propylene epoxide through propylene epoxidation reaction |
| CN103012324A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Propylene epoxidation reaction method |
-
2003
- 2003-03-28 CN CNA031160875A patent/CN1534033A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012485A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Acetylacetone shrinkage benzoyl hydrazine molybdenum complex and preparation method thereof |
| CN103012486A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103012325A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Method for producing propylene epoxide through propylene epoxidation reaction |
| CN103012324A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Propylene epoxidation reaction method |
| CN103012324B (en) * | 2011-09-22 | 2014-09-10 | 中国石油化工股份有限公司 | Propylene epoxidation reaction method |
| CN103012325B (en) * | 2011-09-22 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing propylene epoxide through propylene epoxidation reaction |
| CN103012486B (en) * | 2011-09-22 | 2015-10-21 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103012485B (en) * | 2011-09-22 | 2015-10-21 | 中国石油化工股份有限公司 | Acetylacetone shrinkage benzoyl hydrazine molybdenum complex and preparation method thereof |
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