CN104926656A - Self-replacement reaction method for cis-methyl oleate by using ruthenium Schiff base indenyl ylide catalyst - Google Patents
Self-replacement reaction method for cis-methyl oleate by using ruthenium Schiff base indenyl ylide catalyst Download PDFInfo
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
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Abstract
The invention discloses a self-replacement reaction method for cis-methyl oleate by using a ruthenium Schiff base indenyl ylide catalyst. The self-replacement reaction method comprises the following steps: adding a catalyst C50H52ClN3ORu and cis-methyl oleate to a two-opening flask, stirring, and setting the reaction temperature to be 80 DEG C; performing repeated and alternate operations of vacuum pumping and nitrogen charging on a reaction container, finally adding methylbenzene under the condition of nitrogen protection, and then charging nitrogen for performing a closed reaction; preparing a gas chromatograph sample; selecting 1h, 2h, 3h, 4h, 5h and 6h as time points of gas chromatograph tests, and measuring the catalysis yield of methyl oleate self-catalytic reaction. The method has the characteristics of short preparation period, simple operation, high efficiency and energy saving, the methyl oleate self-replacement reaction can be completed within 24h, the yield is 48.3%, and the method has significant practical value.
Description
Technical field
The invention belongs to the field of metallo organic material technology of preparing, be specifically related to the method for a kind of ruthenium schiff bases indenyl ylide catalyzer for the self-replacement(metathesis)reaction of cis Witconol 2301.
Background technology
Olefin metathesis can by the mutual exchange be described as easily by the molecule between the alkylidene group of metal carbene complexes catalysis or metal carbene.Since Banks and Bailey found this reaction in 1964, along with the performance of catalyzer constantly improves, to become in petrochemical industry the technological line of important production alkene, polymkeric substance and a fine chemical product at present.Particularly due to the development of petroleum industry, the demand that global industry market increases day by day to propylene and high-carbon normal olefine, the development of olefin metathesis reaction catalyst technology and application obtain huge progress.
Research and develop and transfer in the method for change core metal atom to the emphasis of the good catalyzer work of functional group tolerance, by experimental results demonstrate, although other transition metal also show can synthetic metals carbon double bond, ruthenium is the most effective metal seemingly, and osmium and iridium have the active of replacement(metathesis)reaction but the reactive system that they participate in compares that ruthenium cost is very expensive and activity is not very high.
The different series Ru carbene complex that the people such as Grubbs develop successively, carbon-to-carbon double bond demonstrates good chemo-selective, has had more reaction site, such as alcohol, acyl, amine, aldehyde and carboxylic acid.Compared with Schrock catalyzer, ruthenium carbene complex does not need harsh reaction conditions relatively, and this makes them more easily be operated when carrying out catalyzed reaction.
Ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu has satisfactory stability, is a kind of high reactivity, ruthenium metal carbene catalyst that storage performance is good, and the research for Novel nail olefin metathesis catalyst provides greatly reference value.At present, also not about the report of ruthenium schiff bases indenyl ylide catalyzer in the self-replacement(metathesis)reaction of Witconol 2301.
Summary of the invention
The object of this invention is to provide the method for a kind of ruthenium schiff bases indenyl ylide catalyzer for the self-replacement(metathesis)reaction of cis Witconol 2301.The present invention has short, simple to operate, the energy-efficient feature of determination period, shows ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu has good Witconol 2301 catalytic performance.
For achieving the above object, the technical solution used in the present invention is:
Ruthenium schiff bases indenyl ylide catalyzer is used for a method for the self-replacement(metathesis)reaction of cis Witconol 2301, comprises the following steps:
1) by catalyzer C
50h
52clN
3the stoichiometric ratio of ORu and each atom of cis Witconol 2301 weighs, C
50h
52clN
3the mol ratio of ORu and Witconol 2301 is 1:50, and solvent is chosen as toluene, and the concentration of substrate in toluene is 500ppm;
2) by catalyzer C
50h
52clN
3oRu and cis Witconol 2301 are added in two mouthfuls of flasks, and stir, temperature of reaction is set as 80 DEG C;
3) vacuumizing and inflated with nitrogen alternate operation is repeatedly carried out to reaction vessel, under the condition of nitrogen protection, finally add the toluene of 5ml, be then filled with nitrogen, carry out capping;
4) preparative gas chromatograph sample: extract 0.1ml system response liquid from above-mentioned olefin metathesis reaction system liquid, join in silicagel column, add 1ml methylene dichloride or toluene, by the method for balloon pressurization, system response liquid is poured the gas chromatograph connected at the bottom of silicagel column post to test in bottle, thus the catalyzer of solid and reaction solution are kept apart;
5) choose 1h, the time point that 2h, 3h, 4h, 5h, 6h test as gas chromatograph, measure the catalysis productive rate of Witconol 2301 oneself catalyzed reaction.
In such scheme, described step 5) in gas chromatograph test parameter be: injector temperature is 250 DEG C, and injection port input nitrogen pressure is 10psi, and splitting ratio is 10; Chromatographic column place baking oven design temperature is 220 DEG C; Fid detector temperature is 250 DEG C, and inputting hydrogen pressure is 30ml/min, and input air pressure is 300ml/min.
In such scheme, brown-red powder shape catalyzer C
50h
52clN
3the quality purity 98% of ORu, the purity 99% of white cis Witconol 2301, the purity 99.9% of white anhydrous toluene.
Compared with prior art, beneficial effect of the present invention has:
1) the present invention is first to ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3the thermostability of ORu is tested, and result proves that the thermostability of ruthenium schiff bases indenyl ylide catalyzer is better than commercially available catalyzer, and the storage that improve olefin metathesis reaction catalyzer is worth, and is more conducive to industrialized production.
2) the present invention is first by ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu is applied to the self-replacement(metathesis)reaction of cis Witconol 2301, and set reaction conditions, ruthenium schiff bases indenyl ylide catalyst activity is very high on the one hand, Witconol 2301 oneself replacement(metathesis)reaction can complete in 24h, the productive rate measured is 48.3%, and this is the maximum output that can obtain so far; Prove that some does not need the olefin metathesis reaction starting catalytic rate fast, catalyzer C in industrial production on the other hand
50h
52clN
3the delayed effect of the olefin metathesis reaction that the thermostability that ORu is good produces has very large economic worth.
3) during the present invention measures about olefin metathesis reaction productive rate, the method of preparative gas chromatograph sample is pioneering, preparation technology is: from olefin metathesis reaction system liquid, extract 0.1ml system liquid, join in homemade little silicagel column, add 1ml reaction solvent, by the method for balloon pressurization, system liquid is poured the gas chromatograph connected at the bottom of little silicagel column post and test in bottle.
Accompanying drawing explanation
Fig. 1 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3the structural representation of ORu.
Fig. 2 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu's
1h-NMR collection of illustrative plates.
Fig. 3 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3after ORu heat stability testing 6h
1h-NMR collection of illustrative plates.
Fig. 4 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu thermostability performance test curve.
Fig. 5 is the self-replacement(metathesis)reaction schematic diagram of cis Witconol 2301.
Fig. 6 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu is about the gas-chromatography collection of illustrative plates of the self-replacement(metathesis)reaction productive rate mensuration of cis Witconol 2301.
Fig. 7 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu measures curve about the self-replacement(metathesis)reaction productive rate of cis Witconol 2301.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment and accompanying drawing, but content of the present invention is not only confined to the following examples.
In following examples, as no specific instructions, the reagent of employing is commercially available chemical reagent.
First the present invention tests ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3the thermostability of ORu, comprises the following steps:
1) the catalyzer C of 120mg is weighed
50h
52clN
3oRu, measures the deuterochloroform of 3ml, mixing add in graduated cylinder, prepare 6 nuclear magnetic tubes, the system liquid extracting 0.5ml respectively joins in nuclear magnetic tube, get wherein one carry out
1the mensuration of H-NMR, the model of nuclear magnetic resonance analyser is NMR spectrometer with superconducting magnet, and specification is AVANCE
iIItM 500MHz.
2) open magnetic heat agitated device, temperature is set as 100 DEG C, is placed in oil bath pan by all the other 5 nuclear magnetic tubes in step 1, to be clamped by nuclear magnetic tube make it erect with pliers.
3) get a nuclear magnetic tube every 1h heat-up time, after cooling 2min rapidly by the condition of ice-water bath, carry out
1the mensuration of H-NMR.After 6h, stop heating.
Fig. 2 be do not carry out heating operation ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu's
1h-NMR collection of illustrative plates, Fig. 3 is the ruthenium schiff bases indenyl ylide catalyzer C of heating after 6 hours
50h
52clN
3oRu's
1h-NMR collection of illustrative plates, ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu throws away the survival rate of 35% when 100 DEG C after 6 hours, compare other commercially available olefin metathesis reaction catalyst stabilities good.Fig. 4 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu thermostability performance test curve.
The invention provides this ruthenium schiff bases indenyl ylide catalyzer for the method for the self-replacement(metathesis)reaction of cis Witconol 2301, comprise the following steps:
1) by catalyzer C
50h
52clN
3the stoichiometric ratio of ORu and each atom of cis Witconol 2301 weighs, and takes catalyzer C
50h
52clN
3oRu 0.0025g, cis Witconol 2301 0.0169g and dry toluene 5ml, prepare one piece of white magneton crossed by toluene wash, is packaged in two mouthfuls of round-bottomed flasks of the 50ml that two adapters are housed, and open magnetic heat agitated device, temperature is set as 80 DEG C.Brown-red powder shape catalyzer C
50h
52clN
3the quality purity 98% of ORu, the purity 99% of white cis Witconol 2301, the purity 99.9% of white anhydrous toluene.
2) two mouthfuls of round-bottomed flasks adapter is in connected state; another adapter connects balloon; carry out the process vacuumized, vacuumizing with the process number of rounds of inflated with nitrogen is 3 times, is finally in the state of inflated with nitrogen; take the adapter connecting balloon away; under the condition of nitrogen protection, add the toluene of 5ml, connect adapter, be filled with nitrogen; when balloon is in full state, close nitrogen protection and carry out sealing treatment.
3) 1h is chosen, 2h, 3h, 4h, 5h, the time point that 6h tests as gas chromatograph, the technique of preparative gas chromatograph sample is: from olefin metathesis reaction system liquid, extract 0.1ml system response liquid, joins in homemade little silicagel column, adds 1ml reaction solvent, by the method for balloon pressurization, system response liquid being poured the specification connected at the bottom of little silicagel column post is in the gas chromatograph test bottle of 1.5ml, thus the catalyzer of solid and reaction solution is kept apart.
4) model of gas chromatograph is Agilent Technology GC7890A, automatic sampler G4513A.Gas chromatograph is about the method for measuring of Witconol 2301 oneself catalyzed reaction catalysis productive rate, and setup parameter is: injector temperature is 250 DEG C, and injection port input nitrogen pressure is 10psi, and splitting ratio is 10; Chromatographic column place baking oven design temperature is 220 DEG C; Fid detector temperature is 250 DEG C, and inputting hydrogen pressure is 30ml/min, and input air pressure is 300ml/min.
Fig. 6 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3the gas-chromatography collection of illustrative plates that after ORu carries out 6h about the self-replacement(metathesis)reaction of cis Witconol 2301, productive rate measures, after 6h, productive rate is 48.3%.Fig. 7 is ruthenium schiff bases indenyl ylide catalyzer C
50h
52clN
3oRu measures curve about the self-replacement(metathesis)reaction productive rate of cis Witconol 2301.
The above is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, make some improvement and conversion, these all belong to protection scope of the present invention.
Claims (3)
1. ruthenium schiff bases indenyl ylide catalyzer is used for a method for the self-replacement(metathesis)reaction of cis Witconol 2301, it is characterized in that, comprises the following steps:
1) by catalyzer C
50h
52clN
3the stoichiometric ratio of ORu and each atom of cis Witconol 2301 weighs, C
50h
52clN
3the mol ratio of ORu and Witconol 2301 is 1:50, and solvent is chosen as toluene, and the concentration of substrate in toluene is 500ppm;
2) by catalyzer C
50h
52clN
3oRu and cis Witconol 2301 are added in two mouthfuls of flasks, and stir, temperature of reaction is set as 80 DEG C;
3) vacuumizing and inflated with nitrogen alternate operation is repeatedly carried out to reaction vessel, finally under the condition of nitrogen protection, add toluene, be then filled with nitrogen, carry out capping;
4) preparative gas chromatograph sample: extract 0.1ml system response liquid from above-mentioned olefin metathesis reaction system liquid, join in silicagel column, add 1ml methylene dichloride or toluene, by the method for balloon pressurization, system response liquid is poured the gas chromatograph connected at the bottom of silicagel column post to test in bottle, thus the catalyzer of solid and reaction solution are kept apart;
5) choose 1h, the time point that 2h, 3h, 4h, 5h, 6h test as gas chromatograph, measure the catalysis productive rate of Witconol 2301 oneself catalyzed reaction.
2. the method for claim 1, is characterized in that, described step 5) in gas chromatograph test parameter be: injector temperature is 250 DEG C, injection port input nitrogen pressure be 10psi, splitting ratio is 10; Chromatographic column place baking oven design temperature is 220 DEG C; Fid detector temperature is 250 DEG C, and inputting hydrogen pressure is 30ml/min, and input air pressure is 300ml/min.
3. the method for claim 1, is characterized in that, brown-red powder shape catalyzer C
50h
52clN
3the quality purity 98% of ORu, the purity 99% of white cis Witconol 2301, the purity 99.9% of white anhydrous toluene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565866A (en) * | 2016-01-29 | 2017-04-19 | 上海克琴化工科技有限公司 | Schiff base ligand ruthenium metal catalyst, preparation and applications thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101193840A (en) * | 2005-06-06 | 2008-06-04 | 陶氏环球技术公司 | Metathesis process for preparing an alpha, omega-functionalized olefin |
| CN103492357A (en) * | 2011-04-20 | 2014-01-01 | 考格尼斯知识产权管理有限责任公司 | Method for producing unsaturated compounds |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101193840A (en) * | 2005-06-06 | 2008-06-04 | 陶氏环球技术公司 | Metathesis process for preparing an alpha, omega-functionalized olefin |
| CN103492357A (en) * | 2011-04-20 | 2014-01-01 | 考格尼斯知识产权管理有限责任公司 | Method for producing unsaturated compounds |
Non-Patent Citations (1)
| Title |
|---|
| DOMINIK M. OHLMANN, ET AL.: ""Isomerizing Olefin Metathesis as a Strategy To Access Defined Distributions of Unsaturated Compounds from Fatty Acids"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 134, 20 July 2012 (2012-07-20), pages 13716 - 13729, XP055043186, DOI: doi:10.1021/ja303822c * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565866A (en) * | 2016-01-29 | 2017-04-19 | 上海克琴化工科技有限公司 | Schiff base ligand ruthenium metal catalyst, preparation and applications thereof |
| CN106565866B (en) * | 2016-01-29 | 2020-01-31 | 上海克琴科技有限公司 | Schiff base ligand ruthenium metal catalyst, and preparation and application thereof |
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Application publication date: 20150923 |