CN105618146A - Ruthenium carbene catalyst and synthetic method thereof - Google Patents
Ruthenium carbene catalyst and synthetic method thereof Download PDFInfo
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Abstract
The invention provides a ruthenium carbene catalyst. The ruthenium carbene catalyst is characterized by being a compound with a structural formula shown in the specification; the synthetic method of the ruthenium carbene catalyst, namely the compound comprises the following steps: rutheniumchloride hydrate and ligand react to produce a ruthenium complex, the ruthenium complex and a diphenyl diazomethane compound react to produce a ruthenium carbene complex, and then the ruthenium carbene complex and tricyclohexylphosphine react to produce the target ruthenium carbene catalyst. The ruthenium carbene catalyst is prepared by selecting rutheniumchloride hydrate, ligand, substituted diphenyl diazomethane and the like as the main materials, therefore the raw materials are simple and easily obtainable, and industrial large-scale production is facilitated.
Description
Technical field
The present invention relates to organic synthesis field, in particular it relates to a kind of ruthenium metal carbene catalyst and synthetic method thereof.
Background technology
From the 1950's since heterogeneous olefin metathesis catalyst containing W, Mo or Re oxide comes out, Schrock and Grubbs et al. have developed again in succession has one-component, controlled, the better Mo metal carbene (J.Am.Chem.Soc.1998 of stability of activity, 120,9720-9721.) and Ru (J.Am.Chem.Soc.1999,121,2674-2678.) metal carbene homogeneous catalyst.
Particularly the ruthenium metal carbene catalyst of Grubbs et al. exploitation is increasingly widely applied because the stability of oxygen and protonic solvent is had by it in pharmacy and materials industry.
This type of catalyst owing to it is to the good toleration of the polar group containing proton, various need to utilize in the synthesis of RCM (ringclosingmetathesis) drug molecule building new macrocyclic structure have important effect:
Synthesis such as antitumor drug Epothilone (J.Am.Chem.Soc.1997,119,7960-7973.) and the micromolecular compound BILN2061 (Org.Process.Res.Dev.2005,9,513-515.) suppressing HCV virus.
Summary of the invention
It is desirable to provide a kind of novel ruthenium metal carbene catalyst.
A kind of ruthenium carbone catalyst provided by the invention, it is characterised in that for the compound shown in following structure:
Wherein, R1For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, alkoxyl and substituted alkoxy, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
R2For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, alkoxyl and substituted alkoxy, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro.
Additionally, in the present invention, R1And R2It preferably is selected from H, Me, Et, Ph, Cl, Br, I.
In addition, the preparation method that present invention also offers above-mentioned ruthenium carbone catalyst, it is characterized in that: after being obtained ruthenium complex by hydrate ruthenium trichloride with ligand reaction, after reacting generation Ru carbene complex with hexichol base class diazomethane compound, with formation target ruthenium carbone catalyst after thricyclohexyl phosphine reaction.
Concrete synthesis technique is as follows:
Step one, hydrate ruthenium trichloride and ligand L are heated in organic solvent to 40-80 DEG C, react 3-12 hour, obtain ruthenium complex Cl2RuLn;
Wherein, n is the integer of 1-10;
Above-mentioned ligand L is selected from can with any ligand compound of Ru metal generation complexation reaction, it is preferable that from triphenylphosphine (PPh3) or 1,5-cyclo-octadiene (COD);
The mass ratio of above-mentioned hydrate ruthenium trichloride and part is 1:3-8; It is preferably 1:4-5; (equivalents of part is 3-8 times. )
Reaction temperature in above-mentioned steps is preferably 50-60 DEG C;
The response time of above-mentioned steps is preferably 4-5 hour;
The above-mentioned organic solvent mixture of one or more in the alcohol that boiling point is 40-80 DEG C, dichloromethane, chloroform, tetrachloromethane, oxolane, dioxane, benzene, toluene, it is preferred to use alcohols solvent. Optimum bit selecting methanol or ethanol.
In addition, in above-mentioned course of reaction, preferably employ and put into ligand L again after hydrate ruthenium trichloride low-temperature heat in a solvent being dissolved, it is warming up to target temperature and carries out complexation reaction, when there being solid matter to produce in reaction system, can terminating reaction, the mode of cooled, crystallization and filtration obtains solid product, its productivity, more than 95%, generally can obtain the productivity of almost 100%.
Step 2, by ruthenium complex Cl2RuLnIt is dissolved in organic solvent, keeps at the temperature of 0 DEG C, drip hexichol base class diazomethane compound, generate Ru carbene complex;
The mixture of one or more that above-mentioned organic solvent can reach in the organic solvent in-78 DEG C selected from the alcohol that boiling point is 40-80 DEG C, dichloromethane, chloroform, tetrachloromethane, oxolane, dioxane, benzene, toluene and other apparent freezing points, it is preferred to the one in dichloromethane, chloroform, tetrachloromethane, oxolane.
The mass ratio of above-mentioned ruthenium complex and hexichol base class diazomethane compound is 1-10:1 (mol ratio is 1:0.5-3, it is preferred to 1:1-2); The preferable amount of hexichol base class diazomethane compound is, in the process of dropping hexichol base class diazomethane solution, the phenomenon of exotherm occurs in reaction, and what maintenance reaction system was mild carries out in process, changes as dropping terminal with system color.
The structure of above-mentioned hexichol base class diazomethane compound is as follows:
R1For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, alkoxyl and substituted alkoxy, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
R2For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, alkoxyl and substituted alkoxy, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
Its manufacture method is as described below: the Benzophenonehydrazones replaced, anhydrous sodium sulfate, ether, saturated potassium hydroxide-ethanol solution and yellow mercury oxide are added in pressure bottle, jolting reaction 75-120min.
Filtering, at room temperature removal of solvent under reduced pressure, residue is dissolved in petroleum ether, again filters, filtrate decompression is evaporated off solvent, and remaining grease is the diphenyl diazomethane replaced.
Also it is not excluded in the present invention using other modes that can be used for generating the diphenyl diazomethane of replacement.
The structure of above-mentioned Ru carbene complex is as follows:
R1For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, alkoxyl and substituted alkoxy, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
R2For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, alkoxyl and substituted alkoxy, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
L is selected from can with any ligand compound of Ru metal generation complexation reaction, it is preferable that from triphenylphosphine (PPh3) or 1,5-cyclo-octadiene (COD).
Step 3, raise system temperature to 30-50 DEG C, in above-mentioned Ru carbene complex solution, add tricyclohexyl phosphine, after stirring reaction no longer changes to system color, post-treated obtain target ruthenium carbone catalyst; Its productivity reaches more than 65%.
In above-mentioned tricyclohexyl phosphine and reaction, the mol ratio of ruthenium metal is 2-2.5:1.
In this step, the above-mentioned post-treated process obtaining target ruthenium carbone catalyst, particularly as follows: reactant is through being evaporated off organic solvent, adds mixed solvent making beating, purification in the temperature range of 50-80 DEG C, obtains target ruthenium carbone catalyst after filtration.
Wherein, above-mentioned mixed solvent is selected from two or more mixture in the carbon number ketone less than 20, alcohols, ethers, esters equal solvent. It preferably is selected from the mixture of the boiling point ketone less than 150 DEG C and alcohols solvent; The mass ratio of this ketones solvent and alcohols solvent is 1:2-5. Several most preferably from acetone, methylisobutylketone, methanol, ethanol.
The mass ratio of above-mentioned mixed solvent and tricyclohexyl phosphine is 5-10:1.
In above-mentioned reactions steps two and three; carrying out when preferably in inert gas shielding, concrete steps are preferably, after being dissolved in organic solvent by ruthenium complex intermediate; it is cooled to-78 DEG C--30 DEG C (it is preferably-50 DEG C--40 DEG C) after, the solution of dropping diazonium compound. Temperature reaction, reaction system color adds tricyclohexyl phosphine white solid after changing. Continue reaction to tricyclohexyl phosphine white solid molten to the greatest extent and system color no longer change, organic solvent in reaction system is evaporated off, residue pull an oar after purification filtration in ketone/alcohols mixed solvent, obtains pure catalyst solid.
The effect of the present invention and effect:
The present invention selects hydrate ruthenium trichloride, part, substituted diphenylamine base Azimethylene. etc. to prepare ruthenium carbone catalyst as main material, and raw material is simple, be easy to get and be easy to industrialized great production.
Additionally, the technique that the present invention adopts, its condition is simple, operation is convenient, response speed is fast, by-product is few, productivity is high, and post processing that need not be complicated carries out the separation of net product.
It addition, this reaction is applicable to the classes of compounds that on phenyl ring, difference replaces, user can regulate the electrical to reach to regulate the purpose of catalyst catalytic performance of ruthenium Cabbeen by the substituent group on two phenyl ring of change.
Detailed description of the invention
Embodiment 1
In the there-necked flask of 2L, add the absolute methanol of 1.3L, add hydrate ruthenium trichloride 100g, be completely dissolved to solid in 20 DEG C of stirrings, be subsequently adding triphenylphosphine 400g. React 4 hours in 50 DEG C of heated and stirred, have red brown solid product to precipitate out, reaction system is cooled to room temperature, filter out solid product, after drying, obtain about 400g red brown solid product RuCl2(PPh3)3, yield 100%.
By 50gRuCl2(PPh3)3Add to 500mL there-necked flask, when nitrogen protection, add 150mL dichloromethane and dissolve, at 0 DEG C, drip the solution of 20.25g diphenyl diazomethane (being dissolved in 100mL dichloromethane). Having a small amount of gas slowly to release in reaction bulb, reactant liquor is become aubergine from brown always, rises to room temperature and is further continued for stirring reaction 30 minutes. Add tricyclohexyl phosphine 30g, react 30 minutes, stopped reaction.
After methylene chloride is evaporated off, addition 250mL acetone is slowly dropped to room temperature, precipitates out a large amount of mauve glittering crystal after being stirred vigorously making beating 2 hours at 50 DEG C. 20g aubergine solid product is obtained after filtration.
The spectrum analysis data of this product:
Molecular formula: C49H76Cl2P2Ru
M/z:898.38 (100.0%)
ElementalAnalysis:C:65.41; H:8.49; P:6.81
HNMR(400MHz):
��=7.52-7.44 (6H, m); 7.35 (4H, d, J=8Hz); 1.57-1.40 (66H, m).
Embodiment 2
In the there-necked flask of 2L, add the dehydrated alcohol of 1.3L, add hydrate ruthenium trichloride 100g, be completely dissolved to solid in 25 DEG C of stirrings, be subsequently adding triphenylphosphine 500g. React 4 hours in 60 DEG C of heated and stirred, have red brown solid product to precipitate out, reaction system is cooled to room temperature, filter out solid product, after drying, obtain about 400g red brown solid product RuCl2(PPh3)3��
By 50gRuCl2(PPh3)3Add to 500mL there-necked flask, when nitrogen protection, add 150mL oxolane and dissolve, at-10 DEG C, drip 12g3, the solution that 3 '-dimethyl diphenyl Azimethylene. (is dissolved in 100mL oxolane). Having a small amount of gas slowly to release in reaction bulb, reactant liquor is become aubergine from brown always, rises to room temperature and is further continued for stirring reaction 60 minutes. Add tricyclohexyl phosphine 35g, react 15 minutes, stopped reaction.
After solvents tetrahydrofurane is evaporated off, addition 250mL acetone/ethanol (25/75) is slowly dropped to room temperature, precipitates out a large amount of mauve glittering crystal after being stirred vigorously making beating 1 hour at 80 DEG C. 32g aubergine solid product is obtained after filtration.
The spectrum analysis data of this product:
Molecular formula: C51H80Cl2P2Ru
M/z:926.42 (100.0%)
ElementalAnalysis:C:65.99; H:8.62; P:6.71
Embodiment 3
In the there-necked flask of 2L, add the anhydrous tetrahydro furan of 1L, add hydrate ruthenium trichloride 100g, be completely dissolved to solid in 25 DEG C of stirrings, be subsequently adding triphenylphosphine 300g. React 5 hours in 80 DEG C of heated and stirred, have red brown solid product to precipitate out, reaction system is cooled to room temperature, filter out solid product, after drying, obtain about 380g red brown solid product RuCl2(PPh3)3��
By 50gRuCl2(PPh3)3Add to 500mL there-necked flask, when nitrogen protection, add 150mL oxolane and dissolve, at-40 DEG C, drip 35g3, the solution that 3 '-two fluoro-diphenyl diazomethane (is dissolved in 100mL oxolane). Having a small amount of gas slowly to release in reaction bulb, reactant liquor is become aubergine from brown always, rises to room temperature and is further continued for stirring reaction 15 minutes. Add tricyclohexyl phosphine 35g, react 60 minutes, stopped reaction.
After solvents tetrahydrofurane is evaporated off, addition 200mL ether/acetone (15/85) is slowly dropped to room temperature, precipitates out a large amount of mauve glittering crystal after being stirred vigorously making beating 0.5 hour at 80 DEG C. 35g aubergine solid product is obtained after filtration.
The spectrum analysis data of this product:
Molecular formula: C49H74Cl2F2P2Ru
M/z:934.37 (100.0%)
ElementalAnalysis:C:62.99; H:8.02; P:6.55
Embodiment 4
In the there-necked flask of 2L, add the absolute methanol of 1L, add hydrate ruthenium trichloride 100g, be completely dissolved to solid in 25 DEG C of stirrings, be subsequently adding triphenylphosphine 800g. React 8 hours in 60 DEG C of heated and stirred, have red brown solid product to precipitate out, reaction system is cooled to room temperature, filter out solid product, after drying, obtain about 400g red brown solid product RuCl2(PPh3)3��
By 50gRuCl2(PPh3)3Add to 500mL there-necked flask, when nitrogen protection, add 150mL chloroform and dissolve, at-30 DEG C, drip 25g5, the solution that 5 '-dimethoxy-diphenyl diazomethane (is dissolved in 100mL chloroform). Having a small amount of gas slowly to release in reaction bulb, reactant liquor is become aubergine from brown always, rises to room temperature and is further continued for stirring reaction 10 minutes. Add tricyclohexyl phosphine 25g, react 45 minutes, stopped reaction.
After solvent chloroform is evaporated off, addition 120mL methanol/methylisobutylketone (30/60) is slowly dropped to room temperature, precipitates out a large amount of mauve glittering crystal after being stirred vigorously making beating 1 hour at 50 DEG C. The dark violet red solid product of 42g is obtained after filtration.
The spectrum analysis data of this product:
Molecular formula: C51H80Cl2O2P2Ru
M/z:959.10 (100.0%)
ElementalAnalysis:C:63.81; H:8.37; O:3.35
Embodiment 5
In the there-necked flask of 2L, add the absolute methanol of 1L, add hydrate ruthenium trichloride 100g, be completely dissolved to solid in 25 DEG C of stirrings, be subsequently adding triphenylphosphine 400g. React 8 hours in 60 DEG C of heated and stirred, have red brown solid product to precipitate out, reaction system is cooled to room temperature, filter out solid product, after drying, obtain about 400g red brown solid product RuCl2(PPh3)3��
By 100gRuCl2(PPh3)3Add to 1000mL there-necked flask; when nitrogen protection; add 400mL dichloromethane to dissolve; 4 are dripped at-78 DEG C; 4 '-diphenyl-diphenyl diazomethane (is dissolved in 300mL dichloromethane; count roughly 30-50g) solution become pale red to reactant liquor from brown, rise to room temperature and be further continued for stirring reaction 30 minutes. Add tricyclohexyl phosphine 60g, react 90 minutes, stopped reaction.
After methylene chloride is evaporated off, addition 200mL methanol is slowly dropped to room temperature, precipitates out a large amount of mauve glittering crystal after being stirred vigorously making beating 1 hour at 80 DEG C. The dark violet red solid product of 85g is obtained after filtration.
The spectrum analysis data of this product:
Molecular formula: C61H84Cl2P2Ru
M/z:1050.45 (100.0%)
ElementalAnalysis:C:69.73; H:8.00
In above-described embodiment one to five, formed in the process of ligand compound in step one, triphenylphosphine can replace for other ligand compounds, particularly preferably replace with 1,5-cyclo-octadiene (COD), the results showed, its reaction result is basically identical with above-described embodiment, therefore, no longer do and repeat to discuss.
Claims (10)
1. a ruthenium carbone catalyst, it is characterised in that for the compound shown in following structure:
Wherein,
R1For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
R2For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro.
2. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 1, it is characterised in that:
After being obtained ruthenium complex by hydrate ruthenium trichloride with ligand reaction, after reacting generation Ru carbene complex with hexichol base class diazomethane compound, with formation target ruthenium carbone catalyst after thricyclohexyl phosphine reaction.
3. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 2, it is characterised in that:
Step one, hydrate ruthenium trichloride and ligand L are heated in organic solvent to 40-80 DEG C, react 3-12 hour, obtain ruthenium complex Cl2RuLn;
Step 2, by ruthenium complex Cl2RuLnIt is dissolved in organic solvent, at the temperature of 0 DEG C, drips hexichol base class diazomethane compound, generate Ru carbene complex;
Step 3, raise system temperature to 30-50 DEG C, in above-mentioned Ru carbene complex solution, add tricyclohexyl phosphine, after stirring reaction no longer changes to system color, post-treated obtain target ruthenium carbone catalyst;
Wherein, n is the integer of 1-10;
The structure of described hexichol base class diazomethane compound is as follows:
R1For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
R2For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
The structure of described Ru carbene complex is as follows:
R1For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
R2For monosubstituted on phenyl ring or polysubstituted hydrogen, alkyl and replacement alkyl, aryl and substituted aryl, heteroaryl and substituted heteroaryl, halogen, hydroxyl, amido, cyano group, nitro;
Described ligand L is selected from triphenylphosphine or 1,5-cyclo-octadiene.
4. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 3, it is characterised in that:
The mass ratio of described hydrate ruthenium trichloride and part is 1:3-8;
The mass ratio of described ruthenium complex and hexichol base class diazomethane compound is 1-10:1;
In described tricyclohexyl phosphine and reaction, the mol ratio of ruthenium metal is 2-2.5:1.
5. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 3, it is characterised in that:
The organic solvent in described step one or the step 2 mixture of one or more in the alcohol that boiling point is 40-80 DEG C, dichloromethane, chloroform, tetrachloromethane, oxolane, dioxane, benzene, toluene.
6. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 3, it is characterised in that:
Reaction temperature in described step one is 50-60 DEG C;
The response time of described step one is 4-5 hour;
The mass ratio of described hydrate ruthenium trichloride and part is 1:4-5.
7. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 3, it is characterised in that:
In step 2, dropping hexichol base class diazomethane compound after system temperature is down to less than-30 DEG C.
8. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 3, it is characterised in that:
In step 3, the described post-treated process obtaining target ruthenium carbone catalyst, particularly as follows: reactant is through being evaporated off organic solvent, adds mixed solvent making beating, purification, obtains target ruthenium carbone catalyst after filtration in the temperature range of 50-80 DEG C;
Wherein, described mixed solvent is selected from two or more mixture in the carbon number ketone less than 20, alcohols, ethers, esters solvent.
9. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 8, it is characterised in that:
Described mixed solvent is selected from the mixture of the boiling point ketone less than 150 DEG C and alcohols solvent;
The mass ratio of described ketones solvent and alcohols solvent is 1:2-5.
10. the synthetic method of a kind of ruthenium carbone catalyst as claimed in claim 8, it is characterised in that:
The mass ratio of described mixed solvent and tricyclohexyl phosphine is 5-10:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468191A (en) * | 2020-05-26 | 2020-07-31 | 上海化工研究院有限公司 | Synthetic method of ruthenium carbene catalyst |
| CN113563200A (en) * | 2021-07-03 | 2021-10-29 | 复旦大学 | Method for preparing linear amine by olefin selective hydroaminomethylation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555260A (en) * | 2009-05-19 | 2009-10-14 | 厦门大学 | Method for synthesizing first-generation Grubbs catalyst |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555260A (en) * | 2009-05-19 | 2009-10-14 | 厦门大学 | Method for synthesizing first-generation Grubbs catalyst |
Non-Patent Citations (2)
| Title |
|---|
| HELMUT WERNER ET AL: ""A New Family of Carbenerhodium (1) Complexes: Ligand Variation as the Key to Success"", 《CHEM. EUR. J.》 * |
| PETER SCHWAB ET AL: ""Synthesis and Applications of RuCl2(=CHR′)(PR3)2:The Influence of the Alkylidene Moiety on Metathesis Activity"", 《J. AM. CHEM. SOC.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468191A (en) * | 2020-05-26 | 2020-07-31 | 上海化工研究院有限公司 | Synthetic method of ruthenium carbene catalyst |
| CN113563200A (en) * | 2021-07-03 | 2021-10-29 | 复旦大学 | Method for preparing linear amine by olefin selective hydroaminomethylation |
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Application publication date: 20160601 |