CN101775043A - Method for synthesizing second generation Grubbs catalyst - Google Patents
Method for synthesizing second generation Grubbs catalyst Download PDFInfo
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- CN101775043A CN101775043A CN201010044835A CN201010044835A CN101775043A CN 101775043 A CN101775043 A CN 101775043A CN 201010044835 A CN201010044835 A CN 201010044835A CN 201010044835 A CN201010044835 A CN 201010044835A CN 101775043 A CN101775043 A CN 101775043A
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Abstract
The invention discloses a method for synthesizing a second generation Grubbs catalyst, which relates to a catalyst, in particular to a metal carbine compound (H2IMes)(PCy3)(Cl)2Ru=CHPh(H2IMes is 1,3-di-(2,4,6-trimethylphenyl)imidazole alkyl, and PCy3 is tricyclohexyl phosphine) with favorable olefin double-decomposition catalytic activity, namely the second generation Grubbs catalyst. The method comprises the following step of reacting a zero valence ruthenium compound Ru(p-cymene)(COD)(p-cymene is paracymene, and COD is 1,5-cyclooctadiene) with PCy3, PhCHCL2 and a nitrogen heterocyclic carbine compound in toluene or other hydrocarbon solvents to obtain the second generation Grubbs catalyst. The invention has low cost and easy acquisition of used raw materials, simple and safe operation process, easy control and high yield and is particularly suitable for industrialized large production.
Description
Technical field
The present invention relates to a kind of catalyzer, especially relate to a kind of metal carbene compound (H with good olefin metathesis catalytic activity
2IMes) (PCy
3) (Cl)
2Ru=CHPh (H
2IMes is 1,3-two-(2,4, the 6-trimethylphenyl) imidazolidine; PCy
3Be tricyclohexyl phosphine), i.e. the synthetic method of s-generation Grubbs catalyzer (Ma Yuguo, university chemistry, 2006,21,1).
Background technology
Olefin metathesis reaction be most important in the organic chemistry also be one of the most useful reaction type, this reaction makes and is chemically inert pair of bond energy coupling enough each other usually, greatly expanded the imagination space of people when the construction compound skeleton.Simultaneously, because this reaction has reaction conditions gentleness, productive rate height, and most organic groups need not protection in this reaction, therefore has been subjected to the extensive attention of academia and industry member in recent years.
The metal carbene compound is the metal alkylidene compound of the two keys (M=C) of a class containing metal-carbon, because of they effectively the various types of olefin metathesis reactions of catalysis receive publicity.In these metal carbene metathesis catalysts, the Grubbs catalyzer especially is subjected to people's attention.The first-generation Grubbs catalyzer RuCl that nineteen ninety-five emerges
2(the Cy of (=CHPh)
3)
2Not only reaction substrate there is the good functional group property held, and aqueous vapor in the reaction system and air are also had tangible stability, be fit to breadboard normal running, but it lacks gratifying reactive behavior.And the s-generation Grubbs catalyzer (H that developed in 1999
2IMes) (PCy
3) (Cl)
2Ru=CHPh not only possesses all advantages of first-generation catalyzer, and its reactive behavior also improves simultaneously, almost reaches perfect degree, and very high commercial application value is arranged.
Although s-generation Grubbs catalyzer (H
2IMes) (PCy
3) (Cl)
2Ru=CHPh has so important purposes in the Synthetic Organic Chemistry field, but its synthetic method only limits to a kind of method at present, promptly synthesizes s-generation Grubbs catalyzer (Scholl, M. by the part substitution reaction to first-generation Grubbs catalyzer; Ding, S.; Lee, C.W; Grubbs, R.H.Org.Lett.1999,1,953).
Summary of the invention
It is raw material (COD) with zeroth order ruthenium compound Ru (p-cymene) cheap and preparation easily that purpose of the present invention aims to provide a kind of, by the synthetic with high yield s-generation Grubbs catalyzer (H of simple and safe operation steps
2IMes) (PCy
3) (Cl)
2The method of Ru=CHPh.
Concrete synthetic route of the present invention is as follows:
Its concrete synthesis step is as follows:
1) with compound H
2IMes (H) is (1,3-two-(2,4, the 6-trimethylphenyl)-2-chlorine imidazolidine) or compound H (Cl)
2IMes (H) (BF
4) (1,3-two-(2,4, the 6-trimethylphenyl)-2-Tetrafluoroboric acid base imidazolidine) and KNSi (CH
3)
3In solvent, react, more after filtration, concentrate, after the crystallization, washing, drying compound H
2Imes;
2) with compound H
2IMes and Ru (p-cymene) (COD), PhCHCl
2, PCy
3In a kind of varsol, react, after concentrated, crystallization, filtration, washing, drying, get compound (H again
2IMes) (PCy
3) (Cl)
2Ru=CHPh, i.e. s-generation Grubbs catalyzer.
In step 1), described compound H
2IMes (H) (Cl) (1,3-two-(2,4, the 6-trimethylphenyl)-2-chlorine imidazolidine) is preferably 0.40g, 1.16mmol, described compound H
2IMes (H) (BF
4) (1,3-two-(2,4, the 6-trimethylphenyl)-2-Tetrafluoroboric acid base imidazolidine) be preferably 0.46g, 1.16mmol, described KNSi (CH
3)
3Be preferably 0.53mL, 1.16mmol; Described solvent is preferably tetrahydrofuran (THF) or normal hexane etc.; The time of described reaction is preferably 0.5～2h.
In step 2) in, described compound H
2Imes is preferably 181mg, 0.59mmol, described Ru (p-cymene) (COD) is preferably 200mg, 0.59mmol, described Ru (p-cymene) (COD) in, p-cymene is a p-Methylisopropylbenzene, COD is 1, the 5-cyclooctadiene; Described PhCHCl
2Be preferably 0.10mL, 0.79mmol, described PCy
3Be preferably 165mg, 0.59mmol; Described varsol preferably is selected from pentane, normal hexane, heptane, benzene or toluene etc.; The temperature of described reaction is preferably 20～80 ℃, and the time of reaction is preferably 12～48h.
Compare with the synthetic method of existing s-generation Grubbs catalyzer, the present invention has following outstanding advantage:
The present invention is a raw material (COD) with easy synthetic zeroth order ruthenium compound Ru (p-cymene), has synthesized s-generation Grubbs catalyzer (H efficiently
2IMes) (PCy
3) (Cl)
2Ru=CHPh, agents useful for same is all cheap and easy to get in each step of the present invention, simple and safe operation process and be easy to control, total recovery is good, is a kind of synthetic s-generation Grubbs catalyzer (H that can be applied to industrialized production
2IMes) (PCy
3) (Cl)
2The method of Ru=CHPh.
Description of drawings
Fig. 1 is (H
2IMes) (PCy
3) (Cl)
2Ru=CHPh's
31The P{H}NMR spectrogram.In Fig. 1, X-coordinate is chemical shift (ppm); Nmr frequency is 162.0MHz, and the deuterated reagent that detects usefulness is C
6D
6, chemical shift is 29.19ppm.
Fig. 2 is (H
2IMes) (PCy
3) (Cl)
2Ru=CHPh's
1H NMR spectrogram.In Fig. 1, X-coordinate is chemical shift (ppm); Nmr frequency is 400.1MHz, and the deuterated reagent that detects usefulness is C
6D
6
Embodiment
The present invention will be further described for following examples.Unless otherwise indicated, all experimental procedures below are all carried out under room temperature and anhydrous and oxygen-free condition.
In reaction flask, add H
2(Cl) (0.40g, 1.16mmol), THF (10mL), the dissolving back adds KNSi (CH to Imes (H)
3)
3(0.53mL, 1.16mmol), stirring at room 0.5h drains filtrate after removing by filter residue, after the vacuum-drying compound H
2IMes, productive rate 83%.
In reaction flask, add compound H
2IMes 2 (181mg, 0.59mmol), Ru (p-cymene) (COD) (200mg, 0.59mmol), PCy
3(165mg, 0.59mmol) and toluene (10mL), the dissolving back adds PhCHCl
2(0.10mL, 0.79mmol), stirring reaction 30h under the room temperature is concentrated into about 1mL with solution decompression, adds 10mL methyl alcohol, separates out the puce solid, filters with core, and solid gets compound (H with 3 * 3mL methanol wash after the vacuum-drying
2IMes) (PCy
3) (Cl)
2Ru=CHPh3, productive rate 50%.Fig. 1 provides (H
2IMes) (PCy
3) (Cl)
2Ru=CHPh's
31The P{H}NMR spectrogram, Fig. 2 provides (H
2IMes) (PCy
3) (Cl)
2Ru=CHPh's
1H NMR spectrogram.
1H?NMR(CDCl
2，400MHz)δ19.70(s，1H)，7.35-7.00(m，9H)，3.46(s，4H)，2.70-0.80(m，51H)；31PNMR(CDCl2，162MHz)δ29.2(s)。Through actual test shows, this compound has functional group's suitability very widely, and very stable, can exist in ethanol, water and carbonic acid soln, reveals to put in air and can not decompose in several weeks, just can operate with the machine technology that has of standard.It has the catalytic performance that is better than first-generation Grubbs catalyzer simultaneously, uses s-generation Grubbs catalyzer and can shorten the reaction times effectively or reduce catalyst consumption.
Compound H
2The operation of IMes 2 is identical with the operation among the embodiment 1, with reactant H
2IMes (H) (Cl) changes H into
2Imes (H) (BF
4), productive rate 84%.
Compound (H
2IMes) (PCy
3) (Cl)
2The synthesis step of Ru=CHPh 3 is identical with embodiment 1.
Compound H
2The operation of IMes 2 is identical with the operation among the embodiment 1, and solvent changes hexane into, stirring at room 2h, productive rate 85%.
Compound (H
2IMes) (PCy
3) (Cl)
2The synthesis step of Ru=CHPh 3 is identical with embodiment 1.
Compound H
2The operation of IMes 2 is identical with the operation among the embodiment 1.
Compound (H
2IMes) (PCy
3) (Cl)
2The synthesis step of Ru=CHPh 3 is identical with embodiment 1, changes into 50 ℃ of following stirring reaction 12h, productive rate 45%.
Claims (9)
1. the synthetic method of s-generation Grubbs catalyzer is characterized in that its concrete synthetic route is as follows:
2. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 1 is characterized in that concrete synthesis step is as follows:
1) with compound H
2IMes (H) is (1,3-two-(2,4, the 6-trimethylphenyl)-2-chlorine imidazolidine) or compound H (Cl)
2IMes (H) (BF
4) (1,3-two-(2,4, the 6-trimethylphenyl)-2-Tetrafluoroboric acid base imidazolidine) and KNSi (CH
3)
3In solvent, react, more after filtration, concentrate, after the crystallization, washing, drying compound H 2Imes;
2) with compound H
2IMes and Ru (p-cymene) (COD), PhCHCl
2, PCy
3In a kind of varsol, react, after concentrated, crystallization, filtration, washing, drying, get compound (H again
2IMes) (PCy
3) (Cl)
2Ru=CHPh, i.e. s-generation Grubbs catalyzer.
3. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 1), described compound H
2IMes (H) (Cl) (1,3-two-(2,4, the 6-trimethylphenyl)-2-chlorine imidazolidine) is 0.40g, 1.16mmol, described compound H
2IMes (H) (BF
4) (1,3-two-(2,4, the 6-trimethylphenyl)-2-Tetrafluoroboric acid base imidazolidine) be 0.46g, 1.16mmol, described KNSi (CH
3)
3Be 0.53mL, 1.16mmol.
4. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 1), and described solvent is tetrahydrofuran (THF) or normal hexane.
5. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 1), and the time of described reaction is 0.5～2h.
6. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 2) in, described compound H
2Imes is 181mg, and 0.59mmol, described Ru (p-cymene) are 200mg (COD), 0.59mmol, described Ru (p-cymene) (COD) in, p-cymene is a p-Methylisopropylbenzene, COD is 1, the 5-cyclooctadiene.
7. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 2) in, described PhCHCl
2Be 0.10mL, 0.79mmol, described PCy
3Be 165mg, 0.59mmol.
8. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 2) in, described varsol is selected from pentane, normal hexane, heptane, benzene or toluene.
9. the synthetic method of s-generation Grubbs catalyzer as claimed in claim 2 is characterized in that in step 2) in, the temperature of described reaction is 20～80 ℃, the time of reaction is 12～48h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549504A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | NHC-metal-imidazole structured catalyst and preparation method thereof |
| CN111440327A (en) * | 2020-03-24 | 2020-07-24 | 中国工程物理研究院材料研究所 | Deuterated supramolecular polymer and preparation method thereof |
-
2010
- 2010-01-12 CN CN201010044835A patent/CN101775043A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549504A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | NHC-metal-imidazole structured catalyst and preparation method thereof |
| CN104549504B (en) * | 2013-10-09 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of NHC-metal-glyoxaline structure type catalyst and preparation method thereof |
| CN111440327A (en) * | 2020-03-24 | 2020-07-24 | 中国工程物理研究院材料研究所 | Deuterated supramolecular polymer and preparation method thereof |
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Application publication date: 20100714 |