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Method for in-situ formation of metathesis catalysts

a technology of organic olefin and catalyst, which is applied in the direction of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, ruthenium organic compound, etc., can solve the problems of less active types of complexes and relatively cumbersome syntheses of these complexes

Inactive Publication Date: 2013-08-08
MATERIA
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The patent describes a method for making a new type of organometallic compound, called an olefin metathesis catalyst. This catalyst can be used to create other new organometallic compounds by combining two different chemicals together. The method involves using a special chelating compound that can attach to a specific metal, and adding a specific chemical to change its structure and make it more effective as a catalyst. This invention also covers some of the specific structures of these new organometallic compounds. The new catalyst can be used to create new compounds by combining olefins or other chemicals, which has potential uses in a variety of fields.

Problems solved by technology

However, the syntheses of these complexes are relatively cumbersome, usually involving more than one step and requiring isolation of the catalysts to remove catalyst-inhibiting by-products such as liberated phosphine ligands (Scheme 1).
However, these types of complexes proved less active in olefin metathesis than their ruthenium-alkylidene counterparts.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

Synthesis of 3,5-dimethoxybenzophenone

[0096]

[0097]This compound was previously prepared by a two-step process.v However, we prepared it by a one-step method adapted from another literature procedure.vi Neat 3,5-dimethoxybenzonitrile (16.0 g, 98.1 mmol) was added to a 2.0 M solution of phenylmagnesium chloride in THF (98.0 mL, 196.1 mmol). The reaction mixture was refluxed for 24 hours at 70° C. The solution was then transferred into a mixture of concentrated aqueous HCl (100 mL) and ice (300 g). The mixture was allowed to warm up to room temperature and stirred for 24 hours. The product was extracted with ether (3×300 mL) and the combined organic layers were washed with brine (200 mL) and water (150 mL) before being dried with anhydrous magnesium sulfate. The filtrate was dried in vacuo to afford 3,5-dimethoxybenzophenone as a yellow solid in 75% yield. 1H NMR (CDCl3): δ 7.84 (d, 3JH—H=7.2 Hz, 1H), 7.61 (t, 3JH—H=7.6 Hz, 2H), 7.50 (t, 3JH—H=7.6 Hz, 2H), 6.95 (d, 3JH—H=2.4 Hz, 1H), 6...

example 1a

Synthesis of 3,5-diisopropoxybenzophenone

[0098]

[0099]3,5-Diisopropoxybenzophenone was prepared from 3,5-diisopropoxybenzonitrile following a procedure analogous to that described above for the preparation of 3,5-dimethoxybenzophenone (Example 1). 3,5-Diisopropoxybenzonitrile was synthesized according to a literature procedure (Wang, E.-C.; Lin, G.-J. A New One Pot Method for the Conversion of Aldehydes into Nitriles Using Hydroxyamine and Phthalic Anhydride. Tetrahedron Lett. 1998, 39, 4047-4050).

example 2

Synthesis of 1-(3,5-Dimethoxyphenyl)-1-Phenylprop-2-yn-1-ol

[0100]

[0101]The following method was adapted from a literature procedure.vii Anhydrous THF (50 mL) was cooled to −78° C. Purified acetylene gas was gently bubbled through the THF for 1 hour. A 2.5 M solution of n-butyllithium in THF (8.2 mL, 20.5 mmol) was then added drop-wise and the mixture was stirred vigorously for 20 minutes. 3,5-Dimethoxybenzophenone (5.0 g, 20.5 mmol) was dissolved in 10 mL of anhydrous THF and the solution was slowly dropped into the reaction flask. The mixture was stirred vigorously for 20 minutes at −78° C. before being allowed to slowly warm to room temperature. A 5% aqueous solution of NH4Cl (60 mL) was added and the mixture stirred for 30 minutes. The product was extracted with ether (3×100 mL) and the combined organic layers were washed with brine (100 mL) and water (75 mL) before being dried with anhydrous magnesium sulfate. The filtrate was dried in vacuo to afford 1-(3,5-dimethoxyphenyl)-1-p...

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Abstract

Synthetic methods for the in-situ formation of olefin metathesis catalysts are disclosed, as well as the use of such catalysts in metathesis reactions of olefins and olefin compounds. In one aspect, a method is provided for synthesizing an organometallic compound of the formulacomprising contacting a precursor compound of the formula (X1X2MLjL1kL3m)i with an acetylenic compound comprising a chelating moiety, optionally, in the presence of a neutral electron donor, wherein M is a Group 8 transition metal, L, L1, L2, and L3 are neutral electron donors, X1 and X2 are anionic ligands, j is 1, 2, or 3; k is zero, 1, or 2; m is zero or 1; n is 1 or 2; and i is an integer; with the proviso that k is zero when the precursor compound is contacted with the acetylenic compound in the presence of the neutral electron donor, and R1 and R2 are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein R1 and R2 are linked and together form one or more cyclic groups, R2 and L2 are linked and together form one or more cyclic groups, and any other two or more of X1, X2, L1, L2, L3, R1, and R2 can be taken together to form one or more cyclic groups. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

Description

TECHNICAL FIELD[0001]This invention relates generally to organometallic olefin metathesis catalysts, and more particularly to the in-situ formation of such olefin metathesis catalysts, as well as the use of such catalysts in metathesis reactions of olefins and olefin compounds. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.BACKGROUND[0002]Olefin metathesis has become an exceptionally powerful and applicable method for the formation of carbon-carbon bonds in organic and polymer synthesis. Ruthenium-based complexes (1-3) are the most commonly employed olefin metathesis catalysts in academic and industrial laboratories, because they can be handled in air and are tolerant of various organic functional groups.(see (a) Schrodi, Y.; Pederson, R. L. Aldrichim. Acta 2007, 40, 45-52. (b) Grubbs, R. H. Adv. Synth. Catal. 2007, 349, 34-40). However, the syntheses of these complexes are relatively cumbersom...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): B01J31/12C07C6/04
CPCB01J31/2265B01J2231/543B01J2531/821B01J2531/825C07C67/333C07C2101/10C07C6/04C07D211/96C07D223/04C07F15/0046C07D207/48B01J31/122C07C69/74C07D207/46C07D211/94C07C2601/10B01J31/2295B01J31/2404
Inventor SCHRODI, YANN
Owner MATERIA
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