# Patent

## Title
Metathesis catalyst

## Abstract

The current invention describes new metathesis catalysts, a method for their preparation and their use in metathesis reactions.

## Background
The current invention describes new metathesis catalysts, a method for their preparation and their use.
BACKGROUND
Numerous metathesis catalysts are already known; refer to for example: Tetrahedron Lett. 1999, 40, 1091-1094, J. Am. Chem. Soc. 2000, 122, 58-71, Angew. Chem. 2003, 115, 1944-1968. It is known from these publications that substrates comprising acetal-groups considerably inhibit metathesis reactions.


DESCRIPTION
New metathesis catalysts comprising acetal-groups with the formula (I) have been found in which




    
    
        Ru stands for ruthenium,
        R1 stands for alkyl,
        R2 stands for alkyl,
        R3 stands for hydrogen or for an electron-withdrawing substituent,
        Hal stands for chlorine or bromine, independently of each other,
        Lig stands for the ligand Lig1 or Lig2.
    
    


It was further found that the catalysts of formula (I) can be produced from compounds of formula (II)




In which R1, R2 and R3 have the above given meanings, by reaction with 2nd generation Grubbs catalyst (see Aldrich Chemistry Handbook Fine Chemicals 2009-2010, page 1453) in the presence of CuCl (J. Org. Chem. 2004, 69, 6894-6896).
It was finally found out that the catalysts of formula (I) are suitable for the modification of butadiene acrylonitrile copolymers.




wherein

    
    
        R4 stands for mesityl.
    
    


Especially preferred are catalysts of formula (I), in which

    
    
        R1 stands for methyl or ethyl,
        R2 stands for C6-C18 alkyl,
        R3 stands for hydrogen or C1-C18 alkyl or stands for an electron-withdrawing substituent from the series nitro and SO2N(C1-C18 alkyl),
        Hal stands for chlorine or bromine, independently of each other,
        Lig stands for
    
    






wherein

    
    
        R4 stands for mesityl.
    
    


First Exemplary Embodiment
Preparation of the catalyst of formula (I), wherein R1=Me, R2=C12H25, R3=NO2, Hal=C1, Lig=Lig1.




In a Schlenk apparatus, the 2nd-generation Grubbs catalyst (0.108 g, 0.13 mmol) is mixed with a solution of compound (I-1):




(0.059 g, 0.14 mmol) in 5 ml dichloromethane and 25 mg of copper-(I)-chloride and was stirred for about 50 minutes to about 60 minutes at ambient temperature under an argon atmosphere. The solvent was then removed under vacuum and the residue was purified by column chromatography. The catalyst (I) was obtained as a green solid.
Second Exemplary Embodiment
Preparation of the catalyst of formula (I), wherein R1=Me, R2=C12H25, R3=NO2, Hal=C1, Lig=Lig1.




In a Schlenk apparatus, the 2nd-generation Grubbs catalyst (0.108 g, 0.13 mmol) is mixed with a solution of compound (I-1):




(0.059 g, 0.14 mmol) in 5 ml dichloromethane and 25 mg of copper-(I)-chloride and was stirred for about 50 minutes to 60 minutes under reflux in an argon atmosphere. The solvent was then removed under vacuum and the residue stirred in ethylacetate, filtered and evaporated again. The residue was purified by column chromatography (15% ethylacetate/cyclohexane). The catalyst (I) was obtained as a green solid.

## Claims

1. Compounds of formula (I)



in which
Ru stands for ruthenium,
R1 stands for alkyl,
R2 stands for alkyl,
R3 stands for an electron-withdrawing substituent,
Hal stands for chlorine or bromine, independently of each other,
Lig stands for the ligand Lig1 or Lig2, wherein




and wherein R4 stands for mesityl.

2. The compounds of formula (I)



wherein
Ru is ruthenium,
R1 is methyl or ethyl,
R2 is C6-C18 alkyl,
R3 is hydrogen, C1-C18 alkyl, or an electron-withdrawing substituent from the series nitro and SO2N(C1-C18 alkyl),
Hal is chlorine or bromine, independently of each other,
Lig is




and wherein
R4 is mesityl.