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1. WO2007140954 - COMPLEX OF RUTHENIUM AND OSMIUM, METHOD OF PRODUCTION THEREOF AND USE THEREOF AS (PRE)CATALYSTS OF THE METATHESIS REACTION

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Patent claims

1. Complexes of ruthenium or osmium as (pre)catalysts of the metathesis reaction represented by formula 1, in which
M denotes ruthenium or osmium,
L denotes a neutral ligand, selected from the group comprising amines, imines, phosphines (preferably), stilbines, arsines, alcohols, thiols, ethers and thioethers or the N-heterocyclic carbene ligand (NHC) represented by formula 9, where
B denotes the methylene (-C-), 1,2-ethylene (-C-C-), 1,3-propenyl (- C-C-C-), 1,2-ethenylene (-C=C-) or azaethenyl (-N=C-) residue, unsubstituted or substituted with halogens, C5-C24 aryl, C1-C6 alkyl, C1-C13 perfluoroalkyl, C1-C6 cycloalkyl groups, moreover the alkyl groups may be joined together in a ring; preferably B denotes 1,2- ethylene (-CH2-CH2-)
R and R' denote, independently of one another, C5-C24 aryl, C5-C24 perfluoroaryl, C1-C26 alkyl, C1-C26 perfluoroalkyl, C1-C7 cycloalkyl groups, unsubstituted or substituted with halogens, C5-C24 aryl, C1- Ce alkyl, C1-C13 perfluoroalkyl, C1-C6 cycloalkyl groups, moreover the alkyl groups may be joined together in a ring, preferably R and R' denote, independently of one another, phenyl groups substituted with C1-C26 alkyl residues, most preferably 2,4,6-trimethylphenyl
X and X' denote an anionic ligand, selected independently of one another from the group comprising anions of halogens, the phenolate anion (C6H5O") and perfluorophenolate anion (C6F5O"), residues of arylcarboxylic, alkylcarboxylic, perfluoroalkylcarboxylic, alkylsulphonic, arylsulphonic, perfluoroalkylsulphonic acids, preferably chlorine
R1 denotes hydrogen, C1-C5 alkyl, C2-C5 alkene or C3-C7 cycloalkyl, preferably hydrogen
R2, R3, R4, R5, R6, R7 denote, independently, C1-C25 alkyl, C1-C25 perfluoroalkyl, C5-C24 aryl, C2-C25 alkene or C3-C7 cycloalkyl, the nitro (- NO2), cyano (-CN), carboxyl (-C00H), ester (-COOR"), sulphone (- SO2R"), formyl (-CH0), sulphonamide (-SO2NR"2), or ketone (-COR") group, in which groups R" has the following meaning: C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl,
A denotes either nitrogen or carbon placed with an R5 group having the meaning given above.

2. Complexes according to Claim 1, characterized in that the compounds with formula 1 have the form of an isomer of formula Ia, in which atoms X and X' are arranged trans relative to one another, as shown in Fig. Ia and an isomer of formula Ib, in which atoms X and X' are arranged cis relative to one another as shown in Fig. Ib.

3. Complexes according to Claim 1, characterized in that, in formula 1, A denotes nitrogen or carbon, in ligand L1, B denotes a 1,2-ethylene (-C-C-) residue, R and R' denote a phenyl residue substituted in at least one of the ortho positions, preferably with a mesityl (2,4,5-trimethylphenyl; Mes) residue.

4. Method of production of complexes of ruthenium and osmium of formula 1, in which:
M denotes ruthenium or osmium,
L denotes a neutral ligand, selected from the group comprising amines, imines, phosphines, preferably stilbines, arsines, alcohols, thiols, ethers and thioethers or the N-heterocyclic carbene ligand (NHC) represented by formula 9, where
B denotes the methylene (-C-), 1,2-ethylene (-C-C-), 1,3-propenyl (- C-C-C-), 1,2-ethenylene (-C=C-) or azaethenyl (-N=C-) residue, unsubstituted or substituted with halogens, with C5-C24 aryl, C1-C6 alkyl, C1-C13 perfluoroalkyl, C1-C6 cycloalkyl groups, moreover the alkyl groups may be joined together in a ring; preferably B denotes 1,2-ethylene (-CH2-CH2-)
R and R1 denote, independently of one another, C5-C24 aryl, C5-C24 perfluoroaryl, C1-C26 alkyl, C1-C26 perfluoroalkyl, C1-C7 cycloalkyl groups, unsubstituted or substituted with halogens, C5-C24 aryl, C1- C6 alkyl, C1-C13 perfluoroalkyl, C1-C6 cycloalkyl groups, moreover the alkyl groups may be joined together in a ring, preferably R and R' denote, independently of one another, phenyl groups substituted with C1-C26 alkyl residues, most preferably 2,4,6-trimethylphenyl
X and X' denote an anionic ligand, selected independently of one another from the group comprising anions of halogens, the phenolate anion (C6H5O") and perfluorophenolate anion (C6F5O"), residues of arylcarboxylic, alkylcarboxylic, perfluoroalkylcarboxylic, alkylsulphonic, arylsulphonic, perfluoroalkylsulphonic acids, preferably chlorine
R1 denotes hydrogen, C1-C5 alkyl, C2-C5 alkene or C3-C7 cycloalkyl, preferably hydrogen
R2, R3, R4, R5, R6, R7 denote, independently, C1-C25 alkyl, C1-C25 perfluoroalkyl, C5-C24 aryl, C2-C25 alkene or C3-C7 cycloalkyl, the nitro (-NO2), cyano (-CN), carboxyl (-C00H), ester (-COOR"), sulphone (-SO2R"), formyl (-CH0), sulphonamide (-SO2NR"2), or ketone (-COR") group, in which groups R" has the following meaning: C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl,
A denotes either nitrogen or carbon placed with an R5 group having the meaning given above,
characterized in that an intermediate of formula 5, in which R1, R2, R3, R4,

R5, R6, R7 and A have the meaning given above, is reacted with a carbene complex of ruthenium or osmium of formula 6, in which:
M denotes ruthenium or osmium,
L, L1 and L2 denote, independently of one another, a neutral ligand selected from the group comprising amines, imines, phosphines, preferably stilbines, arsines, alcohols, thiols, ethers and thioethers or an N-heterocyclic carbene ligand (NHC) represented by formula 9, with L2 optionally denoting hydrogen - absence of a ligand (vacancy),
R and R denote, independently of one another, C5-C24 aryl groups, C1-C26 alkyl groups, C1-C7 cycloalkyl groups, unsubstituted or substituted with halogens, with C5-C24 aryl groups, with C1-C6 alkyl, C1-C13 perfluoroalkyl and C1-C6 cycloalkyl groups, and optionally groups R8 and R9 are joined together in a ring or form a fragment of an aromatic compound, preferably R8 denotes hydrogen and R9 denotes phenyl,
X and X' have the meaning given above

5. Method according to Claim 4, characterized in that compounds of formula Ia and Ib are obtained as shown in Scheme II, in a reaction between an N- heterocyclic aromatic compound of formula 5 and a complex of ruthenium or osmium of formula 6, optionally in the presence of a copper(I) salt, preferably copper(I) chloride.

6. Method according to Claim 4, characterized in that the reaction is carried out in chlorinated solvents, or in aliphatic, cycloaliphatic and aromatic hydrocarbons, or in mixtures thereof, preferably in methylene chloride for a time from 1 min to 250 h at a temperature from 0 to 1500C.

7. Method according to Claim 4, characterized in that a pure isomer of formula Ib or a mixture of isomers of formula Ia and of formula Ib, with ratio of Ia to Ib from 100:0 to 0:100, is obtained as a result of isomerization of a solution of compound Ia in chlorinated solvents, preferably methylene chloride, or in aliphatic, cycloaliphatic and aromatic hydrocarbons, or in mixtures thereof for a time from 1 minute to 250 h at a temperature from 0 to 1500C.

8. Method according to Claim 4, characterized in that the sequences of synthesis for production of complexes of formula 1 are shown in Schemes I, III and V, and for synthesis of complexes of formula 10, 11, 12 in Schemes II, IV and VI-XII.

9. Use of complexes of formula 1, in which R1, R2, R3, R4, R5, R6, R7 and A have the meaning given above, characterized in that they are used as (pre)catalysts in a metathesis reaction.

10. Use according to Claim 9, characterized in that compounds of formula 1 are used as (pre)catalysts of ring-closure metathesis, of cross metathesis and of metathesis of the "alkene-alkyne" (ene-yne) type.

11. Use according to Claim 9, characterized in that compounds of formula 1 are used in polymerization processes.