Production method of cyclic compounds by olefin metathesis reaction and use of ruthenium catalysts in production of cyclic olefines by olefin metathesis reaction

A method for producing a cyclic compound Mx,

• wherein:
• AB and CD are each independently a group selected from C1-C10 alkyl, C2-C25 alkenyl;
• GF is an ether (—O—), ester (—C(O)O—), carbonyl (—C(O)—), amido (—C(O)NR—), malonate (—C(COOR)2—) group, wherein R is independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy or a halogen atom;
• characterised in that olefin Dy with the formula
• wherein:
• AB and CD are each independently a group selected from such as a hydrogen atom, C1-C10 alkyl, C1-C10 perfluoroalkyl, C3-C7 cycloalkyl, C2-C25 alkenyl, C2-C25 perfluoroalkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C2-C25 perfluoroalkinyl, C3-C25 cycloalkinyl, C5-C24 aryl, C5-C20 heteroaryl, C5-C24 perfluoroaryl, 3-12-membered heterocycle, which may be optionally substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C1-C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C5-C20 heteroaryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, 3-12-membered heterocycle;
• Ra, Rb, Rc i Rd are each independently a C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy or a halogen atom;
• GF is an ether (—O—), ester (—C(O)O—), carbonyl (—C(O)—), amido (—C(O)NR—), malonate (—C(COOR)2—) group, wherein R is independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy or a halogen atom;
• are subjected to olefin metathesis reaction with the compound of the formula 1,
• wherein:
• X1 and X2 are each independently an anionic ligand selected from such as halogen atoms, —CN, —SCN, —OR′, —SR′, —O(C═O)R′, —O(SO2)R′, —OSi(R′)3 group, wherein R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or a halogen atom;
• R11, R12 are each independently a hydrogen atom, a halogen atom, optionally substituted C1-C25 alkyl, optionally substituted C1-C25 perfluoralkyl, optionally substituted C2-C25 alkene, optionally substituted C3-C7 cycloalkyl, optionally substituted C2-C25 alkenyl, optionally substituted C3-C25 cycloalkenyl, optionally substituted C2-C25 alkinyl, optionally substituted C3-C25 cycloalkinyl, optionally substituted C1-C25 alkoxy, optionally substituted C5-C24 aryloxy, optionally substituted C5-C20 heteroaryloxy, optionally substituted C5-C24 aryl, optionally substituted C5-C20 heteroaryl, optionally substituted C7-C24 aralkyl, optionally substituted C5-C24 perfluoroaryl, optionally substituted 3-12-membered heterocycle;
• wherein the substituents R11 and R12 may be interconnected to form a ring selected from the group consisting of C3-C7 cycloalkyl, C3-C25 cycloalkenyl, C3-C25 cycloalkinyl, C5-C24 aryl, C5-C20 heteroaryl, C5-C24 perfluoroaryl, 3-12-membered heterocycle, each of which may be substituted with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C1-C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C5-C20 heteroaryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, 3-12-membered heterocycle, in which case the dotted line between G and R12 is not a chemical bond;
• wherein the substituents R11 i R12 preferably are a hydrogen atom or aryl independently substituted with the following groups:
• alkoxy (—OR′), sulfide (—SR′), sulfoxide (—S(O)R′), sulfonium (—S+R′2), sulphonic (—SO2R′), sulfonamide (—SO2NR′2), amino (—NR′2), ammonium (—N+R′3), nitro (—NO2), cyano (—CN), phosphonium (—P(O)(OR′)2), phosphinium (—P(O)R′(OR′)), phosphonous (—P(OR′)2), phosphine (—PR′2), phosphine oxides (—P(O)R′2), phosphonium (—P+R′3), carboxy (—COOH), ester (—COOR′), amide (—CONR′2), amide (—NR′COR″), formyl (—CHO), ketone (—COR′), in which groups R′ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl;
• L is selected from such as:
• a)
• wherein:
• R1 is a heteroaryl group;
• R2, R3, R4, R5, R6 are each independently a hydrogen atom, a C1-C25 alkyl group, a C1-C25 alkoxy group or a C2-C25 alkenyl group, wherein the substituents R2, R3, R4, R5, R6 may be interconnected to form a substituted or unsubstituted cyclic C4-C10 or polycyclic C4-C12 system;
• R7, R1, R9, i R10 are each independently a hydrogen atom or a C1-C25 alkyl group, R7 and/or R8 can be connected with R9 and/or R10 to form a cyclic system;
• n is 0 or 1;
• b)
• wherein:
• Ar is an aryl group which is substituted with hydrogen atoms or is optionally substituted with at least one of the following groups:
• C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C2-C20 heterocycle, C4-C20 heteroaryl, C5-C20 heteroaryloxy, C7-C24 aralkyl, C5-C24 perfluoroaryl, or a halogen atom;
• R5, R6, R7 and R8 are each independently a hydrogen atom or one of the following groups:
• C1-C25 alkyl, C3-C12 cycloalkyl, C1-C5 perfluoroalkyl, C2-C12 alkenyl, C5-C20 aryl, C5-C24 aryloxy, C2-C20 heterocyclo, C4-C20 heteroarylo, C5-C20 heteroaryloxy, C7-C24 aralkyl, C5-C24 perfluoroaryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C4-C20 heteroaryl, C5-C20 heteroaryloxy, or a halogen atom;
• moreover, R5 and R6 and/or R7 i R′ may be interconnected to form a cyclic system;
• c)
• wherein:
• the combination A+X− and D is a hydrogen atom, or
• A is independently a substituent containing a tertiary amine group or a quaternary ammonium group, which may be a N(R1)(R2) or N+(R1)(R2)(R3) group, wherein R1, R2 and R3 are each independently one of the following groups:
• C1-C25 alkyl, C1-C12 perfluoroalkyl, C3-C7 cycloalkyl, C1-C25 alkoxy, C5-C20 aryl, C5-C24 aryloxy, C5-C24 perfluoroaryl, C5-C20 heteroaryl;
• alternatively, A is one of the following groups:
• C1-C25 cycloaminoalkyl, C1-C25 cyclodiaminoalkyl, C1-C25 cyclotriaminoalkyl, C1-C25 cyclotetraaminoalkyl, C1-C25 cycloaminoammonioalkyl, wherein the at least one nitrogen atom is independently substituted with at least one R1 group, wherein R1 is independently one of the following groups:
• C1-C25 alkyl, C1-C12 perfluoroalkyl, C3-C7 cycloalkyl, C1-C25 alkoxy, C5-C20 aryl, C5-C24 aryloxy, C5-C24 perfluoroaryl, C5-C20 heteroaryl so that at least one nitrogen atom in the ring forms a quaternary ammonium group;
• X is independently a halogen atom, or CF3SO3−, BF4−, PF6−, and ClO4−;
• D is independently one of the following groups:
• C1-C25 alkyl, C1-C12 perfluoroalkyl, C3-C7 cycloalkyl, C1-C25 alkoxy, C5-C20 aryl, C5-C24 aryloxy, C5-C24 perfluoroaryl, C5-C20 heteroaryl, or C2-C25 alkenyl, C1-C25 α,ω-dialkoxy, (CH2CH2O)n, polyether, where n comprises from 1 to 25, a C1-C25 thioalkyl group, a C1-C25 α,ω-dithioalkyl group, a C1-C25 α,ω-diheteroalkyl group, a C1-C25 aminoalkyl group;
• E is a single bond or independently a C1-C25 alkyl group, a C1-C12 perfluoroalkyl group, a C3-C7 cycloalkyl group, a C1-C25 alkoxy group;
• X1 and X2 are each independently an anion ligand selected from such as halogen atoms;
• R2, R2′, R3, R3′ i R4 are each independently a hydrogen atom, a halogen atom, a C1-C25 alkyl group, a C3-C7 cycloalkyl group, a C1-C25 alkoxy group, a C5-C24 perfluoroaryl group, a C5-C20 heteroaryl group or a C2-C25 alkenyl group, wherein the substituents R2, R2′, R3, R3′ and R4 may be interconnected to form a substituted or unsubstituted cyclic C4-C10 or polycyclic C4-C12 system;
• and
• G is selected from the substituents L listed above or G is a heteroatom selected from the group comprising an oxygen, nitrogen, sulphur, phosphorus, fluorine, chlorine, bromine and iodine atom, optionally substituted with a group selected from such as hydrogen atom C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C7 cycloalkyl, C5-C24 aryl, C5-C24 perfluoroaryl, C5-C20 heteroaryl, C7-C24 aralkyl, 3-12 membered heterocycle, the following groups:
• —COR′ acyl, (—CN) cyano, (—COOH) carboxy, (—COOR′) ester, (—CONR′2) amide, (—SO2R′) sulfonic, (—CHO) formyl, (—SO2NR′2) sulfonamide, (—COR′) ketone, wherein the R′ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl, C5-C24 perfluoroaryl, C7-C24 aralkyl, in which case the dotted line is a direct bond between the heteroatom and the R12 substituent, in the form of an aryl optionally substituted by 1-4 substituents independently selected from the group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perfluoroalkyl, C2-C25 alken, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C5-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, C5-C20 heteroaryl, 3-12-membered heterocycle, one of the following groups:
• (—OR′) alkoxy, (—SR′) sulfide, (—NO2) nitro, (—CN) cyano, (—COOH) carboxy, (—COOR′) ester, (—CONR′2) amide, (—CONR′COR′) imide, (—NR′2) amino, (—N+R′3) ammonium, (—NR′COR′) amide, (—NR′SO2R′), sulfonamide (—SO2R′), sulfonic (—CHO), formyl (—SO2NR′2), sulfonamide (—COR′), ketone, in which groups R′ is as follows:
• C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl, C5-C24 perfluoroaryl, C7-C24 aralkyl;
• wherein the metathesis reaction is optionally carried out in the presence of other additives enhancing the process of the reaction.