The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof,b) a bidentate phosphine, arsine or stibine ligand, andc) an acid,
The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof,b) a bidentate phosphine, arsine or stibine ligand, andc) an acid, wherein the ligand is present in at least a 2:1 molar excess compared to the metal or the metal in the metal compound, and that the acid is present in at least a 2:1 molar excess compared to the ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.
대표청구항▼
1. A process for the carbonylation of an ethylenically unsaturated compound comprising contacting ethene with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst system, which system is obtained by combining: a) palladium or a compound thereof,b) a bidentate phosph
1. A process for the carbonylation of an ethylenically unsaturated compound comprising contacting ethene with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst system, which system is obtained by combining: a) palladium or a compound thereof,b) a bidentate phosphine, arsine, or stibine ligand, andc) an acid,wherein said ligand is present in at least a 2:1 molar excess compared to said palladium metal or said palladium metal in said metal compound, and said acid is present in at least a 2:1 molar excess compared to said ligand. 2. A process as claimed in claim 1 wherein the ratio of said ligand to said metal is in the range 5:1 to 750:1. 3. A process as claimed in claim 1 wherein the ratio of said ligand to said metal is in the range 10:1 to 500:1. 4. A process as claimed in claim 1 wherein the ratio of said ligand to said metal is in the range 20:1 to 40:1. 5. A process as claimed in claim 1 wherein the ratio of said acid to said ligand is in the range 20:1 to 40:1. 6. A process as claimed in claim 1 wherein the molar ratio of said acid to said metal is in the range 10:1 to 75000:1. 7. A process as claimed in claim 1 wherein the molar ratio of said acid to said metal is in the range 100:1 to 25000:1. 8. A process as claimed in claim 1 wherein the molar ratio of said acid to said metal is in the range 200:1 to 400:1. 9. A process as claimed in claim 1 wherein said ligand is a bidentate phosphine ligand. 10. A process as claimed in claim 1 wherein said ligand is of general formula (I) wherein:Ar is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms;A and B each independently is lower alkylene;K, D, E and Z are substituents of the aryl moiety (Ar) and each independently is hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, OR19, OC(O)R20, C(O)R21, C(O)OR22, NR23R24, C(O)NR25R26, C(S)R25R26, SR27, C(O)SR27, or -J-Q3(CR13(R14)(R15)CR16(R17)(R18) where J is lower alkylene; or two adjacent groups selected from K, Z, D and E together with the carbon atoms of the aryl ring to which they are attached form a further phenyl ring, which is optionally substituted by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR19, OC(O)R20, C(O)R21, C(O)OR22, NR23R24, C(O)NR25R26, C(S)R25R26, SR27 or C(O)SR27;R1 to R18 each independently is lower alkyl, aryl, Het or at least one (CRxRyRz) group attached to Q1, Q2 and/or Q3, i.e. CR1R2R3, CR4R5R6, CR7R8R9, CR10R11R12, CR13R14R15, or CR16R17R18, is the group (Ad) wherein:Ad each independently is an optionally substituted adamantyl or congressyl radical bonded to the phosphorus atom via any one of its tertiary carbon atoms, the said optional substitution being by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR19, OC(O)R20, C(O)R21, C(O)OR22, NR23R24, C(O)NR25 R26, C(S)R25R26, SR27 or C(O)SR27; or if both (CRxRyRz) groups attached to either or both Q1 and/or Q2, or Q3 (if present) together with either Q1 or Q2 (or Q3) as appropriate, form an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]decyl group or derivative thereof, or form a ring system of formula whereinR49 and R54 each independently is hydrogen, lower alkyl or aryl;R50 to R53, when present, each independently is hydrogen, lower alkyl, aryl or Het; andY is oxygen, sulfur or N—R55; andR55, when present, is hydrogen, lower alkyl or aryl;R19 to R27 each independently represent is hydrogen, lower alkyl, aryl or Het; andQ1, Q2 and Q3 (when present) each independently is phosphorus, arsenic or antimony and in the latter two cases references to phosphorus above are amended accordingly. 11. A process as claimed in claim 10 wherein R1 to R18 each independently is lower alkyl, aryl, or Het. 12. A process as claimed in claim 10 wherein said ligand is: (Ad)s(CR7R8R9)TQ2-A-(K,D)Ar(E,Z)—B-Q1(Ad)u(CR1R2R3)v,wherein K, D, E and Z is -J-Q3(Ad)w(CR13(R14)(R15)x,wherein S and U are 0, 1 or 2 provided that S+U≧1;wherein T and V are 0, 1 or 2 provided that T+V≦3; andwherein W and X are 0, 1 or 2. 13. A process as claimed in claim 1 wherein said ligand is of general formula (III): wherein:A1 and A2, and A3, A4 and A5 (when present), each independently is lower alkylene;K1 is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, —OR19, —OC(O)R20, —C(O)R21, —C(O)OR22, —N(R23)R24, —C(O)N(R25)R26, —C(S)(R27)R28, —SR29, —C(O)SR30, —CF3 or -A3-Q3(X5)X6;D1 is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, —OR19, —OC(O)R20, —C(O)R21, —C(O)OR22, —N(R23)R24, —C(O)N(R25)R26, —C(S)(R27)R28, —SR29, —C(O)SR30, —CF3 or -A4-Q4(X7)X8;E1 is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, —OR19, —OC(O)R20, —C(O)R21, —C(O)OR22, —N(R23)R24, —C(O)N(R25)R26, —C(S)(R27)R28, —SR29, —C(O)SR30, —CF3 or A5-Q5(X9)X10;or both D1 and E1 together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an optionally substituted phenyl ring:X1 is CR1(R2)(R3), congressyl or adamantyl,X2 is CR4(R5)(R6), congressyl or adamantyl, or X1 and X2 together with Q2 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]decyl group or derivative thereof, or X1 and X2 together with Q2 to which they are attached form a ring system of formula IIIa X3 is CR7(R8)(R9), congressyl or adamantyl,X4 is CR10(R11)(R12), congressyl or adamantyl, or X3 and X4 together with Q1 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]decyl group or derivative thereof, or X3 and X4 together with Q1 to which they are attached form a ring system of formula IIIb X5 is CR13(R14)(R15), congressyl or adamantyl,X6 is CR16(R17)(R18), congressyl or adamantyl, or X5 and X6 together with Q3 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]decyl group or derivative thereof, or X5 and X6 together with Q3 to which they are attached form a ring system of formula IIIc X7 is CR31(R32)(R33), congressyl or adamantyl,X8 is CR34(R35)(R36), congressyl or adamantyl, or X7 and X8 together with Q4 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.1 {3,7}]decyl group or derivative thereof, or X7 and X8 together with Q4 to which they are attached form a ring system of formula IIId X9 is CR37(R38)(R39), congressyl or adamantyl,X10 is CR40(R41)(R42), congressyl or adamantyl, or X9 and X10 together with Q5 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.1.{3,7}]decyl group or derivative thereof, or X9 and X10 together with Q5 to which they are attached form a ring system of formula IIIe Q1 and Q2, and Q3, Q4 and Q5 (when present), each independently is phosphorus, arsenic or antimony;M is a Group VIB or VIIIB metal or metal cation thereof;L1 is an optionally substituted cyclopentadienyl, indenyl or aryl group;L2 is one or more ligands each of which are independently selected from hydrogen, lower alkyl, alkylaryl, halo, CO, P(R43)(R44)R45 or N(R46)(R47)R48;R1 to R18 and R31 to R42, when present, each independently is hydrogen, lower alkyl, aryl, halo or Het;R19 to R30 and R43 to R48, when present, each independently is hydrogen, lower alkyl, aryl or Het;R49, R54 and R55, when present, each independently is hydrogen, lower alkyl or aryl;R50 to R53, when present, each independently is hydrogen, lower alkyl, aryl or Het; Y1, Y2, Y3, Y4 and Y5, when present, each independently is oxygen, sulfur or N—R55;n=0 or 1;and m=0 to 5;provided that when n=1 then m equals 0, and when n equals 0 then m does not equal 0. 14. A process as claimed in claim 13 wherein if both K1 is -A3-Q3(X5)X6 and E1 is A5-Q5(X9)X10, then D1 is -A4-Q4(X7)X8. 15. A process as claimed in claim 10 or 13, wherein adamantyl is unsubstituted adamantyl or adamantyl substituted with one or more unsubstituted C1-C8 alkyl substituents, or a combination thereof. 16. A process as claimed in claim 10 or 13, wherein 2-phospha-adamantyl is unsubstituted 2-phospha-adamantyl or 2-phospha-adamantyl substituted with one or more unsubstituted C1-C8 alkyl substituents, or a combination thereof. 17. A process as claimed in claim 10 or 13, wherein 2-phospha-adamantyl includes one or more oxygen atoms in the 2-phospha-adamantyl skeleton. 18. A process as claimed in claim 10 or 13, wherein congressyl is unsubstituted congressyl. 19. A process according to claim 1 wherein the palladium is in the metal form. 20. A process according to claim 1, wherein the catalyst system includes in a liquid reaction medium a polymeric dispersant dissolved in a liquid carrier, said polymeric dispersant being capable of stabilising a colloidal suspension of particles of the Group VI or VIIIB metal or metal compound of the catalyst system within the liquid carrier. 21. A process according to claim 1, wherein the carbonylation of ethene is performed in one or more aprotic solvents. 22. A process according to claim 10, wherein Q1, Q2 and Q3 (when present) is phosphorus.
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