Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/5027—Polyphosphines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
  • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/006—Palladium compounds
  • C07F15/0066—Palladium compounds without a metal-carbon linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F17/00—Metallocenes
  • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
  • C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine

Definitions

• the present invention relates to a process for the carbonylation of selected ethylenically unsaturated compounds, particularly alkoxy and hydroxy-carbonylation thereof, novel bidentate ligands and novel catalyst systems incorporating such ligands.
• EP-A-0227160, EP-A-0495547 and EP-A-0495548 disclose that bidentate phosphine ligands provide catalyst systems which enable high reaction rates to be achieved.
• C3 alkyl bridges between the phosphorus atoms are exemplified in EP0495548 together with tertiary butyl substituents on the phosphorus .
• a catalyst system capable of catalysing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining:
• the said ratio can be in the range 125:1 to 485:1, more preferably 150:1 to 450:1, even more preferably 175:1 to 425:1, yet even more preferably 200:1 to 400:1, most preferably 225:1 to 375:1.
• Y represents a group which is at least as sterically hindering as phenyl and when there are two or more substituents Y they are each as sterically hindering as phenyl and/or combine to form a group which is more sterically hindering than phenyl .
• the cone angle of the at least one group Y or the sum of the cone angles of two or more Y groups is at least 10°, more preferably, at least 20°, most preferably, at least 30°.
• Cone angle should be measured according to the method of Tolman ⁇ C. A. Tolman Chem. Rev. 77, (1977), 313-348 ⁇ except that the apex angle of the cone is now centred at the midpoint of the aromatic ring.
• This modified use of Tolman cone angles has been used in other systems to measure steric effects such as those in cyclopentadienyl zirconium ethene polymerisation catalysts (Journal of Molecular Catalysis: Chemical 188, (2002), 105-113).
• R 40 , R 41 and R 42 are independently hydrogen, alkyl, -BQ 3 -X 3 (X 4 ) (wherein B, X 3 and X 4 are as defined herein and Q 3 is defined as Q 1 or Q 2 above) , phosphorus, aryl, arylene, alkaryl, arylenalkyl, alkenyl, alkynyl, het, hetero, halo, cyano, nitro, -OR 19 , -OC(O)R 20 , -C(O)R 21 , -C(O)OR 22 , -N (R 23 ) R 24 , -C (0) N (R 25 ) R 26 , -SR 29 , C(O)SR 30 , -C (S) N (R 27 ) R 28 , -CF 3 , -SiR 71 R 72 R 73 or alkylphosphorus .
• the at least one aromatic ring can be part of a metallocene complex, for instance when R is a cyclopentadienyl or indenyl anion it may form part of a metal complex such as ferrocenyl, ruthenocyl, molybdenocenyl or indenyl equivalents.
• the hydrocarbyl aromatic structure may be monocyclic or polycyclic.
• the cyclic aromatic atoms may be carbon or hetero, wherein references to hetero herein are references to sulphur, oxygen and/or nitrogen.
• the Q 1 and Q 2 atoms are linked to available adjacent cyclic carbon atoms of the at least one aromatic ring.
• the cyclic hydrocarbyl structure is polycylic it is preferably bicyclic or tricyclic.
• the further cycles in the aromatic structure may or may not themselves be aromatic and aromatic structure should be understood accordingly.
• a non-aromatic cyclic ring(s) as defined herein may include unsaturated bonds.
• cyclic atom is meant an atom which forms part of a cyclic skeleton .
• the immediately adjacent cyclic atoms on either side of the said available adjacent cyclic atoms are preferably not substituted.
• an aromatic phenyl ring joined to a Q 1 atom via position 1 on the ring and joined to a Q atom via position 2 on the ring has preferably one or more said further aromatic cyclic atoms substituted at ring position 4 and/or 5 and the two immediately adjacent cyclic atoms to the said available adjacent cyclic atoms not substituted at positions 3 and 6.
• this is only a preferred substituent arrangement and substitution at ring positions 3 and 6, for example, is possible.
• R 50 to R 53 when present, each independently represent alkyl, aryl or Het;
• X 3 represents CR 7 (R 8 ) (R 9 )
• X 4 represents CR 10 (R 11 ) (R 12 )
• X 1 represents
• Q 1 and Q 2 both represent phosphorus linked to the R group at ring positions 1 and 2.
• one of A or B is omitted ie Q 2 or Q 1 is connected directly to the group R and the other Q group is not connected directly to the group R and is a Ci to C 6 alkylene, preferably -CH 2 - or -C 2 H 4 -, most preferably, -CH 2 -.
• the catalyst compounds of the present invention may act as a "heterogeneous" catalyst or a "homogeneous” catalyst, preferably, a homogenous catalyst.
• the compounds of the process of the invention are fixed to the surface of an insoluble support, optionally via a covalent bond, and the arrangement optionally includes a bifunctional spacer molecule to space the compound from the insoluble support.
• the mixed phosphine (7) was prepared in a two step process; the cyclic sulphate was sequentially reacted with the lithium salt of Bu t 2 PH.BH 3 (4) followed by the lithium salt of Ph 2 PH (5) .
• the boron protected phosphine (6) was then de-boronated by the addition of tetrafluoroboric acid the in-situ prepared bis-phosphonium salt was then reduced to the free phosphine (7) by addition of potassium hydroxide .
• the other three mixed phosphines were prepared in a similar manner to (7) .
• the catalytic solution was added to the pre-evacuated autoclave and heated to 100 0 C at which point the pressure generated by the solvent was 2.3 bar.
• the autoclave was then pressured to 12.3 bars with addition of CO: ethene (1:1 gas) charged from a 10 litre reservoir at higher pressure.
• a regulatory valve ensures that the pressure of the autoclave is maintained throughout the reaction at 12.3 bars through constant injection of gas from the 10 litre reservoir.
• the pressure of the reservoir as well as the reactor temperature was logged throughout the reaction period of 3 hrs .
• the moles of product produced at any point in the reaction can be calculated from the drop in reservoir pressure by assuming ideal gas behaviour and 100% selectivity for methyl propionate, allowing reaction TON with the particular ligand to be obtained.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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