EP1735263A1 - Process for the carbonylation of ethylenically or acetylenically unsaturated compounds - Google Patents
Process for the carbonylation of ethylenically or acetylenically unsaturated compoundsInfo
- Publication number
- EP1735263A1 EP1735263A1 EP05716797A EP05716797A EP1735263A1 EP 1735263 A1 EP1735263 A1 EP 1735263A1 EP 05716797 A EP05716797 A EP 05716797A EP 05716797 A EP05716797 A EP 05716797A EP 1735263 A1 EP1735263 A1 EP 1735263A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- represent
- atom
- groups
- phosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000008569 process Effects 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 25
- 230000006315 carbonylation Effects 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 phosphino group Chemical group 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000962 organic group Chemical group 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 125000004429 atom Chemical group 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 150000001450 anions Chemical class 0.000 claims description 22
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 claims description 3
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- GVFQLFXNYFKVCA-UHFFFAOYSA-N phosphinan-4-one Chemical group O=C1CCPCC1 GVFQLFXNYFKVCA-UHFFFAOYSA-N 0.000 claims 3
- DJXHXILQRDQZGU-UHFFFAOYSA-N 2-phosphatricyclo[3.3.1.13,7]decane Chemical group C1C(P2)CC3CC1CC2C3 DJXHXILQRDQZGU-UHFFFAOYSA-N 0.000 claims 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims 1
- 235000011037 adipic acid Nutrition 0.000 claims 1
- 239000001361 adipic acid Substances 0.000 claims 1
- 229940017219 methyl propionate Drugs 0.000 claims 1
- 239000000047 product Substances 0.000 description 28
- 239000000376 reactant Substances 0.000 description 25
- 239000002253 acid Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 125000001424 substituent group Chemical group 0.000 description 20
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 125000005842 heteroatom Chemical group 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000005864 Sulphur Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000007306 turnover Effects 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910000856 hastalloy Inorganic materials 0.000 description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- JMQFXZOWEUWLSL-UHFFFAOYSA-N ditert-butyl-[2-(chloromethyl)prop-2-enyl]phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC(=C)CCl JMQFXZOWEUWLSL-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical group CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 2
- GSPFJJBPZHIIHL-UHFFFAOYSA-N 8-(2-{[di(tert-butyl)-phosphino]-methyl}phenyl)-1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo[3.3.1.1{3,7}]decane Chemical compound CC(C)(C)P(C(C)(C)C)CC1=CC=CC=C1P1C(O2)(C)CC3(C)OC2(C)CC1(C)O3 GSPFJJBPZHIIHL-UHFFFAOYSA-N 0.000 description 2
- QJCMAJXWIAFFED-UHFFFAOYSA-N 9-phosphabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1P2 QJCMAJXWIAFFED-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010703 silicon Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- CLDXNENUMZXSSG-UHFFFAOYSA-N (2-bromophenyl)methyl-ditert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC1=CC=CC=C1Br CLDXNENUMZXSSG-UHFFFAOYSA-N 0.000 description 1
- MCIZZOZQDIJBGO-UHFFFAOYSA-N 1,3,5-trimethyl-4,6,9-trioxa-2-phosphatricyclo[3.3.1.1{3,7}]decane Chemical compound O1C(C2)CC3(C)OC1(C)OC2(C)P3 MCIZZOZQDIJBGO-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- LZSYGJNFCREHMD-UHFFFAOYSA-N 1-bromo-2-(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1Br LZSYGJNFCREHMD-UHFFFAOYSA-N 0.000 description 1
- ZJDNAQRUUYRJLW-UHFFFAOYSA-N 2,2,6,6-tetramethylphosphinan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)P1 ZJDNAQRUUYRJLW-UHFFFAOYSA-N 0.000 description 1
- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 description 1
- XZNLSDPNMNWCRE-UHFFFAOYSA-N 2,6-bis(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=C(C(F)(F)F)C=CC=C1C(F)(F)F XZNLSDPNMNWCRE-UHFFFAOYSA-N 0.000 description 1
- MRUDNSFOFOQZDA-UHFFFAOYSA-N 2,6-dichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC=C1Cl MRUDNSFOFOQZDA-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- 125000006280 2-bromobenzyl group Chemical group [H]C1=C([H])C(Br)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- LOUORYQQOPCXGD-UHFFFAOYSA-N 2-methylpropan-1-ol Chemical compound CC(C)CO.CC(C)CO LOUORYQQOPCXGD-UHFFFAOYSA-N 0.000 description 1
- RABUMNZAAOXBOH-UHFFFAOYSA-N 2-methylpropan-2-ol;propan-1-ol Chemical compound CCCO.CC(C)(C)O RABUMNZAAOXBOH-UHFFFAOYSA-N 0.000 description 1
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- XJFZOSUFGSANIF-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)prop-1-ene Chemical compound ClCC(=C)CCl XJFZOSUFGSANIF-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- RRZPCBLAZBRYCL-UHFFFAOYSA-N 4-ethyl-2-methylthiolane 1,1-dioxide Chemical compound CCC1CC(C)S(=O)(=O)C1 RRZPCBLAZBRYCL-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910006111 GeCl2 Inorganic materials 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- WGNVMQNPNHALJH-UHFFFAOYSA-N [2-(phosphanylmethyl)phenyl]methylphosphane Chemical compound PCC1=CC=CC=C1CP WGNVMQNPNHALJH-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- GKMQWTVAAMITHR-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O.CCC(C)O GKMQWTVAAMITHR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical class C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical class C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- FJILYPCZXWVDMD-UHFFFAOYSA-N ditert-butyl(3-ditert-butylphosphanylpropyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CCCP(C(C)(C)C)C(C)(C)C FJILYPCZXWVDMD-UHFFFAOYSA-N 0.000 description 1
- QMMVETDQZQGRSR-UHFFFAOYSA-N ditert-butyl-[(2-decylphenyl)methyl]phosphane Chemical compound CCCCCCCCCCC1=CC=CC=C1CP(C(C)(C)C)C(C)(C)C QMMVETDQZQGRSR-UHFFFAOYSA-N 0.000 description 1
- XXUAPGBVQMBPQI-UHFFFAOYSA-N ditert-butyl-[2-(9-phosphabicyclo[3.3.1]nonan-9-ylmethyl)prop-2-enyl]phosphane Chemical compound C1CCC2CCCC1P2CC(=C)CP(C(C)(C)C)C(C)(C)C XXUAPGBVQMBPQI-UHFFFAOYSA-N 0.000 description 1
- AVNDRVMKYWBUIV-UHFFFAOYSA-N ditert-butyl-[2-(9-phosphabicyclo[3.3.1]nonan-9-ylmethyl)prop-2-enyl]phosphane 9-phosphabicyclo[3.3.1]nonane Chemical compound C12CCCC(CCC1)P2.C(C)(C)(C)P(C(C)(C)C)CC(CP2C1CCCC2CCC1)=C AVNDRVMKYWBUIV-UHFFFAOYSA-N 0.000 description 1
- UOIQQAZXHJFHHT-UHFFFAOYSA-N ditert-butyl-[2-(phosphanylmethyl)prop-2-enyl]phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC(=C)CP UOIQQAZXHJFHHT-UHFFFAOYSA-N 0.000 description 1
- ZDKQIBJEARFSJE-UHFFFAOYSA-N ditert-butyl-[[2-(ditert-butylphosphanylmethyl)phenyl]methyl]phosphane Chemical compound C(C)(C)(C)P(C(C)(C)C)CC1=C(C=CC=C1)CP(C(C)(C)C)C(C)(C)C.C(C)(C)(C)P(C(C)(C)C)CC1=C(C=CC=C1)CP(C(C)(C)C)C(C)(C)C ZDKQIBJEARFSJE-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- KJALUUCEMMPKAC-UHFFFAOYSA-N methyl pent-3-enoate Chemical class COC(=O)CC=CC KJALUUCEMMPKAC-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 229940124305 n-propanol Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 125000002872 norbornadienyl group Chemical group C12=C(C=C(CC1)C2)* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- DFOXKPDFWGNLJU-UHFFFAOYSA-N pinacolyl alcohol Chemical compound CC(O)C(C)(C)C DFOXKPDFWGNLJU-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- 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
- 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
-
- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
- C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
-
- 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
- C07F9/6571—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 and oxygen atoms as the only ring hetero atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
Definitions
- the present invention provides a process for the carbonylation of ethylenically or acetylenically unsaturated compounds.
- carbonylation refers to the reaction of alkenes or alkynes, i.e. ethylenically or acetylenically non-conjugated unsaturated compounds, under catalysis by a transition metal complex with carbon monoxide and a co-reactant having a mobile hydrogen atom, as for instance described in EP-A-0, 495, 548 and EP-A- 0,565,199, WO-A-96/19434, WO-A-98/42717, WO-A-01/68583 and WO-A-01/72697.
- EP-A-0, 495, 548 discloses a catalyst system comprising a palladium cation and diphosphine bidentate ligands bearing di-alkyl-substituted phosphino groups, such as for instance 1,3 bis (di-tertiary butyl phosphino) propane, and the use of such catalysts in various carbonylation reactions. Although the disclosed catalyst systems show a good activity in carbonylation reactions, application of the process on an industrial scale requires further improvements in catalyst activity and selectivity for the desired products.
- catalyst systems based on a metal cation selected from 8, 9 or 10 of the Periodic Table of Elements and an unsymmetrical diphosphine ligand 5 exhibit improved catalyst activity in the carbonylation of ethylenically or acetylenically unsaturated compounds, thereby resulting in a significantly improved carbonylation process.
- the subject invention relates to a 10 process for the carbonylation of an ethylenically or acetylenically unsaturated compound by contacting the unsaturated compound with carbon monoxide and a co- reactant having a mobile hydrogen atom in the presence of a catalyst system comprising: 15 (a) a source of a palladium and/or platinum; and (b) an unsymmetrical diphosphine of formula I, R 1 R 2 pi _ R 3 _ P 2 ⁇ R 4 R 5 ( D wherein P 1 - and P ⁇ represent phosphorus atoms; R-3
- J- represents a divalent organic bridging group
- R 1 , R ⁇ , 20 R ⁇ and R ⁇ each individually, or R 1 - and R 2 jointly, and/or R 4 and R5 jointly represent organic substituents that are covalently bound to the phosphorus atom; with the proviso that R 1 , R2, R ⁇ and R ⁇ are selected in such way, that the phosphino group R R2 > pi is different from the phosphino 25 group P 2 ⁇ R 4 R 5 .
- a catalyst system obtainable by combining (a) a source of a metal cation of palladium or, platinum with a diphosphine ligand as 30 defined above.
- a source of one or more these metal cations may be used in the various carbonylation reactions.
- palladium (Pd) is particularly preferred for carbonylation reactions involving olefinically unsaturated substrates
- platinum (Pt) is highly preferred for acetylenically unsaturated substrates, and for ethylenically unsaturated compounds if branched products are desired.
- suitable metal sources are metal compounds such as salts of Pd and/or Pt and nitric acid, sulphuric acid or sulphonic acids, salts of Pd and Pt and/or carboxylic acids with up to 12 carbon atoms, Pd and/or Pt complexes, e.g.
- the catalyst system further comprises as component (b) an unsymmetrical diphosphine of formula I, R 1 R 2 > pi _ R 3 _ P 2 ⁇ R 4 R 5 ( D wherein P 1 - and P ⁇ represent phosphorus atoms, R3 represents a divalent;.
- the beneficial effect of an unsymmetrical diphosphine compared to the corresponding symmetrical diphosphines is exhibited even if the substituents Rl and R2 attached to PI are very similar to the substituents R4 and R5 attached to P2.
- the difference in substituents results in a difference in the electron density at the phosphorus atoms.
- the presence of two binding phosphorus sites with different electronic density in the ligands then appears to have a beneficial effect on the reaction rate.
- the difference in electron donating ability of the phosphino fragments P ⁇ R ⁇ R 2 and p2 4 R 5 0 f the subject ligands may conveniently be measured by method developed by C. Tolman for monodentate phosphine ligands as described in Chemical Reviews, 1977, Vol. 77, pages 313-348.
- the electron- donating ability of a phosphine ligand is determined by reacting one equivalent of a (monodentate) phosphine with Ni(CO)4 to make P ⁇ R ⁇ R 2 a Ni (CO) 3 (phosphine) complex, and then measuring the carbonyl nCO IR stretching frequency (very sharp at high energy mode) of the Ni (CO) 3 (phosphine) complex.
- the two phosphorus atoms will have a different electron density.
- the substituents R! to R 4 are thus selected in such way, that one of the phosphorus atoms P ⁇ or P 2 has a lower electron density than the other phosphorus atom, as illustrated by a separate, lower nCO IR stretching frequency that can be measured for a transition metal carbonyl complex of the ligand (b) .
- the difference in electron density between the phosphorus atoms pi or P 2 may conveniently be achieved by selecting at R1, R 2 , R 4 and R ⁇ in such way, that one of the phosphorus atoms pi or P 2 has at least one more electron donating substituent R! and/or R 2 , as compared to R 4 and R 5 , or vice versa.
- Particularly high catalyst activities were found with ligands wherein R 1 and R 2 together, or each individually represent electron-donating groups as compared to a
- organic group represents an unsubstituted or substituted, aliphatic or arylaliphatic radical having from 1 to 30 carbon atoms, which is covalently connected to the phosphorus atom by a carbon atom.
- the organic groups R 1 -, R 2 , R 4 and R ⁇ may each independently be a monovalent group, or R 1 and R 2 together and/or R ⁇ and R ⁇ together may be divalent groups .
- the groups may further contain one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus and/or be substituted by one or more functional groups comprising for example oxygen, nitrogen, sulfur and/or halogen, for example by fluorine, chlorine, bromine, iodine and/or a cyano group.
- R ⁇ represents an organic group containing a tertiary carbon atom through which this group is linked to the phosphorus atom.
- R 1 and R 2 , or R 4 and R ⁇ represent an organic group containing a tertiary carbon atom through which each group is linked to the phosphorus atom, and an even higher and yet unprecedented activity was found where all of R 1 , R 2 , R 4 and R 5 represent an organic group containing a tertiary carbon atom through which each group is linked to the phosphorus atom.
- the subject invention also relates to the process for the carbonylation wherein all of Rl, R 2 , R4 and R ⁇ represent an organic group containing a tertiary carbon atom through which each group is linked to the phosphorus atom.
- the tertiary carbon atom through which one or more of the groups R ⁇ , R 2 , R 4 or R ⁇ preferably are connected to the phosphorus atom tertiary carbon atom, i.e.
- a carbon atom covalently bonded to the phosphorus and to three substituents other than hydrogen may be substituted with aliphatic, cycloaliphatic, or aromatic substituents, or may form part of a substituted saturated or non-saturated aliphatic ring structure, all of which may contain heteroatoms .
- the tertiary carbon atom of R 1 - and R 2 or
- R 4 and R ⁇ may be substituted with alkyl groups, thereby making the tertiary carbon atom part of a tertiary alkyl group, or by ether groups.
- suitable organic groups are tertiary-butyl, 2- (2-methyl) butyl, 2-(2-ethyl) butyl, 2-(2-phenyl) butyl, 2- (2-methyl) pentyl, 2-(2-ethyl)pentyl, 2- (2-methyl-4-phenyl) pentyl, 1-(1- methyl) cyclohexyl groups and 1-adamantyl-groups (wherein 1 or 2 adamantyl or trioxa-adadamtyl-groups are bonded to phosphorus atom via a tertiary bridge head atom) .
- the groups R 1 and R 2 , or R 4 and R5 may be each individually different organic groups, due to the use of lower amounts of different raw materials in the synthesis the groups R 1 and R 2 , or R 4 and R 5 preferably represent the same tertiary organic group. Yet more preferably, R! and R 2 , or R 4 and R ⁇ represent tertiary butyl groups. Accordingly, the subject invention also pertains to the process, wherein either both R 1 and R 2 , or both R 4 and R 5 represent a tertiary butyl group.
- the substituents of the second phosphorus atom i.e.
- R 1 and R 2 together, or R 4 and ⁇ together preferably represent a divalent group that is directly attached to the phosphorus atom via two tertiary carbon atoms.
- This divalent group may have a monocyclic or a polycyclic structure.
- R 1 and R 2 together or R 4 and R ⁇ together may also represent an optionally substituted divalent cycloaliphatic group, wherein the cycloaliphatic group is linked to the phosphorus atom via two tertiary carbon atoms.
- Examples of preferred divalent groups are unsubstituted or substituted C4-C3Q-alkylene groups in which CH2 ⁇ groups may be replaced by ether linkages through oxygen atoms, or other hetero groups.
- Suitable divalent groups include 1,1,4, 4-tetramethyl-buta-l, - diyl-, 1, -dimethyl-l, 4-dimethoxy-buta-l, 4-diyl-,
- Particularly preferred monocyclic structures comprising R 1 and R 2 together, or R 4 and R 5 together include 2,2,6, 6-tetrasubstituted phosphinan-4-one or -4-thione structures.
- Ligands comprising such structures may be conveniently obtained under mild conditions as described in Merrir and Day, Journal of Organic Chemistry, J. Am. Che . Soc, 27 (1962) 1824-1827, for instance by reaction of a secondary phosphine with 2,6- dimethyl-2, 5-heptadien-4-one (also known as diisopropylidene acetone, or phorone) .
- a particularly preferred polycyclic structure including R ⁇ - and R 2 or R 4 and R ⁇ together is for instance the 2-phospha-tricyclo [3.3.1.1 ⁇ 3, 7 ⁇ ] decyl group that is substituted in 1,3 and 5 position (thus providing the tertiary carbon atoms through which the group is connected to the phosphorous atom) , or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms.
- Tricyeio [3.3.1.1 ⁇ 3, 7 ⁇ ] decane is the systematic name, for a compound more generally known as adamantane .
- 2-PA 1,3, 5-trisubstituted 2-phospha-tricyclo [3.3.1.1(3,7 ⁇ decyl group or a derivative thereof will thus be referred to as "2-PA" group (as in 2-phosphadamantyl group) throughout the specification.
- the 2-PA group is substituted on one or more of the 1, 3, 5 positions, and optionally also on the 7 position, with a monovalent organic group R ⁇ from 1 to 20 atoms, preferably from 1 to 10 carbon atoms, yet more preferably from 1 to 6 carbon atoms.
- R 7 include methyl, ethyl, propyl and phenyl.
- the 2-PA group is substituted on each of the 1, 3, 5 and 7 positions, suitably with identical groups R 7 , yet more preferably with methyl groups.
- the 2-PA group further contains preferably additional heteroatoms other than the 2-phosphorus atom in its skeleton. Suitable heteroatoms are oxygen and sulphur atoms. More suitably, these heteroatoms are found in the 6, 9 and 10 positions.
- the most preferred bivalent radical is the 2-phospha-l, 3, 5, 7-tetramethyl-6, 9, 10-trioxadamantyl group.
- diphosphine ligands (b) fr the catalyst system according to the subject invention are compounds according to formula (II) , whe ein R ⁇ together with R 2 , or R 4 together witf ⁇ R5, together with the respective phosphorus atoms pi or P 2 , respectively, form a 2-phospha-l, 3, 5, 7-tetramethyl- 6, 9, 10-trioxadamantyl group, or a 2,2,6, 6-tetramethyl phosphinan-4-one, and wherein the other substituents Rl and R2, or R4 and R5 each individually represent a tertiary butyl group.
- a "divalent organic bridging group” R3 is understood the group connecting the phosphorus atoms pi and P 2 via the shortest connection in the ligand.
- the bridging group R ⁇ preferably may have a structure as represented by formula (III), -Ra m -Rb- R c n _ ( III ) wherein R a and R b independently represent the same or different optionally substituted methylene groups; R ⁇ represents an organic group comprising the bivalent bridging group C ⁇ -C 2 through which R ⁇ is connected to R a and R c ; m and n independently represent a natural number in the range of from 0 to 3, wherein the rotation about the bond between the carbon atoms of the bridging group
- C- and C 2 of the bridging group is restricted at a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C 1 , C 2 and the atom directly bonded to C 1 in the direction of P 1 , and the plane occupied by the three atom sequence C ⁇ -, C 2 and the atom directly bonded to C 2 in the direction of P 2 , is in the range of from 0 to 120°.
- bond and rotation are as defined in Hendrickson, Cram and Hammond, Organic
- Rotation according to the subject invention means that the atoms attached to C 1 - and C 2 respectively rotate about the axis that runs through the centre of the bond between C-- and
- the rotation about a bond is called “free” when the rotational barrier is so low that different conformations are not perceptible as different chemical species on the time scale of the experiment.
- the inhibition of rotation of groups about a bond due to the presence of a sufficiently large rotational barrier to make the phenomenon observable on the time scale of the experiment is termed "hindered rotation” or “restricted rotation” (as defined in IUPAC Compendium of Chemical Terminology, 2 nd Edition (1997), 68, 2209).
- a suitable experiment can for instance be an ⁇ H-NMR-experiment as described in
- the bond between C ⁇ and C there is no free rotation about the bond between C 1 and C 2 at the temperature range at which the subject process is conducted.
- This temperature range may conveniently be in between 0 °C to 250 °C, but preferably the subject process is conducted in the range of from 10 °C to 200 °C, and yet more preferably in the range of from 15 C C to 150 °C, and again more preferably in the range of from 18 °C to 130 °C.
- the rotation about the bond is considered hindered, if no rotation is measurable in the liquid state or in solution, i.e. at a temperature range where the ligand is liquid if determined under neat' conditions, or in solution of a suitable solvent.
- the rotation about the bond C 1 --C 2 of the bidentate ligand is hindered or restricted in solution or liquid state of the ligand.
- the rotation about the bond C ⁇ -C 2 of the bidentate ligand is preferably hindered or restricted in the temperature range of the subject process.
- the bridging group B comprises a chain of 2 optionally substituted carbon atoms C ⁇ and C . These carbon atoms C ⁇ and C 2 form the direct bridge between RiR 2 ?
- a dihedral angle is generally defined as the angle formed by two intersecting planes.
- the dihedral angle according to the subject process is the angle formed by the plane occupied by the three atom sequence composed of the three atoms C 2 , C 1 and the atom directly bonded to C 1 in direction of P 1 , and the plane occupied by the three atom sequence C ⁇ -, C 2 and the atom directly bonded to C 2 in direction of P 2 is in the range of from 0 to 120°, of the four atom sequence (atom directly bonded to C ⁇ in direction of pi) -C ⁇ -C 2 - (atom directly bonded to C 2 in the direction of P 2 ) .
- the dihedral angle is the angle between the plane occupied by the three atom sequence R a -cl-C 2 of the four atom sequence R a -C 1 -C 2 -R c and the other three atoms C 1 -C 2 -R c of the four atom sequence R a -C 1 -C -R c .
- Each plane is understood to run through the central points of the respective atoms.
- the dihedral angle as defined above is ranging from 0° to 120°. Since a higher catalytic activity of the catalyst system is thereby obtainable, the dihedral angle preferably is in the range of from 0° to 70, yet more preferably in the range of from 0° to 15°, and most preferably in the range of from 0° to 5°.
- ligands allowing rotation about the bond cl-C 2 are less able to form a conformationally stable bidentate complex with the palladium centre.
- the bond formed between C ⁇ and C 2 may be a saturated or an unsaturated bond as occurring in ethylenically unsaturated or aromatic compounds.
- R ⁇ can be expressed by C 1 R'R"-C 2 R"'R"
- the bidentate diphosphine ligand according to the present invention is thus suitably characterised by formula IV
- R' and R", and R'" and R" represent hydrogen or the same or different optionally substituted organic group, provided that only one of R' and R", and only one of R' " and R”" is hydrogen. If C 1 and C 2 are connected by an ethylenically unsaturated double bond, C ⁇ and C 2 also cannot rotate freely.
- the ligand chain connecting pi and P 2 via C-*- and C 2 may in principally exist in two isomeric forms, a trans-configuration, and a cis-configuration.
- the dihedral angle is about 180°
- the dihedral angle is about 0°.
- the substituents R' to R"" in formula IV or V can themselves be independent substituents, thus only connected to each other via the carbon atoms C ⁇ and C 2 , or preferably have at least one further connection.
- the substituents may further comprise carbon atoms and/or heteroatoms.
- the restriction of the free rotation may conveniently be achieved by the bridging group C- ⁇ -C 2 forming part of a molecular structure that impedes rotation about the bond
- This molecular structure may conveniently be for instance a) an ethylenically unsaturated double bond, wherein the rotation is impeded by the energetically advantageous overlap of ⁇ -bonds, and/or b) a cyclic hydrocarbyl structure, in which the rotation is restricted due to the steric interaction of substituents R' to R"", or due to steric strain induced by a cyclic structure formed by R' to R"" together, or by combination of the above factors, such as in aromatic or non-aromatic cyclic structures.
- Conformational stability and hence rigidity may also c) be achieved if the nature of the substituents R' and R", and/or R'" and R"" is such that even if not connected to each other they impede rotation about the bond C ⁇ -C 2 , for instance by strong steric interactions.
- R' to R" in formula IV or V represent hydrogen.
- R b preferably is a cyclic hydrocarbyl structure that is optionally substituted by hetereoatoms, yet more preferably an aliphatic or aromatic hydrocarbyl structure.
- This structure may be part of an optionally further substituted saturated or unsaturated polycyclic structure, which also optionally may contain heteroatoms such as nitrogen, sulphur, silicon or oxygen atoms.
- Suitable structures R b include for instance substituted cyclohexyl, cyclohexenyl, cyclohexadienyl, substituted cyclopentane, cyclopentenyl or cyclopentadienyl structures, all of which may optionally contain heteroatoms such as nitrogen, sulphur, silicon or oxygen atoms, with the proviso that the rotation about the bond C ⁇ -C 2 is restricted, that the dihedral angle is in the range of from 0° to 120°, and that there is preferably no rotation about the bond formed by C 1 - and C 2 induced by conformational changes, as for instance in highly restrained acetal structures such as 2, 2-dimethyl-l, 3-dioxolane.
- R 3 represents a divalent polycyclic hydrocarbyl ring structure.
- Such polycyclic groups are particularly preferred due to the high conformational stability and hence high restriction against free rotation about the bond between C ⁇ - and C 2 .
- Examples of such particularly preferred hydrocarbyl groups include norbornyl, norbornadienyl, isonobornyl, dicylcopentadienyl, octahydro-4,
- R preferably represents an optionally substituted divalent aromatic group which is linked to the phosphorus atoms via the groups R a and R c .
- the aromatic group can be a monocyclic group, such as for example a phenyl group or a polycyclic group, such as for example a naphthyl, anthryl or indyl group.
- the aromatic group R contains only carbon atoms, but R 3 can also represent an aromatic group wherein a carbon chain is interrupted by one or more hetero atoms, such as nitrogen, sulphur or oxygen atom in for example a pyridine, pyrrole, furan, thiophene, oxazole or thiazole group.
- the aromatic group Rb represents a phenyl group or naphtylene group.
- Suitable substituents include groups containing hetero-atoms such as halides, sulphur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide and groups of the general formula -0-H, -O-X, -CO-X, -CO- O-X, -S-H, -S-X, -CO-S-X, -NH2, -NHX, -N0 , -CN, -CO-NH 2 , -CO-NHX, -C0-NX2, -CI3 or -CF3, in which X independently represents alkyl groups having from 1 to 4 carbon atoms like methyl, ethyl, propyl, isopropyl and n-butyl.
- the aromatic group When the aromatic group is substituted it is preferably substituted with one or more aryl, alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms. Suitable groups include methyl, ethyl, tri ethyl, iso- propyl, tetramethyl and iso-butyl, phenyl and cyclohexyl. Most preferably, however, the aromatic group R is non-substituted and only linked to the groups R a and R c which connect it with the phosphorus atoms . Yet more preferably, R a and R c are alkylene groups, and thus connected at adjacent positions, for example the 1 and 2 positions, of the aromatic group.
- m and n in formula III, IV and V independently may represent a natural number in the range of from 0 to 3. If the m and n are 0, then the phosphorus atoms i and P 2 are directly connected to bridge formed by the carbon atoms C ⁇ and C 2 . If one of m or n equals 0, then either C 1 - or C 2 will be directly connected to pi or
- R a and R c connect p and P 2 to R b .
- R a and/or R c These different may then be the same or individually different groups.
- R a and/or R c preferably are lower alkylene groups (by lower alkylene groups is understood alkylene groups comprising from 1 to 4 carbon atoms) .
- alkylene groups can be substituted, for example with alkyl groups or heteroatoms, or non-substituted, and may for instance represent methylene, ethylene, trimethylene, iso- propylene, tetramethylene, iso-butylene and tert- butylene, or may represent methyloxy, ethyloxy and similar groups.
- R a and/or R c is a methylene group.
- Particularly suitable aromatic groups for R ⁇ 3 include aryl groups such as disubstituted phenyl or naphthyl groups, and substituted alkyl phenyl groups such as tolyl and xylyl groups, groups.
- Preferred due to the high stability of the obtained ligands and catalysts are tolyl and xylyl groups, wherein the methylene substituent or methylene substituents at the aromatic ring serve as groups R a and/or R c .
- C 1 and C 2 are part of an aromatic ring, whereas at least one of R a and/or R c represent methylene groups attached to adjacent atoms C 1 and C 2 in the aromatic ring.
- an especially preferred ligand family according to the subject invention is that wherein C ⁇ and C 2 are part of a phenyl ring; m is 0 or 1; n is 1, and R a and R c are methylene groups.
- m and n 1
- ligands based on the 1, 2-di (phosphinomethyl) benzene or l-phosphino-2- (phosphino methyl) -benzene groups are particularly suited for the subject process due to the high rigidity of the aromatic backbone, easy synthetic availability, and due to the very good results obtained with the derived catalyst system.
- Such a ligand is for instance 1- (1, 3, 5, 7-tetramethyl-l, 3, 5-trimethyl-6, 9, 10-trioxa-2-phosphatricyclo [3.3.1.1 ⁇ 3 ' 7 1] decyl-2- (di- tert-butylphosphinomethyl) benzene .
- these ligands were employed in a catalyst composition comprising the unsymmetrical bidentate diphosphine ligand and a source of palladium, platinum, or rhodium.
- the latter was found effective in particular for hydroformulation reaction, i.e. carbonylation reactions ion the presence of a source of hydride, such as molecular hydrogen, in particular in the presence of a source of an anion.
- the subject process permits to convert non-conjugated ethylenically and acetylenically unsaturated compounds to the corresponding products with very high turnover numbers due to the high catalyst activity.
- Suitable ethylenically or acetylenically unsaturated compounds are ethylenically or acetylenically unsaturated compounds having from 2 to 50 carbon atoms per molecule, or mixtures thereof. Suitable ethylenically and acetylenically unsaturated compounds may have one or more isolated unsaturated bonds per molecule. Preferred are compounds having from 2 to 20 carbon atoms, or mixtures thereof, yet more preferred are compounds having at most 18 carbon atoms, yet more at most 16 carbon atoms, again more preferred compounds have at most 10 carbon atoms.
- the ethylenically or acetylenically unsaturated compound may further comprise functional groups or heteroatoms, such as nitrogen, sulphur or oxide.
- the ethylenically or acetylenically unsaturated compound is an olefin or a mixture of olefins.
- Such olefins can be converted by reaction with carbon monoxide and a co-reactant with a high regioselectivity towards the linear carbonylation product.
- Suitable ethylenically or acetylenically unsaturated compounds include acetylene, methyl acetylene, propyl acetylene, ethylene, propylene, butylene, isobutylene, pentene, pentene nitriles, methyl 3-pentenoates, 2- and 3-pentenoic acid.
- Another preferred feedstock are mixtures of olefins, or mixtures of olefins and saturated compounds obtained for instance in a
- Fischer-Tropsch synthesis step In such a synthesis, usually a mixture of olefins and saturated hydrocarbons is obtained.
- the content of olefins in this mixture may vary, and may be increased by starting of with the synthesis product of an iron-catalyzed Fischer-Tropsch synthesis step.
- An even higher olefinic content of the mixture may be obtained by catalytic dehydrogenation or thermal cracking in the presence of steam.
- the subject process in particular suited for reacting such mixtures, as it selectively reacts with olefinic or acetylenically non-conjugated compounds in such a mixture without affecting the other saturated compounds, and hence allows an easy separation of the carbonylated products from the saturated hydrocarbons.
- ethylenically or acetylenically unsaturated compounds may be converted into very different chemical compounds, such as aldehydes, esters, acids or acid anhydride, thioesters, amides, and alcohols or others.
- the specific nature of the product is depending on the nature of the co-reactant having a mobile hydrogen atom.
- the co-reactant according to the present invention may thus be any compound having a mobile hydrogen atom, and which is capable of reacting as a nucleophile with the diene under catalysis. The nature of the co-reactant largely determines the type of product formed.
- a suitable co-reactant is water, a carboxylic acid, alcohol, ammonia or an amine, a thiol, or a combination thereof.
- the catalyst systems may be used in "hydroformylation reactions", “hydrocarboxylation reactions”, “hydroesterification reactions” or “hydroamidation reactions”.
- the co-reactant is water
- the product obtained will be a carboxylic acid.
- Anhydrides are obtained inasmuch as the co-reactant is a carboxylic acid.
- the product of the carbonylation is an ester.
- R, R' and/or R" represent optionally heteroatom- substituted organic radicals, preferably alkyl, alkenyl or aryl radicals.
- ammonia or amines When ammonia or amines are employed, a small portion of these co-reactants will react with acids present under formation of an amide and water. Hence, in the case of ammonia or amine-co-reactants, there is always water present.
- Preferred alcohol co-reactants are alkanols with 1 to 20, more preferably with 1 to 6 carbon atoms per molecule, and alkanediols with 2-20, more preferably 2 to 6 carbon atoms per molecule.
- the alkanols can be aliphatic, cycloaliphatic or aromatic.
- Suitable alkanols in the process of the invention include methanol, ethanol, ethanediol, n-propanol, 1,3- propanediol, iso-propanol, 1-butanol, 2-butanol (sec- butanol) , 2-methyl-1- propanol (isobutanol) , 2-methyl-2 ⁇ propanol (tert-butanol) , 1-pentanol, 2- pentanol, 3- pentanol, 2-methyl-l-butanol, 3-methyl-l-butanol (isoamyl alcohol), 2-methyl-2-butanol (tert-amyl alcohol), 1- hexanol, 2-hexanol, 4-methyl-2-pentanol, 3, 3-dimethyl-2- butanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1,2-ethylene glycol and 1, 3-propylene
- Preferred amines have from 1 to 20, more preferably 1 to 6 carbon atoms per molecule, and diamines have from 2-20, more preferably 2 to 6 carbon atoms per molecule.
- the amines can be aliphatic, cycloaliphatic or aromatic. More preferred due to the high turnovers achieved are ammonia and primary amines.
- Thiol co-reactants can be aliphatic, cycloaliphatic or aromatic.
- Preferred thiol co-reactants are aliphatic thiols with 1 to 20, more preferably with 1 to 6 carbon atoms per molecule, and aliphatic dithiols with 2-20, more preferably 2 to 6 carbon atoms per molecule.
- the subject carbonylation reaction is also known as a hydrofor ylation reaction in the case that the co- reactant is a hydride source, such as molecular hydrogen.
- a hydrofor ylation reaction in the case that the co- reactant is a hydride source, such as molecular hydrogen.
- This can be achieved by supplying carbon monoxide and hydrogen to the reaction in equimolar or non-equimolar ratios, e.g. in a ratio within the range of 5:1 to 1:5, preferably 3:1 to 1:3.
- they are supplied in a ratio within the range of 2:1 to 1:2, and will result in alcohol mixtures.
- Fischer-Tropsch product streams are used as feedstocks, the obtained product mixtures can be suitably used for sanitary or other related applications.
- the carbonylation can be suitably carried out at moderate reaction conditions.
- reaction pressures in the range of 5 to 100 bar are preferred, lower or higher pressures may be selected, but are not considered particularly advantageous. Moreover, higher pressures require special equipment provisions.
- the unsaturated starting material and the formed product as well as the co-reactant may act as reaction solvent. Hence, the use of a separate solvent might not be necessary.
- the carbonylation reaction may be carried out in the additional presence of a solvent, in particular in the start-up phase of the reaction.
- saturated hydrocarbons e.g.
- paraffins and isoalkanes are recommended and furthermore alcohols, the saturated hydrocarbons and alcohols preferably having from 1 to 10 carbon atoms per molecule, such as methanol, butanol, 2-ethylhexan-l-ol, nonan-1-ol, or in general terms the alcohols formed as carbonylation product; ethers such as 2, 5, 8-trioxanonane (diglyme), diethylether and anisole, and ketones such as methylethylketone. Solvents, comprising or substantially consisting of sulphones are also preferred.
- Sulphones are in particular preferred, for example dialkylsulphones such as di ethyl- sulphone and diethylsulphone and cyclic sulphones, such as sulfolane, 2-methylsulfolane and 2-methyl-4-ethyl- sulfolane.
- the ratio of moles of bidentate diphosphine, i.e. catalyst component (b) , per mole atom of palladium cations, i.e. catalyst component (a) ranges from 0.5 to 10, preferably from 0.8 to 8, and yet more preferably from 1 to 5.
- catalyst component (b) per mole atom of palladium, i.e. catalyst component (a), is not critical. Preferably it ranges from 0.1 to 100, more preferably from 0.5 to 10.
- a more preferred catalyst the active species is based on an equimolar amount of bidentate diphosphine ligand per mole palladium.
- the molar amount of bidentate diphosphine ligand per mole palladium is preferably in the range of 1 to 3, more preferably in the range of 1 to 2, and yet more preferably in the range of 1 to 1.5. In the presence of oxygen, slightly higher amounts may be beneficial.
- the catalyst system or composition further preferably comprises a source of an anion.
- a suitable source of anion may be a strong, or a weak coordinating anion.
- Various anions may be used as counter-ion to the metal cation. Examples thereof include anions that are the conjugated base of acids having a pKa (measured at 18 °C in water) of less than 6, preferably less than 4.
- the anions derived from these acids do not or only weakly co-ordinate with the metal cation, by which is meant that little or no covalent interaction occurs between the anion and the cation. Catalysts based on these anions exhibit a good activity.
- Suitable anions include anions derived from Bronsted acids, such as from phosphoric acid and sulphuric acid, and in particular from sulphonic acids and (halogenated) carboxylic acids, such as trifluoroacetic acid, 2,6-di chlorobenzoic acid, and 2, 6-bis (trifluoromethyl) benzoic acid or trifluoroacetic acid, etc.
- Anions derived from sulphonic acids are particularly preferred, for example methanesulphonic acid, trifluoromethanesulphonic acid, tert-butanesulphonic acid, p-toluenesulphonic acid and 2,4, 6-trimethylbenzenesulphonic acid.
- complex anions are suitable, such as the anions generated by a combination of a Lewis acid such as BF3, B(CgF5)3, AICI3, SnF , Sn(CF3S03)2r SnCl2 or GeCl2, with a protic acid, preferably having a pKa of less than 5, such as a sulphonic acid, e.g. CF3SO3H or CH3SO3H or a hydrohalogenic acid such as HF or HC1, or a combination of a Lewis acid with an alcohol.
- a sulphonic acid e.g. CF3SO3H or CH3SO3H or a hydrohalogenic acid such as HF or HC1, or a combination of a Lewis acid with an alcohol.
- the source of anions is a carboxylic acid, which can serve both as promoter component, as well as solvent for the reaction.
- the source of anions is an acid having a pK a below 3.6
- catalyst component (c) is an acid having a pK a below 3.0, and yet more preferably a pK a of above 2.0.
- Suitable acids include acetic acid, propionic acid, butyric acid, pentanoic acid, pentenoic acid and nonanoic acid.
- the acid corresponding to the desired product of the reaction can be used as the catalyst component (c) .
- Catalyst component (c) can also be an ion exchanging resin containing carboxylic acid groups. This advantageously simplifies the purification of the product mixture.
- the co-reactant is an amine or ammonia
- the source of an anion of the catalyst system is an acid, preferably the amount of ammonia or amine is less than stoichiometric based on the amine functionality.
- the co-reactant when the co-reactant is ammonia, and to a lesser extent a primary amine, a small amount of the acid present will react to an amide under liberation of water. Hence, there is also always a small amount of acid formed from the unsaturated compound, carbon monoxide and the water, which in turn replaces acid converted to amide by the direct reaction as described above.
- the molar ratio of the source of anions, and palladium, platinum, or rhodium is not critical. However, it suitably is between 2:1 and 10 7 :1 and more preferably between 10 2 :1 and 10°: 1, yet more preferably between
- the amount of the acid to co-reactant should be chosen such that a suitable amount of free acid is present. Generally, a large surplus of acid over the co-reactant is preferred due to the enhanced reaction rates.
- the quantity in which the complete catalyst system is used is not critical and may vary within wide limits.
- Suitable pressures are in the range of 0.1 to 15 MPa (1 to 150 bar), preferably in the range of 0.5 to 8.5 MPa (5 to 85 bar). Carbon monoxide partial pressures in the range of 0.1 to 8 MPa (1 to 80 bar) are preferred, the upper range of 4 to 8 MPa being more preferred. Higher pressures require special equipment provisions .
- the carbonylation reaction is further conveniently carried out at a temperature in the range of 30 to 200 °C, preferred temperatures being in the range of 50 to 180 °C.
- the carbon monoxide can be used in its pure form or diluted with an inert gas such as nitrogen, carbon dioxide or noble gases such as argon, or co-reactant gases such as ammonia.
- an inert gas such as nitrogen, carbon dioxide or noble gases such as argon, or co-reactant gases such as ammonia. The invention will be illustrated by the following non-limiting examples .
- Figure 1 9- (2- ⁇ [di (tert-butyl) hosphino] ethyl ⁇ -2- propenyl) -
- a mixture of di-tert-butylphosphine (5 g, 34.1 mmol) and 3-chloro-2-chloromethyl-l-propene (14,04 g, 69 mmol) was dissolved in degassed acetonitrile (70 ml) and heated to 60 °C for 16 hours. The solvent was removed in vacuo and the product was suspended in hexane (50 ml) . After filtration the product was washed with hexane (2 times 40 ml) .
- the white solid salt was neutralized in a mixture of toluene (50 ml) and water (30 ml) with HNEt2 (5 ml) under reflux conditions.
- the toluene layer was separated, washed with water (2 times 30 ml) and removed in vacuo, to yield 3.14 g (40%) of di (tert-butyl) [2- (chloromethyl) - 2-propenyl] phosphine.
- the product could be characterized by showing a distinct resonance signals in 31p NMR at ⁇ - + 21.7 ppm. 2.82 g (20 mmol) of the 9-phosphabicyclo [3.3.1] nonane was dissolved in THF (90 ml).
- the mixture was washed twice with water (40 ml and 20 ml) and the toluene was removed in vacuo giving 6.71 g of a red/orange oil.
- the product was crystallized twice from (boiling) methanol, giving a white solid (2.83 g, 42%).
- the product could be characterized by showing two distinct resonance signals in 31p NMR at + 22.1 ppm and - , 36.5 ppm.
- Figure 2 8- (2- ⁇ [di (tert-butyl) phosphino]methyl ⁇ -2- propenyl) -1, 3, 5,7-tetramethyl-2, 4, 6-trioxa-8- phosphatricyclo [3.3.1.1. ⁇ 3,7 ⁇ ] decane
- Figure 3 8- (2- ⁇ [di (tert-butyl) phosphino] methyl ⁇ phenyl) 1,3,5, 7-tetramethyl-2, 4, 6-trioxa-8-phosphatricyclo- [3.3.1.1 ⁇ 3,7 ⁇ ]decane 8.25 g (33 mmol) 2-bromobenzylbromide and 5 g (34.2 mmol) di-tert-butyl phosphine in 40 ml degassed acetonitrile were measured into a 100 ml glass reactor under an inert atmosphere, and then stirred for a period of 12 hours at ambient temperature.
- Examples 4 to 6 and Comparative Examples A, B and C Conversion of 1-octene with methanol
- a 250 ml magnetically stirred autoclave, made of HASTELLOY C (HASTELLOY C is a trademark) was successively charged with 40 ml of methanol, 20 ml 1- octene, and 0.5 mmol of methanesulfonic acid, and a catalyst solution comprising 0.1 mmol palladium acetate and 0.2 mmol of the respective ligand in 10 ml of methanol.
- the autoclave was closed, evacuated, and pressurized with 3 MPa carbon monoxide.
- the reactor was then heated to 70 °C, and maintained at this temperature for 10 hours.
- the reactor was then heated to 85 °C, and a catalyst solution comprising 0.05 mmol palladium acetate and 0.1 mmol of the respective ligand in 5 ml of methanol was injected into the autoclave, thereby raising the carbon monoxide pressure by an additional 5 bar.
- the autoclave was maintained at 85 °C for 10 hours.
- the reaction mixture was analysed with GLC. The turn over frequency is defined as amount of converted products, and given in mol olefin per mol Pd per hour for the batch operation as presented in, Table I.
- Example 4 the ligand was 9- (2- ⁇ [di (tert-butyl) phosphino] methyl ⁇ -2-propenyl) -9- phosphabicyclo [3.3.1] nonane prepared in Example 1.
- the ligand was 8-(2- ⁇ [di (tert-butyl) phosphino]methyl ⁇ -2-propenyl) - 1,3,5, 7-tetramethyl-2, 4, 6-trioxa-8- phosphatricyclo[3.3.1.1.3,7] decane prepared in Example 2.
- the ligand was 8- (2- ⁇ [di ( tert-butyl) phosphino]methyl ⁇ phenyl) - 1,3,5, 7-tetramethyl-2,4, 6-trioxa-8-phospha- tricyclo [3.3.1.1 ⁇ 3, 7 ⁇ ] decane prepared in Example 3.
- the ligand was a symmetrical ligand with two 9-phosphabicyclo [3.3.1] nonane rings attached to an isobutene structure (9- [2- (9- phosphabicyclo [3.3.1] non-9-ylmethyl) -2-propenyl] -9- phosphabicyclo [3.3. l]nonane) .
- the ligand was the symmetrical bis-di-tert-butyl phosphino-analogue (di ( ert-butyl) (2- ⁇ [di ( tert- butyl) phosphino]methyl ⁇ -2-propenyl) phosphine) .
- the ligand was the symmetrical bis-trioxa-adamantyl-ligand (1, 3, 5, 7-tetramethyl-8- ⁇ 2- [1,3,5, 7-tetramethyl-2, , 6-trioxa-8- phosphatricyclo [3.3.1.1 ⁇ 3,7 ⁇ ] dec-8-yl) methyl] -2- propenyl ⁇ -2, 4, 6-trioxa-8-phospha- tricyclo [3.3.1.1 ⁇ 3, 7 ⁇ ] decane) .
- the ligand was the symmetrical bis-trioxadamantyl-ligand ( [1, 3, 5, 7-tetramethyl-8- ⁇ 2- [1, 3, 5, 7-tetramethyl-2, 4, 6- trioxa-8-phosphatricyclo[3.3.1.1. ⁇ 3,7 ⁇ ]dec-8- yl) methyl] benzyl ⁇ -2 , , 6-trioxa-8-phosphatricyclo- [3.3.1.1 ⁇ 3, 7 ⁇ ]decane) .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for the carbonylation of unsaturated compounds by contacting the unsaturated compound with carbon monoxide in the presence of a catalyst system comprising: (a) a source of palladium and/or platinum; and (e) an unsymmetrical bidentate diphosphine ligand of formula (I), R1R2 > P1 - R3 - P2 < R4R5 (I) wherein P1 andp P2 represent phosphorus atoms; R3 represents a divalent organic bridging group; and R1, R2, R4 and R5 each individually, or Rl and R2 jointly, and/or R4 and R5 jointly represent organic groups that are covalently linked to the phosphorus; and wherein R1, R2, R4 and R5 are chosen in such way, that the phosphino group R1R2 > P1 differs from the phosphino group P2 < R4R5.
Description
PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY OR ACETYLENICALLY UNSATURATED COMPOUNDS
Field of the invention The present invention provides a process for the carbonylation of ethylenically or acetylenically unsaturated compounds. Background of the invention In this specification, the term carbonylation refers to the reaction of alkenes or alkynes, i.e. ethylenically or acetylenically non-conjugated unsaturated compounds, under catalysis by a transition metal complex with carbon monoxide and a co-reactant having a mobile hydrogen atom, as for instance described in EP-A-0, 495, 548 and EP-A- 0,565,199, WO-A-96/19434, WO-A-98/42717, WO-A-01/68583 and WO-A-01/72697. This process results in carboxylic acid products, or carboxylic acid derivatives, such as esters, amides or anhydrides, depending on the nature of
the co-reactant. EP-A-0, 495, 548 discloses a catalyst system comprising a palladium cation and diphosphine bidentate ligands bearing di-alkyl-substituted phosphino groups, such as for instance 1,3 bis (di-tertiary butyl phosphino) propane, and the use of such catalysts in various carbonylation reactions. Although the disclosed catalyst systems show a good activity in carbonylation reactions, application of the process on an industrial scale requires further improvements in catalyst activity and selectivity for the desired products.
Summary of the invention It has now been found that catalyst systems based on a metal cation selected from 8, 9 or 10 of the Periodic Table of Elements and an unsymmetrical diphosphine ligand 5 exhibit improved catalyst activity in the carbonylation of ethylenically or acetylenically unsaturated compounds, thereby resulting in a significantly improved carbonylation process. Accordingly, the subject invention relates to a 10 process for the carbonylation of an ethylenically or acetylenically unsaturated compound by contacting the unsaturated compound with carbon monoxide and a co- reactant having a mobile hydrogen atom in the presence of a catalyst system comprising: 15 (a) a source of a palladium and/or platinum; and (b) an unsymmetrical diphosphine of formula I, R1R2 pi _ R3 _ P2 < R4R5 (D wherein P1- and P^ represent phosphorus atoms; R-3
?, J- represents a divalent organic bridging group; and R1, R^, 20 R^ and R^ each individually, or R1- and R2 jointly, and/or R4 and R5 jointly represent organic substituents that are covalently bound to the phosphorus atom; with the proviso that R1, R2, R^ and R^ are selected in such way, that the phosphino group R R2 > pi is different from the phosphino 25 group P2 < R4R5. Detailed description of the invention The subject process makes use of a catalyst system obtainable by combining (a) a source of a metal cation of palladium or, platinum with a diphosphine ligand as 30 defined above. A source of one or more these metal cations may be used in the various carbonylation reactions. Of these metal cations, palladium (Pd) is
particularly preferred for carbonylation reactions involving olefinically unsaturated substrates, whereas platinum (Pt) is highly preferred for acetylenically unsaturated substrates, and for ethylenically unsaturated compounds if branched products are desired. Examples of suitable metal sources are metal compounds such as salts of Pd and/or Pt and nitric acid, sulphuric acid or sulphonic acids, salts of Pd and Pt and/or carboxylic acids with up to 12 carbon atoms, Pd and/or Pt complexes, e.g. with carbon monoxide and/or acetyl acetonate, or Pd and/or Pt combined with a solid material such as an ion exchanger. Pd and/or Pt acetate and acetyl acetonate are examples of preferred metal sources . The catalyst system further comprises as component (b) an unsymmetrical diphosphine of formula I, R1R2 > pi _ R3 _ P2 < R4R5 (D wherein P1- and P^ represent phosphorus atoms, R3 represents a divalent;.;organic bridging group, and R1-, R2, R4 and R5 each individually, or R1 and R2 jointly and/or R4 and R^ jointly represent organic substituents that are covalently bound to the phosphorus atom; with the proviso that R1, R2, R and R^ are selected in such way, that the phosphino group R^R2 > pi is different from the phosphino group P2 < R4R5. The beneficial effect of an unsymmetrical diphosphine compared to the corresponding symmetrical diphosphines is exhibited even if the substituents Rl and R2 attached to PI are very similar to the substituents R4 and R5 attached to P2. Without wishing to be bound to any particular theory, it is believed that the difference in substituents results in a difference in the electron
density at the phosphorus atoms. The presence of two binding phosphorus sites with different electronic density in the ligands then appears to have a beneficial effect on the reaction rate. The difference in electron donating ability of the phosphino fragments P^R^R2 and p2 4R5 0f the subject ligands may conveniently be measured by method developed by C. Tolman for monodentate phosphine ligands as described in Chemical Reviews, 1977, Vol. 77, pages 313-348. In this method, the electron- donating ability of a phosphine ligand is determined by reacting one equivalent of a (monodentate) phosphine with Ni(CO)4 to make P^R^R2 a Ni (CO) 3 (phosphine) complex, and then measuring the carbonyl nCO IR stretching frequency (very sharp at high energy mode) of the Ni (CO) 3 (phosphine) complex. The more electron density the phosphine ligand donates to a metal centre, and hence the higher the electron-donating ability, the lower the nCO IR stretching frequency measured. In the diphosphine (b) , even if only one of the substituents R1, R2, R4 or R^ differs from the other substituents, the two phosphorus atoms will have a different electron density. The substituents R! to R4 are thus selected in such way, that one of the phosphorus atoms P^ or P2 has a lower electron density than the other phosphorus atom, as illustrated by a separate, lower nCO IR stretching frequency that can be measured for a transition metal carbonyl complex of the ligand (b) . The difference in electron density between the phosphorus atoms pi or P2 may conveniently be achieved by selecting at R1, R2, R4 and R^ in such way, that one of the phosphorus atoms pi
or P2 has at least one more electron donating substituent R! and/or R2, as compared to R4 and R5, or vice versa. Particularly high catalyst activities were found with ligands wherein R1 and R2 together, or each individually represent electron-donating groups as compared to a
PPh2~group, whereas R4 and R^ together or each individually represent an electron-accepting group as compared to a PPh2~group. Within the context of the subject specification, the term "organic group" represents an unsubstituted or substituted, aliphatic or arylaliphatic radical having from 1 to 30 carbon atoms, which is covalently connected to the phosphorus atom by a carbon atom. The organic groups R1-, R2, R4 and R^ may each independently be a monovalent group, or R1 and R2 together and/or R^ and R^ together may be divalent groups . The groups may further contain one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus and/or be substituted by one or more functional groups comprising for example oxygen, nitrogen, sulfur and/or halogen, for example by fluorine, chlorine, bromine, iodine and/or a cyano group. Although increased catalyst activity as compared to each of the analogous symmetrical ligands was shown by all non-symmetric bidentate ligands tested, a particularly high increase in catalyst activity was found with ligands wherein at least one of R1 and R2, or R4 and
R^ represents an organic group containing a tertiary carbon atom through which this group is linked to the phosphorus atom.
A yet higher activity was found where both R1 and R2, or R4 and R^ represent an organic group containing a tertiary carbon atom through which each group is linked to the phosphorus atom, and an even higher and yet unprecedented activity was found where all of R1, R2, R4 and R5 represent an organic group containing a tertiary carbon atom through which each group is linked to the phosphorus atom. Therefore, most preferably, the subject invention also relates to the process for the carbonylation wherein all of Rl, R2, R4 and R^ represent an organic group containing a tertiary carbon atom through which each group is linked to the phosphorus atom. The tertiary carbon atom through which one or more of the groups R^, R2, R4 or R^ preferably are connected to the phosphorus atom tertiary carbon atom, i.e. a carbon atom covalently bonded to the phosphorus and to three substituents other than hydrogen, may be substituted with aliphatic, cycloaliphatic, or aromatic substituents, or may form part of a substituted saturated or non-saturated aliphatic ring structure, all of which may contain heteroatoms . Preferably, the tertiary carbon atom of R1- and R2, or
R4 and R^ may be substituted with alkyl groups, thereby making the tertiary carbon atom part of a tertiary alkyl group, or by ether groups. Examples of suitable organic groups are tertiary-butyl, 2- (2-methyl) butyl, 2-(2-ethyl) butyl, 2-(2-phenyl) butyl, 2- (2-methyl) pentyl, 2-(2-ethyl)pentyl, 2- (2-methyl-4-phenyl) pentyl, 1-(1- methyl) cyclohexyl groups and 1-adamantyl-groups (wherein 1 or 2 adamantyl or trioxa-adadamtyl-groups are bonded to phosphorus atom via a tertiary bridge head atom) .
Although the groups R1 and R2, or R4 and R5 may be each individually different organic groups, due to the use of lower amounts of different raw materials in the synthesis the groups R1 and R2, or R4 and R5 preferably represent the same tertiary organic group. Yet more preferably, R! and R2, or R4 and R^ represent tertiary butyl groups. Accordingly, the subject invention also pertains to the process, wherein either both R1 and R2, or both R4 and R5 represent a tertiary butyl group. The substituents of the second phosphorus atom, i.e.
R1 and R2 together, or R4 and ^ together preferably represent a divalent group that is directly attached to the phosphorus atom via two tertiary carbon atoms. This divalent group may have a monocyclic or a polycyclic structure. Accordingly, R1 and R2 together or R4 and R^ together may also represent an optionally substituted divalent cycloaliphatic group, wherein the cycloaliphatic group is linked to the phosphorus atom via two tertiary carbon atoms. Examples of preferred divalent groups are unsubstituted or substituted C4-C3Q-alkylene groups in which CH2~ groups may be replaced by ether linkages through oxygen atoms, or other hetero groups. Suitable divalent groups include 1,1,4, 4-tetramethyl-buta-l, - diyl-, 1, -dimethyl-l, 4-dimethoxy-buta-l, 4-diyl-,
1, 1,5,5-tetramethyl-penta-l, 5-diyl-, 1, 5-dimethyl-l, 5- dimethoxy-penta-1, 5-diyl-, 3-oxa-l, 5-dimethoxy-penta-l, 5-diyl-, 3-oxa-l, 1,5, 5-tetramethyl-penta-l, 5-diyl-, 3- oxa-1, 5-dimethyl-l, 5-dimethoxy-penta-l, 5-diyl- and similar divalent radicals.
Particularly preferred monocyclic structures comprising R1 and R2 together, or R4 and R5 together include 2,2,6, 6-tetrasubstituted phosphinan-4-one or -4-thione structures. Ligands comprising such structures may be conveniently obtained under mild conditions as described in Welcher and Day, Journal of Organic Chemistry, J. Am. Che . Soc, 27 (1962) 1824-1827, for instance by reaction of a secondary phosphine with 2,6- dimethyl-2, 5-heptadien-4-one (also known as diisopropylidene acetone, or phorone) . A particularly preferred polycyclic structure including R^- and R2 or R4 and R^ together is for instance the 2-phospha-tricyclo [3.3.1.1{3, 7} ] decyl group that is substituted in 1,3 and 5 position (thus providing the tertiary carbon atoms through which the group is connected to the phosphorous atom) , or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms. Tricyeio [3.3.1.1{3, 7 } ] decane is the systematic name, for a compound more generally known as adamantane . The
1,3, 5-trisubstituted 2-phospha-tricyclo [3.3.1.1(3,7}decyl group or a derivative thereof will thus be referred to as "2-PA" group (as in 2-phosphadamantyl group) throughout the specification. The 2-PA group is substituted on one or more of the 1, 3, 5 positions, and optionally also on the 7 position, with a monovalent organic group R^ from 1 to 20 atoms, preferably from 1 to 10 carbon atoms, yet more preferably from 1 to 6 carbon atoms. Examples of R7 include methyl, ethyl, propyl and phenyl. More preferably, the 2-PA group is substituted on each of the 1, 3, 5 and 7 positions, suitably with identical groups R7, yet more preferably with methyl
groups. The 2-PA group further contains preferably additional heteroatoms other than the 2-phosphorus atom in its skeleton. Suitable heteroatoms are oxygen and sulphur atoms. More suitably, these heteroatoms are found in the 6, 9 and 10 positions. The most preferred bivalent radical is the 2-phospha-l, 3, 5, 7-tetramethyl-6, 9, 10-trioxadamantyl group. Very good results have been obtained in the carbonylation of ethylenically unsaturated compounds with catalyst system comprising bidentate diphosphine ligands whereby R-- and R2 are each individually organic groups only connected to each other via a phosphorus atom, whereas R^ and R^ together represent a bivalent organic group that is bonded to the second phosphorus atom via two tertiary carbon atoms. Accordingly, especially preferred diphosphine ligands (b) fr the catalyst system according to the subject invention are compounds according to formula (II) , whe ein R^ together with R2, or R4 together witfø R5, together with the respective phosphorus atoms pi or P2, respectively, form a 2-phospha-l, 3, 5, 7-tetramethyl- 6, 9, 10-trioxadamantyl group, or a 2,2,6, 6-tetramethyl phosphinan-4-one, and wherein the other substituents Rl and R2, or R4 and R5 each individually represent a tertiary butyl group. Within the subject application, by a "divalent organic bridging group" R3 is understood the group connecting the phosphorus atoms pi and P2 via the shortest connection in the ligand. The bridging group R^ preferably may have a structure as represented by formula (III),
-Ram-Rb-Rcn_ ( III ) wherein Ra and Rb independently represent the same or different optionally substituted methylene groups; R^ represents an organic group comprising the bivalent bridging group C^-C2 through which R^ is connected to Ra and Rc; m and n independently represent a natural number in the range of from 0 to 3, wherein the rotation about the bond between the carbon atoms of the bridging group
C- and C2 of the bridging group is restricted at a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C1, C2 and the atom directly bonded to C1 in the direction of P1, and the plane occupied by the three atom sequence C^-, C2 and the atom directly bonded to C2 in the direction of P2, is in the range of from 0 to 120°. The terms bond and rotation are as defined in Hendrickson, Cram and Hammond, Organic
Chemistry, 3rd Edition, 1970, pages 175 to 201. Rotation according to the subject invention means that the atoms attached to C1- and C2 respectively rotate about the axis that runs through the centre of the bond between C-- and
C . The rotation about a bond is called "free" when the rotational barrier is so low that different conformations are not perceptible as different chemical species on the time scale of the experiment. The inhibition of rotation of groups about a bond due to the presence of a sufficiently large rotational barrier to make the phenomenon observable on the time scale of the experiment is termed "hindered rotation" or "restricted rotation" (as defined in IUPAC Compendium of Chemical Terminology,
2nd Edition (1997), 68, 2209). A suitable experiment can for instance be an ^H-NMR-experiment as described in
Hendrickson, Cram and Hammond, Organic Chemistry, 3rd Edition, 1970, pages 265 to 281 and in F.A. Bovey, Nuclear Magnetic Resonance Spectroscopy, (New York,
Academic Press, 1969), p. 1-20, provided that there are hydrogen atoms present in the ligand that will exhibit a suitable shift influenced by the bond between C^ and C . Preferably, there is no free rotation about the bond between C1 and C2 at the temperature range at which the subject process is conducted. This temperature range may conveniently be in between 0 °C to 250 °C, but preferably the subject process is conducted in the range of from 10 °C to 200 °C, and yet more preferably in the range of from 15 CC to 150 °C, and again more preferably in the range of from 18 °C to 130 °C. The rotation about the bond is considered hindered, if no rotation is measurable in the liquid state or in solution, i.e. at a temperature range where the ligand is liquid if determined under neat' conditions, or in solution of a suitable solvent.
Accordingly, the rotation about the bond C1--C2 of the bidentate ligand is hindered or restricted in solution or liquid state of the ligand. Preferably, the rotation about the bond C^-C2 of the bidentate ligand is preferably hindered or restricted in the temperature range of the subject process. The bridging group B comprises a chain of 2 optionally substituted carbon atoms C^ and C . These carbon atoms C^ and C2 form the direct bridge between RiR2?1-Ra m- and -Rc n-P2R5R6, so that the phosphorus atoms pl and P2 and the optionally substituted methylene groups
Ra m and Rc n are connected via the bridging group ci-C2 to form the diphosphine ligands (b) . Although many different restricted conformations are possible for the subject ligands, a particular dihedral angle was found to be of high importance for the activity of the catalyst system. A dihedral angle is generally defined as the angle formed by two intersecting planes. The dihedral angle according to the subject process is the angle formed by the plane occupied by the three atom sequence composed of the three atoms C2, C1 and the atom directly bonded to C1 in direction of P1, and the plane occupied by the three atom sequence C^-, C2 and the atom directly bonded to C2 in direction of P2 is in the range of from 0 to 120°, of the four atom sequence (atom directly bonded to C^ in direction of pi) -C^-C2- (atom directly bonded to C2 in the direction of P2) . "In the direction of P^- or P2" herein has the meaning that the relevant atom is situated i that part of the ligand chain that connects C^ and pi, or C2 and P2, respectively. For instance, in the case that m and n are equal to 1, the dihedral angle is the angle between the plane occupied by the three atom sequence Ra-cl-C2 of the four atom sequence Ra-C1-C2-Rc and the other three atoms C1-C2-Rc of the four atom sequence Ra-C1-C -Rc. Each plane is understood to run through the central points of the respective atoms. In the case that m and n of formula (III) should equal 0, the four atom sequence would accordingly be P1-C1-C2-P2, and the two planes would be defined as pi-ci-C2 and C1^2-)?2 .
In the ligands according to the subject process, the dihedral angle as defined above is ranging from 0° to 120°. Since a higher catalytic activity of the catalyst system is thereby obtainable, the dihedral angle preferably is in the range of from 0° to 70, yet more preferably in the range of from 0° to 15°, and most preferably in the range of from 0° to 5°. Without wishing to be bound to any particular theory, it is believed that ligands allowing rotation about the bond cl-C2 are less able to form a conformationally stable bidentate complex with the palladium centre. The bond formed between C^ and C2 may be a saturated or an unsaturated bond as occurring in ethylenically unsaturated or aromatic compounds. In the case of a saturated bond connecting C^ and C2, R^ can be expressed by C1R'R"-C2R"'R"", and the bidentate diphosphine ligand according to the present invention is thus suitably characterised by formula IV
R1R P1-Ra m-C1R'R"-C2R"'R""-Rc rι-P2R4R5 (IV) .
In this embodiment, R' and R", and R'" and R"" represent hydrogen or the same or different optionally substituted organic group, provided that only one of R' and R", and only one of R' " and R"" is hydrogen. If C1 and C2 are connected by an ethylenically unsaturated double bond, C^ and C2 also cannot rotate freely. In this case, R can be expressed by C^R'= C2R", and the bidentate diphosphine ligand according to the present invention is thus suitably characterised by formula (V) :
R1R2P1-Ra m-C1R' =C2R"-RCn-p2R5R6 ( V) .
If the bond between C1 and C2 is an ethylenically unsaturated bond, the ligand chain connecting pi and P2 via C-*- and C2 may in principally exist in two isomeric forms, a trans-configuration, and a cis-configuration. According to the above definition, in the trans- configuration the dihedral angle is about 180°, whereas in the cis-configuration, the dihedral angle is about 0°. The substituents R' to R"" in formula IV or V can themselves be independent substituents, thus only connected to each other via the carbon atoms C^ and C2, or preferably have at least one further connection. The substituents may further comprise carbon atoms and/or heteroatoms. The restriction of the free rotation may conveniently be achieved by the bridging group C-^-C2 forming part of a molecular structure that impedes rotation about the bond
C^-C2 at ambient temperature, and more preferably at a temperature range from 0 to 250 °C, and preferably from 15 to 150 °C. This molecular structure may conveniently be for instance a) an ethylenically unsaturated double bond, wherein the rotation is impeded by the energetically advantageous overlap of π-bonds, and/or b) a cyclic hydrocarbyl structure, in which the rotation is restricted due to the steric interaction of substituents R' to R"", or due to steric strain induced by a cyclic structure formed by R' to R"" together, or by combination of the above factors, such as in aromatic or non-aromatic cyclic structures. Conformational stability and hence rigidity may also c) be achieved if the nature of the substituents R' and R", and/or R'" and R"" is such that even if not connected to each other they impede
rotation about the bond C^-C2, for instance by strong steric interactions. To this goal, yet more preferably, none of R' to R"" in formula IV or V represent hydrogen. Rb preferably is a cyclic hydrocarbyl structure that is optionally substituted by hetereoatoms, yet more preferably an aliphatic or aromatic hydrocarbyl structure. This structure may be part of an optionally further substituted saturated or unsaturated polycyclic structure, which also optionally may contain heteroatoms such as nitrogen, sulphur, silicon or oxygen atoms. Suitable structures Rb include for instance substituted cyclohexyl, cyclohexenyl, cyclohexadienyl, substituted cyclopentane, cyclopentenyl or cyclopentadienyl structures, all of which may optionally contain heteroatoms such as nitrogen, sulphur, silicon or oxygen atoms, with the proviso that the rotation about the bond C^-C2 is restricted, that the dihedral angle is in the range of from 0° to 120°, and that there is preferably no rotation about the bond formed by C1- and C2 induced by conformational changes, as for instance in highly restrained acetal structures such as 2, 2-dimethyl-l, 3-dioxolane. In one particularly preferred embodiment, R3 represents a divalent polycyclic hydrocarbyl ring structure. Such polycyclic groups are particularly preferred due to the high conformational stability and hence high restriction against free rotation about the bond between C^- and C2. Examples of such particularly preferred hydrocarbyl groups include norbornyl, norbornadienyl, isonobornyl, dicylcopentadienyl, octahydro-4,
7-methano-lH-indenemethanyl, α- and β-pinyl, and 1,
8-cineolyl, all of which may optionally be substituted, or contain heteroatoms as defined above. In case that the bidentate ligand has chiral centres, it may be in any R,R-, S,S- or R,S-meso form, or mixtures thereof. Both meso forms and racemic mixtures can be employed, provided that the dihedral angle is in the range of from 0 to 120°. In the diphosphine of formula II, R preferably represents an optionally substituted divalent aromatic group which is linked to the phosphorus atoms via the groups Ra and Rc. Such an aromatic cyclic structure is preferred due to its rigidity, and to a dihedral angle being generally in the range of 0 to 5 ° . The aromatic group can be a monocyclic group, such as for example a phenyl group or a polycyclic group, such as for example a naphthyl, anthryl or indyl group. Preferably, the aromatic group R contains only carbon atoms, but R3 can also represent an aromatic group wherein a carbon chain is interrupted by one or more hetero atoms, such as nitrogen, sulphur or oxygen atom in for example a pyridine, pyrrole, furan, thiophene, oxazole or thiazole group. Most preferably the aromatic group Rb represents a phenyl group or naphtylene group.
Optionally the aromatic group B is substituted. Suitable substituents include groups containing hetero-atoms such as halides, sulphur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide and groups of the general formula -0-H, -O-X, -CO-X, -CO- O-X, -S-H, -S-X, -CO-S-X, -NH2, -NHX, -N0 , -CN, -CO-NH2, -CO-NHX, -C0-NX2, -CI3 or -CF3, in which X independently represents alkyl groups having from 1 to 4 carbon atoms like methyl, ethyl, propyl, isopropyl and n-butyl. When
the aromatic group is substituted it is preferably substituted with one or more aryl, alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms. Suitable groups include methyl, ethyl, tri ethyl, iso- propyl, tetramethyl and iso-butyl, phenyl and cyclohexyl. Most preferably, however, the aromatic group R is non-substituted and only linked to the groups Ra and Rc which connect it with the phosphorus atoms . yet more preferably, Ra and Rc are alkylene groups, and thus connected at adjacent positions, for example the 1 and 2 positions, of the aromatic group. The symbols m and n in formula III, IV and V independently may represent a natural number in the range of from 0 to 3. If the m and n are 0, then the phosphorus atoms i and P2 are directly connected to bridge formed by the carbon atoms C^ and C2. If one of m or n equals 0, then either C1- or C2 will be directly connected to pi or
P2. Without wishing to be bound to any particular theory, it is believed that the effect resulting from the particular arrangement of the central bridge formed by C1- and C2 on the phosphorus atoms, and hence on the catalyst complex, will be diluted by the presence of a larger number of groups Ra and/or Rc. Also, it is believed that if both and n equal 0, the distance between the phosphorus atoms may be rather short, such that the ligand binds less strongly to the palladium centre atom of the catalyst complex. Accordingly, due to generally good catalyst activity found with such ligands, m preferably equals 0 or 1, whereas n preferably is in the range of from 1 to 3, more preferably from 1 to 2 and most preferably 1.
If m and/or n have a value above 1, then several optionally substituted groups Ra and Rc connect p and P2 to Rb. Ra and/or Rc. These different may then be the same or individually different groups. Hence, Ra and/or Rc preferably are lower alkylene groups (by lower alkylene groups is understood alkylene groups comprising from 1 to 4 carbon atoms) . These alkylene groups can be substituted, for example with alkyl groups or heteroatoms, or non-substituted, and may for instance represent methylene, ethylene, trimethylene, iso- propylene, tetramethylene, iso-butylene and tert- butylene, or may represent methyloxy, ethyloxy and similar groups. Most preferably, at least one of Ra and/or Rc is a methylene group. Particularly suitable aromatic groups for R^3 include aryl groups such as disubstituted phenyl or naphthyl groups, and substituted alkyl phenyl groups such as tolyl and xylyl groups, groups. Preferred due to the high stability of the obtained ligands and catalysts, are tolyl and xylyl groups, wherein the methylene substituent or methylene substituents at the aromatic ring serve as groups Ra and/or Rc. Most preferably, C1 and C2 are part of an aromatic ring, whereas at least one of Ra and/or Rc represent methylene groups attached to adjacent atoms C1 and C2 in the aromatic ring. Accordingly, an especially preferred ligand family according to the subject invention is that wherein C^ and C2 are part of a phenyl ring; m is 0 or 1; n is 1, and Ra and Rc are methylene groups. In yet another especially preferred ligand family due to easy synthetic accessibility, m and n equal 1. Accordingly, such ligands
based on the 1, 2-di (phosphinomethyl) benzene or l-phosphino-2- (phosphino methyl) -benzene groups are particularly suited for the subject process due to the high rigidity of the aromatic backbone, easy synthetic availability, and due to the very good results obtained with the derived catalyst system. Such a ligand is for instance 1- (1, 3, 5, 7-tetramethyl-l, 3, 5-trimethyl-6, 9, 10-trioxa-2-phosphatricyclo [3.3.1.1^3'71] decyl-2- (di- tert-butylphosphinomethyl) benzene . Very good results were also obtained with unsymmetrical bidentate diphosphine ligand of formula VI, R1R2 > pi - CH2-C(=X)-CH2 - P2 < R4R5 (VI) wherein X represents an oxygen atom, a sulphur atom, an amino group, or a optionally substituted alkylene group, pl and P2 represent phosphorus atoms; Rl, R2, R4 and R5 each individually, or R1 and R2 jointly, and/or R4 and R^ jointly represent organic groups that are covalently linked to the phosphorus; and wherein R1 to R4 are chosen in such way, that the phosphino group R^R > pi differs from the phosphino group P2 < R4RX In these ligands, Ra equals CH2, m is 1, Rb equals C=CH2, and Rc equals CH2.
In these ligands, the divalent organic bridging group R3 is represented by the tertiary alkylene carbon atom C(=X). X preferably is an optionally substituted alkylene group, more preferably a methylene group, so that R3 equals -C(=CH2)-- In these ligands, rotation about this carbon atom is also highly restricted due to the stiffness of the alkylene structure, and the dihedral angle formed by P1-CH2-C(=CH ) - and C (=CH2)-CH2"P2 is in the range of from 0° to 120°.
Preferably, these ligands were employed in a catalyst composition comprising the unsymmetrical bidentate diphosphine ligand and a source of palladium, platinum, or rhodium. The latter was found effective in particular for hydroformulation reaction, i.e. carbonylation reactions ion the presence of a source of hydride, such as molecular hydrogen, in particular in the presence of a source of an anion. The subject process permits to convert non-conjugated ethylenically and acetylenically unsaturated compounds to the corresponding products with very high turnover numbers due to the high catalyst activity. Suitable ethylenically or acetylenically unsaturated compounds are ethylenically or acetylenically unsaturated compounds having from 2 to 50 carbon atoms per molecule, or mixtures thereof. Suitable ethylenically and acetylenically unsaturated compounds may have one or more isolated unsaturated bonds per molecule. Preferred are compounds having from 2 to 20 carbon atoms, or mixtures thereof, yet more preferred are compounds having at most 18 carbon atoms, yet more at most 16 carbon atoms, again more preferred compounds have at most 10 carbon atoms. The ethylenically or acetylenically unsaturated compound may further comprise functional groups or heteroatoms, such as nitrogen, sulphur or oxide. Examples include carboxylic acids, esters or nitriles as functional groups. In a preferred embodiment, the ethylenically or acetylenically unsaturated compound is an olefin or a mixture of olefins. Such olefins can be converted by reaction with carbon monoxide and a co-reactant with a high regioselectivity towards the linear carbonylation product. Suitable ethylenically or acetylenically unsaturated compounds include acetylene, methyl
acetylene, propyl acetylene, ethylene, propylene, butylene, isobutylene, pentene, pentene nitriles, methyl 3-pentenoates, 2- and 3-pentenoic acid. Another preferred feedstock are mixtures of olefins, or mixtures of olefins and saturated compounds obtained for instance in a
Fischer-Tropsch synthesis step. In such a synthesis, usually a mixture of olefins and saturated hydrocarbons is obtained. The content of olefins in this mixture may vary, and may be increased by starting of with the synthesis product of an iron-catalyzed Fischer-Tropsch synthesis step. An even higher olefinic content of the mixture may be obtained by catalytic dehydrogenation or thermal cracking in the presence of steam. The subject process in particular suited for reacting such mixtures, as it selectively reacts with olefinic or acetylenically non-conjugated compounds in such a mixture without affecting the other saturated compounds, and hence allows an easy separation of the carbonylated products from the saturated hydrocarbons. According to the subject process, ethylenically or acetylenically unsaturated compounds may be converted into very different chemical compounds, such as aldehydes, esters, acids or acid anhydride, thioesters, amides, and alcohols or others. The specific nature of the product is depending on the nature of the co-reactant having a mobile hydrogen atom. The co-reactant according to the present invention may thus be any compound having a mobile hydrogen atom, and which is capable of reacting as a nucleophile with the diene under catalysis. The nature of the co-reactant largely determines the type of product formed. A suitable co-reactant is water, a carboxylic acid, alcohol, ammonia or an amine, a thiol, or a combination thereof. In other words, the catalyst systems may be used in
"hydroformylation reactions", "hydrocarboxylation reactions", "hydroesterification reactions" or "hydroamidation reactions". Inasmuch as the co-reactant is water, the product obtained will be a carboxylic acid. Anhydrides are obtained inasmuch as the co-reactant is a carboxylic acid. For an alcohol co-reactant, the product of the carbonylation is an ester. Similarly , the use of ammonia (NH3) or a primary or secondary amine RNH or R'R"NH will produce an amide, whereas the use of a thiol RSH will produce a thioester. In the above-defined co-reactants, R, R' and/or R" represent optionally heteroatom- substituted organic radicals, preferably alkyl, alkenyl or aryl radicals. When ammonia or amines are employed, a small portion of these co-reactants will react with acids present under formation of an amide and water. Hence, in the case of ammonia or amine-co-reactants, there is always water present. Preferred alcohol co-reactants are alkanols with 1 to 20, more preferably with 1 to 6 carbon atoms per molecule, and alkanediols with 2-20, more preferably 2 to 6 carbon atoms per molecule. The alkanols can be aliphatic, cycloaliphatic or aromatic. Suitable alkanols in the process of the invention include methanol, ethanol, ethanediol, n-propanol, 1,3- propanediol, iso-propanol, 1-butanol, 2-butanol (sec- butanol) , 2-methyl-1- propanol (isobutanol) , 2-methyl-2~ propanol (tert-butanol) , 1-pentanol, 2- pentanol, 3- pentanol, 2-methyl-l-butanol, 3-methyl-l-butanol (isoamyl alcohol), 2-methyl-2-butanol (tert-amyl alcohol), 1- hexanol, 2-hexanol, 4-methyl-2-pentanol, 3, 3-dimethyl-2- butanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1,2-ethylene glycol and 1, 3-propylene glycol, of which methanol is the most preferred due to the high turn over
achievable and due to the particular usefulness of the obtained products. Preferred amines have from 1 to 20, more preferably 1 to 6 carbon atoms per molecule, and diamines have from 2-20, more preferably 2 to 6 carbon atoms per molecule. The amines can be aliphatic, cycloaliphatic or aromatic. More preferred due to the high turnovers achieved are ammonia and primary amines. Thiol co-reactants can be aliphatic, cycloaliphatic or aromatic. Preferred thiol co-reactants are aliphatic thiols with 1 to 20, more preferably with 1 to 6 carbon atoms per molecule, and aliphatic dithiols with 2-20, more preferably 2 to 6 carbon atoms per molecule. The subject carbonylation reaction is also known as a hydrofor ylation reaction in the case that the co- reactant is a hydride source, such as molecular hydrogen. This can be achieved by supplying carbon monoxide and hydrogen to the reaction in equimolar or non-equimolar ratios, e.g. in a ratio within the range of 5:1 to 1:5, preferably 3:1 to 1:3. Preferably they are supplied in a ratio within the range of 2:1 to 1:2, and will result in alcohol mixtures. In particular when Fischer-Tropsch product streams are used as feedstocks, the obtained product mixtures can be suitably used for sanitary or other related applications. The carbonylation can be suitably carried out at moderate reaction conditions. Hence temperatures in the range of 50 to 200 °C are recommended, preferred temperatures being in the range of 70 to 160 °C. Reaction pressures in the range of 5 to 100 bar are preferred, lower or higher pressures may be selected, but are not considered particularly advantageous. Moreover, higher pressures require special equipment provisions.
In the process of the invention, the unsaturated starting material and the formed product as well as the co-reactant may act as reaction solvent. Hence, the use of a separate solvent might not be necessary. Conveniently, however, the carbonylation reaction may be carried out in the additional presence of a solvent, in particular in the start-up phase of the reaction. As such, saturated hydrocarbons, e.g. paraffins and isoalkanes are recommended and furthermore alcohols, the saturated hydrocarbons and alcohols preferably having from 1 to 10 carbon atoms per molecule, such as methanol, butanol, 2-ethylhexan-l-ol, nonan-1-ol, or in general terms the alcohols formed as carbonylation product; ethers such as 2, 5, 8-trioxanonane (diglyme), diethylether and anisole, and ketones such as methylethylketone. Solvents, comprising or substantially consisting of sulphones are also preferred. Sulphones are in particular preferred, for example dialkylsulphones such as di ethyl- sulphone and diethylsulphone and cyclic sulphones, such as sulfolane, 2-methylsulfolane and 2-methyl-4-ethyl- sulfolane. The ratio of moles of bidentate diphosphine, i.e. catalyst component (b) , per mole atom of palladium cations, i.e. catalyst component (a), ranges from 0.5 to 10, preferably from 0.8 to 8, and yet more preferably from 1 to 5. The ratio of moles of bidentate diphosphine, i.e. catalyst component (b) , per mole atom of palladium, i.e. catalyst component (a), is not critical. Preferably it ranges from 0.1 to 100, more preferably from 0.5 to 10. A more preferred catalyst the active species is based on an equimolar amount of bidentate diphosphine ligand per mole palladium. Thus, the molar amount of bidentate
diphosphine ligand per mole palladium is preferably in the range of 1 to 3, more preferably in the range of 1 to 2, and yet more preferably in the range of 1 to 1.5. In the presence of oxygen, slightly higher amounts may be beneficial. Preferably, the catalyst system or composition further preferably comprises a source of an anion. A suitable source of anion may be a strong, or a weak coordinating anion. Various anions may be used as counter-ion to the metal cation. Examples thereof include anions that are the conjugated base of acids having a pKa (measured at 18 °C in water) of less than 6, preferably less than 4. The anions derived from these acids do not or only weakly co-ordinate with the metal cation, by which is meant that little or no covalent interaction occurs between the anion and the cation. Catalysts based on these anions exhibit a good activity. Suitable anions include anions derived from Bronsted acids, such as from phosphoric acid and sulphuric acid, and in particular from sulphonic acids and (halogenated) carboxylic acids, such as trifluoroacetic acid, 2,6-di chlorobenzoic acid, and 2, 6-bis (trifluoromethyl) benzoic acid or trifluoroacetic acid, etc. Anions derived from sulphonic acids are particularly preferred, for example methanesulphonic acid, trifluoromethanesulphonic acid, tert-butanesulphonic acid, p-toluenesulphonic acid and 2,4, 6-trimethylbenzenesulphonic acid. Also complex anions are suitable, such as the anions generated by a combination of a Lewis acid such as BF3, B(CgF5)3, AICI3, SnF , Sn(CF3S03)2r SnCl2 or GeCl2, with a protic acid, preferably having a pKa of less than 5, such as a sulphonic acid, e.g. CF3SO3H or CH3SO3H or a
hydrohalogenic acid such as HF or HC1, or a combination of a Lewis acid with an alcohol. Examples of such complex anions are BF2~, SnCl3~, [SnCl2.CF3SO3] - and PFg-. Preferably, the source of anions is a carboxylic acid, which can serve both as promoter component, as well as solvent for the reaction. Again more preferably, the source of anions is an acid having a pKa below 3.6
(measured in aqueous solution at 18 °C) , and yet more preferably catalyst component (c) is an acid having a pKa below 3.0, and yet more preferably a pKa of above 2.0.
Examples of suitable acids include acetic acid, propionic acid, butyric acid, pentanoic acid, pentenoic acid and nonanoic acid. Very conveniently the acid corresponding to the desired product of the reaction can be used as the catalyst component (c) . Catalyst component (c) can also be an ion exchanging resin containing carboxylic acid groups. This advantageously simplifies the purification of the product mixture. In the case that the co-reactant is an amine or ammonia, and the source of an anion of the catalyst system is an acid, preferably the amount of ammonia or amine is less than stoichiometric based on the amine functionality. Inadvertently, when the co-reactant is ammonia, and to a lesser extent a primary amine, a small amount of the acid present will react to an amide under liberation of water. Hence, there is also always a small amount of acid formed from the unsaturated compound, carbon monoxide and the water, which in turn replaces acid converted to amide by the direct reaction as described above. The molar ratio of the source of anions, and palladium, platinum, or rhodium is not critical. However,
it suitably is between 2:1 and 107:1 and more preferably between 102:1 and 10°: 1, yet more preferably between
10 :1 and lO^.l, and most preferably between 102:1 and
104:1 due to the enhanced activity of the catalyst system. Accordingly, if a co-reactant should react with the acid serving as source of anions, then the amount of the acid to co-reactant should be chosen such that a suitable amount of free acid is present. Generally, a large surplus of acid over the co-reactant is preferred due to the enhanced reaction rates. The quantity in which the complete catalyst system is used is not critical and may vary within wide limits.
Usually amounts in the range of 10""° to 10~1, preferably in the range of 10-7 to 10-2 mole atom of palladium per mole of olefin are used, preferably in the range of 10~5 to 10-2 gram atom per mole. The process may optionally be carried out in the presence of a solvent, however preferably the acid is used as solvent and as promoter. The carbonylation reaction according to the present invention is carried out at moderate temperatures and pressures. Suitable reaction temperatures are in the range of 0-250 °C, more preferably in the range of 50-200 °C, yet more preferably in the range of from 80-150 °C. The reaction pressure is usually at least atmospheric. Suitable pressures are in the range of 0.1 to 15 MPa (1 to 150 bar), preferably in the range of 0.5 to 8.5 MPa (5 to 85 bar). Carbon monoxide partial pressures in the range of 0.1 to 8 MPa (1 to 80 bar) are preferred, the upper range of 4 to 8 MPa being more preferred. Higher pressures require special equipment provisions .
The carbonylation reaction is further conveniently carried out at a temperature in the range of 30 to 200 °C, preferred temperatures being in the range of 50 to 180 °C. In the process according to the present invention, the carbon monoxide can be used in its pure form or diluted with an inert gas such as nitrogen, carbon dioxide or noble gases such as argon, or co-reactant gases such as ammonia. The invention will be illustrated by the following non-limiting examples .
Example 1: Preparation of 9- (2-{ [di (tert-butyl) phosphino] methyl } -2-propenyl) -9-phosphabicyclo [3.3.1] nonane 9-phosphabicyclo [3.3.1] nonane
Figure 1: 9- (2- { [di (tert-butyl) hosphino] ethyl} -2- propenyl) - A mixture of di-tert-butylphosphine (5 g, 34.1 mmol) and 3-chloro-2-chloromethyl-l-propene (14,04 g, 69 mmol) was dissolved in degassed acetonitrile (70 ml) and heated to 60 °C for 16 hours. The solvent was removed in vacuo and the product was suspended in hexane (50 ml) . After filtration the product was washed with hexane (2 times 40 ml) . The white solid salt was neutralized in a mixture of toluene (50 ml) and water (30 ml) with HNEt2 (5 ml) under reflux conditions. The toluene layer was separated, washed with water (2 times 30 ml) and removed in vacuo, to yield 3.14 g (40%) of di (tert-butyl) [2- (chloromethyl) - 2-propenyl] phosphine.
The product could be characterized by showing a distinct resonance signals in 31p NMR at δ - + 21.7 ppm. 2.82 g (20 mmol) of the 9-phosphabicyclo [3.3.1] nonane was dissolved in THF (90 ml). To this solution, a 1.6 M solution of n-BuLi in hexane (12.5 ml, 20 mmol) at -50 °C was added. The mixture was allowed to warm to 0 °C for fifteen minutes and then cooled to -70 °C, after which and a solution of 4.7 g (20 mmol) di (tert-butyl) [2- (chloromethyl) -2-propenyl] -phosphine obtained as described above in 10 ml THF was added. The mixture was allowed to warm to ambient temperature, and was subsequently quenched with water (5 ml) . The solvents were removed in vacuo and toluene (60 ml) was added. The mixture was washed twice with water (40 ml and 20 ml) and the toluene was removed in vacuo giving 6.71 g of a red/orange oil. The product was crystallized twice from (boiling) methanol, giving a white solid (2.83 g, 42%). The product could be characterized by showing two distinct resonance signals in 31p NMR at + 22.1 ppm and -, 36.5 ppm.
Example 2: Preparation of 8- (2- { [di (tert- butyl) phosphino]methyl} -2-propenyl) -1,3,5, 7-tetramethyl- 2,4, 6-trioxa-8-phosphatricyclo [3.3.1.1. {3,7} ] decane
Figure 2: 8- (2-{ [di (tert-butyl) phosphino]methyl}-2- propenyl) -1, 3, 5,7-tetramethyl-2, 4, 6-trioxa-8- phosphatricyclo [3.3.1.1. {3,7}] decane
To a solution of HPCage*BH3 (1.34 g, 5.83 mmol; Pcage = 1, 3, 5, 7-tetramethyl-2, 4, 6-trioxa-8-phospha- tricycle[3.3.1.1. {3, 7}]decane) in THF (20 ml) was added a 1.6 M solution of n-BuLi in hexane (3.64 ml, 5.83 mmol) at -78 °C. The mixture was allowed to warm to 0 °C for fifteen minutes and cooled to -78 °C again, after which a solution of di (tert-butyl) [2- (chloromethyl) -2-propenyl] - phosphine as described under (1.37 g, 5.83 mmol) in THF (5 ml) was added. The reaction mixture was allowed to warm to RT. HNEt (10 ml) was added and the reaction mixture was refluxed for a few hours, until NMR- measurements showed that the deprotection was complete) . Subsequently, the solvents were removed in vacuo, and the solid product was recrystallized from methanol (50 ml) upon gradual cooling. The isolated yield was 1.5 g (62%), and the product could be characterized by showing two distinct resonance signals in 31 N R at + 20.3 ppm (P- tert. Bu) and - 34.3 ppm (P-Cage) .Example 3: Preparation of 8- (2-{ [di (tert- ;i butyl) phosphino]methyl}phenyl) -1, 3, 5, 7-tetramethyl-2, , 6- trioxa-8-phosphatricyclo [3.3.1.1(3,7}] decane
Figure 3: 8- (2-{ [di (tert-butyl) phosphino] methyl}phenyl) 1,3,5, 7-tetramethyl-2, 4, 6-trioxa-8-phosphatricyclo- [3.3.1.1{3,7}]decane 8.25 g (33 mmol) 2-bromobenzylbromide and 5 g (34.2 mmol) di-tert-butyl phosphine in 40 ml degassed acetonitrile were measured into a 100 ml glass reactor
under an inert atmosphere, and then stirred for a period of 12 hours at ambient temperature. The acetonitrile was then removed in vacuo and 30 ml degassed toluene, 30 ml degassed water and 7.5 ml triethylamine were added. To this mixture 10 ml ethanol was added to improve phase separation. Upon phase separation, the upper layer containing the toluene was separated and evaporated to dryness. The remainder was 9 g (28.6 mmol, 87%) of (2-bromobenzyl) (di- ert-butyl) phosphine as a light yellow oil exhibiting a resonance peak in 31p N R at +34.16 ppm. 2.5 g (7.9 mmol) of the thus obtained 2-bromobenzyl (di-tert-butyl) phosphine, 2.24 g DABCO (20 mmol), 1.94 g 1,3, 5-trimethyl-4, 6, 9-trioxa-2-phosphatricyclo- [3.3.1.1{3,7}]decane (9 mmol) and 0.23 g Pd(PPh3)4 (0.2 mmol) in 10 ml toluene were added into a 250 ml glass vessel under inert atmosphere, and the content of the vessel was heated to 140 °C under stirring for 12 hours. The mixture was than allowed to cool to 100 °C, and was then filtered. The filtrate was cooled to room temperature, then 30 ml of methanol added were added and the mixture cooled for a period for 12 hours to -35 °C, 8- (2-{ [di ( ert-butyl) -phosphino] -methyl}phenyl) -1,3,5,7- tetramethyl-2, , 6-trioxa-8-phosphatricyclo [3.3.1.1{3,7}]- decane was isolated as yellow crystals (2.2 g, 4.9 mmol, 62%) , and could be characterized by showing two distinct resonance signals in 31p NMR at +38.08 and -38.96 ppm. Examples 4 to 6 and Comparative Examples A, B and C: Conversion of 1-octene with methanol A 250 ml magnetically stirred autoclave, made of HASTELLOY C (HASTELLOY C is a trademark) , was successively charged with 40 ml of methanol, 20 ml 1- octene, and 0.5 mmol of methanesulfonic acid, and a
catalyst solution comprising 0.1 mmol palladium acetate and 0.2 mmol of the respective ligand in 10 ml of methanol. The autoclave was closed, evacuated, and pressurized with 3 MPa carbon monoxide. The reactor was then heated to 70 °C, and maintained at this temperature for 10 hours. Finally the autoclave was cooled, depressurized, and the reaction mixture was analysed with GLC. The turn over frequency is defined as amount of converted products, and given in mol olefin per mol Pd per hour for the batch operation as presented in Table I. Examples 7 and 8: Conversion of ethylene with methanol A 250 ml magnetically stirred autoclave, made of HASTELLOY C (HASTELLOY C is a trademark) , was successively charged with 45 ml of methanol, and 0.5 mmol of methanesulfonic acid. The autoclave was closed, evacuated, and pressurized with 3 MPa carbon monoxide and 20 MPa ethylene. The reactor was then heated to 85 °C, and a catalyst solution comprising 0.05 mmol palladium acetate and 0.1 mmol of the respective ligand in 5 ml of methanol was injected into the autoclave, thereby raising the carbon monoxide pressure by an additional 5 bar. The autoclave was maintained at 85 °C for 10 hours. Finally the autoclave was cooled, depressurized, and the reaction mixture was analysed with GLC. The turn over frequency is defined as amount of converted products, and given in mol olefin per mol Pd per hour for the batch operation as presented in, Table I. In Example 4 according to the invention, the ligand was 9- (2-{ [di (tert-butyl) phosphino] methyl} -2-propenyl) -9- phosphabicyclo [3.3.1] nonane prepared in Example 1. In
Examples 5 and 7 according to the invention, the ligand was 8-(2-{ [di (tert-butyl) phosphino]methyl} -2-propenyl) - 1,3,5, 7-tetramethyl-2, 4, 6-trioxa-8-
phosphatricyclo[3.3.1.1.3,7] decane prepared in Example 2. In Examples 6 and 8 according to the invention, the ligand was 8- (2-{ [di ( tert-butyl) phosphino]methyl}phenyl) - 1,3,5, 7-tetramethyl-2,4, 6-trioxa-8-phospha- tricyclo [3.3.1.1{3, 7 } ] decane prepared in Example 3. In Comparative Example A, the ligand was a symmetrical ligand with two 9-phosphabicyclo [3.3.1] nonane rings attached to an isobutene structure (9- [2- (9- phosphabicyclo [3.3.1] non-9-ylmethyl) -2-propenyl] -9- phosphabicyclo [3.3. l]nonane) . In Comparative Example B, the ligand was the symmetrical bis-di-tert-butyl phosphino-analogue (di ( ert-butyl) (2-{ [di ( tert- butyl) phosphino]methyl} -2-propenyl) phosphine) . In Comparative Example C, the ligand was the symmetrical bis-trioxa-adamantyl-ligand (1, 3, 5, 7-tetramethyl-8-{2- [1,3,5, 7-tetramethyl-2, , 6-trioxa-8- phosphatricyclo [3.3.1.1{3,7}] dec-8-yl) methyl] -2- propenyl} -2, 4, 6-trioxa-8-phospha- tricyclo [3.3.1.1{ 3, 7 } ] decane) . In Comparative Example D, the ligand was the symmetrical bis-trioxadamantyl-ligand ( [1, 3, 5, 7-tetramethyl-8-{2- [1, 3, 5, 7-tetramethyl-2, 4, 6- trioxa-8-phosphatricyclo[3.3.1.1. {3,7}]dec-8- yl) methyl] benzyl } -2 , , 6-trioxa-8-phosphatricyclo- [3.3.1.1{3, 7} ]decane) . In Comparative Example E, the ligand was the symmetrical 1, 2-bis (di-tert- butylphosphinomethyl) benzene ( [1, 2-phenylenebis- (methylene) ]bis (di-tert-butylphosphine) ) . The results are depicted in Table 1.
Table I
From the above data, it is clear that the unsymretrical ligands clearly outperform the symmetrical ligands in catalyst activity and selectivity for the desired linear products. Moreover, the use of two different kinds of substituents R^, R2, R4 and R^, wherein R1 and R2 have a different electron-donating ability on pi as compared to R4 and R5 on P2, and wherein all substituents R1, R2, R4 and R^ are bonded to the phosphorus atoms via tertiary carbon atoms results in yet unprecedented catalyst activity and selectivity for the linear carbonylation products.
Claims
1. Process for the carbonylation of unsaturated compounds by contacting the unsaturated compound with carbon monoxide in the presence of a catalyst system comprising: (a) a source of palladium and/or platinum; and
(d) an unsymmetrical bidentate diphosphine ligand of formula I, R1R2 > pi _ R3 _ P2 < R4R5 (j wherein pi and P2 represent phosphorus atoms; R-3 represents a divalent organic bridging group; and R^, R2,
R4 and R5 each individually, or R1 and R2 jointly, and/or
R4 and R^ jointly represent organic groups that are covalently linked to the phosphorus; and wherein R1-, R2,
R4 and R^ are chosen in such way, that the phosphino group R!R2 > P1 differs from the phosphino group P2 < R4R5_
2. A process according to claim 1, wherein R! and R2 have higher electron donor ability on ^- than R4 and R^ on P2.
3. A process according to claim 1 or claim 2, wherein R! and R2 independently represent the same or different optionally substituted organic group and which groups are solely connected to each other via the phosphorus atom pl; and wherein R4 and R^ together represent an organic bivalent group linked to the phosphorus atom P2.
4. A process according to any one of claims 1 to 3, wherein R1, R2, R4 and R5 each represent an organic radical which is covalently connected to the respective phosphorus atom via a tertiary carbon atom.
5. A process according to any one of claims 1 to , wherein R1- and R2 together, or R4 and R^ together represent a 2-phosρha-adamantane structure or a phosphinan-4-one structure.
6. A process according to any one of claims 1 to 5, wherein wherein R3 represents a group -Ra m-Rb-Rc n- (III), wherein Ra and )?P independently represent the same or different optionally substituted methylene groups;
Rb represents an organic group comprising a bivalent bridging group C-^-C2 through which B is connected to Ra and Rc; m and n independently represent a natural number in the range of from 0 to 4, and wherein the rotation about the bond between the carbon atoms G^ and C2 of the bridging group is restricted at a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C--, C2 and the atom directly linked to C1 in the direction of pi, and the plane occupied by the three atom sequence C1, C2 and the atom directly linked to C^ in the direction of P2, is in the range of from 0 to 120°.
7. A process according to claim 7, wherein Rb represents an aryl group, and wherein m is 0 or 1, n is 1, and the phosphorus atoms PI and P2 are connected to R through the respective methylene groups Ra or Rc or directly in adjacent positions on the aryl group.
8. A process according to claim 6 or 7, wherein R! and
R2 represent tertiary butyl groups, and R4 and R^ together represent a 2-phospha-adamantane structure or a phosphinan-4-one structure.
9. A process according to anyone of claims 1 to 8, wherein ethylene is converted to methyl propionate in presence of methanol.
10. A process according to anyone of claims 1 to 8, wherein pentenoic acid is converted to adipic acid.
11. A catalyst composition comprising:
(a) a source of palladium, and/or platinum; and (b) an unsymmetrical bidentate diphosphine ligand of formula I, R1R2 > pi _ R3 _ P2 < R4R5 ( ) wherein pi and P2 represent phosphorus atoms; R^ represents a divalent organic bridging group; and Rl, R2, R4 and R5 each individually, or R1 and R2 jointly, and/or R4 and R^ jointly represent organic groups that are covalently linked to the phosphorus; and wherein Rl, R2, R4 and R^ are chosen in such way, that the phosphino group RIR2 > P-^ differs from the phosphino group P2 < R R5.
12. A catalyst composition according to claim 11, wherein
R1 and R2 represent tertiary butyl groups, and R4 and R^ together represent a 2-phospha-adamantane structure or a phosphinan-4-one structure.
13. A catalyst composition according to claims 11 or 12, wherein R3 represents a group -Ra m-Rb-Rc n- ( HI ) , wherein Ra and P independently represent the same or different optionally substituted methylene groups; Rb represents an organic group comprising a bivalent bridging group C^-C2 through which Rb is connected to Ra and Rc; m and n independently represent a natural number in the range of from 0 to 4, and wherein the rotation about the bond between the carbon atoms C1- and C2 of the bridging group is restricted at a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C^, C2 and the atom directly linked to C^ in the direction of pi, and the plane occupied by the three atom sequence c , C2 and the atom directly linked to C2 in the direction of P2, is in the range of from 0 to 120°.
14. A catalyst composition according to claim 13, wherein
Rb represents an aryl group, and wherein m is 0 or 1,- n is 1, and the phosphorus atoms Pi and P2 are connected to R through the respective methylene groups Ra or Rc or directly in adjacent positions on the aryl group.
15. A catalyst composition according to any one of claims 11 to 14, further comprising a source of an anion.
16. An unsymmetrical bidentate diphosphine ligand of formula VI, R1R2 > pi - CH2-C(=X)-CH2 - P2 < R4R5 (VI) wherein X represents an oxygen atom, a sulphur atom, an amino group, or a optionally substituted alkylene group; wherein pi and P2 represent phosphorus atoms; Rl, R2, R4 and R^ each individually, or R! and R2 jointly, and/or R4 and R5 jointly represent organic groups that are covalently linked to the phosphorus; and wherein Rl to R4 are chosen in such way, that the phosphino group
R!R2 > P1 differs from the phosphino group P2 < R R5.
17. An unsymmetrical bidentate diphosphine ligand according to claim 16, wherein X represents a methylene group.
18. A catalyst composition comprising an unsymmetrical bidentate diphosphine ligand according to claim 16 or claim 17, and a source of palladium, platinum, or rhodium.
19. A catalyst composition according to claim 18, further comprising a source of an anion.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04251065 | 2004-02-26 | ||
PCT/EP2004/050794 WO2004103948A1 (en) | 2003-05-22 | 2004-05-13 | Process for the carbonylation of a conjugated diene |
EP04257283 | 2004-11-24 | ||
PCT/EP2005/050803 WO2005082830A1 (en) | 2004-02-26 | 2005-02-25 | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1735263A1 true EP1735263A1 (en) | 2006-12-27 |
Family
ID=37432304
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05716797A Withdrawn EP1735263A1 (en) | 2004-02-26 | 2005-02-25 | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1735263A1 (en) |
JP (1) | JP2007524700A (en) |
KR (1) | KR20060129489A (en) |
BR (1) | BRPI0507918A (en) |
CA (1) | CA2557362A1 (en) |
TW (1) | TW200600495A (en) |
WO (1) | WO2005082830A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1651587A1 (en) | 2003-07-03 | 2006-05-03 | Lucite International UK Limited | Process for the hydroformylation of ethylenically unsaturated compounds |
GB0403592D0 (en) | 2004-02-18 | 2004-03-24 | Lucite Int Uk Ltd | A catalyst system |
GB0411951D0 (en) | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
AU2006314268C1 (en) | 2005-11-17 | 2014-01-09 | Lucite International Uk Limited | Carbonylation of ethylenically unsaturated compounds |
GB0607494D0 (en) | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
JP2010511600A (en) | 2006-12-02 | 2010-04-15 | ルーサイト インターナショナル ユーケー リミテッド | A novel carbonylated ligand and its use in the carbonylation of ethylenically unsaturated compounds. |
GB0812297D0 (en) * | 2008-07-04 | 2008-08-13 | Lucite Int Uk Ltd | Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds |
FR2950349B1 (en) * | 2009-09-18 | 2011-08-26 | Rhodia Operations | ORGANOPHOSPHORIC COMPOUNDS, CATALYTIC SYSTEMS COMPRISING THESE COMPOUNDS, AND HYDROCYANATION METHOD USING THESE CATALYTIC SYSTEMS |
US20120309613A1 (en) | 2009-12-15 | 2012-12-06 | Lucite International Uk Limited | Carbonylation process |
GB0921875D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
GB201000078D0 (en) | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
GB201122054D0 (en) | 2011-12-21 | 2012-02-01 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
EP3976570A1 (en) * | 2019-05-27 | 2022-04-06 | DSM IP Assets B.V. | Selective hydrogenation of alkynes to alkenes in the presence of a phosphorus compound and an organic sulphur compound |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR880007418A (en) * | 1986-12-10 | 1988-08-27 | 오노 알버어스 | Selective Carbonylation Process of Conjugated Diene and Catalyst System without Organic Nitrogen-Containing Hot Air |
US5495041A (en) * | 1995-02-22 | 1996-02-27 | Dsm N.W. | Process for the preparation of a pentenoate ester |
US6137012A (en) * | 1998-10-13 | 2000-10-24 | E. I. Du Pont De Nemours And Company | Phosphole and diphosphole ligands for catalysis |
US6706912B2 (en) * | 2000-03-14 | 2004-03-16 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds |
DE10106348A1 (en) * | 2001-02-09 | 2002-08-14 | Basf Ag | Compound suitable as a catalyst or for producing a catalyst system |
MXPA02001147A (en) * | 2001-03-19 | 2004-04-21 | Warner Lambert Co | Synthesis of non-c2-symmetric bisphosphine ligands as catalysts for asymmetric hydrogenation. |
DE10148712A1 (en) * | 2001-10-02 | 2003-04-17 | Basf Ag | New 2-phosphatricyclodecane diphosphine derivatives useful as components of palladium catalysts for carbonylating conjugated dienes |
-
2005
- 2005-02-25 WO PCT/EP2005/050803 patent/WO2005082830A1/en not_active Application Discontinuation
- 2005-02-25 BR BRPI0507918-7A patent/BRPI0507918A/en not_active Application Discontinuation
- 2005-02-25 KR KR1020067019391A patent/KR20060129489A/en not_active Application Discontinuation
- 2005-02-25 EP EP05716797A patent/EP1735263A1/en not_active Withdrawn
- 2005-02-25 TW TW094105891A patent/TW200600495A/en unknown
- 2005-02-25 CA CA002557362A patent/CA2557362A1/en not_active Abandoned
- 2005-02-25 JP JP2007500222A patent/JP2007524700A/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2005082830A1 * |
Also Published As
Publication number | Publication date |
---|---|
BRPI0507918A (en) | 2007-07-10 |
TW200600495A (en) | 2006-01-01 |
CA2557362A1 (en) | 2005-09-09 |
JP2007524700A (en) | 2007-08-30 |
KR20060129489A (en) | 2006-12-15 |
WO2005082830A1 (en) | 2005-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2005082830A1 (en) | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds | |
JP5771707B2 (en) | Method for the carbonylation of ethylenically unsaturated compounds and their catalysts | |
KR100744207B1 (en) | Bidentate ligands useful in catalyst system | |
US6156934A (en) | Diphosphines | |
US20060235241A1 (en) | Process for the carbonylation of a conuugated diene | |
EP2521616B1 (en) | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporating such ligands | |
AU2009265367B2 (en) | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporating such ligands | |
AU2003259322B2 (en) | A catalyst system | |
US7265242B2 (en) | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds | |
CN115819234A (en) | Method for olefin carbonylation reaction | |
JP2005504850A (en) | Diphosphine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20060725 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20070803 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20071214 |