EP1438133A1 - Phosphinite - Google Patents
PhosphiniteInfo
- Publication number
- EP1438133A1 EP1438133A1 EP02801309A EP02801309A EP1438133A1 EP 1438133 A1 EP1438133 A1 EP 1438133A1 EP 02801309 A EP02801309 A EP 02801309A EP 02801309 A EP02801309 A EP 02801309A EP 1438133 A1 EP1438133 A1 EP 1438133A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- transition metal
- catalyst
- pentenenitrile
- methyl
- phosphinite
- 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- Withdrawn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
- 125000005538 phosphinite group Chemical group 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 48
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims description 39
- 229910052723 transition metal Inorganic materials 0.000 claims description 36
- 150000003624 transition metals Chemical class 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 21
- 238000006317 isomerization reaction Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 10
- 150000002825 nitriles Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 238000005669 hydrocyanation reaction Methods 0.000 description 21
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 125000004437 phosphorous atom Chemical group 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 9
- -1 n-Bu- tyl Chemical group 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- IQNYBCIGGNQJDL-UHFFFAOYSA-N (4-methylphenyl) dihydrogen phosphite Chemical compound CC1=CC=C(OP(O)O)C=C1 IQNYBCIGGNQJDL-UHFFFAOYSA-N 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- ISBHMJZRKAFTGE-ONEGZZNKSA-N (e)-pent-2-enenitrile Chemical compound CC\C=C\C#N ISBHMJZRKAFTGE-ONEGZZNKSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IHXNSHZBFXGOJM-HWKANZROSA-N (e)-2-methylbut-2-enenitrile Chemical compound C\C=C(/C)C#N IHXNSHZBFXGOJM-HWKANZROSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- NLEUXPOVZGDKJI-UHFFFAOYSA-N nickel(2+);dicyanide Chemical compound [Ni+2].N#[C-].N#[C-] NLEUXPOVZGDKJI-UHFFFAOYSA-N 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- UIUWNILCHFBLEQ-UHFFFAOYSA-N pent-3-enoic acid Chemical compound CC=CCC(O)=O UIUWNILCHFBLEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DNZZPKYSGRTNGK-PQZOIKATSA-N (1z,4z)-cycloocta-1,4-diene Chemical compound C1C\C=C/C\C=C/C1 DNZZPKYSGRTNGK-PQZOIKATSA-N 0.000 description 1
- IHXNSHZBFXGOJM-HYXAFXHYSA-N (z)-2-methylbut-2-enenitrile Chemical compound C\C=C(\C)C#N IHXNSHZBFXGOJM-HYXAFXHYSA-N 0.000 description 1
- UVKXJAUUKPDDNW-IHWYPQMZSA-N (z)-pent-3-enenitrile Chemical compound C\C=C/CC#N UVKXJAUUKPDDNW-IHWYPQMZSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XMDBKXFFPNRIQD-UHFFFAOYSA-N dichloro-(4-fluorophenyl)phosphane Chemical compound FC1=CC=C(P(Cl)Cl)C=C1 XMDBKXFFPNRIQD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- PXRDVIVDFIVDHI-UHFFFAOYSA-N diphenylphosphane;hydrochloride Chemical class [Cl-].C=1C=CC=CC=1[PH2+]C1=CC=CC=C1 PXRDVIVDFIVDHI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000000543 intermediate Substances 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
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- BKHZQJRTFNFCTG-UHFFFAOYSA-N tris(2-methylphenyl) phosphite Chemical compound CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C BKHZQJRTFNFCTG-UHFFFAOYSA-N 0.000 description 1
- AZLGDNBTDKZORI-UHFFFAOYSA-N tris(3-methylphenyl) phosphite Chemical compound CC1=CC=CC(OP(OC=2C=C(C)C=CC=2)OC=2C=C(C)C=CC=2)=C1 AZLGDNBTDKZORI-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Definitions
- the present invention relates to new phosphinites, in particular chelate phosphonites, processes for their preparation, their use as ligands in transition metal complexes, new transition metal complexes, processes for their preparation, their use as catalysts and processes in the presence of such transition metal complexes as catalysts.
- R1, R2, R4 independently of one another are hydrogen, an alkyl or alkylene group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, with the proviso that at least one of the groups R1, R2, R4 is not equal to H,
- n 0, 1 or 2
- transition metal complexes as well as processes for their preparation, their use as ligands in transition metal complexes, new transition metal complexes, processes for their preparation, their use as catalysts and processes in the presence of such transition metal complexes as catalysts.
- the radicals R1, R2, R4 are independently hydrogen, an alkyl or alkylene group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, with the proviso that at least one of the groups R1, R2, R4 is not equal to H.
- R1 is hydrogen
- R2 can be hydrogen and R4 can be an alkyl or alkylene group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms or R2 can be one
- R2 and R4 can be hydrogen or R2 independently of Rl can be an alkyl or alkylene group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms and R4 are hydrogen or R2 is hydrogen and R4, independently of Rl, is an alkyl or alkylene group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms, or R2 and R4 are, independently of one another and independently of Rl, an alkyl or Alkylene group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
- the alkyl or alkylene group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, in particular 1 to 4 carbon atoms, advantageously selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-Bu- tyl, s-butyl, i-butyl and t-butyl, in particular from the group consisting of methyl, ethyl, n-propyl, i-propyl and t-butyl, into consideration.
- the alkoxy group having 1 to 8 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, advantageously selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy and t- Butoxy, especially methoxy.
- R3 represents H or a methyl group.
- the phenyl groups connected to a phosphorus atom can be unsubstituted or can carry 1 or 2 substituents X independently of one another per phenyl group, so that the values 0, 1 or 2 result for n.
- the two phenyl groups connected to a phosphorus atom can be substituted in the same way or differently, and in the case of a different substitution the differences relate both to the number of the substituents and to the type of the substituents.
- formulas 1, 2 and 3 comprise both the same and a different substitution of the phenyl groups connected to a phosphorus atom.
- X is F, Cl or CF 3 , preferably F or CF 3 .
- the two radicals XI and X2 can independently represent F, Cl or CF 3 , that is to say F and F, F and Cl, F and CF 3 , Cl and Cl, Cl and CF 3 , CF and CF 3 , preferably F and F, CF 3 and CF 3 .
- n 1 and X equal to F
- a substitution in the m position to the phosphorus atom connected to the phenyl ring in a phenyl ring connected to a phosphorus atom can be considered.
- a substitution in the p-position to the phosphorus atom connected to the phenyl ring in a phenyl ring connected to a phosphorus atom can be considered.
- n 2 and XI and X2 equal to F
- a substitution in the two m positions to the phosphorus atom connected to the phenyl ring in a phenyl ring connected to a phosphorus atom can be considered.
- n 2 and X equal to CF 3
- a substitution in the two m-positions to the phosphorus atom connected to the phenyl ring is considered phosphorus atom in a phenyl ring connected to a phosphorus atom.
- Particularly preferred phosphinites are those of the formulas Ia-Ij below with the meanings of the groups R1, R2, R3 and R4 indicated in Table 1.
- radicals R1, R2, R3 and R4 have the following meanings:
- phosphinites are those according to ⁇
- R 1 and R 2 have the following meanings:
- Phosphinite I can be prepared in accordance with the production process described in US Pat. Nos. 5,523,453 and 5,693,843 for the phosphinite ligands described there, for example by reacting an optionally substituted (Xn-phenyl) (Xn-phenyl) phosphine chloride with one of the groups R1, R2 , R3 and R4 carrying diol.
- the presentation is efficient and economical from easily accessible starting materials.
- the diphenylphosphine chlorides used as the starting compound and their preparation are known per se, for example from: H. Schindlbauer, Monthly Bulletin Chemistry, Volume 96, 1965, pages 1936-1942.
- the process described there for the preparation of 4-fluorophenyldichlorophosphine can be used analogously to the preparation of the (Xn-phenyl) (Xn-phenyl) phosphine chlorides.
- the optimal parameters for the production of the respective phenyl) (Xn-phenyl) phosphine chlorides can easily be determined by a few simple preliminary tests.
- the phosphinites I can be used as ligands in transition metal complexes.
- transition metals here are advantageously the metals of the 1st to 2nd and 6th to 8th subgroups of the periodic table, preferably the 8th subgroup of the periodic table, particularly preferably iron, cobalt and nickel, in particular nickel.
- nickel it can have different values, such as 0, +1, +2, +3.
- Nickel (0) and nickel (+2), in particular nickel (0), are preferred.
- a chemical compound containing a transition metal or preferably a transition metal with a phosphinite I can be used, wherein a single phosphinite I or a mixture of several phosphinites I can be used as phosphinite I.
- the transition metal can be obtained before the reaction from suitable chemical compounds, for example by reduction with base metals such as zinc, from salts such as chlorides.
- salts such as chlorides, bromides, acetylacetonates, sulfates, nitrates, for example nickel (2) chloride, or Ni (0) complex compounds, such as bis, are advantageously used for this purpose (1, 5-cyclooctadiene) Ni (0).
- the valence of the transition metal in the complex can be with suitable oxidizing or reducing agents, for example base metals, such as zinc, or hydrogen in chemically bound form, such as sodium borohydride, or in molecular form Shape, or be changed electrochemically.
- suitable oxidizing or reducing agents for example base metals, such as zinc, or hydrogen in chemically bound form, such as sodium borohydride, or in molecular form Shape, or be changed electrochemically.
- reaction of a complex compound of Ni (0) with organic monophosphine, monophosphinite, monophosphonite or monophosphite ligands with a phosphinite I is suitable in accordance with the process described in German application 10136488.1.
- the molar ratio of transition metal to phosphinite I can be in the range between 1 and 6, preferably 2 to 5, in particular 2, 3 or 4.
- the transition metal complexes can be free of ligands other than the phosphinites I.
- the transition metal complexes can contain further ligands, for example nitriles, such as acetonitrile, adiponitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenonitrile, olefins, such as butadiene, or phosphorus compounds, such as organic monophosphines , Monophosphinites, monophosphonites or monophosphites.
- nitriles such as acetonitrile, adiponitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenonitrile, olefins, such as butadiene, or phosphorus compounds, such as organic monophosphines , Monophosphinites, monophosphonites or monophosphites.
- Such transition metal complexes can in principle be prepared in such a manner as described in the literature, for example in DE-OS-2 237 703, US-A-3, 850, 973, US-A-3, 766, 237 or US-A-3, 903, 120, for the preparation of transition metal complexes which contain tri-o-tolyl-phosphite, tri-m-tolyl-phosphite or tri-p-tolyl-phosphite, by using these phosphites partially or completely replaced the phosphinites I according to the invention.
- transition metal complexes according to the invention can be used as a catalyst, in particular as a homogeneous catalyst.
- transition metal complexes according to the invention as a catalyst in the addition of hydrocyanic acid to olefinic double bonds, in particular those which are conjugated to a further olefinic double bond, for example butadiene, to obtain a mixture comprising 2-methyl-3- butenenitrile and 3-pentenenitrile.
- Equally advantageous is the use as a catalyst in the addition of hydrocyanic acid to olefinic double bonds which are not associated with a further olefinic double bond, for example of 3-pentonitrile or 4-pentenenitrile or mixtures thereof, preferably 3-pentenenitrile, with retention of adiponitrile, or of 3-pentenoate or 4-pentenoate or mixtures thereof, preferably 3-pentenoate, to give 5-cyanovaleric acid ester.
- transition metal complexes according to the invention as a catalyst in the isomerization of organic nitriles, in particular those in which the nitrile group is not conjugated to an olefinic double bond, for example 2-methyl-3-butenenitrile to give 3-pentenenitrile , proven.
- advantageous ⁇ way is the use as a catalyst in the isomerization of organic nitriles in which the nitrile group is conjugated to an olefinic double bond.
- Processes for the addition of hydrocyanic acid to an olefinic double bond or for the isomerization of organic nitriles can in principle be carried out in such a manner as is described, for example, in WO 99/13983 or WO 99/64155, in that the phosphonites described there by the phosphinites I according to the invention partially or completely replaced.
- 1,3-butadiene-containing hydrocarbon mixtures are available on an industrial scale.
- a hydrocarbon mixture with a high total olefin content is referred to as a C-cut, with about 40% being 1,3-butadiene and the rest being monoolefins and polyunsaturated hydrocarbons and alkanes.
- These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl acetylene.
- Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
- Suitable heterogeneous catalyst systems generally comprise a transition metal compound on an inert support.
- Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides etc. and mixtures thereof. A1 2 0 3 , Si0 and mixtures thereof are preferably used as carriers.
- the heterogeneous catalysts used are those described in US Pat. Nos. 4,587,369; US-A-4, 704, 492 and US-A-4, 493, 906, which are incorporated herein by reference in their entirety.
- Suitable copper-based catalyst systems are marketed by Dow Chemical as KLP catalysts.
- a pretreated, partially hydrogenated C-cut can be continuous, semi-continuous or discontinuous.
- the hydrogen cyanide is added continuously.
- Suitable reactors for continuous implementation are that
- the hydrogen cyanide is added to 1,3-butadiene or a 1,3-butadiene-containing hydrocarbon mixture in a semi-continuous manner.
- the semi-continuous process includes: a) filling a reactor with the hydrocarbon mixture, if appropriate a part of the hydrogen cyanide and an optionally in situ generated hydrocyanation catalyst according to the invention and optionally a solvent,
- Suitable pressure-resistant reactors are known to the person skilled in the art and are described, for. B. in Ulimann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 769 ff.
- an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining. The following should preferably be observed for the above steps:
- the pressure-resistant reactor is filled with the partially hydrogenated C-cut or butadiene, hydrogen cyanide, a hydrocyanation catalyst and, if appropriate, a solvent.
- Suitable solvents are the aromatic hydrocarbons, such as toluene and xylene, or tetrahydrofuran mentioned above in the preparation of the catalysts according to the invention.
- the reaction of the mixture is generally carried out at elevated temperature and pressure.
- the reaction temperature is generally in a range from about 0 to 200 ° C., preferably about 50 to 150 ° C.
- the pressure is generally in a range from about 1 to 200 bar, preferably about 1 to 100 bar, in particular 1 to 50 bar, particularly preferably 1 to 20 bar.
- Hydrogen cyanide is fed in during the reaction in accordance with its consumption, the pressure in the autoclave remaining essentially constant.
- the reaction time is about 30 minutes to 5 hours.
- the reaction time can be followed by a post-reaction time of 0 minutes to about 5 hours, preferably about 1 hour to 3.5 hours, during which no more hydrogen cyanide is fed into the autoclave. During this time, the temperature becomes essentially constant on the Leave the previously set reaction temperature.
- the workup is carried out according to common methods and includes the separation of the unreacted 1, 3-butadiene and the unreacted hydrogen cyanide, for. B. by washing or extracting and the distillative workup of the remaining reaction mixture to separate the valuable products and recover the still active catalyst.
- the hydrogen cyanide is added to the
- adiponitrile from a butadiene-containing mixture can be divided into three steps by adding 2 molar equivalents of hydrogen cyanide:
- Step 1 contained 3-pentenenitriles to various n-pentenenitriles.
- the highest possible proportion of 3-pentenenitrile or 4-pentenenitrile and the lowest possible proportion of conjugated 2-pentenenitrile and 2-methyl-2-butenenitrile which may act as a catalyst poison should be formed.
- the catalysts according to the invention based on phosphinite ligands are also suitable for position and double bond isomerization in step 2 and / or the second addition of hydrogen cyanide in step 3.
- the catalysts used according to the invention not only show a high selectivity with regard to the monoaddition products obtained in the hydrocyanation of 1,3-butadiene-containing hydrocarbon mixtures, but they can also be mixed with an excess of hydrogen cyanide in the hydrocyanation without that there is a noticeable deposition of inactive nickel (II) compounds, such as nickel (II) cyanide.
- the catalysts containing a phosphonite I are therefore not only suitable for continuous hydrocyanation processes in which an excess of hydrogen cyanide in the reaction mixture can generally be effectively avoided, but also for semi-continuous processes and batch processes, in which there is generally a large excess of hydrogen cyanide.
- the catalysts used according to the invention and the processes for hydrocyanation based on them generally have higher catalyst recycle rates and longer catalyst service lives than known processes. In addition to improved economy, this is also advantageous from an ecological point of view, since the nickel cyanide formed from the active catalyst with hydrogen cyanide is highly toxic and must be worked up or disposed of at high cost.
- the systems according to the invention are generally suitable for all customary hydrocyanation processes.
- the hydrocyanation of unactivated olefins e.g. of styrene and 3-pentenenitrile.
- hydrocyanic acid to an olefinic double bond in the presence of a catalyst system according to the invention in particular the addition to butadiene, a butadiene or to 3-pentenenitrile, 4-pentenenitrile or mixtures of such pentenenitriles, or the isomerization of organic nitriles in the presence of a catalyst system according to the invention, in particular the isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile can advantageously be carried out in the presence of one or more Lewis acids as promoters which influence the activity, selectivity or both of the catalyst system according to the invention.
- Inorganic and organic compounds in which the cation is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum are suitable as promoters , Cadmium, rhenium and tin.
- Examples include ZnBr 2 , Znl 2 , ZnCl 2 , ZnS0 4 , CuCl 2 , CuCl, Cu (0 3 SCF 3 ) 2 , CoCl 2 , CoI 2 , Fel 2 , FeCl 3 , FeCl 2 , FeCl 2 (THF) 2 , TiCl 4 (THF) 2 , TiCl 4 , TiCl 3 , CITi (O-iso-Pr) 3 , MnCl 2 , ScCl 3 , AICI3, (C 8 H 17 ) A1C1 2 , (C 8 H 17 ) 2 A1C1, (iso-C 4 H 9 ) 2 A1C1, Ph 2 AlCl, PhAlCl 2 , ReCl, ZrCl 4 , ZrCl 2 , NbCl 5 , VC1 3 , CrCl 2 , M 0 CI 5 , YC1 3 , CdCl
- Suitable promoters are further described in the patents US 3,496,217, US 3,496,218 and US 4,774,353. These include metal salts such as ZnCl 2 , CoI 2 and SnCl 2 , and organometallic compounds such as RA1C1 2 , R 3 Sn0 SCF 3 , and R 3 B, where R is an alkyl group or aryl group.
- US Patent No. 4,874,884 describes how synergistically effective combinations of promoters can be selected to increase the catalytic activity of the catalyst system.
- Preferred promoters include CdCl 2 , FeCl 2 , ZnCl 2 , B (C 6 H 5 ) 3 and (C 6 H 5 ) 3 SnZ, where Z is CF 3 S0 3 , CH 3 C 6 H 4 S0 3 or (C 6 H 5 ) 3 BCN stands.
- the molar ratio of promoter to nickel in the catalyst system can be between 1:16 to 50: 1.
- a further advantageous embodiment of the hydrocyanation can be taken from US 5,693,843, the contents hereby inte grated ⁇ is, with the proviso that, instead of the catalysts mentioned in this patent writing ⁇ an inventive system or a mixture of such systems is used.
- nickel (0) - (m / p-tolyl phosphite) stands for a mixture containing 2.35% by weight of Ni (0), 19% by weight of 3-pentenenitrile and 78.65% by weight of m / p -Tolyl phosphite with a m: p ratio of 2: 1.
- Ni (COD) 2 stands for Ni (0) -bis- (1,4-cyclooctadiene), 2M3BN for 2-methyl-3-butenenitrile, t2M2BN for trans-2-methyl-2-butenenitrile, c2M2BN for cis-2- Methyl-2-butenenitrile, t2PN for trans-2-pentene nitrile, 4PN for 4-pentenenitrile, t3PN for trans-3-pentenenitrile, c3PN for cis-3-pentenenitrile, MGN for methylglutaronitrile, 3PN for the sum of t3PN and c3PN , BD for 1, 3-butadiene, HCN for hydrocyanic acid, ADN for adiponitrile and THF for tetrahydrofuran.
- the HCN conversion to 2M3BN / 3PN was 88.0%.
- the ratio 2M3BN / 3PN was 3/1.
- Example 2 (1 mmol Ni (0)) 1 eq. -Nickel ( 0 ) - ( m / p-tolyl phosphite) was stirred with 1.2 eq Ligan d 1 in THF for 12 hours. This solution was 462 eq. D B an d 390 equivalents of HCN in THF, filled at 25 ° C in a glass autoclave and heated to 80 ° C. The temperature profile of the reaction (slightly exothermic reaction) was determined with an internal thermometer and, after 180 minutes, GC chromatography (GC weight percent, internal standard: ethylbenzene) determined the HCN conversion to 2M3BN and 3PN. The following results were obtained:
- the HCN conversion to 2M3BN / 3PN was 98%.
- the ratio 2M3BN / 3PN was 2/1.
- the HCN conversion to 2M3BN / 3PN was 92%.
- the ratio 2M3BN / 3PN was 2.7 / 1.
- the HCN conversion to 2M3BN / 3PN was 9.8%.
- the ratio 2M3BN / 3PN was 1 / 3.4.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10150286A DE10150286A1 (de) | 2001-10-12 | 2001-10-12 | Phosphinite |
DE10150286 | 2001-10-12 | ||
PCT/EP2002/011108 WO2003033142A1 (de) | 2001-10-12 | 2002-10-04 | Phosphinite |
Publications (1)
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EP1438133A1 true EP1438133A1 (de) | 2004-07-21 |
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Application Number | Title | Priority Date | Filing Date |
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EP02801309A Withdrawn EP1438133A1 (de) | 2001-10-12 | 2002-10-04 | Phosphinite |
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US (1) | US20050090677A1 (zh) |
EP (1) | EP1438133A1 (zh) |
JP (1) | JP2005505611A (zh) |
KR (1) | KR20040048948A (zh) |
CN (1) | CN1568225A (zh) |
AR (1) | AR036791A1 (zh) |
BR (1) | BR0213108A (zh) |
CA (1) | CA2462720A1 (zh) |
DE (1) | DE10150286A1 (zh) |
MX (1) | MXPA04002764A (zh) |
MY (1) | MY143360A (zh) |
WO (1) | WO2003033142A1 (zh) |
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US7880028B2 (en) | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
US9040734B2 (en) | 2010-07-07 | 2015-05-26 | Invista North America S.A R.L. | Process for making nitriles |
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AR038161A1 (es) | 2002-01-24 | 2004-12-29 | Basf Ag | Procedimiento para separar acidos de mezclas de reaccion quimicas con la ayuda de liquidos ionicos |
US7709674B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L | Hydrocyanation process with reduced yield losses |
US8906334B2 (en) | 2007-05-14 | 2014-12-09 | Invista North America S.A R.L. | High efficiency reactor and process |
JP2011515411A (ja) * | 2008-03-19 | 2011-05-19 | インビスタ テクノロジーズ エス エイ アール エル | シクロドデカトリエンの製造方法およびラウロラクトンの製造方法 |
DK2614070T3 (en) | 2010-09-07 | 2017-10-16 | Invista Technologies Sarl | NICKEL COMPOSITIONS FOR THE MANUFACTURE OF NICKEL METAL AND NICKEL COMPLEXS |
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GB1112539A (en) * | 1965-11-26 | 1968-05-08 | Du Pont | Preparation of organic nitriles |
US3496217A (en) * | 1967-05-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins |
US3766237A (en) * | 1972-01-25 | 1973-10-16 | Du Pont | Hydrocyanation of olefins |
US3850973A (en) * | 1973-09-26 | 1974-11-26 | Du Pont | Hydrocyanation of conjugated diolefins |
US4493906A (en) * | 1983-03-08 | 1985-01-15 | The Dow Chemical Company | Catalyst for the selective hydrogenation of acetylenes |
FR2553760B1 (fr) * | 1983-10-25 | 1986-05-02 | Inst Francais Du Petrole | Procede d'hydrogenation selective en presence de solvant des composes acetyleniques d'une coupe d'hydrocarbures c4 riche en butadiene |
US4774353A (en) * | 1986-06-05 | 1988-09-27 | E. I. Du Pont De Nemours And Company | Triorganotin catalyst promoters for hydrocyanation |
US4704492A (en) * | 1986-12-24 | 1987-11-03 | Mobil Oil Corporation | Selective hydrogenation of acetylenic impurities in crude butadiene |
US5175335A (en) * | 1991-11-12 | 1992-12-29 | E. I. Du Pont De Nemours And Company | Enantioselective hydrocyanation of aromatic vinyl compounds |
US5523453A (en) * | 1995-03-22 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Process for hydrocyanation |
US5693843A (en) * | 1995-12-22 | 1997-12-02 | E. I. Du Pont De Nemours And Company | Process for hydrocyanation of diolefins and isomerization of nonconjugated 2 alkyl-3-monoalkenenitriles |
US6171966B1 (en) * | 1996-08-15 | 2001-01-09 | Applied Materials, Inc. | Delineation pattern for epitaxial depositions |
US5710344A (en) * | 1996-11-08 | 1998-01-20 | E. I. Du Pont De Nemours And Company | Process to prepare a linear aldehyde |
MY124170A (en) * | 1997-07-29 | 2006-06-30 | Invista Tech Sarl | Hydrocyanation processes and multidentate phosphite ligand and nickel catalyst compositions therefor |
ZA986369B (en) * | 1997-07-29 | 2000-01-17 | Du Pont | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles. |
DE19740180A1 (de) * | 1997-09-12 | 1999-03-18 | Basf Ag | Katalysator, umfassend wenigstens einen Nickel(0)Komplex auf Basis eines Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
DE19825212A1 (de) * | 1998-06-05 | 1999-12-09 | Basf Ag | Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines zweizähnigen Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
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-
2001
- 2001-10-12 DE DE10150286A patent/DE10150286A1/de not_active Withdrawn
-
2002
- 2002-10-04 WO PCT/EP2002/011108 patent/WO2003033142A1/de not_active Application Discontinuation
- 2002-10-04 CN CNA028201027A patent/CN1568225A/zh active Pending
- 2002-10-04 CA CA002462720A patent/CA2462720A1/en not_active Abandoned
- 2002-10-04 BR BR0213108-0A patent/BR0213108A/pt not_active IP Right Cessation
- 2002-10-04 JP JP2003535929A patent/JP2005505611A/ja not_active Withdrawn
- 2002-10-04 KR KR10-2004-7005252A patent/KR20040048948A/ko not_active Application Discontinuation
- 2002-10-04 MX MXPA04002764A patent/MXPA04002764A/es not_active Application Discontinuation
- 2002-10-04 US US10/491,911 patent/US20050090677A1/en not_active Abandoned
- 2002-10-04 EP EP02801309A patent/EP1438133A1/de not_active Withdrawn
- 2002-10-09 MY MYPI20023759A patent/MY143360A/en unknown
- 2002-10-10 AR ARP020103814A patent/AR036791A1/es not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO03033142A1 * |
Cited By (20)
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US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US8394981B2 (en) | 2006-07-14 | 2013-03-12 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US7880028B2 (en) | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
US9040734B2 (en) | 2010-07-07 | 2015-05-26 | Invista North America S.A R.L. | Process for making nitriles |
US9040733B2 (en) | 2010-07-07 | 2015-05-26 | Invista North America S.A.R.L. | Process for making nitriles |
US9045391B2 (en) | 2010-07-07 | 2015-06-02 | Invista North America S.A.R.L. | Process for making nitriles |
US9051241B2 (en) | 2010-07-07 | 2015-06-09 | Invista North America S.A.R.L. | Process for making nitriles |
US9051242B2 (en) | 2010-07-07 | 2015-06-09 | Invista North America S.A.R.L. | Process for making nitriles |
US9133108B2 (en) | 2010-07-07 | 2015-09-15 | Invista North America S.A.R.L. | Process for making nitriles |
US9133107B2 (en) | 2010-07-07 | 2015-09-15 | Invista North America S.A.R.L. | Process for making nitriles |
US9169197B2 (en) | 2010-07-07 | 2015-10-27 | Invista North America S.A. R.L. | Process for making nitriles |
Also Published As
Publication number | Publication date |
---|---|
CN1568225A (zh) | 2005-01-19 |
BR0213108A (pt) | 2004-09-21 |
MXPA04002764A (es) | 2004-06-29 |
JP2005505611A (ja) | 2005-02-24 |
CA2462720A1 (en) | 2003-04-24 |
WO2003033142A1 (de) | 2003-04-24 |
US20050090677A1 (en) | 2005-04-28 |
DE10150286A1 (de) | 2003-04-17 |
MY143360A (en) | 2011-04-29 |
KR20040048948A (ko) | 2004-06-10 |
AR036791A1 (es) | 2004-10-06 |
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