EP0876214A1 - Process for the preparation by hydrogenation of catalysts based on a transition metal and phosphine - Google Patents
Process for the preparation by hydrogenation of catalysts based on a transition metal and phosphineInfo
- Publication number
- EP0876214A1 EP0876214A1 EP96942425A EP96942425A EP0876214A1 EP 0876214 A1 EP0876214 A1 EP 0876214A1 EP 96942425 A EP96942425 A EP 96942425A EP 96942425 A EP96942425 A EP 96942425A EP 0876214 A1 EP0876214 A1 EP 0876214A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphine
- nickel
- phenyl
- radical
- sulfo
- 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- Withdrawn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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- -1 ammonium cations Chemical class 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 150000003003 phosphines Chemical class 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 159000000000 sodium salts Chemical class 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002841 Lewis acid Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 150000007517 lewis acids Chemical class 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004437 phosphorous atom Chemical group 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 150000003623 transition metal compounds Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 5
- NLEUXPOVZGDKJI-UHFFFAOYSA-N nickel(2+);dicyanide Chemical compound [Ni+2].N#[C-].N#[C-] NLEUXPOVZGDKJI-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000002815 homogeneous catalyst Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002816 nickel compounds Chemical class 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 150000001649 bromium compounds Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 3
- YXTDAZMTQFUZHK-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;tin(2+) Chemical compound [Sn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O YXTDAZMTQFUZHK-ZVGUSBNCSA-L 0.000 claims description 2
- AWBVCFFRSGPMEQ-UHFFFAOYSA-N 2-(dihydroxymethylphosphanyl)ethylphosphanylmethanediol Chemical compound OC(O)PCCPC(O)O AWBVCFFRSGPMEQ-UHFFFAOYSA-N 0.000 claims description 2
- NCUWAYXOOPNJAQ-UHFFFAOYSA-N 2-[2-hydroxyethyl(hydroxymethyl)phosphanyl]ethanol Chemical compound OCCP(CO)CCO NCUWAYXOOPNJAQ-UHFFFAOYSA-N 0.000 claims description 2
- YIWMINXBASHXHT-UHFFFAOYSA-N 2-[[1-[2-bis(2-sulfophenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-(2-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C(=CC=CC=1)S(O)(=O)=O)C=1C(=CC=CC=1)S(O)(=O)=O)C1=CC=CC=C1S(O)(=O)=O YIWMINXBASHXHT-UHFFFAOYSA-N 0.000 claims description 2
- PZIJUXHDLWNNRW-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)phosphanyl]ethanol Chemical compound OCCP(CCO)CCO PZIJUXHDLWNNRW-UHFFFAOYSA-N 0.000 claims description 2
- KYDUPUQPORWKNE-UHFFFAOYSA-N 2-[bis(2-phosphonoethyl)phosphanyl]ethylphosphonic acid Chemical compound OP(O)(=O)CCP(CCP(O)(O)=O)CCP(O)(O)=O KYDUPUQPORWKNE-UHFFFAOYSA-N 0.000 claims description 2
- IUQGTWGOYQRFOX-UHFFFAOYSA-N 2-chloro-5-[(4-chlorophenyl)-(4-chloro-3-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound C1=C(Cl)C(S(=O)(=O)O)=CC(P(C=2C=CC(Cl)=CC=2)C=2C=C(C(Cl)=CC=2)S(O)(=O)=O)=C1 IUQGTWGOYQRFOX-UHFFFAOYSA-N 0.000 claims description 2
- GDCJAPJJFZWILF-UHFFFAOYSA-N 2-ethylbutanedinitrile Chemical compound CCC(C#N)CC#N GDCJAPJJFZWILF-UHFFFAOYSA-N 0.000 claims description 2
- MNXAODVNBYGTNJ-UHFFFAOYSA-N 2-methoxy-5-[(4-methoxyphenyl)-(4-methoxy-3-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound C1=CC(OC)=CC=C1P(C=1C=C(C(OC)=CC=1)S(O)(=O)=O)C1=CC=C(OC)C(S(O)(=O)=O)=C1 MNXAODVNBYGTNJ-UHFFFAOYSA-N 0.000 claims description 2
- NZEDJKVPAZIBIE-UHFFFAOYSA-N 2-methyl-5-[(4-methylphenyl)-(4-methyl-3-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound C1=CC(C)=CC=C1P(C=1C=C(C(C)=CC=1)S(O)(=O)=O)C1=CC=C(C)C(S(O)(=O)=O)=C1 NZEDJKVPAZIBIE-UHFFFAOYSA-N 0.000 claims description 2
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 claims description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- JJUUMBUITPMHBU-UHFFFAOYSA-N 3-(dihydroxymethylphosphanyl)propylphosphanylmethanediol Chemical compound OC(O)PCCCPC(O)O JJUUMBUITPMHBU-UHFFFAOYSA-N 0.000 claims description 2
- SWXCGZAWKVSWNL-UHFFFAOYSA-N 3-[2-carboxyethyl(phenyl)phosphanyl]propanoic acid Chemical compound OC(=O)CCP(CCC(O)=O)C1=CC=CC=C1 SWXCGZAWKVSWNL-UHFFFAOYSA-N 0.000 claims description 2
- YICAEXQYKBMDNH-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)phosphanyl]propan-1-ol Chemical compound OCCCP(CCCO)CCCO YICAEXQYKBMDNH-UHFFFAOYSA-N 0.000 claims description 2
- VHQVWVBUIMMANM-UHFFFAOYSA-N 3-[phenyl-(3-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=C(C=CC=2)S(O)(=O)=O)=C1 VHQVWVBUIMMANM-UHFFFAOYSA-N 0.000 claims description 2
- QXJSYPPVFUFYNH-UHFFFAOYSA-N 3-bis(3-carboxyphenyl)phosphanylbenzoic acid Chemical compound OC(=O)C1=CC=CC(P(C=2C=C(C=CC=2)C(O)=O)C=2C=C(C=CC=2)C(O)=O)=C1 QXJSYPPVFUFYNH-UHFFFAOYSA-N 0.000 claims description 2
- ZBMZOFSLQIPSPW-UHFFFAOYSA-N 3-bis(3-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S(O)(=O)=O)C=2C=C(C=CC=2)S(O)(=O)=O)=C1 ZBMZOFSLQIPSPW-UHFFFAOYSA-N 0.000 claims description 2
- HEMCNETVISWSCS-UHFFFAOYSA-N 4-[phenyl-(4-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1P(C=1C=CC(=CC=1)S(O)(=O)=O)C1=CC=CC=C1 HEMCNETVISWSCS-UHFFFAOYSA-N 0.000 claims description 2
- SKRNRTUXOAPCPG-UHFFFAOYSA-N 4-bis(4-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1P(C=1C=CC(=CC=1)S(O)(=O)=O)C1=CC=C(S(O)(=O)=O)C=C1 SKRNRTUXOAPCPG-UHFFFAOYSA-N 0.000 claims description 2
- FSHOIRSSPIUYCR-UHFFFAOYSA-N 5-bis(4-methoxyphenyl)phosphanyl-2-methoxybenzenesulfonic acid Chemical compound C1=CC(OC)=CC=C1P(C=1C=C(C(OC)=CC=1)S(O)(=O)=O)C1=CC=C(OC)C=C1 FSHOIRSSPIUYCR-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- YZDZJAHFUOFFRN-UHFFFAOYSA-N C1=CC(P(=O)=O)=CC=C1P(C=1C=CC(=CC=1)P(=O)=O)C1=CC=C(P(=O)=O)C=C1 Chemical compound C1=CC(P(=O)=O)=CC=C1P(C=1C=CC(=CC=1)P(=O)=O)C1=CC=C(P(=O)=O)C=C1 YZDZJAHFUOFFRN-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- GWBSCOLBYGGOGQ-UHFFFAOYSA-J S(=O)(=O)([O-])C1=C(C=CC=C1)P(C1=C(C=CC=C1)S(=O)(=O)[O-])CC1C(CC1)CP(C1=C(C=CC=C1)S(=O)(=O)[O-])C1=C(C=CC=C1)S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+] Chemical compound S(=O)(=O)([O-])C1=C(C=CC=C1)P(C1=C(C=CC=C1)S(=O)(=O)[O-])CC1C(CC1)CP(C1=C(C=CC=C1)S(=O)(=O)[O-])C1=C(C=CC=C1)S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+] GWBSCOLBYGGOGQ-UHFFFAOYSA-J 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- PHJJWPXKTFKKPD-UHFFFAOYSA-N [Ni+3].[O-]P([O-])[O-] Chemical compound [Ni+3].[O-]P([O-])[O-] PHJJWPXKTFKKPD-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- ALYMILAYQDOMFU-UHFFFAOYSA-L nickel(2+);dithiocyanate Chemical compound [Ni+2].[S-]C#N.[S-]C#N ALYMILAYQDOMFU-UHFFFAOYSA-L 0.000 claims description 2
- LONQOCRNVIZRSA-UHFFFAOYSA-L nickel(2+);sulfite Chemical compound [Ni+2].[O-]S([O-])=O LONQOCRNVIZRSA-UHFFFAOYSA-L 0.000 claims description 2
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- NGVDGCNFYWLIFO-UHFFFAOYSA-N pyridoxal 5'-phosphate Chemical compound CC1=NC=C(COP(O)(O)=O)C(C=O)=C1O NGVDGCNFYWLIFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229940007163 stannous tartrate Drugs 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- VKUCSUOFPDBCFM-UHFFFAOYSA-N 2-methyl-5-[(4-methyl-2-sulfophenyl)-(4-methyl-3-sulfophenyl)phosphanyl]benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(C)=CC=C1P(C=1C=C(C(C)=C(C=1)S(O)(=O)=O)S(O)(=O)=O)C1=CC=C(C)C(S(O)(=O)=O)=C1 VKUCSUOFPDBCFM-UHFFFAOYSA-N 0.000 claims 1
- BLKHMRKPMVSVGG-UHFFFAOYSA-N 5-bis(4-chloro-3-sulfophenyl)phosphanyl-2-chlorobenzenesulfonic acid Chemical compound C1=C(Cl)C(S(=O)(=O)O)=CC(P(C=2C=C(C(Cl)=CC=2)S(O)(=O)=O)C=2C=C(C(Cl)=CC=2)S(O)(=O)=O)=C1 BLKHMRKPMVSVGG-UHFFFAOYSA-N 0.000 claims 1
- AHFDGJNQHADPSR-UHFFFAOYSA-N 5-bis(4-methoxy-3-sulfophenyl)phosphanyl-2-methoxybenzenesulfonic acid Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC=C1P(C=1C=C(C(OC)=CC=1)S(O)(=O)=O)C1=CC=C(OC)C(S(O)(=O)=O)=C1 AHFDGJNQHADPSR-UHFFFAOYSA-N 0.000 claims 1
- JPRYVMISSYVCFV-UHFFFAOYSA-N 5-bis(4-methyl-3-sulfophenyl)phosphanyl-2-methylbenzenesulfonic acid Chemical compound C1=C(S(O)(=O)=O)C(C)=CC=C1P(C=1C=C(C(C)=CC=1)S(O)(=O)=O)C1=CC=C(C)C(S(O)(=O)=O)=C1 JPRYVMISSYVCFV-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052691 Erbium Inorganic materials 0.000 claims 1
- 229910052688 Gadolinium Inorganic materials 0.000 claims 1
- 125000005595 acetylacetonate group Chemical group 0.000 claims 1
- RRSCGNXXNRAXJC-UHFFFAOYSA-N bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1PC1=CC=C(C)C=C1 RRSCGNXXNRAXJC-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- ZQTKEEICVJSECI-UHFFFAOYSA-N sulfophosphanylethane Chemical compound S(=O)(=O)(O)PCC ZQTKEEICVJSECI-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000002825 nitriles Chemical class 0.000 description 11
- 238000005669 hydrocyanation reaction Methods 0.000 description 10
- 239000003708 ampul Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000003969 polarography Methods 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- ZMVZFANRWNMUGO-UHFFFAOYSA-N 3-[1-(3-sulfophenyl)-1-sulfophosphanylethyl]benzenesulfonic acid Chemical compound S(=O)(=O)(O)C=1C=C(C=CC=1)C(C)(PS(=O)(=O)O)C1=CC(=CC=C1)S(=O)(=O)O ZMVZFANRWNMUGO-UHFFFAOYSA-N 0.000 description 1
- RFRJNCUTSGDHDR-UHFFFAOYSA-N 5-bis(4-methylphenyl)phosphanyl-2-methylbenzenesulfonic acid Chemical class C1=CC(C)=CC=C1P(C=1C=C(C(C)=CC=1)S(O)(=O)=O)C1=CC=C(C)C=C1 RFRJNCUTSGDHDR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 241000276457 Gadidae Species 0.000 description 1
- 101000693728 Homo sapiens S-acyl fatty acid synthase thioesterase, medium chain Proteins 0.000 description 1
- 102100025541 S-acyl fatty acid synthase thioesterase, medium chain Human genes 0.000 description 1
- JOVHNTIMXPAYOU-UHFFFAOYSA-N bis(4-chlorophenyl)phosphane Chemical compound C1=CC(Cl)=CC=C1PC1=CC=C(Cl)C=C1 JOVHNTIMXPAYOU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004408 titanium dioxide Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
-
- 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
- B01J31/2414—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 comprising aliphatic or saturated rings
-
- 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
-
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/96—Water
Definitions
- the present invention relates to a process for the preparation, by reduction using hydrogen, of compounds which can be used as catalysts.
- the compounds targeted by the process of the invention comprise at least one transition metal with an oxidation state of 0 or 1 associated with at least one water-soluble phosphine monodentate or bidentate.
- Such compounds can be used, for example, as catalysts in place of the catalysts used in the hydrocyanation reaction of ethylenic compounds, as described in patent FR-A-2338253. In the present text, they will be called catalysts without this limiting their field of use.
- the present invention allows their regeneration.
- the transition metal which they contain, thus leading in the more or less long term to at least partial deactivation of said catalysts .
- the process for the preparation of catalysts comprising at least one transition metal with an oxidation state of 0 or 1 associated with at least one water-soluble phosphine monodentate or bidentate, consists in treating with hydrogen, in the absence of carbon monoxide, an aqueous solution containing at least one transition metal compound and at least one water-soluble monodentate or bidentate phosphine.
- the water-soluble phosphine used in the process of the invention is a monodentate phosphine corresponding to the general formula (I):
- Ar1, Ar2 and Ar3, identical or different, represent aryl or aryl groups comprising one or more substituents such as:
- -COOM, -SO3M, -PO3M, M representing an inorganic or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals in which the salts of arylcarboxylic acids, arylsulfonic acids or arylphosphonic acids are soluble in water,
- R > 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms,
- - D1, D2, D3, identical or different represent an alkyl group, a cycloalkyl group, an alkyl or cycloalkyl group comprising one or more substituents such as: - alkoxy radical having 1 to 4 carbon atoms,
- - hydrophilic group such as: -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals of which the salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water,
- R which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH
- - L represents a simple 14,iel link or a divalent hydrocarbon radical such as an alkylene radical, a cycloalkylene radical, an arylene radical, a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being directly linked to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one of the atoms phosphorus .or both via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as those defined for AM, Ar2, Ar3, D1, D2 and D3.
- the salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water, lead, zinc and tin.
- water soluble is meant in the present text a compound soluble at least 0.01 g per liter of water.
- the preferred water-soluble phosphines are the phosphines of formula (I) or of formula (II) in which Ar1, Ar2 and Ar3 are phenyl groups or phenyl groups comprising one or two substituents as defined above, D1, D2 and D3 represent a alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 5 to 8 carbon atoms having one or more substituents as defined previously, L is a simple supply link, an alkylene radical having from 1 to 6 carbon atoms, a monocyclic or bicyclic cycloalkylene radical having from 4 to 12 carbon atoms, a phenylene radical, a diphenylene radical, a naphthylene radical, a radical dinap
- a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being directly linked ent to one or both of the phosphorus atoms or being bonded to one or both of the phosphorus atoms via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as an alkyl group having 1 to 4 carbon atoms.
- the preferred water-soluble phosphines are the phosphines of formula (I) or of formula (II) in which:
- -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, cations derived from sodium, potassium, calcium or barium, ammonium cations, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cations derived from zinc, lead or tin,
- R which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms
- phosphines of general formula (i) By way of nonlimiting examples of phosphines of general formula (i), mention may in particular be made of alkali or alkaline-earth salts, ammonium salts, quaternary ammonium salts of (3-sulfo-4-methylphenyl) di (4-methylphenyl) -phosphine; (3-sulfo-4-methoxy phenyl) di (4-methoxy-phenyl) -phosphine; (3-chloro-4-phenyl) di (4-chloro-phenyl) -phosphine; di (3-sulfo phenyl) phenyl-phosphine; di (4-sulfo phenyl) phenylphosphine; di (3-sulfo-4-methylphenyl) (4-methyl-phenyl) -phosphine; di (3-sulfo-4-methoxy phenyl) phosphine; di
- phosphines of general formula (II) there may be mentioned in particular the sodium salt of 2,2'-bis [di (sulfonatophenyl) phosphino] -1,1'- binaphthyl, the sodium salt 1,2-bis [di (sulfonatophenyl) phosphinomethyl] cyclobutane (CBDTS), 1,2-bis (dihydroxymethyl-phosphino) ethane, 1,3-bis (dihydroxymethylphosphino) propane, the sodium salt of 2,2 '- bis [di (sulfonatophenyl) phosphinomethyl] -1, l'-binaphtyl.
- CBDTS 1,2-bis [di (sulfonatophenyl) phosphinomethyl] cyclobutane
- 1,2-bis (dihydroxymethyl-phosphino) ethane 1,3-bis (dihydroxymethylphosphino) propane
- the sulfonate groups for example, can be introduced by the reaction of SO3 in sulfuric acid.
- the carboxylate, phosphonate and quaternary ammonium groups can likewise be introduced by applying the chemical methods known for this type of synthesis.
- transition metal compounds compounds of nickel, cobalt, iron, palladium, platinum, rhodium and iridium are used, at least partially at a degree of oxidation different from 0. compounds soluble in water or capable of passing into solution under the conditions of the reaction.
- the rest linked to the metal is not critical, as long as it satisfies these conditions.
- the most preferred compounds are those of nickel. Mention may be made, by way of nonlimiting examples, of compounds such as nickel carboxylates (in particular acetate, formate, citrate), nickel carbonate, nickel bicarbonate, nickel borate, nickel bromide, nickel chloride, nickel iodide, nickel thiocyanate, nickel cyanide, nickel hydroxide, nickel hydrophosphite, phosphite nickel, nickel phosphate and derivatives, nickel nitrate, nickel sulfate, nickel sulfite, nickel aryl and alkyl sulfonates.
- nickel carboxylates in particular acetate, formate, citrate
- nickel carbonate nickel bicarbonate
- nickel borate nickel bromide
- nickel chloride nickel iodide
- nickel thiocyanate nickel cyanide
- nickel hydroxide nickel hydrophosphite
- phosphite nickel nickel phosphate and derivatives
- nickel nitrate nickel sulfate
- the nickel compound need not itself be water soluble.
- nickel cyanide poorly soluble in water dissolves well in an aqueous solution of water-soluble phosphine, in particular sulfonated.
- the reduction by hydrogen of the transition metal compound, in the presence of at least one water-soluble phosphine monodentate or bidentate can be carried out in homogeneous phase, optionally in the presence of a homogeneous catalyst soluble in the reaction medium or in heterogeneous phase in the presence of a catalyst insoluble in the reaction medium.
- catalysts of this type of catalysis such as for example water-soluble phosphine complexes of rhodium, iridium, cobalt, ruthenium, nickel or palladium.
- heterogeneous catalyst it is possible to use the various metals or compounds of these metals, deposited on a support or not, which are generally used in catalytic hydrogenation.
- these metals the most commonly used are the metals of group VIII of the Periodic Table of the Elements, as published in Ha ⁇ dbook of chemistry and physics, 51 st Edition (1970-1971) of The Chemical Rubber Co.
- the metals of this group VIII which are more particularly suitable, mention may be made of platinum, palladium, ruthenium and nickel.
- the supported catalysts are advantageously used.
- the supports are very varied. Among them, non-limiting mention may be made of aluminas, carbon black, silicas, the various metal oxides such as cerine, zirconia, titanium dioxide, metal salts such as calcium carbonate, barium sulphate.
- aluminas carbon black
- silicas the various metal oxides such as cerine, zirconia, titanium dioxide, metal salts such as calcium carbonate, barium sulphate.
- Raney nickel and Raney cobalt are preferably used. Raney nickel is particularly suitable.
- the catalytic reduction is generally carried out under a hydrogen pressure measured at 25 ° C from 1 to 200 bars and at a temperature from 5 ° C to 200 ° C.
- the hydrogen pressure measured at 25 ° C is from 1 to 150 bars and the temperature is from 10 "C to 120 ° C.
- the solution of the transition metal compound to be reduced may further comprise compounds whose role is to supplement the catalyst prepared by the process of the invention.
- These compounds are in particular Lewis acids.
- Lewis acid is meant in the present text, according to the usual definition, compounds that accept electronic doublets. It is possible to use in particular the Lewis acids cited in the work edited by GA OLAH "Friedel-Crafts and related Reactions", volume I, pages 191 to 197 (1963).
- the Lewis acids which can be used in the reaction mixture are chosen from the compounds of the elements of groups Ib, llb, lila, IIIb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the Periodic Table of Elements , as published in Handbook of chemistry and physics, 51st Edition (1970-1971) of The Chemical Rubber Co, insofar as said compounds are at least partially soluble and stable in water or more generally in the aqueous solution to be treated .
- salts especially halides, preferably chlorides and bromides, sulfates, nitrates, sulfonates, especially trifluoromethanesulfonates, carboxylates, acetyiacetonates, tetrafluoroborates and phosphates .
- Lewis acids By way of nonlimiting examples of such Lewis acids, mention may be made of zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesutfonate, zinc acetate, zinc nitrate, tetrafluoroborate zinc, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, bromide stannous, stannous sulfate, stannous tartrate, chlorides, bromides, sulfates, nitrates, carboxylates or trifluoromethane ⁇ sulfonates of rare earth elements like lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadoiinium, terbium, dysprosium, holmium, Perbium, thulium, y
- the Lewis acid used generally represents from 0 to 50 moles per mole of transition metal compound, more particularly of nickel compound, and preferably from 0 to 10 moles per mole.
- An interesting variant of the process of the invention consists in regenerating a spent catalyst, that is to say a catalyst which has been used and which has become at least partially inactive.
- a catalyst based on water-soluble phosphine monodentate or bidentate and a transition metal with the oxidation state 0 or 1, optionally also containing one or more Lewis acids, used in the hydrocyanation reaction of butadiene and / or pentene-nitriles is gradually deactivated, in particular by oxidation of the transition metal.
- This, and more particularly nickel is transformed at least in part into cyanide.
- the aqueous phase containing in particular the water-soluble phosphine monodentate or bidentate and the compound of the transition metal at least partially at a degree of oxidation greater than 0, can be easily separated from the organic phase.
- This aqueous phase can contain variable amounts of compounds initially introduced such as butadiene and / or pentene-nitriles or formed during the reaction such as adiponitrile, methyl-glutaronitrile, ethyl-succinonitrile, pentene-nitriles, methylbutene-nitriles.
- the aqueous phase is treated as described above in order to regenerate the catalyst by reduction of the transition metal which is at a degree of oxidation greater than 0.
- COD cyclo-octadiene
- Example 11 reduction of Ni (CN) 2 on Pt / C and hydrocyanation of pentene-3 nitrile
- CE2 * comparative test with a solution of Ni (CN) 2 (TPPTSNa3) 2 + ZnCl2 (0.5mol / kg) not treated with hydrogen.
- the vial is placed in an autoclave which is pressurized to 100 bar of hydrogen and heated to 100 ° C (duration indicated in table 3).
- the autoclave is decompressed and the analysis of the aqueous solution is carried out by polarography.
- the nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration.
- CE4 * comparative test with a solution of Ni (CN) 2 (TPPTSNa3) 2 + ZnCl2 (0.5mol / kg) not treated with hydrogen.
- the ampoule is placed in an autoclave which is pressurized to 100 bar of hydrogen and stirred at room temperature (about 25 ° C) for 1 hour.
- the reactor is decompressed and the analysis of the aqueous solution is carried out by poiarography.
- the nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration. No nickel precipitate is observed and in each test the quantity of total nickel assayed corresponds, with the details close to the analysis, to the quantity introduced at the start of the test.
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Abstract
The present invention relates to a process for the preparation through hydrogenation of compounds which can be used as catalysts. The disclosed compounds comprise more specifically at least one transition metal with an oxydation degree of 0 or 1 associated to at least one monodentate or bidentate hydrosoluble phosphine. The process for the synthesis of catalysts comprises the hydrogenation of an aqueous solution containing at least one compound of a transition metal and a monodentate or bidentate hydrosoluble phosphine.
Description
PROCEDE DE PREPARATION PAR HYDROGENATION DE CATALYSEURS A BASE DE METAL DE TRANSITION ET DE PHOSPHINE PROCESS FOR THE PREPARATION BY HYDROGENATION OF CATALYSTS BASED ON TRANSITIONAL METAL AND PHOSPHINE
La présente invention concerne un procédé de préparation, par réduction à l'aide d'hydrogène, de composés pouvant être utilisés comme catalyseurs.The present invention relates to a process for the preparation, by reduction using hydrogen, of compounds which can be used as catalysts.
Les composés visés par le procédé de l'invention comportent au moins un métal de transition au degré d'oxydation 0 ou 1 associé à au moins une phosphine hydrosoluble monodentate ou bidentate.The compounds targeted by the process of the invention comprise at least one transition metal with an oxidation state of 0 or 1 associated with at least one water-soluble phosphine monodentate or bidentate.
De tels composés peuvent être utilisés par exemple comme catalyseurs à ia place des catalyseurs mis en oeuvre dans la réaction d'hydrocyanation de composés éthyléniques, telle que décrite dans le brevet FR-A-2338253. Dans le présent texte, ils seront nommés catalyseurs sans que cela limite leur domaine d'utilisation.Such compounds can be used, for example, as catalysts in place of the catalysts used in the hydrocyanation reaction of ethylenic compounds, as described in patent FR-A-2338253. In the present text, they will be called catalysts without this limiting their field of use.
Outre la synthèse de tels catalyseurs, la présente invention permet leur régénération. En effet, lors de l'utilisation de tels catalyseurs pour l'hydrocyanation de composés éthyléniques, il se produit une oxydation progressive du métal de transition qu'ils contiennent, conduisant ainsi à plus ou moins longue échéance à une désactivation au moins partielle desdits catalyseurs.In addition to the synthesis of such catalysts, the present invention allows their regeneration. In fact, during the use of such catalysts for the hydrocyanation of ethylenic compounds, there occurs a progressive oxidation of the transition metal which they contain, thus leading in the more or less long term to at least partial deactivation of said catalysts .
Le procédé de préparation de catalyseurs, comportant au moins un métal de transition au degré d'oxydation 0 ou 1 associé à au moins une phosphine hydrosoluble monodentate ou bidentate, consiste à traiter par l'hydrogène, en l'absence de monoxyde de carbone, une solution aqueuse contenant au moins un composé d'un métal de transition et au moins une phosphine hydrosoluble monodentate ou bidentate.The process for the preparation of catalysts, comprising at least one transition metal with an oxidation state of 0 or 1 associated with at least one water-soluble phosphine monodentate or bidentate, consists in treating with hydrogen, in the absence of carbon monoxide, an aqueous solution containing at least one transition metal compound and at least one water-soluble monodentate or bidentate phosphine.
L'expression "en l'absence de monoxyde de carbone" signifie que l'on met en oeuvre dans le procédé de l'invention un hydrogène de qualité industrielle, ne contenant éventuellement que des teneurs résiduelles très faibles en monoxyde de carbone, c'est-à-dire habituellement inférieures à 0,01 % en mole par mole, et qu'il n'est ajouté aucune quantité supplémentaire dudit monoxyde de carbone.The expression "in the absence of carbon monoxide" means that an industrial grade hydrogen is used in the process of the invention, possibly containing only very low residual contents of carbon monoxide, ie that is, usually less than 0.01 mol% per mol, and that no additional amount of said carbon monoxide is added.
La phosphine hydrosoluble mise en oeuvre dans le procédé de l'invention est une phosphine monodentate répondant à la formule générale (I) :The water-soluble phosphine used in the process of the invention is a monodentate phosphine corresponding to the general formula (I):
P (Ar1)a (Ar2)b (Ar3)c (D1)d (D2)e (D3)f (I)P (Ar1) a (Ar2) b (Ar3) c (D1) d (D2) e (D3) f (I)
dans laquelle :in which :
- Ar1 , Ar2 et Ar3, identiques ou différents, représentent des groupes aryle ou aryle comportant un ou plusieurs substituants tels que :- Ar1, Ar2 and Ar3, identical or different, represent aryl or aryl groups comprising one or more substituents such as:
- radical alkyle ou alcoxy ayant 1 à 4 atomes de carbone,- alkyl or alkoxy radical having 1 to 4 carbon atoms,
- atome d'halogène,
- groupe nitrile,- halogen atom, - nitrile group,
- groupe nitro,- nitro group,
- groupe hydrophile comme :- hydrophilic group such as:
-COOM, -SO3M, -PO3M, M représentant un reste cationique minéral ou organique choisi parmi le proton, les cations dérivés des métaux alcalins ou alcalino- terreux, les cations ammonium -N(R)4 dans la formule desquels les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, les autres cations dérivés de métaux dont les sels des acides arylcarboxyliques, des acides arylsulfoniques ou des acides arylphosphoniques sont solubles dans l'eau,-COOM, -SO3M, -PO3M, M representing an inorganic or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals in which the salts of arylcarboxylic acids, arylsulfonic acids or arylphosphonic acids are soluble in water,
-N(R>3 dans la formule duquel les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone,-N (R> 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms,
-OH,-OH,
- a, b et c représentent indépendamment les uns des autres 0 ou 1,- a, b and c represent independently of each other 0 or 1,
- D1 , D2, D3, identiques ou différents, représentent un groupe alkyle, un groupe cycloalkyle, un groupe alkyle ou cycloalkyle comportant un ou plusieurs substituants tels que : - radical alcoxy ayant 1 à 4 atomes de carbone,- D1, D2, D3, identical or different, represent an alkyl group, a cycloalkyl group, an alkyl or cycloalkyl group comprising one or more substituents such as: - alkoxy radical having 1 to 4 carbon atoms,
- atome d'halogène,- halogen atom,
- groupe nitrile,- nitrile group,
- groupe nitro,- nitro group,
- groupe hydrophile comme : -COOM, -SO3M, -PO3M, M représentant un reste cationique minéral ou organique choisi parmi le proton, les cations dérivés des métaux alcalins ou alcalino- terreux, les cations ammonium -N(R)4 dans la formule desquels les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, les autres cations dérivés de métaux dont les sels des acides carboxyliques, des acides sulfoniques ou des acides phosphoniques sont solubles dans l'eau,- hydrophilic group such as: -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals of which the salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water,
-N(R)3 dans ia formule duquel les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, -OH-N (R) 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH
- d, e et f représentent indépendamment les uns des autres 0 ou 1 ,- d, e and f represent independently of each other 0 or 1,
- la somme (a+b+c+d+e+f) est égale à 3
ou bidentate répondant à la formule générale (II) :- the sum (a + b + c + d + e + f) is equal to 3 or bidentate corresponding to the general formula (II):
(Ar1)a (Ar2)b (D1)d (D2)e P-L-P (Ar1)g (Ar2)h (D1)j (D2)j (II)(Ar1) a (Ar2) b (D1) d (D2) e PLP (Ar1) g (Ar2) h (D1) j (D2) j (II)
dans laquelle :in which :
- Ar1 , Ar2, D1 et D2 ont les significations indiquées précédemment pour ia formule (I),- Ar1, Ar2, D1 and D2 have the meanings indicated above for the formula (I),
- a, b, d, e, g, h, i et j représentent chacun 0 ou 1 ,- a, b, d, e, g, h, i and j each represent 0 or 1,
- la somme (a+b+d+e) est égale à 2,- the sum (a + b + d + e) is equal to 2,
- la somme (g+h+i+j) est égale à 2, - L représente un lien vaientiel simple ou un radical hydrocarboné divalent tel qu'un radical alkylene, un radical cycloalkylène, un radical arylène, un radical dérivant d'un hétérocycle comportant un ou deux atomes d'oxygène, d'azote ou de soufre dans le cycle, ces différents radicaux cycliques étant liés directement à l'un des atomes de phosphore ou aux deux atomes de phosphore ou étant lié à l'un des atomes de phosphore .ou aux deux par l'intermédiaire d'un radical alkylene linéaire ou ramifié ayant de 1 à 4 atomes de carbone, le ou les cycles éventuellement parties du radical divalent L pouvant comporter un ou plusieurs substituants tels que ceux définis pour AM, Ar2, Ar3, D1, D2 et D3.- the sum (g + h + i + j) is equal to 2, - L represents a simple vaisiel link or a divalent hydrocarbon radical such as an alkylene radical, a cycloalkylene radical, an arylene radical, a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being directly linked to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one of the atoms phosphorus .or both via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as those defined for AM, Ar2, Ar3, D1, D2 and D3.
On peut citer, comme exemples de métaux dont les sels des acides carboxyliques, des acides sulfoniques ou des acides phosphoniques sont solubles dans l'eau, le plomb, le zinc et l'étain.As examples of metals, the salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water, lead, zinc and tin.
Par l'expression soluble dans l'eau, on entend dans le présent texte un composé soluble à au moins 0,01 g par litre d'eau. Les phosphines hydrosolubles préférées sont les phosphines de formule (I) ou de formule (II) dans lesquelles Ar1, Ar2 et Ar3 sont des groupes phényle ou des groupes phényles comportant un ou deux substituants tels que définis précédemment, D1, D2 et D3 représentent un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle ayant 5 à 8 atomes de carbone, un groupe alkyle ayant de 1 à 6 atomes de carbone ou cycloalkyle ayant 5 à 8 atomes de carbone comportant un ou plusieurs substituants tels que définis précédemment, L est un lien vaientiel simple, un radical alkylene ayant de 1 à 6 atomes de carbone, un radical cycloalkylène monocyclique ou bicyciique ayant de 4 à 12 atomes de carbone, un radical phénylène, un radical diphénylène, un radical naphtylène, un radical dinaphtylène.un radical dérivant d'un hétérocycle comportant un ou deux atomes d'oxygène, d'azote ou de soufre dans le cycle, ces différents radicaux cycliques étant liés directement à l'un des atomes de phosphore ou aux deux atomes de phosphore ou étant lié à l'un des atomes de phosphore ou aux deux par l'intermédiaire d'un radical alkylene linéaire ou ramifié ayant
de 1 à 4 atomes de carbone, le ou les cycles éventuellement parties du radical divalent L pouvant comporter un ou plusieurs substituants tels que groupe alkyle ayant 1 â 4 atomes de carbone.By the expression water soluble, is meant in the present text a compound soluble at least 0.01 g per liter of water. The preferred water-soluble phosphines are the phosphines of formula (I) or of formula (II) in which Ar1, Ar2 and Ar3 are phenyl groups or phenyl groups comprising one or two substituents as defined above, D1, D2 and D3 represent a alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 5 to 8 carbon atoms having one or more substituents as defined previously, L is a simple supply link, an alkylene radical having from 1 to 6 carbon atoms, a monocyclic or bicyclic cycloalkylene radical having from 4 to 12 carbon atoms, a phenylene radical, a diphenylene radical, a naphthylene radical, a radical dinaphthylene. a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being directly linked ent to one or both of the phosphorus atoms or being bonded to one or both of the phosphorus atoms via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as an alkyl group having 1 to 4 carbon atoms.
Les phosphines hydrosolubles préférées sont les phosphines de formule (I) ou de formule (II) dans lesquelles:The preferred water-soluble phosphines are the phosphines of formula (I) or of formula (II) in which:
- le ou les substituants de Ar, Ar2 et Ar3, identiques ou différents, représentent des groupes tels que :- the substituent (s) of Ar, Ar2 and Ar3, identical or different, represent groups such as:
- radical alkyle ou alcoxy ayant 1 à 2 atomes de carbone,- alkyl or alkoxy radical having 1 to 2 carbon atoms,
- atome de chlore, - groupe hydrophile comme :- chlorine atom, - hydrophilic group such as:
-COOM, -SO3M, -PO3M, M représentant un reste cationique minéral ou organique choisi parmi le proton, les cations dérivés du sodium, du potassium, du calcium ou du baryum, les cations ammonium, tetraméthylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, les cations dérivés du zinc, du plomb ou de l'étain,-COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, cations derived from sodium, potassium, calcium or barium, ammonium cations, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cations derived from zinc, lead or tin,
-N(R)3 dans la formule duquel les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone,-N (R) 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms,
-OH globalement deux au moins desdits substituants de Ar1, Ar2, Ar3, D1, D2 et D3 pour les phosphines de formule (I) et de AM , Ar2, D1 et D2 pour les phosphines de formule (II) étant un groupe hydrophile tel que défini précédemment.-OH generally at least two of said substituents of Ar1, Ar2, Ar3, D1, D2 and D3 for the phosphines of formula (I) and of AM, Ar2, D1 and D2 for the phosphines of formula (II) being a hydrophilic group such as defined above.
A titre d'exemples non limitatifs de phosphines de formule générale (i), on peut citer notamment les sels alcalins ou alcalino-terreux, les sels d'ammonium, les sels d'ammonium quaternaire des (sulfo-3 méthyl-4 phenyl) di (méthyl-4 phényl)-phosphine ; (sulfo-3 méthoxy-4 phenyl) di(méthoxy-4 phényl)-phosphine ; (sulfo-3 chloro-4 phenyl) di(chloro-4 phényl)-phosphine ; di(sulfo-3 phenyl) phényl-phosphine ; di(sulfo-4 phenyl) phényi-phosphine ; di(sulfo-3 méthyl-4 phenyl) (méthyl-4 phényl)-phosphine ; di(sulfo-3 méthoxy-4 phenyl) (méthoxy-4 phenyl) phosphine ; di(sulfo-3 chloro-4 phenyl) (chloro-4 phenyl) phosphine ; tri(sulfo-3 phényl)-phosphine ; tri(sulfo-4 phényl)-phosphine ; (tri(sulfo~3 méthyl-4 phényl)-phosphine ; tri(sulfo-3, méthoxy-4 phényl)-phosphine ; tri(sulfo-3 chloro-4 phényl)-phosphine ; (sulfo-2 mόthyl-4 phenyl) (sulfo-3, méthyl-4 phenyl) (disulfo-3,5 méthyl-4 phényl)-phosphine ; (sulfo-3 phenyl) (sulfo-3 chloro-4 phenyl) (disulfo-3,5 chloro-4 phényl)-phosphine, la tris(hydroxyméthyl) phosphine, la tris(2-hydroxyéthyl) phosphine, la tris(3-hydroxypropyl) phosphine, la tris(2-carboxyméthyl) phosphine, le sel de sodium de la tris(3-carboxylatophényl) phosphine, la tris(3-carboxyéthyl) phosphine, l'iodure de la tris(4-triméthylammoniumphényl) phosphine, le sel de sodium de la
tris(2-phosphonatoéthyl) phosphine, la bis(2-carboxyéthyl) phenyl phosphine, l'hydroxyméthyl bis(2-hydroxyéthyl) phosphine, le sel de sodium de la tris(paraphosphophényl) phosphine, le sel de sodium de la bis(métasulfophényl) paracarboxyphényl phosphine, le sel de sodium de la bis(métasulfophényl) sulfo-2 éthyl phosphine.By way of nonlimiting examples of phosphines of general formula (i), mention may in particular be made of alkali or alkaline-earth salts, ammonium salts, quaternary ammonium salts of (3-sulfo-4-methylphenyl) di (4-methylphenyl) -phosphine; (3-sulfo-4-methoxy phenyl) di (4-methoxy-phenyl) -phosphine; (3-chloro-4-phenyl) di (4-chloro-phenyl) -phosphine; di (3-sulfo phenyl) phenyl-phosphine; di (4-sulfo phenyl) phenylphosphine; di (3-sulfo-4-methylphenyl) (4-methyl-phenyl) -phosphine; di (3-sulfo-4-methoxy phenyl) (4-methoxy-phenyl) phosphine; di (3-sulfo-4-chloro phenyl) (4-chloro-phenyl) phosphine; tri (3-sulfo phenyl) -phosphine; tri (4-sulfo phenyl) -phosphine; (tri (sulfo ~ 3 methyl-4 phenyl) -phosphine; tri (sulfo-3, methoxy-4 phenyl) -phosphine; tri (sulfo-3 chloro-4 phenyl) -phosphine; (sulfo-2 methyl-4 phenyl) (sulfo-3, methyl-4 phenyl) (disulfo-3,5 methyl-4 phenyl) -phosphine; (sulfo-3 phenyl) (sulfo-3 chloro-4 phenyl) (disulfo-3,5 chloro-4 phenyl) -phosphine, tris (hydroxymethyl) phosphine, tris (2-hydroxyethyl) phosphine, tris (3-hydroxypropyl) phosphine, tris (2-carboxymethyl) phosphine, sodium salt of tris (3-carboxylatophenyl) phosphine , tris (3-carboxyethyl) phosphine, iodide of tris (4-trimethylammoniumphenyl) phosphine, the sodium salt of tris (2-phosphonatoethyl) phosphine, bis (2-carboxyethyl) phenyl phosphine, hydroxymethyl bis (2-hydroxyethyl) phosphine, sodium salt of tris (paraphosphophenyl) phosphine, sodium salt of bis (metasulfophenyl ) paracarboxyphenyl phosphine, the sodium salt of bis (metasulfophenyl) sulfo-2 ethyl phosphine.
A titre d'exemples non limitatifs de phosphines de formule générale (II), on peut citer notamment le sel de sodium du 2,2'-bis[di(sulfonatophényl)phosphino]-1,1'- binaphtyl, le sel de sodium du 1,2-bis[di(sulfonatophényl)phosphinométhyl] cyclobutane (CBDTS), le 1,2-bis(dihydroxyméthyl-phosphino) éthane, le 1,3-bis(dihydroxyméthylphosphino) propane, le sel de sodium du 2,2'- bis[di(sulfonatophényl)phosphinométhyl]-1 , l'-binaphtyl.By way of nonlimiting examples of phosphines of general formula (II), there may be mentioned in particular the sodium salt of 2,2'-bis [di (sulfonatophenyl) phosphino] -1,1'- binaphthyl, the sodium salt 1,2-bis [di (sulfonatophenyl) phosphinomethyl] cyclobutane (CBDTS), 1,2-bis (dihydroxymethyl-phosphino) ethane, 1,3-bis (dihydroxymethylphosphino) propane, the sodium salt of 2,2 '- bis [di (sulfonatophenyl) phosphinomethyl] -1, l'-binaphtyl.
On peut bien évidemment utiliser un mélange de plusieurs de ces phosphines. Certaines des phosphines hydrosolubles de formule (I) ou (II) sont disponibles dans le commerce. Pour la préparation des autres, on peut se référer aux procédés généraux ou particuliers de synthèse des phosphines décrits dans les ouvrages généraux comme HOUBEN-WEYL, Method der organischen Chemie, organische Phosphor Verbindungen, teil 1 (1963).It is obviously possible to use a mixture of several of these phosphines. Some of the water-soluble phosphines of formula (I) or (II) are commercially available. For the preparation of the others, reference may be made to the general or particular processes for the synthesis of phosphines described in general works such as HOUBEN-WEYL, Method der organischen Chemie, organische Phosphor Verbindungen, teil 1 (1963).
Enfin, pour la préparation des dérivés hydrosolubles non décrits, on peut à partir des phosphines ne comportant pas de substituants hydrosolubles définis précédemment, procéder facilement à l'introduction d'un ou plusieurs de ces substituants hydrophiles. Ainsi les groupements sulfonates par exemple peuvent être introduits par la réaction de SO3 dans l'acide sulfurique. Les groupes carboxylates, phosphonates, ammonium quaternaires peuvent de même être introduits en appliquant les méthodes chimiques connues pour ce type de synthèse.Finally, for the preparation of the water-soluble derivatives not described, it is possible, from phosphines not containing water-soluble substituents defined above, to easily introduce one or more of these hydrophilic substituents. Thus, the sulfonate groups, for example, can be introduced by the reaction of SO3 in sulfuric acid. The carboxylate, phosphonate and quaternary ammonium groups can likewise be introduced by applying the chemical methods known for this type of synthesis.
On utilise de préférence comme composés des métaux de transition des composés du nickel, du cobalt, du fer, du palladium, du platine, du rhodium et de l'iridium, au moins partiellement à un degré d'oxydation différent de 0. On utilise des composés solubles dans l'eau ou capables de passer en solution dans les conditions de la réaction. Le reste lié au métal n'est pas critique, dès l'instant qu'il satisfait à ces conditions.Preferably, as transition metal compounds, compounds of nickel, cobalt, iron, palladium, platinum, rhodium and iridium are used, at least partially at a degree of oxidation different from 0. compounds soluble in water or capable of passing into solution under the conditions of the reaction. The rest linked to the metal is not critical, as long as it satisfies these conditions.
Parmi les composés précités, les composés les plus préférés sont ceux du nickel. On peut citer à titre d'exemples non limitatifs des composés tels que carboxylates de nickel (notamment acétate, formiate, citrate), carbonate de nickel, bicarbonate de nickel, borate de nickel, bromure de nickel, chlorure de nickel, iodure de nickel, thiocyanate de nickel, cyanure de nickel, hydroxyde de nickel, hydrophosphite de nickel, phosphite de
nickel, phosphate de nickel et dérivés, nitrate de nickel, sulfate de nickel, sulfite de nickel, aryl- et alkyl-sulfonates de nickel.Among the aforementioned compounds, the most preferred compounds are those of nickel. Mention may be made, by way of nonlimiting examples, of compounds such as nickel carboxylates (in particular acetate, formate, citrate), nickel carbonate, nickel bicarbonate, nickel borate, nickel bromide, nickel chloride, nickel iodide, nickel thiocyanate, nickel cyanide, nickel hydroxide, nickel hydrophosphite, phosphite nickel, nickel phosphate and derivatives, nickel nitrate, nickel sulfate, nickel sulfite, nickel aryl and alkyl sulfonates.
Il n'est pas nécessaire que le composé du nickel soit lui même soluble dans l'eau. Par exemple, le cyanure de nickel peu soluble dans l'eau se dissout bien dans une solution aqueuse de phosphine hydrosoluble, notamment sulfonée.The nickel compound need not itself be water soluble. For example, nickel cyanide poorly soluble in water dissolves well in an aqueous solution of water-soluble phosphine, in particular sulfonated.
La réduction par l'hydrogène du composé de métal de transition, en présence d'au moins une phosphine hydrosoluble monodentate ou bidentate, peut être effectuée en phase homogène, éventuellement en présence d'un catalyseur homogène soluble dans le milieu réactionnel ou en phase hétérogène en présence d'un catalyseur insoluble dans le milieu réactionnel.The reduction by hydrogen of the transition metal compound, in the presence of at least one water-soluble phosphine monodentate or bidentate, can be carried out in homogeneous phase, optionally in the presence of a homogeneous catalyst soluble in the reaction medium or in heterogeneous phase in the presence of a catalyst insoluble in the reaction medium.
Comme catalyseur homogène, on peut utiliser les catalyseurs habituels de ce type de catalyse tels que par exemple des complexes phosphine hydrosoluble de rhodium, iridium, cobalt, ruthénium, nickel ou palladium.As homogeneous catalyst, it is possible to use the usual catalysts of this type of catalysis such as for example water-soluble phosphine complexes of rhodium, iridium, cobalt, ruthenium, nickel or palladium.
Comme catalyseur hétérogène, on peut utiliser les différents métaux ou composés de ces métaux, déposés sur un support ou non, qui sont généralement employés en hydrogénation catalytique. Parmi ces métaux, les plus couramment mis en oeuvre sont les métaux du groupe VIII de la Classification périodique des Eléments, telle que publiée dans Haπdbook of chemistry and physics, 51 st Edition (1970-1971) of The Chemical Rubber Co. Parmi les métaux de ce groupe VIII qui conviennent plus particulièrement, on peut citer le platine, le palladium, le ruthénium et le nickel.As heterogeneous catalyst, it is possible to use the various metals or compounds of these metals, deposited on a support or not, which are generally used in catalytic hydrogenation. Among these metals, the most commonly used are the metals of group VIII of the Periodic Table of the Elements, as published in Haπdbook of chemistry and physics, 51 st Edition (1970-1971) of The Chemical Rubber Co. Among the metals of this group VIII which are more particularly suitable, mention may be made of platinum, palladium, ruthenium and nickel.
Les catalyseurs supportés sont utilisés avantageusement. Les supports sont très variés. Parmi eux, on peut citer non limitativement les alumines, le noir de carbone, les silices, les différents oxydes métalliques comme la cérine, ta zircone, le dioxyde de titane, des sels métalliques comme le carbonate de calcium, le sulfate de baryum. Parmi les catalyseurs hétérogènes non supportés, le nickel de Raney et le cobalt de Raney sont utilisés de préférence. Le nickel de Raney convient tout particulièrement bien.The supported catalysts are advantageously used. The supports are very varied. Among them, non-limiting mention may be made of aluminas, carbon black, silicas, the various metal oxides such as cerine, zirconia, titanium dioxide, metal salts such as calcium carbonate, barium sulphate. Among the unsupported heterogeneous catalysts, Raney nickel and Raney cobalt are preferably used. Raney nickel is particularly suitable.
La réduction catalytique est effectuée généralement sous une pression d'hydrogène mesurée à 25°C de 1 à 200 bars et à une température de 5°C à 200°C. De préférence, la pression d'hydrogène mesurée à 25°C est de 1 à 150 bars et la température est de 10 "C à 120°C.The catalytic reduction is generally carried out under a hydrogen pressure measured at 25 ° C from 1 to 200 bars and at a temperature from 5 ° C to 200 ° C. Preferably, the hydrogen pressure measured at 25 ° C is from 1 to 150 bars and the temperature is from 10 "C to 120 ° C.
La solution du composé de métal de transition à réduire peut en outre comprendre des composés dont le rôle est de compléter le catalyseur préparé par le procédé de rinvention. Ces composés sont notamment des acides de Lewis. Par acide de Lewis, on entend dans le présent texte, selon la définition usuelle, des composés accepteurs de doublets électroniques.
On peut mettre en oeuvre notamment les acides de Lewis cités dans l'ouvrage édité par G.A. OLAH "Friedel-Crafts and related Reactions", tome I, pages 191 à 197 (1963).The solution of the transition metal compound to be reduced may further comprise compounds whose role is to supplement the catalyst prepared by the process of the invention. These compounds are in particular Lewis acids. By Lewis acid is meant in the present text, according to the usual definition, compounds that accept electronic doublets. It is possible to use in particular the Lewis acids cited in the work edited by GA OLAH "Friedel-Crafts and related Reactions", volume I, pages 191 to 197 (1963).
Les acides de Lewis qui peuvent être mis en oeuvre dans le mélange réactionnel sont choisis parmi les composés des éléments des groupes Ib, llb, lila, lllb, IVa, IVb, Va, Vb, Vlb, Vllb et VIII de la Classification périodique des éléments, telle que publiée dans Handbook of chemistry and physics, 51st Edition (1970-1971) of The Chemical Rubber Co, dans la mesure où lesdits composés sont au moins partiellement solubles et stables dans l'eau ou plus généralement dans la solution aqueuse à traiter. Ces composés sont le plus souvent, mais de manière non limitative, des sels, notamment des halogénures, de préférence chlorures et bromures, des sulfates, des nitrates, des sulfonates, notamment des trifluorométhanesulfonates, des carboxylates, des acétyiacétonates, des tétrafluoroborates et des phosphates.The Lewis acids which can be used in the reaction mixture are chosen from the compounds of the elements of groups Ib, llb, lila, IIIb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the Periodic Table of Elements , as published in Handbook of chemistry and physics, 51st Edition (1970-1971) of The Chemical Rubber Co, insofar as said compounds are at least partially soluble and stable in water or more generally in the aqueous solution to be treated . These compounds are most often, but not limited to, salts, especially halides, preferably chlorides and bromides, sulfates, nitrates, sulfonates, especially trifluoromethanesulfonates, carboxylates, acetyiacetonates, tetrafluoroborates and phosphates .
A titre d'exemples non limitatifs de tels acides de Lewis, on peut citer le chlorure de zinc, le bromure de zinc, l'iodure de zinc, le trifluorométhanesutfonate de zinc, l'acétate de zinc, le nitrate de zinc, le tétrafluoroborate de zinc, le chlorure de manganèse, le bromure de manganèse, le chlorure de nickel, le bromure de nickel, le cyanure de nickel, l'acétylacétonate de nickel, le chlorure de cadmium, le bromure de cadmium, le chlorure stanneux, le bromure stanneux, le sulfate stanneux, le tartrate stanneux, les chlorures, bromures, sulfates, nitrates, carboxylates ou trifluorométhane¬ sulfonates des éléments des terres rares comme le lanthane, le cérium, le praséodyme, le néodyme, le samarium, l'europium, le gadoiinium, le terbium, le dysprosium, l'holmium, Perbium, le thulium, l'ytterbium et le lutétium, le chlorure de cobalt, le chlorure ferreux, le chlorure d'yttrium. On peut bien entendu mettre en oeuvre des mélanges de plusieurs acides deBy way of nonlimiting examples of such Lewis acids, mention may be made of zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesutfonate, zinc acetate, zinc nitrate, tetrafluoroborate zinc, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, bromide stannous, stannous sulfate, stannous tartrate, chlorides, bromides, sulfates, nitrates, carboxylates or trifluoromethane¬ sulfonates of rare earth elements like lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadoiinium, terbium, dysprosium, holmium, Perbium, thulium, ytterbium and lutetium, cobalt chloride, ferrous chloride, yttrium chloride. It is of course possible to use mixtures of several acids of
Lewis.Lewis.
Parmi les acides de Lewis qui peuvent être utilisés, on peut citer tout particulièrement le chlorure de zinc, le bromure de zinc, le sulfate de zinc, le tétrafluoroborate de zinc, le chlorure stanneux, le bromure stanneux, les mélanges chlorure de zinc/chlorure stanneux, le chlorure de nickel, le bromure de nickel, l'acétylacétonate de nickel.Among the Lewis acids which can be used, mention may be made most particularly of zinc chloride, zinc bromide, zinc sulfate, zinc tetrafluoroborate, stannous chloride, stannous bromide, zinc chloride / chloride mixtures stannous, nickel chloride, nickel bromide, nickel acetylacetonate.
L'acide de Lewis mis en oeuvre représente généralement de 0 à 50 moles par mole de composé de métal de transition, plus particulièrement de composé du nickel, et de préférence de 0 à 10 moles par mole. Une variante intéressante du procédé de l'invention consiste à régénérer un catalyseur usé, c'est-à-dire un catalyseur ayant servi et étant devenu au moins partiellement inactif. Ainsi, un catalyseur à base de phosphine hydrosoluble monodentate ou bidentate et d'un métal de transition au degré d'oxydation 0 ou 1 ,
contenant aussi éventuellement un ou plusieurs acides de Lewis, utilisé dans la réaction d'hydrocyanation du butadiène et/ou de pentène-nitriles se désactive progressivement, en particulier par oxydation du métal de transition. Celui-ci, et plus particulièrement le nickel, est transformé au moins en partie en cyanure. En fin de réaction d'hydrocyanation, la phase aqueuse contenant notamment la phosphine hydrosoluble monodentate ou bidentate et le composé du métal de transition au moins partiellement à un degré d'oxydation supérieur à 0, peut être aisément séparée de la phase organique. Cette phase aqueuse peut contenir des quantités variables de composés initialement introduits comme le butadiène et/ou les pentène-nitriles ou formés en cours de réaction comme l'adiponitrile, le méthyl-glutaronitrile, l'éthyl-succinonitrile, les pentène-nitriles, les méthylbutène-nitriles. La phase aqueuse est traitée comme décrit précédemment afin de régénérer le catalyseur par réduction du métal de transition se trouvant à un degré d'oxydation supérieur à 0.The Lewis acid used generally represents from 0 to 50 moles per mole of transition metal compound, more particularly of nickel compound, and preferably from 0 to 10 moles per mole. An interesting variant of the process of the invention consists in regenerating a spent catalyst, that is to say a catalyst which has been used and which has become at least partially inactive. Thus, a catalyst based on water-soluble phosphine monodentate or bidentate and a transition metal with the oxidation state 0 or 1, optionally also containing one or more Lewis acids, used in the hydrocyanation reaction of butadiene and / or pentene-nitriles is gradually deactivated, in particular by oxidation of the transition metal. This, and more particularly nickel, is transformed at least in part into cyanide. At the end of the hydrocyanation reaction, the aqueous phase containing in particular the water-soluble phosphine monodentate or bidentate and the compound of the transition metal at least partially at a degree of oxidation greater than 0, can be easily separated from the organic phase. This aqueous phase can contain variable amounts of compounds initially introduced such as butadiene and / or pentene-nitriles or formed during the reaction such as adiponitrile, methyl-glutaronitrile, ethyl-succinonitrile, pentene-nitriles, methylbutene-nitriles. The aqueous phase is treated as described above in order to regenerate the catalyst by reduction of the transition metal which is at a degree of oxidation greater than 0.
Les exemples qui suivent illustrent l'invention.The following examples illustrate the invention.
Abréviations utilisées :Abbreviations used:
3PN = pentène-3 nitrile3PN = pentene-3 nitrile
ADN = adiponitrileDNA = adiponitrile
RT = sélectivité en un composé obtenu par rapport au composé de départ transformé t.o. = tum-over = nombre de mmol de dinitriles formés par mmol de Ni(0) engagéRT = selectivity in a compound obtained compared to the transformed starting compound t.o. = tum-over = number of mmol of dinitriles formed per mmol of Ni (0) used
COD = cyclo-octadiène.COD = cyclo-octadiene.
Exemples 1 à 10 : réduction de Ni(CN)2 sur catalyseur hétérogèneExamples 1 to 10: reduction of Ni (CN) 2 on a heterogeneous catalyst
On charge dans une ampoule de verre de 5 ml :The following are loaded into a 5 ml glass ampoule:
- le catalyseur d'hydrogénation (10 % molaire en métal par rapport au Ni(CN)2 à réduire) (masse indiquée dans le tableau ci-après),the hydrogenation catalyst (10 mol% of metal relative to the Ni (CN) 2 to be reduced) (mass indicated in the table below),
- 2,4 g d'une solution aqueuse de Ni(CN)2 (0,127 mol/kg), de triphénylphosphinetrisulfonate de Na (TPPTSNa3) (0,5 mol/kg) et de ZnCl2 (0,41 mol/kg),2.4 g of an aqueous solution of Ni (CN) 2 (0.127 mol / kg), of triphenylphosphinetrisulfonate Na (TPPTSNa3) (0.5 mol / kg) and of ZnCl2 (0.41 mol / kg),
- 100 μl de pentène-3 nitrile (3PN) (0,42 mol/kg). (Ces concentrations sont exprimées par rapport à l'ensemble du mélange réactionnel)
L'ampoule est placée dans un autoclave qui est pressurisé à 50 bar d'hydrogène et chauffé à 100°C pendant 1 heure. En fin d'essai, le réacteur est décomprimé et l'analyse de la solution aqueuse est réalisée par polarographie. La concentration en nickel (0) est calculée par la différence entre la concentration en nickel total et la concentration en nickel (II) résiduel.- 100 μl of pentene-3 nitrile (3PN) (0.42 mol / kg). (These concentrations are expressed relative to the entire reaction mixture) The ampoule is placed in an autoclave which is pressurized to 50 bar of hydrogen and heated at 100 ° C for 1 hour. At the end of the test, the reactor is decompressed and the analysis of the aqueous solution is carried out by polarography. The nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration.
Tableau 1Table 1
Exemple 11 : réduction de Ni(CN)2 sur Pt/C et hydrocyanation du pentène-3 nitrileExample 11: reduction of Ni (CN) 2 on Pt / C and hydrocyanation of pentene-3 nitrile
a) préparation du catalyseura) preparation of the catalyst
On charge dans une ampoule de verre de 125 ml :The following are loaded into a 125 ml glass ampoule:
- 60 g d'une solution aqueuse de Ni(CN)2 (0,135 mol/kg) dans laTPPTSNa3 (0,5 mol/kg)- 60 g of an aqueous solution of Ni (CN) 2 (0.135 mol / kg) in TPPTSNa3 (0.5 mol / kg)
- 3,39 g de ZnCl2 (24,9 mmol de Zn)- 3.39 g of ZnCl2 (24.9 mmol of Zn)
- 6,25 g de Pt/C (0,8 mmol de Pt)- 6.25 g Pt / C (0.8 mmol Pt)
- 1 g de pentène-3 nitrile (12,3 mmol).- 1 g of pentene-3 nitrile (12.3 mmol).
L'ampoule est placée dans un autoclave qui est pressurisé à 50 bar d'hydrogène et chauffé à 100°C pendant 1 heure. En fin d'essai, le réacteur est décomprimé et l'analyse polarographique de la solution aqueuse indique une concentration en nickel (0) de 0,051 mol/kg (= solution 11a).
b) test de la solution 11a en hydrocyanation du pentène-3 nitrileThe ampoule is placed in an autoclave which is pressurized to 50 bar of hydrogen and heated at 100 ° C for 1 hour. At the end of the test, the reactor is decompressed and the polarographic analysis of the aqueous solution indicates a nickel (0) concentration of 0.051 mol / kg (= solution 11a). b) test of solution 11a in hydrocyanation of pentene-3 nitrile
Tableau 2Table 2
Conditions opératoires du test d'hydrocyanation : 3PN = 300 mmol, 65°C, 3 h. CE1* = essai comparatif avec un catalyseur préparé par échange des iigands COD de Ni(COD)2 par TPPTSNa3 + ZnCI2 (0,5 mol/kg).Operating conditions of the hydrocyanation test: 3PN = 300 mmol, 65 ° C, 3 h. CE1 * = comparative test with a catalyst prepared by exchange of the COD iigands of Ni (COD) 2 by TPPTSNa 3 + ZnCI 2 (0.5 mol / kg).
CE2* = essai comparatif avec une solution de Ni(CN)2(TPPTSNa3)2 + ZnCl2 (0,5mol/kg) non traitée par l'hydrogène.CE2 * = comparative test with a solution of Ni (CN) 2 (TPPTSNa3) 2 + ZnCl2 (0.5mol / kg) not treated with hydrogen.
Exemples 12 à 16 : Réduction de Ni(CN)2 en phase homogèneExamples 12 to 16: Reduction of Ni (CN) 2 in the homogeneous phase
On charge dans une ampoule de verre de 5 ml :The following are loaded into a 5 ml glass ampoule:
- 2,4 g d'une solution aqueuse contenant Ni(CN)2 (0,09 mol/kg), Ni(0) (0,03 mol/kg) et TPPTSNa3 (0,5 mol/kg), - éventuellement un dérivé du zinc (voir tableau 3),- 2.4 g of an aqueous solution containing Ni (CN) 2 (0.09 mol / kg), Ni (0) (0.03 mol / kg) and TPPTSNa 3 (0.5 mol / kg), - possibly a zinc derivative (see Table 3),
- 25 μl de pentène-3 nitrile (0,25 mmol).- 25 μl of pentene-3 nitrile (0.25 mmol).
L'ampoule est placée dans un autoclave qui est pressurisé à 100 bar d'hydrogène et chauffé à 100°C (durée indiquée dans tableau 3). En fin d'essai, l'autoclave est décomprimé et l'analyse de la solution aqueuse est réalisée par polarographie. La concentration en nickel (0) est calculée par la différence entre la concentration en nickel total et la concentration en nickel (II) résiduel.The vial is placed in an autoclave which is pressurized to 100 bar of hydrogen and heated to 100 ° C (duration indicated in table 3). At the end of the test, the autoclave is decompressed and the analysis of the aqueous solution is carried out by polarography. The nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration.
Tableau 3
Exemple 17 : réduction de Ni(CN)2 en phase homogène et hydrocyanation du pentène-3 nitrileTable 3 Example 17: reduction of Ni (CN) 2 in homogeneous phase and hydrocyanation of pentene-3 nitrile
a) préparation du catalyseura) preparation of the catalyst
On charge dans une ampoule de verre de 125 ml :The following are loaded into a 125 ml glass ampoule:
- 45 g d'une solution aqueuse de Ni(CN)2 (0,135 mol/kg) dans la TPPTSNa3 (0,5 mol/kg)- 45 g of an aqueous solution of Ni (CN) 2 (0.135 mol / kg) in TPPTSNa3 (0.5 mol / kg)
- 15 g d'une solution aqueuse de Ni(0) (0,11 mol/kg) dans ia TPPTSNa3 (0,5 mol/kg)- 15 g of an aqueous solution of Ni (0) (0.11 mol / kg) in ia TPPTSNa3 (0.5 mol / kg)
- 2 g de ZnCl2 (14,7 mmol de Zn)- 2 g of ZnCl2 (14.7 mmol of Zn)
- 0,6 g de pentène-3 nitrile (7,4 mmol).- 0.6 g of pentene-3 nitrile (7.4 mmol).
L'ampoule est placée dans un autoclave qui est pressurisé à 100 bar d'hydrogène et chauffé à 100°C pendant 1 heure. En fin d'essai, l'autoclave est décomprimé et l'analyse polarographique de la solution aqueuse indique une concentrattion en nickel (0) de 0,078 mol/kg (= solution 17a).The vial is placed in an autoclave which is pressurized to 100 bar of hydrogen and heated at 100 ° C for 1 hour. At the end of the test, the autoclave is decompressed and the polarographic analysis of the aqueous solution indicates a concentration of nickel (0) of 0.078 mol / kg (= solution 17a).
b) test de la solution 17a en hydrocyanation du pentène-3 nitrileb) test of solution 17a in hydrocyanation of pentene-3 nitrile
Tableau 4Table 4
Conditions opératoires du test d'hydrocyanation : 3PN = 300 mmol, 65°C, 3 h. CE3* = essai comparatif avec un catalyseur préparé par échange des Iigands COD de Ni(COD)2 par la TPPTSNa3 + ZnCI2 (0,5 mol/kg).Operating conditions of the hydrocyanation test: 3PN = 300 mmol, 65 ° C, 3 h. CE3 * = comparative test with a catalyst prepared by exchange of IOD CODs of Ni (COD) 2 with TPPTSNa 3 + ZnCI 2 (0.5 mol / kg).
CE4* = essai comparatif avec une solution de Ni(CN)2(TPPTSNa3)2 + ZnCl2 (0,5mol/kg) non traitée par l'hydrogène.
Exemples 18 à 20 : réduction de Ni(CN)2 sur catalyseur hétérogèneCE4 * = comparative test with a solution of Ni (CN) 2 (TPPTSNa3) 2 + ZnCl2 (0.5mol / kg) not treated with hydrogen. Examples 18 to 20: reduction of Ni (CN) 2 on a heterogeneous catalyst
On charge dans une ampoule de verre de 5 ml :The following are loaded into a 5 ml glass ampoule:
- le catalyseur d'hydrogénation (masse indiquée dans le tableau 5 ci-après), - 2,2 g d'une solution aqueuse de Ni(CN)2 (0,12 à 0,13 mol/kg), de triphénylphosphinetrisulfonate de Na (TPPTSNa3) (0,5 mol/kg) et de ZnCl2 (0,100 g),- the hydrogenation catalyst (mass indicated in Table 5 below), - 2.2 g of an aqueous solution of Ni (CN) 2 (0.12 to 0.13 mol / kg), of triphenylphosphinetrisulfonate Na (TPPTSNa3) (0.5 mol / kg) and ZnCl2 (0.100 g),
- 100 μl de pentène-3 nitrile (3PN) (0,42 mol/kg). (Ces concentrations sont exprimées par rapport à l'ensemble du mélange réactionnel)- 100 μl of pentene-3 nitrile (3PN) (0.42 mol / kg). (These concentrations are expressed relative to the entire reaction mixture)
L'ampoule est placée dans un autoclave qui est pressurisé à 100 bar d'hydrogène et agité à température ambiante (environ 25°C) pendant 1 heure. En fin d'essai, le réacteur est décomprimé et l'analyse de la solution aqueuse est réalisée par poiarographie. La concentration en nickel (0) est calculée par ta différence entre la concentration en nickel total et la concentration en nickel (II) résiduel. On n'observe aucun précipité de nickel et dans chaque essai la quantité du nickel total dosé correspond, aux précisions près de l'analyse, à la quantité introduite au début de l'essai.The ampoule is placed in an autoclave which is pressurized to 100 bar of hydrogen and stirred at room temperature (about 25 ° C) for 1 hour. At the end of the test, the reactor is decompressed and the analysis of the aqueous solution is carried out by poiarography. The nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration. No nickel precipitate is observed and in each test the quantity of total nickel assayed corresponds, with the details close to the analysis, to the quantity introduced at the start of the test.
Tableau 5Table 5
Exemples 21 à 25 : réduction de Ni(CN>2 sur catalyseur hétérogèneExamples 21 to 25: reduction of Ni (CN> 2 on heterogeneous catalyst
On charge dans une ampoule de verre de 5 ml : - le catalyseur d'hydrogénation (nature et masse indiquées dans le tableau 6 ci-après),The following are loaded into a 5 ml glass ampoule: the hydrogenation catalyst (nature and mass indicated in table 6 below),
- 2,2 g d'une solution aqueuse de Ni(CN)2 (0,112 mol/kg) et de triphénylphosphinetrisulfonate de Na (TPPTSNa3) (0,5 mol/kg), - 130 à 150 μl de pentène-3 nitrile (3PN). (Ces concentrations sont exprimées par rapport à l'ensemble du mélange réactionnel)
L'ampoule est placée dans un autoclave qui est pressurisé à 100 bar d'hydrogène et agité à différentes températures (indiquées dans le tableau 6 ci-après sous l'abréviation T°C) pendant différentes durées. En fin d'essai, le réacteur est décomprimé et l'analyse de la solution aqueuse est réalisée par polarographie. La concentration en nickel (0) est calculée par la différence entre la concentration en nickel total et la concentration en nickel (II) résiduel.- 2.2 g of an aqueous solution of Ni (CN) 2 (0.112 mol / kg) and of sodium triphenylphosphinetrisulfonate (TPPTSNa3) (0.5 mol / kg), - 130 to 150 μl of pentene-3 nitrile ( 3PN). (These concentrations are expressed relative to the entire reaction mixture) The bulb is placed in an autoclave which is pressurized to 100 bar of hydrogen and stirred at different temperatures (indicated in table 6 below under the abbreviation T ° C) for different durations. At the end of the test, the reactor is decompressed and the analysis of the aqueous solution is carried out by polarography. The nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration.
On n'observe aucun précipité de nickel (sauf un très léger dans l'exemple 23 correspondant à moins de 0,003 mol/kg) et dans chaque essai la quantité du nickel total dosé correspond, aux précisions près de l'analyse, à la quantité introduite au début de l'essai.No nickel precipitate is observed (except for a very slight precipitate in Example 23 corresponding to less than 0.003 mol / kg) and in each test the quantity of total nickel dosed corresponds, with the details close to the analysis, to the quantity introduced at the start of the test.
Tableau 6
Table 6
Claims
REVENDICATIONS
1) - Procédé de préparation de catalyseurs comportant au moins un métal de transition au degré d'oxydation 0 ou 1 , associé à au moins une phosphine hydrosoluble monodentate ou bidentate, caractérisé en ce qu'il consiste à traiter par l'hydrogène, en l'absence de monoxyde de carbone, une solution aqueuse contenant au moins un composé d'un métal de transition et au moins une phosphine hydrosoluble monodentate ou bidentate.1) - Process for the preparation of catalysts comprising at least one transition metal with an oxidation state of 0 or 1, associated with at least one water-soluble phosphine monodentate or bidentate, characterized in that it consists in treating with hydrogen, the absence of carbon monoxide, an aqueous solution containing at least one compound of a transition metal and at least one water-soluble phosphine monodentate or bidentate.
2) - Procédé selon ta revendication 1, caractérisé en ce que la phosphine hydrosoluble mise en oeuvre est une phosphine monodentate répondant à la formule générale (I) :2) - Method according to your claim 1, characterized in that the water-soluble phosphine used is a phosphine monodentate corresponding to the general formula (I):
P (Ar1)a (Ar2)b (Ar3)c (D1)d (D2)β (D3)f (DP (Ar1) a (Ar2) b (Ar3) c (D1) d (D2) β (D3) f (D
dans laquelle :in which :
- AM, Ar2 et Ar3, identiques ou différents, représentent des groupes aryle ou aryle comportant un ou plusieurs substituants tels que :- AM, Ar2 and Ar3, identical or different, represent aryl or aryl groups comprising one or more substituents such as:
- radical alkyle ou alcoxy ayant 1 à 4 atomes de carbone, - atome d'halogène,- alkyl or alkoxy radical having 1 to 4 carbon atoms, - halogen atom,
- groupe nitrile,- nitrile group,
- groupe nitro,- nitro group,
- groupe hydrophile comme :- hydrophilic group such as:
-COOM, -SO3M, -PO3M, M représentant un reste cationique minéral ou organique choisi parmi le proton, les cations dérivés des métaux alcalins ou alcalino- terreux, les cations ammonium -N(R)4 dans la formule desquels les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, les autres cations dérivés de métaux dont les sels des acides arylcarboxyliques, des acides arylsulfoniques ou des acides arylphosphoniques sont solubles dans l'eau,-COOM, -SO3M, -PO3M, M representing an inorganic or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals in which the salts of arylcarboxylic acids, arylsulfonic acids or arylphosphonic acids are soluble in water,
•N(R)3 dans la formule duquel les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone,N (R) 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms,
-OH,-OH,
a, b et c représentent indépendamment les uns des autres 0 ou 1 ,
- D1, D2, D3, identiques ou différents, représentent un groupe alkyle, un groupe cycloalkyle, un groupe alkyle ou cycloalkyle comportant un ou plusieurs substituants tels que :a, b and c represent independently of each other 0 or 1, - D1, D2, D3, identical or different, represent an alkyl group, a cycloalkyl group, an alkyl or cycloalkyl group comprising one or more substituents such as:
- radical alcoxy ayant 1 à 4 atomes de carbone, - atome d'halogène,- alkoxy radical having 1 to 4 carbon atoms, - halogen atom,
- groupe nitrile,- nitrile group,
- groupe nitro,- nitro group,
- groupe hydrophile comme :- hydrophilic group such as:
-COOM, -SO3M, -PO3M, M représentant un reste cationique minéral ou organique choisi parmi le proton, les cations dérivés des métaux alcalins ou alcalino- terreux, les cations ammonium -N(R)4 dans la formule desquels les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, les autres cations dérivés de métaux dont les sels des acides carboxyliques, des acides sulfoniques ou des acides phosphoniques sont solubles dans l'eau,-COOM, -SO3M, -PO3M, M representing an inorganic or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals whose salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water,
-N(R)3 dans la formule duquel les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone,-N (R) 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms,
-OH - d, e et f représentent indépendamment les uns des autres 0 ou 1 ,-OH - d, e and f independently represent 0 or 1,
- la somme (a+b+c+d+e+f) est égale à 3- the sum (a + b + c + d + e + f) is equal to 3
ou bidentate répondant à la formule générale (II) :or bidentate corresponding to the general formula (II):
(AM)a (Ar2)b (D1)d (D2)e P-L-P (AM)g (Ar2)n (D1)j (D2)j (II)(AM) a (Ar2) b (D1) d (D2) e PLP (AM) g (Ar2) n (D1) j (D2) j (II)
dans laquelle :in which :
- AM, Ar2, D1 et D2 ont les significations indiquées précédemment pour ia formule (I), • a, b, d, e, g, h, i et j représentent chacun 0 ou 1, - ia somme (a+b+d+e) est égale à 2,- AM, Ar2, D1 and D2 have the meanings indicated above for ia formula (I), • a, b, d, e, g, h, i and j each represent 0 or 1, - ia sum (a + b + d + e) is equal to 2,
- la somme (g+h+i+j) est égale à 2,- the sum (g + h + i + j) is equal to 2,
- L représente un lien vaientiel simple ou un radical hydrocarboné divalent tel qu'un radical alkylene, un radical cycloalkylène, un radical arylène, un radical dérivant d'un hétérocycle comportant un ou deux atomes d'oxygène, d'azote ou de soufre dans le cycle, ces différents radicaux cycliques étant liés directement à l'un des atomes de phosphore ou aux deux atomes de phosphore ou étant lié à l'un des atomes de phosphore ou aux deux par l'intermédiaire d'un radical alkylene linéaire ou ramifié ayant de 1 à 4 atomes de carbone, le ou les cycles éventuellement parties du radical divalent
L pouvant comporter un ou plusieurs substituants tels que ceux définis pour AM, Ar2, Ar3, D1, D2 et D3.- L represents a simple supply link or a divalent hydrocarbon radical such as an alkylene radical, a cycloalkylene radical, an arylene radical, a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being linked directly to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one or both of the phosphorus atoms via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may include one or more substituents such as those defined for AM, Ar2, Ar3, D1, D2 and D3.
3) - Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le composé de métal de transition est choisi parmi les composés du nickel, du cobalt, du fer, du palladium, du platine, du rhodium et de l'iridium, solubles dans l'eau ou capables de passer en solution dans les conditions de la réaction.3) - Method according to one of claims 1 or 2, characterized in that the transition metal compound is chosen from compounds of nickel, cobalt, iron, palladium, platinum, rhodium and iridium, soluble in water or capable of passing into solution under the conditions of the reaction.
4) - Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le composé de métal de transition est choisi parmi les composés du nickel tels que les carboxylates de nickel, notamment acétate, formiate et citrate, carbonate de nickel, bicarbonate de nickel, borate de nickel, bromure de nickel, chlorure de nickel, iodure de nickel, thiocyanate de nickel, cyanure de nickel, hydroxyde de nickel, hydrophosphite de nickel, phosphite de nickel, phosphate de nickel et ses dérivés, nitrate de nickel, sulfate de nickel, sulfite de nickel, aryl- et alkyl-sulfonates de nickel.4) - Method according to one of claims 1 to 3, characterized in that the transition metal compound is chosen from nickel compounds such as nickel carboxylates, in particular acetate, formate and citrate, nickel carbonate, bicarbonate nickel, nickel borate, nickel bromide, nickel chloride, nickel iodide, nickel thiocyanate, nickel cyanide, nickel hydroxide, nickel hydrophosphite, nickel phosphite, nickel phosphate and its derivatives, nickel nitrate, nickel sulfate, nickel sulfite, nickel aryl and alkyl sulfonates.
5) - Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la réduction par l'hydrogène est réalisée en milieu homogène.5) - Method according to one of claims 1 to 4, characterized in that the reduction by hydrogen is carried out in a homogeneous medium.
6) - Procédé selon la revendication 5, caractérisé en ce que la réaction est conduite en présence d'un catalyseur homogène soluble dans le milieu réactionnel.6) - Method according to claim 5, characterized in that the reaction is carried out in the presence of a homogeneous catalyst soluble in the reaction medium.
7) - Procédé selon la revendication 6, caractérisé en ce que le catalyseur homogène est chois) parmi les complexes phosphine hydrosoluble de rhodium, iridium, cobalt, ruthénium, nickel ou palladium.7) - Process according to claim 6, characterized in that the homogeneous catalyst is chosen) from the water-soluble phosphine complexes of rhodium, iridium, cobalt, ruthenium, nickel or palladium.
8) - Procédé selon l'une des revendications 1 à 4, caractérisé en ce que ia réduction par l'hydrogène est conduite en milieu hétérogène en présence d'un catalyseur hétérogène insoluble dans le milieu réactionnel.8) - Method according to one of claims 1 to 4, characterized in that ia reduction by hydrogen is carried out in a heterogeneous medium in the presence of a heterogeneous catalyst insoluble in the reaction medium.
9) - Procédé seion la revendication 8, caractérisé en ce que le catalyseur hétérogène est choisi parmi les différents métaux du groupe VIII de la Classification périodique des Eléments ou les composés de ces métaux, déposés sur un support ou non.9) - Method according to claim 8, characterized in that the heterogeneous catalyst is chosen from the various metals of group VIII of the Periodic Table of Elements or the compounds of these metals, deposited on a support or not.
10) - Procédé selon l'une des revendications 8 ou 9, caractérisé en ce que le catalyseur hétérogène est choisi parmi le platine, le palladium, le ruthénium et le nickel.
11) - Procédé selon l'une des revendications 1 à 10, caractérisé en ce que la phosphine hydrosoluble est choisie parmi les phosphines de formule (I) ou de formule (II) dans lesquelles AM, Ar2 et Ar3 sont des groupes phényle ou des groupes phényles comportant un ou deux substituants tels que définis précédemment, D1, D2 et D3 représentent un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle ayant 5 à 8 atomes de carbone, un groupe alkyle ayant de 1 à 6 atomes de carbone ou cycloalkyle ayant 5 à 8 atomes de carbone comportant un ou plusieurs substituants tels que définis précédemment, L est un lien vaientiel simple, un radical alkylene ayant de 1 à 6 atomes de carbone, un radical cycloalkylène monocyclique ou bicyclique ayant de 4 à 12 atomes de carbone, un radical phénylène, un radical diphénylène, un radical naphtylène, un radical dinaphtylène.un radical dérivant d'un hétérocycle comportant un ou deux atomes d'oxygène, d'azote ou de soufre dans le cycle, ces différents radicaux cycliques étant liés directement à l'un des atomes de phosphore ou aux deux atomes de phosphore ou étant lié à l'un des atomes de phosphore ou aux deux par l'intermédiaire d'un radical alkylene linéaire ou ramifié ayant de 1 à 4 atomes de carbone, le ou les cycles éventuellement parties du radical divalent L pouvant comporter un ou plusieurs substituants tels que groupe alkyle ayant 1 à 4 atomes de carbone.10) - Method according to one of claims 8 or 9, characterized in that the heterogeneous catalyst is chosen from platinum, palladium, ruthenium and nickel. 11) - Method according to one of claims 1 to 10, characterized in that the water-soluble phosphine is chosen from the phosphines of formula (I) or of formula (II) in which AM, Ar2 and Ar3 are phenyl groups or phenyl groups having one or two substituents as defined above, D1, D2 and D3 represent an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl group having from 1 to 6 atoms of carbon or of cycloalkyl having 5 to 8 carbon atoms comprising one or more substituents as defined above, L is a simple liquid bond, an alkylene radical having from 1 to 6 carbon atoms, a monocyclic or bicyclic cycloalkylene radical having from 4 to 12 carbon atoms, a phenylene radical, a diphenylene radical, a naphthylene radical, a dinaphthylene radical. A radical derived from a heterocycle comprising one or two oxygen, nitrogen or so atoms ufre in the cycle, these different cyclic radicals being linked directly to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one or both of the phosphorus atoms via a linear alkylene radical or branched having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as an alkyl group having 1 to 4 carbon atoms.
12) - Procédé selon l'une des revendications 1 à 11, caractérisé en ce que la phosphine hydrosoluble est choisie parmi les phosphines de formule (I) ou de formule12) - Method according to one of claims 1 to 11, characterized in that the water-soluble phosphine is chosen from the phosphines of formula (I) or of formula
(II) dans lesquelles:(II) in which:
- le ou les substituants de Ar, Ar2 et Ar3, identiques ou différents, représentent des groupes tels que :- the substituent (s) of Ar, Ar2 and Ar3, identical or different, represent groups such as:
- radical alkyle ou alcoxy ayant 1 à 2 atomes de carbone, - atome de chlore,- alkyl or alkoxy radical having 1 to 2 carbon atoms, - chlorine atom,
- groupe hydrophile comme :- hydrophilic group such as:
-COOM, -SO3M, -PO3M, M représentant un reste cationique minéral ou organique choisi parmi le proton, les cations dérivés du sodium, du potassium, du calcium ou du baryum, les cations ammonium, tetraméthylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, les cations dérivés du zinc, du plomb ou de l'étain,-COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, cations derived from sodium, potassium, calcium or barium, ammonium cations, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cations derived from zinc, lead or tin,
-N(R)3 dans la formule duquel les symboles R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, -OH globalement deux au moins desdits substituants de AM, Ar2, Ar3, D1, D2 et D3 pour les phosphines de formule (I) et de AM, Ar2, D1 et D2 pour les phosphines de formule (II) étant un groupe hydrophile tel que défini précédemment.
13) - Procédé selon l'une des revendications 1 à 12, caractérisé en ce que la phosphine hydrosoluble est choisie parmi les sels alcalins ou alcalino-terreux, les sels d'ammonium, les sels d'ammonium quaternaire des (sulfo-3 méthyl-4 phenyl) di (méthyl- 4 phényl)-phosphine ; (sulfo-3 méthoxy-4 phenyl) di(méthoxy-4 phényl)-phosphine ; (sutfo-3 chloro-4 phenyl) di(ch!oro-4 phényl)-phosphine ; di(sulfo-3 phenyl) phényl- phosphine ; di(sulfo-4 phenyl) phényl-phosphine ; di(sulfo-3 méthyl-4 phenyl) (méthyl-4 phényl)-phosphine ; di(suifo-3 méthoxy-4 phenyl) (méthoxy-4 phenyl) phosphine ; di(sulfo-3 chloro-4 phenyl) (chloro-4 phenyl) phosphine ; tri(sulfo-3 phényl)-phosphine ; tri(sulfo-4 phényl)-phosphine ; (tri(sulfo-3 méthyl-4 phéπyl)-phosphine ; tri(sulfo-3, méthoxy-4 phényl)-phosphine ; tri(sulfo-3 chloro-4 phényl)-phosphine ; (sulfo-2 méthyl-4 phenyl) (sulfo-3, méthyl-4 phenyl) (disulfo-3,5 méthyl-4 phényl)-phosphine ; (sulfo-3 phenyl) (sulfo-3 chloro-4 phenyl) (disulfo-3,5 chioro-4 phényl)-phosphine, la tris(hydroxyméthyl) phosphine, la tris(2-hydroxyéthyl) phosphine, la tris(3-hydroxypropyl) phosphine, la tris(2-carboxyméthyl) phosphine, le sel de sodium de la tris(3-carboxylatophényl) phosphine, la tris(3-carboxyéthyl) phosphine, l'iodure de la tris(4-triméthylammoniumphényl) phosphine, le sel de sodium de la tris(2-phosphonatoéthyl) phosphine, la bis(2-carboxyéthyl) phenyl phosphine, l'hydroxyméthyl bis(2-hydroxyéthyl) phosphine, le sel de sodium de la tris(paraphosphophényl) phosphine, le sel de sodium de la bis(métasulfophényl) paracarboxyphényl phosphine, le sel de sodium de la bis(métasuifophényl) sulfo-2 éthyl phosphine.-N (R) 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH overall at least two of said substituents of AM, Ar2, Ar3, D1, D2 and D3 for the phosphines of formula (I) and of AM, Ar2, D1 and D2 for the phosphines of formula (II) being a hydrophilic group as defined above. 13) - Method according to one of claims 1 to 12, characterized in that the water-soluble phosphine is chosen from alkaline or alkaline-earth salts, ammonium salts, quaternary ammonium salts of (3-sulfo-methyl -4 phenyl) di (4-methylphenyl) -phosphine; (3-sulfo-4-methoxy phenyl) di (4-methoxy-phenyl) -phosphine; (3-chloro-4-phenyl) di (ch! oro-4-phenyl) -phosphine; di (3-sulfo phenyl) phenylphosphine; di (4-sulfo phenyl) phenyl-phosphine; di (3-sulfo-4-methylphenyl) (4-methyl-phenyl) -phosphine; di (3-sulfo-4-methoxy phenyl) (4-methoxy phenyl) phosphine; di (3-sulfo-4-chloro phenyl) (4-chloro-phenyl) phosphine; tri (3-sulfo phenyl) -phosphine; tri (4-sulfo phenyl) -phosphine; (tri (3-sulfo-4-methylphenyl) -phosphine; tri (3-sulfo-4-methoxy-phenyl) -phosphine; tri (3-sulfo-4-chloro-phenyl) -phosphine; (2-sulfo-4-methylphenyl) (3-sulfo, 4-methylphenyl) (3,5-disulfo-4-methylphenyl) -phosphine; (3-sulfo-phenyl) (3-sulfo-4-chloro phenyl) (3,5-disulfo-4-chioro-phenyl) -phosphine, tris (hydroxymethyl) phosphine, tris (2-hydroxyethyl) phosphine, tris (3-hydroxypropyl) phosphine, tris (2-carboxymethyl) phosphine, sodium salt of tris (3-carboxylatophenyl) phosphine , tris (3-carboxyethyl) phosphine, iodide of tris (4-trimethylammoniumphenyl) phosphine, sodium salt of tris (2-phosphonatoethyl) phosphine, bis (2-carboxyethyl) phenyl phosphine, hydroxymethyl bis (2-hydroxyethyl) phosphine, the sodium salt of tris (paraphosphophenyl) phosphine, the sodium salt of bis (metasulfophenyl) paracarboxyphenyl phosphine, the sodium salt of bis (metasuifophenyl) sulfo-2 ethyl phosphine.
14) - Procédé seion l'une des revendications 1 à 12, caractérisé en ce que la phosphine hydrosoluble est choisie parmi le sel de sodium du 2,2' bis[di(sulfonatophényl)phosphino]-1,1'-binaphtyl, le sel de sodium du14) - Method according to one of claims 1 to 12, characterized in that the water-soluble phosphine is chosen from the sodium salt of 2,2 'bis [di (sulfonatophenyl) phosphino] -1,1'-binaphthyl, the sodium salt
1 ,2-bis[di(sulfonatophényl)phosphinométhyl] cyclobutane (CBDTS), le 1 ,2-bis(dihydroxy- méthyl-phosphino) éthane, le 1,3-bis(dihydroxyméthylphosphino) propane, le sel de sodium du 2,2'-bis[di(sulfonatophényl)phosphinométhyl]-1 ,1'-binaphtyl.1, 2-bis [di (sulfonatophenyl) phosphinomethyl] cyclobutane (CBDTS), 1,2-bis (dihydroxy-methyl-phosphino) ethane, 1,3-bis (dihydroxymethylphosphino) propane, the sodium salt of 2, 2'-bis [di (sulfonatophenyl) phosphinomethyl] -1, 1'-binaphtyl.
15) - Procédé selon l'une des revendications 1 à 14, caractérisé en ce que la solution du composé de métal de transition à réduire comprend au moins un acide de Lewis choisi parmi les composés des éléments des groupes Ib, llb, lila, lllb, IVa, IVb, Va, Vb, Vlb, Vllb et VIII de la Classification périodique des éléments, dans la mesure où lesdits composés sont au moins partiellement solubles et stables dans l'eau ou plus généralement dans la solution aqueuse à traiter, de préférence parmi les sels, notamment les halogénures, les sulfates, les nitrates, les sulfonates, notamment les trifluorométhanesuifonates, les carboxylates, les acétylacétonates, les tétrafluoroborates et les phosphates.
16) - Procédé selon la revendication 15, caractérisé en ce que l'acide de Lewis est choisi parmi le chlorure de zinc, le bromure de zinc, l'iodure de zinc, le trifluorométhanesulfonate de zinc, l'acétate de zinc, le nitrate de zinc, le tétrafluoroborate de zinc, le chlorure de manganèse, le bromure de manganèse, le chlorure de nickel, le bromure de nickel, le cyanure de nickel, l'acétylacétonate de nickel, le chlorure de cadmium, le bromure de cadmium, le chlorure stanneux, le bromure stanneux, le sulfate stanneux, le tartrate stanneux, les chlorures, bromures, sulfates, nitrates, carboxylates ou trifluorométhanesulfonates des éléments des terres rares comme le lanthane, le cérium, le praséodyme, le néodyme, le samarium, l'europium, le gadolinium, le terbium, le dysprosium, l'holmium, l'erbium, le thulium, l'ytterbium et le lutétium, le chlorure de cobalt, le chlorure ferreux, le chlorure d'yttrium.15) - Method according to one of claims 1 to 14, characterized in that the solution of the transition metal compound to be reduced comprises at least one Lewis acid chosen from the compounds of the elements of groups Ib, llb, lila, lllb , IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the Periodic Table of the Elements, insofar as said compounds are at least partially soluble and stable in water or more generally in the aqueous solution to be treated, preferably among the salts, in particular the halides, the sulfates, the nitrates, the sulfonates, in particular the trifluoromethanesulfonates, the carboxylates, the acetylacetonates, the tetrafluoroborates and the phosphates. 16) - Method according to claim 15, characterized in that the Lewis acid is chosen from zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, nitrate zinc, zinc tetrafluoroborate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, stannous tartrate, chlorides, bromides, sulfates, nitrates, carboxylates or trifluoromethanesulfonates of rare earth elements like lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, cobalt chloride, ferrous chloride, yttrium chloride.
17) - Procédé selon l'une des revendications 15 ou 16, caractérisé en ce que l'acide de Lewis mis en oeuvre représente de 0 à 50 moles par mole de composé de métal de transition, plus particulièrement de composé du nickel, et de préférence de 0 à 10 moles par mole.17) - Method according to one of claims 15 or 16, characterized in that the Lewis acid used represents from 0 to 50 moles per mole of transition metal compound, more particularly of nickel compound, and preferably 0 to 10 moles per mole.
18) - Procédé selon l'une des revendications 1 à 17, caractérisé en ce qu'il consiste à mettre en oeuvre une solution aqueuse d'un catalyseur usé à régénérer, à base de phosphine hydrosoluble monodentate ou bidentate et d'un métal de transition, et plus particulièrement le nickel, transformé au moins en partie en cyanure, ledit catalyseur usé contenant éventuellement un ou plusieurs acides de Lewis et contenant éventuellement des quantités variables de composés comme le butadiène et/ou les pentène-nitriles ou comme l'adiponitrile, le méthyl-glutaronitrile, l'éthyl- succinonitrile, les méthylbutène-nitriles.18) - Method according to one of claims 1 to 17, characterized in that it consists in using an aqueous solution of a spent catalyst to regenerate, based on water-soluble phosphine monodentate or bidentate and a metal of transition, and more particularly nickel, transformed at least in part into cyanide, said spent catalyst optionally containing one or more Lewis acids and optionally containing variable amounts of compounds such as butadiene and / or pentene nitriles or such as adiponitrile , methyl-glutaronitrile, ethyl-succinonitrile, methylbutene-nitriles.
19) - Procédé selon l'une des revendications 1 à 18, caractérisé en ce que la réduction catalytique est effectuée sous une pression d'hydrogène mesurée à 25°C de 1 à 200 bars et à une température de 5βC à 200°C et de préférence sous une pression d'hydrogène mesurée à 25°C de 1 à 150 bars et à une température de 10 °C à 120°C.
19) - Method according to one of claims 1 to 18, characterized in that the catalytic reduction is carried out under a hydrogen pressure measured at 25 ° C from 1 to 200 bars and at a temperature of 5 β C at 200 ° C and preferably under a hydrogen pressure measured at 25 ° C from 1 to 150 bars and at a temperature from 10 ° C to 120 ° C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9515879A FR2743010B1 (en) | 1995-12-29 | 1995-12-29 | PROCESS FOR THE PREPARATION BY HYDROGENATION OF CATALYSTS BASED ON TRANSITIONAL METAL AND PHOSPHINE |
| FR9515879 | 1995-12-29 | ||
| PCT/FR1996/002023 WO1997024183A1 (en) | 1995-12-29 | 1996-12-18 | Process for the preparation by hydrogenation of catalysts based on a transition metal and phosphine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0876214A1 true EP0876214A1 (en) | 1998-11-11 |
Family
ID=9486266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96942425A Withdrawn EP0876214A1 (en) | 1995-12-29 | 1996-12-18 | Process for the preparation by hydrogenation of catalysts based on a transition metal and phosphine |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5908805A (en) |
| EP (1) | EP0876214A1 (en) |
| JP (1) | JP3320424B2 (en) |
| KR (1) | KR100482531B1 (en) |
| CN (1) | CN1099912C (en) |
| BR (1) | BR9612380A (en) |
| CA (1) | CA2240434C (en) |
| FR (1) | FR2743010B1 (en) |
| RU (1) | RU2167712C2 (en) |
| WO (1) | WO1997024183A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2787349B1 (en) * | 1998-12-22 | 2001-02-02 | Rhone Poulenc Fibres | PROCESS FOR MANUFACTURING A HYDROCYANATION CATALYST |
| FR2787786B1 (en) * | 1998-12-23 | 2001-02-02 | Rhone Poulenc Fibres | PROCESS FOR THE PREPARATION OF WATER-SOLUBLE SULPHONATED ORGANOPHOSPHORUS COMPOUNDS AND CARRYING OUT ORGANIC REACTIONS WITH BIPHASIC CATALYSIS |
| DE19947508A1 (en) * | 1999-10-01 | 2001-04-05 | Basf Ag | Activation of passivated iron to form a catalyst component, useful for hydrogenation, comprises treatment with hydrogen at elevated temperature and pressure in the presence of a nitrile compound. |
| US6215015B1 (en) * | 2000-04-17 | 2001-04-10 | General Electric Company | Catalyst composition and method for producing diaryl carbonates, using bisphosphines |
| FR2850966B1 (en) | 2003-02-10 | 2005-03-18 | Rhodia Polyamide Intermediates | PROCESS FOR PRODUCING DINITRIL COMPOUNDS |
| FR2854891B1 (en) | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | PROCESS FOR PREPARING DINITRILES |
| US7704468B1 (en) * | 2005-09-21 | 2010-04-27 | Battelle Energy Alliance, Llc | Method for forming an extraction agent for the separation of actinides from lanthanides |
| EP1948591A1 (en) | 2005-10-18 | 2008-07-30 | INVISTA Technologies S.à.r.l. | Process of making 3-aminopentanenitrile |
| BRPI0709313A2 (en) | 2006-03-17 | 2011-07-05 | Invista Tech Sarl | separation method and method for the preparation of triorganophosphites |
| US7880028B2 (en) | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
| US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US7799293B2 (en) * | 2006-09-11 | 2010-09-21 | Battelle Energy Alliance, Llc | Actinide extraction methods |
| CN101687658B (en) | 2007-05-14 | 2013-07-24 | 因温斯特技术公司 | High efficiency reactor and process |
| WO2008157218A1 (en) | 2007-06-13 | 2008-12-24 | Invista Technologies S.A.R.L. | Process for improving adiponitrile quality |
| EP2229353B1 (en) | 2008-01-15 | 2018-01-03 | INVISTA Textiles (U.K.) Limited | Hydrocyanation of pentenenitriles |
| CN101910119B (en) | 2008-01-15 | 2013-05-29 | 因温斯特技术公司 | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
| WO2009117498A2 (en) * | 2008-03-19 | 2009-09-24 | Invista Technologies S.A R.L. | Methods of making cyclododecatriene and methods of making laurolactone |
| JP5619753B2 (en) | 2008-10-14 | 2014-11-05 | インヴィスタテクノロジーズ エスアエルエル | Process for producing 2-secondary-alkyl-4,5-di- (linear-alkyl) phenols |
| CN102471218B (en) | 2009-08-07 | 2014-11-05 | 因温斯特技术公司 | Hydrogenation and esterification to form diesters |
| US8815186B2 (en) * | 2009-12-18 | 2014-08-26 | Invista North America S.A.R.L. | Nickel compositions for preparing nickel metal and nickel complexes |
| JP2013536878A (en) * | 2010-09-07 | 2013-09-26 | インヴィスタ テクノロジーズ エスアエルエル | Preparation of nickel phosphorus ligand complex |
| JP6232417B2 (en) * | 2013-03-27 | 2017-11-15 | 株式会社クラレ | Bis (6-methyl-3-sulfophenyl) phenylphosphine and its ammonium salt and process for producing them |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2338253A1 (en) * | 1976-01-13 | 1977-08-12 | Rhone Poulenc Ind | PROCESS FOR HYDROCYANATION OF UNSATURATED ORGANIC COMPOUNDS CONTAINING AT LEAST A DOUBLE ETHYLENIC BOND |
| DE3034353A1 (en) * | 1979-02-12 | 1981-03-26 | Exxon Research Engineering Co | TETRAALKYL PHOSPHONIUM SUBSTITUTED TRANSITION METAL COMPLEXES |
| GB2085874B (en) * | 1980-09-04 | 1984-08-08 | Johnson Matthey Plc | Hydroformylation of olefins |
| JPS5923858B2 (en) * | 1981-01-22 | 1984-06-05 | 三菱化学株式会社 | How to obtain rhodium complexes |
| US5091350A (en) * | 1984-03-26 | 1992-02-25 | Hoechst Aktiengesellschaft | Process for hydroformylation with rhodium catalysts and the separation of rhodium therefrom |
| DE3640614A1 (en) * | 1986-11-27 | 1988-06-09 | Ruhrchemie Ag | METHOD FOR PRODUCING ALDEHYDES |
| US4935550A (en) * | 1988-08-12 | 1990-06-19 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic metal recovery from non-polar organic solutions |
| FR2666250A1 (en) * | 1990-09-05 | 1992-03-06 | Rhone Poulenc Nutrition Animal | NOVEL CATALYSTS, PROCESS FOR THEIR PREPARATION AND THEIR USE. |
| JPH04225841A (en) * | 1990-12-27 | 1992-08-14 | Mitsubishi Kasei Corp | Method for activation of hydroformylation catalyst |
| DE4242723A1 (en) * | 1992-12-17 | 1994-06-23 | Hoechst Ag | Process for the preparation of aldehydes |
| US5290743A (en) * | 1993-03-22 | 1994-03-01 | Arco Chemical Technology L.P. | Process for regenerating a deactivated rhodium hydroformylation catalyst system |
| WO1995014659A1 (en) * | 1993-11-23 | 1995-06-01 | E.I. Du Pont De Nemours And Company | Processes and catalyst compositions for hydrocyanation of monoolefins |
| DE69414240T2 (en) * | 1994-01-20 | 1999-04-22 | Kao Corp | METHOD FOR PRODUCING A COPPER-CONTAINING HYDRATION CATALYST AND METHOD FOR PRODUCING ALCOHOL |
| TW319771B (en) * | 1994-04-05 | 1997-11-11 | Mitsubishi Chem Corp | |
| US5463166A (en) * | 1994-05-27 | 1995-10-31 | Phillips Petroleum Company | Reactivation of alkane isomerization catalysts |
| US5672798A (en) * | 1994-10-14 | 1997-09-30 | Uop | Fluidized bed solid catalyst motor fuel alkylation process |
| US5599758A (en) * | 1994-12-23 | 1997-02-04 | Goal Line Environmental Technologies | Regeneration of catalyst/absorber |
| US5599962A (en) * | 1995-01-31 | 1997-02-04 | E. I. Du Pont De Nemours And Company | Process for the preparation of ruthenium hydrogenation catalysts and products thereof |
| GB9517105D0 (en) * | 1995-08-21 | 1995-10-25 | Bp Chem Int Ltd | Catalyst compositions |
-
1995
- 1995-12-29 FR FR9515879A patent/FR2743010B1/en not_active Expired - Fee Related
-
1996
- 1996-12-18 BR BR9612380A patent/BR9612380A/en not_active Application Discontinuation
- 1996-12-18 JP JP52405897A patent/JP3320424B2/en not_active Expired - Fee Related
- 1996-12-18 EP EP96942425A patent/EP0876214A1/en not_active Withdrawn
- 1996-12-18 RU RU98114248/04A patent/RU2167712C2/en not_active IP Right Cessation
- 1996-12-18 KR KR10-1998-0704980A patent/KR100482531B1/en not_active IP Right Cessation
- 1996-12-18 CA CA002240434A patent/CA2240434C/en not_active Expired - Fee Related
- 1996-12-18 WO PCT/FR1996/002023 patent/WO1997024183A1/en not_active Application Discontinuation
- 1996-12-18 CN CN96199342A patent/CN1099912C/en not_active Expired - Fee Related
- 1996-12-27 US US08/774,910 patent/US5908805A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9724183A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2743010A1 (en) | 1997-07-04 |
| CA2240434C (en) | 2001-09-18 |
| WO1997024183A1 (en) | 1997-07-10 |
| CN1206357A (en) | 1999-01-27 |
| RU2167712C2 (en) | 2001-05-27 |
| JPH11507297A (en) | 1999-06-29 |
| KR19990076853A (en) | 1999-10-25 |
| CA2240434A1 (en) | 1997-07-10 |
| KR100482531B1 (en) | 2005-06-16 |
| CN1099912C (en) | 2003-01-29 |
| JP3320424B2 (en) | 2002-09-03 |
| BR9612380A (en) | 1999-07-13 |
| FR2743010B1 (en) | 1998-02-20 |
| US5908805A (en) | 1999-06-01 |
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