WO2013181092A1 - Hydrolysis catalyst and process - Google Patents
Hydrolysis catalyst and process Download PDFInfo
- Publication number
- WO2013181092A1 WO2013181092A1 PCT/US2013/042613 US2013042613W WO2013181092A1 WO 2013181092 A1 WO2013181092 A1 WO 2013181092A1 US 2013042613 W US2013042613 W US 2013042613W WO 2013181092 A1 WO2013181092 A1 WO 2013181092A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- cycloalkyl
- alkoxy
- cycloalkoxy
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 190
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 184
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 183
- 230000008569 process Effects 0.000 title claims abstract description 175
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 239000003446 ligand Substances 0.000 claims abstract description 484
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 191
- 239000000203 mixture Substances 0.000 claims abstract description 162
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000011574 phosphorus Substances 0.000 claims abstract description 131
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 110
- 239000001301 oxygen Substances 0.000 claims abstract description 109
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 34
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 150000003624 transition metals Chemical class 0.000 claims abstract description 22
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 584
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 463
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 368
- 125000003545 alkoxy group Chemical group 0.000 claims description 341
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 334
- -1 R13 Chemical compound 0.000 claims description 126
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 105
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 98
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 81
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 73
- 238000005669 hydrocyanation reaction Methods 0.000 claims description 68
- 125000004437 phosphorous atom Chemical group 0.000 claims description 68
- 125000001424 substituent group Chemical group 0.000 claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims description 57
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 229910001868 water Inorganic materials 0.000 claims description 46
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 44
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 32
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052794 bromium Inorganic materials 0.000 claims description 24
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 22
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- 150000002825 nitriles Chemical class 0.000 claims description 21
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims description 20
- 125000001188 haloalkyl group Chemical group 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000605 extraction Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 13
- 238000000638 solvent extraction Methods 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 239000012454 non-polar solvent Substances 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 11
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000003495 polar organic solvent Substances 0.000 claims description 9
- ZHDHSBKTLRLUCQ-UHFFFAOYSA-N 6-[4-(6-bromo-1,2-benzothiazol-3-yl)phenoxy]-n-methyl-n-prop-2-enylhexan-1-amine Chemical compound C1=CC(OCCCCCCN(C)CC=C)=CC=C1C1=NSC2=CC(Br)=CC=C12 ZHDHSBKTLRLUCQ-UHFFFAOYSA-N 0.000 claims description 7
- NFGODEMQGQNUKK-UHFFFAOYSA-M [6-(diethylamino)-9-(2-octadecoxycarbonylphenyl)xanthen-3-ylidene]-diethylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C1=C2C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C21 NFGODEMQGQNUKK-UHFFFAOYSA-M 0.000 claims description 3
- JYNZIOFUHBJABQ-UHFFFAOYSA-N allyl-{6-[3-(4-bromo-phenyl)-benzofuran-6-yloxy]-hexyl-}-methyl-amin Chemical group C=1OC2=CC(OCCCCCCN(C)CC=C)=CC=C2C=1C1=CC=C(Br)C=C1 JYNZIOFUHBJABQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- 125000004429 atom Chemical group 0.000 description 21
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 20
- 125000000753 cycloalkyl group Chemical group 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 239000002841 Lewis acid Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 150000007517 lewis acids Chemical class 0.000 description 14
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 14
- 210000002966 serum Anatomy 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 125000005538 phosphinite group Chemical group 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- 0 *c(c(*)c1*)c(*)c(-c2c(*)c(*)c(*)c(*)c2OP(O*)O*)c1OP(O*)O* Chemical compound *c(c(*)c1*)c(*)c(-c2c(*)c(*)c(*)c(*)c2OP(O*)O*)c1OP(O*)O* 0.000 description 2
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 2
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PNXOBXSLUPTIOU-UHFFFAOYSA-N Cc(cc1C)ccc1OP(O)O Chemical compound Cc(cc1C)ccc1OP(O)O PNXOBXSLUPTIOU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 2
- 238000001511 high performance liquid chromatography nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- DPGHISRNNOYQGP-UHFFFAOYSA-N 1-(1,2,3,4,4a,5,6,7-octahydronaphthalen-1-yl)naphthalene Chemical group C1=CC=C2C(C3CCCC4C3=CCCC4)=CC=CC2=C1 DPGHISRNNOYQGP-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- HCERDWRTRFAZCN-UHFFFAOYSA-N Cc(cc1)cc(C)c1OP(O)Oc1ccc(C)cc1C Chemical compound Cc(cc1)cc(C)c1OP(O)Oc1ccc(C)cc1C HCERDWRTRFAZCN-UHFFFAOYSA-N 0.000 description 1
- KLYWMXKRWRCOBW-UHFFFAOYSA-N Cc(cc1)cc(C)c1O[O](C)Oc1ccc(C)cc1C Chemical compound Cc(cc1)cc(C)c1O[O](C)Oc1ccc(C)cc1C KLYWMXKRWRCOBW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical group 0.000 description 1
- BONASJKBJAQWML-UHFFFAOYSA-N OPO.OP(O)O Chemical compound OPO.OP(O)O BONASJKBJAQWML-UHFFFAOYSA-N 0.000 description 1
- BOBIVTKCBMKFJH-UHFFFAOYSA-N P.P(O)O Chemical compound P.P(O)O BOBIVTKCBMKFJH-UHFFFAOYSA-N 0.000 description 1
- GYPUIXZFFQOUPO-UHFFFAOYSA-N PO.OPO Chemical compound PO.OPO GYPUIXZFFQOUPO-UHFFFAOYSA-N 0.000 description 1
- QFIJGEIKVGDVHA-UHFFFAOYSA-N PO.P(O)(O)O Chemical compound PO.P(O)(O)O QFIJGEIKVGDVHA-UHFFFAOYSA-N 0.000 description 1
- 229910018830 PO3H Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FSCUUKMZJSUUAR-UHFFFAOYSA-N [Ni+4].[O-]P([O-])OP([O-])[O-] Chemical class [Ni+4].[O-]P([O-])OP([O-])[O-] FSCUUKMZJSUUAR-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000004858 cycloalkoxyalkyl group Chemical group 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002192 heptalenyl group Chemical group 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002443 hydroxylamines Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 125000003427 indacenyl group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical class [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- ZOGYOOUMDVKYLM-UHFFFAOYSA-N phosphane phosphorous acid Chemical compound P.OP(O)O ZOGYOOUMDVKYLM-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- HABWCPIKWOZMSN-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphite Chemical compound CC1=CC(C)=CC=C1OP(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C HABWCPIKWOZMSN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/322—Hydrocyanation
Definitions
- the invention relates to the regulation of the composition of liquid phosphite blends, such as those utilized as catalyst components in the hydrocyanation reactions of 1 ,3-butadiene to produce 3-pentenenitriles and other unsaturated nitriles. More particularly, this invention relates to the adjustment of process parameters of treatment of ligands used as part of a hydrocyanation catalyst composed of a nickel and at least one bidentate phosphate ligand.
- U.S. Patent No. 6,169,198 describes the process of hydrocyanation (reaction with HCN) of butadiene (BD) to prepare adiponitrile (ADN), and explains that the process can generally be divided into three steps.
- mononitriles such as 3-pentenenitrile (3-PN) are formed by the reaction of HCN with BD, along with other nitriles, including isomers which must be isomerized in subsequent steps to achieve the desired straight chain ADN as a final product.
- Second is the isomerization of species such as 2-methyl-3-butenenitrile (2M3BN).
- Third is a second hydrocyanation of the pentenenitriles to yield the desired ADN.
- U.S. Patent No. 5,981,722 describes and exemplifies a new class of catalysts for such transformations by the use of diphosphite nickel complexes for the hydrocyanation and isomerizations. This class of catalysts is characterized by greater catalytic activity and resistance to HCN-derived degradation reactions.
- U.S. Patent No. 7,470,805 describes a process of hydrocyanation of diolefins in the presence of a catalytic system comprising a transition metal and mono- and pluri-dentate organophosphorus ligands. According to this, the use of a mixture of two ligands, monodentate and pluri (bi and/or tri)dentate, enables the pluridentate ligand to be preserved in the reaction milieu.
- Monodentate and bidentate phosphorus-based ligands depicted as formulae (7) and (8), and (3), respectively, as the structures are termed in U.S. Patent 7,629,484, can be used in preparation of a transition metal-organophosphorus catalyst for reactions such as
- U.S. Patent No. 7,659,422 describes a hydrocyanation process to produce ADN from BD with control of i) the overall feed molar ratio of 2-pentenenitriles to all unsaturated nitriles and ii) the overall feed molar ratio of HCN to all unsaturated nitriles.
- An example is given as a reaction U 2013/042613
- U.S. Patent No. 7,977,502 describes an integrated, continuous process for the production of 3-PN, the refining of 3-PN and the refining of 2M3BN by a process comprising contacting a feed stream in a reaction zone, maintaining residence time to convert about 95% or more of the HCN, distilling to create various streams.
- Nickel-containing solids comprising nickel metal derived from basic nickel carbonates (BNCs) which are highly reactive with both monodentate and bidentate phosphorus-containing ligands in forming nickel metal complexes, which can be for producing pentenenitriles and dinitriles by hydrocyanation.
- BNCs basic nickel carbonates
- the invention can include processes using selective hydrolysis of certain phosphorus- based ligands in a ligand blend or mixture to control relative proportions of monodentate versus bidentate and tridentate ligands.
- the ligand blend can be used to form transition metal complexes, such as nickel complexes, useful for catalysis of organic reactions, such as the hydrocyanation reaction providing nitriles from olefins such as 1,3-butadiene.
- the ligand hydrolysis reactions can be auto-catalyzed by ligand hydrolysis products formed in
- the invention can include a process of hydrolyzing a phosphorus-based ligand for a transition metal catalyst, wherein the ligand comprises at least one phosphite ester group; the process comprising:
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (C 1 -C 10)alkyl, (C3-C 10)cycloalkyl, (C3-C 10)cycloalkyl(C 1 - C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, 13 042613
- phosphorus-based ligands selected from the group consisting of:
- X 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , and X 34 each independently is oxygen or a bond, provided that at least one ofX 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , or X 34 is oxygen;
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (CI -CI 0)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alk
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3 -C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1 -4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycl
- the invention can provide a process for modifying the relative ratio of two phosphorus- based ligands for a transition metal catalyst, wherein each ligand in the blend comprises at least one phosphite ester group, in a ligand blend comprising at least two phosphorus-based ligands, a first component of the blend being selected from the group consisting of a bidendate phosphorus- based ligand of formula (III) and a tridentate phosphorus-based ligand of formula (IIIA):
- X 12 , X 13 , X 14 , X 22 , X 23 Or X 24 is oxygen, and for the ligand of formula (IIIA), X 12 , X 13 , X 14 , X 22 , X 23 ⁇ X 24 , X 32 , X 33 , and X 34 , each independently is oxygen or a bond, provided that at least one ofX 12 , X 13 , X 14 , X 22 , X 23 ⁇ X 24 , X 32 , X 33 , and X 34 , each independently is oxygen or a bond, provided that at least one ofX 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 ,
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alk
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1 -4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C
- a second component of the blend being a ligand comprising a monodentate phosphorus- based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cyclo
- n 0, 1 , or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl -
- the invention can provide a process for maintaining a concentration of a phosphorus- based bidentate ligand or of a phosphorus-based tridentate ligand, or both, within a concentration range, in a phosphorus-based ligand blend further comprising a monodentate phosphorus-based ligand, for a transition metal catalytic complex in a hydrocyanation reaction milieu comprising water and at least one organic liquid, wherein each phosphorus-based ligand in the blend comprises at least one phosphite ester group, the ligand blend comprising at least two phosphorus-based ligands, a first component of the ligand blend being a bidendate phosphorus- based ligand of formula (III) or a tridentate phosphorus-based ligand of formula (IIIA):
- X 12 , X 13 , X 14 , X 22 , X 23 ' or X 24 is oxygen
- X 12 , X 13 , X 14 , X 22 , X 23, X 24 , X 32 , X 33 , and X 34 each independently is oxygen or a bond, provided that at least one ofX I2 , X 13 , X ,4 , X 22 , X 23 ' X 24 , X 32 , X 33 , or X 34 is oxygen;
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alk
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1 -4 (C 1 -C 10)alkyl, (C3-C 10)cycloalkyl, (C 1 - C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl
- a second component of the blend being a ligand comprising a monodentate phosphorus- based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-
- each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, and (C6- C20)aryl(Cl-C10)alkyl; or, optionally, any two of R 1
- n 0, 1 , or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C
- the phosphorus-based ligand comprising at least one phosphite ester group can be a component of a phosphorus-based ligand blend, wherein the ligands contain at least one phosphite ester group, that are used in the presence of a transition metal, such as nickel, for catalysis of an olefin hydrocyanation reaction.
- the ligand blend can be used in conjunction with the nickel for the hydrocyanation of 1,3 -butadiene to yield pentenenitriles such as 3-pentenenitrile, an important intermediate in the synthesis of adiponitrile, or in the further hydrocyanation of pentenenitrile to yield adiponitrile, useful in manufacture of various nylon polymers.
- the invention can provide processes whereby liquid blends (mixtures) of phosphorus- based ligands, each containing at least one hydrolyzable phosphite ester group, wherein the blend includes at least one monodentate ligand (e.g., of formula (IV)) and at least one bidentate ligand (e.g., of formula (III)) or tridentate ligand (e.g., of formula ( ⁇ )), can be adjusted in the relative content of the ligands by monitoring the concentration of hydrolysis catalyst (e.g., of formula (I)), and selectively hydrolyzing and separating, for example, a selectively hydrolyzed monodentate ligand in the presence of a bidentate and/or tridentate ligand.
- a monodentate ligand e.g., of formula (IV)
- bidentate ligand e.g., of formula (III)
- tridentate ligand e.g., of formula ( ⁇ )
- the hydrolysis catalyst can be a ligand hydrolysis product produced by in situ hydrolysis of one or more ligand components of the blend. Also, the hydrolysis catalyst can, if appropriate, be added to the ligand blend, thereby preferentially hydrolyzing particular phosphites, e.g., monodentate ligands with respect to bidentate or tridentate ligands.
- the ligand blend can be present in the hydrocyanation reaction milieu and, as part of a catalyst maintenance subprocess, be adjusted in relative ligand concentrations through this selective hydrolysis and separation of certain ligand blend components.
- the present invention can provide technical solutions to the problem of regulating the proportions of phosphorus-based ligands in a ligand blend for use in a transition metal complex for hydrocyanation reactions, such as when the hydrocyanation reactions are carried out in the presence of even trace or controlled amounts of water.
- Solutions to regulation of levels of monodentate versus bidentate and/or tridentate phosphorus-based ligands in ligand blends are provided that enable the formation of catalysts, e.g., nickel complexes with the ligands of the blend, with favorable properties for use in hydrocyanation reactions.
- Hydrolysis catalysts are provided, which can be derived by hydrolysis of monodentate phosphorus-based ligands, that can selectively hydrolyze monodentate ligands containing at least one phosphite ester bond in the presence of bidentate and/or tridentate ligands containing at least one phosphite ester bond, such that the acidic hydrolysis products of the monodentate ligands can be extracted, such as by liquid-liquid extraction using polar and nonpolar solvents, from the ligand blend, thereby maintaining higher relative concentrations of favorable bidentate/tridentate ligands.
- phrases such as "under conditions suitable to provide” or “under conditions sufficient to yield” or the like, in the context of methods of synthesis, as used herein refers to reaction conditions, such as time, temperature, solvent, reactant concentrations, and the like, that are within ordinary skill for an experimenter to vary, that provide a useful quantity or yield of a reaction product. It is not necessary that the desired reaction product be the only reaction product or that the starting materials be entirely consumed, provided the desired reaction product can be isolated or otherwise further used.
- chemically feasible is meant a bonding arrangement or a compound where the generally understood rules of organic structure are not violated; for example a structure within a definition of a claim that would contain in certain situations a pentavalent carbon atom that would not exist in nature would be understood to not be within the claim.
- the structures disclosed herein are intended to include only “chemically feasible” structures, and any recited structures that are not chemically feasible, for example in a structure shown with variable atoms or groups, are not intended to be disclosed or claimed herein.
- stable compound and “stable structure” are meant to indicate a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture, and formulation into an efficacious therapeutic agent. Only stable compounds are contemplated herein.
- organic radical refers to a portion or fragment or moiety, capable of bonding to another atom, wherein the group is carbon-based.
- carbon-based is meant that at least a portion of the group comprises at least one carbon atom, which can be covalently bonded to other atoms capable of covalent bonding such as hydrogen, nitrogen, oxygen, halogen, sulfur, phosphorus, and the like, as is well known in the art.
- a group e.g., an "alkyl” group or an “aryl” group
- the claim is definite and limited with respect the size of the alkyl group, both by definition; i.e., the size (the number of carbon atoms) possessed by a group such as an alkyl group is a finite number, bounded by the understanding of the person of ordinary skill as to the size of the group as being reasonable for a molecular entity; and by functionality, i.e., the size of the group such as the alkyl group is bounded by the functional properties the group bestows on a molecule containing the group such as solubility in aqueous or organic liquid media. Therefore, a claim reciting an "alkyl” or other chemical group or moiety is definite and bounded.
- substituted refers to an organic group as defined herein in which one or more bonds to a hydrogen atom contained therein are replaced by one or more bonds to a non- hydrogen atom such as, but not limited to, a halogen (i.e., F, CI, Br, and I); an oxygen atom in groups such as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups,
- oxo(carbonyl) groups carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters
- a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups
- a nitrogen atom in groups such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups.
- Non-limiting examples of substituents J that can be bonded to a substituted carbon (or other) atom include F, CI, Br, I, OR', OC(0)N(R') 2 , CN, NO, N0 2 , ON0 2 , azido, CF 3 , OCF 3 , R 1 , O (oxo), S (thiono), methylenedioxy, ethylenedioxy, N(R') 2 , SR', SOR', S0 2 R, S0 2 N(R') 2 , S0 3 R, C(0)R', C(0)C(0)R', C(0)CH 2 C(0)R', C(S)R', C(0)OR', OC(0)R, C(0)N(R') 2 , OC(0)N(R') 2 , C(S)N(R') 2 , (CH 2 ) 0 . N(R')C(O)R', (CH 2 ) 0 .
- R' can be hydrogen or a carbon-based moiety, and wherein the carbon-based moiety can itself be further substituted; for example, wherein R' can be hydrogen, alkyl, acyl,
- Substituent groups J can independently be halo, nitro, cyano, OR, NR 2 , or R, or is C(0)OR, C(0)NR 2 , OC(0)OR, OC(0)NR 2 , N(R)C(0)OR, N(R)C(0)NR 2 or thio/thiono analogs thereof.
- thio/thiono analogs thereof with respect to a group containing an O, is meant that any or all O atoms in the group can be replaced by an S atom; e.g., for group C(0)OR, a
- thio/thiono analog thereof includes C(S)OR, C(0)SR, and C(S)SR; e.g., for group OC(0)NR 2 , a "thio/thiono analog thereof includes SC(0)NR 2 , OC(S)NR 2 , and SC(S)NR 2 ; and so forth.
- a substituent When a substituent is monovalent, such as, for example, F or CI, it is bonded to the atom it is substituting by a single bond.
- a divalent substituent such as O or S can be connected by two single bonds to two different carbon atoms.
- O a divalent substituent
- any substituent can be bonded to a carbon or other atom by a linker, such as (C3 ⁇ 4) n or (CR' 2 ) n wherein n is 1, 2, 3, or more, and each R' is independently selected.
- Alkyl groups include straight chain and branched alkyl groups and cycloalkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.
- branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
- alkyl encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl.
- Representative substituted alkyl groups can be substituted one or more times with any of the groups listed above, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
- Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
- the cycloalkyl group can have 3 to about 8-12 ring members, or, the number of ring carbon atoms range from 3 to 4, 5, 6, or 7.
- Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like.
- Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above.
- Representative substituted cycloalkyl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups or mono-, di- or tri- substituted norbornyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
- cycloalkenyl alone or in combination denotes a cyclic alkenyl group.
- (Cycloalkyl)alkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to a cycloalkyl group as defined above.
- alkoxy refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined above.
- linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like.
- branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like.
- cyclic alkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like.
- An alkoxy group can include one to about 12-20 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms.
- an allyloxy group is an alkoxy group within the meaning herein.
- a methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structures are substituted therewith.
- Aryl groups are cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring.
- aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
- Aryl groups can contain about 6 to about 14 carbons in the ring portions of the groups.
- Aryl groups can be unsubstituted or substituted, as defined above.
- substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substituted naphthyl groups, which can be substituted with carbon or non-carbon groups such as those listed above.
- Aryl groups can also bear fused rings, such as fused cycloalkyl rings, within the meaning herein.
- fused cycloalkyl rings within the meaning herein.
- a tetrahydronaphthyl ring is an example of an aryl group within the meaning herein.
- an aryl ring includes, for example, a partially hydrogenated system, which can be unsubstituted or substituted, and includes one or more aryl rings substituted with groups such as alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, cycloalkylalkyl, cycloalkoxyalkyl, and the like, and also fused with, e.g., a cycloalkyl ring.
- Organophosphorus compounds include molecular entities wherein one or more phosphorus atoms is present, and one or more organic radicals or moieties is also present.
- An organophosphorus compound can further include other elements such as oxygen, halogens, hydrogen, nitrogen, and the like.
- organophosphorus compounds wherein P is a phosphorus atom and R indicates an organic moiety that is bonded via a carbon-phosphorus bond to the phosphorus atom, include
- phosphine PR 3
- P(0)R 3 phosphine oxide
- P(0)R 3 phosphinite
- P(OR)R 2 phosphinite
- P(OR) 2 R phosphonite
- P(ROP(0)R 2 phosphinate
- P(OR) 3 phosphite
- P(0)(OR) 3 phosphate
- a "phosphorus-based ligand” as the term is used herein refers to a ligand containing at least one phosphorus atom, that is suitable for formation of a complex with a transition metal such as nickel, wherein the complex can possess catalytic activity for an organic reaction such as a hydrocyanation reaction of an olefin, such as the hydrocyanation of butadiene to yield pentenenitrile, or the hydrocyanation of pentenenitrile to yield adiponitrile.
- an organic reaction such as a hydrocyanation reaction of an olefin, such as the hydrocyanation of butadiene to yield pentenenitrile, or the hydrocyanation of pentenenitrile to yield adiponitrile.
- phosphorus-based refers to an orgamc compound that contains at least one phosphorus atom, whether or not it has catalytic activity.
- a "monodentate" phosphorus-based ligand contains a single phosphorus atom per molecule, which can complex a metal atom such as nickel.
- a "bidentate” phosphorus-based ligand contains two phosphorus atoms per molecule, both of which can complex a single metal atom, such as a nickel atom.
- a "tridentate” phosphorus-based ligand contains three phosphorus atoms per molecule, all three of which can complex a single metal atom, such as a nickel atom.
- a value of a variable that is necessarily an integer, e.g., the number of carbon atoms in an alkyl group or the number of substituents on a ring is described as a range, e.g., 0-4, what is meant is that the value can be any integer between 0 and 4 inclusive, i.e., 0, 1, 2, 3, or 4.
- the compound or set of compounds, such as are used in the inventive methods can be any one of any of the combinations and/or sub-combinations of the elements as described herein.
- a compound as shown in any of the Examples, or among the exemplary compounds, is provided.
- Provisos can apply to any of the disclosed categories wherein any one or more of the other above disclosed categories or species can be excluded from such categories.
- the catalyst composition can be dissolved in a solvent that is non-reactive toward, and miscible with, the hydrocyanation reaction mixture.
- suitable solvents include, for example, aliphatic and aromatic hydrocarbons with 1 to 10 carbon atoms, and nitrile solvents such as acetonitrile.
- 3PN a mixture of isomeric pentenenitriles, a mixture of isomeric methylbutenenitriles, a mixture of isomeric pentenenitriles and isomeric methylbutenenitriles, or the reaction product from a previous reaction campaign, can be used to dissolve to the catalyst composition.
- the HCN-containing feed, the BD-containing feed, and the catalyst composition are contacted in a reaction zone which can be contained in any suitable equipment known to one skilled in the art.
- a reaction zone which can be contained in any suitable equipment known to one skilled in the art.
- One or more pieces of conventional equipment can be used to provide the reaction zone, for example continuous stirred-tank reactors, loop-type bubble column reactors, gas circulation reactors, bubble column reactors, tubular reactors, or combinations thereof, optionally with apparatus for removing at least a portion of the heat of reaction.
- the reaction temperature is typically maintained within the range of about 80° C to about
- reaction pressure should be sufficient to maintain the reagents in the liquid state, with such pressure at least, in part, a function of the amount of unreacted BD present in the reaction mixture.
- the pressure generally ranges from about 15 psia to about 300 psia (about 103 kPa to about 30 2068 kPa).
- HCN substantially free of carbon monoxide, oxygen, ammonia, and water can be introduced to the reaction as a vapor, liquid, or mixtures thereof.
- cyanohydrins can be used as the source of HCN. See, for example, U.S. Pat. No. 3,655,723.
- the molar ratio of the HCN in the feed to the BD in the feed is in the range of about
- This range of molar ratios can be advantageous over those 40 with a significantly larger excess of BD to HCN in that there can be less unreacted BD to recover and recycle to the process, and yield losses to 2-methylglutaronitrile (MGN) and to BD dimers, oligomers, and related, species can be reduced.
- the molar ratio of the zero-valent nickel in the feed to the BD in the feed is in the range of about 0.00005: 1.00 to about 0.0050:1.00, for example in the range about 0.0001 :1.00 to about 0.0010:1.00.
- the residence time in the reaction zone (for example, the time necessary for the combined feeds to displace one reactor so volume in a continuous-stirred-tank-reactor (CSTR) is typically determined by the desire to maintain the 2M3BN concentration below about 15 weight percent of the total mass of the reaction mixture, for example at or below about 10 weight percent of the total mass of the reaction mixture, and is also related to the catalyst concentration and reaction temperature.
- residence times will be in the range of about 0.5 to about 15 hours, for example in the range of about 1 to about 10 hours.
- Water can be present in commercially available BD. Water can be undesirable in hydrocyanation processes as it can react with the phosphorus-containing ligand to produce hydrolysis products which are less active or inactive for the desired hydrocyanation and isomerization reactions. The ligand hydrolysis products can also promote undesired side reactions.
- BD Prior to its use in hydrocyanation, BD can be purified to remove impurities such as TBC and water.
- TBC can be removed from BD by a variety of techniques, for example by distillation or by passing the liquid BD over an absorbent bed such as alumina. Distillation can also be used to remove other impurities, for example 4-vinyl-l-cyclohexene, from BD.
- Water can be removed from BD by a variety of techniques, for example by passing liquid BD over molecular sieves having a pore size smaller than 10 Angstrom units or by contacting it with alumina.
- a reaction for hydrocyanating 3-pentenenitrile to produce adiponitrile preferably takes place in the presence of a promoter for promoting this reaction.
- the promoter can be a Lewis acid, such as an inorganic compound, an organometallic compound, or combinations thereof, in which a cation of the Lewis acid is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, lanthanum, erbium, ytterbium, samarium, tantalum, and tin.
- the reactions which take place in the first reaction zone for hydrocyanating 1,3-butadiene and the second reaction zone for isomerizing 2-methyl-3- butenenitrile, preferably take place in the absence or substantial absence of such a promoter.
- Dinitriles can be produced in the first reaction zone by the reaction of 3-pentenenitrile (3PN) or 2-methyl-3-butenenitrile (2M3BN) with HCN.
- Lewis acids are capable of promoting the formation of dinitriles in the first reaction zone.
- Lewis acids are preferably not introduced into the first reaction zone in detectable amounts.
- a detectable amount of a Lewis acid can be introduced into the first reaction zone, provided that dinitrile formation is minimized.
- a detectable amount of a Lewis acid can be introduced into the first reaction zone, provided that the amount of dinitriles produced, when none of the Lewis acid is introduced into the first reaction zone, is not increased by more than 5 wt%.
- Lewis acid can be unintentionally introduced into the first reaction zone as a result of a unit upset or operator error.
- the continuous production of 3-pentenenitrile can be maintained, provided that the ratio of atomic equivalents of Ni to moles of Lewis Acid in the first reaction zone is less than 10:1 during the course of at least 95% of the production of 3- pentenenitrile.
- 3-Pentenenitrile produced in the first and second reaction zones can be reacted with hydrogen cyanide to produce dinitriles comprising adiponitrile in a third reaction zone downstream of the first and second reaction zones.
- a catalyst and a Lewis acid promoter can flow through the third reaction zone along with reactants and products.
- the reaction temperature is typically maintained within the range of about 25° C to about 80 °C, for example within the range of about 40° C to about 70° C.
- none of the Lewis acid promoter which flows from the third reaction zone flows into the first reaction zone.
- hydrolysis catalyst that can be used in practicing a process of the invention is a hydrolysis catalyst of formula (I)
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(C 1
- R 11 can be an independently selected (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3- C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(Cl
- each independentl can be a group of formula (II)
- R is selected from the group consisting of (CI -CI 0)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, and (C6-C20)aryl, and each of R , R and R is independently selected from the group consisting of H, (CI - C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3- C 10)cycloalkyl(C 1 -C
- the hydrolysis catalyst of formula (I) can be a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both.
- the catalyst includes at least one acidic P-O-H group.
- either trivalent or pentavalent depictions of these structures is intended to indicate either or both forms, whether X 11 is oxygen or X 11 is a bond.
- formula (IA) when X 11 is a bond, the compound is termed a phosphonite, when X 11 is an oxygen, the compound is termed a phosphite monoester.
- formula (IB) when both X 11 groups are each a bond the compound is termed a phosphinite, when both X 11 groups are each an oxygen, the compound is termed a phosphite diester, and when one X 11 is a bond and the other X 11 is an oxygen, the compound is termed a phosphonite, according to common usage. All these subgenera are included within the definition of the hydrolysis catalyst of formula (I), as is phosphorous acid, H3PO3.
- Each independently selected R 11 can be an aryl group, including an unsubstituted aryl group such as phenyl or naphthyl, or a substituted aryl group, e.g., a methyl-substituted aryl group such as tolyl or xylyl.
- Each independently selected R 11 group can be a group of formula (II)
- R 45 is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxyl, (Cl-ClO)alkoxyl, (C3-C10)cycloalkoxyl, (C3- C10)cycloalkoxyl(Cl-C10)alkyl, and (C3-C10)cycloalkoxyl(Cl-C10)alkoxyl; and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxyl; and each of R 46 , R 47 and R 48 is independently selected
- R 45 is a non-hydrogen substituent, such as an alkyl or alkoxyl group.
- R 11 group of formula (II) only a single ortho position bears a non-hydrogen substituent, although the meta and para positions can be substituted as described herein.
- R 45 can be methyl, ethyl or isopropyl, or can be methoxyl, ethoxyl, or isopropoxyl.
- all of R 46 , R 47 and R 48 can be H.
- R 47 the para substituent, can also be an alkyl or alkoxyl group, such as methyl or methoxyl.
- the group of formula (II) can be a 2,4-xylyl group, i.e., wherein R and R are each methyl, and R and R are each hydrogen.
- each X 1 1 can be oxygen and each R 11 can be a phenyl group, a tolyl group, or a xylyl group.
- the hydrolysis catalyst can be of formula (IA1):
- R 45 is independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, and (C3- C10)cycloalkoxy(Cl-C10)alkoxy, and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alk
- R 45 can be methyl, ethyl or isopropyl; additionally, R 46 can be hydrogen, and R 47 and R 48 can be
- hydrolysis catalyst can be of formula (IA2):
- the hydrolysis catalyst of formula (I) can be produced in the presence of water in a reaction mixture containing phosphorus-based compounds having at least one phosphite ester bond, useful as ligands for catalytic transition metal complexes, or can be added to the phosphite ester ligand blend, or both.
- the production of the catalyst can take place in a hydrocyanation reaction milieu comprising the ligand blend, a transition metal such as nickel, water, and at least one organic component.
- the organic component can comprise pentenenitrile, such as 3 -pentenenitrile, produced by hydrocyanation of butadiene, or adiponitrile, produced by hydrocyanation of pentenenitrile.
- the hydrolysis catalyst can itself be a hydrolytic degradation product of the phosphorus-based ligand during hydrocyanation of an alkene in the presence of even trace or controlled amounts of water.
- Additional hydrolysis catalyst can be deliberately added to bring about hydrolysis of one of more of the components of the ligand blend, such as selective hydrolysis of a monodentate ligand, e.g., of formula (IV), in the presence of a bidentate ligand, e.g., of formula (III) or a tridentate ligand, e.g., of formula (IIIA) in a ligand blend comprising ligands of both formula (III) and/or formula (IIIA), and formula (IV).
- a phosphorus-based ligand subject to hydrolysis i.e., containing at least one phosphite ester bond
- the hydrolysis of which can be catalyzed by the hydrolysis catalyst of formula (I) in carrying out a process of the present invention can be a component of a hydrocyanation catalyst, such as when combined with a transition metal such as nickel, as known in the art.
- the ligand can be, for example, a phosphite, a phosphonite, a phosphinite, a phosphine, or a mixed phosphorus-based ligand or a combination of such members, provided the ligand contains at least one hydrolyzable P-O-C bond, wherein P is a phosphorus atom (which additionally bears other substituents), O is an oxygen atom, and C represent an organic radical, such as an aryl group.
- the phosphorus-based ligand can be monodentate or multidentate, for example, bidentate or tridentate.
- the term "monodentate” is well known in the art, and means that each molecule of the ligand possesses a single phosphorus atom (e.g., a compound of formula (IV)), which can be bonded to a single metal atom.
- the term “bidentate” is well known in the art, and means that each molecule of the ligand possesses two phosphorus atoms (e.g., a compound of formula (III)), and both phosphorus atoms of the ligand can be bonded to a single metal atom.
- the term “monodentate” is well known in the art, and means that each molecule of the ligand possesses two phosphorus atoms (e.g., a compound of formula (III)), and both phosphorus atoms of the ligand can be bonded to a single metal atom.
- tridentate means that each molecule of the ligand possesses three phosphorus atoms (e.g., a compound of formula (IIIA)), and all three phosphorus atoms on the ligand can be bonded to a single metal atom.
- the terms “bidentate” and “tridentate” are also known in the art as chelate ligands.
- the term "mixed phosphorus-based ligand” means a phosphorus-based ligand comprising at least one combination selected from the group consisting of a phosphite- phosphonite, a phosphite-phosphinite, a phosphite-phosphine, a phosphonite-phosphinite, a phosphonite-phosphine, and a phosphinite-phosphine or a combination of such members, provided that there is at least one P-O-C bond, wherein P is a phosphorus atom, O is an oxygen atom, and C represent an organic radical, such as an aryl group, that is subject to hydrolysis under acid catalysis.
- the hydrolysis catalyst of formula (I) as can be used in practice of a process of the invention can be derived from hydrolysis of a phosphorus-based ligand, such as by hydrolysis of a monodentate phosphorus-based ligand. This hydrolysis can occur under the conditions present in a hydrocyanation reaction milieu, in the presence of even a trace or controlled amount of water, to generate the hydrolysis catalyst.
- Suitable phosphorus-based ligands for the transition metal e.g., nickel, complex
- Bidentate and tridentate ligands can be of formulas (III) and (IIIA), respectively, thus including
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alk
- X 12 , X 13 , X 14 , X 22 , X 23 X 24 , X 32 , X 33 , and X 34 can each be oxygen.
- the bridging group Y, Y 1 , and/or Y 2 is bonded to phosphite groups.
- X 12 and X 13 can each be oxygen and X 14 a single bond, or X 12 and X 13 each a oxygen and X 14 a single bond.
- X 22 , X 23 and X 24 can each be oxygen, or X 22 and X 24 can each be oxygen and
- X a single bond, or X and X can each be oxygen and X a single bond, or X can be oxygen and X 22 and X 24 each a single bond, and so forth.
- Each phosphorus atom of in a compound of formula (III), (IIIA), or (IV) can be the central atom of a phosphite, phosphonite, phosphinate, phosphi ite or phosphine, preferably a phosphonite or a phosphite.
- At least one of the X groups of each of formulas (III), (IIIA), and (IV) is an oxygen atom, providing a P-O-C bond that is subject to hydrolysis under acidic conditions, wherein P is a phosphorus atom, O is an oxygen atom, and C represent an organic radical, such as an aryl group.
- the bridging group Y, Y 1 , or Y 2 can each independently be a (C6-C20)arylene group, each ring of which is unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalky(Cl-C10)alkoxy 1, (C3- C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine,
- Y, Y , and/or Y can, combined with the X groups to which it is bonded, be a pyrocatechol, a bis(phenol) or bis(naphthol).
- an “arylene” group is meant a bifunctional group comprising one or more (C6-C20)aryl rings, each ring of which can be unsubstituted, or substituted, e.g., with 1-4 independently selected (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxyl, (Cl- C10)alkoxyl, (C3-C10)cycloalkoxyl, (C3-C10)cycloalkoxyl(Cl-C10)alkyl, and (C3- C10)cycloalkoxyl(Cl-C10)alkoxyl, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, halogen, such as fluorine, chlorine, bromine; halogenated alkyl, such as trifluoromethyl
- the R groups can be as described herein; for example, for formula (III), R , R , R 22 , R 23 , and for the ligand of formula (IIIA), R 12 , R 13 , R 22 , R 23 , and R 34 , each independently is (C 1 -C 10)alkyl, (C3-C 10)cycloalkyl, ( (C3-C 10)cycloalkyl C 1 -C 10)alkyl, (C6-C20)aryl, or (C6- C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl, each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-
- the R groups of formulas (III) and (IIIA) can be aryl radicals, preferably those having from 6 to 20 carbon atoms, which can be unsubstituted or mono- or polysubstituted, in particular by (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxyl, (Cl-ClO)alkoxyl, (C3-C10)cycloalkoxyl, (C3- C10)cycloalkoxyl(Cl-C10)alkyl, and (C3-C10)cycloalkoxyl(Cl-C10)alkoxyl.
- the R 12 and R 13 groups can each be separate or bridged.
- the R 22 and R 23 groups can also each be separate or
- R , R , R and R radicals can each be separate, one pair can be bridged and one pair separate, or both pairs can be bridged, in the manner described.
- the monodentate ligand of formula (IV) can be a monodentate phosphorus-based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1 -4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycl
- the ligand of formula (IV) can be a phosphite, a phosphonite, a phosphinite, and the like, provided that at least one phosphite ester bond, e.g., a P-O-C bond, subject to acid-catalyzed hydrolysis, is present in the ligand.
- R 1 , R 2 and R 3 can independently alkyl, cycloalkyl, alkoxy, or cycloalkyoxy radicals, the alkyl radicals preferably having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl, s-butyl, t-butyl, and the cycloalkyl radical preferably having from 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclpentyl, and cyclohexyl; aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, or 2-naphthyl, preferably having from 6 to 20 carbon atoms, such as ⁇ , ⁇ -biphenyl, ⁇ , ⁇ -binaphthyl.
- R 1 , R 2 and R 3 groups can be bonded together directly, i.e. not solely via the central phosphorus atom.
- R , R and R groups can be selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl. Or, two of the R , R and R groups can be phenyl groups. Or, two of the R , R and R groups can be o-tolyl groups.
- any or all of the R , R and R groups can be xylyl, such as 2,4-xylyl.
- Examples of such compounds (IVa) include: (o-tolyl-0-) 3 P,
- a bidentate phosphite ligand that is useful in the inventive processese, i.e., a compound of formula (III), above, is a ligand having formula (V), shown below
- bidentate phosphite ligands that are useful in the inventive processes include those having the formulae (VI) to (IX), shown below wherein for each formula, R can selected from the group consisting of methyl, ethyl, and isopropyl, and R 18 and R 19 can be independently selected from H and methyl. Or, each of R 17 , R 18 , and R 19 can be independently higher alkyls, or cycloalkyls, alkoxyls, or cycloalkoxyls.
- bidentate phosphite ligands that are useful in the inventive processes include a ligand selected from a member of the group represented by formulae (X) and (XI), in which all like reference characters can have the same meaning, or can be independently selected.
- each R 41 and R 45 can be independently selected from the group consisting of (Cl- C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxyl, and (C3-C10)cycloalkoxyl, and each of R 42 , R 43 , R 44 , R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl- CI 0)alkyl, and (C3-C 10) cycloalkyl.
- the bidentate phosphite ligand can be selected from a member of the group represented by formula (X) and formula (XI), wherein:
- R 41 is methyl, ethyl, isopropyl, or cyclopentyl
- R 42 is H or methyl
- R 43 is H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxyl, or (C3-C10)cycloalkoxyl;
- R 44 is H or methyl;
- R 45 is methyl, ethyl, or isopropyl
- R 46 , R 47 and R 48 are independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxyl, and (C3-C10)cycloalkoxyl.
- the bidentate phosphite ligand can be selected from a member of the group represented by formula (X), wherein:
- R 41 , R 44 , and R 45 are methyl
- R 42 , R 46 , R 47 and R 48 are H;
- R 43 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxyl, or (C3-C10)cycloalkoxyl;
- R 41 is isopropyl
- R 42 is H
- R 43 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxyl, or (C3-C10)cycloalkoxyl;
- ⁇ , ⁇ 44 is H or methyl
- R 45 is methyl or ethyl
- R 46 and R 48 are H or methyl
- R 47 is H, methyl, or tertiary-butyl
- bidentate phosphite ligand can be selected from a member of the group represented by formula XI, wherein:
- R >41 is isopropyl or cyclopentyl
- R is methyl or isopropyl
- R ⁇ R ⁇ and R ⁇ 48 are H.
- the bidentate phosphite ligand can be represented by Formula lerein R 41 is isopropyl; R 42 , R 46 , and R 48 are H; and R 43 , R 44 , R 45 , and R 47 are methyl.
- the ligand of formula (III) is of formula (XII)
- R 12 , R 1J , R 22 and R 23 are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 - R Y1 ° is independently selected from the group consisting of hydrogen, (C1-C10) alkyl, and (Cl-ClO)alkoxy, or wherein two adjacent R Y3 -R Y1 ° groups together form an optionally substituted fused aryl ring.
- the invention can provide a process wherein, for the ligand of formula (XII), R 12 , R 13 , R 22 , and R 23 are each independently phenyl substituted at a respective first ortho- position with a (Cl-ClO)alkyl or (Cl-ClO)alkoxy, at a respective second or/3 ⁇ 4o-position with hydrogen, and wherein respective meta- andjxsra-positions of the R , R , R , and R phenyls can each independently be unsubstituted or be independently substituted with 1-3 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)
- R Y6 and R Y1 ° are independently (C 1 -C 10)alkyl or (C 1 -C 10)alkoxy, and R Y3 , R Y4 , R Y5 ,
- R Y7 , R Y8 , and R Y9 are independently H, (Cl-ClO)alkyl, or (Cl-ClO)alkoxy, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (Cl-ClO)alkyl or (Cl- C10)alkoxy.
- formulae (V) to (XII) are two-dimensional representations of three-dimensional molecules and that rotation about chemical bonds can occur in the molecules to give configurations differing from those shown.
- rotation about the carbon- carbon bond between the 2- and 2'- positions of the biphenyl, octahydrobinaphthyl, binaphthyl , or biphenyl bridging groups of formulae (V) to (XII), respectively can bring the two phosphorus atoms of each bidentate ligand in closer proximity to one another and can allow the phosphite ligand to bind to nickel in a bidentate fashion.
- an optically active moiety such as sec-butyl for R 41 can result in optically active catalysts.
- Particular blends for the process of the present invention are those which contain the ligand of the formula (V), above, and phosphite triesters of the following formulae (XIII) and
- the invention can provide a process of hydrolyzing a phosphorus-based ligand for a transition metal catalyst, wherein the ligand comprises at least one phosphite ester group; the process comprising:
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)
- phosphorus-based ligand selected from the group consisting of::
- X 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , and X 34 each independently is oxygen or a bond, provided that at least one of X , X", X 14 , X , X"' X , X , X 33 , or X 34 is oxygen;
- R 12 , R 13 , R 22 , and R 23 each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein any (C6- C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl- C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C10)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1 -4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycl
- R 1 , R 2 , R 3 , R 11 , R 12 , R 13 , R 22 , R 23 or R 34 can each be an independently selected (C6-
- R 1 , R 2 , R 3 , R 11 , R 12 , R 13 , R 22 , R 23 or R 34 can be a group of formula (II)
- R is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl -C 10)alkyl, (C3 -C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, and (C6-C20)aryl, and each of R , R and R is independently selected from the group consisting of H, (C 1 - C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3- C 10)cycloalkyl
- Y (in formula (III)), or independently selected Y or Y (in formula ( ⁇ )), can be a (C6- C20)arylene group, wherein each ring thereof is independently unsubstituted or is independently substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, (C6- C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl-ClO)haloalkyl.
- the hydrolysis catalyst of formula (I) can a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both.
- the hydrolysis catalyst of formula (I) can itself be a hydrolysis product of a monodentate ligand of formula (IV).
- the phosphorus-based ligand blend, the metal, and even a trace or controlled amount of water, or a larger quantity of water can be present in a reaction wherein, e.g.,.
- butadiene and hydrogen cyanide are present.
- An organic component such as a reaction product, e.g., pentenenitriles (which can be a mix of pentenenitrile isomers such as 2-, 3-, and 4- pentenenitrile) can be present.
- Adiponitrile can also be present.
- Additional components such as solvents, diluents, and the like, can also be present.
- reaction adjuvants such as metal salts (e.g., ZnCl 2 and the like), for example, as co-catalysts and the like, can be present.
- the ligand blend used in the hydrocyanation reaction can be monitored and its contents adj sted as needed.
- the hydrolysis catalyst brings about selective hydrolysis of a monodentate ligand in the presence of a bidentate and or tridentate ligand
- the hydrolyzed monodentate ligand product, an acid phosphite ligand hydrolysis or decomposition product can be removed for the ligand pool, along with any acidic hydrolysis catalyst, by an extraction step.
- a stream of ligand pool material can be processed through a side-process during execution of the main hydrocyanation reaction in a fluidized bed reaction vessel, or other suitable reaction apparatus, for adjustment of concentrations and relative abundances of various ligand blend components.
- This separation of acidic ligand hydrolysis products produced by action of the hydrolysis catalyst of formula (I), along with the acidic catalyst itself, can be carried out by an extraction process.
- the removal step ii) can through extraction between a nonpolar and a polar organic solvent.
- the nonpolar solvent can comprise cyclohexane.
- the polar solvent can be a raffinate from the hydrocyanation reaction of butadiene, comprises adiponitrile, or both.
- a "raffinate" is meant the composition from which the unwanted components have been removed or extracted, i.e., "that which has been refined.”
- each R 41 and R 45 is independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, and (C3- C10)cycloalkoxy(Cl-C10)alkoxy, and each of R 42 , R 43 , R 44 , R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C 10)cycloalkoxy, (C3 -C 10)cycloalkyl(C 1 -C 10)
- R 41 can be methyl, ethyl, isopropyl, or cyclopentyl
- R 42 can be H or methyl;
- R 4J can be H or (Cl-C4)alkyl;
- R 44 can be H or methyl
- R 45 can be methyl, ethyl, or isopropyl
- R 46 , R 47 and R 48 can be independently H or (Cl-C4)alkyl.
- Bidentate phosphorus-based ligands that can be used in the processes of the invention include a ligand of formula (III) that is of formula (VII):
- each R is independently methyl, ethyl, or iso-propyl, and R and R are independently H or methyl.
- a specific bidentate phosphorus-based ligand of formula (III) that can be used in the processes of the invention is a ligand of formula (V):
- Specific bidentate phosphorus-based ligands that can be used in the processes of the invention can include the ligand of formula (III) is of formula (XII)
- R , R , R and R are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 - R Y1 ° is independently selected from the group consisting of hydrogen, (CI -CIO) alkyl, and (Cl-ClO)alkoxy, or wherein two adjacent R Y3 -R Y1 ° groups together form an optionally substituted fused aryl ring.
- the invention can provide processes wherein for the ligand of formula
- R , R , R , and R are each independently phenyl substituted at a respective first ortho- position with a (Cl-ClO)alkyl or (Cl-ClO)alkoxy, at a respective second ort/zo-position with hydrogen, and wherein respective meta- and / a-positions of the R , R , R , and R phenyls can each independently be unsubstituted or be independently substituted with 1-3 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, or (C3- C 10)cycloalkoxy(C 1 -C
- R Y6 and R Y1 ° are independently (Cl-ClO)alkyl or (Cl-ClO)alkoxy
- R Y3 , R Y4 , R Y5 , R Y7 , R Y8 , and R Y9 are independently H, (Cl-ClO)alkyl, or (Cl-ClO)alkoxy, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (Cl-ClO)alkyl or (Cl- C10)alkoxy.
- the hydrolysis catalyst can be of formula (IA1):
- R 45 is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(Cl -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, and (C6-C20)aryl, and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl,
- R 45 can be methyl, ethyl, or isopropyl; and more specifically, in the hydrolysis catalyst of formula (IA1), (IBl), or both, R 45 can be methyl, ethyl, or isopropyl, R 46 can be hydrogen, and R 47 and R 48 can be independently selected from H and methyl.
- the hydrolysis catalyst can have the following formula (IA2):
- hydrolysis catalysts can arise in situ in a hydrocyanation reaction milieu through hydrolysis of a phosphite ester bond of tris(2,4-xylyl)phosphite (formula (XIII), a monodentate ligand of formula (IV).
- hydrolysis catalysts monodentate phosphorus-based ligands, and bidentate/tridentate phosphorus-based ligands as described above can also be used in carrying out the below-described processes of the invention. For the sake of brevity, they are not recapitulated in the description below, but it is apparent that analogous examples are disclosed and claimed herein.
- the invention can provide a process for modifying the relative ratio of two phosphorus- based ligands for a transition metal catalyst, wherein each ligand in the blend comprises at least one phosphite ester group, in a ligand blend comprising at least two phosphorus-based ligands, a first component of the blend being selected from the group consisting of a bidendate phosphorus- based ligand of formula (III) and a tridentate phosphorus-based ligand of formula (IIIA):
- 1 9 1 * 99 9 ⁇ 94 independently is oxygen or a bond, provided that at least one of X , X , X , X , X Or X is oxygen, and for the ligand of formula (IIIA), X 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , and X 34 , each independently is oxygen or a bond, provided that at least one ofX 1 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X , or X is oxygen; for the ligand of formula (III), R , R , R , and R , and for the ligand of formula (IIIA), R 12 , R 13 , R 22 , R 23 , and R 34 , each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- Cl 0)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl -CI 0)alkoxy, (C3-C10)cycloalkoxy(Cl- C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C10)haloalkyl, fluorine, chlorine, bromine, or (Cl- C10)haloalkyl, flu
- a second component of the blend being a monodentate phosphorus-based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X , X , or X is an oxygen; and R , R and R is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C
- the hydrolysis catalyst of formula (I) can be a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), ( ⁇ ), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both. More specifically, the hydrolysis catalyst of formula (I) can be a hydrolysis product of the monodentate ligand of formula (IV). However, it can also arise by hydrolysis of a bidentate ligand of formula (III) or a tridentate ligand of formula (IIIA).
- the ligand degradation products (hydrolysis products) of a ligand type that is selectively hydrolyzed under the reaction conditions in the presence of the hydrolysis catalyst can be separated from the ligand blend, such as, e.g., wherein the removal step ii) is through extraction between a nonpolar and a polar organic solvent.
- the nonpolar solvent can comprise cyclohexane, or similar nonpolar solvents, or mixtures thereof.
- polar solvent can be a raffmate that arises from the extraction process as applied to the reaction milieu resulting from the hydrocyanation reaction of butadiene, comprises adiponitrile, or both.
- the process stream undergoing purification or adjustment of ligand contents can be extracted with a non-polar solvent, partitioned versus a liquid medium containing the ligand blend, which in the extraction process becomes the raffmate of that extraction.
- the components of the ligand blend can be any as described above for phosphorus-based ligands of formulas (III), (IIIA), and (IV).
- the hydrolysis catalyst of formula (I) can be any described above.
- the bidentate ligand can be of formula (V),
- the monodentate ligand can be of formula (XIII)
- hydrolysis catalyst can be of the formula (IA2): or of formula (IB 2):
- the reaction milieu can include cyclohexane and/or toluene, and can also include one or more nitriles, such as pentenenitriles (e.g., 3-pentenenitrile), adiponitrile, or a mixture thereof.
- nitriles such as pentenenitriles (e.g., 3-pentenenitrile), adiponitrile, or a mixture thereof.
- the invention can provide a process for maintaining a concentration of a phosphorus- based bidentate ligand or of a phosphorus-based tridentate ligand, or both, within a concentration range, in a phosphorus-based ligand blend further comprising a monodentate phosphorus-based ligand, for a transition metal catalytic complex in a hydrocyanation reaction milieu comprising water and at least one organic liquid, wherein each phosphorus-based ligand in the blend comprises at least one phosphite ester group, the ligand blend comprising at least two
- phosphorus-based ligands a first component of the ligand blend being a bidendate phosphorus- based ligand of formula (III) and/or a tridentate phosphorus-based ligand of formula (IIIA): a bidentate phosphorus-based ligand of formula (III)
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is independently unsubstituted or is substituted with 1 -4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(Cl -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C10)
- a second component of the blend being a ligand comprising a monodentate phosphorus- based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X , X , or X is an oxygen; and R , R and R is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3
- the hydrolysis catalyst of formula (I) can a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both.
- the hydrolysis catalyst of formula (I) can be a hydrolysis product of the monodentate ligand of formula (IV).
- the concentrations of the various components of the ligand blend can be monitored throughout the hydrocyanation process, and in a continuous hydrocyanation process, the relative concentrations of ligands for the metal-ligand catalyst (e.g., a nickel-phosphoras-based ligand complex) are continuously monitored. These relative ligand proportions can be adjusted through selective hydrolysis and removal (e.g., by extraction) of ligand blend components that become excessive in proportion to other ligand blend components.
- the metal-ligand catalyst e.g., a nickel-phosphoras-based ligand complex
- the removal step ii) can be through extraction between a nonpolar and a polar organic solvent. Unwanted components can be removed up to the point that a favored concentration is achieved for each of the ligand blend components.
- the nonpolar solvent can comprise cyclohexane
- the polar solvent can be the raffinate from extraction of the reaction milieu resulting from the hydrocyanation reaction of butadiene, so can comprise pentenenitriles, can comprise adiponitrile, or both.
- the components of the ligand blend of formulas (III), (IIIA), and/or (IV) can be any of those described above, as can be the hydrolysis catalyst of formula (I).
- the ligand blend can include multiple ligands, such as a mixture of:
- hydrolysis catalyst is of the formula (IA2):
- the relative proportions of these ligands can controlled through monitoring, addition of hydrolysis catalyst if needed, and removal of acidic hydrolysis products resulting from selective hydrolysis of (one or more )monodentate ligands in the presence of the (one or more) bidentate (or tridentate) ligands.
- the reaction milieu can further comprise cyclohexane and/or toluene, and one or more nitriles such as 3-pentenenitrile and/or adiponitrile.
- Diphosphite bidentate ligand (V) can be prepared according to the procedure published in International Application Number PCT/US 10/60381 , International Application Number
- a solution of ligand (V) was a mixture in toluene with the major component (exclusive of solvent) being (V), but also including (XIII), (XIV), and hydrolysis products of (V), (XIII), or (XIV), and other products derived from the compounds used for (V) synthesis.
- a portion of the toluene was distilled and (V) ligand mixture subsequently dissolved in cyclohexane.
- An example composition of the (V) ligand solution in cyclohexane by P NMR is given in Table 1 as example 1 and by HPLC analysis in Table 2.
- Example 1 Ligand (V) solution in cyclohexane was subsequently exposed to water and heat. The experiment was conducted in a 10 ml glass serum vial with a rectangular stir bar and sealed with a Teflon coated septa using a temperature-regulated Reacti-BlockTM aluminum heating block enclosed in a nitrogen purge box and heated to 65 °C. The serum vial was charged with a solution of ligand in cyclohexane, inside a glove-box. Water was added by microsyringe to an initial concentration 2000 or 5000 ppm w .
- Example 2 (V) ligand mixture in cyclohexane was contacted with adiponitrile and subsequently exposed to water and heat.
- ligand (20 g) was mixed with 5 g of adiponitrile. The lower layer was removed and additional 5 g of adiponitrile was added. The lower layer was again removed and the resulting upper layer was analyzed by HPLC and P NMR for changes. The acidic ligand hydrolysis products were reduced from 3.2 to 1.3 mol % of the phosphorus content by 31 P NMR analysis, Table 1.
- a 10 ml glass serum vial was charged with 5 g of the upper layer solution and water was added by microsyringe to an initial concentration 2000 or 5000 ppm w .
- the experiment with water was conducted in a 10 ml glass serum vial with a rectangular stir bar and sealed with a Teflon coated septa using a temperature-regulated Reacti-BlockTM aluminum heating block heated to 65 °C. The heating block was enclosed in a nitrogen purge box. Samples were removed at desired intervals for analysis by HPLC for V, 7, 8, 2,4-xylenol and LHP-V product concentration.
- Phosphorous acid (PO3H3) was added to ligand (V) solution in cyclohexane to obtain 800 ppm w PO 3 H 3 in solution.
- a 10 ml glass serum vial was charged with 1.3 g of 800 ppm w P0 3 H 3 ligand (V) solution in cyclohexane, 3.7 g of mixture of pentenenitrile isomers, and water added to a concentration of the water for the total mixture to be 2000 ppm w .
- the experiment with water was conducted in a 10 ml glass serum vial with a rectangular stir bar and sealed with a Teflon coated septa using a temperature-regulated Reacti-BlockTM aluminum heating block heated to 65 °C.
- Example 4 Removal of acidic phosphorous ester groups by contacting with adiponitrile.
- Phosphorous acid (PO3H3) was added to ligand solution (V) in cyclohexane to obtain 800 ppm w PO 3 H 3 in solution.
- 20 g of the 800 ppm w PO3H 3 ligand (V) solution in cyclohexane was mixed with 5 g of adiponitrile.
- the lower layer was removed and additional 5 g of adiponitrile was added.
- the lower layer was again removed and the resulting upper layer was analyzed by HPLC and 31 P NMR for changes.
- a 10 ml glass serum vial was charged with 1.3 g of the upper layer, and 3.7 g of a mixture of pentenenitriles isomers, and water to obtain an initial concentration 2000 ppm w . inside a glove-box.
- the experiment with water was conducted in a 10 ml glass serum vial with a rectangular stir bar and sealed with a Teflon coated septa using a temperature-regulated Reacti- BlockTM aluminum heating block heated to 65 °C and enclosed in a nitrogen purge box. Samples were removed at desired intervals for analysis by HPLC for (V), (XIII), (XIV), 2,4-xylenol and LHP-V product concentration. Pentenenitrile solution reactivity with ligand at 75 °C.
- Phosphorous acid (P0 3 3 ⁇ 4) was added to ligand (V) solution in cyclohexane to obtain 400 ppm w P0 3 H 3 in solution.
- a 10 ml glass serum vial was charged with 1.3 g of the 400 ppm w PO 3 H 3 ligand (V) solution in cyclohexane, 3.8 g of mixture of pentenenitrile isomers, and water added to an initial concentration of the water for the total mixture to be 6000 ppm w .
- the experiment with water was conducted in a 10 ml glass serum vial with a rectangular stir bar and sealed with a Teflon coated septa using a temperature-regulated Reacti-BlockTM aluminum heating block heated to 75 °C. The heating block was enclosed in a nitrogen purge box. Samples were removed at desired intervals for analysis by HPLC for (V), (XIII), (XIV), 2,4-xylenol and one hydrolysis product of formula V (LHP-V)
- Example 6 Removal of acidic phosphorous ester groups by contacting the ligand (V) solution with adiponitrile.
- Phosphorous acid H 3 P0 3
- ligand solution in cyclohexane was added to ligand solution in cyclohexane to obtain 400 ppm w PO3H in solution.
- 20 g of the 400 ppm w P0 3 H 3 ligand (V) solution in cyclohexane was mixed with 5 g of adiponitrile.
- the lower layer was removed and additional 5 g of adiponitrile was added.
- the lower layer was again removed.
- a 10 ml glass serum vial was charged with a 1.3 g of the upper layer and 3.7 g of a mixture of pentenenitriles isomers. Water was added by microsyringe to an initial concentration 6000 ppm w .
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3 -C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3 -C 10)cycloalky
- phosphorus-based ligand selected from the group consisting of: :
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alk
- the groups Y 1 and Y 2 independently is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-
- C10)cycloalkoxy(Cl-C10)alkyl (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl- C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C10)haloalkyl;
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1 -4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycl
- R 1 , R 2 , R 3 , R 11 , R 12 , R 13 , R 22 , R 23 or R 34 is each an independently selected (C6-C20)aryl group, which is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkyl(C
- R 3 , R 11 , R 12 , R 13 , R 22 , R 23 or R 34 is a group of formula (II)
- R is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C 10)cycloalkyl(C 1 -C 10)alkyl, (C3 -C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3- C10)cycloalkoxy(C 1 -C 10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, and (C6-C20)aryl, and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl- C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3
- Y or independently selected Y 1 or Y 2 , is a (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted independently with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, (C6- C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl-ClO)haloalkyl.
- hydrolysis catalyst of formula (I) is a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both.
- hydrocyanation reaction of butadiene comprises adiponitrile, or both.
- each R and R is independently selected from the group consisting of (C 1 -C 10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, and (C3- C10)cycloalkoxy(Cl-C10)alkoxy, and each of R 42 , R 43 , R 44 , R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3
- R 41 is methyl, ethyl, isopropyl or cyclopentyl
- R 42 is H or methyl
- R 43 is H or (Cl-C4)alkyl
- R 44 is H or methyl
- R 45 is methyl, ethyl, or isopropyl
- R 46 , R 47 and R 48 are independently H or (Cl-C4)alkyl.
- R 17 is methyl, ethyl or iso-propyl, and R 18 and R 19 are independently H or methyl.
- R 12 , R°, R 22 and R i are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 - R Y1 ° is independently selected from the group consisting of hydrogen, (C1-C10) alkyl, and (Cl-ClO)alkoxy, or wherein two adjacent R Y3 -R Y10 groups together form an optionally substituted fused aryl ring.
- R , R , R , and R are each independently phenyl substituted at a respective first or ⁇ o-position with a (Cl-ClO)alkyl or (Cl-ClO)alkoxy, at a respective second ort&o-position with hydrogen, and wherein respective meta- and para- positions of the R 12 , R 13 , R 22 , and R 23 phenyls can each independently be unsubstituted or be substituted independently with 1-3 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C 10)cycloalkyl(C 1 -C 10)alkoxy, or (C3-C 10)cycloalk
- R Y6 and R Y1 ° are independently (Cl-ClO)alkyl or (Cl-ClO)alkoxy
- R Y3 , R Y4 , R Y5 , R Y7 , R Y8 , and R Y9 are independently H, (Cl-ClO)alkyl, or (Cl-ClO)alkoxy, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (Cl-ClO)alkyl or (Cl- C10)alkoxy.
- R 45 is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl- C10)alkoxy, and (C6-C20)aryl, and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cyclo
- each ligand in the blend comprises at least one phosphite ester group, in a ligand blend comprising at least two phosphorus-based ligands, a first component of the blend being selected from the group consisting of a bidendate phosphorus-based ligand of formula (III) and a tridentate phosphorus-based ligand of formula (IIIA):
- X 12 , X 13 , X 14 , X 22 , X 23 ' or X 24 is oxygen
- X 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , and X 34 each independently is oxygen or a bond, provided that at least one of X 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , and X 34 is oxygen;
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)al
- groups Y and Y independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted independently with 1-4 (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3 -C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3- C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl-ClO)haloalkyl;
- a second component of the blend being a ligand comprising a monodentate phosphorus- based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cyclo
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R n is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3 -C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalky
- R 1 , R 2 , R 3 , R 11 , R 12 , R 13 , R 22 , R 23 or R 34 is each an independently selected (C6-C20)aryl group, which is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)
- R is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C 10)cycloalkyl(C 1 -C 10)alkyl, (C3 -C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3- C10)cycloalkoxy(C 1 -C 10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, and (C6-C20)aryl, and each of R , R and R is independently selected from the group consisting of H, (Cl- C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3- C
- Y or independently selected Y 1 or Y 2 , is a (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted independently with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, (C6- C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl-ClO)haloalkyl.
- hydrolysis catalyst of formula (I) is a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both.
- each R and R is independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, and (C3- C10)cycloalkoxy(Cl-C10)alkoxy, and each of R 42 , R 43 , R 44 , R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3
- R 41 is methyl, ethyl, isopropyl, or cyclopentyl
- R 42 is H or methyl
- R 43 is H or (Cl-C4)alkyl
- R 44 is H or methyl
- R 45 is methyl, ethyl, or isopropyl
- R 46 , R 47 and R 48 are independently H or (Cl-C4)alkyl.
- R 17 is methyl, ethyl or iso-propyl
- R i 1 S 8 and R , x 1 y 9 are independently H or methyl
- R 12 , R 13 , R 22 and R 23 are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 - R Y1 ° is independently selected from the group consisting of hydrogen, (CI -CIO) alkyl, and (Cl-ClO)alkoxy, or wherein two adjacent R Y3 -R Y10 groups together form an optionally substituted fused aryl ring.
- R , R , R , and R are each independently phenyl substituted at a respective first oriAo-position with a (Cl-ClO)alkyl or (Cl-ClO)alkoxy, at a respective second ort/zo-position with hydrogen, and wherein respective meta- and para- positions of the R 12 , R 13 , R 22 , and R 23 phenyls can each independently be unsubstituted or be independently substituted with 1-3 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C 10)cycloalkyl(C 1 -C 10)alkoxy, or (C3 -C 10)cycl
- R Y6 and R Y1 ° are independently (Cl-ClO)alkyl or (Cl-ClO)alkoxy
- R Y3 , R Y4 , R Y5 , R Y7 , R Y8 , and R Y9 are independently H, (Cl-ClO)alkyl, or (Cl-ClO)alkoxy, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (Cl-ClO)alkyl or (Cl- C10)alkoxy.
- each R 45 is independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3- C10)cycloalkoxy(Cl-C10)alkoxy, and (C6-C20)aryl, and each of R 46 , R 47 and R 48 is
- H independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl- C10)alkoxy, and (C6-C20)aryl.
- reaction milieu further comprises cyclohexane and/or toluene.
- reaction milieu further comprises one or more nitriles.
- nitriles comprise adiponitnle. 42.
- ⁇ 94 independently is oxygen or a bond, provided that at least one of X , X , X , X , X ' or X is oxygen, and for the ligand of formula (IIIA), X 12 , X 13 , X 14 , X 22 , X 23 ' X 24 , X 32 , X 33 , and X 34 , each independently is oxygen or a bond, provided that at least one of 12 3 14- 22 23 24 32 l X' X' X , X"' X ", X Ji , X , or X is oxygen;
- each independently is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3- C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alk
- the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl- C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl- C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl- C10)haloalkyl;
- a second component of the blend being a monodentate phosphorus-based ligand of formula (IV)
- X 1 , X 2 and X 3 are each independently oxygen or a bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(Cl- C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(Cl-C10)alkyl of R 1 , R 2 , or R 3 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cyclo
- n 0, 1, or 2
- each X 11 is independently oxygen or a bond
- each independently selected R 11 is (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(Cl- CI 0)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C 1 -C 10)alkyl, wherein for any (C6-C20)aryl or (C6- C20)aryl(Cl-C10)alkyl of R 11 , each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycl
- R 1 , R 2 , R 3 , R 11 , R 12 , R 13 , R 22 , R 23 or R 34 is each an independently selected (C6-C20)aryl group, which is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (Cl-ClO)alkyl, (C3- C10)cycloalkyL (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)
- R is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, and (C6-C20)aryl, and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl- C10)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3- C 10)cycloalkyl(C 1
- Y or independently selected Y 1 or Y
- Y is a (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C10)cycloalkyl(Cl-C10)alkoxy, (C3-C10)cycloalkoxy(Cl-C10)alkoxy, (C6-C20)aryl, (C6- C20)aryl(Cl-C10)alkyl, fluorine, chlorine, bromine, or (Cl-ClO)haloalkyl.
- hydrocyanation reaction of butadiene comprises adiponitrile, or both.
- each R and R is independently selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3-C10)cycloalkyl(Cl-C10)alkoxy, and (C3- C10)cycloalkoxy(Cl-C10)alkoxy, and each of R 42 , R 43 , R 44 , R 46 , R 47 and R 48 is independently selected from the group consisting of H, (C 1 -C 10)alkyl, (C3 -C 10)cycloalkyl, (C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy, (C3-C 10)cycloalkyl(C 1 -C 10)alky
- R is methyl, ethyl, isopropyl, or cyclopentyl
- R 42 is H or methyl
- R 43 is H or (Cl-C4)alkyl
- R 44 is H or methyl
- R 45 is methyl, ethyl, or isopropyl
- R 46 , R 47 and R 48 are independently H or (CI -C4)alkyl.
- R 17 is methyl, ethyl or iso-propyl, and R and R are independently H or methyl.
- R 12 , R 13 , R 22 and R 23 are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 - R Y1 ° is independently selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, and (C 1 -C 10)alkoxy, or wherein two adj acent R -R groups together form an optionally substituted fused aryl ring.
- R 12 , R 13 , R 22 , and R 23 are each independently phenyl substituted at a respective first ort/zo-position with a (Cl-ClO)alkyl or (Cl-ClO)alkoxy, at a respective second ort/zo-position with hydrogen, and wherein respective meta- and para- positions of the R , R , R , and R phenyls can each independently be unsubstituted or be independently substituted with 1-3 (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3-C10)cycloalkoxy(Cl-C10)alkyl, (C3- C 10)cycloalkyl(C 1 -C 10)alkoxy, or (C3 -C
- R Y6 and R Y1 ° are independently (Cl-ClO)alkyl or (Cl-ClO)alkoxy, and R Y3 , R Y4 , R Y5 ,
- R Y7 , R Y8 , and R Y9 are independently H, (Cl-ClO)alkyl, or (Cl-ClO)alkoxy, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (Cl-ClO)alkyl or (Cl- C10)alkoxy. 55. The process of any one of statements 42-49, wherein the ligand of formula (III) is of formula (V):
- R 45 is selected from the group consisting of (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl, (C3- C 10)cycloalkoxy(C 1 -C 10)alkyl, (C3-C 10)cycloalkyl(C 1 -C 10)alkoxy, (C3-C 10)cycloalkoxy(C 1 - C10)alkoxy, and (C6-C20)aryl, and each of R 46 , R 47 and R 48 is independently selected from the group consisting of H, (Cl-ClO)alkyl, (C3-C10)cycloalkyl, (Cl-ClO)alkoxy, (C3- C10)cycloalkoxy, (C3-C10)cycloalkyl(Cl-C10)alkyl,
- reaction milieu further comprises cyclohexane and/or toluene.
- reaction milieu further comprises one or more nitriles.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380041070.5A CN104619711B (en) | 2012-06-01 | 2013-05-24 | Hydrolyst and method |
EP13797289.9A EP2870166B1 (en) | 2012-06-01 | 2013-05-24 | Hydrolysis catalyst and process |
KR20147036668A KR20150023513A (en) | 2012-06-01 | 2013-05-24 | Hydrolysis catalyst and process |
US14/404,030 US10087201B2 (en) | 2012-06-01 | 2013-05-24 | Hydrolysis catalyst and process |
JP2015515087A JP2015523344A (en) | 2012-06-01 | 2013-05-24 | Hydrolysis catalyst and process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261654554P | 2012-06-01 | 2012-06-01 | |
US61/654,554 | 2012-06-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013181092A1 true WO2013181092A1 (en) | 2013-12-05 |
Family
ID=49673837
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2013/042613 WO2013181092A1 (en) | 2012-06-01 | 2013-05-24 | Hydrolysis catalyst and process |
Country Status (6)
Country | Link |
---|---|
US (1) | US10087201B2 (en) |
EP (1) | EP2870166B1 (en) |
JP (1) | JP2015523344A (en) |
KR (1) | KR20150023513A (en) |
CN (1) | CN104619711B (en) |
WO (1) | WO2013181092A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10087201B2 (en) | 2012-06-01 | 2018-10-02 | Invista North America S.A R.L. | Hydrolysis catalyst and process |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG11202010910QA (en) | 2018-05-07 | 2020-12-30 | Alnylam Pharmaceuticals Inc | Extrahepatic delivery |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5981722A (en) | 1995-11-20 | 1999-11-09 | Board Of Regents For The University Of Oklahoma | Trypsin inhibitors with insecticidal properties obtained from PENTACLETHRA MACROLOBA |
US6169198B1 (en) | 1997-08-04 | 2001-01-02 | Basf Aktiengesellshaft | Method for producing mixtures of monoolefinic C5-mononitriles by catalytic hydrocyanation |
US20040122251A1 (en) * | 2002-12-23 | 2004-06-24 | Rhodia Polyamide Intermediates | Process of synthesis of compounds having nitrile functions from ethylenically unsaturated compounds |
WO2011087688A1 (en) * | 2009-12-22 | 2011-07-21 | Dow Technology Investments Llc | Controlling the normal:iso aldehyde ratio in a mixed ligand hydroformylation process by controlling the syngas partial pressure |
WO2012005910A1 (en) * | 2010-07-07 | 2012-01-12 | Invista Technologies S.A. R.L. | Process for making nitriles |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3655723A (en) | 1969-10-31 | 1972-04-11 | Du Pont | Hydrocyanation of olefins |
US5886235A (en) | 1995-12-06 | 1999-03-23 | Union Carbide Chemicals & Plastics Technology Corporation. | Metal-ligand complex catalyzed processes |
FR2854891B1 (en) * | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | PROCESS FOR PREPARING DINITRILES |
CN101405292A (en) * | 2006-03-17 | 2009-04-08 | 因温斯特技术公司 | Method for the purification of triorganophosphites by treatment with a basic additive |
US7659422B2 (en) | 2006-07-14 | 2010-02-09 | Invista North America S.A.R.L. | Hydrocyanation process with reduced yield losses |
WO2009091790A1 (en) | 2008-01-15 | 2009-07-23 | Invista Technologies S.A.R.L. | Hydrocyanation of pentenenitriles |
EP2229354B1 (en) | 2008-01-15 | 2013-03-20 | Invista Technologies S.à.r.l. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
CN107383087A (en) | 2009-04-21 | 2017-11-24 | 英威达纺织(英国)有限公司 | For preparing the high selective method of organodiphosphite |
US8815186B2 (en) | 2009-12-18 | 2014-08-26 | Invista North America S.A.R.L. | Nickel compositions for preparing nickel metal and nickel complexes |
WO2012033556A1 (en) | 2010-09-07 | 2012-03-15 | Invista Technologies S.A R.L. | Preparing a nickel phosphorus ligand complex |
CN109369706A (en) | 2012-06-01 | 2019-02-22 | 英威达纺织(英国)有限公司 | Stable ligand mixture and methods for making them |
JP2015523344A (en) | 2012-06-01 | 2015-08-13 | インヴィスタ テクノロジーズ エスアエルエル | Hydrolysis catalyst and process |
-
2013
- 2013-05-24 JP JP2015515087A patent/JP2015523344A/en active Pending
- 2013-05-24 US US14/404,030 patent/US10087201B2/en active Active
- 2013-05-24 KR KR20147036668A patent/KR20150023513A/en not_active Application Discontinuation
- 2013-05-24 WO PCT/US2013/042613 patent/WO2013181092A1/en active Application Filing
- 2013-05-24 EP EP13797289.9A patent/EP2870166B1/en active Active
- 2013-05-24 CN CN201380041070.5A patent/CN104619711B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5981722A (en) | 1995-11-20 | 1999-11-09 | Board Of Regents For The University Of Oklahoma | Trypsin inhibitors with insecticidal properties obtained from PENTACLETHRA MACROLOBA |
US6169198B1 (en) | 1997-08-04 | 2001-01-02 | Basf Aktiengesellshaft | Method for producing mixtures of monoolefinic C5-mononitriles by catalytic hydrocyanation |
US20040122251A1 (en) * | 2002-12-23 | 2004-06-24 | Rhodia Polyamide Intermediates | Process of synthesis of compounds having nitrile functions from ethylenically unsaturated compounds |
US7470805B2 (en) | 2002-12-23 | 2008-12-30 | Rhodia Operations | Process of synthesis of compounds having nitrile functions from ethylenically unsaturated compounds |
WO2011087688A1 (en) * | 2009-12-22 | 2011-07-21 | Dow Technology Investments Llc | Controlling the normal:iso aldehyde ratio in a mixed ligand hydroformylation process by controlling the syngas partial pressure |
WO2012005910A1 (en) * | 2010-07-07 | 2012-01-12 | Invista Technologies S.A. R.L. | Process for making nitriles |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10087201B2 (en) | 2012-06-01 | 2018-10-02 | Invista North America S.A R.L. | Hydrolysis catalyst and process |
Also Published As
Publication number | Publication date |
---|---|
CN104619711B (en) | 2018-02-13 |
EP2870166A1 (en) | 2015-05-13 |
US20150158892A1 (en) | 2015-06-11 |
EP2870166B1 (en) | 2018-07-18 |
KR20150023513A (en) | 2015-03-05 |
US10087201B2 (en) | 2018-10-02 |
EP2870166A4 (en) | 2016-06-01 |
JP2015523344A (en) | 2015-08-13 |
CN104619711A (en) | 2015-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103097343B (en) | For the preparation of the method for nitrile | |
BRPI0713243A2 (en) | process for the continuous production of 3-pentenonitrile | |
EP2870167B1 (en) | Stable ligand mixtures and processes for making same | |
CN107082752B (en) | Separation of solvent from nickel catalyst by distillation | |
EP2870166B1 (en) | Hydrolysis catalyst and process | |
CN104011014B (en) | For the preparation of the method for nitrile | |
EP2855492A1 (en) | Process for stabilizing hydrocyanation catalyst | |
WO2014089492A1 (en) | Composition for improved nickel-ligand solubility | |
EP2928597B1 (en) | Improved process for producing pentenenitriles | |
EP2855493A1 (en) | Stabilized hydrocyanation ligand composition | |
WO2024028715A1 (en) | Processes for producing nitriles and phosphorus-containing catalysts for use in such processes | |
WO2023228077A1 (en) | Multidentate phosphite ligands, catalytic compositions containing such ligands, and catalytic processes utilizing such catalytic compositions | |
WO2024028716A1 (en) | Processes for producing nitriles and phosphorus-containing catalysts for use in such processes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13797289 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14404030 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2015515087 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013797289 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20147036668 Country of ref document: KR Kind code of ref document: A |