WO1999006355A1 - Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles - Google Patents
Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles Download PDFInfo
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- WO1999006355A1 WO1999006355A1 PCT/US1998/014743 US9814743W WO9906355A1 WO 1999006355 A1 WO1999006355 A1 WO 1999006355A1 US 9814743 W US9814743 W US 9814743W WO 9906355 A1 WO9906355 A1 WO 9906355A1
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- Prior art keywords
- alkyl
- formula
- improved process
- aryl
- independently
- Prior art date
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- 238000005669 hydrocyanation reaction Methods 0.000 title claims abstract description 42
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 27
- 150000001993 dienes Chemical class 0.000 title claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- -1 acyclic nitriles Chemical class 0.000 claims abstract description 12
- 230000006872 improvement Effects 0.000 claims abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 26
- 125000006539 C12 alkyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical group C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- APPOKADJQUIAHP-UHMKDZKBSA-N (4e)-hexa-2,4-diene Chemical compound CC=C\C=C\C APPOKADJQUIAHP-UHMKDZKBSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- KBVDKMYIVHHRON-UHFFFAOYSA-N 2-ethenylpentanenitrile Chemical compound CCCC(C=C)C#N KBVDKMYIVHHRON-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims 2
- WYGBYUCRAQJFAF-UHFFFAOYSA-N 2-ethylbut-3-enenitrile Chemical compound CCC(C=C)C#N WYGBYUCRAQJFAF-UHFFFAOYSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 description 25
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 0 CC1(C(CCC=C2)=C2C(*)=CC1)OPOc1ccccc1* Chemical compound CC1(C(CCC=C2)=C2C(*)=CC1)OPOc1ccccc1* 0.000 description 5
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 5
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical group C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000292604 Salvia columbariae Species 0.000 description 1
- 235000012377 Salvia columbariae var. columbariae Nutrition 0.000 description 1
- 235000001498 Salvia hispanica Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- XMQFTWRPUQYINF-UHFFFAOYSA-N bensulfuron-methyl Chemical class COC(=O)C1=CC=CC=C1CS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 XMQFTWRPUQYINF-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NKKMVIVFRUYPLQ-UHFFFAOYSA-N but-2-enenitrile Chemical compound CC=CC#N NKKMVIVFRUYPLQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003251 chemically resistant material Substances 0.000 description 1
- 235000014167 chia Nutrition 0.000 description 1
- UHAVKULAJAUFJI-UHFFFAOYSA-N chloro(dinaphthalen-1-yloxy)phosphane Chemical compound C1=CC=C2C(OP(OC=3C4=CC=CC=C4C=CC=3)Cl)=CC=CC2=C1 UHAVKULAJAUFJI-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc 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
- C07F9/144—Esters of phosphorous acids with cycloaliphatic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/03—Mononitriles
-
- 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
Definitions
- This invention generally relates to an improved liquid phase process useful in the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitriles and to a liquid phase process of isomerization of said nitriles to, among other things, 3- and/or 4-monoalkene linear nitriles.
- the improvement resides in conducting the processes in the presence of zero-valent nickel and a multi dentate phosphite ligand.
- Catalytic hydrocyanation systems particularly pertaining to the hydrocyanation of olefins. are known in the art.
- liquid phase systems useful for the hydrocyanation of butadiene to form pentenenitriles (PN) are known in the art.
- PN pentenenitriles
- Drinkard, U.S. 3,496,215 discloses the hydrocyanation of butadiene using nickel catalysts with monodentate phosphite ligands.
- pentenenitrile is intended to mean cyanobutene.
- butenenitrile means cyanopropene.
- adiponitrile ADN
- Drinkard U.S. 3,536,748, discloses the liquid phase isomerization of 2-methyl-3 -butenenitrile in the presence of a zero valent nickel complex and Chia.
- U.S. 3,676,481 discloses an improvement additionally utilizing tri(hydrocarbyl)boron promoters.
- hydrocyanation of activated olefins such as conjugated olefins (e.g., butadiene and styrene) and strained olefins (e.g., norbornene) proceeds without the use of a Lewis acid promoter, while hydrocyanation of unactivated olefins such as 1-octene and 3 -pentenenitrile normally require the use of a Lewis acid promoter.
- teachings regarding the use of a promoter in the hydrocyanation reaction appear, for example, in U.S. 3,496,217.
- Certain multidentate phosphite ligands useful in the present invention for the hydrocyanation of diolefins have been used for the hydrocyanation of monoolefins.
- Commonly assigned, WO 95/14659 and U.S. Patent 5,512,696, disclose bidentate phosphite ligands preferably used in combination with a Lewis acid promotor to hydrocyanate monoolefins.
- the present invention provides for an improved process for the hydrocyanation of diolefinic compounds, such as butadiene, and isomerization of nonconjugated acyclic nitriles without the need for Lewis acid promoters utilizing zero-valent nickel and a multidentate phosphite ligand wherein there is at least one 1-naphthol terminus present.
- the present invention provides an improved process for the liquid phase hydrocyanation of diolefinic compounds and isomerization of the resulting nonconjugated acyclic nitriles comprising, reacting an acyclic aliphatic diolefinic compound, preferably butadiene, with a source of HCN, wherein the improvement comprises conducting the hydrocyanation and/or isomerzation in the presence of a catalyst precursor composition comprising zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III. IV, V, VI, VII, VIII. IX and X, as set forth below:
- each R 1 is independently a H, halogen, primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR 3 wherein R 3 is a C j to C12 alkyl, or CO 2 R 3 ' wherein R 3' is a Ci to Cj 2 alkyl, or aryl; each R 2 and R 2' are independently a H. halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms.
- R 3 is a C j to C ] 2 alkyl, or CO 2 R 3 ' wherein R 3' is a C ⁇ to C ⁇ 2 alkyl, or aryl; when R 2 ' is not hydrogen, R 2 ' cannot be ortho to the oxygen; each R 5 ' is independently a H.
- halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms OR 3 wherein R 3 is a Cj to C ⁇ 2 alkyl, or CO2R 3 ' wherein R 3 ' is a Cj to C12 alkyl, or aryl; each R 9 is independently H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR 3 wherein R 3 is a C j to C j2 alkyl, or CO 2 R 3 ' wherein R 3 ' is a Cj to C12 alkyl, or aryl; and each X is independently O or CH(R 4 '), wherein R 4 ' is H, aryl, or a C j to
- the present invention provides an improved process for the liquid phase hydrocyanation of diolefinic compounds, reacting an acyclic aliphatic diolefinic compound, preferably butadiene, with a source of HCN, wherein the improvement comprises conducting the hydrocyanation in the presence of a catalyst precursor composition comprising zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III, IV, V, VI, VII, VIII, IX and X, as set forth below:
- each R' is independently a H, halogen, primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR 3 wherein R 3 is a Ci to C j2 alkyl. or CO 2 R 3 ' wherein R 3 ' is a Cj to C 12 alkyl, or aryl; each R 2 and R 2 ' are independently a H.
- each R 5' is independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR 3 wherein R 3 is a C j to C 12 alkyl, or CO2R 3' wherein R 3' is a C] to C 12 alkyl, or aryl; each R 9 is independently H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR 3 wherein R 3 is a C to C12 alkyl, or CO 2 R 3 ' wherein R 3 ' is a Cj to C ⁇ 2 alkyl,
- the reactions are most conveniently performed continuously from hydrocyanation of the starting diolefin to the final 3- and or 4-monoalkene linear nitriles.
- the processes can be conducted stepwise, i.e., the nonconjugated acyclic nitriles resulting from the hydrocyanation can be isolated per se. prior to isomerization.
- nonconjugated acyclic nitriles prepared by any method can be used as starting materials for the isomerization in accordance with this invention.
- the invention also provides for certain multidentate phosphite ligands and catalyst precursor compositions made therefrom useful in these processes.
- these include the ligands of Formulas I-IV and VI-X.
- Catalyst precursor compositions consisting of zero-valent nickel and at least one multidentate phosphite ligand according to Formula I-X are also covered.
- the catalyst precursor compositions useful in the processes of the invention are comprised of a multidentate phosphite ligand and zero-valent nickel.
- the catalyst composition is referred to as a "precursor" only to indicate in all likelihood, during the hydrocyanation reaction the structure of the active catalyst composition may in fact be complexed to an olefin.
- These ligands may be prepared by a variety of methods known in the art, for example, see descriptions in WO 93,03839. U.S. 4,769,498; U.S. 4,688,651, J. Amer. Chem. Soc, 1993, 115. 2066.
- the reaction of di-(l-naphthyl)- phosphorochloridite with 1 , 1 '-binaphthol in the presence of triethylamine gives a ligand according to Formula V.
- the phosphorochloridite may be prepared by a variety of methods known in the art, for example, see descriptions in Polymer. 1992. 33, 161; Inorganic Syntheses, 1966, 8, 68; U.S. 5,210,260; Z. Anorg. Allg. Chem.. 1986, 535, 221.
- phosphoro- chloridites can be prepared in situ from PC1 3 and the phenol. With less bulky groups, purification by high vacuum distillation is typically necessary. High vacuum distillation is difficult for large scale operations.
- An improved process for preparing the phosphorochloridite comprises treatment of N,N-dialkyl diarylphosphoramidite derivatives with HC1.
- ClP(OMe) 2 has been prepared in this mariner, see Z. Naturforsch, 1972, 27 B, 1429; phosphorochlorides derived from substituted phenols have been prepared using this procedure as described in copending, commonly assigned, application Serial No. 08/563,718 filed November 28,1995.
- N.N-dialkyl diarylphos- phoramidites may be prepared by methods known in the art . for example, see descriptions in Tetrahedron Letters, 1993. 34, 6451 and Aust. J. Chem, 1991, 233. It has also been found that phosphorochlorodite of 1 -naphthol can be prepared in situ from PC1 3 and 1-napthol.
- the zero-valent nickel can be prepared or generated according to techniques known in the art (U.S. 3,496,217; 3,631,191; 3,846,461; 3,847,959; and 3,903,120 which are incorporated herein by reference).
- Zero-valent nickel compounds that contain ligands which can be displaced by the organophosphorus ligand are a preferred source of zero-valent nickel.
- Two such preferred zero- valent nickel compounds are Ni(COD) 2 (COD is 1,5-cyclooctadiene) and Ni(P(O-o-C 6 H4CH 3 )3)2(C 2 H 4 ), both of which are known in the art.
- divalent nickel compounds may be combined with a reducing agent, and are then able to serve as suitable sources of zero-valent nickel in the reaction.
- Suitable divalent nickel compounds include compounds of the formula MY2 where Y is halide, carboxylate, or acetylacetonate.
- Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Zn, Fe, Al, Na, or H 2 .
- the actual catalyst precursor is a complex of zero-valent nickel with the multidentate phosphite ligand, which is formed when those two materials are combined.
- An effective catalyst typically requires at least two moles of P atoms for one gram-atom of zero-valent nickel.
- the diolefinic compounds reactants used in this invention include primarily conjugated diolefins containing from 4 to 10 carbon atoms; for example, 1 ,3"butadiene and cis and trans-2.4-hexadienes. Butadiene is especially preferred by reason of its commercial importance in the production of adiponitrile.
- Other suitable diolefinic compounds include diolefinic compounds substituted with groups which do not deactivate the catalyst, for example, s and trans- 1.3- pentadienes.
- Formulas XI and XII illustrate suitable representative starting diolefinic compounds; and Formulas XIII, XIV, and XV represent the products obtained from 1 ,3-butadiene and HCN.
- each one of R 15 and R 16 is H or a C ] to C3 alkyl.
- CH 2 CH-CH 2 -CH 2 -CN CN
- the hydrocyanation reaction can be carried out with or without a solvent.
- the solvent should be a liquid at the reaction temperature and inert towards the unsaturated compound and the catalyst.
- solvents are hydrocarbons such as benzene, xylene, or nitriles such as acetonitrile, benzonitrile, or adiponitrile.
- temperatures of from -25°C to 200°C can be used with from 0°C to 150°C, being the preferred range.
- the reaction may be carried out by charging a reactor with all of the reactants or preferably the reactor is charged with the catalyst or catalyst components, the unsaturated compound and whatever solvent is to be used and the hydrogen cyanide gas is swept over the surface of the reaction mixture or bubbled through said reaction mixture. If desired, when using a gaseous unsaturated organic compound, the hydrogen cyanide and the unsaturated organic compound may be fed together into the reaction medium.
- the molar ratio of HCN to catalyst generally is varied from about 10:1 to 100.000:1, preferably 100:1 to 5,000:1, for a batch operation. In a continuous operation, such as when using a fixed bed catalyst type of operation, a higher proportion of catalyst may be used such as 5:1 to 100,000:1, preferably 100:1 to 5,000:1, HCN to catalyst.
- the reaction mixture is agitated, such as by stirring or shaking.
- the cyanated product can be recovered by conventional techniques such as crystallization of the product from solution or by distillation.
- the 2-alkyl-3-monoalkenenitriles used as the starting materials in the isomerization of this invention can result from the hydrocyanation of diolefin described above or can come from any other available source.
- the olefinic double bond in the 2-alkyl-3-monoalkenenitriles used as the starting materials in the isomerization of this invention cannot be conjugated to the triple bond of the cyano group.
- Suitable starting 2-alkyl-3-monoalkenenitriles can also carry groups which do not attack the catalyst, for example, another cyano group.
- the starting 2-alkyl-3-monoalkenenitriles contain from 5 to 8 carbon atoms, excluding any additional substitution.
- 2-Methy 1-3 -butenenitrile is especially important in the production of adiponitrile.
- Other representative nitriles include 2-ethy 1-3 -butenenitrile and 2-propyl-3-butenenitrile.
- the following Formulas XVI and XVII illustrate suitable representative starting 2-alkyl-3-monoalkenenitriles. When the starting nitrile is 2-methyl-3- butenenitrile, the isomerization products are those shown in Formulas XVIII and XIX.
- R 17 is H or a Cj to C 3 alkyl.
- CH 2 CH-CH 2 -CH 2 CN
- CH 3 -CH 2 CH-CK 2 CN
- Formula XVI is a special case of Formula XVII, where R 17 is hydrogen.
- the isomerization process of this invention can be carried out, for example, at atmospheric pressure and at any temperature in the range of 10-200°C, preferably in the range 60-150°C.
- the pressure is not critical, however, and can be above or below atmospheric pressure if desired.
- Any of the conventional batch or continuous flow procedures may be used either in the liquid phase or in the vapor phase (with respect to the relatively volatile 2-mefhyl-3- butenenitrile reactant and linear pentenenitrile products).
- the reactor may be of any mechanically and chemically resistant material, and is usually of glass or an inert metal or alloy, e.g., nickel, copper, silver, gold, platinum, stainless steel, Monel ® . Hastelloy ® , etc.
- the process is usually carried out "neat", i.e., without an added diluent or solvent. Any solvent or diluent that is nondestructive of the catalyst can be used, however. Suitable solvents include aliphatic or aromatic hydrocarbons (hexane, cyclohexane, benzene), ethers (diethyl ether, tetrahydrofuran. dioxane, glycol dimethyl ether, anisole), esters (ethyl acetate, methyl benzoate). nitriles (acetonitrile, benzonitrile), etc.
- a nonoxidizing environment is desirable in order to retard oxidative deactivation of the catalyst.
- an inert atmosphere e.g., nitrogen
- air is normally and preferably used, although air may be used if desired at the expense of loss of a proportion of the catalyst through oxidation.
- the catalytic nickel complex is soluble to some extent at temperatures within the operable range and is usually completely soluble at the most preferred operating temperature.
- the nickel complex is essentially nonvolatile, whereas the 2-methyl-3-butenenitrile reactant and the linear pentenenitrile products are relatively volatile.
- the catalyst in a continuous flow procedure may be a component of the flowing system in a completely liquid-phase operation, it may be in a mobile nonflowing liquid state in a semi- vapor phase operation, or it may be in a fixed-bed state (usually on a solid support) in a conventional flowing vapor-phase operation.
- the time element in the process is not critical, and may generally be governed by practical considerations.
- the time required for a practical level of conversion of 2-methy 1-3 -butenenitrile to linear pentenenitriles is dependent upon the temperature of reaction, i.e., operation at lower temperature generally requires a longer time than operation at a higher temperature.
- a practical reaction time can be in the range of a few seconds to many hours, depending on the particular conditions and method of operation.
- the molar ratio of 2-methyl-3 -butenenitrile to catalyst is generally greater than 1 : 1, usually in the range from about 5: 1 to 20,000:1, preferably 100:1 to 5,000:1, for a batch or continuous operation.
- HCN Solution 25 wt % solutions of HCN were typically made by weighing 2.00 g of liquid HCN into 6.00 g of valeronitrile. in a glovebox. The resulting solutions were stored at -35°C until their use in experiments.
- Catalyst Solution For a typical multidentate phosphite ligand, 0.84 mmol of P atoms and 0.039 g of Ni(COD) 2 (0.14 mmol) were mixed in either toluene or tetrahydrofuran such that the total solution weight would be 5.00 g. The resulting catalyst solutions were typically used immediately after mixing.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69813233T DE69813233T2 (en) | 1997-07-29 | 1998-07-23 | HYDROCYANATION OF DIOLEFINES AND ISOMATION OF NON-CONJUGATED 2-ALKYL-3-MONOALKENNITRILES |
EP98935733A EP1000020B1 (en) | 1997-07-29 | 1998-07-23 | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US5402297P | 1997-07-29 | 1997-07-29 | |
US60/054,022 | 1997-07-29 |
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WO1999006355A1 true WO1999006355A1 (en) | 1999-02-11 |
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PCT/US1998/014743 WO1999006355A1 (en) | 1997-07-29 | 1998-07-23 | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
Country Status (7)
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US (2) | US6020516A (en) |
EP (1) | EP1000020B1 (en) |
DE (1) | DE69813233T2 (en) |
MY (1) | MY120453A (en) |
TW (1) | TW570912B (en) |
WO (1) | WO1999006355A1 (en) |
ZA (1) | ZA986374B (en) |
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- 1998-07-23 DE DE69813233T patent/DE69813233T2/en not_active Expired - Lifetime
- 1998-07-23 WO PCT/US1998/014743 patent/WO1999006355A1/en active IP Right Grant
- 1998-07-23 EP EP98935733A patent/EP1000020B1/en not_active Expired - Lifetime
- 1998-07-23 US US09/121,146 patent/US6020516A/en not_active Expired - Lifetime
- 1998-07-27 MY MYPI98003413A patent/MY120453A/en unknown
- 1998-08-01 TW TW087112454A patent/TW570912B/en not_active IP Right Cessation
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US9061970B2 (en) | 2008-01-25 | 2015-06-23 | Invista North America S.A.R.L. | Production of compounds comprising nitrile functional groups |
US9233917B2 (en) | 2008-06-17 | 2016-01-12 | Invista North America S.A R.L. | Preparation of nitriles from ethylenically unsaturated compounds |
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WO2010086246A1 (en) | 2009-01-29 | 2010-08-05 | Rhodia Operations | Method for producing compounds including nitrile functions |
Also Published As
Publication number | Publication date |
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ZA986374B (en) | 2000-01-17 |
DE69813233T2 (en) | 2003-12-11 |
EP1000020B1 (en) | 2003-04-09 |
DE69813233D1 (en) | 2003-05-15 |
US6171997B1 (en) | 2001-01-09 |
EP1000020A1 (en) | 2000-05-17 |
MY120453A (en) | 2005-10-31 |
TW570912B (en) | 2004-01-11 |
US6020516A (en) | 2000-02-01 |
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