JP2019147788A - アルコキシカルボニル化のためのプロピル架橋ジホスフィン配位子 - Google Patents
アルコキシカルボニル化のためのプロピル架橋ジホスフィン配位子 Download PDFInfo
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- JP2019147788A JP2019147788A JP2019023541A JP2019023541A JP2019147788A JP 2019147788 A JP2019147788 A JP 2019147788A JP 2019023541 A JP2019023541 A JP 2019023541A JP 2019023541 A JP2019023541 A JP 2019023541A JP 2019147788 A JP2019147788 A JP 2019147788A
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- butene
- ethylenically unsaturated
- alkoxycarbonylation
- pentene
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- 238000007083 alkoxycarbonylation reaction Methods 0.000 title abstract description 8
- 239000003446 ligand Substances 0.000 title abstract description 7
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KQQKVSYSUDUWHU-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C.CC(C)=C(C)C KQQKVSYSUDUWHU-UHFFFAOYSA-N 0.000 claims description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000002184 metal Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- SIAXLNZJVDMSIX-UHFFFAOYSA-N ClP(C(C)(C)C)C1=NC=CC=C1 Chemical compound ClP(C(C)(C)C)C1=NC=CC=C1 SIAXLNZJVDMSIX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006063 methoxycarbonylation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- NMJASRUOIRRDSX-UHFFFAOYSA-N tert-butyl(dichloro)phosphane Chemical compound CC(C)(C)P(Cl)Cl NMJASRUOIRRDSX-UHFFFAOYSA-N 0.000 description 2
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- -1 diphosphine compound Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F15/006—Palladium compounds
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
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- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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Abstract
Description
(R1及びR2は、それぞれ独立的に−(C1−C12)−アルキルである)
a)エチレン性不飽和化合物をまず充填することと、
b)上記の化合物と、Pdを含む化合物とを添加すること、あるいは上記の錯体を添加することと、
c)アルコールを添加することと、
d)COを供給することと、
e)反応混合物を加熱してエチレン性不飽和化合物をエステルに転換させること
のステップを含む。
下記の調製は全て、標準シュレンク技術を用いて保護ガス下で行われた。溶媒を、使用前に適切な乾燥剤で乾燥させた(Purification of Laboratory Chemicals、W.L.F. Armarego(著)、Christina Chai(著)、Butterworth Heinemann(Elsevier)、第6版、Oxford 2009)。
クロロ−2−ピリジル−t−ブチルホスフィンを合成するためのグリニャールは、塩化イソプロピルマグネシウムを用いた「Knochel法」により調製される(Angew. Chem. 2004, 43, 2222-2226)。後処理はBudzelaarの方法(Organometallics 1990, 9, 1222-1227)に従って行われる。
1H NMR (300 MHz, C6D6): δ 8.36 (m, 1H, py), 7.67 (m, 1H, py), 7.03-6.93 (m, 1H, py), 6.55-6.46 (m, 1H, py), 1.07 (d, J = 13.3 Hz, 9H, t-Bu)。
13C NMR (75 MHz, C6D6): δ 162.9, 162.6, 148.8, 135.5, 125.8, 125.7, 122.8, 35.3, 34.8, 25.9, 25.8。
31P NMR (121 MHz, C6D6) δ 97.9。
MS (EI) m:z(相対強度)201 (M+, 2), 147 (32), 145 (100), 109 (17), 78 (8), 57.1 (17)。
(Graham Eastham等、米国特許第6,335,471号に類似)
300mlのParr反応器を使用する。これに適合するのは、社内で製造した、対応する寸法のアルミニウムブロックである。このブロックは、例えばHeidolphが市販しているマグネチックスターラによる加熱に適している。ガラスバイアルの外径に対応する穴6つを含む厚さ約1.5cmの円形金属板を製造し、オートクレーブの内側に備えた。ガラスバイアルと合わせて、小型のマグネチックスターラを備えている。ガラスバイアルにスクリューキャップ及び適当なセプタムを設けて、適当な反応体、溶媒、触媒、添加剤を、ガラス送風機により製造された特別な装置を用いてアルゴン下で充填する。この目的のために、6つの容器を同時に充填する。これにより、1回の実験で同じ温度、且つ同じ圧力で6種の反応を実行することができる。その後、これらのガラス容器をスクリューキャップとセプタムとで閉じ、適切なサイズの小型シリンジカニューレを用いて各セプタムを穿刺する。これにより、反応の後半でガス交換が可能になる。続いて、これらのバイアルを金属板に載置し、金属板をアルゴン下でオートクレーブに移す。オートクレーブをCOでパージし、意図したCO圧力で室温で充填する。次いで、マグネチックスターラを用いて磁気撹拌しながらオートクレーブを反応温度に加熱し、適当な時間反応させる。続いて、オートクレーブを室温に冷却し、圧力をゆっくり解放する。続いて、オートクレーブを窒素でパージする。バイアルをオートクレーブから取り出し、適切な標準物質の規定量を添加する。GC分析を行い、その結果を用いて収率と選択率を判定する。
4mlのバイアルをテトラメチルエチレン(1a)(1.0mol)で中点し、マグネチックスターラバーを添加する。その後、Pd(acac)2(1.52mg、0.5mol%)、L1(2.0mol%)、PTSA×H2O(16.0mg、8.0mol%)、MeOH(2.0ml)を添加する。バイアルをサンプルホルダー上に置き、アルゴン雰囲気下で300mlのParrオートクレーブに順に挿入した。オートクレーブを窒素で3回パージした後、CO圧を40バールに調整した。反応は120℃で15時間進行した。反応終了後、オートクレーブを室温に冷却し、注意深く減圧した。収率と位置選択率は、GCにより判定した。
Claims (13)
- 式(1)の化合物。
(R1及びR2は、それぞれ独立的に−(C1−C12)−アルキルである) - R1及びR2は同じ基(radical)である、請求項1に記載の化合物。
- R1が、tBuである、請求項1及び2のいずれか一項に記載の化合物。
- R2が、tBuである、請求項1から3のいずれか一項に記載の化合物。
- 前記化合物が、構造(L1)を有する、請求項1から4のいずれか一項に記載の化合物。
- Pdと、請求項1から5のいずれか一項に記載の化合物と、を含む、錯体。
- a)エチレン性不飽和化合物をまず充填することと、
b)請求項1から5のいずれか一項に記載の化合物と、Pdを含む化合物とを添加すること、あるいは請求項6に記載の錯体を添加することと、
c)アルコールを添加することと、
d)COを供給することと、
e)反応混合物を加熱してエチレン性不飽和化合物をエステルに転換させること、とを含む、方法。 - 前記エチレン性不飽和化合物が、エテン、プロペン、1−ブテン、シス−2−ブテン、トランス−2−ブテン、イソブテン、1,3−ブタジエン、1−ペンテン、シス−2−ペンテン、トランス−2−ペンテン、2−メチル−1−ブテン、3−メチル−1−ブテン、2−メチル−2−ブテン、ヘキセン、テトラメチルエチレン(2,3−ジメチル−2−ブテン)、ヘプテン、1−オクテン、2−オクテン、ジ−n−ブテン、又はこれらの混合物から選択される、請求項7に記載の方法。
- ステップb)の前記Pdを含む化合物が、PdCl2、PdBr2、Pd(acac)2、Pd(dba)2(dbaはジベンジリデンアセトン)、PdCl2(CH3CN)2から選択される、請求項7及び8のいずれか一項に記載の方法。
- ステップc)の前記アルコールが、メタノール、エタノール、1−プロパノール、1−ブタノール、1−ペンタノール、1−ヘキサノール、2−プロパノール、tert−ブタノール、3−ペンタノール、シクロヘキサノール、フェノール、又はこれらの混合物から選択される、請求項7から9のいずれか一項に記載の方法。
- ステップe)において、前記反応混合物を80℃〜160℃の温度に加熱する、請求項7から10のいずれか一項に記載の方法。
- ステップd)において、COを供給し、反応が20〜50バールのCO圧下で進むようにする、請求項7から11のいずれか一項に記載の方法。
- 前記方法が、f)p−トルエンスルホン酸を添加することをさらに含む、請求項7から12いずれか一項に記載の方法。
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