TWI838728B - 具有開放式３－甲基化外部單元的二亞磷酸酯及其在氫甲醯化的用途、以及使用其之烯烴的氫甲醯化 - Google Patents
具有開放式３－甲基化外部單元的二亞磷酸酯及其在氫甲醯化的用途、以及使用其之烯烴的氫甲醯化 Download PDFInfo
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- TWI838728B TWI838728B TW111114020A TW111114020A TWI838728B TW I838728 B TWI838728 B TW I838728B TW 111114020 A TW111114020 A TW 111114020A TW 111114020 A TW111114020 A TW 111114020A TW I838728 B TWI838728 B TW I838728B
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- Prior art keywords
- hydroformylation
- compound
- olefins
- alkyl
- diphosphites
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 23
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 10
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NPXUKNQBFIIIDW-UHFFFAOYSA-N dichlorophosphinite Chemical compound [O-]P(Cl)Cl NPXUKNQBFIIIDW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- MZTPSHAQKGUMBY-UHFFFAOYSA-N n,n-diethylethanamine;phenol Chemical compound CCN(CC)CC.OC1=CC=CC=C1 MZTPSHAQKGUMBY-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- -1 phosphite dichlorophosphite Chemical compound 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- ILPBINAXDRFYPL-HWKANZROSA-N (E)-2-octene Chemical compound CCCCC\C=C\C ILPBINAXDRFYPL-HWKANZROSA-N 0.000 description 1
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- VIHUHUGDEZCPDK-GQCTYLIASA-N (e)-5-methylhept-2-ene Chemical compound CCC(C)C\C=C\C VIHUHUGDEZCPDK-GQCTYLIASA-N 0.000 description 1
- LXBJRNXXTAWCKU-SNAWJCMRSA-N (e)-6-methylhept-2-ene Chemical compound C\C=C\CCC(C)C LXBJRNXXTAWCKU-SNAWJCMRSA-N 0.000 description 1
- IRUCBBFNLDIMIK-BQYQJAHWSA-N (e)-oct-4-ene Chemical compound CCC\C=C\CCC IRUCBBFNLDIMIK-BQYQJAHWSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- QDMFTFWKTYXBIW-UHFFFAOYSA-N 3-Methyl-1-heptene Chemical compound CCCCC(C)C=C QDMFTFWKTYXBIW-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- XZJZVNABSFJYOK-UHFFFAOYSA-N 3-methylidenenonane Chemical compound CCCCCCC(=C)CC XZJZVNABSFJYOK-UHFFFAOYSA-N 0.000 description 1
- HJXYLVWUVYMJKO-UHFFFAOYSA-N 3-methylidenetridecane Chemical compound CCCCCCCCCCC(=C)CC HJXYLVWUVYMJKO-UHFFFAOYSA-N 0.000 description 1
- GLUPFQMLFXGTNL-UHFFFAOYSA-N 3-methyloct-1-ene Chemical compound CCCCCC(C)C=C GLUPFQMLFXGTNL-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical group O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N propyl ethylene Natural products CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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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
- C07F9/6564—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
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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
- C07F9/6564—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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- 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
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Abstract
一種具有開放式3-甲基化外部單元的二亞磷酸酯及其在氫甲醯化的用途、以及使用其之烯烴的氫甲醯化。
Description
本發明係關於具有開放式3-甲基化外部單元的二亞磷酸酯及其在氫甲醯化(hydroformylation)的用途。
含磷化合物在眾多反應(例如氫化、氫氰化(hydrocyanation)及氫甲醯化)中發揮著配位基的關鍵作用。
在觸媒存在下，烯烴化合物、一氧化碳及氫之間產生包含多一個碳原子的醛之反應稱為氫甲醯化或甲醯化。用於這些反應的觸媒常常是元素週期表之VIII族的過渡金屬之化合物。已知配位基是例如來自膦、亞磷酸酯及亞膦酸酯類的化合物，其各含有三價磷PIII。烯烴之氫甲醯化的情況之良好概述可以見於R.Franke,D.Selent,A.Börner,
“Applied Hydroformylation”,Chem.Rev.,2012,DOI：10.1021/cr3001803。
下列化合物記載於EP 0213639 A2之第98頁的實施例10中：
這裡將化合物(2)用作為1-丁烯之氫甲醯化中的配位基。
本發明之技術目標是提供新穎配位基，其展現和先前技術中已知的配位基相比增加之烯烴的氫甲醯化的正/異(n/iso)選擇性。
藉由如請求項1之化合物而達到上述目標。
結構(I)之化合物：
其中R1、R2、R3、R4係選自：-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
在一個實施方式中，R1、R3係選自：-H、-(C1-C12)-烷基。
在一個實施方式中，R1、R3是-(C1-C12)-烷基。
在一個實施方式中，R1、R3是-tBu。
在一個實施方式中，R1、R3是相同的基。
在一個實施方式中，R2、R4係選自：-H、-O-(C1-C12)-烷基。
在一個實施方式中，R2、R4是-O-(C1-C12)-烷基。
在一個實施方式中，R2、R4是-OMe。
在一個實施方式中，R2、R4是相同的基。
在一個實施方式中，該化合物具有結構(1)：
除了該化合物本身之外，還請求保護用於氫甲醯化反應的催化作用之用途。
上述化合物在用於氫甲醯化反應之催化作用的配位基-金屬錯合物之用途。
另外請求保護將上述化合物用作為配位基的方法。
一種方法，其包含下列方法步驟：a)起初加入烯烴，b)加入上述化合物與含有選自Rh、Ru、Co、Ir的金屬之物質，c)供應H2與CO，d)加熱來自步驟a)至c)的反應混合物，以將該烯烴轉化為醛。
在一個較佳實施方式中，該金屬是Rh。
這裡配位基也可以過量使用，且並非自動地各配位基以如配位基-金屬錯合物的結合形式存在；作為替代，其可以在反應混合物中以游離配位基形式存在。
在常用條件下進行反應。
較佳為80℃至160℃的溫度及10至60bar的壓力。特別較佳為100℃至140℃的溫度及20至50bar的壓力。
在本發明之方法中用於氫甲醯化的反應物是烯烴或烯烴混合物，尤其是具有2至24個碳原子，較佳為3至16個碳原子，且更佳為3至12個碳原子，並具有末端或內C-C雙鍵的單烯烴(monoolefins)，例如1-丙烯、1-丁烯、2-丁烯、1-或2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、3-甲基-1-丁烯、1-、2-或3-己烯、丙烯之二聚合所得之C6烯烴混合物(二丙烯)、庚烯、2-或3-甲基-1-己烯、辛烯、2-甲基庚烯、3-甲基庚烯、5-甲基-2-庚烯、6-甲基-2-庚烯、2-乙基-1-己烯、丁烯之二聚合所得之C8烯烴混合物(二正丁烯、二異丁烯)、壬烯、2-或3-甲基辛烯、丙烯之三聚合所得之C9烯烴混合物(三丙烯)、癸烯、2-乙基-1-辛烯、十二烯、丙烯之四聚合或丁烯之三聚合所得之C12烯烴混合物(四丙烯或三丁烯)、十四烯、十六烯、丁烯之四聚合所得之C16烯烴混合物(四丁烯)、及具有不同碳原子數(較佳為2至4個)的烯烴的共寡聚合(cooligomerization)所產生的烯烴混合物。
使用本發明之配位基的本發明之方法可以用於α-烯烴、末端支鏈、內部與內支鏈烯烴的氫甲醯化。
以下將參照操作實例更詳細闡述本發明。
以下製備都在惰性氣體下使用標準Schlenk技術進行。在使用之前，在適合的乾燥劑上乾燥溶劑。
藉由核磁共振譜法鑑定產物特性。以ppm形式記錄化學位移(δ)。31P NMR信號的引用方式如下：SR31P=SR1H*(BF31P/BF1H)=SR1H*0.4048。
在手套箱中，稱取9g(0.01mol)的二有機亞磷酸酯二氯亞磷酸酯(diorganophosphite dichlorophosphite)加入已經多次填滿並用惰性氣體排淨之250ml Schlenk燒瓶，然後排出並溶於75ml乾燥的甲苯。在第二個已經多次填滿並用惰性氣體排淨之250ml Schlenk燒瓶中，稱取2.2g(2.1ml，0.02mol)的3-甲酚並藉助油泵真空在室溫下乾燥12小時。加入50ml乾燥的甲苯及3ml=2.2g(0.022mol)的經脫氣之三乙胺，同時攪拌並將固體溶解。在室溫下在1.5小時內將二氯亞磷酸酯加至酚-三乙胺溶液。在室溫下攪拌反應15小時，及加入1.5ml(0.011mol)的三乙胺。然後在80℃下攪拌反應混合物1.5小時。在冷卻至室溫後，使
用燒結濾器濾出鹽酸銨固體，藉助油泵真空在40℃下濃縮濾液。在室溫下藉助油泵真空乾燥所得固體15小時。產率：76%，純度：90%。
在手套箱中，稱取9g(0.01mol)的二有機亞磷酸酯二氯亞磷酸酯加入已經多次填滿並用惰性氣體排淨之250mlSchlenk燒瓶，然後排出並溶於75ml乾燥的甲苯。在第二個已經多次填滿並用惰性氣體排淨之250ml Schlenk燒瓶中，稱取2.2g(2.1ml，0.02mol)的2-甲酚並藉助油泵真空在室溫下乾燥12小時。加入50ml乾燥的甲苯及3ml=2.2g(0.022mol)的經脫氣之三乙胺，同時攪拌並將固體溶解。在室溫下在1.5小時內將二氯亞磷酸酯加至酚-三乙胺溶液。在室溫下攪拌反應混合物2小時，然後加熱至80℃。在該溫度下攪拌反應混合物15小時，然後3個循環之計量加入1.5ml(0.011mol)的三乙胺並攪拌15小時。藉由燒結濾器移除鹽酸銨，用1 x 10ml乾燥的甲苯清洗並濃縮至乾
燥。在室溫下乾燥固體15小時並和40ml經脫氣之乙腈攪拌。藉由燒結濾器移除沉澱白色固體，用2批10ml ACN清洗Schlenk燒瓶，乾燥，然後導入手套箱。產率：90%，純度：95%。
在配備保壓閥、氣體流量計及鼓泡攪拌器的16ml熱壓器(來自HEL Group,Hertfordshire,Great Britain)中進行氫甲醯化反應。將用作為基材之正辛烯(Oxeno GmbH，由1-辛烯(3%)、順+反-2-辛烯(49%)、順+反-3-辛烯(29%)、順+反-4-辛烯(16%)、結構同分異構的辛烯(3%)構成之辛烯異構物混合物)在鈉上加熱回流幾個小時及在氬氣下蒸餾。
預先在氬保護氣氛下製備用於實驗的反應溶液。為此，稱取0.0021g的Rh(acac)(CO)2與對應量的亞磷酸酯化合物並用8.0ml甲苯填滿。在各種情況下導入的甲苯質量係以GC分析測定。然後加入1.80g正辛烯(16mmol)。然後將所製備溶液導入熱壓器，其已用氬氣沖刷三次並用合成氣(Linde；H2(99.999%)：CO(99.997%)=1：1)沖刷三次。然後將熱壓器在10bar總壓力下在攪拌(900rpm)下加熱至所欲溫度。在達到反應溫度時，將合成氣壓力增加至20bar及反應在恆壓下進行4小時。在反應時間的最後，將熱壓器冷卻至室溫，減壓同時攪拌並用氬氣沖刷。在反應結束時，移出0.5ml的各反應混合物，用4ml戊烷稀釋及
藉由氣相層析法分析：HP 5890 Series II plus，PONA，50m x 0.2mm x 0.5μm。根據作為內標準的溶劑甲苯定量殘餘烯烴及醛。
[Rh]：120ppm，L：Rh=1：2，p：20bar，T：120℃；t：4h
在氫甲醯化中，有正/異選擇性，其係直鏈醛(=正)與支鏈醛(=異)的比率。這裡正醛之選擇性表示形成此量的直鏈產物。然後剩餘的百分率對應於支鏈異構物。因此，在50%的位置選擇性下，形成等比例之正醛及異醛。
和比較的配位基(2)相比，本發明之化合物(1)獲得增加的正/異選擇性。
所進行的實驗表明藉由本發明之化合物達到指定的目標。
Claims (10)
- 一種結構(I)之化合物：
- 如請求項1之化合物，其中R1、R3係選自：-H、-(C1-C12)-烷基。
- 如請求項1與2中任一項之化合物，其中R1、R3是-(C1-C12)-烷基。
- 如請求項1至2中任一項之化合物，其中R1、R3是相同的基。
- 如請求項1至2中任一項之化合物，其中R2、R4係選自：-H、-O-(C1-C12)-烷基。
- 如請求項1至2中任一項之化合物，其中R2、R4是-O-(C1-C12)-烷基。
- 如請求項1至2中任一項之化合物，其中R2、R4是相同的基。
- 如請求項1至2中任一項之化合物，其中該化合物具有結構(1)：
- 一種如請求項1至8中任一項之化合物的用途，其係用於氫甲醯化反應之催化作用的配位基-金屬錯合物。
- 一種烯烴的氫甲醯化方法，其包含下列方法步驟：a)起初加入烯烴，b)加入如請求項1至8中任一項之化合物與含有選自Rh、Ru、Co、Ir的金屬之物質，c)供應H2與CO，d)加熱來自步驟a)至c)的反應混合物，以將該烯烴轉化為醛。
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| US20120190894A1 (en) * | 2009-10-16 | 2012-07-26 | Wegman Richard W | Gas phase hydroformylation process |
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