CN114249769A - 具有敞开的2,4-甲基化外翼结构单元的二亚磷酸酯 - Google Patents
具有敞开的2,4-甲基化外翼结构单元的二亚磷酸酯 Download PDFInfo
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- CN114249769A CN114249769A CN202111105280.9A CN202111105280A CN114249769A CN 114249769 A CN114249769 A CN 114249769A CN 202111105280 A CN202111105280 A CN 202111105280A CN 114249769 A CN114249769 A CN 114249769A
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- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 27
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052741 iridium 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
- 239000003446 ligand Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 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
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- NPXUKNQBFIIIDW-UHFFFAOYSA-N dichlorophosphinite Chemical compound [O-]P(Cl)Cl NPXUKNQBFIIIDW-UHFFFAOYSA-N 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
- 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 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 compound Chemical class 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
- 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
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-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
- GLUPFQMLFXGTNL-UHFFFAOYSA-N 3-methyloct-1-ene Chemical class CCCCCC(C)C=C GLUPFQMLFXGTNL-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [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
- 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
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000007865 diluting Methods 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
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 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
- 238000006384 oligomerization reaction 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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 239000000758 substrate 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
- 238000005303 weighing Methods 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
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
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- 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
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Abstract
本发明公开了具有敞开的2,4‑甲基化外翼结构单元的二亚磷酸酯及其用于加氢甲酰化的用途。
Description
技术领域
本发明涉及具有敞开的2,4-甲基化外翼结构单元的二亚磷酸酯及其用于加氢甲酰化的用途。
背景技术
在许多反应中,例如在氢化中,在氢氰化中,以及在加氢甲酰化中,含磷化合物作为配体起到关键的作用。
为了获得具有一个碳原子以上的醛而进行的在催化剂存在下在烯烃化合物、一氧化碳和氢气之间的反应被称为加氢甲酰化或羰基化过程。在这些反应中,元素周期表第VIII族过渡金属的化合物常常被用作催化剂。已知的配体例如是得自膦、亚磷酸酯和亚膦酸酯类的化合物,它们各自含有三价磷PIII。关于烯烃的加氢甲酰化的现有技术状况的非常好的综述可在以下文献中找到:R.Franke,D.Selent,A.“AppliedHydroformylation”,Chem.Rev.,2012,DOI:10.1021/cr3001803。
在EP 0213639 A2中,在98页上实施例10中示出了以下化合物:
该化合物(2)在此作为配体用于1-丁烯的加氢甲酰化。
发明内容
本发明的技术目的是提供新的配体,所述新的配体与现有技术中已知的配体相比,在烯烃的加氢甲酰化中表现出增加的正构/异构选择性。
所述目的通过根据权利要求1的化合物实现。
结构(I)的化合物:
其中,R1、R2、R3、R4选自:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
在一个实施方案中,R1、R3选自:-H、-(C1-C12)-烷基。
在一个实施方案中,R1、R3是-(C1-C12)-烷基。
在一个实施方案中,R1、R3是-tBu。
在一个实施方案中,R1、R3是相同的基团。
在一个实施方案中,R2、R4选自:-H、-O-(C1-C12)-烷基。
在一个实施方案中,R2、R4是-O-(C1-C12)-烷基。
在一个实施方案中,R2、R4是-OMe。
在一个实施方案中,R2、R4是相同的基团。
在一个实施方案中,R1、R2、R3、R4不全部同时是-CH3。
在一个实施方案中,所述化合物具有结构(1):
除了所述化合物本身外,其用于催化加氢甲酰化反应的用途也是要求保护的主题。
上述化合物在配体-金属配合物中用于催化加氢甲酰化反应的用途。
还要求保护的主题是其中将上述化合物用作配体的方法。
该方法包括以下方法步骤:
a)将烯烃初始加料,
b)添加上述化合物和含有金属的物质,所述金属选自:Rh、Ru、Co、Ir,
c)供入H2和CO,
d)将得自步骤a)至c)的反应混合物加热,其中所述烯烃转化成醛。
在一个优选实施方案中,所述金属是Rh。
此处,还可以使用过量的配体,并且不是强制要求每个配体作为配体-金属配合物形式以结合方式存在,而是它可以作为游离配体存在于所述反应混合物中。
所述反应是在常规条件下进行的。
优选地,温度为80℃至160℃,和压力为10至60巴。
特别优选地,温度为100℃至140℃,和压力为20至50巴。
在本发明的方法中,用于所述加氢甲酰化的反应物是烯烃或烯烃混合物,尤其是具有2至24个,优选3至16个和更优选3至12个碳原子并具有末端或内部C-C双键的单烯烃,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,在丙烯的二聚中获得的C6烯烃混合物(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,在丁烯的二聚中获得的C8烯烃混合物(二正丁烯,二异丁烯),壬烯,2-或3-甲基辛烯,在丙烯的三聚中获得的C9烯烃混合物(三丙烯),癸烯,2-乙基-1-辛烯,十二碳烯,在丙烯的四聚或丁烯的三聚中获得的C12烯烃混合物(四丙烯或三丁烯),十四碳烯,十六碳烯,在丁烯的四聚中获得的C16烯烃混合物(四丁烯),和通过具有不同碳原子数(优选2至4个)的烯烃的共低聚制备的烯烃混合物。
采用本发明的方法,使用本发明的配体可将α-烯烃、末端支化的、内部的和内部支化的烯烃进行加氢甲酰化。
具体实施方式
下文中将参照实施例详细阐述本发明。
操作过程
一般分析
下文中的所有制备都是在保护气体下使用标准Schlenk技术进行的。在使用前将溶剂经合适的干燥剂干燥。
通过NMR波谱表征产物。以ppm计报道化学位移(δ)。31P NMR信号根据如下定位:SR31P=SR1H×(BF31P/BF1H)=SR1H×0.4048。
合成(1):
在手套箱中,将9g(0.01mol)二有机基亚磷酸酯二氯亚磷酸酯称重加到被固定住的250ml Schlenk瓶中,然后排空并溶解在75mL经干燥的甲苯中。在第二个被固定住的250ml Schlenk瓶中,将2.5g(0.02mol)2,4-二甲基苯酚和3mL(0.022mol)经脱气的三乙胺溶解在50mL甲苯中。在1.5小时内,在室温下将所述氯代亚磷酸酯缓慢且持续地添加到所述苯酚-三乙胺溶液中。使反应混合物在室温下搅拌过夜。将反应混合物加热到80℃。18小时后,使反应混合物穿过玻璃砂芯(gefrittet),并将滤液在油泵真空下在40℃下浓缩。随后,将固体在油泵真空上干燥18小时。然后将固体在50mL经干燥ACN中破碎并搅拌。然后通过玻璃砂芯除去沉淀的白色固体。纯度96%,收率48%。
合成(2)(对比配体)
在手套箱中,将9g(0.01mol)二有机基亚磷酸酯二氯亚磷酸酯称重加到被固定住的250mL Schlenk瓶中,然后排空并溶解在75mL经干燥的甲苯中。在第二个被固定住的250ml Schlenk瓶中,称出2.2g(2.1mL 0.02mol)2-甲基苯酚,并借助于油泵真空在室温下后续干燥12小时。在搅拌下添加50mL经干燥甲苯和3mL=2.2g(0.022mol)经脱气的三乙胺,并将其溶解。在1.5小时内,在室温下将所述二氯亚磷酸酯添加到所述苯酚-三乙胺的溶液中。将反应混合物在室温下搅拌2小时,并然后加热到80℃。将反应混合物在该温度下搅拌15小时,并后续计量加入3×1.5mL(0.011mol)三乙胺,并继续搅拌15小时。通过玻璃砂芯除去氢氯化铵,用1×10mL经干燥甲苯后续洗涤并浓缩至干。将固体在室温下干燥15小时,并与40mL经脱气的乙腈一起搅拌。通过玻璃砂芯除去沉淀的白色固体,用2×10mL ACN后续冲洗所述Schlenk瓶,并且在干燥后引入到手套箱中。收率90%,纯度:95%。
催化实验
在得自英国HEL Group,Hertfordshire的配备有保压装置、气体流量计和喷射搅拌器的16ml高压釜中进行加氢甲酰化。将用作底物的正辛烯(Oxeno GmbH,以下物质组成的辛烯异构体混合物:1-辛烯:3%;顺式+反式-2-辛烯:49%;顺式+反式-3-辛烯:29%;顺式+反式-4-辛烯:16%;结构异构体辛烯:3%)在钠上加热回流数小时,并在氩气下蒸馏。
为了所述实验,事先在氩气气氛下预制备反应溶液。为此,称重加入0.0021g Rh(acac)(CO)2和相应量的亚磷酸酯化合物,并将它们用8.0ml甲苯稀释。测定在每种情况下引入的甲苯的质量用于GC分析。然后添加1.80g正辛烯(16mmol)。然后将所预制备的溶液装入到所述高压釜中,将该高压釜用氩气冲洗三次和用合成气(Linde;H2(99.999%):CO(99.997%)=1:1)冲洗三次。然后将所述高压釜在10巴的总压力下,在搅拌(900rpm)下加热到希望的温度。当达到反应温度时,使合成气压力升高到20巴,并在恒定压力下使反应进行4小时。在反应时间结束后,使所述高压釜冷却至室温,在搅拌下泄压和用氩气冲洗。每种情况下,在反应结束后取出0.5ml的反应混合物,用4ml戊烷稀释,并通过气相色谱法分析:HP 5890Series II plus,PONA,50m×0.2mm×0.5μm。相对于作为内标的溶剂甲苯定量测定残留烯烃和醛。
催化实验的结果
反应条件:
[Rh]:120ppm,L:Rh=1:2,p:20巴,T:120℃;t:4小时
表1:正辛烯的加氢甲酰化
配体 | 正构/异构选择性,以%计 |
1<sup>*</sup> | 72 |
2 | 56 |
*本发明化合物
“选择性”的定义:
在所述加氢甲酰化中,存在正构/异构选择性,其为直链醛(=正构)与支化醛(=异构)的比例。在此,关于正构醛的选择性是指形成了这个量的直链产物。其余的百分比于是对应于支化异构体。因此,在区域选择性为50%的情况下,正构醛和异构醛以相等比例形成。
与对比配体(2)相比,采用本发明的化合物(1)实现了正构/异构选择性的增加。
所进行的实验证明,通过本发明的化合物实现了所提出的目的。
Claims (11)
2.根据权利要求1的化合物,其中R1、R3选自-H、-(C1-C12)-烷基。
3.根据权利要求1和2中任一项的化合物,其中R1、R3是-(C1-C12)-烷基。
4.根据权利要求1至3中任一项的化合物,其中R1、R3是相同的基团。
5.根据权利要求1至4中任一项的化合物,其中R2、R4选自-H、-O-(C1-C12)-烷基。
6.根据权利要求1至5中任一项的化合物,其中R2、R4是-O-(C1-C12)-烷基。
7.根据权利要求1至6中任一项的化合物,其中R2、R4是相同的基团。
8.根据权利要求1至7中任一项的化合物,其中R1、R2、R3、R4不全部同时是-CH3。
10.根据权利要求1至9中任一项的化合物在配体-金属配合物中用于催化加氢甲酰化反应的用途。
11.包含以下方法步骤的方法:
a)将烯烃初始加料,
b)添加根据权利要求1至9中任一项的化合物和含有金属的物质,所述金属选自:Rh、Ru、Co、Ir,
c)供入H2和CO,
d)将得自步骤a)至c)的反应混合物加热,其中所述烯烃转化成醛。
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