CN115109093A - 基于亚膦酸酯-亚磷酸酯的配体 - Google Patents
基于亚膦酸酯-亚磷酸酯的配体 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title abstract description 10
- BONASJKBJAQWML-UHFFFAOYSA-N OPO.OP(O)O Chemical compound OPO.OP(O)O BONASJKBJAQWML-UHFFFAOYSA-N 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 9
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-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
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 3
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 claims 1
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical group C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 230000001105 regulatory effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus 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
- C07F9/6564—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
- C07F9/6568—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 atoms as the only ring hetero atoms
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/65719—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1885—Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
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- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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Abstract
本申请涉及基于亚膦酸酯‑亚磷酸酯的配体，和其在加氢甲酰化中的用途。
Description
本发明涉及基于亚膦酸酯(Phosphonit)-亚磷酸酯的配体，和其在加氢甲酰化中的用途。
WO 2008/071508 A1描述了使用双亚磷酸酯配体的加氢甲酰化方法。尤其描述了配体(D-1)的使用。
本发明所基于的技术问题是提供与现有技术已知的化合物相比在烯烃的加氢甲酰化中提供增加的产率的新型化合物。
该问题通过根据权利要求1的化合物解决。
式(I)的化合物：
其中
R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
术语-(C1-C12)-烷基和-O-(C1-C12)-烷基包括具有1至12个碳原子的直链和支化的烷基。这些优选是-(C1-C8)-烷基或-O-(C1-C8)-烷基，特别优选-(C1-C4)-烷基或-O-(C1-C4)-烷基。
在一个实施方案中，R5和R8为-(C1-C12)-烷基。
在一个实施方案中，R5和R8为-tertBu。
在一个实施方案中，R6、R7选自-(C1-C12)-烷基、-O-(C1-C12)-烷基。
在一个实施方案中，R6和R7为-OCH3或-tertBu。
在一个实施方案中，R1、R2、R3、R4选自-H、-(C1-C12)-烷基。
在一个实施方案中，R1、R2、R3、R4为-H或-tertBu。
在一个实施方案中，该化合物具有结构(1)至(3)之一：
除了化合物本身之外，还要求保护其中使用该化合物的方法。
所述方法包含以下步骤：
a)预置入烯属不饱和化合物；
b)加入如上所述的化合物和包含Rh的物质；
c)供入H2和CO，
d)加热a)-c)的反应混合物，使烯属不饱和化合物转化为醛。
在该方法中，方法步骤a)、b)和c)可以以任何所需顺序进行。然而，通常在步骤a)和b)中已经预置入反应参与物之后加入CO。此外，CO也可以以多步供入，从而例如首先进料一部分CO，然后加热混合物，然后再进料另一部分CO。
在根据本发明方法中用作反应物的烯属不饱和化合物含有一个或多个碳-碳双键。为了简化，这些化合物在下文中也称为烯烃。双键可以是位于末端的或内部的。
在该方法的一个变体中，烯属不饱和化合物不包含除碳-碳双键之外的任何其它官能团。
在该方法的一个变体中，烯属不饱和化合物选自：乙烯、丙烯、1-丁烯、顺式和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式和/或反式-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯或其混合物。
在该方法的一个变体中，包含Rh的物质选自Rh(acac)(CO)2、
[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮酸阴离子；COD＝1,5-环辛二烯)、Rh4CO12。
在该方法的一个变体中，在方法步骤c)中在1-6MPa(10-60巴)的压力下供入CO。
在该方法的一个变体中，在方法步骤d)中将反应混合物加热至80℃至160℃的温度。
下面将参照实施例更详细地说明本发明。
6-((3,3'-二叔丁基-2'-((4,6-二叔丁基苯并[d][1,3,2]二氧磷杂环戊烯
(dioxaphosphol)-2-基)氧基)-5,5'-二甲氧基-[1,1'-联苯基]-2-基)氧基)-6H-二苯并
[c,e][1,2]氧磷杂苯(oxaphosphinin)(1)的合成
向已冷却至0℃的2'-((6H-二苯并[c,e][1,2]氧磷杂苯-6-基)氧基)-3,3'-二叔丁基-5,5'-二甲氧基-[1,1'-联苯基]-2-醇(1.000g；1.7965mmol)和三乙胺(0.5ml)在16mlTHF中的混合物中滴加4,6-二叔丁基-2-氯苯并[d][1,3,2]二氧磷杂环戊烯(0.5151g；1.7965mmol)在5ml的THF中的溶液。在室温下搅拌过夜并过滤，将滤液减压浓缩至干。使得到的固体在50℃/0.1毫巴下干燥2小时，然后溶于16ml热乙腈中。将冷却后形成的固体滤出，用很少量冷乙腈洗涤，并在50℃/0.1毫巴下干燥4小时。产率：0.807g(1.098mmol，61％)。
元素分析(对于C48H56O7P2的计算值＝806.911g/mol):C＝71.56(71.45)；H＝6.96(6.99)；P＝7.44(7.68)。
ESI-TOF HRMS:m/z＝807.3586；[M++H],计算的m/z＝807.35799。
31P NMR(CD2Cl2):δ125.4(d,JPP＝62Hz)；126.9(d,JPP＝33Hz)；127.6(d,JPP＝51Hz)；129.2(d,JPP＝96Hz)；130.4(d,JPP＝51Hz)；133.2(d,JPP＝62Hz)；134.2(d,JPP＝96Hz)；135.0(d,JPP＝33Hz)ppm。
1H NMR(CD2Cl2):δ1.09；1.15；1.17；1.29；1.30；1.31；1.32；1.34；1.35；1.36；1.36；1.37；1.38；1.38；1.39；1.39；1.40；1.41；1.43；1.44；1.47；1.49；1.52；1.58；3.38；3.53；3.62；3.68；3.81；3.83；3.95；3.96ppm。
6-((3,3'-二叔丁基-2'-((5-(叔丁基)苯并[d][1,3,2]二氧磷杂环戊烯-2-基)氧
基)-5,5'-二甲氧基-[1,1'-联苯基]-2-基)氧基)-6H-二苯并[c,e][1,2]氧磷杂苯(3)的合
成
在0℃下向2'-((6H-二苯并[c,e][1,2]氧磷杂苯-6-基)氧基)-3,3'-二叔丁基-5,5'-二甲氧基-[1,1'-联苯基]-2-醇(,5g；0.8982mmol)和三乙胺(0.25ml)在8ml THF中的混合物中滴加5-(叔丁基)-2-氯苯并[d][1,3,2]二氧磷杂环戊烯(0.2071g；0.8982mmol)在3ml THF中的溶液。在室温下搅拌过夜并过滤，将滤液减压浓缩至干。使得到的固体在50℃/0.1毫巴下干燥2小时，然后溶于6.3ml热乙腈中。将在低温冷柜中储存后形成的固体滤出，用很少量冷乙腈洗涤，并在50℃/0.1毫巴下干燥4小时。产率：0.168g(0.274mmol，30％)。
元素分析(对于C44H48O7P2的计算值＝750.8042g/mol):C＝70.37(70.39)；H＝6.26(6.44)；P＝8.12(8.25)。
ESI-TOF HRMS:m/z＝773.2778；[M++Na],计算的m/z＝773.27733。
31P NMR(CD2Cl2):δ126.2(d,JPP＝49Hz)；126.6(d,JPP＝43Hz)；128.3(d,JPP＝86Hz)；128.4(d,JPP＝79Hz)；134.2(d,JPP＝79Hz)；134.7(d,JPP＝86Hz)；136.0(d,JPP＝49Hz)；136.3(d,JPP＝43Hz)ppm。
1H NMR(CD2Cl2):δ1.13；1.13；1.26；1.27；1.31；1.33；1.36；1.36；1.37；1.38；1.49；1.51ppm。
6-((3,3',5,5'-四-叔丁基-2'-((5-(叔丁基)苯并[d][1,3,2]二氧磷杂环戊烯-
2-基)氧基)-[1,1'-联苯基]-2-基)氧基)-6H-二苯并[c,e][1,2]氧磷杂苯(3)的合成
在0℃下向2'-((6H-二苯并[c,e][1,2]氧磷杂苯-6-基)氧基)-3,3',5,5'-四叔丁基-[1,1'-联苯基]-2-醇(0.761g；1.250mmol)和吡啶(0.15ml)在10ml THF中的混合物中滴加5-(叔丁基)-2-氯苯并[d][1,3,2]二氧磷杂环戊烯(0.2883g；1.250mmol)在2ml THF中的溶液。在室温下搅拌过夜并过滤，将滤液减压浓缩至干。使得到的固体在50℃/0.1毫巴下干燥2小时，然后与8ml庚烷一起搅拌。滤出剩余的固体，用很少量冷庚烷洗涤并在50℃/0.1毫巴下干燥4小时。产率：0.720g(1.125mmol，90％)。
元素分析(对于C50H60O5P2的计算值＝802.967g/mol):C＝74.90(74.79)；H＝7.55(7.53)；P＝7.65(7.72)。
ESI-TOF HRMS:m/z＝803.4004；[M++H],计算的m/z＝803.39945。
31P NMR(CD2Cl2):δ125.8(d,JPP＝29Hz)；126.1(d,JPP＝20Hz)；126.2(d,JPP＝28Hz)；126.4(d,JPP＝20Hz)；132.9(d,JPP＝29Hz)；133.4(d,JPP＝28Hz)；136.8(d,JPP＝20Hz)；137.1(d,JPP＝20Hz)ppm。
催化实验
在Premex Reactor AG，Lengau(瑞士)公司的200ml高压釜中进行加氢甲酰化，该高压釜装配有保压阀、气体流量计、喷射搅拌器和压力吸管。为了使水分和氧气的影响最小化，使用作溶剂的甲苯在Pure Solv.MD-7系统中纯化并在氩气下储存。将用作底物的烯烃顺/反-2-戊烯(Aldrich)在钠上加热回流并在氩气下蒸馏。在氩气氛下，在高压釜中混合催化剂前体和配体的各自的甲苯溶液。将[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮酸阴离子；COD＝1,5-环辛二烯)用作催化剂前体。在12巴下于搅拌(1500转/分)下加热高压釜，最终压力为20巴。在达到反应温度后，通过在压力吸管中调节得的正压将烯烃注入高压釜。反应在恒压(来自Bronkhorst(荷兰)公司的闭环压力调节器(Nachdruckregler))下进行4小时。在反应时间结束时，将高压釜冷却至室温，在搅拌的同时减压并用氩气吹扫。每种情形下在关闭搅拌器后立即取出1ml反应混合物，用10ml戊烷将其稀释并通过气相色谱分析：HP5890Series II plus，PONA，50m x 0.2mm x 0.5μm。
使用根据本发明的化合物(1)至(3)和使用对比配体(D-1)进行反应。
反应条件：
烯烃：2-戊烯，溶剂：甲苯，铑的质量比例：100ppm，p：20巴，T:120℃，t:4h，Rh:配体比例＝1:2。
结果汇编于下表中：
| 配体 | 醛的产率[％] |
| 1* | 94 |
| 2* | 98 |
| 3* | 99 |
| D-1 | 14 |
*根据本发明的化合物
如实验结果所示，根据本发明的化合物解决了该问题。
Claims (13)
1.式(I)的化合物:
其中
R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
2.根据权利要求1的化合物，
其中R5和R8为-(C1-C12)-烷基。
3.根据权利要求1和2任一项的化合物，
其中R5和R8为-tertBu。
4.根据权利要求1-3任一项的化合物，
其中R6、R7选自-(C1-C12)-烷基、-O-(C1-C12)-烷基。
5.根据权利要求1-4任一项的化合物，
其中R6和R7为-OCH3或-tertBu。
6.根据权利要求1-5任一项的化合物，
其中R1、R2、R3、R4选自-H、-(C1-C12)-烷基。
7.根据权利要求1-6任一项的化合物，
其中R1、R2、R3、R4为-H或-tertBu。
8.根据权利要求1-7任一项的化合物，
其中该化合物具有结构(1)至(3)之一：
9.方法，包含以下方法步骤：
a)预置入烯属不饱和化合物；
b)加入根据权利要求1-8任一项的化合物和包含Rh的物质；
c)供入H2和CO，
d)加热a)-c)的反应混合物，使烯烃转化为醛。
10.根据权利要求9的方法：
其中方法步骤a)中的烯属不饱和化合物选自：乙烯、丙烯、1-丁烯、顺式和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式和/或反式-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯或其混合物。
11.根据权利要求9和10任一项的方法，
其中包含Rh的物质选自：Rh(acac)(CO)2、[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮酸阴离子；COD＝1,5-环辛二烯)、Rh4CO12。
12.根据权利要求9-11任一项的方法，
其中在方法步骤c)中在1-6MPa(10-60巴)的压力下供入CO。
13.根据权利要求9-12任一项的方法，
其中在方法步骤d)中将所述反应混合物加热至80℃至160℃的温度。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21163479.5A EP4059940A1 (de) | 2021-03-18 | 2021-03-18 | Liganden auf basis von phosphonit-phosphiten |
| EP21163479.5 | 2021-03-18 |
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| CN115109093A true CN115109093A (zh) | 2022-09-27 |
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| US (1) | US20220298189A1 (zh) |
| EP (1) | EP4059940A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19810794A1 (de) * | 1998-03-12 | 1999-09-16 | Basf Ag | Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Phosphonitliganden und Verfahren zur Hydroformylierung |
| DE102006058682A1 (de) | 2006-12-13 | 2008-06-19 | Evonik Oxeno Gmbh | Bisphosphitliganden für die übergangsmetallkatalysierte Hydroformylierung |
-
2021
- 2021-03-18 EP EP21163479.5A patent/EP4059940A1/de not_active Withdrawn
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2022
- 2022-03-16 US US17/696,117 patent/US20220298189A1/en not_active Abandoned
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- 2022-03-18 CN CN202210274306.0A patent/CN115109093A/zh active Pending
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| US20220298189A1 (en) | 2022-09-22 |
| EP4059940A1 (de) | 2022-09-21 |
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