CN115109094A - 基于苯频哪醇的双亚磷酸酯配体 - Google Patents
基于苯频哪醇的双亚磷酸酯配体 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title abstract description 10
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 title abstract description 4
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 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
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 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
- POILWHVDKZOXJZ-ONEGZZNKSA-M (E)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C/C(C)=O POILWHVDKZOXJZ-ONEGZZNKSA-M 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 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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- 239000000463 material 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
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 12
- 125000005605 benzo group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PJZLSMMERMMQBJ-UHFFFAOYSA-N 3,5-ditert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC(O)=C(O)C(C(C)(C)C)=C1 PJZLSMMERMMQBJ-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-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
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 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
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing 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
- 239000012452 mother liquor Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 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
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension 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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- 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
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- 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
- B01J31/18—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
本发明公开了基于苯频哪醇的双亚磷酸酯配体，及其用于加氢甲酰化的用途。
Description
技术领域
本发明涉及基于苯频哪醇的双亚磷酸酯配体，及其用于加氢甲酰化的用途。
背景技术
WO 2008/071508 A1描述了使用双亚磷酸酯配体进行加氢甲酰化的方法。其中尤其描述了配体(D-1)的使用。
发明内容
本发明要解决的技术问题是提供新的化合物，该化合物与从现有技术已知的化合物相比，在烯烃的加氢甲酰化中提供提高的产率。
这个问题通过根据权利要求1的化合物得到解决。
式(I)的化合物：
其中
R1、R2、R3、R4、R5、R6、R7、R8各自彼此独立地选自：-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
表述“(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烷基基团。这些优选是-(C1-C8)-烷基基团或-O-(C1-C8)-烷基基团，特别优选-(C1-C4)-烷基基团或-O-(C1-C4)-烷基基团。
在一个实施方案中，R5和R8是-(C1-C12)-烷基。
在一个实施方案中，R5和R8是-叔丁基。
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是-OCH3或-叔丁基。
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是-H或-叔丁基。
在一个实施方案中，所述化合物具有结构(1)至(6)中的一种：
除了所述化合物本身外，还要求保护其中使用所述化合物的方法。
该方法包括以下方法步骤：
a)将烯属不饱和化合物初始加料；
b)添加如上所述的化合物和包含Rh的物质；
c)输入H2和CO，
d)将得自a)至c)的反应混合物加热，其中所述烯属不饱和化合物转化成醛。
在该方法中，方法步骤a)、b)和c)可以任何希望的顺序实施。然而，通常，在共反应物已经在步骤a)和b)中被初始加料之后实施CO的添加。此外，也可以在两个或更多个步骤中输入CO，使得例如，首先输入所述CO的一部分，然后将混合物加热，和随后输入CO的另一部分。
在根据本发明的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被称为烯烃。所述双键可以在末端或内部。
在所述方法的一个变型方案中，所述烯属不饱和化合物除了碳-碳双键外不包含任何另外的官能团。
在所述方法的一个变型方案中，所述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、二正丁烯或它们的混合物。
在所述方法的一个变型方案中，所述包含Rh的物质选自：Rh(acac)(CO)2、[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮酸根阴离子；COD＝1,5-环辛二烯)、Rh4CO12。
在所述方法的一个变型方案中，在方法步骤c)中将CO在1至6MPa(10至60巴)范围内的压力下输入。
在所述方法的一个变型方案中，在方法步骤d)中将所述反应混合物加热到在80℃至160℃范围内的温度。
具体实施方式
下文中将参照实施例更详细地阐述本发明。
2-((3,3'-二叔丁基-5,5'-二甲氧基-2'-((4,4,5,5-四苯基-1,3,2-二氧杂磷杂
环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)苯并[d][1,3,2]二氧杂磷杂环戊二烯
(dioxaphosphol)(1)的合成：
在室温下向2-((3,3'-二叔丁基-2'-((二氯磷烷基(phosphaneyl))氧基)-5,5'-二甲氧基-[1,1'-联苯]-2-基)氧基)-4,4,5,5-四苯基-1,3,2-二氧杂磷杂环戊烷(0.639g；0.7483mmol)在6ml甲苯中的溶液中滴加邻苯二酚(0.0824g；0.7483mmol)和三乙胺(0.42ml)在3ml甲苯中的混合物。将混合物搅拌过夜并过滤，并将滤液真空浓缩至干。将获得的固体在60℃/0.1毫巴下干燥2小时，并吸收在6.5ml热乙腈中。将在冷却后形成的固体滤出，用稍冷的乙腈洗涤，并真空干燥。产量：0.426g(0.5537mmol，74％)。
元素分析(C54H52O8P2的计算值＝890.945g/mol):C＝72.79(72.80)；H＝5.93(5.88)；P＝6.98(6.95)。
ESI-TOF HRMS:m/z＝891.3212；[M++H]，计算值m/z＝891.3215。
31P NMR(CD2Cl2):d 136.0(d,JPP＝55Hz)；146.9(d,JPP＝55Hz)。
1H NMR(CD2Cl2):d 1.29(s,9H)；1.35(s,9H)；3.74(s,3H)；3.80(s,3H)；6.75(m,1H)；6.82(m,1H)；6.95-7.16(m,22H)；7.32(m,4H)ppm。
5-(叔丁基)-2-((3,3'-二叔丁基-5,5'-二甲氧基-2'-((4,4,5,5-四苯基-1,3,2-
二氧杂磷杂环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)苯并[d][1,3,2]二氧杂磷杂环
戊二烯(2)的合成：
在室温下向2-((3,3'-二叔丁基-2'-((二氯磷烷基)氧基)-5,5'-二甲氧基-[1,1'-联苯]-2-基)氧基)-4,4,5,5-四苯基-1,3,2-二氧杂磷杂环戊烷(0.4384g；0.5135mmol)在4ml甲苯中的溶液中滴加4-叔丁基邻苯二酚(0.0853g；0.5135mmol)和三乙胺(0.29ml)在2ml甲苯中的混合物。将混合物搅拌过夜并过滤，并将滤液真空浓缩至干。将获得的固体在60℃/0.1毫巴下干燥2小时，并吸收在4.3ml热乙腈中。将在冷却后形成的固体滤出，用稍冷的乙腈洗涤，并真空干燥。产量：0.201g(0.261mmol，51％)。
元素分析(C58H60O8P2的计算值＝947.052g/mol):C＝73.51(73.56)；H＝6.63(6.39)；P＝6.81(6.54)。
ESI-TOF HRMS:m/z＝696.3655；[M++Na]，计算值m/z＝696.3660。
31P NMR(CD2Cl2):d 135.7(d,JPP＝44Hz)；136.0(d,JPP＝55Hz)；145.0(d,JPP＝55Hz)；145.1(d,JPP＝44Hz)ppm。
1H NMR(CD2Cl2):d 1.29+1.31(2s,9H)；1.33+1.34(2s,9H)；1.35(s；4.5H)；1.38(s,4.5H)；3.73(s,1.5H)；3.74(s,1.5H)；3.77(s,1.5H)；3.80(s,1.5H)；6.73(m,1H)；6.82(m,1H)；6.90-7.13(m,21H)；7.27-7.37(m,4H)ppm。
4,6-二叔丁基-2-((3,3'-二叔丁基-5,5'-二甲氧基-2'-((4,4,5,5-四苯基-1,3,
2-二氧杂磷杂环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)苯并[d][1,3,2]二氧杂磷杂
环戊二烯(3)的合成：
在-20℃下向3在4ml THF中的溶液中滴加正丁基锂的溶液。将混合物搅拌另外20分钟，然后让其温热至室温，并滴加溶解在1.8ml THF中的氯化次膦酸苯频哪醇酯(Benzopinakol-Phosphorchloridit)。将反应混合物搅拌过夜。随后添加三乙胺A，并然后将三氯化磷在1.5ml THF中的溶液滴加到冷却至0℃的反应混合物中。让混合物温热到室温，并搅拌6小时。
在真空下从混合批料中移除挥发性组分，并将残余物在60℃和0.1-0.5毫巴下干燥2小时。将获得的固体吸收在8ml甲苯中。在室温下向所得的悬浮液中滴加由3,5-二叔丁基邻苯二酚、三乙胺B和3ml甲苯组成的混合物。将混合物搅拌过夜，过滤(G4)，真空移除溶剂，并将固体在60℃和0.1-0.5毫巴下干燥。粗产量：1.03g(95％)。
将粗产物溶解在11ml沸腾乙腈中。使该混合物首先缓慢冷却到室温，并然后将其在-30℃下贮存过夜。在冷却到-30℃的情况下通过使用浸渍砂芯漏斗(Tauchfritte)虹吸掉上清母液而分离出析出的固体，并然后在60℃下真空干燥5小时。产量：0.786g(72％)。
元素分析(C62H68O8P2的计算值＝1003.16g/mol)：C＝74.24(74.23)；H＝6.85(6.83)；P＝6.07(6.18)。
ESI-TOF HRMS:m/z＝1025.4309；[M++H]，计算值m/z＝1025.4287。
31P NMR(CD2Cl2):d 134.1(s,br)；134.5(d,JPP＝77.3Hz)；144.6(d,JPP＝77.3Hz)；145.2(d,JPP＝24.7Hz),两种非对映异构体的混合物。
1H NMR(CD2Cl2):d 1.22(s)；1.27(s)；1.33(s)；1.34(s)；1.36(s)；1.44(s)；1.46(s)；1.47(s)ppm；S＝36H.3.68(s)；3.69(s)；3.77(s)；3.87(s)ppm；S＝12H.6.59-7.43ppm(m,26H)。
2-((3,3',5,5'-四叔丁基-2'-((4,4,5,5-四苯基-1,3,2-二氧杂磷杂环戊烷-2-
基)氧基)-[1,1'-联苯]-2-基)氧基)苯并[d][1,3,2]二氧杂磷杂环戊二烯(4)的合成：
在室温下向4,4,5,5-四苯基-2-((3,3',5,5'-四叔丁基-2'-((二氯磷烷基)氧基)-[1,1'-联苯]-2-基)氧基)-1,3,2-二氧杂磷杂环戊烷(0.7936g；0.8760mmol)在5ml甲苯中的溶液中滴加邻苯二酚(0.0964g；0.8760mmol)和三乙胺(0.49ml)在3ml甲苯中的混合物。将混合物搅拌过夜并过滤，并将滤液真空浓缩至干。将获得的固体在60℃/0.1毫巴下干燥2小时，并然后在7ml乙腈中搅拌1小时。过滤出留下的固体，用稍冷的乙腈洗涤，并真空干燥。产量：0.6197g(0.657mmol，75％)。
元素分析(C60H64O6P2的计算值＝943.1076g/mol)：C＝76.48(76.41)；H＝6.84(6.84)；P＝6.57(6.57)。
ESI-TOF HRMS:m/z＝965.4076；[M++Na]，计算值m/z＝965.4070。
31P NMR(CD2Cl2):d 134.4(d,JPP＝13Hz)；145.6(d,JPP＝13Hz)ppm。
1H NMR(CD2Cl2):d 1.25(s,9H)；1.38(s,9H)；1.46(s,9H)；1.48(s,9H)；6.64(m,2H)；6.85(m,1H)；6.99-7.13(m,19H)；7.33-7.38(m,3H)；7.44(m,1H),7.67(m,2H)ppm。
5-(叔丁基)-2-((3,3'-二叔丁基-5,5'-二甲氧基-2'-((4,4,5,5-四苯基-1,3,2-
二氧杂磷杂环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)苯并[d][1,3,2]二氧杂磷杂环
戊二烯(5)的合成：
在室温下向4,4,5,5-四苯基-2-((3,3',5,5'-四叔丁基-2'-((二氯磷烷基)氧基)-[1,1'-联苯]-2-基)氧基)-1,3,2-二氧杂磷杂环戊烷(0.618g；0.682mmol)在5ml甲苯中的溶液中滴加4-叔丁基邻苯二酚(0.1133g；0.6818mmol)和三乙胺(0.38ml)在3ml甲苯中的混合物。将混合物搅拌过夜并过滤，并将滤液真空浓缩至干。将获得的固体在60℃/0.1毫巴下干燥2小时，并吸收在6ml热乙腈中。将在深冻冰箱中贮存所述溶液后形成的固体滤出，用稍冷的乙腈洗涤，并真空干燥。产量：0.416g(0.477mmol，70％)。
元素分析(C64H72O6P2的计算值＝999.215g/mol):C＝76.75(76.93)；H＝7.20(7.26)；P＝6.15(6.20)。
ESI-TOF HRMS:m/z＝1021.4708；[M++Na]，计算值m/z＝1021.4696。
31P NMR(CD2Cl2):d 136.2(d,JPP＝10Hz)；136.3(d,JPP＝10Hz)；145.7(d,JPP＝10Hz)；145.8(d,JPP＝10Hz)ppm。2种非对映异构体。
1H NMR(CD2Cl2):d 1.24+1.25(2s,9H)；1.35+1.37+1.38(3s,18H)；1.45+1.48+1.49(3s,18H)；6.53(m,2H)；6.79(m,1H)；6.96-7.18(m,18H)；7.31-7.46(m,4H)；7.64(t；JHH＝2.3Hz；1H),7.67(d；JHH＝2.5Hz；1H)ppm。
4,6-二叔丁基-2-((3,3',5,5'-四叔丁基-2'-((4,4,5,5-四苯基-1,3,2-二氧杂
磷杂环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)苯并[d][1,3,2]二氧杂磷杂环戊二烯
(6)的合成：
在室温下向4,4,5,5-四苯基-2-((3,3',5,5'-四叔丁基-2'-((二氯磷烷基)氧基)-[1,1'-联苯]-2-基)氧基)-1,3,2-二氧杂磷杂环戊烷(0.6529g；0.7207mmol)在5ml甲苯中的溶液中滴加3,5-二叔丁基邻苯二酚(0.1602g；0.7207mmol)和三乙胺(0.40ml)在3ml甲苯中的混合物。将混合物搅拌过夜并过滤，并将滤液真空浓缩至干。将获得的固体在60℃/0.1毫巴下干燥2小时，然后在7ml乙腈中搅拌1.5小时，并在过滤后真空干燥。产量：0.5345g(0.5064mmol，70％)。
元素分析(C68H80O6P2的计算值＝1055.322g/mol)：C＝77.49(77.39)；H＝7.57(7.64)；P＝5.90(5.87)。
ESI-TOF HRMS：m/z＝1077.5305；[M++Na]，计算值m/z＝1077.5322。
31P NMR(CD2Cl2):d 132.5(d,JPP＝20Hz)；134.4(s,br)；144.3(d,JPP＝20Hz)；145.3(d,JPP＝11Hz)ppm。2种非对映异构体。
1H NMR(CD2Cl2):d 1.19(s；4.5H)；1.24(s；4.5H)；1.31(s；4.5H)；1.33(s；4.5H)；1.34(s；4.5H)；1.37(s；4.5H)；1.41(s；4.5H)；1.44(s；4.5H)；1.45(s,9H)；1.47(s；4.5H)；1.49(s,4.5H)；6.42(m,1H)；6.73(m；0.5H)；6.85(dd,JHH＝20.3Hz；JHH＝1.99Hz；1H)；6.96-7.16(m,16H)；7.23-7.30(m；1.5H)；7.31-7.43(m,4H)；7.60(dd,JHH＝12.5Hz；JHH＝2.4Hz；1H),7.66(dd,JHH＝8.5Hz；JHH＝2.5Hz；1H)ppm。
催化实验
在配备有压力保持装置、气体流量计、气体鼓泡搅拌器和压力吸管的得自瑞士伦高的Premex Reactor AG公司的200ml高压釜中进行加氢甲酰化。为了使湿气和氧气的影响最小化，在Pure Solv.MD-7系统中纯化用作溶剂的甲苯，并将其在氩气下贮存。将用作底物的烯烃“顺式/反式-2-戊烯”(Aldrich)在钠上加热回流，并将其在氩气下蒸馏。在所述高压釜中，在氩气气氛下，将催化剂前体的甲苯溶液和配体的甲苯溶液混合。将[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮酸根阴离子；COD＝1,5-环辛二烯)用作催化剂前体。将所述高压釜在搅拌下(1500rpm)在12巴下加热以达到20巴的最终压力。在达到反应温度后，将烯烃借助于在压力吸管中建立的超压压注到所述高压釜中。经4小时，在恒定压力(得自荷兰Bronkhorst公司的闭环压力控制器(Nachdruckregler))下进行所述反应。在反应时间结束后，将所述高压釜冷却至室温，在搅拌下卸压，并用氩气冲洗。在关闭搅拌器后立即在每种情况下取出1ml反应混合物，用10ml戊烷稀释，并通过气相色谱法分析：HP 5890SeriesII plus,PONA,50m×0.2mm×0.5μm。
使用根据本发明的化合物(1)至(6)和使用对比配体(D-1)进行所述反应。
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：4小时，Rh:配体的比例＝1:2。
结果整理在下表中：
| 配体 | 醛的产率[％] |
| 1* | 99 |
| 2* | 99 |
| 3* | 99 |
| 4* | 99 |
| 5* | 99 |
| 6* | 99 |
| D-1 | 14 |
*根据本发明的化合物
如实验结果所表明，通过根据本发明的化合物解决了所述技术问题。
Claims (13)
1.式(I)的化合物：
其中
R1、R2、R3、R4、R5、R6、R7、R8各自彼此独立地选自：-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是-(C1-C12)-烷基。
3.根据权利要求1和2中任一项的化合物，其中R5和R8是-叔丁基。
4.根据权利要求1至3中任一项的化合物，其中R6、R7选自：-(C1-C12)-烷基、-O-(C1-C12)-烷基。
5.根据权利要求1至4中任一项的化合物，其中R6和R7是-OCH3或-叔丁基。
6.根据权利要求1至5中任一项的化合物，其中R1、R2、R3、R4选自-H、-(C1-C12)-烷基。
7.根据权利要求1至6中任一项的化合物，其中R1、R2、R3、R4是-H或-叔丁基。
8.根据权利要求1至7中任一项的化合物，其中所述化合物具有结构(1)至(6)中的一种：
9.包括以下方法步骤的方法：
a)将烯属不饱和化合物初始加料；
b)添加根据权利要求1至8中任一项的化合物和包含Rh的物质；
c)输入H2和CO，
d)将得自a)至c)的反应混合物加热，其中烯烃转化成醛。
10.根据权利要求9的方法，其中在方法步骤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、二正丁烯或它们的混合物。
11.根据权利要求9或10中任一项的方法，其中所述包含Rh的物质选自：Rh(acac)(CO)2、[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮酸根阴离子；COD＝1,5-环辛二烯)、Rh4CO12。
12.根据权利要求9至11中任一项的方法，其中在方法步骤c)中将CO在1至6MPa(10至60巴)范围内的压力下输入。
13.根据权利要求9至12中任一项的方法，其中在方法步骤d)中将所述反应混合物加热到在80℃至160℃范围内的温度。
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| TW202302618A (zh) | 2023-01-16 |
| EP4059939A1 (de) | 2022-09-21 |
| PL4059939T3 (pl) | 2023-09-25 |
| EP4059939B1 (de) | 2023-06-07 |
| US20220298188A1 (en) | 2022-09-22 |
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