CN109535197B - 一种稳定亚磷酸盐配体的方法及其应用 - Google Patents
一种稳定亚磷酸盐配体的方法及其应用 Download PDFInfo
- Publication number
- CN109535197B CN109535197B CN201811553420.7A CN201811553420A CN109535197B CN 109535197 B CN109535197 B CN 109535197B CN 201811553420 A CN201811553420 A CN 201811553420A CN 109535197 B CN109535197 B CN 109535197B
- Authority
- CN
- China
- Prior art keywords
- ligand
- reaction
- phosphite
- cyclodextrin
- phosphite ligand
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 36
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 33
- -1 cyclodextrin compound Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 238000007037 hydroformylation reaction Methods 0.000 claims description 12
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001116 FEMA 4028 Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 3
- 229960004853 betadex Drugs 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 15
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005810 carbonylation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229940097362 cyclodextrins Drugs 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DNNUUTAVMJAIKT-UHFFFAOYSA-N 5-hydroxypentylphosphonic acid Chemical compound OCCCCCP(O)(O)=O DNNUUTAVMJAIKT-UHFFFAOYSA-N 0.000 description 1
- BBVARVTURNYWGV-UHFFFAOYSA-N 7-methyloctyl benzoate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1 BBVARVTURNYWGV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-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
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 238000006884 silylation reaction 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
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
-
- 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
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—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
- 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
- C07C45/505—Asymmetric hydroformylation
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种稳定亚磷酸盐配体的方法及其应用,在亚磷酸盐配体存在的反应体系中加入环糊精类化合物,以抑制配体的降解;在所述反应体系中,所述亚磷酸盐配体作为反应的催化剂或者与过渡金属共同组成反应的催化剂。通过该方法可以有效抑制反应体系中亚磷酸盐配体的分解,提高亚磷酸盐配体的寿命,进一步达到提高反应效率的目的。
Description
技术领域
本发明属于催化反应领域,具体涉及一种提高催化反应配体寿命的方法,尤其涉及一种催化反应中提高亚磷酸盐配体寿命的方法。
背景技术
亚磷酸盐配体与过渡金属组成的催化剂应用广泛。如US 4464515和4503196中公开用于不饱和化合物共轭双烯的氢化过程中,欧洲专利申请366212和177999中公开用于烯烃的低聚或二聚中,US 911518中公开用于光学活性药物的合成过程中,US4810815和4714773中公开用于丁二烯氢氰化为己二腈的过程中;US 5103033和欧洲申请459464中公开用于烯烃的氢化硅烧硅烷化。US 3499933公开了将一种含铑的亚磷酸盐配合物用于羰基化反应。
在反应过程中,亚磷酸盐配体会逐渐降解。US 4599206和4717775公开了一种亚磷酸盐配体的降解机理。在这一机理中,该配体在反应混合物中水的存在下进行缓慢水解。该分解产物然后与反应混合物中的醛类产物和附加的水,经一系列步骤反应生成羟烷基膦酸。该酸又进一步催化配体水解。这种不可避免的“连锁”效应使残留在反应溶液中的亚磷酸盐配体的水解变得非常快速。
目前解决亚磷酸盐配体降解的方法有三种:US 4567306中提出将叔胺加到反应体系中,将生成的羟烷基膦酸及时中和淬灭,避免发生自催化降解反应。但是加入的叔胺会催化体系中醛类化合物发生聚合反应,导致脚料率大幅增加;US 4712775中提出使反应混合物通过弱碱性离子交换树脂将自身催化产生的磷酸副产物从含有配体的体系中除去,并将处理过的混合物再循环到反应器中。但这种方式会导致贵金属催化剂的损失,并且需要增加设备投资;B.Costisella,H.Gross(J·Prakt.Chem.,317(5),798-806)报道了环氧化物和磷酸形成磷酸酯类化合物来抑制配体水解,但同样的,环氧也会与体系中的醛类产物形成副产物,而且必须不断补加以维持合适浓度。
环糊精是大环超分子,是环状葡萄糖的低聚物。环糊精具有内腔疏水的特性,能够与许多有机和无机分子通过主-客体识别形成包合物及分子组装体,从而形成微型反应器。Nakamura A,(Inoue Y.J.Am.Chem.Soc.,2003,125(4):966)在利用环糊精作为微反应器进行不对称[4+4]光环化二聚反应过程中,通过表征证实了环糊精包合物的存在(见附图1)。但文章中使用环糊精仅仅是用来提高某类反应的空间选择性,未有利用其空腔疏水性能防止亚磷酸盐水解的报道(见附图1)。
发明内容
本发明主要针对上述问题,提供一种新的稳定亚磷酸盐配体的方法,该方法通过一次性向氢甲酰化反应体系添加0.01wt%-5wt%的环糊精类超分子化合物,有效解决了亚磷酸盐配体降解的问题。
一种稳定亚磷酸盐配体的方法,包括:在亚磷酸盐配体存在的反应体系中加入环糊精类化合物,以抑制配体的降解。
在所述反应体系中,所述亚磷酸盐配体作为反应的催化剂或者与过渡金属共同组成反应的催化剂。
作为优选,所述反应体系为氢甲酰化反应体系。
作为优选,所述的环糊精类化合物为一次性加入,以反应混合物总重计,添加量为0.01wt%-5wt%;优选为0.1wt%-2wt%。
作为优选,所述的环糊精类化合物为环糊精或其衍生物。
作为优选,所述的环糊精类化合物为环糊精及其衍生物含6~12个D-吡喃葡萄糖单元,优选为含有6、7、8个葡萄糖单元的分子,即α、β和γ环糊精及其衍生物。
本发明中的方法适用于CN 1092058A中所提到的各种亚磷酸盐配体,作为优选,所述的亚磷酸盐配体选自三有机亚磷酸盐配体或多亚磷酸盐配体中的一种;
所述的三有机亚磷酸盐配体的结构如下式所示:
其中,R’为烃基,包括烷基或者芳基;优选为C1~C6烷基、取代或者未取代的苯基、取代或者未取代的萘基,所述的苯基或萘基上的取代基可以为甲基、甲氧基或者卤素等,例如:
所述的多亚磷酸盐配体的结构如下式所示:
其中,Ar是为取代或者未取代的芳基,包括苯基和稠环芳烃,优选为萘基;X独立地为数值0或1;Y是代表m价的烃基,m为2-6,Y进一步优选为亚烷基(即m=2),更优选为C1~C10亚烷基;A独立表示一个二价桥基(例如:-CR1R2-、-O-、-S-、-NR3-、-SiR4R5-或-CO-等,其中,R1和R2分别表示H、C1~C12烷基、苯基、甲苯基或甲氧苯基,R3、R4或R5分别表示H或-CH3),n为0或1。例如:
本发明还提供了一种进行氢甲酰化反应的方法,包括:在反应溶剂中加入亚磷酸盐配体和铑催化剂,然后加入所述的环糊精类化合物,搅拌使环糊精与亚磷酸盐配体形成包合物,然后升温通入烯烃原料和混合气(一氧化碳和氢气)进行氢甲酰化反应,反应结束后得到氢甲酰化产物。
其中,所述氢甲酰化反应的温度一般为70-140℃,优选80-120℃。
所述烯烃原料与混合气没有比例限制;混合气比例(一氧化碳:氢气)也无特殊限制,一般约70:30~30:70,优选50:50。
所述反应溶剂并无特殊要求,只要能溶解反应原料和催化剂形成均相,且沸点高于产品以利于精馏分离,优选四乙二醇二甲醚、四甘醇二甲醚、二甲基甲酰胺、二甲基亚砜。
同现有技术相比,本发明的有益效果体现在:
(1)本发明中所添加的环糊精不会催化甲酰化反应体系发生副反应,尤其是醛类产物的聚合副反应;
(2)本发明中所添加的环糊精性质稳定,随反应时间的增加无需补加即可维持有效浓度;
(3)本发明中所需环糊精类添加剂简单易得,成本低廉,有利于生产上大规模应用。
附图说明
图1为现有技术中环糊精包合物的结构示意图;
图2为实施例2的羰基化反应转化率与产物正异比随时间的变化结果图;
图3为实施例2~6中30天不同溶剂的平均转化率和平均正异比的变化结果图;
图4为实施例7~10中30天不同原料的平均转化率和平均正异比的变化结果图;
图5为实施例11~14中30天不同配体的平均转化率和平均正异比的变化结果图。
具体实施方式
以下实施例有利于对本发明作进一步详细描述,但不对本发明构成限制。
实施例1
参考US 5364950中评价配体稳定性的方法,模拟氢甲酰化反应的溶液。该溶液含有72ppm铑,0.6wt%的配体A(6,6’-[3,3’,5,5’-四(1,1-二甲基乙基)1,1’-二苯基-2,2’-二基]二氧]二-二苯并[d,f][1,3,2]-二膦氧配体),约84wt%丁醛,约8.2wt%四甘醇二甲醚作为溶剂和约7.1wt%联苯酚。将五等份的该溶液填充分配到用氮气清洗的容器中。留下样品A不变,作为对照。在样品B到E中加入0.2wt%羟基戊基膦酸和0.6wt%水(均基于容器中内容物的总重计算)。样品B中不再添加任何物质,样品C中加入5wt%的叔丁胺,样品D中加入5wt%的氧化苯乙烯并在样品E中加入1wt%β环糊精。在相同实验条件下,定时取出样品溶液测定残留于溶液中的配体的量。表l表明了24小时后残留的原始配体百分数。通过比较说明本发明实现了改善的目的。
表1
样品 | 配体残留百分数% |
1A | 100 |
1B | 0 |
1C | 67 |
1D | 33 |
1E | 99 |
配体A具体结构式如下:
实施例2
参考US 5364950实施例12中利用两釜串联羰基化反应评价配体稳定性的方法,用β环糊精(占总混合物质量0.7wt%)代替1,2-环氧十二烷。反应持续124天,相比于US5364950中描述的每三天补加一次0.2wt%的1,2-环氧十二烷,本反应过程中未进行配体和环糊精的补加,其他条件与US 5364950保持一致。图2显示了羰基化反应转化率与产物正异比随时间的变化,每三天取样一次,共测试124天。如图2中所示,在124天反应过程中,催化剂的活性没有变化,产物的正异比基本稳定在95左右(高的正异比可能是由于环糊精的空腔具有择形效应)。这恒定的活性表明在反应过程中并没有过量的配体发生降解。
实施例3
除了将反应溶剂四乙二醇二甲醚等体积更换为二甲基亚酰胺,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例4:
除了将反应溶剂四乙二醇二甲醚等体积更换为二甲基亚砜,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例5:
除了将反应溶剂四乙二醇二甲醚等体积更换为乙二醇,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例6:
除了将反应溶剂四乙二醇二甲醚等体积更换为苯甲酸异壬酯,运行时间改为30天,其他工艺条件与实施例2保持一致。
比较实施例2~6,通过分别计算30天的平均转化率和平均正异比来比较几种不同溶剂的区别,结果图3所示:
由图3的变化结果图中可以看出,二甲基甲酰胺和二甲亚砜的效果略好与其他溶剂。
实施例7
除了将反应原料变为丙烯,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例8
除了将反应原料变为1-辛烯,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例9
除了将反应原料变为苯乙烯,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例10
除了将反应原料变为异丁烯,运行时间改为30天,其他工艺条件与实施例2保持一致。
比较实施例7-10,通过分别计算30天的平均转化率和平均正异比来该方法对不同原料的适用情况,结果图4所示:
由图4变化结果图中可以看出,该方法对实施例中所述烯烃均有较好的适用性,30天的平均转化率和正异比均较稳定;而且对不同烯烃能显著提高产物的正异比。
实施例11
除了将配体变为以下结构,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例12
除了将配体替换为以下结构,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例13
除了将配体替换为以下结构,运行时间改为30天,其他工艺条件与实施例2保持一致。
实施例14
除了将配体替换为以下结构,运行时间改为30天,其他工艺条件与实施例2保持一致。
比较实施例11-14,通过分别计算30天的平均转化率和平均正异比来该方法对不同原料的适用情况,结果如图5所示:
由图5变化结果图中可以看出,该方法对亚磷酸盐配体具有普遍适用性,实施例11可能是由于配体上的基团与所选用的环糊精空腔尺寸出现不匹配,导致保护效果出现差异。
Claims (7)
2.根据权利要求1所述的稳定亚磷酸盐配体的方法,其特征在于,所述反应体系为氢甲酰化反应体系。
3.根据权利要求1所述的稳定亚磷酸盐配体的方法,其特征在于,在所述反应体系中,所述亚磷酸盐配体作为反应的催化剂或者与过渡金属共同组成反应的催化剂。
4.根据权利要求1所述的稳定亚磷酸盐配体的方法,其特征在于,所述的环糊精类化合物为一次性加入,以反应混合物总重计,添加量为0.01wt%-5wt%。
5.根据权利要求4所述的稳定亚磷酸盐配体的方法,其特征在于,所述的环糊精类化合物为一次性加入,以反应混合物总重计,添加量为0.1wt%-2wt%。
6.一种进行氢甲酰化反应的方法,其特征在于,包括:在反应溶剂中加入亚磷酸盐配体和铑催化剂,然后按照权利要求1~5任一项所述的稳定亚磷酸盐配体的方法加入环糊精类化合物,搅拌使环糊精类化合物与亚磷酸盐配体形成包合物,然后升温通入烯烃原料和混合气进行氢甲酰化反应,反应结束后得到氢甲酰化产物;
所述的混合气为一氧化碳和氢气。
7.根据权利要求6所述的进行氢甲酰化反应的方法,其特征在于,所述的烯烃原料包括乙烯、丙烯、1-辛烯、苯乙烯或异丁烯。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811553420.7A CN109535197B (zh) | 2018-12-19 | 2018-12-19 | 一种稳定亚磷酸盐配体的方法及其应用 |
PCT/CN2019/095104 WO2020124996A1 (zh) | 2018-12-19 | 2019-07-08 | 一种稳定亚磷酸盐配体的方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811553420.7A CN109535197B (zh) | 2018-12-19 | 2018-12-19 | 一种稳定亚磷酸盐配体的方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109535197A CN109535197A (zh) | 2019-03-29 |
CN109535197B true CN109535197B (zh) | 2020-04-21 |
Family
ID=65855320
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811553420.7A Active CN109535197B (zh) | 2018-12-19 | 2018-12-19 | 一种稳定亚磷酸盐配体的方法及其应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN109535197B (zh) |
WO (1) | WO2020124996A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109535197B (zh) * | 2018-12-19 | 2020-04-21 | 山东新和成维生素有限公司 | 一种稳定亚磷酸盐配体的方法及其应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3553298A (en) * | 1967-10-20 | 1971-01-05 | Hooker Chemical Corp | Hydrolytic stabilized phosphite esters |
SI9300506A (en) * | 1992-09-29 | 1994-06-30 | Union Carbide Chem Plastic | Process for stabilizing phosphite ligands |
CN1092075A (zh) * | 1992-10-05 | 1994-09-14 | 希巴-盖吉股份公司 | 用胺类化合物稳定三价磷化合物的方法 |
CN104955568A (zh) * | 2012-09-25 | 2015-09-30 | 陶氏技术投资有限责任公司 | 用于稳定亚磷酸酯配体抵抗降解的方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109535197B (zh) * | 2018-12-19 | 2020-04-21 | 山东新和成维生素有限公司 | 一种稳定亚磷酸盐配体的方法及其应用 |
-
2018
- 2018-12-19 CN CN201811553420.7A patent/CN109535197B/zh active Active
-
2019
- 2019-07-08 WO PCT/CN2019/095104 patent/WO2020124996A1/zh active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3553298A (en) * | 1967-10-20 | 1971-01-05 | Hooker Chemical Corp | Hydrolytic stabilized phosphite esters |
SI9300506A (en) * | 1992-09-29 | 1994-06-30 | Union Carbide Chem Plastic | Process for stabilizing phosphite ligands |
CN1092058A (zh) * | 1992-09-29 | 1994-09-14 | 联合碳化化学品及塑料技术公司 | 稳定亚磷酸盐配体的方法 |
CN1092075A (zh) * | 1992-10-05 | 1994-09-14 | 希巴-盖吉股份公司 | 用胺类化合物稳定三价磷化合物的方法 |
CN104955568A (zh) * | 2012-09-25 | 2015-09-30 | 陶氏技术投资有限责任公司 | 用于稳定亚磷酸酯配体抵抗降解的方法 |
CN104955568B (zh) * | 2012-09-25 | 2017-05-03 | 陶氏技术投资有限责任公司 | 用于稳定亚磷酸酯配体抵抗降解的方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2020124996A1 (zh) | 2020-06-25 |
CN109535197A (zh) | 2019-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3257873B1 (en) | Method for preparing oligomerization catalyst system, and oligomerization catalyst system prepared by same | |
CN104837851B (zh) | 不对称的双亚磷酸酯 | |
Hebrard et al. | Cobalt-catalyzed hydroformylation of alkenes: generation and recycling of the carbonyl species, and catalytic cycle | |
JP5134687B2 (ja) | リンを含むオレフィン系化合物のヒドロホルミル化反応のための触媒組成物およびそれを用いたヒドロホルミル化方法 | |
Pierantozzi et al. | Preparation and catalytic properties of polymer-and silica-supported bimetallic clusters | |
JP6517215B2 (ja) | リン系配位子を含む触媒組成物及びそれを用いたヒドロホルミル化方法 | |
KR101095775B1 (ko) | 올레핀계 화합물의 히드로포밀화 반응용 촉매 조성물 및 이를 이용한 올레핀계 화합물의 히드로포밀화 방법 | |
EP3260460B1 (en) | Ligand compound, organic chrome compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using same | |
KR101411040B1 (ko) | 히드로포밀화 반응용 촉매 조성물 및 이를 이용한 히드로포밀화 방법 | |
CN109937090B (zh) | 处理加氢甲酰化催化剂溶液的方法 | |
CN109776294B (zh) | 一种烯烃氢甲酰化反应方法 | |
TW201035033A (en) | Hydroformylation process with doubly open-ended bisphosphite ligand | |
CN109311793B (zh) | 用于生产醛的催化剂和方法 | |
EP3712126B1 (en) | Method for producing aldehyde and method for producing alcohol | |
CN109535197B (zh) | 一种稳定亚磷酸盐配体的方法及其应用 | |
Dahan et al. | Dendritic effect in polymer-supported catalysis of the intramolecular Pauson–Khand reaction | |
CN104870086B (zh) | 用于氢甲酰化反应的催化剂组合物及使用该催化剂组合物氢甲酰化烯烃的方法 | |
EP3101039A1 (en) | Ligand compound, organic chrome compound, catalyst system for olefin oligomerization, and method for oligomerizing olefin using same | |
KR100191082B1 (ko) | 중합체 제조 방법 | |
EP3190118B1 (en) | Ligand compound, organic chrome compound, catalyst system for olefin oligomerization, and method for oligomerizing olefin using same | |
Castelbou et al. | Ligand effect in the Rh-NP catalysed partial hydrogenation of substituted arenes | |
Li et al. | Cationic palladium catalyzed nonalternating copolymerization of ethylene with carbon monoxide: Microstructure analysis and computational study | |
KR20100092169A (ko) | 인을 포함하는 촉매 조성물을 이용한 알데히드의 제조방법 | |
US3931332A (en) | Stabilized hydroformylation reaction systems | |
JP2016503755A (ja) | ヒドロホルミル化方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |