CN1857776A - Application of substituted bidentate amido phosphite ligand on binaphthol skeleton in hydroformylation of olefin - Google Patents
Application of substituted bidentate amido phosphite ligand on binaphthol skeleton in hydroformylation of olefin Download PDFInfo
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Abstract
The present invention relates to the application of substituted bidentate amido phosphete ligand on binaphthol skeleton in catalyzing hydroformylation of olefin. Under inert gas or N2 atmosphere, ligand I and Rh salt react in organic solvent to obtain ligand I/Rh catalyst. Under inert gas or N2 atmosphere, olefin substrate is added into solution of ligand I/Rh catalyst and CO and H2 are filled to react to obtain hydroformylated product, or aldehyde group containing compound. The present invention has high reaction conversion rate.
Description
Technical field
The substituted bidentate phosphoramidite ligand that the present invention relates to the dinaphthol skeleton is used to prepare the catalyst of hydroformylation reaction.This catalyst can be used for the hydroformylation reaction of catalyzed alkene compound, the synthetic compound that contains aldehyde radical.
Background technology
Hydroformylation of olefin can be converted into basic chemical raw materials alkene cheap and easy to get multiple important fine chemicals easily and effectively, is the homogeneous catalysis process of production scale maximum up to now.[Qian Yanlong, Liao Shijian, " homogeneous catalysis progress ", Chemical Industry Press, Beijing, 1989], [Yin Yuanqi, " carbonyl synthetic chemistry ", Chemical Industry Press, Beijing, 1995], [Bhaduri, S.; Mukesh, D.HomogeneneousCatalysis:Mechanisms and Industrial Applications, John Wiley ﹠amp; Sons, 2000, pp85-103.], [Frohning, C.D.; Kohlpaintner, C.W.in Applied Homogeneous Catalysiswith Organometallic Compounds, ed.By Cornils, B.; Herrmann, W.A.VCH, Weinheim, New York, 1996, Vol 1, pp29-104.], [Trzeciak, A.M.; Zi ó lkowski, J.J.Coord.Chem.Rev.1999,190-192,883-900.].Industrial; the hydroformylation reaction of alkene mainly comes catalysis to realize by two kinds of metals of Co, Rh; but since last century the seventies; the ligand modified rhodium catalyst of phosphorus has just been dominated the hydroformylation reaction research of alkene, and has progressively been replaced the main use object that Co catalysts becomes industrial hydroformylation process with its high activity, outstanding selectivity and gentle outstanding advantages such as reaction condition.[Falbe，J.Proplene and its Industrial Derivatives，Chap.9.Ed.By Hancock，E.G.1973.]，[Falbe，J.Carbon Monoxide in Organic Synthesis：Springer-Verlag，New York.1970.]，[Cornils，B.；in Falbe，J.New Synthesis with Carbon Monoxide，Springer-Verlag，New York.1980.]。The phosphorus part is the key of phosphorus/rhodium catalyst, and it has determined activity of such catalysts and selectivity.According to the different of atom that link to each other with P, the phosphorus part can be divided into phosphine part that P links to each other with three carbon atoms, phosphite ester ligand that P links to each other with one or more O atoms again, contain phosphoramidite ligand three classes that P links to each other with one or more N atoms.[Brester，A.V.；Chem.Engineering Nov.1976，8，90.]，[M.Beller，B.Cornils，C.D.Frohling，C.W.Kohlpaintner，J.Mol.Catal.A.Chem.1995，104，17.]，[Billig，E.；Abatjoglou，A.G.；Bryant，D.R.U.S.Pat.4 769498，1988(to Union Carbide).]，[van Leeuwen，P.W.N.M.；Roobeek，C.F.J.Organomet.Chem.1983，258，343；Brit.Pat.2,068,377，U.S.Pat.4,467,116，1983(to Shell Oil)；Chem.Abstr.1984，101，191142.]。Phosphoramidite ligand is generally synthetic than being easier to, and is difficult for oxidizedly, and shows good catalytic activity and selectivity in the hydroformylation of olefin of Rh (I) catalysis.[van der Slot，S.C.；Duran，J.；Luten，J.；Kamer，P.C.J.；van Leeuwen，P.W.N.M.Organometallics 2002，21，3873-3883.]，[Magee，M.P.；Luo，W.；Hersh，W.H.Organometallics 2002，21，362-372]。Different with preceding two class parts, the research of bidentate phosphoramidite ligand in the hydroformylation of olefin of Rh (I) catalysis that such part, especially pyrroles replace is also fewer.Aspect practical, applied for an international monopoly by people such as Ojima in 2004, the substituted bidentate phosphoramidite ligand that they will have optically active xenol skeleton is applied to multiple asymmetric catalysis.[Ojima，I.；Takai，M.；Takahashi，T.；Urata，Hisao(Mitsubishi Chemical Corporation；TheResearch Foundation of State University of New York，Japan).PCT Int.Appl.WO2004076464 A2 10 Sep 2004，83 pp.]。1999, people such as Ahlers applied for the patent that the substituted bidentate phosphoramidite ligand of dinaphthol skeleton is used in the hydrogen cyanation of alkene, the research but the application of such part in the hydroformylation reaction of alkene also had no talent.[Tam，W.；Foo，T.；Garner，J.M.(E.I.Du Pontde Nemours & Co.，USA).PCT Int.Appl.(1999)，WO 9952632 A1 19991021]。This patent is used in the hydroformylation reaction of substituted bidentate phosphoramidite ligand at alkene of dinaphthol skeleton having applied on such basis just.
Summary of the invention
Purpose of the present invention provides the substituted bidentate phosphoramidite ligand I of dinaphthol skeleton to be used to prepare the catalyst of hydroformylation reaction.This catalyst can be used for the hydroformylation reaction of catalyzed alkene compound, the synthetic compound that contains aldehyde radical.
Ligand i has following structure:
R
1And R
2Can be respectively the heterocycle that contains N, as
Or
Or
R wherein
xAnd R
X 'Can be respectively hydrogen, C
1～C
10Alkyl, C
1～C
10Alkoxyl, C
1～C
10Alkanoyl, C
1～C
10Ester group, halogen or itrile group, for example hydrogen, methyl, methoxyl group, ethyl, ethyoxyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, suberyl, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl, halogen, formoxyl, acetyl group and acyl group, carbomethoxy, ethoxycarbonyl, propyl ester base or itrile group etc.The N atom of heterocycle directly links to each other with the P atom.
R
3And R
4Can be respectively
Or
Or
Or
Or O-R
w, R wherein
xAnd R
X 'Can be respectively hydrogen, C
1～C
10Alkyl, C
1～C
10Alkoxyl, C
1～C
10Alkanoyl, C
1～C
10Ester group, halogen or itrile group, for example hydrogen, methyl, methoxyl group, ethyl, ethyoxyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, suberyl, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl, halogen, formoxyl, acetyl group, propiono, carbomethoxy, ethoxycarbonyl, propyl ester base or itrile group etc.; R
wCan be respectively hydrogen or C
1～C
10Alkyl, for example hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, suberyl, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl etc.
R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15And R
16Can be respectively hydrogen, C
1-12Alkyl,
O-R
w, C
1～C
10Alkanoyl, C
1～C
10Ester group, halogen or itrile group etc., described C
1～C
10Alkanoyl for example formoxyl, acetyl group, propiono, described C
1～C
10Ester group for example carbomethoxy, ethoxycarbonyl, propyl ester base etc., described alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, suberyl etc. for example, wherein R
x, R
X 'Can be respectively hydrogen, C
1～C
10Alkyl, C
1～C
10Alkoxy or halogen, for example hydrogen, methyl, methoxyl group, ethyl, ethyoxyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, suberyl, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl or halogen etc., R
y, R
Y ', R
Y ", R
z, R
Z 'And R
wCan be respectively hydrogen or C
1～C
10Alkyl, for example hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, suberyl, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl etc.
Ligand i can be synthetic by following method, is exactly by phosphorus chlorine
With
Obtain with corresponding two phenolic compounds, 1 reaction, this process can be represented with following reaction equation:
Purpose of the present invention provides the purposes of ligand i, and promptly ligand i can be used for preparing the catalyst of hydroformylation reaction, catalysis hydroformylation reaction.This Preparation of catalysts process can be represented with following reaction equation:
Can specify as follows to above-mentioned preparation process:
At inert gas such as Ar gas or N
2Under the gas atmosphere, ligand i and Rh salt stir in organic solvent and can obtain ligand i/Rh catalyst, i.e. the catalyst that combines with Rh salt of ligand i.Wherein the reaction condition of Tui Jianing is: the mol ratio of ligand i and Rh salt is: 1-100: 1, and further recommending mol ratio is 2～50: 1; Reaction temperature: 0 ℃-100 ℃, further the recommendation response temperature is 60～100 ℃, the reaction time: 0.1-20h.
The catalyst of above-mentioned preparation can be used for the hydroformylation reaction of catalyzed alkene compound, the synthetic compound that contains aldehyde radical, and the reaction condition that this catalytic process is recommended is as follows:
At inert gas such as Ar gas or N
2Under the gas atmosphere, in the solution of ligand i/Rh catalyst, add olefin substrate, charge into CO and H respectively
2, reaction can obtain the hydroformylation product, promptly contains the compound of aldehyde radical.Wherein the mol ratio of alkene and ligand i/Rh catalyst is: 100-100000: 1, and reaction temperature: 20 ℃-120 ℃, reaction time: 0.1-100h, CO pressure: 0.5-100 atmospheric pressure, H
2Pressure: 0.5-100 atmospheric pressure.Described olefin substrate is recommended as C
2～C
50Alkene, further be recommended as C
2～C
30Alkene.
The organic solvent that uses in said method of the present invention can be benzene,toluene,xylene, trimethylbenzene, acetonitrile, ether, oxolane, glycol dimethyl ether, chloroform, carrene, methyl alcohol, ethanol, isopropyl alcohol, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone etc.
The Rh salt that in said method of the present invention, uses can be Rh (acac) (CO)
2, Rh (acac) (C
2H
4), [Rh (C
2H
4)
2Cl]
2, [Rh (cod) Cl]
2, [Rh (CO)
2Cl]
2Or Rh (cod) BF
4Deng.Described acac represents acetylacetone,2,4-pentanedione, and cod represents 1, the 5-cyclo-octadiene.
The substituted bidentate phosphoramidite ligand I that the invention provides the dinaphthol skeleton is used to prepare the new purposes of the catalyst of hydroformylation reaction, by the hydroformylation reaction of catalyzed alkene compound, and the synthetic compound that contains aldehyde radical, reaction conversion ratio height.
Specific implementation method
Help further to understand the present invention by following embodiment, but do not limit the content of invention.
Embodiment 1: following bidentate phosphoramidite ligand synthetic
Two pyrroles's phosphorus chlorine
Synthetic by phosphorus trichloride and pyrroles: as in a 500mL there-necked flask, to add anhydrous tetrahydro furan (200mL) and phosphorus trichloride (8.7mL under the argon atmospher respectively, 0.1mol), 0 ℃ drips pyrroles (13.9mL, 0.2mol) and triethylamine (28mL, 0.2mol) anhydrous tetrahydro furan (50mL) solution, after dropwising in 2 hours, slowly be warming up to room temperature and stir and spend the night, remove by filter triethylamine hydrochloride under the argon atmospher, the most of solvent of pressure reducing and steaming, residue is collected 80 ℃ of (1mmHg) cuts and is got colorless oil 16.0g, yield 81% through the decompression distillation purifying.
1H NMR(300MHz，CDCl
3)δ7.07-7.10(m，4H)，6.39(t，J＝2.1Hz，4H)；
31P NMR(121.46MHz，CDCl
3)δ104.35(s)。
Under argon gas atmosphere, (1.13g 5.7mmol) and anhydrous tetrahydro furan (10mL), is cooled to 0 ℃, drips (±)-BINOL to add two pyrroles's phosphorus chlorine in the Schlenk of 50mL pipe respectively
(0.65g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains colorless oil 1.0g to column chromatography, putting refrigerator and cooled freezes product and is solidified into white solid, yield 62%.
M.p.88-90℃；
1H NMR(300MHz，CDCl
3)δ＝7.90(d，J＝8.4Hz，4H)，7.47(t，J＝7.5Hz，2H)，7.32(t，J＝7.6Hz，2H)，7.24(d，J＝9.9Hz，2H)，7.15(d，J＝8.7Hz，2H)，6.46-6.49(m，8H)，6.10(dd，J＝15.6，1.8Hz，8H)；
31P NMR(121.46MHz，CDCl
3，)δ109.31(s)；IR(KBr pellet)v3101，1621，1590，1505，1454，1232，1179，1053，1037，960，803，730cm
-1，Elemental analysis(％)：calcd.for C
36H
28N
4O
2P
2：C70.82，H 4.62，N 9.18；found：C 70.95，H 4.87N 8.95。
Embodiment 2: following bidentate phosphoramidite ligand synthetic
Two pyrroles's phosphorus chlorine
Synthetic by phosphorus trichloride and indoles: as in a 500mL there-necked flask, to add anhydrous tetrahydro furan (200mL) and phosphorus trichloride (8.7mL under the argon atmospher respectively, 0.1mol), 0 ℃ drips indoles (23.4g, 0.2mol) and triethylamine (28mL, 0.2mol) anhydrous tetrahydro furan (50mL) solution, after dropwising in 2 hours, slowly be warming up to room temperature and stir and spend the night, remove by filter triethylamine hydrochloride under the argon atmospher, the most of solvent of pressure reducing and steaming, residue is collected 120 ℃ of (0.1mmHg) cuts and is got colorless oil 24.5g, yield 82% through the decompression distillation purifying.
Under argon gas atmosphere, in the Schlenk of 50mL pipe, add two indoles phosphorus chlorine (1.71g respectively, 5.7mmol) and anhydrous tetrahydro furan (10mL), be cooled to 0 ℃, drip (±)-BINOL (0.65g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains white solid 1.3g, yield 70% to column chromatography.
Embodiment 3: following bidentate phosphoramidite ligand synthetic
Two (3-methylpyrrole) phosphorus chlorine
Synthetic by phosphorus trichloride and 3-methylpyrrole: as in a 500mL there-necked flask, to add anhydrous tetrahydro furan (200mL) and phosphorus trichloride (8.7mL under the argon atmospher respectively, 0.1mol), 0 ℃ drips 3-methylpyrrole (16.2g, 0.2mol) and triethylamine (28mL, 0.2mol) anhydrous tetrahydro furan (50mL) solution, after dropwising in 2 hours, slowly be warming up to room temperature and stir and spend the night, remove by filter triethylamine hydrochloride under the argon atmospher, the most of solvent of pressure reducing and steaming, residue is collected 100 ℃ of (1mmHg) cuts and is got colorless oil 20.5g, yield 91% through the decompression distillation purifying.
Under argon gas atmosphere, in the Schlenk of 50mL pipe, add two (3-methylpyrrole) phosphorus chlorine (1.29g respectively, 5.7mmol) and anhydrous tetrahydro furan (10mL), be cooled to 0 ℃, drip (±)-BINOL (0.65g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains colorless oil 1.2g to column chromatography, putting refrigerator and cooled freezes product and is solidified into white solid, yield 78%.
Embodiment 4: following bidentate phosphoramidite ligand synthetic
Phenol oxygen base pyrroles phosphorus chlorine
Synthetic by phosphorus trichloride, phenol and pyrroles: as in a 500mL there-necked flask, to add anhydrous tetrahydro furan (200mL) and phosphorus trichloride (8.7mL under the argon atmospher respectively, 0.1mol), 0 ℃ drips phenol (9.4g, 0.1mol) and triethylamine (14.0mL, 0.1mol) anhydrous tetrahydro furan (25mL) solution, after dropwising in 1 hour, continue to stir 2 hours; 0 ℃ drips pyrroles (7.0mL, 0.1mol) and triethylamine (14.0mL, 0.1mol) anhydrous tetrahydro furan (25mL) solution, after dropwising in 1 hour, slowly be warming up to room temperature and stir and spend the night, remove by filter triethylamine hydrochloride under the argon atmospher, the most of solvent of pressure reducing and steaming, residue is collected 102 ℃ of cuts and is got colorless oil 17.0g, yield 75% through the decompression distillation purifying.
Under argon gas atmosphere, in the Schlenk of 50mL pipe, add phenol oxygen base pyrroles phosphorus chlorine (1.29g respectively, 5.7mmol) and anhydrous tetrahydro furan (10mL), be cooled to 0 ℃, drip (±)-BINOL (0.65g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains colorless oil 1.1g, yield 72% to column chromatography.
Embodiment 5: following bidentate phosphoramidite ligand synthetic
Under argon gas atmosphere, (1.13g 5.7mmol) and anhydrous tetrahydro furan (10mL), is cooled to 0 ℃, drips (±)-3,3 '-dimethyl-BINOL to add two pyrroles's phosphorus chlorine in the Schlenk of 50mL pipe respectively
(0.72g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains white solid 1.1g, yield 75% to column chromatography.
Embodiment 6: following bidentate phosphoramidite ligand synthetic
Under argon gas atmosphere, (1.13g 5.7mmol) and anhydrous tetrahydro furan (10mL), is cooled to 0 ℃, drips (±)-3,3 '-diphenyl-BINOL to add two pyrroles's phosphorus chlorine in the Schlenk of 50mL pipe respectively
(1.01g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains the solid thing 1.4g of white, yield 80% to column chromatography.
Embodiment 7: following bidentate phosphoramidite ligand synthetic
Under argon gas atmosphere, (1.13g 5.7mmol) and anhydrous tetrahydro furan (10mL), is cooled to 0 ℃, drips (±)-3,3 '-two bromo-BINOL to add two pyrroles's phosphorus chlorine in the Schlenk of 50mL pipe respectively
(1.02g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains orange solid thing 1.5g, yield 85% to column chromatography.
Embodiment 8: following bidentate phosphoramidite ligand synthetic
Under argon gas atmosphere, (1.13g 5.7mmol) and anhydrous tetrahydro furan (10mL), is cooled to 0 ℃, drips (±)-6,6 '-two bromo-BINOL to add two pyrroles's phosphorus chlorine in the Schlenk of 50mL pipe respectively
(1.02g, 2.3mmol) and anhydrous triethylamine (0.82mL, 5.9mmol) anhydrous tetrahydro furan (5mL) solution, slowly be warming up to room temperature and stir and spend the night, stop reaction, decompression is revolved and is desolvated, and (eluent: benzinum: ethyl acetate=5/1) separation obtains orange solid thing 1.5g, yield 85% to column chromatography.
Embodiment 9-33: bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis 1-octene
The ratio of part/Rh has been carried out screening (embodiment 9-13), and result of experiment sees Table one; The concentration of substrate has been carried out screening (embodiment 14-17), and experimental result sees Table two; Catalyst amount has been carried out screening (embodiment 18-22), and experimental result sees Table three; To CO and H
2Pressure carried out screening (embodiment 23-28), experimental result sees Table four; Reaction time has been carried out investigating (embodiment 29-33), and experimental result sees Table five.Specific operation process for this experiment is carried out representative illustration with the course of reaction of embodiment 20 and 21.
Embodiment 21: in argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, (17.7mg 0.029mmol), puts down interior air three times with the argon replaces reaction, adds 1.0mLRh (acac) (CO) to add the bidentate phosphoramidite ligand
2Anhydrous toluene solution (every milliliter of toluene is dissolved with Rh (acac) (CO)
20.25mg (0.00097mmol)), stir 10min; (7.5mL is 48.4mmol) with interior mark decane 0.5mL to add substrate 1-octene.In glove box, reaction bulb is transferred in the autoclave, autoclave is sealed the taking-up glove box, use CO/H
2Replace three times gas, gas CO/H
2(1: 1) stirs 1.5h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, get a reactant liquor and be diluted to 1mL, GC analyzes the molar content of conversion ratio, just different ratio and each component.Conversion ratio is 77%, and just different ratio is 225, and hundred parts of content of mole of linear chain aldehyde are 93.0%, and the molar content of 2-octene is 6.6%.The nmr analysis of linear chain aldehyde:
1H NMR (300MHz, CDCl
3) δ=0.88 (t, J=6.9Hz, 3H), 1.27-1.35 (m, 10H), 1.60-1.66 (m, 2H), 2.45 (d, J=5.7Hz, 2H), 9.77 (t, J=1.8Hz, 1H).
Embodiment 20: in argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, added Rh (acac) (CO)
20.3mg (22mg 0.035mmol), uses the interior air of argon replaces reaction bulb three times, and (9.0mL 58.1mmol) with interior mark decane 0.6mL, stirs 10min to add substrate 1-octene (0.00116mmol), to add the bidentate phosphoramidite ligand again.In glove box, reaction bulb is transferred in the autoclave, autoclave is taken out glove box, use CO/H
2Replace three times gas, charge into synthesis gas CO/H
2(1: 1) stirs 4h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, get a reactant liquor and be diluted to 1mL, GC analyzes the molar content of conversion ratio, just different ratio and each component.Conversion ratio＞99%; Just different ratio is 201; Hundred parts of content of mole of linear chain aldehyde are 93.0%; Hundred parts of content of mole of 2-octene are 6.6%.
The screening of the ratio of table one part/Rh (embodiment 9-13)
a
| Embodiment | The mol ratio of substrate/catalyst | The ratio of part/Rh | Reaction time (h) | Conversion ratio (%) | Just different ratio b | Linear chain aldehyde c (％) | The 2-octene d (％) | TOF e (h -1) |
| 9 10 11 12 13 | 6000 20000 20000 20000 20000 | 0 2 5 10 50 | 2 2 2 2 2 | 45 59 82 83 75 | 2.5 8.8 92 195 206 | 42.0 59.0 91.0 93.5 92.8 | 41.0 35.0 7.6 6.1 6.8 | 796 3840 7577 7790 6990 |
aReaction condition: 80 ℃, P
CO=P
H2=10bar, the concentration of 1-octene is 2.0M, reaction dissolvent is a toluene, in just be designated as-ten alkane.The molar content of conversion ratio, just different ratio and each component of product is all crossed gas phase analysis and is determined.
bThe ratio of linear chain aldehyde and branched chain aldehyde.
cLinear chain aldehyde accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
dThe 2-octene accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
eThe molal quantity of the aldehyde (linear chain aldehyde+branched chain aldehyde) that generates of every mole of Rh catalysis per hour.
The screening of table two concentration of substrate (embodiment 14-17)
a
| Embodiment | The mol ratio of substrate/catalyst | The ratio of part/Rh | Concentration of substrate (M) | Reaction time (h) | Conversion ratio (%) | Just different ratio b | Linear chain aldehyde c (％) | The 2-octene d(％) | TOF e (h -1) |
| 14 15 11 16 17 | 20000 20000 20000 50000 50000 | 5 5 5 5 5 | 0.67 1.0 2.0 2.0 f | 2.25 2 2 4.25 4.28 | 46 67 82 71 74 | 211 193 92 19 6.1 | 93 92 91 79 58 | 6.9 7.2 7.6 17 33 | 3807 6218 7577 6933 5792 |
aReaction condition: 80 ℃, P
CO=P
H2=10bar, reaction dissolvent are toluene, in just be designated as-ten alkane.The molar content of conversion ratio, just different ratio and each component of product is determined by gas phase analysis.
bThe ratio of linear chain aldehyde and branched chain aldehyde.
cLinear chain aldehyde accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
dThe 2-octene accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
eThe molal quantity of the aldehyde (linear chain aldehyde+branched chain aldehyde) that generates of every mole of Rh catalysis per hour.
fSolvent-free.
The screening of table three catalyst amount (embodiment 18-22)
a
| Embodiment | The mol ratio of substrate/catalyst | The ratio of part/Rh | Concentration of substrate (M) | Reaction time (h) | Conversion ratio (%) | Just different ratio b | Linear chain aldehyde c (％) | The 2-octene d (％) | TOF e (h -1) |
| 18 19 15 11 16 20 21 22 | 3000 10000 20000 20000 50000 50000 50000 100000 | 5 5 5 5 5 30 30 30 | 0.64 1.0 1.0 2.0 2.0 f h h | 2 3 2 2 4.25 4 1.5 2 | 90 95 67 82 71 99 77 94 | 155 256 193 92 19 201 225 81 | 93 92 92 91 79 93.0 93.0 89.4 | 6.9 7.4 7.2 7.6 17 6.6 6.6 9.4 | 1257 2937 6218 7577 6933 g 24000 42582 |
aReaction condition: 80 ℃, P
CO=P
H2=10bar, solvent are toluene, and just-ten alkane is interior mark.The molar content of conversion ratio, just different ratio and each component of product is determined by gas phase analysis.
bThe ratio of linear chain aldehyde and branched chain aldehyde.
cLinear chain aldehyde accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
dThe 2-octene accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
eThe molal quantity of the aldehyde (linear chain aldehyde+branched chain aldehyde) that generates of every mole of Rh catalysis per hour.
fSolvent-free.
gBecause Conv.＞99%, TOF does not calculate.
hAccurate solvent-free: every 7.5mL 1-octene adds 1mL toluene (being used for Preparation of Catalyst).
Table four CO and H
2The screening (embodiment 23-28) of pressure
a
| Embodiment | P(H 2) (bar) | P(CO) (bar) | Reaction time (h) | Conversion ratio (%) | Just different ratio b | Linear chain aldehyde c (％) | The 2-octene d (％) | TOF e (h -1) |
| 23 21 24 25 26 21 27 28 | 10 10 10 10 5 10 20 50 | 5 10 20 50 10 10 10 10 | 1.5 1.5 1.5 3 1.7 1.5 1.5 1.5 | 93 77 53 67 69 77 80 72 | 365 225 131 79 162 225 241 241 | 86 93.0 94.3 94.4 92.4 93.0 92.7 93.8 | 13.5 6.6 5.0 4.2 7.1 6.6 6.9 5.7 | 26800 24000 16800 10700 18900 24000 24800 22600 |
aReaction condition: 80 ℃, the mol ratio of substrate/catalyst is 50000, and the ratio of part/Rh is 30, and solvent is a toluene, and just-ten alkane is interior mark, and every 7.5mL 1-octene adds 1mL toluene (being used for Preparation of Catalyst).The molar content of conversion ratio, just different ratio and each component of product is determined by gas phase analysis.
bThe ratio of linear chain aldehyde and branched chain aldehyde.
cLinear chain aldehyde accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
dThe 2-octene accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
eThe molal quantity of the aldehyde (linear chain aldehyde+branched chain aldehyde) that generates of every mole of Rh catalysis per hour.
The investigation in table five reaction time (embodiment 29-33)
a
| Embodiment | Reaction time (h) | Conversion ratio (%) | Just different ratio b | Linear chain aldehyde c (％) | The 2-octene d (％) | TOF e (h -1) |
| 29 30 21 31 32 33 | 0.5 1.0 1.5 2.0 2.5 4.5 | 33 52 77 86 95 100 | 201 194 225 218 233 221 | 94.0 94.0 93.0 93.7 92.5 92.9 | 5.2 5.5 6.6 5.9 7.2 6.8 | 31284 24570 24000 20231 17632 10252 |
aReaction condition: 80 ℃, P
CO=P
H2=10bar, the mol ratio of substrate/catalyst is 50000, and the ratio of part/Rh is 30, and solvent is a toluene, and just-ten alkane is interior mark, every 7.5mL 1-octene adds 1mL toluene (being used for Preparation of Catalyst).The molar content of conversion ratio, just different ratio and each component of product is determined by gas phase analysis.
bThe ratio of linear chain aldehyde and branched chain aldehyde.
cLinear chain aldehyde accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
dThe 2-octene accounts for gross product (gross product: molar percentage linear chain aldehyde+branched chain aldehyde+2-octene).
eThe molal quantity of the aldehyde (linear chain aldehyde+branched chain aldehyde) that generates of every mole of Rh catalysis per hour.
Embodiment 34: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (22.7mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 5g, conversion ratio is 58%.Get a reactant liquor and be diluted to 0.5mL, it is 58.4 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 98.3%.The product nmr analysis:
1H NMR (300MHz, CDCl
3) δ=0.96 (t, J=7.5Hz, 3H), 1.62-1.70 (m, 2H), 2.40 (dt, J=7.2,1.8Hz, 2H), 9.76 (t, J=1.8Hz, 1H).
Embodiment 35: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (30.0mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 4g, conversion ratio is 47%.Get a reactant liquor and be diluted to 0.5mL, it is 31 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 96.9%.
Embodiment 36: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (24.7mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 4.5g, conversion ratio is 52%.Get a reactant liquor and be diluted to 0.5mL, it is 37 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 97.4%.
Embodiment 37: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (24.6mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 5g, conversion ratio is 58%.Get a reactant liquor and be diluted to 0.5mL, it is 29 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 96.7%.
Embodiment 38: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (23.6mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 4.5g, conversion ratio is 52%.Get a reactant liquor and be diluted to 0.5mL, it is 21 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 95.5%.
Embodiment 39: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (28.2mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 4.0g, conversion ratio is 47%.Get a reactant liquor and be diluted to 0.5mL, it is 15 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 93.8%.
Embodiment 40: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (28.3mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 5.0g, conversion ratio is 58%.Get a reactant liquor and be diluted to 0.5mL, it is 35 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 97.2%.
Embodiment 41: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis propylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, add Rh (acac) (CO)
20.8mg (28.3mg 0.037mmol), replaces argon gas three times, adds the 6mL dry toluene, stirs 10min (0.0031mmol), to add the bidentate phosphoramidite ligand again; In glove box, catalyst solution is transferred in the autoclave, autoclave is sealed the taking-up glove box, and adding substrate propylene (5g, 119mmol).Charge into synthesis gas CO/H
2(1: 1) stirs 0.75h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, weighing, reactant liquor weightening finish 5.5g, conversion ratio is 64%.Get a reactant liquor and be diluted to 0.5mL, it is 60 that GC analyzes just different ratio, and the molar content of linear chain aldehyde is 98.4%.
Embodiment 42: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis 1-hexene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, (17.7mg 0.029mmol), puts down interior air three times with the argon replaces reaction, adds 1.0mL Rh (acac) (CO) to add the bidentate phosphoramidite ligand
2Anhydrous toluene solution (every milliliter of toluene is dissolved with Rh (acac) (CO)
20.25mg (0.00097mmol)), stir 10min; Adding substrate 1-hexene (6mL, 48.4mmol).In glove box, reaction bulb is transferred in the autoclave, autoclave is sealed the taking-up glove box, use CO/H
2Replace three times gas, charge into synthesis gas CO/H
2(1: 1) stirs 4h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, get a reactant liquor
1H NMR analyzes the molar content of conversion ratio, just different ratio and each component.Conversion ratio is 98%, detects less than branched chain aldehyde, and the molar content of linear chain aldehyde is 96.2%, and the molar content of 2-hexene is 3.8%.The product nmr analysis:
1H NMR (300MHz, CDCl
3) δ=0.88 (t, J=6.6Hz, 3H), 1.29-1.35 (m, 6H), 1.60-1.63 (m, 2H), 2.42 (dt, J=7.2,2.1Hz, 2H), 9.77 (t, J=2.1Hz, 1H).The amount of 2-hexene seldom, (m 2H), can determine that according to integration its molar content is 3.8% to δ=5.39-5.45 of two ethylene linkage H.
Embodiment 43: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis 1-laurylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, (7.1mg 0.012mmol), puts down interior air three times with the argon replaces reaction, adds 1.0mL Rh (acac) (CO) to add the bidentate phosphoramidite ligand
2Anhydrous toluene solution (every milliliter of toluene is dissolved with Rh (acac) (CO)
20.25mg (0.00097mmol)), add the 3mL dry toluene again, stir 10min; Adding substrate 1-laurylene (4.3mL, 19.4mmol).In glove box, reaction bulb is transferred in the autoclave, autoclave is sealed the taking-up glove box, use CO/H
2Replace three times gas, charge into synthesis gas CO/H
2(1: 1) stirs 4h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, get a reactant liquor
1H NMR analyzes the molar content of conversion ratio, just different ratio and each component.Conversion ratio＞99% detects less than branched chain aldehyde, and the molar content of linear chain aldehyde is 95.2%, and the molar content of 2-laurylene is 4.8%.The product nmr analysis:
1H NMR (300MHz, CDCl
3) δ=0.88 (t, J=6.6Hz, 3H), 1.25-1.31 (m, 18H), 1.59-1.65 (m, 2H), 2.43 (t, J=7.2Hz, 2H), 9.77 (t, J=1.8Hz, 1H).The amount of 2-laurylene seldom, (m 2H), can determine that according to integration its molar content is 4.8% to δ=5.39-5.45 of two ethylene linkage H.
Embodiment 44: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis 1-tetradecylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, (7.1mg 0.012mmol), puts down interior air three times with the argon replaces reaction, adds Rh (acac) (CO) to add the bidentate phosphoramidite ligand
2Anhydrous toluene solution 1.0mL (every milliliter of toluene is dissolved with Rh (acac) (CO)
20.25mg (0.00097mmol)), add the 3mL dry toluene again, stir 10min; Adding substrate 1-tetradecylene (4.9mL, 19.4mmol).In glove box, reaction bulb is transferred in the autoclave, autoclave is sealed the back take out glove box, use CO/H
2Replace three times gas, charge into synthesis gas CO/H
2(1: 1) stirs 5h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, get a reactant liquor
1H NMR analyzes the molar content of conversion ratio, just different ratio and each component.Conversion ratio＞99% detects less than branched chain aldehyde, and the molar content of linear chain aldehyde is 96.2%, and the molar content of 2-tetradecene is 3.8%.The product nmr analysis:
1H NMR (300MHz, CDCl
3) δ=0.88 (t, J=6.6Hz, 3H), 1.25-1.30 (m, 22H), 1.57-1.62 (m, 2H), 2.41 (dt, J=7.5,1.8Hz, 2H), 9.77 (t, J=1.8Hz, 1H).The amount of 2-tetradecene seldom, (m 2H), can determine that according to integration its molar content is 3.8% to δ=5.39-5.43 of two ethylene linkage H.
Embodiment 45: the bidentate phosphoramidite ligand
The hydroformylation of Rh complex catalysis 1-octadecylene
In argon gas atmosphere, the reaction bulb anhydrous and oxygen-free is handled, (7.1mg 0.029mmol), puts down interior air three times with the argon replaces reaction, adds 1.0mL Rh (acac) (CO) to add the bidentate phosphoramidite ligand
2Anhydrous toluene solution (every milliliter of toluene is dissolved with Rh (acac) (CO)
20.25mg (0.00097mmol)), add the 5mL dry toluene again, stir 10min; Adding substrate 1-octadecylene (6.3mL, 19.4mmol).In glove box, reaction bulb is transferred in the autoclave, autoclave is sealed the back take out glove box, use CO/H
2Replace three times gas, charge into synthesis gas CO/H
2(1: 1) stirs 5h to 20bar down at 80 ℃.Stop reaction, reactor is cooled off with frozen water, carefully bleed off reacting gas in the fume hood, get a reactant liquor
1H NMR analyzes the molar content of conversion ratio, just different ratio and each component.Conversion ratio＞99% detects less than branched chain aldehyde, and the molar content of linear chain aldehyde is 97.6%, and the molar content of 2-octadecylene is 2.4%.Seal product and place in the refrigerator, separate out white solid.M.p.58-60 ℃; The product nmr analysis:
1H NMR (300MHz, CDCl
3) δ=0.88 (t, J=6.6Hz, 3H), 1.26-1.30 (m, 30H), 1.57-1.62 (m, 2H), 2.41 (dt, J=7.5,1.8Hz, 2H), 9.76 (t, J=1.8Hz, 1H).The amount of 2-octadecylene seldom, (m 2H), can determine that according to integration its molar content is 2.4% to δ=5.39-5.43 of two ethylene linkage H.
Claims (10)
1. the application of substituted bidentate phosphoramidite ligand in catalysis hydroformylation reaction of a dinaphthol skeleton, the substituted bidentate phosphoramidite ligand of described dinaphthol skeleton has following structural formula:
In the formula, R
1And R
2Be respectively the heterocycle that contains N
Or
Or
R wherein
xAnd R
X 'Be respectively hydrogen, C
1～C
10Alkyl, C
1～C
10Alkoxyl, C
1～C
10Alkanoyl, C
1～C
10Ester group, halogen or itrile group;
R
3And R
4Be respectively
Or
Or
Or
Or O-R
w, R wherein
xAnd R
X 'Be respectively hydrogen, C
1～C
10Alkyl, C
1～C
10Alkoxyl, C
1～C
10Alkanoyl, C
1～C
10Ester group, halogen or itrile group; R
wBe hydrogen or C
1～C
10Alkyl;
R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15And R
16Be respectively hydrogen, C
1-12Alkyl,
O-R
w, C
1～C
10Alkanoyl, C
1～C
10Ester group, halogen or itrile group, R wherein
x, R
X 'Be respectively hydrogen, C
1～C
10Alkyl, C
1～C
10Alkoxy or halogen, R
y, R
Y ', R
Y ", R
z, R
Z 'And R
wBe respectively hydrogen or C
1～C
10Alkyl.
2. application as claimed in claim 1 is characterized in that under at least a catalysis that is selected from described part of claim 1 and Rh salt alkene and CO and H
2Hydroformylation reaction takes place.
3. application as claimed in claim 2, it is characterized in that described Rh salt be Rh (acac) (CO)
2, Rh (acac) (C
2H
4), [Rh (C
2H
4)
2Cl]
2, [Rh (cod) Cl]
2, [Rh (CO)
2Cl]
2Or Rh (cod) BF
4, wherein, acac represents acetylacetone,2,4-pentanedione, and cod represents 1, the 5-cyclo-octadiene.
4. application as claimed in claim 2 is characterized in that at inert gas or N
2Under the gas atmosphere, part as claimed in claim 1 and Rh salt react in organic solvent earlier and obtain ligand i/Rh catalyst.
5. application as claimed in claim 4 is characterized in that the mol ratio of described part and Rh salt is: 1-100: 1, and reaction temperature: 0 ℃-100 ℃, the reaction time: 0.1-20h.
6. application as claimed in claim 4 is characterized in that at inert gas or N
2Under the gas atmosphere, in the solution of described ligand i/Rh catalyst, add olefin substrate, CO and H
2, reaction obtains the hydroformylation product.
7. application as claimed in claim 6, the mol ratio that it is characterized in that described alkene and ligand i/Rh catalyst is 100-100000: 1, reaction temperature is 20 ℃-120 ℃, and the reaction time is 0.1-100h, and described CO pressure is the 0.5-100 atmospheric pressure, H
2Pressure is the 0.5-100 atmospheric pressure.
8. application as claimed in claim 2 is characterized in that described alkene is C
2～C
50Alkene.
9. application as claimed in claim 2 is characterized in that being used for the catalyst of hydroformylation reaction, and described catalyst is made up of described rhodium salt and at least a described part of claim 1 that is selected from.
10. application as claimed in claim 9 is characterized in that described catalyst is that the molar ratio of described part and Rh salt is 1-100: 1.
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| JP2016500123A (en) * | 2012-12-04 | 2016-01-07 | ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー | A bidentate ligand for the hydroformylation of ethylene. |
| US9795952B2 (en) | 2012-12-04 | 2017-10-24 | Dow Technology Investments Llc | Bidentate ligands for hydroformylation of ethylene |
| CN107915758A (en) * | 2017-11-15 | 2018-04-17 | 万华化学集团股份有限公司 | Phosphoramidite ligand, catalyst and the method for preparing 4 acetoxyl group butyraldehyde |
| CN107915758B (en) * | 2017-11-15 | 2019-10-29 | 万华化学集团股份有限公司 | Phosphoramidite ligand, catalyst and the method for preparing 4- acetoxyl group butyraldehyde |
| CN109942750A (en) * | 2019-01-14 | 2019-06-28 | 青岛科技大学 | Porous organic polymer and its preparation method and application containing bidentate phosphoramidite ligand |
| CN111454136A (en) * | 2019-01-22 | 2020-07-28 | 中国科学院上海高等研究院 | Catalyst for catalyzing hydroformylation reaction of gem-disubstituted aromatic olefin and preparation method and application thereof |
| CN112851708A (en) * | 2021-01-19 | 2021-05-28 | 成都欣华源科技有限责任公司 | Method for preparing olefine aldehyde by catalyzing terminal alkyne or terminal conjugated eneyne and diphosphine ligand used by method |
| CN114539460A (en) * | 2022-01-24 | 2022-05-27 | 哈尔滨工业大学（深圳） | Method for synthesizing macromolecule loaded asymmetric catalyst |
| CN114539460B (en) * | 2022-01-24 | 2023-05-02 | 哈尔滨工业大学（深圳） | Synthesis method of macromolecule supported asymmetric catalyst |
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