CN117683065A - Phosphine ligand containing silicon-hydrogen group, preparation method and application thereof - Google Patents
Phosphine ligand containing silicon-hydrogen group, preparation method and application thereof Download PDFInfo
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- CN117683065A CN117683065A CN202311676412.2A CN202311676412A CN117683065A CN 117683065 A CN117683065 A CN 117683065A CN 202311676412 A CN202311676412 A CN 202311676412A CN 117683065 A CN117683065 A CN 117683065A
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003446 ligand Substances 0.000 title claims abstract description 65
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 58
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 41
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 32
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 phosphine compound Chemical class 0.000 claims description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 125000006267 biphenyl group Chemical group 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000005046 Chlorosilane Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 4
- XNAFLNBULDHNJS-UHFFFAOYSA-N dichloro(phenyl)silicon Chemical compound Cl[Si](Cl)C1=CC=CC=C1 XNAFLNBULDHNJS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 150000002504 iridium compounds Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 150000003284 rhodium compounds Chemical class 0.000 claims description 2
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 2
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 20
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 8
- 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 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- FAHUKNBUIVOJJR-UHFFFAOYSA-N 1-(4-fluorophenyl)-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine Chemical compound C1=CC(F)=CC=C1C1C2=CC=CN2CCN1 FAHUKNBUIVOJJR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XIONUQPOXCUMMB-UHFFFAOYSA-N (2-bromophenyl)-diphenylphosphane Chemical compound BrC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XIONUQPOXCUMMB-UHFFFAOYSA-N 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XQTRLZHQNYWEQN-UHFFFAOYSA-N bis(4-bromophenyl)-phenylphosphane Chemical compound C1=CC(Br)=CC=C1P(C=1C=CC(Br)=CC=1)C1=CC=CC=C1 XQTRLZHQNYWEQN-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IGSUJBNDAWQLST-UHFFFAOYSA-N chloro-di(propan-2-yl)silicon Chemical compound CC(C)[Si](Cl)C(C)C IGSUJBNDAWQLST-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a phosphine ligand containing a silicon hydrogen group, a preparation method and application thereof, wherein the phosphine ligand containing the silicon hydrogen group comprises a monophosphine ligand containing the silicon hydrogen group and a diphosphine ligand containing the silicon hydrogen group, the monophosphine ligand containing the silicon hydrogen group has a structure shown as a formula (I), the diphosphine ligand containing the silicon hydrogen group has a structure shown as a formula (II), and the monophosphine ligand containing the silicon hydrogen group and the diphosphine ligand have alkyl substitution, alkoxy substitution or phenyl substitutionThe catalyst composed of one or two of phosphine ligands containing the silicon hydrogen groups and transition metal can catalyze the hydroformylation reaction of olefin or the hydro-esterification reaction of olefin, and the catalyst shows excellent activity, selectivity and stability. The phosphine ligand containing the silicon-hydrogen group can greatly reduce the production cost of preparing aldehyde by hydroformylation of olefin or preparing carboxylic ester by esterification of olefin.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and relates to a phosphine ligand containing a silicon-hydrogen group, a preparation method and application thereof.
Background
The hydroformylation of olefins (Hydrofoormstation) refers to the reaction of olefins with synthesis gas (H) 2 And CO) a process for forming an aldehyde one more carbon under the action of a phosphine ligand modified transition metal catalyst. Olefin hydroesterification (hydroalkoxycarbonation) refers to the process of forming a (methyl) carboxylate of one carbon more of an olefin with carbon monoxide (CO) and an alcohol (e.g., methanol) over a phosphine ligand modified transition metal catalyst. The core of the olefin hydroformylation reaction and the hydrogen esterification reaction is the selection of a catalytic system, the research of the catalytic system of the olefin hydroformylation reaction is mainly concentrated on transition metals such as Co, rh, ir, pd, ru and the like, and only metal Co and Rh are really used for industrial scale production at present; the research of olefin hydro-esterification reaction catalytic system mainly focuses on Pd transition metal, but has not had wide industrial application. To date, catalysts for olefin hydroformylation processes have undergone 4 generations of evolution-unmodified Co 2 (CO) 8 Catalyst (generation 1), tertiary phosphine ligand modified Co catalyst (generation 2), PPh 3 Ligand modified Rh catalyst system (3 rd generation), bisphosphite modified Rh catalyst (4 th generation) with water-soluble phosphine ligand TPPTS modified rhodium catalyst (U.S. Pat. No. 62, 2005,249,2946-2961; R.Lazzaroni, coordinatin. Chem. Rev.,2010,254,696-706; R.Franke, D.Selent, A.Boerner, chem. Rev.,2012,112,5675-5732;P.W.N.M.van Leeuwen,in Homogeneous Catalysts:Understanding the Art,Kluwer 2004).
Research shows that the active catalysts for catalyzing the hydroformylation reaction and the hydroesterification reaction of olefin are carbonyl coordinationMetal hydrogen species such as HCo (CO) in olefin hydroformylation reactions 4 、HCo(CO) x L 4-x 、HRh(CO) x L 4-x HPd (CO) in olefin hydro-esterification x L 3-x (L represents a ligand). Therefore, efficient provision of hydride ions, and thus formation of metallic hydrogen active species, is critical to achieving a highly active catalyst.
Disclosure of Invention
The invention aims to provide a phosphine ligand containing a silicon-hydrogen group, one or more catalysts consisting of the phosphine ligand containing the silicon-hydrogen group and transition metal are used for efficiently catalyzing the hydroformylation reaction of olefin or the hydro-esterification reaction of olefin, and the catalysts show excellent activity, selectivity and stability.
The invention provides a phosphine ligand containing a silicon hydrogen group, which comprises a monophosphine ligand containing the silicon hydrogen group and a diphosphine ligand containing the silicon hydrogen group, wherein the monophosphine ligand containing the silicon hydrogen group has a structure shown as a formula (I), and the diphosphine ligand containing the silicon hydrogen group has a structure shown as a formula (II);
in the formula (I), the silicon atom and the phosphorus atom in the silicon hydrogen group are positioned at the ortho position, the meta position or the para position of the benzene ring, and the R 1 Independently selected from any one of C1-C4 alkyl, C1-C4 alkoxy, or phenyl, said R 2 Independently selected from any one of C1-C4 alkyl or phenyl;
in the formula (II), the silicon atom and two phosphorus atoms in the silicon hydrogen group are simultaneously positioned at the ortho, meta or para positions of the benzene ring, and R is 1 Independently selected from any one of C1-C4 alkyl, C1-C4 alkoxy or phenyl, R 2 Independently selected from any one of C1-C4 alkyl or phenyl.
The preparation method of the phosphine ligand containing the silicon hydrogen group comprises the following steps:
(1) Taking (o-, m-, or p-halogenated phenyl) dialkyl (or diphenyl) phosphine as a raw material, mixing the raw material with n-butyllithium according to an equimolar ratio, and reacting at the temperature of minus 78 ℃ for 0.5 to 2 hours to obtain (o-, m-, or p-phenyl lithium) dialkyl (or phenyl) phosphine compounds;
(2) The (ortho-, meta-, or para-phenyl lithium) dialkyl (or diphenyl) phosphine compound is mixed with diphenyl chlorosilane or dialkyl chlorosilane or dialkoxy chlorosilane according to equimolar, and then reacts for 1-4 hours under the condition of-78-room temperature to obtain a monophosphine ligand (I-a) containing a silicon hydrogen group;
(3) Starting from [ bis- (ortho, meta, or para-halophenyl) ] alkyl (or phenyl) phosphine, with n-butyllithium in a ratio of 1:2 molar ratio, and reacting for 0.5-2 hours at-78 ℃ to obtain [ bis- (ortho, meta or para-phenyl lithium) ] alkyl (or phenyl) phosphine compound;
(4) The prepared [ bis- (ortho, meta, or para-phenyllithium) ] alkyl (or phenyl) phosphine compound is mixed with phenyl dichlorosilane or alkyl dichlorosilane, or alkoxy dichlorosilane according to a ratio of 1:2 molar ratio, and reacting for 1-4 hours under the condition of-78-room temperature to obtain the monophosphine ligand (I-b) containing the silicon-hydrogen group;
the preparation of the diphosphine ligand (II) containing the silicon hydrogen group comprises the following steps:
(1) Taking (o-, m-, or p-halogenated phenyl) dialkyl (or phenyl) phosphine as a raw material, mixing the raw material with n-butyllithium according to an equimolar ratio, and reacting at the temperature of minus 78 ℃ for 0.5 to 2 hours to obtain (o-, m-, or p-phenyl lithium) dialkyl (or phenyl) phosphine compounds;
(2) The (ortho-, meta-, or para-phenyllithium) dialkyl (or phenyl) phosphine produced was reacted with phenyldichlorosilane or alkyldichlorosilane, or alkoxydichlorosilane, in a ratio of 2: mixing the components according to a molar ratio of 1, and reacting for 1-4 hours at-78-room temperature to obtain a diphosphine ligand (II) containing a silicon-hydrogen group;
a catalyst, which consists of the phosphine ligand and transition metal, wherein the phosphine ligand is one or two of a mono phosphine ligand containing a silicon hydrogen group and a diphosphine ligand containing a silicon hydrogen group; the transition metal comprises one of a metallic cobalt compound, a metallic ruthenium compound, a metallic rhodium compound, a metallic iridium compound or a metallic palladium compound;
the molar ratio of the phosphine ligand containing the silicon-hydrogen group to the transition metal is 1-20:1.
The application of the catalyst is applied to olefin hydroformylation or olefin hydroesterification.
The olefin comprises one of C3-C16 terminal olefin, C3-C16 internal olefin and C4-C10 diene.
The catalyst is applied to olefin hydroformylation reaction, and specifically comprises the following steps: the catalyst and olefin react for 2 to 20 hours in a high-pressure reaction kettle at the temperature of between 60 and 130 ℃ and under the pressure of 1.0 to 6.0MPa to obtain aldehyde with one carbon more than the carbon number of the olefin; the mass ratio of the transition metal to the olefin in the catalyst is 50-1300 ppm, and the volume ratio of the carbon monoxide to the hydrogen in the synthesis gas is 1:1.
The catalyst is applied to olefin hydrogen esterification reaction, and specifically comprises the following steps: the catalyst, the olefin and the methanol react for 6 to 24 hours in a high-pressure reaction kettle at the temperature of 60 to 130 ℃ and under the pressure of 1.0 to 6.0MPa, so that the methyl carboxylate with one more carbon than the olefin is obtained; the mass ratio of the transition metal to the olefin in the catalyst is 50-1300 ppm, and the mol ratio of the olefin to the methanol is 1:1-5.
The catalyst and the olefin hydroformylation reaction or the olefin hydro-esterification reaction catalyzed by the catalyst are carried out in a high-pressure reaction kettle in a batch or continuous mode.
The catalyst composed of one or two combinations of phosphine ligands containing the silicon hydrogen groups and transition metal provided by the invention has excellent activity, selectivity and stability in the hydroformylation reaction of olefin or the hydro-esterification reaction of olefin, and the cost for preparing aldehyde by the hydroformylation reaction of olefin or preparing carboxylic ester by the hydro-esterification reaction of olefin can be greatly reduced by using the phosphine ligands containing the silicon hydrogen groups.
Detailed Description
The present invention is described in more detail with reference to the following examples. However, these examples are merely illustrative of the present invention and are not intended to be limiting in any way. The reagents involved in the examples are all commercially available products.
Examples 1 to 4: synthesis of a Monophosphine ligand L1-L4 containing a Hydrogen-silicon group
Example 1
The synthesis method of L1 comprises the following steps: tetrahydrofuran (20 mL) was added to (2-bromophenyl) diphenylphosphine (4.5 mmol) under nitrogen, and after 30 minutes at-78deg.C, n-butyllithium (7.5 mmol) was added dropwise. After stirring for 30 minutes at-78℃dimethylchlorosilane (5 mmol) was added dropwise. After stirring was continued at-78 ℃ for 30 minutes, the reaction solution was gradually warmed to room temperature, and distilled under reduced pressure to obtain a white solid, which was subjected to flash column chromatography using n-hexane as an eluent to obtain a white crystalline compound in 56% yield.
Example 2
The synthesis method of L2 comprises the following steps: to bis- (4-bromophenyl) phenylphosphine (5 mmol) was added tetrahydrofuran (20 mL) under nitrogen. After 30 minutes at-78℃n-butyllithium (12 mmol) was added dropwise. After stirring for 30 minutes at-78℃methyldichlorosilane (5 mmol) was added dropwise. After stirring was continued for 30 minutes at-78 ℃, the reaction solution was gradually warmed to room temperature. The white solid was obtained by distillation under reduced pressure, and flash column chromatography using n-hexane as an eluent gave the compound as white crystals in 43% yield.
Example 3
The synthesis method of L3 is the same as that of L1, and the raw material dimethyl chlorosilane is replaced by diisopropyl chlorosilane. The structure is shown as a structural formula L3.
Example 4
The synthesis method of L4 is the same as that of L1, and the raw material dimethyl chlorosilane is replaced by diphenyl chlorosilane. The structure is shown as a structural formula L4.
Example 5: synthesis of a bisphosphine ligand L5 containing a sila group
The synthesis method of L5 comprises the following steps: tetrahydrofuran (20 mL) was added to (2-bromophenyl) diphenylphosphine (10 mmol) under nitrogen, and after 30 minutes at-78deg.C, n-butyllithium (12 mmol) was added dropwise. After stirring for 30 minutes at-78℃methyldichlorosilane (5.0 mmol) was added dropwise. After stirring was continued for 30 minutes at-78 ℃, the reaction was allowed to gradually return to room temperature. The white solid was obtained by distillation under reduced pressure, and flash column chromatography using a mixture of n-hexane and ethyl acetate as an eluent gave the compound as white crystals in 66% yield.
Examples 6 to 10
30mmol of 1-octene and 0.015mmol of Rh (acac) (CO) are added into a stainless steel autoclave with a polytetrafluoroethylene lining in sequence 2 And 0.12mmol L1 (L2, L3, L4 or/and L5), CO and H 2 The volume ratio of the synthesis gas is 1 to 4.0MPa, and the reaction is carried out for 2 hours at 120 ℃ after sealing. After the reaction is finished, cooling to room temperature, decompressing, taking an organic phase, and analyzing by using gas chromatography to determine the yield of the product nonanal. Table 1 shows phosphine ligands L1 to L5 and Rh (acac) (CO) containing a hydrosilylation group 2 Experimental results of the preparation of nonanal by hydroformylation of 1-octene catalyzed by the composed catalyst.
TABLE 1 phosphine ligands L1 to L5 and Rh (acac) (CO) with different hydrosilylation groups 2 Catalytic result of the catalyst composition on the reaction of preparing nonanal from 1-octene hydroformylation a
a Rh(acac)(CO) 2 0.05mol%, phosphine ligand containing silicon hydrogen group 0.4mol%, 1-octene 30mmol, CO/H 2 (1:1) 4.0MPa,120℃for 2 hours.
b And (5) gas chromatography analysis.
Examples 11 to 16
30mmol of 1-hexene, 10mL of methanol and 0.3mmol of Pd (OAc) were sequentially added into a stainless steel autoclave lined with polytetrafluoroethylene 2 And 0.6mmol L1 (L2, L3, L4 or/and L5), CO to 3.0MPa, and after sealing, at 100deg.C for 8 hours. After the reaction is finished, cooling to room temperature, decompressing, and analyzing the reaction liquid by using gas chromatography to determine the yield of the product methyl heptanoate. Table 1 shows phosphine ligands L1 to L4 containing a hydrosilylation group and Pd (OAc) 2 Experimental results of methyl heptanoate prepared by esterification of 1-hexene with hydrogen catalyzed by the composed catalyst.
TABLE 2 phosphine ligands L1 to L5 and Pd (OAc) containing different hydrosilylation groups 2 Catalytic result of catalyst composition on reaction of preparing methyl heptanoate by esterifying 1-hexene with hydrogen a
a Pd(OAc) 2 1mol%, phosphine ligand containing silicon hydrogen group 2.0mol%, 1-hexene 30mmol,MeOH 10mL,CO4.0MPa,100 ℃,8 hours.
b And (5) gas chromatography analysis.
Examples 17 to 24
Table 3 shows the results in L3 and Rh (acac) (CO) 2 The catalyst is formed and used for catalyzing the hydroformylation reaction of different olefins. 30mmol of olefin and 0.015mmol of Rh (acac) (CO) are added into a stainless steel autoclave with a polytetrafluoroethylene lining in sequence 2 0.12mmol L3, CO and H are charged 2 The volume ratio of the synthesis gas is 1 to 4.0MPa, and the reaction is carried out for 2 hours at 120 ℃ after sealing. After the reaction is finished, cooling toThe reaction solution is analyzed by gas chromatography at room temperature and decompressed, and the yield of the product aldehyde is determined.
TABLE 3 ligands L3 and Rh (acac) (CO) 2 Catalytic results of hydroformylation of different olefins with a composed catalyst a
a Rh(acac)(CO) 2 0.05mol%, L3.4 mol%, olefin 30mmol, CO/H 2 (1:1) 4.0MPa,120℃for 2 hours.
b And (5) gas chromatography analysis.
Examples 25 to 32
Table 4 shows the values in L1 and Pd (OAc) 2 The catalyst is formed to catalyze the hydrogen esterification reaction of different olefins. Into a stainless steel autoclave lined with polytetrafluoroethylene, 30mmol of olefin, 10mL of methanol, and 0.3mmol of Pd (OAc) were successively added 2 And 0.6mmol L1, CO to 3.0MPa, and after sealing, at 100deg.C for 8 hours. After the reaction is finished, cooling to room temperature, decompressing, and analyzing the reaction liquid by using gas chromatography to determine the yield of the product carboxylic ester.
TABLE 4 ligands L1 and Pd (OAc) 2 Catalytic result of hydrogen esterification reaction of different olefins by using catalyst a
a Pd(OAc) 2 1mol%, L1.0 mol%, olefin 30mmol,MeOH 10mL,CO4.0MPa,100 ℃for 8 hours.
b And (5) gas chromatography analysis.
Examples 33 to 37
Table 5 gives L3 and Rh (acac) (CO) 2 The catalyst is circularly used in the hydroformylation of 1-octene. The catalyst can be recycled for 5 times and still maintain certain activity and stability. 30mmol of 1-octyl hydrocarbon and 0.02mmol of Rh (acac) (CO) are sequentially added into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining 2 0.12mmol L3, CO and H are charged 2 The synthesis gas with the volume ratio of 1 is reacted for 2 hours at 120 ℃ to 4.0 MPa. After the reaction is finished, cooling to room temperature, decompressing, and analyzing the reaction liquid by using gas chromatography to determine the yield of the product aldehyde. Then the reaction solution is not separated, 30mmol of 1-octene is continuously added, and CO and H are filled in 2 The synthesis gas with the volume ratio of 1 is reacted for 2 hours at 120 ℃ to 4.0MPa, and the catalyst is recycled for 5 times.
Tables 5 L3 and Rh (acac) (CO) 2 Recycling result of catalyst composition in hydroformylation of 1-octene
a Rh(acac)(CO) 2 0.05mol%, L3.4 mol%, 1-octene 30mmol (per addition), CO/H 2 (1:1) 4.0MPa,120℃for 2 hours.
b And (5) gas chromatography analysis.
Examples 38 to 42
Table 6 gives L1 and Pd (OAc) 2 The catalyst is circularly used in the esterification reaction of 1-octene. Into a stainless steel autoclave with polytetrafluoroethylene lining, 30mmol of 1-Xin Xiting, 10mL of methanol and 0.3mmol of Pd (OAc) are added in sequence 2 And 0.6mmol L1, CO to 3.0MPa, and after sealing, at 100deg.C for 8 hours. After the reaction is finished, cooling to room temperature, decompressing, and analyzing the reaction liquid by using gas chromatography to determine the yield of the product methyl nonanoate. Then, without separation, 30mmol of 1-octene and 5mL of methanol were continuously added, CO was charged to 4.0MPa, and the reaction was carried out at 100℃for 8 hours, thus recycling the catalyst a total of 5 times.
TABLE 6 L1 and Pd (OAc) 2 Catalyst composition for esterification of 1-hexene with hydrogenRecycling result a in the application
a Pd(OAc) 2 1mol%, L1.0 mol%, 1-hexene 30mmol (added each time), initial MeOH 10mL (5 mL added cyclically), CO4.0MPa,100℃for 8 hours.
b And (5) gas chromatography analysis.
Claims (7)
1. A phosphine ligand containing a silicon hydrogen group, which is characterized in that the phosphine ligand containing a silicon hydrogen group comprises a monophosphine ligand containing a silicon hydrogen group and a biphosphine ligand containing a silicon hydrogen group, and is characterized in that the monophosphine ligand containing a silicon hydrogen group has a structure shown as a formula (I), and the biphosphine ligand containing a silicon hydrogen group has a structure shown as a formula (II);
in the formula (I), the silicon atom and the phosphorus atom in the silicon hydrogen group are positioned at the ortho position, the meta position or the para position of the benzene ring, and the R 1 Independently selected from any one of C1-C4 alkyl, C1-C4 alkoxy or phenyl, R 2 Independently selected from any one of C1-C4 alkyl or phenyl;
in the formula (II), the silicon atom and two phosphorus atoms in the silicon hydrogen group are simultaneously positioned at the ortho, meta or para positions of the benzene ring, and R is 1 Independently selected from any one of C1-C4 alkyl, C1-C4 alkoxy or phenyl, R 2 Independently selected from any one of C1-C4 alkyl or phenyl.
2. A process for the preparation of a phosphine ligand comprising a hydrosilylation group as claimed in claim 1, characterized in that the preparation of the monophosphine ligand comprising a hydrosilylation group (I) comprises the steps of:
(1) Taking (o-, m-, or p-halogenated phenyl) dialkyl (or diphenyl) phosphine as a raw material, mixing the raw material with n-butyllithium according to an equimolar ratio, and reacting at the temperature of minus 78 ℃ for 0.5 to 2 hours to obtain (o-, m-, or p-phenyl lithium) dialkyl (or diphenyl) phosphine compounds;
(2) The (ortho-, meta-, or para-phenyl lithium) dialkyl (or diphenyl) phosphine compound is mixed with diphenyl chlorosilane or dialkyl chlorosilane or dialkoxy chlorosilane in equal mole, and then reacts for 1-4 hours under the condition of-78-room temperature to obtain a monophosphine ligand (I-a) containing a silicon hydrogen group;
(3) Starting from [ bis- (ortho, meta, or para-halophenyl) ] alkyl (or phenyl) phosphine, with n-butyllithium in a ratio of 1:2 molar ratio, and reacting for 0.5-2 hours at-78 ℃ to obtain [ bis- (ortho, meta or para-phenyl lithium) ] alkyl (or phenyl) phosphine compound;
(4) The prepared [ bis- (ortho, meta, or para-phenyllithium) ] alkyl (or phenyl) phosphine compound is mixed with phenyl dichlorosilane or alkyl dichlorosilane, or alkoxy dichlorosilane according to a ratio of 1:2 molar ratio, and reacting for 1-4 hours under the condition of-78-room temperature to obtain the monophosphine ligand (I-b) containing the silicon-hydrogen group;
the preparation of the diphosphine ligand (II) containing the silicon hydrogen group comprises the following steps:
(1) Taking (o-, m-, or p-halogenated phenyl) dialkyl (or phenyl) phosphine as a raw material, mixing the raw material with n-butyllithium according to an equimolar ratio, and reacting at the temperature of minus 78 ℃ for 0.5 to 2 hours to obtain (o-, m-, or p-phenyl lithium) dialkyl (or phenyl) phosphine compounds;
(2) The (ortho-, meta-, or para-phenyllithium) dialkyl (or phenyl) phosphine produced was reacted with phenyldichlorosilane or alkyldichlorosilane, or alkoxydichlorosilane, in a ratio of 2: mixing the components according to a molar ratio of 1, and reacting for 1-4 hours at-78-room temperature to obtain a diphosphine ligand (II) containing a silicon-hydrogen group;
the R is 1 Independently selected from any one of C1-C4 alkyl, C1-C4 alkoxy or phenyl, R 2 Independently selected from any one of C1-C4 alkyl or phenyl.
3. A catalyst, characterized in that the catalyst consists of a phosphine ligand and a transition metal, wherein the phosphine ligand is one or a combination of two of a mono phosphine ligand containing a silicon hydrogen group and a biphosphine ligand containing a silicon hydrogen group as described in claim 1 or 2; the transition metal comprises one of a metallic cobalt compound, a metallic ruthenium compound, a metallic rhodium compound, a metallic iridium compound or a metallic palladium compound;
the molar ratio of the phosphine ligand containing the silicon-hydrogen group to the transition metal is 1-20:1.
4. Use of the catalyst of claim 3, wherein the catalyst is used in an olefin hydroformylation reaction or an olefin hydroesterification reaction.
5. The use according to claim 4, wherein the olefin comprises one of a C3-C16 terminal olefin, a C3-C16 internal olefin, and a C4-C10 diene.
6. The use according to claim 4 or 5, wherein the catalyst is used in the hydroformylation of olefins, comprising in particular: the catalyst and olefin react for 2 to 20 hours in a high-pressure reaction kettle at the temperature of between 60 and 130 ℃ and under the pressure of 1.0 to 6.0MPa to obtain aldehyde with one carbon more than the carbon number of the olefin; the mass ratio of the transition metal to the olefin in the catalyst is 50-1300 ppm, and the volume ratio of the carbon monoxide to the hydrogen in the synthesis gas is 1:1.
7. The use according to claim 4 or 5, wherein the catalyst is used in the esterification of olefins, and specifically comprises: the catalyst, the olefin and the methanol react for 6 to 24 hours in a high-pressure reaction kettle at the temperature of 60 to 130 ℃ and under the pressure of 1.0 to 6.0MPa, so that the methyl carboxylate with one more carbon than the olefin is obtained; the mass ratio of the transition metal to the olefin in the catalyst is 50-1300 ppm, and the mol ratio of the olefin to the methanol is 1:1-5.
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