CN117700326A - Method for catalyzing hydrocracking of carbamate compounds and preparation method of nitrogen-phosphine tridentate ligand ruthenium catalyst - Google Patents
Method for catalyzing hydrocracking of carbamate compounds and preparation method of nitrogen-phosphine tridentate ligand ruthenium catalyst Download PDFInfo
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- CN117700326A CN117700326A CN202311534928.3A CN202311534928A CN117700326A CN 117700326 A CN117700326 A CN 117700326A CN 202311534928 A CN202311534928 A CN 202311534928A CN 117700326 A CN117700326 A CN 117700326A
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- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003446 ligand Substances 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 55
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000004657 carbamic acid derivatives Chemical class 0.000 title claims abstract description 15
- -1 carbamate compound Chemical class 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- FCWVRKJMJWKOCD-UHFFFAOYSA-N 2-diphenylphosphanylacetaldehyde hydrobromide Chemical class Br.C=1C=CC=CC=1P(CC=O)C1=CC=CC=C1 FCWVRKJMJWKOCD-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 150000003017 phosphorus Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- LILXDMFJXYAKMK-UHFFFAOYSA-N 2-bromo-1,1-diethoxyethane Chemical compound CCOC(CBr)OCC LILXDMFJXYAKMK-UHFFFAOYSA-N 0.000 claims description 9
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- MVJRXTSUBHUUPN-UHFFFAOYSA-M carbon monoxide;ruthenium(1+);triphenylphosphane;chloride Chemical compound [O+]#[C-].[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MVJRXTSUBHUUPN-UHFFFAOYSA-M 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000012321 sodium triacetoxyborohydride Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- HIBWBGPAYVUZSE-UHFFFAOYSA-N 2-dicyclohexylphosphanylacetaldehyde hydrobromide Chemical class Br.C1CCCCC1P(CC=O)C1CCCCC1 HIBWBGPAYVUZSE-UHFFFAOYSA-N 0.000 description 15
- 239000012265 solid product Substances 0.000 description 15
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- ILLFDHRDCAUCTG-UHFFFAOYSA-N 4-methoxyquinolin-8-amine Chemical compound C1=CC=C2C(OC)=CC=NC2=C1N ILLFDHRDCAUCTG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical group C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for catalyzing hydrocracking of carbamate compounds and a preparation method of a phosphine-nitrogen tridentate ligand ruthenium catalyst. The preparation method comprises three steps of preparing diphenylphosphino-acetaldehyde hydrobromide dimer, preparing a nitrogen phosphine ligand and preparing a nitrogen phosphine tridentate ligand ruthenium catalyst. According to the invention, hydrogen is used as a green reducing agent to crack the carbamate compound into alcohol and amine with high added value, and the ruthenium catalyst shows high catalytic activity in hydrogenation fracture of an amide bond.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to a catalyst for hydrocracking, and in particular relates to a method for catalyzing hydrocracking of carbamate compounds and a preparation method of a nitrogen-phosphine tridentate ligand ruthenium catalyst.
Background
Reduction of carboxylic acids and derivatives thereof is important in scientific and industrial applications, and conventional reduction methods often require the use of stoichiometric amounts of hydrogenation reagents (e.g., lithium aluminum hydride, sodium borohydride, borane, etc.) to produce equivalent amounts of hydrogenation byproducts. Hydrogen is used as a green reducing agent, has the characteristics of high atom economy, less three wastes and the like, and is widely applied to the catalytic hydrogenation reaction of unsaturated carbon-carbon bonds, carbon-oxygen bonds, carbon-nitrogen bonds and other functional groups. However, the hydrogenation of carboxylic acids and their derivatives under mild conditions using hydrogen is very challenging, and especially carbamates are one of the most difficult compounds to reduce among all carbonyl compounds, essentially because the carbonyl groups of carbamates are conjugated to oxygen and nitrogen atoms and the hydrogenation activity of carbon-oxygen double bonds is much lower than in common carbonyl compounds.
The current report on the success of catalytic hydrogenation of carbamates is as follows: milstein uses bipyridine type nitrogen phosphine tridentate ligand-ruthenium catalytic system to realize catalytic hydrogenation of carbamate, important chemical raw materials alcohol and amine are obtained, but the application range of the substrate is narrow, and safety risk exists in the reaction at 110 ℃ by using tetrahydrofuran solvent. Ito uses Cp-Ru catalytic system to realize the catalytic hydrogenation of specific cyclic carbamate, and obtain raw material chiral alcohol, but the catalytic system has poor universality. The catalytic hydrogenation of carbamate is realized by using a diphenylphosphine substituted diethylamine-manganese catalytic system by Werner and isopropanol as a hydrogen source through a transfer hydrogenation way, and the catalytic system has wider substrate application range, but lower catalytic efficiency, and has high requirement on water-oxygen sensitive operation and difficult scale up.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a method for catalyzing hydrocracking of a carbamate compound and a preparation method of a nitrogen-phosphine tridentate ligand ruthenium catalyst, and solves the technical problems of low hydrocracking catalytic efficiency and poor substrate applicability of the carbamate compound in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for catalyzing hydrocracking of carbamate compounds takes a nitrogen-phosphine tridentate ligand ruthenium catalyst as a catalyst, and catalyzes the carbamate compounds to carry out hydrocracking reaction in a reaction system containing organic alkali and toluene in a hydrogen atmosphere to generate amine and alcohol; the chemical structural formula of the nitrogen phosphine tridentate ligand ruthenium catalyst is shown as the following formula I:
in formula I:
R 1 selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl and phenyl;
R 2 selected from the group consisting of hydrogen, alkoxy, alkyl, and dimethylamino;
the chemical structural formula of the carbamate compound is shown as the following formulas II and III:
in formula II:
R 3 selected from methyl, ethyl, isopropyl, n-butyl, phenyl and benzyl;
R 4 selected from phenyl, substituted phenyl, 2-pyridyl, 1-naphthyl, alpha-methylbenzyl, benzyl, n-hexyl, indole, piperidine and morpholine;
R 5 selected from hydrogen, methyl and phenyl;
in formula III:
n is a positive integer of 26 or more and 32 or less;
the preparation method of the nitrogen-phosphine tridentate ligand ruthenium catalyst specifically comprises the following steps:
step one, preparing diphenylphosphino-acetaldehyde hydrobromide dimer:
dissolving organic phosphorus salt in a solvent to prepare an organic phosphorus salt solution; adding an organic phosphorus salt solution into a reaction container, then dropwise adding 2-bromoacetaldehyde diethyl acetal under stirring at the temperature of minus 30 ℃, adding hydrobromic acid aqueous solution after the system naturally heats to 20-30 ℃ after the dropwise adding is finished, and stirring at the temperature of 40 ℃ for 6-8 hours; after the reaction liquid is cooled, firstly distilling off the solvent, then carrying out suction filtration to obtain a filter cake, and leaching, pumping the solvent and drying the filter cake to obtain diphenylphosphino-acetaldehyde hydrobromide dimer;
the chemical structural formula of the organic phosphorus salt is shown as the following formula IV:
in formula IV:
m is selected from ions corresponding to hydrogen and alkali metal elements;
r1 is selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl or phenyl;
step two, preparing a nitrogen-phosphine ligand:
adding the diphenylphosphino-acetaldehyde hydrobromide dimer prepared in the step one, aminoquinoline compounds, sodium triacetoxyborohydride and a solvent into a reaction vessel, and stirring for 8-12 hours at 20-30 ℃ in a nitrogen protection atmosphere; after the reaction is finished, adding a saturated ammonium chloride aqueous solution into the reaction solution to quench the reaction; extracting a product by adopting ethyl acetate, back-extracting an organic phase obtained by extraction by adopting saturated saline water, and finally sequentially drying, concentrating the organic phase and purifying by column chromatography to obtain a nitrogen-phosphine ligand;
the chemical structural formula of the aminoquinoline compound is shown as the following formula V:
in formula V:
R 2 selected from the group consisting of hydrogen, alkoxy, alkyl, and dimethylamino;
preparing a nitrogen-phosphine tridentate ligand ruthenium catalyst:
adding the nitrogen phosphine ligand prepared in the second step, tris (triphenylphosphine) carbonyl ruthenium chloride and a solvent into a reaction vessel, and stirring for 9-12 hours at 110 ℃ in a nitrogen protection atmosphere; after the reaction is finished, carrying out suction filtration on the reaction liquid to obtain a filter cake, and leaching and drying the filter cake to obtain the nitrogen-phosphine tridentate ligand ruthenium catalyst.
The invention also has the following technical characteristics:
specifically, the hydrocracking reaction conditions are as follows: the hydrogen pressure is 20-30 bar, the reaction temperature is 110-130 ℃, and the reaction time is 2-6 hours.
Specifically, the carbamate compound is N-phenyl methyl carbamate; the mass ratio of the N-phenyl methyl carbamate to the nitrogen phosphine tridentate ligand ruthenium catalyst is (80-120): (5-7).
Specifically, the carbamate compound is polyurethane; the mass ratio of the polyurethane to the nitrogen phosphine tridentate ligand ruthenium catalyst is (300-500): (5-15).
Specifically, the organic base is potassium tert-butoxide.
Specifically, in the first step, the molar ratio of the 2-bromoacetaldehyde diethyl acetal, the organic phosphorus salt and the hydrobromic acid is 1:1-2:1.5-3.
Specifically, in the second step, the molar ratio of the diphenylphosphino-acetaldehyde hydrobromide dimer, the aminoquinoline compound and the sodium triacetoxyborohydride is 1: (1-2): (2-4).
Specifically, in the third step, the molar ratio of the nitrogen-phosphine ligand to the tris (triphenylphosphine) carbonyl ruthenium chloride is (1-1.5): 1.
specifically, the solvent is selected from tetrahydrofuran, toluene, 2-methyltetrahydrofuran, ethyl acetate, methylene chloride, chloroform and methanol.
The invention also provides a preparation method of the nitrogen-phosphine tridentate ligand ruthenium catalyst.
Compared with the prior art, the invention has the beneficial technical effects that:
according to the method for catalyzing the hydrocracking of the carbamate compound, disclosed by the invention, hydrogen is taken as a green reducing agent to crack the carbamate compound into alcohol and amine with high added value, and the ruthenium catalyst shows high-efficiency catalytic activity in the hydrogenation cleavage of an amide bond. In addition, the method is simultaneously suitable for non-polymer and polymer carbamate compounds, namely, the substrate has wide applicability.
According to the preparation method of the nitrogen-phosphine tridentate ligand ruthenium catalyst, an amino quinoline compound is used as a ligand framework, phosphine structural units are introduced through reductive amination reaction to synthesize the nitrogen-phosphine tridentate ligand, and the nitrogen-phosphine tridentate ligand and metal ruthenium salt are used for complexing to prepare the novel ruthenium catalyst, so that the ruthenium catalyst has high structural rigidity, coordination capacity and catalytic efficiency.
The technical scheme of the invention is further described below by referring to examples.
Detailed Description
In the invention, the following components are added:
the urethane compound refers to a compound having a urethane group, and includes a polymer having a urethane group in the main chain, such as polyurethane.
The synthetic route of the ruthenium catalyst of the invention is as follows:
wherein:
m is hydrogen or an alkali metal element;
R 1 methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl;
R 2 is hydrogen, alkoxy, alkyl, dimethylamino.
The hydrocracking reaction process of the non-polymer carbamate compound catalyzed by the ruthenium catalyst is as follows:
wherein:
R 3 methyl, ethyl, isopropyl, n-butyl, phenyl, benzyl;
R 4 phenyl, substituted phenyl, 2-pyridyl, 1-naphthyl, alpha-methylbenzyl, benzyl, n-hexyl, indole, piperidine and morpholine;
R 5 is hydrogen, methyl, phenyl.
The hydrocracking reaction process of the polyurethane catalyzed by the ruthenium catalyst is as follows:
wherein: n=26 to 32.
All materials and reagents used in the present invention are those known in the art unless specifically stated otherwise.
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
the present example shows a process for the preparation of diphenylphosphino-acetaldehyde hydrobromide dimer (2) -1, comprising in particular the following steps: dissolving diphenyl potassium phosphate in tetrahydrofuran to prepare an organic phosphorus salt solution (0.5M); to a dry three-necked flask equipped with a constant pressure dropping funnel and thermometer, 34mL of an organic phosphorus salt solution was added, then 3.4g of 2-bromoacetaldehyde diethyl acetal was added dropwise with stirring at-30℃and the system was naturally returned to room temperature after the addition, then 6.8mL of 10wt.% hydrobromic acid aqueous solution was added, and stirring was carried out at 40℃for 8 hours. After the reaction solution was cooled to room temperature, half of the solvent was distilled off, suction filtration was performed, and the cake was rinsed with 10mL of water and 10mL of ethyl acetate in this order, and the solvent was drained off, and 10g of a white solid product was obtained after vacuum drying.
In this example, the white solid product was identified and characterized as follows:
1 H NMR(500MHz,d 6 -DMSO)：δppm 7.32－7.41(m,20H),5.21(dd,1H),5.08(dd,1H),2.76(m,2H),2.98(m,2H).
31 P{H}NMR(202MHz,d 6 -DMSO):δppm 21.1(s),30.4(s).
from the above structural characterization data, the white solid product produced in this example was diphenylphosphino-acetaldehyde hydrobromide dimer (2) -1. In this example, the yield of diphenylphosphino-acetaldehyde hydrobromide dimer (2) -1 was 94.3%. The nuclear magnetic resonance spectrum signal of the product is weak and difficult to measure.
The reaction route in this example is as follows:
wherein:
represents 2-bromoacetaldehyde diethyl acetal;
represents diphenyl potassium phosphate;
HBr represents hydrobromic acid;
represents diphenylphosphino-acetaldehyde hydrobromide dimer (2) -1.
Example 2:
the present example shows a process for the preparation of dicyclohexylphosphino-acetaldehyde hydrobromide dimer (2) -2, comprising in particular the following steps: dissolving dicyclohexyl phosphine potassium in tetrahydrofuran to prepare an organic phosphorus salt solution (0.5M); to a dry three-necked flask equipped with a constant pressure dropping funnel and a thermometer, 19mL of an organic phosphorus salt solution was added, then 1.7g of 2-bromoacetaldehyde diethyl acetal was added dropwise with stirring at-30℃and the system was naturally returned to room temperature after the addition, then 3.4mL of 10wt.% hydrobromic acid aqueous solution was added, and stirring was carried out at 40℃for 6 hours; after the reaction solution was cooled to room temperature, half of the solvent was distilled off, suction filtration was performed, and the cake was rinsed with 10mL of water and 10mL of ethyl acetate in this order, and the solvent was drained off, and after vacuum drying, 4.7g of a white solid product was obtained.
In this example, the white solid product was identified and characterized as follows:
1 H NMR(500MHz,CD 3 CN)：δppm 1.42－2.19(m,44H),2.80(q,2H),3.08(m,2H),5.39(dd,1H),5.23(dd,1H).
31 P{H}NMR(202MHz,CD 3 CN):δppm 27.2(s),28.1(s).
from the above structural characterization data, the white solid product produced in this example was diphenylphosphino-acetaldehyde hydrobromide dimer (2) -2. In this example, the yield of diphenylphosphino-acetaldehyde hydrobromide dimer (2) -2 was 84%. The nuclear magnetic resonance spectrum signal of the product is weak and difficult to measure.
The reaction route in this example is as follows:
wherein:
represents potassium dicyclohexyl phosphine;
represents dicyclohexylphosphino-acetaldehyde hydrobromide dimer (2) -2.
Example 3:
the embodiment provides a preparation method of a nitrogen phosphine ligand (3) -1, which specifically comprises the following steps: to the dried Schlenk tube, 618mg of diphenylphosphino-acetaldehyde hydrobromide dimer (2) -1, 288mg of 8-aminoquinoline, 848mg of sodium triacetoxyborohydride and 15mL of tetrahydrofuran were added and stirred at room temperature (20-30 ℃) under nitrogen protection for 12 hours; then 10mL of saturated ammonium chloride aqueous solution is added into the reaction liquid under the protection of nitrogen to quench the reaction, stirring is carried out for 10 minutes, 20mL of ethyl acetate is added for extraction, the organic phase is back extracted with 20mL of saturated saline solution, anhydrous sodium sulfate is dried for 30 minutes, the organic phase is concentrated, and finally, the rapid column chromatography purification is carried out under the inert gas atmosphere, thus obtaining 592mg of colorless liquid product.
In this example, the colorless liquid product was identified and its nuclear magnetic data were as follows:
1 H NMR(500MHz，CDCl 3 )：δppm 8.67(d，1H)，8.00(d，1H)，7.46(m，4H),7.32(m，6H),7.01(d，4H),6.51(d，1H),6.31(s，1H),3.45(m，2H),2.60－2.46(m，2H)；
13 C NMR(125MHz，CDCl 3 )：δppm 146.82,144.25,138.17,135.95,132.86,132.71,128.76,128.67,128.57,128.52,128.05,127.72,121.37,113.93,104.66,40.51,40.32,28.38,28.28；
31 P NMR(202MHz，CDCl 3 )：δppm-21.09.
from the above structural characterization data, the colorless liquid product prepared in this example was the nitrogen phosphine ligand (3) -1. In this example, the yield of the nitrogen phosphine ligand (3) -1 was 83% and the content was 95%.
The reaction route in this example is as follows:
wherein:
represents 8-aminoquinoline;
represents sodium triacetoxyborohydride;
THF represents tetrahydrofuran;
represents the nitrogen phosphine ligand (3) -1.
Example 4:
the embodiment provides a preparation method of a nitrogen phosphine ligand (3) -2, which specifically comprises the following steps: to the dried Schlenk tube, 220mg dicyclohexylphosphino-acetaldehyde hydrobromide dimer (2) -2, 96mg of 8-aminoquinoline, 283mg of sodium triacetoxyborohydride and 8mL of tetrahydrofuran were added and stirred at room temperature under a nitrogen atmosphere for 8 hours; then 5mL of saturated ammonium chloride aqueous solution is added into the reaction liquid under the protection of nitrogen to quench the reaction, stirring is carried out for 10 minutes, 10mL of ethyl acetate is added for extraction, the organic phase is back extracted with 10mL of saturated saline solution, anhydrous sodium sulfate is dried for 20 minutes, the organic phase is concentrated, and finally, the organic phase is purified by rapid column chromatography under the inert gas atmosphere, thus 196mg of colorless liquid product is prepared.
In this example, the colorless liquid product was identified and characterized as follows:
1 H NMR(500MHz,CDCl 3 )δppm:1.17-1.30(m,10H),1.57-1.62(m,2H),1.69-1.79(m,10H),1.85-1.89(m,2H),3.41-3.46(m,2H),6.30(s,1H),6.66-6.67(dd,1H),7.02-7.05(m,1H),7.34-7.40(m,2H),8.03-8.05(dd,1H),8.70-8.71(dd,1H).
13 C NMR(126MHz,CDCl 3 )δppm:21.83,27.36,27.46,29.07,30.41,33.37,43.23,104.84,113.88,121.46,127.92,128.79,136.08,138.31,144.58,146.92.
31 P{1H}NMR(202MHz,CDCl 3 )δppm:-8.61.
from the above structural characterization data, the colorless liquid product prepared in this example was the nitrogen phosphine ligand (3) -2. In this example, the yield of the nitrogen phosphine ligand (3) -2 was 80% and the content was 95%.
The reaction route in this example is as follows:
wherein:
represents the nitrogen phosphine ligand (3) -2.
Example 5:
the embodiment provides a preparation method of a nitrogen phosphine ligand (3) -3, which specifically comprises the following steps: to the dried Schlenk tube, 309mg of diphenylphosphino-acetaldehyde hydrobromide dimer (2) -1, 174mg of 4-methoxy-8-aminoquinoline, 424mg of sodium triacetoxyborohydride and 10mL of tetrahydrofuran were added and stirred at room temperature under a nitrogen blanket for 10 hours; then 10mL of saturated ammonium chloride aqueous solution is added into the reaction liquid under the protection of nitrogen to quench the reaction, stirring is carried out for 10 minutes, 10mL of ethyl acetate is added for extraction, the organic phase is back extracted with 10mL of saturated saline solution, anhydrous sodium sulfate is dried for 20 minutes, the organic phase is concentrated, and finally, the rapid column chromatography purification is carried out under the inert gas atmosphere, thus obtaining 340mg of colorless liquid product.
In this example, the colorless liquid product was identified and characterized as follows:
1 H NMR(500MHz，CDCl 3 )：δppm 8.96(d，1H)，7.81(d，1H),7.65(d，1H),7.47(d，1H),7.42(m，6H),7.33(m，1H),7.15(d，4H),6.52(s，1H),3.81(s，3H),3.43(m，2H),2.62－2.48(m，2H)；
13 C NMR(125MHz，CDCl 3 )：δppm 166.31,151.26,143.11,138.92,137.88,132.71,128.76,128.67,128.57,128.52,128.05,127.72,120.41,113.93,104.66,56.7,42.53,42.36,29.57,29.39；
31 P NMR(202MHz，CDCl 3 )：δppm-22.18.
from the above structural characterization data, the colorless liquid product prepared in this example was the nitrogen phosphine ligand (3) -3. In this example, the yield of the nitrogen phosphine ligand (3) -3 was 88% and the content was 96%.
The reaction route in this example is as follows:
wherein:
represents 4-methoxy-8-aminoquinoline;
represents the nitrogen phosphine ligand (3) -3.
Example 6:
the embodiment provides a preparation method of a nitrogen-phosphine tridentate ligand ruthenium catalyst (1) -1, which specifically comprises the following steps: to the dried Schlenk tube, 392mg of the nitrogen phosphine ligand (3) -1, 490mg of ruthenium tris (triphenylphosphine) carbonyl chloride and 5mL of toluene were added and stirred under nitrogen at 110℃for 12 hours; and then carrying out suction filtration on the reaction liquid under the protection of nitrogen, sequentially eluting a filter cake by using 5mL of toluene and 5mL of diethyl ether, rapidly transferring the obtained solid into a round bottom flask, and carrying out vacuum drying to obtain 444mg of a dark yellow solid product.
In this example, the dark yellow solid product was identified and characterized as follows:
1 H NMR(500MHz，DMSO-d6)：δppm 9.71(s，1H)，8.72(dd，2H)，8.38(d，1H),8.21(d，1H),7.98(t，3H),7.66(d，3H),7.55－7.38(m，2H),7.28(t，2H),6.91(t，2H),4.14(m，1H),3.25(m，2H),1.86－1.58(m，1H),-14.3(s，1H)；
13 C NMR(125MHz，DMSO-d6)：δppm 156.68,146.26,142.68,139.32,132.86,132.71,131.76,131.67,131.57,130.52,130.35,130.12,129.97,129.83,129.56,129.42,129.21,128.83,128.16,124.51,57.38,57.08；
31 P NMR(202MHz，DMSO-d6)：δppm 9.31.
from the above structural characterization data, the dark yellow solid product produced in this example was ruthenium catalyst (1) -1. In this example, the yield of ruthenium catalyst (1) -1 was 85% and the content was 97%.
The reaction route in this example is as follows:
Ru(CO)(PPh) 3 ClH represents ruthenium tris (triphenylphosphine) carbonyl chloride;
TOL represents toluene;
ruthenium catalyst (1) -1 is represented.
Example 7:
the embodiment provides a preparation method of a nitrogen-phosphine tridentate ligand ruthenium catalyst (1) -2, which specifically comprises the following steps: to the dried Schlenk tube, 135mg of the nitrogen phosphine ligand (3) -2, 163mg of tris (triphenylphosphine) carbonyl ruthenium chloride and 2mL of toluene were added and stirred under nitrogen at 110℃for 9 hours; and then carrying out suction filtration on the reaction liquid under the protection of nitrogen, sequentially eluting a filter cake by using 5mL of toluene and 5mL of diethyl ether, rapidly transferring the obtained solid into a round bottom flask, and carrying out vacuum drying to obtain 145mg of a dark yellow solid product.
In this example, the dark yellow solid product was identified and characterized as follows:
1 H NMR(500MHz，DMSO-d6)：δppm 9.62(d，1H)，9.14(d，1H)，8.28(m，1H),8.21(d，1H),7.78(d，1H),7.68－7.62(m，1H),7.02(s，1H),4.44－4.32(m，1H),3.28－3.15(m，2H),1.96-1.91(m,2H),1.82-1.73(m,11H),1.44-1.26(m,10H),-10.6(s，1H)；
31 P NMR(202MHz，DMSO-d6)：δppm 27.46.
from the above structural characterization data, the dark yellow solid product produced in this example was ruthenium catalyst (1) -2. In this example, the yield of ruthenium catalyst (1) -2 was 82% and the content was 96%. The nuclear magnetic resonance spectrum signal of the product is weak and difficult to measure.
The reaction route in this example is as follows:
/>
ruthenium catalysts (1) -2 are represented.
Example 8:
the embodiment provides a preparation method of a nitrogen-phosphine tridentate ligand ruthenium catalyst (1) -3, which specifically comprises the following steps: to the dried Schlenk tube, 212mg of the nitrogen phosphine ligand (3) -3, 245mg of tris (triphenylphosphine) carbonyl ruthenium chloride and 3mL of toluene were added and stirred under nitrogen at 110℃for 10 hours; and then carrying out suction filtration on the reaction liquid under the protection of nitrogen, sequentially eluting a filter cake by using 5mL of toluene and 5mL of diethyl ether, rapidly transferring the obtained solid into a round-bottom flask, and carrying out vacuum drying to obtain 237mg of yellow solid product.
In this example, the yellow solid product was identified and characterized as follows:
1 H NMR(500MHz，DMSO-d6)：δppm 9.98(s，1H),8.43(d，1H),8.28(d，1H),8.01(d，1H),7.79－7.71(m，4H),7.68－7.55(m，4H),7.50－7.41(d，2H),7.28－7.21(d，2H),4.11－4.05(m，1H),3.82(s，3H),3.26－3.13(m，2H),1.83－1.62(m，1H),-14.3(s，1H)；
31 P NMR(202MHz，DMSO-d6)：δppm 9.18.
from the above structural characterization data, the yellow solid product produced in this example was ruthenium catalysts (1) -3. In this example, the yield of ruthenium catalyst (1) -3 was 86% and the content was 96%. The nuclear magnetic resonance spectrum signal of the product is weak and difficult to measure.
The reaction route in this example is as follows:
ruthenium catalysts (1) -3 are represented.
Example 9:
the embodiment provides a method for catalyzing the hydrocracking of N-phenyl methyl carbamate by using a ruthenium catalyst, which specifically comprises the following steps: 1.1g of methyl N-phenylcarbamate, 63mg of the ruthenium catalyst (I) -1 prepared in example 6, 27mg of potassium tert-butoxide and 2mL of toluene are added into an autoclave, the autoclave is closed, the system is replaced by nitrogen for 3 times, then the system is replaced by hydrogen for 3 times, the hydrogen pressure of the system is controlled at 20bar, and the system is stirred for 2 hours at 110 ℃; and cooling the system to room temperature, slowly releasing pressure in a fume hood, and opening the autoclave after the pressure of the system is reduced to one atmosphere to obtain a product.
In this example, after analysis of the above products by GC-MS, it was found that the products were aniline and methanol. After the product is purified by column chromatography, the obtained purified product is subjected to nuclear magnetism identification, and the result is as follows:
1 H NMR(500MHz，CDCl 3 )：δppm 7.15－7.26(m，2H),6.71－6.83(m，3H),3.8(s，2H)；
13 C NMR(125MHz，CDCl 3 )：δppm 146.48,129.21,118.33,115.08.
from the above structural characterization data, it can be seen that one of the products produced in this example is indeed aniline, and that the other product can be determined to be methanol based on the principle of chemical reaction. In this example, the yield of aniline was 91%.
The reaction route in this example is as follows:
wherein:
represents methyl N-phenylcarbamate;
KO t bu represents potassium tert-butoxide;
represents aniline;
CH 3 OH represents methanol.
Example 10:
this example shows a process for the catalytic hydrocracking of methyl N-phenylcarbamate using a ruthenium catalyst, which is substantially identical to example 9, with the difference that: the ruthenium catalyst was ruthenium catalyst (1) -2 prepared in example 7.
In this example, after analysis of the product by GC-MS, it was found that the product was aniline and methanol. In this example, the yield of aniline was 89%.
Example 11:
this example shows a process for the catalytic hydrocracking of methyl N-phenylcarbamate using a ruthenium catalyst, which is substantially identical to example 9, with the difference that: the ruthenium catalysts were ruthenium catalysts (1) -3 prepared in example 8.
In this example, after analysis of the product by GC-MS, it was found that the product was aniline and methanol. In this example, the yield of aniline was 94%.
Example 12:
this example shows a process for the catalytic hydrocracking of polyurethane using the ruthenium catalyst (1) -3 prepared in example 8, which comprises in particular the following steps: 414mg of polyurethane (weight average molecular weight: 11000), 10mg of ruthenium catalyst (I) -3 prepared in example 8, 4.5mg of potassium tert-butoxide and 1mL of toluene are added into an autoclave, the autoclave is closed, the system is replaced by nitrogen atmosphere for 3 times, the system is replaced by hydrogen atmosphere for 3 times, the hydrogen pressure of the system is controlled at 30bar, and the system is stirred for 6 hours at 130 ℃; and cooling the system to room temperature, slowly releasing pressure in a fume hood, and opening the autoclave after the pressure of the system is reduced to one atmosphere to obtain a product.
In this example, after analysis of the above products by GC-MS, it was found that the products were 4,4' -methylenedianiline and 1, 5-pentanediol. After the product is purified by column chromatography, the obtained purified product is subjected to nuclear magnetism identification, and the result is as follows:
1 H NMR(500MHz，CDCl 3 )：δppm 7.05－6.93(m，4H)，6.69－6.58(m，4H)，3.80(s，2H),3.48(brs，4H)；
13 C NMR(125MHz，CDCl 3 )：δppm 144.56,132.18,129.75,115.43,40.33.
from the above structural characterization data, one of the products obtained in this example was identified as 4,4' -methylenedianiline, and the other product was identified as 1, 5-pentanediol based on the chemical reaction principle.
In this example, the yield of product 4,4' -methylenedianiline was 51%; after purification and separation by flash column chromatography, the separation yield of 4,4' -methylenedianiline was 45%.
The reaction route in this example is as follows:
wherein:
represents polyurethane;represents 4,4' -diaminodiphenylmethane;
represents pentanediol. />
Claims (10)
1. A method for catalyzing hydrocracking of carbamate compounds is characterized in that the method takes a nitrogen-phosphine tridentate ligand ruthenium catalyst as a catalyst, and the carbamate compounds are catalyzed to carry out hydrocracking reaction in a reaction system containing organic alkali and toluene in a hydrogen atmosphere to generate amine and alcohol;
the chemical structural formula of the carbamate compound is shown as the following formula III:
in formula III:
n is a positive integer of 26 or more and 32 or less;
the preparation method of the nitrogen-phosphine tridentate ligand ruthenium catalyst comprises the following steps: firstly, preparing diphenylphosphino-acetaldehyde hydrobromide dimer by taking organic phosphorus salt, 2-bromoacetaldehyde diethyl acetal and hydrobromic acid as reaction raw materials; then diphenyl phosphino-acetaldehyde hydrobromide dimer and aminoquinoline compound are used as reaction raw materials to prepare a nitrogen-phosphine ligand; finally, taking the nitrogen phosphine ligand and the tri (triphenylphosphine) carbonyl ruthenium chloride as reaction raw materials to prepare the nitrogen phosphine tridentate ligand ruthenium catalyst.
2. The method for catalyzing hydrocracking of a carbamate according to claim 1, wherein the hydrocracking reaction conditions are: the hydrogen pressure is 20-30 bar, the reaction temperature is 110-130 ℃, and the reaction time is 2-6 hours.
3. The method for catalyzing hydrocracking of carbamate compounds according to claim 1, wherein the mass ratio of carbamate compounds to the ruthenium catalyst serving as a tridentate nitrogen-phosphine ligand is (300-500): (5-15).
4. The method for catalyzing hydrocracking of carbamate compounds according to claim 1, wherein the preparation method of the nitrogen-phosphine tridentate ligand ruthenium catalyst comprises the following steps:
step one, preparing diphenylphosphino-acetaldehyde hydrobromide dimer:
dissolving organic phosphorus salt in a solvent to prepare an organic phosphorus salt solution; adding an organic phosphorus salt solution into a reaction container, then dropwise adding 2-bromoacetaldehyde diethyl acetal under stirring at the temperature of minus 30 ℃, adding hydrobromic acid aqueous solution after the system naturally heats to 20-30 ℃ after the dropwise adding is finished, and stirring for 6-8 hours at the temperature of 40 ℃; after the reaction liquid is cooled, firstly distilling off the solvent, then carrying out suction filtration to obtain a filter cake, and leaching, pumping the solvent and drying the filter cake to obtain diphenylphosphino-acetaldehyde hydrobromide dimer;
the chemical structural formula of the organic phosphorus salt is shown as the following formula IV:
in formula IV:
m is selected from ions corresponding to hydrogen and alkali metal elements;
R 1 selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl and phenyl;
step two, preparing a nitrogen-phosphine ligand:
adding the diphenylphosphino-acetaldehyde hydrobromide dimer prepared in the step one, aminoquinoline compounds, sodium triacetoxyborohydride and a solvent into a reaction vessel, and stirring for 8-12 hours at 20-30 ℃ in a nitrogen protection atmosphere; after the reaction is finished, adding a saturated ammonium chloride aqueous solution into the reaction solution to quench the reaction; extracting a product by adopting ethyl acetate, back-extracting an organic phase obtained by extraction by adopting saturated saline water, and finally sequentially drying, concentrating the organic phase and purifying by column chromatography to obtain a nitrogen-phosphine ligand;
the chemical structural formula of the aminoquinoline compound is shown as the following formula V:
in formula V:
R 2 selected from the group consisting of hydrogen, alkoxy, alkyl, and dimethylamino;
preparing a nitrogen-phosphine tridentate ligand ruthenium catalyst:
adding the nitrogen phosphine ligand prepared in the second step, tris (triphenylphosphine) carbonyl ruthenium chloride and a solvent into a reaction vessel, and stirring for 9-12 hours at 110 ℃ in a nitrogen protection atmosphere; after the reaction is finished, carrying out suction filtration on the reaction liquid to obtain a filter cake, and leaching and drying the filter cake to obtain the nitrogen-phosphine tridentate ligand ruthenium catalyst;
the chemical structural formula of the nitrogen phosphine tridentate ligand ruthenium catalyst is shown as the following formula I:
in formula I:
R 1 selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl and phenyl;
R 2 selected from the group consisting of hydrogen, alkoxy, alkyl, and dimethylamino.
5. The method for catalyzing hydrocracking as claimed in claim 4, wherein in the first step, the molar ratio of the 2-bromoacetaldehyde diethyl acetal, the organic phosphorus salt and the hydrobromic acid is 1:1-2:1.5-3.
6. The method for catalyzing hydrocracking of carbamate according to claim 4, wherein in the second step, the molar ratio of diphenylphosphino-acetaldehyde hydrobromide dimer, aminoquinoline compound and sodium triacetoxyborohydride is 1: (1-2): (2-4).
7. The method for catalyzing hydrocracking of carbamate according to claim 4, wherein in the third step, the molar ratio of the nitrogen-phosphine ligand to the tris (triphenylphosphine) carbonyl ruthenium chloride is (1-1.5): 1.
8. the method for catalyzing the hydrocracking of a carbamate according to claim 4, wherein the solvent is selected from the group consisting of tetrahydrofuran, toluene, 2-methyltetrahydrofuran, ethyl acetate, methylene chloride, chloroform and methanol.
9. The method for catalyzing hydrocracking of a carbamate compound as set forth in claim 1, wherein said carbamate compound is replaced by a compound of formula ii:
in formula II:
R 3 selected from methyl, ethyl, isopropyl, n-butyl, phenyl and benzyl;
R 4 selected from phenyl, substituted phenyl, 2-pyridyl, 1-naphthyl, alpha-methylbenzyl, benzyl, n-hexyl, indole, piperidine and morpholine;
R 5 selected from hydrogen, methyl and phenyl.
10. The preparation method of the nitrogen-phosphine tridentate ligand ruthenium catalyst is characterized in that firstly, organic phosphorus salt, 2-bromoacetaldehyde diethyl acetal and hydrobromic acid are used as reaction raw materials to prepare diphenyl phosphino-acetaldehyde hydrobromide dimer; then diphenyl phosphino-acetaldehyde hydrobromide dimer and aminoquinoline compound are used as reaction raw materials to prepare a nitrogen-phosphine ligand; finally, taking the nitrogen phosphine ligand and the tri (triphenylphosphine) carbonyl ruthenium chloride as reaction raw materials to prepare the nitrogen phosphine tridentate ligand ruthenium catalyst.
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