CN107629090B - N, N-coordinated rhodium complex, synthetic method and application thereof - Google Patents
N, N-coordinated rhodium complex, synthetic method and application thereof Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 16
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000006268 reductive amination reaction Methods 0.000 claims abstract description 65
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- -1 dimethylamino Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 150000001448 anilines Chemical class 0.000 claims description 5
- 150000008062 acetophenones Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 150000002902 organometallic compounds Chemical class 0.000 abstract 1
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 62
- 238000003756 stirring Methods 0.000 description 33
- 239000000203 mixture Substances 0.000 description 32
- 238000004817 gas chromatography Methods 0.000 description 31
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 30
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 30
- 238000013022 venting Methods 0.000 description 28
- 239000000758 substrate Substances 0.000 description 27
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 18
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 10
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 9
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 description 9
- PDLCCNYKIIUWHA-UHFFFAOYSA-N 1-(4-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=C(C(C)=O)C=C1 PDLCCNYKIIUWHA-UHFFFAOYSA-N 0.000 description 9
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 9
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 description 9
- NLPHXWGWBKZSJC-UHFFFAOYSA-N 4-acetylbenzonitrile Chemical compound CC(=O)C1=CC=C(C#N)C=C1 NLPHXWGWBKZSJC-UHFFFAOYSA-N 0.000 description 9
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 8
- UYFJYGWNYQCHOB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)(C)C)C=C1 UYFJYGWNYQCHOB-UHFFFAOYSA-N 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VONGYFFEWFJHNP-UHFFFAOYSA-N methyl 1h-pyrrole-2-carboxylate Chemical compound COC(=O)C1=CC=CN1 VONGYFFEWFJHNP-UHFFFAOYSA-N 0.000 description 3
- DFYJCXSOGSYMAJ-UHFFFAOYSA-N (4-tert-butylphenyl)-phenylmethanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 DFYJCXSOGSYMAJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- 229910006124 SOCl2 Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SFGNNBCWQOIVAZ-UHFFFAOYSA-N 1h-pyrrole-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CN1 SFGNNBCWQOIVAZ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organometallic compound synthesis, and particularly relates to N, N-coordination rhodium metal complexes, a synthesis method and application thereof2The invention has simple synthesis method, the complex can be used as a catalyst for catalyzing reductive amination reaction of series acetophenone and aniline derivatives, and the product yield is good and is more than 90%.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic metal compounds, and particularly relates to N, N-coordination rhodium complexes, a synthesis method and application thereof.
Background
In nature, amino is widely existed in various natural products, such as antibiotics, proteins, alkaloids and the like, and meanwhile, as important raw materials and intermediates of chemicals, amine compounds have important positions, wherein, ketone (aldehyde) reacts with amine (ammonia) to form the amine compounds in the presence of reducing agents, which is research methods widely applied to .
Disclosure of Invention
Compared with the previously reported cationic metal rhodium catalysts, the neutral rhodium compound in the invention has better solubility in an organic solvent and more excellent catalytic efficiency, and in addition, the hydrogen cleaning reagent is used as a hydrogen source to avoid a large amount of waste residues generated by using metal hydrides such as borohydride and the like as the hydrogen source.
The technical scheme of the invention is specifically introduced as follows.
The technical scheme of the invention is specifically introduced as follows.
The invention provides N, N-coordination rhodium metal complexes, which have a structure shown in a formula I:
the invention also provides a synthesis method of N, N-coordination rhodium metal complexes, which comprises the following steps:
1) firstly, 1H-pyrrole-2-carboxylic acid methyl ester is taken as a raw material and hydrolyzed under alkaline condition to generate 1H-pyrrole-2-carboxylic acid; then 1H-pyrrole-2-carboxylic acid was dissolved in SOCl2Carrying out medium reflux reaction to generate 1H-pyrrole-2-acyl chloride; finally, under the alkaline condition, 1H-pyrrole-2-acyl chloride reacts with pyrazole to generate a ligand L, wherein the structure of the ligand L is shown as a formula II:
2) ligand L and Rh (COD)2Cl reacts under the alkaline condition to generate the N, N-coordination rhodium metal complex.
In the present invention, in step 2), ligands L and Rh (COD)2The mol ratio of Cl is 0.95: 1-1.05: 1.
In the invention, in the step 2), the alkali adopted in the alkaline condition is NaH.
The present invention further provides the use of an N, N-coordinated rhodium metal complex as described above in an amine reduction reaction of acetophenone and aniline derivatives.
In the invention, the structures of the derivatives of acetophenone and aniline are respectively shown as formula III and formula IV:
wherein: r1，R2Is monosubstituted; r1、R2Independently selected from hydrogen, straight or branched chain C1～C10Alkyl, straight or branched C1～C10 of alkoxy, halogen, CN or dimethylamino.
In the present invention, R1Selected from hydrogen, straight or branched C1～C4Radical, straight-chain or branched C1～C10 of alkoxy, halogen, CN or dimethylamino2Selected from hydrogen, straight or branched C1～C4Radical, straight-chain or branched C1～C10 of alkoxy or halogen.
The application method comprises the following specific steps:
reacting acetophenone derivatives, aniline derivatives, N, N-coordinated rhodium metal complexes and MeOH in the presence of H2Under the action of the reaction, heating and pressurizing to perform reductive amination reaction to obtain the amine compound.
Compared with the prior art, the preparation method has the advantages that the synthesis method is simple, the selectivity is excellent, the complex serving as a catalyst can be used for catalyzing the reductive amination reaction of series acetophenone and aniline derivatives, and the product yield is good and is over 90%.
Drawings
FIG. 1 shows the single crystal structure of complex 1.
Detailed Description
The invention is further illustrated by the following example , but is not limited to the following example.
Example 1: synthesis of ligand L
To a solution of methyl 1H-pyrrole-2-carboxylate (1.25g, 10mmol) in MeOH at room temperature was added aqueous KOH (2.24g, 40mmol) and stirred for 7H. After the reaction was complete, 0.5M HCl was added to a solution pH of 8, extracted, filtered, and concentrated in vacuo to give 1H-pyrrole-2-carboxylic acid. Dissolving 1H-pyrrole-2-carboxylic acid in SOCl2Refluxing for 2H (20mL), and removing the solvent in vacuum to obtain 1H-pyrrole-2-acyl chloride. Pyrazole (0.68g, 10mmol), 1H-pyrrole-2-carbonyl chloride, Et at 0 deg.C3N (1.5g) in Et2Stirring in O for 2 h. The resulting mixture was concentrated and purified by silica gel column chromatography (n-hexane: ethyl acetate 6: 1) to obtain ligand L (1.35g, 85% total yield) as a pale yellow solid.
Elemental analysis: c8H7N3O：C 59.62，H 4.38，N 26.07；found：C 59.38，H 4.35，N 26.22.
Example 2: synthesis of Complex 1
Ligand L (48.0mg, 0.3mmol), Rh (COD)2Cl (121mg, 0.3mmol), NaH (8.6mg, 0.36mmol) in CH2Cl2Stirring for 2h to obtain a crude product. After rotary evaporation and recrystallisation, analytically pure rhodium complex 1 was obtained (81.43mg, 73% yield).
Elemental analysis: c16H18N3ORh：C 51.76，H 4.89，N11.32；found：C 51.68，H 4.85，N11.27.
EXAMPLE 3 -like procedure for reductive amination
series acetophenone (0.5mmol), aniline (0.5mmol) derivative, complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask, the flask was transferred to an autoclave and after three cycles of pressurization/venting reacted with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis.
Example 4: reaction 1 for catalyzing reductive amination of acetophenone and aniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of acetophenone, aniline:
acetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Example 5: reaction 2 for catalyzing reductive amination of 4-methylacetophenone and aniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-methylacetophenone with aniline:
the substrate 4-methylacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave with three cycles of pressurization/ventingAfter and H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis in 95% yield.
Example 6: reaction 3 for catalyzing reductive amination of 2-methylacetophenone and aniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 2-methylacetophenone with aniline:
the substrate 2-methylacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 91% yield.
Example 7: reaction 4 for catalyzing reductive amination of 4-methoxyacetophenone and aniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-methoxyacetophenone, aniline:
the substrate 4-methoxyacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 8: reaction 5 for catalyzing reductive amination of 4-cyanoacetophenone and aniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-cyanoacetophenone, aniline:
the substrate 4-cyanoacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source is disconnected and the autoclave is allowed to standAfter stirring for 12h, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Example 9: reaction 6 for catalyzing reductive amination of 4-chloroacetophenone and aniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-chloroacetophenone and aniline:
the substrate 4-chloroacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis in 93% yield.
Example 10: reaction 7 for catalyzing reductive amination of 4-fluoroacetophenone and aniline
The complex 1 prepared in example 2 is used to catalyze the reductive amination reaction of 4-fluoroacetophenone and aniline:
the substrate 4-fluoroacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Example 11: reaction 8 for catalyzing reductive amination of 4-dimethylaminoacetophenone and aniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-dimethylaminoacetophenone with aniline:
the substrate 4-dimethylaminoacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction. After stirring for 12h, letThe resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 12: reaction 9 for catalyzing reductive amination of 4-isopropylacetophenone and aniline
The complex 1 prepared in example 2 is used to catalyze the reductive amination of 4-isopropylacetophenone by aniline:
the substrate 4-isopropylacetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Example 13: catalytic reductive amination reaction 10 of 4-tert-butyl acetophenone and aniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-tert-butyl acetophenone and aniline:
the substrate 4-tert-butyl acetophenone (0.5mmol), aniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 91% yield.
Example 14: reaction 11 for catalyzing reduction amination of acetophenone, 4-methoxyaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of acetophenone, 4-methoxyaniline:
acetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction. After stirring for 12h, the autoclave was cooled and slowly releasedThe resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 15: reaction 12 for catalyzing reductive amination of 4-methylacetophenone and 4-methoxyaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-methylacetophenone, 4-methoxyaniline:
the substrate 4-methylacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Example 16: catalytic reductive amination reaction 13 of 2-methylacetophenone and 4-methoxyaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 2-methylacetophenone, 4-methoxyaniline:
the substrate 2-methylacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 92% yield.
Example 17: reaction 14 for catalyzing reductive amination of 4-methoxyacetophenone, 4-methoxyaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-methoxyacetophenone, 4-methoxyaniline:
the substrate 4-methoxyacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source is disconnected and the autoclave is heated to reactAfter stirring for 12h, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, yield 90%.
Example 18: catalytic reductive amination of 4-cyanoacetophenone, 4-methoxyaniline reaction 15
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-cyanoacetophenone, 4-methoxyaniline:
the substrate 4-cyanoacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 19: reaction 16 for catalyzing reductive amination of 4-chloroacetophenone and 4-methoxyaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-chloroacetophenone and 4-methoxyaniline:
the substrate 4-chloroacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis in 95% yield.
Example 20: reaction 17 for catalyzing reductive amination of 4-fluoroacetophenone and 4-methoxyaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-fluoroacetophenone and 4-methoxyaniline:
the substrate 4-fluoroacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 91% yield.
Example 21: reaction 18 for catalyzing reductive amination of 4-dimethylamino acetophenone, 4-methoxyaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-dimethylaminoacetophenone, 4-methoxyaniline: the substrate 4-dimethylaminoacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis in 96% yield.
Example 22: reaction 19 for catalyzing reductive amination of 4-isopropylacetophenone and 4-methoxyaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-isopropylacetophenone and 4-methoxyaniline:
the substrate 4-isopropylacetophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were charged to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 92% yield.
Example 23: catalytic reductive amination reaction 20 of 4-tert-butyl acetophenone and 4-methoxyaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-tert-butyl acetophenone and 4-methoxyaniline:
the substrate 4-tert-butylbenzophenone (0.5mmol), 4-methoxyaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave, aAfter three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 24: reaction 21 for catalyzing reductive amination of acetophenone, 4-chloroaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of acetophenone, 4-chloroaniline:
acetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 25: catalytic reductive amination of 4-methylacetophenone, 4-chloroaniline reaction 22
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-methylacetophenone, 4-chloroaniline:
the substrate 4-methylacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 91% yield.
Example 26: catalytic reductive amination of 2-methylacetophenone, 4-chloroaniline 23
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 2-methylacetophenone, 4-chloroaniline:
the substrate 2-methylacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave with three cycles of pressurization/ventingAfter and H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis in 95% yield.
Example 27: reaction 24 for catalyzing reductive amination of 4-methoxyacetophenone, 4-chloroaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-methoxyacetophenone, 4-chloroaniline:
the substrate 4-methoxyacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 92% yield.
Example 28: catalytic reductive amination of 4-cyanoacetophenone, 4-chloroaniline 25
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-cyanoacetophenone, 4-chloroaniline:
the substrate 4-cyanoacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Example 29: reaction 26 for catalyzing reductive amination of 4-chloroacetophenone and 4-chloroaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-chloroacetophenone and 4-chloroaniline:
the substrate 4-chloroacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave, after three cycles of pressurization/ventingAnd H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis in 93% yield.
Example 30: catalytic reductive amination of 4-fluoroacetophenone, 4-chloroaniline 27
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-fluoroacetophenone and 4-chloroaniline:
the substrate 4-fluoroacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 31: reaction 28 for catalyzing reductive amination of 4-dimethylaminoacetophenone and 4-chloroaniline
The complex 1 prepared in example 2 was used to catalyze the reductive amination of 4-dimethylaminoacetophenone, 4-chloroaniline:
the substrate 4-dimethylaminoacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 91% yield.
Example 32: reaction 29 for catalyzing reductive amination of 4-isopropylacetophenone and 4-chloroaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-isopropylacetophenone and 4-chloroaniline:
the substrate 4-isopropylacetophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were charged to a 10mL flask. The flask was transferred to an autoclave through three cyclesAfter pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 94% yield.
Example 33: catalytic reductive amination reaction 30 of 4-tert-butyl acetophenone and 4-chloroaniline
The complex 1 prepared in example 2 is used for catalyzing the reductive amination reaction of 4-tert-butyl acetophenone and 4-chloroaniline:
the substrate 4-tert-butylbenzophenone (0.5mmol), 4-chloroaniline (0.5mmol), complex 1(5 mol%) and MeOH (2mL) were added to a 10mL flask. The flask was transferred to an autoclave and after three cycles of pressurization/venting with H2The source was disconnected and the autoclave was heated to the desired temperature for the reaction after 12h of stirring, the autoclave was cooled and the pressure was slowly released the resulting mixture was added to the internal standard (n-tridecane) to obtain drops for GC analysis, 90% yield.
Claims (3)
- The application of N, N-coordination rhodium metal complexes in reductive amination reaction of acetophenone and aniline derivatives, wherein the N, N-coordination rhodium metal complexes have a structure shown in formula I:wherein:
the structures of the derivatives of acetophenone and aniline are respectively shown in formula III and formula IV:
wherein: r1，R2Is monosubstituted; r1、R2Independently selected from hydrogen, straight or branched chain C1～C10Alkyl, straight or branched C1～C10 of alkoxy, halogen, CN or dimethylamino. - 2.Use according to claim 1, wherein R is1Selected from hydrogen, straight or branched C1～C4Radical, straight-chain or branched C1～C10 of alkoxy, halogen, CN or dimethylamino2Selected from hydrogen, straight or branched C1～C4Radical, straight-chain or branched C1～C10 of alkoxy or halogen.
- 3. The application of claim 1, wherein the application method comprises the following specific steps:reacting acetophenone derivatives, aniline derivatives, N, N-coordinated rhodium metal complexes and MeOH in the presence of H2Under the action of the reaction, heating and pressurizing to perform reductive amination reaction to obtain the amine compound.
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