CN103159802B - Heteronuclear ruthenium-gold bicyclic metal compound and its preparation method and use - Google Patents
Heteronuclear ruthenium-gold bicyclic metal compound and its preparation method and use Download PDFInfo
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- CN103159802B CN103159802B CN201310077547.7A CN201310077547A CN103159802B CN 103159802 B CN103159802 B CN 103159802B CN 201310077547 A CN201310077547 A CN 201310077547A CN 103159802 B CN103159802 B CN 103159802B
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Abstract
The invention discloses a heteronuclear ruthenium-gold bicyclic metal compound and its preparation method and use and belongs to the technical field of organic synthesis. The heteronuclear ruthenium-gold bicyclic metal compound has the advantages of easy preparation, easy modification, high stability, high catalytic activity and long service life. The preparation method has simple processes, strong operability and a high yield. The heteronuclear ruthenium-gold bicyclic metal compound obtained by the preparation method can be used as a bimetallic catalyst for catalyzing a coupling reaction of benzpyrole, methyl ketone and primary alcohol, has catalytic characteristics of ruthenium and gold, has the advantages of wide substrate range, mild conditions, high yield, high efficiency and practicability and low use amount, and can react with a cheap weak base. The heteronuclear ruthenium-gold bicyclic metal compound as a catalyst can obviously improve atom economy and synthesis efficiency of a 3-substituted beta-indolone synthesis reaction.
Description
Technical field
The present invention is specifically related to the bis-cyclometallated compound of heteronuclear ruthenium gold, and the preparation method of this metallic compound and application, belongs to technical field of organic synthesis.
Background technology
Benzazole compounds is important organic raw material and chemical, not only can synthetic dyestuff, spices, can also be used as plant hormone, active alkaloid, and can treat various diseases, therefore they have important use very widely at industry, agricultural and field of medicaments thereof.Particularly 3-substituted indole derivative, for many natural products and the corresponding structure with the important skeleton of bioactive compounds, it has been exactly the derivative that wherein a class is important that 3-replaces beta indolone.That is familiar with 3-substituted indole derivative purposes along with people gos deep into, and especially attracts people's attention to the research of its synthetic method.Usual 3-replaces beta indolone by indoles and α, and beta-unsaturated carbonyl compound Michael reaction occurs and realizes, and conventional catalyzer is solid strong acid or Lewis acid.Solid strong acid environmental pollution is comparatively large, reaction conditions is harsher.In recent years through the effort of chemist, at transition metal Lewis acid catalysis indoles and α, beta-unsaturated carbonyl compound synthesis 3-replaces beta indolone aspect and obtains very large progress.But be avoid using a large amount of strong acid, need with various special α, beta-unsaturated carbonyl compound is substrate, which limits its application aborning.
α, beta-unsaturated carbonyl compound is obtained by ketone and aldehyde generation condensation reaction usually.Compared with aldehyde, alcohol extensively exists, and by product that is relatively cheap, nontoxic, reaction is water, has higher Atom economy, environmentally friendly.For improving Atom economy and the combined coefficient of reaction, the reaction that one kettle way multi-component reaction builds multiple covalent linkage causes the broad interest of chemists, and reaction utilizes transition intermediate, realizes multi-component stacking reaction.The method has the features such as simple to operate, high resource utilization, the high property collected, and can have the compound of structure diversity, complicacy in a large number by Fast back-projection algorithm.Realize polycomponent cascade reaction, just need corresponding various metals concerted catalysis to react.In numerous transition metal complexes, Cyclometalated compound has and is easy to preparation and modifies, stability and catalytic activity high, the advantages such as the life-span is long, make them in organic synthesis and catalytic chemistry, play very important role.Though Cyclometalated compound has more report, the Cyclometalated compound of heteronuclear also rare report.
Summary of the invention
The object of this invention is to provide the bis-cyclometallated compound of a kind of heteronuclear ruthenium gold.
Meanwhile, the present invention also provides the preparation method of the bis-cyclometallated compound of a kind of heteronuclear ruthenium gold.
In order to realize above object, the technical solution adopted in the present invention is:
The bis-cyclometallated compound of heteronuclear ruthenium gold, its general structure is:
In formula: X, X
1, Y, Y
1independently be selected from C atom or atom N, when X and Y is different, get same atoms, X
1with Y
1asynchronously get same atoms; Z, Z
1independently be selected from Cl
-, Br
-or I
-; L is tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes; R
1, R
2independently be selected from the straight chained alkyl of H atom or 1 ~ 10 C.
Described tertiary phosphine-ligand is
Described tetrahydroglyoxaline ring carbenes is
The preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold; step is as follows: the monokaryon ring ruthenium compound according to mol ratio being halogen atom: the monokaryon ring gold compound containing which borate group of Knit-the-brows: soluble palladium salt: alkaline matter A=(1 ~ 1.6): 1:(0.05 ~ 0.15): (1 ~ 5) is got each material and is joined in solvent; temperature be 80 ~ 120 DEG C, heating reflux reaction 10 ~ 48 hours under protection of inert gas; reaction terminates rear filtration; evaporate to dryness; recrystallization, obtains the bis-cyclometallated compound of heteronuclear ruthenium gold.
The general structure of the monokaryon ring ruthenium compound of described halogen atom is:
In formula: X, Y are independently selected from C atom or atom N, but get same atoms when X and Y is different; Z is selected from Cl
-, Br
-or I
-; Z
3be selected from Cl, Br or I; L is tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes; R
1for the direct-connected alkyl of H atom or 1 ~ 10 C.
Described tertiary phosphine-ligand is
Described tetrahydroglyoxaline ring carbenes is
The general structure of the described monokaryon ring gold compound containing which borate group of Knit-the-brows is:
In formula: X
1, Y
1independently be selected from C atom or atom N, X
1with Y
1asynchronously get same atoms; Z
1be selected from Cl
-, Br
-or I
-; R
2for the direct-connected alkyl of H atom or 1 ~ 10 C.
Described soluble palladium salt is Palladous chloride or palladium.
Described alkaline matter A is sodium carbonate, salt of wormwood, cesium carbonate, sodium phosphate or potassiumphosphate.
Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
Described rare gas element is nitrogen or helium.
The solvent that described recrystallization adopts is the mixed solvent of methylene dichloride and sherwood oil.
Moreover the present invention also provides the bis-cyclometallated compound of a kind of heteronuclear ruthenium gold to replace the application of beta indolone as Catalyzed by Pt/M Bimetallic Nano indoles, methyl ketone and primary alconol three components linked reaction synthesis preparation 3-.
The general structure that described 3-replaces beta indolone is:
in formula: R
3, R
4independently be selected from-H ,-CH
3,-C
2h
3,-C
3h
7,-C
4h
9or aryl; The general structure of described aryl is:
in formula: R
5for-CH
3,-C
2h
3,-C
3h
7,-Cl ,-Br ,-F ,-CN ,-OCH
3,-COCH
3or-OH, R
5in 2,3,4 any position.
Reaction mechanism is as follows:
The general structure of described primary alconol is:
in formula: R
3for-H ,-CH
3,-C
2h
3,-C
3h
7,-C
4h
9or aryl; The general structure of described aryl is:
in formula: R
5for-CH
3,-C
2h
3,-C
3h
7,-Cl ,-Br ,-F ,-CN ,-OCH
3,-COCH
3or-OH, R
5in 2,3,4 any position.
The general structure of described methyl ketone is:
in formula: R
4for-H ,-CH
3,-C
2h
3,-C
3h
7,-C
4h
9or aryl; The general structure of described aryl is:
in formula: R
5for-CH
3,-C
2h
3,-C
3h
7,-Cl ,-Br ,-F ,-CN ,-OCH
3,-COCH
3or-OH, R
5in 2,3,4 any position.
The described bis-cyclometallated compound catalyzing indole of heteronuclear ruthenium gold, it is as follows that methyl ketone and primary alconol three components linked reaction synthesis preparation 3-replace the step of beta indolone: be the bis-cyclometallated compound of heteronuclear ruthenium gold according to mol ratio: indoles: methyl ketone: alcohol: alkaline matter B=(0.005 ~ 0.1): 1:(1 ~ 3): (2 ~ 6): (1 ~ 6) is got each material and joined in solvent B, it is 80 ~ 120 DEG C in temperature, heating reflux reaction 12 ~ 48 hours under protection of inert gas, react complete and be cooled to room temperature, add and urge agent of going out to urge reaction of going out, be separated, concentrated, purifying, namely obtain 3-after drying and replace beta indolone.
Described alkaline matter B is sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide or potassium hydroxide.
Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
Described agent of going out of urging is water.
Described separation method is for be separated with dichloromethane extraction.
Beneficial effect of the present invention:
The bis-cyclometallated compound of heteronuclear ruthenium gold of the present invention has advantages such as being easy to preparation, modification, stable, catalytic activity is high, the life-span is long, the catalysis characteristics that simultaneously can play ruthenium, gold is replaced in the synthesis preparation feedback of beta indolone at 3-, replace beta indolone by consecutive reaction synthesis preparation 3-, catalytic activity is high.The method that the present invention prepares the bis-cyclometallated compound of heteronuclear ruthenium gold is simple, workable, productive rate is high, the obtained bis-cyclometallated compound of heteronuclear ruthenium gold as Catalyzed by Pt/M Bimetallic Nano indoles, methyl ketone and primary alconol three components linked reaction, can have reaction substrate scope wide, mild condition, productive rate is high, the advantages such as highly effective, and the consumption of catalyzer is less, and cheap weak base can be used to react.The synthesis preparation feedback using the bis-cyclometallated compound catalysis 3-of heteronuclear ruthenium gold to replace beta indolone can significantly improve Atom economy and the combined coefficient of reaction.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but does not form any limitation of the invention.
The general structure of the bis-cyclometallated compound of heteronuclear ruthenium gold of embodiment 1 ~ 20 is as follows:
In formula, in each embodiment, unit structure is as shown in table 1 below.
The structure of each group in the bis-cyclometallated compound of table 1 embodiment 1 ~ 20 heteronuclear ruthenium gold
Embodiment 1
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: in the 50ml there-necked flask that stirring and refluxing device is housed, add triethyl phosphine monokaryon ring ruthenium compound (1.05mmol) of chloride atom, monokaryon ring gold compound (1mmol), Palladous chloride (0.10mmol), potassiumphosphate (3.0mmol) and 20ml dry toluene containing which borate group of Knit-the-brows, temperature be 110 DEG C, stirring reaction filtered after 20 hours under nitrogen atmosphere, steam after solvent with methylene dichloride (CH
2cl
2) with the mixed solvent recrystallization of sherwood oil, obtain the bis-cyclometallated compound of yellow product 1 heteronuclear triethyl phosphine ruthenium gold, productive rate 86.8%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.86 (d, 1H, Ph-H), 8.61 (d, 1H, Ph-H), 8.15 (s, 1H, Ph-H), 7.66-7.32 (m, 11H, Ph-H), 1.32 (q, 12H, CH
2), 1.08 (t, 18H, CH
3).
Embodiment 2
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: add containing triphenylphosphine monokaryon ring ruthenium compound (1.2mmol) of atomic iodine, monokaryon ring gold compound (1mmol), palladium (0.05mmol), sodium phosphate (2.0mmol) and the 20ml anhydrous dioxane containing which borate group of Knit-the-brows in the 50ml there-necked flask that stirring and refluxing device is housed, temperature be 110 DEG C, stirring reaction filtered after 12 hours under nitrogen atmosphere, steam after solvent with methylene dichloride (CH
2cl
2) with the mixed solvent recrystallization of sherwood oil, obtain the bis-cyclometallated compound of yellow product 2 heteronuclear triphenylphosphine ruthenium gold, productive rate is 88.1%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.63 (d, 1H, Ph-H), 8.58 (d, 1H, Ph-H), 8.12 (d, 2H, Ph-H), 7.69-7.40 (m, 20H, Ph-H), 7.11-7.39 (m, 19H, Ph-H), 2.39 (s, 3H, CH
3).
Embodiment 5
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: in the 50ml there-necked flask that stirring and refluxing device is housed, add trimethyl-phosphine monokaryon ring ruthenium compound (1.1mmol) of bromine atom, monokaryon ring gold compound (1mmol), palladium (0.08mmol), salt of wormwood (3.0mmol) and 20ml anhydrous tetrahydro furan containing which borate group of Knit-the-brows, temperature be 80 DEG C, stirring reaction filtered after 10 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain the bis-cyclometallated compound of yellow product 5 heteronuclear trimethyl-phosphine ruthenium gold, productive rate 92.6%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.56 (d, 1H, Ph-H), 8.53 (d, 1H, Ph-H), 8.11 (d, 2H, Ph-H), 7.63-7.45 (m, 8H, Ph-H), 7.13 (m, 1H, Ph-H), 2.61 (q, 2H, CH
2), 1.36 (t, 3H, CH
3), 1.12 (d, 18H, CH
3).
Embodiment 8
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: in the 50ml there-necked flask that stirring and refluxing device is housed, add tri isopropyl phosphine monokaryon ring ruthenium compound (1.3mmol) of chloride atom, monokaryon ring gold compound (1mmol), Palladous chloride (0.12mmol), sodium carbonate (2.5mmol) and 20ml dry-out benzene containing which borate group of Knit-the-brows, temperature be 100 DEG C, stirring reaction filtered after 20 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain the bis-cyclometallated compound of yellow product 8 heteronuclear tri isopropyl phosphine ruthenium gold, productive rate 91.6%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.59 (d, 1H, Ph-H), 8.56 (d, 1H, Ph-H), 8.10 (d, 2H, Ph-H), 7.65-7.43 (m, 8H, Ph-H), 7.13 (m, 1H, Ph-H), 2.63 (q, 2H, CH
2), 2.10 (m, 4H, CH
2), 1.32 (t, 3H, CH
3), 1.08 (d, 36H, CH
3).
Embodiment 10
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: in the 50ml there-necked flask that stirring and refluxing device is housed, add three cyclohexyl phosphine monokaryons ring ruthenium compound (1.6mmol) of chloride atom, monokaryon ring gold compound (1mmol), palladium (0.06mmol), cesium carbonate (2.0mmol) and 20ml anhydrous dioxane containing which borate group of Knit-the-brows, temperature be 110 DEG C, stirring reaction filtered after 30 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain the bis-cyclometallated compound of yellow product 10 heteronuclear three cyclohexyl phosphine ruthenium gold, productive rate 96.0%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.78 (d, 1H, Ph-H), 8.59 (d, 1H, Ph-H), 8.12 (s, 1H, Ph-H), 7.21-7.72 (m, 9H, Ph-H), 2.62 (t, 2H, CH
2), 2.38 (s, 3H, CH
3), 1.21-1.63 (m, 69H, CH).
Embodiment 12
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: the N adding N-p-methoxyphenyl-N '-p-methoxyphenyl imidazole carbenes monokaryon ring ruthenium compound (1.3mmol) of bromine atom, monokaryon ring gold compound (1mmol), Palladous chloride (0.12mmol), potassium hydroxide (5.0mmol) and 20ml containing which borate group of Knit-the-brows in the 50ml there-necked flask that stirring and refluxing device is housed, dinethylformamide, temperature be 120 DEG C, stirring reaction filtered after 36 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain yellow product 12 heteronuclear N-p-methoxyphenyl-N '-bis-cyclometallated compound of p-methoxyphenyl imidazole carbenes ruthenium gold, productive rate 85.6%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.60 (d, 1H, Ph-H), 8.53 (d, 1H, Ph-H), 8.10 (d, 2H, Ph-H), 7.73-7.46 (m, 10H, Ph-H), 7.18-6.95 (m, 2H, Ph-H), 6.93 (d, 4H, Ph-H), 6.89 (d, 4H, Ph-H), 3.82 (s, 12H, CH
3).
Embodiment 14
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: add containing N-methyl-N '-Methylimidazole Cabbeen monokaryon ring ruthenium compound (1.5mmol) of atomic iodine, monokaryon ring gold compound (1mmol), palladium (0.08mmol), salt of wormwood (3.5mmol) and the 20ml dry toluene containing which borate group of Knit-the-brows in the 50ml there-necked flask that stirring and refluxing device is housed, temperature be 110 DEG C, stirring reaction filtered after 24 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain yellow product 14 heteronuclear N-methyl-N '-bis-cyclometallated compound of Methylimidazole Cabbeen ruthenium gold, productive rate 81.8%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.62 (d, 1H, Ph-H), 8.57 (d, 1H, Ph-H), 8.08 (d, 2H, Ph-H), 7.68-7.46 (m, 7H, Ph-H), 7.43 (m, 4H, NCHCHN), (7.10-6.98 m, 2H, Ph-H), 4.20 (s, 12H, CH
3), 2.57 (t, 2H, CH
2), 0.98-1.62 (m, 15H, CH).
Embodiment 16
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: the N-2 adding bromine atom in the 50ml there-necked flask that stirring and refluxing device is housed, 4,6-trimethylphenyl-N '-2,4,6-trimethylphenyl imidazole carbenes monokaryon ring ruthenium compound (1.2mmol), monokaryon ring gold compound (1mmol), Palladous chloride (0.10mmol), sodium phosphate (5mmol) and 20ml anhydrous tetrahydro furan containing Knit-the-brows any borate group, temperature be 80 DEG C, stirring reaction filtered after 16 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain yellow product 16 heteronuclear N-2, the bis-cyclometallated compound of 4,6-trimethylphenyl-N '-2,4,6-trimethylphenyl imidazole carbenes ruthenium gold, productive rate 94.5%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.85 (d, 1H, Ph-H), 8.61 (d, 1H, Ph-H), 8.17 (d, 1H, Ph-H), 7.72-7.46 (m, 12H, Ph-H), 7.36 (m, 4H, NCHCHN), 7.27 (m, 2H, Ph-H), 2.55 (q, 18H, CH
3), 2.52 (s, 3H, CH
3).
Embodiment 18
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: add containing N-phenyl-N '-phenylimidazole Cabbeen monokaryon ring ruthenium compound (1.6mmol) of atomic iodine, monokaryon ring gold compound (1mmol), Palladous chloride (0.06mmol), potassiumphosphate (3.5mmol) and the 20ml anhydrous dioxane containing which borate group of Knit-the-brows in the 50ml there-necked flask that stirring and refluxing device is housed, temperature be 110 DEG C, stirring reaction filtered after 24 hours under nitrogen atmosphere, used CH after steaming solvent
2cl
2with the mixed solvent recrystallization of sherwood oil, obtain yellow product 18 heteronuclear N-phenyl-N '-bis-cyclometallated compound of phenylimidazole Cabbeen ruthenium gold, productive rate 83.5%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.80 (d, 1H, Ph-H), 8.62 (d, 1H, Ph-H), 8.17 (s, 1H, Ph-H), 7.87-7.59 (m, 14H, Ph-H), (7.55-7.23 m, 18H, Ph-H), (6.95 m, 2H, Ph-H), 2.61 (q, 2H, CH
2), 1.30 (t, 3H, CH
3).
Embodiment 20
In the present embodiment, the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold is: N-N '-two o-isopropyl phenyl imidazole carbenes monokaryon ring ruthenium compound (1.05mmol) adding chloride atom in the 50ml there-necked flask that stirring and refluxing device is housed, containing the monokaryon ring gold compound (1mmol) of Knit-the-brows any borate group, palladium (0.05mmol), salt of wormwood (3.5mmol) and 20ml anhydrous tetrahydro furan, it is 80 DEG C in temperature, under nitrogen atmosphere, stirring reaction filtered after 12 hours, the mixed solvent recrystallization of CH2Cl2 and sherwood oil is used after steaming solvent, obtain yellow product 20 heteronuclear N-o-isopropyl phenyl-N '-bis-cyclometallated compound of o-isopropyl phenyl imidazole carbenes ruthenium gold, productive rate 96.6%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows:
1h NMR: δ=8.86 (d, 1H, Ph-H), 8.60 (d, 1H, Ph-H), 8.16 (s, 1H, Ph-H), 7.68-7.30 (m, 13H, Ph-H+NCHCHN), 6.90 (m, 2H, Ph-H), 6.82 (d, 4H, Ph-H), 2.90-2.99 (m, 8H, CH), 1.60 (s, 12H, CH
3), 1.51 (d, 6H, CH
3), 1.40 (d, 6H, CH
3), 1.12 (d, 6H, CH
3), 0.95 (d, 6H, CH
3), 0.82 (d, 6H, CH
3), 0.58 (d, 6H, CH
3).
Embodiment 21
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 1 to prepare catalyzes and synthesizes preparation 3-replacement-beta-phenyl Propiophenone-1-H-indolone; preparation method is: under high pure nitrogen protection; the toluene of 0.05mmol heteronuclear ruthenium gold bis-cyclometallated compound 1,1.0mmol indoles, 1.5mmol methyl phenyl ketone, 2.5mmol benzylalcohol, 3mmol sodium carbonate and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 24 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter, filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-beta-phenyl Propiophenone-1-H-indolone, productive rate 88.5% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=7.98 (bs, 1H, Ph-H), 7.92 (d, 2H, Ph-H), 7.54-6.93 (m, 13H, Ph-H), 5.08-5.03 (t, 1H, CH), 3.84-3.66 (m, 2H, CH
2).
Embodiment 22
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 3 to prepare catalyzes and synthesizes preparation 3-replacement-beta-phenyl to brom-acetophenone-1-H-indolone; preparation method is: under high pure nitrogen protection; the dioxane of 0.1mmol heteronuclear ruthenium gold bis-cyclometallated compound 3,1.0mmol indoles, 2.0mmol parabromoacetophenone, 3.5mmol benzylalcohol, 3mmol potassium hydroxide and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 30 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-beta-phenyl to brom-acetophenone-1-H-indolone, productive rate 89.1% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=7.91 (bs, 1H, Ph-H), 7.47-7.03 (m, 13H, Ph-H), 5.28 (s, 1H, CH), 3.75 (d, 2H, CH
2).
Embodiment 23
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 6 to prepare catalyzes and synthesizes preparation 3-replacement-2-butanone-1-H-indolone; preparation method is: under high pure nitrogen protection; the benzene of 0.005mmol heteronuclear ruthenium gold bis-cyclometallated compound 6,1.0mmol indoles, 2.0mmol acetone, 3mmol ethanol, 5mmol potassiumphosphate and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 100 DEG C are heated to oil bath under magnetic stirring, reaction backflow 40 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-2-butanone-1-H-indolone, productive rate 83.6% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=7.96 (bs, 1H, Ph-H), 7.37-7.07 (m, 4H, Ph-H), 6.99 (s, 1H, Ph-H), 3.07-3.03 (m, 2H, CH), 2.87-2.82 (m, 2H, CH), 2.14 (s, 3H, CH
3).
Embodiment 24
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 8 to prepare catalyzes and synthesizes preparation 3-replacement-beta-phenyl to anisole acetone-1-H-indolone; preparation method is: under high pure nitrogen protection; the tetrahydrofuran (THF) of 0.08mmol heteronuclear ruthenium gold bis-cyclometallated compound 8,1.0mmol indoles, 3.0mmol p-methoxy-acetophenone, 5mmol benzylalcohol, 3mmol sodium hydroxide and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 80 DEG C are heated to oil bath under magnetic stirring, reaction backflow 48 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-beta-phenyl to anisole acetone-1-H-indolone, productive rate 93.2% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.03 (bs, 1H, Ph-H), 7.96-7.89 (d, 2H, Ph-H), 7.53-6.75 (m, 12H, Ph-H), 5.02-4.97 (t, 1H, CH), 3.80-3.73 (m, 2H, CH
2), 3.72 (s, 3H, CH
3).
Embodiment 25
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 11 to prepare catalyzes and synthesizes preparation 3-replacement-beta-phenyl ethyl-para-hydroxyphenyl ketone-1-H-indolone; preparation method is: under high pure nitrogen protection; the dioxane of 0.1mmol heteronuclear ruthenium gold bis-cyclometallated compound 11,1.0mmol indoles, 2.0mmol parahydroxyacet-ophenone, 4mmol benzylalcohol, 4mmol sodium phosphate and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 80 DEG C are heated to oil bath under magnetic stirring, reaction backflow 48 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-beta-phenyl ethyl-para-hydroxyphenyl ketone-1-H-indolone, productive rate 87.3% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=7.93-7.77 (m, 3H, Ph-H), 7.55-6.90 (m, 12H, Ph-H), 6.56 (s, 1H, Ph-H), 5.88 (s, 1H, CH), 5.08-4.99 (m, 1H, CH), 3.85-3.67 (m, 2H, CH
2).
Embodiment 26
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 13 to prepare catalyzes and synthesizes preparation 3-replacement-beta-phenyl ortho-nitrophenyl acetone-1-H-indolone; preparation method is: under high pure nitrogen protection; the toluene of 0.1mmol heteronuclear ruthenium gold bis-cyclometallated compound 13,1.0mmol indoles, 2.2mmol ortho-nitroacetophenone, 3.5mmol benzylalcohol, 4mmol sodium carbonate and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 45 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-beta-phenyl ortho-nitrophenyl acetone-1-H-indolone, productive rate 94.6% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.67 (s, 3H, Ph-H), 8.41-7.85 (m, 12H, Ph-H), 7.74 (d, 1H, Ph-H), 7.56-7.27 (m, 6H, Ph-H), 7.25 (s, 1H, Ph-H), 7.18-7.15 (m, 2H, Ph-H), 7.04 (s, 1H, Ph-H), 7.01 (s, 1H, Ph-H), 5.18 (t, 1H, Ph-H), 3.92-3.74 (m, 2H, CH
2).
Embodiment 27
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 16 to prepare catalyzes and synthesizes preparation 3-and replaces-β-p-methylphenyl Propiophenone-1-H-indolone; preparation method is: under high pure nitrogen protection; the bis-cyclometallated compound 16 of 0.13mmol heteronuclear ruthenium gold, 1.0mmol indoles, 3.0mmol is added to methyl phenyl ketone, 6mmol to the tetrahydrofuran (THF) of xylyl alcohol, 3mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 80 DEG C are heated to oil bath under magnetic stirring, reaction backflow 38 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated with silica gel thin-layer chromatography, obtains straight product 3-and replaces-β-p-methylphenyl Propiophenone-1-H-indolone, productive rate 91.7%.The nmr analysis data of this compound are as follows:
1hNMR: δ=8.05 (bs, 1H, Ph-H), 7.99-7.90 (d, 2H, Ph-H), 7.51-6.73 (m, 12H, Ph-H), 5.01-4.97 (t, 1H, CH), 3.82-3.75 (m, 2H, CH
2), 2.58 (s, 3H, CH
3).
Embodiment 28
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 18 to prepare catalyzes and synthesizes preparation 3-replacement-Beta-methyl to anisole acetone-1-H-indolone; preparation method is: under high pure nitrogen protection; the N of 0.1mmol heteronuclear ruthenium gold bis-cyclometallated compound 18,1.0mmol indoles, 3.0mmol p-methoxy-acetophenone, 6mmol propyl alcohol, 6mmol salt of wormwood and 3ml is added in the Schlek reaction tubes of 10ml; dinethylformamide; with nitrogen replacement reaction tubes 3 times; then 120 DEG C are heated to oil bath under magnetic stirring, reaction backflow 36 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-Beta-methyl to anisole acetone-1-H-indolone, productive rate 96.0% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.01 (bs, 1H, Ph-H), 7.95-7.87 (d, 2H, Ph-H), 7.50-6.73 (m, 7H, Ph-H), 5.01-4.98 (t, 1H, CH), 3.82-3.72 (m, 2H, CH
2), 3.70 (s, 3H, CH
3), 1.35 (s, 3H, CH
3).
Embodiment 29
The bis-cyclometallated compound of heteronuclear ruthenium gold that the present embodiment adopts embodiment 20 to prepare catalyzes and synthesizes preparation 3-replacement-beta-phenyl adjacency pair dichloropropiophenone-1-H-indolone; preparation method is: under high pure nitrogen protection; the dioxane of 0.1mmol heteronuclear ruthenium gold bis-cyclometallated compound 20,1.0mmol indoles, 4.0mmol adjacency pair dichloroacetophenone, 5mmol benzylalcohol, 6mmol potassium hydroxide and 3ml is added in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then 110 DEG C are heated to oil bath under magnetic stirring, reaction backflow 48 hours.Remove oil bath, water-bath drops to room temperature; Add 3ml water to reaction solution, with the dichloromethane extraction three times of 5ml, merge organic phase and also use anhydrous MgSO
4dry 30 minutes, filter; Filtrate concentrates with rotatory evaporator, and raffinate take petrol ether/ethyl acetate as developping agent, is separated, obtains straight product 3-replacement-beta-phenyl adjacency pair dichloropropiophenone-1-H-indolone, productive rate 95.6% with silica gel thin-layer chromatography.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.04 (bs, 1H, Ph-H), 7.94-7.91 (d, 2H, Ph-H), 7.55-7.14 (m, 7H, Ph-H), 7.05-6.68 (m, 4H, Ph-H), 5.05-5.00 (t, 1H, CH), 3.84-3.63 (m, 2H, CH
2).
Claims (7)
1. the bis-cyclometallated compound of heteronuclear ruthenium gold, is characterized in that: its general structure is:
In formula: X, X
1, Y, Y
1independently be selected from C atom or atom N, when X and Y is different, get same atoms, X
1with Y
1asynchronously get same atoms; Z, Z
1independently be selected from Cl, Br or I; L is tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes; R
1, R
2independently be selected from the straight chained alkyl of H atom or 1 ~ 10 C;
Described tertiary phosphine-ligand is
Described tetrahydroglyoxaline ring carbenes is
2. the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold as claimed in claim 1, it is characterized in that: step is as follows: the monokaryon ring ruthenium compound according to mol ratio being halogen atom: the monokaryon ring gold compound containing Knit-the-brows any borate group: soluble palladium salt: alkaline matter A=(1 ~ 1.6): 1:(0.05 ~ 0.15): (1 ~ 5) is got each material and is joined in solvent, it is 80 ~ 120 DEG C in temperature, heating reflux reaction 10 ~ 48 hours under protection of inert gas, reaction terminates rear filtration, evaporate to dryness, recrystallization, obtain the bis-cyclometallated compound of heteronuclear ruthenium gold, described alkaline matter A is sodium carbonate, salt of wormwood, cesium carbonate, sodium phosphate or potassiumphosphate,
The general structure of the monokaryon ring ruthenium compound of described halogen atom is:
in formula: X, Y are independently selected from C atom or atom N, but get same atoms when X and Y is different, and Z is selected from Cl, Br or I, Z
3be selected from Cl, Br or I, L is tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes, R
1for the direct-connected alkyl of H atom or 1 ~ 10 C;
The general structure of the described monokaryon ring gold compound containing which borate group of Knit-the-brows is:
in formula: X
1, Y
1independently be selected from C atom or atom N, but X
1with Y
1asynchronously get same atoms, Z
1be selected from Cl, Br or I, R
2for the direct-connected alkyl of H atom or 1 ~ 10 C.
3. the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium gold according to claim 2, is characterized in that: described soluble palladium salt is Palladous chloride or palladium.
4. the bis-cyclometallated compound of heteronuclear ruthenium gold as claimed in claim 1 synthesizes the application prepared 3-and replace beta indolone in catalyzing indole, methyl ketone and primary alconol three components linked reaction.
5. the application of the bis-cyclometallated compound of heteronuclear ruthenium gold according to claim 4, is characterized in that: the general structure of described primary alconol is:
in formula: R
3for-H ,-CH
3,-C
2h
3,-C
3h
7,-C
4h
9or aryl; The general structure of described aryl is:
in formula: R
5for-CH
3,-C
2h
3,-C
3h
7,-Cl ,-Br ,-F ,-CN ,-OCH
3,-COCH
3or-OH, R
5in 2,3,4 any position.
6. the application of the bis-cyclometallated compound of heteronuclear ruthenium gold according to claim 4, is characterized in that: the general structure of described methyl ketone is:
in formula: R
4for-H ,-CH
3,-C
2h
3,-C
3h
7,-C
4h
9or aryl; The general structure of described aryl is:
in formula: R
5for-CH
3,-C
2h
3,-C
3h
7,-Cl ,-Br ,-F ,-CN ,-OCH
3,-COCH
3or-OH, R
5in 2,3,4 any position.
7. the application of the bis-cyclometallated compound of heteronuclear ruthenium gold according to claim 4, it is characterized in that: the described bis-cyclometallated compound catalyzing indole of heteronuclear ruthenium gold, it is as follows that methyl ketone and primary alconol three components linked reaction synthesis preparation 3-replace the step of beta indolone: be the bis-cyclometallated compound of heteronuclear ruthenium gold according to mol ratio: indoles: methyl ketone: alcohol: alkaline matter B=(0.005 ~ 0.1): 1:(1 ~ 3): (2 ~ 6): (1 ~ 6) is got each material and joined in solvent B, it is 80 ~ 120 DEG C in temperature, heating reflux reaction 12 ~ 48 hours under protection of inert gas, react complete and be cooled to room temperature, add and urge agent of going out to urge reaction of going out, be separated, concentrated, purifying, namely obtain 3-after drying and replace beta indolone, described alkaline matter B is sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide or potassium hydroxide, described solvent B is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050095203A1 (en) * | 2001-07-05 | 2005-05-05 | Vladimir Grushin | Photoactive lanthanide complexes with phosphine oxides, phosphine oxide-sulfides, pyridine N-oxides, and phosphine oxide-pyridine N-oxides, and devices made with such complexes |
| CN1637004A (en) * | 2003-12-24 | 2005-07-13 | 三星Sdi株式会社 | Binuclear organometallic complexes and organic electroluminescent display device using the same |
| CN1835799A (en) * | 2003-08-11 | 2006-09-20 | 默克专利有限公司 | Immobilizable ruthenium catalysts having n-heterocyclic carbene ligands |
| WO2007091446A1 (en) * | 2006-02-08 | 2007-08-16 | Japan Science And Technology Agency | Method for producing diphosphine compound, diphosphine compound produced by such production method, and intermediate product |
| CN101805374A (en) * | 2010-03-19 | 2010-08-18 | 郑州泰基鸿诺药物科技有限公司 | Ferrocenyl cycloimine palladium-phosphine adduct and preparation and application therefore |
-
2013
- 2013-03-11 CN CN201310077547.7A patent/CN103159802B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050095203A1 (en) * | 2001-07-05 | 2005-05-05 | Vladimir Grushin | Photoactive lanthanide complexes with phosphine oxides, phosphine oxide-sulfides, pyridine N-oxides, and phosphine oxide-pyridine N-oxides, and devices made with such complexes |
| CN1835799A (en) * | 2003-08-11 | 2006-09-20 | 默克专利有限公司 | Immobilizable ruthenium catalysts having n-heterocyclic carbene ligands |
| CN1637004A (en) * | 2003-12-24 | 2005-07-13 | 三星Sdi株式会社 | Binuclear organometallic complexes and organic electroluminescent display device using the same |
| WO2007091446A1 (en) * | 2006-02-08 | 2007-08-16 | Japan Science And Technology Agency | Method for producing diphosphine compound, diphosphine compound produced by such production method, and intermediate product |
| CN101805374A (en) * | 2010-03-19 | 2010-08-18 | 郑州泰基鸿诺药物科技有限公司 | Ferrocenyl cycloimine palladium-phosphine adduct and preparation and application therefore |
Non-Patent Citations (4)
| Title |
|---|
| Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres;Yvonne Halpin等;《Dalton Transactions》;20090402(第21期);第4146-4153页 * |
| Synthesis and Properties of Dinuclear Ru(II)/Os(II) Complexes Based on a Heteroditopic Phenanthroline-Terpyridine Bridging Ligand;Eugenio Coronado等;《Inorganic Chemistry》;20100702;第49卷(第15期);第6897-6903页 * |
| Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach;Lynda Cassidy等;《Dalton Transactions》;20090211(第20期);第3923-3928页 * |
| 佟欣.201310077547.《STN检索报告》.2014, * |
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