CN103012504A - Heteronuclear palladium gold bicyclo metal compound as well as preparation method and application of compound - Google Patents
Heteronuclear palladium gold bicyclo metal compound as well as preparation method and application of compound Download PDFInfo
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- CN103012504A CN103012504A CN2012105919403A CN201210591940A CN103012504A CN 103012504 A CN103012504 A CN 103012504A CN 2012105919403 A CN2012105919403 A CN 2012105919403A CN 201210591940 A CN201210591940 A CN 201210591940A CN 103012504 A CN103012504 A CN 103012504A
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Abstract
The invention provides a heteronuclear palladium gold bicyclo metal compound as well as a preparation method and an application of the compound, belonging to the field of organic synthesis. The technical scheme is as follows: the heteronuclear palladium gold bicyclo metal compound has a general formula as shown in the specification, wherein in the formula, X, X1, Y and Y1 are C atoms or N atoms, the same atoms are used when X is different from Y, and the same atoms are used when X1 is different from Y, Z and Z1 are selected from Cl<-1>, Br<-1> and I<-1>, L is tertiary phosphine ligand or N-heterocyclic carbenes ligand, R1 and R2 are H or straight-chain alkyl in which C is equal to 1-10. The preparation method comprises the following synthesis steps of: adding mononuclear cyclo-palladium compound containing halogen atoms, mononuclear cyclo-gold compound containing borate ester and alkali in an organic solvent; under the protection of inert gas, carrying out heating reflux; and after the reaction is finished, filtering, drying by distillation, and re-crystallizing, so as to obtain the compound. According to the invention, the heteronuclear palladium gold bicyclo metal compound also is used as a catalyst to catalyze the reaction of O-N-substituted halogeno benzene and alkyne so as to synthesize 1,2-substituted indole, and the reaction is economic and efficient, so that the compound has important application value.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to one group of heteronuclear porpezite dicyclo metallic compound, and the preparation method of this compounds and purposes.
Background technology
Benzazole compounds is important organic raw material and chemical, and in recent years, this compounds has attracted people's very big concern.Benzazole compounds not only can synthetic dyestuff, spices, but also can be used as plant hormone, active alkaloid, can treat various diseases, so they have very widely important use at industry, agricultural and field of medicaments thereof.Along with people to the going deep into of benzazolyl compounds purposes understanding, also more and more to the research of its synthetic method.Adopt traditionally acid catalyzed Fischer synthesis method, but it has the shortcomings such as the low and regioselectivity of productive rate is poor, the method need to be take phenylhydrazine and derivative thereof as raw material in addition, and they are easily oxidized, unstable in air.Pass through in recent years organic chemist's effort, do not come take fragrant hydrazine derivative as raw material to make great progress aspect the synthesis of indole derivative at transition metal-catalyzed aniline etc.
Transition metal-catalyzed synthesis method reaction conditions is gentle, yield is high, reaction substrate is wide, environmental pollution is less.Its synthesis material mainly concentrates on aniline cheap and easy to get and alkynes or alkene at present, and palladium is that the maximum catalytic effects of report also are best in the transition-metal catalyst.In numerous palladium complex catalyzer, the ring palladium compound has that catalytic activity is high, the life-span is long, be easy to preparation, modify, to advantages such as heat and air-stables, so that they are playing the part of very important role in organic synthesis and catalytic chemistry.The ring palladium compound has a lot of reports, and heteronuclear ring palladium compound rare report also.Consider that palladium has good catalytic activity to the linked reaction of halogenated aryl hydrocarbon and alkynes, gold also has good catalytic effect to the addition of alkynes simultaneously, we synthesize heteronuclear porpezite dicyclo metallic compound, the reaction of catalyzing N-replacement halogeno-benzene and alkynes, the catalysis characteristics of performance palladium, gold is by consecutive reaction synthesis of indole derivative.So far, yet there are no the synthetic of heteronuclear porpezite dicyclo metallic compound and replace the reaction of halogeno-benzene and alkynes, the report of synthetic preparation 1,2-substituted indole as the adjacent N-of Catalyzed by Pt/M Bimetallic Nano with it.
Summary of the invention
The object of the present invention is to provide one group of heteronuclear porpezite dicyclo metallic compound, the synthetic method of this compounds also is provided simultaneously.Another object of the present invention is that the heteronuclear porpezite dicyclo metallic compound that obtains is made bimetallic catalyst, catalyzes and synthesizes 1,2-substituted indole.
Based on above-mentioned purpose, the present invention has adopted following technical scheme: heteronuclear porpezite dicyclo metallic compound has following general formula:
Described tertiary phosphine-ligand is selected from:
Described N-heterocyclic carbene ligand is selected from:
The wherein phosphorus atom in the tertiary phosphine-ligand and metal-complexing; In the N-heterocyclic carbene ligand between two nitrogen-atoms with carbon atom and the metal-complexing of lone-pair electron.
The preparation method of described heteronuclear porpezite dicyclo metallic compound, step is: monokaryon ring palladium compound, monokaryon ring gold compound and alkali are joined in the organic solvent, heating reflux reaction under protection of inert gas, filtration after reaction finishes, evaporate to dryness and recrystallization namely get heteronuclear porpezite dicyclo metallic compound; Wherein monokaryon ring palladium compound has following general formula:
The mole of described monokaryon ring palladium compound, monokaryon ring gold compound and alkali is 1～2 ︰, 1 ︰ 1～5.
Among the described preparation method, alkali is yellow soda ash, salt of wormwood, cesium carbonate, sodium phosphate or potassiumphosphate; Described organic solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF; Temperature of reaction is 80-120 ℃, and the reaction times is 12-48h, with methylene dichloride product is carried out recrystallization after the end that refluxes.
The purposes of described heteronuclear porpezite dicyclo metallic compound: described heteronuclear porpezite dicyclo metallic compound is used as bimetallic catalyst.
The purposes of described heteronuclear porpezite dicyclo metallic compound: utilize the adjacent N-of described heteronuclear porpezite dicyclo metallic compound catalysis to replace halogeno-benzene and alkyne reaction, synthetic 1,2-substituted indole; Described 1, the 2-substituted indole has following general formula:
R
3, R
4For-H ,-CH
3,-C
2H
3,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13Or aryl,
Described 1, the synthesis step of 2-substituted indole is: heteronuclear porpezite dicyclo metallic compound, adjacent N-are replaced halogeno-benzene, alkynes and alkali join in the organic solvent, under the protection of inert gas 80～120 ℃ of reactions 12～48 hours; Reaction is finished, and is down to room temperature, adds shrend and goes out, and use dichloromethane extraction, concentrates, namely gets product 1, the 2-substituted indole behind the purifying.
Described 1, in the synthesis step of 2-substituted indole, the mol ratio that heteronuclear porpezite dicyclo metallic compound, adjacent N-replace halogeno-benzene, alkynes and alkali is 0.005～0.2 ︰, 1 ︰, 1～3 ︰ 1～6.
Described 1, in the synthesis step of 2-substituted indole, alkali is yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide, potassium hydroxide, potassium tert.-butoxide or sodium tert-butoxide; Described organic solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
Heteronuclear porpezite dicyclo metallic compound provided by the invention has that catalytic activity is high, thermostability and the advantages such as air stability is strong, the life-span is long, and is easy to preparation and modifies.Be the adjacent N-of Catalyzed by Pt/M Bimetallic Nano with it and replace halogeno-benzene and alkyne reaction synthetic 1, the 2-substituted indole, have the advantages such as catalyst levels is less, the reaction substrate scope is wide, reaction conditions is gentle, used weak base low price, productive rate height, the reaction of this type of economical and efficient has important using value.In the preparation method of heteronuclear porpezite dicyclo metallic compound provided by the invention, monokaryon ring palladium compound is that substrate plays again katalysis in reaction, therefore need not additionally to add palladium catalyst; Itself and monokaryon ring gold compound generation linked reaction generate heteronuclear porpezite dicyclo metallic compound, the coordination ability that can overcome polydentate ligand too by force, easily generates the shortcoming of title complex, and a synthetic convenience, the practical new way of providing of heteronuclear dicyclo metallic compound is provided.
Embodiment
The present invention will be further described below in conjunction with specific embodiment:
Embodiment 1
One group of heteronuclear porpezite dicyclo metallic compound, general formula is:
Concrete structure can be:
Embodiment 2
The preparation of heteronuclear triphenylphosphine porpezite dicyclo metallic compound (1): in the 50ml there-necked flask of stirring and refluxing device is housed, add 1.3mmol monokaryon ring palladium compound (the triphenylphosphine monokaryon ring palladium compound of bromine atom), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 2.0mmol salt of wormwood, 20ml dry toluene, filter behind the stirring reaction 12h under 110 ℃ of temperature, the nitrogen atmosphere, steam behind the solvent with methylene dichloride (CH
2Cl
2) recrystallization, obtaining yellow product (1), productive rate is 91.2%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.60 (d, 1H, Ph-H), 8.57 (d, 1H, Ph-H), 8.10 (d, 2H, Ph-H), 7.65-7.41 (m, 11H, Ph-H), 7.10-7.36 (m, 12H, Ph-H).
The concrete structure of monokaryon ring palladium compound and monokaryon ring gold compound is referring to table 1, and is lower same.
Embodiment 3
The preparation of heteronuclear tri isopropyl phosphine porpezite dicyclo metallic compound (3): in the 50ml there-necked flask of stirring and refluxing device is housed, add 1mmol monokaryon ring palladium compound (the tri isopropyl phosphine monokaryon ring palladium compound of chloride atom), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 2.5mmol yellow soda ash, 20ml anhydrous tetrahydro furan, filter behind the stirring reaction 20h under 80 ℃ of temperature, the nitrogen atmosphere, use the CH2Cl2 recrystallization after steaming solvent, obtain red product (3), productive rate 92.6%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.57 (d, 1H, Ph-H), 8.53 (d, 1H, Ph-H), 8.10 (d, 2H, Ph-H), 7.60-7.47 (m, 8H, Ph-H), 7.11 (m, 1H, Ph-H), 2.36 (s, 3H, CH
3), 2.06 (m, 3H, CH), 1.10 (d, 18H, CH
3).
Embodiment 4
The preparation of heteronuclear three (p-methylphenyl) phosphine porpezite dicyclo metallic compound (5): in the 50ml there-necked flask of stirring and refluxing device is housed, add 1.2mmol monokaryon ring palladium compound (three (p-methylphenyl) phosphine monokaryon ring palladium compound of bromine atom), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 3.0mmol cesium carbonate, the anhydrous dioxane of 20ml, filter behind the stirring reaction 30h under 110 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (9), productive rate 96.8%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.82 (d, 1H, Ph-H), 8.62 (d, 1H, Ph-H), 8.18 (s, 1H, Ph-H), 7.65-7.36 (m, 10H, Ph-H), 7.43 (d, 6H, Ph-H), 7.21 (m, 6H, Ph-H), 2.60 (q, 2H, CH
2), 2.38 (s, 9H, CH
3), 1.26 (t, 3H, CH
3).
Embodiment 5
The preparation of heteronuclear biphenyl two cyclohexyl phosphine porpezite dicyclo metallic compounds (8): in the 50ml there-necked flask of stirring and refluxing device is housed, add 1.1mmol monokaryon ring palladium compound (the biphenyl two cyclohexyl phosphine monokaryon ring palladium compounds of chloride atom), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 3.0mmol potassiumphosphate, the anhydrous N of 20ml, dinethylformamide, filter behind the stirring reaction 12h under 120 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (8), productive rate 95.9%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.86 (d, 1H, Ph-H), 8.61 (d, 1H, Ph-H), 8.15 (s, 1H, Ph-H), 7.98 (1H, s, Ph-H), 7.66-7.38 (m, 17H, Ph-H), 7.12 (1H, s, Ph-H), 2.61 (q, 2H, CH
2), 2.35 (m, 2H, CH), 2.02 (m, 2H, CH), 1.83-1.04 (m, 36H, CH
2+ CH
3).
Embodiment 6
The preparation of heteronuclear N-phenyl-N '-phenylimidazole Cabbeen porpezite dicyclo metal compound (10): in the 50ml there-necked flask of stirring and refluxing device is housed, add the 2.0mmol monokaryon ring palladium compound (N of bromine atom, N '-diphenyl-imidazole Cabbeen monokaryon ring palladium compound), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 2.0mmol potassiumphosphate, the anhydrous dioxane of 20ml, filter behind the stirring reaction 35h under 110 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (10), productive rate 87.2%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.86 (d, 1H, Ph-H), 8.69 (d, 1H, Ph-H), 8.13 (s, 1H, Ph-H), 7.99 (1H, s, Ph-H), 7.68-7.35 (m, 18H, Ph-H), 2.61 (q, 2H, CH
2), 2.35 (m, 2H, CH), 1.28 (s, 3H, CH
3).
Embodiment 7
The preparation of heteronuclear N-p-methoxyphenyl-N '-p-methoxyphenyl imidazoles Cabbeen porpezite dicyclo metal compound (12): in the 50ml there-necked flask of stirring and refluxing device is housed, add the 1.8mmol monokaryon ring palladium compound (N that contains the iodine atom, N '-di-p-methoxy phenylimidazole Cabbeen monokaryon ring palladium compound), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 3.0mmol cesium carbonate, 20ml dry-out benzene, filter behind the stirring reaction 40h under 100 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (12), productive rate 86.2%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.63 (d, 1H, Ph-H), 8.58 (d, 1H, Ph-H), 8.13 (d, 2H, Ph-H), 7.69-7.43 (m, 10H, Ph-H), (7.13-6.98 m, 2H, Ph-H), 6.95 (d, 4H, Ph-H), 6.88 (d, 4H, Ph-H), 3.82 (s, 12H, CH
3).
Embodiment 8
Heteronuclear N-2,4,6-trimethylphenyl-N '-2,4, the preparation of 6-trimethylphenyl imidazoles Cabbeen porpezite dicyclo metallic compound (14): in the 50ml there-necked flask of stirring and refluxing device is housed, add the 1.1mmol monokaryon ring palladium compound (N of bromine atom, N '-two (2,4, the 6-trimethylphenyl) imidazoles Cabbeen monokaryon ring palladium compound), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 5mmol potassiumphosphate, 20ml toluene, filter behind the stirring reaction 16h under 110 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (14), productive rate 96.1%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.85 (d, 1H, Ph-H), 8.61 (d, 1H, Ph-H), 8.17 (d, 1H, Ph-H), 7.70-7.29 (m, 16H, Ph-H), 2.53 (s, 3H, CH
3), 2.46 (s, 18H, CH
3).
Embodiment 9
The preparation of heteronuclear N-methyl-N '-Methylimidazole Cabbeen porpezite dicyclo metallic compound (16): in the 50ml there-necked flask of stirring and refluxing device is housed, add the 1.5mmol monokaryon ring palladium compound (N that contains the iodine atom, N '-methylimidazole Cabbeen monokaryon ring palladium compound), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 3.5mmol yellow soda ash, 20ml dry toluene, filter behind the stirring reaction 24h under 110 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (16), productive rate 83.8%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.60 (d, 1H, Ph-H), 8.59 (d, 1H, Ph-H), 8.10 (d, 2H, Ph-H), 7.66-7.40 (m, 8H, Ph-H), 6.98 (d, 1H, Ph-H), 4.16 (s, 6H, CH
3), 2.63 (q, 2H, CH
2), 1.29 (s, 3H, CH
3).。
Embodiment 10
The preparation of heteronuclear N-o-isopropyl phenyl-N '-o-isopropyl phenyl imidazoles Cabbeen porpezite dicyclo metallic compound (18): in the 50ml there-necked flask of stirring and refluxing device is housed, add the 1.1mmol monokaryon ring palladium compound (N of chloride atom, N '-two (2, the 6-diisopropyl phenyl) imidazoles Cabbeen monokaryon ring palladium compound), 1mmol monokaryon ring gold compound (the monokaryon ring gold compound that contains Knit-the-brows any boric acid ester group), 3.5mmol salt of wormwood, 20ml anhydrous tetrahydro furan, filter behind the stirring reaction 48h under 80 ℃ of temperature, the nitrogen atmosphere, use CH after steaming solvent
2Cl
2Recrystallization obtains red product (18), productive rate 98.5%.Products obtained therefrom is carried out nuclear magnetic resonance spectroscopy, and data are as follows:
1HNMR: δ=8.83 (d, 1H, Ph-H), 8.66 (d, 1H, Ph-H), 8.21 (s, 1H, Ph-H), 7.67-7.39 (m, 13H, Ph-H), 6.95 (m, 2H, Ph-H), 6.88 (d, 4H, Ph-H), 2.91-2.97 (m, 4H, CH), 1.68 (s, 6H, CH
3), 1.51 (d, 3H, CH
3), 1.45 (d, 3H, CH
3), 1.16 (d, 3H, CH
3), 0.97 (d, 3H, CH
3), 0.85 (d, 3H, CH
3), 0.56 (d, 3H, CH
3).
The structure of monokaryon ring palladium compound and monokaryon ring gold compound among the table 1 embodiment 2-10
Embodiment 11
Synthesizing of 2-phenyl-1-phenyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the toluene that adds 0.05mmol heteronuclear porpezite dicyclo metallic compound (1), the adjacent N-phenyl of 1.0mmol bromobenzene, 2.5mmol benzyne, 3mmol yellow soda ash and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 100 ℃ with oil bath, back flow reaction 48 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains straight product 2-phenyl-1-phenyl-1-H-indoles, productive rate 89.6%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.62 (d, 1H, Ph-H), 7.25-7.02 (m, 13H, Ph-H), 6.72 (d, 1H, Ar-H).
Embodiment 12
Synthesizing of 2-phenyl-1-p-methylphenyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the dioxane that adds 0.1mmol heteronuclear porpezite dicyclo metallic compound (3), the adjacent N-p-methylphenyl of 1.0mmol phenyl-iodide, 2mmol benzyne, 2mmol salt of wormwood and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 110 ℃ with oil bath, back flow reaction 30 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains straight product 2-phenyl-1-p-methylphenyl-1-H-indoles, productive rate 88.5%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.60 (d, 1H, Ph-H), 7.22-7.00 (m, 12H, Ph-H), 6.70 (d, 1H, Ar-H), 2.31 (s, 3H, CH
3).
Embodiment 13
1-is synthetic to group-4 ethyl formate phenyl-2-phenyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; add 0.2mmol heteronuclear porpezite dicyclo metallic compound (5), the adjacent N-of 1.0mmol in the Schlek reaction tubes of 10ml to the tetrahydrofuran (THF) of group-4 ethyl formate phenyl phenyl-iodide, 3mmol benzyne, 6mmol potassiumphosphate and 3ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 80 ℃ with oil bath, back flow reaction 40 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains straight product 1-to group-4 ethyl formate phenyl-4-Phenylindole, productive rate 86.2%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.98 (d, 2H, Ph-H), 7.58 (m, 1H, Ph-H), 7.23 (m, 1H, Ph-H), 7.19 (d, 2H, Ph-H), 7.16-7.12 (m, 5H, Ph-H), (7.10 d, 1H, Ph-H), 7.09 (d, 1H, Ph-H), 6.71 (d, 1H, Ar-H), 4.29 (q, 2H, CH
2), 1.29 (t, 3H, CH
3).
Embodiment 14
Synthesizing of 2-normal-butyl-1-p-methylphenyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the dioxane that adds 0.1mmol heteronuclear porpezite dicyclo metallic compound (8), the adjacent N-p-methylphenyl of 1.0mmol chlorinated benzene, 2.0mmol normal-butyl alkynes, 4mmol cesium carbonate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 110 ℃ with oil bath, back flow reaction 36 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains straight product 1-to group-4 ethyl formate phenyl-4-Phenylindole, productive rate 85.6%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.74 (m, 1H, Ph-H), 7.48 (d, 2H, Ph-H), 7.38 (d, 2H, Ph-H), 7.30-7.15 (m, 3H, Ph-H), 6.56 (s, 1H, Ar-H), 2.78 (t, 2H, CH
2), 2.32 (s, 3H, CH
3), 1.75 (q, 2H, CH
2), 1.49 (q, 2H, CH
2), 1.03 (t, 3H, CH
3).
Embodiment 15
2-is synthesizing of base-1-rubigan-1-H-indoles just: under rare gas element (high pure nitrogen) protection; the N that adds 0.05mmol heteronuclear porpezite dicyclo metallic compound (10), the adjacent N-rubigan of 1.0mmol bromobenzene, the just basic alkynes of 2.5mmol, 3mmol potassium hydroxide and 3ml in the Schlek reaction tubes of 10ml; dinethylformamide; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 120 ℃ with oil bath, back flow reaction 30 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains just base-1-rubigan-1-H-indoles of straight product 2-, productive rate 90.5%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.80 (m, 1H, Ph-H), 7.72 (d, 2H, Ph-H), 7.49 (d, 2H, Ph-H), 7.36-7.25 (m, 3H, Ph-H), 6.64 (s, 1H, Ar-H), 2.81 (t, 2H, CH
2), 1.79 (q, 2H, CH
2), 1.55-1.40 (m, 6H, CH
2), 1.08 (t, 3H, CH
3).
Embodiment 16
Synthesizing of 2-(1-naphthalene) base-1-phenyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the benzene that adds 0.10mmol heteronuclear porpezite dicyclo metallic compound (12), the adjacent N-phenyl of 1.0mmol phenyl-iodide, 2.5mmol1-naphthalyne, 3mmol sodium hydroxide and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 100 ℃ with oil bath, back flow reaction 24 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains straight product 2-(1-naphthalene) base-1-phenyl-1-H-indoles, productive rate 93.3%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.69 (d, 2H, Ph-H), 7.62 (d, 1H, Ph-H), 7.38-7.12 (m, 13H, Ph-H), 6.75 (d, 1H, Ar-H).
Embodiment 17
Synthesizing of the 1-tertiary butyl-2-normal-butyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the toluene that adds 0.05mmol heteronuclear porpezite dicyclo metallic compound (15), the adjacent N-tert-butylbromo of 1.0mmol benzene, 2.0mmol normal-butyl alkynes, 2mmol sodium phosphate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 110 ℃ with oil bath, back flow reaction 40 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains the straight product 1-tertiary butyl-2-normal-butyl-1-H-indoles, productive rate 92.5%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.67-7.64 (m, 1H, Ph-H), 7.57-7.54 (m, 1H, Ph-H), 7.19-7.12 (m, 2H, Ph-H), 6.33 (d, 1H, Ar-H), 2.73 (t, 2H, CH
2), 1.64-1.54 (m, 2H, CH
2), 1.45 (s, 9H, CH
3), 1.33-1.20 (m, 2H, CH
2), 0.85 (t, 3H, CH
3).
Embodiment 18
Synthesizing of the 1-tertiary butyl-2-cyclopropyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the dioxane that adds 0.01mmol heteronuclear porpezite dicyclo metallic compound (17), the adjacent N-tert-butylbromo of 1.0mmol benzene, 2.5mmol cyclopropyl alkynes, 6mmol sodium phosphate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 110 ℃ with oil bath, back flow reaction 12 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains the straight product 1-tertiary butyl-2-cyclopropyl-1-H-indoles, productive rate 91.5%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.69-7.66 (m, 1H, Ph-H), 7.51-7.48 (m, 1H, Ph-H), 7.11-7.00 (m, 2H, Ph-H), 6.24 (s, 1H, Ar-H), 2.16-2.04 (m, 1H, CH), 1.94 (s, 9H, CH
3), 1.01-0.84 (m, 4H, CH
2).
Embodiment 19
Synthesizing of 1-p-methoxyphenyl-2-phenyl-1-H-indoles: under rare gas element (high pure nitrogen) protection; the toluene that adds 0.005mmol heteronuclear porpezite dicyclo metallic compound (18), the adjacent N-p-methoxyphenyl of 1.0mmol bromobenzene, 1.0mmol benzyne, 6mmol potassiumphosphate and 3ml in the Schlek reaction tubes of 10ml; with nitrogen replacement reaction tubes 3 times; then under magnetic agitation, be heated to 110 ℃ with oil bath, back flow reaction 12 hours.Remove oil bath, water-bath drops to room temperature; Add the 3ml shrend to reaction solution and go out, then use the dichloromethane extraction three times of 5ml, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Filtrate is concentrated with rotatory evaporator, and raffinate separates with silica gel thin-layer chromatography take petrol ether/ethyl acetate as developping agent, obtains straight product 1-p-methoxyphenyl-2-phenylindone, productive rate 89.5%.The nmr analysis data of this compound are as follows:
1HNMR: δ=7.57 (m, 1H, Ph-H), 7.40-7.25 (m, 5H, Ph-H), 7.15-7.00 (m, 3H, Ph-H), 6.85 (d, 2H, Ph-H), 6.71 (d, 2H, Ph-H), 6.55 (s, 1H, Ar-H), 3.67 (s, 3H, CH
3).
Claims (10)
1. heteronuclear porpezite dicyclo metallic compound is characterized in that, this compound has following general formula:
2. heteronuclear porpezite dicyclo metallic compound as claimed in claim 1 is characterized in that, described tertiary phosphine-ligand is selected from:
Described N-heterocyclic carbene ligand is selected from:
3. the preparation method of claim 1 or 2 described heteronuclear porpezite dicyclo metallic compounds, it is characterized in that, step is: monokaryon ring palladium compound, monokaryon ring gold compound and alkali are joined in the organic solvent, heating reflux reaction under the protection of rare gas element, filtration after reaction finishes, evaporate to dryness and recrystallization namely get heteronuclear porpezite dicyclo metallic compound; Wherein monokaryon ring palladium compound has following general formula:
X, Y, Z, L, R
1With X, Y, Z, L, the R in the described heteronuclear porpezite dicyclo metallic compound
1Connotation is identical, Z
2Be selected from-Cl ,-Br or-I; The general formula of monokaryon ring gold compound is:
4. the preparation method of heteronuclear porpezite dicyclo metallic compound as claimed in claim 3 is characterized in that, the mole of described monokaryon ring palladium compound, monokaryon ring gold compound and alkali is 1～2 ︰, 1 ︰ 1～5.
5. the preparation method of heteronuclear porpezite dicyclo metallic compound as claimed in claim 3 is characterized in that, described alkali is yellow soda ash, salt of wormwood, cesium carbonate, sodium phosphate or potassiumphosphate; Described organic solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF; Temperature of reaction is 80-120 ℃, and the reaction times is 12-48h, and reaction is carried out recrystallization with methylene dichloride to product after finishing.
6. the purposes of the described heteronuclear porpezite of claim 1 dicyclo metallic compound is characterized in that, described heteronuclear porpezite dicyclo metallic compound is used as bimetallic catalyst.
7. the purposes of heteronuclear porpezite dicyclo metallic compound as claimed in claim 6 is characterized in that, utilizes the adjacent N-of described heteronuclear porpezite dicyclo metallic compound catalysis to replace halogeno-benzene and alkyne reaction, synthetic 1,2-substituted indole; Described 1, the 2-substituted indole has following general formula:
R
3, R
4For-H ,-CH
3,-C
2H
3,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13Or aryl,
R
5=-CH
3,-C
2H
3,-C
3H
7,-C
l,-Br ,-F ,-CN ,-OCH
3,-COCH
3,-COCH
2CH
3The general formula that described adjacent N-replaces halogeno-benzene is
8. the purposes of heteronuclear porpezite dicyclo metallic compound as claimed in claim 7, it is characterized in that, described 1, the synthesis step of 2-substituted indole is: heteronuclear porpezite dicyclo metallic compound, adjacent N-are replaced halogeno-benzene, alkynes and alkali join in the organic solvent, reacted 12～48 hours at 80～120 ℃ under the protection of inert gas; Reaction is finished, and is down to room temperature, adds shrend and goes out, and use dichloromethane extraction, concentrates, namely gets product 1, the 2-substituted indole behind the purifying.
9. the purposes of heteronuclear porpezite dicyclo metallic compound as claimed in claim 8 is characterized in that, the mol ratio that described heteronuclear porpezite dicyclo metallic compound, adjacent N-replace halogeno-benzene, alkynes and alkali is 0.005～0.2 ︰, 1 ︰, 1～3 ︰ 1～6.
10. such as the purposes of heteronuclear porpezite dicyclo metallic compound as described in claim 8 or 9, it is characterized in that, described alkali is yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide, potassium hydroxide, potassium tert.-butoxide or sodium tert-butoxide; Described organic solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
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| CN111250692A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Heteronuclear bimetallic atom material stable in solution |
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| CN111250692A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Heteronuclear bimetallic atom material stable in solution |
| CN111250692B (en) * | 2018-11-30 | 2021-11-09 | 中国科学院大连化学物理研究所 | Heteronuclear bimetallic atom material stable in solution |
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