CN104402943A - 2-pyridyl benzimidazole palladium copper heteronuclear compound, preparation method and application thereof - Google Patents
2-pyridyl benzimidazole palladium copper heteronuclear compound, preparation method and application thereof Download PDFInfo
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- CN104402943A CN104402943A CN201410580427.3A CN201410580427A CN104402943A CN 104402943 A CN104402943 A CN 104402943A CN 201410580427 A CN201410580427 A CN 201410580427A CN 104402943 A CN104402943 A CN 104402943A
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Abstract
The invention relates to a 2-pyridyl benzimidazole palladium copper heteronuclear compound, the general formula of which is shown as the specification. Specifically, X is Cl<->, Br<-> or I<->; L is a tertiary phosphine ligand; P is a diphosphine ligand; R and R1 can be -H, -CH3, -C2H5 or -OCH3; and R is at any position of aromatic ring 7-10, and R1 is at any position of pyridine ring 3-5. The compound can serve as a bimetallic catalyst to catalyze the three-component reaction of 2-acetylpyridine, 2-amino halogenated benzylalcohol and arylboronic acid so as to synthesize a 2-pyridyl quinoline derivative.
Description
Technical field
The present invention relates to technical field of organic synthesis, be specifically related to 2-pyridyl benzoglyoxaline palladium copper and heterocaryotize compound and its preparation method and application.
Background technology
Organometallic Chemistry is organic chemistry and inorganic chemical cross discipline, and organometallics is used as reagent or catalyzer achieves huge achievement in Synthetic Organic Chemistry.The chemical reaction of present Catalyzed by Organometallic Compounds has been great chemical industry, pharmaceutical industry and fine chemical industry foundation stone.In numerous transition metal organometallic compounds, palladium compound with the catalytic performance of its brilliance in organic chemistry and Industrial Catalysis in occupation of critical role, be one of forward position of studying of chemist always.Even to this day, increasing Novel Palladium compound is synthesized out the requirement to adapt to differential responses, but heteronuclear ring palladium cuprous metal inactivators compound also rare report.In addition, quinoline and its derivates is a kind of important heterogeneous ring compound, is widely used in the industrial production such as medicine, healthcare products, agricultural chemicals.In recent years, on traditional synthetic route basis, having developed the novel method catalyzing and synthesizing quinoline with transition metal complex, avoided a large amount of uses of mineral acid, is current most study and a kind of the most promising method.For improving Atom economy and the combined coefficient of reaction, one kettle way multi-component reaction causes the broad interest of chemists.Multi-component reaction realizes multi-component superposition, 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.Our design and synthesis heteronuclear ring palladium cuprous metal inactivators compound, the reaction of catalysis 2-acetylpyridine, 2-amino halogen benzylalcohol and aryl boric acid, plays the catalysis characteristics of palladium, copper, prepares 2-pyridyl quinoline by one kettle way three components Reactive Synthesis.So far, also do not have 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound synthesis and react using it as Catalyzed by Pt/M Bimetallic Nano three components, the report of synthesis preparation 2-pyridyl quinoline.The method catalyst levels is little, has reaction conditions gentleness, and reaction substrate scope is wide, and the advantages such as productive rate is high, economical and efficient, have important using value.
Summary of the invention
The object of the invention is the deficiency for solving the problems of the technologies described above; a kind of 2-pyridyl benzoglyoxaline palladium copper is provided to heterocaryotize compound and its preparation method and application; this 2-pyridyl benzoglyoxaline palladium copper compound that heterocaryotizes can be used as the three components reaction of Catalyzed by Pt/M Bimetallic Nano 2-acetylpyridine, 2-amino halogen benzylalcohol and aryl boric acid, synthesis 2-pyridyl quinoline.
The present invention is the deficiency solved the problems of the technologies described above, and the technical scheme adopted is: a kind of 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound, and the general formula of this compound is:
，
Wherein X is Cl
-, Br
-or I
-; L is tertiary phosphine-ligand; P is biphosphine ligand; R, R
1for-H ,-CH
3,-C
2h or-OCH
3; R is any position on aromatic ring 7-10, R
1any position on pyridine ring 3-5.
Described L is the one in following tertiary phosphine-ligand:
Described P is the one in following biphosphine ligand:
,
or
(Ph=phenyl ring).
The preparation method that 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound, gets the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline and Li
2pdX
4with sodium-acetate reaction, reaction terminates rear filtration, the solid obtained and tertiary phosphine-ligand and reacts, and reacts to terminate rear evaporate to dryness and namely recrystallization obtains 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound;
Wherein, the general formula of the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline is:
, R, R
1, the R that P and described 2-pyridyl benzoglyoxaline palladium copper heterocaryotize in compound, R
1, P connotation is identical.
The cuprous diphosphine compound of described 2-pyridyl benzoglyoxaline, Li
2pdX
4, sodium-acetate and tertiary phosphine-ligand add-on mole be 1:1 ~ 1.5:1 ~ 1.5:1 ~ 1.5.
2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation method of compound, optimally: get the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline, Li
2pdX
4add in methyl alcohol with sodium-acetate, control temperature of reaction is 10-30 DEG C, carry out reaction 12-30h, reaction terminates rear filtration, add in methylene dichloride or acetone by the solid that tertiary phosphine-ligand and filtration obtain, control temperature of reaction is 10-30 DEG C, carries out reaction 1-6h, the mixed solvent that reaction terminates rear methylene dichloride/sherwood oil carries out recrystallization to product, obtains 2-pyridyl benzoglyoxaline palladium copper and to heterocaryotize compound.
2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the purposes of compound as bimetallic catalyst; be specially: react using the 2-pyridyl benzoglyoxaline palladium copper compound that heterocaryotizes as the three components of Catalyzed by Pt/M Bimetallic Nano 2-acetylpyridine, 2-amino halogen benzylalcohol and aryl boric acid, synthesis 2-pyridyl quinoline.
2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the purposes of compound as bimetallic catalyst; optimally: heterocaryotized by 2-pyridyl benzoglyoxaline palladium copper compound, 2-acetylpyridine, 2-amino halogen benzylalcohol, aryl boric acid and alkali join in solvent; under nitrogen protection, 80 ~ 160 DEG C are reacted 6 ~ 48 hours; after reaction terminates; be down to room temperature; add water to urge and go out, namely obtain 2-pyridyl quinoline product with after dichloromethane extraction, concentrated, purifying, drying.
The heterocaryotize add-on mol ratio of compound, 2-acetylpyridine, 2-amino halogen benzylalcohol, aryl boric acid and alkali of described 2-pyridyl benzoglyoxaline palladium copper is 0.01 ~ 0.2:1:1 ~ 2:1 ~ 3:2 ~ 6; Described alkali is sodium carbonate, salt of wormwood, cesium carbonate, sodium phosphate, sodium hydroxide or potassium hydroxide; Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
beneficial effect
(1), the present invention reacted by the ring palladiumization of the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline, and synthesis preparation 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound, provides a practical method for preparing Heteronuclear bimetallic complex; Heterocaryotize compound for Catalyzed by Pt/M Bimetallic Nano 2-acetylpyridine, 2-amino halogen benzylalcohol and aryl boric acid one kettle way are to prepare 2-pyridyl quinoline with 2-pyridyl benzoglyoxaline palladium copper.
(2), heteronuclear palladium copper compound catalyzer of the present invention is easy to synthesis, and catalyst levels is little, and catalytic reaction condition is gentle, and reaction substrate scope is wide, and the advantages such as productive rate is high, economical and efficient, have important using value.
Embodiment
2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound, and the general formula of this compound is:
，
Wherein X is Cl
-, Br
-or I
-; L is tertiary phosphine-ligand; P is biphosphine ligand; R, R
1for-H ,-CH
3,-C
2h or-OCH
3; R is any position on aromatic ring 7-10, R
1any position on pyridine ring 3-5.
Described L is the one in following tertiary phosphine-ligand:
Described P is the one in following biphosphine ligand:
,
or
(Ph=phenyl ring).
Concrete structure can be as follows:
embodiment 1:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (1)
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound A(1 mmol), Li
2pdCl
4(1 mmol), sodium-acetate (1 mmol), 10ml anhydrous methanol, filter after temperature 10 DEG C, stirring reaction liquid 12h.Gained solid joins in 10ml flask, then adds triphenylphosphine (1 mmol) and 5ml methylene dichloride successively after drying, at 20 DEG C after stirring reaction liquid 1h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 1, productive rate is 86%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.71 (d, 1H), 7.93 (d, 1H), 7.81 (d, 2H), 7.57-7.63 (m, 21H), 7.26-7.35 (m, 17H), 1.83 (t, 4H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound A is as follows:
。
embodiment 2:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (3):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound B(1 mmol), Li
2pdBr
4(1.2 mmol), sodium-acetate (1.1 mmol), 12ml anhydrous methanol, filter after temperature 20 DEG C, stirring reaction liquid 20h.Gained solid joins in 10ml flask, then adds triphenylphosphine (1.2 mmol) and 5ml methylene dichloride successively after drying, at 30 DEG C after stirring reaction liquid 3h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 3, productive rate is 88%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.70 (d, 1H), 7.91 (d, 1H), 7.78 (d, 2H), 7.53-7.61 (m, 21H), 7.24-7.33 (m, 16H), 2.48 (s, 3H), 1.81 (t, 4H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound B is as follows:
。
embodiment 3:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (6):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound C(1 mmol), Li
2pdCl
4(1.5 mmol), sodium-acetate (1.5 mmol), 15ml anhydrous methanol, filter after temperature 30 DEG C, stirring reaction liquid 30h.Gained solid joins in 10ml flask, then adds trimethyl-phosphine (1.3 mmol) and 5ml acetone successively, at 15 DEG C after stirring reaction liquid 6h, steam solvent after drying, and with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 6, productive rate is 85%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.75 (d, 1H), 7.87 (d, 1H), 7.73 (d, 2H), 7.50-7.59 (m, 12H), 7.20-7.34 (m, 8H), 3.85 (s, 3H), 1.80 (t, 4H), 0.98 (s, 9H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound C is as follows:
。
embodiment 4:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (8):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound D(1 mmol), Li
2pdI
4(1.1 mmol), sodium-acetate (1.1 mmol), 11ml anhydrous methanol, filter after temperature 18 DEG C, stirring reaction liquid 24h.Gained solid joins in 10ml flask, then adds trimethyl-phosphine (1.4 mmol) and 5ml acetone successively, at 22 DEG C after stirring reaction liquid 2h, steam solvent after drying, and with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 8, productive rate is 89%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.52 (s, 1H), 7.75 (s, 1H), 7.60 (s, 2H), 7.43-7.51 (m, 12H), 7.16-7.28 (m, 9H), 2.57 (q, 3H), 2.46 (s, 3H), 1.82 (t, 4H), 1.23 (t, 3H), 0.96 (s, 9H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound D is as follows:
。
embodiment 5:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (10):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound E(1 mmol), Li
2pdCl
4(1.2 mmol), sodium-acetate (1.2 mmol), 12ml anhydrous methanol, filter after temperature 25 DEG C, stirring reaction liquid 20h.Gained solid joins in 10ml flask, then adds triphenylphosphine (1.2 mmol) and 5ml acetone successively after drying, at 20 DEG C after stirring reaction liquid 5h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 10, productive rate is 80%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.82 (d, 1H), 7.96 (d, 1H), 7.84 (d, 2H), 7.58-7.69 (m, 16H), 7.25-7.38 (m, 26H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound E is as follows:
。
embodiment 6:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (12):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound F(1 mmol), Li
2pdCl
4(1.3 mmol), sodium-acetate (1.5 mmol), 13ml anhydrous methanol, filter after temperature 22 DEG C, stirring reaction liquid 30h.Gained solid joins in 10ml flask, then adds tri isopropyl phosphine (1.3 mmol) and 5ml methylene dichloride successively after drying, at 10 DEG C after stirring reaction liquid 4h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 12, productive rate is 87%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.76 (d, 1H), 7.93 (d, 1H), 7.82 (d, 2H), 7.53-7.61 (m, 8H), 7.22-7.34 (m, 14H), 2.48 (s, 3H), 1.39 (m, 3H), 1.12 (d, 18H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound F is as follows:
。
embodiment 7:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (15):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound G(1 mmol), Li
2pdCl
4(1.1 mmol), sodium-acetate (1.2 mmol), 10ml anhydrous methanol, filter after temperature 15 DEG C, stirring reaction liquid 15h.Gained solid joins in 10ml flask, then adds three cyclohexyl phosphines (1.3 mmol) and 5ml methylene dichloride successively after drying, at 20 DEG C after stirring reaction liquid 3h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 15, productive rate is 85%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.73 (s, 1H), 7.93 (d, 1H), 7.78 (s, 2H), 7.50-7.62 (m, 10H), 7.23-7.37 (m, 16H), 3.84 (s, 3H), 2.39 (s, 3H), 1.18-1.65 (m, 30H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound G is as follows:
。
embodiment 8:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (16):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound H(1 mmol), Li
2pdCl
4(1.2 mmol), sodium-acetate (1.5 mmol), 10ml anhydrous methanol, filter after temperature 20 DEG C, stirring reaction liquid 22h.Gained solid joins in 10ml flask, then adds biphenyl-2-cyclohexyl phosphine (1.2 mmol) and 5ml methylene dichloride successively after drying, at 30 DEG C after stirring reaction liquid 6h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 16, productive rate is 82%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.77 (s, 1H), 7.95 (s, 1H), 7.71 (s, 1H), 7.50-7.62 (m, 12H), 7.23-7.37 (m, 24H), 2.47 (s, 3H), 2.42 (s, 2H), 1.20-1.69 (m, 20H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound H is as follows:
。
embodiment 9:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (19):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound I(1 mmol), Li
2pdCl
4(1.4 mmol), sodium-acetate (1.5 mmol), 10ml anhydrous methanol, filter after temperature 26 DEG C, stirring reaction liquid 26h.Gained solid joins in 10ml flask, then adds triphenylphosphine (1.3 mmol) and 5ml methylene dichloride successively after drying, at 25 DEG C after stirring reaction liquid 5h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 19, productive rate is 83%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=8.86 (d, 1H), 7.99 (d, 1H), 7.72 (s, 2H), 7.50-7.67 (m, 18H), 7.28-7.45 (m, 28H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound I is as follows:
。
embodiment 10:2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation of compound (21):
In 25ml flask, add 2-pyridyl benzoglyoxaline cuprous diphosphine compound J(1 mmol), Li
2pdCl
4(1.2 mmol), sodium-acetate (1.4 mmol), 10ml anhydrous methanol, filter after temperature 23 DEG C, stirring reaction liquid 24h.After gained solid is dried, join in 10ml flask, add 2 ' successively again, 4 ', 6 '-tri isopropyl biphenyl-2-cyclohexyl phosphine (1.2 mmol) and 5ml acetone, at 25 DEG C after stirring reaction liquid 3h, steam solvent, with the mixed solvent recrystallization of methylene dichloride and sherwood oil, obtain product 21, productive rate is 85%.Carry out nuclear magnetic resonance spectroscopy to products obtained therefrom, data are as follows: 1H NMR: δ=7.76 (d, 2H), 7.47-7.60 (m, 16H), 7.23-7.37 (m, 22H), 3.26 (m, 3H), 2.49 (s, 3H), 2.40 (s, 2H), 1.21-1.73 (m, 38H).
The structural formula of described 2-pyridyl benzoglyoxaline cuprous diphosphine compound J is as follows:
。
the synthesis of embodiment 11:2-pyridyl-6-phenylquinoline:
In the flask of 10 ml, add 0.01mmol 2-pyridyl benzoglyoxaline palladium copper to heterocaryotize compound
(1), 1mmol 2-acetylpyridine, 1mmol 2-amino-6-bromobenzyl alcohol, 1mmol phenylo boric acid, 2mmol salt of wormwood and 3ml dioxane, be heated to 110 DEG C with 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-6-phenylquinoline, productive rate is 82%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.72 (d, 1H), 8.62 (d, 1H), 8.59 (d, 1H), 8.30 (d, 1H), 8.18 (d, 1H), 7.92-7.95 (m, 2H), 7.85 (t, 1H), 7.66 (d, 2H), 7.57-7.63 (m, 2H), 7.29-7.33 (m, 2H).
2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the purposes of compound as bimetallic catalyst: heterocaryotized by 2-pyridyl benzoglyoxaline palladium copper compound, 2-acetylpyridine, 2-amino halogen benzylalcohol, aryl boric acid and alkali join in solvent; under nitrogen protection, 80 ~ 160 DEG C are reacted 6 ~ 48 hours; after reaction terminates; be down to room temperature; add water to urge and go out; namely 2-pyridyl quinoline product is obtained, described reaction scheme with after dichloromethane extraction, concentrated, purifying, drying:
；
The general formula of described 2-pyridyl quinoline is:
, Aryl can on quinoline ring 1-4 any position.
The general formula of described 2-amino halogen benzylalcohol is:
, X is Cl
-, Br
-, I
-, can on phenyl ring 1-4 any position.
The general formula of described aryl boric acid is:
, Aryl is identical with the Aryl connotation in described 2-pyridyl quinoline.
the synthesis of embodiment 12:2-pyridyl-6-p-methoxyphenyl quinoline
In the flask of 10 ml, add 0.05mmol 2-pyridyl benzoglyoxaline palladium copper to heterocaryotize compound
(3), 1mmol 2-acetylpyridine, 1.2mmol 2-amino-6-iodine benzylalcohol, 1.5mmol to the toluene of methoxyphenylboronic acid, 3mmol sodium carbonate and 3ml, be heated to 80 DEG C with oil bath under magnetic stirring, reaction backflow 6 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-6-p-methoxyphenyl quinoline, productive rate is 90%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.75 (d, 1H), 8.66 (d, 1H), 8.57 (d, 1H), 8.31 (d, 1H), 8.21 (d, 1H), 7.97-7.99 (m, 2H), 7.90 (t, 1H), 7.69 (d, 2H), 7.36-7.38 (m, 2H), 7.04 (d, 2H), 3.89 (s, 3H).
the synthesis of embodiment 13:2-pyridyl-5-p-methylphenyl quinoline
In the flask of 10 ml, add 0.08mmol 2-pyridyl benzoglyoxaline palladium copper to heterocaryotize compound
(6), 1mmol 2-acetylpyridine, 1.5mmol 2-amino-5-bromobenzyl alcohol, 3mmol to the dioxane of methylphenylboronic acid, 6mmol cesium carbonate and 3ml, be heated to 110 DEG C with 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-5-p-methylphenyl quinoline, productive rate is 92%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.77 (d, 1H), 8.65 (d, 1H), 8.56 (d, 1H), 8.32 (d, 1H), 8.21 (d, 1H), 8.00-8.04 (m, 2H), 7.90-7.94 (m, 1H), 7.65 (d, 2H), 7.42-7.47 (m, 1H), 7.37 (d, 2H), 2.46 (s, 3H).
embodiment 14:2-pyridyl-7-is to the synthesis of ethylphenyl quinoline
Add in the flask of 10 ml 0.2mmol 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound (
9), 1mmol 2-acetylpyridine, 1.5mmol 2-amino-7-chlorobenzyl alcohol, 2mmol to the DMF of ethylbenzene boric acid, 6mmol cesium carbonate and 3ml, be heated to 160 DEG C with 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-7-to ethylphenyl quinoline, productive rate is 83%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.78 (d, 1H), 8.63 (d, 1H), 8.58 (d, 1H), 8.30 (d, 1H), 8.22 (d, 1H), 8.02-8.06 (m, 2H), 7.91-7.95 (m, 1H), 7.68 (d, 2H), 7.45-7.49 (m, 1H), 7.39 (d, 2H), 2.58 (q, 3H), 1.24 (t, 3H).
the synthesis of embodiment 15:2-pyridyl-8-(2-pyridyl) quinoline
Add in the flask of 10 ml 0.06mmol 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound (
12), the tetrahydrofuran (THF) of 1mmol 2-acetylpyridine, 1.2mmol 2-amino-8-bromobenzyl alcohol, 2mmol 2-pyridine boronic acid, 6mmol sodium phosphate and 3ml, be heated to 80 DEG C with 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-8-(2-pyridyl) quinoline, productive rate is 85%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.85 (d, 1H), 8.79 (d, 1H), 8.67 (d, 1H), 8.57 (d, 1H), 8.26 (d, 1H), 8.00-8.07 (m, 2H), 7.95 (m, 1H), 7.66 (d, 2H), 7.45-7.50 (m, 1H), 7.35 (d, 2H).
the synthesis of embodiment 16:2-pyridyl-5-(2-furyl) quinoline
Add in the flask of 10 ml 0.12mmol 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound (
15), the benzene of 1mmol 2-acetylpyridine, 1.4mmol 2-amino-5-chlorobenzyl alcohol, 2.5mmol 2-furan boronic acid, 5mmol sodium hydroxide and 3ml, be heated to 100 DEG C with 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-5-(2-furyl) quinoline, productive rate is 78%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.75 (d, 1H), 8.62 (d, 1H), 8.53 (d, 1H), 8.30 (d, 1H), 8.20 (d, 1H), 8.07 (m, 1H), 7.90-7.94 (m, 1H), 7.65 (d, 1H), 7.46 (d, 1H), 7.37 (d, 1H), 6.43 (d, 2H).
the synthesis of embodiment 17:2-pyridyl-6-(1-naphthyl) quinoline
Add in the flask of 10 ml 0.10mmol 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound (
17), the dioxane of 1mmol 2-acetylpyridine, 1.2mmol 2-amino-6-iodine benzylalcohol, 2.6mmol 1-naphthalenylboronic acid, 5mmol potassium hydroxide and 3ml, be heated to 110 DEG C with oil bath under magnetic stirring, reaction backflow 20 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain the synthesis of straight product 2-pyridyl-6-(1-naphthyl) quinoline, productive rate is 84%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.71 (d, 1H), 8.63 (d, 1H), 8.58 (d, 1H), 8.32 (d, 1H), 8.19 (d, 1H), 7.93-7.96 (m, 2H), 7.68-7.80 (d, 4H), 7.55-7.66 (m, 3H), 7.32-7.37 (m, 2H).
the synthesis of embodiment 18:2-pyridyl-6-(3-aminomethyl phenyl) quinoline
Add in the flask of 10 ml 0.16mmol 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound (
19), the benzene of 1mmol 2-acetylpyridine, 1.1mmol 2-amino-6-chlorobenzyl alcohol, 2.2mmol 2-methylphenylboronic acid, 5mmol cesium carbonate and 3ml, be heated to 100 DEG C with oil bath under magnetic stirring, reaction backflow 16 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-6-(3-aminomethyl phenyl) quinoline, productive rate is 88%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.78 (d, 1H), 8.68 (d, 1H), 8.59 (d, 1H), 8.34 (d, 1H), 8.25 (d, 1H), 8.01-8.06 (m, 2H), 7.91-7.96 (m, 1H), 7.67 (d, 2H), 7.40-7.44 (m, 1H), 7.34 (d, 2H), 2.45 (s, 3H).
the synthesis of embodiment 19:2-pyridyl-7-(2-thienyl) quinoline
Add in the flask of 10 ml 0.15mmol 2-pyridyl benzoglyoxaline palladium copper heterocaryotize compound (
21), the toluene of 1mmol 2-acetylpyridine, 1.5mmol 2-amino-7-bromobenzyl alcohol, 3mmol 2-thienyl boric acid, 5mmol salt of wormwood and 3ml, be heated to 110 DEG C with 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 methylene dichloride as developping agent, and be separated with silica gel thin-layer chromatography, obtain straight product 2-pyridyl-7-(2-thienyl) quinoline, productive rate is 75%.The nmr analysis data of this compound are as follows:
1h NMR: δ=8.72 (d, 1H), 8.60 (d, 1H), 8.47 (d, 1H), 8.26 (d, 1H), 8.17 (d, 1H), 8.02 (m, 1H), 7.82-7.87 (m, 1H), 7.61 (d, 1H), 7.40 (d, 1H), 7.31 (d, 1H), 7.07 (m, 2H).
Claims (9)
1.2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound, it is characterized in that: the general formula of this compound is:
，
Wherein X is Cl
-, Br
-or I
-; L is tertiary phosphine-ligand; P is biphosphine ligand; R, R
1for-H ,-CH
3,-C
2h
5or-OCH
3;r is any position on aromatic ring 7-10, R
1any position on pyridine ring 3-5.
2. 2-pyridyl benzoglyoxaline palladium copper as claimed in claim 1 heterocaryotizes compound, it is characterized in that: described L is the one in following tertiary phosphine-ligand:
Described P is the one in following biphosphine ligand:
,
or
, wherein Ph represents phenyl ring.
3. 2-pyridyl benzoglyoxaline palladium copper as claimed in claim 1 or 2 heterocaryotizes the preparation method of compound, it is characterized in that: get the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline and Li
2pdX
4with sodium-acetate reaction, reaction terminates rear filtration, the solid obtained and tertiary phosphine-ligand and reacts, and reacts to terminate rear evaporate to dryness and namely recrystallization obtains 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes compound;
Wherein, the general formula of the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline is:
, R, R
1, the R that P and described 2-pyridyl benzoglyoxaline palladium copper heterocaryotize in compound, R
1, P connotation is identical.
4. 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation method of compound as claimed in claim 3, it is characterized in that: the cuprous diphosphine compound of described 2-pyridyl benzoglyoxaline, Li
2pdX
4, sodium-acetate and tertiary phosphine-ligand add-on mole be 1:1 ~ 1.5:1 ~ 1.5:1 ~ 1.5.
5. 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the preparation method of compound as claimed in claim 3, it is characterized in that: get the cuprous diphosphine compound of 2-pyridyl benzoglyoxaline, Li
2pdX
4add in methyl alcohol with sodium-acetate, control temperature of reaction is 10-30 DEG C, carry out reaction 12-30h, reaction terminates rear filtration, add in methylene dichloride or acetone by the solid that tertiary phosphine-ligand and filtration obtain, control temperature of reaction is 10-30 DEG C, carries out reaction 1-6h, the mixed solvent that reaction terminates rear methylene dichloride/sherwood oil carries out recrystallization to product, obtains 2-pyridyl benzoglyoxaline palladium copper and to heterocaryotize compound.
6. 2-pyridyl benzoglyoxaline palladium copper as claimed in claim 1 heterocaryotizes the purposes of compound as bimetallic catalyst.
7. 2-pyridyl benzoglyoxaline palladium copper as claimed in claim 6 heterocaryotizes the purposes of compound as bimetallic catalyst; it is characterized in that: react using the 2-pyridyl benzoglyoxaline palladium copper compound that heterocaryotizes as the three components of Catalyzed by Pt/M Bimetallic Nano 2-acetylpyridine, 2-amino halogen benzylalcohol and aryl boric acid, synthesis 2-pyridyl quinoline.
8. 2-pyridyl benzoglyoxaline palladium copper as claimed in claim 7 heterocaryotizes the purposes of compound as bimetallic catalyst; it is characterized in that: heterocaryotized by 2-pyridyl benzoglyoxaline palladium copper compound, 2-acetylpyridine, 2-amino halogen benzylalcohol, aryl boric acid and alkali join in solvent; under nitrogen protection, 80 ~ 160 DEG C are reacted 6 ~ 48 hours; after reaction terminates; be down to room temperature; add water to urge and go out, namely obtain 2-pyridyl quinoline product with after dichloromethane extraction, concentrated, purifying, drying.
9. as claimed in claim 7 or 8 2-pyridyl benzoglyoxaline palladium copper heterocaryotizes the purposes of compound as bimetallic catalyst, it is characterized in that: the heterocaryotize add-on mol ratio of compound, 2-acetylpyridine, 2-amino halogen benzylalcohol, aryl boric acid and alkali of described 2-pyridyl benzoglyoxaline palladium copper is 0.01 ~ 0.2:1:1 ~ 2:1 ~ 3:2 ~ 6; Described alkali is sodium carbonate, salt of wormwood, cesium carbonate, sodium phosphate, sodium hydroxide or potassium hydroxide; Described solvent is dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.
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| CN108148097A (en) * | 2018-03-07 | 2018-06-12 | 沈阳药科大学 | Benzimidazoles compound cobalt complex and its application containing pyridine |
| CN108218925A (en) * | 2018-03-07 | 2018-06-29 | 沈阳药科大学 | Imidazopyridine compound cobalt complex and its application |
| CN109320530A (en) * | 2018-11-09 | 2019-02-12 | 湖北大学 | High efficiency blue cuprous halide complex and its synthetic method and application containing thioxene double phosphines and triphenylphosphine ligand |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148097A (en) * | 2018-03-07 | 2018-06-12 | 沈阳药科大学 | Benzimidazoles compound cobalt complex and its application containing pyridine |
| CN108218925A (en) * | 2018-03-07 | 2018-06-29 | 沈阳药科大学 | Imidazopyridine compound cobalt complex and its application |
| CN108218925B (en) * | 2018-03-07 | 2020-05-01 | 沈阳药科大学 | Cobalt complex of imidazopyridine compound and application thereof |
| CN109320530A (en) * | 2018-11-09 | 2019-02-12 | 湖北大学 | High efficiency blue cuprous halide complex and its synthetic method and application containing thioxene double phosphines and triphenylphosphine ligand |
| CN109320530B (en) * | 2018-11-09 | 2020-12-08 | 湖北大学 | High-efficiency blue light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and synthetic method and application thereof |
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