CN103788130B - A kind of synthetic method of diphenylphosphine imidazoles of novel phosphorus-containing organic ligand 1 (9 anthryl) 2 and application - Google Patents
A kind of synthetic method of diphenylphosphine imidazoles of novel phosphorus-containing organic ligand 1 (9 anthryl) 2 and application Download PDFInfo
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Abstract
1 (9 anthryl) 2 diphenylphosphine imidazoles (L) is a kind of phosphorous nitrogen phosphine bidentate ligand containing imidazoles, and it easily can react one-step synthesis by the deprotonation of anthryl imidazoles and then with diphenyl phosphine chloride.The part is convieniently synthesized, and normal temperature condition presence stable in the air can realize large-scale industrial production.The part (L) and palladium chloride situ catalytic Sonogashira cross-coupling reactions, have good reactivity to aryl iodide and aryl bromide.The catalyst inherits the advantages of traditional phosphine catalyst dosage is few, overcomes the shortcomings that aryl bromide hardly possible is reacted.Reaction carries out making alkali using cesium carbonate in acetonitrile system, and catalyst amount is small, reaction condition is gentle, the reaction time is short, convenient post-treatment, has important application in the synthesis of important industrial chemicals arylalkyne, there is very big application prospect in the industrial production.
Description
【Technical field】
The present invention relates to the preparation of the catalyst ligand for cross-coupling reaction, particularly a kind of phosphorous organic ligand 1-
The synthetic method of (9- anthryls) -2- diphenylphosphines-imidazoles (L) and its application, category methodology of organic synthesis field.
【Background technology】
The halogenated aryl hydrocarbon coupling reaction of palladium chtalyst provides substantial amounts of possibility for chemical synthesis, from the 1970s not
Same industrial process is set up according to such reaction.It is extensive that the advantage of these coupling reactions is that Pd catalysis has to substrate
Tolerance, reaction yield is higher.In order to more produce this kind of reactive applications in chemical industry, large scale experiment is realized
Synthesis, the cost of experiment must be reduced largely.It is badly in need of available part that will be cheap during this, this part needs to urge
Change such reaction and can enough easily to synthesize.
The transition metal complex of Phosphine ligands can be as the catalyst precarsor or catalyst of many important reactions, especially
The unique high catalytic activity of trivalent Phosphine ligands metal complex, is favored, such as be applied to catalysis by people always
Sonogashira reactions, Heck reactions, Suzuki reactions etc..In Phosphine ligands introduce nitrogen-atoms with multiple coordination sites,
Coordination mode complicated and changeable and regulatable molecular shape change, can assemble to obtain with transition metal ions many structures it is novel,
There is the metal complex of unique function, there is the great potential applied to catalytic reaction.
Therefore, we, which design, has synthesized 1- (9- anthryls) -2- diphenylphosphines-part of the imidazoles (L) as palladium-catalyzed reaction,
Not only the nitrogen containing trivalent phosphine list of coordination units but also comprising regulatory molecule and assembled metal is former in the compound that we report first
Sub and big π systems.By anthryl imidazoles deprotonation, then reacted with diphenyl phosphine chloride, you can easily prepare the part.
Because the production of the part is simple, raw material is easy to get, therefore it is especially suitable for largely producing in the industry.
Arylalkyne is a kind of important reaction intermediate, and the synthesis of arylalkyne has great importance.At present, arylalkyne
Primary synthetic methods are reacted using Sonogashira, and phosphine/palladium catalyst is the custom catalystses of Sonogashira reactions.We
The reactivity of the part of our designs is monitored using Sonogashira reactions as template reaction, it is desired to be able to which what is obtained is anti-
Answer effect.
【The content of the invention】
The invention provides a kind of synthesis side of new phosphorous organic ligand 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L)
Method, part synthesis is simple, and raw material is easy to get, and part presence stable in the air, is adapted to industrialized production.It is organic using this
Phosphine nitrogen ligand/PdCl2Situ catalytic Sonogashira cross-coupling reactions, the catalyst system and catalyzing for aryl iodide, aryl bromide it is anti-
Should be active very high, reaction system is simple, convenient post-treatment.
Technical scheme：
A kind of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L), it is characterised in that be that a kind of phosphorous nitrogen phosphine containing imidazoles is double
Tooth part, containing strong coordination atom phosphorus atoms, there is big steric hindrance and produce the big common of weak interaction for metal and aromatic hydrocarbons
Yoke system, its structure are as follows：
The synthetic method of 1- (9- the anthryls) -2- diphenylphosphines-imidazoles (L), it is characterised in that following steps：
(1) preparation of intermediate N (9- anthryls) imidazoles
1) under zero degrees celsius, hydrobromic acid is added into the dichloromethane solution of anthracene, is slowly dropped into hydrogen peroxide, is added dropwise to complete
Afterwards, room temperature is warming up to, reacts 12h.Reaction solution is washed, and organic layer is dry, is spin-dried for, and is dissolved with a certain amount of dioxane, filters, filter
Liquid concentrates, and adds methanol to separate out light yellow solid 9- bromine anthracenes.
2) under nitrogen protection, 9- bromines anthracene, imidazoles, cuprous iodide, potassium carbonate, KI is added in DMSO, are warming up to 130
Degree Celsius reaction 24 hours.Reaction is cooled to room temperature after terminating, and reaction solution is poured into water and extracted with dichloromethane, filters,
Filtrate liquid separation, filter residue refilter after being dissolved with methanol/dichloro, filtrate and last time filter it is organic mix, be spin-dried for, mistake post separation
Obtain yellow solid 9- imidazoles anthracenes.
(2) preparation of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L)
Under nitrogen protection, compound 9- imidazoles anthracenes are dissolved in tetrahydrofuran, subzero -78 DEG C is cooled to, positive fourth is added dropwise
Base lithium, insulation reaction 3h, diphenyl phosphine chloride is added dropwise, insulation then heats to room temperature reaction 12h for 1 hour, after the completion of reaction, uses
Ammonium chloride is quenched, and is spin-dried under the protection of reaction solution nitrogen, with dichloro, recrystallizing methanol, obtains white solid 1- (9- anthryls) -2- hexichol
Base phosphine-imidazoles (L).
Described anthracene, hydrobromic acid, hydrogen peroxide, the mol ratio of dichloromethane are 1: 1-2: 1-20: 20-200
Described 9- bromines anthracene, imidazoles, cuprous iodide, potassium carbonate, KI, the mol ratio of dimethyl sulfoxide (DMSO) are 1: 1-6:
0.1-3∶1-20∶0.5-3∶20-200
Described 9- imidazoles anthracene, n-BuLi, diphenyl phosphine chloride, the mol ratio of tetrahydrofuran are 1: 1-3: 1-3: 20-
200
The application of described 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L), it is characterised in that：
Phosphine nitrogen ligand 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) situ catalytic Sonogashira cross-coupling reactions,
Form alkynes coupled product.Method is：Acetonitrile is solvent under inert gas shielding, with 1- (9- anthryls) -2- diphenylphosphines-imidazoles
(L)/PdCl2As catalyst, cesium carbonate makees alkali, halogenated aryl hydrocarbon, is reacted 3 hours at 70 DEG C of phenylacetylene, TLC detections, reaction knot
Room temperature is cooled to after beam, column chromatography for separation, obtains product.
Described halogenated aryl hydrocarbon be an aryl bromide, an iodo aromatic hydrocarbon, to methoxyl group iodo aromatic hydrocarbon, to nitro iodo aromatic hydrocarbon
Deng
By this research, we simply can largely synthesize 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L), for coupling
Reaction industryization provides available part.
【Brief description of the drawings】
Fig. 1 is phosphine nitrogen ligand 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) synthetic route
Fig. 2 is ligand 1-(9- anthryls)-2- diphenylphosphines-imidazoles (L)31P NMR spectras
Fig. 3 is ligand 1-(9- anthryls)-2- diphenylphosphines-imidazoles (L)1H NMR spectras
Fig. 4 is ligand 1-(9- anthryls)-2- diphenylphosphines-imidazoles (L)13C NMR spectras
【Specific embodiment】
It will be helpful to understand the present invention by following embodiments, but be not intended to limit present disclosure.
Embodiment 1：
Thermometer is loaded onto in 500ml three neck round bottom flask, adds 8.9g (50mmol) anthracene, 200ml dichloromethane, cooling
40% hydrobromic acid aqueous solution 17.6ml (60mmol) is added to zero degrees celsius, after stirring, 5ml is added dropwise in 15min
(50mmol) hydrogen peroxide (30%), is incubated 30min after being added dropwise, then heats to and 12h is stirred at room temperature.Reaction solution through washing,
It is spin-dried for after drying, adds 60ml dioxane, filtering in solids, filtrate concentration adds methanol and separates out light yellow solid 9- bromines
Anthracene, 11.6g, yield 91%.1H NMR(400MHz,CDCl3) δ 8.52 (d, J=8.9Hz, 2H, Ar-H), 8.44 (s, 1H, Ar-
H), 8.00 (d, J=8.4Hz, 2H, Ar-H), 7.60 (t, J=7.5Hz, 2H, Ar-H), 7.50 (t, J=7.5Hz, 2H, Ar-H)
Embodiment 2
In tri- mouthfuls of round bottoms of 250ml burn, nitrogen protection is lower to add 4.32g (17mmol) 9- bromine anthracenes, imidazoles 2.72g
(40mmol), potassium carbonate 5.52g (40mmol), cupric iodide 0.7g (3.7mmol), KI 2.82g (17mmol), add
80ml dimethyl sulfoxides, reaction are heated to 130 degrees Celsius under nitrogen protection, react 24 hours, and reaction is cooled to room temperature after terminating,
Reaction solution is poured into 200ml water and extracted with dichloromethane, is filtered, filtrate liquid separation, filter residue dissolved with methanol/dichloro after after
Filter, filtrate and last time filter it is organic mix, be spin-dried for, mistake post separation obtains yellow solid 9- imidazoles anthracene 3.6g, yield 87%.1H
NMR (400MHz, CDCl3) δ 8.61 (s, 1H, Ar-H), 8.09 (d, J=8.1Hz, 2H, Ar-H), 7.80 (s, 1H,
Imidazole-H), 7.62-7.41 (m, 7H, Ar-H, imidazole-H), 7.29 (s, 1H, imidazole-H)
Embodiment 3
In 100ml there-necked flasks, 1.22g9- imidazoles anthracene (5mmol) is added, 40ml tetrahydrofurans, it is Celsius to be cooled to -78
Degree, 2.5M n-BuLis 2.2ml (5.5mmol) is added dropwise, n-BuLi is added dropwise, insulation reaction 3h, diphenyl phosphorus chloride is added dropwise
1.22g (5.5mmol), insulation then heat to room temperature reaction 12h for 1 hour, after the completion of reaction, are quenched with ammonium chloride, reaction solution
It is spin-dried under nitrogen protection, with dichloro, recrystallizing methanol, obtains white solid N- aryl -2- diphenylphosphine imidazoles 1.6g, yield
76%.1H NMR(400MHz,CDCl3) δ 8.57 (s, 1H, Ar-H), 8.02 (d, J=8.5Hz, 2H, Ar-H), 7.65 (s, 1H,
Imidazole-H), 7.46-7.39 (m, 2H, Ar-H), 7.31 (m, 8H, Ar-H), 7.22 (t, J=4.7Hz, 5H, Ar-H,
Imidazole-H), 7.15 (d, J=8.8Hz, 2H, Ar-H)31P NMR(162MHz,CDCl3)δ-31.38.
13C NMR (101MHz, CDCl3) δ 149.80 (d, J=7.1Hz), 135.35 (d, J=4.9Hz), 133.79 (d, J=
20.9Hz), 132.03 (s), 131.16 (s), 129.35 (d, J=1.6Hz), 129.15 (s), 128.84 (s), 128.78 (s),
128.36 (s), 128.26 (d, J=7.6Hz), 127.29 (s)
Phosphine nitrogen ligand 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L)/palladium chloride situ catalytic Sonogashira intersects
Coupling reaction, form carbon-to-carbon alkynes coupled product.Method is：Acetonitrile (2ml) is solvent under inert gas shielding, with N- anthryls-
2- diphenylphosphines imidazoles/PdCl2As catalyst, cesium carbonate (1.2mmol) makees alkali, halogenated aryl hydrocarbon (0.5mmol), phenylacetylene
Reacted 3 hours at 70 DEG C of (0.6mmol), TLC detections, reaction is cooled to room temperature after terminating, column chromatography for separation, obtains product.
Process conditions are：0.5mmol halogeno-benzenes, 0.6mmol phenylacetylenes, 1.2mmol alkali, 1mol%Pd (II), 1mol%
Ligand L, 70 DEG C of reaction 4h
The reactivity that 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L)/palladium chloride is reacted Sonogashira
1- (9- anthryls) -2- diphenylphosphines-imidazoles (L)/palladium chloride has reaction well to live Sonogashira reactions
Property and substrate applicability, 90% yield are basically reached to iodo aromatic hydrocarbon yield, aryl bromide can also reach good yield.1-
(9- anthryls) -2- diphenylphosphines-imidazoles (L)/palladium chloride catalytic reaction condition is gentle, post processing is easy, reaction yield is high, fits
Close industrialization demand.New novel phosphorus-containing organic ligand 1- (9- the anthryls) -2- diphenylphosphines-imidazoles, it is coupling reaction industry
Change provides a kind of synthesis easily optional part, possesses huge business potential in the development of chemical industry in future.
Claims (6)
1. a kind of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L), it is characterised in that be a kind of phosphorous nitrogen phosphine bidentate containing imidazoles
Part, containing strong coordination atom phosphorus atoms, there is big steric hindrance and produce the big conjugation of weak interaction with aromatic hydrocarbons for metal
System, its structure are as follows：
2. a kind of synthetic method of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) as claimed in claim 1, it is characterised in that such as
Lower step：
(1) preparation of intermediate N (9- anthryls) imidazoles
At (1) 0 DEG C, hydrobromic acid is added into the dichloromethane solution of anthracene, is slowly dropped into hydrogen peroxide, after being added dropwise to complete, be warming up to
Room temperature, react 12h；Reaction solution is washed, and organic layer is dry, is spin-dried for, and is dissolved with dioxane, filters, and filtrate concentration, adds methanol to analyse
Go out light yellow solid 9- bromine anthracenes；
(2) under nitrogen protection, 9- bromines anthracene, imidazoles, cuprous iodide, potassium carbonate, KI is added in DMSO, are warming up to 130 DEG C
React 24h；Reaction is cooled to room temperature after terminating, and reaction solution is poured into water and extracted with dichloromethane, filters, filtrate liquid separation,
Filter residue with being refiltered after methanol and dichloromethane dissolving, filtrate and last time filter it is organic mix, be spin-dried for, mistake post separation obtains yellow
Color solid 9- imidazoles anthracenes；
(2) preparation of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L)
Under nitrogen protection, compound 9- imidazoles anthracenes are dissolved in tetrahydrofuran, are cooled to -78 DEG C, n-BuLi, insulation is added dropwise
3h is reacted, diphenyl phosphorus chloride is added dropwise, insulation 1h then heats to room temperature reaction 12h, after the completion of reaction, is quenched with ammonium chloride,
It is spin-dried under the protection of reaction solution nitrogen, with dichloromethane, recrystallizing methanol, obtains white solid 1- (9- anthryls) -2- diphenylphosphines-miaow
Azoles (L).
3. 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) synthetic method as claimed in claim 2, it is characterised in that：It is described
9- bromines anthracene, imidazoles, cuprous iodide, potassium carbonate, KI, dimethyl sulfoxide (DMSO) mol ratio be 1: 1-6: 0.1-3: 1-20:
0.5-3∶20-200。
4. 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) synthetic method as claimed in claim 2, it is characterised in that：It is described
9- imidazoles anthracene, n-BuLi, diphenyl phosphine chloride, tetrahydrofuran mol ratio be 1: 1-3: 1-3: 20-200.
5. the application of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) as claimed in claim 1, it is characterised in that：
Phosphine nitrogen ligand 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) situ catalytic Sonogashira cross-coupling reactions, formed
Alkynes coupled product；Method is：Acetonitrile is solvent under inert gas shielding, with 1- (9- anthryls) -2- diphenylphosphines-imidazoles/
PdCl2As catalyst, cesium carbonate makees alkali, halogenated aryl hydrocarbon, and 3h, TLC detections are reacted at 70 DEG C of phenylacetylene, and reaction cools down after terminating
To room temperature, column chromatography for separation, product is obtained.
6. a kind of application of 1- (9- anthryls) -2- diphenylphosphines-imidazoles (L) as claimed in claim 5, it is characterised in that described
Halogenated aryl hydrocarbon for an aryl bromide, an iodo aromatic hydrocarbon.
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| CN109746045A (en) * | 2018-10-31 | 2019-05-14 | 六盘水师范学院 | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application |
| CN110124732A (en) * | 2019-04-13 | 2019-08-16 | 复旦大学 | Polymer catalyst and preparation method thereof for metal catalyzed coupling reaction |
| CN113912618A (en) * | 2021-10-09 | 2022-01-11 | 香港中文大学深圳研究院 | Dioxa [5] spiroalkene compound and preparation method and application thereof |
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