CN110483225A - A kind of water phase Suzuki cross-coupling reaction of the palladium chtalyst without additional ligand - Google Patents
A kind of water phase Suzuki cross-coupling reaction of the palladium chtalyst without additional ligand Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
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- C—CHEMISTRY; METALLURGY
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- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Abstract
A kind of water phase Suzuki cross-coupling reaction the invention discloses palladium chtalyst without additional ligand, is solvent by catalytic species, water of palladium, using quaternary ammonium base and emulsifier, carries out efficient palladium chtalyst carbon-carbon bond cross-coupling reaction synthesis biaryl hydrocarbon compound.Reaction system of the present invention is green, reaction condition is mild, and at relatively high temperatures, catalysis 3 minutes achievable, provides possibility to carry out catalysis on thermopnore.And catalyst is without additional ligand, quaternary ammonium base plays the role of stably catalyzed species palladium compared to traditional inorganic base to a certain extent, the dosage of palladium is reduced, and can directly be utilized again during recycling, reusable 8 times or more under the premise of not significantly reducing active.The step of catalysate can crystallize precipitation directly in system, obtain sterling by the method for filtration washing, eliminate column chromatography, it is easy to operate and safe.In addition, the reaction system is good to reaction substrate universality, there is biggish practical application value.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to one kind is simple, palladium chtalyst efficiently, green is matched without additional
The water phase Suzuki cross-coupling reaction of body.
Background technique
The aryl boric acid class compound of transition metal palladium chtalyst and the Suzuki cross-coupling reaction of halogenated aryl hydrocarbon are to construct
The effective ways of carbon-carbon bond have been widely used in natural products, drug, advanced function material and fine-chemical intermediate
Synthesis.Currently, the palladium obtained in the case where adding organic ligand (such as triphenylphosphine) is industrially mainly used to cooperate
Object is as homogeneous catalyst, and using traditional organic solvent as reaction medium, entire catalytic process usually requires nitrogen or argon gas
Atmosphere is protected, and operating process is cumbersome, and can cause environmental pollution.In recent years, Green Chemistry obtains more and more
Concern, water have many advantages, such as a kind of ideal reaction medium it is resourceful, cheap and easy to get, nontoxic, pollution-free, with water be Jie
There are many reports for the Suzuki reaction system of matter, but most of reaction systems need to be added water soluble ligand to promote reaction
Carry out, the synthesis step of most of ligands is more complicated, expensive, and after reacting ligand separation it is also more time-consuming,
And in order to avoid catalytic species palladium is inactivated because of reunion during the reaction, it is more to the demand of palladium the problems such as answer it
It is restricted with range.And either in homogeneous catalysis or heterogeneous catalytic system, the separating-purifying of product is required to make
The method chromatographed with column, it is cumbersome, and need during product separating-purifying using petroleum ether, silica gel etc., toxicity is big, cost
It is high.In addition, traditional product process for separation and purification makes catalyst system be difficult to reuse, increases sewage discharge pressure and disappear
Consume cost.
Summary of the invention
The object of the present invention is to provide one kind using palladium as catalytic species and without additional ligand, and water is solvent, and quaternary ammonium base is
The method of the Suzuki cross-coupling reaction of alkali, efficient catalytic aryl boric acid class compound and halogenated aryl hydrocarbon, this method catalyst
Dosage it is few, recycling for catalyst not only may be implemented, and only by simply recrystallization product biaryl can be realized
The separating-purifying of hydrocarbon compound.
For above-mentioned purpose, the technical scheme adopted by the invention is that: by aryl shown in halogenated aryl hydrocarbon, Formula II shown in Formulas I
Boric acid compound, palladium catalyst, quaternary ammonium base, emulsifier and water sequentially add in reactor, 20~50 DEG C in air atmosphere
It is stirred to react 1~10 hour or 50~80 DEG C and is stirred to react 3~60 minutes, be down to room temperature naturally, analysis is stood at -10~30 DEG C
Solid out is filtered and is washed with water, and obtains biaryl hydrocarbon compound shown in pure formula III；Formulas I is directly rejoined into filtrate
Aryl boric acid class compound shown in shown halogenated aryl hydrocarbon, Formula II continues the conjunction of Suzuki cross-coupling reaction according to the method described above
At biaryl hydrocarbon compound shown in formula III, reaction equation is as follows:
In Formulas I and III, the R1For aryl or substituted aryl；X represents Cl, Br or I；In Formula II and III, the R2
Selected from C1~C4Alkyl, C3~C6Naphthenic base, aryl, any one in substituted aryl.
Above-mentioned aryl specifically can be phenyl, thienyl, naphthalene, pyrenyl, benzothienyl, furyl, benzofuran
Base, pyrrole radicals, any one in benzopyrrole base, substituted aryl are halogen, nitro, cyano, ester group, formoxyl, acetate, C1
~C4Alkyl, C1~C4Replace above-mentioned aryl for 1~3 kind in alkoxy, trifluoromethyl.
Above-mentioned palladium catalyst is selected from four ammino palladium of dichloride, tetrakis triphenylphosphine palladium, palladium chloride, bis- (triphenylphosphines) two
Palladium chloride, palladium acetylacetonate, bis- (acetonitrile) palladium chlorides, palladium chloride (Π-cinnamyl) dimer, palladium acetate, in sodium tetrachloropallate
Any one, preferably four ammino palladium of dichloride, tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides, palladium acetylacetonate, chlorine
Change any one in palladium.The palladium catalyst additional amount is the 0.0006%~0.20% of halogenated aryl hydrocarbon mole.
Above-mentioned quaternary ammonium base is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen
Amine-oxides, four pentyl ammonium hydroxide, tetradecyltrimethylammonium ammonium hydroxide, cetyltrimethylammonium hydroxide, double ten alkyl
Any one in dimethyl hydrogen amine-oxide, preferably tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, four pentyl ammonium hydroxide, ten
Tetraalkyl trimethylammonium hydroxide, cetyltrimethylammonium hydroxide, any one in didecyl Dimethy ammonium hydroxide.
Above-mentioned emulsifier is selected from Span 80, triton x-100, Qula and leads to X-114, Qula logical X-102, cetyl three
Any one in methyl bromide ammonium, preferably triton x-100, Qula lead to X-114, Qula leads to X-102, cetyl trimethyl bromine
Change any one in ammonium, the quality of emulsifier and water is 1:10~200, and the quality of preferred emulsifier and water is 1:20~150.
In the above method, the preferably molar ratio of halogenated aryl hydrocarbon and aryl boric acid class compound, quaternary ammonium base is 1:0.8~2:
1.5~3.
Compared with prior art, the invention has the following advantages:
1, for the present invention using palladium as catalytic species, palladium is from a wealth of sources, carries out Suzuki cross-coupling reaction under alkaline condition
Biaryl hydrocarbon compound is made, is not necessarily to N2Equal inert gas shieldings；Catalyst avoids ligand in catalytic process without additional ligand
In influence and isolating ligands to reaction complex process, reduce costs.
2, catalyst system of the present invention uses water as solvent, reaction condition green, no operational hazards；Catalyst is in the reaction
Catalytic activity is high in system: halogenated aryl hydrocarbon and the molar ratio of palladium in catalyst still can be after reacting 2 hours when being 1:30ppm
Realize conversion completely；High catalytic efficiency: some substrates react under higher temperature (such as 80 DEG C) 3 minutes can fully reacting (its
The Suzuki coupling reaction of his Pd catalysis usually requires even a couple of days a few hours), under Catalysis Rate and microwave heating condition
Speed is suitable.
3, the recyclable property of catalyst is good in reaction system of the present invention.After reaction, filtered filtrate without
Specially treated is needed, directly rejoining substrate can reuse, and catalytic efficiency is not significantly reduced after reaction 8 times.
In addition, the recycling property of quaternary ammonium base and emulsifier is good in reaction system.After reaction, product can be in room temperature or low temperature
Pure biaryl hydrocarbon compound can be obtained by filtering in lower crystallization, and separation is simple, and reaction solution can be recycled, and reduces
The consuming cost of catalyst, quaternary ammonium base and emulsifier；It is good to reaction substrate universality, under the catalyst system, bromo and
The halide of chloro equally can have biggish practical application value with highly effective reaction.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
By 0.188g (1.2mmol) 4- methoxyphenylboronic acid, 0.106mL (1.0mmol) bromobenzene, 0.0008g dichloride four
Ammino palladium (wherein Pd is 0.0012mmol), 0.40g (2mmol) tetrapropylammonium hydroxide, 0.1mL triton x-100,7mL water
It is added in reaction flask, is stirred to react at 45 DEG C 60 minutes, stop reaction, rock and be uniformly down to room temperature naturally, stand 1 hour,
White solid is precipitated, is subsequently placed in sufficient crystallising 2 hours at -2 DEG C, filters and be washed with water, obtain pure methoxyl group -1 4-,
1 '-biphenyl, yield 99.0%.0.188g (1.2mmol) 4- methoxyphenylboronic acid, 0.106mL are directly added into filtrate
(1.0mmol) bromobenzene, re-starts reaction according to the method described above.Experimental result is shown, after catalyst circulation 8 times, 4- methoxyl group-
1,1 '-biphenyl yield still can achieve 70.0%, extend the reaction time to 4 hours, methoxyl group -1 4-, 1 '-biphenyl yield is still
It so can achieve 97.0%.
Embodiment 2
In the present embodiment, the dosage of four ammino palladium of dichloride is 0.00002g (wherein Pd is 0.00003mmol), when reaction
Between extend to 3 hours, other steps are same as Example 1, obtain pure methoxyl group -1 4-, 1 '-biphenyl, yield 99.0%.
Embodiment 3
In the present embodiment, with two in 0.00018g palladium acetylacetonate (wherein Pd is 0.0006mmol) alternative embodiment 1
Four ammino palladium of chlorination, and be stirred to react at 45 DEG C 4 hours, other steps are same as Example 1, obtain pure 4- methoxyl group-
1,1 '-biphenyl, yield 99.0%.
Embodiment 4
In the present embodiment, in 0.00069g tetrakis triphenylphosphine palladium (wherein Pd is 0.0006mmol) alternative embodiment 1
Four ammino palladium of dichloride, reaction time extend to 4 hours, other steps are same as Example 1, obtain pure methoxyl group -1 4-,
1 '-biphenyl, yield 99.0%.
Embodiment 5
In the present embodiment, implemented with bis- (triphenylphosphine) palladium chlorides of 0.00042g (wherein Pd is 0.0006mmol) replacement
Four ammino palladium of dichloride in example 1, reaction time extend to 4 hours, other steps are same as Example 1, obtain pure 4- first
Oxy-1,1 '-biphenyl, yield 99.0%.
Embodiment 6
It in the present embodiment, is reacted 3 hours at 20 DEG C, other steps are same as Example 1, obtain pure 4- methoxyl group-
1,1 '-biphenyl, yield 98.0%.
Embodiment 7
In the present embodiment, with the tetrapropyl hydroxide in equimolar cetyltrimethylammonium hydroxide alternative embodiment 1
Ammonium, other steps are same as Example 1, obtain pure methoxyl group -1 4-, 1 '-biphenyl, yield 99.0%.
Embodiment 8
In the present embodiment, with the triton x-100 in 0.2g cetyl trimethylammonium bromide alternative embodiment 1, other
Step is same as Example 1, obtains pure methoxyl group -1 4-, 1 '-biphenyl, yield 99.0%.
Embodiment 9
In the present embodiment, with the bromobenzene in equimolar 1- bromonaphthalene alternative embodiment 1, other steps are same as Example 1, obtain
Obtain pure 1- (4- methoxyphenyl) naphthalene, yield 99.0%.
Embodiment 10
In the present embodiment, with the bromobenzene in equimolar 4- methoxybromobenzene alternative embodiment 1, other steps and embodiment 1
It is identical, obtain pure 4,4 '-dimethoxy -1,1 '-biphenyl, yield 99.0%.
Embodiment 11
In the present embodiment, with equimolar to the bromobenzene in 5 bromine benzotrifluoride alternative embodiment 1, other steps and embodiment 1
It is identical, obtain pure 4- methoxyl group -4'- (trifluoromethyl) -1,1'- biphenyl, yield 95.0%.
Embodiment 12
In the present embodiment, with the bromobenzene in equimolar 1- bromine pyrene alternative embodiment 1, other steps are same as Example 1, obtain
Obtain pure 1- (4- methoxyphenyl) pyrene, yield 98.0%.
Embodiment 13
In the present embodiment, with the bromobenzene in equimolar 4- iodobenzene formonitrile HCN alternative embodiment 1, other steps and 1 phase of embodiment
Together, pure 4- methoxyl group -4'- (cyano) -1,1'- biphenyl, yield 96.0% are obtained.
Embodiment 14
In the present embodiment, with the 4- methoxyphenylboronic acid in equimolar phenyl boric acid alternative embodiment 1, other steps and implementation
Example 1 is identical, obtains pure biphenyl, yield 99.0%.
Embodiment 15
In the present embodiment, with equimolar to the bromobenzene in bromo-acid alternative embodiment 14, after fully reacting, hydrochloric acid is added
It is neutralized, then rocks and be uniformly down to room temperature naturally, stand 1 hour, white solid is precipitated, is subsequently placed at -2 DEG C and sufficiently ties
It is 2 hours brilliant, it filters and is washed with water, obtain pure 4- acetate -1,1'- biphenyl, yield 99.0%.
Embodiment 16
In the present embodiment, with the 4- methoxyphenylboronic acid in equimolar 4- nitrobenzene boronic acid alternative embodiment 1, other steps
It is same as Example 1, obtain pure 4- nitro -1,1'- biphenyl, yield 99.0%.
Embodiment 17
In the present embodiment, with the bromobenzene in equimolar 4- methyl bromobenzene alternative embodiment 1, other steps and 1 phase of embodiment
Together, pure 4- methyl-1,1 '-biphenyl, yield 99.0% are obtained.
Claims (7)
1. a kind of water phase Suzuki cross-coupling reaction of palladium chtalyst without additional ligand, it is characterised in that: by halogenated virtue shown in Formulas I
Aryl boric acid class compound shown in hydrocarbon, Formula II, palladium catalyst, quaternary ammonium base, emulsifier and water sequentially add in reactor, in air
It is stirred to react 1~10 hour or 50~80 DEG C and is stirred to react 3~60 minutes for 20~50 DEG C in atmosphere, room temperature is down to naturally, -10
It is stood at~30 DEG C and solid is precipitated, filtered and be washed with water, obtain biaryl hydrocarbon compound shown in pure formula III；Into filtrate
It is directly added into aryl boric acid class compound shown in halogenated aryl hydrocarbon, Formula II shown in Formulas I and re-starts Suzuki friendship according to the method described above
Pitch biaryl hydrocarbon compound shown in coupling reaction synthesis formula III；
In Formulas I and III, the R1For aryl or substituted aryl；X represents Cl, Br, I；In Formula II and III, the R2It is selected from
C1~C4Alkyl, C3~C6Naphthenic base, aryl, any one in substituted aryl；
Above-mentioned palladium catalyst is selected from four ammino palladium of dichloride, tetrakis triphenylphosphine palladium, palladium chloride, bis- (triphenylphosphine) dichlorides
It is palladium, palladium acetylacetonate, bis- (acetonitrile) palladium chlorides, palladium chloride (Π-cinnamyl) dimer, palladium acetate, any in sodium tetrachloropallate
One kind, with the molar amount of palladium in catalyst, additional amount is the 0.0006%~0.20% of halogenated aryl hydrocarbon mole；
Above-mentioned quaternary ammonium base is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide
Ammonium, four pentyl ammonium hydroxide, tetradecyltrimethylammonium ammonium hydroxide, cetyltrimethylammonium hydroxide, double ten alkyl-dimethyls
Any one in base ammonium hydroxide；
Above-mentioned emulsifier is selected from Span 80, triton x-100, Qula and leads to X-114, Qula logical X-102, cetyl trimethyl
The quality of any one in ammonium bromide, the emulsifier and water is 1:10~200.
2. water phase Suzuki cross-coupling reaction of the palladium chtalyst according to claim 1 without additional ligand, it is characterised in that:
The aryl is phenyl, thienyl, naphthalene, pyrenyl, benzothienyl, furyl, benzofuranyl, pyrrole radicals, benzopyrene
Any one in base is coughed up, the substituted aryl is halogen, nitro, cyano, ester group, formoxyl, acetate, C1~C4Alkyl, C1~
C4The aryl of 1~3 kind of substitution in alkoxy, trifluoromethyl.
3. water phase Suzuki cross-coupling reaction of the palladium chtalyst according to claim 1 or 2 without additional ligand, feature exist
In: the palladium catalyst is selected from four ammino palladium of dichloride, tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides, acetyl
Any one in acetone palladium, palladium chloride.
4. water phase Suzuki cross-coupling reaction of the palladium chtalyst according to claim 1 or 2 without additional ligand, feature exist
In: the quaternary ammonium base is selected from tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, four pentyl ammonium hydroxide, tetradecyl trimethyl
Base ammonium hydroxide, cetyltrimethylammonium hydroxide, any one in didecyl Dimethy ammonium hydroxide.
5. water phase Suzuki cross-coupling reaction of the palladium chtalyst according to claim 1 or 2 without additional ligand, feature exist
In: the emulsifier leads to X-114 selected from triton x-100, Qula, Qula leads to X-102, appoints in cetyl trimethylammonium bromide
It anticipates one kind.
6. water phase Suzuki cross-coupling reaction of the palladium chtalyst according to claim 5 without additional ligand, feature exists
In: the quality of the emulsifier and water is 1:20~150.
7. water phase Suzuki cross-coupling reaction of the palladium chtalyst according to claim 1 or 2 without additional ligand, feature exist
In: the molar ratio of the halogenated aryl hydrocarbon and aryl boric acid class compound, quaternary ammonium base is 1:0.8~2:1.5~3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478291A (en) * | 2022-03-10 | 2022-05-13 | 西安爱德克美新材料有限公司 | Preparation method of monomer diamine compound of polyimide |
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| CN102617256A (en) * | 2012-02-29 | 2012-08-01 | 大连理工大学 | Method for preparing biaryl compound in pure water |
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| CN114478291A (en) * | 2022-03-10 | 2022-05-13 | 西安爱德克美新材料有限公司 | Preparation method of monomer diamine compound of polyimide |
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