CN101475493B - Preparation method of organic cation-anion pair - Google Patents
Preparation method of organic cation-anion pair Download PDFInfo
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- CN101475493B CN101475493B CN 200910077448 CN200910077448A CN101475493B CN 101475493 B CN101475493 B CN 101475493B CN 200910077448 CN200910077448 CN 200910077448 CN 200910077448 A CN200910077448 A CN 200910077448A CN 101475493 B CN101475493 B CN 101475493B
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Abstract
The invention discloses a method for preparing organic anion-cation pairs, which belong to the field of preparation of polymers. The method for preparing the organic anion-cation pairs comprises: a, mixing and dissolving tetraalkyl ammonium hydroxide or tetraalkyl phosphine hydroxide and an acid into water, and obtaining a reaction mixture; b, stirring the obtained reaction mixture for 8 to 12 hours under the protection of nitrogen N2, and obtaining ion-exchange products; C, performing freeze drying on the obtained ion-exchange products for 24 to 48 hours, and obtaining solid ion-exchange products after freeze drying; and d, performing vacuum drying on the obtained solid ion-exchange products for 24 to 36 hours at a temperature of between 30 and 50 DEG C, and obtaining the organic anion-cation pairs. The method for preparing the organic anion-cation pairs has simple technique, is convenient to prepare, effectively reduces the cost of alkali in coupling reaction due to low cost of quaternary ammonium hydroxide, and well solves the problem that inorganic alkali is difficult to dissolve in an organic solvent because quaternary ammonium cation or quaternary phosphine cation is easy to dissolve in the organic solvent.
Description
Technical field
The present invention relates to macromolecule material preparation area, relate in particular to the right preparation method of a kind of organic cation-anion.
Background technology
Quaternary ammonium salt and season phosphonium salt be typical cats product, at industrial textile auxiliary, daily chemical products functional agent, the Biocidal algae-killing agent etc. of also being used as, also can be used for preparing organobentonite, organobentonite is a kind of rheology modifier, it is used for the flowability of control paint in coatings industry, be used for preparing drilling well oil oar and as the lubricant in the various processing in field drilling; Be the most frequently used phase-transfer catalyst in addition, compare with other phase-transfer catalysts that its distinguishing feature is nontoxic and low price.
Transition metal-catalyzed linked reaction is important means (de Meijere, the A. etc. of modern organic synthesis; Metal-catalyzed cross-coupling reactions; Wiley-VCH, Weinheim, 2004), the method applies to synthetic organic intermediate in a large number, as: medicine, chemical etc.Present employed transition metal mainly concentrates on palladium Pd, copper Cu, and on the nickel, and employed alkali mainly is basic metal or alkaline earth salt (as: potassiumphosphate K
3PO
4, salt of wormwood K
2CO
3, yellow soda ash Na
2CO
3, yellow soda ash Cs
2CO
3), the problem that this class alkali faces is in organic solvent, and particularly the solvability in the non-polar solvent is very poor, and this will cause the poor repeatability of reacting and be unfavorable for the problem such as amplification scale.Therefore, be necessary to seek a kind of being simple and easy to, and the Novel alkali in the metal catalyzed coupling reaction that can be used on that in organic solvent, has good solubility.
Summary of the invention
Based on existing problem in the above-mentioned prior art, the purpose of embodiment of the present invention provides the right preparation method of a kind of organic cation-anion, utilize quaternary ammonium hydroxide or season phosphine alkali, prepare all types of organic cation-anions pair with a kind of cheaply ion-exchange, in metal catalyzed coupling reaction as the alkali that is easy to dissolve.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of organic cation-anion right preparation method, comprising:
A. obtain reaction mixture after tetra-alkyl ammonium hydroxide or hydroxide phosphine and acid is miscible in water;
The described reaction mixture that b. will obtain is in nitrogen N
2Protection is lower stirred 8～12 hours, obtained ion exchange product;
C. the described ion exchange product that obtains is carried out lyophilize 24～48 hours, obtain the solid-state form ion exchange product after the freeze-drying;
D. with the vacuum-drying after 24～36 hours under 30～50 ℃ of temperature condition of the solid-state form ion exchange product that obtains, namely obtain organic cation-anion pair.
Described tetra-alkyl ammonium hydroxide refers to meet the single compound of following (a) formula constitutional features, and the hydroxide phosphine refers to meet the single compound of following (b) formula constitutional features:
(a) formula and (b) in the formula, R
1, R
2, R
3, R
4In every all independent representatives have the alkyl of 1-12 carbon atom.
Acid among the described step a is organic acid or any mineral acid.
The consumption of described acid is and the moles such as tetra-alkyl ammonium hydroxide or hydroxide phosphine that the mole dosage of described water is 50-60 times of sour mole dosage.
Vacuum-drying in the described steps d is for carrying out vacuum-drying under 100～150Pa vacuum tightness.
Preferred temperature of reaction is 40 ℃ in the described steps d.
Can be found out by the technical scheme that the invention described above embodiment provides, embodiment of the present invention by take quaternary ammonium hydroxide or season phosphine alkali as raw material, its ion-exchange with acid is obtained organic cation-anion pair, further dewatering obtains its solid form.This organic cation-anion applies in the metal catalyzed coupling reaction can be used as alkali, at mild conditions, or even obtains coupled product under the room temperature condition; It is simple, easy to prepare that the method prepares the right technique of organic cation-anion, and because quaternary ammonium hydroxide is inexpensive, effectively reduce the cost of alkali in the linked reaction (with respect to Cs
2CO
3), quaternary ammonium cation or season the phosphine positively charged ion in organic solvent, have good solubility, well solved the problem that mineral alkali is insoluble in organic solvent, in addition owing to can regulate and control quaternary ammonium cation or the cationic substituting group chain length of season phosphine and steric hindrance, the acid ion that autotelic selection is all types of, thus can realize under the effect of such alkali that metal catalyzed coupling reaction obtains coupled product under a series of mild conditionss.From the mildness of reaction conditions, the aspects such as the simplification of experimental implementation have demonstrated the organic cation-anion advantage incomparable to (mineral alkali) of the method preparation.
Embodiment
Embodiment of the present invention provides a kind of organic cation-anion right preparation method, utilize quaternary ammonium hydroxide or season phosphine alkali, prepare all types of organic cation-anions pair with a kind of cheaply ion-exchange, the organic cation-anion that makes applies in the metal catalyzed coupling reaction can be used as alkali, and the preparation method specifically comprises:
Tetra-alkyl ammonium hydroxide or the hydroxide phosphine aqueous solution is miscible rear at N with acid
2Protection is lower stirred 8～12 hours, obtained ion exchange product, and after its freeze-drying, lyophilize 24h obtains the solid-state form ion exchange product, and this solid-state form ion exchange product of vacuum-drying under 30～50 ℃ of temperature obtains this organic cation-anion pair behind the 24h.
Can be used for metal catalyzed coupling reaction with the above-mentioned organic cation-anion that makes to as alkali, reaction method specifically comprises:
With the above-mentioned organic cation-anion that makes to mixing with transition-metal catalyst, and at N
2Protection is lower add the reagent that the mixture by solvent, halogenated aryl hydrocarbon and nucleophilic reagent forms after, 20～50 ℃ of temperature, N
2Protection is lower, stirs 12-36h, obtains coupled product.
The method by with quaternary ammonium hydroxide or season phosphine alkali as raw material, prepare all types of organic cation-anions pair with a kind of cheaply ion-exchange, and it applied to metal catalyzed coupling reaction as alkali.Wherein, used quaternary ammonium hydroxide or season phosphine alkali raw material can be by the salt of seeing in quaternary ammonium salt or season by chemical electrolysis method (US2001025798), ion exchange method (Platonowa etc., Russian Journal of General Chemistry, (1957), 297 (engl.Ausg)) or chemical precipitation method (Damerau etc., Zeitschrift fuer Chemie, (1983), 23,62) obtain.Reaction formula is as follows:
Quaternary ammonium hydroxide is inexpensive, can effectively reduce the cost of alkali in the linked reaction (with respect to Cs
2CO
3), quaternary ammonium or season the phosphine positively charged ion in organic solvent, have good solubility, well solved the problem that mineral alkali is insoluble in organic solvent, in addition owing to can regulate and control quaternary ammonium or the cationic substituting group chain length of season phosphine and steric hindrance, the acid ion that autotelic selection is all types of can have been realized metal catalyzed coupling reaction under a series of mild conditions under the effect of the alkali of this type.
For ease of the understanding to embodiment of the present invention, the present invention is described further below by specific embodiment.
Embodiment one
Present embodiment provides a kind of organic cation-anion right preparation method, be a kind of utilize quaternary ammonium hydroxide or season phosphine alkali be raw material, prepare the right method of all kinds organic cation-anion with cheaply ion-exchange, the organic cation-anion that makes applies in the metal catalyzed coupling reaction can be used as alkali, and the method specifically comprises:
A. obtain reaction mixture after tetra-alkyl ammonium hydroxide or hydroxide phosphine and acid is miscible in water;
The described reaction mixture that b. will obtain is in nitrogen N
2Protection is lower stirred 8～12 hours, obtained ion exchange product;
C. the described ion exchange product that obtains is carried out lyophilize 24～48 hours, obtain the solid-state form ion exchange product after the freeze-drying;
D. with the vacuum-drying after 24～36 hours under 30～50 ℃ of temperature condition of the solid-state form ion exchange product that obtains, namely obtain organic cation-anion pair, wherein, vacuum-drying generally is under preferred 40 ℃ of temperature, carry out under the condition of the vacuum tightness of 100～150Pa.
The tetra-alkyl ammonium hydroxide that adopts among the above-mentioned steps a refers to meet the single compound of following (a) formula constitutional features, and the hydroxide phosphine refers to meet the single compound of following (b) formula constitutional features:
(a) formula and (b) in the formula, R
1, R
2, R
3, R
4In every all independent representatives have the alkyl of 1-12 carbon atom.
The acid of using among the step a of aforesaid method is organic acid or any mineral acid, the consumption of acid be with step a in the moles such as employed tetra-alkyl ammonium hydroxide or hydroxide phosphine.
The organic cation-anion that makes among the above-mentioned preparation method is to can be used as the alkali in the metal catalyzed coupling reaction, and the organic cation-anion that utilizes aforesaid method to make carries out the method for metal catalyzed coupling reaction, can carry out in the steps below, comprising:
The organic cation-anion that makes in the aforesaid method to as alkali, is mixed with transition-metal catalyst, and in nitrogen N
2The reagent that the lower mixture that adds solvent, halogenated aryl hydrocarbon and nucleophilic reagent of protection forms forms reaction mixture; Transition-metal catalyst wherein is Pd catalyzer and part, or in Cu catalyzer and the part arbitrary group, and its consumption is that the halogenated aryl hydrocarbon mole ratio in the mixture of solvent, halogenated aryl hydrocarbon and nucleophilic reagent of the mole number of catalyzer and adding is 0.01～0.1.In the reagent that the mixture of solvent, halogenated aryl hydrocarbon and nucleophilic reagent forms, solvent can adopt methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dioxane, tetrahydrofuran (THF), acetonitrile, methylene dichloride, aniline, chlorobenzene, dimethylbenzene, toluene, water, methyl alcohol, ethanol, Virahol, the mixture of any one or more in the propyl carbinol; The consumption of solvent, halogenated aryl hydrocarbon and nucleophilic reagent by molar ratio is: solvent: halogenated aryl hydrocarbon=50: 1, halogenated aryl hydrocarbon: nucleophilic reagent=1: 1.5 or 1: 3;
With the described reaction mixture that obtains in 20～50 ℃ of temperature, nitrogen N
2Protection is lower, stirs 24～36h, namely obtains coupled product; Temperature during general formation coupled product is preferably 25 ± 3 ℃ of room temperatures.
In the method for the embodiment of the invention and since adopt as the tetra-alkyl ammonium hydroxide of quaternary ammonium hydroxide or season phosphine alkali the hydroxide phosphine be raw material, its ion-exchange with acid is obtained organic cation-anion pair, further dewatering obtains its solid form.This organic cation-anion applies in the metal catalyzed coupling reaction can be used as alkali, can be at mild conditions, or even obtain coupled product under the room temperature condition; It is simple, easy to prepare that the method prepares the right technique of organic cation-anion, and because quaternary ammonium hydroxide is inexpensive, effectively reduce the cost of alkali in the linked reaction (with respect to Cs
2CO
3), quaternary ammonium cation or season the phosphine positively charged ion in organic solvent, have good solubility, well solved the problem that mineral alkali is insoluble in organic solvent, in addition owing to can regulate and control quaternary ammonium cation or the cationic substituting group chain length of season phosphine and steric hindrance, the acid ion that autotelic selection is all types of, thus can realize under the effect of such alkali that metal catalyzed coupling reaction obtains coupled product under a series of mild conditionss.From the mildness of reaction conditions, the aspects such as the simplification of experimental implementation have demonstrated the organic cation-anion advantage incomparable to (mineral alkali) of the method preparation.
Embodiment two
Present embodiment provides a kind of right method of organic cation-anion for preparing, and it specifically comprises the steps:
A. the acid that with tetra-alkyl ammonium hydroxide or tetraalkyl hydroxide phosphine is raw material and equimolar amount obtains the first mixture in the aqueous solution;
B. stirred 12 hours with nitrogen protection, the organic ion of ammonium salt positively charged ion or phosphonium salt positively charged ion and acid radical anion is to product;
C. above-mentioned organic ion can be obtained the organic ion of the ammonium salt positively charged ion of solid-state form or phosphonium salt positively charged ion and acid radical anion after to the product lyophilize to product;
D. with the organic ion of the ammonium salt positively charged ion of solid-state form or phosphonium salt positively charged ion and acid radical anion to product 30～50 ℃ of lower vacuum-dryings 24 hours, namely obtain organic cation-anion pair; In the reality, preferred drying temperature is 40 ℃, and the time is 24h, and some dry times are longer, then can obtain better drying effect.
Among the above-mentioned preparation method, described alkyl comprises: the fatty group of carbonatoms 1-12 (comprising positive structure, side chain, and contain unsaturated group), aromatic base; Acid group comprises: mineral acid and organic acid;
The tetra-alkyl ammonium hydroxide as main raw material that adopts refers to meet the single compound of following (a) formula constitutional features, and the hydroxide phosphine refers to meet the single compound of following (b) formula constitutional features:
(a) formula and (b) in the formula, R
1, R
2, R
3, R
4In every all independent representatives have the alkyl of 1-12 carbon atom.
The above-mentioned organic cation-anion that makes can be used as alkali, is used for metal catalyzed coupling reaction, and concrete reactions steps is as follows:
The organic cation-anion that makes in the aforesaid method as alkali, and after mixing, transition-metal catalyst is obtained reaction mixture;
With above-mentioned reaction mixture in 20～50 ℃ temperature, at N
2Protection is lower, and the reaction reagent stirring reaction that adding solvent, halogenated aryl hydrocarbon and nucleophilic reagent mix 12-36 hour obtains coupled product; Preferred temperature of reaction is 25 ± 3 ℃ of room temperature in the reality, and the reaction times is preferably 18-24 hour, can adopt the mode of stirring to react.
In the aforesaid method, used catalyzer is Pd catalyzer and part, in Cu catalyzer and the part arbitrary group, and its consumption is; These catalyzer specifically comprise metal catalytic center: PdCl
2, Pd (OAc)
2, Pd (dba)
2, CuI, CuBr, CuCl,, Cu
2O, CuO, CuI
2, Cu (OAc)
2, CuCl
2, CuBr
2Deng, part: PPh
3, DPPF, X-PHOS, L-PROLINE, the 1.10-phenanthroline, ethylene glycol, DMEDA, TMEDA etc., and be not limited to described these.Catalyzer preferably adopts Cu catalyzer and part, as: CuI and L-PROLINE, CuI and 1.10-phenanthroline etc., in the reality, catalyzer preferably uses CuI and L-PROLINE, and the consumption of catalyzer is 0.01～0.1 times (catalyzer mole number and described halogenated aryl hydrocarbon mole ratio) of described halogenated aryl hydrocarbon consumption;
In above-mentioned metal catalyzed coupling reaction, solvent is organic solvent in the reaction reagent that solvent, halogenated aryl hydrocarbon and nucleophilic reagent mix, preferred employing can be dissolved the right solvent of organic cation-anion fully, and solvent preferably uses single solvent in the reality, and that most preferably adopt is DMF; Halogenated aryl hydrocarbon in the reaction reagent is chlorobenzene, in the bromobenzene, iodobenzene and its substitutive derivative any, preferred iodobenzene and derivative thereof in the reality; Nucleophilic reagent in the reaction reagent can adopt fatty amines, aromatic amine, and any in nitrogen heterocyclic ring and the sulfur alcohol compound, any nucleophilic reagent all can use in the metal catalyzed coupling reaction of the embodiment of the invention in practice.
In above-mentioned reaction method, the product that is obtained by halogenated aryl hydrocarbon and nucleophilic reagent coupling refers to contain heteroatomic aromatic compound, comprise N-phenylbenzylamine, N propyl aniline, N-n-hexyl aniline, N-cyclohexyl aniline, pentanoic, N-phenylimidazole, N-phenylpyrazole, N-Phenylindole, phenylbenzyl thioether etc., comprise simultaneously their phenyl ring substitutive derivative.
For clearer subsequent embodiment is described, the below provides the symbol abbreviation expression of each raw material of using among each embodiment, and in each embodiment, the place of using the symbol abbreviation all refers to content corresponding to corresponding symbol abbreviation, and is specific as follows:
The DMSO methyl-sulphoxide
The DMF DMF
The NMP N-Methyl pyrrolidone
DMEDA N, N '-dimethyl-ethylenediamine
GC vapor-phase chromatography (for detection of the content of coupled product in the reaction solution)
Embodiment three
This enforcement provides a kind of organic cation-anion right preparation method, is that raw material prepares tetrabutyl ammonium oxalate by oxalic acid and 4-n-butyl ammonium hydroxide specifically, and is specific as follows:
With oxalic acid (4.338 grams; 0.0482mol) to add concentration be 25% 4-n-butyl ammonium hydroxide (100 grams; 0.0964mol) in the aqueous solution; this solution was stirred 12 hours under nitrogen protection; lyophilize to adularescent solid tetra-n-butyl ammonium oxalate generates; again with gained tetra-n-butyl ammonium oxalate 40 ℃ of lower vacuum-dryings 24 hours, can obtain final tetra-n-butyl ammonium oxalate ion-pair compound.
Embodiment four
This enforcement provides a kind of organic cation-anion right preparation method, is that raw material prepares tetrabutyl ammonium adipate by hexanodioic acid and 4-n-butyl ammonium hydroxide specifically, and is specific as follows:
(7.0421 grams, 0.0482mol) adding concentration is that (100 grams are 0.0964mol) in the aqueous solution for 25% TBAH with hexanodioic acid.This solution was stirred 12 hours under nitrogen protection.Lyophilize to adularescent solid tetra-n-butyl ammonium adipate generates, again with gained tetra-n-butyl ammonium adipate 40 ℃ of lower vacuum-dryings 24 hours, can obtain final tetra-n-butyl ammonium adipate ion-pair compound.
Embodiment five
This enforcement provides a kind of organic cation-anion right preparation method, is that raw material prepares tetrabutyl ammonium adipate by carbonic acid gas and 4-n-butyl ammonium hydroxide specifically, and is specific as follows:
Carbonic acid gas is passed into the TBAH of concentration as 25% in the mode of slow bubbling, and (100 grams, 0.0964mol) in the aqueous solution, reaction continues 24 hours always.Lyophilize to adularescent solid tetra-n-butyl bicarbonate of ammonia generates, again with gained tetra-n-butyl bicarbonate of ammonia 40 ℃ of lower vacuum-dryings 24 hours, can obtain final tetra-n-butyl bicarbonate of ammonia ion-pair compound.
Embodiment six
This enforcement provides a kind of organic cation-anion right preparation method, is that raw material prepares tetrabutyl ammonium phosphate by phosphoric acid and 4-n-butyl ammonium hydroxide specifically, and is specific as follows:
(3.7028 grams, 0.0321mol) add concentration is that (100 grams are 0.0964mol) in the aqueous solution for 25% TBAH to phosphoric acid with 25%.This solution was stirred 12 hours under nitrogen protection.Lyophilize to adularescent solid tetra-n-butyl ammonium phosphate generates, again with gained tetra-n-butyl ammonium phosphate 40 ℃ of lower vacuum-dryings 24 hours, can obtain final tetra-n-butyl ammonium phosphate ion-pair compound.
Embodiment seven
This enforcement provides a kind of organic cation-anion right preparation method, is that raw material prepares tetrabutyl hexanodioic acid phosphine by adipic acid and tetra-n-butyl hydroxide phosphine specifically, and is specific as follows:
It is that (100 grams are 0.1448mol) in the aqueous solution for 40% normal-butyl hydroxide phosphine that hexanodioic acid (10.5712g, 0.0724mol) is added concentration.This solution stirred 12 hours under nitrogen protection.Lyophilize to adularescent solid tetra-n-butyl ammonium adipate generates, again with gained tetra-n-butyl ammonium adipate 40 ℃ of lower vacuum-dryings 24 hours, can obtain final tetra-n-butyl ammonium adipate ion-pair compound.
Embodiment eight
This embodiment provides organic cation-anion that the preparation method by the embodiment of the invention makes to as alkali, prepares the N-phenylbenzylamine by the C-N coupling, and is specific as follows:
With CuI (9.5mg, 0.05mmol), iodobenzene (56 μ L, 0.5mmol), benzylamine (82 μ L, 0.75mmol), tetra-n-butyl ammonium adipate (0.471g, 0.75mmol), L-PROLINE (11.5mg, 0.1mmol), and 0.5mL DMF adding passes in the reaction tubes of nitrogen protection; With reaction tubes sealing, 25 ℃ of lower stirring reactions 24 hours, reaction solution is crossed chromatography column obtain product N-phenylbenzylamine 86mg, productive rate 95% (in iodobenzene).
Present embodiment only describes the utilization in the metal linked reaction the organic cation-anion that the preparation method of the embodiment of the invention makes as raw material with iodobenzene and benzylamine, those skilled in the art, according to the record in the specification sheets and the thinking that provides, can estimate to meet the requirements halogenated aryl hydrocarbon and aliphatic amide all can be implemented in the method for the embodiment of the invention, prepare coupled product, therefore, no longer repeating to enumerate other halogenated aryl hydrocarbon of employing and aliphatic amide is the embodiment that raw material prepares the C-N coupled product.
Embodiment nine-12
Following several embodiment provides the organic cation-anion that is made by the preparation method in the embodiment of the invention to as alkali, prepares pentanoic by the C-N coupling, and is specific as follows:
To the tetra-n-butyl ammonium adipate in the alternative embodiment eight, all the other operate similar embodiment eight with several different organic cation-anion that makes among the embodiment three～six, and the design parameter of operation is referring to table 1.
Table 1 to as alkali, is realized Cu catalysis C-N coupling with all types of organic cation-anions
Embodiment 13-16
Following several embodiment provides the organic cation-anion that is made by the preparation method in the embodiment of the invention to as alkali, prepares the N-phenyl heterocycles by the C-N coupling, and is specific as follows:
To the tetra-n-butyl ammonium adipate in the alternative embodiment eight, all the other operate similar embodiment eight with several different organic cation-anion that makes among the embodiment three～six, and the design parameter of operation is referring to table 2.
Table 2 to as alkali, is realized Cu catalysis C-N coupling with all types of organic cation-anions
Above-mentioned several embodiment only describes the utilization in the metal linked reaction organic cation-anion as raw material with iodobenzene and pyrazoles, those skilled in the art, according to the record in the specification sheets and the thinking that provides, can estimate to meet the requirements halogenated aryl hydrocarbon and nitrogen heterocyclic ring all can be implemented in the method for the embodiment of the invention, prepare coupled product, therefore, no longer repeating to enumerate other halogenated aryl hydrocarbon of employing and nitrogen heterocyclic ring is the embodiment that raw material prepares the C-N coupled product.
Embodiment 17-20
These several embodiment provide by organic cation-anion as alkali, prepare thio-ether type compounds by the C-S coupling, and are specific as follows:
To the tetra-n-butyl ammonium adipate in the alternative embodiment eight, all the other operate similar embodiment eight with several different organic cation-anions, and the design parameter of operation is referring to table 3.
Table 3 to as alkali, is realized Cu catalysis C-S coupling with all types of organic cation-anions
Above-mentioned several embodiment only describes the utilization in the metal linked reaction organic cation-anion as raw material with iodobenzene and benzyl sulfhydrate, those skilled in the art, according to the record in the specification sheets and the thinking that provides, can estimate to meet the requirements halogenated aryl hydrocarbon and sulfur alcohol compound all can be implemented in the method for the embodiment of the invention, prepare coupled product, therefore, no longer repeating to enumerate other halogenated aryl hydrocarbon of employing and sulfur alcohol compound is the embodiment that raw material prepares the C-N coupled product.
Embodiment 21
Present embodiment provides a kind of organic cation-anion that makes with the preparation method of the embodiment of the invention to as alkali, prepares the method for pentanoic by Pd catalysis C-N coupling, and is specific as follows:
With Pd (OAc)
2(2.2mg, 0.01mmol), chlorobenzene (106 μ L; 1mmol); aniline (135 μ L, 1.5mmol), tetra-n-butyl ammonium adipate (0.93g; 1.5mmol); X-PHOS (7.2mg, 0.3mmol) and 0.5mL DMF pass in the reaction tubes of nitrogen protection, and reaction tubes is sealed; 45 ℃ of lower stirring reactions 24 hours, reaction solution is crossed chromatography column obtain product pentanoic (85% yield).
Only organic cation-anion is described the utilization in the metal linked reaction as raw material with chlorobenzene and aniline in the present embodiment, those skilled in the art, according to the record in the specification sheets and the thinking that provides, can estimate to meet the requirements halogenated aryl hydrocarbon and arylamine all can be implemented in the method for the embodiment of the invention, prepare coupled product, therefore, no longer repeating to enumerate other halogenated aryl hydrocarbon of employing and arylamine is the embodiment that raw material prepares the C-N coupled product.
The above; only be the better embodiment of the present invention; but protection scope of the present invention is not limited to this; because of the succession between each embodiment the present invention is not caused any restriction yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (6)
1. the preparation method that organic cation-anion is right is characterized in that, comprising:
A. obtain reaction mixture after tetra-alkyl ammonium hydroxide or hydroxide phosphine and acid is miscible in water;
The described reaction mixture that b. will obtain is in nitrogen N
2Protection is lower stirred 8～12 hours, obtained ion exchange product;
C. the described ion exchange product that obtains is carried out lyophilize 24～48 hours, obtain the solid-state form ion exchange product after the freeze-drying;
D. with the vacuum-drying after 24～36 hours under 30～50 ℃ of temperature condition of the solid-state form ion exchange product that obtains, namely obtain organic cation-anion pair.
2. the right preparation method of organic cation-anion according to claim 1, it is characterized in that, described tetra-alkyl ammonium hydroxide refers to meet the single compound of following (a) formula constitutional features, and the hydroxide phosphine refers to meet the single compound of following (b) formula constitutional features:
(a) formula and (b) in the formula, R
1, R
2, R
3, R
4In every all independent representatives have the alkyl of 1-12 carbon atom.
3. the right preparation method of organic cation-anion according to claim 1 is characterized in that, the acid among the described step a is organic acid or any mineral acid.
4. according to claim 1 or 3 described preparation methods, it is characterized in that the consumption of described acid is and the moles such as tetra-alkyl ammonium hydroxide or hydroxide phosphine, the mole dosage of described water be sour mole dosage 50-60 doubly.
5. the right preparation method of organic cation-anion according to claim 1 is characterized in that, the vacuum-drying in the described steps d is for carrying out vacuum-drying under the vacuum tightness of 100～150Pa.
6. the right preparation method of organic cation-anion according to claim 1 or 5 is characterized in that, preferred temperature of reaction is 40 ℃ in the described steps d.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931845A (en) * | 2006-09-29 | 2007-03-21 | 华东师范大学 | Alkaline ionic liquid and its prepn process and application |
| CN101182300A (en) * | 2007-12-12 | 2008-05-21 | 河北工业大学 | Quaternary ammonium ionic liquid as well as preparation and application method thereof |
-
2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931845A (en) * | 2006-09-29 | 2007-03-21 | 华东师范大学 | Alkaline ionic liquid and its prepn process and application |
| CN101182300A (en) * | 2007-12-12 | 2008-05-21 | 河北工业大学 | Quaternary ammonium ionic liquid as well as preparation and application method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Fang Dong.Mannich reaction in water using acidic ionic liquidasrecoverable and reusable catalyst.《catalysis letters》.2007,第116卷(第1-2期),76-80. * |
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