CN102850156B - A kind of method of synthesizing adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour - Google Patents
A kind of method of synthesizing adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour Download PDFInfo
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- CN102850156B CN102850156B CN201210383747.0A CN201210383747A CN102850156B CN 102850156 B CN102850156 B CN 102850156B CN 201210383747 A CN201210383747 A CN 201210383747A CN 102850156 B CN102850156 B CN 102850156B
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Abstract
The invention discloses a kind of adjacent amino two aryl oxides and the amino two fragrant thioether synthetic methods of neighbour, in solvent alcohol or water under the effect of alkali, add iron and/or copper catalyst, the open loop linked reaction of catalysis aryl halides and benzazoles compound prepares adjacent amino two aryl oxides or adjacent amino two fragrant thioethers, and reaction expression is expressed as follows.Linked reaction of the present invention prepares the method for amino two aryl oxides of neighbour and the amino two fragrant thioethers of neighbour, and catalyzer is cheap and toxicity is little, and reaction is direct and Atom economy is high, and substrate source is extensive and stable, applied widely.Under the reaction conditions optimized, target product separation yield is up to 96%.
Description
Technical field
The present invention relates to a kind of method of synthesizing adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour.
Background technology
Adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour are important organic intermediates, are widely used in biology and field of medicaments, show the characteristics such as unique anti-inflammatory, antitumor, anti-infective, antipsychotic and antidepressant.The method of synthesizing this type of material has caused to be paid close attention to widely, and has made some progress.
The synthesis of adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour, modal and the most direct method is the linked reaction that transition metal-catalyzed carbon-oxygen and carbon-sulfide linkage are formed, but the initial reactant that the method is used is Ortho-Aminophenol and near amino thiophenols, they are difficult to preparation and are easily oxidized, meanwhile, the existence of various active functional group causes the problem of reaction preference.In order to avoid these problems, be developed two-step approach: use stable o-NP and ortho-nitrophenyl thiophenol first to carry out being formed the linked reaction of carbon-oxygen and carbon-sulfide linkage as reactant; And then obtained intermediate product is carried out the reduction of nitro.Although two-step approach achieves high selectivity, reaction will be carried out in two steps, reduces the efficiency of reaction and creates more impurity or waste.Subsequently, again through further improving, report " one kettle way " of adjacent amino two aryl oxides and the amino two fragrant thioethers synthesis of neighbour: the reduction of linked reaction and nitro simultaneously one pot carry out.But the narrow application range of this reaction, only has the substrate of very electron-deficient to react.
There is poor selectivity in the synthetic method of current disclosed report, produce refuse mainly with and the shortcoming such as narrow application range, before the present invention, there is not been reported for a kind of general, efficient and eco-friendly method preparing adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour.
Summary of the invention
Main purpose of the present invention is, the defect that the method overcoming adjacent amino two aryl oxides of existing synthesis and the amino two fragrant thioethers of neighbour exists, and the method for adjacent amino two aryl oxides of a kind of synthesis newly and the amino two fragrant thioethers of neighbour is provided, under copper and/or iron catalyst effect, adjacent amino two aryl oxides and the amino two fragrant thioethers of neighbour are synthesized in aryl halides and azole heterocycle direct open loop coupling, substrate source is extensive, functional group's consistency is good, catalyzer is cheap and toxicity is little, active good without the need to part, target product yield is high, applied widely.
The present invention for achieving the above object and solve its technical problem, by the following technical solutions:
A kind of adjacent amino two aryl oxides and the amino two fragrant thioether synthetic methods of neighbour, it is characterized in that, with alcohol or water for solvent, add copper catalyst and/or iron catalyst, under the effect of alkali, benzazoles compound (II) and aryl halides (III) open loop linked reaction, obtained adjacent amino two aryl oxides or adjacent amino two fragrant thioethers (I), reaction expression is expressed as follows:
ⅡⅢⅠ。
The general structure of amino two aryl oxides of neighbour synthesized by method of the present invention and the amino two fragrant sulfide compounds of neighbour be (
i):
In formula:
x=O or S;
R
1~ R
4or R
5~ R
9be selected from arbitrarily hydrogen, the alkyl of C1 ~ C12 straight or branched or aminoalkyl, the alkoxyl group of C1 ~ C12 straight or branched, the perfluor substituted alkyl of C1 ~ C12 straight or branched, the cycloalkyl of C3 ~ C12, the 0 ~ aryl that all replaces or aryloxy, the 0 ~ heteroaryl that all replaces or heteroaryl oxygen base, the 0 ~ amido that all replaces or aryl amine or heteroaryl amido, fluorine, chlorine, bromine, iodine, hydroxyl, amino, carbonyl, carboxyl, ester group, alkylsulfonyl, sulfonic group, sulfonate group, phosphate-based or nitro; Or, R
7or R
85 ~ 6 rings are connected to adjacent substituents.
Described heteroaryl is the heteroaryl of five ~ ten-ring containing N, O or S.
Described benzazoles compound is benzothiazole, replaces benzothiazole, benzoxazoles or replace benzoxazoles, has the structure shown in formula II, wherein R
5~ R
9as hereinbefore defined.
Ⅱ。
Described aryl halides has the structure shown in formula III, wherein R
5~ R
9as hereinbefore defined, Y is chlorine, bromine or iodine.
Ⅲ。
Described iron catalyst includes but not limited to iron powder, iron protochloride, Iron diacetate, ferrous sulfate, Ferrox, ferrous fluoride, ferrous bromide, iron iodide, iron trichloride, ferric oxide; Copper catalyst includes but not limited to copper powder, cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, Red copper oxide, cupric oxide, copper sulfate, neutralized verdigris, trifluoroacetic acid copper, copper trifluoromethanesulfcomposite.
Described catalyzer also can be the combination of both arbitrary proportions arbitrarily in copper or iron catalyst.
Described alkali is mineral alkali or organic bases.Mineral alkali includes but not limited to sodium carbonate, salt of wormwood, cesium carbonate, potassiumphosphate, Potassium monofluoride, cesium fluoride, sodium methylate, sodium ethylate, potassium ethylate, trimethyl carbinol lithium, sodium tert-butoxide, potassium tert.-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide or cesium hydroxide; Organic bases includes but not limited to tetrabutyl ammonium fluoride, TBAH, triethylamine, diisopropylethylamine, Tributylamine, pyridine, the aniline that nitrogen replaces, 1,4-diazabicylo [2.2.2] octane, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene or 1,5-diazabicylo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene.
Described solvent alcohol includes but not limited to methyl alcohol, ethanol, Virahol, propyl carbinol, the trimethyl carbinol, ethylene glycol, glycerine, and molecular-weight average is the polyoxyethylene glycol (PEG200 ~ 2000) of 200 ~ 2000.
In described method, the mol ratio of aryl halides, benzazoles compound, catalyzer, alkali is 1-2:1:0.005-0.5:1-10.The weight ratio of benzazoles compound and solvent is 1:5 ~ 1000.
In described method, linked reaction temperature is 20-200
oc, the reaction times is 1-48 hour.
By technique scheme, the method for adjacent amino two aryl oxides of synthesis of the present invention and the amino two fragrant thioethers of neighbour at least has following advantages:
The invention provides a kind of in alcohol or water the benzazoles compound of iron or copper catalysis and the cross-coupling reaction of aryl halides prepare the novel method of adjacent amino two aryl oxides and the amino two fragrant thio-ether type compounds of neighbour.The method catalyzer is cheap and toxicity is little; Reaction is direct and Atom economy is high; Reaction is without the need to part and activity is good; Substrate source extensively and stable, the good and substrate of substrate functional group consistency applied widely.Described method is simple, and under the reaction conditions optimized, after target product is separated, yield is up to 96%, is the method for adjacent amino two aryl oxides of a kind of efficient, eco-friendly synthesis and the amino two fragrant thioethers of neighbour.
Amino two aryl oxides of neighbour prepared by the inventive method and the amino two fragrant thioethers of neighbour have unique biology, pharmacologically active and function, can as pharmaceutical intermediate, active drug molecule, Small-molecule probe and fluorescent material.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, be described in detail as follows below with preferred embodiment of the present invention.
Embodiment
For further setting forth the present invention for the technique means reaching predetermined goal of the invention and take and effect, to the technical scheme embodiment proposed according to the present invention, feature and effect thereof, be described in detail as follows.
Embodiment 1 ~ 12 relates to the synthesis of adjacent amino two fragrant thioethers, and experimental result lists in table
1:
Table
1the building-up reactions of the amino two fragrant thioethers of neighbour of metal catalytic
[a]
[a] reaction conditions is shown in embodiment; [b] post separation yield.
Embodiment 1
Copper powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 1:25mL reaction flask), be filled with nitrogen protection, add benzothiazole (0.5mmol) and iodobenzene (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 96%.
Embodiment 2
Copper powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 2:25mL reaction flask), be filled with nitrogen protection, add benzothiazole (0.5mmol) and adjacent toluene iodide (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 94%.
Embodiment 3
Add copper powder (0.05mmol) in compound 3:25mL reaction flask, sodium carbonate (1.0mmol) and PEG-4000 (2.0g), be filled with nitrogen protection, adds benzothiazole (0.5mmol) and paraiodoaniline (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 93%.
Embodiment 4
Add copper powder (0.05mmol) in compound 4:25mL reaction flask, sodium hydroxide (1.0mmol) and PEG-6000 (2.0g), be filled with nitrogen protection, adds benzothiazole (0.5mmol) and to bromo-iodobenzene (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 90%.
Embodiment 5
Add copper powder (0.05mmol) in compound 5:25mL reaction flask, triethylamine (1.0mmol) and ethanol (2.0g), be filled with nitrogen protection, adds benzothiazole (0.5mmol) and to fluorine iodobenzene (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 92%.
Embodiment 6
Add copper powder (0.05mmol) in compound 6:25mL reaction flask, pyridine (1.0mmol) and the trimethyl carbinol (2.0g), be filled with nitrogen protection, adds 6-methylbenzothiazole (0.5mmol) and to fluorine iodobenzene (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 81%.
Embodiment 7
Cuprous chloride (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 7:25mL reaction flask), be filled with nitrogen protection, add 6-nitrobenzene thiazole (0.5mmol) and adjacent toluene iodide (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 96%.
Embodiment 8
Neutralized verdigris (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 8:25mL reaction flask), be filled with nitrogen protection, add 6-nitrobenzene thiazole (0.5mmol) and to bromo-iodobenzene (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 88%.
Embodiment 9
Metal iron powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 9:25mL reaction flask), be filled with nitrogen protection, add 6-nitrobenzene thiazole (0.5mmol) and to fluorine iodobenzene (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 91%.
Embodiment 10
Iron protochloride (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 10:25mL reaction flask), be filled with nitrogen protection, add 6-nitrobenzene thiazole (0.5mmol) and adjacent iodine pyridine (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:3:1) obtains weak yellow liquid.Productive rate 78%.
Embodiment 11
Iron trichloride (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 11:25mL reaction flask), be filled with nitrogen protection; add 5; 6-dichlorobenzothiazole (0.5mmol) and the chloro-5-iodobenzene (1.0mmol) of 1,2,4-tri-.Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:2:1) obtains weak yellow liquid.Productive rate 86%.
Embodiment 12
Metallic copper and iron powder (0.05mmol) is added in compound 12:25mL reaction flask; cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g); be filled with nitrogen protection, add 5-iodine benzothiazole (0.5mmol) and 1-(2-iodophenyl)-
n,N-dimethyl methylamine (1.0mmol).Reaction mixture is 140
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:2:1) obtains weak yellow liquid.Productive rate 75%.
Embodiment 13 ~ 20 relates to the synthesis of adjacent amino two aryl oxides, and experimental result lists in table
2:
Table
2the building-up reactions of amino two aryl oxides of neighbour of metal catalytic
[a]
[a] reaction conditions is shown in embodiment; [b] post separation yield.
Embodiment 13
Copper powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 13:25mL reaction flask), be filled with nitrogen protection, add benzoxazoles (0.5mmol) and iodobenzene (1.0mmol).Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 93%.
Embodiment 14
Copper powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 14:25mL reaction flask), be filled with nitrogen protection, add 5-fluorine benzoxazoles (0.5mmol) and iodobenzene (1.0mmol).Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 95%.
Embodiment 15
Copper powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 15:25mL reaction flask), be filled with nitrogen protection, add 5-bromine benzoxazoles (0.5mmol) and iodobenzene (1.0mmol).Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 90%.
Embodiment 16
Copper powder (0.05mmol) is added, cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g in compound 16:25mL reaction flask), be filled with nitrogen protection; add 6-chlorobenzene diozaiole (0.5mmol) and 5-iodo-1; 2,3,4-naphthane (1.0mmol).Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 84%.
Embodiment 17
Metal iron powder (0.05mmol) is added in compound 17:25mL reaction flask; cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g); be filled with nitrogen protection, add 6-chlorobenzene diozaiole (0.5mmol) and iodo-1, the 3-(methylenedioxy) heterocyclic pentene (1.0mmol) of 4-.Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:2:1) obtains weak yellow liquid.Productive rate 76%.
Embodiment 18
Metal iron powder (0.05mmol) is added in compound 18:25mL reaction flask; cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g); be filled with nitrogen protection, add 5-chlorobenzene diozaiole (0.5mmol) and 2,4-bis-chloroiodobenzone (1.0mmol).Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:1:1) obtains weak yellow liquid.Productive rate 90%.
Embodiment 19
Metal iron powder (0.05mmol) is added in compound 19:25mL reaction flask; cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g); be filled with nitrogen protection, add 6-chlorinated oxazoline [5,4-b] pyridine (0.5mmol) and 2-iodo-benzoic acid methyl esters (1.0mmol).Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:2:1) obtains weak yellow liquid.Productive rate 72%.
Embodiment 20
Metal iron powder (0.05mmol) is added in compound 20:25mL reaction flask; cesium carbonate (1.0mmol) and polyoxyethylene glycol-600(2.0g); be filled with nitrogen protection, add 6-chlorinated oxazoline [5,4-b] pyridine (0.5mmol) and the iodo-2-picoline (1.0mmol) of 3-.Reaction mixture is 100
oreact complete to raw material reaction under C.Cool to room temperature, after removing solvent under reduced pressure, column chromatography for separation (sherwood oil: ether: triethylamine=30:3:1) obtains weak yellow liquid.Productive rate 68%.
Amino two aryl oxides of neighbour above prepared by each embodiment and the amino two fragrant thio-ether type compounds of neighbour all can be used as pharmaceutical intermediate, activated drug molecule, Small-molecule probe or fluorescent material and use.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art are understood that, are not departing within the scope of technical solution of the present invention, when carrying out changing or modifying obtaining corresponding embodiment, such as, for described substituent R
1~ R
4or R
5~ R
9can carry out within the scope of the present invention replacing, change or modifying, all can realize the inventive method.In every case be the aim not departing from technical solution of the present invention, any amendment done above embodiment according to of the present invention, modification or equivalent with equivalent change, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. the synthetic method of amino two aryl oxides of neighbour and the amino two fragrant thioethers of neighbour, it is characterized in that, take molecular-weight average as the polyoxyethylene glycol of 600 be solvent, under the effect of alkali cesium carbonate, add copper catalyst and/or iron catalyst, the aryl halides of formula III structure and the benzazoles compound open loop linked reaction of formula II structure, amino two aryl oxides of neighbour of obtained formula I structure or adjacent amino two fragrant thioethers, reaction expression is expressed as follows:
(Ⅱ)(Ⅲ)(Ⅰ)
In formula:
x=O or S;
R
1~ R
4or R
5~ R
9be selected from arbitrarily hydrogen, the alkyl of C1 ~ C12 straight or branched or aminoalkyl, the alkoxyl group of C1 ~ C12 straight or branched, the perfluor substituted alkyl of C1 ~ C12 straight or branched, the cycloalkyl of C3 ~ C12, the 0 ~ aryl that all replaces or aryloxy, the 0 ~ heteroaryl that all replaces or heteroaryl oxygen base, the 0 ~ amido that all replaces or aryl amine or heteroaryl amido, fluorine, chlorine, bromine, iodine, hydroxyl, amino, carbonyl, carboxyl, ester group, alkylsulfonyl, sulfonic group, sulfonate group, phosphate-based or nitro;
Or, R
7or R
85 ~ 6 rings are connected to adjacent substituents;
Y=chlorine, bromine or iodine.
2. according to claim
1described synthetic method, is characterized in that, described heteroaryl is the heteroaryl of five ~ ten-ring containing N, O or S.
3. according to claim
1described synthetic method, is characterized in that, the mol ratio of described aryl halides, benzazoles compound, catalyzer, alkali is 1-2:1:0.005-0.5:1-10.
4. according to claim
1described synthetic method, is characterized in that, described catalyzer is the mixture of iron catalyst and copper catalyst arbitrary proportion.
5. according to claim
1described synthetic method, is characterized in that, described iron catalyst is iron powder, iron protochloride, Iron diacetate, ferrous sulfate, Ferrox, ferrous fluoride, ferrous bromide, iron iodide, iron trichloride or ferric oxide; Described copper catalyst is copper powder, cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, Red copper oxide, cupric oxide, copper sulfate, neutralized verdigris, trifluoroacetic acid copper or copper trifluoromethanesulfcomposite.
6. according to claim
1described synthetic method, is characterized in that, described benzazoles compound and the weight ratio of solvent are 1:5 ~ 1000.
7. according to claim
1described synthetic method, is characterized in that, in described method, linked reaction temperature is 20-200
oc, the reaction times is 1-48 hour.
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