CN105130841A - Preparation method of 3-iodophenyl azide compound - Google Patents
Preparation method of 3-iodophenyl azide compound Download PDFInfo
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- CN105130841A CN105130841A CN201510427453.7A CN201510427453A CN105130841A CN 105130841 A CN105130841 A CN 105130841A CN 201510427453 A CN201510427453 A CN 201510427453A CN 105130841 A CN105130841 A CN 105130841A
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Abstract
The invention discloses a preparation method of a 3-iodophenyl azide compound, 1-(3-azidopropyl)-3-iodo-4-methoxybenzene. With 3-(3-iodo-4-methoxyphenyl)acrylic acid as an initial raw material, the preparation method includes the steps of reduction, hydrogenation, MS treatment and an azido reaction to obtain a target product 5. The target product is employed as a template small molecule to synthesize various compound libraries.
Description
Technical field
The present invention relates to a kind of novel processing step of medicine intermediate, particularly the preparation method of the iodo-4-anisole of a kind of 3-iodophenyl triazo-compound 1-(3-Azidopropyl)-3-.
Technical background
The iodo-4-anisole of compound 1-(3-Azidopropyl)-3-, structural formula is:
This compound 3-iodophenyl triazo-compound 1-(3-Azidopropyl)-3-iodo-4-anisole and relevant derivative have widespread use in pharmaceutical chemistry and organic synthesis.The synthesis of current 3-iodophenyl triazo-compound 1-(3-Azidopropyl)-3-iodo-4-anisole is comparatively difficult.Therefore, need exploitation raw material to be easy to get, easy to operate, reaction is easy to control, the synthetic method that overall yield is suitable.
Summary of the invention
The invention discloses the preparation method of the iodo-4-anisole of a kind of 3-iodophenyl triazo-compound 1-(3-Azidopropyl)-2-, with 3-(the iodo-4-p-methoxy-phenyl of 2-) vinylformic acid for starting raw material, obtain target product 5 through reduction, hydrogenation, upper Ms, azido reaction, synthetic route as shown in Figure 1.Synthesis step is as follows:
(1) 3-(the iodo-4-p-methoxy-phenyl of 3-) vinylformic acid is starting raw material, obtains 2 through reduction reaction,
(2) carry out hydrogenation reaction 2, obtain 3,
(3) carry out upper Ms 3 and be obtained by reacting 4,
(4) carry out azido reaction 4 and obtain 5,
One preferred embodiment in, described reduction reaction is prepared compound 2 reagent used and is selected from Lithium Aluminium Hydride; Described hydrogenation reaction is prepared compound 3 reagent used and is selected from palladium carbon; Described upper Ms reacts the reagent preparing compound 4 used and is selected from triethylamine; The reagent that described azido reaction prepares compound 5 used is selected from sodiumazide.
One preferred embodiment in, the solvent that described reduction reaction prepares compound 2 used is selected from tetrahydrofuran (THF); Described hydrogenation reaction prepares compound 3 solvent selected from methanol used; Described upper Ms reacts the solvent preparing compound 4 used and is selected from methylene iodide; The solvent that described azido reaction prepares compound 5 used is selected from DMF.
One preferred embodiment in, described reduction reaction prepare compound 2 temperature of reaction used be 0 DEG C to room temperature; It is room temperature that described hydrogenation reaction prepares compound 3 temperature used; Described upper Ms reaction prepare compound 4 temperature used be 0 DEG C to room temperature; It is room temperature that described azido reaction prepares compound 5 temperature used.
The present invention relates to the preparation method of the iodo-4-anisole of a kind of 3-iodophenyl triazo-compound 1-(3-Azidopropyl)-3-, there is no other Patents bibliographical informations at present.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the iodo-4-anisole of compound 1-(3-Azidopropyl)-3-.
The present invention is further described by the following embodiment, and these descriptions are not be further limited content of the present invention.One skilled in the art will understand that the equivalent replacement that technical characteristic of the present invention is done, or improve accordingly, still belong within protection scope of the present invention.
Specific embodiment mode
Embodiment 1
(1) synthesis of 3-(the iodo-4-p-methoxy-phenyl of 3-) third-2-alkene-1-alcohol
16g3-(the iodo-4-p-methoxy-phenyl of 2-) vinylformic acid is joined in 200ml tetrahydrofuran (THF), be cooled to 0 DEG C, slowly add 6g Lithium Aluminium Hydride in batches, stirred overnight at room temperature, adds water and ethyl acetate, extraction separatory, collect organic phase, drying, concentrated, obtain 7g3-(the iodo-4-p-methoxy-phenyl of 3-) third-2-alkene-1-alcohol.
(2) synthesis of 3-(the iodo-4-p-methoxy-phenyl of 2-) the third-1-alcohol
7g3-(the iodo-4-p-methoxy-phenyl of 3-) third-2-alkene-1-alcohol is joined in 40ml methyl alcohol, adds 0.5g10% palladium carbon, pass into hydrogen, stirred overnight at room temperature, filters, and collects filtrate, concentrated, obtain 5g3-(the iodo-4-p-methoxy-phenyl of 3-) the third-1-alcohol.
(3) synthesis of 3-(the iodo-4-p-methoxy-phenyl of 3-) propyl Methanesulfonate
5g3-(the iodo-4-p-methoxy-phenyl of 3-) the third-1-alcohol is joined in 50ml methylene iodide, add 3g triethylamine, be cooled to 0 DEG C, add 2.9gMsCl, stirring at room temperature 2 hours, add water again, extraction separatory, collects organic phase, dry, concentrated, on residuum, silicagel column is separated to obtain 3.4g3-(the iodo-4-p-methoxy-phenyl of 3-) propyl Methanesulfonate.
(4) synthesis of the iodo-4-anisole of 1-(3-Azidopropyl)-3-
3g3-(the iodo-4-p-methoxy-phenyl of 3-) propyl Methanesulfonate is joined 30mlN, in dinethylformamide, add 4g sodiumazide, stirring at room temperature 6 hours, adds water and ethyl acetate, extraction separatory, collect organic phase, drying, concentrated, on residuum, silicagel column is separated to obtain the iodo-4-anisole of 2.5g1-(3-Azidopropyl)-3-.
Claims (5)
1. an a kind of 3-iodophenyl triazo-compound 1-(3-Azidopropyl) preparation method of the iodo-4-anisole of-3-, with the iodo-4-p-methoxy-phenyl of 3-(3-) vinylformic acid is for starting raw material, obtain target product 5 through reduction, hydrogenation, upper Ms, azido reaction, synthetic route is as follows:
2. method according to claim 1, it is characterized by 4 described step reactions is,
(1) the iodo-4-p-methoxy-phenyl of 3-(3-) vinylformic acid is starting raw material, obtains 2 through reduction reaction,
(2) carry out hydrogenation reaction 2, obtain 3,
(3) carry out upper Ms 3 and be obtained by reacting 4,
(4) carry out azido reaction 4 and obtain 5,
3. according to the method for claim 1-2, it is characterized in that, described reduction reaction is prepared compound 2 reagent used and is selected from one or both mixture in borine, Lithium Aluminium Hydride; Described hydrogenation reaction is prepared compound 3 reagent used and is selected from the mixture of one or more in palladium carbon, palladium hydroxide, Raney's nickel; Described upper Ms reaction is prepared compound 4 reagent used and is selected from the mixture of one or more in triethylamine, pyridine, salt of wormwood, sodium hydroxide; The reagent that described azido reaction prepares compound 5 used is selected from sodiumazide.
4. according to the method for claim 1-2, it is characterized in that, described reduction reaction is prepared compound 2 solvent used and is selected from tetrahydrofuran (THF), methylene iodide, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile; Described hydrogenation reaction prepares compound 3 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), methylene iodide, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile; Compound 4 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, acetonitrile, tetrahydrofuran (THF), dioxane, methylene iodide, triiodomethane, toluene, o-Xylol, p-Xylol, m-xylene, N are prepared in described upper Ms reaction, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide; Described azido reaction prepares compound 5 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), methylene iodide, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile.
5. according to the method for claim 1-2, it is characterized in that, it is 0 DEG C of reflux temperature to solvent that described reduction reaction prepares compound 2 temperature of reaction used; It is room temperature that described hydrogenation reaction prepares compound 3 temperature used; It is 0 DEG C of reflux temperature to solvent that compound 4 temperature used is prepared in described upper Ms reaction; It is room temperature that described azido reaction prepares compound 5 temperature used.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883140A (en) * | 2017-02-26 | 2017-06-23 | 长沙深橙生物科技有限公司 | A kind of preparation method containing azido micromolecular compound |
| CN107043335A (en) * | 2017-05-31 | 2017-08-15 | 湖南华腾制药有限公司 | A kind of preparation method of 2 fluorophenyl azido compound |
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2015
- 2015-07-20 CN CN201510427453.7A patent/CN105130841A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883140A (en) * | 2017-02-26 | 2017-06-23 | 长沙深橙生物科技有限公司 | A kind of preparation method containing azido micromolecular compound |
| CN107043335A (en) * | 2017-05-31 | 2017-08-15 | 湖南华腾制药有限公司 | A kind of preparation method of 2 fluorophenyl azido compound |
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Application publication date: 20151209 |