CN102603495A - Preparation method of aromatic iodide in water phase - Google Patents
Preparation method of aromatic iodide in water phase Download PDFInfo
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- CN102603495A CN102603495A CN 201110020942 CN201110020942A CN102603495A CN 102603495 A CN102603495 A CN 102603495A CN 201110020942 CN201110020942 CN 201110020942 CN 201110020942 A CN201110020942 A CN 201110020942A CN 102603495 A CN102603495 A CN 102603495A
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Abstract
The invention relates to a preparation method of an aromatic iodide aromatic compound. The method comprises: subjecting aromatic hydrocarbon, hydrogen peroxide, a catalyst able to promote hydrogen peroxide decomposition to stirring and reaction in water under normal pressure. At the end of the reaction, the mixed reaction solution automatically falls into a water phase and an oil phase, and the separated oil phase is the iodide aromatic compound. The method of the invention utilizes the hydroxyl free radical generated from catalytic decomposition of hydrogen peroxide as an oxidizing agent to conduct catalytic oxidation iodination reaction in the water phase, and has the characteristics of no need of strong acidic catalyst, mild reaction condition, high conversion rate, high selectivity, simple operation, and environmental friendliness.
Description
Technical field
The invention belongs to chemical technology field, utilize hydrogen peroxide catalyzed decomposition generation hydroxyl radical free radical to reach the activation iodine molecule is further realized the iodide reaction of high efficiency aromatic hydrocarbons in water technology thereby relate to.
Background technology
In organic synthesis, because the chemical property of iodo aromatic compound is more active, many reactions can take place, for example substitution reaction etc., thus the compound that changes into other types perhaps directly is used for synthesizing of new compound.Therefore, introducing the iodine atom usually is the first step reaction that changes molecule performance, synthetic new compound, in organic synthesis, plays important function served as bridge.Compound method commonly used at present mainly contains: directly iodo method and Indirect Iodine are for method.Indirect Iodine widespread use for method has the gentle relatively characteristics of efficient height, condition, but the main drawback that this method faces is raw materials cost that it is higher and loaded down with trivial details polystep reaction process.Compare Indirect Iodine for method, directly the iodo method has characteristics with low cost.But because the water-soluble salt of iodine or iodine,, a little less than the electrophilic substitution effect very of itself, often need will contain iodine reagent down to be oxidized to the iodine species that show nominal price, and just can make the iodide reaction generation at strong oxidizing condition like Soiodin (NaI) etc.Oxidising agent commonly used at present comprises the salt of nitric acid, high valence state, or some special reagent.Have part document utilization ydrogen peroxide 50 to come activation iodine, but because the oxidation capacity of ydrogen peroxide 50 itself is strong not enough, these systems often all need add a large amount of strongly-acid material example hydrochloric acid etc. and make catalyzer.
More than the remarkable shortcoming that exists of these systems be: (1) reaction is normally carried out in organic solvent, and cost is high, pollutes heavy; (2) reaction needs strongly-acid material example hydrochloric acid, nitric acid usually, and condition is harsh; (3) special strong oxidising agent preparation cost is high, strong toxicity.These but a big factor that harsh reaction conditions and complex operating steps become the direct iodo method of restriction.How to seek a kind of efficiently, still there is challenge in the iodide reaction method of green aromatic hydrocarbons.
As everyone knows, hydroxyl radical free radical has very strong oxidation capacity, its oxidation capacity even be only second to fluorine.But up to the present, still have nothing to do in using hydroxyl radical free radical to come activation iodine to realize the report of technology of the iodide reaction of high efficiency aromatic hydrocarbons.
Summary of the invention
The object of the present invention is to provide a kind of brand-new, green, direct iodo method of aromatic hydrocarbons efficiently.This method utilizes ydrogen peroxide 50 catalytic decomposition process generation great amount of hydroxy group radical (seeing figure one) to come activation iodine, further in water solvent, accomplishes the iodide reaction of the aromatic hydrocarbons of high conversion, highly selective.
Iodo scheme of the present invention is following:
(1) deionized water, aromatic compound and iodine reagent are mixed, add the reagent that an amount of catalyzing hydrogen peroxide decomposes, like nano ceric oxide.
(2) heat this mixed system, in this reaction system, drip concentration simultaneously and be 30% ydrogen peroxide 50, heat 10-100 ℃; 0.5 afterreaction finished in～10 hours; Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase is the thick product of aryl iodo substance; Thick product can obtain pure iodo aromatic compound through column chromatography for separation.Reclaim nano ceric oxide from isolating aqueous phase spinning, after the washing drying, can reuse.
Characteristics of the present invention comprise:
(1) utilize the ydrogen peroxide 50 catalytic decomposition process to produce the great amount of hydroxy group radical and come activation iodine, oxidisability is better than ydrogen peroxide 50 itself far away, and reaction conditions is gentle, and reaction conversion ratio is high, and is simple to operate.
(2) this method is applicable to 1, the 3-m-xylene, and 1, two methyl-phenoxides between 3-, methyl-phenoxide,
Toluene, benzene, multiple aromatic compound such as chlorobenzene;
(3) the single often iodo product of the iodo aromatic compound that obtains, and iodine the position of substitution is fixed;
(4) this is reflected at aqueous phase and carries out, and be a typical green process, and product is easily separated.
(5) utilize nano ceric oxide catalysis decomposing hydrogen dioxide solution, efficient nano ceric oxide high, that exist as solid state is easy to reclaim repeated use.
Embodiment
Embodiment 1
Get 1, two methyl-phenoxides, 0.14 gram joins in the 1ml deionized water between 3-, and adds 0.12 gram elemental iodine and 0.08 gram nano ceric oxide.Under 10 ℃, add the 2ml ydrogen peroxide 50, magnetic agitation 30 minutes.Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase obtains getting 4-iodo 1 through column chromatography for separation, two methyl-phenoxides between 3-, and recording product yield is 97%.
Embodiment 2
Get benzene 0.1 gram, join in the 1ml deionized water, and add 0.12 gram elemental iodine and 0.08 gram nanometer titanium dioxide crystalline substance.Under 80 ℃ of reflux conditions, add the 2ml ydrogen peroxide 50, magnetic agitation 8 hours.Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase obtains iodobenzene through column chromatography for separation.The transformation efficiency that records benzene is 78%.The spinning cerium dioxide, with the cerium dioxide recycled for multiple times that reclaims, the efficient that records cerium dioxide catalysis decomposing hydrogen dioxide solution does not change, and this reaction conversion ratio is constant basically.
Embodiment 3
Get m-xylene 0.11 gram, join in the 1ml deionized water, and add 0.1 gram Soiodin and 0.04 gram ceria nano-crystalline.Under 50 ℃ of reflux conditions, add the 2ml ydrogen peroxide 50, magnetic agitation 90 minutes.Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase obtains 4-iodo 1 through column chromatography for separation, the 3-m-xylene, and recording product yield is 92%.
Embodiment 4
Get methyl-phenoxide 0.11 gram, join in the 1ml deionized water, and add 0.12 gram elemental iodine and 0.08 gram ceria nano-crystalline.Under the reflux condition, add the 2ml ydrogen peroxide 50, magnetic agitation 2 hours.Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase obtains 4-phenyl-iodide methyl ether through column chromatography for separation, and recording product yield is 89%.
Embodiment 5
Get toluene 0.1 gram, join in the 1ml deionized water, and add 0.1 gram Soiodin and 0.02 gram ceria nano-crystalline.Under 70 ℃ of reflux conditions, add the 2ml ydrogen peroxide 50, magnetic agitation 4 hours.Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase obtains 4-iodo toluene through column chromatography for separation, and recording toluene conversion is 80%.
Embodiment 6
Get chlorobenzene 0.12 gram, join in the 1ml deionized water, and add 0.12 gram elemental iodine and 0.08 gram ceria nano-crystalline.Under 100 ℃ of reflux conditions, add the 2ml ydrogen peroxide 50, magnetic agitation 10 hours.Mixed reaction solution is left standstill, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase obtains 4-iodo chlorobenzene through column chromatography for separation, and recording the chlorobenzene transformation efficiency is 73%.
Description of drawings
The electron paramagnetic resonance spectrum of Fig. 1 hydroxyl radical free radical.The electron paramagnetic resonance spectrum of hydroxyl radical free radical.(a) ydrogen peroxide 50 and 5,5-dimethyl--1-pyrroles N-oxide compound (DMPO) coexistence, no radical signal; (b) cerium dioxide and DMPO coexistence system, no radical signal; (c) the hydroxyl radical free radical signal appears in ydrogen peroxide 50, cerium dioxide and DMPO coexistence system.In the aromatic hydrocarbons iodide reaction, under reaction reagent and reaction conditions that the present invention uses, only under the situation that hydroxyl radical free radical exists, iodide reaction is taken place, shown the decisive role of hydroxyl radical free radical.
Claims (5)
1. the preparation method of an aqueous phase aryl iodo substance is characterized in that, aromatic hydrocarbons, contains iodine reagent, ydrogen peroxide 50, can promote the catalyzer of decomposing hydrogen dioxide solution in water, to mix, and under normal pressure, heating condition, stirs, reaction.Reaction after finishing is left standstill mixed reaction solution, and mixed reaction solution is divided into water oil two phases automatically, and separated oil phase is the thick product of aryl iodo substance, and thick product can obtain pure iodo aromatic compound through column chromatography for separation.
Described aromatic hydrocarbons, its chemical structural formula is following:
Wherein, R is one or more substituted radicals, comprises hydrogen, power supplying groups or electron-withdrawing group.
2. according to the described preparation method of claim 1, it is characterized in that containing the water-soluble salt that iodine reagent can be iodine or iodine, like Soiodin (NaI) etc.
3. preparation method according to claim 1 is characterized in that promoting that the catalyzer of decomposing hydrogen dioxide solution is a nano ceric oxide.
4. preparation method according to claim 1 is characterized in that this iodide reaction carries out in water.
5. preparation method according to claim 1, it is characterized in that this is reflected under the heating condition carries out, and Heating temperature is 10～100 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365243A (en) * | 2017-07-21 | 2017-11-21 | 中南民族大学 | A kind of method of one pot process benzoquinone class compound |
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2011
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365243A (en) * | 2017-07-21 | 2017-11-21 | 中南民族大学 | A kind of method of one pot process benzoquinone class compound |
| CN107365243B (en) * | 2017-07-21 | 2020-11-06 | 中南民族大学 | Method for synthesizing p-phenylene benzoquinone compound by one-pot method |
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Application publication date: 20120725 |