CN100355710C - Method for preparing aryl iodo substance - Google Patents
Method for preparing aryl iodo substance Download PDFInfo
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- CN100355710C CN100355710C CNB200510111515XA CN200510111515A CN100355710C CN 100355710 C CN100355710 C CN 100355710C CN B200510111515X A CNB200510111515X A CN B200510111515XA CN 200510111515 A CN200510111515 A CN 200510111515A CN 100355710 C CN100355710 C CN 100355710C
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- iodo
- bismuth
- preparation
- reaction
- methylene dichloride
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Abstract
The present invention relates to a method for preparing arene iodo substances, which belongs to the technical field of chemical engineering. Active arene and bismuth salt catalysts are added in a round bottom flask and are stirred in solvent to react under the condition of air or 1 pressure atmosphere oxygen, and reaction mixture is diluted by adding solvent, is filtered and then is washed by sodium thiosulfate water solution until unreacted iodine is washed out. The water phase is extracted by solvent, organic phases are merged, dried by magnesium sulfate anhydrous and filtered, and the solvent is eliminated through reduced pressure distillation. Then, iodo arene is obtained through separation by adopting column chromatography. The present invention utilizes air as oxidants for catalysis oxidation iodination reaction and has the advantages of moderate reaction conditions, convenient operation and friendly environments.
Description
Technical field
That the present invention relates to is the preparation method of a kind of method of chemical technology field, particularly a kind of aryl iodo substance.
Background technology
Iodo aromatic hydrocarbons is the important organic chemicals that a class is widely used in fields such as biology, medicine, organic synthesis.Preparation iodo aromatic hydrocarbons is finished by the aromatic hydrocarbons iodide reaction.Usually need some exacting terms, as: HNO
3/ H
2SO
4, NIS/CF
3SO
3H etc.; Or some special reagent, as: ICl/Ag
2SO
4/ H
2SO
4, NIS/CH
3CN and [(CH
3)
4N]
+[ICl
2]
-Deng; Nitric acid/sulfuric acid [HNO
3/ H
2SO
4], N-iodo fourth two lactan/trifluoromethanesulfonic acid [NIS/CF
3SO
3H] etc.; Or some special reagent, as: iodine chloride/Sulfuric acid disilver salt/sulfuric acid [ICl/Ag
2SO
4/ H
2SO
4], N-iodo fourth two lactan/acetonitrile [NIS/CH
3CN] and the tetramethyl-dichloro close ammonium iodate { [(CH
3)
4N]
+[ICl
2]
-Etc..
Through the literature search of prior art is found, people such as Neumann disclose aromatic hydrocarbons and molecular iodine at heteropolyacid [H in " American Chemical Society's organic chemistry " periodical 2003 annuals the 24th phase of the 68th phase the 9510th page (" J.Org.Chem " .2003,68,9510.)
5PV
2Mo
10O
40] make catalyzer, 2 normal atmosphere oxygen, 80 ℃ of heating conditions generate the reaction of iodo aromatic hydrocarbons down.The defective of this method has: (1) catalyst system therefor is a transistion metal compound, all can produce environmentally harmful material in its preparation process and after using; (2) need to use 2 atmospheric pure oxygens, inconvenient operation, production cost height; (3) need be heated to high temperature, inconvenient operation, consumes energy, production cost height.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of aryl iodo substance is provided, make it at room temperature make catalyzer with bismuth salt, airborne oxygen is made oxygenant, and the direct oxidation iodo generates iodo aromatic hydrocarbons.Reaction conditions gentleness of the present invention, easy and simple to handle, environmental friendliness.
The present invention is achieved through the following technical solutions, and the present invention is specific as follows:
In round-bottomed flask, add active aromatic hydrocarbons, bismuth salt catalyst, under air or 1 normal atmosphere oxygen condition, in solvent, stir, react.In reaction mixture, add solvent cut, filter, wash with sodium thiosulfate solution then, to the unreacted iodine of flush away (organic phase by redness to colourless).Water is used solvent extraction again.Merge organic phase, use anhydrous magnesium sulfate drying, filter, underpressure distillation removes and desolvates, and gets iodo aromatic hydrocarbons through column chromatography for separation again.
Reaction formula of the present invention is formula as follows:
In the present invention, raw material is the active aromatic hydrocarbons of structure shown in (I), and R can be an electron-donating group, can be one or more, comprises the combination of power supplying groups and non-power supplying groups.Preferred substituted group is a methoxyl group, as methyl-phenoxide.
In the present invention, the bismuth salt catalyst is a trivalent bismuth salt, can be five water Bismuth trinitrates, also can be five water Bismuth trinitrate [Bi (NO
3)
35H
2O] and bismuth chloride [BiCl
3] combination.
In the present invention, operable solvent is aprotic polar solvent, non-polar solvent, acid proton solvent or neutral solvent, wherein aprotic polar solvent, preferably methylene dichloride; Non-polar solvent, preferably 1, the 2-ethylene dichloride; Acid proton solvent, preferably acetic acid; Neutral solvent, preferably acetonitrile.
In the present invention, the reaction times is 0.25～24 hour, and temperature of reaction is 0 ℃～50 ℃.
In the present invention, the amount of substance of bismuth salt catalyst (mole number) is according to the amount of substance decision of reactant, and generally can adopt 0.1% to 10%, two kind of bismuth salt amount ratio of the amount of reactant species is between 5: 1 to 1: 5.
Because the present invention utilizes bismuth salt to make catalyzer, air oxidant aromatic hydrocarbons direct oxidation iodo has been avoided the use of a large amount of inorganic oxidizer, uses the stable air oxidant that is easy to get, economy, environmental friendliness simultaneously.
In addition, the reaction among the present invention can be carried out at ambient temperature, and reaction reagent need not to carry out processed, and reaction system need not have water conservation yet in the reaction process, and is easy and simple to handle.
The present invention at room temperature, the active aromatic hydrocarbons of raw material, bismuth salt catalyst, atmospheric oxidation agent together in solvent stirring reaction obtain product iodine for aromatic hydrocarbons.Its beneficial effect is: (1) catalyst system therefor is nontoxic nontransition metal bismuth salt mixture, and the industrial goods supply and marketing is all arranged, and need not preparation in advance, and reclaims conveniently; (2) use oxygenant to be atmospheric air, and need not to handle before the air use.Easy to operate, with low cost; (3) reaction is at room temperature carried out, and room temperature range is wide, is not subjected to weather effect.Easy and simple to handle, save energy.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the scope of the invention is not limited to following embodiment.
Embodiment 1
At room temperature (25 ℃), (110.7mg, 1.02mmol), (140.7mg, 0.55mmol), (12.5mg, 0.026mmol), (8.5mg 0.027mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate iodine to add methyl-phenoxide in the 25ml round-bottomed flask.After 6 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 4-phenyl-iodide methyl ether 216.2mg, and yield is 90%.
Embodiment 2
Under 0 ℃ of condition, (108.8mg, 1.00mmol), (140.4mg, 0.55mmol), (12.2mg, 0.025mmol), (7.8mg 0.025mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate iodine to add methyl-phenoxide in the 25ml round-bottomed flask.After 24 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 4-phenyl-iodide methyl ether 187.2mg, and yield is 80%.
Embodiment 3
Under 50 ℃ of conditions, (108.9mg, 1.00mmol), (140.5mg, 0.55mmol), (12.4mg, 0.026mmol), (8.6mg 0.027mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate iodine to add methyl-phenoxide in the 25ml round-bottomed flask.After 4 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 4-phenyl-iodide methyl ether 199.1mg, and yield is 85%.
Embodiment 4
At room temperature (25 ℃) add 1,3 in the 25ml round-bottomed flask, and (128.7mg, 1.07mmol), (139.7mg, 0.55mmol), (13.0mg, 0.027mmol), (10.9mg 0.035mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate iodine 5-trimethylbenzene.After 6 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 2-iodo-1,3, and 5-trimethylbenzene 212.1mg, yield are 80%.
Embodiment 5
At room temperature (25 ℃), (170.9mg, 0.99mmol), (142.1mg, 0.56mmol), (12.8mg, 0.026mmol), (7.9mg 0.025mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate iodine to add β-Nai Yimi in the 25ml round-bottomed flask.After 6 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product alpha-iodine generation-β-Nai Yimi 289.9mg, and yield is 98%.
Embodiment 6
At room temperature (25 ℃), (112.7mg, 0.92mmol), (128.8mg, 0.51mmol), (13.3mg, 0.027mmol), (10.3mg 0.033mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate iodine to add 4-methylbenzene methyl ether in the 25ml round-bottomed flask.After 12 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.
1The amount that HNMR measures product 2-iodo-4-methylbenzene methyl ether in the crude product is 147.5mg, and yield is 78%.
Embodiment 7
At room temperature (25 ℃), (110.3mg, 1.02mmol), (184.9mg, 1.1mmol), (12.3mg, 0.025mmol), (9.5mg 0.030mmol) stirs in the 1ml acetonitrile bismuth chloride Bismuth trinitrate potassiumiodide to add methyl-phenoxide in the 25ml round-bottomed flask.After 6 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 4-phenyl-iodide methyl ether 77.5mg, and yield is 31%.
Embodiment 8
At room temperature (25 ℃), and adding 2-methylbenzene methyl ether in the 25ml round-bottomed flask (61.3mg, 0.50mmol), potassiumiodide (85.3mg, 0.51mmol), Bismuth trinitrate (12.0mg, 0.025mmol), (154.4mg 0.49mmol) stirs in 1ml acetate bismuth chloride.After 6 hours, stopped reaction.In reaction mixture, add methylene dichloride 10ml, filter, wash (10ml * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 4-iodo-2-methylbenzene methyl ether 89.4mg, and yield is 72%.
Embodiment 9
Under 44 ℃, (118.9mg, 1.10mmol), (149.8mg, 0.59mmol), (11.7mg, 0.024mmol), (11.0mg 0.035mmol) stirs in the 1mL acetonitrile bismuth chloride Bismuth trinitrate iodine to add methyl-phenoxide in the 25mL round-bottomed flask.After 6 hours, stopped reaction.In reaction mixture, add methylene dichloride 10mL, filter, wash (10mL * 3 time) with the 0.5M sodium thiosulfate solution then, to the unnecessary iodine of flush away (organic phase by redness to colourless).Water again with methylene dichloride 10mL extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter, methylene dichloride is removed in underpressure distillation.Column chromatography for separation gets product 4-phenyl-iodide methyl ether 233.3mg, and yield is 90%.
Embodiment 10
At room temperature (25 ℃), (121.1,1.12mmol), (127.1mg, 0.50mmol), (6.6mg, 0.014mmol), (8.9mg 0.028mmol) stirs in 1mL acetic acid bismuth chloride Bismuth trinitrate iodine to add methyl-phenoxide in the 25mL round-bottomed flask.After 8 hours, stopped reaction.The amount of product 4-phenyl-iodide methyl ether in the GC assaying reaction liquid, yield is 84%.
Embodiment 11
At room temperature (25 ℃) add methyl-phenoxide (0.5mL, 5mmol make solvent) in the 25mL round-bottomed flask, (132.2mg, 0.52mmol), (13.1mg, 0.027mmol), (8.8mg 0.028mmol), stirs bismuth chloride Bismuth trinitrate iodine.After 1 hour, stopped reaction.The amount of product 4-phenyl-iodide methyl ether in the GC assaying reaction liquid, yield is greater than 99%.
Embodiment 12
At room temperature (25 ℃), under the condition of logical 1 normal atmosphere oxygen, (133.8,1.24mmol), (127.4mg, 0.50mmol), (24.8mg 0.051mmol), stirs in the 3mL acetonitrile Bismuth trinitrate iodine then to add methyl-phenoxide in 25mL Schlenk pipe.Reacted 18 hours, the amount of product 4-phenyl-iodide methyl ether in the GC assaying reaction liquid, yield is 89%.24 hours, the amount of product 4-phenyl-iodide methyl ether in the GC assaying reaction liquid, yield is greater than 99%.
Claims (7)
1, a kind of preparation method of aryl iodo substance, it is characterized in that, in round-bottomed flask, add active aromatic hydrocarbons, the bismuth salt catalyst, under air or 1 normal atmosphere oxygen condition, in acetonitrile or acetate, stir, reaction, in reaction mixture, add methylene dichloride or 1, the dilution of 2-ethylene dichloride, filter, wash with sodium thiosulfate solution then, to the unreacted iodine of flush away, water is again with methylene dichloride or 1, the extraction of 2-ethylene dichloride merges organic phase, uses anhydrous magnesium sulfate drying, filter, methylene dichloride or 1 are removed in underpressure distillation, and the 2-ethylene dichloride gets iodo aromatic hydrocarbons through column chromatography for separation again.
2, the preparation method of aryl iodo substance according to claim 1 is characterized in that, described active aromatic hydrocarbons, its structure shown in (I),
Wherein, R is one or more electron-donating groups, or the combination of power supplying groups and non-power supplying groups.
3, the preparation method of aryl iodo substance according to claim 1 is characterized in that, described active aromatic hydrocarbons, its structure shown in (I),
Wherein, R is a methoxyl group.
4, the preparation method of aryl iodo substance according to claim 1 is characterized in that, described bismuth salt catalyst is a trivalent bismuth salt.
5, the preparation method of aryl iodo substance according to claim 1 is characterized in that, described bismuth salt catalyst is five water Bismuth trinitrates, or the combination of five water Bismuth trinitrates and bismuth chloride.
6, the preparation method of aryl iodo substance according to claim 1 is characterized in that, the reaction times is 0.25～24 hour, and temperature of reaction is 0 ℃～50 ℃.
7, the preparation method of aryl iodo substance according to claim 5 is characterized in that, two kinds of bismuth salt five water Bismuth trinitrates and bismuth chloride amount ratio are between 5: 1 to 1: 5.
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|---|---|---|---|
| CNB200510111515XA CN100355710C (en) | 2005-12-15 | 2005-12-15 | Method for preparing aryl iodo substance |
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|---|---|---|---|
| CNB200510111515XA CN100355710C (en) | 2005-12-15 | 2005-12-15 | Method for preparing aryl iodo substance |
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|---|---|
| CN1775716A CN1775716A (en) | 2006-05-24 |
| CN100355710C true CN100355710C (en) | 2007-12-19 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106739A (en) * | 1986-09-29 | 1988-04-13 | 伊斯曼柯达公司 | The preparation method of iodinating aromatics |
| CN88101781A (en) * | 1987-03-25 | 1988-11-02 | 伊斯曼柯达公司 | The preparation method of the aromatic substance that iodine replaces |
| US4922041A (en) * | 1987-05-22 | 1990-05-01 | Kali-Chemie Ag | Method for producing CF3 I |
| CN1257476A (en) * | 1997-05-23 | 2000-06-21 | 耐克麦德英梅金公司 | Preparation of tri-iodo benzene compound |
| CN1322710A (en) * | 2001-04-26 | 2001-11-21 | 上海交通大学 | Prepn of triphenylamine derivative |
-
2005
- 2005-12-15 CN CNB200510111515XA patent/CN100355710C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106739A (en) * | 1986-09-29 | 1988-04-13 | 伊斯曼柯达公司 | The preparation method of iodinating aromatics |
| CN88101781A (en) * | 1987-03-25 | 1988-11-02 | 伊斯曼柯达公司 | The preparation method of the aromatic substance that iodine replaces |
| US4922041A (en) * | 1987-05-22 | 1990-05-01 | Kali-Chemie Ag | Method for producing CF3 I |
| CN1257476A (en) * | 1997-05-23 | 2000-06-21 | 耐克麦德英梅金公司 | Preparation of tri-iodo benzene compound |
| CN1322710A (en) * | 2001-04-26 | 2001-11-21 | 上海交通大学 | Prepn of triphenylamine derivative |
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| CN1775716A (en) | 2006-05-24 |
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