CN1706786A - Synthesis of 2-methoxyl-5-iodophenol - Google Patents
Synthesis of 2-methoxyl-5-iodophenol Download PDFInfo
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- CN1706786A CN1706786A CN 200510025860 CN200510025860A CN1706786A CN 1706786 A CN1706786 A CN 1706786A CN 200510025860 CN200510025860 CN 200510025860 CN 200510025860 A CN200510025860 A CN 200510025860A CN 1706786 A CN1706786 A CN 1706786A
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- methoxyl group
- methoxyl
- phenol
- iodophenol
- phenol ester
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Abstract
The present invention relates to the synthesis process of 2-methoxyl-5-iodophenol. The synthesis process includes the following steps: the reaction of 2-methoxyl-phenol and p-toluenesulfonyl chloride in triethylamine solvent to prepare p-toluenesulfo-(2-methoxyl) phenol ester; the reaction of p-toluenesulfo-(2-methoxyl) phenol ester, metal chloride and iodine monochloride to produce great amount of solid; suction filtering, washing with glacial acetic acid and water washing to obtain p-toluenesulfo-(2-methoxyl-5-iodo) phenol ester; and final deprotection of p-toluenesulfo-(2-methoxyl-5-iodo) phenol ester to obtain 2-methoxyl-5-iodophenol. The present invention has the advantages of simple operation, low material cost, high yield, high product purity, etc. and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of 2-methoxyl group-5 iodophenol.
Background technology
The discotic mesogenic that with the triphenylene is skeleton is a kind of potential one dimension organic conductor photoelectric material, has extremely important application and development prospect.Wherein 2-methoxyl group-5 iodophenol is the important intermediate of synthetic discotic mesogenic, and important commercial exploitation prospect is arranged.
At present in the prior art, 2-methoxyl group-5 iodophenol synthetic mainly contains following two kinds of methods
The rough synthetic route that one: Neville Boden etc. proposed in 1994 in this route, is at first carried out acetylize protection, halogenation then, deprotection base again with Acetyl Chloride 98Min. to the 2-methoxyphenol.The synthetic route of NevilleBoden is as follows:
Productive rate was low when there was halogenation in this synthetic route, by product is many, the shortcoming of separation difficulty, was unsuitable for mass production.And the methoxyl group locating effect of phenyl ring is poor in its this structure, and product is purified needs the high-temperature vacuum vacuum distillation equipment when separating.
Its two: the disclosed synthetic method of calendar year 2001 Japanese Patent, its synthetic route is as follows:
The locating effect of the phenyl ring of this route is better slightly than article one, but its inferior separating effect, and the agents useful for same price is more expensive, is not suitable for industrial production.
Summary of the invention
The objective of the invention is to adopt the protecting group of Tosyl chloride, provide a kind of and have higher orientation effect, and aftertreatment is simple, the method for Synthetic 2-methoxyl group that purity is very high-5 iodophenol as reaction.
For achieving the above object, the present invention adopts following reaction mechanism:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
The method of a kind of 2-methoxyl group-5 iodophenol of the present invention is characterized in that, this method has following steps:
A. tosic acid-(2-methoxyl group) phenol ester is synthetic: 2-methoxyl group-phenol is dissolved in the triethylamine solvent, after stirring, adds Tosyl chloride, controlled temperature continues to stir 5-15 hour in 0-30 ℃ of scope, and placement is spent the night; Filter, the gained solid washs with triethylamine, water respectively, gets white solid, is tosic acid-(2-methoxyl group) phenol ester, and wherein the ratio of 2-methoxyl group-phenol and Tosyl chloride is 1: the 1-2 equivalent;
B. tosic acid-(2-methoxyl group-5-iodine) phenol ester is synthetic: gained tosic acid among the step a (2-methoxyl group) phenol ester is dissolved in the Glacial acetic acid, add the normal metal chloride catalyst of 0.5-1.5 then, stirring makes its whole dissolvings, dropwise adds 2-2.5 equivalent iodine monochloride again in half an hour; Continue stirring reaction, to there being a large amount of solids to generate; Suction filtration, Glacial acetic acid is washed, washing; Can get white solid, be tosic acid-(2-methoxyl group-5-iodine) phenol ester;
C.2-methoxyl group-5-iodophenol is synthetic: with gained tosic acid among the step b (2-methoxyl group-5-iodine) phenol ester, be dissolved in the mixing solutions of distilled water and dehydrated alcohol, the volume ratio of this mixing solutions is 1: 0.5-1.5; And then add 1-1.5 Equivalent Hydrogen potassium oxide, be warming up to 60-90 ℃ of backflow 12-18 hour; Pressure reducing and steaming ethanol after reacting completely, gained mixture are neutralized to solution with dilute hydrochloric acid and are neutral; Use ethyl acetate extraction, anhydrous magnesium sulfate drying spends the night; Filter, the white solid that obtains behind the pressure reducing and steaming solvent is used the dehydrated alcohol recrystallization again, obtains white crystal, is 2-methoxyl group-5-iodophenol.
Compared with prior art, synthetic method of the present invention has that step is few, productive rate is high, reaction conditions is gentle, the simple advantage of aftertreatment.Because after the inventive method adopts Tosyl chloride protection hydroxyl; halogenation is carried out in the methoxyl group contraposition that can be controlled at phenyl ring; slough protecting group again; therefore have that working method is easy, the separation of the locating effect of reagent low price, phenyl ring and product is easy, productive rate is high and the purity advantage of higher, is suitable for industrial production.
Embodiment
Embodiment one: the concrete steps of present embodiment are as follows:
1, tosic acid-(2-methoxyl group) phenol ester is synthetic:
Get 2-methoxyl group-phenol 30 grams and be dissolved in 300 milliliters of triethylamines, after stirring, add the equivalent Tosyl chloride, controlled temperature is continuing stirring 6 hours below 15 ℃, and placement is spent the night.Filter, the gained solid gets white solid 63 grams, productive rate 93.3%, fusing point 82.1-82.3 ℃ respectively with triethylamine, washing twice.Infrared IR:3003cm
-1, 1597cm
-1, 1499cm
-1, 1257cm
-1, 1185cm
-1, 867cm
-1, 781cm
-1, 758cm
-1Nuclear-magnetism
1H-NMR (CDCl
3) δ: 7.52 (dd, 4H), 7.16 (m, 2H), 6.88 (m, 2H), 3.55 (s, 3H), 2.44 (s, 3H).
2, tosic acid-(2-methoxyl group-5-iodine) phenol ester is synthetic:
Take by weighing tosic acid (2-methoxyl group) phenol ester 33 grams, be dissolved in 200 milliliters of Glacial acetic acid, add 31.2 gram Zinc Chloride Anhydrouss then, stir and make its whole dissolvings, in half an hour, dropwise add 25 gram iodine monochlorides again.Stirring at room 12 hours has a large amount of solids to generate.Suction filtration, Glacial acetic acid is washed, washing.Get white solid 42.5 grams, fusing point 147.5-149.2 ℃, productive rate 89.6%.Infrared IR:3000cm
-1, 2841cm
-1, 1595cm
-1, 1493cm
-1, 1295cm
-1, 1184cm
-1, 888.4cm
-1, 875cm
-1, 783cm
-1, 755cm
-1Nuclear-magnetism
1H-NMR (CDCl
3) δ: 7.62 (d, 2H), 7.32 (d, 2H), 7.44 (d, 1H), 7.41 (s, 1H), 6.60 (d, 1H), 3.55 (s, 3H), 2.46 (s, 3H)
3,2-methoxyl group-5-iodophenol is synthetic:
Take by weighing 30 gram tosic acid (2-methoxyl group-5-iodine) phenol esters,, and then add 20 gram potassium hydroxide, be warming up to 80 ℃ and refluxed 24 hours with 100 ml distilled waters and 100 milliliters of dehydrated alcohol heating for dissolving.Pressure reducing and steaming ethanol after reacting completely, gained mixture are neutralized to solution with dilute hydrochloric acid and are neutral.With 200 milliliters of ethyl acetate extractions, anhydrous magnesium sulfate drying spends the night.Filter, the white solid that obtains behind the pressure reducing and steaming solvent is used the dehydrated alcohol recrystallization again, obtains white crystal 15.8 grams.Fusing point 87.3-88.3 ℃, productive rate 87.2%.Infrared IR:3397cm
-1, 3470,1583cm
-1, 1500cm
-1, 1256cm
-1, 1222cm
-1, 857cm
-1, 798cm
-1Nuclear-magnetism
1H-NMR (CDCl
3) δ: 7.23 (d, 1H), 7.15 (dd, 1H), 6.59 (d, 1H), 5.58 (s, 1H), 3.85 (s, 3H).
Claims (1)
1. the synthetic method of 2-methoxyl group-5 iodophenol is characterized in that, this method has following steps:
A. tosic acid-(2-methoxyl group) phenol ester is synthetic: 2-methoxyl group-phenol is dissolved in the triethylamine solvent, after stirring, adds Tosyl chloride, controlled temperature continues to stir 5-15 hour in 0-30 ℃ of scope, and placement is spent the night; Filter, the gained solid washs with triethylamine, water respectively, gets white solid, is tosic acid-(2-methoxyl group) phenol ester, and wherein the ratio of 2-methoxyl group-phenol and Tosyl chloride is 1: the 1-2 equivalent;
B. tosic acid-(2-methoxyl group-5-iodine) phenol ester is synthetic: gained tosic acid among the step a (2-methoxyl group) phenol ester is dissolved in the Glacial acetic acid, add the normal metal chloride catalyst of 0.5-1.5 then, stirring makes its whole dissolvings, dropwise adds 2-2.5 equivalent-iodine chloride again in half an hour; Continue stirring reaction, to there being a large amount of solids to generate; Suction filtration, Glacial acetic acid is washed, washing; Can get white solid, be tosic acid-(2-methoxyl group-5-iodine);
C.2-methoxyl group-5-iodophenol is synthetic: with gained tosic acid among the step b (2-methoxyl group-5-iodine) phenol ester, be dissolved in the mixing solutions of distilled water and dehydrated alcohol, the volume ratio of this mixing solutions is 1: 0.5-1.5; And then add 1-1.5 Equivalent Hydrogen potassium oxide, be warming up to 60-90 ℃ of backflow 12-18 hour; Pressure reducing and steaming ethanol after reacting completely, gained mixture are neutralized to solution with dilute hydrochloric acid and are neutral; Use ethyl acetate extraction, anhydrous magnesium sulfate drying spends the night; Filter, the white solid that obtains behind the pressure reducing and steaming solvent is used the dehydrated alcohol recrystallization again, obtains white crystal, is 2-methoxyl group-5-iodophenol.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100258601A CN1313426C (en) | 2005-05-17 | 2005-05-17 | Synthesis of 2-methoxyl-5-iodophenol |
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| CNB2005100258601A CN1313426C (en) | 2005-05-17 | 2005-05-17 | Synthesis of 2-methoxyl-5-iodophenol |
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| CN1706786A true CN1706786A (en) | 2005-12-14 |
| CN1313426C CN1313426C (en) | 2007-05-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001979A (en) * | 2010-11-18 | 2011-04-06 | 上海工程技术大学 | Preparation method of 2-(2', 2'-difluoroethoxyl)-6-trifluoromethyl phenyl propyl sulfide |
| WO2011143819A1 (en) * | 2010-05-19 | 2011-11-24 | Rhodia (China) Co., Ltd. | Process for preparing an ortho-substituted 5-halophenol and a synthesis intermediate thereof |
| CN114262263A (en) * | 2021-12-28 | 2022-04-01 | 河北美星化工有限公司 | Preparation method of 4-iodophenol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1391553A (en) * | 1999-11-18 | 2003-01-15 | 味之素株式会社 | Novel intermediate for sweetener with high sweetness and process for producing the same |
| JP2001316300A (en) * | 2000-05-10 | 2001-11-13 | Ajinomoto Co Inc | Method for producing benzene iodide delivative and new intermediate |
-
2005
- 2005-05-17 CN CNB2005100258601A patent/CN1313426C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011143819A1 (en) * | 2010-05-19 | 2011-11-24 | Rhodia (China) Co., Ltd. | Process for preparing an ortho-substituted 5-halophenol and a synthesis intermediate thereof |
| CN102958913A (en) * | 2010-05-19 | 2013-03-06 | 罗地亚（中国）投资有限公司 | Process for preparing an ortho-substituted 5-halophenol and a synthesis intermediate thereof |
| EP2574192A4 (en) * | 2010-05-19 | 2013-12-25 | Rhodia China Co Ltd | Process for preparing an ortho-substituted 5-halophenol and a synthesis intermediate thereof |
| US8975431B2 (en) | 2010-05-19 | 2015-03-10 | Rhodia Operations | Process for preparing an ortho-substituted 5-halophenol and a synthesis intermediate thereof |
| KR101516471B1 (en) | 2010-05-19 | 2015-05-04 | 로디아 오퍼레이션스 | Process for preparing an ortho-substituted 5-halophenol and a synthesis intermediate thereof |
| CN102958913B (en) * | 2010-05-19 | 2015-11-25 | 罗地亚（中国）投资有限公司 | The method of the 5-halogenated phenols that preparation ortho position replaces and synthetic intermediate thereof |
| CN102001979A (en) * | 2010-11-18 | 2011-04-06 | 上海工程技术大学 | Preparation method of 2-(2', 2'-difluoroethoxyl)-6-trifluoromethyl phenyl propyl sulfide |
| CN114262263A (en) * | 2021-12-28 | 2022-04-01 | 河北美星化工有限公司 | Preparation method of 4-iodophenol |
| CN114262263B (en) * | 2021-12-28 | 2024-04-19 | 河北美星化工有限公司 | Preparation method of 4-iodophenol |
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|---|---|
| CN1313426C (en) | 2007-05-02 |
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