CN1706786A

CN1706786A - The synthetic method of 2-methoxy-5 iodophenol

Info

Publication number: CN1706786A
Application number: CN 200510025860
Authority: CN
Inventors: 万文; 王朋玉; 袁忠谦
Original assignee: University of Shanghai for Science and Technology
Current assignee: University of Shanghai for Science and Technology
Priority date: 2005-05-17
Filing date: 2005-05-17
Publication date: 2005-12-14
Anticipated expiration: 2025-05-17
Also published as: CN1313426C

Abstract

本发明涉及一种2－甲氧基－5碘苯酚的合成方法。本发明方法分三步进行，首先以2－甲氧基－苯酚和对甲苯磺酰氯为反应物，以三乙胺为溶剂，制备对甲苯磺酸－(2－甲氧基)苯酚酯；然后用对甲苯磺酸(2－甲氧基)苯酚酯与金属氯化物及一氯化碘反应，至有大量固体生成；抽滤，冰醋酸洗，水洗；可得对甲苯磺酸－(2－甲氧基－5－碘)苯酚酯；最后对甲苯磺酸(2－甲氧基－5－碘)苯酚酯脱除保护基团得到2－甲氧基－5－碘苯酚。本发明方法具有操作方法简便、试剂价格便宜、苯环的定位效果及产物的分离简便、产率高、和纯度较高的优点，适合于工业生产。The invention relates to a synthesis method of 2-methoxy-5 iodophenol. The method of the present invention is carried out in three steps. First, 2-methoxy-phenol and p-toluenesulfonyl chloride are used as reactants, and triethylamine is used as a solvent to prepare p-toluenesulfonic acid-(2-methoxy)phenol ester; then Use p-toluenesulfonic acid (2-methoxy)phenol ester to react with metal chloride and iodine monochloride until a large amount of solid is formed; filter with suction, wash with glacial acetic acid, and wash with water; p-toluenesulfonic acid-(2- Methoxy-5-iodo)phenol ester; finally p-toluenesulfonic acid (2-methoxy-5-iodo)phenol ester removes the protecting group to obtain 2-methoxy-5-iodophenol. The method of the invention has the advantages of simple and convenient operation method, cheap reagent price, easy positioning effect of benzene ring and easy separation of products, high yield and high purity, and is suitable for industrial production.

Description

The synthetic method of 2-methoxyl group-5 iodophenol

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. a synthetic method of 2-methoxy-5 iodophenol, is characterized in that, the method has the steps:

a. Synthesis of p-toluenesulfonic acid-(2-methoxy)phenol ester: 2-methoxy-phenol is dissolved in triethylamine solvent, after stirring evenly, add p-toluenesulfonyl chloride, control temperature at 0- Within the range of 30°C, continue to stir for 5-15 hours, and place it overnight; filter, and wash the obtained solid with triethylamine and water respectively to obtain a white solid, which is p-toluenesulfonic acid-(2-methoxy)phenol ester, Wherein the ratio of 2-methoxyl-phenol to p-toluenesulfonyl chloride is 1: 1-2 equivalents;

b. Synthesis of p-toluenesulfonic acid-(2-methoxyl-5-iodo)phenol ester: the obtained p-toluenesulfonic acid (2-methoxyl)phenol ester in step a is dissolved in glacial acetic acid, then add 0.5 - 1.5 equivalents of metal chloride catalyst, stir to dissolve it completely, and then add 2-2.5 equivalents of iodine chloride dropwise within half an hour; continue to stir the reaction until a large amount of solids are formed; suction filtration, glacial acetic acid washing, water washing ; A white solid can be obtained, which is p-toluenesulfonic acid-(2-methoxy-5-iodine);

Synthesis of c.2-methoxy-5-iodophenol: the p-toluenesulfonic acid (2-methoxy-5-iodo)phenol obtained in step b is dissolved in a mixed solution of distilled water and absolute ethanol, The volume ratio of the mixed solution is 1:0.5-1.5; then add 1-1.5 equivalents of potassium hydroxide, heat up to 60-90°C and reflux for 12-18 hours; Neutralize until the solution is neutral; extract with ethyl acetate, dry over anhydrous magnesium sulfate; filter, evaporate the solvent under reduced pressure to obtain a white solid, and recrystallize with absolute ethanol to obtain a white crystal, which is 2- Methoxy-5-iodophenol.