HU Yu－lin，LU Ming，ZHENG Jian－dong

（1.College of Material Science and Chemical Engineering，Chuzhou University，Chuzhou 239000，Anhui China；2.College of Chemical Engineering，Nanjing University of Science and Technology，Nanjing 210094，China）

Novel and Efficient Hydrolysis of Benzyl Chloride Catalyzed by PEG1000－DAIL［BF4］／Fe2（SO4）3Under Homogeneous Catalysis＊

HU Yu－lin1，2，LU Ming2，ZHENG Jian－dong1

（1.College of Material Science and Chemical Engineering，Chuzhou University，Chuzhou 239000，Anhui China；2.College of Chemical Engineering，Nanjing University of Science and Technology，Nanjing 210094，China）

Benzyl alcohol was obtained in 96%high yield by hydrolysis of benzyl chloride，which was catalyzed by the recyclable temperature－dependant phase－separation catalytic system that comprised of the ionic liquid PEG1000－DAIL［BF4］，toluene and ferric sulfate（Fe2（SO4）3）under homogeneous catalysis in aqueous media.The reaction mixture was stirred for 40min at 110℃.The method has the advantages of high yield of easy operation.The catalytic system can be recycled or reused without any significant loss of catalytic activity.The mechanism of hydrolysis reaction and the process of catalysis in the thermoregulated ionic liquid bi－phase system are also proposed.

benzyl alcohol；benzyl chloride；ionic liquid；thermoregulated biphasic system

Ionic liquids（ILs），with their interesting physical and chemical properties with a negligible vapor pressure，unique permittivity and excellent thermal stability，have recently been widely used as reaction media，separation solvents，and novel electrolytes［31－39］.However，these ILs has inevitable one or more disadvantages such as low recovery ratio，high cost，etc.In view of both the advantages and disadvantages of homogeneous and heterogeneous catalysts，and to improve catalyst recovery，multiphase systems，such as phase－transfer catalysis［40］，thermoregulated phase－transfer catalysis［41］，and liquid－liquid biphasic catalysis［42］，have been studied.Recently，some novel temperature－dependent ionic liquid biphasic catalytic systems have been reported［43－46］，and because of their advantages such as high yield and stability at high temperatures，reusability in the reaction，etc.，they provide us a novel route for the separation of product from the reaction system and recycling of catalysts.The objectives of the present work are to report a novel and efficient procedure for synthesis of benzyl alcohol by hydrolysis of benzyl chloride catalyzed by PEG－1000－based dicationic acidic ionic liquid（PEG1000－DAIL［BF4］）in combination with ferric sulfate（Fe2（SO4）3）and toluene in aqueous media（scheme 1）.

Scheme 1 Hydrolysis of Benzyl Chloride

2 Experiment

2.1 Apparatus and Reagents

All the chemicals were commercial sources without any pretreatment.All reagents were of analytical grade.The ionic liquids were synthesized according to the literature procedures［47］.High performance liquid chromatography（HPLC）experiments was performed on a liquid chromatograph（Dionex Softron GmbH，America），consisting of a pump（P680）and ultraviolet－visible light detector（UVD）system（170U）.Elemental analysis was performed on a Vario EL III instrument（Elmentar Analysen Systeme GmbH，Germany）.

2.2 Preparation of Benzyl Alcohol

A mixture of benzyl chloride（1.26g，10mmol），water（10mL，0.5mol），F(xiàn)e2（SO4）3（1.0g，2.5mmol），and PEG1000－DAIL［BF4］（10mL，9mmol）were added in a 100mL round flask equipped with reflux condenser and oil－bath.The reaction mixture was stirred for 40min at 110℃，and the reaction progress was monitored by HPLC.Upon completion，the mixture was cooled to room temperature.The organic phase was separated by decantation and dried with anhydrous sodium sulfate.Then the crude mixture was purified by column chromatography on silica gel to afford a colorless oil of benzyl alcohol（1.03 g，96%yield）.The next operation was performed under identical reaction conditions.

3 Results and Discussion

In a preliminary study，the hydrolysis of benzyl chloride was carried out in oil－water biphasic system in the presence and absence of P EG1000－DAIL［BF4］at 110℃.As shown in figure 1，in the absence of PEG1000－DAIL［BF4］，the hydrolysis reaction proceeded very slowly，and only 24%yield was obtained af－ter 1h.The results mean that Fe2（SO4）3alone does not work as an effective catalyst in the hydrolysis reaction.Reaction performed with PEG1000－DAIL［BF4］proceeded very rapidly and the yield reached 96%in 1h，which demonstrated the high catalysis efficiency of PEG1000－DAIL［BF4］.

The effects of different ionic liquids such as PEG600－DAIL，PEG800－DAIL，PEG1000－DAIL，PEG1000－DAIL［BF4］，PEG1000－DAIL［PF6］，and PEG1000－DAIL［OTf］were shown in figure 2，and it was observed that PEG1000－DAIL［BF4］demonstrated the best performance.The different catalytic abilities of the ILs（PEG600－DAIL，PEG800－DAIL，and PEG1000－DAIL）should be attributed to their different abilities of forming homogeneous catalysis mediums by exhibiting a temperature－dependent phase behavior with toluene（i.e.the thermoregulated biphasic behavior of mono－phase under high temperature and bi－phase under room temperature）.Under the same conditions，the IL which forms homogeneous catalysis medium in combination with toluene more easily will lead to a larger increase in the effective reactant concentration，which increases the encounter probability between the reactive species.Thus，the observed rate and yield of the reaction is PEG1000－DAIL＞PEG800－DAIL＞PEG600－DAIL.

Figure 1 Plot of the Hydrolysis Degree vs.Time in Presence and in Absence of PEG1000－DAIL［BF4］

Figure 2 Influences of Different Types of ILs on the Hydrolysis

Figure 3 Influences of Different Types of Cocatalysts on the Hydrolysis

As shown in figure 3，it was observed that a lower yield of the product was obtained while the same reaction condition was carried out in the absence of a cocatalyst.The result indicates that the cocatalyst must play an important role in accelerating the rate of the reaction to some extent.In this reaction，we tried to use some types of cocatalysts in the reaction，the results showed that Fe2（SO4）3，CuSO4and Cu（OAc）2were almost the cocatalysts of similar effectiveness.Among them，F(xiàn)e2（SO4）3was found to be the most effective cocatalyst in terms of yield and reaction rate.

The influences of the amount of concentrated PEG1000－DAIL［BF4］at 110oC are shown in figure 4.In the absence of IL，the hydrolysis reaction proceeded slowly，the yield of benzyl alcohol increased with the increase in PEG1000－DAIL［BF4］amount.The yield reached maximum at 1.0of the volume ratio（IL／water＝1）.However，further addition of the IL，under the same conditions，did not enhance significantly the yield.

Figure 5shows the influences of reaction temperature on the hydrolysis.The catalytic activities increased with the increase in reaction temperature，and the yield reached maximum at 110oC.However， with further increase in the temperature，the yield decreased slowly.This is due to the formation of dibenzyl ether at higher temperatures observed in LC chromatogram.These results show that the moderate temperature，such as 110℃，enhanced the reaction.

Figure 4 Influences of the Amount of PEG1000－DAIL［BF4］on the Hydrolysis

Figure 5 Influences of Reaction Temperature on the Hydrolysis

Figure 6 Repeating Reactions Using Recovered PEG1000－DAIL［BF4］

In addition，the catalytic system could be typically recovered and reused for subsequent reactions with no appreciable decrease in yields and reaction rates（figure 6）.The recycling process involved the removal of the top oil layer（toluene containing product）by decantation.The bottom aqueous layer（catalytic system）was concentrated in vacuum to remove the water and hydrogen chloride（the hydrolysis product）.Fresh substrates and toluene were then recharged to the residual P EG1000－DAIL［BF4］／Fe2（SO4）3and the mixture was heated to react once again.The procedure was repeated 8 times in the hydrolysis of benzyl chloride，and only 5.6%loss of weight was observed.

The excellent catalytic abilities of PEG1000－DAIL［BF4］／Fe2（SO4）3suggest that the hydrolysis reaction among benzyl chloride，water，toluene，ferric sulfate and PEG1000－DAIL［BF4］has a particular mechanism.Scheme 2shows a possible mechanistic pathway for the synthesis of benzyl alcohol.Before the hydrolysis，there exists an obvious oil－water biphasic system：the under layer（water phase）consists of PEG1000－DAIL［BF4］，F(xiàn)e2（SO4）3，and water，PEG1000－DAIL［BF4］is dissolved completely in the aqueous medium；the upper layer（oil phase）consists of benzyl chloride and toluene.During the process of hydrolysis，the oil－water biphasic system disappears and a homogeneous reaction medium is formed.In this case，it is considered that the stable benzyl cation is formed during the hydrolysis process.［21－23］Firstly，benzyl chloride reacts with the Fe3＋and BF－4to form transition state（I）；and then，I eliminates the chlorine ion（Cl－）to yield the stable benzyl cation（II）；then II is attacked by the nucleophile（H2O）yielding the transition state（III）；finally III eliminates the proton（H＋）to yield the desired product benzyl alcohol（IV）.After the completion of the reaction，a complete phase－separation is formed again after cooling to room temperature，the upper layer of toluene containing product is removed by decantation，and the under layer of the catalytic system，containing PEG1000－DAIL［BF4］／Fe2（SO4）3and hydrochloric acid is concentrated to remove generated water through water knockout drum and then recycle.The PEG1000－DAIL［BF4］plays a very important role in the hydrolysis process to locally concentrate the reacting species near them by exhibiting a temperature－dependent phase behavior with toluene（i.e.the thermoregulatedm biphasic behavior of mono－phase at high temperature and biphase at room temperature），which leads to a large increase in the effective reactant concentration and the excellent yield of benzyl alcohol is obtained accordingly.

Scheme 2 Possible Mechanism for the Hydrolysis of Benzyl Chloride

4 Conclusion

In conclusion，we have developed a novel and efficient synthetic pathway for the preparation of benzyl alcohol by hydrolysis of benzyl chloride catalyzed by PEG1000－DAIL［BF4］／Fe2（SO4）3in aqueous media in a 96%excellent yield.Compared with the synthetic methods reported in previous literatures［7－30］，the novel method has the advantages of high yield and easy operation.Simple reaction conditions，good thermoregulated biphasic behavior of IL and facile manipulations in the isolation of the product are the attractive features of this methodology.Moreover，the excellent recyclability of the catalytic system makes this procedure cleaner，which is a good example of green chemistry technology.

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（責(zé)任編輯 易必武）

新型有效的PEG1000－DAIL［BF4］／Fe2（SO4）3均相催化氯化芐水解反應(yīng)

胡玉林1，2，陸 明2，鄭建東1
（1.滁州學(xué)院材料與化學(xué)工程學(xué)院，安徽滁州 239000；2.南京理工大學(xué)化工學(xué)院，江蘇南京 210094）

在離子液體PEG1000－DAIL［BF4］、甲苯和Fe2（SO4）3組成的溫控兩相催化體系作用下，氯化芐的均相催化水解反應(yīng)能夠高效地進(jìn)行，在110℃攪拌反應(yīng)40min，產(chǎn)物苯甲醇收率高達(dá)96%.該新方法收率高，操作簡(jiǎn)單，催化體系可以較好地回收循環(huán)使用而且催化活性基本保持不變.同時(shí)，對(duì)水解反應(yīng)的機(jī)理和溫控兩相催化的過(guò)程也進(jìn)行了闡述.

苯甲醇；氯化芐，水解；離子液體；溫控兩相體系

O621.3

A

O621.3

B

10.3969／j.issn.1007－2985.2013.03.012

1007－2985（2013）03－0055－07

1 Introduction

Benzyl alcohol is a promising key intermediate in the synthesis of a variety of chemicals such as pharmaceuticals，dyes，flavors，perfume，food additive，etc［1－6］.Methods concerning the manufacture of benzyl alcohol have been well documented in previous papers［7－30］，such as hydrolysis of benzyl chloride，oxidation of toluene，reduction of benzoic acid or benzaldehyde［7－14］.The most commonly employed procedures for preparation of benzyl alcohol have been the use of alkalines and the phase transfer catalysts as the promoted catalysts［15－21］.However，alkaline hydrolysis has the disadvantages of additional use of base，formation of dibenzyl ether and production of aqueous waste liquors.There are also investigations into the hydrolysis in homogeneous mixtures of benzyl chloride，water，water－soluble solubilizer（e.g.alcohol，acetic acid，dioxin，DMSO）and the metal salts（e.g.HgCl2，Hg（NO3）2，Na2WO4，CuSO4，CuCl）as the catalysts［22－26］.Among these metal salts，copper and its salts are effective catalysts［26］.These catalyst systems，in general，suffer from the inherent problems of isolation of the hydrolysis products，difficulty of catalyst recovery，environmental hazards，toxicity，and so on.Other notable methods include the use of microwave and elevated water［27－30］.Some of these procedures have invariable one or more disadvantages such as high cost，high temperature，special apparatus，and so on.Consequently，there is a great need to develop an efficient procedure for the synthesis of benzyl alcohol.

＊Received date：2013－01－09

Supported by National Basic Research Program（973）of China（613740101）；NSFC－NSAF Research Program（11076017）

Biography：HU Yu－lin（1982－），male，was born in Changde City，Hunan Province，lecture，doctor，majoring in organic chemistry and green chemistry.