Acetalization of Carbonyl Compounds with Diols Catalyzed by InCl3·4H2O

DENG Gui-sheng，REN Tie-gang

(College of Chemistry and Chemical Engineering，Hunan Normal University，Changsha 410081，China)

Acetalization of Carbonyl Compounds with Diols Catalyzed by InCl3·4H2O

DENG Gui-sheng*，REN Tie-gang

(College of Chemistry and Chemical Engineering，Hunan Normal University，Changsha 410081，China)

Acetalization of aromatic and aliphatic aldehydes with diols catalyzed by InCl3·4H2O was carried out in refluxing benzene to give the corresponding acetals in 76%～85%yields.And ketone acetals were obtained in 75%～82%yields in the same method.

acetalization;diols;carbonyl compounds;indium trichloride

Acetals play an important role in synthetic carbohydrates［1］and steroid chemistry.In pharmaceutical，phytopharmaceutical，fragrance and lacquer industries，acetals are used both as intermediates and as end products［2-3］.Meanwhile，acetalization of carbonyl compounds as a method for protection of carbonyl group has been widely used in organic synthesis.There are many available methods reported in literatures.Among them，most involved the removal of water under acid-catalyzed condition［4］.Various catalysts have been used in the process，such as organic acid(sulfamic acid［5］)，solid acid［6］，acidic ionic liquid［7-8］，heteropolyacid［9］，Lewis acid(InF［10］，GaCl3［11］， NbCl3［12］)，cation-exchanged montmorillonite［13］，Rh(Ⅲ)triphos moieties［14］，TMSCl［15］，bis-trimethylsilyl ether of ethane-1，2-diols and trimethylsilyl triflate［16］，etc.Acetalization catalyzed by cadmium iodide under microwave irradiation has also been reported［17］.

Some reported methods are limited because of use of corrosives，effluent pollution or sensitivity to water，etc.Lewis acid-catalyzed acetalization is of current interest owing to its activity and stability.In particular，InCl3has been widely applied in various catalytic reactions because of operational simplicity and inertness to water.For example，InCl3-Me3SiCl-promoted Mukaiyama aldol reaction［18-20］，Knoevenagel condensation and the addition of allylic stannanes to aldehydes［21］，cross-aldol condensation［22］and diacetalization of 2，2-bis(hydroxymethyl)-1，3-propanediol［23］have been disclosed.On the basis of the consideration，we tried to exploit InCl3-catalyzed acetalization of carbonyl compounds with diols.

In our procedure，the reaction of carbonyl compounds with diols was carried out in the presence of InCl3·4H2O.The commercially available benzaldehyde 1a and 1，2-ethandiol 2a were first used as a model to screen appropriate solvents.The results are summarized in Table 1.As expected，2-phenyl-1，3-dioxolane 3a was generated in various refluxing solvents.Yields were high in refluxing benzene，toluene，cyclohexane and THF，however，low in refluxing DMF and dichloromethane.Benzene was the best solvent based on the yield.

Table 1 Solvent effect on yieldof the reaction of benzaldehyde 1a with 1，2-ethandiol 2a*

Representative carbonyl compounds 1 and diols 2 submitted to the above optimal conditions.The results were summarized in Table 2.The acetalization of aromatic or aliphatic aldehydes and aliphatic ketone with 1，2-ethandiol 2a and 1，2-propandiol 2b gave the corresponding acetals in good to excellent yield(entries 3a-3i in Table 2).In the case of 1，3-propandiol 2c，similar results were obtained(entries 3j-3m in Table 2).In comparison with aromatic or aliphatic aldehydes，the reaction of aliphatic ketone with diols gave the corresponding acetals in lower yields，and but for longer reaction time(entries 3g，3i and 3m in Table 2).

Table 2 Acetalization of carbonyl compounds with diols catalyzed by InCl3·4H2O*

In summary，an efficient and facile method for InCl3-catalyzed synthesis of the acetals via reaction of carbonyl compounds with diols has been demonstrated in this paper.InCl3is a mild catalyst，not sensitive to water and commercially available.This new method has several advantages，such as mild reaction conditions，high yields，simple operation，high reaction efficiency and adaptability to aromatic，aliphatic aldehydes and ketones.

Experimental Section

1H NMR spectra were recorded on Varian Mercury 200 spectrometer in CDCl3solution using tetramethylsilane(TMS)as the internal standard.IR spectra were recorded on a Nicolet instrument corporation's IR-510P spectrometer.

Typical procedure for acetalization of carbonyl compounds with diols catalyzed by InCl3·4H2O.A mixture of benzaldehyde(2.12 g，20 mmol)，1，2-ethandiol(1.24 g，20 mmol)and InCl3·4H2O(0.058 g，2 mmol)in benzene(15 mL)was stirred at reflux for 2 h，using a Dean-Stark apparatus for removal of water.The reaction was monitored by TLC.After cooling，the combined organic layer was concentrated.The residue was distilled in vacuum to afford acetal 3a(2.56 g，83%yield).

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O621.3

A

1000-2537(2012)04-0035-05

四水合三氯化铟催化羰基化合物与二元醇的缩醛反应

邓桂胜*，任铁钢

(湖南师范大学化学化工学院，中国长沙 410081)

在四水合三氯化铟催化下，于苯中加热回流，脂肪及芳香醛与二元醇的缩醛反应形成相应的缩醛，产率76% ～85%.用同样方法，能够获得缩酮，产率达75% ～82%.

缩醛反应;二元醇;羰基化合物;三氯化铟

2012-05-14

湖南省教育厅科研基金资助项目(03C247)

*

，E-mail:gsdeng@hunnu.edu.cn

(编辑 杨春明)