Selective Oxidation of Cyclopentene to Glutaraldehyde Catalyzed by Heteropolyphosphatotungstate Ionic Liquids†

doi:10.7503/cjcu20170355

Abstract

Abstract:

With H₂O₂ as oxidant, a series of heteropolyphosphatotungstate ionic liquids was used to catalyze the selective oxidation of cyclopentene(CPE) to prepare glutaraldehyde(GA). Among these catalysts, [π-C₅H₅NC₁₆H₃₃]₃PW₄O₁₆ exhibited the best catalytic activity. PW₄ $O 16 3 -$ easily combined with H₂O₂ to form W—O—O—W. Using [π-C₅H₅NC₁₆H₃₃]₃PW₄O₁₆ as catalyst, the effects of the amount of catalyst, molar ratio of H₂O₂ to CPE, type and dosage of solvent, reaction temperature and reaction time on the catalytic behavior were investigated and discussed, respectively. The results show the best reaction conditions as follows: 5 mL of ethyl acetate, n(Cat.)∶n(H₂O₂)∶n(CPE)=0.03∶50∶33, 35 ℃, 18 h. The conversion of cyclopentene could reach 100%, and the yield of glutaraldehyde was 87%. After the reaction, the catalyst could automatically precipitate from the reaction liquid. After the upper liquid was poured out, the remaining catalyst could be directly reused by the addition of fresh reactants. Under the optimal reaction conditions, the recycling efficiency of the catalyst [π-C₅H₅NC₁₆H₃₃]₃PW₄O₁₆ was investigated. Because the structure of the catalyst didn’t change before and after reaction by the analysis of FTIR spectra, [π-C₅H₅NC₁₆H₃₃]₃PW₄O₁₆ has exhibited a good recyclability. After 7 recycles, the yield of glutaraldehyde was still above 80%.

Key words: Heteropolyacid ionic liquid, Cyclopentene, Catalytic oxidation, Glutaraldehyde, Hydrogen peroxide

CLC Number:

O643
O621

TrendMD:

ZHANG Jinshuai, YU Fengli, TAO Renqing, XIE Congxia, YUAN Bing, YU Shitao. Selective Oxidation of Cyclopentene to Glutaraldehyde Catalyzed by Heteropolyphosphatotungstate Ionic Liquids^†[J]. Chem. J. Chinese Universities, 2017, 38(12): 2248.

Figures/Tables 9

Table 1 Effects of different catalysts on the catalytic performance*

Catalyst	t/h	Conversion(%)	Yield(%)	Recovery(%)
	18	1
Ⅰ	18	7	2	83
Ⅱ	12	98	72	32
Ⅲ	18	100	87	92
Ⅳ	18	82	55	95

Fig.1 FTIR spectra of catalysts Ⅰ(a), Ⅲ(b) and recycled catalyst Ⅲ(c)

Table 2 Effect of different solvents on the catalytic performance*

Solvent	Conversion(%)	Yield(%)	Recovery(%)
PhMe	42	23	97
TBP	67	9	95
CH₃CN	40	21	93
DMF	22	1	98
Acetone	25	6	57
Ethyl acetate	100	87	92
Butyl acetate	95	82	80

Fig.2 Effect of reaction temperatures on the yield of GAReaction conditions: 0.03 mmol catalyst Ⅲ, 1.5 mmol H2O2, 1 mmol CPE, 5 mL ethyl acetate.

Fig.3 Effect of catalyst amounts on the yield of GA over catalystReaction conditions: 1.5 mmol H2O2, 1 mmol CPE,5 mL ethyl acetate, 35 ℃.

Fig.4 Effect of H2O2/CPE molar ratios on the reaction Reaction conditions: 0.03 mmol catalyst Ⅲ,1 mmol CPE, 5 mL ethyl acetate, 35 ℃.

Fig.5 Effect of ethyl acetate volumes on the reaction Reaction conditions: 0.03 mmol catalyst Ⅲ,1.5 mmol H2O2, 1 mmol CPE, 35 ℃, 18 h.

Fig.6 Reusability of catalyst on the reactionReaction conditions: 0.03 mmol catalyst Ⅲ, 1.5 mmol H2O2, 1 mmol CPE, 5 mL ethyl acetate, 35 ℃, 18 h.

Scheme 1 Reaction mechanism of CPE selective oxidation to GA

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