Phase Transfer Catalytic Oxidation of Cyclopentene to Glutaraldehyde by Vanadium Molybdenum Heteropolyacid Salts

doi:10.6023/cjoc202209027

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (4): 1444-1451.DOI: 10.6023/cjoc202209027 Previous Articles Next Articles

ARTICLES

钒钼杂多酸盐相转移催化环戊烯氧化制备戊二醛

张旭征^a, 于凤丽^b^,^*(), 袁冰^b, 解从霞^b, 于世涛^a^,^*()

a 青岛科技大学化工学院生态化工国家重点实验室培育基地青岛 266042
b 青岛科技大学化学分子与工程学院青岛 266042

收稿日期:2022-09-21 修回日期:2022-10-14 发布日期:2022-12-14
通讯作者: 于凤丽, 于世涛
基金资助:
国家自然科学基金(21878166); 山东省自然科学基金(ZR2020MB131)

Phase Transfer Catalytic Oxidation of Cyclopentene to Glutaraldehyde by Vanadium Molybdenum Heteropolyacid Salts

Xuzheng Zhang^a, Fengli Yu^b(), Bing Yuan^b, Congxia Xie^b, Shitao Yu^a()

a State Key Laboratory Base of Eco-chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042
b College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042

Received:2022-09-21 Revised:2022-10-14 Published:2022-12-14
Contact: Fengli Yu, Shitao Yu
Supported by:
National Natural Science Foundation of China(21878166); Natural Science Foundation of Shandong Province(ZR2020MB131)

1. .pdf(1021KB)

Abstract

A series of heteropolyacid phase transfer catalysts containing high-valent molybdenum, vanadium and other metals were designed and synthesized to catalyze the oxidation of cyclopentene to glutaraldehyde, and the best imidazolyl molybdate-vanadate catalyst [C₄H₉N₂C₃H₃(CH₃)]₅VMo₇O₂₆ was screened out. The conditions of solvent type, H₂O₂ dosage, catalyst dosage, reaction temperature and time were optimized. Under the optimized reaction conditions [V(ethyl acetate)∶V(water)=4∶1, n(Cat.)∶n(H₂O₂)∶n(CPE)=1∶170∶41.6, 50 ℃, 6 h], 88.7% cyclopentene conversion and 62.1% glutaraldehyde selectivity were obtained, and the catalyst still maintained high catalytic activity after 7 cycles of use.

Key words: hydrogen peroxide, cyclopentene, glutaraldehyde, phase transfer catalysis, heteropolyacid ionic liquid

Cite this article

Xuzheng Zhang, Fengli Yu, Bing Yuan, Congxia Xie, Shitao Yu. Phase Transfer Catalytic Oxidation of Cyclopentene to Glutaraldehyde by Vanadium Molybdenum Heteropolyacid Salts[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1444-1451.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 13

Entry	Catalyst	Acid strength/mV	Conversion/%	Selectivity/%
Entry	Catalyst	Acid strength/mV	Conversion/%	Glutaraldehyde	Cyclopentanediol	Others
1			2
2	[C₆H₁₃NC₅H₅]₄Mo₈O₂₆	145	58.5	32.4	40.1	27.5
3	[C₆H₁₃NC₅H₅]₃HMo₈O₂₆	158	52.0	31.3	40.5	28.2
4	[C₆H₁₃NC₅H₅]H₃Mo₈O₂₆	209	55.9	30.7	45.2	24.1
5	[C₆H₁₃NC₅H₅]₅VMo₇O₂₆	24	83.2	51.6	43.7	4.7
6	[C₄H₉N₂C₃H₃(CH₃)]₅VMo₇O₂₆	34	88.7	62.1	32.2	5.7
7	[C₂H₅N₂C₃H₃(CH₃)]₅VMo₇O₂₆	37	77.9	57.1	30.3	12.6
8	[C₈H₁₇N₂C₃H₃(CH₃)]₅VMo₇O₂₆	29	90.1	61.3	34.5	4.2

Table 1. Effects of different catalysts on the catalytic performance

Figure 1. FT-IR spectra of catalyst [C4H9N2C3H3(CH3)]5VMo7- O26 before and after reaction

Figure 2. 1H NMR spectrum of the catalyst [C4H9N2C3H3(CH3)]5VMo7O26

Figure 3. TG curve of the catalyst [C4H9N2C3H3(CH3)]5VMo7- O26

Figure 4. XRD spectrum of the catalyst [C4H9N2C3H3(CH3)]5V- Mo7O26

Ethyl acetate/mL	Water/mL	CPE conversion/%	GA selectivity/%
5	0	89.1	47.2
4	1	88.5	61.9
3	2	83.0	55.2
2	3	78.2	53.6
1	4	70.6	44.1

Table 2. Influence of different oil/water ratios on the reaction

Figure 5. Influence of hydrogen peroxide dosage on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, 45 ℃, 6 h

Figure 6. Influence of the catalyst dosage on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 45 ℃, 6 h

Figure 7. Influence of reaction temperature on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 6 h

Figure 8. Influence of reaction time on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 45 ℃, 6 h

Figure 9. Reusability of the catalyst on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 45 ℃, 6 h

Figure 10. Continuous on-line FT-IR spectra of cyclopentene reaction system Reaction time: a, 0 min; b, 5 min; c, 10 min; d, 15 min; e, 20 min; f, 25 min; g, 30 min

Scheme 1. Possible reaction mechanism of CPE selective oxidation to GA

References 16

[1]	(a) Song, X. Y.; Guo, J. W.; Cui, Y. D.; Zhang, K. Fine Petrochem. 1999, 16, 46. (in Chinese)
	(宋晓锐, 郭建维, 崔英德, 张昆, 精细石油化工, 1999, 16, 46.)
	(b) Jiang, Z. H. Petrochem. Ind. Appl. 2009, 28, 8. (in Chinese)
	(江镇海, 石油化工应用, 2009, 28, 8.)
	(c) Jiang, Z. H. Shanghai Chem. Ind. 2009, 34, 33. (in Chinese)
	(江镇海, 上海化工, 2009, 34, 33.)
[2]	(a) Li, X. C.; Chen, J. F.; Li, S. Y.; Zhang, Z. Z. Chem. Ind. Eng. Prog. 2002, 22, 222. (in Chinese)
	(李兴存, 陈进富, 李术元, 张忠智, 化工进展, 2002, 22, 222.)
	(b) Li, Y.; Zhang, C. P. Chem. Intermed. 2002, 2, 8. (in Chinese)
	(刘颖, 张传平, 化工中间体, 2002, 2, 8.)
	(c) Chen, M. M.; Fang, Y. X.; Zhang, Y. C. Guangzhou Chem. Ind. 2003, 31, 51. (in Chinese)
	(陈敏敏, 方岩雄, 张永成, 广州化工, 2003, 31, 51.)
	(d) Zhang, X. X.; Song, Y. Y.; Li, M. Chem. Technol. Mark. 2005, 28, 13. (in Chinese)
	(张学旭, 宋云英, 李明, 化工科技市场, 2005, 28, 13.)
	(e) Hao, C. L. Chem. Technol. Mark. 2010, 33, 38. (in Chinese)
	(郝春来, 化工科技市场, 2010, 33, 38.)
[3]	(a) Yan, Q. D.; Gao, J. R. Chem. Times 2007, 21, 57. (in Chinese)
	(闫启东, 高建荣, 化工时刊, 2007, 21, 57.)
	(b) Qian, B. Z.; Zhu, J. F. Petrochem. Technol. Appl. 2008, 26, 86. (in Chinese)
	(钱伯章, 朱建芳, 石化技术与应用, 2008, 26, 86.)
[4]	(a) Jin, R.; Xia, X.; Dai, W.; Deng, J. F.; Li, H. Catal. Lett. 1999, 62, 201. doi: 10.1023/A:1019094905328
	(b) Jin, R.; Xia, X.; Xue, D.; Deng, J. F. Chem. Lett. 1999, 28, 371. doi: 10.1246/cl.1999.371
	(c) Chen, H.; Dai, W. L.; Deng, J. F. Catal. Lett. 2002, 81, 131. doi: 10.1023/A:1016032711528
[5]	Wu, P. Ph.D. Dissertation, Hebei University of Technology, Shijiazhuang, 2013. (in Chinese)
	(吴鹏, 博士论文, 石家庄, 河北科技大学,2013.)
[6]	Zhang, J.; Mai, J.; Chen, J.; Wang, X.; Mai, Y. ChemistrySelect 2022, 7, 4.
[7]	(a) Furukawa, H.; Nakamura, T.; Inagaki, H. Chem. Lett. 1988, 17, 877. doi: 10.1246/cl.1988.877
	(b) Lee, K. Y.; Itoh, K.; Hashimoto, M.; Mizuno, N.; Misono, M. Stud. Surf. Sci. Catal. 1994, 82, 583.
[8]	Amarasekara, A. S. Chem. Rev. 2016, 116, 6133. doi: 10.1021/acs.chemrev.5b00763 pmid: 27175515
[9]	(a) Wang, Z. N.; Wang, J. Y.; Si, Y. H. Chem. Ind. Eng. Prog. 2008, 28, 1057. (in Chinese)
	(王仲妮, 王洁莹, 司友华, 化学进展, 2008, 28, 1057.)
	(b) Zhang, S. J.; Liu, X. M.; Yao, X. Q. Sci. China, Ser. B: Chem. 2009, 39, 1134. (in Chinese)
	(张锁江, 刘晓敏, 姚晓倩, 中国科学B辑: 化学, 2009, 39, 1134.)
	(c) Jiang, P. P.; Li, X. T.; Leng, Y.; Zhang, P. B. Chem. Ind. Eng. Prog. 2014, 33, 2815. (in Chinese)
	(蒋平平, 李晓婷, 冷炎, 张萍波, 化工进展, 2014, 33, 2815.)
[10]	Ding, Y. N.; Xie, C. X.; Yu, F. L. Chem. Bull. 2019, 82, 231. (in Chinese)
	(丁亚男, 解从霞, 于凤丽, 化学通报, 2019, 82, 231.)
[11]	Zhang, C. J.; Liu, X.; Cui, G. N.; Dong, L. M.; Sui, F. Y.; Pang, H. J. Mol. Struct. 2022, 8, 15.
[12]	Verma, S.; Joshi, A.; De, S. R.; Jat, J. L. New J. Chem. 2021, 46, 2005. doi: 10.1039/D1NJ04950J
[13]	Qi, Y.; Han, Q.; Wu, L.; Li, J. New J. Chem. 2021, 45, 19264. doi: 10.1039/D1NJ02427B
[14]	Raj, N. K. K.; Ramaswamy, A. V.; Manikandan, P. J. Mol. Catal. A: Chem. 2005, 277, 37.
[15]	Zhou, M. D.; Liu, M. J.; Huang, L. L. Green Chem. 2014, 17, 1186. doi: 10.1039/C4GC01411A
[16]	Krivosudský, L.; Roller, A.; Rompel, A. Acta Crystallogr., Sect. C: Struct. Chem. 2019, C75, 872.

钒钼杂多酸盐相转移催化环戊烯氧化制备戊二醛

Phase Transfer Catalytic Oxidation of Cyclopentene to Glutaraldehyde by Vanadium Molybdenum Heteropolyacid Salts

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 13

References 16

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yi Zhou, Zhuojun Li, Minghui Hu, Zhaohua Yan, Sen Lin. Oxidation of Sulfides with SO₂F₂/H₂O₂/Base [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1545-1550.
[2]	Jiaojiao Li, Lifu Ban, Lijun Tang. Research Progress in Mitochondrial Targeting Fluorescent Probes for Hydrogen Peroxide [J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 241-249.
[3]	Yang Min, Xia Lili, Zhou Xiaoqin, Jia Chengli, Ji Min, Wang Peng. A Ratiometric Fluorescent Probe for Imaging Hydrogen Peroxide in Living Cells [J]. Chinese Journal of Organic Chemistry, 2020, 40(9): 2888-2894.
[4]	Li Wei, Jia Xu, Guo Zhenbo, Jiang Wenting, Zhang Pingzhu, Wei Chao, Li Xiaoliu. Imaging of Hydrogen Peroxide During the Ischemia Reperfusion Process in Living Cells with An Aggregation Induced-Emission Probe [J]. Chinese Journal of Organic Chemistry, 2020, 40(7): 1934-1940.
[5]	Han Man-Yi, Pan Hong, Yao Ziyun, Li Qi. n-Bu₄NBr Catalyzed Brook Rearrangement/Alkylation Reaction [J]. Chinese Journal of Organic Chemistry, 2020, 40(12): 4274-4283.
[6]	Zheng Tianjiao, Chen Xuanying, Zhu Liangliang, Wang Daolei, Zou Qi, Zeng Tao, Chen Wenbo. A New Dicyano-vinyl Modified Difurylperhydrocyclopentene Photoswitch: Fluorescent Properties, Sensing Ability and in vivo Application [J]. Chin. J. Org. Chem., 2019, 39(9): 2492-2498.
[7]	Li Sha, Yang Wenhan, Luo Xian, Yao Changsheng. An Efficient N-Heterocyclic Carbene (NHC)-Catalyzed Synthesis of Polysubstituted Cyclopentene [J]. Chin. J. Org. Chem., 2019, 39(5): 1404-1410.
[8]	Liu Keyan, Ou Hui, Shi Xianying, Dong Xuefen, Ma Wenjuan, Wei Junfa. Recent Progress in the Selective Oxidation of Sulfides withHydrogen Peroxide [J]. Chin. J. Org. Chem., 2014, 34(4): 681-692.
[9]	Chen Jinquan, Kang Tairan, Liu Jinglin, He Long, Liu Quanzhong. Phase Transfer Catalyzed Enantioselective and Diastereoselective Conjugate Additions of Glycinate Imine to Unsaturated Imines Formed in situ from Sulfonylindoles [J]. Chin. J. Org. Chem., 2013, 33(07): 1483-1489.
[10]	Tang Zilong, Chang Shuhong, Yan Lin, Cui Meiyan, Liu Hanwen. Synthesis and Fungicidal Activity of Novel 3-(1,3,4-Thiadiazolyl)-1,3-bezoxazines [J]. Chin. J. Org. Chem., 2012, 32(07): 1241-1246.
[11]	Zhang Shengjian, Zhao Yingxian, Zhang Hong. Synthesis of 2,3-Dimethyl-2,3-dinitrobutane by Oxidative Coupling of Acetone Oxime [J]. Chin. J. Org. Chem., 2012, 32(04): 786-789.
[12]	Ji Li, Liu Jinqiang, Qian Chao, Chen Xinzhi. Advances in the Application of Urea-Hydrogen Peroxide to Oxidation Reactions [J]. Chin. J. Org. Chem., 2012, 32(02): 254-265 .
[13]	LIU Yang, ZENG Qing-Le, TANG Hong-Yan, GAO Shan, YANG Zhi-Ren, ZHANG Song, LIU Jian-Chuan. Progress on Organic Synthesis Using Hydrogen Peroxide as a Green Chemical Reagent [J]. Chin. J. Org. Chem., 2011, 31(07): 986-996.
[14]	ZHANG Fu-Li, TANG Kun. Epoxidation of Cyclohexene Catalyzed by Metal Iron Schiff Base Complexes [J]. Chin. J. Org. Chem., 2011, 31(06): 921-924.
[15]	ZHANG Guo-Fu, WANG Yong, DING Cheng-Rong, LIU Ren-Hua, LIANG Xin-Miao. Recent Advances in Oxybromination of Aromatic Compounds [J]. Chin. J. Org. Chem., 2011, 31(06): 804-813.