Formylation of Phenols and Paraformaldehyde Catalyzed by Ammonium Acetate

doi:10.6023/cjoc202011014

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (5): 2038-2044.DOI: 10.6023/cjoc202011014 Previous Articles Next Articles

ARTICLES

乙酸铵催化的酚与多聚甲醛的甲酰化反应研究

李倩¹, 杨丽¹, 刘伟¹, 王天昀¹, 朱月杰¹, 杜正银¹^,^*()

1 西北师范大学化学化工学院兰州 730070

收稿日期:2020-11-09 修回日期:2020-12-26 发布日期:2021-02-07
通讯作者: 杜正银
基金资助:
国家自然科学基金(21262028); 国家自然科学基金(21762039); 甘肃省自然科学基金(20JR5RA521)

Formylation of Phenols and Paraformaldehyde Catalyzed by Ammonium Acetate

Qian Li¹, Li Yang¹, Wei Liu¹, Tianyun Wang¹, Yuejie Zhu¹, Zhengyin Du¹^,^*()

1 College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070

Received:2020-11-09 Revised:2020-12-26 Published:2021-02-07
Contact: Zhengyin Du
About author:
* Corresponding author. E-mail: clinton_du@126.com
Supported by:
National Natural Science Foundation of China(21262028); National Natural Science Foundation of China(21762039); Natural Science Foundation of Gansu Province(20JR5RA521)

1. 212038S.pdf(1481KB)

Abstract

The reaction of naphthol and paraformaldehyde in acetic acid solution with ammonium acetate as a catalyst resulted in the synthesis of a series of hydroxynaphthalenes in yields of up to 86%. Several phenols were also transformed into the corresponding salicylaldehydes under the same reaction conditions in moderate yields of 42%~58%. A rational mechanism was also proposed based on the facts of experimental observations. This metal-free process has the advantages of mild reaction conditions, simple operation and low cost.

Key words: naphthol, phenol, paraformaldehyde, formylation reaction, green synthesis

Cite this article

Qian Li, Li Yang, Wei Liu, Tianyun Wang, Yuejie Zhu, Zhengyin Du. Formylation of Phenols and Paraformaldehyde Catalyzed by Ammonium Acetate[J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 2038-2044.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 38

[1]	Vojacek, S.; Beese, K.; Alhalabi, Z.; Swyter, S.; Bodtke, A.; Schulzke, C.; Jung, M.; Sippl, W.; Link, A. Arch. Pharm. Chem. Life Sci. 2017, 350, e1700097. doi: 10.1002/ardp.v350.7
[2]	Lu, C.; Hu, J. H.; Wang, Z. C.; Xie, S. H.; Pan, T. T.; Huang, L.; Li, X. S. Med. Chem. Commun. 2018, 9, 1862. doi: 10.1039/C8MD00315G
[3]	Xiao, J. M.; Feng, L.; Zhou, L. S.; Gao, H. Z.; Zhang, Y. L.; Yang, K. W. Eur. J. Med. Chem. 2013, 59, 150. doi: 10.1016/j.ejmech.2012.11.019
[4]	Dobashi, Y.; Ohkatsu, Y. Polym. Degrad. Stab. 2008, 93, 436. doi: 10.1016/j.polymdegradstab.2007.11.011
[5]	Deb, M. L.; Pegu, C. D.; Borpatra, P. J.; Baruah, P. K. RSC Adv. 2016, 6, 40552. doi: 10.1039/C6RA04567G
[6]	Goswami, S.; Maity, S.; Das, A. K.; Maity, A. C. Tetrahedron Lett. 2013, 54, 6631. doi: 10.1016/j.tetlet.2013.09.126
[7]	Su, H. Y.; Huang, W. W.; Yang, Z. Y.; Lin, H.; Lin, H. K. J. Inclusion Phenom. Macrocyclic Chem. 2012, 72, 221. doi: 10.1007/s10847-011-9969-7
[8]	Long, F. J. Fluoresc. 2017, 27, 1331. doi: 10.1007/s10895-017-2067-5 pmid: 28353208
[9]	Qin, J. C.; Fan, L.; Li, T. R.; Yang, Z. Y. Synth. Met. 2015, 199, 179. doi: 10.1016/j.synthmet.2014.11.030
[10]	Ugi, I. Adv. Synth. Catal. 1997, 339, 499.
[11]	Terret, N. K.; Gardener, M.; Gordon, D. W.; Kobylecki, R. J.; Steele, J. Tetrahedron 1995, 51, 8135. doi: 10.1016/0040-4020(95)00467-M
[12]	(a) Duff, J. C. J. Chem. Soc. 1941,547.
	(b) Duff, J. C. J. Chem. Soc. 1944,276.
[13]	Reimer, K.; Tiemann, F. Chem. Ber. 1876, 9, 824. doi: 10.1002/(ISSN)1099-0682
[14]	Hofsløkken, N. U.; Skattebøl, L. Acta Chem. Scand. 1999, 53, 258. doi: 10.3891/acta.chem.scand.53-0258
[15]	Ma, K. R.; Huang, Z. Q.; Tang, X. D.; Zhang, P. C.; Shi, G. L. Chem. World 1987, 2, 58. (in Chinese).
	(马克荣, 黄治清, 唐宪达, 张鹏程, 石桂林, 化学世界, 1987, 2, 58.)
[16]	Xia, S. P.; Lv, Y. M.; Cheng, X. Y. Sichuan Chem. Ind. 2004, 7, 10. (in Chinese).
	(夏士朋, 吕云妹, 成新燕, 四川化工, 2004, 7, 10.)
[17]	Zhao, S. F.; Chen, N. Y.; Mei, S. H.; Sun, J. G.; Hao, W. D. J. Wuhan Univ. Technol. 2006, 28, 73. (in Chinese). doi: 10.1007/s11595-013-0643-3
	(赵胜芳, 陈年友, 梅水华, 孙国建, 郝卫东, 武汉理工大学学报, 2006, 28, 73.)
[18]	Yue, X. L.; Wang, Z. Q.; Li, C. R.; Yang, Z. Y. Tetrahedron Lett. 2017, 58, 4532. doi: 10.1016/j.tetlet.2017.10.044
[19]	Balali, E.; Shameli, A.; Naeimi, H.; Ghanbari, M. M. Orient. J. Chem. 2013, 29, 1611. doi: 10.13005/ojc
[20]	Naeimi, H.; Zakerzadeh, E. New J. Chem. 2018, 42, 4590. doi: 10.1039/C7NJ04794K
[21]	(a) Wu, H.; Wu, J. C.; Du, Z. Chin. J. Org. Chem. 2017, 37, 1127. (in Chinese). doi: 10.6023/cjoc201610034
	(吴慧, 武俊成, 杜正银, 有机化学, 2017, 37, 1127.) doi: 10.6023/cjoc201610034
	(b) Hu, B.; Zhang, Y. M.; Wang, T. Y.; Du, Z. J. Liaocheng Univ. (Nat. Sci.) 2020, 33, 67. (in Chinese).
	(胡贝, 张源民, 王天昀, 杜正银, 聊城大学学报(自然科学版), 2020, 33, 67.)
	(c) Zhang, W.; Dong, T.; Wang, T.; Du, Z. J. Liaocheng Univ. (Nat. Sci.) 2019, 32, 35. (in Chinese).
	(张文莹, 董涛生, 王天昀, 杜正银, 聊城大学学报(自然科学版), 2019, 32, 35.)
[22]	(a) Stover, J. S.; Shi, J.; Jin, W.; Vogt, P. K.; Boger, D. W. J. Am. Chem. Soc. 2009, 131, 3342. doi: 10.1021/ja809083d
	(b) Aridoss, G.; Laali, K. K. J. Org. Chem. 2011, 76, 8088. doi: 10.1021/jo201374a
[23]	Ou, W.; Huang, P. Sci. China: Chem. 2020, 63, 11. doi: 10.1007/s11426-019-9586-3
[24]	Yue, X.-L.; Wang, Z.-Q.; Li, C.-R.; Yang, Z.-Y. Tetrahedron Lett. 2017, 58, 4532. doi: 10.1016/j.tetlet.2017.10.044
[25]	Zhao, Q. G.; Wei, Q. C.; Xuan, M. D. Org. Lett. 2010, 12, 2202. doi: 10.1021/ol100381g
[26]	Vojacek, S.; Beese, K.; Alhalabi, Z.; Swyter, S.; Bodtke, A.; Schulzke, C.; Jung, M.; Sippl, W.; Link, A. Arch. Pharm. Chem. Life Sci. 2017, 350, e1700097. doi: 10.1002/ardp.v350.7
[27]	Burton, H. J. Chem. Soc. 1945,280.
[28]	Muhammad, A.; David, O. M.; Paris, E. G. J. Chem. Soc., erkin Trans. 1 2002,1470.
[29]	Andrew, C.; Benniston; Jérôme, F. Tetrahedron Lett. 2008, 49, 4292. doi: 10.1016/j.tetlet.2008.04.134
[30]	Musgrave, O. C.; Skoyles, D. J. Chem. Res. 2006, 2006, 456. doi: 10.3184/030823406777980736
[31]	Asthanaa, M.; Syiemliehb, I.; Kumarc, A.; Lalb, R. A. Inorg. Chim. Acta 2020, 502, 119286. doi: 10.1016/j.ica.2019.119286
[32]	Li, L. J.; Fu, B.; Qiao, Y.; Wang, C.; Huang, Y. Y.; Liu, C. C.; Tian, C.; Du, J. L. Inorg. Chim. Acta 2014, 419, 135. doi: 10.1016/j.ica.2014.04.036
[33]	Zysman-Colman, E.; Arias, K.; Siegel, J. S. Can. J. Chem. 2009, 87, 440. doi: 10.1139/V08-176
[34]	Balali, E.; Shameli, A.; Naeimi, H.; Ghanbari, M. Orient. J. Chem. 2013, 29, 1611. doi: 10.13005/ojc
[35]	Antúnez, D. J. B.; Greenhalgh, M. D.; Fallan, C.; Slawin, A. M. Z.; Smith, A. D. Org. Biomol. Chem. 2016, 14, 7268. doi: 10.1039/C6OB01326K
[36]	Horton, D. A.; Bourne, G. T.; Coughlan, J.; Kaiser, S. M.; Jacobs, C. M.; Jones, A.; Ruhmann, A.; Turnerb, J. Y.; Smythe, M. L. Org. Biomol. Chem. 2008, 6, 1386. doi: 10.1039/b800464a
[37]	Knuutlnen, J. S.; Kolehmainen, E. T. J. Chem. Eng. Data 1983, 28, 139. doi: 10.1021/je00031a039
[38]	Casiraghi, G.; Casnati, G.; Puglia, G.; Sartori, G. Synthesis 1980,124.

Entry	Catalyst (mol%)	Solvent	Time/h	Yield^b/%
1	—	None	12	—
2	—	Isopropanol	12	Trace
3	—	Ethanol	12	Trace
4	—	HOAc	12	26
5	—	HOAc	12	35
6	FeCl₃ (10)	HOAc	12	Trace
7	Ce(NH₄)₂(NO₃)₆ (10)	HOAc	12	Trace
8	NH₄Cl (10)	HOAc	12	38
9	TBAB (10)	HOAc	12	26
10	CTAB (10)	HOAc	12	31
11	AcONH₄ (10)	HOAc	5	70
12	AcONH₄(20)	HOAc	5	76
13	AcONH₄ (50)	HOAc	5	85
14	AcONH₄ (100)	HOAc	5	85
15^c	AcONH₄ (100)	HOAc	5	70

Entry	Catalyst (mol%)	Solvent	Time/h	Yield^b/%
1	—	None	12	—
2	—	Isopropanol	12	Trace
3	—	Ethanol	12	Trace
4	—	HOAc	12	26
5	—	HOAc	12	35
6	FeCl₃ (10)	HOAc	12	Trace
7	Ce(NH₄)₂(NO₃)₆ (10)	HOAc	12	Trace
8	NH₄Cl (10)	HOAc	12	38
9	TBAB (10)	HOAc	12	26
10	CTAB (10)	HOAc	12	31
11	AcONH₄ (10)	HOAc	5	70
12	AcONH₄(20)	HOAc	5	76
13	AcONH₄ (50)	HOAc	5	85
14	AcONH₄ (100)	HOAc	5	85
15^c	AcONH₄ (100)	HOAc	5	70

乙酸铵催化的酚与多聚甲醛的甲酰化反应研究

Formylation of Phenols and Paraformaldehyde Catalyzed by Ammonium Acetate

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 38

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yang Li, Jinding Yuan, Di Zhao. Deep Eutectic Solvent of 1,3-Dimethylurea/L-(+)-Tartaric Acid for the Green Synthesis of (E)-2-Styrylquinoline-3-carboxylic Acid Derivatives [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3268-3276.
[2]	Suzhen Zhang, Wenwen Zhang, Hui Yang, Qing Gu, Shuli You. Rhodium-Catalyzed Enantioselective Spiroannulation of 2-Alkenylphenols with Alkynes [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2926-2933.
[3]	Lu Liu, Shuguang Zhang, Renwei Hu, Xiaoxiao Zhao, Jingnan Cui, Weitao Gong. Synthesis and Properties of Phenolic Resin Polymers Based on Pillar[5]arene [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2808-2814.
[4]	Xiaojing Hu, Feixiang Guo, Runqing Zhu, Bingqi Zhou, Tao Zhang, Lizhen Fang. Synthesis of p-Alkoxy Phenol and Its Application after Dearomatization [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2239-2244.
[5]	Jian Ji, Jinhua Liu, Cong Guan, Xuwen Chen, Yun Zhao, Shunying Liu. High Regioselective Synthesis of N²-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1168-1176.
[6]	Jing Liu, Jintao Chen, Tingting Liu, Jia Liu, Yaofu Zeng. Recent Advances in the Reactions of β-Naphthol at α-Position [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 379-410.
[7]	Jiawei Huang, Xiaoman Li, Liang Xu, Yu Wei. Electrochemical Decarboxylation Coupling of α-Keto Acids with Thiophenols: A New Avenue for the Synthesis of Thioesters [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 756-762.
[8]	Shuo Li, Mingliang Wang, Laiyun Zhou, Lanzhi Wang. Magnetic Nano-Supported p-Toluenesulfonic Acid Catalyzed Synthesis of Fused Polycyclic 1,5-Benzoxazepines via Domino Reactions [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3977-3988.
[9]	Saimi Naibijiang, Lei Zhang, Shalamu Maidina, Jing Zeng, Abudu Rexit Abulikemu. Green Synthesis of Thiosulfonates and Sulfonyl Halides [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 236-243.
[10]	Zhentao Pan, Tong Liu, Yongmin Ma, Jianbo Yan, Ya-Jun Wang. Construction of Quinazolin(thi)ones by Brønsted Acid/Visible-Light Photoredox Relay Catalysis [J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2823-2831.
[11]	Jiantao Zhang, Cong Zhang, Zidong Zheng, Peng Zhou, Weibing Liu. Research Progress of Sulfoxonium Ylides in the Construction of Five/Six-Membered Nitrogen-Containing Heterocycles [J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2745-2759.
[12]	Ze Guo, Di Wu, Lili Wang, Zheng Duan. BF₃•Et₂O Promoted Dienone-Phenol Type Rearrangement to Synthesize Phosphepine with Aggregation Induced Luminescence (AIE) Effect [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2481-2487.
[13]	Runye Gao, Lingling Zuo, Fang Wang, Chuanying Li, Huajiang Jiang, Pinhua Li, Lei Wang. Recent Advances in Controllable Organic Reactions Induced by Visible Light without External Photocatalyst [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 1883-1903.
[14]	Tingshu Cao, Xiangyang Wei, Min Luo, Yifei Wang, Zijun Pan, Cheng Xu, Guodong Yin. PhI(OAc)₂-Promoted Dehydrogenation Oxidation for the Synthesis of 2-(Aryl/alkylthio)phenols and 10H-Phenothiazines [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2079-2088.
[15]	Qun Han, Kun Xu, Faning Tian, Shengyang Huang, Chengchu Zeng. A Practical Transamidation Strategy for the N-Deacylation of Amides [J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1123-1128.