PRODUCTION, CHARACTERIZATION AND USAGE OF A NOVEL DISULFONIC ACID-FUNCTIONALIZED IONIC LIQUID AS A HIGHLY EFFICIENT AND DUAL-FUNCTIONAL CATALYST FOR THE SYNTHESIS OF 1,8-DIOXO-9,10-DIARYL-DECAHYDROACRIDINES

We have produced a novel ionic liquid {N,N,N',N'-tetramethylethylene-diaminium-N,N'-disulfonic acid trifluoroacetate ([TMEDSA][TFA]₂)}, and identified it by analysis of ¹H NMR, ¹³C NMR, ¹⁹F NMR, mass, TG (thermogravimetry) and DSC (differential scanning calorimetry) data. Then, we have applied [TMEDSA][TFA]₂ as a dual-functional catalyst for the production of 1,8-dioxo-9,10-diaryl-decahydroacridines by the multi-component reaction of dimedone with arylaldehydes and primary amines. Furthermore, we have proposed a plausible and attractive mechanism based on dual-functionality of the catalyst. Due to dual-functionality of [TMEDSA][TFA]₂ (possessing acidic and basic sites), and also possessing two sites of each, it was highly effective and general, and produced the products in high yields.

Keywords:
N,N,N',N'-tetramethylethylene-diaminium-N,N'-disulfonic acid trifluoroacetate ([TMEDSA][TFA]₂); ionic liquid; dual-functional catalyst; 1,8-dioxo-9,10-diaryl-decahydroacridine; multi-component reaction

Authorship

Mostafa Karami

Department of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, IranPayame Noor UniversityIranTehran, IranDepartment of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, Iran

Abdolkarim Zare ^**e-mail: abdolkarimzare@pnu.ac.ir^##alternative e-mail: abdolkarimzare@yahoo.com

Department of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, IranPayame Noor UniversityIranTehran, IranDepartment of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, Iran

*e-mail: abdolkarimzare@pnu.ac.ir

#alternative e-mail: abdolkarimzare@yahoo.com

SCIMAGO INSTITUTIONS RANKINGS

Department of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, IranPayame Noor UniversityIranTehran, IranDepartment of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, Iran

Figures | Tables

Figures (11)
Tables (3)

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Scheme 1
The preparation of [TMEDSA][TFA]₂

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Figure 1
The ¹H NMR spectrum of [TMEDSA][TFA]₂

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Figure 2
The ¹³C NMR spectrum of the catalyst

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Figure 3
The ¹⁹F NMR spectrum of [TMEDSA][TFA]₂

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Figure 4
The mass spectrum of [TMEDSA][TFA[₂

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Figure 5
The TG diagram of [TMEDSA][TFA]₂

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Figure 6
The TG, DTG and DTA diagrams of the catalyst

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Figure 7
The DSC curve of [TMEDSA][TFA[₂

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Scheme 2
The model reaction for the synthesis of 1,8-dioxo-9,10-diaryl-decahydroacridines

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Figure 8
The acidic and basic sites of [TMEDSA][TFA]₂

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Scheme 3
The proposed mechanism

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Table 1
Influence of the catalyst quantity, solvent and temperature on the model reaction

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Table 2
The synthesis 1,8-dioxo-9,10-diaryl-decahydroacridines catalyzed by [TMEDSA][TFA]₂

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Table 3
Comparison of the results and reaction conditions of [TMEDSA][TFA]₂ with the reported catalysts

Scheme 1 The preparation of [TMEDSA][TFA]₂

Figure 1 The ¹H NMR spectrum of [TMEDSA][TFA]₂

Figure 2 The ¹³C NMR spectrum of the catalyst

Figure 3 The ¹⁹F NMR spectrum of [TMEDSA][TFA]₂

Figure 4 The mass spectrum of [TMEDSA][TFA[₂

Figure 5 The TG diagram of [TMEDSA][TFA]₂

Figure 6 The TG, DTG and DTA diagrams of the catalyst

Figure 7 The DSC curve of [TMEDSA][TFA[₂

Scheme 2 The model reaction for the synthesis of 1,8-dioxo-9,10-diaryl-decahydroacridines

Figure 8 The acidic and basic sites of [TMEDSA][TFA]₂

Scheme 3 The proposed mechanism

Table 1 Influence of the catalyst quantity, solvent and temperature on the model reaction

Entry	Mol% of [TMEDSA][TFA]₂	Solvent	Temp. (ºC)	Time (h)	Yield^a a Isolated yield. (%)
1	5	EtOH	Reflux	8	87
2	7	EtOH	Reflux	5	92
3	10	EtOH	Reflux	3	95
4	13	EtOH	Reflux	3	95
5	10	MeOH	Reflux	4	93
6	10	Solvent-free	78	2	28
7	10	MeCN	78	3	94
8	10	EtOAc	Reflux	3	93
9	10	THF	Reflux	4	90
10	10	CH₂Cl₂	Reflux	7	85
11	10	1,4-Dioxane	78	3	92
12	10	H₂O	78	12	21
13	10	EtOH	60	5	70
14	10	EtOH	70	4	78

^a
Isolated yield.

Table 2 The synthesis 1,8-dioxo-9,10-diaryl-decahydroacridines catalyzed by [TMEDSA][TFA]₂


Product	Ar	R	Time (h)	Yield^a a Isolated yield. (%)	M.p. (ºC) [Lit.]
1a	C₆H₅	Me	4	93	257-259 (260-262)¹⁰10 Shen, W.; Wang, L.-M.; Tian, H.; Tang, J.; Yu, J.-J.; J. Fluorine Chem. 2009, 130, 522.
1b	4-MeC₆H₄	Me	4	93	297-299 (296-297)²⁸28 Wang, X.-S.; Zhang, M.-M.; Jiang, H.; Shi, D.-Q.; Tu, S.-J.; Wei, X.-Y.; Zong, Z.-M.; Synthesis 2006, 4187.
1c	4-MeOC₆H₄	Me	3	91	279-281 (281-283)¹⁰10 Shen, W.; Wang, L.-M.; Tian, H.; Tang, J.; Yu, J.-J.; J. Fluorine Chem. 2009, 130, 522.
1d	3,4,5-(MeO)₃C₆H₂	Me	3	87	222-224 (224-226)²⁹29 Soliman, H. A.; Mubarak, A. Y.; El-Mekabati, A.; Elmorsy, S. S.; Chem. Sci. Trans. 2014, 3, 819.
1e	4-HOC₆H₄	Me	7	90	350-352 (352-354)¹⁶16 Hasaninejad, A.; Shekouhy, M.; Miar, M.; Firoozi, S.; Synth. React. Inorg. Nano-Met. Chem. 2016, 46, 151.
1f	3-O₂NC₆H₄	Me	5	94	283-285 (283-284)¹⁰10 Shen, W.; Wang, L.-M.; Tian, H.; Tang, J.; Yu, J.-J.; J. Fluorine Chem. 2009, 130, 522.
1g	4-O₂NC₆H₄	Me	3	95	272-274 (272-274)¹²12 Ghasemzadeh, M. A.; Safaei-Ghomi, J.; Molaei, H.; C. R. Chim. 2012, 15, 969.
1h	4-ClC₆H₄	Me	3	95	268-270 (269-271)¹⁰10 Shen, W.; Wang, L.-M.; Tian, H.; Tang, J.; Yu, J.-J.; J. Fluorine Chem. 2009, 130, 522.
1i	2-ClC₆H₄	Me	3	88	288-290 (285-287)³⁰30 Jin, T. S.; Zhang, J. S.; Guo, T. T.; Wang, A. Q.; Li, T. S.; Synthesis 2004, 2001.
1j	4-BrC₆H₄	Me	3	91	267-269 (270-272)²⁸28 Wang, X.-S.; Zhang, M.-M.; Jiang, H.; Shi, D.-Q.; Tu, S.-J.; Wei, X.-Y.; Zong, Z.-M.; Synthesis 2006, 4187.
1k	C₆H₅	H	3	92	253-255 (255-256)¹⁶16 Hasaninejad, A.; Shekouhy, M.; Miar, M.; Firoozi, S.; Synth. React. Inorg. Nano-Met. Chem. 2016, 46, 151.
1l	4-MeOC₆H₄	H	3	89	217-219 (219-222)¹⁶16 Hasaninejad, A.; Shekouhy, M.; Miar, M.; Firoozi, S.; Synth. React. Inorg. Nano-Met. Chem. 2016, 46, 151.

^a
Isolated yield.

Table 3 Comparison of the results and reaction conditions of [TMEDSA][TFA]₂ with the reported catalysts

Catalyst	Conditions	Time range	Yield range (%)	Ref.
[TMEDSA][TFA]₂	EtOH, Reflux	3-7 h	87-95	This work
Nano-ZrO₂-SO₃H	Solvent-free, 100 ºC	35-65 min	84-94	⁸8 Amoozadeh, A.; Rahmani, S.; Bitaraf, M.; Bolghan Abadi, F.; Tabrizian, E.; New J. Chem. 2016, 40, 770.
Fe₃O₄@SiO₂-MoO₃H nanoparticles	Solvent-free, 90 ºC	20-55 min	88-94	⁹9 Kiani, M.; Mohammadipour, M.; RSC Adv. 2017, 7, 997.
Imidazolium salts containing perfluoroalkyl tails	EtOH, Reflux	4 h	79-91	¹⁰10 Shen, W.; Wang, L.-M.; Tian, H.; Tang, J.; Yu, J.-J.; J. Fluorine Chem. 2009, 130, 522.
Tungstophosphoric acid nanoparticles supported on polyamic acid	EtOH-H₂O, Reflux	40-60 min	50-92	¹¹11 Nasr-Esfahani, M.; Rafiee, Z.; Kashi, H.; J. Iran. Chem. Soc. 2016, 13, 1449.
Nano-Fe₃O₄	Solvent-free, 120 ºC	10-50 min	70-95	¹²12 Ghasemzadeh, M. A.; Safaei-Ghomi, J.; Molaei, H.; C. R. Chim. 2012, 15, 969.
β -Cyclodextrin	H₂O, Ultrasound, 80 ºC	61-81 min	72-94	¹³13 Chate, A. V.; Rathod, U. B.; Kshirsagar, J. S.; Gaikwad, P. A.; Mane, K. D.; Mahajan, P. S.; Nikam, M. D.; Gill, C. H.; Chin. J. Catal. 2016, 37, 146.
Fe₂O₃-ZrO₂	MeCN, Reflux	3-5 h	80-90	¹⁴14 Pradhan, S.; Mishra, B. G.; RSC Adv. 2015, 5, 86179.
Nano-TiO₂	Solvent-free, 75 ºC	10-60 min	70-90	¹⁵15 Khazaei, A.; Moosavi-Zare, A. R.; Mohammadi, Z.; Khakyzadeh, V.; Afsar, J.; J. Chin. Chem. Soc. 2016, 63, 165.
Sulfonated polyethylene glycol	H₂O, 90 ºC	3-6 h	73-89	¹⁶16 Hasaninejad, A.; Shekouhy, M.; Miar, M.; Firoozi, S.; Synth. React. Inorg. Nano-Met. Chem. 2016, 46, 151.
Sulfated zirconia	EtOH, 70 ºC	8 h	89-95	³¹31 Kahandal, S. S.; Burange, A. S.; Kale, S. R.; Prinsen, P.; Luque, R.; Jayaram, R. V.; Catal. Commun. 2017, 97, 138.
N-Propyl benzoguanamine sulfonic acid supported on magnetic Fe₃O₄ nanoparticles	EtOH-H₂O, 100 ºC	15-20 min	84-95	³²32 Gholami Dehbalaei, M.; Foroughifar, N.; Pasdar, H.; Khajeh-Amiri, A.; New J. Chem. 2018, 42, 327.
Baker’s yeast	MeCN, Ultrasound, r.t.	2.9-4.3 h	70-84	³³33 Chate, A. V.; Sukale, S. B.; Ugale, R. S.; Gill, C. H.; Synth. Commun. 2017, 47, 409.
HCl	DMF, 100 ºC	30-75 min	61-90	³⁴34 Saljooghi, A. S.; Khabazzadeh, H.; Khaleghi, M.; J. Iran. Chem. Soc. 2017, 14, 727.
Cellulose sulfuric acid	MeCN, Reflux	4-7 h	40-85	³⁵35 Rajack, A.; Yuvarajua, K.; Praveena, C.; Murthy, Y. L. N.; J. Mol. Catal. A: Chem. 2013, 370, 197.
NH₄Cl	Solvent-free, 120 ºC	45-120 min	84-91	³⁶36 Banerjee, B.; Brahmachari, G.; J. Chem. Res. 2014, 38, 701.

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PRODUCTION, CHARACTERIZATION AND USAGE OF A NOVEL DISULFONIC ACID-FUNCTIONALIZED IONIC LIQUID AS A HIGHLY EFFICIENT AND DUAL-FUNCTIONAL CATALYST FOR THE SYNTHESIS OF 1,8-DIOXO-9,10-DIARYL-DECAHYDROACRIDINES

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[1] *e-mail: abdolkarimzare@pnu.ac.ir