ZnII doped and immobilized on functionalized magnetic hydrotalcite (Fe3O4/HT-SMTU-ZnII): A novel, green and magnetically recyclable bifunctional nanocatalyst for the one-pot multi-component synthesis of acridinediones under solvent-free conditions

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II

Zn doped and immobilized on functionalized magnetic

II

hydrotalcite (Fe O /HT-SMTU-Zn ): a novel, green and

3

4

Received 00th January 20xx,

Accepted 00th January 20xx

magnetically recyclable bifunctional nanocatalyst for one-pot

multi-component synthesis of acridinediones under solvent-free

conditions

DOI: 10.1039/x0xx00000x

www.rsc.org/

a

Z. Zarei and B. Akhlaghinia *

II

Zn doped and immobilized on functionalized magnetic hydrotalcite (Fe

3

O

4

/HT-SMTU-Zn ) was prepared for the first time

as a stable, long-lived, highly efficient and exceptional reusable magnetic nanocatalyst for the one-pot multi-component

synthesis of acridinediones as an important class of heterocyclic compounds. The synthesized catalyst was characterized

by various spectroscopic and microscopic techniques such as Fourier transform infrared (FT-IR) spectroscopy, X-ray

diffraction (XRD) analysis, Brunauer, Emmett and Teller (BET) surface area analysis, temperature programmed desorption

(TPD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy

(TEM), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), inductively coupled plasma atomic

emission spectroscopy (ICP-OES) and CHNS analysis. The results of characterizations showed the superparamagnetic

nature of catalyst with average particle size of 20-60 nm which is plate-like in shape. Also, the results of TPD analysis

showed that the nanocatalyst has both acidic sites (site density: 22.66 mmol/g) and basic sites (site density: 8.49 mmol/g),

II

and can act as a bifunctional nanocatalyst. The loading amount of Zn (doped and immobilized) on functionalized magnetic

hydrotalcite was indicated to be 4 mmol/g, obtained from ICP-OES analysis. The catalytic activity of this new magnetic

II

nanocatalyst (Fe

3

O

4

/HT-SMTU-Zn ) was examined in the multi-component reaction of aromatic aldehydes, dimedone, and

+

various primary amines/ or NH

4

in solvent free condition towards the preparation of acridinedione derivatives in short

period of time. In all cases, the catalyst could be easily recovered magnetically for at least six runs and the obtained

product was isolated using a simple work-up procedure. In our protocol, solvent free condition avoids the problems such

as cost, handling, safety and pollution which are related to solvent use. The characteristics of the present methodology

make the reaction suitable for scale-up and commercialization.

6

medicinally important compounds, so far, a great number of these

1

. Introduction

compounds have been synthesized and clinically used as anti-

7

8

microbial and antibacterial agents. Broad synthetic possibilities

are available in the literature due to the presence of several

Acridinediones as an important class of nitrogen heterocyclic

compounds were discovered in 19th century. Acridinediones with

9

reaction centers in acridinediones. Usual synthetic route for the

1

,4-dihydropyridine (DHP) ring are the core structure of a number

synthesis

of

acridinediones

involves

multi-component

of biologically interesting compounds which are similar to

Nicotinamide Adenine Dinucleotide (NADH, an important vital co-

cyclocondensation of two molecules of dimedone (5,5-dimethyl-

1,3-cyclohexadione) and various aromatic aldehydes in the

presence of nitrogen source like different primary amines /or

1

enzyme in biological systems). Moreover, acridinedione derivatives

2

3

are reported that they can be used as anti-fungal, anti-tumor,

6

,10,11

4

5

ammonium acetate.

These synthetic methods have been

anti-cancer, anti-glaucoma and are used in laser dyes due to their

3

,4

catalyzed by utilizing various homogeneous or heterogeneous

high fluorescence efficiency. As acridinedione derivatives are

12

13

14

15

,

catalysts such as Amberlyst-15, CTAB, DBSA, FSG-Hf(Npf

2

)

4

5

c

16

O,

17

H

2

SO

4

,

Zn(OAc)

2

.2H

2

CeCl

3

.7H

2

O,

pyridinium hydrogen

1

8

19

20

21

sulfate, p-dodecylbenzene sulfonic acid, [Hmim]TFA, B(C F ) ,

6

5 3

22

,

23

+ 24

vitamin B

1

CAN, melamineformaldehyde resin supported H ,

1

25

26

27

28

33

proline, SiO

2

-Pr-SO

3

3 2 3 2

H, MCM-SO H, CdO, Fe O @SiO -PW,

2

9

30

31

32

Fe O , γ-Fe O , Fe O @SiO , NiFe O @SiO -FHS, ZnFe O ,

3

4

2

3

4

2

4

2

2 4

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4

35

36

Pt NPs@GO, GO and SiO

2

-I. While many of the reported By considering the fact that the separation of hydrotalcite-based

3

7

methods are effective, some of them have lots of limitations and catalysts from the reaction mixture is difficult to some extent,

suffer from drawbacks such as time-consuming methods for replacement of conventional separation methods (centrifugation

separating the catalyst, prolonged reaction time, tedious and filtration) with magnetic separation approach is a fascinating

4

5, 46

preparation processes in the synthesis of the catalysts, low technique.

Thus, incorporation of magnetic nanoparticles

38, 39

efficiency and high reaction temperatures, the cost of the catalysts, (MNPs) into the hydrotalcite structure

provides easy separation

side reactions, effluent generation, harsh reaction conditions and of catalysts from the reaction mixture using a simple magnetic bar

unsatisfactory yields. In view of the above-mentioned limitations, along with prevention of MNPs agglomeration, as well.

introducing a green and highly efficient method applying a new Considering all the above reasons (especially environmentally

heterogeneous, magnetic reusable and nonhazardous nanocatalyst benign nature of magnetic hydrotalcites) and the versatility of

II

for the synthesis of acridinedione is of importance.

2 2 3 4

Zn(OAc) .2H O encouraged us to synthesize Fe O /HT-SMTU-Zn

Organic synthesis under the conditions with respect to the principle and study its utility in organic synthesis. Following our efforts

of green chemistry was still continued to be explored today. Among toward the development of efficient and environmentally benign

4

7

the attempts made in connection with this issue, also performing heterogeneous nanocatalysts in synthetic organic chemistry,

one-pot reaction (combination of more than two or three different herein we wish to report an efficient, green and novel method, for

reactants in a single step via covalent bonds) using green and the synthesis of acridinedione derivatives via one-pot multi-

environmentally friendly catalyst and mild reaction conditions component cyclocondensation of two molecules of dimedone (5,5-

should be concern.

For this purpose, to improve the long-term durability and activity of the presence of nitrogen source like different primary amines /or

catalysts, hydrotalictes (HTs) and magnetic hydrotalcites (MHTs) ammonium ion in solvent-free conditions by the help of Fe /HT-

dimethyl-1,3- cyclohexadione) and various aromatic aldehydes in

3

O

4

II

have been widely studied as promising supporting materials for SMTU-Zn as a highly efficient, robust, magnetically reusable

catalysts in organic reactions. Hydrotalictes as a layer double nanocatalyst (Scheme 1). Target molecules have been characterized

+

2

+3

1

13

hydroxide (LDH) (represented by a general formula of [M (1-x)M

by FT-IR, H-NMR and C-NMR data and mass spectral analyses,

x+

n- x

x-

2+

3+

x(OH)

2

]

[A /n. mH

2

O] where M and M are di and trivalent respectively.

n-

metal ions and A indicates the interlayer anions) with abundant

surface hydroxyl groups

consist of alternating cationic

2

+

2-

(

6 2 3

Mg Al (OH)16 as the brucite-like) layers, anionic (CO ) interlayers

and Mg-Al mixed oxides which are chemically active sites (strong

basic sites) for use in catalytic reactions and also act as the

3

7-44

anchoring sites for metal nanoparticles.

II

3 4

Scheme 1 Synthesis of acridinedione derivatives in the presence of Fe O /HT-SMTU-Zn .

2

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PRO, CCD, Australia. The magnetic property of catalyst was

measured using a vibrating sample magnetometer (VSM,

Magnetic Danesh pajoh Inst). All yields refer to isolated

products after purification by thin layer chromatography or

2

. Experimental

2

.1. General

All chemical reagents and solvents were purchased from recrystallization.

Merck and Sigma-Aldrich chemical companies and were used

as received without further purification. The purity 2.2. Preparation of HT(I)

determinations of the products were accomplished by TLC on An aqueous solution (60 mL) containing Mg(NO ) .6H O (10.25

3

2

silica gel polygram STL G/UV 254 plates or GLC on a shimadzu g, 40 mmol) and Al(NO ) .9H O (7.50 g, 20 mmol) was taken

model GC-17A instrument.

3

2

into a 250 mL flask. Then, the mixed solution (60 mL)

The FT-IR spectra were recorded on pressed KBr pellets using containing NaOH (4 g, 100 mmol) and NaHCO (2.1 g, 25 mmol)

3

an AVATAR 370 FT-IR spectrometer (Therma Nicolet was prepared and added drop by drop into the solution with

spectrometer, USA) at room temperature in the range vigorous stirring at 60 °C. Afterward, the resulting suspension

-1

between 4000 and 400 cm with a resolution of 4 cm . The was stirred for 24 h at 60 °C. Subsequently, the obtained white

NMR spectra were obtained in Brucker Avance 300 MHz solid was filtered and washed with deionized water until the

6

instruments in DMSO-d . Mass spectra were recorded with a pH reached 7 to remove the alkali metal ions. The obtained

CH7A Varianmat Bremem instrument at 70 eV electron impact Mg-Al hydrotalcite (

ionization, in m/z (rel %). Elemental analyses were performed 100 °C for 12 h.

using a Thermo Finnigan Flash EA 1112 Series instrument. The

I) (molar ratio Mg/Al = 2) was then dried at

crystal structure of catalyst was analyzed by XRD using a D8 2.3. Preparation of Fe O /HT (II)

3

4

ADVANCE-Bruker diffractometer operated at 40 kV and 30 mA In a three-necked 500 mL round-bottom flask equipped with

utilizing Cu Kα radiation (λ= 0.154 A°). The BET surface area argon gas inlet tube and dropping funnel, a mixture of

and pore size distribution were measured on a Belsorp mini II FeCl .6H O (2.1 g, 8 mmol) and FeCl .4H O (1.05 g, 5.2 mmol)

3

2

system at -196

were carried

CAT-A characterization system equipped with

°C using N as the adsorbate. TPD experiments was dissolved in 100 mL deionized water. Afterwards, the

2

out

in

an

automated

BEL resulting mixture was stirred for 5 to 10 minutes at 80 °C

TCD under Ar atmosphere, and then hydrotalcite (

)(4 g) and NaOH

a

I

detector which detects the concentration in the gas stream solution (100 mL, 5%) were simultaneously added into the

and the adsorbed amount is calculated from the concentration solution. The resulting suspension was stirred at 80 °C for 24 h.

change. In order to remove water and other contaminants, the The synthesized Fe O /HT (II) (as a brown powder) was then

3

4

samples (50 mg in all cases) were pretreated collected by an external magnet and washed with distilled

successively in air and helium flow (850 for h) water (2 × 100 mL) until the pH reached 7. Subsequently

before NH and CO adsorption. The samples were then Fe O /HT (II) was dried at 50 °C for 12 h.

cooled to room temperature and then subjected to He/NH₃

mixture (90/10 v/v) and He/CO mixture (90/10 v/v) at a flow 2.4. Preparation of Fe O /HT-(CH ) Cl (III)

rate of 50 ml/min at 50 C for 1 h, respectively. Scanning Fe O /HT(II) (2 g) was dispersed in toluene (10 mL) by

°C

1

3

2

3

4

2

3

4

2 3

°

3

4

electron microscopy (SEM) images also recorded using sonication for 30 minutes. 3-Chloropropyltrimethoxysilane (2

Leo1450 VP scanning electron microscope operating at an g, 8 mmol) was then added to the suspension at room

acceleration voltage 20 kV. Elemental compositions were temperature. Afterwards, the resultant mixture was refluxed

determined with an SC7620 Energy-dispersive X-ray analysis for 12 h. Successively, Fe O /HT-(CH ) Cl (III) was magnetically

3

4

2 3

(EDX) presenting a 133 eV resolution at 20 kV. Transmission collected, washed with ethanol (2× 10 mL) and dried at 50 °C

electron microscopy (TEM) was performed with a Leo 912 AB for 12 h.

microscope (Zeiss, Germany) with an accelerating voltage of

120 kV. TGA analysis was carried out on

a Shimadzu 2.5. Preparation of Fe O /HT-SMTU (IV)

3 4

Thermogravimetric Analyzer (TG-50) in the temperature range To a suspension of the obtained Fe O /HT-(CH ) Cl (III) (2 g) in

3

4

2 3

-1

of 25–950 °C at a heating rate of 10 °C min under air ethanol (10 mL) (by sonication for 30 minutes), potassium

atmosphere. Inductively coupled plasma atomic emission carbonate (0.96 g, 7mmol) and S-methylisothiourea

spectroscopy (ICP-OES) was carried out on a Varian, VISTA- hemisulfate salt (1g, 7 mmol) were added. The resultant

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mixture was refluxed for 12 h. Then, Fe O /HT-SMTU (IV) was isolated yield: 90%; mp 259-261 °C (from EtOH ) (lit., 260-262 °C);

3

4

1

separated magnetically, washed with ethanol (2× 10 mL), and

then dried at 50 °C for 12 h.

H NMR: δH (300 MHz; DMSO-d ; Me Si) 7.65-7.42 (5H, m, Ph), 7.23

6

4

(2H, d, J = 6 Hz, Ph), 7.06 (2H, d, J = 6 Hz, Ph), 5.05 (1H, s, CH), 3.37

(

3H, s, CH ), 2.25-2.17 (4H, m, 2CH ), 2.01 (2H, d, J = 15.9 Hz, CH ),

3

2

II

2

.6. Preparation of Fe

To a solution of Zn(OAc)

20 mL), the obtained Fe O /HT-SMTU (IV) (2 g) was added and 135.0, 130.5, 129.9, 128.8, 127.9, 113.5, 50.0, 41.4, 32.4, 31.9, 29.8,

3

O

4

/HT-SMTU-Zn (V) nanoparticles

2 3 3

1.76 (2H, d, J = 15.9 Hz, CH ), 0.88 (6H, s, 2CH ), 0.72 (6H, s, 2CH );

1

3

2

.2H

2

O (1.4 g, 6 mmol) in dry methanol

C NMR: δC (75 MHz; DMSO-d ; Me Si) 195.4, 150.6, 143.8, 138.9,

6

4

(

3

4

+

refluxed for 12 h. Afterward, the resulting suspension was 26.5, 21.1; MS, m/z 440 (M , 82%) 345 (100, M - C H ), 91 (54,

7

collected using an external magnet and washed repeatedly C H ).

with water (2 × 50 mL) and dried at 100 °C for 12 h.

7

9

-(4-bromophenyl)-3,3,6,6-tetramethyl-10-phenyl-3,4,6,7,9,10-

2

9

.7. Typical procedure for preparation of 3,3,6,6-tetramethyl- hexahydroacridine-1,8(2H,5H)-dione (4d): Yellow solid; isolated

2

9

1

yield: 95%; mp 253-255 °C (from EtOH ) (lit., 254-256 °C); H NMR:

δH (300 MHz; DMSO-d ; Me Si) 7.67-7.58 (3H, m, Ph), 7.47-7.44

A mixture of benzaldehyde (0.1g, 1 mmol), dimedone (0.28 g, 2 (4H, m, Ph), 7.28 (2H, d, J = 8.4 Hz, Ph), 5.03 (1H, s, CH), 2.56-2.19

,10-diphenyl-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-

II

dione (4a) in the presence of Fe

3

O

4

/HT-SMTU-Zn (V)

6

4

mmol) and aniline (0.09g, 1 mmol) in the presence of (4H, m, 2CH

2

), 2.02 (2H, d, J = 18 Hz, CH

), 0.89 (6H, s, 2CH ), 0.73 (6H, s, 2CH

round-bottomed flask and stirred at 70 °C under solvent free DMSO-d ; Me

conditions. After completion of the reaction which was 129.9, 119.2, 112.9, 49.4, 41.4, 32.43, 32.31, 29.7, 26.6; MS, m/z

2

), 1.82 (2H, d, J = 18 Hz,

II

13

Fe O /HT-SMTU-Zn (

V

) (0.008 g, 4 mol%) was taken into a CH

2

3

); C NMR: δC (75 MHz;

Si) 195.5, 151.0, 146.1, 138.8, 131.2, 130.5, 130.3,

4

3

4

6

+

6 4

monitored by TLC (n-hexane: EtOAc, 1:2), the reaction mixture 505 (M +2, 47%), 503 (52, M ), 344 (71, M - C H Br).

was dissolved in ethyl acetate, and the nanocatalyst was

9

-(3-bromophenyl)-3,3,6,6-tetramethyl-10-phenyl-3,4,6,7,9,10-

separated by an external magnet. Afterwards, the combined

organic phase was washed with water (2×10 mL) and

concentrated to give the crude product. Finally, the resulting

crude product was purified by thin layer chromatography using

ethyl acetate: n-hexane (2:1) as an eluent to give the pure

desired product as yellow solid (% 95, 0.40 g).

hexahydroacridine-1,8(2H,5H)-dione (4e): Yellow solid; isolated

-1

yield: 90%; mp 250-252 °C (from EtOH); FT-IR (KBr): νmax/cm 3175,

1

3

059, 2955, 2879, 2810, 1647, 1609, 1489, 1145, 1011; H NMR: δH

300 MHz; DMSO-d ; Me Si) 7.67-7.58 (2H, m, Ph), 7.48 (1H, d, J =

.5 Hz, Ph), 7.41-7.24 (6H, m, Ph), 5.04 (1H, s, CH), 2.26-2.19 (4H, m,

(

6

4

1

2

1

3

CH

2

3

), 2.07-1.76 (4H, m, 2CH

2

), 0.89 (6H, s, 2CH

3

), 0.73 (6H, s,

1

3

); C NMR: δC (75 MHz; DMSO-d ; Me Si) 195.5, 151.1, 149.2,

6

4

2.8. Spectral data

38.7, 131.1, 130.8, 129.9, 129.1, 126.7, 121.5, 112.8, 49.9, 41.4,

+

6 4

2.4, 29.7, 26.5; MS, m/z 504 (M , 65%), 344 (100, M - C H Br);

3

1

2

,3,6,6-tetramethyl-9,10-diphenyl-3,4,6,7,9,10-hexahydroacridine- Elemental analysis: Found: C, 69.08; H, 5.93; N, 2.79. Calc. for

,8(2H,5H)-dione (4a): Yellow solid; isolated yield: 95%; mp 252- C₂₉H₃₀BrNO : C, 69.05; H, 5.99; N, 2.78%.

2

25

1

54 °C (from EtOH ) (lit., 254-256 °C); H NMR: δH (300 MHz;

; Me Si) 7.65-7.43 (4H, m, Ph), 7.63 (2H, d, J = 6 Hz, Ph),

.26 (2H, t, J = 8 Hz, Ph), 7.11 (2H, t, J = 8 Hz, Ph), 5.10 (1H, s, CH),

.26-2.10 (4H, m, 2CH ), 2.02 (2H, d, J = 15.9 Hz, CH ), 1.78 (2H, d, J

15.9 Hz, CH ), 0.88 (6H, s, 2CH ), 0.72 (6H, s, 2CH ); C NMR: δC

4

-(3,3,6,6-tetramethyl-1,8-dioxo-10-phenyl-1,2,3,4,5,6,7,8,9,10-

DMSO-d

6

4

decahydroacridin-9-yl)benzonitrile (4f): Yellow solid; isolated yield:

7

2

=

-1

9

2

⁵^%^;^m^p²¹⁰^-²¹³^°^C⁽^f^r^o^m^E^t^O^H⁾^;^F^T^-^I^R⁽^K^B^r⁾^:^νmax/cm 3060, 3031,

2

1

3

954, 2870, 2834, 2229, 1645, 1577, 1508, 1033; H NMR: δH (300

2

3

MHz; DMSO-d

6 4

; Me Si) 7.73 (2H, d, J = 8.1 Hz, Ph), 7.67-7.58 (3H,

(75 MHz; DMSO-d

6

4

; Me Si) 195.5, 150.7, 146.7, 138.9, 130.5, 129.8,

m, Ph), 7.54 (2H, d, J = 8.1 Hz, Ph), 7.48-7.46 (2H, m, Ph), 5.12 (1H, s,

1

4

28.3, 128.0, 126.2, 113.4, 50.0, 41.45, 32.4, 29.8, 26.5; MS, m/z

+

CH), 2.26-2.00 (4H, m, 2CH

2

3

), 2.05-1.76 (4H, m, 2CH

2

), 0.88 (6H, s,

6 5 6

26 (M , 60%), 348 (100, M - C H ), 328 (30, M - C H10O).

1

2

CH ), 0.71 (6H, s, 2CH ); C NMR: δC (75 MHz; DMSO-d ; Me Si)

3

6

4

9

-(4-methoxyphenyl)-3,3,6,6-tetramethyl-10-phenyl-3,4,6,7,9,10-

195.5, 152.0, 151.4, 138.6, 132.4, 130.5, 130.0, 129.2, 119.4, 112.4,

+

hexahydroacridine 1,8(2H,5H)-dione (4b): Yellow solid; isolated 109.1, 49.8, 41.4, 33.4, 32.4, 29.6, 26.6; MS, m/z 450 (M , 88%),

2

5

1

+

yield: 95%; mp 216-218 °C (from EtOH) (lit., 218-220 °C); H NMR: 344 (100, M - C H N); Elemental analysis: Found: C, 79.92; H, 6.72;

7

4

δH (300 MHz; DMSO-d

6 4

; Me

30 2 2

Si) 7.65-7.40 (5H, m, Ph), 7.22 (2H, d, J N, 6.21. Calc. for C30H N O : C, 79.97; H, 6.71; N, 6.22%.

=

8.7 Hz, Ph), 8.81 (2H, d, J = 8.7 Hz, Ph), 4.99 (1H, s, CH), 3.70 (3H,

3

,3,6,6-tetramethyl-10-phenyl-9-(pyridin-4-yl)-3,4,6,7,9,10-

s, CH ), 2.24-2.16 (4H, m, 2CH ), 1.87 (4H, dd, J = 17.4 Hz, J = 15.9

3

2

1

3

hexahydroacridine-1,8(2H,5H)-dione (4g): Yellow solid; isolated

Hz, 2CH

2

), 0.88 (6H, s, 2CH

3

), 0.72 (6H, s, 2CH ); C NMR: δC (75

3

-1

yield: 85%; mp 205-207 °C (from EtOH); FT-IR (KBr): νmax/cm 3060,

MHz; DMSO-d ; Me Si) 195.5, 157.7, 150.4, 139.0, 138.9, 130.5,

6

4

1

3

028, 2954, 2929, 2868, 1641, 1573, 1512; H NMR: δH (300 MHz;

1

29.8, 128.9, 128.2, 113.7, 113.6, 55.3, 50.0, 41.4, 32.4, 31.4, 29.7,

+

DMSO-d ; Me Si) 8.46 (2H, d, J = 6 Hz, Pyridine), 7.64-7.59 (3H, m,

26.5; MS, m/z 455 (M , 98%), 344 (100, M - C

7

H

7

O).

6

4

Ph), 7.47-7.45 (2H, m, Ph), 7.30 (2H, d, J = 6 Hz, Pyridine), 5.04 (1H,

s, CH), 2.26-2.20 (4H, m, 2CH ), 2.04 (2H, d, J = 15 Hz, CH ), 1.78 (2H,

3

,3,6,6-tetramethyl-10-phenyl-9-(p-tolyl)-

2

,4,6,7,9,10hexahydroacridine-1,8(2H,5H)-dione (4c): Yellow solid;

4

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1

3

d, J = 15 Hz, CH

2

), 0.89 (6H, s, 2CH

3

), 0.73 (6H, s, 2CH

3

); C NMR: δC 10-(2-bromophenyl)-3,3,6,6-tetramethyl-9-phenyl-3,4,6,7,9,10-

(

75 MHz; DMSO-d

6

; Me

4

Si) 195.5, 154.5, 151.5, 149.9, 138.6, 130.0, hexahydroacridine-1,8(2H,5H)-dione (4m): Yellow solid; isolated

+

-1

1

6

7

23.3, 112.0, 49.8, 41.4, 32.5, 32.4, 29.6, 26.6; MS, m/z 426 (M , yield:75%; mp 269-271 °C (from EtOH ); FT-IR (KBr): νmax/cm 3060,

+

1

4%), 344 (100, M - C

4

H

4

N); Elemental analysis: Found: C, 78.54; H, 2956, 2934, 2887, 1639, 1576, 1144, 1087; H NMR: δH (300 MHz;

: C, 78.84; H, 7.09; N, 6.57%. DMSO-d ; Me Si) 7.97 (1H, d, J = 6 Hz, Ph), 7.66-7.51 (5H, m, Ph),

.24 (2H, t, J = 8 Hz, ph), 7.08 (1H, t, J = 8 Hz, Ph), 5.0 (1H, s, CH),

.24-2.16 (4H, m, 2CH ), 1.99 (2H, d, J = 18 Hz, CH ), 1.50 (2H, d, J =

8 Hz, CH ), 0.88 (6H, s, 2CH

.05; N, 6.54. Calc. for C28

H

30

N

2

O

2

6

4

7

2

1

0-(4-methoxyphenyl)-3,3,6,6-tetramethyl-9-phenyl-3,4,6,7,9,10-

2

hexahydroacridine-1,8(2H,5H)-dione(4h): Yellow solid; isolated

13

2

3

), 0.78 (6H, s, 2CH

3

); C NMR: δC (75

29

1

yield: 90%; mp 213-215 °C (from EtOH ) (lit., 215-216 °C); H NMR:

MHz; DMSO-d ; Me Si) 195.4, 149.7, 146.7, 137.6, 134.0, 132.7,

6

4

δH (300 MHz; DMSO-d ; Me Si) 7.39-7.28 (3H, m, Ph), 7.26-7.08

6

4

132.0, 129.8, 129.0, 127.9, 126.0, 124.7, 113.5. 49.9, 41.6, 33.5,

+

(

6H, m, Ph), 5.07 (1H, s, CH), 3.87 (3H, s, OCH

3

), 2.53-2.18 (4H, m,

), 0.90 (6H, s, 2CH ), 0.73 (6H, s,

); C NMR: δC (75 MHz; DMSO-d ; Me Si) 195.5, 159.7, 151.3,

3

2.2, 30.2, 26.0; MS, m/z 504 (M , 83%), 426 (100, M - C

Elemental analysis: Found: C, 69.02; H, 5.67; N, 2.78. Calc. for

30BrNO : C, 69.05; H, 5.99; N, 2.78%.

6 5

H );

2

1

3

CH

2

3

), 2.04-1.80 (4H, m, 2CH

2

3

13

CH

6

4

C

29

H

2

46.7, 131.4, 128.3, 127.9, 126.2, 115.4, 113.3, 60.2, 55.9, 50.0,

+

2.3, 32.3, 29.8, 26.5; MS, m/z 545(M , 68%), 374 (73, M - C

).

6

H

5

), 43 3,3,6,6-tetramethyl-9-phenyl-10-(pyridin-2-yl)-3,4,6,7,9,10-

hexahydroacridine-1,8(2H,5H)-dione (4n): Yellow solid; isolated

(100, COCH

2

-1

yield: 30%; mp 255-257 °C (from EtOH); FT-IR (KBr): νmax/cm 3051,

1

10(3,4dimethylphenyl)3,3,6,6tetramethyl9phenyl3,4,6,7,9,10hexa

3

026, 2957, 2869, 1641, 1583, 1178, 1144, 1122; H NMR: δH (300

hydroacridine1,8(2H,5H)-dione (4i): Yellow solid; isolated yield:

MHz; DMSO-d ; Me Si) 8.76 (1H, s, Pyridine), 8.13 (1H, td, J = 7.8

6

4

-

1

9

0%; mp 251-253 °C (from EtOH ); IR (KBr): νmax/cm 3084, 3031,

Hz, J = 1.8 Hz, Pyridine), 7.66-7.62 (2H, m, Pyridine), 7.40-7.37 (2H,

m, Ph), 7.27-7.22 (2H, m, Ph), 7.10 (1H, t, J = 6 Hz, Ph), 5.04 (1H, s,

CH), 2.25-2.18 (4H, m, 2CH ), 1.99 (2H, d, J = 18 Hz, CH ), 1.70 (2H,

1

2

960, 2937, 2872, 2822, 1641, 1575, 1176, 1141, 998; H NMR: δH

(

300 MHz; DMSO-d ; Me Si) 7.38-7.33 (3H, m, Ph), 7.28-7.23 (2H, m,

6 4

2

1

3

Ph), 7.12-7.08 (3H, m, Ph), 5.08 (1H, s, CH), 6.05 (6H, s, 2CH

.17 (4H, m, 2CH ), 2.0 (2H, d, J = 15 Hz, 2CH ), 1.82 (2H, d, J = 15

Hz, 2CH ), 0.89 (6H, s, 2CH ), 0.73 (6H, s, 2CH

MHz; DMSO-d ; Me Si) 195.4, 151.0, 146.8, 138.1, 136.5, 128.3,

28.0, 126.2, 113.3, 50.0, 41.3, 32.4, 32.3, 29.7, 26.6, 19.9, 18.6;

3

), 2.26-

d, J = 18 Hz, CH

2

3 3

), 0.88 (6H, s, 2CH ), 0.72 (6H, s, 2CH ); C NMR: δC

2

(

75 MHz; DMSO-d ; Me Si) 195.5, 151.8, 150.6, 149.9, 146.7, 140.1,

6 4

1

3

2

3

); C NMR: δC (75

1

2

28.2, 128.2, 126.2, 125.5, 125.4, 113.5, 50.0, 40.8, 32.6, 32.5, 29.6,

+

6

4

6 5 2

1.6; MS, m/z 426 (M , 47%), 345 (82, M - C H ), 44 (100, COCH );

1

Elemental analysis: Found: C, 78.20; H, 7.08; N, 6.51. Calc. for

: C, 78.84; H, 7.09; N, 6.57%.

+

MS, m/z 454 (M , 28%), 374 (100, M - C

14, C ); Elemental analysis: Found: C, 82.09; H, 7.22; N, 3.76.

Calc. for C31 : C, 82.08; H, 7.78; N, 3.09%.

6 5 8 9

H ), 346 (25, M - C H ), 77

28 30 2 2

C H N O

(

6 5

H

35NO

2

3,3,6,6-tetramethyl-9-phenyl-3,4,6,7,9,10-hexahydroacridine-

1

,8(2H,5H)-dione (4o): Yellow solid; isolated yield: 95%; mp 276-

2

5

1

3,3,6,6-tetramethyl-9-phenyl-10-(p-tolyl)-3,4,6,7,9,10-

2

78 °C (from EtOH ) (lit., 277-279 °C); H NMR: δH (300 MHz;

; Me Si) 9.32 (1H, s, NH), 7.18-7.17 (5H, m, Ph), 4.84 (1H, s,

CH), 2.53-2.37(4H, m, 2CH ), 2.32-1.84 (4H, m, 2CH ), 1.03 (6H, s,

hexahydroacridine-1,8(2H,5H)-dione(4j):Yellow solid; isolated

DMSO-d

6

4

29

yield: 92%; mp 259-261 °C (from EtOH) (lit., 260-262 °C); MS, m/z

2

+

4

⁴⁰⁽^M⁺^,⁷⁰^%⁾^,⁴³⁽⁴⁶^,^C^O^C^H2⁾^.

2CH ), 0.88 (6H, s, 2CH ); MS, m/z 349 (M , 6%), 269 (100, M -

3

C

6

H

5

), 77 (34, C

6 5

H ).

3,3,6,6-tetramethyl-9-phenyl-10-(m-tolyl)-3,4,6,7,9,10-

hexahydroacridine-1,8(2H,5H)-dione (4k): Yellow solid; isolated

9

-(4-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-

-1

^yⁱ^e^l^d^:⁹⁵^%^;^m^p²⁶²^-²⁶⁴^°^C⁽^f^r^o^m^E^t^O^H⁾^;^F^T^-^I^R⁽^K^B^r⁾^:^νmax/cm 3064,

hexahydroacridine-1,8(2H,5H)-dione (4p): Yellow solid; isolated

1

2

5

3

031, 2958, 2869, 2819, 1641, 1577, 1143, 1122; H NMR: δH (300

yield: 95%; mp 277-280 °C (from EtOH) (lit., 278-280 °C); MS, m/z

+

MHz; DMSO-d

.28-7.23 (3H, m, Ph), 7.13-7.08 (2H, m, Ph), 5.08 (1H, s, CH), 2.43

3H, s, CH ), 2.26-2.18 (4H, m, 2CH ), 2.0 (2H, d, J = 15 Hz, 2CH

.82 (2H, d, J = 15 Hz, 2CH ), 0.89 (6H, s, 2CH ), 0.73 (6H, s, 2CH

C NMR: δC (75 MHz; DMSO-d ; Me

6 4

; Me Si) 7.53-7.48 (1H, m, Ph), 7.40-7.33 (3H, m, Ph),

3

80 (M , 60%), 269 (100, M - C H ), 77 (60, C H ).

6 5 6 5

7

(

3

2

), 9-(4-chlorophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-

1

2

3

); hexahydroacridine-1,8(2H,5H)-dione (4q): Yellow solid; isolated

1

3

25

Si) 195.5, 150.8, 146.8, 138.8, yield: 95%; mp 315-317 °C (from EtOH ) (lit., 317-320 °C); MS, m/z

6

4

+

1

30.5, 128.3, 128.0, 126.2, 113.3, 50.0, 41.3, 32.4, 29.7, 26.6, 21.3; 383 (M , 51%), 268 (100, M - C

6

H

5

).

+

MS, m/z 440 (M , 68%), 43 (52, COCH ); Elemental analysis: Found:

2

9

-(4-bromophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-

2

C, 81.92; H, 7.57; N, 3.18. Calc. for C30H33NO : C, 81.97; H, 7.57; N,

hexahydroacridine-1,8(2H,5H)-dione (4r): Yellow solid; isolated

3

.19%.

3

2

yield: 95%; mp 239-241 °C (from EtOH) (lit., 240-242 °C); MS, m/z

+

10-(4-chlorophenyl)-3,3,6,6-tetramethyl-9-phenyl-3,4,6,7,9,10-

429 (M + 2, 54%), 427 (98, M ).

hexahydroacridine-1,8(2H,5H)-dione (4l): Yellow solid; isolated

3

4

yield: 90%; mp 301-303 °C (from EtOH) (lit., 300-302 °C); FT-IR

3. Results and discussion

-1

(

KBr): ν_m_a_x/cm 3092, 3056, 2955, 2937, 2888, 2868, 1640, 1576;

+

II

MS, m/z 459 (M , 82%), 379 (100, M - C

6

H

5

), 344 (25, M - C

6

H

4

Cl).

3.1. The characterization of Fe O /HT-SMTU-Zn

3

4

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-1

51

HT (

precipitation method. For synthesis of Fe

treated with an alkaline mixed salt-solution of ferrous and that appear at 1580 and 1406 cm (corresponding to

I) was easily and reproducibly prepared through the co- vibration (1552 cm ) (Fig. 1d). Finally, the coordination of

3

O

4

/HT (II), HT ( ) was Zn(OAc) .2H O can be confirmed by the stretching vibrations

I

2

-1

-

1

ferric ions. Afterward, the surface of Fe O /HT (II) was stretching modes of carboxylate groups) and 619 cm

3

4

5

2, 53

modified by 3-chloropropyltriethoxysilane and then by S- (corresponding to stretching vibrations of Zn-S bond).

methylisothiourea hemisulfate salt to produce Furthermore, this coordination can be verified by decreasing

Fe O /HT(CH ) Cl (III), Fe O /HT-SMTU(IV) respectively. Doping the intensity and frequency of the hydroxyl groups (Fig. 1e).

3

4

2 3

3 4

and immobilization of Zn(OAc)

2

.2H

2

O on Fe

3

O

4

/HT-SMTU(IV

/HT- Zn (

presented in Fig. 2. As seen in Fig. 2a, the as-synthesized

/HT-SMTU- hydrotalcite nanoparticles exhibited the characteristic

V) was performed by using various spectroscopic and diffraction peaks at around 2Ɵ =11.2°, 22.6°, 34.5°, 38.0°,

)

The XRD patterns of HT (

I

), Fe

3

O

4

/HT(II), Fe

3

O

4

/HT-SMTU-

II

th

II

was conducted in dry refluxing methanol to obtain Fe

3

O

4

V

) and the 6 reused Fe /HT-SMTU-Zn

3

O

4

(V) have been

II

SMTU-Zn (

V) nanoparticles ( Scheme 2).

Structural and chemical characterizations of Fe

II

Zn (

3 4

O

microscopic techniques such as Fourier transform infrared (FT- 45.7°, 60.3° and 61.5° which fitted well to the crystal planes of

IR) spectroscopy, X-ray diffraction (XRD) analysis, Brunauer, (003), (006), (012), (015), (018), (110) and (113) of the

3

Emmett and Teller (BET) surface area analysis, temperature hydrotalcite. The basal spacing d003 is 7.63 nm which is

8

programmed desorption (TPD), scanning electron microscopy typical for hydrotalcite-like materials containing carbonate

5

SEM), energy-dispersive X-ray spectroscopy (EDX), anions. This pattern clearly revealed that no impurity phases

4

(

transmission electron microscopy (TEM), thermogravimetric due to MgAl (OH) or Mg (CO (OH) .4H O were detected and

2

8

5

3

)

4

2

5

analysis (TGA), vibrating sample magnetometry (VSM), the material is pure. Moreover in Fig. 2b, in comparison with

4

inductively coupled plasma atomic emission spectroscopy (ICP- the pattern of the as-synthesized hydrotalcite, the additional

OES) and CHNS analysis.

peaks at 2Ɵ = 29.8°, 35.4°, 43,3°, 57.3°, and 62.9° were found

Preparation and successful surface functionalization of the which can be assigned to (220), (311), (400), (511) and (440)

magnetic hydrotalcite can be confirmed by FT-IR spectroscopy planes, confirming the presence of the magnetic (Fe O ) phase

3

4

7

(

Fig. 1). The FT-IR spectra of the HT (

Fe /HT-(CH Cl(III), Fe /HT-SMTU(IV

SMTU-Zn (

the broad band at 3447-3400 cm was indicative of the OH size of the Fe

symmetric stretching vibration of Mg-OH and Al-OH on the pattern of Fe

I

), Fe

3

O

4

/HT (II), as cubic lattice in the hydrotalcite structure (JCPDS:19-0629).

3

O

4

2

)

3

O

4

)

and Fe

3 4

O

/HT- It is worth mentioning that the intensities of diffraction peaks

II

V

) were illustrated in Fig.1(a-e). As shown in Fig.1a, are lower than that of hydrotalcite, probably due to the small

-1

49

NPs. Also, compared with Fig.2b, the

3

O

4

II

/HT-SMTU-Zn (

3

O

4

V

)

nanocatalyst (Fig. 2c)

surface of the hydrotalcite structure. Additional vibration exhibited several additional reflection peaks at 2Ɵ = 31.8°,

-

mode at 1634 cm could be attributed to the stretching 47.6°, 68.1° and 69.1°, corresponding to the (002), (102), (112)

1

vibrations of water molecules in hydrotalcite structure. and (201) planes of hexagonal phase of ZnO (JPCDS: 36-

5

II

Meanwhile, two adsorption bands appearing at 1366 and 670 1451). Owing to the same ionic radius of Zn and Mg ions,

-1

II

cm were corresponded to the asymmetric stretching entrance of Zn ions into the structure space of hydroxyl and

2

-

II

) and the consequently replacing the Mg ions led to formation of ZnO.

56

vibration of C-O (indicating the presence of CO

3

II

angular bending mode of carbonate species, respectively. This Thus, it can be concluded that Zn ions was immobilized on the

shows that the carbonate anions are present between layers surface of functionalized Fe O /HT (II) and doped into the HT

3

4

3

9, 48

of hydrotalcite.

In the FT-IR spectrum of Fe

b), compared to HT ( ), the intensity of the adsorption band at crystallite size of Fe

366 cm became weaker, indicating intercalate Fe O into 21 nm.

3

O

4

/HT (II) (Fig.

(I) matrix as well. According to the Deby-Scherer equation, the

II

1

I

3 4

O /HT-SMTU-Zn (V) was estimated to be

-1

3

4

9

HTs structure. Also, the presence of Fe

3 4

O NPs in hydrotalcite

structure can be identified by the broader band appearing

-1

around 789-565 cm (corresponded to the stretching vibration

of Fe-O bonds) which was covered by stretching vibrations of

4

7

Al-O and Mg-O bonds. In the FT-IR spectrum of Fe

CH ) Cl(III (Fig. 1c), grafting of

chloropropyl)trimethoxysilane on the surface of Fe

was authenticated by three new absorption bands at 2941,

3

O

4

/HT-

(

)

(3-

2

3

3 4

O /HT (II)

-1

2

884 (related to the C-H stretching vibrations ) and 1111 cm

5

related to the C-C stretching vibration). It is worth nothing

0

(

that the symmetric stretching vibration of Si-O bonds at

-1

around 680-670 cm was covered by M-O stretching vibrations

3 4

which cannot be distinguished. In FT-IR spectrum of Fe O /HT-

SMTU (IV), the existence of the grafted S-methylisothiourea

groups has been proved by the appearance of the N-H bending

6

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II

Scheme 2 The preparation of Zn doped and immobilized on functionalized magnetic hydrotalcite (Fe

II

/HT-SMTU-Zn ).

3

O

4

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The nitrogen adsorption-desorption isotherms and pore size

distribution curves of HT( ), Fe /HT(II) and Fe /HT-SMTU-

) were shown in Fig. 3 (a-c). As can be seen in Fig. 3 a and

I

3

O

4

3 4

O

II

Zn (

V

II

3

c, HT

(

I

)

and Fe

3

O

4

/HT-SMTU-Zn

(

V

)

showed the

characteristics of type II isotherm with H3-type hysteresis

using the Brunauer, Emmett, and Teller (BET) method. The

shape of these isotherms demonstrated the existence of

5

7

mesoporous or macroporous structure.

Although, the

3 4

isotherm of Fe O /HT (II) indicates H1-type hysteresis (Fig. 3

5

b), which suggested agglomerates of spherical particles. The

7

specific surface area, pore volume and mean pore diameter of

II

/HT-SMTU-Zn (

HT(

I

), Fe

3

O

4

/HT(II) and Fe

3

O

4

V

) were shown in

Table 1. The increased BET surface area and decreased pore

volume of Fe

into the HT (

3

O

4

/HT (II) confirmed the entrance of Fe

3

O

4

NPs

5

9

) pores. Likewise, the mean pore diameter of

I

II

Fe O /HT-SMTU-Zn (V) was also increased upon the reduction

3

4

6

0

of microporous contribution. Notably, functionalization of

2

Fe

3 4

O /HT(II) reduced the surface area from 59 m /g to 54 m /g

II

in Fe O /HT-SMTU-Zn

4

(V) nanocatalyst due to blocking or

3

Fig. 1 FT-IR spectra of (a) HT (

I

), (b) Fe O /HT (II), (c)

3

47s

4

occupation of some pores by anchored organic segments.

Furthermore, the pore size distribution curves (based on the

Barrett-Joyner-Halenda (BJH) method), showed that all three

samples have irregular pore size distribution.

Fe

3

O

4

/HT-(CH

/HT-SMTU-Zn (

).

2

)

3

Cl

(

III), (d) Fe

3

O

4

/HT-SMTU (IV), (e)

II

th

) and (f) 6 reused Fe O /HT-SMTU-

3

O

II

V

3 4

Zn (V

Table 1 Specific surface area (S_B_E_T), pore volume and mean pore

II

diameter of HT (I), Fe

3

O

4

/HT (II) and Fe

3

O

4

/HT-SMTU-Zn (V).

Sample

Total pore

volume

S

BET

Mean pore

diameter

(nm)

2

-1

(m g )

3

-1

(cm g )

HT(I)

0.80

0.20

0.40

57.69

59.88

54.34

38.53

1.29

12.17

Fe

3

O

4

/HT (II)

II

Fe O /HT-SMTU-Zn (V)

3

4

Fig. 2 The XRD patterns of (a) HT (

I

), (b) Fe

3 4

O /HT (II), (c)

II

Fe O /HT-SMTU-Zn (

th

V) and (d) 6 reused Fe O /HT-SMTU-

3

4

3 4

II

Zn (

V

).

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higher than 300 °C, is due to the presence of the strongest

2

basic sites (O anions). Also, it is worth mentioning that the

-

61

II

presence of Zn caused a clear decrease in the concentration

6

of basic sites (Fig.4d). The obtained results are presented in

1

Table 2.

Fig. 3 Nitrogen adsorption–desorption isotherms and pore size

distribution curves of (a) HT (I), (b) Fe O /HT (II) and (c)

3 4

II

3 4

Fe O /HT-SMTU-Zn (V).

Fig.4 NH

II

Zn (

3

-TPD profiles of (a) HT(

I

) and (b) Fe

3

O

4

/HT-SMTU-

/HT-

V

), and CO -TPD profiles of (c) HT(

2

I

) and (d) Fe O

3 4

Type and strength of the basic and acid sites were investigated

II

SMTU-Zn (

V

).

by Temperature programmed desorption of ammonia (NH

3

-

)

TPD) and carbon dioxide (CO -TPD) (Fig.4). The samples (HT (

2

I

II

and Fe

in vacuum. Ammonia and CO

As shown in Fig. 4a, the TPD-NH

NH desorption peaks at about 130-293 °C, and 300-380 °C

3

O

4

/HT-SMTU-Zn (

V

)) were activated at 850 °C for 1 h

were adsorbed at 50 °C for 1 h.

profile of HT( ) exhibited two

Table 2 Acidity and basicity calculated from the TPD profiles.

2

3

I

Sample

Total acidity

Total basicity

3

(mmol/g)

13.52

related to the moderate and strong acid sites, respectively.

The first ammonia desorption peak as a shoulder can be

HT(I)

13.43

assigned to the presence of Brønsted acid sites on the HT(I)

− 61

surface, generated by the occurrence of OH groups.

II

Fe

3

O

4

/HT-SMTU-Zn (V)

22.66

8.49

Furthermore, the second peak can be desorbed from the Lewis

3

acid sites attributed to the Al -O -Mg species present in the

+

2-

2+

II

The morphologies of HT (

I

), Fe

3

O

4

/HT-SMTU-Zn

th

(

V

) and the

3

structure of the mixed oxides and Al cations in octahedral

+

II

reused Fe

by SEM. The images were shown in Fig. 5. As given in Fig. 5a

and 5b, the as-synthesized HT ( ) shows irregular plate-like

morphology, representing the character of layered materials.

3 4

O /HT-SMTU-Zn (V) after 6 cycle were ascertained

6

1

sites. Compared to HT(

I

), increase in the total acidity of the

II

Fe O /HT-SMTU-Zn (V) nanocatalyst was caused by the

3

4

I

II

presence of Zn (Fig.4b). This phenomena is related to the

4

0

difference in the electronegativity of Mg and Zn results in

61

Interestingly, it was observed that Fe O NPs were dispersed

4

3

2

+

2-

2+

2-

more acidic Zn –O pairs than Mg –O pairs. Furthermore,

the TPD-CO profile of the HT( ) showed two distinguishable

on the surface of plate-like sheets of HT(I) (Fig. 5c).

2

I

desorption peaks (Fig.4c). The first desorption peak observed

at 190-250 °C is assigned to the formation of bidentate

2

carbonates on both Mg -O and Al -O pairs (moderate-

+

2-

3+ 2-

strength basic sites). An additional peak at a temperature

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a good agreement with the results deduced from the XRD (Fig.

).

8

II

), (c) Fe O /HT-SMTU-Zn (

Fig. 5 SEM image of (a, b) HT (

th

and (d) 6 reused Fe

I

V

)

3

4

II

Fig. 7 TEM image of (a, b) Fe O /HT-SMTU-Zn (

th

II

/HT-SMTU-Zn (

V

) and (c, d)6

3

4

3

O

4

V

).

II

reused Fe O /HT-SMTU-Zn (

V

).

3

4

Furthermore, the EDS analysis confirmed the presence of

Al, Mg, O, C, S, N, Si, Fe and Zn elements in nanocatalyst

structure as shown in Fig. 6. Likewise, the considerable

II

intensity of Zn , indicating the successful doping and

II

coordination of Zn on Fe O /HT-SMTU (IV). It is worth note

3

4

that no impurity elements was detected in the nanocatalyst

structure.

3 4

Fig. 8 Particle size distribution histogram of Fe O /HT-SMTU-

II

Zn (

V).

To investigate thermal stability of Fe

3

O

4

/HT(

3 4

I), Fe O /HT-

II

/HT-SMTU-Zn (

II

(CH ) Cl (III) and Fe O /HT-SMTU-Zn (IV), the TGA analysis

Fig. 6 The EDS analysis of Fe

3

O

4

V

).

2 3 3 4

were performed under the air atmosphere at the heating rate

of 10 °C/min from 25 to 950 °C (Fig. 9). The TGA of the

Also, the TEM analysis was carried out to obtain the direct

information about the structure and morphology of Fe /HT-

). As

) is plate-like in shape with the non-

NPs in its matrix. Furthermore,

3 4

Fe O /HT (II) (Fig. 9a) shows two major weight losses. The first

3 4

O

step (23-220°C, 11.82%) corresponds to the loss of physically

adsorbed water on the surface of nanoparticles or between

layers. The second step (220-600°C, 10.13%) due to the loss of

II

th

II

SMTU-Zn

shown in Fig. 7 (a-d), HT(

uniformly entrapped Fe

distribution histogram of Fe

the average diameter of nanoparticles is 20-60 nm, which is in

(V) and the 6 reused Fe O /HT-SMTU-Zn (V

3 4

I

3

O

4

62

the interlayer carbonate. Decarbonation was occurred at

II

3

4

O /HT-SMTU-Zn (V) revealed that

2

3 4

20°C instead of 440 °C which confirmed the presence of Fe O

62

3 4 2 3

NPs in HT(I) matrix. Similarly, Fe O /HT-(CH ) Cl (III) showed

1

0 | J. Name., 2012, 00, 1-3

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two major weight losses steps (Fig. 9b). It is clear that the first

decomposition step was corresponded to the physically

adsorbed water on the surface of Fe O /HT-(CH ) Cl (III) (23-

3

4

2 3

2

10 °C, 8%). Removal of organic segment was happened at

II

3 4

210-650 °C (24.13%). TGA thermogram of Fe O /HT-SMTU-Zn

(IV) was shown in Fig. 9c. Two weight loss steps were also

obvious. Evaporation of the absorbed physical and chemical

water on the catalyst surface was happened at 23-200 °C

(10.25 %). The main weight loss (37.01%) at 200-700 °C could

be assigned to the complete decomposition of the organic

segments grafted on the surface of catalyst.

According the results obtained from TGA thermogram (Fig.

3 4

9c), the amount of organic linkers anchored on Fe O /HT (II)

was estimated to be 1.23 mmol/g. These results were also in

good agreement with the obtained elemental analysis data (C

=

3.06 %, N = 1.20 % and S = 0.87%).

Magnetic characterization of Fe

II

3

O

4

/HT (II) and Fe

3

O

4

/HT-

SMTU-Zn

(V) was investigated using vibrating sample

magnetometer at room temperature (Fig. 10). As can be seen Fig. 10 Magnetization curves of (a) Fe O /HT (II) and (b)

3

4

II

in Fig. 10a, magnetization value of Fe

lower than the magnetization value of Fe

due to the placement of Fe O NPs into the hydrotalcite

3

O

4

/HT (II) (10.6 emu/g) is Fe

3 4

O /HT-SMTU-Zn (V).

3 4

O

NPs (73 emu/g)

3

4

7o

3.2. The synthesis of acridinedione derivatives in the

II

presence of Fe O /HT-SMTU-Zn (V)

matrix.

Fe /HT-SMTU-Zn (

emu/g) decreased which was ascribed to organic moiety

grafted on the surface of Fe /HT (II) (Fig. 10 b). It is worth

Besides, specific saturation magnetization of

II

3

4

3

O

4

3 4

V) compared to Fe O /HT (II) (6.15

In the initial stages of investigation, the reaction between

dimedone (2 mmol), benzaldehyde (1 mmol), and aniline (1

mmol) was performed in solvent-free conditions and in the

absence of any catalyst at 80 °C (Table 3, entry 1). It was found

that the desired product was not formed even after long

3 4

O

nothing that the magnetic hysteresis was absent for two

composites, indicating a superparamagnetic behavior which

3 4

can be attributed to the presence of Fe O NPs with very small

4

9

particle size. These magnetic properties were high enough

for magnetic separation of the nanocatalyst from the reaction

mixture with an external magnet.

period of time (180 min). The crucial role of Fe

3

O

4

/HT-SMTU-

was highlighted in the preparation of 3,3,6,6-

tetramethyl-9,10-diphenyl-3,4,6,7,9,10-hexahydroacridine-

,8(2H, 5H)-dione, when in a set of experiments, the model

reaction was performed in the presence of HT ( ), Fe

/HT-SMTU (IV) and

) nanoparticles (Table 3, entries 2-7).

II

Zn

(V)

1

I

3 4

O ,

Fe

3

O

4

/HT(II), Fe

3 4 2 3 3 4

O /HT(CH ) Cl(III), Fe O

II

4

/HT-SMTU-Zn

(V

II

3 4

As shown in Table 3, Fe O /HT-SMTU-Zn (V) is the most

efficient catalyst which causes the highest yield of desired

product in shorter reaction time on model reactions. In order

to determine the optimum conditions, the effect of

temperature and the catalyst loading on reaction rate as well

as on yield of corresponding product was also investigated. It

could be seen that a remarkable yield of desired product was

observed at 70 °C by using 4 mol% of catalyst (Table 3, entries

8

-13). Further to improve the product yield, the solvent effect

was investigated. For this purpose, water as well as some

organic solvents (EtOH, EtOH/H O, MeOH, DMF, EtOAc,

CH CN, toluene and 1,4-dioxane) were examined. After

2

3

careful investigations, it was observed that, under solvent

free conditions compared to the other used solvents, the

reaction proceeded more efficiently (Table 3, entries 14-22).

Recently, the demand for clean and efficient chemical

synthetic methods is becoming more urgent. Solvent-free

3 4 3 4

Fig. 9 The TGA thermograms of (a) Fe O /HT (II), (b) Fe O /HT-

II

2 3 3 4

(CH ) Cl (III) and (c) Fe O /HT-SMTU-Zn (IV).

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multicomponent reactions as one of the most usual solutions of aldehyde). Furthermore, the disappearance of two

-1

afford a clean, safe and easy manner to modernize classical absorption bands at 3330-3250 cm , related to the –NH

2

chemical procedures. It is often claimed that the best solvent is group of primary amine, also confirm the consumption of

6

no solvent. With this optimistic result in hand (Table 3 entry aniline and completion of the reaction. On the other hand, the

3

1

2), the model reaction was further performed in the presence appearance of the key absorption bands around 1645-1640

-1

2 2

of Zn(OAc) .2H O (4 mol%). In this context the reasonable yield cm (due to stretching vibration of conjugated carbonyl) and

-1

was obtained in long reaction time (Table 3, entry 23). To 1577-1573 cm (related to the stretching vibration of

II

1

ascertain the influence of doped Zn ions (as ZnO) in the conjugated C=C) proved the formation of acridinediones. In H-

preparation of acridinedione derivatives, the model reaction NMR spectra of the synthesized products, a sharp singlet

was also performed using ZnO (4 mol%) by applying optimized resonating at around 5.12-4.99 ppm established the presence

1

3

reaction conditions. After prolonged reaction time the of methine group on 9-position. Besides, in the C-NMR

expected product was obtained in low yield (Table 3, entry 24). spectra of all compounds, the appearance of peaks

II

The results revealed that the immobilized and doped Zn ions corresponding to the carbonyl carbon at a lower chemical shift

are both effective in reaction progress.

(195.53-195.51 ppm) than unconjugated C=O (220-200 ppm)

Encouraged by these results, we next examined the generality and two signals at 167.76-150.76 and 154.40-146.10 ppm

and efficiency of this approach for the synthesis of a wide (associate with C=C bond), are document for the ring-closing

variety of acridinedione derivatives by the reaction of a wide reaction which resulted in the synthesis of acridinediones.

range of substituted aldehydes, dimedone and different

+

substituted amines / or NH

4

ion. The results are summarized

in Table 4. It could be seen that aromatic aldehydes with

electron withdrawing groups participated in the condensation

reaction more quickly than the aromatic aldehydes bearing

electron donating groups (Table 4, entries 2 and 3 vs entries 4-

6). On the other hand, electron-rich amines afforded high

product yields rapidly in comparison with electron-poor

amines (Table 4, entries 8-11 vs entries 12-13). As shown in

+

4 4 4 2 3

Table 4, in comparison, using NH OAc, NH Cl and (NH ) CO

as nitrogen source in condensation reaction gave the desired

product more efficiently than aromatic amines. Although, the

reaction of the aromatic aldehydes bearing both electron

donating and electron withdrawing groups, dimedone and

+

NH

4 4 4 4 2 3

(used as NH OAc, NH Cl and (NH ) CO ), proceeded

with equal efficiency (Table 4, entries 15-26). The

condensation reaction was also examined with aliphatic

aldehydes and aliphatic amines, but no desired product was

formed even after long reaction time. Moreover applying

additional amounts of catalyst loading cannot promote the

reaction well.

Some of the obtained products (4a-d, 4h, 4j, 4i and 4o-r)

were known and characterized on the basis of comparing their

physical data (color and melting points), spectroscopic data as

well as analytical data with those of authentic samples

reported in the literature. Also, the structure of the selected

1

compounds were further recognized by FT-IR, HNMR and

1

3

CNMR spectroscopy. The novel synthesized compounds (4e

,

4f

,

4g, 4i, 4k, 4m and 4n) were also characterized by using

elemental analysis technique. The progress of the reaction was

monitored by the disappearance of starting materials and

formation of the product on TLC which confirmed the

completion of the reaction. In the FT-IR spectra, the complete

consumption of aldehyde is confirmed by the disappearance of

-1

the sharp absorption band at 1720 cm (related to the C=O

stretching vibration of aldehyde), and two absorption bands at

-

1

-1

720 cm and 2695 cm (due to the C-H stretching vibration

2

1

2 | J. Name., 2012, 00, 1-3

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Table 3 Optimization of various reaction parameters for the synthesis of 3,3,6,6-tetramethyl-9,10-diphenyl-

,4,6,7,9,10-hexahydroacridine-1,8 (2H, 5H)-dione .

3

Entry

Molar ratio of (benzaldehyde/

dimedone/ aniline)

1/2/1

Catalyst

(mol %)

-

Solvent

Temp.

( C )

Time

(min)

30/180

Isolated

Yield (%)

0

°

1

-

80

70

65

60

70

a

2

1/2/1

0.1(g)

30/180

30

15

30

95

90

80

95

90

80

50

70

60

40

20

30

10

5

b

3

0.1(g)

c

4

0.1(g)

d

5

0.1(g)

e

6

0.1(g)

7

5

8

9

30

5

30

1

0

1

2

3

4

5

6

7

8

9

0

1

2

5

30

1

2

7

30

4

30

3.5

4

30

H O

2

30

4

EtOH

30

4

H O (1:1)

/

MeOH

DMF

EtOH

30

2

4

30

4

30

4

EtOAc

30

4

CH CN

3

30

4

Toluene

30

4

1,4-Dioxane

30

f

2

3

4

-

150

90

g

2

4

20

a

b

c

The reaction was performed in the presence of HT (I). The reaction was performed in the presence of Fe

reaction was performed in the presence of Fe O /HT (II). The reaction was performed in the presence of Fe O /HT-

) Cl (III). The reaction was performed in the presence of Fe O /HT-SMTU (IV). The reaction was performed in the

2 3 3 4

presence of Zn(OAc) .2H O. The reaction was performed in the presence of ZnO.

3

O

4

.

The

d

3

4

3

4

e

f

(

CH

g

2

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II

3 4

Table 4 One-pot synthesis of 1,8-dioxo-decahydroacridines in the presence of Fe O /HT-SMTU-Zn (V) under

solvent free condition.

1

2

R

Entry

R

Product

Time (min)

Isolated Yield (%)

1

2

3

4

5

6

7

8

9

H

4-MeO

4-Me

4-Br

3-Br

4-CN

4-Pyridyl

H

C

6

H

5

4a

4b

4c

4d

4e

4f

20

50

15

40

15

25

40

60

10

5

95

90

95

90

95

85

90

92

95

90

75

30

95

90

95

90

95

90

94

92

90

87

90

88

4g

4h

4i

4-MeOC H

6

4

H

3,4-Di-MeC

6

4

H

3

1

2

0

1

2

3

4

5

6

7

8

9

0

1

2

3

4

5

6

H

4-MeC

3-MeC

6

H

4j

H

6

4k

4l

H

4-ClC

6 4

H

2-BrC H

6

4

4m

4n

4o

4p

4q

4r

H

2-Pyridyl

H

NH

4

OAc

4-MeO

4-Cl

4-Br

H

5

NH

4

Cl

4o

4p

4q

4r

15

20

10

15

20

10

4-MeO

4-Cl

4-Br

H

(NH

4

)

2

CO

3

4o

4p

4q

4r

4-MeO

4-Cl

4-Br

(NH ) CO

4

2

3

(NH

)

CO

1

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1

According to documents reported in literature recommended Since we are interested in developing more environmentally

6

mechanism pathway for the synthesis of acridinedione benign and economically viable synthetic methods, we tried to

II

derivatives catalyzed by Fe

3

O

4

/HT-SMTU-Zn (

V

)

as

a

recycle the catalyst and reuse it under the same reaction

/HT-SMTU-

) nanoparticles were separated by using an external

component cyclocondensation reaction was established by magnet and washed with H O, EtOAc several times, dried at 70

/HT-SMTU-Zn °C and reused in another set of reaction. It was observed that

). In this context, even after a long reaction time, no product the recycled magnetic nanocatalyst can be reused for six

was obtained (Table 3, entry 1). Initially, the acidic active sites consecutive trials in effective and satisfy yields in comparison

3 4

bifunctional catalyst is shown in Scheme 3. The essential condition. After completion of the reaction, Fe O

II

3 4

catalytic activity of Fe O /HT-SMTU-Zn (V) in this multi- Zn (V

2

II

3 4

performing the reaction in the absence of Fe O

(V

II

th

(

Zn ) increase the electrophilicity of carbonyl groups of with fresh catalyst (Fig. 11). In FT-IR spectrum of 6 reused

aldehydes as well as the enolization of dimedone (5,5- catalyst (Fig. 1f) presence of three absorption bands at 1576,

-1

dimethyl-1,3-cyclohexadione) which could be facilitated by 1408 and 620 cm (Fig. 1f) due to the stretching modes of

acidic/ or basic sites (see TPD analysis section) of catalyst. carboxylates groups and Zn-S bond evidently established the

Then the nucleophilic attack of

which was followed by water elimination afforded analysis showed that freshly prepared catalyst contains 32026

Knoevenagel product II Subsequently, the Knoevenagel ppm, 0.32 g or 4.89 mmol of Zn per 1 g of catalyst, while the

product II reacted in Michael fashion with another molecule of

I to activated form of aldehyde stability of the catalyst after six cycles. Furthermore, ICP-OES

.

th

6

reused catalyst contains 30984 ppm, 0.30 g or 4.58 mmol of

II

dimedone (5,5-dimethyl-1,3-cyclohexadione) and furnished Zn per 1g of catalyst. It indicates that 93% of Zn could be

the rapid formation of intermediate III. By lowering the found in the structure of the catalyst after six runs. Also, the

reaction rate (at room temperature) the Knoevenagel product obtained results from the XRD pattern (Fig. 2 d). SEM (Fig. 5c

th

II and intermediates III were isolated and identified by FT-IR and 5d) and TEM images (Fig. 7c and 7d) of the 6 recovered

spectroscopy, mass spectrometry and comparison of their catalyst clearly indicate there was no significant difference in

6

4

melting points with authenic samples.

chemical structure of catalyst before and after six runs.

FT-IR spectroscopy of Knoevenagel product II and intermediate

-1

III revealed the absorption bands at 2955-2853 cm and 2957-

-1

2

839 cm related to symmetric stretching vibration of

methylene group (CH ), respectively. The presence of carbonyl

groups (C=O) were also confirmed as the strong absorption

2

-

1

-1

bands at 1561 cm , 1508 cm , 1655 cm and 1596 cm .

The existence of a molecular ion peak at m/z 258 and 398 in

the mass spectra, also established the formation of

Knoevenagel product II and intermediates III, respectively (see

Supporting Information, pages 46–48). As under the reaction

conditions, dimedone could be condensed with amine,

possible formation of the corresponding product III' was

investigated in details. Based on our studies, we found that

dimedone is more reactive towards Knoevenagel product II

than amine. Since III' was not produced in the reaction mixture

even in trace amounts. Afterwards, the intermediate III was

attacked by amine molecule on the carbonyl (C=O) moiety by

II

/HT-SMTU-Zn (

the help of Fe

3

O

4

V

) and gave the intermediate

IV. Finally, intramolecular attack of nitrogen atom to activated

Fig. 11 Synthesis of 3,3,6,6-tetramethyl-9,10-diphenyl-3,4,6,7,9,10-

hexahydroacridine-1,8(2H,5H)-dione in the presence of reused

carbonyl group and consequent removal of one water

molecule affords

V as final product with high yield. Then the

II

Fe O /HT-SMTU-Zn (V).

3

4

re-generated catalyst re-enters the catalytic cycle.

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II

Scheme 3 Recommended mechanism pathway for the preparation of acridinedione derivatives catalyzed by Fe O /HT-SMTU-Zn (V).

3

4

1

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.3. Hot filtration test

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3

The heterogeneous nature of the nanocatalysts was

investigated by a hot filtration test on model reaction under

the optimized conditions. In this test, after continuing the

reaction for 10 minutes, the catalyst was magnetically

separated from the reaction mixture (60% conversion). Then,

the resulting filtrate was allowed to react for an additional

time (10 minutes) at 70 °C and monitored by TLC. It was

revealed that after separation of the catalyst no increase in the

final conversion was observed. This result clearly

II

demonstrated that Zn was doped and strongly coordinated in

II

Scheme 4 The chemical structure of Zn (EDTA) complex

.

the structure of Fe

3 4

O /HT-SMTU (IV), and no leaching of Zn

took place during the catalytic reaction.

3.4. Poisoning Test

Further to discern homogenetiy / heterogenetiy nature of the

catalyst, a poisoning test was carried out under the optimized

reaction conditions. Ethylenediamine tetraacetic acid (EDTA)

was used as an excellent scavenger because of its high affinity

II

to capture Zn ions that caused the formation of a stable

6

5

complex (VI) (Scheme 4). Toward this point, the model

reaction was performed in two separate flasks, in the absence

and in the presence of EDTA. The reaction progress was

monitored by GLC. Time-dependent correlation of the product

yield (Fig. 12) revealed that improvement of the reaction has

Fig. 12 Time-dependent correlation of the product yield of model

reaction in the presence (a) and in the absence (b) of EDTA

not

been

affected

in

the

presence

of

(

Ethylenediaminetetraacetic acid).

ethylenediaminetetraacetic acid (EDTA) considerably. It means

II

that no leaching of Zn took place during the course of the

4

. Conclusion

reaction into the reaction media which confirmed the truly

heterogeneous nature of the catalyst.

II

In summary we have successfully synthesized Zn doped and

In this line of work, to show the merit of the present

immobilized on functionalized magnetic hydrotalcite

II

/HT-SMTU-Zn ) from readily available starting materials.

protocol for synthesis of acridinedione derivatives, we have

II

/HT-SMTU-Zn (

(Fe

3

O

4

compared the result using Fe

3

O

4

V

) on model

II

Careful characterization of Fe

3

O

4

/HT-SMTU-Zn

(

V

)

by

reaction with those obtained using other catalysts that have

been recently published in the literature (Table 5). As shown in

Table 5, the use of high temperatures (Table 5, entries 1-5),

homogenous catalytic systems, tedious product purification

procedures (Table 5, entries 6-15), toxic solvents (Table 5,

entries 16 and 17) and long reaction times to obtain the

spectroscopic and microscopic techniques revealed that the

new nanocatalyst has plate-like shape with average particle

size 20-60 nm, superparamagnetic behavior and 4 mmol/g

II

loading of Zn . Besides, the nanocatalyst has both acidic and

basic properties, and thus act as a bifunctional nanocatalyst. It

was then applied as a magnetically recyclable heterogeneous

catalyst for the one-pot multicomponent synthesis of

acridinedione derivatives under solvent free condition. It

should be pointed out that high efficiency, generality,

simplicity, excellent yields of products, short reaction times,

mild reaction conditions, clean reaction profiles, eco-friendly,

easy separation of catalyst with the assistance of an external

magnetic field and reusability of the nanocatalyst up to 6

cycles without significant degradation in activity are promising

desired product (Table 5, entries 18-21) are disadvantages of

II

/HT-SMTU-Zn (

some of these methods. Therefore, Fe

3

O

4

V

) as

a heterogeneous and green catalyst is more efficient than

most of the catalysts with respect to the reaction time and

yield of the product. Moreover, the newly synthesized

nanocatalyst with great catalytic performance is found to be

easily recovered from reaction mixture using an external

magnet and reused. The results well suggested the superiority

of the current approach to the previously reported methods in

this regard.

points of the presented methodology which make it

a

desirable and useful approach for the preparation of

acridinedione derivatives as an important class of nitrogen

heterocyclic compounds. Notably, the catalyst is not air or

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moisture sensitive thus no extra care should be taken in

storing or handling it.

II

Table 5 Comparison between efficiency of Fe

3 4

O /HT-SMTU-Zn (V) and some other catalysts for the

a

synthesis of 3,3,6,6-tetramethyl-9,10-diphenyl-3,4,6,7,9,10-hexahydroacridine-1,8(2H, 5H)-dione.

Entry

Catalyst

Fe O

Solvent

Temp

°C )

Time

(min)

Yield

(%)

Ref

(

1

2

3

4

5

6

7

8

9

Solvent-free

120

100

120

110

100

130

80

25

6

85

96

92

98

96

91

90

98

79

87

90

79

98

90

94

92

93

87

85

90

95

29

30

31

27

26

16

17

66

18

5c

19

21

22

23

1

3

4

γ-Fe O

2

3

Fe O @SiO

H O

2

30

3

4

2

CdO

Solvent-free

8

MCM-SO H

10

3

Zn(OAc) .2H O

H O

2

2(h)

3(h)

30

2

CeCl .7H O

[bmim][BF₄]

Solvent-free

MeCN

3

2

b

DBH

Pyridinium Hydrogen Sulfate

H SO

2(h)

48

1

2

0

1

2

3

4

5

6

7

8

9

0

1

2

H O

2

r.t

2

4

p-Dodecylbenezenesulfonic Acid

H

O

100

r.t

6

2

B(C F )

5 3

Solvent-free

1.5(h)

24

6

Vitamin B₁

H O

2

100

50

c

CAN

PEG

EtOH

DMF

EtOH

4(h)

5(h)

50

L-Proline

Pt NPs@GO

GO

65

75

34

35

67

68

20

100

78

60

d

SBNPSA

2(h)

4(h)

5(h)

2.5(h)

30

e

BAIS

H O

2

100

80

f

[Hmim]TFA

Solvent-free

EtOH

SiO₂-I

80

36

II

Present

study

Fe O /HT-SMTU-Zn

Solvent-free

70

3

4

a

b

.

c

Molar ratio of benzaldehyde/ dimedone/ aniline (1/2/1). 1,3-Dibromo 5,5-dimethylhydantoin Ceric

ammonium nitrate. Silica-bonded N-propyl sulfamic acid. BrØnsted acidic imidazoluim salts. 1-

d

e

f

Methylimidazolium triflouroacetate.

Acknowledgements

The authors gratefully acknowledge the partial support of this

4

(a) S. A. Gamage, J. A. Spicer, G. J. Atwell, G. J. Finlay, B. C.

study by Ferdowsi University of Mashhad Research Council

Baguley and W.A. Denny, J. Med. Chem., 1999, 42, 2383; (b) M.

Filho, O. Pessoa, M.Z. Hernandes, M. Lima, S. L. Galdino and I.

Pitta, Med. Chem. Res., 2013, 22, 2421.

(Grant no. p/3/29781).

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0 | J. Name., 2012, 00, 1-3

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New Journal of Chemistry

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DOI: 10.1039/C7NJ03281A

Graphical Abstract

II

R¹

Zn

doped and immobilized on

functionalized magnetic hydrotalcite

O

II

(

Fe O /HT-SMTU-Zn ): a novel, green

3 4

N

CHO

NH₂

and magnetically recyclable bifunctional

nanocatalyst for one-pot multi-

no solvent

R²

R¹

R²

component synthesis of acridinediones

under solvent-free conditions

Or

+

-

(

NH ) X

4

R1

II

Fe O /HT-SMTU-Zn

3

4

O

Zeinab Zarei and Batool Akhlaghinia*

1

2

R , R = aryl

N

H

-

2-

X = AcO , Cl , CO

3

Zn^I^I

ZnO

Fe3O4

II

Herein, the catalytic activity of novel synthesized Fe O /HT-SMTU-Zn nanocatalyst, in green and efficient synthesis of

3

4

acridinediones is described.

Article Doi

ZnII doped and immobilized on functionalized magnetic hydrotalcite (Fe3O4/HT-SMTU-ZnII): A novel, green and magnetically recyclable bifunctional nanocatalyst for the one-pot multi-component synthesis of acridinediones under solvent-free conditions

DOI: 10.1039/c7nj03281a

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Authors:

Article abstract of DOI:10.1039/c7nj03281a

Full text of DOI:10.1039/c7nj03281a

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