A one-pot synthesis of 5,5-disubstituted hydantoin derivatives using magnetic Fe<sub>3</sub>O<sub>4</sub> nanoparticles as a reusable heterogeneous catalyst

Javad Safari; Leila Javadian

doi:10.1016/j.crci.2013.06.005

A one-pot synthesis of 5,5-disubstituted hydantoin derivatives using magnetic Fe₃O₄ nanoparticles as a reusable heterogeneous catalyst

Javad Safari ¹ ; Leila Javadian ¹

¹ Laboratory of Organic Compound Research, Department of Organic Chemistry, College of Chemistry, University of Kashan, PO Box: 87317, 51167 Kashan, Iran

Comptes Rendus. Chimie, Volume 16 (2013) no. 12, pp. 1165-1171.

Résumé

A facile and rapid method for the one-pot synthesis of 5,5-disubstituted hydantoins in the presence of magnetic Fe₃O₄ nanoparticles has been developed. The multicomponent reactions of carbonyl compounds (aldehydes and ketones), potassium cyanide and ammonium carbonate were carried out under solvent-free conditions to obtain various hydantoin derivatives. The magnetic catalyst could be readily separated by an external magnet from the reaction mixture. This procedure has many advantages, such as the use of a reusable magnetic catalyst, high yields, short reaction times, simplicity and very easiness with implementing the methodology.

Supplementary Materials:
Supplementary material for this article is supplied as a separate file:

mmc1.docx

Métadonnées

Reçu le : 2013-02-05
Accepté le : 2013-06-11
Publié le : 2013-08-13

DOI : 10.1016/j.crci.2013.06.005

Mots clés : Fe₃O₄ nanoparticles, Heterogeneous, Magnetic catalyst, Hydantoin, Solvent-free

Affiliations des auteurs :

Javad Safari ¹ ; Leila Javadian ¹

¹ Laboratory of Organic Compound Research, Department of Organic Chemistry, College of Chemistry, University of Kashan, PO Box: 87317, 51167 Kashan, Iran

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Javad Safari; Leila Javadian. A one-pot synthesis of 5,5-disubstituted hydantoin derivatives using magnetic Fe₃O₄ nanoparticles as a reusable heterogeneous catalyst. Comptes Rendus. Chimie, Volume 16 (2013) no. 12, pp. 1165-1171. doi : 10.1016/j.crci.2013.06.005. https://comptes-rendus.academie-sciences.fr/chimie/articles/10.1016/j.crci.2013.06.005/

Version originale du texte intégral

1 Introduction

Hydantoins, 2,4-imidazolidine-diones, are a familiar five-membered heterocycles including a useful reactive urea moiety [1,2]. Various hydantoin-containing natural and synthetic products show different biological activities, such as anti-ulcer [3], anti-tumor [4], antiviral [5], antimicrobial [6], anti-diabetic [7], anti-arrhythmic [8], anticonvulsant [9] properties; they can also be used for agrochemical (herbicidal and fungicidal) applications [10]. Several methods are used for the preparation of hydantoins [11–15]. 5,5-Disubstituted hydantoins are often made by Bucherer–Bergs synthesis and Reed syntheses [16,17]. However, some of the reported methods suffer from drawbacks, such as poor yields, long reaction times, expensive substrates, difficult reaction conditions, complexity of work-up and co-occurrence of several side reactions, as well as environmental concern. Therefore, the development of simple, high-yielding and eco-friendly methods using new catalysts for the preparation of hydantoin derivatives would be highly desirable.

Recently, iron oxide magnetic nanoparticles (Fe₃O₄ MNPs) have gained increasing interest in many areas, due to their properties, including super paramagnetic activities, high surface area, low toxicity, and simple separation by an external magnetic field [18–20]. Magnetic particles are used in different fields, such as medicinal applications, drug delivery, and industry [21]. Additionally, Fe₃O₄ nanoparticles (nano-Fe₃O₄) have emerged as a valuable group of heterogeneous catalysts due to their application in nanocatalysis. Fe₃O₄ nanoparticles are economic nanocatalysts and are environmentally benign. Moreover, they can be easily separated and recycled from the products by an external magnet [22]. During the past decades, magnetic nanocatalysts were used in several organic reactions, including the synthesis of α-aminonitriles [23], the coupling of phenols with aryl halides [24], the Suzuki reaction [25], the synthesis of propargylic amines [26], the synthesis of sulfonamides [27], the synthesis of quinoxalines [28], the Sonogashira–Hagihara coupling reaction [29], the aza–Michael addition, and the Paal–Knorr reaction [30].

In this study, high activation and regeneration of Fe₃O₄ nanoparticles as heterogeneous catalyst in the synthesis of hydantoins are shown. The use of MNPs not only gives high yields in short reaction times, but it is also a cheap and facile method.

Herein, we wish to report a simple and one-pot procedure for the synthesis of 5,5-disubstituted hydantoins using magnetic Fe₃O₄ nanoparticle as a magnetic catalyst (Scheme 1).

Scheme 1
Synthesis of hydantoin derivatives by using magnetic Fe₃O₄ nanoparticles under solvent-free conditions.

2 Results and discussion

In this work, we prepared hydantoin derivatives using the Bucherer–Bergs reaction in the presence of Fe₃O₄ nanoparticles as a solid catalyst under solvent-free conditions. Firstly, Fe₃O₄ nanoparticles were prepared by chemical co-precipitation with a size range of 18 nm. Fig. 1 shows the XRD patterns of the Fe₃O₄ nanoparticles.

The XRD patterns of the particles show six characteristic peaks reveal a cubic iron oxide phrase (2h = 30.35, 35.95, 43.45, 53.70, 57.25, 62.88, 71.37, 74.46). These are related to their corresponding indices (220), (311), (400), (331), (422), (333), (440) and (531), respectively. It implies that the resultant nanoparticles are pure Fe₃O₄ with a spinel structure. The crystal size of MNPs can be determined from the XRD pattern by using the Debye–Scherrer equation:

D (h k l) = \frac{0.94 λ}{β \cos θ}

D(hkl) is the average crystalline diameter, 0.94 is the Scherrer constant, λ is the X-ray wavelength, β is the half-width of XRD diffraction lines and θ is the Bragg angle, in degree. The (311) peak of the maximum intensity was picked out to estimate the nanoparticles’ diameter. The XRD patterns of maghemite and magnetite are very close. Thus, the lattice parameter must be precisely determined. Magnetite is an inverse spinel with a lattice parameter of 8.3941 Å. Cations are arranged with one Fe³⁺ per filled tetrahedral hole, and the remaining Fe³⁺ and Fe²⁺ are distributed in the octahedral holes.

The lattice parameter of the synthesized magnetite is 8.3850 Å, which is consistent with the expected lattice parameter for magnetic Fe₃O₄ particles. This value is closer to that of stoichiometric magnetite (8.3941 Å) than to that of maghemite (8.346 Å) [31,32].

A SEM image is shown in Fig. 2a. The SEM image shows that magnetite nanoparticles have a mean diameter of about 18 nm and a nearly spherical shape, which is consistent with XRD results. The SEM image shows the shape and size of the nanoparticles. Also, transmission electron microscopy (TEM) analyses were used for characterization. The TEM image discloses the spherical Fe₃O₄ particles with an average size of about 18 nm (Fig. 2b).

Fig. 2
SEM (a) and TEM (b) images of MNPs.

Fig. 3 shows the Fourier transform infrared (FT–IR) spectra of MNPs. The absorbance band at 580 cm⁻¹ is ascribed to the Fe–O stretching vibration, which is consistent with the reported IR spectra for spinel Fe₃O₄ [33]. The difference between the spectra of maghemite and magnetite is related to the absence of Fe²⁺ cations, and the presence of vacancies within the OH sites. It should be noted that the IR spectrum of Fe₂O₃ (maghemite) reported in the literature is more complicated than that of Fe₃O₄ (magnetite) [34–36].

In continuation of our research to optimize the reaction conditions, the synthesis of 5-phenylhydantoin as a model reaction was chosen for the synthesis of 5,5-disubstituted hydantoins. We examined the model reaction in the presence of an optimized molar ratio of nanocatalyst (1 mol%), aldehyde or ketone (1 mmol), potassium cyanide (1.3 mmol), and ammonium carbonate (6 mmol) in different solvents, such as ethanol, methanol, DMSO, CH₃CN, ethanol:H₂O (ratio of 1:1) and solvent-free conditions at 70 °C. As shown in Table 1, solvent-free conditions are the best ones for the synthesis of hydantoins.

Entry	Solvent	Time (min)	Yield (%)^b
1	Ethanol	20	80
2	Methanol	20	70
3	Methanol:H₂O	17	80
4	DMSO	20	50
5	CH₃CN	20	48
6	Ethanol:H₂O	17	90
7	Solvent-free	15	93

^a Catalyst amount (1 mol%) under solvent-free conditions.

^b Isolated yield of the pure compound.

After this, the reaction was carried out both in the presence and in the absence of the Fe₃O₄ nanocatalyst. We evaluated the model reaction in the presence of 0.1, 0.5, 1.0, 2.0 and 5.0 mol% of MNPs to find out the effect of the amount of catalyst. As indicated in Table 2, the maximum yield (95%) was obtained when 1 mol% of nanocatalyst was used. Increasing this amount of nano-Fe₃O₄ did not cause any increase of the yield.

Entry	Catalyst (mol%)	Time (min)	Yield (%)^a
1	0.0	30	20
2	0.1	20	75
3	0.5	15	91
4	1.0	15	95
5	3.0	15	95
6	5.0	15	95

^a Under solvent-free condition at 70 °C.

Also, in order to further improve the conditions of the reaction, we investigated the model reaction in solvent-free conditions and with 1 mol% of MNPs at room temperature, 40, 50, 70, 90, and 110 °C to find out the effect of the temperature on the progress of the reaction. It was observed that the higher reaction temperature gave the higher yield. As shown in Table 3, the optimum temperature for the reaction was 70 °C.

Entry	Temperature (°C)	Yield (%)	Time (min)
1	RT	27	30
2	40	80	20
3	50	87	15
4	70	95	15
5	90	95	15
6	110	95	15

Therefore, we selected magnetic Fe₃O₄ nanoparticles as an efficient catalyst for the synthesis of hydantoin derivatives at 70 °C under solvent-free conditions.

Next, we performed the synthesis of diverse 5,5-disubstituted hydantoins with different substituted carbonyl compounds (aldehyde or ketone) under optimized reaction conditions in excellent yields (Table 4). The carbonyl compounds containing electron-withdrawing groups on the aromatic ring were found to be likely more reactive and could react with ammonium carbonate rapidly. In contrast, the ketones (or aldehydes) containing electron-donating groups on the aromatic ring have shown lower reactivity.

Entry	R¹	R²	Product^b	Time (min)/Yield (%)^c	Mp_rep/Mp_lit (°C)
1	H	C₆H₅	4a	17/95	(164–165)/(163) [37]
2	H	4-CH₃C₆H₅	4b	19/88	(183–184)/(182.5) [38]
3	H	4-OCH₃C₆H₅	4c	23/95	(193–197)/–
4	H	2-OCH₃C₆H₅	4d	31/88	(183–185)/(186–187) [38]
5	H	2-ClC₆H₅	4e	20/95	(178–179)/(176) [38]
6	H	n-Bu	4f	14/97	(142–143)/(139.5) [38]
7	H	i-Bu	4g	17/95	(214–217)/(212.5–216) [38]
8	CH₃	i-Bu	4h	25/98	(148–150)/(148) [38]
9		4i	25/99	(219–221)/(220) [37]
10	CH₃	C₆H₅	4j	30/88	(197–199)/(195–196) [39]
11	CH₃	4-ClC₆H₄	4k	30/95	(261–262)/(262–263) [40]
12	CH₃	3-CH₃C₆H₄	4l	33/97	(180–182)/(175–180) [39]
13	CH₃	3-ClC₆H₄	4m	27/96	(180–183)/(180–182) [39]
14	C₆H₅	C₆H₅	4n	54/85	(295–296)/(297–298) [41]
15		4o	60/81	(323–326)/(324–325) [38]

^a Aldehyde or ketone (1 mmol), KCN (1.3 mmol), (NH₄)₂CO₃ (6 mmol), Fe₃O₄ MNPs (1 mol%)

^b All the products were characterized by IR, ¹H NMR and ¹³C NMR spectra.

^c Isolated yields.

At the end of the reaction, the magnetic Fe₃O₄ nanoparticles were washed with diethylether and dried at 130 °C for 4 h. Also, the reusability of the MNPs was surveyed. We found that after reusing the MNPs four times, no change was observed in their catalytic activity.

Moreover, a plausible mechanism for the formation of hydantoin derivatives is shown in Scheme 2. Fe₃O₄ nanoparticles as a Lewis acid can activate the carbonyl group of the ketone (or the aldehyde) (1) to increase the electrophilic character of the carbonyl groups and decrease the energy of the transition state [33]. This was followed by the attack of ammonia on the activated carbonyl group, resulting in the formation of imine. The α-aminonitrile compound is prepared via the nucleophilic attack of imine by the cyanide ion in the presence of nano-Fe₃O₄ as a nanocatalyst. From the condensation of α-aminonitrile with carbon dioxide, hydantoin (4) was produced. In fact, Fe₃O₄ nanoparticles are required for the formation of both the imine and the α-aminonitrile [42]. Also, a Lewis acid, such as Fe₃O₄ nanoparticles may assist in the formation of the hydantoin from aminonitrile by the treatment with carbon dioxide [43].

Scheme 2
Possible mechanism for the preparation of hydantoin derivatives.

3 Conclusions

In conclusion, we reported an efficient approach for the preparation of 5,5-disubstituted hydantoin derivatives via the one-pot three-component condensation of aldehyde (or ketone), KCN and (NH₄)₂CO₃ in the presence of magnetic Fe₃O₄ nanoparticles as a safe and inexpensive magnetic catalyst under solvent-free conditions. The separation of the MNPs was very effective, simple and economical. The heterogeneous magnetic catalyst could be reused several times without significant loss of the catalytic performance of MNPs. It is of interest to note that this procedure will find important applications in the synthesis of hydantoin derivatives.

4 Experimental method

4.1 Materials and techniques

Chemical reagents in high purity were purchased from the Merck Chemical Company. All the materials were of commercial reagent grade. Melting points were determined in open capillaries using an Electrothermal Mk3 apparatus and are uncorrected. ¹H NMR and ¹³C NMR spectra were recorded with a Bruker DRX-400 spectrometer at 400 and 100 MHz, respectively. NMR spectra were obtained in DMSO-d₆ solutions and are reported as parts per million (ppm) downfield from tetramethylsilane as the internal standard. The abbreviations used are: singlet (s), doublet (d), triplet (t) and multiplet (m). FT–IR spectra were obtained with potassium bromide pellets in the range 400–4000 cm⁻¹ with a PerkinElmer 550 spectrometer. The elemental analyses (C, H, N) were obtained with both Carlo Erba Model EA 1108 and PerkinElmer 240c analyzers. The UV–vis measurements were obtained with a GBC cintra 6 UV–vis spectrophotometer. The melting points were obtained with a micro melting point apparatus (Electrothermal, MK3) and are uncorrected. Nanostructures were characterized using a Holland Philips Xpert X-ray powder diffraction (XRD) diffractometer (Cu Kα, radiation, λ = 0.154056 nm), at a scanning speed of 2°/min from 10 to 100° (2h). Scanning electron microscope (SEM) micrographs were taken with a FEI Quanta 200 SEM operating at a 20-kV accelerating voltage. The samples for SEM were prepared by spreading a small drop containing the nanoparticles onto a silicon wafer and then drying them almost completely in the air at room temperature for 2 h, and finally transferring them onto SEM conductive tapes. Transmission electron microscopy (TEM) studies of the nanostructures were carried out with a JEOL JEM 3010 instrument operating at an accelerating voltage of 300 kV. Sonication was performed in a Shanghai Branson-BUG40-06 ultrasonic cleaner (with a frequency of 40 kHz and a nominal power of 200 W).

4.2 Preparation of the Fe₃O₄ nanoparticles

Fe₃O₄ nanoparticles were prepared using chemical co-precipitation as described in the literature [44]. Briefly, 5.83 g of FeCl₃.6H₂O (0.02 mol) and 2.14 g of FeCl₂.4H₂O (0.01 mol) were dissolved in 100 mL of deionized water at 85 °C under N₂ atmosphere. Then, 10 mL of 25% NH₄OH were injected into the mixture. The black magnetic nanoparticles were formed in the last step. Afterwards, the reaction mixture was cooled. The catalyst was isolated using the magnetic field and washed three times with distilled water and a solution of NaCl. The obtained nanocatalyst size was estimated around 18 nm by TEM.

4.3 General procedure for the synthesis of 5,5-disubstituted hydantoins (4a–m) by Fe₃O₄ nanoparticles

In a 50-mL round-bottomed flask were poured aldehyde or ketone (1 mmol), potassium cyanide (1.3 mmol), ammonium carbonate (6 mmol), and magnetic Fe₃O₄ nanoparticles (1 mol%) sequentially. The suspension was stirred at 70 °C in solvent-free conditions. The progress of the reaction was monitored by TLC (petroleum ether:ethyl acetate, 1:1.2 v/v). Upon completion, the mixture was cooled to room temperature and neutralized with diluted hydrochloric acid. Then, the magnetic catalyst was removed by an external magnet and reused. The obtained product was purified by crystallization from water–ethanol. The structure of the products was characterized by comparison of their physical and spectra data with those previously reported.

4.4 Spectral data of products

4.4.1 5-Phenyl imidazolidine-2,4-dione (C₉H₈N₂O₂, 4a)

White powder crystals; UV (CH₃OH) λ_max: 284 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.79 (s, 1H, N₃–H), 8.41(s, 1H, N₁–H), 7.31 (t, J = 6.8 Hz, 1H), 7.35 (d, J = 6.89 Hz, 2H), 7.40 (t, J = 6.89 Hz, 2H) and 5.16 (s, 1H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 173.77 (C₄ = O), 157.67 (C₂O), 136.49 (C), 129.09 (2CH), 128.77 (2CH), 127.11 (CH), 62.26 (C_spiro); IR (KBr cm⁻¹) $\bar{ν}$ : 3500 (N–H, s), 3300 (N–H, s), 3150 (C–H), 3024 (C–H), 1745 (C = O), 1720 (CO), 1450 (CC) and 1420 (N–H, b). Anal. calcd. for C₉H₈N₂O₂ (176.141): C 61.37, H 4.57, N 15.90, O 18.16; found: C 61.39, H 4.60, N 15.88, O 18.14.

4.4.2 5-(4-Methyl phenyl)-imidazolidine-2,4-dione (C₁₀H₁₀N₂O₂, 4b)

White crystal; UV (CH₃OH) λ_max: 276 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.74 (s, 1H, N₃–H), 8.35 (s, 1H, N₁–H), 7.19 (s, 4H), 5.09 (s, 1H) and 2.29 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 174.82 (CO), 157.97 (CO), 138.01 (C), 133.57 (2CH), 129.64 (2CH), 127.08 (C), 61.46 (C–H), 21.15 (C–H); IR (KBr cm⁻¹) $\bar{ν}$ : 3524 (N–H, s), 3426 (N–H, s), 3050 (C–H), 2970 (C–H), 1777 (CO), 1755 (CO), 1500 (CC) and 1448 (N–H, b). Anal. calcd. for C₁₀H₁₀N₂O₂ (190.167): C 63.16, H 5.29, N 14.73, O 16.82; found: C 63.17, H 5.32, N 14.71, O 16.85.

4.4.3 5-(4-Methoxyphenyl)-imidazolidine-2,4-dione (C₁₀H₁₀N₂O₃, 4c)

White needles; UV (CH₃OH) λ_max: 280 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 9.3 (s, 1H, N₃–H), 8.34 (s, 1H, N₁–H), 7.21 (d, J = 7.7 Hz, 2H), 6.94 (d, J = 7.7 Hz, 2H), 5.08 (s, 1H) and 3.74 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.71 (CO), 160.04 (CO), 158.37 (C), 127.12 (2CH), 120.03 (2CH), 113.63 (C), 61.04 (C_spiro), 55.20 (C–H); IR (KBr cm⁻¹) $\bar{ν}$ : 3350 (N–H, m), 3215 (N–H, s), 1779 (CO, s), 1732 (CO, s), 1610 (CC, w), 1515 (CC, w) and 1246 (C-O, m). Anal. calcd. for C₁₀H₁₀N₂O₃ (206.166): C 58.25, H 4.88, N 13.58, O 23.28; found: C 58.27, H 4.84, N 13.61, O 23.27.

4.4.4 5-(2-Methoxyphenyl)-imidazolidine-2,4-dione (C₁₀H₁₀N₂O₃, 4d)

White needles; UV (CH₃OH) λ_max: 274 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 9.40 (s, 1H, N₃–H), 7.99 (s, 1H, N₁–H), 7.30 (d, J = 7.00 Hz, 1H), 7.08–6.92 (m, 2H), 6.85 (d, J = 7.00 Hz, 1H), 4.85 (s, 1H) and 4.01 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.01 (CO), 161.12 (CO), 157.62 (C), 128.13 (2CH), 119.11 (2CH), 114.02 (C), 62.01 (C_spiro), 54.17 (C–H); IR (KBr cm⁻¹) $\bar{ν}$ : 3348 (N–H, m), 3217 (N–H, s), 1780 (CO, s), 1729 (CO, s), 1612 (CC, w), 1518 (CC, w) and 1250 (C–O, m). Anal. calcd. for C₁₀H₁₀N₂O₃ (206.166): C 58.25, H 4.88, N 13.58, O 23.28; found: C 58.22, H 4.90, N 13.65, O 23.30.

4.4.5 5-(2-Chlorophenyl)-imidazolidine-2,4-dione (C₉H₇N₂O₂Cl, 4e)

White needles; UV (CH₃OH) λ_max: 275 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 9.70 (s, 1H, N₃–H), 8.03 (s, 1H, N₁–H), 7.90 (d, J = 6.98 Hz, 1H), 7.71 (t, J = 6.98 Hz, 1H), 7.35–7.36 (m, 2H) and 5.13 (s, 1H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 168.71 (CO), 151.04 (CO), 158.37 (C), 127.12 (2CH), 120.03 (2CH), 113.63 (C), 61.04 (C_spiro); IR (KBr cm⁻¹) $\bar{ν}$ : 3350 (N–H, m), 3215 (N–H, s), 1779 (CO, s), 1732 (CO, s), 1613 (CC, w) and 1514 (CC, w). Anal. calcd. for C₉H₇N₂O₂ Cl (210.450): C 51.33, H 3.33, N 13.30, O 15.22; Cl 16.82; found: C 51.29, H 3.35, N 13.35, O 15.24.

4.4.6 5-n-Butyl-imidazolidine-2,4-dione (C₇H₁₂N₂O₂, 4f)

White needles; UV (CH₃OH) λ_max: 319 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.52(s, 1H, N₃–H), 7.89(s, 1H, N₁–H), 1.49–1.52 (t, J = 5 Hz, 2H), 1.55–1.57 (m, 2H), 0.91–0.93 (m, J = 5 Hz, 2H) and 0.81–0.79 (t, J = 5 Hz, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.51 (CO), 158.50 (CO), 67.21 (C), 46.73 (C–H), 23.87 (C–H), 22.23 (C–H), 20.85 (C–H).; IR (KBr cm⁻¹) $\bar{ν}$ : 3201 (N–H, s), 3189 (N–H, s), 2899 (C–H), 2875 (C–H), 1775 (CO), 1730 (CO) and 1437 (N–H, b). Anal. calcd. for C₇H₁₂N₂O₂ (156.090): C 53.85, H 7.68, N 17.95, O 20.52; found: C 53.87, H 7.69, N 17.93, O 20.51.

4.4.7 5-Isobutyl-imidazolidine-2,4-dione (C₇H₁₂N₂O₂, 4g)

White needles; UV (CH₃OH) λ_max: 321 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.43 (s, 1H, N₃–H), 7.74 (s, 1H, N₁–H), 1.49–1.53 (m, 2H), 1.43–1.49 (m, 1H), 0.88–0.89 (d, J = 5 Hz, 3H) and 0.81–0.79 (d, J = 5 Hz, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.51 (CO), 158.53 (CO), 67.20 (C), 46.72 (C–H), 23.92 (C–H), 22.19 (C–H), 20.97 (C–H).; IR (KBr cm⁻¹) $\bar{ν}$ : 3204 (N–H, s), 3212 (N–H, s), 2975 (C–H), 2978 (C–H), 1774 (CO), 1722 (CO) and 1411 (N–H, b). Anal. calcd. for C₇H₁₂N₂O₂ (156.090): C 53.85, H 7.68, N 17.95, O 20.52; found: C 53.86, H 7.69, N 17.94, O 20.51.

4.4.8 5-Isobutyl-5-methyl-imidazolidine-2,4-dione (C₈H₁₄N₂O₂, 4h)

White needles; UV (CH₃OH) λ_max: 312 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.52(s, 1H, N₃–H), 7.89(s, 1H, N₁–H), 1.57–1.51 (m, 2H), 1.46–1.42 (m, 1H), 1.20 (s, 3H), 0.87–0.86 (d, J = 5 Hz, 3H) and 0.79–0.77 (d, J = 5 Hz, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.46 (CO), 158.47 (CO), 67.16 (C_spiro), 46.67 (C–H), 23.99 (C–H), 22.17 (C–H), 20.92 (C–H).; IR (KBr cm⁻¹) $\bar{ν}$ : 3197 (N–H, s), 3117 (N–H, s), 2981 (C–H), 2971 (C–H), 1771 (CO), 1720 (CO) and 1403 (N–H, b). Anal. calcd. for C₈H₁₄N₂O₂ (170.177): C 56.46, H 8.28, N 16.46, O 18.80; found: C 56.47, H 8.27, N 16.48, O 18.82.

4.4.9 1,3-Diazaspiro[4,5]decane-2,4-dione (C₈H₁₂N₂O₂, 4i)

White needles; UV (CH₃OH) λ_max: 348 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.47 (s, 1H, N₃–H), 8.38 (s, 1H, N₁–H), 1.62–1.45 (m, 9H) and 1.21–1.27 (m, 1H).; ¹³C NMR (DMSO-d₆, 100 MHz) δ: 179.61 (CO), 157.51 (CO), 62.89 (C_spiro), 39.76 (2CH₂), 25.33 (2CH₂), 21.71 (CH₂).; IR (KBr cm⁻¹) $\bar{ν}$ : 3250 (N–H), 3199 (N–H, s), 3069 (C–H, s), 2936 (C–H, s), 1776 (CO, m), 1734 (CO, s), 1456 (N–H, b, s), 1411 (s), 1292 (m), 1228 (m), 1072 (m), 942 (m), 780 (m) and 753 (m). Anal. calcd. for C₈H₁₂N₂O₂ (168.106): C 57.15, H 7.18, N 16.66, O 19.03; found: C 57.17, H 7.19, N 16.64, O 19.01.

4.4.10 5-Methyl-5-phenyl-imidazolidine-2,4-dione (C₁₀H₁₀N₂O₂, 4j)

White needles; UV (CH₃OH) λ_max: 252 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.75(s, 1H, N₃–H), 8.62 (s, 1H, N₁–H), 7.47–7.45 (d, J = 6 Hz, 2H), 7.40–7.36 (t, J = 6 Hz, 2H), 7.32–7.31 (t, J = 6 Hz, 1H) and 1.64 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.16 (CO), 157.41 (CO), 127.41 (C), 127.38 (2CH), 126.79 (2CH), 123.70 (2CH), 71.22 (C_spiro), 22.14 (C–H); IR (KBr cm⁻¹) $\bar{ν}$ : 3282 (N–H,s), 3208 (N–H, s), 3064 (C–H,m), 2989 (C–H, m), 1731 (CO, s), 1726 (CO, s) and 787 (C–H, b). Anal. calcd. for C₁₀H₁₀N₂O₂ (190.167): C 63.16, H 5.29, N 14.73, O 16.82; found: C 63.17, H 5.27, N 14.74, O 16.80.

4.4.11 5-Methyl-5-(4-chloro phenyl)-imidazolidine-2,4-dione (C₁₀H₉ClN₂O₂, 4k)

White needles; UV (CH₃OH) λ_max: 272 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.6 (s, 1H, N₃–H), 8.64 (s, 1H, N₁–H), 7.49 (d, J = 8.3, 2H), 7.47 (d, J = 8.3, 2H) and 1.63 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 177.14 (CO), 156.69 (CO), 139.39 (C), 133.16 (C), 128.89 (2CH), 127.77 (2CH), 64.06 (C_spiro), 25.51 (CH₃); IR (KBr cm⁻¹) $\bar{ν}$ : 3274 (N–H, s), 3209(N–H, s), 1778 (CO, m), 1725 (CO, s), 1489 (CC, w), 1447 (CC, w), and 1401 (N–H, b, m). Anal. calcd. for C₁₀H₉ClN₂O₂ (224.624): C 53.47, H 4.03, N 12.47, O 14.24, Cl 15.78; found: C 53.46, H 4.04, N 12.49, O 14.27, Cl 15.80.

4.4.12 5-Methyl-5-(3-methyl phenyl)-imidazolidine-2,4-dione (C₁₁H₁₂N₂O₂, 4l)

White powder; UV (CH₃OH) λ_max: 268 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 10.73 (s, 1H, N₃–H), 8.56 (s, 1H, N₁–H), 7.42–7.25 (s, 3H), 7.12 (s, 1H), 2.30 (s, 3H) and 1.87–1.61 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 166.16 (CO), 157.41 (CO), 137.99 (C), 131.30 (CH), 128.16 (CH), 127.31 (CH), 126.73 (CH), 123.32 (C), 72.43 (C_spiro), 22.14 (CH₃), 20.84 (CH₃); IR (KBr cm⁻¹) $\bar{ν}$ : 3290 (N–H, s), 3211 (N–H, s), 3050 (C–H, m), 2972 (C–H, m), 1798 (CO, m), 1730 (CO, s), 1018 (m), and 762 (C–H, b). Anal. calcd. for C₁₁H₁₂N₂O₂ (204.194): C 64.70, H 5.91, N 13.71, O 15.67; found: C 64.72, H 5.94, N 13.69, O 15.65.

4.4.13 5-(3-Chlorophenyl)-5-methyl imidazolidine-2,4-dione (C₁₀H₉N₂O₂Cl, 4m)

White crystal; UV (CH₃OH) λ_max: 270 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 9.86 (s, 1H, N₃–H), 7.99 (s, 1H, N₁–H), 7.54–7.47 (m, 2H), 7.18 (d, J = 6.5, 1H), 7.01 (t, J = 6.5, 1H) and 2.09 (s, 3H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 176.4 (CO), 158.2 (CO), 156.3 (C), 139.0 (CH), 132.8 (CH), 128.5 (CH), 127.4 (CH), 126.2 (C), 63.7 (C_spiro), 25.1 (CH₃); IR (KBr cm⁻¹) $\bar{ν}$ : 3285 (N–H, s), 3214(N–H, s), 3042 (C–H, m), 2800 (C–H, m), 1763 (CO, m) and 1716 (CO, s). Anal. calcd. for C₁₀H₉N₂O₂Cl (224.624): C 53.47, H 4.03, N 12.47, O 14.24, Cl 15.78; found: C 53.44, H 4.02, N 12.51, O 14.29, Cl 15.82.

4.4.14 5,5-diphenylhydantoin (C₁₅H₁₂N₂O₂, 4n)

White needles; UV (CH₃OH) λ_max: 276 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 11.1 (s, 1H, N₃–H), 9.33 (s, 1H, N₁–H) and 7.36 (m, 10H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 175.26 (CO), 156.43 (CO), 140.39 (2C), 128.96 (2CH), 128.48 (4CH), 127.04 (4CH), 70.66 (C_spiro); IR (KBr cm⁻¹) $\bar{ν}$ : 3270 (N–H, s), 3200 (N–H, s), 1770 (CO, m), 1730 (CO, s), 1710 (C₄O_asym, s), 1400 (N–H, b), 760 (C–H, b) and 740 (C–H). Anal. calcd. for C₁₅H₁₂N₂O₂ (252.249): C 71.42, H 4.79, N 11.10, O 12.68; found: C 71.45, H 4.80, N 11.12, O 12.66.

4.4.15 Spiro[fluorene-9,4-imidazolidine]-2,4-dione (C₁₅H₁₀N₂O₂, 4o)

Yellow powder; UV (CH₃OH) λ_max: 250 nm; ¹H NMR (DMSO-d₆, 400 MHz) δ: 11.1 (s, 1H, N₃–H), 9.33 (s, 1H, N₁–H), 7.89–7.85 (t, J = 6.7 Hz, 2H), 7.50–7.45 (m, 4H) and 7.37–7.34 (t, J = 6.7, 2H); ¹³C NMR (DMSO-d₆, 100 MHz) δ: 175.26 (C₄O), 156.43 (C₂O), 140.39 (2C), 128.96 (2C), 128.48 (4CH), 127.04 (4CH), 70.66 (C_spiro), IR (KBr cm⁻¹) $\bar{ν}$ : 3270 (N–H, s), 3200 (N–H, s), 1770 (CO, m), 1730 (C₄O, s), 1400 (N–H, b, w), 760 (C–H, b) and 740 (C–H, w). Anal. calcd. for C₁₅H₁₀N₂O₂ (250.245): C 71.42, H 4.79, N 11.10, O 12.68; found: C 71.40, H 4.82, N 11.11, O 12.70.

Acknowledgements

We gratefully acknowledge the financial support from the Research Council of the University of Kashan for supporting this work by Grant No. 256722/XI.

Bibliographie

[1] J. Charton; A.C. Gassiot; P. Melnyk; S. Girault-Mizzi; C. Sergheraert Tetrahedron Lett., 45 (2004), p. 7081

[2] D. Azarifar; M.A. Zolfigol; B. Maleki Bull. Korean Chem. Soc., 25 (2004), p. 23

[3] D. Zhang; D. Ye; E. Feng; J. Wang; J. Shi; H. Jiang; H. Liu J. Org. Chem., 75 (2010), p. 3552

[4] C.S. Basappa; S. Ananda Kumar; K. Nanjunda Swamy; K.S. Sugahara; Rangappa Bioorg. Med. Chem., 17 (2009), p. 4928

[5] P.T. Todorov; E.D. Naydenova C. R. Chimie, 13 (2010), p. 1424

[6] A. Mandal; R.S.G. Krishnan; S. Thennarasu; S. Panigrahi; A.B. Mandal Colloids Surf. B: Biointerfaces, 79 (2010), p. 136

[7] A. Volonterio; A.C. Ramirez de; M. Zanda J. Org. Chem., 70 (2005), p. 2161

[8] Y. Brouillette; V. Lisowski; J. Guillon; S. Massip; J. Martinez Tetrahedron, 63 (2007), p. 7538

[9] A. Alizadeh; E. Sheikhi Tetrahedron Lett., 48 (2007), p. 4887

[10] Y.D. Gong; H.Y. Sohn; M.J. Kurth J. Org. Chem., 63 (1998), p. 4854

[11] S.K. Ahmed; J.G. Etoga; S.A. Patel; R.J. Bridges Bioorg. Med. Chem. Lett., 21 (2011), p. 4358

[12] J. Safari; N.M. Arani; I.A. Ramezan Chin. J. Chem., 28 (2010), p. 255

[13] A.N. Moshtael; J. Safari Ultrason. Sonochem., 18 (2011), p. 640

[14] Kh. Faghihi; M. Hagibeygi Eur. Polym. J., 39 (2003), p. 2307

[15] S.M. Dumbries; D.J. Diaz; L. McElwee-White J. Org. Chem., 74 (2009), p. 8862

[16] W.T. Read J. Am. Chem. Soc., 44 (1992), p. 1746

[17] E. Gallienne; G.G. Muccioli; D.M. Lambert; M. Shipmam Tetrahedron Lett., 49 (2008), p. 6495

[18] B. Karami; S.J. Hoseini; S. Nikoseresht; S. Khodabakhshi Chin. Chem. Lett., 23 (2012), p. 173

[19] B. Karami; S.J. Hosseini; K. Eskandari; A. Ghasemi; H. Nasrabadi Catal. Sci. Technol., 2 (2012), p. 331

[20] P. Riente; C. Mendoza; M.A. Pericas J. Mater. Chem., 21 (2011), p. 7350

[21] J. Perez; M. Nat; A.-H. Lu; E.L. Salabas; F. Schuth; J. Gao; W. Zhang; P. Huang; B. Zhang; X. Zhang; B. Xu J. Am. Chem. Soc., 2 (2007), p. 535

[22] M.Z. Kassaee; H. Masrouri; F. Movahedi Appl. Catal. A: Gen., 395 (2011), p. 28

[23] M.M. Mojtahedi; M. Abaee; T. Alishiri Tetrahedron Lett., 50 (2009), p. 2322

[24] R. Zhang; J. Liu; S. Wang; J. Niu; C. Xia; W. Sun Chem. Catal. Chem., 3 (2011), p. 146

[25] A. Taher; J.-B. Kim; J.-Y. Jung; W.-S. Ahn; M.-J. Jin Synlett (2009), p. 2477

[26] T. Zeng; W. Chen; C.M. Cirtiu; A. Moores; G. Song; C. Li Green Chem., 12 (2010), p. 570

[27] F. Shi; M.K. Tse; S. Zhou; M.-M. Pohl; J. Radnik; S. Hü bner; K. Jähnisch; A. Brü ckner; M. Beller J. Am. Chem. Soc., 131 (2009), p. 1775

[28] H.Y. Lü; S.H. Yang; J. Deng; Z.H. Zhang Aust. J. Chem., 63 (2010), p. 1290

[29] H. Firouzabadi; N. Iranpoor; M. Gholinejad; J. Hoseinib Adv. Synth. Catal., 353 (2011), p. 125

[30] V. Polshettiwar; R.S. Varma Tetrahedron, 66 (2010), p. 1091

[31] T.J. Daou; J.M. Grene’che; G. Pourroy; S. Buathong; A. Derory; C. Ulhaq-Bouillet; B. Donnio; D. Guillon; S. Begin-Colin Chem. Mater., 20 (2008), p. 5869

[32] M.E. Fleet Acta Cryst., B37 (1981), p. 917

[33] B. Karami; Kh. Eskandari; A. Ghasemi Turk. J. Chem., 36 (2012), p. 601

[34] T.J. Daou; J.M. Grene‘che; G. Pourroy; S. Buathong; A. Derory; C. Ulhaq-Bouillet; D. Donnio; S. Guillon; Begin-Colin Chem. Mater., 20 (2008), p. 5869

[35] M.A. Verg’ es1; R. Costo; A.G. Roca; J.F. Marco; G.F. Goya; C.J. Serna; M.P. Morales J. Phys. D: Appl. Phys., 41 (2008), p. 1

[36] M.A. Ghasemzadeh; J. Safaei-Ghomi; H. Molaei C. R. Chimie, 15 (2012), p. 969

[37] N.O. Mahmoodi; Z. Khodaee Arkivoc (2007), p. 29

[38] H.R. Henze; R.J. Speer J. Am. Chem. Soc., 64 (1942), p. 522

[39] N.D. Divjak; N.R. Banjac; N.V. Valentic; G.S. Uscumlic J. Serb. Chem. Soc., 74 (2009), p. 1195

[40] J. Li; L. Li; T. Li; H. Li; J. Liu Ultrason. Sonochem., 3 (1996), p. 141

[41] Kh. Faghihi; Kh. Zamani; Sh. Mallakpour Polym. Iran J., 11 (2002), p. 339

[42] M.M. Mojtahedi; M.S. Abaee; T. Alishiri Tetrahedron Lett., 50 (2009), p. 2322

[43] R.G. Murray; D.M. Whitehead; F.L. Strat; S.J. Conway Org. Biomol. Chem., 6 (2008), p. 988

[44] R. Massart IEEE Trans. Magn., 17 (1981), p. 1247

Commentaires - Politique

1 Introduction

2 Results and discussion

3 Conclusions

4 Experimental method

4.1 Materials and techniques

4.2 Preparation of the Fe3O4 nanoparticles

4.3 General procedure for the synthesis of 5,5-disubstituted hydantoins (4a–m) by Fe3O4 nanoparticles

4.4 Spectral data of products

4.4.1 5-Phenyl imidazolidine-2,4-dione (C9H8N2O2, 4a)

4.4.2 5-(4-Methyl phenyl)-imidazolidine-2,4-dione (C10H10N2O2, 4b)

4.4.3 5-(4-Methoxyphenyl)-imidazolidine-2,4-dione (C10H10N2O3, 4c)

4.4.4 5-(2-Methoxyphenyl)-imidazolidine-2,4-dione (C10H10N2O3, 4d)

4.4.5 5-(2-Chlorophenyl)-imidazolidine-2,4-dione (C9H7N2O2Cl, 4e)

4.4.6 5-n-Butyl-imidazolidine-2,4-dione (C7H12N2O2, 4f)

4.4.7 5-Isobutyl-imidazolidine-2,4-dione (C7H12N2O2, 4g)

4.4.8 5-Isobutyl-5-methyl-imidazolidine-2,4-dione (C8H14N2O2, 4h)

4.4.9 1,3-Diazaspiro[4,5]decane-2,4-dione (C8H12N2O2, 4i)

4.4.10 5-Methyl-5-phenyl-imidazolidine-2,4-dione (C10H10N2O2, 4j)

4.4.11 5-Methyl-5-(4-chloro phenyl)-imidazolidine-2,4-dione (C10H9ClN2O2, 4k)

4.4.12 5-Methyl-5-(3-methyl phenyl)-imidazolidine-2,4-dione (C11H12N2O2, 4l)

4.4.13 5-(3-Chlorophenyl)-5-methyl imidazolidine-2,4-dione (C10H9N2O2Cl, 4m)

4.4.14 5,5-diphenylhydantoin (C15H12N2O2, 4n)

4.4.15 Spiro[fluorene-9,4-imidazolidine]-2,4-dione (C15H10N2O2, 4o)