Applied Catalysis A: General 451 (2013) 7178

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Applied Catalysis A: General

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Sulfated zirconia; an efcient and reusable acid catalyst for the selective synthesis of 4-phenyl-1,3-dioxane by Prins cyclization of styrene
Vijaykumar S. Marakatti, Ganapati V. Shanbhag , A.B. Halgeri
Materials Science Division, Poornaprajna Institute of Scientic Research (PPISR), Bidalur Post, Devanahalli, Bangalore-562110, Karnataka State, India

a r t i c l e

i n f o

a b s t r a c t
Prins cyclization of styrene with paraformaldehyde was carried out over sulfated zirconia (SZ) catalyst in liquid phase. The SZ catalysts were synthesized by precipitation method with different sulfur impregnation and characterized by XRD, FT-IR, Nitrogen sorption, NH3 -TPD. The SZ showed best performance among different types of acid catalysts. The acidity of SZ optimized by different concentrations of H2 SO4 treatment inuences the selectivity for dioxane. The sulfur loading, nature of solvent, temperature, catalyst amount, mole ratio and reusability of catalyst were investigated. The SZ catalyst synthesized by impregnating 2N sulfuric acid was found to be highly selective for the synthesis of 4-phenyl-1,3dioxane (93%) with almost complete conversion of styrene (100%). The catalyst was recycled thrice with negligible decrease in the yield of 4-phenyl-1,3-dioxane. 2012 Elsevier B.V. All rights reserved.

Article history: Received 21 July 2012 Received in revised form 12 October 2012 Accepted 10 November 2012 Available online xxx Keywords: Prins cyclization Sulfated zirconia Styrene Paraformaldehyde 1,3-Dioxane

1. Introduction The Prins reaction is an important carboncarbon bond forming reaction in organic synthesis. It is an acid catalyzed condensation of olen with aldehyde leading to the formation of synthetic organic chemicals like 1,3-dioxanes, 1,3-diols and unsaturated alcohols [1]. Classically, Prins investigated the reaction of styrene with formaldehyde in water/glacial acetic acid media using mineral acid (H2 SO4 ) as catalyst to give 4-phenyl-1,3-dioxane [2]. Subsequently, homogeneous catalysts like Wells-Dawson type heteropoly acids [3] and triuoromethanesulfonic acid [4] were examined, but these catalysts suffer from drawbacks such as environmental pollution, equipment corrosion, tedious work up and difcult recyclability. In order to overcome the following problems, heterogeneous solid acid catalysts have been designed and developed for the Prins cyclization reaction. Many heterogeneous solid acid catalysts have been reported for the Prins cyclization reaction of styrene which include MoO3 /SiO2 [5], sulfonic group functionalized SBA15[6], zeolites [7], organic heteropolysalts [8] and InBr3 catalyst in dialkylimidazolian -based ionic liquids [1]. The chemicals derived from Prins cyclization nd their wide applications in organic processes such as solvents, protecting groups and intermediates for the synthesis of target molecules in pharmaceuticals [58]. Especially,

Corresponding author. Tel.: +91 27408552; fax: +91 23611836. E-mail addresses: shanbhag@poornaprajna.org, gvshanbhag@yahoo.co.in (G.V. Shanbhag). 0926-860X/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apcata.2012.11.016

4-phenyl-1,3-dioxane obtained from Prins cyclization of styrene is applied in industry as high boiling solvent, plasticizer, curing agent and pigment dispersant. Furthermore, it is employed in the production of plastic polymers as a monomer and additive [9]. Over the past two decades, application of anion modied metal oxides for organic transformations have been received much attention. Among them, sulfated zirconia catalyst attracted much attention due to its high activity in alkane isomerization at low temperatures [10]. Its high thermal stability, resistance to thermal extrusion, easy preparation methods and less cost offer several advantages over other acid catalysts. The zirconia has been commonly studied for its utilization as support however, strong active sites can also be generated on zirconia by modications such as H2 SO4 treatment. These active sites produce super acidity in sulfated zirconia, due to which it is further exploited in bulk petrochemical processes like alkylation, acylation, isomerization and cracking [11]. The continuous development of this catalyst generated interest in the synthesis of ne and specialty chemicals like nopol, coumarins, organic esters, N, N-diphenylenediamines etc. [12,13]. The reaction of -pinene with formaldehyde to give an alcohol (nopol) has been reported on sulfated zirconia catalyst [13]. However, to the best of knowledge, sulfated zirconia catalyst has not been studied so far for Prins cyclization reaction of olen with aldehyde to produce 1,3-dioxane derivatives. In this study, sulfated zirconia catalyst was compared to other solid acid catalysts for its activity and selectivity. The effect of sulfation, nature of different solvents and general applicability of catalyst for Prins cyclization

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were also studied. Physicochemical properties of the catalyst were correlated with the activity and product selectivity. 2. Materials and methods

at 200 C for 1 h in ow of helium gas. Then samples were saturated with anhydrous ammonia gas at 50 C for 30 min and nally ushed with He gas at 50 C for 1 h to remove physisorbed ammonia. 2.4. Catalytic activity studies

2.1. Materials Zirconium oxychloride, paraformaldehyde (hereafter PF), cesium carbonate and silicotungstic acids were obtained from the Loba Chemie, India. Ammonia and styrene were purchased from S.D Fine Chem, India. Ammonium paratungstate and amberlyst-15 were obtained by Alfa Aesar, USA. The montmorillonite K-10 clay was purchased from SigmaAldrich, USA. The zeolites HZSM-5 (35), H-Y (16), H-Mordenite (16) and H- Beta (25) (SiO2 /Al2 O3 is in parenthesis) were kindly donated by Sd-Chemie India Pvt Ltd. All the chemicals were used directly without further purication. 2.2. Catalyst preparation Sulfated zirconia (hereafter SZ) catalyst was prepared by the precipitation method using ZrOCl2 8H2 O and liquid ammonia solutions as reported in the literature method [13,14]. In a typical procedure, 25 g of zirconium oxychloride (ZrOCl2 8H2 O) was dissolved in 200 ml of deionized water. To this solution, aqueous ammonia was added dropwise with continuous stirring till the pH value of 8 was reached. The precipitating solution was ltered and washed thoroughly with deionized water several times to remove the chloride present in the precipitate (absence of chloride was determined by AgNO3 test). Thus obtained Zr(OH)4 precipitate was dried in an oven at 120 C for 12 h. The dried Zr (OH)4 clumps were ground with mortar and pestle to get a ne powder. The dried Zr(OH)4 was sulfated by suspending 1 g the Zr(OH)4 powder into 10 ml of H2 SO4 solution of desired concentration (1N, 1.5N, 2N and 3N). After stirring for 60 min, the catalyst was ltered, washed with water, dried and nally calcined at 650 C for 4 h. The catalysts obtained are indicated by symbol SZ-XN, where X stands for the concentration of sulfuric acid treated. Other solid acid catalysts WO3 /ZrO2 and cesium salt of silicotungstic acid acid were synthesized by literature methods [15,16] and used for the Prins reaction. 2.3. Catalyst characterization The phase purity and crystalline properties of all sulfated zirconia catalysts were determined by the X-ray diffractometer instrument (Bruker D-2 Phaser) with Cu K Source ( -1.542 A). The samples were analyzed in the 2 range of 1070 with scanning rate of 0.02 degrees per second. To investigate the nature of acid sites and bonding of sulfate ions on the surface of zirconia support, FT-IR (alpha-T, Bruker) spectra were obtained in the range of 14001700 cm1 and 9001400 cm1 respectively. The samples for acidity measurement were prepared in the pellet form by mixing KBr and catalyst in 10:1 ratio. Pellets were saturated with small amount of pyridine followed by degassing at 150 C for 1 h. The FTIR spectra in transmittance mode after pyridine treatment were subtracted with that of untreated catalyst to obtain the peaks only due to pyridineacid interaction. Nitrogen sorption measurements were carried out at 77 K in a Nova 1000 Quantachrome instrument. Prior to analysis the samples were heated to 150 C for 1 h. Specic surface areas of SZ catalysts were determined by BrunauerEmmettTeller (BET) equation. Average pore diameter and total pore volume were measured by BJH method. The temperature programmed desorption of ammonia were performed in the temperature range of 50600 C with ramp rate of 10 C/min. Before the TPD measurements, samples were pretreated Prins cyclization of styrene with PF was carried out in a liquid phase batch reactor. In a typical experiment, required amounts of styrene (20 mmol) and paraformaldehyde (60 mmol) were taken in a 100 ml round bottom ask containing solvent (10 ml) and appropriate amount of catalyst (7 wt% of total reactant). The round bottom ask tted with the condenser was heated over oil bath with continuous stirring. The required temperature of the oil bath was controlled and monitored by the PID temperature controller and thermometer, respectively. During the course of reaction, samples were withdrawn at certain intervals of time, centrifuged and the liquid was analyzed by gas chromatograph (Shimadzu-2041, FID detector) equipped with RTX-5 column (0.25 mm I.D and 30 m length). The oven temperature programme was 80 C (5 min), 80240 C (15 C/min), 240 C (5 min). All the products were identied by the GCMS analysis. The conversion and selectivity were directly calculated from GC peak areas in wt%. The yield was calculated by the GC analysis using the formula, Product yield (wt%) = [Conversion (wt%) Selectivity (wt%)]/100. 3. Results and discussion 3.1. Characterization of catalysts The XRD patterns of zirconia and SZ catalysts calcined at 650 C are as shown in Fig. 1. The unpromoted zirconia showed peaks at 2 = 24, 28.2, 31.5 and 30.2, 34.5, 35.4, 50.2, 60.2, 62.9 due to the presence of monoclinic and tetragonal phases respectively. But SZ exhibited predominant peaks only due to the tetragonal phase. The sulfation of hydrous zirconia with sulfuric acid shows a strong inuence on the phase modication from thermodynamically more stable monoclinic phase to tetragonal phase, which is in accordance with the literature [11,12]. The N2 adsorptiondesorption isotherm of all the SZ catalysts showed the type-IV isotherm with H2 type hysteresis loop conrming the presence of mesopores (Fig. 2) [13]. The surface area of zirconia increased considerably after sulfation due to the change in its physical properties. The specic surface area of SZ catalyst

Fig. 1. XRD patterns of promoted and unpromoted zirconia catalysts. TTetragonal phase, MMonoclinic phase.

V.S. Marakatti et al. / Applied Catalysis A: General 451 (2013) 7178 Table 1 Structural and textural properties of sulfated zirconia catalysts. Catalyst ZrO2 SZ-1N SZ-1.5N SZ-2N SZ-3N Sulfur content (wt%) 0.92 1.12 1.48 1.70 Surface area (m2 /g) 23 53.76 54.73 57.72 46.40 Average pore diameter (A) 33.93 34.72 35.82 36 36.12

73

Total pore volume (cm3 /g) 0.02 0.046 0.05 0.052 0.042

Fig. 2. Nitrogen adsorptiondesorption isotherms and pore size distribution of SZ2N catalyst.

increased with increase in H2 SO4 concentration up to 2N and surface area decreased thereafter. The decrease in surface area after 2N could be due to the change in crystal structure and sulfate migration into bulk phase of zirconia. The average pore diameter increased with increase in sulfur loading whereas pore volume increased with increase in surface area of the catalyst. Similar observations are reported by other researchers also [17,18]. FT-IR analysis of SZ, revealed the presence of sulfate ions and bonding of sulfate ions with zirconia support as shown in Fig. 3. The FT-IR analysis in the nger print region showed the presence of 995 cm1 peak due to the symmetric ( 1) vibrations of S O whereas 1041, 1141 and 1236 cm1 peaks were observed due to the asymmetric ( 3) vibrations of O S O bonds [19]. The peaks clearly indicate that the impregnation of sulfate ions on the surface of zirconia was in bidentate fashion. Increase in the intensity of peaks due to sulfate ions indicates the increase in the

incorporation of sulfur (from 1 to 2N H2 SO4 ), which is further conrmed by elemental analysis (Table 1). The less intensity of SZ-3N peak compared with that of other SZ catalysts indicates the less sulfur content on the surface which could be due to the migration of sulfur into bulk phase of zirconia. The adsorption of pyridine base on the surface of solid acid catalyst is one of the characterization techniques to measure surface acidity. The use of IR spectroscopy to detect adsorbed pyridine allows one to distinguish the Brnsted and Lewis acidity present on the surface of the catalyst. The interaction of pyridine nitrogen with acidic sites gives rise to two different frequency of bending vibration. The bending vibrations around 1445 cm1 and 1540 cm1 are assigned as Lewis and Brnsted acid sites, respectively and a peak at 1495 cm1 is due to both Brnsted and Lewis acidity. The intensity of Brnsted (B) and Lewis (L) acid sites obtained from the absorbance at 1540 and 1443 cm1 respectively and corresponding B/L ratios were measured. FTIR pyridine adsorption spectra of zirconia and SZ catalysts calcined at 650 C are as shown in Fig. 4. Zirconia exhibited only one peak at 1443 cm1 due to the presence of weak Lewis acid sites. The SZ showed peak at 1540 cm1 and 1443 cm1 indicating the presence of both Brnsted and Lewis acidity. It is well-known that, sulfate groups inductively withdraw the electron density from zirconia support and as a result, Lewis acid sites are created on zirconia whereas the Brnsted acid sites are due to protons generated by sulfate groups. The B/L ratio of the sulfated zirconia catalyst increased with increase of sulfur content as shown in Table 2. This could be due to the covering of Lewis acid sites with sulfate groups on the zirconia surface. The B/L ratios of other screened solid acid catalysts were also determined from pyridine FT-IR analysis (Fig. 5) and compared with SZ as shown in Table 4. Cesium salt of silicotungstic acid showed high Brnsted acidity (B/L = 3.9) whereas other catalysts like amberlyst-15, zeolites, Montmorillonite K-10 and tungstated zirconia gave B/L ratio in between 2.5 and 1.8. The SZ-2N showed the lowest B/L ratio (1.4) indicating the presence of higher Lewis acidic sites among different catalysts tested.

Fig. 3. FT-IR spectra of sulfated zirconia catalysts.

Fig. 4. Acidity measurement of SZ catalysts by pyridine FT-IR analysis.

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Table 2 Acidity measurement by NH3 -TPD and Py-FTIR analysis. Catalyst NH3 -TPD Total acidity (mmol NH3 /g) SZ-1N SZ1.5N SZ-2N SZ-3N 3.5 1.7 1.4 0.8 Py-FT-IR Brnsted acidity (IB ) 0.0332 0.0197 0.0256 0.0280 Lewis acidity (IL ) 0.0478 0.0171 0.0183 0.0184 B/L (IB /IL ) 0.69 1.15 1.4 1.52

decreasing total acidity (increasing B/L ratio). These excess sulfate groups on the surface of zirconia in the form of isolated and poly sulfates do not contribute to acidity [22]. 3.2. Catalytic activity study Prins cyclization of styrene to dioxane is a two step reaction in which rst step is the formation of intermediate carbocation (I) formed by the reaction of styrene with one formaldehyde molecule. In the second step, the intermediate carbocation (I) reacts with another formaldehyde molecule to form cyclic 4-phenyl-1,3dioxane (hereafter dioxane) or it can undergo deprotonation to yield cinnamyl alcohol as a side product as shown in Scheme 1. 3.2.1. SZ catalyst with different sulfur loading The Prins cyclization of styrene with PF was investigated for SZ catalyst with different sulfur loading and compared with its precursor. The Zr(OH)4 and ZrO2 showed almost no activity due to the absence of acid sites. The sulfation of zirconia with 1N, 1.5N and 2N sulfuric acid resulted in different amounts of sulfur loading on zirconia as shown in Table 1. The presence of sulfate ions on zirconia has enormous effect on the activity and selectivity of the reaction. Increase in sulfur content on ZrO2 increased the selectivity for dioxane but decreased styrene conversion as shown in Table 3. The conversion of styrene mainly depends upon the total number of acid sites. The decrease in conversion of styrene was due to the decrease in the total acidity from SZ-1N to SZ-3N as conrmed by TPD of ammonia. The complete conversion was obtained with SZ-1N to SZ-2N catalysts after 7 h reaction but the conversion was lower for SZ-3N (72%) due to lower acidity. The selectivity for dioxane mainly depends upon the ratio of Brnsted and Lewis acidity (B/L), and sulfur content. The increase in the selectivity for dioxane from SZ-1N to SZ-3N is due to the increase in B/L ratio and sulfur content. The SZ-3N with highest B/L ratio (1.5) gave a maximum selectivity of 95% whereas SZ-1N with lowest B/L ratio of 0.69 gave only 75.8% selectivity. It indicates that the presence of both Brnsted and Lewis acidity in appropriate amounts is essential for the selective synthesis of dioxane. Similar type of synergistic effect of Lewis and Brnsted acidity in Prins cyclization was reported elsewhere [23]. The SZ-2N catalyst with
Table 3 Catalytic activity over modied zirconia catalysts. Catalyst Conversion (wt%) 3h Blank Zr(OH)4 ZrO2 SZ-1N SZ-1.5N SZ-2N SZ-3N SZ-2Na 87.8 76.3 73 59 7h 1.8 1.6 2.5 100 100 99.8 72 Selectivity (wt%) 3h 74.6 78 88 95 7h 72 70 74 75.8 80.2 92.3 95

Fig. 5. Acidity measurement of all the screened solid acid catalyst by Pyridine-FTIR analysis.

To determine the amount and strength of acid sites, a temperature programmed desorption prole of all the SZ samples were measured (Fig. 6). The initial broad desorption peak in the temperature range of 50250 C was due to the coordination of ammonia with weak Lewis acid sites. Two medium peaks in the range of 250450 C were attributed to the medium strong acid sites and the desorption peaks at higher temperatures was due to the presence of strong Brnsted acid sites, which imparts SZ a super acidic property [20]. The presence of weak, medium and strong acid sites indicates the uneven distribution of acid sites in SZ catalysts. The amount of total acid sites decreased from 3.5 to 0.8 mmol of NH3 /g from SZ-1N to SZ-3N. At low sulfur content (1N H2 SO4 ) the sulfation takes place on the O Zr O sites where Brnsted and Lewis acidity are generated by sulfate andZr- sites respectively resulting in high acidity [21]. As the concentration of H2 SO4 increases, more number of sulfate groups masks the Lewis acidic sites and thereby

Fig. 6. Temperature programmed desorption prole of sulfated zirconia catalyst with different sulfur loading.

Reaction conditions: catalyst amount = 7 wt%, styrene = 20 mmol, PF = 60 mmol, temperature = 80 C. a Aqueous formaldehyde instead of PF under reux.

dichloroethane = 10 ml,

V.S. Marakatti et al. / Applied Catalysis A: General 451 (2013) 7178

75

Scheme 1. Plausible mechanistic pathway of Prins cyclization of styrene with paraformaldehyde.

B/L ratio 1.4 and 1.4 mmol/g acid sites showed high conversion and selectivity. The increase of sulfur content decreased the total acidity indicating the presence of certain isolated and poly sulfate groups on the surface of zirconia which are not contributing to acidity [22]. These anionic sulfate groups possibly stabilize the intermediate carbocation (I) resulting in the formation of dioxane rather than cinnamyl alcohol as shown in Scheme 1. Similar type of relation was established in the stabilization of acylation carbocation by sulfate anion for acylation of naphthalene [24]. Hence dioxane selectivity increased with increase in sulfur content for SZ catalysts. An effort was also made to use aqueous formaldehyde instead of PF but reaction did not occur even under reux conditions due to the formation of binary waterorganic phase as reaction media and incompatibility of water as solvent. 3.2.2. Catalyst screening Prins cyclization of styrene with PF was carried out over different types of solid acid catalysts namely, zeolites (H-ZSM-5, H-Y, H-beta), clay (K-10 montmorillonite), ion exchange resin (amberlyst-15), tungstated zirconia, cesium salt of silicotungstic acid and their activities were compared with the SZ-2N catalyst (Table 4). Prior to that, a blank reaction was carried out without catalyst resulting in low conversion (1.8%) and 72% selectivity for dioxane. The conversion of styrene was almost complete over most of the solid acid catalysts (except for zeolites). The selectivity for dioxane was different over different acid catalysts, which can be explained based on the distribution of Brnsted and Lewis acid sites in catalyst. The well known strong Brnsted acid catalyst, Cs3.5 H0.5 SiW12 O40 and Montmorillonite K-10 with high B/L ratio of
Table 4 Catalytic performance of various solid acid catalysts for Prins cyclization reaction. Catalyst SO4 /ZrO2 (2N) WO3 /ZrO2 (7 wt% W) H-Beta(25) Amberlyst-15 Montomorlonite-K-10 Cs3.5 H0.5 SiW12 O40 H-ZSM-5(38) H-Y(16) H-Mordenite
2

3.96 and 2.3 showed low selectivity of 67%. The tungstated zirconia and H-beta with B/L ratio of 1.97 and 1.95 resulted in improved selectivity of 82 and 88% respectively. The sulfated zirconia with still lower B/L ratio of 1.4 showed selectivity of 93%. Thus, the selectivity for dioxane decreased with increase of B/L ratio indicating the role of Lewis acidity in Prins cyclization. Interestingly, the selectivity for dioxane was higher (87%) for amberlyst-15 catalyst with high B/L ratio (2.18). This shows that Brnsted acid sites such as SO3 H groups in amberlyst or sulfate groups in SZ are helpful for Prins cyclization of styrene to dioxane compared with other catalysts. The lower activity of medium and large pore zeolites like ZSM-5, H-Mordenite and H-Y could be attributed to the diffusion limitation due to pore size restriction. 3.2.3. Study of nature of solvents The effect of different solvents on Prins cyclization reaction of styrene over SZ catalyst was examined. The reaction was carried out in different solvents as mentioned in Table 5. A correlation was established between solvent parameters like dielectric constant, acceptor (AN) and donor numbers (DN) with the activity of SZ-2N catalyst. The reaction with SZ-2N catalyst without solvent gave a low product yield (56%). This indicates that a proper solvent is necessary, probably to facilitate the generation of formaldehyde from PF. At rst, effect of dielectric constant on the activity of reaction was determined by taking different solvents with similar dielectric constants (DC). The solvent triethyl amine (DC 2.42), cyclohexane (DC 2.02) and toluene (DC 2.38) with almost same DC showed different yields for dioxane as shown in Table 5. This indicates that the dielectric constant has no inuence on catalytic activity of SZ.

Acidity B/L 1.44 1.98 1.92 2.18 2.30 3.96 2.01 3.21 1.4

Time (h) 7 7 7 1 2 2 7 7 7

Conversion (wt%) 99.8 96 22 100 100 97 1 1 2

Selectivity (wt%) 93 82 88 87 67 68 30 50 46

Yield (wt%) 92.8 78.7 19.3 87 67 66 0.3 0.5 0.9

Reaction conditions: catalyst amount = 7 wt%, dichloroethane = 10 ml, styrene = 20 mmol, PF = 60 mmol, temperature = 80 C.

76 Table 5 Effect of solvent on Prins cyclization reaction. Solvent No solvent Cyclohexane Toluene 1,2-Dichloro ethane Nitrobenzene Acetonitrile Triethylamine Isopropyl alcohol

V.S. Marakatti et al. / Applied Catalysis A: General 451 (2013) 7178

Dielectric constant (DC) 2.02 2.38 10.1 34.8 36 2.42 18.3

Acceptor number (A.N) 0 8.2 16.7 14.8 19.3 1.4 33.5

Donor number (D.N) 0 0 0 4.4 14.1 61 21.1

Yield for dioxane 56 47 64 92 22 0 0 0

Reaction conditions: catalyst = SZ-2N, catalyst amount = 7 wt%, solvent = 5 ml, styrene = 10 mmol, PF = 30 mmol, temperature = 80 C, reaction time = 7 h.

Further detailed study of solvent properties like AN and DN gave better understanding on the role of solvent in the reaction. AN and DN of different solvents were rst reported by Gutman which are a measure of acidic or basic nature of solvents [25]. Subsequently these values have been accepted and used by several researchers [24,26]. With an increase in AN of solvent from cyclohexane to dichloroethane, increased the product yield whereas increase in DN of solvent from nitrobenzene to triethyl amine, decreased the product yield. From the above result, it is clear that the solvent with high AN and low DN gives a higher yield of dioxane. The high AN of

solvent represents Lewis acidic property, which induces the formation of formaldehyde from PF without inuencing the active sites of the catalyst. The solvents with high DN are Lewis basic in nature which tends to coordinate with Lewis acceptors with various interactions [27]. Therefore, solvent with high DN like acetonitrile, triethyl amine preferentially adsorb on the acid sites of SZ resulting in blockage of active sites. It also reduces the formation of formaldehyde from PF resulting in poor yield. The protic solvents such as isopropyl alcohol, which possess high donor numbers are not helpful for the reaction. Among all the solvents, 1,2-dichloroethane with high AN and low DN showed best performance.

Fig. 7. Inuence of reaction conditions. (a) Effect of temperature: conditions: catalyst = SZ-2N, catalyst amount = 7 wt%, dichloroethane = 10 ml, styrene = 20 mmol, PF = 60 mmol, time = 7 h. (b) Effect of styrene: PF mole ratio: conditions: catalyst = SZ-2N, catalyst amount = 7 wt%, dichloroethane = 10 ml, temperature = 80 C, time = 7 h. (c) Effect of catalyst amount: conditions: catalyst = SZ-2N, dichloroethane = 10 ml, styrene = 20 mmol, PF =60 mmol, temperature = 80 C, time = 7 h. (d) Effect of reaction time: conditions: catalyst = SZ-2N, catalyst amount = 7 wt%, dichloroethane = 10 ml, Styrene =20 mmol, PF = 60 mmol, temperature = 80 C, time = 7 h.

V.S. Marakatti et al. / Applied Catalysis A: General 451 (2013) 7178 Table 6 Prins cyclization over different olens. Entry Olens Time (h) Dioxane yield (wt%)

77

1.

45.1

12

84.6

2.

55.2

87

3.

92

MeO

4.

Cl
10 26

N
5. 3 0

6.

C6H13

Reaction conditions: catalyst = SZ-2N, catalyst amount = 7 wt%, toluene = 5 ml, olens = 10 mmol, PF = 30 mmol, temperature = 70 C.

3.2.4. Inuence of reaction conditions The effect of reaction temperature was studied using SZ-2N catalyst with styrene to PF mole ratio of 1:3 using 7 wt% of catalyst. The conversion of styrene increased with increase in temperature as shown in Fig. 7a. The low conversion of styrene (0.6%) at lower reaction temperature of 40 C can be attributed to less in situ formation of formaldehyde from PF. At higher temperature of 100 C, the formation of formaldehyde was fast and as a result, complete conversion of styrene was reached within 5 h. The temperature also had an effect on selectivity of dioxane. The increase in temperature decreased the selectivity of dioxane from 94% to 87% due to the formation of side products. The reaction at 80 C showed good conversion and selectivity and hence selected for further study. The effect of mole ratio of styrene to PF was studied at 80 C using SZ-2N catalyst. The mole ratio of styrene to PF was varied from 1:1 to 1:4 as shown in Fig. 7b. The conversion of styrene remained almost constant (99.9%) at different PF concentrations however, the selectivity for dioxane increased with increase in mole ratio due to the decrease of side products. There was only a marginal increase in activity when PF concentration was increased from 1:3 to 1:4. Based on the above results, 1:3 mole ratio was selected for this reaction to get high conversion (99.8%) and selectivity (93%). The study of catalyst amount on Prins cyclization was conducted by taking different weight % of SZ-2N catalyst with respect to the total reactant weight (Fig. 7c). As the catalyst concentration was increased from 3 to 7 wt%, both the conversion and selectivity increased from 66 to 99.8% and 77 to 93% respectively after 7 h reaction. Further increase in the catalyst amount from 7 to 9 wt% increased the conversion in a less time (5 h) but selectivity remained almost the same.

Effect of reaction time for Prins cyclization of styrene with PF was carried out under optimized reaction conditions (Fig. 7d.). The conversion of styrene after 1 h was 27 wt% and further increase in reaction time, increased the conversion and reached of 99.8% after 7 h. But the conversion of styrene/hour decreased as reaction time increased. With increase of reaction time from 1 to 7 h increased the selectivity for dioxane from 82% to 93% as shown in Fig. 7d. The lower selectivity at the beginning of the reaction could be due to the less generation of formaldehyde from PF and hence, side product cinnamyl alcohol was formed predominantly. The formation of cinnamyl alcohol decreased with reaction time and thereby improving dioxane selectivity, which is in agreement with the reported literature [3]. 3.2.5. Applicability of catalyst for different olens To gain more insight into the scope and limitations of our catalyst for Prins reaction, different types of olens were used. The reaction was conducted with different substituted styrenes like 4-methoxystyrene, 4-chlorostyrene, -methylstyrene and other olens like 2-vinylpyridine and 1-octene (Table 6). Electron donating groups on styrene ( OCH3 ), facilitated the reaction with 92% dioxane yield within 3 h whereas electron withdrawing groups like Cl on aromatic ring of styrene decreased the olen reactivity (26% yield). In case of side ring chain substituted -methylstyrene, the reactivity was higher compared with that of styrene which could be due to inductive effect of methyl group resulting in high product yield (87% in 8 h). However, aliphatic olens such as 1-octene did not show reactivity for Prins reaction. Heterocylic aromatic olens like 2-vinylpyridine were also not active which could be due

78 Table 7 Catalyst recycle study. Catalyst cycle 1 2 3 4

V.S. Marakatti et al. / Applied Catalysis A: General 451 (2013) 7178

Dioxane yield (wt%) 92.8 91.9 91 90.7

Reaction conditions: catalyst = SZ-2N, catalyst amount = 7 wt%, dichloroethane = 10 ml, styrene = 20 mmol, PF = 60 mmol, temperature = 80 C, time = 7 h.

styrene and paraformaldehyde by Prins cyclization was reported. The SZ showed best performance among different types of acid catalysts. Medium and large pore zeolites exhibited low conversions due to pore size restriction whereas montmorillonite clay and cesium salt of silicotungstic acid exhibited lower selectivity. The acidity of SZ optimized by different concentrations of H2 SO4 treatment inuences the selectivity for dioxane. Increase of sulfation by treating with high concentration of H2 SO4 decreased the total number of acid sites in SZ as inferred by the TPD. The presence of solvent with high acceptor and low donor number is necessary for SZ catalyst to show high activity and selectivity in Prins reaction. The SZ synthesized by treating 2N H2 SO4 was found to be highly active (100%), selective (93%) and reusable catalyst for Prins cyclization reaction. Acknowledgements Vijaykumar S.M acknowledges the Admar Mutt Education Foundation (AMEF) for providing scholarship. VSM is thankful to the Manipal University for permitting this research as a part of the Ph.D programme. The authors dedicate present work to Sri H.H Vibhudesha Teertha Swamiji, Founder, PPISR, Bangalore. References
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Fig. 8. XRD pattern of recycled catalyst.

to the basic nature of the compound. The reactivity trend was found in the following order 4-methoxystyrene > -methyl styrene > styrene > 4-chlorostyrene > 1-octene 2 -vinylpyridine. 3.2.6. Leaching and recycling test Leaching test was carried out for Prins reaction to investigate the leaching of any active sites of catalyst into reaction media. The reaction was carried out using SZ-2N catalyst at reaction temperature of 80 C with styrene to PF mole ratio of 1:3. Reaction was stopped after 1 h (27% conversion) and hot reaction mixture containing catalyst was ltered. To the ltrate, required amount of PF was added and reaction was continued for next 10 h. The conversion remained constant even after 10 h of reaction time, indicating no leaching of active sites into the reaction media. For a recycling test, the catalyst was ltered after the reaction, washed with acetone followed by drying for 2 h at 120 C and nally calcined at 500 C for 1 h. It was then used in the Prins reaction with fresh reaction mixture. The catalyst showed good recyclability with minimal decrease in activity after 4 cycles (Table 7). XRD patterns of catalyst after each recycle showed the intense peak of tetragonal phase indicating the structural integrity of the catalyst (Fig. 8). 4. Conclusions Application of sulfated zirconia (SZ) as highly selective and reusable catalyst for the synthesis of 4-phenyl-1,3-dioxane from