Friedel–Crafts acylation of 2-methoxynaphthalene over zeolite catalysts

Applied Catalysis A: General 201 (2000) 159–168

Friedel–Crafts acylation of 2-methoxynaphthaleneover zeolite catalysts

Debasish Das, Soofin Cheng∗Chemistry Department, National Taiwan University, 1 Roosevelt Road, Section 4, Taipei 106, Taiwan

Received 17 May 1999; received in revised form 10 December 1999; accepted 15 December 1999

Abstract

The Friedel–Crafts acylation of 2-methoxynaphthalene was carried out in the liquid-phase batch conditions using H-mordenite, H-beta and H-Y zeolite as catalysts. All the catalysts showed 35–40% conversion in the temperature range of100–150◦C. 1-Acyl-2-methoxynaphthalene was formed as the primary product. When acetyl chloride was used as the acylatingagent, a higher yield of 6-acyl-2-methoxynaphthalene was obtained through rearrangement of the sterically hindered 1-acylisomer to the 6-acyl isomer. The presence of extra-framework aluminum in the catalyst facilitates the isomerization of 1-acylisomer to the desired 6-acyl isomer. The final product selectivity was found to be more dependent on the nature of theacylating agents and the reaction temperature and less on the type of the zeolite structure. © 2000 Elsevier Science B.V. Allrights reserved.

Keywords:Friedel–Crafts acylation; Zeolites; H-mordenite; H-beta; H-Y; 2-Methoxynaphthalene

1. Introduction

Friedel–Crafts acylation is one of the most impor-tant methods for the synthesis of aromatic ketones [1].The synthesis of aromatic ketones is of special im-portance in the fine chemicals industry, as many syn-thetic fragrances and pharmaceuticals contain an acylgroup. In general, Lewis-acid metal chloride catalystsare employed for aromatic acylation. Unfortunately,use of such conventional catalysts is associated witha number of problems. A major drawback of thesecatalysts is that they are non-regenerable and morethan a stoichiometric amount of the catalyst is needed.Besides, the work-up steps involving hydrolysis ofthe resultant intermediate complex produce hazardous

∗ Corresponding author. Tel.:+886-2-2363-8017;fax: +886-2-2363-6359.

corrosive waste products. Disposal of such wasteproducts also leads to other environmental problems.

Many of these drawbacks can be overcome by us-ing recoverable and regenerable solid catalysts likezeolites. Therefore, the use of zeolites and other solidacid catalysts in the manufacture of fine chemicalsand chemical intermediates is gaining much moreattention in recent years. The Friedel–Crafts acyla-tion reaction mechanism, as proposed by Olah [1],involves acylation either by an adduct of the catalystand the acylating agent or by free acylium ions, de-pending on the reaction conditions. In heterogeneouszeolite-catalysed acylation, a similar mechanism is as-sumed to apply, in which the adduct is formed by theinteraction of the surface acid sites with an acylatingagent (Fig. 1). Chiche et al. [2] investigated the acyla-tion of toluene and xylene by a series of straight-chaincarboxylic acids over lanthanide-exchanged zeolites.

0926-860X/00/$ – see front matter © 2000 Elsevier Science B.V. All rights reserved.PII: S0926-860X(00)00438-5

160 D. Das, S. Cheng / Applied Catalysis A: General 201 (2000) 159–168

Fig. 1. Mechanism of zeolite catalyzed acylation of aromatics.

Similar reactions over USY and ZSM-5 zeoliteswere reported recently in the literature [3,4]. Acyla-tion of aromatic ethers like anisole [5–8], phenetole[8], veratrole [9] and 2-methoxynaphthalene [9–11]over zeolite catalysts was also reported. Acylation of2-methoxynaphthalene is of particular interest if theketone functionality can be placed at the 6-position,since this compound could then be used as a pre-cursor to the anti-inflammatory drug naproxen [12].Harvey and Mäder [10] studied this reaction overzeolite USY, H-beta and ZSM-12 and showed thatin all cases 1-acyl-2-methoxynaphthalene was ob-tained as the major product. In comparison to otherzeolites, H-beta with narrower 12-ring channelsand no super cages showed slightly increased se-lectivity for 6-acyl-2-methoxynaphthalene. It wasproposed that the more confined internal environ-ment of H-beta restricts access to the 1-position of2-methoxynaphthalene [10]. Recently, mesoporousmolecular sieve material of MCM-41 type [11] andcation-exchanged clays [9] were also studied forthe acylation of 2-methoxynaphthalene. However, inboth cases, acylation occurred predominantly in the1-position only. On the other hand, it was noticedthat with Zn-impregnated MCM-41 high selectivity to6-acyl-2-methoxynaphthalene can be obtained in polarsolvents like nitrobenzene [11]. Thus, it is clear thatthe selectivity to the 6-acyl-2-methoxynaphthaleneis not only controlled by the pore geometry or porestructure of the zeolite used, other factors also playimportant roles.

In the present work, acylation of 2-methoxynaph-thalene was carried out in the liquid-phase conditions

in the presence of H-mordenite zeolite. Effects of re-action temperature, nature of the acylating agent, andthe substrate/acylating agent ratio were also investi-gated in order to increase the yield of the 6-acyl iso-mer. Acylation of 2-methoxynaphthalene over otherzeolites has been reported earlier [10]. In this workthe results obtained with H-mordenite zeolite werecompared with those obtained with other zeolites likeH-beta and HY. Unlike H-beta and HY, which havethree-dimensional channel structures, H-mordenitepossesses a two-dimensional channel structure. Theeffect of the zeolite structure on product selectivitywas also examined.

2. Experimental

Zeolite mordenite (Si/Al=9.5) was received inits protonic form from Tosoh Chemicals as Refer-ence Catalyst No. 28. Zeolite NH4-beta and NH4-Ywere obtained from PQ Corporation and Advchemlaboratories, respectively. They were converted intotheir protonic forms by calcination in air at 550◦Cfor 6 h. The Si/Al ratio, ion-exchange level and thesurface area of the zeolite samples are given inTable 1. Acid-washed mordenite sample (to removeextra-framework aluminum) was prepared by stir-ring the parent sample with dilute hydrochloric acid(0.5 N) in a beaker for 15 min. The solid was thenfiltered, washed with water and dried at 120◦C.

Acylation reaction was carried out under batch con-ditions with reflux set-up in the temperature range of100–150◦C. Both acetyl chloride and acetic anhydridewere used as the acylating agents to study the effect ofthe nature of the acylating agent. Sulfolane (bp 285◦C)was used as the solvent. A typical reaction conditionwas as follows: 3.2 mmol of 2-methoxynaphthaleneand 3.2 mmol of acetyl chloride were well mixed in

Table 1Physical properties of the zeolite samples

Zeolite Si/Al Ion-exchange Surfacetype level (%) area (m2/g)

Mordenite 9.5 98 380Beta 12.5 97 680Y 2.6 92 560Mordenite (acid-washed) 10.7 – –

D. Das, S. Cheng / Applied Catalysis A: General 201 (2000) 159–168 161

10 ml solvent along with 1 ml nitrobenzene (internalstandard). To this mixture 150 mg of freshly activated(400◦C, 2 h) catalyst was added quickly while still hot.The reaction temperature was then raised slowly to thedesired value. Samples were taken periodically andanalyzed by gas chromatography (Restek-1 capillarycolumn, 30 m) to monitor the progress of the reaction.Product identification was carried out by using avail-able standard compounds and also by GC-Mass anal-ysis (HP 6890-5973). All the chemicals (AR grade)were obtained from Aldrich or Acros Organics andwere used without further purification.

In order to examine the regenerability of the cata-lyst, the solid phase was separated from the reactionmixture by filtration, washed with dichloromethane,dried at 100◦C and finally calcined at 500◦C for 24 h toremove the carbonaceous deposits before further use.

X-ray powder diffraction patterns were recordedon a Scintag X1 diffractometer using Cu Ka radiation(λ=0.154 nm). Solid state27Al MAS NMR measure-ments were carried out using a Bruker MSL 500 spec-trometer with 4 mm cylindrical zirconia rotors spun at12 kHz. Spectra were obtained at 130.319 MHz with20◦ pulse duration of 1ms and recycle delay of 200 ms.Chemical shifts were recorded with reference toaqueous Al(NO3)3 solution.

3. Results and discussion

Fig. 2 shows the change in 2-methoxynaphthaleneconversion with reaction time at different reactiontemperatures and also using different acylating agents.Acetyl chloride and acetic anhydride both can createonly one acyl group. Acetic acid formed in the reac-tion with acetic anhydride is not reactive, as separateexperiments conducted with acetic acid showed that ithas no acylation activity under the reaction conditions.It was found that at 100◦C acetyl chloride showedmuch higher conversion than that obtained with aceticanhydride. It appears that acetyl chloride is moreeffective for acylation than acetic anhydride. As thereaction temperature was raised, conversion increasedrapidly and the maximum value was reached muchfaster. At higher temperatures, both acylating agentsyielded very similar conversions. The conversionreached the maximum value of ca. 30% at around 9 hTOS at 125◦C. However, further increase in reaction

Fig. 2. Conversion of 2-methoxynaphthalene as a function ofreaction time on H-mordenite catalysts using acetyl chloride (opensymbols) and acetic anhydride (solid symbols) (substrate:acylatingagent=1:1 molar ratio); (h, j: 100◦C; 4, m: 125◦C, s, d:150◦C; dotted lines for conversion with acid-washed mordenite at125◦C).

temperature reduced the conversion by facilitatingthe reverse deacylation reaction [10]. Such decreasein conversion by deacylation was more noticeable athigher reaction temperatures.

Higher conversion with acid chloride over acidanhydride was also observed in the benzoylation ofm-xylene [3]. The authors proposed that the acid chlo-ride or HCl liberated during the reaction interactedwith the extra-framework aluminum species in thecatalyst to form catalytically active aluminum com-plexes. However, we have not observed any significantdifference in conversion (Fig. 2) when acid-washedmordenite (to remove extra-framework aluminum)was used as catalyst.

The distribution of the three acylated isomers ob-tained with both acetyl chloride and acetic anhydrideat 125◦C are given in Fig. 3. It can be seen that, withacetic anhydride, 1-acyl-2-methoxynaphthalene wasobtained as the major product, as observed earlier byother workers also [9–11]. As the reaction proceeded, a


Fig. 3. Selectivity to different acyl-2-methoxynaphthalenes as afunction of reaction time on H-mordenite catalysts at 125◦C us-ing acetyl chloride (open symbols) and acetic anhydride (solidsymbols) (substrate:acylating agent=1:1 molar ratio); (h, j:1-acyl-2-methoxynaphthalene,4, m: 8-acyl-methoxynaphthalene,s, d: 6-acyl-2-methoxynaphthalene; dotted lines for selectivitywith acid-washed mordenite catalyst).

minor quantity (<10%) of 6-acyl-2-methoxynaphtha-lene was formed and a negligible amount of 8-acyl-2-methoxynaphthalene was detected. However,the product pattern obtained with acetyl chlorideas the acylating agent was quite different. Initially,1-acyl-2-methoxynaphthalene was the predominantproduct. Nevertheless, as the reaction proceeded, itsselectivity decreased markedly, accompanied by anincrease in 6-acyl-2-methoxynaphthalene selectivityas well as by formation of a small quantity (<5%)of 8-acyl-2-methoxynaphthalene. The sharp decreaseof the 1-acyl isomer with concomitant increase ofthe other two isomers suggests that the 6- and 8-acylisomers probably arise from the isomerization of theprimary product, 1-acyl-2-methoxynaphthalene.

It is well known that the presence of an electron-donating group like methoxy activates the 1-, 6, and8-positions of the naphthalene ring. The 1-positionis more active than the other two positions, and acy-

Scheme 1. Acylation of 2-methoxynaphthalene and isomerizationof the acyl group.

lation of 2-methoxynaphthalene generally occurs atthis kinetically controlled position. However, migra-tion of the acyl group from 1- to 6-position [13] andprotiodeacylation of the acyl group at the 1-position[14] results in the formation of the thermodynam-ically most stable 6-acylated isomer (Scheme 1).Steric hindrance to acylation is in the order 1- >8->6-position. Hence, the isomerisation of the stericallyhindered ketones like 1-acyl-2-methoxynaphthaleneto sterically less hindered isomers like 6- and8-acyl-2-methoxynaphthalene will be favored.

Fig. 4 shows the plots of yields of individualisomers with conversion of 2-methoxynaphthaleneusing both acetic anhydride and acetyl chloride. Itcan be seen that, with acetic anhydride, yields of1- and 6-acyl-2-methoxynaphthalene both increasedlinearly with the rise in conversion. However, yieldsof 1-acyl-2-methoxynaphthalene were much higherthan those for 6-acyl-2-methoxynaphthalene. On theother hand, with acetyl chloride as acylating agent,yields of 1-acyl-2-methoxynaphthalene reached amaximum at about 25% conversion and decreasedwith further increase in conversion, whereas yieldsof 6-acyl-2-methoxynaphthalene were much lowerinitially but increased continuously with increase inconversion. It appears that the reaction follows twodifferent mechanisms [15] with acetic anhydride andacetyl chloride. In the former case, formation of the


Fig. 4. Yields of different acyl-2-methoxynaphthalenes as a function of conversion with H-mordenite catalysts at 125◦C using (A)acetic anhydride and (B) acetyl chloride (substrate:acylating agent=1:1 molar ratio); (h, j: 1-acyl-2-methoxynaphthalene,4, m:8-acyl-2-methoxynaphthalene,s, d: 6-acyl-2-methoxynaphthalene).

1-acyl and 6-acyl isomers are independent of eachother and possibly formed via two parallel reactions.Conversion of 1-acyl to other stable isomers like6-acyl and 8-acyl was negligible.

In the latter case, the reaction follows a combinationof parallel and sequential paths. Initially, at lower con-version, 1-acyl-2-methoxynaphthalene was the majorproduct, but at higher conversions, it isomerizes tomore stable 6-acyl-2-methoxynaphthalene. Isomeriza-tion of 1-acyl isomer was found to be enhanced bythe presence of extra-framework aluminum species(vide infra).

Fig. 5 shows the variation in the yields of differentacylated isomers with reaction time at 125◦C. It can beseen that the yields of 6-acyl-2-methoxynaphthaleneincreased much more rapidly when acetyl chloride

was used as the acylating agent. Conversely, yields of6-acyl-2-methoxynaphthalene remained almost con-stant at<2% with acetic anhydride.

These results show that, with acetyl chloride as theacylating agent, acylation and consecutive rearrange-

Fig. 5. Yields of different acyl-2-methoxynaphthalenes as a func-tion of reaction time on H-mordenite catalysts at 125◦C usingacetyl chloride (open symbols) and acetic anhydride(solid symbols) (substrate: acylating agent=1:1 molar ratio);(h, j: 1-acyl-2-methoxynaphthalene,4, m: 8-acyl-2-methoxy-naphthalene,s, d: 6-acyl-2-methoxynaphthalene).


ment of the 1-acyl isomer leads to the increased for-mation of the desired 6-acyl isomer. In contrast, withacetic anhydride, the rearrangement of the 1-acyl iso-mer was very limited and the product mostly containsonly 1-acyl isomer and very little 6-acyl isomer. Themaximum yield of 6-acyl-2-methoxynaphthalene thatcan be achieved by changing the experimental parame-ters like temperature, reaction time, substrate/acylatingratio was found to be only 15% with acetic anhydride.

It appears that the rearrangement of 1-acyl isomer(through deacylation-reacylation) is more favored inthe presence of acetyl chloride than in that of aceticanhydride. Deacylation may also be facilitated by theHCl liberated from acetyl chloride during the courseof the reaction. However, when 0.5 ml of 37 wt.%

Fig. 6. 27Al MAS NMR spectra of H-mordenite catalyst, (a) fresh, (b) after reaction using acetic anhydride, (c) after reaction using acetylchloride and (d) acid-washed mordenite.

HCl acid was added to a reaction mixture containing2-methoxynaphthalene and acetic anhydride, after 1 hof reaction at 150◦C no sharp change in the productselectivity was observed. After further 9 h of reac-tion the product mostly contained only 1-acyl iso-mer. This indicates that rearrangement of the 1-acylisomer is not caused by HCl liberated from acetylchloride. It was reported earlier that extra-frameworkaluminum species present in the catalyst may reactwith acetyl chloride to form strong acid centers [3].Fig. 6 shows that the aluminum atoms in the origi-nal H-mordenite sample are mostly in the tetrahedralposition. However, a small fraction of octahedral orextra-framework aluminum is also present, as indi-cated by a broad peak at about 0 ppm. For acid-washed


mordenite (curve d), the intensity of the peak at 0 ppmwas slightly lower, indicating the presence of loweramounts of extra-framework aluminum species. Whenacid-washed mordenite was used as catalyst, the se-lectivity towards 6-acyl-isomer (Fig. 3 dotted lines)was found to be less than that obtained with untreatedmordenite. This indicates that acetyl chloride mayinteract with the extra-framework aluminum sites toform strong acid centers which may be responsible forthe rearrangement of 1-acyl isomer to the other ther-modynamically favored isomers. Earlier workers alsonoticed that, in the presence of Lewis acid catalystslike Zn-MCM-41, acylation of 2-methoxynaphthalenewith acetyl chloride initially formed the sterically hin-dered 1-acyl-2-methoxynaphthalene as the primaryproduct. However, during the course of the reaction,the 1-acyl isomer easily underwent rearrangement togive higher yields of 6-acyl-2-methoxynaphthalene[11]. Thus, the rearrangement of the primary prod-uct, 1-acyl isomer, was most probably caused bythe strong acid centers formed by interaction ofthe extra-framework aluminum species with acetylchloride.

The effect of reaction temperature on the productdistribution is shown in Fig. 7. As observed earlier, se-lectivity to 6-acyl-2-methoxynaphthalene was alwaysfound to be higher with acetyl chloride, whereas aceticanhydride yielded 1-acyl-2-methoxynaphthalene asthe major product. Increase in reaction temperaturewas found to favor the migration of acyl group from1-position to 6-position. Also, the rearrangement ofthe 1-acyl isomer to 6-and 8-acyl-isomer was morenoticeable when acetyl chloride was used as the acy-lating agent. With acetyl chloride, the 6-acyl isomercan be obtained with ca. 90% selectivity at 150oC.

Increasing the amount of acylating agent inthe reaction mixture was found to increase the2-methoxynaphthalene conversion. Increase of sub-strate/acylating agent ratio from 1:1 to 1:2 resultsin about 50% increase in conversion, however, theselectivity towards different acylated isomers did notchange much.

For comparison, acylation of 2-methoxynaphthalenewith acetyl chloride was also carried out in pres-ence of other zeolites like H-beta and HY; the re-sults are presented in Table 2. All the three catalystsinvestigated showed about 30–40% conversion of2-methoxynaphthalene in the reaction temperature

Fig. 7. Selectivity to different acyl-2-methoxynaphthalene iso-mers as a function of reaction temperature after 3 h us-ing acetyl chloride (open symbols)and acetic anhydride (solidsymbols) (substrate:acylating agent=1:1 molar ratio); (h, j:1-acyl-2-methoxynaphthalene,4, m: 8-acyl-methoxynaphthalene,s, d: 6-acyl-2-methoxynaphthalene).

range of 100–150◦C. It was observed that at 100◦C,HY showed higher activity than the other two cata-lysts. However, as the reaction temperature was raisedto 150◦C, the initial high conversion dropped rapidlywith the progress of reaction, indicating faster dea-cylation of the primary product. Zeolite H-beta andH-mordenite also showed some deacylation at highertemperatures, but the drop in conversion was not assharp as that observed with HY.

Table 2 also shows the selectivity towards dif-ferent acylated isomers of 2-methoxynaphthalenefor different catalysts studied. A high selectivitytowards 6-acylated isomer was noticed, especiallyat a reaction temperature of 150◦C. In the caseof HY, larger amounts of 8-acyl isomer were alsoformed. In contrast, earlier works on the acyla-tion of 2-methoxynaphthalene with acetic anhydrideover USY and H-beta showed predominant for-mation of 1-acyl isomer only [10]. Acylation of2-methoxynaphthalene on mesoporous molecular


Table 2Acylation of 2-methoxynaphthalene by acetyl chloride in sulfolane catalysed by different zeolitesa

Catalyst Reaction temp. (◦C) Conversion (%)b Selectivity to different isomers (%)b

1-acyl 6-acyl 8-acyl

H-beta 100 35 30 65 5150 40 13 77 10

H-Y 100 41 60 36 4150 35 – 82 18

H-mordenite 100 31 59 38 3150 40 23 69 8

a Substrate:acylating agent=1:2.b After 6 h reaction time.

sieve material, MCM-41 and on cation-exchangedclays was also reported to give substitution predom-inantly on 1-position only [9,11] as the 1-positionin the naphthalene ring is highly activated by thepresence of a nearby methoxy group. At the onsetof reaction, 1-acyl isomer was formed predominantlybut with the progress of reaction most of it rearranged(rearrangement was much faster at higher tempera-tures) to more stable 6-acyl and 8-acyl isomers. Itwas observed that at 100oC H-beta showed high-est selectivity towards 6-acylated isomer (ca. 65%),while HY and H-mordenite showed higher selectivity(ca. 60%) towards sterically hindered 1-acyl isomer.

Fig. 8. Yields of 6-acyl-2-methoxynaphthalene with different zeolite catalysts with acetyl chloride as acylating agent (substrate:acylatingagent=1:2 molar ratio); (H-beta at 100◦C h, 150◦C j: HY at 100◦C s, 150◦C d; H-mordenite at 100◦C 4, 150◦C m).

However, at 150oC, larger amounts of 6- and 8-acylisomers were formed at the expense of the 1-acylisomer. This further confirms that the increased yieldof the 6-acyl isomer at higher reaction temperaturewas due to the rearrangement of the primary product,1-acyl-2-methoxynaphthalene. Friedel–Crafts acyla-tion is usually irreversible, but at higher temperaturesdeacylation of the acyl group at 1-position can oc-cur [10,14]. Since this phenomenon does not involvethermodynamically more stable and sterically unhin-dered 6-acyl or less hindered 8-acyl isomers, a highreaction temperature usually leads to a change in thedistribution of the products.


It appears that at lower reaction temperature, H-betahas better selectivity for 6-acyl isomer than the othertwo catalysts have. Earlier workers [10] also observedbetter selectivity for H-beta at 100◦C and assignedit to the more confined pore geometry in beta zeo-lite. However, at higher temperatures, rearrangementof 1-acyl isomer to 6-acyl isomer takes place muchfaster. It can be seen that with HY zeolite 1-acyl iso-mer has been completely isomerized to other isomersafter 6 h at 150◦C. Isomerization of 1-acyl isomer wasrelatively less for H-mordenite and H-beta, possiblydue to their narrower one-dimensional pore geometry.However, it may be mentioned that the natures of theacylating agent and of the reaction temperature playmore important roles than the zeolite structure indetermining the final product selectivity.

Fig. 8 shows the yields of 6-acyl-2-methoxynaphtha-lene with reaction time on different zeolite catalysts.At 100◦C, H-beta showed much higher yields of6-acyl isomer than the other two catalysts. InitiallyH-mordenite and HY showed similar yields. Never-theless, as the reaction proceeds HY showed higheryields than mordenite. At a higher temperature, e.g.,150◦C, the yields of 6-acyl isomer increased rapidlywith mordenite and after 6 h both mordenite andH-beta showed similar yields. On the other hand,with HY the yields of 6-acyl isomer decreased con-tinuously at 150◦C due to decrease in conversion (bydeacylation) and also due to increased formation of8-acyl isomer. The amount of 8-acyl isomer formedat 150◦C with HY was almost twice that producedwith H-beta.

Although acetyl chloride showed good conversionand high selectivity towards the 6-acyl-2-methoxy-naphthalene, one possible drawback of using acetylchloride is that the acid liberated during the course ofthe reaction may affect the crystallinity of the catalystand also may cause some dealumination. We havechecked the crystallinity of the used H-mordenite cat-alyst by X-ray diffraction and also examined the na-ture of the aluminum sites by27Al MAS NMR. Fig. 9shows the XRD patterns of the parent and the usedH-mordenite catalysts. The structure of the zeolite re-mains intact after the reaction and no appreciable lossof crystallinity was observed. Chemical analysis ofthe used catalysts showed a slight loss of aluminumafter reaction. The27Al MAS NMR spectra of the par-ent and used catalysts (Fig. 6) show that after reaction

Fig. 9. Powder XRD patterns of the H-mordenite catalyst: (a)before reaction and (b) after reaction.

the intensity of the peak at 0 ppm increased, indicatinghigher amounts of extra-framework aluminum afterreaction. However, both acetyl chloride and aceticanhydride were found to have similar effects.

For practical applications, a good catalyst must beeasily regenerable so that it can be used repeatedly.

Table 3Regenerability of H-mordenite in the acylation of 2-methoxy-naphthalene by acetyl chloride in sulfolane at 150◦Ca

Cycle Conversion (%)b Selectivity to different isomers (%)b

1-acyl 6-acyl 8-acyl

1 40 23 69 82 36 21 71 83 33 27 65 8

a Substrate:acylating agent 1:2.b After 6 h reaction time.


Excellent regenerability of H-mordenite catalyst wasobserved, as shown in Table 3. Although there wasslight loss of activity (due to loss of aluminum), theselectivity towards different acylated isomers wasalmost unchanged up to three catalytic cycles.

4. Conclusions

H-mordenite showed very good activity for liquidphase acylation of 2-methoxynaphthalene. The finalproduct selectivity was found to be dependent moreon the nature of the acylating agents and the reactiontemperature than on the type of the zeolite structure.With acetyl chloride as the acylating agent, rear-rangement of the primary product, 1-acyl isomer to6- or 8-acyl isomer, was predominant. The presenceof extra-framework aluminum in the catalyst leads toa very high selectivity towards desired 6-acyl isomer,possibly through formation of strong acid centers withacetyl chloride. H-mordenite catalyst also showedexcellent regenerability for repeated use.

Comparison with other zeolite catalysts shows thatat moderate temperature H-beta has better selectivityfor the 6-acyl isomer than the HY and H-mordenite.However, at higher temperatures, yields of the 6-acylisomer were found to be similar with all three catalystsdue to faster isomerization of the 1-acyl isomer to6-acyl isomer.

Acknowledgements

The financial support and a post-doctoral researchfellowship (DD) from the National Science Council,

Taiwan, are gratefully acknowledged. The authors arealso thankful to Tosoh Chemicals, Japan, for a freesample of H-mordenite catalyst and to Dr. Hong–PingLin for recording the27Al MAS NMR spectra.

References

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Friedel–Crafts acylation of 2-methoxynaphthalene over zeolite catalysts

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