Ž .Journal of Molecular Catalysis A: Chemical 157 2000 275–278www.elsevier.comrlocatermolcata

Letter

The novel use of Ni, Co, Cu and Mn heterogeneous catalystsfor the Heck reactionq

Suresh Iyer ), Vinay V. Thakur( )Organic Chemistry Synthesis DiÕision Synthes , National Chemical Laboratory, Pune 411 008, India

Received 4 November 1999; received in revised form 7 February 2000; accepted 25 February 2000

Abstract

ŽNovel Ni, Co, Cu and Mn heterogeneous catalysts, catalyze the reaction of aryl and vinyl halides with olefins Heck.reaction to give substitution products. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Heck reaction; Heterogeneous; Catalyst

The Pd catalyzed vinylation of aryl and vinylhalides has been extensively investigated by

w xHeck and others 1–3 because of its wideapplication in organic synthesis. There are a fewreports on the use of Nickel complexes for this

w xreaction 4–7 . We have reported the use of Co,Ž .Rh, Ir, Cu and Ni 0 complexes for the same

w x8–10 . The use of PdrC and other supportedPd catalysts for the Heck reaction has also been

w xreported 11–13 . The use of Ni, Cu and Coheterogeneous catalysts for hydrogenation reac-

w xtions is well known 14–16 . We report here the`first application of these catalysts for a C C

bond formation reaction viz. the Heck reaction.The rationale behind the use of such catalysts

Ž .was the low oxidation state 0 or 1 of thedifferent metals in these catalysts and hence, the

q NCL Communication No: 6585.) Corresponding author. Fax: q91-20-5893153.

Ž .E-mail address: siyer@dalton.ncl.res.in S. Iyer .

possibility of their undergoing oxidative addi-tion reactions.

A number of supported and other heteroge-neous catalysts, 20% NirHY-Zeolite, 20%NirAl O , 20% CorAl O , 20% CurAl O ,2 3 2 3 2 3

U–Ni–A, Co and Mn were prepared followingw xliterature procedures 14–17 . The vinylation of

4-MeO-iodobenzene with ethyl acrylate in thepresence of these catalysts proceeded in high

Ž .yields giving trans-ethyl cinnamate Scheme 1 .The result of these experiments is listed inTable 1. A number of aryl iodides and styrylbromide reacted with a variety of olefins in thepresence of these catalysts, to give substitutionproducts in moderate to high yields.

ŽIn a typical reaction, iodobenzene 0.234 g, 1. Ž . Žmmol , ethylacrylate 5 mmol , K CO 0.2762 3

. Ž .g, 2 mmol , catalyst 0.025 g and N-methyl-Ž .pyrrolidinone 5 ml were taken in a round

bottom flask and heated to 1508C. The reactionprogress was monitored by TLC and most reac-tions were complete in 5–48 h. After comple-

1381-1169r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.Ž .PII: S1381-1169 00 00190-4

( )S. Iyer, V.V. ThakurrJournal of Molecular Catalysis A: Chemical 157 2000 275–278276

Scheme 1.

tion of reaction, the contents were poured intodil. HCl and extracted with ethyl acetate. Col-umn chromatography gave the pure product inhigh yields.

In addition to the supported catalysts pre-pared, the Urushibara methodology was usedfor the preparation of heterogeneous catalystfrom CoCl , MnCl and the Urushibara Ni2 2

catalyst from NiCl . Typically, the Urushibara2

catalysts were prepared by the reduction of thecorresponding metal halides with Zn dust. Thesecatalysts were also found to be active for theHeck reaction. Comparison of the results withdifferent catalysts and olefins revealed the sup-ported Ni catalyst to be more reactive than theothers. Vinyl acetate gave low yield of thesubstitution product. The Urushibara Ni catalystgave only moderate yields of the substitutionproducts. Reaction of styryl bromide withstyrene and ethyl acrylate gave the substituted

Ž .dienes in low yields 15–29% . With theUrushibara Co catalyst, all the olefins, exceptvinyl acetate gave the expected product, inmoderate to low yields. In the reaction ofiodobenzene with styrene catalyzed byCorAl O , stilbene was obtained in 56% yield.2 3

Good yield of the substitution product was ob-tained in the reactions of other aryl iodides withethyl acrylate catalyzed by CorAl O . No reac-2 3

tion was observed with methyl methacrylate.CurAl O gave high yield of the substitu-2 3

tion product even with methyl methacrylate.The Mn catalyst also gave moderate yields ofthe substituted products from the reaction ofdifferent olefins and aryl halides. Longer reac-tion time was required for methylmethacrylate,methacrolein and vinyl acetate. In addition, theyields were low, due to polymerization of these

olefins under the harsh reaction conditions. Noneof these catalysts could activate aryl bromidesor chlorides. Unlike the homogeneous catalysts,no addition of ligands was necessary for theseheterogeneous catalyst mediated reactions. Re-action of 4-Cl-iodo-benzene with methyl-methacrylate gave a mixture of the ester andcarboxylic acid while 4-iodo-nitro-benzene gave4-nitro-phenylmethyl methacrylate as the onlyproduct in the presence of Bu N as base.3

Leaching and recycling studies were also car-ried out on these catalysts. In the leaching ex-

Žperiment, product formation 7–53% for the.different catalysts was observed, when the re-

actions were maintained at 1508C for 24 h. Theleaching experiment was carried out as follows.The catalyst and rest of the reaction mixture,except the olefin, were maintained at 1508C for24 h, followed by filtration to remove the cata-lyst and base. More base was added, followedby ethyl acrylate and the reaction mixture heatedto 1508C for 24 h. Product formation was ob-served by TLC. This indicates that a consider-able amount of the heterogeneous catalyst un-dergoes leaching under the reaction conditions.

In the recycling experiment, three to fourrecycles were carried out with all the catalysts.NirHY-Zeolite, NirAl O , CurAl O and2 3 2 3

U–Ni–A gave )70% yield on the first recycleand above 40% yield on the second recycle.With NirHY-Zeolite catalyst, the second recy-cle also resulted in 73% yield. The third recyclegave 15–20% yield of the product with the restof the starting material being recovered. U–Co–A, CorAl O and U–Mn–A gave only 15–33%2 3

yield of the product in the first recycle, 7–10%in the second and only traces of the product inthe third recycle with recovery of the startingmaterial. Traces of product were also observedin a blank reaction, where, only the alumina

Ž .support neutral Al O , was used without the2 3

catalyst.The XPS data of these catalysts reveal the

presence of the metals, in the 0 and q1 oxida-tion state. The probable mechanism of the reac-tion should be similar to the homogeneous cata-

( )S. Iyer, V.V. ThakurrJournal of Molecular Catalysis A: Chemical 157 2000 275–278 277

Table 1Ž .Heterogeneous catalysis Ni, Cu, Co of the Heck reaction

( )S. Iyer, V.V. ThakurrJournal of Molecular Catalysis A: Chemical 157 2000 275–278278

lyst for the Heck reaction. We have thus shownthe first use of a number of new heterogeneouscatalysts for the Heck reaction. These catalysts

`can also be used for other such C C bondformation reactions.

Acknowledgements

We thank DST for a research grant, VVT fora SRF from CSIR and Dr. M.V. RajasekharamŽ .C.E. Division for providing us some of thecatalysts.

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