LETTER
Graphite-Supported Ketodecarboxylation of Carboxylic Diacids
495
The mechanism of thermal decarboxylation of diacids in (10) (a) Alas, M.; Crochemore, M. (Rhône-Poulenc Chimie), Eur.
Patent Appl. EP 626,364 (FR 93/6,477, 28 May 1993); Chem.
the presence of metallic oxides has been already dis-
cussed. Concerning the reactions described here, since
iron(II) and iron(III) oxides are catalysts (Table 2, entries
2
3
Abstr. 1995, 122, 105296s; (b) Alas, M.; Crochemore, M.
Rhône-Poulenc Chimie), Eur. Patent Appl. EP 626,363 (FR
(
Appl. 93/6,476, 28 May 1993); Chem. Abstr. 1995, 122,
105297t.
6
and 7), the Fe O catalysis could involve these two oxid-
3 4
ation states of iron. After the transient formation of
iron(II) and iron(III) carboxylates from the diacid and
Fe O , the decarboxylative thermolysis of these two salts
could give the cyclic ketone with regeneration of the cat-
alyst.
(
11) (a) Liang, S.; Fischer, R.; Stein, F.; Wulff-Döring, J. (BASF
Aktiengesellschaft) PCT Int. Appl. WO 99 61,402 (DE Appl.
19,823,835, 28 May 1998); Chem. Abstr. 1999, 131, 352841y;
3
4
(
b) Fischer, R.; Liang, S.; Pinkos, R.; Stein, F. (BASF
Aktiengesellschaft) PCT Int. Appl. WO 99 12,883 (DE Appl.
9,739,441, 11 Mar 1999); Chem. Abstr. 1999, 130, 224607u.
1
In conclusion, the graphite-supported thermal decomposi- (12) (a) Kagan, H. B. Pure Appl. Chem. 1976, 46, 177; (b) Setton,
tion of carboxylic diacids produces five- and six-mem-
bered cycloalkanones very efficiently. Under such ”dry“,
solvent-free conditions, and even at high temperature the
diacid is confined on the support and the ketone is ob-
tained on distillation as the only organic compound. A
medium grade commercial powdered graphite appeared
the most suitable, as among its impurities the magnetite
R. Intercalation Compounds of Graphite and Their Reactions;
In Preparative Chemistry Using Supported Reagents; Lazlo,
P., Ed.; Academic Press : London, 1987, Chap. 15, pp 255-
2
1
83; (c) Fürstner, A. Angew. Chem., Int. Ed. Engl. 1993, 32,
64; (d) Wiesendanger, R.; Anselmetti, D. Phys. Chem.
Mater. Low-Dimens. Struct. 1992, 16, 1; (e) Madsen, L. L.;
Joergensen, J. F.; Carneiro, K. Synth. Met. 1993, 55, 335;
(f) Lambin, G.; Devaux, M. H.; Calderone, A.; Lazzaroni, R.;
Bredas, J. L.; Clarke, T. C., Rabe, J. P. ibid. 1993, 57, 4365;
(
Fe O ) is a very efficient catalyst for the reaction.
3 4
(g) Conto, M. S.; Liu, X. Y.; Meekes, H.; Bennema, P. J. Appl.
In order to save energy, the method can also take advan-
tage of MW heating. Thus, the diacid was brought to ele-
vated temperature through the medium of graphite
support which heats strongly and quickly under MW irra-
diation, while avoiding the vaporization of the diacid.
Phys. 1994, 75, 627; and references therein.
(
13) (a) Audhuy-Peaudecerf, M.; Berlan, J.; Dubac, J.; Laporterie,
A.; Laurent, R.; Lefeuvre, S. French Patent 1994, n°94/
09073; (b) Laurent, R. Thesis, Université Paul Sabatier,
Toulouse, France 1994; (c) Laporte, C. Thesis, Université
Paul Sabatier, Toulouse, France 1997; (d) Garrigues, B.;
Laporte, C.; Laurent, R.; Laporterie, A.; Dubac, J. Liebigs
Ann. 1996, 739; (e) Garrigues, B.; Laurent, R.; Laporte, C.;
Laporterie, A.; Dubac, J. ibid. 1996, 743; (f) Garrigues, P.;
Garrigues, B.; C.R. Acad. Sci. Paris, t.1 Sér. IIc: Chim. 1998,
Acknowledgement
Support of this work by the Centre National de la Recherche Scien-
tifique and Rhodia Organique Fine are gratefully acknowledged.
We thank Professor M. Onyszchuk (McGill University) for his as-
sistance in the preparation of the manuscript.
1
, 545; (g) Laporte, C.; Oussaid, A.; Garrigues, B.; C.R. Acad.
Sci. Paris, t.1 Sér. IIc: Chim. 2000, 3, 321; (h) Marquié, J.
Thesis, Université Paul Sabatier, Toulouse, France 2000.
14) Dabirmanesh, Q.; Fernando, S.I.S.; Roberts, R.M.G. J. Chem.
Soc., Perkin Trans.1 1995, 743.
(
(
References and Notes
15) (a) Ben Alloum, A. Thesis, Université de Caen, France 1991;
(
1
b) Villemin, D.; Hachemi, M.; Lalaoui, M. Synth. Commun.
996, 2461.
16) (a) Kodomari, M.; Suzuki, Y.; Yoshida, K. Chem. Commun.
997, 1567; (b) Suzuki, Y.; Matsushima, M.; Kodomari, M.
(
1) (a) Peligot, E. Justus Liebigs Ann. Chem. 1834, 12, 854;
b) Friedel, C. ibid. 1858, 108, 122; (c) Limpricht, H. ibid.
858, 108, 183; (d) Fittig, R. ibid. 1859, 110, 17.
(
1
(
1
(
2) (a) Kwart, H.; King, K. In The Chemistry of Carboxylic Acids
and Esters; Patai, S., Ed.; Wiley-Interscience: London, 1969,
Chap. 8, pp 341-37; (b) March, J. Advanced Organic
Chemistry; Wiley: New York, 4th Ed., 1992, p 496; and
references therein.
Chem. Lett. 1998, 319. (c) Lapin, Y.A.; Sanchez, I.H. (Great
Lakes Chemical Corporation), U.S. Patent 1999, n°5,969,159.
17) Laporte, C.; Baulès, P.; Laporterie, A.; Desmurs, J.-R.;
Dubac, J. C. R. Acad. Sci. Paris, t.1, Sér. II c 1998, 141.
18) Mailhe, A. Compt. Rend. 1913, t. 157, 219.
(
(
(
(
(
(
3) Senderens, J.-B. Compt. Rend. 1909, t. 148, 927.
4) Sabatier, P.; Mailhe, A. Compt. Rend. 1914, t. 158, 985.
5) (a) Rand, L.; Wagner, W.; Warner, P. O.; Kovac, L. R. J. Org.
Chem. 1962, 27, 1034. (b) Hites, R. A.; Biemann, K. J. Am.
Chem. Soc. 1972, 94, 5772; (c) Bouchoule, C.; Blanchard, M.;
Thomassin, R. Bull. Soc. Chim. Fr. 1973, 1773; and
references therein.
6) (a) Ruzicka, L.; Brugger, W.; Pfeiffer, M.; Schinz, H.; Stoll,
M. Helv. Chim. Acta 1926, 9, 499; (b) Ruzicka, L.; Brugger,
W.; Seidel, C.F.; Schinz, H. ibid. 1928, 11, 496; (c) Ruzicka,
L.; Stoll, M.; Schinz, H. ibid. 1928, 11, 670; (d) Ruzicka, L.;
Schinz, H.; Pfeiffer, M. ibid. 1928, 11, 686; and references
therein.
19) Typical Procedure for the Synthesis of Cyclopentanone
(
(
5). Conventional Heating (Table 1, entry 1). To a 2.19 g
15 mmol) sample of adipic acid (1), 5 g of graphite A were
added, and the mixture was ground in a mortar prior to being
placed in the reactor. The flask, surmounted by a Dean-Stark
condenser equipped with an ice-cold finger, was immersed in
a preheated tubular electric furnace and heated at 450 °C for
(
3
0 min. The ketone 5 condensed mainly in the cold trap, and
the remainder was extracted from graphite powder with ether.
A 90% overall yield in 5 was determined by GC analysis
(internal standard: cyclohexanone). To obtain a larger sample
of product, four successive runs were performed, and the
combined organic phases were distilled to obtain 4.29 g (85%
yield) of pure 5 (bp. 130-131 °C). Microwave Heating (Table
(
(
(
7) Thorpe, J.F.; Kon, G. A. R. Org. Syntheses, Coll. Vol. I 1941,
192.
2
, entry 1.) The same mixture as before was introduced in the
8) Liberman, A. L.; Vasina, T.V. Izv. Akad. Nauk. SSSR, Ser.
Khim. 1968, 3, 632.
quartz reactor of the MW apparatus, surmounted by the same
Dean-Stark condenser. MW irradiation was programmed
using the computer for a sequential process in which the
sample was exposed for periods of 2 min separated by periods
9) Siegel, H.; Eggersdorfer, M. Ketones; In Ullman’s
Encyclopedia of Industrial Chemistry; Gerhartz, W., Ed.;
VCH: Weinheim (Germany), 1990, Vol. A15, pp 77-96.
Synlett 2001, No. 4, 493–496 ISSN 0936-5214 © Thieme Stuttgart · New York