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Synthetic Communications: AnInternational Journal for RapidCommunication of SyntheticOrganic ChemistryPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/lsyc20

Clay Catalysis: DryCondensation of BarbituricAcid with Aldehydes UnderMicrowave IrradiationDidier Villemin a & Bouchta Labiad aa I.SM.Ra, U.A.480 CNRS, Université de Caen, F14050, Caen cedex, FrancePublished online: 24 Oct 2006.

To cite this article: Didier Villemin & Bouchta Labiad (1990) Clay Catalysis: DryCondensation of Barbituric Acid with Aldehydes Under Microwave Irradiation,Synthetic Communications: An International Journal for Rapid Communication ofSynthetic Organic Chemistry, 20:21, 3333-3337

To link to this article: http://dx.doi.org/10.1080/00397919008051567

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SYNTHETIC COMMUNICATIONS, 2 0 ( 2 1 ) , 3333-3337 (1990)

CLAY CATALYSIS: DRY CONDENSATION OF BARBITURIC ACID WITH ALDEHYDES UNDER MICROWAVE IRRADIATION

Didier Villemin* and Bouchta Labiad

I.S.M.Ra, U.A.480 CNRS, Universite' de Caen, F 14050 Caen cedex, France.

Abstract: Barbituric acid (1) and arylcarboxyaldehydes (2) were condensated to 5-(arylmethylene)-2,4,6 (lff, 3H, 5ff) pyrimidinetrione (3 )in presence of acidic clay KSF without solvent under microwave irradiation.

The derivatives of the barbituric acid are important class of hypnotic, sedative and anesthetic compounds *.Alkylidene barbituric acids are useful intermediates in synthesis of alkylbarbituric derivatives 2 3 heterocyclic compounds 3 and as electrically neutral Lewis acids 4. Recently they were study as non linear opticiil materials 5 . The barbituric acid like the Meldrum acid 6 and the tetronic acid 7 are strong acids:

pKa=4.01, Continuing the study of dry condensation under microwave irradiation of heterocylic compound containing an acidic methylene group , we described herein the dry condensation of barbituric acid with aldehydes. The reaction of barbituric acid with carbonyl compounds was found as early as 1864 and yielded to mono and biscondensation products 8. We have already reported that alumina catalyzed the formation of monocondensation product of piperonal under dry condition 9. Although alumina catalyzed this reaction, more

*To whom correspondence should be addressed

3333

Copyright 0 1991 by Marcel Dekker. Inc

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3334 VILLEMIN AND LABIAD

Reaction: Condensation of burbituric acid > ( I ) with aldehyde ( 2 ) to

r?iorwcondensation product (3):

Montmorillonite KSF micrqwaves -

acidic catalyst like Montmorillonite clays were more suitable. Reaction took place slowly at room temperature, but microwaves irradiation 10 allowed fast and efficient dry condensation of the barbituric acid with aldehydes. The obtained results are reported in table I with Montmorillonite KSF, similar results were obtained with Montmorillonite K10.

Table I : Reaction of barbituric acid (1) with aldehyde (2) on Montmorillonite KSF under microwaves irradiation (2450 MHz).

aldehyde (2) conditions yield microwave

a) 3,4-methenedioxybenzaldehyde 420 W,5 mm 85 b) 3,4,5-trimethoxybenzaldehyde 420 W, 5 mm 92

d) 4-chlorobenzaldehyde 560 W, 5 mm 68 e) thiophene-2-carboxaldehyde 350 W, 5 mm 92

c) 4-dimethylaminobenzaldehyde 350 W, 5 mm 73

f) 2-furaldehyde 350 W, 5 mm 86 g) 3-(2 fury]) acrolein 350 W, 4 mm 95 h) 5-nitro-2-furaldehyde 350 W, 4 mni 98

We thank Sud-Chemie for the generous gift of Montmorillonite K10 and KSF.

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CLAY CATALYSIS

EXPERIMENTAL

3335

For the instrumental equipment see ref 7. All proton NMR spectra (PMR) were recorded in d6- DMSO solution General procedure :

Barbituric acid(1) (5 mmol), aldehyde(2) (6 mmol) and Montmorillonite KSF (1 g) were ground with solid aldehyde or were mixed with liquid aldehyde. The mixture placed in an open Pyrex Erlenmeyer flask (25 ml) was irradiated with a microwave oven (see table). After cooling the product was extracted with dimethylformamide(DMF, 1.5 ml) and the solvent was evaporated in vacuo. The resulting solid was ground and washed with ether (30 ml), filtered and dried.

5-[(3,4-methylenedioxyphenyl) methylenel-2,4,6 (lH, 3H, 5H) pyrimidinetrione (3 a) Yellow solid ; T (dec) 265" ; PMR : 6 : 6.2 (s, 2H, OCH2O) 7.1 (d, IH, H arom. J= 8 Hz), 7.8 (dd, IH, H arom, J= 8 Hz), 8.3 (m, 2H, 1 arom + 1 CH=), 11.2(s, H, NH), 11.35 (s, H, NH) ; IR (KBr) : 3530-3460 (vNH), 1730 (vC=O), 1685 (NHCONH), 166.5 ; UV (EtOH) hrnax ( loge): 254 (4.0), 386 (3.9).

5-[(3,4,5-trimethoxyphenyl) methylenel-2,4,6 (1 H, 3H, SH) pyrimidinetrione (3 b) Yellow solid ; T (dec) 268" ; PMR 6 : 3,70 (s, 9H, OCH3) ; 7.75 (s, 2H, H arom), 8.20 (s, lH, CH=), 11.50 (s, IH, NH), 11.65 (s, IH, NH) ; IR (KBr) : 4630-3465 (vNH), 1730 (vC=O), 1685 (NHCONH), 1650 ; UV (EtOH) hmax ( log&) : 254 (4.00), 378 (3.95).

S-[(4-dimethylaminophenyl) methyIene]-2,4,6 ( l H , 3H, 5H) pyrimidinetrione (3 c) Red solid ; T (dec) 262", lit . I1 T (dec) 264" ; PMR 6 : 3.15 (s, 6H, N (CH3)2), 6.80 (d, 2H, H arom., J= 8 Hz) 8.20 (s, IH, CH=), 8.45 (d, 2H, H arom., J= 8 Hz), 11,00 (s, lH, NH), 11.10 (s, lH, NH) ; IR (KBr) : 3530-3460 (vNH),

hmax 1710 (VC=O), 1680 (NHCONH), 1650 (vC=O), 1610 (vC=C) ; UV (EtOH)

(log&): 2.54 (3.3, 348 (3.59, 462 (3.4).

5-[4-chlorophenyl) methylenel-2,4,6 (lH, 3H, 5H) pyrimidinetrione (3 d) Orange-red solid ; T (dec) 268O, lit.11 T dec 271' ; PMR 6 : 750 (d, 2H, H arorn, J= 8 Hz), 8.10 (d, 2H, H arom, J= 8 Hz), 8.30 (s, lH, CH=), 11.25 (s, lH, NH), 11.40 (s, lH, NH) ; IR (KBr) : 3520-3480 (vNH), 1750 (vC=O), 1690

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3336 VILLEMIN AND L A B I A D

(NHCONH), 1650 (vC=O), 1550 (vC=C) ; UV (EtOH) hmax ( log&) : 254 (4.03, 322 (3.85).

5-[2-thienylmethylene1-2,4,6 ( l H , 3H, 5H) pyrimidinetrione (3 e) Yellow solid ; T (dec) 270", lit.12 T (dec) 271' ; PMR 6 : 7.35 (m, IH, H arom), 8.20 (m, 2H, H arom), 8.55 (s, lH, CH=), 11.30 (s, IH, NH), 11.35 (s, lH, NH) ; IR (KBr) : 3520-3480 (vNH), 1750 (vC=O), 1690 (NHCONH), 1650 (vC=O), 1550 (vC=C); UV (EtOH) hmax ( loge) : 255 (3.85), 260 @.SO), 377 (3.95).

5-[2-furfurylidene1-2,4,6 ( l H , 3H, 5H) pyrimidinetrione (3 f) Yellow-green solid : T (dec) 264", lit . * T (dec) 260" ; PMR 6 : 6.90 (m, lH, H arom), 8.05 (s, lH, H arom), 8.25 (s, lH, CH=), 8.50 (m, IH, H arom), 11.50 (s, lH, NH), 11.60 (s, IH, NH) ; IR (KBr) : 3515-3475 (vNH), 1740 (vC=0),1685( NHCONH), 1650 (vC=O), 1560, 1540 (vC=C) ; U V (EtOH) hmax (loge) : 254 (3.6), 368 (3.9).

5-(2-furanyl-2-prupenylidene)-2,4,6 ( l H , 3H, 5H) pyrimidinetrione

Red solid ; T (dec) 260", 1it.l T (dec) 260" ; PMR 6 : 6.80 (m, IH, H arom), 7.10 (d, lH, H arom, J= 3 Hz) 7.60-8.00 (m, 3H, H arom + CH=CH), 8.25 (s, lH, CH=C), 11.40 (s, lH, NH), 11.55 (s, lH, NH) ; IR (KBr) : 3520-3480

1560-1530 ; UV (EtOH) hmax ( loge) : 258 (3.85), 410 (4.20).

5-(5-nitrofurylidene)-2,4,6 ( l H , 3H, 5H) pyrimidinetriune (3 k ) Yellow solid ; T (dec) 264", lit. l.3 T (dec) 260" ; PMR 6 : 7.80 (d, lH, H arom, J= 4 Hz), 8.10 (s, lH, CH=), 8.60 (d, IH, H aiom., J= 4 Hz), 11.30 (s, IH, NH), 11,45 (s, lH, NH) ; IR (KBr) : 3520-3475 (vNH), 174.5 (vC=O), 1700 (NHC0,NH) ; 1675 (vC=O), 1600 (vC=C) ; UV (EtOH) hmax ( loge) : 254 (3.80), 340 (3.95).

(3 8)

(vNH), 1730 vC=O), 1690 (NHCONH), 164.5 (vC=O), 1615-1590 (vCZC),

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(Received i n UK 17 September, 1990)

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