3-Acetyl-4-hydroxy-6-methyl-2-oxo-2H-pyran (Dehydroacetic acid abbreviated as DHA) has been isolated from natural sources1-2 and is also industrially utilizing

a number of synthetic procedures. 3-6 The reactions of DHA and its derivatives have been shown to have a wide utility in organic synthesis. These developments along with the studies on related pyrone derivatives have been reviewed.7
OH 4 5 H3C 6 O 1 3 2 O O CH3

DHA Since DHA has several reactive sites, the molecule is susceptible to attack by the nucleophilic and electrophilic reagents. A nucleophile can, in principle, attack the carbonyl of the acetyl side chain located at 3-position, the carbon atom terminating the conjugated carbon chain at 6position, the lactone carbonyl at 2-position and the carbonyl carbon at 4-position of the molecule. On the other hand, an electrophile can attack either at C(3) or C(5). As part of our investigations dealing with the synthesis and mechanistic studies of heterocyclic compounds, we have reported some useful transformations of DHA and its derivatives.8-10. A Literature survey reveals that the reactions of DHA and its derivatives with different reagents can provide a versatile route to the synthesis of a wide variety of heterocyclic compounds

i)

Chalcones and cinnamonyl derivatives

Treatment of DHA(1) with aromatic and heteroaromatic aldehydes via microwave assisted Knoevenagel condensation yields 3-cinnamoyl-4-hydroxy-6-methyl-2-oxo-2H-pyrans(2). However, it was found that isolated yields (75-92%) were improved with short span of time (410 min). 11
O CH3 H3C O 1 O

CH3

ArCHO Piperidine, CHCl3, Reflux

CH3

O Ar

H3C

O 2

Scheme 1

ii) Reaction of DHA with 5-chloro-3-methyl-1-phenylpyrazole-4-carbaldehyde via claisen-schmidt condensation to afford heterochalcones,which on subsequent treatment with arylhydrazines undergo cyclisation to give hetroaryl-2-pyrazolines.12
Cl 1 Ph N N OHC CH3 3 OH O 4
H3C O O Cl N Ph

Methanol, piperidine H3C Reflux

O CH3

Cl N

Ph

N CH3 CH3

Reflux
OH N N R 5

N CH3

iii) Condensation of 3-acetyl-6-methyl-2-oxo-2H-pyran- 4-yl difluoridoborate complex I with heterocyclic aldehydes provided complexes 2, 3 and 5 by heating of the starting compounds in Ac2O or AcOHH2SO4 mixture. By a reaction of dehydracetic acid (III) with boron trifluoride etherate we obtained its boron complex, 3-acetyl-6-methyl-2-oxo-2H-pyran-4-yl difluoridoborate (IV) (Scheme 1). From condensation of compound IV with aromatic aldehydes VaVd difluoridoborates VIaVId were obtained (Scheme 2). From condensation of compound IV with aromatic aldehydes VaVd difluoridoborates VIaVId were obtained which on treatment with Na2CO3,EtOH,H2O leads to the hydroxyketonesVIIa-VIId. compound IV reacted also with the derivatives of cinnamaldehyde, 4-dimethylaminocinnamaldehyde (VIIIa) and 4methoxycinnamaldehyde (VIIIb) (Scheme 3).compound 4 reacts with aromatic aldehyde to give IX . 3-Acetyl-6-methyl-2-oxo-2H-pyran-4-yl difluoridoborate (IV) was also brought into condensation with heterocyclic aldehydes (Scheme 4). In this reaction boron complexes XII and XV were obtained. Compound XVIIa was also synthesized by condensation of boron complex IV with two equiv of the corresponding aldehyde. The reaction proceeded simultaneously at both reaction sites. The treatment of boron complexes obtained VIaVId, IXa, IXb, XII, XV,
XVIIa, XVIIb, and XVIId with sodium carbonate in aqueous-alcoholic medium followed by acidification resulted in the formation of the corresponding hydroxyketones VIIa VIId, Xa, Xb, XIII, XVI, XVIIIa, XVIIIb, and XVIIId. (4-6). 13

F F B O O CH3 H3C O 6 O

BF3O(C2H5)2
1

F F B O O R CH3 Ac2O,AcOH.H 2SO 4 H3C O H3C O 7 S CHO F

F B O O

S O R

R=N(CH3)2Br Table 5
F H3C N H3C 7 Ac2o or AcOH,H 2SO 4 H3C O O N 8
H3C CH3 F B O N 7 XIV Ac2O CH3 H3C O O CHO O H3C H3C N R 1) Na 2CO 3 EtOH,H 2O CH3 2) HCl H3C O O OH O H3C H3C N CH3 R F

F B S CHO O O 1) Na 2CO 2 EtOH,HCl 2) HCl S H3C CH3 9 H3C O O N CH3 OH O

H3C

10

11

Sr no. 1 2.

R N(CH3)2 Br

Inhibition of IN Catalytic activity IC50(M) 3-processing Strand transfer Selectivity index >100 >100 92 32 3.2

Scheme 2
F
CHO F F B O O CH3 H3C O O R
4

F B
R1

R1 R2

R2 R3

H3C

O R4 12(a-d)

R3

Ac2O or AcOH,H2SO4
OH O R1

(1) Na2CO3,EtOH,H2O (2) HCl

H3C

R2

O R4 13(a-d)

R3

R1 = R2 = R4 = H, R3 = N(CH3)2 (a), OCH3 (b); R1 = H, R2 = R3 = R4 = OCH3 (c); R1 = OCH3, R2 = R3 = H, R4 =Br (d). Scheme 3
F F B O O R1 R2 H3C N CH3 Ac2O H3C O O R4 12a,12Ib,12d R3 H3C N CH3 O O R4 14a, 14b, 14c R3 CHO F F B O O R1 R2

OH

R1 R2

1) Na 2CO 3 EtOH,H 2O 2) HCl

O H3C N CH3

O R4 15a, 15b, 15c

F F B

R3

F F B O O CH3 H3C O O R CHO

Ac2O or AcOH, H2SO4

OH O

H3C

16a,16b

1) Na2CO3 ,EtOH, H2O 2) H2O

H3C O O 17a,17b R

R = N(CH3)2 (a), OCH3 (b). Scheme 4

R=C6H6

III) PYRANOPYRAZOLES
Cl O CH3 RNHNH2 H3C O 18 O NHNHR COCH
3

PCl5 ground,
6hrs

EtOH Stir 15 min H3C

O 19

RNHNH 2, Method B AcOH, Reflux

AcOH, Reflux

Method A

R N 20 N CH3

H3C

O 21

IV)

5-SUBSTITUTED-4-METHOXY-6-METHYL-2-PYRONES

3-Bromo-4-methoxy-6-methyl-2-pyrone 5 was synthesized in two steps from commercially available triacetic acid lactone in 55% overall yield (Fig. 1). Bromination of commercially available dehydroacetic acid at 0 C, followed by deacetylation with 90% sulphuric acid and then methylation provides 5-bromomethoxy- 6-methyl-2-pyrone 6 starting material in 46% yield.15
OCH 3 Br Br OCH 3

H3C

O 22

H3C

O 23

Fig 1 Substrates 5 and 6 for Suzuki cross-coupling

Coupling of various arylboronic acids with 5a

OCH 3 Br R B(OH) 2 or H3C O B O 24 S 25-28 H3C O O

+
H3C O 23 O

Pd(OAC)2

OCH 3 R

Compound 7 8 9 10 11
OCH 3 Br

Pyrone (R) CH3(CH2)2 CH3(CH2)3 CH3(CH2)4 CH3(CH2)5 C6H5-

+
H3C O 23 O

R B(OH) 2 29

Pd(OAc)2

OCH 3 R

H3C

O 30-35

Compound 12 13 14 15 16

Pyrone (R) CH3(CH2)2 CH3(CH2)3 CH3(CH2)4 CH3(CH2)5 C6H5-

. Coupling of various arylboronic acids with 5a

OCH 3 Br

R
OCH 3 OCH 3

C6H5B(OH)2R
H3C O 22 36-41 O H3C O O

+
H3C O 42 O

Entry Pyrone (R) 7

17 19 20 21 22 23

H, 17 P-CH3,19 P-Cl,20 P-CH3O,21 m-NO,22 p-CHO,23

. Coupling of various arylboronic acids with 6a

OCH 3 Br

R
OCH 3

C6H5B(OH)2R
H3C O 23 O

i
H3C O 43-48 O

Compound 24 25 26 27 28 29

Pyrone(R) H p-CH3 p-Cl p-CH3O m-NO2 p-CHO

v) 2H-PYRANS AND 2H-PYRIDINES Arylhydrazines reacted with DHA(1) to give the corresponding 2Hpyran2one hydrazones (2), which on treatment with hydrazine hydrate afforded the corresponding 1amino2Hpyridin2ones (3). Reaction of 3 with nitrous acid, aromatic aldehyde and substituted benzenesulfonyl chlorides yielded the corresponding 2Hpyridine2one derivatives.16
OH 1 NNHR CH3 O 49 O OH NNHR CH3 N CH3 50 O

RNHNH2 Reflux 15 min, stand for 2h H3C

N2H4 Reflux H C 3 2h

CH3

NNHR CH3 CH3 NNHR CH3 H3C 52 O NHCOHNR

2

CH3

NNHR H3C CH3 N H O 51

H3C 53

O NHCOHNR
2

stirring 2h
50

R2NCO Reflux 5h R1CHO , Reflux 5h CH3

R2NCS, Reflux 5h
CH3 NNHR CH3 H3C O NHSO 2R2 55

R2SO2Cl, reflux 4h

NNHR CH3

H3C N=CHR 54

O
1

NH OH N CH3 H3C O 56 CH3 H3C O O 55 O

SO 2NHCONHR

NH OH N

SO 2NH 2

R1NCO, Reflux 8-10 h

R2NCS, Reflux 5-8 h

NH OH N CH3 H3C O 57 O

SO 2NHCSNHR

Compound 2a 2b 2c 3a

C6H5pH2NSO2CH pClCHC6H5-

R1 `or R2 9

3b 3c 4a 5a 5c 5d 6a 6b 7a 7b 7c 8a 8b 9a 9b 9c 10a 10b 11a 11b 11c 12a

pH2NSO2CHpClCHC6H5C6H5C6H5pClCHC6H5C6H5C6H5C6H5C6H5C6H5C6H5-

Cyclohexyl pClCHCyclohexyl CH3CH3(CH3)2CH2 C6H5pCH3CH pCH3OCH C6H5pCH3CH Cyclohexyl C6H5pClCHCH3 Cyclohexyl Cyclohexyl C6H5pClCHCyclohexyl

vi) Pyrimidines

Reaction of DHA with aromatic aldehydes yields 3-cinnamoyl-4-hydroxy-6-methyl-2-oxo-2Hpyrans (2) which on treatment with S-Benzyl isothiouronium chloride (SBT) in the presence of piperidine as a base give the 6-substituted-4-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-2-Sbenzylthiopyrmidine .17
OH O H2N Cl Ar H N 2 O 58 O
+ -

SCH 2Ph SCH 2Ph OH N N Ar H3C O 59 O

ArCHO Piperidine, H C CHCl3,reflux 3

Piperidine

10

Table 19 Compound 3b 3i 3j VII) Ar 3-FC6H4 2-Thienyl 4-Pyridyl

AZETIDINONES

Treatment DHA (1) with primary aromatic amines to yield Schiff bases by using microwave system. Schiff bases irradiated with dimethyl formamide in presence of triethyl amine and chloroacetyl chloride to afford azetidinones.18
R1 1 OH R2 C H OH 2 5 R3 60 CH3 C O O 61 OH CH3 C H3C O O 62 N O R1 R2 N R1 R2 H2N

MW 300W, H3C 10 min

R3

DMF, TEA, ClCH2COCl MW 300 W, 7 min

Cl

R3

Table 22.Physical data of compounds (2a-2g) and (3a-3g)

Compounds 2a 2b 2c 2d 2e 2f 2g 3a 3b 3c 3d 3e 1 2 3 4 5 6 7 8 9 10 11 12

R1 -OCH3 -CH3 -Br -Br -H -OH -H -OCH3 -CH3 -Br -Br -H

R2 -H -H -Cl -H -H -H -H -H -H -Cl -H -H

R3 -H -H -H -H -H -H -Cl -H -H -H -H -H 11

Yield (%) 67 80 75 80 70 69 72 76 74 72 74 74

3f 3g viii)

13 14

-OH -H

-H -H

-H -Cl

72 65

Pyrazoles and Thiazoles

Condensation of 3-(2-bromoacetyl)-4 hydroxy-6-methyl-2H-pyran-2-one (1), thiosemicarbazide (2) and various carbonyl compound give the thiazole and pyrazole derivatives.19
O R1 R2 OH N S R2 R1 NH N

NH H2N S 63

NH2

rt, 10 min
H3C O O

O H3C

CH3

rt, 10 min

64

H3C N OH N S N

CH3

H3C

O 65

scheme 25 Compound 4a 4b 4c 4d 4e 4f 4g R1 CH3 CH3 CH3 CH3 CH3 Cyclohexylidine H R2 CH3 C6H5 p-tolyl p-anisyl Et cyclohexylidine Ph 12 Yield (%) 92 80 80 82 80 81 77

1 2 3 4 5 6 7

4h 4i 4j ix)

8 9 10

H H H

O-hydroxyphenyl p-tolyl p-anisyl

87 80 78

Isoxazolyl thiazolyl pyrazoles

The reaction of DHA(1) with thiosemicarbazide which is converted into the hydrazones.the rearrangement in ethanol-acetic acid mixture to afford the key intermediate 1-(5-hydroxy-3-methyl-1substituted pyrazol-4-yl)-1,3-butanediones which on treatment with hydroxylamine hydrochloride to yield 1-(4-phenyl/4-substitutedphenyl)thiazol-2-yl)-3-methyl-4-(3-methylisoxazol-5-yl)-H-pyrazol-5-ol. 20
N NH OH NNHCSNH CH3
2

NH2CSNHNH2/ EtOH
1

RCOCH2Br, NaOAc /EtOH Reflux

OH

N CH3

Reflux
H3C O 66 O

H3C

O 67

EtOH /AcOH Reflux

S

N N

NH2OH,HCl EtOH /AcOH

N

CH3 O N H3C N HO S 69 N R

Reflux
N CH3

HO HO O CH3 68

Table 29 compounds 3a 3b 3c 3d R C6H5 P-CH3-C6H5 P-OCH3C6H5 P-Cl-C6H5 Yield (%) 76 71 73 67 13

4a 4b x)

C6H5 P-CH3-C6H5

57 59

Pyrazolo[4,3-c]pyridine-4-ones

All 3,6-dimethyl-l-phenyl-l~-pyrazolo[4,3-c]pyridine-4- one derivatives (5) were prepared from dehydroacetic acid (1) as the starting material. The reaction of 1 with an appropriate phenylhydrazine derivative (2) in ethanol afforded hydrazone derivatives (3), which were converted to fused compounds (4) by dehydrating in the presence of p-toluenesulfonic acid. The ammonolysis of 4 with saturated ethanolic ammonia afforded lactam derivatives (5) in fair yield (Scheme I). Alkoxy (71, acyloxy (81, and methylsulfonyloxy (9) derivatives were prepared by the methods shown in Scheme II. Briefly, demethylation of methoxy derivative (5a) with pyridine hydrochloride afforded the hydroxy derivative (6). Alkylation of 6 with an appropriate alkyl halide in the presence of anhydrous potassium carbonate, acylation of 6 with an appropriate acid anhydride in pyridine, and methylsulfonylation of 6 with methylsulfonyl chloride in the presence of tiethylamine afforded 7, 8, and 9, respectively (Scheme 11). Thiation of 4 with phosphorus pentasulfide afforded thiolactone derivatives (lo), which were converted in the same manner as described for 5 to the thiolactam derivative (11). The acetoxy derivative (13) was obtained by demethylation of llb and subsequent acetylation of 12 in the same manner as described for 8 (Scheme 111).21
O H3C H2NHN 1 H3C O 70 71 O OH CH3 NNH O

H+

N N CH3

NH3

O H3C NH N N CH3

72

14

O O NHCl 72b H3C NH N N CH3 H3C NH

(RCO)2O

N N CH3

OCOR OH 73 74

S H3C NH N N CH3

NH3
71

R
75

S N HCl 11b N N CH3

+

H3C NH

OH 76

Table31 Compound 8a 11a 12 1 2 3 R CH3 H Yield (%) 78 75 68

15

xi)

Pyrazolo-oxazin-2-ones

DHA reacts with phenylhydrazine to give the 1,3-dicarbonyl compound 2 . Reaction of derivatives 2 with aliphatic and aromatic primary amines lead to pyrazolyl-enaminones 3 which react with thiophosgene in presence of triethylamine to give N-substituted substituted pyrazolooxazin-2-thione compounds.22
1

NH2NHPh CH3COOH, H3C

R CH3 N

RNH2 EtOH ,
H3C

NH

CH3 N

HO 77

N ph

HO

N ph 78

SCCl2, 0C Et3N, CH2Cl2

S R N H3C O N N ph 79 O CH3

Scheme 24 Table33 Compounds 4a 4b 4c 4d 4e 4f 4g R CH3CH2 CH3CH2CH2 CH2C6H4 C6H6 4-CH3-C6H4 4-OCH3-C6H4 4-Br-C6H4 Yield (%) 74 71 76 82 86 80 72

1 2 3 4 5 6 7

xii) Pyrazolo-oxazinones Scheme 1 outlines our general strategy developed to obtain the pyrazolo-oxazinones 4ak. This procedure starts with the reaction of the commercially available dehydroacetic acid 1 with phenylhydrazine to give in two steps the 1,3-dicarbonyl compound 2 according to the literature procedure.34 Exposure of 2 to aliphatic and aromatic primary amines led to pyrazoloenaminones 3ak using the method reported in the reference.35 Ring closure of compounds 3ak

16

with triphosgene in dichloromethane in the presence of triethylamine provided the target compounds 4ak in 7085% yields.23
R CH3 N HO 80 81 N ph

NH2NHPh CH3COOH, H3C

RNH2 EtOH ,
H3C

NH

CH3 N

HO

N ph

(CCl3O)2CO, 0C Et3N, CH2Cl2

O R N H3C O N N ph 82 O CH3

a. R= C2H5 d. R= 2-thienyl b. R= n-C4H9 e. R= C6H5-CH2 c. R= isobutyl f. R= C6H5 g. R= 4-CH3C6H4 j. R= 4-ClC6H4 h. R= 4-CH3OC6H4 K. R= 4-BrC6H4 i. R= 4-CH3O2CC6H4 Scheme 25. Compound 4a 4b 4c 4d 4e 4f 4g 4h 4i 4j 4k R C2H5 n-C4H9 (CH3)2CHCH2 2-thienyl C6H5-CH2 C6H5 4-CH3C6H4 4-CH3OC6H4 4CH3O2CC6H4 4-ClC6H4 4-BrC6H4 Yield (%) 78 76 74 71 72 82 85 84 70 72 72

17

xii)

Pyrano[2,3-c] pyrazol-4-ones
R NHNH NH
2

OH

N CH3

+
R 83

EtOH
H3C O 84 O

Scheme 26

Table 37
Tale VVVVVVVVVVVVVVVVVVVVVVVVVVVVVVVVVVVV1TTTTTGGLKK4646464646 AJJT binding activity

Comp 1a 1b 1c 2a 2b

R H NO2 NH2 H NO2

R1 CH3 CH3 CH3 -

R2 H H H -

Yield (%) 25 20 30 20 25

XIV) PYRIDAZINE

3-Acetyl-4-hydroxy-6-methyl-2H-pyran-2-one (dehydroacetic acid) (1) prepared from ethylacetoacetate, on refluxing with Conc. H2SO4 gives 4-hydroxy-6-methyl-2- pyrone . This on coupling with diazonium chloride, prepared by conventional diazotization technique from an amine of the formula R-NH2 (where R is phenyl or substituted phenyl) gave hydrazone , which on treatment with an aqueous acid yields pyridazine-3-carboxylic acid.25
N2 Cl O O H3C O OH
+ -

90% H2SO4 Reflux, CH3 7hrs

1

Reflux, 1hr H3C

18

OH NH NH

i) Reflux, 3 hrs ii) Conc HCl, 40-70% H3C

O OH

H3C

N N

Scheme 16 Table26

S NO 1 2 3 4 5 6 7 8 9

Compounds 5a 5b 5c 5d 5e 5f 5g 5h 5i

R 4-F 4-CN 4-CF3 3-F 2,4-Difluoro 3,5-Difluoro 3,4-Difluoro 4-COOH 4-CONH2

Yield(%) 68 35 40 76 56 45 42 40 45

Metal complexes i) The ligand have been synthesized by the condensation of dehydroacetic acid (3-acetyl-6-methyl(2H) pyran-2,4(3H)-dione or DHA), o-phenylene diamine and fluoro benzaldehyde.(26)
NH2 NH2 1

3hrs
N OH

+
NH2

reflux, ethanol

c H3C O O CH3

19

O H F H N

reflux, ethanol, 6 hrs

H3C

N c

OH

CH3

Scheme 27

CH3

H3C

O C

N H

CH3

H3C

Figure . Proposed structure of the metal complexes, where M= Cu(II), Ni(II), Co(II), Mn(II) and Fe(III). ii) The new ruthenium(II) carbonyl complexes of dehydroacetic acid thiosemicarbazone of the type [Ru(dhatsc)(CO)(B)(EPh3)] (Scheme 1) have been obtained from the reaction of [RuHCl(CO)(B)(EPh3)2] (where E = P, B = PPh3, py, pip (or) mor; E = As, B = AsPh3) with tridentate Schiff base H2dhatsc in dry benzene in 1:1 molar ratio.(27)

20

H3C O [RuHCl(CO)(B)(EPh
3) 2]

NH

C CH2

NH2

OH

H3C

Benzene, Reflux 10 h 1:1

H3C O O H3C H3C C O N

+

B CH 3
C S

EPh3
C NH2

Scheme 28. Structure of ruthenium(II) carbonyl complexes of dhatsc

Table 39 Analytical data of ruthenium(II) carbonyl complexes of DHATSC

S.no 1 2 3 4 5 Complexes [Ru(dhatsc)(CO)(PPh3)2] [Ru(dhatsc)(CO)(Py)(PPh3)2] [Ru(dhatsc)(CO)(PiP)(PPh3)2] [Ru(dhatsc)(CO)(Mor)(PPh3)2] [Ru(dhatsc)(CO)(AsPh3)2]

iii) The solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with asymmetrical tetradentate Schiff bases derived from o-phenylenediamine (H2L1)/4-methyl o-phenylenediamine (H2L2), 3Acetyl-6-methyl-pyran-2,4-dione (Dehydroacetic acid) and 2-hydroxy-1-naphthaldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, uv-visible, i.r, 1H-nmr. spectra, X-ray diffraction, thermal analysis, and screened for antimicrobial activity.(28)

21

H3C

OH

HO

O H3C

N H

R = H / CH3 Figure 1. Structure of ligand

H3C

M
O H3C N N H

Figure 2(a)
H3C

OH2
O H3C N

M
N

OH2

Fig. 2(b)k
22

R = H / CH3 Fig.2. The proposed structure of the complexes. (a)When M = Cu(II) and Ni(II); (b) When M = Co(II), Mn(II) and Fe(III)
iv)

The solid complexes of MnII, FeIII, CoII, NiII and CuII with 3-(3-furan-2yl-acryloyl)-6-methylpyran-2,4-dione(L1) and 3-(3-thiophene-2yl-acryloyl)-6-methyl-pyran-2,4-dione (L2) have been synthesized.(29)
OH O R

H3C

Fig. 1. Structure of ligand. Legends: R=O or S.

R

H3C

OH2
O O O O

M
O O

CH3

Fig. 2. The proposed structure of the complexes. Legends: R=O or S. X = H2O; When M = MnII, CoII, NiII and CuII, X = Cl; When M = FeIII.

The solid complexes of MnII, FeIII, CoII, NiII and CuII with 3-(3-furan-2yl-acryloyl)-6-methylpyran-2,4-dione(L1) and 3-(3-thiophene-2yl-acryloyl)-6-methyl-pyran-2,4-dione (L2) have been synthesized.(30)
23

OH

O R

H3C

Fig. 1. Structure of ligand. Legends: R=O or S.

R

H3C

OH2
O O O O

M
O O

CH3

Fig. 2. The proposed structure of the complexes. Legends: R=O or S. X = H2O; When M = MnII, CoII, NiII and CuII, X = Cl; When M = FeIII

1 Rivera C.; Pineyro,E.; Giral,F. Dehydroacetic acid in anthers of Solandra nitida (Solanaceae) Experientia, 1976, (32), 1490. 2. Ohno,H.; Saheki, T.; Awaya,J.; Nakagawa,A.; Omura,S. J. Antibiot., 1978, 31(11), 11161123 3. F. Arndt, and P. Nachtwey, Chem Ber., 1954, 57, 1489; (Chem. Abstr., 1925, 19, 286).

24

4. Steele, A. B.; Boese, and M. F. Dull. Heterogeneous Catalysis and Fine Chemicals II. J. Org. Chem., 1949, 14, 460.

5. Kaushol,R. Heterogeneous Catalysis and Fine Chemicals II J. Indian Chem. Soc., 1946, 23, 16. 6. Pechmann,V.B. Heterocyclic Compounds.1891, (24), 194 7. M. M. Manas, and R. Pleixats, Advances in Heterocyclic Chemistry J. Am9. Chem. Soc., 1992, 53, 1. 8. Singh,S.P.; Grover,M.; Tarar,L.S.; Elguero,J.; Martinez,A. A 1H and 13c Nmr study of the structure and tautomerism of 4-pyrazolylpyrazolinones . J. Heterocycl. Chem., 1990, 27, 865.

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