INTRODUCTION:

The synthesis of chalcone linked with imine group in same compound became of great importance in organic chemistry to synthesis of various compounds.

α,β-Unsaturated ketones are biogenetic precursors of flavonoids in higher plants. Also known chemically as chalcones, they consist of open-chain flavonoids in which the two aromatic rings are joined by a three carbon chain [1,2]. They display a wide range of pharmacological properties, including cytotoxity toward cancer cell lines [3,4], anti mitotic , anti mutagenic [5] The chemistry of chalcones has generated intensive scientific interest due to their biological and industrial application. Chalcones are natural biocides and are well known intermediates in the synthesis of heterocyclic compounds exhibiting various biological activities[6] Chalcones and their derivatives possess some interesting biological properties such as antibacterial, antifungal, insecticidal, anesthetic, anti inflammatory, analgesic. Etc[7,8]

Pyrimidine derivatives play avital role in many biological processes and in synthesis of many drugs. Many derivatives of pyrimidine have displayed diverse biological activities such as antitumor, hypnotensive, antiulcer, and anticonvulsant[9]

EXPERIMENTAL:

Materials

All the chemicals were supplied by BHD and Fluka and used without further purification.

Measurement

-The melting point of compounds were determinate by Electro thermal melting point apparatus.

-C.H.N Elemental analysis were carried out by micro analytical unit of 1180 C.H.N Elemental analyzer.

-FT.IR spectra were recorded using (KBr pellets) 4000-400 cm-1 on FT.IR tests can .Shimadzu 8000 Series.

-The 1H-NMR spectra were obtained in DSMO solvent using (Bruker, Ultra .Shield 3000MKZ, Switzerland).

Synthesis of chalcones [10]

Equimolar quantity (0.001mol) of 4-aminoacetophenone and p-nitro benzaldehyde mixed and dissolved in 30 mL of ethanol. To this, 40% sodium hydroxide solution (5 mL) added slowly and mixed occasionally for (5 h), at room temperature. Completion of the reaction was identified by TLC using Silica gel-G. The solvent was evaporated and the precipitation was recrystallized from absolute EtOH to give Comp.(I) Scheme (1).

Synthesis of Schiff bases (Ia-c):

Ethanolic mixture of compound (I)(0.001mole) with 4-dimethyle amino benzaldehyde, (0.001mole) were refluxed for 8hr at 65⁰C in presence of EtOH(30 ml) with addition (2) drops of glacial acitic acid. The reaction was monitored by TLC using Silica gel-G. The solvent was evaporated and the precipitation was recrystallized from absolute EtOH to give Comp.(Ia-c) Scheme (2)

Synthesis of Pyrimidines from Chalcones [11]:

A mixture of Schiff bases (Ia-c) of (0.01mole), urea or thiourea or guanedin (0.01mole) in absolute ethanol (25mL) and potassium hydroxide (5mL) refluxed on a water bath for(8h) The reaction was monitored by T.L.C and The solvent was evaporated and the precipitation was recrystallized from absolute EtOH to give comp.(Ia₁-c₁).

Table 1. Physical data of compounds .

Comp.	M.f	M.Wt	m.p C°	Yield %,gm
I	C₁₅ H₁₂ N₂ O₃	268	120-122	0.21gm 73 %
Ia	C₂₄H₂₁N₃ O₃	399	141-143	0.25gm 64 %
Ib	C₂₃ H₁₅ N₃O₄	397	189-191	0.39gm 75 %
Ic	C₂₃ H₁₈ N₂O₅	402	160-162	0.24gm 61 %
Ia1	C ₂₅H ₂₂N₆ O₂	438	105-107	0.29gm 63 %
Ib1	C ₂₄H ₁₆N₆ O₃	436	134-136	0.3 gm 65.7 %
Ic1	C ₂₄H ₁₉N₅ O₄	441	149-`151	0.32 gm 69 %
Ia2	C ₂₅ H ₂₁N₅ O₂ S	455	128-130	0.31 gm 65 %
Ib2	C ₂₄H ₁₅N₅ O₃S	453	165-167	0.35 gm 73.9 %
Ic2	C ₂₄H ₁₈N₄ O₄	458	180-182	0.36 gm 75 %
Ia3	C ₂₅H ₂₁N₅ O₃	439	144-146	0.33 gm 71.8 %
Ib3	C ₂₄H ₁₅N₅ O₄	437	178-180	0.29 gm 63 %
Ic3	C ₂₄H ₁₈N₄ O₅	442	198-200	0.38 gm 82 %

RESULT AND DISCUSSION:

1-(3-aminophenyl)-3-(4-chlorophenyl)prop-2-en-1-one (I)

IR (KBr, cm^-1): 1647 (C=O)ketone, 1610 (CH=CH) ethylene, 1600(CH=CH) aromatic, 3225-3371 (-NH₂), 3100(-CH) alkenes, 3076(-CH) aromatic

1-{4-[(4-dimethyleaminobenzylidene)amino]phenyl}-3-(4-nitrophenyl)prop-2-en-1-one(Ia)

IR (KBr, cm-1): 1680 (C=O)ketone, 1654 (N=CH) imine, 1600(CH=CH) ethene, 1595(CH=CH) aromatic, 2995(-CH) aliphatic.

3-({4-[3-(4-nitrophenyl)acryloyl]phenyl}imino)isoindolin -1-one (Ib)

IR (KBr, cm^-1): 1732 (C=O) amide, 1680 (C=O)ketone, 1670 (N=CH) imine, 1614 (CH=CH) ethene, 1519(CH=CH) aromatic, 3192(-CH) alkene, 3421(-NH). ¹H NMR (DMSO, δ, ppm) : 2. 20 (1H, d, -CO-CH=), 6. 95 – 7. 75 (18H, Ar-H ) 10. 20 (1H, -CO-NH-).

1-{4-[(2-hydroxy-3-methoxybenzylidene)amino]phenyl}-3-(4-nitrophenyl)prop-2-en-1-one(Ic)

IR (KBr, cm^-1): 1683 (C=O)ketone, 1650 (N=CH) imine, 1626(CH=CH) ethene, 1595(CH=CH) aromatic, 2966(-CH) aliphatic, 3080(-CH) aromatic, 3120(-CH) alkene, 3394 (-OH). ¹H NMR (DMSO, δ, ppm) : 3. 85 (3H, P-OCH3), 2. 20 (1H, d, -CO-CH=), 6. 90 – 7. 60 (18H, Ar-H ) 8. 80(1H, CH=N), 11. 20(1H, O-H).

4-(4-(4-(dimethyl amino ) benzylidene amino)phenyl)-6-(4-nitro phenyl)pyrimidine-2-amino (Ia₁)

IR (KBr, cm^-1) : 1685 (C=N)endo cyclic, 1635(N=CH) imine, 1550(CH=C) aromatic, 2900(-CH) aliphatic, 3255-3400 (-NH₂). Anal. Calcd. For C₂₅H₂₁N₆O₂ : C, 68. 49; H, 5. 02; N, 19. 17. Found: C: 68. 21; H: 5. 00; N: 19. 05%.

3-(4-(2-amino-6-(4-nitro phenyl)pyrimidine-4-yl)phenyl imino)isoindolin-1-one (Ib₁)

IR (KBr, cm^-1): 1637(C=O) amide, 1620 (C=N)endo cyclic, 1590 (N=CH) imine, 1568(CH=CH) aromatic, 3385(-NH), 3277-3473 (-NH₂), 3174 (-CH) aromatic

5-((4-(2-amino-6-(4-nitrophenyl)pyrimidine-4-yl) phenyl imino)methyl-2-methoxy phenol (Ic₁)

IR (KBr, cm^-1): 1670 (C=N)endo cyclic, 1656 (N=CH) imine, 1568(CH=CH) aromatic, 2900(-CH) aliphatic, 3220-3330(-NH₂), 3356 (-OH). ¹H NMR (DMSO, δ, ppm) : 3. 50 (3H, P-OCH3), 6. 90 – 7. 65 (18H, Ar-H ) 8. 70(1H, CH=N), 11. 40(1H, O-H), 9. 40(2H, -NH₂).

4-(4-(4-(dimethyl amino ) benzylidene amino)phenyl)-6-(4-nitro phenyl)pyrimidine-2-thiol (Ia₂)

IR (KBr, cm^-1) : 1681 (C=N)endo cyclic, 1651(N=CH) imine, 1618(CH=CH) aromatic, 2922(-CH) aliphatic, 3165 (-CH) aromatic, 2850 (-SH). Anal. Calcd. For C₂₅H₂₁N5O₂S: C, 63. 93; H, 4. 61; N, 15. 38. Found: C: 63. 48; H: 4. 32; N: 14. 62%.

3-(4-(2-mercapto-6-(4-nitro phenyl)pyrimidine-4-yl)phenyl imino)isoindolin-1-one (Ib₂)

IR (KBr, cm^-1) : 1699(C=O) amide, 1645 (C=N)endo cyclic, 1616 (N=CH) imine, 1568(CH=CH) aromatic, 3396(-NH), 2840 (-SH), 3105 (-CH) aromatic.

5-((4-(2-mercapto-6-(4-nitrophenyl)pyrimidine-4-yl) phenyl imino)methyl-2-methoxy phenol (Ic₂)

IR (KBr, cm^-1): 1685 (C=N)endo cyclic, 1654 (N=CH) imine, 1560(CH=CH) aromatic, 2928(-CH) aliphatic, 2854(-SH), 3460 (-OH), 3182 (-CH) aromatic. ¹H NMR (DMSO, δ, ppm) : 3. 50 (3H, P-OCH3), 6. 85 – 7. 60 (18H, Ar-H ) 8. 70 (1H, CH=N), 11. 50(1H, O-H), 12. 6 (1H, S-H).

4-(4-(4-(dimethyl amino ) benzylidene amino)phenyl)-6-(4-nitro phenyl)pyrimidine-2-ol (Ia₃)

IR (KBr, cm^-1): 1690 (C=N)endo cyclic, 1640(N=CH) imine, 1624(CH=CH) aromatic, 2924(-CH) aliphatic, 3387 (-OH), 3184(-CH) aromatic. Anal. Calcd. For C₂₅H₂₁N5O₃: C, 68. 33; H, 4. 78; N, 15. 94. Found: C: 68. 03; H: 4. 43; N: 15. 65%.

3-(4-(2-hydroxy-6-(4-nitrophenyl)pyrimidine-4-yl)phenyl imino)isoindolin-1-one (Ib₃)

IR (KBr, cm^-1): 1662 (C=O) amide, 1650 (C=N)endo cyclic, 1616 (N=CH) imine, 1575(CH=CH) aromatic, 3320(-NH), 3410 (-OH).

4-(4-(3-hydroxy-4-methoxy benzylidene amino) phenyl)-6-(4-nitrophenyl)pyrimidine-2-ol (Ic₃)

IR (KBr, cm^-1): 1674 (C=N)endo cyclic, 1600 (N=CH) imine, 1575(CH=CH) aromatic, 2928(-CH) aliphatic, 3050(-CH) aromatic, 3356-3400(-OH). ¹H NMR (DMSO, δ, ppm) : 3. 40 (3H, P-OCH3), 6. 95 – 7. 65 (18H, Ar-H ) 8. 98(1H, CH=N), 11. 50(1H, O-H).

Fig .(1) FT-IR Spectrum for Comp. (I)

Fig .(2) FT-IR Spectrum for Comp. ( Ia)

Fig .(3) FT-IR Spectrum for Comp. ( Ib)

Fig .(4) FT-IR Spectrum for Comp. ( Ic)

Fig .(5) FT-IR Spectrum for Comp. ( Ia1)

Fig. (6) FT-IR Spectrum for Comp.(Ib1)

Fig .(7) FT-IR Spectrum for Comp. ( Ic1)

Fig .(8) FT-IR Spectrum for Comp. ( Ia₂)

Fig .(9) FT-IR Spectrum for Comp. ( Ib₂)

Fig .(10) FT-IR Spectrum for Comp. ( Ic₂)

Fig .(11) FT-IR Spectrum for Comp. ( Ia₃)

Fig .(12) FT-IR Spectrum for Comp. ( Ib₃)

Fig .(13) FT-IR Spectrum for Comp. ( Ic₃)

Fig .(14) 1H-NMR Spectrum for Comp. ( Ib)

Fig .(15) 1H-NMR Spectrum for Comp. ( Ic)

Fig . (16) 1H-NMR Spectrum for Comp. ( Ic₁)

Fig . (17) 1H-NMR Spectrum for Comp. ( Ic₃)

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