International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013 Available online at http://www.ijsrpub.

com/ijsrk ISSN: 2322-4541; 2013 IJSRPUB http://dx.doi.org/10.12983/ijsrk-2013-p580-596

Full Length Research Paper Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solvent-free Conditions
Ganesamoorthy Thirunarayanan
Department of Chemistry, Annamalai University, Annamalainagar-608002, India; Email: drgtnarayanan@gmail.com
Received 17 October 2013; Accepted 21 November 2013

Abstract. Present study describes the efficient synthesis of some unsaturated 1,3-oxazine-2-amines including thirteen 4-(6methoxy-2-naphthyl)-5,6-dihydro-6(substituted phenyl)-4H-1,3-oxazine-2-amines by KF/Al2O3 catalysed solvent-free cyclization of enones with urea under microwave irradiation. The yields of the synthesized oxazines are more than 85%. The catalytic activity of this catalyst was studied by increasing the catalyst quantity from 0.05 to 0.25g in the step-wise cyclization of chalcone and urea. The optimum quantity of the catalyst for this cyclization will be found to be 0.2 g. The effect of solvent on the cyclization reaction was studied with conventional heating method and microwave irradiation technique. Comparatively, the microwave assisted solvent-free method gave more yields of the product. In this study, the effect of substituents also studied. The electron donating substituted chalcones gave more yield than electron-withdrawing substituted chalcones. This synthetic methodoly offers easy work-up procedure, non-hazardousness, shorter reaction time, environmentally benign reaction and better yield. The physical constants, analytical and spectroscopic data are supported for establishment of their structure. Key words: Unsaturated 1,3-oxazine-2-amines; ,-Unsaturated ketones; KF/Al2O3; Environmentally benign reaction; IR and NMR spectra

1. INTRODUCTION The unsaturated 1,3-oxazine-2-amine and their derivatives are an important six membered heterocyclics possess one nitrogen, oxygen atom, one double bond and the amine group bonded in 2nd position carbon from oxygen (Banarjee et al., 2009;Yakovlev et al., 1994; Jacob et al., 1986). These oxazines are exists more than ten isomeric structures depend upon the relative position of unsaturation and the hetero atoms (Manjula et al., 2009). These isomeric structural moieties are important for their biological activities such as antimicrobial, antiplasmodial (Mathew et al., 2010), anti-cancer (Elarfi and Al-Difar, 2012), anti-depressants (Tiwari et al., 2011), cytotoxicity(Das et al., 2009), antiosteoplastic(Zhou et al., 2006), anti-tumour (Wang et al., 2008), anti-oxidant(Ando et al., 2006), antituberculosis (Benameur et al., 1996), anti-neoplastic (Roy et al., 2009), antagonists (Blaser et al., 2012), anti-inflammatory(Seal et al., 1997), anti-infectants (brudli et al., 2010), IKB kinase beta (Akhter et al., 2011) and PTP-1B inhibition (Gothi et al., 2011). These oxazine derivatives were applied for improving the super resolution microscope (Oh et al., 2010), synthesis of eosinophils (Cho et al., 2006), identification and separation of neutrophils (Lee et al., 2013). Many oxazine derivatives were used as dyes (Kass, 1995a). Numerous solvent assisted and solvent-free

synthetic methods were available for the synthesis of oxazine derivatives (Kass, 1995b). Currently, scientists, organic chemists are interested for solventfree synthesis (Verma et al., 2013; Jung et al., 2006; MaMillan and Washburne, 2013; Thirunarayanan and Sekar, 2013;) due to non-hazardousness, easy work-up procedure, shorter reaction time and high yields. Hetero Diels-alder reaction (Manjula et al., 2009), ring closure reaction (Khalilzadeh et al., 2009), Betti base induced condensation (Verma et al., 2013), Mannich type condensation-cyclization (Jacob et al., 1986) and cyclization of chalcones (Elarfi and AlDifar, 2012) were used for the synthesis of oxazine derivatives. Verma et al. (2013) have synthesised some benzoxazine/oxazine fused isoquinolines and naphthyridines by solvent-free method. Elarfi and Aldifar (2012) have synthesised some 1, 3-oxazine derivatives by solvent-assisted method from chalcones and urea. Using eco-friendly method, more than 75% yield of dihydro-2H-benzo- and naphtho-1, 3-oxazine derivatives were prepared by Mathew et al. (2010). Efficient synthesis of some 1, 3-oxazine-4-thiones by N-methylimidazole promoted solvent-free method was reported by Khalilzadeh et al. (2009). Sapkal et al., have studied the role of ammonium acetate for solvent-free synthesis of 1,3-disubstituted-2,3dihydro-1H-naphyl oxazines (Sapkal et al., 2009; Turgut et al., 2007). Within the above view, there is no information available in the literature for the KF/Al2O3 catalyzed

580

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solventfree Conditions

solvent-free synthesis of unsaturated 1,3-oxazine-2amines including 4-(6-methoxy-2-naphthyl)-5,6dihydro-4H-1,3-oxazine-2-amines. Therefore the author have taken effort to synthesize 1,3-oxazine-2amines including 4-(6-methoxy-2-naphthyl)-5,6dihydro-4H-1,3-oxazine-2-amines and recorded their infrared and NMR spectra for establishing the structure. 2. MATERIALS AND METHODS 2.1. General All chemicals were used in this study were purchased from Sigma-Aldrich and Merck Chemical companies. Mettler FP51 melting point apparatus was used for determining the melting point of all synthesized oxazines in open glass capillaries and is uncorrected. The AVATAR-300 Fourier transform spectrophotometer was used for recording infrared spectra (KBr, 4000-400 cm-1) of all oxazines in KBr disc. The Bruker AV400 series type NMR spectrometer was utilized for recording NMR spectra

of all oxazine, operating at 400MHz for 1H and100 MHz for 13C spectra in CDCl3 solvent using TMS as internal standard. Mass spectra of all synthesized oxazines were recorded on SHIMADZU mass spectrometer using chemical ionization technique. 2.2. Synthesis of 4-(aryl)-5,6-dihydro-6-(substituted phenyl)-4H-1,3-oxazine-2-amines An appropriate equi-molar quantities of chalcones (2 mmol), urea (2mmol) and 0.2 g of KF/Al2O3 were taken in a 50 mL beaker, closed with the lid. This mixture was subjected to microwave irradiation for 24 minutes at 650W (Scheme 1) (Samsung, Microwave Oven, 100-700W). After completion of the reaction, dichloromethane (20 mL) was added, followed by simple filtration. The solution was concentrated and the obtained solid was purified by re-crystallization with ethanol. The synthesized oxazines were characterized by their physical constants, IR, 1H and 13 C NMR and Mass spectral data (See Appendix-1 for IR, 1H NMR and Mass spectra of selective compounds).

Scheme 1: Synthesis of 4-aryl-5,6-dihydro-6-(substituted phenyl)-4H-1,3-oxazine-2-amines by KF/Al2O3 catalyzed cyclization of aryl chalcones and urea under microwave irradiation.

3. RESULTS AND DISCUSSIONS Attempts made for synthesis of oxazine derivatives by cyclization of chalcones possess electron withdrawing as well as electron donating substituents, urea and in the presence of catalyst KF/Al2O3 under microwave irradiation. Hence the author have

synthesized some substituted 1,3-oxazine derivatives by the cyclization of 2 mmole of chalcone, 2 mmole of urea under microwave irradiation with 0.2g of KF/Al2O3 catalyst at 550W for 4-6 minutes (Samsung Grill, GW73BD Microwave oven, 230V A/c, 50Hz, 2450Hz, 100-750W (IEC-705), (Scheme 1). During the course of this reaction KF/Al2O3 catalyzes

581

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

cyclization between chalcone and urea followed by rearrangement gave the 1, 3-oxazine-2-amines. The yield of the oxazine in this reaction is more than 80%. The chalcone containing electron donating substituent (OCH3) gave higher yields than electron-withdrawing (halogens, NO2) substituents. Further we have investigated this cyclization reaction with equi-molar quantities of the styryl 6-methoxy-2-naphthyl ketone (entry 11) and urea under the same condition as above. In this reaction the obtained yield was 90%. The effect of catalyst on this reaction was studied by varying the catalyst quantity from 0.05 g to 0.25 g. As the catalyst quantity is increased from 0.05 to 0.25 g, the percentage of yield of product is increased from 84 to 90%. Further increase in the catalyst amount beyond 0.2 g, there is no significant increase in the percentage of

the product. The effect of catalyst loading is shown in Fig. 1. The optimum quantity of catalyst loading was found to be 0.2 g. The results, analytical and mass spectral data are summarized in Table 1 (See Appendix-1 for IR, 1H NMR and Mass spectra of selective compounds). The effect of solvents on the yield was also studied with methanol, ethanol, dichloromethane and tetrahydrofuran from each component of the catalyst (entry 11). Similarly the effect of microwave irradiation was studied on each component of the catalyst. The effect of solvents on the yield of oxazines derivatives was presented in Table 2. From the table, highest yield of oxazines obtained from the cyclization of chalcone and urea with the catalyst KF/Al2O3 in microwave irradiation. The infrared and nmr spectroscopic data of selective 1,3-oxazine-2-amines are summarized in Table 3.

Fig. 1: The effect of catalyst loading

582

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solvent-free Conditions Table 1: Analytical, physical constants, yield and mass fragment of 4-aryl-5,6-dihydro-6(substituted phenyl)-4H-1,3-oxazine-2-amines
Entry R R M.W. Yield (%) 83 m.p.(C) Mass (m/z) 252[M+], 236, 175, 160, 84, 77, 43, 42, 16

252

134-136

HO

268

80

144-145 (145-146)[6]

268[M+], 252, 251, 236, 175, 160, 99, 93, 84, 77,43, 42, 16

CH3 N CH3

295

82

65-66 (65-66)[6]

295[M+], 280, 265, 279, 251, 236, 175, 160, 118, 84, 77, 44, 43, 42, 30, 16, 15

OCH3

282

80

122-123

282[M+], 266, 251, 236, 205, 190, 175, 160, 107, 91, 84, 77, 43, 42, 31, 16

288

84

115-116

286[M+], 288[M2+], 270, 266, 251, 175, 160, 111, 107, 99, 84, 77, 43, 42, 35, 16

Cl
6 282 88 132-133 282[M+], 266, 251, 256, 236, 205, 190, 175, 160, 107, 91, 84, 77, 43, 42, 31, 16

H3CO

583

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

266

86

112-113

266[M+], 251, 250, 175, 160, 91, 84, 77, 43, 42, 31, 16, 15

H3C
8 297 84 141-142 297[M+], 281, 251, 175, 168, 160, 122, 84, 77, 45, 43, 42, 16

O2N
9 302 87 98-99 302[M+], 286, 225, 210, 159, 127, 99, 84, 77, 52, 43, 42, 16

10

302

86

109-110

302[M+], 286, 320, 301, 278,259, 225, 175,161, 127, 99, 91, 84, 77, 52, 43, 42, 35,16

11

332

90

106-107

332[M], 317, 316, 305, 255,225, 210, 175, 168, 157, 124, 99, 91, 84, 77, 59, 43, 42, 31, 16,15,

H3CO
12

NH2

347

85

114-115

347[M+], 331, 316, 255, 198, 190, 175, 168, 157, 134, 92, 91, 77, 43, 42, 31, 16, 15,

H3CO

584

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solvent-free Conditions
13 347 85 117-119 347[M+], 331, 255, 198, 175, 168, 157, 92, 91, 77, 43, 42, 31, 16, 15,

NH2

H3CO
14

Br

411

87

128-129

411[M+], 413[M2+], 331, 316, 255, 240, 210, 157, 154, 91, 84, 77, 43, 42, 31, 16, 15

H3CO
15

Cl

366

88

116-117

366[M+], 368[M2+], 335, 331, 278, 255, 209, 182,168, 157, 154, 127, 111, 99, 91, 77, 58, 35, 31, 16, 15

H3CO
16 366 89 122-123 366[M+], 368[M2+], 335, 331, 278, 255, 182,168, 157, 127, 111, 91, 77, 58, 43, 42, 35, 31, 16, 15

Cl

H3CO
17

CH3 N
H3CO

375

91

137-138

375[M+], 360, 359, 345, 344, 331, 255, 218, 203, 161, 157, 120, 99, 91, 77, 44, 43, 42, 31, 30,16, 15,

CH3
348 86 112-113 348[M+], 332, 331, 317, 255, 191, 157, 127, 99, 93, 91, 77, 58, 42, 31, 17, 16, 15,

18

OH

H3CO

585

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

19

362

91

148-149

362[M+], 347, 331, 304, 255, 205, 198, 164, 157, 107, 93, 91, 77, 58, 43, 42, 31, 16,15,

OCH3

H3CO
20 346 90 118-119 346[M+], 331, 330, 315, 255, 189, 157, 15, 99, 93, 91, 77, 58, 43, 42, 31, 16, 15,

CH3

H3CO
21

O2N

377

87

135-136

377[M+], 361, 346, 331, 319, 255, 220, 212, 205, 198, 179, 165, 157, 122, 91, 84, 77, 58, 46, 43, 41, 31, 16, 15

H3CO
22

NO2

377

84

125-126

377[M+], 361, 346, 331, 319, 255, 220, 205, 198, 165, 157, 91, 84, 77, 46, 43, 41, 31, 16, 15,

H3CO
23 377 85 128-129 377[M+], 361, 331, 319, 255, 220, 212, 198, 179, 165, 157, 91, 84, 77, 58, 43, 41, 31, 16, 15

NO2

H3CO

586

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solventfree Conditions Table 2: The effect of solvents in conventional heating and without solvent in microwave irradiation on yield of oxazine amine (entry 11).
Solvents MeOH 59 EtOH 62 DCM 60 THF 68 90 MW

MeOH=Methanol; EtOH=Ethanol; DCM= Dichloromethane; THF=Tetrahydrofuran; MW=Microwave

4. CONCLUSIONS Some unsaturated 1,3-oxazine-2-amine derivatives including 4-(6-methoxy-2-naphthyl)-5,6-dihydro-6(substituted phenyl)-4H-1,3-oxazine-2-amines have been synthesized by solvent free cyclization of aryl chalcone and urea in presence of KF/Al2O3 catalyst under microwave irradiation. This synthetic methodology offers solvent-free cyclization, nonhazardous, shorter reaction time, easy-workup procedure and better yields. The analytical and spectral data were supported for these oxazines derivatives. ACKNOWLEDGEMENT The author thank to DST NMR facility, Department of Chemistry, Annamalai University, Annamalainagar-608 002, India for recording NMR spectral of compounds. REFERENCES Akhter M, Husain A, Akhter N, Khan MSY (2011). Synthesis, antiinflammatory and antimicrobial activity of some new 1-(3-Phenyl-3,4-Dihydro2H-1,3-Benzoxazin-6-yl)-ethanone derivatives. Indian J. Pharm. Sci., 73: 101-104. Ando Y, Ando K, Yamaguchi M, Kunitomo J, Koida M, Fukuyama R (2006). A novel oxazine ring closure reaction affording (Z)-((E)-2styrylbenzo[b]furo[3,2-d][1,3]oxazin-4ylideno)acetaldehydes and their antiosteoclastic bone resorption activity. Bioorg. Med. Chem. Lett., 16(22): 5849-5854. Banerjee A, Ganguly S, Chattopadhyay T, Banu K S, Patra A, Bhattacharya S, Zangrando E, Das D (2009). Metal-assisted oxazolidine/oxazine ring formation in dinuclear zinc(II) complexes: synthesis, structural aspects, and bioactivity. Inorg Chem., 48(18): 8695-8702. Blaser A, Palmer BD, Sutherland HS, Kmentova I, Franzblau SG, Wan B (2012). Structure-activity relationships for amide-, carbamate-, and urealinked analogues of the tuberculosis drug (6S)2-nitro-6-{[4-(trifluoromethoxy)benzyl]oxy}-

6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine. J. Med. Chem., 55(1): 312-326. Benameur L, Bouaziz Z, Nebois P, Bartoli MH, Boitard M, Fillion H (1996). Synthesis of furonaphth[1,3]oxazine and furo[1,3]oxazinoquinoline derivatives as precursors for an o-quinonemethide structure and potential antitumor agents. Chem. Pharm. Bull. (Tokyo), 44(3): 605-608. Brudeli B, Moltzau LR, Andressen KW, Krobert KA, Klaveness J, Levy FO (2010). Synthesis and pharmacological properties of novel hydrophilic 5-HT4 receptor antagonists. Bioorg. Med. Chem., 18(24): 8600-8613. Cho SY, Baek JY, Han SS, Kang S K, Ha JD, Ahn JH (2006). PTP-1B inhibitors: cyclopenta[d][1,2]oxazine derivatives. Bioorg. Med. Chem. Lett., 16 (3):499-502. Das BC, Madhukumar AV, Anguiano J, Mani S (2009). Design, synthesis and biological evaluation of 2H-benzo[b][1,4] oxazine derivatives as hypoxia targeted compounds for cancer therapeutics. Bioorg. Med. Chem. Lett., 19(15): 4204-4206. Elarfi MJ, Al-Difar HA (2012). Synthesis of some heterocyclic compounds derived from chalcones. Sci. Rev. Chem. Communn., 2(2): 103-107. Gothi D, Joshi JM (2011). Resistant TB: Newer Drugs and Community Approach. Recent Pat Antiinfect Drug Discov., 6(1): 27-37. Jacob P, Benowitz NL, Yu L, Shulgin AT (1986). Determination of nicotine N-oxide by gas chromatography following thermal conversion to 2-methyl-6-(3-pyridyl)tetrahydro-1,2oxazine. Anal. Chem., 58(11): 2218-2221. Jung C, Mller BK, Lamb D C, Nolde F, Mllen K, Bruchle C (2006). A new photostable terrylene diimide dye for applications in single molecule studies and membrane labeling. J. Am. Chem. Soc., 128(15): 5283-5291. Kass L (1995a). A selective stain for eosinophils using two oxazine dyes applied sequentially. Biotech Histochem., 70(1): 19-23. Kass L (1995b). Identification of neutrophils with an oxazine dye. Biotech Histochem., 70(1):29-33.

587

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

Khalilzadeh MA, Yavari I, Hossaini Z, Sadeghifar H (2009). N-Methylimidazole promoted efficient synthesis of 1,3-oxazine-4-thiones under solvent-free conditions. Monatsch Chem., 140: 467-471. Lee S F, Vrolet Q, Frstenberg A (2013). Improved Super-Resolution Microscopy with Oxazine Fluorophores in Heavy Water. Angew. Chem. Inter. Ed., 52(34): 89488951. MacMillan JH, Washburne SS (2013). Detailed Synthetic Procedure for 4-(4-bromophenyl)1,3(3H) Oxazine-2,6-Dione and related 4 and 5aryl substituted -1,3(3H) Oxazine-2,6-Diones. Spectroscopic and analytical data are included. Temple University, http://www.archive.org. Manjula MK, Rai KML, Gaonkar SL, Raveesha KA, Satish S (2009). Synthesis of new series of 5,6dihydro-4H-1,2-oxazines via hetero Deils-Alder reaction and evaluation of antimicrobial activity. Eur. J. Med. Chem., 44: 280-288. Mathew B P, Kumar A, Sharma S, Shukla P K, Nath M (2010). An eco-friendly synthesis and antimicrobial activities of dihydro-2H-benzoand naphtho-1,3-oxazine derivatives. Eur. J. Med. Chem., 45: 502-1507. Oh K S, Lee S, Choi J K, Lee B H (2010) Identification of novel scaffolds for IB kinase beta inhibitor via a high-throughput screening TR-FRET assay. Comb. Chem. High. Throughput Screen., 13(9):790-797. Roy K, Mitra I, Saha A (2009). Molecular shape analysis of antioxidant and squalene synthase inhibitory activities of aromatic tetrahydro-1,4oxazine derivatives. Chem. Biol. Drug. Des., 74(5): 507-516. Sapkal S B, Shelke K F, Kategaonkar AH, Shingare MS (2009). Dual role of ammonium acetate for solvent-free synthesis of 1,3-disubstituted-2,3dihydro-1H-naphth-[1,2e][1,3]-oxazine. Green Chem. Lett., 2(2): 57-60. Seal L, Von Hoff D, Lawrence R, Izbicka E, Jamison RM (1997). An in vitro assessment of the antineoplastic potential of 2H-1,3-oxazine2,6(3H)-dione (3-oxauracil), a novel

pyrimidine. Invest. New Drugs., 15(4) : 289293. Thirunarayanan G, Mayavel P, Thirumurthy K (2012). Fly-ash:H2SO4 catalyzed solvent free efficient synthesis of some aryl chalcones under microwave irradiation. Spectrochim. Acta., 91A:18-22. Thirunarayanan G, Sekar KG (2013). Solvent-free Synthesis and Spectral Studies of Some 9Anthryl-1H-Pyrazolines International Journal of Scientific Research in Knowledge (IJSRK)., 1(8), 305-313, Tiwari V, Meshram J, Ali P, Sheikh J (2011). Tripathi U Novel oxazine skeletons as potential antiplasmodial active ingredients: Synthesis, in vitro and in vivo biology of some oxazine entities produced via cyclization of novel chalcone intermediates. J. Enzyme Inhib. Med. Chem., 26(4): 569-78. Turgut Z, Pelit E, Koycil A (2007) synthesis of new 1,3-disubstituted-2,3-dihydro-1H-naphth[1,2e][1,3]oxazines. Molecules., 12: 345-352. Verma A K, Chioudhary D, Saunthwal RK, Rustagi V, Patel M, Tiwari RK (2013). On Water: Silver-catalyzed domino approach for the synthesis of Benzoxazine/Oxazine fused isoquinolines and naphthyridines from oalkenyl aldehydes. J. Org. Chem., 78(13): 6657-6669. Wang S, Li Y, Liu Y, Lu A, You Q (2008). Novel hexacyclic camptothecin derivatives. Part 1: synthesis and cytotoxicity of camptothecins with an A-ring fused 1,3-oxazine ring. Bioorg. Med. Chem. Lett., 18(14): 4095-4097. Yakovlev IP, Prepyalov AV, Ivin BA (1994). Unsaturated 4H-1,3-Oxazines (Review). Chem. Heterocycl. Compd., 30(3):255-271. Zhou D, Harrison BL, Shah U, Andree TH, Hornby GA, Scerni R (2006). Studies toward the discovery of the next generation of antidepressants. Part 5: 3,4-Dihydro-2Hbenzo[1,4]oxazine derivatives with dual 5HT1A receptor and serotonin transporter affinity. Bioorg. Med. Chem. Lett., 16(5): 1338-1341.

588

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solvent-free Conditions Table 3: Infrared and NMR spectroscopic data of 4-aryl-5,6-dihydro-6(substituted phenyl)-4H-1,3-oxazine-2-amines
Entry IR(, cm-1) NH C=N 3534 3564 3526 3514 3536 3525 3535 3558 3523 3526 3553 3545 3532 3543 3540 3545 3540 3553 3538 3544 3559 3555 3555 1598 1628 1614 1610 1599 1621 1597 1624 1589 1598 1592 1592 1598 1606 1592 1618 1602 1589 1634 1623 1622 1615 1634
1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

NH (s) 2.345 2.295 2.214 2.361 2.173 2.277 2.187 2.317 2.295 2.291 2.234 2.114 2.123 2.223 2.121 2.124 2.034 2.223 2.242 2.219 2.334 2.324 2.190

H(, ppm) H4 H5 (dd) (dd) 2.625 2.425 2.598 2.491 2.412 2.918 2.753 2.811 2.897 2.384 2.301 2.354 2.243 2.253 2.222 2.246 2.229 2.248 2.365 2.246 2.236 2.232 2.234 2.214 2.465 2.458 2.542 2.350 2.299 2.246 2.436 2.201 2.221 2.212 2.224 2.215 2.276 2.264 2.334 2.378 2.398 2.338 2.259 2.334 2.367 2.334

13

H5 (dd) 2.214 2.201 2.269 2.230 2.113 2.217 2.176 2.223 2.236 2.245 2.267 2.329 2.321 2.043 2.034 2.156 2.138 2.164 2.126 2.136 2.121 2.178 2.032

H6 (dd) 4.257 4.351 4.451 4.652 4.714 4.593 4.669 4.709 4.652 4.252 4.238 4.667 4.667 4.646 4.623 4.787 4.769 4.236 4.334 4.483 4.667 4.630 4.633

Ar-H (m) 6.545-7.345 6.289-7.258 6.358-7.298 6.257-7.987 7.174-7.291 6.781-7.352 6.956-7.378 7.273-8.165 6.259-7.962 6.325-7.852 6.332-7.834 6.554-7.933 6.514-7.921 6.723-7.734 6.865-7.834 6.646-7.987 6.638-7.978 6.672-7.878 6.848-7.968 6.296-7.869 6.822-7.534 6.862-7.588 6.526-7.993

Substt. ----3.658 (s, NMe2) 4.023 (s, CH3) --3.997 (s,OCH3) 2.536 (CH3) --------4.867 (s, NH2) 4.886 (NH2) ----3.746 3.723 ((s, NMe2) --4.247 (s,OCH3) 2.39 (CH3) -------

C2 165.33 164.82 164.35 164.03 164.17 163.21 164.90 165.23 164.99 165.02 165.67 165.46 165.25 164.15 165.35 164.89 164.89 165.87 164.48 164.98 165.62 165.40 165.35

C4 52.56 51.36 52.36 52.28 52.07 52.19 52.76 52.78 51.36 52.01 52.98 52.72 52.28 52.34 52.42 52.50 52.78 52.36 52.47 52.51 52.34 52.33 52.83

C(, ppm) C5 C6 47.33 47.98 47.01 48.74 47.95 47.94 47.17 48.26 47.29 48.02 47.54 47.26 47.26 47.65 47.63 47.23 47.12 47.46 47.24 47.13 47.86 47.86 48.24 65.90 66.25 65.98 65.39 67.03 66.79 66.84 67.25 66.25 66.36 66.56 67.36 67.33 67.76 66.65 66.46 67.48 66.76 66.87 66.34 66.67 66.78 66.30

Ar-C 125.36-142.25 126.25-139.38 122.68-139.25 121.36-141.25 126.43-139.40 114.54-137.36 125.77-139.04 126.37-142.10 124.37-146.02 125.36-146.28 121.11-139.34 121.76-138.65 121.80-139.43 121.34-141.23 118.75-139.76 118.35-139.67 121.87-141.56 118.34-139.76 115.76-158.65 114.34-148.98 115.51-159.34 115.74-159.98 116.49-157.98

Substt. ----44.38 NMe2 62.38 (OCH3) --56.78 (OCH3) 25.37 (CH3) ------------------45.33 NMe2 --59.44 (OCH3) 24.89 (CH3) -------

589

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

Appendix-1

IR spectrum of compound 11

IR spectrum of compound 14

IR spectra of compound 16 590

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solventfree Conditions

IR spectra of compound 19

IR spectra of compound 23

Mass spectra of compound 11 591

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

Mass spectra of compound 14

Mass spectra of compound 16

Mass spectra of compound 19 592

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solventfree Conditions

Mass spectra of compound 23

H NMR spectrum of compound 11

593

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

H NMR spectrum of compound 14

H NMR spectrum of compound 16

594

Thirunarayanan Aryl , -Unsaturated Ketones as Efficient Precursor for Synthesis of Unsaturated 1,3-oxazine-2-amines under Solventfree Conditions

H NMR spectrum of compound 19

H NMR Spectrum of compound 23

595

International Journal of Scientific Research in Knowledge (IJSRK), 1(12), pp. 580-596, 2013

Dr. G. Thirunarayanan has completed his M.Sc., degree in chemistry with first class in Bharathidasan University, Tiruchirappalli-620 024, India. The M.Phil., and Ph.D., research degrees were persued at Annamalai University, Annamalainagar-608 002, India in the field of Physical Organic Chemistry in 1997 and 1999 respectively. His primary area of research is Synthesis, Green synthesis, Catalysis, Spectral LFER studies, Redox LFER, biological activities of Chalcone and their derivatives. At present Dr. G. Thirunarayanan is a Faculty Member as Assistant Professor of Chemistry at Annamalai University. He has published more than 80 research articles in reputed and refereed national and international journals.

596