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10 11 Cl Cl N N H N H N N N Cl 4-j (85) N N H N H N N N Cl 4-k (80) 21 22 Cl Cl N N H N N H NH N H N N N N N N S 4-u (91) Br 4-v (80) a All reactions were run on a 0.7 mmol scale of 3 {a-j} ethanol: water (4:1) (1 ml) with phenyl acetylene (1.2 equiv), Cu(OAc)2 (5 mol % ) and hydrazine hydride (2 equiv). The mixture was irradiated in a sealed tube (CEM Discover @ ) at a ceiling temperature of 100 o C and 35 maximum power for the stipulated time. b isolated yields. Yields are shown in (). Table-2: Microwave assisted one pot decoration of 2-AI-T Framework a . A diverse set of 2-AI-T scaffold were synthesized with these optimized conditions. Ten different hydroxy salt 3 {a-j} (n = 1 or 2) were reacted with different (hetero) aromatic or alkyl acetylenes (Table-2) to test the generality of this new microwaveassisted one pot method (Table 2). All reactions were completed within 5 min using microwave irradiation at ceiling temperature of 100 o C and 35W power. The yields varied from good to excellent, although in some cases lower yields were observed (Table 2, No-15,16 and 19). However in case of morpholine substitution (table-2, No- 15-16) probably due to decomposition of starting hydroxy salt 3 {h} lower yields were observed. Interestingly when 4,5-disubstituted hydroxy salt react with acetylene only 16% of desired product 4{s} was observed due to steric hindrance of 4-Mephenyl substitution on dimorth rearrangement. Motivated by the importance of the final target to develop new general method toward widely functionalized 2-AI-T framework, we next examined the extension of this procedure to other acetylene. The reaction proceeded effectively with aliphatic and aromatic terminal acetylenes to give the corresponding 2-AI-T (Table 2). Thus, a variety of substituted 2-AI-T containing aromatic, aliphatic, cyclic and heterocyclic substitution at the C-4 position of the triazole ring were obtained.
4.4 Possible Mechanism Regarding the mechanism of transformation of 2-hydroxy 2,3-dihydro-1Himidazo[1,2-a]pyrimidin-4-ium salts 3 into 2-amino-1H-imidazole-triazole 4, we presume that the reaction proceeds via an unusual Dimroth type rearrangement (Scheme-3). Br Br R 2 N NH 2NH 2 R 2 N N N N3 n R2 N H N OH R1 N H 3 N R 1 Ring Opening N R 1 OH 25 o C n N 3 NH 2NH 2 MW R 2 N Cu(OAc) 2 CuNP NH 2 N N H ·HBr a b N R 1 OH Generation of "nano-Cu" R 3 "Click" Reaction N n N N R 3 Dimroth Rearrangement Scheme-3: Proposed mechanism for One-pot reaction: In the first step the 2-hydroxy-2,3-dihydroimidazo[1,2-a]pyrimidinium salt (3) undergoes cleavage of the pyrimidine ring (a), resulting in the generation of pyrazole and 2-amino-5-hydroxyimidazolidine (b), meanwhile copper nanoparticle 16 generated by reduction of Cu(OAc)2 using 1 equiv of NH2NH2.H2O takes part in click reaction. This intermediate (b), which is in equilibrium with the open form c can cyclize again leading by dehydration upon microwave irradiation, results in the rearranged 2amino-1H-imidazoles triazole (4). R 2 HN R 1 NH 2 O N H 2O N N n N n c 4 N N N R 3 R 3
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Saurashtra University Re - Accredit
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JANUARY-2011 Statement under O. Ph.
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Acknowledgment This thesis arose in
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since I was a child. My Mother Hans
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CHAPTER - 2 Microwave Assisted Synt
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5.5 Results and discussion 156 5.6
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Ms Mesyl MW Microwave NBS N-bromosu
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1. Microwave Assisted Organic Synth
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1.4 Heating Mechanism In microwave
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1.5. Effects of solvents Every solv
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1.7 Application of microwave in org
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aromatic amines, Lancini’s group
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1.9 2-Aminoimidazole Alkaloids The
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Recently group of Erik 83 described
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1.10 Methods for the preparation of
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R 1 O X R 2 NH 2 H 2N NAc R 1 HN R
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this manifold, was reported in 1925
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Another route to 4(5)-acyl-2-amino-
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this series of compounds against th
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documented. Extra care is needed be
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Very recently the research group of
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OH a,b O N H2N N Boc N 3 H N R N N
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1.12.2 Biofilm Growth Cycle 1) Plan
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can survive both the onslaught of a
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[26] Leadbeater, N. E. (2004) Chemi
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[86] Kreutzberger, A. (1962) J. Org
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Microwave Assisted Synthesis & Stru
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2.1 Introduction As described in ch
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2.3 Proposed Mechanism: Regarding t
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No. 12 60 120 traces 84 a All react
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the development of biofilm related
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In first instance, a series of 2-hy
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Br N N N R 1 OH Br N N N R 1 OH Fig
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do have a very strong effect agains
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2.6 Conclusion In the present study
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2.8 Biological assays 2.8.1 Static
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2.9 Experimental protocol: 2.9.1 Ge
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temperature of 80 °C and a maximum
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29.5,29.4, 29.2, 27.0, 22.6, 14.1.
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Yield: 78 %. 1 H NMR (300 MHz, CDCl
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N Br N N C 14H 29 OH Yield: 72 %. 1
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(75.5 MHz, CDCl3): δ = 167.7, 154.
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N Br N N C 14H 29 OH Cl Yield: 90 %
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2-(3,4-Dichlorophenyl)-2-hydroxy-1-
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N Br N N C 8H 17 OH NO 2 Yield: 49
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C3H7 HN N N H Cl Cl Yield : 70 %. 1
Page 95 and 96: (s, 1H), 3.16 (s, 3H), 1.80 (m, 2H)
Page 97 and 98: 5-(4’-Nitrobiphenyl-4-yl)-N-octyl
Page 99 and 100: 2.11 Representative NMR spectra 2.1
Page 101 and 102: 2.11.3 10.4329 0.7429 151.5720 10.0
Page 103 and 104: [21] Matz C, McDougald D, Moreno A.
Page 105 and 106: Chapter-3 Structure Activity Relati
Page 107 and 108: imidazoles, where the addition of a
Page 109 and 110: 3.4 Result and Discussion It was fo
Page 111 and 112: No. H 2N Compound Code N N C8H17 R1
Page 113 and 114: medium used in the set-up to monito
Page 115 and 116: H 2N N N N H2N N R R Figure-1 Effec
Page 117 and 118: 3.5.3 Cyclo-alkyl 2-aminoimidazoles
Page 119 and 120: 3.6. Conclusion In the present stud
Page 121 and 122: 3.8. Experimental protocols 3.8.1 G
Page 123 and 124: 122.6, 54.6, 33.3(×2), 27.3 (×2),
Page 125 and 126: Yield: 52 %. 1 H NMR (300 MHz, CDCl
Page 127 and 128: 5-(4-Chlorophenyl)-1-cyclooctyl-1H-
Page 129 and 130: Yield: 50 %. Mp: 76-78 ° C. 1 H NM
Page 131 and 132: 5-(4-Chlorophenyl)-1-cyclobutyl-1H-
Page 133 and 134: Yield: 66%. 1 H NMR (300 MHz, CDCl3
Page 135 and 136: 3.10 Representative NMR spectra 3.1
Page 137 and 138: 3.11 References [1] (a) Alvi K. A,
Page 139 and 140: Copper Catalyzed Microwave Assisted
Page 141 and 142: 4.1 Introduction There are only a f
Page 143 and 144: (Table-1, No- 6). Next reaction tem
Page 145: No. Product, Yield b (%) No. Produc
Page 149 and 150: 4.7 Experimental protocols 4.7.1 Ge
Page 151 and 152: Yield: 69 %. 1 H NMR (300 MHz, CDCl
Page 153 and 154: 1-(3-Azidopropyl)-2-(3,4-dichloroph
Page 155 and 156: Yield: 84 %. 1 H NMR (300 MHz, DMSO
Page 161 and 162: 1H), 1.66 (m, 6H), 1.70 (m, 2H). 13
Page 163 and 164: 5.48 Hz, 2H), 3.59 (m, 2H), 3.16 (d
Page 165 and 166: 4.10 References [1] For a general r
Page 167 and 168: Crystal and Molecular Structure Ana
Page 169 and 170: 5.1 Introduction The membrane efflu
Page 171 and 172: oscillation range of 5˚ and proces
Page 173 and 174: C12-C13 1.372(4) C32-C37 1.390(3) C
Page 175 and 176: Fig.-3: Packing of the molecules wh
Page 177 and 178: 1 H NMR (400 MHz CDCl3): δ = 7.57-
Page 179 and 180: 5.9.2 13 C spectra of bs-DP-7
Page 181 and 182: SUMMARY The work represented in the
Page 183 and 184: CONFERENCES/SEMINARS/WORKSHOPS ATTE
Page 185: PUBLICATIONS [1] One-Pot Microwave-
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Scheme 2 Competitive formation of 1
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Table 2 continued 9 10 11 12 N hydr
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8. Colson G, Raboult L, Lavelle F,
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