Thesis-Final 03 June 2011 pdf - Jacobs University

More documents

Recommendations

Info

Results and discussion Chapter 3 are as expected due to the Karplus relationship which describes the dependence between 3 J HCCH coupling constants and the dihedral angle between the two coupling protons. Values of 3 J HCCH coupling constants between two equatorial protons are observed between 4 and 5.5 Hz (eg. H-4 and H-5 or H-5 and H-6 eq ). The values of 3 J HCCH between equatorial and axial protons are found to be very small due to a dihedral angle close to 90 0 . <strong>Final</strong>ly the values of 3 J HCCH between two axial protons are found to be very large (eg 11.7 Hz for the coupling pair H-3 and H-2 ax ) because of a dihedral angle close to 180 0 . 8 16 24 32 40 48 56 64 72 80 F1 Chemical Shift (ppm) 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 F2 Chemical Shift (ppm) Figure 37: 1 H 13 C-HMQC of Quinide, (51) The stereochemical relationship between all protons was also confirmed by 1 H 1 H- NOESY spectroscopy. Most characteristically the two axial protons H-6 ax and H-2 ax show a strong NOE effect between them. All further NOE effects observed are in full agreement with the structure. The 13 C-NMR shows seven signals as expected. The carbonyl carbon is found at 179.77 ppm as expected, and C-1 and C-5 are to be found at 72.51 and 77.46 ppm respectively. The 1 H 13 C-HMQC spectrum allows unambigious identification and assignment of C-4 at 66.79 ppm, C-3 at 64.96 ppm, C- 6 at 37.74 ppm and C-2 at 36.35 ppm. The infrared spectrum shows absorptions for the carbonyl ester and the OH groups as expected. The mass spectrum shows the molecular ion and a series of fragment ions corresponding to dehydrated fragments of the quinic acid ester (lactone). 60
Results and discussion Chapter 3 Synthesis of 3, 4-isopropiylidene quinide (Quinide acetal), (45)-p183 Scheme 6: Quinide acetal formed by common acetalisation The quinide acetal was produced by thermodynamic acetalisation of quinic acid. The acetalisation was accomplished by refluxing quinic acid, p-toluenesulfonic acid, 2,2-dimethoxy propane (DMP) and acetone for 2 hours providing the shown compound in 76-90 % yield. The crystals were suitable for single crystal X-ray diffraction and could be obtained from EtOAc-PE (25:4) solvent combination.The compound was first described and synthesized by Sefkow. 310 The crystal data and structure of the product are given below and have not been reported in the literature yet. The structure was solved by Dr. M. Dickman in the laboratory of Prof. U. Kortz. Figure 38: Crystal structure of the quinide acetal 61
Page 1 and 2:
Synthesis of Chlorogenic Acids & Ch
Page 3 and 4:
“Imagination is more important th
Page 5 and 6:
Abbreviations Ac Ac 2 O AcOH MeCN C
Page 7 and 8:
CONTENT Chapter 1 vi
Page 9 and 10:
Content Chapter 1 Preparation of ac
Page 11 and 12:
Content Chapter 1 (1S, 3R, 4R, 5R)-
Page 13 and 14:
Background Chapter 2 Phenolic Phyto
Page 15 and 16:
Background Chapter 2 Types of polyp
Page 17 and 18:
Background Chapter 2 Stilbenes cont
Page 19 and 20:
Background Chapter 2 Biosynthesis o
Page 21 and 22: Background Chapter 2 Biological act
Page 23 and 24: Background Chapter 2 terpenoids, to
Page 25 and 26: Background Chapter 2 Table 2: Bioav
Page 27 and 28: Background Chapter 2 These well kno
Page 29 and 30: Background Chapter 2 Hydroxycinnami
Page 31 and 32: Background Chapter 2 small amounts
Page 33 and 34: Background Chapter 2 Cinnamate tran
Page 35 and 36: Background Chapter 2 used in the is
Page 37 and 38: Background Chapter 2 acid is implic
Page 39 and 40: Background Chapter 2 Chlorogenic ac
Page 41 and 42: Background Chapter 2 HO O HO OH C O
Page 43 and 44: Background Chapter 2 acyl migration
Page 45 and 46: Background Chapter 2 Reported Synth
Page 47 and 48: Background Chapter 2 1-O-Cinnamoylq
Page 49 and 50: Background Chapter 2 O O O H + CinO
Page 51 and 52: Background Chapter 2 chloride gave
Page 53 and 54: Background Chapter 2 Synthesis of 1
Page 55 and 56: Background Chapter 2 Esterification
Page 57 and 58: Background Chapter 2 Synthesis of 3
Page 59 and 60: Background Chapter 2 Table 5: Chlor
Page 61 and 62: Background Chapter 2 roasting degre
Page 63 and 64: Aims and objectives As described ch
Page 65 and 66: Results and discussion Chapter 3 Pr
Page 67 and 68: Results and discussion Chapter 3 co
Page 69 and 70: Results and discussion Chapter 3 Pr
Page 71: Results and discussion Chapter 3 1.
Page 75 and 76: Results and discussion Chapter 3 Ta
Page 77 and 78: Results and discussion Chapter 3 Fi
Page 79 and 80: Results and discussion Chapter 3 Sy
Page 85 and 86: Results and discussion Chapter 3 Th
Page 87 and 88: Results and discussion Chapter 3 an
Page 89 and 90: Results and discussion Chapter 3 20
Page 93 and 94: Results and discussion Chapter 3 Ta
Page 97 and 98: Results and discussion Chapter 3 Ge
Page 103 and 104: Results and discussion Chapter 3 pp
Page 113 and 114: Results and discussion Chapter 3 ch
Page 123 and 124:
Results and discussion Chapter 3 Sc
Page 125 and 126:
Results and discussion Chapter 3 Th
Page 127 and 128:
Results and discussion Chapter 3 di
Page 129 and 130:
Results and discussion Chapter 3 gr
Page 131 and 132:
Results and discussion Chapter 3 20
Page 133 and 134:
Results and discussion Chapter 3 Sy
Page 135 and 136:
Results and discussion Chapter 3 pp
Page 137 and 138:
Results and discussion Chapter 3 Sc
Page 139 and 140:
Results and discussion Chapter 3 sp
Page 141 and 142:
Results and discussion Chapter 3 ap
Page 143 and 144:
Results and discussion Chapter 3 Fi
Page 145 and 146:
Results and discussion Chapter 3 In
Page 147 and 148:
Page 149 and 150:
Results and discussion Chapter 3 mu
Page 151 and 152:
Page 153 and 154:
Results and discussion Chapter 3 Th
Page 155 and 156:
Page 157 and 158:
Results and discussion Chapter 3 Qu
Page 159 and 160:
Page 161 and 162:
Page 163 and 164:
Results and discussion Chapter 3 In
Page 165 and 166:
Page 167 and 168:
Results and discussion Chapter 3 CH
Page 169 and 170:
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
Results and discussion Chapter 3 Sy
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Results and discussion Chapter 3 Al
Page 183 and 184:
Conclusions Chapter 4 Conclusions A
Page 185 and 186:
Conclusions Chapter 4 Mono-acyl chl
Page 187 and 188:
Conclusions Chapter 4 The products
Page 189 and 190:
Conclusions Chapter 4 Di-acyl chlor
Page 191 and 192:
Conclusions Chapter 4 Poly-acyl chl
Page 193 and 194:
EXPERIMENTAL Chapter 5 181
Page 195 and 196:
Synthesis of starting materials Qui
Page 197 and 198:
Annex Chapter 6 Acetyl ferulic acid
Page 199 and 200:
Annex Chapter 6 3, 4-dimethoxycinna
Page 201 and 202:
Annex Chapter 6 3, 4-O-Isopropylide
Page 203 and 204:
Annex Chapter 6 1-(β, β, β-trich
Page 205 and 206:
Annex Chapter 6 (1S, 3R, 4R, 5R)-1-
Page 207 and 208:
Page 209 and 210:
Page 211 and 212:
Annex Chapter 6 (1R,3R,4S,5R)-1-dim
Page 213 and 214:
Annex Chapter 6 (1R, 3R, 4S, 5R)-1-
Page 215 and 216:
Annex Chapter 6 (1R, 3R, 4S, 5R)-1-
Page 217 and 218:
Annex Chapter 6 5- diacetylcaffeoyl
Page 219 and 220:
Annex Chapter 6 5- acetyl p-coumaro
Page 221 and 222:
Annex Chapter 6 5-cinnamoyl bisacet
Page 223 and 224:
Annex Chapter 6 5-O-feruloylquinic
Page 225 and 226:
Annex Chapter 6 5-O-dimethoxycinnam
Page 227 and 228:
Page 229 and 230:
Annex Chapter 6 (1S,3R,4R,5R)-1-(β
Page 231 and 232:
Annex Chapter 6 (1S,3R,4R,5R)-1-(β
Page 233 and 234:
Page 235 and 236:
Page 237 and 238:
Page 239 and 240:
Annex Chapter 6 (1S,3R,4R,5R) 1- (
Page 241 and 242:
Annex Chapter 6 (1S,3R,4R,5R)-3, 4-
Page 243 and 244:
Annex Chapter 6 (1S,3R,4R,5R)-3,4-b
Page 245 and 246:
Annex Chapter 6 (1S,3R,4R,5R)-1,3-d
Page 247 and 248:
Annex Chapter 6 (1S,3R,4R,5R)-1,3-b
Page 249 and 250:
Annex Chapter 6 (1S,3R,4R,5R)-1,4-d
Page 251 and 252:
Annex Chapter 6 Quinide tri-acetate
Page 253 and 254:
Annex Chapter 6 (1S, 3R, 4R, 5R)-1,
Page 255 and 256:
Page 257 and 258:
Page 259 and 260:
Annex Chapter 6 745 [M+H], 544 [M-C
Page 261 and 262:
Annex Chapter 6 (C-24), 121.95 (C-3
Page 263 and 264:
Annex Chapter 6 (acetylferuloyl) qu
Page 265 and 266:
REFERENCES Chapter 6 253
Page 267 and 268:
References Chapter 6 21 D. Strack,
Page 269 and 270:
References Chapter 6 62 K. Herrmann
Page 271 and 272:
References Chapter 6 104 N. Shibuya
Page 273 and 274:
References Chapter 6 148 B. Möller
Page 275 and 276:
References Chapter 6 187 M. Nardini
Page 277 and 278:
References Chapter 6 221 M. F. Andr
Page 279 and 280:
References Chapter 6 264 L. Panizzi
Page 281:
References Chapter 6 303 J. Hucke,
show all

Thesis-Final 03 June 2011 pdf - Jacobs University

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?