Thesis-Final 03 June 2011 pdf - Jacobs University

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Conclusions Chapter 3 Starting materials Quinide (1L-1 (OH), 3, 4,/5-Tetrahydroxycyclohexane carboxcylic acid) (51) made available by converting quinic acid to quince acid lactone. This product was then used as starting materials for most of the reactions. The method which was used for the synthesis of 3, 4-O-Isopropylidene quinide (45) was established by John C. Rohloff in 1998. The same method used to make 3, 4-O- Isopropylidene quinide (415) in order to use for further synthesis. As a new approach 3, 4-O-Isopropylidene quinic acid, (46) was synthesised by applying 3, 4-O- Isopropylidene quinide (415) in THF/H2O and LiOH suspension at room temperature which was again used for some of the synthesis. Troc protection and removal of protecting group was described by Thomas B. Winholdz and David B.R. Johnson in 1967. The same method was applied for producing Troc protected quinide 1-(β, β, β- trichloroethoxycarbonyl)-3, 4-O-isopropylidene quinide, (47). After removal of acetal group from the structure 1-(β, β, β-trichloroethoxycarbonyl) quinide, (48) was obtained. This compound was used for the synthesis of mono-acyl, di acayl and polyacyl chlorogenic acid and lactone synthesis. The Troc protected quinide at first position has not been reported in the literature yet. First synthesis of bisacetonide in order to make derivates of chlorogenic acids was published by M. Sefkow and his group in 2001. M. Sefkow’s published method was slightly improved by using different quantities and compound was optimised as white crystals at the end of the reaction. Figure 134: Synthesised starting materials 172
Conclusions Chapter 4 Mono-acyl chlorogenic acids Mono-acyl chlorogenic acids synthesis achieved in four different ways by using 3, 4- O-Isopropylidene quinide, Troc protected quinide, bisacetonide and quinide as starting materilas. The products produced from 3, 4-O-Isopropylidene quinide were all pure after the reactions and didn’t require any purification. The products which are synthesised from Troc protecting quinide and quinide needed further purification which was performed by flash chromatography using chloroform /acetone mixture. It was reported that the hydrogen atom in chloroform is capable of hydrogen bonding to a suitable electron donor molecule. Therefore this combination (chloroform /acetone) wouldn’t be a good solvent choice. Surprisingly, it gave very sufficient results for the synthesis of chlorgenic acids purifications. The products produced from 3, 4-O-Isopropylidene quinide at -1 position The synthesised compounds were obtained by acylation of quinide acetal with 1.1 equivalent cinnamoyl chloride by using DMAP in dichloromethane and N, N, N- Triethylamine solution. These esters were stirred in THF/ H 2 O solution to provide corresponding mono-acyl chlorogenic acids. The list of the products synthesised from 3, 4-O-Isopropylidene quinide (45) as shown below; Part I: Figure 135: Synthesised mono-acyl chlorogenic acid lactones leading mono-acyl chlorogenic acids 173
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Synthesis of Chlorogenic Acids & Ch
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“Imagination is more important th
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Abbreviations Ac Ac 2 O AcOH MeCN C
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CONTENT Chapter 1 vi
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Content Chapter 1 Preparation of ac
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Content Chapter 1 (1S, 3R, 4R, 5R)-
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Background Chapter 2 Phenolic Phyto
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Background Chapter 2 Types of polyp
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Background Chapter 2 Stilbenes cont
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Background Chapter 2 Biosynthesis o
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Background Chapter 2 Biological act
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Background Chapter 2 terpenoids, to
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Background Chapter 2 Table 2: Bioav
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Background Chapter 2 These well kno
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Background Chapter 2 Hydroxycinnami
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Background Chapter 2 small amounts
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Background Chapter 2 Cinnamate tran
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Background Chapter 2 used in the is
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Background Chapter 2 acid is implic
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Background Chapter 2 Chlorogenic ac
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Background Chapter 2 HO O HO OH C O
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Background Chapter 2 acyl migration
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Background Chapter 2 Reported Synth
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Background Chapter 2 1-O-Cinnamoylq
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Background Chapter 2 O O O H + CinO
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Background Chapter 2 chloride gave
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Background Chapter 2 Synthesis of 1
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Background Chapter 2 Esterification
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Background Chapter 2 Synthesis of 3
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Background Chapter 2 Table 5: Chlor
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Background Chapter 2 roasting degre
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Aims and objectives As described ch
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Results and discussion Chapter 3 Pr
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Results and discussion Chapter 3 co
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Results and discussion Chapter 3 Pr
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Results and discussion Chapter 3 1.
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Results and discussion Chapter 3 Sy
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Results and discussion Chapter 3 Ta
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Results and discussion Chapter 3 Fi
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Results and discussion Chapter 3 Th
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Results and discussion Chapter 3 an
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Results and discussion Chapter 3 20
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Results and discussion Chapter 3 Ta
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Results and discussion Chapter 3 Ge
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Results and discussion Chapter 3 pp
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Results and discussion Chapter 3 ch
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Results and discussion Chapter 3 Sc
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Results and discussion Chapter 3 di
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Results and discussion Chapter 3 gr
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Page 133 and 134: Results and discussion Chapter 3 Sy
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Page 167 and 168: Results and discussion Chapter 3 CH
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Page 183: Conclusions Chapter 4 Conclusions A
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
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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
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Annex Chapter 6 (1S, 3R, 4R, 5R)-3-
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Annex Chapter 6 (1S, 3R, 4R, 5R)-3-
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Annex Chapter 6 (1S,3R,4R,5R) 1- (
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Annex Chapter 6 (1S,3R,4R,5R)-3, 4-
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Annex Chapter 6 (1S,3R,4R,5R)-3,4-b
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Annex Chapter 6 (1S,3R,4R,5R)-1,3-d
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Annex Chapter 6 (1S,3R,4R,5R)-1,3-b
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Annex Chapter 6 (1S,3R,4R,5R)-1,4-d
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Annex Chapter 6 Quinide tri-acetate
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Annex Chapter 6 (1S, 3R, 4R, 5R)-1,
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Annex Chapter 6 745 [M+H], 544 [M-C
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Annex Chapter 6 (C-24), 121.95 (C-3
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Annex Chapter 6 (acetylferuloyl) qu
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REFERENCES Chapter 6 253
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References Chapter 6 21 D. Strack,
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References Chapter 6 62 K. Herrmann
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References Chapter 6 104 N. Shibuya
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References Chapter 6 148 B. Möller
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References Chapter 6 187 M. Nardini
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References Chapter 6 221 M. F. Andr
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References Chapter 6 264 L. Panizzi
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References Chapter 6 303 J. Hucke,
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