Thesis-Final 03 June 2011 pdf - Jacobs University

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Results and discussion Chapter 3 Quinide was synthesized by heating quinic acid at 220°C for one hour in the absence of solvent. The product was purified by recrystallisation from EtOH. Quinide was obtained in 30% yield by this quinic acid lactonisation. Figure 34 : 1 H NMR of Quinide, (51) All spectroscopic data ( 1 H-NMR, 13 C-NMR, IR and elemental analysis) are in full agreement with the proposed structure. The 1 H-NMR spectrum shows two triplets and one doublet of doublet of doublet at 4.91, 4.16 and 3.87 ppm corresponding to the three protons HCO next to an oxygen atom. Furthermore four signals at 2.48, 2.42, 2.13 and 1.94 ppm correspond to the four non-equivalent protons of the two sets of CH 2 groups. Because of chemical shift considerations the most downfield proton at 4.91 was assigned to H-5, the proton next to the lactone functionality. From the 1 H 1 H- COSY spectrum the signal at 4.16 ppm can be identified as H-4 due to crosspeaks to H-5. The multiplet at 3.87 ppm was consequently assigned as H-3. A cross peak from H-3 to the signals at 2.13 and 1.94 ppm shows that these two signals correspond to the H-2 CH 2 moiety confirmed by their crosspeak. The two H-6 protons are identified at 2.48 and 2.42 ppm. Interestingly a further crosspeak is evident in the 1 H 1 H-COSY spectrum between the two signals at 2.42 ppm and 2.13 ppm due to a 4 J HCCCH long range W-coupling. This automatically identifies the two signals as the two equatorial protons, since such a W-coupling can only occur between two equatorial protons. 58
Results and discussion Chapter 3 1.5 2.0 2.5 3.0 3.5 4.0 4.5 F1 Chemical Shift (ppm) 5.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 F2 Chemical Shift (ppm) Figure 35: 1 H 1 H-COSY -NMR of Quinide, (51) 5.5 Figure 36: 13 C NMR of Quinide, (51) Moreover it is worth noting that the H-6-CH 2 protons are unexpectedly shifted downfield if compared to the H-2 CH 2 protons. The coupling constants in the quinide 59
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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
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
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Results and discussion Chapter 3 Th
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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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Results and discussion Chapter 3 20
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Results and discussion Chapter 3 Sy
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Results and discussion Chapter 3 pp
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Results and discussion Chapter 3 Sc
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Results and discussion Chapter 3 sp
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Results and discussion Chapter 3 ap
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Results and discussion Chapter 3 Fi
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Results and discussion Chapter 3 In
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Results and discussion Chapter 3 mu
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Results and discussion Chapter 3 Qu
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Results and discussion Chapter 3 In
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Results and discussion Chapter 3 CH
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Results and discussion Chapter 3 Sy
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Results and discussion Chapter 3 Al
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Conclusions Chapter 4 Conclusions A
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Conclusions Chapter 4 Mono-acyl chl
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Conclusions Chapter 4 The products
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Conclusions Chapter 4 Di-acyl chlor
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Conclusions Chapter 4 Poly-acyl chl
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EXPERIMENTAL Chapter 5 181
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Synthesis of starting materials Qui
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Annex Chapter 6 Acetyl ferulic acid
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Annex Chapter 6 3, 4-dimethoxycinna
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Annex Chapter 6 3, 4-O-Isopropylide
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Annex Chapter 6 1-(β, β, β-trich
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Annex Chapter 6 (1S, 3R, 4R, 5R)-1-
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Annex Chapter 6 (1R,3R,4S,5R)-1-dim
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Annex Chapter 6 (1R, 3R, 4S, 5R)-1-
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Annex Chapter 6 (1R, 3R, 4S, 5R)-1-
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Annex Chapter 6 5- diacetylcaffeoyl
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Annex Chapter 6 5- acetyl p-coumaro
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Annex Chapter 6 5-cinnamoyl bisacet
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Annex Chapter 6 5-O-feruloylquinic
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Annex Chapter 6 5-O-dimethoxycinnam
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Annex Chapter 6 (1S,3R,4R,5R)-1-(β
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Annex Chapter 6 (1S,3R,4R,5R)-1-(β
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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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