Narcissus and Daffodil

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Synthesis of galanthamine 311 mercially available compound) these authors obtained a 23% yield in three stages, the yield of (±)-1 from 7 (which is commercially available) is 2.14% (30 times higher). Kametani et al. (1969a,b) used the following route for the synthesis of 4-benzyloxyphenylacetic acid (10) (Figure 12.5). 10 was obtained from 7 through the aldehyde 36 and the intermediate imino-propionitrile of structure 37 (Vaghani and Merchant, 1961). However, in this scheme, the total yield of 10 was not indicated, and only half of the starting material was inserted into the target compound. Another component, 2-bromo-4-methoxy-5-benzyloxy-benzaldehyde (29), was obtained in three steps starting from 3,4-dimethoxybenzaldehyde (38) by 3-monodemethylation with concentrated H 2 SO 4 to isovanilline (18) (61%) (Brossi et al., 1967), and bromination with bromine in acetic acid to give the expected compound 39 in 67% yield (Henry and Sharp, 1930; Raiford and Ravely, 1940). The total yield of 29 after O-benzylation was about 33% (Jackson and Martin, 1966), which after total conversion should exceed 54%. Recently, a more advanced route (Figure 12.5) was proposed from isovanilline (18), which after O-benzylation to 12 (98%) and bromination in acetic acid in the presence of NaOAc produced 29 in 79% yield (Bolton et al., 1987), or a total 47% yield (77% taking into consideration a complete conversion of products on the hydrolysis reaction step). Similarly, Kametani et al. (1973) synthesised (±)-1 via (±)-N-norgalanthamine ((±)-44) (Figure 12.6). The substrate for oxidation was obtained in three steps from the acid 30 via the acylchloride 31, coupled with the amine 40 to produce the amide 41, which was debenzylated to 42 in 72% total yield. On K 3 [Fe(CN) 6 ] oxidation, the key compound (±)-43 was obtained in only 0.7% yield. The latter was reduced with LiAlH 4 to (±)-44 in 32% yield. The final formaldehyde-formic acid methylation of (±)-44 produced the desired (±)-1 in 70% yield, corresponding to 0.11% total yield. In another synthesis of (±)-1, Kametani et al. (1971a) used the intermediate isomeric amide 48 (a positional carbonyl isomer of 33). Starting from 4-benzyloxyphenylacetic acid (10) converted to acyl chloride (11), and the bromoamine 46 obtained from bromoaldehyde (29) in two steps without isolation of the intermediate 45 (75%), the desired amide 47 was produced in 72.3% yield (Figure 12.6). After elimination of protective benzyl groups with hydrobromic acid, the resulting dihydroxy-amide 48 was oxidised with K 3 [Fe(CN) 6 ] to afford a tetracyclic amide of structure (±)-49 in low yield (1.9%). A subsequent LiAlH 4 reduction afforded 12.3% of (±)-1 and 4.9% of (±)-4. Thus, the total yield of the title compound according to this scheme was 0.095%, which was 99 times lower than that according to the alternative route via the intermediate 33. The oxidation of unprotected amide 52 (obtained from 28 and 50 via 51) with VOCl 3 produced the expected cyclic compound (±)-53 in 2% yield (Figure 12.7), which was reduced to (±)-1 and (±)-4, with (±)-1 isolated in 61% yield. The 0.77% total yield of the latter is 12 times lower than that shown according to the route in Figure 12.4 with the application of bromo amide (Kametani et al., 1971b; Kametani, 1972b). In another modification of (±)-1 synthesis, Kametani et al. (1972) used the isomeric 2-bromo derivative 54 as a starting material (Figure 12.8). The latter was transformed via 55 (63%) and 56 (86%) into the acid chloride 57, and coupled with the methylamine derivative 28 to give the amide 58 (37%). Hydrochloric acid debenzylation produced diphenol 59 (77%), which on irradiation with a mercury lamp afforded the key compound (±)-53 in only 1% yield. LiAlH 4 reduction as
312 V.N. Bulavka and O.N. Tolkachev PhCH O 2 MeN Br MeO MeO NH2 O O 30 31 O NH O NH MeO Br MeO O Br 43 44 OH 47 48 49 O O HO O HO HO O O NH MeO Br 40 41 42 29 OCH Ph 2 OCH Ph 2 PhCH O 2 PhCH O 2 Br N Me NH Me NH MeO OCH Ph MeO OCH Ph Br 45 46 MeN Br MeO 2 OH MeO Br 2 NMe O 10 11 1 1 + 4 Figure 12.6 Synthesis of galanthamine (1) via N-norgalanthamine (44) (above; Kametani et al., 1973) and via belladine-type phenylacetamide (48) (below; Kametani et al., 1971a).
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Narcissus and Daffodil
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Narcissus and Daffodil The genus Na
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Contents Preface to the series vii
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Preface to the series There is incr
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Preface My interest in flower-bulb
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Acknowledgements I would like to th
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Gordon R. Hanks Crop and Weed Scien
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Figures 1.1 The effect of bulb stor
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Figures/Plates xvii 7.8 Accumulatio
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Figures/Plates of different segment
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2 G.R. Hanks Information about the
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4 G.R. Hanks (1999), and the polysa
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3 2 4 1 1 3 2 4 5 Flowering in 1976
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8 G.R. Hanks Figure 1.6 Diagrammati
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10 G.R. Hanks (Rees, 1969). When fl
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12 G.R. Hanks Figure 1.8 The relati
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14 G.R. Hanks root system of commer
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16 G.R. Hanks Cremer, M.C., Beijer,
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18 G.R. Hanks Roh, S.M. and Lee, J.
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20 A.C. Dweck Figure 2.1 The narcis
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22 A.C. Dweck Julians Hertfordshire
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24 A.C. Dweck Herefordshire, if daf
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26 A.C. Dweck the basis of an ancie
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28 A.C. Dweck Britten, J. and Holla
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3 Classification of the genus Narci
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(1) (2) (3)
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34 B. Mathew d. Section Jonquillae
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36 B. Mathew N. cyclamineus DC. Flo
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38 B. Mathew 1c. Section Ganymedes
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40 B. Mathew umbel, fragrant; peria
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42 B. Mathew recognition whatsoever
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44 B. Mathew Note: N. elegans shows
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46 B. Mathew ssp. praecox Gatt. and
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(1) (2) (3) (4)
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50 B. Mathew Table 3.1 Horticultura
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52 B. Mathew RHS (1958) The Classif
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54 G.R. Hanks grown for galanthamin
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56 G.R. Hanks such as drying stores
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Table 4.4 Areas of Narcissus cultiv
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60 G.R. Hanks Following planting in
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62 G.R. Hanks lost, resulting in th
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64 G.R. Hanks pathogen-tested nucle
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Figure 4.1 Mean monthly weather dat
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68 G.R. Hanks (as well as natural e
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70 G.R. Hanks compaction and its ef
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72 G.R. Hanks bulbs with base rot)
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74 G.R. Hanks Figure 4.3 Modern fro
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76 G.R. Hanks caution. Higher rates
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78 G.R. Hanks can also be prevented
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80 G.R. Hanks Figure 4.4 A typical
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82 G.R. Hanks Planting date The pra
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84 G.R. Hanks Hanks and Jones, 1986
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86 G.R. Hanks On sloping sites, gro
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88 G.R. Hanks Insecticide and nemat
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90 G.R. Hanks bulb growth, especial
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92 G.R. Hanks Figure 4.7 Changes in
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94 G.R. Hanks methods have been tes
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96 G.R. Hanks the boxes, exiting at
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98 G.R. Hanks usually collected in
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100 G.R. Hanks respond to ethylene
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102 G.R. Hanks using thiabendazole
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104 G.R. Hanks required for the eff
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106 G.R. Hanks and cross-cutting, s
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108 G.R. Hanks In practice, moulds
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110 G.R. Hanks that, with enterpris
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112 G.R. Hanks Balatková, V., Tupy
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114 G.R. Hanks (Narcissus pseudonar
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116 G.R. Hanks Flint, G.J. (1983) E
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118 G.R. Hanks Hanks, G.R. and Rees
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120 G.R. Hanks Khatib, K. al (1996)
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122 G.R. Hanks Luyten, I. (1935) Ve
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124 G.R. Hanks O’Neill, T.M., Man
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126 G.R. Hanks Ruamrungsri, S., Rua
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128 G.R. Hanks Thompson, P.A. (1977
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130 G.R. Hanks Williams, M. (1996)
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132 J.B. Briggs Table 5.1 Typical g
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134 J.B. Briggs Table 5.3 Actual gr
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136 J.B. Briggs Table 5.4 Actual co
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138 J.B. Briggs Table 5.5 Capital c
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140 J.B. Briggs ADAS (1987a) Narcis
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142 J. Bastida and F. Viladomat Fig
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Table 6.1 Narcissus alkaloid struct
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Table 6.1b Continued Alkaloid name
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Table 6.1d Tazettine type O O R1 R2
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Table 6.1f Continued MeO Alkaloid n
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Table 6.2 Continued Species* Alkalo
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162 J. Bastida and F. Viladomat Tab
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Table 6.3 Continued Alkaloid* Formu
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Table 6.3 Continued Alkaloid* Formu
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176 J. Bastida and F. Viladomat Tab
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178 J. Bastida and F. Viladomat Cri
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180 J. Bastida and F. Viladomat It
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184 J. Bastida and F. Viladomat is
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186 J. Bastida and F. Viladomat and
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Table 6.4 Continued Alkaloid Activi
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196 J. Bastida and F. Viladomat tac
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198 J. Bastida and F. Viladomat Ang
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200 J. Bastida and F. Viladomat Boi
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202 J. Bastida and F. Viladomat lyc
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204 J. Bastida and F. Viladomat Fug
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206 J. Bastida and F. Viladomat Han
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208 J. Bastida and F. Viladomat Kin
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210 J. Bastida and F. Viladomat of
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212 J. Bastida and F. Viladomat Sp
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214 J. Bastida and F. Viladomat Wil
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216 C. Codina and, consequently, hi
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218 C. Codina easily lost on transf
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220 C. Codina they might be more su
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222 C. Codina µ g/g FW µ g/g FW 3
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224 C. Codina Kinetin As observed i
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226 C. Codina Table 7.3 Total produ
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228 C. Codina Accumulation of alkal
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230 C. Codina Accumulation of alkal
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232 C. Codina Effect on growth and
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234 C. Codina mg/g DW mg/g DW 0.90
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236 C. Codina mg/g DW mg/g DW 1.4 1
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238 C. Codina mg/g DW mg/g DW 1.5 1
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240 C. Codina Hanks, G.R. and Jones
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8 Narcissus and other Amaryllidacea
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244 O.A. Cherkasov and O.N. Tolkach
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9 Studies on galanthamine extractio
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258 M. Kreh Table 9.1 Results of ga
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Page 307 and 308: 11 Extraction and quantitative anal
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Page 317 and 318: Table 11.1 GC and HPLC procedures f
Page 319 and 320: Table 11.1 Continued References Det
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Page 363 and 364: 342 D. Brown cortex and hippocampus
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Page 369 and 370: 348 D. Brown (1994) go on to mentio
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Page 375 and 376: 354 D. Brown Snorrason, E. and Stef
Page 377 and 378: 356 D. Brown examination of a brain
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362 D. Brown statistically signific
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364 D. Brown ( Jann, 1998); see Tab
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366 D. Brown REFERENCES Bartus, B.T
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368 D. Brown Wilcock, G.K., Scott,
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370 K. Ingkaninan, H. Irth and R. V
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16 Narcissus lectins Els J.M. Van D
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382 E.J.M. Van Damme and W.J. Peuma
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17 Narcissus in perfumery HISTORY C
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394 C. Remy Figure 17.2 Flower coll
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Figure 17.3 Narcissus flowers sprea
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398 C. Remy CONCLUSION The use of n
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400 C.G. Julian and P.W. Bowers Fig
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406 C.G. Julian and P.W. Bowers sym
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19 Review of pharmaceutical patents
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410 J.R. Murray to certain RNA viru
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412 J.R. Murray occurs in a two-pha
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414 J.R. Murray cognitive function
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416 J.R. Murray given at a time bet
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418 J.R. Murray Hofmannor, D., Mosc
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420 Index Backache, 403 Bacterial d
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422 Index Divisions (classification
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424 Index Leaf numbers, 11 Leaf sco
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426 Index Poet’s cultivars, 34 Po
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428 Index Subgenus (taxonomy); Ajax
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