A. Abdusamatov

d-Caaverine and a new alkaloid - lirinidine — From Liriodendron tulipifera

SummaryFrom the leaves ofLiriodendron tulipifera have been isolated d-caaverine and a new aporphine alkaloid—lirinidine—with the composition C18H19O2N, [α]D25 +78° (c 0.19; chloroform).On the basis of features of its UV, IR, NMR, and mass spectra and chemical transformations, the structure of 5-hydroxy-6-methoxyaporphine has been established for lirinidine.

Alkaloids ofLiriodendron tulipifera

The alkaloids of the tulip treeLiriodendron tulipifera L., family Magnoliaceae, are considered. More then 20 alkaloids have been isolated during different vegetation periods from various organs of the plant growing in Uzbekistan, and these have been assigned to the aporphine alkaloids and their dehydro, oxo, and 7-hydroxy derivatives; only two alkaloids proved to be derivatives of proaphorphine and of tetrahydroberberine. On the basis of the results of a comparative study of the NMR spectra of aporphines unsubstituted in ring D and some chemical transformations, the structure and configuration of the (R)-3-hydroxy-1,2-dimethoxyaporphine have been proposed for the new alkaloid lirinine. The absolute configurations, possible biogenetic interconnections, and mutual transitions of the alkaloids ofL. tylipifera that are derivatives of aporphine, oxoaporphine, and dehydroaporphine are discussed. A summery table is given which includes 41 alkaloids found in this plant.

Alkaloids of Pedicularis macrochila

M. K. Yusupov and A. S. Sadykov, Zh. Gbshch. Khim., 34._.., 1672 (1964). K. M. Zuparova, B. Chommadov, M. K. Yusupov, and A. S. Sadykov, Khim. Pr i rodn . Soedin., 487 (1972). F. Shantavy [Santavy], Scientific P a p e r s of the Lenin Tashkent State Univers i ty . The Chemis t ry of Plant Substances [in Russian] (1972), p. 7. A. K. Kasymov, M. K. Yusupov, l~. Kh. Timbekov, and Kh. A. As ian .v , Khim. Pr i rodn . Soedin., 194 (1975).

The dynamics of the accumulation and mutual transformation of alkaloids in Liriodendron tulipifera

SummaryAs the result of a study of the leaves ofLiriodendron tulipifera L. according to the vegetation periods, it has been established that they contain the maximum amount of alkaloids in the spring and early vegetation period of the plant (0.32%) and the minimum amount when they are in the yellowed state in the autumn (0.11%).Transitions from N-methylcrotsparine to lirinidine, from d-caaverine to lirinidine and d-nornuciferine, and from the latter to lysicamine have been established.

Lirinine — A new alkaloid from Liriodendron tulipifera

Summary1. The leaves ofLiriodendron tulipifera have yielded a new alkaloid, lirinine. On the basis of a study of the UV, IR, NMR and mass spectra of lirinine the structure of 5-hydroxy-2,6-dimethoxyaporphine has been proposed for it.

Alkaloids of Liriodendron tulipifera

Summary1. The leaves ofL. tulipifera L. have yielded lirinine N-oxide and a new amorphous base with the composition C20H23O3N, [α]D25-52.9° (c 0.171; chloroform), M+ 325 (mass spectrometrically).2. On the basis of its UV, IR, and mass spectra and chemical transformations, the structure of 2,5,6-trimethoxyaporphine has been established for the new alkaloid.

Pediculinine — A new alkaloid from Pedicularis olgae

SummaryA new substance — pediculinine, C10H13NO, mp 133–134°C — has been isolated from the chloroformic fraction of the combined alkaloids ofP. olgae. Structure (I) has been proposed for the new alkaloid on the basis of UV, IR, NMR, and mass spectra and chemical characteristics.

Mass spectrometric study of the structure of indicaine and plantagonine

The mass spectrum of indicaine [1] has strong peak s of ions with m/e 161 (88%), 160 (23%), 146 (100%), 133 (10010), 132 (34%), 118 (4007o), 117 (65°1o), 91 (35%), and 77 (8%). The presence of these peaks shows that the fragmentation of indicaine takes place mainly in two directions: 1) The methyl group is eliminated from the molecular ion with m/e 161 and the maximum peak with m/e 146 which loses a CO group appears and forms an ion with m/e 118. The presence of a metastable peak with m/e 95.5 (calculated, 95.4) confirms the transition m/e 146-118. The ion with m/e 118 eliminates a CH2--CH group, being converted into a fragment with m/e 91. The latter, by losing a --CH2 group, gives an ion with m/e 77. 2) The fragmentation begins from the ion (M-l) + with m/e 160. The expulsion of the CO group from the ion with m/e 160 leads to the formation of an ion with m/e 132. By splitting out a methyl radical, this ion is converted into an ion with m/e 117. Then the ion with m/e 117 loses a CH~CH group, being converted into a fragment with m/e 91. The mass spectrum of plantagonine has strong peaks of ions with m/e 117 (3090), 162 (50%), 133 (1501o), 118 (100~/o), 91 (27~o), 77 (9%). The molecular ion of plantagonine, with m/e 177, loses a methyl group to form an ion with m/e 162, which loses a CO 2 group and is converted into an ion with m/e 118. Subsequent fragmentation takes place in the same way as for indicaine.

Alkaloids of the leaves of Cocculus laurifolius the structure of coclafine

Cocculine, isoboldine, norisoboldine, and a new erythrinan alkaloid, coclafine, for which the structure and absolute configuration of 3S,5R-3,15-dihydroxyerythrin-Δ1(6)-ene have been established, have been isolated from the leaves ofCocculus laurifolius DC.

Ungvedine — A new alkaloid fromUngernia vvedenskyi

I. A. Nabiev, R. Shakirov, and S, Yu. Yunusov, Khim. Prir. Soedin., 676, 679 (1976). 2. F. Bohlmann, Ber., 91, 2157 (1958). 3. R. N. Nuriddinov, R. Shakirov, and S. Yu. Yunusov, Khim. Prir. Soedin., 316 (1967). 4. R. N~ Nuruddinov and S. Yu. Yunusov, Khim. Prir. Soedin., 458, 767 (1971). 5. H. Budzikiewicz, Tetrahedron, 20, 2267 (1964). 6. R. N. Nuriddinov and S. Yu. Yunusov, Khim. Prir. Soedin., i01, 258 (1968). 7. T. Masamune, N. Sato, K. Kobayashi, I. Yamazaki, and Y. Mori, Tetrahedron, 23, 1591 (1967). 8. T. M~ Moynehan, K. Schofield, R. A. Y. Jones, and A. R. Katritsky, J. Chem. Soc., 2637 (1962). 9. R.N. Niriddinov and S. Yu. Yunusov, Khim. Prir. Soedin., 260, 334 (1968). I0. R. N= Nuriddinov, A. I. Saidkhodzhaev, M. R. Yagudaev, and S. Yu. Yunusov, Khim. Prir. Soedin., 333 (1968).