Annotinine. I. The Relationship of Functional Groups<sup>1</sup>

Valenta, Z.; Stonner, F. W.; Bankiewicz, C.; Wiesner, K.

doi:10.1021/ja01593a064

Cited by 10 publications

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“…The relationship oE these groups to one another has been demonstrated by Wiesner et a/. (2) and by MacLean and Prime (3). This relationship is represented in the partial formula below.…”

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Lycopodium Alkaloids:vii. The Reaction of Annotinine With Phenyl Lithium

Perry¹,

MacLean²,

Manske³

1958

Can. J. Chem.

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Annotinine, Cl61121031\T, reacted with phenyl lithium to yield diphenylallnoti~line, C28H3J03N, containing two hydrosyl functions. Oxidation of diphenylannotinine by the Oppenauer procedure yielded a monohydroxyketone, C28Ha~03X, while oxidation with chrolnic acid yielded a dihydroxyketone, CPSH~IO.~N. A rnechanis~n for the formation of these cornpounds is discussed in relation to the chemistry of annotinine.Annotinine, C I~H~~O~N , is known to contain an epoxide function, a lactone ring, and a tertiary nitrogen atom (I). The relationship oE these groups to one another has been demonstrated by Wiesner et a/. (2) and by MacLean and Prime (3). This relationship is represented in the partial formula below.The structure of annotinine is now known (4, 5 ) but for the purposes of this paper the partial structure above suffices.Some years ago we found that annotinine reacted readily with phenyl lithium to form diphenylannotinine,, C28H330aN (I), which was isolated a t that time in an amorphous state. Diphenylannotinine did not dehydrate readily as would be expected of a diphenplcarbill01 nor did it show any reactions characteristic of a compound containing an epoxide function. Our formula also differed from that of WIeier and Marion (6), who proposed the formula CZ8Ha5O4N for the product of reaction of annotinine with phenpl lithium. Because of the anomalous behavior of diphe~lylan~loti~li~le and because of the difference between our results and those of NIeier and h/irarion, we have investigated the reaction more thoroughly.We have now obtained dipheng7Iannotini1le in crystalline form. This compound has a pronounced tendency to solvate, which may explain the formula of NIeier and Marion and the difficulty in obtaining good analytical results for the base. Drastic oxidation of diphe~lyla~lnoti~li~le yielded traces of benzophenone, which indicated that both phenpl residues were attached to the same carbon atom. Oxidation by the Oppenauer procedure using potassium tertiary butoxide or alumi~zum isopropoxide yielded the monohydroxyketone, C28H3103N (11). Both I and I1 were oxidized by chromic acid in acetic acid to the dihydroxyketone, C28H3104N (111), which is apparently identical with the product iso-'Manuscript received i n original form Septenzber 12, 1857, and, as revised, Aprzl 24, 1958. Conlribzltion front the Burke Chentical Laboratories, Hanzzlton College, 11cc1Waster University, Hamilton, Ontario, and the Research Laborator~es, Dominion Rubber Co. Lld., Guelph, Ontario. Part of this work was take?tfrom a thesis subtnttted by G.

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“…The relationship oE these groups to one another has been demonstrated by Wiesner et a/. (2) and by MacLean and Prime (3). This relationship is represented in the partial formula below.…”

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confidence: 80%

“…The oxidation by the Oppenauer procedure to give a single carbony1 group is not without precedent. Annotinine hydrate, which has hydroxyl groups in positions 3 and 7, yields only a C7 ketone (2). The chromic acid oxidation is more unusual, for in this case a fourth oxygen is introduced.…”

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confidence: 99%

Lycopodium Alkaloids:vii. The Reaction of Annotinine With Phenyl Lithium

Perry¹,

MacLean²,

Manske³

1958

Can. J. Chem.

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“…The absolute configuration of annotinine has been investigated by optical rotatory dispersion studies on the keto ester CXXVIII, derived from the alkaloid (170). Application of the octant rule to the Cotton An alkaloid, norsecurinine, has been found in the roots of Securinega virosa.…”

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confidence: 99%

Lactonic Alkaloids

Pinder¹

1964

Chem. Rev.

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“…In a later paper they established the presence of a lactone ring and an ether ring in the molecule (2). The size of the ether ring and its relationship to the nitrogen atom were demonstrated by AIIacLean and Prime (3) while Wiesner et al were able to relate the lactone ring t o the other functions in the molecule (4). Several total structures for the alkaloid have been proposed in the past by Wiesner et al (4, 5 , 6 ) on the basis of dehydrogenation experiments on annotinine and its derivatives.…”

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Lycopodium Alkaloids: Vi. Reactions of the Diphenyl Derivative of Desoxodihydroannotinine

Betts¹,

MacLean²

1958

Can. J. Chem.

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Desosodihydroannotinine reacted \vith phenyl lithium to yield a diphenyl derivative, C28H3j0?2\: (111). This compound yielded a ketone, C2BH330?N (V), LIPOII oxidation by the Oppenauel-procedure and a dihydrosyketone, C?BH3303N (VI), ~ipon oxidation \vith chromic acid. 11 ketoneVIII, epimeric with V, was obtained by treatment of I11 with potassii~m tertiary butoside in cyclohexanone. Both V and VIII underwe~lt elimination of their diphenyl carbin01 groups LIPOII treatment with potassium tertiary butoside to yield an unsaturated ketone, C I~H~~O N (IX), alicl benzohydrol. These reactions are discussed in relation to the recently proposed structures for the parent all:aloid, annotinine.Annotinine, C16HZ103N, the major alltaloid of Lycopodiu?n annotinurn, was first isolated by Manslte and Marion (1). In a later paper they established the presence of a lactone ring and an ether ring in the molecule (2). The size of the ether ring and its relationship to the nitrogen atom were demonstrated by AIIacLean and Prime (3) while Wiesner et al. were able to relate the lactone ring t o the other functions in the molecule (4). Several total structures for the alkaloid have been proposed in the past by Wiesner et al. (4, 5 , 6 ) on the basis of dehydrogenation experiments on annotinine and its derivatives. In their latest publicatioil (7) they have established the detailed structure of ring B (formula A) and have suggested that formula A adequately explains the reactions of annotinine.Martin-Smith, Greenhalgh, and Marion (8) have also proposed a structure for annotinine which is represented in formula B. Arguments were advanced that their structure explained the dehydrogenation reactions of annotinine equally as well as previous structures of Wiesner's. However, the seven-membered nature of ring A is not consistent with the work of Betts and MacLean (9). Nor is the structure of ring B consistent with the latest work of Miiesner et al. (7), nor with the results of the present study.* Annotinine (I) was converted to desoxodih~~droaililotini~let (11) by the method of Manske and R/Iarion (2). This compound has the same ring structure as annotinine but lacks the epoxide function (9). I t reacted readily with phenyl lithium t o yield diphenyldesoxodihydroani~otii~ine, C28H350?N (111). This compound dehydrated readily with 'iManuscript received Septe?irber 12, 1957. Co?ztribzrtion fro~rz thc Burke Che711zcal Laboratories, Ha?nilto?z Collcgc, 116ciVIaster University, Ha711ilto?z, Onlario. 2Holder of a National Research Coz~ncil Studentship, 1956-57. *For?~zzrla B has siwce becn withdrawn by 116arion and Przybylska (Caw. J . Chenr. 35, 1075 SF. 1968 boiling, aqueous hydrochloric acid to yield the anhyclro derivative, C28H330N (lV), which has an ultraviolet spectrum characteristic of a 1,l-diphenylethylei~e despite the fact that the compound would not absorb hydrogen a t lolv pressures nor oxidize with ease. Oxidation of I11 with aluminum isopropoxicle in the presence of cyclohexanone yielded the hydroxy ketone, C28H3302...

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Annotinine. I. The Relationship of Functional Groups¹

Cited by 10 publications

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Lycopodium Alkaloids:vii. The Reaction of Annotinine With Phenyl Lithium

Lycopodium Alkaloids:vii. The Reaction of Annotinine With Phenyl Lithium

Lactonic Alkaloids

Lycopodium Alkaloids: Vi. Reactions of the Diphenyl Derivative of Desoxodihydroannotinine

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Annotinine. I. The Relationship of Functional Groups1

Cited by 10 publications

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Lycopodium Alkaloids:vii. The Reaction of Annotinine With Phenyl Lithium

Lycopodium Alkaloids:vii. The Reaction of Annotinine With Phenyl Lithium

Lactonic Alkaloids

Lycopodium Alkaloids: Vi. Reactions of the Diphenyl Derivative of Desoxodihydroannotinine

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Annotinine. I. The Relationship of Functional Groups¹