Other alkaloids

Lycopodium Alkaloids. Gerard and MacLean (1986) reported the analysis of Lycopodium species by GC-MS. Most of the alkaloids previously reported to occur in the species examined could also be found using the GC system. One of the exceptions was lycodiflexine, which might not be sufficiently volatile since its molecular weight (562) is well above that of the other components of the extract. Besides the alkaloids reported, other minor alkaloids could be detected by this method. The retention index of 15 alkaloids is included. 

Polyhydroxylated Alkaloids. Polyhydroxy derivatives of pyrrolidine, piperidine, and indolizidine alkaloids have recently been isolated from plants and microorganisms. A number of these compounds have shown potent gluco-sidase inhibitory activity and have generated interest because of their ability to inhibit replication of retroviruses. 

length (m) X i.d. (mm) Injector Temperature program (°C) Detector Carrier gas  

A gas chromatographic method for the separation of these compounds was reported by Nash et al. (1986). Trimethylsilyl derivatives of the polyhydroxy alkaloids were analyzed in a packed column of medium polarity. More recently Molyneux et al. (1991) used a 30m x 0.32 mm i.d. SE-30 capillary column to analyze the trimethylsilyl derivatives of this type of alkaloid. 

In this chapter, the utility of GC in the analysis of alkaloids has been illustrated. Spectral information of unknown compounds from a mixture can be obtained by coupling a GC to a MS or to a FT-IR. For determination of known compounds in mixtures, other more common detectors can be used, such as FID, ECD (electron capture detection), or PND, for it is often sufficient to compare their retention time with the retention time of authentic samples. Furthermore, GC-MS also allows biosynthetic and metabolic studies using stable isotopes. 

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C10HJ4N2. When pure nicotine is a colourless liquid, b.p. 247 C, but darkens on exposure to air and light. Crude nicotine contains smalt amounts of other alkaloids, but ( —)-nicotine is the principal component. 

Present along with other alkaloids in the hemlock extract used to poison Socrates)... 

Reactions at the aromatic nucleus that are quite different from the usual mild condensations and rearrangements which apparendy generate the typical alkaloids already discussed must be iavolved. Securinine (137) is reported to stimulate respiration and increase cardiac output, as do many other alkaloids, but it also appears generally to be less toxic (98). 

Nuts have many uses, both industrial and domestic. For instance, the ivory nut, or tagua, is a source material for the manufacture of buttons and turnery articles. The kola nut supplies ingredients for popular cola beverages in the United States (see Carbonated beverages). StTychnos nux-vomica provides the important medicine and poison, strychnine. The areca or betel nut is chewed by the Indian and Malayan people as a narcotic a slice of the nut is placed in a leaf of the pepper plant Piper betle) together with a pinch of lime the mixture is an acrid, astringent narcotic that dyes the mouth red, blackens and destroys the teeth. The areca nut contains, among other alkaloids, arecoline, an active anthelminthic widely used in veterinary practice for the treatment of tapeworm infections. 

Billing 7 has provided a scheme for distinguishing between the hemlock bases and other alkaloids, such as sparteine, nicotine and lobeline. 

The names, formulae and structures of these alkaloids are given in the following table. The esters of tropine or -tropine are known as tropeines or -tropeines respectively. The first eleven items in the table are sometimes called the solanaceous alkaloids, but they are not the only alkaloids, or even the only type of alkaloid, found in the botanical family Solanaceas. They are also sometimes referred to as the mydriatic alkaloids though other alkaloids also exert this action. 

Estimation of Other Alkaloids in Opium. Of the other alkaloids the most important is codeine, and processes for its estimation in opium have been described by Cespari, Andrews,and Annett and co-workers methods for its assay in admixture with other drugs in tablets and other products are also available. The estimation of papaverine has been described by Issekutz,i and of narcotine by Snesarov. As to methods for the separation and estimation of two or more of these subsidiary alkaloids, codeine and narcotine have been dealt with by van der Widen,narcotine and papaverine by Annett and Bose, ( and the bromination of codeine and narceine has been studied by Vaisberg et al. with a view to estimation by this means. 

The first scheme for the separation of the six chief alkaloids of opium, VIZ., morphine, codeine, thebaine, papaverine, narcotine and narceine, is probably that of Plugge. Much later Kljatschkina investigated for each of these six bases the properties by means of which isolation and estimation could probably be effected and, on the basis of the results, devised a plan for such analyses. More recently Anneler has published a detailed account of a scheme with the same objective. l Attention had already been given to complex, systematic analyses of this kind, in connection with examination of the mixtures of opium alkaloids, which have long been in use in medicine in these at first only morphine and other alkaloids were determined, but in the more recent schemes provision is made for the estimation of each alkaloid. ... 

Special Reactions of Papaverine. Papaverine undergoes a number of reactions, which are of interest as providing methods of synthesis for other alkaloids, of which examples will be found under laudanosine, laudanine, laudanidine, codamine (pp. 187-195), berberine (p. 331), corydaline (p. 284), and glaucine (p. 311). 

Haworth, Koepfli and Perkin have shown that, like other alkaloids of the protoherherine series, tetrahydropalmatine is convertible by the general process (p. 302) into an alkaloid of the cryptopine type. The... 

Sinomenium acutum Rehd and Wils. Sinactine (Z-tetrahydro-epiberberine) and other alkaloids (p. 268). 

Among other alkaloids closely related to tetrandrine is fangchinoline (item 15d list, p. 351), a demethyltetrandrine already described loc. cit.). 

Like other alkaloids of this group, quinine forms molecular compounds with a variety of organic substances. With benzene and toluene it produces compounds of the formulae B. CgHg and B. C,Hg respectively, with phenol it gives the crystalline product B. CgHjOH, and similar combinations with polyhydric phenols, ethers, aldehydes and ketones are known. One of the most characteristic of these substances is cupreine-quinine, a combination of the two alkaloids, obtainable from cuprea bark, and at first regarded as a new alkaloid, and named homoquinine. ... 

Alkaloids of Remijia Purdieana. The bark of Bemijia Purdieana, a tree related to that yielding cuprea bark, contains a little cinchonine and a series of other alkaloids, for which Hesse gives a scheme of separation with descriptions. 

Jacobs and Craig found two other alkaloids in the mother liquors accumulated during the isolation of atisine from A. heterophyllum. 

Delphinium Staphisagria L. From the seeds of this species, the oil of which is used as a pediculicide, Brandes isolated delphinine in 1819, and this and other alkaloidal components were subsequently examined by various workers including Marquis, Kara-Stojanov, Ahrens, Keller, Walz and most recently by Jacobs and Craig. ... 

In recent years much interest has been displayed in the Indian species and other alkaloids, named in the following list, have been isolated from it, though it should be noted that doubts have been expressed by several authors as to the individuality of some of these substances. 

In a comprehensive review of this subject Schopf (1937) gave a preliminary description of a number of other syntheses of this kind, including that of teloidine, already referred to. Suggestions for other alkaloidal syntheses were also made and the conditions under which such reactions might take place in plants discussed. 

Most of the early work carried out on the synthesis of these compounds was aimed at the elucidation of the structures of various harmala and other alkaloids. It will not be presented here in historical sequence but rather in a systematic fashion according to the starting materials and the synthetic methods used. 

Two other alkaloids 47 and 48 were isolated in addition to Neooxygambirtannine 44 (67T3129). Anhydroalstonatine from Alstonia venenata is a closely related structure (77IJC(B)183) (Scheme 18). 

Demethylvasconine (85) (9-methoxy-5-methyl-phenanthridin-8-olate) presented in Scheme 31 was found in Crinum kirkii (95P1291) (Amaryllidaceae). Although published as cation, no information about the anion of this alkaloid is given. Its relationship to other alkaloids of this class, however, makes a betainic structure more than likely and this is confirmed by a comparison of the NMR data of 85 with the cationic and betainic alkaloids presented in Table III. This betaine is isoconjugate with the 2-methylphenanthrene anion and thus defined the alkaloid as a member of class 1 (odd alternant hydrocarbon anions). Whereas substitution of the isoconjugate phenanthridinium moiety at the 1-position with an anionic fragment results in zwitterions (cf. Section III.D), the phenanthridinium-2-olate is a mesomeric betaine. 

The chromatograms are freed from mobile phase in a stream of warm air, then immersed in the dipping solution for 2 s or homogeneously sprayed with the appropriate spray solution. Then, in the case of N-ethyl derivatives, the plate is heated to 105-110 °C for 2 min to accelerate the reaction [7]. Heating (e. g. to 80-105 °C for 15 min) can also lead to color intensification and color change in the case of other alkaloids [5, 6]. 

Note It is possible to differentiate amino acids by color on the basis of the markedly different shades produced [2, 3]. Proline and hydroxyproline, that only react weakly with ninhydrin, also yield pink-red colored derivatives [2]. Ergot alkaloids and LSD are detected by spraying with 10% hydrochloric add and then heating to 110°C for 20 min after they have been treated with the reagent [9]. Ergot alkaloids and LSD yield red to purple zones when treated in this manner other alkaloids, e.g. reserpine, emetine, quinine, strychnine, pilocarpine, atropine, scopolamine, cocaine and opium alkaloids, do not give a reaction [9]. 

The profound physiological effects of alkaloids have been known for centuries. For example, Socrates was put to death with an extract of hemlock, which contains a poisonous alkaloid, coniine. Other alkaloids have long been valued for their beneficial medical effects. Examples include morphine (a painkiller), quinine (used to treat malaria), and atropine (used to treat Parkinson s disease and in eye drops that dilate the pupils). 

Kirch et al. (1995) examined individual plants collected in Corsica, Elba, Sardinia, Liguria, and Provence for alkaloids and observed four groups, one characterized by sparteine [119] (see Fig. 2.34 for structures 119-124), one characterized by lupanine-based alkaloids [120 and 121], one that had a very low level of alkaloid production, and one that lacked sparteine and lupanine-based compounds, but did accumulate other alkaloids such as anagyrine [122], ammodendrine [123], and compounds based on cytisine [124], their outlier group. The distribution of these four chemotypes is presented in Table 2.10. 

Spar = Sparteine type Lupa = Lupanine type Lows = Low alkaloid content Others = Other alkaloid types. 

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