Acetylated alkaloids

Kreh, M., R. Matusch, and L. Witte. 1995. Acetylated alkaloids from Narcissus pseudonarcissus. Phytochemistry 40 1303-1306. 

Acetopenone glucoside Acetyl harpagide Acetylated alkaloids Acetylcholine Acetylenes... 

Same derivatives of a number of mucronines and abyssenines were not accessible (Section IV, E). Mass spectra of the substituted N-acetylaminoaldehydes resemble those of the acetylated alkaloids even... 

The alkaloid delcosine was first isolated by Goodson 44) from the roots of D. ajacis L. and tentatively named alkaloid C. Marion and Edwards isolated delcosine from D. consolida 45) and it was later found that the two materials were identical 46). Another of the bases isolated by Goodson 44) was an acetylated alkaloid tentatively named alkaloid B, which gave rise to alkaloid C on hydrolysis. Thus alkaloid B is monoacetyldelcosine 46). The alkaloids lucaconine and monoacetyllucaconine, isolated from the roots of A. lucidtisculum Nakai 47-51), have also been shown to be identical with delcosine and monoacetyldelcosine, respectively 51). Likewise, the identities of Takao base I, from A.japonicum Decne. 52) and delphamine 53) have been found to be identical with delcosine 54, 55). The alkaloid previously reported as Shimoburo base II, from A.japonicum 56) is identical with 14-dehydro-... 

Dieckmann reaction, 4, 471 Indolizidine alkaloids mass spectra, 4, 444 Indolizidine immonium salts reactions, 4, 462 Indolizi dines basicity, 4, 461 circular dichroism, 4, 450 dipole moments, 4, 450 IR spectra, 4, 449 reactivity, 4, 461 reviews, 4, 444 stereochemistry, 4, 444 synthesis, 4, 471-476 Indolizine, 1-acetoxy-synthesis, 4, 466 Indolizine, 8-acetoxy-hydrolysis, 4, 452 synthesis, 4, 466 Indolizine, I-acetyl-2-methyI-iodination, 4, 457 Indolizine, 3-acyloxy-cyclazine synthesis from, 4, 460 Indolizine, alkyl-UV spectra, 4, 449 Indolizine, amino-instability, 4, 455 synthesis, 4, 121 tautomerism, 4, 200, 452 Indolizine, 1-amino-tautomerism, 4, 38 Indolizine, 3-amino-synthesis, 4, 461, 470... 

Acetic Acid Acetic anhydride Acetoacetanilide Acetone cyanhydnn Acetyl chloride Acrolein Acrylonitrile Alcohols Alkaloids... 

Ammodendrine, C jH oONj, HjO (No. 1, table, p. 116). The base has m.p. 73 °, becomes anhydrous at 70-80°, and then melts at 50-60°, Wd i 0°. The salts are amorphous and deliquescent except the hydriodide B. HI, which forms a crystalline precipitate, m.p. 218-20°, from alcohol, and the perchlorate, m.p. 199-200°. An amorphous A-benzoyl derivative was obtained. With methyl iodide ammodendrine behaves as a secondary base, yielding first A-methylammodendrine hydriodide (a crystalline precipitate, m.p. 183-5°, from a mixture of alcohol and acetone), and at the second stage iV-methylammodendrine methiodide, m.p. 163-5°. On hydrogenation ammodendrine furnishes a dihydro-base, which is hydrolysed into acetic acid and 2 3 -dipiperidyl, C oHjoNj, and must be dZ-A-acetyl-3-a-piperidylpiperidine. Ammodendrine should therefore be acetyltetrahydroanabasine and is of biological interest as the first recorded occurrence of this type of alkaloid in the Leguminoss. ... 

Anhalonine and Lophophorine. Spath and Gangl showed that each of these alkaloids contains a methylenedioxy group and that the quarternary iodide prepared from dZ-anhalonine is identical with lophophorine methiodide so that lophophorine must be N-methylanhalonine. Anhalonine was synthesised from 3 4-methylenedioxy-5-methoxybenzaldehyde by condensation with nitromethane, reduction of the product to the corresponding -ethylamine, the acetyl derivative (VII) of which, on treatment with phosphoric anhydride, condensed to 6-methoxy-7 8-methylenedioxy-l-methyl-3 4-dihydrofsoquinoline, m.p. 60-2°. This, on reduction, furnished the corresponding tetrahydrofsoquinoline, which proved to be anhalonine (VIII), and on conversion to the quaternary methiodide the latter was found to be lophophorine (IX) methiodide. The possible alternative, 8-methoxy-6 7-methylenedioxy-l 2-dimethyl-l 2 3 4-tetrahydrofsoquinoline, was prepared by Freund s method and the methiodide shown not to be identical with lophophorine methiodide. 

Tuduranine, CjgHjgOgN. This member of the aporphine group (p. 306) is the most recent addition to Sinomenium alkaloids and was isolated by Goto from the mother liquors of sinomenine. It is crystalline, has m.p. 125° (with softening at 105°), and yields a sparingly soluble hydrochloride, m.p. 286° (dec.), [a] f — 148° (dilute MeOH), is freely soluble in alkali, and gives feeble ferric chloride and diazo-colour reactions and a fuchsin-red colour with formaldehyde and sulphuric acid. It behaves as a secondary base and yields a diacetyl derivative, m.p. 170°, [a] / — 321-71° (MeOH), which does not form a methiodide, but can be hydrolysed to A -acetyl-tuduranine, m.p. 277°, — 395-24°, and this can be methylated to... 

NMca. CHa. CHj. O. CO. CH CH. C6H2(OMe)a. OAc, from which the acetyl group was readily eliminated yielding a product, which on treatment with methyl iodide was converted into sinapine iodide, NMcgl. CHj. CHj. O. CO. CH CH. CgH2(OMe)2. OH, identical with that obtainable from the natural alkaloid. 

Lettre and Fernholz have tested a series of colchicine derivatives, including a group of alkylcolchiceines, on experimentally induced tumours all proved to be less potent than the parent alkaloid. A -Acetyl-j3-p-anisyl-y-(3 4 5-trimethoxyphenyl)-propylamine,... 

The acetyl group in aconitine may be eliminated in two other ways (a) by heating aconitine in sealed tubes with methyl alcohol, when methylbenzoylaconine, m.p. 210-1°, is formed, or (b) by heating the alkaloid at its melting-point, when pyraconitine, C32H43O9N, m.p. 167-5° (171°, Schulze), [a] ° — 112-2° (EtOH), is formed. The latter yields crystalline, laevorotatory salts, and on hydrolysis by alkalis affords benzoic acid and pyraconine, C2sH3gOgN, amorphous, [a]n — 91° (HgO), but yields a crystalline hydrochloride, B. HCl. 2-5H20, m.p. 154° (135°, Schulze), Md - 102° (HgO) (- 124-6°, Schulze). ... 

Addendum. In a recent paper Bertho et al. have described a new process for the isolation of kurchi alkaloids. From the final residue a new base, C23H34N2, m.p. 129 5°, was isolated as the carbonate, m.p. 91° it provides the following salts B, 2HI, 2H2O, dec.) 174° B, 2HCIO4, 2.5H2O, m.p. 283°, and a mono-acetyl derivative, m.p. 254°. In a second paper Bertho, Schonberger and Kaltenbom describe further products obtained in the oxidation of conessine by chromic acid and by potassium permanganate. ... 

The acetylation of isotripiperideine by means of a ketone in nonpolar media affords a compound which decomposes in acidic media to piperideine and a monoacety.l derivative of the enamine form of tetrahydro-anabasine (195). This monoacetyl derivative is identical with the alkaloid amodendrine (312). A similar acylation with cinnamoylchloride affords the alkaloid orensine (196) (313), the optically active form of which is the natural alkaloid adenocarpine (314). The hydrolysis of alkaloid santiaguine gives a-truxilic acid (314). 

In synthesis of the alkaloid tjipanazole E (19b), the required symmetric dichloro-indolo[2,3-fl]carbazole 20a was obtained in a two-step procedure starting fi-om 4-chlorophenylhydrazine hydrochloride and 1,2-cyclohexanedione employing a Fischer indolization. Subsequent attachment of an acetyl-protected glucopyranosyl moiety to one of the nitrogens, followed by cleavage of the protective groups with ammonia in methanol, produced the desired natural product (91X7739). 

Acetyl-pyridine werden (ahnlich wie Acetophenon) bei Anwesenheit optisch aktiver Alkaloide in Athanol/waBr. Acetatpuffer (1 1) bei —0,7 bis —0,8 V an Quecksilber zu den entsprechenden Alkoholen reduziert. In Gegenwart von Strychnin wird 1-Pyridyl-(2)-athanol zu 50% d.Th. (47,5% opt. Ausbeute) 1 -Pyridyl-(4)-dthanol zu 40% d.Th. (40% opt. Ausbeute) gebildet. Mit Brucin sind die optischen Ausbeuten stets deutlich ge-ringer (max. 27%)- Aus 3-Acetyl-pyridin entsteht stets das inaktive l-Pyridyl-(3)-athanol (40% d.Th.)2. 

Alkaloids produce variously colored chromatogram zones (yellow, pink, brown, purple) on a light background [2]. Indole and the catechins appear red [4, 5, 8, 9, 12, 16]. If the catechins are acetylated it is necessary to heat to 105 °C for 5 min after treatment with the reagent [8]. Lysergic acid derivatives should also be heated to 75 °C for 5 min. 

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