Über das Alkaloid Lonicerin aus Callichilia barteri. 137. Mitteilung über Alkaloide

The alkaloid lonicerine was isolated from Callichilia barteri (Apocynaceae). By chemical and spectroscopic evidence it could be shown to be 16-epi-aspidodasycarpine ( 1 ).     

Über Poterinchemie. 82. Mitteilung. Bildung von Formimidoyl-Derivaten aus Aminen und Benzylisocyanid; Eine neue Umpolungsmöglichkeit für bestimmte C-Atome

Formation of Formimidoyl Derivatives from Amines and Benzylisocyanide; A New Possibility of Umpolung for Certain C-Atoms Cu(I)Cl can give a colorless and well-crystallized complex with 4 molecules of benzylisocyanide. This complex is able to transfer the benzylisocyanide ligands to primary and secondary amines and to form N-benzylformimidoyl derivatives. Catalyic hydrogenolysis removes the benzyl group, and free formimidoyl compounds are obtained in good yield. The method which succeeds with aliphatic amines, could not be applied to the secondary amino group of tetrahydropterines.     

Über Juliprosin,ein weiteres Alkaloid aus Prosopis julifloraA.DC. 180. Mitteilung über organische Naturstoffe

Juliprosine, a Further Alkaloid Isolated from Prosopis juliflora A .DC . By catalytic hydrogenation of the second base juliprosine ( 2 ) isolated from Prosopis juliflora (Leguminosae) the hexahydroderivative 5 was formed. The same product was obtained also by catalytic hydrogenation of juliprosopine ( 1 ) of known structure. The absolute configuration of 2 was deduced by comparison of [M]_D values of Prosopis alkaloids of known absolute configuration.     

Über in 6-Stellung basisch substituierte Morphanthridine. 8. Mitteilung über siebengliedrige Heterocyclen

Morphanthridines III with a basic substituent in position 6, which show neuroleptic activity, have been synthesised as follows: Chlorination of the lactams I with POCl₃ gave the iminochlorides II, which were converted by bases to the amidines III. The 11-oxo-morphanthridines VI and VII were synthesised using the same procedure, 2-(1-methylpiperazine-4-carbonyl)-2′-amino-benzophenone (XI) was obtained directly from the 6-chloro-11-oxo-morphanthridine (V) or by extended heating of VI with N-methylpiperazine. Reduction of the 11-oxo-compounds VI and VII with NaBH₄ gave the 11-hydroxy-compounds IX and X. 3-(2-aminophenyl)-phtalide (VIII) resulted from the acid hydrolysis of IX.     

Über Pterinchemie. 60. vorläufige Mitteilung [1]. Eine neue,regiospezifische Synthese von L-Biopterin

A new, regiospecific synthesis of L -biopterine Pure L -biopterine (I) is obtained in 35–40% yield by condensation of 5-desoxy-L -arabinose-hydrazone acetate with 2,4,5-triamino-6-hydroxy-pyrimidine, followed by oxidation of the formed tetrahydro-derivative and deacetylation of the L -bioterine diacetate. Catalytic reduction of the L -biopterine gives the expected mixture of two diastereomeric tetrahydro-L -biopterines.     

Über eine neue Ringschlussreaktion mit 3-Dimethylaminopropyl-carbinolen zu Oxolanen. Mitteilung über Grignard-Reaktionen mit Halogenalkylaminen [1]

A new ring-closure reaction is described, consisting in the treatment of basic carbinols of types 2 , 8 , 13 , 16 , with sodamide or sodium hydride, and adding to the sodium salts formed an alkyl halide. Oxolanes of types 5 , 9 , 14 , 17 , 20 , are formed.     

Über Pterinchemie. 49. Mitteilung. Eine neue Synthese von 5-Formyl-6, 7-dimethyl-5,6,7,8-tetrahydropterin und 5,6,7-Trimethyl-5,6,7,8-tetrahydropterin

Starting with 5-formyl-6,7-dimethyl-5,6,7,8-tetrahydropterine (II), a new synthesis of 5,6,7-trimethyl-5,6,7,8-tetrahydropterine (III) is described. Thereby the chemical behaviour of the 5-formyl group in II is investigated, in order to enable the unequivocal differentiation between formylation at position 5 and at position 10 in folic and tetrahydrofolic acid derivatives. ¹³C-NMR. spectra of II and III are discussed.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. I

The compound [HCCl=C(NPCl₃)(PCl₃)[PCl₆], VI, is formed in the reaction between acetonitrile and PCl₅. Reaction of H₂S with VI results in the formation of the chloride and by further reactions of this chloride with BCl₃ and SbCl₅ the tetrachloroborate and hexachloroantimonate salts respectively, are obtained. Chloroacetonitrile can be made to react with PCl₅ to give HCCl?C(NPCl₃)Cl, II, by use of suitable conditions. There is no indication that mixtures of cis/trans isomers of VI or II exist as has been previously postulated. The ¹H and ³¹P NMR spectra of the above-mentioned compounds and numerous further products from the reactions of CH₃CN, ClCH₂CN and Cl₂CHCN with PCl₅ are discussed in detail. II occurs in a cisoid and a transoid conformation.     

Über neue Sulfinyl- und Carbonyl-Pseudohalogen-Verbindungen

New Sulfinyl and Carbonyl Pseudohalogen Compounds FSO(NCO) ( 1 ) is formed as well during the attempt of synthesizing fluoroformyl sulfinylimide from OCFBr and Hg(NSO)₂ by an unexpected rearrangement as from OSFCl and Hg(NCO)₂ directly. FSO(NSOF₂) ( 2 ) was obtained analogously. Trying to get OS(NCO)₂, OC(NCO) (NSO) ( 3 ) was formed again by rearrangement as well as from ClCO(NCO) and Hg(NSO)₂.     

Über Alkaloide aus Laurelia novae-zelandiae A. CUNN. 5. Mitteilung über natürliche und synthetische Isochinolinderivate

From an extract of Laurelia novae-zelandiae A. CUNN . the aporphine alkaloids (?)-pukateine (I), (?)-pukateine methyl ether (II), (?)-roemerine (IV), (?)-mecambroline (V), (+)-boldine (VII), (+)-isoboldine (VIII), (+)-laurolitsine (IX), and the proaporphine alkaloid (+)-stepharine (X) were isolated. Compounds II and V were up to now not described as natural alkaloids. These and the alkaloids IV, VII, VIII, IX and X are new for L. novae-zelandiae.     

Über Dienketene aus o-Chinolacetaten

On Dien-Ketenes from o-Quinol-Acetates A detailed picture of the photochemistry of o-quinol-acetates is presented. (RS)-6-Acetoxy-6-methyl-, (RS)-6-acetoxy-2,6-dimethyl-, (RS)-6-acetoxy-5,6-dimethyl-, (RS)-6-acetoxy-2,4,6-trimethyl-, (RS)-6-acetoxy-2,3,4,6-tetramethyl-, and (RS)-6-acetoxy-2,3,4,5,6-pentamethyl-2,4-cyclohexadien-1-ones serve as representative educts. There are two separate main photochemical routes conveniently designated as ¹(π*, n) or ³(π*, π) tracks. The latter may also be attained by sensitization and leads to phenols. The former, by α-cleavage furnishes dienketens as indispensable phototransients. Photolysis of dien-ketens follows one or more of three reaction channels, each of which yields a particular type of photoproduct: heat-induced monocyclization affords 2,4-cyclohexadien-1-ones, heat-induced bicyclization stereoselectively furnishes bicyclo[3.1.0]hex-3-en-2-ones, and multi-step addition of protic nucleophiles stereoselectively gives 1,4-, 1,6- and/or 1,2-adducts. By X-ray analysis or NOE studies, the structure of isolated photoproducts is established. Conventional spectroscopy at low or flash spectroscopy at normal temperature yield information on the formation and decay of kinetically unstable intermediates. Photoproduct composition depends on the pattern of substitution of the educts, on the solvents, and on the nucleophiles that might be present. Substituents primarily exert an influence upon the population of the various conformers of the dien-keten. Solvents affect the rate of the divers reaction paths competing for the phototransient. Nucleophiles play more than a trivial role when adducts are formed. With the detailed view of a dien-keten's role on hand, the photoproduct from a given o-quinol-acetate or more general from a linear conjugated cyclohexadienone is now predictable.     

Über Phosphorstickstoff-Verbindungen. XXXI. Über neue viergliedrige Ringsysteme mit Stickstoff,Phosphor und Kohlenstoff im Ring

A P? N compound XI, formula see ?Inhaltsübersicht”?, has been prepared containing three interconnected four-membered rings. On chlorination of XI P₂(NCH₃)₂Cl₆ is re-formed, besides a further product being very probably compound XII with hexa-coordinated phosphorus. Interaction between the known Cl₄P(NCH₃)₂ CCl₂ and NN′-dimethyl urea yields III and another compound, VII, with phosphorous of coordination number six.     

Über Pterinchemie. 64. Mitteilung. Die Kristallstruktur von 6-Methyl-7,8-dihydropterin-monohydrochlorid-monohydrat

The crystal structure of 6-methyl-7,8-dihydropterine-monohydrochloride-monohydrate The crystal structure of the title compound has been determined by X-ray analysis (direct methods) and refined with 990 structure amplitudes to R = 0.025. The crystal system is triclinic, space group P1 , with unit cell dimensions a = 5.859, b = 7.686, c = 12.107, α = 71.84, β = 76.35, γ = 85.80. The molecule is protonated at the N(5)-position and is planar. The atoms H(19) and H(20) are with 0.818 Å above respectively with ?0.705 Å under the plane.     

Über Pterinchemie 67. Mitteilung Zum Verlauf der katalytischen Reduktion von 6, 7-Diphenylpterin

On the pathway of the catalytic reduction of 6,7-diphenylpterin The pathway of the hydrogen addition to the pyrazine ring of 6, 7-diphenylpterin ( 1a ) during acid-catalyzed reduction was elucidated. Initial hydrogenation of the 5, 6-double bond produces 6, 7-diphenyl-5, 6-dihydropterin ( 2a ); this then undergoes a [1, 2]-H-rearrangement, which yields the thermodynamically more stable 6, 7-diphenyl-7, 8-dihydropterin ( 3a ). Subsequent reduction of 3a gives 4 .