9(11)-Secoestra-11,17-dioic acids and related compounds

While hydrogenations of 2b furnished a mixture in which the rac 14α isomer 8b predominated, the rac lactone 6 was hydrogenolyzed to give the rac 14β diacid 9a. Clemmensen reduction of 6 gave the rac 14α tetrahydro compound 7a. Another route to 8 involved conversion of the d-ketoacid 11b into 23b via the cyanolactone 20b or the amidolactone 21b. Base-catalyzed elimination at 206° yielded the Δ¹⁶ diester 27 which was hydrogenated to 8c. An analogous conversion was also carried out in the ring B reduced series 13 → 20a + 21a → 23a → 25a → 26. In the 14β series, using the same sequence of reactions, the rac ketoacid 10a was transformed into the rac lactone ester 29. In distinction from the 14α series, treatment with alkali at 206° gave only partial elimination, the double bond migrating to the 14,15 position to furnish 2. Evidence is presented that amides of the ketoacid 13a exist in the hydroxylactam form 30 and can be readily O-alkylated to furnish 22. Attempts to aromatize ring B of 13a with DDQ led to lactones 15 and 16, while reaction of the ester 13b with DDQ gave the pentaene 17 and the hexaene 18, establishing that dehydrogenation proceeded stepwise in the sequence Δ⁸, Δ¹⁴ and finally Δ⁶.     

Detection of lysergic acid diethylamide, delta-9-tetrahydrocannabinol and related compounds by plasma chromatography.

Plasma chromatography as a method for ultratrace qualitative and quantitative detection of organic compounds is especially well suited for detection of gas chromatographic effluents. The optimum range of sample quantity is 10-6 to 10-12 g for detection and identification of a compound by use of its characteristic positive and negative mobility spectra. The type of reference mobility spectra produced by alkanes, aromatics, esters, halogenated compounds, nitrogenated compounds and organic acids have been previously reported. This study presents the reference mobility spectra produced for lysergic acid diethylamide (LSD), delta-9-tetrahydrocannabinol (delta-9-THC), digitoxigenin and several biochemical compounds of research significance. LSD and delat-9-THC in a mixture can be detected and identified by plasma chromatography positive mobility spectra in quantities of 10-7 g or less. All the compounds investigated in this study display strong MH-+ ions along with other ions primarily of the type (M)NO-+, (M)2H-+. None of these compounds exhibits negative mobility spectra.     

The stoichiometric hydrogenation of 9-methylidenefluorene and related compounds with hydridocobalt tetracarbonyl

9-Methylideneflourene (IIa) reacts rapidly with HCo(CO)₄ at -67° C to give a quantitative yield of 9-methylfluorene (IIIa); k₂  (13.4 ± 0.5) × 10^-2 l mol^-1_S^-1. Although the internal olefin, 9-ethylidenefluorene (IIb) reacts more slowly than IIa, it is hydrogenated about 2.5 times as fast as the terminal olefin, 1,1-diphenylethylene (I). Measurement of the rate of the reaction of IIb with DCo(CO)₄ and comparison with HCo(CO)₄ shows a very large inverse isotope effect k_H/k_D of 0.43.     

Di-isophorone and related compounds. Part 9 1-(substituted)aminodi-isophoranes and their cyclodehydration products

The interaction of 1-chlorodi-isophor-2(7)-en-3-one (or its 5,11-bisnorhomologue) with aromatic, heteroaromatic, or saturated heterocyclic amines produces 1-(substituted)aminodi-isophor-2(7)-3n-3-ones by nucleophilic replacement of the bridgehead halogen. Subsequent cyclodehydration affords, in certain examples, substituted 2,3,5,6,7,8-hexahydro-1H,9h-5,8a-methanocycloocta[gh]phenanthridines (2,3-dehydro-1-anilinodi-isophor-2,7-dien-3-ols). Some physical and chemical properties of these novel amines and condensed pentacylic bases are described.Part 8,Allen, A. A., Kurzer, F., Mh. Chem.112, 617 (1978).     

Substituted pyrimidines. II. 1,3-Dimethylisocytosine and related compounds

1,3-Dimethyl-1,2-dihydro-2-imino-4(3H)pyrimidinone (1,3-dimethylisocytosine) was prepared by methylation of 2-amino-3-methyl-4(3H)pyrimidinone and was degraded in alkaline solution to a mixture of 3-methyl-2-methylamino-4(3H)pyrimidinone, 1,3-dimethyl-2,4-(1H,3H)pyrimid-indione, 2-methylamino-l-methyl-4(1H)pyrimidinone, 1-methyl-2,4-(1H,3H)pyrimidindione and 3-methyl-2,4-(1H,3H)pyrimidindione. Thiation of the title compound gave both 1,2-dihydro-1,3-dimethyl-2-thio-4(3H)pyrimidinone and 1,3-dimethyl-2,4-(1H,3H)pyrimidinedithione. The title compound is a tautomerically fixed pyrimidine and its uv spectra were compared with related compounds, notably 3-methyl-2-dimethylarnino-4(3H)pyrimidinone which is also tautomerically fixed.     

HPLC of antibiotics. 1. Streptolydigin and related compounds

Two new acyltetramic acids related to streptolydigin have been isolated from fermentations of Streptomyces lydicus. The principal members of this complex were resolved by TLC on silica gel. However, the methods of detection, permanganate spray or bioautography, were not suitable for both crude fermentation broths and purified extracts. Gas chromatography is unsuitable for the detection of either underivatized or silylated streptolydigins. High performance liquid chromatography (HPLC) particularly on triethylaminoethyl cellulose is rapid and sensitive and is the method of choice for the analysis of both crude and purified samples. Using high performance liquid chromatography, two components were detected in the complex, which are not observed using any of the other chromatographic procedures.     

Benzoxazines and related compounds

The action of a nitrating mixture on 2-substituted 4,4-diethyl-4H-1,3-benzoxazines gives the corresponding 6-nitro derivatives, which can be isolated as such or as the hydrolysis products –N-acyl-,-diethyl-2-hydroxy-5-nitrobenzylamines. The latter cyclize to the corresponding 4H-1,3-benzoxazines under the influence of perchloric acid.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 303–305, March, 1972.     

Benzoxazines and related compounds

A simple method has been elaborated for synthesizing 2-substituted 4,4-dialkyl-4H-1, 3-benzoxazines by the interaction between nitriles and o-oxyphenyldialkylcarbinols under the influence of acids.For part I, [1].     

Hydroacridines and related compounds

One hydrogen atom is replaced by lithium in the reaction of 1,2,3,4-tetrahydroacridine and sym-octahydroacridine with phenyllithium; effective replacement of a second hydrogen atom by lithium becomes possible after replacement of the first lithium by an alkyl group. This makes it possible to achieve step-wise alkylation.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 673–675, May, 1972.     

Gibberellins and related compounds

Conclusions A study was made of the photochemical aromatization of the 2-keto derivative of gibberellic acid in various solvents. Unusual fragmentation of the B ring, with the formation of the seco-structure, was observed when the reaction was run in benzyl alcohol.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2037–2040, September, 1971.     

Hydroacridines and related compounds

The stereochemistry of the hydride reduction of N-substituted 4a-cyano-, 4a,10a-dicyano-, and 4a,10a-peroxy-9-phenylperhydroacridines was studied. The configuration of a series of isomeric N-substituted 9-phenylperhydroacridines was established.See [1] for communication XIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 508–512, April, 1977.