New rearrangement in biphenyl series

Conclusions 2'-Lithium-2-tert-butylsulfonylbtphenyl rearranges to 2'-tert-butylbiphenyl-2-sulfinic acid, which confirms the previously proposed mechanism for the formation of this acid by the action of butyllithium on tert-butyl phenyl sulfone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2367–2368, October, 1973.     

Ene syntheses in the s-triazine series

β-Oxo-s-triazines undergo an ene synthesis with dienophiles. The ease of the reaction depends on the substituents of the triazine ring and on the nature of the enophile.     

Methods of isolating alkaloids of the colchicine series

This review considers methods for the isolation of colchicine, colchamine, and colchicoside. The literature for the period from 1884 to 1997 has been used. I. G. Kutateladze Institute of Pharmacochemistry, Academy of Sciences of the Georgian SSR, Tbilisi. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 592–600, September–October, 1990.     

Methods of isolating alkaloids of the colchicine series

This review considers methods for the isolation of colchicine, colchamine, and colchicoside. The literature for the period from 1884 to 1997 has been used.I. G. Kutateladze Institute of Pharmacochemistry, Academy of Sciences of the Georgian SSR, Tbilisi. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 592–600, September–October, 1990.     

New sterically hindered di-o-quinones of the biphenyl series

New di-o-quinones of the biphenyl series, namely, 2,2′-dialkyl-5,5′-di-tert-butylbiphenyl-3,4,3′,4′-diquinones, were synthesized. Their structures were established by IR and NMR spectroscopy. The molecular structure of 2,2′-dimethyl-5,5′-di-tert-butylbiphenyl-3,4,3′,4′-diquinone was established by X-ray structural analysis. The structure is characterized by orthogonal (the torsion angle is 82.9°) mutual arrangement ofo-benzoquinone fragments. ESR studies demonstrated that chemical reduction of diquinone proceeds in four oneelectron stages to form paramagnetic mono- and trianions as intermediates. Quinopyrocatechols, which are intermediates in the synthesis of di-o-quinones, were isolated and characterized. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 804–809, April, 1997.     

异环二取代二茂铁衍生物的合成

从芳基二茂铁的汞化产物中首次分离出四种异环二取代产物 1-氯汞基-1'-芳基二茂铁。1-氯汞基-1'-芳基二茂铁与碘作用得到四种相应的碘代产物。氯汞基二茂铁及1-氯汞基-1'-芳基二茂铁经[ClRh(CO)~2]~2 催化偶联反应制得联二茂铁和三种1'、1''-二芳基联二茂铁。以上化合物的组成与结构经元素分析、IR 和^1H NMR确证, 其中10种为新化合物。     

Studies on the syntheses of hydrogenated quinolines and isoquinolines as analgesics—XVII The steric structure of N-methyl-8-aza-des-N-morphinan

The configuration of positions 13 and 14 in N-methyl-8-aza-des-N-morphinan has been investigated. Potassium t-but-oxide in t-butanol converts N-acetyl-10-oxo-8-aza-des-N-morphinan (XVI) into 10-hydroxy-8,10-(-oxo-ethano)-8-aza-des-N-morphinan (XVII). Formation of these new lactams is possible only when rings B and C are cis. It follows, therefore, that 8-aza-des-N-morphinan synthesized in this investigation has B/C in cis and C/D in trans positions the same as the steric structure of morphinan (M).     

Studies on the syntheses of heterocyclic compounds—CCCLXXI Synthetic approach to camptothecin

Picolinic acid 1-oxide (III) was esterified with thionyl chloride and ethanol to the ester IV, whose treatment with phosphoryl chloride gave ethyl 6-chloropicolinate (V). Hydrolysis of V with hydrochloric acid gave 6-oxo-1,6-dihydropicolinic acid (VI). Simultaneous condensation and cyclisation of the methyl ester of VI with methyl acrylate in the presence of sodium carbonate in dimethylformamide yielded the bicyclic ketoester (VIII). Hydrolysis and decarboxylation of VIII with hydrochloric acid gave 3-keto-pyrrolidino[2.1-f]-2-pyridone (IX). Friedänder condensation of IX with 2-aminobenzaldehyde gave the camptothecin analogue II.     

Studies on argentine plants—XX The syntheses of fargarine II

Fagarine II has been synthesized starting from tetrahydropseudoberberine and its proposed structure (V) confirmed.     

Studies on the imidazole series

The reaction of 2-mercaptoimidazole and its 4(5)-aryl- and 4,5-diaryl-substituted derivatives with -halogenoketones has yielded a number of alkyl-, acyl-, and aryl-substituted imidazo[2,1-b]thiazoles.For part XLV, see [1].     

Molecular structure and mesomorphism in the series of discotic esters derived from benzene,triazine, biphenyl,and triphenylene

New mesogenic discotic triazine-based esters were synthesized and shown to form a low-temperature monotropic columnar mesophase. Using as examples the newly synthesized compounds and previously prepared discotic esters on the basis of benzene, biphenyl, and triphenylene, the effects of the nature and size of the central fragment and the number, position, length, and rigidity of peripheral substituents therein on the mesomorphic properties (in particular, the ability to form columnar and nematic mesophases) were examined. The main structural factors stabilizing columnar and nematic mesophases were revealed. Nematic mesomorphism was shown to be favored by increased size of the central fragment of the discogen molecule and by the presence of cyclohexane fragments in peripheral substituents.     

Studies toward the enantioselective syntheses of oxylipins: total synthesis and structure revision of solandelactone E

An efficient and general entry to unsaturated cyclopropane- and lactone-containing oxylipins of marine origin has been designed and applied to the first enantioselective total synthesis of solandelactone E. The synthesis, which proceeds in a total of 23 steps from commercially available materials, features a diastereoselective acetal-directed cyclopropanation of an electron-deficient diene, a regioselective Sharpless enantioselective dihydroxylation, and a stereoselective [2,3]-sigmatropic rearrangement of a selenoxide to effect a 1,3-transposition of an allylic alcohol. Comparison of spectral data for the synthetic solandelactone, thus prepared, with data in the literature led to a revision of the original structural assignments of the C(11)-epimeric solandelactones.     

Molecular structure of biphenyl in an argon matrix

The infrared spectrum of biphenyl was measured in an Ar matrix at 20 K. A comparison of the results with the spectra of this molecule in the solid liquid states shows that the structure of biphenyl in the matrix is similar to that in the liquid state, that is, the molecule is non-planar.     

Studies on the chemical syntheses and on the characteristics of polyaniline derivatives

Syntheses of parent polyaniline and methyl, methoxy, and ethoxy ortho-substituted polyanilines were performed using the conventional chemical methodology and monitored using the new open-circuit-potential (V_oc) profile technique. The intermediate pernigraniline oxidation state was identified and isolated at the V_oc maximum (A) during the conventional chemical synthesis of poly(o-methoxyaniline) in the emeraldine oxidation state. The introduction of the substituent on the aniline ring leads to longer polymerization times and lower V_oc values. Syntheses in the presence of two different monomers in solution were also investigated and showed preferential polymerization of the monomer with the lowest V_oc potential. All polymers produced were characterized by elemental analysis, gel permeation chromatography, UV-VIS spectroscopy, and cyclic voltammetry. The influence of the substituent on the V_oc profile and on the polymer characteristics are rationalized in terms of steric and electronic effects. © 1995 John Wiley & Sons, Inc.