Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

9-(2′,5′-Dimethyl-4′-pyridyl)fluorene in syntheses of fluorospirodihydrofuropyridine and pyridofluoranthene

1,2,5-Trimethyl-4-(9-fluorenylidene)piperidine, which is formed by condensation of fluorene with 1,2,5-trimethyl-4-piperidone, is converted catalytically to 9(2,5-dimethyl-4-pyridyl)fluorene, from which 2-methylpyrido[4,5-a]fluoranthene and its demethylated analog were obtained by catalytic dehydrocyclization. Oxidation of 9-(2,5-dimethy1-4-pyridyl)fluorene gave 9-(2,5-dimethyl-4-pyridyl)9-fluorenol and fluorene-9-spiro-4-(6-oxo-2-carboxypyrido[4,5-c]-4-6-dihydrofuran). 6-Methyl-2-phenyl-7-(9-fluorenyl)indolizine was synthesized by the Chichibabin method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1090, August, 1978.     

Organoboron compounds. 374. Cyclic compounds of the chelate type from 2-pyridyl-and 2-pyrimidinylaminoboranes and dicyclohexylcarbodiimide

Conclusions New chelate compounds of boron, in which the chelating agents are, respectively, N.N-dicyclohexyl-N'-(2-pyridyl)guanidine and N,N-dicyclohexyl-N'-(2-pyrimidinyl)guanidine, have been synthesized by adding 2-pyridylaminodiorganylboranes and 2-pyrimidinylaminodiorganylboranes to dicyclohexylcarbodiimide.For the preceding report see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 659–663, March, 1980.     

Umsetzungen des Diphenylphosphinsäureanilids

Zusammenfassung Diphenylphosphinsäureanilid-kalium wurde in Lösung von Dioxan erhalten und mit Alkylhalogeniden zu Diphenylphosphinsäure-alkylaniliden umgesetzt. Mit Methylenjodid entsteht N,N-Bis-[diphenylphosphinsäure]-N,N-diphenylmethylendiamid, während mit Äthylenbromid Acetylen und Diphenylphosphinsäureanilid erhalten wird. Mit Ph₂P(O)Cl bzw. PhP(O)Cl₂ erhält man N,N-Bis-[diphenylphosphinsäure]-N-phenyl-amid bzw. Phenylphosphonsäure-N,N-diphenyl-N,N-bis-[diphenylphosphinsäure]-diamid.     

Podand-porphyrins with peripheral chelates

Alkylation of 5-(3-nitro-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with chloropyridines[2,6-dichloromethyl-and 2-chloromethyl-6-(2-nitrophenoxymethylpyridine)] as well as condensation by a mixed-aldehyde method starting with formylpyridines [2-(2-nitro-4-formylphenoxymethyl)-6-(2-nitrophenoxy-methyl-) or 2,6-di(2-nitro-4-formylphenoxymethyl)pyridine], benzaldehyde, and pyrrole are used to synthesize previously unknown podand-porphyrins containing from one to four peripheral chelates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–481, April, 1991.     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

Die Dissoziationskonstanten von 2,3′-und 2,4′-Dihydroxydiphenylmethanderivaten

The pK-values of the first and second degree of dissociation of 2.3-dihydroxy-6-methyl-3.5-dinitro-diphenylmethane, 2.3-dihydroxy-6-methyl-5-nitro-diphenylmethane, 2.3-dihydroxy-5.6-dimethyl-3-nitro-diphenylmethane, 2.4-dihydroxy-3. 5-dimethyl-3.5-dinitro-diphenylmethane, 2.4-dihydroxy-3. 5-dimethyl-5-nitro-diphenylmethane and 2.4-dihydroxy-3.5.5-trimethyl-3-nitrodiphenylmethane were determined in aqueous solution at 25°C by the spectrophotometric method. The observed pK-values are compared with those of 2-methyl-4.6-dinitro-phenol, 2-methyl-4-nitrophenol, 2.4-dimethyl-6-nitrophenol, 3.4-dimethylphenol and 2.4.6-trimethylphenol which serve as model compounds for the single phenolic units.     

Esters of (1,2, 5-trimethyl-4-hydroxy-4-piperedyl)- and phenyl-(1,2, 5-trimethyl-4-hydroxy-4-piperidyl) acetic acids

The methyl ester of a new hydroxy acid of the piperidine series (-phenyl--(1,2, 5-trimethyl-4-hydroxy 4-piperidyl)acetic acid) has been prepared. Ethyl -(1,2, 5-trimethyl-4-hydroxy-4-piperidyl)acetate has been converted into the substituted pyridine, 1,1-diphenyl-2-(2-5-dimethyl-4-pyridyl)ethylene.     

Chromium(III) and oxovanadium (IV) complexes of some urea derivatives

Summary The preparation of eight new complexes of Cr^III and VO^IV with urea derivatives is reported here. The ligands used were 2-imidazolidinone (ethyleneurea, EU),N,N'-dimethyl-2-imidazolidinone (N,N -dimethylethyleneurea, DMEU), 2-imidazolidinethione (ethylenethiourea, ETU), andN, N, N, N -tetramethyl-2-imidazolidone (tetramethylurea, TMU). The previously reported complex VOCl₂(TMU)₂ was also prepared. All nine complexes were investigated with regard to conductimetry as well as visible and i.r. spectroscopy. All carbonyl-containing complexes exhibit a metal-oxygen bond, whereas in ETU complexes a metal-nitrogen bond seems to be favoured.     

The structure effect of N,N,N′,N′-alkylamide in the extraction of uranium and thorium

In this paper, nine N,N,N,N-tetraalkyldiamides have been synthesized and the extracting ability for uranium and thorium under different conditions has been studied. All results were compared with those obtained by using tributyl phosphate (TBP) under exactly the same conditions. The extracting ability of thorium and uranium for different N,N,N,N-tetraalkyldiamides is discussed.     

Über Inhaltstoffe der Iris germanica (Schwertlilie)

Acetovanillon and the known flavonoids irisolidone, irigenin, irisolone, tectorigenin and dihydroquercetin-7.3-dimethylether were detected in the rhizomes of Iris germanica. Also a few unknown compounds could be isolated and their structure elucidated; 9-methoxy-7-(3.4.5-trimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4.5-tetramethoxy-6.7-methylenedioxyisoflavone (III A); 9-methoxy-7-(3.4-dimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4-trimethoxy-6.7-methylenedioxyisoflavone(III B); 9-hydroxy-7-(p-hydroxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.4-dihydroxy-6.7-methylenedioxyiosoflavone (IX); 5.7-dihydroxy-3-(3-hydroxy-4-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.3-trihydroxy-6.4-dimethoxyisoflavone (XI B); 5.7-dihydroxy-3-(4-hydroxy-3-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.4-trihydroxy-6.3-dimethoxyisoflavone (XI C).The structure determination was effected by combined spectroscopical and chemical methods.

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Herrn Prof. Dr.F. Hecht mit den besten Wünschen zum 70. Geburtstag gewidmet.     

Palladium and platinum guanine complexes

Summary Reaction of [MCl₂(H₄Y)] or (H₆Y)[MCl₄] compounds (M = Pd or Pt; Y = EDTA, PDTA or CDTA) with guanine (Gu-H) in 0.5 M HCl yields new complexes MCl₂(Gu-H)(H₂O which have been characterized by elemental analyses in conjunction with electronic, i.r. and n.m.r. spectra. A dimeric structure with two bridging chloride ligands, including coordination of guanine through atom N(9), is proposed for both compounds.Abbreviations used in the paper EDTA 1,2-diaminoethane-N,N,N,N-tetraacetate - PDTA 1,2-diaminopropane-N,N,N,N-tetraacetate - CDTA trans-1,2-diaminocyclohexane-N,N,N,N-tetraacetate - Gu-H guanine - 9-EtGu-H 9-ethylguanine     

1,2-bis(2',6'-dimethyl-i',3'-dioxa-6'-aza-2'-silacyclooctyl-2')ethane and the corresponding ethylene and acetylene derivatives

Conclusions The reaction of 1,2-bis(methyldimethoxysilyl)ethane and the corresponding ethylene and acetylene derivatives with bis(2-hydroxyethyl)methylamine gives 1,2-bis(2,6-dimethyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)ethane and the corresponding ethylene and acetylene derivatives. Analogously, 1,2-bis(vinyldimethoxysilyl)acetylene gave 1,2-bis(2-vinyl-6-methyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)acetylene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1420–1421, June, 1988.     

Phenolic derivatives of 2-pyrone

The cyclization of 1,1-dichloro-5-(2,5-dimethoxyphenyl)-1,3-pentadien-5-one and the product of its partial demethylation leading to the corresponding derivatives of 2-pyrone and 2-(,-dichlorovinyl)-6-methoxy-4-chromanone has been studied. Irradiation causes the dimerization of 1,1-dichloro-5-(2,5-dimethoxyphenyl)-1,3-pentadien-5-one.For part I, see [1].     

Benzoylation of 1,4-diaza-1,3-butadienes: Synthesis of representatives of a new chemical class—1,2-diamino-1-chloroethylenes

Trans-N,N-dialkyl-N,N-dibenzoyl-1,2-diamino-1-chloroethylenes — the first representatives of a new chemical class — and N,N-dialkyl-N,N-dibenzoyl-1,2-diaminoethylenes were obtained by benzoylation of N,N-dialkyl-1,4-diaza-1,3-butadienes. On increase in pressure to 10,000 atm, the yields of the N,N-dibenzoylated 1,2-diamino-1-chloroethylenes increase, and those of the N,N-dibenzoylated 1,2-diaminoethylenes decrease.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2038–2041, September, 1989.     

Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

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Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

Synthesis of pyridinyl-4-pyrimidinamine derivatives

Summary N-(1-Methyl-2-pyridin-3(4)-yl-vinyl)acetimidoylchlorides (5, prepared byBeckmann rearrangement of the oximes of 3-methyl-4-pyridin-3(4)-yl-3-buten-2-ones (4)) react with cyanamide and N,N-dialkylcyanamides in the presence of titanium(IV) chloride to give 4-amino-2,6-dimethyl-5-pyridinyl-pyrimidine derivatives (7).

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Synthese von Pyridinyl-4-pyrimidinamin-Derivaten

Zusammenfassung N-(1-Methyl-2-pyridin-3(4)-yl-vinyl)acetimidoyl-chloride (5, dargestellt durchBeckmann-Umlagerung der Oxime von 3-Methyl-4-pyridin-3(4)-yl-3-buten-2-onen (4)) reagieren mit Cyanamid und N,N-Dialkylcyanamid in Gegenwart von Titan(IV)chlorid zu 4-Amino-2,6-dimethyl-5-pyridinyl-pyrimidin-Derivaten (7).