2-(N-Alkyl-p-hydroxyanilino)-1,4-benzochinone ausp-Benzochinonen und primären aliphatischen Aminen

In acetic (aqueous or chloroform) solutionp-benzoquinones yield with primary aliphatic amines mainly 2-(N-alkyl-p-hydroxy-anilino)-1,4-benzoquinones besides the 2-alkylamino- and 2,5-bis(alkylamino)-quinones. The methyl-, ethyl-,n-propyl-,n-butylhomologues ofp-benzoquinone and the isomer methylderivatives of toluquinone are described. Their structure were established by spectroscopic (UV/VIS, IR, NMR) methods and by synthesis of the methylderivative3 a fromp-benzoquinone andp-hydroxy-N-methylaniline. The influence of other acids on the reaction was studied.

Herrn Prof. Dr.G. Zigeuner, Universität Graz, mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Die Reaktion von 7,14-Cyclo-7,8-dihydrocodeinon mit Diazomethan

Reaction of 7,14-cyclo-7,8-dihydrocodeinone (1) with diazomethane gives a mixture, from which nine compounds were isolated; the structures of seven (4a–c, 5, 6, 7a and8) could be determined. Insertion of a methylene group between carbon atoms 5 and6 of1 leads with opening of the ether bridge to7a as the major product.

Herrn Univ.-Prof. Dr.G. Zigeuner mit den besten Wünschen zum 60. Geburtstag gewidmet.     

2H-Isoindol-4,7-dione durch Addition von Azomethinyliden an 1,4-Benzochinone

Summary A new approach to the synthesis of 2H-isoindole-4,7-diones is described. Heating -amino acids with carbonyl compounds generates azomethine ylides through the elimination of water and carbon dioxide. The ylides were captured by quinones forming 2H-isoindole-4,7-diones, 2,3,3a,7a-tetrahydro-1H-isoindole-4,7-diones and 2,3-dihydro-1H-pyrrolo[2,1-a]isoindole-6,9-diones. The structures were established on the basis of spectroscopy (NMR, mass).

Herrn Univ.-Prof. Dr. G. Zigeuner zum 70. Geburtstag gewidmet     

Synthese und Reaktivität von 2- und 3-hydroxylierten Dihydro-1,4-Benzoxazinen

2 can be pyrrolized to yield3 a, which in turn may be hydrolyzed with HCl to3 b. Acetylation of3 a followed by a reaction with trifluoroacetic acid (TFA) gives3 e. Elimination of ethanol from3 a or of water from3 e is not possible. Treatment of1 a with pyridine/acetic anhydride andTFA or with acetic acid/acetic anhydride affords4 a and4 b, resp. Reaction of4 b in benzene/p-toluenesulfonic acid for 2 hours yields both ethers5I and5II, whereas after 6 hours 4-acetyl-4H-1,4-benzoxazine (6) is obtained. The structures of all products are established by chemical and spectroscopic methods.

Teile aus der DissertationW. Kropp, Universität Wien, 1977.     

Die Phosphonat-Phosphat- und Phosphat-Phosphonat-Umlagerung und ihre Anwendung,Teil 2: Stereochemie der Phosphonat-Phosphat-Umlagerung am Kohlenstoff am Beispiel der Isomerisierung von (R)-(+)- und (S)-(−)-(1-Hydroxy-1-phenylethyl)-phosphonsäure-diethylester

Summary The phosphonate-phosphate-rearrangement of (R)-(+)- and (S)-(–)-6 was investigated at room temperature in various organic solvents and mixtures of organic solvent and of up to 7% of water, using potassiumt-butoxide, potassium hydroxide, andDBU as bases. The rearrangement is shown to occur with retention of configuration at carbon. The highest enantiomeric excess (10.7%) for phosphate8 was observed using a mixture ofDMSO and water (100:7) containingDBU as base. Under these conditions the cleavage of phosphonate6 into acetophenone and phosphite predominates and the yield of phosphate8 is only 7.7%.

     

Zur Reaktion von Hydrazinen mit Fluorsilanen und lithiierten Aminen

Lithium salts of hydrazines react with fluorosilanes under formation of fluorosilylhydrazines and LiF. Five membered rings are obtained in the reaction of bis(fluorosilyl)-hydrazines with lithiated amines. The mass,¹H-and¹⁹F-nmr spectra of the compounds are reported.

     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 22. Mitt.: Die Reaktion von Trimethylsilylcarbonsäureamiden mit Halogen(diorganyl)boranen

Trimethylsilylacetamide and trimethylsilyltrifluoroacetamide react with halogenodiorganylboranes to monomeric or dimeric amidoboranes depending on the organyl substituents. The compounds were characterized analytically and spectroscopically (NMR:¹H,¹⁹F,¹¹B; MS; IR).

21. Mitt.:A. Meller, W. Maringgele, K. Hennemuth undU. Sicker, J. Z. anorg. allg. Chem., im Druck.     

Synthese und Reaktionsverhalten von 3-(Bis(alkylthio)methylen)-3H-isobenzofuran-1-on-und 2-(Bis(alkylthio)methylen)-3(2H)-benzofuranon-Derivaten

Summary 3(Bis(alkylthio)methylene)-3H-isobenzofuran-1-ones2a–e and 2-(bis(alkylthio)methylene)-3(2H)-benzofuranone derivatives4a–c are obtained by reaction of phthalides1a–d or 3(2H)-benzofuranone (coumaranone3), respectively, with carbon disulfide under basic conditions followed by alkylation. The reaction behaviour of the new compounds2 and4 is investigated. 2-((2-Dimethylthio-1-oxo)ethyl)benzoic acid N,N-dimethylamide (7a) and 2-((2-dimethylthio-1-oxo)ethyl)-benzoic acid 2-methylpiperidide (7b) are surprisingly formed instead of the methylthio substitution products by treatment of2a with the corresponding amine in the presence of aluminum chloride.

Herrn Professor Dr. Dr. h. c.Waldemar Adam zum 60. Geburtstag gewidmet     

Reaktion von primären Alkylhydroperoxiden mit Amidoschwefelsäurechlorid: Alkyl(amidosulfonyl)peroxide

The novel peroxides H₂NSO₂OOCH₂ R (1 a:R=CH₂CH₃;1 b:R=CH₂CH₂CH₃) are obtained by reaction of sulphamoyl chloride with the appropriate hydroperoxides in the presence of pyridine (temperature below –30 °C, solvent diethyl ether). The solvent-free liquids1 deflagrate at ca. 0 °C. Hydrolysis or ammonolysis of1 generates the hydroperoxide and sulphamic acid or sulphamide, respectively. Controlled thermolysis of1 affords sulphamic acid and carbonyl compounds, i.e. propanal andn-propyl propanoate from1 a, butanal, 2-methylpropanal andn-butyln-butyrate from1 b. These products suggest a nonradical cyclic decomposition path-way.

     

1-Phenylamino-2-imidazoline und 1,2,5,6-Tetrahydro-1,2,4-triazine aus N-(2-Chloralkyl)-imidchloriden

1-Phenylamino-2-imidazolines3 and 1,2,5,6-tetrahydro-1,2,4-triazines4, 5 and6 are synthesized from N-(2-chloralkyl)-imidchlorides1 and phenylhydrazines. As intermediates are obtained the hydrochlorides of amidrazones2 which cyclise. The structure of the different heterocyclic systems are determined by¹H- and¹³C-NMR-spectroscopy.

     

Synthesis of N-nitrooxazolidines and N-nitrotetrahydro-1,3-oxazines from N-(2-hydroxyalkyl)- and N-(3-hydroxyalkyl)sulfamates

A method was developed for the preparation of functionally substituted N-nitrooxazolidines and N-nitrotetrahydro-1,3-oxazines by nitration of the products obtained in the reactions of N-(2-hydroxyalkyl)- and N-(3-hydroxyalkyl)sulfamates with formaldehyde.     

Studien zur Chemie von thienoanellierten O,N- und S,N-haltigen Heterocyclen, 10. Mitt.: Synthese von 2- substituierten Thieno-Diltiazemderivaten

Summary The syntheses of 2-acetyl-, 2-benzyl-, and 2-ethyl-thieno-diltiazem derivatives are described starting from the corresponding 5-substituted 3-nitro-2-thiophenthiolvia reaction with racemic methyltrans-3-(4-methoxyphenyl)-glycidate under different conditions (solvent, catalyst, temperature) to obtain purethreo orerythro products. The nitro groups of these products were reduced and the resulting amino esters cyclized. The thieno[2,3-b][1,4]thiazepin-5(4H)-ones were N-alkylated and acetylated in position 3. The desired 2-substituted 4-(2-dimethylaminoethyl)-4,5,6,7-tetrahydro-7-(4-methoxyphenyl)-5-oxothieno[2,3-b][1,4]thiazepin-6-yl acetates were isolated in good yields.

     

Etherspaltung an Pyridinen mit ungewöhnlichem Halogenierungsverlauf zu isomeren Diamino-pyridon-carbonitrilen und ihre Verwendung als Kupplungskomponenten

Ether cleavage of the two isomeric diamino-methoxy-pyridine-carbonitriles1 and2 leads to the isomeric 4,6-diamino-2(1H)-pyridone-3-carbonitrile (3 a) and 2,4-diamino-6(1H)-pyridone-3-carbonitrile (4 a), resp. Dependent on the reaction conditions in glacial acetic acid containing hydrogen bromide or potassium iodide the halogenated pyridones (3 b, 4 b–c) can be obtained.pK _s -values and UV-spectra of the pyridones are discussed.3 a and4 a can be used as azo-coupling components, yielding the azo-dyes5 and6. Similarly 4-amino-6-hydroxy-2(1H)-pyridones (7 a–b) are coupled with several aryl- and heteroaryl-diazoniumsalts to form the azo-dyes8 a–g.

Herrn emer. o. Univ.-Prof. Dr.Otto Hromatka zum 80. Geburtstag gewidemet.     

Synthesis ofN-(3-azido-2-nitroxypropyl)-,N-(2,3-diazidopropyl)-, andN-(2-azido-3-methoxypropyl)-N-alkylnitramines

N-(3-Azido-2-nitroxypropyl)-N-alkylnitramines andN-(2,3-diazidopropyl)-N-alkylnitramines were prepared by nitration and azidation ofN-alkyl-N-(2-hydroxy-3-chloropropyl)sulfamates andN-(3-azido-2-hydroxypropyl)-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 206–208, January, 1999.     

Zur Umsetzung von 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-onen mit Diazoalkanen, 2. Mitt.

Summary 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-ones2 undergo regio- and stereospecific 1,3-dipolar cycloaddition reactions with diazomethane or diazoethane to yield 3,4,6a,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones3, which slowly isomerize in solution to give the 3,4,8,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones5. The carbon of the diazoalkane dipole is attached to carbon C-8 of the benzoxazinone. The structures of the obtained products were determined by¹H- and¹³C-NMR spectroscopy. An X-ray crystal structure analysis of3 a was carried out at room temperature:C₁₁H₁₅N₃O₃,M _r =237.26, orthorhombic, Pc2₁n,a=9.173 (5),b=9.133 (4),c=13.281 (6),V=1112.6 (9) ų,Z=4,d _x =1.416 g/cm^–3, =0.93 cm^–1,R=4.33%,R _w =3.95% (919 observations, 168 parameters).

Herrn Prof. Dr. W. Fleischhacker zum 60. Geburtstag gewidmet     

1,4-Carbazolchinone ausp-Benzochinon und primären aliphatischen Aminen. Das vermeintliche und das wahre 2-Methylamino-benzochinon

The compound which is obtained in the reaction of 1,4-benzoquinone with methylamine in chloroform was supposed to be 2-methylaminobenzoquinone; actually it is 6-hydroxy-9-methyl-3-methylamino-1,4-carbazolquinone. The structure is proved by spectroscopic methods, through derivates, zinc dust distillation and via synthesis from 2,5,2,5-biphenyl-diquinone. A second main product, 2,5-bis(methylamino)quinone, is obtained; varying the reaction conditions shows especially the influence of the solvent. One of the intermediate products is the true 2-methylamino-1,4-quinone. Other substituted 9-alkyl-3-alkylamino-6-hydroxy-1,4-carbazolquinones can be prepared by reaction with the corresponding primary amines.

     

Darstellung und Charakterisierung von Halogeno(diethyldithiocarbamato) (triethyl- und triphenylphosphin)palladium(II)-Komplexen

The Complexes [Pd(PEt ₃)₂ dtc]X (1) and Pd(PR ₃)Xdtc (2, 3) (dtc=S₂CNEt ₃;X=Cl, Br, I;R=Et, Ph) have been prepared. Conductivity, susceptibility, UV and IR measurements show that the cations [Pd(PEt ₃)₂ dtc]⁺ of1 and the complexes2, 3 have square-planar structure.

     

Hydrophile Polymergele mit reaktiven Gruppen, 2. Mitt.: Chelatharze auf Basis von Glucose- und Saccharosemethacrylaten

A widely applicable method for the preparation of chelating resins based on glucose- and sucrosemethacrylate-gels is described. Primary aromatic amino groups were bonded to the carrier by esterification with 4-nitrobenzoylchloride and subsequent reduction of the nitro groups with sodium dithionite. Diazotation and coupling with various chelating ligands (8-hydroxyquinoline, dithizone, anthranilic acid, salicylic acid and pyrogallol) afforded chelating resins with capacities of max. 1.7 mmol/g. Sucrosemethacrylate-gels were etherified with 4-nitrobenzylchloride, epichlorohydrin, 4-nitrophenyl glycide ether (IIb), acrylonitrile and 4-nitrophenylacrylamide (IVb). Reaction of the gels with IIb or IVb and subsequent reduction of the nitro groups yielded reactive carriers with ether-linked primary aromatic amino groups. Diazotation and coupling with 8-hydroxyquinoline yielded chelating resins. The capacities of the gels were 0.6–0.7 mmol/g and these resins were extremely stable to changes inpH.

     

Die Kristallstruktur von TlFeSe2 und TlFeS2

TlFeSe₂ is monoclinic, space groupC2/m–C _2h ³ ,a=11.973 Å,b=5.490 Å,c=7.110 Å, =118.2°,Z=4.TlFeS₂ is isotypic witha=11.636 Å,b=5.304 Å,c=6.799 Å, =116.7°.The crystal structure of TlFeSe₂ has been determined from single crystal diffractometer data. Isotypy of the sulfide has been confirmed from powder diffraction data. The crystal structure containing infinite linear chains of edgesharing FeX ₄-tetrahedra, and its relationship to the thio- and selenoferrates of the alkali metals are discussed. The mineral raguinite is very probably isotypic to synthetic TlFeS₂.

     

Synthese und Geruch von (E)- und (Z)-bis-homo-ß-Santalol

Summary The synthesis of the title compounds is described. Guided by theoretical considerations and molecular modeling studies, the influence of the bulky group opposite to the osmophorically important primary hydroxyl function on the odour impression is determined. The organoleptic evaluation proved the predicted sandal like odour of the (Z)-isomer and its also predicted absence with (E)-isomer. A moderate increase of the volume of the bulky group shows no influence on the sandalwood odour of the new analogue.