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.

     

Thermodynamische Untersuchungen ann-Alkan/n-Alkin-Systemen

Heats of mixing (H ^E)ofn-octane with 1,2,3,4-isomers ofn-octyne,n-heptane withn-1-heptyne andn-nonane withn-1-nonyne at temperatures from 298.15 to 318.15 K were measured with aCalvet-type microcalorimeter. The results are presented in tables and correlated with theRedlich-Kister equation.

     

Synthese von 1-Ary1-4-methylthio-2-azetidinonen

TheN-arylthioformimidates4 a-e, which may be obtained byS-alkylation of the thioformanilides3 a-e, react with chloroacetylchloride/triethylamine to yield the (3R,4S/3S,4R)-1-aryl-3-chloro-4-methylthio-2-azetidinones5 a-e and the formanilides6 a-e. Dehalogenation of5 b-e with tri-n-butyltinhydride yield the title compounds7 b-e. Hydrogenolysis of7 b and7 c yields7 f and7 g.

     

Reductivetrans-2,6-diallylation of pyridines with allylboranes. Synthesis oftrans- andcis-2,6-diallyl-1,2,5,6-tetrahydropyridines and their deuterated derivatives

The reductivetrans-2,6-diallylation of pyridines with triallyl- and allyl(dialkyl)boranes has been discovered. Heating (40–100 °C) of pyridine, deuteropyridine, or 3-bromopyridine complexes with triallylborane in the presence of alcohols (ROH or CH₃OD), water, or Et₂NH results in the respectivetrans-2,6-diaIlyl-1,2,5,6-tetrahydropyridines (2,3,22, or25) in 20–97 % yields. A preparative method for the isomerization oftrans-2,6-diallyl compounds2 and25 into the respectivecis-isomers4 and28 by heating them with triallyl- or allyl(dialkyl)boranes (125–150 °C) has been suggested. The hydrogenation oftrans- orcis-2,6-diallyl-1,2,5,6-tetrahydropyridines gavetrans- orcis-2,6-dipropylpiperidines, respectively. Thecis- andtrans-configurations of compounds2 and4 were established by analyzing the NMR spectra ofN-benzyl (7 and13) andN,N-dimethyl (6 and 14) derivatives of piperidine derivatives5 and8. A possible mechanism for the reductive diallylation of pyridines has been discussed.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 693–704, April, 1994.This study was financially supported by the Russian Foundation for Basic Research (Project 93-03-18193).     

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.     

Effects of micellar structure on solubilization ofn-octane andn-octanol

The solubilization ofn-octane andn-octanol in nonionic micelles of octaethylene glycoln-alkyl ethers was investigated by means of various techniques including solubilization, fluorescence, and dynamic light-scattering measurement. With respect to the effect of alkyl chain length of the surfactants, different solubilization behavior was observed betweenn-octane andn-octanol. That is to say, it was shown that the solubilization ofn-octane increases with an increase in the alkyl chain length, while that ofn-octanol decreases. An interpretation of these solubilization mechanisms is explained from the standpoint of the volume of hydrophobic and hydrophilic regions in a micelle.     

The easy hydrolysis of hexacyanocyclopropane, ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate, 1,2,2,3,3-pentacyanocyclopropane-1-carboxamide, andN,N-dimethyl-1,2,2,3,3-pentacyanocyclopropane-1-carboxamide tor-1,c-2,c-3-tricyanocyclopropane-t-carboxamide

Hydrolysis of hexacyanocyclopropane (1a), ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate (1b), 1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1c), andN,N-dimethyl-1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1d) in 95% acetic acid yieldsr-1,c-2,c-3-tricyanocyclopropane-t-1-carboxamide (3). The structure of3 was proved by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 454–456, March, 1998.     

Vergleichende Reaktivitätsuntersuchungen am neuen Codimeren aus Malonitril und Cyanessigester an Carbonylverbindungen

The reactivity of 3-amino-2,4-dicyano-methyl-(1d) and-ethyl-crotonate (1e), resp., a new type of codimer from malononitrile and cyanoacetate, was investigated. Condensation reactions with aromatic aldehydes (2a-g), with heterocyclic aldehydes (2j-l), nitrosobenzenes (3a-c) ando-hydroxybenz-and-naphtaldehydes (4a-f), resp., are described, the differences in reactivity, compared with dimer malononitrile and dimeric forms of cyanoacetate (1a-c) are negligible. Condensation compounds of1a with cycloalkanones (5a-c) are able to cyclise with sulfur to cycloalkanonothieno-pyridines (6a-b), while the cycloalkano-derivatives of1d gave no ring closure.

Herrn Prof. Dr.O. E. Polansky zum 60. Geburtstag in Erinnerung an gemeinsame Tätigkeiten auf dem Gebiet der Nitrilchemie gewidmet.     

Über Darstellung und Reaktivität von 2,4-Diazabicyclo[3.3.1]nonan-3-onen

The 2-cyclohexenones1 a andd resp. react with urea in HCl/EtOH to give 1-hydroxy-4-methyl-7-phenyl- and 1-hydroxy-2,4-diazabicyclo[3.3.1]nonane-3-ones3a and3d resp., whereas the 2-cyclohexenones1b andc resp. transformed by urea to 1,7-dimethyl- and 1-methyl-4-ureido-2,4-diazabicyclo[3.3.1]nonan-3-ones9b andc resp. In the condensation of isophorone1e with urea a product C₁₃H₂₈N₈O₄ of indisdinct structure was formed, whereas the bicyclus3e could not be isolated.Reaction ofAcOAc with3a yielded the 5-methyl-3-oxo-7-phenyl-2,4-diazabicyclo[3.3.1]non-1-ylacetate (15); on heating of3a with acids decomposition to1a and urea took place. NoWagner-Meerwein-rearrangement was observed. The MS-spectra of3a andd are discussed; NMR- and IR-data are reported.No significant herbicidal, fungicidal or insecticidal activity was found in screening-tests on3a.

     

Transformations of pyridine and deuteropyridine under the action of trimethallylborane and alcohols. Synthesis oftrans- andcis-2,6-dimethallyl-1,2,3,6-tetrahydropyridines and theirN-derivatives

Reductivetrans-2,6-dimethallylation of pyridine and deuteropyridine with trimethallylborane in the presence of alcohols proceeds at room temperature,i.e., under substantially milder conditions than the analogous reaction with the participation of triallylborane.trans-2,6-Di(2-methylallyl)-1,2,3,6-tetrahydropyridine (3) was obtained in a yield of 87%. When heated with trimethallylborane (130–135°C, 2.5 h), compound3 underwent isomerization tocis-2,6-di(2-methylallyl)-1,2,3,6-tetrahydropyridine (4). Hydrogenation oftrans- (3) andcis-isomers (4) yieldedtrans- andcis-2,6-diisobutylpiperidines, respectively. The heterocycles obtained wereN-functionalized by reactions with MeI, PhCH₂Cl, ethylene oxide, and perfluoropropyloxirane. The stereochemistry of thecis- andtrans-isomers (3 and4) was established based on the NMR spectra of theirN,N-dimethyl salts and the products of the reaction with ethylene oxide.trans-2,6-Dimethallyl-2,3,4,5,6-pentadeutero-1,2,3,6-tetrahydropyridine and a number of its derivatives were prepared from the complex of trimethallylborane with C₅D₅N. A probable mechanism of the reductivetrans-2,6-diallylation of pyridines with allylboranes in the presence of alcohols is discussed. This article is dedicated to Prof. W. Siebert (Heidelberg) on the occasion of his 60th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1361–1370, July, 1997.     

Preparation oftrans- andcis-2-allyl-6-alkyl(aryl)-1,2,3,6-tetrahydropyridines based on the reductivetrans-2,6-dialkylation of pyridine. Synthesis of (±)-epidihydropinidine and (±)-dihydropinidine

A general method for the preparation of unsymmetricaltrans-2-allyl-6-alkyl(aryl)-1,2,3,6-tetrahydropyridines6 based on a combination of 1,2-addition of RLi to pyridine andtrans-6-allylation with triallylborane in the presence of methanol was elaborated. It was shown thattrans-piperideines (6 (R=Alk, Ph) isomerize into the correspondingcis-2-allyl-6-alkyl(phenyl)-3-piperideines14 on heating with triallylborane followed by deboronation of aminoborane (16) with methanol and an alkali. The stereochemistry of compounds6 and14 was determined by two-dimensional NOE spectroscopy. A possible mechanism of the formation oftrans-amines6 and their transformation intocis-isomers14 is discussed. Alkaloids (±)-epidihydropinidine (trans-2-methyl-6-propylpiperidine2a, 70%) and (±)-dihydropinidine (cis-2-methyl-6-propylpiperidine1d, 71%) were synthesized by hydrogenation of compound6a (R=Me) and14a (R=Me), respectively, over Raney nickel. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–474, March, 1998.     

Preparation and steric structure of 3(2H)-pyridazinones and 1,2-oxazin-6-ones fused with three- to six-membered saturated carbocycles or norbornane skeleton

Summary Reactions ofcis-2-(4-methylbenzoyl)-cyclopropane- (1) and-cyclobutanecarboxylic acids (2), the stereoisomeric cyclohexyl homologues (3 and4), and di-endo-3-(4-methylbenzoyl)-bi-cyclo-[2.2.1]heptane-2-carboxylic acid (5) with hydrazines yield the cycloalkane-condensed (3(2H)-pyridazinones6–9 and the norbornane di-endo-fused derivatives10. With hydroxylamine, compounds1 and3–5 were transformed to the cycloalkane- and norbornane-condensed 1,2-oxazin-6-ones11–14. Transformation of3–5 led to thetrans-hexahydroanthrone17a and its methylene-bridged analogue24. From the stereoisomeric hexahydro-1(3H)-isobenzofuranones20 and21, the partly saturated anthrones were also prepared; the products (16b and17b) contain the methyl substituent in position 6. On reduction,16b yield the 2-methyloctahydroanthracene22. The structures of the compounds were proved by¹H and¹³C NMR spectroscopy, making use of NOE, DEPT, and CH-COSY techniques.

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Synthese und räumliche Struktur von mit drei- bis sechsgliedrigen gesättigten Homocyclen oder Norbornan kondensierten 3(2H)-Pyridazinonen und 1,2-Oxazin-6-onen

Zusammenfassung Die Reaktion voncis-2-(4-methylbenzoyl)-cyclopropan-(1) und-cyclobutancarbonsäuren (2), der stereoisomeren cyclohexyl-Homologen (3 und4) und von di-endo-3-(4-methylbenzoyl)-bicyclo[2.2.1]heptan-2-carbonsäure (5) mit Hydrazinen ergibt die cycloalkankondensierten 3(2H)-Pyridazinone6–9 und das methylenüberbrückte di-endo-Derivat10. Die Verbindungen1 und3–5 wurden mit Hydroxylamin zu den cycloalkan- und norbornankondensierten 1,2-Oxazin-6-onen11–14 umgesetzt.3–6 reagierten zumtrans-Hexahydroanthron17a und seinem methylenüberbrückten Analogen24. Die teilweise gesättigten Anthrone wurden auch aus den stereoisomeren Hexahydro-1(3H)-isobenzofuranonen20 und21 hergestellt (16b und17b), wobei der Methylsubstituent jedoch in Position 6 lokalisiert ist. Reduktion von16b ergab das 2-Methyloctahydroanthracen22. Die Strukturen der Verbindungen wurden durch NMR-Spektroskopie abgesichert (¹H,¹³C, DEPT, CH-COSY, NOE).

     

Allylic lithiation of methylenecyclobutanes

Methylenecyclobutanes undergo a lithiation reaction in the presence of n-BuLi or n-BuLi/KO^tBu from −78 °C to room temperature or to 40 °C in THF within 3 h and then quenching with a variety of electrophiles to give the corresponding addition products (alcohols) in moderate to good yields within 2 h. The alcohols can be easily oxidized to the ketones, which can be transformed to the substituted cyclopentenes in the presence of AlCl₃ within short reaction time.     

Synthesis and photoinduced isomerization ofansa{·5,·5′-[1,1′-(1-silacyclopent-3-ene-1,1-diyl)bis(indenyl)]} dichlorozirconium The crystal structure of itsmeso form

ansa{·⁵,·⁵′-[1,1′-(1-silacyclopent-3-ene-1,1-diyl)bis(indenyl)]} dichlorozirconium (1a,b) was synthesized. The crystal structure ofmeso-[(1,4-CH₂CH=CHCH₂)Si(C₉H₆)₂ZrCl₂] (1b) was established by X-ray diffraction analysis. Photoinduced interconversion of the racemic (1a) andmeso forms was studied under various conditions. The photostationary state (rac: meso=55∶45) was established rapidly when solutions ofansa-zirconocene were irradiated with visible light. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2351–2356, November, 1998.     

On the interaction of metal extractant reagents. Investigation of the aggregation ofdi(2,4,4-trimethylpentyl)phosphinic acid anddi(n-octyl)phosphinic acid in toluene by vapour-pressure osmometry

Summary The aggregation equilibria ofdi(2,4,4-trimethylpentyl)phosphinic acid (HDTMPP) anddi(n-octyl)phosphinic acid (HDOP) dissolved in toluene have been investigated by vapour-pressure osmometry (VPO) at different temperatures. The experimental data have been treated both graphically and numerically, and the average aggregation numberñ as well as the aggregation constant have been determined. The results suggest that dimers are formed and that the dimerization constant decreases with temperature. Finally, the enthalpies for the aggregation ofdi(2,4,4-trimethylpentyl)phosphinic acid anddi(n-octyl)phosphinic acid in toluene have been estimated using thevan't Hoff equation.

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Über die Wechselwirkung metallextrahierender Reagentien. Untersuchung der Aggregation vondi-(2,2,4-Trimethylpentyl)-phosphinsäure unddi-(n-Octyl)-phosphinsäure in Toluol mittels Dampfdruckosmometrie

Zusammenfassung Die Aggregationsgleichgewichte von in Toluol gelösterdi-(2,4,4-Trimethylphentyl)-phosphinsäure (HDTMPP) unddi-(n-Octyl)-phosphinsäure (HDOP) wurden mittels Dampfdruckosmometrie (VPO) bei verschiedenen Temperaturen untersucht. Die experimentellen Daten wurden sowohl graphisch als auch numerisch ausgewertet; es wurden sowohl die mittlere Aggregationszahlñ als auch die Aggregationskonstante bestimmt. Die Resultate lassen vermuten, daß Dimere gebildet werden und die Dimerisationskonstante mit der Temperatur abnimmt. Mit Hilfe dervan't Hoffschen Gleichung wurden die Enthalpien der Aggregation vondi-(2,4,4-Trimethylpentyl)-phosphinsäure unddi-(n-Octyl)-phosphinsäure in Toluol abgeschätzt.

     

The effect of substituents (CH3 and NH2) in positions 4 and 6 on the acid-base properties of 2(1H)-pyrimidinethiones

The acid-base properties of 4,6-dimethyl- and 4,6-diamino-2(1H)-pyrimidinethiones (1 and2) were investigated by potentiometric titration. Dissosiation of1 and protonation of its anion occur in two steps, the first of which affords the deprotonated dimer [HA₂)^–. The relative stability of the dimer depends on the nature of the solvent. The effect of kinetic factors on the acid-base behavior of1 was elucidated by comparing the results of potentiometric titrations carried out under various kinetic conditions. It was concluded that the difference between the acid-base properties of1 and2 results from the electron-donating effect of the amino groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2145–2148, December, 1994.     

Synthesis of partially saturated N-substituted 4H-3,1-benzothiazine-2(1H)-thiones

Summary Acid-catalyzed reaction of 2-arylidenecyclohexanones1 with N-substituted dithiocarbamic acids2 gave open-chain addition products3 and4. Dehydration of3 and4 afforded only one of the three possible isomeric N-substituted 4H-3,1-benzothiazine-2(1H)-thiones5 and6.

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Synthese von partiell gesättigten N-substituierten 4H-3,1-Benzothiazin-2-(1H)-thionen

Zusammenfassung Die säurekatalysierte Reaktion von 2-Arylidencyclohexanonen1 mit N-substituierten Dithiocarbaminsäure2 ergab die offenkettigen Additionsprodukte3 und4. Die Dehydratation von3 und4 führte ausschließlich zu einem der drei möglichen N-substituierten 4H-3,1-Benzothiazin-2(1H)-thion-Isomeren5 und6.

     

Zur Synthese und Struktur derp-Indazolchinone und ihrer Methylierungsprodukte Untersuchungen über Chinone, 8. Mitt.

Summary Thep-benzoquinones5e-j react with diazomethane (after dehydrogenation) to 6-anilino-2e, dimethylamino-2h, phenylthio-2i, and methylthioindazolquinone2j. Methylation with dimethylsulfate of these as well as of the already known indazolquinones 6-toluidino-2f, 6-methylanilino-2g, 5-tert.butyl-2m, 5,6-methyl- (isomer mixture)2l,n, and benz-indazolquinone2o yield the 1-and 2-N-methyl derivatives3 and4. The structure of the 2-methyl derivatives is established by reaction of the corresponding benzoquinones with 3-methylsydnon in the case of4e,4g. UV/VIS-, IR- and¹H-NMR-spectroscopy (in CDCl₃ andDMSO) were used for structure determination. Comparison of the UV/VIS-spectra of2–4 shows that the indazolquinones are existing as 2 H-4,7-diones. For the structure elucidation of the 1- rs. 2-methylderivatives (whichh can be attributed to the methylation products) NMR-spectroscopy is well suited even without knowing the second isomer (solvent-effect). The course of the reaction of quinones with diazomethane and of the methylation reactions of the indazolquinones is discussed.

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

Zur Bildung von Xylol-tricarbonylchrom (Dimethylbenchrotrenen) aus Di-n-butylether und Hexacarbonylchrom

The reaction of fluorenone ethyleneketal (9), diphenic anhydride as well as of biphenyls such as4 with Cr(CO)₆ in refluxing di-n-butylether (BE) gives dimethylbenchrotrenes [xylene-Cr(CO)₃,7] which are also formed by refluxing pureBE with Cr(CO)₆—although with much lower yields. Similarily, from di-n-pentylether and Cr(CO)₆ isobutyl- and 1-methyl-3-propyl-benchrotrene (13 and14) were obtained, whilst from di-n-propyl- and-hexylether, resp., and Cr(CO)₆ no benchrotrenes could be isolated.Tentative assumptions on the catalytic action of certain functional groups were confirmed by the reaction ofBE and Cr(CO)₆ in the presence of carbonamides, such as acetamide, urea and pyrrolidone, where 1,4-dimethylbenchrotrene (7 c) was formed with appreciable yields.Studies using dideuteratedBE showed that—at least for the reaction of9 with Cr(CO)₆ (giving a much lower yield of7 than with undeuteratedBE)—a simple bimolecular mechanism can be excluded.

     

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