Pseudochalkogenverbindungen. XXIV. Cyanamido-trimetaphosphimate

Pseudochalcogeno Compounds. XXIV. Cyanamido Trimetaphosphimates Synthesis and properties of sodium cyanamido trimetaphosphimates Na₃[P₃(NH)₃O_6?n(NCN)_n] (n:2,4) are reported. This compounds may be obtained by cautious hydrolysis of the corresponding hydrocyanamido-chloro-trimetaphosphimates, P₃N₃Cl_6?n(NHCN)_n. For sodium trimetaphosphimate, Na₃[P₃(NH)₃O₆] a simple, modified synthetic route is described. Possibilities of the formation of pseudochalcogeno-trimetaphosphimates of the type [P₃(NH) ₃O_6?n{C(CN)₂}_n]^3? (n = 2, 4) are discussed.     

Trifluormethyl-schwefel-stickstoff-verbindungen. IX. Trifluormethansulfonamide

Trifluoromethanesulphonamide forms the following salts: CF₃SO₂NAg₂·NH₃, CF₃SO₂NAg₂, (CF₃SO₂NH)₂Hg and CF₃SO₂NH·NH₄. These salts are more reactive than the initial amide. CF₃SCl reacts with both silver salts to give the corresponding mono- and di-substituted derivatives, CF₃SO₂N(SCF₃)₂ and CF₃SO₂NHSCF₃, respectively. With phosgene and thiophosgene, CF₃SO₂NAg₂ reacts to give the pseudohalides CF₃SO₂NCO and CF₃SO₂NCS, respectively.     

Fluordiazadiphosphetidine, 5. Mitt.

Reaction of (CH₃NPF₃)₂ with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH₃N)₄P₃F₇, the new spiro-isomer F₃P(CH₃N)₂PF(CH₃N)₂PF₃ and the spiro-compound F₃P(CH₃N)₂PF(CH₃N)₂PF(CH₃N)₂PF₃, an isomer of the known compound (CH₃N)₆P₄F₈.     

N.m.r. studies on aromatic compounds. I—13C n.m.r. spectra of some mono- and disulpho-substituted hydroxycarboxylic acids

Carbon-13 n.m.r. spectra of 3-hydroxy-4-sulpho-2-naphthoic, 3-hydroxy-5-sulpho-2-naphthoic, 3-hydroxy-7-sulpho-2-naphthoic, 5-sulphosalicylic, 3-hydroxy-5,7-disulpho-2-naphthoic, 1-hydroxy-4,7-disulpho-2-naphthoic, and 3,5-disulphosalicylic acids were recorded with and without proton noise-decoupling. Analyses of the spectra were carried out for all compounds except 3-hydroxy-5-sulpho-2-naphthoic acid which dimerized. The fine splitting caused by long-range coupling was used in identifying the lines of the ¹³C n.m.r. spectra.     

Direct synthesis of fluorinated peroxides. 9. Some reactions of perfluorotertiarybutyl hydroperoxide.

The reaction of (CF₃)₃COOH with perfluoroacyl fluorides in the pressure of NaF results in the formation of new peroxy esters of the type, (CF₃)₃COOC(O)R_f. Addition of the hydroperoxide to CF₃NCF₂ yields the unstable amine (CF₃)₃COOCF₂N(H)CF₃. These reactions of (CF₃)₃COOH are compared with analogous reactions of CF₃OOH and SF₅OOH.     

Die sterischen Bedingungen der Fragmentierungsreaktion I. Teil. Stereoisomere 3-Chlortropane. Fragmentierungsreaktionen, 14. Mitteilung

The steric requirements for the synchronous fragmentation of γ-aminohalides as previously postulated have been confirmed by a study of the solvolysis of stereoisomeric 3β- and 3β-chloro-tropanes and -nortropanes. 3β-chloro-tropanes ( 7 a ) and 3β-chloro-nortropane ( 7 b ), which fulfil the stereoelectronic requirements, undergo quantitative fragmentation in 80 vol.% ethanol. They react 1.35 × 10⁴ and 1.35 × 10³ times, respectively, as fast as the ‘homomorphous’ exo-3-chloro-bicyclo[3.2.1]octane ( 12 a ). Fragmentation therefore takes place by the synchronous mechanism.     

Indole derivatives. XXIII. 3-Indolylethylene glycol

Lithium aluminum hydride reduction at room temperature of 3-hydroxyacetylindole and 3-benzyloxyacetylindole in tetrahydrofuran gives, respectively, 3-indolyethyleneglycol and 3-indolylethylene glycol monobenzylate. Sodium borohydride reduction of 3-hydroxyacetylindole gives tryptophol, and the reduction of 3-benzyloxyacetylindole gives tryptophol benzylate. Aluminum amalgam converts 3-hydroxyacetylindole and 3-benzyloxyacetylindole to 3-acetylindole.For part XXII see [1]     

Unsymmetrically substituted furoxans. Part 11. Methylfuroxancarbaldehydes

The two isomeric 3-methyl-4-furoxancarbaldehydes ( 2a ) and 4-methyl-3-furoxancarbaldehyde ( 2b ) have been prepared. Discussion of their structures, thermal equilibration and kinetic of thermal conversion from the 3-methyl to the 4-methyl isomer are also reported. (Phenylsulfonyl)hydrazones 3a and 3b have been prepared as derivatives in view of their potential antitumoral properties.     

Alkyl N-methylfuroxanylcarbamates. Synthesis and structure. II

From 3-methyl-4-furoxancarboxylic acid hydrazide and 4-methyl-3-furoxancarboxylic acid hydrazide the corresponding azides have been synthesized. 3-Methyi-4-furoxancarboxylic acid azide normally underwent the Curtius reaction to give the expected carbamic acid derivative. The degradation of 4-methyl-3-furoxancarboxylic acid azide led to the N-(4-methylfuroxan-3-yl)-carbamic acid derivative at low temperatures and to N-(3-methylfuroxan-4-yl)carbamic acid derivative at higher temperatures.     

Fluordiazadiphosphetidine, 17. Mitt.

The reactions of (CH₃NPF₃)₂ and F₃P(CH₃N)₂PF₂OCH₃ with lithium-1,1,1-trimethyl-N-(trimethylsilyl)-silanamide yield two new dispiro-compounds:XF₂P(CH₃N)₂PF(NSiCH₃)₂PF(CH₃N)₂PF₂ X withX=F, OCH₃. Synthesis, mass-spectra and X-ray structures are discussed.

Herrn Prof. Dr.K. L. Komarek zum 60. Geburtstag gewidmet.     

Fluordiazadiphosphetidine, 16. Mitt.

The reaction of (CH₃NPF₃)₂ with NH₃ and primary aliphatic and aromatic amines in the molar ratio 3:2 yields (CH₄NPF₄)₂ and the monoamino substituted fluordiaza-diphosphetidines. These react with N-Trimethylsilyl-methylamine to the mixed diamino substituted compounds.With 1,4-Diazabicyclo[2.2.2]octan as HF-acceptor a second step of nucleophilic substitution with NH₃ and primary amines is possible. In the case of ammonia a by- product has been identified as the 1:1 adduct of (CH₃NPF₂NH₂)₂ with 1,4-diazabicyclo[2.2.2]octan.

Herrn Prof. Dr.O. Hromatka zum 80. Geburtstag gewidmet.     

Azimine. VII. Herstellung durch Oxydation von Triazanen

Azimines. VII

1 Teil VI, s. [1].

. Preparation by Oxidation of Triazanes A novel method for the preparation of certain azimines 4 by oxidation of 1,2,3-trisubstituted triazanes 3 is described. Treatment of 3-aryl-triazane-1,2-diesters 3a-3c with lead tetraacetate afforded the 3-aryl-azimine-1,2-diesters 4a-4c . The precursor triazanes 3a-3c were prepared by addition of p-substituted anilines to diisopropyl diazene-1,2-dicarboxylate 1b . A comparison of the spectral properties of the azimines 4 with those of the correspondingly substituted triazanes 3 reveals the unsaturated and dipolar nature of the azimines 4 .     

Triterpenoid saponins from Ilex mamillata C.Y. Wu ex C.J. Tseng

Two new triterpenoid saponins, ilemaminosides A and B (1 and 2) along with six known saponins (3-8) were isolated from 70% ethanolic extract of the leaves of Ilex mamillata C.Y. Wu ex C.J. Tseng. The new saponins were characterised as 3-O-α-L-arabinopyranosyl-ilexgenin B (1) and 3-O-β-D-glucopyranosyl-(1?→?3)-α-L-arabinopyranosyl-ilexgenin B (2). The structures of compounds 1 and 2 were elucidated on the basis of the chemical and spectroscopic methods, and the structures of known compounds were identified by comparison of their spectroscopic data with those reported in the literature. The compounds showed inhibitory activities in anti-inflammatory assay in?vitro with IC(50) values in the range 25.37-38.33?μg?mL(-1).     

Triaziridine. 6. Mitteilung. Substituententransformationen an Triaziridinen

Substituent Transformations on Triaziridines Several novel triaziridines were prepared by substituent transformations starting from the known dialkyl-triaziridine-carboxylates 1a – c , with the aim to study the influence of the substitution pattern on the properties of the triaziridine ring. The dialkyl-triaziridines 2a – c were obtained by (t-BuO^?)-mediated demethylation and decarboxylation and the dialkyl-triaziridine-methanols 4a – c by LiAlH₄ reduction. Further reduction of the tosylates of 4a , b with LiAlH₄ gave the methyl-dialkyl-triaziridines 3a , b . The dialkyl-triaziridines 2a , c could not be N-methylated directly with CH₃I, but the anions 10a , c , obtained from 2a, c with CH₃Li, yielded 3a , c . N-Methylation of 2a with (CH₃)₃OBF₄ did not afford 3a but rather the methyl-triaziridinium salt 11 . The dialkyl-triaziridine 2c has pK_a > 14, its protonated species < 2. A concept that the electron pairs on the triaziridine N-atoms are more strongly localized than on amine N-atoms explains (a) that the dialkyl-triaziridine 2c is hardly basic, (b) that the LiAlH₄ reductions of the esters 1 stop at the stage of the methanols 4 , and (c) that the methanols 4a , b do not cleave like aminomethanols.     

Derivate des Methylendioxybenzols, 24. Mitt.

Zusammenfassung Es wird die Synthese des isomerenfreien 2,3-Methylendioxyallylbenzols (o-Safrols) (1 d) durch Einwirkung von Chlorbrommethan auf 2,3-Dihydroxy-allylbenzol (1 b) beschrieben.Durch Behandlung des 4-Hydroxy-3-methoxy-allylbenzols (3 a) mit Kaliumnitrosodisulfonat, Reduktion des entstehenden 3-Methoxy-5-allyl-o-benzochinons (4) mit Natriumdithionit und Methylenierung des 3-Methoxy-5-allyl-brenzcatechins (5) bildet sich Myristicin (3 b) in guter Ausbeute.

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Derivatives of methylenedioxy-benzene, XXIV: Synthesis of o-safrole and of myristicine

Preparation of 2.3-methylenedioxy-allylbenzene (o-safrole) (1 d) free of isomers by reaction of 2.3-dihydroxy-allylbenzene (1 b) with CH₂BrCl is described.Treating 4-hydroxy-3-methoxy-allylbenzene (3 a) with potassium nitrosodisulfonate gives 3-methoxy-5-allyl-o-benzoquinone (4) which ist reduced to 3-methoxy-5-allyl-pyrocatechol (5) with sodium dithionite. Methylenation of3 c gives myristicin with good yield.

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23. Mitt.:F. Dallacker, W. Edelmann undA. Weiner, Ann. Chem.,719, 112 (1968).     

Microbial metabolism. Part 5. Dihydrokawain

Preparative scale fermentation of (6S)-dihydrokawain (1) with Rhizopus arrhizus (ATCC 11145) gave 3'-hydroxydihydrokawain (2) and (8S)-hydroxydihydrokawain (3). Structure elucidation of the metabolites was based on spectroscopic data. The C-8 absolute configuration of (3) was assessed via its Mosher's esters.     

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.     

C-glycosylic derivatives. XV. Vinylogues of homo-C-glycosides

1,2-O-Isopropylidene-3-O-methyl-α-D-xylo-pentodialdo-1,4-furanose and its 3-O-benzyl analog have been reacted with pyridinyl-3-methylenetriphenylphosphorane and benzimidazolyl-2-methylenetriphenylphosphorane. The unsaturated sugars so obtained are vinylogs of homo-C-glycosides whose conformation is easily determined. They constitute useful model compounds for pharmacologic studies.     

Thermal analysis graphite intercalation compounds with dichlorides of some d-elements: A.S. Skoropanov,G.S. Petrov,A.A. Vecher,Yu.N. Novikov and M.E. Vol'pin,Thermochim. Acta, 90 (1985) 339-342

Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me₂ (4), 3,5-Me₂ (5), 3-NH₂ (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed.     

S.C.F.M.O. study of Hafner's hydrocarbons

SCF MO calculations have been made for Hafner's hydrocarbons using neglect of differential overlap after the manner ofPople andPariser andParr. ^* transitions have been calculated by a limited configuration interaction method. The results show that agreement between predicted spectra and observed spectra is quite good for the heptalene derivative and reasonably good for the pentalene derivative. It is suggested that both molecules are aromatic in contradiction to predictions by Craig's rule.

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Zusammenfassung SCF MO-Rechnungen mit zero differential overlap nach der Methode vonPople, Pariser undParr wurden fürHafner's Kohlenwasserstoff angestellt. Mittels begrenzter Konfigurationswechselwirkung (wurden)die ^*-Übergänge berechnet, wobei die Ergebnisse im Fall des Heptalen-Derivates verhältnismäßig gut, in dem des Pentalen-Derivates jedoch nur ungefähr mit dem Experiment übereinstimmen. Darüber hinaus sprechen die Resultate im Gegensatz zur Craig'schen Regel dafür, daß beide Moleküle aromatischen Charakter haben.

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Résumé Nous avons effectué des calculs SCF MO pour les hydrocarbures deHafner, en négligeant le recouvrement différentiel d'aprèsPople etPariser etParr. Quelques transitions ^* ont été calculées par interaction de configurations limitée. L'accord avec l'expérience est assez bon pour le dérivé de l'heptalène, et raisonable pour le dérivé du pentalène. Les deux molécules semblent être aromatiques, contrairement à la règle de Craig.