Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 8. Mitt.

N-substituted halogenoacetamides react with halogenoboranes to the title compounds. The corresponding N-substituted halogenoimines result as byproducts. The importance of inductive and steric effects of the substituents is shown by the fact, that certain N-substituted halogenoacetamides react under formation of N-substituted halogenoimines only.¹H-,¹¹B-, and¹⁹F-NMR spectra, mass spectra and characteristic IR group frequencies are reported.

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7. Mitt.:W. Maringgele undA. Meller, Mh. Chem.108, 751 (1977).     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 12. Mitteilung

N-Trimethylsilylamides react with aminohalogenoboranes in nearly quantitative yield to monomeric amido(bis)aminoboranes. From the reaction of N-substituted acylamides with bis(amino)halogenoboranes and dialkoxyhalogenoboranes respectively and triethylamine corresponding amido-bis(amino)-and amido-bis(alkoxy)boranes were obtained in high yields. In certain cases equilibria between monomeric and dimeric forms are observed.¹H,¹¹R, and¹⁹F.-n.m.r. spectra, mass spectra and characteristic i.r. group frequencies are reported.

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11. Mitt.:W. Maringgele undA. Meller, Chem. Ber., eingereicht.     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen. XLI. Synthese von 9-Bora-10-oxa-phenanthrenen,Bis(2′-oxy-terphenylyl)halogenoboranen und Bis(9-bora-10-oxa-phenanthrenyl)-oxiden

Reaction of Metal and Metalloid Compounds with Polyfunctional Molecules. XLI. Synthesis of 9-Bora-10-oxa-phenanthrenes, Bis(2′-oxy-terphenylyl)halogenoboranes, and Bis(9-bora-10-oxa-phenanthrenyl)oxides The reaction of 2′-hydroxy-m-terphenyl and 2-hydroxy-biphenyl resp. with n-C₄H₉Li and Na resp. and subsequent addition of trihalogenoboranes yields 9-halogeno-9-bora-10-oxa-phenanthrenes 1, 2, 5 and A besides 9-2′-oxy-m-terphenylyl-9-bora-10-oxa-phenanthrene 3 and bis-(9-bora-10-oxa-phenanthrenyl)oxides 4 and 6 . Under somewhat different reaction conditions one obtains also the bis(2′-oxy-terphenylyl)halogenoboranes 7 and 8 , tris(2-oxy-biphenylyl)-borane 9 and t-butyl-chloro-(2-oxy-biphenylyl)borane 10. 11 results from reaction of 2 with lithated hexamethyldisilazane. The compounds are characterized analytically and spectroscopically (¹H, ¹¹B-nmr spectra; mass spectra). For 4 and 6 X-ray analyses were performed.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 16. Mitt.

The reaction of trimethylsilylcarbonamides with halogeno-diorganyl-boranes resp. trihalogenoboranes or organodihalogenoboranes gives monomeric resp. dimeric amidoboranes (borylcarbonamides) and derivatives of 4,8-diaza-1,5-dibora-2,6,9-trioxabicyclo[3.3.1]nonadienes. By reaction of the free acylamides with halogenoboranes in most cases the imide halides could be isolated as the only products. By reaction of the hydrochloride of bis(dimethylamino)-hydroxyborane withn-butyl-lithium followed by addition of the imide halides, the corresponding imidoylamines were formed.¹H,¹¹B, and¹⁹F-nmr spectra, mass spectra and characteristic ir group frequencies are reported.

15. Mitt.:W. Maringgele undA. Meller, Z. anorg. allg. Chem., im Druck.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 7. Mitt.: Thioamidoborane

N-substituted thioamides react with bromo(organyl)boranes under formation of the corresponding thioamidoboranes and HBr. The¹¹B-NMR-spectra as well as the boiling points show, that these compounds are mostly dimeric at room temperature, resp. monomeric in the vapor-phase.¹H-,¹¹B-NMR-spectra and the mass spectra are reported.

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6. Mitt.:W. Maringgele undA. Meller ²     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen,XIX. Synthese von Amidoborazinen

Reaction of Metal and Metalloid Compounds with Polyfunctional Molecules. XIX. Synthesis of Amidoborazines By reaction of 2-chloro-1,3,4,5,6-pentamethylborazin with silylated carbonic acid amides and thioamides resp. the corresponding amidoborazines are obtained. By reaction of lithiated hexamethyldisilazane with 2-chloro-1,3,4,5,6-pentamethylborazine, the 2-hexamethyldisilazanyl-1,3,4,5,6-pentamethylborazine is formed. ¹H, ¹¹B, and ¹⁹F n.m.r. spectra, mass spectra and characteristic i.r. group frequencies are reported.     

Metallkomplexe von N-substituierten 3-Imino-isoindolinonen

Metal Complexes of N-substituted 3-Imino-isoindolinones The condensation of 3-imino-isoindolinone 4 and benzimidazoles or benzthiazoles containing activated methyl-, methylen- or aminogroups ( 5 resp. 6 ), yields the iso-indolinone-ligands 1 and 2. Metal ions such as Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ form (1:2)-complexes with these ligands of very high chemical and photochemical stabilities. The magnetic properties of these complexes indicate that the geometry around the central atoms is distorted tetrahedral. A X-ray diffraction study of one of the Co(II)-complexes confirms these findings.     

α-Substituierte phosphonate—36 : α-Phosphonoenamine und acylphosphonate durch horner-olefinierung

Phosphonoenamines are formed by Horner-Olefination of N-substituted aminomethane-bis-phosphonic acid esters. These exist, depending on N-substitution, carbonyl compound, and condition of the reaction as pure E- or Z-isomeres resp. as E,Z-mixture. The stereochemistry unambiguously could be derived from the ¹H- resp. ¹³C-NMR-spectra. Mild hydrolysis of the phosphonoenamines yields acylphosphonates; ³¹P-NMR-data shows, that these exist as a mixture of keto-enol-form. The enol-form of this products could be isolated in crystalline form. Phenylacetylphosphonate, unambiguously synthesized from phenylacetylchloride and triethylphosphite also exist as a mixture of the keto-enol-form.     

Chlor-dimethylaminosulfonium-Salze Darstellung und IR-Spektren

Chloro-dimethylaminosulfonium Salts. Preparation and I. R. Spectra By reaction of bis-dimethylamino-mono- resp. -disulfane with a mixture of chlorine/antimony(V) chloride the chloro dimethylaminosulfonium hexachloroantimonates(V) [(CH₃)₂N]₂SCI^⊕SbCl₆^? (I) and (CH₃)₂NSCI₂^⊕SbCl₆^? (II) are yielded. The i. r. spectra of these compounds were measured and assigned.     

Synthese,Struktur und dynamisches Verhalten von Cyclopentadienylboranen

The cyclopentadienylboranes I–XI have been synthesized by the reaction of halogenoboranes with cyclopentadienyl-trimethylsilanes, -trimethylstannanes and -lithium compounds. Substitution reactions at the boron atom in III and VIII with tetramethylstannane and dimethylamine lead to the cyclopentadienylboranes XII–XV. The structures of I–XV have been investigated by ¹H-, ¹³C- and ¹¹B-n.m.r. measurements. The 5-trimethylsilyl-cyclopentadienylboranes show a dynamic behaviour due to sigmatropic rearrangements. The influence of a boryl ligand on the speed of these rearrangements is discussed.     

14‐Membered Cyclopeptides from Paliurus ramosissimus and P. hemsleyanus

Six 14‐membered cyclopeptide alkaloids, i.e., ramosines A–C, mucronine J, and lotusines A and D, were isolated from the roots of Paliurus ramosissimus, and an additional four, hemsines A–D, from the roots of P. hemsleyanus. Among these, ramosines A–C ( 1, 5 , and 6 , resp.) and hemsines A and B ( 7 and 8 , resp.) are new bases of the amphibine‐B type, and hemsines C and D ( 9 and 10 , resp.) are new integerrine‐type alkaloids. Additionally, ramosine C ( 6 ) represents the first 14‐membered cyclopeptide alkaloid possessing a substitution (? OH) at C(13′). Their structural elucidations were based on spectral analysis and molecular‐modeling studies. Pronounced solvent effects in the ¹H‐ and ¹³C‐NMR spectra of these two types of alkaloids were observed.     

N-acetyl-DL-leucinate cobalt(II), nickel(II) and zinc(II) complexes

Summary Complexes of the type M(AcLeu)₂ · B₂ (M = Co^II, Ni^II or Zn^II; B = H₂O, py, 3-pic, 4-pic; AcLeu =N-acetyl-DL-leucinate ion) and M(AcLeu)₂ B (M = Co^II or Zn^II and B = o-phen) were prepared and investigated by means of magnetic and spectroscopic measurements. The i.r. spectra of all the complexes are consistent with bidentate coordination of the amino acid to the metal ion. The room temperature solid state electronic spectra indicate that the symmetry of this species is closer toD _4h and that MO₆ and MO₄N₂ chromophores are present in the M(AcLeu)₂ · 2 H₂O and M(AcLeu)₂B_n · x H₂O (B = py, 3-pic, 4-pic, n=2 and x=0 for M = Ni^II; B = o-phen, n=1 and x=0 for M = Co^II; B = py, 3-pic, 4-pic, n=1 and x=1 for M = Co^II) complexes, respectively. By comparing the Dq values of the amino acid and those of other N-substituted amino acids previously studied, a spectrochemical series of the the cobalt(II) and nickel(II) complexes is proposed. The¹ H n.m.r. spectra of the zinc(II) complexes confirm the proposed stereochemistry.     

SYNTHESIS OF SOME DITHIOCARBAMATE DERIVATIVES AND THEIR ANTIMICROBIAL ACTIVITY

Some new, 2-[(N-substituted aminothiocarbonylthio)acetyl]aminothiazole, N-substituted aminothiocarbonylthioacetylaminodiphenylmethane and 9-[(N-substituted aminothiocarbonylthio)acetyl]aminofluorene derivatives were synthesized by reacting 2-(chloroacetyl) aminothiazole, chloroacetylaminodiphenylmethane, and 9-(chloroacetyl)aminofluorene with secondary amine dithiocarbamate derivatives in acetone respectively. The structure elucidation of the compounds was performed by IR, ¹H-NMR, and FAB⁺-MS spectral data. The substances were tested for their antimicrobial activity.     

E.p.r. studies on dichloromono(1-phenylamidino-o-alkylurea)copper(II) complexes. Evidence for field induced partial ordering in the solid state and some unusual features in solution

E.p.r. and optical absorption studies have been conducted on dichloromono(1-phenylamidino-o-alkylurea)copper(II) complexes (Alkyl = Me, Et, Pr, Bu or Pe). The e.p.r. spectra of solids, recorded at 300 K, confirmed the square-planar geometry with the unpaired electron in the dx ²–y ² orbital of copper. Magnetic field-induced partial molecular alignment has been observed in some of the polycrystalline samples when cooled in a magnetic field of 1 T at 77 K. E.p.r. spectra at 77 K in pyridine and DMF has shown axial ligation of solvent molecules (pyridine and DMF), whereas in MeOH and DMSO at least three structurally different Cu^II species have been identified. These features are consistent with differences in electronic absorption spectra in the powder and in solution.     

NMR-Spektren vontrans—Chalcon-oxim,-semicarbazon und-thiosemicarbazon und ihren cyclischen Isomeren (3,5-Diphenyl-2-isoxazolin und 1-substituierte 3,5-Diphenyl-2-pyrazoline)

Zusammenfassung Frühere Strukturvorschläge für dastrans-Chalcon-oxim, semicarbazon und thiosemicarbazon¹ werden mit Hilfe von NMR-Spektren richtiggestellt: Die sauer katalysierte Reaktion führt zwar zum Oxim, Semicarbazon und Thiosemicarbazon destrans-Chalcons; basische Katalysatoren bewirken dagegen eine interne Cyclisierung zu 3,5-Diphenyl-2-isoxazolin bzw. zu 1-substituierten 3,5-Diphenyl-2-pyrazolinen. Die Zuordnungen in den NMR-Spektren wurden durch Vergleich mittrans-Dypnon und seinem Semicarbazon getroffen.

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NMR spectra of trans-chalcone oxime, semicarbazone and thiosemicarbazone and their cyclic isomers (3,5-diphenyl-2-isoxazoline and 1-substituted 3,5-diphenyl-2-pyrazolines)

Earlier tentatively assigned structures fortrans-chalcone oxime, semicarbazone and thiosemicarbazone, resp., have been corrected by means of NMR spectra: open-chain structures have been found for the title compounds formed in the acid catalyzed reaction, whereas basic catalysts lead to intramolecular cyclization with formation of 3,5-diphenyl-2-isoxazoline and 1-substituted 3,5-diphenyl-2-pyrazolines resp. Assignments in the NMR spectra were made by comparison with those from authentic samples oftrans-dypnone and its semicarbazone.

     

Rotation barriers in N-substituted 2,4,6-trimethylpyridinium cations

The α-methyl and β-protons in ¹H-NMR spectra, the α-methyl, α-ring, and β-ring carbons in ¹³C-NMR spectra of N-substituted 2,4,6-trimethylpyridinium salts III are anisochronous. Dynamic NMR spectroscopy affords appreciably higher activation enthalpies ΔG≠ for rotation around the N(sp²)C(sp³) bond than ΔG≠ for the analogously substituted mesityl derivatives, in agreement with the shorter $\text{N}\text{+}$C than the CC bond.     

Pteridine studies: III—13C n.m.r. data of pteridine,some of its derivatives and their covalent σ-adducts with ammonia and water

¹³C n.m.r. spectral data of pteridine and nineteen of its derivatives (containing one or more chloro, methylthio, methyl, t-butyl or phenyl substituents) are reported. The ¹³C n.m.r. spectrum of the title compound has been assigned conclusively. ¹³C n.m.r. substituent effects are shown to be very useful in discerning between 6- and 7-substituted pteridines. Additionally, the ¹³C n.m.r. spectra of several covalent amination products, i.e. the 3,4-dihydro-4- amino- and the 5,6,7,8-tetrahydro-6,7-diaminopteridine derivatives, formed by dissolving the appropriate pteridine in liquid ammonia, have been recorded. The ¹³C n.m.r. spectra of the corresponding covalent hydrates are also reported.     

Osmium(II)-Phthalocyanine: Darstellung und Eigenschaften von Di(acido)phthalocyaninatoosmaten(II)

Osmium(II) Phthalocyanines: Preparation and Properties of Di(acido)phthalocyaninatoosmates(II) “H[Os(X)₂Pc^2?]” (X = Br, Cl) reacts in basic medium or in the melt with (ⁿBu₄N)X forming less stable, diamagnetic, darkgreen (ⁿBu₄N)₂[Os(X)₂Pc^2?]. Similar dicyano and diimidazolido(Im) complexes are formed by the reaction of “H[Os(Cl)₂Pc^2?]” with excess ligand in the presence of [BH₄]^?. The cyclic voltammograms show up to three quasireversible redoxprocesses: E_1/2(I) = 0.13 V (X = CN), ?0.03 V (Im), ?0.13 V (Br) resp. ?0.18 V (Cl) is metal directed (Os^II/III), E_1/2(II) = 0.69 V (Cl), 0.71 V (Br), 0.83 V (CN), 1.02 V (Im) is ligand directed (Pc^2?/?) and E_1/2(III) = 1.17 V (Cl) resp. 1.23 V (Br) is again metal directed (Os^III/IV). Between the typical “B” (～16.2 kK) and “Q” (～29.4 kK), “N regions” (～34.1 kK) up to seven strong “extra bands” of the phthalocyanine dianion (Pc^2?) are observed in the uv-vis spectrum. Within the row CN > Im > Br > Cl, most of the bands are shifted slightly, the “extra bands” considerably more to lower energy in correlation with E_1/2(I). The vibrational spectra are typical for the Pc^2? ligand with D_4h symmetry. M.i.r. bands at 514, 909, 1 173 and 1 331 cm^?1 are specific for hexa-coordinated low spin Os^II phthalocyanines. In the resonance Raman (r.r.) spectra polarized, depolarized or anomalously polarized deformation and stretching vibrations of the Pc^2? ligand will be selectively enhanced, if the excitation frequency coincides with “extra bands”. With excitation at ～19.5 kK the intensity of the symmetrical Os? X stretching vibration at 295 cm^?1 (X = Cl), 252 cm^?1 (X = Im) and 181 cm^?1 (X = Br) is r.r. enhanced, too. The asymmetrical Os? X stretching vibration is observed in the f.i.r. spectrum at 345 cm^?1 (X = CN), 274 cm^?1 (X = Cl), 261 cm^?1 (X = Im) and 200 cm^?1 (X = Br).     

Vier- und achtgliedrige metallhaltige Bor–Stickstoff-Heterocyclen. Bildung und Strukturen in Abhängigkeit von der Raumerfüllung der Substituenten

Four and Eight Membered Metal Containing Boron–Nitrogen-Heterocycles. Formation and Structures in Dependence on the Steric Requirement of their Substituents TripB(NRLi)₂ (Trip = 2,4,6-triisopropylphenyl, R = Me ( II a ), CH₂Me ( II b ), CHMe₂ ( II c ), CMe₃ ( II d ) reacts with dibromo(dimethyl)tin to give eight membered ( III a , III b ) and four membered metallacycles ( IV c and IV d ). If tetrahalides (GeCl₄, SnCl₄) are the reaction partners, the spiro compounds V c and VI d are obtained from II c and II d resp. The compounds are characterized by their m.s. and n.m.r. (¹H, ¹¹B, ¹³C, ¹⁹F, ¹¹⁹Sn) spectra and by elemental analyses. An X-ray structure analysis was performed for III a .     

Sodium Hypochlorite Reactions. III. The Catalytic Nakagawa and Related Systems

Mainly through the extensive investigations of Nakagawa and coworkers, nickel peroxide has emerged as a powerful oxidant for organic compounds. For example, it has been used for the oxidation of alcohols to aldehydes or carboxylic acids,^2,3 allylic hydroxyl (selectively) to the carbonyl group,⁴ α-ketols to α-diketones,⁵ α-glycols, α-ketols, α-hydroxyl and α-keto acids to cleavage products,⁶ aldehydes to amides or nitriles in the presence of ammonia,⁷ phenols to quinones,^8,9 certain Schiff bases to benzoxazoles,¹⁰ amines to azo compounds or nitriles,^11,12 diarylamines to hydrazines,¹³ carbazoles to dimers and trimers,¹⁴ hydrazones to diazo compounds,^15,16 1-aminobenzotriazole to benzyne,¹⁷ N-substituted hydroxylamines to azoxy compounds,¹⁸ phenylacetonitrile to dimeric products,¹⁹ a thiouracil to a uracil derivative,²⁰ thiols to disulfides and sulfides to sulfones,²¹ N-substituted phenothiazines to sulfoxides and sulfones,²¹ haloforms to hexahaloethanes.²³