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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Biologically Important Carbohydrates, 19. On the Regioselectivity of the vic. cis-Oxyamination of 3,4-Unsaturated Carbohydrates: Directed Syntheses of 4-Amino-4-deoxy- and of 3-Amino-3-deoxyaldosidesThe oxyamination of methyl 2-O-benzyl-3,4-dideoxy-α-D-glycero-pent-3-enopyranoside (1) with chloramine-T/[OsO4] yields a 2:1 mixture of methyl 2-O-benzyl-4-deoxy-4-tosylamino- (2) and of methyl 2-O-benzyl-3-deoxy-3-tosylamino-β-L-arabinoside (3). In the presence of a phase transfer catalyst the ratio is 4.5:1. In contrast benzyl 2-O-acetyl-3.4-dideoxy-α-D-glycero-pent-3-enopyrano-side (13) reacts with formation of the corresponding 4-deoxy-4-tosylamino- (14) and 3-deoxy-3-tosylamino-arabinoside 15 in the ratio 1:2. With reference to the preparative importance of this „reversal“ a hypothesis is given for the reasons of the observed regio orientation: in the reaction 1→2 + 3 through space interactions are supposed.
    Notes: Methyl-2-O-benzyl-3,4-didesoxy-α-D-glycero-pent-3-enopyranosid (1) reagiert mit (Chloramin-T/[OsO4 ] zu Methyl-2-O-benzyl-4-desoxy-4-tosylamino- (2) und Methyl-2-O-benzyl-3-desoxy-3-tosylamino-β-L-arabinosid (3) im Verhältnis 2:1. In Gegenwart eines Phasentransfer-Katalysators entstehen die isomeren im Verhältnis 4.5:1. Dagegen führt das Benzyl-2-O-acetyl-3,4-didesoxy-α-D-glycero-pent-3-cyanopyranosid (13) zum entsprechenden 4-Desoxy-4-tosylamino- (14) und 3-Desoxy-3-tosylamino-arabinosid 15 im Verhältnis 1:2. Auf die präparative Bedeutung dieser Umkehrung wird hingewiesen. Für ihre Ursachen wird eine Hypothese entwickelt: als Grund für die Regioorientierung bei 1→ 2 + 3 werden „through space“-Wechselwirkungen angenommen.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 1765-1774 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Triarylmethyl Systems, IV. Synthesis and Reactions of α-Hydroxy- and α-Halo-α-aryl[1.n]paracyclophanesBy bromination of hydrocarbons 1a-d and 6 α-bromo-α-aryl[1.n]paracyclophanes with n = 5-8 (2a-d, 7) were prepared. Via 2a-d α-hydroxy-α-aryl[1.n]paracyclophanes 3a-d were obtained, starting from which the α-chloro and α-fluoro derivatives 4a-d and 5a,b, resp., were synthesized. - Compounds of the types 2-5 were of interest as representatives of a special triarylmethyl system for which, due to the [1.n]paracyclophane structure, unusual steric and electronic effects were to be expected. The formation of p,p′-bridged triarylmethyl radicals 8 from 2a-d and their dimerisation were investigated. Rate constants for the hydrolysis of α-bromo and α-chloro compounds 2a-d and 4a-d proceeding via the carbenium ions 9 were determined in water/acetone by conductivity measurements. Stabilities of 9 (n = 5-8), formed from the hydroxy compounds 3a-d in conc. sulfuric acid, were determined; their dependence on n is discussed in terms of specific steric and electronic effects of the α-aryl[1.n]paracyclophane system. Some spectroscopic data are reported for the carbanions 10.
    Notes: Durch Bromierung der Kohlenwasserstoffe 1a-d und 6 wurden α-Brom-α-aryl[1.n]paracyclophane mit n = 5-8 (2a-d,7) dargestellt. Aus 2a-d erhielt man die α-Hydroxy-Verbindungen 3a-d, von denen aus die α-Chlor- und α-Fluor-Derivate 4a-d bzw. 5a,b zugänglich waren. - Verbindungen des Typs 2-5 interessierten als Vertreter eines besonderen Triarylmethyl-Systems, für das als Folge der [1.n]Paracyclophan-Struktur ungewöhnliche sterische und elektronische Effekte zu erwarten waren. Die Bildung der p,p′-überbrückten Triarylmethyl-Radikale 8 aus 2a-d und ihre Dimerisierung wurden untersucht. Die Geschwindigkeiten der über Carbenium-Ionen 9 verlaufenden Hydrolysen der α-Brom- und α-Chlor-Verbindungen 2a-d bzw. 4a-d in Wasser/Aceton wurden durch Leitfähigkeitsmessungen bestimmt und mit denen der entsprechenden Di- und Triphenylmethyl-Derivate verglichen. Die Stabilitäten der aus den α-Hydroxy-Verbindungen 3a-d in konz. Schwefelsäure erzeugten Carbenium-Ionen 9 mit n = 5-8 wurden ermittelt; ihre Abhängigkeit von n wird unter dem Gesichtspunkt der sterischen und elektronischen Effekte des α-Aryl[1.n]paracyclophan-Systems diskutiert. Einige spektroskopische Daten der Carbanionen 10 werden mitgeteilt.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 1755-1764 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Triarylmethyl Systems, III. Synthesis of α-Aryl[1.n]paracyclophanesAs triarylmethyl systems with unusual sterical orientation of the aryl rings α-aryl[1.n]paracyclophanes with n = 5-8 (1a-d, 8a,b) were synthesized via the corresponding dithia[1.(n + 2)]-paracyclophanes (2a-d, 6a,b) and the disulfones (3a-d, 7a,b) derived therefrom. The sterical situation in these α-aryl[1.n]paracyclophanes is discussed, especially on the basis of 1H NMR data.
    Notes: Als Triarylmethyl-Systeme mit ungewöhnlicher räumlicher Orientierung der Aryl-Ringe wurden α-Aryl[1.n]paracyclophane mit n = 5-8 (1a-d, 8a,b) über die entsprechenden Dithia-[1.(n + 2)]paracyclophane (2a-d, 6a,b) und die davon abgeleiteten Disulfone (3a-d, 7a,b) dargestellt. Die sterischen Verhältnisse dieser α-Aryl[1.n]paracyclophane werden, besonders anhand von 1H-NMR-Spektren, diskutiert.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 454 (1979), S. 24-30 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: α ω-Alkane-bis-dimethylarsine Sulfides and Selenides, a Novel Class of LigandsThe reaction of α,ω-alkane-bis-dimethylarsanes (CH3)2As—(CH2)n—As (CH3)2 with sulfur and selenium results in formation of the sulfides and selenides, respectively, (CH3)2As(X)—(CH2)n—As(CH3)2 or (CH3)2As(X)—(CH2)n—As(X)(CH3)2 (X = S, Se), which form chelat-complexes with the salts CoX2 · 6 H2O (X = Cl-, Br-, I-, NO3-). The UV-spectra of the complexes are presented and discussed.
    Notes: Die Umsetzung der α,ω-Alkan-bis-dimethylarsane (CH3)2 As—(CH2)n—As(CH3)2 mit Schwefel und Selen führt zu den Sulfiden und Seleniden (CH3)2As(X)—(CH2)n—As(CH3)2 bzw. (CH3)2As(X)—(CH2)n—As (X)(CH3)2 (X = S, Se), die mit den Salzen CoX2 · 6 H2O (X = Cl-, Br-, I-, NO3-) Chelat-Komplexen bilden. Die UV-Spektren der Komplexe werden mitgeteilt und diskutiert.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 151-155 
    ISSN: 0009-2940
    Keywords: Tripodal ligands ; Phosphane ligands ; Thioethers ; Manganese complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of fac-[(P2SPh-P,P')Mn(CO)3Br] and fac-[(PS2Ph-P,S)Mn(CO)3Br] [P2SPh: Z = PPh2; PS2Ph: Z = SPh in CH3C-(CH2PPh2)(CH2SPh)(CH2Z)] with silver hexafluorophosphate yields the η3-tripodal manganese complexes [(P2SPh-P,P',S)Mn(CO)3]PF6 (7) and [(PS2Ph-P,S,S')Mn(CO)3]PF6 (9), respectively, whereas the reaction of CH3C(CH2PPh2)2-(CH2SH) with Mn(CO)5Br gives directly [CH3C(Ph2-PCH2)2(CH2S)-P,P',S]Mn(CO)3 (11). Both ionic complexes 7 and 9 undergo stereospecifically ligand substitution upon treatment with Br-, I-, N-3, SCN- and CN- to give syn-fac-[(P2SPh-P,P')Mn(CO)3X] and syn-fac-[(PS2Ph-P,S)Mn(CO)3X] (X = Br, I, SCN, N3, CN) respectively, but the neutral complex 11 fails to undergo such a substitution reaction with these ions. However, reaction of I- with the complex [(PSMe)-P,P',S]Mn(CO)3]BF4 (20) [P2SMe = CH3C(CH2-PPh2)2(CH2SCH3)), which is obtained from the S-alkylation of 11 with (CH3)3OBF4, affords syn-fac-[(P2SMe)-P,P']Mn(CO)3I (22s) exclusively. The possible reaction mechanism of this ligand substitution is discussed.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 498 (1983), S. 64-74 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2-Dimethylarsino-ethanolThe reaction of 2-dimethylarsino ethanol Me2As-CH2CH2—OH with various metal carbonyles results in the formation of complexes of the general formula (CO)n-1Z—L respectively (CO)n-2ZL2; the ligands are able to form chelate complexes; the reaction with the halides R—X results in the formation of arsonium salts.
    Notes: Die Umsetzung von 2-Dimethylarsino-ethanol Me2As—CH2CH2—OH mit verschiedenen Metallcarbonylen führt zu Komplexen des Typs (CO)n-1Z—L bzw. (CO)n-2ZL2; durch Cyclisierung der Liganden werden Chelat-Komplexe erhalten; die Reaktion mit Halogeniden R—X führt zu Arsonium-Salzen.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 472 (1981), S. 75-82 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Inorganic Pode-Type MoleculesThe reaction of monosubstituated polyethylenglykoles [m = 0 - 4, R = Cl, OCH3, OAs(CH3)2, OSi(CH3)3] with amino compounds (CH3)xE[N(CH3)2]y(E = Si, x = y = 2; E = Si, x = 1, y = 3; E = P, x = 0, y = 3; E = As, y = 0, y = 3) results in the formation of pode-type molecules of the formula . The synthesis and rearrangement of these compounds by heating is described.
    Notes: Durch Umsetzung monosubstituierter Polyethylenglykole [m = 0 bis 4, R=Cl, OCH3, OAs(CH3)2, OSi(CH3)3] mit Amino-Verbindungen (CH3)xE[N(CH3)2]y (E = Si, x = y = 2; E = Si, x = 1, y = 3; E = P, x = 0, y = 3; E = As, x = 0, y = 3) gelingt die Synthese von Tintenfisch-Molekülen der Formel , Die Synthese sowie die Umlagerungen, die einige dieser Verbindungen beim Erhitzen eingehen, werden beschrieben.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 501 (1983), S. 89-94 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2-Methylarsino-ethanolSynthesis and reactions of 2-methylarsino-ethanol MeAs(H)—CH2CH2—OH are described. These reactions result in the formation of bifunctional arsanes of the general formula MeAs(CH2CH2—X)2 and MeAs(CH2CH2—X)CH2CH2—Y, respectively, with different groups X and Y.
    Notes: Synthese und Reaktionen von 2-Methylarsino-ethanol, MeAs(H)—CH2CH2—OH, werden beschrieben, die zur Bildung bifunktioneller Arsane des allgemeinen Formeltyps MeAs(CH2CH2—X)2 bzw. MeAs(CH2CH2—X)CH2CH2—Y führen, wobei X und Y verschiedene Gruppen sind.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 466 (1980), S. 179-182 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arsinic Acid Esters of Tri- and Tetraethylene Glycol, a Novel Class of Pode-type MoleculesThe reaction of tri- and tetraethylene glycol with dimethylaminodimethylarsane Me2As—NMe2 results in formation of the cacodyl derivates which yield with aminoarsanes pode-type molecules.
    Notes: Die Umsetzung von Tri- und Tetraethylenglykol mit Dimethylaminodimethylarsan Me2As-NMe2 führt zu den Kakodylverbindungen die mit Aminoarsanen Moleküle vom Podanden-Typ liefern.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 477 (1981), S. 139-143 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complexes of the Ni2+ and Co2+ Ions with Sulfides and Selenides of di-, tri-, and tetratertiary ArsanesThe reaction of the sulfides (selenides) of di-, tri- and tetra-tertiary arsanes with the salts CoCl2 · 6 H2O respectively Ni(ClO4)2 · 6 H2O results in the formation of chelat complexes, in which the metal ions are tetrahedrally surrounded by the ligands. The UV spectra of the complexes are discussed.
    Notes: Die Reaktion der Sulfide (Selenide) di-, tri- und tetratertiärer Arsane mit den Salzen CoCl2 · 6 H2O bzw. Ni(ClO4)2 · 6 H2O führt zu Chelat-Komplexen, in denen die Metallionen tetraedrisch koordiniert sind. Die UV-Spektren der Komplexe werden diskutiert.
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