ChemInform Abstract: REACTIONS OF DIAMINOSULFANES WITH COPPER(II) SALTS (original) (raw)

Reaktionen von Diaminosulfanen mit Kupfer(II)-Salzen

Monatshefte f�r Chemie Chemical Monthly, 1983

Reactions of Diaminosulfanes with Copper(II) Salts Reactions of bis(diethylamino)-and dimorpholinosulfane with [Cu(H20)6](C104)2 in acetonitrile and with CuC1 e-2 H20 in ethanol yield Cu(I) compounds and SQ. The reaction product of dimorpholinosulfane and CuCle in ethanol is OC4HsNSOC2Hs. The reactions are discussed.

Untersuchungen zur Reaktivität von Cyclopentadienylchromsulfiden Gegenüber Luftsauerstoff und Elektrophilen und Röntgenstrukturanalyse von Cp*2Cr2(μ,η2-S2)(μ-S2) (Cp* = η5-C5Me5)

Journal of Organometallic Chemistry, 1989

The sulfur-rich complex Cp*2Cr,(~,q1-S,S)(~,q2-S,)(~-S) (I) reacts with PPh,, under abstraction of the uncoordinated sulfur, to give Cp*2Cr2(~,q2-&)(yS)2 (II) thus confiig the existence of a labile sulfur in I. An X-ray diffraction study of II has shown this process to proceed without rearrangement of the original framework. This means that both the S2-and the Z$'-ligand lie in a plane perpendicular to the MM plane bisecting it. The S atoms form a trapezoid in contrast to the arrangement found in Cp*2Cr2&, which seems to be influenced by the p,$-S,S ligand. Air oxidation of I gives the SO,-adducts Cp*2CrzS4. SO, (IV) and Cp*2CrzS5-SO, (V). II gives these complexes IV and V only in trace amounts, but the oxidation of a weakly bound sulfur atom enhances this reaction. The SO, thus formed adds to nucleophilic sulfur bridges to give the products in good yields. This is independently confirmed by the formation of IV or V by reaction of I or II, respectively, with SO,-pyridine. The oxidation of I by Br, or I, is accompanied by the loss of one sulfur to yield compounds with the formulation Cp*,Cr,S,X, (X = Br, I). Cp*,Cr,S,I, can be reduced with Li,S, under sulfide transfer to give I. Der schwefelreiche Komplex Cp*,Cr,(p,q'-S,S)@, v2-&)(p-S) (I) reagiert mit PPh, unter Abstraktion des nicht metallkoordinierten Schwefels zu Cp*,Cr,(p,q*s,XPS)* (11) was die Priisenz eines labilen Schwefels in I beweist. Wie eine 0022-328X/89/%03.50 Q 1989 Elsevies Sequoia S.A.

Phosphorhaltige Kohlenhydrate, IV. Reaktion von Glucopyranosylhalogeniden mit Dialkylphosphit-Salzen und Trialkylphosphit

Chemische Berichte, 1973

Eingegangen an1 2. August 1972 Tetra-0-acetyl-x-D-glucopyranosylbromid (1) reagiert mit BrHgPO(0R)z oder AgPO(OR)2 t-AgC104 zur 3,4,6-TriO -acetyl-1 , 2 4 4 1-em-(dialkylphosphono)athyliden]-x-D-glucopyranose (2). Das Phosphonat 2 kann auch direkt aus dem 1,2-Gluco-acetoxonium-Salz 6 rnit P(OR)3 unter Entalkylierung des primar gebildeten Quasiphosphoniumsalzes 3 dargestcllt werden. Mit P(OR)3 reagiert die Bromverbindung 1 zur Hex-1-enopyranose I l a (80%) und zum Acetalphosphonat 12 (1 5 %). Pyranosylhalogenide mit nicht zur Nachbargruppenreaktion befahigten Snbstituenten am C-2 liefern mit P(OR), nur Hex-1-enopyranosen 11. Die Bromverbindung 1 ergibt rnit AgPO(0Me)z P-Glucosylphosphit 20, das zu P-G lucosylphosphat 21a oxidiert wird. Mit AgPO(0At)Z werden entsprechend die a-Formen 23 und 24 erhalten. Iler Mechanismus der Bildung von 2 und 11 wird diskutiert. Phosphorus-containing Carbohydrates, IV') Reaction of Glucopyranosyl Halides with Salts of Dialkylphosphites and with Trialkylphosphites Tetra-0-acetyl-aD -ghxopyranosyl bromide (1) reacts with BrHgPO(OR)2 or AgPO(OR)2 f-AgC104 to yield 3,4,6-tri-0-acetyl-l,2-0-[1-exo-(dialkylphosphono)ethylidene]-a-~-glucopyranose (2). The phosphonate 2 can be obtained directly from the 1 ,Z-gluco-acetoxonium salt 6 with P(OR)3 via dealkylation of the primarily formed quasi-phosphonium salt 3. Treatment of the bromo compound 1 with P(0R)j yields the hex-I-enopyranose l l a (80%) and acetal phosphonate 12 (15%). Pyranosyl halides without a substituent at C-2 capable of neighbouring group reaction react with P(OR)3 to yield exclusively hex-I-enopyranoses 11. The bromo compound 1 reacts with AgPO(OMe)2 to give 13-glucosylphosphite 20 which is oxidized to p-glucosylphosphate 21a. In the same way the a-forms 23 and 24 are obtained with AgPO(0Et)z. The mechanism of the formation of 2 and 11 is discussed. Kurzlichl) haben wir Zuckerphosphonate aus geschiitzten Aldosen init freier Aldehydgruppe durch Wittig-und Horner-Reaktion dargestellt. Durch Michaelis-Arbuzov-Reaktion lassen sich 6-Phosphonate von Hexoseund 5-Phosphonate von Pentose-Derivaten darstellenz). Hierzu werden 6-Halogenhexopyranose-oder