infrared and ultraviolet spectra and optical rotation) of the natural and synthetic products. Glycosidation of (2) was also effected when sodium iodide was used instead of silver perchlorate, or even without addition of either of these compounds, although then more vigorous reaction conditions were required. In this way we obtained a glucoside of uric acid from (2) and a-acetobromoglucose. This had the same ultraviolet spectrum (measured at pH 1, 7, and 14) as (1). This product, so far unknown in nature, is therefore a 3-glucosyluric acid. Received, January 23rd. 1963 [Z 435/263 IE] [l] Communication No. 18 on organosilicon compounds; Communication No.We have found that p-nitrosotoluene rapidly adds on one equivalent of sodium to form a deep green, apparently colloidal solution of the free radical (1) when shaken under nitrogen with powdered sodium in dry ether at 5-10°C. The multilineal electron spin resonance spectrum [l] shows that the unpaired electron is located to a considerable extent in the benzene ring. The free radical ( I ) is converted by shaking for 1 hour with excess sodium into the reddish-brown substance (3), which is insoluble in ether and which reforms the green radical when shaken with oxygen (0.5 mole). f IThe same reaction in tetrahydrofuran leads to a red solution of (3), which is transformed to a clear deep-green solution of (1) by measured addition of oxygen. In this solution, about 25 % of the monosodium adduct exist in the free radical form (ESR measurement). Hence (1) is probably in equilibrium with a dimer (5), which possesses no unpaired electrons. Hydrolysis of (1) gives a 48 % yield of 4,4'-azoxytoluene, very predominandy in the cis-form [2]; N-@-tol yl)hydroxylamine is formed by hydrolysis of (3). p-Nitrosodimethylaniline shows the same behaviour towards sodium asp-nitrosotoluene; the free radical (2) formed (ESRspectrum) is bluish-green, and the compound (4) is red and has no free radical character. We have not yet succeeded in detecting a monosodium adduct of nitrosobenzene with an unpaired electron.When its solution in ether is shaken under nitrogen at 2OoC with powdered sodium, diazofluorene ( I ) rapidly adds on a sodium atom to form a deep-blue free radical (2). which is very sensitive to oxygen. According to electron spin resonance measurements, about 60 ' %, of the sodium adduct exist in the freeradical form. Anequilibriumis therefore assumed between (2) and a dimer with no unpaired electron.When (2) is hydrolysed under nitrogen, bifluorenyl (3) is formed in 32 % yield. Hydrolysis in the presence of oxygen gives 28 % bifluorenylidene and 34 % fluorenoneazine.The deep-blue solution containing the free radical (ESRspectrum) of the monosodium compound with the canonical form (4) obtained from diphenyldiazomethane [l] behaves similarly upon hydrolysis. Unlike other comparable free radicals [2,3], the radicals (2) and (4) do not take up a second sodium atom under the roaction conditions stated. I J ) (4)Om mole of nitrogen is rapidly released from phenyl azide (5) by the action...

The reactions of sodium hydrazide with organic compounds are reviewed for the first time. The great variety of these reactions is mainly due to the extraordinary ease with which the hydrazide ion adds onto unsaturated compounds, usually to form unstable adducts that achieve stability in various ways. Addition Reactions a) With Alkenes b) With Alkynes c) With Nitriles d) Carbonyl Compounds a) With Aromatic Heterocycles b) With Aryl Halides Reduction Reactions Compounds Substitution Reactions a) Reduction of Unsaturated and Aromatic This review describes approaches for improved preparations of 19-norsteroids. They are based on novel total syntheses of estrone and on intramolecular functionalization and elimination of the C-I9 methyl groitp in androstane derivatives.(131 J f 3. Angew. Chem. internat. Edit. 1 VoI. 3 (1964) / No. 5

Anionoradikale, lV1) uber radikalische und nicht-radikalische Alkalimetalladdukte aromatischer Azoxyverbindungen rn Beim Schiitteln rnit feinverteiltem Natrium in inerten wasserfreien Losungsmitteln bilden cisund trans-Azoxybenzoldie cis-Verbindung rascherein blaues, radikalisches Mononatriumaddukt, das bei langerer Einwirkung von Natrium in ein braunrotes, nicht-radikalisches Dinatriumaddukt iibergeht. Wasser hydrolysiert sowohl das Monoals auch das Dinatriumaddukt zu Azobenzol; im Falle des Mononatriumaddukts entstehen daneben Wasserstoffperoxid und wenig Azoxybenzol. Das Mononatriumaddukt ist auch aus dem Dinatriumaddukt durch partielle Entmetallierung mit Sauerstoff (Natriumperoxid-Bildung), Benzylchlorid (Bibenzyl-Bildung) oder Azoxybenzol erhaltlich. -Weitere radikalische und nicht-radikalische Alkalimetalladdukte wurden durch Umsetzen von Lithium und Kalium Spektrum des radikalischen Monokalium-azoxybenzols wird diskutiert. Systematische Untersuchungen, insbesondere von Schlenk und Mitarbb.3), uber die Einwirkung von Alkalimetallen in inerten wasserfreien Losungsmitteln auf organische Verbindungen rnit CC-, CNund CO-Doppelbindungen sowie CC-und CN-Dreifachbindungen erschlossen zwischen 19 10 und 1930 neue Arten stabiler Radikale, von denen die Metallketyle4) die bekanntesten sind.Die Alkalimetallanlagerung in inerten Losungsmitteln an Doppelbindungen rnit semipolar gebundenen Substituenten wurde erst in jiingster Zeit naher erforscht. Dabei wurde der Nachweis fur die Bildung stabiler Radikale bei der Einwirkung von 1 ) 111.

infrared and ultraviolet spectra and optical rotation) of the natural and synthetic products. Glycosidation of (2) was also effected when sodium iodide was used instead of silver perchlorate, or even without addition of either of these compounds, although then more vigorous reaction conditions were required. In this way we obtained a glucoside of uric acid from (2) and a-acetobromoglucose. This had the same ultraviolet spectrum (measured at pH 1, 7, and 14) as (1). This product, so far unknown in nature, is therefore a 3-glucosyluric acid. Received, January 23rd. 1963 [Z 435/263 IE] [l] Communication No. 18 on organosilicon compounds; Communication No.We have found that p-nitrosotoluene rapidly adds on one equivalent of sodium to form a deep green, apparently colloidal solution of the free radical (1) when shaken under nitrogen with powdered sodium in dry ether at 5-10°C. The multilineal electron spin resonance spectrum [l] shows that the unpaired electron is located to a considerable extent in the benzene ring. The free radical ( I ) is converted by shaking for 1 hour with excess sodium into the reddish-brown substance (3), which is insoluble in ether and which reforms the green radical when shaken with oxygen (0.5 mole). f IThe same reaction in tetrahydrofuran leads to a red solution of (3), which is transformed to a clear deep-green solution of (1) by measured addition of oxygen. In this solution, about 25 % of the monosodium adduct exist in the free radical form (ESR measurement). Hence (1) is probably in equilibrium with a dimer (5), which possesses no unpaired electrons. Hydrolysis of (1) gives a 48 % yield of 4,4'-azoxytoluene, very predominandy in the cis-form [2]; N-@-tol yl)hydroxylamine is formed by hydrolysis of (3). p-Nitrosodimethylaniline shows the same behaviour towards sodium asp-nitrosotoluene; the free radical (2) formed (ESRspectrum) is bluish-green, and the compound (4) is red and has no free radical character. We have not yet succeeded in detecting a monosodium adduct of nitrosobenzene with an unpaired electron.When its solution in ether is shaken under nitrogen at 2OoC with powdered sodium, diazofluorene ( I ) rapidly adds on a sodium atom to form a deep-blue free radical (2). which is very sensitive to oxygen. According to electron spin resonance measurements, about 60 ' %, of the sodium adduct exist in the freeradical form. Anequilibriumis therefore assumed between (2) and a dimer with no unpaired electron.When (2) is hydrolysed under nitrogen, bifluorenyl (3) is formed in 32 % yield. Hydrolysis in the presence of oxygen gives 28 % bifluorenylidene and 34 % fluorenoneazine.The deep-blue solution containing the free radical (ESRspectrum) of the monosodium compound with the canonical form (4) obtained from diphenyldiazomethane [l] behaves similarly upon hydrolysis. Unlike other comparable free radicals [2,3], the radicals (2) and (4) do not take up a second sodium atom under the roaction conditions stated. I J ) (4)Om mole of nitrogen is rapidly released from phenyl azide (5) by the action...

Fur die Porenradien des Silicon-Austauschers ergeben sich folgende Werte: H+-Form, 20-50 mesh: r = 11,4 A H+-Form, 200-400 mesh: r = 11,5 A Na+-Form, 20-50 mesh: r = 10,5 14 K+-Form, 20-50 mesh: r = 11.3 A Sie liegen in dem durch die B.B.M.-Methode (vgl. Tabelle 1) abgegrenzten Bereich, wodurch auch die Zuverlassigkeit des friiher l) erarbeiteten Verfahrens hinreichend bestatigt wird. Die weitgehend homookapillare Struktur I a R t den Silicon-Austauscher als I onensieb geeignet erscheinen. H y d r a t w a s s e r s Berechnung des