Additionsprodukte von Aldehyden mit dem Dinatriumsalz des Nitro-hydroxylamins und mit der Benzolsulfhydroxamsäure; über die Nicht-Existenz des Nitrosyls von A. Angeli (original) (raw)
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Chemische Berichte, 1987
Mile End Road. London E14NS Eingegangen am 2. Februar 1987 Aus Dichlor(q'-pentamethylcyc1opentadienyl)boran (1) und Stickstoff-Donoren entstehcn unterschiedlich strukturierte Lewis-Siure/Base-Addukte. Mit den zweizihnigen Molekiilen 2,2'-Bipyridin und t,lO-Phcnanthrolin wcrdcn die Boronium-Salzc 2 und 3 gebildet. Aus den einzahnigen Molekiilen Trimethylamin, Triethylamin, Pyridin, lsochinolin und Chinolin entstehen mit 1 die neutralen Abdukte 6-10, aus Acridin und Phenanthridin dagegen die Borenium-Salze 11 und 12. Das Boronium-Salz 5 entsteht aus Iod(q'-pentamethylcyclopentadienyl)bor(l +)-tetraiodoborat (4) und zwei biquivalenten Pyridin. Die Komplexe 9-12 zcrsetzen sich in Dichlormcthan zu den Bortrichlorid-Amin-Addukten 13-16. Die gelben bis tiefroten Cyclopentadienylbor-Komplexe mit aromatischen Aminen zeigen aufgrund von Exciplcx-oder Excimer-Bildung eine auFillige Lumineszenz. Die Festkorperstrukturen von 8 und 9 wurden durch Riintgenstruktruranalyse untersucht. "B-und 'H-NMR-Daten aller Addukte werden diskutiert.
Helvetica Chimica Acta, 1990
Glycolaldehyde phosphate aldomerizes in aqueous NaOH solution to a product mixture containing the racemates of the two diastereoisomeric tetrose 2,4-diphosphates and eight hexose 2,4,6-triphosphates. At room temperature in the absence of air and after 7 days, a solution 0 . 0 8~ in glycolaldehyde phosphate (= formylmethyl dihydrogenphosphate) and 2M in NaOH gives products, in up to 80% yield, with a tetrose/hexose derivative ratio of ca. 1 : 10 and with rue-allose 2,4,6-triphosphate comprising up to 50% of the mixture of sugar phosphates. When the reaction is run under the same conditions but in the presence of 0.5 mol-equiv. of formaldehyde, sugar phosphates are formed in up to 45% yield, with pentose 2,4-diphosphates now predominating over hexose triphosphates by a ratio of 3:1. rue-Ribose 2,4-diphosphate is found to be the major component, the ratios among ribose, arabinose, lyxose, and xylose 2,4-diphosphates being 52:14: 23: 11 in a representative experiment. The pentose diphosphates are constitutionally stable under the reaction conditions (observed for 23 weeks), but the diastereoisomeric ratios slowly change with time (to 22:34:30:14 after 23 weeks), showing that ribose 2,4-diphosphate is not the thermodynamically favored diastereoisomer. The observed product distributions in both the pentose and the hexose series (after 1 week) reveal an aldolization mode that is preferentially erythro in the product-determining step (the reaction of glycolaldehyde phosphate as its enolate with glycerinaldehyde 2-phosphate and tetrose 2,4-diphosphdte, respectively). An attempt is made to rationalize both this fact and the kinetic predominance of ribose 2,4-diphosphate in the pentose series and allose 2,4,6-triphosphate in the hexose series. Their configuration along the C-chain can be interpreted as corresponding to a minimum number of 1-5 repulsions in the packing of phosphate and OH substituents and minimal steric interaction between substituents at the reaction centers in the transition state of the product-determining step. The aldomerization of glycolaldehyde phosphate in the presence of formaldehyde is a variant of the formose reaction. It avoids the formation of complex formose product mixtures, largely as a consequence of the fact that aldoses which are phosphorylated at the C(2) 4. Mitteilung uber die Chemie von a -Aminonitrilen. 3. Mitteilung: [I].
Nitrilotriessigsäure und ihre Natriumsalze. MAK-Begründung, Nachtrag
2020
The German Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area has re-evaluated the Carcinogen Category, the maximum concentration at the workplace (MAK value) and the Pregnancy Risk Group of nitrilotriacetic acid [139-13-9] and its sodium salts [
Journal f�r Praktische Chemie/Chemiker-Zeitung, 1995
The thiazines lb-e, g, h react with isoamyl ni-triteMClg by nitrosation of the 3-methyl group to the 3cyano-thiazines 3b+, g, h. As by-products the mesoionic pyridazinium salts 4b, e are formed. The compounds 4b-i and 4-le-i became main products by the nitrosation of lb-i with sodium nitrite/HCl. In this case as by-products the oximes 2b-d were isolated, which can be transferred with sodium nitrite into 4b-d. The regioselectivity of the nitrosation reaction of 1 is influenced by the substituents of the aryl group.
N-[o-Nitro-benzoyl]-anthranilsäure als Umwandlungsprodukt vono-Nitro-benzaldehyd
European Journal of Inorganic Chemistry, 1960
o-Nitro-benzaldehyd kann sich unter dem Einfluß von Polyphosphorsäure und in Gegenwart von aromatischen Kohlenwasserstoffen zu N-[o-Nitro-benzoyl]-anthranilsäure (I) autokondensieren. Die Ausbeute an I ist von dem verwendeten aromatischen Kohlenwasserstoff abhängig; sie ist am höchsten mit Anthracen, das dabei zum Teil zu Anthrachinon oxydiert wird.
Helv Chim Acta, 1990
Glycolaldehyde phosphate aldomerizes in aqueous NaOH solution to a product mixture containing the racemates of the two diastereoisomeric tetrose 2,4-diphosphates and eight hexose 2,4,6-triphosphates. At room temperature in the absence of air and after 7 days, a solution 0 . 0 8~ in glycolaldehyde phosphate (= formylmethyl dihydrogenphosphate) and 2M in NaOH gives products, in up to 80% yield, with a tetrose/hexose derivative ratio of ca. 1 : 10 and with rue-allose 2,4,6-triphosphate comprising up to 50% of the mixture of sugar phosphates. When the reaction is run under the same conditions but in the presence of 0.5 mol-equiv. of formaldehyde, sugar phosphates are formed in up to 45% yield, with pentose 2,4-diphosphates now predominating over hexose triphosphates by a ratio of 3:1. rue-Ribose 2,4-diphosphate is found to be the major component, the ratios among ribose, arabinose, lyxose, and xylose 2,4-diphosphates being 52:14: 23: 11 in a representative experiment. The pentose diphosphates are constitutionally stable under the reaction conditions (observed for 23 weeks), but the diastereoisomeric ratios slowly change with time (to 22:34:30:14 after 23 weeks), showing that ribose 2,4-diphosphate is not the thermodynamically favored diastereoisomer. The observed product distributions in both the pentose and the hexose series (after 1 week) reveal an aldolization mode that is preferentially erythro in the product-determining step (the reaction of glycolaldehyde phosphate as its enolate with glycerinaldehyde 2-phosphate and tetrose 2,4-diphosphdte, respectively). An attempt is made to rationalize both this fact and the kinetic predominance of ribose 2,4-diphosphate in the pentose series and allose 2,4,6-triphosphate in the hexose series. Their configuration along the C-chain can be interpreted as corresponding to a minimum number of 1-5 repulsions in the packing of phosphate and OH substituents and minimal steric interaction between substituents at the reaction centers in the transition state of the product-determining step. The aldomerization of glycolaldehyde phosphate in the presence of formaldehyde is a variant of the formose reaction. It avoids the formation of complex formose product mixtures, largely as a consequence of the fact that aldoses which are phosphorylated at the C(2) 4. Mitteilung uber die Chemie von a -Aminonitrilen. 3. Mitteilung: [I].
Justus Liebigs Annalen der Chemie, 1969
Umsetzung von 2-Nitro-cyclohexandiol-(l.3) (11) mit Benzylmercaptan fiihrt zu 2-Nitro-cyclohexan-dithiolen mit trans-, chiro-und cis-Konfiguration (5 -7). deren Mengenverhaltnis von den Reaktionsbedingungen abhangt. -Aus 1.4-Dinitro-1.4-didesoxy-neo-inosit (13) erhalt man analog ein 1.4-Dinitro-cyclohexantetrathiol (15), aus dem Dinitrotetraacetat I6 dagegen, infolge Aromatisierung und nucleophiler Verdrangung einer Nitro-durch eine Mercapto-Gruppe, 2-Nitro-5-benzylmercapto-phenol (17). -Konfiguration und Konformation der Nitrodithiole sowie der durch Oxydation erhaltenen Sulfone 8-10 ergeben sich aus den NMR-Spektren.
Liebigs Annalen der Chemie, 1982
Durch Umsetzung ~0 1 1 1,3,4,6-Tetra-O-acetyl-(3-~-glucosamin-hydr~chl~rid (1) oder 1,3,4,6-Tetra-0-acetyl-P-D-galactosamin-hydrochlorid (10) mil Bromcarbonsaure-met hylestern in siedendem Aceton in Gegenwart von Natriumhydrogencarbonat als Base werden die N-(l,3,4,6-Tetra-O-acetyl-2-desoxy-(3-o-glucopyranos-2-yl)amin~~saure-met hylester 2 -5 und -(3-o-galactopyranos-2-yl)aminoslure-methylester 11 -12 erhalten. Nitrosierung der Zuckeraminosaure-Derivate mit Dislickstofftrioxid in Chloroform bei 0°C fiihrt zu den N-Nitroso-7.uckeraminosaure-Derivaten 6 -9 und 13-14.
Chemische Berichte, 1968
Der sterische Verlauf der Cyclisierung von Glutardialdehyd und P-Phenyl-glutardialdehyd mit Nitromethan, Nitroiithan, I-Nitro-propan und Phenylnitrornethan wird durch die GroRe des Restes R der Nitromethylen-Komponente RCHzNO2 bestimmt. Bei R = H oder CH3 entstehen bevorzugt Produkte mit aquatorialer Orientierung der Nitro-bzw. Hydroxyl-Gruppen (all-trans-Konfiguration). Bereits bei R = CzHs, insbesondere jedoch bei R = CsH5 sind Verbindungen mit chiraler Konfigurdtion die Hauptprodukte. ~ Die Nitrodiole 6, 8,22, 24, 29 und 36 lassen sich durch saure Acetylierung in die Di-0-acetate, durch katalytische Hydrierung in die entsprechenden Amindiole, als Hydroacetate, N-Acetate bzw. Triacetate charakterisiert, uberfuhren. --Die Konfiguration und Konformation der dargestellten Nitrodiole bzw. ihrer Folgeprodukte ergab sich aus einer, z. T. durch Spinentkopplung gestutzten, Analyse der Ringprotonen-NMR-Signale bei 100 MHz (Abbild. 1 ~~ 4).