Synthese, Struktur und einige Reaktionen [N‐(N′,N′,N″,N″‐tetramethyl)‐guanidinyl]‐substituierter Phosphorylverbindungen (original) (raw)
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Journal of Fluorine Chemistry, 1999
Metathetical reactions between element halides and Hg(NSO) 2 , AgNSO or (CH 3) 3 SiNSO, respectively, provide the compounds (CH 3) 3 N : B(NSO) 3 , (CF 3) n Ge(NSO) 4Àn (n 3,2), (C 6 F 5) n Ge(NSO) 4Àn (n 0,1,2,3), (C 6 F 5) 3 SnNSO, Si(NSO) 4 , (C 6 F 5) 2 PNSO and (C 6 F 5) 2 Te(NSO) 2. The stability decreases moving from C 6 F 5 to CF 3-substituted derivatives and with an increasing degree of NSOsubstitution. All compounds eliminate SO 2 at various temperatures, but only in the cases of (CF 3) 3 GeNSO and (CF 3) 2 Ge(NSO) 2 could the pure decomposition products (CF 3) 3 GeNSNGe(CF 3) 3 and (CF 3) 2 Ge(NSN) 2 Ge(CF 3) 2 be isolated and characterized. In both reactions, the SO 2-elimination is quantitative. The educts (C 6 F 5) n P[N(SiMe 3) 2 ] 3Àn (n 1,2) are synthesized for the ®rst time from C 6 F 5 PCl 2 or (C 6 F 5) 2 PBr and LiN[Si(CH 3) 3 ] 2 , but they did not condense with SOCl 2 to the corresponding sul®nylaminophosphanes. With SbF 5 and (CF 3) 3 GeNSO no SO 2 formation is observed; instead a F/NSO exchange yielding F 4 SbNSO and (CF 3) 3 GeF takes place. Inhaltsu È bersicht Reaktionen zwischen Elementhalogeniden und Hg(NSO) 2 , AgNSO bzw. (CH 3) 3 SiNSO fu Èhren zu den Verbindungen (CH 3) 3 N : B(NSO) 3 , (CF 3) n Ge(NSO) 4Àn (n 3,2), (C 6 F 5) n Ge(NSO) 4Àn (n 0,1,2,3), (C 6 F 5) 3 SnNSO, Si(NSO) 4 , (C 6 F 5) 2 PNSO und (C 6 F 5) 2 Te(NSO) 2. Die Stabilita Èt der C 6 F 5 Derivate ist gro Èûer als die der CF 3-substitutierten und mit zunehmenden NSO-Substitutionsgrad nimmt sie ebenfalls ab. In allen Fa Èllen wird bei unterschiedlichen Zersetzungstemperaturen SO 2 abgespalten, aber nur im Falle von (CF 3) 3 GeNSO kann (CF 3) 3 GeNSNGe(CF 3) 3 sowie ausgehend von (CF 3) 2 Ge(NSO) 2 auch (CF 3) 2 Ge(NSO) 2 Ge(CF 3) 2 isoliert und charakterisiert werden. Die SO 2-Abspaltung ist in beiden Fa Èllen quantitativ. Die erstmals aus C 6 F 5 PCl 2 bzw. (C 6 F 5) 2 PBr und LiN[Si(CH 3) 3 ] 2 synthetisierten Edukte (C 6 F 5) n P[N(SiMe 3) 2 ] 3Àn (n 1,2) reagieren nicht mit SOCl 2 zu den entsprechenden Sul®nylaminophosphanen. Mit SbF 5 reagiert (CF 3) 3 GeNSO nicht unter SO 2-Abspaltung, sondern es erfolgt ein F/NSO-Austausch zu F 4 SbNSO und (CF 3) 3 GeF.
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].
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].
Darstellung, Reaktionen und Strukturen spirobicyclischer Phosphorane
Chemische Berichte, 1980
Durch Reaktion von trimethylsilyl-substituierten Harnstoffen rnit Dichlorphenylphosphan erhielten wir die spirobicyclischen Phosphorane l b und l c rnit einer h3P-h5P-Bindung. Mit Chlor oder PCl, reagieren l ac unter Eliminierung von Dichlorphenylphosphan zu den spirobicyclischen Verbindungen 2a -c rnit zwei gespannten Vierringen. Die Struktur von 2a wurde durch eine Rontgenanalyse belegt. Das Phosphoratom in 2a nimmt nicht die erwartete rechteckigpyramidale Konfiguration ein, sondern hat eine annahernd trigonal-bipyramidale Geometrie. Die
Zeitschrift für Naturforschung B, 2010
Zeitschrift für Naturforschung B, 1987
It is difficult to achieve nucleophilic attack on a carbon atom bonded on two trifluoromethyl groups. However, N-[1-chloro-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-dimethylformamidine (1) reacts readily with H2O, MeOH, EtSH and P(OMe)3 even under mild conditions to form products 2, 3, 4 and 5. The reaction between 1 and Ph2PH is complex but leads in nearly quantitative yield to N-[2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-dimethylformamidinium chloride 6 which has been characterized by an X-ray structure analysis. A reaction mechanism is proposed.
Justus Liebigs Annalen der Chemie, 1968
Eingegangen am 20. September 1967 Indantrion (1) bildet mit Trialkylphosphiten 2 : 1-Addukte, vermutlich cyclische Pentaoxyphosphorane 5. Aus 5 c entsteht rnit Sauren das bekannte Phosphat 2c. Triphenylphosphin reagiert rnit 1 zum Ylid 10, dessen C = P-Bindung rnit elementarem Schwefel gespalten werden kann. Aus p-Thiokresol bzw. Diphenyldithiophosphinsaure und 1 entstehen 1 : 1-Addukte, die nach ihren Spektren und chemischen Eigenschaften rnit der Struktur 9 b, c im Einklang sind.-2-Benzyliden-indandion-(1.3) (11) addiert 1 Mol Diphenyldithiophosphinsaure zur Verbindung 12, deren Struktur spektral gesichert ist. Mustafn und Mitarbeiter 2) haben kiirzlich iiber farblose 2 : 1-Addukte der Struktur 2 aus Indantrion (1) und Dialkylphosphiten berichtet. Untersuchungen iiber eine Umsetzung cyclischer vicinaler Triketone rnit Trialkylphosphiten scheinen nicht bekannt zu sein. Ramirez und Mitarbeiter3) erhielten aus Diphenylpropantrion (3) undTrialkylphosphiten 1 : I-Addukte, die als ungesattigte Pentaoxyphosphorane 4 formuliert wurden. So schien es wunschenswert, unsere fruheren Untersuchungenz) auf die Umsetzung von 1 rnit Trialkylphosphiten auszudehnen.