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In eine Suspension von 10:5 g (0,05 Mol) 1-Methdnsulfonyl-3-n-butylthioharnstoff in 65 in1 Chlorbenzol werden 5 g (0,05 Mot) Phosgen in 40 ml Chlorbenzol tropfenweise bei 5 "C eingetragen. Nach einstundigem Ruhren bei Zimmertemperatur erhitzt man zum Sieden und entfernt das iiicht umgesetzte Phosgen mit Stickstoff. Durch Abdestillieren des LLisungsmittels und Vakuumdestillation des Riickstandes gewinnt man 7,O g (79,5 %) Methansulfonyl-n-butylcarbodiimid, K p = 103-105°C/0,3 Torr; nk435 = 1,4798 (vgl. Abschnitt IV, 2). In eine Suspension von 8,5 g (0,023 Mol) 1-p-Toluolsulfonyl-3-phenylthiol1arnstoff in 50 ml Chlorbenzol wird tropfenweise eine Losung von 2,8 g (0,028 Mol) Phosgen in 35 nil Chlorbenzol eingetragen. Nach einstundigem Ruhren wird das Losungsmittel im Vakuum abdestilliert. Aus dem Ruckstand, 9 g (97,3 %), Fp = 128-131 "C, kann analysenreines 3-Phenyl-4-p-toluolsulfonylimino-l,3-thiazetidin-2-on, F p = 137 bis 139 "C, durch Umkristallisation aus Athylacetat erhalten werden (vgl. Abschn. IV, 2). 17. 2-Phenylimino
In eine Suspension von 10:5 g (0,05 Mol) 1-Methdnsulfonyl-3-n-butylthioharnstoff in 65 in1 Chlorbenzol werden 5 g (0,05 Mot) Phosgen in 40 ml Chlorbenzol tropfenweise bei 5 "C eingetragen. Nach einstundigem Ruhren bei Zimmertemperatur erhitzt man zum Sieden und entfernt das iiicht umgesetzte Phosgen mit Stickstoff. Durch Abdestillieren des LLisungsmittels und Vakuumdestillation des Riickstandes gewinnt man 7,O g (79,5 %) Methansulfonyl-n-butylcarbodiimid, K p = 103-105°C/0,3 Torr; nk435 = 1,4798 (vgl. Abschnitt IV, 2). In eine Suspension von 8,5 g (0,023 Mol) 1-p-Toluolsulfonyl-3-phenylthiol1arnstoff in 50 ml Chlorbenzol wird tropfenweise eine Losung von 2,8 g (0,028 Mol) Phosgen in 35 nil Chlorbenzol eingetragen. Nach einstundigem Ruhren wird das Losungsmittel im Vakuum abdestilliert. Aus dem Ruckstand, 9 g (97,3 %), Fp = 128-131 "C, kann analysenreines 3-Phenyl-4-p-toluolsulfonylimino-l,3-thiazetidin-2-on, F p = 137 bis 139 "C, durch Umkristallisation aus Athylacetat erhalten werden (vgl. Abschn. IV, 2). 17. 2-Phenylimino
conclusions based on the crystalline state to the dissolved state. A complex of this nature may be formed in one of two ways:I . The central cation reacts with monomers or small isopolyanions ; 2. The central cation reacts with the preformed isopolyanion.Only in the second case can reliable conclusions regarding the isopolyanion be based on the structure of the complex. Both reactions evidently are possible in the formation of hetero-com.plexes. Thus the fact that "true" metatungstate ions do not react with phosphoric acid shows very clearly that, for example, the dodecatungstatophosphate ion, which is similar to the true metatungstate ion 1541, can be formed in accordance with 1 ; it is formed on acidification of a solution containing monotungs:ate and phosphate ions. The complexes we have described, on the other hand, evidently are formed in accordance with 2, so that there is a direct relation between these complexes and the isopolyanions originally present in the solution. Some of the many reasons for this conclusion are: The formation of different complexes with cations from paratungstate solutions of the same concentration and pH but of different ages would not be understandable if the heterocomplexes were formed from fragments and not from the different polytungstate ions present in each case.True metatungstate ions and decavanadate ions are broken down only slowly in alkaline solutions. Since complex formation with these polyanions is instantaneous, it is hardly possible that it could proceed via fragments.The reaction of methyl red with molybdate in the ratio 1 : 12 could not be explained without assuming the prior existence of dodecamolybdate ions with cavities capable of accommodating the dye.We have attempted in this paper to outline, with the aid of some examples, the present state of research on polyacids, and to describe a number of new methods that have contributed to progress in this field. New insights into the chemistry of the polyacids will undoubtedly be gained in the future by the use of numerous and versatile chemical and physical methods, and by a logical combination of all the individual results.
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