Tris dimethylamino

FLATffiRETARDANTS - PHOSPHORUS FLATffi RETARDANTS] (Vol 10) Tris(dimethylamino)borane [4375-83-1]... 

Phosphorus derivatives of different structures have been prepared including pyrazol-1-ylphosphines PPzs, PhPPz2 and Ph2PPz (Pz for pyrazolate anion (72CRV497,80MI40402)). By transamination with tris(dimethylamino)phosphine, pyrazoles and indazole are converted into (291) and (292), respectively (67CR(C)(265)1507). 3,5-Dimethylpyrazole reacts with amidodichlorophosphates to yield triamides (293) whereas 1-substituted pyrazolones yield amidophosphates (294) (71LA(750)39). 

Perhaps the most firmly based report for the formation of an azete involves flash pyrolysis of tris(dimethylamino)triazine (303). This gave a red pyrolysate believed to contain the highly stabilized azete (304) on the basis of spectroscopic data. The putative azete decomposed only slowly at room temperature, but all attempts to trap it failed (73AG(E)847). Flash pyrolysis of other 1,2,3-triazines gives only acetylenes and nitriles and it is not possible to tell whether these are formed by direct <,2-l-<,2-l-<,2 fragmentation of the triazine or by prior extrusion of nitrogen and collapse to an azete (81JCR(S)162). 

Halofluoroalkenes may be prepared by using fluorodihalomethanes or fluoro-halomethanes in olefination procedures similar to those descnbed above. Ruoro-trichloromethane treated with tris(dimethylamino)phosphine forms the corresponding phosphomum salt, which can then be used in the Wirtig procedure. The reaction depends on the nature of the solvent in tetrahydrofuran, little olefination if any occurs however, when benzomtrile is added to the mixture, ylide formation is promoted [50] (equation 48) (Table 19). 

NMR spectroscopy is ideal for detecting charged fluorinated intermediates and has been applied to the study of increasingly stable carbocation and carbanion species. Olah [164, 165] has generated stable fluorocarbocations m SbFj/SOjClF at low temperatures The relatively long-lived perfluoro-rerr-butyl anion has been prepared as both the cesium and tris(dimethylamino)sulfonium (TAS) salts by several groups [166, 167, 168], Chemical shifts of fluonnated carbocations and carbanions are listed m Table 23. 

It has been reported by Burgada (I09a) that highly enolized ketones form enamines when they are treated with tris[dimethylamino]phosphine. Only condensation products are formed when slightly enolized ketones are treated with this reagent. 

Both von Hirsch 1U) and Weingarten and White 39) have reported the amination of aldehydes and ketones by tris(dimethylamino)arsine (142) to yield the corresponding gem diamine (143) or enamine (144). Von Hirsch s... 

A reagent more reactive than tris(dimethylamino)arsine employed by Weingarten and White 39) was tetrakis(dimethylamino)titanium (145). With this compound it was possible to prepare N,N-dimethyl(l-isopropyl-2-methylpropcnyl)amine (147) from diisopropyl ketone. Weingarten and White 39) have suggested a possible mechanism for this reaction (see p. 88). If benzaldehyde 39,111), formaldehyde 111), or acetaldehyde 39) is used, the corresponding gem diamine or aminal (143) is formed. 

Tris(dimethylamino)sulfonium difluorotrimethylsilicate (TSAF), THF, 0°, 5 h, 64% yield. A TES and two phenolic TIPS groups were also cleaved. 

BOP.benzotriazol-1 -yloxy-tris(dimethylamino)-phosphonium hexafluorophosphate... 

Tlie desulfurization of thiono compounds is another frequently used synthetic approach for the formation of double bonds via carbenoid intermediates. By this methodology, some indigoid 1,3,5,7-tetraazafulvalenes 88 and 90 were synthesized (83BSB781 90JPR949).Tliis dimerization starting from 2,4,5-tris(dimethylamino)imidazolium chloride via the appropriate thione 87 has been realized in the presence of phosphanes or phosphites to... 

Therapeutic Function Antitumor agent Chemicei Name 2,4,6-Tris(dimethylamino)-1,3,5-tria2lne Common Name Hexamethylmelamine Structurai Formuia (CHj) N... 

Triphenylsilyl potassium, 141 Tris(dimethylamino)sulphonium difluoro-trimethylsilicate, 136... 

Cobalt, dinitratobis[tris(dimethylamino)phosphine oxide]-angular parameters, 1,57... 

Uranium. tetrathiocyanatotetrakis[tris-(dimethylamino)phosphine oxide]-structure, 1.87 Uranium carbide nuclear fuels dissolution, 6, 928 Uranium complexes, 3,1131-1215 carbamic acid... 

Nitrobenzene reacts with the O-trimethylsilyl ketene acetal 663 in the presence of tris(dimethylamino)sulfur(trimefhylsilyl)difluoride (Me2N)3S(Me3SiF2) (TASF) to give the O-silylated adduct 1007 a, which can be oxidized in situ, e. g. by bromine, to give the 4-substituted nitrobenzene 1008 in an overall yield of 79% [87] (Scheme 7.28). With less hindered ketene-acetals, however, mixtures of ortho- and para-substituted nitrobenzenes are obtained. Yet, on reaction of 4-fluoronitroben-zene with the cyclic O-trimethylsilyl ketene acetal 1009 the ortho-substitution product 1010 is obtained in 79% yield [87]. 

Geranyl chloride can be prepared from geraniol by the careful use of triphenylphosphine in carbon tetrachloride. Tris(dimethylamino)phosphine reacts with carbon tetrachloride to form the complex (42) which can be used to form the enol esters (43) from acid anhydrides. Similarly, aldehydes form the alkenes (44), and esters or amides of trichloroacetic acid are converted to glycidic esters. ... 

C. Nucleophilic Attack on Other Atoms.—Amidoximes have been shown to react with tris(dimethylamino)phosphine by displacing dimethylamine to give the phosphine oxides (52), but some N-substituted aromatic amidoximes give derivatives of (53). ... 

Bis(trifluoromethyl)nitroxide displaces the dimethylamino-group from tris(dimethylamino)phosphine to form (59). 

The anhydride (72) gives quite different products, (73) and (74), with tris(dimethylamino)phosphine to those previously obtained with triethyl phosphite. The formation of (73) and (74) is suggested to involve keten intermediates and an alternative mechanism is proposed for the phosphite reaction. 

The reaction of aldehydes with carbon tetrachloride in the presence of excess tris(dimethylamino)phosphine has been used to prepare vinyl dihalides in yields of 50—70%. It is suggested that the reaction takes place via an intermediate salt (77), although the formation of this salt seems more likely to be analogous to the Perkow reaction than to involve attack on oxygen. 

The alcoholysis and transamination of various aminophosphines have been studied as functions of the basicity of the attacking nucleophile and the substituents on phosphorus. As might be expected the reaction is facilitated by electron-withdrawing groups on phosphorus. The hydrolysis of tris(dimethylamino)phosphine (90) to phosphorous acid has been investigated using thin-layer chromatography and the amides (91) and (92) have been identified as intermediates. 

The chromatographic behaviour of condensed phosphates was found to be strongly influenced by water content and pH. The Ry of tris(dimethyl-amino)phosphine chalcogenides is generally lower than those of the trialkyl-phosphine chalcogenides but the difference is greatest for the P " compounds, and whereas the trialkylphosphines have the highest Ry values in the whole series, tris(dimethylamino)phosphine has the lowest. ... 

---