Tris-N-(N′,N′,N″,N″-tetramethylguanidyl)phosphine Oxide – Synthesis and Reaction with Acids

The phosphoryl compound (O:)P(TMG)3 (TMG = N’,N’,N”,N”-tetramethylguanidyl) (6) was synthesized during attempts to obtain the potentially very basic (but still unknown) compound P(TMG)3 (1). Its reaction with HCl resulted in the triply protonated species 7. The crystal structure of compound 7 was determined; it crystallizes as a bis-dichloromethane solvate. Each protonated nitrogen forms a hydrogen bond to one chloride. A series of protonation experiments was conducted in order to test the behaviour of 6 towards weak acids.

Darstellung und Charakterisierung von 2-substituierten 5,6-Benzo-1-methyl- 3-R-1,3,2-diazaphosphorin-4-onen (R = 2-Morpholinoethyl, 1-Adamantyl) mit Phosphor in den Koordinationszahlen drei, vier und fünf / Synthesis and Characterization of 2-Substituted 5 ,6-Benzo-1-methyl-3-R -1,3,2- diazaphosphorin-4-ones (R = 2-Morpholinoethyl, 1-Adamantyl) Containing Phosphorus with Coordination Numbers Three, Four and Five

The reaction of N-methylisatoic anhydride with 2-morpholinoethylamine or 1-aminoadamantane furnished N-methyl-N′-(2-morpholinoethyl)anthranilamide 1 and N-methyl-N′- ( l-adamantyl)anthranilamide 2, respectively. 1 and 2 are intermediates in the synthesis of the 2-chloro-3-methyl-1,3,2 λ3-diazaphosphorinones 3 and 4 by reaction of 1 and 2 with PCI3. The reaction of 3 with bis(2-chloroethyl)amine hydrochloride/triethylamine or (2-chloroethyl)amine hydrochloride/triethylamine formed the 2-substituted diazaphosphorinones 5 and 6. Hydrolysis of 3 led to the 2-oxo-λ4P-compound 7. The reaction of 6 with hexafluoroacetone furnished the (λ5) phosphorane 8. 5 reacted with C7H8Cr(CO)4 to form complex 9 whereas oxidation of 5 with the H2O2: urea 1:1 adduct yielded the phosphoryl compound 10. The crystal structure of 1 displays two independent molecules that show different chain conformations. Both molecules form chains parallel to the y-axis by intermolecular N (amide)-H···O(amide) bonds. The crystal structure of 6 shows a half-boat conformation for the phosphorinone ring; the P atom lies out of the plane. Again the molecules are linked by H-bonds into chains parallel to the y-axis.

Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil IX. Umsetzungen einiger 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-dione mit Hexafluoraceton / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part IX. Reaction of some 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-diones with Hexafluoroacetone

The reactions of 2-(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (1), 2-bis(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2A3-phosphorinan- 4,6-dione (2), 2-methoxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (3) and 2-trimethylsiloxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (5) with hexafluoracetone are described. In the case of 2 and 3 the reaction furnished the spirocyclic compounds 7 and 8. 2-Bis(2-chloroethyl)amino-1,3,5-triphenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (4) did not react. In the case of 1 and 5 rearrangement reactions took place; the (2-chloroethyl)amino substituent of 1 reacted with one of two equivalents of hexafluoroacetone with formation of the spirocyclic phosphorane 6. The reaction of 5 with tetrabromoorthobenzoquinone gave the phosphoryl compound 9. Compounds 6 - 8 were characterized via their 1H-, 13C-, 19F- and 31P-NMR and mass spectra, compound 9 via its 1H-, 13C- and 31P-NMR and mass spectra. An X-ray crystal structure determination of 8 was conducted; in the six-membered ring the phosphorus atom lies 73 pm out of the plane of the other atoms, and displays trigonal bipyramidal coordination.

Beiträge zur Chemie des 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan- 6-on Ringsystems: Röntgenstrukturanalysen an einem Bis(2-chlorethyl)amino- und einem Acetamido-substituierten Derivat / Chemistry of the 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-one Ring System: X-Ray Crystal Structure Analysis of a Bis(2-chloroethyl)amino- and of an Acetamido-Substituted Derivative

The reaction of 4,5-benzo-2-chloro-3-methyl-1,3,2-oxazaphosphorinan-6-one 1 with 1,2-bis- (trimethylsiloxy)ethane led to the bisphosphoryl species 2a and to the isomeric bisphosphite derivative 2b. The reaction of 1 with heptamethyldisilazane furnished the expected diphos­phorus compound 3, with two λ3P(III) atoms linked by a methylamino group. Substitution of the chlorine atom of 1 by the 2-chloroethylamino and bis(2-chloroethyl)amino group led to the oxazaphosphorinanones 4 and 6. By oxidation of 4 with the hydrogen peroxide/urea 1:1-adduct, the phosphoryl compound 5 was formed. Oxidation of 4,5-benzo-2-diethyl- amino-3-methyl-1,3,2-oxazaphosphorinan-6-one 7 [1] with hydrogen peroxide, sulfur and se­lenium led to the corresponding phosphoryl, thiophosphoryl and selenophosphoryl com­pounds 8-10. Analogously, the reaction of the dimethylamino- and acetamido-substituted derivatives 11 and 13 [1] with elemental sulfur furnished the thiophosphoryl compounds 12 and 14. X-ray crystal structure determinations of 4 and 14 confirmed the molecular structures, proposed in accord with NMR spectroscopic and mass spectrometric data. The heterocyclic rings are essentially planar. In 14 a hydrogen bond N-H···O (amide) is observed.