ISSN:
0009-2940
Keywords:
Nitrilimines
;
Phosphorus heterocycles
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reactions involving the λ3-phosphorus atom of N-[bis(diisopropylamino)phosphanyl)]-C-[(bis(diisopropylamino) -thio-phosphoranyl)nitrilimine (1) are reported. Addition of elemental sulfur or selenium to 1 leads, by a formal [1 + 4] cycloaddition, to 1,3,4,2λ5-thiadiazaphosphole 3a or 1,3,4,2λ5-selenodiazaphosphole 3b in 85 and 84% yield, respectively. Reactions of 1 with dimethyl acetylenedicarboxylate and tetracyanoethylene afford the corresponding [2 + 4] adducts 1,2,3λ5-diazaphosphinine 6 (80% yield) and 1,2,4,3λ5-triazaphosphinine 10 (80% yield). Phenyl azide reacts with 1 with loss of nitrogen to give 1,2,4,3λ5-triazaphosphole 15 (74% yield), while the reaction of 1 with α-diazo ketone 17 leads with conservation of the N2 grouping to the formation of 1,2,4,3λ5-triazaphosphole 20 (85% yield). Addition of methyl trifluoromethanesulfonate to 1 affords N-[bis(diisopropylamino)methylphosphonioyl]-C-[bis(diisopropylamino)thiophosphoranyl]nitrilimine 22. In contrast to 1, the new stable nitrilimine 22 is strongly electrophilic. [2 + 3] cycloadditions are observed with ethyl vinyl ether, styrene, methyl acrylate and phenylacetylene to furnish the corresponding pyrazolines 23 - 25 and pyrazole 26 in good yields. Water adds to 22 by a 1,3-addition process to give hydrazine 27 (88% yield). The lithium salt 30 of [bis(diisopropyl-amino)thiophosphoranyl](diazo)methane reacts with [bis(pentafluorophenyl)](chloro)phosphane to afford the corresponding diazo compound 32 (50% yield) while the reaction with (chloro)(phenyl)[2,4,6-tris(trifluoromethyl)phenyl]phosphane furnishes nitrilimine 33 in 82% yield. Only 1,3-addition reactions with water or diisopropylamine leading to hydrazine 34 (65% yield) and hydrazone 35 (54% yield) are observed on treatment with this new poorly reactive nitrilimine.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240812
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