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  • 1
    ISSN: 1434-1948
    Keywords: Phosphorus ; Ferrocenes ; Phosphorylated iminophosphoranes ; Dendrimers ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several R3P=N-P(X)R′2 and Fe[C5H4Ph2P=N-P(X)R′2]2 derivatives (X = S, O) are readily obtained from Staudinger reactions between phosphanes and N3-P(X)R′2. The P=N-P=X groups are easily alkylated on the × atom with methyl or isopropyl triflates. The alkylation induces a lengthening of the P-X bond, as shown by X-ray diffraction studies. This corresponds to a weakening of the P-X bond which can be cleaved with P(NMe2)3 to yield [P=N-P:] linkages. The presence of tricoordinated phosphorus atoms opens the way to a versatile reactivity, including the reaction with alkyl iodides and functionalized azides. These molecules are good models for screening which types of reagents and reactions could be used with macromolecules possessing also P=N-P=X linkages, such as dendrimers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-193X
    Keywords: Dendrimers ; Macrocycles ; Phosphorus heterocycles ; Hydrazones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three types of tetraazamacrocycles (1,4,8,11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane-5,7-dione) are grafted on the surface of phosphorus-containing dendrimers possessing P(S)Cl2 end groups (for generations 1 and 3: this corresponds to three and twelve macrocycles, respectively) and on the model compound PhCH=NN(Me)P(S)Cl2. Depending on the nature of the macrocycle, the reaction induces the formation of five-membered rings (diazaphospholanes) or of six-membered rings (diazaphosphorinanes). The structure of the adducts is deduced from 13C NMR spectra and from X-ray diffraction studies of the reaction products (8, 9, 10) of the model compound.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Phosphorus macrocycles ; Molecular modeling ; Cyclocondensation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of new phosphorus dialdehydes PhP(O)-[(CH2)nCH=CHC6H4CHO]2 (4a-c, 5a) (n = 0:4, n = 1:5; a:para, b:meta, c:ortho), with thiophosphonic bis(hydrazide) PhP(S)[NMeNH2]2 (6) yields macrocyclic compounds 9b′, c′, 10a′, 9a″, b″, c″, 10a″ and 9c′″, arising from the cyclocondensation of one, two, or three equivalents of each reagent, respectively. Molecular modeling of 4a-c, 5a, 6 and of the intermediate monocondensation products 7a-c, 8a was carried out and points out the importance of the geometry of the starting reagents in the competition between inter- and intramolecular cyclocodensation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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