François Sournies

An answer to the spiro versus ansa dilemma in cyclophosphazenes: Part XI. The first macro-SPIRO and macro-ANSA species from dioxodiamines☆

Abstract Aminolysis of N3P3Cl6 by dioxodiamines in suitable conditions leads to two kinds of cyclophosphazenic macro-ANSA and macro-SPIRO species which will be used for further applications as macrocyclic ligands.

Crystal and molecular structure of the two MACRO-ANSA and MACRO-SPIRO isomeric cyclotriphosphazenes N3P3Cl4 [HN(CH2)3O(CH2)4O(CH2)3NH]

Abstract Reaction of N 3 P 3 Cl 6 with 4,9-dioxadodecane-1,12-diamine (coded as 3O4O3) proceeds cleanly to yield two isomeric cyclotriphosphazenic species, namely MACRO-ANSA (3O4O3) and MACRO-SPIRO (3O4O3), depending on experimental conditions. These two chemicals crystallize in monoclinic and orthorhombic systems, respectively. MACRO-ANSA (3O4O3): P 2 1 / n , a =15.405(7), b =8.728(2), c =15.685(5)A, β=98.10(3)°, V =2088 A 3 , Z =4, D X =1.52(3) Mg m −3 , R =0.077 for 1743 unique observed reflections and 247 variable parameters. MACRO-SPIRO (3O4O3): P 2 1 2 1 , a =12.638(4), b =17.364(9), c =19.334(14) A, V =4242A 3 , Z =8, D X =1.50(5) Mg m −3 , R =0.046 for 1395 unique observed reflections and 441 variable parameters. The structures of these two isomers exhibit a spatial arrangement N 3 P 3 Cl 4 with [HNue5f8(CH 2 ) 3 ue5f8Oue5f8(CH 2 ) 4 ue5f8Oue5f8(CH 2 ) 3 ue5f8NH] as a 17-membered arch onto two P atoms of the N 3 P 3 ring for the MACRO-ANSA derivative and as a 15-membered loop on one P atom of the N 3 P 3 ring for the MACRO-SPIRO compound.

An answer to the spiro versus ANSA dilemma in cyclophosphazenes: Part XII. The first MEGA-SPIRO and MEGA-ANSA species from trioxodiamines☆

Abstract Aminolysis of N 3 P 3 Cl 6 by trioxodiamines in suitable conditions yields two kinds of cyclophosphazenic MEGA-ANSA and MEGA-SPIRO species which constitute new macrocyclic ligands.

Crystal and molecular structure of a new allotropic variety of the mega-spiro cyclophosphazene from diethylene glycol bis-(3-aminopropyl)-ether, N3P3Cl4[HN(CH2)3O(CH2)2O(CH2)2O(CH2)3 NH)]

Abstract Reaction of N 3 P 3 Cl 6 with diethylene glycol bis-(3-aminopropyl)-ether (coded as 3O2O2O3) using a toluene/Na 2 CO 3 interface process yields cleanly the MEGA-SPIRO (3O2O2O3) species, the crystal and molecular structure of which was recently reported (allotropic variety A, orthorhombic, Pca 2 1 , Z =4). The same reaction, when performed in THF, leads to the MEGA-ANSA (3O2O2O3) isomer as the very major product, traces of MEGA-SPIRO (3O2O2O3) being separated by skillful SiO 2 column chromatography. This chemical crystallizes in the monoclinic system, C 2/ c, a =10.95(9), b =23.26(4), c =17.12(6) A, β=94.1(1)°, V =4350 A 3 , Z =8, D X =1.51(2) Mg m −3 , R =0.068 for 2188 unique observed reflections and 226 variable parameters. As expected the structure exhibits a spatial arrangement N 3 P 3 Cl 4 with (HNue5f8(CH 2 ) 3 ue5f8Oue5f8(CH 2 ) 2 ue5f8Oue5f8(CH 2 ) 2 ue5f8Oue5f8(CH 2 ) 3 ue5f8NH) as a 16-membered loop on one phosphorus atom of the N 3 P 3 ring (as in the allotropic variety A) but the conformation of this loop is different from the one in A. Thus, one may conclude that reaction of N 3 P 3 Cl 6 with diethylene glycol bis-(3-aminopropyl)-ether in THF yields a second allotropic variety B of the MEGA-SPIRO (3O2O2O3) as a by-product.

An answer to the spiro versus ansa dilemma in cyclophosphazenes Part XIV. The first MACRO-BINO and MEGA-BINO species from oxodiamines☆

Abstract Aminolysis of N 3 P 3 Cl 6 by oxodiamines in ethyl ether-Na 2 CO 3 saturated water (interface process) and in (2:1) stoichiometric conditions leads to MACRO-BINO and MEGA-BINO species which are starting materials for further syntheses of cyclophosphazenic crown ethers and cryptands.

An anwser to the sprio versus ansa dilemma in cylophosphazenes Part XV. The first MACRO-diBINO and MEGA-diBINO non-geminal species from oxodiamines

Abstract Aminolysis of N 3 P 3 Cl 6 by oxodiamines in ethyl ether-Na 2 CO 3 saturated water (interface process) [(1:1) stoichiometric conditions] or in 2-propanol [(1:2) stoichiometric conditions] leads stereoselectively and/or stereospecifically to MACRO-diBINO and MEGA-diBINO species which constitute a new class of macrocylic crown ethers.

Crystal and molecular structure of the megaspiro cyclophosphazenic species from diethylene glycol bis-(3-aminopropyl)-ether, N3P3Cl4{(HN(CH2)3O(CH2)2O(CH2)2 O(CH2)3NH)}☆

Abstract Reaction of N 3 P 3 Cl 6 with diethylene glycol bis-(3-aminopropyl)-ether (coded as 3O2O2O3) using a tolueneue5f8Na 2 CO 3 interface process leads to the MEGA-SPIRO (3O2O2O3) species neat. This chemical, C 10 H 22 N 5 O 3 P 3 Cl 4 , M r =493.03, crystallizes in the orthorhombic system, Pca 2 1 , a =15.453(3), b =13.978(2), c =9.818(2) A, V =2121(2) A 3 , Z =4, D X =1.55(1), D m =1.55(3) Mg m −3 , λ(Mo K α)=0.70926 A, F (000)=1016, T =291 K, R =0.038 for 1491 unique observed reflections and 250 variable parameters. The structure exhibits a spatial arrangement N 3 P 3 Cl 4 with HNue5f8(CH 2 ) 3 ue5f8Oue5f8(CH 2 ) 2 ue5f8Oue5f8(CH 2 ) 3 ue5f8NH as a 16-membered loop on one phosphorus atom of the N 3 P 3 ring.

Crystal and molecular structure of the first dibino non-geminal macrocyclic dicyclophosphazene, & {;N3P3Cl4[HN(CH2)3O(CH2)2O(CH2)3NH]&};2

Abstract Reaction of N 3 P 3 Cl 6 with the 4,7-dioxadecane-1,10-diamine (coded as 3O2O3) using an Et 2 O/Na 2 CO 3 water interface process leads to the DIBINO non-geminal 30-membered macrocyclic dicyclophosphazene &{;N 3 P 3 Cl 4 [HNue5f8(CH 2 ) 3 ue5f8Oue5f8(CH 2 ) 2 ue5f8Oue5f8(CH 2 ) 3 ue5f8NH]&}; 2 . This 30-crown-ether-like architecture crystallizes in the triclinic system, P 1 , a =9.019(6), b =9.224(5), c =11.542(8) A, α=94.87(4), β=95.97(4), γ=99.68(3)°, V =936(1) A 3 , D x =1.599 Mg m −3 , R =0.049 for 2862 unique reflections and 199 variable parameters. The structure exhibits a spatial arrangement of two N 3 P 3 Cl 4 with two [HNue5f8(CH 2 ) 3 ue5f8Oue5f8(CH 2 ) 3 ue5f8Oue5f8(CH 2 ) 3 ue5f8NH] as bridges on different P atoms of N 3 P 3 rings. Moreover, the two N 3 P 3 rings are trans to the average plane of the 30-membered macrocycle (“chair” conformation).

Raman studies on anticancer inorganic ring–dna interactions: Part 1. HexaziridmocyclotriphosphazeneN3P3(NC2H4)6

Abstract A Raman investigation of hexaziridinocyclotriphosphazene3DNA interactions in vitro suggests that the alkylating sites on DNA for this powerful antitumour agent are the N(7) and N H 2 positions of adenine.

An answer to the spiro versus ansa dilemma in cyclophosphazenes: Part XIII. Synthesis and crystal structure of the first di-MACROSPIRO and di-MEGASPIRO species from di- and tri-oxodiamines

Abstract Aminolysis of N 3 P 3 Cl 6 by dioxodiamines and trioxodiamines in suitable conditions yields di-MACROSPIRO and di-MEGASPIRO species which constitute new di-macrocyclic monocyclophosphazenic architectures. X-Ray structures of di-SPIRO derivatives from 4,9-dioxadodecane-1,12-diamine and from 4,7,10-trioxatridecane-1,13-diamine reveal two highly unsymmetrical 15- and 16-membered loops, respectively, grafted on the same N 3 P 3 ring.