Jc Vandegrampel

DERIVATIVES OF CIS-NPCL2(NSOCL)2 AND (NPCL2)2NSOCL .5. PREPARATION OF NPCL2(NSOPH)2 AND (NPCL2)2NSOPH - REACTIONS OF NPCL2(NSOPH)2 WITH DIMETHYLAMINE

Reaction of (NPCl2)2NSOCl or (NPCl2)2NSOF with benzene in the presence of AlCl3 yields (NPCl2)2NSOPh. By the same procedure two isomeric forms of NPCl2(NSOPh)2 can be obtained from cis-NPCl2(NSOCl)2. The phenylated products were characterized by IR, mass and 31P NMR spectra. Reactions of one of the isomers of NPCl2(NSOPh)2 with (CH3)2NH yield NPClN(CH3)2(NSOPh)2 (molar ratio 1:2) and NP[N(CH3)2]2(NSOPh)2 (molar ratio 1:6.8). The structures of the amino substituted derivatives were determined by means of 1H NMR measurements.

DERIVATIVES OF NPCL2(NSOCL)2 AND (NPCL2)2NSOCL .20. REACTIONS OF SOME INORGANIC RING-SYSTEMS WITH N,N'-DIMETHYLETHYLENEDIAMINE

Reactions of the ring systems (NPCl2)3, (NPCl2)2NSOX, and NPCl2(NSOX)2 (X = Cl, Ph) with N,N′-dimethylethylenediamine lead to mono-, bis-, and tris(spirocyclic) compounds as the only characterizable products. The 1H and 31P NMR parameters are reported and briefly discussed.

DERIVATIVES OF NPCL2(NSOCL)2 AND (NPCL2)2NSOCL .23. REACTIVITY IN AMINOLYSIS REACTIONS BY NH3

Reactions of the cyclic systems (NPCl2)2NSOX and NPCl2(NSOX)2 (X = F, Cl, Ph) with NH3 in diethyl ether or acetonitrile at low temperature provide convincing evidence that the P-bonded chlorine atoms are replaced by NH2 groups along a geminal pathway. No disruption of the S-F and S-Ph bonds occurs. Aminolysis of NPCl2(NSOCl)2 proceeds to NP(NH2)2(NSOCl)2, followed by decomposition, (NPCl2)2NSOCl can be transformed to NPClNH2NP(NH2)2NSOCl without cleavage of the ring skeleton

DERIVATIVES OF CIS-NPCL2(NSOCL)2 AND (NPCL2)2NSOCL .10. AMINOLYSIS OF CIS-NPCL2(NSOF)2 AND (NPCL2)2NSOF

The aminolysis of the ring systems cis-NPCl2(NSOF)2 and (NPCl2) 2NSOF by cyclic amines in acetonitrile at room temperature shows the S-F bond to be stable towards a nucleophilic attack. The amino derivatives are characterized by their spectral data. Structure assignments are based on 31P NMR spectroscopy.

DERIVATIVES OF CIS-NPCL2(NSOCL)2 AND (NPCL2)2NSOCL, .6. PYRIDINIUM DERIVATIVES OF CIS-NPCL2(NSOF)2 AND CIS-NPCL2(NSOCL)2

The compounds with composition NPCl(NSOF)2(C5H5N)OH (1) and NPCl(NSOCl)2 (C5H5N)OH (2) are prepared by reaction of cis-NPCl2(NSOX)2 (X = F, Cl) with pyridine in ether. The pyridinium derivatives are colourless crystalline solids. Tentative structure assignments are given based on NMR data.

DERIVATIVES OF CIS-NPCL2(NSOCL)2 AND (NPCL2)2NSOCL .4. ISOTHIOCYANATO DERIVATIVES OF CIS-NPCL2(NSOF)2

The compounds NPClNCS(NSOF)2 and NP(NCS)2(NSOF)2 are prepared by reaction of cis-NPCl2(NSOF)2 with KSCN. The mono(isothiocyanato) derivative obtained is a colourless liquid, consisting of two isomers in a ratio of 1:3.8; the bis(isothiocyanato) compound is a white crystalline solid.

DERIVATIVES OF CIS-NPCL2(NSOCL)2 AND (NPCL2)2NSOCL .9. SUBSTITUTION-REACTIONS OF CIS-NPCL2(NSOCL)2 WITH PIPERIDINE

Aminolysis of cis-NPCl2(NSOCl)2 by piperidine in acetonitrile at room temperature proceeds via a non-geminal substitution pattern. During the first substitution step the reactivity of a SOCl-centre appears to be greater than that of a PCl2-centre. The second and third substitution step successively take place at the PCl2- and remaining SOCl-centre. The different isomeric forms of the mono-, bis-, tris-, and tetrakis(piperidino) derivatives are characterized by means of 31P NMR data. Application of 13C NMR leads in two cases to a structure assignment.