Fluorinated cyclothiaphosphazenes: Synthesis, structure and reactivity

Article abstract of DOI:10.1080/10426509608037972

Reaction of chlorocyclothiaphosphazenes NPCl₂(NSOX)₂ (X = Cl, Ph) and (NPCl₂)₂NSOX (X = Cl, F, Ph) with KSO₂F in bulk leads to fluorination at the phosphorus centers. The substitution reaction follows a geminal pattern. Reactions of trans-NPF₂(NSOPh)₂ with Grignard reagents RMgX (R = Me, 'Bu) show substitution of fluorine by alkyl groups to be a slow process. The more reactive PhMgBr gives an acceptable reaction rate and good yields. Organolithium reagents offer organo-substituted cyclothiaphosphazenes in low to moderate yields, depending on the reagent used. Crystals of cis-NPF₂(NSOPh)₂ are monoclinic, space group P2₁/n, with a = 13.665(7) A, b = 10.676(1) A, c = 9.897(3) A, β= 90.55(3)°, V = 1443.8(9) A³, and Z = 4. The final R and wR values are 0.034 and 0.043, respectively. The PN and SN bond lengths vary from 1.571(2) to 1.590(2) A.

Full text of DOI:10.1080/10426509608037972

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Phosphorus, Sulfur, and Silicon and
the Related Elements
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FLUORINATED
CYCLOTHIAPHOSPHAZENES:
SYNTHESIS, STRUCTURE AND
REACTIVITY
Herman F. M. Schoo a b , Herman Winter a c , Andries Jekel a ,
Auke Meetsma a & Johan C. Van De Grampel a
a Department of Polymer Chemistry , University of Groningen ,
Nijenborgh 4, 9747 AG, Groningen, The Netherlands
b Philips Research Laboratories, Pr. Holstlaan , 5600 MD,
Eindhoven, The Netherlands
c DSM Research , PO Box 18, 6160 MD, Geleen, The Netherlands
Published online: 24 Sep 2006.
To cite this article: Herman F. M. Schoo , Herman Winter , Andries Jekel , Auke Meetsma & Johan
C. Van De Grampel (1996) FLUORINATED CYCLOTHIAPHOSPHAZENES: SYNTHESIS, STRUCTURE
AND REACTIVITY, Phosphorus, Sulfur, and Silicon and the Related Elements, 115:1, 261-271, DOI:
10.1080/10426509608037972
To link to this article: http://dx.doi.org/10.1080/10426509608037972
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