Mechanism of the Reaction between Alkyl or Aryl Grignard Reagents and Hexachlorocyclotriphosphazene

An Explanation of Bi(cyclophosphazene) Formation1,2

Harry R. Allcock, James L. Desorcie, Paul J. Harris

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

An understanding has been obtained of the complex mechanisms that are followed when alkyl or aryl Grignard reagents react with (NPCl2)3 (2) in tetrahydrofuran. The main products are monoalkylcyclotriphosphazenes (3) and bi-(cyclotriphosphazenes) (4). The predominance of one product or the other depends on the reaction temperature and on the organic functionality of the Grignard reagent. The structural characterization of the bi(cyclotriphosphazenes) is described together with the reaction pathways that lead to bi(cyclotriphosphazene) formation. Two competitive pathways exist. Nucleophilic substitution on 2 yields the monoalkylcyclotriphosphazenes (3), while metal-halogen exchange on 2, followed by chlorine replacement, generates the metallophosphazene intermediate (6). Species 3 and 6 react to form the bi(cyclophosphazenes). Compounds 3 can also result from metal-halogen exchange between 6 and 2. Steric effects play a powerful role in directing the course of the reaction. The possible application of these results to macromolecular synthesis is discussed.

Original languageEnglish (US)
Pages (from-to)2814-2819
Number of pages6
JournalJournal of the American Chemical Society
Volume105
Issue number9
DOIs
StatePublished - Jan 1 1983

Fingerprint

Halogens
Metals
Chlorine
Substitution reactions
Temperature
hexachlorocyclotriphosphazene
tetrahydrofuran

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

@article{08e31d2100d949a99d0b3687d1827472,
title = "Mechanism of the Reaction between Alkyl or Aryl Grignard Reagents and Hexachlorocyclotriphosphazene: An Explanation of Bi(cyclophosphazene) Formation1,2",
abstract = "An understanding has been obtained of the complex mechanisms that are followed when alkyl or aryl Grignard reagents react with (NPCl2)3 (2) in tetrahydrofuran. The main products are monoalkylcyclotriphosphazenes (3) and bi-(cyclotriphosphazenes) (4). The predominance of one product or the other depends on the reaction temperature and on the organic functionality of the Grignard reagent. The structural characterization of the bi(cyclotriphosphazenes) is described together with the reaction pathways that lead to bi(cyclotriphosphazene) formation. Two competitive pathways exist. Nucleophilic substitution on 2 yields the monoalkylcyclotriphosphazenes (3), while metal-halogen exchange on 2, followed by chlorine replacement, generates the metallophosphazene intermediate (6). Species 3 and 6 react to form the bi(cyclophosphazenes). Compounds 3 can also result from metal-halogen exchange between 6 and 2. Steric effects play a powerful role in directing the course of the reaction. The possible application of these results to macromolecular synthesis is discussed.",
author = "Allcock, {Harry R.} and Desorcie, {James L.} and Harris, {Paul J.}",
year = "1983",
month = "1",
day = "1",
doi = "10.1021/ja00347a048",
language = "English (US)",
volume = "105",
pages = "2814--2819",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "9",

}

Mechanism of the Reaction between Alkyl or Aryl Grignard Reagents and Hexachlorocyclotriphosphazene : An Explanation of Bi(cyclophosphazene) Formation1,2. / Allcock, Harry R.; Desorcie, James L.; Harris, Paul J.

In: Journal of the American Chemical Society, Vol. 105, No. 9, 01.01.1983, p. 2814-2819.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Mechanism of the Reaction between Alkyl or Aryl Grignard Reagents and Hexachlorocyclotriphosphazene

T2 - An Explanation of Bi(cyclophosphazene) Formation1,2

AU - Allcock, Harry R.

AU - Desorcie, James L.

AU - Harris, Paul J.

PY - 1983/1/1

Y1 - 1983/1/1

N2 - An understanding has been obtained of the complex mechanisms that are followed when alkyl or aryl Grignard reagents react with (NPCl2)3 (2) in tetrahydrofuran. The main products are monoalkylcyclotriphosphazenes (3) and bi-(cyclotriphosphazenes) (4). The predominance of one product or the other depends on the reaction temperature and on the organic functionality of the Grignard reagent. The structural characterization of the bi(cyclotriphosphazenes) is described together with the reaction pathways that lead to bi(cyclotriphosphazene) formation. Two competitive pathways exist. Nucleophilic substitution on 2 yields the monoalkylcyclotriphosphazenes (3), while metal-halogen exchange on 2, followed by chlorine replacement, generates the metallophosphazene intermediate (6). Species 3 and 6 react to form the bi(cyclophosphazenes). Compounds 3 can also result from metal-halogen exchange between 6 and 2. Steric effects play a powerful role in directing the course of the reaction. The possible application of these results to macromolecular synthesis is discussed.

AB - An understanding has been obtained of the complex mechanisms that are followed when alkyl or aryl Grignard reagents react with (NPCl2)3 (2) in tetrahydrofuran. The main products are monoalkylcyclotriphosphazenes (3) and bi-(cyclotriphosphazenes) (4). The predominance of one product or the other depends on the reaction temperature and on the organic functionality of the Grignard reagent. The structural characterization of the bi(cyclotriphosphazenes) is described together with the reaction pathways that lead to bi(cyclotriphosphazene) formation. Two competitive pathways exist. Nucleophilic substitution on 2 yields the monoalkylcyclotriphosphazenes (3), while metal-halogen exchange on 2, followed by chlorine replacement, generates the metallophosphazene intermediate (6). Species 3 and 6 react to form the bi(cyclophosphazenes). Compounds 3 can also result from metal-halogen exchange between 6 and 2. Steric effects play a powerful role in directing the course of the reaction. The possible application of these results to macromolecular synthesis is discussed.

UR - http://www.scopus.com/inward/record.url?scp=0012736014&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0012736014&partnerID=8YFLogxK

U2 - 10.1021/ja00347a048

DO - 10.1021/ja00347a048

M3 - Article

VL - 105

SP - 2814

EP - 2819

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 9

ER -