Process for the synthesis of cycloorganylphosphanes and di(alkyli metal/alkaline earth metal) oligophosphanediides
View Patent ↗The invention relates to a process for the preparation of cycloorganylphosphanes of formula 1 (R 1 P) n by reaction of dihalo(organyl)phosphanes of formula R 1 PHal 2 with: a) activated zinc in an organic solvent, or with: b) an alkali metal or alkaline earth metal in a non-polar organic solvent in the presence of an activator, wherein R 1 is C 1 –C 12 alkyl; C 3 –C 12 cycloalkyl, aryl or heteroaryl, Hal is F, Cl, Br or I, and n is a number from 3 to 20. The invention relates also to novel di(alkali metal/alkaline earth metal) oligophosphanediides and to the use thereof in the preparation of organophosphorus compounds.
1. A process for preparing a cycloorganylphosphane of formula I
(R 1 P) n I
by reaction of a dihalo(organyl)phosphane of the formula R 1 PHal 2 ,
wherein
R 1 is C 1 –C 12 alkyl; C 3 –C 12 cycloalkyl, aryl or heteroaryl,
Hal is F, Cl, Br or I, and
n is a number from 3 to 20,
with
a) activated zinc in an organic solvent, or with
b) sodium in a non-polar organic solvent in the presence of tetramethylethylenediamine, wherein the ratio by volume of non-polar solvent to tetramethylethylenediamine is from 10:0.1 to 10:5.
2. A process according to claim 1 for preparing a cycloorganylphosphane of formula I by reaction of a dihalo(organyl)phosphane of the formula R 1 PHal 2 with activated zinc in an ethereal solvent.
3. A process according to claim 1 for preparing a cycloorganylphosphane of formula I by reaction of a dihalo(organyl)phosphane of the formula R 1 PHal 2 with sodium in a non-polar organic solvent in the presence of tetramethylethylenediamine, wherein the ratio by volume of non-polar solvent to tetramethylethylenediamine activator is from 10:0.1 to 10:5.
4. A process according to claim 3 wherein the non-polar organic solvent is toluene.
5. A process according to claim 1 wherein R 1 is phenyl.
6. A di(alkali metal/alkaline earth metal) oligophosphanediide of the structural formula 2, 3 or 4
wherein
R is C 1 –C 6 alkyl; C 3 –C 6 cycloalkyl, aryl or heteroaryl;
M is Li, Na, K, Cs or Mg;
Hal is F, Cl, Br or I;
L is an activator; and
n and m denote the number of coordinated molecules L, which may be from 1 to 8.
7. A di(alkali metal/alkaline earth metal) oligophosphanediide according to claim 6 wherein R is phenyl and L is tetramethylethylenediamine or 1,2-dimethoxyethane.
8. A process for the preparation of a di(alkali metal/alkaline earth metal) oligophosphanediide of formula (2), (3) or (4) according to claim 6 by reaction of a dihalo(organyl)phosphane of the formula RPHal 2 , wherein
R is C 1 –C 12 alkyl; C 3 –C 12 cycloalkyl, aryl or heteroaryl,
Hal is F, Cl, Br or I, and
n is a number from 3 to 20,
with an alkali metal or alkaline earth metal in a non-polar organic solvent in the presence of an activator, wherein the molar ratio of alkali metal or alkaline earth metal to RPHal 2 is >1.
9. A process for the preparation of an organophosphorus compound
by reaction of a di(alkali metal/alkaline earth metal) oligophosphanediide of formula (2), (3) or (4) according to claim 6 with
an alkyl halide, trimethylsilyl chloride, sulfur, an arylcarboxylic acid chloride or trimethylsilyl choride and subsequently a carboxylic aicd chloride.
10. A process according to claim 2 wherein R 1 is phenyl.
11. A process according to claim 3 wherein R 1 is phenyl.