Relating to organic processes

A compound of formula (I) to (III) ##STR1## in which the symbols R to R.sub.6 are organic radicals. These compounds can be used as intermediates in the production of a phosphite-HALS product.

Up until now, one of the standard methods for preparing phosphites 
containing hindered amine light stabilizers (hereinafter defined as 
"Phosphite-HALS" compounds) is to react a phenol- or alcohol-containing a 
HALS group with phosphorus trichloride in the presence of a tertiary amine 
which acts as an acceptor for the liberated HCl. 
A voluminous precipitate of the corresponding amine hydrochloride results, 
which causes stirring problems and so requires the presence of inert 
solvent or an excess of amine to give a stirrable slurry. After the 
reaction, this hydrochloride has to be filtered off, which is time 
consuming and results in loss of product. Filtration and washing with 
solvent has to be performed under inert conditions, if the highly reactive 
intermediate is to be isolated for purification. 
To overcome this problem, we have discovered new intermediate phosphine 
compounds for forming these phosphite-HALS. 
According to the invention there is provided a compound of formula (I), 
(II), (III) 
##STR2## 
in which R is hydrogen, --OH, --C.sub.1-24 alkyl, --O--C.sub.1-24 alkyl, 
--O--CO--C.sub.1-24 alkyl, --O--CO-phenyl, or --CO--R.sub.7 ; where 
R.sub.7 is --CH.dbd.CH.sub.2, --C(C.sub.1-4 alkyl).dbd.CH.sub.2, 
--C.sub.1-24 alkyl, --C.sub.1-24 alkenyl, phenyl, benzyl, --CO-phenyl, 
--CO--O--C.sub.1-24 alkyl --COOH or NR.sub.8 R.sub.9 ; where each R.sub.8 
and R.sub.9 independently is selected from hydrogen, C.sub.1-24 alkyl, 
C.sub.5-12 cycloalkyl, C.sub.6-12 aryl (preferably phenyl), C.sub.6-12 
aryl-C.sub.1-12 alkyl (preferably phenyl-C.sub.1-12 alkyl) and C.sub.1-12 
alkyl-C.sub.6-12 aryl (preferably C.sub.1-12 alkylphenyl); or 
R.sub.8 and R.sub.9 form a 4-8 membered ring containing the N-atom and 3-7 
carbon atoms. The ring can also contain further heteroatoms such as N, O, 
S or P; 
each R.sub.1 is independently C.sub.1-5 alkyl or both groups R.sub.1 form a 
group --(CH.sub.2).sub.5 --; 
each R.sub.2 is independently C.sub.1-5 alkyl or both groups R.sub.2 form a 
group --(CH.sub.2).sub.5 --; 
R.sub.3 is --NR.sub.8 R.sub.9, where R.sub.8 and R.sub.9 are defined above; 
R.sub.4 is a group selected from R.sub.3 or R.sub.5 ; where the 
significance of R.sub.4 is independent of that of R.sub.3 or R.sub.5, 
where R.sub.5 is a group of formula (.alpha.) 
##STR3## 
R.sub.6 is R.sub.4 or Hal; Hal is Cl or Br, (preferably Cl); and 
Y is --O--, --NH-- or --N--(C.sub.1-24 alkyl)-. 
Preferably each R.sub.1 and R.sub.2 is methyl. 
Preferably R is R' where R' is hydrogen, --O--CO-phenyl, --C.sub.1-18 
alkyl, --O--C.sub.1-18 alkyl, oxygen or --CO--R.sub.7 ' where R.sub.7 ' is 
--CH.dbd.CH.sub.2, C.sub.1-8 alkyl, --CO--C.sub.1-8 alkyl or 
--CO--O--C.sub.1-4 alkyl. 
Preferably R.sub.3 is R.sub.3 ' where R.sub.3 ' is selected from 
di(C.sub.1-24 alkyl)amino, di(C.sub.5-12 cycloalkyl)amino, di(C.sub.6-24 
aryl)amino, di(C.sub.7-24 alkylaryl)amino or di(C.sub.7-24 arylalkyl)amino 
or --NH(C.sub.2-24 alkyl), preferred cyclic derivatives are morpholino and 
piperidinyl residues. 
More preferably R.sub.3 is R.sub.3 " where R.sub.3 " is --N(C.sub.2-4 
alkyl).sub.2 or --HN(C.sub.2-4 alkyl). 
Preferably R.sub.9 is R.sub.9 ' where R.sub.9 ' is hydrogen or C.sub.1-24 
alkyl. 
Preferably in R.sub.8 and R.sub.9, aryl is phenyl. 
According to a further aspect of the invention, it is possible to prepare 
compounds of formula (I) 
##STR4## 
by reacting 1 mole of a compound of formula (II) or (III) 
##STR5## 
with 1 mole of a compound of formula (IV) 
EQU R.sub.3 --H (IV) 
where the symbols are as defined above. 
Alternatively and preferably, a compound of formula (I), in which R.sub.4 
has the same significance as R.sub.3, can be prepared by reacting 1 mole 
of a compound of formula (V) 
##STR6## 
with one mole of a compound of formula (VI) 
EQU P(R.sub.3).sub.3 (VI) 
The amino group in P(R.sub.3).sub.3 is preferably derived from a secondary 
linear, branched or cyclic amine with a boiling point in the range of 
30.degree. C. to 150.degree. C. 
Compounds of formula (II) can be prepared by reacting, in the presence of 
tertiary amine, one mole of a compound of formula (V) 
##STR7## 
with 1 mole of a compound of formula (VIII) 
EQU P(Hal).sub.3 (VIII) 
optionally followed by reacting with 1 mole of a compound of formula (IX) 
EQU R.sub.4 --H (IX) 
in which the symbols are as defined above. 
Compounds of formula (III) can be prepared by the same process as described 
above for forming a compound of formula (II) but in the absence of 
tertiary amine. 
Compounds of formula (V) and (VIII) are known or can be made from known 
compounds by known methods. 
Compounds of formula (VI) can be prepared by reacting 6 moles of a compound 
of formula (VII) 
EQU R.sub.3 --H (VII) 
with one mole of a compound of formula (VIII) 
EQU P(Hal).sub.3 (VIII) 
where Hal is halogen. 
3 moles of R.sub.3 --H are used up binding the liberated HCl. 
A preferred compound of formula (VIII) is PCl.sub.3. 
The reaction of a compound of formula (II) or (III) with a compound of 
formula (IV) to form a compound of formula (I) is carried out at 
temperatures, -20 to +100.degree. C., more preferably 0-60.degree. C. 
Optionally a conventional organic solvent may be used. 
Compounds of formula (I) can be used to prepare compounds of formula (X) or 
(XI). 
##STR8## 
in which R.sub.10 is C.sub.1-30 alkoxy, C.sub.2-30 alkenyloxy, C.sub.5-12 
cycloalkoxy, and phenoxy unsubstituted or substituted by 1 to 3 groups 
selected from C.sub.1-24 alkyl, C.sub.1-24 alkoxy and hydroxy; and 
R.sub.11 is a significance of R.sub.10 or R.sub.5, where the significance 
of R.sub.11 is independent of R.sub.10 or R.sub.5, where R.sub.5 is a 
group of formula (.alpha.) defined above; or 
R.sub.10 and R.sub.12 form a phosphorus containing ring of formula (b) 
##STR9## 
where X is a group of formula (c) 
##STR10## 
where R.sub.8 is as defined above, n is 0 to 3, Z is --CH.sub.2 --, 
--CH(C.sub.1-4 alkyl)-, --C(C.sub.1-8 alkyl).sub.2 -, --O--, --S-- or a 
direct bond. 
m is 2 to 4; and 
when m is 2, R.sub.40 is --(OCH.sub.2).sub.2 --C(C.sub.1-12 alkyl).sub.2 
when m is 3, R.sub.40 is --(OCH.sub.2).sub.3 --C(C.sub.1-12 alkyl) or 
--(OC.sub.1-12 alkyl).sub.3 -N or 
when m is 4, R.sub.40 is --(OCH.sub.2).sub.4 --C. 
Compounds of formula (X) are prepared by reacting one mole of a compound of 
formula (I) with 
1 to 2 moles of a compound of formula (XII) 
EQU H--R.sub.10 (XII) 
or 1 mole of a compound of formula (XIII) 
##STR11## 
where the symbols are as defined above. 
Compounds of formula (XI) 
##STR12## 
can be prepared by reacting m moles of a compound of formula (I) 
##STR13## 
in which R.sub.4 is R.sub.5 ; and where R.sub.5 is a group of formula 
(.alpha.) 
##STR14## 
R.sub.3 is --N(C.sub.1-6 alkyl).sub.2 with 1 mole of a compound of formula 
(XX) 
EQU (H).sub.m --R.sub.40 (XX) 
The reaction of a compound of formula (I) with a compound of formula (XII) 
or (XIII) is preferably carried out at elevated temperatures, preferably 
from 80-200.degree. C., more preferably at 100-160.degree. C. A solvent 
may or may not be required dependent on the state of the reactants. 
Compound of formula (XII) and (XIII) are known or may be prepared by known 
methods from known compounds. Compounds of formula (X) and (XI) can also 
be made from a known compound. 
The use of the new compounds of formula (I), (II) or (III) (preferably 
those of formula (I)) as intermediates offers an attractive possibility 
for carrying out the reaction with alcohols or phenols to form compounds 
of formula (X) or (XI) in homogenous solution or even without using 
solvents. Furthermore, the amount of R.sub.3 --H (which can be distilled 
off) gives an useful measure of the reaction. No problematic filtration 
needs to be performed if compounds of formula (I) are used. The workup and 
purification can be performed conventionally. The absence of acidic 
impurities, such as amine hydrochlorides, can improve the hydrolytic 
and/or thermal stability of the final products, because it is known that 
such impurities can cause catalytic deterioration of the final compounds 
under the conditions mentioned. 
The phosphite-HALS products (i.e. compounds of formula (X) and (XI)), are 
well known as processing stabilizers for polymeric materials and as light 
stabilizers for said polymeric materials. 
Polymeric materials that can be stabilized by phosphite-HALS (e.g. 
compounds of formula (X) or (XI)) include homopolymers, copolymers and 
polymer blends described in British Patent Application No. 2,276,387 A 
published Sep. 28, 1994 equivalent to U.S. Pat. No. 5,488,079, or U.S. 
Ser. No. 08/248282 May 23, 1994, abandoned. 
Preferred polymeric materials that can be stabilized are polyolefins, such 
as polypropylene, polyethylene (e.g. high density polyethylene, low 
density polyethylene, linear low density polyethylene or medium density 
polyethylene), polybutylene, poly-4-methylpentene and copolymers thereof 
as well as polycarbonate, polystyrene and polyurethane. 
Also preferred polymeric materials that can be stabilized by compound of 
formula (X) and (XI) are polyurethanes prepared from isocyanate resins and 
polyols many of which are commercially available such as those described 
in GB 2,276,387 A, equivalent to U.S. Pat. No. 5,488,079. 
Such polymeric materials are as described in Saechtling: Kunststoff 
Taschenbuch 23. Ausgabe--published by Carl Hanser Verlag 1986 (esp. p. 
339-410). The contents of this book are incorporated herein by reference. 
Phosphite-HALS compounds (e.g. compounds of formula (X) or (XI)) may be 
incorporated by known methods into the polymeric material to be stabilized 
as described in British Patent Publication No. 2,276,387, equivalent to 
U.S. Pat. No. 5,488,079. 
Phosphite-HALS compounds (e.g. compounds of formula (X) or (XI)) are 
especially suitable for use in polyolefins and especially 
.alpha.-polyolefins prepared using processing catalysts known as 
Generation II to Generation V catalysts and which have not been subjected 
to a catalyst removal step, as described in British Patent Publication No. 
2,276,387, equivalent to U.S. Pat. No. 5,488,079. 
Further, in this specification, where a range is given, the figures 
defining the range are included therein. Further, any group capable of 
being linear or branched is linear or branched unless indicated to the 
contrary. 
For the avoidance of doubt, in this specification t-butyl means tertiary 
butyl, (--C(CH.sub.3).sub.3). 
The contents of British Patent publication No. GB 2,276,387 equivalent to 
U.S. Pat. No. 5,488,079, and U.S. Ser. No. 08/248282 filed on May 23, 
1994, abandoned, are incorporated herein by reference.

The invention will now be illustrated by the following Examples. 
EXAMPLE 1 
Synthesis of 
di(1,2,2,2,6-penta-methyl-piperidin-4-oxy)-(diethylamino)phosphine 
Under inert conditions, 2 moles of 1,2,2,6,6-penta-methyl-piperidin-4-ol 
are mixed with 1 mole of tris(diethylamino)phosphine and heated to 
140.degree. C. over a 6 hour period. During this time, 88% of theory of 
diethylamine are distilled off. The residue is fractionated in vacuum and 
the product distills at 156.degree. C./0.05 Torr and yields 55% of a 
colorless oil which is of 
di(1,2,2,6,6-penta-methyl-piperidin-4-oxy)-(diethylamino)-phosphine: The 
chemical shift of substance in the phosphorus NMR spectra, .delta.(.sup.31 
P), is as follows: .delta.(.sup.31 P)=144.3 ppm. 
EXAMPLE 2 
Synthesis of 
di(2,2,6,6-tetra-methyl-piperidin-4-oxy)-(diethylamino)phosphine 
Under inert conditions 2 moles of 2,2,6,6-tetra-methyl-piperidin-4-ol are 
mixed with 1 mole of tris(diethylamino)phosphine and heated to 140.degree. 
C. over a 6 hour period. During this time, 95% of theory of diethylamine 
is distilled off. The residue is fractionated in vacuum and the product 
distills at 140.degree. C./0.15 Torr and yields 48% of a colorless oil, 
which is di(2,2,6,6-tetra-methyl-piperidin-4-oxy)-(diethylamino)phosphine. 
The chemical shift of substance in the phosphorus NMR spectra is as 
follows: .delta.(.sup.31 P)=144.3 ppm. 
EXAMPLE 3 
Synthesis of 
(2,2,6,6-tetra-methyl-piperidin-4-oxy)-bis(diethylamino)phosphine 
Under inert conditions 1 mole of 2,2,6,6-tetra-methyl-piperidin-4-ol is 
mixed with 1 mole of tris(diethylamino)phosphine and heated to 130.degree. 
C. over a 4 hour period. During this time 97% of theory of diethylamine is 
distilled off. The residue is fractionated in vacuum and the product 
distills at 89-92.degree. C./0.07 Torr and yields 65% of a colorless oil, 
which is 
(2,2,6,6-tetra-methyl-piperidin-4-oxy)-bis(diethylamino)phosphine. The 
chemical shift of substance in the phosphorus NMR spectra is as follows: 
.delta.(.sup.31 P)=131.6 ppm. 
EXAMPLE 4 
Synthesis of 
(1,2,2,6,6-penta-methyl-piperidin-4-oxy)-bis(diethylamino)phosphine 
Under inert conditions 1 mole of 1,2,2,6,6-penta-methyl-piperidin-4-ol is 
mixed with 1 mole of tris(diethylamino)phosphine and heated to 130.degree. 
C. over a 4 hour period. During this time 92% of the calculated amount of 
diethylamine is distilled off. The residue is fractionated in vacuum and 
the product distills at 115.degree. C./0.15 Torr and yields 70% of a 
colorless oil, which is 
(1,2,2,6,6-penta-methyl-piperidin-4-oxy)-bis(diethylamino)phosphine. The 
chemical shift of substance in the phosphorus NMR spectra is as follows: 
.delta.(.sup.31 P)=131.5 ppm. 
EXAMPLE 5 
Synthesis of di(2,2,6.6-tetra-methyl-piperidin-4-yl)-octadec-1-yl-phosphite 
Under inert conditions 0.1 mole of 
di(2,2,6,6-tetra-methyl-piperidin-4-oxy)-(diethylamino)-phosphine is mixed 
with 0.1 mole of octadecan-1-ol and heated to 160.degree. C. over a 6 hour 
period. During this time 76% of theory of diethylamine is distilled off. 
The oily residue is crystallized out by stirring at room temperature with 
acetonitrile. The yield of 
di(2,2,6,6-tetra-methyl-piperidin-4-yl)-octadec-1-yl-phosphite is 66%. The 
chemical shift of substance in the phosphorus NMR spectra is as follows: 
.delta.(.sup.31 P)=138.7 ppm.