Organometallic monoacylarylphosphines

Details Organometallic monoacylarylphosphines Organometallic monoacylarylphosphines

2001-10-22

2003-06-17

Ashton, Rosemary (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Imaging affecting physical property of radiation sensitive...

Radiation sensitive composition or product or process of making

C430S325000, C430S923000, C522S018000, C522S064000

Reexamination Certificate

active

06579663

ABSTRACT:

The present application relates to organometallic monoacylarylphosphines, to the preparation thereof, and to the use thereof as starting materials for the preparation of acylphosphines, acylphosphine oxides or acylphosphine sulfides.
Various metalated phosphines have become known as intermediates in the preparation of acylphosphine oxides. Thus, for example, in EP 40721, acylphosphines are obtained by reaction of acyl halides with metalated diorganophosphines or silylated phosphines or diorganophosphines.
By oxidation of the acyldiorganophosphines, the corresponding acylphosphine oxide photoinitiators can be prepared therefrom. Swiss Patent Application No 2376/98 discloses a one-pot process for the preparation of bisacylphosphine oxides in which dichloroorganophosphines are metalated, then reacted with acyl halides to give the corresponding acylphosphines and then, by oxidation or sulfurization, the bisacylphosphine oxides or bisacylphosphine sulfides are obtained.
Arylacylphosphines and the corresponding metalated compounds are not known in the prior art.
U.S. Pat. No. 5,399,770 discloses a bisacylphosphine oxide having two different acyl groups, and U.S. Pat. No. 5,218,009 specifically discloses a monoacylphosphine oxide having two different non-acyl substituents on the phosphorus atom.
For the technology, readily accessible starting materials for the preparation of acylphosphine oxides and acylphosphine sulfides are of great importance. Of particular interest are starting materials which permit the preparation of “unsymmetrical” bisacylphosphine oxides and bisacylphosphine sulfides, i.e. those with two different acyl groups, in a simple manner.
A process for the preparation of metalated arylacylphosphines which are suitable as starting materials for the preparation of acylphosphine oxide or acylphosphine sulfide photoinitiators has been found. The phosphines, phosphine oxides and phosphine sulfides obtained are novel.
The invention provides compounds of the formula I
in which
Ar is a group
or Ar is cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthracyl or an O—, S— or N-containing 5- or 6-membered heterocyclic ring, where the radicals cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthracyl or O—, S— or N-containing 5- or 6-membered heterocyclic ring are unsubstituted or substituted by halogen, C
1
-C
4
alkyl and/or C
1
-C
4
alkoxy;
R
1
and R
2
independently of one another are C
1
-C
20
alkyl, OR
11
, CF
3
or halogen;
R
3
, R
4
and R
5
independently of one another are hydrogen, C
1
-C
20
alkyl, OR
11
or halogen; or in each case two of the radicals R
1
, R
2
, R
3
, R
4
and/or R
5
together form C
1
-C
20
alkylene, which can be interrupted by O, S or NR
14
;
R
6
, R
7
, R
8
, R
9
and R
10
independently of one another are hydrogen, C
1
-C
20
alkyl; C
2
-C
20
alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; or R
6
, R
7
, R
8
, R
9
and R
10
OR
11
, phenyl or halogen;
R
11
is hydrogen, C
1
-C
20
alkyl, C
2
-C
20
alkenyl, C
3
-C
8
cycloalkyl, phenyl, benzyl or C
2
-C
20
alkyl which is interrupted once or more than once by O or S and which is unsubstituted or is substituted by OH and/or SH;
R
14
is hydrogen, phenyl, C
1
-C
12
alkyl or C
2
-C
12
alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; and
M is hydrogen, Li, Na or K.
C
1
-C
24
alkyl is linear or branched and is, for example, C
2
-C
24
alkyl, C
1
-C
20
alkyl, C
1
-C
18
alkyl, C
1
-C
12
alkyl, C
1
-C
8
alkyl, C
1
-C
6
alkyl or C
1
-C
4
alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl or tetraicosyl.
For example, R
1
, R
2
, R
3
, R
1
′, R
2
′ and R
3
′ are C
1
-C
8
alkyl, in particular C
1
-C
6
alkyl, preferably C
1
-C
4
alkyl, particularly preferably methyl.
C
1
-C
20
alkyl, C
1
-C
18
alkyl, C
1
-C
12
alkyl, C
1
-C
6
alkyl and C
1
-C
4
alkyl are likewise linear or branched and have, for example, the meanings given above apart from the corresponding number of carbon atoms.
R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
, R
13
, R
19
, R
20
, R
21
, R
22
and R
23
are, for example C
1
-C
8
alkyl, in particular C
1
-C
6
alkyl, preferably C
1
-C
4
alkyl, for example methyl or butyl.
C
2
-C
24
alkyl which is interrupted once or more than once by O, S or NR
14
is, for example, interrupted 1-9 times, e.g. 1-7 times or once or twice, by O, S or NR
14
. If the radicals are interrupted by two or more O, S or NR
14
, then the O atoms, S atoms or NR
14
groups are in each case separated from one another by at least one methylene group. The O atoms, S atoms or NR
14
groups are thus not directly consecutive. The alkyl radical can be linear or branched. For example, structural units such as —CH
2
—O—CH
3
, —CH
2
CH
2
—O—CH
2
CH
3
, —[CH
2
CH
2
O]
z
—CH
3
, where z=1 to 9, —(CH
2
CH
2
O)
7
CH
2
CH
3
, —CH
2
—CH(CH
3
)—O—CH
2
—CH
2
CH
3
, —CH
2
—CH(CH
3
)—O—CH
2
—CH
3
, —CH
2
SCH
3
or —CH
2
—N(CH
3
)
2
arise.
C
2
-C
20
alkyl, C
2
-C
18
alkyl, C
2
-C
12
alkyl which are interrupted by O and optionally by S are likewise linear or branched and can, for example, have the meanings given above apart from the given number of carbon atoms. Here too, the O atoms are not consecutive.
C
1
-C
18
haloalkyl is C
1
-C
18
alkyl as described above which is mono- or polysubstituted by halogen. This is, for example, perfluorinated C
1
-C
18
alkyl. Examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, in particular trifluoromethyl or trichloromethyl.
C
3
-C
24
cycloalkyl, e.g. C
5
-C
12
cycloalkyl, C
3
-C
12
cycloalkyl, C
3
-C
8
cycloalkyl, stands both for individual alkyl ring systems and also bridged alkyl ring systems. Furthermore, the radicals can also contain linear or branched alkyl groups (as described above apart from the corresponding number of carbon atoms). Examples are cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloicosyl, adamantyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl. Further examples are
C
3
-C
8
cycloalkyl, e.g. C
3
-C
6
cycloalkyl, can have the meanings given above apart from the corresponding number of carbon atoms.
C
3
-C
18
cycloalkyl substituted by C
1
-C
20
alkyl, OR
11
, CF
3
or halogen is preferably tri- or disubstituted in the 2,4,6- or 2,6-positions respectively, of the cycloalkyl ring. Preference is given to 2,4,6-trimethylcyclohexyl and 2,6-dimethoxycyclohexyl.
C
2
-C
24
alkenyl radicals are mono- or polyunsaturated, and are linear or branched and are, for example, C
2
-C
18
alkenyl, C
2
-C
8
alkenyl, C
2
-C
6
alkenyl or C
2
-C
4
alkenyl. Examples are vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl or dodecenyl, in particular allyl. C
2
-C
18
alkenyl has the same meanings as given above apart from the corresponding number of carbon atoms.
If C
2
-C
24
alkenyl radicals are interrupted, for example, by O, then the following structures are, for example, included: —(CH
2
)
y
—O—(CH
2
)
x
—CH═CH
2
, —(CH
2
)
y
—O—(CH
2
)
x
—C(CH
3
)═CH
2
or —(CH
2
)
y
—O—CH═CH
2
, where x and y independently of one another are a number from 1 to 21.
C
3
-C
24
cycloalkenyl, e.g. C
5
-C
12
cycloalkenyl, C
3
-C
12
cycloalkenyl, C
3
-C
8
cycloalkenyl, stands both for individual alkyl ring systems and also bridged alkyl ring systems and can be mono- or polyunsaturated, e.g. mono- or diunsaturated. Furthermore, the radicals can also contain linear or branched alkyl groups (as described above apart from the corresponding number of carbon atoms). Examples are cyclopropenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclododecenyl, cycloicosenyl, in particular cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.
C
6
-C
14
aryl is, for example, C
6
-C
10
aryl. Examples are phe

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