Organometallic monoacylalkylphosphines

Details Organometallic monoacylalkylphosphines Organometallic monoacylalkylphosphines

2001-05-31

2004-05-18

Berman, Susan (Department: 1711)

Organic compounds -- part of the class 532-570 series

Organic compounds

Phosphorus containing

C568S015000, C522S064000

Reexamination Certificate

active

06737549

ABSTRACT:

The present application relates to organometallic monoacylalkylphosphines, to the preparation thereof, and to the use thereof as starting materials for the preparation of unsymmetrical mono- and bisacylphosphines, -phosphine oxides or sulfides.
Various metalated phosphines have become known as intermediates in the preparation of a-cylphosphine 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. WO 00/32612 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 sulfides are obtained.
Alkylacylphosphines and the corresponding metalated compounds are not known in the prior
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 sulfides are of great importance. Of particular interest are starting materials which permit the preparation of “unsymmetrical” bisacylphosphine oxides and sulfides, i.e. those with two different acyl groups, in a simple manner.
A process for the preparation of metalated alkylacylphosphines which are suitable as starting materials for the preparation of acylphosphine oxide or acylphosphine sulfide photoinitiators has been found. The majority of 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, anthracyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the radicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 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 R
5
together form C
1
-C
20
alkylene, which can be interrupted by O, S or NR
14
;
R
6
is C
1
-C
24
alkyl, unsubstituted or substituted by cycloalkenyl, phenyl, CN, C(O)R
11
, C(O)OR
11
, C(O)N(R
14
)
2
, OC(O)R
11
, OC(O)OR
11
, N(R
14
)C(O)N(R
14
), OC(O)NR
14
, N(R
14
)C(O)OR
11
, cycloalkyl, halogen, OR
11
, SR
11
, N(R
12
)(R
13
) or
C
2
-C
24
alkyl which is interrupted once or more than once by nonconsecutive O, S or NR
14
and which is unsubstituted or substituted by phenyl, OR
11
, SR
11
, N(R
12
)(R
13
), CN, C(O)R
11
, C(O)OR
11
, C(O)N(R
14
)
2
and/or
C
2
-C
24
alkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NR
14
and which is unsubstituted or substituted by OR
11
, SR
11
or N(R
12
)(R
13
);
C
5
-C
24
cycloalkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NR
14
and which is unsubstituted or substituted by OR
11
, SR
11
or N(R
12
)(R
13
);
C
7
-C
24
arylalkyl which is unsubstituted or substituted on the aryl group by C
1
-C
12
alkyl, C
1
-C
12
alkoxy or halogen;
C
4
-C
24
cycloalkyl which is uninterrupted or interrupted once or more than once by O, S and/or NR
14
and which is unsubstituted or substituted by OR
11
, SR
11
or N(R
12
)(R
13
);
or C
8
-C
24
arylcycloalkyl or C
8
-C
24
arylcycloalkenyl;
R
11
is H, 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
12
and R
13
independently of one another are hydrogen, C
1
-C
20
alkyl, C
3
-C
8
cycloalkyl, phenyl, benzyl or 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
12
and R
13
together are C
3
-C
5
alkylene which is uninterrupted or interrupted by O, S or NR
14
;
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], —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. The O atoms are not consecutive here either.
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
4
-C
24
cycloalkyl, C
5
-C
12
cycloalkyl, C
4
-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, 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 substituted in both ortho positions 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
alkeny

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