Organosilyl radical generators and their applications

Details Organosilyl radical generators and their applications Organosilyl radical generators and their applications

2000-11-30

2002-12-03

McPherson, John A. (Department: 1756)

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, C556S402000, C540S004000, C544S069000, C544S229000, C522S026000, C522S028000, C522S063000, C522S065000, C548S110000, C548S405000, C546S013000

Reexamination Certificate

active

06489081

ABSTRACT:

The present application refers to novel compounds generating organosilyl radicals upon irradiation with light, and to the use of thus generated organosilyl radicals for various chemical reactions such as for example polymerization.
In Acc. Chem. Res. Vol. 25, 188-194 (1992) and Chem. Rev. Vol. 95, 1229-1251 (1995), various applications of organosilyl radicals are disclosed. However, the methods of generating organosilyl radicals are still limited. For instance, organosilyl radicals can be generated by treatment of organosilyl hydride with conventional radical initiators such as for example benzoyl peroxide as described in Chem. Rev. Vol. 95, 1229-1251 (1995), or by photolysis of poly(organosilane)s as is disclosed in Chem. Rev. Vol. 95,1527-1588 (1995).
In technique radicals useful for initiating chemical reactions, especially polymerization reactions, are needed.
Subject of this invention therefore are novel compounds of formula 1, which generate organosilyl radicals by irradiation of light and
R
1
, R
2
, and R
3
independently of one another are hydrogen; C
1
-C
20
alkyl which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, phenylthio, F, Cl, Br, I, CN, (C
1
-C
8
-alkyl)O(CO)—, (C
1
-C
4
alkyl)-(CO)O— or/and di(C
1
-C
4
alkyl)amino; or R
1
, R
2
, and R
3
independently of one another are C
3
-C
6
alkenyl; or are phenyl which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, phenylthio, F, Cl, Br, I, CN, (C
1
-C
8
alkyl)O(CO)—, (C
1
-C
4
alkyl)-(CO)O— or/and di(C
1
-C
4
alkyl)amino; or R
1
and R
2
together are C
2
-C
9
alkylene, o-xylylene, 2-butenylene, C
3
-C
9
oxaalkylene or C
3
-C
9
azaalkylene;
R
4
, R
5
, R
6
, and R
7
independently of one another are sec-C
3
-C
20
alkyl, tert-C
4
-
20
alky or phenyl wherein these radicals are unsubstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, phenylthio, F, Cl, Br, I, CN, (C
1
-C
8
alkyl)O(CO)—, (C
1
-C
4
alkyl)-(CO)O— or/and di(C
1
-C
4
alkyl)amino;
or R
4
and R
5
, and/or R
6
and R
7
together are C
2
-C
9
alkylene, o-xylylene, 2-butenylene, C
3
-C
9
oxaalkylene or C
3
-C
9
azaalkylene, or R
4
and R
6
, and/or R
5
and R
7
together are branched C
2
-C
9
alkylene, o-xylylene, 2-butenylene, C
3
-C
9
oxaalkylene or C
3
-C
9
azaalkylene.
C
1
-C
20
alkyl is linear or branched and is, for example, C
1
-C
18
—, C
1
-C
14
—, C
1
-C
12
—, C
1
-C
8
—, C
1
-C
6
— or C
1
-C
4
alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertbutyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl.
sec-C
3
-C
20
alkyl is branched C
3
-C
20
alkyl, for example, isopropyl, sec-butyl.
tert-C
3
-C
20
alkyl is branched C
3
-C
20
alkyl, for example, tert-butyl, tert-amyl.
C
2
-C
9
alkylene is linear or branched alkylene, for example C
2
-C
7
alkylene, C
2
-C
6
alkylene, C
2
-C
4
alkylene, namely, ethylene, propylene, 1-methylethylene 1,1-dimethyl-ethylene, 2,2-dimethylpropylene, butylene, 1-methylbutylene, 1-methylpropylene, 2-methyl-propylene, pentylene, hexylene, heptylene, octylene, or nonylene.
C
3
-C
9
oxaalkylene is linear or branched C
3
-C
9
alkylene, having a meaning as defined above and being interrupted by one or more, e.g. 1-6, 1-5, 1-4 or 1, 2, or 3, non-successive O atoms. C
3
-C
9
oxaalkylene for example, produces structural units such as —CH
2
CH
2
—O—CH
2
—, —CH
2
CH
2
—O—CH
2
CH
2
—, —[CH
2
CH
2
O]
y
—, —[CH
2
CH
2
O]
y
—CH
2
—, where y=1-4, —(CH
2
CH
2
O)
3
CH
2
CH
2
—, —CH
2
—CH(CH
3
)—O—CH
2
—CH(CH
3
)— or —CH
2
—CH(CH
3
)—O—CH
2
—CH
2
CH
2
—.
C
3
-C
9
azaalkylene is linear or branched C
3
-C
9
alkylene as described above, which is interrupted by one or more, e.g. 1-6, 1-5, 1-4 or 1, 2, or 3 N-atoms. C
3
-C
9
azaalkylene produces, for example, structural units such as —CH
2
CH
2
—NH—CH
2
—, —CH
2
CH
2
—N(CH
3
)—CH
2
—, —CH
2
CH
2
—NH—CH
2
CH
2
—, —CH
2
CH
2
—N(CH
3
)—CH
2
CH
2
—, —[CH
2
CH
2
NH]
y
—, —[CH
2
CH
2
O]
y
—CH
2
—, where y=1-4, —[CH
2
CH
2
N(CH
3
)]
3
—, —(CH
2
CH
2
NH)
3
CH
2
CH
2
—, —CH
2
—CH
2
—CH(CH
3
)—NH—CH
2
—CH(CH
3
)—, —CH
2
CH(CH
3
)—N(CH
3
)—CH
2
—CH(CH
3
)— or —CH
2
—CH(CH
3
)—NH—CH
2
—CH
2
CH
2
—.
C
3
-C
6
alkenyl, for example C
3
-C
5
alkenyl, radicals are mono- or polyunsaturated and are linear or branched. Examples are allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, or 5-hexenyl, especially allyl. C
1
-C
4
alkoxy is linear or branched, namely, methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, preferably methoxy.
C
1
-C
4
alkylthio is linear or branched, namely, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, preferably methylthio or butylthio.
Substituted phenyl is substituted one to five times, for example once, twice or three times, especially once or twice. Substituents are, for example in position 2, 3, 4, 5 or 6, especially in position 2, 6 or 3 of the phenyl ring.
The terms “and/or” or “or/and” in the present context are meant to express that not only one of the defined alternatives (substituents) may be present, but also several of the defined alternatives (substituents) together, namely mixtures of different alternatives (substituents).
The term “at least” is meant to define “one” or “more than one”, for example one or two or three, preferably one or two.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The present compounds of formula I are prepared in general by treatment of a metallated organosilyl compound (II) with a corresponding halogenoborane (III) in an appropriate solvent such as tetrahydrofuran and n-hexane:
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
are as defined above. X is chloro or bromo, M is an alkali metal, preferably Li.
The reaction is carried out in a suitable solvent, e.g. an ether, such as tetrahydrofurane (THF) or an aliphatic hydrocarbon, such as n-hexane. For example, other aprotic solvents such as petrol ethers and aromatic hydrocarbons as well as dialkyl ethers are suitable for this reaction, too.
Usually the reaction is conducted using the educt in a molar ratio of 1:1.
The organosilyl lithium usually is prepared from lithium metal and organosilyl halide in an appropriate solvent, e.g. THF (ca. 1 mol/l). The organosilyl borane is prepared by dropwise addition of the organosilyl lithium to the halogenoborane in an appropriate solvent, e.g. n-hexane or THF (ca. 1 mol/l).
The person skilled in the art is aware of convenient reaction temperatures. The temperatures usually depend on the solvent used and generally range between 0° C. and ambient temperature.
Preparation examples of organosilyl borane educts, as used for the synthesis of the compounds according to the invention, are described in Organometallics 1995, 14, 3112-3115. The preparation of halogenoboranes is, for example described in J. Organomet. Chem. 1993, 455, 37-46.
Preference is given to the compounds of formula I, wherein R
1
, R
2
, and R
3
independently of one another are C
1
-C
20
alkyl which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, phenylthio, F, Cl, Br, I, CN, (C
1
-C
8
alkyl)O(CO)—, (C
1
-C
4
alkyl)-(CO)O— or/and di(C
1
-C
4
alkyl)amino, or R
1
, R
2
, and R
3
independently of one another are C
3
-C
6
alkenyl, or phenyl which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, phenylthio, F, Cl, Br, I, CN, (C
1
-C
8
alkyl)O(CO)—, (C
1
C
4
alkyl)-(CO)O— or di(C
1
-C
4
alkyl)amino.
In preferred compounds of formula I R
4
, R
5
, R
6
, and R
7
independently of one another are sec-C
3
-C
20
alkyl which is un

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