Phenyl alkyl ketone substituted by cyclic amine and a...

Details Phenyl alkyl ketone substituted by cyclic amine and a... Phenyl alkyl ketone substituted by cyclic amine and a...

1999-06-10

2001-02-20

Berman, Susan W. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C522S034000, C522S063000, C522S065000, C540S611000, C544S078000, C544S087000, C544S106000, C544S162000, C544S175000, C544S392000, C544S395000, C546S194000, C546S237000, C564S342000, C564S336000, C564S343000, C568S306000, C568S309000

Reexamination Certificate

active

06191182

ABSTRACT:

The present invention relates to novel phenyl alkyl ketones which are substituted by cyclic amine, to a novel process for the preparation thereof, to their use for the preparation of photoinitiators for the photopolymerisation of ethylenically unsaturated compounds, as well as to a photopolymerisable composition comprising such photoinitiators.
EP-B-0284 561 discloses &agr;-aminoacetophenones which are used as photoinitiators. These compounds are prepared by a series of process steps which, in the case of aromatic amines, always start from a derivative of a p-fluorophenylalkylen-1-one, the fluoro in p-position being replaced with an amino group in the final step of the synthesis. This replacement is carried out in an organic solvent, such as dimethylformamide or dimethylsulfoxide, in the presence of potassium carbonate.
One aim of the invention was, inter alia, to develop, on the one hand, reactions which avoid the use of fluoroaromates because these are ecologically problematical, require undesirable waste disposal and because, owing to their relatively high reactivity, they are susceptible to amines and, on the other hand, to get away from organic solvents because working in those results in more or less dark-coloured products with by-products, i.e. in less pure products and lower yields.
The processes known from the literature wherein, in a phenyl alkyl ketone containing halogen in p-position, the halogen in the phenyl nucleus, in particular fluoro or chloro, is replaced with an amine radical, are carried out:
a) in an organic solvent (e.g. EP-B-0138754, reaction of 1-(4-fluorophenyl)-2-methyl-propan-1-one with piperidine in dimethylsulfoxide; CH 200 365, reaction of p-chlorostearophenone with dimethylamine in ethanol in the presence of copper powder as catalyst; T. Ibata, Y. isogami, J. Toyoda, Bull. Chem. Soc. Jpn. 64(1)42-49 (1991), reaction of chloroacetophenone with pyrrolidine in tetrahydrofuran using extremely high pressures (7,2 kbar); J. Org. Chem. 31(7), 2319-21 (1966), reaction of 1-(4-fluorophenyl)propan-1-one with alicyclic amines, such as piperidine, in dimethylformamide or dimethylsulfoxide, or
b) without solvents (e.g. B. G. Kresze and H. Goetz, Chem. Berichte 90, 2161, 2174 (1957)), reaction of p-bromoacetophenone with piperidine under reflux with 19% yields of 1-(4-piperidinophenyl)ethanone; or
c) in water (e.g.: T. Lundstedt, P. Thoren, R. Carlson, Acta Chemica Scand. B 38, 1984 No. 8 S. 717-719; reaction of p-chloroacetophenone with dimethylamine under pressure in water; U.S. Pat. No. 1,946,058, reaction of p-chloroacetophenone with aqueous ammonia in water under pressure in the presence of copper oxide as catalyst; JP 78-40404, reaction of p-chloroacetophenone with mono- or dialkylamines in water under pressure and in the presence of copper powder as catalyst) where, on the one hand, explosions occurred and, on the other hand, the yields are less than 80%.
Surprisingly, it has now been found that under specific conditions a reaction of p-halophenyl alkyl ketones, in particular of the corresponding p-bromo compounds and p-chloro compounds with amines, especially cyclic amines, in water proceeds very selectively and well, giving high yields.
Only few of such phenyl alkyl ketones, which are substituted in p-position in the phenyl nucleus by a cyclic amine and which additionally have a free methylene group in &agr;-position to the keto group, are known; reference is made to, inter alia, EP-B-0 138 754 (2-methyl-1(4-piperidinophenyl)propan-1-one); CH 200365 (p-dimethylaminostearophone, where the dimethylamino radical according to the description may also be replaced with piperidine without, however, any concrete example being given); G. Kresze and H. Goetz, Chem. Berichte 90, 2161, 2174 (1957), (1-(4-piperidinophenyl)ethanone); T. Ibata, Y. Isogami, J. Toyoda, Bull. Chem. Soc. JPn. 64(1), 42-49 (1991), (1-(4-pyrrolidone) aceto-phenone); and J. Org. Chem. 31(7), 2319-21 (1966), (1-(4-piperidinophenyl)propan-1-one).
The invention, and at the same time the solution to the given problem, relates to novel phenyl alkyl ketones substituted by cyclic amine in p-position, which may be used, inter alia, as novel intermediates for the preparation of specific photoinitiators, as well as to a novel process for the preparation of these intermediates.
The novel phenyl alkyl ketones p-substituted by cyclic amine are compounds of formula (I)
wherein:
R
1
and R
2
together are straight-chain or branched, unsubstituted or substituted C
3
-C
20
-alkylene which may be interrupted by one or more than one —O—, —S— or —N(R
4
) group, R
3
is straight-chain or branched, unsubstituted or substituted C
2
-C
20
alkyl, and R
4
is hydrogen, straight-chain or branched C
1
-C
3
alkyl, straight-chain or branched C
3
-C
5
-alkenyl, C
7
-C
9
-phenylalkyl, C
1
-C
4
-hydroxyalkyl or phenyl where, if R
1
and R
2
together unsubstituted tetramethylene, R
3
is unsubstituted C
6
alkyl.
If R
1
and R
2
together are a C
3
-C
20
alkylene radical, said radical is, owing to the linking N-atom, a heterocyclic ring system. This N-heterocyclic ring system may be interrupted by one or more than one additional hetero atom, such as an —O—, —S— and/or —N(R
4
) group, and it can additionally be substituted once or several times.
Suitable C
3
-C
20
alkylene radicals are straight-chain as well as branched alkylene radicals, and substituents may be e.g. hydroxy, C
1
-C
4
alkoxy, hydroxymethyl, C
1-C
4
alkoxymethyl, —COO(C
1
-C
4
alkyl) or also phenyl.
Straight-chain or branched C
3
-C
20
alkylene radicals are typically tri-, tetra-, penta-, hexa-, hepta-, octa-, deca-, dodeca- or octadecamethylene, and 2,2-dimethyltrimethylene or 1,3,3-trimethyltetramethylene.
C
3
-C
20
Alkylene which is interrupted by oxygen, sulfur or —N(R
4
)- can be interrupted once or several times and is typically:
—CH
2
—CH
2
—O—CH
2
—CH
2
—, —CH
2
—CH(CH
3
)—O—CH(CH
3
)—CH
2
—, —CH
2
—CH
2
—(O—CH
2
—CH
2
—)
2
—O—CH
2
—CH
2
—, —CH
2
—CH
2
—(O—CH
2
—CH
2
—)
3
—O—CH
2
—CH
2—, —CH
2
—CH
2
—(O—CH
2
—CH
2
—)
4
—O—CH
2
—CH
2
—, —CH
2
—CH
2
—O—CH
2
—CH
2
—, —CH
2
—CH
2
—(O—CH
2
—CH
2
—)
2
—NH—CH
2
—CH
2
—O—CH
2
—CH
2
—, —CH
2
—CH
2
—(O—CH
2
—CH
2
—)
2
—NH—(CH
2
—CH
2
—O—)
2
—CH
2
—CH
2
—, —CH
2
—CH
2
—S—CH
2
—CH
2
—, —CH
2
—CH
2
—NH—CH
2
—CH
2
—, —CH
2
—CH
2
—N(CH
3
)—CH
2
—CH
2
—, —CH(CH
3
)—CH
2
—NH—CH(CH
3
)—CH
2
—, —CH
2
—CH
2
—NH—CH
2
—CH
2
—NH—CH
2
—CH
2
—, —CH
2
—CH
2
—CH
2
—NH—CH
2
—CH
2
—CH
2
—NH—CH
2
—CH
2
—CH
2
—, —CH
2
—CH
2
—(NH—CH
2
—CH
2
—)
2
—NH—CH
2
—CH
2
—, —CH
2
—CH
2
—(NH—CH
2
—CH
2
—)
4
—NH—CH
2
—CH
2
—, —CH
2
—CH
2
—NH—CH
2
—CH
2
—CH
2
—NH—CH
2
—CH
2
—NH—CH
2
—CH
2
—CH
2
— or —CH
2
—CH
2
—CH
2
—NH—CH
2
—CH
2
—CH
2
—NH—CH
2
—CH
2
—NH—CH
2
—CH
2
—CH
2
—.
R
1
and R
2
, together with the linking N-atom, are typically the following heterocyclic radicals:
A 6-ring system heterocyclic radical may not be substituted in 6-position.
A 6-ring system is preferred, in particular morpholino.
R
3
defined as unsubstituted or substituted C
2
-C
20
alkyl radical may also be straight-chain or branched. Illustrative examples thereof are the following alkyl radicals:
ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, isopropyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, isodecyl, 1-methylundecyl or 1,1,3,3,5,5-hexamethylhexyl.
These C
2
-C
20
alkyl radicals may additionally be substituted once or several times, e.g. by cyclohexyl, phenyl, C
1
-C
4
alkoxy or phenoxy.
In this case, the R
3
radicals are typically: 2-methoxyethyl, 3-butoxypropyl, 2-isopropoxyethyl, 4-phenoxybutyl, 2-phenylethyl or 3-phenylpropyl.
Particularly preferred alkyl radicals R
3
are unsubstituted, straight-chain or branched alkyl radicals having 2 to 10 carbon atoms, preferably those having 2 to 7 carbon atoms, particularly preferably those

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