Compositions: coating or plastic – Materials or ingredients – Pigment – filler – or aggregate compositions – e.g. – stone,...
Reexamination Certificate
2000-02-09
2001-06-19
Green, Anthony (Department: 1755)
Compositions: coating or plastic
Materials or ingredients
Pigment, filler, or aggregate compositions, e.g., stone,...
C106S495000, C106S497000, C106S498000, C546S049000, C548S453000
Reexamination Certificate
active
06248165
ABSTRACT:
The present invention relates to novel single-phase mixed crystals, also known as solid compounds, and solid solutions of two different symmetrical 1,4-diketopyrrolopyrroles and to the use thereof as pigments. The present invention further relates to single-phase ternary solid solutions which contain at least two different symmetrical 1,4-diketopyrrolopyrroles and a third component which is a quinacridone or a third 1,4-diketopyrrolopyrrole.
1,4-Diketopyrrolopyrroles, including symmetrical and asymmetrical 1,4-diketopyrrolopyrroles, i.e. of the
wherein A and B are aryl groups, their preparation and the use thereof as pigments are disclosed, inter alia, in U.S. Pat. No. 4,579,949. U.S. Pat. No. 4,778,899 discloses a process for the preparation of pure asymmetrical 1,4-diketopyrrolopyrroles. This process consists of an elaborate synthesis which is carried out via the stage of special amino esters or pyrrolinones.
U.S. Pat. No. 4,783,540 furthermore discloses that solid solutions can be obtained by mixing two different 1,4-diketopyrrolopyrroles, preferably in the ratio of 65-90:10-35% by weight, and carrying out subsequent treatment such as kneading, grinding or precipitating. Solid solutions containing a diketopyrrolopyrrol-type pigment and a pigment of another class, for example, a quinacridone or quinacridonequinone, are described in U.S. Pat. No. 4,810,304. The disclosed solid solutions are characterized by their X-ray diffraction patterns, the X-ray diffraction patterns of the solid solutions being different from the sum of the X-ray diffraction patterns of the single components.
It has now been found that mixtures of two different symmetrical 1,4-diketopyrrolopyrroles of formulae
in a molar ratio of 1:1, form novel mixed crystals which, very surprisingly, are isomorphous with the crystals of the corresponding asymmetrical 1,4diketopyrrolopyrroles of the
These products are single-phase products whose X-ray diffraction pattern differs from that of the single components of the mixed crystal and also from that of their physical mixture. The X-ray diffraction pattern of the mixed crystal and that of the asymmetrical single component is, however, virtually identical.
Accordingly, the invention relates to mixed crystals of 1,4-diketopyrrolo[3,4-c]pyrroles, consisting of two different compounds of formulae
in a molar ratio of 1:1, wherein A and B, which must be different, are each a group of formula
wherein
R
1
and R
2
are each independently of the other hydrogen, halogen, C
1
-C
18
alkyl,
C
1
-C
18
alkoxy, C
1
-C
18
alkylmercapto, C
1
-C
18
alkylamino, C
1
-C
18
alkoxycarbonyl,
C
1
-C
18
alkylaminocarbonyl, -CN, —NO
2
, trifluoromethyl, C
5
-C
6
cycloalky,
C═N—(C
1
-C
18
alkyl), phenyl,
imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl,
G is —CH
2
—, —CH(CH
3
)—, —C(CH
3
)
2
—, —CH═N—, —N═N—, —O—, —S—, —SO—, —SO
2
—, —CONH— or —NR
7
—,
R
3
and R
4
are each independently of the other hydrogen, halogen, C
1
-C
6
alkyl,
C
1
-C
18
alkoxy or —CN, R
5
and R
6
are each independently of the other hydrogen, halogen or
C
1
-C
6
alkyl, and R
7
is hydrogen or C
1
-C
6
alkyl, with the proviso that, if one of the radicals
A and B is phenyl, then the other cannot be p-chlorophenyl.
Substitutents defined as halogen are typically iodo, fluoro, preferably bromo and, most preferably, chloro;
C
1
-C
6
alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, hexyl, and C
1
-C
18
alkyl is in addition typically heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.
C
1
-C
18
Alkoxy is, also in C
1
-C
18
alkoxycarbonyl, typically methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, hexyloxy, decyloxy, dodecyloxy, hexadecyloxy or octadecyloxy.
C
1
-C
18
Alkylmercapto is, for example, methylmercapto, ethylmercapto, propylmercapto, butylmercapto, octylmercapto, decylmercapto, hexadecylmercapto or octadecylmercapto.
C
1
-C
18
Alkylamino is, also in C
1
-C
18
alkylaminocarbonyl, typically methylamino, ethylamino, propylamino, hexylamino, decylamino, hexadecylamino or octadecylamino.
C
5
-C
6
Cycloalkyl is typically cyclopentyl and, preferably, cyclohexyl.
Of particular interest are those novel mixed crystals wherein A and B in formulae I and II are each a group of formula
wherein
R
1
and R
2
are each independently of the other hydrogen, chloro, bromo,
C
1
-C
4
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylamino, phenyl or CN,
G is —O—, —NR
7
—, —N═N— or —SO
2
—,
R
3
and R
4
are hydrogen, and R
7
is hydrogen, methyl or ethyl,
and more particularly those mixed crystals wherein A and B in formulae I and II are each a group of formula
wherein R
1
and R
2
are each independently of the other hydrogen, methyl, tert-butyl, chloro, bromo or CN. At least one of R
1
and R
2
is preferably hydrogen.
The novel mixed crystals may be prepared starting from physical mixtures of the above defined components of formulae I and II in general accordance with the following per se known processes:
by contacting in polar organic solvents, preferably by stirring the component mixture at reflux temperature,
by alkaline precipitation of the component mixture from polar organic solvents, such as DMSO, or by stirring the component mixture in polar organic solvents in the presence of alkali metal alcoholates, alkali metal hydroxides or quaternary ammonium compounds, or
by acid precipitation, for example, by dissolving the component mixture in acid and precipitating the solid solution by dilution with water,
by grinding methods, for example, by grinding the component mixture in a ball mill in the presence of grinding media, separating the component mixture from the grinding media, and subsequently subjecting the powder to a crystal growth step, for example, by stirring the component mixture in dilute acid, such as 2% sulfuric acid.
by preparing a premilled powder of the component mixture and subsequently subjecting the premilled powder to a ripening step using an organic solvent or an aqueous media, preferably in the presence of a surfactant.
which processes may be carried out in general accordance with the processes disclosed in detail, inter alia, in U.S. Pat. No. 4,783,540.
A novel method of preparation is that wherein the compounds of formulae I and II, including also those wherein A and B are each independently of the other phenyl and p-chlorophenyl, are reacted by per se known methods with a dicarbonate of formula
D—O−D (III),
or with a trihaloacetate of formula
(R
8
)
3
C—D (IV),
or with an azide of formula
DN
3
(V),
or with a carbonate of formula
D—OR
9
(VI),
or with an alkylidene-iminooxyfoimate of formula
wherein D is a group of formula
R
8
is chloro, fluoro or bromo, R
9
is C
1
-C
4
alkyl or phenyl which is unsubstituted or substituted by halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or —CN, RIO is —CN or —COOR
9
, and R
11
, is phenyl which is unsubstituted or substituted by halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or —CN, R
12
, R
13
and R
14
are each independently of one another hydrogen, C
1
-C
6
alkyl or C
2
-C
5
alkenyl, and at least two of R
12
, R
13
and R
14
must be alkyl or alkenyl, in the molar ratio of 1:2 in an aprotic organic solvent in the presence of a base as catalyst, to soluble compounds of formulae
and these compounds are either
a) mixed homogeneously in powdered form by generally known methods in the molar ratio of 1:1, or
b) mixed homogeneously in powdered form by generally known methods in the molar ratio of 1:1 and the mixture is dissolved in a solvent, or
c) first dissolved and then mixed in solution in the mixture ratio of 1:1,
and subsequently
the desired mixed crystal is precipitated from the dry or dissolved mixture by thermal, photolytic or chemical treatment.
R
12
, R
13
and R
14
defined as C
2
—C
5
alkenyl are typically vinyl, allyl, methallyl, n-but-2-enyl, 2-methyl-prop-2-enyl or n-pent-2-enyl.
R
12
and R
1
Babler Fridolin
Hao Zhimin
Hendi Shivakumar Basalingappa
Iqbal Abul
Ciba Specialty Chemicals Corporation
Crichton David R.
Green Anthony
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