Symmetrical triazine derivatives

Details Symmetrical triazine derivatives Symmetrical triazine derivatives

1999-05-17

2001-04-17

Jones, Dameron L. (Department: 1619)

Drug, bio-affecting and body treating compositions

Live hair or scalp treating compositions

Uv protectant

C544S003000, C544S187000, C544S190000, C424S070100, C424S401000

Reexamination Certificate

active

06217856

ABSTRACT:

The present invention relates to symmetrical triazine derivatives, to the preparation of these compounds as well as to their use for protecting organic materials from the harmful effects of UV radiation.
O-alkylated o-hydroxyphenyltriazines (HPT) containing at least one o-hydroxyl group or at least two alkoxyphenyl substituents are known, e.g. from EP-A-0,743,309, as cosmetic UV absorbers having good spectral properties and good technical application properties. However, the preparation of such triazine derivatives, which are derived from the unsymmetrical basic structure
requires multistep synthesis processes.
In the above formula, R
a
and R
b
are a reactive radical, in particular a phenyl radical which is mono- or polysubstituted by hydroxyl groups.
Symmetrical triazine compounds which may be prepared from the symmetrical basic structure
are easier to access in simple one-bach processes.
Such “triazine basic structures” may be prepared, for example, by trimerising corresponding benzonitrile compounds or, starting from cyanuric chloride, by Grignard reaction or Friedel-Crafts alkylation. Subsequent etherification of the free OH groups makes it possible to prepare the desired triazine derivatives may be prepared in a two-step reaction.
Accordingly, this invention relates to symmetrical triazine derivatives of formula
wherein
R
1
and R
2
are each independently of the other hydrogen; C
1
-C
12
alkyl; or C
1
-C
12
alkoxy; and R
3
is C
1
-C
12
alkyl; or C
1
-C
12
alkoxy.
C
1
-C
12
Alkyl or C
1
-C
12
alkoxy are straight-chain or branched alkyl radicals, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl or dodecyl, or methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy or dodecyloxy.
Particularly preferred compounds are those of formula (1), wherein
R
3
is C
1
-C
12
alkoxy, in particular C
5
-C
12
alkoxy; and
R
1
and R
2
have the meaning given in formula (1).
Very particularly preferred compounds are those conforming to formula
wherein
R
4
and R
5
are each independently of the other hydrogen; C
1
-C
12
alkyl; or C
1
-C
12
alkoxy; and
R
6
is C
1
-C
12
alkyl; or C
1
-C
12
alkoxy.
Important compounds are, in particular, those of formula (2), wherein
R
4
is hydrogen; and
R
5
and R
6
are C
5
-C
12
alkoxy;
or those compounds of formula (2), wherein
R
4
and R
5
are C
5
-C
12
alkyl; and
R
6
is hydrogen.
Very particularly preferred compounds are those of formula
wherein
R
7
is C
5
-C
12
alkoxy; and
R
8
is hydrogen; or C
1
-C
5
alkyl.
The triazine derivatives of this invention can be used as single compounds or as mixtures of different single compounds with each other.
The novel symmetrical triazine derivatives of formula (1) can, in particular, also be used as mixtures with triazine compounds of formula
In formula (4),
R
10
is hydrogen; C
6
-C
12
alkyl; or C
2
-C
6
alkenyl; and
R
11
is C
1
-C
12
alkoxy.
C
2
-C
6
Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl or 3-methyl-but-2-enyl.
The mixtures of triazine compounds of formula (1) and formula (4) are another subject matter of this invention.
The novel triazine derivatives of formula (1) may be prepared in different manner. In a Grignard reaction, for example, 1 mol of cyanuric chloride is reacted with 3 mol of the corresponding phenylmagnesium bromide compound which, depending on the meaning of R
1
, R
2
and R
3
of formula (1), may contain an alkyl radical and/or one or several free hydroxyl groups. Processes for the preparation of this intermediate are known and are described, inter alia, in EP-A-0,557,559.
This intermediate is also obtainable by Friedel-Crafts alkylation of cyanuric chloride with the corresponding phenyl compounds which, depending on the meaning of R
1
, R
2
and R
3
in formula (1), may contain an alkyl radical and/or one or several free hydroxyl groups, in the presence of a Lewis acid, preferably aluminium chloride.
According to A. Ninagawa, M. Kawazoe, H. Matsuada, Makromol.Chem. 180, (1979), 2123, this intermediate is also obtainable by cyclotrimerisation of a benzonitrile compound containing an alkyl radical and/or one or more than one hydroxyl group, depending on the meaning of R
1
, R
2
and R
3
in formula (1).
The end products corresponding to formula (1) are obtainable in a second reaction step by etherifying the hydroxyl group of the intermediates obtained in the first reaction step by alkylation in accordance with customary methods.
A further subject matter of this invention relates to the processes for the preparation of the novel triazine derivatives.
The inventive symmetrical triazine derivatives of formula (1) or mixtures of these compounds with triazine compounds of formula (4) as well as compounds of formula
wherein
Ar is a radical of formula
 R
1
is hydrogen; hydroxy; C
1
-C
12
alkyl; or C
1
-C
12
alkoxy;
R
2
is hydroxy; C
1
-C
12
alkoxy; or benzyloxy;
R
3
is hydroxy; C
1
-C
12
alkyl; or C
1
-C
12
alkoxy; and
R
4
is hydrogen; or C
1
-C
12
alkoxy; or
R
1
and R
2
, together with the phenyl radical, are a heterocyclic five-membered ring which is condensed with benzene, preferably a radical of formula (5a)
are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, against the harmful effects of UV radiation.
Illustrative examples of compounds of formula (5) are
Accordingly, these compounds are suitable as light stabilisers in cosmetic, pharmaceutical and veterinary preparations. They can be obtained in dissolved form or, it they are only sparingly soluble or insoluble, they can be incorporated in the preparations in micronised form having an average particle size in the range of 0.02 to 2, preferably of 0.05 to 1.5 and, most preferably, of 0.1 to 1.0 &mgr;m.
Accordingly, another object of this invention is the provision of a cosmetic preparation for skin or hair, which comprises at least one compound of formula (1) or (5) as well as carriers or auxiliaries which are cosmetically compatible with skin and hair, or to a cosmetic formulation for skin or hair, which comprises a mixture of
a) at least one or more than one compound of formula (1) or (5), and
b) a compound of formula (4)
together with carriers or auxiliaries which are cosmetically compatible with skin and hair.
In addition to the novel UV absorbers, the cosmetic formulations can also contain one or more than one further UV protective of the following substance classes:
1. p-aminobenzoic acid derivatives, typically 2-ethylhexyl 4-dimethylaminobenzoate;
2. salicylic acid derivatives, typically 2-ethylhexyl salicylate;
3. benzophenone derivatives, typically 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;
4. dibenzoylmethane derivatives, typically 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;
5. diphenylacrylates, typically 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and 3-(benzo-furanyl)-2-cyanoacrylate;
6. 3-imidazol-4-yl-acrylic acid and 3-imidazol-4-yl-acrylate;
7. benzofuran derivatives, preferably 2-(p-aminophenyl)benzofuran derivatives, disclosed in EP-A-582,189, U.S. Pat. No. 5,338,539, U.S. Pat. No. 5,518,713 and in EP-A-613,893;
8. polymeric UV absorbers, such as the benzylidenemalonate derivatives described, inter alia, in EPA-709,080;
9. cinnamic acid derivatives, typically the 2-ethylhexyl 4-methoxycinnamate or isoamylate or cinnamic acid derivatives disclosed, inter alia, in U.S. Pat. No. 5,601,811 and WO 97/00851;
10. camphor derivatives, typically 3-(4′-methyl)benzylidenebornan-2-one, 3-benzylidene-bornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer, 3-(4′-trimethylammonium) benzylidenebornan-2-one methyl sulfate, 3,3′-(1, 4-phenylenedime-thine)-bis (7,7-dimethyl-2-oxo-bicyclo-[2.2.1]heptane-1-methansulfonic acid) and the salts thereof, 3-(4′-sulfo)benzylidenebornan-2-one and the s

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