Phthalocyanine and use of phthalocyanine as a marking agent

Details Phthalocyanine and use of phthalocyanine as a marking agent Phthalocyanine and use of phthalocyanine as a marking agent

1999-11-19

2002-01-22

Solola, T. A. (Department: 1626)

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

Organic compounds

Azo

C534S707000, C534S708000, C534S726000, C540S123000, C540S124000, C540S125000, C540S127000, C540S128000, C540S140000, C208S014000, C208S370000

Reexamination Certificate

active

06340745

ABSTRACT:

The present invention relates to novel phthalocyanines of the formula I
where
Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AlCl, AlOH, AlOCOCH
3
, AlOCOCF
3
, SiCl
2
or Si(OH)
2
,
at least four of the radicals R
1
to R
16
are each independently of the others a five- or six-membered saturated nitrogen-containing heterocyclic radical which is bonded to the phthalocyanine structure via a ring nitrogen atom and which can additionally contain one or two further nitrogen atoms or a further oxygen or sulfur atom, and
any remaining radicals R
1
to R
16
are each hydrogen, halogen, hydroxysulfonyl or C
1
-C
4
-dialkylsulfamoyl,
subject to the proviso that tetrakispiperidinylphthalocyanine shall be excluded,
to the use of heterocyclyl-substituted phthalocyanines for marking liquids, and to mineral oils comprising such phthalocyanines.
J. Gen. Chem. USSR, 51 (1981), 1405-1411, discloses the preparation of tetrakispiperidinylphthalocyanine. WO-A-94/02570 and WO-A-96/10620 describe phthalocyanines as markers for liquids, especially mineral oils.
However, it has been found that the markers described therein still have defects in their application properties, especially insufficient solubility and insufficient chemical stability in solution.
It is an object of the present invention to provide suitable phthalocyanines having an improved property profile.
We have found that this object is achieved by the phthalocyanines of the formula I more particularly defined at the beginning.
Any alkyl appearing in the formulae mentioned herein may be straight-chain or branched.
Halogen is for example fluorine, chlorine, bromine or iodine.
C
1
-C
4
-Dialkylsulfamoyl is for example dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, diisopropylsulfamoyl, dibutylsulfamoyl or N-methyl-N-ethylsulfamoyl.
Suitable five- or six-membered saturated nitrogen-containing heterocyclic radicals which are attached to the phthalocyanine structure via a ring nitrogen atom and can additionally contain one or two further nitrogen atoms or a further oxygen or sulfur atom in the ring are derived for example from pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine or thiomorpholine as basic structure.
The heterocyclic radicals can be monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted. Preferred substituents are C
1
-C
4
-alkyl, benzyl, phenylethyl or phenyl.
Suitable heterocyclic radicals are for example pyrrolidin-1-yl, 2- or 3-methylpyrrolidin-1-yl, 2,4-dimethyl-3-ethylpyrrolidinyl, pyrazolidin-1-yl, 2-, 3-, 4- or 5-methylpyrazolidin-1-yl, imidazolidin-1-yl, 2-, 3-, 4- or 5-methylimidazolidin-1-yl, oxazolidin-3-yl, 2-, 4- or 5-methyloxazolidin-3-yl, isoxazolidin-2-yl, 3-, 4- or 5-methylisoxazolidin-2-yl, piperidin-1-yl, 2-, 3-, 4-methyl-, -ethyl- or -benzyl-piperidin-1-yl, 2,6-dimethylpiperidin-1-yl, piperazin-1-yl, 4-(C
1
-C
4
-alkyl)piperazin-1-yl, such as 4-methyl- or 4-ethylpiperazin-1-yl, morpholin-4-yl, thiomorpholin-4-yl or thiomorpholin-4-yl S,S-dioxide.
Preferred heterocyclic radicals are derived from pyrrolidine, piperidine, piperazine or morpholine as basic structure.
Preference is given to phthalocyanines of the formula I wherein four of the radicals R
1
to R
16
are each a heterocyclic radical.
Preference is further given to phthalocyanines of the formula I wherein four of the radicals R
1
to R
16
are each a heterocyclic radical and the remaining radicals R
1
to R
16
are each hydrogen.
Preference is further given to phthalocyanines of the formula I which have heterocyclic radicals which are monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted, by C
1
-C
4
-alkyl, benzyl, phenylethyl or phenyl.
Preference is given to phthalocyanines which conform to the formula Ia or Ib
where
the radicals R
4
, R
8
, R
12
and R
16
and also R
2
, R
6
, R
10
and R
14
are each a heterocyclic radical and Me is in each case as defined above, and also their positional isomers in relation to the radicals R
4
, R
8
, R
12
and R
16
and also R
2
, R
6
, R
10
and R
14
.
Of particular interest are phthalocyanines of the formula Ia or Ib, where R
4
, R
8
, R
12
and R
16
and also R
2
, R
6
, R
10
and R
14
are each pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholin-4-yl, which radicals can be monosubstituted, disubstituted or trisubstituted, preferably monosubstituted, by C
1
-C
4
-alkyl, benzyl, phenylethyl or phenyl.
Preference is also given to phthalocyanines of the formula I in which the substituents are selected from a combination of the above-recited preferred substituents.
The novel phthalocyanines of the formula I are obtainable in a conventional manner, for example as described in J. Gen. Chem. USSR 51 (1981) 1405-1411, F. H. Moser, A. L. Thomas, The Phthalocyanines, CRC Press, Boca Rota, Fla., 1983, or J. Am. Chem. Soc. 106 (1984) 7404-7410. For instance, phthalonitriles which, in conformance with the formula I, bear suitable substituents can be made to react in an inert diluent in the presence of a base, optionally in the presence of a metallizing reagent.
The present invention further provides for the use of phthalocyanines of the formula II
where
Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AlCl, AlOH, AlOCOCH
3
, AlOCOCF
3
, SiCl
2
or Si(OH)
2
,
at least four of the radicals R
1
to R
16
are each independently of the others a five- or six-membered saturated nitrogen-containing heterocyclic radical which is bonded to the phthalocyanine structure via a ring nitrogen atom and which can additionally contain one or two further nitrogen atoms or a further oxygen or sulfur atom, and
any remaining radicals R
1
to R
16
are each hydrogen, halogen, hydroxysulfonyl or C
1
-C
4
-dialkylsulfamoyl,
as markers for liquids.
Preference is given to the use of phthalocyanines of the formula I wherein four of the radicals R
1
to R
16
are each a heterocyclic radical.
Preference is further given to the use of phthalocyanines of the formula I wherein four of the radicals R
1
to R
16
are each a heterocyclic radical and the remaining radicals R
1
to R
16
are each hydrogen.
Preference is further given to the use of phthalocyanines of the formula I which have heterocyclic radicals which are monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted, by C
1
-C
4
-alkyl, benzyl, phenylethyl or phenyl.
Particular preference is given to the use of phthalocyanines which conform to the formula Ia or Ib
where
the radicals R
4
, R
8
, R
12
and R
16
and also R
2
, R
6
1
R
10
and R
14
are each a heterocyclic radical and Me is in each case as defined above, and also their positional isomers in relation to the radicals R
4
, R
8
, R
12
and R
16
and also R
2
, R
6
, R
10
and R
14
.
Of particular interest is the use of phthalocyanines of the formula Ia or Ib, where R
4
, R
8
, R
12
and R
16
and also R
2
, R
6
, R
10
and R
14
are each pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholin-4-yl, which radicals can be monosubstituted, disubstituted or trisubstituted, preferably monosubstituted, by C
1
-C
4
-alkyl, benzyl, phenylethyl or phenyl.
It is frequently necessary to mark liquids in order that the liquids thus marked may be detected later, for example in use, by means of suitable methods.
In this way it is possible, for example, to distinguish fuel oil and diesel oil.
Suitable solvents for marking according to the invention by means of the compounds more particularly defined above are especially organic liquids, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, neopentanol or hexanol, glycols, such as 1,2-ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 2,3- or 1,4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol, ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol

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