Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-04-18
2002-05-07
Ford, John M. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C514S183000, C514S184000, C252S299610, C252S301260, C252S587000, C534S015000, C540S121000, C540S122000, C540S124000, C540S139000, C540S140000
Reexamination Certificate
active
06384027
ABSTRACT:
The present invention relates to phthalocyanine analogs, in particularly to azaphthalocyanines (pyridinoporphyrazines). It further relates to compositions containing these compounds, and methods of use of such compounds and compositions.
Phthalocyanine is shown in
FIG. 1
(
a
). The nomenclature for the numbering of the Benzo portion is also included in the above depiction. Generally substituents in the R2, 3, 9, 10, 16, 17, 23, 24 positions are referred to as peripheral groups and substituents in the R1, 4, 8, 11, 15, 18, 22, 25 positions are referred to as non-peripheral groups.
Often, phthalocyanine is abbreviated to Pc.
Pcs in condensed phases possess interesting optical absorption signatures. semiconductivity and optoelectronic properties which are often sensitive to molecular packing. Normally, the planar molecules are prone to form co-facial or near co-facial assemblies. These “Face-to-Face” structures include the simple aggregates found in solution,
2
the longer columnar stacks in the liquid crystal phases of mesogenic derivatives,
3
and the classic “herring bone” columnar packing in the most common polymorphs of the unsubstituted compounds.
4
Polymeric columnar structures include the “shish-kebab” polymers formed when the central metal atoms of neighbouring Pc units are covalently or coordinatively linked via bridging atoms or molecules.
5
The unusual properties that Pcs and Pc analogs exhibit means they have many applications.
UK Patent GB 2,229,190 B relates to certain novel substituted phthalocyanines, methods for their preparation and to certain uses thereof. For example the compounds described in GB 2,229,190 B are suitable for use in optical recording media. Kuder in J. of Imaging Science, vol. 32, (1988), pp51-56 discusses how phthalocyanine dyes may be used in laser addressed optical recording media; in particular it sets out how active layers may be deposited.
UK Patent Application 9317881.2 describes substituted metallophthalocyanines and phthalocyanines as PDT agents.
Patent application WO 93/09124 describes the use of water soluble salt or acid forms of transition metal phthalocyanines for use in photodynamic therapy. In this patent application, phthalocyanines containing second or third row transition metals with a d6 low-spin electronic configuration are disclosed. The compounds exemplified in patent application WO 93/09124 contain Ru.
Phthalocyanine derivatives have also been used in Langmuir Blodgett films as described in UK Patent 2,229,190 B.
The redox behaviour of phthalocyanines is also of interest. Some uses which exploit the redox properties of phthalocyanines include electrocatalysis, photocatalysis, photovoltaics, electric conduction, photoconductivity and electrochromism. These uses (amongst others) of phthalocyanines are discussed by A. B. P. Lever in Chemtech, 17, pp506-510, 1987.
Certain pyridinoporphrazines (azaphthalocyanines, or AzaPcs)have been prepared and reported in the literature. These include tetrapyridino derivatives and bipyridino derivatives having Cr, Co, Cu, Fe and Ni centres. Thus Linstead
7
first demonstrated the replacement of all four benzene rings of the Pc nucleus by pyridine in his classic investigations in the 1930s, obtaining a mixture of insoluble isomeric dyes from 3,4-dicyanopyridine. Subsequently, Shibamiya and coworkers prepared unsubstituted macrocycles containing combinations of both benzenoid and pyridinoid rings.
8
The absorption spectra of these compounds were described, although not with reference to any particular applications.
It can thus be seen that the provision of novel Pc derivatives (or uses for such derivatives) particularly those with novel absorption signatures, would provide a contribution to the art.
DISCLOSURE OF THE INVENTION
The present inventors have now produced and characterised novel organic solvent-soluble AzaPcs in which a pyridinoid ring is incorporated in or around the Pc nucleus. Such compounds provide, inter alia, for the generation of “Edge-to-Face” assemblies via metal-nitrogen coordination involving the pyridyl nitrogen atom of one molecule and the metal ion of a second molecule.
Although Edge-to-Face assembles have been constructed earlier using porphyrin derivatives,
6
they have not as yet been realised within the Pc series. Such compounds have unexpected and industrially applicable properties in a variety of technical fields as is described in further detail hereinafter.
Thus according to one aspect of the invention there is disclosed an AzaPc of Formula I (FIG.
1
(
b
)):
wherein:
M is selected from:
a metal atom; a metal compound; 2H whereby one H is bonded to each of the two nitrogen atoms depicted as being bonded to M (positions 29 and 31 shown)
and wherein:
one or more of the Q groups is selected from: formula II or formula III, with the remaining Q groups each being formula IV:
wherein:
R
33
and R
34
are independently selected from: H or methyl
R
35
is selected from: H; C
1
to C
4
alkyl; C
2
to C
4
alkenyl; methoxy; butoxy; propoxy; NH
2
; NH—(C
1
to C
4
alkyl); N—(C
1
to C
4
alkyl)
2
, S—(C
1
to C
4
alkyl).
each R
n
and R
p
group is independently selected from: C
1
to C
32
alkyl; C
2
to C
32
alkenyl; X—O—Y; X—phenyl X
2
COOX
1
; X
2
CONR
1
R
11
; H; halide
wherein:
X and X
2
are independently selected from: a chemical bond; —(CH
2
)
n
— wherein n is an integer from 1 to 32; —(CH
2
)
a
—CH═CH(CH
2
)
b
where a and b are independently selected from integers 0-32 and a+b totals 32.
X
1
and Y are independently selected from: C
1
to C
32
alkyl; C
2
to C
32
alkenyl; H
R
1
and R
11
are independently selected from: H; C
1
to C
32
alkyl; C
2
to C
32
alkenyl; —(CH
2
)
n
—
with the proviso that where more than one Q is Formula II with the remaining Q group being Formula IV, at least one of the R
33
, R
34
, R
35
, R
n
, or R
p
groups is not H.
In a further, preferred aspect of the invention, there is disclosed an AzaPc having formula V (FIG.
1
(
f
)).
Wherein:
M is selected from:
a metal atom; a metal compound; 2H whereby one H is bonded to each of the two nitrogen atoms depicted as being bonded to M (positions 29 and 31 shown)
R
3
is H or methyl
R
1
and R
4
are independently selected from: H; C
1
to C
4
alkyl; C
2
to C
4
alkenyl; methoxy; butoxy; propoxy; NH
2
; NH—(C
1
to C
4
alkyl); N—(C
1
to C
4
alkyl)
2
, S—(C
1
to C
4
alkyl).
R
8
to R
25
are the same or different and are independently selected from:
C
1
to C
32
alkyl; C
2
to C
32
alkenyl; X—O—Y; X—phenyl
X
2
COOX
1
; X
2
CONR
1
R
11
; H; halide
wherein:
X and X
2
are independently selected from: a chemical bond: —(CH
2
)
n
— wherein n is an integer from 1 to 32; —(CH
2
)
a
—CH═CH(CH
2
)
b
where a and b are independently selected from integers 0-32 and a+b totals 32.
X
1
and Y are independently selected from: C
1
to C
32
alkyl; C
2
to C
32
alkenyl; H
R
1
and R
11
are independently selected from: H; C
1
to C
32
alkyl; C
2
to C
32
alkenyl; —(CH
2
)
n
—
Most preferably the compound has formula VI (as shown in FIG.
1
(
g
), wherein M=2H, Ni, Zn, Co, Cu, Pd, Ru or Al.
Referring to formula I, formula VI has one Q group of formula II with the remaining Q groups each being formula IV. R
33
, R
34
and R
35
are H; R
n
are C
8
alkyl and R
p
is H.
Preferred Compounds
Preferred compounds of the present invention are those wherein any one or more of the following apply:
All non-peripheral R groups (e.g. R
n
in formula III and IV) are H.
All R groups other than those attached to pyridyl nuclei are alkyl containing up to 32 (preferably up to 20, more preferably between 4-14 or between 8-12) C atoms where 1 or more adjacent CH
2
groups may be replaced by O or a double bond, and the remaining R groups are all H.
All peripheral R groups other than those attached to pyridyl nuclei are alkyl containing up to 32 (preferably up to 20, more preferably between 4-14 or between 8-12) C atoms, and the remaining R groups are all H.
The R groups attached to the or each pyridyl nucleus on the C atoms adjacent the N (i.e. R
33
,R
34
,R
1
,R
3
as a
Ford John M.
Nixon & Vanderhye
QinetiQ Limited
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