U.S. patent number RE34,480 [Application Number 07/940,309] was granted by the patent office on 1993-12-14 for naphthalocyanine compounds.
This patent grant is currently assigned to Yamamoto Kagaku Gosei Co., Ltd.. Invention is credited to Tsunehito Eda.
United States Patent |
RE34,480 |
Eda |
December 14, 1993 |
Naphthalocyanine compounds
Abstract
Naphthalocyanine compounds represented by the general formula
##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may
be the same or different, are each a straight chain or branched
chain alkyl group of 5 to 12 carbon atoms and M is a metal selected
from the group consisting of Cu, Ni, Mg, Pb, Pd, V, Co, .[.Nb,.].
Al, Sn, In, Fe and Ge, or its oxide, chloride or bromide, are
bluish green or green crystals and are superior in absorption or
near infrared rays of 750 and 850 nm, highly resistant to light,
heat, acids and alkalis, soluble in organic acids, liquid crystals
and resins, and accordingly are very useful as a dyestuff capable
of absorbing near infrared rays.
Inventors: |
Eda; Tsunehito (Kashihara,
JP) |
Assignee: |
Yamamoto Kagaku Gosei Co., Ltd.
(Osaka, JP)
|
Family
ID: |
27461088 |
Appl.
No.: |
07/940,309 |
Filed: |
September 3, 1992 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
631700 |
Jul 17, 1984 |
04622179 |
Nov 11, 1986 |
|
|
Foreign Application Priority Data
|
|
|
|
|
Jul 19, 1983 [JP] |
|
|
58-130272 |
Mar 5, 1984 [JP] |
|
|
59-41618 |
|
Current U.S.
Class: |
540/139;
540/140 |
Current CPC
Class: |
C09B
47/0673 (20130101) |
Current International
Class: |
C09B
47/04 (20060101); C09B 47/067 (20060101); C09B
047/04 () |
Field of
Search: |
;540/140,139 |
Foreign Patent Documents
|
|
|
|
|
|
|
1580683 |
|
Sep 1969 |
|
FR |
|
321131 |
|
May 1972 |
|
SU |
|
Other References
Mikhalenko et al., Chemical Abstracts, vol. 77 (1972) 116052n.
.
Beavan, Chemical Abstracts, vol. 97, (1982) 129504z..
|
Primary Examiner: Raymond; Richard L.
Attorney, Agent or Firm: Armstrong, Westerman, Hattori,
McLeland & Naughton
Claims
I claim:
1. A naphthalocyanine compound represented by the general formula
##STR8## characterized in that R.sub.1, R.sub.2, R.sub.3 and
R.sub.4, which may be the same or different, are each a straight or
branched alkyl group of 5 to 12 carbon atoms and M is a metal
selected from the group consisting of Cu, Ni, Mg, Pb, Pd, V, Co,
.[.Nb,.]. Al, Sn, In, Fe and Ge or its oxide, chloride or
bromide.
2. A naphthalocyanine compound as claimed in claim 1, characterized
by being tetra-tert-amylvanadylnaphthalocyanine.
3. A naphthalocyanine compound as claimed in claim 1, characterized
by being copper tetra-tert-amylnaphthalocyanine.
4. A naphthalocyanine compound as claimed in claim 1, characterized
by being nickel tetra-tert-amylnaphthalocyanine.
5. A naphthalocyanine compound as claimed in claim 1, characterized
by being magnesium tetra-tert-amylnaphthalocyanine.
6. A naphthalocyanine compound as claimed in claim 1, characterized
by being lead tetra-tert-amylnaphthalocyanine.
7. A naphthalocyanine compound as claimed in claim 1, characterized
by being palladium tetra-tert-amylnaphthalocyanine.
8. A naphthalocyanine compound as claimed in claim 1, characterized
by being cobalt, tetra-tert, sec-mixed amylnaphthalocyanine. .[.9.
A naphthalocyanine compound as claimed in claim 1, characterized by
being
niobium tetra-tert, sec-mixed amylnaphthalocyanine..]. 10. A
naphthalocyanine compound as claimed in claim 1, characterized by
being
aluminum tetra-tert, sec-mixed amylnaphthalocyanine chloride. 11. A
naphthalocyanine compound as claimed in claim 1, characterized by
being
tin tetra-tert, sec-mixed amylnaphthalocyanine. 12. A
naphthalocyanine compound as claimed in claim 1, characterized by
being indium tetra-tert,
sec-mixed amylnaphthalocyanine. 13. A naphthalocyanine compound as
claimed in claim 1, characterized by being iron tetra-tert,
sec-mixed
amylnaphthalocyanine chloride. 14. A naphthalocyanine compound as
claimed in claim 1, characterized by being germanium tetra-tert,
sec-mixed
amylnaphthalocyanine. 15. A naphthalocyanine compound as claimed in
claim 1, characterized by being tetra-tert, sec-mixed
amylvanadylnaphthalocyanine. 16. A naphthalocyanine compound as
claimed in claim 1, characterized by being
tetra-tert-heptylvanadylnaphthalocyanine.
7. A naphthalocyanine compound as claimed in claim 1, characterized
by
being tetra-tert-octylvanadylnaphthalocyanine. 18. A
naphthalocyanine compound as claimed in claim 1, characterized by
being tetra-tert-dodecylvanadylnaphthalocyanine.
Description
This invention relates to novel naphthalocyanine compounds. More
particularly, the present invention relates to novel
naphthalocyanine compounds represented by the general formula (I)
##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may
be the same or different, are each a straight chain or branched
chain alkyl group of 5 to 12 carbon atoms and M is a metal selected
from the group consisting of Cu, Ni, Mg, Ph, Pd, V, Co, .[.Nb,.].
Al, Sn, In, Fe and Ge, or its oxide, chloride or bromide.
Naphthalocyanine compounds represented by the general formula (I)
according to the present invention, are bluish green or green
crystals and are superior in absorption of near infrared rays of
750 to 850 nm, highly resistant to light, heat, acids and alkalis,
soluble in organic solvents, liquid crystals and resins, and
accordingly are very useful as a dyestuff capable of absorbing near
infrared rays.
In recent years, extensive research has been made on the
utilization of a semiconductor laser beam in writing and
reading-out for video discs, liquid crystal display instruments,
optical character readers and the like. In order to increase the
efficiency of writing and reading-out by the use of a semiconductor
laser beam, a substance capable of absorbing semiconductor laser
beams, namely, near infrared rays is indispensable. Hence,
development of a substance superior in absorption of near infrared
rays has strongly been desired.
Cyanine dyestuff is well known as an organic compound absorbing
near infrared rays. Although the cyanine dyestuff well absorbs near
infrared rays, it is very poor in light resistance and durability.
Hence, there are a number of limitations in actual use of cyanine
dyestuff. Also, metal complexes of oxime and thiol are known as
organic compounds absorbing near infrared rays. These complexes are
inferior in absorption of near infrared rays and, in certain media,
the complexes release the metal resulting in loss of the ability to
absorb near infrared rays.
In order to overcome the above-mentioned draw-backs of conventional
dyestuffs which absorb near infrared rays, the present inventor has
focused on naphthalocyanine compounds and has made extensive
research with the particular objective of improving the solubility
of naphthalocyanine compounds. As a result, it was found that
introduction of alkyl groups of 5 to 12 carbon atoms as shown in
the general formula (I) greatly enhances the solubility of
naphthalocyanine compounds in organic solvents, etc. Based on this
finding, the present invention has been completed.
As shown in the art, in production of optical discs, a coating
method such as spin-coating as a means of forming a recording film
at a low cost is drawing attention. In order to enable the
formation of a recording film by a coating method, it is
indispensable that the dyestuff used by soluble in the solvent
used. Therefore, improvement of the solubility in solvents of the
dyestuff is very useful.
As naphthalocyanine compounds, there has been known
tetra-6-tert-butylvanadylnaphthalocyanine of the following general
formula (II) described in Zh. Obs. khim, 42 696-699 (1972):
##STR3## wherein R.sub.5 is tert-butyl. However, as shown in Table
1, this compound has a much lower solubility in organic solvents
than the compounds of the general formula (I) according to the
present invention.
TABLE 1 ______________________________________ Solubility in
Toluene Substituent of vanadylnaphthalocyanine Solubility (%)
______________________________________ tert-heptyl (present
invention) 11 tert-amyl (present invention) 6 tert, sec-mixed amyl
(present invention) 7 tert-butyl 2
______________________________________
MEASUREMENT OF SOLUBILITY
In a 20 ml test tube were placed 1 g of a naphthalocyanine compound
and 5 ml of toluene. After the tube was tightly stoppered, the
content was subjected to ultrasonic shaking at 50.degree. C. for 10
min. Then, the tube was allowed to stand at room temperature for 30
min. and the content was filtered. The filtrate was concentrated to
dryness. The solubility of the naphthalocyanine in toluene was
calculated using the following equation. ##EQU1## R.sub.1, R.sub.2,
and R.sub.3 and R.sub.4 of naphthalocyanine compounds of the
present invention can bond to 6 to 7 positions of all naphthalene
nuclei of naphthalocyanine. Each of these groups can be a mixed
group.
Specific examples of naphthalocyanine compounds according to the
present invention, wavelengths at which these naphthalocyanine
compounds show their respective largest absorption peaks in
toluene, and absorptivity coefficients of the naphthalocyanine
compounds are shown in Table 2. It is to be noted that the
naphthalocyanine compounds according to the present invention are
not restricted to the compounds shown in Table 2.
TABLE 2 ______________________________________ Wavelength at
Absorptivity largest absorp- coefficient Substituent M tion peak
(nm) (log .epsilon.) ______________________________________
tert-amyl Cu 771 5.24 tert-amyl Ni 765 5.14 tert-amyl Mg 781 5.16
tert-amyl Pb 782 5.12 tert-amyl Pd 782 5.12 tert-amyl VO 808 5.37
tert, sec-mixed amyl Co 757 5.09 .[.tert, sec-mixed amyl No 782
5.06.]. tert, sec-mixed amyl Al--Cl 781 5.04 tert, sec-mixed amyl
Sn 781 4.08 tert, sec-mixed amyl In 805 5.09 tert, sec-mixed amyl
Fe--Cl 782 5.13 tert, sec-mixed amyl Ge 781 5.07 tert, sec-mixed
amyl VO 809 5.32 tert-heptyl VO 809 5.27 tert-octyl VO 809 5.41
tert-dodecyl VO 813 5.29 ______________________________________
Wavelengths at which naphthalocyanine compounds of the present
invention show largest absorption peaks vary by the type of M of
the general formula (I), however, do not vary much by the type of
substituents (R.sub.1, R.sub.2, R.sub.3 and R.sub.4).
Naphthalocyanine compounds of the present invention can be
produced, for example, by reacting, with heating,
2,3-dicyanonaphthalenes represented by the following formula (III):
##STR4## (wherein R.sub.6 is an alkyl group of 5 to 12 carbon
atoms) with a metal chloride in the presence of urea.
2,3-Dicyanonaphthalenes of the general formula (III) used in
production of naphthalocyanine compounds of the present invention
are synthesized as follows.
1. Synthesis of 6-tert-amyl-2,3-dicyanonaphthalene (V) ##STR5##
To 450 g of o-xylene is added 15 g of anhydrous ferric chloride.
The mixture is saturated with dry hydrogen chloride gas. Thereto is
added dropwise 100 g of 2-methyl-2-butene at 10.degree. C. to
20.degree. C. in 30 min. The mixture is stirred at the same
temperature for 5 hr. Then, 100 g of 10% sulfuric acid is added
thereto and insolubles are removed by filtration. The organic layer
of the filtrate is separated. The layer is washed with a dilute
aqueous sodium hydroxide solution and then with hot water.
Thereafter, excessive o-xylene is distilled off. The residue is
subjected to distillation under reduced pressure, whereby 210 g of
a colorless liquid is obtained. The liquid has a boiling point of
114.degree. to 116.degree. C. at 20 mm Hg. The following analytical
results confirmed that the liquid was
6-tert-amyl-2,3-dimethylbenzene (IV).
Elemental analysis:
______________________________________ C H
______________________________________ Calculated: 88.54 11.46
Measured: 88.77 11.42 ______________________________________
Infrared spectrum:
Has characteristic peaks of 1,2,4-substituents at 880 cm- and 820
cm-.
To 500 ml of carbon tetrachloride are added 35 g of
6-tert-amyl-2,3-dimethylbenzene (IV), 140 g of N-bromosuccinimide
and 1 g of benzoyl peroxide. The mixture is refluxed for 12 hr.
under irradiation by an incandescent lamp. After cooling, the solid
portion is removed by filtration. The filtrate is freed of carbon
tetrachloride by distillation. To the residue is added 100 ml of
n-hexane and the mixture is stirred. The resulting precipitate is
collected by filtration and dried in air to obtain 70 g of a white
crystal. It had a melting point of 64.5.degree. to 66.degree.
C.
49 G of this white crystal, 8 g of fumaronitrile and 100 g of
sodium iodide are added to 700 ml of dimethylformamide, and the
mixture is stirred at 70.degree. to 75.degree. C. for 7 hr. After
cooling, the reaction mixture is placed in 1 liter of water.
Thereto is added 150 ml of 10% sodium hydrogen sulfite. The whole
mixture is subjected to extraction with 500 ml of toluene. The
resulting toluene layer is washed with hot water and then
concentrated by distillation of toluene. To the residue is added
100 ml of n-hexane and the mixture is stirred. The resulting
precipitate is collected by filtration and recrystallized from
benzene/petroleum ether to obtain 13 g of a slightly colored
crystal. The crystal had a melting point of 94.5.degree. to
96.degree. C. The following analytical results confirmed that the
crystal was 6-tert-amyl-2,3-dicyanonaphthalene (V).
Elemental analysis:
______________________________________ C H N
______________________________________ Calculated: 82.21 6.51 11.28
Measured: 82.18 6.48 11.31
______________________________________
Infrared spectrum:
Has a characteristic peak of nitrile at 2240 cm-.
2. Synthesis of 6-tert, sec-mixed amyl-2,3-dicyanonaphthalene (VI)
##STR6##
O-xylene is amylated in the presence of aluminum chloride in the
same manner as in the Synthesis 1 whereby 4-tert, sec-mixed
amyl-o-xylene is obtained. This compound is brominated and reacted
with fumaronitrile in the same manner as in the Synthesis 1 whereby
6-tert, sec-mixed amyl-2,3-diacyanonaphthalene (VI) is obtained as
a slightly brown viscous oil. The infrared spectrum of this
compound has characteristic peaks of nitrile at 2240 cm- and 2225
cm-.
3. Synthesis of 6-tert-heptyl-2,3-dicyanonaphthalene (VII)
##STR7##
In the same manner as in the Synthesis 1 except that
2-methyl-2-hexene is used in place of 2-methyl-2-butene, there is
obtained 6-tert-heptyl-2,3-dicyanonaphthalene (VII) as a slightly
brown viscous oil. The infrared spectrum of this compound has a
characteristic peak of nitrile at 2230 cm-.
Next, the present invention will be explained specifically by way
of Examples.
EXAMPLE 1
Production of tetra-tert-amylvanadylnaphthalocyanine
15 Grans of 6-tert-amyl-2,3-dicyanonaphthalene, 3.8 g of vanadyl
trichloride and 70 g of urea were reacted at 195.degree. to
200.degree. C. for 2 hrs. After cooling, the reaction mixture solid
was mixed with 300 ml of 5% hydrochloric acid. The mixture was
heated to 50.degree. C., whereby the solid became friable. Stirring
was conducted at 50.degree. C. for 30 min. The insolubles were
collected by filtration and the cake thus obtained was again
treated with 300 ml of 5% hydrochloric acid and then washed with
hot water. Then, the cake was combined with 200 ml of 10% sodium
hydroxide and they were stirred at 70.degree. C. for 30 min. The
insolubles were collected by filtration. The resulting cake was
again treated with 200 ml of 10% sodium hydroxide and washed with
hot water. Subsequently, the cake was combined with 200 ml of
methanol and they were refluxed for 30 min. The insolubles were
collected by filtration and dried to obtain 10 g of a crude
product. The crude product was combined with 300 ml of toluene and
they were stirred at 80.degree. C. for 30 min. The insolubles were
removed by filtration and the toluene solution was subjected to
silica gel column chromatography to obtain 2.4 g of a refined
product.
Elemental analysis confirmed that this was a product of the
captioned compound.
______________________________________ C.sub.68 H.sub.64 N.sub.8 OV
C H N ______________________________________ Calculated: 77.02 6.10
10.57 Measured: 77.21 6.21 10.32
______________________________________
Tetra-tert-amylvanadylnaphthalocyanine thus obtained was a green
crystal. Its solubility in toluene as measured according to the
above mentioned method was 6% (0.6 g of residue).
Near infrared absorption spectrum for toluene solution:
Wavelength at largest absorption peak: 808 nm
Absorptivity coefficient (log .epsilon.): 5.37
EXAMPLE 2
Production of copper tetra-tert-amylnaphthalocyanine
20 Grams of 6-tert-amyl-2,3-dicyanonaphthalene (V), 3.4 g of cupric
chloride, 0.1 g of ammonium molybdate and 80 g of urea were reacted
at 195.degree. to 200.degree. C. for 2 hrs. After cooling the
reaction mixture solid was mixed with 300 ml of 5% hydrochloric
acid. The mixture was heated to 50.degree. C. and the solid became
gradually friable. The mixture was stirred at 50.degree. C. for 30
min. The insolubles wre collected by filtration. The cake thus
obtained was treated again with 300 ml of 5% hydrochloric acid and
then washed with hot water. Subsequently, the cake was combined
with 200 ml of 10% sodium hydroxide, and they were stirred at
70.degree. C. for 30 min. The insolubles were collected by
filtration. The cake obtained was again treated with 200 ml of 10%
sodium hydroxide and then washed throroughly with hot water. The
cake was combined with 200 ml of methanol and the mixture was
refluxed for 30 min. The insolubles were collected by filtration
and dried to obtain 8 g of a crude product. The crude product was
combined with 300 ml of toluene and they were stirred at 80.degree.
C. for 30 min. The insolubles were removed by filtration and the
toluene solution was subjected to silica gel column chromatography
to obtain 1.5 g of a refined product as a bluish green crystal.
Elemental analysis confirmed that this was a product of the
captioned compound.
______________________________________ C.sub.68 H.sub.64 N.sub.8 Cu
C H N ______________________________________ Calculated: 77.27 6.12
10.60 Measured: 77.38 6.02 10.51
______________________________________
The solubility of the product in toluene as measured according to
the above mentioned method was 7%.
Near infrared absorption spectrum for toluene solution:
Wavelength at largest absorption peak: 771 nm
Absorptivity coefficient (log .epsilon.): 524
EXAMPLE 3
Production of tetra-tert, sec-mixed amylvanadylnaphthalocyanine
20 Grams of a mixture of 6-tert-amyl-2,3-dicyanonaphthalene and
6-sec-amyl-2,3-dicyanonaphthalene, 5,6 g of vanadyl trichloride and
50 g of urea were reacted at 190.degree. to 195.degree. C. for 1
hr. To the reaction mixture solid after cooling was applied the
same procedure as in Example 1. The crude product obtained was
refined by column chromatography to obtain 3.4 g of the intended
product.
Elemental analysis confirmed that this product was the intended
product.
______________________________________ C.sub.68 H.sub.64 N.sub.8 OV
C H N ______________________________________ Calculated: 77.02 6.10
10.57 Measured: 77.17 5.98 10.49
______________________________________
Tetra-tert, sec-mixed amylvanadylnaphthalocyanine thus obtained was
a green crystal. Its solubility in toluene as measured according to
the above mentioned method was 7% (0.6 g of residue).
Near infrared absorption spectrum for toluene solution:
Wavelength at largest absorption peak: 809 nm
Absorptivity coefficient (log .epsilon.): 5.32
EXAMPLE 4
Production of Indium tetra-tert, sec-mixed amylnaphthalocyanine
20 Grams of 6-tert, sec-mixed amyl-2,3-dicyanonaphthalene, 5 g of
Indium chloride, 0.1 g of ammonium molybdate and 80 g of urea were
reacted at 198.degree. to 200.degree. C. for 2 hrs. The reaction
mixture was treated in the same manner as in Example 1. Finally, by
refining by column chromatography, there was obtained 3 g of the
intended product as a green crystal. Elemental analysis confirmed
that this product was the intended product.
______________________________________ C.sub.68 H.sub.64 N.sub.8 In
C H N ______________________________________ Calculated: 73.69 5.83
10.11 Measured: 73.81 5.72 10.04
______________________________________
The solubility of this compound in toluene as measured according to
the above mentioned method was 7%.
Near infrared absorption spectrum for toluene solution:
Wavelength at largest absorption peak: 805 nm
Absorptivity coefficient (log .epsilon.): 5.09
EXAMPLE 5
Production of tetra-tert-heptylvanadylnaphthalocyanine
6 Grams of 6-tert-heptyl-2,3-dicyanonaphthalene, 1.2 g of vanadyl
trichloride and 22 g of urea were reacted at 195.degree. to
198.degree. C. for 2 hrs. The reaction mixture was treated in the
same manner as in Example 1. Finally, refining by the column
chromatography was conducted, whereby 1 g of the intended product
was obtained as a green crystal.
Elemental analysis confirmed that this was a product of the
captioned compound.
______________________________________ C.sub.76 H.sub.80 N.sub.8 VO
C H N ______________________________________ Calculated: 77.84 6.89
9.56 Measured: 77.73 6.92 9.64
______________________________________
The solubility of this compound in toluene as measured according to
the above mentioned method was 11%.
Near infrared absorption spectrum for toluenee solution:
Wavelength at largest absorption peak: 809 nm
Absorptivity coefficient (log .epsilon.): 5.27
As described above, there are provided, according to the present
invention, naphthalocyanine compounds which are useful dyestuffs
absorbing near infrared rays and well soluble in organic
solvents.
Naphthalocyanine compounds according to the present invention can
be used as near infrared rays-absorbing dyestuffs for various
applications such as optical recording media, liquid crystal
display instruments, ball pens for OCR, optical filters, coloring
and dyeing of resins, coloring of inks and coatings and the
like.
* * * * *