U.S. patent application number 11/142443 was filed with the patent office on 2005-10-20 for diaminostilbene derivatives.
Invention is credited to Kimura, Keizo, Nakai, Yasufumi, Yabuki, Yoshiharu.
Application Number | 20050230662 11/142443 |
Document ID | / |
Family ID | 34738950 |
Filed Date | 2005-10-20 |
United States Patent
Application |
20050230662 |
Kind Code |
A1 |
Kimura, Keizo ; et
al. |
October 20, 2005 |
Diaminostilbene derivatives
Abstract
The following
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivative is well soluble in water: 1 in which each of R.sup.11
and R.sup.12 is hydrogen, or a specifically substituted or
unsubstituted alkyl group; each of R.sup.21 and R.sup.22 is
hydrogen, a specifically substituted or unsubstituted alkyl group,
a specifically substituted or unsubstituted aryl group; M is
hydrogen, alkali metal, alkaline earth metal, ammonium, or
pyridinium.
Inventors: |
Kimura, Keizo;
(Minami-ashigara-shi, JP) ; Yabuki, Yoshiharu;
(Minami-ashigara-shi, JP) ; Nakai, Yasufumi;
(Minami-ashigara-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
34738950 |
Appl. No.: |
11/142443 |
Filed: |
June 2, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11142443 |
Jun 2, 2005 |
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09678330 |
Oct 3, 2000 |
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6919452 |
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Current U.S.
Class: |
252/301.21 ;
252/301.23; 544/193.2 |
Current CPC
Class: |
C07D 251/68
20130101 |
Class at
Publication: |
252/301.21 ;
252/301.23; 544/193.2 |
International
Class: |
C07D 043/02; C09K
011/06 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 30, 1999 |
JP |
11-280694 |
Claims
1. 4,4'-Bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
compound having the following formula: 19in which each of L.sup.1
and L.sup.2 is an alkylene group having 2 to 8 carbon atoms which
has an intervening ether bonding; each of R.sup.11 and R.sup.12
independently is hydrogen, methyl, ethyl, n-propyl, n-butyl, or
2-sulfoethyl; each of R.sup.21 and R.sup.22 independently is
hydrogen, methyl, ethyl, n-propyl, isopropyl, 2-hydroxyethyl,
2-hydroxypropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl,
2-sulfoethyl, 2-(2-hydroxyethoxy)ethyl,
2-[2-(2-hydroxyethoxy)ethoxy]ethy- l, phenyl, naphthyl,
4-hydroxyphenyl, 3,5-dicarboxyphenyl, 4-methoxyphenyl, and
3-isopropylphenyl; and M is an alkali metal atom.
2. 4,4'-Bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
compound of claim 1, wherein at least one of L.sup.1 and L.sup.2 is
a divalent group which is represented by the following formula:
--(CH.sub.2CH.sub.2O).sub.- nCH.sub.2--in which n is an integer of
1 to 3.
3. 4,4'-Bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
compound of claim 2, wherein n in the formula is 1 or 2.
4. 4,4'-Bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
compound of claim 1, wherein each of R.sup.11 and R.sup.12 in the
formula independently is a hydrogen or methyl.
5. 4,4'-Bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
compound of claim 1, wherein each of R.sup.21 and R.sup.22 in the
formula independently is hydrogen, methyl, ethyl, isopropyl,
2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
2,3-dihydroxypropyl, 2-(2-hydroxyethoxy)ethyl,
2-[2-(2-hydroxyethoxy)ethoxy]ethyl, phenyl, or 4-hydroxyphenyl.
6. An aqueous solution in which a
4,4'-Bis(1,3,5-triazinylamino)stilbene-2- ,2'-disulfonic acid
compound of claim 1 is dissolved in water.
7. A method of brightening a surface of material with fluorescence
which comprises applying onto the surface an aqueous solution in
which a 4,4'-Bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
compound of claim 1 is dissolved in water.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a
4,4'-bis(1,3,5-triazinylamino)st- ilbene-2,2'-disulfonic acid
derivative which is favorably employable in an aqueous fluorescent
brightening solution, an aqueous photographic silver halide
emulsion, an aqueous solution for processing a photographic silver
halide-containing material. The invention further relates to use of
the 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivative for brightening a variety of materials with
fluorescence.
BACKGROUND OF THE INVENTION
[0002] Tamehiko Noguchi describes in Journal of Society of Organic
Synthetic Chemistry (Yuki Gosei Kagaku Kyoukaishi), vol. 19, p. 920
(1961) and vol. 20, p. 64 (1962) that
4,4'-bis(1,3,5-triazinylamino)stilb- ene-2,2'-disulfonic acid
derivatives are useful as fluorescent brightening agents.
[0003] U.S. Pat. No. 2,875,058, No. 2,933,390, and No. 2,945,762
describe 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic
acid derivatives are employable as additives for a photographic
silver halide emulsion.
[0004] German Patent (DE) No. 1,945,316 discloses
4,4'-bis-(1,3,5-triaziny- lamino)stilbene-2,2'-disulfonic acid
derivatives which show high fluorescent brightening effect on
cellulose fibers. The disclosed derivatives have a sulfoethylamine
substituent group on the 2-position of its triazine ring and
additionally a morpholine or alkanolamine substituent group on the
4-position. Examples of the alkanolamines are monoethanolamine,
methylethanolamine, diethanolamine, isopropanolamine, and
diisopropanolamine.
[0005] The 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic
acid derivatives to be employed in the form of aqueous solutions
such as photographic silver halide emulsions and aqueous solutions
for processing photographic silver halide-containing material are
preferably well soluble in water or an aqueous solution. In more
detail, the derivatives should be rapidly dissolved in an aqueous
medium and then should be hardly deposited during the storage of
the aqueous solution.
[0006] Japanese Patent Provisional Publications No. 6-329,936 and
No. 6-332,127 disclose
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivatives which are employable as fluorescent brightening agents
for an aqueous solution for processing photographic silver halide
material. The disclosed derivatives have high solubility in the
aqueous solution and are hardly deposited even when the processing
solution is kept at low temperatures. The latter 6-332,127
publication indicates that a preferred compound is such derivative
that the triazine ring is substituted on its 2-position with
ethylamine having a sodium sulfonate salt [therefore, four sodium
sulfonate groups are introduced into the derivative] and further
substituted on its 4-position with an alkanolamine (e.g.,
2-methyethanolamine).
SUMMARY OF THE INVENTION
[0007] According to the studies of the present inventors, the known
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivatives do not show satisfactory solubility in an aqueous
medium from the viewpoints of practical use of the fluorescent
brightening agent.
[0008] It is an object of the present invention to provide
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivatives which show increased solubility in an aqueous
medium.
[0009] As a result of further studies performed by the inventors,
it has been discovered that the desired high solubility is attained
by introducing into the 4-position of the triazine ring of the
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivative an amino group having an alkylene substituent of 2 to 8
carbon atoms in which the alkylene substituent has a hydroxyl group
or a hydroxyalkyl group of 1 to 3 carbon atoms as a substituent or
has an intervening ether bonding.
[0010] Accordingly, the present invention resides in a
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivative having the following formula (1): 2
[0011] in which
[0012] each of R.sup.11 and R.sup.12 independently is a hydrogen
atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group
having 1 to 20 carbon atoms which has one or more substituents
selected from the group consisting of hydroxyl, sulfo, and
alkoxy;
[0013] R.sup.21 is a hydrogen atom, an alkyl group having 1 to 20
carbon atoms, an alkyl group having 1 to 20 carbon atoms which has
one or more substituents selected from the group consisting of
hydroxyl, sulfo, and alkoxy, an aryl group having 6 to 20 carbon
atoms, an aryl group having 6 to 20 carbon atoms which has one or
more substituents selected from the group consisting of hydroxyl,
carboxyl, alkyl, or alkoxy, or a group represented by the formula
of -L.sup.1-CH.sub.2OH wherein L.sup.1 is an alkylene group having
2 to 8 carbon atoms which has one or more substituents selected
from the group consisting of hydroxyl and hydroxylalkyl having 1 to
3 carbon atoms or which has an intervening ether bonding;
[0014] R.sup.22 is a hydrogen atom, an alkyl group having 1 to 20
carbon atoms, an alkyl group having 1 to 20 carbon atoms which has
one or more substituents selected from the group consisting of
hydroxyl, sulfo, and alkoxy, an aryl group having 6 to 20 carbon
atoms, an aryl group having 6 to 20 carbon atoms which has one or
more substituents selected from the group consisting of hydroxyl,
carboxyl, alkyl, or alkoxy, or a group represented by the formula
of -L.sup.2-CH.sub.2OH wherein L.sup.2 is an alkylene group having
2 to 8 carbon atoms which has one or more substituents selected
from the group consisting of hydroxyl and hydroxylalkyl having 1 to
3 carbon atoms or which has an intervening ether bonding; and
[0015] M is a hydrogen atom, an alkali metal atom, an alkaline
earth metal atom, ammonium group, or pyridinium group.
[0016] The 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic
acid derivatives of the invention is included in the general
formula (SR) of the diaminostilbene compound for fluorescent
brightening agent which is disclosed in the aforementioned Japanese
Patent Provisional Publication No. 6-332127. However, the
specifically defined 4,4'-bis(1,3,5-triazinyla-
mino)stilbene-2,2'-disulfonic acid derivatives of the invention are
not described in the publication.
[0017] The present invention further resides in an aqueous solution
containing a 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic
acid derivative of the above-mentioned formula (1).
[0018] The invention furthermore resides in a method of brightening
a surface of material with fluorescence which comprises applying a
4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic acid
derivative of the formula (1) onto the surface of material.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic
acid derivatives of the invention is represented, as mentioned
above, by the following formula (1): 3
[0020] In the formula (1), an alkyl group for R.sup.11 and R.sup.12
has 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, more
preferably 1 to 4 carbon atoms. The alkyl group can be a straight
chain alkyl group, a branched chain alkyl group, or a cyclic alkyl
group. The alkyl group can have one or more substituent groups.
Examples of the substituent groups include a hydroxyl group, a
sulfo group, and an alkoxy group. The alkoxy group preferably has
such alkyl group as mentioned above.
[0021] Examples of the alkyl groups for R.sup.11 and R.sup.12
include methyl, ethyl, n-propyl, isopropyl, n-octyl,
2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-sulfoethyl,
2-methoxyethyl, 2-(2-hydroxyethoxy)ethyl,
2-[2-(2-hydroxyethoxy)ethoxy]ethyl; and
2-(2-[2-(2-hydroxyethoxy)-ethoxy]ethoxy)ethyl.
[0022] Each of R.sup.11 and R.sup.12 preferably is hydrogen,
methyl, ethyl, n-propyl, n-butyl, or 2-sulfoethyl, and more
preferably hydrogen, methyl, ethyl, or 2-sulfoethyl. Most preferred
is hydrogen or atom.
[0023] Examples of the alkyl groups for R.sup.21 and R.sup.22 are
those described hereinbefore for R.sup.11 and R.sup.12. Preferred
examples of R.sup.21 and R.sup.22 include hydrogen, methyl, ethyl,
n-propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl,
2-hydroxypropyl, 2,3-dihydroxypropyl, 2-sulfoethyl,
2-(2-hydroxyethoxy)ethyl, and 2-[2-(2-hydroxyethoxy)ethoxy]ethyl.
More preferred examples include hydrogen, methyl, ethyl, isopropyl,
2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
2,3-dihydroxpropyl, and 2-(2-hydroxyethoxy)ethyl. Most preferred
are hydrogen and methyl.
[0024] The aryl group for R.sup.21 and R.sup.22 has 6 to 20 carbon
atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8
carbon atoms. The aryl group can have one or more substituents.
Examples of the substituents include a hydroxyl group, a carboxyl
group, an alkyl group, and an alkoxy group. The alkyl group and
alkoxy group of the substituent can be the same as those described
hereinbefore for R.sup.11and R.sup.12. Examples of the substituted
and unsubstitued aryl groups for R.sup.21 and R.sup.22 include
phenyl, naphthyl, 4-hydroxyphenyl, 3,5-dicarboxyphenyl,
4-methoxyphenyl, and 3-isopropylphenyl. The aryl group preferably
is phenyl or 4-hydroxyphenyl.
[0025] The alkylene group for L.sup.1 and L.sup.2 is an alkylene
group having 2 to 8 carbon atoms which has, as a substituent, a
hydroxyl group or a hyroxyalkyl group having 1 to 3 carbon atoms.
Otherwise, the alkylene group has an ether bonding which intervenes
the alkylene chain at an optional position.
[0026] Preferred examples of the alkylene group for L.sup.1 and
L.sup.2 include those of the following formulas 1) to 5): 4
[0027] More preferred are those of the above-mentioned formulas 1)
to 4), namely, alkylene groups having one or more hydroxyl
substituent groups. Most preferred are those of the formulas 1) and
4).
[0028] Other preferred examples of the alkylene group for L.sup.1
and L.sup.2 include that represented by the following formula
(2):
--(CH.sub.2CH.sub.2O).sub.nCH.sub.2-- (2)
[0029] in which n is an integer of 1 to 3, preferably 1 or 2. Most
preferably, n is 1.
[0030] In the formula (1), M is a hydrogen atom, an alkali metal
atom, an alkaline earth metal atom, ammonium group, or pyridinium
group. Examples of the alkali metal atoms include Li, Na, K, Rb,
Cs, and Fr. Examples of the alkaline earth metal atoms include Ca,
Sr, Ba, and Ra. Preferred are Na and K. Examples of the ammonium
groups include triethylammonium and tetrabutylammonium.
[0031] Representative examples of the formula (1) of the invention
are illustrated below: 5678910
[0032] When the alkylene group for L.sup.1 or L.sup.2 of the
formula (1) has a hydroxyl or hydroxyalkyl substituent and contains
in its structure two or more asymmetric carbon atoms to which the
substituent is attached, there are a plurality of stereoisomers
having the same formula. Any of the isomers can be employed singly
or in combination.
[0033] The 4,4'-bis(1,3,5-triazinylamino)stilbene-2,2'-disulfonic
acid derivative of the formula (1) can be prepared by referring to
the descriptions of Journal of Society of Organic Synthetic
Chemistry, vol. 17, page 528 (1959) [written by Hirotsugu Matsui]
and Japanese Patent No. 2,618,748.
[0034] In more detail, the compound of the formula (1) can be
prepared by the steps of reacting a diaminostilbene derivative with
cyanuric chloride, reacting the resulting
4,4'-bistriazinylaminostilbene derivative with taurine, and finally
reacting the resulting product with hydroxyalkylamine. Otherwise, a
process starting from a dialkylaminostilbene derivative can be
adopted.
[0035] The reaction can be performed in a solvent such as water or
an organic solvent (e.g., alcohol, ketone, ether or amide). Water
and water-miscible organic solvents are preferred. The reaction
solvent can be a mixture of appropriate solvents. Preferred is an
aqueous acetone solvent. Generally, a base is employed in the
reaction. Examples of the bases include organic bases such as
triethylamine, pyridine, and 1,8-diazabicyclo[5,4,0]-7-undecene,
and inorganic bases such as sodium hydroxide, potassium hydroxide,
sodium carbonate, potassium carbonate, sodium hydrogen carbonate,
and sodium hydride. The inorganic bases such as sodium hydroxide,
potassium hydroxide, sodium carbonate and potassium carbonate are
preferably employed. The reaction is generally performed at a
temperature in the range of -20.degree. C. to 120.degree. C.,
preferably -10.degree. C. to 90.degree. C. In more detail, the
reaction in the first step is preferably performed at a temperature
of -10.degree. C. to 10.degree. C.; the reaction in the second step
is preferably performed at a temperature of 0.degree. C. to
40.degree. C.; and the reaction in the third is preferably
performed at a temperature of 50.degree. C. to 90.degree. C.
[0036] The present invention is further described by the following
non-restricting examples.
EXAMPLE 1
[0037] The aforementioned compound (I-1) of the invention was
prepared according to the following scheme: 11
[0038] 1) Preparation of Compound 3
[0039] In a three-necked flask were placed 103.5 g of Compound 1
and 680 mL of acetone. The content was chilled to -5.degree. C. by
placing the flask in an ice-acetone bath. To the chilled content
was dropwise added under stirring an aqueous solution of 101.9 g of
Compound 2 and 58.3 g of sodium carbonate in 960 mL of water for a
period of one hour. The temperature of the flask content increased
to -1.degree. C. After the dropwise addition was complete, the
ice-acetone bath was removed, and the flask content was further
stirred for one hour. The precipitated crystalline product was
collected on filter by suction, to obtain the desired Compound 3.
Thus obtained product was submitted to the next step without drying
and purifying.
[0040] 2) Preparation of Compound 4
[0041] In a three-necked flask were placed the Compound 3 obtained
above and 1.9 L of water. The content was stirred on a water bath,
and to the stirred content was added 68.8 g of taurine. Further, an
aqueous solution of 58.3 g of sodium carbonate in 275 mL of water
was dropwise added for a period of one hour under stirring. After
the dropwise addition was complete, the water bath was removed and
the stirring was continued for 3 hours. To the stirred content was
added 550 g of sodium chloride, and the stirred is continued for
one hour. The precipitated crystalline product was collected on
filter by suction, to obtain the desired Compound 4. Thus obtained
product was submitted to the next step without drying and
purifying.
[0042] 3) Preparation of Compound (I-1)
[0043] In a three-necked flask were placed the Compound 4 obtained
above and 825 mL of water. The content was stirred at room
temperature, and to the stirred content was dropwise added 125.3 g
of Compound 5 at room temperature, while the stirring was
continued. After the dropwise addition was complete, the content
was stirred at an inner temperature of 85.degree. C. for 3 hours.
The reaction mixture was concentrated in a rotary evaporator. When
the residual content reduced to approximately 800 mL, a crystalline
product precipitated and the concentration procedure was stopped.
The content was then stirred with chilling with ice, and the
precipitated crystalline product was collected on filter by
suction. To thus obtained crystalline product was added 1.5 L of
methanol, and the resulting mixture was stirred for one hour under
reflux. The reaction mixture was cooled to room temperature, and
subjected to filtration using suction, to obtain 206.0 g (yield:
72%) of the desired Compound (I-1).
.lambda..sub.max(H.sub.2O)=346.3
nm(.epsilon.=4.83.times.10.sup.4)
[0044] The obtained product of Compound (I-1) had a purity of 96.0%
(determined by liquid chromatography).
[0045] The liquid chromatography was carried out under the
following conditions:
[0046] Column: TSK-gel ODS-80 (available from Toso Co., Ltd.)
[0047] Eluents:
[0048] Eluent A (20 mL of PIC A reagent, available from Waters
Corp., was added to 1 L of water)
[0049] Eluent B (20 mL of PIC A reagent was added to a mixture of
800 mL of methanol and 200 mL of water)
[0050] Eluent A/Eluent B=50/50 (0 min.).fwdarw.0/100 (35 min.)
[0051] Detecting wavelength: 346 nm
[0052] The purity was determined from a peak area of the
chromatographic chart.
EXAMPLE 2
[0053] The aforementioned compound (I-4) of the invention was
prepared according to the following scheme: 12
[0054] In a three-necked flask were placed Compound 4 which had
been prepared in the same manner as in Example 1 (i.e., same scale
and same synthetic process) and 825 mL of water. The content was
stirred at room temperature, and to the stirred content was
dropwise added 144.6 g of Compound 6 at room temperature for 10
minutes, while the stirring was continued. After the dropwise
addition was complete, the content was stirred at an inner
temperature of 85.degree. C. for 3 hours. The reaction mixture was
concentrated in a rotary evaporator. When the residual content
reduced to approximately 900 mL, a crystalline product precipitated
and the concentration procedure was stopped. The content was then
stirred with chilling with ice, and the precipitated crystalline
product was collected on filter by suction. To thus obtained
crystalline product was added 1.5 L of methanol, and the resulting
mixture was stirred for one hour under reflux with heating. The
reaction mixture was cooled to room temperature, and subjected to
filtration using suction, to obtain 216.5 g (yield: 78%) of the
desired Compound (I-4).
.lambda..sub.max(H.sub.2O)=346.5
nm(.epsilon.=4.77.times.10.sup.4)
[0055] The obtained product of Compound (I-4) had a purity of 94.4%
(determined by liquid chromatography which was performed in the
same manner as in Example 1).
EXAMPLE 3
[0056] The aforementioned compound (I-11) of the invention was
prepared according to the following scheme: 13
[0057] In a three-necked flask were placed Compound 4 which had
been prepared in the same manner as in Example 1 (i.e., same scale
and same synthetic process) and 825 mL of water. The content was
stirred at room temperature, and to the stirred content was
dropwise added 144.4 g of Compound 7 at room temperature for 10
minutes, while the stirring was continued. After the dropwise
addition was complete, the content was stirred at an inner
temperature of 85.degree. C. for 3 hours. The reaction mixture was
concentrated in a rotary evaporator. When the residual content
reduced to approximately 800 mL, a crystalline product precipitated
and the concentration procedure was stopped. The content was then
stirred with chilling with ice, and the precipitated crystalline
product was collected on filter by suction. To thus obtained
crystalline product was added 1.5 L of methanol, and the resulting
mixture was stirred for one hour under reflux with heating. The
reaction mixture was cooled to room temperature, and subjected to
filtration using suction, to obtain 249.7 g (yield: 85%) of the
desired Compound (I-11).
.lambda..sub.max(H.sub.2O)=354.5
nm(.epsilon.=4.92.times.10.sup.4)
[0058] The obtained product of Compound (I-11) had a purity of
97.3% (determined by liquid chromatography which was performed in
the same manner as in Example 1).
EXAMPLE 4
[0059] The aforementioned compound (I-22) of the invention was
prepared according to the following scheme: 14
[0060] In a three-necked flask were placed Compound 4 which had
been prepared in the same manner as in Example 1 (i.e., same scale
and same synthetic process) and 825 mL of water. The content was
stirred at room temperature, and to the stirred content was
dropwise added 268.5 g of Compound 8 at room temperature for 10
minutes, while the stirring was continued. After the dropwise
addition was complete, the content was stirred at an inner
temperature of 85.degree. C. for 3 hours. The reaction mixture was
concentrated in a rotary evaporator. When the residual content
reduced to approximately 900 mL, a crystalline product precipitated
and the concentration procedure was stopped. The content was then
stirred with chilling with ice, and the precipitated crystalline
product was collected on filter by suction. To thus obtained
crystalline product was added 1.5 L of methanol, and the resulting
mixture was stirred for one hour under reflux with heating. The
reaction mixture was cooled to room temperature, and subjected to
filtration using suction, to obtain 302.9 g (yield: 88%) of the
desired Compound (I-22).
.lambda..sub.max(H.sub.2O)=348.6
nm(.epsilon.=4.36.times.10.sup.4)
[0061] The obtained product of Compound (I-22) had a purity of
96.1% (determined by liquid chromatography which was performed in
the same manner as in Example 1).
EXAMPLES 5 and 6
[0062] The aforementioned Compound (I-2) and compound (I-12) were
prepared in manner similar to those described in Examples 1 to
4.
[0063] EXAMPLE 7
[0064] Compounds I-1, I-2, I-4, I-11, I-12, and I-22 obtained
above, and the Comparison Compounds a, b, c and d were subjected to
evaluation of solubility in water.
[0065] Water (100 mL) was added to 20 g of each sample, and the
mixture was placed on a warm bath (at 40.degree. C.), and stirred
using a magnetic stirrer, so that the added sample was dissolved in
the warm water. Then, the obtained aqueous solution was placed on
an ice bath under stirring.
[0066] The conditions of the aqueous mixture in the dissolving
procedure and the aqueous solution on the ice bath were observed
for evaluating solubility in water at 40.degree. C. and 0.degree.
C. The results are seen in the following Table.
1 Compound Solubility at 40.degree. C. Solubility of 0.degree. C.
Comp. I-1 dissolved within 120 sec. No deposition within 180 sec.
Comp. I-2 dissolved within 150 sec. No deposition within 180 sec.
Comp. I-4 dissolved within 150 sec. No deposition within 180 sec.
Comp. I-11 dissolved within 120 sec. No deposition within 180 sec.
Comp. I-12 dissolved within 140 sec. No deposition within 180 sec.
Comp. I-4 dissolved within 140 sec. No deposition within 180 sec.
Comp. a some insoluble remained at 300 sec. Not examined Comp. b
some insoluble remained at 300 sec. Not examined Comp. c dissolved
at 200 sec. Deposition found at 120 sec. Comp. d dissolved at 180
sec. Deposition found at 150 sec. 15 Comparison Compound a 16
Comparison compound b 17 Comparison compound c described in DE
1946316 18 Comparison compound d described in Japanese Patent
Application No.6-332127
[0067] EXAMPLE 8
[0068] In 1 mL of water was dissolved 10 mg of each of Compounds
I-1, I-2, I-3, I-4, I-5, I-11, I-12, I-13, I-14, I-21, and I-22.
The aqueous solution was diluted with methanol to give 5 mL of an
aqueous methanol solution.
[0069] The resulting aqueous methanol solution was applied on to a
filter paper sheet, and the paper sheet was dried. Thus treated
filter paper sheet was irradiated with a UV light (.lambda.=254
nm). All paper sheets emitted blue fluorescence.
* * * * *