Note: Descriptions are shown in the official language in which they were submitted.
`` 1077489
The present invention relates to novel benzofuran derivatives, a
process for their preparation and their use as optical brighteners.
It has already been known to prepare symmetrical 2,5-bis-[benzo-
furyl-~2~-1,3,4-oxdiazoles (German Offenlegungsschrift No. 2,031,774) and to
use them as optical brighteners for organic materials.
The present invention provides colorless to slightly yellow benzo-
furan derivatives which fluoresce in solution in a range of from about 410 to
450 nm. Accord~ng to the invention there is provided a compound of the formula:
Q)~U~-o~LDl~r
wherein P and Q are Cl-C4-alkyl, Cl-C4-alkoxy, phenyl, alkali metal salt of
sulfonic acid, Cl-C4-carboalkoxy, halogen or P and Q together form a fused
benzene ring; R is hydrogen or Cl-C4-alkyl and D is a direct bond or a group
of following formulae:
-CH-CH-, -C-C-, ~3, _~, ~ ,
~ , ~ , ~ , ~ CH=CH-,
I; .
CH=CH ~ , ~ CH=CH- or -CH=CH ~ CH=CH-.
~ Non-chromophoric substituents, i.e. preferably lower alkyl, alkenyl,
¦ alkoxy, aryl, preferably phenyl groups, optionally functionally modified carboxy
or sulfo groups, acyl, acylamino or sulfonyl groups, as well as halogen atoms,
may be bound to
- 2 -
,
, : . .: , - ,
- -. : : ~ : - :
.
, . ~ - ,
.
.
~- . . . . .
.
. .
. 1077489
-
the aromatic ring system A. It is also possible that several of
the above groups, which are identical or different, are bound
to A at the same time.
The expression of "lower" used in connection with alip-
hatic radicals is to designate groups having up to 4 carbon atoms.
In the definitions given for A and R~ functionally modi-
fied carboxy groups are to designate first of all the salts there-
of with colorless cations, alkali metal or ammonium ions being
preferred; furthermore, there are to be understood particularly
the cyano group, the carboxylic acid ester group or the carb-
oxylic acid amide group. By carboxylic acid ester groups, there
are to be understoot in particular those of the general for~ula
COOR , in which Rl represents a phenyl radical or an optionally
branched lower alkyl group, these radicals possibly containing
, further substituents, such as a dialkylamino, trialkylammonium
or alkoxy group of a preferably low molecular weight. By a
carboxylic acid amide group there is to be understood in par-
ticular a group of the formula CoNR2R3, in which the radicals
R2 and R3 are hydrogen atoms or lower, optionally substituted,
alkyl groups, which may also form a hydroaromatic ring together
with the nitrogen atom, furthermore, acid hydrazides of the
formula CoNHNR2R3, in which R2 and R3 are defined as above, and
the analogous thio derivatives. -
In a manner analogous to the above specifications, a
functionally modified sulfo group is meant to designate the salts
with colorless cations, preferably alkali metal or ammonium ions,
and also those derivatives in which the S02 group is bound
to a hetero atom, as is the case with the sulfonic acid ester
group and with the sulfonamide group. By sulfonic acid
-- 3 --
.. . ..
- ~ . , : . . : .
- . . : , ,
1077489
ester group there is to be understood in particular a group of the formula
S020Rl, in which Rl is defined as above, and by sulfonic acid amide group
there is to be understood a group of the formula So2NR2R3, in which R2 and
R3 have the above-specified meanings.
By acyl group there is to be understood in particular a group
of the formula CoR4, in which R4 stands for an optionally substituted,
preferably lower alkyl radical or phenyl radical.
By sulfonyl radical there is to be understood in particular a
radical of the formul~ S02R , in which R5 stands for an optionally substitut-
ed lower alkyl or phenyl group, this group possibly containing as substituent
preferably a lower dialkylamino, trialkylammonium, acylamino or sulfo group.
Of the compounds of the general formula (1), those compounds areparticularly interesting which correspond to the general formula t2)
.
e ~ (z~,
Q Q
wherein
E represents one of the following groups:
-C -C- , -CH~CH ~ CH=CH- , ~ CH=CH-
- , . . - -, ........................ . ~, ...
, . : .. . ,, . . - ~ ,
" . . .. ..
. . HOE 75./~ ~62
~-' 1077489
preferably
15~ -, '~ , ~ )
in particular a direct bond or
-CH=C~- , ~ ,
.
~ CH=CH ~ , ~ C~=CH- ?
T represents hydrogen or halogen atoms, lower alkyl groups~
: . optionally functionally modified carboxy or sulfo groups or
phenyl groups,
P and Q represent, independently from each other, hydrogen -
- or hal.ogen atoms, lower alkyl, alkoxy or phenyl
- groups, optionally functionally modified carboxy or
sulfo groups, or P and Q together stand for a lower
alkylene group or a fused benæene nucleus. .
Due to the significance with regard to their application,
; those compounds of the general formulae (1) and (2) are to be
mentioned in particular which correspond to the generaI
formula-.(3):
~ ~ ~ . (3)
Q Q
_ ,
29~ :
: - - 5
-, ~, . -
. - . . ,
.
. , ' ' ,' , ~ . , ' ' ' .: '
.
. .. . .
HOE i~/F 062
1077489
~ .
E, P and Q have the meanings specified in the general
formula (2),
X represen~s hydrogen atoms or lower alkyl groups.
The benzofuran derivatives of the invention can be syn-
thesized according to various methods. A preferred variant
is described in the following.
By reacting 2 moles of a carboxylic acid derivati~e of
the general formula (4)
~ ~ R
A ~ C (4)
~o
with 1 mole of a carboxylic acid derivative of the general
formula (5)
C-D-C~ (5)
wherein in the formulae (4) and (5) one of the symbols Z and
Z' stands for a halogen atom, especially chlorine, and the
other for the group -NH-NH2, in indifferent organic solvents
or solvent mixtures, optionally while using an acid-binding
agent~ ~or example a tertiary amine base, at a temperature
between room temperature and about 220C, bis-diacylhydrazides
are obtained which correspond to the formula (6)
A ~ ¢ ~ -D- ~ /~ ~ A t6)
from which the benzofuran derivatives of the invention cor-
29 responding to the general formula (~) can be prepared by
,
~ . _ t, _
. .
. . ,
'~ . '
HOE i~/F 0~2
iO77489
splitting off 2 moles of water.
In the formulae (4), (5) and (6), A, R and D have the
meanings specified in the general formula (1).
The oxdiazole cyclization processes, during which water is
split off are carried out either with ~ehydratin~ agents; s~lch
as thionyl chloride, phosphoroxychloride or polyphosphoric acid,
at a temperature in the range of from about 50C to about
220C, or the diacyl-hydrazides of the general formula (6) are
heated in indifferent sol~ents or solvent mixtures in the
presence of acid catalysts, such as, for example, organic
sulfonic acids, Lewis acids or mineral acids, in particular
p-toluene-sulfonic acid, boric acid or ZnCl2.
As indifferent solvents, there may be used, among others,
aromatic or aliphatic, optionally halogenated, hydrocarbons
boiling at a high temperature, for example, trichlorobenzenes,
dichlorobenzenes, xylenes, etc., or high-boiline esters of
aromatic carboxylic acids, such as benzoic acid-methylester.
Generally, the cyclization reactions are carried out at a
temperature in the range of from about 150C to about 250C.
As carboxylic acids of the general formula (4a)
.
A ~ COOH (4a~ ,
which are at the basis of the acid halides and/or hydrazides of
the formula (4), there may be used, for example:
- - 7 -
.
- ,. . ..
.. - . . . . .
- ..
.
.. . . ~ .. . . ~,... -.
.: :
. - . .
HOE 75/F 062
77489
~CQOH Hs~`~OOH , ~cc~soH
H;sC" ~:0011 ~C ~COOH b~COOH
--- . ~ ~H3
~ CH5 H3 C ~ CH3 ~
'' H3C~COOH .H3C~)JI~COOE ~C~COOH
.
pH5 t~Hs
- ~COOH HsC ~LbOOE ~ ~ s
,~ . . C~;s . .
,! -: 1 5
, ~ ~ (C~ C~Db (~b )~5 0~COOil
.,~, ~ .
o~ CHs ~C~H6 ,[~
COO~ COOH Cl OOH
.~ , ' .
C C OOH CN~b OOH Cl~C OOH
.
Cl~COOH ~bOOH
i : C l
29
..
: j -- 8 --
` :'. .' ~
... ' ~ :
. .. . . .
': . : ... ..
: . - , .. . ..
HOE 75/F 062
~ 1077489
~ ' , ,
~COO~I CEIS~ COOH ~COOH
H6 C2~3~ C~3 ~D~ CH5 0 ~D~
COO~I OOH CHs O COOH
As carboxylic acids of the general formula (5a)
- ~Q ~0
0 ~0 (~) ~
which are at the basis of the acid halides and/or hydrazides of
the formula (5), the following may be used~ for example:
HO2C-CO2H ~02C-C~=C~I-CO2II HO2 C-C~C-CO2E~
1 5 .
2C~co2~ HO2C~co2~ Eo2C4~cE=cH-co2H
~02C~ch=cH-~3cooH XO2C-CH=Cl~CFi=CH-CO2n
~2G~co2E ~2C~ Fl02C~
6~ ~CO2E . CO2H
HO2C~co2~ HO2C~co2H . H2C J~c02~
The reaction products of the abo~e-mentioned processes may
of course be subjected to further known modifications, for
example~ they may be sulfonated by means of sulfonating agents,
29 such as H2S04, mixtures of H2S04 and S03 or chlorosulfonic acid;
_ g _
~_.~...
.
,, . . - . . .. .
. - . . . - : . , . ~ ~. : -
. . ~, . .. . .
,. -
~ ~2
1077489
furthermore, they may be subjected to those modifications
which - starting with sulfo or carboxy-containing molecules,
for example - lead to compounds containing functionally modi-
fied sulfo or carboxy groups, and/or the said groups may be
modif ed to gi-v-c othGr gruups ul ~iis kind or tne free acids.
Furthermore, it is possible, for example, to introduce
chloromethyl groups or to oxydize methyl groups in known
manner. In the same way, the reaction products may be halo-
genatedj and the halogen atoms introduced may be further
reacted, for-example, chlorine or bromine may be exchanged for
the -C-N group or the amine function.
Due to their fluorescing capacity, the novel compounds of
the invention can be used in a wide field of applica~ion.
Above all, they serve for the optical brightening of ~arious
synthetic, semL-synthetic and natural materials having a high
molecular weight.
By synthetic organic materials having a high molecular
weight there are to be understood polymerization, polycon-
densation and polyaddition products, as well as the after-
treatment products thereof, for example:
Polymers on the basis of ~ unsaturated carboxylic acids,
of olefinic hydrocarbons or of halogenated hydrocarbons (such
as polyolefins, polyvinylchloride, polyvinylidene chloride,
polyacrylonitrile, and others),
- 10 -
~ . ~ .
'
'
. . -- .
HOE ;~/F 062
-- " 1077489
polycondensates on the basis of bi- or polyfunctional
compounds with condensable groups, or their homo- and co-
condensation products (such as polyesters, polyamides, maleinate
resins, polycarbonates, silicone resins, and others),
polyaddition products, such as, for example, cross-linked
or non-cross-linked polyurethanes as well as epoxy resins.
As semi-synthetic organic materials there may be mentioned,
for example, cellulose esters and cellulose ethers, nitro-
cellulose, regenerated ce~lulose and plastic materials on the
basis of casein.
Natural materials which can be brightened optically are,
for examp]e, protein materials, such as wool, si]kand leather;
cellulose materials, such as cotton, paper, wood paste in a
fine distribution; moreover caoutchouc, guttapercha or balata.
The organic materials to be brightened optica~ly may be
present in various processing states (raw materials, semi-
finished goods or finished goods) and states of aggregation,
for example 9 as plates, sheets, shaped articles, chips, granules,
foam plastics; films, foils, coating materials~ ribbons; threads,
fibers, for example, in the form of endless threads, staple
fibers, flocks, yarns, ropes, twisted yarns, fiber fleeces,
felts, cotton wool, textile fabrics, bonded fabrics and knitted
fabrics; furthermore, they may be present in the form of
powders, cements, pastes, waxes, adhesive and putty materials,
etc.
It is of course possible to use the novel optical brigh-
teners also in any case where organic materials of the kind
specified above have been combined with inorganic materials
29 ~ in any manner.
_ 11 - :
: "
~ HOE 75l~ 062
1077489
However, the compounds of the invention are used preferably
for the optical brightening of fibers, textile materials,
plastics and paper.
The anionic compounds of the invention which are soluble
in wat~r ~re p~rticular]y suitable for the optical brightening
of native and regenerated cellulose fibers and of wool and
synthetic polyamide fibers.
Those compounds of the invention which are insoluble in
water and which are suita~ble particularly for the optical
brightening of polyester and polyamide fibers, as well as of
cellulose fibers, regenerated cellulose fibers and of ~hose
cellulose and regenerated cellulose fibers which have been
finished with synthetic resins in order to obtain easy-to-care
properties, by themselves or in admixture with synthetic
15 ~ fibers, may be used while being dissolved in organic solvents,
or in the form of an aqueous dispersion, advantageously with
the addition of dispersing agents. As dispersing agents there
may be used, for example, soaps, polyglycolethers derived from
fatty alcohols, fatty amlnes or alkyl phenols, waste liquors
of cellulose sulfite or condensation products of optionally
alkylated naphthalene-sulfonic acids with formaldehyde.
The compounds of the invention are distinguished in par-
ticular by the fact that they may be used in the presence of
oxid~tive and reductive bleaching agents, for example, hydrogen
peroxide, sodium hypochlorite and sodium chlorite, as well as
sodium hyposulfite; without any adverse influence on the
optical brightening effect. The optical brighteners may be
combined with other finishing agents to improve the effect
29 and to facilitate the process. Agents of this kind are,
- 12 -
.
.. . .
- - ~ ,
:
'
` HOE 75/~ 062
~```` 1077489
for example, retarders, carriers, dispersing agents, softeners,
compounds having an oleophobic and hydrophobic effect, pre- -
paration-agents, emulsifiers, washing and wet-ting agents.
Particularly good brightening effects are sometimes ob-
tained. if the comnounds Qf the `n~.~entien ~re combincd i'h
other optical brighteners. Such combinations are especially
interesting, if the shade produced by the brightening effect
i8 to be changed.
The brightening of the~fiber material with the aqueous or
optionally organic brightening bath is carried out either accord-
ing to the batchwise exhaustion method at a temperature of pre-
ferably from about 20 to 150C or under the conditions of
~ thermosoling, in which process the textile material is brought
; to a moisture content of from about 50 to 120 % with the
brightening solution and/or dispersion, by impregnation and
squeezing-off, or by spraying. Subsequently the textile
material is subjected, for about 10 to about 300 seconds, to
a high-temperature treatment, preferably by means of dry heat
of from about 120 to about 240C. It is ~lso possible to
combine this thermosoling process with other finishing
operations, for example, the finishing with synthetic resins
~ to obtain easy-to-care properties. The brighteners of the in-
; vention are marked by a good fastness to the catalysts and
additives common for this process, such as magnesium chloride,
zinc nitrate or polyethylene dispersions.
Benzofurans of the general formula (1) may also be added
to detergents. These latter substances may also contain the
common filling and auxiliary agents, such as alkali metal
29 silicates, alkali metal polyphosphates and alkali metal poly-
- 13 -
. . ' ... ...
` ~E~ _062
1077489
,_, .
metaphosphates, alkali metal borates, alkali metal salts of
carboxymethyl cellulose, foam stabilizers, such as alkanol-
amides of higher fatty acids, or complexing agents, such as
soluble salts of ethylene-diamine-tetraacetic acid or of di-
ethylene-triamine-pentaacetic acid. as well as chemical
bleaching agents, such as perborates or percarbonates. Very
good results are also obtained, in the case of detergents
containing perborates, in the presence of perborate acti-
vators. Nor do the common disinfectants used in detergents
adversely affect the brightening effects of the compounds of
the invention.
Furthermore, the compounds o~ the invention may be added
to high-molecular-weight organic materials before and/or
during the forming process. Thus, for examplej they may be
added to the moulding material, if ~ilms, foils, ribbons or
shaped articles are produced, or they may be dissolved in the
spinning solution before spinning. In the case of polyamide-6,
polyamide-6,6 or linear polyesters of the polyethylene-glycol
terephthalate type, for example, suitable compounds may also
be added to the starting materials having a low molecular
weight, prior to polycondensation or polymerisation.
Those compounds of the invention which have been sub-
stituted by one or preferably two carboxy or carbalkoxy groups~
may be bound to linear polyester molecules and synthetic poly~
; 25 amides by an ester or an amide bond, if they are added to
these materials under suitable conditions, or are preferably
added to their starting compounds. Brighteners incorporated in
the substrate in this manner by a chemical bond are distin-
29 ~ guished by an extremely high fastness to sublimation and to
- - - 14 -
- - - - - ~
..
-
'. ` ' ~ ' ' ~:
HOE 75L~ 062
1077489
,
solvents.
Olefinically unsaturated compounds of the invention which
contain, in addition to the fluorescing system, at least one
polymerizable olefinic double bond may be used for the pre-
paration of fluoresing polymers and/or polymer mixtures by
being polymerized, while maintaining the fluorescing system,
as such or in admixture with other monomer or polymer vinyl
compounds. These fluorescing polymers may subsequently also
be mixed with non-fluorescing ones. Polymers which have been
brightened optically in this manner are marked by a high
degree of whiteness. Moreover, a high fastness to subli~ation
and to solvents is ensured due to the chemical bond between
the brightener molecules and the polymers.
The amount of the compounds of the general formula (1) to
be used according to the invention, calculated on the material
to be brightened optically, may vary within a wide range, de-
pending on the field of application and the desired effect.
It can easily be determined by means of simple preliminary tests
and is generally in the range of from about 0.01 to about 2 %.
The following Examples serve to illustrate the invention.
E X A M P L E 1:
_ . _ _ _
32.5 Grams o~ benzo~uran-2-carboxylic acid-hydrazide (100)
were dissolved in 1000 ml of o-dichlorobenzene, and at 120C
9 ml of oxalylchloride were added dropwise. The mixture was
heated for another 30 minutes at 120C, then it was allowed
to cool to room temperature, was suction-filtered, washed with
methanol, and the white powder obtained was dried in vacuo
at 60C.
29 Yield: 40.7 g of compound (101)
- 15 -
- -
.. . .
. HOE 75~ û62
1077489
~ Melting point: 332 - 334C (raw product)
~$C~ o,C~-~C~¢3 (101),
8.0 Grams of bis-diacyl compound (101) were refluxed for
4 hours in 59 ml of phosphoroxychloride, were then added to
- 500 g of ice, were suction-filtered, washed until neutral and .
` dried ln vacuo at 60C.
: 10 Yield: 5.6 g o~ compound (102)
The compound could be recrystallized from DMF.
Melting point: 326 - 328C.
Analysis: C20H1004N4 (370 3)
. Calc.: C 64.86 H 2.72 N 15.13
!` 15 Found: C 64.6 H 2.8 N 14.9
N-~ ~ (102~.
In an analogous manner, the Examples 2 to 8 speci~ied
in Table 1 were synthesized.
-C~. T-ble 1 -
''
'~
~ 16 -
. . . .
~~t=` .~
" ' ' ' '
,,
_ 013 751F 062
1077489
--` .
l ~ ,
F~ N O~
. ~
bO _ 0 ~ .
~ , "~ ~ ~ W
,~ I ~ ' ~ ~ I O
2~ ~' ~
. .. ._ .. __ .
r- t_
~0 Z ~l O ~1 0 ~) ~ N r~ 1 O ~1 0
~t ~ ~ ~ ` ~J ~-i ~ r~ ~ 1~ ~ ~ ~i ~1
S~ - ~ ~
r1 t~ ~ ~; ~ ~ r~ O~ O
~" ~ ~ ~ ~ N
~0 ~1 ~ '
K~ 0
~o ~o u~ ~o a~
_ ~o ~o ~o~o~o ~o ~o ~o ~ ~-~
d ~ 'd
~3 S~ O ~ O~ ,
.~ O ~lS ' O ~d O t~ O ~ o 0 o td
a) ~ .. _ 0~-- 0~-- 0~-- 0~ _ oD oD-- o~
:~ ~ ~ o ~ ~ 'P ~ ~ ~ ~ s~ N
~ ~ D O F D o F D
, ~ ~. . .. _ ... . _ . __ ___
F~l F O O O o O O O
. ~ E4 ~ _
~, u~ .~ ~ ~ ..
. ~) i~ E~~3 F ~ ~ F ~
1 -- N
_ - - - h - -
1~1 U~ _ _ ~
~ ~1 ~ . . ' .
. ~ ~ ~ o
;~ _ ~ .
-- 17 --
. . .
, .. , .. . ~ .
- . .
. . . . - . '
,, . . ; ' '. ~ ' ''
: ' . . . -
HOE 75/F 062
la774ss
E X A M P L E 9:
17.6 Grams of benzofuran-2-carboxylic acid-hydrazide were
dissolved in 500 ml of trichlorobenzene, at 120C 7.6 g of
fumaric acid-dichloride were added dropwise, and the mixture
wae continued +o bQ stirrQd for 15 mi r.-~tes at 12QC. The
reaction mixture was then heated to 210C, and 30 ml o~ thionyl-
chloride were added dropwise within 3 hours. After the mix-
ture had been allowed to cool t~ room temperature, i-t was
suction-filtered. The filter residue was washed with methanol
and was dried.
Yield: 13 6 Grams of compound (103)
The compound could be recrystallized from 1-chloronaph-
thalene; melting point: above 360C.
AnalysiS: C22H12N44 (~9
Calculated: C 66.67 H 3.05 N 14.14
Found: C 66.7 H 3.2 N 13.4
~ ~ C~=C~ ~ ~ ~ (103
E X A M P L E _10_
8.3 Grams of terephthalic acid-dichloride, 17.6 g of benzo-
furan-2-carboxylic acid-hydrazide and 13 g of N,N-dimethyl-
aniline were refluxed for 1 1/4 hours in 300 ml of chloro-
benzene. The mixture was allowed to cool, the precipitate
was suction filtered, was washed with chlorobenzene, sus-
pended in water, and the adhering chlorobenzene was distilled
with steam. 5ubsequently the mixture was suction-filtered,
the white powder was washed with water and dried in vacuo
at 60C.
- 18 _
'
~,
HOE 75LF ~62
1077 489
Yield: 21.3 g of compound (104)
Melting point: 302 - 305C
~ ~ O 0~ ~ ~ O 0~ ~ (104~.
5 Grams of compound (104) were heated, together with 0.5 g
of p-toluene-sulfonic acid, for 1 hour at a temperature in
the range of from 210 to 220C, in 60 ml of trichlorobenzene,
in which process about 25 ml of a mixture of trichlorobenzene
and water were distilled off. After the reaction mixture had
been allowed to cool to room temperature, the crystal paste .
was suction-filtered, was washed with benzene and methanol and
was dried in vacuo at 60C.
Yield: 3.2 g of compound (105)
Melting point: 351 - 352C
~ Analysis: C26H14N44 (446-40)
: Calculated: C 69.95 H 3.16 N 11.88
Found: . C 69.8 H 3.2 N 12.2
~ ~ ~ (lU5
E X A M P L E 11-
17.6 Grams of benzofuran-2-carboxylic acid-hydrazide,
12.7 g of naphthalene-dicarboxylic acid-dichloride and 16 g of
N,N-dimethylaniline were heated at a temperature of from 100
to 110C for 2 1/4 hours, in 200 ml of o-dichlorobenzene;
subsequently the mixture was heated to 170C, and within
30 minutes, 24 g of thionylchloride were added dropwise. After
29 having been cooled, the precipitate was suction-filtered, was
. - 19 _
' J
' " ' ' -' : :
." ' ' ' ~
"
~, ' , ' .
:,.' '' ' ,
EIOE ~ F 062
. _ _ _ _ _ _
_~ 1077489
washed with methanol and dried.
Yield: 11.8 g of compound (106)
Melting point: 323 - 324C (recrystallized from DMF)
Analysis: C30H16N44 (496.46)
Caleulated- ~ 72-57 H 3~24N 11.28
Found: C 72.0 H 3.2N 11.0
~ , r~ ,. (106) ,
E X A M P L E 12:
.
17.6 Grams of benzofuran-2-carboxylic acid-hydrazide,
14.0 g of 4,4'-diphenyldicarboxylic acid~dichloride and 16 g
of pyridine were heated in 550 ml o~ toluene for 3 hours at
110C. 24 Grams of thionylchloride were added, and the
mixture was refluxed for another 1 1/2 hours. After having
been cooled, the precipitate was suction-filtered, was washed
with toluene and methanol and dried.
Yield: 24 g of compound (107).
The compound could be recrystallized from benzoic acid-
methylester.
Melting point: above 360C
Analysis: C32H184N4 (529.49)
Calculated: C 73.56 H 3.47 N 10.72
Found: C 73.6 H 3.5 N 10.4
.
(1~7).
In an a~a1ogous manner the Examples 13 to 18 specified in
Table 2 were synthesized.
-Cf. Table 2 _ 20 _
'
' ' ' .
'
. ~
~077489
~ ....
.o ~
~ - ~
O ~ e~ D
o~ ~ ~ o ~
~ ~ ~ U~ o ~ o
r~ ~ ~ ~ ~ V I `D
~ ~ ~ oo ~
~ ~_ ~ `O ~5 A t-~ A
X ~ D O O
!~
O O O O ~ ~
_~ O _I O ~ ~ U~ U~ O oo ~ ~
!r .. .. .. .. .. ..
.~ ~ ~ ~ n ~ ~ ~ ~ ~ ~
b~ .~ ~ ~
.rl _I N ~ I X 1~ ~ 1~ _1 _I ~ ~
h ~ ~ .. .. .. .. .. ..
a: ~ e~ t ~ O O
r~ I` I` ~ ~ I`
o 4. Cd 2 ~ 2 ~ ~ ~. 2 ~ .~~ 'd
5~ _ .
h ~ O ~_ O ~_ O O ~_ o
~: ~ Z~ U~ Z~t ~ æ~ ~ z~ ~D z~ ~ æ~ ~o
g ~ . N O N O ~ ~ N 00 N N N N .
rl ~_I 2 U~ 2 U~ 3 ~ 2 t` 2 OD 2 ~
,, ~ _1 i~ ~ o~ U7 O~D
.
. ~ ~
3 ~ ~ 1
u~ ~ O r~
~Z O O O O o O
-æ
,
~ ~ E ~ o I ~
~ ~
~ ~ a a
~ ~ U~
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., ~ ~
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-
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la774ss
E X A M P L E 19:
In a manner analogous to Example 3, the bis-diacyl compound (108)
was prepared on the basis of benzofuran-2-carboxylic acid-hydrazide and 4-
carboxy-cinnamic acid-tichloride.
Melting point: 317 - 319C.
~H ~H NH - NH
H=CH ~ 108).
9.9 Grams of compound tlO8) weTe heated to 150C in 250 ml of o-
dichlorobenzene, and during 1 hour, 6 ml of thionyl-chloride were added drop-
wise. The mixture was heated at 150C for another 10 hours, then it was
allowed to cool to room temperature, the precipitate was suction-filtered and
was recrystallized from o-dichlorobenzene.
Yield: 6.1 g of compound (109)
Melting point: 324 - 326C
Analysis: 28 16 4N4 (472.4)
Calculated: C 71.1 H 3.41 N 11.8
Found: C 70.6 H 3.5 N 11.5
~ o~ ~ ~109)-
E X A N P L E 20:
15.3 Grams of 4,4'-stilbene-dicarboxylic acid-dichloride and 17.6 g
of benzofuran-2-carboxylic acid-hydrazide were heated in 1 1 of trichloro-
benzene for 30 minutes at 120C. Subsequently 0.5 g of p-toluene-sulfonic
acid was added, and the mixture was heated for 5 1/2 hours at a temperature of
from 210 to 220C. In the course of this process 850 ml of a
- 22 -
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E~OE 7~ ~ 062
107748~
sol~-ent-water mixture were distilled off. The reaction mix-
ture was allowed to cool to room temperature, then the pre-
cipitate was suction-filtered, was washed with methanol and
dried.
Yie1d: 25.Q g of ras~ produc~ of c^~p^~d (110~ hich cou'd be
recrystallized from DMF.
Melting point: 329 - 330 C
Analysis: C34H20N44 (548.53)
Calculated: C 74.44 ~ H 3.68 N 10.21
Found: C 73.9 H 3.6 N 10.1
~ CHaCET ~ ( 110 )
E X A M P L E_ 21:
In a manner analogous to Example 7, compound (111) was
prepared on the basis of 12.7 g of p~phenylene-diacrylic acid-
dichloride, 17.6 g of benzofuran-2-carboxylic acid-hydrazide
and 0.5 g of p~toluene-sulfonic acid in 1 l of trichloro-
benzene.
The compound could be recrystallized from DMF.
Melting point: 313 - 315C
Analysis: C30H18N44 (498.47)
Calculated: C 72.2 H 3.6 N 11.24
Found: C 72.3 H 3.7 N 11.1
CB=CII ~ CB=CB-~ ~ ~ (lll),
~ 23 -
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HOE i5/F 062
1077489
E X A M_P L_E 22:
9.4 Grams of compound (109) were introduced into 35 ml of
chlorosul~onic acid, at a temperature of from O to 5C, the
mixture was stirred for 2 hours at a temperature of from 5
to 20C, was heated for 30 minutes at 60C and was then allowed
to cool to room temperature. Subsequently the mixture was
poured onto 300 g of ice~ the colorless crystal paste ob-
tained was suction-filtered and was washed thoroughly with cold
water (up to pH 6).
The raw sulfochloride was suspended in 300 ml of water and
was hydrolyzed with 34 ml of about 2N NaOH during 5 hours at
60C, then it was neutralized. The clear light yellow solution
was concentrated.
Yield: 15.4 g (94 %) of compound (112)
~15 Melting point: > 360C; the aqueous solution was fluorescing
with an intense blue color shade.
Absorption in DMF / ~2 (3:2) : ~max = 366 ~nm~
AnalYSis: C28H14N410S2Na ( 7
contained 4.61 % of H20 and 10.05 /0 of NaCl
Calculated (84.4 %): C 41.4 N 7.0 S 8.0
Found: C 41.3 N 6.9 S 7-9
NaOs5 ~ ~ ~ ~>-CH=C~ ~ ~ SOsNa (112),
Examples 23 to 25 were prepared in an analogous manner:
E X A M P L E 23:
NaO5~ ~ SO5Na (ll3)
29 Meltlng point:> 360C; the aqueous solution was fluorescing
- 24 -
. . . . . .. . . . . ..
. . ~ . . . ~ . . : . . , : .
-. . . .
:
. .. . . .
-- 1077489
with an intense blue color shade.
Analy-si 5: C32H16N410S2Na2 (726.5g)
contained 1.5 h of H20 and 10.6 % of NaCl
Calculated: (87.9 %): C 46.4 N 6.76 S 7.75 -
Found: C 45.9 N 6~4 S 7.8.
E X A M P D E 24-
C~3
Na 05 s~3~ S05 Na (114)
Melting point: > 360C; the aqueous solution was fluorescing
with an intense blue color shade.
Absorption in DMF / H20 (3:2) :~max = 347 l~nm~
nal~sis: C34H20N4o1os2Na2 (75
contained 6.4 % of H20 and 11.1 /0 of NaCl
Calculated (82.5 %): C 44.7 N 6.1 S 7.0
Found: C 44.7 N 6.0 S 7.0
E X A M P L E 25:
NaO s ~ ~ ~ OS~ a (115)
Melting point: > 360C; the aqueous solution was fluoresoing
wlth an intense blue color shade (slightly
greenish).
Absorption in DMF / H20 (3:2) : Amax - 361 ~nm~ -
_a~ C40H18N416S4Na4 (1030.39)
contained 3.3 % of H20 and 15.0 % of NaCl
Calculated (81.7 %): C 38.0 N 4.4 S 10.2
29 Found: C 37.4 ~ 4.3 S 9.5
- 25 -
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.
HOE 7,_F 062
-"` 1077489
E X A M P L E 26:
A cotton fabric which had been previously bleached in
known manner with hydrogen peroxide was treated, in a goods-
to-liquor ratio o~ 1 : 20, with a solution containing 0.3 %
of an optical brightener o~ the formula (115), calculated on
the weight of the textile material. The bath was brought to
60C, and the mat`erial was moved mechanically in the liquor
for 30 minutes. After rinsing at a falling temperature and
drying, the cotton fabri~ showed an excellent degree of ~rhite-
ness.
E X A M P L E 27:
An unbleached knitted fabric made of cotton was treated inportions o~ 10 kilograms each for 60 minutes at 80C, in a
goods-to-liquor ratio of 1 : ZO, with a solution containing
per liter o.6 part by weight o~ sodium chlorite, formic acid
to adjust a pH value of 3.5, and 0.16 % of an optlcal brightener
of the formula (112). After the subsequent rinsing and drying,
the fabric showed a very high degree of whiteness.
- ~ ' , ... .
E X ~ M P IJ E 28:
A fabric made of polyamide-6.6 fibers was treated in the
high-temperature dyeing apparatus, in a goods-to-liquor ratio
of 1 : 10, with a solution containing 0.3 ~ of a brl~htener
o~ the formula (115). The bath was heated to 125C9 and the
material was treated in the bath for 45 minutes. A~ter rinsing
and drying~the ~nitted polyamide fabric had an excellent degree
` of whiteness.
..
. -
- 26
.
. . . . . . - . .
HOE _75/F 062
`` ` :1077489
E X A M P L E 29:
A polyacrylonitrile fabric having at least 85 % of poly-
acrylonitrile in the molecule was impregnated with a solution
containing per liter 100 g of dimethylol~dihydroxy-ethylene-
urea, in which i g OI the brighiener OI the Iormula ( 114) nad
been previously dissolved. The fabric was brought to a
moisture content of 100 % between rollers and was then dried
at 120C to a residual moisture of 3 %. The fabric thus
treated had a high degree of whiteness.
.
'
.
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-... . . . . . .
~-. . -
