CA1080718A - 2-stilbenyl-1,2,3-triazoles which contain carboxyl groups - Google Patents
2-stilbenyl-1,2,3-triazoles which contain carboxyl groupsInfo
- Publication number
- CA1080718A CA1080718A CA234,833A CA234833A CA1080718A CA 1080718 A CA1080718 A CA 1080718A CA 234833 A CA234833 A CA 234833A CA 1080718 A CA1080718 A CA 1080718A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- formula
- alkoxy
- stilbenyl
- triazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/22—Naphthotriazoles
- C07D249/24—Naphthotriazoles with stilbene radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
Abstract
Abstract of the Disclosure Process for the manufacture of 2-stilbenyl-1,2,3-triazoles of the formula by reacting a 2-tolyl-1,2,3-triazole of the formula with an anil of the formula
Description
The present invention provides a process for the manufacture of 2-stilbenyl-1,2,3-triazoles which contain carboxyl groups, novel 2-stilbenyl-1,2~3-triazoles which contain carboxyl groups and a process for optically brightening synthetic organic material which comprises the use of these novel compounds~
A number of different processes for the manufacture o stilbene compounds are kno~n, One such process of wide application has become ~nown as the "anil synthesis" (cf.
for example Helvetica Chimica Ac~a r)O, (1~67) 906 ~, 55 (1972) 818-851 and 2300-2329 and 57, (197~) 81 ff.). As condition for the course of the anil s~nthesis, hot~c-ver, the absence o~ salt-forming substituents, e.g. of ~he carboxylic acid group, in tl~e reactants has so ~ar b~en given (cf.
Helvetica Chimica Acta 509 (1967) 912 and 52~ (lg6~3j 2574).
Surprisingly, it has now been found that 2-stilbenyl-1,2,3-triazoles which contaln carboxyl ~roups can be manufac-tured in good yield by means of the anil syn~hesis. This process makes it possible to manufacture commerciallyimp3rt~llt compounds in a particularl~ advantageous manner. A substantial number of nel~ compounds, as well as of known ones which ithas hitherto only been possible to obtain in part by roundabou~
methods, can ncw be manufactured in simple manner and in improved yield.
" "
~D~ - 2 - ~ ~
.
';~ ' '.
~.: ~,.
Th~ classic process for manufacturing 2-stilbenyl-naphthotriazoles consists in starting from 4-nitrostilbene derivatives of the formula (~), reducing these to thc 4-amino-stilbenes which are then diazotlsed, coupled with 2-naphthylam-ines and then oxidis~dO It is known that 41-nitrostilbene derivatives are only ob~ained from p-nitrotoluene derivatives in accord~nce with the following r~action equa~ion in satisfactory yield if X represents an.electronegative radical, eOg. -NO2, CN, -SO20phenyl, SO3H, -COOH, -CON(alkyl)2 o~ -SO2N(al~Yl)2:
R
NO2 ~ CH3 ~ CHO ~ -~ N2 ~ CH=CH ~
X X .
~ owever, this reaction takes place with poor yield or even fails i X represents hydrogen or other non-electr~-negative substituents.
The presen~ invention àccordingly provides a process for the manufacture of 2 stilb~nyl-1,2,3-triazoles of the formul~
X \ N ~ - C~ ~ CH ~ ~ COOR
N ~
wherein A represents a benzene or naphthalene ring which is un-substituted or substituted by one or more non-chromophoric groups : selected from alkyl, fluorine, bromine, chlorine, alkoxy, alkoxy-alkoxy, aryloxy, aralkoxy, aryloxyalkoxy, alkenyloxy, aryl, alkylmercapto, alkenylmercapto, arylmercapto, arylsulphonyl, . . , cyano, carboxy, carbalkoxy, carbamoyl, sulphamoyl, sulphonyl, or methylenedioxy, and Rl represen-ts alkyl of 2 to 4 carbon atoms~ haloalkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, or phenoxyalkyl of 1 to 3 carbon atoms in the alkyl moiety, and if A represents a benzene ring sub-stituted by non-chromophoric groups, Rl can also represent hydrogen or an alkali metal, alkaline earth metal, ammonium or amine s~lt cation~ which process comprises reacting a
A number of different processes for the manufacture o stilbene compounds are kno~n, One such process of wide application has become ~nown as the "anil synthesis" (cf.
for example Helvetica Chimica Ac~a r)O, (1~67) 906 ~, 55 (1972) 818-851 and 2300-2329 and 57, (197~) 81 ff.). As condition for the course of the anil s~nthesis, hot~c-ver, the absence o~ salt-forming substituents, e.g. of ~he carboxylic acid group, in tl~e reactants has so ~ar b~en given (cf.
Helvetica Chimica Acta 509 (1967) 912 and 52~ (lg6~3j 2574).
Surprisingly, it has now been found that 2-stilbenyl-1,2,3-triazoles which contaln carboxyl ~roups can be manufac-tured in good yield by means of the anil syn~hesis. This process makes it possible to manufacture commerciallyimp3rt~llt compounds in a particularl~ advantageous manner. A substantial number of nel~ compounds, as well as of known ones which ithas hitherto only been possible to obtain in part by roundabou~
methods, can ncw be manufactured in simple manner and in improved yield.
" "
~D~ - 2 - ~ ~
.
';~ ' '.
~.: ~,.
Th~ classic process for manufacturing 2-stilbenyl-naphthotriazoles consists in starting from 4-nitrostilbene derivatives of the formula (~), reducing these to thc 4-amino-stilbenes which are then diazotlsed, coupled with 2-naphthylam-ines and then oxidis~dO It is known that 41-nitrostilbene derivatives are only ob~ained from p-nitrotoluene derivatives in accord~nce with the following r~action equa~ion in satisfactory yield if X represents an.electronegative radical, eOg. -NO2, CN, -SO20phenyl, SO3H, -COOH, -CON(alkyl)2 o~ -SO2N(al~Yl)2:
R
NO2 ~ CH3 ~ CHO ~ -~ N2 ~ CH=CH ~
X X .
~ owever, this reaction takes place with poor yield or even fails i X represents hydrogen or other non-electr~-negative substituents.
The presen~ invention àccordingly provides a process for the manufacture of 2 stilb~nyl-1,2,3-triazoles of the formul~
X \ N ~ - C~ ~ CH ~ ~ COOR
N ~
wherein A represents a benzene or naphthalene ring which is un-substituted or substituted by one or more non-chromophoric groups : selected from alkyl, fluorine, bromine, chlorine, alkoxy, alkoxy-alkoxy, aryloxy, aralkoxy, aryloxyalkoxy, alkenyloxy, aryl, alkylmercapto, alkenylmercapto, arylmercapto, arylsulphonyl, . . , cyano, carboxy, carbalkoxy, carbamoyl, sulphamoyl, sulphonyl, or methylenedioxy, and Rl represen-ts alkyl of 2 to 4 carbon atoms~ haloalkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, or phenoxyalkyl of 1 to 3 carbon atoms in the alkyl moiety, and if A represents a benzene ring sub-stituted by non-chromophoric groups, Rl can also represent hydrogen or an alkali metal, alkaline earth metal, ammonium or amine s~lt cation~ which process comprises reacting a
2-tolyl-1,2,3-triazole of the formula (2) N
A ~ N - ~ CH3 wherein A is as defined above, with an anil of the formula t3) ~ Cl~ c N ~ ~r COORlL
wherein Rl is as defined akove and Ar represents an unsubsti~
tuted or a substituted aromatic radical, in the presence of a strongly basi.c alkali compound in a strongly polar, neutral to basic organic solvent or mixtures thereof.
:: - 4 -.... .. _ .. .. . . . .
. . : . ~, . .
. . .
~', ' "~ ' , ',: . .' '~ ' ~ . ~' ' , ' ' .
' ~ ' '' ' ' ' ' ' ' , ' ' ' ' Preferred carbamoyl and sulphamc,~l. radicals can be represented by the ormulae - CON ~ and - ~)2N~
Zl æ
respectively, wherein each o~ Z and ~1 independently repr~se~
hydrogen, preferably alkyl of 1 to 4 carbon atoms~ or together with the nitrogen atom they r~p;esent .the completion of a non-aromatic ring with 5 to 7 members, e.g. a morpholino or piperidino ring.
The term "carbc)xy" is to be understood as meallin~
herein the radical -COO~I, wherein M represents hydrogen or a salt-forming cation. Possible salt-forming cations ~I are in general ~hose of al~aline ear~h meta].s, e.g. ca~cium, barium or magnesium, as well as of alkali metals, e.g. sodiu~
or potassium, and also ammonium which is subs.ituted by alkyl or hydro~yallcyl of 1 to 4 carbon atoms or is unsubs~ituted, or amine salt~ of cyclic anlines, e.g. ~yridine, morplloline or piperidine. Besides hydrogen, M preferably represents in particular the potassiun~ and ~he sodiur.l cationO
, " ;.,~
. ' . ' ~ . ', ' - ' : . . .. - . . ..
The aromatic radical Ar is made up as a rule from one or more 6-membered carbocycles; preferably it represents a substituted or an unsubstituted naphthalene radical and especially a chlorine-substituted or an unsuhstituted phenyl radical.
An interesting process for the manufacture of 2-stilbenyl-1,2,3~triazoles of the formllla (4) ~ N ~ ~ Cll= CH ~ COORl R4 ~5 wherein Rl represents hydrogen or an alkali metal, alkaline earth metal, ammonium or amine salt cation, R2 represents hydrogen, alkoxy of 1 to 4 carbon atoms, carboxyalkoxy of 2 to 6 carbon atoms or together with R3 represents methylene-dioxy, R3 represents hydrogen, alkoxy of 1 to 4 carbon atoms, carboxyalkoxy of 2 to 6 carbon atoms, alkoxyalkoxy of 2 to 6 carbon atoms, phenoxy, phenoxyalkoxy of 1 to 3 carbon atoms in the alkyl moiety, chlorine, alkylmercapto, phenylmercapto, alkyl of 2 to 4 carbon atoms, or together with R2 represents methylenedioxy or together with R4 represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by chlorine, alkoxy of 1 to 4 carbon atoms or -SO2N\ 1 or -CON\ 1 , in which each of Yl and Y2 independently represents alkyl of 1 to 4 carbon atoms, R4 represents hydrogen or together with R3 represents the com-pletion of an unsubstituted naphthalene ring or of a naphtha-lene ring which is substituted by chlorine, alkoxy of 1 to 4 carbon atoms or -SO2N\ 1 or -CON ~ 1 , in which each of Yl and Y~ independently represents alkyl of 1 to 4 carbon atoms, .
'~. " ~ ' ,' '',' ' .
.
.' ' , ,. ' ' :
~., R5 represents hydrogen, chlor:ine, alkoxy of 1 to 4 carbon atoms, preferably methoxy, -CON\ 1 , -S02N\ 1 , in which Yl and Y2 have the meanings already assigned to them, or represents -502-phenyl, which comprises reacting a 2-tolyl-1,2,3-triazole of the formula (5) R2 ~ N
R
wherein R2, R3, R4 and R5 have the indicated meanings, with an anil of the formula (6) Arl - N = Cll ~ COOR~
wherein Arlrepresents phenyl, chlorophenyl or naphthyl and Rl has the indicated meaning.
A preferred process for the manufacture of 2-stil-benyl-1,2,3-triazoles of the formula (7) Rq\~ \` ~ CH - Cll~ ~ COOR
R3 ~ N/ \=<
I~,.13",~
. . . . : : . .
, : . . , ~, : ~. . :
: ~, . . . : ~ : .
: : : . . . , , . : : .:
::
: . . .: : : .. : -: . ' .: : . ' ' . . ~ ' ~ : . ' . :
:
:: ::: : : . :
J~ ~
wherein Ri represents a hydrogen, alkali rnetal, alkaline earth metal, ammonium or amine salt ion, R2 represents hydrogen, alkoxy of 1 to 4 carbon atoms or together with R3 represents methylenedioxy, R3 represents hydxogen, alkoxy of 1 to 4 carbon atoms, phenoxy, phenoxyalkoxy of 1 to 3 carbon atoms in the alkoxy moiety, chlorine, or together with R2 represents methy-lenedioxy or together with R~ represen-ts the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by alkoxy of 1 to 4 carbon atoms, R4 represents hydrogen or together with R3 represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by alkoxy of 1 to 4 carbon atoms, and R5 repre-sents hydrogen, methoxy or -CONYlY2, whereln each of Yl and Y2 independently represents alkyl of 1 to 4 carbon atoms which comprises reacting a 2-tolyl-1,2,3-triazole of the formula (8) R ~ / ~ ~ 3 R~ ~5 wherein R2, R3, R4 and R5 have the indicated meanings, with an anil of the ~ormula (9) 1 N Cl ~ COOR
.
.~i~ .
..
': . ~ ' ' . ~ ~
T~
wherein Arl represents phenyl, chlorophenyl or naphthyl and Rl has the meaning indicated above.
An especially preferred process for the manufacture of 2-stilbenyl-naphtho-1,2,3-triazoles of the formulae (10) ~ N / CH=CH ~ COOR
and (11) ~X ~3C~=CH {}COOR
,~ ..
1.. . . . ... . .... . . . . .
: . . .: . : .. : : . . . .
~hereill R'~' represents a hydrogen, alkali metal, an~lonium or an~ne salt ion, and R~ represents hydroge~ or alkoYy of 1 to 4 carbon atoms, is that which comprises reactin.g a 2-tolyl--naphtho 1,2,3 triazole oX ~he formula (12~ ~ \N - ~ C~l3 : ~6 ' wherein R6 has the indicated meaning, with an anil of the :Eormula . (13) h ~P`l ~ ~ = CH - ~ or .~
(143 h ~ N = CH ~ - COOR',' wherein h represen~s chlorine or hydrogen and R'l has the meaning previously assigned to it. The process for the manufacture of compounds of the formulae (10) and (11), wherein RS is hydrogen, is particularly preferred~
Also deserving of mention is the procPss for the manufacture of 2 stilbenyl-benzo 1,2,3-trl.azoles of the formula ' . . . . . .
.. . . .
:
. , ~. . . . . .
. . .
(15) ~ N _ ~ _ C~ C~ COOR~
wherein Rl, R2 and R3 have the meanings previously assigned to them, which process comprises reacting a 2-tolyl-benzo~
1,2,3-triazole of the formula (16) ~ N - ~ - Cl~3 wherein R2 and R3 have the meanings assigned to them hereirl-before, with an anil of the formula (17) h - ~ N = CH ~ COOR
wherein h and Rl have the meanings assigned to them herein~
- before~
The reaction produc~ of the formulae (1), ~4) 5 (7)~
(10), (11) and (lS) can, if appropriate, be esterified.
The esterification is carried out in a manner known per se by reacting the acid with an alkanol, alkenol, phenol, hydroxyalkylbenzene or cycloalkanol, as e.g. methano~
ethanol, n-propanol, isopropanol, n-butanol~ sec. butanol 9 i~obutanol, tert. butanol, n-hexanol, n-octanol32-ethy~e~anol, ; ; . . . :
- . . . . .
.
ethylene chlorollydrin, propylene chlorohydrin, 3-chloro~
propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ethe;, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, l-methoxy-2~propanol, butylglycolate glycolic nitrile, 3-hydroxypropion:itrile, ethyl lactate,allyl alcohol, crotyl alcohol, phenol, o , m- and p-cresol,o chloro-phenyl, tert. butylphenol, benzyl alcohol, 2--phenoxyethanolS
l-phenylethanol, cyclopentanol and cyclohexanol. The esteriIi-cation is effected, for example, in the presence of an acid catalyst, such as sulphuric acidg hydrogen chloride or p-toluenesulphonic acid, optionally with simultaneous removal of the water of reaction as an azeotrope with a suitable entrainer, as e.g. perchloroethylene, xylene, chlorobenzene or higher boiling petroleum ether fractions. Ho~7ever~ it ~s also posslble to manufacture the esters by ~ay of the corresponding carboxylic chlorides by reacting the carboxylic acids first ~ith thionyl chloride, phosphoroxy chloride etc.
and heating the reaction products, with or ~ithout isolating them first, with the alcohols or phenols.
The process according to the invention also makes it possible to manufacture in good yield interesting compounds of the formula (1), wherein the benzene nucleus does not necessarlly contain electronegative substituents.
Within to scope of compounds of formula (7) and of .. , .. ... . ~ .
their esters the co~pounds of particular interest are a3 2-s~ilbenyl-1,233-tria~oles of the ~orm~lla , . :,: .
,: . , , . . :
~18) N
A ~ C~-l = C~i - ~ COOR~
wherein A represents a benzene or naphthalene ring which i5 unsubstituted or substitu~:ed by non~chromophoric groups and R' represents all~l of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoallcyl of 1 to 4 carbon a~oms~ alkenyl of 3 or 4 carbon atoms or phenoxyall~yl of 1 to 3 carbon atoms in the alkyl moiety and in case A represents a benzene ring subscituted.
by non~chromophoric groups R' also represents hyd.rogen or a salt forming~cation, b) 2-stilbenyl-1~2,3-triazoles of the formula ~ / - ~ Ci~ = Cl~ _ ~ COOR" , wherein Rl' represents alkyl of 2 to 4 carbon atoms) and c) the compound o the formula (20) ~ / ~ -Cll = Cll - ~ CC2~5 and for the optically br;ghtening of polyesters in the spinning melt the compound.s of the form~lla ~ ~ ~ ~.3 - :
~ '- , ' . . . , : . ' .
. . .
R3 ~N~ ~U=C~I.~COOR'i ' wherein Rl ' represents a hydrogen, ~lkalimetalg ammonium, ~min~ s~.lt ion or alkyl with 1 to 4 carbon atoms, R'2 represents hydrogen 5 alkoxy with 1 to 4 carbon atoms or togetller with R'3 represents methylene-dio~y and R'3 represents aikoxy with 1 to 4 carbon atoms or to~ethex w~ith R'2 ~eprescnts methylen~3dioxg~, and p.-articulary those compounds o~ the formula R2~ ~ ~ ~ H=~ COOH
wherein R'2' represents hydrogen or alkoxy with-l to 4 carbon stoms, particularly methoxy and R'3' represents alkoxy with 1 to 4 carbon atoms, ~articularly methoxy.
2-stilbenyl-1-,2,3-triazoles of the formulae tl~ lg3 and (~
wherein ~, R" and R"l are different rom hydrogen or a salt~rm~
ca~on can be manuactured by esteri~ication in kno~n manner ~` of the correspond;ng carboxylic acid with an alcoholg for example ethanol, n-propanol, isopropanol, n-butanol, ~ec.
butanol, isobutanol, ~ert. butallol, ethylene chlorohydrin, propylene chlorohydrin, 3-chloro-1-propanol, ethylenæ. glycol - 13 a-:
.
monomet~ 71 a-nd monoekhyl ether, ethylene glycol monobutyl ether~ e~hylene glyco'l isopropyl ether, allyl alcohol~ crotyl alcohol, 2-phenoxyethanol, 3 phenoxypropanol, l-phenylethanol~
cyclopentanol and benzyl alcoholO
` The starting materials, i.e. the compounds of the formulae (2)~ (3), (5), (6), (8), (9), (11) and (12), are kno~n or can be manu~actured in a manner which is kno~n per se. The anils of the formu'Lae (3~, (6) 5 (9) and (12) are therefore manufactured by reacting an aromatic amine or a substituted or unsubstituted naphrhylamine or aniline or an unsubstitllted or a chlorine~substituted aniline with, for e~ample, o-carbo~ybenzaldellyde, m-carboxybenzaldehyde, p-carboxybenzaldehyde, 2 carboxy-5-methoxy-benzaldehyde, 2-methyl-4-carboxybenzaldehyde,2-chloro-5-carboxybenza'ldehyd~
The manufacture of the 2-tolyl-naphthotriazoles is effected in accordance ~ith Helv. Chim. Acta 55 (1972) 849 and that of the 2-~olyl-benzo~riazoles iII accordance with Helv. Chim Acta 55 (197~) 2325.
The compounds containing methyl groups can b~
reacted with the anils in the presence of a ~uitaible stron~ly polar, neutral to alkaline organic solvent or mixtures t'hereo which do not contain atoms, in particular hydrogen atoms,th.-~can be rep:Laced by alkali metals. 'Ln practlce, suitable solvents o~ this kind are primarily dialkylated acylamides of :, . .
` " . ' ' ' ' ' : ' : '" - . : ' , : ~ ' thc ~ype (23) EalkYl)2~] ~ acyl whereill;'alkyl" represents a lower alkyl group of 1 to 4 carbon atoms, in particular a methyl group, "acyll' represents the radical of a lower carboxylic acid of 1 to 4 carbon atoms, in particular formic or phosphoric acid~ and ~ indic~tes the basicity of the acid. As important examples of such solvents there may be mentioned: diethyl formamide, dimethyl acetamide and especially dimethyl formamide and hexamethylphosphoric triamide~ Suitable solvents are also N-alkyl-lactames of 5 to 10 carbon atoms, e.gO N-methylpyrrolidone and tetra-alkylurea.s, such as tetrame~hylur~a.
As has been mentioned already, a strongly basic allcali compound is also neGessary for carrying out the reaction. Suî~able for this purpose, depending on the nature of the solvent and the reactivity of the anil, are alkali metal alcoholates or hydroxides, in particular potassium and sodium compounds of the composition ~24) KCm~ 2m-1 and ~aOCmH
` , ~' : .~-.. ~.. . .
, .~ - .. . .
respectively~ wherein m is an inte~er froi~l 1 to 6, for ~xample potassium llydroxide~ po~assiurl t~r~. butylate7 sodi~lm tert.
butylat~ or sodium methylate. When using such alkali alcoholates the process must be carried out in virtually anhydrous medium;
whereas a small water content of up to app. 15% is permissable ~hen using potasisiu[n hydroxide. It is advantageous to use potassium hydroxide and sodium methyla~e e.g. in combination with hexamethylphosphoric triamide at elevated temperatur~
e,g, at 110-130C. It is of course also possible to use miY~tures of such bases. The use of potassium tertc butylat2 is preferL-ed.
The compounds containing methyl groups are desirably reacted with the anils in ea~uivalent amounts, so tha~ there is no substantial excess of either component, although on occasion an excess of anil of up to app. 50% can often be of advantage. It is advantageous to use at least the equivalent amount o alkali compound, i~e~ at least 1 mole of a compound with e~g. one K0 group to 1 mole of aldehyde anil. When using potassium hydroxide, it is preferable to do so in ~ to 8 times the e~uivalent amount. Particularly good yields are obtained on using potassium tert. butylate in one to si~ times, preferably two to four times, ~he equivalent amount.
The reaction according to the invention can usu211y be carried out at temperatur~s in the range be~een a~out 10 and 150~C~ When usin~ par~iculclrly reactive anils and ~1.
. . , . .' " , " ' '''; ' .. ' .
, ' ' ' ~, ' .. ; ' . :
~ - \
and p~rticular]y energetic catalysts, e.g. potassium te-rt.
butylate, the reaction takes place frequently even at room temperature, in which case it is not necessary to apply heat externallyO This is especially advantageous if the reactants contain ring compounds or substitueIIts which can be easil~
opened or split off by alkali or which can be chemically changed in some other way. Thls applies, for example, to anils which contain chlorine substituents which can be easi]y split of. However, it tnost advantageous to carry out the -process at e~evated temperature, especially when using sodium alcoholates and po~assium hydroxide. For example, the reac~
mixture is heated slowly to 30 to 90C and then kept at this temperatwre for a time, e.g from-l hour to 2 hours~
The manufacture ofthe anil and the reaction thereof with the tolyl compound can alsobe carried out consecutively i~
the one reaction vessel.For example, thealdehydeis heated~h excess aniline in dimethyl formamide and the reactioll mi~ture is completely evapora~ed to dryness in vacuo. A tolylcomponent and dimethyl formamide are added and the usual procedure is carried outO
The final products can be worked up from the reaction mixture by conventional methods which are known per se. The isolation o~ the carboxylic acids in salt form is e~-Eected for example ~y precipitation with water~ while the free ~arbo~lic acids can be precipitated by acidiEicat;on with a strong mineral acidS as for example aqueous hydrochloric acid. The w ~7 _ . ' ' - " .
'' ' -cornpounds vf the ~o-rmulae (1), (4)~ (7), (10), (11) and (15) and the esters thereof are mostly useful fluorescent brightenersO They can be used in known manner for brightenirlg organic materials of high molecular we;ght of the most widely differenc kind, preferably synthetic organi.c materials, in which connection the free carboxylic acids and the esters thereo are used ~ith advantage for polyester and the carbo ~ylic acicl salts for polyamide and polyacrylonltrileD
The carboxylic acid esters are particularly suitable for brightening polyester materials by the hlgh temperature exhaustion process.
Witllout any restriction belng implied by the following classification, examples of organic materials are:
I. Synthetic organic materials or high moiecular w~ht:
a) polymerisation products based on organic compounds containing at least one polymerisable carbon-carbon ~ou~le bond, t:hat is to say their homopol.ymers or copolymers as well as ~heir aftertreatment products, ~or example, crosslinking, grating or degradation products, polymer b]ends, or products obtained by modi~ication of reactive groups, or example polymers based on ~,~-unsaturated carboxylic acids or deriva~
tives o~ such carboxylic acids, especially on acrylic compo~md for example acryl.ic esters, acrylic acid, acrylonitrile, acrylic amîdes and their derivati~es or their methacryL
.. , - :
, ...
analogues~ on o].efin hydrocarbons (for example ethylene, propylene~ styrenes or dienes and also ABS polymers), and polymers based on vinyl and vinylidene compourlds (for exa~ple vinyl chloride, vinyl alcohol and vinylidene chloride);
b) polymerisation products which can be obtained by ring opening, for example~ polyamides of the polycaprolacta~
type, and also poiymers which are obtained both by polyaddi-tion and by polycondensation., for example polyethers or polyacetals, c) polycondensation products or precondensates based on bifunctiorlal or polyunctional compounds with conc~ellsable groups~ tlleir homocondensation and co-condensation products5 and aftert:reatment products, for example polyesters, especial~
ly saturated (for example ethylene glycol terephthali.c acid polyester~ or lmsaturated (for example maleic acid~dialcohol ;
polycondensates as well as their crosslinking products with copolymeri.sable vinyl monomers), unbranched and branched (also including those based on pol~rhydric alcohols, for ex-ample alkyd resins) polyesters, polyamides (for example hexa-methylenediamine adipate), maleic resins~ melamine resins, their precondensates and analogues, polycarbonates and sili~
cones;
,, .
d) polyaddition products, such as polyurethanes (CL'05S-linked and non-crossl;nked~ and epoxide resi.ns~
.; .
.
:
'~
IIr Regenerated man--made organic materials, ~or exalr,ple, cell1l1vse esters of varying degrees of esterification (so-called 2 1/2 acetate or triacetate) or cellu]ose ethers, regenerated cellulose (viscose or cuprammonium cellulose), or their aftertreatment products, and casein plastics.
III. Natural organic rnaterials of animal or vegetable origin~ for exaslple based on cellulose or proteins, SUC'Q as cotton, wool, linen, silk, va-cnish gums, starch and caseins The organic materials to be optically brightened can be in the most diverse states of processing (raw materlals5 semi-flnish~d ~oods or ~inished goods3. On the other hand, they can be in the form of structures o~ the most diverse shapes, for example predominantly three-dimensionals~-uctures such as sheets~ profiles, injection mouldings, various ma-chined articles, chips, granules or ~oams, and also pre-dominantly two-dimensional structures, such as films3 foils laccluers, coatings and impregnations, or predominantly one-dimensional bodies, such as filaments, fib:ces~ flocks and ~iL^es. The said materials can, on the other hand? also be in ~n unshaped state, in the most diverse homog~neous or inhomogeneous forms of division, as ~or example, in the form of powders, solutions, emulsions, dispersions, latices,pastes or waxes.
--, : - , . ~ : . .. .
Fibrc ma~erials canS for example, be in the form o~
endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile ilament yarns, threads, non-wovens, felts, waddings, ~locked structures or woven textile or bonded textile farbrics, knitted fabrics and papers, cardboards or paper pulps.
The compounds to be used according to the invention are of importance, inter alia, for the treatment of organ:ic textile materials, especially woven textile fabrics. If fi-bres which can be in the form of staple fibres or endless filaments or in the form of hanks, woven fabrics, knitted fabrics, fleeces~ flocked substrates or bonded fabrics, are to be optically brightened according to the invention, this is advantageously effected in an aqueous medium, wherein the compounds in question are present in a finely divided form (suspensions, so-called microdispersions~ or optionally solutions). If desired, dispersing agents, stabilisers~
wetting agents and further assistan~s can be added du~ing tlle treatment.
Depending on the type of brightener compound used~
it can be advantageous to carry out the treatment in a neu-tral or alkaline or acid bath. The treatment is usually car-ried out at temperatures of 20 to 140~C, for example at the boiling point of the bath or near it (about 90~C).
_ 21 -J
:. . .. .
- ~ . .
' . ' ' ' ' , ~ ' ~
~.
Solutions or emulslons in organic solvents oan also be us~d for the finishing acco^ding -~o the invention of textile sub strates, as i.s practised in the dyeing industry in so--called solvent dyeing (pad~heat fixing application., or eY.haustio dyeing processes in dyeing machines).
The new fluorescent brigllteners according to the present invention can further be added to, or incorporated in, the materials before or cluring their shaping. Th~ls they C2L1 for ex2rllple be added to the compression moulding composition or injection moulding composition during the manufact-lre of films, sheets (for example ~orking into polyvinyl chloride :i.n a single roller mill) or mouldings~
If the fashioning of man-made synthetic or regenera~
ted man-made organlc materials is effected by spilm.ing proces~
ses or fîom spinning solutions/melts, the fluorescent brigh~
1. eners can be applied by the ollowing processes:
addition to the starting substances (for example mo-nomers) or intermediates (~or example precondensates or pre-polymers), that is to say before or durillg the polymerisation~
polycondensation or polyaddition, sprinkling in powder form on polymer chips or granu-les for spinlllng solut:ions/nleltsg ; - ~2 ~
. . . , . ~ . , ~ . ~ .
'~
~ '7~ ~
bath dyeing of polymer chips or granules for spinning solutions/melts 3 metered addition to spinning melts or spinningsolu-tions, and application to the spun tow before stretching.
The fluorescent brighteners according to the present invention can, for example, also be emp]oyed in the follow~ng use forms:
a) in mixtures with dyestuffs (shading) or pigments (coloured pigments or especially, for example, ~hite ~ments~, or as an additive to dye baths, printing pastes, dischargf~
pastes or reserve pastes9 or for ~he af~er~reatrnent of dyein~, prints or discharge prints;
b) in mixtures with carriers, wetting agen.s, plasti.
cisers, swelling agents, anti~oxidants, ultraviolet absorbe-rs~
heat stabilisers and chemical bleaching agents(ch~l~r7~bleac.1n or bleaching bath additives);
c~ inadmixture with crossllnking agents or finishing agents (for example starch or synthetic finishes), and in combination with the most diverse textile ~in.ishing processes~
especially synthetic resin finishes (for example creaseprouf inishes such as wash-and-wear~ permanent~press or non-iron~ 7 . . ' ~' ' '. ' ' as ~ell as flameproof ~inishes, soft llandle finishes, anti-soiling finishes or anti-static fillishes, or antimicrobial .inishes;
d) incorporation of the fluorescent brighteners into polymeric carriers (polymerisation, polycondensation or poly-addition products, in a di~ssolved or dispersed form, for use, for example, in coating agents~ impregnating agents or bin-ders (solutions, dispersions and emulsions) for textiles, non-wovens, papers and leather;
e) as additives to master batches;
~ as additives to the most diverse industrl.al products .-in order to render these more marketable (for e.xample im-proving the appearance of soaps, detergents, pigments);
.
g) in combination with other optically brighLening sub- . :
stances;
h) in spinning bath preparatio~s, that is to say as ad~
ditives to spinning baths which are used for imploviIlg th~
slip for th~ further processing of synthetic fibres, or ~rom special bath before the stretching of the fi.bre;
i) as scintillators forvarious purposes of a pho~o graphic nature, for example, for electrophotographic repro--duction, or the optical brightening of photographic layers, optional].y in combination with white pigments,forexampleTiO
j) depending on the substitution as laser dyes.
If the brightcning process is combined with te~tile ~ ' ' ' ~ ' ' ' .. ~;
, ' . ~ ~ ' . , , , ' ' ' ' .
' '' .' r ' ' ~
~s~
treatmerlt or finishing methods, t~le combined treatment can in many casPs advatageol~sly be carri2d out ~^1ith the aid of appropriate stable preparatio-ns which contain the fluorescent brightener compounds in such a concentration that the desired brightening effect is achieved.
In certain cases, the fluorescent brighteners are made ~ully effective by an a~ter-treatment. This can be, for example, a chemical treatment (for example acid treatment)~ a thermal treatment (for example heat) or a combined chemic~l/
thermal trèatment. Thus, for example,the appropriate procedure to follow in brightening a number of fibre substrates, for example polyester fibres~ with the fluorescent brighteners according to the invention, is to impregnate these fibres~ h the aqueous dispersions (or optionally also solutions) of the brighteners at temperatures below 75C, for example at room temperature, and to subject them to a dry heat treatment a~
tem~eratures above lOO~C, it being generally advisable .dli-tionally to dry the fibre material beforehand at a moderately eleva~ed ternperature, for example at not less than 60C and up to about 130~C. The heat treatmellt in the dry state is then advantageously carried out at temperature bet~een 120 and 225~C, for example by heating in a drying chamber~ by ironing ~ithln the specified temperature range or by treat~
ment with dry, superheated steam. The drying and dry heat treatment ~an also be carried out in i~mediate succession or be ~ombined in a single process stage~
g~
The amount of fluorescent brightener manufactured aceording to the invention to be used, referred to the weighc of the material to be brightened, can vary ~7ithin wide limit5.
marked and lasting effect can be obtained even with very insignificant amounts, in certain cases 0.0001 percent by weightO ~ut it is also possible to use amounts of up to appO
0~8 percent by weight and, on occasion, up to app. 2 percent by weigllt. For mos~ practical purposes, it is preferable to use amounts between 0.0005 and O.S percent by weight.
The following Examples illustrate the in~ention, the percentages being by weight unless othe~i.se stated.
Melting and boiling points, unless otherwise indicated, are uncorrected and to some extent approximate, ~ 26 ~
. ~ .
~` '. ~. ' : ' .'` . ' , . . . .
Example 1 With stirring and passage of nitrogen, 134.7 g of po~assium ~ert. butylate are added in small amounts at 60C
to a solution of 77.8 g of the compound of the formula .
(101) ~ ~ ~ _ ~ CH
~ / 3 .
and 67,5 g of the anil o~ terephthal ~ldehyde acid in 1 litre of anhydrous dimethyl formamide, in the process of which the reaction mixture turns violet in colour. The temperature is allo~ed to rise to 80~C and kept thereat for 1 hour. After the reaction mixture has been cooled in an ice bath, it is trea~ed with 200 ml of wa~er, acidified with 120 ml of ~onc.
hydrochloric acid, and the prPc.ipitated product is filtered off with suction and ~ashed repeatedly ~ith ~ater, methanol, acetone and chloroform. The ilter product is dried in vacuo at 100C to yield 114,4 g (=97.4% of theory) of ~he carboxylic acid of the formula (102) ~ N ~ CH - CH ~ COOH
~ ~7 -, ' Y7~
It is purifiPd by recrystallisation from dimethyl formamide and a small arnount of water and then from diethylene glycol and by ex~rac~ion with ethyl alcohol to give lurninous, ]ight yellow crystals which melt at 350C (with decomp.).
114.4 g of the crude carboxylic acid of the formula (102) a~e stirred under reflux in 31.9 ml of thionyl chloride and 1 litre o chlorobenzene until the evolution o- hydrogen chloride h~as ceased and a solution is obtained (c. 1 hour~.
About 600 ml of solvent are distilled off and the residue is cooled. The precipitate is filtered off with suction and ~ashed with 2 x 100 ml of chlorobenzene and driedg to yield 108.~ g (--91% of theory) of the acid chloride of the fon~ula N ~ CH = CU ~ COCl as ligh~ yellow crystals with a melting point of 224C.
12~3 g of the compound of the formula (103~ are dissolved under reflux in 90 ml of anhydrous chloroben~ene.
With stirring~ sufficient absolute alcohol is cautiously aclded dropwise to the hot solution to lower the reflux tempera~lreto about 125C, whereupon vigorous evolution of hydrogen cl~loride ensues. After reflu~ing for 1 hour, a furtller 80 ml of absO
alcohol are added and the batch is refluxed for a further hour with stirring. Filtration is effected at room temperature, ~ .. .. .
'` ` .` : ~ : .
.` ' ' ~ ' ' . :. ' .; . . .
the resldue is washed with alcohol and dried at 100C in vacuum to yield the ethyl ester of the formula (104) ~XN / Cll = CH ~3- COOC2115 in the form of pale yellow crystal~. Yield - c. 90% Gf thc~o~y~
m~p. 171-172C after recrystallisation from ethylene glyc:ol monomethyl ether.
The carboxylic acids and their esters of the general formula (105) lis~ed in Table I can be manufactured in similar manner.
~105) / N ~ -C~ = CH ~ ~3 .
~ - 29 ~
- . . . ~ , . .. . .
: . . : . . .
.~ 3t'~
TABLE I
~ _ _ . . . _ _ . . _. __ . . . ~
No ~ Rl R2 R3 R4 recrystallisation m~p. C
. . ~ . .... .... . _ _ . _ .... I
106 -Cl / ~H3 H COOH H TCB -'~ . 350 107 -CO~ ~C~13 H -COOll H DCB ,n-butanol 272 lOg H ~I-COOH -OCH3 TCB 358 lO9 H -COOH~l H DC~ 25l 110 -Cl ~CH3 H~OOn C4~; U n butanol,toluene 168 lll -CoN~cH3 H -COOC~13 H benzene,n-propanol 198 112 H H ~Cn-C4~ - OCH3 nonane,n-butanol l52 113 ~ . -COOCI13 H _ nonane~n-butanol . _ -~
*TCB - l,2,4~triclllorobenzene, DCB = o-d;chlorobenzene .
In the manufacture of the compound of the formula (102)~ it is also possible to use the p-chloroanil instead of the anil of terephthal aldehyde acid, The anil of terephthal aldehyde acid can also be replaced by its methyl or ethyl ester~ when saponification occurs during the reaction.
.
: ~ 30 ~
.. .~ . ;.. , . , ~ ,~ . . . .
.
.. . . . . . . . . . . . .
E~ample 2 With stlrring and passage o~ nitrogen, 11.5 g of pulverised 88% potassium hydroxide are added at 60C to a solution of 7.8 g of the compound of the formula (101) and 6.75 of~the anil of terephtllal aldehyde acld in 180 .nl of hexarrlethylphosphoric triamide. The temperature is raised slowly to 120C and kept thereat for L hour. After it has cooled, the dark blue xeaction mixture is treated with 200 ml o water and acidified with 20 ml of concentrated hydrochloric acid. The precipitate is iltered off with suction, ~ashed repeatedly ~ith water~ methanol, acetone and chloroform and clried il~ vacuo at 100C. Yield: 11.1 g ~ 9~.6% of theory) o the cornpound of tlle formula (102)~
- The cornpound of the formula (102) ls also obta_ned by using sodium methylate instead of potassium hydroxide and other~ise carrying out ~he same procedure.
Example 3 Wi~h stixring and passage of nitrogen, 11.5 g of sodium tert. butylate are add~d in small amounts at 50C to a solution of 7.8 g of the compound of the formula (101) and 6.7S g of the anil of terephthal aLdeilyde acid in 180 ml of anhydrous dimethyl formamide. The temper2ture is kept for hour at 80C and then for 1 hour at 100C. After tlle batch ~ 31 ~
.. - -: ,.. , . ,. . ... : : ., . . . , . - , . .-.. : . .,. . , : . : . , :: .... . . :,. , :. . ; . : ,. ,: . .:
. : . - :. :: . ~ .. .. . . . .. , , : , : ..
:, , . .. . : , :
: ... ~ . . .. .. -: . . ~ : .
: - .: ~. . . ..
.
has b~en cooled in an ice bathj the dark reaction product i5 treated with 40 ml of water a.nd acidifjed ~lth 2S ml of conc hydrochloric acid~ The precipitate is fllterd off ~i~h ~lCtiOn~
washed repeatedly wlth water, metllanol~ acetone and chloroform and dried in vacuo at 100C. Yield: 8c8 g of the compound of the formula (102)0 The compound of the form~lla (10~) is also obtaine(3 by using potassium tert. butylate instead of sodium tert.
butylate and tetramethylurea, diethyl formarnide or N-methyl-pyrrolidone as solvent~ at a reaction temperature o 90Cn .
Example 4 8.1 g of 2-(p-tolyl)~5~6-dimethoxy~benztria~ole are reacted wi.th 6~75 g of the anil of terephthal aldehyde acid . in accordance with Example 1. Yield: 11.3 g of the carboxylic acid of t-he formula .
(~14) .
Cl~30 / \ N ~ CH - Cll ~ -C001 ~1~ 0 ~ -which is recrystallised from dimethyl ormdmide: m.p. 338~C.
Esterification with n-butanol yields the n~butyl . ester of the ormula _ . , . . ~ . : . .
. . ~ . .. ~ ' : ' . . . .
: i ' .: , ' .. . . , . . . .. ~ .. . -. -, : ~
. .. . . . .
. . . . , . : .
.
~115) C~130 ~ \ ~ - CH = Cll ~ CnO-nC4Hg C~30 with a melting point of 170C after recrystallisation from petroleum ether (b.p. 170-206C) and ethylene glycol mono-methyl ether.
The compounds of the general formula (116) R5 N
R ~ N - 4 -Cl = Cll- ~ - R4 listed in Table II are obtained in corresponding manner.
' '"
, ~.
~ 33 , - . . .: . . - . , , - ~ . , ., . : , :.. : .. ~ .. , .. .. . :;: . : . . . . . . .. .. ..
A ~ N - ~ CH3 wherein A is as defined above, with an anil of the formula t3) ~ Cl~ c N ~ ~r COORlL
wherein Rl is as defined akove and Ar represents an unsubsti~
tuted or a substituted aromatic radical, in the presence of a strongly basi.c alkali compound in a strongly polar, neutral to basic organic solvent or mixtures thereof.
:: - 4 -.... .. _ .. .. . . . .
. . : . ~, . .
. . .
~', ' "~ ' , ',: . .' '~ ' ~ . ~' ' , ' ' .
' ~ ' '' ' ' ' ' ' ' , ' ' ' ' Preferred carbamoyl and sulphamc,~l. radicals can be represented by the ormulae - CON ~ and - ~)2N~
Zl æ
respectively, wherein each o~ Z and ~1 independently repr~se~
hydrogen, preferably alkyl of 1 to 4 carbon atoms~ or together with the nitrogen atom they r~p;esent .the completion of a non-aromatic ring with 5 to 7 members, e.g. a morpholino or piperidino ring.
The term "carbc)xy" is to be understood as meallin~
herein the radical -COO~I, wherein M represents hydrogen or a salt-forming cation. Possible salt-forming cations ~I are in general ~hose of al~aline ear~h meta].s, e.g. ca~cium, barium or magnesium, as well as of alkali metals, e.g. sodiu~
or potassium, and also ammonium which is subs.ituted by alkyl or hydro~yallcyl of 1 to 4 carbon atoms or is unsubs~ituted, or amine salt~ of cyclic anlines, e.g. ~yridine, morplloline or piperidine. Besides hydrogen, M preferably represents in particular the potassiun~ and ~he sodiur.l cationO
, " ;.,~
. ' . ' ~ . ', ' - ' : . . .. - . . ..
The aromatic radical Ar is made up as a rule from one or more 6-membered carbocycles; preferably it represents a substituted or an unsubstituted naphthalene radical and especially a chlorine-substituted or an unsuhstituted phenyl radical.
An interesting process for the manufacture of 2-stilbenyl-1,2,3~triazoles of the formllla (4) ~ N ~ ~ Cll= CH ~ COORl R4 ~5 wherein Rl represents hydrogen or an alkali metal, alkaline earth metal, ammonium or amine salt cation, R2 represents hydrogen, alkoxy of 1 to 4 carbon atoms, carboxyalkoxy of 2 to 6 carbon atoms or together with R3 represents methylene-dioxy, R3 represents hydrogen, alkoxy of 1 to 4 carbon atoms, carboxyalkoxy of 2 to 6 carbon atoms, alkoxyalkoxy of 2 to 6 carbon atoms, phenoxy, phenoxyalkoxy of 1 to 3 carbon atoms in the alkyl moiety, chlorine, alkylmercapto, phenylmercapto, alkyl of 2 to 4 carbon atoms, or together with R2 represents methylenedioxy or together with R4 represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by chlorine, alkoxy of 1 to 4 carbon atoms or -SO2N\ 1 or -CON\ 1 , in which each of Yl and Y2 independently represents alkyl of 1 to 4 carbon atoms, R4 represents hydrogen or together with R3 represents the com-pletion of an unsubstituted naphthalene ring or of a naphtha-lene ring which is substituted by chlorine, alkoxy of 1 to 4 carbon atoms or -SO2N\ 1 or -CON ~ 1 , in which each of Yl and Y~ independently represents alkyl of 1 to 4 carbon atoms, .
'~. " ~ ' ,' '',' ' .
.
.' ' , ,. ' ' :
~., R5 represents hydrogen, chlor:ine, alkoxy of 1 to 4 carbon atoms, preferably methoxy, -CON\ 1 , -S02N\ 1 , in which Yl and Y2 have the meanings already assigned to them, or represents -502-phenyl, which comprises reacting a 2-tolyl-1,2,3-triazole of the formula (5) R2 ~ N
R
wherein R2, R3, R4 and R5 have the indicated meanings, with an anil of the formula (6) Arl - N = Cll ~ COOR~
wherein Arlrepresents phenyl, chlorophenyl or naphthyl and Rl has the indicated meaning.
A preferred process for the manufacture of 2-stil-benyl-1,2,3-triazoles of the formula (7) Rq\~ \` ~ CH - Cll~ ~ COOR
R3 ~ N/ \=<
I~,.13",~
. . . . : : . .
, : . . , ~, : ~. . :
: ~, . . . : ~ : .
: : : . . . , , . : : .:
::
: . . .: : : .. : -: . ' .: : . ' ' . . ~ ' ~ : . ' . :
:
:: ::: : : . :
J~ ~
wherein Ri represents a hydrogen, alkali rnetal, alkaline earth metal, ammonium or amine salt ion, R2 represents hydrogen, alkoxy of 1 to 4 carbon atoms or together with R3 represents methylenedioxy, R3 represents hydxogen, alkoxy of 1 to 4 carbon atoms, phenoxy, phenoxyalkoxy of 1 to 3 carbon atoms in the alkoxy moiety, chlorine, or together with R2 represents methy-lenedioxy or together with R~ represen-ts the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by alkoxy of 1 to 4 carbon atoms, R4 represents hydrogen or together with R3 represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by alkoxy of 1 to 4 carbon atoms, and R5 repre-sents hydrogen, methoxy or -CONYlY2, whereln each of Yl and Y2 independently represents alkyl of 1 to 4 carbon atoms which comprises reacting a 2-tolyl-1,2,3-triazole of the formula (8) R ~ / ~ ~ 3 R~ ~5 wherein R2, R3, R4 and R5 have the indicated meanings, with an anil of the ~ormula (9) 1 N Cl ~ COOR
.
.~i~ .
..
': . ~ ' ' . ~ ~
T~
wherein Arl represents phenyl, chlorophenyl or naphthyl and Rl has the meaning indicated above.
An especially preferred process for the manufacture of 2-stilbenyl-naphtho-1,2,3-triazoles of the formulae (10) ~ N / CH=CH ~ COOR
and (11) ~X ~3C~=CH {}COOR
,~ ..
1.. . . . ... . .... . . . . .
: . . .: . : .. : : . . . .
~hereill R'~' represents a hydrogen, alkali metal, an~lonium or an~ne salt ion, and R~ represents hydroge~ or alkoYy of 1 to 4 carbon atoms, is that which comprises reactin.g a 2-tolyl--naphtho 1,2,3 triazole oX ~he formula (12~ ~ \N - ~ C~l3 : ~6 ' wherein R6 has the indicated meaning, with an anil of the :Eormula . (13) h ~P`l ~ ~ = CH - ~ or .~
(143 h ~ N = CH ~ - COOR',' wherein h represen~s chlorine or hydrogen and R'l has the meaning previously assigned to it. The process for the manufacture of compounds of the formulae (10) and (11), wherein RS is hydrogen, is particularly preferred~
Also deserving of mention is the procPss for the manufacture of 2 stilbenyl-benzo 1,2,3-trl.azoles of the formula ' . . . . . .
.. . . .
:
. , ~. . . . . .
. . .
(15) ~ N _ ~ _ C~ C~ COOR~
wherein Rl, R2 and R3 have the meanings previously assigned to them, which process comprises reacting a 2-tolyl-benzo~
1,2,3-triazole of the formula (16) ~ N - ~ - Cl~3 wherein R2 and R3 have the meanings assigned to them hereirl-before, with an anil of the formula (17) h - ~ N = CH ~ COOR
wherein h and Rl have the meanings assigned to them herein~
- before~
The reaction produc~ of the formulae (1), ~4) 5 (7)~
(10), (11) and (lS) can, if appropriate, be esterified.
The esterification is carried out in a manner known per se by reacting the acid with an alkanol, alkenol, phenol, hydroxyalkylbenzene or cycloalkanol, as e.g. methano~
ethanol, n-propanol, isopropanol, n-butanol~ sec. butanol 9 i~obutanol, tert. butanol, n-hexanol, n-octanol32-ethy~e~anol, ; ; . . . :
- . . . . .
.
ethylene chlorollydrin, propylene chlorohydrin, 3-chloro~
propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ethe;, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, l-methoxy-2~propanol, butylglycolate glycolic nitrile, 3-hydroxypropion:itrile, ethyl lactate,allyl alcohol, crotyl alcohol, phenol, o , m- and p-cresol,o chloro-phenyl, tert. butylphenol, benzyl alcohol, 2--phenoxyethanolS
l-phenylethanol, cyclopentanol and cyclohexanol. The esteriIi-cation is effected, for example, in the presence of an acid catalyst, such as sulphuric acidg hydrogen chloride or p-toluenesulphonic acid, optionally with simultaneous removal of the water of reaction as an azeotrope with a suitable entrainer, as e.g. perchloroethylene, xylene, chlorobenzene or higher boiling petroleum ether fractions. Ho~7ever~ it ~s also posslble to manufacture the esters by ~ay of the corresponding carboxylic chlorides by reacting the carboxylic acids first ~ith thionyl chloride, phosphoroxy chloride etc.
and heating the reaction products, with or ~ithout isolating them first, with the alcohols or phenols.
The process according to the invention also makes it possible to manufacture in good yield interesting compounds of the formula (1), wherein the benzene nucleus does not necessarlly contain electronegative substituents.
Within to scope of compounds of formula (7) and of .. , .. ... . ~ .
their esters the co~pounds of particular interest are a3 2-s~ilbenyl-1,233-tria~oles of the ~orm~lla , . :,: .
,: . , , . . :
~18) N
A ~ C~-l = C~i - ~ COOR~
wherein A represents a benzene or naphthalene ring which i5 unsubstituted or substitu~:ed by non~chromophoric groups and R' represents all~l of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoallcyl of 1 to 4 carbon a~oms~ alkenyl of 3 or 4 carbon atoms or phenoxyall~yl of 1 to 3 carbon atoms in the alkyl moiety and in case A represents a benzene ring subscituted.
by non~chromophoric groups R' also represents hyd.rogen or a salt forming~cation, b) 2-stilbenyl-1~2,3-triazoles of the formula ~ / - ~ Ci~ = Cl~ _ ~ COOR" , wherein Rl' represents alkyl of 2 to 4 carbon atoms) and c) the compound o the formula (20) ~ / ~ -Cll = Cll - ~ CC2~5 and for the optically br;ghtening of polyesters in the spinning melt the compound.s of the form~lla ~ ~ ~ ~.3 - :
~ '- , ' . . . , : . ' .
. . .
R3 ~N~ ~U=C~I.~COOR'i ' wherein Rl ' represents a hydrogen, ~lkalimetalg ammonium, ~min~ s~.lt ion or alkyl with 1 to 4 carbon atoms, R'2 represents hydrogen 5 alkoxy with 1 to 4 carbon atoms or togetller with R'3 represents methylene-dio~y and R'3 represents aikoxy with 1 to 4 carbon atoms or to~ethex w~ith R'2 ~eprescnts methylen~3dioxg~, and p.-articulary those compounds o~ the formula R2~ ~ ~ ~ H=~ COOH
wherein R'2' represents hydrogen or alkoxy with-l to 4 carbon stoms, particularly methoxy and R'3' represents alkoxy with 1 to 4 carbon atoms, ~articularly methoxy.
2-stilbenyl-1-,2,3-triazoles of the formulae tl~ lg3 and (~
wherein ~, R" and R"l are different rom hydrogen or a salt~rm~
ca~on can be manuactured by esteri~ication in kno~n manner ~` of the correspond;ng carboxylic acid with an alcoholg for example ethanol, n-propanol, isopropanol, n-butanol, ~ec.
butanol, isobutanol, ~ert. butallol, ethylene chlorohydrin, propylene chlorohydrin, 3-chloro-1-propanol, ethylenæ. glycol - 13 a-:
.
monomet~ 71 a-nd monoekhyl ether, ethylene glycol monobutyl ether~ e~hylene glyco'l isopropyl ether, allyl alcohol~ crotyl alcohol, 2-phenoxyethanol, 3 phenoxypropanol, l-phenylethanol~
cyclopentanol and benzyl alcoholO
` The starting materials, i.e. the compounds of the formulae (2)~ (3), (5), (6), (8), (9), (11) and (12), are kno~n or can be manu~actured in a manner which is kno~n per se. The anils of the formu'Lae (3~, (6) 5 (9) and (12) are therefore manufactured by reacting an aromatic amine or a substituted or unsubstituted naphrhylamine or aniline or an unsubstitllted or a chlorine~substituted aniline with, for e~ample, o-carbo~ybenzaldellyde, m-carboxybenzaldehyde, p-carboxybenzaldehyde, 2 carboxy-5-methoxy-benzaldehyde, 2-methyl-4-carboxybenzaldehyde,2-chloro-5-carboxybenza'ldehyd~
The manufacture of the 2-tolyl-naphthotriazoles is effected in accordance ~ith Helv. Chim. Acta 55 (1972) 849 and that of the 2-~olyl-benzo~riazoles iII accordance with Helv. Chim Acta 55 (197~) 2325.
The compounds containing methyl groups can b~
reacted with the anils in the presence of a ~uitaible stron~ly polar, neutral to alkaline organic solvent or mixtures t'hereo which do not contain atoms, in particular hydrogen atoms,th.-~can be rep:Laced by alkali metals. 'Ln practlce, suitable solvents o~ this kind are primarily dialkylated acylamides of :, . .
` " . ' ' ' ' ' : ' : '" - . : ' , : ~ ' thc ~ype (23) EalkYl)2~] ~ acyl whereill;'alkyl" represents a lower alkyl group of 1 to 4 carbon atoms, in particular a methyl group, "acyll' represents the radical of a lower carboxylic acid of 1 to 4 carbon atoms, in particular formic or phosphoric acid~ and ~ indic~tes the basicity of the acid. As important examples of such solvents there may be mentioned: diethyl formamide, dimethyl acetamide and especially dimethyl formamide and hexamethylphosphoric triamide~ Suitable solvents are also N-alkyl-lactames of 5 to 10 carbon atoms, e.gO N-methylpyrrolidone and tetra-alkylurea.s, such as tetrame~hylur~a.
As has been mentioned already, a strongly basic allcali compound is also neGessary for carrying out the reaction. Suî~able for this purpose, depending on the nature of the solvent and the reactivity of the anil, are alkali metal alcoholates or hydroxides, in particular potassium and sodium compounds of the composition ~24) KCm~ 2m-1 and ~aOCmH
` , ~' : .~-.. ~.. . .
, .~ - .. . .
respectively~ wherein m is an inte~er froi~l 1 to 6, for ~xample potassium llydroxide~ po~assiurl t~r~. butylate7 sodi~lm tert.
butylat~ or sodium methylate. When using such alkali alcoholates the process must be carried out in virtually anhydrous medium;
whereas a small water content of up to app. 15% is permissable ~hen using potasisiu[n hydroxide. It is advantageous to use potassium hydroxide and sodium methyla~e e.g. in combination with hexamethylphosphoric triamide at elevated temperatur~
e,g, at 110-130C. It is of course also possible to use miY~tures of such bases. The use of potassium tertc butylat2 is preferL-ed.
The compounds containing methyl groups are desirably reacted with the anils in ea~uivalent amounts, so tha~ there is no substantial excess of either component, although on occasion an excess of anil of up to app. 50% can often be of advantage. It is advantageous to use at least the equivalent amount o alkali compound, i~e~ at least 1 mole of a compound with e~g. one K0 group to 1 mole of aldehyde anil. When using potassium hydroxide, it is preferable to do so in ~ to 8 times the e~uivalent amount. Particularly good yields are obtained on using potassium tert. butylate in one to si~ times, preferably two to four times, ~he equivalent amount.
The reaction according to the invention can usu211y be carried out at temperatur~s in the range be~een a~out 10 and 150~C~ When usin~ par~iculclrly reactive anils and ~1.
. . , . .' " , " ' '''; ' .. ' .
, ' ' ' ~, ' .. ; ' . :
~ - \
and p~rticular]y energetic catalysts, e.g. potassium te-rt.
butylate, the reaction takes place frequently even at room temperature, in which case it is not necessary to apply heat externallyO This is especially advantageous if the reactants contain ring compounds or substitueIIts which can be easil~
opened or split off by alkali or which can be chemically changed in some other way. Thls applies, for example, to anils which contain chlorine substituents which can be easi]y split of. However, it tnost advantageous to carry out the -process at e~evated temperature, especially when using sodium alcoholates and po~assium hydroxide. For example, the reac~
mixture is heated slowly to 30 to 90C and then kept at this temperatwre for a time, e.g from-l hour to 2 hours~
The manufacture ofthe anil and the reaction thereof with the tolyl compound can alsobe carried out consecutively i~
the one reaction vessel.For example, thealdehydeis heated~h excess aniline in dimethyl formamide and the reactioll mi~ture is completely evapora~ed to dryness in vacuo. A tolylcomponent and dimethyl formamide are added and the usual procedure is carried outO
The final products can be worked up from the reaction mixture by conventional methods which are known per se. The isolation o~ the carboxylic acids in salt form is e~-Eected for example ~y precipitation with water~ while the free ~arbo~lic acids can be precipitated by acidiEicat;on with a strong mineral acidS as for example aqueous hydrochloric acid. The w ~7 _ . ' ' - " .
'' ' -cornpounds vf the ~o-rmulae (1), (4)~ (7), (10), (11) and (15) and the esters thereof are mostly useful fluorescent brightenersO They can be used in known manner for brightenirlg organic materials of high molecular we;ght of the most widely differenc kind, preferably synthetic organi.c materials, in which connection the free carboxylic acids and the esters thereo are used ~ith advantage for polyester and the carbo ~ylic acicl salts for polyamide and polyacrylonltrileD
The carboxylic acid esters are particularly suitable for brightening polyester materials by the hlgh temperature exhaustion process.
Witllout any restriction belng implied by the following classification, examples of organic materials are:
I. Synthetic organic materials or high moiecular w~ht:
a) polymerisation products based on organic compounds containing at least one polymerisable carbon-carbon ~ou~le bond, t:hat is to say their homopol.ymers or copolymers as well as ~heir aftertreatment products, ~or example, crosslinking, grating or degradation products, polymer b]ends, or products obtained by modi~ication of reactive groups, or example polymers based on ~,~-unsaturated carboxylic acids or deriva~
tives o~ such carboxylic acids, especially on acrylic compo~md for example acryl.ic esters, acrylic acid, acrylonitrile, acrylic amîdes and their derivati~es or their methacryL
.. , - :
, ...
analogues~ on o].efin hydrocarbons (for example ethylene, propylene~ styrenes or dienes and also ABS polymers), and polymers based on vinyl and vinylidene compourlds (for exa~ple vinyl chloride, vinyl alcohol and vinylidene chloride);
b) polymerisation products which can be obtained by ring opening, for example~ polyamides of the polycaprolacta~
type, and also poiymers which are obtained both by polyaddi-tion and by polycondensation., for example polyethers or polyacetals, c) polycondensation products or precondensates based on bifunctiorlal or polyunctional compounds with conc~ellsable groups~ tlleir homocondensation and co-condensation products5 and aftert:reatment products, for example polyesters, especial~
ly saturated (for example ethylene glycol terephthali.c acid polyester~ or lmsaturated (for example maleic acid~dialcohol ;
polycondensates as well as their crosslinking products with copolymeri.sable vinyl monomers), unbranched and branched (also including those based on pol~rhydric alcohols, for ex-ample alkyd resins) polyesters, polyamides (for example hexa-methylenediamine adipate), maleic resins~ melamine resins, their precondensates and analogues, polycarbonates and sili~
cones;
,, .
d) polyaddition products, such as polyurethanes (CL'05S-linked and non-crossl;nked~ and epoxide resi.ns~
.; .
.
:
'~
IIr Regenerated man--made organic materials, ~or exalr,ple, cell1l1vse esters of varying degrees of esterification (so-called 2 1/2 acetate or triacetate) or cellu]ose ethers, regenerated cellulose (viscose or cuprammonium cellulose), or their aftertreatment products, and casein plastics.
III. Natural organic rnaterials of animal or vegetable origin~ for exaslple based on cellulose or proteins, SUC'Q as cotton, wool, linen, silk, va-cnish gums, starch and caseins The organic materials to be optically brightened can be in the most diverse states of processing (raw materlals5 semi-flnish~d ~oods or ~inished goods3. On the other hand, they can be in the form of structures o~ the most diverse shapes, for example predominantly three-dimensionals~-uctures such as sheets~ profiles, injection mouldings, various ma-chined articles, chips, granules or ~oams, and also pre-dominantly two-dimensional structures, such as films3 foils laccluers, coatings and impregnations, or predominantly one-dimensional bodies, such as filaments, fib:ces~ flocks and ~iL^es. The said materials can, on the other hand? also be in ~n unshaped state, in the most diverse homog~neous or inhomogeneous forms of division, as ~or example, in the form of powders, solutions, emulsions, dispersions, latices,pastes or waxes.
--, : - , . ~ : . .. .
Fibrc ma~erials canS for example, be in the form o~
endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile ilament yarns, threads, non-wovens, felts, waddings, ~locked structures or woven textile or bonded textile farbrics, knitted fabrics and papers, cardboards or paper pulps.
The compounds to be used according to the invention are of importance, inter alia, for the treatment of organ:ic textile materials, especially woven textile fabrics. If fi-bres which can be in the form of staple fibres or endless filaments or in the form of hanks, woven fabrics, knitted fabrics, fleeces~ flocked substrates or bonded fabrics, are to be optically brightened according to the invention, this is advantageously effected in an aqueous medium, wherein the compounds in question are present in a finely divided form (suspensions, so-called microdispersions~ or optionally solutions). If desired, dispersing agents, stabilisers~
wetting agents and further assistan~s can be added du~ing tlle treatment.
Depending on the type of brightener compound used~
it can be advantageous to carry out the treatment in a neu-tral or alkaline or acid bath. The treatment is usually car-ried out at temperatures of 20 to 140~C, for example at the boiling point of the bath or near it (about 90~C).
_ 21 -J
:. . .. .
- ~ . .
' . ' ' ' ' , ~ ' ~
~.
Solutions or emulslons in organic solvents oan also be us~d for the finishing acco^ding -~o the invention of textile sub strates, as i.s practised in the dyeing industry in so--called solvent dyeing (pad~heat fixing application., or eY.haustio dyeing processes in dyeing machines).
The new fluorescent brigllteners according to the present invention can further be added to, or incorporated in, the materials before or cluring their shaping. Th~ls they C2L1 for ex2rllple be added to the compression moulding composition or injection moulding composition during the manufact-lre of films, sheets (for example ~orking into polyvinyl chloride :i.n a single roller mill) or mouldings~
If the fashioning of man-made synthetic or regenera~
ted man-made organlc materials is effected by spilm.ing proces~
ses or fîom spinning solutions/melts, the fluorescent brigh~
1. eners can be applied by the ollowing processes:
addition to the starting substances (for example mo-nomers) or intermediates (~or example precondensates or pre-polymers), that is to say before or durillg the polymerisation~
polycondensation or polyaddition, sprinkling in powder form on polymer chips or granu-les for spinlllng solut:ions/nleltsg ; - ~2 ~
. . . , . ~ . , ~ . ~ .
'~
~ '7~ ~
bath dyeing of polymer chips or granules for spinning solutions/melts 3 metered addition to spinning melts or spinningsolu-tions, and application to the spun tow before stretching.
The fluorescent brighteners according to the present invention can, for example, also be emp]oyed in the follow~ng use forms:
a) in mixtures with dyestuffs (shading) or pigments (coloured pigments or especially, for example, ~hite ~ments~, or as an additive to dye baths, printing pastes, dischargf~
pastes or reserve pastes9 or for ~he af~er~reatrnent of dyein~, prints or discharge prints;
b) in mixtures with carriers, wetting agen.s, plasti.
cisers, swelling agents, anti~oxidants, ultraviolet absorbe-rs~
heat stabilisers and chemical bleaching agents(ch~l~r7~bleac.1n or bleaching bath additives);
c~ inadmixture with crossllnking agents or finishing agents (for example starch or synthetic finishes), and in combination with the most diverse textile ~in.ishing processes~
especially synthetic resin finishes (for example creaseprouf inishes such as wash-and-wear~ permanent~press or non-iron~ 7 . . ' ~' ' '. ' ' as ~ell as flameproof ~inishes, soft llandle finishes, anti-soiling finishes or anti-static fillishes, or antimicrobial .inishes;
d) incorporation of the fluorescent brighteners into polymeric carriers (polymerisation, polycondensation or poly-addition products, in a di~ssolved or dispersed form, for use, for example, in coating agents~ impregnating agents or bin-ders (solutions, dispersions and emulsions) for textiles, non-wovens, papers and leather;
e) as additives to master batches;
~ as additives to the most diverse industrl.al products .-in order to render these more marketable (for e.xample im-proving the appearance of soaps, detergents, pigments);
.
g) in combination with other optically brighLening sub- . :
stances;
h) in spinning bath preparatio~s, that is to say as ad~
ditives to spinning baths which are used for imploviIlg th~
slip for th~ further processing of synthetic fibres, or ~rom special bath before the stretching of the fi.bre;
i) as scintillators forvarious purposes of a pho~o graphic nature, for example, for electrophotographic repro--duction, or the optical brightening of photographic layers, optional].y in combination with white pigments,forexampleTiO
j) depending on the substitution as laser dyes.
If the brightcning process is combined with te~tile ~ ' ' ' ~ ' ' ' .. ~;
, ' . ~ ~ ' . , , , ' ' ' ' .
' '' .' r ' ' ~
~s~
treatmerlt or finishing methods, t~le combined treatment can in many casPs advatageol~sly be carri2d out ~^1ith the aid of appropriate stable preparatio-ns which contain the fluorescent brightener compounds in such a concentration that the desired brightening effect is achieved.
In certain cases, the fluorescent brighteners are made ~ully effective by an a~ter-treatment. This can be, for example, a chemical treatment (for example acid treatment)~ a thermal treatment (for example heat) or a combined chemic~l/
thermal trèatment. Thus, for example,the appropriate procedure to follow in brightening a number of fibre substrates, for example polyester fibres~ with the fluorescent brighteners according to the invention, is to impregnate these fibres~ h the aqueous dispersions (or optionally also solutions) of the brighteners at temperatures below 75C, for example at room temperature, and to subject them to a dry heat treatment a~
tem~eratures above lOO~C, it being generally advisable .dli-tionally to dry the fibre material beforehand at a moderately eleva~ed ternperature, for example at not less than 60C and up to about 130~C. The heat treatmellt in the dry state is then advantageously carried out at temperature bet~een 120 and 225~C, for example by heating in a drying chamber~ by ironing ~ithln the specified temperature range or by treat~
ment with dry, superheated steam. The drying and dry heat treatment ~an also be carried out in i~mediate succession or be ~ombined in a single process stage~
g~
The amount of fluorescent brightener manufactured aceording to the invention to be used, referred to the weighc of the material to be brightened, can vary ~7ithin wide limit5.
marked and lasting effect can be obtained even with very insignificant amounts, in certain cases 0.0001 percent by weightO ~ut it is also possible to use amounts of up to appO
0~8 percent by weight and, on occasion, up to app. 2 percent by weigllt. For mos~ practical purposes, it is preferable to use amounts between 0.0005 and O.S percent by weight.
The following Examples illustrate the in~ention, the percentages being by weight unless othe~i.se stated.
Melting and boiling points, unless otherwise indicated, are uncorrected and to some extent approximate, ~ 26 ~
. ~ .
~` '. ~. ' : ' .'` . ' , . . . .
Example 1 With stirring and passage of nitrogen, 134.7 g of po~assium ~ert. butylate are added in small amounts at 60C
to a solution of 77.8 g of the compound of the formula .
(101) ~ ~ ~ _ ~ CH
~ / 3 .
and 67,5 g of the anil o~ terephthal ~ldehyde acid in 1 litre of anhydrous dimethyl formamide, in the process of which the reaction mixture turns violet in colour. The temperature is allo~ed to rise to 80~C and kept thereat for 1 hour. After the reaction mixture has been cooled in an ice bath, it is trea~ed with 200 ml of wa~er, acidified with 120 ml of ~onc.
hydrochloric acid, and the prPc.ipitated product is filtered off with suction and ~ashed repeatedly ~ith ~ater, methanol, acetone and chloroform. The ilter product is dried in vacuo at 100C to yield 114,4 g (=97.4% of theory) of ~he carboxylic acid of the formula (102) ~ N ~ CH - CH ~ COOH
~ ~7 -, ' Y7~
It is purifiPd by recrystallisation from dimethyl formamide and a small arnount of water and then from diethylene glycol and by ex~rac~ion with ethyl alcohol to give lurninous, ]ight yellow crystals which melt at 350C (with decomp.).
114.4 g of the crude carboxylic acid of the formula (102) a~e stirred under reflux in 31.9 ml of thionyl chloride and 1 litre o chlorobenzene until the evolution o- hydrogen chloride h~as ceased and a solution is obtained (c. 1 hour~.
About 600 ml of solvent are distilled off and the residue is cooled. The precipitate is filtered off with suction and ~ashed with 2 x 100 ml of chlorobenzene and driedg to yield 108.~ g (--91% of theory) of the acid chloride of the fon~ula N ~ CH = CU ~ COCl as ligh~ yellow crystals with a melting point of 224C.
12~3 g of the compound of the formula (103~ are dissolved under reflux in 90 ml of anhydrous chloroben~ene.
With stirring~ sufficient absolute alcohol is cautiously aclded dropwise to the hot solution to lower the reflux tempera~lreto about 125C, whereupon vigorous evolution of hydrogen cl~loride ensues. After reflu~ing for 1 hour, a furtller 80 ml of absO
alcohol are added and the batch is refluxed for a further hour with stirring. Filtration is effected at room temperature, ~ .. .. .
'` ` .` : ~ : .
.` ' ' ~ ' ' . :. ' .; . . .
the resldue is washed with alcohol and dried at 100C in vacuum to yield the ethyl ester of the formula (104) ~XN / Cll = CH ~3- COOC2115 in the form of pale yellow crystal~. Yield - c. 90% Gf thc~o~y~
m~p. 171-172C after recrystallisation from ethylene glyc:ol monomethyl ether.
The carboxylic acids and their esters of the general formula (105) lis~ed in Table I can be manufactured in similar manner.
~105) / N ~ -C~ = CH ~ ~3 .
~ - 29 ~
- . . . ~ , . .. . .
: . . : . . .
.~ 3t'~
TABLE I
~ _ _ . . . _ _ . . _. __ . . . ~
No ~ Rl R2 R3 R4 recrystallisation m~p. C
. . ~ . .... .... . _ _ . _ .... I
106 -Cl / ~H3 H COOH H TCB -'~ . 350 107 -CO~ ~C~13 H -COOll H DCB ,n-butanol 272 lOg H ~I-COOH -OCH3 TCB 358 lO9 H -COOH~l H DC~ 25l 110 -Cl ~CH3 H~OOn C4~; U n butanol,toluene 168 lll -CoN~cH3 H -COOC~13 H benzene,n-propanol 198 112 H H ~Cn-C4~ - OCH3 nonane,n-butanol l52 113 ~ . -COOCI13 H _ nonane~n-butanol . _ -~
*TCB - l,2,4~triclllorobenzene, DCB = o-d;chlorobenzene .
In the manufacture of the compound of the formula (102)~ it is also possible to use the p-chloroanil instead of the anil of terephthal aldehyde acid, The anil of terephthal aldehyde acid can also be replaced by its methyl or ethyl ester~ when saponification occurs during the reaction.
.
: ~ 30 ~
.. .~ . ;.. , . , ~ ,~ . . . .
.
.. . . . . . . . . . . . .
E~ample 2 With stlrring and passage o~ nitrogen, 11.5 g of pulverised 88% potassium hydroxide are added at 60C to a solution of 7.8 g of the compound of the formula (101) and 6.75 of~the anil of terephtllal aldehyde acld in 180 .nl of hexarrlethylphosphoric triamide. The temperature is raised slowly to 120C and kept thereat for L hour. After it has cooled, the dark blue xeaction mixture is treated with 200 ml o water and acidified with 20 ml of concentrated hydrochloric acid. The precipitate is iltered off with suction, ~ashed repeatedly ~ith water~ methanol, acetone and chloroform and clried il~ vacuo at 100C. Yield: 11.1 g ~ 9~.6% of theory) o the cornpound of tlle formula (102)~
- The cornpound of the formula (102) ls also obta_ned by using sodium methylate instead of potassium hydroxide and other~ise carrying out ~he same procedure.
Example 3 Wi~h stixring and passage of nitrogen, 11.5 g of sodium tert. butylate are add~d in small amounts at 50C to a solution of 7.8 g of the compound of the formula (101) and 6.7S g of the anil of terephthal aLdeilyde acid in 180 ml of anhydrous dimethyl formamide. The temper2ture is kept for hour at 80C and then for 1 hour at 100C. After tlle batch ~ 31 ~
.. - -: ,.. , . ,. . ... : : ., . . . , . - , . .-.. : . .,. . , : . : . , :: .... . . :,. , :. . ; . : ,. ,: . .:
. : . - :. :: . ~ .. .. . . . .. , , : , : ..
:, , . .. . : , :
: ... ~ . . .. .. -: . . ~ : .
: - .: ~. . . ..
.
has b~en cooled in an ice bathj the dark reaction product i5 treated with 40 ml of water a.nd acidifjed ~lth 2S ml of conc hydrochloric acid~ The precipitate is fllterd off ~i~h ~lCtiOn~
washed repeatedly wlth water, metllanol~ acetone and chloroform and dried in vacuo at 100C. Yield: 8c8 g of the compound of the formula (102)0 The compound of the form~lla (10~) is also obtaine(3 by using potassium tert. butylate instead of sodium tert.
butylate and tetramethylurea, diethyl formarnide or N-methyl-pyrrolidone as solvent~ at a reaction temperature o 90Cn .
Example 4 8.1 g of 2-(p-tolyl)~5~6-dimethoxy~benztria~ole are reacted wi.th 6~75 g of the anil of terephthal aldehyde acid . in accordance with Example 1. Yield: 11.3 g of the carboxylic acid of t-he formula .
(~14) .
Cl~30 / \ N ~ CH - Cll ~ -C001 ~1~ 0 ~ -which is recrystallised from dimethyl ormdmide: m.p. 338~C.
Esterification with n-butanol yields the n~butyl . ester of the ormula _ . , . . ~ . : . .
. . ~ . .. ~ ' : ' . . . .
: i ' .: , ' .. . . , . . . .. ~ .. . -. -, : ~
. .. . . . .
. . . . , . : .
.
~115) C~130 ~ \ ~ - CH = Cll ~ CnO-nC4Hg C~30 with a melting point of 170C after recrystallisation from petroleum ether (b.p. 170-206C) and ethylene glycol mono-methyl ether.
The compounds of the general formula (116) R5 N
R ~ N - 4 -Cl = Cll- ~ - R4 listed in Table II are obtained in corresponding manner.
' '"
, ~.
~ 33 , - . . .: . . - . , , - ~ . , ., . : , :.. : .. ~ .. , .. .. . :;: . : . . . . . . .. .. ..
- 3~ -_~_ ~
',,i O r1 t;~ ~ IJ~
O _~
~ I~ U~O C~ O U) O ~) P~ r~ O O
E~; ~ '1 a _~_ ~ C~ ~, P~ ~ O O O O O O ~I D
O O O C) O O O -- O '.
V C~ ) 0 ~ r-l ~1 . ~ O
C~ ~ ~ S~ ~
~; ~ O
_ ~ 3 ~ r~
, T ~ o ~ C~ ~ o ,~
~D C~ C~ X o a ~: ~ ~ s~
. ~ ~ o O O O o ~ ~ $
____ ~ ~ ol o ~ ~ o ~ ~ ~ ~ .
o o o o C~ o ~
~ d .- _ .._~
~ o H ~ ~
~ r~ o~ a~ o ~J ~ ~ ~ ~ .
~ O ~
. ~ . H C~
~ ' , . .
: : . . ': , . ' . ~ . .
' , ' ~ ' ~J~J"~$
Ex~ampl e r) Esterification of the car1~oxylic acid of the formula (102~ with methanol, n butanol, 3-phenoYyproparlol, isopropanol, ethylene chlorohydrin, ethylene glycol mono--methyl ether, alkyl alcohol, phenol, 3-hydroxypropionitrile;
cycloheYanol, n~propanol, isobutanol, sec. bucanol, tert~
- butanol instead of with ethanol yields the esters of the general formula (124) ~ ~ \ N ~ C~ H~ ~ ~ C00 ~ N /
lis~ed in Table III.
.: ' - , . . .. . .
- - : . . .
~ - ~ . , , , . ,, : : ' , ,:
' ' . :.. ,............ , . . ! , . .
TI~BLE III
.
Formula ~o ~ R . m. p . C
~ ___ ( 12 5 ) -CH3 22 7 (126) -C4~9 130 (127) -(CH2)3 0-~3 140 ~128) -CH(CH3)2 166 ( 12 9 ) -Cli2C~2Cl 1 74 (130) -CH2CH2-OCH3 7.50 (131 ) -CH2-CH=CH2 144 ( 1 32) ~3 200 ( 13~ ) -CH2CH2CN 183 .
(134) ~ . 17~
(135) -CH2CH2CH3 147 (13~) -Cl12-CH(CH3)2 146 . / CH3 . .
. . ( 137 ) -CH \ C2H5 147 ( 138 ) _ . .. . ~ 123 :-, .- ~ ,. : .
, ,: . .
.. .
.
, .
,. . . . ... . . . .
~xa=ple 6 ~ sing softened water~ a bath is prepared which contains per litre 0.16% (referred to the weight of the fabric to be briglltened) of the compound of the formula (104) (~hich has been predispersed with a small amount of water and app. 1 gram of a dispersant~ e.g. an ethoxylated stearyl alcohol) and app. 2 g of a carrier. A suitable carr~r is, for example, a mixture of dodecylbenzenesulphonate (as triethanolamine salt), ethoxylated ricinolic acid, n-hexanol and ethylene glycol in 1,2,4-trichlorobenæene.
A polyester fabric is put into this bath at 40C
~liquor ratio 1:25). The bath is heated to 97C in the course o~ 30 minutes and held at thi~ temperature for a further 30 minutes. After rinsing and drying it, a very strongly brigh-tened polyester fabric is obtained.
.
Example 7 Polyester fabric is trea~ed in an autoclave in a bath of the ollowing composition (liquor ratio 1:25):
0.16% (re~erred to ~he weight o~ the fabric to be brightened) of the compound of the formula (I0~) - in finely dispersed form, 1.0 g of an e~hoxylated stearyl alcohol, - ' , ... . . . . . .
1, , ' ' ~. ~ , 1000 ml of softened w~ter.
'l'he bath is heated in the course of 30 min~tes from 40~C to 175C and held thereat for a further 30 minu~es. The bath is then cooled and the fabric is rinsed and dried. A
brilliant l~hite polyester fabric is obtained~
Following the same procedure it is also possible to use the cornpounds of the formulae (126), (128), (135~, (136)~ (137) or (138), Example 8 A polyester fabric (based on ~erephthalic acid/
ethylene glycol) is padded at room temperature with an aqueous dispersion which contains per litre 2 g o~ one of the compounds of the formulae (104), (126), (7?8)~ (135)9 ~136), (137) or (138) and 1 g of an adduct of about 8 moles of ethylene oxide and 1 mole of p-tert. octylphenol, and subsecluently dried at app. 100C. The treat~d material exhibits a strong white effect.
A strong white effect is also obtained by using instead of the abo~e polyester fabric one that is obtained by condensation witll 2 to S molar percent of isophthalic acid-5-sodi~m sulphonate (Dacron 64).
Example 9 100 parts of terephthalic acid/ethylene glycol polyester granules are intimately mixed on each occasion , .j .
~ 3~ ~
.
. . .
.. ~ , . .:
: . ~
. .
with 0,~5 part of one of the compounds of the f^~rn~la~ 2)~
(10~-~)7 (126)g (1~8), (1l4)~ ~115~,(117) or (118) and melt~d, with stirring, at 285C. The spinnin~ melt is spun through conventional spinnerets to ~ive strongly whitened polyester fibres.
.
Example 10 _ _ , . . .
A polyamide fabric (Perlon) is put at 60C, in the liquor ratio o 1:40, into a bath which contains (referred to the weight of the fabric) 0,1% of one of the f]uorescent brighteners of the formulae (102), (104), (126) or ('l28) and~
per litre, 1 g of 80% acetic acid and 0.25 g of an adduct o ~0 to 35 moles of e~hylene oxide and 1 mole of commercial stearyl alcohol. The bath is heated within 30 minutes to boiling ~emperature and kept at the boil for 30 mînutes. The abric is then rinsed and dried. ~ strong white effect of good light iastness is obtained.
Similarly good white effec,ts are obtained by using a ~abric made of polyamide 66 (nylon) instead o~ polyamide 6 Finally, it is also to carry Ot1t the process under high temperature conditlons, e.g. over the course of 30minu~s at 130C. For this kind of applica~ion it is advisable ~o add 3 g/l of hydrosulphite to the solution~
,'. ~ ' . ' ' . ~': ' ' : ', . . - .
.
Exalllple 11 lO,000 g of polyam-Lde chips obtained in known rnanner from hexameth~lenediamine adipate are mixed for 1~ hours in a roller vessel with 30 g of titanium dioxide (rutile modifica-tion) and 5 g of one of the compounds of the formulae (102), (104~, (12~) or (128). The treated chips are me].ted in a boiler which is heated with oil or diphenyl vapour to 300-310C, after expulsion of the atmospheric o~ygen with steam~
and stlrred ror half an hour. The melt is ~hen pressed out:
through a spinneret under a nitrogen pressure o F 5 atmosO
(gauge) and th~ spun, cooled filament is wound on a spool.
l'he threads obtained exhibit a good white effect.
Simi.larly good results a~e obtained by uslng a polyamide obtained from -caprol.actam instead of from hexa~
. methylenediamine adipate.
E~ample 12 A cellulose acetate fabric is put a~ 50C into an aqueous bath (liquox ratio 1:30 ~o 1:40) which conLains 0.15C/o (based on the weight of the fabric~ of one of the compounds o~ the formulae (104), (126) or (128). The temperature of the treatment bath is brought to 90-95C and l.~ept thereat for 30 to 45 minutes. After the fabric has been rinsed and dried, a good white effect is obtained~
~0 ~
: ' . - ., , .:'' - ' . ' ' ~:
.
Example 13 An intimate mixture of 100 parts o. polyvinyl chloride, 3 parts of a stabiliser (Advas~at BD 100 : Ba/Cd complex), 2 parts of titanium dioxide, 59 parts o dioctyl phthalate and 0.01 to 0.2 part of one of the compounds of the formulae (102)~ (104), (i26) or (128) 7 are rolled out to a sheet on a calender at 150C to 155C.
The resultant opaque pol~7vinyl chlori.de sheet has a markedly higher white content than a sheet that does not contain the 1uorescent brightenerO
Example 1 A casting compound that consists of pol~acry~Dnitri:le~
0,2 g of titanium dioxide (anatase modifi~ation) as mattin~
agent, and 40 ml of dimethyl formamide, and which con~ain Smg of one of the compounds of t~e formulae (102~; (10~), (126) or (128), is poured onto a glass plate and dra~n out wi.th ~ me~al ~od to form a thin filsn. After it has dried, the film has a pronounced white effect.
Example 15 A 27% polyurethane casting compound in ethyl ace~a~e which contains, referred to the plastics dry weight, 2% of titanium dioxide (anatase modification) 9 5% of a stabiliser and 5% of a eatalyst as well as 0.05% of th.e compound o~ the .. , .. . , ... ,, , . - . -: ~,. , ., -: :: , - . . .
~, . . . ..
.. . . . . . . .
formula (104) or (126), is poured onto a glass plate and drawn out with a metal rod to form a thin film. After it has driedS the film has a pronounced white effect.
.
Example 16 100 parts of polystyrene and 0.1 part of one of the compounds of the formulae (104), (126) or (128) are melted in a ~ube of 1 cm diameter for 20 minutes at 210C excluding air, After the melt has cooled, a brightened polystyrene compound of good light fastness is obtained.
Example 17 Polypropylene fibres are treated with 0~02 to 0.4%
of the formula (104) for 60 minutes at 60~ to 100C in a bath (liquor ratio 1:40) which conta:ins per litre 5 g of an adduct o~ app. 35 moles of ethylene ox:;de and 1 mole of octadecyl alcohol, and 0.5 g of trisodium phosphateO The material is then rinsed and dried. The polypropylene fibres have a markedly higher white content than untreated fibres.
A similar effect is obtained by usin~ 1 ~ of 85%
formic acid instead of 0.5 g of trisodium phosphate.
42 ~
': . .. . .
. .
~, ' .
. .
',,i O r1 t;~ ~ IJ~
O _~
~ I~ U~O C~ O U) O ~) P~ r~ O O
E~; ~ '1 a _~_ ~ C~ ~, P~ ~ O O O O O O ~I D
O O O C) O O O -- O '.
V C~ ) 0 ~ r-l ~1 . ~ O
C~ ~ ~ S~ ~
~; ~ O
_ ~ 3 ~ r~
, T ~ o ~ C~ ~ o ,~
~D C~ C~ X o a ~: ~ ~ s~
. ~ ~ o O O O o ~ ~ $
____ ~ ~ ol o ~ ~ o ~ ~ ~ ~ .
o o o o C~ o ~
~ d .- _ .._~
~ o H ~ ~
~ r~ o~ a~ o ~J ~ ~ ~ ~ .
~ O ~
. ~ . H C~
~ ' , . .
: : . . ': , . ' . ~ . .
' , ' ~ ' ~J~J"~$
Ex~ampl e r) Esterification of the car1~oxylic acid of the formula (102~ with methanol, n butanol, 3-phenoYyproparlol, isopropanol, ethylene chlorohydrin, ethylene glycol mono--methyl ether, alkyl alcohol, phenol, 3-hydroxypropionitrile;
cycloheYanol, n~propanol, isobutanol, sec. bucanol, tert~
- butanol instead of with ethanol yields the esters of the general formula (124) ~ ~ \ N ~ C~ H~ ~ ~ C00 ~ N /
lis~ed in Table III.
.: ' - , . . .. . .
- - : . . .
~ - ~ . , , , . ,, : : ' , ,:
' ' . :.. ,............ , . . ! , . .
TI~BLE III
.
Formula ~o ~ R . m. p . C
~ ___ ( 12 5 ) -CH3 22 7 (126) -C4~9 130 (127) -(CH2)3 0-~3 140 ~128) -CH(CH3)2 166 ( 12 9 ) -Cli2C~2Cl 1 74 (130) -CH2CH2-OCH3 7.50 (131 ) -CH2-CH=CH2 144 ( 1 32) ~3 200 ( 13~ ) -CH2CH2CN 183 .
(134) ~ . 17~
(135) -CH2CH2CH3 147 (13~) -Cl12-CH(CH3)2 146 . / CH3 . .
. . ( 137 ) -CH \ C2H5 147 ( 138 ) _ . .. . ~ 123 :-, .- ~ ,. : .
, ,: . .
.. .
.
, .
,. . . . ... . . . .
~xa=ple 6 ~ sing softened water~ a bath is prepared which contains per litre 0.16% (referred to the weight of the fabric to be briglltened) of the compound of the formula (104) (~hich has been predispersed with a small amount of water and app. 1 gram of a dispersant~ e.g. an ethoxylated stearyl alcohol) and app. 2 g of a carrier. A suitable carr~r is, for example, a mixture of dodecylbenzenesulphonate (as triethanolamine salt), ethoxylated ricinolic acid, n-hexanol and ethylene glycol in 1,2,4-trichlorobenæene.
A polyester fabric is put into this bath at 40C
~liquor ratio 1:25). The bath is heated to 97C in the course o~ 30 minutes and held at thi~ temperature for a further 30 minutes. After rinsing and drying it, a very strongly brigh-tened polyester fabric is obtained.
.
Example 7 Polyester fabric is trea~ed in an autoclave in a bath of the ollowing composition (liquor ratio 1:25):
0.16% (re~erred to ~he weight o~ the fabric to be brightened) of the compound of the formula (I0~) - in finely dispersed form, 1.0 g of an e~hoxylated stearyl alcohol, - ' , ... . . . . . .
1, , ' ' ~. ~ , 1000 ml of softened w~ter.
'l'he bath is heated in the course of 30 min~tes from 40~C to 175C and held thereat for a further 30 minu~es. The bath is then cooled and the fabric is rinsed and dried. A
brilliant l~hite polyester fabric is obtained~
Following the same procedure it is also possible to use the cornpounds of the formulae (126), (128), (135~, (136)~ (137) or (138), Example 8 A polyester fabric (based on ~erephthalic acid/
ethylene glycol) is padded at room temperature with an aqueous dispersion which contains per litre 2 g o~ one of the compounds of the formulae (104), (126), (7?8)~ (135)9 ~136), (137) or (138) and 1 g of an adduct of about 8 moles of ethylene oxide and 1 mole of p-tert. octylphenol, and subsecluently dried at app. 100C. The treat~d material exhibits a strong white effect.
A strong white effect is also obtained by using instead of the abo~e polyester fabric one that is obtained by condensation witll 2 to S molar percent of isophthalic acid-5-sodi~m sulphonate (Dacron 64).
Example 9 100 parts of terephthalic acid/ethylene glycol polyester granules are intimately mixed on each occasion , .j .
~ 3~ ~
.
. . .
.. ~ , . .:
: . ~
. .
with 0,~5 part of one of the compounds of the f^~rn~la~ 2)~
(10~-~)7 (126)g (1~8), (1l4)~ ~115~,(117) or (118) and melt~d, with stirring, at 285C. The spinnin~ melt is spun through conventional spinnerets to ~ive strongly whitened polyester fibres.
.
Example 10 _ _ , . . .
A polyamide fabric (Perlon) is put at 60C, in the liquor ratio o 1:40, into a bath which contains (referred to the weight of the fabric) 0,1% of one of the f]uorescent brighteners of the formulae (102), (104), (126) or ('l28) and~
per litre, 1 g of 80% acetic acid and 0.25 g of an adduct o ~0 to 35 moles of e~hylene oxide and 1 mole of commercial stearyl alcohol. The bath is heated within 30 minutes to boiling ~emperature and kept at the boil for 30 mînutes. The abric is then rinsed and dried. ~ strong white effect of good light iastness is obtained.
Similarly good white effec,ts are obtained by using a ~abric made of polyamide 66 (nylon) instead o~ polyamide 6 Finally, it is also to carry Ot1t the process under high temperature conditlons, e.g. over the course of 30minu~s at 130C. For this kind of applica~ion it is advisable ~o add 3 g/l of hydrosulphite to the solution~
,'. ~ ' . ' ' . ~': ' ' : ', . . - .
.
Exalllple 11 lO,000 g of polyam-Lde chips obtained in known rnanner from hexameth~lenediamine adipate are mixed for 1~ hours in a roller vessel with 30 g of titanium dioxide (rutile modifica-tion) and 5 g of one of the compounds of the formulae (102), (104~, (12~) or (128). The treated chips are me].ted in a boiler which is heated with oil or diphenyl vapour to 300-310C, after expulsion of the atmospheric o~ygen with steam~
and stlrred ror half an hour. The melt is ~hen pressed out:
through a spinneret under a nitrogen pressure o F 5 atmosO
(gauge) and th~ spun, cooled filament is wound on a spool.
l'he threads obtained exhibit a good white effect.
Simi.larly good results a~e obtained by uslng a polyamide obtained from -caprol.actam instead of from hexa~
. methylenediamine adipate.
E~ample 12 A cellulose acetate fabric is put a~ 50C into an aqueous bath (liquox ratio 1:30 ~o 1:40) which conLains 0.15C/o (based on the weight of the fabric~ of one of the compounds o~ the formulae (104), (126) or (128). The temperature of the treatment bath is brought to 90-95C and l.~ept thereat for 30 to 45 minutes. After the fabric has been rinsed and dried, a good white effect is obtained~
~0 ~
: ' . - ., , .:'' - ' . ' ' ~:
.
Example 13 An intimate mixture of 100 parts o. polyvinyl chloride, 3 parts of a stabiliser (Advas~at BD 100 : Ba/Cd complex), 2 parts of titanium dioxide, 59 parts o dioctyl phthalate and 0.01 to 0.2 part of one of the compounds of the formulae (102)~ (104), (i26) or (128) 7 are rolled out to a sheet on a calender at 150C to 155C.
The resultant opaque pol~7vinyl chlori.de sheet has a markedly higher white content than a sheet that does not contain the 1uorescent brightenerO
Example 1 A casting compound that consists of pol~acry~Dnitri:le~
0,2 g of titanium dioxide (anatase modifi~ation) as mattin~
agent, and 40 ml of dimethyl formamide, and which con~ain Smg of one of the compounds of t~e formulae (102~; (10~), (126) or (128), is poured onto a glass plate and dra~n out wi.th ~ me~al ~od to form a thin filsn. After it has dried, the film has a pronounced white effect.
Example 15 A 27% polyurethane casting compound in ethyl ace~a~e which contains, referred to the plastics dry weight, 2% of titanium dioxide (anatase modification) 9 5% of a stabiliser and 5% of a eatalyst as well as 0.05% of th.e compound o~ the .. , .. . , ... ,, , . - . -: ~,. , ., -: :: , - . . .
~, . . . ..
.. . . . . . . .
formula (104) or (126), is poured onto a glass plate and drawn out with a metal rod to form a thin film. After it has driedS the film has a pronounced white effect.
.
Example 16 100 parts of polystyrene and 0.1 part of one of the compounds of the formulae (104), (126) or (128) are melted in a ~ube of 1 cm diameter for 20 minutes at 210C excluding air, After the melt has cooled, a brightened polystyrene compound of good light fastness is obtained.
Example 17 Polypropylene fibres are treated with 0~02 to 0.4%
of the formula (104) for 60 minutes at 60~ to 100C in a bath (liquor ratio 1:40) which conta:ins per litre 5 g of an adduct o~ app. 35 moles of ethylene ox:;de and 1 mole of octadecyl alcohol, and 0.5 g of trisodium phosphateO The material is then rinsed and dried. The polypropylene fibres have a markedly higher white content than untreated fibres.
A similar effect is obtained by usin~ 1 ~ of 85%
formic acid instead of 0.5 g of trisodium phosphate.
42 ~
': . .. . .
. .
~, ' .
. .
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of 2-stilbenyl-1,2,3-triazoles of the formula wherein Rl represents hydrogen or an alkali metal, alkaline earth metal, ammonium or amine salt cation, R2 represents hydrogen, alkoxy of 1 to 4 carbon atoms, carboxyalkoxy of 2 to 6 carbon atoms or together with R3 represents methylenedioxy, R3 represents hydrogen, alkoxy of 1 to 4 carbon atoms, carboxy-alkoxy of 2 to 6 carbon atoms, alkoxyalkoxy of 2 to 6 carbon atoms, phenoxy, phenoxyalkoxy of l to 3 carbon atoms in the alkyl moiety, chlorine, alkyl-mercapto, phenylmercapto, alkyl of 2 to 4 carbon atoms, or together with R2 represents methylenedioxy or together with R4 represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by chlorine, alkoxy of 1 to 4 carbon atoms or or , in which each of Y1 and Y2 independently represents alkyl of 1 to 4 carbon atoms, R4 represents hydrogen or together with R3 represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by chlorine, alkoxy of 1 to 4 carbon atoms or or , in which each of Y1 and Y2 independently represents alkyl of 1 to 4 carbon atoms, R5 represents hydrogen, chlorine, alkoxy of 1 to 4 carbon atoms, , , in which Y1 and Y2 have the meanings already assigned to them, or represents -SO2-phenyl, which comprises reacting a 2-tolyl-1,2,3-triazole of the formula wherein R2, R3, R4 and R5 have the indicated meanings, with an anil of the formula wherein Ar1 represents phenyl, chlorophenyl or naphthyl and R1 has the indicat-ed meaning, in the presence of a strongly basic alkali compound in a strongly polar, neutral to basic organic solvent.
2. A process according to claim 1 for the manufacture of 2-stilbenyl-1,2,3-triazo1es of the formula wherein R? represents a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion, R? represents hydrogen, alkoxy of 1 to 4 carbon atoms or together with R? represents methylenedioxy, R? represents hydrogen, alkoxy of 1 to 4 carbon atoms, phenoxy, phenoxyalkoxy of 1 to 3 carbon atoms in the alkoxy moiety, chlorine, or together with R? represents methyl-enedioxy or together with R? represents the completion of an unsubstituted naphthalene ring or of a naphthalene ring which is substituted by alkoxy of 1 to 4 carbon atoms, R? represents hydrogen or together with R? represents the completion of an un-substituted naphthalene ring or of a naphthalene ring which is substituted by alkoxy of 1 to 4 carbon atoms, and R? represents hydrogen, methoxy or -CONY1Y2, wherein each of Y1 and Y2 in-dependently represents alkyl of 1 to 4 carbon atoms; which comprises reacting a 2-tolyl-1,2,3-triazole of the formula wherein R? to R? have the meanings assigned to them hereinbefore, with an anil of the formula wherein Ar1 represents phenyl, chlorophenyl or naphthyl and R? has the meaning assigned to it hereinbefore.
3. A process according to claim 2 for the manufacture of 2-stilbenyl-naphtho-1,2,3-triazoles of the formula wherein R? represents a hydrogen, alkali metal, ammonium or amine salt ion, R6 represents hydrogen or alkoxy of 1 to 4 carbon atoms, which comprises reacting a 2-tolyl-naphtho-1,2,3-triazole of the formula , wherein R6 has the indicated meaning, with an anil of the formula , wherein h represents chlorine or hydrogen and R? has the meaning already assigned to it.
4. A process according to claim 3 for the manufacture of 2-stilbenyl-naphtho-1,2,3-triazoles of the formula , wherein R? and R6 have the meanings assigned to them in claim 3.
5. A process according to claim 2 for the manufacture of 2-stilbenyl-benzo-1,2,3-triazoles of the formula wherein R?, R? and R? have the meanings assigned to them in claim 2.
6. A process according to claim 1 which comprises the use of an alkali metal compound of the formula KOCm-1H2m-1 or NaOCmH2m+1 wherein m is an integer from 1 to 6, as strongly basic alkali compound.
7. A process according to claim 1 which comprises the use of potassium or sodium tert. butylate or potassium hydroxide as strongly basic alkali compound.
8. A process according to claim 1 which comprises the use of dialkyl amides of formic acid or of phosphoric acid or tetraalkyl ureas of 1 to 4 carbon atoms in the alkyl moiety as well as N-alkyl lactames of 5 to 10 carbon atoms, as strongly polar, neutral to basic organic solvent.
9. A process according to claim 8 which comprises the use of dimethyl formamide, diethyl formamide, hexamethylphosphor-ic triamide, tetramethylurea or N-methylpyrrolidone as solvent.
10. A 2-stilbenyl-1,2,3-triazole of the formula wherein A represents a benzene or naphthalene ring which is unsub-stituted or substituted by one or more non-chromophoric groups selected from alkyl, fluorine, bromine, chlorine, alkoxy, alkoxy-alkoxy, aryloxy, aralkoxy, arloxyalkoxy, alkenyloxy, aryl, alkyl-mercapto, alkenylmercapto, arylmercapto, arylsulphonyl, cyano, carboxy, carbalkoxy, carbamoyl, sulphamoyl, sulphonyl, or methyl-enedioxy, and R1 represents alkyl of 2 to 4 carbon atoms, halo-alkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, or phenoxyalkyl of 1 to 3 carbon atoms in the alkyl moiety, and if A represents a benzene ring substituted by non-chromophoric groups, R' can also represent hydrogen or an alkali metal, alkaline earth metal, ammonium or amine salt cation.
11. A 2-stilbenyl-1,2,3-triazole according to claim 10 of the formula , wherein R? represents alkyl of 2 to 4 carbon atoms.
12. A 2-stilbenyl-1,2,3-triazole according to claim 11 of the formula .
13. A 2-stilbenyl-1,2,3-triazole according to claim 10 of the formula wherein R?' represents a hydrogen, alkalimetal, ammonium, amine salt ion or alkyl with 1 to 4 carbon atoms, R? represents hydrogen, alkoxy with 1 to 4 carbon atoms or together with R? represents methyleue-dioxy and R? represents alkoxy with 1 to 4 carbon atoms or together with R? represents methylenedioxy.
14. A 2-stilbenyl,1,2,3-triazole according to claim 13 of the formula wherein R?' represents hydrogen or alkoxy with 1 to 4 carbon atoms and R?' represents alkoxy with 1 to 4 carbon atoms.
15. A stilbenyl-1,2,3-triazole according to claim 14 of the formula
16. A 2-stilbenyl-1,2,3-triazole according to claim 14 of the formula
17. A process for optically brightening a synthetic organic material selected from synthetic high molecular weight organic materials, regenerated man-made organic materials and natural organic materials of animal or veget-able origin, which comprises incorporating therein or applying thereto a 2-stilbenyl-1,2,3-triazole as defined in claim 10.
18. A process according to claim 17 for optically brightening polyesters which comprises incorporating in a polyester spinning melt a 2-stilbenyl-1,2,3-triazole as defined in claim 13.
19. A process according to claim 18 wherein a 2-stilbenyl-1,2,3-triazole of the formula is used wherein R2'" represents hydrogen or alkoxy with 1 to 4 carbon atoms and R3"' represents alkoxy with 1 to 4 carbon atoms.
20. A process according to claim 18 wherein a 2-stilbenyl-1,2,2-triazole of the formula is used.
21. A process according to claim 18 wherein a 2-stilbenyl-1,2,3,-triazole of the formula is used.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1222574A CH618057GA3 (en) | 1974-09-09 | 1974-09-09 | Process for optically brightening textile organic materials with 2-stilbenyl-1,2,3-triazoles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1080718A true CA1080718A (en) | 1980-07-01 |
Family
ID=4381051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,833A Expired CA1080718A (en) | 1974-09-09 | 1975-09-05 | 2-stilbenyl-1,2,3-triazoles which contain carboxyl groups |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5152437A (en) |
| BE (1) | BE833162A (en) |
| CA (1) | CA1080718A (en) |
| CH (1) | CH618057GA3 (en) |
| DE (2) | DE2539537A1 (en) |
| ES (1) | ES440784A1 (en) |
| FR (1) | FR2283894A1 (en) |
| GB (2) | GB1508329A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442479A (en) * | 1977-09-12 | 1979-04-04 | Mitsui Toatsu Chemicals | Fluorecent brightening of synthetic fiber material in organic solvent |
| US4366189A (en) * | 1979-12-21 | 1982-12-28 | Ciba-Geigy Corporation | 4-Heterocyclyl-4'-vinylstilbenes |
| US4539161A (en) * | 1980-07-25 | 1985-09-03 | Ciba-Geigy Corporation | Amine oxide compounds |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1029792B (en) * | 1951-09-06 | 1958-05-14 | Geigy Ag J R | Optical brighteners |
| DE2010764C3 (en) * | 1969-03-07 | 1975-08-28 | Nippon Kayaku K.K., Tokio | 4- (2-triazolyl) -2-cyano-stilbenes |
| BE789446A (en) * | 1971-10-02 | 1973-03-29 | Ciba Geigy | TREATMENT OF OPTICAL BRIGHTENERS OF THE TRIAZOLYL-STILBENE TYPE THAT CAN BE INCORPORATED IN DETERGENTS |
| IT966203B (en) * | 1971-10-07 | 1974-02-11 | ALKHYLBENZOSSZOLYLSTIL BENICI WHITENERS |
-
1974
- 1974-09-09 CH CH1222574A patent/CH618057GA3/en unknown
-
1975
- 1975-09-05 CA CA234,833A patent/CA1080718A/en not_active Expired
- 1975-09-05 DE DE19752539537 patent/DE2539537A1/en not_active Ceased
- 1975-09-05 DE DE19752539461 patent/DE2539461A1/en not_active Withdrawn
- 1975-09-08 GB GB36883/75A patent/GB1508329A/en not_active Expired
- 1975-09-08 GB GB36884/75A patent/GB1508330A/en not_active Expired
- 1975-09-08 ES ES440784A patent/ES440784A1/en not_active Expired
- 1975-09-08 BE BE159818A patent/BE833162A/en unknown
- 1975-09-08 FR FR7527429A patent/FR2283894A1/en active Granted
- 1975-09-09 JP JP50108617A patent/JPS5152437A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5152437A (en) | 1976-05-10 |
| DE2539461A1 (en) | 1976-03-18 |
| FR2283894B1 (en) | 1978-04-07 |
| CH618057B (en) | |
| GB1508329A (en) | 1978-04-19 |
| DE2539537A1 (en) | 1976-03-18 |
| GB1508330A (en) | 1978-04-19 |
| ES440784A1 (en) | 1977-03-16 |
| CH618057GA3 (en) | 1980-07-15 |
| FR2283894A1 (en) | 1976-04-02 |
| BE833162A (en) | 1976-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3890305A (en) | Divinyldiphenyl compounds | |
| US3849163A (en) | Process for the optical brightening of organic materials | |
| CA1099727A (en) | Benzofuranyl-benzimidazoles | |
| US4317782A (en) | Distyryl compounds | |
| US3682946A (en) | New bis-naphthoxazolyl-derivatives | |
| US3956395A (en) | Distyrylbenzene disulfone derivatives | |
| EP0136259B1 (en) | 4-heterocyclyl-vinyl-4'-styryl-biphenyls | |
| CA1080718A (en) | 2-stilbenyl-1,2,3-triazoles which contain carboxyl groups | |
| US3825534A (en) | Styryl compounds,processes for their manufacture and their use | |
| US3351591A (en) | 4-azolyl-4'-oxdiazolyl-stilbenes | |
| US4014870A (en) | Stilbene compounds | |
| DE2405056A1 (en) | NEW BENZOFURAN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE AS OPTICAL BRIGHTENERS | |
| US4166176A (en) | Fluorescent dyestuffs | |
| US3850914A (en) | Novel alkyl-benzoxazolyl-p-phenyl stilbenes | |
| US4206072A (en) | Benzoxazolyl-phenyl-stilbenes | |
| US3328310A (en) | Optically brightened organic compositions | |
| EP0002042A1 (en) | Diamino-1,3,5-triazinylstilbene compounds, a process for their preparation and their use as optical brighteners | |
| US4013713A (en) | Diarylvinyl-dihydrophenanthrene compounds | |
| US4013642A (en) | Heterocyclic compounds containing sulpho groups | |
| US4172045A (en) | Process for the manufacture of 2-stilbenyl-1,2,3-triazoles which contain carboxyl groups, novel 2-stilbenyl-1,2,3-triazoles which contain carboxyl groups and the use thereof as fluorescent brighteners | |
| DE2309614A1 (en) | AZOLE COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND THEIR USE | |
| US4508784A (en) | 4-Styryl-4'-vinylbiphenyls, the production thereof and use thereof as fluorescent | |
| US3758460A (en) | Styryl compounds | |
| US3898234A (en) | 4,4{40 -Dinaphthyl-1,1{40 ,8,8{40 -tetracarboxylic acid diimides | |
| US3679669A (en) | Phenyl-1,3,4-oxdiazole compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19970702 |