BE628694A - - Google Patents

Description

       

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  Nomlles ph6nylT-pyrszolylcoumorins, which can be used in particular as optical brighteners.



  The present invention 8 for the purpose of further
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 velles 3: phenyl -? - pyrazolyl-coumerinee, a process for preparing these bodies and the application of 3-phenyl-7pyrazolyl-coumarins as optical brighteners.



   The Applicant has found that interesting derivative * of coumarin is obtained by condensing
 EMI1.3
 a 3-phenyl-7-hydrazino-coumarin, which may carry other constituents, or a compound which reacts such as a 3-phenyl-7-hydrazino-coumarin, with a compound containing a group c: olrdicarbonylo aliphatic, or ov4 & 4 a compound containing a group capable of reacting as an aliphatic α1-dlcarbonyl group, and optionally by sulfonating the 3-phenyl-7-pyrazolyl - ('). coumarina thus obtained and, if desired, converting it to an amide by the 'acid halide intermediate

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 EMI2.1
 aulfonic.



  The 3-phenyl-7-hydra2lno-coumarinas which can be used according to the invention and, consequently also, the new 3-phenyl-7-pyrazolyl-coumarins, can also bear, on the 3-phanyl residue, one or more substituents. , for example alkyl groups, such as methyl, ethyl, pxopyl # isopropyl or butyl groups, halogens, such as 10.

   fluorine, but more particularly chlorine or bromine, groups
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 alkoxy, such as methoxy #ethoxy, propoxy or butoxy groups, alkylene or alkyleno-ether groups linked to the benzene ring by neighboring positions, such as
 EMI2.3
 tetramethylbne and m4thylene-dioxyl groups also sulfonic acid groups, "sulfamylol groups substituted or not on nitrogen, for example N-alkyl- and N, N-dialkyl-sulfemyl groups optionally suffered! - killed, such as groups N-methyl-, N-ethyl-, N-butyl-, N-hydroxyethyl-, N-methoxy-ethyl, Nethoxy ethyl, Nr dimethylaminoethyl-.

   N-dimethyl- and N-diethylsulfamyl groups, alkylsulfonyl groups, such as methyl.ulfonyl, ethylsulfonyl or butylsulfonyl groups, alkoxycarbonyl groups, such as methylsulfonyl, ethylsulfonyl or butylsulfonyl groups, alkoxycarbonyl groups, such as losbonyl groups, ethoxycarbonyl, butoxycarbonyl, benzyloxycarbonyl or cyclohexyloxycarbonyl, carbemyl groups which may or may not be substituted with nitrogen, such as
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 diethyl, dibutyl- or dicyclohoxyl-carbamyl groups.



   The 4 position of the coumarins which can be used or prepared according to the invention is occupied by the reference.

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 by a hydrogen atom, otherwise by a lower alkyl group, and in this case, preferably, by the methyl group. The benzo residue of coumarin can also carry substituents, for example methyl groups occupying, for example, the 6 position.
 EMI3.1
 



  The 3-phenyl-7-hydrazino-coumarins which can be used as a starting material are readily obtained from the known 3-phenyl-7-amino-coumarinos by diazotization and reduction of the diazo group to the hydrazino group, the reduction being effected. with the usual agents, such as for example soluble soils of sulfurous acid, zinc in alkaline solution, or soils
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 stannous in acidic solution.

   Instead of the free hydrezino compounds, it is possible to use derivatives of these compounds which react in the same way, for example, more stable salts with strong mineral acids, such as
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 quo 49% oh4othydretot # le% bromhydroto4 # lo4 tul (4t * # $ optionally also the corresponding hydrazino-H-sulfonic acids or the corresponding N-scylydxcxino compounds which are condensed with the dicarbony-liquex compounds under conditions which cause in at the same time the release of the hydrazino groups.



   In the compounds which can be used according to the
 EMI3.4
 vention which contain a grouping. -dlc8fbonyii- aliphatic, this bivalent group may be raised at each of its ends, & hydrogen atoms
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 or to monovalent organic residues, for example to elkylos groups # to arl: cyles groups, such as. the benzyl group, to cycloalkylas groups, cemrt3 the cycloh0) 'yl group, aryl groups, such as the group

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 phenyl # to alkylphenyl, alkoxyphenyl or halophenyl groups, that is to say that one can use, as the starting material, the dialddehyde of P-keto. aldehydes and a * - (diketones or compounds which
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 react like these bodies.

   Meso carbon atom
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 of this group a. Ô-.dicarbonyl can also
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 carry a monovalent substituent of the nature mentioned above, in particular a lower alkyl group. As compounds which can be used according to the invention.
 EMI4.5
 tion, which contain a group a. '-dicarbonY11quo aliphatic, there will be mentioned 1,3., diketanoa, such as for example acetylacetone, propionylacetone, butyryloketono # acetyl-isobutyryl-metheno, acetyl-c4proyl-mdthenep dibenzoyl-methane, benzoylacetono , propionyl-acitophononoo buttylacdto-phenonot phenylacetyl-acetophnono of P-keto-aldehydes or .o4 '.. and "ydb.ym4thVlno-c'tofte. which react in the same way, for example dimethylacetal from -c4to - butyraldehyde, formylacetone or hydroxymethyino.

   acetone, 2-hydroxymdthylene-diethyl ketonone, diethyl., acetyl-acetaldehyde, trimethylacetyl-acetaldehyde, isovaleryl-acetaldehyde, w formyiac6tophnone or 1 '-hydrottymethylene-acetophenone, hydroxymethylbno. cyclohexanone; 0-dialddhides or acetals, alpha-8cyloxym6thylene- and alpha-alkoxymethylbno-alddhyde-
 EMI4.6
 acetals which react in the tiny way, for example
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 tetraethylacetal of malonic aldehyde, acetal of 0-4thoxy-scroldins As compounds which can be used
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 according to the invention which contain an apto group to
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 react as an a, f '.. aliphatic dicsrbonyl residue,

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 one can envisage for example \ the a-hydroxymethylene ketones already mentioned as well as their outside,

     esters or enilides, in addition ketals of aldehydes or keto
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 nose and more precisely derivatives of the dialddhides, aldehyde-ketones or diketones mentioned above in which- a single carbonyl group or los soft are
 EMI5.3
 acetalia. It is also possible to envisage derivatives of the a.1i -dicarbonyl compounds mentioned above which, instead of carbonyl groups, contain .ldlm1de groups. or c'timides non-cyclic or a group # .8rnlnom6thy.tbne-c8rbonyl or carbimido. As an exemption, the anile of -.nilino-acro14ine will be mentioned.



  Finally, one can also use, instead of OOMPol'iú, "- d1CarbOnYliQuOI mentioned above, their adducts with alkali hydrogen sulphites', in which case it is appropriate to carry out the conditioning under conditions such as the carbonyl group is regenerated * In these compounds, all the organ-
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 nics may still carry 1nortol substituents. The condensation of 7-liydrazino-3-ph4nyl coumarin or of a derivative thereof which reacts in the bleak way, with the compound 1.3..dïcarbonyliqua or with a corresponding acetal, is advantageously carried out in a polar organic solvent, in presence of protons or acid reaction accelerators.

   A suitable solvent is glacial acetic acid which can optionally be used in admixture with other solvents. In the examples given below, more details will be found on how to carry out the procedure conveniently. condensation.



   A variant of the preparation process

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 EMI6.1
 conformal 7-pyraMlyl-3-phenyl-coumarlnos. the invention consists in reacting 7-hydrazino-3-phenyl-
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 EMI6.3
 Coumarins having compounds which contain a P-alkynylcarbonyl group or a moiety reacting as an α, ... alkynylcarbonyl group.



  For example, a.p-alkynyl-
 EMI6.4
 ketones or -aldehydes or their acetals, as well as
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 a-halo9'no-a.-alk4nyl-c'tone. bu -aldehydes and their acdtall. In these compounds, the carbon atom in position 0 of the alkynyl roste or of the alkenyl residue
 EMI6.6
 can carry either only hydrogen or also.
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 organic residues, such as alkyl or phenyl residues.



  As alkynyl ketones and alkynyl-alddhides
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 or as compounds react in the same way, we use
 EMI6.9
 read pcr example ph4nylet, Vnyl-ptiénylcdtone # diethylacetal of propargyliquo aldehyde, didthyl- acetal of mdthylpropirgylic aldehydep phenylproporgyltic aldehyde, diethyloketal of phenylpropargyliquo aldehyde - α-bromo-cinnanique, 114-bromo-acroldin, α-bromo-acrolein di4ethylacetal or α-bromostyryl-phenyl-ketone (c: -bromo-chalcone).
 EMI6.10
 



  A second variant of the preparation process
 EMI6.11
 tion of 7-pyrazolyl-3-phnyl-côumarinos in accordance with the invention notes A condense of the 3-phnyl-7-hydra-tino-coumarins mentioned above, with compounds containing α # OA-lc4nyl-carbonyl groups or with
 EMI6.12
 compounds containing groups which, under the condi- tions of condensation, react as a group

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 a..1c'nylc4rbonylOt condensation which leads to 7a pvr "oUnyl-3-rhdnyl-coumlr1nol, and! I of hydroo4nozo these dornibres on pyretolyi3phnyl-coumerinQn corresponds to dantot.



  As utilliablos compounds according to the invontion and which contain QfOUP.I.llc'nyl-clrbony141, we will first mention the chalconoup law that is to say for example a-bonzyl1d'n, -c'tonol which are capable of reacting, in a known manner, with hydr42ines and thus generating PYII.o11nol. We maintain by exonplo In bonsilacdtone, rtyryl-dthylc6tono, to rtyryitort3o butyl-cdtone, ph4nyl-viny1-c'ton., Phny 1-preprfnyi- citona, composed of which the benzlniquoi nuclei can 'Oll.mont portor of inert substitutes , t <l <that groups tlky.te <t halogens or groupos alkouye
 EMI7.2
 Commo compote containing an apto group
 EMI7.3
 11 react as a group G.1! Alabnyianibonylo under the conditions of the reaction, there will be mentioned ketones containing, on a carbon atom, a substituent # 'n' * # '#' & 'loctrophl1.

   labilet, for example a halogen or an amino group, such as the tertiary groupa nmino bases of 'onniche The condensation of a-Vl1d.nè-c'tone. with 14 hydrazine group, which results in pyrotolinof 4 # preferably in acidic organic solution, for example in the presence of acetic acid or mineral acids, such as halohydric acids.

   The ¯-haloq4no- ketones are condensed together with the presence of df4ccOP '
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 acid turns, for example in the presence of carbonates
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 alkalis, the Mannich bases are reacted in

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 neutfe, gt their halohydrataa in prince of carbonates
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 alkaline *
 EMI8.3
 To dehydrogonar the pvrlzol1- nyl substituent an aubstitu4nte pyrazolylest, for example, it is made to act in the form of an organic solution, for example with chloranil, of which the xylbnqe has ancoru halo Qn .., such as chlorine or bromine, or upstream dosages of oxidationg such as sulfur or air in the presence of an oxygen carrier, such as strong salts Of which this variant wgeloment,

   the cyclization is suitably made in an acid medium @
 EMI8.4
 According to another variant of the process * do
 EMI8.5
 preparation dos 3-phnyl-7-pyrazolyl-? oumarinea, one condenses dos benzaidehydet containing, in position 2, a
 EMI8.6
 hydroxyl group or a substituent converted to a
 EMI8.7
 hy group (hydroxylo # and, in position 4, an optionally substituted pyrosol group, pnr dot known methods of acetic acid derivatives whose carbon atom has another optionally substituted phenyl r ato, condensation which provides the derivative * of the corresponding P * 'pMnyl "acrylic acid, after which dYontu01 is released.

   
 EMI8.8
 loment in the form of hydroxyl group the substituent carried
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 by the remainder "-p14nyle we position ortho of the acrylo remainder,
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 and this hydroxyl group is cyclized with the carboxyl function of the acrylic acid residue to create the ring
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 coumarin. Lee benzalddhydes necessary as a body '
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 starting points in this variant are for example the'-2
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 hydroxy-4-pyrazolyl-benzaiddhyde and corrotiating derivatives of benznlddhyde bearing substituents on
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 the pyrazolo nucleus. However, we will mention as parti-
 EMI8.15
 particularly favorable 4-pyrazolyl-bonzolddhydou
 EMI8.16
 

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 which carry, in position 2, an alkoxy group as a substituent convertible into a hydroxyl group.

   The 2-
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 hydroxy-4-pyrazolyl-bonznid <5hyd8 so readily prepared by the synthesis of Reimrr and Tiomann by introducing an aldehyde group in the ortho position of m-pyra-
 EMI9.2
 zolyl-phenoi by means of chloroform and a caustic potash lye.
 EMI9.3
 



  As condensable derivatives of the ocetic acid which destroys the α-carbon atom, a pli4n group, lo or a substituted phenyl group, it is possible to envisage, for example, pht <nylac4tiquo acid or its ostors, more cuHtromont its alkylicfuox esters. , but preferably the '! phjnyl-ec6ton1trilo8 (cyanides of bGnzy, ioj.
In the two starting substances, the aromatic nuclei can optionally carry substitutes.
 EMI9.4
 further killing substituents which are inert under the reaction conditions, such as halogen atoms, alkyl groups, and possibly also
 EMI9.5
 alkoxy groups.



  The condensation which should lead to the compound 0 "ph" nylacj? Yliqu0 is carried out by known methods, for example in alcohol is pr4sonce of caustic alkalis, alkali alkalis or pip4ridino * If one uses o-alkoxy -alddhides for the condensation, then the hydroxyl group must then be released. This release takes place suitably with anhydrous aluminum chloride in inert organic solvents, such as
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 the goodzhnnt chlorobenzeno or nitrobonzno, possibly also in a melt of aluminum chloride and sodium chloride, or in a melt.

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 EMI10.1
 pyridino hydrochloride) or alternatively with a solution of hydrobromic acid in glacial acetic acid. Sub-
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 go, coumarinic cyclization is achieved at the same time.

   In this case, it is not necessary that the
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 cr1 group: the alkyl, the residue of acrylic acid is in free form. It may well be in a functionally modified form, for example as an ester, a helper and, preferably, a njtrtlee.
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 When coumarinic cyclization ho se
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 not already produced during group deselkylation
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 alkoxy, or when obtained, as reaction product
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 from the first stage, a dr1v <:

  "acid P - (2 hydroxyph <înyl) - acryliquop one carries out beforehand tagousomont the cyclization
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 with a solution of a halohydriquo acid in an acid
 EMI10.9
 lower fat But other condensing agents can also be used, for example zinc chloride
 EMI10.10
 or concentrated phosphoric acid
 EMI10.11
 tes 3 ... phnYl..7 ", pYft.Uoly! ... couml3r1nea according to the invention can carry, on the 3-phdnyle residue # a sulphonic acid group, or an 8l.t! famylo 6von group ...
 EMI10.12
 also carrying substituents on nitrogen.

   These
 EMI10.13
 groups can already be found in the 3phryl-hydrasina-ecaumari, nas utl1j & 4QS as reao '* tionnall partners, as for example in the acids 3 - phenyl.7 .. hydrazino "coumarins'-3'- or 4'-sulfoniquos, or in (3'- or -N-dithyisulfamyl.-phny.-7.-hydraxlna coumarinos, bias # often, it is also possible to do

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   introduce the sulfo group only after the condensation reaction according to the invention, by sulfonation.
 EMI11.1
 If desired, the sulfanic acid group formed *, preferably meta or parially of the 3-phenyl residue, can be converted, in known manner, for example with chlorides of mineral acids, such as thionyl chloride,

   we halogen group
 EMI11.2
 sulfonyl which can then be reacted with do? amino, by known methods, to convert it
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 in sulfamylo group, the amide group can also dtra introduced by treatment of the compound 3phenyl7 pyrazolyl-coumariniquo with chlorosulfoniquo acid, then reaction of the sulfochloruro formed with the amines.
 EMI11.4
 



  The 7 <pyrazolyl'-3 "phenyl-coutrines according to the invention are aristri, ii.wd * o, colorless substances, Itfçfcfftmtnt yellow. They correspond to the following general formula:
 EMI11.5
 
 EMI11.6
 In this formula, the symbols RIP R2 and Reg each represent a hydrogen atom or an aliphatic, 'licvcJiqu.,'. 11Phatlquo or aromatic residue, B5 represents an optionally substituted phenyl residue, and R is preferably hydrogen. ass still a lower alkyl residue. The new 7c * 'pyrazolyl-3-phenyl-coumarinos have a violet fluorescent vivo when dissolved in

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 organic solvents, such as alkanols, dioxane, dimethylformamide.

   In very small quantities they will give to the yellowed organic matter in which they have been incorporated or on which they have been deposited by conventional methods, an appearance of pure white in daylight, and this is why they constitute d. Interesting optical brighteners. In comparison with the known comparable optical brighteners, which belong to the coumarin series and which carry a nitrogen substituent in position 7, the compounds of the present invention are distinguished by better light oslidity. , by a more neutral whiteness effect and, as a consequence of this latter property, by a better color in the evening, as well as by a good stability to heat, They are therefore suitable as optical arurants,

   in particular for synthetic polyester fibers, for example the polymeric ester of terephthalic acid with polyol backing, and for cellulose acetate fibers, in particular for cellulose triacetate fibers, as well as for fibers synthetic polyamides. They also improve the appearance of acrylonitrile polymers and copolymers when incorporated into molten resins prior to spinning, of plastics, such as polyvinyl chloride, polyvinylidene chloride, polystyrenes, polyethylene. , polypropylene, polymethacrylate, ocpolymers of these bodies with each other or with other polymerizable compounds.

   They can also be in-

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 EMI13.1
 corporor in products intended for labeling, for example, for the intake of textile fibers, such as polyvinyl alcohol, or in resins or resin layers which are used for the treatment of textiles *
For application on textiles, we
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 aqueous bath, mn advantageously uses 3-phtnyl 7-pyrazolyl-coumarins in the finely divided state, the presence of .dispersants are incorporated into the polymer plastics, for example, by dissolution in a monomeric base material or in low weight molecular before polymerization, or
 EMI13.3
 dissolving in the fossouplissoge agent to be incorporated, or by addition to the spinning mass before passing through the die.



   It is recommended, for the application in aqueous bath on textiles, to use the
 EMI13.4
 3-phenyl-7''pyrazolyl-'coumarino '% 6n amounts of about 0.01 to 0.1% based on the weight of the fiber for bluing plastics, the amount of ozu-
 EMI13.5
 rant to use to go from 4.05 fi 0. ' Depending on the material <Los.3-phenyl-7-pyrazolyl-countarinos according to the invention can also be used in the detergent. The amount of diozurants conforms to the invontin. add to the detergents are then advantageously between 0.05 and 0.2% relative to the dry weight.



   The following examples illustrate the present invention without in any way limiting its scope. Unless otherwise indicated, the parts referred to in these examples are by weight,

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 EMI14.1
 We introduce 25.2 parts of @ -phenyl-
 EMI14.2
 7-hydrazino-coumarino in a solution of 20 parts of acetyloketone ot 250 parts of glacial acetic acid, and, while stirring, the mixture is heated to 100 ° C. for an hour * After cooling, the seed is filtered off, the precipitate obtained is washed, it is washed. with cold ethanol and, while treating it with decolorizing black, it is rocrystallized in toluene.

   We thus obtain
 EMI14.3
 3phenyl7-¯3 r .5r-dimthylpyrazolyl- (1 r) wr. aau marine on fine, almost colorless needles that melt at 210 C.



   The product dissolves in acetone with a blue violet fluorescence The new compound works very well for the brightening of various organic bodies, especially synthetic textile fibers and polymer plastics *
 EMI14.4
 The 3-phenyl-7-hydrazino-.coumarino used
 EMI14.5
 in this example, compound. which fnd 11..1 'C, can be prepared starting from 3-phenyl-7-aminocoumarino in the following manner: in nitrogen and hydrochloric solution of 3-phnyi-eminc hydrochloride.

   coumsrino, the yellow diazonium sol obtained is converted by treatment with sodium sulfite into coumarinvl- (7) -hydrazino-N-sulfoniquo acid

 <Desc / Clms Page number 15>

 corresponding and hydrolysed the latter by heating with a mineral acid to convort it into a hydrazino compound or sol of such a compound. From the mineral soil, the free hydrazine base is isolated by
 EMI15.1
 reaction with an aqueous solution dianmoniaquo.



  If we replace in this example the 25.2 parts of 3-nhonyl-7- * hydrazino-or! Arino pnr 26.6 parts of 3- (m-tol, lJ - ,. h, i zzino.- neck: nrine, by 26.6 shared do 3- (p-.tolyl-t-hydra.ïno-coumarinc or by 28.7 partins from 3..ipchlor3phcrlyJ.j.?. tylrazitaw coumarin is obtained, anal .oquu, 3.os following pyrazoliquos derivatives:
 EMI15.2
 CH-C = N, CH C jr- * .stista'jx aunttxs' rifî -C4 == N fondant & n980 "C.



  3 H ('== C - (OH 0 Co melting 179 "1800C t / CO CH 1 OH3 zaza CH3.CUWNN ¯'N ° CH, 6am <P3 paiUottos j6u <A \ - .. X ndtr.s melting at 4tres fondant HCC 2 1 CH3 c'1H1 a., "..,.: -: t CH., - C-.N. ,, Ar'CH C # pailletta maza! CH3 CN C- (Ct rillettes ja <.- , N p, .... Ntros fondant! X \ / \. '' 3723f3 C t CH3
 EMI15.3
 c2OH15N202
These three compounds are also a blue violet fluorescence in organic solution and

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 EMI16.1
 il $ being able to Otto used for the azure of the divare .ub.t.to.



  Los produced intu = ddiairje mentioned above, see lA 3- (m-tolyl) -7-hyd: tazino-coumerino (melting point of hydrochloride 1 26C? C avoc of the composition), the 3. (p-tolyl) -7-hydrazino-coumarlno (melting point 1215 C avuc decomposition) and 3- (p-'chioroph <enyl) -7-hydrazino-caumarino (melting point t 22DOr- with decomposition), is prepared as the 3-ph <! nyl-7-hydrazino'-coumarino d> 5jà described, from doa 3..axy1 7-min.cotxnorinas
 EMI16.2
 corresponding *
 EMI16.3
 EXAMPLE 2 1
 EMI16.4
 
 EMI16.5
 Dleporso, stirring, 28.9 parts of 3-ph.ny hydrochloride ... hydroxy, na. aaumarino in 280 pirtios by volume of ethylene glycol 5thor moaoorthyliqua, with an addition * 19.8 parts of diW;

  thYlac4t & l du 0-cetobutyroldihydea We heat the uusponsinn obtonuo, stir it, laying 3 bouror
 EMI16.6
 
 EMI16.7
 At 90 ° C. to 00 ° C., a solution of 15 parts of sodium acetate crystallized in 30 parts of water was added to the brown milongo, and the gold was cooled to room temperature * an eGparo by filtration. 3 bxunâtxo which is drilled, it is washed with alcohol and water and it is purified by rocristellisati3t in a

 <Desc / Clms Page number 17>

 
 EMI17.1
 8dlângo do benzene ot do ligroyhoo We get 3- 'ph6rryl? "5-mGthylpyraxolyl- (1) 'coumex3no on fine felted needles which melt at 188 C. The new coumarinic derivative has a purple fluorescence when dissolved in dioxane.

   In solution
 EMI17.2
 The product has an absorption maximum at 335'in (log t max 4.44). Co compound is also suitable for rotting organic substrate.



   Similarly, the same coumarin compound is obtained if, instead of 28.9 perties do
 EMI17.3
 3-ph <Snyl-'7-hydraxino '<' coufMrinof hydrochloride 33 µl parts of 3 <-ph 'nyl-7-hydrazino-coutarino-N-sulfoniquo acid are used.



  If we replaced in this example the 28.9 parts of hydrochloride of 3-phnyl. L-7-hydraxino cour1no by 30.3 parts of hydrochloride of 3- (m-tolyl) -7-hydrzino-coumatlne, one obtains , do analogously, the 3 .. (m..tolyl)? '"' â..mljtttylpys, ezolyl (i). coumarin which melts at 153 C. This pyraxolic derivative also has, in organic solution, a violet fluorescence and it can be used as an azurago agent. Its maximum absorption is light in methanol
 EMI17.4
 sa ^ found at 335 mi 'f log Max at 4.4, EXAMPLE 3
 EMI17.5
   Now \ introduces 25.2 parts of 3-phnyl-
 EMI17.6
 7,

  hydrazino-coumarino in a 16 part solution

 <Desc / Clms Page number 18>

 
 EMI18.1
 P-Ketobutyr4lddhyde dimethylacetal in 300 parts of ltdthyleno-glycolp monoethyl ethor and heated to 100 C. A dark young solution is obtained which has a blue green fluorescence and which contains no
 EMI18.2
 more than 3-phenyl-7-hydrazit) o-coumarino libro. After adding 2 parts of 30% hydrochloric acid, the mixture is maintained at 100-110 C for 6 hours.
 EMI18.3
 with stirring, then left to cool to room temperature. Take care of the brown r4ctlonD.lle solution, 3 phSnylT.3..cnethylpyraxolyl- (1) '.

      crude coumarin precipitates in bright yellowish crystals * The product is separated by filtration, washed with alcohol ot, to purify it, it is recrystallized from
 EMI18.4
 chlorobenzene # lo tolueno or ethylene glycol moncethyl ether with the addition of bleaching charcoal.
 EMI18.5
 



  The pure oumariniquo compound forms crystals of slightly yellowish hue which melt at 216.1 ° C. In organic solution, the new coumarinic derivative exhibits a bright blue violet fluorescence. Maximum absorption of light in methanol is obtained.
 EMI18.6
 found at 346 m ,, & 4 r logr X 4.54. The product is an excellent brightener for various oral substrates, such as synthetic textile fibers.
 EMI18.7
 based on polyesters and polyit5ides, such as polyester fibers based on acid, glycol t & r4phtBUque ot, di- to tri-acetylcellulosos fibers, synthetic polypeptide fibers based on adipic acid and hoxamethylenediamine or based on ù -amino acid. caprorque or its lactamo.



   Other brighteners of similar efficacy are obtained by using, in this example, instead of

 <Desc / Clms Page number 19>

 
 EMI19.1
 16 'parts of dimethylacdtel of 0-ce-tobutyrolddhyde, corresponding amounts of dimethylacdtui of propionylacetald4hydo or of dim ± thylac6 * tai of pMnylQclStylac6tBld6hydo.



  EXAMPLE 4 t
 EMI19.2
 Stir overnight at temperature
 EMI19.3
 ambient 26 parts of dinothylacetal eu p-cetobutyparties raldehyde and 26.6 / of 3- (p-tolyl) -7-hydrazino-coumarino in 500 parts on volume of mon ether (lmth't'11quo do l "thylbno-glycol ot, after adding 25 parts of glacial acetic acid, the mixture is heated to 90 ° C. for 6 hours * After cooling, the yellow reaction product is separated by filtration, washed with
 EMI19.4
 ethylene monomethyl ether-.g, ycol ot with alcohol, and recrystallized from toluene
 EMI19.5
 by adding bleaching charcoal.

   The 3- (p-tolyl) -7- * / "3 '-! W! Thylpyrazolyl' - (t ') 7" coumarin obtained forms yellowish crusts melting at 24 ° C! and, in organic solution, it fluoresces blue violet. The new compound can be used for brightening polyamide or polyester fibers which were mentioned in detail in Example 3.



   If we replace in this example the
 EMI19.6
 26.6 parts of 3- (e-tolyl) .7-hydrazino-ceunarlno per 28.7 parts of 3- (p-chlorophdnyl) -7-hydrazlno-

 <Desc / Clms Page number 20>

 
 EMI20.1
 coumarin $ -on obtains the 3 .. (pchlorophfnyl) 7 "3. methYl" pYMZolyl- (') 7-coumarin which melts at 244 * Ce In organic solution this coumarinic derivative 8 also has a blue violet fluorescence and it can be used for blueing organic substrates.



    EXAMPLE 5:
 EMI20.2
 
 EMI20.3
 9.75 parts of bonzoyloketone are introduced into 125 parts of glacial acetic acid and reacted with 12.6 part of 3-phnyi..7-hydraxino coumarin, first laying for 1 hour at temperature.
 EMI20.4
 ambient, well laying 5 hours at 90u95 C, while stirring. After cooling, the mixture is separated by filtration
 EMI20.5
 the r6ct10nnol product yellowish and purified by recrystallization from tolubnoo La 3..phenyl? ..



  "3 ..m'tl-tyl-5.phGnylpyTaaOlyl. (T) 7..coumoxinQ obtained crystallizes in colorless needles melting at 204 C and it has a blue violet fluorescence in a mixture
 EMI20.6
 alcohol and dimethylform & mjdeo The product is useful for the azurogo of synthetic textile fibers.
 EMI20.7
 Its maximum absorption 00 light in methonOl is 338 m .. y log Y. "# 4.42,

 <Desc / Clms Page number 21>

 If we replace this example with the
 EMI21.1
 9.75 parts of bonoy1.1c6tono pcr (z) parts of dibonzoylmethano, one obtains, operating in an analogous manner, 3-phnyl? .. '"3, .. diphnylpyrazolyl (1'% - coumarin, slightly yellowish, which melts 230 C. Co also produces, when in organic solution, has a blue violet fluorescence.

   Its maximum absorption
 EMI21.2
 do the light in methanol is 344 mi. 4 - 109 G max: 8 4.50 ...



  EXAMPLE 6:
 EMI21.3
   12.6 parts of 3-
 EMI21.4
 phenyl-7-hydrazino-coumarin in 125 parts of glacial acetic acid and 10 parts of the sodium salt of W-hydroxymthylencr.ac6tvphenone (Bulcw and Sichererp B 34, 3Q91) are added. The resulting yellow slurry is then brought to and maintained at reflux for 5 hours with stirring. After cooling, the yellow precipitate is separated by filtration, washed with glacial acetic acid, alcohol and
 EMI21.5
 water, and it is purified nar recrtallisaticn dwrs; toluene. We thus obtain the 3-phenyl-7 - / "5'phenyl-pyrazolyl- (l ') 7-coumarin sought in the form of yellow crystals which melt 1235 C and which, in alcoholic solution, give a purple fluorescence. blue*.

   This,

 <Desc / Clms Page number 22>

 product can also be used for brightening organic substrates.



   EXAMPLE 7 t
 EMI22.1
 
12.6 parts of 3-phdnyl-7-hydrazinocoumarino are suspended in 125 parts of glacial acetic acid and, for 10 minutes, 12 per-
 EMI22.2
 Tets of t6trodthylecdtal from aldehydo malonic at room temperature. Then heated to 90 C
 EMI22.3
 and continued stirring for 8 hours at 90-100 C. On cooling, it forms, in the dark brown solution, a yellowish precipitate which is separated by filtration after complete cooling, washed with glacial acetic acid and with water and purifies by recris-
 EMI22.4
 tellisatjon in chlorobenzenea 3-phenyl-7-pyrazolyl- (1 ') - counarino (melting point:

   s 2290C) has a violet fluorescence in organic solution and is suitable for the brightening of organic plastics, for example horn or excavations of polyvinyl chloride or synthetic polyester fibers.



   The same product is obtained if, in this example, the 12 parts of tetraethylacetal of malonic aldehyde are replaced by 9 parts of dimethylacetal of malonic aldehyde.



  EXAMPLE 8:
 EMI22.5
 
 EMI22.6
 

 <Desc / Clms Page number 23>

 
A mixture of 12.6 parts of 3-phenyl- 3 is boiled under reflux for 12 hours, with stirring.
 EMI23.1
 7-hYdr411no-coumarin and 10.4 parts 3 benzalacetphonated in 150 parts of glacial acetic acid, and allowed to cool. The 3..phenyl-7-L '3 .5., Diphdnyi PYJ'azol1nyl. (L') J-co4ft1odne, yellow precipitate, is separated by filtration, washed with glacial acetic acid and alcohol, and dried. The pyrazolin derivative forms a yellow powder ot, in organic solution, it has a green to blue green fluorescence.

   To transform
 EMI23.2
 the pyrazolino nucleus into a pyrazole nucleus, is added 30 minutes at 30-40 C, 8.8 parts of bromine to 22.1 parts of the pyrazoline obtained in 220 parts of chloroform, and the brownish reaction mixture is stirred, a 5C6C1 C.,. until it no longer breaks down hydrobromic solution, then the chloroform is removed by distillation, the dark residue is mixed well with a solution of 10
 EMI23.3
 parts of crittaillot sodium aorta including 100 parts of alcohol and 100 parts of water, the
 EMI23.4
 a brown precipitate, washed with alcohol and water, dried for a short time and recrystallized as a result.

   toluene in the presence of bleaching charcoal. We obtain.-
 EMI23.5
 thus 3phnyl? - '. 5-diphenyipyraxolyl (1') ", 7 coumarin in the form of yellowish crystals melting. 230 C,
 EMI23.6
 compound which is identical to that which was prepared according to Example 5, EXAMPLE 9
 EMI23.7
 

 <Desc / Clms Page number 24>

 
 EMI24.1
 12.6 parts of 3phenyl 1-hydt4zino-coumorin are suspended in 150 parts of acetic acid.
 EMI24.2
 glacial. 9.6 parts of diethyl are added over 10 minutes.
 EMI24.3
 propyl aldehyde acetal and the mixture is encrypted at 100OC for 6 hours with stirring.

   After cooling, the product is separated by filtration, which
 EMI24.4
 has precipitated, washed with glacial acetic acid
 EMI24.5
 and alcohol and re: ristallite in G toluene.



  This gives the 3phtny ... 7..pyrez lyi- (1) -aoumarine described in Example 7, a compound which melts at 2k8.29 C.



  EXAMPLE 1Q 8 a) Preparation of 1- (m-sulfophenyl) .. 3-mdthyà 'rozoloo 104 parts of: 1do .ph'nyl-hydro-zine-m-sulphonic are dissolved in 700 parts of water with 2 p partios of sodium hydroxide and 90 parts of 1,1-dimdthoxy-3-oxo.tene are added to 10OC with stirring (tion. The resulting mixture is then stirred for 14 hours t 2 "0n # and for 3 hours at 9U..1004C, then char-
 EMI24.6
 good decolorizer the clear brownish solution, we filter
 EMI24.7
 and the sodium salt of 1- (m-sulfophenyl) -3 is released.



  , methyl-pyrazole by addition of 20% sodium chloride
 EMI24.8
 After cooling, the product is separated by filtration @
 EMI24.9
 it is washed with a 15% aqueous solution of sodium chloride ot it is dried at 80 ° C. under reduced pressure. We
 EMI24.10
 thus obtains a yellowish gray powder which dissolves easily in water,
 EMI24.11
 b) Preparation of 1- (in-hydroxyphenyl) -3-methyl-pyrazole *
 EMI24.12
 We heat in an autoclave for
 EMI24.13
 6 hours at 26C, -2700C (pressure t 37 atmospheres), under
 EMI24.14
 nitrogen, 418 parts of the sodium salt of sulfonic acid

 <Desc / Clms Page number 25>

 
 EMI25.1
 prepared under a) with a solution of 440 parts of sodium hycroxide in 1000 parts of water, dissolved (hot)

   the brownish crystalline slurry obtained in 1200 parts of water, filtered hot with decolorizing charcoal and
 EMI25.2
 precipitates 1- (m-hydroxyphenyl) -3-methyl-pyrazole formed by addition of 145 parts of acetic acid. The crude product obtained forms a brownish powder. To purify it,
 EMI25.3
 1- (m-hydroxy: .henyl) -3 is recrystallized. crude methyl-pyraxola in 600 parts by volume of benzine. The compound put formalin white crystals melting at 104 C.
 EMI25.4
 c) Preparation of 2hydroxya-J'â'-mdthyipyraxolyl (1 '"-
 EMI25.5
 bonzld6h²de ..



  105 parts of 1- (m-hydroxyphenyl) -3 methylpyrazole, 173 parts of sodium hydroxide} 325 parts by volume of ethinol and 360 parts of water are dissolved at 70 ° C. and added in 15- 20 minutes, 72-77 ° C, with stirring, 115 parts chloroforma. Stirring of the resulting dark brown solution was continued for one hour at 72-75 ° C, and was allowed to stand for 14 hours at room temperature.

   The water and solvents are removed by distillation under reduced pressure, the residue of brown water is dissolved in 1000 parts /, filtered and acidified with acetic acid until the litmus paper has set. . The resinous body which has precipitated is separated by decantation and diluted with 1000 parts by volume
 EMI25.6
 dther.

   --1.a ethereal solution is then freed of the insoluble parts by filtration and it is evaporated * This gives a brownish oil (crude aldehyde) which is subjected to the subsequent reaction with cyanide.
 EMI25.7
 benyl0.The product gives a purple color reaction

 <Desc / Clms Page number 26>

 blue with an alcoholic solution of ferric chloride,
 EMI26.1
 d) 3-ph'nyl-7- ± "3 '-rndthylpyrazol-yl- (1' # -coumarin.



   In 250 parts by volume of 100% alcohol, 100 parts of the crude aldehyde obtained under c) are dissolved and 52 parts by volume of
 EMI26.2
 Benxylo cyanide and 10 parts of piperidine are then heated to 75-8O C for one hour, then another 25 parts of piperidin are added and the mixture is boiled at reflux for 20 hours * The yellow solution obtained is introduced.
 EMI26.3
 in 3000 pirtios one volume of acetic acid 10? and the mixture obtained is boiled, laying 4 hours with stirring It thickens a brown oil which, on cooling, solidified into a brown The product thus obtained drinks is separated from the aqueous solution by d *, ttntaUon , then it is 6.1 * .yd nvoc 500 parts of alcohol.

   In this process, the brown resinous by-products dissolve in the alcohol and, after separation of the alcohol by filtration, a light gray solid is obtained. From do co
 EMI26.4
 Finally, 3-phcnyl-7 - / * 3'-methylpyrozoly1- (1 ') - 7-coUMorin can be isolated in its pure state. sought by recrystallization of a mixture of lonzèno and iigrosnet The product is identical to the coumarfninuo derivative prepared according to Example 3.



  EXAMPLE 11
 EMI26.5
 

 <Desc / Clms Page number 27>

 
 EMI27.1
 76 parts of 3..phsnyl7, "'3. Mthylp'yrGzolyl- (11> .. 7-coumarin,. 20-25OC, imitation, in 750 parts per volume of sulfuric acid monohydrate are dissolved. Stirring is continued for 14 hours at room temperature to form a clear solution, brownish in color, which fluoresces violet in daylight.

   The additional operations are then carried out: the sulphonation mixture is poured, with stirring, onto 3000 parts of ice, one adds to the white slurry obtained 1500 parts by volume of saturated aqueous sodium chloride solution, the mixture is heated to 50-70 ° C., cooled again, the product is filtered off, suspended again in 3000-4000 parts of water and neutralized, with stirring, with dilute sodium carbonate solution. filtration, the new compound is dried at 70-80 C.

   The
 EMI27.2
 3- (m-sulfophdnyl) -7- (3'-m4thyl - "" pyn-lolyl) sodium sol. CoumQrin8 forms a thick yellow powder which is soluble in water. The dilute aqueous solution has a fluorine.
 EMI27.3
 rescence blue violet and it can. 8be used for optical brightening of polyamide fibers.



   Very efficient products are obtained
 EMI27.4
 neighbor if we replace, in this example, 3-h4nvl-? - "'3a..methylpyrazolyl- (1',", aoumnri.no by a corresponding quantity of 3- (p..meti, ylphenyl ) 7-i3 '.. ethylpyrwr ZOlyl- (11) .7-coumarlne or 4e 3- (pchlorophfnyl)? .. 3' methyl-pyrazolyi- (1 ')> -. ^, Ormarin.



  EXAMPLE 12:
 EMI27.5
 

 <Desc / Clms Page number 28>

      
 EMI28.1
 30 parts of 3-phohyl-? '.. mthyipyrazolyl (1 d -, - coumarino) are dissolved in 300 parts of chlorosulfonic acid and stirring is continued for 14 hours at temperature. ambient temperature.
 EMI28.2
 while on ice, the sulfochlotide is made to appear all in the form of a yellowish precipitate.

   The product was filtered off, washed with water and dried. For the
 EMI28.3
 preparation of the sulfonamides, the tulfochloride thus obtained is used. To prepare the sulfochloride, it is also possible to use, with the same success, the sodium salt of In 3- (rrraulfa;

  hény,) .. 7 .., "'3'm6thy'.pyrazolyl (1' j" ''. comtro rine obtonuo according to Example 11,
 EMI28.4
 10 Pot1ei of the sulfochloride described above is suspended in 150 parts by volume of chlorobenzene and 6 parts of 3-clinrf thylemino-propyleminoe are added to 45OCt. The yellow suspension obtained is then stirred for 30 minutes. lo heated to boiling for a short time, filtered hot, the filtrate is allowed to cool, the crystals formed are separated by filtration and they are purified by
 EMI28.5
 rocristallisation in chlorobcnzënOt The pale yellow needles melting at 210 C and dissolve in which dilute acetic acid gives a violet fluorescence.
 EMI28.6
 r2af '; 2604N4S calculated t bt,? 9! VS ; 5.62 H 12.01% N 6087 ik S, found:

   61.64% C f 5.58% H 12.03% N 7.09% S,
The new brightening agent can be used, in an acid solution, for optical bleaching of fibers.
 EMI28.7
 do polyncrylonitriloo

 <Desc / Clms Page number 29>

 By operating as described above, we prepared
 EMI29.1
 the amides responding. the following formula, j
 EMI29.2
 in which X can take the following meanings t
 EMI29.3
 X m N "2 X -NH..C .:

  -Oi3 X. -NH-CHg X Mr -> .- C2H5 X. # NH-Cf-CH2-OC2H5 X. -t.I.OH..Ct101.! X. -NEi..CtCHN (H) 2 X. -m (C-H "3) 2 X s -tJ (H5) 2 These sulphonomides can be used for the bluing of polyester and polyamide fibers * EXAMPLE 13
We dye at 75 C for 30 minutes 10 parts
 EMI29.4
 of a tiu of short fibers, slightly young polyomidi based on adipic acid and hexnmethylbne-diamine (Nylon do. the Company E.1.

   Du Pont de Nemours Wilmington, Delaware, USA,) in a dye bath containing 0.01 part of 3-phenyl7, "" 3 r5..cJim ° thyl. pyrazolyl - (<') ¯7-coumarino ot 0.2 part of an ether of oleic alcohol and pentadecyl glycols, the bath length being 1:40, then rinsed and dried The nylon fabric as well treated appears, in daylight, much whiter than the same fabric that was not treated * EXAMPLE 14:
With a bath length of 1:

   50, we dye,
 EMI29.5
 at 95-100 C, laying 30 minutes, 10 parts of a tissue,

 <Desc / Clms Page number 30>

 
 EMI30.1
 {"yellowish brown appearance, in polyoater based on terephthalic acid and glycol, referred to as" Dacron ", in a bath containing 0.005 part of 3-pheny 1-7-3 '-athylpyrazolyl- (l') ¯7-coumarin ot 0.3 part of an ether of oleic alcohol ot ponta-
 EMI30.2
 decyl-glycol, rinsed and sbcho. The fabric thus treated has a much whiter appearance than a control sample of bleak provenance which has not been treated.



  EXAMPLE 15 t
With a bath length of 1:30, you
 EMI30.3
 toint laying 30 minutes 75 C, 10 parts of an undyed yarn thereforeetyl-cellulose, in a bath containing 0, ùt partit do 3 .. (m-tcxyl) .7 - '' 3 '.. m6thylyxa; .ty1- . (1 ') "Coumarin in the finely dispersed state. After rinsing and drying, the yarn thus treated .- a much whiter appearance.
 EMI30.4
 than before 1 treatment 0 EXAMPLE 16:
With a bath length of 1:10, washed for 30 minutes, at 70 ° C., 100 parts of an untreated nylon fabric, in a washing bath containing 0.05
 EMI30.5
 part of la'.s-phnyl-75-.réthylpyrazolyl (1 ') w coumarin obtained according to Example 2 as well as 8 parts of a synthetic detergent, rinsed and dried.

   The fabric thus treated has a much brighter appearance than a fabric washed with the addition of optical brightener.

 <Desc / Clms Page number 31>

 



    EXAMPLE 17
At a bath length of 1:30, 90-100 C is dyed, for 30 minutes, 10 parts of a
 EMI31.1
 polyethylene glycol terephthaate fabric in a bath which contains 0.01 part? 3 -. (P-chlorophé> nyl) ¯7- "" 3 ..n # thyipyrozoiyl (1) .courttarins, 0.3 part of o-dichlorobenzene as well as 0.1 part of dinctylphenol ether and dodecoglycol After rinsing and drying the fabric has a distinctly whiter appearance than before the treatment * EXAMPLE 18:

   
At room temperature where it is treated with
 EMI31.2
 scarf a fabric of polyethylene terephthalate fibers. lene-glycol with a bath which contains, in 1000 parts of water, 0.6 part of 3- (p..tolyi) .7..3.: id.imthyl py7rfxolyl (ft j '.. coumarin and 1, 5 part of nonylphdnol ether and doddcaglycol, the tissue is dried to a toneu) p f4.1dual fn l1qUia. 5% and dried at 60.degree. C. The fabric was then heated for 15 minutes at 125-130 ° C. Thereby obtained a fabric having a brilliant white appearance.



  EXAMPLE 19 1
Has 100 parts of poly-
 EMI31.3
 Ethylone-glycol phthalote is added, in a mixer, a solution of 0.05 part of 3phdnylL.l .. methyl-pyrazolyl -. (1 ') - com'tarine in toluene and the whole is worked out. Then we remove the solvent,
 EMI31.4
 z 70-90 "C, under reduced pressure, while continuing to work the mixture.

   The clippings having undergone this preliminary treatment are introduced, with 0.4 part

 <Desc / Clms Page number 32>

 of titanium dioxide, in a stainless steel eutocleve, Away from air, the parings are heated to 270-280 C, the molten mass obtained is immersed well, using a stirrer, laying 1 hour at 270 C under a low nitrogen pressure, the mixture is kept for 30 minutes at the temperature indicated without stirring, then the liquid polymer is forced, by means of nitrogen, through a nozzle in the form of ribbons or filaments.



  The polyester fibers thus prepared have a very high degree of whiteness.



  EXAMPLE 20 '
At approximately 80 ° C., 300 parts of hexane-diamine adipate are dissolved in 300 parts of distilled water. Into this solution are introduced 1.8 parts of sebacic acid, 1.2 part of bioxydo do titano (* notes @) and 0.3 part of 3-phenyl-7- [3'.5'-dimethyl-pyrazolyl- (1 ')] - coumerin, and stirred until the distribution is homogeneous * The liquid mixture is introduced, away from oxygen, into the stainless steel autoclave, heated to about 150 C, then the temperature is raised to 280 C. in one hour. During this time the pressure in the autoclave is allowed to drop below 30 atmospheres by the escape of water vapor.

   When the maximum temperature of 280-290 ° C has been reached, the pressure is allowed to drop to atmospheric pressure in 10 to 20 minutes, removing the volatile fractions by blowing. The mass is then maintained at 280 ° C. for 4 hours, away from oxygen and at atmospheric pressure.

   At the end of this lapse of time, the condensation has sufficient

 <Desc / Clms Page number 33>

   progressed so that the polycondensate can be spun, at all pressure, through a buso placed at the bottom of the autoclave. The superpolyamide fibers thus obtained are of a brilliant white which has good fastness to light. the
 EMI33.1
 If we replace this example / C, 3 part of 3 "'; - ph6nyl-7-L3'. 5'-dlthyl-pyrazo.lyl- (1 ') .1-coumorino by 0.15 partio Doing 3-phenyl-7- ± "3'-methyl-pyrDzolyl- (1 ') - 1-coumnrin a similar good effect is obtained.



    EXAMPLE 2.1
In a rotary mixer, 500 parts of polyamide shavings are mixed together for 10 hours.
 EMI33.2
 with boae des -coprola, ctorne, 1.5 part of titanium dioxide and 0.25 part of 3-phenyl-7- ± * 3 -methyl-pYro-> ZOlYl- (Í '). 7-coumorin, melted the mixture is 250-260 ° C. in an oxygen-free Qcio1noxYdablo autoclave, then the molten mixture is forced through a die with nitrogen and the strands are drawn to 400%. a brilliant white fiber is obtained which has good fastness to light.



   EXAMPLE 22:
 EMI33.3
 A mixture consisting of 0.06 part of 3phdnyl-pyrsxolyl (t ') -coumarin, 67 parts of polyvinyl chloride powder, 33 parts of polyvinylchloride powder, 33 parts of polyvinyl chloride powder, 33 parts of polyvinyl chloride powder, was frozen for 15 minutes on a roller mixer dioctyl, 2 parts of di-n-butyl-dilauryl-dih3tdxoxystannote and 0.3 part of sodium pentaoctyl tripolyphosphate, and this mixture is then stretched into sheets. Los chloride excavations do

 <Desc / Clms Page number 34>

 polyvinyl thus prepared have, in daylight,
 EMI34.1
 a fluorttconco vio) otte and a distinctly whiter appearance than similar excavations which have been prepared without the addition of this brightener.



  EXAMPLE 23
We work, as described in
 EMI34.2
 previous example 0.03 part of 3phbnyll3 methylpyrezolyl (1e 'coumorino and 7 parts of titanium dioxide, (anatase) with 61 parts of chloride of
 EMI34.3
 polyvinyl # 33 parts of dioctyl phthalato, 2 parts of dibutyltin dileurato and 0.3 part of
 EMI34.4
 sodium and pentboctyl tripolyehosphote, to make an opaque excavation. The sheet thus prepared appeared much whiter than a control sample prepared without the addition of brightener.



  EXAMPLE 24:
 EMI34.5
 0.2 part of 3-phenyl-7 is homogenized.



  5smthylpyrazolyl (1)% - Jcoiiarina, 5 parts of titanium hioxydo (onatase), 75 parts of acetyl-
 EMI34.6
 Cellulose and 25 parts of phthalato do dicthylo dnne 900 parts décdtono, to obtain a cloudy solution which is poured onto glass plates * After
 EMI34.7
 evaporation of the acetone gives an opaque and detachable film which is of a clearer white than a control sample prepared without brightener.


    

Claims (1)

EMI35.1 ABSTRACT The present invention includes noted; 1) As new industrial products EMI35.2 a) the 3 phdnyl 7-pyrazolyl (1f) coumairins corresponding to the following general formula t EMI35.3 in which R1, R2 and R3 each represent a EMI35.4 hydrogen atom or an aliphatic, alkyl, aralph: 1tiqu (or aromatic, R4 represents a hydrogen atom or a rosto alkyl EMI35.5 infd, aur and 'R5 represents a phnyl group cS..entuel1om8nt sublt! - killed, b) more or less colored materials $ EMI35.6 whose appearance has been improved with the help of; phnyl, 7. pyrazolyl- (10) -coun * rinoo all specified 1), 2) A process for the preparation of 3- phdrryl7.rpYrazo, y1aoumarinesisalon which leads to a phenyl7hydrazinocoumarino, which may have other substituents, or a compound capable of reacting: 0111 "10 a 3-plienyl-7-hydrazi-io.-coumarinop with a compound containing an a. Y -d1carborylo IU.phl group ... tiquo, or with a compound containing a group capable of reacting oomroo an a, -dicarbonyia aiipMtiquo group, <Desc / Clms Page number 36> EMI36.1 and optionally the 3-ph <5nyl¯7-pyrozolyl (1) -coumarlno thus obtained is sulfonated and, if desired, it is further amidated via the sulfonic acid halide, ' 3) Varieties of the process specifia soue 2 m having the following peculiarities taken EMI36.2 We will separate out according to the various poustblock combinations a) condense a 3-phdnyl7-hydraxino counedrae, which may have further substituents or another apto compound to react such as a 3-ppGnyl ™. hydrrzinocoumnrino, with a compound containing an a.-alkynyl-carbonylo group, to obtain a 3.phdttyt? pyrazolyl (1) coumarin b) condenses a 3-phdnyl-7-hydrr: iac coumarino, which may have other substituents, or a compound opts to react in the same way, with a EMI36.3 compote qwi aentj) .an% a gtflypo ap .ôâe *? n.yl-eayH> 9nyA aliphatic or an apto b group to react in the same way, to obtain uno 3-phGnYl-7-pyrazolinyl '' (1 ')' 'coumarin, and one ddshydrog: no the latter in 3-phenyl * 7-pyrazolyjL- (t') - countarine corresponding; c) benz aldehydes are condensed which carry, in position 2 of the benzene ring, a hydroxyl group or a convertible substituent or a hydroxyl group, and, in position 4, a pyrazolo residue possibly substituted, with derivatives of the acid acetic whose carbon atom a still carries a phenyl group or a substituted phenyl group, condensation which leads to ss-phenyl- acid derivatives. <Desc / Clms Page number 37> corresponding acrylics, optionally converted to a group. hydroxylic. free the acido @ cry- lic residue occupying the ortho position on the rosto ss-phenyl, and the coumerinic cyclization is carried out by condensation of the hydroxyl group with the carboxylic function of the @crylic acid residue.