CH366391A - Process for lightening casting, pressing and spinning masses - Google Patents

Process for lightening casting, pressing and spinning masses

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Publication number
CH366391A
CH366391A CH99762A CH9976257A CH366391A CH 366391 A CH366391 A CH 366391A CH 99762 A CH99762 A CH 99762A CH 9976257 A CH9976257 A CH 9976257A CH 366391 A CH366391 A CH 366391A
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Switzerland
Prior art keywords
sep
group
alkyl
naphthaldehyde
aryl
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CH99762A
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German (de)
Inventor
Roderich Dr Raue
Werner Dr Mueller
Walther Dr Retter
Link Josef
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Bayer Ag
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Publication of CH366391A publication Critical patent/CH366391A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/56—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups bound to carbon atoms of six-membered aromatic rings and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
    • C07C49/835—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups having unsaturation outside an aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with an alkyl or cycloalkyl radical attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coloring (AREA)
  • Artificial Filaments (AREA)
  • Pyrrole Compounds (AREA)

Description

  

  



  Verfahren zum Aufhellen von Gie¯-, Pre¯- und Spinnmassen
Es hat sich gezeigt, dass fluoreszierende, keinen Farbstoffcharakter besitzende, in Wasser unlösliche bzw. schwerlösliche Verbindungen der Formel
EMI1.1     
 in der X für einen ein-oder zweiwertigen aromatischen oder heterocyclischen Rest, wie z.

   B. für einen Phenyl-und Naphthylrest bzw. einen Indolyl-, Carbazolyl-oder Thienylrest, und   R1    für eine Acylgruppe, für eine freie oder veresterte Carboxylgruppe, für eine Carbonamidgruppe, die auch durch Alkyl-, Alkylen-, Aryl-oder Aralkylreste substituiert sein kann, oder für die Cyangruppe steht, während R2 Wasserstoff, eine Alkyl-, Cycloalkyl-oder Arylgruppe, eine Acylgruppe, die Carboxylgruppe, die auch verestert sein kann, eine Carbonamidgruppe, die auch durch Alkyl-, Alkylen-, Aryl-oder Aralkylreste substituiert sein kann, oder die Cyangruppe bedeutet, und n gleich   1    oder 2 ist, sich mit sehr gutem Erfolg als Aufhellungsmittel für   Giess-,      Press-und    Spinnmassen verwenden lassen.



   In Athylenverbindungen der genannten Art, welche einen aromatischen Rest X aufweisen, kann dieser einen oder mehrere Substituenten tragen, wie z. B. die Hydroxylgruppe, eine Alkoxygruppe, eine Alkyl-, Aryl-, Aralkyl-, Acylgruppe, ein Halogen, die Nitro-oder Cyangruppe, die Sulfonsäuregruppe, die Carboxylgruppe, die auch verestert sein kann, die Carbonamid-oder   Sulfonamidgruppe,    die auch durch Alkyl-, Aryl-oder Aralkylreste substituiert sein   kön-    nen sowie schliesslich die Aminogruppe, die auch durch gegebenenfalls sulfonierte Alkyl-, Aryl-oder Aralkylreste substituiert sein kann.



   Besonders geeignete Athylen-Verbindungen sind    d    diejenigen, die im aromatischen Kern, vorzugsweise in o-Stellung zur Methingruppe, eine Hydroxylgruppe tragen, und unter diesen Verbindungen erweisen sich im allgemeinen wiederum diejenigen als die besten, bei welchen in der oben angegebenen Formel Ri und R2 die Cyangruppe oder eine gegebenenfalls substituierte Carbonamidgruppe bedeuten.



   Die in Wasser unlöslichen bzw. schwerlöslichen Athylen-Verbindungen der genannten Art-hierzu gehören insbesondere die sulfongruppenfreien-lassen sich zum Aufhellen von Guss-,   Press-und    Spinnmassen aus synthetischen Polykondensaten, wie Polyestern, Polyamiden und Polyurethanen sowie aus Polymerisaten, wie Polyacrylnitril, Polystyrol und aus Celluloseestern verwenden.



   Die zu verwendenden   Aufhellungsmittel    zeichnen sich gegenüber bekannten Aufhellungsmitteln im   all-    gemeinen durch grössere Ausgiebigkeit aus und ergeben vielfach Effekte von neutralerem Weiss und besserer Lichtechtheit ; dies gilt vor allem hinsichtlich der Anwendung der Mittel auf Massen aus Cellu  loseestern,    Polyacrylnitrilen, Polyestern, Polyamiden und Polyurethanen.



      Beispiel I   
Eine Spinnlösung aus 200 Gew.-Teilen Acetylcellulose und 800 Gew.-Teilen Aceton setzt man 0, 02 bis 0, 2   Gew.-Teile      ss-(2-Oxynaphthyl-l)-a-cyan-a-    carbonamido-äthylen in Form einer 10    /o igen Lösung    in Dimethylformamid zu und verspinnt die Mischung in üblicher Weise. Die erhaltenen Fasern besitzen einen hohen Weissgrad, der Effekt ist sehr gut lichtbeständig.



   Beispiel 2
10 kg Polystyrolgranulat werden mit 10 g   #- (2-      Oxynaphthyl-l)-a,      a-dicarbonamido-äthylen    vermischt und in einer Spritzmaschine bei 250  zu Formlingen verarbeitet. Die so erhaltenen Formkörper sind in hervorragender Weise aufgehellt. Setzt man der Spritzmasse noch 100 g Titandioxyd als Weisspigment zu, so erhält man ebenfalls Produkte von ausgezeichnetem Weissgrad.



   Die Herstellung der zu verwendenden Äthylenverbindungen kann nach verschiedenen an sich bekannten Verfahren erfolgt sein, beispielsweise durch Umsetzung aromatischer oder heterocyclischer Aldehyde mit Verbindungen, die eine aktive Methylengruppe enthalten, unter Zusatz alkalischer Kondensationsmittel, eventuell in Gegenwart eines Lösungsoder Verdünnungsmittels, wie eines Alkohols oder Benzols.



   Zu den hierfür in Betracht kommenden Aldehyden gehören z. B.



   Salicylaldehyd,   
3-Chlorsalicylaldehyd,
5-Chlorsalicylaldehyd,   
3,   5-Dichlorsalicylaldehyd,       4-Dimethylaminosalicylaldehyd,   
4-Oxy-benzaldehyd,    Aldehydokresotinsäuren,   
Anisaldehyd,   
2-Oxy-1-naphthaldehyd,
3-Chlor-2-oxy-1-naphthaldehyd,
6-Chlor-2-oxy-1-naphthaldehyd,
7-Chlor-2-oxy-1-naphthaldehyd,
3-Methoxy-2-oxy-1-naphthaldehyd,
6-Methoxy-2-oxy-1-naphthaldehyd,   
2, 6-Dioxy-naphthalin-1, 5-dialdehyd,    1-Oxy-2-naphthaldehyd,   
1-Oxy-4-methoxy-2-naphthaldehyd,    1-Oxy-4-chlor-2-naphthaldehyd,       1-Oxy-4-brom-2-naphthaldehyd,
2-Methoxy-1-naphthaldehyd,
2-Athoxy-1-naphthaldehyd,   
Benzaldehyd,    4-Chlorbenzaldehyd,   
3-Nitrobenzaldehyd,
Terephthalaldehyd,

     
1-Naphthaldehyd,
1-Methyl-2-phenylindol-3-aldehyd,       N-äthylcarbazol-3-aldehyd    und
2-Thiophen-aldehyd, während als Verbindungen mit aktiver Methylengruppe beispielsweise die folgenden genannt seien :
Malonsäure, Cyanessigsäure,   Acetessigsäure    sowie deren Ester, Amide, Anilide, Alkyl-, Aralkyl-und
Cycloalkylamide, Aceton, Acetylaceton, Aceto phenon, Benzylcyanid und Malondinitril.



   Man erhält eine Verbindung der genannten Art beispielsweise wie folgt :
34, 4 Gew.-Teile   2-Oxy-l-naphthaldehyd    (0, 2 Mol) und 19, 6 Gew.-Teile Cyanacetmethylamid (0, 2 Mol) wurden in 150 Volumteilen Alkohol unter Erwärmen gelöst. Bei   40  wurden    dann 3 Volumteile Piperidin eingetropft, wobei eine leichte Temperaturerhöhung stattfand. Das Reaktionsgemisch wurde anschliessend langsam zum Sieden erwärmt, noch 2 Stunden unter Rückfluss gekocht und dann abgekühlt. Hierbei kristallisierte das   SB-(2-Oxy-naphthyl)-a-cyan-a-N-    methylcarbonamido-äthylen in blassgelben Nadeln vom Schmelzpunkt 162  aus. Die Lösung des Amids in Methanol, angesäuert mit Essigsäure, zeigt in gro sser Verdünnung eine intensiv blaue Fluoreszenz.



   In analoger Weise können aus nachstehenden Komponenten entsprechende Athylen-Verbindungen hergestellt werden :
EMI2.1     


<tb>  <SEP> Schmelzpunkt
<tb> AIdehydkomponente <SEP> Methylenkomponente <SEP> der <SEP> entsprechenden
<tb>  <SEP> Äthylenverbindung
<tb>   Benzaldehyd <SEP> Cyanessigsliurelithylester <SEP> 51o    <SEP> 
<tb>   3-Nitrobenzaldehyd <SEP> Malonsäurediäthylester <SEP> 77o    <SEP> 
<tb>   4-Oxybenzaldehyd <SEP> Cyanessigsäureäthylester <SEP> 173    <SEP> bis <SEP>    178     <SEP> 
<tb>   Anisaldehyd <SEP> Cyanessigsäureäthylester <SEP> 84     <SEP> 
<tb>   4-Dimethylaminosalicylaldehyd <SEP> Cyanessigsäuremethylamid <SEP> 172    <SEP> bis <SEP>    174     <SEP> 
<tb>   5-Chlorsalicylaldehyd 

  <SEP> Cyanessigsäureäthylester <SEP> 134     <SEP> (Zers.)
<tb>   Naphthalin-1-aldehyd <SEP> Cyanessigsäureäthylester <SEP> 78     <SEP> 
<tb>   2-Oxy-1-naphthaldehyd <SEP> Cyanessigsäurebutylamid <SEP> 75    <SEP> bis <SEP> 76 
<tb>   2-Oxy-1-naphthaldehyd <SEP> Cyanessigsäurebenzylamid <SEP> 160    <SEP> bis <SEP> 162 
<tb>   2-Oxy-l-naphthaldehyd <SEP> Cyanessigsäurepiperidid <SEP> 235     <SEP> 
<tb>   2-Oxy-1-naphthaldehyd <SEP> Acetylaceton <SEP> 1260    <SEP> (Zers.)
<tb>   2-Methoxy-l-naphthaldehyd <SEP> Cyanessigsäureäthylester <SEP> 60    <SEP> bis <SEP> 61 
<tb>   1-Oxy-2-naphthaldehyd <SEP> Cyanacetamid <SEP> 167-169     <SEP> (Zers.)

  
<tb> Terephthalaldehyd <SEP> Cyanessigsäure <SEP> 280 <SEP> bis <SEP> 285 
<tb>   Terephthalaldehyd <SEP> Cyanessigsäureäthylester <SEP> 199    <SEP> bis <SEP> 200 
<tb> Terephthalaldehyd <SEP> Malonsäure <SEP> 190 <SEP> bis <SEP> 200 
<tb>   2-Thiophenaldehyd <SEP> Cyanessigsäureäthylester <SEP> 95o    <SEP> 
<tb>   1-Methyl-2-phenylindol-3-aldehyd    <SEP> Cyanessigsäureäthylester <SEP> 144 
<tb>



  



  Process for whitening Giē, Prē and spinning masses
It has been shown that fluorescent, water-insoluble or sparingly soluble compounds of the formula which have no dye character
EMI1.1
 in which X is a mono- or divalent aromatic or heterocyclic radical, such as.

   B. for a phenyl and naphthyl radical or an indolyl, carbazolyl or thienyl radical, and R1 for an acyl group, for a free or esterified carboxyl group, for a carbonamide group which is also substituted by alkyl, alkylene, aryl or aralkyl radicals can be, or represents the cyano group, while R2 is hydrogen, an alkyl, cycloalkyl or aryl group, an acyl group, the carboxyl group, which can also be esterified, a carbonamide group, which can also be substituted by alkyl, alkylene, aryl or aralkyl radicals can be substituted, or denotes the cyano group, and n is 1 or 2, can be used with very good success as brightening agents for casting, molding and spinning compounds.



   In ethylene compounds of the type mentioned, which have an aromatic radical X, this can carry one or more substituents, such as. B. the hydroxyl group, an alkoxy group, an alkyl, aryl, aralkyl, acyl group, a halogen, the nitro or cyano group, the sulfonic acid group, the carboxyl group, which can also be esterified, the carbonamide or sulfonamide group, which also by Alkyl, aryl or aralkyl radicals can be substituted and, finally, the amino group, which can also be substituted by optionally sulfonated alkyl, aryl or aralkyl radicals.



   Particularly suitable ethylene compounds are those which have a hydroxyl group in the aromatic nucleus, preferably in the o-position to the methine group, and among these compounds, in general, those in which R i and R 2 in the formula given above prove to be the best denote the cyano group or an optionally substituted carbonamide group.



   The water-insoluble or sparingly soluble ethylene compounds of the type mentioned - these include in particular those free from sulfone groups - can be used for lightening casting, molding and spinning compounds from synthetic polycondensates, such as polyesters, polyamides and polyurethanes, and from polymers such as polyacrylonitrile, polystyrene and made from cellulose esters.



   The lightening agents to be used are generally distinguished from known lightening agents by greater abundance and often result in effects of more neutral white and better lightfastness; This is especially true with regard to the application of the agent to masses of Cellu lose esters, polyacrylonitriles, polyesters, polyamides and polyurethanes.



      Example I.
A spinning solution of 200 parts by weight of acetyl cellulose and 800 parts by weight of acetone is put in the form of 0.02 to 0.2 parts by weight of ss- (2-oxynaphthyl-1) -a-cyano-a-carbonamido-ethylene a 10% solution in dimethylformamide and the mixture is spun in the usual way. The fibers obtained have a high degree of whiteness and the effect is very lightfast.



   Example 2
10 kg of polystyrene granulate are mixed with 10 g of n - (2-oxynaphthyl-1) -a, a-dicarbonamido-ethylene and processed into moldings in an injection molding machine at 250. The moldings obtained in this way are lightened in an outstanding manner. If 100 g of titanium dioxide are added as a white pigment to the injection molding compound, products with an excellent degree of whiteness are also obtained.



   The ethylene compounds to be used can be prepared by various processes known per se, for example by reacting aromatic or heterocyclic aldehydes with compounds containing an active methylene group, with the addition of alkaline condensing agents, possibly in the presence of a solvent or diluent such as an alcohol or benzene.



   The aldehydes which can be considered for this purpose include, for. B.



   Salicylaldehyde,
3-chlorosalicylaldehyde,
5-chlorosalicylaldehyde,
3, 5-dichlorosalicylaldehyde, 4-dimethylaminosalicylaldehyde,
4-oxy-benzaldehyde, aldehydocresotinic acids,
Anisaldehyde,
2-oxy-1-naphthaldehyde,
3-chloro-2-oxy-1-naphthaldehyde,
6-chloro-2-oxy-1-naphthaldehyde,
7-chloro-2-oxy-1-naphthaldehyde,
3-methoxy-2-oxy-1-naphthaldehyde,
6-methoxy-2-oxy-1-naphthaldehyde,
2,6-Dioxy-naphthalene-1, 5-dialdehyde, 1-oxy-2-naphthaldehyde,
1-oxy-4-methoxy-2-naphthaldehyde, 1-oxy-4-chloro-2-naphthaldehyde, 1-oxy-4-bromo-2-naphthaldehyde,
2-methoxy-1-naphthaldehyde,
2-ethoxy-1-naphthaldehyde,
Benzaldehyde, 4-chlorobenzaldehyde,
3-nitrobenzaldehyde,
Terephthalaldehyde,

     
1-naphthaldehyde,
1-methyl-2-phenylindole-3-aldehyde, N-ethylcarbazole-3-aldehyde and
2-thiophene aldehyde, while compounds with an active methylene group include, for example, the following:
Malonic acid, cyanoacetic acid, acetoacetic acid and their esters, amides, anilides, alkyl, aralkyl and
Cycloalkylamides, acetone, acetylacetone, acetophenone, benzyl cyanide and malondinitrile.



   A compound of the type mentioned is obtained, for example, as follows:
34.4 parts by weight of 2-oxy-1-naphthaldehyde (0.2 mol) and 19.6 parts by weight of cyanoacetmethylamide (0.2 mol) were dissolved in 150 parts by volume of alcohol with heating. At 40, 3 parts by volume of piperidine were then added dropwise, a slight increase in temperature taking place. The reaction mixture was then slowly heated to boiling, refluxed for a further 2 hours and then cooled. The SB- (2-oxynaphthyl) -a-cyano-a-N-methylcarbonamido-ethylene crystallized out in pale yellow needles with a melting point of 162. The solution of the amide in methanol, acidified with acetic acid, shows an intense blue fluorescence in large dilution.



   Appropriate ethylene compounds can be prepared in a similar manner from the following components:
EMI2.1


<tb> <SEP> melting point
<tb> Aldehyde component <SEP> Methylene component <SEP> of the corresponding <SEP>
<tb> <SEP> ethylene compound
<tb> Benzaldehyde <SEP> cyanoacetic acid ethyl ester <SEP> 51o <SEP>
<tb> 3-Nitrobenzaldehyde <SEP> Malonic acid diethyl ester <SEP> 77o <SEP>
<tb> 4-Oxybenzaldehyde <SEP> ethyl cyanoacetate <SEP> 173 <SEP> to <SEP> 178 <SEP>
<tb> Anisaldehyde <SEP> Ethyl cyanoacetate <SEP> 84 <SEP>
<tb> 4-Dimethylaminosalicylaldehyde <SEP> Cyanoacetic acid methylamide <SEP> 172 <SEP> to <SEP> 174 <SEP>
<tb> 5-chlorosalicylaldehyde

  <SEP> ethyl cyanoacetate <SEP> 134 <SEP> (dec.)
<tb> Naphthalene-1-aldehyde <SEP> Ethyl cyanoacetate <SEP> 78 <SEP>
<tb> 2-Oxy-1-naphthaldehyde <SEP> Cyanoacetic acid butylamide <SEP> 75 <SEP> to <SEP> 76
<tb> 2-Oxy-1-naphthaldehyde <SEP> Cyanoacetic acid benzylamide <SEP> 160 <SEP> to <SEP> 162
<tb> 2-Oxy-1-naphthaldehyde <SEP> Cyanoacetic acid piperidide <SEP> 235 <SEP>
<tb> 2-Oxy-1-naphthaldehyde <SEP> Acetylacetone <SEP> 1260 <SEP> (decomp.)
<tb> 2-methoxy-l-naphthaldehyde <SEP> ethyl cyanoacetate <SEP> 60 <SEP> to <SEP> 61
<tb> 1-Oxy-2-naphthaldehyde <SEP> Cyanacetamide <SEP> 167-169 <SEP> (decomp.)

  
<tb> Terephthalaldehyde <SEP> Cyanoacetic Acid <SEP> 280 <SEP> to <SEP> 285
<tb> Terephthalaldehyde <SEP> Ethyl cyanoacetate <SEP> 199 <SEP> to <SEP> 200
<tb> Terephthalaldehyde <SEP> Malonic acid <SEP> 190 <SEP> to <SEP> 200
<tb> 2-thiophenaldehyde <SEP> ethyl cyanoacetate <SEP> 95o <SEP>
<tb> 1-Methyl-2-phenylindole-3-aldehyde <SEP> Ethyl cyanoacetate <SEP> 144
<tb>

Claims (1)

PATENTANSPRUCHE I. Verfahren zum Aufhellen von Giess-, Press- und Spinnmassen aus synthetischen Polykondensaten oder Polymerisaten oder aus Celluloseestern, dadurch gekennzeichnet, dass man den genannten Massen eine fluoreszierende, keinen Farbstoffcharakter besitzende, in Wasser unlösliche bzw. PATENT CLAIMS I. A process for lightening casting, molding and spinning masses made from synthetic polycondensates or polymers or from cellulose esters, characterized in that the said masses are given a fluorescent, non-coloring material, insoluble in water or schwerlösliche Verbindung der Formel EMI3.1 in der X für einen ein-oder zweiwertigen aromatischen oder heterocyclischen Rest und R für eine Acylgruppe, eine freie oder veresterte Garboxylgruppe, eine Carbonamidgruppe, die durch Alkyl-, Alkylen-, Aryl-oder Aralkylreste substituiert sein kann, oder die Cyangruppe steht, während R2 Wasserstoff, eine Alkyl-, Cycloalkyl-oder Arylgruppe, eine Acylgruppe, die Carboxylgruppe, die auch verestert sein kann, eine Carbonamidgruppe, die durch Alkyl-, Alkylen-, Aryl-oder Aralkylreste substituiert sein kann, oder die Cyangruppe bedeutet, und n gleich 1 oder 2 ist, zusetzt. poorly soluble compound of the formula EMI3.1 in which X stands for a mono- or divalent aromatic or heterocyclic radical and R for an acyl group, a free or esterified carboxyl group, a carbonamide group which can be substituted by alkyl, alkylene, aryl or aralkyl radicals, or the cyano group, while R2 denotes hydrogen, an alkyl, cycloalkyl or aryl group, an acyl group, the carboxyl group, which can also be esterified, a carbonamide group which can be substituted by alkyl, alkylene, aryl or aralkyl radicals, or the cyano group, and n is 1 or 2, adds. II. Gemäss dem Verfahren nach Patentanspruch 1 aufgehellte Giess-, Press-und Spinnmassen. II. According to the method of claim 1, whitened casting, molding and spinning compounds.
CH99762A 1956-03-01 1957-02-15 Process for lightening casting, pressing and spinning masses CH366391A (en)

Applications Claiming Priority (1)

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DEF19663A DE1010047B (en) 1956-03-01 1956-03-01 Whitening agents

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CH366391A true CH366391A (en) 1962-12-31

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CH99762A CH366391A (en) 1956-03-01 1957-02-15 Process for lightening casting, pressing and spinning masses
CH360047D CH360047A (en) 1956-03-01 1957-02-15 Durable whitening agents

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BE (1) BE555326A (en)
CH (2) CH366391A (en)
DE (1) DE1010047B (en)
FR (1) FR1185438A (en)
GB (1) GB846148A (en)
NL (2) NL214984A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL250327A (en) * 1959-04-08
US3254046A (en) * 1963-06-24 1966-05-31 Monsanto Co Spin dyeing of polyacrylonitrile fibers with 1-30 parts per million of polymethine and triarylmethane dyes
JP2846091B2 (en) * 1990-09-25 1999-01-13 オリヱント化学工業株式会社 Indole compounds and their uses

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NL214984A (en)
NL105255C (en)
DE1010047B (en) 1957-06-13
GB846148A (en) 1960-08-24
FR1185438A (en) 1959-07-31
BE555326A (en)
CH360047A (en) 1962-02-15

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