EP0000900B1 - Spirobipyranes, their use and pressure-sensitive copying materials containing them - Google Patents

Spirobipyranes, their use and pressure-sensitive copying materials containing them Download PDF

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Publication number
EP0000900B1
EP0000900B1 EP78100629A EP78100629A EP0000900B1 EP 0000900 B1 EP0000900 B1 EP 0000900B1 EP 78100629 A EP78100629 A EP 78100629A EP 78100629 A EP78100629 A EP 78100629A EP 0000900 B1 EP0000900 B1 EP 0000900B1
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Prior art keywords
methyl
color
spirodipyrans
formula
pressure
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German (de)
French (fr)
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EP0000900A1 (en
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Hans Dr. Baumann
Andreas Dr. Oberlinner
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/15—Spiro-pyrans

Definitions

  • the spirodipyrans of the formula are weakly colored to colorless compounds, the solutions of which give red-violet to blue colorations in an inert, organic solvent in contact with electro-attracting substances.
  • electron acceptor substances are carbon or mineral acids, kaolin, bentonite, activated clay, aluminum silicate, attapulgite or any clay, acidic polymeric materials such as condensation products from phenols and / or phenolsulfonic acids, also metal oxides or salts such as zinc oxide, aluminum oxide, zinc chloride, Iron stearate or cobalt naphthenate.
  • the new spirodipyrans of formula 1 are suitable as color formers for pressure-sensitive recording materials or copying materials.
  • the spirodipyrans of formula 1 according to the invention have the advantage in pressure-sensitive copying systems that the color formers show practically no tendency towards color formation on uncoated coating base paper. When copying, there is therefore no mirror writing on the back of the cover sheet coated with the color former. For the same reason, if the capsules are inadvertently destroyed, the side of the sheet carrying the microcapsule layer is not soiled (stained).
  • the spirodipyrans according to the invention have the advantage over the spirodipyrans known from DE-OS 22 32 364, 23 23 803 and 24 30 568, which carry a dialkylamino group in the 7-position, that the spirodipyrans of the present invention are on coating base paper and not on Give practically no coloring to active clay coated paper.
  • the color former known from Example 1 of DE-OS 22 32 364 stains coating base paper about 12.5 times as strongly as the dye of Example 8 of the present invention.
  • the spirodipyrans Compared to the spirodipyran known from Example 15 of DE-OS 26 11 600, which bears a morpholine group in the 7-position and a diethylamino group in the 7'-position and which is the closest to the spirodipyrans of the present invention, the spirodipyrans have the present invention with the same behavior on coating base paper and a significantly higher color strength.
  • the color strength of the color former known from Example 15 of DE-OS 26 11 600 is only 29% of that of the color former from Example 2 of the present invention.
  • spirodipyrans in a known manner in organic solvents such as chlorinated paraffins, halogenated or partially hydrogenated biphenyl, alkylbenzene, alkylnaphthalene, alkylated dibenzylbenzene, paraffin oil, mineral oil or else in customary solvents such as toluene, xylene, in the form of a solution or suspension in microcapsules and thus to coat the paper surface with the use of binders and other aids such as spacers.
  • Organic solvents such as chlorinated paraffins, halogenated or partially hydrogenated biphenyl, alkylbenzene, alkylnaphthalene, alkylated dibenzylbenzene, paraffin oil, mineral oil or else in customary solvents such as toluene, xylene, in the form of a solution or suspension in microcapsules and thus to coat the paper surface with the use of binders and other aids such as spacers.
  • Pressure-sensitive papers
  • Suitable methods for producing microcapsules are e.g. in US-PS 2,800,457 and 2,800,458 and in DE-PS 21 19 933.
  • spirodipyrans (I) according to the invention are more stable in aqueous suspension than color formers which contain dialkylamino groups (DE-OS 22 32 364, 23 23 803 and 24 30 568), practically colorless microcapsule dispersions are obtained with the former.
  • the spirodipyrans of the general formula I according to the invention can also be finely divided into wax or oil-wax mixtures by the process described in US Pat. No. 3,103,404 and carriers, such as foils or paper, coated with these mixtures.
  • Pressure-sensitive materials are obtained which are suitable for copying on papers coated with electron acceptor substances and which are removed after use like carbon paper.
  • C 1 to C 16 alkyl for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. Butyl, isobutyl, tert. Butyl, n-pentyl, isopentyl, n-hexyl, n-nonyl, i-nonyl, n-octyl, i-octyl, n-decyl, i-decyl, n-dodecyl, i-dodecyl, n-hexadecyl.
  • the color formers are synthesized according to the following reaction scheme in a manner known per se by cyclization of the o-hydroxylaryl-styryl compounds of the formula IV.
  • the latter are obtained, for example, by condensation of benzopyrylium salts of the formula II with N-substituted p-aminosalicylaldehydes of the formula III:
  • the condensation is expediently carried out in inert organic solvents, such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons or acetonitrile, optionally in the presence of acidic or basic condensing agents, such as zinc chloride, phosphoric acid, hydrogen chloride, toluenesulfonic acid, boric acid, pyridine, piperidine, triethylamine, ammonium acetate, under the usual condensation conditions .
  • inert organic solvents such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons or acetonitrile
  • acidic or basic condensing agents such as zinc chloride, phosphoric acid, hydrogen chloride, toluenesulfonic acid, boric acid, pyridine, piperidine, triethylamine, ammonium acetate, under the usual condensation conditions .
  • the condensation is carried out at temperatures in the range from 20 to 120 ° C.
  • the ring closure to the pyran derivative can take place together with the condensation or subsequent to it in the same or in a separate operation.
  • the ring closure is carried out in the presence of bases, such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner.
  • bases such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner.
  • bases such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner.
  • the crystallized spirodipyran compounds which precipitate out of this solution are, e.g. usable as color formers for copying processes by recrystallization or reprecipitation.
  • the color former also shows this slight tendency to form when writing on uncoated paper, where there is almost no color development, while a color former with a diethylamino group instead of the morpholine ring develops a clearly visible blue copy.
  • the compound develops a blue color in contact with acidic substances.
  • the color former melts at 101 to 102 ° C and develops a blue color with electron acceptor substances.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Description

Die Erfindung betrifft Spirodipyrane der allgemeinen Formel

Figure imgb0001
in der

  • A den Rest eines ankondensierten Benzolringes oder einen in 2,1-Stellung ankondensierten Naphthalinring und
  • R1 C1- bis C16-Alkyl bedeutet.
The invention relates to spirodipyrans of the general formula
Figure imgb0001
 in the
  • A the remainder of a fused-on benzene ring or a naphthalene ring fused in the 2,1-position and
  • R 1 is C 1 to C 16 alkyl.

Die Spirodipyrane der Formel sind schwach farbige bis farblose Verbindungen, deren Lösungen in einem inerten, organischen Lösungsmittel in Kontakt mit elektroenanziehenden Substanzen rotviolette bis blaue Färbungen geben. Typische Beispiele für Elektronenakzeptorsubstanzen sind Carbon-oder Mineralsäuren, Kaolin, Bentonit, aktivierter Ton, Aluminiumsilikat, Attapulgit oder jeder beliebige Ton, sauer reagierende polymere Materialien wie Kondensationsprodukte aus Phenolen und/oder Phenolsulfonsäuren, ferner Metalloxide oder -salze wie Zinkoxid, Aluminiumoxid, Zinkchlorid, Eisenstearat oder Cobaltnaphthenat.The spirodipyrans of the formula are weakly colored to colorless compounds, the solutions of which give red-violet to blue colorations in an inert, organic solvent in contact with electro-attracting substances. Typical examples of electron acceptor substances are carbon or mineral acids, kaolin, bentonite, activated clay, aluminum silicate, attapulgite or any clay, acidic polymeric materials such as condensation products from phenols and / or phenolsulfonic acids, also metal oxides or salts such as zinc oxide, aluminum oxide, zinc chloride, Iron stearate or cobalt naphthenate.

Aufgrunde dieser Eigenschaften sind die neuen Spirodipyrane der Formel 1 als Farbbildner für druckempfindliche Aufzeichnungsmaterialen oder Kopiermaterialien geeignet.Because of these properties, the new spirodipyrans of formula 1 are suitable as color formers for pressure-sensitive recording materials or copying materials.

Die erfindungsgemäßen Spirodipyrane der Formel 1 haben in druckempfindlichen Durchschreibesystemen den Vorteil, daß die Farbbildner auf nicht beschichtetem Streichrohpapier praktisch keine Tendenz zur Farbbildung zeigen. Beim Durchschreiben entsteht daher auf der Rückseite des mit dem Farbbildner beschichteten Deckblattes keine Spiegelschrift. Aus dem gleichen Grund erfolgt bei ungewollter Zerstörung der Kapseln keine Verschmutzung (Anfärbung) der Seite des Blattes, welche die Mikrokapselschicht trägt.The spirodipyrans of formula 1 according to the invention have the advantage in pressure-sensitive copying systems that the color formers show practically no tendency towards color formation on uncoated coating base paper. When copying, there is therefore no mirror writing on the back of the cover sheet coated with the color former. For the same reason, if the capsules are inadvertently destroyed, the side of the sheet carrying the microcapsule layer is not soiled (stained).

Die erfindungsgemäßen Spirodipyrane haben gegenüber dem aus den DE-OS 22 32 364, 23 23 803 und 24 30 568 bekannten Spirodipyranen, die in der 7-Stellung eine Dialkylaminogruppe tragen, den Vorteil, daß die Spirodipyrane der vorliegenden Erfindung auf Streichrohpapier und auf nicht mit aktivem Clay beschichteten Papier praktisch keine Färbung geben. Z.B. färbt der aus Beispiel 1 der DE-OS 22 32 364 bekannte Farbbildner Streichrohpapier ungefähr 12,5mal so stark an wie der Farbstoff des Beispiels 8 der vorliegenden Erfindung. Im Vergleich zu diesem Farbbildner färben die aus der DE-OS 23 23 803, Beispiel 2 und aus der DE-OS 24 30 568, Beispiel 5 bekannten Farbbildner Streichrohpapier ungefähr 4mal, bzw. 3,2mal stärker an.The spirodipyrans according to the invention have the advantage over the spirodipyrans known from DE-OS 22 32 364, 23 23 803 and 24 30 568, which carry a dialkylamino group in the 7-position, that the spirodipyrans of the present invention are on coating base paper and not on Give practically no coloring to active clay coated paper. E.g. the color former known from Example 1 of DE-OS 22 32 364 stains coating base paper about 12.5 times as strongly as the dye of Example 8 of the present invention. In comparison to this color former, the color formers known from DE-OS 23 23 803, Example 2 and from DE-OS 24 30 568, Example 5, dye base paper approximately 4 times or 3.2 times more strongly.

Gegenüber dem aus Beispiel 15 der DE-OS 26 11 600 bekannten Spirodipyran, das in der 7-Stellung eine Morpholingruppe und in der 7'-Stellung eine Diäthylaminogruppe trägt und das zu den Spirodipyranen der vorliegenden Erfindung als das nächstliegende anzusehen ist, weisen die Spirodipyrane der vorliegenden Erfindung bei gleichem Verhalten auf Streichrohpapier une wesentlich höhere Farbstärke auf. So beträgt die Farbstärke des aus Beispiel 15 der DE-OS 26 11 600 bekannten Farbbildners nur 29% der des Farbbildners aus Beispiel 2 der vorliegenden Erfindung.Compared to the spirodipyran known from Example 15 of DE-OS 26 11 600, which bears a morpholine group in the 7-position and a diethylamino group in the 7'-position and which is the closest to the spirodipyrans of the present invention, the spirodipyrans have the present invention with the same behavior on coating base paper and a significantly higher color strength. The color strength of the color former known from Example 15 of DE-OS 26 11 600 is only 29% of that of the color former from Example 2 of the present invention.

Vorteilhaft ist es, die erfindungsgemäßen Spirodipyrane in bekannter Weise in organischen Lösungsmitteln wie Chlorparaffinen, halogeniertem oder teilhydriertem Biphenyl, Alkylbenzol, Alkylnaphthalin, alkyliertem Dibenzylbenzol, Paraffinöl, Mineralöl oder auch in üblichen Lösungsmitteln wie Toluol, Xylol, in Form einer Lösung oder Suspension in Mikrokapseln einzuschließen und damit unter Mitverwendung von Bindemitteln und weiteren Hilfsmitteln wie Abstandshaltern die Papieroberfläche zu beschichten. Man erhält druckempfindliche Papiere, die in kontakt mit elektronenanziehenden Materialien bei entsprechendem Schrieb. oder Typendruck ein Schriftbild in rotvioletter bis blauer Farbe geben.It is advantageous to include the spirodipyrans according to the invention in a known manner in organic solvents such as chlorinated paraffins, halogenated or partially hydrogenated biphenyl, alkylbenzene, alkylnaphthalene, alkylated dibenzylbenzene, paraffin oil, mineral oil or else in customary solvents such as toluene, xylene, in the form of a solution or suspension in microcapsules and thus to coat the paper surface with the use of binders and other aids such as spacers. Pressure-sensitive papers are obtained which come into contact with electron-attracting materials with a corresponding writing. or type printing give a typeface in red-violet to blue color.

Geeignete Verfahren zur Herstellung von Mikrokapseln sind z.B. in den US-PS 2 800 457 und 2 800 458 und in der DE-PS 21 19 933 beschrieben.Suitable methods for producing microcapsules are e.g. in US-PS 2,800,457 and 2,800,458 and in DE-PS 21 19 933.

Da die erfindungsgemäßen Spirodipyrane (I) auch in wäßriger Suspension stabiler sind als Farbbildner, die Dialkylaminogruppen enthalten (DE-OS 22 32 364, 23 23 803 und 24 30 568), erhält man mit ersteren praktisch farblose Milrokapseldispersionen.Since the spirodipyrans (I) according to the invention are more stable in aqueous suspension than color formers which contain dialkylamino groups (DE-OS 22 32 364, 23 23 803 and 24 30 568), practically colorless microcapsule dispersions are obtained with the former.

Man kann die erfindungsgemäßen Spirodipyrane der allgemeinen Formel I auch nach dem in der US-PS 3 103 404 beschriebenen Verfahren in Wachs oder Öl-Wachsmischungen fein verteilen und mit diesen Mischungen Träger, wie Folien oder Papier beschichten. Man erhält druckempfindliche Materialien, die zum Durchschreiben auf mit Elektronenakzeptorsubstanzen beschichteten Papieren geeignet sind und die nach Gebrauch wie Kohlepapier entfernt werden.The spirodipyrans of the general formula I according to the invention can also be finely divided into wax or oil-wax mixtures by the process described in US Pat. No. 3,103,404 and carriers, such as foils or paper, coated with these mixtures. Pressure-sensitive materials are obtained which are suitable for copying on papers coated with electron acceptor substances and which are removed after use like carbon paper.

Für R1 sind als C1- bis C16-Alkyl z.B. zu nennen: Methyl, Äthyl, n-Propyl, Isopropyl, n-Butyl, sec. Butyl, Isobutyl, tert. Butyl, n-Pentyl, Isopentyl, n-Hexyl, n-Nonyl, i-Nonyl, n-Octyl, i-Octyl, n-Decyl, i-Decyl, n-Dodecyl, i-Dodecyl, n-Hexadecyl.For R 1, the following can be mentioned as C 1 to C 16 alkyl, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. Butyl, isobutyl, tert. Butyl, n-pentyl, isopentyl, n-hexyl, n-nonyl, i-nonyl, n-octyl, i-octyl, n-decyl, i-decyl, n-dodecyl, i-dodecyl, n-hexadecyl.

Aus technischen Gründen sind Verbindungen der Formel bevorzugt, in der R1 für C,- bis C4-Alkyl steht.For technical reasons, compounds of the formula in which R 1 is C 1 -C 4 -alkyl are preferred.

Besonders bevorzugte Farbbildner sind:

Figure imgb0002
in denen R = -CH3, -C2H5, -CH(CH3)2 oder -CH2CH(CH3)2 bedeuten.Particularly preferred color formers are:
Figure imgb0002
 in which R = -CH 3 , -C 2 H 5 , -CH (CH3) 2 or -CH 2 CH (CH 3 ) 2 .

Die Synthese der Farbbildner erfolgt nach dem folgenden Reaktionsschema in an sich bekannter Weise durch Cyclisierung der o-Hydroxylaryl-styryl-verbindungen der Formel IV. Letztere werden z.B. durch Kondensation von Benzopyryliumsalzen der Formel II mit N-substituierten p-Aminosalicylaldehyden der Formel III erhalten:

Figure imgb0003
The color formers are synthesized according to the following reaction scheme in a manner known per se by cyclization of the o-hydroxylaryl-styryl compounds of the formula IV. The latter are obtained, for example, by condensation of benzopyrylium salts of the formula II with N-substituted p-aminosalicylaldehydes of the formula III:
Figure imgb0003

Die Kondensation erfolgt zweckmäßigerweise in inerten organischen Lösungsmitteln, wie Alkoholen, Carbonsäuren, Carbonsäureanhydriden, Carbonsäureamiden, Kohlenwasserstoffen oderAcetonitril, gegebenenfalls in Gegenwart saurer oder basischer Kondensationsmittel, wie Zinkchlorid, Phosphorsäure, Chlorwasserstoff, Toluolsulfonsäure, Borsäure, Pyridin, Piperidin, Triäthylamin, Ammoniumacetat unter üblichen Kondensationsbedingungen.The condensation is expediently carried out in inert organic solvents, such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons or acetonitrile, optionally in the presence of acidic or basic condensing agents, such as zinc chloride, phosphoric acid, hydrogen chloride, toluenesulfonic acid, boric acid, pyridine, piperidine, triethylamine, ammonium acetate, under the usual condensation conditions .

In der Regel wird die Kondensation bei Temperaturen im Bereich von 20 bis 120°C ausgeführt.As a rule, the condensation is carried out at temperatures in the range from 20 to 120 ° C.

Der Ringschluß zum Pyranderivat kann zusammen mit der Kondensation oder anschließend an diese im selben oder in einem getrennten Arbeitsgang erfolgen. Der Ringschluß wird in Gegenwart von Basen, wie Natrium- oder Kaliumhydroxid, Natrium- oder Kaliumcarbonat, Natrium- oder Kaliumacetat, Ammoniak, aliphatischen Amine, Pyridin, in üblicher Weise durchgeführt. Die aus dieser Lösung sich abscheidenden kristallisierten Spirodipyranverbindungen sind direkt oder nach einer Reinigung z.B. durch Umkristallisieren oder Umfällen als Farbbildner für Kopierverfahren verwendbar.The ring closure to the pyran derivative can take place together with the condensation or subsequent to it in the same or in a separate operation. The ring closure is carried out in the presence of bases, such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner. The crystallized spirodipyran compounds which precipitate out of this solution are, e.g. usable as color formers for copying processes by recrystallization or reprecipitation.

Für die Herstellung der Verbindungen (IV) kommen als Ausgangsverbindungen der Formeln II und III z.B. in Betracht:

  • a) Pyryliumsalze der Formel II in Form ihrer Chloride, Perchlorate, Tetrafluorborate, Tetrachloroferrate, Trichlorzinkate:
    • 2,3-Dimethyl-benzopyryliumsalz,
    • 2-Methyl-3-i-propyl-benzopyryliumsalz,
    • 2-Methyl-3-i-butyl-benzopyryliumsalz,
    • 2-Methyl-3-decyl-benzopyryliumsalz,
    • 2-Methyl-3-i-pentyl-benzopyryliumsalz,
    • 2-Methyl-3-n-pentyl-benzopyryliumsalz,
    • 2-Methyl-3-äthyl-benzopyryliumsalz,
    • 2-Methyl-3-nonyl-benzopyryliumsalz,
    • 2,3-Dimethyl-naphtho-(2,1 -b)pyryliumsalz,
    • 2-Methyl-3-i-propyl-naphtho-(2,1-b)pyryliumsalz,
    • 2-Methy)-3-i-buty)-naphtho(2,1 -b)pyryliumsalz,
    • 2-Methyl-3-i-pentyl-naphtho(2,1-b)pyryliumsalz, und
  • b) als Aldehyd der Formel III: 4-N-Morpholinyl-salicylaldehyd.
For the preparation of the compounds (IV), the following are suitable as starting compounds of the formulas II and III:
  • a) Pyrylium salts of the formula II in the form of their chlorides, perchlorates, tetrafluoroborates, tetrachloroferrates, trichlorozincates:
    • 2,3-dimethyl-benzopyrylium salt,
    • 2-methyl-3-i-propyl-benzopyrylium salt,
    • 2-methyl-3-i-butyl-benzopyrylium salt,
    • 2-methyl-3-decyl-benzopyrylium salt,
    • 2-methyl-3-i-pentyl-benzopyrylium salt,
    • 2-methyl-3-n-pentyl-benzopyrylium salt,
    • 2-methyl-3-ethyl-benzopyrylium salt,
    • 2-methyl-3-nonyl-benzopyrylium salt,
    • 2,3-dimethyl-naphtho (2,1-b) pyrylium salt,
    • 2-methyl-3-i-propyl-naphtho (2,1-b) pyrylium salt,
    • 2-methyl) -3-i-buty) -naphtho (2,1-b) pyrylium salt,
    • 2-methyl-3-i-pentyl-naphtho (2,1-b) pyrylium salt, and
  • b) as the aldehyde of the formula III: 4-N-morpholinyl-salicylaldehyde.

Die Herstellung und Isolierung der Verbindungen der Formel wird in den folgenden Ausführungsbeispielen weiter erläutert. Die im folgenden genannten Teile beziehen sich auf das Gewicht.The preparation and isolation of the compounds of the formula is further explained in the following working examples. The parts mentioned below refer to the weight.

Beispiel 1example 1

165 Teile 2,3-Dimethyl-benzopyrylium-trichlorozinkat und 105 Teile 4-N-Morpholinylsalicylaldehyd werden in 900 Teilen Methanol zwei Stunden unter Rückfluß erhitzt. Der kristalline Farbstoff wird aus dem abgekühlten Reaktionsgemisch isoliert und in 500 Teilen 25%iger Ammoniaklösung und 1 000 Teilen Toluol bis zur vollständigen Aufhellung gerührt. Die Toluolphase wird abgetrennt, mit Natriumsulfat getrocknet und auf ein Drittel ihres ursprünglichen Volumens eingeengt. Durch Zugabe von 250 Teilen Methanol werden aus dieser Lösung 130 Teilen 3'-lrethyl-7-N-morpholinyl-2,2'-spirodi-(2H-1-benzopyran) der Formel

Figure imgb0004
gefällt.
Schmelzpunkt 136 bis 138°C.165 parts of 2,3-dimethyl-benzopyrylium trichlorozincate and 105 parts of 4-N-morpholinylsalicylaldehyde are refluxed in 900 parts of methanol for two hours. The crystalline dye is isolated from the cooled reaction mixture and stirred in 500 parts of 25% ammonia solution and 1,000 parts of toluene until it has completely brightened. The toluene phase is separated off, dried with sodium sulfate and concentrated to a third of its original volume. By adding 250 parts of methanol, 130 parts of 3'- 1- methyl-7-N-morpholinyl-2,2'-spirodi- (2H-1-benzopyran) of the formula are converted from this solution
Figure imgb0004
 like.
Melting point 136 to 138 ° C.

Wird eine Lösung dieser Verbindung in Mikrokapseln eingeschlossen und auf Papier als Beschichtung aufgebracht, so erhält man beim Auflegen und Beschriften auf einer sauren Nehmerschicht, wobei die Kapseln zerstört werden und deren Inhalt mit der Nehmerschicht in Berührung gebracht wird, eine intensive blaue Durchschrift.If a solution of this compound is enclosed in microcapsules and applied to paper as a coating, an intense blue copy is obtained when placed and labeled on an acidic receiver layer, the capsules being destroyed and the contents of which are brought into contact with the receiver layer.

Aufgrund der sehr geringen Selbstfarbentwicklungsfähigkeit des Farbbildners erfolgt praktisch keine Farbenentwicklung (Spiegelschrift) auf dem die Kapselschicht tragenden Blatt durch die aus den zerstörten Kapseln freigesetzte Farbbildnerlösung.Due to the very low self-color development ability of the color former, there is practically no color development (mirror writing) on the sheet carrying the capsule layer due to the color former solution released from the destroyed capsules.

Diese geringe Farbbildungstendenz zeigt der Farbbildner auch beim Durchschreiben auf nicht beschichtetem Papier, wo nahezu keine Farbentwicklung erfolgt, während ein Farbbildner mit einer Diäthylaminogruppe anstelle des Morpholinringes eine deutlich sichtbare, blaue Durchschrift entwickelt.The color former also shows this slight tendency to form when writing on uncoated paper, where there is almost no color development, while a color former with a diethylamino group instead of the morpholine ring develops a clearly visible blue copy.

Beispiele 2 bis 7Examples 2 to 7

Analog den Angaben in Beispiel 1 werden Farbbildner der Formel

Figure imgb0005
hergestellt.
Figure imgb0006
 Analogous to the information in Example 1, color formers of the formula
Figure imgb0005
 produced.
Figure imgb0006

Beispiel 8Example 8

19 Teile 2,3-Dimethyl-naphthopyryliumtrichlorozinkat und 11 Teile 4-N-Morpholinylsalicylaldehyd werden in 150 Teilen Alkohol zwei Stunden unter Rückfluß erhitzt. Der kristalline Farbstoff wird isoliert und wie in Beispiel 1 beschrieben in die farblose Spirodipyranform überführt. Man erhält 13 Teile des Farbbildners 3'-Methyl-7-N-morpholinyl-spiro-(2H-1-benzopyran)-2,2'-(2H)-naphtho(2,1-b)-pyran der Formel

Figure imgb0007
mit einem Schmelzpunkt von 154 bis 155°C.19 parts of 2,3-dimethyl-naphthopyrylium trichlorozincate and 11 parts of 4-N-morpholinylsalicylaldehyde are refluxed in 150 parts of alcohol for two hours. The crystalline dye is isolated and converted to the colorless spirodipyran form as described in Example 1. 13 parts of the color former 3'-methyl-7-N-morpholinyl-spiro- (2H-1-benzopyran) -2,2 '- (2H) -naphtho (2,1-b) -pyran of the formula are obtained
Figure imgb0007
 with a melting point of 154 to 155 ° C.

In Kontakt mit sauer reagirenden Substanzen entwickelt die Verbindung eine Blaufärbung.The compound develops a blue color in contact with acidic substances.

Praktisch keine Farbentwicklung erfolgt hingegen auf nicht mit Elektronenakzeptoren beschichtetem Papier. Eine vergleichsweise intensive blaugrüne Farbentwicklung erhält man mit einem Farbbildner, der durch eine Diäthylaminogruppe anstelle des Morpholinringes in 7-Stellung substituiert ist.On the other hand, there is practically no color development on paper that is not coated with electron acceptors. A comparatively intense blue-green color development is obtained with a color former which is substituted in the 7-position by a diethylamino group instead of the morpholine ring.

Beispiel 9Example 9

Entsprechend den Angaben in Beispiel 8 werden 21 Teile 2-Methyl-3-1-butyl- naphthopyryliumtrichlorozinkat und 11 Teile 4-N-Morpholinylsalicylaldehyd in 300 Teilen Alkohol zwei Stunden unter Rückfluß erhitzt.According to the information in Example 8, 21 parts of 2-methyl-3-1-butyl-naphthopyrylium trichlorozincate and 11 parts of 4-N-morpholinylsalicylaldehyde in 300 parts of alcohol are heated under reflux for two hours.

Man erhält 5 Teile 3'-i-Butyl-7-N-morpholinyl-spiro(2H-1-benzopyran)-2,2'-(2H)-naphtho-(2,1-b)-pyran der Formel

Figure imgb0008
5 parts of 3'-i-butyl-7-N-morpholinyl-spiro (2H-1-benzopyran) -2,2 '- (2H) -naphtho- (2,1-b) -pyran of the formula are obtained
Figure imgb0008

Der Farbbildner schmilzt bei 101 bis 102°C und entwickelt mit Elektronenakzeptorsubstanzen eine blaue Färbung.The color former melts at 101 to 102 ° C and develops a blue color with electron acceptor substances.

Beispiel 10 und 11Examples 10 and 11

Analog den Angaben in den Beispielen 8 und 9 werden die Farbbildner der Formel

Figure imgb0009
erhaltenAnalogous to the information in Examples 8 and 9, the color formers of the formula
Figure imgb0009
 receive

Die Bedeutung von R1 und die beim Kontakt mit sauer reagierenden Substanzen entwickelten Farbtöne sind in der folgenden Tabelle angegeben.

Figure imgb0010
The meaning of R 1 and the color shades developed on contact with acidic substances are shown in the following table.
Figure imgb0010

Claims (4)

1. Spirodipyrans of the general formula
Figure imgb0013
where R1 is C1- C18-alkyl and A is the radical of a fused benzene or 2,1-naphthalene ring.
2. Spirodipyrans as claimed in claim 1, characterised in that R1 in the formula is C1-C4 alkyl.
3. The use of the spirodipyrans as claimed in claim 1 or 2 as dye forming component for pressure-sensitive recording materials.
4. Pressure-sensitive recording materials, characterised in that they contain spirodipyrans as claimed in claim 1 or 2 as dye forming components.
EP78100629A 1977-08-18 1978-08-09 Spirobipyranes, their use and pressure-sensitive copying materials containing them Expired EP0000900B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772737207 DE2737207A1 (en) 1977-08-18 1977-08-18 COLOR PICTURES FOR COPYING
DE2737207 1977-08-18

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EP0000900A1 EP0000900A1 (en) 1979-03-07
EP0000900B1 true EP0000900B1 (en) 1981-01-14

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2611600C2 (en) * 1976-03-19 1986-12-18 Basf Ag, 6700 Ludwigshafen Spirodipyrans and their uses
JPS5545713A (en) * 1978-09-27 1980-03-31 Hodogaya Chem Co Ltd 7-substituted-spiropyran derivative
DE2847690A1 (en) * 1978-11-03 1980-05-22 Basf Ag COLOR IMAGE FOR COPYING PROCESS
AT385272B (en) * 1986-04-02 1988-03-10 Koreska Licensing Ges M B H Process for the preparation of novel spirodipyrans with two basic substituents
AU2001288432A1 (en) 2000-09-01 2002-03-22 Icos Corporation Materials and methods to potentiate cancer treatment

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NL126585C (en) * 1959-06-19
NL125655C (en) * 1959-07-15
FR2046319A5 (en) * 1969-04-23 1971-03-05 Fuji Photo Film Co Ltd Colour forming printing ink
DE2323803C3 (en) * 1973-05-11 1983-12-01 Basf Ag, 6700 Ludwigshafen Spirodipyrans and their use as color formers for copying processes
DE2363702A1 (en) * 1973-12-21 1975-07-10 Licentia Gmbh Spiro-naptho (2,3-b) pyran colour formers - for storage of (high frequency) signals
DE2430568C3 (en) * 1974-06-26 1979-02-08 Basf Ag, 6700 Ludwigshafen Spirodipyrans and their use as color formers for pressure-sensitive recording materials
DE2611600C2 (en) * 1976-03-19 1986-12-18 Basf Ag, 6700 Ludwigshafen Spirodipyrans and their uses

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DE2737207A1 (en) 1979-03-01
EP0000900A1 (en) 1979-03-07
US4161589A (en) 1979-07-17
DE2860328D1 (en) 1981-03-12

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