EP0000900A1 - 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
EP0000900A1
EP0000900A1 EP78100629A EP78100629A EP0000900A1 EP 0000900 A1 EP0000900 A1 EP 0000900A1 EP 78100629 A EP78100629 A EP 78100629A EP 78100629 A EP78100629 A EP 78100629A EP 0000900 A1 EP0000900 A1 EP 0000900A1
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alkyl
spirodipyrans
substituted
methyl
morpholinyl
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German (de)
French (fr)
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EP0000900B1 (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 I 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 the formula I are suitable as color formers for pressure-sensitive recording materials or copying materials.
  • the spirodipyrans of the formula I 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).
  • spirodipyrans 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 in common solvents such as toluene, xylene, in the form of a solution or suspension in Enclose microcapsules and thus coat the paper surface with the use of binders and other aids such as spacers.
  • This gives pressure-sensitive papers which, in contact with electron-attracting materials, give a typeface in red-violet to blue color when printed in accordance with type or type.
  • 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.
  • the spirodipyrans (I) according to the invention are more stable than color formers which contain dialkylamino groups even in aqueous suspension, the former gives practically colorless microcapsule dispersions.
  • 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.
  • carbo-C 1 to C 6 -alkoxy preferably carbo-C 1 to C 4 -alkoxy groups are suitable for the fused-on 2,1-naphthalene system (A).
  • the unsubstituted fused benzene and 2,1-naphthalene radical are particularly preferred.
  • R 1 Of the radicals mentioned for R 1 , C 1 -C 4 -alkyl, methoxyphenyl, ethoxyphenyl, ethylphenyl, methylphenyl and chlorophenyl are preferred, and very particularly preferred for R 1 is C 1 -C 4 -alkyl.
  • trimethylene groups for R 1 and R 2 include: trimethylene, ⁇ , ⁇ , ⁇ -trimethyltrimethylene, ß-tert. Butyltrimethylene, ß-n-octyltrimethylene, ß-n-dodecyltrimethylene, Bn-nonyltrimethylene.
  • N-isoindolinyl and especially N-morpholinyl is preferred.
  • spirodipyrans of the formula are for use as color formers preferred, in which R 1 , R2 and A have the meanings given above.
  • 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 compounds of the formula IV can also be prepared in a manner known per se by reacting the chalcones of the formula V with aldehydes of the formula III according to the following scheme:
  • condensation is expediently carried out in inert organic solvents, such as alcohols, carboxylic acids, carboxylic acid anhydrides, carboxamides, hydrocarbons or acetonitrile, if appropriate 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 customary 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 separate out from this solution are e.g. by recrystallization or order to use as a color former for copying.
  • 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 when it comes into contact with acidic substances.
  • Example 35 According to the information in Example 35, 21 parts of 2-methyl-3-i-butyl-naphthopyrylium trichlorozincate and 11 parts of 4-N-morpholinylsalicylaldehyde in 300 parts of alcohol are refluxed for two hours.
  • 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)

Abstract

Spirodipyrane der Formel <IMAGE> in der A den Rest eines ankondensierten Benzolringes oder 2,1-Naphthalinringes, die nicht substituiert oder durch Alkyl, Alkoxy, Nitro, Chlor, Brom oder Carbalkoxy substituiert sein können R¹ Alkyl, Phenyl, substituiertes Alkyl oder Phenalkyl und R² Wasserstoff oder R¹ und R² zusammen Trimethylen oder durch 1,2 oder 3 Alkyl substituiertes Trimethylen und B N-Morpholinyl, substituiertes Morpholinyl, Thiomorpholinyl-S-dioxid, N-(N'-Alkyl)-piperazinyl oder N-Isoindolinyl bedeuten und diese Spirodipyrane als Farbbildner enthaltende druckempfindliche Aufzeichnungsmaterialien. Die Pirodipyrane gehen mit Elektronenakzeptoren rotviolette bis blaue Färbungen, dagegen auf nicht mit Elektronenakzeptoren beschichtetem Papier keine Anfärbung.Spirodipyrans of the formula <IMAGE> in which A is the residue of a fused-on benzene ring or 2,1-naphthalene ring, which can be unsubstituted or substituted by alkyl, alkoxy, nitro, chlorine, bromine or carbalkoxy, R 1 alkyl, phenyl, substituted alkyl or phenalkyl and R² is hydrogen or R¹ and R² together are trimethylene or trimethylene substituted by 1,2 or 3 alkyl and B is N-morpholinyl, substituted morpholinyl, thiomorpholinyl-S-dioxide, N- (N'-alkyl) -piperazinyl or N-isoindolinyl and these Spirodipyrans as color formers containing pressure sensitive recording materials. The pirodipyrans go red-violet to blue in color with electron acceptors, but no staining on paper not coated with electron acceptors.

Description

Die Erfindung betrifft Spirodipyrane der allgemeinen Formel

Figure imgb0001
in der

  • A den Rest eines ankondensierten Benzolringes, der nicht substituiert oder durch C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Nitro, Chlor, Brom oder Carbo-C1- bis C6-alkoxy substituiert ist, oder einen in 2,1-Stellung ankondensierten Naphthalinring, der nicht substituiert oder durch Chlor, Brom oder Carbo-C1- bis C6-alkoxy substituiert ist,
  • R1 C1- bis C16-Alkyl, Phenyl, durch C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Chlor oder Brom substituiertes Phenyl oder C7- bis C10-Phenalkyl und
  • R2 Wasserstoff oder
  • und R2 zusammen eine Trimethylenbrücke oder eine Trimethylenbrücke, in der ein, zwei oder drei H-Atome durch C1- bis C12-Alkyl substituiert sind,
  • B N-Morpholinyl, durch ein oder zwei Methyl substituiertes N-Morphinyl, N-Thiomorpholinyl-S-dioxid, N-(N'-C1- bis C4-Alkyl)-piperazinyl oder N-Isoindolinyl bedeuten.
The invention relates to spirodipyrans of the general formula
Figure imgb0001
 in the
  • A is the residue of a fused-on benzene ring which is unsubstituted or substituted by C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, nitro, chlorine, bromine or carbo-C 1 - to C 6 -alkoxy, or a naphthalene ring fused in the 2,1-position which is unsubstituted or substituted by chlorine, bromine or carbo-C 1 -C 6 -alkoxy,
  • R 1 is C 1 to C 16 alkyl, phenyl, phenyl substituted by C 1 to C 4 alkyl, C 1 to C 4 alkoxy, chlorine or bromine or C 7 to C 10 phenalkyl and
  • R 2 is hydrogen or
  • and R 2 together is a trimethylene bridge or a trimethylene bridge in which one, two or three H atoms are substituted by C 1 to C 12 alkyl,
  • B is N-morpholinyl, N-morphinyl, N-thiomorpholinyl-S-dioxide, N- (N'-C 1 - to C 4 -alkyl) -piperazinyl or N-isoindolinyl or N-morpholinyl, substituted by one or two methyl.

Die Spirodipyrane der Formel I 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 I 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.

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

Die erfindungsgemäßen Spirodipyrane der Formel I 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 the formula I 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).

rVorteilhaft 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 Schreib- oder Typendruck ein Schriftbild in rotvioletter bis blauer Farbe geben.it is r Advantageously, spirodipyrans 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 in common solvents such as toluene, xylene, in the form of a solution or suspension in Enclose microcapsules and thus coat the paper surface with the use of binders and other aids such as spacers. This gives pressure-sensitive papers which, in contact with electron-attracting materials, give a typeface in red-violet to blue color when printed in accordance with type or type.

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, erhält man mit ersteren praktisch farblose Mikrokapseldispersionen.Since the spirodipyrans (I) according to the invention are more stable than color formers which contain dialkylamino groups even in aqueous suspension, the former gives practically colorless microcapsule dispersions.

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.

Als Substituenten am ankondensierten Phenylrest (A) kommen außer den bereits genannten im einzelnen z.B. in Betracht:

  • C1- bis C4-Alkyl: Isopropyl, n-Propyl, Isobutyl, sec.Butyl, tert.Butyl, insbesondere Methyl oder Äthyl; Cl- bis C4-Alkoxy:
  • Isopropoxy, Propoxy, n-Butoxy, Isobutoxy, vorzugsweise Methoxy oder Äthoxy; Carbo-C1- bis C6-alkoxy; Carbo-n-hexoxy, vorzugsweise Carbo-Ci- bis C4-alkoxy wie Carbomethoxy, Carboäthoxy, Carbo-n- und-i-propoxy, Carbo-butoxy, Carboisobutoxy, Carbo-tert.butoxy, Carbo-sec.-butoxy.
As substituents on the fused-on phenyl radical (A), apart from those already mentioned, the following are suitable, for example:
  • C 1 to C 4 alkyl: isopropyl, n-propyl, isobutyl, sec.butyl, tert.butyl, in particular methyl or ethyl; C l to C 4 alkoxy:
  • Isopropoxy, propoxy, n-butoxy, isobutoxy, preferably methoxy or ethoxy; Carbo-C 1 to C 6 alkoxy; Carbo-n-hexoxy, preferably carbo-C i - to C 4 -alkoxy such as carbomethoxy, carboethoxy, carbo-n- and i-propoxy, carbo-butoxy, carboisobutoxy, carbo-tert.butoxy, carbo-sec.-butoxy .

Am ankondensierten 2,1-Naphtalinsystem (A) kommen neben Chlor und Brom die vorstehend genannten Carbo-C1- bis C6-alkoxy-, vorzugsweise Carbo-C1- bis C4-alkoxygruppen in Betracht.In addition to chlorine and bromine, the above-mentioned carbo-C 1 to C 6 -alkoxy, preferably carbo-C 1 to C 4 -alkoxy groups are suitable for the fused-on 2,1-naphthalene system (A).

Für A sind der unsubstituierte ankondensierte Benzol- und 2,1-Naphthalinrest besonders bevorzugt.For A, the unsubstituted fused benzene and 2,1-naphthalene radical are particularly preferred.

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. Von diesen sind Cl- bis C4-Alkyl bevorzugt.
For R 1, the following are examples of C 1 to C 16 alkyl:
  • 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. Of these, C l - to C 4 -alkyl preferred.

Neben dem unsubstituierten Phenyl kommt als substituiertes Phenyl für R1 z.B. im einzelnen in Betracht:

  • Cl- bis C4-Alkoxyphenyl, wie Butoxy-, Propoxy-, Methoxy-oder Äthoxyphenyl; C1- bis C4-Alkylphenyl wie Isobutylphenyl; tert. Butylphenyl, sec. Butylphenyl, Propylphenyl, Isopropylphenyl, Äthyl- und Methylphenyl; Chlorphenyl, Bromphenyl.
In addition to the unsubstituted phenyl, the following can be considered as substituted phenyl for R 1, for example:
  • C l - to C 4 alkoxyphenyl, such as butoxy, propoxy, methoxy or ethoxyphenyl; C 1 to C 4 alkylphenyl such as isobutylphenyl; tert. Butylphenyl, sec. Butylphenyl, propylphenyl, isopropylphenyl, ethyl and methylphenyl; Chlorophenyl, bromophenyl.

Als Phenalkylreste sind für R1 z.B. zu nennen:

  • Benzyl, B-Phenyläthyl, ß-Phenylpropyl, γ-Phenylpropyl, γ-Phenylbutyl und δ-Phenylbutyl. L
Examples of phenyl radicals for R 1 are :
  • Benzyl, B-phenylethyl, ß-phenylpropyl, γ-phenylpropyl, γ-phenylbutyl and δ-phenylbutyl. L

Von den für R1 genannten Resten sind C1- bis C4-Alkyl, Methoxyphenyl, Äthoxyphenyl, Äthylphenyl, Methylphenyl und Chlorphenyl bevorzugt, ganz besonders bevorzugt ist für R1 C1- bis C4-Alkyl.Of the radicals mentioned for R 1 , C 1 -C 4 -alkyl, methoxyphenyl, ethoxyphenyl, ethylphenyl, methylphenyl and chlorophenyl are preferred, and very particularly preferred for R 1 is C 1 -C 4 -alkyl.

Als Trimethylengruppen sind für R1 und R2 im einzelnen z.B. zu nennen : Trimethylen, α,γ,γ -Trimethyltrimethylen, ß-tert. Butyltrimethylen, ß-n-Octyltrimethylen, ß-n-Dodecyltrimethylen, B-n-Nonyltrimethylen.Examples of trimethylene groups for R 1 and R 2 include: trimethylene, α, γ, γ -trimethyltrimethylene, ß-tert. Butyltrimethylene, ß-n-octyltrimethylene, ß-n-dodecyltrimethylene, Bn-nonyltrimethylene.

Für B ist N-Isoindolinyl und vor allem N-Morpholinyl bevorzugt.For B, N-isoindolinyl and especially N-morpholinyl is preferred.

Für die Verwendung als Farbbildner sind aus anwendungstechnischen Gründen Spirodipyrane der Formel

Figure imgb0002
bevorzugt, in der R1, R2 und A die vorstehend angegebenen Bedeutungen haben.For technical reasons, spirodipyrans of the formula are for use as color formers
Figure imgb0002
 preferred, in which R 1 , R2 and A have the meanings given above.

Aus technischen Gründen sind Verbindungen der Formel Ia bevorzugt, in denen R2 für Wasserstoff und R1 für C1- bis C4-Alkyl stehen. Von diesen sind insbesondere solche Verbindungen der Formel Ia bevorzugt, in der R2 für Wasserstoff, R1 für C1- bis C4-Alkyl und A für den unsubstituierten Rest eines ankondensierten Benz- oder 2,1-Naphthalinringes steht.For technical reasons, preference is given to compounds of the formula Ia in which R 2 is hydrogen and R 1 is C 1 -C 4 -alkyl. Of these, particular preference is given to those compounds of the formula Ia in which R 2 is hydrogen, R 1 is C 1 -C 4 -alkyl and A is the unsubstituted radical of a fused-on benzene or 2,1-naphthalene ring.

r Ganz besonders bevorzugte Farbbildner sind:

Figure imgb0003
und
Figure imgb0004
in denen R = -CH3, -C2H5, -CH(CH3)2 oder -CH2-CH(CH 3)2 bedeuten. r G anz particularly preferred color formers are:
Figure imgb0003
 and
Figure imgb0004
 in which R = -CH 3 , -C 2 H 5 , -CH (CH 3 ) 2 or - C H 2 - C H ( 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. Die Verbindungen der Formel IV können auch durch Umsetzung der Chalkone der Formel V mit Aldehyden der Formel III nach dem folgenden Schema in an sich bekannter Weise hergestellt werden:

Figure imgb0005
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 compounds of the formula IV can also be prepared in a manner known per se by reacting the chalcones of the formula V with aldehydes of the formula III according to the following scheme:
Figure imgb0005

Die Kondensation erfolgt zweckmäßigerweise in inerten organischen Lösungsmitteln, wie Alkoholen, Carbonsäuren, Carbonsäureanhydriden, Carbonsäureamiden, Kohlenwasserstoffen oder Acetonitril, gegebenenfalls in Gegenwart saurer oder basischer Kondensationsmittel, wie Zinkchlorid, Phosphorsäure, Chlorwasserstoff, Toluolsulfonsäure, Borsäure, Pyridin, Piperidin, Triäthylamin, Ammoniumacetat unter üblichenThe condensation is expediently carried out in inert organic solvents, such as alcohols, carboxylic acids, carboxylic acid anhydrides, carboxamides, hydrocarbons or acetonitrile, if appropriate 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 customary conditions

r Kondensationsbedingungen. r K ondensationsbedingungen.

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 Um fällen 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 separate out from this solution are e.g. by recrystallization or order to use as a color former for copying.

Für die Herstellung der Verbindungen (IV) kommen als Ausgangsverbindungen der Formeln II, III und V 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-benzopyriyliumsalz,
    • 2,3-Tetramethylen-benzopyryliumsalz,
    • 2-Methyl-3-decyl-benzopyryliumsalz,
    • 2-Methyl-3-i-pentyl-benzopyryliumsalz,
    • 2-Methyl-3-n-pentyl-benzopyryliumsalz,
    • 2,3-Dimethyl-6-chlor-benzopyriyliumsalz,
    • 2-Methyl-3-äthyl-benzopyryliumsalzl
    • 2,3-Dimethyl-6-brom-benzopyryliumsalz,
    • 2-Methyl-3-phenyl-benzopyryliumsalz,
    • 2-Methyl-3-benzyl-benzopyryliumsalz,
    • 2,3-Dimethyl-8-methoxy-benzopyryliumsalz,
    • 2,3-Dimethyl-7-methoxy-benzopyryliumsalz,
    • 2,3-(γ-tert.-Butyl-tetramethylen)-benzopyryliumsalz,
    • 2,3-Dimethyl-8-carbomethoxy-benzopyryliumsalz,
    • 2,3-Dimethyl-8-earboäthoxy-benzopyryliumsalz,
    • 2,3-Dimethyl-6-tert.-butyl-benzopyryliumsalz,
    • 2,3-Dimethyl-6-nitro-benzopyryliumsalz,
    • 2,3,6-Trimethyl-benzopyryliumsalz,
    • 2-Methyl-3-nonyl-benzopyryliumsalz,
    • 2-Methyl-3-phenäthyl-benzopyryliumsalz,
    • 2-Methyl-3-(4'-methylphenyl)-benzopyryliumsalz,
    • 2-Methyl-3-(4'-chlorphenyl)-benzopyryliumsalz,
    • 2,3-(γ-n-Octyl-tetramethylen)-benzopyryliumsalz,
    • 2,3-(γ-Dodecyl-tetramethylen)-benzopyryliumsalz,
    • 2,3-(γ-Nonyl-tetramethylen)-benzopyryliumsalz,
    • 2,3-(ß,γ,γ-Trimethyl-tetramethylen)-benzopyryliumsalz,
    • 2,3-Dimethyl-naphtho(2,1-b)pyryliumsalz,
    • 2,3-Dimethyl-7-chlor-naphtho(2,1-b)pyriyliumsalz,
    • 2,3-Dimethyl-7-brom-naphtho(2,1-b)pyryliumsalz,
    • 2,3-Dimethyl-10-carbomethoxy-naphtho(2,1-b)pyryliumsalz,
    • 2,3-Tetramethylen-naphtho(2,1-b)pyryliumsalz,
    • 2,3-(γ-tert.butyl-tetramethylen)-naphtho(2,1-b)pyrylium- salz,
    • 2-Methyl-3-i-propyl-naphtho-(2,1-b)pyryliumsalz,
    • 2-Methyl-3-i-butyl-naphtho(2,1-b)pyryliumsalz,
    • 2-Methyl-3-i-pentyl-naphtho(2,1-b)pyryliumsalz,
    • 2,3-Dimethyl-10-carboäthoxy-naphtho(2,1-b)pyryliumsalz
  • b) Aldehyde der Formel III: '
    • 4-N-Morpholinyl-salicylaldehyd,
    • 4-N-Isoindolinyl-salicylaldehyd,
    • 4-N-(N'-Methyl)-piperazinyl-salicylaldehyd,
    • 4-N-(3',5'-Dimethyl)-morpholinyl-salicylaldehyd,
    • 4-(N-Thiomorpholinsulfonyl)-salicylaldehyd
  • c) Chalkone der Formel V:
    • 1-o-Hydroxyphenyl-2-phenyl-buten-(1)-on-(3),
    • 1-o-Hydroxyphenyl-2-p-tolyl-buten-(1)-on-(3),
    • 1-o-Hydroxyphenyl-2-p-chlorphenyl-buten-(1)-on-(3).
For the preparation of the compounds (IV), the following are suitable as starting compounds of the formulas II, III and V, for example:
  • 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-benzopyriylium salt,
    • 2,3-tetramethylene-benzopyrylium salt,
    • 2-methyl-3-decyl-benzopyrylium salt,
    • 2-methyl-3-i-pentyl-benzopyrylium salt,
    • 2-methyl-3-n-pentyl-benzopyrylium salt,
    • 2,3-dimethyl-6-chloro-benzopyriylium salt,
    • 2-methyl-3-ethyl-benzopyrylium salt l
    • 2,3-dimethyl-6-bromo-benzopyrylium salt,
    • 2-methyl-3-phenyl-benzopyrylium salt,
    • 2-methyl-3-benzyl-benzopyrylium salt,
    • 2,3-dimethyl-8-methoxy-benzopyrylium salt,
    • 2,3-dimethyl-7-methoxy-benzopyrylium salt,
    • 2,3- (γ-tert-butyl-tetramethylene) benzopyrylium salt,
    • 2,3-dimethyl-8-carbomethoxy-benzopyrylium salt,
    • 2,3-dimethyl-8-earboethoxy-benzopyrylium salt,
    • 2,3-dimethyl-6-tert-butyl-benzopyrylium salt,
    • 2,3-dimethyl-6-nitro-benzopyrylium salt,
    • 2,3,6-trimethyl-benzopyrylium salt,
    • 2-methyl-3-nonyl-benzopyrylium salt,
    • 2-methyl-3-phenethyl-benzopyrylium salt,
    • 2-methyl-3- (4'-methylphenyl) benzopyrylium salt,
    • 2-methyl-3- (4'-chlorophenyl) benzopyrylium salt,
    • 2,3- (γ-n-octyl-tetramethylene) benzopyrylium salt,
    • 2,3- (γ-dodecyl-tetramethylene) benzopyrylium salt,
    • 2,3- (γ-nonyl-tetramethylene) benzopyrylium salt,
    • 2,3- (ß, γ, γ-trimethyl-tetramethylene) -benzopyrylium salt,
    • 2,3-dimethyl-naphtho (2,1-b) pyrylium salt,
    • 2,3-dimethyl-7-chloro-naphtho (2,1-b) pyriylium salt,
    • 2,3-dimethyl-7-bromo-naphtho (2,1-b) pyrylium salt,
    • 2,3-dimethyl-10-carbomethoxy-naphtho (2,1-b) pyrylium salt,
    • 2,3-tetramethylene-naphtho (2,1-b) pyrylium salt,
    • 2,3- (γ-tert.butyl-tetramethylene) -naphtho (2,1-b) pyrylium salt,
    • 2-methyl-3-i-propyl-naphtho (2,1-b) pyrylium salt,
    • 2-methyl-3-i-butyl-naphtho (2,1-b) pyrylium salt,
    • 2-methyl-3-i-pentyl-naphtho (2,1-b) pyrylium salt,
    • 2,3-dimethyl-10-carboethoxy-naphtho (2,1-b) pyrylium salt
  • b) aldehydes of the formula III:
    • 4-N-morpholinyl-salicylaldehyde,
    • 4-N-isoindolinyl-salicylaldehyde,
    • 4-N- (N'-methyl) -piperazinyl-salicylaldehyde,
    • 4-N- (3 ', 5'-dimethyl) morpholinyl salicylaldehyde,
    • 4- (N-thiomorpholine sulfonyl) salicylaldehyde
  • c) Chalcones of the formula V:
    • 1-o-hydroxyphenyl-2-phenyl-buten- (1) -on- (3),
    • 1-o-hydroxyphenyl-2-p-tolyl-buten- (1) -on- (3),
    • 1-o-hydroxyphenyl-2-p-chlorophenyl-buten- (1) -one- (3).

Die Herstellung und Isolierung der Verbindungen der Formel I 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 I 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'-Methyl-7-N-morpholinyl-2,2'- spirodi-(2H-1-benzopyran) der Formel

Figure imgb0006
gefällt.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'-methyl-7-N-morpholinyl-2,2'-spirodi- (2H-1-benzopyran) of the formula are converted from this solution
Figure imgb0006
 like.

Schmelzpunkt 136 bis 138°C.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 33Examples 2 to 33

Analog den Angaben in Beispiel 1 werden Farbbildner der Formel

Figure imgb0007
hergestellt.
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
 Analogous to the information in Example 1, color formers of the formula
Figure imgb0007
 manufactured.
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011

Beispiel 35Example 35

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 imgb0012
mit einem Schmelzpunkt von 154 bis 1550C.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 imgb0012
 with a melting point of 154 to 155 0 C.

In Kontakt mit sauer reagierenden Substanzen entwickelt die Verbindung eine Blaufärbung.The compound develops a blue color when it comes into 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 eineDiäthylaminogruppe 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 36Example 36

Entsprechend den Angaben in Beispiel 35 werden 21 Teile 2-Methyl-3-i-butyl-naphthopyryliumtrichlorozinkat und 11 Teile 4-N-Morpholinylsalicylaldehyd in 300 Teilen Alko- ' hol zwei Stunden unter Rückfluß erhitzt.According to the information in Example 35, 21 parts of 2-methyl-3-i-butyl-naphthopyrylium trichlorozincate and 11 parts of 4-N-morpholinylsalicylaldehyde in 300 parts of alcohol are refluxed 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 Formel5 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 imgb0013
Der Farbbildner schmilzt bei 101 bis 102°C und entwickelt mit Elektronenakzeptorsubstanzen eine blaue Färbung.
Figure imgb0013
 The color former melts at 101 to 102 ° C and develops a blue color with electron acceptor substances.

Beispiele 37 bis 45Examples 37 to 45

Analog den Angaben in den Beispielen 35 und 36 werden die Farbbildner der Formel

Figure imgb0014
erhalten.Analogous to the information in Examples 35 and 36, the color formers of the formula
Figure imgb0014
 receive.

Die Bedeutung der Substituenten R1, R2, R4 und -B und die beim Kontakt mit sauer reagierenden Substanzen entwickelten Farbtöne sind in der folgenden Tabelle angegeben.

Figure imgb0015
The meaning of the substituents R 1 , R 2 , R 4 and -B and the color shades developed on contact with acidic substances are given in the following table.
Figure imgb0015

Claims (9)

1. Spirodipyrane der allgemeinen Formel
Figure imgb0016
in der A den Rest eines ankondensierten Benzolrings, der nicht substituiert oder durch C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Nitro, Chlor, Brom oder Carbo-C1- bis C6-alkoxy substituiert ist, oder einen in 2,1-Stellung ankondensierten Naphthalinring, der nicht substituiert oder durch Chlor, Brom oder Carbo-C1- bis C6-alkoxy substituiert ist, R1 C1- bis C16-Alkyl, Phenyl, durch C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Chlor oder Brom substituiertes Phenyl, oder C7- bis C10-Phenalkyl und R 2 Wasserstoff oder R1 und R2 zusammen eine Trimethylenbrücke oder eine Trimethylenbrücke, in der ein, zwei oder drei H-Atome durch C1- bis C12-Alkyl substituiert sind, und B N-Morpholinyl, durch ein oder zwei Methyl substituiertes N-Morpholinyl, N-Thiomorpholinyl-S-dioxid, N-(N'-C1- bis C4-Alkyl)-piperazinyl oder N-Isoindolinyl
bedeuten.1. Spirodipyrans of the general formula
Figure imgb0016
 in the A is the residue of a fused-on benzene ring which is unsubstituted or substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, nitro, chlorine, bromine or carbo-C 1 -C 6 -alkoxy, or a naphthalene ring fused in the 2,1-position which is unsubstituted or substituted by chlorine, bromine or carbo-C 1 -C 6 -alkoxy, R 1 is C 1 to C 16 alkyl, phenyl, phenyl substituted by C 1 to C 4 alkyl, C 1 to C 4 alkoxy, chlorine or bromine, or C 7 to C 10 phenalkyl and R 2 is hydrogen or R 1 and R 2 together form a trimethylene bridge or a trimethylene bridge in which one, two or three H atoms are substituted by C 1 to C 12 alkyl, and B N-morpholinyl, one or two methyl-substituted N-morpholinyl, N-thiomorpholinyl-S-dioxide, N- (N'-C 1 - to C 4 -alkyl) -piperazinyl or N-isoindolinyl
mean. 2. Spirodipyrane gemäß Anspruch 1, dadurch gekennzeichnet, daß in der Formel B N-Morpholinyl bedeutet.2. Spirodipyrans according to claim 1, characterized in that in the formula B is N-morpholinyl. r3. Spirodipyrane gemäß Anspruch 1, wobei in der Formel R C1- bis C4-Alkyl, Methoxyphenyl, Äthoxyphenyl, Äthylphenyl, Methylphenyl oder Chlorphenyl, R 2 Wasserstoff und B N-Morpolinyl
bedeuten und A die in Anspruch 1 angegebene Bedeutung hat. r 3. S pirodipyrans according to claim 1, wherein in the formula RC 1 - to C 4 alkyl, methoxyphenyl, ethoxyphenyl, ethylphenyl, methylphenyl or chlorophenyl, R 2 is hydrogen and B N-Morpolinyl
mean and A has the meaning given in claim 1. 4. Spirodipyrane gemäß Anspruch 3, dadurch gekennzeichnet, daß A für einen ankondensierten Benzrest, für einen durch Methyl, Äthyl, Methoxy oder Äthoxy oder durch Carbo-C1- bis C4-alkoxy substituierten Benzrest, für einen ankondensierten 2,1-Naphthalinring oder für einen durch Carbo-C1- bis C4-alkoxy substituierten Naphthalinring steht. 4. Spirodipyrans according to claim 3, characterized in that A for a fused-on benz residue, for a benz residue substituted by methyl, ethyl, methoxy or ethoxy or by carbo-C 1 to C 4 -alkoxy, for a fused-on 2,1-naphthalene ring or for one by carbo-C 1 to C 4- alkoxy substituted naphthalene ring. 5. Spirodipyrane gemäß Anspruch 1, wobei in der Formel R1 C1- bis C4-Alkyl, R 2 Wasserstoff und B N-Morpholinyl
bedeuten und A die in Anspruch 1 angegebene Bedeutung hat. 5. Spirodipyrans according to claim 1, wherein in the formula R 1 C 1 to C 4 alkyl, R 2 is hydrogen and B N-morpholinyl
mean and A has the meaning given in claim 1. 6. Spirodipyrane gemäß Anspruch 1, wobei in der Formel R1 C1- bis C4-Alkyl, R 2 Wasserstoff, A den ankondensierten unsubstituierten Rest eines Benz- oder 2,1-Naphthalinringes und B N-Morpholinyl
bedeuten.6. Spirodipyrans according to claim 1, wherein in the formula R 1 C 1 to C 4 alkyl, R 2 is hydrogen, A the condensed unsubstituted residue of a benz or 2,1-naphthalene ring and B N-morpholinyl
mean. 7. Spirodipyrane gemäß Anspruch 1, dadurch gekennzeichnet, daß R 2 Wasserstoff, R1 Methyl, Äthyl, Isopropyl oder Isobutyl, A der Rest eines nicht substituierten ankondensierten Benz- oder 2,1-Naphthalinringes und B N-Morpholinyl
bedeuten.7. Spirodipyrans according to claim 1, characterized in that R 2 is hydrogen, R 1 is methyl, ethyl, isopropyl or isobutyl, A is the residue of an unsubstituted fused benz or 2,1-naphthalene ring and B N-morpholinyl
mean. 8. Verwendung der Spirodipyrane gemäß den Ansprüchen 1 bis 7 als Farbbildner für druckempfindliche Aufzeichnungsmaterialien.8. Use of the spirodipyrans according to claims 1 to 7 as color formers for pressure-sensitive recording materials. 9. Druckempfindliches Aufzeichnungsmaterial, dadurch gekennzeichnet, daß dieses als Farbbildner Spirodipyrane gemäß Patentanspruch 1 enthält.9. Pressure-sensitive recording material, characterized in that it contains spirodipyrans as color formers according to claim 1.
EP78100629A 1977-08-18 1978-08-09 Spirobipyranes, their use and pressure-sensitive copying materials containing them Expired EP0000900B1 (en)

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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
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022318A (en) * 1959-07-15 1962-02-20 Ncr Co Derivatives of 3-phenyl-spiro
GB889586A (en) * 1959-06-19 1962-02-21 Ncr Co Derivatives of 3-methyl-spiro(2h-1-betanaphthopyran-2,2[2h-1-benzopyran])
DE2019822A1 (en) * 1969-04-23 1971-01-14 Fuji Photo Film Co Ltd Printing materials
DE2232364A1 (en) * 1972-07-01 1974-03-28 Basf Ag NEW SPIRODIPYRANES AND COLOR FORMERS FOR COPYING
DE2323803A1 (en) * 1973-05-11 1974-12-05 Basf Ag NEW SPIRODIPYRANES AND COLOR FORMERS FOR COPYING
DE2430568A1 (en) * 1974-06-26 1976-01-15 Basf Ag COLOR PICTURES FOR COPYING
DE2611600A1 (en) * 1976-03-19 1977-09-22 Basf Ag COLOR PICTURES FOR COPYING

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* Cited by examiner, † Cited by third party
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DE2363702A1 (en) * 1973-12-21 1975-07-10 Licentia Gmbh Spiro-naptho (2,3-b) pyran colour formers - for storage of (high frequency) signals

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB889586A (en) * 1959-06-19 1962-02-21 Ncr Co Derivatives of 3-methyl-spiro(2h-1-betanaphthopyran-2,2[2h-1-benzopyran])
US3022318A (en) * 1959-07-15 1962-02-20 Ncr Co Derivatives of 3-phenyl-spiro
DE2019822A1 (en) * 1969-04-23 1971-01-14 Fuji Photo Film Co Ltd Printing materials
DE2232364A1 (en) * 1972-07-01 1974-03-28 Basf Ag NEW SPIRODIPYRANES AND COLOR FORMERS FOR COPYING
DE2323803A1 (en) * 1973-05-11 1974-12-05 Basf Ag NEW SPIRODIPYRANES AND COLOR FORMERS FOR COPYING
DE2430568A1 (en) * 1974-06-26 1976-01-15 Basf Ag COLOR PICTURES FOR COPYING
DE2611600A1 (en) * 1976-03-19 1977-09-22 Basf Ag COLOR PICTURES FOR COPYING

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