Classifications

• • 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)

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Citations (7)

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• 1977
  • 1977-08-18 DE DE19772737207 patent/DE2737207A1/de not_active Withdrawn
• 1978
  • 1978-08-08 US US05/932,015 patent/US4161589A/en not_active Expired - Lifetime
  • 1978-08-09 DE DE7878100629T patent/DE2860328D1/de not_active Expired
  • 1978-08-09 EP EP78100629A patent/EP0000900B1/fr not_active Expired
  • 1978-08-18 JP JP10012578A patent/JPS5441880A/ja active Pending

Patent Citations (7)

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