DE1950766A1 - Thermographic imaging material - Google Patents

Description

PATENTANWÄLTE 25/77 8 MUNCH EN 22 ²² '

DR.-ING. WOLFF, H. BARTELS, thierschstrasse 8

DR. BRANDES, DR.-ING. HELD TEiEFON = (O ₈ Ii) ₂₉₃₂₉₇

Reg. No. 122 117

EASTMAN KODAK COMPANY, 3 ^ 3 State S.treet, Rochester; New York State, United States of America

Thermographic imaging material

The invention relates to a thermographic image recording material, consisting of a support and at least one heat-sensitive dye.

Bs is known, the heat sensitivity of various dyes for the production of thermographic imaging materials to take advantage of. The usefulness of the dyes for the production of thermographic image recording materials is based ensure that the dyes change color when exposed to heat. The warmth can do that Dyes either through direct contact, for example by bringing a hot original or a hot recording pen into contact. On the other hand, can a recording material with one or more of the heat-sensitive dyes also in contact with a graphic Template, which radiant heat absorbs differently strong

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Has districts to be irradiated with heat rays. By the heat pattern generated in the original becomes heat-sensitive in the ' Layer of the image recording material produces a visible image corresponding to the original without this the original is destroyed or damaged.

A wide variety of heat radiation sources are suitable for carrying out such thermographic copying processes. One Particularly advantageous radiation sources are tungsten filament lamps, since the radiation they emit is rich in infrared and visible light, which is why tungsten filament lamps are particularly suitable for thermographic copying processes for copying of originals with image areas that absorb infrared radiation. * ■

A disadvantage of the previously known, - containing dyes, thermographic imaging materials is that the The dyes contained in them are only slightly heat-sensitive, which is why they are proportionate to the production of legible copies need to be irradiated for a long time.

The object of the invention was therefore to provide a thermographic image recording material consisting of a layer support and at least one heat-sensitive dye, 'to indicate which contains at least one such heat-sensitive dye that the material can be removed without prolonged heat irradiation suitable for making legible copies as well as image recordings.

Surprisingly, it has been found that organic dyes with at least one heterocyclic ring then excellent useful as heat-sensitive dyes for making thermographic image recording materials when they at least one heterocyclic ring with the group N-OR,

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wherein R is an optionally substituted alkyl, acyl or Aryl radical is included.

The invention thus provides a thermographic image recording material, consisting of a support and at least one heat-sensitive dye, which thereby characterized in that the image recording material is heat sensitive Dye means a dye having a heterocyclic ring with the group N-OR, where R is optionally substituted alkyl, acyl or aryl radical, contains one of the following formulas:

ι -:

τ τ · _J η ν ^θ

11 ^l β '1

TTT '

¹¹¹ R Γ

or

^R 2 ^R 2

IV Q ₂ NOR ₅ -—NQ ₉ 2 T

R /

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- 4 -which mean:

those to complete an optionally substituted, 5- or 6-membered, heterocyclic Ring's required atoms;

R is an optionally substituted alkyl, aryl or acyl radical;

R- is an optionally substituted methine or polymethine group with a terminal, for Cyanine dyes customary, heterocyclic ring, an anilinovinyl radical or optionally one substituted styryl radical;

Rj and R * each represent a hydrogen atom or optionally one substituted alkyl or aryl radical;

Rc is an alkylene or alkyleneoxy radical with 1 to 8

Carbon atoms in the alkylene chain or a radical of the formula: - ^ f-CH ₂ arylene-f-CH ₂ -> ^ - O _u -, in which s and t * denote numbers from 1 to 8 and u * O or 1;

Rg is an optionally substituted methine or

Polymethine group with a terminal heterocyclic ring customary for merocyanine dyes, an optionally substituted allylidene radical or an aldehyde radical;

Q ₂ and Qg the atoms required to complete an S- or 6-membered, heterocyclic ring and
an acid anion.

The arylene radical of the formula given under Rg preferably exists from an optionally substituted phenylene radical

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The usefulness of the dyes of the structural formulas given for the production of thermographic recording materials is based on the fact that when exposed to heat rays they split into fragments and change their color in the process. In the individual case The degradation or disintegration mechanism that sets in depends somewhat on the structure of the dyes used in the individual case away. However, based on observations, the degradation or destruction of the dyes proceeds through the action of Heat rays, for example, according to the following reaction scheme:

1 '+ CH ₃ O-

CH = CH-CH = C

O-CH,

hv

CH ₃ O + I +

H ⁺ ♦

C ₂ H ₅

more fragments

CH = CH-CH = C

There is thus a kind of photo-bleaching by heterolytic splitting of the nitrogen-oxygen bond with the generation of an ion of the formula RO ⁺ and a dye base, which can break down into further fragments or fragments.

According to the invention for the production of the recording material The dyes used are quickly destroyed according to the radiated heat radiation. ·

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The usability of the dyes described for the preparation of animal photographic image recording materials, e.g., copy recording materials, is based on the fact that they lose their original color during irradiation and im general to be bleached.

As particularly advantageous dyes for the production of thermographic Image recording materials have been found to have the structural formula III given.

The dyes can be used in various ways for the preparation of the thermographic image recording materials will. For example, suitable supports, in particular those with low thermal conductivity, can be coated with the dyes or the dyes can also be applied to the substrate in the form of solutions, so that the support absorbs the dye or dyes in the solution.

According to one embodiment of a thermographic imaging material According to the invention, a layer support made of paper is used, the paper being transparent, translucent or can be opaque.

It has often been found to be advantageous to use a layer support which allows radiant energy to pass through, in particular when the original to be copied does not transmit or transmit such radiation, d. H. at least the template or the image recording material should transmit or transmit thermal radiation.

In an advantageous manner, those layer supports made of, for example, paper or other fibrous materials or polymers, which have a charring ^{temperature of above 125 °} C., are used.

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The heat-sensitive dyes used according to the invention are preferably applied to a translucent or pakic layer support. After the recording material has dried, the heat-sensitive copying material can then be brought into contact with an original which has heat-absorbing areas, for example in contact with an original containing letters, whereupon the sandwich formed is irradiated with infrared radiation Strongly absorbing radiation, converting the radiation into heat, which is transferred to the image recording material and here brings about an image-appropriate color change in such a way that the parts of the image-recording layer which were exposed to the heat radiation change their color. to which no thermal energy was supplied, keep their original color unchanged. , *.

Advantageously, the heat-sensitive dyes after dispersing in a customary binder, they can be applied in the form of layers to the substrate. For the production Suitable binders for such thermographic image recording materials are, for example, ethyl cellulose, polyvinyl alcohol, Gelatine, collodion, polyvinyl acetal, cellulose ester, hydrolyzed cellulose esters and the like.

Gelatin has proven particularly advantageous.

When using a colloidal binder, the concentration can the same can be very different and the contrast of the image reproduction or image copy to be produced can be determined by concentration of the binder used vary widely.

If necessary, the for the production of the heat-sensitive Layers used in dispersions or pigments or other dyes or color formers are added. In some cases

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an increase in contrast can be achieved by using an additional colored pigment in the binder.

The source of radiation, e.g. B. an infrared lamp, can be so arranged that the infrared radiation first hits the back of the original. It has proven to be useful In such a procedure it often turned out to be on the reverse side of the original to apply an insulating surface through which the thermal radiation emitted by the original is absorbed, localized and intensified.

On the other hand, it is also possible, for example, to use the heat-sensitive Bringing the layer of the image recording material into contact with the original having heat-absorbing areas, for example in contact with the block letters of a print template, and then the sandwich from either the back of the original or the back of the imaging material irradiate here. Such copying processes are known, for example from US Pat. No. 2,663,657.

In addition to reflective exposure, as just explained, the image recording material of the invention can also use bireflective processes are processed. In these processes, it is useful to use layer supports which are for radiant energy are easily permeable, for example, are easily permeable to infrared radiation. Preferably the support is further relatively thin, so that the heat generated in the print areas or print characters of the original artwork is easily absorbed the heat-sensitive layer of the recording material can be transferred and there to a piner color change accordingly can lead to the back districts or print characters of the template.

If necessary, the substrate can consist of normal paper, that has been made temporarily or temporarily transparent

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so that exposure as described can be carried out can. The substance or compound making the paper transparent can then be removed again after exposure, see above that again an opaque or opaque reflective layer support is present. Process for making paper transparent are known. They therefore do not need to be described in more detail here.

That for the manufacture of the thermographic imaging material Heat-sensitive dyes used according to the invention do not need to be applied uniformly to a layer support to become, d. H. A wide variety of patterns of heat-sensitive dye can also be produced on the support be, d. H. For example, it is possible to use lines or dashes or just dots from the heat-sensitive layer on a layer support or to apply the heat-sensitive dyes. Such recording materials can be used for special purposes, in particular in the field of repro technology.

Aside from infrared lamps, you can use them to irradiate the image recording material according to the invention, the usual known radiation sources are used, which are thermographisciier in the context Procedures are used. The radiation source is expedient according to the absorption properties of the one to be reproduced Selected template. This means that the radiation emitted by the radiation source should be as strong as possible from the image areas the original to be reproduced is absorbed and converted into thermal energy are transferred, which then acts on the heat-sensitive dye or dyes.

For irradiating a thermographic image recording material According to the invention, incandescent lamps, for example, are therefore also suitable, since such incandescent lamps generally have a lot

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- ίο -

Radiant energy contained by the pictorial areas of many
Originals is easily absorbed.

In those cases where the radiant energy is not through the Substrate to which the thermosensitive dye is coated, transmitted or transferred should do so copying material, d. H. the original to be copied that transmit or transmit radiant energy, causing exposure can be done through the back of the image areas exhibiting template.

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In the given structural formula II, R- represents a methine or polymethine group with a terminal, for cyanine dyes common heterocyclic ring, the group may be substituted or unsubstituted, for example be substituted by an alkyl or aryl radical, and 2. B. have one of the following structural formulas:

-CH-CH -, - CH-, -C (CH ₃ ) -, -C (C ₆ H ₅ ) - or -CH = CH-CH =.

For cyanine dyes usual heterocyclic rings through which the methine group can be completed, for example, in the book by Mees and Jones ("The Theory of the Photographic Process ", MacMillan Verlag, 3rd Edition, pages 198-232.

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If R, has the meaning of an anilinovinyl radical, then has this preferably the formula:

-CH = CH-N

where R »is a hydrogen atom or an alkyl radical having preferably 1 to 8 carbon atoms.

If R- has the meaning of an optionally substituted one Styryl radical, this preferably has the formula:

-CH = CH

wherein J ^ is a hydrogen atom, an alkyl radical with preferably 1 to 8 carbon atoms ,, an aryl radical, preferably the phenyl or naphthyl series or an amino radical, including i a dialkyl amino radical, for example a dimethylamino radical, can be.

If R has the meaning of an optionally substituted Alkyl radical, this preferably has 1 to 8 carbon atoms and consists, for example, of a methyl, ethyl or butyl radical, or, for example, of a suTfoalkyl radical, ζ. Β. · Of the formula - / CH ^ 30--, or an aralkyl radical, e.g. B. a Benzyl or pyridinato-oxyalkyl salt residue, e.g. B. of the formula "CCH ^) J-O-Y, where Y is an optionally substituted pyridinium salt radical is.

If R has the equivalent of a recipient substituted aryl remainder, this preferably consists of an optionally substituted phenyl or narhthyl radical, z, B, a phenyl, Caphthyl or tolyl residue,

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preferably the formula _Q

ii

-CR ₆

in which R _{6 is} an alkyl radical having 1 to 8 carbon atoms or an aryl radical, preferably of the phenyl or naphthyl series, ie, for example, a methyl, ethyl, propyl, butyl, phenyl or naphthyl radical.

The 5- or 6-membered heterocyclic compound completed by Z The ring can be apart from the nitrogen atom already present in the ring optionally contain at least one further heteroatom, for example an oxygen, sulfur, selenium or Nitrogen atom. Z preferably represents those required to complete a pyridine, dBfe or quinoline ring Atoms "

The methine group represented by Rg may be a methine group the definition given in connection with R. Terminal heterocyclic rings customary for merocyanine dyes are for example in the already mentioned book by Mees and Jones "The Theory of the Photographic Process".

If Rg has the meaning of an optionally substituted one Allylidenrestes, this can for example from a Dicyanoallylidenrest, an alkylcarboxyallylidene radical or an alkylsulfonylallylidene radical, the alkyl groups of these radicals preferably have 1 to 8 carbon atoms.

If R2 and R. have the meaning of alkyl radicals, then show they preferably have 1 to 12 carbon atoms, especially 1 to 4 carbon atoms. Do R ~ · and R. have the meaning of Aryl radicals, these preferably consist of aryl radicals

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Phenyl or naphthyl series, ie R ₂ and Rj, can be, for example, methyl, 'ethyl, propyl, isopropyl, butyl, decyl or dodecyl radicals or phenyl, tolyl, naphthyl, methoxyphenyl, chlorophenyl or Nitrophenyl radicals.

Q ₂ and Qg preferably represent those 5- or 6-membered, heterocyclic rings which are typical of cyanine dyes and, in addition to the nitrogen atoms already present, may contain a further heteroatom, for example an oxygen, sulfur, selenium or nitrogen atom.

For example, X can be an acid anion, as in Cy.aninfarbstoffen occurs, for example a chloride, bromide, iodide, perchlorate sulfamate, thiocyanate, p-toluenesulfonate, methyl sulfate or tetrafluoroborate anion.

Rc can be, for example, an ethyleneoxy, trimethyleneoxy, Tetramethyleneoxy, propylidenoxy, ethylenedioxy or phenylenebisethoxy radical.

According to a particular embodiment of the invention, the recording material contains a photobleachable dye Dye of one of the following formulas:

Rp

Nt ⁸⁸ CHr-CH-, C-HL = LJ TL = C -f- CH = CH ~ Ϊ ~ ΓΤ NR _x X

3 OR

X®

OR E D

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R ₂

Q ₂ - /

HCHJYC <LLt ι. gi m

G Χ ^θ

-N = C-C ^ = L- L-f-C - (- CH = CH- ^ r-N R,

ι ni 'g-1 3

RO-N - (- CH = CH-C ^ = L-L = ^ C ^ c-O or RO-NH-CH-CH-C-f "L-L

where mean:

R is an optionally substituted aryl, alkyl or acyl radical;

R _{2 is} a hydrogen atom or an alkyl or aryl radical as defined above;

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R, an optionally substituted alkyl,

Alkenyl, aryl or alkoxy radical;

Q ,, Q ₂ , Q ,, the atoms required to complete 5- or 6-membered Qh and Qy ger »heterocyclic rings;

L is an optionally substituted methine group;

R ^ and Rj each represent a cyano, ester or alkylsulfonyl radical;

D, E and J each represent a hydrogen atom or an alkyl or aryl radical;

θ
X an acid anion;

G is an anilino or optionally substituted

.ierten aryl radical;

g = 1 or 2;

m = 1, 2 or 3 and

η = 1, 2, 3 or M.

In the structural formulas given, Q ₁ , Q 2, Q ..., Q ₇ and Qq represent the atoms which are required to complete 5- or 6-membered heterocyclic rings, as are typical for cyanine dyes. The rings can consist of sensitizing or desensitizing rings and can have a second heteroatom, for example an oxygen, sulfur, selenium or nitrogen atom.

For example, §1 » Qp» ^ 3 »% ^and ^ 9 ^can stand for the atoms that form one:

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Thiazole ring, ζ. B. a thiazole; 4-methylthiazole-; 3-ethylthiazole-; 4-phenylthiazole-; 5-methylthiazole-; S-phenylthiazole-; 4,5-dimethylthiazole-; 4,5-diphenylthiazole-; 4- (2-thienyl) thiazole-; Benzothiazoles 4-chlorobenzothiazole-; 4- or 5-nitrobenzothiazole-; 5-chlorobenzothiazole-; 6-chlorobenzothiazole-; 7-chlorobenzothiazole-; 4-methylbenzothiazole-; 5-methylbenzothiazole-; 6-methylbenzothiazole-; 6-nitrobenzothiazole-; 5-bromobenzothiazole-; 6-brojnobenzothiazole-; 5-chloro-6-nitrobenzothiazole-; 4-phenylbenzothiazole-; 4-methoxybenzothiazole-; 5-methoxybenzothiazole-; 6-methoxybenzothiazole-; 5-iodobenzothiazole-; 6-iodobenzbthiazole-; 4-ethoxybenzothiazole-; 5-ethoxybenzothiazole-; Tetrahydrobenzothiazole; 5,6-dimethoxybenzothiazole-; 5,6-dioxymethylene benzothiazole; 5-hydroxybenzothiazole-; 6-hydroxybenzothiazole-; a-naphthothiazole-; ß-naphthothiazole-; ß, ß-naphthothiazole-; 5-methoxy-ß, ß-naphthothiazole-; 5-ethoxyß-naphthothiazole-; 8-methoxy-a-naphthothiazole-; 7-methoxy-anaphthothiazole-; 4'-methoxythianaphtheno-7 ^f , 6 ', 4,5-thiazole or a naphthothiazole ring substituted by a nitro radical;

an oxazole ring, e.g. B. a 4-methyloxazole; 4-nitro-oxazole "; 5-methyloxazole-; 4-phenyloxazole-; 4,5-diphenyloxazole-; 4-ethyloxazole-; 4,5-dimethoxazole-; 5-phenyloxazole-; Benzoxazole-; 5-chlorobenzoxazole-; 5-methylbenzoxazole-; 5-phenylbenzoxazole-; 5- or 6-nitrobenzoxazole-; S-chloro-6-nitrobenzoxazole-; 6-methylbenzoxazole-; 5,6-dimethylbenzoxazole-; 4,6-dimethylbenzoxazole-; S-methoxybenzoxazole-jS-ethoxybenzoxazole-; 5-chlorobenzoxazole-; 6-methoxybenzoxazole-; 5-hydroxybenzoxazole-; 6-hydroxybenzoxazole-; os-naphthoxazole-; ß-naphthoxazole or a naphthoxazole ring substituted by a nitro radical;

a selenazole ring, e.g. B. a 4-methylselenazole; 4-nitroselenazole-; 4-phenylselenazole-; Benzoselenazole-; 5-chlorobenzoselenazole-; 5-methoxybenzoselenazole-; S-hydroxybenzoselenazole-;

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5- or 6-nitrobenzoselenazole-; S-chloro-o-nitrobenzoselenazole-; Tetrahydrobenzoselenazole-; ct-naphthoselenazole-; ß-naphthoselenazole or a naphthoselenazole ring substituted by a nitro radical;

a thiazoline ring, e.g. B. a thiazoline; 4 ~ methylthiazoline or 4-nitrothiazoline ring;

a pyridine ring, e.g. B. a 2-pyridine; 5-methyl-2-pyridines 4-pyridine-; 3-methyl-4-pyridine or a pyridine ring substituted by a nitro radical;

a quinoline ring, e.g. B. a 2-quinoline; 3-methyl-2-quinoline-; 5-ethyl-2-quinoline-; 6-chloro-2-quinoline-; 6-nitro-2-quinoline-; 8-chloro-2-quinoline-; 6-methoxy-2-quinoline-; 8-ethoxy-2-quinoline-; 8-hydroxy-2-chiholin-; 4-quinoline-; 6-methoxy-4-quinoline-; 6-nitro-4-quinoline-; 7-methyl-4-quino-lin-;
8-chloro-4-quinoline-; 1-isoquinoline-; 6-nitro-1-isoquinoline-;
3,4-dihydro-1-isoquinoline or 3-isoquinoline ring;

a 3,3-dialkylindolenin ring, preferably with a nitro
or cyano radical, e.g. B. a 3,3-dimethyl-5- or 6-nitroindolenine; 3,3-dimethyl-5- or 6-cyanoindolenine ring;

an imidazole ring, e.g. B. an imidazole; l-alkylimidazole-j
1-alkyl-4-phenylimidazole-; 1-alkyl-4,5-diethylimidazole-;
Benzimidazole-; 1-alkylbenzimidazole-; 1-alkyl-5-nitrobenzimidazole-; 1-aryl-S ^ -dichlorobenzimidazole-; 1-alkyl-α-naphthimidazole ring; or 1-aryl-β-naphthimidazole or 1-alkyl-5-methoxy-α-naphthimidazole ring.

an imidazo ^ "4,5-b _- 7-quinoxaline ring, e.g. a 1-alkylimidazo /" 4 _> 5-b _D 7-quinoxaline ring, e.g. B, a 1-ethylimidazo - / "4, S-b_7quinoxaline-; 6-chloro-1-ethylimidazo / ~ 4 _> 5-b _ot> 7-

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quinoxaline-; l-Alkenylimidazo / ~ 4,5-b_7quinoxaline-, ζ. B. 1-Allyl imidazo ^ ~ 4,5-b_7quinoxaline-; 6-chloro-1-allylimidazo ^ "4,5-b_7-quinoxaline-; 1-arylimidazo ^ 4,5-b-7quinoxaline, e.g. B. a 1-phenylimidazo / ~ 4,5-b_7-quinoxaline- or 6-chloro-1-phenylimidazo - / "4,5-b-7-quinoxaline ring;

a 3,3-dialkyl-3H-pyrrolo / 2,3-b-7-pyridine ring, e.g. B. a 3,3-dimethyl-3H-pyrrolo ^ ~ 2,3-b_7pyridine or 3,3-diethyl-3H-pyrrolo ^ ~ 2,3-b_7pyridine ring;

a thiazolo ^ 4,5-b_7quinoline ring ;.

Have R, and R ^ the meaning of ester radicals, they can z. B. consist of methoxycarbonyl and ethoxycarbonyl radicals. Have R ^ and R ₇ the meaning of alkylsulfonyl radicals, so these can z. B. consist of methyl sulfonyl and ethyl sulfonyl radicals. The ester or alkylsulfonyl radicals preferably contain 1 to 8 carbon atoms.

The heterocyclic ring completed by Q ₄ can, for example, have a nitrogen, sulfur, selenium or oxygen atom as a hetero atom or several of these atoms. For example, Q. can stand for the atoms that complete a:

2-pyrazolin-5-one ring, e.g. B. a 3-methyl-1-phenyl-2-pyrazolin-5-one, l-phenyl-2-pyrazolin-5-one or l- (2-benzothiazolyl) -3-methyl-2-pyrazolin-5-one ring;

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an isoxazolone ring, e.g. B. a 3-phenyl-S- (4ll) -isoxazolone- or 3-itethyl-S- (4II) -isoxazolone ring;

an oxindole ring, e.g. B. a 1-alkyl-2,3-dihydro-2-oxindole ring;

a 2,4,6-triketohexahydropyrimicIine ring, e.g. B. a barbituric acid or 2-thiobarbituric acid ring with its 1-alkyl derivatives, z. B. 1-methyl, I-ethyl, 1-propyl or 1-ilcptyl derivatives, or 1,3-dialkyl derivatives, e.g. IJ. 1,3-dimethyl-, 3,3 - "Diethyl-, 1,3-dipropyl-, 1,3-diisopropyl-, 1,3-di cyclohexyl-

or 1,3-DiCß-methoxyethyl) derivatives, or 1,3 ~ diaryl derivatives, z. B. 1,3-diphenyl, 1,3-di (p-chlorophynyl) or 1,3-di (p-ethoxycarbonylphynyl derivatives, or 1-aryl derivatives, e.g. B. 1-phenyl, 1-p-chlorophenyl or 1-p-Xthoxycarbonylphcnylderivaten, or 1-alkyl-3-aryl derivatives, e.g. B. l-ethyl-3-phenyl- or 1-n-IIep ty l-3-phenyl derivatives;

a rhodanine ring, d. H. a 2-thio-2,4-tliiazolidinedione ring, z. B. a rhodanine or 3-alkylrhodanine ring, e.g. B. a 3-ethylrhodanine or 3-allylrhodanine ring, or a 3-carboxyalkyl rhoclanine ring, ζ. B. cinon 3- (2-carboxyethyl) -rliodanine- or 3- (4-carboxybutyl) rhodanine ring, or a 3-sulfoalkylrhodanine ring, z. B. a 3- (2-sulfoethyl) rhodanine, 3-C3-sulfopropy1) rhodanine or 3- (4-sulfobutyl) rhodanine ring, or a 3-arylrhodanine ring, e.g., a 3-I'henylrhodanine ring;

a 2 (3II) -imidazo / 1,2-α-7 pyridone ring;

a 2-furanone ring, e.g. B. a 3-cyano-4-plicnyl-2 (51I) furanone ring;

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a thiophan-3-one-l, l-dioxide ring, ζ. B. a Benzo / b_7 ~ tjiioplien-. ^7th (2II) -one-1,1-dioxide ring;

a 5, 7-dioxo-6, 7-dihydro-5-thiazolo / ~ 3,2-α-7-pyrimidine ring, z. B. a 5,7-dioxo-3-phenyl-6,7-dihydro-5-thiazolo / 3.2-α-7-pyrimidine ring;

a 2-thio-2,4-oxazolidinedione ring, d. H. a 2-thio-2,4- (3II, 5II) -oxazoldione ring, z. B. a 3-ethyl-2-thio-2,4-oxazolidinedione-, 3-C2-5 sulfo (ethyl) -2-thio-2, 4-oxazolidinedione-, 3- (4-sulfobutyl) -2-thio-2 , 4-oxazolidinedioii- or 3- (3-carboxypropyl) 2-thio-2,4-oxazolidinedione ring;

a thianaphthenone ring, e.g. B. a 2- (2II) thianaphthenone ring;

a 2-thio-2,5-thiazolidinedione ring; d. H. a 2-thio-2,5- (3H, 4Il) -thiazoldione ring, z. B. a 3-ethyl-2-thio-2,5-t.hiazolidinedione ring;

a 2, <1-thiazolidinedione ring, e.g. B. a 2,4-thiazolidinedione, 3-Ätliyl-2,4-thiazolidinedione-, 3-phonyl-2, 4-thiazol.idindione- or 3 - «-? '.' apl \ thyl-2,4-thiazolidinedione ring;

a thiazolidinone ring, e.g. For example, a 4-thiazolidinone, 3-ethyl ⁱ -4-t] iiazolidinon-, 3-phenyl-4-thiazolidinone or 3-a-Naphthy1-4-thiazolidinone ring;

a 2-thiazolin-4-one ring _> e.g. B. a 2-ethylmercapto-2-thiazolin-4-one, 2-alkylphynylamino-2-thiazol-4-one or 2-diplienylamine-2-thiazolin-4-one ring;

a 2-IΓilino-4-oxazol-idinonring _> ie a pseudohydantoin ring;

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a 2,4-imidazolidinedione ring, d. Ii. an llydantoin ring, e.g. a 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 3 ~ Phenyl-2,4-imidazolidinedione-, .3-ct ^ Naphthyl-2,4-imidazolidinedione-, 1,3-diethyl-2,4-imidazolidinedione-, l ~ ethyl-3-phenyl-2,4-imidazolidinedione-, l-Ethyl-2 ~ a-naphth! r / l-2,4-imidazolidinedione- or 1,3-diphenyl-2,4-yne; idazolidinedione ring;

a 2-thio-2,4-imidazolidinedione ring, d. H. a 2-thiohydantoin ring, z. B. a 2-T3iio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, 3-C4-Sul £ obutyl) -2-thio-2,4-imidazolidinedione-, 3- (2-carboxyethyl) -2-thio-2,4-imidazolidinedione-, 3-phenyl-2-tliio-2,4-imidazolidinedione-, 3-otliaphthyl-2-thio-2,4-imidazolidinedione-, 1,3-diethyl-2-thio-2,4-imidazolidinedione-, l-ethyl-3-phenyl-2-thio-2,4-imidazolidinedione-, l-ethyl-3-cc-naphthyl-2-thio-2;, 4-imidazolidinedione or 1,3-diphenyl-2-thio-2,4-imidazolidinedione ring, or one

2-Iraidazoli.ti ~ 5 ~ onring, e.g. ß. a 2-propylmercapto-2-iraidazole

in-S-onring.

Q ₂ preferably represents the atoms which form an optionally substituted pyridine, VBM || or complete the quinoline ring.

D, E and J preferably represent aryl radicals.

Nuclei in which Q ,, Q ₂ , Q ₃ , Q ^, Q ₇ and Q ^ stand for the atoms which are necessary to complete an imidazo ^ ~ 4,5-b_ / quinoxaline ring or a thiazole, oxazole ring substituted by a nitro radical , Selenazole, thiazoline, pyridine, quinoline, indole or imidazole ring are so-called desensitizing or desensitizing rings.

INSPECTED

If R- has the meaning of an optionally substituted one Alkyl radical, this preferably has 1 to 12, in particular 1 to 4, carbon atoms. R, can thus for example consist of a methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl or dodecyl radical, or one Hydroxyalkyl radical, e.g. B. a ß-hydroxyethyl or ω-hydroxybutyl radical, or an alkoxyalkyl radical, e.g. B. a ß-methoxyethyl or lo-butoxybutyl radical, or a carboxyalkyl radical, z. B. a ß-Carboxyäthyl- or ω-Carboxybutylrest, or one Alkoxy radical, e.g. B. a methoxy or ethoxy radical, or one Sulfoalkyl radical, e.g. B. a ß-sulfoä.thyl- or ω-sulfobutyl radical, or a sulfatoalkyl radical, e.g. B. a ß-sulfatoethyl or ω-sulfatobutyl radical, or an acyloxyalkyl radical, e.g. B. a ß-acetoxyethyl, γ-acetoxypropyl or ω-butyryloxybutyl radical, or an alkoxycarbonylalkyl radical, e.g. B. a ß-Methoxycarbonyläthyl- or ω-Äthoxycarbonylbutylrest, or an aralkyl radical, z. B. a benzyl or phenethyl radical.

If R, has the meaning of an alkenyl radical, this consists, for example, of an allyl, 1-propenyl or 2-butenyl radical.

If R, has the meaning of an optionally substituted aryl radical, this preferably consists of an optionally substituted aryl radical of the phenyl or naphthyl series and consists, for example, of a phenyl, tolyl, maphthyl, Methoxyphenyl or chlorophenyl radical.

L can be, for example, a methine group substituted by an alkyl or aryl radical, for example a group of the following structural formulas: .-.

-CH =, -C (CH ₃ ) =, -C (C ₆ H ₅ ) =.

Preferably L is a methine group of the formula -C =, in which

T is a hydrogen atom, an alkyl radical with 1 to T

4 carbon atoms or an aryl radical of the benzene series, e.g. B. a phenyl

rest, is.

- 009816/1326

Possess D, E, and J is the meaning _of alkyl radicals, as these preferably have from 1 to 12, especially 1 to 4 carbon atoms, and for example consist of methyl, ethyl, propyl, isopropyl, butyl, decyl or Dodecylresten.

If D, E and J have the meaning of aryl radicals, these preferably consist of aryl radicals of the phenyl or naphthyl series and consist, for example, of phenyl, tolyl, naphthyl, methoxyphenyl, chlorophenyl or nitrophenyl radicals.

X may in turn be, for example, a perchlorate, tetrafluorotetracyanoquinodimethane W borate, chloride, bromide, iodide, sulfamate, thiocyanate, p-toluenesulfonate or methyl sulfate.

If G has the meaning of an aryl radical, this preferably consists of an aryl radical of the phenyl or naphthyl series, for example a phenyl, naphthyl, dialkylaminophenyl, tolyl, chlorophenyl or nitrophenyl radical. Does G mean of an anilino radical, this preferably has the meaning of a radical of the formula: //

^R 3

wherein R _{3 is} a hydrogen atom or an alkyl or acyl radical 'each having 1 to 8 carbon atoms.

_{The radical R 5} shown in structural formula IV can be, for example, an ethylene, trimethylene, tetramethylene, propylidenoxy, ethyleneoxy or phenylenebisethoxy radical.

If R has the meaning of an optionally substituted one Alkyl radical, this can expediently up to 12, preferably 1 to 8 and in particular 1 to 4 carbon atoms, i.e. R can be, for example, a methyl, ethyl, propyl, Isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl radical, or an alkaryl radical, such as, for example, a benzyl radical, or a sulfoalkyl radical, for example a ß-sulfoüthyl-, 6J-sulfobutyl- or to -sulfopropyl radical.

009816/1326

If R has the meaning of an acyl radical, this can be given by the formula: O

-C-R

are shown, where R is an optionally substituted alkyl radical of the meaning given or an aryl radical, preferably the phenyl or naphthyl series, d. H. for example a methyl, phenyl, naphthyl, propyl or benzyl radical.

In the formulas, Q ₂ preferably represents the atoms which are necessary to complete a pyridine, indole or quinoline ring.

Furthermore, D, E and J preferably represent aryl radicals.

In an advantageous manner, Q ₁ , Qo »Q3, Q ₇ and Q _g can also stand for the atoms which are required to complete an imidazole / ~ 4,5-b_ / quinoxaline ring or a thiazole, oxazole, selenazole substituted by a nitro group -, thiazoline, pyridine, quinoline, indole or imidazole ring are required. These rings are desensitizing rings.

Typical compounds consisting of dyes and which can be used according to the invention are, for example:

009816/1326

Table I.

1. 3-ethyl-1'-methoxyoxa-2'-pyridocarbocyanine perchlorate;

2. 1'-ethoxy-3-ethyloxa-2'-pyridocarbocyanine tetrafluoroborate;

3. 3'-ethyl-1-methoxy-2-pyridothiacyanine iodide;

4. 1-ethoxy-3-ethyl-2-pyridothiacyanine tetrafluoroborate;

5. l-benzyloxy-3'-ethyl-2-pyridothiacyanine iodide;

6. 3'-ethyl-1-methoxy-2-pyridothiacarbocyanine iodide;

7. 1-ethoxy-3 ^f -ethyl-2-pyridothiacarbocyanine tetrafluoroborate;

8. Anhydro-3 ¹ -ethyl-1- (3-sulfopropoxy) -2-pyridothiacarbocyanine hydroxide;

9. l-Benzyloxy-3'-ethyl-2-pyridothiacarbocyanine perchlorate;

10. 3'-ethyl-1-methoxy-2-pyridothiadicarbocyanine perchlorate;

11. l'-methoxy-1,3,3-trimethylindo-2'- ⁱ pyridocarbocyanine picrate;

12. 3'-ethyl-1-methoxy-4 ', 5-benzo-2-pyridothiacarbocyanine perchlorate;

13. l-ethoxy-3 ¹ -ethyl-4 ¹ , 5'-benzo-Z-pyridothiacarbocyanine tetrafluoroborate;

14 l ^l -ethoxy-3-äthyloxa-2'-carbocyahintetrafluoroborat;

15. 1'-Ethoxy-3-ethylthia-2-cyanine tetrafluoroborate;

16. 1 ⁵ -Xthoxy = 3-ethylthia-2'-carbocyanine tetrafluoroborate;

17. 1'-ethoxy-3-ethylthia-2'-dicarbocyanine tetrafluoroborate;

18. 1-methoxy-S'-methyl-Z-pyridothiazolinocarbocyanine perchlorate;

19. 3'-ethyl-1-methoxy-4-pyridothiacyanine perchlorate;

20. 3'-ethyl-1-methoxy-4-pyridothiacarbocyanine perchlorate;

21. 1,1'-dirnethoxy-2,2'-diphenyl-3,3'-indolocarbocyanine perchlorate;

22. 1-methoxy-1'-methyl-2,2 ', 10-triphenyl-3,3'-indolocarbocyanine perchlorate;

23. Ι, Ι'-diethoxy-2,2'-diphenyl-3,3'-indolocarbocyanine perchlorate;

24. 1-ethoxy-1'-methy1-2,2 ', 10-triphenyl-S ^' - indolocarbocyanine perchlorate;

25. 1'-ethoxy-3-ethyl-4,5-benzothia-2'-carbocyanine tetrafluoroborate;

26. 2-β-anilinovinyl-1-methoxypyridinium-p-toluenesulfonate;

2 7. l-ethyl-l'-methoxy-4,5-benzothia-4'-carbocyahine perchlorate;

009816/1326

28. S'-Ethyl-1-methoxyHj'-nitro-4-phenyl-S-indolothiacarbocyanine-p-toluenesulfonate;

29. 1-Ethoxy-3 ^f -ethyl-6'-nitro-2-phenyl-3-indolothiacarbocyanine p-toluenesulfonate;

30. 1,3-dially1-1'-methoxy-2-pheny! Imidazo / '4,5-b-7-quinoxalino-3'-indolocarbocyanine perchlorate;

31. 1,3-diallyl-l'-ethoxy-2'-phenylimidazo / ~ 4,5-b-7-quinoxalino-3 ¹ -indolocarbocyanine perchlorate;

32. 1-methoxy-2-methylpyridinium p-toluenesulfonate;

33. l-methoxy-4-methylpyridinium p-toluenesulfonate;

34. Anhydro-2-methyl-1- (3-sulfopropoxy) pyridinium hydroxide;

35. 1-ethoxy-2-methylpyridinium tetrafluoroborate;

36. 1-benzyloxy-2-methylpyridinium bromide;

37. 1-ethoxy-2-methylquinolinium tetrafluoroborate;

38. l-methoxy-2-phenylindole;

39. l-ethoxy-2-phenylindole;

40. I ¹ -methoxy-1,3,3-trimethyl 1-5-nitro-2'-phenylindo-3'-indolocarbocyanine perchlorate;

41. 1-methoxy-l ^1, 3 ', 3'-trimethyl-2-phenyl-3-indolo-2'-pyrrolo / 2,3-b_ ~ / pyridocarbocyaninperchlorat;

42. 1'-ethoxy-1,3,3-trimethyl 1-5-nitro-2'-phenylindo-3'-indolocarbocyanine-p-toluenesulfonate;

43. 1-ethoxy-l ¹ , 3 ', 3'-trimethyl-2-phenyl-3-indolopyrrolo / "2,3-b_ / · pyridocarbocyanine perchlorate;

44. 1,1'-ethylenedioxybispyridinium dibromide;

45. 1,1'-trimethylenedioxybispyridinium dibromide;

46. 1,1'-tetramethylenedioxybis (2-methylpyridinium) dibromide;

47. 1,1'-tetramethylenedioxybis C4-methylpyridinium) dibromide;

48. 1,1'-tetramethylenedioxybispyridinium dibromide;

49. 1,1'-pentamethylenedioxybispyridinium dibromide;

50. l-methoxy-2-phenylindole-3-carboxaldehyde;

51. l-ethoxy-2-phenylindole-3-carboxaldehyde;

52. 1-acetoxy-2- (4-dimethylaminostyryl) pyridinium perchlorate;

5 3. l-Benzoyloxy-2- (4-dimethylaminostyryl) pyridinium perchlorate;

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54. 1,3-diethyl-5- / ~ (l-methoxy-2ClII) -pyridylidene) ethylidene-7-2-thiobarbituric acid;

55. 3-Ethyl-5- / ~ (l-methoxy-2 (lH) -pyridylidene) ethylidene_7-. rhodanine;

56. 1,3-diethyl-5 - / "(l-methoxy-2 (liI) -pyridylidene) ethylidene-7-barbituric acid;

57. 2- (3,3-dicyanoallylidene) -1-methoxy-1,2-dihydropyridine;

58. 2 - / "Cl-methoxy-2 (1H) -pyridylidene) ethylidene_7benzo /" b_7-thiophen-3 (2H) -one-1,1-dioxide;

59. 3-Cyano-5 - ^ "(1-methoxy-2 (1H) -pyridylidene) ethylidene_7-4-phenyl-2 (5H) -furanone.

009816/1326

Manufacture of the dyes

1.) Preparation of compound no. 32 (method A)

A mixture of 10.9 g of 2-picoline N-oxide and 27.9 g of methyl p-toluenesulfonate was heated on the steam bath with constant stirring until an exothermic reaction began. After completion of the supply of external heat, the temperature rose to a maximum of about 120 ⁰ C. The mixture was then cooled, diluted with 200 ml of acetone and quenched. The deposited precipitate was filtered off and washed with acetone. The yield of reaction product was 23.2 g, corresponding to 79 % of theory. The melting point of the compound ^ ag at 113-4 ⁰ C.

2.) Preparation of compound no. 36 (method B)

10.9 g of 2-picoline N-oxide and 18.8 g of benzyl bromide were dissolved in 25 ml of acetone and the solution was refluxed for 10 minutes. After dilution with 150 ml of acetone, the solution was cooled. The deposited precipitate was filtered off and washed with acetone. The yield of reaction product was 19.0 g, corresponding to 68 % of theory. The melting point was 113 to 114 ^° C.

3.) Establishing compound no.26

5.90 g of compound no. 32 and 2.98 g of ethyl isoformanilide in 5 ml of dimethylformamide were heated on the steam bath for 1/2 hour. The mixture was then diluted with 50 ml of acetone and quenched. The resulting yellow precipitate was filtered off and washed with acetone. The yield was 3.3 g, corresponding to 41 % of theory. The melting point of the compound was 172 to 173 ^° C.

009816/1326

4.) Establishing compound no. 1

3-ethyl-1'-methoxyoxa-2'-pyridocarbocyanine perchlorate

CH = CH-CH =

ClO,

2.22 g of 1-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.17 g of 2-ß-acetanilidovinyl-3-ethylbenzoxazolium iodide and 1.4 ml of triethylamine in 20 ml of ethanol were refluxed for 2 minutes. Then a solution of 0.61 g of sodium perchlorate in hot methanol was added. After cooling, the reaction product separated out. It was filtered off and washed with ethanol. The yield of reaction product was 1.50 g, corresponding to 77 % of theory. The melting point of the compound was 146 to 147 ⁰ G.

5.) Establishing connection no. 3

S'-ethyl-1-methoxy-I-pyridothiacyanine iodide

4.44 g of 1-methoxy-2-methylpyridinium p-toluenesulfonate, 4.00 g 3-ethyl-2-phenylthiobenzothiazolium iodide and 2.8 ml of triethylamine

009816/1328

were refluxed in 20 ml of ethanol for 10 seconds. After quenching, the deposited precipitate was filtered off and washed with ethanol. The yield of reaction product was 1.55 g, corresponding to 38 % of theory. The melting point of the compound was 159 to 160 ^° C.

6.) Establishing compound no. 6

S'-ethyl-1-methoxy-Z-pyridothiacarbocyanine iodide

= CH- CH- =:

2.22 g of 1-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.25 g of 2-ß-acetanilidovinyl-3-ethylbenzothiazolium iodide and 1.4 ml of triethylamine were refluxed in 20 ml of ethanol for 2 minutes. The mixture was then quenched and the resulting precipitate was filtered off and washed with ethanol. The yield was 1.27 g, corresponding to 58 % of theory. The melting point of the compound was 115 ^° C.

7.) Establishing compound no. 10

3 ^t -ethyl-1-methoxy-2-pyridothiadicarbocyanine perchlorate

CH = CH-CH = CH-CH '

ClO,

009816/1326

3.54 g of l-methoxy-2-methylpyridinium p-toluenesulfonate, 4.76 g of 2- (4-acetanilido-1,3-butadienyl) -3-ethylbenzothiazolium iodide and 1.8 ml of triethylamine were in 20 ml of dimethylformamide for 2 minutes stirred for a long time at room temperature. The mixture was then diluted with 400 ml of ether. The ethereal layer was then decanted off and the oily residue was dissolved in 50 ml of methanol. A solution of sodium perchlorate in methanol was then added to the resulting solution. The mixture was cooled, whereupon the deposited precipitate was filtered off and washed with methanol. The yield of reaction product was 0.95 g, corresponding to 22 % of theory.

8.) Production of compound no. 11

I ¹ -Methoxy-1,3,3-trimethylindo-2 ^f -pyridocarbocyanine picrat - __

CH = CH-CH

COO ¹

2.22 g of 1-methoxy-2-methylpyridinium p-toluenesulfonate, 2.23 g 2-ß-Acetanilidovinyl-l, 3,3-trimethyl-3H-indolium iodide and 1.4 ml of triethylamine were refluxed for 2 minutes in 20 ml of ethanol.

009816/1328

temperature heated. The resulting solution was then cooled and a solution of 1.15 g of picric acid in ethanol was added. After cooling, the deposited precipitate was filtered off and washed with ethanol. The yield of reaction product was 1.12 g, corresponding to 40 % of theory.

9.) Establishing connection no. 12

3'-ethyl-1-methoxy-4 ', 5 ^f -benzo-2-pyridothiacarbocyanine perchlorate

CH-CH-CH =;

OCH.

^C 2 ^H 5

• ^C10 ₄ "

2.22 g of l-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.57 g of 2-ß-anilinovinyl-1-ethylnaphtho ^ "1,2-d_7thiazolium-p-toluenesulfonate and 1.4 ml of triethylamine in 25 ml of acetic anhydride was added with stirring 5 minutes heated to 4O ⁰ C long. a small amount of undissolved compounds were filtered off and the filtrate was diluted with excess ether. the ethereal layer was then decanted off and the residue was dissolved in 25 ml of methanol. then, a A solution of 0.61 g of sodium perchlorate in methanol was added. After cooling, the precipitate which had separated out was filtered off and washed with methanol. The yield of reaction product was 1.48 g, corresponding to 65% of theory.

009816/1326

10.) Establishing compound no. 21

1,1'-Whore thoxy-2,2'-diphenyl-3,3'-indolocarbocyanine perchlorate ^^

H ₃ CON

CH-CH-CH =

STILL,

ClO,

2.23 g of 1-methoxy-2-phenylindole were dissolved in 10 ml of hot acetic acid, whereupon 2.0 g of trimethoxypropene and 1.0 ml of 48% hydrobromic acid were added with stirring. The mixture was allowed to cool and then diluted with excess ether. The ethereal layer which formed was decanted off, whereupon the viscous residue was dissolved in 60 ml of methyl alcohol. Thereupon 1.5 ml of oily perchloric acid were added, whereupon the mixture was chilled. The deposited precipitate was filtered off and washed with methanol, water and ether. After recrystallization from methanol and acidification with perchloric acid, 1.48 g of pure dye, corresponding to 52 % of theory, were obtained. The melting point of the dye was 228 to 23O ⁰ C.

11.) Establishing compound no. 22

1-methoxy-l ^1- methy1-2,2 ', 10-tripheny1-3,3'-indolocarbo cyanine perchlorate

009816/1326

H ₃ CON

CH = CH-C =

© NCH.

ClO

1.26 g of S-formyl-1-methoxy ^ -phenylindole and 1.55 g of 1-methyl-2-methylenebenzyl-2-phenylindole were dissolved in 10 ml of hot acetic acid. Then 1.0 ml of oily perchloric acid in 3 ml of acetic acid were added, whereupon the mixture was allowed to cool. After standing for 2 hours at room temperature, the solid precipitate which had separated out was filtered off and washed with methanol and ether. After recrystallization from methanol acidified with perchloric acid, 1.92 g of pure dye, corresponding to 59 % of theory, were obtained. The melting point of the dye
ranged from 258 to 259 ⁰ C.

12.) Production of compound no. 28

3 ¹ -Ethyl-1-methoxy-6'-nitro-2-phenyl-3-indolothiacarbo cyanine-p-toluenesulfon a t

H ₃ CON

CH = CH

p-TS

009816/1326

1.26 g of S-formyl-1-methoxy - ^ - phenylindole, 1.98 g of 3-ethyl-2-methyl-6-nitrobenzothiazolium p-toluenesulfonate and 10 ml of acetic anhydride were heated to reflux temperature for 1 minute. After cooling, an excess of ether was slowly added. The deposited solid precipitate was filtered off and washed with ether. After recrystallization from methanol acidified with p-toluenesulfonic acid, 2.64 g of pure dye, corresponding to 84 % of theory, were obtained.

13.) Production of compound no. 30

, yypy ^^ quinoxalino-3'-indolocarbocyanine perchlorate

H ₃ CON

CH-CH

CH ₂ CH = CH ₂

ClO

CH ₂ CH = CH ₂

This dye was prepared according to the method described in the example, with the exception, however, that 2.18 gl, 3-diallyl-2-methylimidazo / ~ 4,5-b_7quinoxalinium-p-toluenesulfonate instead of S-ethyl - ^ - methyl- o-nitrobenzothiazolium p-toluenesulfonate were used. After recrystallization from a mixture of 65 ml of acetonitrile and 1 ml of 60 % perchloric acid, 1.78 g of pure dye, corresponding to 60% of theory, were obtained. The melting point of the dye was 229 to 231 ^° C. ·

009816/1326

14.) Establishing compound no. 38

l-methoxy-2-phenylindole

OCIL

3.0 g of sodium was dissolved in 200 ml of methanol. Then 20.9 g of 1-hydroxy-2-phenylindole, prepared as in Ber. ^ 8 (1895), page 585, and Bert. 2j9 (1896), page 2063, and 25.6 g of methyl iodide were added, whereupon the mixture was heated to reflux temperature for 1 hour. The resulting solution was then quenched, whereupon the deposited precipitate was filtered off and washed with methanol. The yield of reaction product was 15.9 g, corresponding to 71 l of theory. The melting point of the compound was 51 to 52 ^° C.

15.) Production of compound no. 40

1'-Methoxy-1,3,3-trimethyl-5-nitro-2'-pheny lidos'-indolocarbocyanine perchlorate ■ ·

H ₃ CON

CH = CH

ClO,

009816/1326

1.26 g of S-formyl-1-methoxy ^ -phenylindole, 1.30 g of 1,2,3,3-tetramethyl-5-nitro-3H-indolium-p-toluenesulfonate and 10 ml acetic acid ranhydride were heated to reflux temperature for 1 ΜίημΙβ, After cooling, excess ether was added. The ethereal layer was decanted off, leaving the viscous residue was dissolved in 25 ml of methanol. Then 1.0 ml of 60% perchloric acid in 5 ml of methanol was added. The mixture was then quenched, whereupon the deposited precipitate was filtered off and washed with methanol. After recrystallization 1.20 g of pure dye, corresponding to 43 l of theory, were obtained from a mixture of methanol and acetonitrile. The melting point of the dye was 266 ° C.

16.) Establishing compound no. 41

1-methoxy-1 ', 3', 3'-trimethyl-2-phenyl-3-indolo-2'- pyrrolo / 2,3-b_ / pyridocarbocyanine perchlorate

H ₃ CON

CH.

ClO,

1.26 g of S-formyl-1-methoxy ^ -phenylindole, 0.87 g of 1,3,3-trimethyl-2-methylene-2,3-dihydropyrrolo / 2,3-b-7-pyridine and 0.95 g of p-toluenesulfonic acid monohydrate and 10 ml of acetic anhydride were heated to reflux temperature for 1 minute. The mixture was then cooled and diluted with ether, after which the ethereal layer was decanted off. The residue was in 25 ml Dissolved methanol, whereupon 1.0 ml of 60% perchloric acid in 5 ml

0 0 9 816/1326

Methanol were added. After cooling, the solid precipitate which had separated out was filtered off and washed with methanol. After a single recrystallization from acetonitrile, 1.78 g of pure dye, corresponding to 69 % of theory, were obtained. The melting point of the dye was 235 to 239 ^° C.

17.) Preparation of compound no. 50 S-formyl-l-methoxy-Z-phenylindole

CHO

5.2 ml of phosphoryl chloride were slowly added to 15 ml of dimethylformamide with cooling so that the temperature did not rise above 20 ^° C. A solution of 11.15 g of 1-methoxy-2-phenylindole in 30 ml of dimethylformamide was then slowly added, the temperature being kept below 25 ^° C. The mixture was then ^{heated to 40 °} C. for 45 minutes and then poured into 390 ml of ice water. Then 70 ml of a 5 N sodium hydroxide solution were added, whereupon a viscous mass separated out. The mixture was ^{heated to 65 °} C., the lumps that had formed breaking up. The precipitate was filtered off and washed with water. The yield of reaction product was 11.95 g, corresponding to 96 % of theory. Of the. MELTING was 116 to 117 ⁰ C, and did not change after recrystallization from ethanol.

009816/1326

According to those described in Preparation Examples 1 to 17 Procedure Compounds 18-49 were made. The individual tables can be found in the two following tables HI and IV applied manufacturing methods, the yields achieved, the melting points of the compounds obtained.

Connect
manure
No. TABLE I. II method
in
example Solution
middle the end
prey
in % Mp. ⁰ C 237-41 Manuf
lungs bei
game no. 2 Interim
binding
No. -6 Ä 43 dec. 18th 4th 35 5 Ä 33 dec. 19th 5 35 5 Ä 18th 125-30 20th 7th 36 6th Ä 89 dec. 21 8th 35 6th M ^ 45 128-31 22nd 9 34 '4 M. 45 125 23 13th 36 9
(without NaClO ₄ EA
) 81 dec. 24 14th 35 6th M. 38 143 25th 15th 37 5. M. 47 dec. 26th 16 37 6th M. 63 138-9 27 18th 37 9
(Reaction
temp. 80 °) EA 35 127-8 2 8 19th 32 5 Ä 20th 186-7 29 20th 33 4th M. 58 128 30th 23 33 10 IT 36 219-21 31 24 39 11th IT 55 205-9 32 25th 51 11th DF / EA ⁽² ) 40 dec. 33 29 37 12th EA 100 dec. 34 31 51 13th .EA 58 220-1 35 42 51 15th
(without NaClO ₄ EA
) 65 194-200 41 43 51 16 EA 69 42 51

009 8 16/1326

TABLE IΥ

O
O
CD
OO

Manufacturing
game no.

36
37
38
39
40
43
44
45
46
47
48
49

Connecting s-

No.

33 34 35 37 39 44 45 46 .47 48 49 51

base

4-Picoline-N oxide

2-Picoline-N oxide

2-Picoline-N oxide

Quinaldine N oxide

l-hydroxy-2 phenylindole

Pyridine-N-oxide

Pyridine-N-oxide

2-Picoline-N oxide

4-Picoline-N oxide

Pyridine-N-oxide

Pyridine-N-oxide

l-ethoxy-2-phenylindole

Alkylating agents

Me thy1-ρ-toluenesulfonate

1,3-propane sultone

- · Triethyloxonium tetrafluoroborate

Triethyloxonium tetrafluoroborate

Ethyl iodide

Solution loot method medium %

1,2-dibroraoethane

1,3-dibromop r op an

1,4-dibromobutane

1,4-dibromobutane

1,4-dibromobutane

1,5-dibromopentane A
B.
B.
B.

acetone

CHCl ₃

CHoCIo

Example Ä
14th

CH ₃ CN

97 95 80 90

100 81

100 88 39 91

Mp. ⁰ C

153-4 202-3 53-7 115-7 oily 170-1 151-3 153-4 109-11 172

example
17th

115-7 95-6

■ Fs » 1

(1) Reaction mixture diluted with acetone to precipitate of the dye

(2) Reaction ^{temperature 25 °} C., without addition of NaClO.

Λ = ethyl alcohol M = methyl alcohol EA = acetic anhydride ES = acetic acid DF = dimethylformamide

50.) Establishing compound no. 54

l, 3-piäthyl-5- / ~ (l-methoxy-2 (lH) -pyridylidene) ethylidene_7 2-thiobarbituric acid

3.99 g of 2-ß-anilinovinyl-l-methoxypyridinium-p-toluenesulfonate, 2.00 g of 3-diethyl-2-thiobarbituric acid and 20 ml of acetic anhydride were stirred together, after which 5 ml of triethylamine were added. The mixture was then stirred for a few minutes until everything had dissolved. The solution was then seeded by adding a seed crystal obtained by diluting a small amount of the reaction mixture with excess ether. The mixture was then chilled for a few hours. The precipitated dye was filtered off and washed first with methanol and then with ether. The yield of pure dye was 1.48 g, corresponding to 44 % of theory. The melting point of the compound was 171 to 172 ⁰ C dec.

0098 16/1326

Compounds 55 to 59 were prepared in the manner described in Preparation Example 50. The yields obtained and the melting points of the compounds can be found in Table IV.

TABLE V

Manufacturing
example no. Connecting
No. yield
% Mp. ⁰ C 51 55 47 75.5. 52 56 25th 154-5 53 57 73 dec. 54 58 79 169-70 55 59 88 1334

009816/1326

The following examples are intended to illustrate the invention in more detail:

Beis]) iel 1

Bs became a thermographic image recording material thereby made that a paper support with a coating composition made of glaze and dye No. 12 coated ivurdc.

A graphic template with printing areas was in contact with brought the uncoated side of the paper support. The sandwich was then irradiated with an infrared lamp. In the heat-sensitive layer of the image recording material a facsimile copy of the original is thus produced.

Example 2

It became another thermographic image recording material prepared and tested according to the method described in Example 1, with the exception, however, that instead of the dye No. 12 the dyes 1 - 10, 16 - 20, 27, 29, 32 - 39, 4.1 and 44 - 53 were used. Excellent copies of the original were obtained in all cases.

Example 5

An image recording material according to the invention was thereby obtained produced that a coating compound on an aluminum support of gelatin and dye # 32 was applied. On the back of the recording material, i. H. the uncoated side, an image was then drawn with a hot pen. This way it was sensitive to heat Layer of the image recording material obtained a corresponding image.

0098 16/1328

Claims (1)

PATENT CLAIM E 1. Thermographic image recording material, consisting of a layer support and at least one heat-sensitive Dye, characterized in that the image recording material comprising a dye as a heat-sensitive dye a heterocyclic ring with the group N-OR where R is optionally substituted alkyl, acyl or aryl radical, contains one of the following formulas: ■ 7 ^R 8 OR π; ' _& ή R ₁ x * N OR III R ₄ - - -} R ₂ Χ ^θ or OR R, IV Qo N 4- N, Oo 2 Χ ^β T ' ^R 4 «4 009816/132 where mean: Z to complete an optionally substituted S- or 6-membered heterocyclic ring required atoms; R is an optionally substituted alkyl, aryl or acyl radical; Rj is an optionally substituted methine or poly methine group with a terminal heterocyclic ring customary for cyanine dyes, an anilinovinyl radical or an optionally substituted styryl radical; R2 and R ^ each represent a hydrogen atom or optionally one substituted alkyl or aryl radical; Rg is an alkylene or alkyleneoxy radical having 1 to 8 carbon atoms in the alkylene chain or a radical of the formula: - £ · CH ₀ arylene-f-CHL-W-0 -, in which: s and t * are numbers from 1 to 8 and u = 0 or T; Rg is an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for merocyanine dyes, optionally one substituted allylidene radical or an aldehyde radical; Q2 and Qg which are used to complete a 5- or 6-part, heterocyclic ring required atoms and X is an acid anion. 009816/1326 .- 47 - 2. Thermographic image recording material according to claim 1, characterized in that it is used as a heat sensitive dye contains a dye of one of the formulas given, • where Q2 is the one to complete a pyridine, quinoline or indole ring represents required atoms. 5. Thermographic image recording material according to Claims 1 to 2, characterized in that it is used as heat-sensitive Dye contains a dye of one of the following formulas: N = £ = CH — ClI ^eB 5 = in ^% C - (- 1 / -LH = - L ~ C - (- Cl I - CH-); - "n - R * X® j ^ ^J g-1 ^ nI ^ gI 3 ^R 2 OR Ii D R ₂ ClI-Cll ^ = ~ j = C - ^ - L = L - ^ - GX ^e 009816/1226 RO- N = C- -CKLL-) ~ c '- <- CH = CH- ^ y-Ν- R ₃ . Χ® J R _? RO- N-C-CH ^ = CH -) -; --- C - = (= L- L => ~ = C 'c = O or R ₀ , η _ ..
RO - NC-CII-CH-) 5- CK = LL ^ = C where mean: R is an optionally substituted aryl, Alkyl or acyl radical; R ₂ 'is a hydrogen atom or an alkyl or aryl radical. the meaning already given; R, an optionally substituted alkyl, alkenyl, aryl or alkoxy radical; Q ,, Qp, Q ^, the atoms required to complete 5- or 6-membered Qh ■ and Q ₇ ßer, heterocyclic rings; L is an optionally substituted methine group; 009816/1 326 R ^ and Ry each represent a cyano, ester or alkylsulfonyl radical; 'ü, H and J each represent a hydrogen atom or an alkyl or aryl radical; X is an acid anion; G is an anilino or optionally substituted aryl radical; g = 1 or 2; m = 1, 2 or 3 and η ■ '= 1,2,3 or 4. 4. Thermographic image recording material according to claims 1 to 3, characterized in that it contains at least one heat-sensitive dye of the formula: where mean: R is an optionally substituted alkyl or Acyl rest j 1 * 2 and R4 each have a hydrogen atom or, if necessary, one substituted alkyl or aryl radical and X is an acid anion. 009816/1326 5. Thermographic image recording material according to claims 1 to 4, characterized in that it is the heat-sensitive Contains compound as a layer in a binder dispersed on the support. 6. Thermographic image recording material according to claims 1 to 5, characterized in that it is an aluminum substrate having. 009816/1326