DE1472822A1 - Use of trinuclear dyes in photographic light-sensitive materials - Google Patents

Description

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Use of Trinuclear Dyes In Light-sensitive Photographic Materials.

Trinuclear dyes are known to be like complexes Cyanine dyes, complex merocyanine dyes and * Holopolar dyes for use as optical sensitizing agents in photographic silver halide demulsions. These dyes have the Property of extending the sensitivity of silver halide demulsions, including those in color photographic materials, to longer wavelengths. Applicable in practice Active dyes not only have to have suitable sensitizing properties, but also light be soluble, especially in aqueous medium, thus it is incorporated into photographic * emulsions.

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and also easily recovered during the development process of the photographic material the emulsion layers can be removed «so that in the images produced from the photographic material caused no or only minimal discoloration becomes · Especially with color photographic materials such sensitizing dyes must be used » which cause at most a very slight discoloration «

It is also known to use so-called bleachable dyes in light-filtering hydrophilic colloid layers in light-sensitive photographic elements his · FQr light filter sheets suitable dyes do not only have to light a certain

\ ■ ■ ■ ■ ■

absorb lengths, but can also be easily bleached; and or easily during normal photographic Have the development process removed from the photographic material

The invention was based on the finding that certain new trinuclear dyes with at least one nucleus, the

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by at least one by a secondary A substituted alkyl group is excellent for use as dyes in photographic layers. The dyes used according to the invention are complex cyanine dyes, complex merocyanine dyes and holopolar dyes with excellent spectral sensitization properties and excellent solubility behavior in aqueous media due to the latter property

>> _f i _Λ · discoloration

because they have lower SXXIIIMS in photographic materials than the previously known dyes.

As a result, the binding affects the use of trihukiearen 'dyes with at least one core of the by means of a secondary amino group

Each ^{1 is} substituted, the following

R-N (-CH = CH)

(sCH-CR, ¹

n-i

: CH-C (sCH-CH) == NR ₃ , PI \. *

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II. RN (-CH = CH) Ci = CH-CR ₁ ) r = CC = CC = D or

jl ¹ H-IX / \ /

W W,

III. R-N (-CH = CH) - C = CH-C (-CH = CH) CH = C (-CH = CH) 1

J-I II m-1 P-I

N-Y

where mean:

R and R _{2 are} alkyl groups;

R. a hydrogen atom, an alkyl or aryl group; Z and Z ₁ to complete eties thiazole; Benzothia

t zol-; Naphthothiazole-; Thlanaphtheno-7 ^f , 6 ^f , 4,5-

zol-; Oxazole-; Benzoxazole-; Naphthoxazole-; Selenazole-; Benzoselenazole-; Naphthoselenazole-; Thiazoline-; 2-pyridine-; 4-pyridine-; 2-quinoline-; 4-quinoline-; 1-isoquinoline-; 3-isoquinoliri-; 3,3'-dialkylindolenine-; Imidazole; Benzimidazole or naphthaimi-

dazolringes required atoms; j, m and ρ 1 or 2;
η is a number from 1 to 4;
Y and Y _{1 are} hydrogen atoms, alkyl groups, aryl groups or one

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N
^R 4

O or

Group,

in which 1 is a number from 2 to 4 and FL ·, R ^ and R _{5 represent} alkyl groups and wherein at least one of the groups Y or Y _{1 represents} a group having a tertiary nitrogen atom;

W and W ₁ oxygen, sulfur or selenium atoms or one

wherein Rg represents an alkyl or aryl group;

X is an acid residue »;

D and D _{1 are} oxygen, sulfur or selenium atoms and Q is -C = N-; -SC-; -0-C-; -NC- or

t π η ι η

R ₇ DDY ₁ D -CNC- group,

It t N

DY ₁ D ₁ wherein R _{7 is} a hydrogen atom, an alkyl, aryl,

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Represents amino, carbonamides, sulfonamido, sulfamyl or carbamyl groups and D, D ₁ and Y _{1 have} the meaning given,

in light-sensitive silver halide layers and / or light-filtering layers of a photographic material.

The alkyl groups represented by R and R ₂ preferably have 1 to 8 carbon atoms, ie they consist, for example, of methyl, sulfoethyl, carboxyäthy1, hydroxypropyl, sulbbutyl, carboxybutyl, hexyl or octyl groups

The 5- and 6-membered heterocyclic rings formed by Z and Z _{1 can individually consist of, for example:}

Rings of the thiazole series, such as, for example, thiazole; 4-methylthiazole-; 4-phenylthiazole-; 5-methylthiazole-; 5-phenylthiazole-; 4,5-dimethylthiazole-; 4,5-diphenylthiazole or * J- (2-thienyl) thiazole rings. and the like; Rings of the benzothiazole series, such as, for example, denzothiazole-j 4-chlorobenzothlazole-; 5-chlorobenzothiazole-; 6-chlorobenzothiazole-; 7-chlorobenzothiazole-; 4-methylbenzothiazole-; 5-methylbenzothiazole-; 6-methylbenzothiazole-; 5-bromobenzothiazole-; 6-bromobenzothiazole-; 4-phenylbenzothiazole-; 5-phenylbenzothiazole-j 4-methoxybenzothiazole-; 5-methoxybenothia-

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zol-; 6-methoxybenzothiazole-; 5-iodobenzothiazole-j 6-iodobenzothiazole-; 4-ethoxybenzothiazole-; 5-ethoxybenlaothiazole-; Tetrahydrobenzothiazole-; 5,6-dimethoxybenzothiazole-; 5,6-dioxymethylene benzothiazole; 5-hydroxybenzothiazole or 6-hydroxybenzothiazole rings and the like.

Naphthothiazole series rings, e.g., α-naphthothiazole-; ß-naphthothiazole-; 5-methoxy-β-naphthothiazole-; 5-ethoxy-β-naphthothiazole-; 8-methoxy-α-naphthothiazole 7-methoxy-α -naphthothiazole rings and the like;

Rings of Thionaphtheno-7 ¹ 6 ·, 4,5-thiazole, such as a 4'-Methoxythianaphtheno-7 ', 6', 4,5-thiazole ring; Rings of the oxazole series, for example a 4-methyloxazole; 5-ethyloxazole-; 4-phenyloxazole-; M, 5-diphenyloxazole-; 4-ethyloxazole-; 4,5-dimethyloxazole or a 5-phenyloxazole ring and the like;

Rings of the benzoxazole series, such as, for example, a benzoxazole; 5-chlorobenzoxazole-; 5-methylbenzoxazole-; 5-phenylbenzoxazole-; 6-methylbenzoxazole-; Sjo-dirnethylbenzoxazole-; 4,6-dimethylbenzoxazole-; 5-methoxybenzoxazole-; 5-ethoxybenzoxazole-; 5-chlorobenzoxazole-; 6-methoxybenzoxazole-; 5-hydroxybenzoxazole or a 6-hydroxybenzoxazole ring and the like. Rings of the naphthoxazole series, such as an a-naphtoxazole or β-naphtoxazole and the like; Rings of the üelenazole series, such as a 4-methylselenazole; 4-phenylselenazole ring and the like;

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Rings of the ßenzoselenazole series, such as, for example, a benzoselenazole 5-chlorobenzoselenazole; 5-methoxybenzoselenazole-; 5-hydroxybenzoselenazole or a tetrahydrobenzoselenazole ring and the like;

Rings of the naphthoselenazole relhe, such as an ot-naphthoselenazole or B-naphthoselenazole ring; Rings of the thiazoline series such as a thiazoline or a 4-methylthiazoline ring and the like; Rings of the 2-pyridine series such as a 2-pyridine-i or 5-methyl-2-pyridine ring and the like; Rings of the 4-pyridine series such as a 4-pyridine or 3-methyl-4-pyridine ring and the like; Rings of the 2-quinoline series, such as a 2-quinoline; 3-methyl-2-quinoline-; 5-ethyl-2-quinoline-; 6-chloro-2-quinoline-; 8-chloro-2-quinoline; 6-methoxy-2-quinoline-; 8-ethoxy-2-quinoline or an 8-hydroxy-2-quinoline ring and the like;

Rings of the 4-quinoline series, such as a 4-quinoline; 6-methoxy-4-quinoline-; 7-methyl-4-quinoline or a 8 * -chloro-4-quinoline rinse and the like; Rings of the 1-isoquinoline series, such as a 1-isoquinoline or a 3,4-dihydro-1-isoquinoline ring and the like; Rings of the 3-isoquinoline series, such as a 3-isoquinoline ring and the like;

a ring of the 3,3-dialkylindolenin series, for example / 3,3-di-

melhylindolenin-; 3,3,5-trimethylindolenine or a 3,3,7-

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Trimethylindolene ring and the like;

Rings of the imidazole series, such as an imidazole; 1-alkylimidazole-; 1-alkyl-4-phenylimidazole or a 1-alkyl-4,5-dimethylimidazole ring and the like; Rings of the benzimidazole series, such as a benzimidazole; 1-alkyl-benzimidazole or an 1-alkyl-5,6-dichlorobenzimidazole ring and the like;

Rings of the naphthimidazole series, such as, for example, an X- alkyl-anaphthimidazole ring or a 1-alkyl-β-naphthimidazole or 1-alkyl-5-methoxy-β-naphthimidazole ring and the like.

If R _{1 has} the meaning of an alkyl group, this can

for example consist of a methyl, ethyl or butyl group and the like, while phenyl or tolyl groups and the like are suitable as aryl groups.

If Y and Y ₁ are alkyl groups, these can for example consist of methyl, methoxyethyl or butyl groups and the like. Possible aryl groups are, for example, phenyl or tolyl groups and the like.

For example, Ro, R ₁ J and Rc can be alkyl groups such as methyl, propyl, butyl or hexyl groups and the like. Rg can have the same meaning if Rg has the meaning of an alkyl group. If Rg represents an aryl group, this B can for example consist of a phenyl or tolyl group

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group and the like.

X represents, for example, a chloride, bromide, iodide, perchlorate, Sulfamate, thiocyanate, p-toluenesulfonate, benzenesulfonate, Methyl sulfate residue and the like.

R ₇ represents a group which is often in the three-position of 2-pyrazolin-5-ones, ie for example a methyl, isopropyl, tertiary butyl, hexyl, phenyl, tolyl, halophenyl, methylamino -jDiethylamino, phenylamino, ethylcarbamido, phenylcarbonamido, butylsulfonamido, phenylsulfonamido, propylsulfamoyl, phenylsulfamoyl, ethjicarbamoyl or phenylcarbamoyl and the like.

The dyes used according to the invention are in aqueous media, especially in the presence of an equivalent of one

η
Easily soluble in acid and excellently suited for the spectral sensitization of photographic hydrophilic silver halide emulsions. Because of their good solubility in aqueous media, the dyes can easily be incorporated into photographic emulsions and the rest can be easily and completely removed from the emulsion layers during the development process.

The dyes of the formula I can be prepared in a simple manner by reacting a merocyanine dye of the following formula: 909813/1301

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- li -

I \

IV. RN (-CH = CH) CC = CH-CR ₁ ) SC C = S

JI η-1 \ _w /

wherein R, Z, j, R ₁ , η and W have the meaning already given and L represents a Y or a Y 'group, where, if the latter group is a substituted aminoalkyl group, this advantageously consists of a hydro salt of the amine , with dimethyl sulfate and dimethylformamide and subsequent reaction of the quaternary salt obtained with a compound of the following formula:

V. CH - C (= ΠΗ-ΠΗΪ NO-

³ p-li ²

wherein Z ₁ , p, R ₂ and χ have the meaning already given.
seated / Preferably the reaction of the quaternary salt with a compound of the formula V takes place by heating the two reaction components in a solvent in the presence of a basic condensing agent, in particular a trialkylamine, for example triethylamine, tributylamine and the like. or a dialkylaniline, such as N, i \ i-dimethylaniline; N, N-diethylaniline and the like. Or a heterocyclic tertiary amine such as pyridine, quinoline or an N-alkylpiperidine and the like. Or an alkali metal alcoholate such as sodium ethylate and the like.

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Dyes of the formula II can advantageously be prepared by reacting a compound of the formula IV with dimethyl sulfate and dimethylformamide and then
Condensation of the quaternary salt obtained with a compound of the following formulas:

0 0

η η

VI. C N-L or C N-L

ft if

" ² V

C = SH ₂ CC = S

where W, W. and L have the meaning already given.
sit _f / The condensation can conveniently be carried out in an inert solvent in the presence of one of the basic condensation agents already described. It has proven advantageous to heat the reaction mixture to reflux temperature.

The dyes of the formula III can be used in an advantageous manner by condensation of a dye of the formula:

0 η

VII. R-N (-CH = CH) K) = CH-C C N-Y

CH ₃

in which R, Z, j, Y and Q have the meanings already given, with a quaternary cyclammonium salt of the following formula: ^{9098 13/1301}

-I "χ.

TTTTT TD KT / —ΓΊΧ / ** TT \ / ^ VXXJ. · ^ P ^- -OV - * - »" ~ ΙΉ · j * ^

χ P-I

be prepared, where in formula VIII R ₂ , χ, Z ₁ and ρ have the meaning already given and Rg the meaning of an alkyl group, for example a methyl, ethyl, benzyl group or an aryl group, for example a phenyl, tolyl group and the like . owns. The implementation can be advantageous. Way be carried out in an inert solvent in the presence of a basic condensing agent of the type described, it has been found to be advantageous to heat the reaction mixture to reflux temperature.

The dyes of the formula IV in which n = 1 can by condensation of a quaternary

Cyclammonium salt of the formula:

IXI R-N (SCH-CH) = C-SRt • J-I χ

where R, x, Z, J and Rg have the meaning already given

en
with a compound of the following formula:

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X. C N-Y

t t

H ₀ CC = S

² V

in which W and Y have the meanings already given, are prepared in an inert solvent, preferably in the presence of a basic condensing agent and preferably by heating.

The dyes of the formula IV in which η = 2 to 4 can advantageously be prepared by condensation of a quaternary cyclammonium salt of the formula:

XI RN (= CH-CH) ₌ C (-CH = CR ₁ )

wherein R, x, Z, j, R ₁ and η have the meaning already given J have an -N 'group, a -SR ₁₁ group or a

^R 10 is a halogen atom, such as a chlorine or bromine atom and the like; Rg is a hydrogen atom, an alkyl group or the acyl group of a carboxylic acid residue and R _{10 is} an aryl group or R _g and R ₁₀ together are the non-metallic atoms that are needed to complete a heterocyclic ring.

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for example a piperidino or a morpholino ring are required and R ^ _{1 represent} a lower alkyl group, with a compound of the formula X.

The dyes of the formula VII can advantageously be prepared by condensation of a compound of the formula XI, in which R _{1 represents} a methyl group and η = 2, with a compound of the following formula:

Il

XII. C-N-Y

H ₂ CQ

in which Q and Y have the meanings already given, are prepared.

The preparation of some dyes of the formula I which can be used according to the invention is described below.

Dye 1

2- {j (2-benzothiazoly ethoperchlorate) methylene "1-λ- (λ-dimethylaminopropy1) -5- Q [1-methylnaphtho Q, 2-dl thiazolin-2-yldene) -l-phenylethyl or Q-M-thlazolidinone

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C = CH-C =

(CH ₂ J ₃ N (CH ₃ )

CH

2.1 g (1 mole) 3- (3-dimethylaminopropyl) -5-f (1-methylnaphtho jfl, 2-dJ thiazolin-2-ylidene) -1-phenylethylidene / rhodanine hydroperchlorate were added to 10 ml of dimethyl sulfate and 10 ml of dimethylformamide, whereupon the mixture was carefully heated until a solution was formed. The solution was then allowed to stand at room temperature for 1 hour calmly. The reaction product was precipitated with ether and washed with ether. The oily residue was in 30 ml Pyridine dissolved and with 2.0 g (1 mol + 100 *) 3-ethyl-2-methylbenzothiazolium iodide and 5 ml of triethylamine are added, whereupon the solution is heated to reflux temperature for 5 minutes became. The reaction mixture was then poured into 75 ml of methanol and made basic by the addition of piperidine became. The reaction mixture was then quenched and the dye was filtered off. The dye obtained was twice by dissolving in dimethylformamide and precipitating with methanol, which dissolved sodium perchloride

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rat contained, recrystallized. The resulting dye formed green crystals with a coppery sheen. the Yield was 18%. The melting point was 283 to 284 ° (dec.)

Dye 2

2- [~ (5-chloro-2-benzothiazolyl ethoperchlorate) methylene] -3- (3-dimethylaminopropy 1) -5- f ~ (1-methylnaphthofl ~ 2-.dJ] thiazole n-2-ylidene) -1-phenylethylidene ~ I-4-thiazolidinone

»Cii-c = c

2.1 g (1 mol) of 3- (3-dimethylaminopropyl) -5-Ql-methylnaphtho-Q, 2-d} thiazolin-2-ylidene) -l-phenylethylidene] rhodanine hydroperchlorate were added to 6 ml of dimethyl sulfate and 4 ml of dimethylformamide whereupon the solution was gently heated over an open flame until the formation of methyl mercaptan could be observed. The reaction mixture was then allowed to cool and 10 ml of pyridine were added.

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After the exothermic reaction had ended, the solution was treated with 2.6 g (1 mol + 100 *) of S-chloro-S-ethyl ^ -methylbenzothiazolium- ε-toluenesulfonate and 2 ml of triethylamine, whereupon the solution was carefully heated for 2 minutes became. The mixture was then poured into 40 ml of methanol, basified with piperidine, and quenched. The dye obtained was recrystallized twice by dissolving it in dimethylformamide and precipitating it with methanol containing dissolved sodium perchlorate. The dye formed green crystals with a melting point of 262 to 264 ° (dec). The yield was 3β%.

Dye 3

2- [2-benzoxazolyl methoperchlorate) methyleneX73- (3-dlmethylamlnopropyl) -5-1 ^ l-methylnaphthori _fl 2-d1thiazoln-2-vllden) -l-phenylethylidenel-4-thlazolldino n

C »CH-C

ClO ₁

This dye was prepared like dye 2 with the Except, however, that an equivalent amount of 3-ethyl-2 «

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methyl benzoxazolium iodide instead of 5-chloro-3-ethyl-2-methylbenzothiazolium-ε-toluenesulfonate was used. The dye recrystallized twice turned green Crystals with a melting point of 262 to 264 ° C (dec). The yield was $ 36.

The following dyes are those of the formula II.

dye

3- (3-Diniethylaininopropyl) -2- R3T (3-dimethylaminoprop.vl) -M-oxo-2-thioxo-5-thiazolidinvliden] -5- ( "~ (1-r ² * methvlnaphtho Π- althiazolin-2- ylidene) -l-phen.vläthylide ή ~ | -4-thi azolidinone

1.03 ε (1 mole) 3- (3-dimethylaminopropyl) -5-Ql-methylnaphtho {j., 2-i] thiazolin-2-ylidene) -1-phenylethylidene] rhodanine hydroperchlorate were added to 5 ml of dimethyl sulfate and 2 ml of dimethylformamide, whereupon the solution cautiously

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heated over a flame until a slight smell of methyl mercaptan was noticeable. The reaction mixture was then allowed to cool and treated with 5 ml of pyridine. When the following exothermic reaction had ended, the mixture was treated with 1.0 g (1 mol + 10055) of 3- (3-dimethylaminopropyl) rhodanine hydroperchlorate and 2 ml of triethylamine and heated carefully for about 2 minutes. The resulting reaction mixture was then poured into a solution of 40 ml of methanol and 5 ml of piperidine and the solution was quenched. The dye obtained was filtered off and dried. The dye was extracted twice by dissolving in dimethylformamide i. and precipitation recrystallized by adding methanol. The dye formed green crystals with a golden sheen and had a melting point of 265 to 267 (dec). The yield was 12 %.

Dye 5

2-r3- (2-Dlmethylaminoethyl) -4-oxo-2-thioxo-5-thlazolidine.vllderJ-3- (3-dimethylaminopropyl) -5-Ql-methylnaphthoD. »2- (Q thlazolin-2-yllden) - 1-phenylethylidene] -4-thlazolldinone

(CH ₂ KN (CH.) ,, (CH _p ) ₉ N (CH,) ρ

P = CH-C = C X

^C 6 ^H 5 N ^

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This dye was prepared as dye k , but instead of the rhodanine used to prepare dye 4, an equivalent of 3- (2-dimethylaminoethy1) rhodanine hydroperchlorate was used. The recrystallized dye formed green crystals with a copper sheen and had a melting point of 273 to 275 ° C (dec). The yield was

Dye 6

3- (3-Diethylaminopropyl) -2- Γ3- (3-dimethylaminopropyl) -4-oxo-2-thioxo-5-thiazolidinylidene-5-R1-ethylnaphtho

β, 2-d] thlazolin-2-ylidene) -1-phenylethylidene] -4-thiazo lidinone

CS

This dye was made as Dye 4 except that it was used in place of the one used for making of the dye 4 used rhodanine an equivalent Amount of 3- (3-diethylaminopropyl) -5- [l-ethylnaphtho-

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[j, 2-d7] thiazolin-2-ylidene) -l-phenylethylidene] rhodanine hydroperchlorate was used. The recrystallized dye formed green crystals with golden ones Gloss and a melting point of 254 to 256 ° C (dec). The yield was 45 ?.

Dye 7

5-p3-ethyl-2-benzothiazolnylidene) ethylid] -2-ii- (2-morpholinoethyl) -4-oxo-2-thioxo- ^t S-thiazolidinylid {] - ^ - phenyl-4-thiazolidinone

C = CH

N-CH ₂ CH ₂ N

^ ₁ H,

2.46 g (1 mole) 3- (2-morpholinoethyl) rhodanine, 5.82 g (1 mol) 5-ß3-ethyl-2-benzothiazolinylidene) ethylide O-2-methylmercapto ^ -oxo-S-phenyl ^ -thiazolinium-jD-toluenesulphonate and 3.08 ml (2.2 moles) of triethylamine were added to 25 ml of acetic anhydride, followed by stirring for 5 minutes was heated to reflux temperature for a long time. The resulting reaction mixture was then allowed to cool and take Stir in 300 ml of ether. The dark green tarry precipitate which separated out was separated off with

Washed with ether and then stirred with hot acetone. The 90981 3/1301

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Acetone suspension of the dye was cooled with Ether diluted and filtered. The obtained dye was made by dissolving in dimethylformamide and diluting recrystallized with methanol. Then the

Dye twice more by dissolving in pyridine and adding

■ took » recrystallized from methanol. The dye formed green crystals with a melting point of> 310 ° C. The yield was 4Ϊ.

Dye 8

5-j "(l-Äthylnaphthori.2-d" l thlazolin-2-.vliden) -l-phen.vläthylen} - ^ - (2-morphollnoäthyl) -2-j ^ -f g-mprphollnoäthyl) - ^ - oxo ^ -thioxo-S-thlazolldinylidert] -M-thlazolidinone

The dye was prepared as dye 7, but a molar equivalent of quaternized 5-QätliylnaphthoQ, 2-d] thiazolin-2-ylidene) -l-phenylethylidene] -3- (2-morpholinoethyl) rhodanine used. The solid dye reaction product obtained was washed with boiling benzene and boiling toluene and then washed twice by dissolving in pyridine and diluting recrystallized with benzene. The dye formed purple crystals with a golden tinge and possessed a melting point of 2 ^ 5 to 247 ° C (dec). The yield was 13Ϊ.

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- 21 -

χ ·

Dye 9

1- (2-Diethylaminoethyl) -5- R 1-Ethylnaphtho f ~ l. 2-di thiazolin-2-.vlidene) - (1-methynaphtho Π. 2-dl thiazolin-2-ylidene ) isopropylidene] -3-phenyl-2-thlobarblturic acid

s ^

C = CH-C-CH = C

W .Cv \ i

Γ ti S \ '

^υ 2 ^η 5 OC CO CH

A mixture consisting of 1.0 g (1 mol) of 1- (2-diethylarainoethyl) -5-β1-ethylnaphtho Ql, 2-J] thiazolin-2-ylidene) isoj * propyliden] -3-phenyl-2-thiobarbituric acid, 1.3 g (1 mol + 100 £) l-methyl-2-methylthionaphthoQ, 2-d] thiazolium- £ - toluenesulfonate and 0.1 g (1 mol + 100?) Trläthylamln were Heated to reflux temperature in 25 ml of pyridine for 10 minutes. The resulting solution was allowed to cool and poured into ether, whereupon the failed low-

The blow was filtered off and washed with ether. The tfohe Dye was dissolved in 600 ml of hot pyridine and the solution was filtered hot and methanol to the solution was added. After cooling, the dye was removed

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filtered. After another recrystallization, they became shiny green crystals with a melting point of 300 ° C. are obtained. The yield was

Dye 10

1- (2-diethylaminoethy 1-5- Cdi (1-ethyinaphtho | ~ 1.2- (D thlazolin-2-ylidene) isopropylidene / -S-phenyl ^ -thiobarburic acid

This dye was prepared as dye 9 with the exception that instead of the intermediate used to prepare dye 9, a molar equivalent of 1-ethyl-2-ethylthionaphtho [1 ₎ 2-d] -thiazolium ethyl sulfate was used. The dye, which had been recrystallized twice, was obtained in the form of shiny green crystals with a melting point of 291 to 292 ° C. (dec.) In a yield of 8% .

Dye 11

1- (2-Dläthvlaminoäthvl) -5-Q1-äthvlnaphtho jj. _r 2- £ | thiazolin-2-yliaen) - (l-methylnaphthor "i» 2-cn thiazolin-2-ylidene) isopropylidene "! -3 ~ P ^nen -Vl.e ^ar fc ^| ifc ^urs a'ure

This dye was made like Dye 9 except that it was used in place of the one used for making

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of the dye 9 used thlobarbituric acid derivatives ^ 1- (2-Diethylaminoethy1) -5-Q1-ethylnaphtho Q, 2-dJ-thiazolin-2-ylidene) isopropylidene] -3-phenylbarbituric acid was used. The recrystallized dye formed green crystals with a melting point of 300-3O2 ° C (dec.) · The yield was 1555.

Dye 12

1- (2-Dläthylamlnoäth.vl) -5- [di (1-ether vlnaphtho Tl . 2-dl thiazolin-2-ylidene) isopropylideneI-3-phenylbarbituric acid

This dye was prepared in the same way as dye 11, but instead of that used for the preparation of dye 11 used quaternary cyclammonium salt l-ethyl-2-äthylthionaphtho Q, 2-d] thiazolium ethyl sulfate was used. The recrystallized dye formed green crystals with a melting point of 298 to 299 ° C (dec). The yield was £ 21.

The preparation of compounds of the formulas V, VIII, IX and XIZ is known. The making of connections of the Formulas IV, VI, X and XII are described below.

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3- (3-Dlmethylamlnopropy1) -5- [X 1-methylnaohtho [l. 2-d] thiazolin-2-yldene) -1-phenylethylidene] rhodanine hydroperchlorate

14.8 g (1 mol) 2- (1-chlorostyryl) -l-methylnaphtho- [1,2-E | - thiazole chloride and 12.8 g (1 mol) 3- (3-dimethylaminopropydrhodanine hydroperchlorate were dissolved in 80 ml dimethylformamide the solution was treated with 16.8 ml of triethylamine and the solution was refluxed for 5 minutes, the hot reaction mixture was filtered and the filtrate was treated with a solution of 5.0 g of sodium perchlorate in 100 ml of ethanol acidified with acetic acid and allowed to cool. The precipitated dye was filtered off and contained by dissolving in dimethylformamide and precipitation with ethanol, which dissolved sodium perchlorate, recrystallized. The dye formed green crystals having a melting point 236-238 ⁰ C (dec). The yield was 59%.

3- (3-diethy laminopropyl) rhodaninh.vdroperchlorate

22.6 g (1 mole) of bis-carboxymethyl trithiocarbonate were obtained suspended in 150 ml of water, whereupon 11.6 g of sodium carbonate were added. 13.0 g (1 mol) of N, N-diethyl-1,3-propanediamine were then added to the solution, whereupon Was heated on the steam bath for 1 1/2 hours. There-

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SL?

The solution was then concentrated by adding Hydrochloric acid made strongly acidic and using a rotating evaporator until a vis-

oils ■ '

kosen ü-fckiee- evaporated. The oil was dissolved in 70 ml of water and a solution of 18.3 g of sodium perchlorate in 50 ml of water was added. It was then left to cool. The thick oil which separated out was then washed once with a sodium perchlorate solution and then three times with isopropyl alcohol. The last traces of the isopropyl alcohol were removed in vacuo. The product was then crystallized by stirring with a small amount of methanol. Pink-red crystals with a melting point of 102 to 10 ¹ I ⁰ C (dec.) * Were obtained. The yield was 35?

3- (2-Dimeth.v laminoäth.vl) rhodaninh.v droperchlorate

This compound was prepared in the same way, but Ν, Ν-dimethylethylenediamine was used.

3- (3-Diethylaminopropyl) -5-ri-ether vlnaphthori.2-dlthlazolin-2-ylidene) -l-phen.vläthylldenTrhodaninh.y droperchlorat

15.0 g (1 mol) of 1-ethy1-2- (2-ethylthiostyryl) naphtho [ΐ, 2-5> thiazolium ethyl sulfate and 10.2 g (1 mol) 3- (3-diethylamino-

9 0 9 8 13/1301

iH

propyl) rhodanine hydroperchlorate were dissolved in 50 ml of dimethylformamide and 9 ml of triethylamine, whereupon the solution was heated on the steam bath for 1 hour. The reaction mixture was then poured into a solution of 100 ml of methanol and 10 ml of piperidine, whereupon it was allowed to cool. The dye was then filtered off and dried. The dye was recrystallized by dissolving it in dimethylformamide and precipitating with methanol. The dye formed green crystals with a melting point of 196 to 197 ° (dec). The A yield was 56%.

1- (2-Diethylaminoethyl) -5-R1-ethylnaphtho fl. 2-dlthiazolin-2-yldene) isopropylidene-3-phenyl-2-thiobarbituric acid

A mixture consisting of S _t k g (1 mol) l- (2-diethylaminoethy1) -3-pheny1-2-thiobarbituric acid hydroperchlorate, 8.0 g (1 mole) 1-ethy 1-2-methylnaphthoQ, 2-cT) thiazoliunip-toluenesulfonate and 3.6 g (1 mol + $ 100) ethyl orthoacetate were heated to reflux temperature for 3 minutes in 50 ml pyridine. The reaction mixture was then poured into water, whereupon the precipitate which separated out was filtered off, washed with water and dried. The precipitate was then dissolved in 300 ml of hot pyridine, whereupon 2.8 ml of triethylamine and 300 ml of methanol were added? After he-

909Ö13 / 1301

The dye was filtered off when cold. After another recrystallization, the dye was in a yield of 11? obtain. The dye formed orange-red crystals with a melting point of 260 to 261 ^° C. (dec).

1- (2-diethylaminoethyl) -3-phenyl-2-thiobarbituric acid hydroperchlorate

A solution of 67.5 g (1 mol) of phenyl isothiocyanate in 100 ml of benzene was added dropwise with stirring to a Given a solution of 58.5 g (1 mol) of N, N-diethylethylenediamine. The reaction that took place was exothermic. The reaction mixture was then left at room temperature for 2 hours stirred for a long time, whereupon 200 ml of an ethanolic hydrogen chloride solution (90 g per liter of HCl) were added became. The resulting solution was then concentrated using a rotary evaporator. The residue was recrystallized from 600 ml of ethanol. The yield of 1- (2-diethylaminoethyl) -3-phenyl-2-thiourea hydrochloride was $ 90.

A solution of 28.2 g (1 mol) of malonyl dichloride in 100 ml Chloroform was added dropwise with stirring to 57.4 g (1 mol)

909813/1301
+) in 500 ml of benzene

1- (2-Diethylaminoethyl) -3-phenyl-2-thiourea hydrochloride added in 200 ml of chloroform. After the addition was completed, the reaction mixture became one hour heated for a long time on the steam bath. The mixture obtained was then concentrated using a rotary evaporator. The residue was dissolved in water, whereupon a aqueous solution of Ί9 g (1 mol + 100%) sodium per-

a
chlorate was added. The deposited precipitate was filtered off, washed with water and dried. After recrystallization from a dimethylformamide / ethanol mixture, colorless crystals with a melting point of 224 to 225 ° C. (dec.) Were obtained. The yield was

1- (2-diethylaminoethyl) -5 ^ Rl-ethylnaphthori.2-d1thlazolin-2-.vllden) isopropylidene ") -3-phen.vlbarbituric acid

This dye, like the corresponding one, became a thiobarbituric acid nucleus corresponding dye was produced, but l- (2-diethylaminoethyl) -3-phenylbarbituric acid hydroperchlorate was used used. The purified dye formed brownish crystals with a melting point of 225 to 226 ° C (dec). The yield was

90981 3/1301

l- (2-Diethylaminoethyl) -3-phenylbarbituric acid hydroperchlorate

This compound, like the corresponding thiobarbituric acid salt, was prepared by using phenyl isocyanate in place of phenyl isothiocyanate. The recrystallized compound formed colorless crystals with a melting point of 223 to 22 ¹ J ⁰ C (dec.). The yield was 56%.

The dyes described are outstandingly suitable for the optical sensitization of the most varied Silver halides, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, Silver bromoiodide, silver chlorobromoiodide and the like, those in the most varied of hydrophilic colloids, such as those used for the production of light-sensitive, photographic Layers are used, can be dispersed. Suitable hydrophilic colloids are, for example, gelatin, Albumin, agar-agar, gum arabic, alginic acid and the like, as well as synthetic compounds such as polyvinyl alcohol, Polyvinylpyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetates and the like.

909813/1301

H72822

The concentration of the dyes in the emulsions can be varied as far as possible. Appropriate concentrations for example, between about 5 to about 100 mg per liter of flowable emulsion. Of course it depends the concentration used in the individual case on the dye itself, the type of light-sensitive material In the emulsion and the specially desired effects.

As already mentioned, the acid used according to the invention is very easily soluble in water, especially in the presence of an equivalent. However, other methods of incorporating the dyes can of course also be used. For example, the dyes can be incorporated into the emulsion layers by bathing the photographic material in a solution of the dye. Also, photographic elements comprising a silver halide film vacuum evaporated onto a support can be advantageously sensitized by bathing in a solution of one of the dyes.

909813/1301

U72822

3ff

The superhalide photographic emulsions to which the dyes are added can of course other additives such as chemical sensitizers such as about sulfur-containing sensitizers, e.g. allylthiocarbamide, Thiourea, allyl isothiocyanate, cystine and the like, various gold compounds such as potassium chloroaurate, Auritrichloride and the like, as described in U.S. Patents 2,50,085; 2,597,856 and 2,597,915 described. A wide variety of other suitable chemical sensitizers may be mentioned, for example Palladium compounds such as palladium chloride as described in U.S. Patent 2,50,086 described, potassium chloropalladate, as described, for example, in US Pat. No. 2,598,079, and the like. or mixtures of such sensitizers. Antifoggants can also be added to the emulsions such as ammonium chloroplatinate, as described in US Pat. No. 2 566 2 ^ 5, ammonium chloroplatinite, as described in US Pat. No. 2,566,263, BenzotJiriazol, Nitrobenzimidazol, 5-Nitroindazol, Benzidine, Mercaptans and the like, as described in Mees' book "The Theory of the Photographic Process" Macmillan pub., P 460, or mixtures thereof. Suitable

909813/1301

I ¹ p

Hardeners that can be added to the emulsions are, for example, formaldehyde, as in the USA patent

1 763 533 described, chromium aluminum sulfate, as in the U.S. Patent 1,763,533, glyoxal as described in US Pat. No. 1 87O 354, dibromacrolein, as described in British Patent 406,750 and the like. The emulsions can also contain color couplers, for example those as described in US Pat U.S. Patent 2,423,730 and U.S. Patent

2,640,776 or mixtures of these Additions. The emulsions can also be used as dispersants for the color couplers, such as those disclosed in US Pat. No. 2,322,027 and US Pat 2 304 940.

The emulsions can be applied to a wide variety of substrates, for example made of paper, glass, Cellulose acetate, cellulose nitrate, synthetic plastics such as polyesters, polyamides, polystyrenes and the like

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

909813/1301

example 1

Different proportions of the same gelatin silver bromoiodide emulsion, with 0.77 mol-2 iodide of the type described by Trivelle and Smith in Phot. Journal, £ 9_, 330 (1939) by adding solutions of the dyes indicated below in a suitable solvent sensitized. The sensitized emulsions were then coated on cellulose acetate film supports, 432 mg of silver were accounted for on an area of 929 cm. The resulting film samples were then tested in an Eastman IB sensitometer with an intensity scale and a step wedge spectrograph exposed, 3 minutes developed for a long time in a Kodak D-19 developer, fixed in a conventional sodium thiosulfate fixing bath, washed and dried. The results obtained are shown in Table I below.

Table I. Awareness Dye Mr. Spectral Area my λ Max, my 550-720
56-715
5IO-7OO 1
2
3 675
675
660

909813/1301 originally inspected

a »

Similar results were obtained with the other complex cyanine dyes.

Example 2

A portion of a silver bromoiodide emulsion as in Example 1 described, and a portion of a silver chlorobromide emulsion, the 40 MoI-? Bromide were used with the dyes 7 and 8 sensitized. The dyes were incorporated into the emulsions in the form of solutions. The films obtained were then exposed and developed as described in Example 1. The results obtained are shown in Table II below.

Table II

Dye No. Emulsion Spectral Sensitivity λ Max, my area my

7 silver bromoiodide 645 520-700

8 silver chlorobromide 680 550-730

Example 3

Example 1 was repeated using dyes 9, 10, 11 and 12 in place of dyes 1, 2 and 3. The results obtained are shown in Table III below.

909813/1301

3fr

Tabel III Awareness raising dye No. Spectral Area mp λ Max, my 530-705
53Ο-7ΟΟ
-725
-725 9
10
11
12th 675
670
685
685

909613/1301

Claims (2)

H72822 - 3β-- Dr. Expl. Claims 1. Use of trinuclear dyes with at least a nucleus which is substituted by at least one alkyl group substituted by a secondary amino group is, of the following formulas: -Z- O = C N-Y --Zi- R-N (-CH = CH) ^ C (SCH- I I / ₁ ) S = SC C = CH-C (= CH-CH) = NR ^τ n-1 \ / PI \ W X 0 ti O = C N-Y C IJ-Y. II. R-N (-CH = Cu) C (= CH-CR.) = C J ¹ « ¹ C == CC = D or / ν III. H-N (-CH = CH) -— 7C = CH- J-I ^ -CH = C (-CH = CH) N-R, / C = O ^ .N-Y where mean: 909813/1301 R and R _{2 are} alkyl groups; R _{1 is} a hydrogen atom, an alkyl or aryl group; Z and Z ₁ the eur completion of a thiazole; Beneothiazole-; Naphthothiazole Thanaphtheno-T ¹ ^ ¹ , 4,5-thlazole-; Oxazole-; Benzoxazole-; Naphthoxazole-; Selenazole-; Benzoselenazole-; Naphthoselenazole-; Thiazoline-j 2-Pyrldln-j ^ I-Pyridln-} 2-Chlnolln-; ll-quinoline-; l-isochinoln-j 3-Ieoquinoline-; 3 »3 ^f -Dlalkylindolenln-j imidazole-j Benelmidazole or Naphthhlmidazolringeu required atoms; J, m and ρ 1 or 2; η is a number from 1 to 4; Y and Y ₁ Waeseretoff atoms, alkyl groups, aryl groups or a or - (CH ₂ ) JN ^ ^ " ^Η 5 ^Oru PP ·» 90981371301 U72822 - ■ ** - ■■■; ■ In which I is a number from 2 to k and R ₃ , R ^ and Rc represent alkyl groups and where at least one of the groups Y or T _{1 represents} a group with a tertiary Sticketoffatom: W and W _{1 are} oxygen, sulfur or selenium atoms or a ^ NRg group, in which Rg is an alkyl or aryl group; X is an acid residue; D and D ₁ oxygen, sulfur or selenium atoms and one -CaN-; -S-C-; -C-N-C-
NfN D. Group, .0-C-
N ; -N -
ι C-
N or ^R 7 D. ^γ ι D. in which R _{7 represents} a hydrogen atom, an alkyl, aryl, amino, carbonamido, sulfonamide, sttlfamyl or carbamyl group and D, D ₁ and Y _{1 have} the meaning given, in photosensitive silver halide layers and or Light filtering layers of a photographic material. 2. Use of dyes naoh claim 1, daduroh gekennseichnet that they consist of aust 909813/1301 ■ - «■ '■■■ U72822 2 «Q> -Benxothlasolyläthoperohiorat) -methylene) -3- (3-di-Mtthylamlnopropyl) -5- Q 1-methylnaphtho Q, 2- (T] -thiazolin-2-ylidene) -1-phenyläthylideg] -4-thla * olidinone $ 2- Q 5-chloro-2-benliot hiazolylethoperchlorate) -methylene] -3 ** (3-dimethylaminopropyl) -5- Q l-methyl-naphtho {jl, 2-d] -thia * olln-2-ylidene) - l-phenylethylidene] -M-thiaiolidinone; 1- (2-diethylaminoethy1) -5-01-ethyl-naphtho |>, 2- £ j thia- ■ olin-2-ylidene) - (1-methylnaphtho Q., 2-J] -thia »olln-2- y11-den) ieopropylldeij3-3-phenylbarbituric acid} 1- (2-Dläthylamlnoäthyl) -5-Cdi (l-ethyl-naphtho- [1,2- £ 3-thiaoln-2-ylldene) leopropylidenja-phenylbarblture acid; 3- (3-Di-methylamino-propy1) -2-Q- (3-dimethylamino-propy1) - 4-o »o-2-thioxo-5-thiaaolidinylidene] -5-Q 1-methylnaphtho-Q, 2-j] thla8olln-2-yllden) -l-phenylethylideiO-4-thlaxoll- / dinone or ' 5- Q 1-XthylnaphthoQ, 2-iJthlaaolin-2-yllden) -1-phenyl ethylene] -3- (2-morpholinoethyl) -2-Q- (2-morpholinoethyl) - f 4-oxo-2-thioxo-5 -thlaiolidinyllden] -iJ-thlatolldÄnon. 90-13 / 1301