DE1158646B - Process for the production of basic dyes - Google Patents

Description

GERMAN

PATENT OFFICE

F 28319 IVc / 22 e

REGISTRATION DATE: APRIL 25, 1959

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL: DECEMBER 5, 1963

It has been found that valuable basic dyes of the general formula can be used

Process for the production of
basic dyes

A /

CR ₂

Axe/ \

CH = CH-C =

R ₆

= C-R ₄

NO ₇

Rs

in which A stands for a radical of an aromatic ring system, Ri and R ₂ for an alkyl, cycloalkyl or aralkyl radical, R ₄ for hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, the carboxylic acid group, a carbonamide group or a carboxylic acid ester group, Re represents an alkyl, cycloalkyl, aralkyl or aryl radical, R7 represents an alkyl or aralkyl radical and Rs represents an alkyl, cycloalkyl, aralkyl or aryl radical, while X 'represents the equivalent of an acid radical, if one sulfonic acid group-free compounds of the general formula

Ri

l \

CR ₂

A _1n / S

ι CH-CH = C-

II

R ₃

-CR ₄

Il

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Dr. Roderich Raue

and Dr. Hubertus Psaar, Leverkusen,

have been named as inventors

R ₅

one l-methylene-indoline-w-aldehydes of the general formula

Ri

in which A, Ri, R ₂ and Re have the meaning given above, with sulfonic acid group-free pyrazolone compounds of the general formula

HC =
O = C

= C-R ₄

NO ₇

N-

Rs

in which R ₄ , R7 and Rs have the meaning given above, condensed in preferably an acidic medium, or when using 2-methylene indolines of the general formula

«Ri

in which A, Ri, R ₂ and R _{4 have} the meaning given above, while R3 and R5 independently represent hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, reacts with alkylating or aralkylating agents, or if

v I. -C V A Γ R ₆ 1\ CR ₂ A. ^/ \ CH ₂ 309 767/373

in which A, Ri, R2 and Re have the meaning given above, with sulfonic acid group-free pyrazolone-4-aldehydes of the general formula

OCH-C =

= C-R ₄

NO ₇

VI

N ^/ Rs

in which R4, R7 and Rs have the meaning given above own, or their functional derivatives, condensed in preferably acidic medium.

The compounds of general formula II are available in various ways, e.g. B. in that one 2-methyleneindoline-co-aldehydes of the general formula

VII

CHO

15th

As alkylating or aralkylating agents, for example, dimethyl sulfate, diethyl sulfate, Methyl iodide, ethyl iodide and 4-toluenesulfonic acid methyl and ethyl ester and benzyl chloride into consideration. The implementation of the compounds of formula II the alkylating agents can be carried out with heating in a solvent. Suitable Solvents are e.g. B. toluene, xylene, chlorobenzene and o-dichlorobenzene. Particularly useful is to carry out the reaction in an excess of an alkylating agent at elevated temperature and if necessary to be carried out under increased pressure.

Suitable representatives of the methylene indoline and pyrazolone components corresponding to the general formulas III to X are, for. B. the following connections:

Compounds of the general formulas III and VII:

3,3-dimethyl-2-methylene-indoline-cu-aldehyde, 1,3 _; 3-trimethyl-2-methylenindoline-w-aldehyde, l-ethyl-S ^ -dimethyW-methylenindoline-aldehyde,

in which A, Ri, R2 and R3 have the meaning given above have, with sulfonic acid group-free pyrazolones of the general formula

H ₂ C =

—R ₄

C N

R ₅

VIII

35

in which R ₄ and Rs have the meaning given above, condensed in a preferably alkaline medium, or by using 2-methylene indolines of the general formula

40

45

IX

in which A, Ri, R2 and R3 have the meaning given above have, with sulfonic acid group-free pyrazolone-4-aldehydes the general formula

55

HIGH = C-

CR ₄

60

ω-aldehyde,

ω-aldehyde,
1,3,3-trimethyl-5-nitro-2-methylene indoline

co-aldehyde,
l ^^ J-Tetramethyl-S-nitro ^ -methyleneindoline-

ω-aldehyde,
! ^, S-trimethyl-S-methoxy ^ -methyleneindolinco-aldehyde,

fo-aldehyde,
ih

indoline-co-aldehyde,
l-Ethyl-S ^ -dimetnyl-S-ethoxy ^ -methylene-

indoline-co-aldehyde,
l-Ethyl-S ^ -dimethyl-S-carbäthoxy ^ -methylene-

indoline-w-aldehyde,
ihl

cü-aldehyde,
i

R ₅

in which R ₄ and R _{5 have} the meaning given above, or their functional derivatives, preferably condensed in an acidic medium.

65 ω-aldehyde,
! ^, S-trimethyl-S-acetamino ^ -methyleneindoline-ω-aldehyde,
^, S-trimethyl-S-äthylsulfonylamino- or -S-phenylsulfonylamino ^ -methyleneindoline-ω-aldehyde,

1,3,3-triethyl-2-methylenindoline-w-aldehyde, 1,3,3-trimethylbenzo- (4,5) -2-methylenindoline-

ω-aldehyde,
1,3,3-trimethyl-benzo- (6,7) -2-methyleneindoline-

co-aldehyde,
!, S ^ -trimethyl-S-sulfamido ^ -methyleneindoline- (u-aldehyde and its N-alkyl or N-aryl

Derivatives,
!, ^, S-trimethyl-S-methylsulfonyl ^ -methylene-

indoline-w-aldehyde.

Compounds of the general formulas V and IX:

2,3,3-trimethylindolenine,

!, Sp-trimethyl ^ -methyleneindoline,

l-ethyl-S ^ -dimethyl ^ -methyleneindoline, !, S ^ .S-tetramethyl ^ -methyleneindoline, !, S ^ -trimethyl-S-bromo ^ -methyleneindoline,

, yy l ^^ J-tetramethyl-S-nitro ^ -methyleneindoline,

hlidli

y
Esters and amides of 1,3,3-trimethyl

2-methylenindoline-5-carboxylic acid, l-ethyl-S ^ -dimethyl-S-ethoxy ^ -methylene-

indoline,
l-ethyl-S ^ -dimethyl ^ -methyleneindoline-5-carboxylic acid ethyl ester,

^, yy! ^, S-trimethyl-S-acetamino-l-methyleneindoline, 1 ^, S-trimethyl-S-methylsulfonylamino- or

-S-phenylsulfonylamino - ^ - methylenindoline, lAS-triethyl ^ -methyleneindoline, 1,3,3-trimethyl-benzo- (4,5) -2-methylene-indoline, 1,3-trimethyl-benzo- (6,7) -2-methylene-indoline, !, S ^ -trimethyl-S-methylsulfonyl-l-methylene

indoline,
the amide or the N-alkyl or N-aryl amides of 1, S ^ -trimethyl ^ -methyleneindoline-5-sulfonic acid.

Compounds of the general formula VIII:

S-methyl-S-pyrazolone,
1-phenyl-S-methyl-S-pyrazolone, l-phenyl-S-pyrazolone - ^ - carboxylic acid ethyl ester, l-phenyl-S-pyrazolone-S-carboxamide, l-phenyl-S-pyrazolone-S-carboxylic acid, l- (2'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (3'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-dichlorophenyl) -3-methyl-5- pyrazolone, H3'-nitrophenyl) -3-methyl-5-pyrazolone, 1- (4'-nitrophenyl) -3-methyl-5-pyrazolone, 1- (4'-methylphenyl) -3-methyl-5-pyrazolone.

Compounds of the general formula X:

3-methyl-5-pyrazolone _: 4-aldehyde, l-phenyl-S-methyl-S-pyrazolon ^ -aldehyde, l-phenyl-3-carbethoxy-5-pyrazolone-4-aldehyde, 1 - (p-toluyl) -3-methyl-5-pyrazolone-4-aldehyde.

Compounds of the general formula IV: l-phenyl-2,3-dimethylpyrazolon-5, l-phenyl ^ -methyl-S-pyrazolone-S-carboxylic acid ethyl ester,

l-phenyl ^ -methyl-S-pyrazolon-S-carbonamide, l- (2'-chlorophenyl) -2,3-dimethyl-5-pyrazolone, l- (3'-chlorophenyl) -2,3-dimethyl-5-pyrazolone,

ihl

5-pyrazolone,
l- (3'-nitrophenyl) -2,3-dimethyl-5-pyrazolone, l- (4'-methylphenyl) -2,3-dimethyl-5-pyrazolone,

1- (2'-cyanoethyl) -2,3-dimethyl-5-pyrazolone, 1- (4'-nitrophenyl) -2,3-dimethyl-5-pyrazolone. Compounds of the general formula VI:

l-phenyl ^ -dimethyl-S-pyrazolon ^ -aldehyde, l-phenyl ^ -methyl-S-carboethoxy-S-pyrazolone-

4-aldehyde,
l-phenyl-i-methyW-carbonamido-S-pyrazolone-

4-aldehyde,
l- (2'-chlorophenyl) -2,3-dimethyl-5-pyrazolone-

4-aldehyde,
1 - (3 '-ChlorphenyO ^^ - dimethyl-S-pyrazolone-

4-aldehyde,
1- (2 ^/ , 5'-dichlorophenyl) -2,3-dimethyl-5-pyrazolone-4-aldehyde,

1 - (3'-nitrophenyl) -2,3-dimethyl-5-pyrazolone-

4-aldehyde,
l- (4'-nitrophenyl) -2,3-dimethyl-5-pyrazolone-

4-aldehyde,
1 - (4'-methylphenyl-2,3-dimethyl-5-pyrazolone-

4-aldehyde,
l- (2'-cyanoethyl) -2,3-dimethyl-5-pyrazolone-

4-aldehyde.

The new basic dyes are eminently suitable for coloring materials made of polyacrylonitrile or as-dicyanethylene as the main component exist. They generally give brilliant colorations in shades of yellow to orange, which are next to

! 5 very good general fastness properties are characterized by the fact that they can be etched in pure white. The dyes are also suitable for dyeing paper, e.g. B. for use in rubber printing or as a yellow component in copier inks, as well as for dyeing leather and lignin-containing fibers such as coconut, jute or sisal. The dyes can also be added to the spinning masses in the manufacture of synthetic fibers before spinning.
Compared to the methine dye known from Example 1 of US Pat. No. 2,032,502, the methine dye which is obtainable according to the process and alkylated on the nitrogen atom of the pyrazolone component has significantly improved water solubility. The parts given in the following examples are parts by weight.

example 1

25 parts of the condensation product of 1,3,3-trimethyl-5-carbomethoxy-2-methylindoline- (w-aldehyde and 1-phenyl-3-methyl-5-pyrazolone are heated ^{in 40 parts to 70 ° C. in the course of 15 minutes} The reaction mixture is then ^{heated to 110 °} C., kept at this temperature for 3 hours, then poured into 200 parts of water at 50 ^° C. and stirred until the excess dimethyl sulfate has decomposed. The reaction solution is now heated to boiling, clarified with activated charcoal and mixed with 20% common salt. The precipitated basic dye can be further purified by redissolving it in hot water and salting out with common salt. The dye is obtained in the form of an orange-yellow, very easily water-soluble powder.

If you want to dye polyacrylonitrile fibers with the dye, you bring them in the liquor ratio 1:40 in an aqueous bath at 40 ⁰ C, which contains 0.75 g of 30% acetic acid, 0.4 g of sodium acetate and 0.2 g of des per liter Contains dye, the bath heats to the boil within 20 to 30 minutes and holds it at this temperature for 30 to 60 minutes. The polyacrylonitrile fibers are then rinsed and dried. A reddish yellow dyeing with very good light and wet fastness properties is obtained; it can be etched in pure white.

Mix 20 parts of the dye with 50 parts of malachite green, 15 parts of methyl violet and 15 parts Fuchsin, the result is a copy black that can be mixed with mineral oil, carnauba wax and wool fat to make a copy color processed, enables even copying out according to known working methods.

Similar good results are achieved with the basic dyes that are produced according to the one described above Mode of operation by methylating the condensation

Products are available, which consist of those in the temperature and the tone of those with the basic color sequences The components listed in the table are dyes that can be achieved on polyacrylonitrile are posed. The most advantageous methylation in each case is also given.

Methylene indoline component Pyrazolone component Methylation
temperature hue 1, S ^ -trimethyl-S-carbomethoxy-
2-methylene-indoline-co-aldehyde 1 - (4'-methylphenyl) -3-methyl-
5-pyrazolone 130 ° C Reddish yellow l ^^ - trimethyl-S-carbomethoxy-
2-methylene-indoline-cy-aldehyde 1 - (2'-chlorophenyl) -3-methyl-
5-pyrazolone 110 ⁰ C yellow 1 ^, S-trimethyl-S-carbomethoxy-
i-methyleneindoline-w-aldehyde l- (3'-chlorophenyl) -3-methyl-
5-pyrazolone 110 ⁰ C Reddish yellow 1, S ^ -trimethyl-S-carbomethoxy-
2-methylene indoline-w-aldehyde l- (2 ', 5'-dichlorophenyl) -3-methyl-
5-pyrazolone 110 ⁰ C yellow 1 ^, B-trimethyl-S-carbomethoxy-
2-methylene indoline (u-aldehyde 1 - (3'-nitrophenyl) -3-methyl-
5-pyrazolone 140 ° C yellow 1, S ^ -trimethyl-S-carbomethoxy-
2-methyleneindoline-ct) aldehyde 1- (4'-nitrophenyl) -3-methyl-
5-pyrazolone 140 ° C yellow 1,3, S-trimethyl-S-carbomethoxy-
2-methylene indoline-w-aldehyde 1 - (4'-aminophenyl) -3-methyl-
5-pyrazolone 110 ⁰ C Yellowish tinge
orange 1,3, S-trimethyl-S-carbomethoxy-
2-methylene-indoline-ft) -aldehyde 1 - (3'-carboxyphenyl) -3-methyl-
5-pyrazolone 130 ° C Reddish yellow 1 ^, S-trimethyl-S-carbomethoxy-
2-methylene indoline-a) aldehyde 3-methyl-5-pyrazolone HO ⁰ C Reddish yellow ! ^, S-trimethyl-S-carbomethoxy-
2-methylene-indoline-cu-aldehyde 1-phenyl-S-carbethoxy-S-pyrazolone 110 ⁰ C Yellowish tinge
orange 1 ^, S-trimethyl-S-carbomethoxy-
2-methylene-indoline-cu-aldehyde 1-phenyl-5-pyrazolone-
3-carboxamide 120 ° C Reddish yellow l ^^ - trimethyl ^ -methyleneindoline-
eu-aldehyde 1-phenyl-S-methyl-S-pyrazolone HO ³ C yellow ! ^, S-trimethyl ^ -methyleneindoline-
ω-aldehyde l- (4'-methylphenyl) -3-methyl-
5-pyrazolone 110 ⁰ C yellow l ^^ - trimethyl ^ -methyleneindoline-
ω-aldehyde 1 - (3'-chlorophenyl) -3-methyl-
5-pyrazolone HO ⁰ C yellow 1,3,3-trimethyl-2-methylene indoline
co-aldehyde l- (3'-nitrophenyl) -3-methyl-
5-pyrazolone 120 ° C yellow l ^^ - trimethyl ^ -methyleneindoline-
ω-aldehyde 1-phenyl-S-carbethoxy-S-pyrazolone 110 ⁰ C Reddish yellow l ^^^ - Tetramethyl-l-methyleneindoline-
ω-aldehyde 1-phenyl-S-methyl-S-pyrazolone 110 ⁰ C yellow l ^^ - trimethyl-S-methoxy ^ -methylene-
indoline-co-aldehyde 1-phenyl-S-methyl-S-pyrazolone HO ⁰ C Reddish yellow !, S ^ -trimethyl-S-methoxy ^ -methylene-
indoline-w-aldehyde 1 - (4'-nitrophenyl) -3-methyl-
5-pyrazolone 120 ° C Reddish yellow l, 3,3-trimethyl-5-chloro-2-methylene
indoline-co-aldehyde 1-phenyl-S-methyl-S-pyrazolone 110 ⁰ C yellow indoline-w-aldehyde 1-phenyl-3-methyl-5-pyrazolone 120 ° C orange 1,3,3,7-tetramethyl-5-nitro-
2-methylene-indoline-co-aldehyde 1-phenyl-S-methyl-S-pyrazolone 110 ⁰ C Reddish yellow l-EthyW ^ -dimethyl-S-carbäthoxy-
2-methylene-indoline-cu-aldehyde 1-phenyl-S-methyl-S-pyrazolone 110 ⁰ C Reddish yellow

Example 2

20.8 parts of the condensation product from!, S ^ -trimetiiyl-S-carbomethoxy ^ -methyleneindoline-aldehyde and 1-phenyl-S-methyl-S-pyrazolone are ^{heated to 70 °} C. with 150 parts of chlorobenzene, then with 6.9 parts of dimethyl sulfate and slowly heated to 110 ⁰ C. At 85 ^° C., the starting material goes completely into solution. After the reaction mixture has been ^{heated to HO 0} C for 3 hours with stirring, it is cooled and the dyestuff which has precipitated out is filtered off with suction. For cleaning, the dye is dissolved in 500 parts of boiling water, clarified with activated charcoal and salted out with 75 parts of common salt. The basic dye obtained is identical to the dye described in Example 1.

If the starting material used is the condensation product of! ^, S-trimethyl-S-carbomethoxy-2-methyleneindoline-eu-aldehyde and 3-methylpyrazolone, and toluene as the solvent, is obtained at the same procedure, a basic dye that stains polyacrylonitrile in a reddish yellow.

Example 3

10 parts of the condensation product of 1,3,3-trimethyl-S-carbomethoxy ^ -methyleneindoline-co-aldehyde and 1-phenyI-3-methyl-5-pyrazolone are introduced into 25 parts of diethyl sulfate heated to 70 ° C. over the course of 15 minutes . The temperature is gradually increased to 14O ⁰ C, wherein the condensation product goes into solution. After the reaction mixture is kept under stirring for 3 hours at 14O ⁰ C, the mixture is cooled, the melt slightly and poured into 100 parts of water at 50 ⁰ C., heated to boiling, uses activated carbon to the solution is filtered and cooled them off. The basic dye formed is precipitated by adding 25 parts of sodium chloride and 6 parts of perchloric acid. For cleaning, the dye is dissolved in 1000 parts of water, clarified with activated charcoal and salted out with 50 parts of common salt.

On yarns and fabrics made of polyacrylonitrile, the dye gives a very reddish-tinged yellow heifer good light and wet fastness.

Example 4

10 parts of the condensation product of 1,3,3-trimethyl-S-carbomethoxy ^ -methyleneindoline-co-aldehyde and 1 -PhenyW-methyl-S-pyrazolone are divided into 25 parts 4-toluenesulfonic acid methyl ester heated to 70 ° C registered. After the reaction mixture has been heated to 120 ° C and 3 hours at this temperature is stirred, the excess 4-toluenesulfonic acid methyl ester driven off with steam. Then, after the addition of activated charcoal, steam is introduced again for a short time; Then it will be the solution is nitrated and, when it has cooled, mixed with 30 parts of table salt. The unusual one basic dye can be dissolved again in hot water for further cleaning and mixed with table salt are salted out.

On polyacrylonitrile materials, the dye gives a very good reddish-tinged yellow coloration Authenticity properties.

Example 5 ^6s

8 parts of the condensation product of 1,3,3-trimethyl-S-carbomethoxy ^ -methyleneindoline-w-aldehyde and l-phenyl-3-methyl-5-pyrazolone are melted down with 30 parts of methyl iodine in the bomb tube and heated to 140 ° C for 3 hours. After the Reaction mass has cooled, it is rinsed with 100 parts of water in a flask and expelled Excess methyl iodide is removed with steam. Then the remaining solution is added Another 500 parts of water, heated to boiling, clarified with activated charcoal and salted the formed basic dye with 200 parts of table salt.

The dye colors materials made of polyacrylonitrile in a strong reddish-yellow shade; has the coloring good fastness properties. A basic dye with also very good fastness properties is obtained if ethyl iodide is used instead of methyl iodide.

Example 6

12.5 parts of 1,3,3-trimethyl-5-nitro-2-methylen-indoline-co-aldehyde and 9.4 parts of 1-phenyl-2,3-dimethyl-5-pyrazolone are dissolved in 50 parts of chloroform and stirred slowly mixed with a solution of 7.8 parts of phosphorus oxychloride in 20 parts of chloroform. The temperature of the solution rises to the boiling point of chloroform. After the reaction mixture is stirred for 30 minutes at 6O ⁰ C, the solvent in vacuum (30 mm Hg). The residue is taken up in 250 parts of water at room temperature, and the basic dye formed is precipitated with sodium chloride.

The dye is finished with that according to Example 1 by methylation of the condensation product 1,3,3-trimethyl-5-nitro-2-methylene-indoline-cu-aldehyde and 1 - phenyl - 3 - methyl - 5 - pyrazolone are identical.

Example 7

8.7 parts of l, 3,3-trimethyl-2-methyleneindoline and 11 parts of l-phenyl ^ .S-dimethyl-S-pyrazolone ^ -aldehyde are dissolved in 70 parts of 90% acetic acid and heated on a boiling water bath for 1 hour. The solution is then cooled to room temperature and poured into 300 parts of water. The one with Basic dye precipitated from common salt dyes polyacrylonitrile fibers yellow.

In place of l ^^ - trimethyl ^ -methyleneindoline 1, S ^ -trimethyl-S-carbomethoxy ^ -methylene indoline a, one obtains a dye which with that according to Example 1 by methylation of the condensation product from 1,3,3 - trimethyl - 5 - carbomethoxy-2-methyleneindoline-öj-aldehyde and 1-phenyl-3-methyl-5-pyrazolone obtained identical dye and dyes polyacrylonitrile fibers in reddish yellow tones.

Example 8

10.2 parts of l, 3,3-trimethyl-5-methoxy-2-methyleneindoline and 12.5 parts of l-phenyl ^ -isopropyl-S-methyl-5-pyrazolone-4-aldehyde are dissolved in 50 parts of chloroform and under Stirring a solution of 7.8 parts of phosphorus oxychloride in 20 parts of chloroform was added dropwise. The solution is stirred for 30 minutes at 6O ⁰ C and distilling off the solvent. The residue is dissolved in 250 parts of water and the dye is precipitated with sodium chloride.

The dye dyes polyacrylonitrile fibers in yellow tones.

309 767/373

If one uses instead of l-phenyl-2-isopropyl- - methyl - 5 - pyrazolone - 4 - aldehyde the equivalent amount of 1 - phenyl - 2 - benzyl - 3 - methyl - 5 - pyrazolone - 4 - aldehyde a reddish yellow dye is obtained in the same way.

Claims (1)

PATENT CLAIM: Process for the preparation of basic dyes of the general formula IO Ri Y- ' al \ CR ₂ A _n / \ ι CH = CH-C- -CR ₄ NO ₇ R ₈ X ' 20th in which A stands for a radical of an aromatic ring system, Ri and R2 for an alkyl, cycloalkyl or aralkyl radical, R4 for hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, the carboxylic acid group, a carbonamide group or a carboxylic acid ester group, Re for an alkyl, cycloalkyl, aralkyl or aryl radical, R? represents an alkyl or aralkyl radical and Rs represents an alkyl, cycloalkyl, aralkyl or aryl radical, while X 'represents the equivalent of an acid radical, characterized in that compounds of the general formula free of sulfonic acid groups are used 40 45 CH- CH = C- -CR ₄ R ₅ in the A, Ri, R2 and R4 those given above Have meaning, while R3 and R5 independently represent hydrogen, an alkyl, Cycloalkyl, aralkyl or aryl radicals are with alkylating or aralkylating agents or that 2-methyleneindoline-co-aldehydes the general formula in the A, Ri, R2 and Re the above Have meaning with sulfonic acid group-free pyrazolone compounds of the general formula = C -CR ₄ NO ₇ Rs in which R ₄ , R ₇ and Rs have the meaning given above, condensed in preferably acidic medium or that 2-methylene indolines of the general formula in which A, Ri, R2 and Re have the meaning given above have, with sulfonic acid group-free pyrazolone-4-aldehydes or their functional Derivatives of the general formula OCH-C = CR ₄ NO ₇ Rs in which R ₄ , R ₇ and Re have the meaning given above, preferably condensed in an acidic medium. Considered publications:
U.S. Patent No. 2,032,502. When the application was announced, an explanatory table was displayed. 309 * 767073 11. S3