DE1569742A1 - Aminodiphenyl indolyl methane dyes - Google Patents

Description

Amlnodiphenyl indolyl methane dyes

The present invention relates to valuable new aminodiphenyl indolyl methane dyes of the general formula

(D

In this formula, R denotes hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid ester, optionally N-substituted carbonamide, acyl, alkylsulfonyl or arylsulfonyl group, R ₁ denotes hydrogen, an alkyl, aralkyl -, cycloalkyl or aryl radical, R _{2 is} hydrogen, an alkyl, cycloalkyl or AFalkyl radical> R, "hydrogen, an alkyl or aryl group, a GarbOn acid ester group, an optionally N-substituted carbonamide group or an alkoxy group, R _{4 is} hydrogen, an alkyl -, aralkyl, cycloalkyl or aryl radical and X is an anionic radical; the new dyes can be in the aliphatic, cycloaliphatic and aromatic radicals, including the benzene rings represented by the formula,

Le A 10 169 0 0 9 Ö 3 1/0 2 7 2 ORIGINAL IWSPECTiO

, New. _; U ηterlagen (Art 7 g ι from * a No. ι sentence a άή Äncjerunase «. % 4. a. In _v

2 T569742

other substituents (non-ionic substituents) with exception of sulfonic acid and carboxylic acid groups. Examples of possible non-ionic substituents are: lower alkyl and alkoxy radicals with 1 - 4 carbon atoms, Aralkyl, such as benzyl, aralkoxy, such as benzyloxy, aryl, such as phenyl and phenyl radicals substituted by nonionic radicals, e.g. chlorophenyl, methylphenyl, ethylphenyl, nitrophenyl, Cyanophenyl etc., aryloxy groups such as phenyloxy, halogen substituents, in particular Cl and Br, carboxylic acid ester groups, in particular carboxylic acid methyl ester and ethyl ester groups, optionally N-substituted carbonamide groups, where lower alkyl groups are preferred as N-substituents, the can be further substituted, e.g. by Cl, Br and OH, the Cyano, nitro, hydroxyl or araino group, alkylsulfonyl, such as methylsulfonyl and ethylsulfonyl, arylsulfonylj such as Benzenesulfonyl and p-toluenesulfonyl, acyloxy groups, such as Acetoxy and propionyloxy, acylamino groups such as acetylamino, Propioriylamino, ethylsulfonylamino, methylsulfonylamino, Benzoylamino, benzenesulfonylaraino etc. and acyl residues, like the benzoyl and acetyl radicals.

A group of particularly valuable Tarbstofie in the context of the. new products of the general formula (I) corresponds to the formula

Le A 10-169 - 2 -

BATH ORIGINAL

0 0 9831/0272

(Ia)

In this formula, R ^{1 stands} for hydrogen or a lower alkyl radical, in particular methyl or ethyl, R ¹ .. for hydrogen,: a lower alkyl radical, in particular methyl, ethyl, propyl, butyl, a phenyl radical, which is replaced by chlorine, bromine, lower alkyl - Or alkoxy radicals can be further substituted, or benzyl, R ¹ 2 for hydrogen, or a lower alkyl radical, such as methyl or ethyl, or the benzyl radical, R ¹ , for methyl, phenyl, or substituted by chlorine, bromine or lower alkyl or alkoxy radicals Phenyl, and R ¹ . represents hydrogen, a lower alkyl radical, such as methyl, ethyl, and benzyl, and Z represents a halogen, in particular Cl- or Br-, a lower alkyl, such as methyl, ethyl or propyl, or a lower alkoxy such as methoxy or ethoxy substituents; X means an anionic radical.

The new dyes are obtained by using 4-aminobenzophenones the general formula

R - / "V-C-

= / Q Y =

(II)

wherein R, R ₁ and R «have the meaning given above,

Le A 10 169

009831/0272

with indole derivatives of the general formula 1569742

(in)

where R- and R. have the meaning given, condensed in the presence of acidic condensing agents to give dyes of the formula (I) and the starting components free of sulfonic acid and carboxylic acid groups.

As a starting material for the production of the invention The following aminobenzophenones, for example, are suitable dyes:

4-aminobenzophenone, 4-N, N-dimethylaminobenzophenone, 4-N ₁ N-diethylaminobenzophenone, 4-N, N-dibutylaminobenzophenone, 4-N-methyl-N-oxethylaminobenzophenone, 4-N-methyl-N-chloroethylaminobenzophenone, 4- N-methyl-N-cyanoethylaminobenzophenone, 4-N-ethyl-N-cyanoethylaminobenzophenone, 4-N-ethyl-N-chloroethylaminobenzophenone, 4-N-ethyl-N-oxäthylaminobenzophenone, 4-N-butyl-N-oxäthylaminobenzophenone, 4-N-butyl-N-chloroethylaminobenzophenone, 4-N, N-dioxäthylaminobenzophenone _f 4-N, lf-dichloroethylaminobenzophenone, 4-N-methyl-N-benzylaminobenzophenone, 4-N-ethyl-N-benzylaminobenzophenone, 4-N- Phenyl-N-methylaminobenzophenone, 4-N- (4'-ethoxyphenyl) -N-methylaminobenzophenone, 4-N- (2'-ethoxyphenyl) -N-methylaminobenzophenone, 4-N- (4'-chlorophenyl) -N-methylaminobenzophenone , 2-methyl-4-N _f N-diethylaminobenzophenone, ^ -Chlor ^ -NyN-diethylaminobenzophenone, 2-methyl-4-M- <> xethyl-N-ethylamiobenzophenone, 2-chloro-4'-N ^ -dimethylaminobenzophenone,

ΐβ A 10 169. 4 _β

00983Ί / 0272

2-bromo-4 ^f ^ N, N-diethylaminobenzophenone, S-aminobenzophenone, 4-ethyl-4'-N, N-diethylaminobenzophenone, 4-cyano-4 ^t -N, N-diethylaminobenzophenone, 2-chloro-4 ^l - N-phenyl-N-methylaminobenzophenone, 2-chloro-4 ^l -N- (4 ^l'- ethoxyphenyl) -N-methylaminobenzophenone, 3-chloro-r4'-N-phenyl - N-methylaminobe.nzophenone, '4- Phenyi_4 «_N-phenyl-N-methylaminobenzophenone, 4-Ä" bhyi- ^ "- li-phenyl-N-ffiethylaminobenzophenone, 4-methyl-4'-N- (4" - ethoxyphenyl) -N-methylaminobenzophenone, 4- Methyl-4'-N, N-dimethylaminobenzophenone, 4-meth.yl-4'-N-phenyl-N-methylaminobenzophenone, 4-cyano-4 ^l -N _> N-dimethylaininobenzoplienone, 4-carbomethoxy-4 «-N, N-dimethyXaminobenzophenon, ^ -Methyleulfonyl ^ '- N-phenyl-K-methylaminobenzophenon.

Suitable indole derivatives are, for example!

2-methylindole, 2-phenylindole, 2,5-dimethylindole, 2-methyl-5-chloroindole, 2-phenyl-5-methylindole _f 2-phenyl-5-chloroindole, 1,2-dimethylindole, 1-methyl ^ 2- phenylindole, 1,2,5-trimethylindole, 1,5-dimethyl ~ 2-phenylindole, l ^ -dimethyl-S-chlorindole, l-methyl - ^ - phenyl-S-chlorindole, -l-xthyl-2-methylylindole, 1-ethyl-2-phenylindole, l-ethyl-2,5-dimethylindole, l-ethyl-2-phenyl-5-methylindole, l-ethyl-2-methyl-5-chloroindole, l-ethyl-2-phenyl- 5-chloroindole, 1-benzyl-2-methylindole, 1,4,7-trimethyl-2-phenylindole, in-butyl-2-phenylindole, 1-isobutyl-2- (4'-chlorophenyl) -4,6-dimethylindole , l-cyanoethyl-2-methylindole, l-cyanoethyl-2-phenylindole.

0098if / 0'272

Suitable acidic condensing agents are, for example!

Hydrochloric acid, sulfuric acid, phosphoric acid, phosphorus oxychloride, thionyl chloride, phosgene, zinc chloride, aluminum chloride, tin chloride or p-toluenesulfonic acid.

■■ ^: "'Jfi&' Üe äictΤου · -kaiin fzi- present" · ' ^or-: Ab'we äettheiV ·: ei »es. Inert solvents. Suitable solvents are, for example, chlorobenzene, o-dichlorobenzene, toluene, xylene, benzene, ligroin, dioxane, cyclohexane, carbon tetrachloride, chloroform and in some cases also methanol, ethanol and acetone.

The reaction is generally carried out at elevated temperature, for example at 40 - 120 run ⁰ C - 16O ⁰ C, preferably at 70th

The anionic radicals X "" can be both inorganic and organic ions? Examples include: Cl ", Br", J "*, CELSO /", C ₂ H ₅ SO. ", p-toluenesulfonate, HSO / *, benzenesulfonate, p-chlorobenzenesulfonate, phosphate, acetate, Pormiate, propionate, oxalate, lactate, maleate, orotonate, tartrate, citrate, NOj ", perchlorate, ZnCl ,. The nature of the anionic radicals is irrelevant for the properties of the dyes, provided that they are largely colorless radicals which do not adversely affect the solubility of the dyes.

A further process can be used to remove part of the

Le A 10 169 - 6 -

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inventive dyes also by condensation of Benzoin oils of the general formula

(IV)

with aromatic amines of the general formula

■ rv ζ * ⁵

^X R ₆

wherein R, R, and R ^ have the meaning given, while Rc for hydrogen, an alkyl, cycloalkyl or aralkyl radical and L for an alkyl, cycloalkyl, aralkyl or aryl radical

ο ■. .

stands,

obtained in the presence of acidic condensing agents.

Suitable benzoylindoles of the general formula (IV) are for the preparation of the dyes according to the invention, for example:

l-methyl-2-phenyl-3-benzoylindole, l, 2-dimethyl-3- * benzoylindole,

indole, ■ 1,2-dimethyl-3-benzoyl-5-chloroindole, 1-methyl-2-phenyl ^ 3-benzoyl-5-chloroindole, l-ethyl - ^ - methyl ^ -benzoylindole, 1-ethyl-2-phenyl-3-benzoylindole, l-benzyl-2-methyl-3-benzoylindole, 1,4,7-imethyl-2-phenyl-3-benzoylindole, l-n-butyl-2-phenyl-3-beneoylindole, l-cyanoethyl-2-methyl-3-benzoylindole, l-cyanoethyl-2-

-7- 009831/0272 *

phenyl-3-benzoylindole, l-methyl-2- (2'-chlorophenyl) -3-benzoylindole, l-methyl-2-phenyl-3- (2'-chlorobenzoyl) indole, 1-methyl-2-phenyl- 3- (3'-chlorobenzoyl) indole, 1-methyl - ^ - phenyl - ^ - (4 · - methylbenzoyl) indole, 1,2-dimethyl-3- (2'-chlorobenzoyl) indole, 1,2 -Dimethyl-3- (3'-chlorobenzoyl) -indole, 1,2-dimethyl-3- (4 ^f -. ^ '■' methy ^ benzoy ^ -indql · and l-ethyl-2-phenyl-3- (2'-chlorobenzoyl) diindole.

Suitable aromatic amines of the general formula (V) are, for example:

Ν, Ν-dimethylaniline, Ν, Ν-diethylaniline, N, N-dibutylaniline, N-methyl-N-oxethylaniline, Ν, Ν-dioxäthylaniline, N-methyl-N-chloroethylaniline, Ν, Ν-dichloroethylaniline, 1-N- Ethyl-N-oxethylamino-3-methylbenzene, 1N-ethyl-N-chloroethylaraino-3-methylbenzene. N-butyl-N-oxethylaniline, 3-chloro-lN, N-diethylaniline, 3-chloro-N, N-dimethylaniline, N-methyl-N-benzylaniline, N-ethyl-N-benzylaniline, lN-ethyl- N-benzylamino-3-methylbenzene, H-methyldiphenylamine, N-ethyldiphenylamine, N-cyanoethyldiphenylamine, N- (A-) ethoxyphenyl) -N-methylaniline, 3-methoxy-lN, N-.dimethylaniline and 3-lthoxy- lN, N-diethylaniline.

Particularly suitable acidic condensing agents for this process are phosphorus oxychloride, thionyl chloride, phosgene, zinc chloride, Aluminum chloride etc.

Another suitable method of representing the new Dyes is that you can get benzanilides of the general

"Formula. ORIGINAL INSPECTED <'

'■ ■ · ■ -8-

Le A 10 169. 009831/0272

OR ₇

/ (VI)

wherein R has the meaning given, while R _{1 represents} hydrogen or the alkyl radical and R _{Q represents} an aromatic one

with aromatic amines of the general formula (V) in the presence of acidic condensing agents and then without isolation of the intermediate with indoles of the general Formula (III) condensed.

As benzanilides (VI) that are suitable for this process, are mentioned for example:

Benzanilide, 2-chlorobenzanilide, 3-chlorobenzanilide, 2-methylbenzanilide, 3-methylbenzanilide, 4-methylbenzanilide, 2-methoxy benzanilide, 2-ethoxybenzanilide, 2,4-dimethylbenzanilide, 2,5-dichlorobenzanilide and 2,6-dichlorobenzanilide,

AIb aromatic amines (V) are used for this production method the same compounds suitable for the second procedural route were specified. As indole compounds, those indicated as being suitable in the first preparation route can be used. Also suitable as acidic condensing agents here are phosphorus oxychloride, thionyl chloride, phosgene, zinc chloride, Aluminum chloride and others . ■

_{L (SA 10 169.} G. ·.. ■ ■ OeSGINAL INSPECTED

00983 1/0272

The products obtainable according to the process are extremely valuable dyes which are used for dyeing and printing materials made of leather, tannin cotton, cellulose acetate, synthetic super polyamides and polyurethanes, and for dyeing fibers containing lignin such as coconut, jute and sisal .'köruien.v .Bi « ^; ε & η & · -more .- ^

liquids, stamp inks, ballpoint pen pastes and can also be used in rubber printing. They are particularly suitable for dyeing and printing materials that consist entirely or partially of polymerized acrylonitrile and / or vinylidenecyanide or of acid-modified aromatic polyesters and are characterized by very good lightfastness, wet fastness, rubbing fastness and sublimation fastness. They also have very good drawability on these fibers and have good over-dyeing fastness. The dyes form lightfast pigments with anionic precipitants such as clay, tannin and phosphotungsten (molybdenum) acids, which can advantageously be used in paper printing.

Example 1:

37.8 parts by weight of N-phenyl-N-methylaminobenzophenon, 27 "2 parts by weight l-methyl-2-phenylindole and 35 parts by weight of phosphorus oxychloride are heated together to 10O ⁰ C and held for 3 hours at this temperature. The still warm melt are added to 600 parts by volume of 50 ⁰ C hot water, and the pH-value by adding 140 parts by volume of 20 # 2, a sodium acetate solution.

Le A 10 169 - 10 -

ORIGINAL INSPECTED

> ^: '"" 009831/027 2

Then the precipitation of the dye is completed Add 30 parts by weight of table salt and let the approach stir for a few hours. The color resin obtained is separated off, dissolved in 4000 parts by volume of boiling water, the solution with Activated charcoal clarified and the dye after bich the solution 'has cooled down a little by adding 90 parts by volume of a · ·· ; Solution of zinc chloride in the same amount by weight of water failed. The dye is stirred for some time, filtered off with suction and washed with 10 ^ iger saline solution. The thus obtained Dye conforms to the formula

ZnCl.

and dyes polyacrylonitrile fibers in a lightfast, bluish green.

Valuable dyes are also obtained if, in the above example, the equivalent amounts of the indole derivatives listed in the table below are used instead of 1-methyl-2-phenylindole.
Indole derivative color on polyacrylonitrile fibers

2-phenylindole -

2-methylindole 1,2-dimethylindole 1-methyl-2-phenyl-5- »ethox3rindole

bluish green greenish blue greenish blue. Bluish green '^

Le A 10 169

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009831/0272

OHiGJNAL INSPECTiD

Indole derivative

Jfg

1-ethyl-2-phenylindole i-ethyl-2-methylindole 1-ethyl-2-phenyl-5-methylindole 1 _f 5-dimethyl-2-phenylindole i-cyanoethyl-2-phenylindole i-cyanoethyl-2-methylindole 1-ethyl-2-phenyl-7-chloroindole .. · .1 | .6-P.imethy.1-2-phenylindole. ' . ., ";'1-Isobutyl-2-phenyl indole 1-ethyl-1-phenyl-0-methylindole 1-n-butyl-2-phenyl-6-methylindole 1-n-butyl-2-phenylindole

Example 2;

. 15697A2

Color on polyacrylonitrile

blues. Green Blue

Green Blue
bluest. Green steamed bluest. Green g * d. bluest. Green steamed bluest. Green fluff. Green and blue. Green '"steamed blue. Green blue. Green slightly steamed blue. Green

45 parts by weight of 4-N, N ~ dimethylaminobenzophenone, 41.4 parts by weight of 1-methyl-2-phenylndole and 50 parts by weight of phosphorus oxychloride are combined and heated to 100 ° C. for 3 hours. The still warm melt is discharged at 1000 Volurateile water of 50 ⁰ C and the reaction mixture with 320 parts by volume of 20 $ sodium acetate solution at a pH of 2 is set. After the solution has cooled, the dye is precipitated by adding 100 parts by weight of common salt and 150 parts by volume of a solution of zinc chloride in the same amount by weight of water. For further purification, the dye is dissolved in boiling water, clarified with activated charcoal and precipitated by adding 30 parts by volume of zinc chloride solution. The dye obtained in this way dyes polyacrylonitrile fibers in a lightfast greenish blue.

If the reaction is carried out according to the method given above, using the aminobenzophenones and indole derivatives listed in the table below, dyes are also obtained which are characterized by very good coloring properties *

Le A 10 169 ORlGINAb! SN $ P £ CTED

to act

Aminob enz ο phenon indole

Color on polyacrylonitrile.

4-dimethylaminobenzo phenone

4- dimethylaminobenzo phenone

4-diethylaminobenzophenone

phenone

4-diethylaminobenzo phenone

4-diethylaminobenzo phenone

4-dimethylamino-4'-methylbenzophenone

4-dimethylamino-4'-methylbenzophenone

4-dimethylamino-3'-chlorobenzophenone

4-dimethylamino-3'-chlorobenzophenone

4-dimethylamino-2. Chlorobenzophenone

4-dimethylamino-2-chlorobenzophenone

4-diethylaminobenzophenone .

4-diethylamino-4 ^f methylbenzophenone

4-diethylamino-4'-. methylbenzophenone

4-diethylamino-3 'chlorobenzophenone

4-diethylamino-3'-chlorobenzophenone

4-dimethylamino-3'-methylbenzophenone

L · K to

1,2-methylindole

2-methyl-1-ethyl-6,7-benzoindole

bluish purple

Blue-gray.

l-methyl-2-phenyl blue indole. '.., - ■.

2-phenylindole

2-methyl-1-ethyl-6,7-benzoindole

1,2-dimethylindole

l-methyl-2-phenylindole

1,2-dimethylindole

l-methyl-2-phenyl indole

1,2-dimethylindole

l-methyl-2-phenyl indole

1,2-dimethylindole

Green Blue

Gray purple

reddish purple

green thiohigos BLUE

reddish blue

- Blue

reddish blue

- Blue

Blue violet

1,2-Dimethylindole bluish violet

l-methyl-2-phenyl-blue-green indole

1,2-dimethylindole BXtM

l-methyl-2-phenyl- strongly greenish indole blue

1,2-Dimethylindöl reddish purple

00 9S31 / 027

! ■ inobenxophenon

4-dimethylamino-4'-methyl benzophenone

4-dimethylamino-3'-chlorobenzophenone

4-Diaethylamino-2-chloro benzophenone

Diethylamino-4'-methyl oenzophenone

) 4-Dimethylamino-2 ', 5 · - dichlorobenzophenone

H ₁ ''

Il

4-D! Methylamine-3'methyl 4 * -nitro-benzophenone Indole 2-methylindole

2-phenylindole 2-methylindole

2-phenylindole 2-methylindole

2-phenylindole 2-methylindole

1,2-dimethylindole

Color tuxf poly aoryl nitrile etark blue * Bordo

Blue green

ged. rotat. blue

ged. st. grünst · Blau et. bluest. violet

greenest. Blue purple

blue

1-methyl-2-phenylindole is green. blue

2-methylindole rotst. blue

2-phenylindole green. blue

1,2-dimethylindole green. blue

1-methyl-2-phenylindole blue green

4-diethylamino-2'-chlorobenzophenone

4-cyanoethy1-methyI aminobenzophenone

4-diethylamino-3 · ae ethyl benzophenone

4- (p-Xthoxyphenyl) methyl-amino-4'-methyl btnzophenon 1,2-dimethylindole

1-methyl-2-phenylindole

1,2-dimethylindole

Blue greens. blue

violet

1-methyl-2-phenylindole green * blue

1,2-Dinethylindole st. rotst. blue

i-methyl-2-phenylindole st. greenest. blue

1,2-diamethylindole grst. blue

1-methyl-2-phenylindole blue. green

L <? A 10 009831/0272

Aminobenzophenone

Indole

Color on polyacrylonitrile

4- (p-Xthoxyphenyl) -methyl-amino-3'-chlorobehzophenone ' 1,2-DiKethy1indole

green t. blue

4- (p-Ethoxyphenyl) -methyl-1-Methy1-2-phenylindole bluish. green amino-3'-chlorobenzophenone

4-diethylamino-2-chlorobenzophenone

4-cyanoethyl methyl aminobenzophenone

^ -Phenylmethylainino-J-nitro-4'-methylbenzophenone

4-phenylmethylamino-3-chlorobenzophenone

4-Phenylmethylamino-4 · ■ methyl benzophenone

4 *> phenylmethylamino- 2 ', 5 · -diohlofbenzophenone

4-phenylmethylamino-5 'methylbenzophenone

4-diethylaoino-3'-cklorbenzophenone

4-diethylamino-3 ^l ethyl-benzophenone 2-methylindole 2-phenylindole

2-methylindole 1,2-dimethylindole

redden. blue

grst. Blue teal

redden. Purple green. blue

"UMethyl-2-phenylindole blue. Green "blues. Green

1,2-dimethylindole

greenest. Blue greens. blue

i-methyl-2-phenylindole bluish. green "- ■ blue. Green

1,2-dimethylindole

greenest. blue

1-methyl-2-phenylindole bluish. green 1,2-dimethylindole green. Bleu 2-phenylindole «blue-green

2-methylindole 2-phenylindole

2-methylindole

redden. Blue teal

blues. violet

Le A 10 I69 - 15.-

00 9831/0272

Aminobenzophenone

4; -Phenylmethylamino-4 '* ■ methylbenzophenone

4-dimethylamine-3 - nitro-4'-methylbenzophenone

4-phenylmethylamino 2 ', 5'-dichlorobenzophenone

4-Diaethylamino-3'- ■ ethyl-4'-nitro-benzophenone

4-bimethylamino-3'-nitrobenzophenone

4-Diaethylamino-3 · -aethy1-4'-nitro-benzophenone

4-Diaethylaiiino-3 «■ nitrobenzophenone

4-diethylamino-3'- methy1-4'-nitro-benzo- phenone

4-diethylamino-3 · nitrobenzophenone

4-diethylamino-2 ·, 5 '· dichlorobenzophenone.

4-DiBethylaaino-2'-chlorobentophenone

4-Di "* thyl *" ino-2 ", 5'-dichlorobenzophenone

4-Ph "nylaethylamino-2 _'l 5'-diohlorbenzophenon Indole

2-phenylindole 2-methylindole

2-phenylindole 2-methylindole

2-phenylindole 1,2-dimethylindole

Shade ali £ 69742 Polyacrylonitrile

bluest. green

Bluish gray

rotst. Dark blue

st. Bluish green. blue

bluest. Green greens. blue

i-methyl-2-phenylindole blue green

"green. Blue

1,2-Diaefhylindole 2-phenylindole

2-methylindole
η

2-phenylindole 1,2-dimethylindole

Blue steamed bluest. green

ged. green * blue steamed rotst. blue

ged. greenest. Blue greens. blue

1-methyl-2-phenylindole blue green

"'Green. Blue

1,2-dimethylindole

Blue blue

1-methyl-2-phenylindole green. blue

i-ethyl-2-methylindole rotst. blue

" Blue

"Greens. Blue

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Amlnobenzophenone

Indoil

15697Α2 "

Hue on Polyacrylni tri1

4-diethylamifto-2'-chlorobenzophenone

4-phenylmethylamino-2'-chlorobenzophenone

4-diethylamino-benzophenone

4-Diniethylainino-3'-chlorobenzophenone

4-phenylmethylamino-4'-methylbenzophenone 4-di-n-propyiaminobenzophenone

4-dimethylamino-2-chlorobenzophenone

4-dimethyl $ .mino-2 ⁽ , 5! - dichlorobenzophenone

4-diethylamino-2-chlorobenzophenone

4-phenylmethylamino-2'-chlorobenzophenone

4-diethylamino benzophenone

4-Dijnethylamino-2. -Chlor- " benzophenoni

4-dimethylamino-2 ', 5 «-di-" chiorbenzophenon

4-diethylamino-2 «-chlor-" beiizophenon

4- »PhenyliDethylaiDino-2 · -" chlorobenzophenone

l-ethyl-2-moethylindole blue

»Green. blue

"· Ged _f rotst. Blue

η ged. reddened «blue

ged. green »blue ged. redden. blue

ged. green · blue green. blue

"·. .... '·." ■ green. blue

greenest. blue

" Green Blue

_t 5-Di2nethyl-2-phenylindole steamed. Blue green

1-ethyl-2-niethylindole
1,2-dimethylindole

1-methy1-2-phenylindole 1-ethyl-2-phenylindole

4-bimethylamino-2'-chlorobenzophenone

4-diethylamino-2 ^f -chlorobenzophenone

4 ^ Diniethylamino * 2 ·, 5'-dichlorobenzophenone

4-p-Xthoxyphenyl-iaethylaminobenzophenone 1-Xthyl-2-phertyl-5 _i methylindole

1-Xthyl-2-methylindOl

1-ethyl-2-phenylindole

ged. grst. Blue greens. Blue greens. Blue bluish. green

greenest. Blue greens. blue greenest. Blue green blue blues. CrUn

Lq A 10 169 0 9 8 31/0272

Aminobenzophenone indole * shade on polyacrylonitrile

4-diethylaminobenzophenone i-cyanoethyl-2-phenylindo'l dark blue

4-diethylamino-2 · chloro- «somewhat green. blue

benzophenone

4-diethylaminobenzophenone 1-cyanoethyl-2-methylindole red. Dark blue

4-Di-n-propylaaino-1,2-dimethylindole clear, slightly green. blue 2.5'-dichlorobenzophenone

"1-Methyl-2-phenylindole clear green. Blue

4-di-n-propylamino-2 »-" blue

ohlorbenzophenon

¹¹ 1,2-dimethylindole clear blue

4-diethylaminobenzophenone 1-ethyl-2-phenyl-'7-blue-gray

chlorindole

4-N-phenylmethylamino-1-cyanoethyl-2-phenylindole clear blue-green 2 · -chlorobenzophenone

. 4- (N-p-Äthoxyphenyl-N · -. "·. Steamed blue-green.. -:

methyl) -amino-benzophenone

4-Phenylmethylamino-2'-i-cyanoethyl-2-methylindole strongly green. blue ohlorbenzophenon

4- (N-p-Ethoxyphenyl-N-1-cyanoethyl-2-methylindole, dark blue-green ethyl) aminobenzophenone

4- (p-methylphenyl-methyl) -1-methyl-2-phenylindole bluish. green • aminobenzophenone ......

¹¹ 1,2-dimethylindole steamed greenest. blue

4-N- (p-ethoxyphenyl-1,2-dimethylindole clear, greenish blue r methylamino) -2'-chlorobenzophenone

¹¹ 1-methyl-2-phenylindole clear, bluish. green

4-diethylamino-benzo-1,6-dimethyl-2-phenyl-ged. Blue green phenone indole

4-Diethylamino-2'-ohlor- "steamed, strongly green. Blue

benzophenone

4-diethylaminobonzo- 1-isobutyl-2-phenylindole, ged. green «blue phenone

4-diethylamino-2'-ohlor- "clear green. Blue

benzophenone

4-phenylmethylamino-2'-2-phenylindole olive

ohlorbenzophonon

»2-Metliylindole a bit green. blue

"1-1-bobutyl-2-phenylindole bluish. Green

'1,7-Dimethyl-2-phenylindole bluish. Qrün

© OPY Le A 10 169 - 18 - 0088 3 1/0272 '

Amlnobenzophenone

Indole

Shade-on polyacrylonitrile

■ 4-diethylamino-benzophenone

4-diethylamino-2'-chlorobenzophenone

4-phenylmethylamino-2'-chlorobenzophenone

4-diethylamino-benzophenone

4-diethylamino-2-chlorobenzophenone

4-phenylmethylamino-2'-chlorobenzophenone

4-diethylamino-benzophenone

4-N- (cyanoethyl-methyl) ■ amino-2 -chlorobenzophenone

-4-diethylamino-benzophenone

methylindole

4-diethylamino-2'-chlorobenzophenone

4-pßenylmethylamino-2 '■ chlorobenzophenone

4-N- (cyanoethyl-methy1) ■ amino-2'-chlorobenzophenone

4-phenylmethylamino-3> bromobenzophenone

4-dimethylamino-5-bromobenzophenone

4-bioethylamino-5-bromo-2'-chlorobenzophenone 1-n-butyl - ^ - phenyl-omethylindole

1-n-Butyl-2-phenyl-6-me thy1indol

1-Benzyl-2-phenyl-7-methylindole

1-benzyl-2-phenylindole
1,2-dimethylindole

1-methyl-2-phenylindole
1-n-butyl-2-phenylindole

_ II 2-phenylindole

2-methylindole
1,2-dimethylindole

1-methyl-2-phenylindole
1,2-bimethylindole

1-methyl-2-phenylindole
1,2-bimethylindole

ged. Blue green

strong greenery. Blue empty bluish. Green teal

strong greenery. Blue clear bluish. Green steamed st. bluest. green

Gray-green
bluest. violet

ged. sth. Blue steamed green. blue

slightly green, blue clear blue-green steamed greenest. blue

sth. blues. Violet blue

ged. blueBt. Green sth. violet

sth. green sth. rotst. blue

1-methyl-2-phenylindole green. blue

Le A 10 169

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009831/0272

Aminobenzophenone

4-diethylamino-3-bromobenzophenone

4-dimethylamino-2-methylbenzophenone

4-diethylamino-2'-bromobenzophenone

4-diethylamino-2-bromobenzophenone

4-phenylmethylamino-2 · ■ bromobenzophenone

4-amino-2 ^l -chlorobenzophenone

4-Dimethylamino-2-methyl-2'-bromo-benzo phenone

4-DiBethylamino-r2-ethyl-2'-chlorobenzophenone

Indole

1,2-dimethylindole 1-methyl-2-phenylindole i-methyl-2-phenylindole

1,2-dimethylindole

1-ethyl-2-phenylindole

1,2-dimethylindole Color aJ 569742 Polyacrylni trl1 i «?

bluest. violet

ged. strong green · blue bluish. Green

dull greenery. Blue is blue. green due to greenest. blue

1-methyl-2-phenylindole green. blue

1-ethyl-2-phenylindole 1-methyl-2-phenylindole

1,2-dimethylindole

1-ethyl-2-phenylindole

1,2-dimethylindole 1-methyl-2-phenylindole 1,2-dimethylindole

1-methyl-2-phenylindole 1,2-dimethylindole

strong bluish. green

greenest. Blue 'very bluish. Green strongly bluish. Red

empty, blue. Violet green. blue

strong greenery. Blue violet. blue

1-methyl-2-phenylindole strongly green. blue

4-N-B-chloroethyl-N-methyl-1,2-dimethylindole amino-2-methylbenzophenone

¹¹ 1-methyl-2-phenylindole

4-benzylethylamino-2-i-methyl-2-phenylindole a «ethylbenzophenone

". 1,2-Dimethylindole

4-diethylamino-2-athoxy-1-methyl-2-phenylindole benzophenone

4-N- (4'-Xthoxyphenyl) -H-methylamino-2'-chlorobenzophenone

Le A 10 169

1,2-dimethylindole

2-methylindole

- 20 -

rotst. blue bluest. green blues . green I.
greenery, " Blue blue rotst. blue blue

831/0272

Aminobenzophenone

Indole

Color on polyacrylonitrile

~ 2-chloro-4'-dibenzylamino-1-methyl-2-phenylindole benzophenone

2-chloro-4'-dibenzylamino-1,2-dimethylindole benzophenone

2-chloro-4'-dibenzylamino-2-phenylindole benzophenone

4-methyl-4'-ethylbenzyl-1-methyl-2-phenylindole aminobenzophenone

4-methyl-4'-ethylbenzylaminobenzophenone

2-chloro-4'-ethylbenzylaminobenzophenone

1,2-dimethylindole 1,2-dimethylindole 1-methyl-2-phenylindole

2-chloro-4'-ethylbenzylaminobenzophenone

4-ethylbenzylaminobeiizo-1-methyl-2-phenylindole phenone

4-Xthylbenzylaminobenzo- - 1,2-dimethylindole - · phenone

2-chloro-4 '"methylbenzylaminobenzophenone

2-chloro-4'-ethylbenzylaminobenzophenone

2 ~ chloro-4'-ethylbenzylaminobenzophenone

4-ethylbenzylaminobenzo-2-methylindole phenone

^ -Aethylbenzylaminobenzo-2-phenylindole phenone

1-methyl-2-phenylindole 2-phenylindole

2-methylindole

4-phenylmethylamino-5'-bromo-benzophenone

4-Ethyl-benzylamino-2- methyl-2- bromo-benzophenone

1-methyl-2-phenylindole

1,2-dimethylindole

1-methyl-2-phenylindole

1,2-dimethylindole

4 ~ Aainp-2 ', 5'-dichloro-1-methyl-2-phenylindole

benzophenone

¹¹ 1,2-dimethylindole

greenish blue reddish blue bluish green

bluish green strongly bluish Bordo greenish blue strongly greenish blue bluish green

reddish blue. . , greenish blue bluish green

Blue-gray

reddish blue bluish green
greenest. Blue-gray strong blue · Bordo green. blue

sth. green blue red violet
yellow. Red

A 10 169

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Aroinobenzophenone

Indole

4-diethylamino-2- 1-methyl-2-phenyl-indole ethoxy-2'-chlorobenzophenone

¹¹ 1,2-dimethyl indole

4-chloroethyl-n-butyl- » amino-benzophe non

¹¹ 1-methyl-2-phenyl-indole

4-chloroethyl-methylamine-1,2-dimethyl-indole

benzophenone

". 1-methyl-2-phenyl-indole

4-di-n-propylamino-benzo-1-n-butyl-2-phenyl-6-phenone

Color on polyacrylonitrile

ged. etv. greenest. blue

ged · bluest · violet d. etv. rotst. blue

methyl indole

1-n-butyl-2-phenyl-indole

4-ot-naphthyl-methylamino-benzophenone

4- (X.-Naph'thyl-methyl- ' amino-2 ■ -chlorobenzophenone

4-ethyl-benzyl-amino-2'-bromo-benzophenone

4-bioethylamino-2'-methoxy-benzophenone

4-ot-naphthyl-raethylamino-2'-bromo-benzophenone

4-diethylamino-2 - methyl benzophenone

4-phenylmethyl-amino-2'-methoxy-benzophenone

4-ß-chloroethyl-ethyiamino-2-methyl-2'-chlorobenzophenone

1,2-dimethyl indole

1-methyl-2-phenyl-indole

Il '.... L

1,2-dimethyl-indole 1-methyl-2-phenyX-indole

1,2-dimethyl indole

1-methyl-2-phenyl-indole

1,2-dimethyl indole 1-methyl-2-phenyl-indole blue green

1,2-dimethyl-indole 1-methyl-2-phenyl-indole

1,2-dimethyl indole

1-methyl-2-phenyl-indole

1,2-dimethyl indole

1-methyl-2-phenyl-indole

1,2-dimethyl indole greenest.

ged. zl. redden. blue

grünst, Bl & u

Blue green

ged. greenest. Blue etv. favorable blue

bluest. green

clear blue green '

etv. greenest. blue

clear _y strongly green. blue

clear blue

ged. strong green »blue

ged. ttv «green» blue

etv. green. Blue steamed etv. green. blue

bluest. Purple blue, green

ged. greenest. Blue steamed Blue green

greenest. 11au

Le A 10 169

ORIGINAL INSPECTED

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• Indole 1569742 • Amlnobenzophenone Hue on violetest. Blue. ■. ' ·. 1-methy1-2-phenyl-indole Polyacrylonitrile green 4-phenylmethyl-aemino- Blue green 2'-methyl-benzophenone 1,2-dimethyl indole Gray i-methyl-2-phenyl-indole blue ged. green 4-Biäthyiamino-3 «- greenest. blue methoxy-benzophenone 1,2-dimethyl indole Blue-gray Il
. ■ - = ■■ '!;' ^^ - · ί · ■ - .: ■ - ■ 1-methyl-2-phenyl-indole rotst. blue reddish blue 4-phenylmethyl-amino- green 3'-methoxy-benzophenpn 1,2-dimethyl indole greenish blue 11 i-methyl-2-phenyl-irfdol ged. greenest. blue 4-ethyl-behzyl-amino- strong greenery. blue 2 ^l -methyl-benzophenone 1,2-dimethyl indole turquoise M. 1-methyl-2-phenyl-indole rotst. blue 4-ethyl-benzyl-amino- greenest. blue 2 ^l -methoxy-benzophenone 1,2-dimethyl indole - greenish blue 1-methyl-2-phenyl-indole 4-phenylmethyl-amino- 4-phenyl-benzophenone 1,2-dimethyl indole bluish green Ji-methyl-2-phenyl-indole 4-diethylamino-4'rphenyl 1,2-dimethyl indole benzophenone l-methyl-2- blue phenylindole 4-dimethylamino-3'- 1,2-bimethyl methylbenzophenone indole ^ -N-phenyl-N-methyl- amino-2'-chlorobenzo l-methyl-2- phenone phenylindole 4-H-Pheny1-N-methy1- - ■ amino-2'-chlorobenzo 1,2-diraethyl phenone indole 4-N- (4 '* -ethoxy phenyl) - K-methylaminobenzo- l-methyl-2- phenone phenylindole 4-H- (4 ^l -Xthoxy- phenyl) -N-methyl- 2-methylindole aminobehzophenone 4-N- (4th »-ethoxy phe-

y p nyl) -H-methylaminobenaophenone

Le A 10 16 9 ;.

- 23 -

0 0 9 8 3 1/0 2 7 2

I JUJ / ti.

Example 3;

19.7 parts by weight of 4-aminobenzophenone and 14.5 parts by weight of 1,2-dimethylindole be entered 200 parts by weight of alcohol in 'and added to the reaction mixture at 3O ⁰ C with 50 parts by weight of concentrated hydrochloric acid (d = 1.19). After the batch ^{has been heated to 80 °} C., it is stirred for 3 hours at this temperature. Then 120 parts by volume of alcohol are distilled off and the deeply colored residue is added to a mixture of 250 parts by volume of saturated sodium chloride solution and 250 parts by weight of ice. The dye suspension is left to stir overnight, filtered off with suction and the dye is purified by recrystallization from water and precipitation with common salt. "'

Instead of 1,2-dimethylindole, it is also possible to use use the indoles below to make dyes by the above process.

Indole

Color shade on polyacrylonitrile

2-methylindole 1-methyl-2-phenylindole

1-Xthyl-2-methylindole 1-ethyl-2-phenylindole 1,5-dimethyl-2-phenylindole 1-ethyl-2-pheny1-5-methylindole 1-cyanoethyl-2-phenylindole

Red-violet blue-violet

bluest. ruby

empty, slightly bluish violet empty bluish. violet blunted, wg. bluest. Purple rotst. violet

If the 4-aminobenzophenone is replaced by ring-substituted 4-aainobenzophenones and these are set in the manner described with indole um, the following color shades are obtained when dyeing polyacrylonitrile: 1

Le A 10 169

009831/0272

■; ■■: .ι;. '/ - ■ /: ■■ Sf ■ ■. . ■ ;;

Benzophenone ' indole hue

-benzo- 1,2-bioethylindole strongly blue. Rooa

phenone

4-Anino ~ 3-bromo-benzo- ■ "'reddened. Bordo

phenone

1-benzo-1-methyl-2-phenylindole blunt rotst.

phenon violet

"2-Methylindole bluish. Pink

4-Attino-2'-chloroberizo-1,2-dimethylindole bluust. Red phenone

4-Amino-2 ', 5'-dimethyl-i-methyl-2-phenyl-indoi g «d. rotst. violet benzophenone,

• ι 2-methyl-indole bluust. ruby

1,2-dimethyl-indole bluest. ruby

Example 4:.

Polyacrylonitrile fibers are introduced at 4O ⁰ C in Plottenverhältnis 1:40 in an aqueous bath containing per liter 0.75 g of 30 # acetic acid, 0.38 g of sodium acetate and 0.3 g of a formula represented Aminodiphenylindolylmethanfarbstoffes described in Example 1 contains. The mixture is heated to the boil within 20-30 minutes and the bath is kept at this temperature for 30-60 minutes. The polyacrylonitrile fibers are then rinsed and dried. The result is a blue-tinged green dyeing of very good lightfastness, which is also distinguished by very good overdyeing fastness in acetic and sulfuric acid B »de aueseioluaet ·

Example 5t

From 2 parts by weight of the aminodiphenylndolylidethane dye, the production of which was described in Example 2, 60 parts by weight of glycerine - 20 parts by weight of water and 20 parts by weight of fuel, a stamping ink is prepared which gives clear, long-lasting prints. ; « _ΛΛΛΛΛ

009831/0272 Le A 10 169 - 25 - »

Example 6:

Eastindian Bastard leather, which is prepared in a conventional manner for dyeing is at a liquor ratio of 1:10 with 1% of the dye described in Example 2, which had been previously made into a paste with the same amount 30 # acetic acid, at 40 ⁰ C for 45 minutes in Walkfaß colored. The leather is prepared in a known manner. A greenish blue dyeing with good fastness properties is obtained.

Example 7:

19.7 parts by weight of benzanilide and 22.7 parts by weight of N-methyl-4-ethoxydlphenylamine are heated to 100 ° C. with 40 parts by weight of phosphorus oxychloride for 3 hours. Subsequently one carries etwlehtettil 20.7 · l-methyl-2-phenylindole, and heated for a further 3 hours at IQO ⁰ C. The still warm melt is discharged to 1000 parts by volume of water and adjusted # 20 sodium acetate to pH 2 with 275 parts by volume. The batch is left to stir for several hours, the color resin is separated off, it is dissolved in 3000 parts by volume of boiling water with the addition of 300 parts by volume of glacial acetic acid and the solution is clarified with activated charcoal.The dye is precipitated from the filtrate by adding 50 parts by volume of a solution of zinc chloride the equal weight of water.

The dye colors materials made of polyacrylonitrile in a bluish green with very good fastness properties.

Le A 10 169 - 26 - ^ ₀ ORIGINAL

009831 / Q272

100 parts by weight of phenylO ^ bensoylinaol * $ ß * 9 weight parts of Kotiiyioiphenylamln and 184 weight cells of phosphorus oxychloride are thinned and heated to 1GO ⁰ C. "The mixture is then stirred for 6 hours at this ^{1 day} dt © hot Sclimelzö under Rüliren in SOÖÖ iröltiaifceilö Wass0i% It is separated © inigo Sttuidon gerUlirfc and then dor dye of hater him lößt don RUokstand in kOOQ Voluaitoilen boiling V / asööi-, clears IAIT Aktivkohlo and "

& V & The dye obtained by adding 200 qewiolite parts of katrivrachloride dyes polyacrylic tri-fibers in one

bluish green »· ......

You can also get valuable dyes * if you go into the above Böispipl instead of H-Hctliyldiphs / üylainin die Equiv & lenton Mangen of the table below Anlliuderivate oinsötzti

ffnrbtpn nvif Polyp.ftrylni ^ ril, .-

. ■ "bloustichig Grttn.

diphonyXojriin; ·:

ti ^ ii-DiHthyiAriilin · strong 'grUnetichis blue

iJ, K-Din3st4iy! aniline, (srUnotichlg lUau

Le A 10 169

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ORIGINAL

009831/0272

Claims (1)

Patent claims: 1) Process for the preparation of aminodiphenyl-indolylmethane dyes, characterized in that one compounds of the general formula g V = / wherein R is hydrogen, an alkyl, aralkyl or aryl, nitro, cyano, carboxylic acid ester, optionally N-substituted carboxamido, acyl, Alkylsul fonyl- or arylsulfonyl group, R. ₁ Hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical. And Rp denotes hydrogen, an alkyl, cycloalkyl or aralkyl radical, with indole derivatives of the general formula where R, for hydrogen, an alkyl or aryl group, a carboxylic ester group, an optionally H-substituted carbonamide group or a Alkoxy group and R. Waeeerstoff, an alkyl, Is aralkyl, cycloalkyl or aryl radical, condensed in the presence of acidic condensing agents in the 3-position, whereby the initial components can have further substituents with the exception of sulfonic acid and carboxylic acid groups,
.it A 10 169 - 28 - 009831/0272 o? 9 2) modification of the method according to claim 1, characterized in that that one benzoylindole derivatives of the general formula wherein R ₁ IU and R have the meaning given in claim 1, with aromatic amines of the formula where R ^ for hydrogen, an alkyl, cycloalkyl or aralkyl radical and Rg represents an alkyl, cycloalkyl, aralkyl or aryl radical, reacts in the presence of acidic condensing agents, the Auagangekomporienten may have further substituents with the exception of sulfonic acid and carboxylic acid groups * 3) Modification of the method according to claim!, Thereby marked-Etichnet, that you can get benzanilides of the general formula 0 R " wherein R has the meaning given in claim 1, R "represents hydrogen or an alkyl radical and Rg stands for an aromatic radical, with aromatic amines of the general formula Lt A 10 169 - 29 - 0098 31/02 7 2 ^W R ₆ wherein R ₅ and Rg have the meaning given in claim 2, reacted in the presence of acidic condensing agents and the condensation product • ations product without intermediate with indole derivatives general formula wherein R, and R, have the meaning given in claim 1, condensed in 3-position, and web * -the output components may have further substituents with the exception of sulfonic acid and carboxylic acid groups * 4) The method as claimed in claims 1 and 3, characterized in that »on single output components in which R stands for hydrogen or a lower alkyl radical, R ₁ for hydrogen, a lower alkyl radical, a bentyl radical or, if appropriate, a chlorine or bromine radical , lower alkyl or alkoxy radical · further · * substituted phenyl radical, R "for hydrogen, a lower alkyl radical or bentyl radical, R, for methyl, phenyl or phenyl substituted by chlorine, bromine, lower alkyl or alkoxy radicals, R. for hydrogen or lower alkyl radicals or bensyl and Z stand for halogen, lower alkyl or alkoxy substituents. ¹⁶⁹ " ³⁰ -00983 1/0272 ί 5) Aminodiphenylindolylmethane dyes free of sulfonic acid and carboxylic acid groups the formula wherein R is hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid. ester, optionally N-substituted carbonamide, acyl or an alkylsulfonyl or arylsulfonyl group, R _{1 is} hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, R «hydrogen, an alkyl, cycloalkyl or aralkyl radical, R- Hydrogen, an alkyl or aryl group, a carboxylic ester group, an optionally K-substituted carbonamide group or an alkoxy group., R. Hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical and X an anionic radical and in which the aliphatic, cycloaliphatic and aromatic radicals can have further substituents with the exception of sulfonic acid and carboxylic acid groups. 6) Aminodiphenylindolylme.thane dyes free from sulfonic acid and carboxylic acid groups the formula R - LA 10 169 4 009831/0 27 2 in which R * stands for hydrogen or a lower alkyl radical, R ¹ ^ for hydrogen, a lower alkyl radical, benzyl or a phenyl radical optionally further substituted by chlorine, bromine, lower alkyl or alkoxy radicals, R'ρ for hydrogen, a lower alkyl radical or.den Beneyl radical, R 'for methyl, phenyl or by chlorine, bromine or lower alkyl or alkoxy ■ · radicals substituted phenyl, R for hydrogen, a lower alkyl radical or benzyl, Z for a halogen substituent, a lower alkyl or lower alkoxy radical and X stands for an anionic radical. 7} Process for coloring and * printing polymers and copolymers of acrylonitrile or on. Dicyanoethylene, da'arch characterized that dyes of the form of Arjpruchs 5 or 6 are used. • ^f u ·, ■ 8) Use of dyes of the formulas of claim 5 or Sum dyeing of leather, tanned cotton, synthetic super polyamides and polyurethanes, of writing fluids, of lignin-containing fibers and for printing pastes. 9) Materials made from polymers or copolymers of acrylonitrile or as. Dicyanethylene colored or printed ■ with dyes of. Claims 5 or 6. Le A 10 169 - 32 - 008131/02 ?! BATH ORIGINAL