DE1445447A1 - Process for the production of new substituted 3H-indoles - Google Patents

Description

intended for
Disclosure

. July X968

Allied Chemical Corporation, Mew York, NY ₃ USA

Process for the production of new substituted 3H ~ indoles

The invention relates to a process for the preparation of ^ H-indole derivatives.

The new 3,2-disubstituted 2H ~ indoles are lightly colored or practically colorless electron donors, which on contact generate intense colors in the yellow to red part of the visible spectrum with acidic electron acceptors. The new Compounds can therefore be used as precursors in "duplication materials, such as those described in U.S. Patents 2,505,470 and 2,548,366 to produce intense red to yellow colors.

Compounds that act as electron donors and are slightly colored to practically colorless on contact with acidic compounds Electron acceptors such as kaolin, bentonite or other acidic ones Clays, zinc sulfide, calcium fluoride or organic acids (for example tannic acid, benzoic acid or succinic acid) but colorings are known.

Documents (Art. 7, Paragraph 1, Paragraph 2, No. 1, Clause 3 of the Andetungsges. V. 4, 9.

909807/1041

The valuable properties of these known, homogeneous compounds have led to the development of so-called "colorless carbon papers" and variations thereof. Lump printing papers and copier materials of this type are described, for example, in U.S. Patent 2,505,470. The paper or other material tdrä with a solution of N-bis-Cp-dlsiethylaaiinopiienyl) -methylaniline (as chromogenic electron clonator) in the form of discrete particles in combination with a solid insulating material, such as an organic hydrophilic film-forming material, and an acidic clay coated * When applying pressure by means of a pen or as a blow, for example with a typewriter type, the homogeneous connection is combined with the. acidic clay that acts as an electron aceptor, creating a blue-colored impression. In the United States Patent 2,548,366 are materials of this type described in which the RUekfläohe Each cover sheet of a Ansah! superimposed sheets are coated with a dispersion of a suitable solution of a homogeneous substance in a crackable hydrophilic colloidal film and the next sheet below is coated with an acidic clay serving as an electron acceptor or contains this as a filler. When applying pressure by means of a pen or a typewriter type, a colored imprint is created on the surface containing the acidic clay at the pressure or abutment points.

Such electron donors in combination with acidic electron acceptoxes have also been used for other purposes. All previously known compounds of this type (such as crystal violet lactone) and the. in the US Patents 2,474,084 _s, S-described compounds 2 505 470 828 541 _t 2-828342, 2900 588, 2948755, 2 735 98I, 98I 2 738 and 2,983,756, however, only dyes erzsugen iss

909807 / Ί041 _BAD

the blue to green region of the visible spectrum, and there are so far no compounds are known with which yellow, red or black dyeings can be ersielt, although it is desirable SuSerst _f the area of the dyeings to extend such that it also includes such dyes.

It has now been found that certain new 3> 2 ~ disubstituted 5H ~ indoles possess properties that make them suitable for the above Make the mentioned uses excellently suitable and in particular the production of yellow to red colorations enable.

The invention relates to a method for production new jJH indole derivatives which can be used as color precursors in duplicating materials and which are only weakly colored or are practically colorless on contact with acidic electron receptors however, intense colorations in the yellow to red area of the visible spectrum result and the general Formula:

(CH-CH) _n -A

wherein R is halogen, alkyl, alkoxy, alkylsulfonyl or sulfamoyl, χ 0 or a whole number from 1 to 4, each of the radicals R ¹ and R is alkyl or aralkyl, A is either

7 ~~

Sr

909807/1041

wherein one of the radicals X and Y is hydroxy, alkanoylamino,

linfklkyl-H-cycloalkyl-aBiino, N-AXkyl-H-cyano-M-Älkyl-H-chloroalkylamino or phenylamino and the other is hydrogen, halogen, hydroxy, alkyl, alkoxy or aralkyl and the phenyl ring nooh with further halogen, alkyl -, nitro or alkoxy radicals can be substituted, or

wherein each of Fr and R is hydrogen or alkyl or both together form a condensed benzene core, R ^ is hydrogen or alkyl and R is alkyl, alkoxy, phenyl or naphthyl and η is an integer from 1 to 5, which is characterized in that a compound of the formula:

rait a compound of the formula i

Q-A

wherein one of the radicals P and Q is hydrogen and the other is OHC- (CH = CH) _n-1 .

909807/1041

The new compounds have a conjugated odd-numbered methine chain that connects the indolynitrogen with the nitrogen atom in residue A. In contrast to the cyanine dyes, in which a tertiary or quaternary nitrogen (or an oxygen and a quaternary nitrogen) must be bound via an odd-numbered methine chain, the precursors of the present invention have two tertiary nitrogen atoms or a tertiary nitrogen atom at the ends of the methine chain and a secondary nitrogen atom.

The preferred compounds of the invention are weak colored or practically colorless »If it is protonated, eh, brought into contact with an acidic electron absorber will »produce deep yellow or red stable and light« · real color tones.

The new compounds are in many different solvents soluble. Not only do they have considerable solubility in common solvents such as benzene, toluene, Dioctyl phthalate and chlorinated® diphenyls, but also in petroleum fractions * such as light petrol used as solvents, white mineral oil and gasoline, as well as in alcohols such as methanol, ethanol, diethylene glycol and glycerine. This makes the compounds of the invention super ordinarily valuable, and the range of colorations used in the above mentioned reproduction materials can be achieved can be expanded considerably. I.e. the new connections can be used to generate stable deep yellow to red colored compounds through contact with blue electron acceptors or acidic materials that cause the indolyl nitrogen to protonate. This protonation

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leads to the formation of Rssonarus structures with the development or intensification of color in the protonated compounds, whereby deep hues are generally obtained.

For example, the new compound is of the formula

C - CH - CH

which is practically colorless, upon contact it is acidic protonated, and the resulting compound is the following deeply colored rssonan hydride is converted;

CH,

9 "

JS

C]

CH = CH <

Γ \

CH,

909 807/1041

According to the colorless connection of the structure?

OH,

= CH - CH = CH

after protonation into the strongly colored resonance hybrid:

+ M «CH ar CH -.CH a CH

)H

»CH - CH a CH - CH

overfilled, and the connection of the structure?

909807/1041

BATH ORIGINAL

14 * 5447

After contact with an acid, it produces the Hesonansis sysid

H η C-

Among the substituents that may be present in the radical A, include »chlorine, bromine, fluorine, methyl, ethyl, propyl, butyl, Äßiyl, Hexyl, Methoxy, Äthoxy, Propoxy, Butoscy ^ Araoxy, Hexoxy, Phenyl, maphthyl; methylsulfonyl, ethy! sulfonyl, pheny! sulfonyl

909807/1041

m O, «

Kaphthyleulfonyl, Sulfasioyl, NjN-Diraethylsulfonajnido and H «Ethy lsulf onamido.

Examples of the substituted amino groups X or Y are acetamido, butyramido, dimethylamine) -, DiUt hy lam ine-, N-a-Cyenoäthyl-methylamino-f, H-a-Chloratbylmethylamino-, M-cyelohexyl-propylamine residues.

Particularly preferred are compounds in which the radical A has the formula

where X βIn ^. Sydroxyl-, (lower alkanoyl) -amino-, di- (lower alkyl) -amino- or N- (lower alkyl) -N «(Ö * cyanoäthyl) · aainogrupp «, or the formula

where R is a low molecular weight alicyl radical, low molecular weight alkoxy or phenyl radical and ΈΡ is hydrogen or a low molecular weight alkyl radical. The term "low" or "low molecular weight" means * that the Oruppo in question contains no more than six carbon atoms.

909807 / ICU 1

ίο -

The compounds according to the invention include those in which the benzene nucleus is free of substituents and those in which it has 1 to k identical or different inert subatifcutents R, for example halogen, alkyl and alkoxy radicals, especially those which are of low molecular weight Derive hydrocarbons, carry alkylsulfonyl * especially methyl or ethylsulfonyl and sulfamoyl radicals.

Preferred compounds of the present invention bind free of chromophoric groups and of groups containing a hydrogen cation because these preferred compounds are pale or practically colorless and therefore special well suited for use in materials and systems of the type specified above *

Those which are particularly suitable for the purpose indicated above Compounds according to the invention are those in which R is hydrogen, R and R are alkyl radicals, in particular low molecular weight hydrocarbon alkyl radicals, are and Fr and R and Ir are alkyl. Particularly noteworthy are compounds of the following formula:

909807 * 1041

wherein S and & low molecular weight alkyl radicals., preferably KöttKyl or Ethyireste, and X is a hydroxyl ·, (low. Alkaooyl 1-SBIiIiO-, preferably acetamido- or di- (lower. Alkyl) aaino-grttppe, preferably a dimethylamine or diethylasrino group is.

Examples of these and other compounds according to the invention are 2- [4- (N-ß-cyanoethyl-N-ß! Etfeyl) -eminostyryl] -3, 3-diiRethy 1 -3H-UBdOl; 2 ~ (4, H, N-DiMthylaminostyry 1) -3,3-diraethyl ~ 3H = indolj 2- (4-Hydroxyst) 2- (4-Aoetamidoetyryl) «3,3-diRi®thyl» 3H «in (aol .3 S-C2- (i ~ B 2-paenyl ~ indoi-3-yl) -Mthylenl - ^ i ^
2- (4-H, Hf-Diiaethylfiminostyryl) «Yes ^

2-C2- (i-S§ethyl-indol-3-yl) -ethylenej-3 * 3 and 2- [4- {4-H, H -dimethylaniinophenyl) -1,5-butadienyl] »3 * 3-diraethyl-3H-indole.

The simplest method of carrying out the process of the invention with regard to the availability of the starting materials and the required apparatus consists in the condensation of a 2-methyl-3 »3-disubstituted 3H-xndola with a suitable aminoarylaldehyde, hydroxyarylaldehyde or heterocyclic aldehyde in the presence of an acidic condensation agent . The condensation is preferably carried out in the presence of an inert solvent such as isopropanol and at a temperature between 50 and % B (K.

The condensation of the indole with the aldehyde is indicated in advance in the presence of an acid such as phosphoric acid, salt acid, sulfur Felsic acid, bisrastinic acid, acetic acid or another acid with a pK value of at least about 10.

909807/1041

Bar catalyst is preferably present in an amount that is equal to the amount of 3H ~indole Qulmolar. In the presence of smaller amounts, the reaction rate is reduced, while the presence of an amount greater than about that 10 times the molar equivalent no major influence on the Reaction rate as the preferred amount.

Preferably, a solvent is used which does not react with the reactants, but in which one of the Reaction participant is soluble or both co-action participants are soluble. In most cases, compounds containing hydroxyl groups, such as aliphatic alcohols, for example, are suitable Methanol, ethanol, propanols, butanols, pentanols, hexanols, heptanols and octanols, and glycols, for example ethylene glycol, diethylene glycol and trimethylene glycol. Ethers, such as diethyl ethers, can either be used alone or in a mixture with a hydroxyl-containing solvent or more solvents containing hydroxyl groups be used. In addition, the acidic condensation agents, for example acetic acid, can have a double function exercise, i.e. both as catalysts and as solvents to serve.

The temperature at which the process is carried out can vary within a wide range. The reaction temperature is not an essential feature of the process, but can, within certain limits, accelerate the condensation, so that the reaction time is kept within an appropriate range. Accordingly, temperatures in the range from 50 to IBO ⁰ C are usually preferred. If the reaction is carried out at temperatures below about 50 ° C., it takes an unusually long time to complete, while at temperatures of

ORIGINAL BATH 909807/1041

considerably more than Ι8θ <ΰ decomposition and Hebsn reactions will predominate and may reduce the yield of the desired product.

A preferred method of preparing the new compounds consists in using a mixture of practically equimolar amounts of a 2-Metfayl ~ 2 * 3-disubstitulart®n ~ 3H 'incrol3 and an o- or p- (substituted amino) - "aryl & ldehyds example Xsopropanol * erhitat in solution in a solvent" with the slow addition of a solution of about 2 molar proportions of phosphoric acid in the same solvent to aer boiling solution at reflux and "to end the mass ausr®iahend long ^ to the condensation further em reflux for Boiling heated. The product formed is separated from the mother liquor®, for example by decanting, and dissolved in water. The solution is thought to be alkaline compared to Brilliant Yellow. The product which separates out is purified by dissolving it in acetone, reprecipitation by dilution with dilute aqueous alkali metal hydroxide, "filtered off", washed with water and dried.

The following 2H-indoles are suitable for use in this process 2,3,3-Triraethyl-3H-indolj 2-Mefchyl-3,2-di-

2- »ethyl-5-hexylsulfonyl-3H-indole and J-

The following aryl aldehydes and heterocyclic aldehydes are suitable for use in the process:

lit
07/1041

hexyl-H ^ propyl) -aminofoensaldshyöj

4 "(8" a "Chlorafcbyl ~ 8" rnefci35rl) 4 «. (JS» Phenyl) «" Srsinobensaidshydj

S-Hyöroxy »3 * 5 -dimeti ^ lbeasaldelayd | 4-I | ydro3 £ y »2J ₅ 3 ₅ 6-fcrim © thyI-bensaldehyds S ^ S-Dihydro ^ ybensaldeh pyrrole« - ^ «car & ex & ldehydi SMethyl« 1 »

s 2- »Mstho.xy ~ in

ph <sny3.) -h © ptatri © nal urid 9- (p-diethylaminophenyl) -nonatefera ~ enal.

The Brfindiaig will be explained in more detail below with the aid of examples explained. Parts and Prosentangafcsn related to see on weight; unless otherwise stated. For the most part bszelofcnsn the volume by weight of the same number share water of 4 ^ © ingested wii? d «

Example 3L

To a refluxing mixture (temperature about 94 parts of 4- (K-ft-0yanoSthyl- ⁱ I ° methyl) -sfflinobenaaldehyde

90 98 0 7 / to 41

* 15

and 80 parts by volume of 2,3,3-trimethyl-3H-indole in 3,000 parts by volume of isopropanol, a solution of 70 parts by volume of 85% orthophosphoric acid in 130 parts by volume of isopropanol was added dropwise over the course of one hour. I) The initially pale yellow solution quickly turned deep red and a fiery precipitate appeared in the mixture. The mass was refluxed for about four hours and then cooled to ambient temperature. The supernatant solution was decanted off from the tar-like product, and the product was washed twice with 100 parts by volume of isopropanol each time. The washed product was dissolved in 1000 parts of warm water, and the solution was taken after cooling to the temperature of the environment by the addition of 65 Volumäeilen aqueous sodium 'hydroxide 50 ⁰ Bs' against Brilliant Yellow alkaliseh. The supernatant aqueous liquid was decanted from the tarry precipitate, and the precipitate was washed by decanting with water. The tar was then dissolved in about 600 to 650 parts of acetone, and the resulting solution was added dropwise to 5000 parts of water of about 20 "€ which contained 40 volumes of 50 ° C aqueous Hatriurahydroayd". The resulting yellow pestilent slurry was slurried again in 2000 parts of water containing 20 parts by volume of aqueous sodium hydroxide at 20 ° Be, and the slurry was stirred for a few hours and then filtered.The filter cake was washed with water and then dried in vacuo at 50%.

In this way, 137 parts of light yellow® crystals (analysis: & $, calculated 12.6, found 12.04, P 10S-10S / C, uncorr.} obtained from 2- [4- (N «S-eyanoätliyX" N «! sethyl) -arainosi; r / r-ylj ~ 3» 3-diiriethyl «-3H ° indole the formal:

909807/1041

* 16 -

- CH »CH

passed and in methanol and other low molecular weight Alcohols were soluble. If an i # alcoholic solution on filter paper soaked with succinic acid, was applied, it was momentarily a leutonde, deep red color generated.

Example 2

In the manner described in Example S. 8.9 parts of 4 "N, *? - diethyleninobenzaldehyde with 8.0 parts of 3H-indole were converted to 2" (4 _> N, N
indole of the formula:

c -c:

C - CH - CH-

condenses.

90980771041

- 17 ~

If a drop of an Iji-igon alcoholic solution this Product on filter paper »that soaked with succinic acid was, was upset »so was momentarily a shining, deep bluish-red color produced.

In exactly the same way, 2-methyl-3 * 3 ~ dibenzyl-3H-indole can be mixed with 4- (11 «cyclohexyl-N-propyl) -aniino-benzaldehyde or 2-H, H-diraethylamino-4-benEylbenzaldehyd condensed werdec> being the compounds of the following formulas are formed:

respectively.

C - CH «CH

In contact with acids, these compounds are colored brightly.

909807/1041

Also, ^ i ^

with *! - Dimetfoylamino ~ annamal <3 © hyd or 5- (pphenyl) -pentadienal au ' compounds ά®ν Formeint

C ₆ H ₁₃ SO ₂

i ^ V - c - o _m ^

b _M .CH ^ CH-CH-CH'-CH = C

di © become brightly colored on contact with acids, condensed.

Example 3

A mixture of 6.1 parts of p-hydroxyfcanaaldehyde and 8.0 parts 2,3 * 5-Trir «0tliyl-3H-indole was, in 100 parts by volume iso ~ propsnol dissolved, and the solution was heated to boiling under reflux. During the following 20 minutes, it became a solution of 7 parts by volume of 85% orthophosphoric acid in 15 parts by volume Isopropanol drop by drop from the boiling point on the reflux Solution added. When the acidic solution was added, it separated

- ·. BATH

909807 h 041

an orange pest from the mixture. The mixture was refluxed for about 4 hours and then on the Ambient temperature cooled. The product was filtered off and the filter cake was made with about 50 parts isopropanol washed. The washed product was about 16 hours in 400 parts of water, the 5 parts by volume of aqueous Contained ammonia, slurried again. The slurry was filtered and the filter cake was dried.

11 parts of 2- (4-hydroxystyryl) -5,3-thinethyl-3H were obtained indole of the formula:

- CH * CH

in the form of slightly yellow crystals of F 214-216 ⁴ C (uncorr.). (Analysis: £, calculated 5.32, found 5.29) “It was soluble in methanol and other low molecular weight alcohols. If a 1 to 1 alcoholic solution was dripped onto filter paper that was soaked in succinic acid, a bright, deep yellow color was produced momentarily.

In exactly the same catfish, 6-chloro-2,3,3-trlmethyl- ^ H-> indol-2 or _4-t Xthoxy 3,3-trimethyl-2H »indole with 4-fluoro-2-hydroxybenzaldehyde to give the compounds of the formulas:

909807/1041

^ C ~ CH = CH- / \ h OH

which are colored bright on contact with acids, condenses will.

3-Benzyl-2,3-dimethyl-3H-yneol with 4-hydroxy. 3-methoxyben2aldehyde can also be used or 4-Hydro: Ky-2, 3 »6-trimethy: L-benzaldehyde to connections of the formulas «

90980 7/1041

which are strongly colored on contact with acids, condenses will,

Example 4

A mixture of 8.2 parts of p-aoetamidobenzaldehyde and 8.0 parts of a ^ S-triinethyl-JH-indole was added to 100 parts by volume of isopropanol boiling under reflux. To the refluxing solution was added over SO minutes, a solution of 7 parts by volume of 85 ~ # Lger orthophosphoric acid in It parts by volume of isopropanol, and ■ the resulting mixture was about 16 hours and boiled m reflux. The mass was cooled to ambient temperature and the supernatant alcoholic solution was decanted from the tarry product. The product was dissolved in 500 parts of hot water and the solution was cooled to about 25 ° C. and made alkaline to bright yellow with aqueous sodium hydroxide. The slightly yellow-brown precipitate formed was filtered off, washed well with water and dried in vacuo at 50 ".

This gave 2 ~ (4 ~ aetamldostyryl) 0 <«3 ~ dimethyl ~ 3H-indole of the 7om» left

4, 909807/1041

C -CU

C ** CH «CH

in the form of slightly yellow-brown crystals which decomposed at 147.5 °. (Analysis: N $>, calculated, 8 ₃ 70 * found 8.77) - "It was soluble in low molecular weight alcohols. When a 1 $ solution was applied to filter paper soaked with succinic acid, it was instantaneous a deep yellow-brown color,

ϊη exactly the same manner, 5-SulfaRiyi-2 _J 3/5-triniethyl-3K = indole with 4- {N 'phenyl.) ~ aminobenzaldehy-d or 4' {Wa-chloroethyl-W-methyl) -aminobenzaldahyd to the connections of the formulas:

909807 ( ¹ IOiI

BATH ORIGINAL

Cl

which become strongly colored on contact with acid, condensed will"

Example g

A mixture of 7.9 parts of 2, JS; 5-trimethyl-3H-indole and 11.7 parts of 1-Wethyi-2-pnenylindol-3 «carbo3ialäQiiyoi in 100 parts by volume of xeopropanol was heated to the boil and held at reflux. Became the boiling Oemisch within about 15 minutes a solution of 7 parts by volume of 85 # orthophosphoric acid in 15 parts by volume Isopropanol added. The resulting mixture became 43 hours heated at reflux and then for about 16 hours at the Ambient temperature. The tar-like condensation product thus obtained was about 200 Parts of acetone were dissolved, and the solution was divided into 1000 parts Water, which contained about 10 parts of sodium hydroxide of 50 Be, poured «The volatile part of the aqueous oil “Ischee was made by heating the mixture on a steam bath dampened, and the remaining red tarry Oil went into a semi-solid after standing for about 16 hours Mass upper. Ss was then dissolved in about 175 parts of acetone, and the aqueous solution was dissolved in about 1000 parts of water with the addition of about 5 parts of sodium hydroxide

ft

9807/1041

poured. The aqueous mixture was on a steam bath heated to drive off acetone and the aqueous residue allowed to stand for about 16 hours. The solid precipitate was filtered off from the fatty mixture and at $ <WJ im Vacuum dried.

S-Ca-il-3,3 «diethyl.3H-indole was obtained of the formula a

In the form of a slightly yellow solid of F 64-7i <€ (uncorr.) »( Analyze Ujt, calculated 7 * 5 * found 1» 2). Ee was liJslioh m low molecular weight alcohols with the formation of slightly yellow solutions. When a drop of a 1% solution in denatured ethyl alcohol was applied to filter paper »which was soaked in succinic acid, a deep orange color was almost instantaneously created»

BATH ORIGINAL

909807 * 1041

In exactly the same way, 2 ^, 3-Trifflethyl-5H-indole alt S-iletliyl-1-pn ^ nylpyrrol ^ -earboxaldeshyd or 1-Kthyl- SHiHMipiifclqrliiidol-5-carboxaldQhyd to compounds of the formulas:

the b «i contact with acids stixk colored« are condensed.

& * A · « BCK wmrwen Oenieeh of 7.9 ropes of 2,3 # 3-Triraethyl- and 11.7 parts of 1-methyl- ε-phenylindo 1-3-oarboxin 100 Voluetellen of glacial acetic acid was one drop by drop

90980 ^ 1041

Lorning of 7 parts by volume of orthophosphoric acid in 15 parts by volume of glacial acetic acid was added. The Gemiseli was erteitst and at RüekfluÖ to 114 ⁰ C for 4 hours b © l kept this temperature. The mass should be allowed to cool to glimmering temperature and then poured into 750 parts of water and made alkaline by the addition of moderate matrix hydroxide. The Danish must remove the white tar from the absolutely defi-red tar. Bar tar made in about 40o parts. Aöeton dissolved, tmd the © solution miMe "after it was filtered (sludge-filtered) * in 2500 parts of water" to which about 10 Ts-Ue of sodium hydroxide of 50 ° was poured *. At ¹ see separating brown * yellow bodice was filtered off and applied in ®tw & 120 parts Äeefcoü. This © solution was divided into 1000 parts of deness 5 - ^ eil® Natriumlsyärosyd voss 50 ⁰ Bs'

were «poured, and the mixture was stehmi gelae @@ si _? The mass was heated on a steam bath "let" drive off the aentoii "" and the residue was then left to stand for about 16 hours. "The solid obtained was filtered off and ^{vacuumed at 50 8} C"

The Psodulct who is a light yellow pest from F

calculated 7 «5« found 7 #?). His Infrawar that of the product \ ⁷ on Example 5 is deep orangefarben® after dissolving in alcohol and applied on filter paper colorations "

The new ¥ arbinäungen result from contact with an acid

deep yellow to red © shades, ape »si © the ÄiiadeliKUKg d ^ s Bevaiohee der FSrbungen » dl® alt chromogenic electron donors can be obtained can «over there» completely visible gablet from Maub to red.

908807/1041

■ - 87

In addition, the compounds of the present invention enable the generation of black colors in the novel red and yellow chroaogenic sheet metal donors with known compatible chromogenic electron donors " those blue on contact with acidic electron receptors until green shades result in "mixed up" Sas will illustrated by the following example «

Example 7

The following compounds were mixed with one another in the specified proportions:

55 ropes of the red generating compound of Example 1 15 parts of the gslb generating compound of Example 3 30 parts of 4- [bis- (p-dira9thylaminophenyl) methyl] -morpliolin (Described in U.S. Patent Very * 2,981

If there is a solution of the mixture in an alcohol, For example, denatured ethyl alcohol, old paper that has been treated with clay or succinic acid »in contact is brought, then one develops in about one minute intense black color.

Instead of the S, 3i3-3? Riraethyl ** used in the examples 2® *> i & dole and aldehydes can also be other suitable 2-methyl-3,3-disubstituted 3H-indoles and aldehydes * for example the * listed above can be used. Instead of the aldehydes, it is also possible to use the corresponding acetals or related aldehyde precursors or the corresponding methylenediochlorides or methylenedi bromides, for example 4-Aoetajnidobenzal-ohlorld or ^ Dimethylamine benzal-brotnidj can be used.

909807/1041

Furthermore, the new compounds can be prepared by one of the reverse condensation described in the examples, ie by adding a 2- (2 * 3 * ¹ di-substituted 3H-indolylidene) -acetaldehyde with a suitable eyelial component which gives the desired 2nd -ottiega-substituted vinylene substituents, preferably under the influence of an acidic catalyst or condensing agent and condensed in a suitable solvent »

For example, S- (3,5-dimethyl-3H-indolylidene> acetaldehyde can be converted with JH-indole to 2- [2- (indol-3-yl) -ethylene] -3,3-dimethyl-3H-indöl _f or with others suitable, active hydrogen-containing compounds are condensed.

BATH

909807/1041

Claims (1)

P'a't e'nt aftsp rΰ a he 1. Compound of the general formula: wherein R is halogen, alkyl, alkoxy, alkylsulfonyl or sulfamoyl 1st, χ 0 or an integer from i to 4, each of the radicals R and R is alkyl or aralkyl, A is either wherein one of the radicals X and Y is hydroxy, alkanoylamino, Dialkylwnino, H-alkyl-N-cyoloalkyl-aaino, N-alkyl-N-cyano-itylaaiino, N-alkyl-N-chloroalkylamino or phenylamino and the other is hydrogen, halogen, hydroxy, alkyl, alkoxy, or Aralkyl let and the phenyl ring nooh with further halogen, Alkyl, vitro * or alkoxy radicals can be substituted, 909807/1041 Documents ₍ a ". . _v . 4.9. . "5 4 where each of Br and H is hydrogen or alkyl or both together form a fused benzene nucleus, R ^ is hydrogen or alkyl and R ^ is alkyl * alkoxy ,, phenyl or ifaphthyl and η is an integer from 1 to 5 .. 2, connection according to address I * dad urehge te e el η ζ e lehnst, daö R chlorine, lower alkyl * lower alkoxy »lower alkylsulfonyl, pheny, sulfonyl or sulfonyl, for and R each lower alkyl or benzyl, A 2» or Λ -Kyaroxy-, lower alkanoylarsino · © der [N- (nisörig alkyl) -Bf- (cyano-low alkyl)] - aminopheBylj, χ O or 1 and η is an integer from 1 to 5 « 3 * A process for the preparation of novel as Farbprecursoren in VervielfSltiguxigsiiiateriallen usable 3H-Inöolderivate, oils only weakly colored © of which are substantially colorless upon contact * acidic Kiektronenaeceptoren silfe jedooh intensive Flrbiangea in yellow to red region result of the visible spectrum and dl © general ^formula: BAD ORIGINAL 90980? Ii'104 1, Λ > \ H45U7 3t wherein R is halogen, alkyl, alkoxy, alkylsulfonyl or sulfaraoyl, χ is 0 or an integer from 1 to 4, 12th
Each of the notches R χχ ^ ά R alkyl or aralkyl is _tf A either in which one of the radicals X and Y is hydros, alkanoylamino-dialkylaaiino, H-alkyl-lJ-cycloalkylamino, N-alkyl-Nroyanoethylamino, N-alkyl-K ^ hloralkylamino or Phsnyleinlno and the other is hydrogen, halogen, Hydrojiy, Alkyl _? Alkoxy or. Aralkyl solder and the phenyl ring noeli can be substituted with further halogen, alkyl * - * nitro or alkoxy radicals, or BATH 909807/1041