DE3233224A1 - FLUORANE COMPOUNDS, METHOD FOR THEIR PRODUCTION AND USE THEREOF - Google Patents

Description

Henkel, Pfenning, Feiler, Hänzel & Meinig "patent attorneys

European Patent Attorneys Admitted to the European Patent Office

Dr. phil. G handle. Munich Dipl.-Ing J Pfenning. Berlin Dr rer. nat L Feiler. Munich Dipl -Ing W. Hänzel. Munich Dipl -Phys. K. H. Meinig. Berlin Dr. Ing.A. Butenschon. Berlin

Mohlstrasse 37
D-8000 Munich 80

Tel / 089 / 982085-87 Telex: 0529802 hnkld Telegrams ellipsoid

A7O51-O3

SUMITOMO CHEMICAIi COMPANY, LIMITED,
Osaka, Japan

Fluoran compounds, process for their
Manufacture and use of the same

Fluoran Compounds> Process for their manufacture and use thereof

The invention relates to fluoran compounds which can be used as dyes for recording materials and to a Process for their manufacture.

With increasing advances in the field of information recording and transmission, there is an increasing need for pressure- or heat-sensitive recording materials in which a color-forming reaction takes place through contact between almost colorless electron donors and almost colorless electron acceptors. As a rule, a pressure-sensitive recording material consists of an upper layer and a lower layer. The top layer is obtained by dissolving a white electron donor dye (hereinafter referred to as "color-forming substance") in an organic solvent . Emulsifying the resulting solution until the particle size is a few μΩ. is "converting the emulsion into microcapsules with the help of a polymeric compound" such as gelatin and the like, and applying the microcapsules to a layer support. The lower layer is obtained by applying an electron acceptor (hereinafter referred to as "color developer") to a support. When the two are placed on top of each other in such a way that their coated sides are aligned "and a pressure is applied to the whole thing with the help of a pencil", a typewriter, and the like

When exercised, the microcapsules break, releasing the color-forming substance from the capsules and comes into contact with the color developer. An image-appropriate color-forming reaction then takes place away.

Most conventional heat-sensitive recording materials are constructed in such a way that a color-forming substance and a color developer (e.g. bisphenol A) _1, optionally together with a solid flow agent to prevent mutual contact in a binder, e.g. a polymeric substance such as polyvinyl alcohol, are dispersed on a substrate . When the heat-sensitive recording material is heated, at least one component, namely the flow agent, the color-forming substance or the color developer, melts, whereby the color-forming substance and the color developer come into contact. Here, too, a color-forming reaction then takes place with image-appropriate recording.

In the case of chargeable thermosensitive recording materials is between the support and the color-forming layer, color-forming substance, color developer and optionally a conductive layer with a conductive substance is provided to a flux. If you can When the recording material is charged, heat is generated, with a color-forming reaction resulting in an image-appropriate recording

³⁰ tion takes place.

It now insists that by color forming reaction between the color-forming substance and the color developer when exposed to pressure or heat The resulting image may also be suitable for copying purposes

Should there be an increasing need for color-forming substances that produce a black or blackish image. In principle it is possible to »produce black or blackish images by using different mixes suitable color-forming substances of different tones. The disadvantage here is that the used color-forming substances differ in their speed of color formation and (after the picture once emerged) in light and moisture resistance differ, so that the color of the image may change when the recording material is stored. Ss There has been no lack of attempts to produce black or black using a single color-forming dye to produce blackish images. However, there is still no dye that meets all of the requirements, e.g. Tint, authenticity, color formability, costs and the like are sufficient.

If you have a compound of the general formula:

HCH

(D

where mean:
X is a halogen atom;

A an optionally halogen-substituted benzene or naphthalene nucleus,

E * an alkyl, alkoxyalkyl, cycloalkyl, phenylalkyl or phenyl radical,

E is an alkyl »alkoxyalkyl or phenylaityl radical or ir and R together are a remainder of the formulas:

p- or -C ₂ H ₄ OC ₂ H ₄ -

mlt ρ = 4 »5 or 6, where the following applies:» that the phenyl radicals Br and R can optionally be alkyl or halogen substituted »and

R and R individually each optionally an ether bond containing alkyl radical »cycloalkyl radical or phenyl radical or together with the carbon atom of the methine radical a cycloalkyl, tetralinyl or indanyl radical,

wants to produce »one can think of it» an imidver-

binding the general formula:

R0 /> - NHCH < ₂ 20

1 2

in which R, R and X have the meaning given and R is a hydrogen atom or a short-chain one Alkyl radical, with a compound of the general formula:

H COOH

where R »R and A have the meaning given,

to implement.

For the preparation of imide compounds of the general formula (IV), for example that from JP-OS is suitable

ι 142 693/80 known method. In this procedure the amino radical of 3-chloro-4-aminophenol is alkylated with an alkyl bromide or alkyl tosylate »but In addition to the monoalkyl compound, a dialkyl compound is also formed as a by-product. In addition, one remains larger amount of amino compound not converted. The by-product and the unreacted amino compound are difficult to separate. Ultimately, therefore, the desired imide compound is not obtained in high yield and high purity.

In addition, only alkyl bromides or alkyl tosylates can be used as alkylating agents, so that the structure of the desired imide compound is also very limited.

The invention was now based on the object "a method for the production of which can be used as dyes in heat- or pressure-sensitive recording materials To create dyes, especially fluoran compounds, via novel imide intermediates, the desired Provides dyes in high yield and purity.

It has now been shown that the imide intermediates which make the process according to the invention possible of the general formula (IV) in a most expedient manner by reductive alkylation with the aid of a ketone compound can produce. If you have these imide compounds

³⁰ then as intermediates in the manufacture of

Fluoran compounds of the general formula (I) are used, the latter are obtained in high yield and high purity.

The invention thus relates to a process for the preparation of fluoran compounds of the general formula:

, R

HCH <

(D

where mean:

A is an optionally halogen-substituted benzene or naphthalene nucleus;

X is a halogen atom;

1 2
R and R individually in each case an alkyl radical »cycloalkyl radical or phenyl radical, which may have an ether bond, or, together with the carbon atom of the methine radical, a cycloalkyl» tetralinyl or indanyl radical;

R ^ an alkyl, alkoxyalkyl, cycloalkyl, phenylalkyl or phenyl radical;

R is an alkyl, alkoxyalkyl or phenylalkyl radical or R * ¹ and R together are a radical of the formulas:

H ₂ -

" ^(CH 2 ⁾ p" or -C

with ρ = 41

R ⁵ and R ⁶ if necessary

5 or 6, with the proviso that the phenyl radicals

can be alkyl- or halogen-substituted, which is characterized in that one an aniline compound of the general formula:

RO

■ o-

(ID

NH.

wherein Σ has the meaning given and R stands for a hydrogen atom or a short-chain alkyl radical, with a ketone compound of the general formula:

R ³

(III)

wherein R and R correspond to the meaning of R and R. or one in the course of the conversion into a radical R and

2
R represent transitioning group, with catalytic and reductive alkylation to form an imide compound of the general formula:

15th

1 2
wherein Σ, R, R and R have the meaning given, allowed to react and that the resulting imide compound of the general formula (IY) in the presence of a dehydrating condensing agent with a compound of the general formula

Λ - COOH 25

c ^ "~ r ii \

(V)

where A, R ^ and R have the meaning given, implements.

According to the invention, new fluoran compounds of the general formula are thus obtained in particular:

35

. Al · ·

CO

NHCH

(VI)

where mean:

X is a halogen atom;

A is an optionally halogen-substituted benzene or naphthalene nucleus;

R, R can optionally be alkyl- or halogen-substituted, and
7 8

R, R individually each optionally an ether bond having alkyl radical, cycloalkyl radical or phenyl radical or together with the carbon atoms of the methine radical a cycloalkyl, tetralinyl or indanyl radical, with the proviso that the total number of carbon atoms is three or

7 8

is more if both radicals R and R are alkyl radicals stand and A represents a benzene nucleus.

Halogen atoms which can be represented by X are, for example, chlorine, bromine, iodine and fluorine atoms, in particular chlorine-UBd Bromine atoms. Examples of short-chain alkyl radicals which can be represented by R are alkyl radicals having 1 to 4 carbon atom (s), e.g. methyl, ethyl, propyl or butyl radicals or their isomers.

If the radicals R- ⁵ and R ⁴ in the general formula (III)

1 2 correspond in meaning to the radicals R and R,

1 2
the alkyl radicals represented by R and R can have one or more ether bond (s) or one or more

Contain cycloalkyl or phenyl radical (s). Examples of such alkyl radicals are those having 1 to 8 carbon atoms (en). The phenyl radical can also be replaced by at least one short-chain alkyl radical and / or at least one

5 halogen atom may be substituted.

1 2
Examples of radicals R and R are methyl, ethyl, propyl, isobutyl, amyl, methoxymethyl, »methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, benzyl, p-chlorobenzyl, phenethyl, phenylpropyl , Benzyloxymethyl, phenethyloxymethyl, benzyloxyethyl, cyclohexyloxymethyl, cyclohexyloxyethyl or phenoxymethyl radicals.

1 2 As already mentioned, the radicals R and R can be taken together

with the carbon atom of the methine radical form cycloalkyl, tetralinyl or indanyl radicals which are optionally substituted by short-chain alkyl radicals, alkoxy radicals or halogen atoms.
20th

If in the general formula (III) the radicals R ^ and

A 12

R for in the course of the implementation in residues R or R uTergoing Are residues, these can for example from vinyl, propenyl, 2-methyl-2-hydroxypropyl or ■ 2-methyl-2-methoxypropyl radicals exist.

Examples of aniline compounds of the general formula (II) which can be used according to the invention are J-chloro-A-aminophenol,
J-chloro-A-aminoanisole,

3-chloro-4-aminophenetol, 5-bromo-4-aminophenol, 3-bromo-4-aminoanisole, 3-iodo-4-aminophenol or 3-fluoro-4-aminophenol.

Examples of ketone compounds of the general formula (III) which can be used according to the invention are cyclohexanone » Cyclopentanone, ß-tetralone, 2-indanone »acetone, diethyl ketone, Methyl ethyl ketone, methyl isobutyl ketone, methoxyacetone, 4-methoxy-2-butanone, diacetone alcohol, 4-methoxy-4-methyl-2-pentanone, J-dimethoxyacetone, 4-cyclohexyloxy-2-butanone, 4-phenyl-2-butanone, dibenzyl ketone or methyl vinyl ketone.

The reductive alkylation carried out according to the invention is explained in more detail below. To this end For example, an aniline compound represented by the general formula (II), a ketone compound represented by the general formula (III) Reaction solvent and a catalyst are placed in an autoclave and placed therein under elevated pressure reduced temperature with hydrogen.

The ketone compound of the general formula (III) is used in an amount of 1 mol or more, preferably of 1-2 mol (s) are used per mol of aniline compound of the general formula (II).

Suitable reaction solvents are, for example, alcohols such as methanol, ethanol, isopropanol and 2-methoxyethanol and 2-ethoxyethanol, polyhydric alcohol ethers such as ethylene glycol dimethyl ether, diethylene glycol monomethyl ether and diethylene glycol dimethyl ether, dioxane, and the like used ketone compound also as a reaction solution

³⁰ means to serve.

Suitable catalysts are platinum and palladium catalysts, in particular those applied to a support Platinum. Preference is given to platinum catalysts, which are somewhat poisoned with the aid of a sulfur compound became.

In relation to the output amino connection, Expediently 1-30 Mol- # of an organic acid, for example acetic acid »added in order to dehalogenate to prevent.

The reaction takes place under a hydrogen pressure of expediently 490.5-4905, preferably 981-2452.5 kPa "at a temperature of 80 - HO ⁰ C, preferably 110-130 ⁰ C. If the theoretical amount of hydrogen is absorbed and is consumed, no further hydrogen absorption can be determined, and there is also no unreacted aniline compound present.

To isolate the desired reaction product, the contents of the autoclave are used to remove the catalyst filtered and the solvent or excess ketone removed by steam distillation. The one here Any distillation residue is treated with cold or hot water to remove soluble substances .

For further purification one can undergo a crystallization from toluene, η-hexane, etc. or a distillation under reduced pressure.

Thereafter, the resulting imide compound of the general formula (IY) in the molar ratio (IV) / (V) of 0.8-2.0, preferably 1-1.2, in the presence of a dehydrating condensing agent at a temperature of -5-90 ⁰ C, preferably from 10-60 ^° C., for a few hours to a few 10 hours, preferably for 12-48 hours, allowed to react with a compound of the general formula (V).

¹² T 22-

Then the reaction mixture is poured into water » made the whole thing alkaline and heated if necessary. This gives pale white crystals. At the Filtering off, drying and recrystallization gives a fluoran derivative of the general formula (I) in the form white crystals.

As a dehydrating agent in the synthesis of the compound of the general formula (I) from a compound of the general formula (IV) and the general formula (V) sulfuric acid, phosphoric acid, »polyphosphoric acid and the like are suitable.» preferably 85-100 # Sulfuric acid.

Suitable solvents for recrystallization are η-hexane, toluene, monochlorobenzene, chloroform, methyl isobutyl ketone » Methyl glycol, isobutanol, isopropanol, dimethylformamide, dioxane, ethylene glycol dimethyl ether and the like either alone or in combination of two

20 or more.

Examples of those which can be used according to the invention as intermediates in the preparation of the fluoran compounds Imide compounds of the general formula (IV) are: 2-chloro-4-hydroxy-N-cyclohexylaniline, 2 ~ bromo-4-hydroxy-N ~ cyclohexylaniline, 2-fluoro-4-hydroxy-N-cyclohexylaniline, 2-iodo-4-hydroxy-N-cyclohexylaniline,

2 ~ chloro-4-hydro:! Cy-N-cyclopentylaniline, ³⁰ 2-chloro-4-hydroxy-N- (ß-tetralinyl) -aniline, 2-chloro-4-hydroxy-N- (2-indanyl) - aniline, 2-chloro-4-hydroxy-N-isopropylaniline, 2 ~ chloro-4-hydroxy-N- (1'-methylpropyl) -aniline, 2-chloro-4-hydroxy-N- (1'-ethylpropyl) - aniline, ³⁵ 2-chloro-4-hydroxy-N- (1, 3'-dimethylbutyl) -aniline,

l 2-chloro-4-hydroxy-N- (1 ^f -methylhexyl) aniline,

2-chloro-4 ~ hydroxy-N- (1 '-methyl-2' -methoxyethyl) -aniline, 2-chloro-4-hydroxy-N- (1 '-methoxymethyl-2 ♦ -methoxyethyl) -aniline,

2-chloro-4-hydroxy-N- (1 '-methyl-3' -methoxypropyl) -aniline, 2-chloro-4-hydroxy-N- (1 '-ethyl-2-methoxyethyl) -aniline, 2 -Chlor-4-hydroxy-N- (1'-methyl-2'-methoxyethoxyethyl) aniline,
2-chloro-4-hydroxy-N- (1 -methyl-2'-cyclohexyloxyethyl) -

10 aniline,

2-chloro-4-hydroxy-N- (1 '-methyl-3' -cyclohexyloxypropyl) -aniline,

2-chloro-4-hydroxy-N- (1'-methyl-2'-benzyloxyethyl) aniline, 2-chloro-4-hydr oxy-N- (1 '-methyl-3' -benzyloxypropyl) -

l5 aniline,

2-chloro-4-hydr oxy-N- (1 '-methyl-3' -phenethyloxypropyl) -

aniline,

2-chloro-4-hydΓoxy-N- (1 '-methyl-2' -phenoxyethyl) -aniline, 2-chloro-4-hydr oxy-N- (1 · -methyl-2'-phenoxy ethoxy ethyl) -

20 aniline,

2-chloro-4-hydroxy-N- (1'-methyl-2 ^f -phenylethyl) -aniline, 2-chloro-4-hydroxy-N- (1'-methyl-3 '-phenylpropyl) -ax * \ ϊη , 2-chloro-4-hydroxy-N- (1 ^t -'benzyl-2 ^f -phenylethyl) -aniline, 2-chloro-4-methoxy-N-cyclohexylaniline,

25 2-bromo-4-methoxy-N-cyclohexylaniline or

2-chloro-4-methoxy-N- (1'-methyl-3'-methoxypropyl) -aniline.

Examples of the manufacture according to the invention Fluoran compounds usable compounds of the general

30 my formula (V) are:

2- (4 '-N, N-diethylamino-2' -hydroxybenzoyl) -benzoic acid, 2- (4 '-N, NI) imethylamino-2' -hydroxybenzoyl) -benzoic acid, 2- (4 ^f -N, N- Dipropylamino-2 ^f -hydroxybenzoyl) benzoic acid, 2- (4 '-N, N-dibutylamino-2' -hydroxybenzoyl) -benzoic acid, 2- (4 '-N, N-diisobutyllamino-2' -hydr oxyb enz oyl) -b enz ο e acid,

. 3ο-

ι 2- (4 '-N, N-diamylamino-2'-hydroxybenzoyl) benzoic acid, 2- (4'-N, N-dihexylamino-2'-hydroxybenzoyl) benzoic acid » 2- (4'-N, N-dioctylamino-2-hydroxybenzoyl) -benzoic acid, 2- (4'-N-Ethyl-N-butylamino-2'-hydroxybenzoyl) benzoic acid »

2- (4'-NtN-diethylamino-2'-hydroxybenzoyl) -4-chloro-

benzoic acid »

2- (4 '-N, N-3-diethylamino-2-hydroxybenzoyl) -3 »4» 5 »6-tetrachlorobenzoic acid»
2- (4'-N, Ii-diethylamino-2 '-hydroxybenzoyl) -3-naphthoe-

acid"

2- (4 • -N, N-dimethylamino-2 ^f -hydroxybenzoyl) -3-naphthoe-

acid"

2- (4'-N, K-dibutylamino-2 ^f -hydroxybenzoyl) -3-naphthoic acid »

2- (4 '-NjN-DianLyilamino ^ ^l -hydroxybenzoyl) -3-naphthoe-

acid »2- (4'-N-Ethyl-N-butylamino-2'-hydroxybenzoyl) -3-

naphthoic acid>
2- (4'-N, N-diethylamino-2'-hydroxybenzoy3) -5- or -8-chloro-

3-naphthoic acid »2- (4'-N, N-Oiethylamino-2'-hydroxybenzoyl) -5- or -8-bromo-3-naphthoic acid »

2- (4'-N, N-dimethoxyethylamino-2'-hydroxybenzoyl) benzoic acid »

2- (4'-N, N-diethoxyethylamino-2'-hydroxybenzoyl) benzoic acid »

2- (4 '-N, N-33iethoxyethylamino-2' -hydroxybenzoyl) -3-naphthoic acid »
2- (4'-N-methylanilino-2-hydroxybenzoyl) -benzoic acid, 2- (4'-N-ethylanilino-2'-hydroxybenzoyl) -benzoic acid »2- (4'-N-methyl-p-toluidino- 2'-hydroxybenzoyl) benzoic acid »

2- (4'-N-Ethyl-p-toluidino-2'-hydroxybenzoyl) -benzoic acid, 2- (4'-N-Ethyl-o-toluidino-2 ^f -hydroxybenzoyl) -benzoic acid »

2- (4 '-N-ethyl-p-chloroaniliiio- ^' -liydroxybenzoyl) benzoic acid ,

2- (4'-N-Ethyl-p-butylanilino-2'-hydroxybenzoyl) benzoic acid »
2- (4 ^f -N-ethyl-2,4-2cylidino-2 «-hydroxybenzoyl) -benzoe-

acid"

2- (4 '-N-Etliyl-p-toluidiiio-2' -liydroxybeiizoyl) -3-naplithoe-

säTire »

2- (4'-N-methyl-p-toluidino-2 '-hydroxybenzoyl) -3-naph.thoe-ο acid"

2- (4 '-N-Cyclohexyl-li-ynethylamino-2' -hydroxybenzoyl) -

benzoic acid »

2- (4'-N-Cyclohexyl-N-ethylamino- ^ '-hydroxyoenzoyl) -benzoic acid »
2- (4'-N-Cyclohexyl-N-ethylamino ^ '- hydroxybenzoyl) -4-

chlorobenzoic acid,

2- (4 ♦ -N-Cyclohiexyl-IT-methylamino-2 '-hydroxybenzoyl) -3-

napiithoeic acid »

2- (4'-N-Cyclohexyl-N-benzylamino-2 '-liydroxybenzoyl) benzoic acid f

2- (4 ^l -N-Cyclohexyl-N-benzylamino-2'-hydroxybenzoyl) -

3-naphth.o e acid.

2- (4 '- * pyrrolidino- * 2 ^J - ^ hydroxybenzoyl) benzoic acid,

2- (4'-pyrrolidino-2 ^J -hydroxybenzoyl) -3-naphthoic acid,

2 "(4 'pyrrolidino-2 ^J ^ -hydroxybenzoyl)" 3- ^ chlorobenzoic acid,

2- (4 ' -piperidino-2 ' -hydroxybenzoyl) -benzoic acid, 2- * (4 '-morpholino-.2 ^f - = hydroxybenzoyl) -benzoic acid and

2- (A ' -Isoindolino-2 ' - ^ hydroxybenzoyl) benzoic acid.

Of the fluoran compounds according to the invention the general Formula (VI), the fluoran compounds of the following general formulas (VII) and (VIII) are preferred:

MR

(VII)

Q ήΠ

In the formula, R and E each stand for a short-chain Alkyl radical and E for a cycloalkyl radical.

^HCH < _O 8 (VIII)

12th
In the formula, R stands for a short-chain alkyl

7 8 '

rest, while the Eeste R and E have the meaning given own.

Of the eluorane compounds of the general formula (VII) and (YIII) are of particular interest those of the formulas:

HCH (CH ₃ )

and

In the following Table I are some fluoran compounds of the general formula (I) identified in more detail with regard to their radicals and the achievable "shade". Under "shade" is that which can be determined on a thin-layer chromatographic silica gel plate Understanding coloring.

= pH = O

CN

IT) in η m m
X egg κ Π r X X S3 p U X O
CN CN CN U O O U X U U \ / CN O
CN T ^
CN U X X X CN U υ U U X CN CN CN O X O S. U U cn ci S ' X s Z CJ α

VO

in X CN

in

06

in

X s CN

U.N

CN

M U

C -

rH IT »

33 K

m cm

U U

G - '

in S. ■ Η in S. S. X O in CN U U U

cn

r-4 r-H

U O

- 61 -

(Continuation of Table I)

CM CM O CO CM

CH ₃ OC ₂ H ₄

^C 2 ^H 5

CH ₃ OC ₂ H ₄

C ₂ H ₅

CH-

C ₂ H ₅

CH-

CH-

C ₂ H ₅

CH

CH

CH ₂ OCH ₃

CH.

Cl

Br Cl

black

purple-black

«Co ro

(Continuation of Table I)

CH ₃ CH ₃ 3 CH ₃ CH ₃ CH ₃ Cl α green-black Il C ₂ H ₅ ^C 2 ^H 5 H C ₂ H ₅ Il - Il Il
■ I η
ti CH ₃ \ CH ₃
CH ₂ CH ^ "
XH ₃ Il Il
Il Il
Il Il Il Il CH ₂ OCH ₃ Il Il Il H Il O Il Il » Il Il ■ 1 11th black O Il Il Il green-black rc * Il Il Il

(Continuation of Table I)

O H ^C 2 ^H 5 D. CH ₃ CH ₃ CH ₃ CH ₃ Cl α black η CH ₃ Il ■ I CH ₂ OCH ₃ Il Il Il η H Il O Br Il Il Il Il G Il Cl Il Il Il Il K ■ 1 Il H Il Il H Il Il O C ₂ H ₅ Il Il Il η Il Il Il Il H Il Il ti .Hn " - »Η λ * ■ "Λ /

(Continuation of Table I)

G
CC Ό
H
Il Cl
Il
■ I α
U
H black.
H
U

According to the invention, an imide compound is obtained in which the alpha carbon atom attached to the imino residue a tertiary carbon atom, on an industrial scale in higher yield and with higher purity than after

5 the known method.

Using this imide compound, a dye of the general formula (I) is obtained which has hitherto only been used in Form of a mixture with difficult to separate by-products is obtained in very high yield and Purity.

Most of the fluoran compounds obtainable according to the invention represent new compounds. Using such new fluorane derivatives with their unique Recording materials produced by chemical structure as color-forming substances provide images deep black color and show excellent storability, color formability, light resistance and water resistance. For example, one is made using color-forming substances according to the invention produced pressure-sensitive recording material with the described microcapsule layer less susceptible to discoloration when exposed to light. The color images produced therewith also have an excellent one Lightfastness. In the case of heat-sensitive recording materials the uncolored plies or layers are less prone to discoloration when exposed to heat or Exposure to moisture. The color image produced in this way also experiences only a minor change in color when exposed to heat or moisture or discoloration when exposed to light. When the fluorane derivatives according to the invention are used in thermosensitive recording materials for the production of multicolored images, can the color formation be carried out at high temperature

regret. This gives a multicolored image without color mixing. Also such a recording material can be stored stably.

The color-forming substances according to the invention are characterized by a very high solubility in the organic solvents used in the manufacture of pressure-sensitive recording materials.

The fluoran compounds according to the invention have the disadvantages of commercially available color-forming substances for the production of pressure- or heat-sensitive Recording materials do not.

The following are the results of a light resistance test communicated. After color formation has taken place, this is carried out with the aid of fluorane derivatives according to the invention under activated clay. First, a 1 # solution of the respective fluoran compound in toluene is applied to the activated clay coated Layer support of a pressure-sensitive recording material applied for color formation. Then the whole thing is 10 hours or 20 hours with a fluorescent lamp with a light intensity of 32,000 lux exposed. The colors of the unexposed layer or the exposed layer are then included Identified with the help of D65-1O as the light source. Color values L *, a * and b * are obtained here. This becomes

the respective color difference ΔΕ * is determined. 30th

The following Table II shows the lightfastness values of various compounds of the general Formula:

NH-CH

in the color-forming state, expressed as ΔΕ *. The lower the values for ΔΕ * are, the better the light resistance is.

Sand ice product R ^D - 6th rI CH ₂ CH ₂ OCI X H Il A. after. ΛΕ * according to JP-OS ^C 2 ^H 5 R ^b ~ ^CH \ p2 Ό CH ₃ α 10- after It Il C ₂ H ₅ Ό Cl Il perform 20- according to ■ example 16 ■ 1 Il -C ₆ H ₁₃ (H, Il Il diger perform fjem. Example 21 Il Il -C ₂ H ₄ OC ₂ H ₅ Il Il Be diger Il Il Ό Il • I lich Be -acc. Example 23 Il _ _CH / ^C 2 ^H 5
^V C ₂ H ₅ tion lich Il .CH ₃ Il Il 10.5 tion 1 M. 10.0 12.4 2 .'gem. Example 27 CH ₂ OCH ₃ 9.6 13.7 3 Il .CH ₃ Il Il 6.4 13.4 4th .gem. Example 29 Il -CH ^ 7.5 8.2 5 Il OCC 9.8 Il 6.7 6th 9.9 6.6 7th 9.4 5.7 8th 7.8

• t * m ■

(Continuation of Table II)

9 according to example 31 ■ I C ₂ H ₅ "^ CH ₃ Cl approx 5.8 7.7 10 according to example 30 H -Q Il Il 6.4 8.9 11th according to example 37 Il C ₂ H ₅ O Il OC 7.3 8.2 12th according to example 38 H Il CH ₃ Il Il 5.4 8.6 13th gen. Example 39 O- Il CH ~
-CH ς ' ^J
CH ₂ OCH ₃ H Il 4.4 7.9 14th according to example 46 CH ₃ η H Il 7.2 9.5

CO KJ KJ

In the following the invention is illustrated by the examples explained in more detail.

5 Example 1

A 500 ml stirred autoclave is charged with 57.0 g of cyclohexanone, 100 g of ethanol, 7118 g of 3-chloro-4-aminophenol, 3 g of glacial acetic acid and 2 g of 5 # platinum-on-charcoal catalyst. After replacing the prevailing inside the autoclave atmosphere with hydrogen, the temperature is raised to 120 ⁰ C. The reductive alkylation takes place under a hydrogen pressure of 1960 kPa. In accordance with the hydrogen consumption, hydrogen is introduced into the autoclave several times under pressure, until a total of 1 mol of hydrogen per 1 mol of chloraminophenol has been consumed. After the contents of the autoclave have cooled to 60 ^° C., they are removed to remove the catalyst. The removed catalyst is washed with a small amount of ethanol. After the ethanol has been distilled off from the filtrate, the distillation residue is stirred with 1 liter of water. 117 ⁰ C are obtained - The deposited crystals to give 110 g of 2-chloro-4-hydroxy-N-cyclohexylaniline, mp 115 are filtered off, washed with water and dried. The Eeaktionsprodukt obtained is recrystallized from toluene to give white crystals of a Pp 116-117 ⁰ C are obtained. Their elemental analysis and mass spectrum agree with the

calculated values. 30th

Example 2

An autoclave used in Example 1 is with 25.2 g of cyclopentanone, 100 g of ethanol, 43 »1 g of 3-chloro-4-amino-.

phenol, 2 g acetic acid and 2 g 5 f> -platinum-on-carbon-

κ- ι * -

Catalyst loaded. After replacement of the pressure prevailing in the autoclave atmosphere with hydrogen, the temperature is raised to 120 ⁰ C. The reductive alkylation takes place at a hydrogen pressure of 1960 kPa. In accordance with the hydrogen consumption, hydrogen is introduced into the autoclave several times until a total of 1 mole of hydrogen per 1 mole of chloraminophenol has been consumed. After the contents of the autoclave have cooled to 60 ^° C., they are filtered to remove the catalyst. The catalyst is washed with a small amount of ethanol. The ethanol is then distilled off from the piltrate. The case incurred distillation residue is again distilled under reduced pressure to give 57 * 7 g 2-chloro-4-hydroxy-N-cyclopentylanilin in Porm white crystals, b.p. 142-143 ⁰ C at 199 »5 Pa and a melting point of 68 - 69 ⁰ C can be obtained.

^20th Example 3

The reductive alkylation is carried out in accordance with BeisO.iel 2 at 120 ⁰ C. The starting materials are 14 "6 g of .beta.-tetralone, 50 g methanol, 14» 4 g of 3-chloro-4-aminophenol, 3 g of glacial acetic acid and 1.5 g of 5 # -Platinum-on-charcoal catalyst used. After a total of 1 mol of hydrogen per 1 mol of chloraminophenol has been consumed, the contents of the autoclave are filtered to remove the catalyst. The methanol is then distilled off from the piltrate. The resulting distillation residue is stirred with 1 liter of hot water. The oily layer (26.8 g) which separates out is then separated off. The 26.8 g of oily product are brought from an equal amount of toluene to crystallize with 23.8 g of 2-chloro-4-hydroxy-N- (ßtetralinyl) -aniline a PP of 81 - 83 ⁰ C obtained in white crystals Porm will.

l Example 4

The reductive alkylation takes place as in Example 1 at 120 ^° C. The starting materials are 13.9 g of acetone, 40 g of ethanol, 28.7 g of 3-chloro-4-aminophenol, 1.2 g of glacial acetic acid and 0.8 g of 5 # - Platinum-on-carbon catalyst used. The hydrogen consumption is 1 mol of hydrogen per 1 mol of chloraminophenol. After filtering off the catalyst and distilling off the ethanol from the filtrate, the evaporation residue is washed with hot water. Which separates this oily layer is separated and moved from a small amount of toluene for crystallization to give 20 g of 2-chloro-4-hydroxy-N-isopropylaniline white crystals in the form of a Pp 85-86 ⁰ C are obtained.

Example 5

The reductive alkylation, the aftertreatment and the recrystallization are carried out according to Example 4. Instead of the acetone, 25.6 g of diacetone alcohol or 28.6 g of diacetone alcohol methyl ether are used as the starting material. Ultimately, 18 g or 24 g of 2-chloro-4-hydroxy-N-isopropylaniline are obtained. The I ¹ P of the products is 85 - 86 ⁰ C.

The structure of the compounds is confirmed by taking the FD mass spectrum and nuclear magnetic resonance spectrum.

30 Example 6

The reductive alkylation with hydrogen takes place at 120 ^° C. The starting materials used are 130 g of 3-pentanone, 43 »1 g of 3-chloro-4-aminophenol, 3 g of acetic acid and 2 g of 5 # platinum-on-carbon catalyst. After removing the catalyst and excess 3-pentanone, the residue is washed with water. The

oily product is distilled under reduced pressure to give 55 g of 2-chloro-4-hydroxy-N- (1'-ethylpropyl) aniline, bp 120 - 121 ⁰ C are obtained at 159f6 Pa. The reaction product is obtained in oily form.

Example 7

The reductive alkylation with hydrogen is carried out in an autoclave used in Example 1 at 120 ^° C. with 150 g of methyl isobutyl ketone, 71 »8 g of 3-chloro-4-aminophenol, 5 g of glacial acetic acid and 2 g of 96-platinum-on-carbon catalyst carried out. After the catalyst has been filtered off and the methyl isobutyl residue has been distilled off from the filtrate by steam distillation, the oily product which separates out is distilled under reduced pressure. Here, 80.5 g of 2-chloro-4-hydroxy-N- (1 ', 3'-dime thylbutyl) -aniline in the form of white crystals, b.p. 136-137 ⁰ C at 266 Pa, and a mp 64-65 , 5 ⁰ C obtained.

Example 8

The reductive alkylation is carried out with hydrogen at 120 ^° C., 42.1 g of dibenzyl ketone, 28.7 g of 3-chloro-4-aminophenol, 3 g of acetic acid, 100 g of ethanol and 2 g of 5 # platinum-on-carbon Catalyst is run out. After removing the catalyst and the ethanol from the reaction mixture and washing the residue with water, the reaction product is crystallized from toluene. In this case, one obtains 63t5 g of 2-chloro-4-hydroxy-N- (1 x phenylmethyl-2'-phenylethyl) aniline as white crystals of mp 95-97 ⁰ C.

l Example 9

The reductive alkylation is carried out with hydrogen at 120 ^° C., with 22.2 g of 4-phenyl-2-butanone, 21.5 g of 3-chloro-4-aminophenol, 3 g of acetic acid, 40 g of ethanol and 2 g of 5 # - Platinum-on-carbon catalyst is assumed. After removing the catalyst and the ethanol from the reaction mixture, the residue obtained is washed with water and distilled under reduced pressure, 2-chloro-4-hydroxy-N- (1'-methyl-3 ^1- phenylpropyl) aniline having a bp of 146 - 147 ⁰ C at 199.5 Pa is obtained.

Example 10

The reductive alkylation takes place with hydrogen at 120 ^° C., starting from 20 g methoxyacetone, 32.6 g 3-chloro-4-aminophenol, 100 g ethanol, 2 g acetic acid and 2 g 5% platinum-on-carbon catalyst will. After the catalyst and the ethanol have been removed from the reaction mixture, the residue obtained is washed with water and then crystallized from toluene. This gives 25 g of 2-chloro-4-hydroxy-N- (1'-methyl-2'-methoxyethyl) aniline in the form of white

Crystals have a Pp of 82 - 83 ⁰ C.

Example 11

The reductive alkylation takes place according to the example

10, but the methoxyacetone by 25.5 g.

4-methoxy-2-butanone is replaced. After removing the Catalyst and the ethanol from the reaction mixture, the residue obtained is washed with water. 30 g of 3-chloro-4- (1'-methyl-3'-methoxypropylamino) -phenol in the form of an oily product

35. _.

keep.

¹ Example 12

The reductive alkylation is carried out with hydrogen at 120 ⁰ C, whereby 28.5 g of cyclohexanone, 100 g of methanol, 39t4 g of 3-chloro-4-aminoanisole, 1.5 g of glacial acetic acid and 2 g of 5 - platinum on carbon -Catalyst is assumed. After the catalyst and the methanol have been removed from the reaction mixture, the residue obtained is washed with water and then crystallized from η-hexane. Here, 50 g of 2-chloro-4-methoxy-N-cyclohexylaniline obtained in the form of white crystals, Pp 47-48 ⁰ C.

Example 15

Example 12 is repeated, but with the cyclohexanone replaced by methyl ethyl ketone and 1 mol of hydrogen is consumed per 1 mol of amine or the cyclohexanone replaced by methyl vinyl ketone and 2 moles of hydrogen are consumed per 1 mole of amine. You get 2-chloro-4-methoxy-N- (1'-methylpropyl) -aniline in the form of an oily product.

Example 14

The reductive alkylation is carried out with hydrogen at 120 ^° C., with 16.2 g of cyclohexanone, 40 g of ethanol, 28.2 g of 3-bromo-4-aminophenol, 0.9 g of glacial acetic acid and 0.5 g of 5-6 platinum -on-charcoal catalyst is assumed. After removing the catalyst and the ethanol from the

The resulting residue is washed with water and then from toluene and η-hexane to the reaction mixture Brought crystallization. This gives 36.2 g of 2-bromo-4-hydroxy-N-cyclohexylaniline in the form of white

Crystals with a Pp of 103 - 104 ⁰ C.

l Example 15

The reductive alkylation is carried out as in Example 14, but the 3-bromo-4-aminophenol is replaced by 30-3 g of 3-bromo-4-aminoanisole. After the catalyst and the ethanol have been removed from the reaction mixture, the residue obtained is washed with hot water. This gives 35 g of 2-bromo-4-methoxy-N-cyclohexylaniline in the form of an oily product.
10

Example 16

In 219 g 98 #iger sulfuric acid are 31 "3 g of 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid and 22" 6 g of 2-chloro-4-hydroxy-N-cyclohexylaniline at a temperature of 30 ⁰ C or solved below. Thereafter, the reaction mixture to terminate the reaction for 24 hours at 50 - 55 ⁰ C stirred. When the reaction has ended, the reaction mixture is poured into a solution of 2,000 g of ice water and 270 g of 28% aqueous ammonia in order to make the whole thing alkaline. A precipitate separates out and is filtered off. The filter cake is washed with 2,000 g of warm water and then dried, 41 »2 g of 3-DIe ^ yIaDaInO-S-ChIOr-T-CyCIohexylaminofluoran being obtained. The reaction product obtained is recrystallized from isopropanol to give 37 "9 g of white crystals, mp 197 - 198 ⁰ C are obtained. Their structure is determined by elemental analysis, mass spectrum and nuclear magnetic resonance spectrum.

30 confirms.

Example 17

31 »3 g of 2- (4-diethylamino-2'-hydroxybenzoyl) benzoic acid are added to 219 g of 98% sulfuric acid and 21.2 g

Dissolved 2-chloro-4-hydroxy-N-cyclopentylaniline at a temperature of 3O ⁰ C or below. The resulting solution is 24 hours "at a temperature of 50 - stirred 55 ⁰ C. After completion of the reaction, the whole is poured into 2000 g of ice water and made alkaline with 710 g 25 #iger sodium hydroxide The resulting precipitate is filtered, washed with.. 2,000 g of warm water are washed and dried, giving 39.2 g of 3-diethylamino-6-chloro-7-cyclopentylaminofluoran, which is recrystallized from isopropanol, giving 32.0 g of white crystals with a pp of 162.5 163-5 ⁰ C.

15 Example 18

39.8 g of 2- (4'-diamylamino-2'-hydroxybenzoyl) benzoic acid and 22.6 g of 2-chloro-4-hydroxy-N-cyclohexylaniline are dissolved in 219 g of 98% sulfuric acid, whereupon the solution is dissolved for 24 hours is stirred 55 ⁰ C - at 50th

When working up as in Example 16, 41.2 g of 3-diamylamino-6-chloro-7-cyclohe3cylaminofluoΓa ^^ are obtained. This is recrystallized from isopropanol, 32.0 g of white crystals having a Pp of 130.5-131 »5 ^° C. being obtained.

Example 19

31.3 g of 2- (4'-diethylamino-2 ^f -hydroxybenzoyl) benzoic acid and 27 »4 g of 2-chloro-4-hydroxy-N- (β-tetralinyl) aniline are dissolved in 219 g of 95% sulfuric acid , whereupon the solution obtained is ^{stirred at 30 °} C. for 25 h. When worked up according to Example 16 of a Pp of 172 is obtained 25.3 g of 3-diethylamino-6-chloro-7- (beta-tetralinylamino) fluoran in Porm white crystals - 175 ⁰ C.

1 example 20

31 »3 g of 2- (4'-diethylamino-2'-hydrojcybenzoyl) benzoic acid and 18.6 g of 2-chloro-4-hydroxy-N-isopropylaniline are dissolved in 219 g of 98% sulfuric acid hours at 50 - 55 ⁰ C is stirred. When worked up according to Example 16, 36.6 g of 3-diethylamino-6-chloro-7-isopropylaminofluoran obtained This is recrystallized from isopropanol to give 34.0 g of white crystals, Pp 199.5 to 200.5 ⁰ C obtained .

Example 21

In 219 g of 98% sulfuric acid, 31.3 g of 2- (4 ^f -diethylamino-2'-hydroxybenzoyl) benzoic acid and 21.4 g of 2-chloro-4-hydroxy-N- (1'-ethylpropyl) aniline are added dissolved, whereupon the resulting solution is dissolved at 50-55 ^° C. for 24 hours. Working up as in Example 16 gives 38.6 g of 3-diethylamino-6-chloro-7- (1'-ethylpropylamino) fluorane. This is recrystallized from isopropanol to give 34.9 g of white crystals, mp 140 - 141 ⁰ C are obtained.

25 Example 22

In 219 g of 98% sulfuric acid, 31.3 g of 2- (4'-diethylamino-2 ^! -Hydroxybenzoyl) -benzoic acid and 22.8 g of 2-chloro-4-hydroxy-N- (1 ·, 3'-dimethylbutyl ) -aniline dissolved, whereupon the solution obtained at 24 for 50 hours - 55 ⁰ C is stirred. Working up as in Example 16 gives 40.5 g of 3-diethylamino-6-chloro-7- (1 *, 3'-dimethylbutylamino) fluorane. This is recrystallized from isopropanol, 30 g of white crystals of a Pp

156-158 ⁰ C are obtained. 35

1 example 23

In 219 g of 94% sulfuric acid, 31 »3 g of 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid and 21.57 g of 2-chloro-4-hydroxy-N- (1'-methyl-2 ' -methoxyethyl) -aniline, whereupon the resulting solution is ^{stirred at 40 50 0} C for 24 h. Working up as in Example 17 gives 29 »8 g of 3-diethylamino-6-chloro-7- (1'-methyl-2'-methoxyethylamino) fluorane. This is recrystallized from Iropropanol, with 15 "2 g of white crystals Pp of 183 - 185 ⁰ C are obtained.

Example 24

In 238 g of 90% sulfuric acid, 31 »3 g of 2- (4'-di-

¹ ^ ethylamino-2'-hydroxybenzoyl) benzoic acid and 33 »8 g of 2-chloro-4-hydroxy-N- (1 '-phenylmethyl-2' -phenylethyl) -aniline dissolved, whereupon the resulting solution for 24 hours at 60 ⁰ C is stirred. When the reaction has ended, the whole is poured into 2,000 g of ice water, made alkaline with 710 g of 25% sodium hydroxide solution and extracted three times with toluene. The resulting toluene solution is concentrated under reduced pressure. The case incurred concentrate is taken from isopropanol to crystallize to give 10 g of 3-Diethylamlno-6-chloro-7- (1'-benzyl-2'-phenylethylamino) fluoran in the form of white crystals, mp 134 - 137 ⁰ C obtained will.

30 Example 25

31 »3 g of 2- (4'-diethylamino-2 ^f -hydroxybenzoyl) benzoic acid and 24» 0 g of 2-chloro-4-methoxy-N-cyclohexylanine are dissolved in 219 g of 98% sulfuric acid hours at 50 - 55 ⁰ C is stirred.

Then the whole thing is poured into 2,000 g of ice water, with

710 g sodium hydroxide 25 #iger basified, heated to 80 ⁰ C and finally left for 1 hour at this temperature. The precipitate which has separated out is then filtered off and washed with water. After the precipitate has dried, it is heated to the boil with an equal amount of o-dichlorobenzene and then cooled. When diluting with isopropanol, 35 g of S-diethylamino-δ-chloro-Y-cyclohexylaminofluorane are obtained. This is identical to the product obtained according to Example 16.

Example 26

In 219 g of 93% sulfuric acid, 31 »3 g of 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid and 26.0 g of 2-chloro-4-hydroxy-N- (1'-methyl-3 ' -phenylpropyl) aniline dissolved, followed by stirring the resulting solution for 36 h at 30 ⁰ C. Working up as in Example 16 gives 3-diethylamino-6-chloro-7- (1 ^f -methyl-3'-phenylpropylamino) fluorane. This is recrystallized from isopropanol to give 25.7 g of white crystals Pp of 180 - 183 ⁰ C are obtained.

2 B Example 27

In 219 g of 94% sulfuric acid, 31 »3 g of 2- (4 * -diethylamino-2'-hydroxybenzoyl) benzoic acid and 23» O g of 2-chloro-4-hydroxy-N- (1'-methyl-3 ' -methoxypropyl) -aniline, whereupon the resulting solution is ^{stirred at 40 0} C for 24 h. When working up as in Example 17, a crude product is obtained which is crystallized from isopropanol. This gives 3-diethylamino-6-chloro-7- (1'-methyl-3 · -methoxypropylamino) -fluorane in the form of white crystals of Pp of

35 ₁₇ 2 - 174 ⁰ C.

1 example 28

6.26 g of 2- (4'-diethylamino-2 * -hydroxybenzoyl) -benzoic acid and 5 »4 g of 2-bromo-4-hydroxy-N-cyclohexylaniline are dissolved in 45 g of 98% sulfuric acid h at 45 - 50 ⁰ C is stirred. When working up as in Example 17, a crude product is obtained which is crystallized from a 1: 2 solvent mixture of toluene and isopropanol. Here orm of white crystals are obtained 7.5 g 3-3) iethylamino-6-bromo-7-cyclohexylaminofluoran in three of Pp of 177 - 178 ⁰ C.

Example 29

7.28 g of 2- (4'-diethylamino-2'-hydroxybenzoyl) -3-naphthoic acid are dissolved in 60 g of 98% sulfuric acid at a temperature of 30 ^° C. or below. 4.52 g of 2-chloro-4-hydroxy-N-cyclohexylaniline are also dissolved in the solution obtained. The whole is then stirred for 36 hours at a temperature of 30 ^° C., then poured into 300 g of ice water, made alkaline with sodium hydroxide solution and heated ^{to 70 ° C.} The precipitate which has separated out is filtered off, washed with water and dried, 4.50 g of 3-diethylamino-6-chloro-7-cyclohexylaminobenzofluorane being obtained. This is recrystallized from isopropanol to give white crystals of a Pp 172-173 ⁰ C are obtained.

Example 30

Example 29 is made with 4.23 g of 2-chloro-4-hydroxy-N-cyclopentylaniline instead of the 2-chloro-4-hydroxy-N-cyclohexylaniline repeated. This gives 4.23 g of 3-diethylamino-6-chloro-7-cyclopentylaminobenzofluorane.

This is recrystallized from isopropanol to give white crystals of a Pp of 210 - 211 ⁰ C are obtained.

Example 31

Using 60 g of 98% sulfuric acid, 7.28 g of 2- (4 ^t -diethylamino-2 ^l -hydroxybenzoyl) -3-naphthoic acid and 3.71 g of 2-chloro-4-hydroxy-N-isopropylaniline, the reaction is carried out allowed to proceed at 3O ⁰ C h according to example 29 36th Working up as in Example 29 gives 5 »15 g of 3-diethylamino-6-chloro-7-isopropylaminobenzofluorane. This is recrystallized from isopropanol, white crystals of a Pp of

15,216 to 217.5 ⁰ C are obtained.

Example 32

Example 31 is repeated with 4.55 g of 2-chloro-4-hydroxy-N- (1x, 3'-dimethylbutyl) aniline instead of the 2-chloro-4-hydroxy-N-isopropylaniline. This gives 4.86 g of 3-diethylamino-6-chloro-7- (1 ', 3'-dimethylbutylamino) benzofluorane. This is recrystallized from isopropanol to give white crystals of a Pp 108-112 ⁰ C.

²⁵ can be obtained.

Example 33

Example 31 is repeated using 3.99 g of 2-chloro-4-methoxy-N-isopropylaniline instead of the 2-chloro-4-hydroxy-N-isopropylaniline. The condensation takes place with 2- (4 ^l -diethylamino-2 ^l -hydroxybenzoyl) -3-naphthoic acid in 98% sulfuric acid. When the reaction has ended, the reaction mixture is poured into ice water and made alkaline. The here unusual

Crystals are filtered off and dried. The crystals are then heated ^{to a temperature of 170 °} C. with an equal amount of o-dichlorobenzene. After cooling, the whole is diluted with isopropanol. This gives J-diethylamino-e-chloro-T-isopropylaminobenzoefluorane. This product is identical to the reaction product of Example 31.

10 Example 54

Example 31 is repeated with 4 »32 g of 2-chloro-4-hydroxy-N- (1 · - methyl-2 ^f -methoxyethyl) aniline instead of the 2-chloro-4-hydroxy-N-isopropylaniline. This gives 5 »2 g of 3-diethylamino-6-chloro-7- (1'-methyl-2 ^f methoxyethylamino) benzofluorane. This is recrystallized from isopropanol »give white crystals of a Pp 204-205 ⁰ C are obtained.

20 Example 35

Example 29 is repeated using 5 »4 g of 2-bromo-4-hydroxy-N-cyclohexylaniline instead of the 2-chloro-4-hydroxy-N-cyclohexylaniline. The reaction takes place for 18 h at 25 ^° C. Working up as in Example 29 gives 5 »4 g of 3-diethylamino-6-bromo-7-cyclohexylaminofluorane. This is recrystallized from isopropanol to give 2.6 g of white crystals Pp of 167 - 168 ⁰ C are obtained.

Example 56

1.82 g of 2- (4'-N-methyl-p-toluidino-2-hydroxybenzoyl) -benzoic acid and 1.13 g of 2-chloro-4-hydroxy-N-cyclohexylaniline are added to 13 g of 98% sulfuric acid Dissolved temperature of 30 ⁰ C or below. The received

4a-

Lostuig the reaction is stirred for 48 h at 30 ⁰ C then until completion.

After the reaction has ended, the reaction mixture is poured into 100 ml of ice water and made alkaline with 16 g of 28 # strength aqueous ammonia. The precipitate which has separated out is filtered off, washed with 200 g of warm water and dried, 2.3 g of 3- (N-methyl-ptoluidino) -6-chloro-7-cyclohexylaminofluorane being obtained. This is recrystallized from isopropanol "which is 37» 9 g of white crystals is obtained a PP of 218 219 "C 5 ^0. The structure is confirmed by elemental analysis, mass spectrum and nuclear magnetic resonance spectrum.

Example 37

Example 36 is mixed with 1.88 g of 2- (4'-N-ethyl-p-toluidino-2 ^l -hydroxybenzoyl) -benzoic acid instead of 2- (4'-N-methyl-p-toluidino-2'-hydroxybenzoyl) benzoic acid repeated, 2.3 g of 3- (N-ethyl-p-toluidino) -6-chloro-7-cyclohexylaminofluorane being obtained. This is recrystallized from isopropanol, giving white crystals

will receive 188 ⁰ C - one of Pp 187th 25th

Example 38

1.88 g of 2- (4'-N-ethyl-p-toluidino-2 ^f -hydroxybenzoyl) benzoic acid and

0.93 g of 2-chloro-4-hydroxy-N-isopropylaniline dissolved, whereupon the solution is ^{stirred at 30 °} C. for 48 hours to complete the reaction. Working up according to Example 36 gives 3- (N-ethyl-p-toluidino)

6-chloro-7-isopropylaminenofluorane. This is made from Iso-35

recrystallized propanol, white crystals of a

M 1 Pp of 159 - 160 ⁰ C are obtained,

Example 39

Example 36 is mixed with 13 g of 98 # sulfuric acid, 1.88 g of 2- (4'-N-methyl-p-toluidino-2'-hydroxybenzoyl ^ benzoic acid and 1.08 g of 2-chloro-4-hydroxy-N- (1 ^f -methyl-2'-methoxyethyl) aniline repeated to give 3- (N-ethyl-p-toluidino) -6-chloro-7- (1 ^f -methyl-2'-methoxyethylamino) fluorane. this is recrystallized from isopropanol to give white crystals of a Pp of 149 - 152 ⁰ C are obtained.

15 Example 40

Example 36 is mixed with 13 g of 98 # strength sulfuric acid, 1.88 g of 2- (4'-N-ethyl-p-toluidino-2'-hydroxybenzoyl) benzoic acid and 1.06 g of 2-chloro-4-hydroxy-N -cyclopentylaniline repeated, with 3- (N-ethyl ~ p-toluidino) -6-chloro-7-cyclopentylaminofluoran is obtained. This is recrystallized from isopropanol to give white crystals of a Pp of 200 - 202 ⁰ C are obtained.

^25th Example 41

Example 36 is mixed with 13 g of 98 # sulfuric acid, 1.88 g of 2- (4 '-lir-ethyl-p-toluidino-2-hydroxybenzoyl) -benzoic acid and 1.07 g of 2-chloro-4-hydroxy- Repeated N- (1 ^f -ethylpropyl) aniline to give 3- (N-ethyl-p-toluidino) -6-chloro-7- (1'-ethylpropylamino) fluorane. This is recrystallized from isopropanol to give white crystals of a Pp 128-130 ⁰ C are obtained.

1 Example 42

Example 36 is mixed with 219 g of 94% sulfuric acid, 1.88 g of 2- (4'-N-ethyl-p-toluidino-2 ^f -hydroxybenzoyl) benzoic acid and 1 »14 g of 2-chloro-4-hydroxy-N - (1 ', 3'-dimethylbutyl) -aniline repeated to give 3- (N-ethyl-ptoluidino-6-chloro-7- (1'»3'-dimethylbutylaminoj-fluorane), which is recrystallized from isopropanol and hexane , whereby white crystals with a melting point of 184 -r 186 ⁰ C are obtained.
10

Example 43

In 13 g of 98% sulfuric acid, 1.88 g of 2- (4'-N-ethyl-p-toluidino-2'-hydroxybenzoyl) benzoic acid and 1.25 g of 2-chloro-4-methoxy-N-cyclohexylaniline are added a temperature of 30 ^° C. or below, whereupon the solution is ^{stirred at 30 °} C. for 48 h. The whole is then poured into 200 ml of ice water, made alkaline with 25 # strength sodium hydroxide solution, ^{heated to 60 °} C. and left at this temperature for 1 hour. The resulting precipitate is filtered off and washed with water. After drying, the precipitate is heated to the boil together with an equal amount of o-dichlorobenzene. The whole thing is then cooled and diluted with isopropanol. 3- (N-Ethyl-p-toluidino) -6-chloro-7-cyclohexylaminofluorane precipitates out. This is recrystallized from isopropanol, white crystals being obtained. These are with the

Product prepared according to Example 37 is identical. 30th

Example 44

In 60 g of 98 # sulfuric acid 7.35 g 2- (4'-N-cyclohexyl-N-ethylamino-2 * -hydroxybenzoyl) benzoic acid at a temperature of 20 ⁰ C or less * dissolved in

4.52 g of 2-chloro-4-hydroxy-N-cyclohexylaniline are also dissolved in the resulting solution. After the whole thing has been stirred for 48 hours at 25 ^° C., the reaction mixture is poured into 300 g of ice water and made alkaline with sodium hydroxide solution. The precipitate which has separated out is filtered off, washed with water and dried, 8.2 g of 3- (N-cyclohexyl -N-ethylamino) are obtained -6-chloro-7-cyclohexylaminofluoran This is recrystallized from isopropanol to give white crystals of a Pp of 222 -. be obtained 223 ⁰ C.

Example 45

In 25 g of 98 # sulfuric acid are 3 "55 g of 2- (4 ^{f -N-cyclohexyl-N-methylamino-2!} -Hydroxybenz oyl) -b enzo e acid at a temperature of 20 ⁰ C or dissolved underneath. 2.26 g of 2-chloro-4-hydroxy-N-cyclohexylaniline are further dissolved in the solution obtained, whereupon the whole is ^{stirred at 25 °} C. for 48 hours. When the reaction has ended, the reaction mixture is poured into 300 g of ice water and made alkaline with aqueous ammonia. The precipitate which has separated out is filtered off, washed with water and dried, 5> 8 g of 3- (N-cyclohexyl-N-methylamino) -6-chloro-7-cyclohexylamino-fluorane being obtained. This is recrystallized from toluene and isopropanol to give white crystals of a Pp 225-226 ⁰ C are obtained.

30 Example 46

Example 45 is made with 2.16 g of 2-chloro-4-hydroxy-N- (1'-methyl-2 · methoxyethyl) aniline instead of the 2-chloro-4-hydroxy-N-cyclohexylaniline repeated, with 5 »6 g of 3- (N-cyclohexyl-N-ethylamino) -6-chloro-7- (1'-methyl-2'-methoxyethylamino) -fluorane can be obtained. This will

recrystallized from isopropanol to give white crystals of a Pp of 168 - 171 ⁰ C are obtained.

5 Example 47

Example 45 is repeated with 1.86 g of 2-chloro-4-hydroxy-N-isopropylaniline instead of the 2-chloro "4-hydroxy-N-cyclohexylaniline, 5» 3 g of 3- (N-cyclohexyl-N-ethylamino) be obtained -6-chloro-7-isopropylaminofluoran This is recrystallized from isopropanol to give white crystals of a Pp of 207 -. be obtained 108.5 ⁰ C.

15 Example 48

Example 45 is repeated with 2.12 g of 2-chloro-4-hydroxy-N-cyclopentylaniline instead of the 2-chloro-4-hydroxy-N-cyclohexylaniline, with 4.5 g of 3- (N-cyclohexyl-N-ethylamino) -6-chloro-7-cyclopentylaminofluoran can be obtained. This is recrystallized from isopropanol to give white crystals of a Pp of 208 - 21O ⁰ C are obtained.

^25th Example 49

Example 45 is made with 2.70 g of 2-bromo-4-hydroxy-N-cyclohexylaniline instead of the 2-chloro-4-hydroxy-N-cyclohexylaniline, 5.5 g of 3- (N-cyclohexyl-N-ethylamino) -6-bromo-7-cyclohexylaminofluorane obtain

will. This is recrystallized from isopropanol to give white crystals of a Pp of 228 - 23O ⁰ C are obtained.

Example 50

In 100 g of a- (3 »4-dimethylphenyl) -a-phenylethane become

2.0 g fluoran compound of the formula:

solved, whereupon the whole thing together with a solution of 20 g of gum arabic is emulsified in 160 g of water. After adding 20 g of acid-treated gelatin and 160 g Water, the pH of the mixture is adjusted to 5 by adding acetic acid with constant stirring. Then another 50 g of water are added to allow the coacervation to proceed. After setting the pH value to 4.4 by adding acetic acid, 4 g 37 #igen formalin are added, with a rigid Film is formed.

All of the measures described are performed at 5O ⁰ C.

Thereafter, the system is cooled to 10 ⁰ C, to gel the thick liquid film and a film hardening bring about. After adjusting the pH to 9 by adding an aqueous sodium hydroxide solution, the whole is left to stand for a few hours in order to obtain a capsule-forming emulsion. This is then mixed with 30 g of finely powdered cellulose and 100 g of a 1Obigen

* (oQ> -

mixed aqueous solution of oxidized starch, whereupon the whole thing is applied to paper and dried. Here one obtains the upper layer of a "copy paper".

The obtained upper layer (of the copy paper) is placed on a lower layer (of the copy paper), whereupon the whole thing is written on with a pencil or a typewriter. This forms a picture-appropriate black color, i.e. it appears on the lower layer both when a p-phenylphenol polymer is used as well as when using acid-treated, activated clay (as a coating of the lower layer) sharp black letters or characters.

The pressure-sensitive recording material or copy paper produced according to the invention has a excellent storage stability and a high rate of pitting. The colored letters or characters produced with it are against long-lasting ones Resistant to exposure to light and does not change color even when wetted with water.

Example 51

Similar to Example 50, it becomes a pressure sensitive one Recording material or copy paper produced, however, as a fluoran compound such as the Formula:

CH

"VOX

-CO

1 is used.

When the pressure-sensitive recording material obtained is written on with a typewriter, appears a true-to-image black image.

The obtained pressure-sensitive recording material is excellent in storage stability and high speed of color formation. The colored letters or characters produced in this way have an excellent quality light and water resistance.

Example 52

According to Example 50, a pressure-sensitive recording material or copy paper is produced, however, the fluorane compound being one of the formula

CH ₃

* CH: 25

30 is used.

When the pressure-sensitive recording material obtained is written on with a typewriter, appears a true-to-image black image. 35

The obtained pressure-sensitive recording material is excellent in storage stability and high speed of color formation. The colored letters or characters generated in this way have an excellent

5 marked light and water resistance.

Example 53

With the help of a sand mill, 30 g of fluorine compounds are using the formula:

in a mixture of 150 g of an aqueous solution Polyvinyl alcohol solution and 65 g of water (component A) dispersed.

Furthermore, 35 g of bisphenol A and 150 g of a 10bigen aqueous polyvinyl alcohol solution in a corresponding manner in 65 g of water (component B).

33 g of component A and 67 g of component B are mixed together mixed, whereupon the mixture obtained is applied to a base in such a way that

'2

measure when dry - 5 g per m of support surface

Coating is not required.
The sheet-like structure obtained is suitable as a sol-

.6ft

eheε as a heat-sensitive recording material. With With the help of a thermal recorder, an excellent black image can be obtained.

The heat-sensitive recording material prepared in the above manner is excellent in appearance, does not discolor by itself, and exhibits a high rate of color formation. The letters and characters produced with it are excellent
light and water resistant.

example

54

Similar to Example 53 using a
Fluoran compound of the formula:

a thermosensitive recording material was prepared. This does not discolor by itself and has a high speed of color formation. The letters and characters generated with it are excellent
light and water resistant.

example

55

According to Example 53, using 28 g of a fluoran compound of the formula:

and 2 g 3-Ι) 1β ^ 3Γΐ3ΐηίηο-6,7-ΐ3βηζοϊ ^ θΓ3ΐι a heat sensitive Recording material produced. This has similar thermal recording properties like the heat-sensitive recording material according to Example 53.

Claims (21)

15 ■ PATENT CLAIMS 1. Process for the preparation of fluoran compounds the general formula: ρ = , X , 1 (D where mean: A is an optionally halogen-substituted benzene or naphthalene nucleus; on X is a halogen atom; 1 2 R and R individually each optionally an ether bond having alkyl radical, cycloalkyl radical or phenyl radical or together with the carbon atom of the 'ffethinrestes a cycloalkyl, tetralig nyl or indanyl radical; R is an alkyl, alkoxyalkyl, cycloalkyl, phenylalkyl or phenyl radical; an alkyl, alkoxyalkyl or phenylalkyl radical or R ⁵ and _c R together a remainder of the formulas: b CH -
² CH ₂ ^- , - (CH ₂ ) _p -or- with ρ = 4.5 or 6, with the proviso that the phenyl radicals R and R can optionally be alkyl- or halogen-substituted, characterized in that one is an aniline compound the general formula: (ID in which X has the meaning given and R stands for a hydrogen atom or a short-chain alkyl radical, with a ketone compound of the general formula: R ³ ° * ^C \ 4 (HD 3 4 12 where R and R correspond to the meaning of R and R, 1 or a group which changes into a radical R and R in the course of the reaction, under catalytic and reductive alkylation to an imide compound of the general formula: ^NHCH \ 2 1 2
in which X, R, R and R have the meaning given, allowed to react and that the resulting imide compound of the general formula is given in the presence of a dehydrating condensing agent with a compound of the general formula: 6W ^C00H ^^  CO wherein A, R and R have the meaning given to -._ puts. 2. The method according to claim 1, characterized in that the reaction between the compound of the general Formula (II) and the compound of the general formula CEII) under increased hydrogen pressure, with increased Performs temperature and in the presence of a solvent and a catalyst. 3. The method according to claim 2, characterized in that "P. that the reaction is carried out in the presence of an organic acid performs. 4. The method according to claim 3, characterized in that acetic acid is used as the organic acid. 5. The method according to claim 2, characterized in that that a platinum catalyst applied to the support is used as the catalyst. 6. The method according to claim 2, characterized in that that one carries out the reaction at a temperature of 80 to 140 ⁰ C. 7. The method according to claim 2, characterized in that the reaction under a hydrogen pressure of 490.5 to 4905 kPa. 8. The method according to claim 1, characterized in that that the aniline compound of the general formula fll) 3 -Chlor · * 4 - = aminophenol _/
3 ~ chloro-4-aminoanisole,
3-chloro-4-aminophenetol,
3-bromo-4-aminophenol,
3-bromo-4-aminoanisole,
3-iodo-4-aminophenol or
3-fluoro-4-aminophenol used. 9. The method according to claim 1, characterized in that the ketone compound of the general formula (III) _nn cyclohexanone, cyclopentanone, ß-tetralone, 2-indanol acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methoxyacetone, 4-methoxy-2-butanone, diacetone alcohol, 4-methoxy-4-methyl-2-pentanone, dimethoxyacetone, 4-cyclohexyloxy 2-butanone, 4-phenyl-2-butanone, dibenzylke ₂₅ ton or methyl vinyl ketone used. 10. The method according to claim 2, characterized in that with a molar ratio Keionverbindungen the general Formula (III) for the aniline compound of the general 30 nen formula (II) from 1: 1 to 2: 1 works. 11. The method according to claim 1, characterized in that the reaction between the imide compound of general formula (IV) and the compound of the general NEN formula (V) at a temperature of -5 ° to 90 ⁰ C carries out. 12. The method according to claim 1, characterized in that that as dehydrating condensation agents 85-bis 100% sulfuric acid used. 13. The method according to claim 1, characterized in that the imide compound of the general formula (V) ¹⁰ 2 ~ chloro-4-hydroxy-N-cyclohexylaniline, 2-bromo-4-hydroxy-N-cyclohexy! Aniline, -SP- ■ 6 · 2-fluoro-4-hydroxy-cyclohexylaniline, 2-iodo-4-hydroxy-N-cyclohexylaniline, 2-chloro-4-hydroxy-N-cyclopentylaniline, 2-chloro-4-hydroxy-N- (ß-tetralinyl) -aniline, 5 2-chloro-4-hydroxy-N- (2-indanol) aniline, 2-chloro-4-hydroxy-N-isopropylaniline, 2-chloro-4-hydroxy-N- (1'-methylpropyl) -aniline, 2-chloro-4-hydroxy-N- (1'-ethylpropyl) -aniline, 2-chloro-4-hydroxy-N- (1 ', 3'-dimethylbutyl) -aniline, 2-chloro-4-hydroxy-N- (1'-methylhexyl) aniline, 2-chloro-4-hydroxy-N- (1'-methy1-2'-methoxy-ethyl) - aniline,
2-chloro-4-hydroxy-N- (1'-methoxymethyl-2'-metho- xyethyl) aniline, 15 2-chloro-4-hydroxy-N- (1'-methyl-3'-methoxy- propyl) aniline, 2-chloro-4-hydroxy-N- (1'-ethyl-2'-methoxyethyl) -aniline, 2-chloro-4-hydroxy-N- (1'-methyl-2'-methoxyethoxyethyl) aniline, 2-chloro-4-hydroxy-N- (1'-methyl-2 -cyclohexyloxyethyl) aniline, 2-chloro-4-hydroxy-N- (1'-methyl-3'-cyclohexyl- oxypropyl) aniline, 25 2-chloro-4-hydroxy-N- (1'-methyl-2'-benzyloxy- ethyl) aniline, 2-chloro-4-hydroxy-N- (1'-methyl-3'-benzyloxypropyl) aniline, 2-chloro-4-hydroxy-N- (1'-methyl-3'-phenethyl-30 oxypropyl) aniline, 2-chloro-4-hydroxy-N- (1'-methyl-2'-phenoxy- ethyl) aniline,
2-chloro-4-hydroxy-N- (1'-methyl-2'-phenoxy- ethoxyethyl) aniline, 35 2-chloro-4-hydroxy-N- (1'-methyl-2'-phenylethyl) - 'aniline, 2-chloro-4-hydroxy-N- (1'-methyl-3'-phenylpropyl) - aniline, 2-chloro-4-hydroxy-N- (1'-benzyl-2'-phenylethyl) aniline, 2-chloro-4-methoxy-N-cyclohexylaniline, 2-bromo-4-methoxy-N-cyclohexylaniline or 2-chloro-4-methoxy-N- (1'-methyl-3'-methoxy- propyl) aniline 0 is used. 14. The method according to claim 1, characterized in that the compound of the general formula (V) 2- (4 ^! -N, N-Diethylamino-2 '-bydroxybenzoyl) -benzoic acid »2- (4' -N, N-DImetliylamino-2 '-hydroacybenzoyl) -benzoic acid, 2- (4 ^l -N, N- Dipropylamino-2 ^f -hydroxybenzoyl) benzoic acid, 2- (4 ¹ -N, N-dibutylamino-2'-hydroxybenzoyl) benzoic acid, 2- (4 ^f -K, N-diisobutyl amine o-2 * -hydr oxyb enz oyl) -b enz 0 e Bäur e » 2- (4'-N, N-diamylamino-2'-hydroxybenzoyl) -benzoic acid, 2- (4'-NjN-dihexylamino-1-hydroxybenzoyl) -benzoic acid >> 2- (4'-N, N-dioctylamino-2 '-hydroxybenzoyl) -benzoic acid »2- (4'-N-Ethyl-N-butylamino-2 ^f -hydroxybenzoyl) -benzoic acid 2- (4 '-Ni N-Di ethyl amine 0-2' -hydro3cybenzoyl) -4-c] ilor- benzoic acid, 2- (4 · -N, N-diethylamino-2-hydroxybenzoyl) -3 »4» 5 »6-tetrachlorobenzoic acid»
2- (4'-N, N-diethylamino-2'-hydroxybenzoyl) -3-naphtlioe- acid, 2- (4'-NiN-dimethylamino-2 ^l -hydroxybenzoyl) -3-naphthoe- acid, 2- (4'-NiN-dibutylamino-2'-hydroxybenzoyl) -3-naphthoic acid » 2- (4 '-NtN-Diamynamino-Z' -hydroxybenzoyl) -3-naphthoe- acid, 2- (4 -N-ethyl-N-butylamino-2'-hydroxybenzoyl) -3- naphthoic acid »
2- (4'-N, N-diethylamino-2 * -hydroxybenzoya) -5- or -8-chloro 3-naphthoic acid » 2- (4'-N, N-diethylamino-2 ¹ -hydroxybenzoyl) -5- or -8-bromo-3-naphthoic acid » 2- (4'-N, N-dimethoxyethylamino-2'-hydroxybenzoyl) benzoic acid » 2- (4 ^l -N »N-diethoxyethylamino-2'-hydroxybenzoyl) -benzoe- acid" 2- (4'-N, N-diethoxyethylamino-2'-hydroxybenzoyl) -3-naphthoic acid »
2- (4'-N-methylanilino-2'-hydroxybenzoyl) -benzoic acid, 2- (4'-N-ethylanilino-2-hydroxybenzoyl) -benzoic acid, 2- (4'-N-methyl-p-toluidino- 2'-hydroxybenzoyl) -benzoe- Acid » 2- (4'-N-Ethyl-p-toluidino ^ '- hydroxybenzoyl) -benzoic acid » 2- (4'-N-Ethyl-o-toluidino ^ '- hydroxybenzoyl) benzoic acid, -χ- g. 2- (4 '-N-ethyl-p-chloraxiilino ^' -hydroxybenzoyl) -benzoic acid, 2- (4'-N-Ethyl-p-butylanilino ^ '- hydroxybenzoyl) benzoic acid » 2- (4 ^f -N-Ethyl-2,4-xylidino-2 * -hydroxybenzoyl ^ benzoic acid, 2- (4'-N-Ethyl-p-toluidino-2 ^l -hydroxybenzoyl) -3-naphthoic acid »
2- (4'-N-methyl-p-toluidino-2 ^l -hydroxybenzoyl) -3-naphthoe- 10 acid » 2- (4'-N-Cyclohexyl-N-methylamino-Z'-hydroxybenzoyl) - benzoic acid » 2- (4 '-N-Cyclohe3cyl-N-ethylamino-2' -hydroxy uenzoyl) -benzoic acid,
2- (4'-N-Cyclohexyl-N-ethylamino-2'-hydroxybenzoyl) -4 ~ chlorobenzoic acid, 2- (4'-N-Cyclohexyl-N-methylamino-2-hydroxybenzoyl) -3- naphthoic acid » 2- (4'-N-cyclohexyl-N-benzylamino-2'-hydroxybenzoyl) benzoic acid or 2- (4'-N-Cyclohexyl-N-benzylamino-2 ^f -hydroxybenzoyl) - 3 ~ naphthoic acid ■ used. 15. The method according to claim 1, characterized in that with a molar ratio of the imide compound general formula (IV) to compound of general formula (V) from 0.8 to 2.0 works. 16. Process for the preparation of imide compounds of general formula: , R ¹ 'R ² -r- _λ * JtO- where mean: X is a halogen atom; R is a hydrogen atom or a short-chain one _ Alkyl radical and 5 -ι R and 2 R individually each having an ether bond, if applicable Alkyl radical, cycloalkyl radical or phenyl radical or together with the carbon atom of the methine radical a cycloalkyl, tetralinyl or indanyl radical, characterized in that one Aniline compound of the general formula: wherein X and R have the meaning given, with catalytic and reductive alkylation with a ketone compound the general formula: o - c <:. (in) 3 4 12 wherein R and R correspond to the meaning of R and R or one in the course of the conversion into a radical R and R Representing passing group, with catalytic and reductive alkylation to form an I mid-compound of ' Formula (iv) lets react. 17. The method according to claim 16, characterized in 35 that the reaction between the compound of the general formula and the compound of the general formula fill CIII) under increased hydrogen pressure, at higher pressure Temperature and in the presence of a solvent and a - ^ - AA- carries out a catalyst. 18. The method according to claim 17, characterized in that the reaction is carried out in the presence of an organic acid performs. 19. The method according to claim 18, characterized in that acetic acid is used as the organic acid. 20. The method according to claim 17, characterized in that that a supported platinum catalyst is used as the catalyst. , _ 21. The method according to claim 17, characterized in that ο that you can carry out the reaction at a temperature of 80 to 140 ⁰ C performs. 22. The method according to claim 17, characterized in that the reaction under a hydrogen pressure of 490.5 to 4905 kPa. 23. The method according to claim 16, characterized in that the aniline compound of the general formulafll) 3-chloro-4-aminophenol, 3-chloro-4-aminoanisole, 3-chloro-4-aminophenetol, ³⁰ 3-bromo-4-aminopheno1, 3-bromo-4-aminoanisole, 3-iodo-4-aminophenol or 3 -Fluoro-4-aminophenol used. ι. / a 24. The method according to claim 16, characterized in that the ketone compound of the general formula (III) 5 Cyclohexanone, cyclopentanone, ß-tetralone, 2-incanone Acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, Methoxyacetone, 4-methoxy-2-butanone, diacetone alcohol, 4-methoxy-4-methyl-2-pentanone, dimethoxyacetone, 4-cyclohexyloxy-2-butanone, 4-phenyl-2-butanone, dibenzyl ketone or methyl vinyl ketone are used. 25. The method according to claim 16, characterized in that with a molar ratio ketone compound of the general Formula (III) for the aniline compound of the general -yf- . / 13. nen formula (II) from 1: 1 to 2: 1 works. J fluoran compounds of the general formula: (VI) where mean: a halogen atom; an optionally halogen-substituted benzene or naphthalene core; may optionally be alkyl- or halogen-substituted, and individually in each case one optionally having an ether bond Alkyl radical, cycloalkyl radical or phenyl radical or together with the carbon atoms of the Methine radical is a cycloalkyl, tetralinyl or indanyl radical, with the proviso that the total carbon atomic number is 3 'or more if both radicals 7 R and R represent alkyl radicals and A represents a benzene nucleus. 27. Fluoran compounds according to claim 26, characterized in that they have the general formula: (VII) NH-R CO ~ χί- 9 in which R and R each represent a short-chain alkyl radical and R represents a cycloalkyl radical. 28. Fluoranver "connection according to claim 26 of the formula: 29. Fluoran compound according to claim 26, of the formula: CX. 12 ' Cl "NHCHr (VIII) Ό R ⁸ 1 in which R stands for a short-chain alkyl radical and 7 R and R have the meaning given .. _ 30. Fluoran compound .na_ <2h claim 26 of the formula: 3233t2V E. il -ys- 31. Fluoranverbinduna according to claim 26 of the formula: CH. NHCH (CH ₃ ) 32. Pressure or heat sensitive recording material with a support and a fluoran compound of the general type applied thereon as a color-forming electron donor Formula: _ R ^ HCH ' (VI) wherein X, A, R ⁵ , R ⁶ , R ⁷ and have meaning. 1 »Claim ₂ 6 specified