DE2501260A1 - PROCESS FOR THE PREPARATION OF 4-SUBSTITUTED 3-ANILINO-5-PYRAZOLONS - Google Patents

Description

PATENT APPLICATIONS

DR. E. WIEGAND DIPL- "NG. W. NIiMANN DR. M. KOHLER DIPL-ING. C GERNHARDT

MDNCHEN HAMBURG 2501260

TELEPHONE: 555 476 8000 MD NCH E N 2,

TELEGRAMS: CARPATENT. MATH ILDENSTRASSE

TELEX: 529068 KARP D

V. 4223V75 - Ko / Ne January 14, 1975

Fuji ± -hoto Film Co., Ltd. Minazni Ashigara-Shi, Eanagai ^ a (Japan)

Process for the preparation of 4-substituted 3-anilino-5-pyrazolones

The invention relates to a process for the preparation of 4-substituted 3-anilino-5-pyrazolones and, in particular, relates to a process for the preparation of 4-substituted 3-anilino-5-pyrazolones ₍ in which a substituent in a position which is the 4-position of the pyrazolone ring: is introduced before the formation of the fyrazolone ring.

According to the invention, a process for the preparation of 4-substituted 5-anilino-5-P3 ^/ razolones corresponding to the general formula

50 9 8 2 9/0971

(i)

indicated, where R ^, a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, Hp a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an alkylsulfonic acid group, a Carbamido group, an acylamino group, a cyano group, an alkoxycarbonyl group, a sulfoamino group, a Sulfamoyl group, a diacylamino group, a carbamoyl group, a carboxy group, a sulfo group or a Nitro group and Y an alkylamino group, a dialkylamino group, a sulfonamino group, an acylamino group, a diacylamino group, a nitrogen-containing heterocyclic group, with the 4-position of the pyrazolone ring above the nitrogen atom in the heterocyclic ring or a heterocyclic group connected to the 4-position of the Pyrazolone ring means releasable group linked via an oxygen atom, whereby a ring-closing condensation reaction a compound corresponding to the general formula

(III)

509829/0371

wherein Rp and Y are as defined above and R _{7 is} an alkyl group and R ^ is a hydrocarbon group, with a hydrazine corresponding to the general formula

R ₁ NHMI ₂ , '(IV)

wherein R ^ has the preceding meaning carried out will.

It is known that 5-pyrazolones are important compounds for magenta couplers in the photographic field and are valuable substances as intermediates for various drugs and dyes. If for example a common silver halide color photographic light-sensitive material which is a 5-pyrazolone contains, is exposed and color-developed, the 5-pyrazolone acts as a coupler and undergoes oxidative coupling with the para-phenylenediamine type color developing agent and forms the corresponding azomethine dye which forms the magenta image.

Of these, 5-pyrazolones a 4-unsubstituted ^5-I> 7i'azolonkuppler requires stoichiometrically 4 Koi silver halide as an oxidizing agent to form 1 mole of the azomethine dye upon oxidative coupling reaction, as is known in the art. On the other hand, a ^ -pyrazolone, which has a substituent in the 4-position, which can easily be released during the coupling reaction, stoichiometrically only requires 2 pounds of silver halide,

There are various types with releasable groups as substituents in the 4-position of the pyrazole couplers known. Examples are such releasable groups in U.S. Patents 3,253,924, 3,311,476, 3,419,391, 3,522,051, 2,434,272. Also Pyrazoior.-

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couplers with releasable groups involved in coupling released xverden, and their released compound with the silver halide present in the environment in Interaction occurs and results in a development inhibiting effect in this area for the 3ilder formed are known. That is, these 4-substituted 5-pyrazolones release a development inhibitor 2-equivalent couplers (DIE couplers) and are for example U.S. Patents 3,227,554, 3,701,783, 3,148,062, 3,617,291, 3,006,759.

From the above discussion it will be understood that 5-pyrazolones with a releasable substituent in the 4-position very important connections for the production of color photographic photosensitive materials.

So far, 4-substituted 6-pyrazolones, in particular 4-substituted 3-anilino-5-pyr'azolones, according to a Process prepared in which the pyrazolone ring is formed and then a releasable substituent in the 4-position of the pyrazolone ring is introduced. Examples of such methods are given in U.S. Patents 2,434,272, 3 148 062, 3 066 759, 3 522 051, 3 227 554, 3 701 783, 3 617 291, 3 311 476 and 3 419 391 and the German OLS 2 260 203 and other references.

^{The 4-substituted 3-ai>} ylamino-5-pyrazolones which can be prepared by the process according to the invention comprise numerous new compounds. Some of the 4-substituted 3-arylamino-5-pyrazolones, by the method ger-irc of the invention can be prepared, are given in the following patents, o ^"e were c.och in these patents mentioned 4-substituted-Z- Arylamino-5-pyrasolone compounds according to different: Process versus the synthesis process according to the

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discovery made. U.S. Patent 3,617,291 describes processes for the preparation of 4- (2-benzotriazolyl) -5-pyrazolones including examples of such compounds from 3-arylamino-4- (2-benzotriazolyl) -5-pyrazolones. According to this method, after the formation of the 5-Py ^raz ° l ° ^nr i ⁿ 6 ^{is e} i ^Q o-Nitrobenzodiazoniumsalz in der.4-position of the pyrazolone ring bonded through a diazo coupling and the nitro group is subjected to a reductive ring closure reaction to form the 4- Submit (2-benzotriazolyl) -5-pyrazolones. However, this production method is not practical because it is difficult to determine the reaction conditions to be used in the case where 3-arylamino-5-pyrazoiones are used as starting materials, so that the yield is low, and particularly, it is economical Position unfavorable to making 3-arylamino-4- (2-benzotriazolyl) -5-pyrazolonec using this procedure.

In U.S. Patent 3,311-476 there is one method for the preparation of inclusion 4-acyloxy-5-pyrazolones of 3-arylanino-4-acyloxy-5-pyrazolones. To the formation of the 5-pyrazolone ring includes this process However, five procedural stages, the complicated procedure and reaction conditions require. This process also has the disadvantage of a low yield. Therefore this process is also not very suitable industrially.

In U.S. Patent 3,4-19,391 there are two methods for the preparation of 4- aryloxy-5-pyrazolones, including inclusions indicated by 3 - ^ - rylainino-4 ~ aryloxy-5-pyrazolones. One After the formation of the 5-pyrazolone ring, the production process comprises five steps to produce 4-aryloxy-5-pyrazolones to obtain. Because the process involves numerous reaction steps which are complicated and complicated. Require reaction conditions and give poor yields, int

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the preparation of 3-arylamino-4-arlyoxy-5-pyrazolones after this process economical, disadvantageous. Furthermore, the application of this method is limited by the Limited scope of aryloxy groups that can be introduced.

Another manufacturing process is that 4-aryloxy-5-pyrazolones including 3- ^ rylamino-4-aryloxy-5-pyrazolones by introducing an aryloxy group in the 4-position of the pyrazolone ring prior to formation of the ^ pyrazolone ring is introduced. According to this procedure 4 — aryloxy-5-pyrazolones are obtained via four reaction stages, starting from ethyl a-chloroacetoacetate starting material obtain. This process, too, which has numerous levels of progression which are complicated and require complicated reaction conditions and give poor yields, is limited in applicability because the aryl thiocyanate used as one of the reactants is used Furthermore, it is impossible or extremely difficult to define a non-diffusible group into the 3-anilino group of a 3- ^ nilino-4-aryloxy-5-pyrazo ion to be introduced before the formation of the pyrazolone ring. Therefore, this method is also disadvantageous from an economic point of view and has hardly any value as an industrial process.

One object of the invention is therefore a new process for the production of pyrazolone rings, in particular in a new process for the production of 4 ~ substituted 3 - A.nilino-5-pyrazolones.

Another object of the invention is a process for the preparation of 4-substituted 3-anilino-5-pyrazolones using a simple process with high yields.

Another object of the invention consists in sine ¹ -: new process for the preparation of 3- ^ nilino-5-pyrazol ::: one

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with a substituent in the ^ - position, which at the oxidative coupling with color developing agents of the para-phenylenediamine type is releasable.

Another object of the invention is a process for the preparation of various 4-substituted 3-anilino-5-pyrazolones.

Another object of the invention consists in very pure couplers of the 4-substituted 3-anilino-5-pyrazolone type, obtained by the method according to the invention can be.

A further object of the invention consists in couplers "of the 4-substituted 3 - ** nili ^ o-5-pyrazolone type with superior photographic properties.

The objects of the invention can be achieved by performing a ring-closing condensation reaction of an α-substituted ß-Alkoxy-ß-arylaminoacrylic acid ester with a Hydrazine can be achieved.

Those obtainable by the process according to the invention Compounds correspond to the following general formula:

(D

wherein R ,, is a hydrogen atom, an alkyl group, an aralkylene group or an aryl group, R ^ a hydrogen atom, a Alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an alkylsulfonic acid group, a carbamide group, an acylamino group, a cyano group, an alkoxycarbonyl group, a sulfoamino group, an olefanoyl group,

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a diacylamino group, a carbamoyl group, a carboxy group, a sulfo group or an ilitro group and Y is a Alkylamino group, a dialkylamino group, a sulfonamino group, an acylamino group, a diacylamino group, one with the 4-position of the pyrazolone ring via the nitrogen atom nitrogen-containing heterocyclic group connected in the heterocyclic ring or one with the 4-position of the pyrazolone ring via an oxygen atom, releasable group, the process in the Carrying out a ring closure condensation reaction of a compound of the general formula:

(III)

wherein R ~ and Y have the meanings given above and R ^ is an alkyl group and R ^ is a hydrocarbon group mean with a hydrazine according to the general formula:

E ₁ NHHH ₂ , (IV)

wherein R _{1 has} the meaning given above.

An additional embodiment of the invention exists in a process for the preparation of 4-substituted 3-arylamino-5-pyrazolones according to the general I / omel

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(D

where R ^, a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, R ^ a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogenatoa, an alkylsulfonic acid group, a carbamide group, an acylanino group, a cyano group, an alkoxycarbonyl group, a sulfonamino group, a sulfamoyl group, a diacylamino group, a carbamoyl group, a carboxy group, an oil group or a nitro group and Y is an alkylamino group, a dialkylamino group, a sulfonamino group, an acylamino group, a diacylamino group, a nitrogen-containing, with the 4-position des Pyrazolone ring through the nitrogen atom in the heterocyclic ring connected heterocyclic group or a with the 4-position of the pyrazolone ring means releasable group linked via an oxygen atom, with a substitution reaction an α-halogen-ß-alkoxy-ß-arylaminoacrylic acid ester according to the general formula

(II)

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wherein R ^ has the meanings given above, R ^ is an alkyl group and R ^ is a hydrocarbon group and X represent a halogen atom, with Y ~ or YH to form a compound according to the general formula:

(III)

is substituted, wherein Rp, R ^, R ^ and Y are the above Have given meanings, and then a ring-closing condensation reaction the compound of the general formula (III) with a hydrazine of the general formula:

R ₁ NHNH ₂ , (IV)

wherein R ^ has the meanings given above, is carried out.

According to the invention, R ^ means a hydrogen atom an alkyl group, for example an alkyl group having 1 to 20 carbon atoms, a fluorine-substituted alkyl group and the like., an aralkyl group, e.g. Benzyl group, a phenethyl group, a substituted benzyl group with a substituent such as halogen atoms, Nitro groups, alkyl group with 1 to 20 carbon atoms, Acyl amino groups, ζ. B. acyl amino groups with 1 to 30 carbon atoms, a carbamoyl group, for example ei: -or Carbamoyl group, especially an IT-alkyl substituted one. Carbamoyl group with 1 to 20 carbon atoms in the alkyl

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portion, an N-arylcarbamoyl group having 1 to 2 rings in the aryl portion and the like., or an aryl group such as a phenyl group, a biphenyl group, a tri-.phenyl group, an ITaphth hy I group, an aromatic heterocyclic aryl group such as a 2-benzothiazolyl group and the like. Which with one or more substituents such as halogen atoms, nitro groups, alkyl groups such as alkyl groups with 1 to 20 carbon atoms, acylainino groups such as acylamino groups with an alkyl portion with 1 to 20 carbon atoms or an aryl portion such as phenyl group, naphthyl group, substituted phenyl group , substituted naphthyl group or the like, a carbamoyl group, an N-alkylcarbamoyl group, for example an N-alkylcarbamoyl group having 1 to 20 carbon atoms in the alkyl portion, an N-arylcarbamoyl group, an aryloxy group such as a phenoxy group, a substituted phenoxy group with substituents such as halogen atoms ,. Nitro groups, alkyl groups, acy / amino groups, carbamoyl groups, substituted garbamoyl groups, sulfo groups, carboxy groups, sulfonamide groups, ureido groups or the like, an alkoxy group, for example alkoxy groups with 1 to 20 carbon atoms, an alkylthio group, for example alkylthio group, for example an alkylthio group with 1 to 20 carbon atoms, an acyloxy group Acyloxy groups with 1 to 20 carbon atoms, a carboxy group, a sulfo group, an alkylsulfonyl group, for example alkylsulfonyl groups with 1 to 20 carbon atoms in the alkyl portion, an alkoxycarbonyl group, for example alkoxycarbonyl groups with Ί to 20 carbon atoms in the alkoxy portion, a fluorosulfonyl group, a T-reido group _v an N-alkyl group for example N-alkylureido groups with alkyl groups with 1 to 20 carbon atoms, a 17-

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Alkylureido group, for example IT-arylureido groups with a phenyl group, an ITaphthyl group, a substituted one Phenyl group, a substituted naphthyl group or Like., a cyano group, a SuIfοalkylgruppe, for example Sulfoalkyl groups with an alkylene content of 1 to 4 carbon atoms or the like. Can be substituted.

Rp means a hydrogen atom, an alkyl group, for example alkyl groups with 1 to 20 carbon atoms, an alkoxy group, for example alkoxy groups having 1 to 20 carbon atoms, an alkylthio group, for example Alkylthio groups with 1 to 20 carbon atoms, a halogen atom, a sulfoalkyl group, for example sulfoalkyl groups with an alkylene portion with 1 to 4 carbon atoms, a carbamoyl group, for example ii-alkylcarbamoyl groups with 1 to 20 carbon atoms in the alkyl portion, N-arylcarbamoyl groups with 1 to 2 chings in the aryl part, an acylamino group, for example an acylamino group having an alkyl moiety of 1 to 20 carbon atoms or an aryl moiety such as phenyl group, naphthyl group, substituted phenyl group, substituted ilaphthyl group or the like, a diacylamino group, for example Diacylamino groups with alkyl moieties with 1 to 20 carbon atoms or aryl components, such as phenyl groups, ITaphthyl groups, substituted phenyl groups, substituted taphthyl groups or the like. Which may be in the form of either a chain or a cyclic structure, such as, for example as a 5-membered ring or as a 6-membered one Ring and the like, a cyano group, an alkoxycarbonyl group, for example alkoxycarbonyl groups with 1 to 20 carbon atoms in the alkoxy moiety, a sulfamido group, "for example Sulfamide groups with C to 20 carbon atoms, a sulfamoyl group, for example mono- or di-substituted sulfamoyl groups, in particular T: ono-

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or di-substituted sulfamoyl groups having an alkyl moiety containing 1 to 20 carbon atoms or an aryl moiety, such as a phenyl group, a naphthyl group, a substituted one Phenyl group, a substituted naphthyl group or the like., A carboxy group, a sulfo group or a Nitro group.

The radicals R ^ and Rp can have an olloslxchmachende Group or a non-diffusible group for couplers contained, for example, in British patent 774 421, US patents 2,920,961, 3,418,129, 3 658 544, 3 681 076, 3 062 653 and 2 474 293, the Germans OLS 2,216,578, Japanese Patent Applications 35379/73 and 69383/73 and similar references.

As oil-solubilizing groups or non-diffusible Groups can also be called ballast groups, which are a hydrophobic group with about 8 to 32 carbon atoms may also be used. The ballast group can be connected to the core of the coupler via a Imino bond, an ether bond, a carbamide bond, a sulfamide bond, an ureido bond, an ester bond, an imide bond, a carbainoyl bond, a sulfamoyl bond or the like. Be connected.

Illustrative examples of ballast groups are given below.

(I) alkyl groups and alkenyl groups, for example:

-CH ₂ -CH (C ₂ Hc) ₂ , ~ "^ 12 ^ 25 '" ^ 16 ^ 33 * "" ^ 17 ^ 33

(II) alkoxyalkyl groups, for example:

- (CH ₂ ) ₃ -O- (CH ₂ ) _? CH ₅ , - (CH ₂ ) ₃ OCH ₂ -CH- (CH ₂ ) ₈ -CH ₅ ,

C ₂ H ₅ -

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according to Japanese Patent Publication 27563/1964. (III) alkylaryl groups, for example

CuH ₉ Ct)

C ₉ Hi

(IV) alkylaryloxyalkyl groups, for example:

-CH ₂ O

C ₅ Hn (t)

C ₅ HnCt)

c ₅ H ₁₁ Ct)

C ₅ H ₁₁ Ct)

C ₂ H ₅

-CHO

C ₅ HuCt)

509 8 2 9/0971

- (CH ₂ ) ₃ O- <7_ \ VC SH ₁ , Ct) C ₅ H ₁₁ Ct)

CH ₃
-CO- ^ \\

CH ₃ \

C ₁₅ H ₃₁ Cn)

-CH ₂ O - // V) -CsH ₁ χ (t)

CH3-C-CH3

CH ₂ -CH ₉ Ct)

CA

c ₅ H ₁₁ Ct)

sH ₁₁ Ct)

(V) acylamidoalkyl groups, for example:

-CH ₂ CH ₂ N.

, COCi 5H31

-CH2CH2N:

.COC ₁₃ H ₂₇ ^ C ₃ H ₇

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/ ι ₃ H ₂ 7

-CH ₂ Ch ₂ NHCOCH ₂ CH ₂ N ^

C ₃ H ₇

corresponding to U.S. Patent Nos. 3,337 34-4 and 3,4-18,129.
(VI) alkoxyaryl and aryloxyaryl groups, for example

7 ~ 0 - (/ Vc ₁₂ H ₂₅ Cn)

(711) Groups that have both a long-chain aliphatic Radical from the group of alkyl groups or alkenyl groups as well as a water-solubilizing .Rest from the group of carboxy groups or sulfo groups contain, for example:

-CH-CH = CH-Ci ₆ H ₃₃ , -CH-Ci ₆ H ₃₃ CH ₂ COOH SO ₃ H

(VIII) Alkyl groups substituted with an ester group are, for example:

-CH-Ci ₆ H ₃₃ Cn), -CH ₂ -CH ₂ -COOCi ₂ H ₂₅ Cn). COOC ₂ H ₅

(IX) alkyl groups, which with an aryl group or a, heterocyclic ring are substituted, for example

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^ VnHCOCH ₂ CH-C ₁₈ H ₃ 7 (η) COOCH ₃

C ₁₈ H ₃₇ Cn)

(X) aryl groups substituted with an aryloxyalkoxycarbonyl group, for example

Y denotes a substituent connected to the 4-position of the 5-pyrazolone ring via a nitrogen atom or an oxygen atom. The substituents linked through a nitrogen atom include a substituent which does not form a ring and a nitrogen-containing heterocyclic group linked through a nitrogen atom. Examples of the former are an alkyl amino group, for example alkyl amino groups with Λ to 20 carbon atoms in the alkyl portion, a dialkylamino group, for example:

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wise dialkylamino groups with alkyl portions with 1 to 20 carbon atoms, an arylamino group or a biarylamino group, For example anilino groups, naphthylamino groups and the like., Where the aryl portion or the Aryl moieties with one or more sub substituents, such as halogen atoms, nitro groups, alkyl groups, for example Alkyl groups with 1 to 20 carbon atoms, acylamino groups, for example acylamino groups with an alkyl portion having 1 to 20 carbon atoms or an aryl moiety such as a phenyl group, a naphthy group, a substituted phenyl group, a substituted ITaphthyl group Or the like., a carbamoyl group, a ΝΑΙ ky lc ar b amo yl group, for example N-alkylcarbamoyl group having an alkyl moiety having 1 to 20 carbon atoms, an N-arylcarbamoyl group, an aryloxy group, a Alkoxy group, for example alkoxy groups with 1 to 20 carbon atoms, an alkylthio group, an acyloxy group, a carboxy group, a sulfo group, an alkylsulfonyl group, an alkoxycarbonyl group, a Ureido group, a cyano group, a sulfoalkyl group or the like, an acylamino group such as acylamino groups having an alkyl moiety having 1 to 20 carbon atoms or an aryl moiety such as a phenyl group, a Naphthy! Group, which with one or more substituents, such as halogen atoms, nitro groups, alkyl groups with 1 to 20 carbon atoms, acylamino groups, carbamoyl groups, N-alkylcarbamoyl groups, N-arylcarbamoyl groups, Alkoxy groups, arylcxy groups, alkylthio groups, iLcyloxy groups, Carboxy groups, sulfo groups, alkyl sulfone groups, Alkoxycarbonyl groups, ureido groups, cyano groups, oulfoalkyl groups Or the like., may be substituted, a Sulphonamino group, never for example oulphonamino groups an alkyl moiety having 1 to 20 carbon atoms or

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an aryl part that is the same. Definition As with the above acylamino group has a defined aryl moiety, a diacylamino group, for example diacylamino groups, which is an acylamino group with an alkyl moiety having 1 to 20 carbon atoms or an aryl moiety such as a phenyl group, naphthyl group, which with one of those indicated above for the acylamino group Substituents can be substituted, the diacylamino group still either in the form of a chain or a cyclic structure, for example as a 5-membered Ring, as a 6-membered ring and the like., Can be present.

The nitrogen-containing heterocyclic, about a Groups linked to nitrogen atom include nitrogen-containing heterocyclic, basic and weakly acidic groups with a pKa of about 5 to 16. Examples of nitrogen-containing heterocyclic bases are cyclic amino groups, for example a piperidino group, a pyrrolidino group, a morpholino group, a substituted one piperidino group, for example with an alkyl group having 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, a halogen atom and the like. Substituted piperidino groups, a substituted pyrrolidino group, for example with an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, a halogen atom and d ^ l, substituted Pyrrolidino groups, a substituted corpholino group, for example one with an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, a halogen atom and the like. Substituted corpholino groups and like groups. The weakly acidic group with a pKa of about 3 to -16 can be a succinimide group, a substituted 'ijuccininid-

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group, for example with an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, a halogen atom, an aryl group and the like. Substituted succinimide group, a phthalimide group, a substituted phthalimide group, for example with one or more substituents such as halogen atom, nitro groups, Alkyl groups with 1 to 20 carbon atoms, acylamino groups, carbamoyl groups, XT-alkylcarbamoyl groups, N-arylcarbamoyl groups, alkoxy groups, aryloxy groups, alkylthio groups, acyloxy groups, carboxy groups, sulfo groups, alkylsulfonyl groups, alkoximenzoyl groups, substituted sulfo groups, sulfo-benzoyl groups, sulfo-benzo-alkyl groups, sulfo-benzoyl groups, sulfo-thalido-alkyl groups, ureido groups , a hydantoin- (j) -yl group, a 5-substituted hydantoin- (j5) -yl group, for example in the 5-position with a substituent such as alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, 1 to 20 K alkylidene groups Carbon atoms or the like, substituted hydantoin (3) -yl groups, a 1-substituted hydantoin (5) -yl group, for example in the 1-position with a substituent such as an alkyl group with 1 to 20 carbon atoms, an acyl group, such as an acyl group having an aliphatic hydrocarbon portion having 1 to 20 carbon atoms or an aromatic hydrocarbon portion having 1 to 20 carbon atoms and the like, an alkylsulfonyl group such as an alkylsulfonyl group having 1 to 20 carbon atoms and the like, an arylsulfonyl group such as a benzene ring or! Taprithalin ring-containing arylsulfonyl group with 1 to 20 carbon atoms and the like substituted hydantoin- (3) -yl £ ^ru PP ^e > a diglycolimide group, a 2,4-dioxooxazolidinyl- (3) group, a 5-substituted 2,4-dioxcoxazolidine3 * l- (3) group, for example in the ^ -Stellu ^ -j;

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2,4-dioxooxazolidinyl (3) group, a 2,4-dioxothiazolidinyl (3) group, a 5- substituted 2,4-dioxothiazolidinyl (3) group, for example 2,4-dioxothiazolidinyl (3) group substituted in the 5-position with one of the substituents given for the 1-substituted hydantoin (3) -yl group described above , a 1-aryl-3,5-diketo-1 ^^ - triazolidin- ^ yl group, a 2-oxopyrrolidinyl group, a 2-oxopiperidyl group, a 2-oxohexylamino group, a 2-oxodihydropyridyl group, a 4-oxodihydropyridyl group, a 2-thioxodihydropyridyl group , a 4-thioxodihydropyridyl group, a 2,4-dioxotetrahydropyrimidin-3-yl group, a 2,4-dioxohexahydropyrimidin-3-yl group, a 2-oxopyrimidin-1-yl group, a 4-oxodihydropyrimidinyl group, a 2- oxodihydropyrimidinyl group, a 3-oxodihydropyrimidinyl group Oxodihydropyridazin-2-yl group, a 2,6-dioxopiperidino group, a 2,6-dioxo piperazinyl group, a piperazinyl group, a PyrroIyIgruppe, a pyrazolyl group, a pyrazolidinyl group, an edolyl group, a 2-isoindolyl group, a 1-indazolyl group, a 1-benzotriazolyl group, a substituted 1-benzotriazolyl group, for example with a halogen atom, an alkyl group with Λ , an acylamino group such as an acylamino group containing an alkyl moiety having 1 to 20 carbon atoms or an aryl moiety, a carbainoyl group, a suI fön amoyl group, a suIf amoyl group, an i'iitro group, a cyano group, a sulfo group or the like, substituted 1-benzotriazolyl group , an I-benzimidazole group, a substituted 1-benzimidazblyl group, for example one having a halogen atom, an alkyl group having 1 to 20 carbon atoms, an acylamino group having an alkyl moiety having 1 to 20 carbon atoms or an :: i

509829/0 9 71

Aryl moiety and the like, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a nitro group, a cyano group, a sulfo group or the like 1-benzimidazolyl group, a 1-pyrimidinyl group, a 1-imidazolydinyl group, a 1-imidazolinyl group and d ^ l.

The substituents linked via an oxygen atom include an acyloxy group, for example acyloxy groups with an alkyl moiety containing Λ to 20 carbon atoms, an aryl moiety such as a phenyl group or a naphthyl group and the like, an aryloxy group, for example phenyloxy groups, naphthyloxy groups, substituted phenyloxy groups or naphthyloxy groups such as one or more substituents such as halogen atoms, nitro groups, alkyl groups such as alkyl groups with 1 to 20 carbon atoms, acylamino groups, carbamoyl groups, N-alkylcarbamoyl groups, IT-arylcarbamoyl groups, aryloxy groups, alkoxy groups, alkylthio groups, acyloxy groups, carboxy groups, sulfo groups, alkylsulfonyl groups , SuIfoalkyl groups or the like substituted phenyloxy groups or naphthyloxy groups, heterocyclic oxy groups such as 2-pyridyloxy groups, 5- ("1-I ⁾ henylgetrazolyl) oxy groups and the like, an acylaminoxy group, an alkylidene aminooxy group, an arylideneaminooxy group and the like.

Specific examples of 4-substituted 3 - ^ iIi " ⁰ " 5-pyrazolones which can be prepared according to the invention are given below, but these examples serve only for illustration and the present invention is in no way limited to these compounds given as examples is.

Compound 1-1 1-phenyl-3 - / "(2-chloro-5-tetradecanar-.ido} -

anilino7 - ^ - (i-piperidino) -5-pyrazolone

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link 1-2 link 1-3 link 1-4 link link 1-6 link 1-7 link 1-8 link link 1-10 link 1-11 link 1-12 link 1-1? link 1-14

1- (4-chlorophenyl) -3-Z (2-chloro-5-tetradecane

amido) -anilineq / -4- (1-Eiorph.olino) -5-pyrasolone

1-phenyl-3 - / (2-chloro-5-tetradecana! Nido) -

anilinoT-4- (1-morpholino) -5-pyrazolone

1- (4-Nitrophenyi) -3- (2-chloroanilino) -4-

(5- or 6-methyl-1-benzotriazolyl) -5-

pyrazolone

1-C4-nitrophenyl) -3- (o-toluidino) -4- (5-

or 6-meth.yl-i-benzotriazolyl) -5-pyrazolone

3- ^ X 2-chloro-5-tetradecanamido) -aniIino7-

4- (5- or 6-methyl-1-benzotriazolyl) -5-

pyrazolone

1-Benzyl-3-ZX 2-methoxy-5-tetradecyloxy-

carbonyl) -anilino7'-4— (5- or 6-methyl-1-

benzotriazolyl) - $ - pyrazolone

1-Benzyl-3- (4-octadecyloxyanilino) -4- (5-

or 6-bromo-i-benzotriazolyl) -5-pyrazolone

1-Benzyl-3-ZX2-chloro-5-tetradecanamido) -

anilino_7-4— (5- or 6-bromo-1-benzotriazoIyI) -

5-pyrazolone

1-Benzyl-3-ZX2-chloro-5-tetradecanamido) -

anilinq7-4- (5- or 5-methyl-1-benzotri-

azolyl) -5-pyrazolone

1-Benzyl-3-ZX2-chloro-5-tetradecanamido) -

anilincj7-4- (5- or 6-nitro-1-benzotri-

azolyl) -5-pyrazolone

3- (2-chloro-5-nitroanilino) -4- ( 5 , 5-di-

methyl-3-nydantoinyl) -5-pyrazolone

3- (2-chloro-5-nitroanilino) -4- (5,5-di-

methyl-2,4-dioxo-3-oxazolidinyl) -5-pyrazolone

1- (2,4,6-trichlorophenyl) -3 - / (2-chloro-5-

tetradecanamido) -anilino7-4-succininico-

5-pyrazolone

509829/0971

Link; 1-15 1-pnenyl-3-Zl2-methoxy-5-tetradecyloxy-

carbonyl) -anilino7-4- (5- or 6-methyl-

1-benzotriazolyl) -5-pyrazolone compound 1-16 1- (4-nitrophenyl) -3- / l2-methoxy-5-tetra-

decyloxycarbonyl) -anilino7-4- (5- or

6-methyl-1-benzotriazolyl) -5-pyrazolone compound 1-17 1-benzyl-3-Z (2-ynetb.oxy-5-tetradecanainido) -

anilinq / -4- (5- or 6-methyl-1-benzotri-

azolyl) -5-pyrazolone
Compound 1-18 1- (4-chlorobenzyl) -3- ^ 4-methoxy-3-tetra-

decanamido) -anilino7-4- (5- or 6-methyl-

1-benzotriazolj ^r l) -5-pyrazolone compound 1-19 1- (4-nitrophenyl) -3-ZX2-methoxy-5-tetra-

decyloxycarbonyl) -anilino7-4- (515-di-

methyl-2,4-dioxo-3-oxazolidinyl) -5-py.razclo: Compound 1-20 1- (4-ITitrophenyl) -3-ZX2-aetlaoxy-5-tetr5-

decyloxycarbonyl) -anilino7-4- (5,5icLimethyl-

3-hydantoinyl) -5-pyrazolone compound 1-21 1- (2,6-dichloro-4-metiioxyphenyl) -3- / 2-ciiIor-

5- i (2,4-di-tert-arnylphenoxy) -acetaüiido, ^ -

anilino_7-4-phtiiaiimido-5-pyrazolon compound 1-22 1- (2,4-dimethyl-6-chlorophenyl) -3- _i / 2-chloro-

5- (hexadecanamido) -anilinoy-4- (i-pyrrolyl) -

5-pyrazolone
Compound 1-23 1- (2,4,6-Trichlorophenyl) -3-Zl2-chloro-5-

nitro) -anilineq7-4- (1-iiTiidazol3 / l) -5-

pyrazolone
Compound 1-24 1- (2,4,6-Trichlorophenyl) -3- / t Z , 5-din et -: ■; ■:; · -

carbonyl) -anilino7-4- (1,2-dihydro-2-o: .'-

1-pyridyl) -5-pyrazolone
Connection 1-25 1 - Cp-ITi t ropheny 1) - 3-Zl 2- chi ο r- 5-1 et rad ec, y 1 -

oxycarbonyl) -anilinri7-4- (2-o :: ') -' ¹ -piperi.-

dyl) -5-pyrazoion

509829/0971

Compound 1-26 1- (2,4,6-Trichlorophenyl) -3-, £ (2-chloro-5-

tetradecanamido) -anilino7-4-phenoxy-5-pyrazolone

Compound 1-27 1- (2,6-dichloro-4-methoxyphenyl) -3 - / ^ 2-

chloro-5-tetradecylsulfonamido) -anilino7-

4-acetoxy-5-pyrazolone
Compound 1-28 1- (2,4-dichlorophenyl) -3- / T2-methoxy-5-tetra-

decyloxycarbonyl) -anilineq / -4-benzoylanine-

oxy-5-pyrazolone
Compound 1-29 1- (2,4 _> 6-Trichlorophenyl) -3- (2-chloro-5-

tetradecanainido) -anilino-4- (n-propylamino) -

5-pyrazolone
Compound I-3Q 1- (2,6-dichloro-4-methoxyphenyi) -3- (2-chloro-

5-tetradecyloxycarbonyl) -anilino- ^z f- (phenyl-

sulfonamido) -5-pyrazolone compound 1-3 ^ 1- (4 ~ nitroplienyl) -3- (4-octadecyloxyanilino) -

4— (n-butyramido) -5-pyrazolone compound 1-32 1- (2,4,6-tricb.lorophenyl) -3-2l2-chloro-5-

tetradecanamido) -anilind7-4-anilino-5-

pyrazolone

The 4-substituted 3-arylamino-5-pyrazolones, in particular the compounds corresponding to the above general formula (I) can be prepared by a ring-closing condensation reaction of α-substituted β-alkoxy-O-arylaminoacrylic acid esters, in particular Compounds according to the general formula:

= C ^ (III)

^ COOR ₁ ,

509829/0971

with hydrazines according to the general formula

, (IV)

is carried out.

In the general formulas (III) and (IV), the radicals R ^, Rp and Y have the same meaning as given above for the general formula (I), while R ^ is an alkyl group, for example alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups with 1 to 6 carbon atoms, and R ^ a hydrocarbon group, preferably an alkyl group with 1 to 20 carbon atoms or an aryl group and in particular an alkyl group with 1 to 6 carbon atoms or a phenyl group, where the radicals R ^ and R ^ can be the same or different .

Specific examples of α-substituted ß-alkoxy-ßarylaininoacrylic acid esters, in particular compounds corresponding to the general formula (III), which can be used according to the invention, are given below, but these examples serve only for the purpose of illustration and the present invention is not in any V / also limited to these compounds given as examples. Compound III-1 ethyl-α- (1-piperidino) -ß-ethoxy-ß-

(2-chloro-5-tetradecanamido) -anilino-

acrylate
Compound III-2 ethyl-α- (1-morpholino) -ß-ethoxy-ß-

(2-chloro-5-tetradecananido) -anilino-

acrylate
Compound III-3 n-Butyl-aO-morpholino) -ß-n-butoxy - i-

(2-chloro-5-tetradecanane! Ido) -anilino-

acrylate
Compound III-4 ethyl-α- (5- or 6-methyl-i-benzotri-

azolyl) -ß-ethoxy-ß- (2-chloroanilino) -

acrylate

509829/097 1

link Ii I-5 link III-6 link in-? link 111-8 link III-9 link III-1O link III-11 link III-12 link III-13 link III-14- link 111-15 link III-16

Ethyl-α- (5- or 6-methyl-i-benzotria-

zolyl) -ß-ethoxy-ß- (2-methylanilino) -

acrylate

Ethyl-a- (5 ~ or 6-methyl-i-benzotria-

zolyl) -ß-ethoxy-ß- (2-chloro-5-tetradecan-

amido) anilinoacrylate

Ethyl-α- (5- or 6-methyl-i-benzotria-

zolyl) -ß-ethoxy-ß- (2-methoxy-5-tetradecyl-

oxycarbonyl) anilinoacrylate

Ethyl-a- (5- or 6-bromo-1-benzotriazolyl) -

ß-ethoxy-ß- (4 ~ octadecyloxyanilino) acrylate

Ethyl-α- (5- or 6-bromo-1-benzotriazolyl) -

ß-ethoxy-ß- (2-chloro-5-tetradecanamido) -

anilinoacrylate

Ethyl-α- (5- or 6-methyl-1-benzotriazolyl) -

ß-ethoxy-ß- (2-chloro-5-tetradecanamido) -

anilinoacrylate

Ethyl-a- (5- or 6-nitro-1-benzotriazolyl) -

ß-ethoxy-ß- (2-chloro-5-tetradecanamido) -

anilinoacrylate

Ethyl-α- (5 »5-dimeth.yl-3-hydantoinyl) -ß-

ethoxy-ß- (2-chloro-5-ni'troanilino) acrylate

Ethyl-a- (5i5-diniethyl-2,4 ~ dioxo-3-o>: a-

zolidinyl-ß-ethoxy-ß- (2-chloro-5-nitro-

anilino) acrylate

Ethyl-α- succinimi do-ß-ethoxy-ß- (2 ^ -chlor-

5-tetradecanamido) anilinoacrylate

Phenyl-a- (5- or 6-methyl-i-benzotria-

zolyl) -ß-ethoxy-ß- (2-methoxy-5-tetra-

decyloxycarbonyl) anilinoacrylate

Ethyl-α- (5- or 6-methyl-i-benzotria-

zolyl) -ß-ethoxy-ü- (2-metho: Q ^r -5-tetra-

decyloxycarbonyl) anilinoacrylate '

509829/0971

link III-17 link III-18 link III-19 link III-20 link 111-21 link III-22 link III-23 link III-24- link III-25 link III-26 link III-27 link III-28

Ethyl-α- (5- or ö-methyl-i-benzotriazo-

lyl) -ß-ethoxy-ß- (4-ethoxy-5-tetraäecan-

amido) anilinoacrylate

Ethyl-α- (5,5-dimethyl-3-hydantoinyl) -ß-

ethoxy-ß- (2-chloro-5-tetradecanamido) -

anilinoacrylate

Ethyl-α- (5 5 5-dimethyl-2,4-dioxo-3-oxazo-

lydinyl) -ß-ethoxy-ß- (2-methoxy-5-tetra-

decyloxycarbonyl) anilinoacrylate

Ethyl-α- (5,5-dimethyl-3-hydantoinyl) -

ß-ethoxy-ß- (2-methoxy-5-tetradecylo:>: y-

carbonyl) anilinoacrylate

Methyl-a-phthalimido-ß-methoxy-ß - / ^ -

chloro-5- (2,4- di-1 er t.-ainy! phenoxy) -acet-

amidq / -anilinoacrylate

Ethyl- α- (1 -pyrrolyte 1) -ß-ethoxy-ß -. (2- chlo r-

5-pentadecanamido) anilinoacrylate

Ethyl-a-imidazolyl-ß-ethoxy-ß- (2-chloro-5-

nitroanilino) acrylate

Ethyl-a- (1,2-dihydro-2-oxo-1-pyridyl) -

ß-ethoxy-ß- (3? 5-Ui- ^ e thoxycarbonyl) -anili-

noacrylate

Ethyl-a- (2-oxo-1-piperidino) -ß-ethoxy-ß-

(2-chloro-5-tetradecyloxycarbonyl) -anili-

noacrylate

Ethyl-a-phenoxy-ß-ethoxy-ß- (2-chloro-5-

tetradecanamido) anilinoacrylate

Ethyl-a-acetoxy-ß-ethoxy-ß- (2-chloro-5-tetradecylsulfonamido) anilinoacrylate
Ethyl-α- (benzoylaninoxy) -β-ethoxy-: 1- (2-methoxy-5-tetradecyloxycarbonyl) -anilinoacrylate

509829/0971

Ethyl-a-ptienoxy-ß-ethoxy-ß- (2-methoxy-5-

nitroanilino) acrylate

Ethyl-α- (1-morplioliiio) -ß-ät3ioxy-ß- (2-

chloro-5-nitroanilino) acrylate

Ethyl-α- (5-troni-i-benzotriazolyl) -ß-

ethoxy-ß- (4-nitroanilino) acrylate

Ethyl-a-phthalimido-ß-ethoxy-ß- (2-chloro-

5-tetradecanamido) anilinoacrylate

Ethyl-α- (1-piperidino) -ß-ethoxy-ß-anilino-

acrylate

Ethyl-α- (1,2-dihydro-2 ~ oxo-1-pyridyl) -

ß-ethoxy-ß- (4-methoxyanilino) acrylate

Propyl-a- (1-piperidino) -ß-propoxy-ß-

(2-chloroanilino) acrylate

Ethyl-a-phthalimido-ß-ethoxy-ß- (2-ynethyl-

anilino) acrylate

Ethyl-α- (n-propylamino-ß-ethoxy-ß- (2-chloro-

5-tetradecanamido) anilinoacrylate

Ethyl-α- (phenylsulfonamido) -ß-ethoxy-ß-

(2-chloro-5-tetradecyloxycarbonyl) -anilino-

acrylate

Ethyl-α- (n-butyramido) -ß-ethoxy-ß- (4-octa-

decyloxy) anilinoacrylate

'. Ethyl-α-anilino-ß-ethoxy-ß- (2-chloro-5-tetradecanamido) -anilinoacrylate.

Specific examples of hydrazines corresponding to the general formula (IV), which can be used according to the invention, are given below, but these examples only serve to illustrate, without the invention being limited to these examples. Compound IV-1 phenylhydrazine
Link; IV-2 4-chlorophenyl hydrazine

link III-29 link III-3O link III-31 link III-32 link III-33 link III-34 link III-35 link III-36 link III-37 link III-38 link III-39 link II1-40

8 29/0971

4-nitrophenyl hydrazine
Hydrazine
Benzyl hydrazine

2,4,6-trichlorophenyl hydrazine 4-chlorobenzyl hydrazine
2,6-dichloro-4-metiioxyphenylhydrazine 2,4-dimethyl-6-chlorophenylhydrazine 2,4-dichlorophenylhydrazine (2-octadexyloxyplienyl) carbamoylmethylhydrazine

ß-cyanoethylhydrazine
4- ^ 2,4-di-tert-amylphenoxy) -acetamido_7-phenylhydrazine

4- / ä- (3-pentadecylphenoxy) -butyramido7-phenyl'hydrazine
2,4-Dichloroenzylhydrazine 'The preparation of the α-substituted ß-alkoxy-ßarylainino acrylic acid esters, in particular the compounds of the general formula (III), which can be used according to the invention, can be carried out by a process in which an o-l-nitrobenzodiazonium salt is among Coupling in the α-position of a ß-alkoxy-ß-arylaminoacrylic acid ester is reacted, for example the process according to US Pat. -ß-alkoxy-ß-arylaminoacrylate, which of the general formula (III) comprises v / ird, subjected to wix-d. More preferably, these compounds can be converted into an α-halo-β-alkoxy-β-arylaminoacrylic acid, in particular compounds of the general formula

link IV-3 link IV-4 link IV-5 link IV-6 link IV-7 link IV-8 link IV-9 link IV-10 link IV-11 link IV-12 link IV-13 link IV-14 link iv-15

509829/0971

where Rp »^ * ^^ ^ 4 ^^ - ^{e have the} same meaning as in the general formula (III) and X is a halogen atom, for example a chlorine atom, a bromine atom or a fluorine atom, can be prepared with YH or Y ~ *.

For YH and Y ~, which are used in the above substitution reaction, Y has the same meaning as in the general formula (III).

The compounds corresponding to the general formula (II) as used according to the invention can be used by conventional halogenation of known ß-alkoxy-ß-arylaminoacrylic acid esters be made such. B. in British Patents 1,325,828, 1,129,333, 1,129,334. The a-halo-ß-alkoxy-ß-arylaminoacrylic acid esters can preferably be prepared with very high yields and very high stability when halogenation of ß-alkoxy-ß-arylaminoacrylic acid esters with JN [-chlorosuccinimide, N-bromosuccinimide or N-fluorosuccinimide in an aprotic solvent, for example ethyl ether, carbon tetrachloride, chloroform, acetonitrile, dioxane, Benzene, toluene and the like., Is carried out. The compounds obtained by this process are new compounds and so far not described.

Specific examples of compounds according to general formula (II) used according to the invention are given below, but these examples are only intended to explain the

509829/0971

Serving the present invention and the invention is not limited to these examples.

Compound II-1 Compound 11-2

Compound II-3 Compound II-5 Connection I1-6

Ethyl-a-bromo-ß-ethoxy-ß-anilinoacrylate

Ethyl-a-bromo-ß-ethoxy-ß- (2-chloroanilino) -

acrylate

Ethyl-a-bromo-ß-ethoxy-ß- (o-toluidino) -

acrylate compound II-4 ethyl-a-bromo-ß-ethoxy-ß- (p-anisidino) -

acrylate

Ethyl-a-bromo-ß-ethoxy-ß- (4-nitroanilino) -

acrylate

Ethyl-a-bromo-ß-ethoxy-ß- (2-chloro-5-ni "cro-

anilino) acrylate compound II-7 ethyl-a-bromo-ß-ethoxy-ß- (2-methoxy-5-nitro-

anilino) acrylate

Ethyl-a-bromo-ß-ethoxy-ß- ^ 2-chloro-5-

tetradecanamido) anilino / acrylate

Ethyl-a-chloro-ß-ethoxy-ß- _/ ^ f (2-chloro-5-

tetradecanamido) -anilino7-acrylate compound 11-10 Kethyl-a-bromo-ß-i! iethoxy-ß- _< / 1C2-chloro-5-

tetradecanamido) -anilino7-acrylate compound 11-11 ethyl-a-bromo-ß-ethoxy-ß- (4-stearyloxy-

anilino) acrylate compound 11-12 ethyl-a ~ bron-ß-ethoxy-ß- / l2-methoxy-5-

tetradecyloxycarbonyl) -anilino7-acr3rlat compound 11-13 ethyl-a-bromo-ß-ethoxy-ß- ^ X4-methoxy-J—

te trade canamido) -anilino _> / -acryl at compound 11-14 butyl-a-broin-ß-butoxy-ß- ^ 2-chlDr-5-

tetradecanamido) -anilineq7-acryl3.t compound 11-15 phenyl-a-bromo-ß-ethoxy-ß- / X2-r: e fchoxv-

Compound I1-8 Compound II-9

Compound 11-16 propyl-a- _t iodo-ß-propoxy-ß- (2-chlo:

acrylate

509829/0971

- 55 -

Link; II-I7 methyl-a-bromo-ß-methoxy-ß- / 2-chloro-5-

(2,4-di-tert-amylphenoxy) -acetamido anilino_7-acrylate.

Of the compounds represented by the above general formula (II), physical Determinations such as infrared absorption spectrum, nuclear magnetic resonance absorption spectrum and the like are confirmed, that they are tautomers as shown below:

COOR ₁ ,

(ID

(V)

wherein R ₂ , R ₃₅ , R ^ and X have the same meaning as above.

Since the compounds represented by the general formula (II) are vinyl halides, the halogen atom is usually according to X not reactive or has at most a very low reactivity. But the fact that these compounds tautomers with the compounds are represented by the general formula (V) shows that the halogen atom indicated by X undergoes a substitution reaction as easily as a halogen atom in a halo-renated Alkyl can bring about and actually the substitution reaction takes place of the compounds corresponding to the general formula (II) slightly from what one of the characteristics of the present invention.

509829/0971

_ 34 -

The reaction of the α-halogen-ß-alkoxy-ß-arylaminoacrylic acid ester corresponding to the general formula (II) with a base, such as a primary amino or a secondary Amine, e.g. B. an Älkylamin, such as alkylamines with 1 up to 20 carbon atoms, a dialkylanine such as dialkylamines with alkyl proportions of 1 to 20 carbon atoms, a cyclic amine such as pyrrolidine, piperidine, substituted piperidine, for example with alkyl groups 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogen atoms, substituted piperidines, Morpholine, substituted morpholine, such as with alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogen atoms and the like, substituted morpholines and the like. Using 2 to 20 KoI of the amine described above, per mole of the compound of the general formula (II) at temperatures in the range from 10 to 100 G in the absence or in the presence of an inert solvent such as benzene, toluene, acetone, acetonitrile, Methanol, ethanol, dimethylformamide, dimethyl sulfoxide and the like., And provides the compounds according to the general formula (III). Reaction temperature and reaction time vary depending on of the specific connection. In a preferred embodiment, the reaction is carried out using FIG to 10 moles of amine per mole of the compound of the general Formula (II) in the absence or in the presence of a solvent at a temperature in the range from 20 to 50.degree carried out within about 1 to 10 hours. The reaction can especially by adding a compound that for Is capable of removing hydrogen halide, for example a hydrogen halide acceptor, such as a tertiary λτϊπ, Sodium acetate and. Like., be promoted. Uach the original number

509829/0971

the reaction mixture is mixed with a solvent a strong extraction effect, such as jither, ethyl acetate, Chloroform and the like, extracted and the extract washed sufficiently with VTsser, with a dehydrating agent, such as anhydrous sodium sulfate, anhydrous magnesium sulfate and the like, dried and concentrated to obtain the compound represented by the general formula (III). The implementation of the a-halo-ß-alkoxy-ß-arylaminoacrylic acid ester corresponding to the general formula (II) with a weak base or an acidic compound with a hydrogen atom capable of dissociation and a pEa vert " from about 3 to 16, such as succinimide, a substituted one Succinimide, for example with alkyl groups having 1 to 20 carbon atoms, halogen atoms, aryl groups and the like., substituted succinimides, phthalimide, substituted phthalimide, for example with one or more substituents, such as halogen atoms, nitro groups, alkyl groups with 1 to 20 carbon atoms, acylamino groups, carbamoyl groups, N-alkylcarbamoyl groups, N-arylcarbamoyl groups, Alkoxy groups, aryloxy groups, alkylthio groups, acyloxy groups, Carboxy groups, sulfo groups, alkylsulfonyl groups, Alkoxycarbonyl groups, ureido groups, cyano groups, Sulfoalkyl groups and the like, substituted phthalimides, o-sulfobenzoylimide, Hydantoin, 5-substituted hydantoin, for example one in the 5-position with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylidene group having 1 up to 20 carbon atoms, an anisylidene group with 1 up to 20 carbon atoms and the like, substituted hydantoins, 5i5 ~ disubstituted hydantoin, for example nit those given above for the 5-substituted hydantoin Substituents, diglycolimide, 2,4-dioxooxazolidine, 5-substituted 2,4-dioxooxazolidine, for example

509829/0971

with the substituents indicated for the 5-substituted hydantoin indicated above, 5i5'-disubstituiert.es 2,4-dioxooxazolidine, for example with the substituents indicated above for the 5-substituted hydantoin, 2,4-dioxothiazolidine, 1-phenylurazo1, 2- Oxocycloanine, 1,2-dihydro-2-oxo-1-pyridyl, 1,2-dihydro-4-oxo-1-pyridyl, 1,2-dihydro-2-oxo-1-thiopyridyl, 1,2-dihydro- 4-oxo-1-thiopyridyl, uracil, 5i6-dihydrouracil, 2-pyrimidone, 4-pyri'eidone, 3-pyridazone, 2-pyrrazone, 3-P; 7'i ^> idazon, 2,6-dioxopiperidine, 2, 6-Dioxopiperazine, pyrrole, substituted pyrrole, for example with the substituents given above for the 5-substituted hydantoin, imidazole, pyrazoline, indoline, isoindoline, IH-isoindoline, benzotriazole, substituted benzotriazole, for example with a halogenated of an alkyl group having 1 to 20 carbon atoms , an acylamino group such as an acylamino group having an alkyl moiety of Ί to 20 carbon atoms or an aryl moiety, and the like, a C arbamoyl group, a sulfonamide group, a sulfamoyl group, a nitro group, a cyano group, a sulfo group and the like, substituted benzotriazoles, benzimidazole, substituted benzimidazoles, for example with the substituents given above for the substituted benzotriazole, pyrimidine, imidazolides, carboxylic acids with 1 to 20 fatty acids, for example Carbon atoms, aromatic carboxylic acids such as benzoic acid, naphthoic acid and the like, or other carboxylic acids such as nicotinic acid, aromatic hydroxy hydrocarbons, for example phenol, naphthol and the like, an oxime, a hydrocyanic acid, an arylamine, for example aniline, ITaphthylamine and the like, can be effective in the presence of a strong agent effective for removing hydrogen halide, for example a base, such as triaryylamine, trimethylamine, 1,4-diazabiscyclo (2.2.2) octane (LABCO), 1,5-Eiazabiscyci: -

509829/0971

- zn -

(4,3,0) nonene (5) and the like. In an amount of about 1 to 5 mol per ha of the compound of the general formula (II), alternatively after conversion of the above-described acidic compound into an alkali salt, for example a sodium salt, a potassium salt, a magnesium salt, a lithium salt and the like. Inert solvents such as methanol, Ethanol, benzene ,. Toluene, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide and the like are used will. The reaction can be carried out at temperatures in the range from about 0 to 150 ° C and the reaction time, which may vary depending on the specific compound, ranges from 30 minutes to 24 hours. The amount of the above-described alkali salt of the acidic compound can be used within a range of about 1 to 5 moles per mole of the compound of general formula (II) depending on the specific Compound vary, but more than 5 moles is generally unnecessary. In a preferred embodiment the reaction using 1.5 to 3 moles of the above-described alkali metal salt of the acidic Compound, in particular its potassium salt, per mole of the compound corresponding to the general formula (II) in an aprotic polar solvent such as dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide and Like., At a temperature in the range of 20 to 40 C, for example room temperature, which for a minimum Formation of by-products is beneficial carried out. A response time in the range of about 2 to 10 hours is sufficient to obtain preferred results. When the reaction is complete, a solvent with a srarken Extraction effect, such as diethyl ether, ethyl acetate,

509829/0971

Chloroform and the like, in an amount 2 to 10 times Amount by volume of the reaction mixture to the mixture containing the compound of the general formula (III) which was formed in the substitution reaction was added and the mixture with sufficient water to remove the remaining alkali salt of the acidic compound washed. If the alkali salt cannot be removed by washing with water, an aqueous 2- to 5% sodium hydroxide solution was added to the mixture and then the mixture with water for complete removal of the alkali salt washed. Then a dewatering agent is used, such as anhydrous sodium sulfate, anhydrous magnesium sulfate and the like to the extract for drying added and the extract concentrated to obtain a compound of the general formula (III) in pure form.

The compound corresponding to the general formula (III) can in pure form and in high yield after The process described above is produced and can be used in the form of a gel without further purification the next reaction with the hydrazine of the general formula (IV) can be used.

The reaction to obtain the compound of the general formula (I) can be carried out by refluxing the acrylic acid ester of the general formula (III) and the hydrazine of the general formula (IV) in the absence of a solvent or in the presence of an inert solvent such as methanol, Ethanol, acetonitrile, benzene, toluene, dimethylformamide, chloroform, carbon tetrachloride and the like. With regard to the proportions of the reactants " rJ '-" ~ borrowed the acrylic acid ester derivative according to the general formula (III) and of the hydrazine according to the general formula (IV), it was determined in some cases.

509829/0971

states that preferred results are obtained if the hydrazine is used in excess, i.e. H. more than 1 mole to about 10 moles per mole of the acrylic acid ester derivative.

The above-described reaction can advantageously be carried out in the absence of a solvent in most cases in order to minimize the formation of by-products and to avoid the decomposition of the acrylic acid esters. The amount of the hydrazine corresponding to the general formula (IV) is generally preferably in the range from 1 to 3 mol per mol of the acrylic acid ester. A suitable acid, for example acetic acid, propionic acid, phenol, formic acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, cresol and the like, can also be used in the reaction. The reaction can generally be carried out at a temperature in the range of about 20 to 200 ° C for about 1 to 24 hours. The suitable temperature may vary depending on the specific compound, but usually a range of 60 to 130 ° C is particularly effective. In the case of the formation of an α-substituted ß-anilino-ß-hydrazinoacrylic acid ester, which is an intermediate for the pyrazolone according to the general formula (I), the intermediate can easily be converted into the compound according to the general formula (I) by treatment with a strong Alkali such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium alkoxide and the like can be converted in a solvent such as methanol, ethanol and the like under mild conditions.

The following examples serve to explain the invention further, without the invention being limited thereto is. Unless otherwise stated, all are. Parts, percentages, ratios and the like, by weight, based.

509829/0971

example 1

Preparation of 1-phenyl-3-Zl2-chloro-5-tetradecanamido) -anilino / - · 4- (1-piperidino) -5-pyrazolone

Stage 1: Production of ethyl-α- (1-piperidino) -ß-etho}: y- B- / X 2-chloro-5-tetradecane amido; -anilino_7-acryl at

27.9 g (0.05 mol) of ethyl-a-bromo-ß-ethoxy-ß- / X2-chloro-5-tetradecanamido) anilino7-acrylate (Compound H-S, melting point 61 to 64 ° C.) were dissolved in 50 ml of piperidine and left to stand at room temperature for 24 hours. the white crystals obtained were filtered off and washed with ethyl acetate. The ethyl acetate was extracted with the filtrate mixed and this an excess of ethyl acetate added and washed sufficiently with water until a neutral pH and then dried with anhydrous sodium sulfate. After removing the ethyl acetate Under reduced pressure, the remaining oily residue represented the pure desired compound. The yield was 27 g

Step 2 : preparation of compound 1-1

7.57 S phenylhydrazine were added to 27 g of the acrylate obtained in stage 1 and the mixture was heated with stirring to 105 ° to 110 ° C. for 5 hours under nitrogen gas. 50 ml of ethanol were added to the reaction mixture and the substance which did not dissolve in the ethanol was filtered off. The filtrate was left to stand on a cold Orr, with 11 g of the compound ~ 1- ^Λ - n having a melting point of 160 to 163 ° C were obtained.

509829/0971

68 , 7 8th , 09 11 ,8th 68 , 86 8th , 15 11 , 71

Elemental analysis (C ^ H ^ Nt-O

. CH

Calculated (%): Found (%):

The chemical structure of the compound was also made by confirmed the IR spectrum and NMR spectrum analyzes.

Example 2

Preparation of 1- (4-chlorophenyl) -3-.Zl2-chloro-5-tetradecanamido) -aniline7-4- (i-morpholino) -5-pyrazolone (Connection 1-2)

Step 1; Production of ethyl-α- (1-morpholino) -ß-ethoxyß- ^ f (2-chloro-5-tetradecanamido) -anilino7-acrylate

Using the same procedure as in step 1 of Example 1, using 15 S ethyl ct-bromo-ßethoxy-ß - / (2-chloro-5-tetradecanamido) aniline £ 7-acrylate 14.2 g of the pure, oily compound desired were obtained.

Step 2: Establishing the connection 1-2

To 14 g of the acrylate obtained in Step 1 above, 3.5 g of p-chlorophenyl hydrazine were added and treated the mixture using the same procedure as in Step 2 of Example 1, leaving 5 E crystals with a melting point of 160 to 171 ° C were obtained.

509829/0971

Elemental analysis (C,,

H N

Calculated (%): 62.9 7.14 11.1

Found (%): 62.79 7.19 11.3

The structure of the compound was also determined by IR spectrum and HKR spectrum analyzes.

Example 3

Preparation of 1-phenyl-3-Zl2-chloro-5-tetradecanamido) -anilino7-4- (1-morpholino) -5-pyrazolone

Hach the same procedure as in Example 1 using 5.8 g of ethyl a- (i-morpholino) -ß-ethoxy-ß- ^ 2-chloro-5-tetradecanamido) -anilino7-acrylate and 1.3 g of phenylhydrazine and recrystallization from ethanol, 3.8 g of crystals with a melting point of 151 to 153 ° - of 1-phenyl-3- / 12-chloro-5-tetradecanamido) -anilino7-4- (1-morpholino) -5-pyrazolone were obtained .

Elemental analysis (C ,, H ₂ ^ N, -O, .Cl):

Calculated (%): Found (%):

The structure of the compound was also determined by IR spectrum and 2KH-3pectrum analyzes.

C. 5 7th H_ II 66 32 7th , 72 11 66

509829/0971

Example 4

Preparation of 1- (4-nitrophenyl) -3- (2-chloroanilino) -4- (5- or 6-methyl-1-benzotriazolyi; -5-pyrazolone (compound 1-4)

Stage 1_j_ Production of ethyl α- (5- or 6-methyl-1-benzotriazolyl) -ß-ethoxy-ß- (2-chloroanilino) acrylate

35 g of ethyl-a-bromo-ß-ethoxy-ß- (2-chloroanilino) acrylate (Compound II-2) and 25 g of the potassium salt of 5- ^ ethylbenzotriazole were in 250 ml of dimethylformamide at room temperature stirred for 2 hours. The reaction mixture was poured into excess ethyl acetate, sufficient washed with water, with a 2% aqueous sodium hydroxide solution washed and washed again with water until it was neutral. The ethyl acetate phase was washed with anhydrous Sodium sulfate dried and concentrated, 41 g of practically pure, oily desired compound being obtained became.

Step 2: Establishing the connection 1-4

To 8 g of the acrylate obtained in step 1 above, 3 g of p-nitrophenylhydrazine were added and the mixture was stirred at 105 ° C. for 5 hours. Hot Methanol was added to the reaction mixture and the solid which did not dissolve in methanol was filtered off. The solid was washed with hot methanol, and the methanol was washed with the filtrate and concentrated. Recrystallization from acetonitrile gave 5 S of compound 1-4 with a melting point of 175 to 177 ° obtain.

509829/0971

Elemental analysis (Cp-H, -cN ^ O ^ Cl)

C H N

Calculated (%): 57.2 3.47 20.7

Found (%): 57.41 3.46 20.6

The structure of the compound was also determined by IR spectrum and NMR spectrum analyzes.

Example 5

Production of 3-Z "(2-chloro-5-tetradecanamido) -anilino / -4- (5- or 6-methyl-1-benzotriazolyl) -5-pyrazolone (compound 1-6)

Stage 1 : Production of ethyl α- (5- or 6-methyl-ibenzotriazolyl-ß-ethoxy-ß- / X2-chloro-5-tetradecanamido) anilino7-acrylate

Was as in step of Example 4 using the same method with the use of 29 S-ethyl-ct bromß-ethoxy-.beta.-Z (2-chloro-5-tetradecanair _i ido) aniline £ 7-acrylate (Compound II-8 ) and 16 g of the potassium salt of 5-kethylbenzotriazole obtained the practically pure, oily desired compound quantitatively.

Step 2: Establishing the connection 1-6

19 g (0.0304 mol) of the acrylic-tr obtained in step 1 and 1.8 g (85 %> 0.0306 mol) of hydrazine hydrate were dissolved in 150 ml of methanol and the mixture was heated to reflux while stirring. After 2 hours, the same solution of hydrazine hydrate was added and the mixture was refluxed for an additional 30 minutes. After finished-.w

509829/0971

Reaction, the methanol was distilled off and 100 ml of diethyl ether were added to the remaining oily residue added and the mixture, overnight at 10 ° C or below left to stand so that a white solid separated out. The solid was filtered off, sufficient washed with diethyl ether and then with ethyl acetate, dissolved in 50 ml of acetic acid and poured into ice water. Of the White deposited solid was filtered and dried, whereby 6 g of the compound 1-6 with a melting point of 126 C (decomposition) were obtained.

Elerr.entaranalysis

H N

Calculated (%): 63.7 7.10 17.4

Found (%): 63.57 7.24 17.49

The structure of the compound was also determined by IR spectrum and NKR spectrum analyzes.

Example 6

Preparation of 1-Benzyl-3- (4-octadecyloxyanilino) -4- (5- or 6-bromo-1-benzotriazolyl) -5-pyrazolone (compound 1-3)

15 g of ethyl α- (5- or 6-bromo-1-benzotriazolyl) -B-ethoxy-ß- (4-octadecyloxyanilino) acrylate (Melting point 65 to 67 C), which is made by the same procedure as in Step 1 of Example 4 using ethyl-oc-bror.-ß-ethoxy-3- (4-octadecyloxyanilino) acrylate (Compound 11-11) and 5-2 g of benzylhydrazine was obtained heated to 90 ° C for 10 minutes with stirring,

509829/097 1

2.6 g of acetic acid were added and then further heated at the same temperature for 11 hours with stirring. After the completion of the reaction, the reaction mixture was dissolved in ethyl acetate and washed repeatedly with water. The ethyl acetate solution was dried with anhydrous sodium sulfate and concentrated. The remaining oily product was recrystallized from acetonitrile / ethyl acetate, whereby 14.5 g of compound 1-8 with a melting point of 105 to 110 ° C were obtained.

Elemental analysis

Calculated (%): Found (%):

65 , 9 7th , 27 11 , 5 66 , 09 7th , 48 11 , 44

The structure of the compound was also determined by IR spectrum and NMR spectrum analyzes.

Example 7

Preparation of 1-benzyl-3- / t2-chloro-5-tetradecanamido) -anilinoJ-4- (5- or 6-bromo-1-benzotriazolyl) -5-pyi'azolone (Connection 1-9)

To 18 g of ethyl α- (5- or 6-bromo-1-benzotriazolyl) -ß-ethoxy-ß - / ^ 2-chloro-5-tetradecanamido) -aniline27-acrylate, which using the same procedure as in Stage 1 of Example 4 using ethyl-a-bro --.- ß-ethoxy-ß- _< /j2-chlor-5-tetradecanarr.ido )-anilino7-acrylm; (Compound II-8) was obtained, 9.5 S Senzy: hydrazine was added and the Genisch in a bath with a

Temperature from

C for 3 hours with stirring he ":.! -:

509829/0971

After the reaction, a small amount of ethyl acetate was added added to the reaction mixture so that a solid separated out. The solid was filtered off, dried (14 g), dissolved in a small amount of acetic acid and poured into ice water. The white solid was filtered off and recrystallized from acetic acid, whereby 10 g of the compound 1-9 with a melting point of 164.5 to 167 ° C were obtained.

60 , 0 5 , 98 13, 6th 59 , 89 6th , 03 13, 75

Element ar analysis (C ^ g ^^

_C _H N

Calculated (%): Found (%):

The structure of the compound was also determined by IR spectrum and MMR spectrum analyzes.

Example 8

Preparation of 1-benzyl-3- / l2-chloro-5-tetradecanamido) -anilino7-4- (5- or 6-methyl-1-benzotriazolyl) -5-pyrazolone (compound 1-10)

To 21.5 g of ethyl-α- (5- or 6-methyl-1-benzotriazolyl) -ß-ethoxy-ß-Z "( 2-chloro-5-tetradecane amido) -anilino, 7-acrylate, obtained as in Step 1 of Example 5, 12.6 g of benzyl hydrazine was added and the mixture treated in the same manner as in Example 7 and recrystallized from acetonitrile to give 6.5 S of the compound 1-10 with a melting point of 157 to 161 ° C became.

509829/0971

67 , 7 7th , 02 14th , 08 67 , 99 7th , 06 15th

Elemental analysis (C ^ H ^ NnOgCl)

C H 'N

Calculated (%):
Found (%):

The structure of the compound was also determined by IR spectrum and IMR spectrum analyzes.

Example 9

Production of 1-benzyl-3- / t2-chloro-5-tetradecananido) -anilino7-4- (5- or 6-nitro-1-benzotriazolyl) -5-p'yrazolone (compound 1-11)

To 3.3 g of ethyl-a- (5- or 6-nitro-i-benzotriazolyl) -ß-ethoxy-ß-2X2-chloro-5-tetradecane amido) -anilino7-acrylate, the same procedure as in step 1 of Example 4- using ethyl-a-bromo-ß-ethoxy-I2- / l2-chloro-5-tetradecanamido) anilino7-acrylate (Compound II-8) was obtained, 2.3 g of benzyl hydrazine was added and the mixture treated in the same manner as in Example 7. The deposited from ethyl acetate Crystals were dissolved in acetic acid and then poured into ice water. The solid precipitate was filtered off and dried, with 2 g of a white I-eststoffes with a melting point

Element analysis (C.

a melting point of 116 to 118 ° C were obtained.

Calculated (%): 63.0 6.2 ^ΓΤ 16,

Found (%): 63.07 6.29 16.

509829/097 1

The structure of the compound was also determined by IR spectrum and NMR spectrum analyzes.

Example 10

Preparation of 1- (4-nitrophenyl) -3- / T2-methoxy-5-tetradecyloxycarbonyl ) -anilino7-4- (5- or 6-methyl-1-benzotriazolyl) -5-pyrazolone (Connection 1-16)

21.7 g of ethyl α- (5- or 6-methyl-1-benzotriazolyl) -ß-ethoxy-ß- / t2-methoxy-5-tetradecyloxycarbonyl) -anilino7-acrylate, which by the same procedure as in step 1 of Example 4 using ethyl-a-bromo-ß-ethoxyß - ^ (2-riethoxy-5-tetradecyloxycarbonyl) -anilino7-acrylate (Compound 11-12) were obtained with 7 * 8 g p-Nitrophenylh ^ rdrazine mixed at 25 ° C and this 3.0 g of acetic acid were added with stirring. Yes, at 25 ° C had been stirred for 15 minutes, solidified the mixture. The mixture was melted and the mixture was melted by increasing the temperature of the bath to 80 to 83 ° C stirred for 5 hours. Near the completion of the reaction, the mixture started at that indicated above Solidify temperature. By adding acetonitrile to the mixture, crystals were deposited, which were formed Acetonitrile were recrystallized, so that 7.0 g of the Compound 1-16 with a melting point of 140 to. 143 ° C were obtained.

Elemental analysis

C H N

Calculated (%) '- 65.4-6.74-14-, I.

Found (%): 65.59 6.59 '14.21

509829/0971

The structure of the compound was also determined by IR spectrum and MIR spectrum analyzes.

Example 11

Preparation of 1-Benzyl-3 - / (4-methoxy-3-tetradecanaiiiiio) -anilineq7-4- (5 ~ or 6-methyl-1-benzotriazolyl) -5-pyrazolone (compound 1-17)

7.5 g of ethyl cc- (5- or 6-methyl-1-benzotriazolyl) -E-ethoxy-ß - / "(4-methoxy-3-tetradecanamido) -aniline-7-acrylate, which using the same procedure v: ie in stage ' ¹ of Example 4 using ethyl-a-bron-ß-ethoxy-2- £ X4-methoxy-3-tetradecanamido) anilino7-acrylate (compound 11-13) had been obtained, and 3 g of benzylhydrazine were stirred at 80 ° C. for 10 minutes, and 1 »4-5 S acetic acid was added thereto and the mixture was heated at the same temperature for 10 hours. After the reaction, the reaction mixture was dissolved in ethyl acetate and washed sufficiently with water The ethyl acetate phase was dried and concentrated. The residue was recrystallized from acetonitrile / ethyl acetate (volume ratio 2: 1). The crystals were filtered and sufficiently washed with acetonitrile, so that 2.6 g of the compound 1-17 having a melting point of 129 to 130, 5 ° C were obtained.

Elemental analysis

C H N

Calculated (%): 70.0 7.53 "x 5, Ί

Found (%) : 69.99 7.53 15.02

The structure of the compound was also determined by IR spectrum and KKR spectrum analyzes.

509829/0971

Example 12

Production of 1- (4 ~ Nitraph.enyl) -3- / l2-methoxy-5-tetradecyloxycarbonyl) -anilino7-4— (5,5-dimethyl-3-hydantoinyl) -5-pyrazolone (Connection 1-20)

22.0 g of ethyl a- (5,5-dimethyl-3-hydantionyl) -ß-ethoxyß- / j [2-ynethoxy-5-tetradecyloxycarbonyl) -anilino7-acrylate,
obtained by the same procedure as in step 1 of Example 4- using ethyl-a-bromo-ß-ethoxy-ß - ^ (2-methoxy-5-tetradecyloxyearbonyl) anilino_7-acrylate (compound 11-12) was, were mixed with 8.0 g of p-nitrophenylhydrazine at 25 C and 3 _? 1 g of acetic acid was added with stirring. It was stirred at this temperature for 1 hour and then the temperature of the bath to 68 bis
72 ° C and the mixture stirred at this temperature for 8 hours. Near the completion of the reaction, the mixture began to solidify at the temperature indicated above. By adding acetonitrile to the mixture, crystals were deposited. The crystals were in
Dissolved ethyl acetate, 1 g of activated charcoal was added to the solution and the solution was kept at 60 ° C. for 30 minutes, after which it was filtered with Celite. The filtrate was concentrated and the residue was recrystallized from ethanol, whereby
8.6 g of compound 1-20 with a melting point of 158
to 160 ° G were obtained.

Elemental analysis

C HN

Calculated (%) : 62.4 6.95 12.1

Found (%): 62.53 6.86 12.1:

509829/0971

The structure of the compound was also determined by IR spectrum and 3MR spectrum analyzes.

Some of the advantages that can be achieved according to the invention are as follows: The method according to the invention is in terms of cost compared to the usual ones Process advantageous in which the substituent is introduced in the 4-position of the pyrazolone, since high Yields and abbreviated reaction levels achieved. Since the process is one for a very wide range of applications represents a suitable manufacturing process and since pyrazolones, in which various substituents in the 4- ^ position are introduced, can be produced very easily compared to conventional processes, couplers can πit the desired photographic properties can be obtained very easily by the process according to the invention. Furthermore, the 4-substituted J-arylamino-ppyrazolones are used as intermediates and partially with the formation of new 4-substituted? -arylamino-5-pyrazolones converted as a tagakupier or color developer for the color diffusion transfer process for which, for example, the iiitrc group to the A2ri.n0 group can be reduced and then acyiated, so that a non-diffusible group in the coupler molecule can be introduced.

The 3-rylamino-5-pyrazolones which are substituted in the 4-position and obtained according to the invention are so-called two-equivalent couplers which require only half the amount of silver compared to the usual A-equivalents, so that they also contribute to saving silver and result in an improvement in image sharpness due to a reduction in the thickness of the silver emulsion layer. The couplers produced according to de. ™ Verfahr, ~ o: ä.:.: Of the invention also have eir.i "..

509829/0971 BATH ORIGINAL

gene coupling effectiveness. The coupler with the desired Coupling rates can be easily obtained by selecting the substituent at the 4-position. Of the 3- ■ arylamino-5-p7.razolones substituted in the 4-position, which can be prepared by the process according to the invention have those having a 1-benzotriazolyl group in the ^ position special superiority as so-called DIR couplers and their application contributes to improvement the color rendering, the sharpness, the grain and the like.

The substituted in the 4-position obtainable according to the invention 3 - i-rylamino-5-pyrazolones can be used in photographic light-sensitive materials, in particular as magenta couplers for color photographic light-sensitive materials Materials used. You can apply for color photographic photosensitive materials using of silver halides are used as light-sensitive substances, e.g. for color negative films, Color papers, color positive films, 8mm color films, direct Color positive films, direct color positive papers, photosensitive materials for color diffusion transfer process, color photographic light-sensitive materials in accordance with German OLS 2 226 770, color photographic photosensitive materials suitable for the treatment described in U.S. Patent 3,765,891 are suitable and for similar purposes.

The invention has been described above in detail on the basis of specific embodiments without them is limited to this.

509829/0971

Claims (12)

Claims 1. Process for the preparation of 4-substituted 3-Arylamino-5-pyrazolones according to the general Formula: (I) wherein E ^ is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, Rp ^β ^ ^{η is} hydrogen, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an alkylsulfonic acid group, a carbanide group, an acylamino group, a cyano group, an alkoxycarbonyl group, a sulfonamino group , a sulfamoyl group, a diacylamino group, a carbamoyl group, a carboxy group, a sulfo group or a nitro group and T an alkylamino group, a dialkylamino group, a sulfonamino group, an acylamino group, a diacylamino group, one with the 4-position of the pyrazolone ring via the nitrogen atom in the heterocyclic ring linked nitrogen-containing heterocyclic group or a releasable group linked to the 4-position of the pyrazolone ring via an oxygen atom, characterized in that a ring-closing condensation reaction of a compound corresponding to the general formula 509829/0971 Cm) wherein Rp and Y have the meanings given above and R ^ represents an alkyl group with a hydrazine the general formula R ₁ NHNH ₂ , (IY) wherein R ^ is a hydrocarbon group will. 2. The method according to claim 1, characterized in that that the ring closure condensation reaction is carried out in the absence of a solvent. 3. The method according to claim 1, characterized in that that the ring-closing condensation reaction is in the presence an inert solvent is carried out. 4-. Method according to claim 3 »characterized in that that the ring closure condensation reaction is carried out in the presence of an acid. 5. The method according to claim 1 to 4-, characterized in that die'Ringschlusskondensationsreaktion at a temperature in the range of 20 to 200 ° C is carried out. 6. The method according to claim 5> characterized in that that the ring-closing condensation reaction takes place at one temperature is carried out in the range from cZ to 130 ° C. 7 · Procedure nac :. ^ nspruch Λ to 6, characterized in that the ring ^ final condensation reaction is carried out in counter /; kind of a strong alkali. 509829/0971 8. The method according to claim 1 to 7? characterized, that a molar ratio of the hydrazine to the compound of the general formula (III) in the range of about 1: 1 to 10: 1 is used. 9. The method according to claim 8, characterized in that that a molar ratio of the hydrazine to the compound corresponding to the general formula (III) in the range from 1: 1 to 3: 1 is used. 10. The method according to claim 1 to 9i, characterized in that that a compound is used in which Y represents a benzotriazolyl group. 11. Process for the preparation of a 4-substituted one 3-Arylamino-5-pyrazolones according to the general formula (χ, wherein R _x , a hydrogen atom, an alkyl group, an λralkyl group or an aryl group, Rp a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an alkylsulfonic acid group, a carcamide group, an acylamino group, a cyano group, an alkoxycarbonyl group, a sulfonaninod group , a £ \; 1ια-moyl group, a diacylaisino group, a Carbamoylrru; ' ^ - ■: ■, a carboxy group, a sulfo group or a Ni tr: "; - *.": ■: · ^ and Y an alkylamino group, a Liallcylariinogrupc ΐ. ir.c ORIGINAL BATHROOM 509829/097 1 Sulfonanino group, an acylamino group, a diacylamino group, one with the 4-position of the pyrazolone ring above the nitrogen atom in the heterocyclic ring bonded nitrogen-containing heterocyclic group or a with the 4-position of the pyrazolone ring via an oxygen atom linked releasable group, characterized in that a substitution reaction of an α-halogen-β-alkoxy-β-arylaminoacrylic acid ester according to the general formula (II) wherein Rp has the meanings given above, R, an alkyl group and R ^ a hydrocarbon group and X is a halogen atom, with a compound Y ~ or YH to form a compound of the general formula (III) 509829/0971 is carried out, wherein R ₂ , R *, R ^ and Y have the meanings given above, and then a ring-closing condensation reaction of the compound of the general formula (III) with a hydrazine of the general formula (IV) wherein R _x , which has the meaning given above, is carried out. 12. Process for the preparation of α-substituted ß-alkoxy-ß-arylaminoacrylic acid esters of the general formula (III) wherein Rp is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an alkylsulfonic acid group, a carbamido group, an acylamino group, a cyano group, an alkoxycarbonyl group, a Sulfonamino group, a sulfamoyl group, a diacylamino group, a carbamoyl group, a carboxy group, a Sulfo group or a nitro group, R, an alkyl group, R ^ is a hydrocarbon group and Y is an alkyl aino group, a dialkylamino group, a sulfona ^ ino group, an acylamino group, a diacylaciino group, an r.it the 4-position of the pyrazolone ring via the nitrogen atom nitrogen-containing compounds linked in the heterocyclic ring heterocyclic group or one with the 4-position dec Pyrazolone ring linked via an oxygen atom 509829/0971 Settable group mean, characterized in that a cc-halo-ß-alkoxy-ß-arylaminoacrylic acid of the general formula = c; (ID 'COOR * where Rp ₁ R-? and H ^ have the meanings given above: and X represents a halogen atom, is reacted with a compound of the formula YH or Y ~, in which Y has the meanings given above. 509829/0971