DE1810463A1 - 1H-Pyrazolo- [3,2-c] -s-triazoles - Google Patents

Description

1610463

JP A £ E Ii ΐ A Ιί Vi. <I I. T E D; f> feg, v'io'Lffj ϊί. Bar-i-ula., , Dp "» Ing- Hs ld

ti Γ-üiichen 2ϋ, HO, Oct. 1968 'Tni.evftchSvrasß-a- B Telefoas C0811) 29 32 9?

S5? IiÄH KODAK COMPAKY ₃ 3 · Ί3 Offer S'ir-SEFC, Rocheste * _»9 State Πβυ York, United States of America & n

Pyi-aisoio - / "" 3 -?> ^

--triazole

the

soule your

s * sus * Hei? atal-

tj in dsr Paropbotographla. ^ - a Heratollisng of

Wnvhiixippler su -Ver ^ sndan, öis salt den Oxidations

: · K; .u ³ ?? a? Development vs.required developer in the heating of dyestuffs with a negative reaction. It

SiIb ^ »halides, Sp.iisibllisieruKgsfavbst ^ fff? ouch

"j it.-gi; the Eykermimis aiig- ^ uädi? ₉ that lH-Py3

in .ffi ^ bpho-fcogwaphlaohön K; vfc £ j? iali3n are

009844/1504

BAD ORlQfNAt

18T0A63

Fabrics as well as other dyes are suitable, which in turn can be used as Filter dyes, sensitizing dyes and textile dyes let use.

The subject of the invention is 1H-Pyrazo! O ~ / "" 3.2- £ _7-8 «trias © le., characterized by one of the following structural formulas;

where mean:

R, a hydrogen atom, an esterified® carboxyl group an atom or a group, di® in a usual split off graphic color development;

R _{2 is} a group of forms which splits off from a common photographic color change! sCH-R-, where R ^ is aralkyl- © of the ary! group, and

R * is a hydrogen atom or one in photographic color couplers see group »

Are the 3- and / ODSR 6-positions of the compounds of · ¹ angegefo © = · nen formulas substituted by groups R ', as can Diege bc-ispielsweise consist of straight-chain or verzweigtkettigeirs, optionally substituted alkyl groups with preferential price © 1 to 22 carbon atoms, d. ho, for example, methyl-, · Äfchyl ~ _s r-> _s isopropyl-, sec _a -butyl-, tert «-butyl-, t@rt.-amyl-,

009844/1504

..,, SADORfafNÄL

tert-pentyl, n-hexyl, n-dodecyl, n-docosyl, 2-chloro-n-butyl, 2-hydroxyethyl, 2-phenylethyl, 2- (2,4,6-trichloE »Ophenyl) ethyl or 2-aminoethyl groups. The substituents R * can also, for example, have the meaning of optionally substituted aryl groups, preferably those of the phenyl or naphthyl series o In this case, R * can, for example, represent a phenyl, α- or ß-naphthyl, 4-methylphenyl, 2, 4,6-trichloropbenyl-, 3,5-dibromophenyl-, a 2-, 3- or 1-trifluoromethylphenyl-, 2-chloro-a-naphthyl-, 3-xthyl-a-naphthyl-, 2-methoxy- g phenyl - or a 3-aylamldophenyl group.

R ¹ can furthermore be, for example, a heterocyclic group, for example a pyridyl or thieny group. Furthermore, R ^{1 can} , for example, represent an optionally substituted amino group, ie for example a methylanino, diethylamino, n-docosylamino, phenylamino group. , Tolylaalno, ^ (3-sulfobenzamido) aniline, 4-cyanophenylamino, 2-trifluoromethylphenylamino or a benzothiazoloamino group. R * can also stand for an acylamido group, for example an Xthylcarbonamido-, n-Decylcarbonaraido-, Phenylfithylcarbonanddo-, Phenylcarbonaaldo-, 2,4,6-Trichlorophenylcarbonamido-, iJ-Methylphenyl-carbonafflido-, 2-Xthoxyphenylcarbonamido-, 2- / " (2, ¹ I- ä di-tert-amylphenoxy) acetamido_7beniamido, or an α- or 0-naphthylcarbonamido group. R 'can also be, for example, a hydroxyl group or an alkoxy group, e.g. a methoxy, xthoxy, n -Butyloxy, n-hexoxy, n-dodecyloxy, or an n-docosoxy group Non-coupling, phenolic stabilizer group, as described, for example, in the FranzCsIscIier. Patcr. ^ Gohrift; 1 '3 - J ^- - cj ^ and uor Belgian patent specification 093 ji ^ ·

00 9844/1504

If R. has the meaning of an atom or a group which splits off in a customary photographic color development, this atom or this group can, for example, consist of a halogen atom, e.g. B. a chlorine, bromine or iodine atom, or a group of the formulas -SO-H; -COOHj R ^ -O- or Rjj-S-, wherein Rjj is an optionally substituted aryl radical, preferably an optionally substituted aryl radical of the phenyl or naphthyl series, e.g. B. a phenyl or toy group, od «fafttiftiifc Xlfl fl ubflti fc tiiftrt ο Aminoflcnipp o d ^ o tofl iflPiLftlfLflWft 3BtO d op ff i ls *

flcnipp o _

oc or a group of the formula -NNR, -, in which R ₁ . is the radical of an aromatic or heterocyclic diazotronesable amine, for example a 2-methoxyphenyl-, an acyloxy-, a suI-phonyloxy-, a thiocyano- / © in benzotrlazolyl- aresto

Furthermore, R ^ can optionally have the meaning of a development-inhibiting group, such as, for example in British Patent Specification 953,454.

R can, for example, be an optionally substituted alkyl radical, as indicated for R *, d. H. for example a methyl, Xthyl- or Butylreat or a Phenylfithylrest or an optionally substituted aryl radical, as indicated for R *, preferably an optionally substituted aryl radical of the phenyl or Naphthyl series, or a tertiary aminophenyl radical <,

The lH-pyrazolo- / "* 3i2- £ _7-s-triazi> Ie of the invention are in the colorless in most cases, but can also be colored themselves. They couple with the oxidation products of customary photographic color developer compounds, for example p-phenylenediamines, to form dyes.

0098U / 15CU

Compounds of the given formula I, in which FL is a hydrogen atom or a leaving group, couple quite obviously in the 7-position with the formation of purple or so-called Magentaf dyes »

The couplers according to the invention are so-called 2-equivalent couplers, with except that they are 4-equivalent couplers when R is the meaning of a hydrogen atom.

Compounds in which R-, the meaning of a suppurated carboxyl group form yellow dyes. The mechanism of the reaction underlying dye formation is not yet known completely resolved.

Advantageous lH-Pyrasolo- / "* 3.2- £ _7-s-trlazoles are in the following Table I listed:

1. 7-sa ~ L & ur®midophenylthio-6-methyl-3-propyl-1H ~ pyrazolo- / ~ 3 »2-c7 s-triazole;

2ο 3-3 ', 5'-dicarboxyphenyl-ö-heptadecyl-lH-pyrazo10 / "3,2-S _- JS-

triazole;

3o 3-hexyl-6-raethyl-1H-pyrazolo- / ~ 3,2-Ci _- 7-3-triaZQlyl-7-suIfon-

acid;

4. 6-methyl-3-pentadeeyl-7-phenoxy-1H-pyrazolo- / ~ 3 »2- <s _- 7-3-

triazole;

Y- (l-phenyl-iJ-tetrasolylthio) '-

5 * o-3-He3gyl-6-m®thyl-5.H-pyrazolo - / "" 3,2-c 7-s-triazolj

6 » 6« "methyl-3" pheny 1-7-3 '-pyridylazo-1H-pyrazolo - / "" 3,2- triazole;

7. 7-Ac © toxy-6-methyl-3-pentadecyl-1 H -pyrazolo - / "3,2-0

trlasol;

0098U / 1504

8o 3- { ^J 3 - / "* e- (3-t» -Butyl- ⁱ l-hydroxyphenoxy) tetradecanainido _{¥ i>} 7-2-chloro} phenyl-6-methyl ~ lH-pyrazolo- / ~ 3,2 - £ _7-s-triazole;

9 "7 ~ Buty" methylene-6-methyl ~ 3 ~ phenyl-1H-pyrazolo - / "3,2- <| _7-e triazole;

10 "7"^> Ben2ylidene-6-methyl-3 ° phenyl »1H-py2 ^t asolo- / '"3> 2- £ _- 7-8-triazolj

11. 6-Methyl-3-p8ntadecyl-7-thiocyanato-1 H -pyraBolo / "3,2- ^ 7-s triazole;

12 _a 7-BsnzotrIazol-2-yl-6-methyl-3-pβntadecyl-1H-py2 asolo-

13. 6-M®thy 1-7-methylsulfonoxy-3-pentadecyl-1H-pyi? AzQlo- / ~ 3.2- ^

(2-aninophenylazo) ®cyl »6-methyl-7 ~ -» lH ~ pyrazolo / "'3 _J 2-» £ _g 7- »ia« -

triazole;

15. 7-Butylaminomethyl-6-methyl-3-undecyl-1H-py2 »azolo- / ^t " 3 »2-c ^ 7 -s-triasol;

16ο 3- £ -Acetamidoph®nyl-1H-pyrazolo - / ** 3> 2-0 ^ 7-8-triazole;

17 · 3 ° £ -T2 * ifluoroaethylphenyl-1H-pyrazolo - / "3» 2- £ _7-8

18. 3-e-naphthyl-1H-pyrazolo - / "3» 2- £ _7-8-tx »iazole;

19. 3-2 ^l = thienyl-1H-pyrazolo - / "3» 2-c_7-s-triazole;

21 _β 3-Hydroxy-6-methyl-1 H -pyrazolo - / "3» 2-c 7 ~ s ~

22. 3-Xthoxy-6-raethyl-1H-pyrazolo- / ~ 3 »2-c _{> -} 7-8-triazole;

-ea-

009844 / 1S04

The color couplers according to the invention can be closed by a ring ▼ on compounds of the formula XIZ given in the following in the presence of POCl, in an inert solvent, e.g. 6. benzene,

according to the following reaction equation:

NH-HH-CO-R ₇

COOR

♦ H ₂ O (1)

III

COOR ₈ H

IV

Rg, R ₇ and R _{8 here} have the meaning of optionally substituted alkyl, aralkyl or aryl groups.

On the other hand, the compounds of the invention can also be prepared by ring closure of compounds of the following « the specified Forael V in the presence of bromine and sodium acetate in acetic acid, according to the following reaction equation:

N-

NH

NH-N

-CHR ₇ * Brg- »

N 4 2HBr (2)

COOR

COOR

I H

VI

Here, Rg, R ₇ and R ₈ in turn have the meaning already given. If compounds of the formulas IV and VI are treated with sulfuric acid, the group R _{8 is} hydrolyzed, leaving a free carboxyl group. If the treatment of the compound with sulfuric acid is continued, the carboxyl group can be split off, leaving behind the free Ba & e of the following structural formula VII:

Q098U / 15CU

VII

A logosome atom, for example, knows 3Ln the 7-position dupen * tte « handling the connection de? Formula VII With one-halogen in Acetic acid to be introduced "

A sulfo group, for example, can lead to the 7-digit transition with dleura

For example, a phenylthiojy group came into the through condensation of a Veii'bindursg des * Ροϊίβ ©! VII rait in the presence of a base and an inert loatangia agent © lsi

■ An iPhßfiosiygsnippe can in the 7-Stelimiig through Reßlctiora

a connection of the Fostsel VIl with Ha introduced;

could ftt & ii b «kanntdn Ubll4ii6»

ladder®
in tJlaS

iehi «ti © ft € In

viii «it

tlli

«I ff]

U UfK

Compounds of the formula ¥ can be prepared as described by H, Beyer and coworkers in Der * ,, 8 £ _s 2552 (1956) *

If the group R "is to be replaced by a group of the formula -NH-R", the reaction stage (3) is replaced by adding an iBöeyanate of the formula R "NOO in an inert solvent to a compound of the formula VIII according to the formula following Reaktioissgl @ lehwngs

CiI)

NHNHGONHH »

VIII ϊχ

A bond of the formula IX is then used instead of a * dang ö © r F © ria © l III in stage (I) _o

As already explained, see the color couplers from the invention with ύ®η different Dlazoniumswlsehenvsrbi »dUing @ si coupling © the with M®thinfarbst © ffBMisehenprodukt @ si % ® Arn ™ bs% i / _e , methine dyes ^ imsetseni which see for example els FiI- ™

and

Di © unt®r ¥ ext © invention d © r erfindungsgeiaäßen TRIS ^ ol © produced dyes can be durehi following Strukturformeln- "

009844/1504

Yes

- 10

or

XIa

in which Q and Q 'represent the atoms which are necessary for the completion of the chromophoric system, whereby it applies that the 3 " and opposites of the pyrazolotriazole length - if necessary. can be substituted by numerous substitutes occurring in dyes"

The chromophotic system completed by Q and Q 'is found, for example, in azo dyes and methine dyes. or dyes similar to these. " Methine dyes are of particular importance in photography. They can consist, for example, of gyanine dye, cfya'itiine dye bases, meroeyanine or a new class of dyes, which are represented by the following forms. 1 X is marked. Another class of dyes without open label methine groups results from the later formula X / for the case that η is § 0.

Dyes of the following formula X:

CHS = (L-L

0098U / ISOA

■■■ "- ■ ;: ** ρπρ, ::;» * ■■■ ".: ■ ::

18104S3

- Il -

where mean:.

Ra and RQ substituents which can be found in the 3- and / or 6-position of the? 3rraiölo - / * ^P 3 »2- £ _- 7-s-trias bolring, corresponding to R'j

L is a methine group which is optionally substituted

can be, and

η * 0, 1 or 2 »{

can be prepared by condensation of a compound of the formula I ₁ where R _{1 has} the meaning of a hydrogen atom, or one mole of ethyl orthophoniate (Monomethln), A-Xthoxy-acroleinaoetal (trinethine) or olutaoonaldehyde dianilide-Uydroeblorld (pentamethine).

Dyes of the formula t are particularly advantageously suitable for the spectral sensitization of photographic silver halide ions.

Dyes of the formula XI given below:

where R ^, R ₁₀ and %, as well as η ai »b» r »its indicated * meaning bisiteeh and where furthermore mean:

009844/1504

BATH

R .. airse optionally substituted alkyl, aralkyl or ary! Group, see B ₀ of the 'R' defined in the Zueaimnesnheng. ': Type, or an optionally substituted heterocyclic group of the type defined in connection with R ";

For the completion of a heterocyclic ring, as normally occurs in cyanine dyes, the atoms required, that is, for example, the atoms, the completion of an S-fyrrole "^ 3-pyrrole" ·, 2-indole-, 3-xndol «· -, 3." Inöolizin '=' _f 3-indoli2in- © which a 7-pyraaolo- / l2-c * ^f -a "triasol ringso are required"

X is © ir * ίΐΐϊϋοΐιβε acid raditol _ε like © a rtorm & Xerweifx® can be found in cyanine dyes.

E of the given formula XI can be easily: .produced by wetting a compound of the formula. I ₈ wherein R, is a hydrogen atom, with a compound of the following formula XEI in the presence of an acid.

OCH— (Laailihr ^ "!

Forssel XI dyes can be used in particularly beneficial? Way as a filter photographic material «use photographic materi®iieis» since they can be bleached out by photographic developer solutions are.

Dyes represented by the following general formula XIII;

CH = S-IL-L = S) C-C = ¹ O XIII

10

where Rqj, RiQS Ij mwd η dis already indicated® and Z _{2 stands} for the atoms ₈ the % u &
tepocyeliachen ketomethylene ^ stems © i'fordiish Bisad _g <äi © äbli eh © 3? w © is @ in Merosyaninferbstoffen ^ ortisigswaiae a © ® hydantoin »» Thiohydantoin ·· _s . Rhodanin Thi © baa ^ä bitMFSäiire- _s 2-ThIaSoUn - ^ - On- _s 2-Thio => 2 _p il- "2-Iroidasolin - ^ - on-, 2-PyFas © lin-5-on- © the one able © ra are produced dia ^ sh Uaasetgüng a ⁵ compound of the Pona © l I ₂ wherein R ₁ s is H, with a
Formula XIV:

Y £ —CH »(L — L ·« *) C -C = O ■ XIV

where Y- the meaning of an alkoxy- © der Äe @ tanilidograpp @ shows.

Dyes d @ r formula XIII can be particularly ter way Bin spectrally sensibilisier © nd © dyes fis *

0098A4 / 1504

Dye © of the following formula XV:

H «, R ^ Qa% x» L wnd η the b @ rait3 given E stands for di © atoms that lead to

! erweis © In cyanine dyes! » Indolenine, Bensothlasol-, iaiilasol ^ a Chlnolln "or Isoshinolin ^ ingsa _e can be provided i @ l" ht "duj? © !! UssaetZMng © ines · Connection of F®rsa © l I wherein Η-, © in Wasserstoffatoia is «S @ it mel:

LI _n O;

where Ig © in iodate © s _s a is.

Colors @ ff © the F © f®§l Vi are suitable in "/ © apt®illiaffc @ 2? Star spectral SenAilisiairong

009844/1504

The following examples are intended to explain the invention in more detail.

Ι · Manufacture of 1H-pyrasolo- / ~ 3.2- <5_7-s-tria «ols

Example 1 - 7-Ethoxy carbonyl-6 "-methyl-3-phenyl ~ 1H-pyz'ar« olo · / ~ 3,2-e_7-s-triaiol

NH.

CXX) C ₂ H ₅

Br,

NaQOCCH,

A solution τοη 0,6Ί g of bromine in 5 nl glacial acetic acid portions "as within 5 minutes do a mixture of 0.96 r Bens" aldehyde ll Itboxyoarbonjfl-3-nethylpyrarol-5-yl-iiydraEon (H. Beyer Employee, Be r. § £, 2552 (1956)) and 0.3 g sodium acetate in 15 μl acetic acid. The mixture was stirred at room temperature for 90 minutes and then warmed to a steam bath for 15 minutes. Then, the Reaktione- Bischung was cooled and poured with stirring into 100 ml of water. The sticky, precipitated yellow-brown precipitate hardened on standing overnight. The precipitate was filtered off, gewasohen with water and dried in air. It was then recrystallized from aqueous ethanol. There were 0.81 g of reaction product, corresponding to 85 t theory, In Fons of pale yellow Mädeln having a melting point of 172 ° C obtained "

4/1504

Analysis:
Calculated for found:

62.2 Ϊ Cj 5.2 % H; 20.7 ί Η. 62.5 S Cj 5.35 % Hj 20, ή g N.

The color coupler coupled with a 2 ~ amino-5-diethylaminotoluene hydrochloride depilatory solution, through Kaliurapersul » fat had been oxidized, with the formation of a yellow dye © a i & lfc * «" ,, in ethyl acetate at Ί35 mu, 460'with "and a shoulder

Max ;

at l <80 m ».

COOC ₂ H ₅

1 g of 7-ethoxycarbonyl-6-methyl-3-phenyl »1H-pyrazolo- / ~ 3.2 ™ £ _7 ~ s-triazole and θ ml of sulfuric acid of a specific weight of 1.84 were on the steam bath for 45 minutes Temperature from .60 to 70 ⁰ C heated. The clear red clay solution was then cooled and poured into 200 ml of water. The thick, colorless precipitate which had separated out was filtered off, washed with 25 ml of 3 η sulfuric acid and then with 50 ml of water. The reaction product was then recrystallized from aqueous ethanol. The color coupler was produced in this way in the form of shiny needles in a yield of 0.4 g, accordingly

55 % of theory received.

0 0 98 Ä A / 15Ö

Analysis:

Calculated for C ₁₁ H ₁₀ N ₂₁ : 66.7 % C; 5.1 % Hj 28.3 % N.

Found: 66.8 % C; 5.3 % H; 27.85 % N,

The color coupler coupled with a 2-amino-5-diethylamino-toluene-hydrochloride-parbene developer solution which had been oxidized by potassium persulfate to form a purple-red dye with _ην in ethyl acetate at 550 ray.

Max

The coupler coupled in a corresponding manner with an oxidized N-ethyl-N-ß-raethanaulfonamidoethyl ^ -methyl- ^ aminoaniline sulfate developer solution to form a purple dye with a λ _Λ value in ethyl acetate of 5 ^ 3 my.

Max

Example 3 - 6-Mefchyl ~ 3-p-tolyl-1H-pyrazolo- / ~ 3.2- £ _ / ~ a ~ riazole

H
The color coupler was prepared according to that described in Example 2

Process made. The division took place this time duroh implementation of p-toluene aldehyde with 4-ethoxycarbonyl ° 3-methyi-pyra25öi-5 ~ y! Hydrazine and ring closure of the obtained according to the method described in Example 1 «,

The Dax »color coupler was obtained in a yield of 53 % .

melting point of 23C
009844/1504

had a melting point of 23O ⁰ C.

_{The color coupler coupled with an oxidized developer solution of the} composition given in Example 1 to form a dye with a λ value in methanol at 562 μm, in ethyl acetate at 549 mp and in cyclohexane at 540 mti and 516 min.

Example ¹ I-3-o-ChloiOphenyl-6-raethyl-1H-pyrazolo / ~ 3.2- £ -7- a-triazole- »7-oarbonic acid

JOOH H

The coupler became similar to that described in Example 2 Coupler manufactured. The starting compounds were o-chlorine © benzaldehyde and A-ethoxycarbonylO-methylpyrazol-S-ylhdrazine used. The hydrazone obtained was ring-closed according to the method described in Example 1.

The color coupler had a melting point of 156 ⁰ Co He dome · te to that described in Example 1, the oxidized color developing solution to form © Ines dye with _λ τ value measured in Rthylacetat at 5 ^ 0 my,

0 0 9 8 A UI 1 5 0 A

Example 5 - * -p ~ Dimethylaminophenyl-6 «mefchyl ~ XH ~ pyra7.o3 o ·

The color coupler was prepared according to the method described in Example 2 . fchodp- manufactured Ala output Ever bonds were diosina "but used p ~ Dimeth.ylaminaber>;. <ildehyd and ^" Äkhoxycicbu 3-methylpyri'.zf! "5 ylhydrGZiiuPfo done ^one Hingpchluß de α obtained ?: hydrazones in the Example] bcr'f.hrl level wcler

The color coupler had a SohineJ '/, punkfc at 175 ⁰ C u ^ v Tepr · te with that in Example 3 -beachri.iiberiRn, r * ■ ydies ⁱ -eii: ENTV i -: -> C. <löaung to form one dye it off with a-m A _mt! , -V <i> ri ·· _f raeppen in .KihyXncetat, at 55;

Example 6 ~ 3,6 "Dimethyl'-IH-pyrasolo / ~ 2 _i 2« -c _< _ ⁷ -a-tri.a - o '?

0984 A / 15 (H.

BATH ORIGINAL

3.09 g ¹ l ~ ethoxycarbonyl-3-methylpyraaol ~ 5-ylhydrazine / ~ H. Beyer and coworkers, Ber. 8 <?, 2552 (19.56) _7 were mixed with 10 ml of acetic acid and 1.5 ml of acetic anhydride, after which the mixture was heated on the steam bath for 1 hour. The resulting solution was cooled and poured into 50 ml of water. The precipitated crystalline acethydrazide was filtered off after standing overnight, washed with cold ice water and dried. The yield was 3 »g, corresponding to 98 % of the Theo«

φ rie. The melting point of the compound was 130 ⁰ C. The connects * dung was heated with 125 ml of dry benzene and 2.7 ml Phosphoryloxychlorid * l hour at reflux temperature of the mixture, and the mixture overnight at room temperature, was allowed to stand. The benzene was then separated off by distillation, whereupon the oily residue was stirred with 100 ml of water. The mixture was then extracted with 3 × 150 ml of ethyl acetate. The ethyl acetate solution was then dried over calcium sulfate and then evaporated to dryness ₉ whereby a pale yellow, solid mass was obtained, which was recrystallized from ethanol , 05 g obtained «It had a Sehmelsspmik-fc of 172 to 173 ⁰ C The reaction product was with 1β ral cons. Sehw © -

™ acidic acid was added, after which the mixture was heated on the steam bath for 75 minutes. The resulting solution was then cooled and poured into 100 ml of water. After cooling, the mixture was adjusted to a pH of 10 by adding a sodium hydroxide solution. The solution obtained was then extracted with 3 × 150 ml of ethyl acetate, whereupon the organic layer was separated off and dried over calcium sulfate. After removal of the solvent by distillation, a pale yellow, solid mass was obtained. The yield of reaction product was 1.1 g. Dae reaction product eohmols at 190 ⁰ C.

9844/1504

color couplers obtained kuppalte ait a ⁵ oxidized color dsr sntvjleklerlßsung in Example 1 angegebensn

with formation of a dye with a * _ma , ~ value in & l.h acjetat of 528 mp "

X- 6-Hethyl-3- (2, ^, 4-trlmethyl) .pentyl-1H-pyrazu2 ·

CIL

GH ₀ -QH-GIU-C-CH., II

Pyrldine were partly room fairy temperature with 2.2 ¹ J g 3 »5.5-- ^! Pi ^> iii * &"h ^ l- ⁱ hexsmoyl chloride added ^ whereupon the reaction mixture was heated for one hour on the steam bath." After cooling down, the reaction mixture was poured into 250 ml of water. The precipitated oil was old 3 x 100 ml of ethyl acetate extra hard. The 22 ^a preserved Xthylac ^ acetate solution was Calelunjsulfat gsfcro ^ knst and the solvent was vacuum abdestlllisrt. The remaining, dioke, yellow oil (1 g, corresponding to 98 % d-sv theory) was kept in 125 ml of dry Binsol for 5 hours with 3 »9 g of phosphorus oxychloride at the return temperature: the reaction product was then, as in the previous games isolated by extraction with Xthylacetat "-It mi km & 3 ^ 0 g Sinea oil © s C; 2 haltsn" which 90 Minutan ial on the Dampfbad® long with 20 cons Schwefels2ho. »s was heated,

00 98A Λ / 1504

The mixture was then cooled and poured into 250 ml of water poured, the oil was extracted with ethyl acetate, whereupon the Ethyl Acetyl Detachment Was dried over calcium sulfate. Well Removal of the solvent left 2.2 g of an oil. The oil was stirred with 50 ml of a 10% sodium carbonate solution and then with 50 ml of water, whereupon it solidified. The reaction product was aua an Xthanol Waaaer Miachung to " crystallized, whereby a solid, shiny mass with a melting point of 1 * 18 ° C in a yield of 0.1 | g received became.

Example 6 - 6-Methyl-3-n-pentadecyl-1H-pyra3olo / "" 3,2- * c_? - s triaEoyl-7-carboxylic acid

COOH

6 g of ^ -Athoxycarbonyl-J-methylpyrazol-S-ylhydrazine were dissolved in 100 ml of pyrldine, and 8.9 g of palmitium chloride were added to the solution over the course of household items. After standing for 10 minutes, the mixture was heated on the steam bath for 1 hour. After the reaction mixture had cooled, it was poured into 400 ml of water, whereupon the colorless precipitate which had separated out was filtered off and dried. The yield of the reaction product was 11.6 g. The resulting reaction product was then treated with 8.19 g of phosphorus oxychloride in ¹ JOO ml of fcyökkenera Bensol for 7 hours at reflux temperature, whereupon the reaction mixture was reacted as described in the previous sections.

0098A4 / 150A

play has been worked up. The yield of ester was 10 g.

The ester was then concentrated by heating in 80 ml for 45 minutes. Sulfuric acid hydrolyzed on the steam bath. After the reaction mixture had cooled, it was poured into 400 ml of water. The deposited precipitate was filtered off, washed with water and twice from methane :! recrystallized. In this way 2.5 g of a shiny, colored, solid burl; obtained with a melting point of 113 ⁰ C.

Example 9

3-n-Butylamino-6-methyl-1H-pyrazolo / ~ 3 _i 2-c _- 7-B-triazole

2.1 g of iJ-ethoxycarbonyl-S-methylpyrasol-S-ylhydi'azine were mi 1.14 g of n-butyl isocyanate in 10 ml of boiling benzene 3 Stumien l heated. Then 50 ml of dioxane were added, followed by a heated for an additional hour. After standing over sewing Colorless crystals formed which were filtered off / Die The yield was 1.1 g. A second fraction (o, 7 g) was? dursh Concentrate the benzene solution and recrystallize the Obtain residue from ethanol "

009844/1504

The first fraction was refluxed with 1.2 g of phosphorus oxychloride in 250 ml of benzene for 6 hours, a gummy substance separating out. The mixture was left to stand overnight, after which 150 ml of water was added. The benzene was then separated and the gummy mass was extracted with 3 x 150 ml of ethyl acetate. The organic layers were combined and washed twice with 100 ml, after which they were dried over calcium sulfate and concentrated. The residue obtained was recrystallized from an ethanol-water mixture, 0.63 g of glossy crystals having a melting point of 130 to 132 ^° C., corresponding to 60 % of theory, being obtained.

The reaction product was concentrated in 4 ml. Sulfuric acid heated on a steam bath for 90 minutes and, after cooling, in 50 ml Poured water. A crystalline precipitate fell out, which was filtered off, washed twice with 25 ml of water and dried. net was.

The yield of the reaction product was 0.33 g * The melting point of the compound was 68 ⁰ C * Compound kuppelte with an oxidized Parbentwieklerlöeu ng of the composition specified in Example 1 to form a dye with _λ χ value in ethyl acetate at 538 cm.

Example 10

The compounds given below were prepared by ring closure of the corresponding hydrazones according to the procedure given in Example 1.

The hydrazones required to carry out the process were obtained from the corresponding aldehydes and Ί-ethoxycarbonyl-3-methylpyrazol-5-y-hydrazine, which was obtained in 50% yield

dsireh implementation of the corresponding Hydroehlorides (22 g) In 100 ml of methanol with 14 ml of Trläthylainin, heat to »achieve the solution, cooling and filtering off the free base can be obtained.

The hydrolysis and decarboxylation took place as in Example 2 described =,

CA) 6-M @ thyl -? - u-propyl-1H-pyi. * Azolo / ~ 3 »Z-o ^ -e-triazole, I.

Mp, s 129 ° G
(B) 6 ~ M

G _O

⁰ C /

3 ^M 2 * _> 6 ^l -DiehlcMraphenyl-6- &iethyl-lH-> pypa8olo / ^< ~ 3 »2- _i e 7-a- g

triazole ^ T-carboxylic acid α, mp ₀ s 260C

The following two compounds were prepared according to the method described in Example 7, the starting materials being "bindmgeifs 4 »Ethoxycarbonyl-3-methylpyrazole» 5 ~ yl ~ hydra2in and © nt » speaking acid @ cshloride were used »

Fpo »103 to
Cl) -fr-Η '-C2 "" ^ "- Diifcert. .- -amylphynoxy ) butyl-6-raethyl" 1H-pyrazolo "

^e 7 Fp ⁰

00984 / »/ 1 504 '

Example 12 - 6-methyl-3-phenylaraino-1H-pyrazolo / **>, 2- £ _- 7-3- triazole _: ________ __

This compound was prepared according to the procedure described in Example 9 made, starting from H-Xthoxyearbonyl - ^ - methylpyrasol-5-ylhydrazine and phenyl isoeyanate. The compound melted at 2? 3 ° C ',

Example,,!!

The compounds given below were prepared by reacting in each case 2 g of a corresponding 7-position substituted pyrazolotriazole in 30 ral acetic acid with 0.7 g of sulfuryl chloride in 5 ml of acetic acid by heating at 40 to 50 ° for 15 minutes C and a subsequent 5 minutes nourishing warming on a steam bath "Naeh einatündigsm standing room temperature, diluted solutions, each with 200 ral Wasβsr, filtered, whereupon the precipitated reaction products or were each extracted with 3 χ 50 ml of benzene _a the benzene extracts were dried over magnesium sulfate, , whereupon the reaction products were isolated by removing the benzene by distillation.

The reaction products could also be uracrystallized from petroleum ether with a boiling point of k0 to 60 ° C. The yields in all foils b @ i were about 80 %,

Pp = 48 ⁰ C; shiny crystals.
(L) 7-chloro-6-methyl-3-pentadeyl-1H-pyraz © lo / 3.2 ~ s .JF-a-triazole

57 ° C .; shiny crystals.
(M) 7-chloro-6-methyl-3-heptadecyl-1H-pyrazolo / "° 3,2-c_7-e-triaaol Pp. = 76 to 78 ⁰ C; glossy® crystals.

00984 U / 1504

(N) 7-Chloro-3- ^{i- l} - (2 ", ¹ » ^lt -di-tert-aaylphenoxy) butyl-6-rahthyl-H-pyrazolo / ~ 3 »2-c-7-s-triazole

Example 1fr - 7-Bromo-3-4 ^l - (2 ⁿ , i » ⁿ -dl-tert-amylphenoxy) butyl-6 · methyl-1H-pyrazolo / ~ 3,2-c-7-s-triazole

0.6 g 3-4M2% 4 "-Di-tert.-antflphenoxy) butyl-6-methyl-1H-pyrazolo / ~ 3.2-c_7-s-triazole, 0.25 g sodium acetate in 20 ml vinegar-" acid and 0.25 g of bromine were held at room temperature for 40 minutes after which the mixture was heated on a steam bath for 20 minutes. After allowing the reaction mixture to stand at room temperature for 30 minutes, the mixture was poured into 100 ml of water, and the reaction product was extracted with benzene. The reaction product was isolated by concentration of the getrookneten benzene extracts and Umkriatallisation dersäbon from petroleum ether with a Siedeberelch of 60 to 80 ⁰ C in a 5OJC-strength yield as a pale yellow solid mass having a melting point of 176 ⁰ C.

Example 15 - 6-Methyl-7-2 ', 4 · -dinitrophenylthio-S - * "- pyridyl- g 1H-pyrazolo /""3» 2- £ _7-s-triazole

0.3 g of 6-4lethyl-3-4 ^l -pyridyl-lH-pyrazolo / "* 3 _i 2- (C _- 7-s-triazole _f 0.35 g of 2,4-dinitrophenylsulphenyl chloride in 50 ml of benzene were added for 5 hours heated to reflux temperature for a long time and then refrigerated overnight. The deposited precipitate was filtered off and washed with benzene. The color coupler was obtained in a solid, yellow mass with a melting point of 28 ° C. in a yield of 90 % of theory.

The color coupler coupled with an oxidized 2-amino-5-diSfchylaminotoluene Hydrochlorld developer solution to form one

00984 4/1 SOA

purple dyes raii an ^^ "shipyard in Äthyläeetaf nnu

Example 16

The following compounds (O), (P) and CQ) were prepared according to the method described in Examples k, 8 and 9, with the starting compound ^ -i hydrazine anateile of iJ-Xthoxy
hydraein was used. The required hydrazine was ⁵ 'made from the corresponding Aminopyräzoi by Diazofciesnmg and reduction with Katriuniaulfit as v in the production @ n H Xthoxycarbonyi-J-roeishyipyrasol S yihydrasirt described © !! "(Ho B © y§f and Collaboration with · »Ber. U _t 2552 (1956)) * -

The compound possessed a melting point b ?? i Dar color coupler coupled pit eiiser oxidized t-Ajnin @ -5 diiathylaaiinotoluslentWickierIosuiig with the formation of eleventh color substance at λ ^, ^ -War in Ktt ^ ylaeeta ^. §5

The compound had a melting point vo "08 ⁰ Co The ler pimped t it der'unter CO * j angegebsiiien" oxydiert® Eftt * tiekl®rlÖ8u thirty to form a dye with λ, ^. "Value IFI Xthyiaöetat at

The connection had a SshtsaXg-pu & kt b @ i Öer kuppler kuppelte rrdt d @ ^ under C ©) b © s "written © n @ -n _? Ex *? - gierten Eftt *? Iekl @ ri8: süng- uhfeer formation of one with an A ^^^ value in. Kfehyläestät Let §5 ^ nm _c

Example 17

The compounds (R) and (S) listed below were prepared by methods as described in Examples 4 and 8. To prepare the compounds, however, this time ^ -Xthoxycarbonyl-I-propyl-pyrazol-S-ylhydrazine was used instead of ⁱ -Xthoxycarbonyl-3-methylpyrazol-5-ylhydrazine. The hydrazine required was prepared by the method used for the synthesis of ² J-xthoxycarbonyl-3-iaethylpyrasol-5-ylhydrazine from Η. Beyer and employees in Ber. 8 £, 2552 (1956), although ethyl 2-chlorobutyrylaeetat was used instead of Xthyl ^ -ehloroacetoacet & t.

(R) 3- ^t £ -chlorophenyl-6-n-propyl-1H * -pyrasolo / "* 3 _s 2-jB _{<i (} 7-s - feriazolyl 7-carboxylic acid.

The compound had a melting point of 135 ° C (dec). The compound coupled with an oxidizing 2-amino-5-diethylaminotoluene developer solution forming a Dye with a λ value in ethyl acetate at 544 raa.

The © compound coupled with an oxidized 2-Arain © -5 ~

below image © Ines with a * _M ^ _- V / ert in ethyl acetate at 53® nia

II ο Use of the color coupler for -production of voss dye © ω

el JLjB - 7- £ -Methoxyphenylazo-6-methyl- £ "5 * 2-c_J2? -S

4A7T5 0-

OCH,

25 mg of o-arilsidim viurusn in 1 ml. Of a lOfige diase, where the "solution of 25 mg of methyl-3-phenyl-1H

trlaiol in 2 ml of pyridine ^ iage®8b @ n. Des »? @ ^ Slünn © Egg des? Solve with water aws. He

η Chlor-waaser-s £ "3.ί

in Äthsmul'bai

OH

0098A4 / 150

BATH ORIGINAL

50 ag of the color coupler © of Example 2 0.5% ethyl orthoformate was added to 2 ml of acetic acid. The yellow dye formed immediately and crystallized out when the reaction mixture was stirred. The dye was filtered off and old washed acetic acid. The dye was in boiling ethanol suspended and, after cooling, filtered off and washed with ethanol. The yield of dye almost corresponded to the theoretical yield. The dye was in a mixture of ethanol and aqueous caustic soda solution soluble. He owned an ab- |

sorptionaaasiaua In pyridine at 483 ■ * ·

Analysis:

Calculated for C ₂₃ H ₁₈ N ₈ : 68.0 % C; 1.1 % H; 27.6 % N. Found: 67.9 % C; 1.6 % H; 27.5 % N.

The dye sensitized a customary silver chlorobronl deulsion up to 565 after a maximum of sensitization 150 na.

The following dyes were produced in a corresponding manner:

Ethylene-6-ethyl-3-p-tolyl-1H-pyrasolo / "3,2-c_7-8-triatoI;

swthylen-ÖHsethyl-Jn-propyl-1H-pyraEolo / "3, 2-cJ? -b -t riasol; T- Ce- ^ fethjri-S-pHsetsnojqrph · «! i-lH-pyrsjtolo £ * "3,2-c ^ 7-s -t rlasol -7 ylidene) »ethylene-6-« ethyl-3-p- »ethoxyphenyl-1H-pyrasolo - /" 3,2- £ s-trlasol and

7- (6-methyl-3-2 ^l , 6- "dlchlorophenyl-1H-pyra" ol / "3,2-c ^ 7-E-7-ylidene) -« ethylene-6- «ethyl-3-2 · ₁ 6 · • dichlorophenyl-lH-pyrssol-

009844 / 150A

BAD QHiQ _MAL

Example 20 ... - 7-C3 "6 ~ Dimethyi-lH-pyra2 © l © / ~ 3 * 2 ~ js _ra 7 ~ 8- = tri« ®l ° 7-yliden) 3'-i
/ "3,2-c 7-et

CH-atCH

50 ml of the color coupler of Example 6 in 2 ml of acetic acid which decomposes with 0.5 ssl ß-ethoxyacrolein & eetal «It formed directly the dye of the given structural formula. Di®

Mixture was warmed nosh on the Steam Bath® for about 2 minutes and then the mixture was cooled. The addition of aether ⁴ precipitated the dye. The dye was washed with ether and washed with ether. The yield corresponded to the theoretical yield. The dye possessed im in methanol at 5 ^ 2 ray.

The other solution allowed the dye to bleach out with the remaining solutions.

In a corresponding manner, the f @ lg © nde8i dye © is:

7- ( 6-M € thyl-3-phenyl-lH-pyra2 © lo / "3 » 2- ^ 7-et rlaeol-7-y liden)

3 · -allylidene -6-methyl-3-p-tolyl-iH-pyragoX® »£" * 3 »δ-β ,,, Τ-β-ϊ rlaeol";

98 ^ 4/1 50 4

7- C6-Mefchyl-3-n-px ⁱ opyl-1H-pyrazolo- / "'3.2- £ _7-s-triazole -7-ylidene) 3 ^l -allylidene-6-methyl-3-n-propyl -lH-pyrazolo / ~ 3 »2 - c _- 7-s-triaaol

gel8Blel, _21-7 (l »3-Diethyl-4,6-dloxo-hexahydro-2-thio-5

den) -3'-allylid © n-3,6 "3,2-e 7-s-triazole

N X— gh = CH— ■ CH = /

M / ^^ -

₃ - £ NH

¹ p

g of the Parbki applicator wn example 6 and 0.28 g of 1,3-diet "" '"*

4 _l) 6-diO3 £ ® <-5- = ^> 3'-äth®3iyallylidsn) -hexahydy © -2-thiQpy £ 'iMidi23 must 3 © si bathe in 5 ml of ethanol on the steam for 5 minutes mt _s Des "Aäböl formed © magenta dye wnarde dia ^ igh Eingieß® · ^ ILSR Reaktionsaiaehung in 25 ml of water precipitated D @ r Fa ^ bgt®jfT wiarde in virtually the theoretical · Meng © received. Dsx »Dye possessed an Absorptlonsiaaxisimra in methane ©! with iferbat © ff a usual region between 480 and 6 ^ 0 nm sensitized with a pointed © at fSOO

Similar to that described in Example 21. Method wuMäii dl © also produced the following dye ©:

0098 4 kl 15 0 4

7 (1,3-diethyl-4, 6-dloxo-hexahydro-2-thio-5-pyrimidylidene) 3 '-allylidene-6-methyl-3-phenyl-1H-pyrazolo / "3,2-c _- 7"-e-triazole; 7 (1,3-diethy1-4, o-dioxo-hexahydro- ^ - thio-S-pyrimldylidene) 3'-allylidene-6-methyl-3-p-tolyl-1H-pyrazole © / ~ 3,2-c ^ 7-s-triazole; 7 (3-phenyl-2-thio-4-oxo-5-thiazolidylidene) 3 ^l -allylidene-6Hm®thyl '> 3-p-methoxyphenyl »lH- pyrazolo / ~ 3,2- <s _e 7-s-triazole and 7 (3-phenyl-2-fchio- ⁱ »-oxo-5-thiazole dylidene) 3 ^l -allylIden-6-m @ th ^ l» 3- (2,6-dichloi ^ pheny 1) -lH-pyrasolo / ~ 3 »2- <s_7-s ~ triazQl.

Example 22-3-Xthyl-2- (3,6-dlmethyl-lH-pyraEolo / "3,2-c _o 7-striazol- = 7-ylidene) -2 * -äthylidenbesrizihiasolin

0.14 gd @ 3 Parbkupplers from Example 6, 0.45 g 2-2 * · vinylbenzthiazoläthjodld, 0.5 ml Trläthylaiain wiu. 25 ml were put together on the steam for 10 minutes. After cooling, 50 ml of Xther were added, whereupon the dye separated out. The yield of dye festlag O ₄₁ I g The dye had a Absorptionsmaxlnmra in methanol b & l ^ BU

The dye-sensitized conventional silver chlorobr @ mid © mMlg @ ® n © n to δ 10 nm with | a peak at 500 ma.

The dyes listed below are prepared in the manner described in Example 22:

009844/1504

2 * -ethylidene-benzoselenazoline ;

3-Xthyl-2 (6-ethyl-3-p ^ eethoacyphenyl-lH-pyra "olo / *" 3 "2- £ _7-8- triazo1-7-ylidene) -2 '-äthyliden-benzothiazoline j

3-ethyl-2 (6-ethyl-3-P- «ethoxyphenyl-1H-pyra« olo / "3,2- <s-7-etriaxol-7-ylidene) -2 ^l -ethylidene-benzoxazoline;

1,3-difithyl-2- ( 3, i-dlaethyl-1H-pyrazoloO , 2-cJ-b -tria zol -7- ylidene) -2 * -ethylidene-bensinldasoline and J.

1-Xthy l-2- (3,6-diaβthyl-lH-pyΓa «olo /" 3, 2-c _- 7-8-trlasol-7-yIideki! - 2 * -athyllden-1,2-dihydroquinoline.

Example 23 - 1-Xthyl-2,5-dinBthyl-3- <3,6-diacthyl-1H-pysa2? Ol5 - / "" 3 »2-c Za-

0.14 g of 3 »6-Diaethyl-1H-pyraEOlo /" 3,2-c _- 7-8-triazoi, 0.12 g of ethyl-2,5-dleethyl-3-pyrrolaldehyde and X ml of acetic acid like aa on the steam bath Heated for 5 hours, during which the yellow dye of the structural formula given was formed. The dye was isolated by removing the acetic acid in vacuo. The dye obtained had an absorption level in methanol at 436 nm and could be bleached with customary developer solutions (for example with Kodak developer D19b).

00 9844/1504

In the catfish described were the other, in the following listed dyes:

1-Xthy1-3,5-diphenyl-2- (3,6-diraethyl-1H-pyrassolo / ~ 3,2-c-7-etriatol-7-ylidene) methylenepyrrole;

1-Xthy1-3-n »thyl-2- (3,6-dimethyl-1H-pyrazolo /" 3,2-C _- TO-triazol-7-yldene) methyleneindole;

1-ethyl-2-ethyl-3- (3,6-dimethyl-1H-pyra-olo / "3" 2- £ _- 7-8-fefia8ol m. 7-ylldene) ethylene indole;

1-ethyl-2,5-diethyl-3- (6-methyl-3-phenyl-1H-pyra8ol® / "3,2-c _- 7-8 = triasol-7-ylidene) ethylene pyrrole;

1-Xthyl-3 »5-diphenyl-2- (6-ethyl-3-phenyl-1H-pyraEolo / ~ 3> 2-e ^? - s-trlasol-7-ylidene) methylenepyrrole;

1-ethyl-3-ethyl-2- (6H-methyl-3-phenyl-1H-pyraaolo £ "3.2- £ _- 7-> 8-trlasol-7-ylldene) oethylene indole;

1-Xthyl-2-ethyl-3- (6-methyl-3-phenyl-1H-pyra2olo £ "'3 * 2 ° G _? * ° 8-trlaBol-7-ylidene) ethylene indole and

7- (6- »ethyl-3-phenyl-1H-py rarolo /" 3,2-0, .7-8 ^ riaeol -? - V -allylldtn-3,6-dlaethyl-1H-pyrasolo / ~ 3, 2-c _- 7-e-tria «ol ..

Example 2k - 7- (1,3-Diflthyl-4,6-dioxo-hexahydro-2-thio-5-pyrlBidyllden) -3- ^M allyllden-3-p-methylaninophenyl-6-ethyl-1H-pyra-oil / "3 # 2-jC _- 7-8-tria" ol

The dye was prepared according to the procedure described in Example 21 using the color coupler from Example 5 instead of the color coupler from Example 6 *

The dye represented a common silver chlorobromide esntlsion up to 640 na with a peak at 580 mn.

4/1504

Example 25 - 7- (1,3-diethyl-4,6-dioxo-hexahydro-2-thio-5-pyrlmldylden) -3 ^l -allyllden-3-2 ", 6 ^ll -dichlorophenyl-6-methyl-1H- pyrazolo / "* 3,2-c_7-a-triazole

The dye was prepared according to the procedure described in Example 21 using Compound Q of Example instead of the compound of Example 6.

The dye sensitized a common silver chlorobromide demulsion between 510 and 620 nm with a peak at 580 nm.

Example 26 - 3-Ethyl-2- (6-methyl-3-phenyl-1H-pyrazolo / "3,2-c-7-s-triasol-7-ylidene) -2'-ethylidenebenzoxazoline

0.2 g of the color coupler described in Example 2, 0.45 g 2-2 * -

Acetanilido-vinylbenzoxazole & thiodide and 0.42 ml of triethylamine in

20 ml of ethanol were taken together on a steam bath for 10 minutes heated for a long time. The mixture was then cooled and added with 10 ml

Diluted water, whereby the dye precipitated. The dye

was recrystallized from aqueous ethanol. He fell in shape _Λ

orange crystals. "

The dye sensitized in the presence of Leucophor B sine Usual silver chlorobromide emulsion up to 545 nm with a tip at 510 nm.

Example 27 - 3-ethyl-2- (6-raethyl-3-phenyl-1H-pyrazolo / -3 »2-c-7-s-trlazol-7-ylidene) -2 '-fithylldenbenzthia shouldn

The dye was prepared from the color coupler of Example 2 and 2-2 ^t -Acetanilldovinylbenzthlazoläthjodld in ethanol in the presence of triethylamine according to the method described in the example.

009844/1504

The dye, which was isolated in the form of red plates, must be « Sibillates a common silver chlorobroride emulsion up to 600 nm with peaks at 510 and 560 nm.

Example 28 - 5- (6-Methyl-3-phenyl-1H-pyrazolo / "* 3» 2-c _{> e} 7-8-triazol · 7-yl) methylene ~ 3-phenyl-2-thiothiasolid-4-one

0.2 gdss of color couplers from Example 2, 5-ethoxymethylene-3-pheny-rhodanine and 0.42 ml of triethylamine in 20 ml of ethanol were heated together for 10 minutes on the steam bath When the reaction mixture was cooled, it was acidified with atomized hydrochloric acid. The precipitated dye was filtered off and recrystallized from benzene. He came in the form of yellow-orange needles.

The dye sensitized a common silver chlorohromide emulsion up to 610 nm with a peak at 570 nm.

In a corresponding manner, the following were given Dyes made:

5- (6-Methy1-3-phenyl-1H-pyrazolo / "3» 2- £ _7-s-triazol-7-yl) -methylene-1,3-diethyl-2-thiobarbituric acid;

00 98U / 1504

5- (3 "6-Dlaethyl-1H-pyraBolo / ~ 3" 2- <s _- 7-8-tria "ol-7-ryl) methylene 1,3-diethyl-2-thiobarbituric acid and

5- (3,6-Dl "ethyl l-lH-pyra" olo / "3,2- ^ 7-et riasol-7-yl ) methylene- 3-pb * nyl-2-thiothiatolid-l" -one .

009844/1504

Claims (1)

f Af I JTf A Ji § f MU C. Μ S Jinnee declines that “he is one of the * '* MWmM, ** - ill - 3 »IH-Pyrazolo - /" 3,2-c_7-s-triazoles according to Claims 1 and 2, characterized in that they correspond to the given formula I, in which R, as an atom or a group, ie in a conventional splitting off photographic color development means; a halogen a & osa, or a group of the formulas: -SO ₅ H; -COOH; Rij-O-; odsr R ^ -S-, in which R ^ is an optionally substituted aryl or optionally substituted aralsio group, or a group of the formula R ₅ -NsN-, in which R ₁ - is the »best of a diassotable amine or an asyloxy, sulfate, thiocyano, benzotriazolyl» or irra group. Process for the production of
tmch claims 1 to 3 »characterized in that it starts from compounds of formula XII: ₆ -JIy ^ NH-NH-CO-R ₇ COORc Hg, R ™ and R »each represent optionally substituted alkyl, aralkyl or aryl groups or substituted © AEsiao- ä grappcm, tsnä these are based on compounds of formula V in the presence of POCl, with an inert solvent with ring exclusion (C2) : COORg 0098A4 / 1504 where Rg, BU and R »have the meaning given, and this in the presence of bromine and sodium acetate in acetic acid Ring closure implements' 5. Use of 1H-PyraJ5ol © - £ ~ 3 _# 2- £ _e 7-s-triazoles according to claims 1 to 3 as color couplers for the production of dyes dss »Fo my: ^Rl N or where R ^{1 has} the same meaning wau .. Q- m% ü Q * the completion of a horrorophore system Atom® 6. Use of lH-Pyra2 © lo- £ -3 »2-e _e> 7-8-trlss © l-3Si according to claim 5 on the production of dyes of the SLig @ g @ fo @ n © n m @ ln ₃ · ? jforin Q and Q ¹ are the Atcra © darstellsia required for Vürvollstfindigung © iä © 9 Äi © - methine dye. Use of IH = Pyrasol © »/ 3 _a 2- £ _- 7-s eh @ n 5 and 6 sur H @ rst © llu3sg of dyes" dsr Structural form ^:! . " 0098AA / 1504 BATH ORIGINAL . J13 - Ι> or a * M * thlnerupp «; , 3rd efaP room HX and 810463 an optionally substituted alkyl, the to complete © ines in cyaninf & rfo · di® sw Verwllstandigisng © iaiss In ο use up ? Z ₁ di @ IH = manufacture too dye ®n der srigegefo, 3-pyrrole », 2-indole «, 3-indole, 3 ~ indolizine or erf order licliieira represents atoms. 009844/1504