DE3230200A1 - 2-PHENYL-2H-1,2,3-TRIAZOLE, METHOD FOR THE PRODUCTION AND USE THEREOF - Google Patents

Description

40

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koenigsberger Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun.

PATENT LAWYERS

APPROVED REPRESENTATIVES AT THE EUROPEAN PATENT OFFICE REPRESENTATIVES BEFORE THE EUROPEAN PATENT OFFICE

CIBA-GEIGY AG _. -, _. -.

Case 1-13516 / =

Basel, Switzerland)

2-Phenyl-2H-l, 2,3-triazoles, processes for their preparation and their use

The present invention relates to new 2-phenyl-4-alkanoyl- (or benzoylr-) 2H-l, 2,3-triazoles, processes for their preparation, their use for the preparation of 2-phenyl-2H-l, 2,3- triazol-4-yl-acetic acids and their derivatives, which are used as starting products for the production of optical brighteners of the 3- (2'-Pheny1-2 ¹ H-I ', 2', 3'-triazol-4'-yl) - coumarin series can be used. The invention also relates to a process for the preparation of said triazolylacetic acids and new intermediates which occur in the preparation of the 2-phenyl-4-alkanoyl- (or benzoyl-) 2H-1,2,3-triazoles according to the invention.

2-Phenyltriazoles and processes for their preparation are known. See the review article by FR Benson et al. in Chem. Rev. j46, 1 (1950) and by TL Gilchrist et al. in Adv. in Heterocyclic Chem. JL6-, 33 (1974), Academic Press, New York and London; also Chem. Ahstr. Vol. 79 (1973), 66367, CH-PS 485 014, DE-AS 1 168 437, DE-PS 1 226 591, E. Klingsberg, Synthesis 1972 (9) 475-7 and Chem. Ber. 98 (4), 1335-41 (1965) (= Chem. Abstr. Vol. 62 (1965), 16090 d).

The object of the present invention was to create new, specifically substituted 2-phenyl-2H-l, 2,3-triazoles that are particularly represent valuable intermediate products, especially for the production of optical brighteners. Besides, it was also the job of

-Λ "

Invention to find a new synthetic route for 2-phenyl-2H-l, 2,3-triazol-4-yl-acetic acids and their derivatives, which can be used for the production of optical brighteners of 3- (2'-phenyl-2'H -l ', 2', 3'-triazol-4 ^V -yl) coumarin series are of great importance.

It has now surprisingly been found that the new, fiction according to 2-phenyl-4-alkanoyl- (or benzoyl-) 2H-l, 2,3-triazoles these Meet requirements. Some of the new intermediates that appear in the manufacture of these valuable compounds are also Subject of the present invention.

The 2-phenyl-2H-l, 2,3-triazoles according to the invention correspond to formula

(D,

wherein RC -C -alkyl, unsubstituted or substituted phenyl L 1 ο

or benzyl and Z denote unsubstituted or substituted phenyl.

As a substituent for the phenyl ring Z or for R "as phenyl or Benzyl radical are, for example, the following: halogen, alkyl, alkoxy, nitro, cyano, trifluonaethyl, alkenyl, cycloalkyl, substituted alkyl or alkoxy such as alkoxyalkyl, alkoxyalkoxy, hydroxyalkyl, hydroxyalkoxy, haloalkyl, haloalkoxy, cyanoalkyl, Carboxyalkyl, sulfoalkyl, phenylalkyl, phenoxyalkyl or carbalkoxyalkyl, Carboxy and SuIfο and their derivatives, phenylsulfonyl or Phenyl or phenoxy, both of which are represented by halogen, alkyl, alkoxy, carbalkoxy, alkylsulfonyl, cyano, nitro, trifluoromethyl, carboxy or SuIfο and their derivatives one or more times (e.g. double) substituted

1 2 can be tuiert; also groups of the formulas -C-NH ₂ , NY Y,

-S (O) -alkyl or -S (O) -subst. Alkyl, where as substituted η η

Alkyl groups mentioned above come into consideration and where η stands for

1 2

the number O, 1 or 2 and Y and Y independently of one another are hydrogen, Alkyl, substituted alkyl (definitions as above) or

1 2

Y and Y together with the nitrogen atom to which they are attached, form a 5- or 6-membered saturated heterocycle, which optionally still contain 1 or 2 nitrogen, oxygen and / or sulfur atoms as ring members and optionally with alkyl groups can be substituted.

Of the substituents mentioned, the phenyl groups or benzyl groups have R, if they are substituted, 2, preferably one substituent. The phenyl radical Z has in particular 3, preferably 2 or such a substituent, with substituents of the 2nd order or sterically hindering radicals preferably at most occur twice, in particular only once, in the phenyl nucleus.

Halogen is to be understood as meaning chlorine, fluorine or bromine, preferably chlorine. Alkyl and alkoxy groups can have 1-8, e.g. 1-6, in particular 1-4, carbon atoms. The same numbers of carbon atoms apply to alkyl or alkoxy parts in composite radicals (e.g. alkoxyalkyl, alkoxyalkoxy, carbalkoxy, etc.) as well as to substituted Alkyl or alkoxy groups. Alkenyl preferably has 2 to 6, in particular 3 or 4, carbon atoms.

Derivatives of sulfo or carboxyl groups are preferably salts,

12 12

Esters and amides. The amides can have the formula —SO “NY Y or CONY Y

(meaning of Y or Y see above). Saturated Stick

1 2

Substance heterocycles (Y + Y), provided they also have further heteroatoms in the ring, preferably have additional heteroatoms as such an N, 0 or / and S atom. Any alkyl substituents have

preferably 1-4 carbon atoms. Examples of such nitrogen lieterocy ien are about the piperidine, piperazine, imidazolidines pyrrolidine, Morpholine, thiomorpholine or oxazolidine ring.

Salts of carboxy and sulfo groups (in this application, “carboxy” and “SuICo” are also always to be understood as meaning their salts), especially alkali metal, alkaline earth metal, ammonium or amine salt ions. The sulfo groups or carboxy groups then correspond to the formula -COOM baw. -SO M, where M is hydrogen or a salt-forming cation. An alkali metal, ammonium or amine salt ion, for example, can be considered as the salt-forming cation. Among amine salt ions, those of the formula H NR R R- are preferred, in which R., R "and R independently of one another denote hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl, or in which R ₁ and R" together add to one Represent 5- or 6-membered saturated nitrogen heterocycle which can also contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazolidine or morpholine ring, while R- is hydrogen.

In the context of formula (1), the 2-phenyl-2H-1,2,3-triazoles are to be emphasized the formula

R 'C -C _fi -alkyl, unsubstituted phenyl or benzyl or with 1 or substituents from the group halogen, C -C ^ -alkyl, C ^ C ^ -alkoxy, C -C -alkenyl, nitro, cyano, carboxy or sulfo and their derivatives, C -Cp-carbalkoxy or trifluoromethyl-substituted phenyl or benzyl; and R, R, and R ₅ independently of one another are hydrogen, halogen,

Trifluoromethyl, cyano, nitro, C -C, -alkyl, C -C.-haloalkyl, CC, -hydroxyalkyl, C.-Cg-alkoxyalkyl, C ₃ -C, -alkenyl, C -C, -alkoxy, CC, - Haloalkoxy, C ₉ -C, alkoxyalkoxy, unsubstituted or substituted by halogen, C -C -alkyl, C -C -alkoxy, C -C -carbalkoxy, C -C -alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of Formula -COC ¹ Y., or -SCLY., Mono- or polysubstituted phenyl or phenoxy; or a group of the formula -C-NH ₀ , -ΝΥ _Ί Υ _Ο , -SO-Y ₀ , -COOY ₀ , -S (O) - (CC.-

Wl ΪΙ JJ J nlH S

Alkyl) or -S (O) - (C -C haloalkyl), where Y and Y_ independently represent hydrogen or C -C alkyl, Y ₀ denotes hydrogen, C -C alkyl or a salt-forming cation and η stand for the number 0, 1 or 2.

If R is a substituted phenyl or benzyl radical, this preferably has one of the specified substituents.

In particular, in formula (2) R ₀ , R and R- have the following meanings: R- is hydrogen, halogen, trifluoromethyl, cyano, nitro, C -C -alkyl, C -C -haloalkyl, C -C -hydroxyalkyl , C -C, alkoxyalkyl, C ₀ -C, -alkenyl, C -C, -alkoxy, C -C, -haloalkoxy, C -C ^ -alkoxyalkoxy, unsubstituted or substituted by halogen, C -C, -alkyl, C -C, -alkoxy, C ₉ -C carbalkoxy, C -C -alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of the formula -COOY ₃ or -SO ₀ Y ₃ mono- or polysubstituted phenyl or phenoxy; or one of the group of the formula -CM ₉ , "NY ₁ Y ₉ , -SO" Y_, -COOY. ,, -S (O) - (C -C.-Alkyl) or -S (O) -

(C -C haloalkyl), where Y and Y ₉ independently of one another are hydrogen or C -C alkyl, Y _{0 is} hydrogen, C -C ₁ alkyl or a salt-forming cation and η is the number 0, 1 or 2 stand; R / hydrogen, halogen, C -C, -alkyl, C -C, -alkoxy, nitro, cyano, C -C ₄ -haloalkyl, -NY Y ₂ , "SO ₃ Y ₃ , -COOY ₃ or C - ^ - Alkylsulfonyl; R. hydrogen, halogen, C -C, alkyl or C -C alkoxy.

The salt-forming cations Y- are preferably the same in Betracli ' as listed above for M. Preferred are alkali metal and Ammonium ions. Derivatives of sulfo and carbonyl groups are also available preferably those which are given by way of example at the outset under formula (1).

Special mention should be made of the 2-phenyl-1,2,3-triazoles of the formula

Λ Λ

wherein R "is C.-C.-alkyl, benzyl, phenyl which is unsubstituted or substituted with one or 2 substituents from the group consisting of chlorine, C.-C.-alkyl, methoxy, nitro, cyano and / or trifluoromethyl, and R 'and Rj are independent from each other hydrogen, halogen, trifluoromethyl, cyano, nitro, C.-C, ~ alkyl, C.-C, -alkoxy, C.-C.-alkylsulfonyl, unsubstituted or by halogen, C.-C, -alkyl, C -C, alkoxy, cyano, nitro, trifluoromethyl or a group of the formula -COOY 'or -SO ₃ Y ₃ ' substituted phenyl or phenoxy; or a group of the formula -SO ₃ Y ₃ , -COOY or -NY Y- where Y, Y- and Y. are as defined in formula (2) and Y 'stands for hydrogen, an alkali metal or ammonium mimion.

R 'in formula (3) preferably denotes hydrogen, halogen, cyano, nitro, C ₁ -C -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylsulfonyl, -COOY ₃ , -SO ₃ Y ₃ or -NY ₁ Y ₂ .

The 2-phenyl-2H-l, 2,3-triazoles are of particular practical importance the formula

^R 3

w-

wherein R '"C ..- C -alkyl, benzyl or phenyl which is unsubstituted or substituted with 1 or 2 substituents from the group consisting of chlorine, methoxy and / or methyl, R" is hydrogen, halogen, trifluoromethyl, cyano, nitro, C -C, -Alkyl, C -C, -alkoxy, C -C -alkylsulphonyl, phenyl or phenoxy which is unsubstituted or substituted by chlorine, methyl, methoxy, cyano, nitro, sulpho or carboxy or their alkali metal or ammonium salts; or a group of the formula -SO-Yl, -COOY 'or -NY Y., where Y, Y "and Yl are as defined in formula (3), and RV is hydrogen, halogen, C -C, -alkyl or C - Mean C, -alkoxy.

Preferred 2-phenyl-2H-1,2,3-triazoles correspond to the formula

I (5),

where R '' 'is hydrogen, halogen, C -C, alkyl, C -C, alkoxy, cyano, Nitro, sulfo or carboxy and their alkali metal or ammonium salts, C -C alkylsulphonyl, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and its alkali metal or ammonium salts

and R ¹ , "denotes hydrogen, halogen, methyl or methoxy. 4

Particular preference is also given to compounds of the formulas (1) to (4) in which R, R 'R' ¹ or R "'denotes methyl.

-λ-

The processes described below for the preparation of inventive The invention also relates to compounds of the formulas (1) to (5).

A first process for the preparation of compounds of formula (1) and thus also the subordinate formulas (2) to (5) consists in the fact that one has an oxime of the formula

HC = NOH

ZN = N-CH (6), R ₂ -C = O

wherein Z and R_ are as defined in formula (1), in the presence of one Cyclized condensing agent to the corresponding triazole.

The compounds of the formulas (2) to (5) are obtained in an analogous manner, by using starting materials of the formula (6) in which R “as well as the phenyl radical Z has the meanings given in formulas (2) to (5) to have. It is preferable to start from an oxime of the formula (6) in which R2 is methyl.

The condensing agent used in the process according to the invention is used preferably an acid anhydride or an acid halide, for example acetic anhydride, propionic anhydride, acetyl chloride, Benzoyl chloride, benzenesulfochloride, toluenesulfochloride, methanesulfochloride, Ethanesulfonyl chloride, phosphorus oxychloride or thionyl chloride, preferably acetic anhydride.

The process according to the invention gives the best results (high yields, purity of the products) when it is carried out with acetic anhydride as the condensing agent in an aqueous medium. The pH is preferably kept between 10 and 13, in particular between 11 and 12, during the cyclization. The reaction temperature can be between 0 and 100 ^° C., preferably between 0 and 50 ^° C., in particular between 5 and 25 ^° C., is used.

-y-

The reaction medium consists of the preferred variant described of the process according to the invention from acetic anhydride and water. However, a water-miscible organic solvent can also be present in the reaction medium. Instead of the with In the water-miscible solvent, a water-immiscible organic solvent can also be used. This variant can be particularly advisable when a water-insoluble product of the formula (1) is obtained. The end product then dissolves in the organic phase, can be separated from the reaction mixture with this and sent for work-up.

Organic solvents miscible with water are, for example lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-propanol, butanol and ethylene glycol, ethyl glycol monoalkyl ether, Tetrahydrofuran, dioxane, formamide, dimethylformamide and similar solvents can be considered.

As a water-immiscible solvent, for example the following are used: liquid aliphatic hydrocarbons and mixtures thereof, halogenated, preferably chlorinated, aliphatic hydrocarbons, for example methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, perchlorethylene, trichlorethylene i.a., aromatic hydrocarbons such as benzene, toluene, xylene, chlorinated aromatic hydrocarbons such as chlorine, dichloro or trichlorobenzene, etc.

Another inventive method for the preparation of 2-phenyl-2H-l, 2,3-triazoles of the formula (1) and the subordinate Formulas (2) to (5) consist in that one can obtain a compound of the formula

HC = O

Z-N = N-OH (7)

R ₂ -C = O

with hydroxylamine or a salt thereof to form a dioxin of the formula

HC = NOH

Z-N = N-CH (8)

R ₂ -C = NOH

converts, the latter in the presence of a condensing agent to a Triazole of the formula

^z - \ \ 'κ TO

^N NOH

cyclized and hydrolyzed this to the corresponding ketone. In the formulas (7) to (9), the general symbols have the meanings given in formula (1). The compounds of formulas (2) to (5) are obtained in an analogous manner by reacting starting compounds of the formula (7) is used, i _n which R 'and Z indicated the phenyl radical in the formulas (2) to (5) Have meanings. It is preferable to start from compounds of the formula (7) in which R _{2 is} methyl.

The reaction of a compound of the formula (7) with hydroxylamine or a salt thereof (first stage) is expediently carried out in an inert solvent, preferably in pyridine. The reaction temperature can be between 0 and 100, in particular between 0 and 50, preferably between 5 and 25 ^{° C.}

The dioxime of the formula (8) obtained is in the presence of a condensing agent 6yclisiert to the triazole of the formula (9). This second stage can be completely analogous to the cyclization of a compound of the Formula (6), as further just described, can be carried out. As preferred The condensing agent, reaction medium, pH, reaction temperatures and solvent come in this second stage

Zo

-ye-

of the second method according to the invention are exactly the same, as listed above for the cyclization of the compound of formula (6). A repetition can therefore remain under.

The hydrolysis of the triazoles of the formula (9) obtained after the second stage (third stage) can be acidic or alkaline in the customary manner take place. The hydrolysis is preferably carried out in the presence of sodium bisulfite or of formaldehyde or paraformaldehyde. It is used in particular in water or in mixtures of water with a water-miscible organic solvent (examples of such solvents, see above), preferably a lower aliphatic alcohol, carried out, preferably at elevated Temperature, especially at the boiling point of the reaction medium.

The in the two processes just described for producing the Intermediate products of the formulas (6) and (8) obtained from triazoles of the formula (1) are new and are therefore also the subject matter of the present invention Invention.

The oximes are therefore a further aspect of the present invention the formula

HC = NOH

(10),

wherein R _{0 is} C.-C ^ -alkyl, unsubstituted or substituted phenyl 2 1 ο

or benzyl, Z is unsubstituted or substituted phenyl and X or NOH. Preferred meanings of substituents are already explained under formula (1).

Particularly noteworthy are the oximes of the formula

H( z-n = nJ R ₂ -J > N0H Γ

R,

R .. I ³ HC = MOH

4V + T

) .- N = N-CH (11),

wherein X 0 or NOH, R 'C -C, .- alkyl, unsubstituted phenyl or benzyl

zlo

or with 1 or 2 substituents from the group halogen, C -C, -alkyl, C -C, -Alkoxy, C, -C, -alkenyl, nitro, cyano, carboxy or SuIfο and their derivatives, C -C -carbalkoxy or trifluoromethyl substituted Phenyl or benzyl and R ", R, and R_ independently of one another are hydrogen, Halogen, trifluoromethyl, cyano, nitro, C -C, -alkyl, C-C, -haloalkyl, C - ^ - hydroxyalkyl, C ^ Cg-alkoxyalkyl, C ^ C ^ alkenyl, C -C, -alkoxy, C -C -haloalkoxy, C "-C - alkoxyalkoxy, unsubstituted or by halogen, C -C alkyl, C -C alkoxy, C ^ -C carbalkoxy, C -C alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of the formula -COOY., or -SO-Y ,. mono- or polysubstituted Phenyl or phenoxy; or one of the group of the formula -C-NH-, -NY Y ",

-SO ₃ Y ₃ , -COOY ₃ , -S (O) _n - (C ₁ -C ₄ -AnCyI) or -S (O) - (C -C ₄ -haloalkyl), where Y and Y "are independent of one another for hydrogen or C -C -alkyl, Y for hydrogen, C -C -alkyl or a salt-forming cation and η for the number 0, 1 or 2 stand. The substituents R ", R_, R, and R_ preferably have the meanings given according to formula (2).

The oximes of the formula are preferred

f ³ HC = NOH
* τ · T

* X / "" ^{N = N TH}

'R

wherein X 0 or NOH, R- 'C -C -alkyl, benzyl or-unsubstituted or with 1 or

2 substituents from the group consisting of chlorine, methoxy and / or methyl substituted Phenyl, R "hydrogen, halogen, trifluoromethyl, cyano, nitro, Cj-C ^ -alkyl, C -C ^ -alkoxy, C -C ^ -alkylsulfonyl, unsubstituted or substituted by chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts Phenyl or phenoxy; or a group of the formula -SCLY '-COOY'

YY J

or -NY Y ₂ , where Y, Y ₂ and Y 'are as defined in formula (3), and R ^ are hydrogen, halogen, C -C, -alkyl or C -C, -alkoxy, where R ^ is preferably hydrogen , Halogen, C -C ^ -alkyl, CC, -alkoxy, cyano, nitro, sulfo or carboxy and their alkali metal or ammonium salts, C -C.-alkylsulfonyl, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and its alkali metal or ammonium salts and R "is preferably hydrogen, halogen, methyl or methoxy.

In the formulas (10) to (12), R ₂ , R ₂ and R ₂ ″ are preferably methyl and X 0.

The preparation of compounds of formulas (10) to (12) with X = NOH has already been described above [oximation of a compound of the formula (7)]. The preparation of compounds of the formulas (10) to (12) with X = O, i.e. also of compounds of the formula (6), can be carried out in such a way that a compound of the formula

HC = O

Z-N = N-CH

(7)

R ₂ -C = O

with hydroxylamine or a salt thereof in a lower alcohol, preferably ethanol, with the addition of sodium acetate to the corresponding Monoxime of the formula (6) converts (see also the example section).

The starting compounds of the formula (7) are obtained, for example, by diazotizing a corresponding aniline of the formula Z-NH ₉ and coupling the resulting diazonium salt solution with a compound of the formula

, -C-C = C-N

, CH

R ₉ -CC = CN; (14)

H \ h

[see. on this D. Leuchs, Chem. Ber. 98_, 1335 (1965)]; see also example part.

The compounds of the formula (14) are known or can easily be obtained by known methods.

The in the above-described second process for the preparation of compounds of the formula (1) obtained intermediates of Formula (9) are new and also form an object of the present invention. Preferred connections within the Formula (9) correspond to those of formulas (2) to (5), with the difference that they contain the group —C-R ', "C-R", -C-R' "or -C-CH

0 0 0 0

the group -CR ', -CR ", -C-R'" or -C-CH is replaced. Il ^ (I · ^ Ii £ · IJj NOH ■ NOH - NOH NOH

The oxime compounds in which R ₂ , R ₂ , R ' ₂ ' or R " ^{f represent} methyl.

The 2-phenyl-2H-l, 2,3-triazoles of the formula (I) in which R _{9 is} methyl are valuable starting materials for the preparation of 2-phenyl-2H-l, 2,3-triazole-4- yl-acetic acids and their derivatives, which in turn are intermediates for the production of optical brighteners. With the aid of the compounds of the formula (1) according to the invention, a new, particularly favorable way of preparing these practically important triazolylacetic acids is opened. So far, these acetic acids have been produced in a number of ways that

however, all of them have certain disadvantages or difficulties are. See, for example, DE-OS 2,329,991, NL-OS 74-07127, Chem. Abstr. 88 170153η (1978), Chem. Abstr. 87, 201547 (1977).

The other 2-phenyl-2H-l, 2,3-triazoles of the formula (1) in which R _{9 is} different from methyl can also be used as starting materials for the preparation of the above-mentioned 2-phenyl-2H-l, 2, 3-triazol-4-yl-acetic acids and their derivatives are used. For this purpose, they can first be converted by known methods into compounds of the formula (I) in which R _{2 is} methyl, the latter being able to be converted further into the corresponding triazolylacetic acids as described below. For example, triazoles of the formula (1), in which R.sup.1 is different from methyl, can initially be converted into an acid of the formula

(18)

are oxidized, preferably with the help of KMnO. The acids of

Formula (18) can then be converted into the corresponding acid chlorides (e.g. by chlorination with PCI, PCI, SOCl, SO "C1

• j 3 ί. jL £

ua) and the latter with a methyl magnesium halide (CH MgX, X = Cl, Br ₉ J) with the aid of the Grignard reaction to the corresponding triazoles of the formula (1), in which R ₂ = methyl, are reacted. The process steps described above are known per se from textbooks on organic chemistry.

According to the invention, 2-phenyl-2H-1,2,3-triazol-4-yl-acetic acids can be used in a particularly advantageous manner the formula

I (15)

and their derivatives, in which Z is unsubstituted or substituted phenyl and R _{7 is} hydroxy, C -C alkoxy or a group of the formula

or -NY.Y, -, where Y, and Y are independent of one another for hydrogen or C ^ -C -alkyl or Y, and Y together with the Nitrogen atom to which they are attached for a 5- or 6-membered one saturated heterocyclic ring, which optionally also contains an oxygen, sulfur and / or nitrogen atom as ring members and optionally substituted by 1 or 2 C 1 -C 4 alkyl groups can be, and ir stand for a salt-forming cation, produce, by adding a 2-phenyl-2H-l, 2,3-triazole of the formula

Z-tf I (16)

with morpholine, piperidine or dimethylamine and sulfur to one 2-Phenyl-2H-1,2,3-triazol-4-ylthioacetamide of the formula

(17)

where X ^ -N ^ 0, -N _n ^ _/ · or -N (CH ₃ ) "means, converts and · - · · - ·

the latter without isolation to the corresponding 2-phenyl-2H-1,2,3-triazol-4-yl-acetic acid hydrolyzed and optionally an acid obtained in this way by customary methods into a salt, an ester or a Amide transferred.

Definitions for preferred M (salt-forming cation) and preferred 5- or 6-membered saturated heterocyclic rings (Y, + Y ^) in formula (15) are initially in connection with formula (1)

-yr-

1 2
(eg Y + Y) and the same preferred ranges also apply to the compounds of the formula (15).

Preferred triazolylacetic acids within the framework of the formula (15) are obtained if, instead of compounds of the formula (I), those of the formulas (2) to (5) are used as starting materials (in each case with R ~ ⁼ CH-). The optional conversions of compounds of the formula (15) obtained with R ₇ = OH (free acid) into corresponding salts, esters and amides can be carried out by customary salt formation, esterification and amidation processes.

To prepare the triazolylacetic acids of the formula (15), a compound of the formula (16) is preferably reacted with morpholine, piperidine or dimethylamine and sulfur powder. ("Willgerodt-Kindler reaction"). It is also possible to use amines other than those mentioned, for example diethylamine, piperazine, thiomorpholine and other amines commonly used for the Willgerodt-Kindler reaction. The reaction usually takes place without a solvent. The temperature is about 50-15O ⁰ C, preferably 80-12O ⁰ C. The thioamide obtained, which is usually not isolated, can then be converted into the corresponding acetic acid or its salt with the aid of a base in an aqueous medium The base used is preferably an alkali metal hydroxide, in particular NaOH. The hydrolysis is advantageously carried out at an elevated temperature, preferably at the reflux temperature.

Alternatively, the conversion of the acetyltriazoles of the formula (16) into the corresponding triazolylacetic acids with the aid of ammonium polysulphide and subsequent hydrolysis of the intermediate product take place ("Willgerodt reaction"). In this variant, a solvent can also be used can also be used, for example dioxane.

-yr-

Some of the compounds of the formula (15) are known, some of them but new. The compounds of formula (15) are also a subject of the present invention insofar as they are new.

As already mentioned, the triazolylacetic acids and their derivatives of the formula (15) can be used for the production of optical brighteners of the 3- (2'-phenyl-2 ¹ H-I ', 2', 3'-triazol-4'-yl) coumarin series be used. Processes for the preparation of such brighteners using 2-phenyl-2H-1,2,3-triazol-4-yl-acetic acids and their derivatives are described in US Pat. No. 3,966,755 and GB Pat. No. 1,412,049.

As already mentioned at the outset, the literature also discloses, inter alia, 2-phenyl-4-acetyltriazoles which are substituted in the 5-position by a methyl group. See, for example, DE-PS 1,226,591, E. Klingsberg, Synthesis 1972 (9), 475-7 and Chem. Ber. £ 9 (4), 1335-41 (1965). However, the inventive triazoles of the formula (1) which are unsubstituted in the 5-position are surprisingly more valuable intermediates than the 3- (2'-pheny 1-2 ¹ HI ', 2', 3'-triazole which can be prepared from them ^ '- yl ^ coumarin brighteners (via the intermediate stage of the corresponding triazolylacetic acids) have much more favorable brightening properties. They achieve, for example, on textile materials, for example made of synthetic fibers, especially polyester fibers, significantly higher degrees of whiteness than those brighteners that are methyl-substituted in the 5-position 2-phenyl-4-acetyl-2H-l, 2,3-triazoles can be prepared.

In the examples below that illustrate the various aspects of the explain the present invention in more detail, without being intended to express a restriction thereto, are parts and percentages, unless otherwise indicated, parts by weight and percentages by weight. Melting and boiling points are, unless nothing otherwise stated, uncorrected.

Example 1 : 205 g of 2-phenylazoacetoacetaldehyde-1-oxime of the formula

CH = NOH

(201) - ^ j) * -N = N-CH

COCH ₃

are contained in 1250 ml of water at 40 ⁰ C, the 44 g of sodium hydroxide dissolved and cooled with stirring to 15 ° C, wherein the sodium salt of the oxime partially fails. In the course of one hour, 112 g of acetic anhydride are added dropwise with vigorous stirring. The pH from 11.5 to 12 and by external cooling the temperature at 15-17 ⁰ C is maintained by simultaneous dropwise addition of concentrated sodium hydroxide solution. The reaction product deposited after the end of the reaction is filtered off with suction, washed with water and dried. In this way, 179 g (corresponding to 96% of theory) of 4-acetyl-2-phenyl-2H-1,2,3-triazole of the formula are obtained

'"COCH ₃

as a beige product which melts at 95-96 ° C after recrystallization from hexane.

In an analogous manner, using the appropriately substituted 2-Phenylazoacetoacetaldehyde-l-oximes of the formulas (203) - (2 21) (see Example 2) as starting materials, including the 4-acetyl-2-phenyl-2H-1,2,3-triazoles of the formula listed in Table 1 below

R Ν "COCH

obtain.

Table 1

- ytr-

Connection no. R. R ' Melting point
(° C) 103 4-CN H 154-157 104 4-CH ₃ H 82-83 105 3-CH ₃ H 60-61 106 2-CH ₃ H 59-60 107 4-Cl H 110-111 108 3-Cl H 113-114 109 2-Cl • Ή 70-72 110 4-OCH ₃ H 112-113 111 3-OCH ₃ H 72-73 112 2-OCH ₃ H 58-60 113 4-COOH H 261-262 114 4-NO ₂ H 123-125 115 4-0-C ₆ H ₅ H 108-110 116 4-Cl 2-Cl 103-105 117 4-SO ₂ CH ₃ H 176-178 118 3-SO ₃ Na H > 300 119 4- - ^ ^ -COOH H 268-269 120 4-F H 114-118 121 4-Br H 114-116

In an analogous manner, using the correspondingly substituted 2-phenylazoacetoacetaldehyde-1-oximes of the formulas 223 273 (see Example 2) as starting materials also the 4-acetyl-2-phenyl-2H-1,2,3-triazoles listed in the following table la the formula

-2t-

3ο

R ¹

R '

^% COCH "

obtain.

Table la

Connection no. R. R ' R " 123 4-C ₂ H ₅ H H 124 3-Br H H 125 2-F H H 126 4-y H H 127 3-y H H 128 2-y H H 129 4-CF ₃ H H 130 2-CF ₃ H H 131 4-1-C ₃ H ₇ H H 132 4-N (CH ₃ ) ₂ H H 133 3-CH ₃ 4-Br H 134 3-NH ₂ H H 135 3-NHSO CF ₃ H H 136 3-NO ₂ 4-CH ₃ H 137 3-NH ₂ 4-CH ₃ H 138 3-NHSO ₂ CF ₃ 4-CH ₃ H 139 3-Cl 4-CH ₃ H 140 3-NH ₂ 4-Cl H 141 3-NHSO CF. 4-Cl H 142 3-Cl 4-Cl H 143 3-0CH ₀ 4-OCH ₃ j H 144 3-OCH ₃ 5-OCH ₃ H 145 I.
ι 3-Cl 5-Cl H

Table la continuation

Connection no. R. R ' R " 146 2-Br 4-Br H 147 3-NHSO ₂ CF ₃ 4-CH ₃ 6-CHg 148 3-NHSO ₂ CFg 4-CHg 5-CHg 149 2-F 4-F H 150 3-CFg H H 151 · - ·
4-0— ^ ζ * " ⁰¹
= H H 152 2-Cl 6-C.l H 153 2-Cl 3-Cl 4-Cl 154 2-Cl 4-Cl 5-Cl 155 * 3-NO ₂ 4-CHg 6-CHg 156 3-NH ₂ 4-CHg 6-CHg 157 3-CN H H 158 2-CN H H 159 3-SCHg H H 160. 3-SOCHg H H 161 3-NO ₂ H H 162 2-NO ₂ H H 163 2-CHg 4-Br H 164 2-CN 4-Cl H 165 3-CFg 4-Cl H 166 3-CFg 4-NO ₂ H 167 4-CFg 2-NO ₂ H 168 2-CHg 4-Cl H 169 3-NO ₂ 4-Cl H 170 3-OCFg H ^H 171 4-0CHF ₂ H H
I. 172 2-0CHF ₂ H H 173 4-0CF ₂ CHF ₂ H

*) Compound no. 155 had a melting point of 127 - 129 ° C

sz

Likewise, using the correspondingly substituted starting materials of the formula (201) type, the other 2-phenyl-2H-1,2,3-triazoles of the formula (1) are obtained.

Example 2: 2-phenylazoacetoacetaldehyde-l-oxime of the formula (201) is made as follows:

A solution of 170 g of sodium acetate trihydrate in 300 ml of water is added to a suspension of 190 g of 2-phenylazoacetoacetaldehyde of the formula (301) in 300 ml of ethanol, followed by a solution of 76.5 g of hydroxylamine hydrochloride in 100 ml of water suspension is stirred for 5 hours at 50 ⁰ C and cooled to 20 ⁰ C. the precipitate is filtered off with suction, washed with water and dried. 190 g (92.5% of theory) are obtained in this manner 2-Phenylazoacetoacet- 'aldehyde-1 -oxime of the formula (201) with a melting point of 152-153 ⁰ C after crystallization from toluene.

In an analogous manner, using the appropriately substituted 2-Phenylazoacetoacetaldehydes of the formulas (303) - (321) (see Example 3) as starting materials, including the 2-phenylazo-acetoacetaldehyde-1-oximes of the formula listed in the table below

(202). -N

R CH = NOH

manufactured.

Table 2

Connection no. R. R ^f Melting point 203 4-CN H 183-185 204 4-CH ₃ H 195-197 205 3-CH ₃ H 167-168 206 2-CH ₃ H 175-176 207 4-Cl H 196-197 208 3-Cl H 171-172 209 2-Cl H 174-175 210 4-OCH ₃ H 163-165 211 3-OCH ₃ H 131-132 212 2-OCH ₃ H 190-192 213 4-COOH H 243-247 214 4-NO ₂ H 222-224 215 = H 129-131 216 4-Cl 2-Cl 197-199 217 4-SO ₂ CH ₃ H 203-204 218 3-SO ₃ Na H - 219 4- "^" - COOH H 250-252 220 4-F H 221 4-Br H

In an analogous manner, using the appropriately substituted Starting products of the formula (301) type are the 2-fhenylazo-acetoacetaldehyde-1-oximes of the formula listed in Table 2a

R "

R '

CO-CH

Λ- '

-N = N-CH I

CH = NOH

and the other oximes included in the formula (6) are obtained.

Table 2a

Connection no. R. R ' ί R " 223 4-C ₂ H ₅ H H 224 3-Br H H 225 2-F H H 226 4-y H H 227 3-y H H 228 2-y H H 229 4-CFg H H 230 2-CFg H H 231 4-1-C ₃ H ₇ H H 232 4-N (CHg) ₂ H H 233 3-CHg 4-Br H 234 3-NH ₂ H H 235 3-NHSO ₂ CF. H H 236 3-NO ₂ 4-CHg H 237 3-NH ₂ 4-CHg H 238 3-NHSO ₂ CF. 4-CHg H 239 3-Cl 4-CH ₃ H 240 3-NH ₂ 4-Cl H 241 3-NHSO ₂ CFg 4-Cl H 242 3-Cl 4-Cl H 243 j 3-0CHg 4-OCH ₃ H 244 j 3-OCH ₃ 5-OCH ₃ H ί

Table 2a continued

Connection no. R. R ' R " 245 3-Cl 5-Cl H 246 2-Br 4-Br H 247 3-NHSO ₂ CF ₃ 4-CH ₃ 6-CH ₃ 248 3-NHSO ₂ CF ₃ 4-CH ₃ 5-CH ₃ 249 2-F 4-F H 250 3-GF ₃ H H 251 40- '/' - Cl H H 252 2-Cl 6-Cl H 253 2-Cl 3-Cl 4-Cl 254 2-Cl 4-Cl 5-Cl 255 3-NO ₂ 4-CH ₃ 6-GH ₃ 256 3-NH ₂ 4-CH ₃ 6-CH ₃ 257 3-CN H H 258 2-CN H H 259 3-SCH ₃ H H 260 3-SOCH ₃ H H 261 3-NO ₂ H H 262 2-NO ₂ H H 263 2-CH ₃ 4-Br H 264 2-CN 4-Cl H 265 3-CF ₃ 4-Cl H 266 3-CF ₃ 4-NO ₂ H 267 4-CF ₃ '2-NO ₂ H 268
269
270 2-CH ₃
3-NO ₂
3-OCF ₃ 4-Cl
4-Cl
H H
H
H 271 4-OCHF ₂ H H 272 2-0CHF ₂ H H 273 4-0CF ₂ CHF ₂ H H

Example 3 : 2-Phenylazoacetoacetaldehyde of formula (301) is prepared as follows:

A diazonium salt solution prepared in a conventional manner from 1 mol Aniline is left with stirring at 5-6 ° C in an aqueous solution of 1.1 mol of l-dimethylaminobuten- (l) -one (3) [see D. Leuchs, Chem. Ber. _98, 1335 (1965)]. The pH of the coupling solution is kept at 3.8-4 by adding sodium acetate in portions. The mixture is stirred at 12-15 ° C. until the coupling has ended and then suction the yellow coupling product from. This is washed with water and dried. 175 g are obtained in this way (corresponding to 92% of the Theory) 2-phenylazoacetoacetaldehyde of the formula

(301) /

orange yellow as a product which melts after recrystallization from ethanol at 117-118 ⁰ C.

In an analogous manner, using the diazonium salt solutions the correspondingly substituted anilines as starting materials, including the 2-phenylazoacetoacetaldehydes listed in Table 3 below the formula

obtain.

- ztr-

Table 3

Connection no. R. R ¹ Melting point
( ⁰ C) I.
i 303 4-CN H 156-158 304 4-CH ₃ H 103-105 305 3-CH ₃ H 76-77 306 2-CH ₃ H 91-92 307 4-Cl H 122-123 308 3-Cl H 114-115 309 2-Cl H 117-118 310 4-OCH ₃ H 107-109 311 3-OCH ₃ H 94-96 312 2-OCH ₃ H 119-121 313 4-COOH H 234-236 314 4-NO ₂ H 177-178 315 ■ 4-0- / ~ \ H 79-81 316 4-Cl 2-Cl 121-122 317
318 4-SO ₂ CH ₃
3-SO ₃ Na H
H 167-168
> 300 319 4 - ^ ^ -COOH H > 300 320 4-F H 321 4-Br H

In an analogous manner, 'using' the correspondingly substituted Anilines and the corresponding compounds of the l-dimethylaminobuten- (l) -one (3) type as starting products, 2-phenylazoacetoacetaldehydes, which have the same substituents in the phenyl ring as compounds 223 to 273 (Table 2a), as well as the others, 2-phenylazoacetoacetaldehydes comprised by the formula (7) are obtained.

Example 4 :

a) 190 g 2-Phenylazoacetoacetaldehyd of formula (301) are suspended in 400 ml of pyridine at 15 ° C and added with 146 g of hydroxylamine hydrochloride in portions while the temperature is maintained by external cooling at 15-20 ⁰ C. The now dark solution is then stirred for 16 hours at room temperature. The reaction mixture is then mixed with 600 ml of water, stirred well and the separated reaction product is filtered off with suction, washed with water and dried. In this way, 207 g (corresponding to 94 % of theory) of 2-phenylazoacetoacetaldehyde-1,3-dioxime of the formula are obtained

f ³

O = NOH

(401) · ( ^.

CH = NOH

which melts ^{at 159-16O 0} C after recrystallization from a mixture of equal parts of ethanol and water.

b) 220 g of 2-phenylazoacetoacetaldehyde-l, 3-dioxime of the formula (401) are dissolved in 2000 ml of water containing 80 g of sodium hydroxide. With stirring, 205 g of acetic anhydride are added dropwise ^{at 10-15 ° C. in the course of two hours.} Concentrated sodium hydroxide solution is added dropwise at the same time to keep the pH between 11.5 and 12. After the reaction has ended, the suspension is adjusted to a pH of 6 by adding dilute hydrochloric acid and the reaction product which has separated out is filtered off with suction, washed with water and dried. In this way, 200 g (corresponding to 100% of theory) of 4-acetyl-2-phenyl-2H-1,2,3-triazole oxime of the formula are obtained

(402) ·.; w

^N N-OH

as a beige product, which after recrystallization from chlorobenzene melts at 175-176 ° C.

c) 20 g of 4-acetyl-2-phenyl-2H-l, 2,3-triazole-oxime of the formula (402) and 36.4 g of sodium bisulfite are added to a mixture of 100 ml of ethanol and 50 ml of water for 24 hours Stir heated to reflux temperature. After cooling, the mixture is diluted with 200 ml of water, adjusted to pH 3 with hydrochloric acid and the precipitated product is filtered off with suction, washed with water and dried. Obtained in this manner 17.5 g (corresponding to 93.5% of theory) of 4-acetyl-2-phenyl-2H-1,2,3-triazole of the formula (101) as a beige product at 95-96 ⁰ C melts.

Step c) can also be carried out as follows: 20 g of 4-acetyl-2-phenyl-2H-l, 2,3-triazole-oxime of the formula (402) and 4.5 g of paraformaldehyde are in a mixture of 100 ml of water and 10 ml of 30% HCl heated to reflux temperature for 24 hours. After cooling, the mixture is diluted with 200 ml of water, and the precipitated product is filtered off with suction, washed with water and dried. In this way, 17.9 g (corresponding to 96% of theory) of 4-acetyl-2-phenyl-2H-l, 2,3-triazole of the formula (101) are obtained as a beige product, that melts at 95-96 ° C.

Following the method of Example 4 using the appropriate 2-Phenylazo'acetoacetaldehydes of the formulas (303) to (321) as starting products the compounds of the formulas (103) to (121) listed in Table 1 are also obtained, with the corresponding substituted intermediates of the type of, formula (401) and (402) attack.

Example 5 : 250 g of 2- (4-nitrophenylazo) -acetoacetaldehyde-1-oxime of the formula

IH = NOH

are suspended in 1000 ml of water containing 40 g of sodium hydroxide, stirred well for 30 minutes at room temperature, mixed with 1000 ml of methylene chloride and the mixture is cooled ^{to 15 ° C. with stirring.} Over the course of one hour, 204 g of acetic anhydride are added dropwise with vigorous stirring. The pH from 11.5 to 12 and AussenkUhlurrg the temperature at 15-17 ⁰ C is maintained by simultaneous dropwise addition of concentrated sodium hydroxide solution. After the reaction has ended, the two-phase mixture is separated, the organic phase is washed with water, briefly dried over magnesium sulfate and evaporated. In this way, 161 g (corresponding to 69.5 % of theory) of 4-acetyl-2- (4-nitrophenyl) -2H-1,2,3-triazole of the formula are obtained

(114) OJ- ''

tf CO-CH ₃

as a brown product which, after recrystallization from alcohol, in light brown crystals obtained ⁰ C of melting point 123-125.

Example 6: 93.5 g of 3-oxo-3-phenyl-2-phenylazopropionaldehyde-l-oxira of the formula ^^

(601) are suspended in 500 ml of water containing 30 g of sodium hydroxide

dated, stirred well for 30 minutes at room temperature, mixed with 300 ml of methylene chloride and the mixture obtained is cooled ^{to 15 ° C. with stirring.} 71.5 g of acetic anhydride are then added dropwise over the course of 2 hours with vigorous stirring. The pH from 11.5 to 12 and by external cooling the temperature at 15-17 ⁰ C is maintained by simultaneous dropwise addition of concentrated sodium hydroxide solution. After the reaction has ended, the two-phase mixture is separated, the organic phase is washed with water, briefly dried with magnesium sulfate and evaporated, and the residue is distilled in vacuo. In this way, 81.7 g (94% of theory) of 4-benzoyl-2-phenyl-2H-1,2,3-triazole of the formula are obtained

M>

as a yellow-orange substance with a boiling point of 165-17O ° C / 13 Pa and a melting point of 49-51 ° C.

In an analogous manner, the above method is used of 3-0x0-3- (p-methylphenyl) -2-phenylazo-propionaldehyde-1-oxime of the formula (701) as the starting product, the compound of the formula

• - ·

«= \ W χ — κ

(603)

obtained, which has a boiling point of 177-182 ° C / 13 Pa and a melting point of 63-64 ° C.

Example 7 ; 3-0xo-3-phenyl-2-phenylazo-propionaldehyde-l-oxime of the formula (601) is prepared as follows:

Z.U a suspension of 126 g of S-Oxo-S-phenyl ^ -phenylazo-propionaldehyde [known from reports of the German Chem. Ges. 2JL ^ 1697 (1888)] in 500 ml of ethanol a solution of 85 g of sodium acetate

trihydrate in 200 ml of water followed by a solution of 36.5 g of hydoxylamine hydrochloride in 100 ml of water, added dropwise. The suspension is stirred for 20 hours at room temperature, the precipitate formed sucked off, washed with water and dried. 124 g (93% of theory) of 3-oxo-3-phenyl-2-phenylazo-propionaldehyde-1-oxime are thus obtained Formula (601) with a melting point of 192-193 ° C after crystallization from ethanol.

In an analogous manner, the above method is used of 3-oxo-3- (p-mothylphenyl) -2-phenylazo-propionaldehyde [known from Reports of the German Chem. Ges. J59, 108 (1926)] as the starting product the 3-oxo-3- (p-methylphenyl) -2-phenylazo-propionaldehyde-1-oxime of

^Orme * HC = ⁵ NOH

obtained, which has a melting point of 206-207 ⁹ C after crystallization from an ethanol / dimethylformamide mixture.

Example 8 ; ^{17.6 g of powdered sulfur are added at 70 °} C. to a solution of 93.5 g of 4-acetyl-2-phenyl-2H-l, 2,3-triazole of the formula (101) in 56.5 g of morpholine and the resulting powder is added The dark brown melt is stirred at 100-105 ° C. for 4 hours. 250 ml of 17% NaOH are then added dropwise and the reaction mixture is refluxed for a further 4 hours. After cooling to 80 ⁰ C is provided with hydrochloric acid to pH 7 for 30 minutes nachgarührt at this temperature, diluted with water to 1000 ml and filtered to clarification. The now clear solution is adjusted to pH 2 with hydrochloric acid and the beige product which has precipitated is filtered off, washed with water and dried. In this way 90 g (corresponding to 88.5% of theory) of 2-phenyl-2H-1,2,3-triazol-4-ylacetic acid of the formula are obtained

te

(831) \ ^

W CIU-COOH

which melts after recrystallization from a mixture of 1 part toluene and 2 parts of ligroin at 109-110 ⁰ C.

In an analogous manner, using the corresponding substitutes 4-Acetyl-2-phenyl-2H ~ l, 2,3-triazoles of the formulas (1O4) - (113), (116), (117) and (120) as starting products, including those in the following table », listed substituted 2-pheny1-211-1,2,3-triazol-4-yl-acetic acids the formula

R ' _%) \ Λ v ^ O 2) *
R. >"\ }
r \ h ₂ -cooh obtain.

Table 4

Connection no. R. R ^r Melting point
(° c) 803 4-CH ₃ H 116-117 804 3-CH ₃ H 86-87 805 2-CH ₃ H 47-48 806 4-Cl H 151-152 807 3-Cl H 139-140 808 2-Cl H 95-96 809 4-OCH ₃ H 140-141 810 3-OCH ₃ H 78-80 811 2-OCH ₃ H 99-101 812 4-COOH H 264-265 813 4-SO ₂ CH ₃ H 197-198 814 4-Cl 2-Cl 107-109 815 4-F H 136-140

In an analogous manner, using the 2-phenyl-2H-l, 2,3-triazoles of formulas 114, 115, 118, 119, 121 and 123-173 as starting products the correspondingly substituted 2-phenyl-2H-l, 2,3-triazol-4-ylacetic acids are obtained. The aforementioned 2-phenyl-2H-l, 2,3-triazol-4-yl-acetic acids can be converted into derivatives by customary methods, for example into salts, esters, thioesters, amides or thioamides.

Example 9: As already mentioned, the 2-phenyl-2H-l, 2,3-triazol-4-ylacetic acids obtained from the 2-phenyl-2H-l, 2,3-triazo] enes of the formula (1) according to the invention and their derivatives (see formula 15) for the production of optical brighteners, especially those of the 3-triazol-4'-yl-coumarin series, are used (see, for example, US Pat. No. 3,966,755 and GB Pat. No. 1,412,049). For example, such brighteners can be as follows

will be obtained:

a) In a mixture of 13.5 g of the sodium salt of 2-phenyl-2H-l, 2,3-triazol-4-yl-acetic acid of the formula (801) and 135 ml of acetic anhydride, 10.3 g of 2-hydroxy l-naphthaldehyde registered. The reaction mixture is heated to the boil over the course of one hour, while stirring, and refluxed for 5 1/2 hours. After the reaction mixture has cooled to about 80 ⁰ C, is poured into 1700 ml cold water and filtered with suction after several hours the product was washed with water and dried in vacuo at 60 to 70 ⁰ C dried. After pre-cleaning by redissolving from 235 ml of chlorobenzene, a pre-purified product is obtained. After two recrystallizations from chlorobenzene with the aid of fuller's earth, the compound of the formula is obtained

• · · χ ν \

H ι ι ß —:> (901) γ YY V ■ -

vv \

in the form of yellow crystals with a melting point of. 238 to 238.5 ° C.

b) In a mixture of 14.6 g of the sodium salt of 2-phenyl-2H-1,2,3-triazol-4-yl-acetic acid of the formula (801) and 130 ml of acetic anhydride, 9.9 g of 2-hydroxy 4-methoxybenzaldehyde registered. The reaction mixture is heated to boiling within one hour and refluxed for 7 1/2 hours. After the reaction mixture has cooled to about 80 ⁰ C, is poured into 1700 ml of water and filtered off with suction, the reaction product after hydrolysis of the excess acetic anhydride, washed neutral with water and then stirred with a little alcohol to a paste, and suction filtered, the crystal product, and washed again with alcohol. After two recrystallizations from chlorobenzene with the aid of fuller's earth, the compound of the formula is obtained

-Af- "

•
\ /
■
Il Ύ Α • <- , - / • N; / •
\ ψ
/ Ν /
• I. ν \

in the form of yellowish crystals with a melting point of 196 to 196.5 ⁰ C.

If the above procedure b) is followed, the sodium salt of 2-phenyl-2H-l, 2,3-triazol-4-ylacetic acid of the formula (801) is replaced by equivalent amounts of the sodium salts of 2- (m-chlorophenyl) - 2H-l, 2,3-triazol-4-yl-acetic acid of the formula (802), 2- (p-methylphenyl) 2H-l, 2,3-triazol-4-yl-acetic acid of the formula (803) or of 2- (p-methyl-m-chlorophenyl) 2H-l, 2,3-triazol-4-yl-acetic acid, the compounds 2- (m-chloropheny1) -4- (7 ', which can be used as optical brighteners) are obtained -methoxycoumarin-3'-y1) 2H-1,2,3-triazole (melting point: 202-203 ⁰ C), 2 ~ (p-methylphenyl) -4- (7'-methoxycoumarin-3'-yl) 2H- 1,2,3-triazole (melting point 202.5 to 203 ⁰ C) and 2- (p-methyl-m-chlorophenyl) -4- (7 ^l -methoxycumarin-3'-yl) 2H-l, 2, 3-triazole (melting point 241.5 - 242 ⁰ C).

Claims (1)

Patent claims: Phenyl-2H-1,2,3-triazoles of the formula z- wherein R “C -C alkyl, unsubstituted ALo substituted or substituted phenyl or benzyl and Z unsubstituted or substituted phenyl. 2. 2-phenyl-2H-l, 2,3-triazoles according to claim 1 of the formula R 'C -C, -alkyl, unsubstituted phenyl or 3enzyl or with 1 or 2 substituents from the group halogen, C -C, -alkyl, C -C, -alkoxy, C -C, -alkenyl, nitro, cyano, Carboxy.oder sulfo and their derivatives, C "-C ^ -Carbalkox} 'or Trifluonnethyl substituted phenyl or benzyl and R_, R, and R_ independently hydrogen, halogen, trifluoroethyl, cyano, nitro, C -C -alkyl, C - C -haloalkyl, CC, -hydroxyalkyl, C ₉ -C ₆ -alkoxyalkyl, C ₃ -C, -alkenyl, C -C ₄ -alkoxy, ^c ₁ ~ ^c a ~ haloalkoxy, C_-C, alkoxyalkoxy, unsubstituted or by halogen , C -C -alkyl, C -C, -alkoxy, C ₂ -C "-carbalkoxy, C -C -alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of the formula -COOY_ or -SO-Y" one or polysubstituted phenyl or phenoxy; or a group of the formula -fl-NI ^, - ^ - J ₂ * ~ ^S ° 3 ^Y 3 '~ ^CQ0Y 3> ~ ^{S (} ' ⁰⁾ n ~ ^(C l ~ ^C 4 ~ alkyl) or -S (O ) - (C -C -haloalkyl), where Y and _{Y- independently of one another for hydrogen or C 1} -C_ -alkyl, Y "for hydrogen, C -C" -alkyl or a salt-forming cation and η for the number 0, 1 or 2 stand. -X-3. 2-Phenyl-2H-l, 2,3-triazoles according to Claim 2 of the formula R'2 C -C alkyl, benzyl, unsubstituted or with one or 2 substituents from the group consisting of chlorine, C -C alkyl, methoxy, nitro, cyano and / or trifluoromethyl substituted phenyl and Rl and R! independent from one another hydrogen, halogen, trifluoromethyl, cyano, nitro, C -C alkyl, C -C alkoxy, C -C alkylsulfonyl, unsubstituted or by halogen, C -C alkyl, C -C alkoxy, cyano, nitro, trifluoromethyl or a group of the formula -COOYl or ~ SO_Y 'substituted Phenyl or phenoxy; or a group of the formula -SO Y ,, -COOY, or -NY Y ", where Y, Y" and Y_ are as defined in claim 2 and Yi for hydrogen, an alkali metal or ammonium ion stands. 4. 2-phenyl-2H-l, 2,3-triazoles according to claim 3 of the formula where R "' C -C alkyl, benzyl or unsubstituted or with 1 or 2 substituents phenyl substituted from the group consisting of chlorine, methoxy and / or methyl, R "hydrogen, halogen, trifluoromethyl, cyano, nitro, C -C alkyl, C -C, alkoxy, C -C, alkylsulfonyl, unsubstituted or by chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts substituted phenyl or phenoxy; or a group of the formula -SO-Yl, -COOY 'or -NY.Y-, where Y, Y and Y 'are as defined in claim 3, and RV is hydrogen, Halogen, C -C ^ alkyl or C -C alkoxy. 5. 2-phenyl-2H-l, 2,3-triazoles according to any one of claims 1-4, wherein R ₇ , R ', R "or R'" is methyl. 6. 2-phenyl-2H-l, 2,3-triazoles according to claim 5 of the formula wherein R '"is hydrogen, halogen, C -C, -alkyl, G -C, -alkoxy, cyano, nitro, sulfo or carboxy and their alkali metal or ammonium salts, C -C -alkylsulfonyl, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and its alkali metal or ammonium salts and'R ¹ "is hydrogen, halogen, methyl or methoxy. 7. Process for the preparation of 2-phenyl-2H-l, 2,3-triazoles of the formula Λ, -R. where RC -Q -alkyl, unsubstituted- Δ L O tes or substituted phenyl or benzyl and Z is unsubstituted or substituted phenyl, characterized in that one an oxime of the formula HC = NOH Z-N = N-CH, R ₂ -C = O wherein Z _and R _{2 are} as defined above, cyclized in the presence of a condensing agent to give the corresponding triazole. 8. The method according to claim 7 for the preparation of 2-phenyl-2H-l, 2,3-triazoles the formula R " • Yk- where R '' ' C -C alkyl, benzyl or unsubstituted or with 1 or 2 substituents substituted from the group consisting of chlorine, methoxy and / or methyl Phenyl, R "hydrogen, halogen, trifluoroethyl, cyano, nitro, C -C, -alkyl, C -C, -alkoxy, C -C ^ -alkylsulfonyl, unsubstituted or by chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts substituted phenyl or phenoxy; or a group of the formula -SO-Yl, -COOY 'or -NY Y., where Y, Y "and Y 'are as defined in claim 3, and R" is hydrogen, Halogen, C -C, alkyl or C -C, alkoxy, characterized in that that you can get an oxime of the formula wherein R '", R" and R "are as defined above, cyclized in the presence of a condensing agent to give the corresponding triazole. 9. The method according to claim 7 or 8, characterized in that one starts from an oxime in which R ₀ or R '"is methyl. 10. The method according to any one of claims 7-9, characterized in that that the condensing agent used is an acid anhydride or acid halide, for example acetic anhydride, propionic anhydride, acetyl chloride, Benzoyl chloride, benzenesulfochloride, toluenesulfochloride, methanesulfochloride, Ethanesulfochloride, phosphorus oxychloride or thionyl chloride, preferably acetic anhydride, is used. - ßtr- 11. The method according to claim 10, characterized in that the stan Cyclization with acetic anhydride in the presence of water at a pH between 10 and 13 is carried out, the reaction medium optionally also being a water-miscible organic solvent or, in the case of non-water-soluble end products, may contain a water-immiscible organic solvent. 12. Process for the preparation of 2-phenyl-2K-l, 2,3-triazoles of formula Z-I VS wherein R is C -C alkyl, unsubstituted -2 16 tes or substituted phenyl or benzyl and Z denote unsubstituted or substituted phenyl, characterized in that one compound of the formula HC = O ZN = N-CH
R ₂ -C = O with hydroxylamine or a salt thereof to form a dioxime of the formula HC = NOH
ZN = N-CH
R ₉ -C = NOH converts, the latter in the presence of a condensing agent to a triazole of the formula Z-It I ■ \ cyclized and hydrolyzed this to the corresponding ketone. ^N N0H 13th Oxime the formula Η · ( Z-N = N-C > NOH r ^H - = X wherein RC -C -alkyl, unsubstituted
I 1 6 tes or substituted phenyl or benzyl, Z unsubstituted or substituted phenyl and X signify 0 or NOH. 14. Oximes according to claim 13 of the formula ^R 3 ;. -N = N-Ch R ₅ where X is 0 or NOH, R 'C -C -alkyl, unsubstituted phenyl or benzyl or with 1 or 2 substituents from the group halogen, C -C -alkyl, C -C, -Alkoxy, C, -C, -alkenyl, nitro, cyano, carboxy or SuIfο and their derivatives, C -C -carbalkoxy or trifluoromethyl substituted Phenyl or benzyl and R-, R, and R- independently of one another water- • J ^ t O substance, halogen, trifluoromethyl, cyano, nitro, C -C ^ -alkyl, CC ₄ -haloalkyl, C -C, -hydroxyalkyl, C _? -C _fi -alkoxyalkyl, C -C -alkenyl, C -C, -alkoxy, C -C.-haloalkoxy, C "-C _ft -alkoxyalkoxy, unsubstituted or by halogen, C -C, -alkyl, C -C , -Alkoxy, C ₂ -C, .- carbalkoxy, C -C.-alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of the formula -COOY., Or -SO-Y., Mono- or polysubstituted phenyl or phenoxy ; or one of the group of the formula -C-MH-, -NY Y ", -SO-Y, -COOY, -S (O) - (C -C.-alkyl) or -S (O) - (C -C.-haloalkyl) -JJ j HJ.H Tl Jl Q mean, where Y and Y "independently of one another represent hydrogen or C -C "-alkyl, Y_ for hydrogen, C -C" alkyl or a salt-forming one Cation and η stand for the number 0, 1 or 2. 15. Oximes according to claim 14 of the formula where X is O or NOH, R '''C -C -alkyl, benzyl or unsubstituted or phenyl substituted with 1 or 2 substituents from the group chlorine, methoxy and / or methyl, R "hydrogen, halogen, trifluoromethyl, cyano, nitro, C.-C ^ - Alkyl, C.-C.-alkoxy, C -C.-alkylsulfonyl, phenyl or phenoxy which is unsubstituted or substituted by chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts; or a group of the formula - SO-Yl, -COOY 'or -NY Y ₂ , where Y , Y ₂ and Y' are as defined in claim 3 , and RV is hydrogen, halogen, C ~ C, -alkyl or C -C, -alkoxy, where R "is preferably hydrogen, halogen, C -C ^ -alkyl, CC ^ - alkoxy, cyano, nitro, sulfo or carboxy and their alkali metal or ammonium salts, C, -C.-alkylsulphonyl, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and the like Alkali metal or ammonium salts and R "is preferably hydrogen, halogen, methyl or methoxy. 16. Oximes according to any one of claims 13-15, wherein R, R 'or R " ^{1 is} methyl and X is 0 . 17. Use of 2-phenyl ~ 2H-l, 2,3-tria zolen of the formula defined in claim 1 wherein Z is unsubstituted or Substituted phenyl means, as Ausonngsprodukte for the production of 2-phenyl-2H-l, 2,3-tri; i7.ol-M-yl-ossip «'i" rt'n dor formula ¹ I. and their functional derivatives and thus for the production of optical brighteners of the 3- (2 ^T -phenyl-2 ^r H-l ', 2', 3'-triazol-4'-yl) -coumarin series. 18. Process for the preparation of 2-phenyl-2H-l, 2,3-triazol-4-ylacetic acids and their derivatives of the formula wherein Z is unsubstituted or substituted phenyl and R _{7 are} hydroxy, C -C, alkoxy or a group of the formula -OM or -NY, Y ₁ -, where Y, and Y. independently of one another are hydrogen or C -C -alkyl or Y, and Υ - Together with the nitrogen atom to which they are attached, for a 5- or 6-membered saturated heterocyclic ring, which optionally also contains an oxygen, sulfur and / or nitrogen atom as ring members and optionally by 1 or 2 C -C ^ Alkyl groups can be substituted, and M ^ stand for a salt-forming cation, characterized in that a 2-phenyl-2H _{-1,2 y} 3-triazole of the formula with morpholine, piperidine or dimethylamine and sulfur to one 2-? Enyl-2H-l, 2,3-triazol-4-ylthioacetamide of the formula where X- -N ^ 0, -N. · Or -N (CH ₃ ) - means, converts and · - · · - · the latter is hydrolyzed without isolation to the corresponding 2-phenyl-2H- _1,2} 3-triazol-4-yl-acetic acid and, if necessary, an acid obtained in this way is converted into a salt, an ester or an amide by conventional methods. 19. 2-Phenyl-2H-1,2,3-triazol-4-yl-ketoxime of the formula wherein R is C -C, alkyl, unsubstituted tes or substituted phenyl or benzyl and Z denotes unsubstituted or substituted phenyl.