CS212339B2 - Method of making the derivatives of the 1-vinyltriazole - Google Patents

Abstract

Triazoles of formula (I), their acid addition salts and metal salt complexes are new. In (I), R1 is cycloalkyl or opt. substd. alkyl or aryl. R2 is alkyl. R3 is alkyl, cycloalkyl or alkenyl, or opt. substd. cycloalkenyl or aryl, or R2 and R3 together complete opt. substd. cycloalkenyl or cycloalkyl. X is -C(R5)(OR4)- or also carbonyl if R1 is cycloalkyl or opt. substd. alkyl; R4 is H, opt. substd. aralkyl, acyl or opt. substd. carbamoyl. R5 is H, alkyl or opt. substd. aralkyl. (I) are prepd. e.g. by reacting. OCH.CHR2R3 with a triazolylmethyl ketone, then eliminating water. (I) are useful as plant-growth regulators and are more effective than e.g. 2-chloroethyltrimethylammonium chloride. Typical responses observed are: inhibition of vegetative growth in grasses and cereals; increased metabolite content of e.g. sugar beet or soya; stimulation of latex flow in rubber trees; induction of parthenocarpic fruiting; breaking apical dominance and inhibiting suckering defoliation; control of fruit drop and ripening; improving resistance to frost, drought etc. (I) are also fungicides, esp. effective against true mildews such as Erysiphe graminis and have a systemic action so can be applied to plants, soil or seeds.

Description

The present invention relates to a process for the preparation of novel 1-vinyltriazole derivatives which are fungicidally active and have the ability to control plant growth and can therefore be used as active ingredients of plant growth regulating agents and fungicidal agents.

It is already known that certain 2-haloethyltrialkylammonium halides have the ability to control plant growth (cf. U.S. Pat. No. 3,156,554). Thus, for example, 2-chloroethyltrimethylammonium chloride can be used to influence plant growth, in particular by inhibiting vegetative plant growth in important crop plants. On the other hand, the efficacy of this substance, in particular at low application rates, is not always sufficient.

It is further known that 2-chloroethylphosphonic acid has the ability to control growth (cf. DOS 1,667,968). However, the results obtained with this substance are also not always satisfactory.

Furthermore, acylated and carbamoylated derivatives in the phenyl moiety are known to be substituted

3,3-dimethyl-1-phenoxy-1-triazolylbutan-2-ol have good fungicidal activity (cf. DOS 26 00 799). Also suitable for combating fungi are certain, in the phenyl moiety; - substituted

4,4-dimethyl-1-phenyl-2-triazolylpentan-3-ones such as 1- (4-chlorophenyl) -4,4-dimethyl-

2- ^{(1, 2, 4-triazol-1-yl) p} entan- ^{3-one (cf. DOS 27 34 426).} However, the phenomena of these azole derivatives ^are not always sufficient, especially at lower application rates and concentrations. '

We have now found new 1-vinyltriazole derivatives of the general formula I, (I)

ОН. AND

R ¹ -CC = сн-сн

X _R 3

wherein they are C 1 -C 4 alkyl optionally substituted one or two times with halogen, C 1 -C 4 alkylcarbonyloxy or C 1 -C 4 alkylsulfonyloxy;

(C 5 -C 7) cycloalkyl and optionally halogen, C 1 -C 4 alkyl, phenyl, phenoxy, halophenyl and / or phenyl or naphthyl-substituted halophenoxy,

R is C 1 -C 4 alkyl,

R ^{3 is} C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl optionally substituted C 5 -C 7 cycloalkenyl, C 2 -C 4 alkenyl or optionally halogen and / or (C 1 -C 4) alkyl or substituted phenyl or naphthyl, and in addition

3

R @ 1 and R @ 2 together with the carbon atom to which they are attached are optionally C1 -C4 alkyl, substituted C3 -C12 cycloalkenyl or optionally C1 -C4 alkyl or C3 -C3 cycloalkyl. and hydrogen, a C 1 -C 4 alkyl group, or optionally a halogen or a C 1 -C 4 alkyl group substituted with a benzyl group, as well as their acid addition salts and copper (I) chloride complexes.

These novel compounds of formula I have the ability to control plant growth and have valuable fungicidal properties.

According to the invention, the novel 1-vinyltriazole derivatives of the formula I as well as their acid addition salts and their complexes with copper (I) chloride are prepared by the preparation of the compounds of the formula Ia,

(Ia) in which

3

R, R and R are as defined above, reduced in the presence of a solvent with complex hydrides or Grignard compounds of formula IV,

R ⁶ -Mg-Hal (1У) wherein r ⁶ is C 1 -C 4 alkyl or optionally halogen or C 1 -C 4 alkyl substituted benzyl,

Hal halogen, optionally followed by addition of the acid or cupric chloride to the compounds obtained.

Surprisingly, the 1-vinyltriazoles of the present invention, as well as their acid addition salts and their copper (II) chloride complexes, exhibit better plant growth control than the known 2-chloroethyltrimethylammonium chloride and the known 2-chloroethylphosphonic acid, which are well known with the same type of effect. In addition, the compounds of the invention surprisingly have a better fungicidal effect than the prior art acylated and carbamoylated derivatives in the phenyl portion of substituted 3,3-dimethyl-1-phenoxy-1-triazolylbutan-2-ol, and also the known 1- (4) (chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -pentan-3-one, which are the closest chemical and effect related compounds. The active compounds of the formula I thus represent an enrichment of the technique.

The 1-vinyltriazoles of the invention are generally defined by Formula I. In this Formula I, S is preferably an optionally mono- or double-substituted, straight or branched (C 1 -C 4) alkyl group, the substituents being as substituents. preference is given to: halogen, C1 -C4 alkylcarbonyloxy or C1 -C4 alkylsulfonyloxy.

more preferably, preferably a C 5 -C 7 cycloalkyl group and optionally one or two identical or different radicals which are substituted by one or two identical or different radicals are phenyl or naphthyl; a phenoxy group, a halophenyl group, and a halophenoxy group.

R represents a straight or branched alkyl group having 1 to 4 carbon atoms

R @ ³ is preferably straight or branched (C1 -C4) alkyl, (C6 -C7) cycloalkyl, (C1 -C4) alkyl optionally substituted (C6 -C7) cycloalkenyl, (C2 -C7) alkenyl; And optionally substituted phenyl and naphthyl, the substituents being preferably halogen and C1-C4alkyl.

R @ 1 and R @ 2 are, in addition to tbho, preferably together with the carbon atom to which they are attached, optionally C1 -C4 alkyl substituted C5 -C7 cycloalkenyl and C3 -C7 cycloalkyl.

R @ 1 is preferably hydrogen, C1 -C4 alkyl and optionally halogen or C1 -C4 alkyl substituted benzyl.

Very particularly preferred are those compounds of formula (I) wherein:

R ¹ is tert-butyl, isopropyl, chloro-tert, butyl, fluoro-tert-butyl, acetoxy-tert-butyl, methylsulfonyloxy-tert-butyl, 1,3-dichloro-2-methyl-prop -2-yl; 1,3-dibromo-2-methylprop-2-yl, 1,3-difluoro-2-methylprop-2-yl, 1-chloro-3-bromo-2-methylprop-2-yl; 1,3-diacetoxy-2-methylprop-2-yl; cyclohexyl, phenyl, chlorophenyl, bromophenyl, dichlorophenyl, fluorophenyl, methylphenyl, dimethylphenyl, chloromethylphenyl, biphenylyl, phenoxyphenyl, chlorophenylphenyl or chlorophenoxyphenyl;

R is methyl, ethyl, propyl or butyl,

R ³ represents methyl, ethyl, isopropyl, cyclohexyl, cyclohexenyl, methylcyclohexenyl, allyl, methacrylic, phenyl, chlorophenyl, dichlorophenyl or methylphenyl;

R @ ² and R @ 2 taken together with the alkyl atom to which they are attached represent cyclopropyl, cyclobutyl, cyclopentyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl or cyclohexylcyclohexenyl;

r 3 is hydrogen, ethyl, ethyl, isopropyl, benzyl, chlorobenzyl, or dichlorobenzyl.

In addition to the compounds mentioned in the examples, the following may be named the following:

(AND)

R ¹ R ² r3 ---------- Г5 ----- C (OH ₃ ) ₃ ^G 2 ^H 5 > · CH3 H C (CH3) ₃ ОНз ОНз H C (CH3) ₃ CH3 © H C (CH3) ₃ CH3 © H C (CH3) ₃ cyclopropyl H C (CH) 3 cyclobutyl H C (H, ₃ ) cyclopennyl H C ₃ ) ₃ cycloheptyl H H3 CH3 ОНз CH-. О «» з) ₃ cyclohexane ^СНз C (CC ₃ > 3) cyclohexene ОНз С (ОНз) з mmethylcyclohexene ОНз С (ОНз) з ОНз ОНз ^-СН ₂ ~ Ъ) С (ОНз) з cyclohexene -ОН2 — Ъ) С (ОНз) з cyclohexene С (ОНз) з ^^ eth ^ lcykl ^ c ^ h ^^ x ^ en ^—ОН2 ~ ^) CH ₃ 1 ^з С1СН ₂ -О- CH3 CH3 H ч from ₃ IJ С1СН ₂ -О- cyclohexane H ^ОНз © 3 С1СН ₂ -О- cyclohexene H ^6Нз

i ^and 3

ClCH ₉ -CC. AND

CH3

CH, i 3

BrCH, -C2, ^CH3 ? ^H 3 BrCH, -C 2 i ch ₃ ? ^H3 BRC-cyclohexen -CCH3

CH3 CH3 cyclohexane cyclohexene? ^H3 BrCH ₂ -C ² I

CH 3 methylcyclohexene

CH 3 CH 3? ³ FCH, -C 2 I

CH3 cyclohexane

CH,

3

FCH ₂ -CCH 3

^H 3 C-C2 FCHg 1

CH3

CH-Cl

I 2

CH, -C3 i

CH ₂ Cl cyclohexene methylcyclohexene

CH-J ^{CH 3}

C1 ^{H2 C1}

CH 3 -C -cyclohexane

CH2Cl

C « ^2C1

CH ₃ -C- cyclohexene

CH ₂ Cl ₂ ch ₂ Ci

CH ₃ -C- methylcyclohexene

CH2Cl

H H H

H

H

H

H

H

H

H

H

H

H continued table

R ¹

? ^H 3 CH 3 -SO ₂ -O-CH ₂ -C- ^OH 3 CH3 CH3 H ? ^H3 CH3-SO2-O-CH2-C- cyclohexane H CH ₃ ? ^H3 CH3-SO2-O-CH2-C- cyclohexene H CH3 ? ^H 3 CH ₃ -SO 2 -O-CH 2 -C- methylcyclohexene H CH ₃ 9H3 CH3-CO-O-CH2-C- CH3 CH3 H CH3 ? ^H 3 CH ₃ -CO-O-CH ₂ -C - cyclohexane H OH ³ C ^H 3 CH, -CO-O-CH _o -C- 3 2 1 cyclohexene H CH3 CH 3 1 3 CH ₃ -CO-O-CH ₂ -C-3 · 2 1 methylcyclohexene H CH3 0 CH3 ^CH3 H 0 cyclohexane H 0 cyclohexene H

0 methylcyclohexene H CH3 CH3 H © cyclohexane H

Ί continued table

Ř ¹

cyclohexene methylcyclohexene

_{CH3 CH3} cyclohexane, cyclohexene, methylcyclohexene CH ₃ CH ₃ methyl cyclohexene cyclohexene thylcyklohexen

H

H

H

H

H

H

H

H

H

H

Preferred compounds of the invention are also addition products composed of acids and those 1 deri1 two thereof together vinyltriazolu-one of formula I, wherein the radicals R, R and R ^j have the meanings which have already been mentioned as preferred for these radicals.

Acids which may be added are preferably hydrochloric and hydrobromic acid, in particular hydrochloric acid, furthermore nitric acid and 1,5-naphthalenedisulfonic acid.

Additionally preferred compounds of the invention are complexes of compounds of formula ¹ with stannous chloride ^currency.

When 1-cyclchexyl-4,4-dimethyl-2- (1,2,4-triezol-1-yl) pent-1-en-3-one is used as starting materials and the solvent is used. , the reaction sequence can be illustrated by the following reaction scheme:

0, ¹¹ (СНз) зС-С-С = СН

+ ^NaBH 4 _y

OH

If 1-cyclohexyl-4,4-methyl-2- (1,2,4-triazol-1-yl) -pent-1-en-3-one and methylmagnesium bromide is used as starting materials, the reaction may be carried out as follows. according to the invention is represented by the following reaction scheme:

O OH (CH ₃ ) ₃ CC-C = CH- ^) BrMci-CHg ^ (CH ₃ ) ₃ C -С -С £> ^Нз 'А

The compounds of the formula Ia which are required as starting materials for the process according to the invention are obtained by the use of the triazolketones of the formula II

C / ^{N =]}

R ¹ -C-CH _{2 -N'1} \ = N (II) wherein r 1 is as defined above, in reaction with aldehydes of formula III,

(III) in which:

R ² and R ³ have the abovementioned meanings, in solvents and in přítomnooti přítomnooti catalyst and forming isomers based on the cleavage of hydrogen is isolated by conventional methods, the desired isomeric product of the formula Ia,

O II

(Ia) wherein r 1, r 2 and r ³ are as defined above.

The compounds of formula II used herein as starting materials are largely known compounds (cf. DOS 24 32 407, DOS 26 20 022 and DOS 26 38 470). The compounds of formula II, which are still known in the art, are known. can be produced by conventional methods. These compounds are obtained by reacting haloketones in the reaction in the presence of an acid-binding agent with 1,2,4-trazode.

The aldehydes which are further used as starting materials are generally defined by the formula

III. In this formula, R @ ² and R @ ^{3 are} preferably those which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula I according to the invention.

The aldehydes of formula III are generally known compounds of organic chemistry.

Compounds of formula Ia in which r 1 is an optionally substituted alkyl or cycloalkylalkyl group are novel compounds, whereas compounds in which r 2 is an optionally substituted phenyl or naphthyl group are partially known (cf. DOS 26 45 617).

The complex hydrides necessary as reactants for the process of the invention are generally known organic chemistry compounds. Examples which may be mentioned are sodium borohydride and lithium alanate.

The Grignard compounds which are further used as starting materials for the process according to the invention are generally defined by formula IV. In this formula, R @ ^{6 is} preferably C1 -C4 alkyl as well as optionally halogen or C1 -C4 alkyl substituted benzyl. Hal is preferably chlorine, bromine or iodine.

The Grignerd compounds of formula IV are generally known organic chemistry compounds. Examples are methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium bromide and benzylmagnesium bromide.

Suitable solvents for the reduction with complex hydrides are preferably polar organic solvents for the process according to the invention. These preferably include alcohols such as methanol, ethanol, isopropanol or butanol; and ethers such as diethyl ether or tetrahydrofuran.

The reaction temperatures can be varied within a wide range when carrying out the reduction with the complex hydrides of the invention. In general, the reaction is carried out at temperatures between 0 and 30 ° C, preferably at 0 to 20 ° C.

The reduction with the complex hydrides according to the invention is preferably carried out using equimolar amounts of starting materials. In order to isolate the compounds of formula I, the reaction mixture is taken up in dilute hydrochloric acid and extracted with an organic solvent; Further processing is carried out in the usual manner.

Suitable solvents for the reduction with Grignard compounds according to the invention are preferably anhydrous ethers, such as diethyl ether, dibutyl ether and tetrahydrofuran.

The reaction temperatures can be varied within wide limits when carrying out the reduction with the Grignard compounds of the invention. In general, the reaction is carried out at temperatures between 0 and 80 ° C, preferably between 30 and 60 ° C.

The reduction by Grignard compounds according to the invention is preferably carried out using equimolar amounts of starting materials. The isolation of the compounds of formula I is carried out in a conventional and generally known manner.

The compounds of the formula I which have been produced by the process according to the invention can be converted into acid-addition salts or complexes with cupric chloride.

For the preparation of physiologically tolerable acid addition salts of the compounds of the formula I, all physiologically tolerable acids, which preferably include hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore nitric acid and 1,5-naphthalenedisulphonic acid, are suitable.

Acid addition salts of the compounds of formula (I) may be prepared in a simple manner by conventional salt-preparation methods, for example by dissolving the compound of formula (I) in a suitable inert solvent and adding an acid such as hydrochloric acid and isolated in a manner known per se. cleaned with an inert organic solvent.

Copper (II) chloride is suitable for the preparation of complexes of the compounds of formula (I).

ΊΟ

Complexes of compounds of formula I with copper (II) chloride can be prepared in a simple manner by a conventional method, for example by dissolving a metal salt in an alcohol such as ethanol, and adding the compound of formula I. , and optionally by recrystallization.

The active substances used in the invention interfere with the metabolism of plants and can therefore be used as growth regulators.

The process of the present invention is illustrated in more detail but not by way of example.

Example

26-g (0.1 mol) of 1-cyclohexyl-4,4-diethyl-1- (1,2,4-triazol-1-yl-pent-1-en-1-one) is dissolved in 200 ml of methanol and 4.5 g of sodium borohydride are added in portions with stirring and cooling, and after completion of the reaction, the reaction mixture is brought to pH 6 and concentrated, and the residue is taken up in 200 ml of methylene chloride, washed with saturated sodium bicarbonate solution and dried over sodium sulfate. The residue was recrystallized from petroleum ether to give 14.5 g (55% of theory) of 1-cyclhexyl-1,4-dimethyl-2- (1,2,4-triazol-1-yl) pent-1. -en-3-ol at 131 ° C.

Production of starting material:

63.5 g (10.5 moles) of p1-N, N-triazole, 60 g (0.5 moles) of cyclohexanaldehyde, 4.2 g (0.05 moles) of piperidine and 6 g (0.1 moles) glacial acetic acid was heated in 300 ml of toluene under reflux using a water trap. After cooling the reaction solution, it is washed with a saturated sodium chloride solution, the organic phase is dried over sodium sulphate and intensified. The residue is taken up in 500 ml of acetone and a film solution of 90 g (0.25 mol) of naphthalene-1'-disuccinic acid in 500 ml of acetone is added.

The precipitate initially formed is filtered off, the filtrate is destroyed for a longer time and the colorless crystalline residue obtained is taken up in 500 ml of meethrlene chloride. Sodium carbonate solution (1: 1) was then added to the alkaline reaction. Ordinary phases are separated, dried, swallowed and angered. The oily residue was taken up in petroleum ether and allowed to crystallize. 64 g (49% of theory) of 1-cyclohexyl-44-dimethyl-2 (112,4-triazol-1-yl) pent-1-en-3-one of melting point 98 DEG C. are obtained.

Production of the product:

138 g (2 mol) of 1,2,4-toluene are added portionwise at room temperature to 276.4 g (2 mol) of ground potassium carbonate and 269.2 g (2 mol) of alpha-cephrpioaccharin in 500 ml of acetone, whereby the internal temperature rises to the boiling point. The reaction mixture was allowed to stir at reflux for 1 hour and then cooled to room temperature. The reaction solution was filtered and the filtrate was concentrated by distilling off the solvent in vacuo.

The oily residue crystallizes upon the addition of gasoline. 240.8 g (72% of theory) of 3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-one of melting point 62 DEG-64 DEG C. are obtained.

The following compounds of the formula I are summarized in the table in an analogous manner:

-X-C = CH-CH 2

(AND)

Example B ¹ number

melting point (° C)

2 (ch ^ c -CH (OH) - O 151 (Z-Fonna) 3 ⁽ си ₃ ) ₃ с -CH (OH) - 0 ^CH oil 4 Cl c »-h (4- -CH (OH) - 0 oil 5 -CH (OH) - C ₂ H ₅ C ₂ H ₅ oil 6 Cl ^c, 0 ^ - -CH (OH) - O oil 7 (CH3) ₃ C -CCH ₃ (OH) - 0 101 8 (CH3) ₃ C -CH (OH) - 0 154 (HCl) (Z-f ortna)

Cl 9 ci- ^ Oý- -CH (OH) - 10 (c ₃ ) ₃ c -CH (OH) - 11 C ( ^Cl 0 / -CH (OH) - 12 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) -

c ₃ H ₇ CH ₃ oil 0 110 (.CuCl ₂ ) (Z-form) ^C 2 ^H 5 CH ₃ oil 0 oil

continued table

example number r1 X r2 0— melting point (° C) 13 O?· -CH (OH) - 0 156 14. ; _(CH3) jC -CH (OH) - 0 153 (.HNC3) (Z-form) 15 Dec Cl -CH (OH) - 0 oil 16 ^Cí - -CH (OH) - 0 oil 17 0 -CH (OH) - 0 oil 18 -CH (OH) - CH3 oil 19 Dec 4 -CH (OH) - ^C 2 ^H 5 CH3 oil 20 May -CH (OH) - ^C 4 ^H 9 ^C 2 ^H 5 oil 21 C1CH ₂ -C (CH 3) ₂ - -CH (OH) - O oil · 22nd -CH (OH) - ¢ 4) 9 c ₂ h ₅ oil 23 (CH-J-C -CH (OH) - 0 137 (.NO3) (E-forum) 24 ^Cl0404 -CH (OH) - CH ₃ CH3 187 25 C1CH ₂ -C (CH ₃ ) 2 - -CH (OH) - CH ₃ CH3 oil 26 (CH.P3C -CH (OH) - 0 242 (. | NOS) (E-forum) 27 Mar: (CHP3C - CH (OI) - 0 168 (CuCl ₂ ) (E-form)

continued table

example number R ¹ X R ² R ³ melting point (° C) 28 ^c '4 ^> -CH (OH) - 157 29 ^α 43Η ° 4 -CH (OH) - ^C 4 ^H 9 ^C 2 ^H 5 118 30 FCH ₂ -C (CH ₃ ) ₂ - -CH (OH) - oil 31 FCH ₂ -C (CH ₃ ) ₂ - -CH (OH) - O oil 32 ^or 4 ° H ° 4 -CH (OH) - 144 33 C! - <OHO> - -CH (OH) - CjHj «Λ 148 34 FCH ₂ -C (CH ₃ ) ₂ - -CH (OH) - O n2 ° 1.5049 (Z-Fortaa) 35 FCH ₂ -C (CH ₃ ) ₂ - -CH (OH) - Э 1.4910 (Z-form) 36 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - Э _n 2 ° 1.5050 (E-form) 37 38 (CH3) ₃ C (CH _{3) 3} C -CH (OH) -CH (OH) - CH ₃ CH ₃ CH, ^C 2 ^H 5 oil oil 39 (CH ₃ ) ₃ C- -CH (OH) - bléj 40 C1CH ₂ - C (CH ₃ ) ₂ - -CH (CH) - 43 oil 41 (CH ₃ ) ₃ C- -CH (OH) - 43 107 to 108 (Z-form) 42 (CH ₃ ) ₃ C- -CH (OH) - go oil 43 C 1 CH ₂ -C (CH ₃ ) ₂ -CH (OH) - oil

continued table

example number R ¹ X R ² R ³ melting point (° C) 44 FCH ₂ -C (CH ₃ ) ₂ - -CH (OH) - xf oil 45 Cl -CH (OH) - xr " oil 46 XX -CH (OH) - xr " amorphous substance 47 ^F XX -CH (OH) - amorphous substance 48 (CH ₃ ) ₃ C- -CH (OH) - X) oil' 49 (CH ₃ ) ₃ C- -CH (OH) - oil 50 -CH (OH) - amorphous substance (pure iaomer) ⁵¹ Cl c .- <o $ - -CH (OH) - amorphous substance 52 Cl -CH (OH) - XT ™ oil 53 Cl -CH (OH) - amorphous substance. (pure isomer) 54 (CH ₃ ) ₃ C- -CH (OH) - CH ₃ 47 55 (CH ₃ ) ₃ C- -CH (OH) - z® 43

continued table example R ¹ number

iP melting point (° C)

56 (CH ₃ ) ₃ C- -OH (OH) - 57 (CH ₃ ) ₃ C- -CH (OH) - 58 ttC ^ -CKCH ^ - -CH (OH) - 59 FCH ₂ -C (CH ₃ ) 2 - -CH (OH) - 60 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - 61 FCH ₂ -C (CH ₃ ) ₂ - -CH (OH) -

119 (Z-foraa) amorphous substance (Z-foraa)

amorphous substance amorphous substance amorphous substance (Z-foroa)

E- and Z-ω-ora = both possible geometric iso-forms of NDS = 1,5-naphthalenedisulonic acid

Claims (1)

SUBJECT OF THE INVENTION A process for the preparation of 1-vinyltriazole derivatives of the general formula I, OH, I-c-c = ch-ch (I) in which r ' is a C 1 -C 4 alkyl group optionally substituted once or twice by halogen, a (C 1 -C 4) alkylcarbonyloxy group or a (C 4 -C 4) alkylsulfonyl group, a C 5 -C 7 cycloalkyl group and optionally halogen, C1 -C4 alkyl, phenyl, phenoxy, phenoxy, halophenyl or / and halo-phenyl of phenyl or phenyl; R ° R ³ group, straightened by a C1-4 carbon atom; represents an acacia group having from 1 to 4 utalkyl atoms. (C 5 -C 7) cycloalkyl or C 1 -C 4 -alkyl; C 5 -C 7 cycloalksnyl, C 2 -C 4 alkenyl or optionally halogen and / or C 1 -C 4 alkyl substituted by phenyl or naphthyl, and in addition R @ 1 and R @ 2 together with the carbon atom to which they are attached are optionally C1 -C4 alkyl substituted C3 -C12 cycloalkenyl or optionally C1 -C4 alkyl or cyano substituted cycloalkyl. C 3 to C 12 atoms R ⁵ is ^{and the} hydrogen: ^{alk y} nominal SKU ^pi comprising ¹ to 4 carbon at ^hlík with no ^{b -p} o ^or A ^{de H} allogenic or alkyl having 1 to 4 carbon atoms substituted benzyl, like ^from their ED ^ n ^ h. so ¹ ! with tyse ^ and us ^to om ^pl EXU pyridinehydroximoyl chloride with měánatým in značuj ^{y i,} and in that the compounds of formula Ia, 2 1 0 ¹¹ / ^R R ¹ -CC = CH-CH ^ _ IR ³ (Ia) z-Nx N --- У in which 12 í R ^1, R and R have the abovementioned meaning, are reduced in the presence of a solvent with complex hydrides or Grignard compounds of the formula IV, R ⁶ -Mg-Hal (IV) wherein ^R6 is alk ^yl verifies SKU ^p yne with ^{from 1} to 4 and ^t om ^y uh-ku gene popřípa ^ga ^^ ^^ No ^b oe verifies group having 1 to 4 carbon atoms substituted a benzyl group, Hal represents halogen, and ^C e ^F is ^cyclized to obtained the pad ^of sIouč ^^ ¹ requires kyseMna Neto c ^hl ori ^d m ^ea stearate.