CS212338B2 - Means for regulation of the plant growth and fungicide means and method of making the active substance - 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

BACKGROUND OF THE INVENTION The present invention relates to plant growth regulating agents and fungicidal compositions containing novel 1-vinyltriazole derivatives as active ingredients. The invention further relates to a process for the preparation of these novel 1-vinyltriazole derivatives, as well as to their use as plant growth regulators and as 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, especially 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.

It is further known that acylated and carbamoylated derivatives in the phenyl moiety of 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 4,4-dimethyl-1-phenyl-2-triazolylpentan-3-ones substituted in the phenyl moiety, such as 1- (4-chlorophenyl) -4,4-dimethyl-2- (t 2,4-triazol-1-yl) pentan-3-one (cf. DOS 27 34 426). However, the effect of these azole derivatives is not always entirely sufficient, especially at lower application rates and concentrations.

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

212335 (X)

in which they mean

R ^{1 is} 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, optionally halogen, C 1 -C 4 alkyl, phenyl, phenoxy, halophenyl, and / or phenyl or naphthyl-substituted halophenoxy,

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

R 8 and R 8 together with the carbon atom to which they are attached are optionally C 1 -C 4 alkyl substituted by C 3 -C 12 cycloalkenyl or optionally C 1 -C 4 alkyl or C 3 -C 3 -cycloalkyl substituted 12 carbon atoms,

X is -C (OR 4) H 4 and in addition keto when it represents an optionally substituted alkyl or cycloalkyl group wherein it is hydrogen, a C 1 -C 4 alkyl group or optionally a halogen, a C 1 -C 4 alkyl group, a haloalkyl group up to 2 carbon atoms and up to 3 halogen atoms, phenyl and / or substituted benzyl fenolyskuplnou 'or naphthylmethyl, or is an acyl radical -CO-R ¹⁰ or the carbamoyl radical -СО-Ш ^' и ^'2, wherein the means

R ^{10 is} C 1 -C 4 alkyl, C 1 -C 5 haloalkyl, C 1 -C 5 halogen or optionally halogen and / or C 1 -C 4 alkyl substituted by phenyl or benzyl,

R ( ^{11) is} hydrogen or alkyl of 1 to 4 carbon atoms;

2

R is C 1 -C 6 alkyl, haloalkyl of up to 4 carbon atoms and up to 5 halogen atoms or optionally halogen, alkyl of 1 to 4 carbon atoms, haloalkyl of up to 2 carbon atoms and up to 5 halogen atoms; and a phenyl or naphthyl substituted haloalkylmercapto group having 1 to 2 carbon atoms and up to 5 halogen atoms, and

R @ 1 is hydrogen, C1 -C4 alkyl or, optionally, halogen or C1 -C4 alkyl substituted benzyl, and addition salts thereof with 1,5-naphthalenedisulfonic acid, hydrochloric acid, hydrobromic acid and nitric acid, as well as copper (II) chloride complexes which have the ability to control plant growth and have fungicidal properties.

The present invention provides plant growth regulating agents and fungicidal compositions comprising at least one 1-vinyltriazole derivative of the formula I or its addition salt with 1,5-naphthalenedisulfonic acid, hydrochloric acid, hydrobromic acid and nitric acid as an active ingredient. acid or a complex thereof with cupric chloride.

The compounds of formula I may exist in two geometric isomeric forms, depending on the arrangement of the groups which are bonded to the double bond. When X is -C (Or 4) 5, one asymmetric carbon atom is present, so that in this case the compounds of formula I are formed in two optical isomeric forms. The invention relates both to the individual isomers and to the mixture of isomers.

According to the invention derivatives of 1-vinyltriazolu formula I as well as their addition salts with 1,5-naftelendisulfonovou acid, hydrochloric acid, hydrobromic acid and nitric acid, and their complexes with cupric chloride obtained by triazolketony formula II and ^Η Ν = Π

R ¹ -C-CH ₂ - (n)

wherein R ¹ has the above meaning, state in reaction with aldehydes of formula III, O = CH-CH (III) in which R ² and R ³ are as defined above,

in the presence of a solvent and in the presence of a catalyst, and from the isomers formed by hydrogen cleavage, the desired isomeric product of formula (Ia) is isolated by conventional methods,

in which

2 3

R @ 1, R @ 2 and R @ 2 are as defined above, whereupon the compounds obtained are optionally admixed with hydrochloric, hydrobromic, nitric or 1,5-naphthalenedisulfonic acid or copper (II) chloride.

This process of the invention will hereinafter be referred to as process a).

2 3

Other compounds of formula (I) wherein R, R and R are as defined above and X is -C (OH) R 6, as defined above, are prepared according to the process disclosed in U.S. Pat. No. 212,339.

The compounds of formula (Ib) below are prepared by this process.

Further, the compounds of formula (I) may be prepared by:

(c) compounds of formula Ib;

OH

R ¹ -CC = CH-CH

(Ib) wherein

3 5 ·

R, R, R and R are as defined above, reacted with halides of formula V,

H ⁷ -Hal '(V) wherein n is n

R * alkyl, optionally substituted aralkyl, ethyl or optionally substituted carbamoyl; and

Hal * halogen, in the presence of a solvent and optionally in the presence of a strong base, optionally in the presence of an acid binding agent, or is present

(d) compounds of formula Ib;

OH í

-C-C = CH-CH

(Ib) wherein

3 5

R, R, R, and R are as defined above, react with acids of the general formula VI, r ⁸ -or ® (VI) in which:

Q

R is an acyl group, in the presence of a solvent and optionally in the presence of a catalyst, or is

(e) compounds of formula Ib;

OH • I

R-C = CH-CH

(Ib) wherein

R ^1, R ^2, R and R have the abovementioned meanings, are reacted with isocyanates of formula VII,

OC = NR ⁹ (VII) wherein

R @ 1 represents an alkyl group, a haloalkyl group or an optionally substituted aryl group, in the presence of a solvent and optionally in the presence of a catalyst, followed by the addition of hydrochloric, hydrobromic, nitric, 1,5-naphthalenedisulfonic acid or copper chloride.

Finally, it has been found that the novel 1-vinyltriazole derivatives of the formula I, as well as their addition salts with 1,5-naphthalenedisulfonic acid, hydrochloric acid, hydrobromic acid and nitric acid and copper chloride complexes, have considerable plant growth control and potent fungicidal properties. Properties.

Surprisingly, the 1-vinyltriazoles according to the invention, as well as their acid addition salts and their metal salt complexes, show a better plant growth control ability than the known 2-chloroethyltrimethylammonium chloride and the known 2-chloroethylphosphonic acid, which are known as well. with the same type of effect. In addition, the compounds of the invention surprisingly have a better fungicidal effect than the known acylated and carbamoylated derivatives in the phenyl portion of substituted 3,3-dimethyl-1-phenoxy-1-triazolylbutan-2-ol and 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 according to the invention thus represent an enrichment of the technique.

The 1-vinyltriazoles according to the invention are generally defined by the formula I. In this formula I is preferably an optionally mono- or di-substituted, straight or branched alkyl group having from 1 to 4 carbon atoms, preference being given to halogen, alkylcarbonyloxy, C 1 -C 4 alkyl or C 1 -C 4 alkylsulfonyloxy. R @ 5 is furthermore preferably cycloalkyl having 5 to 7 carbon atoms and optionally optionally one or two, the same or different radicals substituted by phenyl or naphthyl, the substituents preferably being: halogen, C1-C4-alkyl; carbon, phenyl, phenoxy, halophenyl and halophenoxy.

O

R represents a straight or branched (C 1 -C 4) alkyl group.

R @ 1 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.

3

R @ 1 and R @ 2 are additionally preferably together with the carbon atom to which they are attached, optionally C1-C4 alkyl, substituted cycloalkenyl of 5-7 carbon atoms and cycloalkyl of 3-7 carbon atoms.

/ 45 1

X is preferably -C (OR) R- and in addition keto, when R is optionally substituted alkyl or cycloalkyl.

R @ 1 is preferably hydrogen, straight or branched (C1 -C4) alkyl and, optionally one or more times, benzyl or naphthylmethyl substituted by the same or different radicals, preference being given to: halogen, C1 -C4 alkyl; 4 halogen atoms, a haloalkyl group having up to 2 carbon atoms and up to 3 identical or different halogen atoms, the halogen atoms being preferably fluorine and chlorine, a phenyl group and a phenyl group. R @ 1 is furthermore preferably an acyl radical -CO-R6 and a carbamoyl radical -co-nr-r ' ² .

R is preferably hydrogen, a (C1-C4) alkyl group as well as a benzyl-substituted, optionally halogen or (C1-C4) alkyl group.

R < ¹⁰ &^gt; is preferably a straight or branched alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, preferably fluorine and chlorine atoms, as well as 1 optionally substituted phenyl or benzyl group and halogen and alkyl having 1 to 4 carbon atoms are preferable.

^{R1 1} is hydrogen, ^and preferably ^to an NC OA ^{b l} k verifies skijnu ^yl having ¹ 4 carbon atom of .ež.

2

R is preferably an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having up to 4 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine atoms, optionally substituted one or more times by the same or different radicals substituted phenyl and naphthyl, the preferred substituents being: halogen, alkyl of 1 to 4 carbon atoms, as well as haloalkyl of up to 2 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine atoms, and preferably a haloalkylmercapto group having 1 to 2 carbon atoms and up to 5 halogen atoms, in particular fluorine and chlorine atoms.

Very particularly preferred are those compounds of formula 'I wherein R ¹ denotes a tert. ^b utylovou, ^and verifies Sopro ^pollen, or c ^{hl-tcrc.but pl} verifies, ^{fluoro-t. b} ut ^yl verifies, acetoxy-tert-butyl, tert.-methylsulfonyloxy-1,3-dichloro-2-meth ^{yl-prop-2-yl;}

1,3-di rom ^{b-2-methylprop-2-yl;} 1,3-difluoro-2-methylpro-22-yl, 1-chloro-3-bromo-2-methylprop-2-yl; 1,3-diecetoxy-2-meth ^yl-2-lprlp yllvlu; cyclohexyl; phenyl, chlorfenyll0lu, bromophenyl, ^ dichllrfcnрllvlo, fluorophenyl, mcthylfenyloolu, dimethylphenyl ^, ^b chllrmet ylfenyloolu, biphenyl, fenlx ^y fcnyloolu, chlorfenylfenylovou or chlořfcnlχyfenрllvou;

R is methyl ^ m, ethyl, ргоруОюи, or ЬиЬуОюи ^.

^rR skip inu me ^tрy lolou. ethyl,, isopropoxy ^yl verifies c lohex ^{yk y} lol ^about u. c ^{y l} klohexeр Ola, mcthylcрkllhcxcnyloootu substitute, mcthakryllooo, chlorfcnyllooou dichllrfcnрllvlo or mcthрlfenрlovlu;

R and RJ, taken together with the carbon atom to which they are attached, represent a cyclorolyl, cyclostyl, cyclostyl, cyclostyl, cyclohexenyl or methylcyclicenyl group;

Skujnu X is -C (OR ^{R) r--} j · ^reference and TAS Stoskolnu kd ^p ro ^p of ^{R 1} uveSná meaning an optionally substituted alkyl or ^cyclo- llalkрlovlo group;

^{rR hydrogen} skujnu meth Lovly ^{y e t} h ^y llvlu n- ^p ro Lovly ^oy, SL ^and RL ^{of pр 1l0lu, isobutylene р} 1l0iu optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of chlorine, fluorine, methyl, fenplem, fcnlxрskuoinlu substituted Ьсм ^ юю SKUs ^{of Ino.} AC-AC ZB ^p te ^to -CO-R ¹ or SrSm ® ^ verifies SKU ^p and ^nu -KOKR ^{'3' 2}

R ^R hydrogen SKU ^ ^ nu πιe'th LIVO _^s) CTH ^ verifies, ^on rl iso ^{oр llvou, benzoic,} chloro-benzo ^^ von or dichlorbcnzylooooL;

n ^ ^r10 skujnu Hýlov, OO ^ o ^ verifies ^even slbutyllolo ^ ^{c h} llrmcth ^р Lovly, dichlormcthyloolo or optionally mono- or polysubstituted fenyloolo or benzyl group with chloro, bromo, or methyl as substitucntp;

R ¹ 'is ^hydrogen, ethyl or metallated SKU ^p yne and

^R12 skujnu methyl, с Хюн ^ c ^hl lreth ^р LOOL, ^ opium, chllrfcn ^{рl lvou,} trifluormethрllOΌou chllrdiflolrmethрlovlu, dichllrflulrmetnyllolu.

The following compounds of the general formula (Ia) can be named individually in addition to the compounds mentioned in the examples:

(Ia)

Β ¹

R ³

C (CH 3> 3 C2H5 ^C A CW ^^ c ₂ H ₅ CH3 C (CH ₃ > 3 CH3 CH3 ^{C (CH} 3> ³ CH ³ 0 C (CH ₃ > 3 ^CH3 O

C (CH3) ₃

C (CH ₃ ) ₃ с ⁽ сн 3 ⁾ 3

C (CH3) ₃

C (CH3) 3 ϊ “ ³

C1CH ₂ Cч a “3 cich, -C2 and ^{CH3 CH3} C1CH - C ² Ц,

C ^H3

C1CH-Ct- ₃

C 3 ^H 3 BrCH, -C ² CH 3

C « ³

BrCH ₂ ^CH 3, -C

C ^H 3

BrCH ₂ -C “

CH3

C ^H 3

Br-CH2 ^-C-3

CH3

BrCH, ^{CH 3} -C cyclopropyl cyclobutyl cyclopentyl, cycloheptyl, norborn-3-en-2-yl cyclohexene cyclohexene methylcyclohexene

CH3 CH3 cyclohexane cyclohexene methylcyclohexene methylcyclohexene

CH3 CH3

212330 continued table

? ^H 3 FCH _O -C 2 i

CH ₃

CH-, 13fch ₉ -cCH ₃

CIL · j 3

FCH ₀ -C 2 i

_CH3 <i ^H 3 -CCH ₂ FCH ₃

CH ₂ C1

CH.-C3 I

CH ₂ C1

CH ₉ C1

I 2

CH ₃ -CCH ₂ Cl

CH ₉ C1

I 2

CH.-CJ I

CH ₂ C1? ^H 2 ^Cl ch ₃ -cCH ₂ Cl

CH ₃ CH 2 -so-o-so, -e 2 2 i

CH ₃ ? ^H 3 CH ₃ -SO ₂ -O-CH 3 -CH ₃ CH ₃ -SO ₂ -O-CH ₂ -CCH ₃ ? ^H3 CH3-SO2-O-CH2-CCH3? ^H 3 CH, -CO-O-CHo- ^C 3 ^H ₃

CH, CH ₃ -CO-O-CH ₂ -CCH ₃ ^NH 3

CH ₃ -CO-O-CH ₂ - ₍₃ JCH cyclohexane, cyclohexene, methylcyclohexene ^CH 3 ^CH 3 methyl cyclohexane, cyclohexene thylcyklohexen CH ₃ CH ₃ methyl cyclohexane, cyclohexene thylcyklohexen _сн з _CH3 cyclohexane cyclohexene, methylcyclohexene table continues? ^H 3

CH ₃ -CO-O-CH ₂ -CJ * I

CH ₃ O - O-O-O-O, -Ct

CH ₂ -O-CO-CH ₃

CH ₂ -O-CO-CH ₃ and ^CH 2 3 3 ^- CC ^ -O-CO-C ^

CH ₂ -O-CO-CH ₃ and 23 ^CH 3 ° C

C 6 -O-CO-CH-j

CH ₂ -O-CO-CH ₃ ^CH 3 -I-.

CH 2 -O-CO-CH 3

CH ₃ CH ₃ Cyclohexene Cyclohexene Methylcyclohexene

CH3 CH3 cyclohexane cyclohexane methfcyclohexene

CH3 CH3

OH

AND

(Ib)

r ’ r2 r3 ---- R5 ------------ c (ch ₃ > 3 ^C 2 ^H 5 CH ₃ H C (CH3) ₃ ch ₃ ^CH 3 H C (CH3) ₃ CH3 0 H <> ‘03 CH ₃ 0 H C (CH3) ₃ cyclopropyl H

to the table

r1 r2 r3 r5 ^C <C ³ > 3 cyclobutyl H C (CH3) ₃ cyclopentyl H C (CH3) ₃ cycloheptyl H C (CH3) ₃ ^CH 3 ^CH3 CH3 с (снз) з cyclohexene CH3 C (CH3>, cyclohexene CH3 C4CH3) ₃ Methyltycyclohexene CH3 C (CH 3) ₃ CH3 ch ₃ - ^CH 2 - (O) C (CH-3) ₃ cyclohexane -CH ₂ ~ o) C (CH 3) ₃ cyclohexene - ^CH 2 ^ O) C (CH 3) ₃ methylcyclohexene ^-CH 2 ? H ₃ C1CH, -C- CH3 CH3 H CH3 ? «3 cich ₂ -c- cyclohexene H CH3 ? H3 C1CH, -C- 2 t cyclohexene H ^CH 3 ^ 3 C1CH, -C- 2 1 me thylcyclohexen H ^CH 3  · CH3 BrCH ₂ -C- CH3 ch ₃ H 4 ? ^H 3 BrCH ₂ -C- cyclohexane H CH ₃ C ^K 3 BrCH ₂ -C- cyclohexene H ^CH 3 ? H3 BrCH ₂ -C- mmthflcyclohexen H

continued table

? ^H 3

FCH ₂ -CCH ₃

Cřk

I J

FCHp-φch ₃

CH-, i 3

FCH ₀ -C2 »

CH ₃ ? ^H 3

FCH ₀ -C ² OH ₃

CH ₂ C1

CH ₃ -CCH ₃ Cl

CH ₂ C1

CH ₃ -CCH ₂ Cl

CH ₂ ^C 1

CH.-C3 i

CH ₂ C1

CH ₂ C1

HER

CH ₂ C1? ^н з CH ₃ -SO ₂ -O-CH ₂ -CCH ₃ ? ^H 3 CH.-SOo-O-CHo-C3 2 2 I ^CH 3

CH ₃ -SO ₂ -O-CH ₂ -CCH _y? ^H 3

CH ₃ -SO ₂ -O-CH ₂ -CСИ ₃ ? ^H 3

CH ₃ -CO-O-CH ₂ -CCH ₃

CH 2 -CO-O-CH 2 -C 3 2

CH ₃ ? ^н з

CH ₃ -CO-O-CH ₂ -CCH ₃

CH ₃ CH ₃ cyclohexane cyclohexene methylcyclohexane

CH ₃ CH ₃ cyclohexane cyclohexene methylcyclohexene ch ₃ ch ₃ cyclohexane cyclohexene methylcyclohexene ch ₃ ch ₃ cyclohexane cyclohexene continued table

R ¹ R ² R ³ ---? --- F ^H CH 3-j-co-oacHg-C- _CH3 me thylcyclohexen H Θ ^CH 3 ch ₃ H ® cyclohexene H © cyclohexene H ® methylcyclohexene H © ch ₃ ch ₃ H © cyclohexene H © cyclohexene H © me thycyclohexene H ch ₃ ch ₃ H ^Cl ^ p) - cyclohexene H ^or 4 ° l · cyclohexene H ^Cl ©> methylcyclohexene * H ch ₃ ch ₃ H ^Cl ^ ' cyclohexene H “4®-” cyclohexene H < methylcyclohexene H

(Xcí)

R ¹ R ² R ³ R ⁴ - c (ck ₃ ) ₃ CH3 CH3 ^С Л . H c (ch ₃ > ₃ cyclohexane ^C2H 5 H C _{(CH3) 3} cyclohexene ^C í! ^H 5 H C _{(CH3) 3} me thylcyclohexen ^ 5 and ? ^H 3 ClCH ₀ -C- c 1 CH3 ^CH ₃ ^C2 «5 ch / ^CH3 CH3 C1CH2-C4 1 cyclohexane ^С Л ^CH 3 CH 3 f ^{H 3} C 1 CH, -C- cyclohexene ^С Л CH ₃ ^CH3 ? ' ³ cich ₂ -c- methylcyclohexene C2H5 CH ₃ CH 3 C ^{H 3} FCH, -C-2 1 CH3  CH3 ^С Л and CH3? ^{H 3} FCH, -C- d 1 cyclohexane ^C 2 ^H ₅ and CH 3 C ³ FCHo-C-2 1 cyclohexene ^С Л and CH3 CH, ₁₃ FCH2 -C- methylcyclohexene ^C 2 ^H ₅ ' and CH3 ^C 5 CH3 ^C A and Cl ^cl cyclohexane ^C ₂ ^H5 and Cl c / kluhfxen ^C 5 ^H 5 and

continued table

R ³ R ⁴ R ⁵ Cl me thylcyclohexen c ₂ H ₅ H C (CH 2) 2 ^CH 3 CH ₃ -ch ₂ - <δ> H C (CH3) ₃ cyclohexane -сн ₂ - ^ о) ~ -с » H C (CH3) ₃ cyclohexene - сн ₂ —Cl H C (CH3) ₃ methylcyclohexene - с ₂ - (Б) - ^C1 H ? C 3 CH ₂ -C 4 ^CH 3 CH ₃ - CH ₂ -Cl H < ^CH 3 CCH 2 -C -CH ₃ cyclohexane -ch ₂ —— ci H ? 3 CICHj-C-. CH ₃ cyclohexene -ch ₂ - (5> ο. H <«« 3 CICHg-C- СИ ₃ methylcyclohexene -ch ₂ - ^ O \ -ci H CH ₃ ч ^CH 3 CH ₃ —Сн ₂ or H FCH ₂ -C 4 cyclohexane -ch ₂ O 10 -ci H ? "З гсн -с- ₂ CH ₃ cyclohexene ^Ch ₂ H @ Hci H

212336 continued table

TLC 3 FCH ₀ -C 2 CH ₃ methylcyclohexene

Cl

Cl

Cl

Cl

Cl

cyclohexene

-ch ₂

cyclohexene

-CH ₂

Cl

Cl

CH ₃ cich ₉ -cl

CH ₃

CH ₃

C1CH ₂ -CH ₃

CH.

I ^J

C1CH _O -C2 I

CH ₃ ? ^H 3

_O -Cl C1CH I ^CH 3

CH.

i 3

FCH ₀ -C 2 CH ₃ f ^H 3

FCH - C2 and ch ₃

CH.

13 fch ₂ -cCH ₃

СН.

I ³ ₀ FCH C4

methylcyclohexene -ch ₂ - H ch ₃ ch ₃ -co-ch ₃ H cyclohexene -co-ch ₃ H cyclohexene -co-ch ₃ H me thylcyclohexen -co-ch ₃ H ch ₃ ch ₃ -co-ch ₃ H cyclohexene _-CO-CH3 H cyclohexene _-CO-CH3 H methylcyclohexene _-CO-CH3 H ch ₃ ch _{3 -CO-CH3} H

continued table

R ¹

cyclohexane -CO-CH3 H cyclohexene -CO-CH3 H

methylcyclohexene --CO CH ₃ ^CH 3 ₂ C1CH -CCHj? "з C1CH2-PCH3? ^H 3

C1CH - C ² H 3? ^H 3 ClCHQ-Cc. i ^CH3 ? ³ FCH2-CCH3? ^H3 FCH - C2 i ch ₃ ? ³ FCH - Cc - 1 CH,? ^H3 FCH - C2 1 ch ₃

Cl c ^ O $ Cl

CH ₃ CH 3 -CO-NHCH 3 cyclohexane -CO-NHCH 3 cyclohexene -CO-NHCH 3 methylcyclohexene -CO-NHCH 3

CH3 CH3 -CO-NHCH3 cyclohexane -CO-NHCH3 cyclohexene -CO-NHCH3 methylcyclohexene -CO-NHCH3

CH3 CH3 -CO-NHCH3 cyclohexane -CO-NHCH3 continued table

CH ₃ ? ^H 3

C1CH, C2 and CH ₃

CH ₃

C1CH _O -C2 i

CH ₃ ? ^H 3 ^C 1 CH ₂ -CCH ₃

CH.

i 3

CIH-c ² CH? ^H 3 fch ₂ -cCH ₃ ? ^H 3

FCH, -Cd 1

CH ₃ ? ^H 3

FCH - C2 and ^CH 3? ^H 3

FCH ₀ -C 2 i

CH ₃

Cl

Cl cyclohexane cyclohexene

^CH 3

-CO -NH

-CO-NH

-CO-NH

methylcyclohexene

-CO-NH

CH ₃

CH ₃

-CO-NH

cyclohexane cyclohexene methylcyclohexene

CH ₃ ^CH 3 cyclohexane

-CO-NH

-CO-NH

-CO-NH

-CO-NH

-CO-NH

continued table

R ¹ · R ² R ³ R ⁴ R ⁵ Cl cyclohexene -CO-NH- ^ CP) H Cl methylcyclohexene -CO-NH-ζθ) H CH, i C1CH-C-2 i ^CH 3 CH3 CH3 . - ^what ^ c) H ? ^H 3 Clch, -C- OH ₃ cyclohexane -CO-Q> H C ^H 3 C1CH - C- · 2 i. 0H ₃ cyclohexene -CO-O> H CH 13 C ¹ CH ² -C ² CH 3 methyloyclohexene -co-o) H C ^H 3 FCH - C - 2 and CH 3 ^CH3 CH3 - ^what - (o) H ^CH 3 FCH, -C-2 and CH 3 cyclohexane - ^c <> - @ H _CH3 FCH 2 and CH 3 -C- cyclohexene - ^what - (o) H CH 13 FCH, -C ² OH ₃ methylcyclohexene -co-φ H Cl ^{c |} - <$ 5 - CH3 CH3 -о- (о) H Clc ^, | -O > - cyclohexane -co- © H

continued table

R ¹

Cl cyclohexene

Cl

methylcyclohexene f ' ³

C1CII.-C2 ²

CH3

C “ ³

ClCH ₂ -C ² I

CHj? ^H 3

C ₁ ^CH ₂ -CCH 3 ^CH 3 CCH 3, -c 2 I ^{C 3} ? ^H 3

FCb-C2 I ™ ³

C ^H 3

FCH, -CCH

C ^H 3

FCH, -C2

CH3

C ' ³ FCH.-C. '4 cn ₃ ch ₃ cyclohexane cyclohexene methylcyclohexene

CH ₃ CH ₃ cyclohexane cyclohexene methylcyclohexene

-CO ~ OHH

- ^what Xo) _to H

-CO-CHCl ₂ H

-CO-CHCl ₂ H

-CO-CHCl ₂ H

-CO-CHCl ₂ H

-CO-CHCl ₂ H

-CO-CHCC ₂ H

-CO-CHCl ₂ H

-CO-CHCl ₂ H

Cl

Cl / C- (O +)

Cl

C ₃ CH 3 -CO-CHC1 ₂ Η cyclohexane -CO-CHC1 ₂ Η cyclohexene -CO-CHCl3 Η methylcyclohexene -CO-CHCC2 Η

continued table

R ¹ R ² R ^{3 r4} Г ⁵ C (CH3) ₃ ch ₃ ch ₃ -CO-CH3 H C (CH3) ₃ cyclohexane -CO-CIH3 H C (CH3) ₃ cyclohexene -CO-CH3 H С (СНз) ₃ methylcyclohexene -CO-CH J Her C (CH3) ₃ ch ₃ čh ₃ -CO-NHCH3 H С (СНз) ₃ cyclohexane -CO-NHCH3 H C (CH3) ₃ cyclohexene -CO-NHCH 3 H C (CH3) ₃ methylcyclohexene -CO-NIHCH 3 if

c (ch ₃ ) ₃ ^CH 3 ^CH 3

-CO · NH

C (CH3) ₃ Cyclohexane

CO-NH 0 c (CH ₃ ) ₃ cyclohexene

-CO--NH- (QC ^(CH 3 ⁾ 3 methylcyclohexene c (CH ₃ ) ₃ )

CH ₃

C (CH ₃ ) is cyclohexane c (CH ₃ > ₃ cyclohexene co

C (CH 3) ₃ methylcyclohexene -what H SMELL.) J 3 CH3 CH3 -CO-CHC1 ₂ H C (CH ₃ > ₃ cyclohexane -CO-CHC1 ₂ H C (CH3) ₃ cyclohexene -CO-CHC1 ₂ H C (CH3) ₃ methylcyclohexene -CO-CHC1 ₂ H

Preferred compounds of the invention are also acid addition products of those de 12,3 rivates of 1-vinyltriazole of formula I, wherein the residues R, R, R 'and X have the meanings already mentioned as being preferred for these residues.

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

In addition, preferred compounds of the invention are complexes of compounds of formula (I) with copper (I) chloride.

If, for example, pinacolyl-1,2,4-triazole and cyclohexanecarbaldehyde are used as starting materials, the following reaction scheme may be used to illustrate the reaction:

-H ₂ O

O

ICH ₃ ) ₃ C -CC = CH-

When 1-cyclohexyl-4,4- (limethyl-1- (1,2,4-triazol-1-yl) -pent-1-en-3-ol and ethyl bromide and sodium hydride are used as starting materials) , the reaction sequence according to process c) can be illustrated by the following reaction scheme:

t-

1) + NaH

2) + C ₂ H _with Br

OC ₂ H ₅ (с ₃ ) ₃ с-с-с = CH

If 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) pent-1-en-3-ol and acetyl chloride and sodium hydride are used as the starting materials, then the reaction sequence according to process c) can be illustrated by the following reaction scheme:

1) -HMaH

2) + CH ₃ -COCl

О-СОСЬЦ

I ^J

CHCl 3 -C = CH

I ^H A

N --- ^U

If 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) pent-1-en-3-ol and acetic anhydride are used as starting materials, the reaction can be carried out according to process d) as shown in the following reaction scheme:

+ (CH ₃ -CO) ₂ O

-CH ₃ COOH ~

O-COCH,

I ³ (chJ ₃ ccc = ch λ I

N --- Й

If 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) -pent-1-en-3-ol and phenyl isocyanate are used as starting materials, the reaction can be carried out according to (e) depicted by the following reaction scheme:

+ 0 = C = N

CO-NH—

O (s ₃ ) ₃ s - C = CH 1 N

N --- ϋ

The triazolketones required as starting materials in carrying out the process of the invention (process a) are generally defined by formula II. In this formula, R @ 1 is preferably those already mentioned in the description of the compounds according to the invention of the formula I as being preferred for these substituents.

The triazolketones of formula II are largely known compounds (erov. DOS 24 31 407, DOS 26 10 022 and DOS 26 38 470). The compounds of formula II, which are not yet known, can be prepared by conventional methods. These compounds are obtained by the reaction of the corresponding haloketones in the presence of an acid binding agent with 1,2,4-trizzole. By way of example, the following compounds of formula II may be mentioned. summarized in the table:

(II)

R ¹ R ¹ -C (CH ₃ > ₃₎ -chcch ₃ ) ₂ -CH ^ CH ₃ and ³ -C-CH, Cl 3 1 2 ^CH 3 V « ³ by HU Dm ch ₃ -e-CH_F ^6h ₃ ² -C-CHoOr 1 2 ch ₃ C 1 -C -CH-, CH ₃ -CH-SO ₀ -O-CH-Č- i 3 CH ₂ Cl 3 2 2 with ^CH 3 1 H ₂ O-CO-CH ₃ CH ₃ -C -h ₂ O-CO-CH ₃ 0 Cl Ч & - » Cl es - ^ci <δ) —CH ₃ “0” ' 0-0 - (θ) -ο-θθ -α · 0

The aldehydes which are further used as starting materials for the process according to the invention (process a)) are generally defined by 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.

Examples of such compounds include the following compounds

O = CH-CH

-ch ₃

O = CH-CH 2 Cl ₂ H ₅

O = CH-CH

CH ₃

С _Л

1-Vinyltriazole derivatives which are used as starting materials for processes c), d)

35 and e) are generally defined by the formula Ib. In this formula, R, R, R and R are preferably those already mentioned in the description of the compounds of formula I according to the invention as being preferred for these substituents.

The halides which are additionally used as starting materials in process (c) are generally defined by the formula V. In this formula, H is preferably a straight or branched alkyl group having 1 to 4 carbon atoms, and optionally one or more times, the same or substituted radicals having from 1 to 2 carbon atoms in the alkyl moiety and 6 to 10 carbon atoms in the aryl moiety such as benzyl or naphthylmethyl, the substituents being preferably halogen, C1 -C4 alkyl; carbon atoms, a haloalkyl group of up to 2 carbon atoms, and up to 3 identical or different halogen atoms, with halogen atoms preferably being fluorine and chlorine, as well as optionally halogen-substituted phenyl or

10 phenoxy. R is further preferably an acyl group -CO-R 6 carbamoyl -CO-NR 4 R ² , where R 1, R 2 and R ² are preferably those already mentioned for these symbols in the context of the description of the compounds of the invention listed as preferred. Hal * in formula V is preferably fluorine, chlorine or bromine.

Halides of the formula V are generally known compounds of organic chemistry.

The acid anhydrides further used as starting materials for process d) are generally defined by formula VI. In this formula, R 1 is preferably an acyl group of formula -CO-R ¹ , in which R 1 preferably has the meanings already indicated for this symbol as preferred in connection with the description of the compounds of the invention.

The acid anhydrides of the formula VI are generally known compounds of organic chemistry.

The isocyanates which are further used as starting materials for process e) are generally

Q defined by formula VII. In this formula, R is preferably an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having up to 4 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine atoms, optionally one or more times, the same or different substituents substituted (C až-C) aryl group such as phenyl and naphthyl, the substituents being preferably: halogen, (C až-C alkyl) alkyl group, as well as haloalkyl of up to 2 carbon atoms and up to 5 identical or different halogen atoms, such as in particular fluorine or chlorine atoms, and preferably haloalkylmercapto having 1 to 2 carbon atoms and up to 5 halogen atoms, such as in particular fluorine atoms and chlorine atoms.

Xocyanates of formula VII are generally known organic chemistry compounds.

Suitable solvents for the process according to the invention are preferably inert organic solvents. These preferably include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; aliphatic and cycloaliphatic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and cumene; halogenated aliphatic and aromatic hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, chlorobenzene and dichlorobenzene.

The process according to the invention is carried out in the presence of a catalyst. All commonly used acidic and especially basic catalysts, as well as mixtures thereof with buffers, can be used. These preferably include Lewis acids such as boron trifluoride, boron trichloride, tin tetrachloride or titanium tetrachloride; organic bases such as pyridine and piperidine; and in particular pyridine acetate.

The reaction temperatures may be varied within a wide range in carrying out the process of the invention. In general, the reaction is carried out at temperatures between 20 and 160 ° C, preferably at the boiling point of the respective solvent.

In the process according to the invention, 1 to 1.5 mol of the aldehyde (III) and a catalytic to 0.2 mole amount of catalyst are used per mole of triazolketone of formula II. In order to isolate the compounds of formula I, both the isomeric double bond positions of the reaction products are separated by conventional methods such as salt formation (cf. examples) or chromatography. The unambiguous structure is determined by spectroscopic data, in particular according to NMR spectral data.

Suitable solvents for process c) according to the invention are preferably inert organic solvents. These preferably include ethers such as diethyl ether and dioxane; aromatic hydrocarbons such as toluene and benzene; chlorinated hydrocarbons such as chloroform, methylene chloride or carbon tetrachloride may also be used in individual cases; as well as ketones such as acetone or methyl ethyl ketone; and nitriles such as acetonitrile. For the sake of simplicity, the acid halide used may optionally also be used as a solvent, with an appropriate excess of the acid halide required.

The reaction temperatures can be varied within a wide range in carrying out process c) according to the invention. In general, the reaction is carried out at temperatures between 20 and 150 ° C, preferably between 20 and 100 ° C, optionally at the boiling point of the solvent in question.

Process (c) according to the invention can also be carried out optionally in the presence of a strong base. These preferably include alkali metal hydrides, alkali metal amides and alkali metal alkoxides such as sodium hydride, sodium amide and potassium tert-butoxide.

Process (c) of the invention may optionally be carried out in the presence of acid binding agents (hydrogen halide acceptors). These include organic bases, preferably tertiary amines such as triethylamine; inorganic bases such as alkali metal hydroxides and alkali metal carbonates.

In carrying out process c) according to the invention, it is preferably used per 1 mol of the compounds of the formula

Ib 1 to 3 moles of the halide of formula V. In order to isolate the reaction products and to remove the solvent from the reaction mixture, water and an organic solvent are added to the residue. The organic phase is separated and worked up in the usual manner. .

In a preferred embodiment, the compound of formula Ib is conveniently used as the starting material, which is converted into an alkoxide by treatment with an alkali metal hydride or an alkali metal amide in a suitable inert organic solvent and reacted immediately with the halide of the formula without isolation. . V, wherein the compounds of the formula I according to the invention are obtained in a single step by cleavage of the alkali metal halide.

According to a further preferred embodiment of the process, the above-mentioned variant is carried out in a reaction of halides of the formula V in which R @ 1 represents an alkyl group or an optionally substituted aralkyl group in a two-phase system such as sodium hydroxide or potassium hydroxide and toluene or methylene chloride. the addition of 0.01 to 1 mol of a phase transfer catalyst such as ammonium or phosphonium compounds such as benzyldodecyldimethylammonium chloride (Zephirol) and triethylbenzylammonium chloride.

Suitable solvents for process d) according to the invention are preferably inert organic solvents. These preferably include the solvents mentioned in process c) as well as the acid anhydrides of the formula VI currently in use.

The catalysts used in process d) may preferably be all customary acidic and basic catalysts such as sulfuric acid, hydrogen chloride, hydrogen bromide, boron trifluoride, zinc chloride, sodium acetate, sodium benzoate, sodium carbonate, calcium oxide, magnesium oxide, pyridine and the like. triethylamine. ,

The reaction temperatures can be varied within a wide range in carrying out process d) according to the invention. Is ^G eneral ^P RAC ^at temperatures between ^{Ch. 20} and ¹⁵⁰ ° ^{above-h of} the ODN ^- 5 between ⁰ and ¹²⁰ ° C.

In carrying out procedure. The process is preferably carried out using equivalent amounts of starting materials. For the sake of simplicity, the acid anhydride of the formula VI used may also be used as a solvent, with an appropriate excess being required. The isolation of the compounds of the formula I is carried out in a conventional manner.

Suitable solvents for process e) according to the invention are preferably inert organic solvents. These preferably include the solvents mentioned in process c).

Preferred catalysts used in process (e) according to the invention are tertiary bases such as triethylamine and pyridine derivatives and organic tin compounds such as dibutyltin dilaurate and tributylin laurate.

The reaction temperature when carrying out the process e) according to the invention may vary within - wide rozmezL · ^G eneral ^of operating at te ^{pl rt i} c ^h limit 0 and ¹⁰⁰ ° C, preferably ^of between ²⁰ and 40 ° C.

The process e) is preferably carried out using equivalent amounts of starting materials. In order to isolate the compounds of formula I, the solvent is distilled off and the residue is removed. is processed by conventional methods. .

The compounds of the formula I which have been produced by the process according to the invention as well as processes c) to e) can be converted into acid addition salts or metal salt complexes.

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

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

For the preparation of complexes of the compounds of the formula I, manganese chloride is suitable.

Complexes of compounds of formula I with a chloride měňnatým may be prepared in a simple manner because ^of BE Nym pos ^t u ^are converted ^{to comm} ice dissolving ^STE n ^e m chlorine ^id um ^en to ^TEH s alkohobi such as ethanol, and ^p r ⁱ given with ^l oučenin ^{eh Y} general formula I Comp on xy-chloro-m em ^en sulfate may be isolated in a known manner, for example by filtration, and optionally purified by recrystallization.

^Teaches nn ^{é alkyl} methacrylate ^p ou ^Gd van ^E according to ^{the Y l d} to engage cut mešboHsmu ROS ^ ^l and in that it is therefore used as growth regulators.

Mode of action of plant growth regulators according to past experience that the active L ^and T e ^for am ^already on plants ^yp USO ^bit is ^d m or n ^e t, and ^KE n ^ oH ^ nk ^{y EFFECTIVE} different. ^Teaches n ^ky substance depends essentially on the time of application, based on the development stage of the seed or plant, and the quantity of active compound when applied to the plants or their environment and the way and ^{if p} ace. In dem k ^{F s} maj ^or Ada ^reg u ^la tor ^y pos growth Rosten Sne ^ s ^{if t} In the newly current ^{I l} to the plants in the desired manner.

Plant growth regulators can be used, for example, to suppress vegetative plant growth. Such inhibition of growth is of economic importance, inter alia, in grassland, since by suppressing grass growth, for example, the frequency of mowing in ornamental gardens, parks and sports facilities, at the edges of roads, at airports and orchards can be reduced. The importance of low growth suppression of herbaceous and woody plants at roadside and near overhead lines or, in general, where strong growth is undesirable.

Important is the use of growth regulators to inhibit the growth in length of cereals, because the snow no ^b of chain ^L and removes not ^{sAFeTy, and P} ol ^{EHA nus} ros ^t l ⁱ np ^Before slcl ^also marks ^d in reception being ^l ed ^k u shortening the stalks. In addition, plant growth regulators can cause grain stalks to increase, which also counteracts lodging. Using growth regulators for shortening the stalks and intensification of bel ST ^E allows the AP ^if U is ^Zn KAC ^{also Yss} amount ic ^h ^ tonojš width ^{W to} increase measurement proceeds ^without fear tfeba cereal lodging.

Suppression of vegetative growth allows for many crops to be denser or planted, so that yields per unit area can be increased. The smaller plants thus grown also have the advantage that the culture is easier to cultivate and harvest.

Suppression of the vegetative growth of plants can also lead to increased yields as nutrients and assimilates are used more intensively for the formation of flowers and fruits than for the growth of vegetative parts of plants.

Growth regulators can often achieve such stimulation of vegetative growth. This is of great importance when vegetative parts of plants are harvested. However, stimulation of vegetative growth can also simultaneously lead to stimulation of generative growth by producing more assimilates, so that for example more fruits can be formed or larger fruits can be produced.

21233®

In many cases, an increase in yields can also be achieved by interfering with the metabolism of the plants without observing changes in vegetative growth. Growth regulators can also act on changes in the composition of plants, which in turn can achieve a better quality of harvested products. Thus, for example, it is possible to increase the sugar content of sugar beet, cane, pineapple as well as citrus fruit, or to increase the protein content of soy or grain. Furthermore, it is also possible, for example, to inhibit the degradation of desired substances contained in plants, such as sugar in cane or sugar beet, by means of growth regulators before or after harvesting. In addition, the production or efflux of secondary plant substances can be positively influenced. An example is the stimulation of latex effluent in rubber trees.

Parthenocarpic fruits (fruits without seeds) may also develop under the influence of growth regulators. Furthermore, it is possible to influence the sex of the flowers with these regulators. Pollen sterility can also be achieved, which is of great importance in breeding and hybrid seed production.

By using growth regulators, it is possible to control the formation of side shoots in plants. On the one hand, the development of side shoots can be promoted by violating the application of domination, which may be very desirable, especially in the cultivation of ornamental plants, even in conjunction with the suppression of growth. On the other hand, it is also possible to inhibit the growth of the side shoots. This effect is of particular interest, for example, in tobacco growing or tomato planting.

The effect of the active substances on the foliage of the plants can be controlled so that the plants can be completely de-leafed at the desired time. Such defoliation is important for facilitating the mechanical harvesting of cotton, but it also plays a major role in other crops, such as the vine, where it facilitates harvesting. Plant defoliation can also be performed to reduce plant transpiration before transplanting.

Growth regulators can also be used to control the fall of fruit. On the one hand, premature fruit loss can be prevented. On the other hand, however, it is also possible to encourage the fall of fruits or even flowers in the sense of a 'chemical thinning' to break the so-called alternative. The alternative is the special behavior of some fruits, consisting of endogenous, very different yields from year to year. Growth regulators can also be used to reduce the force required at harvest time to tear off fruits in crop plants, so that mechanical harvesting or manual harvesting is facilitated.

By means of growth regulators, it is furthermore possible to accelerate or slow down the ripening of the harvested products before or after harvesting. This is particularly advantageous since it can be optimally adapted to market requirements. Furthermore, growth regulators can in many cases serve to improve the coloring of the fruit. In addition, growth regulators can achieve a concentration of fruit ripening within a certain period of time. This creates the prerequisites for, for example, tobacco, tomatoes or coffee plants to be able to carry out fully mechanical or manual harvesting in only one working stage.

The use of growth regulators can also affect seed or bud rest periods, i.e. endogenous annual rhythm, so that plants, such as pineapple or ornamental plants in horticulture, germinate, sprout or bloom when they would not normally rest, sprout or . nekvetly.

Can growth delayers or delayed seed germination be achieved by growth regulators, for example to prevent late frost damage in areas _? with a cooler climate.

Finally, frost, drought or high salt content in the soil can be induced by the growth regulators in the plants, allowing the plants to be grown in areas that would normally be unsuitable for the plants.

The compounds according to the invention are particularly suitable for inhibiting the growth of rice.

The active compounds according to the invention show a strong microbicidal action and can be used in practice to combat undesirable microorganisms. The active compounds described are suitable for use as plant protection agents.

Fungicidal compositions are used in plant protection to combat fungi of the classes Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Since the plants of the active compound according to the invention in concentrations necessary to combat fungal diseases. They can be used for the treatment of aerial parts of plants, seedlings and seeds, as well as for the treatment of soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good results for combating fungi causing diseases of true powdery mildew, such as for combating Erysiphe species, e.g.

It is particularly advantageous that the agents of the invention show not only a protective action but are úHnné and systeodcky what ^made amortized ctodinH rostHny ^p rot ^and Napa ^d en ^Sponge the active compound to the aboveground parts of the plant via the soil and the root or via the seed.

The active compounds can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, natural and synthetic substances impregnated with the active compounds, small particles coated with polymeric substances and coatings for seeds, ^further on to the formulation. ^y from ^AP and! Nym ^IP Risa ^d am ^i, such as fumigating ^{e p} Atron ^{y, k} ou ^r b ^{s d Ozy,} fumigating coils and the like., as well as compositions in the form of concentrates of active substance diffusing fog or cold heat.

These compositions are prepared in known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, with liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. As liquid rozpouHMla ^BC them, ^and I.I. ^s in following ^d State ^E in 'uva ^h in the main: ^aromatics, such as of xylene-toluene or a ^ y ^ AFTA-enes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as © chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexene or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethylsulfoxide; .

By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons as well as butane, propene, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stems.

^J as emulsifiers ^camphor formers ^b not on and ^{/ or} foaming ^IDL n and ^p in pMctázejí ACCOUNT nonionic, Ennio ^g and an ^even onick ^é emulsifiers, such as polyoxyethylene fatty acids, polyoxyethylene fatty alcohol ethers,

For example, alkylaryl polyglycol ether, alkylsulfanates, alkylsulfates, arylsulfonates and protein hydrolysates and as dispersants, for example, lignin, sulfite waste liquors and methylcellulose.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain colorants such as inorganic pigments, for example iron oxide, titanium dioxide, and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper salts. , cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active ingredient.

The active compounds according to the invention may be present in the formulations in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, avian protective agents, growth agents, plant nutrients and soil improvers.

The active compounds according to the invention can be applied as such, in the form of concentrates or further dilution forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is carried out in a conventional manner, for example by watering, dipping, spraying, fogging, evaporating, injecting, anointing, dusting, tossing, dry, wet, wet or suspension pickling or incrustation. Further, it is possible to administer the active compounds by the so-called ULV method or to inject the active compound or even the active compound itself into the soil. Further, plant seed can be treated.

When the compounds of the invention are used as plant growth regulators, the application rates can vary within wide limits. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of active compound are used per 1 ha of soil surface.

When using the substances according to the invention as plant growth regulators, the application is carried out within a preferred time interval, the exact definition of which is classified by climatic and vegetative conditions.

Also, when the compounds of the invention are used as fungicides, the application rate can vary over a wide range depending on the mode of application. The active compound concentrations in the treatment of plant parts in the application forms are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the treatment of seed, generally 0.01 to 10 g of active ingredient per kg, preferably 0.01 to 10 g of active ingredient per kg of seed, is required. In soil treatment, active compound concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, are required at the site of action.

The good performance of the compounds according to the invention results from the following examples.

In these examples, ge uses the following compounds as comparators:

A = С1? СН ₂ -СН ₂ -? - ОН 2-chloroethylphosphonic acid

OH

В Cl-CH ₂ -CH ₂ ^ t- (CH3) ₃ Cp

2-chloroethyltrimethylammonium chloride

O-CO-NHCHo

I ³

O-CH-CH-C (CH ₃ ) ₃ and ₃

N --- U ^{l =} с «- <5> -сн _сн_со _{2-с (снз) 3}

A í | N

N — ϋ

The biological performance of the compositions is illustrated by the following examples, but is not limited thereto.

Example

Test for ethylene production solvent: 30 emulsifier: 1 part by weight of dimethylformamide part by weight of polyoxyethylene sorbitan monolaurate ⁴

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Soybean leaves are cut into pieces of the same size. These leaf pieces are placed together with 1 ml of the active preparation or control solution in airtight containers. After 24 hours, ethylene that has accumulated in the containers is determined by conventional methods of detection. The production of ethylene by the pieces of leaves that were treated with the active agent is compared to the production of ethylene of the control.

It means:

ethylene production as control, + slightly increased ethylene production, ++ strongly increased ethylene production, * ++ very strongly increased ethylene production.

Active substance No. 3 according to the invention shows a strongly increased ethylene production in this test compared to the control, as shown in Table A.

TableA

Test for ethylene production

active substance concentration of active substance in% effect 0 (control) (3) 0.001 ++

Example В

Growth inhibition in barley solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Barley plants are grown in the greenhouse up to 2 leaf stage. At this stage, the plants are sprayed with the active ingredients until wetted. After 3 weeks, the increment was measured for all plants and the growth inhibition in the increment of the control plants was calculated. 100% inhibition of growth means no growth and 0% means growth corresponding to the growth of control plants.

The effect of the compound of the invention Nos. 2, 3 and 12 shows better growth retardation in this test than the prior art compound A as shown in Table B.

Table B

Growth inhibition of active substance concentration of active substance in% growth inhibition in%

- - 0 (control) AND 0.05 30 (known) (2) 0.05 60 (3) 0.05 . 40 (12) 0.05 35

Example 'C

Growth Effect on Sugar Solvent: 30 parts by weight of dimethylformamido

cmulgator: 1 part by weight of olefin (methyl) sorbitanminolaurate

In order to prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Beet plants are grown in the greenhouse until complete formation of the uterine leaves. At this stage, the plants are sprayed with the active agents until wetted. After 14 days sc sc measure the plant growth and calculate sc growth influence in% of the control plant growth. In this case, the 056 growth influence means growth that corresponds to that of the control plants. Negative values indicate growth retardation, positive values indicate growth stimulation compared to control plants.

Effective ^acrylate ky ^p o ^dl ev ^ & cut no. 2, 3, 4, 1 ^2, I ^{4, 16} face-off ^p s this assay le ^p width influencing the growth NMS substance B is known zc prior art as shown in the following table C. TabullkC

Influence of growth in sugar beet active substance concentration of active substance in% influence of growth in%

(control) (B) 0.05 -5 (known) (2) 0.05 -j5 ^: (3) 0.05 -55 ^:

continuation of Table C

active substance concentration of the active substance in% influence growth in * % (16) 0.05 + 20 (4) 0.05 ₂ ^ xx) (14) 0,05 _t _ ₂₅ χχ) (x) (12) 0.05 ’ -50 0.05 -80 (80) 0.05 -30 (81) 0.05 ^-3 5 ^xx) (67) 0.05 -20 Italy (69) 0.05 ^- 2 ^{° C)} (x) (75) 0.05 -25XX) (76) 0.05 . ^-20XX) (89) 0.05 ^-8 0 ^χχ) (x) (90) 0.05 ^-4 0 ^χχ) (x) (91) 0.05 ^-4 0 ^Xx) (x) (93) 0.05 ° ^x) (96) 0.05 ^-100XX) X) (99) 0.05 ^-ggXK) (x) (102) 0.05 - ^jgXX) (x) (107) 0.05 -ygXX) (x) (114) 0.05 -35 ^x) (115) 0.05 ^- 45 ^x)

= dark green leaves ^xx) » ^t lua ^th leaves

Example)

Soybean growth inhibition solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of pelythoxyethylene sorbitol nitrate

In order to produce a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent t of emulsifier t mixture with? make up the desired contentration with water nt.

Rogsi's soybean is grown in a greenhouse until the first lilac leaf is completely formed. At this stage, the plants are sprayed until moistened with the active ingredients. After 3 weeks, the increment was measured for all plants and the growth inhibition in% of the increment of the customs plants was calculated. 100% inhibition of growth means no growth, and 0% means growth of the growth of control plants.

The active compounds according to the invention Nos. 2, 3, 12, 13, 14 and 16, as well as others, show a better growth retardation in this test than substance B, which is known in the art, as can be seen from the following Table O:

Table D

Growth inhibition in soybean active ingredient concentration of active ingredient in% growth retardation in%

- _ 0 (control) (8) 0.05 65 (known) (2) 0.05 95X! XX ⁾ (3) 0.05 100 ^x) XX ⁾ (16) 0.05 90 ^x) XX ⁾ (13) 0.05 70 ^x) XX ⁾ (14) 0.05 85 ^x) XX ⁾ (12) 0.05 95 ^x) XX ⁾ 0.05 40 (74) 0.05 45 (92) 0.05 65 (95) 0.05 85 (103) 0.05 25 ^x) (114) 0.05 25 ^) (115) 0.05 ^30x)

= dark green leaves ^xx '= thick 1'branching'

Example E

Growth retardant per solvent Solvent: 30 parts by weight of dimethylylforaianiide Eintegrator: 1 part by weight of polyoxyethylene sorbitol monolaurate

In order to prepare a suitable active ingredient, 1 part of the active ingredient is mixed with the indicated amount of solvent and emulsifier, and the mixture is made up to the desired volume with water.

Cotton plants are cultivated in the greenhouse until the 5th decontamination leaf is fully unfolded. At this stage, the plants are sprayed with the active ingredients up to the wetting stage. After 3 weeks, the increment of the plants was calculated by calculating the inhibition of growth as a percentage of the increments of the control plants. 10% growth retardation means no growth, and 0% represents growth corresponding to the growth of the control plants.

The active compounds according to the invention Nos. 2, 3, 4 and 12 show a strong growth inhibition in this test in comparison with the control, as can be seen from the following table.

Table E

Growth inhibition of cotton

active substance concentration of active substance in% growth inhibition in% 0 (control) 80 ^x) (2) 0.05 (3) 0.05 40 (4) 0.05 95 (12) 0.05 55

^x '»dark green leaves

Example F

Protective test (shoot treatment) for Erysiphe graminis var. hordei (leaf-destroying mycosis)

To prepare a suitable active ingredient, 0.25 part by weight of the active compound is stirred in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether as emulsifier and 975 parts by weight of water are added. The concentrate obtained is then diluted with water to the desired final concentration.

To determine the protective effect, young barley plants (Amsel species) in the single leaf stage are sprayed to the moistening with the active ingredient prepared and, after drying, dusted with spores of Erysiphe graminis var. hordei.

After six days of cultivation at 21-22 ° C and 80-90% air humidity, the extent of disease on the plants is evaluated. The degree of infestation is expressed as% infestation of the untreated control plants, with 0% indicating no infestation and 100% the same infestation as untreated control plants. The lower the degree of attack, the more effective the test substance is.

In this test, for example, the following compounds show a very good effect, which exceeds that of compounds C, D, and E which are known in the art:

Examples of compounds: 2, 3, 16, 4, 11 and 12.

The results are shown in Table F.

Table F

Protective test (shoot treatment) for Erysiphe graminis var hordei

active substance concentration of active substance in% infestation in% of untreated control (C) 0,025 100 ALIGN! (known) (D) 0,025 50.0 (known) (E) 0,025 58.8 (known) (2) 0,025 0.0 (3) 0,025 0.0 (16) 0,025 0.0 (4) 0,025 0.0 Italy (11) 0,025 0.0 (12) 0,025 0.0

Example G

Test for systemic action on powdery mildew (Erysiphe graminis var. Hordei) - fungal disease of grain shoots

The active ingredient is used in the form of powdered seed dressings. This mordant is prepared by mixing the respective active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to form a finely divided powder containing the active ingredient at the desired concentration.

The barley seed is treated by shaking with prepared stain in a closed glass container. The seed is then sown (3 x 12 grains) 2 cm deep into pots containing a mixture of one volume of standard peat soil and one volume of quartz sand. Germination and emergence of plants takes place under favorable conditions in the greenhouse. 7 days after sowing, when barley plants unfold their first leaf, they are dusted with fresh spores of Erysiphe graminis var. hordei and further cultured at 21-22 ° C and 80-90% relative humidity under 16 hour illumination per day. Typical powdery mildew spots are formed on the leaves within 6 days.

The degree of infestation is expressed as the percentage of infestation of untreated control plants, with 0% indicating no infestation and 100% the same infestation as untreated control plants. The more active the active substance, the lower the extent of the disease.

In this test, for example, the following compounds of the invention exhibit a very good effect which exceeds that of compounds F, G and H known in the art;

Examples of compounds: 2, 3, 4, 11 and 12.

The test results are shown in Table G below.

212339

Table G

Test for systemic action on powdery mildew (Erysiphe graminis var. Hordei) / fungal disease of grain shoots

active substance amount of mordant used in g / kg of seed concentration of active substance in mordant in% attack % of untreated control (F) 10 25 100 ALIGN! (known) (G) 10 25 100 ALIGN! (known) (H) 10 25 100 ALIGN! (known) (2) 10 25 0.0 (3) 10 25 0.0 (4) 10 25 0.0 Italy (11) 10 25 0.0 (12) 10 25 0.0

Example H

Test for mycelial growth:

broth used agar-agar parts by weight

200 parts by weight of potato broth parts by weight of malt parts by weight of dextrose parts by weight of peptone parts by weight of secondary sodium phosphate

0.3 parts by weight of calcium nitrate ratio of solvent mixture to broth:

parts by weight of the solvent mixture

100 parts by weight of agar Nutrient medium Composition of the solvent mixture:

0.19 parts by weight of dimethylformamide or acetone

0.01 part by weight of alkylaryl polyglycol ether as emulsifier

1.80 parts by weight of water are parts by weight of the solvent mixture

The amount of active ingredient required to achieve the desired concentration of active ingredient in the broth is mixed with said amount of solvent mixture. The concentrate was thoroughly mixed with the liquid broth cooled to 42 ° C at the weight ratio indicated, and the mixture was poured into 9 cm diameter Petri dishes. Control plates without the addition of active agent are prepared.

After the broth has cooled and solidified, the plates are counted with each of the fungal species listed below and incubated at about 21 ° C.

i ·

The evaluation is carried out on the basis of the fungal growth rate after 4 to 10 days. The evaluation compares the radial growth of mcceia on the treated broths with that on the control broths. The growth of the fungi is evaluated using the following scale:

up to 3 very slow growth inhibition, up to 7 moderate growth retardation, up to 7 moderate growth retardation, growth the same as for treated control plates.

In this test, for example, the successor to the compound exhibits a very good effect which exceeds the effect of the substance I known in the art:

the compounds of Examples 2 and 3.

The results are shown in the table below:

Table H

Test of the effect on the growth of oycceia

active substance concentration of active substance in% Cooietotrichum coffeanum Pythiuu ultOmuu Phialophora cioerescens Helminthosporiím graoineum Hycosphaerella uuuico- la Pellicularia sasakii (AND) 10 9 9 9 9 9 9 (known) (2) 10 3 2 1 2 1 1 (3) 10 3 3 1 - 1 3

Example I

Growth inhibition in rice solvent: 30 parts by weight of dimethylformamide amide: 1 part by weight of poly (ethylene sorbitan oolalaate)

In order to prepare a suitable active ingredient, 1 part of the active ingredient is mixed with the abovementioned solvent and emulsifier and the mixture is made up to the desired concentration with water.

Roosi's rice is grown in a greenhouse in pots of 10 x 10 x 10 cm in soil to reach the 2-leaf stage. At this stage, the plants are sprayed with active agents until the plants are moistened. After 10 days, all plants were measured for growth and the growth retardation was calculated as a percentage of growth of the control plants. Prioou means 100% non-growth and 0% means growth corresponds to the growth of control plants.

In this test, the active compound 2 according to the invention exhibits a very high growth inhibiting capacity, as shown in Table I.

Table I

Growth inhibition for rice

active substance concentration of active substance in% growth inhibition in% 0 (control) (2) 500 45 1 000 48

Example J

Growth inhibition for irrigated rice (var. Nihonbare)

In the ^IEI m ^{í í} mixing 5 l ^{of DEI says} nn k ^{y s diacrylate} 2.5 ^part by "Newkalgen ^CP -5 ° ^y 30 parts of bentonite and 62.5 parts of talc. 20 parts of water are then added. The resulting slurry is passed through 0.5 mm holes and the product is dried. A granulate having a particle size of 0.5 · mm (0) and a length of about 0.7 mm is obtained.

days old rice plants are grown in bowls of .25 x 20 x 10 cm in which the water exceeds the soil level. After 10 days, the active preparation is applied to water. After a further 14 days, the plant growth height is measured.

R = ethylene or propylene, 9: 1.

In this test, the active compound 2 according to the invention shows a very strong growth retarding ability, as shown in Table J.

Table J

Growth inhibition of rice under irrigation conditions (var. Nihonbare)

active substance concentration of active substance in kg / ha height of height in cm 51.4 (control) (2) 0.25 48.3 0.50 40.8 1.00 38.0 2.00 37.0

Examples P P1 and d 1

83.5 g (0.5 moO) of pinacolyl-1,2,4-thiazole, 60 g (0.54 moO) of cyclohexanaldehyde, 4.2 g (0.05 mol) of piperidine and 6 g (0.1 mol) of glacial acetic acid was heated in 300 ml of toluene under reflux using a water trap. After cooling the reaction solution, the solution was washed with saturated sodium chloride solution, the organic phase was dried over sodium sulfate, filtered and densified. The residue is taken up in 500 ml of acetone and a stirred solution of 90 g (0.25 mol) of naphthalene-1,5-disuioonic acid in 500 ml of acetone is added with stirring.

The precipitate initially formed is filtered off, the filtrate is further concentrated and the colorless crystalline residue obtained is taken up in 500 ml of methylene chloride. Sodium carbonate solution (1: 1) is then added until alkaline. The organic phase is separated, dried, concentrated and concentrated. The oily residue is taken up in petroleum ether and allowed to crystallize. 64 g (49% of theory) of 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triczo-11-l) pent-1-en-3-one of melting point 98 DEG C. are obtained.

Production of starting material (СНз) ₃ С -CO-CH

138 g (2 mol) of 12,4-triazole are added portionwise at room temperature to 276.4 g (2 mol) of ground potassium carbonate and 269.2 g (2 moo) alpha-itlorpioacolios in 500 ml acetone at internal temperature. ascend to boiling point. The mixture was allowed to stir at reflux for 5 hours and then cooled to room temperature. the mixture is filtered and the fraction is 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-triazole-1 ', 1', 1 ', 2', 2 '), m.p.

P Example 2

1 ^ 1101 ^ x1-4,4 ^ 11 ^ 1 ^ 1-2--1,2,4-trico0-1-11) -psot-3-so-3-ol

OH * (C ^^^C-CH-C-CH

Melting point: 131 ° C.

Example 3

A solution of 26.3 g (0.1 mol) of 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triezol-1-yl) pent-1-en-3-ol (Example 2) in 50 ml of dioxane are added dropwise to a suspension of 3 g of 80% sodium hydride in 100 ml of dioxane. After completion of the addition, the mixture was heated at 50 ° C for 1 hour. After cooling, 10.9 g (0.1 mol) of ethyl bromide were added dropwise and the reaction mixture was heated at reflux overnight. After cooling, 10 ml of methanol are added and the mixture is concentrated on a rotary evaporator. The residue was taken up in methylene chloride and washed with water. After drying the organic phase over sodium sulfate, the mixture is filtered and the filtrate is concentrated. The residue was distilled. 11.0 g (37.8% of theory) of 1-cyclohexyl-3-ethoxy-4,4-dimethyl-2- (1,2,4-triazol-1-yl) -pent-1-ene are obtained, boiling point 110 ° C / 9.3 Pa.

Example 1 a d 4

CO-CHq I ^J o

(procedure c):

A solution of 13.15 g (0.05 mol) of 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) pent-1-en-3-ol (Example 2) in 50 ml of dioxane are added dropwise to a suspension of 1.5 g of 80% sodium hydride in 50 ml of dioxane. After the evolution of hydrogen was complete, 3.9 g (0.05 mol) of acetyl chloride were added dropwise. The mixture was heated at reflux for 4 hours. After cooling, the solvent was distilled off in vacuo, the residue was taken up in methylene chloride and extracted with water. The organic phase is dried over sodium sulfate, filtered and the solution is concentrated. The residue was purified over a silica gel column eluting with methanol / chloroform (1: 3) to give 5.6 g (35.4% of theory) of 3-acetoxy-1-cyclohexyl-4,4-dimethyl-2- ( 1,2,4-triazol-1-yl) pent-1-ene as a light yellow oil.

(procedure d):

To a solution of 13.15 g (0.05 mol) of 1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) pent-1-en-3-ol (Example 2) 2 ml of pyridine are added in 100 ml of acetic anhydride. The mixture was stirred at 70 ° C for 4 hours. The reaction mixture was then poured into water and neutralized with sodium bicarbonate. The aqueous phase is extracted several times with ether. The combined ether phases were dried over sodium sulfate and concentrated. 11.2 g (70.8% of theory) of 3-acetoxy-1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) pent-1-ene are obtained in the form of slightly of yellow oil.

Example 5 (procedure e):

CO — NH

To a solution of 13.15 g (0.05 mol) of 1-cyclohexyl-4,4-dimethyl-2- (1H-triazol-1-ylpent-1-ene) -ol (Example 2) in 100 mL of ether 6.5 g (0.055 mol) of phenyl isocyanate and three drops of tributyltin laurate as a catalyst are added and the mixture is stirred at room temperature for 5 days. % of theory) 1-cyclohexyl-4,4-dimethyl-3-phenylcarbamoyloxy-2- (1,2,4-triazol-1-yl) pent-1-ene, m.p.

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

R ¹ -X_c = CH — CH

I я ³

Example no. R ¹ X R ² r3 melting point (° C) 6 (O ^ C -what- O 193 (x | NDS) 7 (C ^^ C -what- O 40 to 48 '8 (CH 3) ₃ C -what- <-y ^H 3 49 9 ’ -what- Э 201 KDS 10 3 -what- C-H4N9 C ₂ H ₅ oil 11 (CH3) ₃ C -CH (OH) - O 151 (Z-form) 12 (CH 2 Cl 2) -CH (OH) - Q ^ ch ₃ oil 13 C ^^ C -CJHOC-jCj-n) - <E> oil 14 (3) 3 ° - ^ch (o-what- (o)) - E> oil 15 Dec (CH3) ₃ C -CH (O-CO-CHC1 ₂₎ - 0 oil 16 (043) ( ^CH 3 -CHCO-CO-N) - & ' oil 17 Cl ^c 'čšč- -CH (OH) - oil 18 -CH (OH) - ^C 2 ^H 5 ^C 2 ^H 5 oil

continued table

example no. R ¹ X and?------- melting point (° C) 19 Dec Cl ^c, 0 ^ - -CH (OH) - O oil 20 May Cl -CH (O-COCH ₃₎ - 0 oil 21 (CH3) ₃ C -CCH ₃ (OH) - 0 101 22nd _{(CH3> 3} C -CH (OH) 0 154 (· HCl) (Z-form) 23 Cl ci ^> - -CH (OH) - ^C 3 «7 CH ₃ oil 24 (CH ₃ ) ₃ C / i -CH (OH) - 0 110 (. CuCl ₂ ) (Z-form) 25 vl ^and <° N -CH (O-CO-NHCH ₃₎ - 0 62 26 Cl ^Cl 0> ~ -CH (OH) - C ₂ 0 CH ₃ oil 27 Mar: Cl - ch (o-what -ζ}) - ^C 3 «7 CH ₃ oil 28 Cl ^Cl 0 ^ - CH (C0-0-CH ₃₎ - ^C 3 ^H 7 ^CH 3 oil 29 (CH3) ₃ C Cl - CH (O - _CH2 - ^ o ^ - CI) - WITH oil (Z-form) 30 C1CH ₂ -C (CH ₃ ) ₂ - -what- 0 51 31 C1CH ₂ -C (CH ₃ ) ₂ - -what- O oil 32 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - 0 oil

continued table

example no .. r1 X r2 r3 melting point (° C) 33 004 -CH (OH) - 0 156 34 (CH3) ₃ C -CH (OH) - я 153 * <_ / (NHO ₃ ) Cl (Z-form) 35 -CH (OH) - oil 36 ° 40- -CH (OH) - 0 oil 37 0 -CH (OH) - 0 oil 38 ^r -0- -CH (OH) - ^С А CH ₃ oil 39 004 -CH (OH) - ^C 2 «5 CH ₃ oil 40 008 -CH (OH) - c ₄ h ₉ C ₂ H ₅ oil 41 C1CH ₂ -C (CH ₃ ) 2 - -CH (OH) - 0 oil 42 _(CH3) .jC -CH ((XC ₃₎ - 0 63 (Z-form) 43 F-@- -CH (OH) - c ₄ h ₉ ^C 2 «5 oil 44 FCH ₂ -C (CH ₃ ) 2 - -WHAT- ^C 4 ^H 9 C2H5 oil 45 (c ₃ ) ₃ c -CH _(OCH3) - 0 104 (E-frame) 46 (CH3) ₃ C • CHIO) - 0 137 (. Mm ₃ ) (E-form) 47 - <004 f / - · · CH ₃ CH ₃ 187

continued table

AND

example no. r ' X R ² r3 \ Melting point (° C) 48 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - CH3 CH3 oil 49 (СН ₃ ) зС -CH (OH) - © 242 (.NDS) 50 (СНз) зС -CH (OH) - © © 168 (CuCl ₂ ) (E-foraa) 51 ^{(CH 3) 3 C} -WHAT- 137 to 140 (. CuCl ₂ ) (El ^ orma) 52 с, © -CH (OH) - © 157 53 С -CH (OH) - C4H9 C2H5 118 54 PhCH 2 C (CH _{3) 2} - -WHAT- © Lej 55 FCH ₂ -C (CH ₃ ) ₂ - -WHAT- © oil 56 PhCH 2 C (CH ₃₎ 2 -CH (OH) - ©. oil 57 FC ^ -CCC ^ ® -CH (OH) - ©. oil 58 FC ^ -CCC ^ ® -WHAT- Oil ‘ (Z-form) ' 59 FC ^ -CCC ^ ® -WHAT- © oil (Z-form) 60 С'С ^ -СССНз © -WHAT- © 103 (E-form) 61 or © ⁴ ® -CH (OH) - 144 62 or © ⁴ ® - CH (Oi) - C ₂ H ₅ C ₂ H ₅ 148 " 63 FCH ^ CCC © ® -CH (OH) - © °, 5049

(Z-form) table continuation

example no. r1 X R ² rP melting point (° C) 64 FC ^ -CtCHj ^ - -CH (OH) - Э n ° 1.4910 (Z-Fox) 65 C1CH ₂ -C (CH 3) ₂ - -CH (OH) - X np ° 1.5050 (E-film) 66 (CH3) jC -what- CH3 CH3 oil 67 (CH3) ₃ C -CH (OH) - CH3 CH ₃ oil 68 30 -what- CH3 C ₂ H ₅ oil 69 (cHj) jC -CH (OH) - CH3 c ₂ h ₅ oil 70 (CH3) jC -co- · CH3 CH3 70 to 74 (x CuCig) 71 (CH3) 3C- -what- CH3 C ₂ H ₅ 60 to 62 (x CuClg) 72 (CH-J ^ C- -what- X oil 73 MC1-CCH3 -what- X oil 74 (CH 3 ^ C- -CH (OH) -. X oil 75 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - - <3 oil у 76 (CH3) ₃ C- -CH (OH) - X 197-108 (Z-film) 77 C1CH2-C (CH3) 2- -WHAT- oil 78 (CH 3 ^ C- -WHAT- XX oil * 79 FCH ₂ -C (CH 3) ₂ - -WHAT- xr ” oil 80 (CH3) ₃ C- -CH (OH) - XX oil 81 C 1 CH 2 Cl ₂ (CH 3) ₂ -CH (OH) - xr " oil

continued table

example δ. R ¹ X R ² R ³ temperature t · ni '(° C)' 82 (ch ₃ ) ₃ c- -what- tf oil, 83 FC ^ -CÍC ^^ - -CH (OH) - tf oil 84 (ch ₃ ) ₃ c- -WHAT- it oil 85 C1CH2-C (CH ₃₎ 2 -WHAT- X oil 86 FC ^ -CÍC ^^ - -WHAT- it oil (Z-form) 87 FC ^ -CdOj ^ - -WHAT- it oil 88 (CH-j ^ C- -WHAT- X oil 89 Cl α-ζο ^ - -CH (OH) - tt oil 90 -CH (OH) - tt ' amorphous substance 91 -CH (OH) -. it amorphous substance 92 £ CH ₃ ) ₃ C- -CH (OH) - X oil 93 (ch ₃ ) ₃ c- -C (O) - oil 94 Cl -CH (OH) - amorphous substance Cl (net 95 -C ^ Otn- it.· isomer) amorphous substance

continued table

Example No. - X R ² R ³ melting point (° C) 96 Cl ^c ' ^x ° ^x - -CH (OH) - oil 97 Cl -CH (OH) - amorphous substance (pure 98 (CH ₃ ) ₃ C- -WHAT- P CH3 isooer) oil 99 (CH 3 ^ C- -CH (OH) - P. CH3 47 100 ALIGN! (CH ^ C- -WHAT- XD oil 101 / ^CH 3 ⁾ 3 ^C - -WHAT- XD 187 (x 1/2 NDS) 102 (CH ^ C- -CH (OH) - XD 43 103 · (CH ₃ ) ₃ C- -CH (OH) - P CH3 119 '(Z-forum) 104 (CH ₃ ) ₃ C- -WHAT- p CH3, oil (Z-foroa) 105 (CH ^ C- -WHAT- avCH3 - <! 9 oil 106 (CH ₃ ) ₃ C- -WHAT- 173 (x 1/2 NDS) 107 (CH ₃ ) ₃ C- -CH (OH) - prCH3 38

the verge of the table

example δ. R ^ X R * R ^R melting point (° C) 108 C1CH ₂ -C (CH ₃ ) ₂ - -what- 80 (Z-form) 109 FCH ₂ -C (CH ₃ ) ₂ - -what- 68 (Z-form) 110 C1CH ₂ -C (CH ₃ ) ₂ - -what- ^ch 'b oil 111 KCH ₃ -C (CH ₃ ) ₂ - -what- CHo в oil 112 FCH ₂ -C (CH ₃ ) ₂ - -what- ^ 2¾ ^G 2 ^ 5 oil 113 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - amorphous substance (Z-form) 1 14 FCH 3 -C (CH), - 2 3 2 -CH (OH) - "’ B amorphous substance 115 C1CH ₂ -C (CH ₃ ) ₂ - -CH (OH) - CH, amorphous в substance 116 FCH ₂ -C (CH ₃ > ₂ - -CH (OH) - amorphous substance (Z-form) 117 C1CH ₂ -C (CH ₃ ) ₂ - -WHAT- ^CH1 B oil 118 FCH ₂ -C (CH ₃ ) ₂ - -what- ^CH 'B oil E- and Z-form - both possible geometric isomeric forms

NDS = 1,5-naphthalenedisulfonic acid

Claims (2)

OBJECT IN JY FIND Plant growth regulating agents and fungicidal agents, characterized in that they contain at least one 1-vinyltriazole derivative of the general formula as active ingredient I, (I) • k in which R ¹ R ² R ³ or atoms cykloR ² and R ³ R ⁴ is 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 halo-phenyl substituted naphthyl, C 1 -C 4 alkyl, C 1 alkyl C 4 -C 4 cycloalkyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl optionally substituted C 5 -C 7 alkenyl, C 2 -C 4 alkenyl or optionally halogen and / or C 1 alkyl optionally substituted by phenyl or naphthyl, and in addition to the carbon atom to which they are attached, optionally represent a (C 1 -C 4) alkyl group substituted by a (C 3 -C 12) cycloalkenyl or optionally (C 1 -C 4) alkyl group Or (C 3 -C 12) -cycloalkyl-substituted cycloalkyl carbon atoms, 4 5 1 represents -C (OR ⁴ ) R and in addition keto when R represents an optionally substituted alkyl or cycloalkyl group, wherein it represents hydrogen, an alkyl group having 1 to 4 carbon atoms or optionally a halogen, an alkyl group having 1 to 4 carbon atoms , halogenoalkyl with up to 2 carbon atoms and up to 3 halogen atoms в, phenyl and / or phenoxy substituted benzyl or naphthylmethyl group, or is an acyl radical -CO-R ^10, or R В? Wherein the carbamoyl radical is -CO-NRR wherein C 1 -C 4 alkyl, C 1 -C 2 haloalkyl of up to 5 halogen atoms or optionally halogen and / or C 1 -C 4 alkyl substituted with phenyl or benzyl, hydrogen or (C1-C4) -alkyl and (C1-C4) -alkyl, (C1-C4) -haloalkyl, up to 5-halogen or optionally halogen, (C1-C4) -alkyl, haloalkyl phenyl or naphthyl substituted with up to 2 carbon atoms and up to 5 halogen atoms and / or haloalkylmercapto substituted with phenyl or naphthyl, and hydrogen, C1-4 alkyl or optionally halogen or alkyl benzyl substituted with 1 to 4 carbon atoms, r ' R ¹² or its addition salt with 1,5-naphthalenedisulfonic acid, hydrochloric, hydrobromic or nitric acid or its complex with copper (II) chloride. 2. A process for the preparation of an active ingredient according to claim 1, in which X represents a radical, R1 represents a C1-C4 alkyl group optionally substituted one or two times by halogen, a C1-C4 alkylcarbonyloxy group. in the alkyl moiety or C 1 -C 4 alkylsulfonyloxy or C 5 -C 7 cycloalkyl, and R ² and R ³ are as defined in point 1, and the 1,5-naphthalenedisulphonic acid, hydrochloric acid editorial salts of the compounds of formula I , hydrobromic or nitric compounds or copper (I) chloride complexes, characterized in that the triazolketones of the general formula (II): R ¹ has the abovementioned meaning, are reacted with aldehydes of the formula XII, 0 = CH-CH \ r ³ (ΙλΙ) in which 2 3 R and R are as defined above in the presence of a solvent and in the presence of a catalyst, and the desired isomeric product of formula (Ia) is isolated from the isomers formed by hydrogen cleavage by conventional methods, O 1 N R‘-C-C = CH-CH I (Ia) in which 1 2 Ί R, R and R are as defined above, whereupon the optionally obtained compounds are converted into the 1,5-naphthalenedisulfonic, hydrochloric, hydrobromic or nitric acid or a copper (II) chloride complex.