CA2037079A1 - 4-(4-tert-butylphenyl)cyclohexylamines, and fungicides containing same - Google Patents

4-(4-tert-butylphenyl)cyclohexylamines, and fungicides containing same

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Publication number
CA2037079A1
CA2037079A1 CA002037079A CA2037079A CA2037079A1 CA 2037079 A1 CA2037079 A1 CA 2037079A1 CA 002037079 A CA002037079 A CA 002037079A CA 2037079 A CA2037079 A CA 2037079A CA 2037079 A1 CA2037079 A1 CA 2037079A1
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Prior art keywords
alkyl
tert
butylphenyl
unsubstituted
alkenyl
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Abandoned
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CA002037079A
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French (fr)
Inventor
Berhard Zipperer
Eberhard Ammermann
Gisela Lorenz
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BASF SE
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BASF SE
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    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
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    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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Abstract

O.Z. 0050/41443 ABSTRACT OF THE DISCLOSURE: 4-(4-tert-butylphenyl)-cyclohexylamines andquaternary ammonium salts thereof of the formulae and

Description

~3 ~ ~rl~

O.Z. 0050/41443 4-(4-tert-Butylphenyl)cyclohexylamines. and fungicides containin~ same The present invention relates to novel 4-t4-tert-butylphenyl~cyclohexylamines and acid-addition salts and quaternary salts thereof, to a process and intermediates for the preparation thereof, to the use thereof as fungicides, to fungicides, and to a method of controlling harmful fungi using these active ingredients.
The compound trans-4-tert-butyl-N-benzylcyclo-hexylamine is known (J. Org. Chem. 48 (1983) 3412-3422), but nothing is known on its fungicidal action.
4-(Cyclohexylmethyl)cyclohexylamine and its N,N-dimethyl derivative are known as fungicides (US
3,981,766), but their fungicidal action is unsatisfac-lS tory.
l-[4-(4-tert-Butylphenyl)cyclohexyl]-2,6-di-methylmorpholine has been described as a fungicide (EP 259 977), but its efficacy is poor in some areas of application, in particular at low application rates and concentrations.
Fungicidal cyclohexylamine~ are disclosed in DE 36 ~0 247. Their fungicidal action is good, but their plant compatibility is unsatisfactory, particularly at relatively high application rates.
We have now found that 4-(4-tert-butylphenyl)-cyclohexylamines and the quaternary ammonium salts thereof, of the formulae Rl CH3 N\ and ~ ~ R2 x~

where R~ is hydrogen, C1-C6-alkyl or C3-C6alkenyl, R2 is Cl-Cl2-alkyl, C~-Cl2-haloalkyl, C~-Cl2-hydroxyalkyl, C3-Cl2-cycloalkyl, C4-C,2-alkylcycloalkyl, C7-C,2-bicyclo-alkyl, C3-C12-alkenyl, unsubstituted, monosubstituted, I

C ~ 7 ~3 ~ 9 - 2 - O.Z. 0050/41443 disubstituted or txisu~stituted phenyl, or unsubstituted, monosubstituted, disubstituted or trisu~stituted phenyl-(cl-c3)alkyl~ possible substituents in each case being identical or different Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, halogen, cyano, hydroxyl or nitro groups, with the proviso that Rl and ~2 are not simultaneously C1-C4~alkyl, xe is a plant-compatible acid anion, and the plant-compatible acid addition salts thereof, have a strong fungicidal action and surprisingly good plant compatibility.
Rl is, for example, hydrogen, straight-chain or branched Cl-C~-alkyl, in particular Cl-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl or neohexyl, or straight-chain or branched C2-C6-alkenyl, such as 2-propen-1-yl, cis- or trans-2-buten-1-yl, 2-methyl-2-propen-1-yl, 3-buten-2-yl or 3-methyl-2-buten-1-yl.
R2 is, for example, straight-chain or branched C~-Cl2-alkyl, in particular C,-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl; C1-C12-haloalkyl such as chloromethyl, bromomethyl, iodomethyl, 2-chloroethyl, 4-chloro-l-butyl, 3-chloro-1-butyl, 3-chloro-2-methyl-1-propyl, 5-chloro-1-pentyl or 6-chloro-1-hexyl; C~-C12-hydroxyalkyl, such as 2-hydroxyethyl, 2-hydroxy-1-propyl, 6-hydroxy-1-hexyl, 8-hydroxy-1-octyl or 10-hydroxy-1-decyl; C3-C12-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl or cyclododecyl; C4-C12-alkylcycloalkyl such a~ methylcyclo-propyl, methylcyclopentyl, 2-, 3- or 4-methylcyclohexyl, 2-, 3- or 4-athylcyclohexyl, 4-isopropylcyclohexyl, 4-tert-butylcyclohexyl, 2,2-, 3,3- or 4,4 dimethylcyclo-hexyl, 2,6-dLmethylcyclohexyl or 3,3,5,5-tetramethyl-.

~3~ 3 - 3 - O.Z. 0050/41443 cyclohexyl; C7-Cl2-bicycloalkyl such as bicyclo[2.2.1]-hept-2-yl, 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl, bicyclo[4.4.0]dec-2-yl or bicyclo[4.4~0]dec-3-yl; phenyl, Cl-C4-alkylphenyl, mono-, di- or trimethylphenyl, ethyl-S phenyl, isopropylphenyl, tert-butylphenyl, Cl-C4-alkoxy-phenyl, mono-, di- or trimethoxyphenyl, n- or tert-butoxyphenyl, Cl-C4-haloalkylphenyl, Cl-C4-haloalkoxy-phenyl, trifluoromethylphenyl, difluoromethoxyphenyl, trifluoromethoxyphenyl, tetrafluoroethoxyphenyl, cyano-phenyl, nitrophenyl, mono-, di- or trichlorophenyl, mono-, di- or trifluorophenyl, chlorofluorophenyl, bromophenyl, aryl(C1-C3)alkyl, such as benzyl, C1-C4-alkylbenzyl, mono-, di- or trimethylbenzyl, tert-butyl-benzyl, halobenzyl, fluorobenzyl, mono-, di- or tri-chlorobenzyl, C1-C4-alkoxybenzyl, mono-, di- or tri-methoxybenzyl, cyanobenzyl, nitrobenzyl, 2-phenylethyl, 2-(methoxyphenyl)ethyl,2-(chlorophenyl)ethyl,2-(fluoro-phenyl)ethyl, 2-(tert-butylphenyl)ethyl, 3-phenylpropyl, 3-(chlorophenyl)propyl or 3-(fluorophenyl)propyl.
xe is an inorganic or organic acid anion, for example chloride, bromide, iodide, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, nitrate, tetrafluoroborate; formate, acetate, oxalate, methanesulfonate, benzenesulfonate, p-toluene-sulfonate or dodecylbenzenesulfonate.
Examples of acids for the preparation of the acid-addition salts are mineral acids, hydrochloric acid, sulfuric acid, nitric acid, formic acid, alkylcarboxylic acids, such as acetic acid, propionic acid, oxalic acid, sulfonic acids, such as methanesulfonic acid, benzene-sulfonic acid, p-toluenesulfonic acid and dodecyl-benzenesulfonic acid.
The novel compounds of the formulae 1 and 2 can exist in two diastereomeric form~, namely as cis-1,4- and as tran~-1,4-disubstituted cyclohexane. Depending on the preparation method, they are obtained either a~ pure diastereomers or as diastereomer mixtures. If desired, , - :

~37~
- 4 - O.Z. 0050/41443 the latter can be re~olved to give pure diastereomer~ by generally known methods, for example by chromatography or fractional crystallization. The present invention relates both to the pure diastereomers and to mixtures thereof.
In some of the radicals R2 according to the invention, further isomers can occur in addition to the abovementioned cis/trans isomerism. Depending on the nature of R2, these isomers may be enantiomers or dia-stereomers. Here too, the diastereomeric compounds can be resolved by conventional methods, for example by chroma-tography or crystallization. All isomeric compounds and mixtures thereof with one another are included in the present invention. The pure diastereomers or enantiomers and the mixtures thereof are suitable for use of the novel amines as fungicides. Preference is given to mixtures.
The present invention also relates to a process for the preparation of the novel amines of the formula 1.
a) These amines can be prepared, for example, by reacting an amine of the formula Rl \R2 where R1 is hydrogen, Cl-C6-alkyl or C3-C6-alkenyl and R2 i~ C1-C12-alkyl, with the proviso that Rl and R2 are not simultaneously C1-C4-alkyl, or is C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C3-Cl2-cycloalkyl, C4-Cl2-alkylcycloalkyl, C,-C12-bicycloalkyl, C3-C12-alkenyl, unsubstituted, mono-substituted, disubstituted or trisubstituted phenyl, or unsubstituted, monosubstituted, disubstituted or tri-substituted phenyl(C1-C3)-alkyl, possible substituents being in each case identical or different C1-C4-alkyl, C1-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, halogen, cyano, hydroxyl or nitro group~, with 4-(4-tert-butylphenyl)cyclohexanone, and reducing - s - O.Z. 0050/41443 the imine (in the case where R1 is hydrogen) or enamine (in the case where Rl is not hydrogen) produced as a reaction product, either directly or after isolation, using a reducing agent to give an amine of the formula 1.
5It is advantageous to remove from the reaction mixture the water of reaction liberated on reaction of an amine of the formula 3 in which R1 and R2 are as defined above with 4-(4-tert-butylphenyl)cyclohexanone. This can be ef~ected, for example, by adding a dehydrating agent 10or by azeotropic distillation. Examples of suitable dehydrating agents are salts which are free of or low in water of hydration, such as sodium sulfate, magnesium sulfate, zinc sulfate, calcium chloride or molecular sieves. The reaction iR carried out in the presence or 15absence of an inert organic solvent and in the presence or absence of a catalytic amount of acid. Suitable solvents are hydrocarbons, such as cyclohexane, benzene, toluene or xylenes, chlorinated hydrocarbons, such as dichloromethane or 1,2-dichloroethane, or ethers, such as 20diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane. Examples of suitable acids are mineral acids, ~uch as sulfuric acid or phosphoric acid, or sulfonic acids, such as methanesulfonic acid, benzenesulfonic acid or p-toluene~ulfonic acid. The amount of acid necessary 25is, for example, from 0 to 10 mol-%, preferably from 0 to 1 mol-%, based on the amine of the formula 3. The reac-tion can be carried out at room temperature or at ele-vated temperature, for example up to the boiling point of the particular solvent. If the reaction temperature which 30is necessary cannot be achieved under atmo~pheric pres-sure or if the reaction proceeds only ~lowly, the reac-tion can be carried out in an autoclave (with or without a solvent) at elevated temperature under the inherent pressure of the reaction mixture. If the water of reac-35tion produced is removed from the reaction mixture by azeotropic distillation, the reaction is carried out at the boiling point of the particular solvent. Preferred I .
~. - . . .

7 ~
- 6 - O.Z. 0050/41443 solvents here are aromatic hydrocarbons, such as benzene, toluene or xylenes.
The unsaturated nitrogen compound (imine or enamine) produced on reaction of an amine of the formula 3 where R1 and R2 are as defined above with 4-(4-tert-butylphenyl)cyclohexanone can be reduced by conventional methods to give an amine of the formula 1. Specific examples of preferred reducing agents are hydrogen, formic acid, or complex hydrides such as sodium boro-hydride or sodium cyanoborohydride. Particular preference is given to hydrogen in the presence of a metallic catalyst. Examples of suitable catalysts are finely divided metals, such as Raney nickel or Raney cobalt, and noble metals, such as palladium or platinum, with or without a solid carrier. The hydrogenation using hydrogen can be carried out with or without pressure (cf., for example, Houben-Weyl, Methoden der Organischen Chemie, Volume 11/1, pp. 602 ff, G. Thieme Verlag, Stuttgart, 1957). It is occasionally advantageous to prepare the amine of the formula 1 in one step from an amine of the formula 3 and 4-(4-tert-butylphenyl)cyclohexanone.
A known process for this purpose in which the reducing agent is formic acid is the reductive amination by the Leuckardt-Wallach method (cf., for example, Houben-Weyl, Methoden der Organischen Chemie, Volume 11/1, pp. 648 ff, G. Thieme Verlag, Stuttgart, 1957).
Another process, which is particularly advantageous for laboratory scale syntheses, uses sodium cyanoborohydride as the reducing agent (cf., for example, C.F. Lane, Syn-thesis 1975, 135). The combination of sodium cyanoboro-hydride and anhydrous zinc chloride has proven particu-larly expedient (cf. S. Kim et al., J. Org. Chem. 50 (1985) 1927).
In this process, the NaBH3CN:ZnC12 molar ratio can be, for example, from 1:2 to 1:0.5, preferably 1:0.5. As far a~ the amount of NaBH3CN employed is concerned, either the amine component 3 or the ketone component can be used ~ ~ 3 '~
- 7 - o.Z. 0050/41443 in an equimolar amount; an excess of the other component may occasionally be advantageous in order to accelerate or complete the reaction. The reaction is preferably carried out in a lower alcohol, such as methanol, 5ethanol, n-propanol or isopropanol, particularly prefer-ably in methanol, as solvent, at between 0C and the boiling point of the particular solvent. The reaction is preferably carried ou~ at room temperature.
The 4-(4-tert-butylphenyl)cyclohexanone used as 10starting material is novel. It can be prepared from known, commercially available 4-phenylcyclohexanone by Friedel-Crafts alkylation of the phenyl ring. Examples of alkylating agents are tert-butyl chloride or bromide, tert-butanol or 2-methylpropene (cf., for example, 15Houben-~eyl, Methoden der Organischen Chemie, Vol. 5/2b, pp. 154 ff., pp. 179 ff., G. Thieme Verlag, Stuttgart, 1981). Preference is given to 2-methylpropene in the presence of a mineral acid, for example sulfuric acid or phosphoric acid, or in the presence of a Lewis acid, such 20as aluminum trichloride, iron(III) chloride or boron trifluoride. Suitable solvents are in particular chlorin-ated hydrocarbons, especially dichloromethane, tetra-chloromethane, and 1,2-dichloroethane. The tert-butyla-tion of the 4-phenylcyclohexanone can be carried out at .
25room temperature or below, preferably at from 0 to 20C.
The amines of the formula 3 where R1 and R2 are as defined above are known compounds and those which are not commercially available can be prepared by known pro-cesses.
30The amines prepared by the above-described proces~, where R1 and R2 are a~ defined above, are gener-ally mixtures of the two possible stereoisomers contain-ing a cis- or trans-1,4-disubstituted cyclohexane ring.
These cis/trans mixtures may, if desired, be resolved 35into their constituents by known methods, for example by chromatography or fractional crystallization.
b) A further process allows the targeted preparation 2~3r~3Y~9 - 8 - O.Z. 0050/41443 of cis- or tran~-4-(4-tert-butylphenyl)cyclohexylamines of the formula 1 where R1 is hydrogen and R2 is Cl-Cl2-alkyl, Cl-Cl2-haloalkyl, Cl-Cl2-hydroxyalkyl, C3-Cl2-cycloalkyl, C4-Cl2-alkylcycloalkyl, C7-Cl2-bicyclo-alkyl, C3-C12-alkenyl, unsubstituted, monosubstituted, disubstituted or trisubstituted phenyl, or unsubstituted, monosubstituted, disubstituted or trisubstituted phenyl-tCl-C3)alkyl, possible substituents in each case being 10 identical or different Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, halogen, cyano, hydroxyl or nitro groups.
This process comprises first converting 4-(4-tert-butylphenyl)cyclohexanone into 4-(4-tert-butyl-15 phenyl)cyclohexanone oxLme by conventional methods using hydroxylamine or a hydroxylamine salt, and subsequently reducing this oxime using sodium in ethanol (cf., for example, Chem. Ind. (London) 1972, 683). The trans-4-(tert-butylphenyl)cyclohexylamine obtained is then 20 reacted in a further step with a carbonyl compound of the formula where R3 and R4 are such that the radical -CH

correspond~ in its entirety to R2 as defined above, and the imine formed is reduced, directly or after isolation, using a reducing agent to give the amine of the formula 1.
If 4-(4-tert-butylphenyl)cyclohexanone oxime is reduced, for example~ using hydrogen, a mix~ure of cis-and trans-4-(4-tert-butylphenyl)cyclohexylamine is obtained, which can be resolved into the pure cis- and trans-isomers by conven~ional methods, for example by J~
- 9 - 0.2. 0050/41443 chromatography, distillation or fractional crystallization of an acid-addition salt with subsequent liberation of the base. The two isomers can then be reacted separately with a carbonyl compound of the S formula R3-e-R4 4 where R3 and R4 are as defined above to give the pure cis-and trans-configured amines of the formula 1.
It is of course also possible to react the mixture of cis- and trans-4-(4-tert-butylphenyl)cyclo-hexylamines with a carbonyl compound of the formula 4 and to resolve the resultant isomer mixture of amines of the formula 1 into its constituents, for example by chromato-graphy or crystallization.
A further way of preparing a cis/trans mixture of 4-(4-tert-butylphenyl)cyclohexylaminescompris2~alkylat-ing cis/trans-4-phenylcyclohexylamine using 2-methyl-propene in the presence of an at least equimolar amount of mineral acid, for example sulfuric acid. Preferred solvents are chlorinated hydrocarbons, eg. dichloro-methane, tetrachloromethane or 1,2-dichloroethane. The alkylation can be carried out at room temperature or below, preferably at from 0 to 20C.
The 4-phenylcyclohexylamine used as a starting material is known. It can be prepared, for example, by hydrogenating 4-aminobiphenyl (R. Egli, C.H. Eugster, Helv. Chim. Acta 58 (1975) 2321) or 4-phenylcyclohexanone oxime (Nightingale et al., J. Org. Chem. 17 (1952) 1017).
The carbonyl compounds of the formula 4 which are required for process b) are common chemicals, and those which are not commercially avaiable can be prepared by conventional methods.
The reaction conditions described in detail for process a) al30 apply similarly to process b).
The above-described process b) gives the amines .

- 10 - O.Z. 0050/41443 of the formula 1 where R1 is hydrogen. These secondary amines can, if desired, be converted into tertiary amines of the formula 1 where Rl is Cl-C6-alkyl or C3-C6-alkenyl by known alkylation reactions.
SIf the alkylating agent used is a methyl compound of the formula where A is a nucleofugic leaving group, eg. chlorine, bromine, iodine, O-SO2-OC~3, O-SO2-CH3 or O-SO2-p-C6H4-CH3, 10and the alkylating agent is employed in excess, 4-(4-tert-butylphenyl)cyclohexylammonium salts of th~ formula 2 where R2 is a~ defined above are obtained.
Thi~ quaternization can be carried out in the presence or absence of a diluent. Examples of suitable lSdiluents are alcohols, such as methanol, ethanol, n- or isopropanol, n-butanol or cyclohexanol, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, esters, such as methyl acetate or ethyl acetate, nitriles, such as acetonitrile or propionitrile, 20nitro compounds, such as nitromethane or nitrobenzene, or other solvents which are inert in thi~ reaction. The alkylation i8 preferably carried out using two to 6 times ~he molar amount of alkylating agent of the formula 5 and at from 20 to 200C. The reaction is expediently carried 2Sout at the boiling point of the particular diluent, or, if none i~ used, of the particular alkylating agent.
It i8 occasionally advantageous to carry out tha quaternization in the pre~ence of an auxiliary base, which can be added in excess or in an equLmolar amount, 30based on the amine 1 to be alkylated. The U8Q of a base which is insoluble in the reaction medium, for example sodium carbonate, pota3sium carbonate or calcium car-bonate, i8 particularly advantageous.
The reaction product obtained is a 4-(4-tert-35butylphenyl)cyclohexylammonium salt of the formula ~3Y~Y~
O.Z. 0050/41443 ~R 2 A~\ 2a where R2 and A are as defined above. If necessary, the anion Ae can be replaced by another, plant-compatible acid anion by conventional methods, for example by ion ex-change chromatography.

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:-- 13 - O.Z. 0050/41443 The examples below are intended to illustrate the preparation of the compounds according to the invention in greater detail.

4-(4 -tert-Butylphenyl)cyclohexanone 170.5 g (1.74 mol) of concentrated sulfuric acid are added dropwise with stirring and cooling at from 0 to 5C to a solution of 50 g (0.287 mol~ of 4-phenylcyclo-hexanone in 600 ml of dichloromethane. 19.5 g (0.35 mol) 19 of isobutylene (2-methylpropene) gas are passed into this mixture over the course of 15 to 20 minutes at from 10 to 15C. The mixture is stirred at room temperature (20C) for a further one hour and 250 ml o~ water are then added dropwise with ice cooling. The organic phase is separated off, washed neutral with water, 10% strength NaOH and again with water, dried over Na2SO4 and evaporated under reduced pressure. The residue is recrystallized from n-pentane, to give 50.7 g (76% of theory) of colorless crystals of melting point 80-82C.
lH-NMR (CDC13): ~ = 7.35 (d, 2H), 7.18 (d, 2H), 3.00 (br, t, lH), 2.50 (m, 4H), 2.21 (m, 2H), 1.95 (m, 2H), 1.30 (9~ 9H).
IR (KBr): v = 2965, 2944, 2867, 1710, 1418, 1160, 832, 808, 570 cm~1.

4-trans-tert-Butyl-4~-cis/trans-(4-tert-butylphenyl)-N,N-dicyclohexylamine (Compound No. 62) 16.1 g (0.07 mol) of 4-(4-tert-butylphenyl)cyclo-hexanone, 21.7 g (0.14 mol) of trans-4-tQrt-butylcyclo-hexylamine and 4.8 g (O.035 mol) of anhydrous zinc chloride are dissolved in 250 ml of methanol. 4.4 g (0.07 mol) of sodium cyanoborohydride are introduced into the solution in portions. The mixture is stirred at room tem?erature for 24 hours, and the ma~ority of the solvent is then stripped off under reduced pressure. The residue taken up in water, rendered alkalin~ usin~ concentrated NaOH and extracted several time~ with me~hyl tert-butyl , - 14 - O.Z. 0050/41443 eth~r. The organic phase is dried over Na2SO4, freed from solvent and then distilled under reduced pressure. After an initial fraction comprising principally 4-t~rt-butyl-cyclohexylamine, 19.3 g (75% of theory) of the title compound are obtained at 210~212C/0.2 ~bar as a color-less, viscous oil. According to GC and lH-NMR analysis, it is a cis/trans mixture in the ratio 2:3.
C26H43N (369.1) Calc. C 84.48 H 11.73 N 3.7g Found C 84.5 H 11.7 N 3.6 Resolution of 4-trans-tert-butyl-4'-cis/trans-4-(tert-butylphenyl)-N,N-dicyclohexylamine 8.0 g of a cis/trans isomer mixture obtained as in Example 2 are resolved by chromatography on a 30 x 3 cm silica gel column (Macherey & Nagel, 0.04-0~06 mm) using cyclohexane/ethyl acetate (4:1) at 0.1 bar of nitro~en. The 4-trans-tert-butyl-4'-cis-(4-tert-butyl-phenyl)-N,N-dicyclohexylamine is eluted first as a colorless ~olid of melting point 54-56C (ethanol). The relative stereochemistry was determined by lH- and l3C-NMR
spectroscopy.
H-NMR (CDC13): inter alia ~ = 3.00 (m, l~~Hoq) ~ 2.55 (m, l-H~), 2.40 (4'-H~).
l3C-NMR (CDCl3)s inter alia ~ = 54.04 (C-l'), 43.69 (C-4'), 34.86 (C-2'(6')), 33.39 (C-3'(5')).
After a mixed fraction (0.8 g), 4-trans-tert-butyl-4'-trans-(4-tert-butylphenyl)-N,N-dicyclohexylamine is obtained, initially as a pale yellow oil, which crystallizes from acetonitrile. Colorless crystals, melting point 112-113C.
H-NMR (CDC13): inter alia ~ = 2.67 (br.m, l'-H~), 2.50 (br. m, l-H~ + 4'H~).
3C-NMR (CDC13): inter alia ~ = 48.42 (C-l'), 42.69 (C-4' )! 30.98 (C-2'(6')), 28.30 (C-3'(5')).

N,N-Dimethyl-4-trans-tert-butyl-4'-cis/trans-t4-tert-butylphenyl)-N,N-dicyclohexylammonium iodide : ' :

- 15 - O.Z. 0050/41443 7.4 g (0~02 mol) of 4-trans-tert-butyl-4'-cis/
trans-(4-tert-butylphenyl)-N,N-dicyclohexylamine (Example 2), 11.4 g (0.08 mol~ of methyl iodide and 10.2 g of sodium carbonate (0.10 mol) are refluxed for 6 hours in 50 ml of ethanol. After cooling, the mixture is filtered, the filtrate is evaporated to dryness under reduced pressure, and the oily residue i5 boiled with 50 ml of ethyl acetate. The mixture is left to stand overnight, and the precipitate is filtered off with suction, washed with ice-cold acetone and dried at 50C under reduced pressure, to give 6.7 g (62% of theory) of quaternary salt as colorless crystals of melting point 184-185C.

cis/trans-4-(4-tert-Butylphenyl)cyclohexylamine 165 g of concentrated H2SO4 (1.68 mol) are added dropwise to 52.5 g (0.30 mol) of well cooled 4-phenyl-cyclohexylamine (cis/trans ratio of about 2:3) at from 0 to 5C. 1,000 ml of dichloromethane diluent are added, and 21.8 g (0.39 mol) of isobutylene gas are passed in over the course of 20 minutes at from 10 to 15C. After one hour at 20C, 250 ml of water are added dropwise with ice cooling. The aqueous phase is extracted twice with CH2Cl2. The combined organic phases are stirred vigorously with 1 1 of 10 percent strength by w.~ight NaOH, then washed with water, dried over Na2SO4 and evaporated under reduced pre~sure. The crude amine, which is about 70%
pure according to gas chromatography, is dissolved in 500 ml of ether and precipitated as tho hydrochloride by passing in HCl gas with ice cooling to give 35.3 g (44.5%
of theory) of a yellowish crystal powder wh$ch decomposes above 240C, IR (KBr): v = 2956, 2932, 2868, 1607, 1510, 1448, 1362, 1268, 831, 574 cm~~.
The free base is obtained therefrom by adding aqueous ammonia solution, extracting the mixture with methyl tert-butyl ether, and drying and e~aporating the organic phase to give a colorless oil (ci~/tranc - 16 - O.Z. 0050/41443 mixture). Characteristic NMR data (CDCl3): cis-4-(4-tert-butylphenyl)cyclohexylamine: ~ l~Heq = 3.19; ~ C-1 =
45.3 ppm.
trans-4-(4-tert-sutylphenyl)cyclohexylamine:
~ l-H~ = 2.70; ~ C-l = 50.2 ppm.

N-Benzyl-N-4-(4-tert-butylphenyl)cyclohexylamine (Compound No. 104) A solution of 11.6 g (0.05 mol) of 4-(4-tert-butylphenyl)cyclohexylamine (cisftrans mixture) and 6.4 g (0.06 mol) of freshly distilled benzaldehyde in 200 ml of toluene is treated with 14.2 g (0.10 mol) of sodium sulfate and stirred at room temperature overnight. After filtration, the toluene is stripped off and replaced by ethanol. 2.7 g (0.07 mol) of sodium borohydride are then added, the mixture is refluxed for one hour and evapor-ated to dryness, and the residue is partitioned between water and methyl tert-butyl ether. The organic phase is washed with water, dried over sodium sulfate and evapor-ated, and the residue is sub~ected to incipient distilla-tion at 2 mbar up to 200C to give 9 g (56% of theory) of a pale reddish resin, a 2:1 tran~/cis isomer mixture according to lH-NMR and gas chromatography.
IR (film) 5 V = 2961, 2927, 2862, 1461, 1452, 1362, 827, 736, 698, 572 cm~l.
Cz3H3lN (321.1) Calc. C 85.92 H 9.72 N 4.36 Found C a5 ~ 5 H 9.9 N 4.1 The following compounds are prepared by measure~
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49 O.Z. 0050/41443 In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, 20 Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, -Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, 30 Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the 35 active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi. Either the fungi themselves, or the plants, seeds, materials or the soil to be protected against fungus attack are treated with a fungicidally effective amount of the active ingredient.
The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water ~`J ~ ~ d ~ 7 ~

O.Z. 0050/41443 is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., 5 methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyl-10 ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); anddispersants such as ligninsulfite waste liquors and methylcellulose.
The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient. The application rates are from 0.02 to 3 15 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials (timber), e.g., on Paecilomyces variotii. When the active ingredients are used for treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 20, 9 per kg of seed are generally required.
The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. A solution of 90 parts by weight of compound no. 62 and 10 parts by weight of N-methyl-a-pyrrolidone, which is suitable for application in the 30 form of very fine drops.
II. A mixture of 20 parts by weight of compound no. 5, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of 35 the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the mixture in water, an aqueous dispersion is obtained.
III. An aqueous dispersion of 20 parts by weight of compound no. 15, 40 40 parts~by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing this mi~ture in water, an aqueous dispersion of the active ingredient is obtained.

' ' "'~
-:
,.

51 O.z. 0050/41443 IV. An aqueous dispersion of 20 parts by weight of compound no. 39, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor 5 oil. By finely distributing this mixture in water, an aqueous dispersion is obtained.
V. A hammer-milled mixture of 80 parts by weight of compound no. 123, 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic 10 acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.
15 VI. An intimate mixture of 3 parts by weight of compound no. 50 and 97 parts by weight of particulate kaolin. The dust contains 3wt% of the active ingredient.
VII. An intimate mixture of 30 parts by weight of compound no. 59, 92 20 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.
Vlll. A stable aqueous dispersion of 40 parts by weight of compound no.
25 61, 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which dispersion can be further diluted.
IX. A stable oily dispersion of 20 parts by weight of compound no. 67,30 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.
35 In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in a greater fungicidal action spectrum.

52 O.Z. 0050/41443 The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
5 Examples of fungicides which may be combined with the novel compounds are:
sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, 10 zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethy~enebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfides, 15 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N -propylenebisdithiocarbamate, zinc N,N'-propylenebisdithioccarbamate and N,N -polypropylenebis(thiocarbamyl) disulfide;
20 nitro derivatives, such as dinitro(l-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, 30 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio[4,5-b]quinoxaline, methyl l-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 35 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 2 f3 3 ~

53 O.Z. 005~/41443 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 5 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilidej 2,4,5-trimethylfuran-3-carboxanilide, 10 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, 15 piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, 20 N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 25 N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1~2,4-triazol-1-yl)-butan-2-one, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol, ~-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine, 30 bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as 35 dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexachlorobenzene, DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate, 40 N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-~ichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, ..

54 O.Z. 0050/41443 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide, 1-[2-(2,4-dichlorophenyl)-pentyl]-lH-l,2,4-triazole, 2,4-difluoro-a-(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-5 chloro-2-aminopyridine, and 1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-lH-1,2,4-triazole.
Use examples For comparison purposes, 1-(4-(4-tert-butylphenyl)-cyclohexyl)-2,6-10 dimethylmorpholine (A) disclosed in EP 259,977, N,N-dimethyl-4-(cyclo-hexylmethyl)-cyclohexylamine (B) and 4(cyclohexylmethyl)-cyclohexylamine (C), both disclosed in U.S. 3,~81,766, and trans-4-tert-butyl-N-benzyl-cyclohexylamine (D) disclosed in Journal of Organic Chemistry, 48 (1983), pp. 3412-3422.
Use Example 1 Action on Plasmopara viticola 20 Leaves of potted vines of the MUller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse.
Then the leaves were infected with a zoospore suspension of Plasmopara 25 viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24C and then in a greenhouse for S days at from 20 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 5, 15, 39, 40, 50, 5g, 61, 62 and 67, applied as 0.025wt% spray liquors, have a better fungicidal action (100%) than prior art comparative agents A and C (75%).
35 Use Example 2 Action on Botrytis cinerea in paprika Paprika seedlings of the ~Neusiedler Ideal ~lite" variety were sprayed,40 after 4 to 5 leaves were well developed, to runoff with aqueous suspen-sions containing (dry basis) 80~o of active ingredient and 20% of emul-sifier. After the sprayed-on layer had dried, the plants were sprinkled with a conidial suspension of the fungus Botrytis cinerea, and placed at 22 to 24C in a chamber of high humidity. After 5 days, the disease had spread to such a great extent on the untreated plants that the necroses covered the major portion of the leaves.

.

~` 2~S~Y~ril~3 O.Z. 0050/41443 The results show that active ingredients 5, 15, 59, 61, 62 and 67, applied as 0.05% spray liquors, have a better fungicidal action (90%) than prior art active ingredients B, C and D (60%).

,

Claims (5)

1. A 4-(4-tert-butylphenyl)-cyclohexylamine and quaternary ammonium salts thereof of the formulae and where R1 is hydrogen, C1-C6-alkyl or C3-C6-alkenyl, R2 is C1-C12-alkyl, C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C3-C12-cycloalkyl, C4-C12-alkylcycloalkyl, C7-C12-bicycloalkyl, C3-C12-alkenyl, unsubstituted, monosubstituted, disubstituted or tri-substituted phenyl, or unsubstituted, monosubstituted, disubstituted or trisubstituted phenyl-(C1-C3)alkyl, the substituents in each case being identical or different and being C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, halogen, cyano, hydroxyl or nitro groups, with the proviso that R1 and R2 are not simultaneously C1-C4-alkyl, X? is a plant-tolerated acid anion, and plant-tolerated acid addition salts thereof.
2. A fungicidal agent containing an inert carrier and a fungicidally effective amount of a 4-(4-tert-butylphenyl)-cyclohexylamine or a quaternary ammonium salt thereof of the formulae and where R1 is hydrogen, C1-C6-alkyl or C3-C6-alkenyl, R2 is C1-C12-alkyl, C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C3-C12-cycloalkyl, C4-C12-alkylcycloalkyl, C7-C12-bicycloalkyl, C3-C12-alkenyl, unsubstituted, monosubstituted, disubstituted or tri-57 O.Z. 0050/41443 substituted phenyl, or unsubstituted, monosubstituted, disubstituted or trisubstituted phenyl-(Cl-C3)alkyl, the substituents in each case being identical or different and being C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, halogen, cyano, hydroxyl or nitro groups, with the proviso that R1 and R2 are not simultaneously C1-C4-alkyl, X? is a plant-tolerated acid anion, or a plant-tolerated acid addition salt thereof.
3. A process for combating fungi, wherein the fungi or the plants, seed, materials or the soil to be protected against fungus attack are treated with a fungicidally effective amount of a 4-(4-tert-butyl-phenyl)-cyclohexylamine or a quaternary ammonium salt thereof of the formulae and where R1 is hydrogen, C1-C6-alkyl or C3-C6-alkenyl, R2 is C1-C12-alkyl, C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C3-C12-cycloalkyl, C4-C12-alkylcycloalkyl, C7-C12-bicycloalkyl, C3-C12-alkenyl, unsubstituted, monosubstituted, disubstituted or tri-substituted phenyl, or unsubstituted, monosubstituted, disubstituted or trisubstituted phenyl-(C1-C3)alkyl, the substituents in each case being identical or different and being C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, halogen, cyano, hydroxyl or nitro groups, with the proviso that R1 and R2 are not simultaneously C1-C4-alkyl, X? is a plant-tolerated acid anion, or a plant-tolerated acid addition salt thereof.
4. A compound of the formula 1 as set forth in claim 1, where R1 is hydrogen and R2 is 4-tert-butylcyclohexyl.
5. A compound of the formula 2 as set forth in claim 1, where R2 is 4-tert-butylcyclohexyl and X? is iodide.

58 O.Z. 0050/41443 A compound of the formula 1 as set forth in claim 1, where R1 is hydrogen and R2 is cyclohexyl.
CA002037079A 1990-03-06 1991-02-26 4-(4-tert-butylphenyl)cyclohexylamines, and fungicides containing same Abandoned CA2037079A1 (en)

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