Note: Descriptions are shown in the official language in which they were submitted.
~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~
R2 CH3
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
H--N 3
\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
R 3--C-R 4 4
where R3 and R4 are such that the radical
R3
-CH
R4
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
CH3-A 5
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
CH3
~R 2 A~\ 2a
CH3
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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The examples below are intended to illustrate the
preparation of the compounds according to the invention
in greater detail.
EXAMPLE 1
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.
EXAMPLE 2
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
EXAMPLE 3
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')).
EXAMPLE 4
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.
EXAMPLE 5
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.
EXAMPLE 6
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%).
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