CA2038831A1

CA2038831A1 - N-(3-phenyl-2-methylpropyl and -methylprop-2-enyl)-azaheterocycles

Info

Publication number: CA2038831A1
Application number: CA002038831A
Authority: CA
Inventors: Matthias Zipplies; Hardo Siegel; Rainer Becker; Dieter Hermeling; Eberhard Ammermann; Gisela Lorenz
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1990-03-23
Filing date: 1991-03-22
Publication date: 1991-09-24
Also published as: KR910016730A; JPH04217967A; EP0447947A1; DE4009411A1

Abstract

O.Z. 0050/41504 Abstract of the Disclosure: N-(3-Phenyl-2-methylpropyl and -methylprop-2-enyl)-azaheterocycles I

I

where R1 is (CH3)3-O- or R2-O-C(CH3)2-, R2 is H or C1-C4-alkyl, Het is a 5-membered to 7-membered azahetero-aliphatic ring whose N atom is bonded to the remaining molecular moiety of I and the ring may also contain an oxygen or sulfur atom which is not adjacent to the nitrogen and/or may carry one or two of the following substituents: C1-C4-alkyl, R3-O-(CH2)n- in which R3 is hydrogen, C1-C4-alkyl or C1- or C2-alkoxycarbonyl and n is 0, 1 or 2, except for compounds in which R3-O- is .alpha. to the nitrogen, and the N-oxides and the salts of I are suit able as fungicides.

Description

` 2~3~3~
O.Z. 0050/41504 N-(3-Phenyl-2-methyl~ropyl and -methylProp~2-enyl~-zaheterocycles The present invention relat~s to novel N-(3-phenyl-2-methylpropyl and -methylprop-2-enyl)-azahetero-S cycle~ of the formula I
R I ~CH--..C--CH 2--Het where the dotted bond is a possible additional bond and R1 is tert-butoxy or a radical R -o-ctcH3~2-in which R% is hydrogen or Cl-C4-alkyl, and Het is a 5 membered to 7-mem~ered azaheteroaliphatic ring whose N a~om i~ bonded to the remaining molecular moiety of I and the ring may also contain, as a further hetero atom, an oxygen or ~ulfur atom which i~ no~ adjacent to the nitrogen and/or may furthermore carry one or two of the following sub~tituent~: Cl-C4-alkyl groups or radi-cal~ R3-o-(CH2) n~ ~ in which R3 is hydrogen, Cl-C4-alkyl or C~- or C2-alkoxycarbonyl and n i~ 0, 1 or 2, with ~he provi~o that R3-o~ i8 not ~ to the nitrogen of the heterocycle, an~ the N-oxide~ and the plant-tolerated acid addition ~alts and quaternary salt~ of I.
The pre~ent invention furthermore relates to a process for tha preparation of the~e compound~, their use a~ fungicides and ungicides which contain these com-pound~ a~ ackive 3ubstance~.
Th~ pre~ant invention also relate~ to 3-phenyl-2-mathylpropanal~ and 3-phenyl-2-methylprop-2-enal6 o the formula II
.
R 1 ~3CH--..f--CHO

in which Rl i~ tert-butoxy or ~O-C(CH3)2-, and 3-phenyl-2-methylpropanols of the formula III

.
.

. . .

- 2 - o.z. 0050/41504 Ql ~ OH IXI
as intermediates.
The literature discloses various fungicidal compounds of the type I which, instead of the radical Rl, contain tert~butyl (DE-A-26 56 747, DE-A-27 52 135, EP-A-O 333 and EP-A-243 940), tert-butyl which may be substituted by chlorine or alkyl (EP-A-174 565~, isopropyl (EP-A-6 992), C4-Cl2-alkyl, phenyl, cycloalkyl, cycloalkylalkyl or aralkyl (DE-A-27 52 096) or unsub-stituted or substituted phenoxy (EP-A-252 8703.
However, the abovementioned compounds are satis-factory only to a limited extent with regard to tolera-tion by plants as well as to their fungicidal action and the duration of action, particularly in the case of low application rates and concentrations.
It is an object of the present invention to provide novel fungicidal substance~.
We have found that this object is achieved by the N-~3-phenyli~obutyl)-azaheterocycles of the formula I
which were defined at the outset.
Tha substituents in the no~el compounds I have the following speciic meanings:
R1 is tert-butoxy or R2-O-C(CH3) 2 in which R2 is hydrogen or Cl-C4-alkyl, such as methyl, ethyl, isopropyl or tert-butyl, preferably tert-butoxy or l-methoxy-l-methylethyl, and Het is a 5-membered to 7-membered a~aheteroaliphatic ring whose N atom is bonded to the remsining molecular moiety I and the ring may also contain, as a hetero atom, an oxygen or sulfur atom which is not adjacent to the nitrogen atom and~or may carry one or two of the follow-ing substituents:
branched or ~traight-chain Cl-C4-alkyl, æuch as methyl, ethyl, isopropyl or tert-butyl, preferably methyl or ethyl, and R3-o-CH2- and R3-o-CHz-CH2- or R3-o-, which is not ~ to the - 3 _ o.z. 0050/41504 nitrogen atom of the heterocycle and in which R3 is hydrogen, Cl-C4-alkyl, such as methyl, ethyl, isopropyl or ter~-butyl, preferably methyl, or methoxycarbonyl or ethoxycarbonyl, in particulax pyrrolidin-l-yl, piperidin-l-yl, azepan-1-yl, morpholin-4-yl, thiomorpholin-4-yl, 2-methyl-pyrrolidin-l-yl, 3-methylpiperidin-1 yl, 4-tert-butyl-piperidin-l-yl,3,4-dimethylpiperidin-1-yl,3,5-dimethyl-piperidin-l-yl, 2,6-dLmethylpiperidin-l-yl, 3-methyl-4-ethylpiperidin-l-yl, 3-ethyl-4-methylpiperidin-1-yl, 2-methylazepan-l-yl, 3-methylazepan-1 yl, 2,5-dimethyl-morpholin-4-yl, cis-2,6-dimethylmorpholin~4-yl, 2,6-dimethylmorpholin-4-yl (cis-/tran~-mixture), 3-hydroxy-piperidin-1-yl, 4-hydroxypiperidin-1-yl, 4-methoxy-piperidin-1-yl~3-hydroxymethylpiperidin-1-yl,4-hydroxy-methylpiperidin-l-yl, 3-methoxymethylpiperdin-1-yl, 4-methoxymethylpiperidin-l-yl, 3-ethoxymethylpiperidin-1 yl, 3-propoxymethylpiperidin-1-yl, 3-acetoxymethyl-piperidin-l-yl, 3-propionoxymethylpiperidin-1-yl, 4-methoxyethylplperidin-l-yl and 3-acetoxyethylpiperidin l-yl .
Particularly suitable compound~ I are those in which R1 i text-butoxy or l-methoxy-l-methylethyl and Het is piperidin-l-yl, azepan-1-yl, mo~pholin-4-yl, 2,6-dimethylpiperidin-1-ylor Ci8 ~-2,b-dimethylmorpholin-4-yl.
Tho Example~ describe preferred compounds I.
The N-(3-phenyl-2-methylpropyl and -methylprop 2-enyl)-azeheterocycles are obtainable in various ways, preferably by the following methodss 1) Reduction of an aldehyde II in the presence of an azaheterocyclic rinq H-Het la) Catalytic reduction with hydrogPn R 1 J~ ~ H 2 ,~H e t II I
The hydrogenation is advantageously carried out 2~g~
- ~ - O.Z. 0050/~1504 in an autoclave at a hydrogen pressure of +;rom 2 to 100, preferably from 90 to 100, bar. A~ a rule, it i8 carried out in the ab~ence of a ~olvent or in an inert solvent or diluent, such aR benzene, toluene, tetrahydrofuran, dioxane or methanol, at a reaction temperature of from 0 to 180C, prefera~ly from 30 to 110C.
Advantageou~ly, the aldehyde II and the aza-heterocycle H-Het are used in a stoichiome~ric ratio, al~hough an excess of one component or the other, for example no~ more than 10~, may al~o be advisable in some ca~es .
Depending on the type of ca~aly~t used, compound~
I having a 2-methylpropylene or a 2-methylprop-2-enylene group a~ a bridge member may be obtained. Catalysts which lead to compounds I having a ~atura~ed bridge msmber are preferred.
Noble metals, such as rhodium and especially palladium, preferably in the form of supported catalysts containing silicate~, such as aluminum silicates and magnesium silicates, and in particular aluminum oxide, titanium dioxide or carbon a~ carrier~ are suitable as catalysts for the hydrogenation.
As a rule, the amount o~ catalyst is from 1 to 50~, preferably from 2 to 10%, based on the amount of aldehyde II used.
In a particularly 3uitable procecs for the preparation of the co~pound~ I having a 2-methylpropylene group as a bridg3 member, an aldehyde Rl-phenyl-4-C~O is reacted with propionaldehyde and an azaheterocycle H-Het 3Q under hydrogenating condition~, as described in DE-A-31 05 446.
lb) Catalytic reduction with a metal hydride ~ + H Het - -~ ~ Het Rl II Metal hydride R1 The reduction i8 advantageously carried out in an , .' : ' .
- . .

.

3 ~
- S - O.Z. 0050/4150~
inert solvent or diluenk, ~or example an alcohol, such as methanol or ethanol.
Example~ of suitable metal hydrides are alkali metal or alkaline earth metal hydrides or the alkali metal salts of boron hydrides or aluminum hydrides.
Sodium cyanoborohydride to which not more than 0.5 mole equivalent of a cocatalyst, such a~ zinc(II) chloride, may also be added, is particularly suitable.
As a rule, from 2 to 4 equivalents, based on the amount of aldehyde II used, of reducing agent are sufficient.
The aldehyde II and azaheterocycle H-Het ar~
usually used in a stoichiometric ratio, although an excess of one component or the other, for e~ample not more than 10%, may also be advisable in some cases.
The reaction is usually carried ou~ at atmos pheric pressure or under the autogenou~ pres~ure of the particular solvent.
The reaction tempera~ure is in general from 0 to 80C.
lc) Reduction with organic reducing agent~
A particularly suitable organic reducing agent is formic acid.
Regarding the solvent~, the stoichiometric amounts and the pressure, the data given for method lb) are applicable.
In the case of liquid reducing agent~, the raaction can al50 be carried out in tha absence of a solvent, in a large exce3~ of the reducing agent, for example not more than 10~, based on the amount of aldehyde II.
The reaction temperature i8 in general from 80 to 180C, preferably from 120 to 160C.
The reaction i~ u~ually carried out at atmos-pheric pres~ure.

2) Nucleophilic substitution by an azaheterocycle 3 8 ~
- 6 - O.Z. 0050/41504 ~L 3~se ~ ~Het R~ + H-Het IV
L is a nucleophilically ~3ubstitutable leaving group, in particular a halogen atom, such as chlorine, bromine or iodine, sulfonyl, such as methanesulfonyl, p-toluenesulfonyl or p-bromosulfonyl, or methylsulfate.
The reaction is advantageously carried out in a solvent or diluent, such as methanol, ethanol, aceto-nitrile, dime~hylformamide or dimethyl sulfoxide, or in a excess of the azaheterocycle.
Examples of suitable bases are alkali metal carbonates, such as sodi~m carbonate and potassium carbonate, bicarbonates, such as sodium bicarbonate and potassium bicarbonate, pyridine, 4-dimethylaminopyridine and triethylamine, or H-Het itself, in not less than a ~3toichiometric amoun~, ba~ed on the amoun~ of I~I, for complete conversion.
Advantageously, all starting compound~ are used in a roughly stoichiometric ratio, although an excess of one componen~ or the o~her, for example not more than lO~, may also be advisable in some cases.
If the a~aheterocycle i~ used as a solvent and/or as a base, H-Xet is pre~ent in a larger excess.
The reaction usually takes place at a suff icient rate at aboYe 30C. In general, the temperature is from 40 to 160C, preferably from 50 to 130C.
Since the reaction i~ not pre~sure-dependen~, it is advantageously carried out at atmospheric pres4ure.
3) Etherlfication of hydroxy compounds I [R1 =
R2-O-C(C~I3)2-]
~~~r~~~~~Het I) Base ~'~~~~~Het (CH3)2c ~ 2~ ~CI-C4- (CH3)2c ~
OH I Alkyl)-L O-(CI-C4-)All~yl I

The reaction iB advantageously carried out in an inert solvent, such as dimethylformamide.
As a rule, the alcohol i~ converted into its .
.

3 ~
- 7 - ~.Z. OOS0/41504 alcoholate by reaction with a strong base, for example sodium hydride or methylmagne~ium bromide, at about 0-~OC .
The subsequent substitution of the leaving group L by the alcoholate ion usually takes place at a suffi-cient ra~e at above 0C.
In general, the temperature is from 20 to 100C.
Advantageou~ly, the s~arting compounds are used in a stoichiometric ratio, although an excess of one component or the othex, for example no~ more than 10%, may b~ advisable in ~ome ca~es.
Since the reaction is not pre~sure dependent, it is prefera~ly carried out at atmospheric pressure.
Examples of the pxeparation ofcompounds of type I
which carry a hydroxyl, hydroxyalkyl or alkoxyalkyl group on the azaheterocycle are de~cribed in ~P-A 174 565.
The starting compounds II are obtainable by conventional methods of alcohol conden~ation reactions of para-substituted aromatic aldehydes with propionaldehyde and, if de~ired, ~ubqequent partial hydrogenation:

RI~CHO ~ 01~3 ,~ C~t. Rl~--II II
The saturated alde~ydes II can also be reduced by conventional methods to alcohol~ III, which can be reacted with a mineral acid or w1th a reactive compound HL in a conventional manner to give the in~ermediateR IV:
~0 H 2 ~OH HL ~L
Rl~ Cat. Rl Rl II (saturated) III IV
The aldehydes II which are novel comprise 3-t4~ hydroxy-1-mQthylethyl)phenyl]-2~methylpropenal, 3-~4-tl-hydroxy-1-methylethyl)phenyl]-2 ~methylpropanal, 3- [ 4-tert-butoxyphenyl ] -2-methylpropellal and 3-[4-~ert-butoxyphenyl~-2-methylpropanal.

.

~3~
~ 8 - O.Z. 0050/4150~
In the preparation of compounds I having a double bond in the isobutyl moiety, the E-isomers are predomin-antly formed as well as a small amount of the Z-isomers.
The two isomers can, if desired, be separated from one another in a conventional manner.
The N-oxide can be prepared by conventional methods from the compounds I, for example by reacting them with an organic peracid, such as metachloroper-benzoic acid.
Suitable acid addition salts are the salts of acids which do not adversely affect the fungicidal action of I, for example the salts of hydrochloric acid, hydro-bromic acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid, acetic acid~ propionic acid, lauric acid, palmitic acid, stearic acid, oxalic acid, malic acid, malonic acid, benzoic acid, methanesulfonic acid, dodecylbenzene ulfonic acid and saccharinic acid.
Other suitable salts are the N-alkylated, in particular methylated and ethylated, and the N-benzylated deriva-tives of the compounds I.
The novel compounds I having a saturated bridgemember contain a center of asymmetry. Furthermore, all acid addition salts, quaternary salts and N-oxides may contain one c0nter of asymmetry at the nitrogen atom of the heterocycle. All optically active compounds act as racemates, the form in which they are obtained in most preparation proce~ses, but can, if desired, al~o be separated inko the pure isomers by the conven~ional methods, for axample by chromatography ovex an optically active adsorbent.
The compounds I are suitable a fungicides.
Preparation Examples . .
, 3'L
g - O.Z. 0050/~150 E~AMPLE 3 4-[3-(4-tert-Butoxyphenyl)-2-methylpropyl]-cis-2,6-dlmethylmorpholine CH3 ~ N 0 CH3-C~

c~3 A mixture of 25 g (0.1 mol) of 3-(4-tert-butoxy-phenyl)-2-methylpropyl p-toluenesulfonate, 25 g (0022 mol) of cis-2,6-dimethylmorpholine and 100 ml of toluene was refluxed for 4 hours and then washed with 10%
strength by weiqht aqueous potassium hydroxide solution~
The organic phase was then worked up in a conventional manner to give the product. Yield: 60% of theory;
bp. 120C/0.1 mbar.
Intermediate A
3-(4-tert-Butoxyphenyl)-2-methylpropan-1-ol C~f OH
CH3--f c~3 10 g (0.58 mol) of p-tert-butoxybenzaldehyde were added to a solution of 600 ml of methanol and 13.3 g of 50~ strength aqueous sodium hydroxide solution in the course of about 10 minutes, a gentle stream of nitrogen being passed through the solution. The mixture was heated to about 40C, after which 36.4 g (0.62 mol) of propionaldehyde were added dropwise in ~he course of 1 hour. Aft~r:stirring had been carried out for a further 30 minutes, the pH was brought to 7.5-8 with 10% strength aqueous sulfuric acid, and the sodium ~ulfate fonmed was filtered off. The resulting 3-(4-tert-buto~yphenyl)-2-methylpropenal wa~ hydrog~nated using 15 g (0.26 mol) of Raney nickel as a catalyst in the course of 3 hours at a hydrogen pre sure of 100 bar and at 60C. After the pressure had been let down and the autoclave cooled, the .

, ~<~ 3 ~
- 10 - O.Z. 0050/41504 content of the autoclave was worked up in a conventional manner to give the product. Yield: 66%; bp.: 133C/0~5 mbar.
Intermediate B
3-(4-tert-Butoxyphenyl)-2 methylpropyl p-toluenesulfonate SO 2~3CH 3 o6 g (0.34 mol) of p-toluenesulfonyl chloride were added to a mixture of 77 g (0.34 mol) of 3-(4-tert-butoxyphenyl)-2-methylpropan-l~ol in 150 ml of pyridine at about 20C. Stirring was carried out for 2 hours, 10after which about 250 ml of toluene and 250 ml of water were added, ~he organic ph~e was ~eparated off and the solvent was removed under reduced pressure. The crude product was reacted, without further purification, with the azaheterocycle to give the end product.

4-{3-~4~ Methoxy-l-methylethyl)-phenyl]-2-methylprop~
2-en-l-yl}-cis-2,6-dimethylmorpholine CH3 1 ~ N ~

C~3 c~3 A mix~ure of 10.0 g (46 mmol) of 3-~4-(l-methoxy-1-methylethyl)-phenyl]-2-methylpropenal [prepared simi-larly to Example 3, Intermediate A, without ~he hydro-genation (yield 87% of theory, bp. ~20C/0.2 mbar)], 5.6 g (48.6 mmol) of cis-2,6-dimathylmorpholine, 3.7 g (27 mmol) of zinc chloride, 3.4 g (54 mmol) of ~odium cyano-borohydride and 100 ml of ab~olute methanol wa~ stirred for 48 hours at about 20C under a protective nitrogen atmosphere. The solvent was then removed under reduced pressure. The re~idue was taken up in about 150 ml of methyl tert-butyl ether and 40 ml of dilllte sodium 3 ~
- 11 - O.~. 0050/4150~
hydroxide solution, the phase~ were ~eparated and the organic portion was worked up in a conventional manner to give thP product. Yield. 54% of theory; bp. 150C/0.3 mbar.

4-{3-[4-(1-Methoxy-l-me~hyl2thyl)-phPnyl]-2-methylprop-yl}-cis-2,6 dimethylmorpholine ~
CH 3~ N () The compound was prepared similarly to Example 8 from 10 g (45 mmol) of 3-[4-tl~methoxy-1-methylethyl)-phenyl]-2-methylpropanal and 6.7 g (58 mmol) of cis-2,6-dimethylmorpholine, u ing 3.7 g (27 mmol) of zinc chlo-ride and 3 . 4 g (54 mmol) of sodium cyanoborohydride.
Yield: 76~ o~ theory; bp. 145C/0.4 mbar.
Intermediate C
3-[4-(1-Methoxy~1-methylethyl)-phenyl]-2-methylpropanal CH3-o ~ CHO

100 g (0.46 mol~ of 3-[4-~1-methoxy-1-methyl-ethyl)-phenyl]-2-methylpropenal (prepared similarly to Example 3, Intermediate A, wi~hout carrying out the hydrogenation (bp. 120C/0.2 mbar)] in 50 g of methanol were hydrogenated for 12 hours at 80C and at a hydrogen pres~ure of 50 bar over a metal cataly t. This consisted of palladium (O.5~) on alumina. After cooling had been carried out and the pressure let down, the mixture wa~
worked up in a conventional manner ~o obtain the product.
Yield: 62~ of theory; bp. 90-94C/0.2 mbar.
Table 1 shows further compound~ I, which were obtained, or are obtainable, similarly to the Example compound~.

'.' , .

.

~ ~J ~
- - 12 - O. Z . 0050/~1504 _ L

._ 3 _ ~'1 ~ ~ ~ ~ 3 O O O O O O C:~ O O O
o o ~ r o ~ o o _ _ _ _ _ e c ~
_ .__ ._ ._ ._ = ~ ._ ~ C _ _ C C _ ' _ _ ~-- ~ O c ~ O ~ c ~ ~ c ( ~ ~. _ :~
,_~9 ~~ ,_ ~D ~ 3 ~ ~ ~ --o 'O- ~ L ~ ~
OL ~`I L "I O S_~I ~ L S_ ~ ~ _ C ~ ~:7 ~ _ ~ ~ --~_~ I 'V ~ L VI I ~ O ~ V :-~ J
3. ~ v ~ ~: ^ ~ v ~ L e cc s s ~ ~ 1 ~ ~ ~ ~S
--v -c c s; c c c c ~ c ~ ~ c ~ ~ c s: c c o ~
o ~ c~
-~ x -- ~ -- -- x xo o o o o ~

~_ L ~ I_ L ~ ~ _ _ ~ V
L U U U U ~J ~J U ~ ~

_l , .~ ` , , . ., ' .

. ~: . : , . , ' '' ' ~3~
- 13 - O. Z . 0050/~1504 -_ o -_ , _ _ ,~
-- -- -- V . _ _ . _ , _ _ ,_ _ ~-- C L ~
-- :~ V C.J ~ Vl C C~
C ~ -- L ::~ -- C -- ~-- -- -- -- -- -- ._~
-- V (~1 '` V ~J I ^ -- -- V C ~ .--.-- C I -- CL
O C :~ -- C _ ~ -- _ -- C ~
~ X o X _ ~ X X ~ X X X X ~ X ~ ~-- J
X O ~-- O :~ 5 0 0 ~ O O O O ~C O -- V ~
-- ~' ~ ~ ~:1 v ~ ",, ~, ., -- ~ -- -- E~
.J L ~ v ~ J X
llJ .: CL S ~ n ~ S ~J ~ ~ I LI C 'D ~ 1J

'Oo O O O O O O O O O O O O O O O O O O
a~ c c ~ ~: c ~: c 1:: ~ c c c c c c c ~_ ~
.~

O

I , I , , ~ , , I I I
OU X X X X ~
O O O O ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ _ _ _ O~ L L L L C~ O O ~n C l O ~ ~ o ~ ~ ~ o ¢ Z

`
.:

', , ' ~ ' : ' ' : . '~' ' ' ;. ' ,' ' ' '" ' " ' ' ' ~ . , ~, : ' , ~ 3.,L

- 14 - O.Z. 0050/~1504 The N-(3-phenyl-2-methylp~opyl and -methylprop-2-enyl)-azaheterocycle~ I have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the cla~ consisting of the AscomycetQs and Basidio-mycetes. Some of them have systemic activity and can be used as foliage and soil fungicides.
They are particularly important for controlling a large number of fungi of various crops, such as wheat, rye, barlPy, oats, rice, corn, gras~, cotton, soybean, coffee, sugar cane, wine, fruit tree~ and ornamentals and vegetable plants, such as cucumbers, beans and cucurbitaceae, as well as on the seeds of these plant.~.
Th~y are particularly suitable for controlling the following plan~ di~ea~e~:
Erysiphe graminis (powdery mildew3 in cereals, Ery~iphe cichoracearum and Sphaerotheca fuliginea on cucurbitaceae, Podosphaera leucotricha on apple~, Uncinula necator on grapevines, Puccinia specie~ on cereals, Rhizoctonia species on co~ton and lawn~, Ustilago species on cereals and 3ugar cane, Venturia inaequalis ~cab) on apples, Helmintho~porium species on cereal~, Septoria nodorum on wheat, Bo~rytis cinerea (gray mold) on strawberriee and grape vines, Cercospora arachidlcola on peanut~, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoe~, ~u~arium and verticillium ~pecies on various plan~s, Pla~mopara viticola on grapevine~ and Alternaria specie~ on vegetables and fruit.
The compounds I ars ve~y par~icularly well suited to controlling Pyricularia oryzae on rice.
The compound~ are applied by spraying or du~ing ~, ~3 ~ 3 - 15 - O.Z. 0050/41504 the plants with the active ingredients or treating the seeds of the plants with the acti~e ingredienk3.
Application is effected before or after infecti on of the plants or seeds with the fungi.
They can be converted into the conventional formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend on the intended use~; they ~hould in any case ensure fine and uniform distribution of the N-(3-phenyl-2-methylpropyl and -methylprop-2-enyl~-aæahetero-cycle. The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and~or carriers, if required with the use of emulsifiers and dispersants; where wa~er i~ used as a diluent, other organic solvents may also be employed as auxiliary solvents. Suitable assistants for this purpose are essentially solvents, such a~ aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (egO mineral oil fractions), alcohol~ (eg. methanol or butanol), ketones (eg. cyclohexanone), amines (eg.
ethanolamine or dLmethylformamide) and water; carriers, such as ground natural minerals (eg. kaolins, clays, talc or chalk) and ground synthetic minerals (eg. finely divided silica or silicates); emulsifiers such aR non-ionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkyl ulfonates and arylsulfonates) and disper~an~s, such a~ lignin3ulfite waste liquors and methylcellulose.
The fungicides contain in general from 0.1 to 95, preferably from 0.5 to 90, % by weight of active ingredien~.
The application rate are from 0.02 to 3 kg of active ingredient per ha, depending on the type of effect desired. The novel compounds can also be used in mater--ial protection (timber protection), for example against Paecilomyces variotii.
The quantity of active ingredient required for A.
- 16 - O.Z. 0050/41504 seed treatment is in general from 0.001 to 50 g, prefer-ably 0.01 to 10 g, per kilogram of sesd.
The agents or the ready-to-use formulations prepared therefrom, such as solutions, emulsions, suspen-S sions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, atomizing, dusting, broadcasting, dressing or pouring.
Exampl~s of such formulations are:
I. A solution of 90 parts by weight of compound No. 3 and lO parts by weigh~ of N-methyl-~-pyrrolidone, which is suitable for use in the form of very small drops;
II. A mixture of 20 parts by weight of compound No. 4, 80 parts by welght of xylene, 10 parts by weight of the adduct of from 8 to 10 moles of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid, 5 partq by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil; a dispersion is obtained by finely dis~ributing the solution in water;
III. An aqueous dispersion of 20 parts by weight of compound No. 5, 40 parts by weight of cyclohexan-one~ 30 parts by weight of isobutanol and 20 parts by weight of the adduct of 40 moles of ~thylene oxide with 1 mole of castor oil;
IV. An aqueou~ di~persion of ~0 parts by weight o compound No. 8, 25 part~ by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling within a range from 210 to 280C and 10 part~ by weight of the adduct o~ 4 mole of ethylene oxid~ and l mole of castor oil;
V. A mixture, milled in a hammer mill, of 80 parts by weight of compound No. 9, 3 parts by weight of th~
~odium salt of diisobutylnaphthalene-~-sulfonic acid, 10 parts by weight of the ~odium salt of a ligninAulfonic acLd obtained from a sulfite waste - 1.7 - o.z. 0050/41504 liquor and 7 parts by weLghk of silica gel powder;
a spray liquor is obtained by finely distributing the mixture in water;
VI. An intLmate mixture of 3 parts by weight of com-pound No. 10 and 97 partR by weight of finely divided kaolin; this dusting agent contains 3% by weight of active ingredient;
VII. An intimate mixture of 30 parts by weight of compound No. 11, 92 parts by weight of silica gel powder and 8 parts by weight of liquid paraffin, which has been sprayed onto the surface of this silica gel; this formulation Lmparts good adhesion to the active ingredient;
VIII. A stable aqueous dispersion of 40 parts by weight of compound No. 12, 10 parts by weight of the sodium salt of a phenylsulfonic acid/ure~formalde-hyde condensate, 2 parts by weight of silica gel and 48 part~ by weight of water, which can be further diluted;
IX. A stable oily dispersion of 20 parts by weight of compound No. 13, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenol-sulfonic acid/urea/formaldehyda condensate and 68 parts by weight of a paraffinic mineral oil.
In these application forms, the novel agents may also be present to~ether with other active ingredients, for example with herbicide~, insecticides, growth regula-tors, fungicides or fertilizer~. In many ca3e~ the fungicidal action spectrum is increased on mixing with fungicides .
Use Example~
The comparison substance u ed was ~ 7~

- 18 ~ O.Z. 0050/41504 which is disclosed in EP-A 262 870 (compound No. 7).

Activity against brown rust on wheat Leaves of pot-grown wheat seedlings of the S Kanzler variety were dusted with spores of brown ru~t (Puccinia recondita). The pots were then placed for 24 hours at from 20 to 22C in a chamber at from 90 to 95%
relative humidity. During this tLme, the spores germina-ted and the germ tubes penetrated into the leaf tissue.
The infected plant~ were sprayed to run-off with 0.025~
strength aqueous spray liquor which contained 80~ of active ingredient and 20~ of emulsifier, the p rcentages being based on dry substance, and, after the spray coating had been dried on, were placed in a greenhouse at from 20 to 2~C and from 65 to 70% relative humidity.
After 8 days, the extent of development of rust funguR on the leaves was evaluated.
The result show~ that, when used as a 0.025 strength by weight spray liquor, active ingredients 9, 10, 11 and 13 have a better fungicidal action (95%) than the known comparative substance (30~).

Activity against wheat mildew Leaves of pot-grown wheat seedlings of the Fruhgold va~iety were sprayed with a 0.025~ strength aqueous spray liquor which contained 80% of active ingredient and 20% of emulsifier, the percen~ages being based on dry material, and, 24 hours after the spray coating had dried on, were dusted with spores of wheat mildew (Erysiphe graminis var. tritici). The test plants were then placed in a greenhouse at from 20 to 22C and from 75 to 80% relative humidity. After 7 days~ ~he extent of development of mildew wa~ evaluated.
The re~ult show~ that, when u~ed as a 0.025%
strength by weight spray liquor, active ingredients 3, 4, 5, 9, 10, ll and 13 have a better fungicidal action (98%~
than the known comparative substance (50~).

Claims

1. An N-(3-phenyl-2-methylpropyl or -methylprop-2-enyl)-azaheterocycle of the formula I

I

where the dotted bond is a possible additional bond and R1 is tert-butoxy or a radical R2-O-C(CH3)2-in which R2 is hydrogen or C1-C4-alkyl, and Het is a 5-membered to 7-membered azahetaroaliphatic ring whose N atom is bonded to the remaining molecular moiety of I and the ring may also contain, as a further hetero atom, an oxygen or sulfur atom which is not adjacent to the nitrogen and/or may furthermore carry one or two of the following substituents: C1-C4-alkyl groups or radi-cals R3-O-(CH2)n-, in which R3 is hydrogen, C1-C4-alkyl or C1- or C2-alkoxycarbonyl and n is 0, 1 or 2, with the proviso that R3-O- is not .alpha. to the nitrogen of the heterocycle, and the N-oxides and the plant-tolerated acid addition salts and quaternary salts of I.

2. A process for the preparation of an N-(3-phenyl-2-methylpropyl or -methylprop-2-enyl)-azaheterocycle as claimed in claim 1, wherein an aldehyde of the formula II

II

is reduced in the presence of an azaheterocyclic ring H-Het and the product is if desired, converted into the N-oxides or the plant-tolerated acid addition salts or quaternary salts.

3. A process for the preparation of an N-(3-phenyl-isobutyl)-azaheterocycle I as claimed in claim 1, wherein a 3-phenyl-2-methylpropanol of the formula III

O. Z . 0050/41504 III
is converted into a 3-phenyl-2-methylpropane derivative of the formula IV

IV

where L is a nucleophilically substituted leaving group, and this compound is reacted with an azaheterocycle H-Het in the presence of a base and the product is, if desired, converted into the N-oxides or the plant-tolerated acid addition salts or quaternary salts.

4. Use of an N-(3-phenyl-2-methylpropyl or -methyl-prop-2-enyl)-azaheterocycle I or its N-oxides or plant-tolerated hydro salts or quaternary salts as claimed in claim 1 as fungicides.

5. A fungicide containing one or more N-(3-phenyl-2-methylpropyl and -methylprop-2-enyl)-azaheterocycle of formula I, their N-oxides or their plant-tolerated hydro salts or quaternary salts as claimed in claim 1 and an inert liquid or solid carrier.

6. A method for controlling fungi, wherein a fungi-cidal amount of an N-(3-phenyl-2-methylpropyl or -methyl-prop-2-enyl)-azaheterocycle I, of its N-oxides and/or plant-tolerated hydro salts or quaternary salts as claimed in claim 1 is allowed to act on fungi, on plants threatened by fungal attack, on their habitat or on the seed of the threatened plants.

7. N-[3-(4-tert-Butoxyphenyl)-2-methylpropyl]-piperidine.

8. N-[3-(4-(1-Methoxy-2-methylethyl)-phenyl)-2-methylpropyl]-piperidine.

9. 4-[3-(4-tert-Butoxyphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine.

10. 4-[3-(4-(1-Methoxy-2-methylethyl)-phenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine.