CA2023125A1 - N-heterocyclomethylspiroheterocycles and fungicides containing them - Google Patents

Abstract

O.Z. 0050/41015 ABSTRACT OF THE DISCLOSURE: N-Heterocyclomethylspiroheterocycles of thegeneral formula I

(I), where A is a radical II, III or IV

, or

Description

202312~
O.Z. 0050/41015 N-Heterocyclomethylspiroheterocycl_c and fungicides containing them The present invention relates to N-heterocyclo-methylspiroheterocycles, fungicides containing them and methods for controlling fungi using these compounds.
It is known that piperidinomethylspirohetero-cycles, for example the compound IX (EP 281 842), have fun~icidal properties.

0~N~> (IX) However, the activity of this known compound is unsatis-factory, particularly at low application rates and concentrations.
We have found that N-heterocyclomethylspiro-heterocycle~ of the general formula I

H~C (I) R I ~(XO~A

where A is a radical II, III or IV

~N ~ ~ or -N ~ 3 ~ (ITI) ~Iv~

R2 is CH3, OH or OCH3, n is from 0 to 3, R3 is hydroxyl, acyloxy, alkoxy, unsubstituted or sub-stituted benzoyloxy, unsubstituted or substituted benzyl-oxy, unsubstituted or substituted alkyl or unsubstituted or substituted alkenyl, where the substituents are unsub-stituted or substituted aryl, hydroxyl, acyloxy, alkoxy 2023i25 - 2 - O.Z. 0050/41015 or benzyloxy, or R3 is aryl which is unsubstituted or substituted by halogen or by alkyl, X is oxygen, sulfur or methylene, Y is hydrogen or hydroxyl and R1 is hydrogen, alkyl or unsubstituted or substituted cyclohexyl or unsubstituted or substituted phenyl, and their addition salts with acids have an excellent fungi-cidal action against phytopathogenic fungi.
Particularly preferred for the purposes of the present invention are N-heterocyclomethylspirohetero-cycles of the general formula I, where A is a radical II, III or IV, as claimed in claim 1, n is 0 or 1, R2 is CH3, OH or OCH3, R3 is hydroxyl, C1-C~-acyloxy, C1-C8-alkoxy or benzoyloxy which is unsubstituted or monosubstituted to trisub-stituted by halogen or Cl-C4-alkyl, benzyloxy which is unsubstituted or monosubstituted to trisubstituted by halogen or C1-C~-alkyl, C1-C8-alkyl which is unsubstituted or substituted by OH, aryl (phenyl), C1-C4-acyloxy, benzoyloxy, C1-C8-alkoxy or benzyloxy, or C3- or C4-alkenyl which i8 unsubstituted or substituted by OH, aryl (phen-yl), C1-C4-acyloxy, benzoyloxy, C1-C8-alkoxy or benzyloxy, or phenyl which is unsubstituted or substituted by 1 to 3 halogen or Cl-C4-alkyl radicals, X is oxygen, sulfur or methylene, Y is hydrogen or hydroxyl, R1 i~ hydrogen, straight-chain or branched alkyl of 1 to 6 carbon atoms or phenyl which is unsubstituted or mono-substituted to trisubstituted by identical or different alkyl radicals of 1 to 4 carbon atoms or halogen radi-cals, or cyclohexyl which is unsubstituted or monosub-stituted to trisubstituted by identical or different C~-C4-alkyl or halogen radicals, and their addition salts with acids.
Surprisingly, the novel compounds have a better - 3 - O.Z. 0~5~
fungicidal action than the known compound of the formula IV, which is similar to the novel compounds.
Formula I gi~es the general definition of the novel compounds.
S In the formula, A is, for example, the trans- or cis-perhydroisoquinolyl or the trans- or cis-perhydroquinolyl radical or a mixture of the corresponding cis/~rans isomers or is the piperidinyl radical, R~ is methyl, hydroxyl or methoxy, n is, for example, 0 or 1, R3 is, for example, hydroxyl, acetoxy, benzoylo~y, Cl-C4-alkoxy, such as methoxy, ethoxy, isopropoxy or tert-butoxy, benzylo~y, Cl-C4-alkyl, such as methyl, ethyl, propyl, isopropyl, sec-butyl, tert-butyl or neopentyl, phenyl, halophenyl, such as 4-fluorophenyl, Cl-C4-alkyl-phenyl, such as 4 tert-butylphenyl, hydroxymethyl, Cl-C4 alkoxymethyl, such as methoxymethyl, ethoxymethyl or tert-butoxymethyl, acetoxymethyl, pivaloyloxymethyl, benzyloxymethyl, benzyl, hydroxyethyl, methoxyethyl~
tert-butoxyethyl, aceto~yethyl or benzoyloxyethyl/
X is, for example, oxygen, sulfur or methylene, oxygen being preferred, Y is hydrogen or hydroxyl, hydrogen being preferred, and Rl is, for exam]ple, hydrogen, methyl, ethyl, 2,2-dimethyl-propyl~ cyclohexyl or phenyl, methyl b~ing preferred.
Other preferred novel compound~ are the adducts of acids and compounds of the formula I in which A, n, X, Y, Rl, R2 and R3 have the abovementioned meaning3.
Such acids are, for example, mineral acids, such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid or nitric acid, or carboxylic acids, such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, succinic acid, tartaric acid, citric acid, salicylic a,~id, p-toluenesulfonic acid or dodecylbenzenesulfonic acid or generally proton-acidic compounds, eg. saccharin. Salts wi~h plant-tolerated ~02312~

- 4 - O.Z. 0050/41015 acid~ are preferred (plant-tolerated salts).
The novel compounds of the formula I may be obtained in the preparation a~ mixtures of stereoisomers (E/Z isomers, diastereomers, enantiomers), which can be separated into the individual components in a conven-tional manner, for example by crystallization or chroma-tography. ~oth the individual isomers and mixtures thereof can be used as fungicides and form the sub~ect of the invention.
The novel compounds of the formula I can be prep-ared in a conventional manner (cf. EP 281 842 and 278 352) by reacting a substituted spiroheterocycle of the general formula V
Rl H~3C~ ~ (V) c~ ,~
where R1 and X have the abovementioned meanings and Z is an electron-attracting, nucleophilically replaceable leaving group, with a heterocycloamine derivative of the general formula VI/VII/VIII

\ I`I~i ~, N YXR 3 or ~ ~
(VI) (Vll) tVIII) where R2, R3, Y and n have the abovementioned meanings, in the presence or absence of a diluent and in the presence or absence of an auxiliary base.
The substituted spiroheterocycles of the general formula (V) are known or can be prepared in a convention-al manner (cf. EP 281 842 or 278 352 and the literature cited therein). Some of the perhydro(iso)quinoline derivatives of the general formulae VI/VII are known;
those which are unknown can be prepared by conventional proce~ses, for example by catalytic hydrogenation of (iso)quinoline derivatives. The piperidine derivatives - 5 - O.Z. 0050/41015 of the general formula VIII are substantially known or can be prepared by conventional processes, by hydrogena-tion of pyridine derivatives or derivatization of 4-hydroxypiperidines or 4-hydroxyalkylpiperidines.

8-tert-Butyl-2-(perhydroisoquinolinomethyl)-1,4-dioxa-spiro[4,5]decane (compound No. 1.1) 10 g (34 mmol) of 8-tert-butyl-2-bromomethyl-1,4-dioxaspirot4,5]decane, 5.2 g (37.4 mmol) of perhydroiso-quinoline (isomer mixture) and 4.7 g (34 mmol) of potas-sium carbonate in 100 ml of acetonitrile were refluxed for 16 hours. The solvent was distilled off under reduced pressure, the resulting residue was taken up with dilute 5% strength NaOH and methyl tert-butyl ether, and the organic phase was washed twice with water, dried over Na2SO4 and evaporated down under reduced pressure. Frac-tionation of the crude product under reduced pressure gave 4.9 g of compound 1.1 (bp. 170C, 0.5 mbar).
Preparation of the starting compound O~Br 30.15 g (120 mmol) of tin(IV) chloride were added dropwise to 115.5 g (750 mmol) of 4-tert-butylcyclohexa-none in 700 ml of absolute dichloromethane at 5C, fol-lowed by the dropwise addition of 205.5 g (1.5 mol) of epibromohydrin ~C\~CH--CH2Br) o in 370 ml of absolute dichloromethane ln the course of 5 hours. The mixture was stirred~overnight at room temp-erature (20C), hydrolyzed with a solution of 42 g of ROH
in 180 ml of water while cooling, and worked up in a con-ventional manner. Distillation of the crude product (279 g) under reduced pressure gave 169 g (77.5~) of 8-tert-butyl-2-bromomethyl-1,4-dioxaspirot4,5]decane of boiling point 110C/0.2 mbar.

2023~2~

- 6 - O.Z. 0050/41015 PREPARATION E~L~MPLE 2 8-tert-~utyl-2-(4-tert-butylpiperidinomethyl)-1,4-dioxaspiro[4,5]decane (compound No. 2.5) 17.4 g (123.6 mmol) of 4-tert-butylpiperidine, 9.0 g (30.9 mmol) of 8-tert-butyl-2-bromomethyl-1,4-dioxaspiro[4,5]decane (cis/trans mixture) and 4.3 g (30.9 mmol) of potassium carbonate in 100 ml of absolute di-methylformamide were heated at 150C for 8 hours. Some of the solvent was distilled off under reduced pressure, the residue was taken up with dilute aqueous sodium hydroxide solution/methylene chloride and the solution was worked up in a conventional manner.
The crude product was distilled under reduced pressure to give 4.5 g of a product of boiling point 190C (0.3 mbar) (diastereomer mixture).
The other novel compounds listed in Tables l and 2 can be prepared in a similar manner.

7 O.Z. 0050/41015 Table 1 H~3C
R1 ~ XO ~ A (I) No. A X R1 m.p./b. . C]
IR (film~ ~cm~1]

1.1 ~ O CH3 170C/0.5 mbar 1.2 ~ CH2 CH3 -N

1.3 ~ C2H5 1.4 ~ O cyclohexyl 1.5 ~ 0 phenyl -N

1.6 ~ O 2-methylpropyl -N

1.7 ~ O CH3 1.8 ~ C2H5 1.9 ~ CH2 CH3 1.10 ~ O CH3 -N

2023~2~

8 O.Z. 0050/41015 Table 1 (contd.) No. A X R1 m.p.~b.p.tC~
IR (fi m) [cm~

1.11 ~ C2H5 12 H3C ~ CH3 -N
N`~'~
1.13 ~ O CH3 H3C ~ CH3 H3C`_-N
1.15 ~ O CH3 1H3C ~ CH3 ~N`_~^~_~CH3 1.17 ~ O CH3 1.18 ~ CH3 CH3 l.l9 ~ O CH3 CH
1.20 ~ O CH3 .' ". ', . ~ .

~023~2~

g O.Z. 0050/41015 Table 1 (contd.) No. A X R1 IR (~i~mjP[cm 1.21 ~ O CH3 -N
trans isomer H

1.22 ~ O CH3 trans isomer H

1.23 ~ 0 CH3 cis isomer H

1.24 ~ O CH3 -N
cis isomer H

1.25 ~ O CH3 H
trans isomer H

1.26 ~ 0 CH3 H

cis isomer 1.27 ~ N~ CH3 H

202~2~

O.Z. 0050/41015 Table 1 (contd. ) No. A X Rl IR (~i~mj [cm ~1 N--1.28 ~ O CH3 OH

1.29 ~ O CH3 OH

1.30 ~ CH3 CH3 ~ N' 1.31 ~ O CH3 OH
~ N--1.32 ~ O CH3 HO
HO`_~^`_--^`N' 1.33 ~ O CH3 ~W
1.34 1 1 1 O CH3 H

~W
1.35 ¦ ¦ ¦ O CH3 H ~ ,.

. ' . ' ' ' .

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11 o.z. 0050/41015 Table 2 H3C ~ O ~ N ~ 3 No. Rl X R3 Y m(~j~ )b;p~ [~3 _ _ 2.1 CH3 C2H5 H
2.2 CH3 O n-C3H7 H
2.3 CH3 O i-C3H7 H
2.4 CH3 O sec-C4Hg H
2.5 CH3 O tert.-C4Hg H 190/0.3 mbar 2.6 CH3 O -c(cH3)2-cH2-cH3 H
2.7 CH3 O -C(CH3)2-CH2-C(CH3)3 H
2.8 CH3 O -OH H 160/0.15 mbar 2.9 CH3 O O-C-CH3 H

2.10 CH3 O H

2.11 CH3 O O-c-c6H5 H

2.12 CH3 O O-C-C(CH3)3 H
2.13 CH3 O -OCH3 H
2.14 CH3 o -OC2H5 H
2.15 CH3 O -O-CH(CH3)2 H
2.16 CH3 O -O-C(CH3)3 H
2.17 CH3 O -CH2-OH H
2. 18 CH3 O -CH20-CH3 H
2.19 CH3 O -CH2-O-C2H5 H

2.20 CH3 O -CH2-O-C-CH3 H
2.21 CH3 O -CH2-CH2-OH H

2.22 CH3 O -CH2-CH2-OCCH3 H
2.23 CH3 C6H5 H

`-" 2 ~

12 O.Z. 0050/41015 Table 2 tcontd.) No. R1 X R3 Y IR t~i~m);P~cm~~
2.24 CH3 C6H5 OH 200/0.1 mbar 2.25 CH3 O 4-F-C6H5 OH
2.26 CH3 O C6Hs-cH2- H oil 2.27 CH3 O C6Hs(cH2)2- H
2.28 CH3 O C6Hs(cH2)3- 1195,1103 cm~~
2.29 CH3 O 4-t-C4Hg-C6H4- H
2.30 CH3 S i-C3H7 H
2.31 CH3 S tert.-C4Hg H
2.32 CH3 S C(CH3)2-CH2cH3 H
2.33 CH3 S OH H
2.34 CH3 S O-CH3 H
2.35 CH3 S O-c2H5 H
R

2.36 CH3 S O-CCH3 H

2.37 CH3 S O-C-C(CH3)3 H
2.38 CH3 S C6H5 H
2.39 CH3 S C6H5 OH
2.40 CH3 CH2 i-C3H7 H
2.41 CH3 CH2 sec-C4Hg H
2.42 CH3 CH2 tert.-C4Hg H
2.43 CH3 CH2 C(CH3)2-CH2CH3 H
2.44 CH3 CH2 C(CH3) rcH2-c(cH3)3 H
2.45 CH3 CH2 OH H
2.46 CH3 CH2 O-CH3 H
2.47 CH3 CH2 O-C2H5 H
R

2.48 CH3 CH2 O-C-CH3 H

2.49 CH3 CH2 o-C-C(CH3)3 H
2.50 CH3 CH2 CH2-OH H
2.51 CH3 CH2 CH2-OCH3 H
2.52 CH3 CH2 CH2-O-C2H5 H

~023125 13 O.Z. 0050/41015 Table 2 (contd.) No. Rl X R3 Y IRm(~iSm);ptcm-l]

2.53 CH3 CH2 CH2-O-CCH3 H
2.54 CH3 CH2 CH2CH2OH H
2.55 CH3 CH2 CH2CH2-OCH3 H
1l 2.56 CH3 CH2 CH2CH2-OCCH3 H
2.57 CH3 CH2 C6H5 H
2.58 CH3 CH2 C6H5 OH
2.59 CH3 CH2 C6Hs-CH2 H
2.60 CH3 CH2 C6Hs-(CH2)3- H
2.61 CH3 CH2 4-tert.-C4Hg-C6H4 H
2.62 H C2H5 H
2.63 H O i-C3H7 H
2.64 H O t-C4Hg H
2.65 H O -OH H
2.66 H O -O-CH3 H
o 2.67 H 0 -O-CCH3 H
2.68 H C6H5 H
2.69 H C6H5 OH
2.70 H O C6HscH2 H
2.71 C2Hs C2H5 H
2.72 C2Hs O n-C3H7 H
2.73 C2Hs O i-C3H7 H
2.74 C2Hs 0 sec-C4Hg H
2.75 C2H5 O tert.-C4Hg H
2.76 C2H5 O -c~cH3)2-cH2-cH3 H
2.77 C2Hs O -C(CH3)2-CH2-C(CH3)3 H
2.78 C2Hs O -OH H

2.79 C2Hs 0 -OeoH3 H

2.80 C2Hs O -O-e-C2H5 H

.
~: .

~0~125 14 O.Z. 0050/41015 Table 2 (contd.) No. Rl X R3 Y IR (~i~m); [cm ~]
o 2.81 C2H5 -o-C-C(CH3)3 H

2.82 C2Hs 0 -O-C-C6Hs H
2.83 C2H5 O -OCH3 H
2.84 C2H5 o -OC2H5 H
2.85 C2Hs O -O-C(CH3~3 H
2.86 C2Hs O -CH2-OH H
2.87 C2Hs O -CH2-O-CH3 H
2.88 C2Hs O -CH2-Oc2H5 H
1l 2.89 C2Hs O -CH2-O-CCH3 H
2.90 C2Hs O -CH2-CH2-OH H

2.91 C2H5 O -CH2-CH2-CCH3 H
2.92 C2Hs C6H5 H
2.93 C2Hs O 4-tert--C4Hg~C6H4 H
2.94 cyclo- O tert.-C4Hg H
hexyl 2.95 C6Hs O tert.-C4Hg H

~02312~

O.Z. 0050/41015 Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the ASco-mycetes and Basidiomycetes classes. 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:
lS 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 species in cotton and lawns, 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 vegetables and fruit.
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 soil to be protected against fungal 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, 2 0 2 3 i 2 ~

16 O.Z. 0050/41015 for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents 5 such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenz-enes), paraffins (e.g., crude oil fractions), alcohols (e.g., 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 10 (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.
15 The fungicidal agents 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 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protect-ing materials (wood), for example against Paecilomyces variotii.
When the active ingredients are used for treating seed, amounts of from0.001 to 50, and preferably from 0.01 to 10, 9 per kg of seed are usually employed.
25 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.
30 Examples of formulations are given below.
I. 90 parts by weight of compound no. 1.1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 2.5 is dissolved in a mixture consisting of 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 the calcium salt of dodecylbenzene-40 sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

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17 o.z. 0050/41015 III. 20 parts by weight of compound no. 1.1 is dissolved in a mixture consisting of 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 pouring the solution into water and finely 5 distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 2.5 is dissolved in a mixture con-sisting of 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 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1.1 is well mixed with 3 parts by 15 weight of the sodium salt of diisobutylnaphthalene-a-sulfonic 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, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
Vl. 3 parts by weight of compound no. 2.5 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
25 VII. 30 parts by weight of compound no. 1.1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 2.5 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica get and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous 35 dispersion.
IX. 20 parts by weight of compound no. 1 is intimately mixed with 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 40 sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

~02~12~

18 O.Z. 0050/41015 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-5 gicides frequently results in an increase in the fungicidal spectrum.
Use examples The compound 8-tert-butyl-2-~piperidino-N-methyl)-1,4-dioxaspiro[4.5~-10 decane ~A) disclosed in EP 281,842 was used for comparison purposes.
Use Example 1 Action on wheat brown rust Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20 to 22C in a high-humidity (90 - 95%) chamber. During this period the spores germinated and the germ tubes penetrated the leaf 20 tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80~ of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20 to 22C and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredients nos. 1.1 and 2.5, applied as 0.006wt% spray liquors, had a better fungicidal action (100%) than prior art comparative agent A (75~).
30 Use Example 2 Action on cucumber mildew Leaves of pot-grown cucumber seedlings of the "Chinesische Schlange"
35 variety were sprayed at the two-leaf stage with a spore suspension of cucumber mildew. After about 20 hours, the plants were sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20-22C and a relative humidity of 70-80%. The 40 extent of fungus spread was determined after 21 days.
The results show that active ingredients nos. 1.1 and 2.5, applied as 0.025% spray liquors, had a better fungicidal action (100%) than prior art comparative agent A (40%).

Claims (8)

1. N-Heterocyclomethylspiroheterocycles of the general formula I

(I), where A is a radical II, III or IV

, or (II) (III) (IV) R2 is CH3, OH or OCH3, n is from 0 to 3, R3 is hydroxyl, acyloxy, alkoxy, unsubstituted or substituted benzoyloxy, unsubstituted or substituted benzyloxy, unsubstituted or substituted alkyl or unsubstituted or substituted alkenyl, where the substituents are unsubstituted or substituted aryl, hydroxyl, acyloxy, alkoxy or benzyloxy, or R3 is aryl which is unsubstituted or substituted by halogen or by alkyl, X is oxygen, sulfur or methylene, Y is hydrogen or hydroxyl, and R1 is hydrogen, alkyl or unsubstituted or substituted cyclohexyl or unsubstituted or substituted phenyl, and their addition salts with acids.

O.Z. 0050/41015

2. N-Heterocyclomethylspiroheterocycles as set forth in claim 1, where A is a radical II, III, or IV

, or (II) (III) (IV) R2 is CH3, OH or OCH3, R3 is hydroxyl, C1-C4-acyloxy, C1-C8-alkoxy or benzoyloxy which is unsubstituted or mono- to trisubstituted by halogen or C1-C4-alkyl, benzyloxy which is unsubstituted or mono- to trisubsti-tuted by halogen or C1-C4-alkyl, C1-C9-alkyl which is unsubsti-tuted or substituted by OH, aryl (phenyl), C1-C4-acyloxy, benzoyloxy, C1-C8-alkoxy or benzyloxy, or C3-C4-alkenyl which is unsubstituted or substituted by OH, aryl (phenyl), C1-C4-acyloxy, benzoyloxy, C1-C8-alkyloxy or benzyloxy, or phenyl which is unsubstituted or substituted by 1 to 3 halogen or C1-C4-alkyl radicals, n is 0 or 1, X is oxygen, sulfur or methylene, Y is hydrogen or hydroxyl, R1 is hydrogen, straight-chain or branched alkyl of 1 to 6 carbon atoms, phenyl whiçh is unsubstituted or mono- to trisubstituted by identical or different alkyl radicals of 1 to 4 carbon atoms or halogen radicals, or cyclohexyl which is unsubstituted or mono- to trisubstituted by identical or different C1-C4-alkyl or halogen radicals, and their addition salts with acids.

3. 8-(tert.-Butyl)-2-(isoquinolinomethyl)-1,4-dioxaspiro[4,5]decane.

4. 8-(Prop-2-yl)-2-(isoquinolinomethyl)-1,4-dioxaspiro[4,5]decane.

21 o.Z. 0050/41015

5. 8-(2-Methylbut-2-yl)-2-[(4-tert-butylpiperidino)methyl]-1,4-dioxa-spiro[4,5]decane.

6. 8-(tert.-Butyl)-1-oxa-2-t(4-tert-butylpiperidino)methyt]-spiro-[4,5]decane.

7. A fungicidal agent containing a solid or liquid carrier and a fungicidally effective amount of a compound of the formula I

(I), where A is a radical II, III or IV

, or (II) (III) (IV) R2 is CH3, OH or OCH3, n is from 0 to 3, R3 is hydroxyl, acyloxy, alkoxy, unsubstituted or substituted benzoyloxy, unsubstituted or substituted benzyloxy, unsubstituted or substituted alkyl or unsubstituted or substituted alkenyl, where the substituents are unsubstituted or substituted aryl, hydroxyl, acyloxy, alkoxy or benzyloxy, or R3 is aryl which is unsubstituted or substituted by halogen or by alkyl, X is oxygen, sulfur or methylene, Y is hydrogen or hydroxyl, and R1 is hydrogen, alkyl or unsubstituted or substituted cyclohexyl or unsubstituted or substituted phenyl, or an addition salt thereof with an acid.

22 0.Z. 0050/41015

8. A process for combating fungi, wherein a fungicidally effective amount of a compound of the formula I

(I), where A is a radical II, III or IV

, or (II) (III) (IV) R2 is CH3, OH or OCH3, n is from 0 to 3, R3 is hydroxyl, acyloxy, alkoxy, unsubstituted or substituted benzoyloxy, unsubstituted or substituted benzyloxy, unsubstituted or substituted alkyl or unsubstituted or substituted alkenyl, where the substituents are unsubstituted or substituted aryl, hydroxyl, acyloxy, alkoxy or benzyloxy, or R3 is aryl which is unsubstituted or substituted by halogen or by alkyl, X is oxygen, sulfur or methylene, Y is hydrogen or hydroxyl, and R1 is hydrogen, alkyl or unsubstituted or substituted cyclohexyl or unsubstituted or substituted phenyl, or an addition salt thereof with an acid, is allowed to act on the fungi, or the materials, areas, plants or seed threatened by fungus attack.