Saccharine salts of substituted hydroxypropylamines, compositions and use

Fungicidal saccharine salts of substituted hydroxypropylamines of the formula ##STR1## in which R.sup.1 is optionally substituted phenyl, phenoxy, phenylthio, phenylalkyl, phenoxyalkyl, or phenylthioalkyl, or optionally substituted cyclohexyl, cylohexyloxy, cyclohexylalkyl, cyclohexyloxyalkyl or cyclohexylthioalkyl, PA1 R.sup.2 is hydrogen or methyl, PA1 R.sup.3 is methyl or ethyl, and PA1 R.sup.4 and R.sup.5 each independently is alkyl or alkenyl, or PA1 R.sup.4 and R.sup.5, together with the nitrogen atom to which they are bonded, are an optionally substituted saturated heterocyclic radical which can optionally contain further hetero atoms.

The present invention relates to new saccharine salts of substituted 
hydroxypropylamines, a process for their preparation and their use as 
agents for combating pests. 
It is already known that saccharine salts of substituted amines, such as, 
for example, the saccharine salt of 5-amino-1,2,4-triazole or the 
saccharine salt of cyclohexylamine, have fungicidal properties (compare 
European Pat. No. 158,074). 
It is furthermore known that certain substituted hydroxyalkylamines, such 
as, for example, 
4-(4-t-butylphenyl)-3-methyl-1-(3-methyl-piperidin-1-yl)-butan-2-ol, have 
fungicidal properties (compare European Pat. No. 129,321). 
However, the activity of these already known compounds is not always 
completely satisfactory in all fields of use, especially when low amounts 
are applied and in the case of low concentrations. 
New saccharine salts of substituted hydroxypropylamines of the general 
formula (I) 
##STR2## 
in which R.sup.1 represents in each case optionally substituted phenyl, 
phenoxy, phenylthio, phenylalkyl, phenoxyalkyl or phenylthioalkyl, or 
represents in each case optionally substituted cyclohexyl, cyclohexyloxy, 
cyclohexylthio, cyclohexylalkyl, cyclohexyloxyalkyl or 
cyclohexylthioalkyl, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents methyl or ethyl and 
R.sup.4 and R.sup.5 independently of one another represent alkyl or 
alkenyl, or 
R.sup.4 and R.sup.5, together with the nitrogen atom to which they are 
bonded, represent an optionally substituted saturated heterocyclic 
radical, which can optionally contain further hetero atoms, 
have been found. 
The compounds of the formula (I) can be obtained as geometric and/or 
optical isomers or isomer mixtures of varying composition. Both the pure 
isomers and the isomer mixtures are claimed according to the invention. 
It has furthermore been found that the new saccharine salts of substituted 
hydroxypropylamines of the general formula (I) 
##STR3## 
in which R.sup.1 represents in each case optionally substituted phenyl, 
phenoxy, phenylthio, phenylalkyl, phenoxyalkyl or phenylthioalkyl, or 
represents in each case optionally substituted cyclohexyl, cyclohexyloxy, 
cyclohexylthio, cyclohexylalkyl, cyclohexyloxyalkyl or 
cyclohexylthioalkyl, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents methyl or ethyl and 
R.sup.4 and R.sup.5 independently of one another represent alkyl or 
alkenyl, or 
R.sup.4 and R.sup.5, together with the nitrogen atom to which they are 
bonded, represent an optionally substituted saturated heterocyclic 
radical, which can optionally contain further hetero atoms, 
are obtained by a process in which substituted hydroxypropylamines of the 
formula (II) 
##STR4## 
in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the 
abovementioned meaning, 
are reacted with saccharine, if appropriate in the presence of a diluent. 
Finally, it has been found that the new saccharine salts of substituted 
hydroxypropylamines of the general formula (I) have an action against 
pests. 
Surprisingly, the saccharine salts of substituted hydroxypropylamines of 
the general formula (I) according to the invention inter alia have a 
better fungicidal activity than the substituted amine saccharine salts 
which are known from the prior art, such as, for example, the saccharine 
salt of 5-amino-1,2,4-triazole or the saccharine salt of cyclohexylamine, 
and likewise have a considerably better fungicidal activity than the 
substituted hydroxyalkylamines known from the prior art, such as, for 
example, 
4-(4-t-butylphenyl)-3-methyl-1-(3-methylpiperidin-1-yl)-butan-2-ol, which 
are closely related compounds chemically and from the point of view of 
their action. 
Formula (I) provides a general definition of the saccharine salts of 
substituted hydroxypropylamines according to the invention. Preferred 
compounds of the formula (I) are those 
in which 
R.sup.1 represents phenyl, phenoxy, phenylthio, phenylalkyl, phenoxyalkyl 
or phenylthioalkyl with in each case 1 or 2 carbon atoms in the alkyl part 
and in each case optionally mono-, di-, tri-, tetra- or pentasubstituted 
by identical or different substituents, possible substituents on the 
phenyl in each case being: halogen, in each case straight-chain or 
branched alkyl, alkoxy and alkylthio with in each case 1 to 5 carbon atoms 
and halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 
1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such 
as, preferably, fluorine or chlorine atoms; or represents cyclohexyl, 
cyclohexyloxy, cyclohexylthio, cyclohexylalkyl, cyclohexyloxyalkyl or 
cyclohexylthioalkyl with in each case 1 or 2 carbon atoms in the alkyl 
part and in each case optionally monosubstituted or polysubstituted by 
identical or different substituents, possible substituents on the 
cyclohexyl in each case being: in each case straight-chain or branched 
alkyl and alkoxy with in each case 1 to 5 carbon atoms, trifluoromethyl 
and trifluoromethoxy, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents methyl or ethyl and 
R.sup.4 and R.sup.5 independently of one another represent straight-chain 
or branched alkyl with 1 to 8 carbon atoms, or represent straight-chain or 
branched alkenyl with 3 to 6 carbon atoms, or 
R.sup.4 and R.sup.5, together with the nitrogen atom to which they are 
bonded, represent a 5- to 7-membered saturated heterocyclic radical which 
has 1 or 2 hetero atoms, preferably nitrogen or oxygen, and is optionally 
mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- or 
decasubstituted by identical or different substituents, possible 
substituents being: methyl, ethyl and hydroxymethyl. 
Particularly preferred compounds of the general formula (I) are those 
in which 
R.sup.1 represents phenyl, phenylmethyl, phenoxymethyl, phenylthiomethyl, 
phenoxy or phenylthio, in each case optionally mono-, di- or 
trisubstituted by identical or different substituents, possible 
substituents on the phenyl in each case being: fluorine, chlorine, 
bromine, methyl, ethyl, n-propyl, i-propyl, n-, i-, s- or t-butyl, 
n-pentyl, 2-methyl-2-butyl, methoxy, ethoxy, n- or i-propoxy, t-butoxy, 
trifluoromethyl, trifluoromethoxy and trifluoromethylthio; or represents 
cyclohexyl, cyclohexylmethyl, cyclohexyloxymethyl, cyclohexylthiomethyl, 
cyclohexyloxy or cyclohexylthio, in each case optionally mono-, di- or 
trisubstituted by identical or different substituents, possible 
substituents on the cyclohexyl in each case being: methyl, ethyl, n- or 
i-propyl, n-, i-, s- or t-butyl, n-pentyl, 2-methyl-2-butyl, methoxy, 
ethoxy, n- or i-propoxy, t-butoxy, trifluoromethyl and trifluoromethoxy, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents methyl or ethyl and 
R.sup.4 and R.sup.5 independently of one another represent methyl, ethyl, 
n- or i-propyl, n-, i-, s- or t-butyl, n-pentyl, allyl, 2-butenyl or 
3-methyl-2-butenyl, or 
R.sup.4 and R.sup.5, together with the nitrogen atom to which they are 
bonded, represent 1-pyrrolidinyl, 1-piperidinyl, 1-piperazinyl, 
4-morpholinyl or 1-hexahydroazepinyl, in each optionally case mono-, di- 
or trisubstituted by identical or different substituents from the group 
comprising methyl, ethyl and hydroxymethyl. 
Especially preferred compounds of the general formula (I) are those 
in which 
R.sup.1 represents phenyl, phenoxy, phenoxymethyl, phenylthiomethyl, 
phenylthio, cyclohexyloxy, cyclohexylmethyl or cyclohexyloxymethyl, in 
each case optionally mono- or disubstituted by identical or different 
substituents from the group comprising chlorine, methyl, t-butyl and 
tri-fluoromethoxy, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents methyl and 
R.sup.4 and R.sup.5, together with the nitrogen atom on which they are 
located, represent 1-piperidinyl, 4-morpholinyl or 1-hexahydroazepinyl, 
optionally mono-, di- or trisubstituted by methyl. 
The following compounds of the general formula (I) may be mentioned 
specifically, in addition to the compounds mentioned in the preparation 
examples: 
##STR5## 
TABLE 1 
______________________________________ 
R.sup.1 R.sup.2 
R.sup.3 
______________________________________ 
##STR6## CH.sub.3 
CH.sub.3 
##STR7## 
##STR8## CH.sub.3 
CH.sub.3 
##STR9## 
##STR10## CH.sub.3 
CH.sub.3 
##STR11## 
##STR12## CH.sub.3 
CH.sub.3 
##STR13## 
##STR14## CH.sub.3 
CH.sub.3 
##STR15## 
##STR16## CH.sub.3 
CH.sub.3 
##STR17## 
##STR18## CH.sub.3 
CH.sub.3 
##STR19## 
##STR20## CH.sub.3 
CH.sub.3 
##STR21## 
##STR22## H CH.sub.3 
##STR23## 
##STR24## H CH.sub.3 
##STR25## 
##STR26## CH.sub.3 
CH.sub.3 
##STR27## 
##STR28## CH.sub.3 
CH.sub.3 
##STR29## 
______________________________________ 
If, for example, 
2,3,3-trimethyl-4-(3-methylphenyl)-1-(morpholin-4-yl)-2-butanol is used as 
the starting compound, the course of the reaction in the process according 
to the invention can be represented by the following equation: 
##STR30## 
Formula (II) provides a general definition of the substituted 
hydroxypropylamines required as starting substances for carrying out the 
process according to the invention. In this formula (II), R.sup.1, 
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 represent those radicals which have 
already been mentioned for these substituents in connection with the 
description of the substances of the formula (I) according to the 
invention. 
The substituted hydroxypropylamines are known in some cases (compare DE-OS 
(German Published Specification) 2,505,423). Some of them are the subject 
of German patent application P 3 627 071 of Aug. 9, 1986, corresponding to 
U.S. application Ser. No. 079,723, filed July 30, 1987, now pending. 
They are obtained, for example, by a process in which epoxides of the 
formula (III) 
##STR31## 
in which R.sup.1, R.sup.2 and R.sup.3 have the abovementioned meaning, 
are reacted with amines of the general formula (IV) 
##STR32## 
in which R.sup.4 and R.sup.5 have the abovementioned meaning, 
if appropriate in the presence of a diluent, such as, for example, 
n-butanol, and if appropriate in the presence of a catalyst, such as, for 
example, acetic acid, at temperatures between 40.degree. C. and 
200.degree. C., and, if appropriate, in a 2nd stage, the substituted 
hydroxypropylamines thus obtainable, of the formula (IIa) 
##STR33## 
in which R.sup.1-1 represents in each case optionally substituted phenyl, 
phenoxy, phenylalkyl or phenoxyalkyl and 
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the abovementioned meaning, 
are then hydrogenated in the phenyl ring in the customary manner with 
molecular hydrogen, if appropriate in the presence of a diluent, such as, 
for example, isopropanol, and if appropriate in the presence of a 
catalyst, such as, for example, ruthenium-on-carbon, at temperatures 
between 80.degree. C. and 200.degree. C. 
The epoxides of the formula (III) are known (compare, for example, U.S. 
Pat. No. 4,615,725) or they can be obtained in a generally known manner, 
for example by a process in which methyl ketones of the formula (V) 
##STR34## 
in which R.sup.1, R.sup.2 and R.sup.3 have the abovementioned meaning, 
are reacted either 
(.alpha.) with dimethyloxosulphonium methylide of the formula (VI) 
##STR35## 
in a manner in which is known per se in the presence of a diluent, such 
as, for example, dimethylsulphoxide, at temperatures between 20.degree. C. 
and 80.degree. C. (in this context, compare the information in J. Am. Soc. 
87, 1363-1364 [1965], or 
(.beta.) with trimethylsulphonium methyl-sulphate of the formula (VII) 
EQU [(CH.sub.3).sub.3 S.sup.+ ]CH.sub.3 SO.sub.4.sup.- (VII) 
in a manner which is known per se in the presence of an inert organic 
solvent, such as, for example, acetonitrile, and in the presence of a 
base, such as, for example, sodium methylate, at temperatures between 
0.degree. C. and 60.degree. C., preferably at room temperature (compare 
also the information in Heterocycles 8, 397 [1977]). 
The methyl ketones of the formula (V) are known (compare, for example, U.S. 
Pat. No. 4,549,900 and DE-OS (German Published Specification) 32 10,725), 
or they can be obtained in an analogous manner by the process described 
therein. 
The epoxides of the formula (III) can also be obtained by a process in 
which corresponding olefin are epoxidized by processes which are known in 
principle, for example by reaction with hydrogen peroxide or with 
peracids. 
The amines of the formula (IV) are generally known compounds of organic 
chemistry. 
Possible diluents for carrying out the process according to the invention 
are inert organic solvents. 
These include, in particular, ethers, such as ethylene glycol dimethyl 
ether or diethyl ether; ketones, such as acetone or butanone; nitriles, 
such as acetonitrile or propionitrile; amides, such as dimethylformamide, 
dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or 
hexamethylphosphoric acid triamide, or alcohols, such as methanol, ethanol 
or propanol. 
The reaction temperatures can be varied within a substantial range in 
carrying out the process according to the invention. The reaction is in 
general carried out at temperatures between 0.degree. C. and 100.degree. 
C., preferably at temperatures between 10.degree. C. and 80.degree. C. 
For carrying out the process according to the invention, equimolar amounts 
of saccharine are employed per mol of substituted hydroxylpropylamine of 
the formula (II). The two reaction partners are dissolved in a suitable 
solvent at the suitable reaction temperature and the solvent is then 
removed by distillation in vacuo. The salts thus obtainable are purified 
with the aid of customary purification methods, for example by 
recrystallization or reprecipitation. The occasionally amorphous salts are 
characterized with the aid of spectroscopic methods (IR; .sup.1 H-NMR). 
The active compounds according to the invention exhibit a powerful action 
against pests and can be used in practice for combating undesirable 
harmful organisms. 
The acitve compounds are suitable for use as agents for combating pests, 
above all as fungicides. 
Fungicidal agents in plant protection are employed for combating 
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, 
Ascomycetes, Basidiomycetes and Deuteromycetes. 
Some causative organisms of fungal diseases which come under the generic 
names listed above may be mentioned as examples, but not by way of 
limitation: Pythium species, such as, for example, Pythium ultimum; 
Phytophthora species, such as, for example, Phytophthora infestans; 
Pseudoperonspora species, such as, for example, Pseudoperonospora humuli 
or Pseudoperonospora cubensis; Plasmopara species, such as, for example, 
Plasmopara viticola; Peronospora species, such as, for example, 
Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, 
Erysiphe graminis; Sphaerotheca species, such as, for example, 
Sphaerotheca fuliginea; Podosphaera species, such as, for example, 
Podosphaera leucotricha; Venturia species, such as, for example, Venturia 
inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres 
or P. graminea (conidia form: Drechslera, syn: Helminthosporium); 
Cochliobolus species, such as, for example, Cochliobolus sativus (conidia 
form: Drechslera, syn: Helminthosporium); Uromyces species, such as, for 
example, Uromyces appendiculatus; Puccinia species, such as, for example, 
Puccinia recondita; Tilletia species, such as, for example, Tilletia 
caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago 
avenae; Pellicularia species, such as, for example, Pellicularia sasakii; 
Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium 
species, such as, for example, Fusarium culmorum; Botrytis species, such 
as, for example, Botrytis cinerea; Septoria species, such as, for example, 
Septoria nodorum; Leptosphaeria species, such as, for example, 
Leptosphaeria nodorum; Cercospora species, such as, for example, 
Cercospora canescens; Alternaria species, such as, for example, Alternaria 
brassicae and Pseudocercosporella species, such as, for example, 
Pseudocercosporella herpotrichoides. 
The good toleration, by plants, of the active compounds, at the 
concentrations required for combating plant diseases, permits treatment of 
above-ground parts of plants, of vegetative propagation stock and seeds, 
and of the soil. 
The active compound according to the invention can thereby be used with 
paraticularly good success for combating cereal diseases, such as, for 
example, against the causative organism powdery mildew of barley (Erysiphe 
graminis), or for combating rice diseases, such as, for example, against 
the rice spot disease causative organism (Pyricularia oryzae), or for 
combating vegetable diseases, such as, for example, against the cucumber 
mildew causative organism (Sphaerotheca fuliginea). It should be 
emphasized that the active compounds according to the invention also have 
systemic properties, in addition to a good protective activity. 
Depending on their particular physical and/or chemical properties, the 
active compounds can be converted to the customary formulations, such as 
solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, natural and synthetic materials impregnated with active 
compound, very fine capsules in polymeric substances and in coating 
compositions for seed, and furthermore in ULV cold mist and warm mist 
formulations. 
These formulations are produced in known manner, for example by mixing the 
active compounds with extenders, that is, liquid solvents, liquefied gases 
under pressure, and/or solid carriers, optionally with the use of 
surface-active agents, and/or foam-forming agents. In the case of the use 
of water as an extender, organic solvents can, for example, also be used 
as auxiliary solvents. As liquid solvents, there are suitable in the main: 
aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated 
aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, 
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as 
cylcohexane or paraffins, for example mineral oil fractions, alcohols, 
such as butanol or glycol as well as their ethers and esters, ketones, 
such as acetone, methyl ethyl ketone, methyl isobutyl ketone or 
cyclohexanone, strongly polar solvents, such as dimethylformamide and 
dimethylsulphoxide, as well as water; by liquefied gaseous extenders or 
carriers are meant liquids which are gaseous at normal temperature and 
under normal pressure, for example aerosol propellants, such as 
halogenated hydrocarbons as well as butane, propane, nitrogen and carbon 
dioxide; as solid carriers there are suitable: for example ground natural 
minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, 
montmorillonite or diatomaceous earth, and ground synthetic minerals, such 
as highly dispersed silicic acid, alumina and silicates; as solid carriers 
for granules there are suitable: for example crushed and fractionated 
natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as 
well as synthetic granules or inorganic and organic meals, and granules of 
organic material such as sawdust, coconut shells, corn cobs and tobacco 
stalks; as emulsifying and/or foam-forming agents there are suitable: for 
example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty 
acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl 
polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as 
well as albumin hydrolysis products; as dispersing agents there are 
suitable: for example ligninsulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, as well as natural phospholipids, such as 
cephalins and lecithins, and synthetic phospholipids, can be used in the 
formulations. Other additives can be mineral and vegetable oils. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain between 0.1 and 95 percent by weight 
of active compound, preferably between 0.5 and 90%. 
The active compounds according to the invention can be present in the 
formulations as a mixture with other known active compounds, such as 
fungicides, insecticides, acaricides and herbicides, and in mixtures with 
fertilizers and growth regulators. 
The active compounds can be used as such or in the form of their 
formulations or the use forms prepared therefrom, such as ready-to-use 
solutions, suspensions, wettable powders, pastes, soluble powders, dusts 
and granules. They are used in the customary manner, for example by 
watering, spraying, atomizing, scattering, dusting, foaming, brushing on 
and the like. It is furthermore possible to apply the active compounds by 
the ultralow volume method or to inject the active compound formulation or 
the active compound itself into the soil. The seed of the plants can also 
be treated. 
In the treatment of parts of plants, the active compound concentrations in 
the use forms can be varied within a substantial range. They are, in 
general, between 1 and 0.0001% by weight, preferably between 0.5 and 
0.001%. 
In the treatment of seed, amounts of active compound of 0.001 to 50 g per 
kilogram of seed, preferably 0.01 to 10 g, are generally required. 
In the treatment of soil, active compound concentrations of 0.00001 to 0.1% 
by weight, preferably 0.0001 to 0.02% by weight, are required at the place 
of action.

PREATION EXAMPLES 
Example 1: 
##STR36## 
0.7 g (0.00385 mol) of saccharine is added to 1.2 g (0.0039 mol) of 
4-(3-methylcyclohexyl)-1-(3-methylpiperidin-1-yl)-2,3,3-trimethyl-butan-2- 
ol in 40 ml of ethanol and the mixture is stirred at 50.degree. C. for 10 
minutes. After the solvent has been removed in vacuo, 1.9 g (100% of 
theory) of 
4-(3-methylcyclohexyl)-1-(3-methylpiperidin-1-yl)-2,3,3-trimethyl-butan-2- 
ol saccharine salt are obtained as an amorphous solid. 
.sub.1 H-NMR (CDCl.sub.3 /TMS): .delta.=3.7-4.0 (m, 2H); 3.55-3.1 (m, 3H); 
2.8 (m, 1H). 
Preparation of the starting compounds of the formula (II) 
##STR37## 
6.8 g (0.022 mol) of 
2,3,3-trimethyl-4-(3-methylphenyl)-1-(3-methylpiperidine)-2-butanol are 
dissolved in 100 ml of isopropanol and hydrogenated with 2 g of 5% 
strength ruthenium-on-carbon at 130.degree. C. under 200 atmospheres in 
the course of 4 hours. The catalyst is filtered off and the solvent is 
distilled off under a water pump vacuum. 
6.7 g (99% of theory) of 
2,3,3-trimethyl-4-(3-methylcyclohexyl)-1-(3-methylpiperidin-1-yl)-2-butano 
l of refractive index n.sub.D.sup.20 : 1.4886 are obtained. 
The structure is confirmed by the NMR spectra and the purity is confirmed 
by gas chromatography. 
##STR38## 
14 g (0.069 mol) of crude 2,3,3-trimethyl-4-(3-methylphenyl)-but-1-ene 
oxide in 10 ml of n-butanol are added dropwise to 6.9 g (0.07 mol) of 
3-methylpiperidine in 40 ml of n-butanol and 0.2 ml of glacial acetic acid 
and the mixture is heated under reflux for 18 hours. The solvent is then 
distilled off under a water pump vacuum. The residue is chromatographed 
over a silica gel column with the eluting agents methylene chloride and 
methylene chloride/methanol (9:1) in succession. 
13.6 g (65% of theory) of 
2,3,3-trimethyl-4-(3-methylphenyl)-1-(3-methylpiperidin-1-yl)-2-butanol 
are obtained as an oil with the refractive index n.sub.D.sup.20 of 1.5134. 
The structure is confirmed by the NMR spectra and the purity is confirmed 
by gas chromatography. 
Preparation of the precursors of the formula (III) 
##STR39## 
96 g (0.5 mol) of 2,2-dimethyl-1-(3-methylphenyl)-butan-3-one are dissolved 
in 630 ml of tetrahydrofuran. This solution is added dropwise to a 
suspension of 132.8 g (0.6 mol) of trimethylsulphoxonium iodide and 68 g 
(0.6 mol) of potassium tert.-butylate in 160 ml of dimethylsulphoxide, 
which has first been stirred at 60.degree. C. for 6 hours. The internal 
temperature increases to 27.degree. C. and the mixture is subsequently 
stirred at 45.degree. C. for 15 hours. The mixture is then poured onto 2 l 
of ice-water and extracted 4 times with 500 ml of methylene chloride each 
time and twice with 500 ml of water. The organic phase is dried and the 
solvent is distilled off in vacuo. 
97.3 g of the crude 2,3,3-trimethyl-4-(3-methylphenyl)-but-1-ene oxide are 
obtained. 
Preparation of the precursors of the formula (V) 
##STR40## 
161 g (3 mols) of potassium hydroxide are introduced into 1.25 l of 
cyclohexane with 24.4 g (0.075 mol) of tetrabutylammonium bromide, and a 
solution of 258 g (3 mols) of methyl isopropyl ketone and 210 g (1.511 
mols) of 3-methylbenzyl chloride is added under reflux. The mixture is 
then heated under reflux over a water separator for 30 hours and filtered 
off with suction over kieselguhr, and the filtrate is distilled in vacuo. 
100 g (35% of theory) of 2,2-dimethyl-1-(3-methylphenyl)-butan-3-one of 
boiling point 52.degree. C./0.15 mbar are thus obtained. 
The following saccharine salts of substituted hydroxypropylamines of the 
general formula (I) are obtained in a corresponding manner and in 
accordance with the general statements on the preparation: 
##STR41## 
TABLE 
__________________________________________________________________________ 
Ex. No. 
R.sup.1 R.sup.2 
R.sup.3 
Physical constant 
__________________________________________________________________________ 
##STR42## CH.sub.3 
CH.sub.3 
##STR43## 
m.p. 150-151.degree. C. 
3 
##STR44## CH.sub.3 
CH.sub.3 
##STR45## 
m.p. 174-175.degree. C. 
4 
##STR46## CH.sub.3 
CH.sub.3 
##STR47## 
m.p. 111-113.degree. C. 
5 
##STR48## CH.sub.3 
CH.sub.3 
##STR49## 
m.p. 108-110.degree. C. 
6 
##STR50## CH.sub.3 
CH.sub.3 
##STR51## 
m.p. 94-99.degree. C. 
7 
##STR52## CH.sub.3 
CH.sub.3 
##STR53## 
m.p. 147-150.degree. C. 
8 
##STR54## CH.sub.3 
CH.sub.3 
##STR55## 
.sup.1 HNMR*: 4.5-4.1 3.7-3.6 3.4-3.3 
9 
##STR56## CH.sub.3 
CH.sub.3 
##STR57## 
.sup.1 HNMR*: 3.5-2.5 
10 
##STR58## CH.sub.3 
CH.sub.3 
##STR59## 
.sup. 1 HNMR*: 4.2-3.55 3.7-3.2 0.85 
11 
##STR60## CH.sub.3 
CH.sub.3 
##STR61## 
.sup.1 HNMR*: 3.95-3.7 3.35 3.2-3.0 
12 
##STR62## H CH.sub.3 
##STR63## 
.sup.1 HNMR*: 1.0 
13 
##STR64## CH.sub.3 
CH.sub.3 
##STR65## 
mp. 114.degree.-120.degree. C. (decomp.) 
4 
14 
##STR66## CH.sub.3 
CH.sub.3 
##STR67## 
mp. 72.degree.-78.degree. C. 
15 
##STR68## CH.sub.3 
CH.sub.3 
##STR69## 
mp. 75.degree.-85.degree. C. 
__________________________________________________________________________ 
*The .sup.1 HNMR spectra were recorded in CDCl.sub.2 with 
tetramethylsilane (TMS) as the internal standard. The chemical shift as 
the .delta. value in ppm is given. 
USE EXAMPLES 
The compounds shown below were employed as comparison substances in the use 
examples which follow: 
##STR70## 
5-Amino-1,2,4-triazole saccharine salt and 
##STR71## 
Cyclohexylamine saccharine salt (both known from European Pat. No. 
158,074) and 
##STR72## 
4-(4-t-butylphenyl)-3-methyl-1-(3-methyl-piperidin-1-yl)-butan-2-ol (known 
from European Pat. No. 129,321) 
EXAMPLE A 
Erysiphe test (barley)/protective 
Solvent: 100 parts by weight of dimethylformamide 
Eulsifier: 0.25 parts by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the 
preparation of active compound until dew-moist. After the spray coating 
has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. 
hordei. 
The plants are placed in a greenhouse at a temperature of about 20.degree. 
C. and a relative atmospheric humidity of about 80%, in order to promote 
the development of powdery mildew pustules. 
Evaluation is carried out 7 days after the inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for example, by the compounds according to the preparation Examples 
2, 3, 4, 5, 6, 7, 12. 
EXAMPLE B 
Pyricularia test (rice)/protective 
Solvent: 12.5 parts by weight of acetone 
Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, and the 
concentrate is diluted with water and the stated amount of emulsifier, to 
the desired concentration. 
To test for protective activity, young rice plants are sprayed with the 
preparation of active compound until dripping wet. After the spray coating 
has dried on, the plants are inoculated with an aqueous spore suspension 
of 
Pyricularia oryzae. The plants are then placed in a greenhouse at 100% 
relative atmospheric humidity and 25.degree. C. 
Evaluation of the disease infestation is carried out 4 days after the 
inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for Example, by the compounds according to the preparation examples 
5, 6, 9 and 10. 
EXAMPLE C 
Pyricularia test (rice)/systemic 
Solvent: 12.5 parts by weight of acetone 
Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, and the 
concentrate is diluted with water and the stated amount of emulsifier, to 
the desired concentration. 
To test for systemic properties, standard soil in which young rice plants 
have been grown is watered with 40 ml of the preparation of active 
compound. 7 days after the treatment, the plants are inoculated with an 
aqueous spore suspension of Pyricularia oryzae. Thereafter, the plants 
remain in a greenhouse at a temperature of 25.degree. C. and a relative 
atmospheric humidity of 100% until they are evaluated. 
Evaluation of the disease infestation is carried out 4 days after the 
inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for example, by the compounds according to the preparation Examples 
5, 6, 9, 10 and 12. 
It will be understood that the specification and examples are illustrative 
but not limitative of the present invention and that other embodiments 
within the spirit and scope of the invention will suggest themselves to 
those skilled in the art.