.alpha.-Hydroxyethylphosphinates, and their production and use

Abstract

A compound of the formula: ##STR1## wherein X is a hydrogen atom, a chlorine atom or a bromine atom and R is an alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower alkoxy(lower)alkyl group, a lower alkylthio(lower)alkyl group, a phenoxy(lower)alkyl group, a phenylthio(lower)alkyl group, a phenyl(lower)alkoxy(lower)alkyl group, a phenyl(lower)alkylthio(lower)alkyl group, a lower cycloalkyl(lower)alkyl group, a lower alkyl(lower)cycloalkyl group, a halo(lower)cycloalkyl group, a lower alkylthio(lower)cycloalkyl group, a lower alkoxy(lower)cycloalkyl group, a lower cycloalkyl(lower)cycloalkyl group, a lower alkoxy(lower)alkoxy(lower)alkyl group, a phenyl(lower)alkyl group, a halophenyl(lower)alkyl group, a lower alkylphenyl(lower)alkyl group, a lower alkoxyphenyl(lower)alkyl group, a phenoxyphenyl(lower)alkyl group, a phenylphenyl(lower)alkyl group, a dihalophenyl(lower)alkyl group, a di(lower)alkylphenyl(lower)alkyl group, a di(lower)alkoxyphenyl(lower)alkyl group, a tri(lower)alkoxyphenyl(lower)alkyl group, a naphthyl(lower)alkyl group or an anthracenyl(lower)alkyl group, which is useful as a fungicide.

Description

The present invention relates to .alpha.-hydroxyethylphosphinates, and their production and use.

The said .alpha.-hydroxyethylphosphinates are representable by the formula: ##STR2## wherein X is a hydrogen atom, a chlorine atom or a bromine atom and R is an alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower alkoxy(lower)alkyl group, a lower alkylthio(lower)alkyl group, a phenoxy(lower)alkyl group, a phenylthio(lower)alkyl group, a phenyl(lower)alkoxy(lower)alkyl group, a phenyl(lower)alkylthio(lower)alkyl group, a lower cycloalkyl(lower)alkyl group, a lower alkyl(lower)cycloalkyl group, a halo(lower)cycloalkyl group, a lower alkylthio(lower)cycloalkyl group, a lower alkoxy(lower)cycloalkyl group, a lower cycloalkyl(lower)cycloalkyl group, a lower alkoxy(lower)alkoxy(lower)alkyl group, a phenyl(lower)alkyl group, a halophenyl(lower)alkyl group, a lower alkylphenyl(lower)alkyl group, a lower alkoxyphenyl(lower)alkyl group, a phenoxyphenyl(lower)alkyl group, a phenylphenyl(lower)alkyl group, a dihalophenyl(lower)alkyl group, a di(lower)alkylphenyl(lower)alkyl group, a di(lower)alkoxyphenyl(lower)alkyl group, a tri(lower)alkoxyphenyl(lower)alkyl group, a naphthyl(lower)alkyl group or an anthracenyl(lower)alkyl group.

In the above significances, the number of carbon atoms in the alkyl group is not more than 13. The term "lower" is generally intended to have not more than 8 carbon atoms, and the term "halo" is intended to mean chlorine, bromine, fluorine and iodine, inclusively. Preferred examples of R include C.sub.1 -C.sub.10 alkyl, C.sub.2 -C.sub.3 haloalkyl, C.sub.5 -C.sub.6 cycloalkyl, C.sub.1 -C.sub.3 alkoxyethyl, C.sub.1 -C.sub.2 alkylthioethyl, phenoxyethyl, phenylthioethyl, phenylmethoxyethyl, phenylmethylthioethyl, C.sub.3 -C.sub.6 cycloalkylmethyl, methylcyclohexyl, chlorocyclohexyl, methylthiocyclohexyl, methoxycyclohexyl, cyclohexylcyclohexyl, methoxyethoxyethyl, benzyl, halobenzyl, C.sub.1 -C.sub.4 alkylbenzyl, C.sub.1 -C.sub.4 alkoxybenzyl, phenoxybenzyl, phenylbenzyl, dichlorobenzyl, dimethylbenzyl, dimethoxybenzyl, trimethoxybenzyl, phenyl(C.sub.2 -C.sub.3)alkyl, chlorophenethyl, methoxyphenethyl, methylphenethyl, naphthyl(C.sub.1 -C.sub.2)alkyl and anthracenylmethyl.

Various fungicides having only a preventive effect have been used for control of plant diseases such as late blight and downy mildew which are caused by infection of Phycomycetes. However, their practical use was limited, since a sufficient controlling effect was hardly produced after the invasion of pathogenic fungi into plant bodies.

It has now been found that the .alpha.-hydroxyethylphosphinates (I) show not only a preventive effect but also a curative effect against plant diseases such as late blight and downy mildew caused by infection of Phycomycetes. Thus, they are useful as fungicides.

Examples of phytopathogenic fungi belonging to Phycomycetes, against which the .alpha.-hydroxyethylphosphinates (I) can exert their fungicidal activity, are as follows: Peronospora brassicae on vegetables and radish, Peronospora spinaciae on spinach, Peronospora tabacina on tobacco, Pseudoperonospora cubensis on cucumber, Plasmopara viticola on grape, Plasmopara nivea on Umbelliferae plants, Phytophthora cactorum on apple, strawberry and carrot, Phytophthora capsici on tomato and cucumber, Phytophthora cinnamomi on pineapple, Phytophthora infestans on potato, tomato and eggplant, Phytophthora nicotianae var. nicotianae on tobacco, kidney bean and onion, Pythium aphanidermatum on cucumber, Pythium sp. on spinach, Pythium sp. on wheat, Pythium debaryanum on tobacco, Pythium rot (i.e. P. aphanidermatum, P. debaryanum, P. irregulare, P. myriotylum, P. ultimum) on soybean and so forth.

Accordingly, they can be used as fungicides applicable to a plowed field, orchard, tea-garden, mulberry-garden, meadow, lawn and so on.

The .alpha.-hydroxyethylphosphinates (I), which may be racemic or optically active, can be produced by various procedures, of which typical examples are as follows:

Procedure (a):

An .alpha.-hydroxyethylphosphinic acid of the formula: ##STR3## wherein X is as defined above is reacted with an alcohol of the formula:

ROH (III) wherein R is as defined above to give the .alpha.-hydroxyethylphosphinate (I). The reaction is usually carried out by treating the .alpha.-hydroxyethylphosphinic acid (II) with the alcohol (III) in an amount of 1.0 to 10 equivalents with respect to the .alpha.-hydroxyethylphosphinic acid (II) in a solvent in the presence or absence of a catalyst at a temperature of the boiling point of the solvent for 1 to 24 hours.

Procedure (b):

An .alpha.-hydroxyethylphosphinate of the formula: ##STR4## wherein R' is an alkyl group or a cycloalkyl group and X is as defined above is reacted with the alcohol (III) to give the .alpha.-hydroxyethylphosphinate (I). The reaction is normally effected by treating the .alpha.-hydroxyethylphosphinate (I') with the alcohol (III) in an amount of 1.0 to 10 equivalents with respect to the .alpha.-hydroxyethylphosphinate (I') in a solvent in the presence or absence of a catalyst at a temperature of 60.degree. to 150.degree. C. for 1 to 24 hours.

Procedure (c):

The .alpha.-hydroxyethylphosphinic acid (II) is reacted with a diazoalkane of the formula:

R"--N.sub.2 (IV) wherein R" is a methyl group or an ethyl group. The reaction is ordinarily performed by treatment of the .alpha.-hydroxyethylphosphinic acid (II) with the diazoalkane (IV) in an amount of 1.0 to 3.0 equivalents with respect to the .alpha.-hydroxyethylphosphinic acid (II) in a solvent at a temperature of 0.degree. to 50.degree. C. for 1 to 5 hours.

The produced .alpha.-hydroxyethylphosphinates (I) may be subjected to usual work-up or, if necessary, to purification by chromatography, recrystallization or distillation.

In the above procedures, examples of the alcohol (III) are an alkanol (e.g. methanol, ethanol, propanol, isopropanol, butanol, 1-methylpropanol, 2-methylpropanol, pentanol, 1-methylbutanol, 1-ethylpropanol, 3-methylbutanol, 2-methylbutanol, 1,2-dimethylpropanol, hexanol, 1-methylpentanol, heptanol, 1-methylhexanol, 1-ethylpentanol, octanol, 1-methylheptanol, nonanol, decanol, undecanol, dodecanol, tridecanol), a cycloalkanol (e.g. cyclopropanol, 2-methylcyclopropanol, cyclobutanol, 2-methylcyclobutanol, cyclopentanol, 2-methylcyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 4-ethylcyclohexanol), a haloalkanol (e.g. 2-fluoroethanol, 2-chloroethanol, 2-boromoethanol, 3-chloroethanol), an alkoxyalkanol (e.g. 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 3-methoxypropanol), an alkoxyalkoxyalkanol (e.g. 2-(2-methoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol), an alkylthioalkanol (e.g. 2-methylthioethanol, 2-ethylthioethanol, 2-isopropylthioethanol), an aralkyloxyalkanol (e.g. 2-benzyloxyethanol, 2-(2-phenylethoxy)ethanol, 2-(4-chlorobenzyloxy)ethanol, 2-(1-naphthylmethoxy)ethanol), a cycloalkylalkanol (e.g. cyclohexylmethanol, 2-cyclohexylethanol), an aralkylthioalkanol (e.g. 2-benzylthioethanol, 2-(4-methylbenzylthio)ethanol), an aryloxyalkanol (e.g. 2-phenoxyethanol, 3-phenoxypropanol, 2-(4-chclophenoxy)ethanol), an arylthioalkanol (e.g. 2-phenylthioethanol, 4-phenylthiobutanol, 2-(1-naphthylthio)ethanol), a halocycloalkanol (e.g. 2-chlorocyclohexanol, 4-bromocyclohexanol), an alkoxycycloalkanol (e.g. 2-methoxycyclohexanol, 4-methoxycyclohexanol), an alkylthiocycloalkanol (e.g. 4-methylthiocyclohexanol, 4-ethylthiocyclohexanol), a cycloalkylcycloalkanol (e.g. 4-cyclohexylcyclohexanol, 2-cyclopentylcyclopentanol), a benzyl alcohol (e.g. benzyl alcohol, 2-fluorobenzyl alcohol, 3-fluorobenzyl alcohol, 4-fluorobenzyl alcohol, 2-chlorobenzyl alcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 2-bromobenzyl alcohol, 3-bromobenzyl alcohol, 4-bromobenzyl alcohol, 2-iodobenzyl alcohol, 3-iodobenzyl alcohol, 4-iodobenzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, 4-isopropylbenzyl alcohol, 4-t-butylbenzyl alcohol, 2methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 2-ethoxybenzyl alcohol, 3-ethoxybenzyl alcohol, 4-ethoxybenzyl alcohol, 2-propoxybenzyl alcohol, 3-propoxybenzyl alcohol, 4-propoxybenzyl alcohol, 2-isopropoxybenzyl alcohol, 3-isopropoxybenzyl alcohol, 4-isopropoxybenzyl alcohol, 4-butoxybenzyl alcohol, 3-phenoxybenzyl alcohol, 4-phenoxybenzyl alcohol, 4-phenylbenzyl alcohol, 2,4-dichlorobenzyl alcohol, 2,3-dichlorobenzyl alcohol, 2,5-dichlorobenzyl alcohol, 2,6-dichlorobenzyl alcohol, 3,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 3-trifluoromethylbenzyl alcohol, 2-fluoro-6-chlorobenzyl alcohol, 2,3-dimethoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 2,5-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 3,5-dimethoxybenzyl alcohol, 2,3,4-trimethoxybenzyl alcohol, 2,4,5-trimethoxybenzyl alcohol, 3,4,5-trimethoxybenzyl alcohol, 2,4,6-trimethoxybenzyl alcohol), a phenethyl alcohol (e.g. 1-phenylethanol, 2-phenylethanol, 1-(4-chlorophenyl)ethanol, 1-(2-fluorophenyl)ethanol, 1-(3-bromophenyl)ethanol, 1-(3,4-dichlorophenyl)ethanol, 1-(4-methylphenyl)ethanol, 1-(4-methoxyphenyl)ethanol, 1-(3-trifluoromethylphenyl)ethanol, 1-(2-chloro-4-bromophenyl)ethanol, 1-(3,4,5-trimethoxyphenyl)ethanol, 2-(4-methylphenyl)ethanol, 2-(4-chlorophenylethanol, 2-(2-methoxyphenyl)ethanol, 2-(4 -methoxyphenyl)ethanol, 2-(2,4-dichlorophenyl)ethanol), a phenylpropyl alcohol (e.g. 1-phenylpropanol, 2-phenylpropanol, 3-phenylpropanol), a naphthyl alcohol (e.g. 1-naphthylmethanol, 2-naphthylmethanol, 2-(b 1-naphthylethanol), an anthracenyl alcohol (e.g. 9-antracenyl alcohol), etc. Any of these alcohols can simultaneously play a role of the solvent for the reaction medium.

Preferred examples of the solvent in the procedure (a) or (b) are aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chlorobenzene), aliphatic hydrocarbons (e.g. hexane, heptane, ligroin), etc. Favorable examples of the solvent in the procedure (c) are ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, etc. They may be employed alone or in combination.

Examples of the catalyst which may be used in the procedure (a) or (b) are mineral acids (e.g. hydrochloric acid, sulfuric acid).

The starting racemic .alpha.-hydroxyethylphosphinic acid (II) can be produced according to the method disclosed in Annales, de Chimie et de Physique., 23, 289-362 (1891). They can be also produced by reacting an acetal of the formula:

XCH.sub.2 CH(OR').sub.2 (V) wherein X and R' are each as defined above with aqueous phosphinic acid in the presence of an acid catalyst (e.g. hydrochloric acid, sulfuric acid), usually at a temperature of 10.degree. to 100.degree. C. for 5 to 24 hours. The amount of the phosphinic acid may be 1.0 to 10 equivalents with respect to the acetal (V).

Some typical examples of the production of the .alpha.-hydroxyethylphosphinic acid (II) are shown in the following Reference Examples.

REFERENCE EXAMPLE 1

A solution of chloroacetaldehyde dimethylacetal (124.5 g) and phosphinic acid (50%, 132 g) was heated at 50.degree. to 60.degree. C. for 26 hours in the presence of conc. hydrochloric acid (10 ml). The resultant mixture was concentrated in vacuo to give 140 g (96.7%) of .alpha.-hydroxy-.beta.-chloroethylphosphinic acid. n.sub.D.sup.22.0 1.4970.

REFERENCE EXAMPLE 2

A solution of bromoacetaldehyde diethylacetal (197 g) and phosphinic acid (50%, 132.0 g) was heated at 60.degree. to 70.degree. C. for 48 hours in the presence of sulfuric acid (0.5 g). The resultant mixture was concentrated in vacuo to give 187.0 g (98.9%) of .alpha.-hydroxy-.beta.-bromoethylphosphinic acid. n.sub.D.sup.23 1.5105.

The optically active .alpha.-hydroxyethylphosphinates (I) can be produced by using an optically active .alpha.-hydroxyethylphosphinic acid (II) in the above mentioned procedures.

Practical and presently preferred embodiments for production of the .alpha.-hydroxyethylphosphinates (I) are shown in the following Examples.

EXAMPLE 1

A solution of .alpha.-hydroxyethylphosphinic acid (2.2 g) and 1-butanol (5.0 g) in benzene (30 ml) was heated for 3 hours with removal of water through a Dean-Stark apparatus. After cooling, the reaction mixture was washed with water, dried over magnesium sulfate and concentrated in vacuo to give 2.71 g (81.6%) of n-butyl .alpha.-hydroxyethylphosphinate (Compound No. 5).

EXAMPLE 2

A 10% solution of diazomethane in ether was gradually added to a stirred and ice-cooled solution of .alpha.-hydroxyethylphosphinic acid (3.0 g) in tetrahydrofuran (10 ml) until the color of the solution turned to yellow. After 10 minutes, the solvent was evaporated in vacuo. The residue was distilled to give 2.28 g (67.3%) of methyl .alpha.-hydroxyethylphosphinate (Compound No. 1).

EXAMPLE 3

A solution of Compound No. 1 (1.03 g) in ethanol (5 g) was heated under reflux for 5 hours. The solvent was evaporated in vacuo, and the residue was distilled to give 430 mg (38.47%) of ethyl .alpha.-hydroxyethylphosphinate (Compound No. 2).

EXAMPLE 4

In the same manner as in Example 2 but using (+)-.alpha.-hydroxyethylphosphinic acid (400 mg; [.alpha.].sub.D =+15.2.degree. (H.sub.2 O)), there was prepared 188 mg of methyl (+)-.alpha.-hydroxyethylphosphinate ([.alpha.].sub.D =+6.7.degree. (CHCl.sub.3)).

EXAMPLE 5

In the same manner as in Example 2 but using (-) -.alpha.-hydroxyethylphosphinic acid (340 mg; [.alpha.].sub.D =-15.5.degree. (H.sub.2 O)), there was prepared 184 mg of methyl (-)-.alpha.-hydroxyethylphosphinate ([.alpha.].sub.D =-7.1.degree. (CHCl.sub.3)).

EXAMPLE 6

A solution of .alpha.-hydroxyethylphosphinic acid (5.5 g) and benzyl alcohol (2.26 g) in benzene (50 ml) was heated for 8 hours with removal of water through a Dean-Stark apparatus. After cooling, the reaction mixture was washed with water, dried over magnesium sulfate and concentrated in vacuo to give 3.65 g (91.2%) of benzyl .alpha.-hydroxyethylphosphinate (Compound No. 36).

EXAMPLE 7

A solution of .alpha.-hydroxyethylphosphinic acid (5.5 g) and 4-chloro-.alpha.-phenethyl alcohol (1.56 g) in benzene (50 ml) was heated for 10 hours with removal of water through a Dean-Stark apparatus. The same work-up as in Example 6 gave 2.38 g (95.7%) of 4-chloro-.alpha.'-phenethyl .alpha.-hydroxyethylphosphinate (Compound No. 68).

EXAMPLE 8

A solution of .alpha.-hydroxy-.beta.-chloroethylphosphinic acid (2.9 g) and 1-butanol (10.0 g) in benzene (30 ml) was heated for 3 hours with removal of water through a Dean-Stark apparatus. The same work-up as in Example 6 gave 2.60 g (64.8%) of n-butyl .alpha.-hydroxy-.beta.-chloroethylphosphinate (Compound No. 82).

EXAMPLE 9

A solution of .alpha.-hydroxy-.beta.-bromoethylphosphinic acid (1.9 g) in tetrahydrofuran (10.0 g) was treated with diaxomethane in ether until the color of the solution turned to yellow. The same work-up as in Example 2 gave 1.70 g (83.7%) of methyl .alpha.-hydroxy-.beta.-bromoethylphosphinate (Compound No. 88).

Some examples of the .alpha.-hydroxyethylphosphinates (I) produced as above are shown in Table 1.

TABLE 1______________________________________CompoundNo. X R Physical constant______________________________________1 H CH.sub.3 n.sub.D.sup.24 1.4563 (98- 100.degree. C./0.15 mmHg)2 H C.sub.2 H.sub.5 n.sub.D.sup.20 1.4552 (93- 96.degree. C./0.06 mmHg)3 H n-C.sub.3 H.sub.7 n.sub.D.sup.20.0 1.45354 H i-C.sub.3 H.sub.7 n.sub.D.sup.25 1.45025 H n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.44856 H i-C.sub.4 H.sub.9 n.sub.D.sup.19 1.44627 H n-C.sub.5 H.sub.11 n.sub.D.sup.20 1.45058 H i-C.sub.5 H.sub.11 n.sub.D.sup.21 1.45059 H n-C.sub.6 H.sub.13 n.sub.D.sup.20 1.451510 H n-C.sub.7 H.sub.15 n.sub.D.sup.20.0 1.450311 H n-C.sub.8 H.sub.17 n.sub.D.sup.20.0 1.457212 H n-C.sub.10 H.sub.21 n.sub.D.sup.19.0 1.456113 H FCH.sub.2 CH.sub.2 n.sub.D.sup.25.0 1.452814 H ClCH.sub.2 CH.sub.2 n.sub.D.sup.18.0 1.474315 H ClCH.sub.2 CH.sub.2 CH.sub.2 n.sub. D.sup.21.0 1.465016 H ##STR5## n.sub.D.sup.20 1.473017 H ##STR6## n.sub.D.sup.20.0 1.475218 H CH.sub.3 OCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.442819 H C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.443520 H i-C.sub.3 H.sub.7 OCH.sub.2 CH.sub.2 n.sub.D.sup.18.0 1.448021 H CH.sub.3 SCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.498022 H C.sub.2 H.sub.5 SCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.488523 H ##STR7## n.sub.D.sup.20.0 1.566524 H ##STR8## n.sub.D.sup.20.0 1.518825 H ##STR9## n.sub.D.sup.20.0 1.526026 H ##STR10## n.sub.D.sup.20.0 1.563027 H ##STR11## n.sub.D.sup. 20.0 1.446028 H ##STR12## n.sub.D.sup.20.0 1.472229 H ##STR13## n.sub.D.sup.20 1.469030 H sec-C.sub.4 H.sub.9 n.sub.D.sup.20 1.446031 H ##STR14## n.sub.D.sup.21 1.563332 H ##STR15## n.sub.D.sup.20 1.556533 H ##STR16## n.sub.D.sup.20 1.523034 H ##STR17## n.sub.D.sup.20 1.565035 H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 n.sub.D.sup.20 1.490036 H ##STR18## n.sub.D.sup.20.0 1.532537 H ##STR19## n.sub.D.sup.20.0 1.511238 H ##STR20## n.sub.D.sup.19.5 1.508539 H ##STR21## n.sub.D.sup.20.0 1.510040 H ##STR22## n.sub.D.sup.20.0 1.549041 H ##STR23## n.sub.D.sup.19.5 1.550042 H ##STR24## n.sub.D.sup.21.0 1.545343 H ##STR25## n.sub.D.sup.20.0 1.563844 H ##STR26## n.sub.D.sup.19.5 1.565145 H ##STR27## M.P. 58-61.degree. C.46 H ##STR28## n.sub.D.sup.20.0 1.572047 H ##STR29## n.sub.D.sup.20.0 1.526148 H ##STR30## n.sub.D.sup.20.0 1.529049 H ##STR31## n.sub.D.sup.19.5 1.528650 H ##STR32## n.sub.D.sup.20.5 1.531051 H ##STR33## n.sub.D.sup.19.5 1.510252 H ##STR34## n.sub.D.sup.20.0 1.515053 H ##STR35## n.sub.D.sup.19.5 1.532054 H ##STR36## n.sub.D.sup.19.5 1.533555 H ##STR37## n.sub.D.sup.20.5 1.539056 H ##STR38## n.sub.D.sup.20.0 1.543257 H ##STR39## n.sub.D.sup.20.5 1.543658 H ##STR40## n.sub.D.sup.20.0 1.542059 H ##STR41## n.sub.D.sup.20.0 1.548860 H ##STR42## Waxy material61 H ##STR43## n.sub.D.sup.19.0 1.563262 H ##STR44## n.sub.D.sup.20.0 1.553763 H ##STR45## n.sub.D.sup.19.5 1.525864 H ##STR46## n.sub.D.sup.20.0 1.523665 H ##STR47## n.sub.D.sup.20.0 1.535066 H ##STR48## n.sub.D.sup.20.0 1.525667 H ##STR49## n.sub.D.sup.19.5 1.522568 H ##STR50## n.sub.D.sup.20.0 1.546069 H ##STR51## n.sub.D.sup.17.0 1.527870 H ##STR52## n.sub.D.sup.19.5 1.521071 H ##STR53## n.sub.D.sup.20.0 1.539072 H ##STR54## n.sub.D.sup.20.0 1.528673 H ##STR55## n.sub.D.sup.21.0 1.524874 H ##STR56## n.sub.D.sup.19.0 1.518575 H ##STR57## n.sub.D.sup.19.5 1.522076 H ##STR58## n.sub.D.sup.20.0 1.570577 H ##STR59## n.sub.D.sup.20.0 1.565378 H ##STR60## n.sub.D.sup.20.0 1.575079 Cl CH.sub.3 n.sub.D.sup.25 1.456280 Cl C.sub.2 H.sub.5 n.sub.D.sup.25 1.455581 Cl n-C.sub.3 H.sub.7 n.sub.D.sup.25 1.453082 Cl n-C.sub.4 H.sub.9 n.sub.D.sup.23 1.456083 Cl i-C.sub.4 H.sub.9 n.sub.D.sup.27 1.445884 Cl sec-C.sub.4 H.sub.9 n.sub.D.sup.27 1.448285 Cl n-C.sub.5 H.sub.11 n.sub.D.sup.27 1.446586 Cl i-C.sub.5 H.sub.11 n.sub.D.sup.27 1.443087 Cl n-C.sub.6 H.sub.13 n.sub.D.sup.27 1.442588 Br CH.sub.3 n.sub.D.sup.25 1.505089 Br C.sub.2 H.sub.5 n.sub.D.sup.25 1.500590 Br n-C.sub.3 H.sub.7 n.sub.D.sup.25.0 1.490591 Br i-C.sub.3 H.sub.7 n.sub.D.sup.25.0 1.486592 Br n-C.sub.4 H.sub.9 n.sub.D.sup.25 1.493593 Br i-C.sub.4 H.sub.9 n.sub.D.sup.25.0 1.489094 Br sec-C.sub.4 H.sub.9 n.sub.D.sup.25 1.486095 Br n-C.sub.5 H.sub.11 n.sub.D.sup.25 1.474996 Cl ##STR61## n.sub.D.sup.25 1.491297 Br ##STR62## n.sub.D.sup.25 1.496098 Cl ClCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.509599 Br ClCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5100100 Cl FCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5001101 Cl CH.sub.3 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.4950102 Cl C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.4865103 Br CH.sub.3 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5115104 Br i-C.sub.3 H.sub.7 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5105105 Br i-C.sub.5 H.sub.11 n.sub.D.sup.25 1.4723______________________________________

In actual application as fungicides, the .alpha.-hydroxyethylphosphinates (I) may be used alone without incorporation of other ingredients. For easier application, however, they are normally employed in admixture with solid or liquid carriers or diluents. The fungicidal compositions can be formulated into any of the ordinarily adopted forms such as, for example, dusts, granules, wettable powders, emulsifiable concentrates, fine particles, aqueous solutions, oil sprays, aerosols and tablets. Such compositions generally contain 0.1 to 99.9% by weight, preferably 2.0 to 80.0% by weight, of the active ingredient.

As the solid carriers or diluents usable for formulation of the fungicidal composition, there may be exemplified plant carriers (e.g. wheat flour, tobacco powder, soybean powder, walnut-shell powder, wooden powder, saw dust, wheat bran, bark dust, cellulose powder, extract residue), fibrous products (e.g. paper, cardboard, rag), crushed synthetic resins, clays (e.g. kaolin, bentonite, terra alba), talcs, other inorganic minerals (e.g. pyrophyllite, celicite, pumice, sulfur powder, diatomaceous earth, white carbon, activated carbon), chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), etc. As the liquid carriers or diluents, there may be employed water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters, nitriles, acid amides (e.g. methylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, carbon tetrachloride), etc.

In addition to the solid or liquid carriers or diluents as exemplified above, there may be used surfactants when desired. Examples of the surfactants are polyoxyethylene phenylphenol polymer, polyoxyethylene aklylaryl ether, sodium laurylsulfate, calcium alkylbenzenesulfonate, alkylsulfates, alkylsulfonates, alkylarylsulfonates, polyethyleneglycol ethers, polyvalent alcohol esters, etc. There may be also used adhesive agents, dispersing agents, stabilizers, etc. Specific examples thereof include casein, gelatin, starch, carboxymethyl cellulose, gum arabic, alginate, calcium ligninsulfonate, bentonite, molasses, polyvinyl alcohol, palm oil, agar, acid isopropyl phosphate, tricresyl phosphate, tall oil, epoxylated oil, surfactants, aliphatic acids and their esters, etc.

Moreover, the fungicidal composition may comprise other fungicides, insecticides, nematocides, acaricides, insect repellents, plant growth regulators, herbicides, fertilizers, soil improvers, etc.

Some typical examples of the fungicidal composition of this invention are shown below. In those examples, part(s) and % are by weight unless otherwise indicated.

EXAMPLE A

Compound No. 37 (2 parts), clay (88parts) and talc (10 parts) were thoroughly pulverized and mixed together to obtain a dust containing 2% of the active ingredient.

EXAMPLE B

Compound No. 6 (30 parts), diatomaceous earth (45 parts), white carbon (20 parts), a wetting agent (sodium laurylsulfate) (3 parts) and a dispersing agent (calcium ligninsulfonate) (2 parts) were thoroughly pulverized and mixed together to obtain a wettable powder containing 30% of the active ingredient.

EXAMPLE C

Compound No. 45 (50 parts), diatomaceous earth (45 parts), a wetting agent (calcium alkylbenzenesulfonate) (2.5 parts) and a dispersing agent (calcium ligninsulfonate) (2.5 parts) were thoroughly pulverized and mixed together to obtain a wettable powder containing 50% of the active ingredient.

EXAMPLE D

Compound No. 18 (20 parts), xylene (60 parts) and an emulsified (polyoxyethylene phenylphenol polymer type) (20 parts) were mixed together to obtain an emulsifiable concentrate containing 20% of the active ingredient.

EXAMPLE E

Compound No. 1 (50 parts), water (45 parts) and a wetting agent (polyoxyethylene alkylaryl ether type) (5 parts) were mixed together to obtain an aqeous solution containing 50% of the active ingredient.

A suitable amount of the fungicidal composition of the invention to be applied is generally from 10 to 1000 grams in terms of the active ingredient per 10 are. In case of the composition form such as a wettable powder, emulsifiable concentrate or aqueous solution, it is normally diluted with water and then applied. The concentration of the active ingredient upon application is preferably within the range of 0.1 to 1% by weight. In case of the composition form such as dust or granules, it is ordinarily applied as such. Since, however, the amount and concentration largely depend upon the composition forms, application times, application methods, application sites, diseases and crops, they may be increased or decreased appropriately.

The following examples show some typical test results supporting the excellent fungicidal activity of the .alpha.-hydroxyethylphosphinates (I). In these examples, the compound numbers correspond to those in Table 1. The compounds used for comparison are as follows:

______________________________________CompoundNo. Structure Remarks______________________________________ ##STR63## Commercially avail- able fungicide "chlorothalo nil"B ##STR64## Commercially available fungi- cide "alliete"C ##STR65## Commercially avail- able fungicide "zineb"D ##STR66## Commercially avail- able fungicide "maneb"______________________________________

EXAMPLE I

Seeds of cucumber (species: "sagamihanjiro") were sowed in soil filled in plastic pots and cultivated in a greenhouse for 14 days to obtain seedlings of cucumber having cotyledons. An aqueous dilution of the test compound in the form of an emulsifiable concentrate or wettable powder was applied onto the seedlings of foliar treatment. Then, the seedlings were grown in the greenhouse for 5 days. A spore suspension of Pseudoperonospora cubensis was sprayed onto the seedlings, which were placed at 20.degree. C. under a humid condition for 3 days and then grown at 20.degree. C. under the irradiation with a fluorescent lamp for 3 days. The state of infection of the test plants was observed, and the preventive value was calculated according to the following equation:

______________________________________Infection index State of infection______________________________________0 No infectious spot on leaf0.5 Infectious spots of less than 5% of the area of leaf1 Infectious spots of less than 20% of the area of leaf2 Infectious spots of less than 50% of the area of leaf4 Infectious spots of not less than 50% of the area of leafDegree of infection (%) = ##STR67##Preventive value (%) = ##STR68##______________________________________

The results are shown in Table 2.

TABLE 2______________________________________Compound Concentration of PreventiveNo. active ingredient (ppm) value (%)______________________________________ 1 200 100 2 200 100 3 200 100 4 200 100 5 200 100 6 200 100 7 200 100 8 200 100 9 200 9510 200 9011 200 7512 200 10013 200 10014 200 10015 200 10016 200 10017 200 10018 200 10019 200 10020 200 10021 200 10022 200 10023 200 10024 200 10025 200 10026 200 10027 200 10028 200 10029 200 10030 200 10036 200 10037 200 10040 200 10047 200 10048 200 10050 200 10053 200 10055 200 10058 200 9564 200 9066 200 10069 200 10074 200 10075 200 10076 200 8580 200 10082 200 9584 200 10088 200 10089 200 10091 200 10094 200 9397 200 91100 200 100105 200 100B 200 44______________________________________

EXAMPLE II

Seeds of cucumber (species: "sagamihanjiro") were sowed in soil filled in plastic pots and cultivated in a greenhouse for 14 days to obtain seedlings of cucumber having cotyledons. The seedlings were treated by soil-drench with an aqueous dilution of the test compound in the form of an emulsifiable concentrate or wettable powder. After 4 days, a spore suspension of Pseudoperonospora cubensis was sprayed onto the seedlings, which were placed at 20.degree. C. under a humid condition for 3 days and then grown at 20.degree. C. under irradiation with a fluorescent lamp for 4 days. The state of infection of the plants was observed, and the preventive value was calculated as in Example I. p The results are shown in Table 3.

TABLE 3______________________________________Compound Amount of active PreventiveNo. ingredient (g/are) value (%)______________________________________ 1 100 100 2 100 100 3 100 100 4 100 100 5 100 100 6 100 100 7 100 10010 100 10013 100 10014 100 10016 100 10018 100 10019 100 10021 100 10036 100 10037 100 10038 100 10039 100 10040 100 10041 100 10042 100 10043 100 10044 100 10045 100 10046 100 10047 100 10048 100 10049 100 10050 100 10051 100 10052 100 10053 100 10054 100 10055 100 10056 100 10057 100 10058 100 10059 100 10060 100 10061 100 10062 100 10063 100 10064 100 10065 100 10066 100 10067 100 10068 100 10069 100 10070 100 10071 100 10072 100 10073 100 10074 100 10075 100 10076 100 10077 100 10078 100 10079 100 10080 100 10081 100 10082 100 10083 100 10084 100 10085 100 10086 100 10087 100 10088 100 10089 100 10090 100 10091 100 10092 100 10093 100 10094 100 10095 100 10096 100 10097 100 10098 100 10099 100 100100 100 100101 100 100102 100 100103 100 100104 100 100105 100 100A 100 0B 100 25______________________________________

EXAMPLE III

Seeds of grape (species: "delaware") were sowed in soil filled in plastic pots and cultivated in a greenhouse for 1 month to obtain seedlings of grape at the 2 to 3-leaved stage. A spore suspension of Plasmopara viticola was sprayed onto the seedlings, which were placed at 23.degree. C. under a humid condition for 2 days. Then, an aqueous dilution of the test compound in the form of an emulsifiable concentrate or wettable powder was applied onto the seedlings by foliar treatment. Thereafter, the seedlings were grown at 23.degree. C. under irradiation with a fluorescent lamp for 14 days. The state of infection of the plants was observed, and the preventive value was calculated as in Example I.

The results are shown in Table 4.

TABLE 4______________________________________Compound Concentration of PreventiveNo. active ingredient (ppm) value (%)______________________________________ 1 500 100 2 500 100 3 500 100 4 500 10013 500 10014 500 10016 500 10018 500 10036 500 10037 500 10039 500 10040 500 10043 500 10047 500 10050 500 10053 500 10054 500 10061 500 10066 500 10068 500 10074 500 10076 500 10079 500 10080 500 10088 500 10089 500 10091 500 10096 500 100100 500 100B 500 69C 1000 0______________________________________

EXAMPLE IV

Seeds of potato (species: "danshaku") were sowed in soil filled in plastic pots and cultivated in a greenhouse for 2 months to obtain seedlings of potato. A spore suspension of Phytophthora infestans was sprayed onto the seedlings, which were placed at 20.degree. C. under a humid condition for 20 hours. Then, an aqueous dilution of the test compound in the form of an emulsifiable concentrate or wettable powder was applied onto the seedlings by foliar treatment. Thereafter, the seedlings were grown at 20.degree. C. under a humid condition for 6 days. The state of infection of the plants was observed, and the preventive value was calculated as in Example I.

The results are shown in Table 5.

TABLE 5______________________________________Compound Concentration of PreventiveNo. active ingredient (ppm) value (%)______________________________________ 1 500 95 2 500 90 3 500 90 5 500 93 8 500 9113 500 9514 500 9716 500 9218 500 9521 500 9036 500 9038 500 9542 500 8543 500 9154 500 9366 500 8771 500 9074 500 9180 500 8788 500 8389 500 9095 500 9399 500 95D 1000 0______________________________________

Claims

1. A compound of the formula: ##STR69## wherein X' is a chlorine atom or a bromine atom.