# Patent

## Title
Method for the preparation of vinyl compounds

## Abstract

This application is a divisional of copending application Ser. No. 487,670, filed on Apr. 22, 1983.

## Background
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:

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:

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:

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.

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.

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.

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).

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).

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).

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)).

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)).

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).

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).

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).

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. ______________________________________ Compound No.     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 1.4535 4       H     i-C.sub.3 H.sub.7 n.sub.D.sup.25 1.4502 5       H     n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.4485 6       H     i-C.sub.4 H.sub.9 n.sub.D.sup.19 1.4462 7       H     n-C.sub.5 H.sub.11 n.sub.D.sup.20 1.4505 8       H     i-C.sub.5 H.sub.11 n.sub.D.sup.21 1.4505 9       H     n-C.sub.6 H.sub.13 n.sub.D.sup.20 1.4515 10      H     n-C.sub.7 H.sub.15 n.sub.D.sup.20.0 1.4503 11      H     n-C.sub.8 H.sub.17 n.sub.D.sup.20.0 1.4572 12      H     n-C.sub.10 H.sub.21 n.sub.D.sup.19.0 1.4561 13      H     FCH.sub.2 CH.sub.2 n.sub.D.sup.25.0 1.4528 14      H     ClCH.sub.2 CH.sub.2 n.sub.D.sup.18.0 1.4743 15      H     ClCH.sub.2 CH.sub.2 CH.sub.2 n.sub. D.sup.21.0 1.4650 16      H ##STR5##        n.sub.D.sup.20 1.4730 17      H ##STR6##        n.sub.D.sup.20.0 1.4752 18      H     CH.sub.3 OCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.4428 19      H     C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.4435 20      H     i-C.sub.3 H.sub.7 OCH.sub.2 CH.sub.2 n.sub.D.sup.18.0 1.4480 21      H     CH.sub.3 SCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.4980 22      H     C.sub.2 H.sub.5 SCH.sub.2 CH.sub.2 n.sub.D.sup.20.0 1.4885 23      H ##STR7##        n.sub.D.sup.20.0 1.5665 24      H ##STR8##        n.sub.D.sup.20.0 1.5188 25      H ##STR9##        n.sub.D.sup.20.0 1.5260 26      H ##STR10##       n.sub.D.sup.20.0 1.5630 27      H ##STR11##       n.sub.D.sup. 20.0 1.4460 28      H ##STR12##       n.sub.D.sup.20.0 1.4722 29      H ##STR13##       n.sub.D.sup.20 1.4690 30      H     sec-C.sub.4 H.sub.9 n.sub.D.sup.20 1.4460 31      H ##STR14##       n.sub.D.sup.21 1.5633 32      H ##STR15##       n.sub.D.sup.20 1.5565 33      H ##STR16##       n.sub.D.sup.20 1.5230 34      H ##STR17##       n.sub.D.sup.20 1.5650 35      H     CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 n.sub.D.sup.20 1.4900 36      H ##STR18##       n.sub.D.sup.20.0 1.5325 37      H ##STR19##       n.sub.D.sup.20.0 1.5112 38      H ##STR20##       n.sub.D.sup.19.5 1.5085 39      H ##STR21##       n.sub.D.sup.20.0 1.5100 40      H ##STR22##       n.sub.D.sup.20.0 1.5490 41      H ##STR23##       n.sub.D.sup.19.5 1.5500 42      H ##STR24##       n.sub.D.sup.21.0 1.5453 43      H ##STR25##       n.sub.D.sup.20.0 1.5638 44      H ##STR26##       n.sub.D.sup.19.5 1.5651 45      H ##STR27##       M.P. 58-61.degree. C. 46      H ##STR28##       n.sub.D.sup.20.0 1.5720 47      H ##STR29##       n.sub.D.sup.20.0 1.5261 48      H ##STR30##       n.sub.D.sup.20.0 1.5290 49      H ##STR31##       n.sub.D.sup.19.5 1.5286 50      H ##STR32##       n.sub.D.sup.20.5 1.5310 51      H ##STR33##       n.sub.D.sup.19.5 1.5102 52      H ##STR34##       n.sub.D.sup.20.0 1.5150 53      H ##STR35##       n.sub.D.sup.19.5 1.5320 54      H ##STR36##       n.sub.D.sup.19.5 1.5335 55      H ##STR37##       n.sub.D.sup.20.5 1.5390 56      H ##STR38##       n.sub.D.sup.20.0 1.5432 57      H ##STR39##       n.sub.D.sup.20.5 1.5436 58      H ##STR40##       n.sub.D.sup.20.0 1.5420 59      H ##STR41##       n.sub.D.sup.20.0 1.5488 60      H ##STR42##       Waxy material 61      H ##STR43##       n.sub.D.sup.19.0 1.5632 62      H ##STR44##       n.sub.D.sup.20.0 1.5537 63      H ##STR45##       n.sub.D.sup.19.5 1.5258 64      H ##STR46##       n.sub.D.sup.20.0 1.5236 65      H ##STR47##       n.sub.D.sup.20.0 1.5350 66      H ##STR48##       n.sub.D.sup.20.0 1.5256 67      H ##STR49##       n.sub.D.sup.19.5 1.5225 68      H ##STR50##       n.sub.D.sup.20.0 1.5460 69      H ##STR51##       n.sub.D.sup.17.0 1.5278 70      H ##STR52##       n.sub.D.sup.19.5 1.5210 71      H ##STR53##       n.sub.D.sup.20.0 1.5390 72      H ##STR54##       n.sub.D.sup.20.0 1.5286 73      H ##STR55##       n.sub.D.sup.21.0 1.5248 74      H ##STR56##       n.sub.D.sup.19.0 1.5185 75      H ##STR57##       n.sub.D.sup.19.5 1.5220 76      H ##STR58##       n.sub.D.sup.20.0 1.5705 77      H ##STR59##       n.sub.D.sup.20.0 1.5653 78      H ##STR60##       n.sub.D.sup.20.0 1.5750 79      Cl    CH.sub.3         n.sub.D.sup.25 1.4562 80      Cl    C.sub.2 H.sub.5  n.sub.D.sup.25 1.4555 81      Cl    n-C.sub.3 H.sub.7 n.sub.D.sup.25 1.4530 82      Cl    n-C.sub.4 H.sub.9 n.sub.D.sup.23 1.4560 83      Cl    i-C.sub.4 H.sub.9 n.sub.D.sup.27 1.4458 84      Cl    sec-C.sub.4 H.sub.9 n.sub.D.sup.27 1.4482 85      Cl    n-C.sub.5 H.sub.11 n.sub.D.sup.27 1.4465 86      Cl    i-C.sub.5 H.sub.11 n.sub.D.sup.27 1.4430 87      Cl    n-C.sub.6 H.sub.13 n.sub.D.sup.27 1.4425 88      Br    CH.sub.3         n.sub.D.sup.25 1.5050 89      Br    C.sub.2 H.sub.5  n.sub.D.sup.25 1.5005 90      Br    n-C.sub.3 H.sub.7 n.sub.D.sup.25.0 1.4905 91      Br    i-C.sub.3 H.sub.7 n.sub.D.sup.25.0 1.4865 92      Br    n-C.sub.4 H.sub.9 n.sub.D.sup.25 1.4935 93      Br    i-C.sub.4 H.sub.9 n.sub.D.sup.25.0 1.4890 94      Br    sec-C.sub.4 H.sub.9 n.sub.D.sup.25 1.4860 95      Br    n-C.sub.5 H.sub.11 n.sub.D.sup.25 1.4749 96      Cl ##STR61##       n.sub.D.sup.25 1.4912 97      Br ##STR62##       n.sub.D.sup.25 1.4960 98      Cl    ClCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5095 99      Br    ClCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5100 100     Cl    FCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5001 101     Cl    CH.sub.3 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.4950 102     Cl    C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.4865 103     Br    CH.sub.3 OCH.sub.2 CH.sub.2 n.sub.D.sup.25 1.5115 104     Br    i-C.sub.3 H.sub.7 OCH.sub.2 CH.sub.2 n.sub.D.sup.25  1.5105 105     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.

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.

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.

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.

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.

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: Compound No.     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" ______________________________________

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 leaf 0.5             Infectious spots of less than 5% of the area of leaf 1               Infectious spots of less than 20% of the area of leaf 2               Infectious spots of less than 50% of the area of leaf 4               Infectious spots of not less than 50% of the area of leaf Degree of infection (%) = ##STR67## Preventive value (%) = ##STR68## ______________________________________

The results are shown in Table 2. ______________________________________ Compound   Concentration of Preventive No.        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              95 10         200              90 11         200              75 12         200             100 13         200             100 14         200             100 15         200             100 16         200             100 17         200             100 18         200             100 19         200             100 20         200             100 21         200             100 22         200             100 23         200             100 24         200             100 25         200             100 26         200             100 27         200             100 28         200             100 29         200             100 30         200             100 36         200             100 37         200             100 40         200             100 47         200             100 48         200             100 50         200             100 53         200             100 55         200             100 58         200              95 64         200              90 66         200             100 69         200             100 74         200             100 75         200             100 76         200              85 80         200             100 82         200              95 84         200             100 88         200             100 89         200             100 91         200             100 94         200              93 97         200              91 100        200             100 105        200             100 B          200              44 ______________________________________

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. ______________________________________ Compound     Amount of active Preventive No.          ingredient (g/are) value (%) ______________________________________ 1           100          100 2           100          100 3           100          100 4           100          100 5           100          100 6           100          100 7           100          100 10           100          100 13           100          100 14           100          100 16           100          100 18           100          100 19           100          100 21           100          100 36           100          100 37           100          100 38           100          100 39           100          100 40           100          100 41           100          100 42           100          100 43           100          100 44           100          100 45           100          100 46           100          100 47           100          100 48           100          100 49           100          100 50           100          100 51           100          100 52           100          100 53           100          100 54           100          100 55           100          100 56           100          100 57           100          100 58           100          100 59           100          100 60           100          100 61           100          100 62           100          100 63           100          100 64           100          100 65           100          100 66           100          100 67           100          100 68           100          100 69           100          100 70           100          100 71           100          100 72           100          100 73           100          100 74           100          100 75           100          100 76           100          100 77           100          100 78           100          100 79           100          100 80           100          100 81           100          100 82           100          100 83           100          100 84           100          100 85           100          100 86           100          100 87           100          100 88           100          100 89           100          100 90           100          100 91           100          100 92           100          100 93           100          100 94           100          100 95           100          100 96           100          100 97           100          100 98           100          100 99           100          100 100          100          100 101          100          100 102          100          100 103          100          100 104          100          100 105          100          100 A            100           0 B            100           25 ______________________________________

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. ______________________________________ Compound   Concentration of Preventive No.        active ingredient (ppm) value (%) ______________________________________ 1         500             100 2         500             100 3         500             100 4         500             100 13         500             100 14         500             100 16         500             100 18         500             100 36         500             100 37         500             100 39         500             100 40         500             100 43         500             100 47         500             100 50         500             100 53         500             100 54         500             100 61         500             100 66         500             100 68         500             100 74         500             100 76         500             100 79         500             100 80         500             100 88         500             100 89         500             100 91         500             100 96         500             100 100        500             100 B          500              69 C          1000             0 ______________________________________

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. ______________________________________ Compound   Concentration of Preventive No.        active ingredient (ppm) value (%) ______________________________________ 1         500             95 2         500             90 3         500             90 5         500             93 8         500             91 13         500             95 14         500             97 16         500             92 18         500             95 21         500             90 36         500             90 38         500             95 42         500             85 43         500             91 54         500             93 66         500             87 71         500             90 74         500             91 80         500             87 88         500             83 89         500             90 95         500             93 99         500             95 D          1000             0 ______________________________________

## Claims

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