JPH07145181A - Phosphinylalkanol derivative, its production and use thereof - Google Patents

Abstract

PURPOSE:To obtain the subject new compound having excellent herbicidal activity and useful as an active ingredient or intermediate for herbicides, by reaction between a phosphinylmethane and a dicarbonyl compound. CONSTITUTION:A new phosphinylalkanol derivative of formula I [R<2> and R<2> are OH, a 1-4C alkoxyl, a 7-9C aralkyloxy, a (substituted)phenoxy, a (substituted) amino, a 1-4C alkyl, a 7-9C aralkyl, phenyl; R<3> is OH, a 1-4C alkoxyl, a 7-9C aralkyloxy, a (substituted)amino, a 1-4C alkyl, a 7-9C aralkyl or phenyl] useful as an active ingredient or intermediate for herbicides {e.g. methyl 3-[bis(dimethylamino) phosophinyl]-2-hydroxy-2-methylpropioniconate} and a salt thereof. This derivative of formula I is obtained by reaction between a phosphinylmethane of formula II (R<1>a and R<2>a are the same with R<1> and R<2>, respectively) and a dicarbonyl compound of formula III (R<3>a is the same as R<3>).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phosphinylalkanol derivative, a method for producing the same, and a method for using this compound.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 56-115793 describes phosphonohydroxyacetic acid and its salts effective against herpetic virus. JP-A-59-67293 and JP-A-61-22
In 9890, a phosphorus-containing functional acetic acid derivative having a herbicidal action and a plant growth regulating action is described. Bulletin of the British Chemical Society (J. Chem. Soc., Chem. Comm., 1988 , 31
7-19), J. Med. Chem., 1974 , 17, 112-15 and Bio.
chemistry, 1990 , 29, 46, 10498-503: Chem. Abstr., 19
90 , 113, 207256k describes (hydroxymethyl) phosphonopropionic acid or its derivatives.
French Patent 2596393 describes (hydroxy) (methyl) phosphinylbutanoic acid and its derivatives. In addition, American Chemical Society Abstracts CA: 80 (23) 132
304p and CA: 67 (15) 73652g describe (hydroxy) (methyl) phosphinyl acetic acid derivatives. Further, (American Chemical Society Abstracts) CA: 93 (11) 114630f describes (hydroxy) (methyl) oxopropylphosphonates.

However, nothing has been known about the phosphinylalkanol derivatives according to the present invention.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have worked on the present invention with the object of establishing a method for synthesizing a phosphinylalkannol derivative and finding its usefulness.

[0005]

[Means for Solving the Problems] (Hydroxy) described in the above-mentioned French Patent No. 2596393.
Among (methyl) phosphinylbutanoic acid and its derivatives, phosphonobutanoic acid having both a hydroxy group and a methyl group and its derivatives are described. However,
The compound described in this French patent publication was a compound in which a hydroxy group and a methyl group were bonded to the carbon atom at the β-position of the carbonyl group. Also, American Chemical Society Abstract C
In the compounds described in A: 80 (23) 132304p and CA: 67 (15) 73652g, a methyl group, a hydroxy group, a carboxyl group and a phosphinyl group are bonded to the same carbon atom. Furthermore, in the (hydroxy) (methyl) oxopropylphosphonates described in Abstracts of Chemical Society of Japan CA: 93 (11) 114630f, the methyl group, the hydroxy group and the phosphinyl group are all bonded to the α carbon of the carbonyl group. ing.

The present inventors have conducted various studies on phosphinylalkanol derivatives in which a hydroxy group and a methyl group are bonded to the α-position of a carbonyl group, and a phosphinyl group is bonded to the β-position. Established its synthetic method,
They have found that they are useful as active ingredients of herbicides, and completed the present invention.

[0007]

The present invention has the following structural features. The first invention relates to a phosphinylalkanol derivative of the formula (I) of Chemical formula 5 and salts thereof with a base. [In the formula, R ¹ and R ² are each independently a hydroxyl group, C ¹ to C ⁴
Alkoxy group, C7-C9 aralkyloxy group, phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1-C4 alkyl group), amino group (this amino group is
C1-C4 alkyl group and / or C7-C9 aralkyl group
1 to 2 may be substituted), C1 to C4 alkyl group,
A C7-C9 aralkyl group or a phenyl group is shown. R ³ is
Hydroxyl group, C1 to C4 alkoxy group, C7 to C9 aralkyloxy group, amino group (this amino group may be substituted with 1 to 2 of C1 to C4 alkyl group and / or C7 to C9 aralkyl group) , C1-C4 alkyl group, C7-C9 aralkyl group or phenyl group]

[Chemical 5]

The second aspect of the present invention is to provide a compound represented by the formula (II-
It relates to a method for producing a phosphinylalkanol derivative of the formula (Ia) by reacting a phosphinylmethane of the a) with a dicarbonyl compound of the formula (III-a). [In the formula,
R ¹ a and R ² a are each independently a hydroxyl group, C1 to C4.
Alkoxy group, C7-C9 aralkyloxy group, phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1-C4 alkyl group), amino group (this amino group is
C1-C4 alkyl group and / or C7-C9 aralkyl group
1 to 2 may be substituted), C1 to C4 alkyl group,
A C7-C9 aralkyl group or a phenyl group is shown. R ³ a
Is a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, an amino group (this amino group may be substituted with 1 or 2 of a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group. Good), C1-C4 alkyl group, C7-C9 aralkyl group or phenyl group]

[Chemical 6]

The third aspect of the present invention is to provide a compound represented by the formula (Ib
And a method for producing a phosphinylalkanol derivative of the formula (Ic) by hydrogenolysis of the phosphinylalkanol derivative of the formula [In the formula, R ¹ b and R ² b are each independently a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, a phenoxy group (wherein the phenoxy group is 1 to 4 of a C1 to C4 alkyl group). 2 may be substituted), amino group (this amino group may be substituted with 1 to 2 of C1 to C4 alkyl group and / or C7 to C9 aralkyl group), C1 to C4 An alkyl group, a C7-C9 aralkyl group or a phenyl group is shown. R ³ b represents a hydroxyl group, C1 -C4 alkoxy, C7 to C9 aralkyloxy group, an amino group (the amino group, C1 -C4 alkyl groups and / or, C7 to C9
Optionally substituted with 1 to 2 aralkyl groups), C1 ~
A C4 alkyl group, a C7 to C9 aralkyl group or a phenyl group is shown. However, at least ^one of R ¹ b, R ² b, and R ³ b
One represents a benzyloxy group or an amino group to which at least one benzyl group is bonded. R ¹ c and R ² c
Are each independently a hydroxyl group, a C1-C4 alkoxy group,
C7-C9 aralkyloxy group, phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1-C4 alkyl group), amino group (this amino group is C1-C4 alkyl group and / or , C7 to C9 aralkyl groups may be substituted), C1 to C4 alkyl groups, C7 to C9 aralkyl groups, or phenyl groups. R ³ c is a hydroxyl group, C1 to C
4 alkoxy groups, C7 to C9 aralkyloxy groups, amino groups (this amino group is a C1 to C4 alkyl group and / or C7
~ C9 may be substituted with 1 to 2 aralkyl groups),
A C1-C4 alkyl group, a C7-C9 aralkyl group or a phenyl group is shown. However, at least among R1c, R2c, and R3c
1 represents a hydroxy group or debenzylated amino group]

[Chemical 7]

The fourth invention relates to a phosphinylalkanol derivative of the formula (I) of Chemical formula 8 and a herbicide containing a salt thereof with a base as an active ingredient. [Wherein R ¹ and R ²
Are each independently a hydroxyl group, a C1-C4 alkoxy group,
C7-C9 aralkyloxy group, phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1-C4 alkyl group), amino group (this amino group is C1-C4 alkyl group and / or , C7 to C9 aralkyl groups may be substituted), C1 to C4 alkyl groups, C7 to C9 aralkyl groups, or phenyl groups. R ³ is a hydroxyl group, C 1 to C ⁴
Alkoxy group, C7-C9 aralkyloxy group, amino group (this amino group is a C1-C4 alkyl group and / or C7
~ C9 may be substituted with 1 to 2 aralkyl groups),
C1 to C4 alkyl group, C7 to C9 aralkyl group or phenyl group]

[Chemical 8]

The present invention will be described in detail below. In the formula below, R ¹ , R ¹ a, R ¹ b, R ¹ c, R ² , R ² a, R ² b, R ²
c, R ³ , R ³ a, R ³ b and R ³ c have the same definition as above.

The reagents used in the series of reactions of the present invention are described. The following can be illustrated as a diluent.
water. Organic acids such as formic acid, acetic acid and propionic acid. benzene,
Hydrocarbons such as toluene, xylene, petroleum ether, pentane, hexane and heptane. Halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. Alcohols such as methanol, ethanol, isopropanol and t-butanol. Ethers such as diethyl ether, dimethoxyethane, diisopropyl ether, tetrahydrofuran, diglyme and dioxane. In addition, carbon disulfide, acetonitrile, acetone, ethyl acetate, acetic anhydride, pyridine, dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, hexamethylphosphoric amide and the like.

In addition to the above diluent, the reaction may be carried out in the presence of a base or an acid. Examples of the base used here include the following. Alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate. Carbonates of alkaline earth metals such as calcium carbonate and barium carbonate. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Oxides of alkaline earth metals such as magnesium oxide and calcium oxide. Alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium. Alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. Alkali metal hydrogen compounds such as sodium hydride and potassium hydride. Organometallic compounds of alkali metals such as methyllithium, ethyllithium, n-butyllithium and phenyllithium. Organic Grignard reagents such as methylmagnesium iodide, ethylmagnesium bromide and n-butylmagnesium bromide. Organometallic compounds of alkali metals and organocopper compounds that can be prepared from Grignard reagents and copper (I) salts. Alkali metal amides such as lithium diisopropylamide.
Ammonium hydroxides such as aqueous ammonia, benzyltrimethylammonium hydroxide, and tetramethylammonium hydroxide. Organic amines such as methylamine, ethylamine, n-propylamine, benzylamine, ethanolamine, dimethylamine, benzylmethylamine, dibenzylamine, triethylamine, triethanolamine and pyridine. As the acid, hydrochloric acid, hydrobromic acid,
Hydroiodic acid, perchloric acid, inorganic acids such as sulfuric acid and formic acid, acetic acid, butyric acid, organic acids such as p-toluenesulfonic acid, boron trifluoride-diethyl ether complex, boron trichloride,
Examples thereof include Lewis acids such as zinc chloride and aluminum chloride.

Organometallic compounds that undergo nucleophilic substitution at the reaction site include methyllithium, ethyllithium, n-propyllithium, i-propyllithium, n-butyllithium,
Examples thereof include alkali metal organometallic compounds such as phenyllithium, and Grignard reagents such as methylmagnesium iodide, ethylmagnesium bromide, n-butylmagnesium bromide, phenylmagnesium bromide, benzylmagnesium bromide, and 4-methylbenzylmagnesium bromide. Organometallic compounds of alkali metals and organocopper compounds that can be prepared from Grignard reagents and copper (I) salts can also be used. Examples of the hydrogenation catalyst include platinum, palladium, and nickel whose surface areas are increased to enhance their activity, and those which carry these metals on activated carbon, carbon, barium carbonate, or alumina. Described in each reaction step of the following description, the reaction temperature and the reaction time are all from the necessity of the reaction operation, within the range that does not adversely affect the yield, the reaction temperature shifts to the low temperature side or the high temperature side, the reaction It doesn't matter if the time is long.

Specific examples of the phosphinylalkanol derivative of the formula (I) include those shown in Table 1.

[Table 1] In Table 1, Ph represents a phenyl group and Bn represents a benzyl group.

To obtain a phosphinylalkanol derivative of formula (Ia), a carbanion is generated from a phosphinylmethane compound of formula (II-a) and added to a dicarbonyl compound of formula (III-a). You can do it. As the phosphinylmethane compound (II-a) used at this time, those prepared by the method described in the literature or commercially available reagents can be used.
Further, as shown in the reaction formula of Chemical formula 9, the chlorine atom of methylphosphonic dichloride is replaced by a compound of formula (IV-e) or a compound of formula (Ve) to give a reaction of formula (II-e) Phosphinylmethane compounds can also be prepared. Where R
¹ e and R ² e are each independently a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, a phenoxy group (wherein the phenoxy group is substituted with 1 to 2 C1 to C4 alkyl groups. Or an amino group (this amino group may be substituted with 1 to 2 C1 to C4 alkyl groups and / or C7 to C9 aralkyl groups).

[Chemical 9]

Further, as shown in the reaction formula of Chemical formula 10, the phosphorus atom of the phosphite derivative of the formula (VI-f) is electrophilically attacked by a methylating agent such as methyl iodide, and It is also possible to replace the hydrogen atom with a methyl group to prepare a phosphinylmethane compound of formula (II-f). At this time,
It is preferable to replace the hydrogen atom on the phosphorus atom with an organometallic compound such as sodium hydride or butyllithium, and then electrophilically attack with a methyl group. Where R ¹ f and
R ² f is each independently a C1 to C4 alkoxy group, C7 to
C9 aralkyloxy group, phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1 to C4 alkyl group), amino group (this amino group is C1 to C4 alkyl group and / or C7 To C9 aralkyl group which may be substituted with 1 to 2), C1 to C4 alkyl group, C7 to C9 aralkyl group or phenyl group.

[Chemical 10]

Methyl pyruvate, butane-2,3-dione,
Pentane-2,3-dione, 4-methylpentane-2,3-dione, hexane-2,3-dione, heptane-2,3-dione, 1-
Phenyl-1,2-propanedione and other compounds (III-a)
Can be prepared by the method described in the literature or commercially available reagents. In the reaction formula of Chemical formula 11, the dicarbonyl compound of formula (III-g) can also be prepared by reacting pyruvic chloride with the compound of formula (VII-g). R ³ g is a C1-C4 alkoxy group, a C7-C9 aralkyloxy group, an amino group (this amino group is a C1-C4
1 to 2 of an alkyl group and / or a C7 to C9 aralkyl group
May be substituted with individual).

[Chemical 11]

The phosphinylalkanol derivative of formula (Ic) is prepared by hydrogenolysis of the phosphinylalkanol derivative of formula (Ib) having a hydroxy group and / or an amino group to which a benzyl group is attached. Then, the benzyl group is removed. In this reaction, palladium carbon or Raney nickel is preferably used among the above hydrogenation catalysts. Of the above-mentioned acids, hydrochloric acid, perchloric acid and acetic acid are preferably used as the reaction accelerator.
The reaction may be performed at room temperature to 40 ° C for 30 minutes to several days.

With the compound of the present invention thus obtained,
Those with acidic protons can form salts in which the hydrogen atom is replaced by a suitable cation. These salts are generally metal salts, in particular alkali metal salts or alkaline earth metal salts, or optionally ammonium salts, alkylated ammonium salts or organic amine salts, and preferably, for example water, methanol or It can be prepared in a solvent such as acetone at a temperature of 20 to 100 ° C.

Although the compound of the present invention can be used as it is as a herbicide, it is usually used in the form of various forms such as powders, wettable powders, granules and emulsions together with formulation auxiliary agents. At this time, one or more compounds of the present invention are contained in the preparation in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 70% by weight. As examples of carriers / diluents and surfactants used as formulation aids, solid carriers include talc, kaolin, bentonite, diatomaceous earth, white carbon, clay and the like. As a liquid diluent, water,
Examples thereof include xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol and the like.

The surfactant is preferably used depending on its effect, and examples of the emulsifier include polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate and the like. As a dispersant,
Examples thereof include lignin sulfonate and dibutylnaphthalene sulfonate. Examples of the wetting agent include alkyl sulfonates and alkyl phenyl sulfonates. The above-mentioned preparations include those to be used as they are and those to be used after being diluted to a predetermined concentration with a diluent such as water. The concentration of the compound of the present invention when diluted and used is
The range of 0.001 to 1.0% is desirable. The amount of the compound of the present invention is 0.01 to 10 kg, preferably 0.05 to 10 per 1 ha.
It is 5 kg. These concentrations and amounts used vary depending on the dosage form, time of use, method of use, place of use, target crop, etc., and can of course be increased or decreased without sticking to the above range. Furthermore, the compound of the present invention comprises other active ingredients,
For example, it can be used in combination with a fungicide, an insecticide, an acaricide or a herbicide.

The phosphinylalkanol derivative according to the present invention, the method for producing the same and the use thereof will be specifically described with reference to production examples, formulation examples and test examples. The present invention is not limited to the following production examples, formulation examples and test examples as long as the gist thereof is not exceeded.

[0024]

【Example】

Production Example 1 3- [Bis (dimethylamino) phosphinyl] -2-hydroxy-2-methylpropionic acid methyl ester [Compound (I-3)] Bisdimethyl methylphosphonate synthesized as in Reference Production Example 1 below. Amide (0.59g, 0.00
(43 mol) in anhydrous tetrahydrofuran and butyllithium (3.5 ml (1.6M sol.), 0.0043 x 1.3 mol) at -50 ° C or below.
Was added and reacted for about 15 minutes, then methyl pyruvate (0.6
6 g, 0.0043 x 1.5 mol) was added. After about 1 hour, acetic acid (0.67
(g, 0.0043 × 2.6 mol) was added, and the concentrated product was washed with ethyl acetate. The washing solution was concentrated and purified with a silica gel column to obtain the desired product. Yield 0.14 g Yield 13% NMR (CDCl3, δ): 1.49 (1.5H, s), 1.50 (1.5H, s), 2.13 (1H, dd, J = 15.14,12.69
Hz), 2.45 (1H, dd, J = 15.14,13.19Hz), 2.57 (6H, d, J = 9.27H
z), 2.59 (6H, d, J = 9.77Hz), 3.77 (3H, s), 5.73 (1H (OH), s) .IR (liq., cm-1): 3332,2936,2820,2364, 1754,1656,1460,1372,1298,1198,
1088,978,920,832,784,766,726.

Production Example 2 3- [bis (benzylmethylamino) phosphinyl]-
2-Hydroxy-2-methylpropionic acid methyl ester [Compound (I-4)] Methylphosphonic acid bisbenzylmethylamide (1.00 g, 0.0033 mol) synthesized as in Reference Production Example 2 below was dissolved in anhydrous tetrahydrofuran. Butyllithium (2.8ml (1.6Msol.), 0.0033 × 1.36mol) was added at -50 ℃ or below, and reacted for about 15 minutes, then methyl pyruvate (0.51g,
0.0033 x 1.5 mol) was added. After about 1 hour, the mixture was partitioned with water-ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, concentrated, and purified with a silica gel column to give the desired product. Yield 0.60 g Yield 45% NMR (CDCl3, δ): 1.52 (1.5H, s), 1.54 (1.5H, s), 2.25 (1H, dd, J = 12.70,15.63
Hz), 2.478 (3H, d, J = 10.26Hz), 2.482 (3H, d, J = 9.76Hz), 2.6
7 (1H, dd, J = 13.19,15.63Hz), 3.80 (3H, s), 3.85 (1H, dd, J =
8.78,14.64Hz), 4.11 (2H, d, J = 7.81Hz), 4.36 (1H, dd, J = 7.3
3,14.64Hz), 5.65 (1H (OH), s), 7.2 ~ 7.5 (10H, complex) .IR (liq., Cm-1): 3332,3076,2956,2364,1752,1608,1500,1458 , 1366,1342,
1296,1196,1088,1002,950,834,762,732,706.

Production Example 3 2-Hydroxy-2-methyl-3-oxobutylphosphonic acid dibenzyl ester [Compound (I-10)] Methylphosphonic acid dibenzyl ester synthesized as in Reference Production Example 3 below. (2.00 g, 0.00724 mol) was dissolved in anhydrous tetrahydrofuran, butyllithium (6 ml (1.6 Msol.), 0.00724 × 1.3 mol) was added at -50 ° C or lower, and the reaction was carried out for about 15 minutes. Then 2,3-butanedione (3.12g, 0.0072g
4 × 5.0 mol) was added and the reaction was carried out for about 1 hour. Water and ethyl acetate were added to the reaction solution for partitioning, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product. Purification was performed by applying an ethyl acetate-hexane silica gel column and then a chloroform silica gel column. Yield 0.52 g Yield 19.8% NMR (CDCl3, δ): 1.37 (1.5H, s), 1.38 (1.5H, s), 2.17 (1H, dd, J = 15.13,17.09
Hz), 2.26 (3H, s), 2.48 (1H, dd, J = 15.13,18.56Hz), 4.64 (1H
(OH), s), 4.8〜5.1 (4H, complex), 7.2〜7.4 (10H, comple
x) .IR (liq., cm-1): 3392,3044,1718,1502,1460,1354,1220,1158,1084,998,9
12,872,736,698.

Production Example 4 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid dibenzylamide [Compound (I-11)] Synthesized as in Reference Production Example 3 below. Methylphosphonic acid dibenzyl ester (1.03 g, 0.0037 mol) was dissolved in anhydrous tetrahydrofuran, and butyllithium (2.4 ml (1.6 M sol.), 0.0037 × 1.04 mol) was added at −50 ° C. or lower, and the mixture was reacted for about 15 minutes. Then, pyruvic acid dibenzylamide (1.00 g, 0.0037 × 1.0 mol) dissolved in anhydrous tetrahydrofuran and synthesized as in Reference Production Example 4 below was added, and the reaction was carried out for about 1 hour. Then, the mixture was partitioned with water-ethyl acetate system, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column. Yield 0.97 g Yield 48% mp 83.0-85.0 ° C (white solid) NMR (CDCl3, δ): 1.60 (1.5H, s), 1.62 (1.5H, s), 2.23 (1H, dd, J = 15.1,16.6 H
z), 3.04 (1H, dd, J = 15.1,18.1Hz), 4.2〜5.4 (8H, complex),
5.45 (1H (OH), s), 7.1 ~ 7.5 (20H, complex) .IR (KBr, cm-1): 3444,3030,2976,2928,2364,1637,1500,1458,1428,1392,
1362,1214,1096,1080,1050,1014,942,912,870,848,730,
696,600,586,550.

Production Example 5 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid diethylamide [Compound (I-12)] Methylphosphonic acid synthesized as in Reference Production Example 3 below. Dissolve dibenzyl ester (1.5 g, 0.0054 x 1.0 mol) in anhydrous tetrahydrofuran, and add butyl lithium (3.6 ml (1.6 Msol.), 0.0054 x 1.3 mol) at -50 ° C or lower,
After reacting for about 15 minutes, pyruvic acid diethylamide (0.70 g, 0.0054 m) synthesized as in Reference Production Example 5 below.
ol) was added. After about 1 hour, the mixture was partitioned with saturated aqueous sodium hydrogen carbonate-ethyl acetate, the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated. Then, the product was purified by a silica gel column to obtain the desired product. Yield 0.95 g Yield 41% NMR (CDCl3, δ): 1.0-1.5 (6H, complex), 1.52 (1.5H, s), 1.53 (1.5H, s), 2.1
8 (1H, dd, J = 15.63,17.09Hz), 2.86 (1H, dd, J = 15.63,18.56H
z), 3.2 ~ 3.5 (3H, complex), 3.9 ~ 4.0 (1H, complex), 4.8 ~
5.1 (4H, complex), 5.30 (1H (OH), s), 7.2〜7.4 (10H, comple
x) .IR (liq., cm-1): 3368,3044,2984,2940,2364,1738,1628,1562,1502,1460,
1430,1384,1216,1144,1084,998,926,878,736,698.

Production Example 6 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid dimethylamide [Compound (I-13)] Methylphosphone synthesized as in Reference Production Example 3 below. Dissolve acid dibenzyl ester (2.00g, 0.0072mol) in anhydrous tetrahydrofuran and add butyllithium (4.8ml (1.6Msol.), 0.0072 × 1.10mol) at -50 ℃ or below,
After reacting for 5 minutes, pyruvic acid dimethylamide (1.00 g, 0.0072 ×) synthesized as in Reference Production Example 6 below.
1.20 mol) was added and reacted for about 1 hour. The mixture was partitioned with water-ethyl acetate system, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column. Yield 0.90 g Yield 32% NMR (CDCl3, δ): 1.52 (1.5H, s), 1.53 (1.5H, s), 2.22 (1H, dd, J = 15.14,17.09
Hz), 2.81 (1H, dd, J = 15.14,18.55Hz), 2.95 (3H, s), 3.27 (3
H, s), 4.8 ~ 5.1 (4H, complex), 5.21 (1H (OH), s), 7.2 ~ 7.4
(10H, complex) .IR (liq., Cm-1): 3352,3044,2948,2364,1638,1502,1460,1384,1460,1384,
1218,1146,1082,998,904,868,738,698.

Production Example 7 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid benzylmethylamide [Compound (I-14)] Synthesized as in Reference Production Example 3 below. Dissolve methylphosphonic acid dibenzyl ester (1.50g, 0.0052 × 1.04mol) in anhydrous tetrahydrofuran, and add butyllithium (3.6ml (1.6Msol.), 0.0052 × 1.10mol) at -50 ℃ or below and react for about 15 minutes. Then, pyruvic acid benzylmethylamide synthesized as in Reference Production Example 7 below.
(1.00 g, 0.0052 mol) was added and reacted for about 1 hour. Then, the mixture was partitioned with water-ethyl acetate system, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column. Yield 1.00 g Yield 41% NMR (CDCl3, δ): 1.57 (1.5H, s), 1.58 (1.5H, s), 2.22 (1H, dd, J = 15.62,17.09
Hz), 2.85 (1.5H, s), 2.93 (1H, dd, J = 15.63,17.20Hz), 3.24
(1.5H, s), 4.4 to 5.1 (6H, complex), 7.1 to 7.5 (complex) .IR (liq., Cm-1): 3356,3040,2940,2364,1638,1500,1458,1400,1218 , 1080,
998,912,868,734,698.

Production Example 8 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid i-propyl ester [Compound (I-15)] Synthesized as in Reference Production Example 3 below. , Methylphosphonic acid dibenzyl ester (1.5 g, 0.0054 × 1.0 mol) was dissolved in anhydrous tetrahydrofuran, and at −50 ° C. or lower, butyllithium (3.6 ml (1.6 Msol.), 0.0054 × 1.3 mol) was added,
After reacting for about 15 minutes, pyruvic acid i-propyl ester (0.70 g, 0.1) synthesized as in Reference Production Example 8 below.
(0054 mol) was added, and after about 1 hour, the mixture was partitioned with saturated aqueous sodium hydrogen carbonate-ethyl acetate, the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated. Then, the product was purified by a silica gel column to obtain the desired product. Yield 1.05g Yield 48% NMR (CDCl3, δ): 1.18 (3H, d, J = 6.35Hz), 1.23 (3H, d, J = 6.35Hz), 1.47 (1.5H,
s), 1.48 (1.5H, s), 2.26 (1H, dd, J = 15.62,17.57Hz), 2.50 (1
H, dd, J = 15.62,18.56Hz), 4.9 ~ 5.1 (5H, complex), 7.33 (10
H, s) .IR (liq., Cm-1): 3380,3044,2988,2364,1738,1502,1460,1378,1216,1094,
998,874,736,698.

Production Example 9 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid benzyl ester [Compound (I-17)] Methylphosphone synthesized as in Reference Production Example 3 below. Dissolve acid dibenzyl ester (1.55g, 0.0056mol) in anhydrous tetrahydrofuran, and add butyllithium (3.8ml (1.6Msol.), 0.0056 × 1.09mol) at -50 ℃ or below
After reacting for 5 minutes, pyruvic acid benzyl ester (1.00 g, 0.0056) was synthesized as in Reference Production Example 9 below.
(× 1.00 mol) was added and the reaction was performed for about 1 hour. Then, the mixture was partitioned with an ethyl acetate-water system, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified with a silica gel column. Yield 0.99g Yield 39% NMR (CDCl3, δ): 1.50 (1.5H, s), 1.51 (1.5H, s), 2.26 (1H, dd, J = 15.13,17.09
Hz), 2.52 (1H, dd, J = 15.14,18.07Hz), 4.8 ~ 5.2 (6H, comple
x), 7.2 ~ 7.4 (15H, complex) IR (liq., cm-1): 3356,3076,3044,2960,2364,1746,1502,1460,1384,1216,
1188,1090,996,922,872,736,698.

Production Example 10 3- (Dibenzyloxyphosphinyl) -2-hydroxy-2-methylpropionic acid methyl ester [Compound (I-18)] Methylphosphone synthesized as in Reference Production Example 3 below. Acid dibenzyl ester (3.00g, 0.0109mol) was dissolved in anhydrous tetrahydrofuran, and butyllithium (13cc (1.6Msol.), 0.0109 × 1.9mol) was added at -50 ° C or lower to give about 20
After reacting for minutes, methyl pyruvate (6.64 g, 0.0109 × 6.
0 mol) was added and reacted for about 1 hour. Water and ethyl acetate were added to the reaction mixture, and the mixture was partitioned, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column. Yield 0.53g Yield 12.5% NMR (CDCl3, δ): 1.45 (1.5H, s), 1,46 (1.5H, s), 2.29 (1H, d, J = 17.6Hz), 2.39
(1H, d, J = 17.8Hz), 3.57 (3H, s), 4.91 (4H, d, J = 8.2Hz), 7.24
(10H, s) .IR (liq.cm-1): 3352,3076,3044,2960,1746,1502,1458,1384,1216,1090,
996,926,874,736,698.

Production Example 11 2-Hydroxy-2-methyl-3-oxobutylphosphonic acid [Compound (I-31)] 2-Hydroxy-2-methyl-3 synthesized as in Production Example 3 above. -Oxobutylphosphonic acid dibenzyl ester [Compound (I-10)] (0.52g, 0.0014mol) was dissolved in methanol / water = 1/1, a small amount of acetic acid and 10% palladium on carbon were added, and the mixture was placed under hydrogen atmosphere. I made it react all day and night. It was filtered using Hyflo Super Cell and concentrated to obtain the desired product. Yield 0.24 g Yield 94% NMR (D2O, δ): 1.21 (1.5H, s), 1.22 (1.5H, s), 2.02 (1H, dd, J = 16.1,16.1Hz
(triplet like)), 2.10 (3H, s), 2.24 (1H, dd, J = 17.6,17.6H
z (triplet like) .IR (liq., cm-1): 2992,2304,1712,1362,1170,1006,772.

Production Example 12 3-phosphono-2-hydroxy-2-methylpropionic acid diethylamide [Compound (I-32)] 3- (dibenzyloxyphosphinyl) synthesized as in Production Example 5 above. 2-Hydroxy-2-methylpropionic acid diethylamide [compound (I-12)] (0.55
g, 0.0013 mol) in methanol / water = 15 ml / 15 ml,
A small amount of acetic acid and 10% palladium carbon were added, and the mixture was reacted overnight under a hydrogen atmosphere. After filtration using Hyflo Super Cell, the product was concentrated to obtain the desired product. Yield 32g Yield 102% NMR (D2O, δ): 0.8-1.1 (6H, complex), 1.38 (3H, s), 2.04 (1H, dd, J = 15.63
~ 18.06Hz (triplet like)), 2.29 (1H, dd, 15.63 ~ 18.06Hz
(triplet like)), 3.0〜3.3 (2H, complex), 3.3〜3.7 (2H, c
omplex) .IR (liq., cm-1): 3376,2988,2300,1614,1470,1444,1386,1366,1278,1150,
1086,990,948,866,790,752,676,490.

Production Example 13 3-phosphono-2-hydroxy-2-methylpropionic acid dimethylamide [Compound (I-33)] 3- (dibenzyloxyphosphinyl) synthesized as in Production Example 6 above. ) -2-Hydroxy-2-methylpropionic acid dimethylamide [compound (I-13)] (0.61
g, 0.00156 mol) was dissolved in methanol / water = 15 ml / 15 ml, a small amount of acetic acid and 10% palladium carbon were added, and the mixture was reacted overnight in a hydrogen atmosphere. It was filtered using Hyflo Super Cell and then concentrated to obtain the desired product. Yield 0.39 g Yield 118% NMR (D2O, δ): 1.31 (3H, s), 1.90 (1H, dd, J = 15.6,16.1Hz), 2.07 (1H, dd, J =
16.1,17.1), 2.50 (6H, s).

Production Example 14 3-phosphono-2-hydroxy-2-methylpropionic acid methylamide [Compound (I-34)] 3- (dibenzyloxyphosphinyl) synthesized in the same manner as in Production Example 7 above. -2-Hydroxy-2-methylpropionic acid benzylmethylamide [Compound (I-14)]
(0.40 g, 0.00085 mol) was dissolved in methanol / water = 10 ml / 10 ml, a small amount of acetic acid and 10% palladium carbon were added, and the mixture was reacted overnight in a hydrogen atmosphere. It was filtered using Hyflo Super Cell and then concentrated to obtain the desired product. Yield 0.18 g Yield 109% NMR (D2O, δ): 1.26 (1.5H, s), 1.27 (1.5H, s), 1.95 (1H, dd, J = 16.6,15.6H
z), 2.18 (1H, dd, J = 16.6,18.6Hz), 2.57 (3H, s).

Production Example 15 3-phosphono-2-hydroxy-2-methylpropionic acid i-propyl ester [Compound (I-35)] 3- (dibenzyloxyphosate synthesized in the same manner as in Production Example 8 above. Finyl) -2-hydroxy-2-methylpropionic acid i-propyl ester [Compound (I-15)]
(0.55 g, 0.00135 mol) was dissolved in methanol / water = 15 ml / 15 ml, a small amount of acetic acid and 10% palladium carbon were added, and the mixture was reacted overnight under a hydrogen atmosphere. After filtration using Hyflo Super Cell, the product was concentrated to obtain the desired product. Yield 0.22 g Yield 72% NMR (D2O, δ): 1.09 (6H, d, J = 6.35Hz), 1.32 (3H, s), 2.05 (1H, dd, J = 15.1〜
16.6Hz (triplet like)), 2.25 (1H, dd, J = 15.6 ~ 17.6Hz (tr
iplet like)), 4.7 ~ 4.9 (1H, complex) .IR (liq., cm-1): 3448,2288,1728,1454,1380,1088,922,850,764,488.

Production Example 16 3-phosphono-2-hydroxy-2-methylpropionic acid methyl ester [compound (I-37)] 3- (dibenzyloxyphosphinyl) synthesized as in Production Example 10 above. ) -2-Hydroxy-2-methylpropionic acid methyl ester [compound (I-18)] (0.4
3 g, 0.0011 mol) in methanol / water = 10 ml / 10 ml,
A small amount of acetic acid and 10% palladium carbon were added, and the mixture was reacted overnight under a hydrogen atmosphere. It was filtered using Hyflo Super Cell and concentrated to obtain the desired product. Yield 0.21 g Yield 96% NMR (D20, δ): 1.31 (1.5H, s), 1.32 (1.5H, s), 2.04 (1H, dd, J = 15.6,17.1H
z), 2.22 (1H, dd, 15.6,18.1Hz), 3.57 (3H, s) .IR (liq.cm-1): 3416,1740,1460,1380,1182,828,762.

Production Example 17 3-phosphono-2-hydroxy-2-methylpropionic acid [Compound (I-38)] 3- (dibenzyloxyphosphinyl) -synthesized as in Production Example 9 above. 2-hydroxy-2-methylpropionic acid benzyl ester [compound (I-17)] (0.60 g, 0.0013 mol) was added to methanol /
It was dissolved in water = 15 ml / 15 ml, a small amount of acetic acid and 10% palladium carbon were added, and the mixture was reacted overnight under a hydrogen atmosphere. After filtration using Hyflo Super Cell, the product was concentrated to obtain the desired product. Yield 0.28 g Yield 115% NMR (D2O, δ): 1.32 (1.5H, s), 1.33 (1.5H, s), 2.24 (1H, dd, J = 15.6 to 18.1H
z (tripletlike)), 2.05 (1H, dd, J = 16.1 to 16.6Hz (triplet
like)). IR (liq., cm-1): OH signal was strong and no other characteristic absorption was observed.

Reference Production Example 1 Methylphosphonic acid bisdimethylamide Methylphosnic dichloride (2.32 g, 0.0175 mol) was dissolved in anhydrous tetrahydrofuran, and the mixture was stirred at room temperature while dimethylamine (12.0 g (50% aqueous solution) was added. so
l.), 0.0175 × 7.6 mol) was connected to a tube and heated to 70 ° C., and vaporized dimethylamine was bubbled into a tetrahydrofuran solution. After bubbling started,
The reaction was stopped in about 1 hour and the mixture was concentrated as it was. The residue was washed with ethyl acetate and the washings were concentrated to obtain the desired product. Yield 2.10 g Yield 88% NMR (CDCl3, δ): 1.40 (3H, d, J = 14.65Hz), 2.59 (12H, d, J = 9.76Hz) .IR (liq., Cm-1): 3464, 2996,2900,2812,2456,2364,1650,1462,1422,1306,
1198,1066,976,890,780,710.

Reference Production Example 2 Methylphosphonic acid bisbenzylmethylamide Methylphosphonic dichloride (1.00 g, 0.0075 mol) was dissolved in dry tetrahydrofuran, and benzylmethylamine (4.00 g, 0.0075 × 4.4 mol) was added at room temperature, The mixture was stirred for about 1 hour. The mixture was partitioned with ethyl acetate-water, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, concentrated, and purified with a silica gel column to give the desired product. Yield 1.76 g Yield 78% NMR (CDCl3, δ): 1.57 (3H, d, J = 14.65Hz), 2.58 (6H, d, J = 10.25Hz), 4.14 (2H,
dd, J = 7.81,15.14Hz), 4.22 (2H, dd, J = 8.30,15.14Hz), 7.2
~ 7.4 (10H, complex) .IR (liq., Cm-1): 3452,3036,2908,2820,2364,1600,1498,1458,1364,1340,
1304,1208,1076,1000,950,890,788,730,702.

Reference Production Example 3 Methylphosphonic acid dibenzyl ester sodium hydride (1.14 g, 60% in mineral oil, 0.019x
An anhydrous tetrahydrofuran suspension (1.5 mol) was stirred under an argon atmosphere, dibenzyl phosphite (5.00 g, 0.019 mol) was added, and the mixture was reacted under ice cooling for about 30 minutes. Methyl iodide (2.37ml, 0.019x2.0mol) was added thereto, and the mixture was kept at 30
It was made to react for minutes. After partitioning with ethyl acetate-0.12N hydrochloric acid, the organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, concentrated, and separated with a silica gel column to obtain the desired product. Yield 4.43g Yield 84% NMR (CDCl3, δ): 1.42 (3H, d, J = 18.0), 4.7-5.2 (4H, complex), 7.26 (10H, s) IR (liq.cm-1): 3760 , 3488,3044,2964,2900,2364,1654,1560,1544,1524,
1502,1460,1502,1460,1420,1384,1314,1240,1082,1000,
922,830,734,698.

Reference Production Example 4 Pyruvic Acid Dibenzylamide To a benzene solution of pyruvic acid (2.00 g, 0.0227 mol), thionyl chloride (2.97 g, 0.0227 × 1.1 mol) and a small amount of dimethylformamide were added and refluxed. After 30 minutes, dibenzylamine (5.37 g, 0.0227 × 1.2 mol) and triethylamine (3.44 g, 0.0227 × 1.5 mol) were added, and the mixture was further refluxed for 30 minutes. Then, water was added and distributed, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified with a silica gel column to obtain the desired product. Yield 5.14g Yield 85% mp 43.0-45.0 ° C NMR (CDCl3, δ): 2.32 (3H, s), 4.39 (4H, d, J = 8.4Hz), 7.18 (10H, s) .IR (liq.cm -1): 3432,3044,2940,1716,1632,1500,1458,1438,1354,1322,
1270,1252,1204,1152,1078,1024,964,942,924,892,848,
824,772,746,722,700,622,594,560,492.

Reference Production Example 5 Pyruvic Acid Diethylamide To a benzene solution of pyruvic acid (3.00 g, 0.034 mol), thionyl chloride (4.4 g, 0.034 × 1.1 mol) and a small amount of dimethylformamide were added and refluxed. After 30 minutes, diethylamine (6.23 g, 0.034 × 2.5 mol) was added, and the mixture was stirred at room temperature for 1 hour. Then, water was added for partitioning, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, concentrated, and purified by distillation. Yield 3.70 g Yield 76% bp 100-110 ° C (bath temp.) (1
8mmHg) NMR (CDCl3, δ): 1.37 (6H, t, J = 6.8Hz), 2.52 (3H, s), 3.43 (2H, q, J = 6.8Hz),
3.71 (2H, q, J = 6.8Hz) .IR (liq., Cm-1): 3596,2988,2944,2364,1716,1640,1544,1442,1386,1358,
1318,1296,1222,1200,1118,1024,972,946,870,790,746,
684,604,578.

Reference Production Example 6 Pyruvate Dimethylamide To a solution of pyruvic acid (3.00 g, 0.034 mol) in benzene, thionyl chloride (4.45 g, 0.034 × 1.1 mol) and a small amount of dimethylformamide were added and refluxed. After 30 minutes, dimethylamine (9.21 g (50% in H2Osol.), 0.034 x 3.0 mol) was added to a benzene solution. After stirring for about 1 hour, water was added for partitioning, the mixture was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and the organic layer was evaporated to obtain the desired product. Yield 2.31g Yield 59% Compound (8) NMR (CDCl3, δ): 2.35 (3H, s), 2.90 (3H, s), 2.93 (3H, s). IR (liq., Cm-1): 2944 , 2364,2252,1716,1660,1512,1422,1356,1268,1226,
1108,1064,1020,984,912,736,704,686,604,578.

Reference Production Example 7 Pyruvic Acid Benzylmethylamide To a benzene solution of pyruvic acid (2.00 g, 0.0227 mol), thionyl chloride (2.97 g, 0.0227 × 1.1 mol) and a small amount of dimethylformamide were added and refluxed. After 30 minutes, benzylmethylamine (3.30g, 1.2mol) and triethylamine
(3.44 g, 0.0227 × 1.5 mol) was added, and the mixture was refluxed for 30 minutes. Then, water was added and distributed, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified with a silica gel column to obtain the desired product. Yield 3.41g Yield 79% NMR (CDCl3, δ): 2.34 (1.5H, s), 2.40 (1.5H, s), 2.85 (3H, s), 4.40 (1H, s), 4.
49 (1H, s), 7.19 (5H, s) .IR (liq., Cm-1): 3040,2940,2364,1716,1650,1500,1458,1420,1358,1222,
1170,1092,1020,962,700.

Reference Production Example 8 Pyruvic Acid i-Propyl Ester To a benzene solution of pyruvic acid (3.00 g, 0.034 mol), thionyl chloride (4.4 g, 0.034 × 1.1 mol) and a small amount of dimethylformamide were added and refluxed. After 30 minutes, i-propyl alcohol (4.1 g, 0.034 × 2.0 mol) was added, and after refluxing for about 30 minutes, water was added and distributed, and the mixture was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, concentrated, and concentrated on a silica gel column. Purified in. Yield 0.70 g Yield 16% NMR (CDCl3, δ): 1.31 (6H, d, J = 6.0Hz), 2.40 (3H, s), 5.06 (1H, sept., J = 6.0H
z) .IR (liq., cm-1): 2996,2944,2364,1828,1736,1624,1472,1424,1380,1306,
1150,1104,982,912,856,812,724,602.

Reference Production Example 9 Pyruvic Acid Benzyl Ester To a benzene solution of pyruvic acid (5.00 g, 0.057 mol), thionyl chloride (7.41 g, 0.057 × 1.1 mol) and a small amount of dimethylformamide were added and refluxed. After 30 minutes, benzyl alcohol (12.3 g, 0.057 × 2.0 mol) was added, and the mixture was refluxed for about 30 minutes. Then, after water was added for distribution, the mixture was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, the organic layer was evaporated, and the residue was purified with a silica gel column to obtain the desired product.
The target product was obtained as a compound having the following two physicochemical properties (a) and (b). In the above Production Example 9, the pyruvic acid benzyl ester (a) was used. (a) Yield 2.92g Yield 29% (b) Yield 3.26g Yield 32% Retention time for high performance liquid chromatography analysis (Column: ODS F411A, Eluent: CH3CN / H2O, Flow rate: 1.0m
l / min.) (a) 2.54min., (b) 2.75min. (a) NMR (CDCl3, δ): 2.38 (3H, s), 5.16 (2H, s), 7.26 (5H, s) .IR (liq., cm-1): 3480,3076,3044,2964,1734,1590,1502,1460,1422,1362,
1298,1268,1216,1140,1082,1022,986,944,908,814,752,
700,608,590. (B) NMR (CDCl3, δ): 2.03 (3H, s), 5.00 (2H, s), 7.23 (5H, s) .IR (liq., Cm-1): 3076,3044,2960,1746 , 1502,1458,1384,1366,1230,1082,
1028,966,920,836,750,700.

Formulation examples and test examples are shown below, but carrier (diluent)
The auxiliaries, their mixing ratios and active ingredients can be varied within wide limits. “Parts” in each formulation example represents parts by weight.

Formulation Example 1 (wettable powder): Compound (I-37) 50
Part, lignin sulfonate 5 parts, alkyl sulfonate
3 parts and 42 parts of diatomaceous earth are mixed and ground to make a wettable powder, and diluted with water before use.

Formulation Example 2 (emulsion): 25 parts of compound (I-18),
65 parts of xylene and 10 parts of polyoxyethylene alkylaryl ether are uniformly mixed to form an emulsion, which is diluted with water before use.

Formulation Example 3 (granules): 8 parts of compound (I-38),
Bentonite 40 parts, clay 45 parts and lignin sulfonic acid 7
The parts are uniformly mixed, further water is added and kneaded, and the mixture is processed into granules by an extrusion-type granulator and used as granules.

Test Example 1 Effect test by foliar treatment Alocust, Kosendangsa, Yasushi mustard, chickweed, Ebisugusa, Amaranthus perforatum, Ichibi, Bindweed, Chamomile, Yaemgra, Flava sativa, Enokologsa, Prunus chinensis, Oat grass,
A medicinal solution of the test compound prepared by adjusting the concentration of the wettable powder as shown in the above formulation example to a predetermined concentration in the foliage part of citrus clover (when each test plant has 1 to 2 leaves), 1 kg / ha and 5 kg / ha. A considerable amount was applied. 14 days after the application, the herbicidal effect was investigated on the basis of the following three levels of 1, 2, and 3. Survey criteria, less than 1: 30%, 2: 30% to less than 70%, 3: 70%
In Table 1 above, the compounds in which R ¹ and R ² are hydroxyl groups and salts thereof with a base showed a herbicidal effect due to a remarkable whitening action.

[0055]

INDUSTRIAL APPLICABILITY The phosphinylalkanol derivative of the above formula (I) of the present invention and salts thereof with a base are useful as an active ingredient of a herbicide.

Claims (4)

[Claims] 1. A phosphinylalkanol derivative represented by the formula (I) and a salt thereof with a base: wherein R ¹ and R ² are each independently a hydroxyl group, C 1
~ C4 alkoxy group, C7 ~ C9 aralkyloxy group, phenoxy group (this phenoxy group is 1 ~ C4 alkyl group
2 may be substituted), amino group (this amino group may be substituted with 1 to 2 of C1 to C4 alkyl group and / or C7 to C9 aralkyl group), C1 to C4 An alkyl group, a C7-C9 aralkyl group or a phenyl group is shown. R ³
Is a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, an amino group (this amino group may be substituted with 1 or 2 of a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group. Good), a C1-C4 alkyl group, a C7-C9 aralkyl group, or a phenyl group] 2. The phosphinylalkanol of formula (Ia) in the reaction formula of formula 2 is obtained by reacting a phosphinylmethane of formula (II-a) with a dicarbonyl compound of formula (III-a). Method for producing derivative [In the formula, R ¹ a and R ² a are each independently a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group,
Phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1 to C4 alkyl group), amino group (this amino group is a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group) 1 to 2 may be substituted), a C1 to C4 alkyl group, a C7 to C9 aralkyl group, or a phenyl group. R ³ a is a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, an amino group (this amino group is substituted with 1 to 2 of a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group. C1 to C4 alkyl group, C7 to C9 aralkyl group or phenyl group] 3. A phosphinylalkanol derivative of formula (Ib) in the reaction formula of formula 3 is hydrolyzed to give a compound of formula (Ic)
A method for producing a phosphinylalkanol derivative of: [wherein R ¹ b and R ² b are each independently a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group,
Phenoxy group (this phenoxy group may be substituted with 1 to 2 of C1 to C4 alkyl group), amino group (this amino group is a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group) 1 to 2 may be substituted), a C1 to C4 alkyl group, a C7 to C9 aralkyl group, or a phenyl group. R ³ b is a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, an amino group (this amino group is substituted with 1 to 2 of a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group. ), A C1 to C4 alkyl group, a C7 to C9 aralkyl group, or a phenyl group. However, R ¹ b, R
^At least one of ² b and R ³ b represents a benzyloxy group or an amino group to which at least one benzyl group is bonded. R ¹ c and R ² c are each independently
Hydroxyl group, C1 to C4 alkoxy group, C7 to C9 aralkyloxy group, phenoxy group (this phenoxy group may be substituted with 1 to 2 C1 to C4 alkyl groups), amino group (this amino group is C1-C4 alkyl group and / or C7-C9
Optionally substituted with 1 to 2 aralkyl groups), C1 ~
A C4 alkyl group, a C7 to C9 aralkyl group or a phenyl group is shown. R ³ c is a hydroxyl group, C1-C4 alkoxy group, C7-C9
Aralkyloxy group, amino group (this amino group is C1 ~
C4 alkyl group and / or 1 to 7 of C7 to C9 aralkyl groups
2 may be substituted), C1-C4 alkyl group, C7-
C9 represents an aralkyl group or a phenyl group. However, R1
At least one of c, R2c and R3c represents a hydroxy group or a debenzylated amino group] [Chemical Formula 3] 4. A herbicide containing a phosphinylalkanol derivative of the formula (I) of formula 4 and salts thereof with a base as an active ingredient [wherein R ¹ and R ² are each independently, Hydroxyl group, C1
~ C4 alkoxy group, C7 ~ C9 aralkyloxy group, phenoxy group (this phenoxy group is 1 ~ C4 alkyl group
2 may be substituted), amino group (this amino group may be substituted with 1 to 2 of C1 to C4 alkyl group and / or C7 to C9 aralkyl group), C1 to C4 An alkyl group, a C7-C9 aralkyl group or a phenyl group is shown. R ³
Is a hydroxyl group, a C1 to C4 alkoxy group, a C7 to C9 aralkyloxy group, an amino group (this amino group may be substituted with 1 or 2 of a C1 to C4 alkyl group and / or a C7 to C9 aralkyl group. Good), a C1 to C4 alkyl group, a C7 to C9 aralkyl group, or a phenyl group]