KR790001957B1 - Process for preparation of 2-sulfomyloxyethyl-phosphonic acid (or 2-sulfonyloxyethyl-thionophosphonic acid) derivatives - Google Patents

Abstract

Title compds [I; R1 = substituted or non-substituted alkyl, alkenyl, aryl; X = O,S ; R2,R3 = same or not OR',SR',N(R')2 (here R' is H, substituted alkyl, alkenyl, aryl) , useful as plant-growth regulators, were prepd, by reaction of II [Y = C1, OR' and III [Z = OR', SR, N(R1)2

Description

Process for preparing 2-sulfonyloxyethyl phosphonic acid (or 2-sulfonyloxyethyl thionophosphonic acid) derivative

The present invention relates to a method for producing a 2-sulfonyloxyethyl phosphonic acid (or 2-sulfonyloxyethyl thionophosphonic acid) derivative represented by the following general formula (1).

Where

R ₁ is a substituted or unsubstituted alkyl group, alkenyl group or aryl group,

X is O or S,

R ₂ and R ₃ are the same or different and each represents a -OR ', -SR' or -N (R ') ₂ group, wherein R' is a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group or aryl group, or Halogen, provided that R 'in the -N (R') ₂ group may be the same or different, and that group may be a morpholine group, but when X is O above, R ₂ and R ₃ are both- The group OR 'and at least one -OR' group is an -OH group, and when X is S, R ₂ and R ₃ cannot both be -N (R ') ₂ groups.

Compound (1) is prepared by reacting a compound of the following general formula (2) with a compound of the following general formula (3).

In the above formula

R ₁ and X are as defined above,

Y is a Cl or -OR 'group where R' is as defined above,

Z is a -OR ', -SR or -N (R') ₂ group, where R 'is as defined above, but in -N (R') ₂ its R 'may be the same or different, and Group may be a -morpholine group).

Since the end of the 19th century, reports of rot caused by ethylene during storage of apples have been found in various phenomena in plants caused by ethylene and simple hydrocarbons. About 40 years ago, ethylene was found to be biosynthesized as a natural plant metabolism, and its importance was recognized as a physiologically new active ingredient that regulates the physiological phenomena of plants. Thus, radical advances have been made in the study of the physiological activity of ethylene in plants, with the result that ethylene has been used to regulate plant growth. However, since ethylene is a gas at room temperature, its allowance for agriculture has been limited. In use, ethylene should be placed in a closed container or used indoors and could not be used directly in the field. In addition, the risk of fire or explosion was not excluded.

Subsequently, ethylene emitters have been found that can generate ethylene after use to regulate plant growth, and it has been reported that these substances exhibit various physiological activities in plant growth. These substances are called plant growth regulators and are effectively used for:

(1) destruction of dormant states

Plant growth regulators bloom plant bulbs to destroy the dormant state of raspberries and grapes, to germinate and to bloom evenly.

(2) increase in the amount of fluid

Ethylene-emissions are widely used to increase the amount of latex in rubber trees and can have the effect of promoting nearly twofold sap formation. Thus, ethylene-emissions can be sprayed onto old rubber trees with low latex secretion ability, thereby significantly increasing their secretion capacity.

(3) Promotion of flowering

By spraying plant growth regulators on ANANAS and pineapple trees, it is possible to continuously cultivate them without any harm, and to increase the yield and yield of both plants.

(4) Sex reversal

Pistil modification of cucumbers, pumpkins and watermelons can be increased by using plant growth regulators, and thus an increase in yield can also be expected. In particular, pistil modification is poor in the case of greenhouse cultivation of cucumbers because of temperature fluctuations, but this drawback can be avoided by using plant growth regulators.

(5) promotion of maturity

Plant growth regulators promote the maturation of various fruits such as pears, persimmons, apples, oranges, peaches or figs. Ripe fruits can be shipped 5-20 days faster, compared to trees that have not been treated with plant growth regulators. Thus it can increase profits because it greatly affects the price of fruits in the distribution and shipping of labor in the harvest.

(6) enhancement of coloring

Plant growth regulators promote yellowing of tobacco leaves, coloring of oranges, apples, and fukus, allowing the harvesting of fruits of uniform color.

(7) Promotion of fall of fruit and leaf

Harvesting labor to collect fruits or leaves of fruit trees can be reduced by using plant growth preparations. In particular, when it is used for trees or shrubs, it is possible to promote the deciduous phenomenon in shrubs or broadleaf vines and to replace the plucking of leaves.

It is already known that β-hydroxycethydrazine or a derivative thereof can be used as a plant growth regulator and has an effect of enhancing the maturation of raw fruits (see Japanese Patent Publication No. 10748/69). It is also known that compounds having a 2-chloroethylphosphonic acid structure can be used as plant growth regulators (see British Patent Specification 1194433).

On the other hand, US Patent No. 3, 834, 888 issued Sep. 10, 1974 describes that compounds of the following structural formula are useful as plant growth regulators.

(Wherein R ₁ and R ₂ are substituted or unsubstituted hydrocarbon groups, X is S or O and A is an anion free from plant damage.)

The present inventors have found that the compounds having the following skeletal structure, which are not described in the prior literature, exhibit excellent plant growth regulation effects on plants of broad range.

For example, as shown in the comparative examples described below, these compounds exhibit superior effects on plant growth regulation effects than 2-chloroethylphosphonic acid, which is commercially available as a representative compound in the second prior art described above. . Conventionally, the compounds of the present invention having the framework as described above and their plant growth effects are not completely known.

Thus, it is an object of the present invention to provide a process for the preparation of compounds having the aforementioned skeletal structure.

The objects and advantages of the present invention will become more apparent from the following description.

In the above general formula (1), R ₁ is a substituted or unsubstituted C ₁ to C ₁₂ straight, branched, or cycloalkyl group, a substituted or unsubstituted C ₂ to C ₁₂ straight, branched, Or a cycloalkenyl group and a substituted or unsubstituted C ₆ -C ₁₄ aryl group. Particularly suitable among the examples of R ₁ are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, secondary-butyl, tert-butyl, pentyl, 2-methyl pentyl, hexyl, heptyl, octyl, nonyl C ₁ -C ₁₂ linear or branched alkyl groups such as decyl, undecyl, or dodecyl, and C ₅ -C ₁₂ cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl or cyclodecyl.

When R ₁ is a substituted alkyl group, this substituent is a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group having 1 to 12 carbon atoms in the alkoxy component, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, Acyl group containing 1 to 12 carbon atoms, acyloxy group containing 1 to 12 carbon atoms, benzoyloxy group, thiocyanate group, isothiocyanate group, acetamide group, phthalimide group, acetylthio group , Phosphono group, sulfonyloxy group, succinimide group, trialkylsilyl group having 1 to 12 carbon atoms in alkyl component, aryl group containing 6 to 14 carbon atoms and alkyl component containing 1 to 12 carbon atoms It is suitable to select from alkylthio groups.

Suitable examples of substituted alkyl groups include α-chloroethyl, γ-bromopropyl, γ-chloropropyl, γ, γ-dichloropropyl, chloromethyl, α-chlorocyclohexyl, β-cyanoethyl, β-methoxycarabo Nylethyl, β-ethoxycarbonylethyl, β-methoxycarboylpropyl, γ-ethoxypropyl, γ-methoxypropyl, γ-phenoxypropyl, γ-ethoxyethyl, β-carboxyethyl, β Carboxypropyl, β-acetylethyl, γ-acetoxypropyl, β-acetoxyethyl, β-benzoylpropyl, β-benzoylethyl, γ-nitropropyl, β-nitroethyl, β-nitro-α-phenylethyl , γ-thiocinanatopropyl, β-thiocyanatoethyl, γ-isothiocyanatopropyl, β-isothiocyanatoethyl, β-phthalimidoethyl, β-succinimidoethyl, β-acet Amidoethyl, β-acetylthioethyl, β-phosphonoethyl, 2- (β-phosphonoethyloxysulfonyl) ethyl, (β-phosphonoethyloxysulfonyl) methyl, γ- Lee there can be a methyl silyl propyl, ethyl trimethyl-β-, and benzyl β- phenylethyl.

Suitable examples of substituted alkyl groups R ₁ include 2-cyano-1-methylethyl, 2-chloro-1-methylethyl, 2-methoxyl, 1-dimethylethyl, 5-methyl-7-nitroseltyl and 4-cara Carboxy-3-methylbutyl is mentioned.

Suitable examples of substituted cycloalkyl groups include 4-chlorocyclohexyl, 4-cyanocyclohexyl, 4-methoxycyclohexyl, 4-ethoxycyclohexyl, 4-carboxycyclohexyl, 2-nitrocyclohexyl and 4-chlorocyclo Octyl.

In the general formula (1), the alkenyl group represented by R ₁ is, for example, vinyl, propenyl, allyl, isopropenyl, butenyl, butadienyl, pentenyl, hexenyl, octenyl and dodecenyl And C ₅ -C ₁₂ cycloalkenyl groups such as C ₂ -C ₁₂ straight or branched alkenyl groups, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclodecenyl and the like. Alkenyl groups containing 5 to 12 carbon atoms are particularly suitable.

Suitable substituents for the alkenyl group R ₁ are the same as those described above in connection with the substituted alkyl group.

Suitable examples of substituted alkenyl groups include β-chlorovinyl, γ-chloropropenyl, γ-cyanopropenyl, γ-nitropropenyl, chloroisopropenyl, γ-phenoxypropenyl, β-carboxyvinyl, β- Methoxy carboylvinyl, β-benzylvinyl, styrene, γ-succinimidopropenyl, γ-phthalimidopropenyl, γ-acetamide propenyl, β-phosphonovinyl and γ-trimethylsilylpropenyl. .

Examples of the substituted cycloalkenyl group include 4-chloro-2-cyclohexenyl or 4-carboxy-2-cyclohexenyl.

Examples of the aryl group in the general formula (1) include phenyl, naphthyl, anthryl, phenanthryl and biphenyl. Examples of the substituent for the aryl group include allyl groups having 1 to 6 carbon atoms, halogen atoms, acetyl groups, amido groups, nitro groups, cyano groups, carboxyl groups, alkoxy groups having 1 to 6 carbon atoms, and hydroxyl groups. , Sulfonyl group, or sulfonyl group.

Suitable examples of substituted aryl groups in formula (1) include tolyl, xylyl, t-butylphenyl, cumenyl, chlorophenyl, bromophenyl, iodophenyl, acetylphenyl, acetamidophenyl, nitrophenyl, cyanophenyl , Carboxyphenyl, methoxyphenyl, ethoxyphenyl, chloronitrophenyl, bromonitrophenyl, chlorotolyl, nitrotolyl, carboxytolyl, chloromethoxyphenyl, cyanotolyl, hydroxyphenyl, nitronaphthyl, chloro Anthryl, cyanophenanthryl, methoxybiphenyl, and the like.

In the general formula (1), R ₂ and R ₃ are -OR 'group (wherein, R' is a hydrogen atom, a substituted or unsubstituted C ₁ ~ C ₁₂ straight-chain, branched, or a cycloalkyl group substituted or unsubstituted C ₂ ~ Selected from C ₁₂ straight, branched or cycloalkenyl groups and substituted or unsubstituted C ₆ to C ₁₄ aryl groups, -SR 'groups wherein R' are the same as described above, -N (R ') ₂ groups, wherein R 'is the same as described above or a morpholino group containing N in said group and the two R' groups are the same or different and are selected from halogen atoms, particularly chlorine. Among the -OR ', -SR' and -N (R ') ₂ groups, R' is the same as mentioned with respect to the R ₁ group.

Examples of the -OR 'group include hydroxyl, methoxy, ethoxy, propoxy, isozerooxy, n-butoxy, tert-butoxy, dodecyloxy, cyclohexyloxy, benzyloxy, chloroethyloxy, phenoxy , Chlorophenoxy, tolyoxy, allyloxy and chloroallyloxy.

Examples of the -SR 'group include mercapto, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, tert-butylthio, dodecylthio, cyclohexylthio, benzylthio, chloroethylthio, phenylthio, Chlorophenylthio, tolylthio and allylthio.

Examples of -N (R ') ₂ groups include dimethylamino, isopropylamido, octylamino, dodecylamino, cyclopentylamino, cyclohexylamino, chloromethylamino, chloroethylamino, ethoxycarbonylmethylamino, cyano Methylamino, nitroethylamino, methoxymethylamino, chlorocyclohexylamino, phosphonomethylamino, phenylamino, tolylamino, cumethylamino, mesitylamino, xylylamino, chlorophenylamino, bromophenylamino, io Dophenylamino, acetylphenylamino, acetamidephenylamino, aminophenylamino, naphthylamino, morpholino groups, and the like.

Specific specific examples of the compound of the general formula (1) of the present invention are illustrated below.

(1) a compound of formula (1-a)

(2) a compound of formula (1-b)

(3) a compound of formula (1-c)

(Except when R ₂ is -OH and R ₃ is -OR ')

2-sulfonyloxyethyl phosphonic acid or 2-sulfonyloxyethyl thionophosphonic acid according to the present invention can be easily prepared from 2-sulfonyloxyethylphosphonic acid diester represented by the following structural formula.

Wherein R ₁ is as defined above and R " contains 1 to 4 carbon atoms such as alkyl, chloromethyl or 2-chloroethyl, suitable for having 1 to 4 carbon atoms such as methyl, ethyl or isopropyl Is an alkenyl group containing 1 to 5 carbon atoms, such as a suitable haloalkyl group or allyl group.)

This method is prepared by reacting a known 2-hydroxyethylphosphonic acid diester (organic reaction, Synthesis Example 6, vol. 1951, page 290) with the corresponding sulfonyl halide.

The compound of the general formula (4) may be obtained by a method similar to a known method for synthesizing sulfone esters from alcohols, although not described in the literature. For example, these compounds are 2-hydroxyethylphosphonic acid diesters under cooling in the presence of a base such as inorganic alkalis such as sodium carbonate, sodium hydroxide, calcium hydroxide or calcium hydroxide, organic amines such as triethylamine, trimethylamine, pyridine or lutidine. Can be obtained by mixing with the corresponding sulfonyl halide. Typically, the reaction temperature is about -20 ° C to about 40 ° C and the reaction time is about 30 minutes to about 40 hours.

Some embodiments of synthesizing the active compound of general formula (1) from the sulfonyloxyethyl phosphonic acid diester of general formula (2) are described below.

(1) Synthesis of Compound of General Formula (1-a)

The compound of formula (1-a) reacts the phosphonic acid diester of formula (4) described above with phosphorus pentachloride (PCl ₅ ) to give the compound of formula (5), ie, the following formula (6) or ( The compound of 7) is obtained, and the resulting phosphonochlorate or phosphonic acid dichloride is prepared by reacting with water, alcohol or phenol of the following general formula (8).

In each formula above,

R ₁ is as described above,

Y is Cl or -OR "group,

R 'and R "are as described above.

The reaction between the compound of formula (5) and phosphorus pentachloride can be carried out in the presence or absence of a solvent. Generally this reaction can be carried out at a temperature between about 0 ° and about 180 ° C., suitably between room temperature and about 150 ° C., for about 1 minute to about 5 hours, generally about 1 minute to about 2 hours. Examples of solvents that can be used in the present invention include aromatic hydrocarbons such as methylene chloride, chloroform or carbon tetrachloride, aromatic hydrocarbons such as toluene, benzene and xylene and ethers such as diethyl ether or ethylene glycol dimethyl ether.

It is preferable to perform reaction of the compound of General formula (6) or (7), and the compound of General formula (8) in presence of a solvent. This reaction is carried out more easily in the presence of a basic compound. Thus, this reaction is suitably carried out in the presence of a basic compound, for example an inorganic alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate, triethylamine, trimethylamine, lutidine or pyridine. The solvent may be the same as those exemplified for the reaction between the compound of formula (2) and phosphorus pentachloride. The reaction is preferably carried out at about -50 ° to about + 100 ° C, preferably at about -10 ° to about + 25 ° C. Suitable reaction times are from 10 minutes to about 20 hours.

Compounds of formula (1-a) wherein R 'is hydrogen can also be prepared by other methods. For example, the phosphonic acid diester of general formula (4) is reacted with trialkylsilyl chloride to obtain trisilyl phosphonate of general formula (9), and the resulting compound is water and / or methanol, ethanol or React with lower alcohols of 1 to 4 carbon atoms like propanol.

Wherein R ₁ is as described above.

Usually, this reaction proceeds in the absence of solvent. However, if necessary, the same solvent as exemplified in the reaction of the compound of formula (4) with phosphorus pentachloride may also be used in this reaction. The reaction temperature is about -10 ° to 70 ° C, preferably about 20 ° to about 40 ° C.

(2) Synthesis of Compound of General Formula (1-b)

The compound of formula (1-b) reacts phosphonic acid dichloride of formula (7) with phosphorus pentasulfide to form thionophosphonic acid dichloride represented by the following formula (10), and the resulting compound is general It can be obtained by reaction with water, alcohol or phenol of formula (5) or thiol of general formula (7).

Wherein R ₁ and R 'are the same as described above.

Usually, the reaction of the phosphonic acid dichloride of general formula (7) with phosphorus penta sulfide is performed in absence of a solvent. However, if desired, it may also be carried out in the presence of a solvent, for example an aromatic hydrocarbon such as toluene, xylene or cumene. This reaction can be carried out at a temperature between about 50 ° and about 200 ° C, in particular between about 120 ° and about 150 ° C. The reaction time is for example between about 1 minute and about 15 hours, preferably between about 5 minutes and about 2 hours.

The reaction of the resulting thionophosphonic acid dichloride of general formula (10) with a compound of general formula (8) or (11) is, for example, suitably about -20 ° to about + 150 ° C., and about to be further conjugated. It may be performed for about 1 minute to about 50 hours at a temperature between 0 ° and about 40 ° C. Since this reaction is easier to carry out in the presence of a basic compound, the reaction can be carried out with a basic compound, for example inorganic alkalis such as sodium carbonate, sodium hydroxide, potassium hydroxide, or calcium carbonate, or triethylamine, trimethylamine, pyridine or lutidine It is suitable to carry out in the presence of an organic amine such as. This reaction can be carried out in the presence or absence of a solvent. Specific examples of the solvent are the same as those exemplified for the reaction of the compound of formula (4) with phosphorus pentachloride.

(3) Synthesis of Compound of General Formula (1-c):

Among the compounds of the formula (1-c), a compound represented by the following formula is reacted with a thiol of the formula (11) in the presence of a basic compound or a phosphonochlorate of the formula (6) or a general formula The phosphonic acid dichloride of (7) can be synthesized by reacting with a thiol of the general formula (11) and then reacting with water, an alcohol or a phenol of the general formula (8) in the presence of a base. This basic compound may be the same as the inorganic alkali and organic amine exemplified above. The reaction temperature is suitably between about -50 ° and about 100 ° C, in particular between about -20 ° and about + 25 ° C. The reaction solvent and reaction time may be the same as those described for the reaction between thionophosphonic acid dichloride of formula (10) and the compound of formula (11).

Wherein R ₁ and R 'are the same as above.

Among the compounds of the general formula (1-c), the compounds having the general formula (1-cB) as follows may be used under the same conditions as described for the preparation of the compounds of the general formula (1-cA). Phonic acid dichloride can be synthesized by reacting with thiol of general formula (11).

Wherein R ₁ and R 'are the same as above.

Among the compounds of the general formula (1-c), the compound having the general formula (1-cC) is represented by the following general formula wherein phosphonoyldichloride of the general formula (7) is a primary or secondary amine in the presence of a basic compound It can be synthesized by reacting with the compound represented by (12). Examples of base compounds are the same as those given above. The reaction conditions are the same as those described in connection with the preparation of the compound of formula (1-c-A).

Wherein R ₁ and R 'are the same as above.

In the formula, R 'is the same as described above, and may represent a morpholino group including N.

Hereinafter, the use of the compound by the method of the present invention will be described.

A compound of the formula (1) prepared by the method of the present invention is used as an active ingredient, and the plant growth adjustment amount thereof and a gas, a liquid, or a solid diluent are formulated into a desired formulation such as a hydrating agent, an emulsifying agent, a liquid or a paste. It can be used as a plant growth regulator. The amount of the active compound of formula (1) can be varied from about 0.0001 to about 99% by weight, suitably 0.001 to 50% by weight, more preferably 0.005 to 10% by weight, based on the weight of the plant growth regulator. Examples of diluents include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl cellosolve, diethylene glycol monoethyl ether, dimethyl sulfoxide, dimethylformamide, isopropyl acetate, kerosene Liquid diluents such as benzene, toluene or petroleum ether, gas diluents such as air, nitrogen, argon, propane, ethane or vinyl chloride and talc, diatomaceous earth, kaolin, montmorillonite, attapulgite, wheat flour and There is a solid diluent such as soy flour.

Thus, for example, the use of the compounds of the general formula (1) according to the present invention in stems, leaves, branches, fruits, seeds, roots or shoots, or in areas where the plants are growing or will be grown, will regulate the growth of the plants. Can be.

The amount of the compound of formula (1) to be used may be appropriately selected depending on the plant to be treated, the time of application, the desired adjusting action, and the like. Typically, this amount is about 10-4, 000 g, suitably about 20-2, 000 g per 10 sites in which the plant will grow or will grow. When the compound is used in the plant itself, for example, when applied to fruits or rubber trees, the amount varies depending on the surface area of the plant or the form of the compound of formula (1). Typically, the compound of formula (1) is used in an amount of about 2 to 100 ml of a liquid composition containing at a concentration of about 10 to 10,000 ppm. When immersing at least a part of a plant, for example, root shoots such as seeds, bulbs or seed potatoes in a compound of formula (1), they are contained at a concentration of about 10 to 10,000 ppm for about 3 minutes to about 6 hours. A predetermined adjustment effect can be obtained by immersing in the liquid composition containing a compound.

The active compound used in the present invention is not limited to one kind, and two or more kinds of compounds may be used as a mixture. Plant growth constituents comprising the compounds of the invention as active ingredients can be used in combination with fertilizers, pesticides, fungicides, preparations and other plant growth regulators.

Hereinafter, the manufacturing method of the method of this invention is explained in full detail as Examples 1-18.

Preparation of Active Compounds

Example 1

-브로모프로필슬포닐클로라이드 6.0g의 용액을 적가 펀넬에 의하여 냉각 용액에 적가했다. 적가 종료 후, 혼합 용액을 24시간 동안 0~5℃에서 방치시켰다. 반응 혼합물을 5% 염산 50ml에 경사하고 디에틸에에테르로 추출시켰다. 추출물을 무수 황산나트륨으로 건조시키고 용매를 감압하에서 유거하였다. 추출물을 무수 황산나트륨으로 건조시키고, 용매를 감압하에서 유거했다. 생성물을 18시간 동안 0.7mmHg 하의 실온에서 더욱 건조시켜 무색 유산의 디메틸 2-(3-브로모프로필슬포닐옥시) 에틸포스포네이트를 얻었다(수율 75몰%). 생성물은 다음과 같은 특성을 나타냈다.3.9 g of dimethyl 2-hydroxyethylphosphonate and 5.9 g of pyridine were dissolved in 40 ml of dry dimethyl ether and the solution was cooled with ice to -5 ° C. Dissolved in 30 ml of dry diethyl ether.

A solution of 6.0 g bromopropylsulfonylchloride was added dropwise to the cooling solution by dropwise funnel. After completion of the dropwise addition, the mixed solution was left at 0-5 ° C for 24 hours. The reaction mixture was tilted to 50 ml of 5% hydrochloric acid and extracted with diethyl ether. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The extract was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The product was further dried at room temperature under 0.7 mm Hg for 18 hours to give dimethyl 2- (3-bromopropylsulfonyloxy) ethylphosphonate as a colorless lactic acid (yield 75 mol%). The product exhibited the following properties.

_n D ²² = 1.4960

Nuclear Magnetic Resonance Spectrum (CDCl ₃ )

δ = 2.30 ppm (dt, 2H), 2.00-2.60 (m, 2H), 3.36-3.70 (m, 4H), 3.77 (d, 6H), 4.38 (dt, 2H)

2.0 g of dimethyl-2- (3-bromopropylsulfonyloxy) ethylphosphonate was dissolved in 30 ml of dry methylene chloride. 2.5 g phosphorus contaminant was added and the mixture was refluxed for 1 h. The solvent was distilled off under reduced pressure, and the byproduct was distilled off under reduced pressure by passing dry sulfur dioxide through the residue. 10 ml of methylene chloride was added to make a solution, and water (1 ml) was added under ice-cooling. The mixture was stirred for 20 minutes at room temperature and the solvent was distilled off under reduced pressure. 20 ml of acetone were added to make a solution. A small amount of activated carbon was added to decolor the solution and remove residual hydrogen chloride. Activated carbon was separated by filtration, and the solvent was distilled off under reduced pressure. The residue was dried in vacuo to give a colorless oily substance which was identified as the first compound falling within the range of the general formula (1-a) above. The yield was 83 mol%. This compound exhibited the following properties.

_n D ^{23 · 5 ° C.} = 1.4935

By the same method as described above, compounds Nos. 2 to 4, 6 and 10 to 16, 18, 19, 31 to 33, 35 to 37 and 41 of general formula (1-a) were prepared.

These characteristics were as follows.

Compound No. 3 _n D ^{23 · 5 ° C.} = 1.4800

4 _n D ^{23 · 5 ° C} = 1.4712

6 _n D ^{23 · 5 ° C} = 1.4673

10 _n D ^{23 · 5 ° C} = 1.4745

11 _n D ^{23 · 5 ° C} = 1.5149

14 _n D ^{23 · 5 ° C} = 1.5040

16 m.p = 110 ~ 113 ℃

41 _n D ^{20 ° C} = 1.4609

Example 2

2.0 g of dimethyl 2- (2-methoxycarboylethylsulfonyloxy) ethylphosphonate was placed in a reactor washed with nitrogen gas, and 4.8 g of phosphorus pentachloride was added with stirring at 140 ° C. After reacting for 10 minutes, the reaction mixture was cooled to room temperature. Dry sulfur dioxide was passed through the mixture and the byproduct was distilled off under reduced pressure. 10 ml of methylene chloride was added to make a solution, followed by dropwise addition of 1.25 g (equivalent) of dodecyl alcohol. The mixture was further cooled to -10 ° C and 0.53 g of pyridine was added dropwise with stirring. After leaving the mixture for one day, the resulting crystals were separated by filtration under reduced pressure. After cooling, water was added to the mother liquor in an amount exceeding the equivalent weight. The mixture was stirred at room temperature for 2 hours and the solvent was distilled off under reduced pressure. 10 ml of water was added to the residues to make a solution. Next, activated carbon was added to decolor the solution, followed by filtration. The mother liquor was concentrated under reduced pressure and dried in vacuo to exhibit the properties identified as compound No. 26 of formula (1-a).

IR spectrum: 3, 400 cm ^-1 , 2, 260, 1, 700, 1, 350, 1, 160, 1, 040, 950

By the same method as described above, the compounds of Compound Nos. 25, 27, 28, 29, and 30 were obtained.

Example 3

60 g of dimethyl 2-hydroxyethylphosphonate and 4.2 g of triethylamine were dissolved in 75 ml of dry dimethyl ether, and the solution was cooled to -5 deg.

를 80몰%의 수율로 얻었다. 생성물은 다음과 같은 특성을 가지고 있었다.4.45 g of methanesulfonyl chloride was dissolved in 75 ml of dry diethyl ether, and the solution was added dropwise to the cooling solution by dropwise funnel having a side tube with stirring. After the dropwise addition, the temperature of the solution was reduced to room temperature and the solution was further stirred for 5 hours. The reaction mixture was concentrated under reduced pressure, and diethyl ether was added again. Insoluble matter was isolated by filtration. The ether phase was washed with water, dried and the solvent was organic. The residue was dried at 0.7 mmHg at room temperature to give a colorless oily material. therefore,

Was obtained in a yield of 80 mol%. The product had the following characteristics.

IR spectrum: 1, 250cm ^-1 (absorption of the unique P = O), 1, 030cm -1, 960cm -1 ( absorption of the unique ^{POC, 1, 360cm -1, 1} , 175cm -1 (O-SO 2 - of Unique absorption).

=1.34ppm(t, 6H), 2.30(dt, 2H), 3.05(s, 3H), 4.14(dq, 4H), 4.45(dt, 2H)NMR spectrum (solvent, CD ₃ OD / CDCl ₃ = 1/7 volume ratio):

= 1.34 ppm (t, 6H), 2.30 (dt, 2H), 3.05 (s, 3H), 4.14 (dq, 4H), 4.45 (dt, 2H)

Mass spectrum: p [parent peak] = 260

A two-necked flask washed with dry argon gas was charged with 2.14 g of diethyl 2-methanesulfonyloxyethylphosphonate and 3.38 g of phosphorus pentachloride and heated to 110 ° C. with stirring. The temperature was then raised to 150 ° C. and the mixture was kept at this temperature for 20 minutes. The reaction mixture was then cooled to room temperature and passed through sulfur dioxide to oxidize unreacted phosphorus contaminants. The byproduct was distilled off under reduced pressure, and 20 ml of diethyl ether was added to dissolve the product. The water was added dropwise to the resulting solution with stirring in an amount exceeding the equivalent weight. The solvent was distilled off under reduced pressure and the residue was dried at 0.77 mmHg at room temperature to obtain a white crystalline material. The crystals were recrystallized from a solvent consisting of 1: 1 volume ratio of chloroform and acetone. Compound No. 38, which is a melting point of 116.5 to 117 占 폚 and was colorless crystals, was obtained in a yield of 67 mol%.

This product exhibited the following properties.

독특한 흡수), 1, 020cm^-1, 970cm^-1(P-O 독특한 흡수), 1, 350cm^-1, 1, 140cm^-1(O-SO₂-독특한 흡수).IR ^{spectrum: 2, 280cm -1, 1,} 650cm -1 (

Unique ^{absorbent), 1, 020cm -1, 970cm} -1 (PO unique ^{absorbent), 1, 350cm -1, 1} , 140cm -1 (O-SO 2 - unique absorption).

=2.26ppm(dt, 2H), 3.10(s, 3H), 4.44(dt, 2H), 5. 36(s, 2H)NMR spectrum (solvent CD ₃ OD / CDCl ₃ = 1/7 volume ratio):

= 2.26 ppm (dt, 2H), 3.10 (s, 3H), 4.44 (dt, 2H), 5. 36 (s, 2H)

Elemental Analysis Values:

C H O P S

Calculated Value (%) 17.65 4.44 47.03 15.17 15.71

Found (%) 18.18 4.39 46.98 15.20 15.50

By the same method as the above, the compound of the compound number 40, 42, 43, 45 and 46 of general formula (1-a) was prepared. The properties of these compounds were as follows.

Example 4

2.6 g of dimethyl 2- (3-ethoxypropylsulfonyloxy) ethylphosphonate was placed in a reactor washed with nitrogen gas, and 4.5 g of phosphorus contaminant was added while stirring at 140 ° C. After reacting for 10 minutes, the reaction mixture was cooled to room temperature, and passed through the dry pot. The resulting byproduct was distilled off under reduced pressure. The remaining oily substance was dissolved in 10 ml of methylene chloride and then water (1 ml) was added with ice cooling. The mixture was stirred at room temperature for 20 minutes, and the solvent was distilled off under reduced pressure. 10 ml of water was added to make a solution, and a small amount of activated carbon was used to decolor the solution and remove residual hydrogen chloride. Activated carbon was separated by filtration, and the solvent was distilled off under reduced pressure. The product was further dried in vacuo to yield a colorless oily substance identified as compound 7 of formula (1-a) in a yield of 62 mol%. This compound had a refractive index ( _n D ^{23 · 5 ° C.} ) of 1.4805.

By the same method, the compound of compound numbers 8, 9, 17, and 20-24 of general formula (1-a) was manufactured. The properties of these compounds were as follows.

Example 5

3.0 g of diethyl 2-methanesulfonyloxyethylphosphonate and 2.4 g of phosphorus pentachloride obtained in the same manner as in Example 3 were dissolved in 20 ml of dry toluene, and the solution was heated to reflux for 2.5 hours at atmospheric pressure. Dry sulfur dioxide was then passed through the reaction mixture to oxidize unreacted phosphorus contaminants. The solvent and byproducts were distilled off under reduced pressure. 20 ml of diethyl ether was added to the resulting oily substance. Water was added to the solution in an amount exceeding the equivalent weight while stirring. The solvent was distilled off under reduced pressure, and the residue was dried at a pressure of 0.7 mmHg at a temperature of room temperature to obtain a colorless oily substance identified as compound 39. The yield was 97 mol%. The product exhibited the following properties.

의 독특한 흡수), 1, 660cm^-1(

독특한 흡수), 950~1, 040cm^-1(P-O-독특한 흡수), 1, 360cm^-1, 1, 180cm^-1(O-SO₂-독특한 흡수).Spectrum: 2,610cm ^-1 , 2,280cm ^-1 (

Unique absorption), 1,660 cm ^-1 (

Unique absorption), 950-1, 040 cm ^-1 (PO-unique absorption), 1,360 cm ^-1 , 1, 180 cm ^-1 (O-SO ₂ -unique absorption).

=1.35ppm(t, 3H), 2.30(dt, 2H), 3.09(s, 3H), 4.11(dq, 2H), 4.47(dt, 2H), 5. 84(s, 1H)NMR spectrum (solvent, CD ₃ OD / CDCl ₃ = 1/7 volume ratio):

= 1.35 ppm (t, 3H), 2.30 (dt, 2H), 3.09 (s, 3H), 4.11 (dq, 2H), 4.47 (dt, 2H), 5. 84 (s, 1H)

Mass spectrum: P-232

By the same method, the 44th compound of Structural Formula (1-a) was prepared. The 1R spectrum of this compound was as follows.

2, 980 cm ^-1 , 2, 280, 1, 595, 1, 360, 1, 190, 1, 175, 1, 040-1,000, 950

Example 6

Dimethyl 2-vinylsulfonyloxyethylphosphonate was prepared from 3.8 g of dimethyl 2-hydroxyethylphosphonate, 1.9 g of pyridine and 4.0 g of 2-chloroethylsulfonylchloride in the same manner as in Example 1. The yield was 20 mol%. The NMR spectrum (CDCl ₃ ) of this product was as follows.

=2.30ppm(dt, 2H), 3.78(d, 6H), 4.32(dt, 2H), 6.1~6.6(m, 3H)

= 2.30 ppm (dt, 2H), 3.78 (d, 6H), 4.32 (dt, 2H), 6.1-6.6 (m, 3H)

Compound No. 34 of Formula (1-a) was prepared in the same manner as in Example 1 from 2.44 g of dimethyl 2-vinylsulfonyloxyethylphosphonate and 2.10 g of phosphorus pentachloride. The yield was 60 mol%. This product showed the following nuclear magnetic resonance spectra.

(CD₃OD)=6.8~6.1ppm(m, 3H), 5.1ppm(s, H), 4.4(dt, 2H), 3.72(d, 3H), 2.28(dt, 2H)

(CD ₃ OD) = 6.8 ~ 6.1ppm (m, 3H), 5.1ppm (s, H), 4.4 (dt, 2H), 3.72 (d, 3H), 2.28 (dt, 2H)

Compounds 35, 36 and 37 of formula (1-a) were prepared by the same method as described above, respectively.

Example 7

By the same method as in Example 3, dimethyl 2-methanesulfonyloxyethylphosphonate was prepared in 1 mol of dimethyl 2-hydroxyethylphosphonate, 39.5 g of pyridine and 11.5 g of methanesulfonyl chloride in a yield of 88 mol%. It was.

=2.31ppm(dt, 2H), 3.09(s, 3H), 3.80(d, 6H), 4.47(dt, 2H)Nuclear Magnetic Resonance Spectrum (CDCl ₃ ):

= 2.31 ppm (dt, 2H), 3.09 (s, 3H), 3.80 (d, 6H), 4.47 (dt, 2H)

13.9 g of dimethyl 2-methanesulfonyloxyethylphosphonate was placed in a reactor and heated to 140-150 ° C. 30.0 g of phosphorus contaminants were added while stirring, and this reaction was performed for 20 minutes. The reaction mixture was cooled to room temperature, and the reaction mixture was passed through dry sulfurous acid gas to oxidize unreacted phosphorus contaminants. The resulting by-product was distilled off under reduced pressure, and phosphorus contaminants were added to the remaining oil liquid. The mixture was heated to 120-130 ° C. for 2 hours and extracted with ether in dry diethyl. The insolubles were separated by filtration and the filtrate was concentrated under reduced pressure. The concentrate was dried in vacuo (0.1 mm Hg) to give 6.2 g of a brown oil in 41.2 mol% yield. This compound exhibits the following properties and was identified as compound 47 of general formula (1-b).

Infrared absorption spectrum (cm ^-1 ): 3, 040, 2, 980, 2, 940, 1, 465, 1, 360, 1, 240, 1, 180, 1, 050, 990, 960, 880, 800, 760 , 720.

=3.15ppm(s, 3H), 3.37(dt, 2H), 4.75(dt, 2H).Nuclear Magnetic Resonance Spectrum (CDCl ₃ ):

= 3.15 ppm (s, 3H), 3.37 (dt, 2H), 4.75 (dt, 2H).

Refractive Index: _n D ²⁵ = 1.4650

By the same method, the 48th compound of general formula (1-b) was prepared. The refractive index ( _n D ^{17 ° C} ) of this product was 1.5536.

Example 8

2.2 g of 2-methanesulfonyloxyethylthiophosphonyl dichloride obtained in Example 7 were cooled with ice, and 2.0 g of water was added dropwise while stirring. After completion of the dropwise addition, the mixture was warmed up to 40 ° C, reacted for 1 hour, and then concentrated at room temperature and reduced pressure. The residue was dissolved in a small amount of water, and a small amount of activated carbon was added thereto. The mixture was stirred and then filtered. The mother liquor was concentrated under reduced pressure and dried in vacuo (0.1 mmHg) to obtain 1.4 g of a highly viscous liquid identified as compound 49 of formula (1-b).

The product showed the following properties and was identified as compound 49.

Infrared absorption spectrum (cm ^-1 ): 3, 020, 2, 930, 2, 600, 2, 290, 2, 160, 1, 630, 1, 350, 1, 250, 1, 170, 1, 040 ~ 920 , 790, 730.

=2.33ppm(dt, 2H), 3.11(s, 3H), 4.45(dt, 2H), 5.47(s, 2H)Nuclear Magnetic Resonance Spectrum (CDCl ₃ ):

= 2.33 ppm (dt, 2H), 3.11 (s, 3H), 4.45 (dt, 2H), 5.47 (s, 2H)

Refractive Index: _n D ²⁵ = 1.5075

By the same method as above, compounds 50 and 52 of General Formula (1-b) were prepared. 52 times the refractive index of the compound _(n D ^{25 ℃)} was 1.5450.

Example 9

2.2 g of 2-methanesulfonyloxyethylthiophosphonic acid dichloride obtained in Example 7 was dissolved in 20 ml of dry diethyl ether, and 1.8 g of benzyl alcohol was added dropwise while stirring. Then, 0.8 g of pyridine was added dropwise under ice cooling with stirring. After completion of the dropwise addition, the mixture was left at room temperature for 1 week to filter out the resulting crystals. The mother liquor was concentrated under reduced pressure and dried in vacuo to yield 1.6 g of a viscous liquid identified as compound of formula (1-b).

By the same method, the 53rd-56th compound of general formula (1-b) was manufactured.

Example 10

7.8 g of dimethyl 2-methanesulfonyloxyethylphosphonate was placed in a reactor and heated to 140-150 ° C. 16.8 g of phosphorus pentachloride was added while stirring, and the reaction was allowed to proceed for 20 minutes. The reaction mixture was cooled to room temperature, and dry sulfurous acid gas was passed through the reaction mixture to oxidize unreacted phosphorus contaminants. The resulting byproduct was distilled off under reduced pressure. The remaining oily liquid was dissolved in 60 ml of dry methylene chloride, and the solution was cooled to -10 to -18 占 폚. 21.3 g of p-chlorobenzenethiol and 11.1 g of pyridine were simultaneously added dropwise to this solution while stirring. After completion of the dropwise addition, the solution was left at 0-5 DEG C for 48 hours. The resulting crystals were filtered off, and the mother liquor was concentrated under reduced pressure to obtain a solid. 100 ml of diethyl ether was added to this solid to extract the soluble material. Then, etheric acid was concentrated under reduced pressure. The resulting solid was recrystallized from petroleum-ether to give colorless acicular crystals identified as compound No. 57 of formula (1-c) in a yield of 30 mol%. This product exhibited the following properties.

Infrared absorption spectrum (cm ^-1 ): 3, 040, 2, 960, 1, 595, 1, 490, 1, 410, 1, 338, 1, 180, 1, 165, 1, 100, 1, 040, 1 , 020, 990, 960, 850, 720.

=2.50ppm(dt, 2H), 3.02(s, 3H), 4.15(d, 4H), 4.40(dt, 2H), 7.32(s, 10H). 융점 : 84~85.5℃Nuclear Magnetic Resonance Spectrum (CDCl ₃ ):

= 2.50 ppm (dt, 2H), 3.02 (s, 3H), 4.15 (d, 4H), 4.40 (dt, 2H), 7.32 (s, 10H). Melting Point: 84 ~ 85.5 ℃

By the same method, compounds 58, 59, 60, 61, 62, 63 and 71 of formula (1-c) were prepared. 58 times the melting point of the compound was 56 ~ 59 ℃, No. 60 times the refractive index of the compound _(n D ^{25 ℃)} is 1.6200.

Example 11

Compound No. 64 of Formula (1-c) was prepared from 7.6 g of dimethyl 2-methanesulfonyloxyethylphosphonate, 9.0 g of phosphorus pentachloride and 6.2 g of ethyl thiol by the same method as described in Example 7. Prepared. The yield was 48 mol%. This product exhibited the following properties.

Infrared absorption spectrum (cm ^-1 ): 3, 020, 2, 970, 2, 940, 1, 460, 1, 350, 1, 270, 1, 170, 1, 135, 1, 040, 940, 8880, 810 , 720.

By the same method, compounds 65 and 72 of General Formula (1-c) were prepared.

Example 12

Compound 68 of formula (1-c) was prepared from 2.3 g of dimethyl 2-methanesulfonyloxyethylphosphonate, 2.3 g of phosphorus pentachloride and 0.46 g of dimethylamine by the same method as described in Example 1. Prepared. The yield was 52 mol%. The IR spectrum of this product was as follows.

2, 980 cm ^-1 , 1, 360, 1, 250, 1, 180, 1, 030, 960-950.

By the same method as described above, compound 69 of general formula (1-c) was prepared.

Example 13

1.2 g of benzylthiol and 3.3 g of dimethyl 2- (p-chlorobenzenesulfonyloxy) ethylphosphonate were prepared in the same manner as described in Example 1 for compound No. 66 of the general formula (1-c). Prepared from 0.2 g. By the same method, the 67th and 70th compound of general formula (1-c) was obtained.

Example 14

7.1 g of diethyl 2-methanesulfonyloxyethylphosphonate was heated to 145 ° C. While stirring, 14.2 g of phosphorus pentachloride was added and these were allowed to react for 30 minutes. The mixture was cooled to room temperature. Sulfur dioxide was passed through this mixture, and the by-products were distilled off under reduced pressure. 50 ml of dry methylene dichloride was added to this residue to give a solution. The solution was cooled to −20 ° C. and 7.5 ml of dry dimethylamine was passed through the solution. After leaving this solution for 48 hours, the solvent was distilled off under reduced pressure. Then 50 ml of dry ether was added and the insoluble material was filtered off. The mother liquor was concentrated under reduced pressure and dried under vacuum (0.7 mmHg) at room temperature to obtain an oily liquid identified as compound 73 having the following characteristics.

Infrared absorption spectrum: 2, 940 cm ^-1 , 1, 460, 1, 360, 1, 310, 1, 265, 1, 175, 990, 725.

Refractive Index ( _n D ^{13 ° C} ) = 1.4623

Example 15

7.1 g of diethyl 2-methanesulfonyloxyethylphosphonate was heated up to 145 ° C and 14.2 g of phosphorus pentachloride was added with stirring. The mixture was allowed to react for 30 minutes and then cooled at room temperature. Sulfurous acid gas was passed through the mixture, and the by-products were distilled off under reduced pressure. 50 ml of dry methylene dichloride was added to the residue to give a solution. The solution was cooled to −20 ° C. and a solution of 11.3 g of aniline dissolved in 20 ml of ethylene dichloride was added dropwise. At 5 ° C., the mixture was left for 48 hours. The resulting precipitate was filtered off. The mother liquor was concentrated under reduced pressure and dried under vacuum (0.7 mmHg) at room temperature to obtain a waxy substance. This product was identified as compound 74 having the following infrared absorption spectrum.

Infrared absorption spectrum: 3, 040 ~ 2, 900cm ^-1 , 1, 590, 1, 495, 1, 350, 1, 180 ~ 1, 120, 1, 020 ~ 930, 750, 690.

Example 16

6.9 g of dimethyl 2-methanesulfonyloxyethylphosphonate was heated to 145 ° C, and 14.8 g of phosphorus pentachloride was added while stirring. The reaction was allowed to react for 20 minutes. The reaction mixture was cooled to room temperature, and then sulfurous acid gas was passed through the mixture. The resulting byproduct was distilled under reduced pressure. 50 ml of methylene dichloride was added to the resulting residue to form a solution. 7.7 g of isopropylamine was added to this methylene chloride solution generated while cooling, and the mixture was left at 5 ° C. for 48 hours. The resulting precipitate was filtered, concentrated under reduced pressure, and then vacuum dried to obtain an oily liquid. This product was identified as compound No. 75 having the following infrared absorption spectrum and refractive index.

Infrared absorption spectrum: 3, 190 cm ^-1 , 2, 970, 1, 370, 1, 300, 1, 210, 1, 170, 1, 130, 1, 040, 930.

Refractive Index ( _n D ^{17 ℃} ): 1.4768

Example 17

By the same method as described in Example 16, a solid material was prepared from 5.9 g of dimethyl 2-methanesulfonyloxyethylphosphonate, 18.7 g of phosphorus pentachloride, and 14.3 g of p-chloroaniline. This product was identified as compound No. 76 having the following infrared absorption spectrum.

Infrared absorption spectrum: 2, 940 cm ^-1 , 1, 490, 1, 350, 1, 280, 1, 222, 1, 168, 1, 090, 940, 810.

Example 18

By the same method as described in Example 16, a viscous material was prepared from 7.5 g of dimethyl 2- (p-toluenesulfonyl) oxyethylphosphonate, 12.2 g of phosphorus pentachloride and 8.6 g of isopropylamine. This product was identified as compound No. 81 having the following infrared absorption spectrum and refractive index.

Infrared absorption spectrum: 3, 240 cm ^-1 , 2, 970, 1, 595, 1, 460, 1, 360, 1, 300, 1, 170-1, 218, 1, 120, 1, 050, 1, 070, 815, 680.

Refractive Index ( _n D ^{17 ℃} ): 1.5027

By the same method as described above, compounds 77-80 and 82-93 of the general formula (1-c) were prepared.

Formulation Examples and Use Examples (all parts are parts by weight)

Formulation Example 1 (Liquid)

A liquid formulation having a concentration of 30% active ingredient was prepared by mixing the following components.

2-methanesulfonyloxyethylthiophosphonate (compound No. 49 of general formula (1-b)) 30 parts

30 parts ethyl alcohol

10 parts propylene glycol

25 parts water

5 parts of polyoxyethylene dodecyl ether

In use, the solution was diluted with water to a desired concentration and then sprayed.

Formulation Example 2 (Liquid)

A liquid formulation having a concentration of 30% active ingredient was prepared by mixing the following components.

2- (2-carboxyethylsulfonyloxy) ethylphosphonic acid (the eighth compound of formula (1-a))

Part 30

Propylene glycol 25 parts

30 parts ethyl alcohol

10 parts water

Alkylbenzenesulfonate (NECGEN, registered trademark of Daiichi Kogyo Seiyaku Co., Ltd.) as a surface active agent

In use, the solution was diluted with water to a desired concentration and then sprayed.

Formulation Example 3 (Emulsifier)

An emulsifier having an active ingredient concentration of 40% was prepared by mixing the following ingredients.

40 parts of dithioester (compound 58 in general formula (1-c)) of S, S-diphenyl-2, and 2-methanesulfonyloxyethylphosphonic acid

50 xylols

10 parts of Sorpol 800 (trademark of polyoxyethylene surfactant, product of Togaku Corporation)

In use, this emulsifier was diluted with water to a desired concentration and then sprayed.

Formulation Example 4 (Emulsifier)

Emulsifiers having an active ingredient concentration of 50% were prepared by uniformly mixing the following ingredients.

50 parts of monoethyl 2- (3-thiocyanatopropylsulfonyloxy) ethylphosphonate (Compound No. 14 of Formula (1-a))

Xylol 40

Sorpol 800 Part 10

In use, this emulsifier was diluted with water to a desired concentration and then sprayed.

Formulation Example 5 (Hydrating)

A hydrating agent having an active ingredient concentration of 30% was prepared by mixing and powdering the following ingredients.

30 parts of 2- (2-carboxyethylsulfonyloxy) ethylthionophosphonic acid (compound No. 50 of General Formula (1-b))

65 equivalents of talc and clay

Sodium alkylbenzenesulfonate 3 parts

Sodium dinaphthyl methane disulfonate 2 parts

In use, this hydrating agent was diluted with water and used at a desired concentration.

Formulation Example 6 (Hydrating)

A hydrating agent having an active ingredient concentration of 40% was prepared by mixing and powdering the following ingredients.

40 parts of 2- (2-phthalimidoethylsulfonyloxy) ethylphosphonic acid (compound No. 17 of general formula (1-a))

55 parts equivalent mixture with Zieklite and Kunilite (trademark for fillers)

3 parts sodium alkylbenzenesulfonate as surfactant

Sodium dinaphthyl methane disulfonate 2 parts

In use, this hydrating agent was diluted with water and used at a desired concentration.

Formulation Example 7 Paste

Paste having an active ingredient concentration of 3% was prepared by uniformly mixing the following components.

3 parts of monomethyl 2- (3-bromopropylsulfonyloxy) ethylsulfonate (the first compound of formula (1-a))

Sorbitol 20 parts

Sorbitol-long chain fatty acid ester

Mineral oil part 10

57 parts of water

Formulation Example 8 (Emulsifier)

50 parts monoethyl 2-methanesulfonyloxyethyl phosphonate

Xylol 40

10 parts of polyoxyethylene compound (Sorpol 800, registered trademark of Toga Chemical Co., Ltd.) as a surfactant

The components were uniformly mixed to obtain an emulsifier having an active ingredient concentration of 50%.

In use, this emulsifier was diluted with water to a desired concentration and then sprayed.

Formulation Example 9 (Liquid)

2-methanesulfonyloxyethylphosphonic acid 30 parts

Propylene glycol 25 parts

30 parts ethyl alcohol

10 parts water

Alkylbenzenesulfonate (NEOGEN, trademark of Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant

These components were uniformly mixed to prepare a liquid having an active ingredient content of 30%. In use, it was diluted and sprayed to the desired concentration.

Formulation Example 10 (Hydrating)

2-methanesulfonyloxyethylphosphonic acid 40 parts

55 parts equivalent mixture with Zieklite and Kunilite (trademark of Kokuho Corporation) as filler

Sorpol 800 (trademark of surfactant) 5 parts

The ingredients were mixed and powdered to prepare a hydrating agent having an active ingredient content of 40%. In use, this hydrating agent was diluted and sprayed to the desired concentration.

Formulation Example 11 (Liquid)

30 parts of 2-methanesulfonyloxyethylphosphonic acid bis (dimethylamide)

30 parts ethyl alcohol

Propylene glycol 25 parts

10 parts water

5 copies of alkylbenzenesulfonate (NEOGEN, registered trademark of Daiichi Kogyo Seiyaku Co., Ltd.)

These components were uniformly mixed to prepare a liquid formulation having an active ingredient concentration of 30%. In use, this liquid was diluted and sprayed to a desired concentration.

Formulation Example 12 (Emulsifier)

50 parts of 2-p-toluenesulfonyloxyethylphosphonic acid bis (isopropylamide)

Xylol 40

10 parts of Sorpol 800 (registered trademark of Toga Chemical Co., Ltd. as a surfactant)

The above components were uniformly mixed to prepare an emulsifier having an active ingredient concentration of 50%. In use, this emulsifier was diluted with water to a desired concentration and then sprayed.

Formulation Example 13 (Hydrating)

40 parts of 2-methanesulfonyloxyethylphosphonic acid bis (dimethylamide)

55 parts equivalent mixture with Zieklite and Kunilite as filler

Sorpol (surfactant) 5 parts

The ingredients were mixed and powdered to prepare a hydrating agent having an active ingredient content of 40%. In use, this hydrating agent was diluted and sprayed to the desired concentration.

Formulation Example 14 (paste)

2-methanesulfonyloxyethylphosphonic acid bis (isopropylamide) 2 parts

Bentonite Part 25

33 minutes

Waselin 20

The components were mixed well with water to prepare a paste having an active ingredient content of 2%.

Test Example 1 Swelling Test of Young Peas

A pot of 9 cm inside was filled with volcanic ash soil. Fifteen pea seeds were planted in each pot and grown for one week in a constant temperature room (cow) at 25 ° C. 2 ml of the hydrating agent of the present invention diluted with water at each concentration shown in Table 1 was uniformly sprayed on the upper part of peas grown to a height of 5-7 cm. These stones were placed in a dark room at 25 ° C, and the degree of swelling of the pea stem was evaluated at the following ratio. The results are shown in Table 1.

-: Less than 5% swelling rate based on untreated compartment

±: swelling ratio 6-20%

+: Swelling ratio 21-40%

++: Swelling ratio 41 ~ 60%

+++: Swelling rate 61 ~ 80%

++++: Swelling ratio 81 ~ 100%

TABLE 1

TABLE 1a

[Test Example 2]

A pot with a diameter of 12 cm was filled with volcanic ash soil. Evenly grown tomatoes (10 leaf steps) were transplanted into each pot. The pot was then placed in a greenhouse, and after the roots of the tomatoes were firmly established, the paste of the compound of the present invention was coated on aluminum foil in an amount of 0.1 g or 0.05 g and used for the fifth node of the tomato plant. . On day 5 after use, the degree of epigastric growth was evaluated.

TABLE 2

[Test Example 3]

Pots with an inner diameter of 12 cm were filled with volcanic ash soil, and evenly grown tomatoes (10 leaf steps) were transplanted into each pot. The pots were left in the greenhouse and when they were fully rooted, the hydrating agents of the compounds of the present invention were dissolved in water to make dilutions to the desired concentrations. 3 ml of each dilution was evenly spread over the leaves and stems of the tomatoes. The tomatoes were then grown in greenhouses for 20 days and then tested for tomato epithelial growth, eugenic root formation, deciduous action, and food damage. The evaluation of this result was shown by the ratio of the following grades.

-: No plant damage

±: slight plant weak

+: Medium weak plant

++: severe plant weak

+++: Extreme plant weakness

TABLE 3

[Test Example 4]

The soil of 15cm in diameter was filled with volcanic ash soil, and 12 Gangnam beans were planted in each flower pot. Then they were grown in the greenhouse for about a week. The eight evenly grown beans were cut with scissors. When the second three pairs of leaves of Gangnam beans were grown, the leaves and stems of Gangnam beans were sprayed with 4 ml of a hydrating agent of the compound of the present invention diluted with water at respective concentrations as indicated in Table 4. Evaluation was carried out in five grades identical to those described in Test Example 1.

TABLE 4

[Test Example 5]

Each of the concentrations shown in Table 5 was sprayed onto the stems and leaves of tobacco plants grown uniformly 8 days after the sowing date and before flowering. The spray amount of the hydrating agent diluted with water was 10 ml per tobacco plant. Then, the tobacco plants were grown in a greenhouse, and on the third day after the treatment, the drop rate of the tobacco flower buds was measured.

At 21 days after treatment, the degree of yellowing of tobacco leaves was measured. The results are shown in Table 5.

TABLE 5

TABLE 5a

[Test Example 6]

Coloring test for orange

Mandarin orange (breed Unshn) having a color similar to that of the firefly's back is covered with 2 ml of a solution of the emulsifier of the present invention diluted in water at the respective concentrations shown in Table 6, and then in a room at a constant temperature at 10 캜. I left it. Ten days after the treatment, the degree of coloring was observed. Test results are presented as the average for five oranges in each region. The evaluation was carried out in the following steps. The results are shown in Table 6.

0: coloring before treatment

1: 20% coloring

2: 40% tinted

3: 60% tinted

4: 80% coloring

5: complete coloring

TABLE 6

[Test Example 7]

50 ml of the aqueous solution of the emulsifier of the present invention diluted to each concentration shown in Table 7 was uniformly sprayed on the stem and leaves of the three-year-old nut tree (height 1.5 m). 15 days after the treatment, the deciduousness was tested. This result is shown in Table 7.

TABLE 7

[Test Example 8]

A 10% W / V solution in which the compound of the present invention was dissolved in palm oil was coated on the leaves of the three-year-old Ficus elastica tree. After two days, the coated front edge was cut off on the side of the leaf scape. The weight of the emulsion secreted from the cut leaves was allowed to penetrate into the previously measured filter paper. The filter paper was then dried in air and its weight was measured. For each concentration, the quantity of milk obtained from the 10 leaves was divided by the weight of the leaves and expressed as a percentage of the value obtained in the untreated plot.

This result is shown in Table 8.

TABLE 8

[Test Example 9]

A 10% W / V solution in which the compound of the present invention was dissolved in palm oil was coated in the form of a tape with a width of 5 cm on the stem of Hevia brasiliensis, just below the emulsion extraction cutout. Every other day, a semi-helical latex extraction cut was made to measure the quantity of dry rubber obtained after a two week period. The results are shown in Table 9. The figures in the table are percentages for the control (coated with palm oil alone).

TABLE 9

[Test Example 10]

The swelling test for young pea plants was carried out in the same manner as in Test Example 1, except for changing the concentrations of the compounds used for the leaves and stems in Table 10 to 1 ml.

The results were evaluated in five grades as follows.

-: No action

+: Medium effect

±: less effect

++: slightly larger effect

+++: very big effect

TABLE 10

[Test Example]

The effect on tomatoes was tested in the same manner as in Test Example 3 using the compounds of the concentrations shown in Table 11.

The results are shown in Table 11.

TABLE 11

[Test Example 12]

The effect on tomato plants was tested in the same manner as in Test Example 5 using the compounds of the concentrations shown in Table 12. This result is shown in Table 12.

TABLE 12

[Test Example 13]

Ripe tomatoes, which have not been colored yet, were harvested and coated with an amount of 2 ml of the hydrating agent of the present invention diluted with water to the concentrations shown in Table 13. The coated tomatoes were left indoors for 10 days and then the degree of coloring was measured. This result is shown in Table 13.

TABLE 13

[Test Example 14]

One week before the persimmon tree (cultivar Fuyu) completely bloomed, the aqueous solution of each of the hydrating agents of the present invention and 2-chloroethylphosphonic acid (comparative compound) were sprayed over the persimmon tree at the concentrations shown in Table 14. Test results were examined 20 days after treatment to determine fruiting rate and fruit to leaf ratio. This result is shown in Table 14. The ratio of fruit to leaf represents the balance between the number of leaves and the number of fruits, which is the number of fruits per leaf.

TABLE 14

This result demonstrates that the drug according to the present invention can harvest fruit to a degree close to the ideal fruit-to-leaf ratio (20 to 25) in Furu persimmon cultivation, and can significantly save labor for picking fruit.

[Test Example 15]

At each concentration shown in Table 15, an aqueous solution of the solution of the present invention was sprayed over the stem and leaves of the pineapple (breed, Singapore Spanish) in an amount of 50 ml per pineapple. At 50 days after the treatment, the flowering rate (the number of pineapples in bloom versus the number of pineapples treated) was measured. The results are shown in Table 15.

TABLE 15

[Test Example 16]

Mandarin orange (breed, Unshu) having a color similar to the transparent color of the firefly's back was immersed for 3 minutes in an aqueous solution of the emulsifier of the present invention diluted to the respective concentrations shown in Table 16, and left for 5 hours in the room. Then they were washed thoroughly with water and dried in air. At 10 days after the treatment, the acidity of the orange was measured to observe the colored state. Test results were expressed as the average of five oranges in one compartment. The coloring state was shown by the ratio similar to the test example 16.

TABLE 16

[Test Example 17]

Stems and leaves of cucumbers (cultivar, Otone No. 1) in the four-leaf stage were grown in a greenhouse after spraying 10 ml of each aqueous solution of the wetting agent of the present invention at the concentrations shown in Table 17. Based on the total number of flowers, the percentage of attached pistils was tested. The results are expressed as the average of four parts per compartment. This result is shown in Table 17.

TABLE 17

[Test Example 18]

The aqueous solution of the emulsifier of the present invention prepared at the respective concentrations shown in Table 18 was sprayed over the stem and leaves of chestnut (3 year old, 1.0-1.5 m in height) in the amount of 50 ml, and sprayed in the amount of 5 ml for the small persimmon did. 15 days after the treatment, the deciduous ratio was tested. A 100% deciduous rate means that all the leaves have fallen, while a 0% deciduous rate means that no leaves have fallen. This result is shown in Table 18.

TABLE 18

[Test Example 19]

Swelling tests for young peas were made in the same manner as described in Test 10 using the compounds of the concentrations shown in Table 19. The results are shown in Table 19.

TABLE 19

[Test Example 20]

A pot with a diameter of 12 cm was filled with volcanic ash soil, and evenly grown Gangnam beans (with vines) were transplanted into two pots. When the pots were left in a greenhouse and the roots of the Gangnam beans were rooted, the hydrating agent of the present invention diluted with water to the respective concentrations shown in Table 20 was evenly sprayed on the stems and leaves of the Beanstalk plants in an amount of 2 ml.

The plant was then grown in a greenhouse for 10 days, after which the growth of the upper jaw, yellowing and deciduous leaves were observed. Evaluation for this effect was expressed in the same ratio as described in the test 10, and the plant damage was evaluated in the same manner as described in Test Example 3. The results are shown in Table 20.

TABLE 20

[Test Example 21]

The test for tobacco plants was carried out in the same manner as described in Test Example 5.

This result is shown in Table 21.

TABLE 21

[Test Example 22]

The coloring test for mandarin orange was carried out in the same manner as described in Test Example 6 using each compound at the concentrations shown in Table 22. This result is shown in Table 22.

Table 22

[Test Example 23]

The effect of promoting deciduous leaves of chestnut was tested in the same manner as described in Test Example 18 using the respective compounds at the concentrations shown in Table 23. This result is shown in Table 23.

TABLE 23

Claims (1)

2-sulfonyloxyethyl phosphonic acid (or 2-sulfonyloxyethyl thionophosphone) of the following general formula (1) characterized by reacting a compound of the following general formula (2) with a compound of the following general formula (3) Acid) process for the preparation of derivatives.

In each formula above, R ₁ is a substituted or unsubstituted alkyl group, alkenyl group or aryl group, X is O or S, R ₂ and R ₃ are the same or different and each is an -OR 'group, -SR' group or -N (R ') ₂ group or halogen, wherein R' is a hydrogen atom or a substituted or unsubstituted alkyl group, an alkenyl group or Although it is an aryl group, provided that the R 'in the -N (R') ₂ group may be the same or different, and the group may be a morpholino group, but when X is O, both R ₂ and R ₃ are- OR ', at least one -OR' group is an -OH group, and when X is S, both R ₂ and R ₃ cannot be -N (R ') ₂ groups, Y is Cl or -OR 'group, Z is -OR 'group, -SR group, or -N (R') ₂ group.