JPH02145552A - Novel quaternary ammonium compound, production thereof and plant growth regulator containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is 6-22C alkyl or alkenyl; R2 is 1-4C alkyl or hydroxyalkyl; R3 and R4 are (BO)xH (B is 1-4C alkylene; x is 1-5); m is 2 or 3; A is 1-10C alkyl, alkylene, hydroxyalkyl, etc.]. EXAMPLE:Di(oleylmethyldihydroxyethylammonium) succiniate. USE:A plant growth regulator effectively used for many species of plants with hardly any phytotoxicity. PREPARATION:A quaternary ammonium compound expressed by formula II (Y is Cl, Br, I or F) is reacted with a compound expressed by the formula A(COOD)m (A is 1-10C alkyl, alkylene, hydroxyalkyl, etc.; D is alkaline or alkaline earth metal) in a solvent (e.g. isobutanol) at 30-100 deg.C to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel quaternary ammonium compound, a method for producing the same, and a plant growth regulator containing the compound as an active ingredient.

[Prior Art] Various kinds of drugs related to plant growth are known, but many of the conventional drugs tend to cause phytotoxicity or are effective only on a limited number of plants.

Therefore, there has been a need for a plant growth regulator that causes less phytotoxicity and is effective for multiple types of plants.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a novel quaternary ammonium compound that has little phytotoxicity and has a plant growth regulating function that is effective for many types of plants, a method for producing the same, and a method for producing the compound as an active ingredient. The present invention provides plant growth regulators.

[Means to solve the problem] The novel quaternary ammonium compounds of the present invention are - killing, It is a quaternary ammonium compound represented by

The method for producing the compound of the present invention includes: -Sardination, R3... (1,) [wherein, R is an alkyl group or alkenyl group having 6 to 22 carbon atoms, and R2 is a carbon number 1 to 22]. 4 represents an alkyl group or a hydroxyalkyl group. R3 and R4 are (BO)xH
, where B is an alkylene group having 1 to 4 carbon atoms,
represents an integer or non-integer from 1 to 5. m represents 2 or 3.

A is an alkyl group having 1 to 10 carbon atoms, an alkylene group, a hydroquine alkyl group, a sulfur-containing alkyl group, [wherein R1 is an alkyl group or alkenyl group having 6 to 22 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms] Represents an alkyl group or a hydroxyalkyl group. R3 and R4 are (BO)xH, where B is an alkylene group having 1 to 4 carbon atoms, and X is an integer or non-integer of 1 to 5. Y represents C], B", I or F.] and a quaternary ammonium compound represented by A (
(3) [wherein A represents an alkyl group having 1 to 10 carbon atoms, an aminoalkyl group, a sulfur-containing aminoalkyl group, a hydroxyalkyl group, a sulfur-containing alkyl group, Or, when these groups are absent, it represents an alkyl group, an aminoalkyl group, or a sulfur-containing atom. ]
It represents a minoalkyl group or represents the case where these groups are absent. D represents an alkali metal or alkaline earth metal atom. m represents 2 or 3. ] and at least one solvent selected from the group consisting of linear or branched alcohols having 1 to 6 carbon atoms, methyl ethyl ketone, dimethyl sulfoxide, dimethyl formamide, dioxane, ethyl acetate, and cyclohexanol. Among these, the method is characterized in that the reaction is carried out in the presence or absence of a small amount of the novel quaternary ammonium compound represented by the above general formula (1).

The compounds of the present invention have little phytotoxicity and have plant growth regulating functions that are effective for many types of plants.

The reaction conditions in the method for producing the compound of the present invention vary depending on the type of reaction solvent, but are as follows in terms of quantity. i.e. 3 to 2 at a temperature of 30°C to 100°C.
After the reaction is stirred for 4 hours, the generated alkali metal halide or alkaline earth metal halide is removed by filtration, and the filtrate is concentrated to obtain the compound represented by (1).

Furthermore, this concentrate can be added to acetone, methyl ethyl ketone,
It can be purified by dissolving it in toluene, benzene, xylene, etc. and filtering it, and then concentrating the filtrate.

In addition, during the reaction of the present invention, 10 w t of the reaction product,
It is also possible to carry out the reaction by adding the compound of general formula (1) in an amount of less than 1%.

Examples of the compound represented by the general formula (2) used in the production method of the present invention include octylmethyldihydroxyethylammonium chloride, laurylmethyldihydroxyethylammonium bromide, oleylethyldihydroxyethylammonium iodide, stearylmethyldihydroxypropylammonium Examples include chloride, hexylethyldihydroxybutylammonium bromide, oleyltrihydroxyethylammonium chloride, lauryltrihydroxyethylammonium chloride, oleylmethyldihydroxyethoxyethylammonium chloride, and the like.

In addition, examples of the compound represented by -killing (3) include potassium maleate, potassium succinate, potassium fumarate, sodium malonate, potassium adipate, potassium malate, potassium citrate, sodium tricarballylate, and tartaric acid. Potassium, potassium aspartate, potassium thiodipropionate, cystine potassium salt,
Examples include sodium thiodiglycolate, potassium oxalate, potassium aconitate, and the like.

The quantitative relationship between the compound of general formula (2) and the compound of general formula (3) used in the production method of the present invention is -
) for one carboxyl group of the compound of general formula (2)
The amount corresponding to one compound of (2) may be sufficient, but it may also be used such that 1 to 1.2 carboxyl groups correspond to one compound of -killing (2).

In addition, during the reaction, the compound of -killing (2) and the general formula (3
) There is no problem even if less than loWtl% of water is present based on the total amount of the compounds.

The reaction in the present invention is expressed as follows.

m [(R-N -R)Ye] + A (COOD) [(R-N ■ ■ R4). ] A (Cooe) + DY The solvent used in the production method of the present invention may be any solvent that can dissolve either or both of the compound of -Kiburi (2) or the compound of -Kaburi (3). Examples of such solvents include linear or branched alcohols having 1 to 6 carbon atoms, ethyl acetate, dioxane, methyl ethyl ketone, cyclohexanol, dimethyl sulfoxide, dimethyl formaldehyde, and the like. The amount of solvent used is -
An amount equivalent to or 10 times the total amount of the compound (2) and the compound (3) is suitable.

As mentioned above, in order to achieve the reaction of the present invention, 3 to 3
A reaction time of 24 hours is sufficient.

After the reaction is completed, the reaction product (compound of the present invention) dissolved in the solvent is separated from the by-produced alkali metal halide or alkaline earth metal halide by filtering it from the reaction system. Compounds of the invention can be obtained by removing the solvent from the filtrate.

If further purification is required, dissolve the concentrate from which the above solvent has been removed in a linear or branched alcohol having 1 to 6 carbon atoms, acetone, benzene, toluene, xylene, etc., filter it, and concentrate the filtrate. Alternatively, the filtrate may be cooled to precipitate crystals.

In addition, in the reaction system, the corresponding compound of general formula (1),
- 1 of the total amount of the compounds of sacrifice (2) and - sacrifice (3)
When adding less than 0 wt 1%, or -
When using chloride or bromide as the compound for killing (2), -10wt of the compound for killing (2),
% or less of alkali iodide may be added. Further, to prevent coloring during the reaction, a small amount of nitrogen gas may be passed through the reactor.

[Example code] Next, the present invention will be specifically explained using examples.

Example 1 81 g of oleyl methyl dihydroxyethylammonium chloride, 20 g of potassium succinate, and 200 g of isobutanol were placed in a four-eye flask equipped with a stirrer and a cooling condenser, and the mixture was heated to 40 to 50°C while passing a small amount of nitrogen gas through it.
The mixture was allowed to react for 6 hours. After the reaction was completed, the formed precipitate was filtered off, and the precipitate was further washed with 30 ml of isobutanol, and then the filtrate and washing liquid were subjected to vacuum evaporation.

This concentrate was dissolved in 200 g of toluene and filtered, and the filtrate was concentrated to obtain 82 g (theoretical amount: 85.6 g) of waxy di(oleylmethyldihydroxyethylammonium) succinate.

Elemental analysis and infrared absorption spectroscopy were performed.

Elemental analysis value (%) C70,65 (70,09) HLl, 61. (11,88) 0 14.89 (14,95)N 3
．． 32 (3,27)C,Q O,01() Infrared absorption spectrum analysis In addition to the absorption attributed to oleylmethyldihydroxyethylammonium, the absorption of -coo attributed to succinate was measured at 1570 cm''-' and 1380 cm-'.

Example 2 Laurylmethyldihydroxyethylammonium bromide 73.6g, sodium aspartate 19.0g
, isopropanol 200g, di(laurylmethyldihydroxyethylammonium) asparaginate 3.5
g was placed in a four-eye flask equipped with a stirrer and a cooling condenser, and the mixture was reacted at 50° C. for 4 hours while passing a small amount of nitrogen gas through the flask. After the reaction was completed, the generated precipitate was filtered off, and the precipitate was further washed with 30 ml of isopropanol, and the filtrate and washing liquid were concentrated under reduced pressure to distill off the isopropanol. After dissolving this concentrate in toluene, insoluble matter was filtered off, and toluene was distilled off from the filtrate under reduced pressure to form a waxy di(
65.7 g (theoretical amount: 70.7 g) of laurylmethyldihydroxyethylammonium) asparaginate were obtained.

Elemental analysis value (%) CB4.53 (64,49) H11,40 (11,45) 0 17.98 (18,10)N 5.
91 (5,94) Br O,008 (calculated values in parentheses) Example 3 Put 81 g of oleylmethyldihydroxyethylammonium chloride, 33 g of cystine potassium salt, and 200 g of isopropanol into a four-eye flask equipped with a stirrer and cooling condenser, and add a small amount. 65 to 7 while passing nitrogen gas through the air.
The reaction was carried out at 5°C for 7 hours. After the reaction was completed, the generated precipitate was filtered off, and the filtrate was concentrated under reduced pressure. After dissolving this concentrate in 200 g of toluene, insoluble matter was filtered off, and the filtrate was concentrated to give 95.2 g of waxy di(oleylmethyldihydroxyethylammonium)cystinate (theoretical ff 19
7.8g) was obtained.

Elemental analysis value (%) CG: 1.72 (63,80) H10,78 (10,83) 0 13.01 (13,08) N 5.
8B (5,72) 3 6.52 (6,54) C) 0.00g (Calculated values in parentheses) Example 4 87.1g of oleyl trihydroxyethylammonium chloride, 21g of sodium tartrate, 200g of isobutanol were mixed with a stirrer. The mixture was placed in a four-eye flask equipped with a cooling condenser and reacted at 80 to 90°C for 7 hours. After the reaction was completed, the generated precipitate was filtered off, and the filtrate was concentrated under reduced pressure. After dissolving this concentrate in 200 g of acetone, insoluble matters were filtered off, and the filtrate was concentrated to obtain 90 g (theoretical amount: 94.8 g) of waxy di(oleyl trihydroxyethylammonium) tartrate.

Elemental analysis 1ia (%) CB5.79 (65,82) H10,93 (10,97) 0 20.21 (20,25) N 2
．． 89 (2,95)C)0.1 ()
Inner needle calculation value Example 5 0.000196.0.0 of the compound obtained in Example 1
Aqueous solutions of 0.01%, 0.01%, and 0.196 were prepared, and soybean, corn, and rice seeds were immersed in these aqueous solutions at 25°C for 12 hours.

Next, vermiculite was placed in a polyethylene cup and these seeds were sown. This was placed in a greenhouse maintained at 25° C. and grown by submerging it in water once a day for 10 days. At the same time, a comparative example (untreated) was prepared by immersing the seeds in water only.

Tables 1 to 3 show the results of measuring the length of stems and leaves, the number of stems and leaves, and the length of roots. As is clear from the table, the compound of the present invention was found to act as a growth regulator for dicotyledonous plants, monocotyledonous plants, and the like.

(Margin below)

Claims (1)

[Claims] 1. General formulas, ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(1) [In the formula, R_1 represents an alkyl group or alkenyl group having 6 to 22 carbon atoms, and R_2 represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms. R_3 and R_4 are (BO
)xH, where B is an alkylene group having 1 to 4 carbon atoms, and x is an integer or non-integer of 1 to 5. m represents 2 or 3. A represents an alkyl group having 1 to 10 carbon atoms, an alkylene group, a hydroxyalkyl group, a sulfur-containing alkyl group, an aminoalkyl group, or a sulfur-containing aminoalkyl group, or represents the case where these groups are absent. ] A novel quaternary ammonium compound represented by: 2. General formulas, ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(2) [In the formula, R_1 represents an alkyl group or alkenyl group having 6 to 22 carbon atoms, and R_2 represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms. R_3 and R_4 are (BO
)xH, where B represents an alkylene group having 1 to 4 carbon atoms, and x represents an integer or non-integer of 1 to 5. Y is Cl
, Br, I or F. ] A quaternary ammonium compound represented by the general formula A(COOD)_m (3) [
In the formula, A represents an alkyl group having 1 to 10 carbon atoms, an alkylene group, a hydroxyalkyl group, a sulfur-containing alkyl group, an aminoalkyl group, or a sulfur-containing aminoalkyl group, or represents the case where these groups are absent. D represents an alkali metal or alkaline earth metal atom. m represents 2 or 3. ] and at least one solvent selected from the group consisting of linear or branched alcohols having 1 to 6 carbon atoms, methyl ethyl ketone, dimethyl sulfoxide, dimethyl formamide, dioxane, ethyl acetate, and cyclohexanol. In the general formula (1) according to claim 1, the reaction is carried out in the presence or absence of a small amount of the novel quaternary ammonium compound represented by the general formula (1) according to claim 1. A method for producing a novel quaternary ammonium compound is shown. 3. Novel fourth compound represented by general formula (1) according to claim 1
A plant growth regulator containing an ammonium compound as an active ingredient.