JPH06312967A - Amido compound or its salt and pant growth regulating agent containing it as active component - Google Patents

Abstract

PURPOSE:To provide an amido compound having an activity to reduce the content of an endogenic ethylene in a plant and useful for keeping freshness of cut flowers, etc., as a plant growth regulating agent. CONSTITUTION:The compound of formula I [R<1>, R<2>, R<3> and R<4> are H or lower alkyl; R<5> and R<6> are H, lower alkyl, alkynyl, alkynyl, halogen, (lower alkyl- substituted) phenyl or (lower alkoxy-substituted) phenyl; (l), (m) and (n) are 0-7 and l+m+n <=7], e.g. N-(3-carboxypropionyl)aminooxyacetic acid disodium salt. The compound of formula I is obtained by reacting a compound of formula II (R<7> is H or lower alkyl) with a compound of the formula M<1>(OH)q [M<1> is alkali or alkaline earth metal; q is 1-2] or a compound of the formula R<8>OM<2> [R<8> is lower alkyl; M<2> is alkali metal].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel amide compound or a salt thereof and a plant growth regulator containing the same as an active ingredient.

[0002]

2. Description of the Related Art Ethylene formed in plants is known to promote plant senescence. If aging can be suppressed, various things can be performed such as extending the life of cut flowers, potted flowers, preventing the fall of flowers and fruits of vegetables and fruit trees, controlling the maturity of fruits, and increasing the yield. Therefore, it has been long awaited to develop a compound that reduces the endogenous ethylene content in plants and utilize it as a plant growth regulator.

[0003]

Means for Solving the Problems As a result of diligent studies to solve the above problems, the present inventors have found that the general formula

[Chemical 2] [Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a lower alkyl group, R ³ and R ⁴ are the same or different and represent a hydrogen atom or a lower alkyl group, and R ⁵ and R ⁶ are The same or different, each represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, or a phenyl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group.
l, m and n are the same or different, 0, 1, 2,
Represents 3, 4, 5, 6 or 7 (provided that 1, m, n
Is less than 7. ). ] It has been found that the amide compound represented by the following or a salt thereof (hereinafter referred to as the compound of the present invention) has an action of lowering the endogenous ethylene content in plants, and can be used as an active ingredient of a plant growth regulator,
The present invention has been completed.

In the above description of the compounds of the present invention, examples of the lower alkyl group include C ₁ -C ₆ alkyl group, examples of the alkyl group include C ₁ -C ₂₀ alkyl group, and examples of the alkenyl group include C ₂ —C ₂₀ alkenyl group,
The alkynyl groups include C ₂ -C ₂₀ alkynyl group, the halogen atom fluorine atom, a chlorine atom, a bromine atom or an iodine atom, include C ₁ -C ₆ alkoxy group such as a lower alkoxy group To be The salt of the compound represented by the general formula [I] is obtained when R ¹ and / or R ² in the general formula [I] is a hydrogen atom, and the salt is an alkali salt such as sodium salt or potassium salt. Examples thereof include salts acceptable as plant growth regulators such as metal salts such as metal salts or alkaline earth metal salts such as calcium salts, substituted ammonium salts such as ammonium salts or triethylammonium salts, and the like.

The compounds of the present invention have the general formula

[Chemical 3][In the formula, R⁷Represents a hydrogen atom or a lower alkyl group
And R³, R^Four, R^Five, R ⁶, L, m and n are as described above.
Have the same meaning. ] The compound shown by the general formula M¹(OH) q [III] [wherein M¹Is an alkali metal atom or alkaline earth gold
Represents a genus atom, and q is M¹Is an alkali metal atom
1 for M¹Represents 2 when is an alkaline earth metal atom
You ] The compound shown by these, or general formula R⁸OM² [IV] [In the formula, R⁸Represents a lower alkyl group, M²Is Arca
Represents a metal atom. ] With a compound represented by
It can be manufactured by This reaction is solvent-free
Or water, alcohol such as methanol, ethanol, etc.
It is carried out in a solvent, and the reaction temperature range is usually 0 to 100.
C, the reaction time range is usually 1 to 48 hours,
The amount of the reagent provided is 1 mol of the compound [II]
The compound [III] or the compound [IV] is 1 to 2 mol.

The compounds of the present invention have the general formula

[Chemical 4] [In the formula, X represents a halogen atom, and R ¹ , R ³ ,
R ⁴ , l, m and n have the same meanings as described above. ] The compound shown by

[Chemical 5] [In the formula, R ² , R ⁵ and R ⁶ have the same meanings as described above. ] It can manufacture by making it react with the compound shown by these. The present invention is carried out using a base and a solvent as necessary, and the reaction temperature range is -20 to 30.
The range of the reaction time is 1 to 4 hours. Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate, organic bases such as triethylamine and pyridine, and solvents include halogenated hydrocarbons such as dichloromethane and chloroform, toluene, benzene and the like. Aromatic hydrocarbons, ethers such as diethyl ether and tetrahydrofuran, water and the like can be mentioned.

Further, the compound of the present invention in which at least one of R ¹ and R ² is a lower alkyl group is hydrolyzed in the presence of a base such as sodium hydroxide in a solvent such as water or alcohol to give R ¹ And salts of compounds in which R ² is a hydrogen atom can be obtained.

After completion of the reaction, the reaction solution is extracted, concentrated, filtered,
The desired compound of the present invention can be obtained by subjecting to ordinary post-treatment such as neutralization and desalting, and further performing operations such as column chromatography and recrystallization as necessary.

Some of the compounds of the present invention which can be produced by the above production method are shown in Tables 1 to 3.

[0010]

[Chemical 6]

[Table 1]

[Table 2]

[Table 3]

The compound [II], which is a starting compound for the compound of the present invention, has the general formula

[Chemical 7] [In the formula, R ³ , R ⁴ , 1, m and n have the same meanings as described above. ] The compound shown by

[Chemical 8] [In the formula, R ⁵ , R ⁶ and R ⁷ have the same meanings as described above. ] It can manufacture by making it react with the compound shown by these.

The compound [II] can be prepared by reacting the compound [VII] with hydroxyamine to give a compound of the general formula

[Chemical 9] The compound of formula [IX] and the general formula

[Chemical 10] [In the formula, R ⁵ , R ⁶ , R ⁷ and X have the same meanings as described above. ] It can also manufacture by reacting with the compound shown by these.

The compound [VI] is a compound of the general formula N-hydroxyphthalimide and

[Chemical 11] [In the formula, R ² , R ⁵ , R ⁶ and X have the same meanings as described above. ] The compound represented by the general formula

[Chemical 12] [In the formula, R ² , R ⁵ and R ⁶ have the same meanings as described above. ] It can manufacture by obtaining the compound shown by these and then reacting a compound [XII] and hydrazine.

The compound [VI] is prepared by reacting acetoxime with the compound [XI] to give a compound of the general formula

[Chemical 13] Alternatively, the compound [XIII] may be hydrolyzed under acidic conditions and further esterified if necessary.

The compound [V] has the general formula

[Chemical 14] [In the formula, R ¹ , R ³ , R ⁴ , 1, m and n have the same meanings as described above. ] It can manufacture by halogenating the compound shown by these. Compound [XIV] can be produced by reacting compound [VII] with compound [IV] and neutralizing them. In addition, the compound [V]
Is the general formula

[Chemical 15] [In the formula, R ³ , R ⁴ , 1, m and n have the same meanings as described above. Formula R ⁸ OH [XVI] wherein the compound represented by], R ⁸ are as defined above. ] It can also manufacture by making it react with the compound shown by these.

Since the compound of the present invention lowers the amount of endogenous ethylene, it is said to prolong the life of cut flowers, potted flowers, prevent falling of flowers and fruits of vegetables and fruit trees, control the maturity of fruits, and increase the yield. It is used as an active ingredient of plant growth regulators for various purposes. Hereinafter, the use for storing cut flowers will be described in more detail by way of example.

When a cut flower is preserved using the compound of the present invention, for example, the cut end of the cut flower may be immersed in an aqueous solution of the compound of the present invention, and no special treatment is required, so that it can be easily carried out by anyone. . Representative examples of the method for storing cut flowers include a method of maintaining the freshness of the cut flowers while soaking them in the aqueous solution, and a method of maintaining the freshness of the cut flowers for a certain period of time. Examples of the former include so-called post-processing such as selling cut flowers in a container such as a bucket at a store, or storing cut flowers in a vase at home or at an exhibition, and the latter includes, for example, flower harvesting. There is a so-called pre-treatment in which the producer performs the drug treatment for a certain period of time, for example, 4, 12 or 24 hours later, and then ships. As described above, the present invention can be used in many situations.

The concentration of the compound of the present invention in the above aqueous solution varies depending on various conditions such as the type of flower to be treated and cannot be specified unconditionally, but it is generally about 1 to 2000 ppm, preferably about 2 in the case of post-treatment. 1000 ppm, about 20-2000 ppm for pretreatment, more preferably about 6-600 ppm for posttreatment, about 20-2000 pp for pretreatment
m (4 hours treatment) or about 20 to 600 ppm (24 hours treatment). When the compound of the present invention is used as a cut flower preservative, it is usually used in the form of an aqueous solution. A suitable surfactant or a polar solvent such as ethanol may be contained in the aqueous solution.

Specific examples of the surfactant include alkylbenzene sulfonate, higher alcohol sulfate ester salt,
Alkyltrimethylammonium chloride, betaine type, sodium lauryl sulfate, naphthalene formaldehyde condensate, polyoxyethylene sorbitan monooleate, polyoxyethylene styryl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene Block polymers, sucrose fatty acid esters and the like can be mentioned. The concentration of the surfactant used varies depending on various conditions such as the type of surfactant, the type of plant, the formulation type, the treatment time and the treatment method, and cannot be specified unconditionally, but generally it is about It is 3 to 1000 ppm, and in the case of post-treatment, it is about 3 to 300 ppm.

The aqueous solution contains nutrients such as nitrogen, phosphoric acid, potassium, sucrose, iron, zinc, etc., which have been conventionally used.
Micronutrients such as manganese, copper, boron, B-Nine,
It is also possible to mix a plant growth regulator such as benzyladenine.

The target flowers include, for example, carnation (Dianthus caryophyllus L.) and lathy (Lathy).
rus odoratus L.), key lily (Liliumelegans Tun)
b.), Western species aconite (Aconitum napellus), Willow milkweed (Asclepias tuberosa L.), Hanaturanoo (Phys)
ostegia virginiana), Delphinium a
jacis L.), Japanese mallow (Lavatera trimestris L.),
Campanula medium L., C.glomerata L.,
C. persicifolia L.), yellow ginger (Dicentra spectab
ilis DC.), Veronica (Veronica L.), Euphorbia fulgens, Astromelia (Alstromeria x hybrida), Freesia (hysia)
brida LHBailey), Dianthus babatus
L.), Snapdragon (Antirrhium majus L.), Scapiosa causasica, Stock (Matthiola in
cana R.Br.), Gypsophila (Gypsophila paniculata)
L.), bougainvillea (Bougainvillea Comm.), Geranium (Pelargonium x hortorum LH Bailey), calceolaria (Calceolaria x hybrida Hort), orchid (Ca
ttleya x hybrida, Cymbidium x hybrida, Paphiopedil
um x hybrida, DendrobiumSwartz, Phalaonopsis x hyb
rida, Oncidium Swartz), Bouvardia S
alisb), statice (Limonium Mill), gloriosa (G
loriosa L.), Cosmos (Cosmos Cav.), Lisianthus (Eustoma russellianum G. Don), Dahlia xc
ultorum Thorser et Reis), Hokusha (Fuchsia L.),
Examples include Santaca (Ixora Chinensis Lam.),
It is not limited to these flowers.

[0022]

EXAMPLES The present invention will be described in more detail with reference to production examples and test examples, but the present invention is not limited to these examples. The compound numbers in the examples are shown in Table 1.
Means a compound number of ~ 3. First, a production example is shown.

Production Example 1 (Production of Compound (18)) Succinic anhydride (1 g), ethyl aminooxyacetate hydrochloride (1.56 g), sodium acetate (0.82 g) and dimethylaminopyridine (0.1 g) were added to 1,2 g. -Dichloroethane (5
0 ml) and heated under reflux for 4 hours. After completion of the reaction, the reaction solution was cooled, 0.5N hydrochloric acid (30 ml) was added for liquid separation, the organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was subjected to silica gel chromatography (developing solvent; hexane: acetic acid). Purification with ethyl = 2: 1) gave N- (ethoxycarbonylmethoxy) succinimide (1.15 g). ¹ H-NMR 60MHz δ (ppm) [Solvent: CDCl ₃ , internal standard:
TMS] 1.38-1.6 (t, 3H), 2.68 (s, 4H), 4.03-4.38 (q, 2H), 4.
65 (s, 2H) The N- (ethoxycarbonylmethoxy) succinimide (1.15 g) obtained above was suspended in a 1N aqueous sodium hydroxide solution (11.6 ml), and the mixture was stirred overnight at room temperature. After completion of the reaction, water in the reaction solution was distilled off under reduced pressure to obtain the desired N- (3-
Carboxypropionyl) aminooxyacetic acid disodium salt (1.3 g) was obtained. ¹ H-NMR 60MHz δ (ppm) [solvent: D ₂ O, external standard:
TMS] 2.37 (s, 4H), 4.20 (s, 2H)

Production Example 2 (Production of Compound (38)) Ethyl aminooxyacetate hydrochloride (4.85 g) was suspended in dichloromethane (50 ml), and triethylamine (6.4 g) was added thereto while stirring at room temperature. It was then cooled in an ice-water bath and 5-methoxycarbonylvaleric acid chloride (5.
(57 g) was added dropwise, the reaction solution was returned to room temperature and further stirred for 2 hours. After completion of the reaction, water (50 ml) was added to the reaction solution for liquid separation, the organic layer was dried over magnesium sulfate and filtered, and then the solvent was evaporated under reduced pressure. Silica gel chromatography of the residue (developing solvent; hexane: ethyl acetate = 2:
Purification in 1) gave the desired ethyl N- (5-methoxycarbonylpentanoyl) aminooxyacetate (1.23 g). ¹ H-NMR 60MHz δ (ppm) [Solvent: CDCl ₃ , internal standard:
TMS] 1.18-1.42 (t, 3H), 1.56-1.80 (m, 4H), 2.03-2.46 (m, 4
H), 3.68 (s, 3H), 4.08-4.43 (q, 2H), 4.47 (s, 2H)

Next, some physical properties of the compounds of the present invention ( ¹ H-NMR 60 MHz δ (pp
m)). Compound (2) [solvent: CDCl ₃ , internal standard: TMS] 1.25-1.5 (t, 3H), 3.78 (s, 3H), 4.14-4.49 (q, 2H), 4.
52 (s, 2H) compound (3) [solvent: D ₂ O, internal standard: 3- (trimethylsilyl) propionic acid-2,2,3,3-d ₄ , sodium salt] 5.21 (s, 2H) compound ( 25) [Solvent: D ₂ O, External standard: TMS] 1.58-2.33 (m, 6H), 4.20 (s, 2H) Compound (34) [Solvent: D ₂ O, Internal standard: 3- (trimethylsilyl) propionic acid - 2,2,3,3-d _4, sodium salt] 1.42-1.72 (m, 4H), 1.92-2.40 (m, 4H), 4.21 (s, 2H)

Next, test examples will be shown. Test Example 1 Carnation Freshness Retention Test Three carnations (variety: Nora) were placed alive in an aqueous solution of each test compound containing 2% sucrose and stored in a growth room at 25 ° C. The freshness of each flower was observed 7 days after the treatment. Freshness was judged according to the following evaluation criteria. A: Fresh B: Start wilting C: Withering / fading progress D: Withering results are shown in Table 4.

[Table 4]

[0027]

INDUSTRIAL APPLICABILITY The compound of the present invention is useful as an active ingredient of a plant growth regulator for keeping freshness of cut flowers and various other uses because it suppresses ethylene production in plants.

Front Page Continuation (72) Inventor Ritsuto Mizutani 4-5-3 Kitahama, Chuo-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. A general formula: [Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a lower alkyl group, R ³ and R ⁴ are the same or different and represent a hydrogen atom or a lower alkyl group, and R ⁵ and R ⁶ are The same or different, each represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, or a phenyl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group.
l, m and n are the same or different, 0, 1, 2,
Represents 3, 4, 5, 6 or 7 (provided that 1, m, n
Is less than 7. ). ] The amide compound shown by these, or its salt. 2. A plant growth regulator comprising the compound according to claim 1 or a salt thereof as an active ingredient.